JPH05158196A - Multilayer silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain the multilayer silver halide color photographic sensitive material high in cyan color developing density and color image fastness by incorporating a specified cyan coupler and an yellow coupler. CONSTITUTION:The photographic sensitive material contains the cyan coupler represented by formula I and the yellow coupler represented by formula II. In formulae I and II, Y is a non-metallic atomic group necessary to form one of 3-to 8-membered hetero rings together with the near N atom, but the N atom does not combine with a carbonyl group; L is alkylene; R<1> is aryl; Z is H or a group to be released by coupling H: R1 is alkylene; R<2> is H, halogen, alkoxyl, or the like; R3 is a group substitutable on the benzene ring; X is H or a group to be released by coupling: and theta is an integer of 0-4, but when it is plural, theta may be same or different.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention provides improved photographic properties and provides stable photographic performance against changes in processing factors.
And a multilayer silver halide color photographic light-sensitive material having improved color image fastness.

[0002]

2. Description of the Related Art Cyan couplers used in positive type silver halide color photographic light-sensitive materials (hereinafter simply referred to as light-sensitive materials) in the current negative-positive system are mainly phenol-type couplers for color reproduction. There is. The phenol couplers are roughly classified into 2-acylamino-5-alkylphenol couplers and 2,5-diacylamino couplers. Typical couplers for these are, for example, US Pat. Nos. 2,369,929 and 2,801,17.
No. 1, No. 3,772,002, No. 2,895,8
No. 26, No. 3,758, 308, No. 4,327,
No. 173, West German Patent Publication No. 3,329,729, and European Patent No. 121,365A can be mentioned. However, 2-acylamino-5-
Cyan dye images formed from alkylphenol couplers suffer from their fastness, especially their large discoloration when stored under conditions of high temperature and high humidity. Two
The 5-diacylaminophenol-based coupler also has improved color image fastness under the conditions of high temperature and high temperature and humidity as compared with the former coupler, but is slightly inferior to the former coupler with respect to light, and further coupled. It has the disadvantage of low activity. Furthermore, the molecular extinction coefficient of the cyan dye formed from both couplers is not so high, and there is the disadvantage that the coating amount of the coupler must be increased to obtain the cyan density required for the light-sensitive material.

On the other hand, there is a 2-ureido-5-acylamino phenol coupler as a coupler belonging to the same phenol coupler. Typical couplers are, for example, U.S. Pat. Nos. 3,446,622 and 4,33.
No. 3,999, No. 4,775,616, No. 4,4
51,559, 4,427,767, JP-A-6
The couplers described in 1-42658 can be mentioned. However, this 2-ureido-5-acylamino-based phenol coupler has a slightly higher absorption density of the chromophores than the above-mentioned phenol-based coupler. It has a p-cyanophenylureido group at the 2-position described in U.S. Pat. No. 4,333,999;
Some couplers, such as couplers having a substituted alkylacylamino group at the position, associate with each other to cause bathochromic shift and improve color image fastness, but both have spectral absorption maximum wavelengths ( Since λmax) has long-wavelength absorption, it is beginning to be used for negative photosensitive materials, but it is not used for positive systems, especially color paper systems at present. In order to obtain higher absorption concentration by utilizing the association of the formed dyes, for example, European Patent Publication No. 271,32
No. 3, No. 271,324 and No. 271,325 disclose couplers having a p-cyanophenylureido group at the 2-position and limiting the acylamino group at the 5-position to a specific group. All of these are intended to improve coupling activity and spectral absorption characteristics for negative photosensitive materials. Moreover, when these couplers are applied to color paper systems, some of the absorption densities of the color images obtained from these couplers certainly show high values, but the λmax of the various colored images obtained is long wavelength. It is not preferable for color reproduction due to absorption, and changes in color density when thinned,
It was found that there are problems such as fluctuations in spectral absorption characteristics and color image fastness depending on storage conditions after processing, and fluctuations in photographic properties during storage of light-sensitive materials.

Further, the use of a phenolic coupler having a ureido group at the 2-position in a color paper system is described, for example, in JP-A-60-256142 and 62-11.
No. 5157, No. 62-153953, No. 62-174
No. 757, JP-A Nos. 1-177546 and 1-1175.
Nos. 47 and 2-27344 describe phenolic couplers having a ureido group, but no description supporting the effects of these couplers is found.
Moreover, when the phenolic coupler having an ureido group described in these is actually used for color paper, the coupling activity, color reproducibility and color image fastness are not sufficient, or when the light-sensitive material is stored or continuously processed. Photographic stability,
In particular, it has become clear that there is a problem in that the photographic property varies greatly with the passage of time from exposure to color development. On the other hand, a phenol-based coupler having an ureido group at the 2-position and an alkylacylamino group substituted at the 5-position with an imidazolidin-2,4-dione-1-yl group as a heterocyclic group is disclosed in JP-A-60-249150. Although it is described in the example, there is no description of a specific effect in a color paper system. An example of using these couplers is a color negative type single layer, and although the color image fastness is improved, it is shown that there is almost no improvement effect on the color forming property. Therefore, the effect of the multi-layer system of color paper and the relation with other layers of the multi-layer system cannot be inferred from these. In addition, JP-A-3-196
No. 037 describes a coupler relating to the present invention.
However, the implementation of the coupler having a ureido group at the 2-position and an alkylacylamino group substituted with an azolyl group at the 5-position according to the present invention in a color paper system is not described as described above. Therefore, the specific effect is unknown. The implementation in the described color paper system was carried out by using an acylamino group at the 2-position, an alkylacylamino group substituted at the 5-position with an azolyl group, or an alkylacylamino group substituted at the 2-position with an azolyl group, and an alkyl group at the 5-position. The couplers and the like which have the basic mother structure are different from those of the couplers according to the present invention, and the couplers are implemented in a single layer system. Therefore, the effect in the multi-layer system cannot be inferred from these, and much less clear for the multi-layer system of color paper.

On the other hand, as the yellow coupler, acetanilide type couplers represented by benzoylacetanilide type and pivaloylacetanilide type are generally used. In color paper, a pivaloyl acetanilide type coupler is mainly used because of the spectral absorption characteristics and color image fastness of the resulting color forming dye. However, the dye has a smaller molecular extinction coefficient and a lower coupling activity than the benzoylacetanilide type coupler. In the current color paper, the blue-sensitive emulsion layer is arranged on the side closer to the support below the red-sensitive emulsion layer and the green-sensitive emulsion layer. As a result, the progress of development of the blue-sensitive emulsion layer is further delayed, which causes problems such as difficulty in shortening the color development processing time and large fluctuation in photographic properties during continuous processing. Therefore, for example, JP-A-61-280249 and JP-A-61-1
Limited use of a yellow coupler having a high relative coupling speed and coating of the coupler (including photosensitive silver halide) by defining the relative coupling speed as described in No. 89536. There was a problem that the amount had to be increased.

[0006]

SUMMARY OF THE INVENTION Therefore, the first object of the present invention is to provide a multilayer silver halide color photographic light-sensitive material which provides high cyan color density and color image fastness. The second objective is a multilayer silver halide color photographic light-sensitive material which does not change in hue depending on the color density and the storage conditions after processing even if the coating amount of the cyan coupler in the silver halide emulsion layer containing the cyan coupler is reduced to make it thinner. To provide. A third object is to provide a multilayer silver halide color photographic light-sensitive material in which fluctuations in photographic properties due to rapid processing and continuous processing are reduced.

[0007]

The above-mentioned object can be achieved by the silver halide color photographic light-sensitive material described below. That is, in a multilayer silver halide color photographic light-sensitive material comprising a silver halide emulsion layer containing a cyan coupler, a silver halide emulsion layer containing a magenta coupler, and a silver halide emulsion layer containing a yellow coupler on a reflective support, the cyan Multilayer silver halide color photograph containing at least one coupler represented by the general formula (1) as a coupler and at least one coupler represented by the general formula (Y) as the yellow coupler. Photosensitive material. General formula (1)

[0008]

[Chemical 3]

In the general formula (1), Y is 3 together with N.
To L represent an alkylene group, R ¹ represents an aryl group, and Z represents a hydrogen atom or a coupling-off group.
However, in the heterocycle, the carbonyl group does not directly bond to N. General formula (Y)

[0010]

[Chemical 4]

In the general formula (Y), R ₁ can be an alkyl group, R ₂ can be a hydrogen atom, a halogen atom, an alkoxy group, an aryloxy group, an alkyl group or a dialkylamino group, and R ₃ can be a benzene ring. Group, X represents a hydrogen atom or a coupling-off group, and γ represents an integer of 0 to 4. However, when γ is plural, plural R ₃ may be the same or different.

The cyan coupler represented by the general formula (1) will be described in detail below. However, in the following explanation,

[0013]

[Chemical 5]

The heterocyclic group represented by is represented by X for convenience. The heterocyclic group represented by X in the general formula (1) is
Total number of carbon atoms (hereinafter referred to as C number) 1 to 30 (preferably 1 to 24), 3 to 8 member (preferably 5 to 7 member), and further N, O, S, Se or Te in the ring. It is a heterocyclic group which may be contained, and may have a substituent (when it can be substituted) or can be condensed (when it can be condensed). When X is a monocycle, examples thereof include 1-pyrrolyl, 1-imidazolyl,
1-pyrazolyl, 1,2,3-triazol-1-yl, 1,2,4-triazol-1-yl, 1,2,4
-Triazol-4-yl, 1,2,3-triazol-1-yl, 1,2,3,4-tetrazol-1-yl, 1,2,3,4-tetrazol-2-yl, 4-pyridone -1-yl and the like, and examples of the case where X is a condensed ring include indol-1-yl, indazol-1-yl,
Benzimidazol-1-yl, benzotriazole-
1-yl, benzotriazol-2-yl, carbazolyl, purin-1-yl, xanthin-1-yl and the like.

The heterocyclic group represented by X may be substituted, and examples of the substituent include a halogen atom, a nitro group,
Cyano group, carboxyl group, alkyl group, aryl group,
Heterocyclic group, alkoxy group, aryloxy group, alkylthio group, arylthio group, acyl group, sulfonyl group, amino group, alkoxycarbonyl group, acyloxy group, carbonamide group, sulfonamide group, carbamoyl group,
Examples thereof include sulfamoyl group, ureido group, alkoxycarbonylamino group and the like.

X is preferably 1-imidazolyl, 1-pyrazolyl, 1,2,4-triazol-1-yl, 1,
2,3,4-tetrazol-1-yl, 1,2,3,4
-Tetrazol-2-yl, benzimidazole-1-
Yl, benzotriazol-1-yl, benzotriazol-2-yl or 1,2,3-triazol-1-
And more preferably 1-pyrazolyl, 1,2,
4-triazol-1-yl, 1,2,3,4-tetrazol-2-yl, benzotriazol-2-yl or 1,2,3-triazol-1-yl.

In the general formula (1), L is a C number of 1 to 30.
(Preferably 1 to 18) represents an alkylene group, and a substituent (for example, a halogen atom, an aryl group, an alkoxy group,
It may have an aryloxy group or an alkoxycarbonyl group).

L is preferably represented by the following general formula (2).

[0019]

[Chemical 6]

In the general formula (2), R ² and R ³ each independently represent a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group or an alkoxycarbonyl group, and m represents an integer of 1 to 6, respectively. .. However, m
When there are a plurality of -CR ² (R ³ )-, they may be the same or different. In the general formula (2), R ² and R ³ are preferably a hydrogen atom, an alkyl group or an aryl group,
m is preferably an integer of 1 to 3, more preferably 1.

In the general formula (1), R ¹ preferably represents an aryl group having a C number of 6 to 36, more preferably 6 to 15, and may be substituted with a substituent selected from the following substituent group A. It may be a condensed ring. Here, the substituent group A is a halogen atom, hydroxyl group, carboxyl group, sulfo group, cyano group, nitro group, amino group, alkyl group, alkenyl group, alkynyl group, cycloalkyl group, aryl group, alkoxy group, aryl. Oxy group, alkylthio group, arylthio group, alkylsulfonyl group, arylsulfonyl group, acyl group, acyloxy group, alkoxycarbonyl group, aryloxycarbonyl group, carbonamido group, sulfonamide group, carbamoyl group, sulfamoyl group, ureido group, alkoxy It refers to a group of substituents consisting of a carbonylamino group, a sulfamoylamino group, an alkoxysulfonyl group, an imide group and a heterocyclic group. More preferable substituents are halogen atom (F, Cl, Br, I), cyano group, nitro group, acyl group (eg acetyl, benzoyl), alkyl group (eg methyl, t-butyl, trifluoromethyl, trichloromethyl). , An alkoxy group (eg, methoxy, ethoxy, butoxy, trifluoromethoxy), an alkylsulfonyl group (eg, methylsulfonyl, propylsulfonyl, butylsulfonyl, benzylsulfonyl), an arylsulfonyl group (eg, phenylsulfonyl, p-tolylsulfonyl, p-chlorophenyl) Sulfonyl), alkoxycarbonyl group (eg methoxycarbonyl, butoxycarbonyl), sulfonamide group (eg methanesulfonamide, trifluoromethanesulfonamide, toluenesulfonamide), Sulfamoyl group (e.g. N,
N-dimethylcarbamoyl, N-phenylcarbamoyl) or a sulfamoyl group (for example, N, N-diethylsulfamoyl, N-phenylsulfamoyl). R ¹ is preferably a phenyl group having at least one substituent selected from a halogen atom, a cyano group, a sulfonamide group, an alkylsulfonyl group, an arylsulfonyl group and a trifluoromethyl group, and more preferably 4-cyano. Phenyl, 4-cyano-3-halogenophenyl, 3-cyano-4-halogenophenyl, 4
-Alkylsulfonylphenyl, 4-alkylsulfonyl-3-halogenophenyl, 4-alkylsulfonyl-
3-alkoxyphenyl, 3-alkoxy-4-alkylsulfonylphenyl, 3,4-dihalogenophenyl,
4-halogenophenyl, 3,4,5-trihalogenophenyl, 3,4-dicyanophenyl, 3-cyano-4,5
-Dihalogenophenyl, 4-trifluoromethylphenyl or 3-sulfonamidophenyl, particularly preferably 4-cyanophenyl, 3-cyano-4-halogenophenyl, 4-cyano-3-halogenophenyl, 3,4
-Dicyanophenyl or 4-alkylsulfonylphenyl.

In the general formula (1), Z represents a hydrogen atom or a coupling-off group (including a leaving atom; the same applies hereinafter). Preferred examples of coupling-off group, a halogen ^{atom, -OR 4, -SR 4, -O} (CO) R 4, -O
^{_{SO 2 R 4, -NH (CO}} ) R 4, -NH (CO) SR
⁴ , —O (CO) OR ⁴ , —O (CO) NHR ⁴ , an arylazo group having a C number of 6 to 30, a C number of 1 to 30, and a nitrogen atom at a coupling active position (position to which Z is bonded). Heterocyclic group to be bonded (eg succinimide, phthalimide,
Hydantoinyl, pyrazolyl, 2-benztriazolyl) and the like. Here, R ⁴ is an alkyl group having a C number of 1 to 36, an alkenyl group having a C number of 2 to 36, and a C number of 3 to 36.
Represents a cycloalkyl group of C, an aryl group having a C number of 3 to 36, or a heterocyclic group having a C number of 2 to 36.
It may be substituted with a substituent selected from the group. Z is more preferably a hydrogen atom, a halogen atom, an alkoxy group, an aryloxy group or an alkylthio group, and particularly preferably a hydrogen atom, a chlorine atom, a group represented by the following general formula (3) or a general formula (4) below. It is a group represented.

[0023]

[Chemical 7]

In the general formula (3), R ⁵ is a halogen atom, a cyano group, a nitro group, an alkyl group, an alkoxy group,
An alkylthio group, an alkylsulfonyl group, an arylsulfonyl group, a carbonamido group, a sulfonamide group, an alkoxycarbonyl group, a carbamoyl group, a sulfamoyl group or a carboxyl group, and n represents an integer of 0 to 5. When n is plural, R ⁵ may be the same or different.

[0025]

[Chemical 8]

In the general formula (4), R ⁶ and R ⁷ are each independently a hydrogen atom or a monovalent group, and T is —CO.
-, - SO -, - SO 2 - or - (PO) R ⁹ - represent. However, R ⁸ and R ⁹ each represent a hydroxyl group, an alkyl group, an aryl group, an alkoxy group, an alkenyloxy group, an aryloxy group or an amino group, and p represents an integer of 1 to 6. Here, when p is plural, -C (R
⁶ ) R ⁷ -may be the same or different.

In the general formula (3), R ⁵ is preferably a halogen atom, an alkyl group (eg methyl, t-butyl, t-octyl, pentadecyl), an alkoxy group (eg methoxy, n-butoxy, n-octyloxy, Benzyloxy, methoxyethoxy), carbonamide group (eg acetamide, 3-carboxypropanamide) or sulfonamide group (eg methanesulfonamide, toluenesulfonamide, p-dodecyloxybenzenesulfonamide), particularly preferably alkyl group Alternatively, it is an alkoxy group. n is preferably 0 to 2
Is an integer of 0, more preferably an integer of 0 or 1.

In the general formula (4), when R ⁶ and / or R ⁷ represents a monovalent group, it is preferably an alkyl group (for example, methyl, ethyl, n-butyl, ethoxycarbonylmethyl, benzyl, n-decyl, n-dodecyl),
Aryl groups (eg phenyl, 4-chlorophenyl, 4
-Methoxyphenyl), an acyl group (for example, acetyl, decanoyl, benzoyl, pivaloyl) or a carbamoyl group (for example, N-ethylcarbamoyl, N-phenylcarbamoyl), R ⁶ and R ⁷ are more preferably a hydrogen atom, an alkyl group or It is an aryl group. T is preferably in the general formula (4) -CO- or -SO ₂
-, More preferably -CO-. In the general formula (4), R ⁸ is preferably an alkyl group, an alkoxy group, an alkenyloxy group, an aryloxy group or a substituted or unsubstituted amino group, and more preferably an alkoxy group or a substituted or unsubstituted amino group.
In the general formula (4), p preferably represents an integer of 1 to 3, more preferably 1.

Specific examples of each substituent in the general formula (1) are shown below. X, that is, an example of a group represented by Chemical formula 5

[0030]

[Chemical 9]

[0031]

[Chemical 10]

Examples of the group represented by L.

[0033]

[Chemical 11]

[0034]

[Chemical 12]

Examples of the group represented by R ¹ .

[0036]

[Chemical 13]

[0037]

[Chemical 14]

Examples of groups represented by Z.

[0039]

[Chemical 15]

[0040]

[Chemical 16]

[0041]

[Chemical 17]

[0042]

[Chemical 18]

[0043]

[Chemical 19]

[0044]

[Chemical 20]

Specific examples of the coupler represented by the general formula (1) are shown below in Tables 1 and 2. However, the capital letters in the table correspond to the capital letters given to the specific examples of the substituent X.

[0046]

[Table 1]

[0047]

[Table 2]

A typical synthetic route of the cyan coupler represented by the general formula (1) is shown below.

[0049]

[Chemical 21]

Here, R is a hydrogen atom or a lower alkyl group (eg, methyl, ethyl), and X is a leaving group (eg, F, Cl, Br, I, mesyloxy, tosyloxy).
Is. Compound c is synthesized by a nucleophilic substitution reaction between compound a and compound b. At this time, triethylamine, N-
It is preferable to use a base such as methylmorpholine, diazabicycloundecene, sodium carbonate or potassium carbonate. The reaction may be carried out without solvent, but acetonitrile, acetone, N, N-dimethylformamide, N, N
A solvent such as dimethylacetamide, N, N′-dimethylimidazolin-2-one, toluene or tetrahydrofuran may be used. The reaction temperature is usually -20 ° C to 15 ° C.
The temperature is 0 ° C, preferably 20 ° C to 100 ° C. When R is an alkyl group, it is induced to c by hydrolysis. It is common to use an aqueous solution of an inorganic base such as an aqueous solution of sodium hydroxide, an aqueous solution of potassium hydroxide, an aqueous solution of sodium carbonate, and water, methanol, ethanol, as a reaction solvent.
A water-miscible solvent such as tetrahydrofuran is selected. The reaction temperature is generally -20 ° C to 100 ° C, preferably 0 ° C to 80 ° C.
Is. For the induction from d to e, thionyl chloride, phosphorus oxychloride, phosphorus pentachloride, oxazolyl chloride, etc. are used,
No solvent, methylene chloride, chloroform, carbon tetrachloride,
The reaction is carried out in a solvent such as dichloroethane, toluene, N, N-dimethylformamide, N, N-dimethylacetamide. The reaction temperature is usually from -20 ° C.
It is 150 ° C, preferably -10 ° C to 80 ° C. Compound f is described in U.S. Pat. No. 4,333,999 and JP-A-60-3.
No. 5731, No. 61-2757, No. 61-42658
No. 63-208562 and the like. The reaction between e and f is usually carried out without solvent or in a solvent such as acetonitrile, ethyl acetate, tetrahydrofuran, dioxane, N, N-dimethylformamide, N, N-dimethylacetamide, N, N′-dimethylimidazolin-2-one, etc. -20 ° C
~ 150 ° C, preferably -10 ° C to 80 ° C. At this time, pyridine, imidazole, N, N
-Weak bases such as dimethylaniline may be used. The cyan coupler represented by the general formula (1) can also be synthesized by a direct dehydration condensation reaction between d and f, and at this time, N, N'-dicyclohexylcarbodiimide, carbonyldiimidazole and the like are used as the condensing agent. The synthesis examples of the cyan coupler represented by the general formula (1) are shown below. Synthesis Example 1 Synthesis of Example Coupler 5-Phenyl-1,2,3,4-tetrazole 14.6
g, 200 ml of N, N-dimethylacetamide was added to 34.6 g of potassium carbonate, and 33.5 g of ethyl 2-bromotetradecanoate was added dropwise while stirring on a steam bath. After the dropping, the mixture was heated with stirring for 3 hours and cooled. 300 ml of ethyl acetate was added to the reaction solution, washed with 400 ml of water three times,
Extracted. The ethyl acetate solution was concentrated with an evaporator, and the residue was dissolved in 200 ml of ethanol. 50 ml of water containing 10 g of sodium hydroxide in an ethanol solution with stirring at room temperature
The solution was added dropwise and stirred for 5 hours. After dilute hydrochloric acid was added to the reaction solution to make it acidic, 300 ml of ethyl acetate was added to the reaction solution,
It was washed with 0 ml of water three times and extracted. The ethyl acetate solution was concentrated with an evaporator, and the residue was added with acetonitrile 300
ml was added and dissolved. The acetonitrile solution was gradually cooled, and the precipitated white crystals were filtered to obtain 35 g of 2- (5-phenyl-1,2,3,4-tetrazol-2-yl) tetradecanoic acid. 2- (5-phenyl-1,2,2
3,4-tetrazol-2-yl) tetradecanoic acid 2
2.4 g and N, N-dimethylformamide (0.2 ml) were dissolved in methylene chloride (60 ml), and oxalyl chloride (7.9 ml) was added dropwise with stirring at room temperature. After stirring for 2 hours, the mixture was concentrated under reduced pressure to give oily 2- (5-phenyl-1,2,3,4).
-Tetrazol-2-yl) tetradecanoic acid chloride was obtained. 5-amino-4-chloro-2- [3 synthesized by the method described in US Pat. No. 4,333,999.
-(4-Cyanophenyl) ureido] phenol 16.
1 g was dissolved in 200 ml of N, N-dimethylacetamide, and 2- (5-phenyl-1,2,2,2) was added at room temperature under a nitrogen stream.
3,4-Tetrazol-1-yl) tetradecanoic acid chloride was added dropwise. After dropping, the mixture was stirred for 2 hours and transferred to a separating funnel. 300 ml of ethyl acetate and 500 ml of water were added for extraction, the ethyl acetate solution was washed with dilute hydrochloric acid and then with an aqueous sodium hydrogen carbonate solution, and then concentrated. Acetonitrile (300 ml) was added to the concentrate, dissolved by heating, and then crystallized. The precipitated crystals were filtered, washed with acetonitrile, and dried to obtain 29.1 g of crystals of the target exemplary coupler 3. The structure of the coupler was confirmed by ¹ H NMR spectrum, mass spectrum and elemental analysis. The melting point was 176-185 ° C.

The cyan coupler of the present invention can be incorporated into a light-sensitive material by an oil-in-water dispersion method. When introducing a cyan coupler, including the cyan coupler of the present invention, into a light-sensitive material, no high-boiling organic solvent is used, or for all couplers,
It is preferable to use the high boiling point organic solvent in a weight ratio of 1.5 or less. A more preferable weight ratio is 0.1 to 1.
The range is 0. The cyan coupler of the present invention provides high color development (high sensitivity, high color density) even when the amount of the high-boiling organic solvent used is reduced, and does not change the spectral absorption characteristics of the obtained color image, resulting in color image fastness. Has the advantage of not deteriorating. The cyan coupler of the present invention may be added to either the photosensitive layer or its adjacent layer (non-photosensitive layer),
Usually, it is preferably added to the red-sensitive emulsion layer. In this case, the cyan coupler is usually used in an amount of 0.002 to 2 mol, preferably 0.01 to 1 mol, per mol of the photosensitive silver halide. Particularly preferably 0.
It is 1 to 0.5 mol. Further, it is preferable that the coating amount per square meter does not exceed 0.5 mmol. It is more preferably 0.01 to 0.4 mmol. It is particularly preferably in the range of 0.01 to 0.3 mmol. The cyan coupler of the present invention may be used alone or in combination of two or more kinds. Further, cyan couplers other than the present invention may be mixed and used. However, when they are used as a mixture, the total amount of the cyan couplers represented by the general formula (1) is preferably 50 mol% or more, and more preferably 75% or more of the total amount of the cyan couplers.

In the present invention, various known techniques can be applied to add the cyan coupler represented by the general formula (1) to the constituent layers of the light-sensitive material. Usually, it can be added by an oil-in-water dispersion method known as an oil protect method. After being dissolved in a solvent, it is emulsified and dispersed in a gelatin aqueous solution containing a surfactant. Alternatively, water or an aqueous gelatin solution may be added to a coupler solution containing a surfactant to form an oil-in-water dispersion with phase inversion. For example, in the oil-in-water dispersion method described in US Pat. No. 2,322,027, a high-boiling organic solvent having a boiling point of about 175 ° C. or higher under normal pressure, such as phthalic acid esters, phosphoric acid esters, and benzoic acid esters. , Fatty acid esters, amides, phenols, alcohols, carboxylic acids, N,
N-dialkylaniline acid, hydrocarbons, oligomers or polymers and / or low boiling organic solvents having a boiling point of about 30 ° C. to about 160 ° C. under normal pressure, such as esters (eg ethyl acetate, butyl acetate, ethyl propionate, β-ethoxyethyl acetate, methyl cellosolve acetate), alcohols (eg secondary butyl alcohol), ketones (eg methyl isobutyl ketone, methyl ethyl ketone, cyclohexanone), amides (eg dimethylformamide, N-methylpyrrolidone), ethers (eg After dissolving the lipophilic photographic organic compound with tetrahydrofuran, dioxane, etc., the hydrophilic colloid such as gelatin is emulsified and dispersed.
The low-boiling organic solvent may be removed from the coupler dispersion by a method such as distillation, washing with noodles or ultrafiltration, and then mixed with a photographic emulsion. In the present invention, in addition to the high boiling point organic solvent which is a plasticizer as described above, a water insoluble polymer compound is also included in the high boiling point organic solvent. Such high boiling point organic solvents include liquids, waxes,
It may be in any form such as solid, and has a dielectric constant (25 ° C.) of 2 to 20 as a physical property value, preferably 3 to 1
The range is 5 and the refractive index (25 ° C.) is 1.30.
A high boiling organic solvent in the range of 1.70, preferably 1.35 to 1.60. The above high boiling point organic solvent is preferably represented by the following formulas [S-1] to [S-9]. Formula [S-1]

[Chemical formula 22]

Formula [S-2]

[Chemical formula 23]

[0054] formula [S-3] (Ar-COO) _b -R ₇ Formula [S-4] (R ₈ -COO) _c -R ₉ Formula [S-5] _{R 10 - (COO-R 11} ) d Formula [S-6]

[0055]

[Chemical formula 24]

Formula [S-7]

[0057]

[Chemical 25]

Formula [S-8]

[0059]

[Chemical formula 26]

[0060] formula [S-9] _{- (A 1) a1 - (} A 2) a2 - ...... - (A n) an

In the formula [S-1], R ₁ , R ₂ and R ₃
Each independently represents an alkyl group, a cycloalkyl group or an aryl group. In the formula [S-2], R ₄ and R
₅ each independently represents an alkyl group, a cycloalkyl group or an aryl group, and R ₆ is a halogen atom (F, C
l, Br, I, the same applies hereinafter), alkyl group, alkoxy group,
It represents an aryloxy group or an alkoxycarbonyl group, and a represents an integer of 0 to 3. When a is plural, plural R ₆ may be the same or different. In the formula [S-3], Ar represents an aryl group, b represents an integer of 1 to 6, and R ₇ represents a b-valent hydrocarbon group or a hydrocarbon group bonded to each other by an ether bond. In the formula [S-4], R ₈ represents an alkyl group or a cycloalkyl group,
c represents an integer of 1 to 6, and R ₉ represents a c-valent hydrocarbon group or a hydrocarbon group bonded to each other by an ether bond. In the formula [S-5], d represents an integer of 2 to 6,
R ₁₀ represents a d-valent hydrocarbon group (excluding an aromatic group), and R ₁₁ represents an alkyl group, a cycloalkyl group or an aryl group. In the formula [S-6], R ₁₂ , R ₁₃ and R ₁₄ each independently represent an alkyl group, a cycloalkyl group or an aryl group. R ₁₂ and R ₁₃ or R ₁₃ and R ₁₄
May combine with each other to form a ring. Formula [S-
7], R ₁₅ represents an alkyl group, a cycloalkyl group, an alkoxycarbonyl group, an alkylsulfonyl group, an arylsulfonyl group, an aryl group or a cyano group,
R ₁₆ is a halogen atom, an alkyl group, a cycloalkyl group,
It represents an aryl group, an alkoxy group or an aryloxy group, and e represents an integer of 0 to 3. When e is plural, plural R ₁₆ may be the same or different. In the formula [S-8], R ₁₇ and R ₁₈ each independently represent an alkyl group, a cycloalkyl group or an aryl group, and R ₁₉ is a halogen atom, an alkyl group, a cycloalkyl group, an aryl group,
Represents an alkoxy group or an aryloxy group, and f is 0
Represents an integer of ~ 4. When f is plural, plural R ₁₉ may be the same or different. In the formula [S-9], A ₁ ,
A ₂ , ..., A _n represent polymerized units provided by different non-color-forming ethylene-like monomers, and a ₁ ,
a _2, ......, a _n represents the weight fraction of each polymer unit, n represents an integer of 1 to 30. Specific examples of the high boiling point organic solvent used in the present invention are shown below.

[0062]

[Chemical 27]

[0063]

[Chemical 28]

[0064]

[Chemical 29]

[0065]

[Chemical 30]

[0066]

[Chemical 31]

Examples of compounds other than the high boiling point organic solvent used in the present invention and / or methods for synthesizing these high boiling point organic solvents are described in, for example, US Pat. No. 2,322,027.
No. 2,533,514, No. 2,772,16
No. 3, No. 2,835,579, No. 3,676,1
No. 37, No. 3,912, 515, No. 3,936,
No. 303, No. 4,080,209, No. 4,12
No. 7,413, No. 4,193,802, No. 23
9,851, 4,278,757, 4,6
36,873, 4,483,918, and 4,
745,049, European Patent 276,319A, JP-A-48-47335, 51-149028, 61-86441, 62-118345, 62-118345.
-247364, 63-167357, 64-
No. 68745 and JP-A No. 1-101543. These high boiling point organic solvents may be used as a mixture of two or more kinds, and may also be used in combination with the high boiling point organic solvents other than those mentioned above.

Next, the yellow coupler represented by formula (Y) used in the present invention will be described in detail. In the general formula (Y), R ₁ represents an alkyl group, R _1
2 is a hydrogen atom, a halogen atom (F, Cl, Br, I, the same applies in the following description of the general formula (Y)), an alkoxy group, an aryloxy group, an alkyl group or a dialkylamino group, and R ₃ is substituted on the benzene ring. X is a hydrogen atom or a group capable of splitting off by a coupling reaction with an oxidation product of an aromatic primary amine developing agent (referred to as splitting group), r
Represents an integer of 0 to 4, respectively. However, when r is plural, plural R ₃ may be the same or different.

Examples of R ₃ are halogen atom, alkyl group, aryl group, alkoxy group, aryloxy group, alkoxycarbonyl group, aryloxycarbonyl group, carbonamido group, sulfonamide group, carbamoyl group, sulfamoyl group, There are alkylsulfonyl groups, arylsulfonyl groups, ureido groups, sulfamoylamino groups, alkoxycarbonylamino groups, nitro groups, heterocyclic groups, cyano groups, acyl groups, acyloxy groups, alkylsulfonyloxy groups, arylsulfonyloxy groups, Examples of the leaving group include a heterocyclic group bonded to the coupling active position with a nitrogen atom, an aryloxy group, an arylthio group, an acyloxy group, an alkylsulfonyloxy group, a heterocyclic oxy group, and a halogen atom.

When the substituent in the general formula (Y) is an alkyl group or contains an alkyl group and there is no particular limitation, the alkyl group may be linear, branched or cyclic.
Alkyl groups that may be substituted or may contain unsaturated bonds (eg, methyl, isopropyl, t-
Butyl, cyclopentyl, t-pentyl, cyclohexyl, 2-ethylhexyl, 1,1,3,3-tetramethylbutyl, dodecyl, hexadecyl, allyl, 3-cyclohexenyl, oleyl, benzyl, trifluoromethyl, hydroxymethyl, methoxyethoxy. , Ethoxycarbonylmethyl, phenoxyethyl). When the substituent in the general formula (Y) is an aryl group or includes an aryl group and is not particularly specified, the aryl group may be an optionally substituted monocyclic or condensed ring aryl group (eg, phenyl, 1-naphthyl, p-tolyl,
o-tolyl, p-chlorophenyl, 4-methoxyphenyl, 8-quinolyl, 4-hexadecyloxyphenyl,
Pentafluorophenyl, p-hydroxyphenyl, p
-Cyanophenyl, 3-pentadecylphenyl, 2,4
-Di-t-pentylphenyl, p-methanesulfonamidophenyl, 3,4-dichlorophenyl).

When the substituent in the general formula (Y) is a heterocyclic group or contains a heterocyclic ring and is not particularly specified, the heterocyclic group is at least O, N, S, P, Se or Te. A 3- to 8-membered optionally substituted monocyclic or condensed-ring heterocyclic group containing one heteroatom in the ring (for example, 2-
Furyl, 2-pyridyl, 4-pyridyl, 1-pyrazolyl, 1-imidazolyl, 1-benzotriazolyl, 2-
Benzotriazolyl, succinimide, phthalimide,
1-benzyl-2,4-imidazolidindione-3-yl).

The substituents preferably used in formula (Y) will be described below. In the general formula (Y), R ₁ preferably represents a tertiary alkyl group having 4 to 30 total carbon atoms (hereinafter abbreviated as C number) which may be substituted, and the substituent may be, for example, a halogen atom, Alkoxy group, aryl group, amino group, carbonamido group,
There is a sulfonamide group.

In the general formula (Y), R ₂ is preferably a halogen atom, which may have a C number of 1 to 1 which may be substituted.
30 alkoxy group, C6-30 aryloxy group, C1-30 alkyl group or C0-30 amino group, and examples of the substituent include a halogen atom, an alkyl group, an alkoxy group, There is an aryloxy group.

In the general formula (Y), R ₃ is preferably a halogen atom, which may be substituted, and has a C number of 1 to 3.
0 alkyl group, C 6-30 aryl group, C 1-
30 alkoxy groups, C2-30 alkoxycarbonyl groups, C7-30 aryloxycarbonyl groups,
Carboxamide group having 1 to 30 C number, sulfonamide group having 1 to 30 C number, carbamoyl group having 1 to 30 C number, 0 number of C
To 30 sulfamoyl groups, C 1-30 alkylsulfonyl groups, C 6-30 arylsulfonyl groups, C
A ureido group having a number of 1 to 30, a sulfamoylamino group having a number of C of 0 to 30, an alkoxycarbonylamino group having a number of C of 2 to 30, a heterocyclic group having a number of C of 1 to 30, an acyl group having a number of C of 1 to 30, It represents an alkylsulfonyloxy group having a C number of 1 to 30, an arylsulfonyloxy group having a C number of 6 to 30, and the substituent thereof is, for example, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group. , Heterocyclic oxy group, alkylthio group, arylthio group, heterocyclic thio group, alkylsulfonyl group, arylsulfonyl group, acyl group, carbonamido group, sulfonamide group, carbamoyl group, sulfamoyl group, alkoxycarbonylamino group, sulfamoyl Amino group, ureido group, cyano group, nitro group, acyloxy group, alkoxycarbonyl group, Lumpur aryloxycarbonyl group, an alkylsulfonyloxy group, an arylsulfonyloxy group. In the general formula (Y), r preferably represents an integer of 1 or 2, and the substitution position of R ₃ is R ₁ —CO—.
A meta position or a para position is preferable with respect to CH (X) -CONH-.

In the general formula (Y), X preferably represents a heterocyclic group or an aryloxy group bonded to the coupling active position with a nitrogen atom. When X represents a heterocyclic group, it is preferably an optionally substituted 5- to 7-membered monocyclic or condensed-ring heterocycle, examples of which include succinimide, maleinimide, phthalimide, diglycolimide, and pyrrole. , Pyrazole, imidazole, 1,
2,4-triazole, tetrazole, indole, benzopyrazole, benzimidazole, benzotriazole, imidazolidine-2,4-dione, oxazolidine-2,4-dione, thiazolidine-2,4-dione,
Imidazolidin-2-one, oxazolin-2-one,
Thiazolin-2-one, benzimidazolin-2-one, benzoxazolin-2-one, benzothiazolin-2-one, 2-pyrrolin-5-one, 2-imidazolin-5-one, indoline-2,3-dione , 2,6-
Dioxypurine, parabanic acid, 1,2,4-triazolidine-3,5-dione, 2-pyridone, 4-pyridone,
2-pyrimidone, 6-pyridazone-2-pyrazone, 2-
Amino-1,3,4-thiazolidine, 2-imino-1,
3,4-thiazolidin-4-one and the like, and these heterocycles may be substituted.

Examples of the substituents of these heterocyclic groups are:
Halogen atom, hydroxyl group, nitro group, cyano group,
Carboxyl group, sulfo group, alkyl group, aryl group,
Alkoxy group, aryloxy group, alkylthio group, arylthio group, alkylsulfonyl group, arylsulfonyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyl group, acyloxy group, amino group, carbonamide group, sulfonamide group, carbamoyl group, There are sulfamoyl group, ureido group, alkoxycarbonylamino group, and sulfamoylamino group. When X represents an aryloxy group, X preferably represents an aryloxy group having a C number of 6 to 30, and may be substituted with a group selected from the substituent group mentioned when X is a heterocyclic group. Good. Examples of the substituent for the aryloxy group include a halogen atom, a cyano group, a nitro group, a carboxyl group, a trifluoromethyl group, an alkoxycarbonyl group, a carbonamido group, a sulfonamide group, a carbamoyl group, a sulfamoyl group, an alkylsulfonyl group, and an aryl group. A sulfonyl group or an acyl group is preferred.

The groups or substituents particularly preferably used in formula (Y) are described below. R ₁ is particularly preferably a t-butyl group. The substituent of R ₂ is particularly preferably a chlorine atom, a fluorine atom, an alkyl group having a C number of 1 to 6 (for example, methyl, trifluoromethyl, ethyl, isopropyl, t-butyl), an alkoxy group having a C number of 1 to 8 (for example, Methoxy, ethoxy, methoxyethoxy, butoxy) or an aryloxy group having 6 to 24 carbon atoms (eg, phenoxy, p-tolyloxy, p-methoxyphenoxy), most preferably a chlorine atom or a methoxy group. R ₃ is particularly preferably a halogen atom, an alkoxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbonamide group, a sulfonamide group, a carbamoyl group or a sulfamoyl group, and most preferably an alkoxy group, an alkoxycarbonyl group or a carbonamide group. Alternatively, it is a sulfonamide group. X is particularly preferably a group represented by the following formula [Y-1] or [Y-2]. Formula [Y-1]

[0078]

[Chemical 32]

[0079] Formula Z in [Y-1] is _{-O-C (R 4) (} R 5) -, - S-C (R 4) (R 5) -, -
_{N (R 6) -C (R} 4) (R 5) -, - N (R 6) -N (R 7)
_{-, - N (R 6)} -CO -, - C (R 4) (R 5) -C (R 8)
Represents (R ₉ )-or -C (R ₁₀ ) = C (R ₁₁ )-. Here, R ₄ , R ₅ , R ₈ and R ₉ represent a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkylsulfonyl group, an arylsulfonyl group or an amino group, R
₆ and R ₇ represent a hydrogen atom, an alkyl group, an aryl group, an alkylsulfonyl group, an arylsulfonyl group or an alkoxycarbonyl group, and R ₁₀ and R ₁₁ represent a hydrogen atom, an alkyl group or an aryl group. R ₁₀ and R ₁₁
May combine with each other to form a benzene ring. R ₄ and R ₅ , R ₅ and R ₆ , R ₆ and R ₇ or R ₄ and R ₈ are bonded to each other to form a ring (for example, cyclobutane, cyclohexane,
Cycloheptane, cyclohexene, pyrrolidine, piperidine) may be formed.

Among the heterocyclic groups represented by the formula [Y-1], the particularly preferable one is Z in the general formula [Y-1].
_{O-C (R 4) (} R 5) -, - N (R 6) -C (R 4) (R 5) -
Or _{-N (R 6) -N (R} 7) - is a heterocyclic group which is.
The C number of the heterocyclic group represented by the formula [Y-1] is 2 to 30,
It is preferably 4 to 20, more preferably 5 to 16. Formula [Y-2]

[0081]

[Chemical 33]

In the formula [Y-2], at least one of R ₁₂ and R ₁₃ is a halogen atom, a cyano group, a nitro group, a trifluoromethyl group, a carboxyl group, an alkoxycarbonyl group, a carbonamido group, a sulfonamide group or carbamoyl. Group, sulfamoyl group, alkylsulfonyl group,
It is a group selected from an arylsulfonyl group or an acyl group, and the other may be a hydrogen atom, an alkyl group or an alkoxy group. R ₁₄ represents a group having the same meaning as R ₁₂ or R _13, and m represents an integer of 0-2. Formula [Y-
2] has 6 to 30 carbon atoms in the aryloxy group,
It is preferably 6 to 24, more preferably 6 to 15. In the formulas [Y-1] and [Y-2], the formula [Y-1]
Is most preferred. The coupler represented by the general formula (Y) is
The substituents R ₁ , X or

[0083]

[Chemical 34]

In the above, a dimer or a multimer having a valence of two or more may be bonded to each other to form a multimer or more. In this case, the number of carbon atoms shown in each of the above substituents may be out of the specified range.

When the coupler represented by the general formula (Y) forms a multimer, a homopolymer or a copolymer of an addition polymer ethylenically unsaturated compound (yellow color-forming monomer) having a yellow dye-forming coupler residue is typical. It is an example, and is preferably represented by the formula [Y-3]. Formula [Y-3]-(G _i ) _gi- (H _j ) _hj -In formula [Y-3], G _i is a repeating unit derived from a color forming monomer and is a group represented by formula [Y-4]. And H _j is a group that is a repeating unit derived from a non-color-forming monomer, i is a positive integer, j is 0 or a positive integer, and g _i and h _j are G _i or G _i or _Represents the weight fraction of H _j . Where i or j
Is plural, G _i or H _j represents that plural kinds of repeating units are included. Formula [Y-4]

[0086]

[Chemical 35]

In the formula, R represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a chlorine atom, and A represents -CONH-, -C.
OO- or a substituted or unsubstituted phenylene group, B represents a substituted or unsubstituted alkylene group, a phenylene group or an aralkylene group, L represents -CONH-,
-NHCONH-, -NHCOO-, -NHCO-,-
OCONH-, -NH-, -COO-, -OCO-,-
CO -, - O -, - S -, - SO 2 -, - NHSO 2 -
Or it represents a -SO ₂ NH-. a, b, and c represent 0 or 1. Q is R ₁ , X of the compound represented by the general formula (Y) or

[0088]

[Chemical 36]

A yellow coupler residue in which one hydrogen atom has been removed is shown below. Examples of the non-color forming ethylene type monomer that does not couple with the oxidation product of the aromatic primary amine developing agent that gives the repeating unit H _j include acrylic acid, α-chloroacrylic acid, α-alkylacrylic acid (for example, methacrylic acid, etc.). ), Amides or esters derived from these acrylic acids (eg, acrylamide, methacrylamide, n-butyl acrylamide, t-butyl acrylamide, diacetone acrylamide, methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate). , T-butyl acrylate, iso-butyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate and β-hydroxymethacrylate), vinyl esters (eg vinyl acetate, vinyl propionate and vinyl laurate), acrylonitrile, methacrylonitrile, aromatic vinyl compounds (eg styrene and its derivatives such as vinyltoluene, divinylbenzene, vinylacetophenone and (Sulfostyrene), itaconic acid, citraconic acid, crotonic acid, vinylidene chloride, vinyl alkyl ethers (eg vinyl ethyl ether), maleic acid esters, N-vinyl-2-pyrrolidone, N-vinyl pyridine and 2- and -4-vinyl. Pyridine and the like.

Acrylic acid esters, methacrylic acid esters and maleic acid esters are particularly preferred. Two or more kinds of non-color-forming ethylene type monomers used here can be used together. For example, methyl acrylate and butyl acrylate, butyl acrylate and styrene, butyl methacrylate and methacrylic acid, methyl acrylate and diacetone acrylamide, etc. can be used.

As well known in the field of polymer couplers, the ethylenically unsaturated monomer to be copolymerized with the vinyl monomer corresponding to the above formula [Y-4] is in the form of the copolymer to be formed, for example, solid. , Liquid, micelles and physical and / or chemical properties, eg solubility (solubility in water or organic solvents), compatibility with photographic colloid composition binders such as gelatin, its flexibility , Thermal stability, coupling reactivity with an oxidized product of a developing agent, and diffusion resistance in a photographic colloid can be favorably influenced. These copolymers may be random copolymers or copolymers having a specific sequence (for example, block copolymer, alternating copolymer). The number average molecular weight of the yellow polymer coupler used in the present invention is usually on the order of thousands to hundreds of thousands, but oligomeric polymer couplers of 5,000 or less can also be used.

The yellow coupler used in the present invention is an organic solvent (eg, ethyl acetate, butyl acetate, ethanol,
Micelle formation in hydrophilic colloid, whether it is a lipophilic polymer soluble in methylene chloride, cyclohexanone, dibutyl phthalate, tricresyl phosphate) or a hydrophilic polymer miscible with hydrophilic colloid such as gelatin aqueous solution. It may be a polymer having possible structures and properties.

The yellow polymer coupler used in the present invention is a gelatin prepared by dissolving a lipophilic polymer coupler obtained by polymerization of a vinyl monomer giving a coupler unit represented by the above formula [Y-4] in an organic solvent. It may be emulsified and dispersed in the form of a latex in an aqueous solution, or may be directly emulsified by an emulsion polymerization method. A method of emulsifying and dispersing a lipophilic polymer coupler in the form of a latex in an aqueous gelatin solution is described in US Pat. No. 3,451,820.
For emulsion polymerization, the method described in US Pat. Nos. 4,080,211 and 3,370,952 can be used. Specific examples of each group and substituent in the general formula (Y) are shown below. Example of R ₁

[0094]

[Chemical 37]

Examples of R ₂

[0096]

[Chemical 38]

Examples of R ₃

[0098]

[Chemical Formula 39]

[0099]

[Chemical 40]

[0100]

[Chemical 41]

[0101]

[Chemical 42]

Example of X

[0103]

[Chemical 43]

[0104]

[Chemical 44]

[0105]

[Chemical 45]

[0106]

[Chemical 46]

Specific examples of the yellow coupler represented by formula (Y) are shown below.

[0108]

[Chemical 47]

[0109]

[Chemical 48]

[0110]

[Chemical 49]

[0111]

[Chemical 50]

[0112]

[Chemical 51]

[0113]

[Chemical 52]

[0114]

[Chemical 53]

[0115]

[Chemical 54]

[0116]

[Chemical 55]

[0117]

[Chemical 56]

[0118]

[Chemical 57]

[0119]

[Chemical 58]

Examples of compounds other than the above-mentioned yellow couplers used in the present invention and / or methods for synthesizing these yellow couplers are described in, for example, US Pat. No. 3,227,55.
No. 4, No. 3,408, 194, No. 3,644, 4
No. 98, No. 3,770,445, No. 3,894.
No. 875, No. 3,933,500, No. 3,97
No. 3,968, No. 4,022,620, No. 4,0
32,347, 4,046,575, and 4,
049,458, 4,057,432, 4,115,121, 4,133,958, 4,157,919, 4,201,584,
No. 4,203,768, No. 4,248,961
No. 4,266,019, 4,286,05
No. 3, No. 4,314, 023, No. 4,326, 0
No. 24, No. 4,327, 175, No. 4,401,
No. 752, No. 4,404,274, No. 4,42
0,556, 4,511,649, 4,6
No. 17,256, No. 4,711,837, No. 4,
729,944, 4,758,501, European Patents 30,747A, 272,041A, 280,330A, 284,081A, 3rd.
13,308A, British Patent No. 1,040,710,
West German Patent No. 3,107,173C, JP-A-58-42
044, 59-174839, 60-6965.
No. 3, No. 62-200349, No. 62-276547.
No. 62-297845, No. 63-43144,
No. 63-123047 and the like.

The yellow coupler of the present invention may be added to either the light-sensitive layer or the non-light-sensitive layer, but it is usually preferably added to the blue-sensitive silver halide emulsion layer before use. In this case, the addition amount of the yellow coupler of the present invention per 1 mol of the photosensitive silver halide is usually 1 × 10 ⁻³ to 2 mol, preferably 1 × 10 ⁻² to 1 mol. Particularly preferably 1 × 10 ^-1 to 5 × 1
It is in the range of 0 ^-1 mol. The yellow coupler of the present invention can be introduced into a light-sensitive material by an oil-in-water dispersion method. At this time, the above high boiling point organic solvent can be used in a weight ratio of 2.0 to zero with respect to the coupler. It is preferably 1.0 to zero, and more preferably 0.5 to 0.1. By adjusting the weight ratio in such a range, it is possible to further improve the stability of continuous processing (there is little variation in photographic properties such as sensitivity and gradation) and the color image fastness to light. The yellow coupler of the present invention may be used alone or in combination of two or more kinds. In the present invention, a coupler in which the yellow dye produced has short-wave absorption is preferable, and specifically, a coupler in which R ₂ has an alkoxy group. Known yellow couplers other than those of the present invention may be mixed and used, and the mixing ratio thereof can be arbitrarily selected.

The yellow coupler represented by the general formula (Y) of the present invention can be comparatively used by combining it with the cyan coupler represented by the general formula (1) of the present invention in the same light-sensitive material, particularly in a color paper system. It is possible to provide a silver halide color photographic light-sensitive material in which fluctuation of photographic properties due to treatment of a yellow coupler having a low coupling rate, particularly a coupler represented by the general formula (Y) in which R ₂ has an alkoxy group is reduced. ..

Next, the "reflection support" used in the present invention will be described. The term "reflective support" refers to one which enhances the reflectivity and makes the dye image formed on the silver halide emulsion layer clear, and such a reflective support includes titanium oxide, zinc oxide on the support. , Those coated with a hydrophobic resin containing a light-reflecting substance such as calcium carbonate and calcium sulfate dispersed therein, and those using a hydrophobic resin containing a light-reflecting substance dispersed therein as a support. For example, baryta paper, polyethylene-coated paper, polypropylene-based synthetic paper, a transparent support provided with a reflective layer, or in combination with a reflective material, such as a glass plate, polyethylene terephthalate, polyester film such as cellulose triacetate or cellulose nitrate, Polyamide film, polycarbonate film,
Examples include polystyrene film and vinyl chloride resin.

As the other reflection type support, a support having a specular reflection or type II diffuse reflection metal surface can be used. The metal surface preferably has a spectral reflectance in the visible wavelength range of 0.5 or more, and the metal surface is preferably roughened or made to be diffuse reflective by using a metal powder. As the metal, aluminum, tin, silver, magnesium, or an alloy thereof is used, and the surface may be the surface of a metal plate, metal foil, or metal thin layer obtained by rolling, vapor deposition, or plating. Above all, it is preferable to obtain the metal by vapor-depositing a metal on another substrate. It is preferable to provide a water resistant resin, especially a thermoplastic resin layer, on the metal surface. An antistatic layer may be provided on the side of the support of the present invention opposite to the side having the metal surface. For details of such a support, see, for example, JP-A-61-210346, JP-A-63-24247, and JP-A-61-210346.
3-24251 and 63-24255. These supports can be appropriately selected depending on the purpose of use.

As the light-reflecting substance, it is preferable to sufficiently knead a white pigment in the presence of a surfactant, and it is preferable to use a pigment particle whose surface is treated with a divalent to tetravalent alcohol. The occupying area ratio (%) of the white pigment fine particles per specified unit area is most typically the observed area is divided into adjacent 6 μm × 6 μm unit areas,
Occupied area ratio of fine particles projected on the unit area (%)
(R ₁ ) can be measured and determined. The coefficient of variation of the occupied area ratio (%) is R ₁ with respect to the average value (R) of R _1.
Can be obtained by the ratio s / R of the standard deviation s of.
The number (n) of the target unit areas is preferably 6 or more.
Therefore, the variation coefficient s / R can be obtained by the following equation 1.

[0126]

[Equation 1]

In the present invention, the coefficient of variation of the occupied area ratio (%) of the fine particles of the pigment is preferably 0.15 or less, particularly 0.12 or less. When it is 0.08 or less, the dispersibility of the particles can be said to be “uniform”.

As the silver halide used in the present invention, silver chloride, silver bromide, silver (iodo) chlorobromide, silver iodobromide and the like can be used, and especially for the purpose of rapid processing, iodide is used. It is preferable to use a silver chlorobromide or silver chloride emulsion having a silver chloride content substantially free of silver of 90 mol% or more, further 95% or more, and particularly 98% or more.

In the light-sensitive material according to the present invention, a hydrophilic colloid layer can be decolorized by a treatment described in European Patent EP 0,337,490A2, pages 27 to 76 for the purpose of improving sharpness of an image. It is preferable to add a dye (among others, an oxonol dye) so that the optical reflection density of the light-sensitive material at 680 nm is 0.70 or more.

The high boiling point organic solvent for photographic additives such as magenta couplers which can be used in the present invention is a compound which is immiscible with water and has a melting point of 100 ° C. or lower and a boiling point of 140 ° C. or higher. Can be used. The melting point of the high boiling point organic solvent is preferably 80 ° C. or lower. The boiling point of the high boiling point organic solvent is preferably 160 ° C. or higher, more preferably 1
It is 70 ° C or higher. For details of these high boiling point organic solvents, refer to JP-A No. 62-215272, No. 1
From page 37, lower right column to page 144, upper right column. Cyan, yellow or magenta couplers are also loadable latex polymers in the presence or absence of the high boiling organic solvents described above (eg US Pat. No. 4,203,7).
No. 16) or dissolved with a polymer insoluble in water and soluble in an organic solvent, and emulsified and dispersed in a hydrophilic colloid aqueous solution. Preferably US Pat.
The homopolymers or copolymers described on pages 12 to 30 of WO857 / 449 and WO88 / 00723 are used, and more preferably a methacrylate or acrylamide polymer, particularly an acrylamide polymer is used. Is preferable in terms of color image stabilization and the like.

Further, in the light-sensitive material according to the present invention, it is preferable to use a color image storability improving compound as described in European Patent EP 0,277,589A2 together with a coupler. In particular, it is preferably used in combination with a pyrazoloazole coupler. That is, the compound (F) that chemically bonds to the aromatic amine-based developing agent remaining after the color development processing to form a chemically inactive and substantially colorless compound and / or the aroma remaining after the color development processing. The use of the compound (C), which forms a chemically inactive and substantially colorless compound by chemically bonding with an oxidant of a group amine type color developing agent, simultaneously or solely, for example, in storage after processing. It is preferable in order to prevent the occurrence of stains and other side effects due to the formation of a coloring dye due to the reaction of the coupler with the color developing agent remaining in the film or its oxidant.

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

Further, the support used in the light-sensitive material according to the present invention is a support provided on a support on the side having a silver halide emulsion layer on which a white polyester support or a layer containing a white pigment is provided for a display. The body may be used.
Further, in order to further 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 set to 0.35 so that the display can be viewed with both reflected light and transmitted light.
It is preferably set in the range of 0.8.

The light-sensitive material of 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.

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

The exposed light-sensitive material can be subjected to a conventional color development process (in the case of a reversal system, a black-and-white development process can also be used together), but in the present invention, a color developing agent, particularly,
N-ethyl-N- (β-methanesulfonamidoethyl)
It is preferred to use the -3-methyl-4-aminoaniline salt. For the purpose of rapid processing, it is preferable to perform 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 and the like) and photographic constituent layers (layer arrangement and the like) applied to the light-sensitive material according to the present invention, and processing methods applied for processing the light-sensitive material. As the treatment additives, those described in the following patent publications, particularly European Patent EP 0,355,660A2 (JP-A-2-139544) are preferably used.

[0138]

[Table 3]

[0139]

[Table 4]

[0140]

[Table 5]

[0141]

[Table 6]

[0142]

[Table 7]

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

A method for processing a silver halide color light-sensitive material using a high silver chloride emulsion having a silver chloride content of 90 mol% or more is described in JP-A-2-207250, page 27, upper left column to page 34, upper right. The method described in the section is preferably applied. Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited thereto.

[0145]

【Example】

Example 1 After a corona discharge treatment was applied to the surface of a paper support laminated on both sides with polyethylene, a gelatin subbing layer containing sodium dodecylbenzene sulfonate was provided, and various photographic constituent layers were further coated to form a layer structure shown below. Was produced. The coating liquid was prepared as follows.

Preparation of coating liquid for first layer Yellow coupler (ExY) 19.2 g, color image stabilizer (Cpd-1) 4.4 g, color image stabilizer (Cpd-7) 0.7
and 3.75 g of color image stabilizer (Cpd-9) with ethyl acetate 2
7.2 cc and 4.8 g of each of the solvents (S-4) and (S-14) were added and dissolved, and this solution was dissolved in 10% sodium dodecylbenzenesulfonate (8 cc) in 10% gelatin aqueous solution.
Emulsified dispersion A was prepared by emulsifying and dispersing in 185 cc. On the other hand, silver chlorobromide emulsion A (cube, average grain size 0.88 μm
3: 7 mixture of a large size emulsion of (1) and a small size emulsion of 0.70 μm (silver molar ratio). Coefficients of variation of grain size distribution were 0.08 and 0.10, respectively, and silver bromide 0.3 mol% was locally contained in a part of grain surface in each size emulsion). In this emulsion, blue-sensitive sensitizing dyes A and B shown below were added to the large-sized emulsion A per mol of silver at 2.0 × 10 ⁻⁴ mol, respectively.
For small size emulsion A, 2.5 × 10 each
^-4 mol is added. The chemical ripening of this emulsion was performed by adding a sulfur sensitizer and a gold sensitizer. The above emulsified dispersion A and this silver chlorobromide emulsion A were mixed and dissolved to prepare a coating solution for the first layer having the following composition.

The coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. As a gelatin hardening agent for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt was used.

Further, Cpd-10 and Cpd-11 are provided in each layer.
Were added so that the total amount was 25.0 mg / m ² and 50.0 mg / m ² , respectively.

The following spectral sensitizing dyes were used in the silver chlorobromide emulsion of each photosensitive emulsion layer.

[0150]

[Chemical 59]

(Each mol of silver halide is 2.0 × 10 ^-4 mol for large size emulsion A and 2.5 × 10 ^-4 mol for small size emulsion A)

[0152]

[Chemical 60]

(Per mol of silver halide, 4.0 × 10 ⁻⁴ mol for large size emulsion B and 5.6 × 10 ⁻⁴ mol for small size emulsion B), and

[0154]

[Chemical formula 61]

(1 mol of silver halide: 7.0 × 10 ^-5 mol for large size emulsion B and 1.0 × 10 ^-5 mol for small size emulsion B)

[0156]

[Chemical formula 62]

(0.9 × 10 ⁻⁴ mol for large size emulsion C and 1.1 × 10 ⁻⁴ mol for small size emulsion C per mol of silver halide)

The following compounds were added to the red-sensitive emulsion layer in an amount of 2.6 × 10 ^-3 mol per mol of silver halide.

[0159]

[Chemical 63]

For the blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer, 1- (5-methylureidophenyl)-
5-mercaptotetrazole with silver halide 1
8.5 × 10 ⁻⁵ mol, 7.7 × 10 ⁻⁴ mol, and 2.
5 × 10 ⁻⁴ mol was added.

For the blue-sensitive emulsion layer and the green-sensitive emulsion layer, 4-hydroxy-6-methyl-1,3,3a, 7-
Tetrazaindene was added in an amount of 1 × 10 ^-4 mol and 2 × 10 ^-4 mol per mol of silver halide, respectively.

Further, in order to prevent irradiation, the following dyes (in parentheses represent coating amount) were added to the emulsion layers.

[0163]

[Chemical 64]

(Layer Constitution) The composition of each layer is shown below. Numbers represent 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) Silver Chlorobromide Emulsion A 0.35 Gelatin 1.22 Yellow Coupler (ExY) 0.82 Color Image Stabilizer (Cpd-1) 0.19 Solvent (S -4) 0.205 Solvent (S-14) 0.205 Color image stabilizer (Cpd-7) 0.06 Color image stabilizer (Cpd-9) 0.16

Second Layer (Color Mixing Prevention Layer) Gelatin 0.64 Color mixing inhibitor (Cpd-5) 0.10 Solvent (S-6) 0.16 Solvent (S-1) 0.08

Third Layer (Green Sensitive Emulsion Layer) Silver chlorobromide emulsion (cubic, 1: 3 mixture of large size emulsion with average grain size 0.55 μm and small size emulsion with 0.39 μm (Ag mole ratio)) The coefficient of variation of the grain size distribution is 0.10 and 0.08, respectively, and in each size emulsion, 0.8 mol% of AgBr is locally contained in a part of the grain surface.) 0.12 Gelatin 1.28 Magenta coupler (ExM ) 0.25 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 (S-1) 0.25 solvent (S-2) 0.25

Fourth Layer (UV Absorbing Layer) Gelatin 1.41 UV Absorbing Agent (UV-1) 0.47 Color Mixing Preventing Agent (Cpd-5) 0.05 Solvent (S-13) 0.24

Fifth Layer (Red Sensitive Emulsion Layer) Silver chlorobromide emulsion (cubic, 1: 4 mixture of large size emulsion having average grain size 0.58 μm and small size emulsion 0.45 μm (Ag mole ratio)) The coefficient of variation of the grain size distribution is 0.09 and 0.11, and AgBr of 0.6 mol% is locally contained in a part of the grain surface in each size emulsion.) 0.17 Gelatin 1.60 Cyan coupler (ExC) 0.34 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-8) 0. 05 Solvent (S-6) 0.17

Sixth Layer (UV Absorbing Layer) Gelatin 0.48 UV Absorbing Agent (UV-1) 0.16 Color Mixing Inhibitor (Cpd-5) 0.02 Solvent (S-13) 0.08

Seventh Layer (Protective Layer) Gelatin 1.10 Polyvinyl alcohol acrylic modified copolymer 0.17 (Modification degree 17%) Liquid paraffin 0.03

[0173]

[Chemical 65]

[0174]

[Chemical 66]

[0175]

[Chemical 67]

[0176]

[Chemical 68]

[0177]

[Chemical 69]

Subsequently, the following samples were prepared. (Samples 102 to 104) The cyan coupler (ExC) used in the fifth layer (red-sensitive emulsion layer) of Sample 101 was replaced with the comparative couplers (b), (c), and (d) in equimolar amounts to obtain a high boiling organic compound. A sample was prepared by adjusting the weight ratio of the solvent (S-6) / cyan coupler to be the same as that of the sample 101 and making no other changes. Comparison coupler (b),
(C) and (d) are shown in Chemical formula 70.

[0179]

[Chemical 70]

(Samples 105 to 115) Sample 101
The cyan coupler (ExC) used in the fifth layer of Example 1 was replaced with the coupler represented by the general formula (1) of the present invention in an equimolar amount, and the weight ratio of (S-6) / cyan coupler was changed to Sample 101.
After adjusting the coating flow rate, adjust the coating flow rate and the coupler
A sample was prepared so that it was applied in a 0.4-fold molar amount of 01 (0.275 mmol / m ² ).

The samples 101 to 115 thus prepared were first prepared by using a sensitometer (F, manufactured by Fuji Photo Film Co., Ltd.
WH type, light source color temperature of 3200 ° K) was used and gradation exposure of a three-color separation filter for sensitometry was applied.
The exposure at this time was performed so that the exposure amount was 250 CMS in the exposure time of 0.1 seconds.

The exposed sample was treated with a paper processor using the following processing steps and processing solution compositions.
Continuous processing (running test) was carried out until the tank capacity for color development was replenished twice, and then the processing was carried out. Treatment process Temperature Time Replenisher ^* Tank capacity Color development 35 ° C 45 seconds 161 ml 17 liter Bleach fixing 30-35 ° C 45 seconds 215 ml 17 liter Rinse 1 30-35 ° C 20 seconds-10 liter Rinse 2 30-35 ° C 20 seconds-10 liters Rinse 3 30-35 ° C. 20 seconds 350 ml 10 liters Dry 70-80 ° C. 60 seconds * Replenishment amount per 1 m ² of light-sensitive material (rinse 3 → 1 3 tank countercurrent method).

The composition of each processing liquid is as follows. [Color developer] [Tank liquid] [Replenisher] 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-aminoaniline 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 Add water 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 (700 g / l) 100 ml Sodium sulfite 17 g Ethylenediaminetetraacetic acid iron (III) ammonium 55 g Ethylenediaminetetraacetate disodium 5 g Ammonium bromide Add 40g water and add 1000ml pH (25 ℃) 6.0

[Rinse Solution] (The tank solution and the replenisher are the same) Ion-exchanged water (3 ppm each for calcium and magnesium)
Less than)

For the processed samples, B, G, R
The reflection densities of the three colors were measured, and their characteristic curves were obtained,
The following performance was evaluated. (1) Photographic property The logarithmic value of the reciprocal of the exposure amount that gives the density of the minimum density (Dmin) +0.5 is found from the characteristic curve, and this is taken as the sensitivity (S). (△
S ₁ ) was calculated. The larger the + value, the higher the feeling. Further, the density value at the position corresponding to the exposure amount of log E = 0.3 is obtained as the exposure amount from the sensitivity (S) point of each sample to the high exposure amount side, and this is set to 100 with the concentration of the sample 101 as a reference. , And the relative value of the concentration (D ₁ %) was calculated.
A value of more than 100 means a higher color density. Table 8 shows the result of the cyan image for these values. (2) Storage stability of sensitive material Two sets of each sample were prepared, one set was stored in a refrigerator at 5 ° C, and the other set was stored at 60 ° C and 40% RH for 7 days. After the completion, these two sets of samples were exposed to light as described above, processed and subjected to density measurement to obtain their characteristic curves. The sensitivity (S) was obtained from these characteristic curves in the same manner as in (1), and the difference (ΔS ₂ ) was calculated with the S value of the same sample stored in a refrigerator at 5 ° C. as a reference. Table 8 shows the results of the cyan image.

(3) Color Image Robustness One of the processed samples was stored under the condition of 80 ° C. for 1 month, and the density was measured again after the completion, and the density before the test was started. The density value after the end of the test at the exposure amount giving 1.5 was read. The other was exposed to a xenon fading tester (100,000 lux) for 9 days, and the density value after the end of the test was read at the exposure amount giving the density of 1.5 before the start of the test. The color image residual ratio (D ₂ and D ₃ %) was determined by calculating the ratio between the density of 1.5 before the test and the density after the test. The closer the value is to 100, the more robust the color image. The results are also shown in Table 8 for a cyan image.

(4) Color reproducibility Three-color separation exposure and processing were performed, and the cyan image obtained by exposure with the R filter was subjected to measurement of reflection density with the B, G, and R filters to obtain its characteristic curve. .. The minimum concentration on the characteristic curve measured with the R filter from these characteristic curves +
From an exposure amount giving a density of 0.5 to a high exposure amount side log E =
B and G respectively corresponding to an exposure dose of 0.3
The B and G concentrations on the characteristic curve measured with the filter were read. For these concentration values obtained for each sample, the difference (ΔD _B and ΔD _G ) from the concentration value of each sample was calculated with reference to Sample 101. The larger the negative value, the smaller the absorption of the cyan color image on the short wavelength side and the higher the saturation of the cyan color image, indicating that the color reproducibility is excellent.
The results are also shown in Table 8.

[0189]

[Table 8]

From the table, the samples 105 to 115 using the cyan coupler represented by the above general formula (1) of the present invention are:
When compared with the samples 101 to 104 using the comparative coupler, the coating flow rate was adjusted to make the coating amount of the coupler as low as 0.4 times the mole (0.275 mmol / m ² ). It can be seen that it exhibits a surprising color forming property that gives a high color density. Furthermore, even in terms of storage stability, color image fastness, and color reproducibility of the light-sensitive material, the couplers of the present invention have excellent performances exceeding those of the comparative couplers. You can see that. The result of measurement of the reflection spectrum of the cyan image obtained from the coupler represented by the general formula (1) of the present invention shows that the maximum absorption wavelength of Comparative Sample 101 is about 646 nm, whereas It was also found that the sample 108 of No. 1 had a wavelength of about 641 nm, and the other samples of the present invention were in the range of ± 3 nm of the sample 108 and were excellent as a spectral absorption region for color paper. It is considered that the absorption wavelength was shifted to a short wavelength and the absorption waveform was sharpened and the absorption on the short wavelength side was reduced, probably because the produced dye was associated in the light-sensitive material. In addition, it is considered that the association of the dyes contributes to the solidification of the color image. By the way, it was confirmed that the maximum absorption wavelength of the reflection spectra of Comparative Samples 103 and 104 having the same ureido group at the 2-position as that of the coupler of the present invention was about 690 nm and long-wave absorption. It is considered that this maximum absorption value is disadvantageous in terms of color reproduction of color paper and further in printing conditions relating to filters of color paper printers.
Further, JP-A-3-196037 describes a cyan coupler according to the present invention, and it is specified in Examples 1 and 2 that a high gradation and a maximum reached density (Dmax) are given. However, Example 1 of JP-A-3-196037
When comparing the samples 102 and 106 of the single-layer samples in Example 1 with the samples 104 (comparative sample) and 105 to 115 (invention) of the present example, the samples 105 to 11 of the present invention of the present example.
No. 5 gives a higher color density than Comparative Sample 104 even if the coating amount of the cyan coupler is reduced to 0.4 times the molar amount, so that the cyan coupler of the present invention (JP-A-3-196037).
(Cyan couplers described in JP-A No. 1993-1999) are also disclosed in JP-A-Hei 3 (1999) -34-A1 when a color developing solution, particularly N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline is used as a color developing agent. It can be understood that it gives a high color density that cannot be inferred from No. 196037.

Example 2 Based on the samples 101 and 108 prepared in Example 1, the yellow coupler (ExY) used in the first layer (blue-sensitive emulsion layer) was prepared according to the above general method of the present invention as shown in Table 9. A coupler represented by formula (Y) and a comparative coupler (1),
Samples 201 to 224 were prepared by replacing (2) with an equimolar amount and adjusting the weight ratio of the high boiling organic solvent / yellow coupler to 0.50 as in Sample 101.

[0192]

[Chemical 71]

Each of the prepared samples was exposed to light as described in Example 1, and the solution having the following processing steps and processing solution composition using a paper processor was used and before the start of continuous processing and 3 times the tank capacity of the color developing solution. Each treatment was performed after the running treatment was performed until the amount was replenished.

Treatment process Temperature Time Replenisher ^* Tank capacity Color development 38.5 ° C 45 seconds 73ml 10 liter Bleach-fix 35 ° C 45 seconds 60ml ^** 10〃 Rinse 35 ℃ 20 seconds-5〃 Rinse 35 ℃ 20 seconds-5〃 Rinse 35 ℃ 20 seconds 360 ml 5 〃 Dry 80 ℃ 60 seconds (* Replenishment amount per 1 m ^{2 of} photosensitive material) (Rins → 3 tank countercurrent method) (** In addition to the above 60 ml, rinse 120 ml was poured per 1 m ^{2 of} light-sensitive material)

The composition of each processing liquid is as follows.

Color developing solution Tank solution Replenishing solution Water 700 ml 700 ml Sodium triisopropylnaphthalene (β) sulfonate 0.1 g 0.1 g Ethylenediaminetetraacetic acid 3.0 g 3.0 g 1,2-dihydroxybenzene-4,6-disulfonic acid Disodium salt 0.5 g 0.5 g Triethanolamine 12.0 g 12.0 g Potassium chloride 6.5 g-Potassium bromide 0.03 g-Potassium carbonate 27.0 g 27.0 g Optical brightener (WHITEX 4B manufactured by Sumitomo Chemical) 1.0 g 3.0 g Sodium sulfite 0.1 g 0.1 g Disodium-N, N-bis (sulfonate ethyl) hydroxylamine 10.0 g 13.0 g N-ethyl-N- (β-methanesulfonamidoethyl)- 3-Methyl-4-aminoaniline sulfate 5.0 g 11.5 g Water was added 1000 ml 1000 ml pH (25 ° C) 10.0 11.0

Bleach-fixing solution Tank solution Replenishing solution Water 600 ml 150 ml Ammonium thiosulfate (700 g / l) 100 ml 250 ml Sodium sulfite 40 g 100 g Ethylenediaminetetraacetic acid iron (III) ammonium 55 g 135 g Ethylenediaminetetraacetic acid 5 g 12.5 g Ammonium bromide 40 g 75 g Nitric acid ( 67%) 30 g 65 g Water was added 1000 ml 1000 ml pH (25 ° C) (in acetic acid and aqueous ammonia) 5.8 5.6

Rinse liquid (tank liquid and replenisher are the same) Ion exchange water (calcium and magnesium are 3 ppm each)
Less than)

For the processed samples, the reflection densities of the three colors B, G, R were measured, and from the characteristic curves, the sensitivity (S) was changed from the sensitivity point to the high exposure amount side as the exposure amount, as in Example 1.
The density values at the exposure of g E = 0.3 were read, and the sensitivity difference (ΔS ₁ ) and the density difference (ΔD ₁ ) of the same sample before and after the start of continuous processing were determined. Table 9 shows the yellow image of the obtained results.

Next, using each of the fresh processing solutions, the sample transport section of the color developing tank was changed to reduce only the color development processing time from 45 seconds to 35 seconds, and the other processing time was not changed. Then, the sensitivity and the color density were read in the same manner as above. From these values, the difference (ΔS ₂ and Δ
D ₂ ) was determined.

Further, the sample for which the concentration measurement has been completed is
After the test was stored under the conditions of 70 ° C and 70% RH for 7 days, the density was measured again after the test, and the density after the test was read at the exposure dose giving the density of 1.5 before the test was started. %) Based on the density of 1.5 before the test was started. The results are also shown in Table 9. All numerical values are shown as absolute values, and the smaller the numerical value, the smaller the fluctuation in photographic property due to processing.

[0202]

[Table 9]

From the above table, samples 213 to 224 produced based on the sample 108 of Example 1 are samples 201 to 2 produced based on the sample 101 of Example 1 which is a comparative sample.
Compared with the respective samples of 12 corresponding yellow couplers, the variation in photographic properties (sensitivity, color density) was small even with the continuous processing of a lower complement amount than the processing of Example 1, and the color development processing time was 35. It can be seen that the development progresses quickly and the photographic property of processing for 45 seconds is reached even if the processing is shortened to seconds. From these results, in Samples 213 to 224 produced based on Sample 108, the cyan coupler was replaced with an equimolar amount with respect to Sample 101, and the coating flow rate of the fifth layer (red-sensitive emulsion layer) was adjusted to adjust the coupler coating amount. Since the sample was reduced to 0.4 times the molar amount, the coating amount of the entire fifth layer was small, so the film thickness was naturally thin, and therefore the first layer (blue It is considered that the sensitive emulsion layer) can be easily developed and can quickly reach a certain photographic property by reducing the film thickness of the upper layer, and the fluctuation of the photographic property in continuous processing can be reduced. Further, it should be noted that it is generally desirable to use a coupler having a high coupling reaction rate as the yellow coupler in order to enable rapid processing and good processing stability in rapid processing. The relative coupling speed is defined in Kaisho 61-80249, and the relative coupling speed is 0.
The use of a yellow coupler having a value of 3 or more, preferably 0.5 or more is disclosed. According to the definition, Y-5, Y-10, and the comparative coupler (1) used in this example have relative coupling speeds of 0.65 and 0.8, respectively.
0 and 1.46. However, the value of Y-48 of the present invention obtained by the same measurement method is as low as 0.18. Nevertheless, the comparative sample 221 in which the coating amount of the fifth layer (red-sensitive emulsion layer) was reduced showed good continuous processing, and similarly in the processing in which the color development processing time was shortened, photographic characteristics were also good. It is obvious from comparison with other samples of the present invention. As described above, the yellow coupler that can be used in combination with the cyan coupler represented by the above general formula (1) of the present invention has a great advantage that it can be selected in a wide range including low activity couplers and can be used. The yellow coupler represented by formula (Y) of the present invention is a comparative coupler.
Samples 201 to 210, 213 to 222 and Sample 21 are superior in color image fastness when compared with (1) and (2).
It is clear from the comparison with 1,212,223,224. In particular, the yellow coupler represented by the general formula (Y) of the present invention has a thickness of the red-sensitive emulsion layer, which is the upper layer (the layer farther from the support) than the layer coated with the coupler (blue-sensitive emulsion layer). It can be seen that although the color image residual rate does not change despite the thinning, the comparative coupler tends to decrease the color image residual rate. When the density of the uncolored part (fog part) of the sample after the test is compared with the density of the uncolored part before the test in terms of B density, samples 213 to 224
Was also found to be lower in concentration than the corresponding samples of Samples 201-212. Samples 213 to 224 are samples 201
It is considered that the thinner layer compared to ˜212 results in less stain due to the smaller residual amount of the drug incorporated in the film by the treatment.

Example 3 Based on the samples 101, 108 and 112 prepared in Example 1, the high boiling point organic solvent S-6 of the fifth layer (red sensitive emulsion layer) was used.
/ Cyan coupler weight ratio is 2.00 and 1.5 respectively
Sample 30 adjusted to 0, 1.00, 0.20
1-312 were produced. These prepared samples are used in Example 1.
The same performance evaluation was performed by applying the exposure described in 1. However, the treatment was carried out using the treatment liquid after the running described in Example 2, and the photographic properties and color reproducibility were based on the sample having the highest S-6 / cyan coupler weight ratio. The results are shown in Table 10.

[0205]

[Table 10]

From the table, the coupler represented by the general formula (1) of the present invention has a weight ratio of S-6 / cyan coupler of 1.50.
From 0.2 to 0.20, there is almost no change in photographic sensitivity, and the color density is slightly increased to a substantially constant value.
There is almost no change in the storage stability of the light-sensitive material. Similarly, the color image fastness does not change and shows high fastness. It was revealed that the color reproducibility was slightly improved. On the other hand, in the comparative sample, when the weight ratio is reduced, the photographic properties, the storage stability of the light-sensitive material, the color image fastness, and the color reproducibility are deteriorated. In this respect, the general formula (1) of the present invention
It is clear that the coupler represented by
This fact is considered to be due to the fact that the dye formed from the coupler represented by the general formula (1) of the present invention was associated in the light-sensitive material film as described in Example 1 above.

The high boiling organic solvent S-6 was added to S-3 and S.
It was confirmed that similar results were obtained when coating was carried out by replacing -9, S-11 and S-13 with each other and the same performance evaluation as described above was carried out.

Example 4 In the processing used in Example 2, the temperature and time of color development in the processing step, and N-ethyl-N- (β-methanesulfone, which is a color developing agent of the tank liquid composition of the color developer, were used. The concentrations and pH of amidoethyl) -3-methyl-4-aminoanilinosulfate were changed as shown in Table 11, and samples 101, 105 and 110 prepared in Example 1 and samples 205 and 206 prepared in Example 2 were changed. , 209,
217, 218 and 221 were used to perform the batch development with the exposure described in Example 1.

[0209]

[Table 11]

The treated sample was subjected to concentration measurement in the same manner as in the previous example to obtain its characteristic curve. From these characteristic curves, the color density value of the photographic property described in (1) of Example 1 was obtained, and the color density of the sample obtained by processing before the start of the running processing in Example 2 above was used as a standard. Then, the difference in the color density was calculated. The results for the yellow and cyan color images are shown in Table 12 as ΔD _B and ΔD _R.

[0211]

[Table 12]

From Table 12, samples 105, 110 and 2 using the cyan coupler represented by the general formula (1) of the present invention are shown.
17, 218, 221 are comparative samples 101, 205, 2
Compared to 06 and 209, stable photographic performance (color development) against changes in color developing agent concentration during color development (Processes A and B), changes in pH of color developer (Processes C and D), and changes in processing temperature of color developer Concentration).
In particular, it can be seen that in the yellow coupler of the blue-sensitive emulsion layer located in the lowermost layer (on the side closer to the support), the change in photographic property due to the change in processing factors is small. It is considered that this is because the coating flow rate of the cyan coupler-containing layer (fifth layer) located in the upper layer (the side farther from the support) was greatly reduced and the film thickness was reduced. Further, as can be seen from the sample 221, the low activity yellow coupler has a small process variation as described in Example 2 above, and it is clear that this type of coupler can be used, which is represented by the general formula (1) of the present invention. It is understood that the combination of the cyan coupler represented by the formula (Y) and the yellow coupler represented by the general formula (Y) exhibits an excellent effect.

Example 5 A multilayer color photographic paper having the following layer constitution was prepared on a paper support having both surfaces laminated with polyethylene and the surface of which was subjected to corona discharge treatment. The coating liquid was prepared as follows.

Preparation of coating liquid for first layer Yellow coupler (ExY) 60.0 g, anti-fading agent (Cp
d-1) 28.0 g and anti-fading agent (Cpd-6) 25.
150 g of ethyl acetate and solvent (Solv-3) 1.
0 cc and 3.0 cc of solvent (Solv-4) were added and dissolved, and this solution was added with sodium dodecylbenzenesulfonate 10
% Gelatin aqueous solution (450 cc) and then dispersed with an ultrasonic homogenizer, and the resulting dispersion is a silver chlorobromide emulsion containing the following blue-sensitizing dye (silver bromide 0.7 mol%) 420
First, a coating solution for the first layer was prepared by mixing and dissolving with g.

The coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. 1,2-Bis (vinylsulfonyl) ethane was used as the gelatin hardening agent for each layer.

The following were used as the spectral sensitizing dye in each layer. Blue-sensitive emulsion layer; anhydro-5-5'-dichloro-3,
3'-disulfoethylthiacyanine hydroxide green-sensitive emulsion layer; anhydro-9-ethyl-5,5'-diphenyl-3,3'-disulfoethyloxacarbocyanine hydroxide red-sensitive emulsion layer; 3,3 ' -Diethyl-5-methoxy-
9,11-Neopentyl thiadicarbocyanine iodide

The following materials were used as stabilizers for each emulsion layer. 1- (2-acetamino-phenyl) -5-mercaptotetrazole and 1-methyl-2-acetylamino-5-mercapto-
1,3,4-triazole and 2- (p-carboxyphenyl) -5-mercapto-
7: 2: 1 mixture of 1,3,4-oxadiazole (molar ratio)

The following materials were used as the anti-irradiation dye. [3-carboxy-5-hydroxy-4- (3- (3-
Carboxy-5-oxo-1- (2,5-bisulfonatophenyl) -2-pyrazolin-4-ylidene) -1-propenyl) -1-pyrazolyl] benzene-2,5-disulfonate-sodium salt N, N ′-(4,8-Dihydroxy-9,10-dioxo-3,7-disulfonate anthracene-1,5-diyl) bis (aminomethanesulfonate) -tetrasodium salt [3-cyano-5-hydroxy -4- (3- (3-cyano-5-oxo-1- (4-sulfonatephenyl)-
2-pyrazolin-4-ylidene) -1-pentanyl)-
1-Pyrazolyl] benzene-4-sulfonate-sodium salt

(Layer Structure) The composition of each layer is shown below. Numbers represent coating amount (g / m ² ). The silver halide emulsion represents the coating amount in terms of silver.

Support: A paper support laminated on both sides with polyethylene and the surface of which has been subjected to corona discharge treatment.

First Layer (Blue Sensitive Layer) The above-mentioned silver chlorobromide emulsion (AgBr 0.7 mol%, cubic, average grain size 0.9 μm) 0.29 gelatin 1.80 yellow coupler (ExY) 0.60 fading Inhibitor (Cpd-1) 0.28 Anti-fading agent (Cpd-6) 0.25 Solvent (S-7) 0.01 Solvent (S-18) 0.03

Second Layer (Color Mixing Prevention Layer) Gelatin 0.80 Color mixing inhibitor (Cpd-2) 0.030 Color mixing inhibitor (Cpd-8) 0.030 Solvent (S-8) 0.03 Solvent (S- 6) 0.09

Third Layer (Green Sensitive Layer) The above-mentioned silver chlorobromide emulsion (AgBr 0.7 mol%, cubic, average grain size 0.45 μm) 0.18 gelatin 1.86 magenta coupler (ExM) 0.23 fading Inhibitor (Cpd-3) 0.15 Anti-fading agent (Cpd-4) 0.10 Anti-fading agent (Cpd-7) 0.15 Solvent (S-8) 0.2 Solvent (S-6) 0.03

Fourth Layer (Color Mixing Prevention Layer) Gelatin 1.70 Color mixing inhibitor (Cpd-2) 0.03 Color mixing inhibitor (Cpd-8) 0.04 Ultraviolet absorber (UV-1) 0.45 Ultraviolet absorption Agent (UV-2) 0.23 Solvent (S-8) 0.05 Solvent (S-6) 0.05

Fifth Layer (Red Sensitive Layer) The above-mentioned silver chlorobromide emulsion (AgBr 4 mol%, cubic, average grain size 0.5 μm) 0.21 gelatin 1.80 cyan coupler (ExC-1) 0.26 Cyan coupler (ExC-2) 0.12 Anti-fading agent (Cpd-6) 0.16 Solvent (S-8) 0.12 Solvent (S-6) 0.07 Color accelerator (Cpd-5) 0.15

Sixth Layer (UV Absorbing Layer) Gelatin 0.70 UV Absorbing Agent (UV-1) 0.26 UV Absorbing Agent (UV-2) 0.07 Solvent (S-8) 0.30 Solvent (S- 6) 0.09

Seventh Layer (Protective Layer) Gelatin 1.07

(ExY) Yellow coupler (Y-2
1) (ExM) magenta coupler 7-chloro-6-tert-butyl-3- (dodecylsulfonylpropyl) -1H-pyrazolo [5,1-C] -1,
2,4-triazole (ExC-1) cyan coupler 2-pentafluorobenzamide-4-chloro-5 [2
-(2,4-Di-tert-amylphenoxy) -3-methylbutylamidophenol (ExC-2) cyan coupler 2,4-dichloro-3-ethyl-6- [α- (2,4-
Di-tert-amylphenoxy) butyramide] phenol

(Cpd-1) Antifading agent Poly-tert-butylacrylamide (average molecular weight 80,
000) (Cpd-2) anti-color mixture 2,5-di-tert-octylhydroquinone (Cpd-3) anti-fading agent 7,7'-dihydroxy-4,4,4 ', 4'-tetramethyl-2, 2'-spirochroman (Cpd-4) anti-fading agent N- (4-dodecyloxyphenyl) -thiomorpholine-1,1-dioxide (Cpd-5) color development accelerator p- (p-toluenesulfonamide) phenyl-dodecane (Cpd-6) Anti-fading agent 2 ', 4'-di-tert-amylphenyl-3,5-di-
tert-Butyl-4-hydroxybenzoate (Cpd-7) anti-fading agent 4,4'-butylidene-bis (3-methyl-6-tert-)
Butylphenol) (Cpd-8) Color mixing inhibitor 2,5-bis (1 ′, 1′-dimethyl-4′-hexyloxycarbonylbutyl) hydroquinone

(UV-1) UV absorber 2- (2-hydroxy-3,5-di-tert-amylphenyl) benzotriazole (UV-2) UV absorber 2- (2-hydroxy-3,5-) Di-tert-butylphenyl) benzotriazole

The manufactured sample is designated as 501. Subsequently, the cyan couplers ExC-1 and ExC-2 used in the fifth layer (red sensitive layer) were used as the cyan couplers represented by the above general formula (1) of the present invention, Sample 502 was (10) and Sample 503 was 503. Is
(25) is replaced with an equimolar amount, the weight ratio of the high-boiling organic solvent / cyan coupler is adjusted to 0.50, which is the same as that of the sample 501, and only the coating flow rate is adjusted without changing the others, and only the fifth layer is coated with the cyan coupler. A sample was prepared by coating so that the amount was 0.35 times the molar amount (0.22 mmol / m ² ).

These samples 501 to 503 were exposed by the method described in Example 1, and the samples which were separately imagewise exposed to the above light-sensitive material were subjected to color development in the following processing steps using a paper processor. Continuous processing (running test) was carried out until the tank was replenished with twice the tank capacity, and then processed to obtain a color image.

Treatment process Temperature Time Replenisher ^* Tank capacity Color development 35 ° C 45 seconds 161 ml 17 liters Bleach fixing 30-36 ° C 45 seconds 215 ml 17 liters Stable 1 30-37 ° C 20 seconds -10 liters Stable 2 30 〜37 ℃ 20 seconds-10 liters Stable 3 30-37 ℃ 20 seconds -10 liters Stable 4 30-37 ℃ 30 seconds 248ml 10 liters Dry 70-85 ℃ 60 seconds * Replenishment amount per 1 m ^{2 of} photosensitive material (stable (4 tank countercurrent system from 4 to 1)

The composition of each processing liquid is as follows. [Color developer] [Tank liquid] [Replenisher] Water 800 ml 800 ml Ethylenediaminetetraacetic acid 2.0 g 2.0 g 5,6-dihydroxybenzene-1,2,4-trisulfonic acid 0.3 g 0.3 g tri Ethanolamine 8.0 g 8.0 g Sodium chloride 1.4 g-Potassium carbonate 25 g 25 g N-Ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulphate 5.0 g 7.0 g Diethylhydroxylamine 4.2g 6.0g Optical brightener (4,4'-diaminostilbene type) 2.0g 2.5g Add water 1000ml 1000ml pH (25 ° C) 10.05 10.45

[Bleach-fixing solution] (tank solution and replenisher are the same) Water 400 ml Ammonium thiosulfate (700 g / l) 100 ml Sodium sulfite 17 g Ethylenediaminetetraacetic acid iron (III) ammonium 55 g Ethylenediaminetetraacetate disodium 5 g Glacial acetic acid 9 g Add water to add 1000 ml pH (25 ℃) 5.40

[Stabilizer] (Same as tank solution and replenisher) Formalin (37%) 0.1 g Formalin-sulfite adduct 0.7 g 5-chloro-2-methyl-4-isothiazolin-3-one 0.02 g 2-Methyl-4-isothiazolin-3-one 0.01 g Copper nitrate 0.005 g Water was added to 1000 ml pH (25 ° C.) 4.0

The processed samples were subjected to the same performance evaluation as in Example 1 by measuring the reflection densities of B, G and R colors. As a result, the samples 502 and 503 using the cyan coupler represented by the general formula (1) of the present invention are comparative sample 501.
Compared to, the coating flow rate was greatly reduced and the coupler coating amount was reduced to 0.
Despite the 35-fold molar amount, the photographic sensitivity and the color density were slightly high. In addition, it was confirmed that there was a remarkable improving effect on the storability of the light-sensitive material with time, color image fastness (fastness particularly under high temperature conditions), and color reproducibility. It was also confirmed that the color image fastness due to irradiation with xenon light was also excellent. Furthermore, as a result of various treatments with different treatment factors carried out in Example 4, a sample using a combination of the cyan coupler represented by the general formula (1) of the present invention and the yellow coupler represented by the general formula (Y) was used. It was also confirmed that in 502 and 503, the variation in the color density of both cyan and yellow color images was smaller than that of the comparative sample 501, and stable performance was obtained.

[0238]

The combined use of the cyan coupler represented by the general formula (1) and the yellow coupler represented by the general formula (Y) gives a high cyan color density, and the stability of the photosensitive material with time and the color image fastness. It is possible to provide a silver halide color photographic light-sensitive material which has excellent color reproducibility and can be used even in a low-activity yellow coupler, and has a small variation in photographic property with respect to changes in processing factors.

FIG. 28

Claims (3)

[Claims] 1. A multilayer silver halide color photographic light-sensitive material comprising a silver halide emulsion layer containing a cyan coupler, a silver halide emulsion layer containing a magenta coupler, and a silver halide emulsion layer containing a yellow coupler on a reflective support. 2. A multilayer silver halide color photographic light-sensitive material containing the coupler represented by the general formula (1) as the cyan coupler and the coupler represented by the general formula (Y) as the yellow coupler. General formula (1) In the general formula (1), Y is a nonmetallic atom group necessary for forming a 3- to 8-membered heterocycle with N, L is an alkylene group, R ¹ is an aryl group, and Z is a hydrogen atom or a coupling. Each leaving group is represented. However, in the heterocycle, the carbonyl group does not directly bond to N. General formula (Y) In the general formula (Y), R ₁ is an alkyl group, R ₂ is a hydrogen atom, a halogen atom, an alkoxy group, an aryloxy group, an alkyl group or a dialkylamino group, and R ₃ is a group which can be substituted on the benzene ring. , X represents a hydrogen atom or a coupling-off group, and γ represents an integer of 0 to 4, respectively. However, when γ is plural, plural R ₃ may be the same or different. 2. The coating amount of all cyan couplers in the layer containing the cyan coupler represented by the general formula (1) does not exceed 0.5 × 10 ⁻³ mol per 1 square meter. Item 1. The multilayer silver halide color photographic light-sensitive material according to Item 1. 3. The ratio of the total weight of the high boiling point organic solvent in the same layer to the total weight of the coupler in the layer containing the cyan coupler represented by the general formula (1) is 1.5 or less. Item 3. The multilayer silver halide color photographic light-sensitive material according to Item 1 or 2.