JPH05204106A - Silver halide color photographic sensitive material and photographic pyrazolotriazole type coupler - Google Patents

Abstract

PURPOSE:To reduce occurrence of yellow stains due to heat and heat coupled with moisture by incorporating at least one kind of the specified pyrazolotriazole type coupler in at least one of silver halide emulsion layers formed on a support. CONSTITUTION:The silver halide emulsion layer contains at least one of the pyrazolotriazole compounds represented by formula I in which each of R1 and R2 is alkyl, such as 1-32C straight or branched alkyl optionally substituted by aryl, acylamino, sulfonamide, or sulfonyl; or Ar1 is aryl, such as optionally substituted phenyl or naphthyl, preferably, 6-30C substituted aryl, especially, phenyl substituted by alkyl or alkoxycarbonyl at the 4-position.

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 specifically 1H-pyrazolo [5,
The present invention relates to a silver halide color photographic light-sensitive material containing 1-c] [1,2,4] triazole type magenta coupler and having improved storage stability and color reproducibility.

[0002]

2. Description of the Related Art Generally, a silver halide color photographic light-sensitive material has a multi-layered light-sensitive layer composed of three kinds of silver halide emulsion layers selectively sensitized to have sensitivity to blue light, green light and red light. Each of the light-sensitive layers contains a photographic coupler capable of developing three colors of yellow, magenta and cyan. A color image can be obtained by subjecting this light-sensitive material to color development processing with a color developing solution after exposure.

Upon color development, an aromatic primary amine as a color developing agent and an photographic coupler undergo an oxidative coupling reaction, and as a result, an azomethine type or indophenol type coloring dye is formed. It is important that the color-forming dyes are vivid yellow, magenta and cyan dyes with little side absorption in order to obtain a color photographic image showing good color reproducibility.

Further, in order to store a color photograph having a good color reproducibility for a long period of time, the color image is stable against light, heat and humidity, and at the same time the light, heat and humidity are not recorded on the uncolored portion during storage. It is important that no yellow stain occurs due to.

In recent years, two types of pyrazolotriazoles have been developed as magenta couplers that give azomethine dyes with little side absorption, and they are being put into practical use as light-sensitive materials. One is Japanese Patent Publication No. 2-44051 and US Pat.
1H-pyrazolo [5,1 shown in No. 40,654, etc.
-B] [1,2,4] triazole magenta coupler, and the other is 1H-pyrazolo [5,1-c shown in Japanese Patent Publication No. 47-27411, U.S. Pat. No. 3,725,067, etc. ] [1,2,4] triazole (1H-
Pyrazolo [3,2-c] -s-triazole)
It is a magenta coupler. These are used for color photographic papers and color negative films, and contribute greatly to improving color reproducibility and film sensitivity.

However, when these couplers are used in a color photographic light-sensitive material (color negative film, color reversal film, etc.), there is a problem of storability. This is a problem in that after processing, the uncolored part develops a yellow stain under heat and moist heat conditions during storage. The occurrence of yellow stains during storage is often viewed as it is. In color reversal photographic materials (such as color reversal film), unsightly stains are produced especially on a white background.
Also in the case of color negative photosensitive materials, the reverse imagewise yellow stain not only hinders faithful color reproducibility but also unnecessarily lengthens the printing time, which is a big problem.

Conventionally, the use of pyrazolotriazole couplers for reversal color photographic materials has been described in US Pat. Nos. 4,942,117 and 5,021,325,
It is described in European Patent Publication Nos. 217,353 and 459,340. However, these patents do not take any measures against the above-mentioned problem of the occurrence of stain during storage, and even if the couplers specifically described in the above patents or patent applications are used, their storage stability is We could not solve the problem (occurrence of yellow stain).

Further, the coupler used in the photographic light-sensitive material is required not only to have the above-mentioned drawbacks but also to have a preferable absorption maximum wavelength, high sensitivity and color developability and good graininess as important performance. However, none of the couplers described in the known patents and literatures satisfy the above requirements.

[0009]

SUMMARY OF THE INVENTION An object of the present invention is to provide a color photographic light-sensitive material (preferably a photographic light-sensitive material, especially a reversal photographic light-sensitive material) which solves the above problems. More specifically, the first object of the present invention is to provide a color photographic light-sensitive material in which the generation of yellow stain due to heat and moist heat in the unexposed area during storage after processing is extremely small. A second object is to provide a color photographic light-sensitive material having excellent color reproducibility and color developability of an azomethine dye, and a third object is to use it in the color photographic light-sensitive material.
1H-pyrazolo [5,1-c] [1, which has excellent color reproducibility and can prevent the generation of yellow stain during storage after processing.
2,4] triazole-based magenta couplers. A fourth object of the present invention is to provide a 1H-pyrazolo [5,1-c] [1,1] dye which has a coloring property as high as possible without deteriorating the graininess (size of dye cloud) and has a preferable absorption maximum wavelength. 2,4] triazole-based magenta couplers.

[0010]

The above-mentioned object is achieved by 1H-pyrazolo [5,1-c] represented by the following general formula (I).
This has been achieved by developing [1,2,4] triazole type magenta couplers and incorporating at least one of them in a silver halide color photographic light-sensitive material.

[Chemical 3] (In the formula, R ₁ and R ₂ represent an alkyl group, and Ar ₁ represents an aryl group.)

The substituents R ₁ , R ₂ and Ar ₁ of the coupler represented by formula (I) of the present invention will be described in detail below.

R ₁ and R ₂ represent an alkyl group, more specifically, a straight chain or branched chain alkyl group having 1 to 32 carbon atoms, and these alkyl groups are a halogen atom, an alkyl group, an aryl group and a hetero group. Cyclic 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, azo group, acyloxy group, carbamoyloxy group, silyloxy group, aryloxycarbonylamino group, imide Group, heterocyclic thio group, sulfinyl group It may have a substituent such as a phosphonyl group, an aryloxycarbonyl group, an acyl group, or an azolyl group.

The unsubstituted alkyl group as R ₁ and R ₂ is preferably a linear or branched alkyl group having 1 to 10 carbon atoms, more preferably methyl group, ethyl group, propyl group, isopropyl group, t- A butyl group, an octyl group, a decyl group and a 1-ethylhexyl group are preferred, and an ethyl group and an isopropyl group are particularly preferred.

Preferred substituted alkyl groups for R ₁ and R ₂ are aryl, acylamino,
An alkyl group having a sulfonamide or sulfonyl group as a substituent, and a more preferable substituted alkyl group is an alkyl group having an acylamino, sulfonamide or sulfonyl group as a substituent.

A particularly preferred substituted alkyl group as R ₁ or R _{2 in} the general formula (I) is a group represented by the following general formula (III). A silver halide color photographic light-sensitive material containing a compound of the general formula (I) in which R ₂ is a substituted alkyl group represented by the general formula (III) is particularly preferable.

[0016]

[Chemical 4] In the formula, R ₇ and R ₈ represent a hydrogen atom, an alkyl group or an aryl group, and R ₉ represents a sulfonyl group or an acyl group. n represents an integer of 0 to 5.

More specifically, the alkyl group and aryl group of R ₇ and R ₈ are the same as the alkyl group defined for R ₁ and R ₂ , and the aryl group has 6 carbon atoms.
Represents a substituted or unsubstituted phenyl group or naphthyl group of ˜30, which may have a substituent which the alkyl group of R ₁ and R ₂ may have.

Preferred R ₇ and R ₈ are a hydrogen atom, an alkyl group of methyl, ethyl, isopropyl and t-butyl,
Or, it is an aryl group of phenyl or naphthyl, more preferably a hydrogen atom or an alkyl group of methyl, ethyl or isopropyl. Particularly preferred is a hydrogen atom or a methyl group.

R ₉ represents a sulfonyl group or an acyl group. Of these, the sulfonyl group will be described in detail first by referring to a substituted or unsubstituted alkanesulfonyl group or a substituted or unsubstituted allenesulfonyl group, more specifically methanesulfonyl, Hexanesulfonyl, dodecanesulfonyl, 2-hexyldecanesulfonyl, 1-
(4-pentadecanoylaminophenyl) methanesulfonyl, 4- (2-n-butyloxy-5-t-octylbenzenesulfonyl) butanesulfonyl, or 2-
Alkanesulfonyl groups such as (4-t-octylphenoxy) ethanesulfonyl, or benzenesulfonyl, 4
-Octadecyloxybenzenesulfonyl, 2-octadecyloxy-5-t-butylbenzenesulfonyl, 2
-Dodecyloxy-5-t-butylbenzenesulfonyl, 2-octyloxy-5-t-octylbenzenesulfonyl, 4-pentadecanoylaminobenzenesulfonyl, 2-octyloxy-5- (2-octyloxy-5-t -Octylbenzenesulfonamido) benzenesulfonyl, 1-naphthalenesulfonyl, or 4-
An allenesulfonyl group such as octyloxy-1-naphthalenesulfonyl. The preferred sulfonyl group for R ₉ is a substituted or unsubstituted allenesulfonyl group.

Next, the acyl group of R ₉ will be described in detail. These acyl groups are a substituted or unsubstituted alkanoyl group or a substituted or unsubstituted aryloyl group.

The acyl group will be described in more detail. Acetyl, hexanoyl, dodecanoyl, tetradecanoyl, hexadecanoyl, 2- (2,4-di-t-).
Octylphenoxy) butanoyl, 2- (2,4-di-
t-octylphenoxy) hexanoyl, 2- [4-
An alkanoyl group such as (4-hydroxybenzenesulfonyl) phenoxy] dodecanoyl, 4-dodecanesulfonylbutanoyl or 2- (4-methoxyphenoxy) dodecanoyl, or benzoyl, 1-naphthalenyl,
4-dodecyloxybenzoyl, 2-octadecyloxybenzoyl, 2,5-dioctyloxybenzoyl,
It is an aryloyl group such as 4-t-octylbenzoyl, 3-tridecylaminobenzoyl, 2,6-dioctyloxybenzoyl or 1,4-dioctyloxy-2-naphthalenyl. A preferred acyl group for R ₉ is a substituted or unsubstituted benzoyl group. n is preferably 0 or 1. Particularly preferably, n = 0.

Ar ₁ represents an aryl group, specifically substituted or unsubstituted phenyl, naphthyl and the like. More specifically, phenyl, 4-methylphenyl,
4-methoxycarbonylphenyl, 4-methanesulfonylphenyl, 4-benzoylphenyl, 4- (4-benzyloxybenzenesulfonyl) phenyl, 2,4-dimethylphenyl, 2,4,6-trimethylphenyl, 2,
4-di-methoxyphenyl, 4-t-octylphenyl, 4-n-nonylphenyl, 4-octadecyloxyphenyl, 4-methyl-3-tetradecanoylaminophenyl, 1-naphthyl, 2-naphthyl, or 4- n
An aryl group such as -octanoyloxy-1-naphthyl.

Preferred Ar ₁ is a substituted aryl group having 6 to 30 carbon atoms, particularly preferably a phenyl group having an alkyl group having 1 to 30 carbon atoms as a substituent at the 4-position or an alkoxy group having 1 to 20 carbon atoms. Is a phenyl group having an alkoxycarbonyl group as a substituent at the 4-position. Such a specific substituent exerts a great effect of improving the raw storage stability of the light-sensitive material.

Among the magenta couplers represented by the general formula (I), a particularly preferred coupler is represented by the following general formula (II).

[0025]

[Chemical 5] In the formula, R ₃ represents an alkyl group, and R ₄ and R ₅ represent a hydrogen atom, an alkyl group or an aryl group. R ₆ represents a sulfonyl group. Ar ₂ represents an aryl group.

Next, the substituents R ₃ , R ₄ , and R of the general formula (II)
₅ , R ₆ and Ar ₂ will be described in detail. R ₃ represents an alkyl group, and is preferably a group having the same meaning as an unsubstituted alkyl group which is preferable as R ₁ and R _{2 in} the general formula (I). R ₄ and R ₅ represent a hydrogen atom, an alkyl group or an aryl group, and the alkyl group and the aryl group have the same meaning as R ₇ and R _{8 in} the general formula (III). R ₆ represents a sulfonyl group, which has the same meaning as the sulfonyl group of R _{9 in} the general formula (III). However, a sulfonyl group having a substituent (having 14 to 40 carbon atoms) which can be a ballast group is preferable. Ar ₂ has the same meaning as Ar _{1 in} formula (I).

When R ₁ or R ₂ or Ar ₁ is a divalent group to form a bis form, R ₁ or R ₂ is a substituted or unsubstituted alkylene group (eg, methylene group, ethylene group, 1 , 10-decylene, -CH ₂ CH
_{2 -O-CH 2 CH 2 -} , etc.), a substituted or unsubstituted phenylene group (e.g., 1,4-phenylene group, 1,3
Phenylene group, 2,5-dimethyl-1,3-phenylene group, 2,5-dichloro-1,3-phenylene group, etc.),
Ar ₁ or Ar ₂ represents a divalent group in which the monovalent group is appropriately substituted.

When the vinyl monomers contain the compounds represented by the general formulas (I) and (II), the linking group represented by any of R _{1 to} R ₈ is an alkylene group (a substituted or unsubstituted alkylene group). And, for example, a methylene group, an ethylene group,
1,10 _{decylene, -CH 2 CH 2 OCH 2 CH} 2
-, Etc., phenylene group (substituted or unsubstituted phenylene group, for example, 1,4-phenylene group, 1,3-phenylene group, 2,5-dimethyl-1,3-phenylene group,
2,5-dichloro-1,3-phenylene group, etc.), -N
HCO -, - CONH -, - O -, - OCO- and aralkylene group (e.g., _{-CH 2 C 6 H 4 CH 2} -, - CH
_{2 CH 2 C 6 H 4 CH} 2 CH 2 -, - CH 2 C 6 H 2 C
L ₂ —CH ₂ —, etc.).

Preferred linking groups include: _{-CH 2 CH 2 -, - CH} 2 CH 2 CH 2 C 6 H 4
_{NHCO -, - C 6 H 4} NHCO -, - CH 2 CH 2 N
_{HCO -, - CH 2 CH 2} OCO -, - CH 2 CH 2 O
_{-CH 2 CH 2 -NHCO -, -} CH 2 CH 2 C 6 H 4
CH ₂ CH ₂ NHCO-

The vinyl group may have a substituent other than those represented by the general formulas (I) and (II), and a preferable substituent is a hydrogen atom, a chlorine atom, or a lower alkyl group having 1 to 4 carbon atoms ( For example, a methyl group and an ethyl group) are represented.

Monomers including those represented by the general formulas (I) and (II) are non-color forming ethylene-like monomers and copolymers which do not couple with the oxidation products of aromatic primary amine developing agents. May be made.

As the non-color-forming, ethylene-like monomer which does not couple with the oxidation product of the aromatic primary amine developing agent, acrylic acid, α-chloroacrylic acid, α-alkylacrylic acid (eg methacrylic acid) And esters or amides derived from these acrylic acids (eg acrylamide, n-butyl acrylamide, t
-Butyl acrylamide, diacetone acrylamide,
Methacrylamide, methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, t-butyl acrylate, iso-butyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, lauryl acrylate, methyl methacrylate, ethyl Methacrylate, n-butylmethacrylate and β-hydroxymethacrylate), methylenedibisacrylamide, vinyl ester (eg vinyl acetate, vinyl propionate and vinyl laurate), acrylonitrile, methacrylonitrile, aromatic vinyl compound (eg styrene). And its derivatives, vinyltoluene, divinylbenzene, vinylacetophenone and sulfostyrene), itaconic acid, citraconic acid, croto Acid, vinylidene chloride, vinyl alkyl ethers (e.g., vinyl ethyl ether),
Maleic acid, maleic anhydride, maleic acid ester, N
-Vinyl-2-pyrrolidone, N-vinyl pyridine, and 2- and 4-vinyl pyridine. The non-color-forming ethylenically unsaturated monomers used here may be used in combination of two or more kinds. For example, n-butyl acrylate and methyl acrylate, styrene and methacrylic acid, methacrylic acid and acrylamide, methyl acrylate and diacetone acrylamide, and the like.

As is well known in the art of polymer color couplers, the non-chromogenic, ethylenically unsaturated monomers for copolymerization with the solid water-insoluble monomer coupler are the physical properties and / or chemistry of the copolymer formed. Properties such as solubility, compatibility with photographic colloid composition binders such as gelatin,
It can be chosen so that its flexibility, thermal stability, etc. are positively affected.

The polymer coupler used in the present invention may be water-soluble or water-insoluble, and among them, the polymer coupler latex is particularly preferable. In the silver halide color photographic light-sensitive material of the present invention, the amount of the magenta coupler used is preferably 0.003 to 5 mol, and more preferably 0.0 to 1 mol of the photosensitive silver halide.
It is 1 to 2 mol, particularly preferably 0.02 to 0.5 mol.

Specific examples of typical magenta couplers in the present invention are shown below, but the present invention is not limited thereto.

[0036]

[Chemical 6]

[0037]

[Chemical 7]

[0038]

[Chemical 8]

[0039]

[Chemical 9]

[0040]

[Chemical 10]

[0041]

[Chemical 11]

[0042]

[Chemical 12]

[0043]

[Chemical 13]

[0044]

[Chemical 14]

[0045]

[Chemical 15]

[0046]

[Chemical 16]

A method for synthesizing the magenta couplers represented by the general formulas (I) and (II) will be described.

The general synthetic method mainly used is the method shown in the scheme (1). Aminopyrazole (A) which is a starting material in this synthetic method is disclosed in JP-A-2-300155.
Can be synthesized by the method shown in No. As a method other than this method, there is a method by substituting the 7-position halogen atom (mainly bromine atom) with a phenoxide anion as shown in JP-B-47-27411. Which of these methods is used can be appropriately selected depending on the structure of the target compound.

[0049]

[Chemical 17]

[Synthesis Example] Next, a specific synthesis example will be described in detail.

Synthesis Example 1 (Synthesis of Exemplified Compound M-1) Exemplified Compound M-1 could be synthesized according to the following scheme.

[Chemical 18]

Synthesis of Compound (2) 1.2 l of acetonitrile was added to 642 g of anhydrous potassium carbonate, and 472 g of methyl p-hydroxybenzoate was added thereto while stirring at room temperature. While heating and refluxing this substance, 258 g of chloroacetonitrile (1) was further added dropwise over 10 minutes. After finishing the dropping
After stirring for 3 hours, the mixture was cooled with water until the internal temperature reached about 30 ° C. This product was poured into 3 liters of ice water and stirred for 1 hour, and then the obtained crystals were filtered by suction and dried to obtain 582 g of the desired compound (2) in a yield of 98%. Melting point: 90.0-92.5 ° C. NMR (CDCl ₃ ): δ = 8.06 (d, 2H, J =
9.3 Hz), 7.01 ((d, 2H, J = 9.3 Hz),
4.84 (s, 2H), 3.91 (s, 3H)

Synthesis of compound (3) 36.0 g of oily sodium hydride (60% by weight) and N,
While stirring 100 ml of N-dimethylacetamide, 130 ml of methyl propionate was added dropwise thereto. While further stirring, 86.0 g of the compound (2) was added to the N, N-
A solution of 150 ml of dimethylacetamide was added dropwise over 1 hour. At this time, the internal temperature was 27 to 30 ° C.
After completion of dropping, the mixture was stirred at an internal temperature of 20 ° C. for 2 hours, 360 ml of n-hexane was added, and the mixture was stirred under ice cooling, and 340 ml of water was added dropwise while keeping the internal temperature at 15 ° C. or lower. Further, 40 ml of saturated saline was added thereto for extraction, and the obtained aqueous layer was washed with 360 ml of n-hexane. The aqueous layer thus obtained was stirred under ice cooling and concentrated hydrochloric acid 72 while keeping the internal temperature at 12 ° C or lower.
ml was added, and the mixture was extracted with 500 ml of ethyl acetate. The obtained ethyl acetate layer was washed 3 times with a mixed solution of 100 ml of saturated saline and 300 ml of water, and dried with anhydrous sodium sulfate. Ethyl acetate was distilled off with a rotary evaporator, 215 ml of isopropyl alcohol was added to the residue, and the mixture was stirred in an ice bath. 28.1 ml of an 80% aqueous solution of hydrazine hydrate is added here at an internal temperature of 15 ° C.
After adding dropwise while maintaining the temperature below, the mixture was stirred at an internal temperature of 15 to 20 ° C. for 3 hours. Then, the mixture was heated under reflux for 3 hours, stirred and cooled with water, and 420 ml of water was added dropwise. The precipitated crystals were filtered by suction to obtain 64.1 g of the target compound (3) in a yield of 55%. Melting point: 151.0 to 152.5 ° C NMR (DMSO-d ₆ ): δ = 11.4 (brs, 1
H), 7.94 (d, 2H, J = 9.3 Hz), 7.00
(D, 2H, J = 9.3 Hz), 4.4 (brs, 2
H), 3.81 (s, 3H), 2.33 (q, 2H, J
= 7.8 Hz), 1.03 (t, 3H, J = 7.8 Hz)

Synthesis of Compound (4) 130.6 g of Compound (3) was added to 386 ml of concentrated hydrochloric acid under stirring in an ice-methanol bath, and the internal temperature was adjusted to 0.
An aqueous solution prepared by dissolving 36.2 g of sodium nitrite in 60 ml of water was added dropwise at -3 ° C, and then stirred at 3-5 ° C for 30 minutes. On the other hand, 209 g of anhydrous tin (II) chloride was added to concentrated hydrochloric acid 386
What was melt | dissolved in ml was prepared, the reaction mixture which consists of said compound (3) was added here at 0-8 degreeC of internal temperature, stirring in an ice-methanol bath. 4-8 after addition is complete
After stirring at 0 ° C. for 1 hour, 1 liter of ethyl acetate and 1.5 liter of water were added for extraction, and the obtained ethyl acetate layer was washed twice with 1 liter of saturated saline. To this, 2 liters of water was added and 125 g of baking soda and then 125 g of sodium carbonate were added while stirring to adjust the pH of the aqueous layer to about 9 for extraction. The obtained ethyl acetate layer was washed twice with 1 liter of saturated saline and then dried over anhydrous sodium sulfate. While stirring this solution under ice cooling, 27 g of hydrochloric acid gas was blown in, and the precipitated crystals were filtered and dried to give 84.2.
It was g. The NMR of this crystal was measured by using ethylene glycol as an internal standard, and as a result, the target compound (4) was contained in an amount of 78.67% by weight. Therefore, the yield was 42%. Mp: 102.0~105.5 ℃ NMR (DMSO-d 6): δ = 10.0 (brs, 2
H), 7.95 (d, 2H, J = 9.4 Hz), 7.01
(D, 2H, J = 9.4 Hz), 6.5 (brs, 3
H), 3.83 (s, 3H), 2.45 (q, 2H, J
= 8.5 Hz), 1.10 (t, 3H, J = 8.5 Hz)

Synthesis of Compound (12) 203 g of alanine was added to 365 g of phthalic anhydride (11), and the mixture was stirred at an internal temperature of 150 ° C. for 3 hours, then 1 liter of water was added, and the precipitated crystals were suction filtered to obtain the desired compound. Compound (1
2) was obtained with a yield of 97%. Melting point: 156.5 to 160.0 ° C NMR (DMSO-d ₆ ): δ = 13.2 (brs, 1)
H), 7.8-8.0 (m, 4H), 4.90 (q, 1)
H, J = 7.8 Hz), 1.60 (d, 3H, J = 7.8)
Hz)

Synthesis of compound (5) 20 ml of benzene was added to 21.9 g of compound (12), and 10 ml of thionyl chloride was added dropwise with stirring under heating and reflux. After heating and refluxing were continued for 30 minutes after completion of dropping, benzene was distilled off with an aspirator to obtain the target compound (5) as an oily substance.

Synthesis of compound (6) 230 ml of acetonitrile was added to 35.6 g of compound (4) (78.14% by weight), and the mixture was stirred in an ice-methanol bath. To this, 48.4 ml of triethylamine was added dropwise,
Continuously, 19.6 g of compound (5) was added to 20 ml of acetonitrile.
What was melt | dissolved in was dripped at 3-8 degreeC of internal temperature. After the dropping is completed, the mixture is stirred for 2 hours, then 200 ml of ethyl acetate and 300 ml of water
Was added and extracted. The obtained ethyl acetate layer was washed 3 times with 300 ml of water and then dried over anhydrous sodium sulfate. Ethyl acetate was distilled off with a rotary evaporator to obtain 40 g of the target compound (6) as a crude product. This product was used for the next step without purification.

Synthesis of compound (7) To 40 g of compound (6) obtained in the previous step, 160 ml of acetonitrile was added and stirred. To this, 25.2 g of triphenylphosphine was added, and 12.8 g of N-chlorosuccinimide was added thereto with stirring while maintaining the internal temperature between 18 and 25 ° C. After the addition was completed, the mixture was stirred at room temperature for 2 hours and then heated under reflux for 1 hour. This was poured into 500 ml of ice water and 300 ml of ethyl acetate was added for extraction. 23 ml of triethylamine was added to the obtained ethyl acetate layer.
Was added and stirred for 5 minutes, and then washed with 200 ml of water four times. The ethyl acetate layer thus obtained was dried over anhydrous Glauber's salt and then concentrated by a rotary evaporator. 80 ml of acetonitrile was added to the obtained residue, and the mixture was stirred under ice-cooling, and the precipitated crystals were suction-filtered to give the desired compound (7) at 60%.
43.6 g of crystals containing wt% were obtained. This was purified by silica gel column chromatography to obtain 26.2 g of the desired compound (7) in a yield of 57% (based on compound (12)). Mp: 175.0~177.0 ℃ NMR (DMSO-d 6): δ = 12.90 (s, 1
H), 7.95 (d, 2H, J = 8.7 Hz), 7.8-
8.0 (m, 4H), 7.03 (d, 2H, J = 8.7
Hz), 5.80 (q, 1H, J = 6.9 Hz), 3.82
(S, 3H), 2.31 (q, 2H, J = 8.0Hz),
1.92 (d, 3H, J = 6.9 Hz), 0.80 (t,
3H, J = 8.0Hz)

Synthesis of compound (8) 132 g of compound (7) was mixed with isopropyl alcohol 300
ml was added, and 17.2 g of hydrazine hydrate was added dropwise with stirring. The mixture was stirred at room temperature for 3 hours as it was, and then stirred for 2 hours while heating under reflux. Hexane 30 after cooling to room temperature
0 ml was added, the precipitated crystals were filtered off, and the obtained filtrate was concentrated with a rotary evaporator to give the desired compound (8) as an oil.
Was obtained as a crude product.

Synthesis of compound (14) 30 g of 4-t-butylphenol (13), 41.4 g of anhydrous potassium carbide and 10 parts of N, N-dimethylformamide.
0 ml was added, the internal temperature was heated to 83 ° C., and the mixture was stirred. Here
70 g of n-octadecyl bromide, internal temperature 83 ~ 86 ℃
After completion of the dropwise addition, the mixture was stirred at an internal temperature of 84 to 86 ° C. for 3 hours. This was poured into 1 liter of ice water, and the obtained waxy substance was suction filtered to obtain 81.4 g of the target compound (14).

Synthesis of Compound (9) To 81.4 g of Compound (14), 400 ml of methylene chloride was added and dissolved, and chlorosulfonic acid 1 was added with stirring under ice cooling.
4.9 ml was added dropwise while keeping the internal temperature at 9 to 14 ° C. After completion of dropping for 1 hour, methylene chloride was distilled off with an aspirator, and 160 ml of N, N-dimethylacetamide was added to the obtained residue to dissolve it. While stirring this, 55 ml of phosphorus oxychloride was added dropwise thereto while maintaining the internal temperature at 60 ° C or lower, and after the addition was completed, the internal temperature was 50 to 60 ° C.
It was stirred for 2 hours. This was poured into 500 ml of ice water, and the precipitated crystals were suction filtered to obtain the desired compound (9) 97.6.
It was obtained in a yield of 97% based on g, 4-t-butylphenol. Melting point: 58.5-60.5 ° C

Synthesis of Exemplified Compound M-1 To the compound (8) obtained in the previous step, 300 ml of N, N-dimethylacetamide and 300 ml of ethyl acetate were added and stirred, and 158.2 g of the compound (9) was added to the mixture (2). The mixture was stirred at room temperature for hours. Triethylamine (44.0 ml) was added dropwise, and the mixture was further stirred for 1 hour. 800 ml of ethyl acetate and 800 water
ml was added and extracted, and the obtained ethyl acetate layer was added to 800 ml of water.
After being washed 4 times with, the extract was dried over anhydrous Glauber's salt and concentrated by a rotary evaporator. Methanol 6 was added to the obtained residue.
00 ml was added and the mixture was stirred, and the obtained crystals were suction filtered to obtain 171 g of the desired exemplary compound M-1 in a yield of 75%. Melting point: 47.0 to 49.5 ° C. NMR (CDCl ₃ ): δ = 9.86 (s, 1H),
7.85 (d, 2H, J = 8.7 Hz), 7.80 (d,
1H, J = 2.7 Hz), 7.44 (dd, 1H, J =
2.7 Hz, 9.3 Hz), 6.82 (d, 2H, J = 8.
7 Hz), 6.74 (d, 1H, J = 9.3 Hz), 6.1
5 (d, 1H, J = 10.7Hz), 4.98 (dq, 1
H, J = 10.7 Hz, 7.3 Hz), 3.9-4.1
(M, 2H), 3.86 (s, 3H), 2.55 (q,
2H, J = 8.0 Hz), 1.1-2.0 (m, 4H),
1.70 (d, 3H, J = 7.3 Hz), 0.89 (t,
3H, J = 8.0Hz)

Synthesis Example 2 In the same manner as in Synthesis Example 1, the coupler (M-
2), (M-3), (M-12), (M-22), (M
-23), (M-24), (M-25), (M-2
6), (M-27), (M-28), (M-29),
(M-30), (M-31), (M-32), (M-3
3), (M-34), (M-35) and (M-36) were synthesized. Their melting points are shown below.

Coupler Melting point (° C.) (M-2) 50.0 to 51.5 (M-3) Not crystallized (M-12) 159.5 to 161.0 (M-22) 102.0 to 103.5 (M-23) Not crystallized (M-24) 〃 (M-25) 167.0 to 169.0 (M-26) 178.0 to 179.5 (M-27) Crystallized No (M-28) 203.0 to 204.5 (M-29) 103.5 to 104.5 (M-30) Not crystallized (M-31) 〃 (M-32) 〃 (M-33) ) 〃 (M-34) 〃 (M-35) 〃 (M-36) 105.5-106.5

The present invention also provides a specific 1H-pyrazolo [5,1-c] to reduce the generation of yellow stains in the unexposed areas during storage after processing of color reversal photographic materials.
It also concerns the use of [1,2,4] triazole magenta couplers. In particular, the present invention relates to the use of the color coupler represented by the general formula (I), which has the general formula (I), preferably the general formula (II), and more preferably the general formula (III) as a partial structure, for the above purpose.

The light-sensitive material of the present invention may have at least one layer of a blue-sensitive layer, a green-sensitive layer and a red-sensitive layer of a silver halide emulsion layer provided 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 a unit photosensitive layer having color sensitivity to any of blue light, green light, and red light,
In the multilayer silver halide color photographic light-sensitive material, the unit light-sensitive layers are generally arranged in order of the red-sensitive layer, the green-sensitive layer and the blue-sensitive layer from the support side. Non-photosensitive layers such as various intermediate layers may be provided between the above-described silver halide photosensitive layers and as the uppermost layer and the lowermost layer.

In the intermediate layer, there is disclosed in JP-A-61-43748.
No. 59-113438, No. 59-113440
Nos. 61-20037 and 61-20038, the couplers, the DIR compounds, etc. may be contained, and a color mixing inhibitor may be contained as is usually used.

A plurality of silver halide emulsion layers constituting each unit photosensitive layer are 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 of layers 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. Also,
JP-A-57-112751, JP-A-62-200350
No. 62-206541, No. 62-206543, etc., a low-sensitivity emulsion layer may be provided on the side farther from the support, and a high-sensitivity emulsion layer may be provided on the side closer to the support.

In order to improve color reproducibility, US Pat. Nos. 4,663,271, 4,705,744, 4,707,436 and JP-A-62-160448 are used.
No. 63-89850, and BL, G described in the specification.
A donor layer (CL) having a multilayer effect, which has a spectral sensitivity distribution different from that of the main photosensitive layer such as L and RL, can be arranged adjacent to or in proximity to the main photosensitive layer.

As described above, various layer structures and arrangements can be selected according to the purpose of each light-sensitive material.
The preferred silver halide contained in the photographic emulsion layer of the photographic light-sensitive material used in the present invention is silver iodobromide, silver iodochloride, or silver iodochlorobromide containing about 30 mol% or less of silver iodide. .. Particularly preferred is silver iodobromide or silver iodochlorobromide containing from about 2 mol% to about 10 mol% silver iodide.

The silver halide grains in the photographic emulsion have regular crystals such as cubes, octahedra and tetradecahedrons, grains having irregular crystal forms such as spheres and plates.
It may have a crystal defect such as a twin plane 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) No.
17643 (December 1978), pp. 22-23, "
I. Emulsion preparation and types ",
And No. 18716 (November 1979), 648.
Pp. 307105 (November 1989), 863.
-865 and Graphide, "Physics and Chemistry of Photography," published by Paul Montel (P.Glafkides, Chemie et Phisique
Photographique, Paul Montel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (GF Duff
in, Photographic Emulsion Chemistry (Focal Press, 1
966)), "Production and Coating of Photographic Emulsions" by Zelikmann et al., Published by Focal Press (VL Zelikman et al., Making
and Coating Photographic Emulsion, Focal Press, 19
64) and the like. US Pat. Nos. 3,574,628 and 3,655.
Monodisperse emulsions described in, for example, 394 and British Patent 1,413,748 are also preferable.

Further, tabular grains having an aspect ratio of about 3 or more can be used in the present invention. Tabular grains are described in Gutoff, Photographic Science and E.
ngineering), Vol. 14, pp. 248-257 (1970)
); U.S. Pat. Nos. 4,434,226 and 4,41
4,310, 4,433,048, 4,43
It can be easily prepared by the method described in 9,520 and British Patent 2,112,157. The crystal structure may be uniform, may have a different halogen composition between the inside and the outside, may have a layered structure, and may have a different composition by epitaxial bonding. Good. Also, a mixture of particles having various crystal forms may be used.

The above-mentioned emulsion may be either a surface latent image type in which a latent image is mainly formed on the surface, an internal latent image type in which a latent image is formed, or a type having a latent image both on the surface and inside. It is generally a type of emulsion. Among the internal latent image type emulsions, core / shell type internal latent image type emulsions described in JP-A-63-264740 may be used. This core /
A method for preparing a shell type internal latent image type emulsion is described in JP-A-59-1.
No. 33542. The thickness of the shell of this emulsion varies depending on development processing and the like, but is preferably 3 to 40 nm, particularly preferably 5 to 20 nm. As the silver halide emulsion, those which are physically ripened, chemically ripened and spectrally sensitized are usually used. The additives used in such a process are Research Disclosure No. 17643 and No. 17643.
18716 and No. 307105,
The relevant parts are summarized in the table below.

The light-sensitive material of the present invention comprises a photosensitive silver halide emulsion having a grain size, a grain size distribution, a halogen composition,
Two or more kinds of emulsions having at least one characteristic of grain shape and sensitivity can be mixed and used in the same layer. Surface-fogged silver halide grains described in US Pat. No. 4,082,553, US Pat. No. 4,62.
No. 6,498 and JP-A No. 59-214852, in which the inside of the grains are fogged, colloidal silver is used as a photosensitive silver halide emulsion layer and / or a substantially non-photosensitive hydrophilic colloid layer. Can be preferably used. The fogged silver halide grain inside or on the surface means a silver halide grain which enables uniform (non-imagewise) development regardless of the unexposed portion and exposed portion of the light-sensitive material. .. A method for preparing a silver halide grain whose inside or surface is fogged is described in US Pat. No. 4,626,498, JP-A-59-2.
No. 14852. The silver halide forming the inner nucleus of a core / shell type silver halide grain having a fogged inside may have the same halogen composition or different halogen compositions. As the silver halide having the inside or surface of the grain fogged, any of silver chloride, silver chlorobromide, silver iodobromide and silver chloroiodobromide can be used. The grain size of these fogged silver halide grains is not particularly limited, but the average grain size is 0.01 to 0.75 μm, particularly 0.05 to 0.6 μm.
Is preferred. The grain shape is not particularly limited and may be regular grains or polydisperse emulsions, but monodisperse grains (at least 95% of the weight or number of silver halide grains are ± 40 of the average grain size). %) Is preferable. In the present invention, it is preferable to use a 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 contain silver chloride and / or silver iodide, if necessary. Preferably silver iodide is 0.
The content is 5 to 10 mol%.

The fine grain silver halide preferably has an average grain size (average value of circle equivalent diameters of projected areas) of 0.01 to 0.5 μm, more preferably 0.02 to 0.2 μm. 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 optically 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. Colloidal silver can be preferably contained in the layer containing the fine grain silver halide grains. The silver coating amount of the light-sensitive material of the present invention is preferably 6.0 g / m ² or less,
It is most preferably 4.5 g / m ² or less. 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, page 23, page 648, right column, page 866 2. Sensitivity enhancer, page 648, right column 3. Spectral sensitizer, pages 23 to 24, page 648, right column 866 to Page 868 Supersensitizer to page 649 Right column 4. Brightener page 24 647 page Right column page 868 Page 5 Antifoggant, page 24 to page 649 Right column 868 to 870 Stabilizer 6. Light absorber , Pages 25 to 26, page 649, right column to page 873, filter dye, page 650, left column, UV absorber 7. anti-staining agent, page 25, right column, page 650, left column, page 872 to right column 8. dye image stabilizer, page 25, page 650, left Column 872 9. Hardener 26 Page 651 Left column 874 to 875 Page 10 Binder page 26 651 Left column 873 to 874 11. Plasticizers and lubricants Page 27 650 Right column 876 12. Coating aid Agents, pages 26 to 27, page 650, right column, pages 875 to 876, surface active agent, 13. Static protection, page 27, page 650, right column, pages 876 to 877, blocking agent, matting agents, pages 878 to 879

In order to prevent deterioration of photographic performance due to formaldehyde gas, US Pat. No. 4,411,9
It is preferable to add a compound capable of being immobilized by reacting with formaldehyde described in No. 87 and No. 4,435,503 to the light-sensitive material. The light-sensitive material of the present invention can be incorporated into U.S. Pat.
JP-A-62-18539, JP-A-1-28355
It is preferable that the mercapto compound described in No. 1 is contained. 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. In the light-sensitive material of the present invention, the international publication WO88 / 04
No. 794, Dyes dispersed by the method described in JP-A-1-502912 or EP317,308A, US Pat. No. 4,420,555, JP-A-1-259358.
It is preferable to incorporate the dyes described in No.

Various color couplers can be used in the light-sensitive material of the present invention, and specific examples thereof are Research Disclosure (RD) No. 17643, VII-mentioned above.
C to G, and No. 307105, VII-C to G. Examples of yellow couplers include U.S. Pat. Nos. 3,933,501 and 4,
022,620, 4,326,024, 4,401,752, 4,248,961, Japanese Patent Publication No. 58-10739, and British Patent No. 1,425,02.
0, 1,476,760, U.S. Pat. No. 3,97.
No. 3,968, No. 4,314,023, No. 4,5
Those described in No. 11,649, European Patent No. 249,473A and the like are preferable.

As the magenta coupler, 5-pyrazolone type compounds and pyrazoloazole type compounds other than the present invention can be used in combination, and US Pat. Nos. 4,310,619 and 4,35.
1,897, European Patent 73,636, US Patents 3,061,432, 3,725,067, Research Disclosure No. 24220 (1984).
June 60), JP-A-60-33552, Research Disclosure No. 24230 (June 1984), JP-A-60-43659, JP-A 61-72238, and JP-A 61-72238.
0-35730, 55-118034, 60-
185951, U.S. Pat. Nos. 4,500,630, 4,540,654, 4,556,630,
Those described in International Publication WO88 / 04795 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 shown in US Pat. Nos. 3,451,820 and 4,084.
No. 0,211, No. 4,367,282, No. 4,4
09,320, 4,576,910, British Patent 2,102,137, European Patent 341,188A 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 and West German Patent (Publication) No. 3 , 234,533 are preferable.

Compounds releasing a photographically useful residue upon coupling are also preferably used in the present invention.
DIR couplers that release development inhibitors are RD1 described above.
7643, Item VII-F and Id. 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. RD No. 11449, 24
No. 241, JP-A No. 61-201247, and other bleach-accelerating agent releasing couplers are effective for shortening the processing time having a bleaching ability, and in particular, the above-mentioned tabular silver halide grains are used. The effect is great when it is added to the material. As a coupler which releases a nucleating agent or a development accelerator imagewise during development, British Patent No. 2,092
7,140, 2,131,188, JP-A-59
Those described in Nos. 157638 and 59-170840 are preferable. Further, JP-A-60-107029, JP-A-60-252340, JP-A-1-44940 and JP-A-1-4940.
Compounds releasing a fog agent, a development accelerator, a silver halide solvent and the like by an oxidation-reduction reaction with an oxidized product of a developing agent described in JP-A-45687 are also preferable.

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, DI described in JP-A-62-24252, etc.
R redox compound-releasing coupler, DIR coupler-releasing coupler, DIR coupler-releasing redox compound or DIR redox-releasing redox compound, coupler releasing a dye that recolors after separation described in European Patent Nos. 173,302A and 313,308A , A ligand releasing coupler described in U.S. Pat. No. 4,555,477, a coupler releasing a leuco dye described in JP-A-63-75747, and a fluorescent dye described in U.S. Pat. No. 4,774,181. Examples thereof include releasing couplers.

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods. Examples of high boiling point solvents used in the oil-in-water dispersion method are described in US Pat. No. 2,322,222.
No. 027 and the like. Specific examples of the high-boiling-point organic solvent having a boiling point of 175 ° C. or higher at atmospheric pressure used in the oil-in-water dispersion method include phthalic acid esters (dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis phthalate (2,4-
Di-t-amylphenyl) phthalate, bis (2,4-
Di-t-amylphenyl) isophthalate, bis (1,
1-diethylpropyl) phthalate etc.), phosphoric acid or phosphonic acid esters (triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxy) Ethyl phosphate,
Trichloropropyl phosphate, di-2-ethylhexyl phenylphosphonate, etc., Benzoic acid esters (2-ethylhexyl benzoate, dodecyl benzoate, 2-ethylhexyl-p-hydroxybenzoate etc.), amides (N, N-diethyldodecane amide, N , N-diethyllaurylamide, N-tetradecylpyrrolidone, etc., alcohols or phenols (isostearyl alcohol, 2,4-di-t-amylphenol, etc.), aliphatic carboxylic acid esters (bis (2-ethylhexyl) ) Sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate, etc.), aniline derivatives (N, N-dibutyl-2-butoxy-5-t-octylaniline, etc.) Hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene), and the like. 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 of latex dispersion method, effects, and specific examples of latex for impregnation are described in US Pat. No. 4,199,363, West German Patent Application (OLS) Nos. 2,541,274 and 2,541,230. It is described in.

In the color light-sensitive material of the present invention, phenethyl alcohol, JP-A-63-257747 and JP-A-62-257747 are used.
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 antiseptics or antifungal agents such as 2- (4-thiazolyl) benzimidazole. Suitable supports that can be used in the present invention are described, for example, in RD. No. 17643, page 28, No. 18716, page 647, right column to page 648, left column, and No. 30710.
5, page 879. The light-sensitive material of the present invention is
The total thickness of all hydrophilic colloid layers on the side having the emulsion layer is preferably 28 μm or less, more preferably 23 μm or less, further preferably 18 μm or less, and 16 μm.
The following are particularly preferred. The film swelling speed T _1/2 is preferably 30 seconds or less, more preferably 20 seconds or less. The film thickness is
Means the film thickness measured at 25 ° C. and 55% relative humidity (2 days), and the film swelling rate T _1/2 can be measured according to a method known in the art. For example, by A. Green et al.
Science and Engineering (Photogr. Sc
i, Eng.), Vol. 19, No. 2, pages 124-129, by using a swellometer of the type described in
It can be measured, and T _1/2 is the time required to reach 1/2 of the saturated film thickness, where 90% of the maximum swollen film thickness reached when the film is processed with a color developer at 30 ° C. for 3 minutes and 15 seconds is taken as the saturated film thickness. It is defined as

The film swelling rate T _1/2 can be adjusted by adding a hardening agent to gelatin as a binder or changing the aging condition after coating. The swelling rate is preferably 150 to 400%. The swelling rate is calculated from the maximum swollen film thickness under the above-mentioned conditions by the formula:
It can be calculated according to (maximum swollen film thickness-film thickness) / film thickness.
The photosensitive material of the present invention is preferably provided with a hydrophilic colloid layer (referred to as a back layer) having a total dry film thickness of 2 μm to 20 μm on the side opposite to the side having the emulsion layer. This back layer preferably contains the above-mentioned light absorber, filter dye, ultraviolet absorber, antistatic agent, hardener, binder, plasticizer, lubricant, coating aid, surface active agent and the like. The swelling ratio of this back layer is 150 to 500%
Is preferred.

The light-sensitive material of the present invention is color-developed with the residual silver halide formed by black and white development. 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. Although aminophenol compounds are also useful as the color developing agent, p-phenylenediamine compounds are preferably used, and typical examples thereof include 3-methyl-4-amino-N, N-diethylaniline and 3- Methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-
Examples thereof include N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-β-methoxyethylaniline and their sulfates, hydrochlorides or p-toluenesulfonates. Among these, especially 3
-Methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline sulfate is preferred. Two or more kinds of these compounds can be used in combination depending on the purpose. Color developers are development inhibitors such as pH buffers such as alkali metal carbonates, borates or phosphates, chloride salts, bromide salts, iodide salts, benzimidazoles, benzothiazoles or mercapto compounds. It is common to include agents or antifoggants. If necessary, various preservatives such as hydroxylamine, diethylhydroxylamine, sulfite, hydrazines such as N, N-biscarboxymethylhydrazine, phenylsemicarbazides, triethanolamine and catecholsulfonic acids,
Organic solvents such as ethylene glycol and diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, competitive couplers, 1-phenyl-
An auxiliary developing agent such as 3-pyrazolidone, a tackifier,
Various chelating agents represented by aminopolycarboxylic acid, aminopolyphosphonic acid, alkylphosphonic acid, and phosphonocarboxylic acid, for example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethylimino Diacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilo-N, N, N-trimethylenephosphonic acid,
Representative examples thereof include ethylenediamine-N, N, N, N-tetramethylenephosphonic acid, ethylenediamine-di (o-hydroxyphenylacetic acid) and salts thereof.

Processing solutions and processing steps for the color reversal light-sensitive material of the present invention will be described. Among the processing steps of the color reversal light-sensitive material of the present invention, the steps from black and white development to color development are as follows. 1) Black-white development-water washing-reversal-color development 2) Black-white development-water washing-light reversal-color development 3) Black-white development-water washing-color development
In place of the rinse process described in No. 804,616, it is possible to simplify the process and reduce waste liquid. Next, the steps after color development will be described. 4) Color development-adjustment-bleaching-fixing-washing-stable 5) Color development-washing-bleaching-fixing-washing-stable 6) Color development-adjusting-bleaching-washing-fixing-washing-stable 7) Color development-washing -Bleaching-washing-fixing-washing-stable 8) Color development-bleaching-fixing-washing-stable 9) Color development-bleaching-bleach-fixing-washing-stable 10) Color development-bleaching-bleach-fixing-washing-stable 11) Color development-bleaching-washing-fixing-washing-stable 12) Color development-adjusting-bleaching fixing-washing-stable 13) Color developing-washing-bleaching fixing-washing-stable 14) Color development-bleaching fixing-washing- Stable 15) Color development-fixing-bleach-fixing-washing-stabilization In the processing steps from 4) to 15), the washing step immediately before the stabilizing step may be eliminated, and conversely the final stabilizing step is not performed. May be. The color reversal process is formed by connecting any one of the processes 1) to 3) to any one of the processes 4) to 15).

Next, the processing liquid of the color reversal processing step of the present invention will be described. Known developing agents can be used in the black-and-white developing solution used in the present invention. Examples of developing agents include dihydroxybenzenes (for example, hydroquinone) and 3-pyrazolidones (for example, 1-phenyl-3-).
Pyrazolidone), aminophenols (eg N-methyl-p-aminophenol), 1-phenyl-3-pyrazolidones, ascorbic acid and US Pat. No. 4,064.
A heterocyclic compound such as a 1,2,3,4-tetrahydroquinoline ring and an indole ring described in No. 7,872 can be used alone or in combination. The black-and-white developer used in the present invention may further contain a preservative (eg, sulfite, bisulfite, etc.), a buffer (eg, carbonate, boric acid, borate, alkanolamine), an alkaline agent (eg, water) as necessary. Oxides, carbonates), dissolution tablets (eg polyethylene glycols, esters thereof), pH adjusters (eg organic acids such as acetic acid), sensitizers (eg quaternary ammonium salts), development accelerators, A surfactant, a defoaming agent, a film hardening agent, a viscosity imparting agent, etc. can be contained. The black-and-white developing solution used in the present invention needs to contain a compound acting as a silver halide solvent, and a sulfite salt added as the above preservative usually serves its function. Specific examples of the sulfite and other silver halide solvents that can be used include KSCN and NaSC.
N, K ₂ SO ₃ , Na ₂ SO ₃ , K ₂ S ₂ O ₅ , Na _{2
S 2 O 5, K 2 S} 2 O 3, and the like Na ₂ S ₂ O _3. The pH of the developer adjusted in this way
The value is chosen to be sufficient to provide the desired density and contrast, but is in the range of about 8.5 to about 11.5. In order to carry out the sensitizing process using such a black-and-white developing solution, it is usually necessary to extend the time up to about 3 times the standard process. At this time, if the processing temperature is increased, the extension time for the sensitization processing can be shortened.

PH of these color developing solution and 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 it 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 reversal bath used after black and white development may contain a known fogging material. That is, stannous ion-organic phosphoric acid complex salt (US Pat. No. 3,617,282), stannous ion organic phosphonocarboxylic acid complex salt (Japanese Patent Publication No. 56-32616), stannous ion-
Aminopolycarboxylic acid complex salt (US Pat. No. 1,209,0
50), etc., stannous ion complex salts, borohydride compounds (US Pat. No. 2,984,567), heterocyclic amine borane compounds (UK Patent 1,012).
1,000), and the like, and the like. The fogging bath (reversal bath) has a wide pH range from the acidic side to the alkaline side.
The range is preferably 2.5 to 10, particularly preferably 3 to 9. Instead of the reversal bath, a light reversal treatment by re-exposure may be performed, and the reversal step may be omitted by adding the above-mentioned fogging agent to the color developing solution. The silver halide color photographic light-sensitive material of the present invention is bleached or bleach-fixed after color development. These treatments may be carried out immediately after the color development without passing through other processing steps, in order to prevent unnecessary post-development, air fog and reduce the carry-in of the color developing solution to the desilvering process. The sensitizing dye contained in the photographic light-sensitive material, the light-sensitive material portion such as dye, and the washing out of the color developing agent impregnated in the photographic light-sensitive material,
In order to render it harmless, it may be subjected to a bleaching treatment or a bleach-fixing treatment after being subjected to processing steps such as stopping, adjusting and washing after color development processing.

The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed simultaneously with the fixing process (bleach-fixing process), or may be performed individually. 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 may 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. Typical bleaching agents are organic complex salts of iron (III), such as aminoamines such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, 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 salt and 1,3-diaminopropanetetraacetic acid iron (III) complex salt are preferable from the viewpoint of rapid treatment and prevention of environmental pollution. .. 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 aminopolycarboxylic acid iron (III) complex salts is usually 4.0 to 8, but a lower pH may 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 bleaching accelerators are described in the following specifications: US Pat. No. 3,893,858, West German Patents 1,290,812, 2,059,988, JP No. 53-32736, No. 53-57831, No. 53
-37418, 53-72623, 53-95.
No. 630, No. 53-95631, No. 53-10423.
No. 2, No. 53-124424, No. 53-141623.
No. 53-28426, Research Disclosure No. 17129 (July 1978), and the like, compounds having a mercapto group or a disulfide group; thiazolidine derivatives described in JP-A-50-140129; JP-B-45. -8506, JP-A-52-20832
No. 53-32735, U.S. Pat. No. 3,706,5
Thiourea derivatives described in No. 61; West German Patent No. 1,12
No. 7,715, iodide salts described in JP-A-58-16235; West German Patent Nos. 966,410 and 2,748,4.
Polyoxyethylene compounds described in No. 30; Japanese Patent Publication No. 4
Polyamine compounds described in JP-A-5-8836; Others, JP-A-49-40943, JP-A-49-59644, and JP-A-53-
94927, 54-35727, 55-265.
Compounds described in No. 06 and No. 58-163940; bromide ions and the like can be used. Among them, a compound having a mercapto group or a disulfide group is preferable from the viewpoint of a large accelerating effect, and particularly, U.S. Pat. No. 3,893,858, West German Patent No. 1,290,812, and JP-A-53-95630.
Compounds described in US Pat. Furthermore, US Pat.
The compounds described in No. 552,834 are also preferable. These bleaching accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when bleach-fixing a color light-sensitive material for photographing. In addition to the above compounds, the bleaching solution and the bleach-fixing solution preferably contain an organic acid for the purpose of preventing bleach stain. A particularly preferred organic acid is a compound having an acid dissociation constant (pka) of 2 to 5, specifically, acetic acid,
Propionic acid, hydroxyacetic acid and the like are preferred.

Examples of the fixing agent used in the fixing solution or 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.

The total time of the desilvering process is preferably as short as possible so long as no desilvering failure occurs. Preferred time is 1 to 3 minutes
Minutes, more preferably 1 minute to 2 minutes. The processing temperature is 25 ° C to 50 ° C, preferably 35 ° C to 45 ° C. In the preferred temperature range, the desilvering rate is improved,
In addition, 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 stirring, Japanese Patent Laid-Open Publication No. Sho 6
No. 62-183461, a method of causing a jet of a processing solution to collide with the emulsion surface of the light-sensitive material described in JP-A-2-183460.
Method to improve the stirring effect, and further move the photosensitive material while the emulsion surface is in contact with the wiper blade provided in the liquid to make the emulsion surface turbulent and further improve the stirring effect. And a method of increasing the circulation flow rate of the entire treatment liquid. Such a stirring improving means is effective in any of the bleaching solution, the bleach-fixing solution and the fixing solution. The improvement of stirring is due to the bleaching agent in the emulsion film,
It is considered that the supply of the fixing agent is accelerated, and as a result, the desilvering rate is increased. Further, the above-mentioned stirring improving means is more effective when a bleaching accelerator is used, and it is possible to remarkably increase the accelerating effect and eliminate the fixing inhibiting 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 60-1912.
It is preferable to have the photosensitive material transporting means described in JP-A No. 58 and 60-191259. JP-A-60-
As described in Japanese Patent No. 191257, 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 material used such as couplers), the application, and the temperature of the rinsing water, the number of rinsing tanks (number of stages), replenishment method such as countercurrent, forward flow, and various other conditions It can be set in a wide range. Of these, the relationship between the number of washing tanks and the water volume in the multi-stage countercurrent system is described in the Journal of the Society of Motion Pictur.
e and Television Engineers Volume 64, p. 248 ~
253 (May 1955 issue).

According to the multistage countercurrent method described in the above-mentioned document,
Although the amount of washing water can be significantly reduced, the increase in the residence time of water in the tank causes problems such as bacteria breeding and adhered floating substances to the photosensitive material. In the processing of the color light-sensitive material of the present invention, as a solution to such a problem, the method of reducing calcium ion and magnesium ion described in JP-A-62-288838 can be used very effectively. In addition, JP-A-57-
No. 8542, isothiazolone compounds, siabendazoles, chlorinated germicides such as chlorinated sodium isocyanurate, and other benzotriazoles, etc. Hiroshi Horiguchi, "Chemistry of Antibacterial and Antifungal Agents" (1986) Sankyo Publishing, Sanitary Technology Association, "Microbial Sterilization, Sterilization, and Antifungal Technology" (1982)
It is also possible to use the bactericide described in "Encyclopedia of Antibacterial and Antifungal Agents" (1986) edited by Japan Society of Industrial Technology and Antifungal Society. The pH of washing water in the processing of the light-sensitive material of the present invention is
It is 4-9, preferably 5-8. The washing water temperature and washing time can be variously set depending on the characteristics and use of the light-sensitive material, but in general, the range of 15 to 45 ° C. for 20 seconds to 10 minutes, preferably 25 to 40 ° C. for 30 seconds to 5 minutes is selected. To be done. 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, JP-A-57-8543 and 58-1
All known methods described in No. 4834 and No. 60-220345 can be used. In addition, subsequent to the water washing treatment, there may be a case where further stabilization treatment is performed, and as an example, it is used as a final bath of a color light-sensitive material for photographing.
Mention may be made of a stabilizing bath containing a dye stabilizer and a surfactant. 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 be added to this stabilizing bath. The overflow solution that accompanies the washing with water and / or the supplement 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, US Pat.
Indoaniline compounds described in No. 342,597, No. 3,342,599, Schiff base type compounds described in Research Disclosure No. 14850 and No. 15159, Aldol compounds described in No. 13924. The metal salt complexes described in U.S. Pat. No. 3,719,492 and the urethane compounds described in JP-A-53-135628 can be mentioned.

The silver halide color light-sensitive material of the present invention comprises
In order to accelerate color development, various 1-
Phenyl-3-pyrazolidones may be incorporated. Typical compounds are disclosed in JP-A-56-64339 and JP-A-57-14.
Nos. 4547 and 58-115438.

Various processing solutions used in the present invention are 10 ° C. to 50 ° C.
Used at ° 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.

[0103]

EXAMPLES The present invention will be specifically described below with reference to examples, but the invention is not limited thereto.

Example 1 Preparation of Comparative Sample A A comparative sample A was prepared by preparing a multi-layer color light-sensitive material having the following compositions on a cellulose triacetate film support having a thickness of 127 μ 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 UV absorber U-1 0.1 g UV absorber U-3 0.04 g UV absorber U-4 0.1 g High boiling organic solvent Oil-1 0.1 g Microcrystalline solid dispersion of dye E-1 0.1 g

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 g

Third layer: intermediate layer Fine grained silver iodobromide emulsion whose surface and inside are fogged (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 Sensitivity 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 N-1 0.3 g Color-mixing inhibitor Cpd-I 2.6 mg UV absorber U-1 0.01 g UV absorber U-2 0.002 g Ultraviolet 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, coefficient of variation 16%, AgI content 0.3 mol%) silver amount 0.02 g gelatin 1. 0 g Additive P-1 0.2 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 0.3 g Coupler C-7 0.05 g Compound Cpd-B 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 Cpd-G 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 0.2 g Coupler C-7 0.2 g Compound Cpd-B 0.03g Compound Cpd-D 0.02g Compound Cpd-E 0.02g Compound Cpd-F 0.05g Compound Cpd-G 0.05g High boiling organic solvent Oil-2 0.01g

Eleventh layer: High-sensitivity green-sensitive emulsion layer Emulsion I Silver amount 0.5 g Gelatin 1.0 g Coupler C-4 0.4 g Coupler C-7 0.1 g Compound Cpd-B 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 Cpd-G 0.02 g Compound Cpd-J 5 mg Compound Cpd-K 5 mg High boiling point organic solvent Oil-10 0.02 g High boiling point organic solvent Oil-2 0.02 g

Twelfth layer: intermediate layer Gelatin 0.6 g

Thirteenth layer: Yellow filter layer Yellow colloidal silver Silver amount 0.07 g Gelatin 1.1 g Color mixing inhibitor Cpd-A 0.01 g High boiling point organic solvent Oil-1 0.01 g Microcrystalline solid of dye E-2 Dispersion 0.05g

Fourteenth layer: Intermediate layer Gelatin 0.6 g

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 Ultraviolet absorber U-1 0.02 g Ultraviolet absorber U-2 0.05 g Ultraviolet absorber U-5 0.3 g Formalin scavenger Cpd-H 0 0.4 g Dye D-1 0.1 g Dye D-2 0.05 g Dye D-3 0.1 g

19th layer: Second protective layer Colloidal silver Silver amount 0.1 mg Fine grain silver iodobromide emulsion (average particle size 0.06 μm, AgI content 1 mol%) Silver amount 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 Surfactant W-2 0.03 g

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-3, W-4, W-5 and W-6 were added to each layer. Further, phenol, 1,2-benzisothiazolin-3-one, 2-phenoxyethanol and phenethyl alcohol were added as antiseptic and antifungal agents.

[0126]

[Table 1]

[0127]

[Table 2]

[0128]

[Table 3]

[0129]

[Chemical 19]

[0130]

[Chemical 20]

[0131]

[Chemical 21]

[0132]

[Chemical formula 22]

[0133]

[Chemical formula 23]

[0134]

[Chemical formula 24]

[0135]

[Chemical 25]

[0136]

[Chemical formula 26]

[0137]

[Chemical 27]

[0138]

[Chemical 28]

[0139]

[Chemical 29]

[0140]

[Chemical 30]

[0141]

[Chemical 31]

[0142]

[Chemical 32]

Next, couplers (C-4) and (C-7) used in the ninth layer (low sensitivity green sensitive emulsion layer) and the tenth layer (medium sensitivity green sensitive emulsion layer) of comparative sample A were prepared. Samples (101) to (101) were conducted in exactly the same manner except that the couplers of the present invention and comparative couplers shown in Table 4 were both replaced by equimolar amounts.
(110) and comparative samples B to H were prepared.

The samples prepared as described above are RMS
White light exposure was applied through a wedge to measure graininess and processed according to the following steps. Treatment process Time Temperature First development 6 minutes 38 ° C Water wash 2 minutes 38 ° C Inversion 2 minutes 38 ° C Color development 6 minutes 38 ° C adjustment 2 minutes 38 ° C Bleach 6 minutes 38 ° C Settling 4 minutes 38 ° C Water wash 4 minutes 38 ° C stable 1 minute 25 ° C

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

(Inversion Solution) Nitrilo-N, N, N-trimethylenephosphonic acid-5 sodium salt 3.0 g stannous chloride dihydrate 1.0 g p-aminophenol 0.1 g sodium hydroxide 8 g glacial acetic acid 15 ml water was added and 1000 ml pH 6.00 pH was adjusted with hydrochloric acid or sodium hydroxide.

(Color Developer) Nitrilo-N, N, N-trimethylenephosphonic acid-5 sodium salt 2.0 g sodium sulfite 7.0 g phosphoric acid trisodium dodecahydrate 36 g potassium bromide 1.0 g potassium iodide 90 mg sodium hydroxide 3.0 g citrazinic acid 1.5 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline · 3/2 sulfuric acid · monohydrate 11 g 3,6-dithiaoctane -1,8-diol 1.0g Water was added and 1000 ml pH 11.80 pH was adjusted with hydrochloric acid or potassium hydroxide.

(Preparation Solution) Ethylenediaminetetraacetic acid / sodium dihydrate / 8.0 g Sodium sulfite 12 g 1-Thioglycerol 0.4 g Sodium formaldehyde bisulfite adduct 30 g Water was added to 1000 ml pH 6.20 pH was hydrochloric acid or Adjusted with sodium hydroxide.

(Bleaching Solution) Ethylenediaminetetraacetic acid.2sodium.dihydrate 2.0 g Ethylenediaminetetraacetic acid.Fe (III) .Ammonium dihydrate 120 g Potassium bromide 100 g Ammonium nitrate 10 g Water 1000 ml pH 5.70 The pH was adjusted with hydrochloric acid or sodium hydroxide.

(Fixer) Ammonium thiosulfate 80 g Sodium sulfite 5.0 g Sodium bisulfite 5.0 g Water was added to 1000 ml pH 6.60 The pH was adjusted with hydrochloric acid or aqueous ammonia hydroxide.

(Stabilizing Solution) Benzisothiazolin-3-one 0.02 g Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.3 g Water was added to 1000 ml pH 7.0

The samples thus treated were tested for graininess and storability (generation of yellow stain). The results are shown in Table 4.

[0153]

[Table 4]

[0154]

[Chemical 33]

[0155]

[Chemical 34]

[0156]

[Chemical 35]

As can be seen from the results in Table 4, the generation of yellow stain in the uncolored part (white) under heating conditions is extremely small in the sample using the coupler of the present invention. This shows that the silver halide color light-sensitive material using the coupler of the present invention is excellent in storage without deterioration of image quality.

Further, when the coupler of the present invention was used, the graininess of the magenta color image was not deteriorated as compared with the comparative sample A which used the conventional 4-equivalent 5-pyrazolone magenta coupler although it was a 2-equivalent coupler. I understand. In comparison, it can be seen that in Comparative Samples B to H, the graininess deteriorates.

Example 2 15.0 g of the coupler (M-1) of the present invention was weighed, 3.0 g of a high boiling point organic solvent and tricresyl phosphate were added, and 15 ml of ethyl acetate was further added to dissolve the solution. Is a 10 wt% gelatin aqueous solution containing 1.5 g of sodium 1,8-di-t-butyl-naphthalenesulfonate 200
emulsified and dispersed in g. The total amount of this emulsified dispersion was 310 g of silver iodobromide emulsion (silver 70.0 g / kg emulsion, silver iodide content 2.
5 mol%) and coated on a triacetate film base having an undercoat layer so that the coated silver amount is 2.15 g / m ^2, and a gelatin layer as a protective layer is dried on the coated layer. Sample 201
Was produced. As the gelatin hardener, 1,2-bis (vinylsulfonylacetamide) ethane was used.

Then, Samples (201) to (210) of the present invention and Comparative Sample (I) were prepared in the same manner except that the coupler (M-1) of Sample 201 was replaced with the coupler shown in Table 5 in an equimolar amount. ~ (L) were created.

Each of the prepared samples was processed according to the processing steps shown in Example 1. The spectral absorption spectrum of each obtained sample was measured. Table 5 shows the maximum absorption maximum wavelength (λmax).

[0162]

[Table 5]

[0163]

[Chemical 36]

[0164]

[Chemical 37]

Further, sample 201 of the present invention and comparative sample (I)
The absorption spectra of (K) and (K) are shown in FIG. When the color gamut was calculated using these absorption spectra,
It was found that the magenta color image obtained using the coupler of the present invention having a λmax in the range of 548 to 558 nm gives a better result than the comparative sample in terms of color reproduction of red system. That is, the material using the conventional coupler is the comparative sample (I), but the color gamut in the red to magenta region is expanded as compared with that, and the expansion improves the saturation without changing the tint. It was a thing. Comparative sample (J)
In the case of (K) and (L), this is 540-543 nm.
It was found that although the color reproduction range was expanded compared with the comparative sample (I), the expansion changed the color in the red to magenta region toward yellowish color. From this result, it was revealed that the sample obtained from the coupler of the present invention had the absorption maximum wavelength preferable for color reproduction.

Example 3 On a subbed cellulose triacetate film support,
Each layer having the composition shown below was coated in multiple layers to prepare a comparative sample M which is a multilayer color light-sensitive material.

(Photosensitive Layer Composition) The main materials used for each layer are classified as follows: ExC: Cyan coupler UV: UV absorber ExM: Magenta coupler HBS: High boiling organic solvent ExY: Yellow coupler H: Gelatin ExS: Sensitizing dye The numeral corresponding to each component indicates the coating amount expressed in g / m ² , and for silver halide, the coating amount in terms of silver. However, with respect to the sensitizing dye, the coating amount is shown in mol unit per mol of silver halide in the same layer.

(Comparative Sample M) First Layer (Antihalation Layer) Black Colloidal Silver Silver 0.18 Gelatin 1.40 ExM-1 0.18 ExF-1 2.0 × 10 ⁻³

Second Layer (Intermediate Layer) Emulsion G Silver 0.065 2,5-di-t-pentadecylhydroquinone 0.18 ExC-2 0.020 UV-1 0.060 UV-2 0.080 UV- 3 0.10 HBS-1 0.10 HBS-2 0.020 Gelatin 1.04

Third Layer (Low Sensitivity Red Sensitive Emulsion Layer) Emulsion A Silver 0.25 Emulsion B Silver 0.25 ExS-1 6.9 × 10 ⁻⁵ ExS-2 1.8 × 10 ⁻⁵ ExS-3 3 .1 * 10 < ^-4 > ExC-1 0.17 ExC-4 0.17 ExC-7 0.020 UV-1 0.070 UV-2 0.050 UV-3 0.070 HBS-1 0.060 Gelatin 0 .87

Fourth Layer (Medium Sensitivity Red Sensitive Emulsion Layer) Emulsion D Silver 0.80 ExS-1 3.5 × 10 ⁻⁴ ExS-2 1.6 × 10 ⁻⁵ ExS-3 5.1 × 10 ⁻⁴ ExC-1 0.20 ExC-2 0.050 ExC-4 0.20 ExC-5 0.050 ExC-7 0.015 UV-1 0.070 UV-2 0.050 UV-3 0.070 Gelatin 1 .30

Fifth Layer (High Sensitivity Red Sensitive Emulsion Layer) Emulsion E Silver 1.40 ExS-1 2.4 × 10 ⁻⁴ ExS-2 1.0 × 10 ⁻⁴ ExS-3 3.4 × 10 ⁻⁴ ExC-1 0.097 ExC-2 0.010 ExC-3 0.065 ExC-6 0.020 HBS-1 0.22 HBS-2 0.10 Gelatin 1.63

Sixth Layer (Intermediate Layer) Cpd-1 0.040 HBS-1 0.020 Gelatin 0.80

Seventh Layer (Low Sensitivity Green Sensitive Emulsion Layer) Emulsion C Silver 0.30 ExS-4 2.6 × 10 ⁻⁵ ExS-5 1.8 × 10 ⁻⁴ ExS-6 6.9 × 10 ⁻⁴ ExM-1 0.021 ExM-2 0.26 ExM-3 0.030 ExY-1 0.025 HBS-1 0.10 HBS-3 0.010 Gelatin 0.63

Eighth Layer (Medium Sensitivity Green Sensitive Emulsion Layer) Emulsion D Silver 0.55 ExS-4 2.2 × 10 ⁻⁵ ExS-5 1.5 × 10 ⁻⁴ ExS-6 5.8 × 10 ⁻⁴ ExM-2 0.094 ExM-3 0.026 ExY-1 0.018 HBS-1 0.16 HBS-3 8.0 × 10 ^-3 gelatin 0.50

Ninth Layer (High Sensitivity Green Sensitive Emulsion Layer) Emulsion E Silver 1.55 ExS-4 4.6 × 10 ⁻⁵ ExS-5 1.0 × 10 ⁻⁴ ExS-6 3.9 × 10 ⁻⁴ ExC-1 0.015 ExM-1 0.013 ExM-4 0.065 ExM-5 0.019 HBS-1 0.25 HBS-2 0.10 Gelatin 1.54

Tenth Layer (Yellow Filter Layer) Yellow Colloidal Silver Silver 0.035 Cpd-1 0.080 HBS-1 0.030 Gelatin 0.95

Eleventh Layer (Low Sensitivity Blue Sensitive Emulsion Layer) Emulsion C Silver 0.18 ExS-7 8.6 × 10 ⁻⁴ ExY-1 0.042 ExY-2 0.72 HBS-1 0.28 Gelatin 1 .10

Twelfth Layer (Medium Sensitivity Blue Sensitive Emulsion Layer) Emulsion D Silver 0.40 ExS-7 7.4 × 10 ⁻⁴ ExC-7 7.0 × 10 ⁻³ ExY-2 0.15 HBS-10 0.050 gelatin 0.78

Thirteenth Layer (High Sensitivity Blue Sensitive Emulsion Layer) Emulsion F Silver 0.70 ExS-7 2.8 × 10 ⁻⁴ ExY-2 0.20 HBS-1 0.070 Gelatin 0.69

Fourteenth Layer (First Protective Layer) Emulsion G Silver 0.20 UV-4 0.11 UV-5 0.17 HBS-1 5.0 × 10 ^-2 Gelatin 1.00

Fifteenth layer (second protective layer) H-1 0.40 B-1 (diameter 1.7 μm) 5.0 × 10 ⁻² B-2 (diameter 1.7 μm) 0.10 B-30 .10 S-1 0.20 Gelatin 1.20

Further, in order to improve the storability, processability, pressure resistance, antifungal / antibacterial property, antistatic property and coating property of each layer, W-1 to W-3, B-4 to B are appropriately added. -6,
F-1 to F-17 and iron salt, lead salt, gold salt, platinum salt, iridium salt and rhodium salt are contained.

[0184]

[Table 6]

In Table 6, (1) Emulsions A to F were reduction-sensitized at the time of grain preparation using thiourea dioxide and thiosulfonic acid according to the examples of JP-A-2-191938. (2) Emulsions A to F were subjected to gold sensitization, sulfur sensitization and selenium sensitization in the presence of the spectral sensitizing dye described in each photosensitive layer and sodium thiocyanate according to the examples of JP-A-2-34090. Has been done. (3) For the preparation of tabular grains, low molecular weight gelatin is used according to the examples of JP-A-1-158426. (4) Dislocation lines as described in JP-A-2-34090 have been observed in tabular grains and normal crystal grains having a grain structure using a high voltage electron microscope.

[0186]

[Chemical 38]

[0187]

[Chemical Formula 39]

[0188]

[Chemical 40]

[0189]

[Chemical 41]

[0190]

[Chemical 42]

[0191]

[Chemical 43]

[0192]

[Chemical 44]

[0193]

[Chemical 45]

[0194]

[Chemical 46]

[0195]

[Chemical 47]

[0196]

[Chemical 48]

[0197]

[Chemical 49]

[0198]

[Chemical 50]

Next, the magenta coupler ExM2 of the seventh layer (low-sensitivity green-sensitive emulsion layer) and the eighth layer (medium-sensitivity green-sensitive emulsion layer) of Comparative Sample M was used as couplers M-1, M-5 and M of the present invention. −
Sample (301) in exactly the same manner except that 9, M-15, M-25, M-30 and M-38 were replaced with equimolar amounts.
~ (307) were created.

The color photographic light-sensitive material prepared as described above was exposed and then processed by the method described below.

Next, the composition of the processing liquid is shown. (Color developer) (Unit g) Diethylenetriaminepentaacetic acid 1.0 1-Hydroxyethylidene-1,1-diphosphonic acid 3.0 Sodium sulfite 4.0 Potassium carbonate 30.0 Potassium bromide 1.4 Potassium iodide 1. 5 mg hydroxylamine sulfate 2.4 4- [N-ethyl-N-β-hydroxyethylamino] -2-methylaniline sulfate 4.5 Water was added to 1.0 liter pH 10.05

(Bleaching Solution) (Unit: g) Ethylenediaminetetraacetic acid sodium ferric trihydrate 100.0 Ethylenediaminetetraacetic acid disodium salt 10.0 3-Mercapto-1,2,4-triazole 0.08 Ammonium bromide 140.0 Ammonium nitrate 30.0 Ammonia water (27%) 6.5 ml Water was added to 1.0 liter pH 6.0

(Fixer) (Unit: g) Ethylenediaminetetraacetic acid disodium salt 0.5 Ammonium sulfite 20.0 Ammonium thiosulfate aqueous solution (700 g / liter) 290.0 ml Water was added to 1.0 liter pH 6.7

(Stabilizing Solution) (Unit: g) Sodium p-toluenesulfinate 0.03 Polyoxyethylene-p-monononylphenyl ether (Average degree of polymerization: 10) 0.2 Ethylenediaminetetraacetic acid disodium salt 0.05 1, 2,4-triazole 1.3 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine 0.75 Water was added to 1.0 liter pH 8.5

Comparing the obtained samples, the samples (301) to (307) using the coupler of the present invention are superior in granularity to the comparative sample (M) using the conventional 5-pyrazolone coupler. It was also found that it has excellent storage stability. From this, it is understood that the coupler of the present invention exhibits excellent performance not only in the reversal color photographic light-sensitive material but also in the negative photographic light-sensitive material.

Example 4 15.0 g of the coupler of the present invention, (M-1), was weighed, and 15.0 g of the high boiling point organic solvent, tricresyl phosphate.
Furthermore, 15 ml of ethyl acetate was further added and dissolved, and this solution was added with a 10 wt% gelatin aqueous solution 200 containing 1.5 g of sodium 1,8-di-t-butylnaphthalenesulfonate.
emulsified and dispersed in g. The total amount of this emulsified dispersion was added to 310 g of silver iodobromide emulsion (silver 70.0 g / kg) emulsion, silver iodide content of 2.5 mol%), and the coating silver amount was 2.15 g / m ^2.
Sample 40 was prepared by coating on a triacetate film base on which an undercoat layer has been formed so that a gelatin layer as a protective layer has a dry film thickness of 1.0 μm.
Created 1.

Then, the couplers (M-1) of Sample 401 were replaced with the couplers shown in Table 7 in equimolar amounts, and Samples (402) to (409) of the present invention and Comparative Sample (N) were prepared in the same manner. ~ (V) were created. Each of the prepared samples was processed according to the processing steps shown in Example 1. Each of the obtained samples was stored at 100 ° C. for 7 days, and the yellow stain concentration in the uncolored portion was measured and compared with that before storage. The results are shown in Table 7.

[0208]

[Table 7]

As can be seen from the results in Table 7, in the storage test conducted on the treated sample under heat and moist heat conditions, yellow stain was generated in the uncolored part (white background) in the sample using the coupler of the present invention. It turns out that is very small. This indicates that the silver halide color photographic light-sensitive material using the coupler of the present invention is excellent in storage without deterioration of image quality.

[0210]

The use of the coupler represented by the general formula (I) or (II) of the present invention in a color photographic light-sensitive material, particularly a reverse color photographic light-sensitive material improves the color reproducibility in the red to magenta region. In addition, the graininess, which is extremely important as a photographic material, is improved. In addition, yellow stains are less likely to occur during long-term storage, and the deterioration of image quality is small.

[Brief description of drawings]

FIG. 1 is transmission absorption spectra of Sample 201 of Example 2 and Comparative Samples (I) and (K).

[Explanation of symbols]

 1 Absorption spectrum of Sample 201 2 Absorption spectrum of Comparative Sample (I) 3 Absorption spectrum of Comparative Sample (K)

Claims (3)

[Claims] 1. A silver halide having at least one silver halide emulsion layer on a support and containing at least one pyrazolotriazole coupler represented by the general formula (I). Color photographic light-sensitive material. [Chemical 1] (In the formula, R ₁ and R ₂ represent an alkyl group, and Ar ₁ represents an aryl group.) 2. A photographic pyrazolotriazole coupler represented by the general formula (II). [Chemical 2] (In the formula, R ₃ represents an alkyl group, R ₄ and R ₅ represent a hydrogen atom, an alkyl group or an aryl group, R ₆ represents a sulfonyl group, and Ar ₂ represents an aryl group.) 3. In the general formula (I), R ₂ is the general formula (II
The silver halide color photographic light-sensitive material according to claim 1, which is represented by the formula I). Formula _{(III) -C (R 7)} (R 8) - (CH 2) n -NHR 9 ( wherein, R ₇ and R ₈ represents a hydrogen atom, an alkyl group, or aryl group, R ₉ is sulfonyl Represents a group or an acyl group, and n represents any integer from 0 to 5.)