JPH0695312A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide a silver halide color photographic sensitive material capable of optionally controlling the tone reproduction performance of high density color without deteriorating rapid processability. CONSTITUTION:The silver halide color photographic sensitive material is characterized by containing yellow, magenta, and cyan color-developing couplers in 3 kinds of silver halide emulsion layers formed on a support and silver halide grains containing >=90mol% in average in each emulsion layer, spectrally sensitizing at least one of the coupler-containing emulsion layers to both of a primary color light in a complementary relation to a color developing dye in the 3 primary color relations and another primary color light, and controlling the sensitivity of this layer to the primary colors except the complementary color light to 1/2-1/32 of that of one of the layers containing the 2 kinds of couplers, and a ratio of the gradient obtained at the time of exposing this layer to the primary color light in the complementary relation to the color developing dye in this layer to the gradient at the time of exposing it to the primary color light out of the complementary relation to this dye to <0.6.

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 In recent years, in order to meet the demand for rapid processing, high silver chloride is used as a light-sensitive material and a processing solution containing neither sulfite nor benzyl alcohol contained in a color developing processing solution of a normal color paper is used. New systems for combined use are being developed and introduced. The photographs obtained with the high-silver chloride color paper used for this new rapid processing have an inherent sensitivity of red-sensitivity, green-sensitivity, and blue-sensitivity because high-silver chloride or silver chloride has no absorption in the visible range. It has the advantage that it does not impair the discrimination function of the above, and does not cause so-called color mixing, but on the other hand, the problem that the color gradation in the high-density area becomes more difficult to express than when using conventional silver chlorobromide. Therefore, it is expected that this problem can be solved without impairing the rapid processability and other advantages. This problem tends to appear particularly when reproducing the original color gradation having vivid red or yellow, and this drawback is magnified in the color paper using silver chloride.

In recent years, pyrazoloazole-based magenta couplers have been known as magenta couplers for color paper. This type of coupler is known to have not only better spectral absorption characteristics of the color forming dye than the 5-pyrazolone type coupler, but also to be fast against light and to have less stain derived from the coupler itself. There are many advantages. Among these pyrazoloazole-based magenta couplers, pyrazolo [5,
1-c] [1,2,4] triazoles and pyrazolo [5,1-b] [1,2,4] triazoles are useful in terms of overall performance of color forming properties, spectral absorption characteristics of color forming dyes, and color image fastness. Pyrazolo [5,1-b] [1,2,4] triazoles described in US Pat. No. 4,540,654 can be preferably used. However, when these couplers are used in the green-sensitive silver halide emulsion layer, even though there are particularly preferable points,
It was also found that the insufficient color gradation as described above is more easily emphasized.

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, Japanese Patent Publication No.
Although a method of providing a photosensitive layer for forming a black dye image as described in 10737 is known, it is difficult to develop a black color coupler that can be sufficiently put to practical use by this method. In addition, there is no description concerning rapid processing and no description about problems in improving color saturation. Further, Japanese Patent Laid-Open No. 61-91657 discloses a method of improving tone reproducibility of a colored image by adding a dye image having a hue different from the specific density of the dye image. There is no mention of the advantage of making it compatible with rapid processing by using, and by using a pyrazoloazole-based magenta coupler, it is possible to increase the saturation and improve the color reproducibility while improving the color gradation. There is no technical suggestion on improving expressiveness.

In JP-A-2-129628, a cyan coupler-containing silver halide emulsion layer is spectrally sensitized into red and blue and / or green so as to impart color gradation to a red image, and magenta and yellow are obtained. 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 (US 4,9
No. 02,609), a method of expanding the exposure latitude by imparting different color sensitivities is disclosed. In these methods, the gradation of the cyan image in the red portion is equal to that of the cyan image. However, it is impossible to freely adjust the color gradation of the high density portion, and the development of new means has been desired.

[0006]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to arbitrarily adjust the tone reproducibility of colors, especially the tone reproducibility of high-density color, and make it compatible with the rapid processability. It is an object of the present invention to provide a silver halide color photographic light-sensitive material excellent in tone reproducibility better even when it is processed rapidly.

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 three types of silver halide emulsion layers containing couplers that develop yellow, magenta and cyan, respectively, on a support, the silver halide contained in each emulsion layer The average silver chloride content is 90 mol% or more, and at least one of the coupler-containing silver halide emulsion layers is used for both the primary color light and the primary color light other than the complementary color with the color-forming dye in the relationship of the three primary colors of light. Is spectrally sensitized, the sensitivity of the layer to primary color light other than the complementary color is 1/2 or less and 1/32 or more with respect to either of the other two coupler-containing emulsion layers, and the color development of the layer A silver halide color photographic light-sensitive material, characterized in that the ratio of the gradation when exposed with primary color light having a complementary color relationship with the dye to the gradation when exposed with primary color light other than the complementary color is less than 0.6. . (2) In a silver halide color photographic light-sensitive material having three types of silver halide emulsion layers containing couplers that develop yellow, magenta and cyan, respectively, on a support, the silver halide contained in each emulsion layer The average silver chloride content is 90 mol% or more, and at least one of the coupler-containing silver halide emulsion layers is a mixture of at least two kinds of silver halide emulsions having different average grain sizes. (A) is at least one of a sensitizing dye having spectral sensitivity to primary color light having a complementary color relationship with a color forming dye, and a sensitizing dye having spectral sensitivity to primary color light other than complementary colors in the relationship of the three primary colors of light. The other emulsion (B) is a sensitized emulsion, and the other emulsion (B) has a color difference from that of the sensitizing dye having a spectral sensitivity to primary color light having a complementary color relationship with the color forming dye. A silver halide color photographic light-sensitive material characterized by being a spectrally sensitized emulsion in which the molar ratio of the addition amount of a sensitizing dye having a spectral sensitivity to external primary color light per silver halide is 50% or less. material. (3) In a silver halide color photographic light-sensitive material having three types of silver halide emulsion layers containing couplers that develop yellow, magenta and cyan, respectively, on a support, the silver halide contained in each emulsion layer The average silver chloride content is 90 mol% or more, and at least one of the coupler-containing silver halide emulsion layers is composed of two or more layers that develop substantially the same color and is contained in one of them. The emulsion (A) is a sensitizing dye having a spectral sensitivity to primary color light which is complementary to the color forming dye in the relationship of the three primary colors of light.
An emulsion (B) contained in the other layer is spectrally sensitized with at least one sensitizing dye having a spectral sensitivity to a primary color light other than the complementary color. ,
The molar ratio of the added amount of the sensitizing dye having the spectral sensitivity to the primary color light other than the complementary color to the sensitizing dye having the spectral sensitivity to the primary color light having a complementary color relationship with the color forming dye per silver halide grain is 50.
% Silver halide color photographic light-sensitive material, which is an emulsion spectrally sensitized. (4) The silver halide color photograph described in the preceding page 1, 2 or 3, wherein the magenta coupler used in the magenta coupler-containing layer is a pyrazoloazole compound represented by the following general formula [M] Photosensitive material.

[0008]

[Chemical 2]

(In the formula, R ₁ represents a hydrogen atom or a substituent. Y ₁ represents a hydrogen atom or a leaving group. Za, Zb,
And Zc is methine, substituted methine, = N- or -NH
Represents-, and one of the Za-Zb bond and the Zb-Zc bond is a double bond and the other is a single bond. The case where the Za-Zb bond is a carbon-carbon double bond includes the case where it is part of an aromatic ring. This includes the case where R ₁ or Y ₁ forms a dimer or higher multimer, and the case where Za, Zb, or Zc is a substituted methine, the substituted methine forms a dimer or higher multimer. )

The present invention will be described in detail below. The color photographic light-sensitive material of the present invention is preferably constituted by coating at least one blue-sensitive silver halide emulsion layer, at least one green-sensitive silver halide emulsion layer and at least one red-sensitive silver halide emulsion layer on a support. In general color photographic printing paper, it is normal that the color printing paper is coated on the support in the above-mentioned order, but the order may be different from this. In these photosensitive emulsion layers,
A silver halide emulsion having sensitivity in each wavelength range,
The color reproduction of the subtractive method is carried out by incorporating a so-called color coupler which forms a dye having a complementary color relationship with the light to be exposed-namely, yellow for blue, magenta for green and cyan for red.

The silver halide emulsion used in the present invention comprises silver chloride, silver chlorobromide or silver chloroiodobromide having a silver chloride content of 90 mol% or more. The silver iodide content is preferably 1 mol% or less, more preferably 0.2 mol% or less. The halogen composition of the emulsion may be different or the same between grains, but it is preferable to use an emulsion having the same halogen composition between grains because it is easy to make the properties of each grain uniform. Regarding the halogen composition distribution inside the silver halide emulsion grains, the so-called uniform structure grains having the same composition in any part of the silver halide grains, or the core inside the silver halide grains and the shell surrounding it. (Shell) [a single layer or a plurality of layers] particles having a so-called laminated structure having a different halogen composition, or a structure having a portion having a different halogen composition inside or on the surface of the particle (edge of the particle when present on the particle surface, It is possible to appropriately select and use particles having a structure in which parts having different compositions are bonded to a corner or a surface. In order to obtain high sensitivity, it is advantageous to use either of the latter two rather than the particles having a uniform structure, and it is also preferable from the viewpoint of pressure resistance. When the silver halide grain has the above structure,
The boundary between the different portions in the halogen composition may be a clear boundary or an unclear boundary by forming a mixed crystal due to the composition difference, and positively imparted a continuous structural change. It may be one.

A so-called high silver chloride emulsion having a high silver chloride content is preferably used for a light-sensitive material suitable for rapid processing.
In the present invention, those having a silver chloride content of 90 mol% or more are used, but those having a higher silver chloride content can also be preferably used. The silver chloride content is more preferably 95 mol% or more, particularly preferably 98 mol% or more. In such a high-silver chloride emulsion, a structure having a silver bromide-rich phase localized in the inside and / or on the surface of the silver halide grain is preferable, as described above. The halogen composition of the localized phase preferably has a silver bromide content of at least 10 mol%, and preferably 20 mol%.
It is more preferable that the number exceeds. These localized phases can be present inside the particles, on the edges, corners or on the surface of the particles, but those present at the corners of the particles are particularly preferable. On the other hand, it is also preferable to use grains having a uniform structure in which the distribution of the halogen composition in the grains is small, for the purpose of suppressing the decrease in sensitivity when the photosensitive material receives pressure.

The average grain size of the silver halide grains contained in the silver halide emulsion used in the present invention (the grain size is defined by the diameter of the circle equivalent to the projected area of the grain and the number average thereof is taken) is 0. 1 μm to 2 μm is preferable. Further, the particle size distribution thereof is preferably a so-called monodispersed coefficient of variation coefficient (standard deviation of particle size distribution divided by average particle size) of 20% or less, preferably 15% or less. At this time, it is also preferable to use the above monodisperse emulsion by blending it in the same layer for the purpose of obtaining a wide latitude, or to perform multi-layer coating. The shape of silver halide grains contained in a photographic emulsion is one having a regular crystal form such as cubic, tetradecahedral or octahedral, and irregular (iregular) such as spherical or plate-like. ) Those having a crystalline form or those having a composite form thereof can be used. It may also be a mixture of materials having various crystal forms. In the present invention, 50% of the particles having the above-mentioned regular crystal form are used in the present invention.
The above content is preferably 70% or more, more preferably 90% or more. In addition to these, an emulsion having tabular grains having an average aspect ratio (diameter in terms of circle / thickness) of 5 or more, preferably 8 or more as a projected area exceeding 50% of all grains can be preferably used.

The emulsion used in the present invention is described by P. Glafkides C
himie et Phisique Photographique (published by Paul Montel,
1967), GF Duffin Photographic Emulsion
Chemistry (Focal Press, 1966), VL Z
Making and Coating Photographic Emu by elikman et al
It can be prepared by the method described in Ision (Focal Press, 1964) and the like. That is, any of an acidic method, a neutral method, an ammonia method and the like may be used, and as a format for reacting the soluble silver salt and the soluble halogen salt, any method such as a one-sided mixing method, a simultaneous mixing method, and a combination thereof may be used. You may use. It is also possible to use a method of forming particles in an atmosphere in which silver ions are excessive (so-called reverse mixing method). As one form of the simultaneous mixing method, a method of keeping pAg constant in the liquid phase in which silver halide is formed, that is, a so-called controlled double jet method can be used. According to this method, a silver halide emulsion having a regular crystal form and a substantially uniform grain size can be obtained.

In the silver halide emulsion used in the present invention, various polyvalent metal ion impurities can be introduced in the process of emulsion grain formation or physical ripening. Examples of compounds used include salts of cadmium, zinc, lead, copper, thallium, etc., or salts or complex salts of Group VIII elements iron, ruthenium, rhodium, palladium, osmium, iridium, platinum and the like. it can.
In particular, the above Group VIII elements can be preferably used.
The amount of these compounds added may vary over a wide range depending on the purpose, but is preferably 10 ^-9 to 10 ^-2 mol with respect to the silver halide. The silver halide emulsion used in the present invention is chemically and spectrally sensitized. Chemical sensitization is sulfur sensitization or selenium sensitization typified by the addition of unstable sulfur compounds,
Noble metal sensitization typified by gold sensitization or reduction sensitization can be used alone or in combination. To the silver halide emulsion used in the present invention, various compounds or their precursors are added for the purpose of preventing fog during the production process of the light-sensitive material, storage or photographic processing, or stabilizing photographic performance. be able to. As specific examples of these compounds, those described on pages 39 to 72 of the above-mentioned JP-A-62-215272 are preferably used. The emulsion used in the present invention may be any type of so-called surface latent image type emulsion in which a latent image is mainly formed on the grain surface, or so-called internal latent image type emulsion in which a latent image is mainly formed inside the grain. Is also good. The gelatin used in the present invention is preferably deionized. Gelatin usually contains a large amount of calcium ions, and often contains 5,000 ppm or more. The deionized gelatin used in the present invention has a calcium ion content of 50.
It is preferable to use one having a content of 0 ppm or less. Deionized gelatin is preferably used in an amount of 10% by weight or more, more preferably 20% by weight or more, and particularly preferably 50% by weight or more, based on the whole gelatin.

In the present invention, in a silver halide emulsion layer containing a coupler that forms a complementary color of a color to which a color gradation is desired, any of primary color light which is in a relationship other than complementary color with a color forming dye in relation to the three primary colors of light. It is necessary that the sensitivity of the layer to either or both of the two emulsion layers is 1/2 or less and 1/32 or more, and the gradation ratio is less than 0.6 with respect to the higher sensitivity of the other two emulsion layers. . When the sensitivity ratio becomes 1/2 or more,
Color mixing that impairs color saturation occurs in a relatively low density portion where color gradation is not required, which is not preferable. On the contrary, if the sensitivity ratio becomes 1/32 or less, the effect of the present invention can hardly be obtained in the first place. More preferably 1/3 or less 1/32
Above, more preferably, it is set to have a sensitivity ratio of 1/4 or less and 1/32 or more. Particularly preferably, it is 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.

The gradation in the present invention will be described by taking the cyan coloring layer as an example. The ratio of the gradation for green or blue light to the gradation for red light needs to be less than 0.6. Gradation in this case is a graph in which the vertical axis represents the change in density due to the cyan coloring dye and the horizontal axis represents the logarithmic value of the exposure amount, so that the density due to the coloring dye increases from 0.1 to 0.6. It is defined as twice the logarithmic value of the required exposure dose. When exposed to light other than complementary color light, other color forming layers may also be exposed to light and develop color, and if the density is measured as it is, the secondary absorption of the cyan part of the color of the other color forming layer is also due to the cyan color forming dye. It may be mistaken for. In such a case, it is necessary to accurately measure the sub-absorption of the cyan portion of the color of the other color-developing layer and remove it from the measured value to prepare a graph of density change due to only the cyan color-developing dye. The same applies to the gradations of the other coloring layers. The gradation ratio relationship in the present invention is applied only when the coupler-containing silver halide emulsion layer is substantially sensitive to the complementary color of the dye which the coupler develops and light other than the complementary color. The gradation ratio is preferably 0.6 or less and 0.05 or more. It is more preferably less than 0.55 and 0.2 or more, and particularly preferably less than 0.5 and 0.3 or more. In order to set the ratio of color gradation to 0.6 or less, it is necessary to use two or more kinds of emulsions having different spectral sensitivities.

Taking a cyan coupler-containing layer as an example, an emulsion that is spectrally sensitized only with a sensitizing dye that is red, which is substantially the complementary color of cyan, and a complementary light-sensitive emulsion and a light other than complementary light are used. Emulsion, that is, red, and a mixture of emulsions that are spectrally sensitized with a light-sensitive sensitizing dye other than red, that is, green or / and blue, are mixed, or both are red. And spectral sensitization with a sensitizing dye that is sensitive to a color other than red, that is, green and / or blue, the sensitivity difference for light excluding red light is 25 more than that for red light.
% And more emulsions are mixed and contained. A sensitizing dye having a complementary color relationship is applied to the magenta coupler-containing layer and the yellow coupler-containing layer in the same manner as above. Claim 3
The same applies when emulsions such as are used in different layers. In the present invention, any one layer of the cyan coupler-containing layer, the magenta coupler-containing layer and the yellow coupler-containing layer may satisfy the above relationship, but a plurality of layers may satisfy the above relationship.

In the present invention, the sensitizing dye is used as follows. That is, the red photosensitive sensitizing dye is a sensitizing dye that gives a peak wavelength of spectral sensitivity at about 590 nm to 720 nm when adsorbed on a silver chloride emulsion, and the blue photosensitive sensitizing dye is adsorbed on a silver chloride emulsion. Sometimes about 390nm
A sensitizing dye that gives a peak wavelength of spectral sensitivity at 510 nm, and a green-sensitive sensitizing dye is a sensitizing dye that gives a peak wavelength of spectral sensitivity at about 510 nm to 590 nm when adsorbed on a silver chloride emulsion. The spectral sensitizing dyes used in the present invention include cyanine dyes, merocyanine dyes, complex merocyanine dyes and the like. In addition, complex cyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes are used.
As the cyanine dye, simple cyanine dye, carbocyanine dye and dicarbocyanine dye are preferably used. These cyanine dyes can be represented by the following general formula (I). General formula (I)

[0020]

[Chemical 3]

In the formula, L represents a methine group or a substituted methine group, R ₁ and R ₂ each represent an alkyl group or a substituted alkyl group, and Z ₁ and Z ₂ each represent a nitrogen-containing 5- to 6-membered heterocycle. It represents an atomic group forming a nucleus, and X represents an anion. n represents 1, 3 or 5,
n ₁ and n ₂ are 0 or 1, respectively, when n = 5, both n ₁ and n ₂ are 0, and when n = 3, at least one of n _{1 and} n ₂ is 0. m represents 0 or 1, but is 0 when forming an intramolecular salt. When n is 5, L's may be linked to each other to form a substituted or unsubstituted 5-membered or 6-membered ring. 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, "combining two or more" includes the case where these groups are independently bonded to the alkyl group and the case where these groups are linked and bonded to the 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. Examples of the anion represented by X Cl ^-, Br ^{-,
_{I -, SO 4 -, NO}} 3 -, ClO 4 - and the like can be given.

In the merocyanine dye or the complex merocyanine dye, as a nucleus having a ketomethylene structure, a pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thiooxazolidine-2,4-dione nucleus, a thiazolidine-2,4-
5 such as dione nucleus, rhodanine nucleus, thiobarbituric acid nucleus
A 6-membered nucleus can be incorporated. In the present invention, a pyrroline nucleus, an oxazoline nucleus, a thiazoline nucleus, a pyrrole nucleus,
Spectral sensitizing dyes other than those mentioned above incorporating thiazole nucleus, oxazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, and nucleus in which alicyclic hydrocarbon ring and further aromatic hydrocarbon ring are fused. Can also be used. Examples of useful spectral sensitizing dyes include German Patent 929,080 and US Pat. No. 2,231,658.
No. 2,493,748, No. 2,503,77
No. 6, No. 2,519,001, No. 2,912, 3
No. 29, No. 3,656,959, No. 3,672,
No. 897, No. 3,694,217, No. 4,02
5, 349, 4,046,572, British Patent Nos. 1,242,588, Japanese Patent Publication Nos. 44-14030 and 52-24844, and the like. In the present invention, those having a benzothiazole nucleus and a benzoxazole nucleus are preferable among the above dyes, and a simple cyanine dye having a benzothiazole nucleus, a carbocyanine dye having a benzoxazole nucleus, and a dicarbocyanine having a benzothiazole nucleus. Dyes are especially preferred.

Usually, in order to spectrally sensitize a silver halide emulsion, a method is used in which after the grains are completely formed, a spectral sensitizing dye is adsorbed on the surface of the grains. On the other hand, U.S. Pat. No. 2,735,766 discloses a method of adding a merocyanine dye during the precipitation formation of silver halide grains, whereby it is possible to reduce the amount of dye which is not adsorbed. Have been described. 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. It is a method such as described in,

After the particle formation is completed, it means that the particles are added and 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, the addition of the spectral sensitizing dye after the completion of grain formation does not require the chemical sensitization even before the initiation of such chemical sensitization. Even in the middle or after the completion of chemical sensitization, it may be added until just before the emulsion is applied, but in the present invention,
The addition of the spectral sensitizing dye as described above is preferably added before preparing the coating liquid. In the aspect of claim (2), it is necessary to add the spectral sensitizing dye before preparing the coating solution. Furthermore, when two or more kinds of emulsions are mixed to prepare a coating solution and the coating solution is used for coating, it is preferable to coat within 6 hours after mixing the emulsions.
It is more preferably within 2 hours, particularly preferably within 30 minutes.

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 from 1 × 10 ⁻⁶ mol to 1 × 10 ⁻² mol per mol of silver halide. Mole,
More preferably, 1 × 10 ⁻⁵ mol to 5 × 10 ⁻³ mol is added.

The spectral sensitizing dyes used in the present invention may be used alone or in combination of two or more kinds. Among the sensitizing dyes preferably used in the present invention, the general formula (I)
Specific examples of the cyanine dye represented by
(V-1) to (V-36) described on pages 10 to 13 of No. 129628 can be mentioned. Along with the spectral sensitizing dye, a dye that does not have a spectral sensitizing effect by itself, or a supersensitizer that does not substantially absorb in the visible region but enhances the sensitizing effect of the spectral sensitizing dye is included. Good.

In the present invention, the aminostilbene compounds substituted with a nitrogen-containing heterocyclic group (for example, those described in US Pat. Nos. 2,933,390 and 3,635,721) are as described above. It is useful for reducing the residual color of a carbocyanine dye having an oxazole nucleus and improving the color sensitizing property of a dicarbocyanine dye having a benzothiazole nucleus,
The combined use is particularly preferable. The aminostilbene compound preferably used in the present invention is 4,4'-bis (s-triazinylamino) stilbene-2,2'-disulfonic acid or 4,4'-bis (pyrimidinylamino) stilbene-2, Examples thereof include 2'-disulfonic acid and alkali metal salts thereof. In these compounds, the s-triazine ring or the 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 more preferable that one or two sites are substituted with a hydroxyl group or an amino group. In order to reduce the 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).

[0031]

[Chemical 4]

In the formula, D represents a divalent aromatic residue,
R ₁₂ , R ₁₃ , R ₁₄ and R ₁₅ are each a hydrogen atom, a hydroxy group, an alkoxy group, an aryloxy group, a halogen atom, a heterocyclic group, a mercapto group, an alkylthio group, an arylthio group, a heterocyclylthio group, an amino group, an alkyl group. It represents an amino group, a cyclohexylamino group, an arylamino group, a heterocyclylamino group, an aralkylamino group or an aryl group. Q ₁ and Q ₂ each represent -N = or -C =. However, at least one of Q ₁ and Q ₂ is -N =. Examples of compounds that are particularly preferably used in the invention include (F-1) to (F-24) described on pages 15 to 18 of JP-A-2-129628. The effect of the present invention is particularly clear when a pyrazoloazole-based coupler is used as the magenta coupler, in other words, when the technique of the present invention is used in such a system, a coloring dye of the pyrazoloazole-based coupler is obtained. High color saturation due to its excellent spectral absorption characteristics and, conversely, a color gradation that is easily damaged by it, can be achieved at the same time, and it also has excellent characteristics in terms of rapid processability and color image fastness. A color photographic light-sensitive material can be obtained. The pyrazoloazole-based magenta coupler used in the present invention is particularly preferably the one represented by the general formula (M).

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 listed in US Pat. No. 4,540,654, and the pyrazolo [1,5-b] [1,2,4] triazoles described in US Pat. No. 4,540,654 are particularly preferred. In addition, the branched alkyl group as described in JP-A-61-65245 has a pyrazolotriazole ring of 2,
Pyrazolotriazole coupler directly connected to the 3 or 6 position,
A pyrazoloazole coupler containing a sulfonamide group in the molecule as described in JP-A-61-65246,
Pyrazoloazole couplers having an alkoxyphenyl sulfonamide ballast group as described in JP-A-61-147254 and EP-A-226,849.
It is preferable to use a pyrazolotriazole coupler having an alkoxy group or an aryloxy group at the 6-position as described in No. 294,785 and No. 294,785. Specific examples of the compounds preferably used are shown below.

[0034]

[Chemical 5]

[0035]

[Chemical 6]

[0036]

[Chemical 7]

[0037]

[Chemical 8]

[0038]

[Chemical 9]

[0039]

[Chemical 10]

[0040]

[Chemical 11]

In the light-sensitive material according to the present invention, a dye capable of being decolorized by a treatment described in European Patent EP 0,337,490A2, pages 27 to 76, is added to a hydrophilic colloid layer for the purpose of improving image sharpness and the like. (Among others, an oxonol dye) is added so that the optical reflection density at 680 nm of the light-sensitive material is 0.70 or more, or a dihydric or tetrahydric alcohol (for example, an alcohol) is added to the water-resistant resin layer of the support. Titanium oxide surface-treated with trimethylolethane) etc.
It is preferable that the content is at least wt% (more preferably at least 14 wt%). The light-sensitive material according to the present invention includes
It is preferred to use with the coupler a color image-storing improving compound as described in EP 0,277,589 A2. In particular, it is preferably used in combination with a pyrazoloazole coupler.

That is, a compound (F) and / or a compound which chemically bonds with an aromatic amine-based developing agent remaining after color development processing to form a chemically inactive and substantially colorless compound.
Alternatively, the compound (G) which chemically bonds with an oxidized product of an aromatic amine color developing agent remaining after the color developing treatment to form a chemically inactive and substantially colorless compound is used simultaneously or alone. However, it is preferable to prevent the occurrence of stains and other side effects due to the formation of a coloring dye due to the reaction of the residual color developing agent in the film or the oxidant thereof with the coupler during storage after processing.

The light-sensitive material according to the present invention has a mildewproofing agent as described in JP-A-63-271247 in order to prevent various molds and bacteria which propagate in the hydrophilic colloid layer and deteriorate the image. It is preferable to add an agent. The support used in the light-sensitive material according to the present invention may be a white polyester support for display or a support provided with a layer containing a white pigment on the support having a silver halide emulsion layer. You may use. 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 preferably set in the range of 0.35 to 0.8 so that the display can be viewed with both reflected light and transmitted light.

The light-sensitive material according to the present invention may be exposed to visible light or infrared light. The exposure method may be 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. Further, upon exposure, it is preferable to use the band stop filter described in US Pat. No. 4,880,726. As a result, light color mixture is removed, and color reproducibility is significantly improved. For the purpose of rapid processing, the exposed light-sensitive material is preferably subjected to bleach-fixing processing after color development. Particularly when the above high silver chloride emulsion is used, 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 etc.) and photographic constituent layers (layer arrangement etc.) applied to the light-sensitive material according to the present invention, and processing methods and processings applied for processing this light-sensitive material. As the additive, those described in the following patent publications, particularly European Patent EP 0,355,660A2 (Japanese Patent Application No. 1-107011) are preferably used.

[0045]

[Table 1]

[0046]

[Table 2]

[0047]

[Table 3]

[0048]

[Table 4]

[0049]

[Table 5]

Further, as a cyan coupler, Japanese Patent Laid-Open No. 2-212058 can be used.
In addition to the diphenylimidazole type cyan coupler described in JP-A-33144, European Patent EP 0,333,185A.
3-Hydroxypyridine cyan couplers described in No. 2 (among others, couplers (42) listed as specific examples, which are converted into 2-equivalent by attaching a chlorine-eliminating group to couplers (6) and (9). Is particularly preferable) and the 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.

[0051]

【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 above liquid was added and mixed for 40 minutes while maintaining 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, red sensitizing dye (V-6) 0.46 × 10 ⁻⁴ mol / mol Ag, and a monodisperse silver bromide emulsion having an average grain size of 0.05 μ was added in an amount of 0.6 mol% as silver halide. In addition, it was optimally chemically sensitized with triethylthiourea and chloroauric acid, and 1- (5-methylureidophenyl) -5-mercaptotetrazole was further added at 7 × 10 ⁻⁴ mol / mol Ag,
Emulsion Em-1 was used. Further, the following compounds were added in an amount of 2.6 × 10 ⁻³ mol per mol of silver halide.

[0052]

[Chemical 12]

On the other hand, in the method of preparing Em-1, the particle formation temperature was lowered to an average particle size of 0.38 μ, and (V−
6) An emulsion Em-4 was obtained in the same manner as the emulsion Em-1, except that the addition amount was 0.56 × 10 ^-4 mol / mol Ag, and a low-sensitivity red light-sensitive emulsion for a cyan coupler-containing silver halide emulsion layer. And A green photosensitive emulsion for a magenta coupler-containing silver halide emulsion layer was prepared as follows. 30 g of coal-treated gelatin was added to 1000 ml of distilled water and dissolved at 40 ° C., and then 5.5 g of sodium chloride and 0.02 g of N, N′-dimethylimidazolidine-2-thione were added to raise the temperature to 50 ° C. Let 62.5 g of silver nitrate, 75 distilled water
A solution dissolved in 0 ml and a solution prepared by dissolving 21.5 g of sodium chloride in 500 ml of distilled water were added to and mixed with the above solution over 40 minutes while maintaining the temperature at 50 ° C. Further, a solution prepared by dissolving 62.5 g of silver nitrate in 500 ml of distilled water and 21.5 g of sodium chloride.
2) and a solution prepared by dissolving the above in 300 ml of distilled water at 50 ° C.
The mixture was added and mixed for 0 minutes.

When the obtained emulsion was observed with an electron microscope, it was an emulsion consisting 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, exemplary compound (V-41) 5 × 10 ⁻⁴ mol / mol A
g, and a monodispersed silver bromide emulsion having an average grain size of 0.05μ were added in an amount corresponding to 0.4 mol% of silver halide, and optimally chemically sensitized with triethylthiourea and chloroauric acid. 1.1 × 10 ⁻³ mol / mol Ag of 1- (5-methylureidophenyl) -5-mercaptotetrazole was added to obtain a green light-sensitive emulsion Em-2 for a magenta coupler-containing silver halide emulsion layer.

On the other hand, in the method for preparing the emulsion Em-2, the temperature at the time of grain formation was lowered, the average grain size was 0.37 μm, and (V-41) was 6 × 10 ⁻⁴ mol / mol Ag.
Emulsion Em-5 was prepared in the same manner as Emulsion Em-2 except the above. 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 is distilled water 100
The solution was added to 0 ml, dissolved at 40 ° C., adjusted to pH 3.8 with sulfuric acid, 5.5 g of sodium chloride and 0.03 g of N, N′-dimethylimidazolidine-2-thione were added, and the temperature was adjusted to 75 ° C. Raised to. 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 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, blue sensitizing dye (V-34) 2 × 10 ⁻⁴ mol / mol Ag
And (V-36) 2 × 10 ^-4 mol / mol Ag, and a monodispersed silver bromide emulsion having an average grain size of 0.05 μ were added in an amount of 0.3 mol% with silver halide, and triethylthiourea was added. , Chemically sensitized with chloroauric acid, and 1- (5-
Methylureidophenyl) -5-mercaptotetrazole was added at 9 × 10 ⁻⁴ mol / mol Ag to give a high-sensitivity blue-sensitive emulsion Em for a silver halide emulsion layer containing a yellow coupler.
-3. On the other hand, in the preparation method of Em-3, the temperature at the time of particle formation was lowered to an average particle size of 0.70 μ, and (V
-34) and (V-36) were added at 2.5 x 1 each.
Emulsion Em-6 was prepared in the same manner as emulsion Em-3 except that it was 0 ^-4 mol / mol Ag to give a low-sensitivity blue light-sensitive emulsion for a silver halide emulsion layer containing a yellow coupler.

The halogen composition and its distribution of the 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.
70% to 65% silver chloride in addition to the main peak corresponding to mol%
A broad diffraction pattern having a center in the vicinity of mol% 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 liquid for the first layer: 19.1 g of a yellow coupler (ExY), 4.4 g of a color image stabilizer (Cpd-1) and 0.7 g of a color image stabilizer (Cpd-7) were added to 27.2 cc of ethyl acetate and Solvents (Solv-3) and (Solv-3
-7) Add 4.1g of each to dissolve, then add 10% of this solution.
10 including 8cc of sodium dodecylbenzene sulfonate
% Gelatin aqueous solution 185 cc to prepare an emulsified dispersion A. Emulsions Em-3 and Em-6 were mixed in a ratio of 3: 7, and then mixed and dissolved with the emulsified dispersion A described above to prepare a coating solution 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, after the cyan coupler was dissolved in ethyl acetate together with the color image stabilizer (Cpd-7), etc. , Emulsified and dispersed). 1-Oxy-3,5-dichloro-s-triazine sodium salt was used as a gelatin hardening agent for each layer. Further, the total amount Cpd-10 and Cpd-11 were added to each so that 25.0 mg / m ² and 50 mg / m ² in each layer.

Further, for the yellow coupler-containing emulsion layer and the magenta coupler-containing emulsion layer, 4-hydroxy-6-
Methyl-1,3,3a, 7-tetrazaindene was added in an amount of 1 × 10 ⁻⁴ mol and 2 × 1 mol per mol of silver halide, respectively.
^0-4 mol was added. Further, the following dyes (the amount in parentheses represents the coating amount) were added to the emulsion layer to prevent irradiation.

[0060]

[Chemical 13]

(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 a white pigment (TiO ₂ ) and a bluish dye (ultraviolet)] First layer (blue-sensitive emulsion layer) Emulsion Em-3 0.09 Emulsion described above Em-6 0.21 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 inhibitor (Cpd-5) 0.08 Solvent (Solv-1) 0.16 Solvent (Solv-4) 0. 08

Third Layer (Green Sensitive Emulsion Layer) The Emulsion Em-2 0.04 The Emulsion Em-5 0.07 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 Four layers (UV absorbing layer) Gelatin 1.58 UV absorbing agent (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 1.34 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 (Ultraviolet Absorbing Layer) Gelatin 0.53 Ultraviolet Absorber ( UV-1) 0.16 Color mixing inhibitor (Cpd-5) 0.02 Solvent (Solv-5) 0.08 Seventh layer (protective layer) Gelatin 1.33 Acrylic modified copolymer of polyvinyl alcohol (Degree of modification 17 %) 0.17 Liquid paraffin 0.03

[0063]

[Chemical 14]

[0064]

[Chemical 15]

[0065]

[Chemical 16]

[0066]

[Chemical 17]

[0067]

[Chemical 18]

[0068]

[Chemical 19]

[0069]

[Chemical 20]

[0070]

[Chemical 21]

[0071]

[Chemical formula 22]

Coating was carried out 30 minutes after the coating solution was prepared.
The sample thus prepared was designated as Sample 101. In Sample 101, an emulsion was prepared by adding a blue-sensitive spectral sensitizing dye to the silver halide emulsions Em-1 and Em-4 used in the cyan coupler-containing layer as shown in Tables 1 and 2. The blue-sensitive spectral sensitizing dye was added before the start of chemical sensitization.

[0073]

[Table 6]

The emulsions obtained in Tables 1 and 2 were prepared as Em1 and E
Combine and replace m4 as shown in Table 3 below,
Samples 102-115 were obtained.

[0075]

[Table 7]

In the sample 101, Em-1 and E
A sample was prepared in which the total amount of m-4 was replaced with the following emulsion alone.

[0077]

[Table 8]

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

Color developing solution Tank solution Replenishing solution Water 800 ml 800 ml Ethylenediamine-N, N, N ', N'-tetramethylenephosphonic acid 1.5 g 2.0 g Potassium bromide 0.015 g-Triethanolamine 8.0 g 12. 0 g sodium chloride 1.4 g-potassium carbonate 25 g 25 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaminoline sulfate 5.0 g 7.0 g N, N-bis (carboxy) Methyl) hydrazine 4.0g 5.0g N, N-di (sulfoethyl) hydroxylamine 1Na 4.0g 5.0g Optical brightener (WHITEX 4B, Sumitomo Chemical Co., Ltd.) 1.0g 2.0g 1000 ml 1000 ml pH (25 ° C) 10.05 10.45

Bleach-fixing solution (same as tank solution and replenisher) Water 400 ml Ammonium thiosulfate (70%) 100 ml Sodium sulfite 17 g Ethylenediaminetetraacetic acid iron (III) ammonium 55 g Ethylenediaminetetraacetate disodium 5 g Ammonium bromide 40 g Water was added. 1000 ml pH (25 ° C) 6.0 Rinse solution (same as tank solution and replenisher) Ion-exchanged water (3 pp each for calcium and magnesium)
m or less) using the developer after the continuous processing thus obtained, the sample 101
To 117 and 201 to 213, Fuji Photo Film Co., Ltd. FWK type sensitometer was used to make SP-1,
2500 Lux through SP-2 and SP-3 filters
Three-color separation / gradation exposure of 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 5 shows the sensitivity and gradation ratio in the blue exposure (SP-1) or the green exposure (SP-2) with respect to the sensitivity and gradation in the red exposure (SP-3) obtained for the samples 101 to 117, and The difference in sensitivity between red exposure and the difference in sensitivity between blue and green exposure of the emulsions mixed and used was shown. The value of the difference in sensitivity of the emulsion was obtained from Samples 201 to 213.

[0081]

[Table 9]

(Gradation Ratio Change Test) Samples 301 and 302 were prepared from the sample 107 prepared above, after the coating liquid was prepared, and the time until coating was 3 hours and 6 hours, respectively. Furthermore, in the sample 107, only the red-sensitive layer was replaced with two layers of the red-sensitive layers of the samples 204 and 206, which were applied in an amount of 30% of the original amount.
Was changed to 70%, and a sample applied 303 minutes after the preparation of the coating solution was designated as 303. Samples coated with these coating solutions after 3 hours and 6 hours were designated as 304 and 305, respectively. The blue / red light gradation ratio of the above samples 301 to 305 and 107 was examined. The results are shown in Table 6.

Table 6 Samples Gradation ratio (blue light / red light) Remark 107 0.48 Present invention 301 0.51 Present invention 302 0.59 Present invention 303 0.45 Present invention 304 0.45 Present invention 305 0.45 The sample in which the emulsion of the present invention is applied in two layers is more preferable because the gradation ratio does not change with time.

(Test of Color Gradation and Color Reproducibility) Regarding Samples 101 to 117 and Sample 303 prepared above, hemp summer sweater of red color, sweater made of the same red extra thick wool, and silk of the same red color This blouse was placed on a gray background, exposed to strong light obliquely from above, and photographed using Fuji Color Super HG400, and the specified processing was performed. After that, the sample was printed through the negative with a Fuji C450 printer and evaluated from the viewpoint of color gradation reproducibility. The evaluation was performed in the following three stages.

The results are shown in Table 7. <Color gradation> A The textures of silk, linen, and soft wool can be distinguished, and the texture can be seen well. B The texture looks crisp, but the hemp and woolen yarns look stiff and stiff as well. 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 Even in the low density area, red is darkened. Or, all the materials are red and the colors are colorful, but the colors cannot be distinguished.

[0086]

[Table 10]

As is clear from the results in Table 7, samples 107, 110 to 112, and 114 to 303 of the present invention.
Then, it can be seen that both have excellent color gradation and color reproducibility.

[0088]

According to the present invention, a color photographic material having excellent suitability for rapid processing, improved color tone reproducibility, particularly color tone reproducibility of high density areas, and excellent color reproducibility can be obtained. It was

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display location G03C 7/38

Claims (4)

[Claims] 1. A silver halide color photographic light-sensitive material having, on a support, three kinds of silver halide emulsion layers each containing a coupler capable of coloring yellow, magenta and cyan, respectively. The average silver chloride content of silver is 90 mol% or more, and at least one of the coupler-containing silver halide emulsion layers has a primary color light and a primary color light other than the complementary color in a complementary color relationship with the color forming dye in the relationship of the three primary colors of light. Are spectrally sensitized to, and the sensitivity of the layer to primary color light other than the complementary color is 1/2 or less 1/32 or more with respect to either of the other two coupler-containing emulsion layers,
And a ratio of a gradation when exposed with primary color light other than the complementary color to a gradation when exposed with primary color light having a complementary color relationship with the color forming dye of the layer is less than 0.6. Silver color photographic light-sensitive material. 2. A silver halide color photographic light-sensitive material having, on a support, three kinds of silver halide emulsion layers each containing a coupler capable of forming yellow, magenta and cyan, respectively. The average silver chloride content of silver is 90 mol% or more, and at least one of the coupler-containing silver halide emulsion layers is a mixture of at least two kinds of silver halide emulsions having different average grain sizes. Emulsion (A) is at least one of a sensitizing dye having a spectral sensitivity to a primary color light complementary to a color forming dye in the relationship of three primary colors of light, and a sensitizing dye having a spectral sensitivity to a primary color light other than a complementary color. The other emulsion (B) is spectrally sensitized with a sensitizing dye having a spectral sensitivity to the primary color light having a complementary color relationship with the color forming dye with respect to the emulsion (A). Of the sensitizing dye having a spectral sensitivity to primary color light other than the complementary color, the emulsion is spectrally sensitized at a molar ratio of 50% or less per silver halide grain. Photographic material. 3. A silver halide color photographic light-sensitive material having, on a support, three kinds of silver halide emulsion layers each containing a coupler capable of forming yellow, magenta and cyan, respectively. The average silver chloride content of silver is 90 mol% or more, and at least one of the coupler-containing silver halide emulsion layers is composed of two or more layers that develop substantially the same color. Emulsion (A) contained in is a sensitizing dye having a spectral sensitivity to primary color light complementary to a color forming dye in the relationship of three primary colors of light, and a sensitizing dye having a spectral sensitivity to primary color light other than a complementary color. Which is spectrally sensitized with at least one of
The emulsion (B) contained in the other layer is spectrally sensitive to primary color light other than the complementary color to the sensitizing dye which has spectral sensitivity to the primary color light complementary to the color forming dye with respect to the emulsion (A). A silver halide color photographic light-sensitive material characterized by being a spectrally sensitized emulsion in which the molar ratio of the sensitizing dye having the formula (1) is 50% or less per grain of silver halide. 4. The magenta coupler used in the magenta coupler-containing layer is a pyrazoloazole compound represented by the following general formula [M].
Alternatively, the silver halide color photographic light-sensitive material as described in 3 above. [Chemical 1] (In the formula, R ₁ represents a hydrogen atom or a substituent. Y ₁ represents a hydrogen atom or a leaving group. Za, Zb and Zc represent methine, substituted methine, ═N— or —NH—, and Z
One of the a-Zb bond and the Zb-Zc bond is a double bond, and the other is a single bond. The case where the Za-Zb bond is a carbon-carbon double bond includes the case where it is part of an aromatic ring. This includes the case where R ₁ or Y ₁ forms a dimer or higher multimer, and the case where Za, Zb, or Zc is a substituted methine, the substituted methine forms a dimer or higher multimer. )