JPH0527379A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain the silver halide color photographic sensitive material improved in red tone reproduction performance. CONSTITUTION:A red-sensitive silver halide emulsion layer containing a cyan coupler formed on a support comprises silver halide emulsion having a silver chloride content of >=90mol% and this emulsion is sensitized so as to have, in addition to the region, spectral sensitization maximum in a wavelength region Xnm satisfying at least one of expressions 1, 2, and 3; 1. X<=lambdaB-30nm, 2. lambdaB+10<=X<=lambdaG-10, 3. lambdaG+10<=X<=lambdaR-50, where lambdaB is the spectral sensitivity maximum wavelength (nm) of the yellow coupler-containing blue-sensitive layer; lambdaG is that of the magenta coupler-containing green-sensitive layer; and lambdaR is that of the cyan coupler-containing red-sensitive layer.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide color photographic light-sensitive material, and more particularly to a silver halide color photographic light-sensitive material excellent in rapid processing suitability and good in color reproducibility and tone reproducibility.

[0002]

2. Description of the Related Art Photographs obtained with high silver chloride color paper suitable for rapid processing have inherent sensitivity of red and green sensitivities because high silver chloride or silver chloride has no absorption in the visible range. Without impairing the discrimination function regarding blue photosensitivity,
Although it has an advantage that so-called color mixing is not caused, there is a problem that the color gradation especially in the high-density portion is more difficult to be expressed than in the case of using conventional silver chlorobromide. This problem is apt to appear particularly when reproducing the original color gradation having vivid red or yellow, and this drawback is magnified in the color paper using high silver chloride.

On the other hand, when a pyrazoloazole-based coupler is used as a magenta coupler, not only the spectral absorption characteristics of the coloring dye are good, but also the stain derived from the coupler itself is small, so that it can be used in a color paper. However, it has been found that the use of this type of coupler in the green-sensitive silver halide emulsion layer is more likely to emphasize the insufficient color gradation as described above.
Therefore, when such a pyrazoloazole-based magenta coupler is used for a color paper using high silver chloride as a silver halide emulsion, insufficient expression of color gradation is easily emphasized.

As a means for improving such insufficient expression of color gradation, for example, a method of providing a photosensitive layer for forming a black dye image as described in JP-B-58-10737 is known. However, it is difficult to develop a black color coupler which can be practically used by this method. In addition, there is no description concerning rapid processing and no description about problems in improving color saturation. In addition, JP-A-61-9
No. 1657 discloses a method of improving tone reproducibility of a colored image by adding a dye image having a hue different from that of a specific density of the dye image. No mention is made of the advantages of compatibility, and the use of pyrazoloazole-based magenta couplers improves saturation and improves color reproducibility while improving the expression of color gradation. There is no technical suggestion.

In JP-A-2-129628, in order to impart a color gradation to a red image, a cyan coupler-containing silver halide emulsion layer is spectrally sensitized into red and blue and / or green, and magenta and yellow are sensitized. This shows a method of further developing cyan in the developed high density portion to enhance the color gradation expression power of red. Further, JP-A-64-68754 (corresponding U.S. Pat. No. 4,902,609) discloses a method of expanding the exposure latitude by imparting different color sensitivities.

[0006]

DISCLOSURE OF THE INVENTION In order to improve the color tone reproducibility, particularly the color tone reproducibility in a high density portion, the present inventor has been shown in the above-mentioned JP-A-2-129628. An experiment was conducted to impart color gradation according to the method. However, although this method certainly improves the color gradation,
When observing the red-colored part of the photographic image from the low-density part to the high-density part, the cyan density increases rapidly at a certain density.For example, in the case of a red woolen sweater, it rapidly becomes dark in the shaded part of the fold. I found that it gives a stiff texture and makes it an unnatural picture.
In the above method, the gradation of the red light exposure in the cyan color forming layer and the gradation of the complementary color exposure of red are the same, and it is unexpected that such a result is apparent.

Therefore, the object of the present invention is to improve the color tone reproducibility, in particular, to improve the color tone reproducibility by shading naturally without causing the red high density portion to be rapidly darkened. An object of the present invention is to provide a silver halide color photographic light-sensitive material which is excellent and suitable for rapid processing.

[0008]

Means for Solving the Problems As a result of intensive studies by the present inventor, the cause of the above-mentioned unnaturalness in the high-density portion of red was given in the examples of JP-A-2-129628 and the like. The spectral sensitivity of the silver halide emulsion contained in the cyan coupler-containing red light-sensitive silver halide emulsion layer at the maximum wavelength position other than the red region is the yellow coupler-containing blue. It is because the spectral sensitivity maximum wavelength of the emulsion contained in the photosensitive silver halide emulsion layer and / or the spectral sensitivity maximum wavelength of the emulsion contained in the magenta coupler-containing green-sensitive silver halide emulsion layer is almost the same position. The inventors have found out that the unnaturalness in the high density portion of red is solved by devising the position of the spectral sensitivity maximum wavelength other than the red region to be imparted, and have completed the present invention.

The objects of the present invention are effectively achieved by the following silver halide color photographic light-sensitive materials. (1) A silver halide having at least one blue light-sensitive silver halide emulsion layer containing a yellow coupler, a green light-sensitive silver halide emulsion layer containing a magenta coupler, and a red light-sensitive silver halide emulsion layer containing a cyan coupler on a support. In the color photographic light-sensitive material, the cyan coupler-containing red light-sensitive silver halide emulsion layer is composed of a silver halide emulsion having a silver chloride content of 90 mol% or more, and the silver halide emulsion has the following relational expression other than in the red region. A silver halide color photographic light-sensitive material, which is sensitized to have a spectral sensitivity maximum at a wavelength X satisfying at least one of 1, 2 or 3. Relational expression 1. X ≦ λ _B −30 2. λ _B + 10 ≦ X ≦ λ _G −10 3. λ _G +10 ≤ X ≤ λ _R -50 (where λ _B is the maximum spectral sensitivity wavelength of the emulsion contained in the yellow coupler-containing blue-sensitive silver halide emulsion layer, λ _G is the magenta coupler-containing green-sensitive silver halide) The maximum spectral sensitivity wavelength of the emulsion contained in the emulsion layer and λ _R represent the maximum spectral sensitivity wavelength in the red region of the emulsion contained in the cyan coupler-containing red light-sensitive silver halide emulsion layer, all in nm. )

(2) The blue light sensitivity and / or green light sensitivity of the cyan coupler-containing red light-sensitive silver halide emulsion layer is higher than the blue light sensitivity of the yellow coupler-containing blue light-sensitive silver halide emulsion layer and the magenta coupler-containing green light sensitivity. 2. The silver halide color photographic light-sensitive material as described in the above item 1, wherein the sensitivity to green light of the silver halide emulsion layer is 1/2 or less and 1/32 or more.

(3) The silver halide color photographic light-sensitive material as described in the above item 1 or 2, wherein the magenta coupler used in the magenta coupler-containing green light-sensitive silver halide emulsion layer is a pyrazoloazole compound.

In the present invention, the spectral sensitivity maximum of the silver halide emulsion contained in the cyan coupler-containing red light-sensitive silver halide emulsion layer other than the red region is included in the yellow coupler-containing blue light-sensitive silver halide emulsion layer. It is important that the spectral sensitivity maximum wavelength of the emulsion and the spectral sensitivity maximum wavelength of the emulsion contained in the magenta coupler-containing green light-sensitive silver halide emulsion layer are in different wavelength regions. It is necessary that the wavelength region satisfy at least one. At this time, for the first time, in terms of color tone reproducibility, particularly in color tone reproducibility in the high density portion, it is possible to obtain an image with a natural feeling without sudden darkening in the high density region.

In the above relational expression 1, X≤λ _B -40
Is more preferable. In relational expression 2, λ _B +1
More preferably, 5 ≦ X ≦ λ _G −20, and λ _B +2
More preferably, 0 ≦ X ≦ λ _G −30. In relational expression 3, λ _G + 20 ≦ X ≦ λ _R −60 is more preferable, and λ _G + 30 ≦ X ≦ λ _R −70 is further preferable.

In the present invention, the blue light sensitivity and / or the green light sensitivity of the cyan coupler-containing red light-sensitive silver halide emulsion layer is the blue light sensitivity of the yellow coupler-containing blue light-sensitive silver halide emulsion layer and the magenta coupler-containing green light sensitivity. 1/2 or less 1/3 for each green light sensitivity of the photographic silver halide emulsion layer
It is preferably 2 or more. When the sensitivity ratio is 1/2 or more, it is not preferable because the color mixture that impairs the color saturation occurs from a relatively low density portion that does not cause a problem in color gradation, and conversely, the sensitivity ratio is 1/32 or less. In that case, the effect of the present invention can hardly be obtained in the first place. The sensitivity ratio is more preferably 1/3 or less and 1/32 or more, and further preferably 1/4 or less and 1/32 or more. Particularly preferably, 1
/ 8 or less and 1/16 or more. The sensitivity in the present invention is defined by the reciprocal of the exposure amount so that the density due to the color forming dye becomes 0.1.

In the present invention, the emulsion contained in the cyan coupler-containing red light-sensitive silver halide emulsion layer contains the following red-light-sensitive sensitizing dye and magenta coupler-containing green light-sensitive silver halide emulsion layer. The following green-sensitive sensitizing dyes are used for the emulsions, and the following blue-sensitive sensitizing dyes are used for the emulsions contained in the yellow coupler-containing green-sensitive silver halide emulsion layer. preferable. That is, the red photosensitive sensitizing dye is a sensitizing dye having a peak wavelength of spectral sensitivity between about 590 nm and 720 nm when adsorbed on a silver chloride emulsion, and the blue photosensitive sensitizing dye is a silver chloride emulsion. 390nm-510n when adsorbed
m is a sensitizing dye having a spectral sensitivity peak wavelength, and a green-sensitive sensitizing dye is a sensitizing dye having a spectral sensitivity peak wavelength between about 510 nm and 590 nm when adsorbed on a silver chloride emulsion. Is.

As the above-mentioned spectral sensitizing dyes, cyanine dyes, merocyanine dyes, complex merocyanine dyes and the like can be used. The cyanine dye is preferably a compound represented by the following general formula (I).

[0017]

[Chemical 1]

The cyanine dye represented by formula (I) will be described in detail below. Examples of the substituent of the substituted methine group represented by L include a lower alkyl group (eg, methyl group, ethyl group, etc.) and an aralkyl group (eg, benzyl group, phenethyl group, etc.).

The alkyl residue represented by R ₁ and R ₂ may be linear or branched, or cyclic. The number of carbon atoms is not limited, but 1 to 8 is preferable, and 2 to 7 is particularly preferable. 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 (for example, a phenyl group, a substituted phenyl group, etc.). These groups may be bonded alone or in combination of two or more to the alkyl group. Further, the sulfonic acid group and the carboxylic acid group may form a salt with an alkali metal ion or a quaternary ion of an organic amine. Here, the combination of two or more includes the case where these groups are independently bonded to an alkyl group and the case where these groups are linked 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 ₁ and R ₂ are methyl group, ethyl group, n-propyl group, n-butyl group and 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 group ) 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 Z ₁ or Z ₂ include oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, pyridine nucleus, oxazoline nucleus, thiazoline nucleus, selenazoline nucleus, imidazoline nucleus, And benzene rings, naphthalene rings or other condensed or unsaturated carbocyclic rings condensed therewith, and these nitrogen-containing heterocycles may be further substituted with substituents (eg alkyl group, trifluoromethyl group, alkoxycarbonyl). Group, cyano group, carboxylic acid group, carbamoyl group, alkoxy group, aryl group, acyl group, hydroxyl group, halogen atom, etc.) may be bonded.

Anions represented by X include Cl ⁻ ,
Br ⁻ , I ⁻ , SO ₄ ⁻ , NO ₃ ⁻ , ClO ₄ ^{− and the} like can be mentioned. Specific examples of the cyanine dye represented by the general formula (I) include those described in JP-A-2-129628.
(V-1) to (V-56) described on pages 0 to 13 can be mentioned. Further, in the merocyanine dye or the complex merocyanine dye, as a nucleus having a ketomethylene structure, a pyrazolin-5-one nucleus, a thiohydantoin nucleus, 2
-5- or 6-membered ring nuclei such as thiooxazolidine-2,4-dione nuclei, thiazolidine-2,4-dione nuclei, rhodanin nuclei, thiobarbituric acid nuclei can be incorporated.

On the other hand, as the blue-sensitizing sensitizing dye and the green-sensitizing sensitizing dye which are provided so as to satisfy the above relational expression, cyanine dye, merocyanine dye, complex merocyanine dye,
It is selected from complex cyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Specific examples of these are listed below,
It is not limited to these.

[0024]

[Chemical 2]

Spectral sensitization of silver halide emulsions is usually carried out after the silver halide grains are completely formed.
A method of adsorbing a spectral sensitizing dye on the surface of these particles is used. In contrast, US Pat. No. 2,735,766
The publication discloses a method of adding a merocyanine dye during the precipitation formation of silver halide grains, and it is stated that it is possible to reduce the dye which does not adsorb. Further, JP-A-55-26589 discloses a method of adding a spectral sensitizing dye during the addition of an aqueous silver salt solution forming a silver halide crystal grain and an aqueous solution of a halogen salt for adsorption. As described above, the spectral sensitizing dye may be added during the formation of the silver halide crystal grains, after the formation thereof, or before the formation thereof. Specifically, before formation is to introduce a spectral sensitizing dye into a reaction vessel in advance before starting a reaction for forming silver halide crystals, and during grain formation means that the above-mentioned patent is used. The term "after the particle formation is completed" means that the particles are adsorbed after the substantial particle formation process is completed. The silver halide emulsion of the present invention is chemically sensitized after the completion of grain formation. However, addition of the spectral sensitizing dye after the completion of grain formation can be performed during the chemical sensitization even before the start of such chemical sensitization. Or even after the completion of chemical sensitization, it may be added just before the emulsion is applied, but in the present invention, the addition of the spectral sensitizing dye as described above is performed in the coating solution. Is preferably added before the preparation of.

The spectral sensitizing dye to be added may be added as it is as a crystal or powder, but it is preferably added after being dissolved or dispersed by some method. To dissolve, alcohols with 1 to 3 carbon atoms, acetone, pyridine,
A water-soluble solvent such as methyl cellosolve or a mixed solvent thereof may be used. Further, a surfactant may be used to disperse micelles or other dispersions. The addition amount of the spectral sensitizing dye depends on the purpose of spectral sensitization and the content of the silver halide emulsion, but is usually 1 × 10 ^-6 mol to 1 × 10 ^-2 mol per mol of silver halide. , More preferably 1 × 10 ⁻⁵ mol to 5 × 10 ⁻³ mol.

A dye that does not have a spectral sensitizing action by itself together with a spectral sensitizing dye, or a supersensitizer that has substantially no absorption in the visible region but enhances the sensitizing action of the spectral sensitizing dye. It may be contained. In the present invention, an aminostilbene compound substituted with a nitrogen-containing heterocyclic group (for example, US Pat. Nos. 2,933,390 and 3,635,335).
No. 721) is useful for reducing the residual color of the carbocyanine dye having the oxazole nucleus and improving the color sensitizing property of the dicarbocyanine dye having the benzothiazole nucleus, and it is particularly preferably used in combination. . Examples of the compounds which are particularly preferably used in the present invention are described in JP-A-2-129628, pages 15-18.
-1) to (F-24) can be mentioned.

The silver halide emulsion of the present invention prevents fog generation and enhances stability of photographic performance during the manufacturing process of a photographic light-sensitive material, during storage until development, or during development. The following compounds may be added and contained for the purpose of That is, first of all, heterocyclic mercapto compounds, such as mercaptothiadiazoles, mercaptotetrazoles, mercaptobenzimidazoles, mercaptobenzothiazoles, mercaptopyrimidines, mercaptothiazoles, etc. Heterocyclic mercapto compounds having a functional group, thirdly azoles, for example, benzothiazolium salts, nitroindazoles, triazoles, benzotriazoles, benzimidazoles (particularly nitro-substituted or halogen-substituted), Fourth, thioketo compounds, such as oxazolidinethione, and fifth, azaindenes, such as tetraazaindenes, more specifically hydroxyazaindenes, aminoazaindenes, especially 4-hydroxy-6-methyiene. -
Many compounds known as antifoggants or stabilizers such as 1,3,3a, 7-tetraazaindene and the like, and further benzenethiosulfinic acids and benzenesulfinic acids can be added and contained. Particularly, the heterocyclic mercapto compound and azaindene are preferably used in the present invention.

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 is substantially iodinated. It is preferably a silver chloride or silver chlorobromide emulsion containing no silver. When the content of silver bromide is high or the content of silver iodide is contained, there are few problems in color gradation to be solved by the present invention, but when the content of silver bromide exceeds 10 mol%, When a light-sensitive material containing a silver halide emulsion is run in a processing solution, the concentration of bromine ions accumulated in the developing solution in equilibrium as a result of development becomes high, the development speed becomes slow, and rapid processing is maintained. There is an inconvenience that you cannot do it.
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. Silver chloride content is 90 mol%
Any amount may be used as long as it is above, but it is preferably 95 mol% or more, further 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 having 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 in the vicinity of the grain surface, or on both of them. This silver bromide localized phase is a so-called core, which surrounds the entire grain inside or on the grain surface.
The shell may have a shell-like structure, or may have a partial lack of shell structure, or may have a localized structure having a plurality of discontinuous and mutually independent partial structures. A preferred example of such a localized structure is one having a localized phase on the surface of the silver halide grain or in the interior close to the surface, and particularly on the edge portion or corner portion of the crystal surface of the grain, or on the crystal plane. Those having is preferred. The halogen composition in the localized phase may have a silver bromide content of 5 mol% or more and 80 mol% or less, and preferably 10 mol% or more and 60 mol% or less.

The remaining silver halide in the localized phase consists of silver chloride, but it is also preferred to contain a trace amount of silver iodide. However, as described above, it is not preferable to exceed 1 mol% with respect to the total amount of silver halide. Further, these localized phases are 0. 0 among silver halides constituting all silver halide grains of the emulsion.
It is preferable to occupy 03 mol% or more and 35 mol% or less, and further preferable to occupy 0.1 mol% or more and 25 mol% or less. The localized phase does not have to consist of a single halogen composition, may have two or more localized phases with distinctly different silver bromide contents, The interface may be formed so that the halogen composition changes continuously.

In order to form the silver bromide localized phase as described above, a water-soluble silver salt and a water-soluble halogen salt containing a water-soluble bromide are added to an emulsion containing silver chloride or high silver chloride grains already formed. The reaction is carried out by the simultaneous mixing method to deposit, or a part of the already formed silver chloride or high silver chloride grains is converted into a silver bromide-rich phase by the so-called halogen conversion method, or silver chloride or high silver chloride is added. It can also be formed by adding fine grained silver bromide or high silver bromide grains in a grain size larger than that of silver chloride grains and crystallizing by recrystallization on the surface of the silver chloride or high silver chloride grains. Such a manufacturing method is described, for example, in European Patent Application Publication No. 0,2.
73,430A2. The silver bromide content of the localized phase can be determined by X-ray diffraction method (for example, described in “Chemical Society of Japan, New Experimental Chemistry Course 6, Structural Analysis” Maruzen) or XP.
S method (for example, described in "Surface Analysis, -IMA, Application of Auger Electron / Photoelectron Spectroscopy-" by Kodansha), etc. can be used for analysis. The silver bromide localized phase can also be known by electron microscope observation or the method described in the above-mentioned European Patent Application Publication No. 0,273,430A2.

The silver halide grains used in the present invention include metal ions other than silver ions (for example, metal ions of group VIII of the periodic table, transition metal ions of group II, lead ions of group IV, group I). It is preferable to include the above-mentioned gold ion, copper ion or the like) or a complex ion thereof in order to exert the color gradation improving effect of the present invention better under various conditions. The metal ions or complex ions thereof may be contained in the entire silver halide grains, the above-described silver bromide localized phase, or any other phase. Among the above metal ions or complex ions thereof, those selected from iridium ion, palladium ion, rhodium ion, zinc ion, iron ion, platinum ion, gold ion, copper ion and the like are particularly useful. It is often the case that these metal ions or complex ions are used in combination, rather than being used alone, to obtain desirable photographic properties. In particular, it is necessary to change the added ionic species and the added amount between the localized phase and other parts of the particle. Is preferred. In particular, iridium ions, rhodium ions, and iron ions are preferably contained in the localized phase.

In order to incorporate a metal ion or a complex ion into the localized phase of the silver halide grain and / or the other portion of the grain, the metal ion or the complex ion is formed before, during or after the formation of the silver halide grain. It may be added directly to the reaction vessel during the subsequent physical ripening, or may be added in advance in the addition solution of the water-soluble halogen salt or water-soluble silver salt. When the localized phase is formed of fine grain silver bromide or high silver bromide, it is added to silver bromide or high silver bromide fine grains by the same method as above, and then added to silver chloride or high silver chloride emulsion. You may. In addition, a metal ion may be contained while forming a localized phase by adding a bromide other than a silver salt, which is relatively insoluble in a metal ion as described above, as a solid or powder.

In order to achieve a sufficiently 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 of the above-mentioned high levels. It is preferable to use a silver chloride emulsion. The silver halide grains used in the present invention can take the form of so-called regular grains such as cubes, octahedra, tetradecahedrons and rhombodecahedrons, and also irregular grains such as spheres and tabular grains. It can also have a particle shape. Further, it may be a particle having a more complicated shape having these crystal faces combined, or a particle having a higher crystal face. These silver halide grains may be mixed.
Preferably used in the present invention is a silver halide grain having a regular crystal form of 5 or less in terms of number of grains or weight.
It is a silver halide emulsion containing 0% or more, more preferably 70% or more, and further preferably 90% or more, and particularly preferably an emulsion containing crystal grains having a (100) crystal face.

Further, in the emulsion used in the present invention, tabular grains having an average aspect ratio (ratio of diameter in terms of circle to main plane of grain / grain thickness) of 5 or more, particularly preferably 8 or more, are represented by the total projected area of grains. When the emulsion accounts for 50% or more, not only is the rapid processing property advantageous, but the effect relating to the color gradation of the present invention is more clearly exhibited. The size of the grains of the silver halide emulsion used in the present invention is not particularly limited as long as the rapid processability is not impaired, but the average diameter when the projected area of the grains is converted into a circle is 0.1 to 1.7.
It is preferably μm. The size distribution of silver halide grains may be wide or narrow, but so-called monodisperse emulsions are better for photographic characteristics such as latent image stability and pressure resistance, and developer pH.
It is preferable in processing stability such as dependency. A value S / d obtained by dividing the standard deviation S of the projected area of the silver halide grains and the diameter distribution when converted into a circle by the average diameter d is preferably 20% or less, and more preferably 15% or less.

The silver chlorobromide emulsion used in the present invention is P. Glafkide.
s (Graph Kidd) "The Chemistry and Physics of Photography" (Paul ・
Montel, 1967), GF Duffin, "The Chemistry of Photographic Emulsions" (Focal Press, 196).
6), "Preparation and coating of photographic emulsions" by VL Zelickman (Focal Press, 1964).
, Etc.) and the like. That is, any of an acidic method, a neutral method, an ammonia method and the like may be used, but the acidic method and the neutral method are particularly preferable in the present invention in terms of reducing fog. To obtain an emulsion in silver halide by reacting a soluble silver salt with a soluble halogen salt, any one of so-called one-side mixing method, simultaneous mixing method or a combination thereof may be used. It is also possible to use a so-called reverse mixing method in which grains are formed under the condition of excess silver ions. In order to obtain the monodisperse grain emulsion preferred in the present invention, it is preferable to use the simultaneous mixing method. As one form of the simultaneous mixing method, it is more preferable to use a method of keeping the silver ion concentration in the liquid phase where silver halide is produced constant, that is, a so-called controlled double jet method. By using this method, it is possible to obtain a silver halide emulsion suitable for the present invention, which has a regular silver halide crystal shape and a narrow grain size distribution.

In the course of such grain formation or physical ripening of silver halide, a cadmium salt, a zinc salt, a lead salt, a thallium salt, or the above-mentioned iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt. Alternatively, its complex salt may coexist. During or after grain formation silver halide solvents (eg, as known, ammonia, thiocyanates, U.S. Pat. No. 3,271,1).
57, JP-A-51-12360, JP-A-53-82.
408, JP-A-53-144319, JP-A-54-
No. 100717 or thioethers and thione compounds described in JP-A No. 54-155828, etc. may be used. When used in combination with the above-mentioned method, the present invention has a regular silver halide crystal shape and a narrow grain size distribution. A preferable silver halide emulsion can be obtained.

In order to remove the soluble salt from the emulsion after physical ripening, it is possible to use Nudel water washing, flocculation sedimentation method, ultrafiltration method or the like. The emulsion used in the present invention can be chemically sensitized by sulfur sensitization, selenium sensitization, reduction sensitization, noble metal sensitization, etc., alone or in combination. That is, a sulfur sensitization method using active gelatin or a compound containing a sulfur compound capable of reacting with silver ions (for example, thiosulfate, thiourea compound, mercapto compound, rhodanine compound, etc.) or a reducing substance (for example, stannous salt) , Amines, hydrazine derivatives, formamidinesulfinic acid, silane compounds, etc.), and metal compounds (such as the aforementioned gold complex salts, platinum, iridium, palladium, rhodium, iron, etc., Group VIII) Noble metal sensitization method using a metal salt or complex salt thereof, etc.) can be used alone or in combination. In the emulsion of the present invention, sulfur sensitization or selenium sensitization is preferably used, and it is also preferable to use gold sensitization in combination with these. In addition, it is preferable that a hydroxyazaidene compound or a nucleic acid is present in the chemical sensitization in order to control sensitivity and gradation.

The effect of the present invention is particularly clear when a pyrazoloazole type coupler is used as the magenta coupler as described above. In other words, when the technique of the present invention is used in such a system, the pyrazoloazole type coupler is used. High color saturation due to the excellent spectral absorption characteristics of the color-forming dye of the coupler of the system, on the contrary, it is possible to satisfactorily achieve both the color gradation that is easily damaged by it, and in terms of rapid processability and color image fastness It is also possible to obtain a color photographic light-sensitive material having excellent characteristics. The magenta coupler used in the present invention is particularly preferably the one represented by the general formula (M).

[0041]

[Chemical 3]

In the general formula (M), R ₁ represents a hydrogen atom or a substituent. Y ₁ represents a hydrogen atom or a coupling-off group, and a halogen atom and an arylthio group are particularly preferable. Za, Zb and Zc are methine, substituted methine,
= N- or -NH-, and represents a Za-Zb bond and Zb-Z.
One of the c bonds is a double bond and the other is a single bond. When the Zb-Zc bond is a carbon-carbon double bond, it includes the case where it is part of an aromatic ring. When R ₁ or Y ₁ or Zb or Zc is a substituted methine, a case where the substituted methine forms a dimer or higher multimer is included.
Specific examples of the substituent of R _1, the substituent of the substituted methine group, and the coupling-off group are described in US Pat. No. 4,540,
Those described in columns 2 to 5 of No. 654 are applied.

Among the pyrazoloazole-based couplers represented by the general formula (M), US Pat. No. 4,500,630 has a small yellow sub-absorption of a coloring dye and a light fastness.
The imidazo [1,2-b] pyrazoles described in US Pat. No. 4,540,654 are preferred and the pyrazolo [1,5-b] [1,2,4] triazoles described in US Pat. No. 4,540,654 are particularly preferred. In addition, a pyrazolotriazole coupler in which a branched alkyl group as described in JP-A-61-65245 is directly linked to the 2-, 3- or 6-position of a pyrazoloazole ring, JP-A-61-
Pyrazoloazole couplers containing sulfonamide groups in the molecule as described in JP-A-65246, JP-A-61-
Pyrazoloazole couplers having an alkoxyphenyl sulfonamide ballast group as described in 147254 and European Patent (Publication) Nos. 226,849 and 29.
It is preferable to use a pyrazolotriazole coupler having an alkoxy group or an aryloxy group at the 6-position as described in No. 4,785. Specific examples of these pyrazoloazole couplers include 9 to 2 of European Patent 355,660A2.
Examples thereof include I-1 to I-50 described on page 8.

In the light-sensitive material according to the present invention, a hydrophilic colloid layer for the purpose of improving the sharpness of an image can be decolorized by the treatment described in European Patent EP 0,337,490A2, pages 27 to 76. A dye (among others, an oxonol dye) is added so that the optical reflection density at 680 nm of the light-sensitive material becomes 0.70 or more, and a dihydric or tetrahydric alcohol (in the water resistant resin layer of the support ( For example, a titanium oxide surface-treated with trimethylolethane etc.
It is preferable to contain 2% by weight or more (more preferably 14% by weight or more).

Photographic additives such as cyan, magenta and yellow couplers which can be used in the present invention are preferably used by dissolving them in a high boiling point organic solvent. The high boiling point organic solvent has a melting point of 100 ° C. or lower and a boiling point of 140 ° C. The above-mentioned water-immiscible compound can be used as long as it is a good solvent for the coupler. The melting point of the high boiling point organic solvent is preferably 80 ° C. or lower. The boiling point of the high boiling point organic solvent is preferably 160 ° C. or higher,
More preferably, it is 170 ° C. or higher. Details of these high boiling point organic solvents are described in JP-A No. 62-215272, page 137, lower right column to page 144, upper right column. Further, the cyan, magenta or yellow coupler is impregnated with a loadable latex polymer (for example, US Pat. No. 4,203,716) in the presence or absence of the above high-boiling organic solvent, or is water-insoluble and organic. It can be dissolved with a solvent-soluble polymer and emulsified and dispersed in a hydrophilic colloid aqueous solution. Preferably, U.S. Pat. No. 4,857,449, columns 7 to 15
Column and No. 12 of International Publication WO88 / 00723
The homopolymers or copolymers described on pages 30 to 30 are used, more preferably methacrylate-based or acrylamide-based polymers, particularly acrylamide-based polymers, for stabilizing the color image.

Further, in the light-sensitive material according to the present invention, it is preferable to use a color image storability improving compound as described in European Patent EP0,277,589A2 together with a coupler. In particular, it is preferably used in combination with a pyrazoloazole coupler. That is, the compound (F) that chemically bonds with the aromatic amine-based developing agent remaining after the color development processing to form a chemically inactive and substantially colorless compound and / or the fragrance remaining after the color development processing. The use of the compound (G), which forms a chemically inactive and substantially colorless compound by chemically bonding with an oxidant of a group amine color developing agent, simultaneously or solely, for example, in storage after processing. It is preferable in order to prevent stains and other side effects due to the formation of a coloring dye due to the reaction of the coupler with the color developing agent remaining in the film or its oxidant.

In order to prevent various molds and bacteria which propagate in the hydrophilic colloid layer and deteriorate the image, the light-sensitive material according to the present invention has an anti-mold property as described in JP-A-63-271247. It is preferable to add an agent.

As the support used in the light-sensitive material of the present invention, a white polyester support for display or a layer containing a white pigment is provided on the support having a silver halide emulsion layer. A support may be used. Further, in order to improve the sharpness, it is preferable to apply an antihalation layer on the silver halide emulsion layer coated side or the back side of the support. In particular, the transmission density of the support is 0.3 so that the display can be viewed with both reflected and transmitted light.
It is preferably set in the range of 5 to 0.8.

The exposure method may be either low illuminance exposure or high illuminance short time exposure, and in the latter case, a laser scanning exposure method in which the exposure time per pixel is shorter than 10 ^-4 seconds is preferable.

In the exposure, US Pat. No. 4,88
It is preferable to use the band stop filter described in No. 0,726. This removes the light mixture,
Color reproducibility is significantly improved.

The exposed light-sensitive material can be subjected to a conventional color development process, but for the purpose of rapid processing, it is preferable to carry out a bleach-fixing process after the color development. In particular, the pH of the bleach-fixing solution is preferably about 6.5 or less, more preferably about 6 or less for the purpose of promoting desilvering.

Silver halide emulsions and other materials (additives and the like) and photographic constituent layers (layer arrangement and the like) applied to the light-sensitive material according to the present invention, and a processing method applied for processing the light-sensitive material. As the processing additives, those described in the following patent publications, particularly European Patent EP0,355,660A2 (JP-A-2-139544) are preferably used.

[0053]

[Table 1]

[0054]

[Table 2]

[0055]

[Table 3]

[0056]

[Table 4]

[0057]

[Table 5]

Further, as a cyan coupler, JP-A-2-
In addition to the diphenylimidazole-based cyan coupler described in 33144, European Patent EP 0,333,185A2
3-Hydroxypyridine cyan couplers (especially the couplers (42) listed as specific examples, which are 4-equivalent couplers with a chlorine leaving group to make them 2-equivalent, couplers (6) and (9) Is particularly preferable) and cyclic active methylene cyan couplers described in JP-A-64-32260 (coupler examples 3, 8, and 34 listed as specific examples are particularly preferable) are also preferably used.

A processing method of a silver halide color light-sensitive material using a high silver chloride emulsion having a silver chloride content of 90 mol% or more is described in JP-A-2-207250, page 27, upper left column to page 34, upper right. The method described in the section is preferably applied.

[0060]

【Example】

Example 1 An emulsion for a light-sensitive silver halide emulsion layer containing a cyan coupler was prepared as follows. Coal-processed gelatin 30g
Was added to 1000 ml of distilled water, dissolved at 40 ° C., the pH was adjusted to 3.8 with sulfuric acid, and 5.5 g of sodium chloride and 0.05 N, N′-dimethylimidazolidine-2-thione were added.
2 g were added and the temperature was raised to 52.5 ° C. A solution prepared by dissolving 62.5 g of silver nitrate in 750 ml of distilled water and a solution prepared by dissolving 21.5 g of sodium chloride in 500 ml of distilled water were mixed.
The solution was added and mixed for 40 minutes while maintaining the temperature at 2.5 ° C. Further, a solution prepared by dissolving 62.5 g of silver nitrate in 500 ml of distilled water and a solution prepared by dissolving 21.5 g of sodium chloride in 300 ml of distilled water were added and mixed at 52.5 ° C. for 20 minutes. When the obtained emulsion was observed with an electron microscope, it was an emulsion composed of cubic grains having an average side length of about 0.46 μ and a coefficient of variation of grain size distribution of 0.09. After washing this emulsion with demineralized water, 0.2
g, the following red sensitizing dye (V-6) 0.46 × 10 ⁻⁴ mol / mol Ag,

[0061]

[Chemical 4]

Monodisperse silver bromide emulsion having an average grain size of 0.05 μ (iridium dichloride hexapotassium 2 × 10 ^-5 mol /
(Containing Ag Ag) was added with silver halide in an amount of 0.6 mol% and chemically sensitized with about 2 × 10 ⁻⁶ mol / mol Ag of triethylthiourea, and further 1- (5-methylureidophenyl)- 5-mercaptotetrazole at 7 × 10 ^-4
Emulsion Em-1 was obtained by adding mol / mol Ag. Further, the following compound was added in an amount of 2.6 × per mol of silver halide.
10 ⁻³ mol was added.

[0063]

[Chemical 5]

On the other hand, in the method of preparing Em-1, the grain forming temperature was lowered to an average grain size of 0.38 μm, and the amount of the sensitizing dye (V-6) added was 0.56 × 10 ⁻⁴ mol / mol. Emulsion Em- in the same manner as emulsion Em-1 except that Ag was used.
4 was obtained to obtain a low-sensitivity red light-sensitive emulsion for a silver halide emulsion layer containing a cyan coupler. A green photosensitive emulsion for a magenta coupler-containing silver halide emulsion layer was prepared as follows. 30 g of coal-processed gelatin was added to 1000 ml of distilled water, dissolved at 40 ° C., and then 5.5 g of sodium chloride and N, N′-dimethylimidazolidine-2-thione 0.0
2 g were added and the temperature was raised to 50 ° C. Silver nitrate 6
A solution prepared by dissolving 2.5 g in 750 ml of distilled water and a solution prepared by dissolving 21.5 g of sodium chloride in 500 ml of distilled water at 50 ° C.
The mixture was added to and mixed with the above liquid in 40 minutes while maintaining the above. Further, a solution of 62.5 g of silver nitrate dissolved in 500 ml of distilled water and a solution of 21.5 g of sodium chloride dissolved in 300 ml of distilled water were added and mixed at 50 ° C. for 20 minutes.

When the obtained emulsion was observed by an electron microscope, it was an emulsion composed of cubic grains having an average side length of about 0.44 μ and a value of 0.08 as a variation coefficient of grain size distribution. After washing this emulsion with demineralized water, nucleic acid 0.
2 g, the following green-sensitive sensitizing dye (V-41) 5 × 10 ⁻⁴ mol / mol Ag, and a monodispersed silver bromide emulsion having an average grain size of 0.05 μ (iridium dichloride dipotassium 2.5 × 10 5).
^-5 mol / mol Ag) 0.4 mol% with silver halide
Appropriately added, triethylthiourea about 2.5 × 10
Chemically sensitized with ^-6 mol / mol Ag, and 1.1 × 10 ^-3 mol / mol Ag of 1- (5-methylureidophenyl) -5-mercaptotetrazole was added to the silver halide emulsion containing magenta coupler. Layer green photosensitive emulsion Em-2
And

[0066]

[Chemical 6]

On the other hand, in the method of preparing the emulsion Em-2, the temperature at the time of grain formation was lowered to an average grain size of 0.37 μm, and the sensitizing dye (V-41) was added at 6 × 10 ⁻⁴ mol / mol Ag. And Others are the same as Emulsion Em-2.
-5 was produced. This emulsion was used as a low-sensitivity green light-sensitive emulsion for a silver halide emulsion layer containing a magenta coupler. A blue-sensitive emulsion for a silver halide emulsion layer containing a yellow coupler was prepared as follows.

30 g of coal-processed gelatin was added to 1000 parts of distilled water.
After dissolving at 40 ° C., the pH was adjusted to 3.8 with sulfuric acid, 5.5 g of sodium chloride and 0.03 g of N, N′-dimethylimidazolidine-2-thione were added to adjust the temperature. Raised to 75 ° C. 12.5g of silver nitrate is added to distilled water 15
A solution dissolved in 0 ml and 4.3 g of sodium chloride were distilled water 1
The solution dissolved in 00 ml was added to and mixed with the above solution over 30 minutes while maintaining the temperature at 75 ° C. Further, a solution prepared by dissolving 112.5 g of silver nitrate in 1100 ml of distilled water and 38.7 sodium chloride.
A solution obtained by dissolving g in 650 ml of distilled water was added and mixed at 75 ° C. for 40 minutes. When the obtained emulsion was observed with an electron microscope, it was an emulsion composed of cubic grains having an average side length of about 0.82 μ and a value of 0.11 as a variation coefficient of grain size distribution.

After washing this emulsion with demineralized water, nucleic acid 0.2
g, the following blue-sensitive sensitizing dye (V-36) 3 × 10 ⁻⁴ mol / mol Ag, and a monodisperse silver bromide emulsion having an average grain size of 0.05 μ (iridium dichloride dipotassium hexachloride 1 × 10 ⁻⁵ mol). /
(Containing Ag Ag) was added in an amount corresponding to 0.3 mol% with silver halide, and triethylthiourea was added in an amount of about 1.2 × 10 ⁻⁶ mol /
Chemically sensitized with mol Ag, and 9 × 1- (5-methylureido-phenyl) -5-mercaptotetrazole.
10 ⁻⁴ mol / mol Ag was added to give a high-sensitivity blue-sensitive emulsion Em-3 for a silver halide emulsion layer containing a yellow coupler.

[0070]

[Chemical 7]

On the other hand, in the method of preparing Em-3, the temperature at the time of grain formation was lowered to an average grain size of 0.70 μm, and the addition amount of the blue-sensitized sensitizing dye (V-36) was 4 respectively.
Emulsion Em-6 was prepared in the same manner as Emulsion Em-3 except that it was set at × 10 ^-4 mol / mol Ag to give a low-sensitivity blue-sensitive emulsion for a silver halide emulsion layer containing a yellow coupler. When the halogen composition and its distribution were observed by the X-ray diffraction method for the above-mentioned green light-sensitive silver halide emulsion for the magenta coupler-containing layer and the blue light-sensitive silver halide emulsion for the yellow coupler-containing layer, they corresponded to 100 mol% of silver chloride. In addition to the main peak, a broad diffraction pattern having a center in the vicinity of 70 to 65 mol% of silver chloride and having a tail in the vicinity of 60 mol% of silver chloride could be slightly observed. After the corona discharge treatment is applied to the surface of the paper support laminated with polyethylene on both sides, a gelatin subbing layer containing sodium dodecylbenzene sulfonate is provided, and various photographic constituent layers are further coated to form a multilayer color having the layer constitution shown below. A printing paper was prepared and used as a sample 101. The coating liquid was prepared as follows.

Preparation of coating solution for the first layer Yellow coupler (ExY) 19.1 g and color image stabilizer (Cpd-1) 4.4 g and color image stabilizer (Cpd-)
7) 0.7 g of ethyl acetate 27.2 cc and solvent (So
lv-3) and (Solv-7) (4.1 g) were added and dissolved, and this solution was dissolved in 10% sodium dodecylbenzenesulfonate (8 cc) in 10% gelatin aqueous solution 185.
Emulsified dispersion A was prepared by emulsifying and dispersing in cc. Emulsion Em
-3 and Em-6 were mixed at a ratio of 3: 7, and then mixed and dissolved with the emulsified dispersion A described above to prepare a coating liquid for the first layer having the composition shown below.

The coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer (also in the fifth layer, the cyan coupler was added to ethyl acetate together with the color image stabilizer (Cpd-7), etc.). After dissolution, it was emulsified and dispersed). 1-Oxy-3,5-dichloro-s-triazine sodium salt was used as a gelatin hardening agent for each layer. In addition, Cpd-
10 and Cpd-11 were added so that the total amount would be 25.0 mg / m ² and 50.0 mg / m ² , respectively. Further, 4-hydroxy-6-methyl-1,3,3a, 7- was added to the yellow coupler-containing emulsion layer and the magenta coupler-containing emulsion layer.
Tetrazaindene was added in an amount of 1 × 10 ^-4 mol and 2 × 10 ^-4 mol per mol of silver halide, respectively. Also,
The following dyes (the amount in parentheses represents the coating amount) were added to the emulsion layer to prevent irradiation.

[0074]

[Chemical 8]

(Layer Structure) The composition of each layer is shown below. The numbers represent the coating amount (g / m ² ). The silver halide emulsion represents the coating amount in terms of silver. Support Polyethylene laminated paper [Polyethylene on the first layer side contains white pigment (TiO ₂ ) and bluish dye (ultraviolet)] First layer (blue-sensitive emulsion layer) Emulsion Em-3 0.09 Emulsion described above Em-6 0.21 Gelatin 1.22 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 0.64 Color mixing inhibitor (Cpd-5) 0.10 Solvent (Solv-1) 0.16 Solvent (Solv-4) 0. 08

[0076] Third layer (green sensitive emulsion layer)   The above emulsion Em-2 0.04   The above-mentioned emulsion Em-5 0.07   Gelatin 1.28   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 (UV absorption layer)   Gelatin 1.41   Ultraviolet absorber (UV-1) 0.47   Color mixing inhibitor (Cpd-5) 0.05   Solvent (Solv-5) 0.24 Fifth layer (red sensitive emulsion layer)   The above emulsion Em-1 0.07   The above emulsion Em-4 0.16   Gelatin 1.04   Cyan coupler (ExC) 0.32   Color image stabilizer (Cpd-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 Sixth layer (UV absorption layer)   Gelatin 0.48   Ultraviolet absorber (UV-1) 0.16   Color mixing inhibitor (Cpd-5) 0.02   Solvent (Solv-5) 0.08 Seventh layer (protective layer)   Gelatin 1.10   Acrylic modified copolymer of polyvinyl alcohol (modification degree 17%) 0.17   Liquid paraffin 0.03

[0077]

[Chemical 9]

[0078]

[Chemical 10]

[0079]

[Chemical 11]

[0080]

[Chemical 12]

[0081]

[Chemical 13]

[0082]

[Chemical 14]

[0083]

[Chemical 15]

[0084]

[Chemical 16]

The sample thus prepared was used as sample 101.
And Next, to silver halide emulsions Em-1 and Em-4 used in the cyan coupler-containing layer of Sample 101, a blue-sensitive spectral sensitizing dye was added as shown in Tables 1 and 2.
-A to 1-M and 4-A to 4-M were prepared, respectively. All of these blue-sensitive spectral sensitizing dyes were added before the start of chemical sensitization.

[0086]

[Table 6]

[0087]

[Table 7]

The emulsions obtained in Tables 1 and 2 were used as sample 101.
Em-1 and Em-4 were combined and replaced as shown in Table 3 below to prepare Samples 102 to 114.

[0089]

[Table 8]

First, the sample 101 was subjected to gray exposure so that the developed silver amount was 30% of the applied silver amount, the following processing steps and processing solution compositions were used, and the tank capacity for color development was set to 2%. Continuous processing (running test) was performed until double replenishment. Processing process Temperature Time Replenisher ^* Tank capacity Color development 35 ℃ 45 seconds 161ml 17L Bleach fixing 30-35 ℃ 45 seconds 215ml 17L Rinse 30-35 ℃ 20sec-10L Rinse 30-35 ℃ 20sec-10L Rinse 30-35 ℃ 20 seconds 350ml 10 liter Dry 70-80 ℃ 60 seconds * Replenishment amount per 1m ² of light-sensitive material. (Rinse → 3 tank countercurrent system) The composition of each processing solution is as follows.

[0091] Color developer Tank solution Replenisher   800 ml water 800 ml   Ethylenediamine-N, N, N ', N'-     Tetramethylenephosphonic acid 1.5g 2.0g   Potassium bromide 0.015g −   Triethanolamine 8.0g 12.0g   Sodium chloride 1.4 g −   Potassium carbonate 25g 25g   N-ethyl-N- (β-methanesulfone     (Midoethyl) -3-methyl-4-amino     Aniline sulfate 5.0g 7.0g   N, N-bis (carboxymethyl) hydra     Gin 4.0g 5.0g   N, N-di (sulfoethyl) hydroxyl     Amine ・ 1Na 4.0g 5.0g   Optical brightener (WHITEX 4B, Sumitomo Chemical) 1.0g 2.0g   Add water 1000ml 1000ml   pH (25 ℃) 10.05 10.45

[0092] Bleach-fix solution (tank solution and replenisher are the same)   400 ml of water   Ammonium thiosulfate (70%) 100 ml   Sodium sulfite 17g   Ethylenediaminetetraacetic acid iron (III) ammonium 55g   Ethylenediaminetetraacetic acid disodium 5g   40 g of ammonium bromide   Add water 1000ml   pH (25 ° C) 6.0 Rinse solution (tank solution and replenisher are the same)   Ion-exchanged water (calcium and magnesium are less than 3ppm each)

For samples 101 to 114, a FWK type sensitometer manufactured by Fuji Photo Film Co., Ltd. was used to make SP-manufactured by the same company.
2,500 through 1, SP-2, SP-3 filters
A three-color separation / gradation exposure of lux 1/10 seconds was applied, and the continuous processing developer prepared as described above was used to perform development processing with the automatic developing machine. The density of the obtained developed sample was measured with a TCD densitometer manufactured by Fuji Photo Film Co., Ltd. The change in density due to color development in the other layers was removed by calculation. Table 4 shows that in Samples 101 to 114, the ratio of the blue light sensitivity of the cyan color developing layer (SP-1) to the blue light sensitivity of the yellow color developing layer and / or the magenta color developing layer of the cyan color developing layer (SP-2). And the spectral sensitivity maximum wavelength of each of the cyan, magenta and yellow color forming layers.

[0094]

[Table 9]

Put a red linen summer sweater, a sweater made of the same red extra-thick woolen yarn, and the same red silk blouse on a gray back, and shine a strong light diagonally from above.
Images were taken using Fuji Color Super HG400 and the specified processing was performed. Next, through this negative, the Fuji C450 printer was used to print on the samples 101 to 114 prepared above, and evaluation was performed from the viewpoint of color gradation reproducibility. The evaluation was performed in the following three stages. The obtained result is the fifth
Shown in the table. <Color gradation> A The texture of silk, linen, and soft wool can be distinguished, and the texture can be seen well. The texture of A'silk, hemp, and soft wool can be distinguished, but the weave is not clear. B The texture is clearly visible, but the hemp and woolen yarns also look stiff and stiff. C There is no three-dimensional effect, and the texture difference of materials such as silk, linen, and wool cannot be expressed. <Color Reproducibility> A Red color is colorful and the difference in color between materials can be seen. B The high density area of red becomes black, but the color is visible. C Red is dark from the low density area to the high density area.
Or, all the materials are uniform red and the colors are colorful, but the colors cannot be distinguished.

[0096]

[Table 10]

The effects of the present invention are clear from the results shown in Table 5. That is, in the sample 101 to which no color gradation is given, the shade of the red part is hardly expressed, and there is no stereoscopic effect.
In addition, the spectral sensitivity maximum wavelength of the silver halide emulsion contained in the cyan coupler-containing red light-sensitive silver halide emulsion layer outside the red region is the maximum spectral sensitivity of the emulsion contained in the yellow coupler-containing blue light-sensitive silver halide emulsion layer. Samples 102 to 106 in which a color gradation is provided so that the wavelength and / or the magenta coupler-containing green light-sensitive silver halide emulsion layer is located at substantially the same wavelength as the maximum spectral sensitivity wavelength of the emulsion.
Then, even if the degree of color gradation is optimized, the high density portion of red abruptly becomes dark and gives an unnatural impression. The shadows can be expressed with a natural feeling without losing the red color and the redness only for the samples 107 to 114 that satisfy the conditions of the maximum spectral sensitivity wavelength of the present invention.

Among Samples 107 to 114, the blue light sensitivity and / or green light sensitivity of the cyan coupler-containing red light-sensitive silver halide emulsion layer was higher than that of the yellow coupler-containing blue light-sensitive silver halide emulsion layer. For each green light sensitivity of the coupler-containing green light-sensitive silver halide emulsion layer, 0.03125 (= 1/32) or more and 0.5 (= 1 /
2) the following samples 108, 110, 112, 113,
114 is more excellent than Samples 107, 109, and 111 in that the texture is clearly expressed.

[0099]

EFFECTS OF THE INVENTION According to the present invention, red tone reproducibility, in particular, high density areas are not suddenly darkened, shades are naturally added to improve color tone reproducibility, and further, color reproducibility is excellent.
Moreover, a color light-sensitive material suitable for rapid processing can be obtained.

Claims (3)

[Claims] 1. A halogen having at least one yellow coupler-containing blue light-sensitive silver halide emulsion layer, magenta coupler-containing green light-sensitive silver halide emulsion layer and cyan coupler-containing red light-sensitive silver halide emulsion layer on a support. In a silver halide color photographic light-sensitive material, the cyan coupler-containing red light-sensitive silver halide emulsion layer has a silver chloride content of 9
Sensitizing the silver halide emulsion to have a spectral sensitivity maximum at a wavelength X satisfying at least one of the following relational expressions 1, 2 or 3 in the region other than the red region except that the silver halide emulsion is 0 mol% or more. A silver halide color photographic light-sensitive material characterized by being added. Relational expression 1. X ≦ λ _B −30 2. λ _B + 10 ≦ X ≦ λ _G −10 3. λ _G +10 ≤ X ≤ λ _R -50 (where λ _B is the maximum spectral sensitivity wavelength of the emulsion contained in the yellow coupler-containing blue-sensitive silver halide emulsion layer, λ _G is the magenta coupler-containing green-sensitive silver halide) The maximum spectral sensitivity wavelength of the emulsion contained in the emulsion layer and λ _R represent the maximum spectral sensitivity wavelength in the red region of the emulsion contained in the cyan coupler-containing red light-sensitive silver halide emulsion layer, all in nm. ) 2. The blue light sensitivity and / or the green light sensitivity of the cyan coupler-containing red light-sensitive silver halide emulsion layer is the blue light sensitivity of the yellow coupler-containing blue light-sensitive silver halide emulsion layer, and the magenta coupler-containing green light-sensitive halogen. 2. The silver halide color photographic light-sensitive material according to claim 1, wherein the green light sensitivity of each silver halide emulsion layer is 1/2 or less and 1/32 or more. 3. The silver halide color photographic light-sensitive material according to claim 1, wherein the magenta coupler used in the magenta coupler-containing green light-sensitive silver halide emulsion layer is a pyrazoloazole compound.