JPH0876329A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE: To enhance color reproduction performance and to reduce the deterioration of performance due to the fluctuation of development processing conditions by incorporating a specified dye in the form of solid dispersion in one layer and specified couplers in another layer. CONSTITUTION: The color photographic sensitive material contains at least one kind of dye represented by the formula in a solid dispersion in at least one layer and at least 2 kinds of couplers to be allowed to develop color different in hue from each other in at least one of photosensitive emulsion layers or its adjacent layer. In the formula, A is an acid nucleus having at least one carboxyl group; each of L<1> -L<3> is an optionally substituted methine group; each of R<1> and R<3> is an H or another atom or a substituent; R<2> is a substituent including a substituent atom; n is 0 or 1; m is 0, 1, 2, 3, or 4, and when m is >=2, R<2> may be same or different; and X is an electron withdrawing group having a Hammett's substituent constant δm of 0.3-1.5.

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 having improved color reproducibility and stability against variations in development processing conditions.

[0002]

2. Description of the Related Art In recent years, the requirements for the performance of color photographic light-sensitive materials have become more and more stringent, and high sharpness, smooth graininess, vivid and faithful color reproduction, stability against variations in development processing conditions, etc. It is desired to improve various photographic characteristics.

In order to obtain more vivid color reproduction, the so-called masking and multi-layer (inter-image) effects disclosed in US Pat. No. 2,521,908 have been used.

The multilayer effect is described in, for example, Hanson et al., "Journa of the Optical Society of Omerica".
l of the Optical Society
of America), vol. 42, pp. 663-66.
Page 9, and A. A. Thiels
Written by "Zeitschrift Für Wiessen Schachrichier Photography Photophysique und Photohiemie
Wissenschaftriche Photog
raphie, photophysique und
Photochemie), Vol. 47, pp. 106-1
18 and 246-255.

By improving the multi-layer effect in this way, it is possible to improve the color reproducibility of the color photographic light-sensitive material, especially the saturation, but it is not sufficient in faithfully reproducing the hue of the subject. .

It has been disclosed to mix couplers that develop different hues for the purpose of improving the fidelity of color reproduction. For example, US Pat. No. 2,59
No. 2,514, in the blue-sensitive silver halide emulsion layer, in addition to the yellow coupler, a cyan coupler and a magenta coupler, in the green-sensitive silver halide emulsion layer, in addition to the magenta coupler, a cyan coupler and a yellow coupler. It is described that a red-sensitive silver halide emulsion layer contains a yellow coupler and a magenta coupler in addition to a cyan coupler to correct the hue shift of the color image of the main coupler, and Japanese Patent Publication No. 33-4881. It is disclosed that an unnatural color feeling is improved by adding an intermediate gray image in addition to the original color image by mixing another color developing agent in addition to the original color developing agent.

In JP-A-62-67537, the relative coupling speed with respect to the main coupler is 0.01 to 0.7, and when an auxiliary coupler which develops a different hue is used together, the color reproduction is impaired. A method for improving shadow reproduction in high density areas without is disclosed.

Further, JP-A-3-265845 discloses a method of realizing a faithful color reproduction by defining the spectral sensitivity distribution of a red light sensitive emulsion layer and containing a yellow coupler in the red light sensitive emulsion layer. ing. Furthermore, Japanese Patent Laid-Open No. 6-1
No. 30599 discloses that the fidelity of color reproduction and the color temperature dependence can be improved by mixing a cyan coupler and a yellow coupler having a specified coupling activity in a red light-sensitive emulsion layer.

Although it has been possible to improve the fidelity of color reproduction to some extent by mixing couplers having different hues as described above, it is possible to obtain a slight difference in the hue of a subject, especially a subject of yellow or blue. It was not sufficient to discriminate the difference in color tone and reproduce faithfully. Also, in the case of mixing couplers that develop different hues, in order to ensure sufficient density of each single color,
It was necessary to increase the amount of coated silver and the amount of coated coupler. Further, in order to minimize color turbidity caused by mixing different couplers, it is necessary to increase the thickness of the intermediate layer to reduce color mixture. As a result, problems such as defective desilvering and residual color during the development process have newly occurred.

[0010]

DISCLOSURE OF THE INVENTION The present invention provides a silver halide color photographic light-sensitive material capable of well discriminating an object having a color reproducibility, particularly a subtly different hue, and faithfully reproducing the color of the object. Is an issue. A further object of the present invention is to provide a silver halide color photographic light-sensitive material that is less likely to deteriorate in performance due to changes in development processing conditions.

[0011]

The objects of the present invention are: 1) On a support, a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, a blue-sensitive silver halide emulsion layer and a non-sensitive In a silver halide color photographic light-sensitive material having a photosensitive intermediate layer, at least one layer contains at least one solid dispersed dye represented by the following general formula (1), and at least one light-sensitive emulsion layer. Alternatively, a silver halide color photographic light-sensitive material characterized in that an intermediate layer adjacent thereto contains two or more kinds of couplers which develop different hues by reaction with an oxidized product of a developing agent.

[0012]

Embedded image

In the formula, A is at least 1 carboxyl group.
And L ¹ , L ² and L ³ each represent an optionally substituted methine group. R ¹ and R ³ each represent a hydrogen atom or a substituent (including a substituent atom). R
² represents a substituent (including a substituent atom). n is 0 or 1
Represents m represents an integer from 0 to 4, and m is 2 to 4
And R ² may be the same or different. X
Represents an electron-withdrawing group having a Hammett substituent constant σ _m of 0.3 or more and 1.5 or less.

2) The silver halide color photographic light-sensitive material as described in (1), wherein X is an alkoxycarbonyl group or a cyano group, and A is an acidic nucleus substituted with a carboxyphenyl group.

3) A silver halide color photographic light-sensitive material as described in 1) or 2) above, wherein the red light-sensitive emulsion layer contains a cyan coupler and a yellow coupler. 4) The light-sensitive material according to 1) or 2) above, wherein the blue-sensitive emulsion layer contains a yellow coupler, and the blue-sensitive emulsion layer and / or an intermediate layer adjacent thereto contains a cyan coupler. A silver halide color photographic light-sensitive material. 5) In the light-sensitive material of 1) or 2) above, blue,
Each of the green and red color sensitive layers is composed of two or more layers having different sensitivities, and the average emulsion grain size of the emulsion layer having the highest sensitivity among the blue light sensitive emulsion layers is the highest among the green light sensitive emulsion layers. A silver halide color photographic light-sensitive material characterized in that it is at least twice as large as the average grain size of the emulsion in the high-emulsion layer.
Achieved by

The light-sensitive material of the present invention will be described in more detail below.

The light-sensitive material of the present invention comprises a support, a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and
It has a blue-sensitive silver halide emulsion layer and a non-photosensitive intermediate layer. It is desirable that at least one, and preferably two, non-photosensitive intermediate layer be present between each color-sensitive layer. Further, each color-sensitive layer is preferably composed of three or more sublayers having different sensitivities. Preferred specific examples of the layer structure of the light-sensitive material of the present invention are shown below, but the present invention is not limited thereto.
That is, from the support side, 1st layer: antihalation layer 2nd layer: intermediate layer 3rd layer: intermediate layer (containing colloidal silver or fogged fine grain silver halide) 4th layer: low-sensitivity red photosensitive emulsion layer 5th layer : Middle speed red photosensitive emulsion layer 6th layer: High sensitivity red photosensitive emulsion layer 7th layer: Intermediate layer 8th layer: Intermediate layer (containing colloidal silver or fogged fine grain silver halide) 9th layer: Low sensitivity green Photosensitive emulsion layer 10th layer: Medium sensitivity green photosensitive emulsion layer 11th layer: High sensitivity green photosensitive emulsion layer 12th layer: Intermediate layer 13th layer: Yellow filter layer 14th layer: Low sensitivity blue photosensitive emulsion layer Fifteenth layer: Medium sensitivity blue photosensitive emulsion layer Sixteenth layer: High sensitivity blue photosensitive emulsion layer Seventeenth layer: First protective layer Eighteenth layer: Second protective layer Nineteenth layer: Third protective layer Same color sensitivity Of the silver coating amount of each layer when it is composed of 3 or more layers with different sensitivity In this case, when the total amount of silver in the color-sensitive layer is 100%, the high-sensitivity layer is preferably 15-40%, the medium-sensitivity layer is 20-50%, and the low-sensitivity layer is 20-50%. . It is desirable that the coating amount of silver in the high-sensitivity layer be smaller than the coating amount of silver in the middle and low-sensitivity layers.

In the compound of the present invention, by selecting such an electron-withdrawing substituent as X in the general formula (I),
In the photographic processing process, the reaction between the compound and the nucleophile in the processing solution (mainly hydroxide ion, sulfite ion) is promoted,
It shows a remarkable effect in improving the decolorizing property. It is presumed that this effect is because the electron density at the reaction point is lowered by the substitution of the electron-withdrawing group on the indole nitrogen atom that is in the conjugate position with the reaction point with the nucleophile to facilitate the reaction.

First, the general formula (I) will be described in detail. Examples of the acidic nucleus represented by A include 5-pyrazolone, isoxazolone, barbituric acid, thiobarbituric acid, pyrazolopyridone, rhodanine, hydantoin, thiohydantoin, oxazolidinedione, pyrazolidinedione, indandione, hydroxypyridone, 1 ，
2,3,4-tetrahydroquinoline-2,4-dione,
3-oxo-2,3-dihydrobenzo [d] thiophene-1,1-dioxide is preferable, 5-pyrazolone, hydroxypyridone, pyrazolopyridone, barbituric acid or isoxazolone is more preferable, and 5-pyrazolone is particularly preferable. Is.

However, A has at least one carboxyl group. This carboxyl group is preferably bonded to the aryl group (or benzene ring) in the molecule. More preferably, it is bonded to a phenyl group. From the viewpoint of binding of the carboxyl group, the preferred compound of the present invention is a compound represented by the following general formula (II).

[0021]

[Chemical 3]

In the formula, k represents 1, 2 or 3. A'represents an acidic nuclear residue. L ¹ , L ² , L ³ , R ¹ , R ² ,
R ³ , X, n and m have the same meaning as in general formula (I). Further, from the viewpoint of acidic nuclei, the preferred compound of the present invention is a compound represented by the following general formula (III).

[0023]

[Chemical 4]

In the formula, R ⁴ and R ⁵ each represent a hydrogen atom or a substituent (including a substituent atom), and at least one of them represents a substituent having a carboxyl group. L ¹ , L ² , L
³ , R ¹ , R ² , R ³ , X and m have the same meanings as in formula (I).

Further, from the viewpoint of binding of a carboxyl group, in the general formula (III), at least one of R ⁴ and R ⁵ (preferably R ⁵ ) is a carboxyl group-substituted phenyl group.

Hammett's substituent constant σ represented by X
Examples of the electron-withdrawing group having _m (for example, described in Chem. Rev., 91, 165 (1991)) of 0.3 or more and 1.5 or less include, for example, a halogen atom (for example, a fluorine atom (σ _m
Value = 0.34 or less), chlorine atom (0.37), bromine atom (0.39), iodine atom (0.35)), trifluoromethyl group (0.43), cyano group (0.56) ),
Formyl group (0.35), acyl group (eg acetyl (0.38)), acyloxy group (eg acetoxy (0.39)), carboxyl group (0.37), alkoxycarbonyl group (eg methoxycarbonyl) (0.
37)), an aryloxycarbonyl group (for example, phenoxycarbonyl (0.37)), an alkylcarbamoyl group (for example, methylcarbamoyl (0.35)), a nitro group (0.71), an alkylsulfinyl group (for example, methyl). Sulfinyl (0.52)), an alkylsulfonyl group (for example, methylsulfonyl (0.60)),
A sulfamoyl group (0.53) etc. are mentioned. Preferably, it is an alkoxycarbonyl group or a cyano group. More preferably, it is an alkoxycarbonyl group.

The methine group represented by L ¹ , L ² and L ³ is
It may have a substituent (for example, a methyl group, an ethyl group, a cyano group, a chlorine atom), but it is preferably unsubstituted, and n is preferably 0.

The substituent represented by R ¹ , R ² or R ³ is
For example, a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms (eg, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, cyclohexyl, methoxyethyl, ethoxyethyl, ethoxycarbonyl). Methyl, ethoxycarbonylethyl, cyanoethyl, diethylaminoethyl, hydroxyethyl, chloroethyl, acetoxyethyl, etc.), a substituted or unsubstituted aralkyl group having 7 to 12 carbon atoms (eg, benzyl, 2-carboxybenzyl, etc.), 6 carbon atoms 18 substituted or unsubstituted aryl groups (eg, phenyl, 4-methylphenyl, 4-methoxyphenyl, 4-carboxyphenyl, 3,5-dicarboxyphenyl, etc.), substituted or unsubstituted C 2 -C 6 Acyl groups (for example, ace Tyl, propionyl, butanoyl, chloroacetyl, etc.), a substituted or unsubstituted sulfonyl group having 1 to 8 carbon atoms (eg, methanesulfonyl, p
-Toluenesulfonyl, etc.), an alkoxycarbonyl group having 2 to 6 carbon atoms (eg, methoxycarbonyl, ethoxycarbonyl, etc.), an aryloxycarbonyl group having 7 to 12 carbon atoms (eg, phenoxycarbonyl, 4-methylphenoxycarbonyl, 4- Methoxyphenoxycarbonyl, etc.), a substituted or unsubstituted alkoxy group having 1 to 4 carbon atoms (eg, methoxy, ethoxy, n-butoxy, methoxyethoxy, etc.), a substituted or unsubstituted aryloxy group having 6 to 10 carbon atoms ( For example, phenoxy, 4-methoxyphenoxy, etc.), a substituted or unsubstituted acyloxy group having 2 to 8 carbon atoms (eg, acetoxy, ethylcarbonyloxy, cyclohexylcarbonyloxy, benzoyloxy, chloroacetyloxy, etc.), 1 carbon atom A substituted or unsubstituted sulfonyloxy group (eg, methanesulfonyloxy, etc.), a carbamoyloxy group having 2 to 8 carbon atoms (eg, methylcarbamoyloxy, diethylcarbamoyloxy, etc.), a substituted or unsubstituted group having 0 to 8 carbon atoms An amino group (for example, unsubstituted amino, methylamino, dimethylamino, diethylamino, phenylamino, methoxyphenylamino, chlorophenylamino, morpholino, piperidino, pyrrolidino, pyridylamino, methoxycarbonylamino, n-butoxycarbonylamino, phenoxycarbonylamino) , Methylcarbamoylamino, phenylcarbamoylamino, acetylamino, ethylcarbonylamino, cyclohexylcarbonylamino, benzoylamino, chloroacetylamino, Sulfonylamino, etc.), a substituted or unsubstituted carbamoyl group having 1 to 8 carbon atoms (eg, unsubstituted carbamoyl, methylcarbamoyl, ethylcarbamoyl, n-butylcarbamoyl, t-butylcarbamoyl, dimethylcarbamoyl, morpholinocarbamoyl, pyrrolidino). Carbamoyl, etc.), a substituted or unsubstituted sulfonamide group having 1 to 8 carbon atoms (eg, methanesulfonamide, p-toluenesulfonamide, etc.), a halogen atom (eg, fluorine, chlorine, bromine), a hydroxyl group, a nitro group, Examples thereof include a cyano group and a carboxyl group.

R ¹ is preferably a hydrogen atom or a substituent selected from an alkyl group, an aryl group, an alkoxycarbonyl group, and an aryloxycarbonyl group. Particularly preferred is a hydrogen atom.

It is preferable that m is 0, 1 or 2.
When m = 1 or 2, R ² is an alkyl group, an aryl group,
It is preferably a substituent selected from an amino group, an alkoxy group, an acyloxy group, a carbamoyl group, a halogen atom, a nitro group and a carboxyl group. Particularly preferably m
= 0.

R ³ is preferably a hydrogen atom or a substituent selected from an alkyl group and an aryl group. Particularly preferred is an alkyl group.

In a preferred combination, the acidic nucleus of A is 5-pyrazolone, hydroxypyridone, pyrazolopyridone, barbituric acid, isoxazolone, and n =
0, m = 0, R ¹ is a hydrogen atom, R ³
Is a hydrogen atom or an alkyl group, and X is a combination of an alkoxycarbonyl group or a cyano group. Particularly preferred is when the acidic nucleus of A is 5-pyrazolone and n = 0.
And m = 0, R ¹ is a hydrogen atom, R ³ is an alkyl group, and X is a combination of alkoxycarbonyl groups.

A'in the general formula (II) represents a residue of the acidic nucleus represented by A. The substitution position of the carboxyl group with respect to the phenyl group may be any position. k represents 1, 2, and 3. It is preferably 1 or 2, and particularly preferably 1.

A preferred combination from the viewpoint of the general formula (II) is that A'is a 5-pyrazolone residue, a hydroxypyridone residue, a pyrazolopyridone residue, a barbituric acid residue or an isoxazolone residue, and k = 1 or 2
R ¹ is a hydrogen atom, a methyl group or a phenyl group, R ³ is a hydrogen atom or an alkyl group, and X is a combination of an alkoxycarbonyl group or a cyano group. Further, a combination of n = 0 and a combination of m = 0 are preferable. Particularly preferred is A ′ is a 5-pyrazolone residue, n = 0, m = 0, k = 1, R ¹ is a hydrogen atom, R ³ is an alkyl group, X is a combination of alkoxycarbonyl groups.

The substituents represented by R ⁴ and R ⁵ in the general formula (III) have the same meanings as the substituents represented by R ¹ , R ² and R ³ . However, at least 1 for R ⁴ or R ⁵
It has one carboxyl group. The substituent represented by R ⁴ is preferably an unsubstituted alkyl group or a substituted or unsubstituted amino group, more preferably an unsubstituted alkyl group or an unsubstituted amino group. More preferably, it is a methyl group or an unsubstituted amino group. The substituent represented by R ⁵ is preferably an aryl group substituted with a carboxyl group. Particularly preferred is a carboxyphenyl group.

A preferable combination from the viewpoint of the general formula (III) is m = 0, R ¹ is a hydrogen atom, and R is
³ is a hydrogen atom or an alkyl group, R ⁴ is an unsubstituted alkyl group, a substituted or unsubstituted amino group, R ⁵ is an aryl group substituted with a carboxyl group, X is an alkoxycarbonyl group or cyano It is a combination of groups.
Particularly preferred is m = 0, R ¹ is a hydrogen atom, R ³ is an alkyl group, R ⁴ is a methyl group or an unsubstituted amino group, and R ⁵ is a carboxyphenyl group. X is a combination of alkoxycarbonyl groups.

The compounds of the present invention are sparingly soluble in water having a pH of 5-7. The term “poorly water-soluble” as used herein refers to a compound having a solubility of 1.0 g / liter (25 ° C.) or less in water having a pH of 5 to 7. In order for the compound of the present invention to be sparingly soluble in water, it must not have a sulfo group or a salt thereof (eg, sodium salt, potassium salt, ammonium salt, etc.) as a substituent.

Specific examples of the compound used in the present invention are shown below, but the present invention is not limited thereto.

[0039]

[Chemical 5]

[0040]

[Chemical 6]

[0041]

[Chemical 7]

[0042]

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[0043]

[Chemical 9]

[0044]

[Chemical 10]

[0045]

[Chemical 11]

[0046]

[Chemical 12]

[0047]

[Chemical 13]

[0048]

Embedded image

The compound of the general formula (I) used in the present invention is a compound in which the active methylene part of the acidic nucleus A (the part bonded to L ¹ in the general formula (I)) is unsubstituted and the general formula (IV ) In an organic solvent (for example, methanol, ethanol, isopropyl alcohol, acetonitrile, N, N-dimethylformamide, N, N-dimethylacetamide, acetic acid, pyridine) at room temperature to reflux. Can be obtained.
When the reaction proceeds slowly, it can be easily synthesized by adding an appropriate amount of acetic acid, acetic anhydride, p-toluenesulfonic acid, triethylamine, pyridine, ammonium acetate or the like.

[0050]

[Chemical 15]

A synthesis example is shown below.

(A) Synthesis of methyl 2- (3-formyl-1-indolyl) propionate (Compound a) 4.4 g of indole-3-carbaldehyde, 5.5 g of methyl 2-bromopropionate, potassium carbonate 8. 3g,
30 ml of N, N-dimethylformamide was mixed and heated and stirred on a steam bath for 3 hours. The reaction solution was allowed to cool to room temperature and then poured into 120 ml of ice water while stirring, and an oily substance precipitated and solidified in due course. This was recrystallized from ethanol to obtain 6.2 g of compound a crystals.

(B) Synthesis of Compound 1 5.5 g of 1-p-carboxyphenyl-3-methyl-5-pyrazolone and 5.8 g of compound a were mixed with 50 ml of N, N-dimethylacetamide and the mixture was placed on a steam bath for 4 hours. Heated. After cooling to room temperature and adding 50 ml of methanol, crystals were collected by filtration. After washing with a small amount of methanol and drying, 7.4 g of compound 1 was obtained. λmax = 406nm (dimethylformamide)

(C) Synthesis of Compound 5 6.6 g of 3-amino-1-p-carboxyphenyl-5-pyrazolone and 6.9 g of compound a were mixed with 30 ml of N, N-dimethylformamide, and the mixture was placed on a steam bath for 4 hours. Heated. After cooling to room temperature, 30 ml of methanol was added and the mixture was stirred at the same temperature for a while and the crystals were collected by filtration. After washing with methanol,
When dried, 7.6 g of compound 5 was obtained. λmax = 41
4nm (dimethylformamide)

In the present invention, the dispersion of the dye is described in JP-A-52.
Dispersing machines such as ball mills, sand mills, colloid mills, vibration ball mills, planetary ball mills, jet mills, roll mills, Manton Gaulins, microfluidizers, disc impeller mills and the like, as described in No. 92716 and WO88 / 04794. Etc. can be arbitrarily selected, but a vertical or horizontal medium disperser is preferable. In any case, it is preferable to use a solvent (for example, water), and it is more preferable to use a dispersing surfactant. As a surfactant for dispersion, Japanese Patent Application Laid-Open No. Sho 5
It is also possible to use an anionic surfactant as described in 2-92716, WO 88/04794, etc., or an anionic polymer as in Japanese Patent Application No. 3-121749, and if necessary, nonionic. Although cationic or cationic surfactants can be used, anionic polymers or anionic surfactants are preferred.

Alternatively, the dye of the present invention may be dissolved in a suitable solvent and then a poor solvent for the dye of the present invention may be added to precipitate fine crystals. Agents may be used. Alternatively, the pH may be controlled in a solvent to be dissolved first, and then the pH may be changed to perform microcrystallization. The dye of the present invention in the dispersion has an average particle size of 0.005 μm to 10 μm, preferably 0.01 μm to 1 μm, more preferably 0.01 μm.
m to 0.5 μm, and in some cases 0.01 μm
To 0.1 μm is preferable. Further, the fine particles of the dye are preferably monodispersed.

At the time of dispersing the dye of the general formula (I), the dye solid may be directly dispersed without any pretreatment.
At this time, it is preferable to use a wet dye solid obtained in the process of synthesizing the dye for dispersion. Further, if necessary, the heat treatment may be performed before and / or after the dispersion, and in order to perform the heat treatment more effectively, it is preferable to perform the heat treatment at least after the dispersion. The heating method is not particularly limited as long as heat is applied to the dye solid, and the temperature is preferably 40 ° C. or higher, and the upper limit is any number as long as the dye is not decomposed, and preferably 250 ° C. or lower. More preferably, it is 50 ° C to 150 ° C. The heating time is not particularly limited as long as the dye does not decompose, 15 minutes to
One week, preferably 1 hour to 4 days. In order to effectively carry out the heat treatment, it is preferable to carry out in a solvent, and the kind of the solvent is not limited as long as it does not substantially dissolve the dye of the general formula (I), and examples thereof include water and alcohols. (For example, methanol, ethanol, isopropyl alcohol, butanol, isoamyl alcohol, octanol, ethylene glycol, diethylene glycol,
Ethyl cellosolve), ketones (eg acetone, methyl ethyl ketone), esters (eg ethyl acetate, butyl acetate), alkylcarboxylic acids (eg acetic acid, propionic acid), nitriles (eg acetonitrile), ethers (eg , Dimethoxyethane, dioxane, tetrahydrofuran) and the like.

The coexistence of organic carboxylic acids during the heat treatment can more effectively solve the problems of the present invention. Examples of the organic carboxylic acid include alkyl carboxylic acids (for example, acetic acid and propionic acid), carboxymethyl celluloses (CMC), aryl carboxylic acids (for example, benzoic acid and salicylic acid).
When used as a solvent, the amount of the organic carboxylic acids is 0.5 based on the weight of the dyes of the general formulas (I), (II) and (III).
~ 100 times the amount can be used. When the organic carboxylic acid is added by using a solvent other than the organic carboxylic acids, it is used in a weight ratio of 0.05 to 100% with respect to the dyes of the general formulas (I), (II) and (III). be able to.

The present invention can be applied to various black and white and color light-sensitive materials. Further, in the present invention, the number of emulsion layers and other hydrophilic colloid layers constituting the light-sensitive material and the types of additives are generally large as compared with black and white, and therefore the thickness of the light-sensitive material is increased, and an oil-soluble additive is added. It is effective for a color light-sensitive material in which the decolorizing property of the dye tends to decrease because it is contained in a large amount.

The dye represented by the general formula (I) can be used in any effective amount, but it is preferable to use it so that the optical density is in the range of 0.05 to 3.0. The amount per single layer 0.5mg / m ² ~1000mg / m ²
, And more preferably from ^{1mg / m 2 ~500mg / m 2} . The addition time may be any step before coating. The dyes represented by the general formulas (I), (II) and (III) can be used in any of the emulsion layer and other hydrophilic colloid layers (intermediate layer, protective layer, antihalation layer, filter layer, back layer, etc.). Can also be used and may be used in a single layer or in a plurality of layers. Addition to the non-photosensitive layer is preferred.

The light-sensitive material prepared by using the present invention may contain a dye other than the present invention as a filter dye or in a hydrophilic colloid layer for various purposes such as prevention of irradiation or halation. As such dyes, oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, anthraquinone dyes, azo dyes are preferably used, and in addition, cyanine dyes, azomethine dyes, triarylmethane dyes, and phthalocyanine dyes are also useful. . These dyes can be added by dissolving in water when they are water-soluble, and can be added as solid fine particle dispersions when they are hardly soluble in water. The oil-soluble dye may be emulsified by an oil-in-water dispersion method and added to the hydrophilic colloid layer.

It has heretofore been known to use solid dispersed dyes in photosensitive materials.

For example, a method of dyeing a specific layer using water-insoluble dye solid fine particles is disclosed in JP-A-56-12639.
No. 63-197943, European Patent No. 15601.
Nos. 274723, 299435, and U.S. Pat. No. 4,950,586.

Particularly, a method of using a solid fine particle dispersion of a dye in which an acid nucleus and a 5-membered heterocycle are bound by a methine chain is disclosed in JP-A-55-155351, JP-A-3-144438 and JP-B-48-17575. European Patent No. 524594A
No. 4,923,788 and the like.
Further, the use of a compound comprising a pyrazolone nucleus and an indole nucleus (or a pyrrole nucleus) as a photographic dye is described in JP-A-5-86056 and JP-A-3-167546.

The present inventors have found that compounds of general formula (I)
As a result, the inventors have found that the spectral characteristics of the dye and the decolorizing property during development can be improved specifically by selecting the above-mentioned electron-withdrawing substituent, and the present invention has been completed.

The light-sensitive material of the present invention contains at least one light-sensitive emulsion layer or an intermediate layer adjacent thereto containing two or more kinds of couplers capable of forming different hues by reaction with an oxidized product of a developing agent. The different hues mean that the maximum values of the spectral absorption of the dye are separated by 50 nm or more.

One of the embodiments of the present invention is a light-sensitive material in which a blue light-sensitive emulsion layer contains a yellow coupler as a main coupler and a cyan coupler as an auxiliary coupler. The ratio of the cyan coupler to all the couplers in the blue-sensitive emulsion layer is preferably 0.2 mol% or more and 10 mol% or less, more preferably 0.5 mol% or more and 5 mol% or less. If it is less than 0.3 mol%, the effect of the present invention is not exhibited, and if it exceeds 10 mol%, color turbidity increases.

When the blue-sensitive emulsion layer is composed of a plurality of sublayers having different sensitivities, it is desirable that the cyan coupler as the auxiliary coupler is mixed more in the high sensitivity sublayer than in the low sensitivity sublayer. The ratio of the cyan coupler in the blue-sensitive emulsion layer having the highest sensitivity is 0.5 mol% or more and 10 mol% or more.
The amount is preferably the following or less, and more preferably 1 mol% or more and 5 mol% or less. The ratio of the cyan coupler in the blue light-sensitive emulsion sublayer having the lowest sensitivity is preferably 0 mol% or more and 3 mol% or less.

The cyan coupler mixed in the blue light-sensitive emulsion layer of the light-sensitive material of the present invention has a relative coupling speed of 0.3 or more and 2.0 or less with respect to the yellow coupler which is the main coupler of the blue light-sensitive emulsion layer. Have. More preferably, 0.
It has a relative coupling speed of 5 or more and 1.5 or less.

When the blue-sensitive emulsion layer is composed of a plurality of sub-layers having different sensitivities and the type of the main coupler is different depending on each sub-layer, the above-mentioned relative to the coupling speed of the yellow coupler contained in the layer in which the cyan coupler is mixed. Cyan couplers having relative coupling rates of are mixed. When the main coupler, the yellow coupler, is composed of two or more compounds in the same layer, the coupling rate of the yellow coupler is the weighted average of the coupling rates of the respective couplers.

In the above embodiments, the auxiliary coupler, the cyan coupler, may be added to the non-photosensitive intermediate layer adjacent to the blue-sensitive emulsion layer. When the blue-sensitive emulsion layer is composed of two or more sub-layers having different sensitivities, the cyan coupler as the auxiliary coupler is preferably added to the intermediate layer adjacent to the blue-sensitive sub-layer with the highest sensitivity. The amount of the cyan coupler added to the intermediate layer is preferably 1 mol% or more and 40 mol% or less, more preferably 2 mol% or more and 20 mol% or less, based on all the couplers in the blue-sensitive emulsion layer. .

Another embodiment of the present invention is a light-sensitive material containing a cyan coupler as a main coupler and a yellow coupler as an auxiliary coupler in a red light-sensitive emulsion layer. The ratio of the yellow coupler to all the couplers in the red light-sensitive emulsion layer is preferably 0.3 mol% or more and 20 mol% or less, and more preferably 1 mol% or more and 10 mol% or less. If it is less than 0.3 mol%, the effect of the present invention is not exhibited, and if it exceeds 20 mol%, color turbidity increases.

When the red light-sensitive emulsion layer is composed of a plurality of sublayers having different sensitivities, it is desirable that the auxiliary coupler, yellow coupler, is mixed more in the high-sensitivity sublayer than in the low-sensitivity sublayer. The ratio of the yellow coupler in the red-sensitive emulsion layer having the highest sensitivity is 2 mol% or more and 30 mol% or more.
It is desirable that the content be 5 mol% or more and 20 mol% or less. The ratio of the yellow coupler in the red-sensitive emulsion layer having the lowest sensitivity is preferably 0 mol% or more and 10 mol% or less, and 0 mol% or more 5
More preferably, it is at most mol%. It has been found that the color temperature dependence can be sufficiently improved by minimizing the color turbidity by mixing more yellow coupler in the high sensitivity sublayer than in the low sensitivity sublayer.

The yellow coupler mixed in the red light-sensitive emulsion layer of the light-sensitive material of the present invention has a relative coupling speed of 0.7 or more and 3.0 or less with respect to the cyan coupler which is the main coupler of the red light-sensitive emulsion layer. Have. More preferably, 0.
It has a relative coupling speed of 8 or more and 2.5 or less.

When the red light-sensitive emulsion layer is composed of a plurality of sub-layers having different sensitivities and the type of the main coupler is different depending on each sub-layer, the above-mentioned is described with respect to the coupling speed of the cyan coupler contained in the layer in which the yellow coupler is mixed. The yellow coupler having a relative coupling rate of is mixed. When the cyan coupler, which is the main coupler, is composed of two or more compounds in the same layer, the coupling rate of the cyan coupler is the weighted average of the coupling rates of the respective couplers.

The relative coupling rate of the coupler can be measured by adding the coupler of interest to the emulsion, developing it with a color developing solution containing citrazinic acid, and measuring the density. That is, the relative coupling speed RY / RC of the yellow coupler and the cyan coupler is represented by the following formula. RY / RC = log (1-DY / DYmax) / log (1
-DC / DCmax) Here, DYmax represents the maximum density of color development of the yellow coupler, DY represents the color density in the middle stage, and DCma
x represents the maximum density of the color developed by the cyan coupler, and DC represents the color density in the intermediate stage.

That is, several DY and DC values obtained by subjecting an emulsion containing mixed couplers to various stages of exposure and color development are represented by log (1-D / Dmax) on two axes orthogonal to each other. The relative coupling speed RY / RC is determined from the slope of the straight line obtained by plotting

Among the yellow couplers and the cyan couplers, the phenol type coupler having a ureido group at the 2-position changes the reactivity and the hue depending on the type and amount of the oil used. It is not preferable to evaluate the reactivity in the presence of a coupler. Therefore, the reactivity of phenolic couplers having a ureido group at the 2-position among yellow couplers and cyan couplers is evaluated as follows.

A sample prepared by adding the objective coupler alone to the emulsion is exposed to color development, and the maximum density of the color image at this time is defined as (Do) max. On the other hand, the maximum density of the color-developed color image when treated with the developer containing 1.5 g of citrazinic acid per liter in the color developer is (D
c) max.

At this time, the coupling coloring property R of the coupler
c / Ro can be relatively evaluated by (Dc) max / (Do) max.

Next, the difference between the present invention and the known case of using different couplers in the same emulsion layer will be described.

In the first invention, the red photosensitive emulsion layer is composed of three or more sublayers having different sensitivities. Each red light-sensitive emulsion sublayer preferably contains a yellow coupler in the following ratio.

X (RH) ≧ X (RM) ≧ X (RL) where X (RH) is the content (mol%) of the yellow coupler with respect to all the couplers contained in the red-sensitive emulsion sublayer having the highest sensitivity. , X (RM) is the content (mol%) of the yellow coupler with respect to all couplers contained in the red-sensitive emulsion sublayer having the medium sensitivity, and X (RL) is the red-sensitive emulsion sublayer having the lowest sensitivity. Represents the content (mol%) of the yellow coupler with respect to all the couplers contained in.

X (RH), X (RM) and X (RL)
The preferred range of is as follows.

2% ≦ X (RH) ≦ 30% 0% ≦ X (RM) ≦ 20% 0% ≦ X (RL) ≦ 10% X (RH), X (RM) and X (RL) are more preferable. The range is as follows.

5% ≦ X (RH) ≦ 20% 2% ≦ X (RM) ≦ 15% 0% ≦ X (RL) ≦ 5%

In the fifth invention, in the light-sensitive material of the present invention, each of the blue, green and red color sensitive layers has different sensitivities.
The average grain size of the emulsion of the most sensitive emulsion layer of the blue-sensitive emulsion layer is more than twice the average grain size of the emulsion of the most sensitive emulsion layer of the green-sensitive emulsion layer. large.

The grain size of the emulsion is determined by a method using an ordinary electron microscope. The average particle size is the number average particle size. When two or more emulsions are mixed in the most sensitive layer, the number average grain size of the mixed emulsion grain sizes is used.

The average grain size of the emulsion in the emulsion layer having the highest sensitivity among the blue light-sensitive emulsion layers is 2.2 times or more the average grain size of the emulsion in the emulsion layer having the highest sensitivity in the green light-sensitive emulsion layers. It is preferably large and 5 times or less.

In the fifth invention, the average grain size of the emulsion in the emulsion layer having the highest sensitivity among the blue-sensitive emulsion layers is 2 times the average grain size of the emulsion layer having the highest sensitivity in the green-sensitive emulsion layers. It is 5 times, more preferably 2 to 4 times.

The average particle size means the number average particle size measured by a usual electron microscope method. By making the above-mentioned particle size ratio twice or more, the amount of the yellow dye used can be reduced without causing spectral color mixing, and the stability during development processing is improved.

When the ratio of the above-mentioned particle sizes is 5 times or more, the graininess of the yellow image is deteriorated, which is not desirable.

Regarding the various techniques and inorganic / organic materials which can be used for the silver halide photographic emulsion of the present invention and the silver halide photographic light-sensitive material using the same, Research Disclosure No. 308119 (19) is generally used.
1989) can be used.

In addition to this, more specifically, for example,
Techniques and inorganic / organic materials that can be used for color photographic light-sensitive materials to which the silver halide photographic emulsion of the present invention can be applied are described in the following parts of EP 436,938A2 and the patents cited below. There is.

Item This section 1) Layer structure Page 146, line 34 to page 147, line 25 2) Silver halide emulsion Page 147, line 26 to page 148, line 12 3) Yellow coupler No. Page 137, line 35 to page 146, line 33, page 149, line 21 to line 23 4) Magenta coupler, page 149, line 24 to line 28; EP 421,453A1 Page 3, line 5 to page 25, line 55 5) Cyan coupler page 149, line 29 to line 33; European patent 432,804A2, page 3, line 28 to page 40, line 2 6 ) Polymer coupler, page 149, lines 34 to 38; European Patent 435,334A2, page 113, line 39 to page 123, line 37 7) Colored coupler, page 53, line 42 to page 137, 34. Line, page 149, lines 39-45 8) Other functionalities page 7 line 1 to page 53 line 41, page 149 page 46 puller line to page 150 line 3; European patent 435,334 page 2 page 3 Lines to page 29, line 50 9) Preservatives and fungicides page 150, lines 25 to 28 10) Formalin page 149, lines 15 to 17 Scavenger 11) Other additives page 153, line 38 Lines 47 to 47; page 75, line 21 to page 84, line 56, page 27, line 40 to page 37, line 40 of EP No. 421,453A1 12) Dispersion method page 150, line 4 Lines to 24th line 13) Support page 150 line 32nd line to 34th line 14) Film thickness / film physical properties page 150 line 35th line to 49th line 15) Color development / black and white development page 150 line 50th line Page 151, Line 47; European Special / Fogging Process, Page No. 442, 323A2, Page 34, Line 11- Line 5, page 35, lines 14 to 22 16) Desilvering process page 151, line 48 to page 152, line 53 17) Automatic processor Page 152, line 54 to page 153, line 2 18) Washing / stabilization process Page 153, lines 3 to 37

[0096]

EXAMPLES The present invention will now be specifically described with reference to examples, but the invention is not limited thereto. Example 1 Preparation of Comparative Sample 101 A sample 101 was prepared by forming a multilayer color light-sensitive material having the following compositions on a cellulose triacetate film support having a thickness of 127 μ and having an undercoat. The numbers represent the amount added per m ² . The effect of the added compound is not limited to the described use. 1st layer: Antihalation layer Black colloidal silver 0.20 g amount of gelatin 1.9 g UV absorber U-1 0.1 g UV absorber U-3 0.04 g UV absorber U-4 0.1 g high Boiling point organic solvent Oil-1 0.1 g Microcrystalline solid dispersion of dye E-1 0.1 g Second layer: intermediate layer Gelatin 0.04 g Compound Cpd-C 5 mg Compound Cpd-J 5 mg Compound Cpd-K 3 mg High Boiling point organic solvent Oil-3 0.1 g Dye D-4 0.8 mg Third layer: intermediate layer Yellow colloidal silver Silver amount 0.01 g Gelatin 0.4 g Fourth layer: low-sensitivity red-sensitive emulsion layer Emulsion A Silver Amount 0.3 g Emulsion B Silver amount 0.2 g Gelatin 0.8 g Coupler C-1 (cyan coupler) 0.04 g Coupler C-2 (cyan coupler) 0.10 g Compound Cpd-C 5 mg High boiling point organic solvent O il-2 0.1 g Additive P-1 0.1 g Fifth layer: Medium speed red-sensitive emulsion layer Emulsion C Silver amount 0.5 g Gelatin 0.8 g Coupler C-1 (cyan coupler) 0.06 g Coupler C-2 (cyan coupler) 0.13 g High boiling point organic solvent Oil-2 0.1 g Additive P-1 0.1 g Sixth layer: high-sensitivity red-sensitive emulsion layer Emulsion D Silver amount 0.4 g Gelatin 1.1 g Coupler C-3 (cyan coupler) 0.65 g Additive P-1 0.1 g Seventh layer: intermediate layer Gelatin 0.6 g Additive M-1 0.3 g Color mixing inhibitor Cpd-I 2.6 mg Dye D-5 0.02 g High boiling point organic solvent Oil-1 0.02 g Eighth layer: Intermediate layer Yellow colloidal silver Silver amount 0.02 g Gelatin 1.0 g Additive P-1 0.2 g Mixed color Inhibitor Cpd-A 0.1 g Compound Cpd-C 0.1 g 9th Layer: low-sensitivity green-sensitive emulsion layer Emulsion E Silver amount 0.1 g Emulsion F Silver amount 0.2 g Emulsion G Silver amount 0.2 g Gelatin 0.5 g Coupler C-4 (magenta coupler) 0.1 g Coupler C-7 (magenta coupler) 0.05 g Coupler C-8 (magenta coupler) 0.20 g Compound Cpd-B 0.03 g Compound Cpd-D 0.02 g Compound Cpd-E 0.02 g Compound Cpd-F 0.04 g Compound Cpd-L 0.02 g High-boiling point organic solvent Oil-1 0.1 g High-boiling point organic solvent Oil-2 0.1 g 10th layer: Medium sensitivity green sensitive emulsion layer Emulsion H Silver amount 0.4 g Gelatin 0.6 g Coupler C-4 (magenta coupler) 0.1 g Coupler C-7 (magenta coupler) 0.2 g Coupler C-8 (magenta coupler) 0.1 g Compound Cpd-B 0.03 Compound Cpd-D 0.02g Compound Cpd-E 0.02g Compound Cpd-F 0.05g Compound Cpd-L 0.05g High boiling organic solvent Oil-2 0.01g Layer 11: High sensitivity green sensitive emulsion layer Emulsion I Silver amount 0.5 g Gelatin 1.0 g Coupler C-4 (magenta coupler) 0.3 g Coupler C-7 (magenta coupler) 0.1 g Coupler C-8 (magenta coupler) 0.1 g Compound Cpd- B 0.08 g Compound Cpd-E 0.02 g Compound Cpd-F 0.04 g Compound Cpd-K 5 mg Compound Cpd-L 0.02 g High boiling point organic solvent Oil-1 0.02 g High boiling point organic solvent Oil-2 0.02 g Twelfth layer: intermediate layer Gelatin 0.6 g Compound Cpd-L 0.05 g High boiling point organic solvent Oil-1 0.05 g Thirteenth layer: Yellow Filter layer Yellow colloidal silver Silver amount 0.07 g Gelatin 1.1 g Anti-color mixing agent Cpd-A 0.01 g Compound Cpd-L 0.01 g High boiling point organic solvent Oil-1 0.01 g Fine crystal solid dispersion of dye E-2 Material 0.05 g 14th layer: low-sensitivity blue-sensitive emulsion layer Emulsion J Silver amount 0.5 g Gelatin 0.8 g Coupler C-5 (yellow coupler) 0.3 g Coupler C-6 (yellow coupler) 0.1 g Coupler C-10 (yellow coupler) 0.1 g Fifteenth layer: medium-speed blue-sensitive emulsion layer Emulsion L Silver amount 0.5 g Gelatin 0.9 g Coupler C-5 (yellow coupler) 0.3 g Coupler C -6 (Yellow coupler) 0.1 g Coupler C-10 (Yellow coupler) 0.1 g 16th layer: High-sensitivity blue-sensitive emulsion layer Emulsion M Silver amount 0.2 g Emulsion N Silver amount 0.2 g Ze Ratin 1.2 g Coupler C-5 (yellow coupler) 0.1 g Coupler C-6 (yellow coupler) 0.1 g Coupler C-10 (yellow coupler) 1.1 g High boiling organic solvent Oil-2 0. 1 g 17th layer: 1st protective layer Gelatin 0.7 g UV absorber U-1 0.2 g UV absorber U-2 0.05 g UV absorber U-5 0.3 g Formalin scavenger Cpd-H 0 0.4 g Dye D-1 0.002 g Dye D-2 0.0005 g Dye D-3 0.001 g Eighteenth layer: Second protective layer Colloidal silver Silver amount 0.1 mg Fine grain silver iodobromide emulsion (average grain size 0.06 μm, AgI content 1 mol%) Silver amount 0.1 mg Gelatin 0.4 g 19th layer: Third protective layer Gelatin 0.4 g Polymethylmethacrylate (average particle size 1.5 μ) 0.1 g Methyl 4: 6 copolymer of methacrylate and acrylic acid (average particle size 1.5 μ) 0.1 g Silicone oil 0.03 g Surfactant W-1 3.0 mg Surfactant W-2 0.03 g In addition to the above composition, all the emulsion layers contain additive F-
1-F-8 were added. In addition to the above composition, gelatin hardener H-1 and coating and emulsifying surfactants W-3, W-4, W-5 and W-6 were added to each layer.

Further, as an antiseptic and antifungal agent, phenol, 1,
2-Benzisothiazolin-3-one, 2-phenoxyethanol, phenethyl alcohol, p-benzoic acid butyl ester were added.

The silver iodobromide emulsions A to N used in Sample 101 are shown in Table 1 below, and their spectral sensitization is shown in Table 2 below.
~ Shown in Table 3.

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[Table 1]

[0100]

[Table 2]

[0101]

[Table 3]

The various compounds used are shown in Chemical Formulas 42 to 55 below.

[0103]

Embedded image

[0104]

[Chemical 17]

[0105]

[Chemical 18]

[0106]

[Chemical 19]

[0107]

Embedded image

[0108]

[Chemical 21]

[0109]

[Chemical formula 22]

[0110]

[Chemical formula 23]

[0111]

[Chemical formula 24]

[0112]

[Chemical 25]

[0113]

[Chemical formula 26]

[0114]

[Chemical 27]

[0115]

[Chemical 28]

[0116]

[Chemical 29]

Example 2 By using the YF dye of the present invention and mixing a cyan coupler in the blue-sensitive emulsion layer or its adjacent layer,
The following examples show that various yellow objects can be discriminated well and can be reproduced faithfully and with good saturation.

Samples 102-104 were prepared by reducing the yellow colloidal silver in the 13th layer of Sample 101 to 0.015 g / m ² and adding the YF solid disperse dye instead. The type and amount of YF dye in each sample are shown in Table 4. Furthermore, sample 1
Cyan coupler C- in the 16th layer of each sample of 01 to 104
2 to 0.03 g / m ^2, and C-1 with the addition of 0.01 g / m ^2, were each prepared sample 105-108. Further, the amounts of the cyan couplers of the sample 108 were changed as shown in Table 4 to prepare samples 109 and 110. Further, the cyan coupler C- is provided on the 17th layer of the sample 104.
2 and the 0.12 g / m ^2, and C-1 0.04g / m ² was added to prepare a sample 111.

[0119]

[Table 4]

Samples 101 to 111 were heated at a temperature of 30 ° C.
After storing at a humidity of 60% for 14 days, it was cut into a sheet size and photographed with a commercially available 4 × 5 size camera using a strobe as a light source. The subject is a mixture of various yellow objects aimed at improvement by the present invention. The spectral reflectances of typical subjects A to C among them are first
Shown in the figure.

The following development processing was carried out on the day after photographing.

Treatment process time Temperature Tank capacity Replenishment amount First development 6 minutes 38 ° C. 12 liters 2200 ml / m ² First water washing 2 minutes 38 ° C. 4 liters 7500 ml / m ² Inversion 2 minutes 38 ° C. 4 liters 1100 ml / m ² color development 6 minutes 38 ° C 12 liters 2200 ml / m ² pre-bleaching 2 minutes 38 ° C 4 liters 1100 ml / m ² bleaching 6 minutes 38 ° C 12 liters 220 ml / m ² fixing 4 minutes 38 ° C 8 liters 1100 Milliliter / m ² Second water washing 4 minutes 38 ° C. 8 liters 7500 ml / m ² Final rinse 1 minute 25 ° C. 2 liters 1100 ml / m ² The composition of each treatment solution was as follows. [First developer] [Tank solution] Replenisher] Nitrilo-N, N, N-trimethylenephosphonic acid-5 sodium salt 1.5 g 1.5 g Diethylenetriaminepentaacetic acid / 5 sodium salt 2.0 g 2.0 g Sodium sulfite 30 g 30 g Hydroquinone potassium monosulfonate 20 g 20 g Potassium carbonate 15 g 15 g Sodium bicarbonate 12 g 15 g 1-Phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone 1.5 g 2.0 g Odor Potassium iodide 2.5 g 1.4 g Potassium thiocyanate 1.2 g 1.2 Potassium iodide 2.0 mg-Diethylene glycol 13 g 15 g Water was added to 1000 ml 1000 ml pH 9.60 9.60 pH was adjusted with sulfuric acid or potassium hydroxide. did. [Reversal liquid] [Tank liquid] [Replenishing liquid] Nitrilo-N, N, N-trimethylenephosphonic acid-5 sodium salt 3.0 g Same as tank liquid Stannous chloride dihydrate 1.0 g p-aminophenol 0.1 g sodium hydroxide 8 g glacial acetic acid 15 ml Water was added to 1000 ml pH 6.00 pH was adjusted with acetic acid or sodium hydroxide. [Color developer] [Tank solution] [Replenisher] Nitrilo-N, N, N-trimethylenephosphonic acid-5 sodium salt 2.0 g 2.0 g Sodium sulfite 7.0 g 7.0 g Trisodium phosphate-12 water Salt 36 g 36 g Potassium bromide 1.0 g-Potassium iodide 90 mg-Sodium hydroxide 3.0 g 3.0 g Citrazine acid 1.5 g 1.5 g N-ethyl-N- (β-methanesulfonamidoethyl)- 3-Methyl-4-aminoaniline / 3/2 sulfuric acid monohydrate 11 g 11 g 3,6-dithiaoctane-1,8-diol 1.0 g 1.0 g sodium bisulfite 5.0 g Water added 1000 ml pH 6.60 pH was adjusted with acetic acid or aqueous ammonia. [Stabilizing liquid] [Tank liquid] [Replenishing liquid] Benzisothiazolin-3-one 0.02 g 0.03 g Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.3 g 0.3 g Polymaleic acid (average Molecular weight 2,000) 0.1 g 0.15 g Water was added to 1000 ml 1000 ml pH 7.0 7.0 pH was adjusted with sulfuric acid or potassium hydroxide.

The color reproduction of each treated sample was evaluated by visual perception. In particular, the evaluation was performed with emphasis on how faithfully various yellow objects can be reproduced, whether the colors can be sufficiently discriminated, and whether the color paste is sufficient. Five people who were in charge of evaluation were working at Ashigara Research Laboratories of Fuji Photo Film Co., Ltd., and had the task of evaluating photographs. The evaluation rank was 5 according to the following criteria for color reproduction and color temperature dependence. It was a graded evaluation.

Score Evaluation 5 Very Excellent 4 Excellent 3 Normal 2 Inferior 1 Very Inferior The evaluation results of color reproduction of each sample are shown in Table 4 by averaging the scores of 5 persons. .

As is clear from Table 4, Y of the present invention
The sample of the present invention containing the F dye and having the cyan coupler mixed in the blue-sensitive emulsion layer or in the layer adjacent to the blue-sensitive emulsion layer was able to discriminate various yellow objects well and faithfully reproduce the color saturation.

Example 3 By using the YF dye of the present invention and mixing a yellow coupler in the red light-sensitive emulsion layer, various blue objects can be well discriminated and can be faithfully reproduced with good saturation. This will be shown in Examples.

In each of Samples 101 to 104, the yellow coupler C-6 was 0.007 / m ^{2 in} the fourth layer, the yellow coupler C-6 was 0.01 g / m ^{2 in} the fifth layer, and the yellow was the sixth layer. Couplers C-6 were added at 0.017 g / m ² to prepare Samples 121 to 124, respectively. Sample 10
0.016 g of yellow coupler C-6 in the 6th layer of 4
Sample 125 was prepared by adding m ² . The amount of each of the fourth, fifth and sixth layers of sample coupler 124 was set to 1 each.
Sample 126 was prepared by reducing it to / 3. The amount of Ye coupler in the fourth, fifth and sixth layers of sample 124 was set to 3 respectively.
Sample 127 was prepared by doubling the number. Samples 121 to 12
The contents of 7 are summarized in Table 5.

[0128]

[Table 5]

Samples 101 to 104 and Samples 121 to
The color reproduction of each of 127 samples was evaluated in the same manner as in Example 2. In this case, various blue subjects were lined up and photographed in order to focus on the improvement of blue reproduction.
FIG. 2 shows the spectral reflection characteristics of representative subjects D to F.

The evaluation results are shown in Table 5. As is clear from Table 5, the samples of the present invention in which the YF dye of the present invention was used and the yellow coupler was mixed in the red light-sensitive emulsion layer, the various blue objects were well discriminated and faithfully and vividly colored. You can see that it is reproduced well.

Example 4 In Sample 110, the emulsion J of the 14th layer was replaced with the emulsion L, the emulsion L of the 15th layer was replaced with the emulsion M, and the emulsions M and N of the 16th layer were replaced by sphere-equivalent average grain sizes of 1. 7 μm, coefficient of variation 13
%, Ag I content of 2.0% was used for the twin crystal grain emulsion, and the dye D-1 in the 17th layer was further increased to 0.016 g / m ² to prepare a tungsten exposure film sample 131. Furthermore, the amount of the dye in the 13th layer was reduced to half and the sample 13
Created 2. With respect to this sample, the same changes as in Examples 2 and 3 were performed, and a color reproducibility test was performed by exposure to tungsten. As a result, the effects of the present invention were exhibited as in Examples 2 and 3.

Sample 132, which has 2.1 times the average particle size of the highest-sensitivity blue photosensitive layer and 1.4 times the average particle size of the highest-sensitivity green photosensitive layer, is sample 13 Even if the amount of yellow dye in the layer was reduced, no deterioration in color reproduction was observed, there was little residual color, and the lack of highlight was very good.

[Brief description of drawings]

FIG. 1 is a graph showing spectral reflectances of subjects A to C.

FIG. 2 is a graph showing spectral reflectances of subjects D to F.

[Explanation of symbols]

 1. Spectral reflectance of subject A 2. 〃 B 〃 3. 〃 C 〃 4. 〃 D 〃 5. 〃 E 〃 6. 〃 F 〃

[Procedure amendment]

[Submission date] May 25, 1995

[Procedure Amendment 1]

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[Correction target item name] 0103

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[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0110

[Correction method] Change

[Correction content]

[0110]

[Chemical formula 23]

[Procedure 3]

[Document name to be amended] Statement

[Name of item to be corrected] 0113

[Correction method] Change

[Correction content]

[0113]

[Chemical formula 26]

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0114

[Correction method] Change

[Correction content]

[0114]

[Chemical 27]

Claims (5)

[Claims] 1. A silver halide color photograph having a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, a blue-sensitive silver halide emulsion layer and a non-photosensitive intermediate layer on a support. In a light-sensitive material, at least one layer contains at least one solid-dispersed dye represented by the following general formula (1), and at least one light-sensitive emulsion layer or an intermediate layer adjacent thereto contains an oxidized product of a developing agent. A silver halide color photographic light-sensitive material characterized by containing two or more types of couplers which develop different hues by reaction with. Embedded image In the formula, A represents an acidic nucleus having at least one carboxyl group, and L ¹ , L ² and L ³ each represent an optionally substituted methine group. R ¹ and R ³ represent a hydrogen atom or a substituent (including a substituent atom). R ² represents a substituent (including a substituent atom). n represents 0 or 1. m is 0 to 4
When m is an integer of 2 to 4, R ^{2 s} may be the same or different. X represents an electron-withdrawing group having a Hammett's substituent constant σ _m of 0.3 or more and 1.5 or less. 2. The silver halide photographic light-sensitive material according to claim 1, wherein X is an alkoxycarbonyl group or a cyano group, and A is an acidic nucleus substituted with a carboxyphenyl group. 3. A silver halide color photographic light-sensitive material according to claim 1, wherein the red light-sensitive emulsion layer contains a cyan coupler and a yellow coupler. 4. The light-sensitive material according to claim 1 or 2, wherein the blue-sensitive emulsion layer contains a yellow coupler and the blue-sensitive emulsion layer and / or an intermediate layer adjacent thereto contains a cyan coupler. A silver halide color photographic light-sensitive material characterized by: 5. The light-sensitive material according to claim 1 or 2, wherein each of the blue, green and red color-sensitive layers is composed of two or more layers having different sensitivities, and the blue-sensitive emulsion layer has the highest sensitivity. The average grain size of the emulsion in the emulsion layer is twice the average grain size of the emulsion in the emulsion layer having the highest sensitivity among the green-sensitive emulsion layers.
A silver halide color photographic light-sensitive material characterized by being 5 times.