JPH0519393A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide the silver halide photographic sensitive material superior in color reproduction performance, sensitivity, gradation, and storage stability by using a combination of flat silver halide grains having specified physical properties and a specified magenta coupler. CONSTITUTION:The flat silver halide grains to be used has a variation coefficient of grain size distribution of <=25% and a variation coefficient of silver iodide content of each grain of <=30%, and an aspect ratio of >=3, and such grains occupy at least 50% of the total silver halide grain projection area. The magenta coupler to be used is represented by formula I in which X is a group to be released by coupling with the oxidation product of a developing agent; and each of Za, Zb, and Zc is optionally substituted methine, =N-, or =NH-.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a photographic light-sensitive material having improved photographic characteristics.

[0002]

2. Description of the Related Art In recent years, in order to improve color reproducibility of silver halide color light-sensitive materials, magenta couplers have been used in place of conventional couplers having a pyrazolone skeleton instead of pyrazoloazoles.

An example of these is US Pat. No. 3,36.
Pyrazolobenzimidazoles described in US Pat. No. 9,897, pyrazolotriazoles described in US Pat. No. 3,725,067, Research Disclosure No. 24, 220
(June 1984), pyrazolotetrazoles,
And Research Disclosure No. 24,230
(June 1984), pyrazolopyrazoles. When these azole type dyes are used, among the absorption of the magenta dye generated by development, the yellow and cyan secondary absorption components are small, color turbidity is reduced, and excellent color reproduction is obtained.

However, since many of these pyrazoloazole type couplers have strong adsorptivity to silver halide, they may cause undesirable effects. In particular, U.S. Pat. Nos. 4,434,226 and 4,439,
No. 520, No. 4,414, 310, No. 4,433,
048, 4,414,306, 4,459,3
No. 53, JP-A-57-209002 and the like disclose the manufacturing method and use technique, and are known to have advantages such as improved color sensitization, improved sensitivity / granularity, improved sharpness, and improved covering power. When used in combination with flat silver halide grains, softening of gradation and broadening of development progress range occur.

Further, JP-A-63-011928 and JP-A-6-119928.
No. 3-151618 discloses a technique in which the size of tabular grains is monodispersed and the abundance ratio of tabular grains is increased, resulting in uneven gradation and uneven sensitization upon sensitized development ( The increase in sensitivity obtained by sensitized development is said to be relatively large in a layer using a pyrazoloazole type coupler), but attempts have been made to reduce it as much as possible. There are many problems that need to be solved in introducing photographic materials into photographic light-sensitive materials in terms of durability and storability of latent images. As an attempt to improve this durability, there is a method of introducing dislocations into grains as described in JP-A-63-220238, which is particularly effective in improving sensitivity, pressure property, storage stability and exposure illuminance dependency. It can be said that this is a remarkable technology. However, when the dislocations are introduced in the above invention, the grain shape is distorted, or the silver iodide content between grains or the distribution of grain size is widened, so that the gradation is softened again. It was insufficient for the request.

[0006]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a silver halide photographic light-sensitive material having excellent color reproduction, high sensitivity, and improved gradation and storability.

[0007]

As a result of intensive studies by the present inventors, the object of the present invention was achieved by the following means. That is, in a photographic light-sensitive material having at least one silver halide emulsion layer on a support, in the silver halide emulsion layer, (1) at least 50% of the total projected area is tabular halogenated with an aspect ratio of 3 or more. Occupied by silver particles,
The variation coefficient of the grain size distribution of the tabular silver halide grains occupying this 50% is 25% or less, and the variation coefficient of the silver iodide content distribution of each grain is 30% or less, which is 50% or more of the total number. A silver halide photographic emulsion characterized by having 10 or more dislocations per grain in the corresponding silver halide grain, and (2) a magenta coupler represented by the general formula (A) described in Chemical formula 2 below. It was achieved by a silver halide photographic light-sensitive material characterized by containing In formula (A), R ₁ represents a hydrogen atom or a substituent,
X represents a hydrogen atom or a group capable of splitting off by a coupling reaction with an oxidized product of an aromatic primary amine developer. Za,
Zb and Zc are methine, substituted methine, = N- or-
Representing NH-, one of the Za-Zb bond and the Zb-Zc bond is a double bond, and the other is a single bond. Zb-Z
The aromatic ring may be condensed at c. This also includes the case where R ₁ or X forms a dimer or higher multimer. In addition, when Za, Zb or Zc is a substituted methine, the case where the substituted methine forms a dimer or higher multimer is also included.

The present invention will be described in more detail below.

In the present invention, the tabular grains (hereinafter referred to as "tabular grains") have two parallel principal planes opposed to each other and have a circle equivalent diameter (having the same projected area as the principal planes). A particle in which the diameter of the circle is three times or more larger than the distance (that is, the thickness of the particle) in the principal plane.

The aspect ratio of the present invention is defined as a value obtained by dividing the equivalent circle diameter of each particle by the method described below by the thickness of the particle.

The average aspect ratio of the emulsion having tabular grains of the present invention is preferably 3-12, and particularly 3-8.
Is preferred.

The average aspect ratio can be obtained by averaging the grain diameter / grain thickness ratio of all tabular grains. A simple method is to use the average diameter of all tabular grains and the average thickness of all tabular grains. It can also be obtained as a ratio with.

The diameter (corresponding to a circle) of the tabular grains of the present invention is 0.
It is 2 to 5.0 μm, preferably 0.3 to 4.0 μm, and more preferably 0.3 to 3.0 μm.

The grain thickness is 0.5 μm or less, preferably 0.05 to 0.5 μm, more preferably 0.08 to
It is 0.3 μm.

In the present invention, the particle diameter and the particle thickness can be measured from electron micrographs of the particles as in the method described in US Pat. No. 4,434,226.

The tabular grains of the present invention are characterized by being monodisperse with a variation coefficient of grain size distribution of 25% or less.
The coefficient of variation referred to here is represented by "a value obtained by dividing the variation (standard deviation) of the grain size obtained from the circle-equivalent diameter and the thickness of the projected area of the tabular grain by the average grain size and multiplying by 100". Be done. Particle size (Rμm)
And are the equivalent circle diameter (rμm) and thickness (dμm) of the projected area
It is calculated from the following formula.

R = {(3/2) r^Twod}^1/3  Uniform grain morphology of silver halide grains and grain size
Of a silver halide emulsion consisting of grains with small variation in
Particle size distribution shows almost normal distribution, standard deviation
Can be easily obtained. Tabular grains of the present invention
The size distribution has a coefficient of variation of 25% or less, preferably 2
It is 0% or less, more preferably 15% or less.

Dislocations are described, for example, in J. F. Hamilto
n, Photo. Sci. Eng. 11 , 57, (19
67) and T.W. Shiozawa, J .; Soc. Pho
t. Sci Japan, 35 , 213, (1972)
It can be observed by a direct method using a transmission electron microscope at a low temperature described in 1. That is, the silver halide grains taken out carefully so as not to apply pressure to the grains causing dislocations on the emulsion are placed on the mesh for electron microscope observation, and damaged by electron beams (printout, etc.).
In order to prevent the above, the sample is cooled and observed by the transmission method. At this time, the thicker the particle, the more difficult it is for the electron beam to pass therethrough.
It can be observed more clearly by using an electron microscope of 0 kV or more). From the photograph of the grains obtained by such a method, the position and number of dislocations can be determined for each grain when viewed from the direction perpendicular to the main plane.

The positions of dislocations in the present invention occur in the major axis direction of the tabular grains from the distance x% of the length from the center to the side to the side, and the value of x is preferably 10.
≦ x <100, more preferably 30 ≦ x <98, still more preferably 50 ≦ x <95. At this time, the shape formed by connecting the positions where the dislocations start is similar to the particle shape, but may not be a perfect similar shape and may be distorted. The direction of the dislocation line is approximately from the center to the side, but it often meanders.

With respect to the number of dislocations of the present invention, grains containing 10 or more dislocations account for 50% (number) of all silver halide grains.
It is preferable that the above exists. It is more preferable that 70% (number) or more of particles containing 10 or more dislocations exist, and particularly preferably 90% (number) or more of particles containing 10 or more dislocations.

In the tabular grains of the present invention, the variation coefficient of the silver iodide content distribution of each grain is 30% or less, more preferably the variation coefficient is 20% or less.

The silver iodide content of each emulsion grain is, for example, X.
It can be measured by analyzing the composition of each particle using a line micro analyzer. The term "variation coefficient of the silver iodide content of individual grains" as used herein means, for example, the silver iodide content when the silver iodide content of at least 100 emulsion grains is measured by an X-ray microanalyzer. It is a value obtained by multiplying the value obtained by dividing the standard deviation by the average silver iodide content by 100. A specific method for measuring the silver iodide content of individual emulsion grains is described in, for example, European Patent 147,868A.

In the present invention, the silver iodide content is measured,
Grains for which the coefficient of variation of the distribution is calculated are arranged in order of increasing projected area from all the grains of the emulsion, and when the projected areas are added, the sum is 50% of the projected area. Use as silver halide grains. Here, in actually obtaining the coefficient of variation, first, the randomly selected 50
For 0 or more grains, test whether each grain is a large tabular silver halide grain to be controlled,
Furthermore, it is necessary to measure the silver iodide content for 50 or more grains randomly extracted from the control grains. Therefore, when there are fine grains having extremely different silver iodide contents, this ignores this silver iodide content when determining the coefficient of variation.

When the coefficient of variation of the silver iodide content distribution of individual grains is large, the appropriate point of chemical sensitization of individual grains (conditions of chemical sensitization suitable for individual grains) is different, and all emulsion grains are It becomes impossible to bring out the performance of.

Silver iodide content Yi (mol%) of individual grains
There may or may not be a correlation between each particle size Xi (micron), but it is desirable that there is no correlation.

Next, the method for producing the tabular grains of the present invention will be described.

The tabular grains can be prepared by appropriately combining methods known in the art. To prepare a tabular emulsion having a narrow grain size distribution as in the present invention,
It is necessary to follow the methods described in JP-A Nos. 63-11928 and 63-151618. The outline is described below in the order of nucleation stage, ripening stage, and growth stage.

The formation of nuclei has a molecular weight of 60,000 or less, preferably 10
Using a low molecular weight gelatin of 100,000 to 40,000 as a dispersion medium, pBr
It is preferably performed under the condition of 1.0 to 2.5.

It is preferable that 50% by weight or more, preferably 70% by weight or more of the dispersion medium is low molecular weight gelatin.

The concentration of the dispersion medium solution is 0.05 to 10% by weight.
Can be used.

Alkali-treated gelatin is usually used as the type of gelatin, but modified gelatin such as acid-treated gelatin and phthalated gelatin can also be used.

In addition, it is more preferable that one or both of the AgNO ₃ aqueous solution and the alkali halide aqueous solution added during nucleation contain gelatin. As the gelatin used here, the aforementioned low molecular weight gelatin is preferable. Also in this case, it is preferable that 50% by weight or more, preferably 70% by weight or more of the disintegrating medium is low molecular weight gelatin.

In this case, the concentration of the dispersion medium solution is 0.05 to
It is 5% by weight, preferably 0.3 to 2.0% by weight.

The temperature may be 5 to 60 ° C., but it is preferably 5 to 48 ° C. when fine tabular grains having an average particle size of 0.5 μm or less are prepared. The I ⁻ content of the solution charged in advance is preferably 0.03 mol / liter or less.
The addition rate of AgNO ₃ is preferably 0.5 g / min to 30 g / min per 1 liter of reaction aqueous solution.

[0035] The composition of the alkali halide solution added, Br ^- for I ^- content, generates AgBr
It is below the solid solution limit of I, preferably below 20 mol%.

The aging method is described in JP-A-63-15161.
Although the items described in No. 8 can be used, the following method is particularly effective in addition to them.

After the nucleation, a part of the emulsion is taken out as a seed crystal and an aqueous gelatin solution is added, or simply after the nucleation, an aqueous gelatin solution is added to adjust the pBr and gelatin concentration. The preferred pBr in this case is low pBr.
(1.4 to 2.0), and the gelatin concentration is 1 to 10% by weight. The gelatin used in this case is usually
An average molecular weight of 80,000 to 30 commonly used in the photographic industry
10,000 and usually 100,000 gelatin is preferred.

Next, the temperature is raised and an aqueous AgNO ₃ solution is added to increase the pBr of the solution to a higher pBr (1.7 to 2.6).
After adjusting to, a silver halide solvent is added. In this case, the concentration of the silver halide agent is 1 × 10 ^{−4 to} 3 × 1.
0 ^-1 mol / liter is preferred.

The pBr during the crystal growth period following the aging process was 1.
It is preferable to keep it at 4 to 3.0. The addition rate of Ag ⁺ and halogen ions during the crystal growth period is 20 to 100% of the crystal critical growth rate, preferably 30 to 100.
It is preferable to use an addition rate that results in a crystal growth rate of%.

That is, the growth atmosphere during the crystal growth period is
The higher the pBr, and the higher the degree of supersaturation, the more the tabular grains become monodispersed as they grow. However, on the high pBr side (pBr2 to 3.0 or a tetrahedral crystal or cubic crystal formation region described later), growth in the thickness direction is accompanied, and thus monodisperse tabular grains having a low aspect ratio can be obtained.

Low pBr side (pBr 1.4 to 2.0 or a region where {111} face crystals such as octahedrons described later are generated)
In addition, tabular grains having a high aspect ratio can be obtained by high saturation growth, but the monodispersity is slightly deteriorated.

In this case. The addition rate of silver ions and halogen ions is increased as the crystal grows. As a method of increasing the addition rate, Japanese Patent Publication No. 48-36890 is available.
No. 52-16364, the addition rate (flow rate) of the silver salt aqueous solution and the halogenated salt aqueous solution having a constant concentration may be increased, or the concentration of the silver salt aqueous solution and the halogen salt aqueous solution may be increased. May be. Alternatively, an ultrafine grain emulsion having a size of 0.10 μm or less may be prepared in advance, and the addition rate of this ultrafine grain emulsion may be increased. Also, a combination of these may be used. The addition rate of silver ions and halogen ions may be increased intermittently or continuously.

As a method of supplying iodide ions during the crystal growth period, a method of adding fine grain Ag1 (grain size of 0.1 μm or less, preferably 0.06 μm or less) emulsion prepared in advance may be used. You may use together with the method of supplying with an alkali halide aqueous solution. In this case, since the fine particles AgI are melted and I ⁻ is supplied, I ⁻ is uniformly supplied, which is particularly preferable.

In the present invention, it is preferred that the silver halide grains contain reduction sensitizing nuclei, but from that viewpoint,
The pH of the solution during the growth period is preferably 8.0 to 9.5.

A silver halide solvent described below can be used to accelerate the growth during the crystal growth period. In that case, the concentration of the silver halide solvent is 0 to 3.0 × 10 ⁻¹ m
ol / liter is preferred.

The generation of dislocations in the tabular grains of the present invention can be controlled by providing a specific high iodine phase inside the grains. Specifically, the substrate grains are prepared and then the high iodine phase is added. It is obtained by covering the outside with a phase having a low silver iodide content with a high iodide phase, and in order to make the silver iodide content of each grain uniform, the formation of the above high iodide phase is performed. It is important to select the conditions appropriately.

The internal high iodine phase refers to a silver halide solid solution containing iodine. In this case, silver iodide, silver iodobromide and silver chloroiodobromide are preferable as the silver halide, but silver iodide or silver iodobromide (silver iodide content of 10 to 40 mol%) is preferable. More preferably, and particularly preferably silver iodide.

It is important that the internal high iodine phase is not uniformly deposited on the plane of the tabular grains of the substrate, but rather is localized. Such localization may occur on any of the principal planes, side surfaces, sides, and corners of the flat plate. Further, it may be selectively and epitaxially coordinated to such a site. As a method for this, it is preferable to use a so-called conversion method in which an iodide salt is added alone.

By the above method, at least 50% of the total projected area is occupied by tabular grains having an aspect ratio of 3 or more, and the variation coefficient of the grain size distribution of the grains occupying 50% is 25% or less, and 50%. Although silver halide photographic grains having 10 or more dislocations per grain can be formed in the above grains, the variation coefficient of the silver iodide content distribution of each grain (hereinafter referred to as intergrain iodide distribution) Was difficult to make uniform. In particular, in order to solve the pressure property, latent image storability, etc., JP-A-63-2202
Introducing dislocations into particles as described in No. 38,
It was difficult to make the intergranular iodine distribution uniform.

In order to make the silver iodide content of individual grains of the emulsion uniform, it is important to make the size and shape after Ostwald ripening as uniform as possible. Further, in the growth stage, an aqueous solution of silver nitrate and an aqueous solution of alkali halide are added by the double jet method while keeping the pAg constant in the range of 6.0 to 10.0. The higher the degree of supersaturation of the solution, the higher the degree of supersaturation such that the crystal growth rate is 30 to 100% of the crystal critical growth rate by the method described in, for example, US Pat. No. 4,242,445. It is desirable to make additions once.

Further, especially the inter-grain iodide distribution is broadened by adding an iodide salt alone when forming dislocations. At that time, however, the following conditions should be selected. It is effective for making the silver iodide content uniform. That is, the pAg before the addition of iodide salt was 8.
The range of 5 to 10.5 is preferable, and the range of 9.0 to 10.5 is preferable. The temperature is preferably maintained in the range of 50 ° C to 30 ° C. Regarding the addition of the iodide salt, it is preferable to add 1 mol% of the iodide salt to the total amount of silver for 30 seconds to 5 minutes under a sufficiently stirred condition.

The silver iodide content of the tabular grains of the substrate is lower than that in the high iodide phase, preferably 0 to 12 mol%, more preferably 0 to 10 mol%.

The outer phase which covers the high iodine phase is lower than the silver iodide content of the high iodine phase, preferably the silver iodide content is 0 to 12 mol%, more preferably 0 to 10 mol%. It is preferably 0 to 3 mol%.

This internal high-iodine phase is 5 mol% to 80% from the center of the grain in the silver amount of the whole grain in the long axis direction of the tabular grain.
It is preferably present in the range of mol%, more preferably 10 mol% to 70 mol%, especially 20 mol% to 60 mol%.
It is preferably within the range of mol%.

Here, the major axis direction of the grains means the diameter direction of the tabular grains, and the minor axis direction means the thickness direction of the tabular grains.

The iodide content of the internal high iodide phase is higher than the average iodide content of silver bromide, silver iodobromide or silver chloroiodobromide present on the grain surface, and preferably 5 times or more. , Particularly preferably 20 times or more.

Furthermore, the amount of silver halide forming the internal high-iodine phase is 50 mol% or less, more preferably 10 mol% or less, especially 5 mol%, based on the total amount of silver.
It is preferably not more than mol%.

As described above, a silver halide solvent is useful for promoting ripening. For example, it is known to have excess halogen ions present in the reactor to accelerate aging. Therefore, it is clear that mere introduction of a halide salt solution into the reactor can accelerate aging.
Other ripening agents may be used, and these ripening agents may be added in the dispersion medium in the reactor in a total amount before adding the silver and halide salts, and one or more ripening agents may be used. It is also possible to add a halide salt, a silver salt or a deflocculant, and to introduce them into the reactor. As another variation, the ripening agent can be introduced independently at the halide salt and silver salt addition stages.

As ripening agents other than halogen ions, ammonia, amine compounds, thiocyanate salts,
For example, alkali metal thiocyanate salts, especially sodium and potassium thiocyanate salts, and ammonium thiocyanate salts can be used. The use of thiocyanate ripening agents is described in US Pat. No. 2,222,264.
Nos. 2,448,534 and 3,320,06
Instructions can be found in No. 9. US Pat. No. 3,271,1
57, 3,574,628 and 3,73
Conventional thioether ripening agents as described in 7,313 can also be used. Alternatively, JP-A-53-
It is also possible to use thione compounds such as those started in No. 82408 and No. 53-144319.

The properties of the silver halide grains can be controlled by allowing various compounds to be present in the silver halide precipitation forming process. Such compounds may be initially present in the reactor, or they may be added along with one or more salts in a conventional manner. US Pat. Nos. 2,448,060 and 2,628,167
Issue 3, Issue 3,737,313, Issue 3,772,031
Issue, and Research Disclosure, Vol. 134,
June 1975, 13452, copper, iridium, lead, bismuth, cadmium, zinc, (sulfur,
The characteristics of silver halide can be controlled by allowing compounds such as chalcogen compounds such as selenium and tellurium), gold and compounds of Group VII noble metals to be present during the silver halide precipitation formation process. Japanese Patent Publication 58-1410
Issue, Moisar et al., Journal of Photographic Science, 25, 197.
As described on pages 7 and 19 to 27, the silver halide emulsion can reduce and sensitize the inside of the grain during the precipitation formation process.

In the tabular grains used in the present invention,
Silver halides having different compositions may be joined by epitaxial joining, or may be joined with compounds other than silver halide such as silver rhodanide and lead oxide. These emulsion grains are described in U.S. Pat. No. 4,094,68.
No. 4, No. 4,142,900, No. 4,459,353
No., British Patent No. 2,038,792, US Patent No. 4,
349,622, 4,395,478, 4,4
33,501, 4,463,087, 3,65
6,962, 3,852,067, JP-A-59-
No. 162540 and the like.

The tabular grains of the present invention are usually chemically sensitized.

Chemical sensitization is performed by James (TH Ja
mes), The Theory of Photographic Process, 4th edition, published by Macmillan, 1977.
(TH James The Theory of
the Photographic Process,
4th ed, Macmillan, 1977) 67-
It can be carried out using activated gelatin as described on page 76, and also Research Disclosure 12
0, April 1974, 12008; Research Disclosure, 34, June 1975, 13452,
US Pat. Nos. 2,642,361 and 3,297,44
No. 6, No. 3,772,031, No. 3,857,711
Nos. 3,901,714, 4,266,018 and 3,904,415, and British Patent No. 1,
315,755, pAg5-10,
It can be carried out at a pH of 5 to 8 and a temperature of 30 to 80 ° C. using sulfur, selenium, tellurium, gold, platinum, palladium, iridium or a combination of a plurality of these sensitizers. Chemical sensitization is optimally performed in the presence of gold and thiocyanate compounds and also in US Pat. No. 3,857,711.
Nos. 4,266,018 and 4,054,45
It is carried out in the presence of a sulfur-containing compound described in No. 7, or a sulfur-containing compound such as hypo, a thiourea compound, and a rhodanine compound. It is also possible to carry out chemical sensitization in the presence of a chemical sensitization aid. As the chemical sensitization aid to be used, compounds known to suppress fog and increase sensitivity in the process of chemical sensitization such as azaindene, azapyritazine and azapyrimidine are used. Examples of chemical sensitization aid modifiers are described in US Pat. Nos. 2,131,038 and 3,41.
1,914, 3,554,757, JP-A-58-
No. 126526 and the above-mentioned "Photographic Emulsion Chemistry" by Duffin, pp. 138-143. In addition to or in place of chemical sensitization, US Pat. No. 3,891,44
As described in No. 6 and No. 3,984,249, reduction sensitization can be performed using, for example, hydrogen,
US Pat. Nos. 2,518,698 and 2,743,18
2 and 2,743,183 with stannous chloride, thiourea dioxide, polyamines and such reducing agents, or at low pAg (eg less than 5) and / or high pH (eg Reduction sensitization can be carried out by treatment. US Pat. No. 3,9
Color sensitization can also be improved by the chemical sensitization methods described in 17,485 and 3,966,476.

Further, JP-A-61-3134 and 61-31
The sensitizing method using an oxidizing agent described in 36 can also be applied.

The compound represented by formula (A) will be described in detail below.

In the general formula (A), a multimer means a compound having two or more groups represented by the general formula (A) in one molecule, and includes a bis form and a polymer coupler. Be done. Here, the polymer coupler may be a homopolymer consisting only of a monomer having a portion represented by the general formula (A) (preferably having a vinyl group, hereinafter referred to as vinyl monomer), or an aromatic primary amine developing agent. Copolymers may be made with non-chromogenic, ethylene-like monomers that do not couple with the oxidation products of.

The compound represented by the general formula (A) is a 5-membered ring-5-membered ring condensed nitrogen heterocyclic coupler, and its color forming nucleus shows isoelectronic aromaticity with naphthalene, and is generally called azapentalene. It has a chemical structure. Among the couplers represented by formula (A), preferred compounds are
1H-imidazo [1,2-b] pyrazoles, 1H-pyrazolo [1,5-b] pyrazoles, 1H-pyrazolo [5,1-c] [1,2,4] triazoles, 1H-
Pyrazolo [1,5-b] [1,2,4] triazoles, 1H-pyrazolo [1,5-d] tetrazole and 1H-pyrazolo [1,5-a] benzimidazoles, each of which is described below. A general formula (A-1) described in Chemical formula 3
It is represented by (A-2), (A-3), (A-4), (A-5) and (A-6). Among these, preferable compounds are (A-1), (A-3) and (A-4). Particularly preferred compounds are (A-3) and (A-4).

The substituents R ^a2 , R ^a3 and R ^a4 in formulas (A-1) to (A-6) are each a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a cyano group or an alkoxy group. Group, aryloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, silyloxy group, sulfonyloxy group, acylamino group, anilino group, ureido group, imide group, sulfamoylamino group, alkylthio group, arylthio group, hetero A cyclic thio group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, a sulfonamide group, a carbamoyl group, an acyl group, a sulfamoyl group, a sulfonyl group, a sulfinyl group, an alkoxycarbamoyl group, or an aryloxycarbonyl group, and X ^a1 is hydrogen. Atom, halogen atom, carboxy Represents a group or an oxygen atom, the coupling-off to base carbon with binding of a coupling position via a nitrogen atom or a sulfur atom.

R ^a2 , R ^a3 , R ^a4 or X ^a1 is 2
It also serves as a valence group and forms a bis form. When the moieties represented by formulas (A-1) to (A-6) are present in the vinyl monomer, R ^a2 , R ^a3 or R ^a4 represents a simple bond or a linking group. The moieties represented by general formulas (A-1) to (A-6) are bonded to the vinyl group via the group.

More specifically, R ^a2 , R ^a3 and R a
^a4 is a hydrogen atom, a halogen atom (eg, chlorine atom, bromine atom), an alkyl group (eg, methyl, propyl, t-butyl, trifluoromethyl, tridecyl, 3).
-(2,4-di-t-amylphenoxy) propyl, 2
-Dodecyloxyethyl, 3-phenoxypropyl, 2
-Hexylsulfonyl-ethyl, cyclopentyl, benzyl), aryl groups (e.g. phenyl, 4-t-butylphenyl, 2,4-di-t-amylphenyl, 4-tetradecanamidophenyl), heterocyclic groups (e.g. 2
-Furyl, 2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl), cyano group, alkoxy group (e.g. methoxy, ethoxy, 2-methoxyethoxy, 2-dodecyloxyethoxy, 2-methanesulfonylethoxy), aryloxy group (e.g. , Phenoxy, 2-methylphenoxy, 4-t-butylphenoxy), heterocyclic oxy group (eg, 2-benzimidazolyloxy), acyloxy group (eg, acetoxy, hexadecanoyloxy), carbamoyloxy group (eg, N -Phenylcarbamoyloxy, N-ethylcarbamoyloxy),
A silyloxy group (eg, trimethylsilyloxy),
Sulfonyloxy group (eg, dodecylsulfonyloxy), acylamino group (eg, acetamide, benzamide, tetradecanamide, α- (2,4-di-t-
Aminophenoxy) butanamide, γ- (3-t-butyl-4-hydroxyphenoxy) butanamide, α-
{4- (4-hydroxyphenylsulfonyl) phenoxy} decanamide), anilino group (for example, phenylamino, 2-chloroanilino, 2-chloro-5-tetradecanamideanilino, 2-chloro-5-dodecyloxycarbonylanilino, N-acetylanilino, 2-chloro-5- {α- (3-t-butyl-4-hydroxyphenoxy) dodecanamide} anilino), ureido group (eg, phenylureido, methylureido, N, N-dibutylureido) ), An imide group (for example, N-succinimide, 3-benzylhindantoinyl, 4- (2-ethylhexanoylamino) phthalimide), a sulfamoylamino group (for example, N, N-dipropylsulfamoylamino, N-methyl-N-decylsulfamoylamino), alkylthio Group (e.g., methylthio, octylthio, tetradecylthio, 2-phenoxyethyl thio,
3-phenoxypropylthio, 3- (4-t-butylphenoxy) propylthio), an arylthio group (for example, phenylthio, 2-butoxy-5-t-octylphenylthio, 3-pentadecylphenylthio, 2-carboxyphenylthio, 4-tetradecanamidophenylthio), a heterocyclic thio group (for example, 2-benzothiazolylthio), an alkoxycarbonylamino group (for example, methoxycarbonylamino, tetradecyloxycarbonylamino), an aryloxycarbonylamino group (for example, phenoxy). Carbonylamino, 2,4-di-ter
t-butylphenoxycarbonylamino), a sulfonamide group (for example, methanesulfonamide, hexadecanesulfonamide, benzenesulfonamide, p-toluenesulfonamide, octadecanesulfonamide, 2-
Methyloxy-5-t-butylbenzenesulfonamide), a carbamoyl group (for example, N-ethylcarbamoyl, N, N-dibutylcarbamoyl, N- (2-dodecyloxyethyl) carbamoyl, N-methyl-N-dodecylcarbamoyl, N- {3- (2,4-di-tert)
-Amylphenoxy) propyl} carbamoyl), an acyl group (for example, acetyl, (2,4-di-tert-amylphenoxy) acetyl, benzoyl), a sulfamoyl group (for example, N-ethylsulfamoyl, N, N-).
Dipropylsulfamoyl, N- (2-dodecyloxyethyl) sulfamoyl, N-ethyl-N-dodecylsulfamoyl, N, N-diethylsulfamoyl), sulfonyl group (for example, methanesulfonyl, octanesulfonyl, benzenesulfonyl) , Toluenesulfonyl),
Sulfinyl group (eg, octylsulfinyl, dodecylsulfinyl, phenylsulfinyl), or alkoxycarbonyl group (eg, methoxycarbonyl,
Butyloxycarbonyl, dodecyloxycarbonyl,
Octadecyloxycarbonyl) and an aryloxycarbonyl group (eg, phenyloxycarbonyl, 3-pentadecylphenyloxy-carbonyl).

X ^a1 is a hydrogen atom, a halogen atom (eg, chlorine atom, bromine atom, iodine atom), a carboxyl group, or a group linked by an oxygen atom (eg, acetoxy, propanoyloxy, benzoyloxy, 2,4-dichloro). Benzoyloxy, ethoxyoxaloyloxy, pyruvinyloxy, cinnamoyloxy, phenoxy, 4-
Cyanophenoxy, 4-methanesulfonamidephenoxy, 4-methanesulfonylphenoxy, α-naphthoxy, 3-pentadecylphenoxy, benzyloxycarbonyloxy, ethoxy, 2-cyanoethoxy, benzyloxy, 2-phenethyloxy, 2-phenoxyethoxy , 5-phenyltetrazolyloxy, 2-benzothiazolyloxy), groups linked by nitrogen atoms (for example, benzenesulfonamide, N-ethyltoluenesulfonamide, heptafluoroptanamide, 2,3,4,5) ，
6-pentafluorobenzamide, octanesulfonamide, p-cyanophenylureido, N, N-diethylsulfamoylamino, 1-piperidyl, 5,5-dimethyl-2,4-dioxo-3-oxazolidinyl, 1-
Benzyl-ethoxy-3-hydantoinyl, 2N-1,
1-dioxo-3 (2H) -oxo-1,2-benzisothiazolyl, 2-oxo-1,2-dihydro-1-pyridinyl, imidazolyl, pyrazolyl, 3,5-diethyl-1,2,4- Triazol-1-yl, 5- or 6-bromo-benzotriazol-1-yl, 5-methyl-1,2,3-triazol-1-yl, benzimidazolyl, 3-benzyl-1-hydantoinyl, 1-benzyl -5-hexadecyloxy-3-hydantoinyl, 5-methyl-1-tetrazolyl, 4-methoxyphenylazo, 4-pivaloylaminophenylazo, 2-hydroxy-4-propanoylphenylazo), or a sulfur atom Linking groups (eg phenylthio, 2-carboxyphenylthio, 2-methoxy-5-t-octylphenylthio, 4 Methanesulfonyl phenylthio,
4-octanesulfonamidophenylthio, 2-butoxyphenylthio, 2- (2-hexanesulfonylethyl) -5-tert-octylphenylthio, benzylthio, 2-cyanoethylthio, 1-ethoxycarbonyltridecylthio, 5-phenyl -2,3,4,5-tetrazolylthio, 2-benzothiazolylthio, 2-dodecylthio-5-thiophenylthio, 2-phenyl-3-dodecyl-1,2,4-triazolyl-5-thio) ..

R ^a2 , R ^a3 , R ^a4 or X ^a1 is 2
When the bis group is formed by forming a valent group, the divalent group may be described in more detail. A substituted or unsubstituted alkylene group (for example, methylene, ethylene, 1,10-decylene, —CH ₂ CH ₂ —). _{O-CH 2 CH 2 -,} ), a substituted or unsubstituted phenylene group (e.g., 1,4-phenylene, 1,3-phenylene, 2,5-dimethyl-1,4
And phenylene, 2,5-dichloro-1,4-phenylene, and —NHCO—R ^a5 —CONH— group (R ^a5 represents a substituted or unsubstituted alkylene group or phenylene group).

R ^a2 and R ^a3 in the case where the compounds represented by the general formulas (A-1) to (A-6) are present in the vinyl monomer.
^{Alternatively} , the linking group represented by R ^a4 is an alkylene group (a substituted or unsubstituted alkylene group such as methylene,
Ethylene, _{1,10-decylene,} -CH ₂ CH 2 OCH
₂ CH ₂ -,), phenylene group (a substituted or unsubstituted phenylene group, such as 1,4-phenylene, 1,3-phenylene, 2,5-dimethyl-1,4-phenylene,
2,5-dichloro-1,4-phenylene), -NHCO
It includes a group formed by combining a group selected from —, —CONH—, —O—, —OCO— and an aralkylene group (for example, those shown in Chemical formula 17 below).

The vinyl group in the vinyl monomer includes those having a substituent other than those represented by the general formulas (A-1) to (A-6). A preferable substituent is a hydrogen atom, a chlorine atom, or a lower alkyl group having 1 to 4 carbon atoms.

Non-color-forming, ethylenic monomers which do not couple with the oxidation products of aromatic primary amine developers include acrylic acid, α-chloroacrylic acid, α-alacrylic acid (eg methacrylic acid) and their derivatives. Amides or esters derived from acrylic acids (eg, acrylamide, n-butyl acrylamide, t-butyl acrylamide, diacetone acrylamide, methacrylamide, methyl acrylate, ethyl acrylate,
n-propyl acrylate, n-butyl acrylate,
t-butyl acrylate, iso-butyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate and β-hydroxymethacrylate), methylenedibisacrylamide, vinyl ester (for example, Vinyl acetate, vinyl propionate and vinyl laurate), acrylonitrile, methacrylonitrile, aromatic vinyl compounds (eg styrene and its derivatives,
Vinyltoluene, divinylbenzene, vinylacetophenone and sulfostyrene), itaconic acid, citraconic acid, crotonic acid, vinylidene chloride, vinyl alkyl ether (eg vinyl ethyl ether), maleic acid, maleic anhydride, maleic acid ester, N-vinyl -2-pyrrolidone, N-vinyl pyridine, and 2
-And 4-vinylpyridine and the like. It also includes the case where two or more non-color-forming ethylenically unsaturated monomers used here are used together.

Examples of compounds of the couplers represented by the general formulas (A-1) to (A-6), synthetic methods, and the like are described in the following documents.

The compound of formula (A-1) is disclosed in JP-A-59-
162548 and the like, compounds of the general formula (A-2) are described in JP-A-60-43659 and the like, compounds of the general formula (A-3) are described in JP-B-47-27411 and the like, and compounds of the general formula (A-4 Compounds of JP-A-59-171956 and JP-A-60-1
72982 and the like, the compound of the general formula (A-5) is described in JP-A-60-33552, and the compound of the general formula (A-6) is described in U.S. Pat. No. 3,061,432 and the like. ing.

Further, JP-A-58-42045 and 59 are the same.
-214854, 59-177553, 59-
177554 and 59-177557 and the like have high color-forming ballast groups represented by the general formula (A-
It is applied to any of the compounds 1) to (A-6).

Specific examples of the pyrazoloazole-based coupler used in the present invention are shown in Chemical formulas 4 to 16 below, but the invention is not limited thereto.

These couplers are generally 2 × 10 ⁻³ to 5 × 10 ⁻¹ mol, preferably 1 × 10 ⁻² to 5 × 10 ⁻¹ mol per mol of silver in the emulsion layer.
Mol added.

The above couplers and the like can be used in combination of two or more kinds in the same layer in order to satisfy the characteristics required for a light-sensitive material, and the same compound can be added in two or more different layers, of course. Absent.

The above coupler can also be used in combination with a magenta coupler having a pyrazone skeleton.

When the tabular grains of the present invention are used in a color light-sensitive material comprising a cyan color developing red sensitive emulsion layer, a magenta color developing green sensitive layer and a yellow color developing blue sensitive layer, they are preferably used in a green sensitive emulsion layer containing a magenta coupler. More preferably, it is also used for a color-sensitive layer arranged at a position farther from the support side than the green-sensitive emulsion layer. When the green-sensitive emulsion layer is composed of two or more layers having different sensitivities, i) When any of the green-sensitive layers contains the coupler and tabular grains of the invention. ii) When any green-sensitive layer contains tabular grains, and the coupler of the present invention is contained only in the lower-sensitive green-sensitive layer. iii) The tabular grains are contained only in the green-sensitive layer having a higher sensitivity than that of the coupler, and the coupler of the present invention is contained only in the green-sensitive layer having a lower sensitivity. iv) contains tabular grains only in the green sensitive layer having higher sensitivity than
When the coupler of the present invention is contained in any green-sensitive layer. And the like, ii) or ii
i) is most preferable, and i) or iv) can also be preferably used.

The tabular grain emulsion of the present invention can be used in combination with a conventional emulsion comprising chemically sensitized silver halide grains (hereinafter referred to as non-tabular grains) in the same silver halide emulsion layer. In the case of a color photographic light-sensitive material, a tabular grain emulsion and a non-tabular grain emulsion can be used in different emulsion layers and / or in the same emulsion layer. Examples of the non-tabular grains include regular grains having regular crystalline bodies such as cubes, octahedra and tetradecahedrons, and grains having irregular crystal shapes such as spherical and potato-like grains. it can. As the silver halide of these non-tabular grains, any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride may be used. Preferred silver halide is 30 mol%
It is silver iodobromide or silver iodochlorobromide containing the following silver iodide. Particularly preferred is silver iodobromide containing 2 to 25 mol% of silver iodide.

The grain size of the non-tabular grains used here is 0.
It may be fine particles of 1 micron or less or large size grains having a projected area diameter of up to 10 microns, and may be a monodisperse emulsion having a narrow distribution or a polydisperse emulsion having a wide distribution.

The non-tabular grains used in the present invention are described in "Physics and Chemistry of Photography" by Graphide, published by Paul Montel (P. Glafkides, Chimie et P.
hysique Photographaque Pa
ul Montel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (G.F. Duffi).
n, Photographic Emulsion
Chemistry (Focal Press, 196)
6), "Production and Coating of Photographic Emulsions" by Zelikmann et al., Published by Focal Prene (VL Zelikman et.
al. Making and Coating Phog
radical Emulsion Focal Pres
s, 1964) and the like. That is, any of an acidic method, a neutral method, an ammonia method, etc. may be used, and a method of reacting a soluble silver salt and a soluble halogen salt may be a one-sided mixing method, a simultaneous mixing method, or a combination thereof. Good. A method of forming grains in the presence of excess silver ions (so-called reverse mixing method) can also be used. As one form of the simultaneous mixing method, a method of keeping pAg in a liquid phase where silver halide is formed constant, that is, a so-called controlled double jet method can be used. According to this method, a silver halide emulsion having a regular crystal form and a substantially uniform grain size can be obtained.

Two or more kinds of silver halide emulsions formed separately may be mixed and used.

The silver halide emulsion comprising the above regular grains can be obtained by controlling pAg and pH during grain formation. For details, see, for example, Photographic Science and Engineering (Photogr).
apic Science and Engineer
ing) Volume 6, 159-165 (1962); Journal of Photographic Science (Jour)
nal of Photographic Science
Ce), 12: 242-251 (1964), U.S. Pat. No. 3,655,394 and British Patent 1,41.
3748.

Regarding the monodisperse emulsion, JP-A-48-
No. 8600, No. 51-39027, No. 51-8309
No. 7, No. 53-137133, No. 54-48521.
No. 54-99419, No. 58-37635, No. 58-49938, Japanese Patent Publication No. 47-11386, US Pat. No. 3,655,394 and British Patent No. 1,41.
3, 748 and the like.

The crystal structure of these non-tabular grains may be uniform, may have different halogen compositions inside and outside, or may have a layered structure. These emulsion grains are disclosed in British Patent No. 1,027,146, U.S. Pat. Nos. 3,505,068, 4,444,877, and Japanese Patent Application No. 58-248469.

In the present invention, a non-photosensitive fine grain emulsion of 0.6 μm or less, preferably 0.2 μm or less is used for the purpose of promoting development, improving storage stability, effectively utilizing reflected light, and the like, and a silver halide emulsion layer and an intermediate layer. Alternatively, it may be added to the protective layer.

The tabular grains of the present invention are preferably used in color photographic light-sensitive materials.

By using the tabular grain emulsion of the present invention in the same and / or different emulsion layer from the non-tabular monodisperse silver halide grain emulsion, it becomes possible to improve sharpness and granularity at the same time. Sometimes.

The monodispersed silver halide emulsion (non-tabular grain) as used herein means that 95% or more of the total weight or the total number of silver halide grains contained therein is within ± 40% of the average grain size, more preferably. Defined to be within ± 30%. The use of a monodisperse silver halide emulsion in a silver halide photographic light-sensitive material can improve the granularity, as described in JP-B-47-11386 and JP-A-55-142329.
57-17235, 59-72440 and the like. In addition, the above-mentioned T. H. James, "The Theory of Photographic Process", 580
~ 0.3 μ-0.8 as described on page 585
The μ monodisperse silver halide grain has a property that it has a large light scattering property with respect to light in a specific wavelength range, but has a relatively small light scattering property with respect to light in other wavelength ranges. It is also known that.

Therefore, the tabular silver halide emulsion having a grain diameter / thickness ratio of 3 or more and the monodisperse silver halide emulsion are appropriately arranged in consideration of the optical characteristics and graininess of each silver halide emulsion. By doing so, it may be possible to simultaneously improve the sharpness and granularity of the silver halide photographic light-sensitive material.

Some examples of such embodiments will be listed.

Example 1) In a light-sensitive material in which a red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer are layered in this order from the support side, the silver halide emulsion layer constituting the blue-sensitive layer has silver halide grains contained therein. When the average grain size is in the range of 0.3 μ to 0.8 μ, a tabular grain emulsion is used in the emulsion layer, and when the average grain size is not in the above range, a single-separated silver halide emulsion is used. This can improve the sharpness of the green-sensitive layer and the red-sensitive layer and the granularity of the blue-sensitive layer.

Example 2) In a light-sensitive material having the same layer arrangement as in Example 1, the average grain size of silver halide grains contained in the silver halide emulsion layer constituting the green-sensitive layer was 0.4 μ to 0. When it is in the range of 8μ, a tabular grain emulsion is used in the emulsion layer, and when the average grain size is not in the above range, a monodisperse emulsion is used to improve the sharpness of the red-sensitive layer while providing a green feeling. It is possible to improve the granularity of the layer.

Example 3) In a light-sensitive material having the same layer arrangement as in Example 1, the emulsion having the same color sensitivity is composed of a plurality of two or more emulsion layers having different sensitivities. When the average particle size of the lower-sensitivity blue-sensitive layer is 0.3 to 0.8 μm, the lower-sensitivity blue is used. By using a tabular grain emulsion in the sensitive layer, the sharpness of the green sensitive layer and the red sensitive layer can be improved.

Example 4) A light-sensitive material having the same layer arrangement as in Example 3 and all of the plurality of green-sensitive layers have an average particle size of 0.4 to 0.8 μm.
In the case of m, it is possible to use tabular grain emulsions for all green-sensitive layers to improve the sharpness of the red-sensitive layer and the granularity of the green-sensitive layer.

When the blue-sensitive layer, the green-sensitive layer and the red-sensitive layer are each composed of a plurality of emulsion layers as in Examples 3 and 4, an emulsion having a large light scattering is used in order to improve sharpness and granularity. It should be considered to use tabular grain emulsions for the layers and monodisperse emulsions for the emulsion layers with low light scattering.
Further, in Example 4, when a tabular grain emulsion is further used for the red-sensitive layer, light scattering between the emulsion layers may be increased to deteriorate the sharpness of the green-sensitive layer on the red-sensitive layer.
In some cases it may not be desirable to use a tabular grain emulsion in the red sensitive layer closest to the support.

The tabular grain emulsion and non-tabular grain emulsion used in the present invention are usually those which have been physically ripened, chemically ripened and spectrally sensitized as described above. Additives used in such a process are Research Disclosure No. 17643 and No. 17643. 18716, and the corresponding parts are summarized in the table below.

Known photographic additives that can be used in the present invention are also described in the above two Research Disclosures, and the points described in the following table are shown.

[0104]

Various color couplers can be used in the light-sensitive material of the present invention. Specific examples thereof include Research Disclosure (RD) No. 1764
3, VII-C to G. As the dye-forming coupler, a coupler which gives the three primary colors of the subtractive color method (that is, yellow, magenta and cyan) by color development is important. Specific examples of the diffusion resistant 4-equivalent or 2-equivalent coupler are RD17643, V
In addition to the couplers described in the patents described in II-C and D, the following can be preferably used in the present invention.

Typical examples of the yellow coupler which can be used in the light-sensitive material of the present invention are hydrophobic acylacetamide type couplers having a ballast group.
Specific examples thereof are described in US Pat. Nos. 2,407,210, 2,875,057 and 3,265,506. The use of a two equivalent yellow coupler is preferred in the present invention and is described in US Pat. No. 3,408,19.
No. 4, No. 3,447,928, No. 3,933,5
No. 01 and No. 4,022,620, etc., or oxygen atom-releasing yellow couplers or JP-B-5
8-10739, U.S. Pat. No. 4,401,752,
No. 4,326,024, RD18035 (1979).
, April), British Patent No. 1,425,020, West German Application Publication Nos. 2,219,917, and 2,261,361.
No. 2,329,587 and No. 2,433.
Typical examples thereof include nitrogen atom-releasing yellow couplers described in JP-A No. 812. The α-pivaloyl acetanilide type coupler is excellent in the fastness, especially the light fastness of the color forming dye, while the α-benzoyl acetanilide type coupler can obtain a high coloring density.

The magenta coupler that can be used in the light-sensitive material of the present invention is a hydrophobic isodazolone type or cyanoacetyl type having a ballast group, preferably 5
-Pyrazolone type couplers. The 5-pyrazolone-based coupler is preferably a coupler in which the 3-position is substituted with an arylamino group or an acylamino group, from the viewpoint of the hue and color density of the color forming dye, and a typical example thereof is U.S. Pat. No. 2,311,082. No. 2,343,703, No. 2,600,788, No. 2,908,573,
No. 3,062,653, No. 3,152,896 and No. 3,936,015. As the leaving group of the 2-equivalent 5-pyrazolone-based coupler, the nitrogen atom leaving group described in US Pat. No. 4,310,619 or the arylthio group described in US Pat. No. 4,351,897 is particularly preferable. Further, the 5-pyrazolone-based coupler having a ballast group described in EP 73,636 provides a high color density.

Cyan couplers which can be used in the light-sensitive material of the present invention include hydrophobic and diffusion resistant naphthol and phenol couplers, and US Pat.
Naphthol couplers described in US Pat. Nos. 4,052,212 and 4,14,293.
Representative examples thereof include oxygen atom desorption type two-equivalent naphthol couplers described in Nos. 6,396, 4,228,233 and 4,296,200. Specific examples of the phenol-based coupler are described in US Pat. Nos. 2,369,939, 2,801,171, 2,772,162, and 2,895,826. There is.

A coupler capable of forming a cyan dye which is fast against humidity and temperature is preferably used in the present invention, and typical examples thereof include a phenol nucleus meta described in US Pat. No. 3,772,002. Phenolic cyan couplers having an ethyl group or higher alkyl group at the -position, US Pat. Nos. 2,772,162 and 3,758,308.
No. 4,126,396, No. 4,334,01
No. 1, 4,327,173, West German Patent Publication No. 3,
2,5-diacylamino-substituted phenol-based couplers described in 329,729 and European Patent 121,365, and US Pat. Nos. 3,446,622, 4,333,999, and 4 , 451, 559 and 4,427, 767, and the like, and phenolic couplers having a phenylureido group at the 2-position and an acylamino group at the 5-position. The cyan couplers described in EP 161,626A in which the 5-position of naphthol is substituted with a sulfonamide group, an amide group, etc. are also excellent in the fastness of a color image and can be preferably used in the present invention.

In order to correct the unwanted absorption of color-developing dyes, it is preferable to mask a color photosensitive material for photographing with a colored coupler. U.S. Pat. No. 4,16
No. 3,670 and Japanese Patent Publication No. 57-39413, yellow colored magenta couplers and U.S. Pat. Nos. 4,004,929, 4,138,258 and British Patent 1,146,368. Typical examples are the magenta colored cyan couplers described.
Other colored couplers are the above-mentioned RD17643, V
It is described in Sections II-G.

The graininess can be improved by using a coupler in which the color forming dye has an appropriate diffusibility. Such couplers are exemplified by magenta couplers in U.S. Pat. No. 4,366,237 and British Patent 2,125,570, and in European Patent No. 96,570 and West German Application No. 3,234. No. 533 describes specific examples of yellow, magenta or cyan couplers.

The dye-forming coupler and the above-mentioned special coupler may form a polymer of a dimer or more. Typical examples of polymerized dye-forming couplers are described in US Pat.
51,820 and 4,080,211. Specific examples of polymerized magenta couplers are:
British Patent No. 2,102,173 and US Patent No. 4,
367,282.

Couplers that release a photographically useful residue upon coupling are also preferably used in the present invention. The DIR coupler that releases the development inhibitor is the above-mentioned RD
The couplers of the patents described in 17643, VII-F are useful.

Preferred in combination with the present invention are:
Developer deactivation type represented by JP-A-57-151944; U.S. Pat. No. 4,248,962 and JP-A-57.
Timing type represented by 154234; Japanese Patent Application No. 5
The reaction type represented by JP-A No. 9-39653 and particularly preferable ones are JP-A Nos. 57-151944 and 58-2.
17932, Japanese Patent Application Nos. 59-75474 and 59-8.
2214, 59-82214 and 59-90.
No. 438 and the like, and developer type deactivating DIR couplers and the reaction type D, such as those described in Japanese Patent Application No. 59-39653.
It is an IS coupler.

In the light-sensitive material of the present invention, a coupler which imagewisely releases a nucleating agent or a development accelerator or a precursor thereof during development can be used. Specific examples of such compounds are described in British Patent Nos. 2,097,140 and 2,131,188. A coupler which releases a nucleating agent or the like having an adsorbing action on silver halide is particularly preferable.
157638 and 59-170840.

The coupler used in the present invention can be introduced into the photographic material by various known dispersion methods.

Examples of the high boiling point solvent used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027.

The steps and effects of the latex dispersion method, and specific examples of latex for impregnation are described in US Pat. No. 4,199,
No. 363, West German Patent Application (OLS) No. 2,541,27
No. 4 and No. 2,541,230.

Suitable supports which can be used in the present invention are described in, for example, RD. No. 17643, p. 28 and ibid.
No. 18716, page 647, right column to page 648, left column.

The color photographic light-sensitive material according to the present invention has the RD. No. 17643, pages 28-29 and ibid.
No. Development can be carried out by a usual method described in the left column to the right column of 651 of 18716.

The color photographic light-sensitive material of the present invention is usually subjected to washing treatment or stabilizing treatment after development, bleach-fixing or fixing treatment.

In the water washing step, two or more tanks are subjected to countercurrent water washing,
It is common to save water. A typical example of the stabilizing treatment is a multi-stage countercurrent stabilizing treatment as described in JP-A-57-8543 instead of the water washing step. In the case of this step, a countercurrent bath of 2 to 9 tanks is required. Various compounds are added to the stabilizing bath for the purpose of stabilizing the image. For example, various buffers (eg borate, metaborate, borax, etc.) for adjusting the membrane pH (eg pH 3-8).
Typical examples include phosphates, carbonates, potassium hydroxide, sodium hydroxide, aqueous ammonia, monocarboxylic acids, dicarboxylic acids, polycarboxylic acids and the like) and formalin. In addition, if necessary, water softener (inorganic phosphoric acid, aminopolycarboxylic acid, organic phosphoric acid, aminopolyphosphonic acid, phosphonocarboxylic acid, etc.), bactericide (benzisothiazolinone, isothiazolone, 4-thiazolinebenzimidazole) , Halogenated phenol, etc.), various additives such as surfactants, optical brighteners and hardeners may be used, and two or more kinds of the same or different target compounds may be used in combination.

Further, it is preferable to add various ammonium salts such as ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium sulfite, and ammonium thiosulfate as a film pH adjuster after the treatment.

The present invention can be applied to various color light-sensitive materials. Typical examples include color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films and color reversal papers.
The present invention also relates to Research Disclosure 1712.
No. 3 (July 1978) and the like, and can also be applied to a black-and-white light-sensitive material utilizing a mixture of three-color couplers.

The present invention will be further described with reference to examples.

[0126]

【Example】

(Example-1) (1) Preparation of emulsion (Preparation of emulsion 1) AgNO ₃ was added by a double jet method to 1 liter of an aqueous solution containing 4.5 g of KBr and 7 g of gelatin having an average molecular weight (M) of 20,000 while stirring. Stirring an aqueous solution (containing 32 g of AgNO ₃ and 0.7 g of M20,000 gelatin and 0.14 ml of HNO ₃ (1N) in 100 ml) and KB “aqueous solution (containing 0.7 g of M20,000 gelatin in 100 ml). While maintaining the pBr value constant, 27.5 cc of each was added at 25 cc / min.The temperature was 30 ° C. Of this emulsion, 350 ml was added.
650 ml of an aqueous gelatin solution (including 20 g of gelatin and 1.2 g of KBr) was added to the seed crystal, and the temperature was raised to 7
After raising the temperature to 5 ° C. and aging for 40 minutes, an AgNO ₃ aqueous solution (A
gNO ₃ (containing 1.7 g) was added in 1 minute and 30 seconds, and then 6.2 ml of NH ₄ NO ₃ (50 wt%) aqueous solution and NH ₃ were added.
6.2 ml of ₃ (25% by weight) aqueous solution was added,
Aged for minutes.

Next, the emulsion was adjusted to pH 7.0, 1 g of KBr was added, and then an aqueous AgNO ₃ solution (AgN in 100 ml was added).
O ₃ and containing 10 g) and the beginning of the 10 minutes the aqueous KBr solution in 8 ml / min, the next 20 minutes to a CDJ addition of silver potential -20mV at 15ml / min. This emulsion was washed with water and redispersed. The obtained emulsion grain replica image is TEM
(Magnification of 3280 times) was observed. The average grain size of the grains of the present invention in the emulsion was 1.1 μm, the average thickness was 0.16 μ, and the average aspect ratio was 6.7. Other properties are shown in Table A below.

(Preparation of Emulsion 2) Total AgN in Emulsion 1
When the addition of 80% of the O ₃ amount is completed, AgNO ₃ and K are added.
Emulsion 2 was prepared by interrupting the addition of the Br aqueous solution, adjusting the temperature to 50 ° C., and adding 830 ml of a KI aqueous solution in about 10 seconds.

At this time, an aqueous KBr solution was added immediately before the addition of the aqueous KI solution to adjust the silver potential to -60 mV.

(Preparation of Emulsions 3, 4 and 5) Emulsions 3 and 4 were prepared by reducing the amount of the KBr aqueous solution added before the addition of the KI aqueous solution in Emulsion 2 to adjust the silver potential to -50 mV, -30 mV and -20 mV. , 5 were prepared.

(Preparation of emulsions 6, 7 and 8) The amount of the KI aqueous solution added to emulsion 2 was 830 to 620 ml.
Emulsion 6 by reducing to 410 ml and 205 ml
7,8 were prepared.

(Preparation of Emulsions 9, 10 and 11) In the emulsion 2, the temperature when AgNO ₃ was added for the first time was 30 ° C.
To 45 ° C, 60 ° C, and 75 ° C to prepare emulsions 9, 10, and 11. (Preparation of Emulsions 12, 13, and 14) In Emulsion 2, the aging time and temperature were 75 ° C., 40 minutes to 60 ° C. 40 minutes, and 5
Emulsions 12, 13, and 14 were prepared by setting the temperature to 0 ° C. for 40 minutes and 50 ° C. for 20 minutes.

The emulsions thus formed are summarized in Table A below.

(2) Preparation of coated sample and its evaluation Sample 101 was prepared by preparing a multi-layer color light-sensitive material having the following composition on a cellulose triacetate film support having a thickness of 127 μm which was undercoated. The numbers represent the amount added per m ² . The effect of the added compound is not limited to the described use.

First layer: antihalation layer Black colloid 0.25 g Gelatin 1.9 g UV absorber U-1 0.04 g UV absorber U-3 0.1 g UV absorber U-4 0.1 g UV absorber U -6 0.1 g High boiling organic solvent Oil-1 0.1 g.

Second layer: intermediate layer Gelatin 0.4 g Dye D-4 0.4 mg Compound Cpd-D 4 mg High boiling point organic solvent Oil-2 0.04 g UV absorber U-2 0.1 g.

Third Layer: Intermediate Layer Finely grained silver iodobromide emulsion with the surface and inside fogged (average grain size 0.06 μm, coefficient of variation 18%, Agl content 1 mol%) silver amount 0.05 g gelatin 0.4 g .

Fourth Layer: Low-Sensitivity Red Sensitive Emulsion Layer Emulsion A Silver amount 0.1 g Emulsion B Silver amount 0.4 g Gelatin 0.8 g Coupler C-1 0.15 g Coupler C-2 0.05 g Coupler C-9 90 0.05 g.

Fifth layer: Medium sensitivity red-sensitive emulsion layer Emulsion C Silver amount 0.5 g Gelatin 0.8 g Coupler C-1 0.2 g Coupler C-2 0.05 g Coupler C-3 0.2 g High boiling point organic solvent Oil -2 0.1 g.

Sixth layer: High-sensitivity red-sensitive emulsion layer Emulsion D Silver amount 0.4 g Gelatin 1.1 g Coupler C-3 0.7 g Coupler C-1 0.3 g Additive P-1 0.1 g.

Seventh layer: Intermediate layer Gelatin 0.6 g Additive M-1 0.3 g Color mixing inhibitor Cpd-K 2.6 mg UV absorber U-1 0.1 g UV absorber U-6 0.1 g Compound Cpd -D 2.0 mg High boiling organic solvent Oil-2 0.04 g.

Eighth layer: intermediate layer Silver iodobromide emulsion with surface and inside fogged (average grain size 0.06 μm, variation coefficient 16%, Agl content 0.3 mol%) Silver amount 0.02 g Gelatin 1 0.0 g Additive P-1 0.2 g Color mixing inhibitor Cpd-J 0.1 g Color mixing inhibitor Cpd-A 0.1 g.

Ninth layer: low-sensitivity green-sensitive emulsion layer Emulsion E Silver amount 0.25 g Emulsion F Silver amount 0.15 g Gelatin 0.5 g Coupler C-4 0.2 g Coupler C-7 0.1 g Coupler C-80 .1 g Compound Cpd-B 0.03 g Compound Cpd-E 0.02 g Compound Cpd-F 0.02 g Compound Cpd-G 0.02 g Compound Cpd-H 0.02 g High boiling point organic solvent Oil-1 0.1 g High boiling point organic Solvent Oil-2 0.1 g.

10th layer: Medium sensitivity green sensitive emulsion layer Emulsion G Silver amount 0.4 g Gelatin 0.6 g Coupler C-4 0.1 g Coupler C-7 0.1 g Coupler C-8 0.1 g Compound Cpd-B 0 0.03 g Compound Cpd-E 0.02 g Compound Cpd-F 0.02 g Compound Cpd-G 0.05 g Compound Cpd-H 0.05 g High boiling point organic solvent Oil-2 0.01 g.

Layer 11: High-sensitivity green-sensitive emulsion layer Emulsion H Silver amount 0.5 g Gelatin 1.0 g Coupler C-8 0.1 g Coupler C-4 0.3 g Compound Cpd-B 0.08 g Compound Cpd-E 0 0.02 g Compound Cpd-F 0.02 g Compound Cpd-G 0.02 g Compound Cpd-H 0.02 g High boiling point organic solvent Oil-1 0.02 g High boiling point organic solvent Oil-2 0.02 g.

Twelfth layer: intermediate layer Gelatin 0.6 g Dye D-2 0.05 g Dye D-1 0.02 g Dye D-3 0.01 g.

Thirteenth layer: Yellow filter layer Yellow colloidal silver Silver amount 0.1 g Gelatin 1.1 g Color mixing inhibitor Cpd-A 0.01 g High boiling point organic solvent Oil-1 0.01 g.

Fourteenth layer: Intermediate layer 0.6 g of gelatin.

Fifteenth layer: low-sensitivity blue-sensitive emulsion layer Emulsion I Silver amount 0.4 g Emulsion J Silver amount 0.2 g Gelatin 0.8 g Coupler C-5 0.6 g.

Sixteenth layer: Medium speed blue-sensitive emulsion layer Emulsion K Silver amount 0.5 g Gelatin 0.9 g Coupler C-5 0.3 g Coupler C-6 0.3 g.

Seventeenth layer: High-sensitivity blue-sensitive emulsion layer Emulsion H Silver amount 0.4 g Gelatin 1.2 g Coupler C-6 0.7 g.

Eighteenth layer: First protective layer Gelatin 0.3 g Ultraviolet absorber U-1 0.04 g Ultraviolet absorber U-2 0.01 g Ultraviolet absorber U-3 0.03 g Ultraviolet absorber U-4 0. 03g UV absorber U-5 0.05g UV absorber U-6 0.05g High boiling point organic solvent Oil-1 0.02g Formalin scavenger Cpd-C 0.2g Cpd-I 0.4g Cpd-L 2.3mg Dye D-3 0.05 g.

19th layer: second protective layer Colloidal silver Silver amount 0.1 mg Fine grain silver iodobromide emulsion (average particle size 0.06 μm, Agl content 1 mol%) Silver amount 0.1 g Gelatin 0.4 g.

20th layer: Third protective layer Gelatin 0.2 g Polymethylmethacrylate (average particle size 1.5 μ) 0.1 g Methyl methacrylate / acrylic acid 4: 6 copolymer (average particle size 1.5 μ) 0.1 g Silicone oil 0.03 g Surfactant W-1 3.0 mg Surfactant W-2 0.03 g.

Phenol as an antiseptic / antifungal agent,
1,2-benzisothiazolin-3-one, 2-phenoxyethanol, and phenethyl alcohol were added.

Further, in addition to the above composition, additives F-1 to F-
-7 was added. Further, in each layer, in addition to the above composition, a gelatin hardening agent H-1 and a coating and emulsifying surfactant W-3 are provided.
~ 6 was added.

Silver iodobromide emulsions A to L used for Sample 101
Are as shown in Tables B and C below. The names or chemical structural formulas of the compounds used in the preparation of Sample 101 are as shown in Chemical Formulas 18 to 34 below.

(Production of Samples 102 to 114) Sample 101
Samples 102 to 114 were prepared in the same procedure as in Sample 101 except that Emulsions-2 to 14 were used in place of Emulsion H (Emulsion 1) used in the 17th high-sensitivity blue-sensitive emulsion layer.

(Evaluation of Paint Sample) The sample pieces of the coated samples 101 to 114 obtained as described above were exposed to a white light wedge at an exposure time of 1/100 second and an exposure amount of 20 CMS, and then developed as follows. Sensitometry was performed, and the sensitivity was determined by the reciprocal of the exposure amount that gives the minimum density of magenta +1.0, and D = 0.5 on the characteristic curve.
And gamma was calculated from the slope of the straight line connecting the point of D = 2.0. Next, two sets of sample pieces of the coated samples 101 to 114 were prepared and subjected to wedge exposure under the same exposure conditions as above, one set immediately after exposure, one set immediately after exposure at 50 ° C. for 55% for 3 days and the same treatment. Then, the sensitivity was calculated from the reciprocal of the exposure dose that gives the minimum density + 1.0, and the storability was evaluated.

[0160]

The composition of each processing solution was as follows.

[0162]

(Reversal Solution) Start Solution / Replenisher Common Unit (g) Nitrilo-N, N, N-trimethylene 2.0 Phosphonic Acid / 5-Sodium Salt Stannous Chloride / Dihydrate 1.0 p-Aminophenol 0.1 Sodium hydroxide 8.0 Glacial acetic acid 15 ml Water was added to 1.0 liter Ammonium sulfite 20 Water was added to 1.0 liter pH (25 ° C.) 6.60 pH was adjusted with acetic acid or aqueous ammonia.

(Color developer) Start solution Replenisher unit (g)

(Adjustment Solution) Start Solution / Replenisher Common Unit (g) Ethylenediaminetetraacetic acid ・ 28.0 sodium salt ・ dihydrate sodium sulfite 12 2-methylcapto-1,3,4-0.5 triazole pH ( 25 ° C.) 6.00 pH was adjusted with hydrochloric acid or sodium hydroxide.

(Bleach) Start Solution / Replenisher Common Unit (g) 1,3-Diaminopropane 3 Tetraacetic Acid 1,3-Diaminopropane 12.0 Ferric Ammonium Tetraacetate Dihydrate Glycolic Acid 4.0 Acetic acid 30 Ammonium bromide 120 Ammonium nitrate 25 Water was added to 1.0 liter pH (25 ° C.) 4.20 pH was adjusted with acetic acid or aqueous ammonia.

(Fixer) Starter / Replenisher common unit (g) Ethylenediaminetetraacetic acid.1.72 Sodium dihydrate Benzaldehyde-o-sulfone 20 Sodium sodium bisulfite 15 Ammonium thiosulfate 250 ml (700 g / liter) 1.0 liter pH was added with water (25 ° C.) 6.00 The pH was adjusted with acetic acid or aqueous ammonia.

(Stabilizing Solution) Unit (g) Sodium p-toluenesulfinate 0.1 Polyoxyethylene-p-monononyl 0.2 Phenyl ether (Average degree of polymerization: 10) Ethylenediaminetetraacetic acid disodium salt 0.05 N-methylol Pyrazole 0.04 mol Formalin 0.02 mol Water was added to 1.0 liter pH 7.2 The above results are shown in Table D below.

The following can be seen from Tables A and D. i) In the emulsions 3, 4, and 5, the number of grains in which dislocations are observed tends to increase in comparison with the emulsion 2, but the intergrain iodide distribution is widened, and the gradation becomes soft. ii) In Emulsions 6, 7, and 8, the intergranular iodide distribution was narrowed in order, but the proportion of grains containing dislocations was decreased, and the latent image storability was extremely deteriorated. iii) Emulsions 9, 10 and 11 have a gradually widened grain size distribution and soft gradation. iv) In emulsions 12, 13, and 14, the proportion of grains having an aspect ratio of 3 or more decreased in order, and soft gradation was observed. v) Emulsion 1, which shows almost no dislocations, is not preferable in terms of softening of gradation and latent image storability.

Example 2 Emulsions (E to H) and couplers C-4, C-7 and C-8 contained in the 9th to 11th layers in Sample 101 of Example 1 were used.
Samples 201 to 215 were prepared in exactly the same manner except that was changed as shown in Table E below. Further, this coated sample was evaluated for photographic characteristics in the same manner as in Example 1. The results are shown in Table F below. The outline of the results was as follows. i) When the coupler C-8 of the present invention was not contained in the 9th and 10th layers, there was almost no effect of improving the storage stability and gradation by the emulsion (comparison between samples 201 and 202). ii) The coupler C-8 of the present invention had the most preferable photographic characteristics when it was contained in the medium- and low-sensitivity green-sensitive layers, and also had good color reproducibility (comparison between samples 203 and 204). iii) Even when the coupler C-8 of the present invention is contained in all of the green-sensitive layers, preferable photographic characteristics were obtained by using it in combination with the emulsion of the present invention (Samples 201, 202, 10).
Comparison of 1,102). iv) Among the emulsions contained in the green-sensitive layer, the resolution of the red-sensitive layer (cyan color-forming layer) on the support side was improved as the composition ratio of the emulsion of the present invention was increased, and a more preferable light-sensitive material was obtained. ..

Example 3 Example 3 and photosensitive material 9 described in JP-A-2-93641
Sample No. 301, except that the coupler ExM-7 of the sixth layer was replaced with the coupler C-8 of the present invention and the emulsion of the eighth layer was replaced with the emulsion 2 of the present invention.
Was produced. It was found that when this was exposed and developed in the same manner as in the above publication, color reproducibility, storability and photographic characteristics were improved.

[0172]

[Chemical 1]

[0173]

[Chemical 2]

[0174]

[Chemical 3]

[0175]

[Chemical 4]

[0176]

[Chemical 5]

[0177]

[Chemical 6]

[0178]

[Chemical 7]

[0179]

[Chemical 8]

[0180]

[Chemical 9]

[0181]

[Chemical 10]

[0182]

[Chemical 11]

[0183]

[Chemical formula 12]

[0184]

[Chemical 13]

[0185]

[Chemical 14]

[0186]

[Chemical 15]

[0187]

[Chemical 16]

[0188]

[Chemical 17]

[0189]

[Chemical 18]

[0190]

[Chemical 19]

[0191]

[Chemical 20]

[0192]

[Chemical 21]

[0193]

[Chemical formula 22]

[0194]

[Chemical formula 23]

[0195]

[Chemical formula 24]

[0196]

[Chemical 25]

[0197]

[Chemical formula 26]

[0198]

[Chemical 27]

[0199]

[Chemical 28]

[0200]

[Chemical 29]

[0201]

[Chemical 30]

[0202]

[Chemical 31]

[0203]

[Chemical 32]

[0204]

[Chemical 33]

[0205]

[Chemical 34]

[0206]

[Table 1]

[0207]

[Table 2]

[0208]

[Table 3]

[0209]

[Table 4]

[0210]

[Table 5]

[0211]

[Table 6]

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Megumi Sakagami 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture Fuji Photo Film Co., Ltd.

Claims (1)

Claims: 1. A photographic light-sensitive material having at least one silver halide emulsion layer on a support, wherein (1) at least 50% of the total projected area is contained in the silver halide emulsion layer. Tabular silver halide grains having an aspect ratio of 3 or more occupy 50% of the tabular silver halide grains, and the variation coefficient of the grain size distribution of the tabular silver halide grains is 25% or less, and the variation coefficient of the silver iodide content distribution of each grain. Is less than 30%, 5 of the total number
1 per grain for silver halide grains equivalent to 0% or more
Halogenated silver halide photographic emulsion characterized by having 0 or more dislocations and (2) a magenta coupler represented by the general formula (A) described in Chemical formula 1 below. Silver photographic light-sensitive material. (In the general formula (A), R ₁ represents a hydrogen atom or a substituent, and X represents a hydrogen atom or a group capable of leaving by a coupling reaction with an oxidized product of an aromatic primary amine developer. Za and Zb. And Zc represents methine, substituted methine, = N- or -NH-, and Za-
One of the Zb bond and the Zb-Zc bond is a double bond, and the other is a single bond. An aromatic ring may be condensed at Zb-Zc. It also includes the case where R ₁ or X forms a dimer or higher multimer. In addition, when Za, Zb or Zc is a substituted methine, it also includes the case where the substituted methine forms a dimer or higher multimer. )