JP2002107884A - Silver halide color photographic sensitive material and dye-forming compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silver halide color photographic sensitive material having high color developing property, ensuring little color mixture during processing and giving a color image, whose hue and light resistance are superior, and to provide a dye-forming compound having a pyrrolotriazole skeleton and capable of exhibiting such a performance. SOLUTION: The dye-forming compound is represented by formula (I), wherein R1 and R2 are each alkyl, cycloalkyl, alkenyl, aryl or a heterocyclic group, R1 and R2 may bond to each other to form a 5- or 6-membered N-containing heterocycle; R3 is alkyl, cycloalkyl or alkenyl; R4 and R5 are each H, alkyl, cycloalkyl, alkenyl, aryl or a heterocyclic group, and R4 and R5 may bond to each other to form a 5- or 6-membered N-containing heterocycle. The silver halide color photographic sensitive material contains the dye-forming compound as a cyan coupler.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a silver halide color photographic light-sensitive material containing a novel cyan coupler and a novel dye-forming compound.

[0002]

2. Description of the Related Art In a silver halide color photographic light-sensitive material, an oxidized aromatic primary amine color developing agent and a coupler react with an exposed silver halide as an oxidizing agent to form indophenol and indoaniline. It is well known that dyes such as indamine, azomethine, phenoxazine, and phenazine are formed and a color image is formed.
In this photographic method, a subtractive color method is used, and a color image is formed by yellow, magenta, and cyan dyes. Of these, phenol or naphthol couplers have been generally used to form cyan dye images. However, the dyes formed from these couplers have an unfavorable absorption in the green region, and thus have a serious problem of significantly lowering color reproducibility, and it is urgently required to solve this. ing.

As means for solving this problem, heterocyclic compounds described in US Pat. Nos. 4,728,598 and 4,873,183, European Patent 249453A2 and the like have been proposed. However, these couplers have problems such as low coupling activity.
European Patent No. 49 discloses a coupler which overcomes these problems.
No. 1197A1, No. 488248, No. 54530
No. 0, No. 628867A1, No. 484909,
U.S. Pat. No. 5,164,289, JP-A-6-3479
No. 60 and the like have been proposed. These couplers are excellent in terms of hue and coupling activity. It is also excellent in that the molecular extinction coefficient of the dye is large.

However, the dyes obtained from these pyrroloazole-based couplers are liable to cause aggregation in the film, and have a problem that the hue is different between the high density part and the low density part. This problem is caused by high boiling organic solvents (oil) during emulsification.
This was particularly noticeable when the amount was small.

As means for solving this problem, Japanese Patent Application Laid-Open
Nos. 189988 and 10-198012 disclose pyrroloazole couplers. Color images obtained from these pyrroloazole-based couplers are certainly excellent in terms of hue, but are still insufficient for color reproduction from green to blue. That is, since the absorption coefficient of a magenta region unnecessary for a cyan image is large, it has not been satisfactory to the recent strong demand for a photograph having better color reproducibility. Further, the color images obtained from these pyrroloazole couplers are not sufficient in terms of light fastness, and further improvement has been desired.

In addition, when these known pyrroloazole couplers are used, color mixing and generation of stain on a white background have been serious problems. The color mixing means that an oxidized form of an aromatic primary amine-based color developing agent generated in another layer, for example, a magenta color-developing layer, is diffused into a cyan color-developing layer containing a pyrrolotriazole-based coupler, and the pyrrolotriazole-based coupler and the cup are mixed. The ring reaction causes unnecessary cyan coloring. Stain on a white background refers to the oxidation of a developing agent generated by oxidizing a small amount of developing agent remaining in a color photographic film after development processing by air oxidation or the like in an unexposed portion that should be white originally. A coupling reaction with the body, which also causes unnecessary cyan coloration (coloring). From the viewpoint of improving the color reproducibility of any of these, this improvement has been strongly desired.
On the other hand, development of dye-forming compounds having excellent hue and light resistance as described above as well as silver halide color photographic light-sensitive materials has been strongly demanded in the industry using dyes, particularly image dyes. .

[0007]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a silver halide color photographic light-sensitive material having high color developability, excellent hue of a color image obtained and excellent light fastness, and a pyrrolotriazole skeleton having such performance. To provide a compound for forming a dye.

[0008]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found a novel compound for forming a dye having a pyrrolotriazole skeleton, and have solved the problems by the following means. (1) A silver halide color photographic material comprising a cyan coupler represented by the following general formula (I). General formula (I)

[0009]

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In the general formula (I), R ¹ and R ² each independently represent an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group or a heterocyclic group. Here, R ¹ and R ² may combine with each other to form a 5- or 6-membered nitrogen-containing heterocyclic ring. R ³ represents an alkyl group, a cycloalkyl group or an alkenyl group. R ⁴ and R ⁵ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group or a heterocyclic group. Here, R ⁴ and R ⁵ may combine with each other to form a 5- or 6-membered nitrogen-containing heterocyclic ring. (2) A cyan dye-forming compound represented by the following general formula (I). General formula (I)

Embedded image In the general formula (I), R ¹ and R ² each independently represent an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group or a heterocyclic group. Here, R ¹ and R ² may combine with each other to form a 5- or 6-membered nitrogen-containing heterocyclic ring. R ³
Represents an alkyl group, a cycloalkyl group or an alkenyl group. R ⁴ and R ⁵ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group or a heterocyclic group. Here, R ⁴ and R ⁵ may combine with each other to form a 5- or 6-membered nitrogen-containing heterocyclic ring.

[0011]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. Here, the substituents on the formula (I) according to the present invention, the substituent includes the following substituent group defined by the name of the R ^40.

That is, the substituent group includes a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.),
An alkyl group (preferably a linear or branched alkyl group having 1 to 40 carbon atoms, for example, methyl, ethyl, propyl, isopropyl, butyl, t-butyl, 1-octyl, tridecyl, etc.), a cycloalkyl group (preferably Is a cycloalkyl group having 3 to 40 carbon atoms, for example, cyclopropyl, 1-ethylcyclopropyl, cyclopentyl, cyclohexyl, 1-norbornyl, 1-adamantyl and the like, an alkenyl group (preferably having 2 to 4 carbon atoms).
0 alkenyl group, for example, vinyl, allyl, 3
-Buten-1-yl or the like), an aryl group (preferably an aryl group having 6 to 32 carbon atoms, for example, phenyl,
1-naphthyl, 2-naphthyl, etc.),

A heterocyclic group (preferably having 5 to 32 carbon atoms);
To an 8-membered heterocyclic group, more preferably a group having at least one atom selected from a nitrogen atom, an oxygen atom and a sulfur atom as a ring-constituting atom.
Thienyl, 4-pyridyl, 2-furyl, 2-pyrimidinyl, 1-pyridyl, 2-benzothiazolyl, 1-imidazolyl, 1-pyrazolyl, benzotriazol-2-yl, etc., cyano group, silyl group (preferably having 3 carbon atoms) ~
40 silyl groups, for example, trimethylsilyl, triethylsilyl, tributylsilyl, t-butyldimethylsilyl, t-hexyldimethylsilyl, etc., hydroxyl group, carboxyl group, nitro group, alkoxy group (preferably having 1 to 40 carbon atoms) For example, methoxy, ethoxy, 1-butoxy, 2-butoxy, isopropoxy, t-butoxy, dodecyloxy, etc.), cycloalkyloxy group (preferably having 3 to 3 carbon atoms)
8 cycloalkyloxy groups, for example, cyclopentyloxy, cyclohexyloxy, etc.), aryloxy groups (preferably aryloxy groups having 6 to 40 carbon atoms, for example, phenoxy, 2-naphthoxy, etc.),

A heterocyclic oxy group (preferably having 1 to 4 carbon atoms)
0 is a heterocyclic oxy group, and more preferably, the heterocyclic part is the heterocyclic part described in the above heterocyclic group.
Phenyltetrazole-5-oxy, 2-tetrahydropyranyloxy, 2-furyloxy, etc., silyloxy group (preferably a silyloxy group having 1 to 40 carbon atoms, for example, trimethylsilyloxy, t-butyldimethylsilyloxy, diphenyl An acyloxy group (preferably an acyloxy group having 2 to 40 carbon atoms, such as acetoxy, pivaloyloxy, benzoyloxy, dodecanoyloxy), an alkoxycarbonyloxy group (preferably having 2 to 40 carbon atoms). An alkoxycarbonyloxy group, for example, ethoxycarbonyloxy, t-butoxycarbonyloxy, etc., a cycloalkyloxycarbonyloxy group (preferably a cycloalkyloxycarbonyloxy group having 4 to 40 carbon atoms) And, for example, cyclohexyloxycarbonyloxy and the like, an aryloxycarbonyloxy group (preferably an aryloxycarbonyloxy group having 7 to 40 carbon atoms, such as phenoxycarbonyloxy), and a carbamoyloxy group (preferably having 1 carbon atom). ~ 40 carbamoyloxy groups,
For example, N, N-dimethylcarbamoyloxy, N-butylcarbamoyloxy, etc.),

A sulfamoyloxy group (preferably a sulfamoyloxy group having 1 to 40 carbon atoms;
N, N-diethylsulfamoyloxy, N-propylsulfamoyloxy, etc.), alkanesulfonyloxy group (preferably an alkanesulfonyloxy group having 1 to 40 carbon atoms, for example, methanesulfonyloxy, hexadecanesulfonyloxy, etc. ), An arylsulfonyloxy group (preferably an arylsulfonyloxy group having 6 to 40 carbon atoms, such as benzenesulfonyloxy), an acyl group (preferably an acyl group having 1 to 40 carbon atoms, such as formyl, Acetyl, pivaloyl, benzoyl, tetradecanoyl, etc.), an alkoxycarbonyl group (preferably an alkoxycarbonyl group having 2 to 40 carbon atoms, for example, methoxycarbonyl, ethoxycarbonyl, octadecyloxycarbonyl, etc.), cycloalkyl An oxycarbonyl group (preferably a cycloalkyloxycarbonyl group having 4 to 40 carbon atoms, such as cyclohexyloxycarbonyl), an aryloxycarbonyl group (preferably an aryloxycarbonyl group having 7 to 40 carbon atoms, for example, Phenoxycarbonyl),

A carbamoyl group (preferably having 1 to 4 carbon atoms)
0 is a carbamoyl group, for example, carbamoyl,
N, N-dibutylcarbamoyl, N-ethyl-N-octylcarbamoyl, N-propylcarbamoyl, etc.),
An amino group [which represents an unsubstituted amino group, an alkylamino group, an anilino group, or a heterocyclic amino group, such as an unsubstituted amino group or an alkylamino group (preferably an alkylamino group having 1 to 32 carbon atoms; N, N-dioctylamino, tetradecylamino, octadecylamino, etc.), anilino group (preferably an anilino group having 6 to 40 carbon atoms, for example, anilino, N-methylanilino, etc.), and heterocyclic amino group (preferably carbon A heterocyclic amino group of Formulas 1 to 40, and more preferably, the heterocyclic portion is the heterocyclic portion described in the above heterocyclic group, for example, 4-pyridylamino and the like, and a carbonamide group (preferably having 2 carbon atoms). ~ 40 carbonamide groups, for example, acetamido, benzamido, tetradecaneamido, etc.),
A ureido group (preferably a ureido group having 1 to 40 carbon atoms, for example, ureido, N, N-dimethylureide,
N-phenylureido, etc.), imide group (preferably an imide group having 10 or less carbon atoms, for example, N-succinimide, N-phthalimido, etc.), alkoxycarbonylamino group (preferably alkoxycarbonylamino having 2 to 40 carbon atoms) And methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino, octadecyloxycarbonylamino, etc., a cycloalkyloxycarbonylamino group (preferably a cycloalkyloxycarbonylamino group having 4 to 40 carbon atoms) , For example, cyclohexyloxycarbonylamino, etc.),

An aryloxycarbonylamino group (preferably an aryloxycarbonylamino group having 7 to 40 carbon atoms, such as phenoxycarbonylamino), a sulfonamide group (preferably a sulfonamide group having 1 to 40 carbon atoms) For example, methanesulfonamide, butanesulfonamide, benzenesulfonamide,
A sulfamoylamino group (preferably a sulfamoylamino group having 1 to 40 carbon atoms, for example, N, N-dipropylsulfamoylamino, N-ethyl-N-dodecylsulfamoyl) An azo group (preferably an azo group having 1 to 40 carbon atoms, such as phenylazo), an alkylthio group (preferably an alkylthio group having 1 to 40 carbon atoms, such as ethylthio, octylthio, etc.), A cycloalkylthio group (preferably a cycloalkylthio group having 3 to 40 carbon atoms such as cyclohexylthio), an arylthio group (preferably an arylthio group having 6 to 40 carbon atoms such as phenylthio), a heterocyclic thio group Group (preferably a heterocyclic thio group having 1 to 40 carbon atoms, A heterocyclic moiety described in the aforementioned heterocyclic group, for example, 2-benzothiazolylthio, 2-pyridylthio, 1-phenyltetrazolylthio, etc., an alkylsulfinyl group (preferably an alkylsulfinyl having 1 to 40 carbon atoms) And, for example, dodecanesulfinyl and the like),

An arylsulfinyl group (preferably an arylsulfinyl group having 6 to 40 carbon atoms;
Benzenesulfinyl and the like, an alkanesulfonyl group (preferably an alkanesulfonyl group having 1 to 40 carbon atoms, such as a methanesulfonyl group and an octanesulfonyl group), an arylsulfonyl group (preferably an arylsulfonyl group having 6 to 40 carbon atoms) For example, benzenesulfonyl, 1-naphthalenesulfonyl and the like, an alkoxysulfonyl group (preferably an alkoxysulfonyl group having 1 to 40 carbon atoms, such as methoxysulfonyl and ethoxysulfonyl), a cycloalkyloxysulfonyl group (preferably Is a cycloalkyloxysulfonyl group having 3 to 40 carbon atoms, for example, cyclopropyloxysulfonyl and the like; an aryloxysulfonyl group (preferably an aryloxysulfonyl group having 6 to 40 carbon atoms); If, phenoxysulfonyl, p-
Methylphenoxysulfonyl, etc.), sulfamoyl group (preferably a sulfamoyl group having 32 or less carbon atoms, for example, sulfamoyl, N, N-dipropylsulfamoyl, N-ethyl-N-dodecylsulfamoyl, etc.), sulfo group, A phosphonyl group (preferably having 1 carbon atom)
And a phosphinoylamino group (preferably a phosphinoylamino group having 2 to 40 carbon atoms), for example, phenoxyphosphonyl, octyloxyphosphonyl, phenylphosphonyl and the like. Ethoxyphosphinoylamino, dioctyloxyphosphinoylamino, etc.).

Next, the compound represented by formula (I) of the present invention will be described. In the general formula (I), R ¹ and R ² are each independently an alkyl group, a cycloalkyl group,
Represents an alkenyl group, an aryl group or a heterocyclic group. These preferred embodiments are the same as alkyl group, cycloalkyl group, alkenyl group, aryl group and heterocyclic group in exemplified for the aforementioned R ^40. R ¹ and R ² may be the same or different. R ¹ and R ² may have a substituent, and examples of the substituent include those described above as R ⁴⁰ . R ¹ and R ² are bonded to each other to form a 5-member or 6-member
A nitrogen-containing heterocyclic ring may be formed. The nitrogen-containing heterocyclic ring may be a saturated heterocyclic ring, an unsaturated heterocyclic ring or an aromatic heterocyclic ring. Those selected from atoms are more preferable. , 4-dihydropyridin-1-yl, 2-
Oxymorpholino, 3-thiazolidine, 3-pyrroline-
1-yl and the like. The above nitrogen-containing heterocyclic ring may have a substituent include those exemplified for the aforementioned R ⁴⁰ is as the substituent.

R ¹ and R ² are preferably an alkyl group, a cycloalkyl group, or an alkenyl group. In this case, the number of carbon atoms is preferably 1 to 10, more preferably 1 to 5. Further, those in which R ¹ and R ² are bonded to each other to form a nitrogen-containing heterocyclic ring are also preferable. Preferred specific examples of the group represented by R ¹ R ² N— which is a partial structure of the general formula (I) are shown below, but the present invention is not limited thereto.

[0021]

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[0022]

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R ³ represents an alkyl group, a cycloalkyl group or an alkenyl group. These preferred embodiments are the same as alkyl group, cycloalkyl group and alkenyl group in exemplified for the aforementioned R ^40. R ³ may have a substituent, and examples of the substituent include those described above as R ⁴⁰ .

R ³ is preferably a group represented by the following formula (II). General formula (II)

[0025]

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In the general formula (II), R ¹¹ and R ¹² each independently represent an alkyl group, a cycloalkyl group or an alkenyl group. These preferred embodiments are the same as alkyl group, cycloalkyl group and alkenyl group in exemplified for the aforementioned R ^40. R ¹³ , R ¹⁴ and R ¹⁵ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group or an alkenyl group. When R ¹³ , R ¹⁴ and R ¹⁵ represent an alkyl group, a cycloalkyl group or an alkenyl group, preferred specific examples thereof are the same as the alkyl group, cycloalkyl group and alkenyl group exemplified as R ⁴⁰ above. R ¹³ , R ¹⁴ and R ¹⁵ are preferably a hydrogen atom.

Z represents a group of carbon atoms necessary to form a 5- to 8-membered ring, and this ring may be substituted and may be a saturated ring or an unsaturated ring. If the ring has a substituent, include those exemplified as the R ⁴⁰ is as the substituent. Examples of the ring formed by Z include a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a cyclohexene ring, and the like. The ring formed by Z is preferably a 5- to 6-membered ring, more preferably a cyclohexane ring which may have a substituent.

R ⁴ and R ⁵ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group or a heterocyclic group. R ⁴ and R ⁵ are an alkyl group,
When it represents a cycloalkyl group, an alkenyl group, an aryl group or a heterocyclic group, preferred specific examples thereof are the aforementioned R ⁴⁰
And the same as the alkyl group, cycloalkyl group, alkenyl group, aryl group and heterocyclic group.
R ⁴ and R ⁵ may be the same or different from each other. Also,
Each group of R ⁴ and R ⁵ may be further substituted with a substituent, and examples of the substituent include those described above as R ⁴⁰ .

One of R ⁴ and R ⁵ is preferably a group other than a hydrogen atom, and both are preferably groups other than a hydrogen atom. R ⁴ and R ⁵ are preferably an alkyl group, a cycloalkyl group or an aryl group, more preferably an alkyl group, and the alkyl group is a linear or branched alkyl group having 1 to 20 carbon atoms. Is most preferred.

R ⁴ and R ⁵ may combine with each other to form a 5- or 6-membered nitrogen-containing heterocyclic ring. The nitrogen-containing heterocycle may be a saturated heterocycle or an unsaturated heterocycle. Also, nitrogen-containing heterocycle may have a substituent include those exemplified for the aforementioned R ⁴⁰ is as the substituent.

Specific examples of the compound represented by formula (I) of the present invention are shown below, but the present invention is not limited to these specific examples.

[0032]

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[0033]

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[0034]

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[0035]

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[0036]

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[0037]

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[0038]

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[0039]

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The compounds represented by the general formula (I) of the present invention are described, for example, in JP-A-7-48376 and JP-A-8-10917.
No. 2, No. 10-198012, and the method described in the literature cited therein or a similar method.

Specific examples of the synthesis of the compound represented by formula (I) of the present invention are shown below. Synthesis Example 1 Synthesis of Exemplified Compound (1) Exemplified Compound (1) was synthesized by the following synthesis route.

[0042]

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Synthesis of Intermediate (I-2) 115.1 g of aminoguanidine sulfate was added to methanol 250
At room temperature, while stirring, 192 ml of a 28% methanol solution of sodium methoxide was added to the mixture suspended in milliliter, followed by compound (I-1) 5
3.1 g were added. The mixture was heated to reflux on a steam bath. After reacting for 1 hour, the mixture was cooled to room temperature, and diluted hydrochloric acid was added to neutralize the reaction solution. The reaction solution was extracted with ethyl acetate, and the organic layer was washed successively with water and saturated saline. After drying the organic layer over anhydrous magnesium sulfate, the solvent is distilled off,
39.6 g (yield 72%) of an intermediate (I-2) was obtained.

Synthesis of Intermediate (I-3) 19.6 g of the above intermediate (I-2) was dissolved in 120 ml of N, N-dimethylformamide.
38.7 g of bromobutane and 78 g of potassium carbonate were sequentially added. This mixture was heated and stirred on a steam bath at an internal temperature of 90 ° C. for 10 hours. After the reaction, the mixture is cooled to room temperature, and ethyl acetate 1
Liters and 500 milliliters of water were added. The organic layer was separated and washed sequentially with water and saturated saline. After the organic layer was dried over anhydrous magnesium sulfate, the solvent was distilled off. The resulting residue was purified by silica gel chromatography to obtain 32.4 g of intermediate (I-3) (yield: 62%).

Synthesis of Intermediate (I-4) A solution prepared by dissolving 32.4 g of the intermediate (I-3) in 200 ml of ethyl acetate was stirred at room temperature with 2,6.
-9.0 ml of lutidine were added. 3.7 ml of bromine were added dropwise to this mixture. After dropping,
After stirring at room temperature for 1 hour, 100 ml of water was added. The organic layer was separated and washed sequentially with water and saturated saline. After the organic layer was dried over anhydrous magnesium sulfate, the solvent was distilled off. The obtained residue was purified by silica gel chromatography to give intermediate (I-4) 37.9.
g (100% yield).

Synthesis of Intermediate (I-5) A solution prepared by dissolving 34.5 ml of a 28% methanol solution of sodium methoxide in 80 ml of N, N-dimethylacetamide was cooled with ice, and the internal temperature was kept at 10 ° C. or lower. , 15.5 ml of methyl cyanoacetate was added dropwise. After stirring for 30 minutes as it is, the intermediate (I-
4) A solution of 37.9 g in 50 ml of N, N-dimethylacetamide was added dropwise. After dropping, 3
After stirring for 0 minutes, an aqueous solution in which 11.8 g of potassium hydroxide was dissolved in 25 ml of water was added. The reaction mixture was stirred on a water bath at 50 ° C. for 3 hours. After completion of the reaction, the reaction solution was poured into a mixture of dilute hydrochloric acid and ice to neutralize the mixture. The reaction solution was extracted with ethyl acetate, and the organic layer was washed successively with water and saturated saline. After the organic layer was dried over anhydrous magnesium sulfate, the solvent was distilled off, thereby obtaining 38.2 g of the intermediate (I-5) as an oil (yield: 100%).

Synthesis of Exemplified Compound (1) In a solution of 38.2 g of the intermediate (I-5) in 70 ml of N, N-dimethylacetamide, 28 ml of pyridine and diallylcarbamoyl chloride 2
4.6 g were sequentially added and reacted at room temperature for 12 hours.
After the completion of the reaction, the reaction mixture was poured into dilute hydrochloric acid. The mixture was extracted with ethyl acetate, and the organic layer was washed sequentially with water and saturated saline. After drying the organic layer over anhydrous magnesium sulfate,
The solvent was distilled off. The residue was purified by silica gel column chromatography to obtain 24.1 g (yield: 53%) of the desired Exemplified Compound (1) as a powder. The structure of the obtained compound was confirmed by ¹ HNMR and mass spectrum.

¹ H NMR (300 MHz, CDCl ₃ ) δ
0.91 (18H, s), 1.08 (3H, d), 1.
1-1.9 (21H, m), 3.24 (4H, t),
4.00 (2H, m), 4.09 (2H, m), 5.2
7 (4H, m), 5.90 (2H, m), 5.95 (1
H, s), 9.65 (1H, br.s) MS m / z 650 (M ⁺ ).

The other compounds of the present invention can be synthesized in a similar manner.

The compound represented by formula (I) of the present invention is useful as a compound for forming a dye. The compound for forming a dye is a compound used for forming a dye, and the dye is a compound having absorption in an infrared, near infrared to visible region. The compound represented by formula (I) of the present invention is more preferably a compound in which the obtained dye is used as an image forming or image forming dye. That is, it is a dye-forming compound for image formation. As a method for obtaining a dye from the compound represented by the general formula (I) of the present invention, for example, an aromatic primary amine compound, particularly an oxidized product of a paraphenylenediamine derivative, an oxidized product of a hydrazine derivative, a diazonium salt or The salt can be easily obtained by reaction with a generator or the like. More specifically, for example, "Color Chemistry Synthe" by Heinrich Zollinger
ses, Properties and Applications of Organic Dyes a
nd Pigments (Second, revised edition), VCH Verlag
sgesellschaft mbH, Weinheim (Germany), 1991, or the references cited therein.

A dye such as an azomethine dye or an azo dye is obtained in advance using the compound represented by the general formula (I), and this dye may be used as a dye or a dye for image formation. As dyes for printers and dye diffusion transfer systems (DTR). Further, the compound may be incorporated into a system provided with a mechanism capable of forming a dye to form a dye in the system. A typical example in this case is use as a coupler for a silver halide color light-sensitive material. The present invention is not limited to the above-described exemplary use examples. In the present invention, the compound represented by the general formula (I) is preferably used as a coupler,
Further, it is preferably used as a cyan coupler, and most preferably used for a silver halide color photographic material, and more preferably for a silver halide color photographic material.

The use of the compound of the present invention in a silver halide color photographic light-sensitive material, which is the most preferred embodiment, will be described below.

The light-sensitive material of the present invention may have at least one layer containing the coupler of the present invention on a support.
The layer containing the coupler of the present invention may be a hydrophilic colloid layer on a support. A general light-sensitive material can be constituted by coating a support with a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer in this order. However, the order may be different from this. Further, an infrared-sensitive silver halide emulsion layer can be used in place of at least one of the above-mentioned photosensitive emulsion layers. These photosensitive emulsion layers contain a silver halide emulsion having sensitivity in each wavelength region and a color coupler which forms a dye having a complementary color relationship with the light to be exposed, thereby performing color reproduction by the subtractive color method. be able to. However, the photosensitive emulsion layer and the color hue of the color coupler may not have the above correspondence. In the present invention, it is particularly preferable to use a cyan coupler in the red-sensitive silver halide emulsion layer.
The content of the coupler of the present invention in the light-sensitive material is suitably from 1 × 10 ⁻³ mol to 1 mol, preferably from 2 × 10 ⁻³ mol to 5 × 10 mol per mol of silver halide in the same layer. ^-1 mole.

The coupler of the present invention can be introduced into a light-sensitive material by various known dispersion methods, dissolved in a high-boiling organic solvent (optionally using a low-boiling organic solvent in combination), emulsified and dispersed in an aqueous gelatin solution, and halogenated. The oil-in-water dispersion method for addition to a silver emulsion is preferred. Examples of high boiling point solvents used in the oil-in-water dispersion method are described in JP-A-5-313327 and JP-A-5-3235.
No. 39, No. 5-323541, No. 6-258803
No. 8-262662, U.S. Pat. No. 2,322,0
No. 27, etc. Further, the steps and effects of the latex dispersion method as one of the polymer dispersion methods and specific examples of the latex for impregnation are described in US Pat. No. 4,199,363.
No., West German Patent Application No. (OLS) 2,541,274,
No. 2,541,230, JP-B-53-41091, and European Patent Publication No. 029104.
PCT for dispersion with organic solvent soluble polymer
International Publication No. WO88 / 00723 and JP-A-5-15
No. 0420 and the like. Methacrylate-based or acrylamide-based polymers are preferred, and acrylamide-based polymers are particularly preferred in view of image fastness.

Here, the high boiling point means a boiling point of 175 ° C. or more at normal pressure. Examples of the high boiling point solvent used in the present invention are described in US Pat. No. 2,322,027 and the like. Specific examples of the high-boiling organic solvent having a boiling point of 175 ° C. or higher at normal pressure include phthalic acid esters such as dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, and bis (2,4-diethyl phthalate). -Tert-amylphenyl) phthalate, bis (2,4-
Di-tert-amylphenyl) isophthalate, bis (1,1-diethylpropyl) phthalate], esters of phosphoric acid or phosphonic acid (for example, triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl) Phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2-ethylhexylphenylphosphonate), benzoic acid esters (for example, 2-ethylhexyl benzoate, dodecyl benzoate, 2-ethylhexyl- p-hydroxybenzoate), amides (for example, N, N-diethyldodecaneamide, N, N-diethyllauramide, N
-Tetradecylpyrrolidone), sulfonamides (eg, N-butylbenzenesulfonamide), alcohols or phenols (isostearyl alcohol, 2,
4-di-tert-amylphenol), aliphatic carboxylic acid esters (for example, bis (2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate), aniline derivatives (N , N-dibutyl-2-butoxy-5-tert-octylaniline), hydrocarbons (eg, paraffin, dodecylbenzene, diisopropylnaphthalene), chlorinated paraffins, and the like. In particular, phosphates and JP-A-6-258803
And the hydrogen-donating compounds described in JP-A-8-262662 are excellent in terms of hue and can be preferably used.

In order to reduce the load on the environment,
In place of phthalates, European Patent EP-9693
It is preferable to use the compounds described in 20A1 and EP-969321A1, and in addition, tributyl citrate, pentaglycerin triester and the like can be mentioned. The dielectric constant of the high-boiling organic solvent varies depending on the purpose, but is preferably 2.0 to 7.0, and more preferably 3.0.
６6.0.

As the auxiliary solvent, an organic solvent having a boiling point of 30 ° C. or more, preferably 50 ° C. or more and about 160 ° C. or less can be used. Typical examples include ethyl acetate, butyl acetate, ethyl propionate, and methyl ethyl ketone. ,
Examples include cyclohexanone, 2-ethoxyethyl acetate, and dimethylformamide.

The emulsified dispersion may be used, if necessary, from the viewpoint of improving the stability over time during storage in the state of the emulsified dispersion, suppressing the change in photographic performance and improving the stability over time in the final coating composition mixed with the emulsion. Thus, all or a part of the auxiliary solvent can be removed by a method such as vacuum distillation, noodle washing or ultrafiltration. The average particle size of the lipophilic fine particle dispersion thus obtained is preferably 0.001 to 1.0 μm, more preferably 0.05 to 0.30 μm, and most preferably 0.08 to 0.20 μm. It is. The average particle size can be measured using a Coulter submicron particle analyzer model N4 (trade name, Coulter Electronics Co., Ltd.) or the like. If the average particle size of the lipophilic fine particle dispersion is large, the coloring efficiency of the coupler may be reduced, or the glossiness of the surface of the photosensitive material may be deteriorated.If the size is too small, the viscosity of the dispersion increases. , It becomes difficult to handle during manufacture.

The amount of the lipophilic fine particle dispersion comprising the coupler of the present invention to be used in the dispersion medium is preferably 2 to 0.1, more preferably 1.
The range is from 0 to 0.2. Here, a typical dispersion medium is, for example, gelatin, and a hydrophilic polymer such as polyvinyl alcohol. The lipophilic fine particle dispersion can contain various compounds according to the purpose together with the coupler of the present invention.

In the coupler of the present invention represented by formula (I), known additives can be used from the viewpoints of improvement in image fastness, processing stability, hue adjustment and the like. For example,
To improve the light fastness, see Japanese Patent Application Laid-Open No. 5-150426.
And the compounds described in JP-A-5-150424 and JP-A-5-150423 can be used. In particular, Japanese Patent Laid-Open No. 5-1
When the compound described in No. 50424 and the compound described in No. 5-150423 are used in combination, the effect is remarkable. In particular, for improving the light fastness in a low color density portion and the light stain on a white background, a cyan coupler described in JP-A-5-204110 may be used in combination, or US Pat. No. 4,797,35.
When the compounds described in No. 0 and the like are used, the improvement effect is remarkable. Further, the compound represented by the general formula (A) described in JP-A-10-333297.
DF), and any of the following compounds described in JP-A-11-258748, which is a vinyl compound represented by the general formula (II) and a compound represented by the general formula (III) An aniline derivative having an oxygen-nitrogen bond or an alkoxy substitution, a diffusion-resistant phenidone derivative represented by the general formula (IV), a diffusion-resistant carboxylic acid represented by the general formula (V), a general formula (VI )), An arylamide derivative represented by the general formula (VII), and a cyclic imide derivative represented by the general formula (VIII) for use in combination with the compound of the present invention. It is preferred. In addition, the description of each of the above-mentioned general formulas in the above-mentioned two patent publications, and the description of these exemplified compounds, synthetic methods, and applicable methods are applied to the present application as they are, and are incorporated as part of the specification of the present application.

In addition to the above, in order to suppress blix discoloration (defective recoloring) by the bleaching solution or the bleach-fixing solution, JP-A-8-62797 and JP-A-9-1997 are incorporated in the hydrophilic colloid layer.
It is preferable to use the polymers described in JP-A-171240 and JP-A-9-329861.

In the light-sensitive material according to the present invention, it is preferable to use a color image preservability improving compound as described in European Patent EP 0277589 A2 together with a coupler. In particular, a combination with a pyrrolotriazole coupler or a pyrazoloazole coupler represented by the general formula (I) of the present invention is preferable. That is, the compound in the above-mentioned patent which chemically bonds with the aromatic amine-based developing agent remaining after the color development process to form a chemically inert and substantially colorless compound and / or after the color development process Simultaneously or solely using the compound in the patent specification, which chemically bonds with the oxidized form of the remaining aromatic amine-based color developing agent to form a chemically inert and substantially colorless compound, For example, it is preferable in order to prevent the generation of stain and other side effects due to the formation of a coloring dye due to the reaction between the color developing agent remaining in the film or the oxidized product thereof and the coupler during storage after processing.

The silver halide photographic light-sensitive material of the present invention includes
In addition, conventionally known photographic materials and additives can be used. For example, a transmissive support or a reflective support can be used as a photographic support. Examples of the transparent support include transparent films such as cellulose nitrate film and polyethylene terephthalate, as well as 2,6-naphthalenedicarboxylic acid (NDCA) and ethylene glycol (EG).
And a polyester of NDCA, terephthalic acid and EG, etc., provided with an information recording layer such as a magnetic layer is preferably used. The reflective support is particularly laminated with a plurality of polyethylene layers and polyester layers,
A reflective support containing a white pigment such as titanium oxide in at least one such water-resistant resin layer (laminate layer) is preferred.

As a more preferred reflection support in the present invention, a support having a polyolefin layer having micropores on a paper substrate on which a silver halide emulsion layer is provided. The polyolefin layer may consist of multiple layers, in which case the polyolefin layer adjacent to the gelatin layer, preferably on the side of the silver halide emulsion layer, has no microvoids (eg polypropylene, polyethylene) and is close to the paper substrate More preferably, it is made of a polyolefin (for example, polypropylene or polyethylene) having micropores on the side. The density of these multilayers or polyolefin layers located between the paper substrate and the photographic component layer is between 0.40 and 0.40.
1.0 g / ml, preferably 0.50 to 0.1 g / ml.
70 g / ml is more preferred. The thickness of the multilayer or one polyolefin layer located between the paper substrate and the photographic component layer is preferably from 10 to 100 μm,
~ 70 µm is more preferred. Further, the thickness ratio of the polyolefin layer and the paper substrate is preferably 0.05 to 0.2,
0.1-0.5 is more preferable.

It is also preferable to provide a polyolefin layer on the opposite side (back side) of the above-mentioned paper substrate from the photographic constituent layer in order to increase the rigidity of the reflection support. In this case, the polyolefin layer on the back side has a matte surface. Preferred is polyethylene or polypropylene, and more preferred is polypropylene. The back side polyolefin layer preferably has a thickness of 5 to 50 μm, more preferably 10 to 30 μm, and further preferably has a density of 0.7 to 1.1 g / ml. In the reflection support of the present invention, a preferred embodiment relating to a polyolefin layer provided on a paper substrate is described in JP-A-10-3.
No. 33277, No. 10-333278, No. 11-52
No. 513, No. 11-65024, EP0880065
And the examples described in EP 0 880 066}.

It is preferable that the water-resistant resin layer contains a fluorescent whitening agent. Further, the fluorescent whitening agent may be dispersed in the hydrophilic colloid layer of the photosensitive material. As the fluorescent whitening agent, preferably, a benzoxazole-based, coumarin-based, or pyrazoline-based fluorescent whitening agent is used, and more preferably, a benzoxazolylnaphthalene-based or benzooxazolylstilbene-based fluorescent whitening agent is used. The amount used is not particularly limited, but is preferably 1 to 100 mg / m ² . The mixing ratio when mixed with the water-resistant resin is preferably 0.0005 to 3% by mass, and more preferably 0.001 to 0.5% by mass, based on the resin. The reflective support may be a transmissive support or a reflective support as described above, on which a hydrophilic colloid layer containing a white pigment is applied. Further, the reflective support may be a support having a mirror-reflective or second-class diffuse-reflective metal surface.

As a support used in the light-sensitive material according to the present invention, a white polyester-based support or a layer containing a white pigment for a display was provided on the support having a silver halide emulsion layer. A support may be used. In order to further improve the sharpness, it is preferable to provide 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 0.35 so that the display can be viewed with both reflected light and transmitted light.
It is preferable to set the value in the range of -0.8.

The light-sensitive material according to the present invention can be decolorized on a hydrophilic colloid layer by a process described in EP 0,337,490 A2, pp. 27-76, for the purpose of improving the sharpness of an image. Dyes (particularly oxonol dyes) are added so that the optical reflection density at 680 nm of the light-sensitive material is 0.70 or more, and dihydric alcohols (for example, It is preferable to contain 12% by mass or more (more preferably 14% by mass or more) of titanium oxide surface-treated with trimethylolethane) or the like.

The light-sensitive material according to the present invention has a hydrophilic colloid layer for the purpose of preventing irradiation and halation, and improving the safety of safelight, and the like. It is preferable to add the dyes described above that can be decolorized by the treatment (among others, oxonol dyes and cyanine dyes). Furthermore, dyes described in European Patent EP 0819977 are preferably added to the present invention. Some of these water-soluble dyes deteriorate color separation and safelight safety when used in an increased amount. Dyes which can be used without deteriorating color separation are described in JP-A-5-127324 and 5-1.
The water-soluble dyes described in Nos. 27325 and 5-216185 are preferred.

In the present invention, instead of the water-soluble dye,
Alternatively, a colored layer that can be decolorized by a treatment in combination with a water-soluble dye is used. The colored layer that can be decolorized by the processing used may be in direct contact with the emulsion layer, or may be arranged so as to be in contact with an intermediate layer containing a processing color mixture inhibitor such as gelatin or hydroquinone. This colored layer is preferably provided below (on the side of the support) the emulsion layer that develops the same primary color as the colored color. It is possible to install all the colored layers corresponding to each primary color individually, or to arbitrarily select and install only a part of them. It is also possible to provide a colored layer that is colored corresponding to a plurality of primary color gamuts. The optical reflection density of the colored layer is within the wavelength range used for exposure (400 nm in normal printer exposure).
It is preferable that the optical density value at the wavelength having the highest optical density in the visible light region of ~ 700 nm and the wavelength of the scanning exposure light source used in the case of scanning exposure is 0.2 or more and 3.0 or less. More preferably, it is 0.5 or more and 2.5 or less, particularly preferably 0.8 or more and 2.0 or less.

In order to form a colored layer, a conventionally known method can be applied. For example, Japanese Patent Application Laid-Open No. 2-282244-3
Dyes described from the upper right column of the page to page 8 and JP-A-3-79
No. 31, page 3, upper right column to page 11, lower left column, a method in which a solid fine particle dispersion is contained in a hydrophilic colloid layer, a method in which an anionic dye is mordanted to a cationic polymer, and a dye is halogenated. Examples thereof include a method of adsorbing fine particles such as silver and fixing it in a layer, and a method of using colloidal silver as described in JP-A-1-239544. As a method of dispersing the fine powder of the dye in a solid state, for example, a method of containing a fine powder dye which is substantially water-insoluble at least at pH 6 or less but is substantially water-soluble at least at pH 8 or more is disclosed in 2-30824
No. 4, pp. 4-13. Also, for example,
A method of mordanting an anionic dye into a cationic polymer is described in JP-A-2-84637, pp. 18-26. For a method for preparing colloidal silver as a light absorber, see U.S. Patent Nos. 2,688,601 and 3,45.
No. 9,563. Among these methods, a method of incorporating a fine powder dye and a method of using colloidal silver are preferred.

The silver halide grains in the silver halide emulsion used in the present invention are preferably cubic or tetradecahedral crystal grains having substantially {100} planes (these grains have rounded apex and higher Or octahedral crystal grains, or 50 of total projected area
% Or more are tabular grains having an aspect ratio of 2 or more composed of {100} planes or {111} planes. The aspect ratio is a value obtained by dividing the diameter of a circle corresponding to the projected area by the thickness of a particle. In the present invention, a cubic or tabular grain having a {100} plane as a principal plane or a tabular grain having a {111} plane as a principal plane is preferably applied.

As the silver halide emulsion used in the present invention, silver chloride, silver bromide, silver iodobromide, silver chloro (iodo) bromide emulsions and the like can be used. A silver chloride or silver chlorobromide emulsion having a content of 95 mol% or more is preferable, and a silver halide emulsion having a silver chloride content of 98 mol% or more is preferable. Among such silver halide emulsions, those having a silver bromide localized phase on the surface of silver chloride grains are particularly preferable because high sensitivity can be obtained and photographic performance can be stabilized. Further, 0.01 to 0.50 mol% per mol of total silver is added to the shell portion of the silver halide grain,
More preferably, those having a silver iodochloride phase of 0.10 to 0.40 mol% are preferable because high sensitivity can be obtained and high illuminance exposure suitability is excellent.

The localized silver bromide phase is preferably formed by epitaxially growing a localized phase having a total silver bromide content of at least 10 mol% or more in the localized silver bromide phase. The silver bromide content of the silver bromide localized phase is preferably in the range of 10 to 60 mol%, most preferably in the range of 20 to 50 mol%.
The silver bromide localized phase is preferably composed of silver in an amount of 0.1 to 5 mol% of the total silver constituting the silver halide grains in the present invention, and is preferably composed of 0.3 to 4 mol% of silver. More preferably, it is constituted. In the localized phase of silver bromide, iridium (III) chloride, iridium (III) bromide,
Iridium (IV) chloride, sodium hexachloroiridate (III), hexachloroiridium (IV)
It is preferable to contain a Group VIII metal complex ion such as potassium acid, hexaammine iridium (IV) salt, trioxalatoiridium (III) salt, and trioxalatoiridium (IV) salt. The addition amount of these compounds may vary over a wide range depending on the purpose, but may be 10 to 1 mol of silver halide.
^-9 to 10 ^-2 mol is preferred.

The silver halide emulsion used in the present invention is
In the course of emulsion grain formation or physical ripening, various polyvalent metal ion impurities other than iridium can be introduced. Examples of compounds used include iron, ruthenium, osmium, rhenium, rhodium, cadmium,
Salts or complex salts of metals of Group VIII of the periodic table such as zinc, lead, copper, and thallium can be used in combination. In the present invention, a metal compound having at least four cyano ligands, such as iron, ruthenium, osmium, and rhenium, is particularly preferred in that it further enhances high illuminance sensitivity and suppresses latent image sensitization. The iridium compound has a great effect on imparting high illuminance exposure suitability. The addition amount of these compounds varies widely depending on the purpose, but is preferably from 10 ^-9 to 10 ^-2 mol per mol of silver halide.

The average grain size of the silver halide grains contained in the silver halide emulsion used in the present invention (the grain size is defined by the diameter of a circle equivalent to the projected area of the grain and the number average thereof is taken) is 0.1. 1 μm to 2 μm is preferred. The particle size distribution is preferably a so-called monodisperse coefficient of variation (a standard deviation of the particle size distribution divided by the average particle size) of 20% or less, preferably 15% or less, more preferably 10% or less. . At this time, for the purpose of obtaining a wide latitude, it is also preferable to use the above monodispersed emulsion by blending it in the same layer, or to perform multi-layer coating.

The silver halide emulsion used in the present invention contains various compounds or their precursors for the purpose of preventing fogging during the production process, storage or photographic processing of the light-sensitive material, or stabilizing photographic performance. Can be added. Specific examples of these compounds are disclosed in the above-mentioned JP-A-62-2.
Those described on page 39 to page 72 of JP-A-15272 are preferably used. Furthermore, a 5-arylamino-1,2,3,4-thiatriazole compound (the aryl residue has at least one electron-withdrawing group) described in EP0447647 is also preferably used.

In the present invention, a hydroxamic acid derivative described in JP-A-11-109576 and a hydroxamic acid derivative described in JP-A-11-32709 are used in order to enhance the storage stability of the silver halide emulsion.
Cyclic ketones having a double bond in which both ends are substituted with an amino group or a hydroxyl group adjacent to the carbonyl group described in No. 4 (especially those represented by the general formula (S1), and paragraph numbers 0036 to 0071) Can be incorporated in the specification of the present application.) And sulfo-substituted catechol and hydroquinones described in JP-A-11-143011 (for example,
4,5-dihydroxy-1,3-benzenedisulfonic acid, 2,5-dihydroxy-1,4-benzenedisulfonic acid, 3,4-dihydroxybenzenesulfonic acid, 2,
3-dihydroxybenzenesulfonic acid, 2,5-dihydroxybenzenesulfonic acid, 3,4,5-trihydroxybenzenesulfonic acid and salts thereof), and the general formulas (I) to (III) of JP-A-11-102045. And hydroxylamines represented by the general formula (A) in U.S. Pat. No. 5,556,741 (column 5, line 56 to U.S. Pat. No. 5,556,741). Eleventh
The description in column 22, line is preferably applied also in the present application, and is incorporated as a part of the specification of the present application).

Spectral sensitization is performed for the purpose of imparting spectral sensitivity to a desired light wavelength range to the emulsion of each layer in the light-sensitive material of the present invention. In the light-sensitive material of the present invention, blue, green,
Examples of spectral sensitizing dyes used for spectral sensitization in the red region include, for example, FM Harmer's Heterocyclic compounds-Cyanine
dyes and related compounds (John Wiley & Sons [New
York, London], 1964). As specific examples of compounds and spectral sensitization methods, those described in the above-mentioned JP-A-62-215272, from page 22, upper right column to page 38, are preferably used. Particularly, as a red-sensitive spectral sensitizing dye for silver halide emulsion grains having a high silver chloride content, JP-A-3-123
The spectral sensitizing dye described in No. 340 is very preferable from the viewpoints of stability, strength of adsorption, temperature dependency of exposure, and the like.

The addition amount of these spectral sensitizing dyes may vary over a wide range depending on the case, and may be 0.5 to 0.5 mol per mol of silver halide.
The range is preferably from × 10 ^-6 mol to 1.0 × 10 ^-2 mol.
More preferably, 1.0 × 10 ⁻⁶ mol to 5.0 × 10 ^−3.
Range of moles.

The silver halide emulsion used in the present invention is usually subjected to chemical sensitization. Regarding the chemical sensitization method, sulfur sensitization represented by addition of an unstable sulfur compound, noble metal sensitization represented by gold sensitization, reduction sensitization, or the like can be used alone or in combination. As the compounds used for chemical sensitization, those described in JP-A-62-215272, from page 18, lower right column to page 22, upper right column are preferably used. Among them, it is particularly preferable that the material is subjected to gold sensitization. This is because, by performing gold sensitization, fluctuations in photographic performance when scanning exposure is performed with a laser beam or the like can be further reduced. For gold sensitization, compounds such as chloroauric acid or a salt thereof, gold thiocyanates, gold thiosulfates, and gold colloids can be used. The addition amount of these compounds may vary widely depending on the case, but is from 5 × 10 ^{−7 to} 5 × per mol of silver halide.
The amount is 10 ⁻³ mol, preferably 1 × 10 ⁻⁶ to 1 × 10 ⁻⁴ mol. In the present invention, gold sensitization may be combined with other sensitization methods such as sulfur sensitization, selenium sensitization, tellurium sensitization, reduction sensitization, and noble metal sensitization using a compound other than a gold compound. Among them, a combination of gold sensitization and sulfur sensitization is preferable.

The silver halide photographic light-sensitive material of the present invention is used for a color negative film, a color positive film, a color reversal film, a color reversal photographic paper, a color photographic paper, etc., and among them, a color photographic paper is preferable.
Color photographic paper has a yellow coloring silver halide emulsion layer,
It is preferable to have at least one layer each of a magenta color-forming silver halide emulsion layer and a cyan color-forming silver halide emulsion layer. A silver halide emulsion layer, a magenta color-forming silver halide emulsion layer, and a cyan color-forming silver halide emulsion layer.

However, a different layer configuration may be adopted. The silver halide emulsion layer containing the yellow coupler may be located at any position on the support. However, when the yellow coupler containing layer contains silver halide tabular grains, the silver halide emulsion layer containing the magenta coupler may be used. It is preferable that the coating is provided at a position farther from the support than at least one of the silver emulsion layer and the cyan coupler-containing silver halide emulsion layer. Further, from the viewpoint of accelerating color development, accelerating desilvering, and reducing residual color by the sensitizing dye, the yellow-coupler-containing silver halide emulsion layer is located farthest from the support than the other silver halide emulsion layers. Preferably, it is coated. Further, from the viewpoint of reducing Blix fading, the cyan coupler-containing silver halide emulsion layer is preferably a layer at the center of the other silver halide emulsion layers, and from the viewpoint of reducing photo-fading, the cyan coupler-containing silver halide emulsion layer is preferably The lowermost layer is preferred. Further, each of the color forming layers of yellow, magenta and cyan may be composed of two or three layers. For example, as described in JP-A-4-75055, JP-A-9-114035, JP-A-10-246940 and U.S. Pat. It is also preferable to provide a color-forming layer provided adjacent to the emulsion layer.

The silver halide emulsion and other materials (additives, etc.) and photographic constituent layers (layer arrangement, etc.) used in the present invention, and the processing methods and processing additions applied for processing this light-sensitive material As the agent, JP-A-62-2
No. 15272, JP-A-2-33144, European Patent EP
No. 0,355,660 A2, particularly those described in European Patent EP 0,355,660 A2 are preferably used. Further, JP-A-5-34
No. 889, No. 4-359249, No. 4-313375
Nos. 4-270344, 5-66527, and 4
-34548, 4-145433, 2-854
Nos. 1-158431, 2-90145 and 3
Also preferred are silver halide color photographic light-sensitive materials described in, for example, JP-A-194539, JP-A-2-93641, and European Patent Publication No. 0520457A2, and a processing method thereof.

In particular, in the present invention, the above-mentioned reflective support, silver halide emulsion, different metal ion species doped in silver halide grains, storage stabilizer of silver halide emulsion or antifoggant , Chemical sensitization method (sensitizer),
Spectral sensitization (spectral sensitizer), cyan, magenta, yellow couplers and their emulsifying and dispersing methods, color image preservability improvers (anti-stain and anti-fading agents), dyes (colored layers), gelatin, photosensitive materials With respect to the layer constitution and the coating pH of the photosensitive material, those described in the patents of Tables 1 and 2 can be particularly preferably applied.

[0086]

[Table 1]

[0087]

[Table 2]

The cyan, magenta and yellow couplers used in combination in the present invention are described in
No. 2-215272, page 91, upper right column, line 4 to page 121, upper left column, line 6, JP-A-2-33144, page 3, upper right column, line 14 to page 18, upper left column, last line and page 30, upper right Columns 6-35, lower right column 11; EP 0355,660A2, page 4, lines 15-27; page 5, lines 30-28, last line, page 45, lines 29-31 Eyes, page 47, lines 23-6
The couplers described on page 3, line 50 are also useful. Also, the present invention relates to the general formulas (II) and (III) of WO-98 / 33760 and the general formula (D) of JP-A-10-221825.
A compound represented by formula (I) may be added, which is preferable.

A more specific description will be given below. As described above, the cyan coupler which can be used in combination with the cyan coupler of the present invention is preferably used in combination with a phenol or naphthol cyan coupler.
A cyan coupler represented by the general formula (ADF) described in JP-A-333297 is preferred. Other cyan couplers include those described in European Patent EP 0 488 248 and EP
Pyrroazole type cyan couplers described in Japanese Patent No. 0491971 A1, 2,5-diacylaminophenol couplers described in U.S. Pat. No. 5,888,716, U.S. Pat. Nos. 4,873,183 and 4,916, 051
Pyrazoloazole-type cyan couplers having an electron-withdrawing group and a hydrogen bonding group at the 6-position described in JP-A No.
No. 71185, No. 8-31360, No. 8-3390
It is also preferable to use in combination with a pyrazoloazole-type cyan coupler having a carbamoyl group at the 6-position described in No. 60.

In addition to the diphenylimidazole cyan couplers described in JP-A-2-33144, 3-hydroxypyridine cyan couplers described in European Patent EP 0 333 185 A2 (including couplers listed as specific examples) (42) 4-equivalent coupler having a chlorine leaving group to give a 2-equivalent coupler, couplers (6) and (9) are particularly preferred) and JP-A-64-322.
No. 60, the cyclic active methylene cyan coupler (among others, coupler examples 3, which are listed as specific examples,
8, 34 are particularly preferred), EP 0 422 622
It can also be used in combination with a pyrrolopyrazole-type cyan coupler described in 6A1 and a pyrroleimidazole-type cyan coupler described in European Patent EP 0484909.

Further, as the yellow coupler, in addition to the compounds described in the above table, European Patent EP0447969
An acylacetamide-type yellow coupler having a 3- to 5-membered cyclic structure in an acyl group described in A1 specification, a malondianilide-type yellow coupler having a cyclic structure described in EP0484822A1, EP-A-95870A1 No. 953831A1,
Pyrrole-2 or 3-yl or indole- described in Nos. 953872A1, 953873A1, 953874A1, 9553875A1 and the like.
2 or 3-ylcarbonylacetic acid anilide-based coupler,
An acylacetamide type yellow coupler having a dioxane structure described in U.S. Pat. No. 5,118,599 is preferably used. Among them, it is particularly preferable to use an acylacetamide type yellow coupler in which the acyl group is a 1-alkylcyclopropane-1-carbonyl group and a malondianilide type yellow coupler in which one of the anilides forms an indoline ring. These couplers can be used alone or in combination.

As the magenta coupler used in the present invention, 5-pyrazolone-based magenta couplers and pyrazoloazole-based magenta couplers described in the publicly known documents in the above table are used.
A pyrazolotriazole coupler in which a secondary or tertiary alkyl group is directly bonded to the 2, 3 or 6-position of the pyrazolotriazole ring as described in JP-A-61-65245 in terms of color development and the like. Pyrazoloazole couplers containing a sulfonamide group in the molecule as described in JP-A-65246, pyrazoloazole couplers having an alkoxyphenylsulfonamide ballast group described in JP-A-61-147254, and Europe Patent No. 226,849
It is preferable to use a pyrazoloazole coupler having an alkoxy group or an aryloxy group at the 6-position as described in A or 294,785A. In particular, as the magenta coupler, a pyrazoloazole coupler represented by the general formula (MI) described in JP-A-8-122984 is preferable, and paragraph numbers 0009 to 0026 of the patent are directly applied to the present application. Incorporated as part of the specification. In addition to this, European Patent Nos. 854384 and 8
Pyrazoloazole couplers having a sterically hindered group at both the 3- and 6-positions described in 84640 are also preferably used.

Like the cyan couplers of the present invention, the magenta or yellow couplers can also be used in the presence (or absence) of the high-boiling organic solvents described in the above table in the loadable latex polymer (for example, US Pat. No. 4,203). , 7
No. 16), or dissolved together with a water-insoluble and organic solvent-soluble polymer, and emulsified and dispersed in a hydrophilic colloid aqueous solution. Water-insoluble and organic solvent-soluble polymers which can be preferably used are described in U.S. Pat. No. 4,857,449, columns 7 to 15 and WO 88/00723, pages 12 to 30. The homopolymer or copolymer described above may be used. More preferably, use of a methacrylate-based or acrylamide-based polymer, particularly, an acrylamide-based polymer is preferred from the viewpoint of color image stability and the like.

In the present invention, known color mixing inhibitors can be used, and among them, those described in the following patents are preferable. For example, high-molecular-weight redox compounds described in JP-A-5-333501, WO98 / 33
No. 760, U.S. Pat. No. 4,923,787, etc .; phenidone and hydrazine compounds;
No. 37, JP-A-10-282615 and German Patent No. 19629142A1 can be used. In particular, the pH of the developer is increased,
In the case of speeding up development, German Patent No. 1961878
It is also preferable to use the redox compounds described in 6A1, EP 839623 A1, EP 842975 A1, German Patent 19806846 A1, French Patent 2760460 A1, and the like.

In the present invention, it is preferable to use a compound having a triazine skeleton having a high molar extinction coefficient as the ultraviolet absorber. For example, the compounds described in the following patents can be used. JP-A-46-3335, 55
-152776, JP-A-5-1970074, 5-
No. 232630, No. 5-307232, No. 6-211
No. 813, No. 8-53427, No. 8-234364
Nos. 8-239368, 9-31067, 1
Nos. 0-115598, 10-147577, 10
182621, German Patent 19739797A,
European Patent No. 711804A and Japanese Patent Publication No. Hei 8-5012
No. 91 and the like. The combination of the cyan coupler of the present invention represented by the general formula (I) and the above-mentioned UV absorber having a triazine skeleton is particularly preferable. In this case, the triazine-based UV absorber is used in combination with the support. It is preferred to add to the non-photosensitive layer farther from the layer containing the cyan coupler represented by formula (I) of the present invention and / or the same layer as the cyan coupler.

As a binder or protective colloid that can be used in the light-sensitive material according to the present invention, gelatin is advantageously used, but other hydrophilic colloids can be used alone or together with gelatin. As a preferred gelatin, heavy metals contained as impurities such as iron, copper, zinc, and manganese are preferably 5 ppm.
Or less, more preferably 3 ppm or less. The amount of calcium contained in the photosensitive material is preferably 20 mg.
/ M ² or less, more preferably 10 mg / m ² or less, and most preferably 5 mg / m ² or less. In the present invention,
In order to prevent various molds and bacteria that propagate in the hydrophilic colloid layer and deteriorate the image, it is preferable to add a bactericidal / antifungal agent as described in JP-A-63-271247. Further, the coating pH of the photosensitive material is preferably from 4.0 to 7.0, and more preferably from 4.0 to 6.5.

The light-sensitive material of the present invention is suitable for a scanning exposure method using a cathode ray (CRT) in addition to being used for a printing system using a normal negative printer. A cathode ray tube exposure apparatus is simpler, more compact, and lower in cost than an apparatus using a laser. Further, adjustment of the optical axis and color is also easy. Various light emitters that emit light in a spectral region are used as necessary for a cathode ray tube used for image exposure. For example, any one of a red light emitter, a green light emitter, and a blue light emitter, or a mixture of two or more thereof is used. The spectral region is not limited to the above red, green, and blue, and a phosphor that emits light in a yellow, orange, purple, or infrared region is also used. In particular, a cathode ray tube which emits white light by mixing these light emitters is often used.

In the case where the photosensitive material has a plurality of photosensitive layers having different spectral sensitivity distributions and the cathode tube also has a phosphor which emits light in a plurality of spectral regions, a plurality of colors are exposed at a time, that is, the cathode ray is exposed. A plurality of color image signals may be input to the tube to emit light from the tube surface. A method of sequentially inputting image signals for each color, sequentially emitting light of each color, and exposing through a film that cuts a color other than that color (plane sequential exposure)
In general, plane-sequential exposure is preferable for high image quality because a cathode ray tube with high resolution can be used.

The photosensitive material of the present invention is a gas laser, a light emitting diode, a semiconductor laser, a semiconductor laser or a second harmonic emission light source (SHG) combining a solid-state laser using a semiconductor laser as an excitation light source and a nonlinear optical crystal.
A digital scanning exposure method using monochromatic high-density light is preferably used. In order to make the system compact and inexpensive, it is preferable to use a semiconductor laser, a semiconductor laser or a second harmonic generation light source (SHG) in which a solid-state laser is combined with a nonlinear optical crystal. Particularly, in order to design an apparatus that is compact, inexpensive, and has a long life and high stability, it is preferable to use a semiconductor laser, and it is preferable to use a semiconductor laser as at least one of the exposure light sources.

When such a scanning exposure light source is used,
The spectral sensitivity maximum wavelength of the photosensitive material of the present invention depends on the scanning used.
It can be set arbitrarily according to the wavelength of the exposure light source.
Solid-state laser using semiconductor laser as excitation light source or
Is obtained by combining a semiconductor laser and a nonlinear optical crystal.
SHG light source can halve laser oscillation wavelength
Therefore, blue light and green light can be obtained. Therefore, photosensitive material
The spectral sensitivity maximum is held in the normal three wavelength ranges of blue, green and red.
It is possible to add. In such scanning exposure
The exposure time is based on the pixel when the pixel density is 400 dpi.
If the size is defined as the exposure time, the preferred exposure
10 for time ^-FourSeconds or less, more preferably 10^-6Seconds
Below.

Preferred scanning exposure methods applicable to the present invention are described in detail in the patents listed in the above table. Further, for processing the light-sensitive material of the present invention, the lower right column of page 26, lower right column of page 26 to the upper right column of page 34 of JP-A-2-207250, and the upper left column of page 5 of JP-A-4-97355 can be used. The processing materials and processing methods described in line 17 to page 20, lower right column, line 20 can be preferably applied. As the preservative used in this developer, the compounds described in the patents listed in the above table are preferably used.

The present invention is preferably applied to light-sensitive materials having rapid processing suitability. The color development time refers to the time from when the photosensitive material enters the color developing solution to when it enters the bleach-fix solution in the next processing step. For example, when processing is performed by an automatic developing machine or the like, the time during which the photosensitive material is immersed in the color developing solution (so-called submerged time) and the time when the photosensitive material leaves the color developing solution and is bleach-fixed in the next processing step The sum of the time during which it is transported in the air toward the bath (so-called air time) is referred to as the color development time. Similarly, the bleach-fixing time refers to the time from when the photosensitive material enters the bleach-fixing solution to when it enters the next washing or stabilizing bath. The term “washing or stabilizing time” refers to the time during which the photosensitive material is in the washing or stabilizing solution and is in the solution for the drying step (so-called submerged time).

In the present invention, the color development time is preferably 60 seconds or less, more preferably 50 seconds or less and 6 seconds or more.
More preferably, it is 30 seconds or less and 6 seconds or more. Similarly, the bleach-fixing time is preferably 60 seconds or less, more preferably 5 seconds or less.
It is 6 seconds or more, preferably 0 second or less, more preferably 30 seconds or less. The washing or stabilization time is preferably 15 minutes.
The time is 0 second or less, more preferably 130 seconds or less and 6 seconds or more.

As a method of developing the photosensitive material of the present invention after exposure, there are a conventional method of developing with a developer containing an alkali agent and a developing agent, and a method of incorporating a developing agent into the photosensitive material and containing no developing agent. In addition to a wet method such as a method of developing with an activator liquid, a thermal development method without using a processing liquid can be used. In particular, since the activator method does not contain a developing agent in the processing solution, it is easy to manage and handle the processing solution, and is a preferable method from the viewpoint of environmental conservation because it has a small load when processing the waste liquid. In the activator method, examples of the developing agent or its precursor incorporated in the photosensitive material include, for example, JP-A-8-234.
No. 388, No. 9-152686, No. 9-152693
And hydrazine-type compounds described in JP-A Nos. 9-218814 and 9-160193.

A developing method in which the amount of silver applied to the light-sensitive material is reduced and image amplification processing (intensification processing) using hydrogen peroxide is preferably used. In particular, it is preferable to use this method for the activator method. Specifically, Japanese Patent Application Laid-Open
An image forming method using an activator solution containing hydrogen peroxide described in JP-A-297354 and JP-A-9-152699 is preferably used. In the activator method, after processing with an activator solution, usually a desilvering process is performed, but in an image amplification processing method using a low silver content photosensitive material,
The desilvering process can be omitted, and a simple method such as washing with water or stabilizing process can be performed. Further, in a method in which image information is read from a photosensitive material by a scanner or the like, a processing mode that does not require desilvering processing can be adopted even when a photosensitive material having a high silver content such as a photosensitive material for photography is used.

As the activator solution, desilvering solution (bleaching / fixing solution), washing and stabilizing solution used in the present invention, known processing materials and processing methods can be used. Preferably, Research Disclosure Item 36544
(September 1994) Pages 536 to 541, JP-A-8
-234388 can be used.

When exposing the light-sensitive material of the present invention to a printer, it is preferable to use a band stop filter described in US Pat. No. 4,880,726. As a result, light color mixing is removed, and color reproducibility is significantly improved. In the present invention, as described in European Patent Nos. EP0789270A1 and EP0789480A1, before applying image information, a yellow microdot pattern may be pre-exposed in advance to control copying.

In the case where the coupler of the present invention represented by the general formula (I) is applied to a color negative film, it is disclosed in
Paragraph Nos. 0115 to 02 of the specification of 1-305396
17 are preferably applied and incorporated as part of the specification of the present application. When the coupler represented by the general formula (I) of the present invention is applied to a color reversal film, paragraph No. 00 of the specification of JP-A-11-84601 is used.
18 to 0021 are preferably applied and incorporated as a part of the specification of the present application.

[0109]

The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto.

Example 1 After a corona discharge treatment was applied to the surface of a support obtained by coating both sides of a paper with a polyethylene resin, a gelatin subbing layer containing sodium dodecylbenzenesulfonate was provided. A photographic constituent layer of the seventh layer was sequentially coated to prepare a sample (001) of a silver halide color photographic light-sensitive material having the following layer constitution. The coating solution for each photographic constituent layer was prepared as follows.

Preparation of Coating Solution for Fifth Layer 190 g of cyan coupler (ExC-2), 44 g of cyan coupler (ExC-3), 900 g of gelatin, 44 g of color image stabilizer (Cpd-1), color image stabilizer (Cpd-6) 7
3 g, color image stabilizer (Cpd-7) 11 g, color image stabilizer (Cpd-9) 58 g, color image stabilizer (Cpd-10) 1
5 g, color image stabilizer (Cpd-14) 15 g, color image stabilizer (Cpd-15) 22 g, color image stabilizer (Cpd-16)
73 g, 73 g of color image stabilizer (Cpd-17), 88 g of color image stabilizer (Cpd-18), color image stabilizer (Cpd-1)
9) 88 g of the solvent (Solv-5) 219 g, the solvent (Solv-8) 146 g, and the solvent (Solv-9) 73
g, and 250 ml of ethyl acetate.
200 ml of 0% sodium dodecylbenzenesulfonate
Was emulsified and dispersed in 6500 g of a 10% aqueous gelatin solution containing the same to prepare emulsified dispersion C. On the other hand, silver chlorobromide emulsion C (cubic, 1: 4 mixture of large size emulsion C having an average grain size of 0.50 μm and small size emulsion C having a size of 0.41 μm (silver mole ratio). , Each 0.0
9 and 0.11. 0.5 mol% of silver bromide for each size emulsion
Was locally contained on a part of the surface of the silver chloride-based grain). This emulsion contains the following red-sensitizing sensitizing dyes G and H in an amount of 6.0 × 10 ⁻⁵ mol per mol of silver per mol of silver and small emulsion C per mol of silver, respectively.
^Are added in an amount of 9.0 × 10 ⁻⁵ mol. The chemical ripening of this emulsion was optimally performed by adding a sulfur sensitizer and a gold sensitizer. The emulsified dispersion C and the silver chlorobromide emulsion C were mixed and dissolved to prepare a fifth layer coating solution having the following composition. The emulsion coating amount indicates a coating amount in terms of silver amount.

The coating solutions for the first to fourth layers and the sixth to seventh layers were prepared in the same manner as the coating solution for the fifth layer. As a gelatin hardener for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt was used. Also, Ab-1, Ab-2 , Ab-3 and Ab-4 the total amount respectively 15.0 mg / m ² in each layer, 60.0mg / m ^2,
It was added to a 5.0 mg / m ² and 10.0 mg / m ^2.

[0113]

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The following spectral sensitizing dyes were used for the silver chlorobromide emulsion of each photosensitive emulsion layer. Blue-sensitive emulsion layer

[0115]

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(Sensitizing dyes A, B and C were used in an amount of 1.4 ×
^10-4 moles, ^1.7x each for small size emulsions
10 ^-4 mol was added. Green sensitive emulsion layer

[0117]

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(Sensitizing dye D was added per mole of silver halide,
3.0 × 10 for large emulsions ^-FourMol, small size
3.6 × 10 for emulsion^-FourMol and sensitizing dye E
Per mole of silver halide and for large emulsions
4.0 × 10^-Five7.0 × for mole, small size emulsions
10^-FiveMol of sensitizing dye F per mol of silver halide.
2.0 × 10 for large emulsions^-FourMole, small
2.8 × 10 for size emulsion^-FourMole was added. ) Red-sensitive emulsion layer

[0119]

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(Sensitizing dyes G and H were converted to silver halide 1
6.0 × 1 per mole for large size emulsions
0 ^-5 mol, respectively 9.0 × 1 to the small size emulsion
0 ^-5 mol was added. Further, the following compound I was added to the red-sensitive emulsion layer in an amount of 2.6 × 10 ^-3 mol per mol of silver halide.

[0121]

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Further, a blue-sensitive emulsion layer, a green-sensitive emulsion layer and
1- (3-methylureidophenyl) was added to the red-sensitive emulsion layer.
) -5-mercaptotetrazole
3.3 × 10 per mole of silver halide^-FourMol, 1.0 × 10^-3
Mol and 5.9 × 10^-FourMole was added. Furthermore, the second
Layer, the fourth layer, the sixth layer and the seventh layer, respectively.
mg / m ^Two0.2 mg / m^Two, 0.6 mg / m^Two, 0.
1mg / m^TwoWas added so that Blue-sensitive emulsion
Layer and the green-sensitive emulsion layer.
Chill-1,3,3a, 7-tetrazaindene,
Per mole of silver halide^-FourMole, 2 × 1
0^-FourMole was added.

Further, a copolymer of methacrylic acid and butyl acrylate (mass ratio 1: 1, average molecular weight 2
(0000 to 400,000) was added at 0.05 g / m ² . Also, disodium catechol-3,5-disulfonate and 2,6-bishydroxyamino-4-diethylamino-1,3,5 were added to the second, fourth and sixth layers.
A mixture of triazines (9: 1 molar ratio)
mg / m ² , 6 mg / m ² and 18 mg / m ² . To prevent irradiation, the following dyes were added to the emulsion layer.

[0124]

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(Layer Structure) The structure of each layer is shown below. The numbers represent the coating amount (g / m ² ). The silver halide emulsion is
It represents the silver equivalent coating amount. Support Polyethylene resin laminated paper [A white pigment (TiO ₂ ;
Content 16% by mass, ZnO; content 4% by mass) and optical brighteners (4,4'-bis (benzoxazolyl) stilbene and 4,4'-bis (5-methylbenzoxazolyl)
8/2 mixture of stilbene: content 0.05% by mass),
Including blue dye (ultramarine)

First Layer (Blue-Sensitive Emulsion Layer) Silver chlorobromide emulsion (cubic, 3: 7 mixture of large-size emulsion A having an average grain size of 0.72 μm and small-size emulsion A having a 0.60 μm emulsion (silver molar ratio) The coefficient of variation of the grain size distribution was 0.08 and 0.10, respectively, and 0.3 mol% of silver bromide was locally contained in a part of the grain surface based on silver chloride in each size emulsion. ) 0.26 Gelatin 1.35 Yellow coupler (ExY) 0.62 Color image stabilizer (Cpd-1) 0.08 Color image stabilizer (Cpd-2) 0.04 Color image stabilizer (Cpd-3) 0 0.08 Color image stabilizer (Cpd-8) 0.01 Solvent (Solv-1) 0.23

Second layer (color mixture preventing layer) Gelatin 0.99 Color mixture inhibitor (Cpd-4) 0.09 Color image stabilizer (Cpd-5) 0.018 Color image stabilizer (Cpd-6) 0.13 Color image stabilizer (Cpd-7) 0.01 Solvent (Solv-1) 0.06 Solvent (Solv-2) 0.22

Third Layer (Green-Sensitive Emulsion Layer) Silver chlorobromide emulsion B (cubic, 1: 3 mixture of large-size emulsion B with an average grain size of 0.45 μm and small-size emulsion B of 0.35 μm (silver mole The coefficient of variation of the grain size distribution was 0.10 and 0.08, respectively. In each size emulsion, 0.4 mol% of silver bromide was locally contained in a part of the grain surface based on silver chloride.) 0.14 Gelatin 1.36 Magenta coupler (ExM) 0.15 UV absorber (UV-1) 0.05 UV absorber (UV-2) 0.03 UV absorber (UV-3) 0.02 UV absorption Agent (UV-4) 0.03 Ultraviolet absorber (UV-6) 0.01 Color image stabilizer (Cpd-2) 0.02 Color image stabilizer (Cpd-4) 0.002 Color image stabilizer (Cpd) -6) 0.09 Color image stabilizer (Cpd-8) 0.02 Image stabilizer (Cpd-9) 0.03 Color image stabilizer (Cpd-10) 0.01 Color image stabilizer (Cpd-11) 0.0001 Solvent (Solv-3) 0.11 Solvent (Solv-4) 0.22 Solvent (Solv-5) 0.20

Fourth layer (color mixture preventing layer) Gelatin 0.71 Color mixture inhibitor (Cpd-4) 0.06 Color image stabilizer (Cpd-5) 0.013 Color image stabilizer (Cpd-6) 0.10 Color image stabilizer (Cpd-7) 0.007 Solvent (Solv-1) 0.04 Solvent (Solv-2) 0.16

Fifth Layer (Red-Sensitive Emulsion Layer) Silver chlorobromide emulsion C (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 (silver mole The coefficient of variation of the grain size distribution was 0.09 and 0.11, respectively. In each size emulsion, 0.5 mol% of silver bromide was contained locally on a part of the grain surface based on silver chloride.) 0.20 Gelatin 1.11 Cyan coupler (ExC-2) 0.13 Cyan coupler (ExC-3) 0.03 Color image stabilizer (Cpd-1) 0.05 Color image stabilizer (Cpd-6) 05 Color image stabilizer (Cpd-7) 0.007 Color image stabilizer (Cpd-9) 0.04 Color image stabilizer (Cpd-10) 0.01 Color image stabilizer (Cpd-14) 0.01 color Image stabilizer (Cpd-15) 0.015 Color image stabilizer (Cpd- 16) 0.05 Color image stabilizer (Cpd-17) 0.05 Color image stabilizer (Cpd-18) 0.06 Color image stabilizer (Cpd-19) 0.06 Solvent (Solv-5) 0.15 Solvent (Solv-8) 0.05 Solvent (Solv-9) 0.10

Sixth layer (ultraviolet absorbing layer) Gelatin 0.66 Ultraviolet absorbing agent (UV-1) 0.11 Ultraviolet absorbing agent (UV-2) 0.06 Ultraviolet absorbing agent (UV-3) 0.06 Ultraviolet absorbing Agent (UV-4) 0.05 Ultraviolet absorber (UV-5) 0.08 Ultraviolet absorber (UV-6) 0.005 Solvent (Solv-7) 0.25 Seventh layer (protective layer) Gelatin 1. 00 Acrylic-modified copolymer of polyvinyl alcohol (degree of modification 17%) 0.04 Liquid paraffin 0.02 Surfactant (Cpd-13) 0.01

[0132]

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[0133]

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[0134]

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[0135]

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[0136]

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[0137]

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[0138]

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[0139]

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[0140]

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Further, the cyan coupler (ExC-2) of the emulsified dispersion C for the fifth layer of the silver halide color photographic light-sensitive material (001) prepared as described above was changed to the same molar amount of the compound shown in Table 3. Samples (101) to (11) similar to Sample (001) except that the cyan coupler was changed by using an emulsified dispersion prepared by the same method except that
2) was produced. The average particle size of the cyan coupler-containing lipophilic fine particle dispersion prepared here was in the range of 0.10 to 0.20 μm.

The above photosensitive material (001) was treated at 25 ° C. and 55% R
After storing in H for 10 days, processed into a 127 mm wide roll, imagewise exposed using Fuji Photo Film Co., Ltd. minilab printer processor PP1258AR, and replenished twice the color developing tank capacity in the following processing steps , Continuous processing (running test). Processing process Temperature Time Replenishment amount * Color development 38.5 ° C 45 seconds 45 ml Bleaching and fixing 38.0 ° C 45 seconds 35 ml Rinse (1) 38.0 ° C 20 seconds-Rinse (2) 38.0 ° C 20 seconds -Rinse (3) ** 38.0 ° C for 20 seconds-Rinse (4) ** 38.0 ° C for 30 seconds 121 ml * Replenishment amount per 1 m ^{2 of} photographic material ** Rinse phosphorus screening system RC50D manufactured by Fuji Photo Film Co., Ltd. Install in (3), take out the rinse liquid from rinse (3), and send it to reverse osmosis membrane module (RC50D) by pump. The permeated water obtained in the tank is supplied to the rinse (4), and the concentrated water is returned to the rinse (3). The pump pressure was adjusted so that the amount of permeated water to the reverse osmosis module was maintained at 50 to 300 ml / min, and the temperature was circulated for 10 hours a day. (Rinsing was carried out in a tank countercurrent system from (1) to (4).)

The composition of each processing solution is as follows. [Color developer] [Tank solution] [Replenisher] Water 800 ml 800 ml dimethylpolysiloxane-based surfactant (silicone KF351A / Shin-Etsu Chemical Co., Ltd.) 0.1 g 0.1 g triethanolamine 11.6 g 11.6 g Ethylenediaminetetraacetic acid 4.0 g 4.0 g 4,5-dihydroxybenzene-1,3-disulfonic acid sodium 0.5 g 0.5 g potassium chloride 10.0 g-potassium bromide 0.040 g 0.010 g triazinylaminostilbene Fluorescent whitening agent (Hakor FWA-SF / Showa Chemical Co., Ltd.) 2.5 g 5.0 g sodium sulfite 0.1 g 0.1 g disodium-N, N-bis (sulfonatoethyl) hydroxylamine 8.5 g 11.1 g N -Ethyl-N- (β-methanesulfonamidoethyl ) -3-Methyl-4-amino-4-aminoaniline / 3/2 sulfuric acid / monohydrate 5.0 g 15.7 g Potassium carbonate 26.3 g 26.3 g Water was added and 1000 ml 1000 ml pH (25 ° C / (Adjusted with potassium hydroxide and sulfuric acid) 10.15 12.50

[Bleach-fixing solution] [Tank solution] [Replenisher] Water 800 ml 800 ml Iron (III) ammonium ethylenediaminetetraacetate 47.0 g 94.0 g 1.4 g 2.8 g m-carboxymethylbenzenesulfine ethylenediaminetetraacetic acid Acid 8.3 g 16.5 g Nitric acid (67%) 16.5 g 33.0 g Imidazole 14.6 g 29.2 g Ammonium thiosulfate (750 g / liter) 107 ml 214 ml ammonium sulfite 16.0 g 32.0 g potassium metabisulfite 23. 1 g 46.2 g Add water 1000 ml 1000 ml pH (adjusted at 25 ° C./acetic acid and ammonia) 6.0 6.0

[Rinse solution] [Tank solution] [Replenisher] 0.02 g 0.02 g of chlorinated sodium isocyanurate Deionized water (conductivity of 5 μS / cm or less) 1000 ml 1000 ml pH 6.5 6.5

Next, each sample was subjected to gradation exposure using a three-color separation optical wedge for sensitometry using a sensitometer (Fuji Photo Film Co., Ltd., FWH type, color temperature of light source: 3200 ° K). The exposure at this time is 25 seconds with an exposure time of 0.1 second.
The exposure was performed so that the exposure amount was 0 lx · sec (lux · sec). Each of the exposed samples was developed using the above-mentioned running processing solution to obtain samples in which yellow, magenta, and cyan were developed.

(Evaluation of Color Reproducibility)
-Rite 350 densitometer (manufactured by The X-rite Company)
It measured using. As shown in Table 3, all of the samples of the present invention exhibited a sufficient color density of Dmax of 2 or more. Next, a magenta density M (C
2.0). The smaller the value of M (C2.0), the smaller the turbidity of the magenta component in cyan and the more excellent the hue.

(Evaluation of Processing Color Mixing)
The density was measured using a write 350 densitometer (manufactured by The X-rite Company) to obtain a cyan density C (M2.0) at a magenta density of 2.0. The smaller the value of C (M2.0), the smaller the amount of cyan color (processed color mixture) during magenta color development.

(Evaluation of Light Fastness) Xenon light (100,000 lux xenon light irradiator) was applied to the sample having the cyan dye image through a UV cut filter having a light transmittance of 50% at 370 nm and a heat ray cut filter. 14
Irradiated for days. The density after the light irradiation at a cyan density of 2.0 before the light irradiation was measured, and the light fastness was represented by the residual density (%). Table 3 summarizes the above results.

[0150]

[Table 3]

[0151]

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The results in Table 3 show that the sample using the cyan coupler of the present invention was replaced with the sample (00) using the conventional cyan coupler.
It shows that the magenta density in cyan is smaller than that of 1) and an excellent cyan color is provided. Also, according to the visual sensory evaluation, the sample of the present invention had an excellent cyan color with less magenta or yellow turbidity in the cyan color than the comparative sample. Further, from the results of the processing color mixing shown in Table 3, the sample of the present invention has little cyan color mixing at the time of magenta coloring, and processing color mixing is improved. Further, from the results of the xenon photofading test in Table 3, it was found that when the cyan coupler of the present invention was used, the light fastness was excellent. The effects of the present invention described above are obtained when the pyrrolotriazole cyan coupler has the specific structure represented by the general formula (I). When the conventional cyan coupler is used, the comparative sample (001) As shown by the results of (111) and (112), the excellent color reproducibility, color mixing, and improvement of light fastness of the present invention cannot be achieved.

Example 2 Each sample was developed and evaluated in the same manner as in Example 2 except that the exposure of each photosensitive material was performed by the scanning exposure described below. As a result, it was confirmed that all the samples using the cyan coupler of the present invention represented by the general formula (I) exhibited excellent hue and light fastness similarly to Example 2.

For the scanning exposure, the scanning exposure apparatus shown in FIG. 1 of JP-A-8-16238 was used. As a light source, a 688 nm light source (R light) using a semiconductor laser and a 532 nm light source (G light
Light) and a 473 nm light source (B light). The amount of R light is modulated using an external modulator and reflected by a rotating polyhedron,
The sample moving perpendicular to the scanning direction was scanned and exposed. The scanning exposure was performed at 400 dpi, and the average exposure time per pixel was 8 × 10 ⁻⁸ seconds. The temperature of the semiconductor laser was kept constant by using a Peltier element in order to suppress a change in light amount due to temperature.

[0155]

According to the novel compound for forming a dye having a pyrrolotriazole skeleton according to the present invention, a dye excellent in hue and light resistance can be obtained, and when used as a cyan coupler in a silver halide color photographic light-sensitive material. It has high color developability, excellent light fastness of the obtained color image, a cyan hue without turbidity, and an excellent effect of color mixing during processing. The silver halide color photographic light-sensitive material of the present invention containing this compound is excellent in color reproducibility and light fastness, and has high illuminance exposure suitability.

Claims (2)

[Claims] 1. A silver halide color photographic material comprising a cyan coupler represented by the following general formula (I). General formula (I) In the general formula (I), R ¹ and R ² each independently represent an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group or a heterocyclic group. Here, R ¹ and R ² may combine with each other to form a 5- or 6-membered nitrogen-containing heterocyclic ring. R ³
Represents an alkyl group, a cycloalkyl group or an alkenyl group. R ⁴ and R ⁵ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group or a heterocyclic group. Here, R ⁴ and R ⁵ may combine with each other to form a 5- or 6-membered nitrogen-containing heterocyclic ring. 2. A cyan dye-forming compound represented by the following general formula (I). General formula (I) In the general formula (I), R ¹ and R ² each independently represent an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group or a heterocyclic group. Here, R ¹ and R ² may combine with each other to form a 5- or 6-membered nitrogen-containing heterocyclic ring. R ³
Represents an alkyl group, a cycloalkyl group or an alkenyl group. R ⁴ and R ⁵ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group or a heterocyclic group. Here, R ⁴ and R ⁵ may combine with each other to form a 5- or 6-membered nitrogen-containing heterocyclic ring.