JPH03240033A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain the photosensitive material having a high sensitivity ad high stability against a fluctuation n processing conditions and further excellent heat resistance and moisture resistance by regulating the sensitivity of red-, green- and blue sensitive silver halide emulsion layers at the time of providing these emulsion layers on a base. CONSTITUTION:At least any of the red- and green sensitive emulsion layers of at least one layer each of the red sensitive silver halide emulsion layers, green sensitive silver halide emulsion layers and blue sensitive silver halide emulsion layers are formed to have the low sensitivity, middle sensitivity and high sensitivity from the side nearer the base at the time of forming the silver halide photographic sensitive material by providing the above-mentioned emulsion layers on the base. The silver iodobromide particles constituted of the cores substantially consisting of a silver iodobromide and the shells which cover the cores and consist of the silver iodobromide or silver iodide having the silver iodide content lower than the silver iodobramide content of the cores are incorporated into at least one layer of any of the emulsion layers which are different in the sensitivity. In addition, the relative standard deviation of the silver iodide contents of the individual particles of the emulsions is confined to<=20%.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention relates to a silver halide photographic light-sensitive material, which is a silver halide photographic material that has high sensitivity, particularly excellent stability against fluctuations in processing conditions, and furthermore has good heat resistance and moisture resistance. This invention relates to silver oxide photographic materials.

[Background of the invention]

Silver halide photographic materials are required to have various performances such as sensitivity, image quality, and gradation, but capri, storage stability, and processing stability are also extremely important factors, and requests for improvements in these areas are increasing year by year. Things are getting tougher. However, a means for simultaneously improving fogging, storage stability over time, and processing stability without reducing sensitivity has not yet been established.

Many methods are conventionally known for sensitizing silver halide photographic materials. Spectral sensitization using sensitizing dyes; noble metal sensitization using salts of noble metals such as gold, platinum, and iridium; sulfur sensitization using activated gelatin, sodium thiosulfate, thioacetamide, allylisothiourea, etc.; colloidal selenium, selenourea Other known methods include selenium sensitization using monovalent tin salts, polyamines, and hydrazine derivatives; and development acceleration using polyionium salts of nitrogen, phosphorus, or sulfur, and polyalkylene glycols.

In the actual photographic industry, these sensitization techniques are appropriately combined according to the purpose to produce the desired silver halide photographic light-sensitive material, and stable images can be obtained even under fluctuations in processing conditions. The current situation is that there is no technology that can fully satisfy various performance requirements, such as processing stability, storage stability over time, and storage stability over time, especially when stored at high temperatures and high humidity.

Grain techniques for increasing the sensitivity of silver halide emulsions include JP-A-60-138538 and JP-A-60-14333.
No. 1, U.S. Patent No. 4,444,877 and JP-A No. 1983-
There are monodisperse type and tabular type core/shell emulsions as shown in No. 99433 and No. 60-35726. This is a method in which the latent image formation process is devised so that the light absorbed inside the silver halide grains is efficiently converted into development nuclei. However, further improvements were desired in terms of storage stability and the like.

In order to improve these drawbacks, attempts have been made to add various fog suppressants to light-sensitive materials.

In particular, U.S. Patent Nos. 1,758,576 and 2,304.9
No. 62, No. 2.697,040, No. 2.697.09
No. 9, No. 2,824,001, No. 2.476, 536
The mercapto compounds described in British Patent No. 2,843.491, British Patent No. 3,251,691, British Patent No. 403,789, British Patent No. 893,428, Japanese Patent Publication No. 58-9939, etc. However, it has not reached a fully satisfactory level, as there is a significant decrease in sensitivity, and there is also deterioration in sensitivity, fog, etc. due to storage over time.

As a method for obtaining photographic materials with high sensitivity and high image quality, for example, Japanese Patent Application Laid-Open No. 113934/1983 discloses a method using a tabular silver halide emulsion having an average aspect ratio of 8 or more. However, due to their morphological properties, tabular grains with a high aspect ratio have too high development activity regardless of the average silver iodide content of the total grain, making it extremely difficult to obtain the desired gradation. Furthermore, the processing stability did not reach a fully satisfactory level.

Furthermore, for the purpose of improving the progress of development, JP-A-60-15
No. 6059 proposes a technique in which a layer containing silver halide grains having substantially no photosensitivity is provided between two emulsion layers with different photosensitivity, and furthermore, Japanese Patent Application Laid-Open No. 1284-1984
No. 29 discloses a technique in which the effects of fluctuations in processing conditions are reduced by incorporating non-light-sensitive silver halide grains in the outer layer of a light-sensitive silver halide emulsion layer furthest from the support.

However, these conventional techniques are still insufficient and have not yet sufficiently improved processing stability.
A solution to this problem was strongly desired.

Furthermore, due to recent market demands, the further downsizing of compact labs (developing equipment) has caused problems such as deterioration of the processing solution, as well as non-uniformity of the processing solution, that is, insufficient stirring of the processing solution. Variations in performance due to this have become a problem, and a solution is expected.

[Purpose of the invention]

An object of the present invention is to provide a silver halide photographic material which is highly sensitive and has excellent stability against fluctuations in processing conditions, as well as excellent heat resistance and moisture resistance.

[Structure of the invention]

As a result of intensive studies, the inventors of the present invention have found that the above object can be achieved by the following method, and have come to form the present invention.

That is, in a silver halide photographic light-sensitive material having at least one layer each of a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a blue-sensitive silver halide emulsion layer on a support, the color-sensitive halogen Among the silver emulsion layers, at least one of the red-sensitive silver halide emulsion layer and the green-sensitive silver halide emulsion layer is composed of, from the side closer to the support, a low-sensitivity silver halide emulsion layer, a medium-sensitivity silver halide emulsion layer, and a high-sensitivity silver halide emulsion layer, and at least one of the low-sensitivity, medium-sensitivity, and high-sensitivity silver halide emulsion layers.
The layer includes a core consisting essentially of silver iodobromide and a core consisting essentially of silver iodobromide or silver bromide covering the core and having a lower silver iodide content than the silver iodobromide of the core. The emulsion contains silver iodobromide grains consisting of a shell, and the relative standard deviation of the silver iodide content of each grain of the emulsion is 20%.
The objects of the present invention have been achieved by a silver halide photographic material characterized by containing the following silver halide emulsion.

The details of the present invention will be specifically explained below.

The silver halide photographic light-sensitive material of the present invention comprises, on a support, a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer,
and a blue-sensitive silver halide emulsion layer, each color-sensitive emulsion layer being present on at least one support. In addition, in the light-sensitive material of the present invention, among these color-sensitive silver halide emulsion layers, at least one of the red-sensitive silver halide emulsion layer and the green-sensitive silver halide emulsion layer,
The structure includes a low-sensitivity silver halide emulsion layer, a medium-sensitivity silver halide emulsion layer, and a high-sensitivity silver halide emulsion layer from the side closest to the support.

In the silver halide photographic light-sensitive material of the present invention, both the green-sensitive silver halide emulsion layer and the red-sensitive silver halide emulsion layer have low sensitivity, medium sensitivity, and high sensitivity silver halide emulsion layers, respectively, from the side closer to the support. It is preferable that the emulsion layer has at least a three-layer structure in which the emulsion layers are coated in sequence.

In addition, each of the blue-sensitive silver halide emulsion layer, the green-sensitive silver halide emulsion layer, and the red-sensitive silver halide emulsion layer has low sensitivity, medium sensitivity, and high sensitivity halogenation, starting from the side closest to the support. It is more preferable to adopt a three-layer structure in which silver emulsion layers are applied in sequence.

In the light-sensitive material of the present invention, the three-layer structure is arranged in the above order starting from the support in either the red-sensitive or green-sensitive silver halide emulsion layer, but for each color malignant layer that does not follow this order. It is also preferable to have a layered structure consisting of three layers, each having a different sensitivity.

The total amount of coated silver in the silver halide color photographic light-sensitive material of the present invention is preferably 100 μ/drrr to 20 μ/d, and more preferably 80 μ/drrr to 40 μm.
g/drTf.

In the present invention, the amount of silver contained in each of the low-speed, medium-speed, and high-speed silver halide emulsion layers is as follows:
00■/drr? It is preferable to increase the number in the order of medium-sensitivity silver halide emulsion layer, low-sensitivity silver halide emulsion layer, and high-sensitivity silver halide emulsion layer, in the range of ~20 μ/d po, and in that case, any ratio can be selected. You can do more with it.

In the present invention, the maximum color density of at least the medium-sensitive silver halide emulsion layer in either the green-sensitive emulsion layer or the red-sensitive emulsion layer is preferably 0.35 or less, and particularly preferably 0.25 or less.

The silver halide emulsion layers in the light-sensitive material of the present invention, that is, the low-sensitivity silver halide emulsion layer, medium-sensitivity silver halide emulsion layer, and high-sensitivity silver halide emulsion layer, as described above, are commonly used in this technical field. It can be constructed using any technology that can be used.

The silver halide photographic light-sensitive material of the present invention can be embodied as various light-sensitive materials, for example, it can be used not only as a negative silver halide color photographic light-sensitive material but also as a positive silver halide color photographic light-sensitive material.

Further, preferred I of the silver halide photographic light-sensitive material of the present invention
The SO sensitivity is 100 or more, more preferably 200 or more, particularly preferably 300 or more.

In this specification, ISO sensitivity refers to the JIS sensitivity shown below.
It is determined according to the test method according to K 7614-1986.

(1) Test conditions The test is conducted indoors at a temperature of 20±5° C. and a relative humidity of 60±10%. The photosensitive material to be tested is left in this condition for at least one hour before being subjected to the test.

(2) n-light ■ The relative spectral energy distribution of the reference light on the exposure surface is shown in Table A below.

(Margin below) Table-A Below: Margin Table-A (Continued) Table-A (Continued) (1) Values are determined by standardizing the value at 560 nm to 100.

Changes in illuminance on the exposed surface are performed using an optical wedge.
The optical wedge used has a spectral transmission density variation of 400 nm in the wavelength range of 360 to 700 r++w at any part.
Within 10% for areas below 5% for areas over 400ns
Use the following.

■ Exposure time is 1/100 second.

(3) Development processing■ From exposure to development processing, the photosensitive material to be tested is maintained at a temperature of 20±5° C. and a relative humidity of 60±10%.

■Development processing should be completed within 30 minutes or more and within 6 hours after exposure.

■ Development processing is performed as follows.

1. Color development---3 minutes 15 seconds 38.
0±0.1°C2, bleaching-1----------
6 minutes 30 seconds 38.0±3.0°C3, water washing------
----------3 minutes 15 seconds 24-41°C
4. Fixation・--1--・----6 minutes 30 seconds
38.0±3.0°C5, water washing・----1・---
-------3 minutes 15 seconds 24-41°C6, stable・--11----3 minutes 15 seconds 38
．． 0±3.0°C7, drying---1---------
----50°C or lower The composition of the treatment liquid used in each step is shown below.

<Color developer> 4-amino-3-methyl-N- Ethyl-N-(β-hydroxy ethyl) aniline sulfate anhydrous sodium sulfite Hydroxylamine % sulfate Anhydrous potassium carbonate sodium bromide Nitrilotriacetic acid Trisodium salt (monohydrate) potassium hydroxide Add water to adjust to 11 (pH = 10.1) <Bleach solution> Iron(III) ethylenediaminetetraacetate ammonium salt Ethylenediaminetetraacetic acid 2 ammonium salt ammonium bromide glacial acetic acid Add water II! , binding, Adjust the pH to 6.0.

10.0 g 150.0 g 10.0 g Using ammonia water 4.75 g 4.25 g 2.0 g 37.5 g 1.3 g 2.5 g 1.0 g 100.0 g (Fixer) Thio Ammonium sulfate 175.0 g Anhydrous sodium sulfite 8.5 g Sodium metasulfite 2.3 g Add water to 11
and adjust the pH to 6.0 using acetic acid.

<Stabilizing solution> Formalin (37% aqueous solution) 1.5IIIi Konidax (manufactured by Konica Corporation) 7.51d Water was added to make 1i.

(4) Concentration measurement Concentration is log. It is expressed as (Φ./Φ). Φ. is the illumination light flux for density measurement, and Φ is the transmitted light flux of the part to be measured. The geometric conditions for concentration measurement are based on the fact that the illumination light flux is parallel light flux in the normal direction, and that the total light flux that is transmitted as a transmitted light flux is used. Correction is performed using a density piece, and during measurement, the papillary surface of the photosensitive material is made to face the light-receiving device. Concentration measurements are performed using status M concentrations of blue, green, and red, and their spectral characteristics are the overall characteristics of the light source, optical system, optical filter, and light receiving device used in the densitometer.
The values shown in Table B should be obtained.

Table-B Status M concentration spectral characteristics (logarithmic display, peak normalized to 5.00) Table-B (continued) Table-B (continued) Red slope Green slope Blue slope Red slope Green slope Blue Slope 0.260/nm, 0.106/r+m, 0.250/nm 0.040/nm, 0.120/nm, 0.220/nm Result of exposure and development as above and density measurement Using this, determine the lSO sensitivity according to the following steps ① to ②.

(2) The exposure amount corresponding to a density 0°15 higher than the minimum density of each of blue, green, and red is expressed in lux-seconds as Em and EG-Ec, respectively.

■ Let E be the one with the largest value (the one with the lowest sensitivity) among Em, Ec, and Et.

■ Calculate the ISO sensitivity S according to the formula below.

Next, the silver halide photographic material of the present invention comprises at least one red-sensitive silver halide emulsion layer each on a support;
It has a green-sensitive silver halide emulsion layer and a blue-sensitive silver halide emulsion layer, and of the color-sensitive silver halide emulsion layer, at least one of the red-sensitive silver halide emulsion layer and the green-sensitive silver halide emulsion layer From the side closest to the support, a low-sensitivity silver halide emulsion layer, a medium-sensitivity silver halide emulsion layer,
and a high-sensitivity silver halide emulsion layer, and at least one of the low-sensitivity, medium-sensitivity, and high-sensitivity silver halide emulsion layers contains the following emulsion. That is, at least one layer of the light-sensitive material of the present invention includes a core consisting essentially of silver iodobromide, and a layer containing silver iodide that covers the core and has a lower silver iodide content than that of silver iodobromide in the core. A photosensitive silver iodobromide emulsion containing silver iodobromide grains consisting of a shell consisting essentially of silver iodobromide, or silver bromide, wherein the iodination of the individual grains of the emulsion is It contains a silver halogenide emulsion (hereinafter also referred to as "emulsion J of the present invention") having a relative standard deviation of silver content of 20% or less.

The emulsion of the present invention will be explained below.

The core of the silver halide grains contained in the emulsion of the present invention (
Preferably, the core consists essentially of silver iodobromide containing 5 mol % or more of silver iodide. The 10-genide silver grains are composed of a shell covering the core and consisting essentially of silver iodobromide or silver bromide, the silver iodide content of which is lower than the silver iodide content of the core. It is preferable to have a heavy structure. The silver iodide content of the core is more preferably 10 mol% or more, and most preferably 20 mol% or more and 44 mol% or less. The silver iodide content of the shell is preferably 5 mol% or less.

The core may uniformly contain silver iodide, or
It may have a multiple structure consisting of phases with different silver iodide contents. In the latter case, the silver iodide content of the phase with the highest silver iodide content is 5 mol % or more, more preferably 1
It is sufficient that the silver iodide content of the shell is lower than that of the highest silver iodide content phase of the core. Further, "j consisting essentially of silver iodobromide" means that it mainly consists of silver iodobromide, but may also contain other components, for example, up to about 1 mol %.

In a further preferred embodiment of the silver halide grains used in the photographic emulsion layer of the silver halide photographic light-sensitive material of the present invention, the silver halide grains have a diffraction angle (2θ) in the range of 38 to 42°, and the silver halide grains are When we obtain a curve of diffraction intensity versus diffraction angle for the (220) plane of The diffraction intensity corresponding to the core part is
These particles have a structure that is 1710 to 3/1 that of the shell part. Particularly preferably, the diffraction intensity ratio is 175.
~3/1, more preferably 173~3/1.

This double structure makes it possible to use a silver iodobromide emulsion with a high silver iodide content without causing a delay in development speed, resulting in a photosensitive material that has excellent graininess even with a small amount of coated silver. can be achieved.

Another preferred embodiment of the silver halide grains contained in the emulsion of the present invention is that the grains have a silver iodobromide phase with a silver iodide content of 10 to 40 mol%, which forms a core inside the grains. The silver bromide phase is coated with a silver halide phase containing lower silver iodide forming a shell, and the surface of the grain is
This is the case when silver iodide is contained in an amount of mol% or more. The silver iodide composition contained in the shell may be uniform or non-uniform. The expression that the surface contains 5 mol % or more of silver iodide means that the average content of silver iodide on the grain surface measured by the XPS method is 5 mol % or more. Preferably, the average content of silver iodide on the surface is 7
It is mol% or more and 15 mol% or less.

Regarding this silver halide grain, JP-A No. 63-1067
Details are given in issue 45. These silver halide grains are preferred because they have good granularity.

Another preferred embodiment of the silver halide grains contained in the emulsion of the present invention is that an inner core consisting essentially of silver iodobromide and/or silver iodide forms a core, and is provided outside the inner core. Silver halide grains having a plurality of outer shells (these outer shells form shells) consisting essentially of silver bromide and/or silver iodobromide, the outermost shell having a silver iodide content of 10 a silver iodide-rich shell having a silver iodide content of 6 mol% or more higher than that of the outermost shell; An intermediate shell having a silver iodide content intermediate between these two shells is provided between the high silver content shell, and the silver iodide content of the intermediate shell is 3 mol% or more higher than the outermost shell. , the silver iodide content of the high silver iodide content shell is 3 mol% or more higher than that of the intermediate shell. This silver halide grain is described in detail in JP-A-61-245151. These silver halide grains are also preferred because they have good granularity.

In the emulsion of the present invention, the relative standard deviation of the silver iodide content of each individual silver iodobromide grain is 20% or less. In the emulsion of the present invention, it is preferable that the iodine content among the grains is even more uniform.

It is preferable that the silver iodide content of each silver halide grain is uniform from the viewpoint of uniformity of chemical sensitization and spectral sensitization.

The silver iodide content of individual silver halide grains and the average silver iodide content in the emulsion of the present invention are determined by the EPMA method (Ele
ctron Probe Micro^nalyzer
It can be obtained by using the method (method).

This method is a technique in which a well-dispersed sample is prepared so that the emulsion grains do not come into contact with each other, and elemental analysis of extremely small portions is performed by X-ray analysis using electron beam excitation by irradiating the sample with an electron beam.

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

If the silver iodide content of a small number of grains (50 in total) is determined by the EPMA method, the average silver iodide content can be determined from the average thereof.

The equipment used for measurement does not require any special specifications, but
In the examples of the present invention described later, the silver iodide content of the emulsion was measured using an X-ray microanalyzer JXA-8621 manufactured by JEOL Ltd. The measurements were performed while cooling to a low temperature to eliminate electron beam damage.

The relative standard deviation of the silver iodide content of individual grains is the standard deviation of the silver iodide content when measuring the silver iodide content of at least 50 emulsion grains in the above measurement. This value is obtained by multiplying the value divided by the content rate by 100.

The emulsion of the present invention is required to have this value of 20% or less, that is, when the distribution of iodine content among grains is measured by the EPMA method, the relative standard deviation is 20% or less. The silver iodide content of the grains is preferably more uniform, and this value is preferably 15% or less, particularly 10% or less.

An emulsion with good uniformity of silver iodide content as described above can be achieved by various means for improving the uniformity, for example, by modifying the manufacturing conditions of the silver halide emulsion.

For example, as shown in Japanese Patent Application No. 63-224002, there is a method for producing an emulsion in which iodide ions are supplied using fine silver iodide grains,
A method of growing silver iodobromide fine grains into seed grains by Ostwald ripening as shown in JP-A-1-183417 is useful.

Preferred silver halide constituting the emulsion of the present invention is silver iodobromide containing 30 mol % or less of silver iodide. Particularly preferred is silver iodobromide containing from 2 mol % to 20 mol % silver iodide.

In addition, in order to achieve both high sensitivity and high image quality,
As described in Japanese Patent No. 0-128443, it is preferable that the average silver iodide content of silver halide in all emulsion layers is 8 mol % or more. It is known that increasing the average silver iodide content of silver halide significantly improves graininess, but if the silver iodide content exceeds a certain level, development speed may be delayed, desilvering may occur, and fixing speed may be reduced. There are drawbacks such as delays. Regarding this point, as described above, the emulsion of the present invention overcomes this problem, can increase the average silver iodide content, and also solves this problem.

In order to constitute the light-sensitive material of the present invention, emulsions other than the emulsion of the present invention may be used in combination, if necessary. In this case, the silver halide composition of the emulsion used in combination is arbitrary; for example, silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide, silver chloride, etc., or a mixture thereof may be used. Good too.

As the emulsion of the present invention or an emulsion other than the present invention to be used in combination as necessary (hereinafter collectively referred to as "emulsion used in the present invention"), monodisperse emulsions as defined below are preferable. As defined by the following formula, if the value obtained by dividing the standard deviation S of the particle size by the average particle size 1 and multiplying it by 100 (hereinafter referred to as the coefficient of variation) is 16 or less, it is considered monodisperse. The emulsion is preferably a monodisperse emulsion in this sense.

×100516% Note that S is the standard deviation in the general definition used in statistics.

The shape of the silver halide grains in the emulsion used in the present invention, for example the monodisperse emulsion mentioned above, may be cubic, octahedral, or tetradecahedral, or may be spherical or plate-like. Well, it's optional.

The average grain size of the silver halide emulsion grains used in the present invention is 0.
．． It is preferably 1 to 5.0 am, more preferably 0.15 to 3.0 μm, particularly preferably 0.2 to 2.0 μm.

Monodisperse emulsions have good graininess, and at the same time, in the size range with little light scattering, they also have excellent image sharpness.
Preferred monodisperse emulsions are described, for example, in JP-A-54-48521, JP-A-54-99419, and JP-A-54-99419.
No. 16124, No. 56-78831, U.S. Patent No. 4.
No. 444.877, JP-A No. 57-182730, No. 5
No. 8-49938, No. 58-37635, U.S. Patent No. 4.446.228, Japanese Patent Application Publication No. 58-106532,
No. 58-107530, No. 58-126531, No. 58-149037, No. 59-10947, No. 59
No. -29243, No. 59-72440, No. 59-14
No. 0443, No. 59148049, No. 59-1775
It is described in detail in No. 35, No. 59-152438, etc.

It is desirable that the emulsion used in the present invention has low fog. Various methods have been known for reducing the looseness of silver halide emulsions. For example, this can be achieved by using a known cuff suppressing agent as an additive. In particular, it is effective to use silver halide produced under conditions where it is difficult to form grains by devising the production conditions of the silver halide emulsion.0For example, February 1, 1990.
In the production of a silver halide emulsion using an ammoniacal silver nitrate aqueous solution, as shown in the patent side (2) of the Japanese application,
By forming silver halide at a pH of 7.5 or lower, a silver halide emulsion with low fog can be obtained.

As a silver halide emulsion with low fog, it is preferable to use a silver halide emulsion in which the ratio of fogged grains in the unsensitized emulsion is 1/200 or less. /200 or less means that for a silver halide emulsion that has not been chemically sensitized, the number of loose grains relative to the total number of silver halide grains when coated on a support and developed is 1/200 or less. 200 or less.

An emulsion preferable for improving graininess or storage fog is one in which the ratio of fogged grains in an unsensitized emulsion is 1, as described above.
/200 or less, and such an emulsion is further chemically sensitized.

In this case, if chemical sensitization is appropriately applied and used in a light-sensitive material, fogging and storage stability can be improved while maintaining high sensitivity.

Here, fog particles refer to particles that are reduced to silver atoms by silver halide in unexposed areas during color development processing to form a dye image. Alternatively, by directly observing the developed silver itself with an electron microscope, it can be distinguished from particles other than fog particles.

In this case, the color developing solution used for color development processing is as follows.

<Color developer 1> Processing time 3 minutes 15 seconds 4-amino-3-methyl-N- Ethyl-N-β-hydroxy Ethylaniline sulfate anhydrous sodium sulfite Hydroxylamine disulfate Anhydrous potassium carbonate sodium bromide Nitrilotriacetic acid trisodium salt (l water salt) potassium hydroxide Add water to make 11, <Color developer 2> Processing time 3 minutes 15 seconds potassium carbonate potassium bicarbonate potassium sulfite 2.5g 1.0g Adjust to pH=10.1.

For example, the following can be mentioned: Treatment temperature: 38°C 4.75g 4.25g 2.0g 37.5g 1.3g Treatment temperature: 38°C 30, Og 2.5g 4.0g Sodium bromide 0.6 g Potassium iodide 1.2 ■ Hydroxyamine sulfate 2.5 g Sodium chloride
0.6 g diethylenetriaminepentaacetic acid 1.0 g 4-amino-3-methyl-
N-Ethyl-N~β-hydroxyethylaniline nitrate 4.8g Potassium hydroxide 1.2g Add water and 1!
and pH 1 using potassium hydroxide or 50% sulfuric acid.
Adjust to 0.06.

Since the development speed of fogging particles is much faster than that of particles other than fogging particles, they can be easily distinguished from other particles. The number of fogged grains in an unsensitized emulsion can be easily counted as a color point by increasing the color development time by 50%, for example.

Therefore, the total number of silver halide grains and the number of fogged grains in a light-sensitive material can be determined by, for example, immediately after color development, stopping with a 3% acetic acid solution, washing with water, and decomposing the gelatin peptizer with a 0.1% aqueous actinase solution. This can be confirmed by observation with a scanning electron microscope, and the ratio of loose grains in the emulsion used in the light-sensitive material can thereby be determined.

Next, an example of measuring the ratio of fogged grains in an unsensitized emulsion will be shown.

The emulsion to be measured was mixed with common photographic additives such as spreading agents, thickeners, and hardeners, as well as the following magenta coupler (M-Cp).
) was added to prepare a coating emulsion, which was coated on a triacetyl cellulose film support to a silver content of 7 .mu./100c4 and dried.

(M-Cp) Q These were divided into two, sample A and sample B, and A was subjected to the following development process.

Processing Steps (38°C) Color Development Bleaching Water Washing Water Deposition Washing Stability Drying The composition of the processing solution used in each processing step is as shown below.

Color developer> 4-amino-3-methyl-N-ethyl-N-β-hydroxyethylaniline, sulfate, anhydrous sodium sulfite, hydroxylamine, z'gL# salt, anhydrous carbonate, anhydrous potassium carbonate, nitrilotriacetic acid, 4. 75 g 4.25 g 2.0 g 37.5 g 1.3 g 5 minutes 30 seconds 4 minutes 30 seconds 3 minutes 4 minutes 3 minutes 2 minutes Sodium salt (monohydrate) 2.5 g Potassium hydroxide 1. Add 0 g water to 11 and adjust pH=Io,I.

<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 10.0 d Add water to bring the pH to 11, and adjust to pH 6 using aqueous ammonia. , adjust to 0.

<Fixer> Ammonium thiosulfate 175.0 g Anhydrous sodium sulfite 8.5 g Sodium metasulfite 2.3 g Add water II
! and adjust the pH to 6.0 using acetic acid.

Stabilizer> Formalin (37% aqueous solution) 1.5 d
Konidax (manufactured by Konica Corporation) 1.5tnl
Add water to make IP.

The processed sample was photographed using an optical microscope and
The number of colored spots is counted for each sheet and used as the number of fog grains in the unsensitized emulsion. At the same time, Sample B was fogged with light, treated with the same color developing solution as above, stopped with a 3% acetic acid solution, and washed with water.

The obtained sample is photographed using an optical microscope in the same manner as sample A, and the total number of silver halide grains is determined.

The emulsion used in the present invention preferably has a ratio of fog grains of 1/200 or less before chemical sensitization, and is preferably 1/200 or less.
00 or less is more preferable. More preferably 1/1
000 or less.

When constituting the light-sensitive material of the present invention, the emulsion of the present invention used and other silver halide emulsions other than the emulsion of the present invention used as necessary are generally preferably subjected to physical ripening,
After chemical ripening, it is generally used that has undergone spectral sensitization depending on the color-sensitive layer to be used. Additives that can be used in such processes include Research Disclosure Nα17
643. No. 18716° and No. 308119
(Respectively, RD17643. RD18716
, and RD308119).

Please write in the table below. Two locations are shown.

Below margin RD308119(7)”C near) (RD 176
43) (RD 111j716) [Item] [And item -1/-1/Chemical aggravating agent 996111-A Section 23 648 Spectral sensitizer Armpit TV-A-^, 8. 23～24 648～
9C, D, H, I, J section supersensitizer 996 rV-A-E, J section 23-24
648~9 Anti-fog machining 998 Vl
24-25 649 Stabilizer 998V
I 24-25 649 Known photographic additives that can be used in the practice of the present invention are also exemplified in the above Research Disclosure.

The relevant information is shown below.

Margin below □”°') Color clouding prevention agent Pigment image stabilizer Brightener Ultraviolet absorber Light absorber Light scattering agent Filter Dye Binder Static inhibitor Hardener Plasticizer Lubricant □1・5-1 Matting agent Development Agent (contained in photosensitive material) 002 002 98 003 003 003 003 003 006 004 006 006 005 007 011 ■-R section■-J section■ 40110 section■ ■ ■ ■ Store■ ■ VT XXB section 4 25-26 25- 26 50 Various couplers can be used in the photosensitive material of the present invention depending on the color desired to be developed in each color photosensitive layer, and specific examples thereof are illustrated in the above-mentioned Research Disclosure. Indicates relevant information.

[Section]

Yellow Coupler Magenta Coupler Cyan Coupler Color FfJ Blur DIR Coupler BAR*Blur (page of RD308119) 1001 ■-D Section 1001 ■-D Section 1001 ■-D Section 1002 ■-G Section 1001 ■-F Section 1002 ■-F Section ( RD 17643 ) ■ Item 0 to 0 ■ Item C-0 ■ Item C-0 ■ Item 0 ■ Item F Alkali-soluble coupler 1001 ■ Item E-Sample Invention When various additives are used in the optical material, these are:
It can be added by the dispersion method described in RD308119X IV.

In the present invention, the above-mentioned 28 pages of RD17643, pages 647-8 of RD18716, and RD3
The supports described in X■ of 08119 can be used.

The photosensitive material of the present invention can be provided with auxiliary layers such as a filter layer and an intermediate layer described in the above-mentioned RD308119--.

The photosensitive material of the present invention can have various layer structures such as normal layer, reverse layer, and unit structure as described in section 1-- of the above-mentioned RD308119.

As described above, the present invention can be suitably applied to color negative films and color positive films for general use or movies, and can also be applied to various kinds of films, such as color reversal films, color papers, and color reversal papers for slides or televisions. It can be applied to color photosensitive materials.

The photosensitive material of the present invention can be found in pages 28-29 of RD 17643, page 615 of RD 18716, and RD 308.
It can be developed by the usual method described in Section XIX of No. 119.

〔Example〕

Examples of the present invention will be described below. However, it goes without saying that the present invention is not limited to the examples described below.

Example 1 Here, the following seed emulsions N to 1. N-2 was prepared.

(Preparation of seed emulsion N-1) 2.0% gelatin aqueous solution 500ml heated to 40°C
- according to the method described in JP-A No. 50-45437,
4M (molar concentration) AgNOs aqueous solution 250 and 4
M-KBr, Kl mixed aqueous solution (KBr: KI
= 98:2 (mole ratio) 4 moles in total) 250 m was processed by Chondrold double jet method to give PAg of 9.0,
It was added over 35 minutes while controlling the pH to 2.0. The gelatin aqueous solution containing silver halide grains in the total amount of added silver was adjusted to pH 5.5 with a potassium carbonate aqueous solution, and then a 5 wt % aqueous solution 3 of Demol N manufactured by Kao Atlas Co., Ltd. was added as a precipitant.
64d and 20w of magnesium sulfate as a polyvalent ion.
244 ml of t% aqueous solution was added to cause coagulation, and the mixture was allowed to settle by standing still. After decanting the supernatant, 1,400 ml of distilled water was added to disperse it again. Furthermore, 20wt of magnesium sulfate
% aqueous solution is 36.4d! A silver halide seed emulsion was prepared by decanting the precipitated supernatant, making the total amount 425 - with an aqueous solution containing 28 g of ossein gelatin, and dispersing at 40°C for 40 minutes.

As a result of electron microscopic observation, this seed emulsion has an average grain size of 0.1
It was a monodisperse agent with a diameter of 16 μm.

(Preparation of Seed Emulsion N-2) By the same method as in the preparation of Seed Emulsion N-1, the average particle size was 0.
Silver iodobromide seed emulsion N- with a diameter of 33 μm and a silver iodide content of 2 mol%
2 was prepared.

Example 2 Here, silver iodide fine grain emulsions used in each of the following sides were prepared as described below.

Add an aqueous solution containing 5% by weight of ossein gelatin to a reaction vessel, and add 1 mol each of a 3.5N silver nitrate aqueous solution and a 3.5N hydrium iodide aqueous solution at a constant rate over 30 minutes while stirring at 40°C. did.

p, Ag during addition was 13.5 using conventional PAg control means.
I kept it. The produced silver iodide has an average grain size of 0.06 μm (
It was a mixture of Dβ-Agl and γ-Agl.

Example 3 Silver halide emulsion Em-1 of the present invention was prepared using three types of aqueous solutions shown below, an emulsion solution containing silver iodide fine grains, and a seed emulsion.

Aqueous solution (b-1) (Average molecular weight -1300) Aqueous solution (b-2) Aqueous solution (b-3) Emulsion solution containing silver iodide fine grains (b-4) Temperature 60''
In state C, an aqueous TFI solution of the above composition (
Add a seed emulsion equivalent to 0.407 mol to b-1), and add p
H and pAg were adjusted using acetic acid and KBr aqueous solution.

After that, the aqueous solution (b-2) was prepared while controlling the pH and PAg as shown in Table-1.

(b-3) and an emulsion solution containing fine silver iodide grains (b-
4) were added by the triple jet method at the flow rates shown in Tables 21, 3 and 4, respectively.

After the addition is complete, add a phenylcarbamyl gelatin aqueous solution and adjust the pH of the mixed solution to sediment the particles.
It was coagulated and washed with demineralized water. Thereafter, the pH was adjusted to 5.80 and the pAg to 8.06 at 40°C.

Thus, the average grain size is 0.99 μm and the average silver iodide content is 8.
A monodispersed silver iodobromide emulsion with a particle size distribution of 0 mol % and a grain size distribution of 11.2% was obtained.

This emulsion is designated as Em-1.

Table 1 shows the prescription particle structure of Em-1 and the volume ratio of each phase.

Table Em-1 Particle Growth Condition Table-2 Table-3 Table-4 Addition pattern of (b-2) Addition pattern of (b-3) Addition pattern of (b-4) → The pH and PAg are kept constant. - means to decrease continuously, ↓ means to decrease rapidly.

Table 5 Example 4 Emulsion Em-2 of the present invention was prepared using the six types of solutions shown below.
It was created.

Solution A*: High iodide silver iodobromide requires an excess of fine silver iodide particles to obtain the desired composition. According to the results obtained from X-ray diffraction, under the conditions of this example, the molar addition rate ratio with silver ions was 1 at the initial stage of forming a phase containing 35 mol% silver iodide.
A high iodine phase of 35 mol% was obtained by adding a certain excess amount so that the iodine content was 0.00%.

*The seed emulsion is a silver iodobromide emulsion with an average grain size of 0.33 μm (cubic side length of the same volume) containing 2 mol% of silver iodide uniformly within the grains.

Solution B After ammoniacal silver nitrate formation, the pH was lowered to 9 with nitric acid.
Ammoniacal silver nitrate 3.5N aqueous solution 669mI? Volume C KBr 3.5N aqueous solution 3774 m/Solution D? Volume E 1.75N KBr aqueous solution Required amount Solution F 56% by weight acetic acid aqueous solution Required amount 60″C, Japanese Patent Publication No. 58-058288, No. 5B-05
Using the mixing stirrer shown in Japanese Patent No. 8289, solution A
11 by simultaneous mixing method of solution B, solution C and solution
It took 4 minutes to add, and the seed crystal grew to 0.81 μm. The addition rate of solution B and solution C was changed in a functional manner with respect to time in accordance with the critical growth rate, and was adjusted appropriately to prevent polydispersity due to the generation of small particles other than the growing seed crystals and Ostwald ripening. was added at a suitable addition rate. By changing the speed ratio (mole ratio) of the solution, that is, the supply of silver iodide fine grain emulsion to the ammoniacal silver nitrate aqueous solution, with respect to the grain size (addition time) as shown in Table 6, a multilayered structure can be obtained. A core/shell type emulsion was prepared.

In addition, by using solutions E and F, p during crystal growth can be
, Ag, and PH were controlled as shown in Table-○. Furthermore, pA
g and PH were measured using a silver sulfide electrode and a glass electrode according to a conventional method.

Next, after desalting according to a conventional method, gelatin was added and redissolved, and the entire emulsion (10 mol) was closed with distilled water at 4250 iff. At this time, at 40°C, pH 5.80, pAg 8
．． Adjusted to 1. According to electron microscopy, this emulsion has
It was found that the emulsion consisted of monodispersed octahedral grains with an average grain size of 0.81 μm.

As can be seen from the estimated AgI content in Table 6, when silver bromide has a high iodide content, it is necessary to add an excessive amount of AgI to obtain the desired composition. According to the results obtained by X-ray diffraction,
Under the production conditions of this example, the molar velocity ratio with silver ions was initially 1.
Example 5 Emulsion solution (D ) A silver halide emulsion (Em 3) of the present invention was prepared by the following method.

aqueous solution (A) *Example This is what I got in 2.

Seed emulsion dispersion aqueous solution (B) Aqueous solution (C) Aqueous solution of the above composition containing Agl fine particles (average particle size 0.06 μm) and vigorously stirred at 60°C (
The above seed emulsion dispersion was added to A) as seed particles, and the pH and PAg were adjusted using acetic acid and a KBr aqueous solution. After that, while controlling the pH and pAg as shown in Table-7,
The aqueous solutions (B), (C), and (D) were added by simultaneous mixing method at the flow rates shown in ~10.

Next, a phenylcarbamyl gelatin solution was added to the above mixture, and the pH was controlled using acetic acid and an aqueous potassium hydroxide solution to remove salts. Desalted emulsion at 50°C
re-dispersed at 40°C, pAg 8.1° pH 5.80
The emulsion liquid volume was 4500 d, and the weight was 62 d.
Finished at 40g.

The obtained emulsion Em-3 had an average grain size of 0.47 μm and 35
Average silver iodide content 8.2 with mole % Agl-containing core
It was a mol% emulsion.

Table 7 Grain growth conditions Table 8 Table 9 Table 10 However, in Table 7, Ag (%) is the ratio of the amount of silver used up to the middle of growth to the amount of silver required to grow the seed grains.

Also, → means keeping pH and pAg constant Comparative example -
1 (Preparation of comparative emulsion Em-A) Silver iodobromide emulsion Em-A (comparative emulsion) was prepared using the following aqueous solutions (a-1) to (a-6).

Aqueous solution (a-1) Aqueous solution (a-2) Aqueous solution (a-3) Aqueous solution (a-4) Aqueous solution (a-5) Aqueous solution (a 6) However, the conditions of p)I and PAg during growth are Table 11 shows the ratio of the amount of silver used.

Table 1 However, in Table 11, Ag (%) is the ratio of the amount of silver used up to the middle of growth to the amount of silver required to grow the seed particles. → also means keeping pH and pAg constant,
') is a continuous decrease.

Comparative Example-2 (Preparation of Comparative Emulsion Em-B) Using the eight types of solutions shown below, the inside of the grain was heated to 50°C.
An aqueous solution of the above composition (a-
1) with an average grain size of 0.33 containing 2 mol% silver iodide
An amount equivalent to 0.407 mol of a μm monodisperse silver iodobromide emulsion was added as seed particles, and the pH and PAg were adjusted using acetic acid and an aqueous KBr solution.

Afterwards, while controlling pH and PAg,
First, add the above aqueous solutions (a-2) and (a-3), then add the aqueous solutions (a-4) and (a-5), then add the aqueous solutions (a-2) and (a-3), and finally Aqueous solution (a-2) and (a-
6) were respectively added by the double jet method.

Then, the pH of the solution obtained above was adjusted to 6.0. pAg 10
．． In accordance with step 1, wash with desalinated water using the usual method, and then wash again at 40 ml.
The pH was adjusted to 6.0 and the PAg to 7.7 at °C to obtain a monodispersed emulsion Em-A having an average grain size of 0.99 μm and an average silver iodide content of 8.0 mol %.

A silver iodobromide emulsion of core/shell type with a silver iodide content of 15 mol%, 5 mol% and 3 mol% in sequence, an average grain size of 0.81 μm, and an average silver iodide content of 7.16 mol%. EmB (comparative emulsion) was prepared.

(Solution A-1) Ossein gelatin 10.8 g Pronone (10% ethanol solution) 20.0 mff1
4-Hydroxy-6-methyl-1,3,3a,7-chitrazaindene (hereinafter referred to as TAI) 200■56%
Acetic acid aqueous solution 32.5#1j128
% ammonia aqueous solution 58.7mN seed emulsion N -2AgX 0.4673t8 equivalent amount 40 with distilled water
Set it to 00d.

(Solution B-1) Ossein gelatin 40 g K B
r 404.6gK1
99.6gTA1
1224■ Make 130M with distilled water.

(?Liquid C-1) ossein gelatin Br I AI 1700mA with distilled water! Make it.

(Solution D-1) ossein gelatin Br I AI Adjust to 800 mN with distilled water.

(?Liquid E-1) A g N Ox 2 (7% ammonia water Make it 1827- with distilled water.

(Solution F-1) A g N O3 28% ammonia water Make 1351d with distilled water.

0 g 791.4 g 58.1 g 2142 ■ 5 g 606.0 g 26.15 g 1605 mg 310.4 g 253++f! 803.3g 6551118! (Solution G-1) 20% KBr aqueous solution pAg adjustment required amount (?8
Solution H-1) 56% acetic acid aqueous solution pH adjustment required amount 40''
In C, JP-A-57-92523, JP-A-57-92
Using the same mixing stirrer as that shown in Publication No. 524, solution E-1 and solution B-1 were added to solution A-1 by the simultaneous mixing method, and at the same time as the addition of B-1 was completed, C-1, F-
1 was added, and D-1 was added at the same time as the addition of C-1 was completed. pAg during simultaneous mixing.

pH control and solution E-1, solution B-1, solution C-1,
The addition rates of solutions D-1 and F-1 were as shown in Table 12.

pAg and pH were controlled by changing the flow rates of solution G-1 and solution H-1 using a roller tube pump with variable flow rate.

Next, the ossein gelatin 19
After dispersing 7.4 g in an aqueous solution, the total amount was reduced to 3 with distilled water.
Adjusted to 000 d. At this time, at 40°C, the pH was set to 6. OO% pAg was adjusted to 7.7.

Table-12 Comparative example of grain growth conditions-3 (Preparation of comparative emulsion Em-C) Using the seven types of solutions shown below,
Silver iodobromide emulsions Em- of core/shell type with silver iodide contents of 5 mol %, 5 mol % and 3 mol %, average grain size o, 47 μm, and average silver iodide content 8.46 mol %. C (comparative emulsion)
It was created.

(Solution A) Ossein gelatin 28.6g Polyisopropylene-polyethyleneoxydisuccinate ester sodium salt 10% ethanol solution 16.5a+14
-Hydroxy-6-methyl-1,3,3a,7-chitrazaindene (hereinafter also referred to as TAI) 247.5■56
72.6% aqueous acetic acid solution 28% ammonia aqueous solution 97.2IId type 1 emulsion (average grain size 0.093 am) 0.1552 equivalent amount Make up to 6600 d with distilled water.

(Solution B) ossein gelatin KBr I AI Bring to 1300 - with distilled water.

(Solution C) ossein gelatin Br I TA+ Make 170M with distilled water.

(/8 liquid D) ossein gelatin Br I AI Make up to 800 II dl with distilled water.

(Solution E) A g N O3 28% ammonia water Table-13 Particle growth conditions 3 g 460.2g 113.3g 665 ■ 7 g 672.6g 49.39 g 870 mg g 323.2g 13.94 g 409 mg 1773.6 g 1470 relatives Make 2983 relatives with distilled water.

(Solution F) 20% KBr aqueous solution Required amount for pAg adjustment (Solution G) 56% acetic acid aqueous solution Required amount for pH adjustment 40°
In C, solution E and solution B were added to solution A by a simultaneous mixing method using a mixing stirrer, C was added at the same time as the addition of B was completed, and D was added at the same time as the addition of C was completed.

Control of PAg, p)l during simultaneous mixing and solution E, solution B
The addition rates of solution C1 and solution were as shown in Table-13.

PAg and pH were controlled by changing the flow rates of solution F and solution G using a roller tube pump with variable flow rate.

After adding solution E, wash with demineralized water, redisperse, and heat at 40°.
The pH was adjusted to 6.0 and the PAg was adjusted to 7.7.

This emulsion is designated as Em-C.

8゜4 with a core/shell structure with an average particle size of 0.47μm
6mo 42% AgI content particles.

Polydisperse silver halide emulsion Em-D according to the following method
, Em-E, and Em-F (comparison) were adjusted.

(Preparation of emulsion Em-D) At 65°C, while stirring at a rotational speed of 320 rpm, add liquid C to liquid A over 1 minute, then add liquid B and D over 90 minutes using a nozzle, and then add liquid Desalination was carried out by the method.

(Preparation of emulsion Em-E) L ossein gelatin 8.0 g C solution H, 0 30 cc At 55°C, while stirring at a rotational speed of 320 rpm, add solution D to solution A for 9 minutes 30 seconds, and add Bi to D 10 seconds after starting liquid addition 1
The mixture was added and mixed at 0 minutes, and after adding Solution C, desalting was performed by a conventional method.

(Preparation of emulsion Em-F) After adding and neutralizing with liquid C, Desalting was carried out by a conventional method.

Ossein gelatin 3.00 g C liquid - acetic acid (56%) 68.0 cc Example 6 On a triacetyl cellulose film support, each layer having the composition shown below was sequentially formed from the support side to produce a multilayer color photograph. A photosensitive material sample-101 was prepared.

In all the descriptions below, the amount of the compound added to the silver halide photographic material is expressed in grams per 1M unless otherwise specified. Furthermore, silver halide and colloidal silver are shown in terms of silver.

Sample 101 (comparison) 1st layer: antihalation layer (HC-1) black colloidal silver 0.2 UV absorber (UV-1)
0.23 high boiling point solvent (Oiffi-1)
0.18 gelatin 1.4
2nd layer: 1st intermediate layer (IL-1) Gelatin 1.3 3rd layer: Low sensitivity red-sensitive emulsion layer (RL) Silver iodobromide emulsion (Em-C) 1.0 Sensitizing dye (
SD-1) 1.8X10-5 mole/silver 1 mole Enhanced dye (SD-2) 2.8X10-' mole/silver 1 mole Sensitizing dye (SD-3) 3,OX 10-' mole/silver 1 mole Lucian coupler (C-1) 0.70 colored cyan coupler (CC-1) 0.066 0.03 0.01 0.64 1.2 DIR compound (D-1) DIR compound (D-3) High boiling point solvent (Off-1) Gelatin No. 4N: Medium red-sensitive emulsion layer (RM) Silver iodobromide emulsion (Em-B) 0.8 sensitizing dye (
SD-1) 2, lX10-' mole/silver 1 mole Sensitizing dye (SD-2) 1.9X10-' mole/silver 1 mole Sensitizing dye (SD-3) 1.9XIQ-' mole/silver 1 mole Lucian coupler (C-1) 0.28 Colored cyan coupler (CG-1) 0.027 DIR compound (D-1) 0.01 High boiling point solvent (Oij2-1) 0.26 Gelatin
0.6 5th layer: high-frequency red-sensitive emulsion layer (
RH) Silver iodobromide emulsion (Em-A) 1.70 Sensitizing dye (SD-1) 1.9 X 10-5 mole/silver 1 mole Enhanced dye (SD-2) 1.7 X 10-' mole/! 1 mol sensitizing dye (SD
-3) 1.7X10-' mol/i 1 mol Cyan coupler (C-1) 0.05 Cyan coupler (C-2) 0.10 Colored cyan coupler (CC-1) 0.02 DIR compound (D- 1) 0.025 High boiling point solvent (Oi 1-1) 0.17 Gelatin 1.2 6th layer: 2nd intermediate layer (I
L-2) Gelatin 0.8 7th layer: Low-range green-sensitive emulsion layer (GL) Silver iodobromide emulsion (E m -C) 1.1 Sensitizing dye (SD-4) 6.8X10-' mol /silver 1 mol aggravating dye (SD-5) 6.2X10-' mol/silver 1 mol magenta coupler (M-1) 0.54 magenta coupler (M-2) 0.19 colored magenta coupler (CM-1) 0 .06 DIR compound (D-2) 0.017DI
R compound (D-3) 0.01 High boiling point solvent (Oif-2) 0.81 Gelatin
1.8 8th layer: medium-sensitivity green-sensitive emulsion 11
(GM) Silver iodobromide emulsion (Em-B) Q,7 sensitizing dye (SD-6) 1.9X10-' mol/silver 1 mol Sensitizing dye (SD-7) 1.2X10-' mol/silver 1 mole sensitizing dye (SD-8) 1.5 x 10-' mole/silver 1 mole magenta coupler (M-1) 0.07 magenta coupler (M-2) 0.03 colored magenta coupler (CM-1) 0. 04 0.018 0.30 0.8 DIR compound (D-2) High boiling point solvent (Off-2) Gelatin 9th layer: High sensitivity green-sensitive emulsion layer (GH) Silver iodobromide emulsion (Em-A) 1 .7 Sensitizing dye (
SD-6) 1.2 X 10-' mol/silver 1 mol sensitizing dye (SD-7) 1.0xlO-'-rr/silver 1 mol sensitizing dye (SD-8) 3.4 X 10 -”mol/silver 1 mole Magenta coupler (M-1) 0.09 Magenta coupler (M-3) 0.04 Colored magenta coupler (CM-1) 0.04 (Oif-2) 0.31 1.2 High Boiling point solvent gelatin 10th layer: Yellow filter layer Yellow colloidal silver stain inhibitor (SC-1) High boiling point solvent (Oiffi-2) Gelatin Formalin scavenger Formalin scavenger (YC) 0.05 0.1 0.13 0.7 (H3-1) 0.09 (MS-2) 0.07 11th layer: Low-speed blue-sensitive emulsion layer (BL) Silver iodobromide emulsion (
Em-B) 0.5 silver iodobromide emulsion (Em-C)
0.5 sensitizing dye (SD-9) 5.2 Hanger (H3-1) 0.08 Sensitizing dye (SD-10) 1.9X10 Yellow coupler (Y Yellow coupler (Y DIR compound (D-1) High boiling point solvent (O4f-2 Gelatin formalism 12th layer: High-frequency blue-sensitive emulsion (BH) silver iodobromide emulsion (
E m -A) 1.0 Sensitizing dye (SI) -
9) 1.8
-10) 7.9X10-5 mol/S 1 mol Yellow coupler (Y-1) 0.15 Yellow coupler (Y-2) 0.05 High boiling point solvent (
Oi 1-2) 0.074 gelatin
1.30 formalin scavenger (
MS-1) 0.05 Formalin scavenger (H3-2) 0.12 13th layer: 1st protective layer (Pro-1) Fine grain silver iodobromide emulsion 0.4 (average grain size 0
．． 08 μm, Agr content 1 mol%) ultraviolet absorber (U
V-1) 0.07 ultraviolet absorber (UV-2)
0.10 high boiling point solvent (Oiffi-1)
0.07 High boiling point solvent (Off-3) 0
．． 07 Formalin scavenger (MS-1) 0.13 Formalin scavenger (MS-2) 0.37 Gelatin 1.3 14th layer: 2nd protective layer (Pro-2) Alkali-soluble matting agent (average particle size 2 μm ) 0.13 Polymethyl methacrylate (average particle size 3 μm) 0.02 Slip agent (WAX
-1) 0.04 gelatin
0.6 In addition to the above composition, coating aid S
u-1, dispersion aid 5u-2, viscosity modifier, hardener H-
1, H-2, stabilizer 5T-1, anti-gaggle agent AF-1,
& : 10.000 and & : 1.100,000
(7) Two types of AF-2 were added.

Each emulsion contains gold Sulfur sensitization was optimally applied. -1～ Margin below 1) -2 -2 M -1 Q Q 0■ M 8 0■ i ! C 1 U■ AX D-1 D-2 D 0■ 0■ 0■ Weight average molecular weight = 3. OOO u S S D D D-6 ■ 5D-7 SD-IQ SD T-1 H SD-9 F-2 Next, the third layer, fourth layer, and fifth layer of the sample 101.

The silver halide emulsions of the 7th layer, 8th layer, and 9th layer are shown below.
Samples 102 to 106 were prepared by making the following changes. Furthermore, the fourth and eighth layers of sample 101 are removed, and the third layer is removed.
Samples 107 to 111 were prepared in which the amounts of silver halide emulsions used in the 5th layer, 7th layer, and 9th layer were changed as follows (see Table 15).

(Silver halide emulsion amount of samples 107 to 111) Third layer:
Low-sensitivity red-sensitive emulsion layer Silver iodobromide emulsion (see Table-15) 1.58 Silver iodobromide emulsion (see Table-15) 1.58 5th layer: High-sensitivity red-sensitivity emulsion layer Silver iodobromide emulsion (See Table-15) 1.93 Silver iodobromide emulsion (See Table-15) 1.02 7th layer: Low-sensitivity green-sensitive emulsion layer Silver iodobromide emulsion (See Table-15) Silver iodobromide emulsion (See Table-15) 9th layer: High-sensitivity green-sensitive emulsion layer Silver iodobromide emulsion (See Table-15) 1.02 1.02 2.49 Table-f 4 Table-15 Prepared as above Using Samples 101 to 111, processing variability was evaluated by the method shown below.

(Evaluation method) Each sample subjected to one-color wedge exposure was subjected to the following development conditions (
3B, 0°C), and further processed by changing only the color developing bath temperature (36.5°C, 39.5°C), and the fog density and sensitivity of each sample were measured.

几・2・Each sample subjected to wedge exposure was subjected to the following development conditions (38,0″C
), but the stirring time interval of the developer (1 time/1 second, 1 time/30 seconds) was changed only during color development. The fog density and sensitivity of each sample were measured.

Using the following evaluation results, the performance of each sample due to processing variations is shown in Table 16.

Processing process (38cc) Processing time Color development 3 minutes 15 seconds Bleaching
Wash with water for 6 minutes and 30 seconds
Fixed for 3 minutes and 15 seconds
Wash with water for 6 minutes and 30 seconds
3 minutes and 15 seconds The composition of the treatment liquid used in each treatment step is as follows.

<Color developer composition) 4-amino-3-methyl-N~ethyl-N-(β-hydroxyethyl)aniline/sulfate 4.8g anhydrous sodium sulfite 0.14g hydroxyamine/% sulfate 1.98g sulfuric acid
0.74 g anhydrous potassium carbonate
28.35 g anhydrous potassium bicarbonate 3.46 g anhydrous potassium sulfite
5.10g potassium bromide
1.16g sodium chloride
0.14g nitrilotriacetic acid trisodium salt (monohydrate) 1.20g potassium hydroxide 1.48g Add water to make 11.

<Bleach solution composition> Ethylenediaminetetraacetic acid iron ammonium salt 100.0 g Ethylenediaminetetraacetic acid diammonium salt 10.0 g Ammonium bromide 150.0g Glacial acetic acid 10. Add Oa/water to 1! and adjust the pH to 6.0 using aqueous ammonia.

<Fixer composition> Ammonium thiosulfate 175.0g Anhydrous sodium sulfite 8.6g Sodium metasulfite 2.3g Add water to make 11, and adjust to pH 6.0 using acetic acid.

<Stabilizing liquid composition> Formalin (37% aqueous solution> 1.5 m
i! Konidax (Konica Corporation M) 7.5
Add ml water to make 11.

As is clear from Table 16, the samples of the present invention are highly sensitive and stable against fluctuations in processing conditions.Example 7 For samples 101 to 111 prepared in Example 6, the development processing conditions are as shown below. Similar results were obtained when the treatment variability was evaluated.

However, the process was continued until three times the capacity of the stabilization tank was filled with replenisher. Further, the stabilization treatment was carried out using a three-tank countercurrent system, in which the replenisher was replenished into the final stabilizing liquid tank, and the overflow liquid flowed into the previous tank.

Furthermore, a portion (275 d/rd) of the overflow liquid from the stabilization tank following the fixing tank was poured into the stabilization tank.

<Composition of color developer used> Potassium carbonate 30 g Sodium hydrogen carbonate 2.7 g Potassium sulfite 2.8 g Sodium bromide
1.3g hydroxylamine sulfate
3.2g sodium chloride
0.6g 4-amino-3-methyl-N-ethyl-N-(β-hydroxyethyl)aniline sulfate 4.6g diethylenetriaminepentaacetic acid 3.0g potassium hydroxide 1.3g Add water to 11
and adjust the pH using potassium hydroxide or 20% sulfuric acid.
Adjust to lo, 01.

<Composition of color developer replenisher used> Potassium carbonate 40 g Sodium bicarbonate 3 g Potassium sulfite
7g sodium bromide
0.5g hydroxylamine sulfate
3.2g 4-amino-3-methyl-N-ethyl-N-(β-hydroxylethyl)aniline 6fim salt 6.0g diethylenetriaminepentaacetic acid 3.0g potassium hydroxide
Add 2g water and 1! and adjust the pH to 10.12 using potassium hydroxide or 20% sulfuric acid.

<Composition of the bleach solution used> 1.3-diaminopropanetetraacetic acid ferric ammonium 0.35 mol ethylenediaminetetraacetic acid disodium 2 g ammonium bromide 150 g glacial acetic acid
40mfl ammonium nitrate
Add 40 g water to make 12, and adjust to pH 4.5 using aqueous ammonia or glacial acetic acid.

Composition of commonly used bleach replenishment solution> 1.3-diaminopropanetetraacetic acid ferric ammonium 0.40 mol ethylenediaminetetraacetic acid disodium 2 g ammonium bromide 170 g ammonium nitrate
50 g glacial acetic acid
61 ad! Add water and 1! Then adjust the pH to 3.5 using aqueous ammonia or glacial acetic acid to maintain the pH of the bleach tank solution.

<Composition of fixer and fixer replenisher used> Ammonium 100osulfate 100g Ammonium thiocyanate 150g Anhydrous sodium bisulfite
20 g sodium metabisulfite 4
．． Add 0g ethylenediaminetetraacetic acid disodium 1.0g water to make 700, and adjust the pH using glacial acetic acid and aqueous ammonia.
Adjust to 6.5.

Composition of the stabilizing solution and stabilizing replenisher used

2 Benzisothiazolin 3-one 0.1 g Hexamethylenetetramine 0.2 g Hexahydro-1,3,5-)lis(2-hydroxyethyl)-5-triazine 0.3 g Water was added to make 11, potassium hydroxide and pH using 50% sulfuric acid
Adjusted to 7.0.

Example 8 The heat resistance and moisture resistance of samples 101 to 111 prepared in Example 6 were evaluated according to the following method.

Stability past value samples 101 to 111 were stored at 65° C. and 40% relative humidity for 3 days.

■Wet test Samples 101 to 111 were stored for one week at 23° C. and 80% relative humidity.

These samples stored over time were subjected to wedge exposure together with the samples not stored over time, processed under the development conditions shown in Example 6, and the preservability was evaluated by comparing the performance with the samples not stored over time.

The results are shown in Table-17.

As is clear from Table 17, the samples of the present invention are also excellent in heat resistance and moisture resistance.

〔Effect of the invention〕

According to the present invention, it was possible to provide a silver halide photographic material that is highly sensitive, has excellent stability against fluctuations in processing conditions, and has excellent heat resistance and moisture resistance.

Claims (1)

[Scope of Claims] 1. A silver halide photographic light-sensitive material having on a support at least one layer each of a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a blue-sensitive silver halide emulsion layer. In the color-sensitive silver halide emulsion layer, at least one of the red-sensitive silver halide emulsion layer and the green-sensitive silver halide emulsion layer is arranged from the side close to the support to the low-sensitivity silver halide emulsion layer, the medium-sensitivity halogen emulsion layer, and the medium-sensitivity halogen emulsion layer. It has a silver halide emulsion layer and a high-sensitivity silver halide emulsion layer, and at least one of the low-sensitivity, medium-sensitivity, and high-sensitivity silver halide emulsion layers consists essentially of silver iodobromide. Silver iodobromide grains consisting of a core and a shell covering the core and consisting essentially of silver iodobromide or silver bromide having a lower silver iodide content than the silver iodobromide of the core. 1. A silver halide photographic material comprising a silver halide emulsion in which the relative standard deviation of the silver iodide content of individual grains of the emulsion is 20% or less.