JPH11174608A - Silver halide color photosensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silver halide emulsion which has high sensitivity, and is excellent in pressure characteristic and remarkably improved in exposure time illumination dependency and silver halide color photosensitive material using it. SOLUTION: In a silver halide color photosensitive material having at least one layer of silver halide emulsion on a support, at least one layer of the silver halide emulsion layer is a silver halide emulsion containing flat silver halide grains having the average aspect ratio of 1.5 or more, the sphere conversion average grain size of 0.2 μm or more and the variation coefficient of the sphere conversion average grain size of 30% or less, and it contains at least two or more kinds of silver halide emulsions different in the sphere conversion average grain size. Further, the average length of dislocation lines of flat silver halide grains which two or more kinds of emulsions contain is substantially constant.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide color photographic light-sensitive material useful in the field of photography, and more particularly to a silver halide having high sensitivity, excellent pressure characteristics, and improved exposure illuminance suitability. The present invention relates to a color photographic light-sensitive material.

[0002]

2. Description of the Related Art In recent years, compact cameras and auto-focus cameras 1
With the spread of eye reflex cameras, films with lenses, and the like, the development of silver halide color photographic materials having high sensitivity and excellent image quality has been strongly desired. Therefore, demands for improved performance of photographic silver halide emulsions are becoming more severe, and higher levels of demands are made on photographic performance such as high sensitivity, excellent graininess, and excellent sharpness.

In response to such demands, for example, US Pat. Nos. 4,434,226, 4,439,520, 4,414,310, 4,433,048, and 4,414, Nos. 306 and 4,459,353 disclose techniques using tabular silver halide grains (hereinafter also simply referred to as "tabular grains"). Advantages such as improvement in sensitivity, improvement in sensitivity / granularity, improvement in sharpness due to specific optical properties of tabular grains, and improvement in covering power are known. However, it is not enough to meet recent high-level demands, and further improvement in performance is desired.

[0004] In connection with the trend toward higher sensitivity and higher image quality, demands for improvement of pressure characteristics in silver halide color photographic light-sensitive materials have been increasing more than ever.
Although it has been considered to improve the pressure characteristics by various means, a technique for improving the stress resistance of the silver halide grains itself is better than a technique using an additive such as adding a plasticizer. The view that it is practically preferable and that the effect is large is promising. In response to these demands, emulsions comprising core / shell type silver halide grains having a silver iodobromide layer having a high silver iodide content have been actively studied. In particular, silver iodobromide emulsions containing core / shell grains having a high silver iodide phase content of 10 mol% or more inside grains have attracted much attention as, for example, emulsions for color negative films.

As a method for increasing the sensitivity of a silver halide emulsion, a technique of introducing dislocation lines into tabular silver halide grains is disclosed in US Pat. No. 4,956,269. It is generally known that when pressure is applied to silver halide grains, fogging or desensitization occurs.However, grains having dislocation lines introduced therein have a problem that they are significantly desensitized by application of pressure. Was. JP-A-3-189642 discloses that tabular silver halide grains having an aspect ratio of 2 or more and having 10 or more dislocation lines in a fringe portion, and the size distribution of the tabular silver halide grains is monodispersed Are disclosed. However, this technique does not improve the significant desensitization caused by the pressure caused by introducing dislocation lines.

Techniques for improving pressure characteristics with core / shell type particles include, for example, JP-A-59-99433 and JP-A-59-99433.
The techniques disclosed in Japanese Patent Nos. 0-35726 and 60-147727 are known. Also, JP-A-63-220238,
Japanese Patent Application Laid-Open No. Hei 1-2201649 discloses a technique for improving sensitivity, graininess, pressure characteristics, exposure illuminance and the like by introducing dislocations into silver halide grains. Japanese Patent Application Laid-Open No. 6-235988 discloses a technique of improving pressure resistance by using multi-structure monodisperse tabular grains having a high iodine layer in an intermediate shell.

Further, as a technique for controlling charge carriers (carriers) in silver halide grains, such as free electrons and holes, a metal doping technique is known. For example, it has been reported by Leubner that the iridium complex doped with silver halide exhibits an electron trapping property (The Journal of Photo.
graphic Science Vol. 31,93
(1983)). Further, for example, JP-A-3-15040 discloses an iridium ion-containing emulsion in which iridium ions are not present on the grain surface and a method for producing the same.
Further, for example, Japanese Patent Application Laid-Open No. 6-175251 discloses that in-plane epitaxy-type grains to which an iridium compound is added during a silver halide grain production step, the sensitivity at 1/100 second exposure,
And a technique that achieves both reciprocity failure characteristics.

However, in these techniques,
As a silver halide color photographic light-sensitive material having high sensitivity, excellent pressure characteristics, and improved exposure illuminance suitability, it has not yet been satisfactory as a material capable of meeting the recent high demands.

[0009]

SUMMARY OF THE INVENTION In view of the above problems, an object of the present invention is to provide a silver halide emulsion having high sensitivity, excellent pressure characteristics, and markedly improved illuminance dependency upon exposure, and a halogen using the same. An object of the present invention is to provide a silver halide color photographic material.

[0010]

The above object of the present invention is achieved by the following constitution.

1. In a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support, at least one of the silver halide emulsion layers is
The average aspect ratio is 1.5 or more, and the sphere-converted average particle size is 0.1.
A silver halide emulsion containing tabular silver halide grains having a sphere-converted average grain size of 2 μm or more and a coefficient of variation of a sphere-converted average grain size of 30% or less, wherein at least two types of silver halide emulsions having different sphere-converted average grain sizes are contained. And a silver halide color photographic light-sensitive material characterized in that the average length of dislocation lines of tabular silver halide grains contained in the two or more emulsions is substantially constant.

2. In a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support, at least one of the silver halide emulsion layers is
The average aspect ratio is 1.5 or more, and the sphere-converted average particle size is 0.1.
A silver halide emulsion containing tabular silver halide grains having a sphere-converted average grain size of 2 μm or more and a coefficient of variation of a sphere-converted average grain size of 30% or less, wherein at least two types of silver halide emulsions having different sphere-converted average grain sizes are contained. And a silver halide color photographic light-sensitive material characterized in that the coefficient of variation of the length of dislocation lines of tabular silver halide grains contained in the two or more emulsions is substantially constant.

3. In a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support, at least one of the silver halide emulsion layers is
The average aspect ratio is 1.5 or more, and the sphere-converted average particle size is 0.1.
A silver halide emulsion containing tabular silver halide grains having a sphere-converted average grain size of 2 μm or more and a coefficient of variation of a sphere-converted average grain size of 30% or less, wherein at least two types of silver halide emulsions having different sphere-converted average grain sizes are contained. A silver halide color photographic light-sensitive material characterized in that the maximum silver iodide content in the dislocation line existing region of the tabular silver halide grains contained in the two or more emulsions is substantially constant.

4. In a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support, at least one of the silver halide emulsion layers is
The average aspect ratio is 1.5 or more, and the sphere-converted average particle size is 0.1.
A silver halide emulsion containing tabular silver halide grains having a sphere-converted average grain size of 2 μm or more and a coefficient of variation of a sphere-converted average grain size of 30% or less, wherein at least two types of silver halide emulsions having different sphere-converted average grain sizes are contained. And a silver halide color photographic light-sensitive material characterized in that the tabular silver halide grains contained in the two or more emulsions have a substantially constant polyvalent metal compound doping amount.

[0015] 5. In a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support, at least one of the silver halide emulsion layers is
The average aspect ratio is 1.5 or more, and the sphere-converted average particle size is 0.1.
A silver halide emulsion containing tabular silver halide grains having a sphere-converted average grain size of 2 μm or more and a coefficient of variation of a sphere-converted average grain size of 30% or less, wherein at least two types of silver halide emulsions having different sphere-converted average grain sizes are contained. A silver halide color photographic light-sensitive material characterized in that tabular silver halide grains contained in the two or more kinds of emulsions have a substantially constant polyvalent metal compound doping position.

Hereinafter, the present invention will be described in detail.

The silver halide grains contained in the silver halide emulsion of the present invention are tabular grains. Tabular grains are crystallographically classified as twins.

A twin is a silver halide crystal having one or more twin planes in one grain, and the classification of the form of the twin is based on the report by Klein and Moiser in Photographic correspondence.
(Korrespondenz) Vol. 99, p100, and Vol. 100, p57.

The tabular grains in the present invention have two twin planes parallel to the main plane. The twin plane can be observed with a transmission electron microscope. The specific method is as follows. First, a silver halide photographic emulsion is coated on a support so that the tabular grains to be contained are substantially parallel to the main plane, thereby preparing a sample. This is cut using a diamond cutter to obtain a thin section having a thickness of about 0.1 μm. By observing this section with a transmission electron microscope, the presence of twin planes can be confirmed.

The distance between two twin planes in the tabular grains of the present invention is determined by observing a section using the above-mentioned transmission electron microscope, and shows a tabular grain having a cross section substantially perpendicular to the main plane. Is arbitrarily selected, and the distance between the two twin planes having the shortest distance among the even twin planes parallel to the main plane is obtained for each particle and averaged.

In the present invention, the twin plane distance is a factor affecting the supersaturation state at the time of nucleation, for example, gelatin concentration, gelatin species, temperature, iodine ion concentration, pBr, p
It can be controlled by appropriately selecting a combination of various factors such as H, ion supply speed, stirring rotation speed, and the like. In general, the more the nucleation is performed in a supersaturated state, the narrower the distance between twin planes can be.

For details regarding the supersaturation factor, see, for example, JP-A-63-92924 or JP-A-1-21363.
The description of No. 7, etc. can be referred to.

In the present invention, the average distance between twin planes is preferably 0.01 μm to 0.05 μm, and more preferably 0.013 μm to 0.025 μm.

The thickness of the tabular grains of the present invention can be obtained by observing a section using a transmission electron microscope as described above, similarly calculating the thickness of each grain, and performing averaging. The thickness of the tabular grains is 0.05 μm to 1.
5 μm is preferred, and more preferably 0.07 μm to 0.1 μm.
50 μm.

The tabular grains of the present invention have an average aspect ratio (average of grain size / grain thickness of individual silver halide grains).
Is 1.5 or more, but preferably the average aspect ratio is 3 or more and 20 or less, and more preferably the average aspect ratio is 5 or more and 10 or less. If the average aspect ratio is less than 1.5, it is difficult to achieve high sensitivity, and if it is more than 20, the pressure resistance is slightly inferior.

The grain size of the tabular grains in the present invention is represented by the sphere-converted grain size of the silver halide grains (the diameter of a sphere having the same volume as the silver halide grains).

The tabular grains of the present invention have an average sphere-equivalent particle size of 0.2 μm or more, preferably from 0.3 μm to 3.0.
μm. If it is less than 0.2 μm, the photosensitivity is insufficient, and if it is more than 3.0 μm, the pressure resistance and the developing characteristics are slightly inferior.

The tabular grains of the present invention are obtained by mixing two or more tabular grains having an average sphere-equivalent particle diameter of 0.2 μm or more. In the present invention, the difference in the average particle diameter means that the difference in the particle diameter of the tabular grains to be mixed is 0.07 μm in terms of a sphere equivalent average particle diameter.
m or more, 0.15μm or more and 2.5μ
m or less. Particle size difference is 0.07μm
If the particle diameter is less than 2.5 μm, the effect of mixing two or more silver halide emulsions is extremely small. If the particle size difference is larger than 2.5 μm, the characteristics of the two or more silver halide emulsions are too far apart. However, the effect of the present invention is undesirably reduced.

The particle diameter can be obtained, for example, by photographing the particle with an electron microscope at a magnification of 10,000 to 70,000 and measuring the particle diameter and particle thickness on the print (measurement particle). The number shall be 1000 or more indiscriminately).

Here, the sphere-equivalent average particle size r is the product of the frequency ni of particles having the sphere-equivalent particle size ri and ri ³ ni × ri ³
Is defined as the particle size ri when the maximum is
Digits and minimum digits are rounded off to the nearest 4).

The coefficient of variation of the sphere-converted average particle diameter of the tabular grains of the present invention is represented by (standard deviation / average sphere-converted particle diameter) × 100 = the coefficient of variation of the sphere-converted average particle diameter [%]. When defined, it is 30% or less, preferably 20% or less. The smaller the coefficient of variation, the better, but the limit is about 3% for industrial production. Within such a range, the effects of the present invention are clearly exhibited. Here, the sphere-converted average particle diameter and the standard deviation are determined from the particle diameter ri defined above.

The average silver iodide content of the tabular grains of the present invention is 1 mol% or more, preferably 1 to 10 mol%.
And more preferably 2 to 7 mol%. 1 mo
If it is less than 1%, it is disadvantageous for high sensitivity, and 10 mol%
If it is higher, the desilvering property in the development processing tends to decrease.

The tabular grains of the present invention are emulsions mainly containing silver iodobromide as described above, but may contain silver halide of another composition, such as silver chloride, as long as the effects of the present invention are not impaired. be able to.

The distribution state of silver iodide in the silver halide grains can be detected by various physical measurement methods, for example, as described in the Abstracts of the Annual Meeting of the Photographic Society of Japan, 1981. It can be measured by low temperature luminescence measurement, EPMA method, or X-ray diffraction method.

In the present invention, the silver iodide content and the average silver iodide content of each silver halide grain are determined by an EPMA method (Electron Probe Micro Ana).
(lyzer method). According to this method, a sample in which emulsion grains are well dispersed so as not to be in contact with each other is prepared, and element analysis of a very small portion can be performed by X-ray analysis by electron beam excitation for irradiating an electron beam. By determining the characteristic X-ray intensity of silver and iodine emitted from each grain by this method, the halogen composition of each grain can be determined. When the silver iodide content of at least 50 grains is determined by the EPMA method, the average silver iodide content is determined from the average thereof.

The tabular grains in the present invention preferably have a more uniform silver iodide content between grains. E
When the distribution of silver iodide content between grains is measured by the PMA method, the relative standard deviation is preferably 30% or less, more preferably 20% or less.

The silver iodide content on the surface of the tabular grains of the present invention is preferably at least 1 mol%, and is preferably 2 to 20 mol%.
% Is even more preferable.

The surface of the tabular grains of the present invention is the outermost layer of the grains including the outermost surface of the silver halide grains, and refers to a depth of up to 50 ° from the outermost surface of the grains. The halogen composition on the surface of the tabular grains of the present invention is determined by an XPS method (X-ray Pho).
Toetron Spectroscopy method:
(X-ray photoelectron spectroscopy) as follows.

That is, the sample was cooled to −110 ° C. or less in an ultra-high vacuum of 1 × 10 E ⁻⁸ torr or less, and irradiated with MgKα as a probe X-ray at an X-ray source voltage of 15 kV and an X-ray source current of 40 mA. Ag 3d5 / 2, Br 3d,
It measures about the electron of I3d3 / 2. The integrated intensity of the measured peak is used as a sensitivity factor (Sensity F
actor), and the halide composition on the silver halide surface is determined from these intensity ratios.

The dislocation lines of the silver halide grains are described, for example, in J. Am. F. Hamilton, Photo. Sci. E
ng. 11 (1967) 57 and T.I. Shiozaw
a, J. et al. Soc. Photo. Sci. Japan, 35
(1972) 213 can be observed by a direct method using a transmission electron microscope at a low temperature. That is, the silver halide grains taken out from the emulsion so as not to apply enough pressure to generate dislocations on the grains are placed on a mesh for an electron microscope so as to prevent damage by electron beams (such as printout). Observation is performed by a transmission method while the sample is cooled. At this time, the thicker the particle, the more difficult it is for an electron beam to pass through, so that a method using a high-pressure electron microscope can observe more clearly. From the grain photograph obtained by such a method, the position and number of dislocation lines in each grain can be determined.

The number of dislocation lines present in one particle is measured as follows. A series of particle photographs with different inclination angles with respect to the incident electrons are taken for each particle to confirm the existence of dislocation lines. At this time, if the number of dislocation lines can be counted, the number of dislocation lines is counted. For example, when dislocation lines exist densely or dislocation lines cross each other,
When the number of dislocation lines per particle cannot be counted, it is counted that there are many dislocation lines.

Many of the dislocation lines existing in the central region of the main plane of the tabular grains of the present invention form a so-called dislocation network, and the number thereof may not be clearly counted.

The tabular grains of the present invention can have dislocation lines in both the central region and the peripheral region of the main plane, but preferably have dislocation lines in the peripheral region.

The central region of the main plane of the tabular grains as used herein refers to a circular portion having a radius of 90% of the radius of a circle having the same area as the main plane of the tabular grains and having a common center. A region having a certain tabular grain thickness. On the other hand, the peripheral region of the tabular grains refers to a region having an area corresponding to the annular region outside the central region, existing around the tabular grains, and having a thickness of the tabular grains.

On the other hand, the dislocation lines existing in the outer peripheral region of the tabular grains of the present invention are observed as lines extending radially from the center of the grains toward the sides, but often meander.

The tabular grains of the present invention have a number ratio of 30%.
Although the above has dislocation lines in the outer peripheral region and the number of dislocation lines in the outer peripheral region is 10 or more per grain, 50% or more (number ratio) of tabular grains are in the outer peripheral region. And the number of dislocation lines in the outer peripheral region is preferably 20 or more per particle.

As a method for introducing dislocation lines into silver halide grains, for example, a method in which an aqueous solution containing iodide ions such as potassium iodide and a water-soluble silver salt solution are added by double jet, or silver iodide is included. A method of adding a fine grain emulsion,
A method of adding only a solution containing iodide ions;
Dislocations which are the origin of dislocation lines can be formed at desired positions using a known method such as a method using an iodide ion releasing agent as described in No. 11781. Among these methods, a method of adding a fine grain emulsion containing silver iodide and a method of using an iodide ion releasing agent are particularly preferable.

When an iodine ion releasing agent is used, sodium p-iodoacetamidobenzenesulfonate,
Iodoethanol, 2-iodoacetamide and the like can be preferably used.

The length of the dislocation line formed in the tabular grains of the present invention is 30 nm or more, preferably 50 nm to 15 nm.
0 nm.

In the present invention, the length of the dislocation line of the tabular grains to be mixed is substantially constant. The fact that the length of dislocation lines is substantially constant means that the ratio of the shortest to longest dislocation lines observed in the mixed tabular grains is 0.77 or more and 1.3 or less. To tell. Within this range, it has been found that the effects of the present invention clearly appear, and it is more preferable that the range be 0.9 or more and 1.1 or less.

The coefficient of variation of the length of the dislocation lines of the tabular grains in the present invention is 30% or less, preferably 25% or less, more preferably 20% or less.

In the present invention, the coefficient of variation of the dislocation line length of the tabular grains to be mixed is substantially constant. The fact that the coefficient of variation of dislocation line length is substantially constant means that the ratio of the smallest variation coefficient to the largest variation coefficient of dislocation line length observed in mixed tabular grains is 0.77 or more and 1.3 or more. Say that:

In the present invention, the silver iodide content in the dislocation line existing region of the tabular grains can be measured by the EPMA method. That is, from the center of the main plane of the tabular grain,
A line segment perpendicular to the side is drawn, measurement points are taken on the line segment at intervals of 5 to 15% of the length of the line segment, and the average silver iodide content in the direction perpendicular to the main plane of each measurement point Is measured. At this time, it is necessary to narrow the measurement spot to 40 nm or less. In addition, it is necessary to cool the measurement temperature to −100 ° C. or less in consideration of damage to the sample. The integration time at each measurement point shall be 30 seconds or more.

The tabular grains of the present invention have a maximum silver iodide content of the dislocation line existing region of 15 mol% or less, preferably 10 m 2, of the silver iodide content determined as described above.
ol% or less, more preferably 5 mol% or less.

In the present invention, the maximum silver iodide content in the dislocation line region of the tabular grains to be mixed is substantially constant. The fact that the maximum silver iodide content in the dislocation line region is substantially constant means that the ratio between the smallest and the largest silver iodide content in the dislocation line region observed in the mixed tabular grains is 0. .7
It means that it is 7 or more and 1.3 or less.

The tabular grains of the present invention contain at least one or more polyvalent metal compounds.

Here, the terms are defined, but "doping" or "doping" means that a substance other than silver ions or halide ions is contained in silver halide grains. The term "dopant" refers to compounds that dope the silver halide grains. The term "metal dopant" refers to a polyvalent metal compound doped into silver halide grains.

As metal dopants, Mg, Al,
Ca, Sc, Ti, V, Cr, Mn, Fe, Co, C
u, Zn, Ga, Ge, Sr, Y, Zr, Nb, Mo,
Tc, Ru, Rh, Pd, Cd, Sn, Ba, Ce, E
u, W, Re, Os, Ir, Pt, Hg, Tl, Pb,
Metal compounds such as Bi and In can be preferably used.

The metal compound to be doped is preferably selected from a single salt or a metal complex. When selecting from metal complexes, 6-coordinate, 5-coordinate, 4-coordinate and 2-coordinate complexes are preferred, and octahedral 6-coordinate and planar 4-coordinate complexes are more preferred. The complex may be a mononuclear complex or a polynuclear complex. The ligands constituting the complex include CN-, C-
O, NO ₂ -, 1,10-phenanthroline, 2,2 '
- bipyridine, SO ₃ -, ethylenediamine, NH _{3, pyridine, H 2 O, NCS-, CO-} , NO 3 -, SO
_{4 -, OH-, N 3 -} , S 2 -, F-, Cl-, Br-,
I- or the like can be used. Particularly preferred metal dopants are K ₄ Fe (CN) ₆ and K ₃ Fe (C
N) ₆ , Pb (NO ₃ ) ₂ , K ₂ IrCl ₆ , K ₃ IrC
_{l 6, K 2 IrBr 6,} InCl 3 , and the like.

The concentration distribution of the metal dopant in the silver halide grains is such that the grains are gradually dissolved from the surface to the inside,
It is determined by measuring the dopant content of each part. Specific examples include the method described below.

Prior to metal quantification, the silver halide emulsion is pretreated as follows. First, 50 ml of a 0.2% actinase aqueous solution is added to about 30 ml of the emulsion, and the mixture is stirred at 40 ° C. for 30 minutes to perform gelatin decomposition. This operation 5
Repeat several times. After centrifugation, 5 times with 50 ml of methanol,
Washing is repeated twice with 50 ml of 1N nitric acid and five times with ultrapure water. After centrifugation, only silver halide is separated. The surface portion of the obtained silver halide grains is dissolved with an aqueous ammonia solution or ammonia whose pH has been adjusted (the ammonia concentration and pH are changed according to the type and amount of silver halide to be dissolved). As a method for dissolving the extreme surface of silver bromide grains in silver halide, about 1 g of silver halide is dissolved in 2 g of silver halide.
About 20% of the particles can be dissolved by using 20 ml of 0% aqueous ammonia. At this time, the amount of silver halide dissolved was determined by centrifuging the aqueous ammonia solution after dissolving the silver halide and the silver halide, and determining the amount of silver present in the obtained supernatant by a high frequency induction plasma mass spectrometer. (ICP-MS), high frequency induction plasma emission spectroscopy (ICP-AES), or atomic absorption. From the difference between the amount of metal contained in the silver halide after surface dissolution and the total amount of silver halide not dissolved, the amount of metal per mole of silver halide present in about 3% of the grain surface can be determined. it can. Metal quantification methods include an aqueous solution of ammonium thiosulfate, an aqueous solution of sodium thiosulfate, or an aqueous solution of potassium cyanide, and a matrix-matched ICP-MS method.
An ICP-AES method or an atomic absorption method can be used.
Among them, potassium cyanide as a solvent and ICP-MS (FISON Elemental An) as an analyzer.
alysis (manufactured by ALYSIS Co., Ltd.).
After dissolving 0 mg in 5 ml of 0.2N potassium cyanide,
An internal standard element Cs solution is added so as to be 10 ppb,
The measurement sample is made up to a volume of 100 ml with ultrapure water. Then, the metal in the measurement sample is quantified by ICP-MS using a calibration curve obtained by combining a matrix using metal-free silver halide. At this time, the exact amount of silver in the measurement sample was obtained by diluting the measurement sample diluted 100 times with ultrapure water to I
It can be quantified by CP-AES or atomic absorption. After such dissolution of the grain surface, the silver halide grains are washed with ultrapure water, and the dissolution of the grain surface is repeated in the same manner as described above, whereby the metal in the silver halide grain internal direction is formed. The quantity can be determined.

By combining the above-mentioned ultrathin section preparation method and the above-described metal determination method, the metal doped in the tabular grains of the present invention can be determined.

The preferred content of the metal dopant in the tabular grains of the present invention is 1 × 10 ^-9 per mol of silver halide.
Mol to 1 × 10 ^-4 mol, more preferably 1 × 10 ^-4 mol.
^-8 mol to 1 × 10 ^-5 mol.

In the present invention, the metal dopant content of the tabular grains to be mixed is substantially constant. The phrase “the metal dopant content is substantially constant” means that the ratio between the smallest and the largest metal dopant contained in the mixed tabular grains is 0.77 or more and 1.3 or less. Within this range, it has been found that the effects of the present invention, particularly the exposure characteristics, are excellent, and it is more preferable that the ratio be 0.9 or more and 1.1 or less.

The tabular grains of the present invention preferentially contain a metal dopant in the peripheral region.

In the tabular grains of the present invention, the ratio of the amount of metal dopant contained in the peripheral region / the amount of metal dopant contained in the central region of the main plane is at least 10 times, preferably at least 20 times, more preferably at least 20 times. It is 30 times or more.

In the present invention, the metal doping position of the tabular grains to be mixed is substantially constant. The phrase that the metal doping position is substantially constant means that the ratio between the smallest and largest metal dopant amounts detected from the peripheral region of the mixed tabular grains is 0.77 or more and 1.3 or less. To tell.

The effect of the metal dopant is effectively exhibited by adding the metal dopant to the base grains in a state of being doped in the silver halide fine grain emulsion in advance. At this time, the concentration of the metal dopant per mole of the silver halide fine particles was 1
X 10 ^-1 mol to 1 x 10 ^-7 mol is preferred, and 1 x 10 ^-3 mol.
The mole is more preferably from 1 to 10 ⁵ mol.

As a method of doping silver halide fine particles with a metal dopant in advance, it is preferable to form fine particles with the metal dopant dissolved in a halide solution.

The halogen composition of the silver halide fine grains may be any of silver bromide, silver iodide, silver chloride, silver iodobromide, silver chlorobromide, and silver chloroiodobromide. It is preferable that

The silver halide fine particles containing the metal dopant can be deposited on the base grains at any time between the formation of the base grains and before the start of chemical sensitization. The period before the start is particularly preferable. By adding the fine grain emulsion in a state where the salt concentration of the base emulsion is low, the silver halide fine grains are deposited together with the metal dopant in a portion where the activity of the base grains is highest. That is, it can be efficiently deposited on the peripheral region including the corners and edges of the tabular grains of the present invention. This deposition does not mean that the silver halide fine particles are aggregated and adsorbed on the base particles as they are, but the silver halide fine particles are dissolved in the reaction system in which the silver halide fine particles and the base particles coexist, and are deposited on the base particles. Regenerating as silver halide. That is, when a part of the emulsion obtained by the above method was taken out and observed with an electron microscope, no silver halide fine particles were observed, and no epitaxial protrusions were observed on the surface of the base particles. Say.

The silver halide fine particles to be added are preferably added in an amount of 1 × 10 ⁻⁷ mol to 0.5 mol per mol of base grains, preferably 1 × 10 ⁻⁵ mol to 1 × 10 ⁻¹ mol. More preferably, the amount of silver is added.

Physical ripening conditions for depositing silver halide fine grains can be arbitrarily selected from 30 ° C. to 70 ° C./10 minutes to 60 minutes.

The tabular grains of the present invention may be either grains whose latent image is mainly formed on the surface or grains mainly formed inside the grain.

The tabular grains of the present invention are produced in the presence of a dispersion medium, that is, in a solution containing the dispersion medium. here,
The aqueous solution containing a dispersion medium refers to an aqueous solution in which a protective colloid is formed in an aqueous solution by gelatin or another substance capable of forming a hydrophilic colloid (a substance capable of serving as a binder), and preferably contains colloidal protective gelatin. Solution.

In the practice of the present invention, when gelatin is used as the protective colloid, the gelatin may be either lime-treated or acid-treated. The details of the method for producing gelatin are described in Arthur Guice, The Macromolecular Chemistry of Gelatin (Academic Press, 1964).

Examples of hydrophilic colloids other than gelatin that can be used as a protective colloid include gelatin derivatives, graft polymers of gelatin with other polymers,
Proteins such as albumin and casein; cellulose derivatives such as hydroxyethylcellulose, carboxymethylcellulose and cellulose sulfates; sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-
There are various kinds of synthetic hydrophilic polymer substances such as homo- or copolymers such as vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole and polyvinylpyrazole.

In the case of gelatin, it is preferable to use gelatin having a jelly strength of 200 or more in a puggy method.

In the present invention, the tabular grains are formed during the step of forming and / or growing the grains, in the form of cadmium salts, zinc salts, lead salts, thallium salts, iron salts, rhodium salts, iridium salts, indium salts (complex salts). Metal ions by using at least one selected from the group consisting of these metal elements.

Means for forming the tabular grains of the present invention include:
Various methods well known in the art can be used. That is, any combination of the single jet method, the controlled double jet method, the controlled triple jet method, etc. can be used, but in order to obtain advanced monodisperse grains, it is necessary to produce silver halide grains. It is important to control the pAg in the liquid phase to be adjusted according to the growth rate of the silver halide grains.
As the pAg value, a region of 7.0 to 12 is used, and preferably a region of 7.5 to 11 can be used.

In determining the rate of addition, refer to
No.-48521, and the technology described in JP-A-58-49938 can be referred to.

The step of preparing tabular grains of the present invention is roughly classified into a nucleation step, an ripening step (nucleus ripening step) and a subsequent growing step. It is also possible to separately grow a previously prepared nuclear emulsion (or seed emulsion). The growth process may include several stages, such as a first growth process and a second growth process. The growth process of the tabular grains of the present invention means all growth processes from the nucleus (or seed) formation to the end of grain growth, and the start of growth refers to the start of the growth process.

In the production of the tabular grains of the present invention, a known silver halide solvent such as ammonia, thioether, thiourea or the like may be present, or a silver halide solvent may not be used.

In the tabular grains of the present invention, in order to form dislocation lines selectively in the outer peripheral region, an iodine ion source (for example, silver iodide) for introducing dislocation lines into the outer peripheral region in the growth step is used. It is important to increase the pAg in the grain growth after adding the fine particles and the iodine ion releasing agent to the base grains. However, if the pAg is too high, so-called Ostwald ripening proceeds simultaneously with the grain growth, and the tabular grains are reduced. The monodispersity deteriorates. Therefore, pA when forming the outer peripheral region of the tabular grains in the growth step
g is preferably from 8 to 12, and more preferably from 9.5 to 11. When an iodine ion releasing agent is used as an iodine ion source, dislocation lines can be effectively formed in the outer peripheral region by increasing the amount of iodine ion releasing agent. The amount of the iodide ion releasing agent to be added is preferably 0.5 mol or more per mol of silver halide, more preferably 2 to 5 mol.

The tabular grains in the present invention may be those from which unnecessary soluble salts have been removed after the growth of the silver halide grains has been completed, or may be those which are still contained.

As in the method described in JP-A-60-138538, desalting can be carried out at any point during silver halide growth. When removing the salts, use Research Disclosure (Research Disc).
Closure (hereinafter abbreviated as RD) 17643 No. II. More specifically, in order to remove the soluble salt from the emulsion after the formation of the precipitate or after the physical ripening, it is possible to use a Noudel washing method performed by gelling gelatin, and inorganic salts, anionic surfactants, Anionic polymer (for example, polystyrene sulfonic acid) or gelatin derivative (for example, acylated gelatin, carbamoylated gelatin, etc.)
A precipitation method (flocculation) using the above method may be used. As a specific example, a method described in JP-A-5-72658 can be preferably used.

The tabular emulsion of the present invention is composed of a mixture of two or more tabular emulsions having different sphere-equivalent average grain sizes, and the mixing ratio thereof can be selected in any range. For example, when two types of tabular emulsions are mixed, the ratio is 90: 1 in terms of silver.
It is preferable to mix at a ratio of 0:10:90,
More preferably, they are mixed at a ratio of 20 to 20:80.
If the ratio is out of the above range, the effect of the silver halide emulsion in a smaller proportion becomes difficult to exert, so that it is not advisable.

The tabular grains of the present invention can be chemically sensitized by a conventional method. That is, sulfur sensitization, selenium sensitization, a noble metal sensitization method using gold or another noble metal compound, or the like can be used alone or in combination.

The tabular grains of the present invention can be optically sensitized to a desired wavelength range using a dye known as a sensitizing dye in the photographic industry. The sensitizing dyes may be used alone or in combination of two or more. A dye which has no spectral sensitizing effect by itself together with the sensitizing dye or a compound which does not substantially absorb visible light and which enhances the sensitizing effect of the sensitizing dye is contained in the emulsion. May be.

The tabular grains of the present invention include an antifoggant,
Stabilizers and the like can be added. It is advantageous to use gelatin as the binder. Emulsion layers and other hydrophilic colloid layers can be hardened and can contain plasticizers, dispersions (latexes) of water-insoluble or soluble synthetic polymers.

A coupler is used in the emulsion layer of the color photographic light-sensitive material. Further, a development accelerator, a developer, a silver halide solvent, a toning agent, a hardening agent, a fogging agent, an antifogging agent, and a coupling with a competing coupler having a color correcting effect and an oxidized form of a developing agent, Compounds that release photographically useful fragments can be used, such as chemical sensitizers, spectral sensitizers, and desensitizers.

The light-sensitive material can be provided with auxiliary layers such as a filter layer, an antihalation layer and an irradiation prevention layer. In these layers and / or the emulsion layers, dyes which flow out of the light-sensitive material or are bleached during the development processing may be contained.

The light-sensitive material can contain a matting agent, a lubricant, an image stabilizer, a formalin scavenger, an ultraviolet absorber, a fluorescent brightener, a surfactant, a development accelerator and a development retarder.

As the support, paper laminated with polyethylene or the like, polyethylene terephthalate film, baryta paper, cellulose triacetate or the like can be used.

[0095]

EXAMPLES The present invention will be described below in detail with reference to examples, but embodiments of the present invention are not limited thereto.

Example 1 << Preparation of Emulsion EM-1 >> [Nucleation Step] The following reaction mother liquor (Gr-1) in a reaction vessel
The pH was adjusted to 1.96 with 1N sulfuric acid while stirring at a stirring rotation speed of 400 rpm using a mixing and stirring apparatus described in JP-A-62-160128. Thereafter, the liquid (S-1) and the liquid (H-1) were added at a constant flow rate for one minute by using a double jet method to form nuclei.

(Gr-1) Alkali-treated inert gelatin (average molecular weight 100,000) 40.50 g Potassium bromide 12.40 g Finish up to 16.2 L with distilled water (S-1) 862.5 g of silver nitrate 4. Finishing to 06 L (H-1) Potassium bromide 604.5 g Finishing to 4.06 L with distilled water [Aging step] After the above nucleation step, add the (G-1) solution, and take 30 minutes to reach 60 ° C. The temperature rose. During this time, the silver potential of the emulsion in the reaction vessel (measured with a silver ion selective electrode using a saturated silver-silver chloride electrode as a reference electrode) was controlled at 6 mV using a 2N potassium bromide solution. Subsequently, the pH was adjusted to 9.3 by adding an aqueous ammonia solution, and after further holding for 7 minutes, the pH was adjusted to 6.1 using an aqueous acetic acid solution. During this period, the silver potential was adjusted to 6 mV using a 2N potassium bromide solution.
Was controlled.

(G-1) Alkali-treated inert gelatin (average molecular weight 100,000) 173.9 g HO (CH ₂ CH ₂ O) _m (CH (CH ₃ ) CH ₂ O) _19.8 (CH ₂ CH ₂ O) _n H (m + n = 9.77) 10 wt% methanol solution 5.80 ml Finish to 4.22 L with distilled water [Growth step] After the ripening step is completed, the above (S-1) liquid and (H-1) While accelerating the flow rate of the solution (the ratio of the addition flow rate at the end to the addition at the start is about 12 times)
Added in 37 minutes. After the completion of the addition, the solution (G-2) was added, and the stirring speed was adjusted to 550 rpm, and then the solution (S-2) and the solution (H-2) were accelerated while increasing the flow rates (at the time of completion). (The ratio of the addition flow rates at the start was about twice). During this time, the silver potential of the emulsion was controlled at 6 mV using a 2N potassium bromide solution. After the addition was completed, the emulsion temperature in the reaction vessel was lowered to 40 ° C. over 15 minutes. Thereafter, the solution (Z-1) and then the solution (SS) were added, the pH was adjusted to 9.3 using an aqueous potassium hydroxide solution, and iodine ions were released while aging for 4 minutes. Thereafter, the pH was adjusted to 5.0 using an aqueous acetic acid solution, and then the silver potential in the reaction vessel was adjusted to −39 mV using a 3N potassium bromide solution. 3) The solution was added for 25 minutes while accelerating the flow rate (the ratio of the addition flow rate at the end to the start was about 1.2 times).

(S-2) Silver nitrate 2.10 kg Finished to 3.53 L with distilled water (H-2) Potassium bromide 859.5 g Potassium iodide 24.45 g Finished to 2.11 L with distilled water (H-3) Potassium bromide 587.0 g Potassium iodide 8.19 g Finish up to 1.42 L with distilled water (G-2) Ossein gelatin 284.9 g HO (CH ₂ CH ₂ O) _m (CH (CH ₃ ) CH ₂ O) _19.8 (CH ₂ CH ₂ O) _n H (m + n = 9.77) 10% by weight methanol solution 7.75 ml Finish up to 1.93 L with distilled water (Z-1) 83.4 g of sodium p-iodoacetamidobenzenesulfonate Finish with 1.00 L with distilled water (SS) 29.0 g with sodium sulfite Finish with 0.30 L with distilled water After desalting according to the method described above, gelatin was added, the emulsion temperature was adjusted to 50 ° C., the pH was adjusted to 7.00, the pAg was adjusted to 9.10, and the (F-1) solution was added, followed by aging for 20 minutes. .
Thereafter, the temperature was lowered to 40 ° C. to adjust the pH to 5.80 and the pAg to 8.06. The emulsion thus obtained was treated with EM-1.
And

From the electron micrograph of the obtained emulsion particles,
Sphere-equivalent average particle size 0.90 μm, average aspect ratio 7.
2. It was confirmed that the particles were tabular particles having a coefficient of variation of 13.4% in average spherical equivalent particle diameter.

(F-1) Fine grain emulsion (*) composed of K ₂ IrCl ₆ -doped silver bromide grains (average grain size: 0.05 μm) 4.70 g * The preparation method of the fine grain emulsion F-2 is as follows. : 6.0% by weight gelatin solution containing 0.06 mol of potassium bromide 5
An aqueous solution 20 containing 7.06 mol of silver nitrate in 000 ml
00 ml, 7.06 mol of potassium bromide and 2.2 ×
2000 ml of an aqueous solution containing 10 ^-5 mol of K ₂ IrCl ₆
Was added over 10 minutes. During the fine particle formation, the pH was controlled at 2.0 using nitric acid, and the temperature was controlled at 40 ° C. After the formation of the particles, the pH was adjusted to 6.0 using an aqueous solution of sodium carbonate. The finished weight was 12.53 kg.

<< Preparation of Emulsion EM-2 >> The addition amount of the solution (Z-1) used in the growth step of the emulsion EM-1 was doubled, and the pH was adjusted to 10.3 to adjust the iodine ion. Emulsion EM-2 was prepared in the same manner as in production of emulsion EM-1, except that EM-2 was released. From the electron micrograph of the obtained emulsion particles, the sphere-equivalent average particle diameter was 0.89 μm, the average aspect ratio was 7.1, and the variation coefficient of the sphere-equivalent average particle diameter was 13.0.
% Tabular grains.

<< Preparation of Emulsion EM-3 >> In the growth step of the emulsion EM-1, the emulsion temperature in the reaction vessel was lowered to 40 ° C. in 15 minutes, and then the solution (Z-1) was added. Instead, the silver potential in the reaction vessel was adjusted to −39 mV using a 3N potassium bromide solution, and the solutions (S-2) and (H-3) were accelerated while increasing the flow rates (at the end and at the start). (The ratio of the addition flow rate is about 1.2 times). When the addition time has elapsed for 15 minutes, the addition is suspended once, and the (Z-1) solution is added in a double amount,
Next, (SS) solution was added, the pH was adjusted to 9.3 with an aqueous solution of potassium hydroxide, and iodine ions were released while aging for 4 minutes. Thereafter, the pH is adjusted to 5.0 using an aqueous acetic acid solution, and the flow rates of the solution (S-2) and the solution (H-3) are accelerated (the ratio of the addition flow at the end to the start is about 1.
(2x) was added in 10 minutes. Other than that, Emulsion EM-3 was prepared by the same manufacturing method as Emulsion EM-1. From the electron micrograph of the obtained emulsion particles, it was confirmed that they were tabular grains having a sphere-equivalent average particle diameter of 0.90 μm, an average aspect ratio of 7.0, and a coefficient of variation of the sphere-equivalent average particle diameter of 13.7%. .

<< Preparation of Emulsion EM-4 >> In the growth step of Emulsion EM-3, the amount of (Z-1) solution was returned to the same amount as in the preparation of EM-1, and the pH was adjusted to 10.3. Emulsion EM-4 was prepared in the same manner as in emulsion EM-3, except that iodine ions were released. From the electron micrograph of the obtained emulsion particles, the sphere-equivalent average particle size was 0.89 μm,
Average aspect ratio 7.2, Coefficient of variation of spherical average particle diameter 1
It was confirmed that the grains were 3.3% tabular grains.

<< Preparation of Emulsion EM-5 >> In the growth step of Emulsion EM-4, the amount of solution (Z-1) was doubled, and
Emulsion EM-5 was prepared in the same manner as Emulsion EM-4, except that the amount of K ₂ IrCl ₆ used at the time of preparing solution (F-1) added at the end of the desalting step was increased by 200 times. did. From the electron micrograph of the obtained emulsion particles, the sphere-equivalent average particle diameter was 0.88 μm, the average aspect ratio was 6.8,
It was confirmed that the particles were tabular grains having a coefficient of variation of a sphere-equivalent average particle diameter of 12.9%.

<< Preparation of Emulsion EM-6 >> In the step of preparing Emulsion EM-5, K ₂ used in the preparation of solution (F-1) was used.
The amount of IrCl ₆ added was returned to the same amount as in the preparation of EM-1,
Further, after adding the solution (F-1) at the end of the desalting step, the emulsion temperature was raised to 50 ° C., the pH was adjusted to 5.90, the pAg was adjusted to 8.00, and the mixture was aged for 20 minutes. Emulsion EM
Emulsion EM-6 was prepared by the same manufacturing method as that of EM-5. From the electron micrograph of the obtained emulsion particles, it was confirmed that they were tabular grains having a sphere-equivalent average particle diameter of 0.89 μm, an average aspect ratio of 7.1, and a coefficient of variation of the sphere-equivalent average particle diameter of 13.1%. .

<< Preparation of Emulsion EM-7 >> In the growth step of Emulsion EM-1, Emulsion E-7 was prepared in the same manner as Emulsion EM-1 except that the amount of solution (Z-1) was doubled.
M-7 was prepared. From the electron micrograph of the obtained emulsion particles, it was confirmed that they were tabular grains having a sphere-equivalent average particle diameter of 0.90 μm, an average aspect ratio of 6.9, and a coefficient of variation of the sphere-equivalent average particle diameter of 13.0%. .

<< Preparation of Emulsion EM-8 >> In the step of preparing Emulsion EM-6, K ₂ used in the preparation of Solution (F-1) was used.
Emulsion E except that the addition amount of IrCl ₆ was increased 200 times.
Emulsion EM-8 was prepared by the same manufacturing method as that for M-6. From the electron micrograph of the obtained emulsion particles, it was confirmed that they were tabular grains having an average sphere-equivalent particle size of 0.91 μm, an average aspect ratio of 7.3, and a coefficient of variation of the sphere-equivalent average particle size of 13.9%. .

<< Preparation of Emulsion EM-9 >> In the growth step of Emulsion EM-4, Emulsion E was prepared in the same manner as Emulsion EM-4 except that the addition amount of Solution (Z-1) was doubled.
M-9 was prepared. From the electron micrograph of the obtained emulsion particles, it was confirmed that the emulsion particles were tabular grains having an average sphere-equivalent particle size of 0.90 μm, an average aspect ratio of 7.1, and a coefficient of variation of the sphere-equivalent average particle size of 13.6%. .

<< Preparation of Emulsion EM-10 >> In the nucleus forming step of the emulsion EM-1, the addition amounts of the solution (S-1) and the solution (H-1) were adjusted. ) Emulsion EM except that the amounts of solution and aqueous ammonia were adjusted.
Emulsion EM-10 was prepared by the same production method as in Emulsion-1. From the electron micrograph of the obtained emulsion particles, it was confirmed that the emulsion particles were tabular grains having an average sphere-equivalent particle diameter of 0.69 μm, an average aspect ratio of 7.0, and a coefficient of variation of the sphere-equivalent average particle diameter of 13.1%. .

<< Preparation of Emulsion EM-11 >> In the nucleus forming step of the emulsion EM-2, the addition amounts of the solution (S-1) and the solution (H-1) were adjusted. ) Emulsion EM except that the amounts of solution and aqueous ammonia were adjusted.
Emulsion EM-11 was prepared in the same manner as in Preparation Example-2. From the electron micrograph of the obtained emulsion particles, it was confirmed that they were tabular grains having a sphere-equivalent average particle diameter of 0.70 μm, an average aspect ratio of 7.0, and a coefficient of variation of the sphere-equivalent average particle diameter of 12.7%. .

<< Preparation of Emulsion EM-12 >> In the nucleus forming step of the emulsion EM-3, the addition amounts of the solution (S-1) and the solution (H-1) were adjusted. ) Emulsion EM except that the amounts of solution and aqueous ammonia were adjusted.
Emulsion EM-12 was prepared in the same manner as in Preparation Example-3. From the electron micrograph of the obtained emulsion particles, it was confirmed that they were tabular grains having a sphere-equivalent average particle diameter of 0.69 μm, an average aspect ratio of 7.2, and a coefficient of variation of the sphere-equivalent average particle diameter of 13.9%. .

<< Preparation of Emulsion EM-13 >> In the nucleus forming step of the emulsion EM-4, the addition amounts of the solution (S-1) and the solution (H-1) were adjusted. ) Emulsion EM except that the amounts of solution and aqueous ammonia were adjusted.
Emulsion EM-13 was prepared in the same manner as in Preparation Example-4. From the electron micrograph of the obtained emulsion particles, it was confirmed that they were tabular grains having a sphere-equivalent average particle diameter of 0.69 μm, an average aspect ratio of 7.0, and a coefficient of variation of the sphere-equivalent average particle diameter of 13.0%. .

<< Preparation of Emulsion EM-14 >> In the nucleus forming step of the emulsion EM-5, the addition amounts of the solution (S-1) and the solution (H-1) were adjusted. ) Emulsion EM except that the amounts of solution and aqueous ammonia were adjusted.
Emulsion EM-14 was prepared by the same manufacturing method as that of Emulsion -5. From the electron micrograph of the obtained emulsion particles, it was confirmed that the emulsion particles were tabular grains having an average sphere-equivalent particle diameter of 0.71 μm, an average aspect ratio of 6.9, and a coefficient of variation of the sphere-equivalent average particle diameter of 13.2%. .

<< Preparation of Emulsion EM-15 >> In the nucleus forming step of the emulsion EM-6, the addition amounts of the solution (S-1) and the solution (H-1) were adjusted. ) Emulsion EM except that the amounts of solution and aqueous ammonia were adjusted.
Emulsion EM-15 was prepared by the same manufacturing method as that of -6. From the electron micrograph of the obtained emulsion particles, it was confirmed that the emulsion particles were tabular grains having an average sphere-equivalent particle size of 0.70 μm, an average aspect ratio of 7.3, and a coefficient of variation of the sphere-equivalent average particle size of 13.5%. .

<< Preparation of Emulsion EM-16 >> In the nucleus forming step of the emulsion EM-7, the addition amounts of the solution (S-1) and the solution (H-1) were adjusted. ) Emulsion EM except that the amounts of solution and aqueous ammonia were adjusted.
Emulsion EM-16 was prepared by the same manufacturing method as that of -7. From the electron micrograph of the obtained emulsion particles, it was confirmed that they were tabular grains having a sphere-equivalent average particle diameter of 0.70 μm, an average aspect ratio of 7.1, and a coefficient of variation of the sphere-equivalent average particle diameter of 13.3%. .

<< Preparation of Emulsion EM-17 >> In the nucleus forming step of the emulsion EM-8, the addition amounts of the solution (S-1) and the solution (H-1) were adjusted. ) Emulsion EM except that the amounts of solution and aqueous ammonia were adjusted.
Emulsion EM-17 was prepared by the same manufacturing method as that of -8. From the electron micrograph of the obtained emulsion particles, it was confirmed that the emulsion particles were tabular grains having an average sphere-equivalent particle diameter of 0.68 μm, an average aspect ratio of 7.0, and a coefficient of variation of the sphere-equivalent average particle diameter of 13.1%. .

<< Preparation of Emulsion EM-18 >> In the nucleus forming step of the emulsion EM-9, the addition amounts of the solution (S-1) and the solution (H-1) were adjusted. ) Emulsion EM except that the amounts of solution and aqueous ammonia were adjusted.
Emulsion EM-18 was prepared by the same manufacturing method as that of Emulsion -9. From the electron micrograph of the obtained emulsion particles, it was confirmed that they were tabular grains having a sphere-equivalent average particle diameter of 0.70 μm, an average aspect ratio of 7.0, and a coefficient of variation of the sphere-equivalent average particle diameter of 13.9%. .

The results of analysis of the compositions, structures, and the like of the emulsions EM-1 to EM-18 are summarized in Table 1.

[0120]

[Table 1]

Example 2 (Preparation of photosensitive material sample) (Preparation of support) Unless otherwise specified, "parts" in Examples of preparation of a support means "parts by weight".

To 100 parts of dimethyl 2,6-naphthalenedicarboxylate and 60 parts of ethylene glycol, 0.1 part of calcium acetate hydrate was added as a transesterification catalyst, and a transesterification reaction was carried out according to a conventional method. To the obtained product, 0.05 parts of antimony trioxide and 0.03 parts of trimethyl phosphate were added. Then, the temperature was gradually increased and the pressure was reduced, and polymerization was performed at 290 ° C. and 0.05 mmHg,
Polyethylene-2,6-naphthalate having an intrinsic viscosity of 0.60 was obtained.

This was vacuum-dried at 150 ° C. for 8 hours, then melt-extruded in a layer form from a T-die at 300 ° C., brought into close contact with a cooling drum at 50 ° C. while applying static electricity, and cooled and solidified. Obtained. This unstretched sheet was stretched 3.3 times in the machine direction at 135 ° C. using a roll-type longitudinal stretching machine.

The obtained uniaxially stretched film was stretched in a first stretching zone at 145 ° C. by 50% of the total transverse stretching ratio using a tenter type transverse stretching machine, and further stretched at a second stretching zone at 155 ° C. at a total transverse stretching ratio of 3%. Stretched to 3 times. Then 10
Heat treatment at 0 ° C for 2 seconds, and further heat treatment zone 200 ° C
For 5 seconds and a second heat setting zone at 240 ° C. for 15 seconds. Next, the film was gradually cooled to room temperature over 30 seconds while relaxing in a transverse direction by 5% to obtain a polyethylene naphthalate film having a thickness of 85 μm.

This is wound around a stainless steel core, and
A heat treatment (annealing treatment) was performed at 10 ° C. for 48 hours to produce a support.

(Coating of Undercoat Layer)
W / m ² / min corona discharge treatment alms, the following under引塗coating solution B-1 on one side was coated to a dry film thickness of 0.4 .mu.m, Corona 12W / m ² / min thereon After the discharge treatment, the undercoating coating solution B-2 shown below was dried to a thickness of 0.06.
It was applied to a thickness of μm.

On the other surface subjected to the corona discharge treatment of 12 W / m ² / min, the following undercoating coating solution B-3 was applied to a dry film thickness of 0.2 μm, and 12 W / m ² / min. ^Two
/ Min corona discharge treatment and the following undercoating coating solution B-
4 was applied to a dry film thickness of 0.2 μm.

Each of the layers was dried at 90 ° C. for 10 seconds after the application, and after applying 4 layers, heat treatment was performed at 110 ° C. for 2 minutes, followed by cooling at 50 ° C. for 30 seconds.

<Undercoat Coating Solution B-1> 125 g of a butyl acrylate / t-butyl acrylate / styrene / 2-hydroxyethyl acrylate copolymer (30/20/25/25 wt%) latex liquid (solid content 30%) Compound (UL-1) 0.4 g Hexamethylene-1,6-bis (ethylene urea) 0.05 g Finish to 1 liter with water <Subbing coating solution B-2> Hydroxidation of styrene / maleic anhydride copolymer Sodium aqueous solution (solid content: 6%) 50 g Compound (UL-1) 0.6 g Compound (UL-2) 0.09 g Silica particles (average particle size: 3 μm) 0.2 g Finish to 1 liter with water <Undercoat coating solution B -3> butyl acrylate / t-butyl acrylate / styrene / 2-hydroxyethyl acrylate copolymer (30/20/25/25 weight ) Latex solution (solid content 30%) 50 g Compound (UL-1) 0.3 g Hexamethylene-1,6-bis (UL-1 finish to 1 liter with ethylene urea) 1.1 g Water: o, p- (C _{9 H 19) 2 C 6 H} 3 O (CH 2 CH 2 O) 12 SO 3 Na UL-2: CH 3 SO 2 O (CH 2) 3 OSO 2 CH 3 < under引塗coating solution B-4> tin oxide Aqueous dispersion of antimony oxide composite fine particles (average particle size: 0.2 μm) (solid content: 40% by weight) 109 g Aqueous dispersion A * 67 g Finished to 1 liter with water * 60 mol% of dimethyl terephthalate as isocarboxylic acid component, isophthalic 30 mol% of dimethyl acid, 10 mol% of sodium salt of dimethyl 5-sulfoisophthalate, 50 mol% of ethylene glycol and 50 mol% of diethylene glycol as glycol components are commonly used. It engaged. The copolymer was stirred in hot water at 95 ° C. for 3 hours to obtain a 15% by weight aqueous dispersion A.

(Coating of Transparent Magnetic Recording Layer) <Preparation of Magnetic Coating Solution 1> Composition (A) Co-coated γ-Fe ₂ O ₃ (major axis: 0.15 μm, minor axis: 0.03 μm, specific surface area: 40 m) ² / g, Hc = 900 Oersted) 5 parts Diacetyl cellulose (degree of acetylation = 55%, Mw = 180,000) 100 parts α-alumina (average particle diameter 0.3 μm) 10 parts Acetone 780 parts Cyclohexanone 340 parts Composition ( A) was dispersed in a sand mill for 40 hours, and then filtered through a filter having an average pore size of 10 μm to obtain a magnetic coating material.

Composition (B) Hardener (manufactured by Nippon Polyurethane Co., Ltd .: CL, solid content: 75%) 20 parts Cyclohexanone 45 parts The composition (B) was mixed using a disper so as not to entrap air.

The composition (B) was continuously added to and mixed with the magnetic paint to obtain a magnetic coating liquid.

The obtained magnetic coating solution was applied to a PEN support on which the above-mentioned subbing layer and antistatic layer had been coated, to a dry film thickness of 0.
It was applied and dried so as to have a thickness of 8 μm.

(Coating of Photographic Emulsion) PEN prepared above
On the opposite side of the support (magnetic recording medium) from the magnetic recording layer side,
A subbing layer coated with the subbing coating solutions B-1 and B-2 under the same conditions is provided, and each layer having the composition shown below is formed sequentially from the support side to obtain a multilayer color photographic light-sensitive material. Made the material.

Multilayer color photographic light-sensitive material samples 101 to 11
Emulsion EM-1 prepared in Example 1 for the preparation of Emulsion No. 8
EM-18 were optimally subjected to gold-sulfur sensitization, and the emulsions EM-1 to EM-18 were mixed in the combinations shown in Table 2 using these emulsions. 50:50 in terms of silver).

[0136]

[Table 2]

The structure of the multilayer color photographic light-sensitive material sample 101 is shown below. Samples 102 to 118 were prepared in the same manner except that the emulsion constitution was changed to that shown in Table 2.

In all of the following descriptions, the amount added in the silver halide photographic material is 1 m ² unless otherwise specified.
Indicates the number of grams per unit. In addition, silver halide and colloidal silver are shown in terms of the amount of silver, and sensitizing dyes are shown in moles per mole of silver halide.

First Layer (Antihalation Layer) Black Colloidal Silver 0.16 UV Absorber UV-1 0.3 Colored Magenta Coupler CM-1 0.044 High Boiling Solvent OIL-1 0.044 Gelatin 1.33 Second Layer (intermediate layer) Antifouling agent AS-1 0.16 High boiling point solvent OIL-1 0.20 Gelatin 1.40 Third layer (low-sensitivity red-sensitive layer) Silver iodobromide a 0.12 Iodobromide Silver b 0.50 sensitizing dye SD-1 3.0 × 10 ^-5 sensitizing dye SD-4 1.5 × 10 ^-4 sensitizing dye SD-3 3.0 × 10 ^-4 sensitizing dye SD-6 3.0 × 10 ^-6 Cyan coupler C-1 0.51 Colored cyan coupler CC-1 0.047 High boiling point solvent OIL-2 0.45 Stain inhibitor AS-2 0.005 Gelatin 1.40 4th layer ( Medium sensitivity red-sensitive layer) Silver iodobromide c 0.64 Sensitized Containing SD-1 3.0 × ^{10 -5} Sensitizing dye SD-2 1.5 × ^{10 -4} Sensitizing dye SD-3 3.0 × 10 ^-4 Cyan coupler C-2 0.22 Colored cyan couplers CC- 1 0.028 DIR compound DI-1 0.002 High boiling solvent OIL-2 0.21 Stain inhibitor AS-3 0.006 Gelatin 0.87 Fifth layer (highly sensitive red-sensitive layer) Silver iodobromide c 0.13 silver iodobromide d 1.14 sensitizing dye SD-1 3.0 × 10 ^-5 sensitizing dye SD-2 1.5 × 10 ^-4 sensitizing dye SD-3 3.0 × 10 ^{− 4} Cyan coupler C-2 0.085 Cyan coupler C-3 0.084 Colored cyan coupler CC-1 0.029 DIR compound DI-1 0.027 High boiling solvent OIL-2 0.23 Stain inhibitor AS-30 .013 gelatin 1.23 6th layer (middle layer) high boiling Point solvent OIL-1 0.29 Stain inhibitor AS-1 0.23 Gelatin 1.00 7th layer (low-sensitivity green color-sensitive layer) Silver iodobromide a 0.245 Silver iodobromide b 0.105 Increase Sensitizing dye SD-6 5.0 × 10 ^-4 Sensitizing dye SD-5 5.0 × 10 ^-4 Magenta coupler M-1 0.21 Colored magenta coupler CM-2 0.039 High boiling point solvent OIL-1 25 Antifouling agent AS-2 0.003 Antifouling agent AS-4 0.063 Gelatin 0.98 Eighth layer (Medium sensitivity green color-sensitive layer) Silver iodobromide e 0.87 Sensitizing dye SD-7 3 0.0 × 10 ^-4 sensitizing dye SD-8 6.0 × 10 ^-5 sensitizing dye SD-9 4.0 × 10 ^-5 Magenta coupler M-1 0.17 Colored magenta coupler CM-2 0.048 Colored Magenta coupler CM-3 0.059 DIR compound DI 2 0.012 High boiling solvent OIL-1 0.29 Stain inhibitor AS-4 0.05 Stain inhibitor AS-2 0.005 Gelatin 1.43 Ninth layer (highly sensitive green color-sensitive layer) Emulsion EM- 0.595 Any of emulsions EM-10 to EM-18 (described in Table 2) 0.595 Sensitizing dye SD-7 4.0 × 10 ^-4 Sensitization Dye SD-8 8.0 × 10 ^-5 Sensitizing dye SD-9 5.0 × 10 ^-5 Magenta coupler M-1 0.09 Colored magenta coupler CM-3 0.020 DIR compound DI-3 0.005 High Boiling point solvent OIL-1 0.11 Antifouling agent AS-4 0.026 Antifouling agent AS-5 0.014 Antifouling agent AS-6 0.006 Gelatin 0.78 10th layer (yellow filter layer) Yellow colloidal silver 0.05 High boiling point solvent OIL-1 0.18 Antifouling agent AS-7 0.16 Gelatin 1.00 Eleventh layer (low-sensitivity blue-sensitive layer) Silver iodobromide g 0.29 Silver iodobromide h 0.19 Sensitizing dye SD-10 8.0 × 10 ^-4 sensitizing dye SD-11 3.1 × 10 ^-4 yellow coupler Y-1 0.91 DIR compound DI-4 0.022 High boiling point solvent OIL-1 0.37 Stain prevention Agent AS-2 0.002 Gelatin 1.29 12th layer (high-sensitivity blue-sensitive layer) Silver iodobromide h 0.13 Silver iodobromide i 1.00 Sensitizing dye SD-10 4.4 × 10 ^-4 sensitizing dye SD-11 1.5 × 10 ^-4 yellow coupler Y-1 0.48 DIR compound DI-4 0.019 high boiling point solvent OIL-1 0.21 stain inhibitor AS-2 0.004 gelatin 1.55 13th layer (first protective layer) Silver iodobromide j 0.30 UV absorber UV-1 0.055 UV absorber UV-2 0.110 High boiling point solvent OIL-2 0.63 Gelatin 1.32 14th layer (second protective layer) Polymer PM-1 0.15 Polymer PM-2 04 Slip agent WAX-1 0.02 DIR compound D-1 0.001 Gelatin 0.55 In addition to the above composition, coating aids SU-1, SU-2,
SU-3, dispersing aid SU-4, viscosity modifier V-1, stabilizers ST-1, ST-2, antifoggant AF-1 (polyvinylpyrrolidone, weight average molecular weight: 10,000), A
F-2 (polyvinylpyrrolidone, weight average molecular weight: 1,
100,000), inhibitors AF-3, AF-4, AF-
5. Hardeners H-1, H-2, H-3, H-4 and preservative Ase-1 were added.

The structures of the compounds used in the above samples are shown below.

SU-1: C ₈ F ₁₇ SO ₂ N (C ₃ H ₇ ) CH ₂ COOK SU-2: C ₈ F ₁₇ SO ₂ NH (CH ₂ ) ₃ N ⁺ (CH ₃ ) ₃
Br ^- SU-3: sodium di (2-ethylhexyl) sulfosuccinate SU-4: sodium tri-i-propylnaphthalenesulfonate ST-1: 4-hydroxy-6-methyl-1,3,3
a, 7-Tetrazaindene ST-2: Adenine AF-3: 1-Phenyl-5-mercaptotetrazole AF-4: 1- (4-Carboxyphenyl) -5-mercaptotetrazole AF-5: 1- (3- acetamidophenyl) -5-mercaptotetrazole H-1: _{[(CH 2 = CHSO 2 CH 2} ) 3 CCH 2 SO 2 C
H ₂ CH _{2] 2 NCH 2 CH 2 SO 3 K} H-2: 2,4- dichloro-6-hydroxy -s- triazine sodium _{H-3: CH 2 = CHSO} 2 CH 2 CH (OH) CH 2 SO
_{2 CH = CH 2 H-4} : (CH 2 = CHSO 2 CH 2 CONHCH 2 -) 2 OIL-1: tricresyl phosphate OIL-2: Di (2-ethylhexyl) phthalate AS-1: 2,5-Bis (1,1-dimethyl-4-hexyloxycanobonylbutyl) hydroquinone AS-2: dodecyl gallate AS-3: docosyl gallate AS-4: 2-octyloxy-5-t-octyl-
N, N-dibutylaniline AS-5: 2,5-di-t-octylhydroquinone AS-6: 2,5-di-t-octyl-1,4-quinone

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Table 3 shows the features of the silver iodobromide.

[0150]

[Table 3]

As a preferred example of forming silver halide grains of the present invention, a production example of silver iodobromide d is shown below.

(Preparation of Seed Emulsion-1) JP-B-58-58
No. 288 and No. 58-58289, a silver nitrate aqueous solution (1.161 mol) and a mixed aqueous solution of potassium bromide and potassium iodide (potassium iodide) were added to the following solution A1 adjusted to 35 ° C. 2 mol%) was added over 2 minutes by a double jet method while keeping the silver potential (measured with a silver ion selective electrode using a saturated silver-silver chloride electrode as a reference electrode) at 0 mV to perform nucleation. Subsequently, the temperature of the solution was raised to 60 ° C. over a period of 60 minutes, and the pH was adjusted to 5.0 with an aqueous sodium carbonate solution.
2 mol) and a mixed aqueous solution of potassium bromide and potassium iodide (potassium iodide 2 mol%) was added over 42 minutes by a double jet method while keeping the silver potential at 9 mV. After the addition was completed, the temperature was lowered to 40 ° C., and desalting and washing were immediately performed using a normal flocculation method.

The obtained seed crystal emulsion had an average sphere-equivalent diameter of 0.24 μm, an average aspect ratio of 4.8, and a maximum side ratio of 1.0% or more of 90% or more of the total projected area of silver halide grains.
~ 2.0 hexagonal tabular grains.
This emulsion is referred to as seed emulsion-1.

Solution A1 Ossein gelatin 24.2 g Potassium bromide 10.8 g Surfactant EO (10% ethanol solution) 6.78 ml 10% nitric acid 114 ml Water 9657 ml EO: HO (CH ₂ CH ₂ O) _m (CH (CH (CH ₃ ) CH ₂ O) _19.8 (CH ₂ CH ₂ O) _n H (m + n = 9.77) (Preparation of silver iodide fine grain emulsion SMC-1) 6.0 weight containing 0.06 mol of potassium iodide While vigorously stirring 5 liters of a 5% aqueous gelatin solution, 2 liters of a 7.06 mol aqueous silver nitrate solution and a 7.06 mol aqueous potassium iodide solution were added over 10 minutes. During this time, the pH was controlled at 2.0 using nitric acid, and the temperature was controlled at 40 ° C. After the preparation of the particles, the pH was adjusted to 5.0 using an aqueous sodium carbonate solution. The average particle size of the obtained silver iodide fine particles is 0.05 μm.
Met. This emulsion is designated as SMC-1.

(Preparation of silver iodobromide d) 700 ml of a 4.5% by weight aqueous solution of inert gelatin containing 0.178 mol of seed crystal emulsion-1 and 0.5 ml of a 10% ethanol solution of surfactant EO At 75 ° C., pAg at 8.4, pH
Was adjusted to 5.0, and particles were formed by the simultaneous mixing method with vigorous stirring according to the following procedure.

1) 2.1 mol silver nitrate aqueous solution and 0.19
5 mol of SMC-1 and an aqueous solution of potassium bromide were added to pAg
While maintaining the pH at 8.4 and the pH at 5.0.

2) Subsequently, the solution was cooled to 60 ° C.
Was adjusted to 9.8. Then, 0.071 mol of SMC
-1 was added and aging was performed for 2 minutes (introduction of dislocation lines).

3) 0.959 mol silver nitrate aqueous solution and 0.1 mol
03 mol of SMC-1 and an aqueous solution of potassium bromide were added to pA
g while maintaining the pH at 9.8 and the pH at 5.0.

Throughout the formation of the particles, each solution was added at an optimum rate so that the formation of new nuclei and the Ostwald ripening between particles did not proceed.

After the completion of the addition, the mixture was washed with water at 40 ° C. using a usual flocculation method, and gelatin was added to redisperse the mixture. The pAg was adjusted to 8.1 and the pH was adjusted to 5.8.

The emulsion obtained had a particle size (cubic 1 of the same volume).
The emulsion was composed of tabular grains having a halogen composition of 0.75 μm in side length, an average aspect ratio of 5.0 and a halogen composition of 2 / 8.5 / X / 3 mol% (X is a dislocation line introduction position) from the inside of the grains. . When this emulsion was observed with an electron microscope, five or more dislocation lines were observed in both the fringe portion and the inside of the grains in 60% or more of the total projected area of the grains in the emulsion. The surface silver iodide content was 6.7 mol%.

After the above-mentioned sensitizing dye is added to the above emulsion and ripened, triphosphine selenide, sodium thiosulfate, chloroauric acid and potassium thiocyanate are added, and the fog-sensitivity relationship is optimized according to a conventional method. Chemical sensitization.

Silver bromoiodides a, b, c, e, g, h, and i were also subjected to spectral sensitization and chemical sensitization in accordance with d above.

A silver halide color photographic light-sensitive material sample was prepared as described above.

<< Evaluation Method >> Each of the obtained photosensitive material samples was evaluated for relative sensitivity, pressure characteristics, and illuminance dependency (suitability) at the time of exposure as described below.

<< Relative Sensitivity >> The relative sensitivity was determined by using a green light (G) and exposing the wedge for sensitometry for 1/200 second, and then performing the following color development processing to obtain a density of Dmin (minimum density) +0.15. Was obtained as a relative value of the reciprocal of the exposure amount which gives the value of (1), and was expressed as a value with the sensitivity of the sample 101 being 100 (a value greater than 100 indicates a higher sensitivity).

<< Relative sensitivity of high illuminance exposure >> The relative sensitivity of the high illuminance exposure was determined by subjecting the wedge exposure for sensitometry to 1 / 10,000 sec. The relative sensitivity of each sample was determined with respect to the value obtained by setting the relative sensitivity of 1/200 second exposure to 100 (the closer the value to the relative sensitivity of 1/200 second exposure in the same sample, the higher the illuminance exposure suitability) Show good things).

<< Relative Sensitivity of Low-Illuminance Exposure >> The relative sensitivity of low-illuminance exposure is as follows. After 8 seconds of sensitometric wedge exposure using green light (G), color development processing is performed. The relative sensitivity of each sample was determined with respect to a value where the relative sensitivity of 200-second exposure was 100 (1 in the same sample).
The closer the value is to the relative sensitivity of / 200 second exposure, the better the low illuminance exposure suitability is.)

<< Pressure Characteristics >> The pressure characteristics are 23 ° C./55%
Under the condition of (relative humidity), using a scratch strength tester (manufactured by Shinto Kagaku Co., Ltd.)
After scanning at a constant speed with a load of g, green light (G)
1/200 wedge exposure for sensitometry using
After the second exposure, the following color development processing is performed, and at the densities of Dmin and Dmin + 0.4, the absolute value ΔD1 (Dmin) and the absolute value ΔD2 (Dmin + 0.4) of the density change of the loaded part are obtained. Sample 10
ΔD1 and ΔD2 of 1 are shown as values each of which is set to 100 (the smaller the value is, the better the value is at 100).

<< Color development processing >> (Processing step) Processing step Processing time Processing temperature Replenishment amount * Color development 3 minutes 15 seconds 38 ± 0.3 ° C. 780 ml Bleaching 45 seconds 38 ± 2.0 ° C. 150 ml Fixing 1 minute 30 38 ± 2.0 ° C. 830 ml Stability 60 seconds 38 ± 5.0 ° C. 830 ml Drying 1 minute 55 ± 5.0 ° C.-* The replenishment amount is a value per 1 m ² of the photosensitive material.

The following color developing solutions, bleaching solutions, fixing solutions, stabilizing solutions and replenishers were used.

<Color developing solution and color developing replenishing solution> Developer replenishing solution Water 800 ml 800 ml Potassium carbonate 30 g 35 g Sodium hydrogen carbonate 2.5 g 3.0 g Potassium sulfite 3.0 g 5.0 g Sodium bromide 1.3 g 0.4 g Potassium iodide 1.2 mg-hydroxylamine sulfate 2.5 g 3.1 g sodium chloride 0.6 g-4-amino-3-methyl-N-ethyl-N-([beta] -hydroxylethyl) aniline sulfate 4.5 g 6 3.3 g Diethylenetriaminepentaacetic acid 3.0 g 3.0 g Potassium hydroxide 1.2 g 2.0 g Add water to make 1 liter, use potassium hydroxide or 20% sulfuric acid to adjust the color developing solution to pH 10.06, and replenish the replenisher. Adjust to pH 10.18.

<Bleach and Bleach Replenisher> Bleach Replenisher Water 700 ml 700 ml 1,3-diaminopropanetetraacetate ammonium (III) ammonium 125 g 175 g ethylenediaminetetraacetic acid 2 g 2 g sodium nitrate 40 g 50 g ammonium bromide 150 g 200 g glacial acetic acid 40 g 56 g of water was added to make up 1 liter, and the bleaching solution was adjusted to pH 4 with ammonia water or glacial acetic acid. In 4, adjust the replenisher to pH 4.0.

<Fixing Solution and Fixing Replenisher> Fixing Solution Replenisher Water 800 ml 800 ml Ammonium thiocyanate 120 g 150 g Ammonium thiosulfate 150 g 180 g Sodium sulfite 15 g 20 g Ethylenediaminetetraacetic acid 2 g 2 g Ammonia water or glacial acetic acid is used to adjust the pH of the fixing solution to 6.2. Then, the pH of the replenisher is adjusted to 6.5, and then water is added to make 1 liter.

<Stabilizing Solution and Stabilizing Replenishing Solution> Water 900 ml p-octylphenol ethylene oxide 10 mol adduct 2.0 g dimethylolurea 0.5 g hexamethylenetetramine 0.2 g 1,2-benzoisothiazolin-3-one 0.1 g siloxane (L-77 manufactured by UCC) 0.1 g ammonia water 0.5 ml After adding water to make 1 liter, the pH was adjusted to 8.0 using ammonia water or 50% sulfuric acid. Adjust to 5.

Table 4 shows the above results.

[0177]

[Table 4]

As is evident from the results shown in Table 4, Samples 101 to 108 of the present invention containing the emulsion of the present invention have high sensitivity and improved pressure characteristics and exposure illuminance suitability. Among them, the sample 102 has a synergistic effect, and it is understood that the sample 102 is particularly excellent.

As described above, according to the present invention, a silver halide photographic emulsion and a silver halide color photographic light-sensitive material having high sensitivity, improved pressure sensitization and pressure desensitization, and excellent exposure illuminance suitability are obtained. be able to.

Example 3 Sample No. 2 of Example 2 115, silver iodobromide d of the fifth layer was changed to any of emulsions EM-1 to EM-9,
Samples 201 to 215 corresponding to Samples 101 to 115 of Example 2 were prepared by using silver iodobromide C of the fifth layer as any one of emulsions EM-10 to EM-18. When evaluation was performed using red light (R) in the same manner as in Example 2, the samples 201 to 208 of the present invention showed the effects of the present invention.

Example 4 Sample No. 2 of Example 2 115, the silver iodobromide i of the twelfth layer is any of emulsions EM-1 to EM-9, and the silver iodobromide h of the twelfth layer is emulsion EM-10 to EM-1.
8, Samples 301 to 315 corresponding to Samples 101 to 115 of Example 2 were produced. When evaluation was performed using blue light (B) in the same manner as in Example 2, the samples 301 to 308 of the present invention showed the effects of the present invention.

[0182]

According to the present invention, it is possible to provide a silver halide emulsion having high sensitivity, excellent pressure characteristics and markedly improved illuminance dependence during exposure, and a silver halide color photographic material using the same. Was.

Claims (5)

[Claims] In a silver halide color photographic material having at least one silver halide emulsion layer on a support, at least one of the silver halide emulsion layers has an average aspect ratio of 1.5 or more. , Sphere equivalent average particle size is 0.2
a silver halide emulsion containing tabular silver halide grains having a mean particle diameter of not less than .mu.m and a coefficient of variation of not less than 30% in sphere equivalent, wherein at least two kinds of silver halide emulsions having different sphere equivalent mean diameters are contained. And a silver halide color photographic light-sensitive material characterized in that the average length of dislocation lines of tabular silver halide grains contained in the two or more emulsions is substantially constant. 2. A silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support, wherein at least one of the silver halide emulsion layers has an average aspect ratio of 1.5 or more. , Sphere equivalent average particle size is 0.2
a silver halide emulsion containing tabular silver halide grains having a mean particle diameter of not less than .mu.m and a coefficient of variation of not less than 30% in sphere equivalent, wherein at least two kinds of silver halide emulsions having different sphere equivalent mean diameters are contained. And a silver halide color photographic light-sensitive material characterized in that the coefficient of variation of the length of dislocation lines of tabular silver halide grains contained in the two or more emulsions is substantially constant. 3. A silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support, wherein at least one of the silver halide emulsion layers has an average aspect ratio of 1.5 or more. , Sphere equivalent average particle size is 0.2
a silver halide emulsion containing tabular silver halide grains having a mean particle diameter of not less than .mu.m and a coefficient of variation of not less than 30% in sphere equivalent, wherein at least two kinds of silver halide emulsions having different sphere equivalent mean diameters are contained. A silver halide color photographic light-sensitive material characterized in that the maximum silver iodide content in the dislocation line existing region of the tabular silver halide grains contained in the two or more emulsions is substantially constant. 4. A silver halide color photographic material having at least one silver halide emulsion layer on a support, wherein at least one of the silver halide emulsion layers has an average aspect ratio of 1.5 or more. , Sphere equivalent average particle size is 0.2
a silver halide emulsion containing tabular silver halide grains having a mean particle diameter of not less than .mu.m and a coefficient of variation of not less than 30% in sphere equivalent, wherein at least two kinds of silver halide emulsions having different sphere equivalent mean diameters are contained. And a silver halide color photographic light-sensitive material characterized in that the tabular silver halide grains contained in the two or more emulsions have a substantially constant polyvalent metal compound doping amount. 5. A silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support, wherein at least one of the silver halide emulsion layers has an average aspect ratio of 1.5 or more. , Sphere equivalent average particle size is 0.2
a silver halide emulsion containing tabular silver halide grains having a mean particle diameter of not less than .mu.m and a coefficient of variation of not less than 30% in sphere equivalent, wherein at least two kinds of silver halide emulsions having different sphere equivalent mean diameters are contained. A silver halide color photographic light-sensitive material characterized in that tabular silver halide grains contained in the two or more kinds of emulsions have a substantially constant polyvalent metal compound doping position.