JP2867353B2 - Silver halide color photographic materials - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide color photographic light-sensitive material, and more particularly to a silver halide color photographic material in which the stability of an emulsified dispersion of a yellow coupler is high and the storage stability of a color image after processing is improved. It relates to a photosensitive material.

[0002]

2. Description of the Related Art In a silver halide color photographic light-sensitive material, an aromatic primary amine developer oxidized by exposing the material to light and developing the color reacts with a dye-forming coupler (hereinafter referred to as a coupler). Thus, a color image is formed.

Generally, in this method, a color reproduction method based on a subtractive color method is used, and in order to reproduce blue, green, and red, yellow, magenta, and cyan color images having complementary colors are formed. For forming a yellow color image, a yellow dye-forming coupler (hereinafter referred to as a yellow coupler)
As acylacetamide couplers and malondianilide couplers, 5-pyrazolone couplers and pyrazolotriazole couplers as magenta couplers for forming magenta color images, and phenol couplers and naphthol couplers as cyan couplers for forming cyan color images, respectively. Commonly used.

[0004] The yellow dye, magenta dye and cyan dye obtained from these couplers have a silver halide emulsion layer or a silver halide emulsion layer which is color-sensitive to radiation which is complementary to the radiation absorbed by the dye. It is generally formed in an adjacent layer.

By the way, yellow couplers, particularly acylacetamide couplers such as benzoylacetoanilide couplers and pivaloylacetoanilide couplers are generally used for image formation. The former generally has a high coupling activity with an oxidized aromatic primary amine developing agent during development, and has a large molecular extinction coefficient of a yellow dye to be produced. It is mainly used for negative films, and the latter is mainly used for color paper and color reversal films because of its excellent spectral absorption characteristics and fastness of yellow dye.

However, benzoylacetanilide type couplers have high coupling reactivity with an oxidized form of an aromatic primary amine developing agent during color development and a large yellow azomethine dye having a high molecular absorption coefficient. There is a disadvantage that the spectral absorption characteristics of the yellow image are inferior,
Pivaloylacetanilide type couplers have excellent spectral absorption characteristics for yellow images, but have low coupling reactivity with oxidized aromatic primary amine developing agents during color development, and generate yellow azomethine dyes. There is a disadvantage that the molecular extinction coefficient is small.

[0007] Here, the high coupling reactivity of the coupler and the large molecular extinction coefficient of the dye formed result in high sensitivity,
It enables high gamma values and high color densities, resulting in so-called high color developability. Further, the excellent spectral absorption characteristics in the yellow image means, for example, absorption characteristics in which the long wavelength side of the spectral absorption is good and the unnecessary absorption in the green region is small.

Therefore, development of a yellow coupler which has both advantages, namely, high color developing property (high coupling reactivity of the coupler and large molecular extinction coefficient of the dye) and excellent spectral absorption characteristics of a color image has been desired. .

US Pat. No. 3,265,506 discloses a pivaloyl group, a 7,7-dimethylnorbornane-1-carbonyl group and a 1-methylcyclohexane-1-carbonyl group as acyl groups of acylacetanilide type couplers. JP-A-47-26133 discloses cyclopropane-.
A 1-carbonyl group, a cyclohexane-1-carbonyl group and the like are disclosed. However, these couplers were inferior in any point, such as poor coupling reactivity, low molecular extinction coefficient of the dye, or poor spectral absorption characteristics of color images.

The novel yellow coupler represented by the general formula ( I-2) used in the present invention has a sufficient coloring property, a high molecular extinction coefficient of the formed dye, and a skirt on the long wavelength side of the formed dye. Is good, and a dye preferable in color reproduction is provided.

Further, the dye produced by the yellow coupler of the present invention has remarkably excellent color image fastness under moist heat conditions as compared with conventionally used benzoylacetanilide type couplers or pivaloylacetoanilide type couplers. In particular, the color photographic light-sensitive material for printing, which requires image stability, has satisfactory performance.

However, the yellow coupler itself used in the present invention is inferior in color image fastness to light, and improvement of the light fastness is one of the important issues especially when it is considered for use in a photosensitive material for printing. Was.

From the viewpoint of improving the preservability of a color image with respect to light, for example, a method using a light stabilizer such as a hindered phenol or a piperidine compound is widely known. In addition, European Patent EP 0 310 552 A1 and EP
No. 0393718 A2 describes a method in which a sulfur-containing cyclic compound is used in combination. However, the light fastness of the coloring dye of the yellow coupler of the present invention is not sufficient by the above method alone, and further improvement has been desired.

Another problem of the coupler of the present invention is that
This is because the stability of the emulsified dispersion of the coupler is poor.
Deterioration of the stability of the emulsified dispersion causes a decrease in the maximum color density of the color image after color development and softening.

[0015]

Accordingly, a first object of the present invention is to provide a novel yellow coupler having excellent color reproducibility by using an emulsion dispersion having excellent stability and a silver halide color photograph containing the same. Provided is a photosensitive material. Second
An object of the present invention is to provide a color light-sensitive material having excellent color image stability by using the yellow coupler.

[0016]

A first object of the present invention is to provide at least one cyan-color-forming silver halide emulsion layer, a magenta-color-forming silver halide emulsion layer, and a yellow-color-forming halogen on a support. a silver halide color photographic light-sensitive material having a silver halide emulsion layer, at least one and following nondiffusible type yellow couplers represented by the following Symbol one general formula (I-2) to the yellow color forming silver halide emulsion layer This is achieved by a silver halide color photographic material characterized by containing an organic compound represented by the general formula (II).

[0017]

Formula (I-2)

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(In the formula , X ³ represents an organic residue necessary for forming a nitrogen-containing heterocyclic group together with> N-, Y represents an aryl group or a heterocyclic group, and Z represents a nitrogen atom.
And a group which is selected from a nitrogen-containing heterocyclic group bonded to the ring position and which is released when the coupler represented by the general formula is subjected to a coupling reaction with an oxidized developing agent. )

Formula (II)

Embedded image (In the general formula (II), R ⁴ , R ⁵ , R ⁶ and R ⁷
Represents a hydrogen atom, an aliphatic group, an aromatic group, an aliphatic oxycarbonyl group, an aromatic oxycarbonyl group, and a carbamoyl group, respectively. Provided that R ⁴ , R ⁵ , R ⁶ and R ⁷
Are not hydrogen atoms at the same time. )

Further, a second object of the present invention is to provide a support having at least one cyan-color-forming silver halide emulsion layer, a magenta-color-forming silver halide emulsion layer, and a yellow-color-forming silver halide emulsion layer. In a silver halide color photographic light-sensitive material, at least one of the above-mentioned diffusion-resistant yellow couplers, an organic compound represented by the general formula (II) and a compound represented by the general formula (III) are contained in the yellow-color-forming silver halide emulsion layer. This is achieved by a silver halide color photographic light-sensitive material characterized by containing an organic compound.

Formula (III)

Embedded image (In the general formula (III), R ⁸ , R ⁹ , and R ¹⁰ represent an alkyl group or an aryl group, and these groups include a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an alkylsulfonyl group, It may be substituted with a substituent such as an arylsulfonyl group, an alkoxycarbonyl group, a carbamoyl group, etc. When R ⁹ and R ¹⁰ are an alkyl group, they are bonded to each other to form a 5- to 7-membered ring. May be.)

The coupler represented by formula ( I-2) will be described in detail below.

[0024]

[0025]

When X ³ represents a nitrogen-containing heterocyclic group formed with> N—, the heterocyclic group preferably has 1 to 1 carbon atoms.
It may contain, for example, 20 or more preferably 1 to 15 hetero atoms other than a nitrogen atom, for example, an oxygen atom or a sulfur atom, preferably a 3 to 12 membered ring, more preferably a 5 or 6 membered ring, substituted or unsubstituted. A substituted, saturated or unsaturated, monocyclic or fused-ring heterocyclic group. Examples of this heterocyclic group include pyrrolidino, piperidino, morpholino, 1-piperazinyl, 1-indolinyl,
2,3,4-tetrahydroquinolin-1-yl, 1-imidazolidinyl, 1-pyrazolyl, 1-pyrrolinyl, 1
-Pyrazolidinyl, 2,3-dihydro-1-indazolyl, 2-isoindolinyl, 1-indolyl, 1-pyrrolyl, 4-thiazin-S, S-dioxo-4-yl or benzoxazin-4-yl.

[0027] When the previous SL nitrogen-containing heterocyclic group X ³ is> formed with N- has a substituent, the following can be listed as examples of the substituents. A halogen atom (for example, a fluorine atom, a chlorine atom), an alkoxycarbonyl group (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, for example, methoxycarbonyl, dodecyloxycarbonyl, hexadecyloxycarbonyl), an acylamino group (preferably carbon Numbers 2 to 30, more preferably 2 to 20, for example, acetamido, tetradecaneamide, 2- (2,4
-Di-t-amylphenoxy) butanamide, benzamide), a sulfonamide group (preferably having 1 to 3 carbon atoms)
0, more preferably 1 to 20. For example, methanesulfonamide, dodecanesulfonamide, hexadecylsulfonamide, benzenesulfonamide), carbamoyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 2 carbon atoms)
0. For example, N-butylcarbamoyl, N, N-diethylcarbamoyl), N-sulfonylcarbamoyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20; for example, N-mesylcarbamoyl, N-dodecylsulfonylcarbamoyl), sulfamoyl group (Preferably has 1 to 30, more preferably 1 to 20 carbon atoms. For example, N-butylsulfamoyl, N-dodecylsulfamoyl, N-
Hexadecylsulfamoyl, N-3- (2,4-di-
t-amylphenoxy) butylsulfamoyl, N, N
-Diethylsulfamoyl), an alkoxy group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20; for example, methoxy, hexadecyloxy, isopropoxy), an aryloxy group (preferably having 6 to 20 carbon atoms, more preferably Is 6 to 10. For example, phenoxy, 4-methoxyphenoxy, 3-t-butyl-4-hydroxyphenoxy, naphthoxy), aryloxycarbonyl group (preferably having 7 to 21 carbon atoms, more preferably 7 to 11; for example, phenoxycarbonyl) ), An N-acylsulfamoyl group (preferably having 2 to 30 carbon atoms, more preferably 2 carbon atoms)
~ 20. For example, N-propanoylsulfamoyl, N-
Tetradecanoylsulfamoyl), a sulfonyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms).
For example, methanesulfonyl, octanesulfonyl, 4-hydroxyphenylsulfonyl, dodecanesulfonyl),
Alkoxycarbonylamino group (preferably having 1 to
30, more preferably 1 to 20. For example, ethoxycarbonylamino), cyano group, nitro group, carboxyl group, hydroxyl group, sulfo group, alkylthio group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20; for example, methylthio, dodecylthio, dodecylcarbamoylmethylthio), ureido Groups (C1-30, more preferably 1-20; for example, N-phenylureido, N-
Hexadecylureido), an aryl group (preferably having 6 to 20, more preferably 6 to 10, for example, phenyl, naphthyl, 4-methoxyphenyl), a heterocyclic group (preferably having 1 to 20, more preferably 1) -10.
A 3- to 12-membered, preferably 5- or 6-membered, monocyclic or condensed ring containing, for example, at least one nitrogen atom, oxygen atom or sulfur atom as a hetero atom. For example, 2-
Pyridyl, 3-pyrazolyl, 1-pyrrolyl, 2,4-dioxo-1,3-imidazolidin-1-yl, 2-benzoxazolyl, morpholino, indolyl), alkyl group (preferably having 1 to 30 carbon atoms) More preferably 1 to
20, linear, branched, cyclic, saturated, unsaturated. For example, methyl, ethyl, isopropyl, cyclopropyl, t-pentyl, t-octyl, cyclopentyl, t-butyl, s
-Butyl, dodecyl, 2-hexyldecyl), acyl group (preferably having 1 to 30 carbon atoms, more preferably 2 to 2 carbon atoms)
0. For example, acetyl, benzoyl), an acyloxy group (preferably having 2 to 30 carbon atoms, more preferably 2 to 2 carbon atoms)
0. For example, propanoyloxy, tetradecanoyloxy), an arylthio group (preferably having 6 to 20, more preferably 6 to 10, for example, phenylthio, naphthylthio), a sulfamoylamino group (preferably having 0 to 30 carbon atoms, Preferably 0 to 20. For example, N-butylsulfamoylamino, N-dodecylsulfamoylamino, N-phenylsulfamoylamino) or N
-Sulfonylsulfamoyl group (preferably having 1 carbon atom)
-30, more preferably 1-20. For example, N-mesylsulfamoyl, N-ethanesulfamoyl, N-dodecanesulfonylsulfamoyl, N-hexadecanesulfonylsulfamoyl) can be mentioned. The above substituents may further have a substituent. Examples of the substituent include the substituents mentioned here.

Preferred substituents among the above are an alkoxy group, a halogen atom, an alkoxycarbonyl group, an acyloxy group, an acylamino group, a sulfonyl group, a carbamoyl group, a sulfamoyl group, a sulfonamide group, a nitro group, an alkyl group or an aryl group. No.

When Y in the general formula ( I-2) represents an aryl group, it is preferably a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, more preferably 6 to 10 carbon atoms. For example, a phenyl group and a naphthyl group are typical examples. When Y in the general formula ( I-2) represents a heterocyclic group , it preferably has 1 to 20 carbon atoms, and more preferably 1 carbon atom.
10 to 10, for example, a nitrogen atom, an oxygen atom as a hetero atom
Or at least one containing at least one sulfur atom
Saturated to ~ 12 membered ring, more preferably 5 or 6 membered ring
Or an unsaturated, substituted or unsubstituted, monocyclic or
It is a condensed ring heterocyclic group. Examples of the heterocyclic group include 3-
Pyrrolidinyl, 1,2,4-triazol-3-yl,
2-pyridyl, 4-pyrimidinyl, 3-pyrazolyl,
2-pyrrolyl, 2,4-dioxo-1,3-imidazoli
Zin-5-yl or pyranyl and the like.

When Y represents a substituted aryl group or a substituted heterocyclic group, examples of the substituent include the aforementioned X ³
Examples of the substituent when has a substituent include the substituents listed above. Preferred examples of the substituent for Y include:
One after the substitution is halogen atom, alkoxycarbonyl group, sulfamoyl group, carbamoyl group, sulfonyl group, N-sulfonylsulfamoyl group, N-acylsulfamoyl group, alkoxy group, acylamino group, N-sulfonylcarbamoyl group, When it is a sulfonamide group or an alkyl group.

A particularly preferred example of Y is a phenyl group in which at least one substituent is in the ortho position. General formula
The group represented by Z in ( I-2) is a coupling-off group , and is selected from a nitrogen-containing heterocyclic group bonded to the coupling position with a nitrogen atom. The leaving group may be a non-photographic useful group or a photographic useful or precursor thereof (for example, a development inhibitor, a development accelerator, a desilvering accelerator, a fogging agent, a dye,
Hardener, coupler, oxidized developing agent scavenger, fluorescent dye, developing agent or electron transfer agent).

When Z is a photographically useful group, those conventionally known are useful. For example, U.S. Pat.
8,962, 4,409,323, 4,43
8,193, 4,421,845, 4,61
8,571, 4,652,516, 4,86
1,701, 4,782,012, 4,85
7,440, 4,847,185, 4,47
7,563, 4,438,193, 4,62
Nos. 8,024, 4,618,571, 4,74
1,994, EP-A-193389A
No. 348139A or No. 272573A, or a leaving group (for example, a timing group) for releasing the photographically useful group.

Z is preferably a 5- or 6-membered, substituted or unsubstituted, saturated or unsaturated, monocyclic or condensed heterocyclic ring having 1 to 15 carbon atoms, more preferably 1 to 10 carbon atoms. Group. The hetero atom may include an oxygen atom or a sulfur atom in addition to the nitrogen atom. Preferred specific examples of the heterocyclic group include 1-pyrazolyl, 1-imidazolyl, pyrrino, 1,2,4-triazole-2.
-Yl, 1,2,3-triazol-1-yl, benzotriazolyl, benzimidazolyl, imidazolidine-
2,4-dione-3-yl, oxazolidine-2,4-
Dion-3-yl, 1,2,4-triazolidine-3,
5-dion-4-yl, imidazolidine-2,4,5-
Trion-3-yl, 2-imidazolinone-1-yl,
3,5-dioxomorpholino or 1-indazolyl. When these heterocyclic groups have a substituent,
As the substituent, substituents listed as the substituent which may be possessed by the X ³ can be cited as examples. As a preferred substituent, one of the substituents is an alkyl group, an alkoxy group, a halogen atom, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylthio group,
It is an acylamino group, a sulfonamide group, an aryl group, a nitro group, a carbamoyl group, a cyano group or a sulfonyl group.

[0034]

[0035]

[0036]

[0037]

[0038]

[0039]

[0040]

Next, the particularly preferred range of the coupler represented by the formula ( I-2) will be described below. The group represented by Y in the general formula ( I-2) is preferably an aromatic group. Particularly preferred is a phenyl group having at least one substituent at the ortho position. The description of the substituent includes those described as the substituent which may be possessed when Y is an aromatic group. The description of the preferred substituent is the same. Groups in general formula (I-2) represented by Z is preferably 5-6 membered, Ru nitrogen-containing heterocyclic group der to bind to the coupling site via a nitrogen atom.

A preferred coupler in the formula ( I-2) is represented by the following formula ( I-4) or (I-5).

[0043]

[0044]

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Formula (I-5)

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In the formula, Z represents the same meaning as described in formula (I- 2 ), Ar represents a phenyl group having at least one substituent on the ortho group, and X ⁶ represents —C
(R ⁰ R ¹ ) -N <represents an organic residue that forms a nitrogen-containing ring group (single ring or condensed ring), and X ⁷ represents —C
An organic residue forming a nitrogen-containing heterocyclic group (monocyclic or condensed ring) together with (R ² ) = C (R ³ ) -N <,
⁰ , R ¹ , R ² and R ³ represent a hydrogen atom or a substituent.

[0047] The general formula (I- 4) and a detailed description and preferred ranges of the groups represented by ^X 6, ^X 7, Ar and Z in (I-5) can be stated in one general formula (I-2) In the description, it has the same meaning as described in the applicable range. When R ^{0 to} R ³ represent a substituent, the aforementioned X ³
Examples of the substituents which may be possessed are listed as examples.

Formula (I- 2), (I-4) or (I-
The couplers represented by 5) include X ³ , X ⁶ , X ⁷ , Y, A
In the groups represented by r, R ⁰ -R ³ and Z, a dimer or higher multimer (for example, a telomer or a polymer) may be formed to be bonded to each other via a divalent or higher group. In this case, the number of carbon atoms may be out of the specified range for each substituent.

Formula (I- 2), (I-4) or (I-
The coupler represented by 5) is a diffusion-resistant coupler. A diffusion-resistant coupler is a coupler having a group having a sufficiently large molecular weight in the molecular weight in order to immobilize the layer to which the coupler is added. It is. Usually, the total carbon number is 8-30,
Preferably an alkyl group of 10 to 20 or a total of 4 to 4 carbon atoms
An aryl group having 20 substituents is used. These diffusion-resistant groups may be substituted in any of the molecules,
Moreover, you may have two or more.

Specific examples of the yellow coupler represented by formula (I- 2), (I-4) or (I-5) are shown below, but the present invention is not limited thereto.

[0051]

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[0052]

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[0053]

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[0054]

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[0055]

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[0056]

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[0057]

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[0058]

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[0059]

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[0060]

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[0061]

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[0062]

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[0063]

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[0064]

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[0065]

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[0066]

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[0067]

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[0068]

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[0069]

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[0070]

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An example of the synthesis of the compound represented by the above general formula ( I-2) is shown below.

[0072]

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Synthesis of Intermediate B Compound A 357.5 g (3.0 mol), Compound BA39
6.3 g (3.0 mol) of 1.2 liter of ethyl acetate,
Dissolved in 0.6 liter of dimethylformamide. While stirring, 631 g of dicyclohexylcarbodiimide
A solution of (3.06 mol) in acetonitrile (400 ml) was added dropwise at 15-35 ° C. After reacting at 20 to 30 ° C for 2 hours, the precipitated dicyclohexylurea was collected by filtration.
500 ml of ethyl acetate and 1 liter of water were added to the filtrate, and the aqueous layer was removed. Next, the organic layer was washed twice with 1 liter of water. After the organic layer was dried over anhydrous sodium sulfate, ethyl acetate was distilled off under reduced pressure, and 692 g of Intermediate A was obtained as an oil.
(98.9%).

[0069] 692 g (2.97 mol) of the intermediate A was dissolved in 3 liters of ethyl alcohol.
At 〜80 ° C., 430 g of 30% sodium hydroxide was added dropwise. After dropping, the mixture was reacted at the same temperature for 30 minutes, and the precipitated crystals were collected by filtration. (Yield: 658 g) The crystals were suspended in 5 liters of water, and 300 ml of concentrated hydrochloric acid was added dropwise at 40 to 50 ° C. while stirring. After stirring at the same temperature for 1 hour, the crystals were collected by filtration to obtain 579 g (95%) of intermediate B. (Decomposition point 127 ° C)

Synthesis of Intermediate D 45.1 g (0.22 mol) of intermediate B, compound C86.
6 g (0.2 mol) was dissolved in 400 ml of ethyl acetate and 200 ml of dimethylacetamide. While stirring, 66 g (0.32 mol) of dicyclohexylcarbodiimide
A solution of acetonitrile (100 ml) was added dropwise at 15-30 ° C. After reacting at 20 to 30 ° C for 2 hours, the precipitated dicyclohexylurea was collected by filtration.

The filtrate contains 400 ml of ethyl acetate and 600 m of water.
After the aqueous layer was removed and the aqueous layer was removed, the organic layer was washed twice with water.
After the organic layer was dried over anhydrous sodium sulfate, ethyl acetate was distilled off under reduced pressure to obtain 162 g of an oil. This oil was crystallized from 100 ml of ethyl acetate and 300 ml of n-hexane to obtain 108 g (87.1%) of an intermediate D. (Melting point 132-134 ° C)

[0077]

[Table 1]

Synthesis of Illustrative Coupler Y-1 Intermediate D 49.6 g (0.08 mol) was dissolved in dichloromethane 300 ml. Add sulfuryl chloride 1 to this solution.
1.4 g (0.084 mol) was added dropwise while stirring at 10 to 15 ° C. After reacting at the same temperature for 30 minutes, 200 g of a 5% aqueous sodium bicarbonate solution was added dropwise to the reaction mixture. After separating the organic layer, it was washed with 200 ml of water and dried over anhydrous sodium sulfate. Dichloromethane was distilled off under reduced pressure to obtain 47 g of an oil.

47 g of this oily substance was added to acetonitrile 200
Then, 28.4 g (0.22 mol) of compound D and 22.2 g (0.22 mol) of triethylamine were added thereto with stirring. After reacting at 40 to 50 ° C. for 4 hours, the mixture was poured into 300 ml of water, and the precipitated oil was extracted with 300 ml of ethyl acetate. The organic layer was washed with 200 g of a 5% aqueous sodium hydroxide solution, and then further twice with 300 m of water.
and washed with water. The organic layer was acidified with dilute hydrochloric acid, washed twice with water, and concentrated under reduced pressure to obtain a residue. (Yield 70 g) The obtained oily substance was mixed with 50 ml of ethyl acetate and 100 ml of n-hexane.
Of the exemplified coupler Y-1.
8 g (80%) were obtained. (Melting point 145-147 ° C)

[0080]

[Table 2]

[0081]

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Synthesis of Intermediate E 90.3 g (0.44 mol) of Intermediate B, Compound E187
g (0.4 mol) was dissolved in 500 ml of ethyl acetate and 300 ml of dimethylformamide. While stirring, a solution of 131.9 g (0.64 mol) of dicyclohexylcarbodiimide in acetonitrile (200 ml) was added for 15 to 30 minutes.
It was added dropwise at ° C. After reacting at 20 to 30 ° C for 2 hours, the precipitated dicyclohexylurea was collected by filtration. 500 ml of ethyl acetate and 600 ml of water were added to the filtrate, the aqueous layer was removed, and the organic layer was washed twice with water. After the organic layer was dried over anhydrous sodium sulfate, ethyl acetate was distilled off under reduced pressure to obtain an oily substance 28.
1 g was obtained. This was heated and dissolved in 1.5 liter of n-hexane, and insolubles were removed by filtration. The n-hexane solution was cooled with water, and the precipitated intermediate E was collected by filtration. Yield 243.4
g (93%) melting point 103-105 ° C

[0083]

[Table 3]

Synthesis of Illustrative Coupler Y-10 39.3 g (0.06 mol) of the intermediate E were dissolved in 200 ml of dichloromethane. 7. Add sulfuryl chloride to this solution.
7 g (0.064 mol) was added dropwise with stirring at 10 to 15 ° C. After reacting at the same temperature for 30 minutes, 200 g of a 4% aqueous sodium bicarbonate solution was added dropwise to the reaction mixture. After separating the organic layer, it was washed with 200 ml of water and dried over anhydrous sodium sulfate. Dichloromethane was distilled off under reduced pressure to obtain 41.3 g of an oil.

41.3 g of this oil was mixed with acetonitrile 1
00 ml, dissolved in 200 ml of dimethylacetamide,
20.8 g (0.16 mol) of compound D and 16.2 g of triethylamine were added with stirring. 3 at 30-40 ° C
After reacting for an hour, the mixture was poured into 400 ml of water, and the precipitated oil was extracted with 300 ml of ethyl acetate. 2% of organic layer
After washing with 300 g of an aqueous sodium hydroxide solution, it was further washed twice. The organic layer was acidified with diluted hydrochloric acid, washed twice with water, and concentrated under reduced pressure to obtain 42 g of a residue. This was crystallized from 200 ml of methanol, and the exemplified coupler Y-10 was added to 3
9.8 g (85%) were obtained. (Melting point 110-112 ° C)

[0086]

[Table 4]

[0087]

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Synthesis of Intermediate F Intermediate B 104.7 g (0.51 mol), compound F18
7.5 g (0.5 mol) was dissolved in 1 liter of ethyl acetate and 400 ml of dimethylformamide. While stirring, 107.3 g of dicyclohexylcarbodiimide
(0.525 mol) of dimethylformamide (100 m
l) The solution was added dropwise at 15-30 ° C. 1 at 20-30 ° C
After reacting for hours, add 500 ml of ethyl acetate and add
The mixture was heated to 60 ° C., and dicyclohexylurea was collected by filtration. After 600 ml of water was added to the filtrate and the aqueous layer was removed, 2 more
Washed twice. After the organic layer was dried over anhydrous sodium sulfate, ethyl acetate was distilled off under reduced pressure to obtain 290 g of an oil. This oily substance was dissolved in 1 liter of ethyl acetate and 2 liters of methanol.
The mixture was heated with 1 liter, insoluble materials were removed by filtration, and the filtrate was cooled with water. Yield 2
67g (95%) melting point 163-164 ° C

[0089]

[Table 5]

Synthesis of Intermediate G 114.0 g (0.2 mol) of Intermediate F was dissolved in 500 ml of dichloromethane. Sulfuryl chloride 2
8.4 g (0.21 mol) was added dropwise with stirring at 10 to 15 ° C. After reacting at the same temperature for 30 minutes, 500 g of a 6% aqueous sodium bicarbonate solution was added dropwise to the reaction mixture. After separating the organic layer, it was washed with 500 ml of water and dried over anhydrous sodium sulfate. When dichloromethane was distilled off under reduced pressure, Intermediate G was precipitated as a crystal. Yield 108.6 g (91%)

Synthesis of Illustrative Coupler Y-6 Intermediate G (29.8 g, 0.05 mol) was dissolved in dimethylformamide (80 ml), and Compound D (12.9 g, 0.1 mol / l) was dissolved.
Mol) and then 10.1 g of triethylamine (0.
10 mol) was added dropwise with stirring at 20-30 ° C. 4
After reacting at 0 to 45 ° C for 1 hour, ethyl acetate 300m
and 200 ml of water. The organic layer was washed twice with 400 g of a 2% aqueous sodium hydroxide solution, and then once more. After making the organic layer acidic with diluted hydrochloric acid, it is washed twice with water,
After concentration under reduced pressure, 34 g of a residue was obtained. This is added to ethyl acetate 50
The mixture was crystallized from a mixed solvent of 150 ml of n-hexane and 150 ml of n-hexane to obtain 19 g of an exemplary coupler Y-6. The crystals were recrystallized with 120 ml of a mixed solvent of ethyl acetate / n-hexane = 1/3 (vol ratio) to obtain 15 g of exemplified coupler Y-6.
(43.5%). (Melting point 135-136 ° C)

[0092]

[Table 6]

[0093]

[0094]

[0095]

Next, the epoxy compound represented by formula (II) of the present invention will be described in detail. General formula (II)
In the formula, R ⁴ , R ⁵ , R ⁶ and R ⁷ are each a hydrogen atom, preferably an aliphatic group having 1 to 30 carbon atoms, an aromatic group having 6 to 42 carbon atoms, and an aliphatic group having 2 to 31 carbon atoms. An oxycarbonyl group (such as a dodecyloxycarbonyl group, an allyloxycarbonyl group), an aromatic oxycarbonyl group having 7 to 43 carbon atoms (such as a phenoxycarbonyl group) or a carbamoyl group having 1 to 42 carbon atoms (a tetradecylcarbamoyl group, phenyl-methyl); Carbamoyl group). However, all of R ⁴ , R ⁵ , R ⁶ and R ⁷ are not hydrogen atoms at the same time.

The term "aliphatic group" as used herein means a linear, branched or cyclic aliphatic hydrocarbon group, and includes saturated and unsaturated groups such as alkyl, alkenyl and alkynyl groups. Representative examples include methyl, ethyl, butyl, dodecyl, octadecyl, iso-propyl, tert-butyl, tert-octyl, cyclohexyl, cyclopentyl, 1-methylcyclohexyl, allyl, vinyl, 2-hexadecenyl, propargyl and the like. .

The aromatic is a substituted or unsubstituted phenyl or naphthyl group having 6 to 42 carbon atoms. These aliphatic groups and aromatic groups further include an alkyl group, an aryl group, a heterocyclic group, and an alkoxy group (for example, methoxy,
2-methoxyethoxy), an aryloxy group (for example,
2,4-di-tert-amylphenoxy, 2-chlorophenoxy, 4-cyanophenoxy), alkenyloxy group (eg, 2-propenyloxy), acyl group (eg, acetyl, benzoyl), ester group (eg,
Butoxycarbonyl, phenoxycarbonyl, acetoxy, benzoyloxy, butoxysulfonyl, toluenesulfonyloxy), amide group (eg, acetylamino, ethylcarbamoyl, dimethylcarbamoyl, methanesulfonamide, butylsulfamoyl), sulfamide group (eg, dipropyls) Rufamoylamino),
Imido groups (eg, succinimide, hydantoinyl), ureido groups (eg, phenylureido, dimethylureide), aliphatic or aromatic sulfonyl groups (eg, methanesulfonyl, phenylsulfonyl), aliphatic or aromatic thio groups (eg, ethylthio) Phenylthio), a hydroxy group, a cyano group, a carboxy group, a nitro group, a sulfo group, a halogen atom and the like.

Specific examples of the compound of the present invention represented by formula (II) are shown below, but it should not be construed that the invention is limited thereto.

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[0101]

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[0102]

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[0103]

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[0104]

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[0105]

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Next, the amide compound represented by formula (III) will be described in detail. In the general formula (III),
R ⁸ , R ⁹ and R ¹⁰ are preferably an alkyl group having 1 to 36 carbon atoms or an aryl group having 6 to 36 carbon atoms, and these groups are a halogen atom, an alkoxy group, an aryl group, an aryloxy group, It may be substituted with a substituent such as an alkylsulfonyl group, an arylsulfonyl group, an alkoxycarbonyl group, and a carbamoyl group. R ⁹ , R ¹⁰
Are both alkyl groups, they may combine with each other to form a 5- to 7-membered ring.

Among the compounds represented by the general formula (III),
The compound represented by the following general formula (IV) is particularly preferred.

General formula (IV)

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In the formula, R ¹¹ is a halogen atom (a fluorine atom,
A chlorine atom, a bromine atom, an iodine atom), an alkyl group having 1 to 24 carbon atoms (for example, methyl, ethyl, isopropyl, tert-butyl, tert-pentyl, cyclopentyl, cyclohexyl, 1,1,3,3-tetra Methylpropyl, n-decyl, n-pentadecyl, tert
-Pentadecyl) or an alkoxy group having 1 to 24 carbon atoms (for example, methoxy, ethoxy, butoxy, octyloxy, benzyloxy, dodecyloxy). R ¹² and R ¹³ are each independently a hydrogen atom or an alkyl group having 1 to 24 carbon atoms (eg, methyl, ethyl, isopropyl, tert-butyl, methoxyethyl, benzyl, 2-ethylhexyl, n-hexyl,
V represents an alkylene group having 1 to 24 carbon atoms (for example, methylene, ethylene, trimethylene, ethylidene, propylidene), and p represents an integer of 1 to 3. However, when p is plural, R ¹¹ may be the same or different. R ¹² and R ¹³ may be bonded to each other to form a 5- to 7-membered ring.

Specific examples of the amide compound represented by the general formula (III) are shown below, but the present invention is not limited thereto. These amide compounds can be synthesized by a conventionally known method, for example, a condensation reaction between a carboxylic anhydride or a carboxylic chloride and an amine. A specific synthesis example is described in, for example, Japanese Patent Publication No. 58-25260.
No. 62,254,149 and U.S. Pat.
71,975 and the like.

[0111]

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[0112]

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[0113]

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[0114]

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[0115]

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The amount of the yellow coupler represented by formula ( I-2) in the present invention is preferably 0.1 mmol / m ² to 2 mmol / m ² per square meter of a silver halide color photographic light-sensitive material. preferably 0.3 mmol ^/ m 2 ~ 1.3, mmol / ^{m 2.}

The amounts of the compounds represented by the general formulas (II) and (III) of the present invention are determined according to the general formula ( I)
It is preferably used in the range of 0.01% by weight to 2.0% by weight, more preferably 0.1% by weight to 1.0% by weight, based on the yellow coupler represented by -2).
% By weight.

In the present invention, general formula (II) or general formula (II)
The compound represented by (III) can be used as a solvent for the yellow coupler or as a part of the solvent.

The cyan, magenta and yellow coloring layers of the silver halide color photographic light-sensitive material of the present invention are generally a red-sensitive layer, a green-sensitive layer and a blue-sensitive layer, respectively. However, these are not necessarily required, and may be, for example, an infrared-sensitive layer, an infrared-sensitive layer, and a red-sensitive layer, respectively. For the present invention, it is preferable that the yellow color-forming layer is applied to a position closest to the support in these layers, and further a magenta color-forming tank and a cyan color-forming layer are applied. The order of applying the magenta and cyan coloring layers may be either.

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

The light-sensitive material according to the present invention may be coated with a hydrophilic colloid layer in order to improve image sharpness and the like by a process described in EP 0,337,490A2, pages 27 to 76, which can be decolorized. Dyes (among which are oxonol dyes) are added so that the optical reflection density at 680 nm of the photosensitive material becomes 0.70 or more, or secondary or quaternary alcohols (for example, Titanium oxide surface-treated with methylolethane)
It is preferable to contain 2% by weight or more (more preferably 14% by weight or more).

The yellow coupler of the present invention may be used in combination with a yellow coupler other than the present invention. In the present invention, as a yellow coupler, a magenta coupler, and a cyan coupler, those described in the following patent publications (described in Table 9 below) can be used. As the magenta coupler, a pyrazoloazole coupler is particularly preferred.

In the present invention, the coating amount of the coupler in each layer is from 0.1 mmol / m ² to 2 mmol / m ² per square meter of a silver halide color photographic light-sensitive material.
And more preferably 0.3 mmol / m ²
１1.3 mmol / m ² . The coating amount of the silver halide emulsion in the silver halide emulsion layer is preferably 2 mol to 10 mol (value converted into Ag atom) per mol of the coupler, more preferably 2 mol to 5 mol. .

The high-boiling organic solvents for photographic additives such as cyan, magenta and yellow couplers used in the present invention are compounds having a melting point of 100 ° C. or less and a boiling point of 140 ° C. or more and are immiscible with water. Any solvent can be used. The melting point of the high boiling organic solvent is preferably 80 ° C. or lower. The boiling point of the high-boiling organic solvent is preferably 160 ° C. or higher,
More preferably, it is 170 ° C. or higher. Details of these high-boiling organic solvents are described in JP-A-62-215272, page 137, lower right column to page 144, upper right column.

The cyan, magenta or yellow coupler may be impregnated with a loadable latex polymer (for example, US Pat. No. 4,203,716) in the presence or absence of the above-mentioned high-boiling organic solvent, or in the presence of water. It can be dissolved together with an insoluble and organic solvent-soluble polymer and emulsified and dispersed in a hydrophilic colloid aqueous solution. Preferably, columns 7 to 15 of U.S. Pat. No. 4,857,449 and pages 12 to of WO 88/00723.
A homopolymer or a copolymer described on page 30 is used,
More preferably, use of a methacrylate-based or acrylamide-based polymer, particularly, an acrylamide-based polymer is preferable in terms of stabilizing a color image.

In the light-sensitive material according to the present invention, it is preferable to use a color image preservability improving compound as described in EP 0,277,589 A2 together with a coupler. In particular, combination use with a pyrazoloazole coupler is preferred. That is, the compound (F) which forms a chemically inactive and substantially colorless compound by chemically bonding with the aromatic amine-based developing agent remaining after the color developing process and / or the aromatic compound remaining after the color developing process. The compound (G) which forms a chemically inert and substantially colorless compound by chemically bonding with an oxidized form of an aromatic amine color developing agent can be used simultaneously or alone, for example, in storage after processing. It is preferable in order to prevent the generation of stains and other side effects due to the formation of a coloring dye due to the reaction between the color developing agent or its oxidized product and the coupler remaining in the film.

The light-sensitive material according to the present invention is provided with a fungicide such as that described in JP-A-63-271247 to prevent various molds and bacteria that propagate in the hydrophilic colloid layer and deteriorate the image. It is preferred to add an agent.

The support for use in the light-sensitive material according to the present invention may be a white polyester support for display or a support in which a layer containing a white pigment is provided on the support having a silver halide emulsion layer. A body may be used. In order to further improve the sharpness, it is preferable to coat an antihalation layer on the side of the support on which the silver halide emulsion layer is coated or on the back surface. In particular, the transmission density of the support is set to 0.1 so that the display can be viewed with both reflected light and transmitted light.
It is preferable to set in the range of 35 to 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. In the latter case, a laser scanning exposure method in which the exposure time per pixel is shorter than 10 ^-4 seconds is preferred.

Further, upon exposure, US Pat.
It is preferable to use the band stop filter described in U.S. Pat. This removes light mixing,
The color reproducibility is significantly improved.

The exposed light-sensitive material can be subjected to a conventional color developing process.
It is preferable to perform bleach-fix processing. In particular, when the high silver chloride emulsion is used, the pH of the bleach-fix solution is preferably about 6.5 or less, more preferably about 6 or less, for the purpose of accelerating desilvering. Silver halide emulsions and other materials (additives, etc.) and photographic constituent layers (layer arrangement, etc.) applied to the light-sensitive material according to the present invention, and processing methods and processing applied to process this light-sensitive material As the additives, those described in the following patent publications, in particular, European Patent EP 0,355,660 A2 (Japanese Patent Laid-Open No. 2-139544) are preferably used.

[0132]

[Table 8]

[0133]

[Table 9]

[0134]

[Table 10]

[0135]

[Table 11]

[0136]

[Table 12]

As the cyan coupler to be used in addition to the diphenylimidazole cyan coupler described in JP-A-2-33144, European Patent EP 0,333,1
No. 85A2, 3-hydroxypyridine cyan couplers (among the couplers (4)
(2) 4-equivalent coupler having a chlorine leaving group to give a 2-equivalent coupler, and couplers (6) and (9) are particularly preferred)
And the use of cyclic active methylene cyan couplers described in JP-A-64-32260 (in particular, coupler examples 3, 8, and 34 listed as specific examples) are also preferable. A method for processing a silver halide color light-sensitive material using a high silver chloride emulsion having a silver chloride content of 90 mol% or more is described in JP-A-2-207250, page 27, upper left column to page 34, upper right column. Is preferably applied.

[0138]

EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples.

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 dodecylbenzenesulfonate was provided, and various photographic constituent layers were further coated. A multilayer color photographic paper (sample 101) having the layer configuration shown was produced. The coating solution was prepared as follows.

Preparation of coating solution for first layer 19.1 g of yellow coupler (ExY) and color image stabilizer
To 4.4 g of (Cpd-1) and 2.3 g of the color image stabilizer (Cpd-7) were added 27.2 cc of ethyl acetate and 8.2 g of a solvent (Solv-1) to dissolve, and the solution was added with 10% dodecylbenzene sulfone. 185 of 10% gelatin aqueous solution containing 8 cc of sodium acid
The resulting mixture was emulsified and dispersed in cc to prepare an emulsified dispersion A. on the other hand,
Silver chlorobromide emulsion A (cubic, average grain size 0.88 μm
3: 7 mixture (larger silver ratio) of large emulsion A and 0.70 μm small emulsion E. The variation coefficients of the grain size distributions are 0.08 and 0.10, respectively. Each size emulsion contains 0.3 mol% of silver bromide locally on a part of the grain surface, and the balance is silver chloride. ) Was prepared. In this emulsion, blue-sensitive sensitizing dyes A and B shown below were contained in an amount of 2.0 × 10 ^-4 mol per mol of silver per mol of silver, and each of the following blue-sensitive sensitizing dyes per mol of silver. 2.5 × 10 ^-4 mol is added. The emulsion was chemically ripened by adding a sulfur sensitizer and a gold sensitizer. The above-mentioned emulsified dispersion A and this silver chlorobromide emulsion were mixed and dissolved to prepare a first layer coating solution 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 hardener for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt was used. Further, Cpd-10 and C
The total amount of pd-11 was 25.0 mg / m ² and 50, respectively.
mg / m ² . The following spectral sensitizing dyes were used for the silver chlorobromide emulsion of each photosensitive emulsion layer.

[0142]

Embedded image (Per mol of silver halide, 2.0 × 10 ⁻⁴ mol for large-size emulsion A and 2.5 × 10 ⁻⁴ mol for small-size emulsion A, respectively)

[0143]

Embedded image (Per mole of silver halide, 4.0 × 10 ^-4 mole for large-size emulsion B, and 5.0 × ^10-4 mole for small-size emulsion B.
6 × 10 ^-4 mol) and

Embedded image (Per 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)

[0144]

Embedded image (Per mol of silver halide: 0.9 × 10 ^-4 mol for large-size emulsion C, and 1.1 × 10 ^-4 mol for small-size emulsion C) The following compounds were added in an amount of 2.6 × 10 ⁻³ mol per mol of silver halide.

[0145]

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The blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer were treated with 1- (5-methylureidophenyl)-
5-mercaptotetrazole was replaced by silver halide 1
8.5 × 10 ⁻⁵ mol, 7.7 × 10 ⁻⁴ mol per mol,
2.5 × 10 ^-4 mol was added. In addition, 4-hydroxy-6-methyl-1, 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.

For the purpose of preventing irradiation, the following dyes were added to the emulsion layer (the coating amount is shown in parentheses).

[0148]

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(Layer Structure) The composition of each layer of the sample 101 is shown below. The numbers represent the coating amount (g / m ² ). The silver halide emulsion represents a coating amount in terms of silver.

Support Polyethylene laminated paper [The polyethylene on the first layer side contains white pigment (TiO ₂ ) and bluish dye (ultramarine)]

First layer (blue-sensitive emulsion layer) Silver chlorobromide emulsion A 0.30 Gelatin 1.56 Yellow coupler (ExY) 0.82 Color image stabilizer (Cpd-1) 0.19 Solvent (Solv) -1) 0.35 Color image stabilizer (Cpd-7) 0.10

Second layer (color mixture prevention layer) Gelatin 0.64 Color mixture prevention agent (Cpd-5) 0.10 Solvent (Solv-1) 0.16 Solvent (Solv-4) 0.08

Third Layer (Green-Sensitive Emulsion Layer) Silver chlorobromide emulsion (cubic, 1: 3 mixture of large size emulsion having an average grain size of 0.55 μm and small size emulsion of 0.39 μm (Ag molar ratio)) The coefficient of variation of the grain size distribution was 0.10 and 0.08, respectively, and 0.8 mol% of AgBr was locally contained in a part of the grain surface in each size emulsion.The balance was silver chloride.) 12 Gelatin 1.20 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 colors Image stabilizer (Cpd-9) 0.02 Solvent (Solv-2) 0.40

Fourth Layer (Ultraviolet Absorbing Layer) Gelatin 1.41 Ultraviolet Absorber (UV-1) 0.47 Color Mixer (Cpd-5) 0.05 Solvent (Solv-5) 0.24

Fifth Layer (Red-Sensitive Emulsion Layer) Silver chlorobromide emulsion (cubic, 1: 4 mixture of large size emulsion having an average grain size of 0.58 μm and small size emulsion of 0.45 μm (Ag molar ratio)). The coefficient of variation of the grain size distribution was 0.09 and 0.11, and in each size emulsion, 0.6 mol% of AgBr was locally contained in a part of the grain surface, with the balance being silver chloride.) 0.23 Gelatin 1.04 Cyan coupler (ExC) 0.32 Color image stabilizer (Cpd-2) 0.03 Color image stabilizer (Cpd-4) 0.02 Color image stabilizer (Cpd-6) 0.18 Color image Stabilizer (Cpd-7) 0.40 Color image stabilizer (Cpd-8) 0.05 Solvent (Solv-6) 0.14

Sixth layer (ultraviolet absorbing layer) Gelatin 0.48 Ultraviolet absorbing agent (UV-1) 0.16 Color mixing inhibitor (Cpd-5) 0.02 Solvent (Solv-5) 0.08

Seventh layer (protective layer) Gelatin 1.10 Acrylic modified copolymer of polyvinyl alcohol (Modification degree 17%) 0.17 Liquid paraffin 0.03

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[0159]

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[0162]

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[0163]

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Next, Sample 10 was prepared except that the yellow coupler (ExY) and the solvent (Solv-1) in the blue-sensitive emulsion layer of Sample 101 were replaced as shown in Table 13.
Samples 102 to 111 were produced in the same manner as in Example 1. The yellow coupler was substituted so as to be equimolar to the sample 101, and the solvent was substituted so as to be the same weight as the sample 101. The sample thus obtained was placed in Group A (A-101).
To A-111). The sample of Group A is a group of samples applied immediately after preparation of the coupler emulsified dispersion.

Next, after preparing emulsified dispersions of Samples 101 to 111 in the same manner and leaving them to stand at room temperature for one week, a coating solution was prepared in the same manner as in Group A, and the samples obtained by coating were used. B
Group (B-101 to B-111).

A sensitometer (manufactured by Fuji Photo Film Co., Ltd., FWH type, color temperature of light source 3200 ° K) is applied to each of the obtained samples.
Was used to give a gradation exposure of a three-color separation filter for sensitometry. The exposure at this time was performed such that the exposure amount was 250 CMS with an exposure time of 0.1 second.

The exposed samples were subjected to continuous processing (running test) using a paper processor using a solution having the following processing step and processing solution composition until the replenishment was twice the tank capacity for color development. Processing process Temperature Time Replenisher ^* Tank capacity Color development 35 ° C 45 seconds 161 ml 17 liter Bleaching and 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 liter rinse 3 30-35 ° C 20 seconds 350ml 10 liter drying 70-80 ° C 60 seconds * Replenishment amount per m ² of photosensitive material (Rinse 3 → 1 in 3 tanks countercurrent system)

The composition of each processing solution is as follows. [Color developer] [Tank solution] [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 1.0 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 (carboxymethyl ) Hydrazine 4.0 g 5.0 g N, N-di (sulfoethyl) hydroxylamine.1Na 4.0 g 5.0 g Fluorescent whitening agent (WHITEX 4B, manufactured by Sumitomo Chemical) 1.0 g 2.0 g pH (25 ° C) 10.05 10.45

[Bleaching-fixing solution] (the tank solution and the replenisher are the same) Water 400 ml Ammonium thiosulfate (70%) 100 ml Sodium sulfite 17 g Ethylenediaminetetraacetic acid (III) 55 g Ethylenediaminetetraacetic acid disodium 5 g Ammonium bromide 40 g Water is added. 1000ml pH (25 ° C) 6.0

[Rinse solution] (The tank solution and the replenisher are the same.) Ion-exchanged water (Calcium and magnesium are each 3 pp.
m or less)

Obtained processed samples (Groups A and B)
The maximum color density (Dmax) of the yellow sample was measured, and the Dmax of each sample in Group B with respect to the Dmax of each sample in Group A was determined as a percentage to calculate the stability of the emulsified dispersion of each sample. Table 13 shows the results of the stability of the emulsified dispersion = Dmax of each sample in Group B / Dmax of each sample in Group A × 100.

Table 13 shows that when the yellow coupler of the present invention and the compound represented by the general formula (II) of the present invention are used, a light-sensitive material having significantly improved stability of the emulsion dispersion of the yellow coupler of the present invention is provided. I found that I could do it. This was unexpected from the assumption that the conventional yellow coupler had no effect of improving the stability of the emulsion even when used in combination with the compound of the formula (II).

[0173]

[Table 13]

Example 2 Emulsified dispersions 201 to 211 for the first layer were prepared in the same manner as in the preparation of sample 101 of Example 1 except that the coupler and the solvent were changed as shown in Table 14. Was prepared. Samples obtained by applying the obtained emulsified dispersion in the same manner as Sample 101 immediately after preparation were used for Group A (A-201 to A-21).
1). Next, after the emulsified dispersions 201 to 211 were allowed to stand at room temperature for one week, samples obtained by coating in the same manner were designated as group B (B-201 to B-211).

The samples of Group A and Group B were subjected to the same color development processing as in Example 1, and the resulting processed samples (Group A and Group B) had the highest yellow color density (Dmax).
) Was measured, and the Dmax of each sample in Group B relative to the Dmax of each sample in Group A was determined as a percentage, and the stability of the emulsified dispersion of each sample was calculated. Stability of emulsified dispersion = Dmax of each sample in group B / Dmax of each sample in group A × 100 Further, using the sample of group A, a fading test was conducted at 60 ° C. and 70%, and the obtained results were obtained. The results are shown in Table 14.

From Table 14, it can be seen that the light-sensitive materials 205-211 using the coupler of the present invention and the compounds represented by the general formulas (II) and (III) of the present invention have excellent stability of an emulsified dispersion and have a yellow image. It turns out that it is excellent in heat fastness.

[0177]

[Table 14]

Example 3 In Example 2, the treated sample A obtained was irradiated with a xenon light source of 76,000 lux for 5 days to conduct a photobleaching test. As a result, the general formula (II) of the present invention was obtained.
Using the compounds represented by (III) and (Sample 2)
07 to 211) were also found to be particularly excellent in light fastness. Table 15 shows the obtained results. Therefore, by using the yellow coupler represented by the general formula ( I-2) of the present invention in combination with the compound represented by the general formulas (II) and (III), the stability, wet heat fastness and light fastness of the emulsified dispersion can be obtained. It can be seen that excellent photosensitive materials can be obtained for all of the above.

[0179]

[Table 15]

Example 4 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 dodecylbenzenesulfonate was provided, and various photographic constituent layers were further coated. A multilayer color photographic paper (300) having the indicated layer configuration was prepared. The coating solution was prepared as follows.

Preparation of Coating Solution for First Layer 132.0 g of yellow coupler (ExY) and a color image stabilizer (Cp
d-1) 15.0 g and 7.5 g of the color image stabilizer (Cpd-2) were dissolved in 25 g of solvent (Solv-2) and 180 cc of ethyl acetate, and the solution was dissolved in 60 cc of 10% sodium dodecylbenzenesulfonate and citric acid. An emulsified dispersion A was prepared by emulsifying and dispersing in 1000 g of a 10% aqueous gelatin solution containing 10 g of an acid. This emulsified dispersion A and the silver chlorobromide emulsion A of Example 1
Were mixed and dissolved to prepare a coating solution for the first layer so as to have the composition shown below. The emulsion coating amount indicates a coating amount in terms of silver amount.

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 hardener for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt was used. Also, Cpd-14 and C
pd-15 in a total amount of 25.0 mg / m ² and 50, respectively.
mg / m ² . The following spectral sensitizing dyes were used for the silver chlorobromide emulsions of the other photosensitive emulsion layers, respectively.

[0183]

[Table 16]

[0184]

[Table 17]

The blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer were treated with 1- (5-methylureidophenyl).
8.5 × 10 ^-5 mol, 7.7 × 10 ^-4 mol and 2.5 × 10 ^-4 mol of ^-5 -mercaptotetrazole were added per mol of silver halide, respectively. Further, 4-hydroxy-6-methyl-to-blue-sensitive emulsion layer and green-sensitive emulsion layer
1,3,3a, 7-Tetrazaindene were added in an amount of 1 × 10 ^-4 mol and 2 × 10 ^-4 mol, respectively, per mol of silver halide. In order to prevent irradiation, a dye represented by the following formula (I) is added to the emulsion layer.

[0186]

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The layer structure of each layer is shown below. The numbers represent the coating amount (g / m ² ). The silver halide emulsion represents a coated amount in terms of silver.

Support Polyethylene-laminated paper [polyethylene on the first layer side contains white pigment (TiO ₂ ) and blue dye (ultra blue)] First layer (blue-sensitive emulsion layer) Silver chlorobromide emulsion A described above 0.27 Gelatin 1.36 Yellow coupler (ExY) 0.75 Color image stabilizer (Cpd-1) 0.15 Color image stabilizer (Cpd-2) 0.06 Solvent (Solv-2) 0.30 Second Layer (color mixture preventing layer) Gelatin 1.00 Color mixture inhibitor (Cpd-4) 0.08 Solvent (Solv-7) 0.03 Solvent (Solv-2) 0.25 Solvent (Solv-3) 0.25

Third Layer (Green-Sensitive Emulsion Layer) Silver chlorobromide emulsion (cubic, 1: 3 mixture of large-sized emulsion B having an average grain size of 0.55 μm and small-sized emulsion B having an average grain size of 0.39 μm (Ag mole) The coefficient of variation of the grain size distribution was 0.10 and 0.08, respectively. In each size emulsion, 0.8 mol% of AgBr was locally contained in a part of the grain surface, and the remainder was silver chloride. 0.13 Gelatin 1.45 Magenta coupler (ExM) 0.16 Color image stabilizer (Cpd-5) 0.15 Color image stabilizer (Cpd-2) 0.03 Color image stabilizer (Cpd- 6) 0.01 Color image stabilizer (Cpd-7) 0.01 Color image stabilizer (Cpd-8) 0.08 Solvent (Solv-3) 0.50 Solvent (Solv-4) 0.15 Solvent (Solv) -5) 0.15 4th layer (color mixture prevention layer) Keratin 0.70 color mixing preventing agent (Cpd-4) 0.05 solvent (Solv-7) 0.02 solvent (Solv-2) 0.18 solvent (Solv-3) 0.18

Fifth layer (red-sensitive emulsion layer) Silver chlorobromide emulsion (cubic, 1: 4 mixture of large-size emulsion C having an average grain size of 0.50 μm and small-size emulsion C of 0.41 μm (Ag molar ratio) The coefficient of variation of the grain size distribution was 0.09 and 0.11, and each emulsion contained 0.8 mol% of AgBr locally on a part of the grain surface, and the remaining silver chloride was silver chloride. 0.20 gelatin 0.85 cyan coupler (ExC) 0.33 ultraviolet absorber (UV-2) 0.18 color image stabilizer (Cpd-9) 0.01 color image stabilizer (Cpd-10) 0 .01 Color image stabilizer (Cpd-11) 0.01 Solvent (Solv-6) 0.22 Color image stabilizer (Cpd-8) 0.01 Color image stabilizer (Cpd-6) 0.01 Solvent (Solv) -1) 0.01 color image stabilizer (Cpd-1) 0.33

Sixth layer (ultraviolet absorbing layer) Gelatin 0.55 Ultraviolet absorbing agent (UV-1) 0.38 Color image stabilizer (Cpd-12) 0.15 Color image stabilizer (Cpd-5) 0.02 Seventh layer (protective layer) Gelatin 1.13 Acrylic modified copolymer of polyvinyl alcohol (degree of modification 17%) 0.05 Liquid paraffin 0.02 Color image stabilizer (Cpd-13) 0.01

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Next, the yellow coupler (ExY) and the solvent (Solv) in the blue-sensitive emulsion layer were mixed with the sample (300).
-2) was replaced with a coupler and a solvent as shown in Tables 18 and 19, respectively.
01 to 346 were produced. At this time, the yellow coupler was substituted so as to be equimolar to the sample 300, and the solvent was substituted so as to be equal in weight to the sample 300. Further, the coating amount of the coating solution was set to 70% with respect to the sample 300 so that the coloring densities became substantially equal. For samples 300 to 346, samples of group A and group B were prepared as in Example 1. The samples were treated in the same manner as in Examples 2 and 3, and the color development and the fading were evaluated. However, the conditions for fading evaluation were 80
℃ ・ 70% ・ 20 days and 100,000 lux Intermittent Xe light source 1
0 days. As can be seen from Tables 18 and 19, also in this case, the stability of the emulsion is greatly improved when the coupler of the present invention is dispersed using the epoxy compound of the present invention. Thereby, photobleaching can be improved.

[0200]

[Table 18]

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[Table 19]

[0202]

According to the present invention, a color photograph having much better color reproducibility can be obtained than when a conventional yellow coupler is used. Further, in the present invention, the stability of the coupler emulsion is excellent, and the obtained color image is also excellent in wet heat fastness and light fastness.

Continuation of the front page (56) References JP-A-64-5048 (JP, A) JP-A-61-45247 (JP, A) JP-A-2-56 (JP, A) JP-A-52-154631 (JP, A) , A) JP-A-3-140952 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) G03C 7/36 G03C 7/392

Claims (2)

(57) [Claims] 1. A silver halide color photographic light-sensitive material having at least one cyan color-forming silver halide emulsion layer, a magenta color-forming silver halide emulsion layer, and a yellow color-forming silver halide emulsion layer on a support. in the lower SL one general formula to the yellow color forming silver halide emulsion layer (I-
A silver halide color photographic material comprising at least one diffusion-resistant yellow coupler represented by formula (2) and an organic compound represented by the following formula (II). General formula (I-2) (In the formula , X ³ represents an organic residue necessary for forming a nitrogen-containing heterocyclic group together with> N—, Y represents an aryl group or a heterocyclic group, and Z represents a nitrogen atom bonded to a coupling position.
And represents a group which is removed when a coupler represented by the general formula is subjected to a coupling reaction with an oxidized developing agent selected from the group consisting of nitrogen-containing heterocyclic groups . ) General formula (II) (Wherein R ⁴ , R ⁵ , R ⁶ and R ⁷ are each a hydrogen atom, an aliphatic group, an aromatic group, an aliphatic oxycarbonyl group,
Represents an aromatic oxycarbonyl group or a carbamoyl group. However, all of R ⁴ , R ⁵ , R ⁶ and R ⁷ are not hydrogen atoms at the same time. ) 2. The silver halide color photographic light-sensitive material according to claim 1, wherein said yellow color-forming silver halide emulsion layer further contains an organic compound represented by the following general formula (III). General formula (III) (In the formula, R ⁸ , R ⁹ and R ¹⁰ represent an alkyl group or an aryl group, and these groups may be further substituted with a substituent. When R ⁹ and R ¹⁰ are an alkyl group, ,
It may combine with each other to form a 5- to 7-membered ring. )