JPH04204642A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain the silver halide color photographic sensitive material adapted to rapid processing and superior in color tone reproduction performance by mixing a silver halide emulsion spectrally sensitized so as to become sensitive to a primary color in a complementary color relation to a color developing dye, with another silver halide emulsion spectrally sensitized to at least one primary color of residual primary colors so as to satisfy specified conditions. CONSTITUTION:The silver halide emulsion (a) sensitized to the primary color in a complementary color relation to the color developing dye is mixed with the silver halide emulsion (b) spectrally sensitized to at least one of the residual primary colors in a silver in (a) to silver in (b) ratio of 1.0-0.1, and the sensitivity of the emulsion (b) is regulated to 1/3-1/32 of the sensitivity of the emulsion (c) spectrally sensitized to the same primary color and this emulsion is contained in an emulsion layer containing a coupler developing a color in a complementary color relation to the primary color to which the emulsion (b) is sensitized, thus permitting the obtained silver halide color photographic sensitive material to obtain both of high-density color tone reproduction performance and rapid processing aptitude.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a silver halide photographic material, and in detail,
This invention relates to a silver halide color photographic material which is excellent in rapid processing properties and has good color reproducibility and tone reproducibility.

(Prior Art) In recent years, in photographic development processing, there has been a demand for silver halide photographic materials that can be processed quickly and have excellent image quality such as color reproducibility and tone reproducibility.

With regard to rapid processing, silver halide photographic materials are processed continuously in automatic processing machines installed at each processing laboratory, and as part of our efforts to improve service to users, we have decided to The need for this is increasing, as it has become necessary to develop the prints and deliver them to the user within a few days, and even more recently, it has become necessary to deliver the prints within a few hours of receipt.

Furthermore, shortening of processing time improves production efficiency and makes it possible to reduce costs, so there is an urgent need to develop rapid processing.

In order to achieve rapid processing, approaches have been taken from both the light-sensitive material and the processing solution. Regarding color development processing, attempts have been made to raise the temperature and pH of the processing solution, to add a color developing agent to a high concentration, and it is also known to add additives such as development accelerators.

Examples of the development accelerator include 1-phenyl-3-pyrazolidone described in British Patent No. 811°185, and U.S. Pat.
N-methyl-p-aminophenol described in , 417,514, N, N, N' described in JP-A-50-15554
, N'-tetramethyl-p-phenylenediamine, and the like.

However, even with these methods, sufficient speed is not achieved and performance deterioration such as increased fog is often accompanied.

On the other hand, it is known that the shape, size, and composition of silver halide grains in silver halide emulsions used in light-sensitive materials have a large effect on development speed, etc., and the halogen composition has a particularly large effect; It has been found that the use of silver halide emulsions containing high silver contents exhibits significantly higher development rates.

On the other hand, the formation of a dye image in a silver halide color photographic light-sensitive material usually occurs when an aromatic primary amine color developing agent reduces silver halide grains in the exposed silver halide color photographic light-sensitive material. This oxidation is carried out by coupling this oxidized product with a coupler previously contained in the silver halide color photographic light-sensitive material. Generally, three types of couplers are used, each of which forms three pigments: yellow, magenta, and cyan, in order to perform color reproduction using the subtractive color method.

In order to achieve better color reproduction, it is necessary to have a very large number of elements in place.In other words, the spectral sensitivity and glabella effect of the photosensitive material for photography, and the spectral sensitivity of the photosensitive material for printing are required. The level of color reproducibility is determined by the matching of color-forming dyes in photosensitive materials for photography, the overlap of the spectral sensitivities of light-sensitive layers with different color sensitivities, the spectral absorption characteristics of color-forming dyes, and color mixing during processing between light-sensitive layers with different color-forming dyes. influence.

In order to improve image quality, tone reproduction is also important, and not only gray gradation but also color gradation is important.

Recent progress in improving the image quality of color photography is largely due to advances in the so-called multilayer effect of photographic light-sensitive materials, which greatly contributes to improved color reproducibility, especially when such light-sensitive materials are used. Color gradation is often not expressed adequately.

(Problem to be Solved by the Invention) In recent years, high silver chloride as mentioned above has been used in photosensitive materials to meet the above-mentioned demand for rapid processing, and the sulfite contained in the color development processing solution for ordinary color paper has been used. New systems are being developed and introduced for use in combination with benzyl alcohol and processing solutions that do not use benzyl alcohol.

The photographs obtained with the high-silver chloride color paper used in this new rapid processing have an inherent sensitivity of red sensitivity, green sensitivity, and blue sensitivity because silver chloride or silver chloride has no absorption in the visible range. without impairing the discriminative function of
Although it has the advantage of not causing so-called color mixing, it has been found that it has the problem that color gradations, especially in high density areas, are harder to express than when using conventional silver chlorobromide. It is hoped that this problem can be solved without compromising processability or other advantages.

This problem is particularly likely to appear when reproducing original color gradations with bright reds and yellows, and this drawback is further amplified in color papers using silver chloride.

In recent years, pyrazoloazole-based magenta couplers have become known as magenta couplers other than the 5-pyrazolone couplers that have been widely used in color papers and the like. For this family of couplers, 5-
It is known that the coloring dye not only has better spectral absorption characteristics than pyrazolone couplers, but also has good fastness to light and less staining due to the coupler itself, and has many practical advantages. Among these pyrazoloazole magenta couplers, pyrazolo (5,1-cl
[1,2,4] t-Riazoles, pyrazolo [
5,1-bl [1,2,4] Triazoles are preferable in terms of overall performance of color-forming properties, spectral absorption characteristics of color-forming dyes, and color image fastness, and are particularly preferred in U.S. Patent No. 4,540,65
Pyrazolo [5,1-bl [1,2,4
] Triazoles can be preferably used.

However, despite these favorable points, when these couplers are used in a green-sensitive silver halide emulsion layer, the aforementioned insufficient color gradation tends to be further accentuated. discovered.

Therefore, when such a pyrazoloazole magenta coupler is used in a color paper using a high silver chloride emulsion as a silver halide emulsion, the insufficiency of color gradation expression is likely to be further emphasized.

As a means to improve the insufficiency of color gradation expression, a method is known, for example, of providing a photosensitive layer that forms a black dye image, as described in Japanese Patent Publication No. 58-10737. However, it is difficult to develop a black-coloring coupler that is sufficiently useful for practical use.

Furthermore, there is no description regarding rapid processing or problems in improving color saturation. Furthermore, JP-A-61-91657 discloses a method for improving the tone reproducibility of a colored image by adding a dye image having a different hue above a certain density of the dye image. There is no mention of the advantage of using a pyrazoloazole magenta coupler to achieve both rapid processing and improving color gradation while increasing saturation and improving color reproducibility. There are no technical suggestions regarding improving expressiveness.

JP-A-2-129628 discloses that in order to impart color gradation to a red image, a cyan coupler-containing silver halide emulsion layer was spectrally sensitized to red and blue and/or green, and magenta and yellow were developed. It shows a method of increasing the expressive power of red color gradation by further developing cyan in high-density areas.

Also, Japanese Patent Application Publication No. 64-68754 (US 4,902.60
No. 9) discloses methods of widening the exposure latitude by imparting different color sensitivities, but in these methods, the gradation of the cyan image in the red area is equivalent to the gradation of the cyan image. However, it is impossible to freely adjust the color gradation in high density areas, and it has been desired to develop a new means.

The purpose of the present invention is to arbitrarily adjust color tone reproducibility, especially high-density color tone reproducibility, and achieve both rapid processability and silver halide silver halide excellent in color reproducibility and color tone reproducibility. An object of the present invention is to provide color photographic materials that can be processed quickly.

(Means for Solving the Problems) It has been found that the objects of the present invention can be achieved by the following silver halide color photographic light-sensitive materials.

(1) In a silver halide color photographic light-sensitive material having a yellow coupler-containing silver halide emulsion layer, a magenta coupler-containing silver halide emulsion layer, and a cyan coupler-containing silver halide emulsion layer on a support, each emulsion layer is The average silver chloride content of the silver halide contained is 90 mol% or more, and at least one layer of the emulsion layer is spectrally sensitized to light of a primary color that is complementary to the color-forming dye in relation to the three primary colors of light. a sensitized silver halide emulsion (a);
containing a silver halide emulsion (b) spectrally sensitized so as to be sensitive to at least one of the remaining primary colors;
The ratio of silver content of emulsion (b) to emulsion (a) is from 0.1 to 1.0, and the sensitivity of emulsion (b) (fog density + 0.05) is necessary to give a color density of The reciprocal of the exposure amount (hereinafter the same shall apply) is spectral sensitized so as to be sensitized to the same primary color as the emulsion contained in the coupler-containing silver halide emulsion layer that develops a color complementary to the spectral sensitivity of the emulsion (b). The sensitivity of emulsion (c) is 1/1 in the primary color.
A silver halide color photographic light-sensitive material characterized in that the silver halide color is 3 to 1/32.

(2) In a silver halide color photographic light-sensitive material having a silver halide emulsion layer containing a yellow coupler, a silver halide emulsion layer containing a magenta coupler, and a silver halide emulsion layer containing a cyan coupler on a support, the content is contained in each emulsion layer. The average silver chloride content of the silver halide to be used is 90 mol% or more, and at least one of the emulsion layers is spectral-enhanced so as to be sensitive to primary color light that is complementary to the color-forming dye in terms of the three primary colors of light. Consisting of a composite layer of a layer consisting of a sensitized silver halide emulsion (a) and a layer consisting of a silver halide emulsion (b) spectrally sensitized so as to be sensitized to at least one of the remaining primary colors, The layer consisting of emulsion (b) may or may not contain a coupler that develops the same color as the layer consisting of emulsion (a). The ratio of the contents of couplers of the same color is 1.0 to 0.0 in molar ratio, and emulsion (b)
The sensitivity of the emulsion (c), which is contained in a coupler-containing emulsion layer that develops a color complementary to the spectral sensitivity of the emulsion, is spectrally sensitized to be sensitive to the same primary color as the emulsion, and the sensitivity of the primary color is A silver halide color photographic material characterized in that the silver halide color photographic material has a ratio of 1/3 to 1/32.

(3) The silver halide color photographic light-sensitive material according to item (1) or item (2), wherein the coupler contained in the magenta coupler-containing silver halide emulsion layer is a pyrazoloazole coupler.

Examples of embodiments of the present invention will be described in detail below.

In the present invention, for each coloring layer, (1) the cyan coupler-containing silver halide emulsion layer is "an emulsion spectrally sensitized to be sensitive to primary color light having a complementary color relationship with the cyan coloring dye, that is, red light". (R) and "an emulsion spectrally sensitized to be sensitive to the primary colors", i.e., a mixing emulsion sensitized with green- or/and blue-sensitive sensitizing dyes (respectively GM, BM, GBM) may be mixed and contained in the same layer, or may be contained in separate layers.

■The magenta coupler-containing silver halide emulsion layer consists of an emulsion (G) sensitized with a green-sensitive sensitizing dye and a mixed emulsion (R) sensitized with a red- and/or blue-sensitive sensitizing dye (respectively R).
M, BM, RBM) may be mixed and contained in the same layer, or may be contained in separate layers.

■The yellow coupler-containing silver halide emulsion layer consists of an emulsion (B) sensitized with a blue-sensitive sensitizing dye and a mixed emulsion (R) sensitized with a red- and/or green-sensitive sensitizing dye (respectively R
M, GM, ROM) may be mixed and contained in the same layer, or may be contained in separate layers.

Here, RM, GM, and BM are "mixing emulsions (b) spectrally sensitized to be sensitive to red, green, and blue, with a small amount of residual primary colors." It is an abbreviation.

GBM, RBM, and RGM are abbreviations for mixing emulsions that have been subjected to two types of spectral sensitization among "mixing emulsions that have been spectrally sensitized to be sensitive to at least one of the remaining primary colors." As a method for performing such two types of spectral sensitization, it is preferable to add two types of dyes that sensitize different spectral regions, but it is preferable to add one type of spectral sensitization that sensitizes these two types of spectral regions. A sensitizing dye may be added.

It is preferable that any one of the above embodiments (1), (2), and (3) corresponds to at least one silver halide emulsion layer in which a coupler is combined with a conventional complementary color sensitizing dye. It is also preferable that the two types of layers correspond to any one of the embodiments (1), (2), and (2) above, or the three types of counterfeit money correspond to the embodiments (1), (2), and (2) above.

In addition to the layer consisting of "an emulsion that has been spectrally sensitized to be sensitive to light of a primary color that is complementary to the color-forming dye," there is a layer that contains "an emulsion that is spectrally sensitized to be sensitive to light of a primary color that is complementary to the color-forming dye." In the case where the layers contain "an emulsion", those layers are preferably provided adjacent to each other.

A layer containing the "spectrally sensitized emulsion so as to be sensitive to at least one of the remaining primary colors" provided adjacent to the layer (
In the past, it is preferable to contain a layer (I) consisting of "an emulsion spectrally sensitized so as to be sensitive to primary color light having a complementary color relationship with the color-forming dye" and a coupler that develops substantially the same color. This coupler coverage ratio of layer (II) to layer (I) is less than or equal to 1.0. It is preferably 0.5 or less, particularly preferably 0.3 or less.

Furthermore, when these layers are provided adjacent to each other, this layer (I[) may not contain a coupler.

The "emulsion spectrally sensitized to be sensitive to at least one of the remaining primary colors" may contain two or more types.

Silver amount ratio of [GM%BM, total of GBM] to (R), or silver amount ratio of [RM, BM, RBM total] to (G), or [RM%GM%R to (B)
The silver content ratio [total GM] is 0.01 or more and 1.0 or less, preferably 0.05 or more and 0.5 or less, particularly preferably 0.1 or more and 0.3 or less.

BM%GM and RM can also be contained in two different coloring layers at the same time. In this case, different sensitivities can be used for each layer.

The silver halide emulsion contained in the cyan coupler-containing photosensitive silver halide emulsion layer of the present invention is a silver halide emulsion containing 90 mol% or more of silver chloride in the halogen composition, and substantially contains silver iodide. A silver chloride or silver chlorobromide emulsion is preferred. If the silver bromide content is high or contains silver iodide, there are fewer color gradation problems to be solved by the present invention, but if the silver bromide content exceeds 10 mol%, When a light-sensitive material containing a silver halide emulsion is run in a processing solution, the concentration of bromide ions that accumulate in the solution as a result of development increases, slowing down the development speed and maintaining rapid processing. The disadvantage is that it cannot be done. The silver iodide content is preferably 1 mol % or less, from the viewpoint of eliminating adverse effects due to processing solution accumulation, and particularly preferably 0.2 mol % or less. The silver chloride content may be any amount as long as it is 90 mol% or more, but it is preferably 95 mol% or more, and more preferably 98 mol% or more. Most preferably it is 99 mol% or more.

The high silver chloride emulsion used in the present invention preferably has a silver bromide localized phase with a relatively high silver bromide content in its silver halide grains. Such a silver bromide localized phase may be present inside the silver halide grain, on the grain surface or near the grain surface, or on both. This localized silver bromide phase may take the form of a so-called core-shell type shell structure that wraps around the entire grain inside the grain or on the grain surface (also, part of the shell structure may be missing, or Furthermore, it may have a localized structure having a plurality of discontinuous and mutually independent partial structures. A preferable example of such a localized structure is a silver halide grain having a localized phase on the surface or inside near the surface. In particular, the edges and corners of the crystal surface of particles,
Alternatively, those having localized phases on the crystal planes are preferable. The halogen composition in the localized phase may be 5 mol % or more and 80 mol % or less in terms of silver bromide content, and preferably 10 mol % or more and 60 mol % or less.

The remaining silver halide of the localized phase consists of silver chloride, but preferably also contains a trace amount of silver iodide. However, as mentioned above, it is not preferable for the amount to exceed 1 mol % based on the total amount of silver halide.

Further, these localized phases preferably account for 0.03 mol% or more and 35 mol% or less of the silver halide constituting all the silver halide grains of the emulsion, and more preferably 0.1 mol%.
It is preferable that it accounts for 25 mol% or less.

The localized phase does not need to consist of a single halogen composition (it may have two or more localized phases with distinctly different silver bromide contents, and it may not be composed of other phases other than the localized phase). The interface may be formed with the halogen composition continuously changing.

In order to form the silver bromide localized phase as described above, a water-soluble silver salt and a water-soluble halide salt containing water-soluble bromide are simultaneously mixed into an emulsion containing already formed silver chloride or high silver chloride grains. or by converting some of the already formed silver chloride or high silver chloride grains into a silver bromide-rich phase using the so-called halogen conversion method, or by reacting and depositing silver chloride or high silver chloride grains It can also be formed by adding silver bromide or high silver bromide grains of finer grain size than the grain size and crystallizing the silver chloride or high silver chloride grains by recrystallization on the surface of the silver chloride or high silver chloride grains.

Such a production method is also described, for example, in European Patent Application No. 273,43OA2.

The silver bromide content of the localized phase can be determined by the XA1 diffraction method (for example, described in ``Chemical Society of Japan, New Experimental Chemistry Course 6, Structural Analysis'', Maruzen) or by the XPS method (for example, ``Surface Analysis, -IMA, Auger Electronics'').・Applications of photoelectron spectroscopy - described in J.
It can also be determined by the method described in No. 43OA2.

The silver halide grains used in the present invention include metal ions other than silver ions (for example, metal ions of Group 1 of the periodic table, metal ions of Group 1 of the periodic table,
By including transition metal ions of Group I, lead ions of Group II, gold ions and copper ions of Group I, etc.) or their complex ions, the color gradation improving effect of the present invention can be improved under various conditions. It is preferable in terms of performance. These metal ions or complex ions thereof may be contained in the entire silver halide grains, in the localized silver bromide phase described above, or in other phases.

Among the metal ions or complex ions thereof, those selected from iridium ions, palladium ions, rhodium ions, iron ions, iron ions, platinum ions, gold ions, copper ions, etc. are particularly useful. Desired photographic properties are often obtained by using these metal ions or complex ions in combination rather than using them alone, and in particular by changing the type and amount of added ions between the localized phase and its opposite part of the particle. It is preferable. In particular, it is preferable that iridium ions, rhodium ions, and iron ions be contained in the localized phase.

In order to incorporate metal ions or complex ions into the localized phase of silver halide grains and/or other parts of the grains, the metal ions or complex ions can be incorporated into the silver halide grains by a physical process before, during or after the formation of the silver halide grains. It may be added directly to the reaction vessel during ripening, or it may be added in advance to the addition liquid of the water droplet halogen salt or water-soluble silver salt. When the localized phase is formed from fine grains of silver bromide or high silver bromide, it is contained in silver bromide or high silver bromide fine grains using the same method as above, and then added to the silver chloride or high silver chloride emulsion. You may. Furthermore, metal ions may be contained while forming a localized phase by adding a relatively sparingly soluble bromide of metal ions other than silver salt, such as those mentioned above, in solid or powder form.

In order to achieve sufficient rapid processability in the present invention, the yellow coupler-containing silver halide emulsion layer, the magenta coupler-containing silver halide emulsion layer, and the cyan coupler-containing silver halide emulsion are all high-silver chloride emulsions as described above. It is preferable to use

The silver halide grains used in the present invention can have the shape of so-called regular grains such as cubes, octahedrons, dodecahedrons, or rhombidodecahedrons, or irregular grains such as spherical and tabular shapes. It can also take the form of particles.

Further, the particles may have a more complex shape having a combination of these crystal planes, or may even have a higher-order crystal plane. These silver halide grains may be mixed. Preferably used in the present invention is a silver halide emulsion containing 50% or more, more preferably 70% or more, still more preferably 90% or more of silver halide grains having a regular crystalline shape in terms of grain number or weight. In particular, emulsions containing crystal grains having (100) crystal faces are preferred.

Further, in the emulsion used in the present invention, tabular grains having an average aspect ratio (ratio of circular diameter/grain thickness to the main plane of the grain) of 5 or more, particularly preferably 8 or more account for 50 or more of the total projected area of the grains. If the emulsion is such that it occupies 100% of the total amount of light, it is not only advantageous in terms of rapid processability, but also the effect of the present invention on color gradation is more clearly expressed.

The grain size of the silver halide emulsion used in the present invention is not particularly limited as long as it does not impair rapid processability, but
The average diameter when the projected area of the particles is converted into a circle is 0.1-
1.7 url is preferable. The size distribution of silver halide grains may be wide or narrow, but so-called monodisperse emulsions are preferred in terms of photographic properties such as latent image stability and pressure resistance, and processing stability such as developer pH dependence.

The value S/d obtained by dividing the standard deviation S of the diameter distribution by the average diameter d when the projected area of silver halide grains is converted into a circle is 20
% or less, more preferably 15% or less7
stomach.

The silver chlorobromide emulsion used in the present invention is P, Glafkide.
"The Chemistry and Physics of Photography" (Ball-Montel, 1967), by G. F. Duffi
“Chemistry of Photographic Emulsions” by N. Duffin (Focal Press, 1966), V. L. Zelic
It can be prepared by applying the method described in ``Preparation and Coating of Photographic Emulsions'' (Focal Press, 1964) by John K+nanf Zerikman, et al. That is,
Any of the acid method, neutral method, ammonia method, etc. may be used,
In particular, acidic methods and neutral methods are preferred in the present invention in terms of reducing fog. Furthermore, in order to obtain a silver halide emulsion by reacting a soluble silver salt and a soluble halide salt, any one of the so-called one-sided mixing method, simultaneous mixing method, or a combination thereof may be used.

It is also possible to use the so-called back-mixing method in which the particles are formed under conditions of excess silver ions. It is preferable to use a simultaneous mixing method to obtain an emulsion of monodisperse grains preferred for the present invention. As one type of simultaneous mixing method, it is more preferable to use a method in which the silver ion concentration in the liquid phase in which silver halide is produced is kept constant, that is, a so-called Chondrald double jet method. By using this method, it is possible to obtain a silver halide emulsion which is preferred for the present invention and has a regular silver halide crystal shape and a narrow grain size distribution.

In the process of grain formation or physical ripening of silver halide, cadmium salt, zinc salt, lead salt, thallium salt, or the above-mentioned iridium salt or its complex salt,
A rhodium salt or a complex salt thereof, an iron salt or a complex salt thereof may be present together.

During or after grain formation, a silver halide solvent (for example, known ones such as ammonia, thiocyanate, U.S. Pat.
No. 0, JP-A-53-82408, JP-A-53-144
319, JP-A-54-100717, JP-A-54-155828, etc.) may be used, and when used in combination with the above method, the silver halide crystal shape becomes regular. A silver halide emulsion preferred for the present invention having a narrow grain size distribution can be obtained.

In order to remove soluble salts from the emulsion after physical ripening, Nudel water washing, flocculation sedimentation, ultrafiltration, or the like can be used.

The emulsion used in the present invention is sulfur-sensitized or selenium-sensitized,
Chemical sensitization can be carried out by reduction sensitization, noble metal sensitization, etc. alone or in combination. That is, active gelatin, a sulfur sensitization method using a compound containing a sulfur compound that can react with silver ions (for example, thiosulfate, thiourea compound, mercapto compound, rhodanine compound, etc.), and a sulfur sensitization method using a reducing substance (for example, stannous salt). , amines, hydrazine derivatives, formamidine sulfinic acid, silane compounds, etc.), and metal compounds (e.g., the aforementioned gold complex salts, platinum, iridium, palladium, rhodium, iron, etc. from Group II of the periodic table). Noble metal sensitization methods using metal salts or complex salts thereof, etc. can be used individually or in combination. In the emulsion of the present invention, sulfur sensitization or selenium sensitization is preferably used, and gold sensitization is also preferably used in combination with these. Further, during these chemical sensitizations, it is preferable to have a hydroxyazaidene compound or a nucleic acid present in order to control sensitivity and gradation.

In the present invention, the sensitizing dye is used as follows. That is, a red-sensitive sensitizing dye is a sensitizing dye that has a peak wavelength of spectral sensitivity of about 590 nm to 720 nm when adsorbed to a silver chloride emulsion, and a blue-sensitive sensitizing dye is a sensitizing dye that has a peak wavelength of spectral sensitivity of approximately 590 nm to 720 nm when adsorbed to a silver chloride emulsion. Sometimes approximately 390nm to 510r++
A sensitizing dye that has a peak wavelength of spectral sensitivity at approximately 510 nm to 590 nm when adsorbed to a silver chloride emulsion, and is usually The silver halide emulsion layer containing a yellow coupler is sensitized with a blue-sensitive sensitizing dye, the silver halide emulsion containing a magenta coupler is sensitized with a green-sensitive sensitizing dye, and the silver halide emulsion layer containing a cyan coupler is sensitized with a red-sensitive sensitizing dye. The sensitivity of the blue-light-sensitive emulsion or the edge-sensitive emulsion of the red-sensitive silver halide emulsion layer containing a cyan coupler is higher than that of the blue-light-sensitive emulsion of the silver halide emulsion layer containing a yellow coupler, respectively. It is preferable that the printer has a sensitivity of 1/3 or less and 1/32 or more relative to the sensitivity of the green light-sensitive emulsion of the silver halide emulsion layer containing a magenta coupler. This is undesirable because color mixture that impairs color saturation occurs even in relatively low-density areas that do not cause problems.
On the other hand, if the sensitivity is only 1/32 or less, hardly any of the effects of the present invention can be obtained in the first place. More preferably, 1
The sensitivity is set to be 74 or less and 1732 or more.

Particularly preferably, it is 1/8 or less and I/16 or more.

The effects of the present invention are particularly clear when a pyrazoloazole coupler is used as the magenta coupler, as described above.In other words, when the technology of the present invention is applied to such a system, pyrazoloazole It is possible to achieve both high color saturation due to the excellent spectral absorption properties of the color-forming dyes of azole couplers, and conversely, a color gradation that is easy to tab, as well as rapid processability and color image fastness. A color photographic material having excellent properties can also be obtained.

Spectral sensitizing dyes used in the present invention include cyanine dyes, merocyanine dyes, composite merocyanine dyes, and the like.

In addition, complex cyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes are used. As cyanine dyes, simple cyanine dyes, carbocyanine dyes, and dicarbocyanine dyes are preferably used. These cyanine dyes can be represented by the following general formula (1).

-Formula (I) R, -N-+CH-CH+=iF8-7C-fL+"r
-C(cH=CHhTp-R.

fX).

In the formula, L represents a methine group or a substituted methine group, R2 and R2 each represent an alkyl group or a substituted alkyl group, and zl and Z2 each represent a nitrogen-containing 5- or 6-membered heterocyclic nucleus. represents an atomic group, and X represents an anion. n represents a numerical value of 1, 3 or 5, n and C2 are each O or l, and when n=5, n
Both l and C2 are 0, and when n=3, either nl or C2 is O. 0m represents O or 1, but is O when forming an inner salt. Also, when n is 5, L
They may be linked together to form a substituted or unsubstituted 5- or 6-membered ring.

The cyanine dye represented by general formula (I) will be explained in detail below.

Examples of the substituents of the substituted methine group represented by the above include lower alkyl groups (eg, methyl group, ethyl group, etc.) and aralkyl groups (eg, benzyl group, phenethyl group, etc.).

The alkyl residue represented by 8 and R2 may be linear or branched (or cyclic).Although there is no restriction on the number of carbon atoms, it is preferably from 1 to 8, especially from 2 to 7.
is particularly preferred. Further, examples of the substituent of the substituted alkyl group include a sulfonic acid group, a carboxylic acid group, a hydroxyl group, an alkoxy group, an acyloxy group, and an aryl group (eg, a phenyl group, a substituted phenyl group, etc.). These groups may be bonded to the alkyl group alone or in combination of two or more. Further, the sulfonic acid group or the carboxylic acid group may form a salt with an alkali metal ion or a quaternary ion of an organic amine. Here, the expression "two or more groups are combined" includes a case where these groups are each independently bonded to an alkyl group, and a case where these groups are connected and bonded to an alkyl group.

Examples of the latter include a sulfoalkoxyalkyl group, a sulfoalkoxyalkoxyalkyl group, a carboxyalkoxyalkyl group, and a sulfophenylalkyl group.

Specific examples of R and R1 are methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group,
2-hydroxyethyl group, 4-hydroxybutyl group, 2
-acetoxyethyl group, 3-acetoxypropyl group, 2
-methoxyethyl group, 4-methoxybutyl group, 2-carboxyethyl group, 3-carboxypropyl group, 2-(2
-carboxyethoxy)ethyl group, 2-sulfoethyl group, 3-sulfopropyl group, 3-sulfobutyl group, 4-sulfobutyl group, 2-hydroxy-3-sulfopropyl group, 2-(3-sulfopropoxy)ethyl group, 2 -acetoxy-3-sulfopropyl group, 3-methoxy-2-(3
-sulfopropoxy)propyl group, 2-[2-(3-sulfopropoxy)ethoxy]ethyl group, 2-hydroxy-3-(3'-sulfopropoxy)propyl group, and the like.

Specific examples of the nitrogen-containing heterocyclic nucleus formed by zI or z2 include oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, pyridine nucleus, oxazoline nucleus,
Examples include a thiazoline nucleus, a selenazoline nucleus, an imidacilline nucleus, and those condensed with a benzene ring, a naphthalene ring, or other saturated or unsaturated carbon rings. Alkyl group, trifluoromethyl group, alkoxycarbonyl group, cyan group, carboxylic acid group, carbamoyl group, alkoxy group, aryl group, acyl group, hydroxyl group,
halogen atoms, etc.) may be bonded.

Anions represented by X include C1-, Br-, I-
.

SO, -, NO, -, C1O, -, etc. can be mentioned.

Merocyanine dyes or composite merocyanine dyes include a pyrazolin-5-one nucleus, a thiohydantoin nucleus, and a 2-thioxazolidine-2 nucleus having a ketomethylene structure.
, 4-dione nucleus, thiazolidine-2,4-dione nucleus, rhodanine nucleus, thiobarbic acid nucleus, etc. can be incorporated.

The present invention includes a biroline nucleus, an oxacylyl nucleus, a thiazoline nucleus, a pyrrole nucleus, a thiazole nucleus, an oxazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, a pyridine nucleus, an alicyclic hydrocarbon ring, and an aromatic ring. Spectral sensitizing dyes other than those described above that incorporate a nucleus of fused hydrocarbon rings can also be used.

Useful spectral sensitizing dyes include, for example, German Patent No. 929
,080, U.S. Patent No. 2,231,658, U.S. Pat.
493,748, 2.503,776, 2,519.001, 2.912,329, 3,656,959, 3.672,897 ,
No. 3,694,217, No. 4,025,349, No. 4,046,572, British Patent No. 1.242.
No. 588, Special Publication No. 44-14030, No. 52-248
Examples include those described in No. 44 and the like.

In the present invention, among the above dyes, those having a benzothiazole nucleus or a benzoxazole nucleus are preferable, such as simple cyanine dyes having a benzothiazole nucleus, carbocyanine dyes having a benzoxazole nucleus, and dicarbocyanine dyes having a benzothiazole nucleus. Dyes are particularly preferred.

Usually, in order to spectral sensitize a silver halide emulsion, a method is used in which grains are completely formed and then a spectral sensitizing dye is adsorbed onto the surface of the grains. On the other hand, U.S. Patent No. 2.735.766 discloses a method of adding a merocyanine dye during precipitation of silver halide grains, which is believed to reduce the amount of dye that is not adsorbed. Are listed. Also, JP-A-55-26
No. 589 discloses a method in which a spectral sensitizing dye is added and adsorbed during addition of an aqueous silver salt solution and a halogen salt aqueous solution to form silver halide crystal grains. In this way, the spectral sensitizing dye may be added during the formation of silver halide crystal grains, after the formation is completed, or even before the formation begins. Specifically, "before the start of grain formation" means that a spectral sensitizing dye is introduced into the reaction vessel before starting the reaction to form silver halide crystals, and "during grain formation" means that the spectral sensitizing dye is introduced into the reaction vessel before starting the reaction to form silver halide crystals. The term "after the completion of particle formation" refers to the addition and adsorption after the substantial process of particle formation has been completed. Although the silver halide emulsion of the present invention is chemically sensitized after the completion of grain formation, the addition of a spectral sensitizing dye after the completion of grain formation may be carried out during chemical sensitization even before the start of such chemical sensitization. However, in the present invention, the above-mentioned spectral sensitizing dyes may be added to the coating solution even after the completion of chemical sensitization. It is preferable that it be added before preparing.

The spectral sensitizing dye to be added may be added as it is in the form of crystals or powder, but it is preferably added after being dissolved or dispersed by some method. For dissolution, a water-soluble solvent such as an alcohol having 1 to 3 carbon atoms, acetone, pyridine, methyl cellosolve, or a mixed solvent thereof may be used. It is also possible to perform micelle dispersion or other dispersion using a surfactant.

The amount of spectral sensitizing dye added depends on the purpose of spectral sensitization and the content of the silver halide emulsion, but it is usually from 1X10-' mol to 1X10-' mol per 1 mol of silver halide.
2 mol, more preferably 1 x 101 mol to 5 x 10-
``Mole is added.

The spectral sensitizing dye used in the present invention may be used alone, but
Two or more types may be used in combination.

Among the sensitizing dyes preferably used in the present invention, formula -8 (
Specific examples of the cyanine dye represented by I) include (V-1) to (V-36) described on pages 10 to 13 of JP-A-2-129628.

Along with the spectral sensitizing dye, it contains a dye that itself does not have a spectral sensitizing effect, or a supersensitizer that has no substantial absorption in the visible region but enhances the sensitizing effect of the spectral sensitizing dye. Good too.

In the present invention, aminostilbene compounds substituted with a nitrogen-containing heterocyclic group (for example, U.S. Pat. No. 2,933,3
No. 90 and No. 3,635.721) are
It is useful for reducing the residual color of the carbocyanine dye having an oxazole nucleus and improving the color sensitization of the dicarbocyanine dye having a benzothiazole nucleus, and is particularly preferably used in combination.

As the aminostilbene compound preferably used in the present invention, 4,4°-bis(S-triazinylamino)stilbene-2,2°-disulfonic acid or 4,4°-
Examples include bis(pyrimidinylamino)stilbene-2,2°-disulfonic acid and alkali metal salts thereof. In these compounds, the S-triazine ring or pyrimidine ring is a substituted or unsubstituted arylamino group, a substituted or unsubstituted alkylamino group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted alkyloxy group, or It is further preferred that one or two positions be substituted with a hydroxyl group, an amino group, or the like. In order to reduce residual color, it is more preferable that this portion be substituted with a highly water-soluble substituent. The highly water-soluble substituent is, for example, a substituent containing a sulfonic acid group or a hydroxyl group.

These compounds are represented by the following general formula (F).

General formula (F) R13R+s In the formula, D represents a divalent aromatic residue, Rl t+ Rl
3.

Rl 4 * Rl! + represents a hydrogen atom, hydroxy group, alkoxy group, aryloxy group, halogen atom, heterocyclic group, mercapto group, alkylthio group, arylthio group, heterocyclylthio group, amino group, alkylamino group, cyclohexylamino group, arylamino group, respectively. group, heterocyclylamino group, aralkylamino group or aryl group.

Ql and Q each represent -N= or 10:.

However, at least one of Q+ and Q2 is -N=.

Examples of compounds particularly preferably used in the present invention include (F-1) to (F-24) described on pages 15 to 18 of JP-A-2-129628.

The silver halide emulsion of the present invention has the purpose of preventing the occurrence of fog and improving the stability of photographic performance during the manufacturing process of photographic light-sensitive materials, during storage before development, or during development. The following compounds can be added and contained. That is, firstly, heterocyclic mercapto compounds such as mercaptothiadiazoles, mercaptotetrazoles, mercaptobenzimidazoles, mercaptobenzothiazoles, mercaptopyrimidines, mercaptothiazoles, etc., and secondly, water-soluble compounds such as carboxyl groups and sulfone groups. the above-mentioned heteromercapto compounds having a functional group, thirdly azoles such as benzothiazo12ium salts, nitroindazoles, triazoles,
Benzotriazoles, benzimidazoles (particularly nitro- or halogen-substituted), fourthly thioketo compounds such as oxazolidinethione, and fifthly azaindenes such as tetraazaindenes, more specifically hydroxyazaindenes. , aminoazaindenes, especially 4-hydroxy-6-methyl-1,3,3a,
? Many compounds known as antifoggants or stabilizers such as -tetraazaindene, benzenethiosulfinic acids, benzenesulfinic acids, etc. can be added. In particular, heteromercapto compounds and azaindenes are preferably used in the present invention.

In the present invention, during and after silver halide grain formation,
Add it during/after chemical sensitization or when coating emulsion.
Mercaptotetrazole compounds which are particularly preferably used for preventing fog and improving processing dependence can be selected from compounds represented by the following general formula (Ia).

- Formula (1a) In the formula, R represents an alkyl group, an alkenyl group, or an aryl group, and X represents a hydrogen atom, an alkali metal atom, an ammonium group, or a cursor.

Examples of the alkali metal atom include a sodium atom and a potassium atom, and examples of the ammonium group include a trimethylammonium chloride group and a dimethylbenzylammonium chloride group. Further, the precursor refers to a group that can form X=H or an alkali metal under alkaline conditions, such as an acethyl group, a cyanoethyl group, a methanesulfonylethyl group, and the like.

Among the above R, the alkyl group and alkenyl group include unsubstituted and substituted groups, and also include alicyclic groups. Substituents for the substituted alkyl group include a halogen atom, an alkoxy group, an aryl group, an acylamino group, an alkoxycarbonylamino group, a ureido group, a hydroxy group, an amino group, a heterocyclic group, an acyl group, a sulfamoyl group, a sulfonamide group,
Examples include a thiourido group, a carbamoyl group, and further a carboxylic acid group, a sulfonic acid group, or a salt thereof.

The above ureido group, thioureido group, sulfamoyl group, carbamoyl group, and amino group are each unsubstituted,
Including those substituted with N-alkyl and those substituted with N-aryl. Examples of aryl groups include phenyl groups and substituted phenyl groups, and examples of substituents include alkyl groups and substituted products of the alkyl groups listed above.

Further, preferred mercaptothiadiazole compounds can be selected from compounds represented by the following general formula (ITa).

General Formula (IIa) In the formula, L represents a divalent linking group, and R represents a hydrogen atom, an alkyl group, an alkenyl group, or an aryl group. The alkyl group, alkenyl group and X of R are the same as those in general formula (Ia).

Specific examples of the divalent linking group represented by L above include the following. n represents 0 or l, and R, , R, and R2 each represent a hydrogen atom, an alkyl group, or an aralkyl group.

In addition to these compounds, those preferably used in the present invention include mercaptobenzimidazoles.

Preferred specific examples of these compounds are listed below.

(I-6) H (I-7) (I-11) δh (I-12) (II-1) (n-2) (n-3) (II-4) (II-5) (n- 6) The photosensitive material according to the present invention has a hydrophilic colloid layer containing European patent EP0 for the purpose of improving image sharpness, etc.
, No. 337.49OA2, pages 27 to 76, dyes that can be decolorized by treatment (especially oxonol dyes) are used when the optical reflection density at 680 nm of the material is 0.7.
0 or more, or 12% by weight or more (more preferably 14 (wt% or more) is preferably contained.

Further, in the light-sensitive material according to the present invention, it is preferable to use a color image preservation improving compound as described in European Patent EP 0,277.589A2 together with a coupler.

Particularly preferred is the combination with a pyrazoloazole coupler.

That is, a compound (F) that chemically bonds with the aromatic amine developing agent remaining after color development processing to produce a chemically inert and substantially colorless compound and/or an aroma remaining after color development processing. For example, in storage after processing, the compound (G) that chemically bonds with the oxidized form of a group amine color developing agent to produce a chemically inert and substantially colorless compound may be used simultaneously or singly. This is preferable in order to prevent staining and other side effects caused by the formation of coloring dyes due to the reaction between the color developing agent or its oxidized product remaining in the film and the coupler.

Furthermore, in order to prevent various types of mold and bacteria that propagate in the hydrophilic colloid layer and cause image deterioration, the light-sensitive material according to the present invention contains an anti-mold agent as described in JP-A No. 63-271247. It is preferable to do so.

The support used in the photosensitive material according to the present invention may be a white polyester support for display or a support in which a layer containing a white pigment is provided on the support on the side having a silver halide emulsion layer. In order to further improve sharpness, it is preferable to coat an antihalation layer on the side of the support coated with the silver halide emulsion layer or on the back side.

In particular, it is preferable to set the transmission density of the support in the range of 0.35 to 0.8° so that the display can be viewed in both reflected light and transmitted light.

The photosensitive material according to the present invention may be exposed to visible light or infrared light, and the exposure method may be low-light exposure or high-light short-time exposure, and especially in the latter case, the Laser scanning exposure systems with exposure times shorter than 10-' seconds are preferred.

Further, during exposure, it is preferable to use a band stop filter described in US Pat. No. 4,880,726. This eliminates optical color mixture and significantly improves color reproducibility.

For the purpose of rapid processing, it is preferable to bleach-fix the exposed light-sensitive material after color development.Especially when the above-mentioned high silver chloride emulsion is used, the pH of the bleach-fix solution should be adjusted to promote desilvering. It is preferably about 6.5 or less, more preferably about 6 or less.

Silver halide emulsions and other materials (additives, etc.) and photographic constituent layers (layer arrangement, etc.) applied to the photosensitive material of the present invention, and processing methods and processing materials applied to process this sensitive material. As additives, the following patent publications, especially European Patent EP0.355.66OA2 (Patent Application Hei 1-1)
07041) are preferably used.

In addition, as a cyan coupler, in addition to the diphenylimidazole cyan coupler described in JP-A No. 2-33144, the cyan coupler described in European Patent EP 0,333.185A2
- Hydroxypyridine cyan couplers (particularly preferred are couplers (6) and (9), in which a 4-equivalent coupler of coupler (42) listed as a specific example is made into 2-equivalent couplers by adding a chlorine leaving group), Japanese Patent Publication No. 64-322
60 (including the cyclic active methylene cyan couplers listed as specific examples 3.8.
34 is particularly preferred).

Example 1 An emulsion for a photosensitive silver halide emulsion layer containing a cyan coupler was prepared as follows.

30g of coal-processed gelatin and 1000TIIIi of distilled water! After dissolving at 40°C, the pH was adjusted to 348 with sulfuric acid, 5.5 g of sodium chloride and 0.02 g of N,N'-dimethylimidazolidine-2-thione were added, and the temperature was adjusted to 52.5. The temperature was raised to ℃. 62.5g of silver nitrate in 77g of distilled water
A solution prepared by dissolving 21.5 g of sodium chloride in 500 ml of distilled water was added to and mixed with the above solution for 40 minutes while maintaining the temperature at 52.5°C. Furthermore, silver nitrate 62
．． A solution of 5g dissolved in 500ml of distilled water and 21.5g of sodium chloride dissolved in 300Tn of distilled water [! and the solution dissolved in
The mixture was added and mixed for 20 minutes at 2.5°C.

When the obtained emulsion was observed under an electron microscope, it was found to be about 0.
The emulsion consisted of cubic grains with an average side length of 46 μm and a coefficient of variation of grain size distribution of 0.09.

After washing this emulsion with desalinated water, a monodisperse silver bromide emulsion containing 0.2 g of nucleic acid, 1 mol Ag of red sensitizing dye (V-6) IXIO-' and an average grain size of 0.05 μm (iridium dipotassium hexachloride) was prepared. 2×10-' mol 1 mol Ag) was added with silver halide equivalent to 0.6 mol %, and chemically sensitized with 2×10-6 mol 1 mol Ag in the form of triethylthiourea. Emulsion Em-1 was prepared by adding 7×10 −' 1 mol Ag of 8) to the emulsion Em-1.

Furthermore, 2.0% of the following compound per mole of silver halide was added.
6 x 104 moles were added.

On the other hand, in the preparation method of Em-1, the particle formation temperature was lowered to make the average particle size 0.38μ, and the amount of (V-6) added was 1
．． Emulsion Em-1 except that 2×10-'mol 1 mol Ag
Emulsion Em-4 was obtained in the same manner as above, and used as a low-sensitivity red-sensitive emulsion for use in a cyan coupler-containing silver halide emulsion layer.

A green-sensitive emulsion for a silver halide emulsion layer containing a magenta coupler was prepared as follows.

30g of coal-processed gelatin and 1000m of distilled water! After dissolving at 40℃, add 5.5g of sodium chloride and N,N
'-dimethylimidazolidine-2-thione 0.02g
was added and the temperature was raised to 50°C. silver nitrate 62.5
g to 750Tnfl of distilled water! A solution obtained by dissolving 21.5 g of sodium chloride in 500 yn12 of distilled water was added to and mixed with the above solution for 40 minutes while maintaining the temperature at 50°C. Furthermore, a solution in which 62.5 g of silver nitrate was dissolved in 500 ml of distilled water and a solution in which 21.5 g of sodium chloride was dissolved in 300 ml of distilled water were added and mixed at 50 DEG C. over 20 minutes.

When the obtained emulsion was observed under an electron microscope, it was found to be about 0.
The emulsion consisted of cubic grains with an average side length of 44μ and a coefficient of variation of grain size distribution of 0.08.

After washing this emulsion with desalinated water, 0.2 g of nucleic acid, 1 mol Ag of 5X 10-' mol of exemplified compound (V-41), and a monodisperse silver bromide emulsion (iridium dipotassium hexachloride) with an average grain size of 0.05 μm were added. 2.5 x 10-' mol 1 mol Ag) was added with silver halide equivalent to 0.4 mol %, and chemically sensitized with 2.5 x 1 O-' mol 1 mol Ag in triethylthiourea, and further exemplified. Compound (I-8) 1.1x
1 mole of Ag was added to prepare a green-sensitive emulsion Em-2 for a silver halide emulsion layer containing a magenta coupler.

On the other hand, in the preparation method of emulsion Em-2, the temperature during grain formation was lowered to give an average grain size of 0.37μ, and (V-4
1) was made into 6×10 −′ mol 1 mol Ag. Others are emulsion E
Emulsion Em-5 was prepared in the same manner as Em-2.

This emulsion was used as a low-speed green-sensitive emulsion for a silver halide emulsion layer containing a magenta coupler.

A blue-sensitive emulsion for a yellow coupler-containing silver halide emulsion layer was prepared as follows.

Add 30 g of coal-treated gelatin to 1000 TIt of distilled water, dissolve at 40°C, and adjust the pH to 3.8 with sulfuric acid.
Add 5.5 g of sodium chloride and 0603 g of N,N'-dimethylimidazolidine-2-thione and bring the temperature to 75°C.
It was raised to . Dissolve 2.5 g of silver nitrate in 150 ml of distilled water and 4.3 g of sodium chloride in 100 ml of distilled water.
1 was added to and mixed with the above solution for 30 minutes while maintaining the temperature at 75°C. Furthermore, a solution of 112.5 g of silver nitrate dissolved in 1100 ml of distilled water and 38.7 g of sodium chloride were added.
was dissolved in 650 ml of distilled water and mixed at 75° C. over 40 minutes.

When the obtained emulsion was observed under an electron microscope, it was found to be about 0.
The emulsion consisted of cubic grains with an average side length of 82μ and a coefficient of variation of grain size distribution of 0.11.

After washing this emulsion with desalinated water, 0.2 g of nucleic acid, 1 mol of blue sensitizing dye (V-34) 2
) 2xlO-'mol 1 mol Ag, average particle size 0,0
A 5μ monodisperse silver bromide emulsion (containing 1 mole of Ag, dipotassium iridium hexachloride, 1X10-5 mol) was added in an amount equivalent to 0.3 mol% of silver halide, and 1.2 x 10-6 of triethylthiourea was added. Chemically sensitized with 1 mol of Ag, and then 9×10-' mol of exemplified compound (1-8) with 1 mol of Ag.
This was added to prepare a high-speed blue-sensitive emulsion Em-3 for a silver halide emulsion layer containing a yellow coupler.

On the other hand, in the preparation method of Em-3, the temperature during particle formation was lowered to make the average particle size 0.70μ, and (V-34), (
The amount of V-36) added was 2.5 x 10-'mol 1, respectively.
Emulsion Em was prepared in the same manner as Emulsion Em-3 except that the mole Ag was changed.
-6 was prepared and used as a low-speed blue-sensitive emulsion for a silver halide emulsion layer containing a yellow coupler.

The halogen composition and distribution of the above green-sensitive silver halide emulsion for the magenta coupler-containing layer and the blue-sensitive silver halide emulsion for the yellow coupler-containing layer were observed by X-ray diffraction, and it was found that the halogen composition was equivalent to 100 mol% of silver chloride. In addition to the main beak, a broad diffraction pattern centered around 70 to 65 mol % of silver chloride and tailed to around 60 mol % of silver chloride could be faintly observed.

After corona discharge treatment is applied to the surface of a paper support laminated on both sides with polyethylene, a gelatin undercoat layer containing sodium dodecylbenzenesulfonate is applied, and various photographic constituent layers are further applied to produce multilayer colors with the layer structure shown below. Photographic paper was prepared and designated as sample 101. The coating solution was prepared as follows.

1st layer coating liquid preparation yellow coupler (ExY) 19. 1 g and 4 g of color image stabilizer (cpd-1) and 0.7 g of color image stabilizer (cpd-7), 27.2 cc of ethyl acetate and 4 g each of solvent (Solv-3) and (Solv-7) .1 g was added and dissolved, and this solution was emulsified and dispersed in 185 cc of a 10% gelatin aqueous solution containing 8 cc of 10% sodium dodecylbenzenesulfonate to prepare emulsified dispersion A.

This emulsion contains the following blue-sensitive sensitizing dye (V-34),
(V-36) per mole of silver is 2, QXlo-4 moles, respectively, for large emulsion Em-3, or 2.5X10-
'Mole has been added. Further, chemical ripening of this emulsion was carried out by adding a sulfur sensitizer and a gold sensitizer. Emulsion Em-3
and Em-6 in a ratio of 3=7, and then mixed and dissolved with the emulsified dispersion A described above to obtain the composition shown below.
A layer coating solution was prepared.

Coating solutions for the second to seventh layers were also prepared in the same manner as the coating solution for the first layer (also in the fifth layer, after the cyan coupler was dissolved in ethyl acetate together with the color image stabilizer (CPD-7), etc. , emulsified and dispersed). As the gelatin hardening agent for each layer, 1-oxy-3,5-dichloro-5-1-riazine sodium salt was used.

Further, Cpd-10 and Cpd-11 were added to each layer in a total amount of 25.0 mg/rrr and 50.0 mg/rrr, respectively.

In addition, 1-(5
-methylureidophenyl)-5-mercaptotetrazole at 8.5 x 10 per mole of silver halide, respectively.
-' mol, 7.7 x 10-4 mol, and 2.5 x 10-' mol were added.

In addition, 4-hydroxy-6-methyl-1,
3,3a,7-tetrazaindene were added in amounts of I×10 −4 mole and 2×10 −′ mole, respectively, per mole of silver halide.

In addition, the following dyes (coating amounts are shown in parentheses) were added to the emulsion layer to prevent irradiation.

(losig/-3) (40s+g/m") and (Layer composition) The composition of each layer is shown below. The number is the coating amount (g/m")
represents. The silver halide emulsion represents the coated amount in terms of silver.

Support polyethylene laminate paper [The polyethylene on the first layer side contains white face N (Ti12) and blue dye (ulmarine blue)] -th layer (blue-sensitive emulsion N) Above emulsion Em-30,09 Above emulsion Em -60,21 Gelatin 1.86 Yellow coupler (ExY) 0.82 Color image stabilizer (cpd-1) 0.19
Solvent (Solv-3) 0.
18 solvent (Solv-7)
0.18 color image stabilizer (cpd-7)
0.06 Second layer (color mixing prevention layer) Gelatin 0.99 Color mixing prevention agent (cpd-5) 0.08 Solvent (Solv-1), 0
．． 16 solvent (Solv-4)
0.08 Fifth layer (green-sensitive emulsion layer) Above emulsion Em-20,04 Above emulsion Em-50,07 Gelatin 1.24 Magenta coupler (ExM) 0.23 Color image stabilizer (cpd-2) 0 .03
Color image stabilizer (cpd-3) 0.
16 color image stabilizer (cpd-4)
0.02 color image stabilizer (cpd-9)
0.02 solvent (Solv-2)
0.40 Fourth layer (ultraviolet absorption layer) Gelatin 1.58 Ultraviolet absorber (UV-1) 0.47 Color mixture prevention agent (cpd-5) 0.05
Solv-5 0
．． 24 Fifth layer (red-sensitive emulsion IN) Above emulsion Em-10,07 Above emulsion Em-40,15 Gelatin 1.34 Cyan coupler (ExC) 0.32 Color image stabilizer (c9d-2) 0.03
Color image stabilizer (cpd-4) 0.
02 color image stabilizer (cpd-6)
0.18 color image stabilizer (cpd-7)
0.40 color image stabilizer (cpd-8)
0.05 solvent (Solv-6)
0.14 6th layer (ultraviolet absorption layer) Gelatin 0.53 ultraviolet m
Absorber (UV-1) 0.16 Color mixture prevention agent (CPD-5) 0.02
Solvent (Solv-5) 0
．． 08 Seventh layer (protective layer) Gelatin 1.3 Acrylic modified copolymer of polyvinyl alcohol (denaturation degree 17%)
) 0.17, liquid paraffin 0゜03([!XY)
l:1 mixture (molar ratio) with yellow coupler (ExM) magenta coupler (HxC) mixture (molar ratio) of 11 by weight each of cyan coupler (cpd-1) color image stabilizer (cpd-2) color image stabilizer Agent (cpd-3) Color image stabilizer (cpd-4) Color image stabilizer (cpd-5) Color mixing inhibitor H (cpd-6) 2:4!4 mixture (weight ratio) of color image stabilizer (cpd -7) Color image stabilizer average molecular weight 60.000 (cpd-8) tit mixture with color image stabilizer (weight ratio) (cpd-9) color image stabilizer (cpd-10) preservative ((:pd- 11) Preservative (UV-1) 4:2:4 mixture (weight ratio) of ultraviolet absorber (Solv-1) Solvent (Solv-2) l:l mixture (volume ratio) of solvent (Solv-2) 3) Solvent (Solv-4) t'ij medium (Solv-5) Solvent COO *Htv (Solv-6) Solvent C5) 1+telIljl(cHt)vcOo(:J+
80:20 mixture (volume ratio) with t\1 (Solv-7) solvent Cm)1+, c) ICII (cut)yCOOCsll
+t\1 (V-6) (V-34) (V-36) (V-41) The amount of sensitizing dye used in emulsions E+a-1, -2 and -3 was changed as shown in Table-1. Then, emulsion Em-7~
Em-15 was prepared.

Samples 102 to 114 were prepared by changing the combination of emulsions from sample 101 as shown in Table 2.

Table 2 Table 2 (Continued) *Adjacent separate layers are made by replacing the silver halide emulsion with the specified one for the original coupler-containing layer and changing the coating amount of the entire layer. The silver content ratio with the containing layer was changed.

First, for sample 101, the amount of developed silver is 3 compared to the amount of silver coated.
Continuous processing (running test) was carried out until twice the tank capacity for color development was replenished using a solution having the following processing steps and processing solution composition.

Maru 1 work 11--1 Concave 凰天l Bimataheno Volume color development 35℃ 45 seconds 1611I11217℃ bleach fixing 30-35℃ 45 seconds 215mJ 17I
2 Rinse■ 30~35℃ 20 seconds -lOβ rinse■ 30~35℃ 20 seconds -lOβ rinse■ 30
~35℃ 20 seconds 350mJ2 10℃ drying 70-80℃ 60 seconds Umbrella replenishment amount is per 1 m'' of photosensitive material (3 tank countercurrent method from rinse ■→■) The composition of each processing solution is as follows. be.

L ni Satoyoji L's 2 prisoners Hiten Yarizu
800mj2 8
00+oI2 Ethylenediamine-N,N,N,N-tetramethylenephosphonic acid 1.5g 2.0gPotassium bromide 0.015g -Triethanolamine 8.0g 12.0g
Sodium chloride 1.4g - Potassium carbonate 25g 25g
N-ethyl-N-(β-methanesulfonamidoethyl)-3-methyl-4-aminoaniline sulfate 5.0 g 7.0
gN,N-bis(carboxymethyl)hydrazine 4. Og 5.0g
N,N-di(sulfoethyl)hydroxylamine/INa 4. Og 5.
0g Fluorescent brightener fWHITEX 4B, manufactured by Sumitomo Chemical) 1.0g
Add 2.0g water and 1000m
ff 1000n+l2pH (25℃)
10.05 10.451 Water
400ml Ammonium thiosulfate (70%
) 100mI2 Sodium sulfite 1
7 g Iron (m) ethylenediaminetetraacetate Ammonium 55 g Disodium ethylenediaminetetraacetate 5 g Ammonium bromide 40 g Add water
1oooa+βpH (25℃) 6.0 1zsuyo (tank liquid and replenisher are the same) Ion exchange water (calcium and magnesium are 3 p each)
pm or less) Next, a coarsely textured bright red costume (wool sweater), a ball of bright yellow wool, and a magenta corduroy cloth are rolled up into appropriate shapes at the same time, placed on the table, and are pulled from diagonally above. After setting the lighting, I took a picture using Fuji Color Negative Super HR100 film,
After developing with Fuji specified process CN-16, each of the above-mentioned samples was printed through this negative using a Fuji 0450 printer, and the same development process was performed using the developer after the continuous processing to produce color prints.

The obtained color prints were subjected to sensory evaluation on the following items according to the following criteria.

Item - Vividness of color The degree to which the magenta cloth, red sweater, and yellow yarn ball looked bright as a whole was divided into three levels. A
: Good B: Slightly inferior C: Inferior.

Item-2 Red color gradation The texture of the red sweater looked three-dimensional and whether shadows were visible or not was divided into three levels. A: Good
B: Slightly inferior C: Inferior.

Item-3 Yellow color gradation The yellow yarn balls were divided into three levels in terms of whether they looked three-dimensional and whether shadows were visible.

A: Good B: Slightly poor C: Poor.

The evaluation results are summarized in Table-3.

As shown in Table 3, it can be seen that the combination of the present invention is able to add color gradation without impairing the vividness of colors, and is able to express details in high density areas well.

Adding tone by appropriately controlling and adding other colors to high-density areas gives features such as reproducing the overall tone and improving three-dimensionality without visually reducing the vividness of the colors. It was shown that it is possible.

(Effects of the Invention) According to the present invention, it is possible to obtain a silver halide color photographic material that can be rapidly processed and has excellent color reproducibility and color tone reproducibility.

Procedural amendment (master) August 16, 1991

Claims (3)

[Claims] (1) In a silver halide color photographic light-sensitive material having a yellow coupler-containing silver halide emulsion layer, a magenta coupler-containing silver halide emulsion layer, and a cyan coupler-containing silver halide emulsion layer on a support, each emulsion layer contains The average silver chloride content of the silver halide to be used is 90 mol% or more, and at least one of the emulsion layers is spectral-enhanced so as to be sensitive to primary color light that is complementary to the color forming dye in relation to the three primary colors of light. a sensitive silver halide emulsion (a);
containing a silver halide emulsion (b) spectrally sensitized so as to be sensitive to at least one of the remaining primary colors;
The ratio of silver content of emulsion (b) to emulsion (a) is from 0.1 to 1.0, and the sensitivity of emulsion (b) (fog density + 0.05) is necessary to give a color density of The reciprocal of the exposure amount (hereinafter the same shall apply) is spectral sensitized so as to be sensitized to the same primary color as the emulsion contained in the coupler-containing silver halide emulsion layer that develops a color complementary to the spectral sensitivity of the emulsion (b). The sensitivity of emulsion (c) is 1/1 in the primary color.
A silver halide color photographic light-sensitive material characterized in that the silver halide color is 3 to 1/32. (2) In a silver halide color photographic light-sensitive material having a silver halide emulsion layer containing a yellow coupler, a silver halide emulsion layer containing a magenta coupler, and a silver halide emulsion layer containing a cyan coupler on a support, the content is contained in each emulsion layer. The average silver chloride content of the silver halide to be used is 90 mol% or more, and at least one of the emulsion layers is spectral-enhanced so as to be sensitive to primary color light that is complementary to the color-forming dye in terms of the three primary colors of light. Consisting of a composite layer of a layer consisting of a sensitized silver halide emulsion (a) and a layer consisting of a silver halide emulsion (b) spectrally sensitized so as to be sensitized to at least one of the remaining primary colors, The layer consisting of emulsion (b) may or may not contain a coupler that develops the same color as the layer consisting of emulsion (a), and the layer consisting of emulsion (b) may or may not contain a coupler that develops the same color as the layer consisting of emulsion (a). The ratio of the contents of couplers of the same color is 1.0 to 0.0 in molar ratio, and emulsion (b)
The sensitivity of the emulsion (c), which is contained in a coupler-containing emulsion layer that develops a color complementary to the spectral sensitivity of the emulsion, is spectrally sensitized to be sensitive to the same primary color as the emulsion, and the sensitivity of the primary color is A silver halide color photographic material characterized in that the silver halide color photographic material has a ratio of 1/3 to 1/32. (3) The silver halide color photographic light-sensitive material according to claim (1) or claim (2), wherein the coupler contained in the magenta coupler-containing silver halide emulsion layer is a pyrazoloazole coupler. .