JPH05165169A - Multilayer silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve cyan and yellow color development performances, storage stability of the photosensitive material, color image fastness, color reproduction performance, and processability by incorporating a specified phenol type cyan coupler and a specified acylacetamido type yellow coupler. CONSTITUTION:The silver halide emulsion layer containing the cyan coupler contains the cyan coupler represented by formula I and the silver halide emulsion layer containing the yellow coupler contains the acylacetamido type yellow coupler having an acyl group represented by formula II. In formulae I and II, Y is a nonmetallic atomic group necessary to form a prescribed ring together with the N atom; L, is alkylene: R<1> is aryl: Z is H or a group to be released by coupling; and Q is a nonmetallic atomic group necessary to form a prescribed ring together with the C atom.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a silver halide having a specific cyan coupler and a specific yellow coupler, which have improved color forming properties and provide stable photographic performance, and have improved color image fastness and color turbidity. The present invention relates to a color photographic light-sensitive material.

[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. 7, 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 have the disadvantage that their fastness is large, especially when they are stored under high temperature or high temperature and high humidity conditions. 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 in order to obtain the cyan density required for the light-sensitive material.

On the other hand, the same phenolic coupler is the 2-ureido-5-acylamino phenolic coupler. As a typical coupler, for example, US Pat.
446,622, 4,333,999, 4,775,616, 4,451,559, 4,427,767, and JP-A-61-42658. The couplers that are used are listed. 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. P- at the second position described in U.S. Pat. No. 4,333,999.
Although some couplers have a cyanophenylureido group and a dye formed like a coupler having an alkylacylamino group substituted at the 5-position to associate with each other to cause bathochromic shift and to improve color image fastness, there are some couplers. Since their spectral absorption maximum wavelength (λmax) is long-wavelength absorption, they are beginning to be used in negative photosensitive materials, but are not currently used in positive systems, especially color paper systems. .. In order to obtain a higher absorption concentration by utilizing the association of the forming dyes, for example, European Patent Publication Nos. 271,323 and 27,
Nos. 1,324 and 271,325 disclose couplers having a p-cyanophenylureido group at the 2-position and an acylamino group at the 5-position, all of which are for negative photosensitive materials. The purpose is to improve the coupling activity and spectral absorption characteristics. 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. However, it is not preferable for color reproduction, and there are problems such as changes in color density when thinned, fluctuations in spectral absorption characteristics and color image fastness due to storage conditions after processing, and fluctuations in photographic properties during storage of photosensitive materials. It turned out that there is.

Further, the use of a phenolic coupler having a ureido group at the 2-position in a color paper system is described in, for example, JP-A-60-256142 and JP-A-62-27344.
62-43540, 62-115157, 6
2-153953, 62-174757, 62
-237451, JP-A-1-177546, 1-
Nos. 117547 and 2-27344 describe a phenolic coupler having a ureido group, but no description supporting the effect of these couplers is found at all. Moreover, when these phenolic couplers having an ureido group described above are actually used for color paper, the coupling activity, color reproducibility and color image fastness are not sufficient, and the photographs during storage and continuous processing of the light-sensitive material are shown. It has become clear that there is a problem in that the stability of the photographic property, especially the photographic property of 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 the use of these couplers is a color negative type single layer, and although it is shown that the color image fastness is improved, there is almost no improvement effect on the color developability. The effect in the system and the relation with other layers in the multi-layer system cannot be analogized. Further, JP-A-3-196037 describes a coupler relating to the present invention. However, the practical use 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 in the above, and its specific effect is unknown. .. The color paper system described has 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 basic mother nucleus structure is different from the coupler and the like according to the present invention, and the coupler is a single layer system. Therefore, it cannot be inferred from these, let alone the layered system of color paper.

On the other hand, as the yellow coupler, an acylacetamide coupler represented by benzoylacetolinide type and pivaloylacetanilide type is generally used. Compared to the latter, the former is generally used in photographic light-sensitive materials that require high sensitivity because the coupling activity with oxidized color developing agent is generally high and the molecular absorption coefficient of the yellow dye produced is rather large, and the latter is It is mainly used for color paper and color reversal system because the yellow dye has excellent spectral absorption characteristics and color image fastness. However, in the pivaloyl acetanilide type coupler, although the spectral absorption characteristics of the yellow color image and the fastness of the color image are excellent, the coupling activity with the oxidized color developing agent during color development is low, and the yellow dye formed is It has a drawback that the molecular extinction coefficient is small. Here, the high coupling reactivity of the coupler and the large molecular extinction coefficient of the resulting dye allow high sensitivity, high gradation and high color density, resulting in so-called high color developability.
In addition, the excellent spectral absorption characteristics in a yellow image are
For example, it means that the absorption density on the long wavelength side of the spectral absorption is low, and the absorption characteristics are small in unnecessary absorption in the green region. Therefore, there has been a demand for the development of a yellow coupler which gives a high coloring density due to a high molecular extinction coefficient of a dye to be produced, and has excellent spectral absorption characteristics of a color image and excellent fastness of a color image.

On the other hand, as an acyl group of an acylacetanilide type coupler, US Pat. No. 3,265,506 discloses a pivaloyl group, 7,7-dimethylnorbornane-1-carbonyl group, 1-methylcyclohexane-1-carbonyl group and the like. However, JP-A 47-26133 discloses a cyclopropane-1-carbonyl group, a cyclohexane-1-carbonyl group and the like. However, these couplers have inferior coupling reactivity, low molecular extinction coefficient of dye, inferior spectral absorption property of color image, or inferior color image fastness. Was there. Furthermore, in the benzoylacetanilide type and pivaloylacetanilide type couplers, which represent the acylacetanilide type couplers, a coupler having an oil-soluble diffusion-resistant group in the molecule is mixed with a high-boiling organic solvent and dissolved, and a finely dispersed dispersion is treated with halogen. When a color light-sensitive material is prepared by mixing with silver halide, there is also a drawback that the above-mentioned color developability is deteriorated when the amount of the high boiling point organic solvent added per unit weight of the coupler is low.

[0007]

SUMMARY OF THE INVENTION It is, therefore, a first object of the present invention to provide a silver halide color photographic light-sensitive material which provides high cyan and yellow color density and high color image fastness. A second object is to provide a silver halide color photographic light-sensitive material in which the coating amount of the cyan coupler in the silver halide emulsion layer containing the cyan coupler is reduced to make the layer thin and the hue does not change due to storage after processing. Especially. A third object of the present invention is to provide a silver halide color photographic light-sensitive material capable of obtaining stable photographic performance with a small process variation even when a process for shortening the color development process time or a continuous process is carried out.

[0008]

The above object can be achieved by the following silver halide color photographic light-sensitive material. That is, in a multilayer silver halide color photographic 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 silver halide emulsion layer containing a cyan coupler contains a coupler represented by the general formula (1) as a cyan coupler, and the silver halide emulsion layer containing the yellow coupler contains a group represented by the general formula (A) as a yellow coupler. A multilayer silver halide color photographic light-sensitive material containing an acylacetamide type coupler having an acyl group. General formula (1)

[0009]

[Chemical 3]

In the formula, Y is a non-metal atom group necessary for forming a 3- to 8-membered heterocycle with N, L is an alkylene group, R ¹ is an aryl group, Z is a hydrogen atom or coupling-off. The groups are respectively represented. However, in the heterocycle, the carbonyl group does not directly bond to N. General formula (A)

[0011]

[Chemical 4]

In the formula, R ₁ represents a monovalent group. Q has 3 to 5 membered hydrocarbon ring or at least one hetero atom selected from N, O, S and P in the ring together with C. 3
Represents a group of non-metal atoms necessary to form a 5-membered heterocycle. However, R ₁ is not a hydrogen atom and does not combine with Q to form a ring.

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

[0014]

[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).

[0020]

[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, even if it is 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.

[0024]

[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.

[0026]

[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

[0031]

[Chemical 9]

[0032]

[Chemical 10]

Examples of the group represented by L.

[0034]

[Chemical 11]

[0035]

[Chemical 12]

Examples of the group represented by R ¹ .

[0037]

[Chemical 13]

[0038]

[Chemical 14]

Examples of groups represented by Z.

[0040]

[Chemical 15]

[0041]

[Chemical 16]

[0042]

[Chemical 17]

[0043]

[Chemical 18]

[0044]

[Chemical 19]

[0045]

[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.

[0047]

[Table 1]

[0048]

[Table 2]

Typical synthetic routes for the cyan coupler represented by the general formula (1) are shown below.

[0050]

[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 a cyan coupler including the cyan coupler of the present invention is introduced into a light-sensitive material, no high boiling organic solvent is used, or a high boiling organic solvent is used in a weight ratio of 1.5 or less based on the weight of the coupler. Preferably. More preferably, the high boiling organic solvent can be used in the range of 0.1 to 1.0. 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).
It is preferably added to the red-sensitive emulsion layer. In this case, the cyan coupler is used per mol of photosensitive silver halide,
Usually, 0.002 to 2 mol is used, preferably 0.0
Use 1 to 1 mole. Particularly preferred is 0.1 to 0.5 mol. The coating amount per square meter does not exceed 0.5 mmol. Preferably 0.
It is from 01 to 0.4 mmol. Particularly preferably 0.
It is in the range of 01 to 0.3 mmol. The cyan coupler of the present invention may be used alone or in combination of two or more kinds. Known 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 color (1) is preferably 50 mol% or more of the total amount of the cyan couplers, more preferably 75% or more.

Next, the acylacetamide type yellow coupler having the group represented by the general formula (A) of the present invention as an acyl group will be described. The acylacetamide type yellow coupler of the present invention is preferably represented by the following general formula (Y).

[0054]

[Chemical formula 22]

In the formula (Y), R ₁ is a monovalent substituent except a hydrogen atom, and Q is selected from C and a 3- to 5-membered hydrocarbon ring or at least one N, S, O, P. R ₂ represents a hydrogen atom, a halogen atom (F, Cl, Br, I or less) of the formula (Y), which represents a non-metal atom group necessary for forming a 3- to 5-membered heterocycle containing a hetero atom in the ring. The same shall apply to the above), an alkoxy group, an aryloxy group, an alkyl group or an amino group, and R ₃ is a group capable of substituting on the benzene ring,
X represents a hydrogen atom or a group capable of leaving by a coupling reaction with an oxidized product of an aromatic primary amine developer (hereinafter referred to as a leaving group), and k represents an integer of 0 to 4, respectively. However, when k is plural, plural R ₃ may be the same or different. Here, as an example of R ₃ , a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group,
Carbonamido group, sulfonamide group, carbamoyl group, sulfamoyl group, alkylsulfonyl group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, alkoxysulfonyl group, acyloxy group,
Nitro group, heterocyclic group, cyano group, acyl group, amino group,
There are an imide group, an alkylsulfonyloxy group, an arylsulfonyloxy group, a carboxyl group, a sulfo group, and a hydroxyl group (hereinafter referred to as the substituent group A), and examples of the leaving group include a heterocyclic group bonded to the coupling active position with a nitrogen atom. , Aryloxy group, arylthio group, acyloxy group, alkylsulfonyloxy group, arylsulfonyloxy group, heterocyclic oxy group and halogen atom. When the substituent in the formula (Y) is an alkyl group or contains an alkyl group, unless otherwise specified, the alkyl group may have a linear, branched or cyclic unsaturated bond even if it is substituted. It means an alkyl group which may be included. When the substituent in formula (Y) is an aryl group or includes an aryl group, the aryl group means a monocyclic or condensed ring aryl group which may be substituted, unless otherwise specified. When the substitution in formula (Y) is a heterocyclic group or includes a heterocyclic group, unless otherwise specified, the heterocyclic group is at least one selected from O, N, S, P, Se and Te.
It means a 3- to 8-membered optionally substituted monocyclic or condensed-ring heterocyclic group containing 4 heteroatoms in the ring.

The substituents preferably used in formula (Y) will be described below. In formula (Y), R ₁ is preferably a halogen atom, a cyano group, or the total number of carbon atoms (hereinafter abbreviated as C number) 1 to 30 which may be substituted.
A monovalent group (for example, an alkyl group or an alkoxy group) or a monovalent group having a C number of 6 to 30 (for example, an aryl group or an aryloxy group), and the substituent thereof is, for example, a halogen atom, an alkyl group or an alkoxy group. Group, nitro group, amino group, carbonamido group, sulfonamide group, acyl group. In formula (Y), Q is preferably 3 together with C.
A hydrocarbon ring having a C number of 3 to 30 which may be substituted with any of 5 to 5 members, or a C ring having a C number of 2 to 30 containing at least one hetero atom selected from N, S, O and P in the ring. Represents a group of non-metal atoms necessary to form a heterocycle. Further, the ring formed by Q together with C may contain an unsaturated bond in the ring. Examples of the ring formed by Q together with C include cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclopropene ring, cyclobutene ring, cyclopentene ring, oxetane ring, oxolane ring, 1,3-dioxolane ring, thietane ring, thiolane ring, pyrrolidine. There is a ring. Examples of the substituent include a halogen atom, a hydroxyl group, an alkyl group, an aryl group, an acyl group, an alkoxy group, an aryloxy group, a cyano group, an alkoxycarbonyl group, an alkylthio group and an arylthio group. In formula (Y), R ₂ is preferably a halogen atom, an optionally substituted alkoxy group having 1 to 30 C atoms, an aryloxy group having 6 to 30 C atoms, an alkyl group having 1 to 30 C atoms, or It represents an amino group having a C number of 0 to 30, and examples of the substituent include a halogen atom, an alkyl group, an alkoxy group, and an aryloxy group. In formula (Y), R ₃ is preferably a halogen atom, any of which may be substituted, an alkyl group having 1 to 30 C atoms, an aryl group having 6 to 30 C atoms, an alkoxy group having 1 to 30 C atoms, C Number 2-30 alkoxycarbonyl group, C number 7-30 aryloxycarbonyl group, C number 1-30 carbonamido group, C number 1-30 sulfonamide group, C number 1-30 carbamoyl group, C Number 0-3
0 sulfamoyl group, C 1-30 alkylsulfonyl group, C 6-30 arylsulfonyl group, C 1
To 30 ureido group, C number 0 to 30 sulfamoylamino group, C number 2 to 30 alkoxycarbonylamino group, C number 1 to 30 heterocyclic group, C number 1 to 30 acyl group, C number It represents an alkylsulfonyloxy group of 1 to 30 or an arylsulfonyloxy group of 6 to 30 carbon atoms, and the substituent thereof is, for example, a substituent selected from the above substituent group A. In the formula (Y), k preferably represents an integer of 1 or 2, and the substitution position of R ₃ is

[0057]

[Chemical formula 23]

On the other hand, the meta position or the para position is preferred.
In 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, X is preferably a 5- to 7-membered monocyclic or condensed heterocyclic group which may be substituted, and examples thereof include succinimide, maleimide, phthalimide, Diglycolimide, pyrrole, pyrazole, imidazole, 1,2,4-triazole, tetrazole, indole, indazole, benzimidazole, benzotriazole, imidazolidine-2,4-dione, oxazolidine-2,4-dione, thiazolidine-2 , 4-dione, imidazolidine-
2-one, oxazolidin-2-one, thiazolidine-
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 heterocycles include the substituents selected from the above substituent group A. When X represents an aryloxy group, X preferably has a C number of 6 to 30.
Which represents an aryloxy group, and may be substituted with a group selected from the substituent group mentioned when X is a heterocycle. Examples of the substituent of 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 arylsulfonyl group. Base,
Alternatively, a cyano group is preferable.

Substituents particularly preferably used in formula (Y) are described below. R ₁ is particularly preferably a halogen atom or an alkyl group, preferably a linear alkyl group having a C number of 1 to 5, and most preferably a methyl, ethyl or n-propyl group. Q is particularly preferably a nonmetallic atom group ring made with C to form a hydrocarbon ring 3-5 membered, e.g., - [CR _{2] 2} -, -
[CR ₂ ] ₃ − and − [CR ₂ ] ₄ −. Where R
Represents a hydrogen atom, a halogen atom or an alkyl group.
However, a plurality of R and CR ₂ may be the same or different. Q is most preferably with C to bind to form a 3-membered ring - [CR _{2] 2} -. 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, a methoxy group or a trifluoromethyl 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. A group, a sulfamoyl group or a sulfonamide group. X is particularly preferably a 5-membered heterocyclic group bonded to the coupling active position at a nitrogen atom (eg, imidazolidin-2,4-dione-3-yl,
Oxazolidin-2,4-dione-yl) or an aryloxy group, most preferably imidazolidine-
It is a 2,4-dione-3-yl group. The coupler represented by the formula (Y) has substituents R ₁ , Q, X or

[0060]

[Chemical formula 24]

In, a dimer or a multimer of more than one may be formed by bonding to each other via a divalent or higher valent group.
In this case, the number of carbon atoms shown in each of the above substituents may be out of the specified range. Specific examples of each substituent in the formula (Y) are shown below.

[0062]

[Chemical 25]

[0063]

[Chemical formula 26]

[0064]

[Chemical 27]

[0065]

[Chemical 28]

[0066]

[Chemical 29]

[0067]

[Chemical 30]

[0068]

[Chemical 31]

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

[0070]

[Chemical 32]

[0071]

[Chemical 33]

[0072]

[Chemical 34]

[0073]

[Chemical 35]

[0074]

[Chemical 36]

[0075]

[Chemical 37]

[0076]

[Chemical 38]

[0077]

[Chemical Formula 39]

[0078]

[Chemical 40]

[0079]

[Chemical 41]

[0080]

[Chemical 42]

[0081]

[Chemical 43]

[0082]

[Chemical 44]

[0083]

[Chemical 45]

The yellow coupler represented by the general formula (Y) is prepared by synthesizing the carboxylic acid represented by the general formula [A] and then using a conventionally known synthesis method (for example, JP-A-51-1026).
No. 36 specification). General formula [A]

[0085]

[Chemical 46]

The carboxylic acid represented by the general formula [A] is
J.Chem.Soc. (C), 1968, 2548, J.Am.Chem.Soc., 1934,
56, 2710, Synthesis, 1971, 258, J. Org. Chem., 1978, 4
3, 1729, CA, 1960, 66, 18533y and the like.

The acylacetamide type coupler having the group represented by the general formula (A) of the present invention as an acyl group is preferably added to the light-sensitive silver halide emulsion layer or a layer adjacent thereto in the light-sensitive material. It is particularly preferable to add it to the photographic silver halide. The total amount added to the light-sensitive material is 1 × 10 ^{−3 to} 1.2 g / m ² , preferably 1 × 10 ^{−2 to} 1.0 g / m ² , and more preferably 1 × 10 ^{−2 to} 1.0 g / m ^2.
× 10 ^{−1 to} 0.8 g / m ² . When it is added to the photosensitive silver halide emulsion layer, it is 5 × 10 ⁻⁴ to 2 mol per mol of silver halide, preferably 1 ×.
10 ^-3 to 1 mol, more preferably 2 × 10 ^{-2 to} 5
It can be used in a range of × 10 ^-1 mol. Two or more kinds of acylacetamide type couplers having the group represented by formula (A) as an acyl group can be used in combination, and can be used together with other known yellow couplers. Furthermore, it can be used by mixing or coexisting with various compounds described later. An acylacetamide type coupler having a group represented by the general formula (A) as an acyl group can be added to a light-sensitive material together with a high boiling point organic solvent described below, and the same amount based on the total weight of the coupler in the layer containing the coupler. It is preferred that the total weight ratio of high boiling organic solvents in the layer is 0.5 or less. The range is more preferably 0.01 to 0.35. The acylacetamide type coupler having the group represented by the general formula (A) of the present invention as an acyl group is a coupler exhibiting high color developability, and when incorporated into a photographic material, the photographic material has excellent storage stability. The obtained color image is a coupler which has a small absorption on the long wavelength side, is excellent in color reproducibility, and gives high color image fastness. Further, it is a coupler which exhibits the above-mentioned excellent properties such that the high color developability is maintained even if the amount of the high boiling point organic solvent described later is reduced.

Use of the cyan coupler represented by the general formula (1) of the present invention and the yellow coupler having the group represented by the general formula (A) as an acyl group in the same light-sensitive material,
In particular, when used in color paper systems, it improves the color reproducibility by improving the absorption characteristics of each color image, provides a well-balanced and high color image fastness of cyan, magenta, and yellow, and improves the photographic property by processing. It is intended to provide a silver halide color photographic light-sensitive material with reduced fluctuation.

In the present invention, in order to add a cyan coupler represented by the general formula (1) and a yellow coupler having a group represented by the general formula (A) as an acyl group to a constituent layer of a light-sensitive material, a known method is known. Various techniques can be applied. 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, US Pat. No. 2,322,027
In the method of oil-in-water dispersion described in the publication, the boiling point is about 175 at normal pressure.
High boiling point organic solvents above ℃, such as phthalates,
Phosphoric acid esters, benzoic acid esters, fatty acid esters, amides, phenols, alcohols, carboxylic acids, N, N-dialkylaniline acids, 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) , A lipophilic photographic organic compound including the coupler of the present invention is dissolved with ethers (for example, tetrahydrofuran, dioxane) and the like, and then emulsified and dispersed in a hydrophilic colloid such as gelatin. 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 a high-boiling point organic solvent may be in any form such as liquid, wax and solid, and has a dielectric constant (25 ° C.) of 2 to 20, preferably 3 to 15 as a physical property value. Yes,
It is a high boiling organic solvent having a refractive index (25 ° C.) of 1.30 to 1.70, preferably 1.35 to 1.60. The above-mentioned high-boiling point organic solvent preferably has the following formula [S
-1] to [S-9]. Formula [S-1]

[0090]

[Chemical 47]

Formula [S-2]

[0092]

[Chemical 48]

[0093] 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]

[0094]

[Chemical 49]

Formula [S-7]

[0096]

[Chemical 50]

Formula [S-8]

[0098]

[Chemical 51]

Formula [S-9] − (A ₁ ) a ₁ − (A ₂ ) a ₂ − …… − (An) _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.

[0101]

[Chemical 52]

[0102]

[Chemical 53]

[0103]

[Chemical 54]

[0104]

[Chemical 55]

[0105]

[Chemical 56]

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 "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.

[0110]

[Equation 1]

In the present invention, the variation coefficient 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. 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 may be decolorized by a treatment described in European Patent EP 0,337,490A2, pages 27 to 76 for the purpose of improving the 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.

High boiling organic solvents for photographic additives such as cyan, yellow or yellow couplers other than those of the present invention which can be used in the present invention have a melting point of 100 ° C. or less and a boiling point of 1 or less.
It is a compound that is immiscible with water at 40 ° C. or higher and can be used as long as it is a good solvent for the coupler. The melting point of the high boiling point organic solvent is preferably 80 ° C. or lower. The boiling point of the high boiling point organic solvent is preferably 160 ° C. or higher, more preferably 170 ° C. or higher. For more information on these high boiling organic solvents,
It is described in JP-A-62-215272, from page 137, lower right column to page 144, upper right column. Further, the above-mentioned cyan, yellow or magenta couplers other than the present invention are impregnated into a loadable latex polymer (for example, US Pat. No. 4,203,716) in the presence or absence of the high boiling point organic solvent. Or by dissolving with a water-insoluble and organic solvent-soluble polymer, and emulsified and dispersed in the hydrophilic colloid aqueous solution. Preferably US Pat. No. 4,857,449 and International Publication WO88
/ 00723, the homopolymers or copolymers described on pages 12 to 30 of the specification are used, and more preferably a methacrylate or acrylamide polymer, particularly an acrylamide polymer is used for stabilizing the color image. Is preferred.

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.

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 according to the present invention may be exposed to visible light or infrared light. The exposure method may be low-illuminance exposure or high-illuminance short-time exposure, and in the latter case, a laser scanning exposure method in which the exposure time per pixel is shorter than 10 ⁻⁴ seconds is preferable.

Further, upon exposure, 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 conventional color development processing (in the case of a reversal system, black-and-white development processing can also be used in combination).
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 a processing method applied to process 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.

[0122]

[Table 3]

[0123]

[Table 4]

[0124]

[Table 5]

[0125]

[Table 6]

[0126]

[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 of 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 disclosed 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.

[0129]

【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 First Layer Coating Solution Yellow coupler (ExY) 20.5 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 3.1 g 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.

[0134]

[Chemical 57]

(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)

[0136]

[Chemical 58]

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

[0138]

[Chemical 59]

(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)

[0140]

[Chemical 60]

(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.

[0143]

[Chemical formula 61]

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.

[0147]

[Chemical formula 62]

(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 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 0.30 Gelatin 1.22 Yellow Coupler (ExY) 0.88 Color Image Stabilizer (Cpd-1) 0.19 Solvent (S -4) 0.13 solvent (S-14) 0.13 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 ) 0.23 color image stabilizer (Cpd-2) 0.03 color image stabilizer (Cpd-3) 0.16 color image stabilizer (Cpd-4) 0.02 color image stabilizer (Cpd-9) 0 .02 solvent (S-2) 0.46

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 with average grain size 0.58 μm and small size emulsion with 0.45 μm (Ag mole ratio)) The coefficient of variation of the grain size distribution is 0.09 and 0.11, and AgBr 0.6 mol% was locally contained in a part of the grain surface in each size emulsion.) 0.23 Gelatin 1.60 Cyan coupler (ExC) 0.35 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-8) 0.175

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

[0157]

[Chemical 63]

[0158]

[Chemical 64]

[0159]

[Chemical 65]

[0160]

[Chemical 66]

[0161]

[Chemical 67]

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-8) / 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 68.

[0163]

[Chemical 68]

(Samples 105-) 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-8) / 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 prepared by first using a sensitometer (F, manufactured by Fuji Photo Film Co., Ltd.) for each sample.
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 a solution having the following processing step and processing solution composition,
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 solution 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] (tank solution and replenisher are the same) Water 400 ml Ammonium thiosulfate (700 g / liter) 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] (tank solution and 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 one 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. These concentration values obtained for each sample are the difference (ΔD _{B from} the concentration value of each sample with reference to the sample 101).
And ΔD _G ) were calculated. 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.

[0173]

[Table 8]

From the table, it can be seen that the cyan coupler represented by the general formula (1) of the present invention is the sample 10 using the comparative coupler.
When compared to 1 to 104, the coating flow rate was adjusted to 0.4 times the coupler coating amount (0.275 mmol / m ² ).
Even if it is set to a high level, it exhibits a remarkable color forming property that gives a high color density. Further, the coupler of the present invention is superior to any of these values in comparison with the values showing the most excellent performance of the comparative coupler in terms of storage stability, color image fastness and color reproducibility of the light-sensitive material. I understand.
The measurement result of the reflection spectrum of the cyan image obtained from the coupler represented by the general formula (1) of the present invention is:
For example, in the comparative sample 108, the maximum absorption wavelength is about 641.
nm, and the other samples of the present invention were in the range of ± 3 nm of Sample 108. On the other hand, the maximum absorption wavelength of Comparative Sample 101 is about 646 nm, and it is clear that the cyan image obtained from the coupler represented by the general formula (1) of the present invention is the best in terms of spectral absorption characteristics. Is. It is considered that this is because the absorption maximum wavelength was shifted to a short wave due to the association of the dye formed in the light-sensitive material, the absorption waveform was sharpened, and the absorption on the short wavelength side was reduced. Therefore, it is clear from the spectral absorption characteristics that the color reproducibility is also excellent. In addition, it is considered that the association of dyes contributes greatly to the solidification of the color image. In other words, the absorption maximum 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 it was confirmed that the samples exhibited long-wavelength absorption. This maximum absorption wavelength is unsuitable for color reproduction of color paper, and is also disadvantageous for printing conditions relating to the suitability of color paper for 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, the single-layer samples 102 and 106 in Example 1 of JP-A-3-196037 and the sample 104 of the present example.
When compared with (Comparative Sample) and 105-115 (Sample of the present invention), Samples 105-115 of the present invention of this example have a cyan coupler coating amount of 0.4 times the molar amount (0.275).
Since the cyan coupler of the present invention (including the cyan coupler described in JP-A-3-196037) provides a color developing solution, particularly a cyan color developer having a color density higher than that of the comparative sample 104 even if it is reduced to millimoles / m ² ). When N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline is used as a color developing agent, it is disclosed in Japanese Patent Application Laid-Open No. 3-1.
It can be understood that it gives a high color density that cannot be inferred from 96037.

Example 2 Comparative couplers (A), (B) and (C) shown in Chemical Formula 69 for the yellow coupler (Y-1) of the first layer (blue sensitive emulsion layer) based on the sample 105 of Example 1. And (D), and as shown in Table 9, the other couplers represented by the above general formula (Y) of the present invention are each substituted in an equimolar amount, and the high boiling point organic solvent / coupler weight ratio is the same. Samples 201 to 215 were prepared by adjusting so as to be 0.3.

[0176]

[Chemical 69]

These prepared samples were exposed together with the sample 105 described above under the exposure conditions described in Example 1, and a paper processor was used to obtain a solution having the following processing steps and processing liquid compositions, which was 3 times the tank capacity for color development. The sample which was separately imagewise exposed until the amount was replenished was subjected to continuous treatment (running treatment) and then to the treatment.

Treatment process Temperature Time Replenisher ^* Tank capacity Color development 38.5 ° C 45 seconds 73ml 10 liters 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)

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 added 1000 ml 1000 ml pH (25 ° C) (with acetic acid and ammonia water) 5.8 5.6 Rinse solution (tank solution and replenisher are the same) Ion-exchanged water (calcium and magnesium are respectively 3ppm
Less than)

For the processed samples, B, G, R
The reflection densities of the three colors were measured, and their characteristic curves were obtained. From these characteristic curves, with respect to the photographic properties and the storage stability of the light-sensitive material, the yellow dye was used in Example 1 (1), (2)
It was obtained by the same method as. The color image fastness was determined in the same manner as in (3) of Example 1 for the test with a light fastness xenon fading tester, and the other was 60 ° C.
The sample was stored under the condition of 70% RH for 35 days, and then stored in
The color image residual rate was calculated according to the method described in (1). Regarding the color reproducibility, the reflection densities of B and G were measured with respect to the yellow color image obtained by exposure with the B filter of three color separation exposure, and the characteristic curve was obtained. From these characteristic curves, B
G on the characteristic curve measured by the filter G at the exposure amount of logE = 0.3 from the exposure amount giving the minimum density +0.5 on the characteristic curve measured by the filter to the high exposure amount side
The density was read. These concentration values obtained for each sample are the concentration difference (Δ) with each sample with reference to the sample 201.
D _B ) was calculated. The larger the negative value, the smaller the absorption on the long wavelength side of the yellow color image and the higher the saturation of the yellow color image, indicating that the color reproducibility is excellent.
The results are summarized in Table 9.

[0182]

[Table 9]

From the table, samples 205 to 21 using the yellow coupler represented by the general formula (Y) of the present invention are shown.
It is apparent that Nos. 5 and 105 give higher color developability (sensitivity, color density) than Comparative Samples 201 to 204, and are excellent in storage stability, color image fastness, and color reproducibility of the light-sensitive material. The comparative sample 20 is an acylacetamide type coupler having an acyl group represented by the general formula (A) of the present invention.
It is also clear that they show excellent performance that cannot be inferred from the couplers cited in 3 and 204. Also,
From the comparison of Samples 105, 213 and 214, in the acylacetamide type coupler having a group represented by the general formula (A) as an acyl group, the hydrocarbon ring in which Q forms a ring together with a carbon atom is a cyclopyropane ring, a cyclobutane ring or a cyclopentane ring. It is also clear that the above-mentioned excellent performances are deteriorated in the order of, and it is understood that the cyclopropane ring exhibits the best performance. When the color image fastnesses of magenta and cyan color images were examined under the same conditions as above, for example, Sample 10
8, D ₂ = 99 (%) and D ₃ = 96 of the magenta color image
(%), Cyan image D ₂ = 100 (%), D ₃ = 98
(%)Met. From this result, the general formula (1) of the present invention
And silver halide color photographic light-sensitive materials using an acylacetamide type coupler having a group represented by the general formula (A) as an acyl group are cyan, magenta and yellow 3.
It has been found that the colors each exhibit a high color image fastness and give good results with a good balance of the three colors.

Example 3 Samples 101 and 108 prepared in Example 1, Example 2
Based on the samples 202 and 210 prepared in 1., the high boiling point organic solvent (S-4 / S-14) of the first layer (blue sensitive emulsion layer) was used.
= 1/1) / yellow coupler weight ratio is 1.00,
0.50, 0.20, 0.10, and at the same time, the weight ratio of the high boiling point organic solvent S-8 / cyan coupler of the fifth layer (red sensitive emulsion layer) is 2.00, 1.50, 0. .25,
Samples 301 to 3 were adjusted to 0.10.
16 was produced. These prepared samples were exposed to light as described in Example 1, and the same performance evaluation was performed. However, for the treatment, the treatment liquid after the running treatment used in Example 2 was used. The photographic properties and color reproducibility were based on the sample having the highest weight ratio of high boiling point organic solvent / coupler. The results are shown in Tables 10 and 11.

[0185]

[Table 10]

[0186]

[Table 11]

From the above table, samples 305 to 308, 108 using the cyan coupler represented by the general formula (1) and the acylacetamide / yellow coupler having the group represented by the general formula (A) as an acyl group according to the present invention. 313 ~
316 and 210 show almost no change in the photographic properties (sensitivity, color density) and color image fastness even when the weight ratio of the high boiling point organic solvent / coupler is 1.50 or less and 0.50 or less, respectively. It is clear that all of them show excellent performance, which is higher than that of. It can also be seen that the color image fastness shows high fastness and balanced fastness. However, also in the comparative sample, the coupler represented by the general formula (1) of the present invention and the acylacetamide coupler having the group represented by the general formula (A) as an acyl group have a high boiling point organic solvent / coupler weight ratio of 1 respectively. When it is 0.50 or less and 0.50 or less, the photographic properties and color image fastness show similarly good results.

Regarding the storage stability and color reproducibility of the light-sensitive material, both the coupler represented by the general formula (1) and the acylacetamide coupler having the group represented by the general formula (A) as an acyl group of the present invention are respectively It was confirmed that the dependency of the high boiling point organic solvent / coupler on the weight ratio was smaller than that of the comparative sample. I will omit about these data.

For the coupler represented by the general formula (1), the high boiling point organic solvent S-8 was changed to S-4, S-9 and S-15, and a sample 305 based on the sample 108 was used.
˜308, but equally good results were obtained. On the other hand, an acylacetamide coupler having a group represented by the general formula (A) as an acyl group is similarly converted into S-
4, S-14 instead of S-1, S-6, S-8, S-1
The same procedure was performed by using S-3 and S-17 alone, but similar results could be obtained.

Example 4 (Y of the acylacetamide coupler having the group represented by the general formula (A) of the present invention as an acyl group, which was used in the first layer (blue-sensitive emulsion layer) of the sample 101 prepared in Example 1. -1) was replaced with the comparative coupler (B) used in Example 2 in an equimolar amount, the high boiling organic solvent / coupler weight ratio was adjusted to the same 0.3, and the others were made the same to prepare Sample 401. In addition to this sample 401, the samples 101, 108, 112 produced in Example 1 and the samples 202, 208, 210, 212 produced in Example 2 were used, and the treatment used in Example 2 was continuously performed before the start of treatment. After completion of the treatment, exposure was performed under the exposure conditions described in Example 1 to perform the treatment. The processed sample was subjected to concentration measurement, and the concentration was measured in (1) of Example 1.
The color density was determined according to the method described in (1), and the color density difference (ΔD _R , ΔD _B ) between the cyan color image and the yellow color image was calculated based on the value before the start of continuous processing. Furthermore, the temperature and time of color development in the processing step of the processing used in Example 2, the color developing agent (N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl) of the tank liquid composition of the color developing solution. The concentration and pH of (-4-aminoaniline sulfate) were changed as shown in Table 12, the exposure described in Example 1 was applied, and batch type development was performed.

[0191]

[Table 12]

As the bleach-fixing solution and the rinsing solution, a new solution having a tank solution composition was used as it was, and processed at the same processing temperature and processing time. For the processed sample, the color density is obtained from the characteristic curve in the same manner as described above, and the color density difference (ΔD _R , ΔD _B ) between the cyan color image and the yellow color image is calculated based on the color density before the start of the same continuous processing. Calculated. The obtained results are summarized in Table 13.

[0193]

[Table 13]

From Table 13, an acylacetamide coupler having the group represented by the general formula (A) of the present invention as an acyl group is used in the first layer (blue-sensitive emulsion layer), and the fifth layer is used.
Samples 108, 112, 20 in which the cyan coupler represented by the general formula (1) of the present invention was used in the layer (red-sensitive emulsion layer).
8, 210 and 212 are comparative samples 401 and 10
Compared with No. 1, 202, changes in processing factors of continuous processing and color development (color developing agent concentration, color developing temperature and time, p
It can be seen that the variation in the color density of both the cyan color image and the yellow color image is small with respect to (change of H). In particular, when the cyan coupler represented by the general formula (1) of the present invention is used in the fifth layer, the above continuous treatment of the yellow coupler of the blue-sensitive emulsion layer of the lowermost layer (the layer closest to the support) and the change of the treatment factor are performed. Variation is smaller in the acylacetamide coupler having the group represented by the general formula (A) as an acyl group of the present invention than in the comparative yellow coupler (B), compared with the comparative samples of Samples 401, 101 and 202. Contrast with inventive samples 108, 112. From this fact, the effect of the combined use of the cyan coupler represented by the general formula (1) of the present invention and the acylacetamide coupler having the group represented by the general formula (A) of the present invention as an acyl group is excellent. Is clear.

Example 5 A multilayer color photographic paper having the following layer structure was prepared on a paper support which was laminated on both sides 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) 20.
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.

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 substances were used as stabilizers for each emulsion layer. 1- (2-acetoamino-phenyl) -5-mercaptotetrazole 2-methylthio-5-mercapto-1,3,4-thiadiazole 1- (p-carboxyphenyl) -2-acetamino-
7: 2: 1 mixture of 5-mercapto-1,3,4-triazole (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 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 Paper support which is laminated on both sides with polyethylene and whose surface is treated by corona discharge

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) 0.20 Solvent (S-7) 0.01 Solvent (S-18) 0.03

Second Layer (Color Mixing Prevention Layer) Gelatin 0.80 Color mixing inhibitor (Cpd-2) 0.03 Color mixing inhibitor (Cpd-8) 0.03 Solvent (S-8) 0.03 Solvent (S- 6) 0.15

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) 0.26 fading Inhibitor (Cpd-3) 0.10 Anti-fading agent (Cpd-4) 0.10 Anti-fading agent (Cpd-7) 0.20 Solvent (S-1) 0.13 Solvent (S-8) 0.13

Fourth layer (color mixing prevention layer) Gelatin 1.70 Color mixing inhibitor (Cpd-2) 0.02 Color mixing inhibitor (Cpd-8) 0.06 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) 0.10 Solvent (S-6) 0.19 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 α-pivaloyl-α- (3-benzyl-1-hydantoinyl) -2-chloro-5- [β- (dodecylsulfonyl) butyramide] acetanilide and α-pivaloyl-
1: 1 mixture with α- (3-benzyl-1-hydantoinyl) -2-methoxy-5- [β- (dodecylsulfonyl) butyramide] acetalinide (molar ratio) (ExM) Magenta coupler 7-chloro-6- (1-Methylcyclopropyl) -3-
Dodecylsulfonylpropyl-1H-pyrazolo [5,1
-C] -1,2,4-triazole and 7-chloro-6-
tert-butyl-3- {3-[(2-butoxy-5-tert
1-octyl) benzenesulfonyl} -1H-pyrazolo [5,1-c] -1,2,4-triazole
Mixture (molar ratio) (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-tetradecyloxyphenyl) -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 mixture 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 sample prepared as described above is used as sample 50.
Set to 1. Next, sample 502 is the first layer (blue-sensitive emulsion layer)
Of the yellow coupler ExY is replaced with an equimolar amount of a mixture of (Y-4) and (Y-8) in a 1: 1 molar ratio, and the cyan coupler ExC of the fifth layer (red-sensitive emulsion layer) is replaced by the one represented by the general formula (1).
Substituting an equimolar amount of a 1: 1 molar ratio mixture of (4) and (8), adjusting the weight ratio of high boiling point organic solvent / coupler to the same as that of sample 501, and adjusting the coating flow rate only for the fifth layer. Then, the coupler was coated so that the coating amount was 0.35 times the molar amount (corresponding to 0.22 mmol / m ² ) to prepare a sample. In Sample 503, ExY of the first layer was replaced with (Y-20) and ExC of the fifth layer was replaced with (25) of the general formula (1) in equimolar amounts, respectively, and the high boiling point organic solvent / coupler weight ratio was the same. Then, a sample was prepared in the same manner as the sample 502.

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 treatment (running test) was performed until the tank capacity was replenished to twice the tank capacity, and then the treatment was performed and the same performance evaluation as in Example 1 and Example 2 was performed.

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 solution 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 Ethylenediaminetetraacetic acid 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

As a result, the cyan coupler represented by the general formula (1) of the present invention was used in the fifth layer, and the acylacetamide coupler having the group represented by the general formula (A) of the present invention as an acyl group was obtained. Sample 502 used for the first layer
And 503 gave higher values in photographic sensitivity and color density for both the cyan color image and the yellow color image than the comparative sample 501. In particular, the cyan coupler drastically reduced the coating flow rate, and even though the coating amount was 0.35 times the molar amount, it still gave a higher concentration than that of Sample 501. In addition, it was confirmed that Samples 502 and 503 were able to obtain good results in both the cyan color image and the yellow color image in comparison with Comparative Sample 501 in terms of storage stability, color image fastness and color reproducibility of the light-sensitive material. Further, as a result of performing various treatments with various treatment factors in Example 4, an acylacetamide yellow coupler having a cyan coupler represented by the general formula (1) of the present invention and a group represented by the general formula (A) as an acyl group. It was confirmed that Samples 502 and 503 using the combination of No. 1 and 2 had a smaller variation in color density for both cyan and yellow color images than Comparative Sample 501, and stable performance was obtained.

[0220]

The combined use of the cyan coupler represented by the general formula (1) and the acylacetamide coupler having an acyl group represented by the general formula (A) results in a high color density in both cyan and yellow images. And has excellent stability over time of the light-sensitive material, color image fastness, and color reproducibility,
Further, it is possible to provide a silver halide color photographic light-sensitive material in which the change in photographic property with respect to processing fluctuations is reduced.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Shigeru Yamazaki 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture Fuji Photo Film Co., Ltd.

Claims (4)

[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. In the above, the silver halide emulsion layer containing the cyan coupler contains a coupler represented by the general formula (1) as a cyan coupler, and the silver halide emulsion layer containing the yellow coupler contains a yellow coupler represented by the general formula (A). A multi-layer silver halide color photographic light-sensitive material comprising an acylacetamide type coupler having a group as an acyl group. General formula (1) In the formula, Y is a non-metal atom group necessary for forming a 3- to 8-membered heterocycle with N, L is an alkylene group, R ¹ is an aryl group, Z is a hydrogen atom or a coupling-off group, Represent each. However, in the heterocycle, the carbonyl group does not directly bond to N. General formula (A) In the formula, R ₁ represents a monovalent group. Q is 3-5 with C
Represents a non-metal atomic group necessary for forming a 3-membered 5-membered heterocycle having at least one heteroatom selected from N, O, S and P in the ring. However, R ₁ is not a hydrogen atom and does not combine with Q to form a ring. 2. 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 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 layer to the total weight of the coupler in the layer containing an acylacetamide type coupler having a group represented by the general formula (A) as an acyl group is 0.5 or less. 3. The multilayer silver halide color photographic light-sensitive material according to claim 1 or 2, wherein 4. The coating amount of the coupler in the layer containing the cyan coupler represented by the general formula (1) is 0.5 per 1 square meter.
The multilayer silver halide color photographic light-sensitive material according to claim 1, 2 or 3, which does not exceed ^{x10 -3} mol.