JPH0553275A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide the silver halide color photographic sensitive material superior in color development performance and light fastness of a magenta dye image. CONSTITUTION:The silver halide color photographic sensitive material has blue-sensitive, green-sensitive, and red-sensitive emulsion layers on a support and this green-sensitive emulsion layer contains at least one kind of pyrazoloazole type coupler, and at least one kind of a compound among the compounds represented by A-I, A-II, A-III, and A-IV. In formujla I, each of R<1> and R<2> is H or a substituent: R<3> is acylamino or sulfonamido; R<4> is a substituent except H; and X is H or a releasable group. In formulae A-I to A-IV, A is a nonmetallic atomic group for forming a 5- or 7-mcmbered ring: X is -0=, -S-, or the like: and II is Cu, Co, Ni, Pd, or Pt.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a silver halide color photographic light-sensitive material.

More particularly, it relates to a silver halide color photographic light-sensitive material which is excellent in color reproducibility and has a markedly improved light fastness of a magenta color image.

[0003]

2. Description of the Related Art A silver halide color photographic light-sensitive material generally has a silver halide emulsion layer which is sensitive to each of the three primary colors of blue, green and red, and each of them develops so-called yellow, magenta and cyan. Reproduce the color image using the subtractive method. Therefore, the reproduced color image largely depends on the color-sensitive property of each layer and the spectral absorption property of the coloring dye. In general, these characteristics are not always the best in theory due to the restrictions of the compound used, such as the coloring property.

In particular, the spectral absorption characteristics of the coloring dye of the magenta coupler are important for color reproduction, and various improvements have been made. Among them, the pyrazoloazole-based magenta coupler is particularly excellent in the spectral absorption property of the coloring dye. For example, the pyrazoloazole-based magenta coupler described in U.S. Pat. No. 3,725,067 has less unnecessary absorption in the blue light region and the red light region as compared with the color image obtained from the 5-pyrazolone type magenta coupler, and color reproduction is small. Not only is it advantageous,
The coupler itself is stable against light, heat, and humidity and is difficult to disperse, so that the obtained image has an excellent yellowing property.

However, a color image obtained from a pyrazoloazole-based magenta coupler has a drawback that it is inferior in light fastness to a color image obtained from a 5-pyrazolone-based magenta coupler.

As a means for improving the light fastness of a color image obtained from a pyrazoloazole type magenta coupler, a method of using a specific compound as an inhibitor is disclosed in, for example, JP-A Nos. 62-92945 and 63-163351. Issue 61
-90156, 61-145554, U.S. Pat.
588,679, 4,590,153, 4,7
35,893.

The light fastness is improved by using the specific examples of the pyrazoloazole-based magenta couplers disclosed in these and an inhibitor, but the improving effect by the inhibitor is not sufficient, or by the inhibitor. Although the improvement effect is considerably large, further improvement is desired because the absolute level of light fastness is not sufficient.

On the other hand, it is known from the coupler structure to introduce a bulky substituent at the 6-position of the pyrazoloazole nucleus as a means for improving the light fastness. Examples of the pyrazoloazole-based magenta coupler in which a bulky substituent is introduced at the 6-position include, for example, US Pat. No. 5,021,32.
No. 5, and these couplers are economical in production cost and excellent in color developability, but the light fastness of a magenta color image obtained from these couplers is still insufficient. However, further improvement was desired.

[0009]

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and it is an object of the present invention to provide a silver halide color which is excellent in color developability and light fastness of a magenta color image. It is to provide a photographic light-sensitive material.

[0010]

As a result of earnest research, the present inventors have found that when a pyrazoloazole-based magenta coupler having a specific structure is used in combination with a specific compound, the effect of improving light fastness is specific. It was found that the light fastness was extremely high and the light fastness level was also very good. That is, the object of the present invention is achieved by the following means.

A blue-sensitive emulsion layer, a green-sensitive emulsion layer, on a support,
In a silver halide color photographic light-sensitive material having at least one red-sensitive emulsion layer, the green-sensitive emulsion layer contains at least one pyrazoloazole type coupler represented by the following general formula (I) and the following general formula (A). -I), (A-I
I), (A-III) and at least one of the compounds represented by (A-IV) are contained in the silver halide color photographic light-sensitive material.

[0012]

[Chemical 6] In the formula, R ¹ and R ² represent a hydrogen atom or a substituent. However, R ¹ and R ² do not become hydrogen atoms at the same time. R
³ represents an acylamino group or a sulfonamide group. R
⁴ represents a substituent other than a hydrogen atom, n is 0, 1 or 2
Is. X represents a hydrogen atom or a group capable of splitting off upon reaction with an oxidized product of an aromatic primary amine color developing agent.

[0013]

[Chemical 7] In formulas (AI) to (A-IV), R is a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a silyl group, a phosphino group, or a protecting group capable of being deprotected under alkaline conditions. Represents. X is -O-, -S-, or

[0014]

[Chemical 8] Represents. R'represents a group defined by R. R ₁ ~ R
₅ may be the same or different, and each is a hydrogen atom, -X
-R, alkyl group, alkenyl group, aryl group, heterocyclic group, alkyloxycarbonyl group, aryloxycarbonyl group, halogen atom, acyl group, sulfonyl group,
It represents a carbamoyl group, a sulfamoyl group, a cyano group, a nitro group, a sulfo group or a carboxyl group.

In the general formula (AI), -X-R, R ₁
Of the groups represented by R ₅ to R ₅ , the substituents in the ortho positions may be bonded to each other to form a 5 to 7 membered ring.

R ₁₀ represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an oxy radical group, a hydroxy group, an acyl group, a sulfonyl group or a sulfinyl group.
R _{11 to} R ₁₄ may be the same or different and each represents a hydrogen atom or an alkyl group. A represents a nonmetallic atom group necessary for forming a 5- to 7-membered ring.

M represents copper, cobalt, nickel, palladium or platinum. R ₂₀ , R ₂₁ , R ₂₂ , R ₂₀ ′, R
₂₁ ′ and R ₂₂ ′ may be the same or different and each represents a hydrogen atom, an alkyl group or an aryl group. R ₂₃
R ₂₃ ′ may be the same or different and each represents a hydrogen atom, an alkyl group, an aryl group, a hydroxyl group, an alkoxy group or an aryloxy group. Where R ₂₃
And R ₂₃ ′ may combine with each other. In addition, R _{20 to} R ₂₃ , R
_{20'~R 23} may form an aromatic ring or a 5-8-membered ring is adjacent groups together among the group '.

A ₁ and A ₃ may be the same or different and each represents an oxygen atom, a sulfur atom, a hydroxyl group,
Mercapto group, alkoxy group, alkylthio group, or

[0019]

[Chemical 9] Represents. Here, R ₃₄ and R ₃₅ may be the same or different and each represents a hydrogen atom, an alkyl group, an aryl group or a hydroxyl group. A ₂ is -O-, -S-, or

[0020]

[Chemical 10] Represents. R ₃₆ represents a hydrogen atom, an alkyl group or an aryl group. R _{30 to} R ₃₃ may be the same or different and each represents a hydrogen atom, an alkyl group or an aryl group. Here, R ₃₀ and R ₃₃ are bonded to each other to form an aromatic ring or 5
A ~ 8-membered ring may be formed. B represents a compound capable of coordinating to M. The conformational number of this compound is 1-5.

Among the groups defined in the general formulas (AI) to (A-IV), the group having a carbon atom may further have a substituent on this carbon atom.

The present invention will be described in more detail below.

R ¹ , R ² , R ³ in the general formula (I),
R ⁴ and X will be described in detail.

R ¹ and R ² are hydrogen atom, halogen atom, alkyl group, aryl group, heterocyclic group, cyano group, hydroxy group, nitro group, carboxy group, sulfo group, amino group, alkoxy group, aryloxy group, Acylamino group, alkylamino group, anilino group, ureido group, sulfamoylamino group, alkylthio group, arylthio group, alkoxycarbonylamino group, sulfonamide group, carbamoyl group, sulfamoyl group, sulfonyl group, alkoxycarbonyl group, heterocyclic oxy group Group, azo group, acyloxy group, albamoyloxy group, silyloxy group, aryloxycarbonylamino group, imide group, heterocyclic thio group, sulfinyl group, phosphonyl group,
It represents an aryloxycarbonyl group, an acyl group, or an azolyl group, and R ⁴ represents a group in which a hydrogen atom has been removed from the substituents exemplified for R ¹ and R ² . R ¹ , R ² and R ⁴ may be a divalent group to form a bis form.

More specifically, R ¹ and R ² are each a hydrogen atom, a halogen atom (eg, chlorine atom, bromine atom), an alkyl group (eg, a straight chain or branched chain alkyl group having 1 to 32 carbon atoms, or aralkyl). Group, alkenyl group, alkynyl group, cycloalkyl group, cycloalkenyl group, and specifically, for example, methyl, propyl, isopropyl, t-butyl, tridecyl, 2-methanesulfonylethyl, 3-
(3-Pentadecylphenoxy) propyl, 3- {4-
{2- [4- (4-hydroxyphenylsulfonyl) phenoxy] dodecanamide} phenyl} propyl, 2-
Ethoxytridecyl, trifluoromethyl, cyclopentyl, 3- (2,4-di-t-amylphenoxy) propyl), aryl groups (eg phenyl, 4-t-butylphenyl, 2,4-di-t-amyl) Phenyl, 2,
4,6-Trimethylphenyl, 3-tridecanamide-
2,4,6-trimethylphenyl, 4-tetradecanamidophenyl), a heterocyclic group (eg, 2-furyl, 2
-Thienyl, 2-pyrimidinyl, 2-benzothiazolyl), cyano group, hydroxy group, nitro group, carboxy group, sulfo group, amino group, alkoxy group (for example, methoxy, ethoxy, 2-methoxyethoxy, 2-dodecylethoxy, 2 -Methanesulfonylethoxy), aryloxy groups (eg phenoxy, 2-methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, 3-t-butyloxycarbamoylphenoxy, 3
-Methoxycarbamoyl), an acylamino group (for example,
Acetamide, benzamide, tetradecanamide, 2
-(2,4-di-t-amylphenoxy) butanamide, 4- (3-t-butyl-4-hydroxyphenoxy) butanamide, 2- {4- (4-hydroxyphenylsulfonyl) phenoxy} decanamide), alkylamino A group (eg, methylamino, butylamino, dodecylamino, diethylamino, methylbutylamino),
Anilino group (eg, phenylamino, 2-chloroanilino, 2-chloro-5-tetradecaneaminoanilino,
2-chloro-5-dodecyloxycarbonylanilino,
N-acetylanilino, 2-chloro-5- {2- (3-
t-butyl-4-hydroxyphenoxy) dodecanamide} anilino), ureido group (eg, phenylureido, methylureido, N, N-dibutylureido), sulfamoylamino group (eg, N, N-dipropylsulfamoyl) Amino, N-methyl-N-decylsulfamoylamino), alkylthio group (for example, methylthio, octylthio, tetradecylthio, 2-phenoxyethylthio, 3-phenoxypropylthio, 3- (4-)
t-butylphenoxy) propylthio), an arylthio group (for example, phenylthio, 2-butoxy-5-t-octylphenylthio, 3-pentadecylphenylthio,
2-carboxyphenylthio, 4-tetradecanamidophenylthio), alkoxycarbonylamino group (for example, methoxycarbonylamino, tetradecyloxycarbonylamino), sulfonamide group (for example, methanesulfonamide, hexadecanesulfonamide, benzenesulfonamide, p-toluenesulfonamide, octanedecanesulfonamide, 2-methoxy-5-t-butylbenzenesulfonamide), carbamoyl group (for example, N-ethylcarbamoyl, N, N-dibutylcarbamoyl, N- (2-dodecyloxyethyl). ) Carbamoyl, N-methyl-N-dodecylcarbamoyl, N- {3
-(2,4-di-t-amylphenoxy) propyl} carbamoyl), a sulfamoyl group (for example, N-ethylsulfamoyl, N, N-dipropylsulfamoyl,
N- (2-dodecyloxyethyl) sulfamoyl, N
-Ethyl-N-dodecylsulfamoyl, N, N-diethylsulfamoyl), sulfonyl group (for example, methanesulfonyl, octanesulfonyl, benzenesulfonyl, toluenesulfonyl), alkoxycarbonyl group (for example, methoxycarbonyl, butyloxycarbonyl) , Dodecyloxycarbonyl, octadecyloxycarbonyl), a heterocyclic oxy group (for example, 1-phenyltetrazole-5-oxy, 2-tetrahydropyranyloxy), an azo group (for example, phenylazo, 4-methoxyphenylazo, 4-pi). Valoylaminophenylazo,
2-hydroxy-4-propanoylphenylazo), acyloxy group (eg acetoxy), carbamoyloxy group (eg N-methylcarbamoyloxy, N-
Phenylcarbamoyloxy), silyloxy group (eg, trimethylsilyloxy, dibutylmethylsilyloxy), aryloxycarbonylamino group (eg,
Phenoxycarbonylamino), imide group (eg, N
-Succinimide, N-phthalimide, 3-octadecenylsuccinimide), a heterocyclic thio group (for example, 2-
Benzothiazolylthio, 2,4-di-phenoxy-1,
3,5-triazole-6-thio, 2-pyridylthio), sulfinyl group (eg, dodecanesulfinyl, 3-pentadecylphenylsulfinyl, 3-phenoxypropylsulfinyl), phosphonyl group (eg, phenoxyphosphonyl, octyloxyphosphonyl) , Phenylphosphonyl), aryloxycarbonyl groups (eg, phenoxycarbonyl), acyl groups (eg, acetyl, 3-phenylpropanoyl, benzoyl, 4-dodecyloxybenzoyl), azolyl groups (eg, imidazolyl, pyrazolyl, 3- (Chloro-pyrazol-1-yl, triazolyl), and R ⁴ represents a group in which a hydrogen atom has been removed from the substituents exemplified for R ¹ and R ² . Among these substituents, the group capable of further having a substituent may further have an organic substituent or a halogen atom linked by a carbon atom, an oxygen atom, a nitrogen atom or an ion atom.

Of these substituents, preferred R ¹ and R
² and R ⁴ are alkyl groups, more preferably R ¹ and R 4.
² is a methyl group and R ⁴ is a 4-methyl group.

R ³ represents an acylamino group or a sulfonamide group, and R ³ may be a divalent group to form a bis form.

More specifically, R ³ is an acylamino group (eg, acetamide, benzamide, tetradecane amide, 2- (2,4-di-t-amylphenoxy) butanamide, 4- (3-t-butyl-4-hydroxy). Phenoxy) butanamide, 2- {4- (4-hydroxyphenylsulfonyl) phenoxy} decanamide, 3-
Dodecanesulfonylpropanamide, 1-dodecaneamide-3-methanesulfonylpropanamide, 1-dodecaneamide-3-methanesulfoxypropanamide), sulfonamide group (for example, methanesulfonamide, hexadecanesulfonamide, benzenesulfonamide, p
-Toluenesulfonamide, octadecanesulfonamide, 2-methoxy-5-t-butylbenzenesulfonamide, 2-octyloxy-5-t-octylbenzenesulfonamide).

Among these substituents, R ³ is preferably an acylamino group, and more preferably, an acylamino group is formed by a carboxylic acid moiety of a substituted or unsubstituted α-amino acid-derived group to give a general formula (I). Is a group bonded to a carbon atom on the benzene ring of.

X represents a hydrogen atom or a group capable of splitting off upon reaction with an oxidation product of an aromatic primary amine color developing agent. The splitting-off group is specifically described as a halogen atom, an alkoxy group, an aryloxy group or an acyloxy group. Group, alkyl or aryl sulfonyloxy group, acylamino group, alkyl or aryl sulfonamide group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, alkyl, aryl or heterocyclic thio group, carbamoylamino group, 5-membered or 6-membered group Examples thereof include a nitrogen heterocyclic group, an imide group, and an arylazo group, and these groups may be further substituted with another substituent.

More specifically, halogen atom (eg, fluorine atom, chlorine atom, bromine atom), alkoxy group (eg, ethoxy, dodecyloxy, methoxyethylcarbamoylmethoxy, carboxypropyloxy, methylsulfonylethoxy, ethoxycarbonylmethoxy), aryl An oxy group (for example, 4-methylphenoxy, 4-
Chlorophenoxy, 4-methoxyphenoxy, 4-carboxyphenoxy, 3-ethoxycarbonylphenoxy, 4-methoxycarbonylphenoxy, 3-acetylaminophenoxy, 2-carboxyphenoxy), acyloxy group (for example, acetoxy, tetradecanoyloxy, benzoyl) Oxy), an alkyl or aryl sulfonyloxy group (eg, methanesulfonyloxy, toluenesulfonyloxy), an acylamino group (eg, dichloroacetylamino, heptafluorobutyrylamino), an alkyl or aryl sulfonamide group (eg, methanesulfonamino) , Trifluoromethanesulfonamino, p-toluenesulfonamino), alkoxycarbonyloxy groups (eg, ethoxycarbonyloxy, benzyl) Xycarbonyloxy), aryloxycarbonyloxy groups (eg phenoxycarbonyloxy), alkyl, aryl or heterocyclic thio groups (eg dodecylthio, 1-carboxydodecylthio, phenylthio, 2-butoxy-5-t-octylphenylthio). , 2-benzyloxycarbonylaminophenylthio, tetrazolylthio), a carbamoylamino group (for example, N-methylcarbamoylamino, N-
Phenylcarbamoylamino) 5- or 6-membered nitrogen-containing heterocyclic group (for example, 1-imidazolyl, 1-pyrazolyl, 1,2,4-triazol-1-yl, tetrazolyl, 3,5-dimethyl-1-pyrazolyl , 4-cyano-1-pyrazolyl, 4-methoxycarbonyl-1-pyrazolyl, 4-acetylamino-1-pyrazolyl, 1,
2-dihydro-2-oxo-1-pyridyl), an imide group (eg, succinimide, hydantoinyl), an arylazo group (eg, phenylazo, 4-methoxyphenylazo), and the like. In addition to these, X is an aldehyde or ketone as a leaving group bonded via a carbon atom.
It may also take the form of a bis-type coupler obtained by condensing an equivalent coupler. Further, X may contain a photographically useful group such as a development inhibitor or a development accelerator. Preferred X is a halogen atom, an alkoxy group, an aryloxy group, an alkyl or arylthio group, and a 5-membered or 6-membered nitrogen-containing heterocyclic group bonded to the coupling active position with a nitrogen atom, particularly preferably a halogen atom, It is a substituted aryloxy group or a substituted 1-pyrazolyl group.

Specific examples of the general formula (I) in the present invention are shown below, but the invention is not limited thereto.

[0033]

[Chemical 11]

[0034]

[Chemical formula 12]

[0035]

[Chemical 13]

[0036]

[Chemical 14]

[0037]

[Chemical 15]

[0038]

[Chemical 16]

[0039]

[Chemical 17]

[0040]

[Chemical 18]

[0041]

[Chemical 19]

[0042]

[Chemical 20]

[0043]

[Chemical 21]

[0044]

[Chemical formula 22]

[0045]

[Chemical formula 23] Next, an example of a synthetic route for Exemplified Compound I-1 is shown.

[0046]

[Chemical formula 24]

[0047]

[Chemical 25] Synthesis of Compound (3) 179 g of Compound (1) was added to a solution prepared by dissolving 48 g of sodium hydroxide in 1.2 liter of water, and the mixture was mixed with the compound (2) from one dropping funnel while vigorously stirring under ice cooling. ) 131.2 g of water was added from another dropping funnel at the same time with an aqueous solution of 24 g of sodium hydroxide dissolved in 100 ml of water.
It dripped over minutes. At this time, the internal temperature rose to 7 ° C.
After completion of dropping, the mixture was continuously stirred for 2 hours, poured into ice water, 185 ml of concentrated hydrochloric acid was added with stirring, and then the mixture was stirred for 30 minutes. The obtained crystals were filtered by suction, washed with water and dried to obtain 155 g of the target compound (3) in a yield of 78%.

Synthesis of Compound (4) To 155 g of Compound (3), 600 ml of ethanol was added and stirred, and an aqueous solution in which 1.0 g of Na ₂ WO ₄ was dissolved in 2 ml of water was added. 100 m of hydrogen peroxide water (34.5% aqueous solution) is added to this while heating under reflux and stirring.
1 was added dropwise, taking care not to over reflux. After the dropwise addition was completed, the mixture was stirred under heating under reflux for 2 hours, cooled to room temperature, and extracted with 500 ml of 1 liter saturated saline of ethyl acetate. The obtained ethyl acetate layer was washed 3 times with 500 ml of saturated saline, dried over anhydrous sodium sulfate, and concentrated to obtain 175 g of a crude product of the desired compound (4) as an oily substance.

Synthesis of compound (5) To 36.4 g of compound (4) was added 50 ml of benzene,
The mixture was stirred under heating under reflux. Thionyl chloride (10 ml) was added dropwise thereto, and the mixture was further stirred with heating under reflux for 30 minutes, and then benzene was distilled off with an aspirator to obtain an oily substance as a crude product of the objective compound (5).

Synthesis of Compound (7) To 840 g of Compound (6), 3 liters of concentrated hydrochloric acid was added, and an aqueous solution prepared by dissolving 293 g of sodium nitrite in 520 ml of water was added thereto while stirring in an ice methanol bath. While the temperature was kept at -5 ° C or lower, the mixture was slowly added dropwise, and after completion of the addition, the mixture was stirred for 30 minutes. On the other hand, anhydrous tin (II) chloride 166
What melt | dissolved 9 g in concentrated hydrochloric acid 3 liters was stirred in an ice-methanol bath, and the reaction mixture which consists of the above-mentioned compound (6) was added here, keeping an internal temperature below 10 degreeC. Then, after stirring for 1 hour, the obtained crystals were suction filtered. To this product, 2 liters of benzene was added, and water was separated and removed by azeotropic operation with stirring. After cooling to room temperature, the remaining crystals were suction filtered and dried to obtain 786 g of the target compound (7). Obtained. When NMR was measured for this substance using ethylene glycol as an internal standard, the purity was 70.4% by weight. Therefore, the true yield is 61%
Met.

Synthesis of compound (9) To 1200 g of compound (8) was added 1.8 liter of methylene chloride, and the mixture was stirred in an ice-methanol bath. 1640 g of bromine was added here while keeping the internal temperature below 0 ° C.
It dripped over time. After completion of dropping, the ice-methanol bath was removed and the mixture was further stirred for 1 hour. Extraction operation was performed by adding 3 liters of saturated saline to the methylene chloride layer. The obtained methylene chloride layer was washed twice with 3 liters of saturated aqueous sodium hydrogen carbonate, washed twice with 3 liters of saturated saline and dried over anhydrous sodium sulfate. Then, methylene chloride was distilled off with a rotary evaporator to obtain 1972 g of the target compound (9) as a crude product.

Synthesis of compound (10) To 26.1 g of metallic magnesium, 10 g of compound (9) and 300 ml of tetrahydrofuran were added and stirred, 0.1 g of iodine was added thereto, and the mixture was stirred with heating under reflux. After 10 minutes, 187 g of the compound (9) was added dropwise while being careful not to make the reflux too violent. After heating and refluxing for 3 hours, the system was cooled with ice. Carbon dioxide gas here 13
2 g was bubbled and stirred while the internal temperature did not exceed 20 ° C. Pour this on ice and add concentrated hydrochloric acid 172
After adding ml, add water until the total volume becomes 3 liters. 1
Stir for hours. The precipitated crystals were filtered by suction, washed with water and dried to obtain 130 g of the target compound (10) in a yield of 79%.

Synthesis of compound (11) To 130 g of compound (10) was added 600 ml of concentrated sulfuric acid, and the mixture was stirred in an ice-methanol bath. Nitric acid (specific gravity 1.
(38, 61% by weight) (59 ml) was added dropwise over 30 minutes while maintaining the internal temperature at 10 ° C or lower. Then, after stirring for 3 hours, the reaction mixture was poured into ice and water was added thereto with stirring to make a total volume of 2.5 liters. After continuing stirring for 1 hour as it was, the obtained crystals were collected by filtration and dried to obtain 150 g of the target compound (11) as crude crystals. This product was recrystallized from a mixed solution of 150 ml of ethanol and 150 ml of water to obtain 122 g of compound (11) in a yield of 74%.

Synthesis of compound (12) To 105 g of compound (11) was added 100 ml of toluene, and the mixture was stirred with heating under reflux. 51 ml of thionyl chloride
After dropwise addition, the mixture was stirred for 30 minutes while heating under reflux, and then toluene was distilled off with an aspirator. Thus, the compound (12) was obtained as a crude product.

Synthesis of Compound (13) Compound (7) (Purity of 70.4% by weight from NMR) 4
To 0.3 g, add 200 ml of acetonitrile, and under ice cooling,
Triethylamine 70. while keeping the internal temperature below 10 ° C.
3 ml was added dropwise. After stirring for 10 minutes as it was, 27.3 g of the compound (12) dissolved in 50 ml of N, N-dimethylacetamide was added dropwise while keeping the internal temperature at 10 ° C or lower. After stirring for 1 hour, the reaction mixture was poured into water, and the obtained crystals were suction filtered to obtain 43.1 g of the desired compound (13) in a yield of 95%.

Synthesis of compound (14) N, N-dimethylamide 2 was added to 43.1 g of compound (13).
00 ml was added and dissolved, and carbon tetrachloride 43.6 was added here.
ml was added and the mixture was stirred at room temperature. To this, 59.3 g of triphenylphosphine was added, and the mixture was stirred for 2 hours, and then stirred with heating at an internal temperature of 80 ° C for 1 hour. 500 ml of ethyl acetate and 500 ml of saturated saline were added thereto for extraction, and the obtained ethyl acetate layer was washed with 500 ml of saturated saline. To the ethyl acetate layer thus obtained, 32 ml of triethylamine was added and stirred for 10 minutes, then saturated saline solution 50
The extract was washed 3 times with 0 ml, dried over anhydrous Glauber's salt, and concentrated by a rotary evaporator. The obtained residue was purified by silica gel column chromatography to obtain the target compound (14), 33.9 g, in a yield of 83%.

Synthesis of Compound (15) To 15 g of reduced iron and 1 g of ammonium chloride, 1 ml of acetic acid and 10 ml of water were added, and the mixture was stirred for 1 hour while heating under reflux. To this, 100 ml of methanol was added, and 18.1 g of the compound (14) was added with stirring under heating under reflux again. Then, the mixture was refluxed and stirred for 1 hour, the insoluble material was filtered off, and the obtained solution was concentrated with a rotary evaporator to obtain the target compound (15) as a residue. The compound (15) was directly used for the next step without purification.

Synthesis of Compound (I-1) To the compound (15) obtained in the previous step, 60 ml of N, N-dimethylacetamide was added and dissolved, and 20 g of the compound (5) was added thereto while stirring. -The solution dissolved in 20 ml of dimethylacetamide was added dropwise. After continuously adding 4.2 ml of pyridine, the mixture was stirred for 3 hours. To this, 30 ml of ethyl acetate and 200 ml of saturated saline were added for extraction,
The obtained ethyl acetate layer was mixed with 100 ml of saturated saline and 10 ml of water.
After washing with 0 ml of the mixed solution four times, and drying with anhydrous sodium sulfate,
It was concentrated on a rotary evaporator. The obtained residue was purified by silica gel column chromatography, and 27.1 g of the target compound I-1 was obtained from the compound (14) in a yield of 80%.

The pyrazoloazole type coupler represented by formula (I) is preferably used in the silver halide light-sensitive material in an amount of 0.1 to 2.0 mmol / m ² , more preferably 0.3 to 1 0.0 mmol / m ² .

The compounds represented by formulas (AI) to (A-IV) will be described in detail.

Among the compounds represented by the general formulas (AI) to (A-IV), the compounds represented by the general formulas (AI) to (A-III) are preferable. Among the compounds represented by formula (AI), the preferred compounds are shown below.

1) A compound in which X is —O— and at least one of R _{1 to} R ₅ is —X—R 2) —X—R is —OH, and R ₃ is aryloxycarbonyl. A compound which is a group 3) A compound in which X is —O— and R ₁ is a substituted benzyl group 4) A compound in which X is —O— and R ₁ is an amide group.

In the compound represented by the general formula (A-II), a compound in which A forms a 5- or 6-membered ring is preferable,
In the compound represented by the general formula (A-III), M represents nickel, and R ₂₀ , R ₂₁ and R ₂₀ '
Compounds in which R ₂₁ ′ and R ₂₁ ′ form an aromatic ring are preferred.

Typical examples of the compounds represented by formulas (A-I) to (A-IV) are shown below, but the compounds used in the present invention are not limited thereto.

[0065]

[Chemical formula 26]

[0066]

[Chemical 27]

[0067]

[Chemical 28]

[0068]

[Chemical 29]

[0069]

[Chemical 30]

[0070]

[Chemical 31]

[0071]

[Chemical 32]

[0072]

[Chemical 33]

[0073]

[Chemical 34]

[0074]

[Chemical 35]

[0075]

[Chemical 36]

[0076]

[Chemical 37]

[0077]

[Chemical 38]

[0078]

[Chemical Formula 39]

[0079]

[Chemical 40] Other preferred compound examples and synthetic methods of the compounds represented by formulas (AI) to (A-IV) of the present invention are described in U.S. Pat. Nos. 2,735,765 and 3,432,300,
No. 3,573,050, No. 3,574,627
No. 3,698,909, 3,700,45
No. 5, No. 3,764,337, No. 3,930,8
No. 66, No. 3,982,944, No. 4,113,
No. 495, No. 4,120,723, No. 4,15
No. 5,765, No. 4,254,216, No. 4,2
No. 45,018, No. 4,268,593, No. 4,
273,864, 4,279,990, 4,332,836, 4,360,589, 4,430,425, 4,483,918,
No. 4,540,653, No. 4,559,297
No. 4,745,050, No. 4,749,64
5, British Patent Nos. 1,156,167 and 2,03
No. 9,068, No. 2,043,931 and No. 2,0
66,975, European Patent Publication Nos. 98,241, 176,845, 178,165, and 26.
4,730, 268,496, 273,4
No. 12, No. 298, 321, Japanese Examined Patent Publication No. 60-2445.
5, JP-A-59-87456, 61-25824.
6, No. 63-95440 and the like.

The compound represented by the general formula (AI) or (A-IV) of the present invention varies depending on the couplers used in combination, but it is 1 per mol of the coupler represented by the general formula (I) present in the same layer. × 10 ^-2 to 10 mol, preferably 3 ×
It is 10 ^{-2 to} 5 mol. If it is less than this range, the effect of the present invention tends to be difficult to be obtained, and if it is more than this range, the coloring reaction is hindered.

The light-sensitive material of the present invention may be provided with at least one layer of a blue-sensitive layer, a green-sensitive layer and a red-sensitive layer of a silver halide emulsion layer on a support. There is no particular limitation on the number and order of layers of the silver halide emulsion layer and the non-photosensitive layer. As a typical example, a silver halide photographic light-sensitive material having on a support at least one light-sensitive layer consisting of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities. And the photosensitive layer is blue light, green light,
And a unit light-sensitive layer having color sensitivity to red light, and in a multilayer silver halide color photographic light-sensitive material, the unit light-sensitive layers are generally arranged in order from the support side to the red-color-sensitive layer and green. The color-sensitive layer and the blue color-sensitive layer are installed in this order.
However, the order of installation may be reversed depending on the purpose, or the order of installation may be such that different photosensitive layers are sandwiched between the same color-sensitive layers.

Non-photosensitive layers such as various intermediate layers may be provided between the above-mentioned silver halide photosensitive layers and as the uppermost layer and the lowermost layer. In the intermediate layer, JP-A Nos. 61-43748, 59-113438, 59-113440 and 6-
The couplers and DIR compounds as described in the specifications of 1-20037 and 61-20038 may be contained, and a color mixing inhibitor may be contained as is commonly used. A plurality of silver halide emulsion layers constituting each unit photosensitive layer are composed of a high-sensitivity emulsion layer and a low-sensitivity emulsion layer as described in West German Patent No. 1,121,470 or British Patent No. 923,045. A two-layer structure can be preferably used. Usually, it is preferable that the layers are arranged so that the sensitivities are gradually lowered toward the support, and a non-photosensitive layer may be provided between each halogen emulsion layer. Further, as described in JP-A Nos. 57-112751, 62-200350, 62-206541, 62-206543, etc., a low-sensitivity emulsion layer and a support are provided on the side remote from the support. A high sensitivity emulsion layer may be provided on the near side.

As a specific example, from the side farthest from the support,
Low sensitivity blue photosensitive layer (BL) / high sensitivity blue photosensitive layer (BH)
/ High sensitivity green photosensitive layer (GH) / Low sensitivity green photosensitive layer (G
L) / high-sensitivity red photosensitive layer (RH) / low-sensitivity red photosensitive layer (RL), or BH / BL / GL / GH / RH /
RL order or BH / BL / GH / GL / RL / RH
Can be installed in order. In addition, Japanese Examined Japanese Patent Publication Sho 55-34
As described in Japanese Patent No. 932, the blue-sensitive layer / GH / RH / GL / RL may be arranged in this order from the side farthest from the support. Also, JP-A-56-25738
No. 62-63936, the blue-sensitive layer / GL / RL from the side farthest from the support.
It can also be arranged in the order of / GH / RH.

Further, as described in JP-B-49-15495, the upper layer is the silver halide emulsion layer having the highest photosensitivity, the intermediate layer is the silver halide emulsion layer having a lower photosensitivity, and the lower layer is the intermediate layer. Another example is an arrangement in which a silver halide emulsion layer having a lower photosensitivity is arranged and three layers having different sensitivities are sequentially lowered toward the support. Even when it is composed of three layers having different sensitivities, as described in JP-A-59-202464, a medium-sensitivity emulsion from the side remote from the support in the same color-sensitive layer. It may be arranged in the order of layer / high-speed emulsion layer / low-speed emulsion layer.

In addition, the layers may be arranged in the order of high-speed emulsion layer / low-speed emulsion layer / medium-speed emulsion layer, or low-speed emulsion layer / medium-speed emulsion layer / high-speed emulsion layer. Also, 4
In the case of more than one layer, the arrangement may be changed as described above. To improve color reproducibility, US Pat. No. 4,663,271
No. 4,705,744, No. 4,707,43
6, JP-A-62-160448, 63-8985.
No. 0 specification, a donor layer (CL) having a multilayer effect having a spectral sensitivity distribution different from that of a main photosensitive layer such as BL, GL, and RL.
Is preferably arranged adjacent to or in proximity to the main photosensitive layer. As described above, various layer configurations and arrangements can be selected according to the purpose of each light-sensitive material.

When the photographic light-sensitive material of the present invention is a color negative film or a color reversal film, a preferred silver halide contained in the photographic emulsion layer contains about 30 mol% or less of silver iodide, iodobromide. It is silver, silver iodochloride, or silver iodochlorobromide. Particularly preferred is about 2 mol% to about 25
Silver iodobromide or silver iodochlorobromide containing up to mol% silver iodide.

When the photographic light-sensitive material of the present invention is a color photographic paper, the silver halide contained in the photographic emulsion layer is selected from silver chlorobromide or silver chloride containing substantially no silver iodide. The following can be preferably used. The term "substantially free of silver iodide" as used herein means that the silver iodide content is 1 mol% or less, preferably 0.2 mol% or less.
Regarding the halogen composition of these silver chlorobromide emulsions, any silver bromide / silver chloride can be used. This ratio can take a wide range depending on the purpose, but the silver chloride ratio is 2
Those having a mol% or more can be preferably used. A so-called high silver chloride emulsion having a high silver chloride content is preferably used for a light-sensitive material suitable for rapid processing. The silver chloride content of these high silver chloride emulsions is preferably 90 mol% or more, more preferably 95 mol% or more. An emulsion of almost pure silver chloride having a silver chloride content of 98 to 99.9 mol% is also preferably used for the purpose of reducing the replenishment amount of the developing solution. Silver halide grains in photographic emulsions have regular crystals such as cubes, octahedra and tetradecahedrons, grains having irregular crystal forms such as spheres and plates, twin planes, etc. It may have a crystal defect of, or a composite form thereof.
The grain size of silver halide may be fine grains of about 0.2 micron or less, or large grains having a projected area diameter of up to about 10 microns, and may be a polydisperse emulsion or a monodisperse emulsion.

The silver halide photographic emulsion which can be used in the present invention is, for example, Research Disclosure (RD) N.
o. 17643 (December 1978), pages 22-23,
"I. Emulsion preparation
ion and types) ", ibid. No. 18716.
(November 1979), page 648, ibid. 30710
5 (Nov. 1989), pages 863-865, and Graphide, "Physics and Chemistry of Photography," published by Paul Montel (P. Glafkides, Chemie et Phi.
sique Photographie, Paul
Montel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press, Inc. (GF Duffin,
Photographic Emulsion Che
mistry (Focal Press, 196
6)), "Production and Coating of Photographic Emulsions" by Zelikmann et al., Published by Focal Press (VL Zelikmanet).
al. , Making and Coating Ph
otographic Emulsion, Focal
Press, 1964) and the like. U.S. Pat. No. 3,574,62
No. 8, 3,655,394 and British Patent Nos. 1,4.
Monodisperse emulsions described in No. 13,748 are also preferable.

Further, tabular grains having an aspect ratio of about 5 or more can be used in the present invention. Tabular grains are described by Gatov, Photography, Science and Engineering (Gutoff, Photograph).
ic Science and Engineering
g), 14: 248-257 (1970); U.S. Pat. Nos. 4,434,226 and 4,414,310.
No. 4,433,048, No. 4,439,520 and British Patent No. 2,112,157, and the like.

The crystal structure may be uniform, may have different halogen compositions inside and outside, may have a layered structure, and silver halides having different compositions may be bonded by epitaxial bonding. May be
Further, it may be bonded with a compound other than silver halide such as silver rhodanide and lead oxide. Also, a mixture of particles having various crystal forms may be used. As the silver halide emulsion, those which have been physically ripened, chemically ripened and spectrally sensitized are usually used. Additives used in such a process are Research Disclosure No. 17643, the same No. 1
8716, and the same No. No. 307105, the relevant parts are summarized in the table below. In the present invention,
It is preferred to use non-photosensitive fine grain silver halide. The non-photosensitive fine grain silver halide is a fine grain of silver halide which is not exposed to light during imagewise exposure for obtaining a dye image and is not substantially developed in the developing treatment, and it is preferable that the fog is not fogged in advance. .. The fine grain silver halide has a silver bromide content of 0 to 100 mol%, and may optionally contain silver chloride and / or silver iodide. Preferred is one containing 0.5 to 10 mol% of silver iodide. The fine grain silver halide has an average grain size (average value of circle equivalent diameter of projected area) of 0.01 to 0.
5 μm is preferable, and 0.02 to 0.2 μm is more preferable. The fine grain silver halide can be prepared in the same manner as in the case of ordinary photosensitive silver halide. In this case, the surface of the silver halide grain does not need to be chemically sensitized nor spectral sensitization. However, prior to adding this to the coating liquid, it is preferable to add a known stabilizer such as a triazole-based, azaindene-based, benzothiazolium-based, mercapto-based compound or zinc compound in advance.

Known photographic additives that can be used in the present invention are also described in the above three Research Disclosures, and the relevant portions are shown in the following table.

Types of additives RD17643 RD18716 RD307105 1. Chemical sensitizer 23 pages 648 pages right column 866 pages 2. Sensitivity enhancer page 648, right column 3. Spectral sensitizer, pages 23 to 24, page 648, right column, page 866 to 868, supersensitizer, page 649, right column, 4. Whitening agent 24 pages 647 pages right column 868 pages 5. Fogging prevention page 24 to 25 page 649 right column 868 to 870 page agents and stabilizers 6. Light absorber, pages 25 to 26, page 649, right column, page 873, filter dye, to page 650, left column, ultraviolet absorber 7. Stain 25 pages right column 650 pages left column 872 pages Inhibitor to right column 8. Dye image Page 25 Page 650 Page left column Page 872 Stabilizer 9. Hardener 26 pages 651 pages left column 874-875 pages 10. Binder, page 26, page 651, left column, pages 873 to 874 11. Plasticizer, lubricant 27 pages 650 pages right column 876 pages 12. Coating aid, pages 26 to 27, page 650, right column, pages 875 to 876, surfactant 13. Static page 27 page 650 page right column 876-877 page inhibitor 14. Matting agent pp. 878-879 Further, in order to prevent deterioration of photographic performance due to formaldehyde gas, fixing is performed by reacting with formaldehyde described in US Pat. Nos. 4,411,987 and 4,435,503. It is preferable to add a compound capable of being converted into a light-sensitive material.

The light-sensitive material of the present invention can be prepared according to US Pat.
0,454, 4,788,132, JP-A-62.
It is preferable to incorporate the mercapto compounds described in JP-A-18539 and JP-A-1-283551. A compound described in JP-A No. 1-106052, which releases a fogging agent, a development accelerator, a silver halide solvent or a precursor thereof, to the light-sensitive material of the present invention, irrespective of the amount of developed silver produced by the development processing. Is preferably contained. Dyes or EP317,308A, U.S. Pat. No. 4,4, which are dispersed in the light-sensitive material of the present invention by the method described in International Publication WO88 / 04794 and International Publication No. 1-502912.
The dyes described in JP-A No. 20,555 and JP-A-1-289358 are preferably contained.

Various color couplers may be used in combination in the present invention, and specific examples thereof include Research Disclosure No. 17643, VII-CG, and the same No. 307105, VII-C to G. Examples of yellow couplers include U.S. Pat. Nos. 3,933,501 and 4,023.
No. 2,620, No. 4,326,024, No. 4,4
No. 01,752, No. 4,248,961, Japanese Patent Publication No. 5
8-10739, British Patent No. 1,425,020,
U.S. Pat. No. 1,476,760 and U.S. Pat. No. 3,973,9.
No. 68, No. 4,314, 023, No. 4,511.
Those described in, for example, No. 649 and European Patent 249,473A are preferable.

As the magenta coupler, 5-pyrazolone compounds and pyrazoloazole compounds other than those of the present invention may be used in combination. For example, U.S. Pat. No. 4,310,619
No. 4,351,897, European Patent No. 73,63.
6, U.S. Pat. Nos. 3,061,432, and 3,72.
No. 5,067, Research Disclosure No. Two
4220 (June 1984), JP-A-60-33552.
No., Research Disclosure No. 24230
(June 1984), JP-A-60-43659 and JP-A-60-43659.
No. 1-72238, No. 60-35730, No. 55-1
No. 18034, No. 60-185951, U.S. Patent Nos. 4,500,630, 4,540,654, 4,556,630, and International Publication WO88 / 0479.
Those described in No. 5 and the like are particularly preferable.

Examples of cyan couplers include phenol-type and naphthol-type couplers, and US Pat.
52,212, 4,146,396, and 4,
No. 228,233, No. 4,296,200, No. 2,369,929, No. 2,801,171, No. 2,772,162, No. 2,895,826,
No. 3,772,002, No. 3,758,308
No. 4,334,011, No. 4,327,17
3, West German Patent Publication No. 3,329,729, European Patent Nos. 121,365A, 249,453A, U.S. Patents 3,446,622, 4,333,999.
No. 4,775,616, No. 4,451,55
9, No. 4,427,767, No. 4,690,8
89, 4,254,212 and 4,296,4
Those described in JP-A No. 199, JP-A-61-42658 and the like are preferable. Further, JP-A 64-553 and 64-5.
54, 64-555 and 64-556, and pyrazoloazole couplers described in US Pat. No. 4,811.
The imidazole couplers described in No. 8,672 can also be used. Typical examples of polymerized dye-forming couplers are U.S. Pat.
080,211, 4,367,282, 4,409,320, 4,576,910, British Patent 2,102,137, European Patent 341,1.
88A and the like.

Examples of couplers in which the color forming dye has an appropriate diffusibility include US Pat. No. 4,366,237, British Patent 2,125,570, European Patent 96,570,
Those described in West German Patent (Publication) No. 3,234,533 are preferable.

Colored couplers for correcting unwanted absorption of color-forming dyes are available from Research Disclosure N.
o. 17643, Item VII-G, ibid. 307105
VII-G, U.S. Pat. No. 4,163,670, JP-B-57-39413, U.S. Pat. No. 4,004,92.
No. 9, No. 4,138,258, and British Patent No. 1,14.
Those described in No. 6,368 are preferable. Further, a coupler described in US Pat. No. 4,774,181 for correcting unnecessary absorption of a coloring dye by a fluorescent dye released upon coupling, and a reaction with a developing agent described in US Pat. No. 4,777,120. It is also preferable to use a coupler having a dye precursor group capable of forming a dye as a leaving group. Compounds that release a photographically useful residue upon coupling are also preferably used in the present invention. DIR couplers that release development inhibitors are described above in RD1764.
3, VII-F section and No. 307105, VII-
Patents described in paragraph F, JP-A-57-151944,
Those described in U.S. Pat. Nos. 57-154234, 60-184248, 63-37346, 63-37350, and U.S. Pat. Nos. 4,248,962 and 4,782,012 are preferable. R. D. No. 11449,
The bleaching accelerator releasing couplers described in JP-A No. 24241 and JP-A No. 61-201247 are effective for shortening the processing time having a bleaching ability. In particular, the tabular silver halide grains described above are used. The effect is great when it is added to a light-sensitive material. As a coupler that releases a nucleating agent or a development accelerator imagewise during development, British Patent No. 2,
097,140, 2,131,188, JP-A-59-157638 and JP-A-59-170840 are preferable. Also, JP-A-60-107029
No. 60-252340, JP-A-1-44940.
Also preferred are compounds capable of releasing a fogging agent, a development accelerator, a silver halide solvent, etc. by an oxidation-reduction reaction with an oxidized product of a developing agent described in JP-A No. 1-45687.

Other compounds that can be used in the light-sensitive material of the present invention include US Pat. No. 4,130,427.
Couplers described in U.S. Pat. No. 4,283,4
No. 72, No. 4,338,393, No. 4,310,
No. 618 and the like, multiequivalent couplers, JP-A-60-18.
5950, DIR described in JP-A-62-24252, etc.
Redox compound releasing coupler, DIR coupler releasing coupler, DIR coupler releasing redox compound or DIR redox releasing redox compound, European Patent No. 1
Nos. 73,302A and 313,308A, which release dyes that restore color after separation, and US Pat.
Examples thereof include a ligand releasing coupler described in US Pat. No. 555,477, a coupler releasing a leuco dye described in JP-A-63-75747, and a coupler releasing a fluorescent dye described in US Pat. No. 4,774,181. Be done. The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods.

Examples of the high boiling point solvent used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027. The boiling point at atmospheric pressure used in the oil-in-water dispersion method is 17
Specific examples of the high boiling point organic solvent having a temperature of 5 ° C. or higher include phthalic acid esters (for example, dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate,
Decyl phthalate, bis (2,4-di-t-amylphenyl) phthalate, bis (2,4-di-t-amylphenyl) isophthalate, bis (1,1-diethylpropyl) phthalate), phosphoric acid or phosphone Ester acid of 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 (eg 2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate), amides (eg N, N-). Diethyldodecane amide, N, N-diethyllaurylamide, N-tetradecylpyrrolidone), alcohols or phenols (isostearyl alcohol, 2,4-di-tert-aminophenol), aliphatic carboxylic acid esters (eg bis (2-
Ethylhexyl) sebacate, dioctyl azelate,
Glycerol tributyrate, isostearyl lactate, trioctyl citrate), aniline derivatives (eg N, N-dibutyl-2-butoxy-5-tert-octylaniline), hydrocarbons (eg paraffin, dodecylbenzene, diisopropylnaphthalene) And so on. As the auxiliary solvent, an organic solvent having a boiling point of about 30 ° C. or higher, preferably 50 ° C. or higher and about 160 ° C. or lower can be used. Typical examples are ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2- Examples include ethoxyethyl acetate and dimethylformamide.

The steps and effects of the latex dispersion method and specific examples of the latex for impregnation are described in US Pat. No. 4,199,3.
63, West German Patent Application (OLS) No. 2,541,274
And No. 2,541,230.

These couplers may also be impregnated with a loadable latex polymer (for example, US Pat. No. 4,203,716) in the presence or absence of the above-mentioned high-boiling organic solvent, or insoluble in water and in an organic solvent. It can be dissolved in a soluble polymer and emulsified and dispersed in a hydrophilic colloid aqueous solution.

Preferably, International Publication No. WO88 / 00
The homopolymers or copolymers described on pages 12 to 30 of the specification of No. 723 are used. Particularly, it is preferable to use an acrylamide polymer in terms of color image stabilization and the like.

In the color light-sensitive material of the present invention, phenethyl alcohol, JP-A-63-257747 and JP-A-62-257747 are used.
No. 272248, and 1,2-benzisothiazolin-3-one, n-butyl p-hydroxybenzoate, phenol, 4-chloro-3,5-dimethylphenol, 2-phenoxyethanol described in JP-A No. 1-80941. It is preferable to add various preservatives or antifungal agents such as-(4-thiazolyl) benzimidazole. The present invention can be applied to various color light-sensitive materials. Color negative film for general use or movies,
Representative examples include color reversal films for slides or televisions, color papers, color positive films, and color reversal papers. Suitable supports that can be used in the present invention are described, for example, in RD. N
o. 17643, page 28, ibid. 18716, 647
Page right column to page 648 left column, and the same No. 307105
Pp. 879.

In the light-sensitive material of the present invention, the total thickness of all hydrophilic colloid layers on the emulsion layer side is preferably 28 μm or less, more preferably 23 μm or less, and 18 μm or less.
m or less is more preferable, and 16 μm or less is particularly preferable.
The film swelling speed T _1/2 is preferably 30 seconds or less, more preferably 20 seconds or less. The film thickness means a film thickness measured under a humidity condition of 25 ° C. and a relative humidity of 55% (2 days), and the film swelling rate T
_1/2 can be measured according to a method known in the art. For example, A Green (A. Gr
een, et al., Photographic Science and Engineering (Photogr. Sci. E)
ng. ) Volume 19, No. 2, by using the type of Swellometer described (swelling meter) pp 124-129, can be measured, T _1/2 is 30 ° C. with a color developing solution, and treated for 3 minutes 15 seconds 90% of the maximum swollen film thickness that reaches at time is the saturated film thickness,
It is defined as the time required to reach 1/2 of the saturated film thickness. The film swelling speed T _1/2 can be adjusted by giving a film-hardening agent to gelatin as a binder or changing the aging condition after coating. The swelling rate is 15
0 to 400% is preferable. The swelling ratio can be calculated from the maximum swollen film thickness under the conditions described above according to the formula: (maximum swollen film thickness-film thickness) / film thickness. The color photographic light-sensitive material according to the present invention has the RD. No. 28 of 17643
~ 29, ibid. 18716, 651 left column to right column, and the same No. Development processing can be performed by a usual method described on pages 880 to 881 of 307105.

The color developing solution used in the development processing of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine type color developing agent as a main component. As the color developing agent, an aminophenol compound is also useful, but a p-phenylenediamine compound is preferably used, and a typical example thereof is 3-methyl-4-amino-N,
N-diethylaniline, 3-methyl-4-amino-N-
Ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-
Examples thereof include ethyl-β-methoxyethylaniline and their sulfates, hydrochlorides or p-toluenesulfonates. Of these, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline sulfate is particularly preferable. Two or more kinds of these compounds can be used in combination depending on the purpose.

The color developer contains a pH buffer such as an alkali metal carbonate, borate or phosphate, a chloride salt, a bromide salt, an iodide salt, a benzimidazole compound, a benzothiazole compound or a mercapto compound. It is common to include such a development inhibitor or an antifoggant. If necessary, hydroxylamine, diethylhydroxylamine, sulfite, hydrazines such as N, N-biscarboxymethylhydrazine, phenylsemicarbazides, triethanolamine, various preservatives such as catecholsulfonic acids, ethylene glycol, Organic solvents such as diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, competing couplers, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, viscosity imparting Agents, aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, various chelating agents represented by phosphonocarboxylic acids, for example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclo Hexane diamine tetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene--
1,1-diphosphonic acid, nitrilo-N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N, N
-Tetramethylenephosphonic acid, ethylenediamine-di (o-hydroxyphenylacetic acid) and their salts can be mentioned as representative examples.

When the reversal process is carried out, black and white development is usually carried out and then color development is carried out. In this black-and-white developing solution, known black-and-white developing agents such as dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone or aminophenols such as N-methyl-p-aminophenol are used alone. Alternatively, they can be used in combination. The pH of the color developing solution and the black and white developing solution is generally 9 to 12.
The replenishing amount of these developing solutions depends on the color photographic light-sensitive material to be processed, but is generally 3 liters or less per 1 square meter of the light-sensitive material, and it is 500 ml or less by reducing the bromide ion concentration in the replenishing solution. You can also do it. When the replenishment amount is reduced, it is preferable to prevent the liquid evaporation and air oxidation by reducing the contact area with the air in the processing tank. The contact area between the photographic processing liquid and air in the processing tank can be represented by the aperture ratio defined below. That is, aperture ratio = (contact area between treatment liquid and air (cm ² )) ÷ (volume of treatment liquid (cm ³ )) The above aperture ratio is preferably 0.1 or less, more preferably 0. 0.001 to 0.05. As a method of reducing the aperture ratio in this way, in addition to providing a barrier such as a floating lid on the surface of the photographic processing liquid in the processing tank, Japanese Patent Laid-Open No. 1-82
No. 033, a method using a movable lid, JP-A-63-63
-216050 can be mentioned as a slit developing treatment method. To reduce the aperture ratio, not only the steps of color development and black and white development, but also the subsequent steps,
For example, it is preferably applied in all steps such as bleaching, bleach-fixing, fixing, washing with water, stabilization and the like. Further, the amount of replenishment can be reduced by using a means for suppressing the accumulation of bromide ions in the developing solution. The time of color development processing is usually set between 2 and 5 minutes, but by using a high temperature and high pH and using a color developing agent at a high concentration,
Furthermore, the processing time can be shortened.

The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed at the same time as the fixing process (bleach-fixing process) or separately. Further, in order to speed up the processing, a processing method of bleach-fixing processing after bleaching processing may be used. Further, treatment with two continuous bleach-fixing baths, fixing treatment before the bleach-fixing treatment, or bleaching treatment after the bleach-fixing treatment can be optionally carried out. As the bleaching agent, compounds of polyvalent metals such as iron (III), peracids, quinones, nitro compounds and the like are used. As a typical bleaching agent, an organic complex salt of iron (III), for example, an amino acid such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, and glycol etherdiaminetetraacetic acid. Polycarboxylic acids or complex salts of citric acid, tartaric acid, malic acid and the like can be used. Of these, aminopolycarboxylic acid iron (III) complex salts such as ethylenediaminetetraacetic acid iron (III) complex salts and 1,3-diaminopropanetetraacetic acid iron (III) complex salts are used from the viewpoint of rapid treatment and prevention of boundary ring contamination. preferable. Further, the aminopolycarboxylic acid iron (III) complex salt is particularly useful in both the bleaching solution and the bleach-fixing solution. The pH of a bleaching solution or a bleach-fixing solution using these iron (III) aminopolycarboxylic acid complex salts is usually 4.0 to 8, but lower pH can be used for speeding up the processing. If necessary, a bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution and their pre-bath. Specific examples of useful bleach accelerators are described in the following specification: US Pat. No. 3,893,85
No. 8, West German Patent Nos. 1,290,812 and 2,05
9,988, JP-A-53-32736, and JP-A-53-5.
7831, 53-37418, and 53-7262.
No. 3, No. 53-95630, No. 53-95631,
No. 53-104232, No. 53-124424, No. 53-141623, No. 53-28426, Research Disclosure No. No. 17129 (1978
July)) and the like having a mercapto group or a disulfide group; thiazolidine derivatives described in JP-A-50-140129; JP-B-45-8506, JP-A-52-20832, 53-32735. , U.S. Pat. No. 3,706,561; thiourea derivatives; West German Patent 1,127,715, JP-A-58-16,2.
35, iodide salt; West German Patent 966,410
Nos. 2,748,430; polyoxyethylene compounds described in JP-B-45-8836; Others JP-A-49-40,943, 49-
59,644, 53-94,927, 54-3.
5,727, 55-26,506, 58-16
Compounds described in 3,940; bromide ion and the like can be used. Among them, compounds having a mercapto group or a disulfide group are preferable from the viewpoint of a large accelerating effect, and in particular, US Pat. No. 3,893,858 and West German Patent 1,290,
Compounds described in JP-A No. 812 and JP-A-53-95,630 are preferable. Further, the compounds described in US Pat. No. 4,552,834 are also preferable. These bleaching accelerators may be added to the light-sensitive material, and these bleaching accelerators are particularly effective when bleach-fixing a color light-sensitive material for photographing.

The bleaching solution and the bleach-fixing solution preferably contain an organic acid in addition to the above compounds for the purpose of preventing bleach stain. A particularly preferred organic acid has an acid dissociation constant (p
Ka) is a compound of 2 to 5, and specifically, acetic acid, propionic acid and the like are preferable.

Examples of the fixing agent used in the fixing solution and the bleach-fixing solution include thiosulfates, thiocyanates, thioether compounds, thioureas and a large amount of iodide salts. Use of thiosulfates Is most commonly used, with ammonium thiosulfate being the most widely used. Further, the combined use of thiosulfate and thiocyanate, thioether compounds, thiourea and the like is also preferable. As a preservative for the fixing solution and the bleach-fixing solution, sulfites, bisulfites, carbonyl bisulfite adducts or sulfinic acid compounds described in European Patent 294769A are preferable. Further, various aminopolycarboxylic acids and organic phosphonic acids are preferably added to the fixing solution and the bleach-fixing solution for the purpose of stabilizing the solution. In the present invention, the fixing solution or the bleach-fixing solution contains p for adjusting the pH.
A compound having a Ka of 6.0 to 9.0, preferably 0.1 to 10 mol / liter of imidazole such as imidazole, 1-methylimidazole, 1-ethylimidazole and 2-methylimidazole is added. .. The total time of the desilvering process is preferably as short as possible in the range where desilvering failure does not occur. The preferred time is 1 to 3 minutes, more preferably 1 to 2 minutes. Also, the processing temperature is 25 ° C.
-50 degreeC, Preferably it is 35 degreeC-45 degreeC. In the preferable temperature range, the desilvering rate is improved and the stain generation after the processing is effectively prevented.

In the desilvering process, it is preferable that the stirring is strengthened as much as possible. As a concrete method for strengthening the stirring, a method of causing a jet of a processing solution to collide with an emulsion surface of a light-sensitive material described in JP-A-62-183460, and stirring using a rotating means of JP-A-62-183461. A method to improve the effect, further a method to improve the stirring effect by moving the light-sensitive material while bringing the emulsion surface into contact with the wiper blade provided in the solution and making the emulsion surface turbulent, circulation of the entire processing solution There is a method of increasing the flow rate. Such stirring improving means includes a bleaching solution, a bleach-fixing solution,
It is effective with any of the fixing solutions. It is considered that the improvement of the stirring speeds up the supply of the bleaching agent and the fixing agent into the emulsion film and, as a result, increases the desilvering rate. Further, the stirring improving means is more effective when a bleaching accelerator is used,
It is possible to remarkably increase the accelerating effect and eliminate the fixing inhibitory action of the bleaching accelerator.

The automatic developing machine used for the light-sensitive material of the present invention is disclosed in JP-A-60-191257 and 60-19125.
It is preferable to have the photosensitive material conveying means described in No. 8 and No. 60-191259. JP-A-60-1
As described in No. 91257, such a conveying means can significantly reduce the carry-in of the treatment liquid from the front bath to the rear bath, and is highly effective in preventing the performance deterioration of the treatment liquid. Such effects are particularly effective in shortening the processing time in each step and reducing the amount of processing liquid replenishment.

The silver halide color photographic light-sensitive material of the present invention is generally washed with water and / or stabilized after the desilvering treatment. The amount of rinsing water in the rinsing process depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), application, and further, the rinsing water temperature, the number of rinsing tanks (number of stages), replenishment system such as countercurrent, forward flow, and other various conditions. It can be set in a wide range.
Among these, the relationship between the number of washing tanks and the amount of water in the multi-stage countercurrent system is described in the Journal of the Society
y of Motion Picture and T
Evolution Engineers Volume 64,
P. 248 to 253 (May 1955 issue). According to the multi-stage counter-current method described in the above literature, the amount of washing water can be significantly reduced, but due to the increase in the residence time of water in the tank, bacteria propagate, and the suspended matter produced adheres to the photosensitive material, etc. Problems arise. In the processing of the color light-sensitive material of the present invention, as a solution to such a problem, JP-A-62-288,838 has been proposed.
The method of reducing calcium ion and magnesium ion described in No. 10 can be used very effectively. Further, isothiazolone compounds and siabendazoles described in JP-A-57-8,542, chlorine-based bactericides such as chlorinated sodium isocyanurate, and benzotriazole are also described by Hiroshi Horiguchi in "Bacterial and Antifungal Agents". Chemistry "(1986)
Sankyo Publishing, Sanitary Technology Association, "Microbial Sterilization, Sterilization, and Antifungal Technology" (1982), Industrial Technology Association, Japan Antibacterial and Antifungal Society, "Antibacterial and Antifungal Encyclopedia," (1986) Can also be used. The pH of washing water in the processing of the light-sensitive material of the present invention is 4 to 9, preferably 5 to 8. The washing water temperature and the washing time can be set variously depending on the characteristics of the light-sensitive material, the use, etc., but generally 15 to 45 ° C. and 20 seconds to 10 seconds.
Minutes, preferably in the range of 25-40 ° C and 30 seconds-5 minutes. Further, the light-sensitive material of the present invention can be directly processed with a stabilizing solution instead of the above washing with water. In such stabilization treatment, Japanese Patent Laid-Open No. 57-8543,
All known methods described in JP-A-58-14834 and JP-A-60-220345 can be used.

In addition, the washing treatment may be followed by a further stabilizing treatment. As an example thereof, a stabilizing agent containing a dye stabilizer and a surfactant used as a final bath of a color light-sensitive material for photographing is used. You can mention the bath. Examples of dye stabilizers include aldehydes such as formalin and glutaraldehyde, N-methylol compounds, hexamethylenetetramine, and aldehyde sulfite adducts. Various chelating agents and antifungal agents can also be added to this stabilizing bath. The overflow solution accompanying the above washing with water and / or supplementation of the stabilizing solution can be reused in other steps such as the desilvering step. In the processing using an automatic processor or the like, when each of the above processing solutions is concentrated by evaporation, it is preferable to add water to correct the concentration. The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and accelerating the processing. For incorporation, it is preferable to use various precursors of color developing agents. For example, U.S. Pat. No. 3,342,597
Indoaniline compounds described in No. 3,342,5
No. 99, Research Disclosure No. 14,8
50 and No. 50. Schiff base type compounds described in JP-A Nos. 15,159,159, aldol compounds described in JP-A No. 13,924, metal salt complexes described in US Pat. No. 3,719,492, and urethane compounds described in JP-A-53-135628. be able to. The silver halide color light-sensitive material of the present invention may contain various 1-phenyl-3-pyrazolidones in order to accelerate color development, if necessary.
Typical compounds are JP-A Nos. 56-64339 and 57-57.
Nos. 144547 and 58-115438. Various treatment liquids in the present invention are 10 ° C to 5 ° C.
Used at 0 ° C. Usually, a temperature of 33 ° C. to 38 ° C. is standard, but a higher temperature is used to accelerate the processing to shorten the processing time, and a lower temperature is used to improve the image quality and the stability of the processing liquid. be able to.

Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited thereto.

[0117]

【Example】

(Example 1) (Preparation of sample 101) After corona discharge treatment was applied to the surface of a paper support laminated on both sides with polyethylene, a gelatin subbing layer containing sodium dodecylbenzenesulfonate was provided, and various photographic constituent layers were further formed. By coating, a multilayer color photographic paper having the following layer constitution was produced. The coating liquid was prepared as follows.

Preparation of coating liquid for first layer Yellow coupler (ExY) 19.1 g and color image stabilizer (Cpd-1) 4.4 g and color image stabilizer (Cpd-)
6) 0.7 g of ethyl acetate 27.2 cc and solvent (S
olv-3) and (Solv-7) 4.1 g each
10% gelatin aqueous solution containing 8 cc of 10% sodium dodecylbenzenesulfonate 1
Emulsified and dispersed in 85 cc to prepare an emulsified dispersion A. On the other hand, silver chlorobromide emulsion A (cube, average grain size 0.88
3: 7 mixture of large size emulsion (μm) and small size emulsion (0.70 μm) (silver molar ratio). The coefficient of variation of the grain size distribution was 0.08 and 0.10, respectively, and silver bromide 0.3 mol% was locally contained in a part of the grain surface in each size emulsion). In this emulsion, blue-sensitizing dyes A and B shown below are 2.0 × 10 ^-4 moles per mole of silver for the large-sized emulsion A, and for the small-sized emulsion A, respectively.
2.5 × 10 ⁻⁴ mol of each is added. The chemical ripening of this emulsion was performed by adding a sulfur sensitizer and a gold sensitizer. The above emulsified dispersion A and this chlorobromide emulsion A were mixed and dissolved to prepare a coating solution for the first layer having the composition shown below.

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

The total amount of Cpd-8 and Cpd-9 in each layer was 25.0 mg / m ² and 50.0 mg / m ^{2 respectively.}
Was added.

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

[0122]

[Chemical 41] (Each mole of silver halide is 2.0 × 10 ⁻⁴ mole for large-sized emulsion A and 2.5 × 10 ⁻⁴ mole for small-sized emulsion A)

[0123]

[Chemical 42] (Per mol of silver halide, 4.0 × 10 ^-4 mol to the large size emulsion B, to the small size emulsion B 5.
6 × 10 ⁻⁴ mol), and

[0124]

[Chemical 43] (Per mol of silver halide, 7.0 × 10 ⁻⁵ mol for large size emulsion B, and 1.0 × 10 ⁻⁵ mol for small size emulsion B)

[0125]

[Chemical 44] (0.9 × 10 ⁻⁴ mol for large size emulsion B and 1.1 × 10 ⁻⁴ mol for small size emulsion C per mol of silver halide) For red-sensitive emulsion layer The following compounds were added in an amount of 2.6.times.10@-3 mol per mol of silver halide.

[0126]

[Chemical 45] Further, 1- (5-methylureidophenyl) -5-mercaptotetrazole was added to the blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer, respectively, in an amount of 8.5 × 10 ^-5 mol / mol of silver halide and 7 / mol. 0.7 × 10 ^-4 mol, 2.5 × 1
^0-4 mol was added.

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

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

[0129]

[Chemical 46] (Layer constitution) The composition of each layer is shown below. Numbers are coating amount (g
/ M ² ). The silver halide emulsion represents the coating amount in terms of silver.

Support Polyethylene laminated paper (the first layer side polyethylene contains a white pigment (TiO ₂ ) and a bluish dye (ultraviolet)).

First layer (blue-sensitive emulsion layer) Silver chlorobromide emulsion A 0.03 Gelatin 1.22 Yellow coupler (ExY) 0.82 Color image stabilizer (Cpd-1) 0.19 Solvent (Solv-3) 0.18 Solvent (Solv-) 7) 0.18 color image stabilizer (Cpd-7) 0.06.

Second layer (color mixing prevention layer) Gelatin 0.64 Color mixing inhibitor (Cpd-5) 0.10 solvent (Solv-1) 0.16 solvent (Solv-4) 0.08.

Third Layer (Green Sensitive Emulsion Layer) Silver chlorobromide emulsion (cubic, 1: 3 mixture (Ag mole ratio) of a large size emulsion having an average grain size of 0.55 μm and a small size emulsion of 0.39 μm). The coefficient of variation of the size distribution is
0.10 and 0.08, in both small size emulsions, AgBr 0.8 mol% was locally contained in a part of the grain surface) 0.12 Gelatin 1.28 Magenta coupler (ExM) 0.23 Color image stabilizer (Cpd-2) 0.03 Color image stabilizer ( Cpd-3) 0.02 solvent (Solv-2) 0.40.

Fourth Layer (UV Absorbing Layer) Gelatin 1.41 UV absorbing agent (UV-1) 0.47 Color mixing inhibitor (Cpd-4) 0.05 Solvent (Solv-5) 0.24.

Fifth layer (red sensitive emulsion layer) Silver chlorobromide emulsion (cubic, 1: 4 mixture of large size emulsion of 0.58 μm average grain size and small size emulsion of 0.45 μm (Ag mole ratio). The coefficient of variation of the distribution is 0.09 and 0.
11. In each size emulsion, 0.6 mol% of AgBr was locally contained in a part of the grain surface.)
0.23 Gelatin 1.04 Cyan coupler (ExC) 0.32 Color image stabilizer (Cpd-2) 0.03 Color image stabilizer (Cpd-3) 0.02 Color image stabilizer (Cpd-5) 0.18 Color image stabilizer (Cpd-6) 0.40 color Image stabilizer (Cpd-7) 0.05 Solvent (Solv-6) 0.14.

Sixth layer (UV absorbing layer) Gelatin 0.48 UV absorbing agent (UV-1) 0.16 Color mixture preventing agent (Cpd-4) 0.02 Solvent (Solv-5) 0.08.

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

[0138]

[Chemical 47]

[0139]

[Chemical 48]

[0140]

[Chemical 49]

[0141]

[Chemical 50]

[0142]

[Chemical 51]

[0143]

[Chemical 52] Preparation of Samples 102 to 140 Samples 102 to 140 were prepared in the same manner as in Sample 101, except that the magenta coupler (ExM) in Sample 101 was replaced with the equimolar magenta coupler shown in Table 1 and the compounds shown in Table 1 were added. Was produced.

First, a sensitometer (FWH, manufactured by Fuji Photo Film Co., Ltd., color temperature of light source: 3200 ° K) manufactured by Fuji Photo Film Co., Ltd. was used for each sample, and gradation exposure of a three-color separation filter for sensitometry was performed. The exposure at this time is 2 with an exposure time of 0.1 seconds.
The exposure amount was 50 CMS.

The exposed sample was treated with a paper processor using the following processing steps and processing solution compositions.
Continuous processing (running test) was carried out until replenishment of twice the tank capacity for color development.

Treatment process Temperature Time Replenishment amount ^* Tank capacity Color development 35 ° C 45 seconds 161 ml 17 liter Bleach fixing 30-35 ° C 45 seconds 215 ml 17 liter Rinse 1 30-35 ° C 20 seconds 10 liter Rinse 2 30-35 ℃ 20 seconds 10 liters Rinse 3 30 to 35 ℃ 20 seconds 350 ml 10 liters Dry 70 to 80 ℃ 60 seconds * Replenishment amount per 1 m ² of light-sensitive material (rinse 3 → 1 3 tank countercurrent method) The composition of the treatment liquid is as follows.

Color developer (tank solution) (replenisher) Water 800 ml 800 ml Ethylenediamine-N, N, N, N-tetramethylenephosphonic acid 1.5 g 2.0 g Potassium bromide 0.015 g Triethanolamine 8.0 g 12.0 g Chloride Sodium 1.4 g-potassium carbonate 25 g 25 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 5.0 g 7.0 g N, N-bis (carboxymethyl) hydrazine 4.0 g 5.0 g N, N-di (sulfoethyl) hydroxylamine / 1Na 4.0 g 5.0 g Optical brightener (WHITEX 4B, Sumitomo Chemical Co., Ltd.) 1.0 g 2.0 g Water is added to 1000 ml 1000 ml pH (25 ° C) 10.05 10.45 ..

[0148]

Rinse solution (same as tank solution and replenisher) Ion-exchanged water (3 pp each for calcium and magnesium)
m or less) After the running test, use a sensitometer for each sample, give a gradation exposure of three color separation filters for sensitometry (0.1 seconds, 250 CMS), and run a paper processor in a running state. Using the same, development processing was performed as in the running test.

The density of these developed samples was measured,
Then, light fastness test was performed by irradiating with xenon light (950001 ux, 1 week). The light fastness was evaluated by the value of the magenta density after the test in the portion where the magenta density before the light fastness test was 1.0.

The above results are summarized in Tables 1 to 6.

[0152]

[Table 1]

[0153]

[Table 2]

[0154]

[Table 3]

[0155]

[Table 4]

[0156]

[Table 5]

[0157]

[Table 6] As is clear from Tables 1 to 6, the magenta coupler Ex
M, MC-2, MC-3, and MC-4 have the general formula (A-
I) to (A-IV) (hereinafter, compound A)
The lightfastness is improved, but the level is still insufficient. Further, the magenta couplers MC-1 and MC-5 have better light fastness than ExM and the like without adding the compound A, but the effect of improving the light fastness by adding the compound A is small and practical. Is still insufficient.

Magenta couplers I-1, I-4, I-3
7 is a magenta coupler MC when compound A is not added
-1, the same light fastness as MC-5, but these,
It can be seen that by adding the compound A to I-1, I-4, and I-37, the light fastness specifically reaches a very good level.

Further, the maximum density values of magenta color images of these samples 101 to 140 were all sufficient.

(Example 2) (Preparation of Sample 201) Sample 201 was prepared by preparing a multilayer color light-sensitive material having the following composition on a cellulose triacetate film support having a thickness of 127 μm and having an undercoat. The numbers represent the amount added per m ² . The effect of the added compound is not limited to the described use.

First Layer: Antihalation Layer Black Colloidal Silver 0.20 g Gelatin 1.9 g Ultraviolet absorber U-1 0.1 g Ultraviolet absorber U-3 0.04 g Ultraviolet absorber U-4 0.1 g High boiling organic solvent Oil-1 0.1 0.1 g of a microcrystalline solid dispersion of Dye E-1.

Second Layer: Intermediate Layer Gelatin 0.40 g Compound Cpd-C 5 mg Compound Cpd-J 5 mg Compound Cpd-K 3 mg High boiling point organic solvent Oil-3 0.1 g Dye D-4 0.4 mg.

Third layer: intermediate layer Fine grained silver iodobromide emulsion with a fogged surface and inside (average grain size 0.06 μm, coefficient of variation 18%, AgI content 1 mol%) silver amount 0.05 g gelatin 0.4 g.

Fourth layer: low-sensitivity red-sensitive emulsion layer Emulsion A Silver amount 0.1 g Emulsion B Silver amount 0.4 g Gelatin 0.8 g Coupler C-1 0.15 g Coupler C-2 0.05 g Coupler C-3 0.05 g Coupler C-9 0.05 g Compound Cpd-C 10 mg High boiling point organic solvent Oil-2 0.1 g Additive P-1 0.1 g.

Fifth layer: Medium-sensitive red-sensitive emulsion layer Emulsion B Silver amount 0.2 g Emulsion C Silver amount 0.3 g Gelatin 0.8 g Coupler C-1 0.2 g Coupler C-2 0.05 g Coupler C-3 0.2 g High boiling point organic solvent Oil-2 0.1 g Additive P-1 0.1 g.

Sixth layer: High-sensitivity red-sensitive emulsion layer Emulsion D Silver amount 0.4 g Gelatin 1.1 g Coupler C-1 0.3 g Coupler C-2 0.1 g Coupler C-3 0.7 g Additive P-1 0.1 g.

Seventh layer: Intermediate layer Gelatin 0.6 g Additive M-1 0.3 g Color mixing inhibitor Cpd-1 2.6 mg UV absorber U-1 0.01 g UV absorber U-2 0.002 g UV absorber U-5 0.01 g Dye D-1 0.02 g Compound Cpd-C 5 mg Compound Cpd-J 5 mg Compound Cpd-K 5 mg High boiling point organic solvent Oil-1 0.02 g.

Eighth layer: intermediate layer Silver iodobromide emulsion with fogged surface and inside (average grain size 0.06 μm, variation coefficient 16%, AgI content 0.3 mol%) Silver amount 0.02 g Gelatin 1.0 g Additive P- 10.2 g Color-mixing inhibitor Cpd-A 0.1 g.

Ninth layer: low-sensitivity green-sensitive emulsion layer Emulsion E Silver amount 0.1 g Emulsion F Silver amount 0.2 g Emulsion G Silver amount 0.2 g Gelatin 0.5 g Coupler C-4 0.1 g Coupler C-7 0.05 g Coupler C-8 0.20 g Compound A-16 0.03 g Compound Cpd-C 10 mg Compound Cpd-D 0.02 g Compound Cpd-E 0.02 g Compound Cpd-F 0.02 g Compound A-33 0.02 g High boiling point organic solvent Oil-1 0.1 g High boiling point organic Solvent Oil-2 0.1 g.

Layer 10: Medium-speed green-sensitive emulsion layer Emulsion G Silver amount 0.3 g Emulsion H Silver amount 0.1 g Gelatin 0.6 g Coupler C-4 0.1 g Coupler C-7 0.2 g Coupler C-8 0.1 g Compound A-16 0.03 g compound Cpd-D 0.02 g compound Cpd-E 0.02 g compound Cpd-F 0.05 g compound A-33 0.05 g high-boiling point organic solvent Oil-2 0.01 g.

Eleventh layer: High-sensitivity green-sensitive emulsion layer Emulsion I Silver amount 0.5 g Gelatin 1.0 g Coupler C-4 0.3 g Coupler C-7 0.1 g Coupler C-8 0.1 g Compound A-16 0.08 g Compound Cpd-C 5 mg compound Cpd-D 0.02 g compound Cpd-E 0.02 g compound Cpd-F 0.02 g compound A-33 0.02 g compound Cpd-J 5 mg compound Cpd-K 5 mg high boiling point organic solvent Oil-1 0.02 g.

Twelfth layer: intermediate layer 0.6 g of gelatin.

Thirteenth layer: Yellow filter layer Yellow colloidal silver Silver amount 0.07 g Gelatin 1.1 g Color mixture inhibitor Cpd-A 0.01 g High boiling point organic solvent Oil-1 0.01 g Dye E-2 microcrystalline solid dispersion 0.05 g.

Fourteenth layer: intermediate layer 0.6 g of gelatin.

Fifteenth layer: low-sensitivity blue-sensitive emulsion layer Emulsion J Silver amount 0.2 g Emulsion K Silver amount 0.3 g Emulsion L Silver amount 0.1 g Gelatin 0.8 g Coupler C-5 0.2 g Coupler C-6 0.1 g Coupler C-10 0.4 g.

Sixteenth layer: Medium sensitivity blue-sensitive emulsion layer Emulsion L Silver amount 0.1 g Emulsion M Silver amount 0.4 g Gelatin 0.9 g Coupler C-5 0.3 g Coupler C-6 0.1 g Coupler C-10 0.1 g.

Seventeenth layer: High-sensitivity blue-sensitive emulsion layer Emulsion N Silver amount 0.4 g Gelatin 1.2 g Coupler C-5 0.3 g Coupler C-6 0.6 g Coupler C-10 0.1 g.

Eighteenth layer: First protective layer Gelatin 0.7 g UV absorber U-1 0.2 g UV absorber U-2 0.05 g UV absorber U-5 0.3 g Formalin scavenger Cpd-H 0.4 g Dye D-1 0.1 g Dye D-2 0.05 g Dye D-3 0.1 g.

19th layer: 2nd protective layer Colloidal silver Silver amount 0.1 mg Fine grain silver iodobromide emulsion (average grain size 0.06 μm, AgI-containing 1 mol%) 0.1 g Gelatin 0.4 g 20th layer: 3rd protective layer Gelatin 0.4 g Polymethylmethacrylate (average particle size 1.5 μ) 0.1 g Copolymer of methylmethacrylate and acrylic acid 4: 6 (average particle size 1.5 μ) 0.1 g Silicone oil 0.03 g Surfactant W-1 3.0 mg.

In addition to the above composition, additives F-1 to F-8 were added to all emulsion layers. In addition to the above composition, gelatin hardener H-1 and coating and emulsifying surfactants W-2, W-3 and W-4 were added to each layer.

Further, as antiseptic and antifungal agents, phenol, 1,
2-Benzisothiazolin-3-one, 2-phenoxyethanol, phenethyl alcohol were added.

[0182]

[Table 7]

[0183]

[Table 8]

[0184]

[Table 9]

[0185]

[Chemical 53]

[0186]

[Chemical 54]

[0187]

[Chemical 55]

[0188]

[Chemical 56]

[0189]

[Chemical 57]

[0190]

[Chemical 58]

[0191]

[Chemical 59]

[0192]

[Chemical 60]

[0193]

[Chemical formula 61]

[0194]

[Chemical formula 62]

[0195]

[Chemical 63]

[0196]

[Chemical 64]

[0197]

[Chemical 65]

[0198]

[Chemical 66] (Production of Samples 202 to 208) Same as Sample 201, except that the magenta coupler C-8 of the ninth layer, the tenth layer, and the eleventh layer in Sample 201 was replaced with the magenta coupler shown in Table 8 in an equimolar amount. Samples 202 to 208 were manufactured. (Evaluation of light fastness) The sample produced as described above
An object that is considered to be a standard was photographed by cutting into a width of 5 mm, and a running test was performed by the following processing steps until the replenishment amount of the first developing solution became three times the tongue capacity of the first developing step. (Samples 201 to 208 were made to be treated in substantially the same amount.) After this running test, a treatment for evaluating light fastness was performed.

The exposure for evaluating the light fastness was performed by wedge exposure with white light.

Treatment process time Temperature Tank capacity Replenishment amount First development 6 minutes 38 ° C. 12 liters 2200 ml / m ² First water washing 2 minutes 38 ° C. 4 liters 7500 ml / m ² Inversion 2 minutes 38 ° C. 4 liters 1100 ml / m ² color development 6 minutes 38 ° C 12 liters 2200 ml / m ² adjustment 2 minutes 38 ° C 4 liters 1100 ml / m ² bleaching 6 minutes 38 ° C 12 liters 220 ml / m ² fixing 4 minutes 38 ° C 8 liters 1100 Milliliter / m ² Second water wash 4 minutes 38 ° C. 8 liters 7500 ml / m ² stability 1 minute 25 ° C. 2 liters 1100 ml / m ² .

The composition of each processing liquid was as follows.

First developer (tank solution) (replenisher) Nitrilo-N, N, N-trimethylenephosphonic acid-5 sodium salt 1.5 g 1.5 g Diethylenetriamine pentaacetic acid / 5 sodium salt 2.0 g 2.0 g Sodium sulfite 30 g 30 g Hydroquinone potassium monosulfonate 20 g 20 g Potassium carbonate 15 g 20 g Sodium bicarbonate 12 g 15 g 1-Phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone 1.5 g 2.0 g Potassium bromide 2.5 g 1.4 g Potassium thiocyanate 1.2 g 1.2 g Potassium iodide 2.0 mg-Diethylene glycol 13 g 15 g Water was added to 1000 ml 1000 ml pH 9.60 9.60 The pH was adjusted with hydrochloric acid or potassium hydroxide.

Inversion solution (tank solution) (replenishment solution) Nitrilo-N, N, N-trimethylenephosphonic acid-5 sodium salt 3.0 g Same as tank solution Stannous chloride dihydrate 1.0 g p-aminophenol 0.1 g Sodium hydroxide 8 g Glacial acetic acid 15 ml Water was added to 1000 ml pH 6.00 The pH was adjusted with hydrochloric acid or sodium hydroxide.

Color developer (tank solution) (replenisher) nitrilo-N, N, N-trimethylenephosphonic acid-5 sodium salt 2.0 g 2.0 g sodium sulfite 7.0 g 7.0 g trisodium phosphate dodecahydrate 36 g 36 g potassium bromide 1.0 g-potassium iodide 90 mg-sodium hydroxide 3.0 g 3.0 g citrazinic acid 1.5 g 1.5 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline 3/2 Sulfuric acid monohydrate 11 g 11 g 3,6-dithiaoctane-1,8-diol 1.0 g 1.0 g Water was added to 1000 ml 1000 ml pH 11.80 12.00 pH was adjusted with hydrochloric acid or potassium hydroxide.

Conditioning Solution (Tank Solution) (Replenishing Solution) Ethylenediaminetetraacetic acid ・ disodium salt ・ dihydrate 8.0 g 8.0 g Sodium sulfite 12 g 12 g 1-Thioglycerol 0.4 g 0.4 g Formaldehyde sodium bisulfite adduct 30 g 35 g of water was added to 1000 ml 1000 ml pH 6.30 6.10 The pH was adjusted with hydrochloric acid or sodium hydroxide.

Bleaching solution (tank solution) (Replenishing solution) Ethylenediaminetetraacetic acid ・ sodium salt ・ dihydrate 2.0 g 4.0 g Ethylenediaminetetraacetic acid ・ Fe (III) ・ Aminmonium ・ dihydrate 120 g 240 g Potassium bromide 100 g 200 g Ammonium nitrate 10 g 20 g Water was added to 1000 ml 1000 ml pH 5.70 5.50 pH was adjusted with hydrochloric acid or sodium hydroxide.

Fixing Solution (Tank Solution) (Replenishing Solution) Ammonium thiosulfate 80 g The same sodium sulfite 5.0 g Sodium bisulfite 5.0 g Water was added to 1000 ml pH 6.60 pH was adjusted with hydrochloric acid or aqueous ammonia.

Stabilizing Solution (Tank Solution) (Replenishing Solution) Benzisothiazolin-3-one 0.02 g 0.03 g Polyoxyethylene-p-monononylphenyl ether (Average degree of polymerization 10) 0.3 g 0.3 g Water 1000 ml 1000 Milliliter pH 7.0 7.0.

The density of the sample after the development treatment was measured, and the light fastness test was conducted in the same manner as in Example 1.

However, xenon light is 1 at 95000 lux.
Irradiated for 0 days.

The results are summarized in Table 10.

[0212]

[Table 10] As is clear from Table 10, the light fastness is specifically improved by the combined use of the magenta coupler of the present invention and the compounds represented by the general formulas (AI) to (A-IV).

Claims (1)

[Claims] 1. A blue-sensitive emulsion layer and a green-sensitive emulsion on a support.
And at least one halogen-sensitive emulsion layer
In the silver halide color photographic light-sensitive material, its green-sensitive emulsion layer
Pyrazoloazole type coupler represented by the following general formula (I)
At least one of the following general formulas (AI) and (AI)
Compounds represented by I), (A-III) and (A-IV)
A halogen containing at least one of
Silver halide color photographic light-sensitive material. [Chemical 1]R in the formula¹, R²Represents a hydrogen atom or a substituent. However
And R¹, R²Cannot be hydrogen atoms at the same time. R
³Represents an acylamino group or a sulfonamide group. R
^FourRepresents a substituent other than a hydrogen atom, and n is 0, 1 or 2
Is. X is a hydrogen atom or an aromatic primary amine coloring
Represents a group capable of splitting off upon reaction with the oxidized form of a developing agent.
You [Chemical 2]In formulas (A-I) to (A-IV), R is a hydrogen atom.
Child, alkyl group, alkenyl group, aryl group, heterocycle
Group, silyl group, phosphino group or under alkaline conditions.
Represents a protecting group that can be protected. X is -O-, -S- or
IsRepresents. R'represents a group defined by R. R₁~ R
_FiveMay be the same or different, and each is a hydrogen atom or -X.
-R, alkyl group, alkenyl group, aryl group, hetero
Ring group, alkyloxycarbonyl group, aryloxy group
Rubonyl group, halogen atom, acyl group, sulfonyl group,
Carbamoyl group, sulfamoyl group, cyano group, nitro
Represents a group, a sulfo group or a carboxyl group. General formula
In (AI), -X-R, R₁~ R_FiveEach group of
The substituents in the ortho positions are bound to each other by 5 to
A 7-membered ring may be formed. R_TenIs a hydrogen atom, alkyl
Group, alkenyl group, aryl group, oxy radical group,
Droxy group, acyl group, sulfonyl group or sulfini group
Represents a radical. R ₁₁~ R₁₄May be the same or different,
Each represents a hydrogen atom or an alkyl group. A is 5
It represents a group of non-metal atoms necessary for forming a 7-membered ring. M
Is copper, cobalt, nickel, palladium or platinum
Represent. R₂₀, R_{twenty one}, R_{twenty two}, R₂₀´ 、 R_{twenty one}'And R_{twenty two}
′ May be the same or different and each represents a hydrogen atom or an
It represents a kill group or an aryl group. R_{twenty three}And R_{twenty three}´ is
They may be the same or different and each is a hydrogen atom or alkyl.
Group, aryl group, hydroxyl group, alkoxy group or
Represents an aryloxy group. Where R_{twenty three}And R_{twenty three}´ is each other
May be combined with. Also R₂₀~ R_{twenty three}, R₂₀'~ R_{twenty three}of
The groups adjacent to each other are bonded to form an aromatic ring or 5
A ~ 8-membered ring may be formed. A₁And A₃Are the same
They may be different, and each is an oxygen atom, a sulfur atom, or a hydride.
Roxyl group, mercapto group, alkoxy group, alkyl group
O group orRepresents. Where R₃₄And R₃₅Are the same or different
Well, hydrogen atom, alkyl group, aryl group, or
Represents a hydroxyl group. A₂Is -O-, -S-
IsRepresents. R₃₆Is a hydrogen atom, alkyl group or aryl
Represents a radical. R₃₀~ R₃₃May be the same or different,
Represents a hydrogen atom, an alkyl group or an aryl group, respectively.
You Where R₃₀And R₃₃Are bonded to each other by an aromatic ring or 5
A ~ 8-membered ring may be formed. B can be coordinated with M
Represents a compound. The conformation number of this compound is 1-5
It Defined in the general formulas (AI) to (A-IV).
Of the groups, those with a carbon atom are further exposed on this carbon atom.
May have a substituent.