JPH04140737A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide the silver halide photographic sensitive material having a high sensitivity and excellent preservable property by incorporating a silver halide emulsion which is specified in the distribution of photosensitive nuclei and has dislocation in the particles into this photosensitive material. CONSTITUTION:The emulsion is preferably negative type silver halide particles and is planar particles having >=2 aspect ratio. The silver halide particles have the dislocation in the particles and have the points where latent images developable by exposing can be formed, i.e. the photosensitive nuclei within the particles. The one max. value exists in the photosensitive nuclei distribution in the particles and the positions where the max. value exists are specified to >=2nm and <=5nm from the particle surfaces.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a silver halide photographic light-sensitive material, and particularly to a silver halide photographic light-sensitive material having excellent photographic sensitivity.

(Prior Art) In recent years, demands on photographic silver halide emulsions have become increasingly strict, and high standards of photographic performance such as high sensitivity, excellent graininess, and sharpness have been made. In response to these demands, improvements in sensitivity including improvement in color sensitization efficiency using sensitizing dyes, improvement in the sensitivity/graininess relationship, improvement in sharpness,
A technique for using tabular grains intended to improve covering power is disclosed in U.S. Pat. Nos. 4,434,226 and 4,414.
．． No. 310, No. 4,433.048, No. 4,414.30
No. 6, No. 4,459,353.

Also, JP-A No. 58-113930, No. 58-11393
No. 4 and No. 59-119350 also contain a multilayer color with high sensitivity and improved graininess, sharpness, and color reproducibility, using a tabular silver halide emulsion with an aspect ratio of 8 or more in the high-sensitivity layer. A photographic material is disclosed.

However, dyes also have the property of desensitizing silver halide emulsions, and optimal spectral sensitization can usually be achieved only with dyes in amounts that are significantly lower than those required to form a continuous monolayer on the emulsion grain surface. Currently, the advantages of tabular grains are not being utilized.

In order to solve this problem, it has long been known that the so-called first type of emulsion, which has ripening nuclei (hereinafter referred to as "photosensitive nuclei") inside the grains that can form a developable latent image upon exposure, is effective. It is being For example, U.S. Patent No. 3,979,21
In No. 3, the inherent desensitization of internal latent image type silver halide during color sensitization is significantly smaller than that of a silver halide emulsion of equal grain size that is chemically sensitized only on the surface, and as a result, a large amount of It is disclosed that color sensitization can be effectively performed using sensitizing dyes. It is also known to have good storage stability because the photosensitive nuclei are not exposed on the surface.

However, it is generally said that photosensitive nuclei are extremely small crystals of silver sulfide, gold silver sulfide, etc. that are epitaxially bonded to silver halide crystals, and their state of existence is unstable. Conventionally, the effect of improving sensitivity by forming an inner layer has not been sufficiently exhibited in twin grains such as normal crystals and tabular grains.

Regarding observation of dislocations in silver halide grains, ■C, R, B
erry, J. App1. Phys, +27, 636
(1956) ■C, R, Berry, D, C, Ski1
man, J, Appl, Phys, +351 ■ J, F,
Hawilton, J., Phot, Sci., Eng.
11.57 (1967) ■T, Shiozawa, J.
Soc, Phat, 5cijap, +34+ 16(
1971) ■T, Shiozawa, J, Soc, P
hot, Sci, Jap, +35+213
(1972), it is possible to observe dislocations in crystals by X-ray diffraction or low-temperature transmission electron microscopy, and by intentionally straining the crystal, various It has been stated that dislocations occur.

Although the silver halide grains in these documents do not have dislocations intentionally introduced during the formation of photographic emulsions, JP-A-63-220 is a silver halide grain in which dislocations are actively introduced.
238, Tokukaihei! It is described in -201649. According to these patents, tabular grains with a certain amount of dislocation lines are superior in photographic properties such as sensitivity and reciprocity, compared to tabular grains without dislocation lines, and when used in photographic materials, the tabular grains have improved sharpness and graininess. Although it has been shown to have excellent sexual performance, it is still not satisfactory.

(Problems to be Solved by the Invention) An object of the present invention is to provide a silver halide photographic material that is highly sensitive and has excellent storage stability.

(Means for Solving the Problems) The objects of the present invention are as follows: (1) The distribution of photosensitive nuclei is 2 nm or more and 50 nm from the particle surface.
1. A silver halide photographic light-sensitive material comprising a silver halide emulsion having a maximum value at a depth of less than or equal to 100 nm, and having dislocations inside its grains.

(2) The silver halide photographic material as described in (1) above, which is a silver halide tabular grain having an aspect ratio of 2 or more.

(3) The silver halide photographic material as described in (1) above, which is a normal crystal silver halide grain having a coefficient of variation in grain size distribution of 20% or less.

(4) The silver halide photographic material described in (1) above, wherein dislocations are concentrated near the vertices of the silver halide grains.

achieved by.

The present invention will be explained in more detail below.

The emulsion of the present invention preferably has negative-working silver halide grains, and its crystal form may be tabular, octahedral, mono
A particle group having a regular crystal shape (normal crystal grain) such as a dihedral or a tetradecahedron and an average aspect ratio of about 1 may be used,
The tabular grains may have irregular crystal shapes such as spherical or potato-shaped, preferably having an aspect ratio of 2 or more, and more preferably having an aspect ratio greater than 3 and less than 8.

The tabular grain herein is a general term for grains having one twin plane or two or more parallel twin planes. The twin plane refers to the (111) plane when the ions at all lattice points on both sides of the (111) plane are mirror images. Sometimes triangular, hexagonal, or rounded circular shapes,
Triangular shaped ones have triangular shaped ones, hexagonal shaped ones have hexagonal shaped ones, and circular shaped ones have mutually parallel outer surfaces.

The average aspect ratio of tabular grains in the present invention is 0.
For tabular grains having a grain size of 1 μm or more, the average value is the value obtained by dividing the grain diameter by the thickness. The thickness of the particles is measured by depositing metal along with latex as a reference from an oblique direction on the particles, measuring the length of the shadow on an electron micrograph, and calculating using the length of the latex shadow as a reference. It's easy to do.

The particle diameter in the present invention is the diameter of a circle having an area equal to the projected area of the parallel outer surface of the particle.

The projected area of particles is determined by measuring the area on an electron micrograph.
It is obtained by correcting the projection magnification.

The diameter of the tabular grains is preferably 0.15 to 5.0 microns. The thickness of tabular grains is 0.05 to 1
．． Preferably, it is 0μ.

The proportion of tabular grains is preferably 50% or more, more preferably 80%, particularly preferably 90% or more of the total projected area.

Moreover, more preferable results may be obtained by using monodisperse tabular grains. The structure and manufacturing method of monodispersed tabular grains are as described in, for example, JP-A-63-151618. The ratio of the length of the side with the maximum length to the length of the side with the maximum length is 2
It is occupied by tabular silver halide grains which are hexagonal and have two parallel surfaces as outer surfaces, and furthermore, the coefficient of variation of the grain size distribution of the hexagonal tabular silver halide grains is It has a monodispersity of 20% or less (value obtained by dividing the variation (standard deviation) of the particle size expressed by the circular diameter of the projected area by the average particle size).

The diameter of the normal crystal particles is preferably 0.1 μ to 5.0 μ, more preferably 0.3 μ to 1.5 μ. The coefficient of variation of the size distribution is preferably 20% or less.

The silver halide grains of the present invention have dislocations inside the grains. Dislocations in silver halide grains are, for example, J, F
, Hamilton, Phot, Sci, E.
ng,,”.

57, (1967), T., Shiozawa, J.
Soc, Phot, Sci.

Japan, Jin, 213, (1972), it can be directly observed using a transmission electron microscope at low temperature. In other words, the silver halide grains are taken out from the milkweed with care so as not to apply pressure that would cause dislocations to the grains, and placed on a mesh for electron microscopy, and the sample is carefully placed to prevent damage (printout, etc.) from the electron beam. Observation is performed using the transmission method in a cooled state. At this time, the thicker the particle, the more difficult it is for the electron beam to pass through it, so it is better to use a high-pressure electron microscope (200 kV or more for a particle with a thickness of 0.25 μ) to observe it more clearly. can.

The position and number of dislocations can be determined from photographs of grains obtained by such a method. In the present invention, the inside of a grain refers to the entire area inside the silver ions or halogen ions present on the surface of the grain. . The dislocations may be formed throughout the grain or locally, but it is preferable that the dislocations be substantially concentrated near the apex of the silver halide grain. Here, the term "near the vertex" refers to the area surrounded by the perpendicular line drawn from the midpoint of the straight line connecting the center of the particle and each vertex to the side of the particle and the perpendicular line. If the particle is rounded, each vertex will be ambiguous; in this case, tangents are drawn and the intersection of the tangents is defined as the particle vertex. The fact that dislocations are substantially concentrated near the apex means that the dislocation density is higher than that of the part of the particle other than the apex area.

Dislocation density is defined by the number of dislocation lines included per unit volume.

The halogen composition of the silver halide grains of the present invention is silver iodobromide,
Silver bromide and silver chloroiodobromide. The halogen structure inside the grain may be of a uniform type, a double structure type, or a multilayer structure type, and a high silver iodide phase may exist inside the grain, on the grain surface, or in the middle part. The particles may have a halogen-converted silver halochloride layer, silver thiocyanate layer, or silver citrate layer inside the grains.

In order to introduce dislocations near the apex of silver halide grains, silver halide with a high silver iodide content is bonded to the apex of the silver halide grain, or silver iodide or silver iodide content is After high silver halide bonding, the grains are grown again.

In order to bond silver iodide or at least silver iodobromide, silver iodochlorobromide, or silver iodochloride having a silver iodide content higher than that of the host grain to the top of the silver halide grain. either by a direct method or by an indirect method via halogen conversion.

A method of bonding a guest made of silver iodide to a host grain having a face-centered cubic rock salt crystal structure by epitaxial growth is disclosed in JP-A-59-162540 (TLS4,463,087).
is disclosed in a broad sense. According to this method, it is stated that by selecting a silver salt that is non-isomorphic with respect to the host grain crystal structure, deposition can be performed by epitaxial growth.

As a result of extensive studies, the present inventors found that using silver halide grains of silver iodobromide as a host, 0.5 to 10 mol% of the host,
Preferably, silver iodide is added to the apex of silver halide grains without using any site director by rapidly adding a rainwater solution of potassium iodide and silver nitrate in an amount of 1 to 6 mol %. Alternatively, it has been found that direct bonding can be achieved by epitaxially forming silver halide with a high silver iodide content.

The preferred addition time is 5 to 062 minutes, more preferably 0.5 to 2 minutes.

The following method may be used to grow silver iodide or silver halide with a high silver iodide content on the tops of silver halide grains. That is, after adding a silver halide solvent to a solution containing host grains, a rainwater solution of potassium iodide and silver nitrate is added, or after adding a silver halide solvent, potassium iodide is added, and then a halide solution is added. This is achieved by adding an aqueous solution (halide is Br or Br+1) and silver nitrate. In this case, it is not necessary to add the rainwater solution rapidly.The aqueous solution is added in an amount of 0.5 to 10 mol%, preferably 2 to 6 mol%, of the host.

Examples of silver halide solvents include thiocyanates, ammonia, thioethers, and thioureas.

For example, thiocyanate (U.S. Pat. No. 2.222.264)
No. 2,448,534, No. 3.320,06
9, etc.), ammonia, thioether compounds (e.g., U.S. Pat. No. 3,271,157, U.S. Pat. No. 3,574,6)
No. 28, No. 3.704,130, No. 4,297,
439, 4,276.347, etc.), thione compounds (for example, JP-A-53-144319, JP-A-53-8)
2408, 55-77737, etc.), amine compounds (e.g., JP-A-54-100717, etc.), 1,000-urea derivatives (e.g., JP-A-55-2982), imidazoles (e.g., JP-A-54-100717) , substituted mercaptotetrazole (for example, JP-A-57-202531).

Next, an indirect method of epitaxially bonding silver iodide or a silver halide portion having a high silver iodide content to the apex of a silver halide grain, preferably a tabular grain, via halogen conversion will be described.

A method of epitaxially growing silver chloride on the apex of tabular grains is disclosed in JP-A-58-108526 (US 4.435.5).
01). When the host tabular grains consist essentially of at least 8 mol% iodide at their surfaces,
Epitaxial growth of silver chloride takes place adjacent to the corner (apex) even in the absence of an orientation-controlling substance, and in order to more narrowly limit epitaxial growth at corners or edges, aqueous iodide or adsorptive orientation-controlling substances can be used. The use of substances is also described.

Example 4 of JP-A-58-108526 describes a method in which a cyanine dye is adsorbed onto silver halide grains, and silver chloride is epitaxially grown on the vertices. When the epitaxial grains obtained in this way are grown after halogen conversion with iodide, dislocations occur not only at the apex but also at the top.
It was found that dislocations are introduced along the edges and within the plane. this is,
It is presumed that this is because the sensitizing dye itself has the function of introducing dislocations.

The present inventors have found that it is preferable to use water-soluble iodide as an orientation controlling substance in order to epitaxially grow silver chloride. Thus, typically potassium iodide is used. 0.0 for host silver halide grains.
Preference is given to using potassium iodide in an amount of 0.3 to 3 mol %, preferably 0.5 to 5 mol %. This amount preferably corresponds to about 50 to 200% of the surface monatomic coverage of the silver halide grains. Thereafter, by adding silver nitrate, potassium chloride, etc. by the double jet method, silver chloride, which meets the purpose of the present invention, can be grown at the top of the silver halide grains. The amount of silver nitrate added here is preferably 0.1 to 10 mol % based on the host silver halide grains.

This article describes the halogen conversion of silver chloride with potassium iodide. Silver halide with high solubility is converted to silver halide with low solubility by adding a halide ion capable of forming silver halide with low solubility. This process is called halogen conversion, and is described in, for example, U.S. Pat. form a phase. If the amount of potassium iodide for halogen conversion is too large, it will cause dispersion of dislocations, and if it is too small, desired dislocations will disappear due to recrystallization that occurs in the subsequent grain growth stage. Furthermore, if an appropriate amount of silver chloride phase does not already exist during this process, potassium iodide undergoes halogen conversion with silver bromide, so that dislocations will not be concentrated during subsequent grain growth. The amount of potassium iodide for halogen conversion is preferably 0.1 to 1Qmof% based on the host silver halide grains, preferably tabular grains.

Next, we will discuss the growth of dislocations.

In the step of directly bonding silver iodide by the above-mentioned direct method and the step of halogen conversion, silver bromide, silver iodobromide, silver chlorobromide, or silver chloroiodobromide of the substrate (host silver halide grains) are bonded together. In this case, an Agl phase having a different crystal form or a silver halide phase having a high silver iodide content is formed at the top of the silver halide grains.

Subsequently, when silver nitrate and potassium bromide or a mixed solution of silver nitrate, potassium bromide, and potassium iodide are simultaneously added, the particles grow further, but at this time, dislocations are introduced starting from the Agl phase. Since the Agl phase is localized near the apex, dislocations are concentrated near the apex. The amount of silver nitrate added at this time is arbitrary as long as it is 5 mof% or more based on the base material. Further, when adding a mixed solution of potassium bromide and potassium iodide, the mixing ratio is preferably 1 to 1 to 0.4 of potassium iodide.

The silver halide emulsion of the present invention can be chemically sensitized using gold, sulfur, or selenium compounds.

The silver halide grains of the present invention have a portion, that is, a photosensitive nucleus, inside the grain where a latent image that can be developed by exposure can be formed.The so-called internal slip type emulsion of the present invention will be described in detail. In other words, there is one maximum value in the distribution of photosensitive nuclei within the particle, and the position of this maximum value is 2 ns from the particle surface.
50n- or less, more preferably 5na+ or more 30n
- or less, and the number of latent images on the particle surface is preferably 1/10 or more and 5/10 or less of the maximum value.

The "distribution of photosensitive nuclei within a particle" as used herein means that the horizontal axis represents the depth of the latent image from the particle surface (xt++a), and the vertical axis represents the number of latent images (y).
where X is S: silver halide emulsion average grain size (n+w) gl:
Amount of silver remaining after performing the following treatment on an unexposed emulsion coated sample Ago: The amount of coated silver before treatment, and y is the amount of silver after performing white exposure for 1/100 seconds.
It is the reciprocal of the exposure amount that gives the density (fogging +0.1) when the following processing is performed. The processing conditions for obtaining the above latent image distribution are: N-methyl-P-aminophenol sulfate 2.5 g Sodium L-ascorbate 10 g Sodium metaborate 35 g Potassium bromide
Add 1g water 1
1! 0 to 10 g/l of sodium thiosulfate is added to a treatment solution (pH 9.6) and treated at 20°C for 7 minutes. Here, the amount of sodium thiosulfate is O~Log/
By changing up to f, the depth from the surface of the latent image in the silver halide grains developed during processing changes, and it is possible to know the change in the latent image liquid in the depth direction.

The depth of the photosensitive nucleus determined as above is 5 from the surface.
If it exists at a depth deeper than on@, even if it is developed with a developer that is practically used for black-and-white, color negative, or color reversal photosensitive materials, the development will be insufficient and the sensitivity will be substantially impaired.

According to the previously reported methods for preparing internal latent image type emulsions, controlling the shell thickness resulted in changing the ratio of surface sensitivity to internal sensitivity. However, the results of this study show that in order to achieve the optimal sensitivity for a certain process, it is preferable to control the particle formation conditions and independently control the mode of latent image distribution and the ratio of surface sensitivity to internal sensitivity. It became clear.

For example, even if the maximum value of the latent image distribution is at a position below 50 nm, if the latent image distribution on the surface becomes 5/10 or more of the maximum value, the internal This is undesirable because the color sensitization effect of the latent image type emulsion tends to be insufficient. Furthermore, if the latent image distribution on the surface is less than one-tenth of the maximum value, development tends to be insufficient with a practical processing solution, making it difficult to obtain substantial sensitivity.

On the other hand, conventional design standards for internal latent image type silver halide grains, which focus only on the difference between the sensitivity when surface development is performed and the sensitivity when internal development is performed, are difficult to achieve optimal sensitivity. It became clear that this was insufficient.

In other words, even if the ratio of surface sensitivity and internal sensitivity is the same (for example, surface sensitivity is 1/2 of internal sensitivity), if the maximum of the latent image distribution exists at a deep position of 50n- or more, practical Depending on the processing, development may be insufficient and the potential optimum sensitivity of the particles cannot be exploited.

As mentioned above, in order to discover the optimal sensitivity, the location where the maximum of the latent image distribution exists is an essential requirement, and considering both the difference between the maximum value and the number of latent images on the surface, it is possible to find an excellent internal latency. It has become clear that image-shaped/'t silver halide grains can be designed.

The practical processing solutions mentioned above are those that are intended to develop only the surface latent image and do not contain a silver halogen solvent, or those that contain a large amount of halogen and are intended to develop the internal latent image. This is not a developer containing a silver oxide solvent.

A method for preparing internal latent image emulsions is described in US Pat. No. 3,979.
No. 21.3, No. 3,966.476, No. 3,206,
No. 313, No. 3,917,485, Special Publication No. 4.3-2
9405, Japanese Patent Publication No. 45-13259, etc. can be used, but in any method,
In order to obtain an emulsion having the latent image distribution as claimed in this patent,
The chemical sensitization method, the amount of silver halide precipitated after chemical sensitization, and the precipitation conditions must be adjusted.

Alternatively, fine silver halide particles may be added and an internal latent image may be formed by Ostwald ripening.

Specifically, in US Pat. No. 3,979,213, an internal latent image type emulsion is prepared by precipitating silver halide again on emulsion grains whose surfaces have been chemically sensitized by a controlled double jet method.

Precipitating silver halide onto the grains in the amounts practiced in this patent results in a surface sensitivity ratio of less than one-tenth of the total sensitivity. Therefore, in order to obtain the latent image distribution of the present invention, the amount of silver halide to be precipitated after chemical sensitization is determined according to US Pat.
Less than what is practiced in No. 1 is preferred.

For the silver halide to be precipitated after chemical sensitization, it is necessary to select a halogen composition that has a solubility that is not lower than that of the surface of the silver halide before chemical sensitization, and preferably has a high solubility. For example, for AgBr, AgCf or AgC11-
11Brx, AgBr preferably AgCffi.

AgCj! ,-, Brx is precipitated.

The silver halide grains of the present invention can preferably be subjected to reduction sensitization during the grain formation process before the formation of photosensitive nuclei.

Applying reduction sensitization during the grain formation process of a silver halide emulsion basically means performing it during nucleation, ripening, and growth. Reduction sensitization may be carried out at any stage during nucleation, which is the initial stage of grain formation, during physical ripening, or during growth. The most preferred method is reduction sensitization during the growth of silver halide grains. Growing here refers to methods in which reduction sensitization is performed while the silver halide grains are growing by physical ripening or addition of a water-soluble silver salt and a water-soluble alkali halide, but growth is temporarily stopped during growth. This means that it also includes a method of performing reduction sensitization in the state and then further growing it.

The above-mentioned reduction sensitization refers to a method of adding a known reducing agent to a silver halide emulsion, a method called silver ripening, and a low pAg of 1 to 7.
Either a method of growing or aging in an Ag atmosphere or a method of growing or aging in a high pH atmosphere of pH 8 to 11 called high p)I aging can be selected. Moreover, two or more methods can also be used together.

The method of adding a reduction sensitizer is a preferred method because the level of reduction enhancement can be finely adjusted.

As reduction sensitizers, stannous salts, amines and polyamines, hydrazine derivatives, formamidine sulfinic acid, silane compounds, borane compounds, etc. are known. In the present invention, a compound selected from these known compounds can be used.

Moreover, two or more kinds of compounds can be used in combination. Preferred compounds as reduction sensitizers include stannous chloride, thiourea dioxide, dimethylamine borane, ascorbic acid, and ascorbic acid derivatives. The amount of the reduction sensitizer to be added depends on the emulsion manufacturing conditions and must be selected, but it is suitably in the range of 10-'' to 10-3 mol per mol of silver halide.

Reduction sensitizers include water, alcohols, glycols,
It can be dissolved in a solvent such as ketones, esters, amides, etc. and added during particle formation.

It may be added to the reaction vessel in advance, but it is preferable to add it at an appropriate time during particle formation. Alternatively, a reduction sensitizer may be added in advance to an aqueous solution of a water-soluble silver salt or a water-soluble alkali halide, and these aqueous solutions may be used to form particles. It is also a preferable method to add the reduction sensitizer solution in several parts or continuously as the particles are formed.

More preferably, a palladium compound is added to the silver halide emulsion of the present invention in an amount of 5XIO-' mol or more and preferably 104 mol or less per mol of silver halide after the grain formation process is completed.

Here, palladium compound refers to palladium divalent salt or
It means salt of high value. Preferably the palladium compound is Rz
It is represented by PdXi or RZPdX. Here, R represents a hydrogen atom, an alkali metal atom or an ammonium group. X represents a halogen atom, and represents a chlorine, bromine or iodine atom.

Specifically, KZPdi4, (NF14)! Pd
C/! 6.

NazPdCl, (NHa)zPdcf4.
LizPdC14゜NazPdCl h or KzPd
Br4 is preferred.

Most preferably, these palladium compounds are used in combination with thiocyanate ion in an amount of 5 times or more the mole of the palladium compound.

The silver halide emulsion of the present invention is preferably used after being spectrally sensitized.

Methine dyes are usually used as the spectral sensitizing dyes used in the present invention, and include cyanine dyes, merocyanine dyes, composite cyanine dyes, composite merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. is included. Any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic nucleus for these dyes. Namely, pyrroline, oxazoline, thiazoline, pyrrole, oxazole, thiazole, selenazole, imidazole, tetrazole, pyridine, etc.; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and an aromatic hydrocarbon ring fused to these nuclei Indolenine, benzindolenine, 9andole, benzoxadole, naphthoxazole, benzothiazole, naphthothiazole, benzoselenazole, benzimidazole, quinoline, etc. can be applied. These nuclei may be substituted on carbon atoms.

Merocyanine dyes or complex lomethyanine dyes contain pyrazolin-5-one, thiohydantoin, 2-thioxaprine-2,4-
5- to 6-membered heterocyclic nuclei such as dione, thiazoline-2,4-dione, rhodanine, and thiobarbic acid can be applied.

Among the above dyes, particularly useful sensitizing dyes for the present invention are cyanine dyes. Specific examples of cyanine dyes useful in the present invention include dyes represented by the following general formula (1).

General formula (1) % formula %) In the formula ZI, Z! is a heterocyclic nucleus commonly used in cyanine dyes, especially thiazole, thiazoline, benzothiazole, naphthothiazole, oxazole, oxazoline, benzoxazole, naphthoxazole, tetrazole, pyridine, quinoline, imidacilline, imidazole,
Represents the atomic group necessary to complete benzimidazole, naphthoimidazole, selenazoline, selenazole, henzoselenazole, naphthoselenazole, indolenine, etc. These nuclei include lower alkyl groups such as methyl, halogen atoms, phenyl groups, hydroxyl groups, alkoxy groups having 1 to 4 carbon atoms, carboxyl groups, alkoxycarbonyl groups, alkylsulfamoyl groups, alkylcarbamoyl groups, acetyl groups, acetoxy group, cyano group,
It may be substituted with a trichloromethyl group, a trifluoromethyl group, a nitro group, etc.

L1 or L2 represents a methine group or a substituted methine group. Examples of substituted methine groups include methine groups substituted with lower alkyl groups such as methyl and ethyl, phenyl, substituted phenyl, methoxy, and ethoxy.

R1 and R7 are alkyl groups having 1 to 5 carbon atoms; substituted alkyl groups having a carboxy group; β-sulfoethyl, T-sulfopropyl, δ-sulfobutyl, 2-(3-sulfopropoxy)ethyl, 2-[2- (3-sulfopropoxy)
Substituted alkyl groups with a sulfo group such as ethyl, 2-hydroxy sulfopropyl, allyl
l) 'S and other substituted alkyl groups commonly used as the N-substituent of cyanine dyes. ml represents 1.2 or 3. Xl- is iodide ion, bromide ion, P
-) Represents an acid anion group commonly used in cyanine dyes, such as luenesulfonate ion and perchlorate ion. n
, or 2, and when it has a betaine structure, n is 1.

Preferably, spectral sensitization is performed using two or more types of sensitizing dyes of general formula (1).

In addition to the above, the following spectral sensitizing dyes may be used. German patent 929,080
No. 2,493,748, U.S. Patent No. 2,503,7
No. 76, No. 2,519,001, No. 2,912,32
No. 9, No. 3,656,956, No. 3,672,897
No. 3,694.217, No. 4.025,349, No. 4,046,572, No. 2,688,545,
2,977.229, 3,397.060, 3,552,052, 3,527,641, 3
．． No. 617.293, No. 3.628.964, No. 3,
No. 666.480, No. 3,672,898, No. 3,6
No. 79,428, No. 3,703,377, No. 3,81
No. 4,609, No. 3,837,862, No. 4,026
, No. 344, British Patent No. L242,588, No. 1,34
No. 4,281, No. 1,507,803, Special Publication No. 1977-
No. 14,030, No. 52-24.844, No. 4349
No. 36, No. 5342.375, JP-A-52-110.
No. 618, No. 52-109, 925, No. 50-80.
It is described in No. 827, etc.

The amount of sensitizing dye added during silver halide emulsion preparation is
Although it cannot be unambiguously stated depending on the type of amount added or the amount of silver halide, the amount added by conventional methods,
That is, 50 to 80% of the saturated coverage can be used.

That is, the preferred amount of sensitizing dye added is silver halide 1
0.001 to 1010 Osl per mole, more preferably 0.01=10vwojl! It is.

The sensitizing dye may be added during the process of forming silver halide grains or during the chemical sensitization process, or may be added during coating.

In particular, methods for adding sensitizing dyes during the formation of silver halide emulsion grains include U.S. Pat.
No. 8,972 and JP-A-61-103.149 may be referred to. Furthermore, European Patent No. 29
1, No. 339-A, and JP-A-64-52.137 may be referred to. For the method of adding a sensitizing dye in the chemical sensitization process, reference may be made to JP-A-59-48,756.

Along with the sensitizing dye, it is a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light,
A substance exhibiting supersensitization may also be included in the emulsion. for example,
Aminostyl compounds substituted with nitrogen-containing heterocyclic groups (e.g., U.S. Pat. No. 2,933,390, Concurrent No. 3,635,7)
21), aromatic organic acid formaldehyde condensates (such as those described in US Pat. No. 3,743,510), cadmium salts, azaindene compounds, and the like. U.S. Patent No. 3,615,613, U.S. Patent No. 3,61
No. 5,641, No. 3.617.295, No. 3,635
, 721 are particularly useful.

The photographic emulsion used in the present invention can contain various compounds for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of the light-sensitive material, or for stabilizing photographic performance. Namely, azoles such as benzothiazolium salts, nitroindazoles, tonoazoles, benzotriazoles, benzimidazoles (particularly nitro- or halogen-substituted); heterocyclic mercapto compounds such as mercaptothiazoles, mercaptobenzothiazoles, Mercaptobenzimidazoles, mercaptothiazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole), mercaptopyrimidines; the above heterocyclic mercapto compounds having a water-soluble group such as a carboxyl group or a sulfone group; thioketo compounds For example, oxazolinthione; azaindenes such as tetraazaindenes (particularly 4-hydroxy-substituted (1,3,3a,7) tetraazaindenes); benzenethiosulfonic acids; benzenesulfinic acid; Many compounds known as stabilizers can be added.

The antifoggant or stabilizer is usually added after chemical sensitization, but more preferably it can be selected during chemical ripening or before the start of chemical ripening. In other words, during the silver salt solution grain formation process, during the addition of the silver salt solution, after the addition until the start of chemical ripening, and during the chemical ripening (during the chemical ripening time, preferably within 50% of the start). more preferably up to 20% of the time).

Specific examples include hydroxyazaindene compounds, benzotriazole compounds, and heterocyclic compounds substituted with at least one mercapto group and having at least two aza nitrogen atoms in the molecule.

The photographic emulsion used in the present invention is based on "Physics and Chemistry of Photography" by Grafkide, published by Paul Montell (P.
des, Chimie et Physique Ph
otographique Paul Montel,
1967), "Photographic Emulsion Chemistry" by Duffin, published by Focal Press (G.F. Duffin.

Photographic EagleSion
Che+wistry, Focal Pres
s.

(1966), “Manufacture and Coating of Photographic Emulsions” by Zelikman.
, Published by Focal Press (V, L, Zelikman
et alMaking and Coating P
Photographic illustration.

Focal Press, 1964). That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble silver salt with the soluble halogen salt may be any one-sided mixing method, simultaneous mixing method, or a combination thereof. good. 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 form of the simultaneous mixing method, a method in which the pAg in the liquid phase in which silver halide is produced can be kept constant, that is, a 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.

The silver halide emulsion consisting of the regular grains described above can be obtained by controlling pAg and pH during grain formation. For more information, please see Photographic Science
and Engineering (Photographic
5science and engineering)
Volume 6, pp. 159-165 (1962); Journal of Photographic Science (Journa
l of Pht.

graphic 5science), 12 volumes,
pp. 242-251 (1964), U.S. Patent No. 3.655
．． No. 394 and US Pat. No. L413,748.

Tabular grains are described in C. Theory and Practice of Photography by Creep (C1e
ve, Photography Theory a
nd Practice (1930)), p. 131;
Gutoff Photographic Science and Engineering Link
5science and engineering
) Volume 14, pp. 248-257 (1970); U.S. Patent Nos. 4,434,226 and 4,414,310;
It can be easily prepared by the methods described in British Patent No. 4,443.048, British Patent No. 4,439.52C, and British Patent No. 2.112.157. The use of tabular grains has advantages such as increased covering power and increased color sensitization efficiency by sensitizing dyes, which are detailed in the above-cited U.S. Pat. No. 4,434,226. .

Further, silver halides having different compositions may be joined by ubitaxial junction, or may be joined with a compound other than silver halide, such as silver rhodanide or lead oxide.

In the particles of the present invention, the shape of the inner core and the overall shape of the outermost shell may be the same or different. Specifically, the inner core has a cubic shape, and the shape of the outermost shelled particle may be cubic or octahedral. Conversely, the inner core may be octahedral and the outermost shelled particle may be cubic or octahedral. Furthermore, although the inner core is a clearly regular particle, the outermost shelled particle may have a slightly distorted shape or an irregular shape.

In addition, the boundaries between particles with these structures with different halogen compositions may be clear boundaries, or may be unclear boundaries due to the formation of mixed crystals due to composition differences, or may be actively continuous boundaries. It may also be one with some structural changes.

The silver halide emulsion used in the present invention is BP-009672
7B1, EP-0064412B1, etc., or DE-2
The surface may be modified as disclosed in JP-A-60-221320, No. 306447C2.

Silver halide solvents are useful to accelerate ripening. For example, it is known to have an excess of halogen ions present in the reactor to promote ripening. It is therefore clear that ripening can be accelerated simply by introducing a silver halide salt solution into the reactor. Other ripening agents can be used. These ripening agents can be blended in their entirety into the dispersion medium in the reactor before adding silver and halide salts, or one or more halide salts, silver salts, or peptizers can be added to the dispersion medium in the reactor. It can also be introduced into the reactor at the same time as adding. As a further variant, the ripening agent can also be introduced independently at the halide salt and silver salt addition stages.

As ripening agents other than halogen ions, ammonia or amine compounds, thiocyanate salts such as alkali metal thiocyanate salts, especially sodium and potassium thiocyanate salts, and ammonium thiocyanate salts can be used.

The silver halide emulsion of the present invention contains a cadmium salt, a zinc salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt, etc. in the process of silver halide grain formation or physical ripening. They may coexist.

The photographic emulsion of the present invention can be applied to various color and black and white light-sensitive materials. Typical examples include color negative films for general use or movies, color reversal films for slides or televisions, color vapors, color positive films, color reversal vapors, color diffusion type photosensitive materials, and heat-developable color photosensitive materials.

Films for plate making such as lithography film or scanner film, direct/indirect medical or industrial X-ray film, negative black and white film for photography, black and white photographic paper, C0M or regular micro film, silver salt diffusion transfer type photosensitive materials and printouts The photographic emulsion of the present invention can also be used in type light-sensitive materials.

A color light-sensitive material that can be used as the photographic emulsion of the present invention is provided with at least one silver halide emulsion layer, which is a blue-sensitive layer, a green-sensitive layer, a red-sensitive layer, or a layer sensitive to infrared light, on a support. There are no particular restrictions on the number or order of the silver halide emulsion layers and non-photosensitive layers. A typical example is a silver halide photographic light-sensitive material having on a support at least one photosensitive layer consisting of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different photosensitivity. is useful for photosensitive materials with improved exposure latitude for photography. In a multilayer silver halide color photographic light-sensitive material, the unit photosensitive layers are generally arranged in the following order from the support side: a red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer. but,
Depending on the purpose, the installation side may be reversed or different color-sensitive layers may be sandwiched between the same color-sensitive layer! llI
You can also take it.

Non-photosensitive layers such as various intermediate layers may be provided between the silver halide photosensitive layers and between the uppermost layer and the lowermost layer.

The intermediate layer includes JP-A Nos. 61-43748 and 59-1.
No. 13438, No. 59-113440, No. 61-20
Coupler and DIR compound as described in No. 037 and No. 61-20038 may be included, and a color mixing inhibitor as commonly used may be included.

A plurality of silver halide emulsion layers constituting each unit photosensitive layer are composed of a high-speed emulsion layer and a low-speed emulsion layer, as described in German Patent No. 1,121,470 or British Patent No. 923.045. A two-layer configuration can be preferably used.

Usually, it is preferable to arrange the layers so that the photosensitivity decreases toward the support, and a non-photosensitive layer may be provided between each halogen emulsion layer. Also, JP-A-57-
No. 112751, No. 62200350, No. 62-20
As described in No. 6541, No. 62-206543, etc., a low-sensitivity emulsion layer may be provided on the side far from the support, and a high-sensitivity emulsion layer may be provided on the side close to the support.

As a specific example, from the side farthest from the support, low sensitivity blue sensitive layer (BL) / high sensitivity blue sensitive layer (BH) / high sensitivity green sensitive layer (GH) / low sensitivity green sensitive layer (GL) / High-sensitivity red-sensitive layer (RH) / Low-sensitivity red-sensitive layer (RL), or BH/BL/GL/G H/RH/RL, or B H/B L/G H/G They can be installed in the order of L/R, L/RH, etc.

Further, as described in Japanese Patent Publication No. 55-34932, the blue-sensitive layer/G H/
They can also be arranged in the order of RH/GL/R/L. Alternatively, as described in JP-A-56-25738 and JP-A-62-63936, blue-sensitive 1ii/GL/RL/GH/RH can be arranged in the order from the farthest side from the support. .

In addition, as described in Japanese Patent Publication No. 49-15495, the upper layer is a silver halide emulsion layer with the highest sensitivity, the middle layer is a silver halide emulsion layer with lower sensitivity, and the lower layer is more sensitive than the middle layer. An example is an arrangement consisting of three layers with different photosensitivity, in which a silver halide emulsion layer with a low density is disposed and the photosensitivity gradually decreases toward the support. Even when it is composed of three layers with different photosensitivity, as described in JP-A No. 59-202464,
In the same color-sensitive layer, the medium-temperature emulsion layer/high-speed emulsion layer/low-speed emulsion layer may be arranged in this order from the side remote from the support.

In addition, high-sensitivity emulsion layer / low-sensitivity emulsion layer / medium-sensitivity emulsion layer,
Alternatively, they may be arranged in the order of low-speed emulsion layer/medium-speed emulsion layer/high-speed emulsion layer, etc.

To improve color reproduction, U.S. Patent No. 4,663.2
No. 71, No. 4,705,744, No. 4,707.
No. 436, JP-A-62-160448, JP-A No. 63-89
A multilayer effect donor Ji having a different spectral sensitivity distribution from the main photosensitive layer such as B L/G L/RL described in the specification of No. 580
(CL,) is preferably arranged adjacent to or close to the main photosensitive layer.

When the present invention is applied to color negative or color reversal films, preferred silver halides contained in the photographic emulsion layer include silver iodobromide, iodochloride, containing an average silver iodide of up to about 30 mole percent. Silver or silver iodochlorobromide.

Particularly preferred are silver iodobromide or silver iodochloride containing an average silver iodide content of from about 2 mole percent to about 25 mole percent.

Although the average grain size of the photographic emulsion of the present invention is arbitrary, it preferably has a projected area diameter of 0.5 to 4 microns, and may be a polydisperse emulsion or a monodisperse emulsion.

Known photographic additives that can be used in combination with the photographic emulsion of the present invention are described in two research dispirators, and the relevant descriptions are shown in the table below.

(Blank below) Superimposed 5 Jii RD 17643 1 Chemical sensitizer 23 pages 2 Sensitivity enhancer 3 Spectral sensitizer 23-24 pages Super sensitizer 4 Brightening agent 24 pages 5 Anti-fogging agent 24-25 pages and stabilizer 6 Light absorbers, pages 25-26 Filter dyes UV absorbers Anti-stain agents Page 25 Right column dyes Image stabilizers Page 25 Hardeners Page 26 Binders Page 26 Plasticizers, lubricants Page 27 Coating aids, 26 - Page 27 Surfactant 13 Static Page 27 Inhibitor RD 18716 Page 648 Right column Same as above Page 648 Right column - Page 649 Right column Page 649 Right column - Page 649 Right column - Page 650 Left column Page 650 Left to right column Page 651 Left column, same as above, page 650, right column, page 650, right column, same as above In addition, in order to prevent deterioration of photographic performance due to formaldehyde gas, U.S. Pat.
It is preferable to add to the photosensitive material a compound that can be immobilized by reacting with formaldehyde, as described in No. 435,503.

The photographic emulsion of the present invention is preferably used in color light-sensitive materials, and various color couplers can be used.
A specific example is the aforementioned Research Disclosure (RD).
) N1117643, ■-C-C d.

As a yellow coupler, for example, U.S. Patent Box 3.9
No. 33,501, No. 4.022.620, No. 4,
No. 326,024, No. 4,401,752, No. 4
, 248,961, Japanese Patent Publication No. 58-10739, British Patent No. 1.425,020, British Patent No. 1.476.760
No., U.S. Patent Box 3.973.968, U.S. Patent No. 4.314
．． No. 023, No. 4,51L649, European Patent Box 24
9.473A, etc. are preferred.

As magenta couplers, 5-pyrazolone and pyrazoloazole compounds are preferred, and U.S. Pat.
No. 0,619, No. 4.35L897, European Patent Box 7
3.636, U.S. Patent Box 3.061.432, U.S. Patent Box 3.725.067, Research Disclosure Seed 24220 (June 1984), JP-A-60-335
No. 52, Research Discology + -k24230
(June 1984), JP 60-43659, JP 61-72238, JP 60-35730, JP 55-
118034, 60485951, U.S. Patent Box 4,500.630, 4,540,654, 4.565,630, International Publication WO3810479
Particularly preferred are those described in No. 5 and the like.

Cyan couplers include phenolic and naphthol couplers, and are described in U.S. Patent Box 4.052,212.
No. 4,146.396, No. 4.228,23
No. 3, No. 4.296,200, No. 2.369,92
No. 9, No. 2.801,171, No. 2,772.1
No. 62, No. 2.895,826, No. 3.772.
No. 002, No. 3,758,308, No. 4.343
,011, European Patent Publication No. 4.327.173, European Patent Publication No. 3,329,729, European Patent Publication No. 121,36
5 A, No. 249453 A, U.S. Patent Boxes 3 and 4
No. 46,622, No. 4.333.999, No. 4,
No. 775,616, No. 4.451.559, No. 4
, No. 427,767, No. 4,690.889, No. 4,254,212, No. 4,296.199, JP-A-6142658, etc. are preferred.

Colored couplers for correcting unnecessary absorption of coloring dyes are available at Research Disclosure Floor 17643.
- Section G, U.S. Patent No. 4,163,670, Japanese Patent Publication No. 1983
-39413, U.S. Patent No. 4.004,929, U.S. Patent No. 4.138,258, British Patent No. 1.146,36
The one described in No. 8 is preferred. Also, U.S. Patent Nos. 4 and 7
No. 74.181, a coupler that corrects unnecessary absorption of a coloring dye by means of a fluorescent dye released during coupling, and a coupler that can react with a developing agent to form a dye, as described in U.S. Pat. No. 4,777,120. It is also preferred to use couplers having a dye precursor group as a leaving group.

Couplers whose coloring dyes have appropriate diffusivity include U.S. Patent No. 4.366.237 and British Patent No. 2.125.
, 570, European Patent No. 96.570, and German Patent Publication No. 3.234.533 are preferred.

Typical examples of polymerized dye-forming couplers are U.S. Pat. Nos. 3,451,820; 4,080,221;
4.367.288, 4.409,320, 4,576.910, British Patent 2.102.1
It is described in No. 73, etc.

Couplers that release photographically useful residues upon coupling are also preferably used in the present invention. The DIR coupler releasing the development inhibitor is RD17643 as previously described.
, Patents described in sections ■ to F, Japanese Patent Application Laid-Open No. 57-15194
No. 4, No. 57-154234, No. 60-184248
Preferred are those described in U.S. Pat. No. 63-37346, U.S. Pat.

Other couplers that can be used in the light-sensitive material of the present invention include competitive couplers described in U.S. Pat. No. 4,130,427, U.S. Pat. , DIR redox compound releasing couplers described in JP-A-60-185950, JP-A-6224525, etc., DIR coupler-releasing couplers, D
IR coupler releasing redox compound or DIR redox releasing redox compound, European Patent No. 173.30
2 A, No. 313,308 Coupler releasing a dye that recolors after separation as described in No. A, R, D, kl1449
, No. 24241, bleach accelerator-releasing couplers described in JP-A-61-201247, etc., U.S. Patent No. 4.553,
Ligand releasing coupler described in No. 477 etc., JP-A-63
Examples include couplers that release leuco dyes as described in US Pat. No. 4,774,181 and couplers that release fluorescent dyes as described in US Pat.

The color photosensitive material of the present invention includes JP-A-63-2577
No. 47, No. 62-272248, and JP-A-1-8
1,2-benzisothiazoline-3 described in No. 0941
-one, n-butyl-P-hydroxybenzoate, phenol, 4-chloro-3,5-dimethylphenol,
It is preferable to apply various preservatives or fungicides such as 2-phenoxyethanol and 2-(4-thiazolyl)benzimidazole.

Suitable supports that can be used in the present invention include, for example, the above-mentioned R
D, page 28 of 17643 and 6 of 18716
It is described from the right column on page 47 to the left column on page 648.

In the photosensitive material using the photographic milkweed of the present invention, the total thickness of all the hydrophilic colloid layers on the side having the emulsion layer is preferably 28 μm or less, more preferably 23 μm or less,
More preferably, the thickness is 20 μm or less. Also, membrane swelling rate TI/□
is preferably 30 seconds or less, more preferably 20 seconds or less.

The film thickness means the film thickness measured at 25° C. and 55% humidity (2 days), and the film swelling rate T,/2 can be measured according to a method known in the art.

For example, Photographic Science and Engineering (Photogr, Sci, Eng, ) by Green et al.
, Vol. 19, No. 2, pp. 124-129, it can be measured by using a swelling meter (swelling membrane), and TI/□ is the maximum value reached when treated with a color developer for 13 minutes and 15 seconds at 30°C. 90% of the swollen film thickness is defined as the saturated film thickness, and is defined as the time required to reach 1/2 of the saturated film thickness.

The membrane swelling rate TI/□ can be adjusted by adding a hardening agent to gelatin as a binder or by changing the aging conditions after coating. Also, the swelling rate is 1
50-400% is preferred.

The swelling ratio is calculated from the maximum swollen film thickness under the conditions described above according to the formula: (maximum swollen film thickness - film thickness)/film thickness.

The color photographic light-sensitive material according to the present invention can be developed by the conventional method described in the above-mentioned RD, No. 17643, pages 28 to 29, and 615, left column to right column, of the same RD, No. 18716.

Furthermore, when performing reversal processing, black and white development is usually performed and then color development is performed. This black and white developer contains known black and white developing agents such as dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone, or aminophenols such as N-methyl-P-aminophenol. It can be used alone or in combination.

Silver halide color photographic light-sensitive materials using the photographic emulsion of the present invention are generally subjected to water washing and/or stabilization steps after desilvering treatment. The amount of water used in the washing process depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), the application, the temperature of the washing water, the number of washing tanks (number of stages), the replenishment method such as countercurrent or forward flow, and various other conditions. Can be set over a wide range.

Among these, the relationship between the number of washing tanks and the amount of water in the multistage countercurrent method is described in the Journal of the 5ociet.
y of Motion Picture and Te
1evision Engineers Volume 64, P
, 248-253 (May 1955 issue).

According to the multi-stage countercurrent method described in the above-mentioned literature, the amount of water used for washing can be significantly reduced, but due to the increase in the residence time of water in the tank, bacteria will breed, and the generated suspended matter will adhere to the photosensitive material. The problem arises. In the processing of the color photosensitive material of the present invention, as a solution to such problems,
The method for reducing calcium ions and magnesium ions described in JP-A No. 62-288, 838 can be used very effectively. Also, JP-A-57-8, 54
Chlorinated disinfectants such as isothiazolone compounds, cyabendazole, chlorinated sodium isocyanurate, etc. described in No. 2, pendotriazole, etc., Hiroshi Horiguchi, "Chemistry of antibacterial and fungicidal agents J (1986), Sankyo Publishing, "Microbial Sterilization, Disinfection, and Anti-Mold Technology" (1982), edited by the Society of Hygiene Technology; "Encyclopedia of Antibacterial and Anti-Mold Agents" (1982) edited by the Society of Industrial Technology;
The fungicides described in 6) can also be used.

The p)I of the washing water in the processing of the photosensitive material of the present invention is 4
-9, preferably 5-8. Various settings can be made depending on the washing water temperature, washing time, characteristics of the photosensitive material, application, etc., but generally the range is 20 seconds to 10 minutes at 15 to 45°C, preferably 30 seconds to 5 minutes at 25 to 40°C. Furthermore, the photosensitive material of the present invention is selected.

Instead of the above-mentioned washing with water, the treatment can be performed directly with a stabilizing solution. In such stabilization treatment, Japanese Patent Application Laid-open No. 57-
No. 8543, No. 5B-14834, No. 60-2203
All known methods described in No. 45 can be used.

Furthermore, following the water washing treatment, a further stabilization treatment may be performed, such as a formalin bath, which is used as a final bath for color photosensitive materials for photography.

The present invention will be further explained below with reference to Examples.

Example-1 (1) Preparation of emulsion A, preparation of base emulsion Preparation of emulsion A-1 (AgBr tabular grains) A 0.7% aqueous solution of low molecular weight gelatin containing 0.91 mol of potassium bromide was heated to 30°C. With constant stirring, a 1.01 molar aqueous solution of potassium bromide and a 0.94 molar aqueous silver nitrate solution were added to this using the double jet method at the same constant flow rate over a period of 1 minute (consuming 12.7% of the total silver nitrate). After adding a further 16% deionized gelatin solution 400 @f7
The temperature was raised to 5°C. Add 0.88 mol silver nitrate aqueous solution and pB
After adjusting r to 2.31 (consuming 3.7% of the total silver nitrate), add 14.7N ammonia aqueous solution and add pl(8.
After physical ripening, 3N nitric acid was added to adjust p)l to 5.5. A 1.33 molar aqueous solution of potassium bromide and a 0.88 molar aqueous silver nitrate solution were simultaneously added over 30 minutes while maintaining the pBr at 3602 (83.6% of the total silver nitrate was consumed). Then, it was desalted by the usual flocculation method to obtain an average aspect ratio of 6.5 and a circular phase of 5 and a diameter of 1.
．． A tabular AgBr emulsion A-1 having a diameter of 0 μm was prepared.

The amount of silver nitrate used was 156 g.

Emulsion A-2 (A in the central region, central annular region and peripheral annular region)
Preparation of a 0.7% aqueous solution of deionized gelatin containing 0.57 mol of potassium bromide with a silver iodide content in the same 3N range of 0/'4.6/12 (g ratio 16.1/67.3/16) (Solution A)1. While keeping Of at 30°C and stirring, a 1.95 mol potassium bromide aqueous solution (solution B) and a 1.9 mol silver nitrate aqueous solution (solution C) were added to this by the double jet method at the same constant flow rate for 30 seconds.
(consumed 2.06% of total silver nitrate). After adding an additional 400 mf of 8% deionized gelatin solution, 75 mf
The temperature was raised to °C. Silver nitrate 1.12 mol aqueous solution (solution D)
was added to adjust the pBr to 2.13 (1.
After physical ripening, a 14.7N ammonia aqueous solution (84% of which had been consumed) was added to adjust the pH to 8.3, and then IN nitric acid was added to adjust the pH to 5.5 again. A 1.34 molar potassium bromide aqueous solution (solution E) and a solution were added simultaneously at accelerated flow rates (end flow rate was 2.5 times the starting flow rate) over 11 minutes while maintaining pBr at 1.56. After (12.8% of the total silver nitrate was consumed), IN NaOH was added to adjust the pH to 9.3. 28. An aqueous solution containing 1.35 mol of potassium bromide and 0.065 mol of potassium iodide (solution F) and solution were added while accelerating the flow rate at the same time (the flow rate at the end was 5.5 times that at the beginning) 28. was added over a period of 5 minutes while maintaining the pBr at 1.56 (6% of total silver nitrate).
(7.3% was consumed). Furthermore, an aqueous solution containing 1.24 mol of potassium bromide and 0.17 mol of potassium iodide (solution G) was added for 10 minutes while simultaneously accelerating the flow rate (the flow rate at the end was twice that at the beginning). pBr
was added keeping the concentration at 2.42 (16% of the total silver nitrate was consumed). Then, it was desalted by the usual flocculation method, and the average aspect ratio was 6.5, and the equivalent circle diameter was 1.0 μm.
Tabular AgBr1 (AgI = 5.0 mol)
Emulsion A-2 was prepared. The amount of silver nitrate used was 156 g. The obtained high aspect ratio tabular silver iodobromide grains had a surface silver iodide concentration of 10.8 mol% and an average silver iodide concentration of 4.9 mol%, and the peripheral annular region had a higher iodine concentration than the central region. Chemical I
It showed that it was n degrees.

B. Preparation of particles with dislocations concentrated near the apex ■ 5
00g of base emulsion A-1, A-2 (0.5moffiA
g) and 350 cc of distilled water were mixed, heated to 40°C, and stirred well. This state was maintained and the following steps were performed.

■ Potassium iodide solution (concentration 0.04 mol /
1) was added over 15 minutes.

■ 4.1moj2% of the silver content of the base emulsion, respectively.
An amount of silver nitrate solution (concentration 1.02 ol/l)
) and sodium chloride solution (1,58 ol/l) were added over 1 minute using a double jet method.

■ Potassium iodide solution in an amount equivalent to 1.302% of the silver content of the base emulsion (0.04 sof/ff1 at a time)
was added over 8 minutes.

■ Silver nitrate solution (concentration 1.02 moj2/l) in an amount corresponding to 50 mof% of the silver amount in the base emulsion.
and potassium bromide solution (concentration 1.02 ol/l) in pB
It was added over 49 minutes while maintaining r=1.73.

■ Desalted by flocculation method.

Emulsion prepared using emulsion A-1 as a base emulsion (emulsion B-1
), an emulsion prepared using emulsion A-2 as a base emulsion (emulsion B
-2) Both have an average aspect ratio of 6.5 and an equivalent circle diameter of 1.
It was 3 μm.

Preparation of particles with dislocations that do not localize C1 Among the procedures ■ to ■ described in B, ■, ■, ■, ■.

Only ■ was performed. An emulsion prepared from emulsion A-2 was designated as emulsion C-2.

D. Preparation of particles free of dislocations Of the procedures ■ to ■ described in B, only ■, ■, and ■ were performed.

An emulsion prepared from emulsion A-2 was designated as emulsion D-2.

(2) Observation of dislocations in grains Dislocations were directly observed for emulsions B-2, C-2, and D-2 using a transmission electron microscope. The electron microscope used was JEM-2000FX II manufactured by JEOL Ltd., and observation was performed at an accelerating voltage of 200 kV and a temperature of -120°C.

FIG. 1 shows a photograph of typical grains obtained by observing emulsion B-2. It is clearly seen that dislocations are concentrated only near the vertices.

FIG. 2 shows a photograph of typical grains obtained by observing emulsion C-2. It can be seen that the dislocations are not concentrated and are uniformly introduced along the edges of the particles.

FIG. 3 is a photograph of typical grains of emulsion D-2. Not a single dislocation was introduced.

(3) For chemically sensitized emulsions B-1, B-2, C-2, and D-2, Na2S
2O3, KSCN, HAuCl m were added so that the highest sensitivity was obtained when exposed for 1 x 100 seconds, and the temperature was increased to 60'C.
It was held for 60 minutes.

(4) A shell for forming an internal latent image was formed by adding silver nitrate and an aqueous halogen solution using a double chef) to form a shell having a halogen composition and thickness as shown in Table 1.

(5) Preparation and evaluation of coating samples The following sensitizing dyes were added to each emulsion shown in Table 1 at 6.5 x 10
After adding 1 offi/moffiAg, the emulsion and protective layer were coated on a cellulose triacetate film support on which an undercoat layer was provided, in the coating amounts shown in Table 2, to prepare a coated sample.

Sensitizing dye emulsion coating conditions (1) Emulsion layer/emulsion...Various emulsions (silver 3.6 x 10-'' mol/bo) Coupler (1.5 x 10-'' mol/rrf) Tricresyl phosphate (1 ,,10g/n()・Gelatin (2,30g/po)(2)
Reservoir layer, 2,4-dichloro-6-hydroxy-3-triazine sodium salt (0.08 g/p), gelatin (1,80 g/p) These samples were heated at 40°C and 70% relative humidity. After being left to stand for 14 hours, it was exposed to light for 1/100 second through a continuous wedge, and the color development shown in Table 3 below was performed.

Further, it was stored for one month under the conditions of 45° C. and relative humidity of 50° C., and exposed and developed in the same manner.

The concentration of the treated sample was measured using a green filter.

Table 3 Process Processing time Processing temperature Color development
2 minutes 00 seconds 40°C bleach fixing 3 minutes OO
Seconds 40°C water washing (1) 20 seconds
Wash with water at 35℃ (2) 20 seconds
Stable at 35℃ 20 seconds 35
°C drying 50 seconds 65
°C Next, the composition of the processing solution will be described.

(Color developer) (Unit g) Diethylenetriaminepentaacetic acid 2. Ol-hydroxyethylidene-3,0 1,1-diphosphonic acid sodium sulfite 4.0 Potassium carbonate 30.0 Potassium bromide
1.4 potassium iodide
1.5 ■ Hydroxylamine sulfate
2.44-[N-ethyl-N-β-hydroxyethylamino]-2-methylaniline sulfate solution was added and pl'! (Bleach-fix solution) Ethylenediaminetetraacetic acid ferric ammonium dihydrate Ethylenediaminetetraacetic acid disodium salt Sodium sulfite Ammonium thiosulfate aqueous solution (70%) Acetic acid (98%) Bleach accelerator 4.5 1.01 10.05 (Unit: g) ) 90.0 5.0 12.0 260.0 5.0sf Add 0.01 mol water to pH 1.0! 6.0 (Water washing liquid) A hotbed column filled with tap water and an H-type strongly acidic cation exchange resin (Amberlite IR-120B, manufactured by Rohm and Haas) and an OH-type anion exchange resin (Amberlite IR-400, manufactured by Rohm and Haas) Water was passed through the reactor to reduce the concentration of calcium and magnesium ions to 3/l or less, and then 20/l of sodium isocyanurate dichloride and 1.5 g/l of sodium sulfate were added.

The pH of this solution is in the range of 6.5-7.5.

(Stabilizing solution) (Unit: g) Formalin (37%) 2. Osj! Polyoxyethylene-p -0,3 Monononylphenyl ether (average degree of polymerization 10) Ethylenediaminetetraacetic acid Add 0.05 disodium salt water to 1.01 pH 5,
0-8.0 Sensitivity was expressed as a relative value of the logarithm of the reciprocal of the exposure amount expressed in lux seconds giving a density of 0.2 above fog. (The sensitivity of emulsion B one day after coating was set as 100.

From the comparison between D-2 and H-1, there is no increase in sensitivity just by layering the inner layer, but when B-1 and E-1, B-2 and F-1,
A comparison between C-2 and G-1 shows that the effect of inner layer formation is remarkable in grains having dislocations. F-1, F-3, F
It can be seen from the comparison of -4 that when the shell thickness is 60 nm, development is delayed and sensitivity is reduced. Furthermore, from a comparison between F-1 and G-1, the sensitivity of particles in which dislocations were present at the apex was high. Comparison of shell solubility is E-1 and E-2, F-1 and F
-2, the higher the solubility of the shell, the higher the sensitivity.

On the other hand, the sensitivity after storage for one month showed almost no change compared to before storage for the shallowly submerged emulsion.

Further, even when the sensitizing dye was added to the emulsions shown in Table 1 before chemical ripening, or added before chemical ripening, and further added after chemical ripening, the emulsions of the present invention had high sensitivity.

Example-2 On a subbed cellulose triacetate film support,
Each layer having the composition shown below was coated in layers, and the emulsions B-1, E-1, E-2°G-1 described in Example-1 were applied to the seventh layer (red-sensitive emulsion layer) of the multilayer color light-sensitive material. 20 samples each containing
1 to 204 were produced.

(Rapid light layer composition) The numbers corresponding to each component indicate the coating amount expressed in g/%, and for silver halide, the coating amount is expressed in terms of silver. However, for sensitizing dyes, the coating amount is expressed in g/%. silver halide 1
The coating amount is expressed in moles.

1st layer (antihalation N) Black colloidal silver Silver 0.18 Gelatin 1.40 2nd layer (intermediate layer) 2.5-di-t-pentadecylhydroquinone 0.18EX-10
,07 E
Donor layer for interlayer effect on red-sensitive layer) Emulsion J
Silver 1.2 emulsion K
Silver 2.0 Sensitizing Dye IV 4
X10-'EX-100,10 HB S -10,10 HB S -20,10 Gelatin 3.0 4th layer (middle layer) EX -50,040 HB S -10,020 Gelatin 0.80 5th layer (
1st red-sensitive emulsion layer) Emulsion A MA O,25 Emulsion B Silver 0.25 Sensitizing Dye I
1.5 Xl0-' Sensitizing dye■ Sensitizing dye■ X-2 X-10 U~1 B5-1 Gelatin 6th layer (second red-sensitive emulsion layer) Emulsion G Sensitizing dye I Sensitizing dye■ Dye ■ X-2 X-3 X-10 i, s xio-5 2.5 Xl0-' 1.4 Xl0-' 2, OxlO-' 0.400 o, os.

O,015 0,07 0,05 0,07 Gelatin 7th layer (third red-glare emulsion layer) Emulsion (any emulsion of B-1, E-1, E-2, G-1) Enhancement dye I Exacerbating dye ■ Exacerbating dye ■ Eχ-3 Eχ-4 X-2 B5-1 B5-2 8th gelatin layer (intermediate layer) X-5 B5-1 9th gelatin layer (1st green-sensitive breast layer) Emulsion A Emulsion B 1.30 Silver 1.60 1, OXl0-' 1.4 Xl0-5 2.0 Xl0-' o, oi.

o,os.

O,097 0,22 0,10 1,63 0,040 0,020 0,80 Silver 0.15 Silver 0,15 Sensitizing dye V Sensitizing dye ■ Sensitizing dye ■ Sensitizing dye ■ X-6 X- 1 X-7 X-8 B5-1 B5-3 Gelatin 10th layer (second green emulsion layer) Emulsion C Sensitizing dye■ Sensitizing dye■ Sensitizing dye■ Sensitizing dye■ X-6 X-22 X -7 3, OXl0-' 1, OXl0-' 3.8 Xl0-' 5, OXl0-' 0.260 0.021 0.030 0.005 0.100 0.010 0.63 Silver 0.45 2, I Sensitizing dye V Sensitizing dye ■ Sensitizing dye ■ Sensitizing dye ■ EX-13 EX-11 EX-1 B5-1 B5-2 Gelatin 12th layer (yellow filter layer) Yellow colloidal silver EX-5 B5-1 Gelatin 0 .160 o, oos 0.50 Silver 1.2 3.5 Xl0-' 8, OXl0-' 3, OXl0-' 0.5 Xl0-' 0.015 0.100 0.025 0.25 0.10 1 .54 Silver 0.05 0.08 0.03 0.95 13th layer (first blue-sensitive emulsion N) Emulsion A Emulsion B Exacerbating dye ■ EX-9 EX-8 B5-1 Gelatin 14th layer (second blue-sensitive emulsion Emulsion G Sensitizing dye ■ EX-9 EX-IQ B5-1 Gelatin 15th layer (third blue-sensitive emulsion layer) Emulsion H Sensitizing dye ■ EX-9 B5-1 Silver 0.10 Silver 0. 12 7, OXl(1-' 0.721 0.042 0.28 1.10 Silver 0.45 2, I Xl0-' 0,154 0.007 0.05 0.78 Silver 0.77 2.2 X10 0.20 0.07 Gelatin 0.69 16th layer (first protective layer) Emulsion■ Silver 0.20U-40
,11 U-50・17 HBS-10,05 Gelatin 1.00 17th layer (
2nd protective layer) Polymethyl acrylate particles (diameter approximately 1.5 μm) 0.54S
-10,20 Gelatin 1.20 In addition to the above ingredients, each layer contains gelatin hardening agents H-1 and EX-1.
4-21 and a surfactant were added. Emulsions A and B used to create the above samples.

The contents of C, E, G, H, I, J, and K are shown in Table 4. In addition, the structural formulas or names of the compounds used to prepare the samples are shown in Table A below.

Samples 201 to 204 thus obtained were exposed and processed using an automatic processor according to the processing method described in Table 5 (until the cumulative replenishment amount of bleaching solution became three times the capacity of the mother liquor tank).
Processed.

Table 5 Processing method Process coloring phenomenon bleaching white Wash with water Fixed arrival processing time 3 minutes 15 seconds 6 minutes 30 seconds 2 minutes lO seconds 4 minutes 20 seconds Processing temperature Replenishment amount 38°C 38°C 24°C 38℃ 3IIIIN 5ta 1 120 axes 1 tank capacity Wash with water (2) 1 minute 00 seconds Stability 1 minute 05 seconds Drying 4 minutes 20 seconds 24°C 1200m 1 38°C 5w 1 55°C *Replenishment amount is 35cm per 1m length Next, the composition of the treatment liquid will be described.

(Color developer) Mother liquid axis) Replenisher (g) Diethylenetriamine 1.0 1.1 Pentaacetic acid 1-hydroxyethyl 3.0 3.2 Den-1.1-diphosphonic acid sodium sulfite 4.0 4.4 Potassium carbonate 30.0 37.0 Potassium bromide 1.4 0.7 Potassium iodide 1.5■ Hydroxylamine
2.4 2.8 Sulfate 4-(N-ethyl-N-4,55,5 β-hydroxylamino)-2-meraniline sulfate Add water 1. OL 1.0L
pH 10,0510,10 (Bleach solution) Sodium ferric ethylenediaminetetraacetate trihydrate Ethylenediaminetetraacetic acid disodium ammonium chloride Ammonium nitrate Aqueous ammonia (27%) Add water and H (Fixer) Ethylenediamine tetraacetate Acid disodium salt Sodium bisulfite Sodium ammonium thiosulfate aqueous solution (70%) Add water to mother liquor (g) Replenisher solution (g) 100, OL20.0 10.0 140.0 30.0 6.5o+ 1 1, OL 6.0 11.0 160.0 35.0 4, Ota I! 1, OL 5.7 Mother liquor (g) replenisher axis) 0.5 0.7 7.0 B, 0 5.0 5.5 170. nmj! 200.0*f 1, OL 1, OL pH 6,76,6 (stable solution) Mother liquor (g) Replenisher solution (g) Formalin (37%) 2.0mA 3.
07! Polyoxyethylene 0.3 0.4
5-p~monononylphunyl ether (average degree of polymerization 10) Ethylenediamine 0.05 0.08 Add disodium tetraacetic acid salt solution 1. OL 1.0Lp
H5, 8-8, 05, 0-8,0 Sensitivity was evaluated by the logarithm of the reciprocal of the exposure amount (relative value with Sample 201 as 100) that gave a density 0.2 higher than the lowest cyan density. (Table 6) Similar to Table 1 Example 1, the emulsion of the present invention had high sensitivity even in the color multilayer coating samples.

Example 3 The color multilayer coating sample of Example 2 was subjected to the following development treatment.

Table 7 Processing method Process Processing time Color development 3 minutes 15 seconds Bleach White 1 minute 00 seconds Bleach fixing 3 minutes 15 seconds Wash with water (1) 40 seconds Wash with water (2) 1 minute 00 seconds Processing temperature 38゛C 38゛C 38℃ 35°C 35℃ Stability 40 seconds Drying 1 minute 15 seconds Next, the composition of the treatment liquid will be described.

(color developer) diethylenetriaminepentaacetic acid 1-hydroxyethylidene -1,1-diphosphonic acid sodium sulfite potassium carbonate potassium bromide potassium iodide hydroxylamine sulfate 4-[N-ethyl-N-β- hydroxyethylamino]= 2-Methylaniline sulfate add water pl'1 (bleaching liquid) Ethylenediaminetetraacetic acid Ferric ammonia water dihydrate salt 38°C 55°C (unit【) 1.0 3.0 4.0 30.0 1.4 1.5 ■ 2.4 4.5 1.02 io, os (Unit: g) 120.0 Ethylenediaminetetraacetic acid disodium salt ammonium bromide ammonium nitrate bleach accelerator 10.0 ioo,.

io,.

0.005M ammonia water (27%) Add water to pi+ (bleach-fix solution) Ethylenediaminetetraacetic acid ammonium dihydrate Ethylenediaminetetraacetic acid disodium salt Sodium sulfite ammonium thiosulfate aqueous solution 15.0M1 1.01 6.3 ( Unit g) 50.0 5.0 12.0 240, Od (70%) Ammonia water (27%) 6.0d Add water 1.0! pH 7.2 (washing solution) Tap water was filled with an H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rowe and Haas) and an OH-type anion exchange resin (Amberlite IR-400). Water is passed through a mixed bed column to reduce the concentration of calcium and magnesium ions to 3 tag/z or less, followed by isocyanuric dichloride-resistant sodium chloride at 2 nm/1. and sodium sulfate 0.15g/42 were added. p of this liquid
H is in the range 6.5-7.5.

(Stabilizing solution) (Unit g) Formalin (37%) 2.0I11 polyoxyethylene-p -0゜3 1,000 tunonylphenyl ether (average degree of polymerization 10) Ethylenediaminetetraacetic acid Add 0.05 disodium salt water and add 1 ．． Ofρ”
5.8-8.0 Even with the processing method shown in Table 7, the sensitivity of the emulsion of the present invention was high as in Example 2.

Example 4 The color multilayer coating sample of Example 2 was subjected to the following development treatment.

8th Processing method step Processing time Processing temperature Replenishment amount 'l Sink amount Color development 3 minutes 15 seconds 37.8℃ 25d 101
Bleach 45 seconds 38℃ 5H1
4 Bleach-fixing (1) 45 seconds 38℃ -41
Bleach fixing (2) 45 seconds 38℃ 3 (ld
4N water washing (1) 20 seconds 38°C-
2F water washing (2) 20 seconds 38℃ 30
d 2f stable 20 seconds 38°C2
0d 2f Drying 1 minute 55℃ *Replenishment amount is per 35mm width 1m length Each process of bleach-fixing and water washing is counter-current flow from (2) to (1), and overflow of bleaching solution All of the solution was introduced into the bleach-fixer (2).

In the above process, the amount of bleach-fix solution carried into the washing process was 2 i per 1 m length of the 35 mm wide photosensitive material.

(Color developer) Mother solution (g) Replenisher (g) Diethylenetriaminepentaacetic acid 5.0 6.0 Sodium sulfite 4.0 5.0 Potassium carbonate 30.0 37.0 Potassium bromide 1°3o, 5 Potassium iodide
1.2 ■ Hydroxylamine sulfate 2.0
3. Add 64-[N-ethyl-N-β-4,76,2hydroxyethylamino]-2-methylaniline sulfate solution 1. Of 1.0fp
H10,0010,15 (Bleach solution) Mother liquor (g) Replenisher solution (g) 1
．． 3-diaminopropane 144.0 206.0
Ferric ammonium tetraacetate hydrate 1.3-diaminopropane tetraacetic acid ammonium bromide Ammonium nitrate Aqueous ammonia (27%) Acetic acid (98%) Add water to pH (bleach-fix solution) Ferric ammonium ethylenediaminetetraacetate Trihydrate Ethylenediaminetetraacetic acid disodium salt Ammonium sulfite Ammonium thiosulfate aqueous solution (700g/I!) Ammonia water (27%) 2.8 4.0 84.0 120.0 17.5 25.0 10.0 1.8 51.1 73.0 1.0 1 1. H 4,33,4 Mother liquor (g) Replenisher solution (g) 50.0 5.0 25.0 12.0 20.0 290, Od 320. Od 6.0 d 15.0d Add water 7 1.011.0fpH6
, 88,0 (Rinse water) Mother liquor and replenisher Common tap water was mixed with H-type strongly acidic cation exchange resin (Amberlite IR-120B, manufactured by Rohmt Haas) and O) (type strong basic anion exchange resin (Amberlite IR-120B) Norite IRA-
400) to reduce the concentration of calcium and magnesium to below 3■/l,
Next, sodium esyanurate dichloride 20■/! and sodium sulfate 1, rum 150*//! was added. The value of this liquid was in the range of 6.5-7.5.

(Stabilizing solution) Common to mother solution and replenisher solution (Unit: g) Formalin (37%) 1.2m Surfactant 0.4 (C+Jz+
0 (CHtCH2O-+-rrH) ethylene glycol i,.

Add water 1.0fpH5
,0-7,0 Even with the processing method shown in Table 8, as in Example 2, the sensitivity of the emulsion of the present invention was high.

Example 5 A monodisperse octahedral emulsion was prepared according to a conventional method, and a monodisperse octahedral emulsion was prepared according to Example (1).
Dislocations were introduced into the grains by methods B, C, or D. Next, chemical sensitization was carried out by the method of Example 1 (3), and a shell was further formed by the method of Example 1 (4). A list of the prepared emulsions is shown in Table 9. The base grains are silver iodobromide with a core/shell ratio of 1/3 (core iodide 30I 11%, shell iodide 01d%). The final particle size was 0-8 μm in average equivalent diameter.

on a subbed cellulose triacetate film support.
A multilayer color photosensitive material consisting of each layer having the composition shown below was prepared.

(Composition of photosensitive layer) For silver hagelonide and colloidal silver, the coating amount is
/rd units, for couplers, additives and gelatins in g/rrr units, and for sensitizing dyes in moles per mole of silver halide in the same layer. .

1st layer (antihalation layer) Black colloidal silver gelatin JV-1 V-2 V-3 v-4 0i! -1 2nd layer (middle layer) Gelatin River 1.0... 0.
2 ... 1.3 ... 0.05 ... 0.05 ... 0.10 ... 0. lO ... 0.10 ... 0.10 Third layer (first red-sensitive emulsion layer) Silver iodobromide emulsion (AgI 7.1 mol%, octahedral multi-structure grains, volume equivalent method diameter 0. 4μ■, coefficient of variation of equivalent sphere diameter 15% Coated silver amount...1.0 Gelatin...2.O3-1
2,8X10-' S -22,0xlO-' S -31,0X10zu Cp-1...0.40 Cp-2...0.040 Cp-3...0.020 Cp-4...・0.0020 0i1-1 ...0.150
i1-2...0.15 4th
Layer (second red-sensitive milking layer) Coated silver amount of any one of emulsions R-1 to R-8 listed in Table-9...1.20 Gelatin...0°8S -
12,0X10-' Cp-1 Cp-2 Cp-3 Cp-4 5th layer (third red-sensitive emulsion layer) Silver iodobromide emulsion (Agr 8 mol%, grains, volume equivalent method diameter 1.1 μ- Coefficient 13% Coated silver amount Gelatin Cp-1 Cp-2 1l-1 1,5XIO-'8.0X10-' ... 0.30 ... 0.03 ... 0.03 ... 0.002 ... 0.12 ... 0.12 Octahedral multiple structure, change in equivalent sphere diameter... 1.0 ... 1.50 1.5X10-'1.5X10-' 8.0X10-- ・... 0.10 ... 0.10 ... O,OS Oi I -2-0,05 6th layer (middle layer) Gelatin ...0.70Cp
d-1,1...0.03 0i1-1...0.05 Seventh layer (first green-sensitive emulsion layer) Silver iodobromide emulsion (8g 17 mol%, octahedral multi-structure grains,
Volume equivalent method diameter 0.4μ, coefficient of variation of sphere equivalent diameter 15% Coated silver amount Gelatin Cp-6 Cp-7 Cp-8 tl-1 ... 1.10 ... 2.50 2, 4X10-' 2, 4X10-' 1, 2X10-' 5, O X 10-' ... 0.15 ... 0. lO ... 0.03 ... 0.02 ... 0.30 O i 1 -2
- 0.30 8th layer (second green-sensitive emulsion layer) Silver iodobromide emulsion (Agl 7.3 mol%, octahedral multi-structure grains, volume equivalent diameter 0.7μ, coefficient of variation of sphere equivalent diameter 9) % Coated silver amount...1.10 Gelatin...0.8OS
-4 2. OXlo-'S
-5 1.9X10-'
S-6 1. IXlo-
'S-7 4. OXlo
-'Cp-5...0. l
OCp-6...0.07
0Cp-7...0.03
0Cp-8...0.02
50i1-1...0.20
0fl-2 ・-0.20 9th
Layer (third green-sensitive emulsion layer) Silver iodobromide emulsion (Agl 7.5 mol%, thick plate aspect ratio 2, volume equivalent method diameter 1.5 μm, coefficient of variation of equivalent sphere diameter 14% Coated silver amount... 1.20 Gelatin...1.8O3-
41,3X10=' S -51,3X10-' S -69,0X10-' S -73,0X10-5 Cp-6-0,20 Cp-7 River 0.03 0 t 1-1 River o, 200 i
I-2-0,05 10th layer (yellow filter layer) Gelatin...1.2 Yellow colloidal silver...O, OaCp d -
12-0,1 0i1-1...O-3 11th layer (first blue-sensitive emulsion layer) Silver iodobromide emulsion (All 6.5 mol%, octahedral multiple structure grains, volume equivalent spherical diameter 0. 4 pm, coefficient of variation of equivalent sphere diameter 9% Coated silver amount...0.20 Silver iodobromide emulsion (8gI 7 mol%, octahedral multi-structure grains, volume equivalent spherical diameter 0.8 μm, equivalent sphere diameter Coefficient of variation 12
% Coated silver amount...0.45 Gelatin...1.75S
-71,0X10-' S -82,0X10-' Cp-9...0.45 Cp-10...0.50 0i1-1...0,200
i1-2...0. IO 1st
2 layers (second blue-sensitive emulsion layer) Silver iodobromide emulsion (Agl 9.7 mol%, plate aspect ratio 2, volume equivalent method diameter 1.6 μ ring, coefficient of variation of sphere equivalent diameter 12% Coated silver amount ・...1.10 Gelatin ...1.2O3-
71,0X10-' S -81,0X10-' Cp-9...0.25 0 i I -1・= 0.060 0 j 1-2 = 0.030 13th layer (first protective layer) Fine particles Silver iodobromide (average grain size 0.o8μra, Agl
2 mol%) ...0.40
Gelatin...1.3°UV
-1 river. , o5 UV-2-0,05 UV-3 River 0.1゜UV-4-0,10 UV-5-0,03 0il-1-0,1 011-2...0.1 14th layer (Second protective layer) Gelatin...0.50 Surfactant (W-11) Polymethyl methacrylate particles...0.2 Slip agent (B-11) -0,03H-1.
...0.4 In addition to the above ingredients, coating aid W-12, dispersion aid W-13,
Hardener H-11, H-12, formalin scavenger
Cpd-13, Cpd-14, Cpd as a preservative
In addition to Cpd-15 and Cpd-16, a stabilizer Cpd-17 and an antifoggant Cpd-18°Cpd-19 were added. The names or chemical structural formulas of the compounds used to prepare the samples are shown in Table 8 below.

The sample thus obtained was exposed and developed according to the method of Example 2. Sensitivity was evaluated by the logarithm of the reciprocal of the exposure amount (relative value when sample 501 is taken as 100) that gives a density 1.0 higher than the lowest cyan density. (Table 10) Table 1 The light-sensitive materials containing the emulsions of the present invention had high sensitivity one day after coating and one month after coating (45° C. 50%).

(Effects of the Present Invention) According to the present invention, a silver halide photographic material having high sensitivity and excellent storage stability can be obtained.

No. table X-1 I X-2 H (i) CJwOCNH X H X-4 X 1I CJ+z(n) X mol, wt.

Approximately 20,000 X-8 CH.

X CH.

X-11 CHl X zHs zH5 C,)1. OSO,.

X I (t)Callq U-3 Dye■ (CL)ssO3H・N(CJSensitizing dye■ Sensitizing dye■ Sensitizing dye■ (CHz) aSOsK Sensitizing dye■ Sensitizing dye■ Sensitizing dye■ H Cut ""Ctl Sow (Jh C0NH
CHzCH, = CH-So□-Cttyo-CONHG
Hz CH CJ, (t) V-2 CH CH3 V- 3 CH C4H*(t) V H canq(t) U■ Tricresyl phosphate! Dibutyl phthalate p-4 Hs p p-6 I p p I H p-9 rl p-1 pd-11 CH pd CH CH pd pd aO3S CHCOOCHz (CFzCh) J C) IzCOOCHz (ChCh)3HNa03S-C
HCOOCIIHI7 CHzCOOCJl+7 (CH.

-CH30□CHt)OCCH wealth SOx (CHz)zJ
(CHz) gsOsK pd-15 pa-i pd CH CH3 pd-1 pd S-2 (C)Iz) 3sO:+Na CO.

(C) It) xsOsNa CHz = CHSO2CHz C0NH-CHz

[Brief explanation of drawings]

FIG. 1 shows emulsion B- according to the present invention in Example 1.
This is an electron micrograph showing the crystal structure of silver halide grains in which dislocations are concentrated near the apex in 2, and the magnification is 4.
0000 times. FIG. 2 is an electron micrograph showing the crystal structure of silver halide grains in which dislocations are present on the sides in Emulsion C-2 of Comparative Example of Example 1, and the magnification is 40,000 times. FIG. 3 is an electron micrograph showing the crystal structure of silver halide grains in which no dislocations have been introduced in Emulsion D-2 of Comparative Example of Example 1, and the magnification is 40,000 times.

Claims (4)

[Claims] (1) Distribution of photosensitive nuclei is 2 nm or more and 50 nm from the particle surface.
1. A silver halide photographic light-sensitive material, comprising an emulsion layer containing silver halide grains having a maximum value at a depth of less than or equal to 100 m, and having dislocations inside the grains. (2) The silver halide photographic material according to claim (1), which is a tabular silver halide grain having an aspect ratio of 2 or more. (3) Claim (1) characterized in that the grains are normal crystal silver halide grains with a coefficient of variation of grain size distribution of 20% or less.
The silver halide photographic material described above. (4) The silver halide photographic material according to claim (1), wherein dislocations are concentrated near the vertices of the silver halide grains.