JPS61275741A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To enhance sensitivity and graininess and the like by sensitizing with a specified sensitizing dye, silver halide grains each having outer shells, each of the shells specified in silver iodide content, formed on the outside of an inner shell (core) made of silver bromide or iodobromide. CONSTITUTION:The core/shell type silver halide emulsion contains silver halide grains composed of <=10mol% iodide in the outermost shell of each grain, and one of the outer shells has the highest content of the iodide more than the content of the outermost layer by <=6mol% in the highest content outer shell, and the inner core has the iodide content higher by >=3mol% than that of the outermost shell and lower by <=3mol% than that of the highest content layer. These silver halide grains are sensitized to give the max. spectral absorption in the wavelength region of >=600nm by using the sensitizing dye represented by general formula (I) in which Z<1>, Z<2> are each a nonmetallic atomic group necessary to form a basic hetero ring; R<1>, R<2> are each alkyl optionally substd. by OH, COOH, or the like; L<1>, L<2>, L<3>, L<4> are each methine; X<1> is an acid anion; l1, l2, m1, m2, m3, n1 are each 0 or 1, and m1+m2+m3=1-3. As a result, deterioration of sensitivity due to high shutter speed can be prevented.

Description

DETAILED DESCRIPTION OF THE INVENTION A. Field of Industrial Application The present invention provides an internal core consisting essentially of silver bromide and/or silver iodobromide, and an internal core provided outside the internal core and consisting essentially of silver bromide and/or silver iodobromide. The present invention relates to a silver halide photographic light-sensitive material containing negative-working silver halide grains having a plurality of outer shells made of silver oxide and/or silver iodobromide.

2. Prior Art In recent years, demands for silver halide emulsions for photography have become increasingly strict, and even higher demands are being made for photographic performance such as high sensitivity, excellent graininess, high sharpness, low fog density, and a sufficiently wide exposure range. There are demands for standards.

In order to meet these demands, silver iodobromide emulsions containing 0 to 10 mol % of iodine are well known as high-sensitivity emulsions. Conventionally, methods for preparing these emulsions include pH conditions such as ammonia method, neutral method, and acidic method.
A single jet method, a double jet method, etc. are known as a method of controlling /', g conditions and a mixing method.

Based on these known techniques, technical means have been elaborately studied and put into practical use for the purpose of achieving higher sensitivity, improved graininess, higher sharpness, and lower fog. Regarding the silver iodobromide emulsions that are the object of the present invention, research has been carried out on emulsions in which not only the crystal habit and grain size distribution but also the iodine concentration distribution within each silver halide grain is controlled.

The most traditional method for achieving 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 is actively incorporated.

A study that theoretically calculated this quantum efficiency and considered the influence of particle size distribution was described, for example, in the Proceedings of the 1980 Tokyo Symposium on Advances in Photography, "Interactions Between Light and Materials," page 91. has been done. According to this research, it is predicted that creating a monodisperse emulsion by narrowing the grain size distribution will be effective in improving quantum efficiency. It is also reasonable to conclude that monodisperse emulsions would be advantageous in order to efficiently achieve high sensitivity while maintaining low fog in a process called chemical sensitization, which will be described in detail later. It is thought that the

In order to produce monodispersed emulsions industrially, Japanese Patent Application Laid-open No. 54-4
As described in Publication No. 8521, 1 limb dense pA
Under the control of g and p +i, it is necessary to control the theoretically determined supply rate of silver ions and halogen ions to the reaction system, and to provide sufficient stirring conditions. Silver halide emulsions produced under these conditions have a cubic, octahedral or tetradecahedral shape. That is, (1
It consists of so-called normal crystal grains having various ratios of 00) planes and (111) planes. It is known that such normal crystal particles can increase sensitivity.

On the other hand, silver iodobromide emulsions comprising polydisperse twin crystal grains have been known as silver halide emulsions suitable for high-speed photographic films.

Further, silver iodobromide emulsions containing tabular twin grains are disclosed in JP-A-58-113927 and others.

On the other hand, in JP-A-53-2240, it was reported that developing activity could be increased and sensitivity could be increased by using laminated silver halide grains in which a plurality of shells were placed on the outside of an inner core.
Publication No. 8, Special Publication No. 43-13162, J, P
Hoto, Sci., 24.198 (1976), etc.

In addition, silver halide grains in which a coating layer is provided as the outermost layer of silver halide grains by halogen substitution are disclosed in West German Patent No.
No. 932650, Japanese Patent Application Laid-open No. 51-2417, 51
Although these silver halide grains may speed up the fixing speed, they also inhibit development and prevent sufficient sensitivity from being obtained. It is not practical as a negative-tone emulsion due to the fact that

In addition, positive type (internal latent image type) silver halide grains having a plurality of coating layers on the outside of the inner core by halogen substitution are known, and are disclosed in U.S. Pat. Nos. 2,592,250 and 4,075. , No. 020 specification, JP-A-55-12754
It is described in detail in Publication No. 9, etc. These silver halide grains are often used in internal latent image type direct positive light-sensitive materials such as those for diffusion transfer, and because of their high internal sensitivity, they cannot be used in the negative-tone emulsion that is the object of the present invention. It is not used at all.

On the other hand, JP-A-58-181037 and JP-A-60-35
Silver halide grains having an outer shell on an inner core and various iodine contents in each layer are disclosed in publications such as No. 726 and JP-A-59-116647.

In the field of silver halide photographic materials, advances in various technologies have recently led to the appearance of color sensitive materials with an ISO display sensitivity exceeding too much. However, as the sensitivity of these photosensitive materials increases, their graininess and sharpness usually deteriorate, resulting in insufficient image quality compared to conventional photosensitive materials, making them unsuitable for consumer viewing purposes. The present situation is extremely unsatisfactory, and a high-sensitivity negative light-sensitive material with excellent graininess and sharpness is desired.

Negative photosensitive materials with even higher sensitivity are required for astrophotography, indoor photography, sports photography, and the like.

Conventionally, it is a well-known technique to add a sensitizing dye to a silver halide emulsion to expand the wavelength range to which the silver halide emulsion is sensitive, thereby sensitizing it spectrally. The sensitizing dye used for the above purpose should have an appropriate spectral sensitizing wavelength range, have high spectral sensitization, and be able to diffuse into other photosensitive layers or be added to other than sensitizing dyes. Those having favorable properties such as no interaction with the agent are selected.

Many proposals have been made in the past regarding sensitizing dyes that satisfy the various conditions described above. According to such proposals, although there are cases in which a single sensitizing dye can produce a satisfactory sensitizing effect, a desirable effect can only be obtained by using a combination of two or more sensitizing dyes. In many cases, it is said that a method of use that also has a supersensitizing effect is more preferable.

Furthermore, many combinations of sensitizing dyes have been proposed that provide practically satisfactory color reproduction even when photographed under light sources with different color temperatures. For example, these are proposed in Japanese Patent Publications Nos. 49-6207, 55-44368, and 55-44369. Furthermore, there is also an invention described in Japanese Patent Publication No. 59-9901, which achieves the same object by combining a compound that does not have a color sensitizing effect by itself with a sensitizing dye.

However, some drawbacks can be seen with such inventions as well. One is that the silver halide photographic light-sensitive material may increase fog by 7 m degrees or decrease sensitivity over time, which may lead to undesirable results in terms of photographic performance. Furthermore, with the increasing sensitivity of silver halide photographic materials, it has become possible to take practically satisfactory photographs even with a small amount of light, but on the other hand, cameras with high shutter speeds have made it difficult to take photographs in bright places. is also becoming possible. It is effective for capturing the momentary movements of sports photos and car races. In such a case, compared to the commonly used silver halide photographic light-sensitive materials of about 50100, exposure is required for a short time with high-intensity light. In that case,
Sensitivity decreases due to high-light reciprocity failure, which is known to those skilled in the art, and for example, when shooting at a shutter speed of 10-4 seconds, the sensitivity often becomes less than half of the displayed sensitivity. sell.

Such high-intensity reciprocity failure is also a major drawback. Improvement proposals have also been made to address these shortcomings. for example,
JP-A-5A-176637 proposes a method for improving the stability of photographic performance of silver halide photographic materials during storage over time by incorporating a black and white silver halide developing agent.

However, in order to improve the high-irradiance reciprocity law failure, which is one of the drawbacks, a method of adding metals such as Ir and Rh during preparation of silver halide emulsions has been proposed, for example, in US Pat. ing. However, with this method, contamination during the manufacturing process, such as insufficient cleaning during the manufacturing process, contaminates other silver halide emulsions that are prepared subsequently, resulting in undesirable adverse effects such as increased fog density and decreased sensitivity. There is also a possibility that

C1 Object of the invention The object of the invention is to provide a silver halide with high sensitivity, excellent sensitivity-fog relationship, wide exposure range, excellent graininess and sharpness, and in particular, which has silver iodide as its silver halide composition. The object of the present invention is to provide a silver halide photographic material which has high red light sensitivity when the grains are spectrally sensitized to the red light region and has excellent high-intensity reciprocity law failure characteristics.

20 Structure of the invention and its effects, that is, the present invention comprises an inner core consisting essentially of silver bromide and/or silver iodobromide, and an inner core provided outside the inner core and consisting essentially of silver bromide and/or silver iodobromide. /or a silver halide photographic material containing negative-working silver halide grains having a plurality of outer shells made of silver iodobromide, wherein the iodine content of the outermost shell of the silver halide grains is 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 both these shells are provided between the outermost shell and the iodine-rich shell. an intermediate shell having an iodine content between , 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 content shell is higher than that of the intermediate shell. 3 mol% or more, and furthermore, the silver halide grains have a maximum spectral absorption wavelength of 60% due to at least one sensitizing dye represented by the following general formula ([).
This invention relates to a silver halide photographic material characterized by being sensitized to 0 nm or more.

General formula (I): (XIQ)nl [However, in this general formula, Zl and Z2 are nonmetallic atomic groups necessary to form a basic heterocycle (from the viewpoint of color sensitization, when used alone It is not preferable that Zl and 21 simultaneously form an oxazole ring or an imidazole ring.

), R1 and R2 are alkyl groups, at least one of which is an alkyl group substituted with a hydroxy group, carboxyl group or sulfo group, Ll, LZ, L3 and L4 are me, chin groups (however, between LI and L3 may be combined to form a carbocycle); Xl is an acid anion: IIzllt
m 1 , Ill z , m 2 and nl are O or 1
(When forming an inner salt, it is O.) (However, ml
+m2+m, =l, 2 or 3 may be. ).

] In the silver halide composition of the silver halide grains according to the present invention, the above-mentioned "substantially consisting of..." means halogen other than silver bromide or silver iodobromide to the extent that the effects of the present invention are not impaired. This means that silver chloride, for example silver chloride, may be contained. Specifically, in the case of silver chloride, the proportion thereof is preferably 1 mol % or less.

To summarize the features of the photographic material according to the present invention,
It is as follows +1) to (8).

(1) By using an emulsion containing core/shell type silver halide grains with a high iodine shell on the inside, high sensitivity, wide exposure range, and excellent graininess can be achieved (compared to non-core/shell emulsions). can get.

(2) Even 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 iodine shell is preferably 6 to 40 mol%, and is 6 mol% or more higher than the outermost shell layer, but if this content is less than 6 mol%, or the iodine content is higher than the outermost shell layer. If the amount is less than 6 mol %, the sensitivity will decrease, and if it exceeds 40 mol %, polydispersity will occur. Therefore, from the viewpoint of sensitivity and sharpness, it is preferable not to exceed 40 mol %.

(4) The difference in iodine content between the middle shell and the outermost shell or high iodine shell should be at least 3 mol%, but this is because if this difference is too small, the effect of the middle shell will be reduced. Because it will be. (Sensitivity decreases.) Also, the upper limit of this difference in iodine content is 35 mol% due to the effect of the intermediate shell (sensitivity,
This is desirable from the viewpoint of effectively bringing out the monodispersity, fog-sensitivity relationship, and sharpness.

(5) If the iodine content in the entire silver halide grain is too high, the developability will be poor, resulting in a decrease in sensitivity; if it is too low, the gradation will be too hard, the exposure range will be narrow, and the graininess will be reduced. Since there is a tendency for deterioration to occur, it is preferable to select a specific range.

(6) Monodisperse emulsions are superior to polydisperse emulsions in terms of sensitivity, brightness, and fog-sensitivity relationships. In other words, in polydispersity, the shell-forming reaction is nonuniform, making it difficult to form an ideal core/shell structure, the presence of microparticles that degrade sharpness, and the chemical sensitization after particle formation being difficult to form. Since the optimum conditions differ depending on the grains, the sensitivity tends to be low and the fog-sensitivity relationship tends to worsen, so monodisperse emulsions are preferably used.

(7) In multilayer color light-sensitive materials, a phenomenon occurs in which the sensitivity of a single layer becomes lower due to the use of multiple layers (referred to as multilayer desensitization effect). Not only is this highly effective, but it can also be used more effectively in multilayer color photosensitive materials due to this heavy N desensitization effect.

(8) Since the silver halide grains are spectrally sensitized by using at least one sensitizing dye represented by the general formula (I), high sensitivity effective in the red light region can be obtained. The light-sensitive material that can be spectrally sensitized according to the present invention can have excellent graininess and sharpness,
It also has a wide exposure range and can improve high-intensity reciprocity law failure characteristics.

In order to further improve the above-mentioned excellent effects, h: iodine content of high iodine shell (mol %) [m: iodine content of intermediate shell (mol %).

II! : When expressed as the iodine content (mol%) of the outermost shell, △
1=th-tz>s mol%, △Ih=Ih-1m
>4 mol%, ΔIj'=Im-11>4 mol%, ΔI>10 mol%, ΔI h>4 mol%, ΔI
It is even better to set #>4 mol%. (■ above) Here,
+7! =0 to 5 mol%, preferably 0 to 2 mol%,
Furthermore, it is desirable to set it to O-1 mol%. Further, rh is preferably 6 to 40 mol%, and even more preferably 10 to 40 mol%.

(■ above) Also, the volume of the outermost shell is 4 to 70 mol% of the entire particle (
, 10 to 50 mol% is more preferable. The volume of the high iodine shell is preferably 10 to 80% of the whole grain, and 20 to 5
0%, more preferably 20 to 45%. The volume of the intermediate shell is preferably 5 to 60%, more preferably 20 to 55%, of the entire particle.

The high iodine shell may be at least a part of the inner shell, but preferably a separate inner core exists inside the high iodine shell.

The iodine content of the internal core is 0 to 40 mol%, 0 to 10
Mol% is preferred, and 0 to 6 mol% is more preferred. The particle size of the inner core is 0.05 to 0.8 μm, and even 0.05 to 0.
．． 4 am is better.

In addition, regarding the characteristic point (2) above, the iodine content in the entire particle is preferably 1 to 20 mol%, preferably 1 to 15 mol%, and more preferably 2 to 12 mol%.

Regarding the characteristic point (2) above, the particle size distribution of the particles may be either polydisperse or monodisperse, but it is preferable to use a monodisperse emulsion with a coefficient of variation of the particle size distribution of 20% or less, and furthermore, the coefficient of variation of the particle size distribution is preferably 20% or less. It is preferable that the amount is 15% or less. This coefficient of variation is defined as , and is a measure of monodispersity.

As a multilayer color photosensitive material with the feature point (■) above, there is a blue-sensitive layer,
A multilayer is constructed from three or more emulsion layers consisting of three types of photosensitive layers: a red-sensitive layer and a green-sensitive layer, and at least one emulsion layer of the red-sensitive layer is coated with the halogen according to the present invention (or as described above). It is desirable to contain silveride grains and a sensitizing dye.

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

To further describe the layer structure of the silver halide grains of the present invention, the internal core and the high iodine shell may be the same as described above, or the internal core may be provided separately inside the high iodine shell. Also good. The inner core and the high iodine shell, the high iodine shell and the middle shell, and the middle shell and the outermost shell may be adjacent to each other, or there may be at least one layer of another shell having an arbitrary composition between each shell. (This is called an arbitrary shell).

These arbitrary shells may be of a single general type with a uniform composition, or
It may be a group of shells with a stepwise change in composition, consisting of multiple shells with a uniform composition, or it may be a continuous shell in which the composition changes continuously within an arbitrary shell; A combination may be used, and there may be a plurality of high-iodity shells and intermediate shells, or there may be only one shell.

Next, an example of the layer structure of silver halide grains according to the present invention will be explained. The iodine content is shown as 1.

1. Inner core = 3-layer structure of high iodine shell Iodine content Shell diameter core (JP3) (Inner core - IOIt of high iodine shell >3 mol% +3-15 mol% 1.2, um 2nd shell (
Medium 1fil□ It ++>3 mol% ■
! -5 mol% 1.4 pm 1st shell #la
i + -o ~to mol% I, -0.5 mol% 1.6. c + m2, 6-layer structure including 4th and 5th shells of arbitrary composition between the inner core and high iodine shell, shell diameter core Φ crime) (inner control illusion arbitrary 1
b=4.0 mol% 0.1 μm 5th shell <-)
4Lt +, -2.0 mol%
0.27μm 4th shell (-) Optional
! , -2.6 mol% 0.8 μm third shell I
7;t)lJJja;Oh It>3 mol% 1. −
15.0 mol% 1.12μ+n 28th (Ifj
btl) It++>3 mol% 1
．． -5.0 mol% 1.44. crm number! Shell (Mld
D r + = 0 to 10 mol% [,
=0.5 mol% l, (i, urn3, with arbitrary fifth and sixth shells between the inner shell and the high iodine shell, and two layers of intermediate shell between the outermost shell and the high iodine shell) 7-layer structure iodine content shell diameter 7th shell (internal control illusion!
, -4 mol% 0.10pm 6th shell (optional insertion W
Arbitrary 1,=2 mol% 0.2
7μm No. 5M <Any push-in Any
1. -8 mol% 0.8μm 4th shell 1m
I4-1+>3 mol% +4-15 mol% 1.12.17 mth ta 'JklLm
I t ”O~to -t-le94 I +
= 0.5 Moa 1/% 1.6 pm4, any 6th and 7th shells between the inner shell and the high iodine shell, and the high iodine shell (5th shell) and the intermediate shell (3rd shell) 8N structure with one layer of arbitrary shell (fourth shell) between the middle shell (third shell) and one layer of arbitrary shell (second shell) between the middle shell (third shell) and the outermost shell Iodine content Shell diameter No. 8 Shell (inner scream optional 1
g-4 mol% 0. IO, IJm 7th shell (I, Tii
:shell)′ Optional 1. =2 mol% 0.27μrn 6th shell ((ball shell)
Optional 16-4 mol% 0.8gm
5th shell (116 J, fi +5-11>3
Mol% +5-15 Mol% 1.12. urn 4th
Shell (optional shell) Arbitrary +4
-9 mol% 1.24μm 3rd shell (1'1ii)a
) l x -1+ -3 mol% I, -5
Mol% 114/7rn 2nd shell (arbitrary RD
fLt 1 t -4.5 mol%
1.50μm first shell (IH shell) 1. =
0-10 mol% 1,=2 mol% 1.6 ur
n5, structure with multiple high iodine shells Iodine content Shell diameter 6th shell (of which 11! IuA-) Arbitrary
1b=4 mol% 0.10μrn 5th
Shell (high iodine shell) Is −+z >3 mol%
I, = 15 mol% 0.27μrn+, -+, >6
Mol% 4th shell (I L tray optional 1
a = 5 MoJI/% 0.80μrn 3rd shell GN
tH wound 1 j-1, > 3 mol% Iz = 15 mol% 1.12 μm■2 1 kmol% 2nd shell (Middle 1 song W It I, > 3 mol%
1, -5 mol% 1.44 μm first shell (outermost tilt!
1=0-10 mol% ++-0.3 mol% 1.6
Layer m The inner core of the silver halide grains of the present invention is described in detail in CI+1m1a at Pl by Glafkides, P.
+ysique.

PhoLohraphique (Paul MOntel, 1967), G.F.

PhoLohraphic' [E.
mulsion ChimisLry) (The Focal Press (TI+e Focal Pres)
s), 1966), V. L. Zelikman (v.
L.

Making and Coating Photographic Imagine (Zelilvan) et al.
gand Coating PhoLohraph
ic Emulsion) (The Focal Press, 19
64). That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble root salt with the soluble halogen salt may be one-sided mixing method, simultaneous mixing method, or a combination thereof. Good too.

It is also possible to use a method in which particles are formed in an excess of silver ions (so-called back-mixing method).

As one type of simultaneous mixing method, a method of keeping I) Ag in the liquid phase in which silver halide is produced, ie, a so-called Chondrald double jet method, can also be used. According to this method, a silver halide emulsion having a regular crystal shape and a nearly uniform grain size can be obtained.

Although two or more silver halide emulsions formed separately may be used as a mixture, it is preferable to use a double jet method or a control double jet method.

The pAg when preparing the inner core varies depending on the reaction temperature and the type of silver halide solvent, but 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, commonly known silver halide solvents such as ammonia and thioether can be used.

The shape of the internal core may be plate-shaped, spherical, twinned, or octahedral, cubic, tetradecahedral, or mixed.

Also, to make the particle size uniform, British patent 1.53
No. 5.016, Special Publication No. 48-36890, No. 52-1
As described in No. 6364, there is a method of changing the addition rate of silver nitrate or aqueous alkali halide solution depending on the grain growth rate, and as described in U.S. Pat. It is preferable to use a method of changing the aqueous solution concentration as described above to grow quickly within a range that does not exceed the critical saturation level.

These methods do not cause re-nucleation and each silver halide grain is uniformly coated, so arbitrary shells, high iodine shells,
It is also preferably used when introducing an intermediate shell or an outermost shell.

If necessary, one or more arbitrary shells may be provided between the high iodine shell and the inner shell of the silver halide grains of the present invention. This high iodine shell can be provided by a conventional halogen substitution method, a method of coating with silver halide, etc. after subjecting the formed inner core or the inner shell to which an arbitrary shell has been provided a desalting step, if necessary.

The halogen substitution method can be carried out, for example, by adding an aqueous solution consisting mainly of an iodo compound (preferably potassium iodo), preferably at a concentration of 10% or less, after the internal core is formed. For details, see U.S. Patent No. 2,592.250, 4.07.
This can be carried out by the methods described in JP-A No. 5,020, JP-A-55-127549, and the like. At this time, in order to reduce the difference in iodine distribution between particles of the high iodine shell, it is desirable to add the iodine compound aqueous solution over a period of 10 minutes or more at a concentration of 10 -2 mol % or less.

Further, as a method for newly coating the inner core with silver halide, it can be carried out, for example, by simultaneously adding an aqueous halide solution and an aqueous silver nitrate solution, that is, by a simultaneous mixing method or a controlled double jet method. For details, see Japanese Patent Application Laid-open No. 53-22408, Japanese Patent Publication No. 43-1
No. 3162, Japanese Patent Application Laid-open No. 14829/1983, J Photo Science (J, Photo, Sci.
), 24, 198 (1976).

pAg when forming a high iodine shell is the reaction temperature,
Although it varies depending on the type and amount of the silver halide solvent, those mentioned above are preferably used. When using ammonia as a solvent, 7 to 11 are preferable.

Methods for forming high iodine shells include simultaneous mixing method,
Controlled double jet method is more preferred.

The intermediate shell of the silver halide grains of the present invention includes a high-iodide shell having a high-iodide shell on the surface, or a high-iodide shell having one or more arbitrary shells on the high-iodide shell as necessary, and an inner core. A silver halide having a halogen composition different from that of the high iodine shell can be further coated on the outside of the grains by a simultaneous mixing method or a controlled double jet method.

Regarding these methods, the method of providing a high iodine shell described above is similarly used.

The outermost shell of the silver halide grains of the present invention includes an intermediate shell having an intermediate shell on the surface, or an intermediate shell having one or more arbitrary shells on the intermediate shell as necessary, a high iodine shell, and an inner shell. Silver halide having a halogen composition different from that of the high iodine shell can be coated on the outside of the grain containing the shell by a simultaneous mixing method or a Chondrald double jet method.

Regarding these methods, the above-mentioned method of providing a high iodine shell is similarly used. One or more optional shells can be provided between the inner shell and the high iodine shell, between the high iodine shell and the intermediate shell, and between the middle shell and the outermost shell, or there is no need to provide one. good. For these arbitrary shells, the above-mentioned method for providing high iodine shells can be similarly used. inner shell, high iodine shell, intermediate shell,
For the outermost shell and arbitrary shells at each position, a desalting process may be performed according to a conventional method as necessary when forming adjacent shells, or shells may be formed continuously without performing a desalting process. You may do so.

Regarding the iodine content of each coating shell of the silver halide grains of the present invention, for example, J, 1. Goldstein (Gol)
dsteln), D.B., Willi
ams) "X-ray analysis in rTEM/ATEM" Scanning Electron I Ron Microscope (1
977), Vol. 1 (I IT Research Institute, p. 651 (March 1977)).

The silver halide grains as the final product after the formation of the outermost shell of the present invention are freed from excess halogen compounds generated during preparation, by-products or unnecessary salts and compounds such as nitrates and ammonia, from the dispersion medium of the grains. May be removed.

Removal methods include the Nodel water washing method commonly used in general emulsions, the dialysis method, inorganic salts, anionic surfactants,
Anionic polymers (e.g. polystyrene sulfonic acid)
, or gelatin derivatives (e.g. acylated gelatin,
A sedimentation method using carbamoylated gelatin (such as carbamoylated gelatin), a pseudo-precipitation R (flocculation) method, etc. can be used as appropriate.

Silver halide grains in other layers containing silver halide grains other than the core/shell type of the present invention can be optically sensitized to a desired wavelength range. There are no particular restrictions on the optical sensitization method; for example, optical sensitization can be carried out using cyanine dyes such as zeromethine dyes, monomethine dyes, dimethine dyes, trimethine dyes, or optical sensitizers such as merocyanine dyes, either alone or in combination. I can do it. Combinations of sensitizing dyes are often used, especially for the purpose of supersensitization. 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 substantially absorb visible light and exhibits supersensitization. These techniques are described in U.S. Pat. Nos. 2.688,545 and 2.912.
No. 329, No. 3,397,060, No. 3,615.6
No. 35, No. 3,628,964, British Patent No. 1.195
．． No. 302, No. 1,242,588, No. 1,293.
No. 862, West German Patent (OLS) 2,030,32
No. 6, No. 2,121,780, Special Publication No. 43-4936
No. 114-14030, Research Disclosure
Volume 176 17643 (Published December 1978) No. 23
It is also described in section 3 of page ■. The selection can be arbitrarily determined depending on the wavelength range to be sensitized, sensitivity, etc., and the purpose and use of the photosensitive material.

Next, the core/shell type halogenated particles of the present invention are sensitized with the dye of the general formula (1).
In, the basic heterocyclic group formed by Zl and 22 is
A monocyclic or condensed 5- or 6-membered nitrogen-containing heterocyclic group known as a nucleus forming a cyanine dye, such as thiazole, thiazoline, imidazole, imidacilline, imidazolidine, thiazolidine, oxazole, oxazoline, Oxazolidine, selenazole, selenazoline, selenazolidine, pyrrole, viroline, pyrrolidine, pyridine, benzothiazole, benzoxazole, benzoselenazole, benzimidazole, indole, indolenine, naphtho(1,2-d)thiazole, naphtho(1,2- d) Oxazole, naphtho (2
, 3-d) oxazole, naphtho(2,1-d)selenazole, naphtho[1,2-d)selenazole, and the like. These heterocyclic groups include alkyl groups (e.g. methyl group, ethyl group, etc.), alkoxy groups (e.g. methoxy group, ethoxy group, etc.), halogen atoms (e.g. chloro atom, bromine atom, fluorine atom, etc.), carbamoyl group, sulfamoyl group. , an alkoxycarbonyl group (for example, methoxycarbonyl, ethoxycarbonyl), a phenyl group, a cyano group, etc. may be substituted.

The compound of the above general formula (1) is preferably of the following -M formula (
11).

General formula (■): In the above general formula (n), Y' represents S % Se, and Yt represents 5SSes 05NR''.

R1 and R1 are synonymous with R+ and Rz. W+ to W represent a lower alkyl group, an alkoxy group, a halogen atom, an aryl group, an alkoxy group, a carbonyl group, a cyano group, a carbamoyl group, or a sulfamoyl group. Wl and R2,
Wt and Ws, Wa and R3, and WS and Wh may be bonded to form a condensed ring. ) (1 is a synonym for XI. R2 is a synonym for n. R6 is an alkyl group,
Represents an aryl group, an aralkyl group, or an alkenyl group. R
represents an alkyl group, an aryl group, or a heterocyclic group, and the alkyl group is preferably a lower alkyl group, such as methyl, ethyl, propyl, etc., with ethyl being preferred. Examples of the heterocyclic group include aromatic heterocyclic groups such as chenyl and furyl, or acidic heterocyclic groups represented by the following general formula (III), and examples of the aryl group include a phenyl group.

General formula (■) 2 Q in general formula ([1)] is, for example, a pyrazolone derivative,
isoxacilone derivative, oxacilone derivative, 2.4
．． ．． 6-) Riketohexahydrobyrimidine derivative, 2
-1,000-oh 2.4.6- Triketohexahydropyrimidine derivative, rhodanine derivative, 2,4-thiazolidinedione derivative, 2-1,000-oh 2,4-oxazolidinedione derivative, thianaftynone derivative, hydantoin derivative,
Represents a group of nonmetallic atoms necessary to form a 5- or 6-membered heterocyclic nucleus selected from indandione derivatives, oxindole derivatives, etc.

Specific examples of sensitizing dyes used with the present invention are shown below, but the present invention is not limited thereto.

(+-6) N(C1R5).

(+-8) (+-10) N-15)
C2 summer (.

(1-16)
Czl[s(li8) (+-28) The amount of the sensitizing dye added in the present invention is 10 to 1000, preferably 20 to 4
It is 00■.

The above sensitizing dyes are used alone or in an amount that produces a supersensitizing effect, or in combination of two or more to achieve the desired spectral wavelength range. When used in combination, the usage ratio is within the optimal amount above. Select arbitrarily.

In the present invention, the silver halide emulsion includes activated gelatin; sulfur sensitizers such as allylthiocarbamide, thiourea,
Sulfur sensitizers such as cystine; selenium sensitizers; reduction sensitizers such as stannous salts, thiourea dioxide, polyamines, etc.; noble metal sensitizers such as gold sensitizers, specifically potassium aurithiocyanate, potassium chloro aureate, 2-aurothio-3-methylbenzothiadurium chloride, etc., or for example, ruthenium, palladium, platinum, rhodium,
Sensitizers of water-soluble salts such as iridium, specifically ammonium chlorovaladate, potassium chloroaurate, and sodium chloroparadate (these types can be used as sensitizers or fog suppressants depending on the amount) Even if chemically sensitized by using a combination of gold sensitizer and sulfur sensitizer (for example, combination of gold sensitizer and sulfur sensitizer, combination of gold sensitizer and selenium sensitizer, etc.), good.

The silver halide emulsion according to the present invention is 1. A sulfur-containing compound is added to form a chemical table 1, and before and during this chemical ripening,
Alternatively, after forming Table 1, at least one nitrogen-containing heterocyclic compound having at least one hydroxytetrazaindene and mercapto group may be included.

When forming a multilayer color light-sensitive material using the present invention, in order to provide blue sensitivity and green sensitivity, an appropriate sensitizing dye is added to 5X10-" to 3XIO-" per mole of silver halide.
Optical sensitization may be achieved by adding 3 moles. Various sensitizing dyes can be used, and each sensitizing dye can be used alone or in combination of two or more. Examples of sensitizing dyes that can be advantageously used in the present invention include the following.

That is, examples of sensitizing dyes used in the blue-sensitive silver halide emulsion layer include West German Patent No. 929.080, US Pat. No. 2,231,658, US Pat.
, No. 503.776, No. 2,519,001, No. 2,
No. 912,329, No. 3,656.959, No. 3,8
No. 72.897, No. 3,694,217, No. 4,02
No. 5,349, No. 4,046,572, British Patent 1.
No. 242,588, Special Publication No. 44-1.4030, No. 5
Examples include those described in No. 2-24844. Examples of sensitizing dyes used in green-sensitive silver halide emulsions include U.S. Pat.
,945. Typical examples thereof include cyanine dyes, merocyanine dyes, and composite cyanine dyes as described in No. '763, British Patent No. 505.979, and the like.

In order to add a sensitizing dye to the silver halide emulsion according to the present invention, a hydrophilic dye solution such as methyl alcohol, ethyl alcohol, acetone, dimethylformamide, or a fluorinated alcohol described in Japanese Patent Publication No. 40659/1984 is added in advance. Organic solvent (used by dissolving it).

The addition may be made at any time such as at the start of chemical ripening of the silver halide emulsion, during ripening, or at the end of ripening, and in some cases, it may be added at a step immediately before coating the emulsion.

The silver halide photographic 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 preventing irradiation. Such dyes include oxonol dyes, hemioxonol dyes, merocyanine dyes and azo dyes. Among them, oxonol dyes, hemioxonol dyes and merocyanine dyes are useful. Specific examples of dyes that can be used include British Patent Nos. 584, 609 and 1,277.
No. 429, JP-A-48-85130, JP-A No. 49-996
No. 20, No. 49-114420, No. 49-12953
No. 7, No. 52-108115, No. 59-25845, U.S. Patent No. 2,274,782, No. 2,533,47
No. 2, No. 2,956,879, No. 3,125,44
No. 8, No. 3,148,187, No. 3,177.078
No. 3,247.127, No. 3; 540,887, No. 3,575,704, No. 3.853.905,
It is described in No. 3,718,472, No. 4,071,312, No. 4,070, and No. 352.

When the silver halide light-sensitive material according to the present invention is used in a multilayer color light-sensitive material, it has two layers of blue-sensitive silver halide emulsion and a green-sensitive silver halide emulsion layer in addition to the red-sensitive silver halide emulsion layer of the present invention. It is preferable to do so. The blue-sensitive silver halide emulsion layer, the green-sensitive silver halide emulsion layer and the red-sensitive silver halide emulsion layer each contain a coupler, that is,
A compound capable of reacting with an oxidized color developing agent to form a dye can be contained.

It is generally preferred that the blue-sensitive silver halide emulsion layer contains a coupler that forms a yellow dye, and as the yellow coupler, a known closed ketomethylene coupler can be used. Among these, penzoylacetanilide and pivaloylacetanilide compounds can be advantageously used.

Specific examples of yellow couplers are disclosed in Japanese Patent Application Laid-Open No. 47-26133,
No. 48-29432, No. 50-87650, No. 51
-17438, No. 51-102636, Special Publication No. 1977
-19956, 46-19031, 51-33
No. 410, No. 51-10783, U.S. Patent No. 2,875
, No. 057, No. 3, 40.8, 194, No. 3.519
, No. 429, etc.

As magenta couplers that can be used in combination with the green-sensitive silver halide emulsion layer, pyrazolone compounds, indashilon compounds, cyanoacetyl compounds, virazolotriazole compounds, etc. can be used. Specific examples of magenta couplers that can be used include JP-A-49-111631 and JP-A-56.
No. -29236, No. 57-94752, Special Publication Showa 4B
-27930, U.S. Patent No. 2,600.788, No. 3
, No. 082,653, No. 3.408.194, No. 3,
No. 519,429 and Research Disclosure 1
There is one described in No. 2443.

Colored magenta couplers that can be used in combination with the green-sensitive silver halide emulsion layer include US Pat. No. 2,801,171;
Examples include those described in Japanese Patent Publication No. 3,519,429 and Japanese Patent Publication No. 48-27930.

As the cyan coupler used in the red-sensitive silver halide emulsion layer of the present invention, phenolic compounds, naphthol compounds, etc. (for example, ureido type cyan couplers, diacyl type cyan couplers, etc.) can be used.

Specific examples include U.S. Pat. No. 2,423.730 and U.S. Pat.
No. 474.293, No. 2,895,836, Japanese Unexamined Patent Publication No. 1973
0-117422, British Patent No. 1,038,331, British Patent No. 543.040, Japanese Patent Publication No. 48-36894, Japanese Patent Publication No. 48-59838, British Patent No. 50-137137, British Patent No. 51-146828, No. 53-105226,
No. 54-115230, No. 56-29235, No. 5
No. 6-104333, No. 56-126833, No. 57
-133650, 57-155538, 57-
No. 204545, No. 5B-118643, No. 59-3
No. 1953, No. 59-31954, No. 59-5965
No. 6, No. 59-124341, No. 59-166956, U.S. Patent No. 2.369,929, No. 2,434,2
No. 72, No. 2,698,794, No. 2,772.16
No. 2, No. 2,801,171, No. 2,895,826
No. 3,253.924, No. 3,311.476, No. 3,458,315, No. 3,476.563,
No. 3,591,383, No. 3,737,316, No. 3,758,308, No. 3,767.411, No. 3
, 790,384, 3.880,661, 3.
No. 926,634, No. 4,004,929, No. 4,0
No. 09.035, No. 4,012,258, No. 4,05
No. 2,212, No. 4,124.396, No. 4,134
, No. 766, No. 4,138.258, No. 4,146,
No. 396, No. 4,149,886, No. 4.178.1
No. 83, No. 4,205.990, No. 4,254.21
No. 2, No. 4, 264, 722, No. 4,288,5
No. 32, No. 4,296,199, No. 4,296.20
No. 0, No. 4,299,914, No. 4,333,999
No. 4,334,011, No. 4,386.155, No. 4,401.752, No. 4,427,767, etc.

A common colored cyan coupler can be used in combination with the red-sensitive silver halide emulsion layer of the present invention.

As a colored cyan coupler, Tokuko Sho 55-324
61 and British Patent Nos. 1, 084, 480, etc. can be used.

In a preferred embodiment when the present invention is used in a multilayer color photographic material, a compound (hereinafter referred to as DII'l (compound)) which releases a development inhibitor or its precursor by reacting with an oxidized form of a color developing agent is used. It is contained in at least one layer of the photosensitive silver halide emulsion layer, and more preferably, when the photosensitive silver halide emulsion layer is composed of two or more layers having different sensitivities, the blue-sensitive silver halide emulsion layer is contained in at least one layer. In at least one of the high-speed layer (BI()) of the silver halide emulsion layer, the high-speed layer (GH) of the green-sensitive silver halide emulsion layer, and the high-speed layer (RI-1) of the red-sensitive silver halide emulsion layer. It is to be contained in.

Typical examples of DIR compounds include DIR couplers in which a group capable of forming a compound having a development-inhibiting effect when separated from the active site is introduced into the active site of the coupler; for example, British Patent No. 935.454; US Patent 3,2
No. 27,554, No. 4,095,984, No. 4.14
No. 9,886, JP-A-57-151944, etc. The above-mentioned DIR coupler has the property that, when subjected to a coupling reaction with an oxidized form of a color developing agent, the coupler core forms a dye while releasing a development inhibitor. Further, in the present invention, U.S. Pat.
No. 8,041, No. 3,958,993, No. 3,961
, No. 959, No. 4,052,213, Japanese Unexamined Patent Publication No. 1983-1
No. 10529, No. 54-13333, No. 55-161
It also includes compounds that release a development inhibitor when subjected to a coupling reaction with an oxidized form of a color developing agent, such as those described in No. 237, but do not form a dye.

Furthermore, JP-A-54-145135 and JP-A-56-1
When reacted with oxidized color developing agents such as those described in No. 14946 and No. 57-154234, the mother nucleus forms a dye or a colorless compound, while the released timing group undergoes an intramolecular nucleophilic substitution reaction. Or so-called timing D, which is a compound that releases a development inhibitor through an elimination reaction.
IR compounds are also included in the invention.

Also, JP-A No. 58-160954, No. 58-16294
Timing DI in which a timing group as described above is bonded to a coupler core that produces a completely diffusible dye when reacted with an oxidized color developing agent described in No. 9.
It also includes R compounds.

According to the present invention, more preferred DIR compounds can be represented by the following general formulas (IV) and (V), and among these, the most preferred DIR compound is a compound represented by the following general formula (V).

General formula (IV): Coup-inhibitor In the formula, Coup is a coupler component (compound) capable of coupling with the oxidized form of a color developing agent, such as open-chain ketomethylene compounds such as acylacetanilides and acylacetate esters, and pyrazolones. , pyrazolotriazoles,
These are dye-forming couplers such as pyrazolinobenzimidazoles, indasilones, phenols, and naphthols, and coupling components that do not substantially form dyes such as acetophenones, indanones, and oxacylones.

In addition, the inhibitor in the above formula is a component (compound) that is released by reaction with a color developing agent and inhibits the development of silver halide.
and preferred compounds include benztriazole,
There are heterocyclic compounds and heterocyclic mercapto compounds such as 3-octylthio-1,2,4-triazole and the like.

Examples of the above-mentioned heterocyclic group include a tetrazolyl group, thiadiazolyl group, oxadiazolyl group, thiazolyl group, oxasilyl group, imidazolyl group, triazolyl group, and the like. Specifically, 1-phenyltetrazolyl group, 1-ethyltetra'/"J/L4.1-(4-hydroxyphenyl)tetrazolyl group, 1,3.4-thiazolyl group, 5-methyl-1 , 3,4-oxadiazolyl group, benzthiazolyl group, benzoxacylyl group, benzimidazolyl group, 4H-1,2,4-)riazolyl group, and the like.

In addition, in the above general formula (IV), the inhibitor is bonded to the active site of Coup.

General formula (■): Coup-TIM E-inhibitor In the formula, the inhibitor is the same as defined in the above general formula (IV). Coup also includes a coupler component that produces a diffusible dye, similar to that defined in general formula (IV). TIME is represented by the following general formula (VI), (■), (■
) and (IX), but are not limited to these.

General formula (■): In the formula, X represents an atomic group necessary to complete a benzene ring or a naphthalene ring. Y represents 10-, ru group or aryl group. ) and is bonded to the coupling position. Further, R and Rsz each represent a group having the same meaning as the above R53, but are substituted at the carotid position and bonded to a heteroatom contained in the inhibitor.

General formula (■): In the formula, W is a group having the same meaning as Y in the above general formula (Vl), and R54 and R5S are also each represented by the general formula (VT).
This group has the same meaning as R5I and R52 in .

R5& is a hydrogen atom, an alkyl group, an aryl group, an acyl group, a sulfone group, an alkoxycarbonyl group, or a heterocyclic residue, and R5? is a hydrogen atom, an alkyl group, an aryl group, a heterocyclic residue, an alkoxy group, an amine group, an acylamido group,
Represents a sulfonamide group, a carboxy group, an alkoxycarbonyl group, a carbamoyl group, and a cyan group. This timing group is bonded to the coupling position of Coup by W, and then an example of a timing group that releases the inhibitor by an intramolecular nucleophilic substitution reaction is shown in the general formula (■).

General formula (■): In the formula N u -E, Nu is a nucleophilic group having an electron-rich oxygen, sulfur or nitrogen atom, and is bonded to the coupling position of Coup. E is an electrophilic group having an electron-poor carbonyl, thiocarbonyl, phosphinyl, or thiophosphinyl group and is bonded to the heteroatom of the inhibitor.

V is a three-dimensional relationship between Nu and E, and from Coup to N
After u is released, it is a linking group that can break the intramolecular nucleophilic substitution reaction with the formation of a 3- to 7-membered ring and thereby release the inhibitor.

General formula (■): Coup-OCHz-inhibitor Coup and inhibitor have the same meanings as above.

The above DIR compounds are preferably added to the light-sensitive silver halide emulsion layer.

In the present invention, two or more types of DIR compounds may be included in the same layer. The same DIR compound may also be included in two or more different layers.

These DIR compounds are generally preferably used in amounts of 2X10-' to 5X10-' moles, more preferably 2X10-' to 5X10-' moles per mole of silver in the emulsion layer.

The pyrazolotriazole of the present invention, such as a non-diffusible coupler or a polymer coupler, which reacts with the oxidized form of a developing agent to form a diffusible dye that bleeds moderately in the silver halide emulsion layer of the present invention and other photographic constituent layers. Couplers other than magenta couplers may be used in combination. Non-diffusible couplers that react with the oxidized form of these developing agents to form diffusible dyes that bleed moderately are described in Japanese Patent Application No. 59-19361 filed by the present applicant.
For polymer couplers, reference can be made to the description in Japanese Patent Application No. 172151/1983.

The method of adding the DIR compound and the like is substantially the same as that for the magenta coupler of the present invention. That is, the above DIR
In order to incorporate the compound etc. into the coating solution for silver halide emulsion and other photographic constituent layers according to the present invention, the D I R
If the compound etc. is alkali-soluble, it may be added as an alkaline solution; if it is oil-soluble, the coupler etc. may be added to a high boiling point solvent (HB S ) according to the method described in the above-mentioned US patent specification. Low boiling point solvent (
It is preferable to dissolve it in combination with LBS), disperse it in the form of fine particles, and add it to the silver halide emulsion. At this time, if necessary, other hydroquinone Rfj4m forms, ultraviolet absorbers, browning inhibitors, etc. may be used in combination. Furthermore, two or more types of DIR compounds may be used in combination. Furthermore, to explain in detail the preferred method of adding DIR compounds, etc. in the present invention, one or more DIR compounds, etc. are added to the organic Acid amides, carbamates, esters, ketones, urea derivatives, ethers, hydrocarbons, etc., especially the high boiling point solvent (HBS) and/or the low boiling point solvent (LBS).
), mixed with an aqueous solution containing the anionic surfactant and/or nonionic surfactant and/or hydrophilic binder, emulsified and dispersed using a high-speed rotating mixer, and added to the silver halide emulsion.

In addition, the above-mentioned DIR compound etc. may be dispersed using the above-mentioned latex dispersion method.

In the present invention, the amount of the coupler added is generally preferably 2X10-'' to 5X10-' mol, more preferably 1X10-2 to 5XIO mol per mol of silver in the emulsion layer. It can be incorporated into the silver halide emulsion layer by a protect dispersion or latex dispersion method, and if the coupler is alkali-soluble, it may be added as an alkaline solution.

The photosensitive material of the present invention may have a so-called reverse layer structure as the structure of its photosensitive emulsion layer;
(See No. 9-193609, No. 59-202065, etc.)
However, a remarkable effect can be obtained especially in an inverted 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, in order from the side farthest from the support: ■ high-sensitivity JW of the blue-sensitive silver halide emulsion layer (BH), low-sensitivity layer (BL) of the blue-sensitive silver halide emulsion layer, and high-speed JW of the green-sensitive silver halide emulsion layer. Sensitive layer (C
, l(), low sensitivity rWI() of green-sensitive silver halide emulsion layer (
GL), the high-speed layer of the red-sensitive silver halide emulsion layer (RH
), a low-speed layer (RL) of a red-sensitive silver halide emulsion layer, or ■ a high-speed layer (RL) of a blue-sensitive silver halide emulsion layer (
BH), high-speed layer of green-sensitive silver halide emulsion layer (GH
), high sensitivity of red-sensitive silver halide emulsion layer [5 (RH),
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 (J!) of the red-sensitive silver halide emulsion layer. ! (RL).

For example, in ■■, especially in ■, the high-sensitivity layer (13H) of the blue-sensitive silver halide emulsion layer, the high-sensitivity layer (GH) of the green-sensitive silver halide emulsion layer, the high-sensitivity layer (13H) of the red-sensitive silver halide emulsion layer ( The silver halide contained in RH) has an average grain size (
The average particle size) is preferably 0.40 to 3.00 μm, more preferably 0.50 to 2.50 μm.

For example, in ■■ of the present invention, especially in ■, a low-speed layer (BL) of a blue-sensitive silver halide emulsion layer, a low-speed layer (GL) of a green-sensitive silver halide emulsion layer, a low-speed layer (GL) of a red-sensitive silver halide emulsion layer. The silver halide contained in the sensitive layer (RL) preferably has an average grain size of 0.20-1.50 μm, more preferably 0.20-1.0 μm.

In addition, the low-speed layer (BL) of the blue-sensitive silver halide emulsion layer, the low-speed layer (GL) of the green-sensitive silver halide emulsion layer, and the low-speed layer (RL) of the red-sensitive silver halide emulsion layer are called medium-speed layers. When separated into low sensitivity layer, the former is 0.30 to 1.50
μm, and the latter is preferably 0.15 to 1.00 μm.

The average grain size of the silver halide contained in the photosensitive silver halide emulsion layer of the present invention can be measured by various methods commonly used in the technical field for the above purpose. A representative method is Loveland's "Particle Size Analysis Method" A, S, T, M, Symposium on Light Microscopy, 1955, 94-12.
2 or in Chapter 2 of ``The Theory of Photographic Processes'' by Mies and James, 3rd edition, published by Macmillan Publishing Co., Ltd. (1966). The particle size can be measured using the particle's projected area or diameter approximation. If the particles are of substantially uniform shape, the particle size distribution can be described fairly accurately as diameter or projected area.

The silver halide photographic material of the present invention may contain various other photographic additives.

For example, Japanese Patent Application Laid-Open No. 46-2128, U.S. Patent No. 2.728.
659, and antifoggants, stabilizers, ultraviolet absorbers, color stain inhibitors, optical brighteners, color image browning inhibitors, and electrostatic agents described in Research Disclosure Magazine No. 17643. Inhibitors, hardeners, surfactants, plasticizers, wetting agents, etc. can be used. In the silver halide color photographic light-sensitive material of the present invention, the hydrophilic colloids used to prepare the emulsion include gelatin, derivative gelatin, graft polymers of gelatin and other polymers, proteins such as albumin and casein, and hydroxyl colloids. Examples include cellulose derivatives such as ethyl cellulose derivatives and carboxymethyl cellulose, starch derivatives, single or copolymer synthetic hydrophilic polymers such as polyvinyl alcohol, polyvinylimidazole, and polyacrylamide.

The support for the silver halide photographic material of the present invention includes:
For example, balaiku paper, polyethylene coated paper, polypropylene synthetic paper, transparent support with a reflective layer or a reflective material, glass plate, cellulose acetate,
There are transparent supports such as polyester films such as cellulose nitrate or polyethylene terephthalate, polyamide films, polycarbonate films, and polystyrene films, and these supports are appropriately selected depending on the intended use of the photosensitive material.

Various coating methods such as dipping coating, air doctor coating, curtain coating, and hopper coating can be used to coat the emulsion layer and other constituent layers used in the present invention. Also, U.S. Patent No. 2.761,791;
It is also possible to use a simultaneous coating method of two or more layers by the method described in No. 941,898.

The present invention is applicable to black and white general use, X-ray use, color use, infrared use,
For micro, silver dye bleaching, reversal, diffusion transfer,
It can be effectively applied to photographic materials for various purposes such as high contrast, photothermography, and heat-developable materials, but is particularly suitable for color sensitive materials for high illuminance.

There are no particular limitations on the method of processing photographic materials using the silver halide emulsion according to the present invention, and any processing method can be applied. For example, a typical example is
A method of carrying out bleach-fixing treatment after color development, and further washing and/or stabilization treatment if necessary; A method of carrying out bleaching and fixing separately after color development, and further carrying out washing and/or stabilization treatment if necessary; or anterior dura, neutralization;
Color development, stop fixing, water washing, bleaching, fixing, water washing, post hardening, water washing in this order, color development, water washing, supplementary color development, stopping, bleaching, fixing, water washing, stabilization in this order, color development Any method may be used for processing, such as a method in which developed silver produced by development is subjected to halogenation bleaching and then color development is performed again to increase the amount of produced dye.

Color developing solutions used in processing the silver halide emulsions of the present invention include, but are not limited to, p 11 color developing agents.
is preferably 8 or more, more preferably pH, l! +<9
-12 alkaline aqueous solution. The aromatic primary amine developing agent used as the color developing agent is a compound having a primary amino group on an aromatic ring and has the ability to develop silver halide exposed to light. Precursors that form such compounds may also be added.

The color developing agent mentioned above is typically p-phenylenediamine type, and the following are preferred examples.

4-Amino-N, N-diethylaniline, 3-methyl-
4-amino-N, N-diethylaniline, 4-amino-
N-ethyl-N-β-hydroxyethylaniline, 3-
Methyl-4-amino-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methoxyethylaniline, 3-methyl-4-amino-N-
Methyl-N-β-methanesulfonamidoethylaniline, 3-methoxy-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methoxy-4=amino-
N-ethyl-N-β-methoxyethylaniline, 3-acetamido-4-amino-N.

N-dimethylaniline, N-ethyl-N-β-[β-(
β-methoxyethoxy)ethoxy]ethyl-3-methyl-4-aminoaniline, N-ethyl-N-β-(β-methoxyethoxy)ethyl-3-methyl-4-aminoaniline, and salts thereof such as sulfates, hydrochloride, sulfite,
p-toluenesulfonate and the like.

Furthermore, for example, JP-A-48-64932, JP-A No. 50-1
31526, No. 51-95849, and those described by Bent et al., Journal of the American Chemical Society, Vol. 73, pp. 3100-3125 (1951) are also mentioned as representative examples.

The amount of these aromatic primary amino compounds to be used depends on where the activity of the developer is set; however, in order to increase the activity, it is preferable to increase the amount used. The amount used ranges from 0.0002 mol/l to 0.7 mol/l. Moreover, two or more compounds can be used in appropriate combination depending on the purpose. For example, 3-methyl-4-amino-N,N-diethylaniline and 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N
-Ethyl-N-β-methanesulfonamidoethylaniline and 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, etc. may be used in any combination depending on the purpose.

The color developing solution used in the silver halide color photographic light-sensitive material according to the present invention further contains various commonly added components, such as alkaline agents such as sodium hydroxide and sodium carbonate, alkali metal bisulfites, and alkali metals. Thiocyanates, alkali metal halides, benzyl alcohol, water softeners, thickeners, development accelerators, and the like can also be optionally included.

Examples of additives other than the above added to the color developing solution include bromides such as potassium bromide and ammonium bromide;
In addition to compounds for rapid processing solutions such as alkali iodide, nitrobenzimidazole, mercaptobenzimidazole, 5-methyl-benzotriazole, l-phenyl-5-mercaptotetrazole, anti-stain agents, anti-sludge agents, preservatives, There are multilayer effect promoters, chelating agents, etc.

Bleaching agents used in bleach solutions or bleach-fix solutions in the bleaching process are generally known to be those in which metal ions such as iron, cobalt, or copper are coordinated with aminopolycarboxylic acids, tetraacids, or organic acids such as citric acid. ing. Representative examples of the above aminopolycarboxylic acids include the following.

Ethylenediaminetetraacetic aciddiethylenetriaminepentaacetic acidpropylenediaminetetraacetic acidnitrilotriacetateiminodiacetic acid ethyl ether diaminetetraacetic acidethylenediaminetetrapropionateethylenediaminetetraacetic acid disodium saltdiethylenetriaminepentaacetic acidpentasodium saltnitrilotriacetic acid sodium salt Bleaching solutions can be used with various bleaching agents as mentioned above. It may also contain additives. When a bleach-fixing solution is used in the bleaching step, a solution containing a silver halide fixing agent in addition to the bleaching agent is used. Further, the bleach-fix solution may further contain a halogen compound such as potassium bromide. Then, as in the case of the above-mentioned bleaching solution, various other additives such as pH buffers, antifoaming agents, surfactants, preservatives, chelating agents, stabilizers, organic solvents, etc. are added and contained. Good too.

Examples of the halogenation-limited adhesive include silver halides and the like used in ordinary fixing processes, such as sodium 100sulfate, ammonium thiosulfate, potassium thiocyanate, sulfur and lithium thiocyanate, thiourea, and 1000000 thiocyanate. Mention may be made of compounds which react to form water-soluble silver salts.

The processing temperatures of the various processing steps such as color development, bleach-fixing (or bleaching, fixing), washing with water, stabilization, drying, etc. performed as necessary for the silver halide color photographic light-sensitive material according to the present invention are determined from the viewpoint of rapid processing. Preferably, the temperature is 30°C or higher.

The silver halide color photographic light-sensitive materials according to the present invention are disclosed in JP-A-58-14834, JP-A-58-105145, and JP-A-58-105145.
Stabilization treatment as an alternative to washing may be performed as shown in Japanese Patent Application No. 8-134634 and No. 58-18631, Japanese Patent Application No. 58-2709 and No. 59-89288, and the like.

Next, an example of producing silver halide grains according to the present invention will be specifically explained.

(1-1) Production of inner core: A silver iodobromide emulsion EM-1 containing 4 mol % of silver iodide was produced using the six types of solutions shown below.

(Solution A-1) Ossein gelatin 39.7 g
Distilled water 3936
mj2 Polyisopropylene-polyethyleneoxydisuccinic acid ester sodium salt 1 Magnesium disulfate 3.6g6
%Nitric acid 75.6mj
! Potassium bromide 2.06
g (Solution B-1) Ossein gelatin 35.4 g
Potassium bromide 807 g Potassium iodide 47 g Polyisopropylene-polyethylene oxydisuccinate sodium salt 10% ethanol solution
35.4m/distilled water
1432 m7! (Solution E-1) Silver nitrate 240g6%
Nitric acid 62m7! Distilled water 1467ml!
(Solution F-1) 25% KBr aqueous solution pAg adjustment required amount (
Solution H-1) 6% nitric acid pH Adjustment amount (?
8 liquids 1-1) 7% carbonic acid) IJum aqueous solution pH adjustment required amount At 40°C, JP-A No. 57-92523, No. 57-
Using the mixing stirrer shown in No. 92524, solution A-
Solutions E-1 and B-1 were added to Example 1 by a simultaneous mixing method. pAg, pfI and solutions E-1, B- during simultaneous mixing
The addition rate of 1 was controlled as shown in Table 1. I) Ag
The pH was controlled by changing the flow rates of solution F-1 and solution H-1 using a variable flow rate roller tube pump.

p) with solution 1-1 3 minutes after the end of addition of solution E-1
(adjusted to 5.5.

Next, the mixture was washed with demineralized water in a conventional manner and dispersed in an aqueous solution containing 125 g of ossein gelatin, and the total amount was adjusted to 4800 m (l) with distilled water.

According to electron microscopy, this emulsion has an average grain size of 0.09.
It was found that the emulsion was a monodisperse emulsion of μm.

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

Table 1 (1-2) Addition of fifth shell: Using the five types of solutions shown below, use the above EM-1 as a seed emulsion, and add silver iodobromide with a silver iodide content of 2 mol%. Emulsion EM-2 with a shell was prepared.

(Solun 1A-2) Ossein gelatin 34.54g
Distilled water 8642 m
10% ethanol solution of polyisopropylene-polyethyleneoxydisuccinate sodium salt
20m/4-hydroxy-6-methyl-1,3,3a.

7-Chitraazaindene 181.32
m, g28% ammonia water
117.4ml! 56% acetic acid aqueous solution
154 ml magnesium sulfate
16 g seed emulsion (EM-1>
0.329 mol equivalent amount (solution B-2) Ossein gelatin 18.72
gKBr 763
．． 8gKl
21.8 g4-hydroxy-6-methyl-1,3,3a.

7-chitraazaindene 2.17g
Magnesium sulfate 7.4g Distilled water 1578 mA
C'm liquid E-2) A g N O31142.4g 28% ammonia water 931.4
mj! Make up to 1921ml with distilled water.

(?Volume F-2) 50% KBr aqueous solution 1) Necessary amount of Ag adjustment (Solution G-2) 56% acetic acid aqueous solution pH Adjustment amount 4
At 0°C, JP-A-57-92523, JP-A-57-9
Using the mixing stirrer shown in No. 2524, solution A-2
Solutions E-2 and B-2 were added to the mixture by a simultaneous mixing method over a minimum time of 32.5 minutes without generation of small particles.

l) Ag, pH and addition rate of solutions E-2 and B-2 during simultaneous mixing were continuously controlled as shown in Table 2. I)
Ag and pH were controlled using a variable flow rate roller tube pump while changing the flow rates of solution F-2, solution G-2, and solution B-2. Two minutes after the addition of solution E-2 was completed, I) Ag was increased to 10.4 and then 2 minutes using solution G-2.
After a few minutes, the pH was adjusted to 6.0 with solution F-2.

Table 2 Next, the mixture was washed with demineralized water using a conventional method and dispersed in an aqueous solution containing 128.6 g of ossein gelatin, and the total volume was adjusted to 3000 ml with distilled water.

According to electron microscopy, this emulsion has an average grain size of 0.27.
The emulsion was found to be a highly monodisperse emulsion with a coefficient of variation in μm and particle size distribution of 12%.

(1-3) Adding a fourth shell: Using the five types of solutions shown below, use the above EM-2 as a seed emulsion, and add a shell of silver iodobromide with a silver iodide content of 2.6 mol%. Emulsion EM-3 was prepared.

(Solution A-3) Ossein gelatin 34.0 g
Distilled water 7779 m
l Polyisopropylene-polyethylene oxydisuccinate sodium salt 10% ethanol solution
20mj! 4-hydroxy-6-methyl-1,3,3a.

7-Chitraazainden 405 m
g28% ammonia water 117
．． 3mj! 56% acetic acid aqueous solution
72ml type 1 emulsion (EM-2)
0.303 mole equivalent (solution B-3) Ossein gelatin 1B, 74
gKBr 760
．． 2gK I
28.4 g4-hydroxy-6-methyl-1,3,3
a.

7-chitraazaindene 1.35g
Distilled water 1574 m
7! (Solution E-3) A g N O: 1 11
48 g28% ammonia water
937 mA 1930 m with distilled water 7! Make it.

(Solution 1"-3) 50% KBr aqueous solution pAg adjustment required amount (
Solution G-3) 56% acetic acid aqueous solution pH adjustment required amount 40
℃, JP-A-57-92523, JP-A-57-92
Using the mixer shown in No. 524, solutions E-3 and B-3 were added to solution A-3 by a simultaneous mixing method over a minimum time of 56.5 minutes without generation of small particles. The pAg, pH, and addition rate of solutions E-3 and B-3 during simultaneous mixing were controlled as shown in Table 3. pAg and pH were controlled using a variable flow rate roller tube pump while changing the flow rates of solution F-3, solution G-3, and solution f3-3. Two minutes after finishing adding solution E-3, add solution G-
3 to bring the pAg to 10.4, and after another 2 minutes solution F-
3 to pH 6.0 for 8 cycles.

Next, the mixture was washed with demineralized water in a conventional manner and dispersed in an aqueous solution containing 128.1 g of ossein gelatin, and the total volume was adjusted to 3000 ml with distilled water.

According to electron microscopy, this emulsion has an average grain size of 0.80.
It was found that the emulsion was a highly monodisperse emulsion with a coefficient of variation in μm and particle size distribution of 10%.

Table 3 (1-4) Application of high iodine shell, intermediate shell, and outermost shell of the present invention: Using the seven types of solutions shown below, the above EM-3 was used as a seed emulsion, and the high iodine shell of the present invention was Emulsion EM-4 was prepared with a degree shell, an intermediate shell, and an outermost shell.

(Solution A-4) Ossein gelatin 22.5 g
Distilled water 6884 m
l Polyisopropylene-polyethylene oxydisuccinate sodium salt lO% ethanol solution
20 mj! 4-hydroxy-6-
Methyl-1,3,3a.

7-Chitraazaindene 28% ammonia water in the amount listed in Table 4 469
m4156% acetic acid aqueous solution 2
58 ml type 1 emulsion 0
．． 8828 mol equivalent amount (solution B-4) Ossein gelatin 24 g
KBr Table-5 Quantity Kl Table-
5-described amount 4-hydroxy-6-methyl-1,3,3a
.

7-Chitraazaindene Distilled water in the amount listed in Table 5 1978
ml (Solution C-4) Ossein gelatin 24 gK
Br Amount listed in Table-6 Kl Mouse 4-hydroxy-6-methyl-1,3,3a listed in Table-6.

7-Chitraazaindene Amount listed in Table 6 Distilled water 1978
ml (Solution D-4) Ossein gelatin 40 [K
Br Mouse Kl listed in Table-7 Amount listed in Table-7 4-hydroxy-6-methyl-1,3,3a.

7-Chitraazaindene Amount listed in Table-7 Distilled water 3296
ml (solution E-4) A g N 031109 g 28% ammonia water 904
Make up to 1866ml with ml11 distilled water.

(Solution F-4) 50% KI3r aqueous solution Required amount for pAg adjustment (Solution G-4) 56% acetic acid aqueous solution Required amount for pH adjustment 50
℃, JP-A-57-92523, JP-A-57-92
Using the mixer shown in No. 524, solutions E-4 and 8-4 were added to solution A-4 by the simultaneous mixing method for 46.6 minutes, and C-4 was added at the same time as the addition of B-4 was completed. 3
At the same time as the addition of C-4 was completed after 5.9 minutes, D-4 was added, and the addition was completed after 25.5 minutes. I during simultaneous mixing
)Ag, pH and solutions E-4, B-4, C-4, D-4
The addition rate of was controlled as shown in Table 8. pAg and pI-1 were controlled by changing the flow rates of solution F-4 and solution G-4 using a variable flow rate roller tube pump. 2 minutes after finishing adding solution E-4, add solution F.
−4 to bring the pAg to 10.4, and after another 2 minutes solution G
-4 f) I-1 was changed to 6.0 three times.

Next, after washing with demineralized water using a conventional method and dispersing it in an aqueous solution containing 127 g of ossein gelatin, a total amount of 3
000m! ! Adjusted to.

According to electron microscopy, this emulsion has an average grain size of 1.60.
The emulsion was found to be a highly monodisperse emulsion with a coefficient of variation in μm and particle size distribution of 11%.

EM-4 is a core/shell type silver iodobromide emulsion with silver iodide contents of 15 mol %, 5 mol %, and 0.3 mol % sequentially from the grain interior (i.e., 11=0.3, I h
= 15, lm = 5).

Margin below ζ, continued on next page. ) Table-4 Solution A-4 Preparation Amount Table-8 11 liters Using the seven types of solutions shown in (1-4) of Production Example 1, K
Br, Kl and 4-hydroxy-6-methyl-1,3,
3a, Table 4, 5 for the amount of 7-chitraazaindene added.
, 6, and 7, except for the amounts described in (1-4) of Production Example 1.
Similarly, EM-5, EM-6, EM-7, EM-
8. EM-9 was manufactured.

These are monodisperse emulsions with an average grain size of 1.60 μm, and the coefficients of variation in grain size distribution are 17%, 15%, and 12%, respectively.
, 16%, 16%.

Production 1- Using the seven types of solutions shown in (1-4) of Production Example 1, K
Br, Kl and 4-hydroxy-6-methyl-1,3,
3a, Table 4 and 5 show the amount of 7-chitraazaindene prepared.
, 6, and 7, except for the amounts described in (1-4) of Production Example 1.
EM-10-F and M-26 were produced in the same manner as above.

These are monodispersed emulsions with an average grain size of 1.60 μm, and the coefficients of variation in grain size distribution are 10%, 10%, and 11%, respectively.
, 12%, 13%, 18%, 19%, 35%, 39%,
10%, 11%, 11%, 11%, 12%, 12%, 1
2% and 13%.

Using the seven types of solutions shown in (1-4) of Production Example 1, K
Br, , Kl and 4-hydroxy-6-methyl-1,3
,3a, ? - Table 4 shows the amount of tetraazaindene prepared.
Production Example 1 (1-4
), EM-28 and EM-29 were produced. Furthermore, pAg, pt (and E-4, B-4, C-4) during mixing
EM-27 was produced by changing the control of the addition rate of D-4 as shown in Table-9, and E was produced as shown in Table-10.
M-30 and M-31 were manufactured. These have an average particle size of 1.60
The emulsions were monodisperse emulsions with particle size distributions of 9%, 18%, 19%, 32%, and 34%, respectively.

(The following is a blank space, continued on the next page.) Table 9 1
Br, Kl and 4-hydroxy-6-methyl-1,3,
3a, ? - Table 4 and 5 for the amount of tetraazaindene prepared.
, 6, 7, and further pAg and pH during mixing.
The addition rates of E-4, B-4, C-4, and D-4 were controlled as shown in Table 11, and EM-32 and EM-33 were controlled as shown in Table 12. EM-34 was manufactured as in Example 1-13.

These are monodisperse emulsions with an average grain size of 1.60 μm, and the coefficients of variation in grain size distribution are 10%, 10%, and 12%, respectively.
Met.

(The following margins are continued on the next page.) Table 11 Table 12 Table 13 ``113J fresh i'' Using the seven types of solutions shown in (1-4) of Production Example 1, K
Br, Kl and 4-hydroxy-6-methyl-1,3,
3a, Table 4 and 5 show the amount of 7-chitraazaindene prepared.
, 6, and 7, except for the amounts described in (1-4) of Production Example 1.
EM-35, 36, and 37 were produced in the same manner as above. Furthermore, I) Ag, pH and E-4, B-4, C during mixing
EM-38 and EM-39 were manufactured by changing the control of the addition rate of -4 and D-4 as shown in Table-12. These are monodisperse emulsions with an average grain size of 1.60 μm, and the coefficients of variation in grain size distribution are 12%, 14%, 13%, 9%, and 11%, respectively.
%Met.

E. Examples Next, the present invention will be explained in more detail with reference to examples. However, in the following Examples, the amount added in the silver halide color photographic light-sensitive material is shown per 1 d unless otherwise specified. In addition, silver halide and colloidal silver are shown in terms of silver.

<Example-1> An antihalation layer (black colloid 11Q, 40 g
and 3.0 g of gelatin. ) Samples II & 1l-1 were prepared by sequentially coating each of the following layers on a transparent support.

[Sample floor 1-1] ... Comparative example N1; Low-sensitivity layer of red-sensitive silver halide emulsion layer (RL-1
) Emulsion consisting of AgBr1 containing 17 mol% Ag (emulsion r
) is color sensitized to red sensitivity, 168 g, and 0.8 g of 1
-hydroxy-4-(β-methoxyethylaminocarbonylmethoxy)-N-(δ-(2,4-di-L-amylphenoxy)butyl]-2-naphthamide (referred to as 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 (referred to as CC-1), 0.015
g of 1-hydroxy-2-[δ-(2,4-di-monoamylphenoxy)n-butyl]naphthamide, 0.0
7 g of 4-octadecylsuccinimide-2-(1-
phenyl-5-tetrazolylthio)-1=indanone (
A red-sensitive silver halide emulsion layer containing a dispersion in which D-1) was dissolved in 0.65 g of tricresyl phosphate (TCP) and emulsified and dispersed in an aqueous solution containing 1.85 g of gelatin. low sensitivity layer.

Layer 2: High-sensitivity layer (I'2H) of red-sensitive halogenated emulsion layer
-1) 1.2 g of EM-5 emulsion sensitized to red with the sensitizing dye listed in NLLI-1 in Table 14, 0.21 g of cyan coupler (C-1), and 0.21 g of cyan coupler (C-1). 0.23 g of TC in which 0.2 g of colored cyan coupler (CC-1) was dissolved
A high-sensitivity layer of a red-sensitive silver halide emulsion layer containing a dispersion of P dissolved in P and emulsified and dispersed in an aqueous solution containing 1.2 g of gelatin.

Layer 3; Intermediate layer (IL) 0.8 g gelatin and 0.07 g 2.5-Z-L
- an intermediate layer containing 0.04 g of dibutyl phthalate (referred to as DBP) in which octylhydroquinone (referred to as HQ-1) was dissolved;

Layer 4: Low-speed layer of green-sensitive silver halide emulsion layer (GL-1
) 0.80 g of Emulsion I color sensitized to green sensitivity and 0.8 g
Contains a dispersion in which 95 g of dinonylphenol in which 0 g of Exemplary Compound (13) and 0.01 g of DIR Compound (D-1) are dissolved is emulsified and dispersed in an aqueous solution containing 2.2 g of gelatin. Low-speed layer of green-sensitive silver halide emulsion layer.

Layer 5: High-speed layer of green-sensitive silver halide emulsion layer (GH-1
) 1.8 g of an emulsion made of AgBr1 containing 16 mol % of Ag, color sensitized to green sensitivity, and 0.25 g of dinonylphenol in which 0.20 g of exemplified compound (13) was dissolved were mixed with 1.9 g of the emulsion. A high-sensitivity layer of a green-sensitive silver halide emulsion layer containing a dispersion emulsified in an aqueous solution containing gelatin.

Layer 6 layer yellow filter (YF) 0.15 g of yellow colloidal silver, 0.11 g of DBP dissolved in 0.2 g of color stain inhibitor (HQ-1), 1
．． One layer of yellow filter containing 5g gelatin.

N7: Low-speed layer of blue-sensitive silver halide emulsion layer (BL-1
) 0.2g and 1.5g of emulsion I color sensitized to blue sensitivity
α-pivaloyl-α-(1-benzyl-2-phenyl-3,5-dioxinimidazolidin-4-yl)-2
-Chloro-5-[α-dodecyloxycarbonyl)ethoxycarbonyl]acedoanilide (referred to as Y-1)? A low-sensitivity layer of a blue-sensitive silver halide emulsion layer containing a dispersion obtained by emulsifying and dispersing 0.6 g of TCP, which is dissolved in water, into an aqueous solution containing 1.9 g of gelatin.

Layer 8: High-speed layer of blue-sensitive silver halide emulsion layer (BH-1
) Emulsion CP consisting of AgBr1 containing 12 mol % of Ag
, a blue-sensitive silver halide emulsion layer containing a dispersion emulsified in an aqueous solution containing 5 g of gelatin.

Layer 9; Protective layer (Pro) 0.23 g of gelatin and polymethyl methacrylate particles (diameter 2.5 μm) and the following ultraviolet absorber UV-1,
Gelatin layer containing an emulsified dispersion of UV-2.

UV-1; 2-(2-benzotriazolyl)4-L-pentylphenol UV-2; 2-(3-cyano-3-(n-dodecylaminocarbonyl)anilidene-1 = ethylpyrrolidine However, gelatin liquid A 10% aqueous solution of medium viscosity gelatin pretreated with a gelatin hardening agent (H-1) at pH 6, 5, and 63° C. for 60 minutes was used.

In addition to the above composition, each layer contains a gelatin hardening agent (H-
2) and a surfactant were added.

Regarding sample 11ial-1 created in this way,
Samples m1-2 to m1-14 were prepared except that the sensitizing dyes and silver halide emulsions shown in Table 14 were used as red-sensitive sensitizing dyes in the RH-1 layer.

Each sample 11k11-・1~1- created in this way
No. 14 was subjected to the following development treatment.

Processing process (38℃) Color development 3 minutes 15 seconds bleaching
Wash with water for 6 minutes and 30 seconds
Fixed for 3 minutes and 15 seconds
Washing with water for 6 minutes and 30 seconds Stabilization for 3 minutes and 15 seconds Drying for 1 minute and 30 seconds The composition of the treatment liquid used in each treatment step is as follows.

[Color developer]

4-Amino-3-methyl-N-ethyl-N-(β-hydroxyethyl)-aniline nitrate 4.75 g Anhydrous sodium sulfite 4.25 g
Hydroxylamine 1/2 sulfate 2.0g
Anhydrous potassium carbonate 37.5
g Sodium bromide 1.3
g Nitrilotriacetic acid trisodium salt (l hydrate) 2.5
g Potassium hydroxide Add 1.0g water to make 1j2.

[Bleach 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.
Add 0 ml water to 11 and adjust to pH=6.0 using aqueous ammonia.

[Fixer] Ammonium 1000sulfate 175.0
g Anhydrous sodium sulfite 8.5
gSodium metasulfite 2.3g
Add water and enjoy! Close and adjust pH to 6.0 using acetic acid.

[Stabilizing liquid]

Formalin (37% aqueous solution) 1.5
ml Konidafukusu (manufactured by Konishiroku Photo Industry Co., Ltd.) 7.5 ml Add water to make 11.

Table 15 shows the sensitometric data of the red-sensitive silver halide emulsion layer.

The sensitivity was determined from the amount of exposure necessary to give an optical density of fog +0.1. Note that the sensitivity is 1150 for sample Na1-1.
It is expressed as relative sensitivity, with seconds being 100.

(The following is a blank space, continued on the next page.) Table 15 As is clear from the above table, samples N [LL-3 to
It can be seen that all of samples Nos. 1 to 9 have high sensitivity at 1750 second exposure, and also at high illumination exposure.

<Example-2> Each emulsion EM-4 to EM-9 and E used in Example 1
M-14 and EM-23 were chemically sensitized according to a conventional method, and each sensitizing dye used in Example 1 was combined with each emulsion in the same manner as shown in Table 14 to perform color sensitization.

Next, each emulsion was added with 4-hydroxy-6-methyl-1,3,3a as a stabilizer. After adding appropriate amounts of -tetrazaindene, saponin as a coating aid, and formalin as a hardening agent, the mixture was coated on a cellulose triacetate base support and dried to prepare samples 11&L2-1 to 2-14.

Divide each sample above into two parts and pass through a red filter into one part.
One part was exposed for 1150 seconds, and the remaining part was exposed to wedge light for 10-4 seconds using a high-intensity sensitometer manufactured by EG&G, and then developed for 2 minutes at 30°C with a developer having the following composition. Washed with water.

(Developer composition) Sulfuric acid-p-methylaminephenol 3g Anhydrous sodium sulfite 50g Hydroquinone 6g Sodium carbonate 29.5g Potassium bromide 1g Add water
The density of the silver image obtained in Example 11 was measured, and red light sensitivity and fog were determined. The method for determining sensitivity was the same as in Example-1. Sensitivity is sample fish 2
1150 seconds of −1 was set as 100, and the relative sensitivity was expressed as shown in Table 16.

(The following is a blank space, continued on the next page.) Table-16 As is clear from the above table, samples 11m1-3 to 2 of the present invention
It is clear that, like Example-1, Sample-9 had high sensitivity in all cases when exposed for 1150 seconds, and maintained high sensitivity even during high-intensity exposure.

<Example-3> Each emulsion (EM-4 to EM-9) used in Example = 1
Chemical sensitization was carried out according to the conventional method, and a sensitizing dye was added to Table 17.
Color sensitization was carried out according to the method, and each emulsion was then treated with 4-
Hydroxy-6-methyl-L3,3a,7-chitrazaindene, saponin as a coating aid, and formalin as a hardening agent were added in appropriate amounts, and then coated on a cellulose triacetate-based support and dried to obtain sample 1'&t.
3-1 to 3-10 were created.

The sample was subjected to wedge exposure for 1150 seconds through a red filter, and then developed in the same manner as in Example-2. The density of the obtained silver image was measured to determine red light sensitivity and fog. How to determine sensitivity is in Example-1
is the same as The sensitivity is 100 for sample 11h3-1,
It is expressed in terms of relative sensitivity and shown in Table-17.

Table 17 However, the amount of sensitizing dye added in the table is the amount per mole of silver halide.

As is clear from the above table, samples 11h3-3 to 3 of the present invention
-7 all have high sensitivity.

Table 18 shows data for the emulsions used in the examples.

(Voluntary) Procedure? Correct 1: September 7, 1985 1, Indication of the case 1985 Patent Application No. 117853 2, Name of the invention Silver halide photographic light-sensitive material 3, Person making the amendment Relationship to the case Patent applicant address Tokyo 1-26-2 Nishi-Shinjuku, Shinjuku-ku, Tokyo Name
(127) Roku Konishi Photo Industry Co., Ltd. 4, Agent 6, Number of inventions increased by amendment (1), r240gJ on the second line from the bottom of page 70 of the specification is corrected to r1200gJ.

(2), Table 5 on page 85 of the same, and Table on page 86 of the same
6zu.

1 or above -

Claims (1)

[Claims] 1. An inner core consisting essentially of silver bromide and/or silver iodobromide, and an inner core provided outside this inner core and consisting essentially of silver bromide and/or silver iodobromide. In the silver halide photographic material containing negative-working silver halide grains having a plurality of outer shells, the iodine content of the outermost shell of the silver halide grain is 10 mol% or less, and the outermost shell An 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, and an iodine content intermediate between these two shells is provided between the outermost shell and the iodine-rich shell. an intermediate shell having an iodine content higher than that of the outermost shell by 3 mol% or more, and an iodine content of the high iodine content shell having an iodine content higher than that of the intermediate shell by 3 mol% or more, and Silver halide photographic sensitization characterized in that the silver halide grains are sensitized with at least one kind of sensitizing dye represented by the following general formula (1) so that the maximum spectral absorption wavelength is 600 nm or more. material. General formula (I): ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [However, in this general formula, Z^1 and Z^2 are nonmetallic atomic groups necessary to form a basic heterocycle; R^ 1 and R^
2 is an alkyl group, at least one of which is an alkyl group substituted with a hydroxy group, carboxyl group, or sulfo group; L^1, L^2, L^3, and L^4 are methine groups (however, L^1 and may bond with L^2 to form a carbocyclic ring.); X^1 is an acid anion; l^1, l^2, m
^1, m^2, m^3 and n^1 are 0 or 1 (however, m
_1+m_2+m_3=1, 2 or 3. )
It is. ]