JPH08110620A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE: To obtain superior hue, coupling activity, and heat and light fastness and to reduce the fluctuation of color development density due to the fluctuation of the composition of a processing solution by incorporating a specified coupler in at least one layer formed on a support. CONSTITUTION: At least one layer formed on a support needs to contain at least one kind of coupler represented by formula I in which Za is -C(R3 )= or -N=, and when Za is -N=, Zb is -C(R3 )=, and when Za is -C(R3 )=, Zb is -N=; each of R1 and R2 is an electron withdrawing group having a Hammett' s substituent constant σp of 0.20-1.0; R3 is a substituent; Y is a group of formula II or -SO2 R5 ; R4 is an alkyl or alkoxy or aryloxy group; R5 is an alkoxy or aryl group; each of R6 and R7 is an alkyl or aryl or alkoxy or aryloxy group; and X is an O or S atom.

Description

Detailed Description of the Invention

[0001]

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

[0002]

2. Description of the Related Art In a silver halide color photographic light-sensitive material, an exposed aromatic silver halide color developing agent is used as an oxidizing agent to react an oxidized aromatic primary amine type color developing agent with a coupler to form indophenol or indoaniline. It is well known that indium, indamine, azomethine, phenoxazine, phenazine and dyes related thereto form color images. In such a photographic system, a subtractive color method is used, and a color image is formed by yellow, magenta and cyan dyes. Of these, phenol or naphthol based couplers are commonly used to form cyan dye images. However, since these couplers have an unfavorable absorption in the green region, they have a serious problem that the color reproducibility is significantly reduced, and it is desired to solve these problems.

As means for solving this problem, the heterocyclic compounds described in US Pat. Nos. 4,728,598 and 4,873,183 and European Patent 0249453A2 have been proposed. However, these couplers have fatal problems such as low coupling activity. As couplers that overcome these problems, European Patent Publication Nos. 491197A1, 488248, and 5 have been disclosed.
The pyrroloazoles described in 45,300 have been proposed. These couplers have different hues, coupling activities,
It is excellent in that respect. However, the dyes produced from the couplers described in these patents do not always have sufficient light fastness, and in particular, they have poor light fastness in the low color density portion. Further, there is a problem that the color density is changed due to the change of the composition of the treatment liquid, and improvement has been practically desired.

[0004]

Therefore, an object of the present invention is to provide excellent hue, coupling activity, heat fastness and light fastness, and to reduce variations in color density caused by variations in processing liquid composition. An object is to provide a silver halide color light-sensitive material containing a coupler.

[0005]

Means for Solving the Problems The present inventors have made diligent studies on a pyrrolotriazole-based coupler,
It has been found that the object of the present invention can be achieved by the following means. That is, it is achieved by a silver halide color light-sensitive material characterized in that at least one layer on a support contains at least one coupler represented by the following general formula (I). General formula (I)

[0006]

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In the general formula (I), Za represents -C (R ₃ ) = or -N =, and when Za represents -N =, Zb
It is -C (R ₃₎ = represents, when Za represents -C (R ₃₎ =, Zb represents -N =. R ₁ and R ₂ each have a Hammett's substituent constant σ _p value of 0.20 or more and 1.0
The following electron-withdrawing groups are represented. R ₃ represents a substituent.
Y is

[0008]

[Chemical 4]

Alternatively, it represents --SO ₂ R ₅ . R ₄ represents an alkyl group, an alkoxy group or an aryloxy group. R ₅ represents an alkyl group or an aryl group. R ₆
R ₇ and R ₇ may be the same or different and each represents an alkyl group, an aryl group, an alkoxy group or an aryloxy group, and R ₆ and R ₇ may combine with each other to form a ring. X represents an oxygen atom or a sulfur atom.

The compound of the present invention is described in detail below. The coupler of the present invention can be specifically represented by the following general formulas (II) and (III).

[0011]

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(Wherein R _{1 to} R ₇ , Y and X are general formulas
It is synonymous with each in (I). In the present invention, the coupler represented by the general formula (II) is particularly preferable.

In the coupler of the present invention, R ₁ and R ₂ are both electron-withdrawing groups of 0.20 or more and 1.0 or less,
It is desirable that the sum of the σ _p values of R ₁ and R ₂ be 0.65 or more. The coupler of the present invention has excellent performance as a cyan coupler by introducing such a strong electron-withdrawing group. The sum of the σ _p values of R ₁ and R ₂ is preferably 0.70 or more, and the upper limit is about 1.8.

In the present invention, R ₁ and R ₂ have a Hammett's substituent constant σ _p value (hereinafter, simply referred to as σ _p value) of 0.
It is an electron-withdrawing group of 20 or more and 1.0 or less. An electron-withdrawing group having a σ _p value of 0.30 or more and 0.80 or less is preferable. The Hammett's rule is an empirical rule proposed by LP Hammett in 1935 to quantitatively discuss the influence of substituents on the reaction or equilibrium of benzene derivatives, which is widely accepted today. There are σ _p and σ _m values in the substituent constants determined by Hammett's rule,
These values can be found in many common publications, but for example, see JA Dean, “Lange's Handbook of Chemistry”.
12th Edition, 1979 (Mc Graw-Hill) and “Special Issue on Chemistry”, 122, 96-103, 1979 (Nankodo), Chemical Reviews, 91, 165-195.
See page, 1991 for details. In the present invention, R ₁ and R ₂
Is defined by the Hammett's substituent constant σ _p value, but it does not mean that the values known in the literature described in these publications are limited to certain substituents, and even if the value is unknown in the literature, Hammett's rule Needless to say, it is included as long as it is included in the range when measured based on.

Specific examples of R ₁ and R ₂ which are electron withdrawing groups having a σ _p value of 0.20 or more and 1.0 or less include an acyl group, an acyloxy group, a carbamoyl group, an aliphatic oxycarbonyl group and an aryloxy group. Carbonyl group, cyano group,
Nitro group, dialkylphosphono group, diarylphosphono group, diarylphosphinyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group,
Arylsulfonyl group, sulfonyloxy group, acylthio group, sulfamoyl group, thiocyanate group, thiocarbonyl group, alkyl group substituted with at least two or more halogen atoms, alkoxy group substituted with at least two or more halogen atoms, at least An aryloxy group substituted with two or more halogen atoms, an alkylamino group substituted with at least two halogen atoms, an alkylthio group substituted with at least two halogen atoms, σ _{p of} 0.20 or more Examples thereof include an aryl group substituted with another electron-withdrawing group, a heterocyclic group, a chlorine atom, a bromine atom, an azo group, or a selenocyanate group. Among these substituents, the group capable of further having a substituent may further have a substituent as mentioned below for R ₃ .

The aliphatic oxycarbonyl group is an aliphatic moiety whose aliphatic moiety may be linear, branched or cyclic and which may contain a saturated or unsaturated bond.
The aliphatic oxycarbonyl group is alkoxycarbonyl,
It includes cycloalkoxycarbonyl, alkenyloxycarbonyl, alkynyloxycarbonyl, cycloalkenyloxycarbonyl and the like.

[0017] Representative sigma _p value is listed sigma _p value of the electron withdrawing groups 0.2 to 1.0, a bromine atom (0.2
3), chlorine atom (0.23), cyano group (0.66),
Nitro group (0.78), trifluoromethyl group (0.5
4), tribromomethyl group (0.29), trichloromethyl group (0.33), carboxyl group (0.45), acetyl group (0.50), benzoyl group (0.43), acetyloxy group ( 0.31), trifluoromethanesulfonyl group (0.92), methanesulfonyl group (0.7
2), benzenesulfonyl group (0.70), methanesulfinyl group (0.49), carbamoyl group (0.3
6), methoxycarbonyl group (0.45), ethoxycarbonyl group (0.45), phenoxycarbonyl group (0.44), pyrazolyl group (0.37), methanesulfonyloxy group (0.36), dimethoxyphosphoryl Group (0.60), sulfamoyl group (0.57) and the like.

Examples of the substituent of R ₁ are preferably a cyano group, an aliphatic oxycarbonyl group (a linear or branched alkoxycarbonyl group having 2 to 36 carbon atoms, an aralkyloxycarbonyl group, an alkenyloxycarbonyl group, an alkynyloxycarbonyl group). Group, cycloalkoxycarbonyl group, cycloalkenyloxycarbonyl group, for example, methoxycarbonyl, ethoxycarbonyl, dodecyloxycarbonyl, octadecyloxycarbonyl, 2-ethylhexyloxycarbonyl, sec-butyloxycarbonyl, oleyloxycarbonyl, benzyloxy. Carbonyl, propargyloxycarbonyl, cyclopentyloxycarbonyl, cyclohexyloxycarbonyl, 2,6-di-t-butyl-4-methylcyclohexyloxycarbonyl Nyl), dialkylphosphono group (dialkylphosphono group having 2 to 36 carbon atoms, for example, diethylphosphono, dimethylphosphono), alkyl or arylsulfonyl group (alkyl or arylsulfonyl group having 1 to 36 carbon atoms, And represents, for example, a methanesulfonyl group, a butanesulfonyl group, a benzenesulfonyl group, a p-toluenesulfonyl group) and a fluorinated alkyl group (a fluorinated alkyl group having 1 to 36 carbon atoms, for example, trifluoromethyl). The substituent for R ₁ is particularly preferably a cyano group, an aliphatic oxycarbonyl group or a fluorinated alkyl group, and a cyano group is most preferable.

As an example of the substituent of R ₂ , preferably R ₁
And the aliphatic oxycarbonyl group, carbamoyl group (C1-C36 carbamoyl group, for example, diethylcarbamoyl, dioctylcarbamoyl), sulfamoyl group (C1-C36 sulfamoyl group, for example, dimethylsulfyl group). Famoyl, dibutylsulfamoyl), a dialkylphosphono group such as those mentioned for R _{1 or} a diarylphosphono group (a diarylphosphono group having 12 to 50 carbon atoms, such as diphenylphosphono or di (p-toluyl)). Phosphono). The substituent of R ₂ is particularly preferably an aliphatic oxycarbonyl group represented by the following general formula.

[0020]

[Chemical 6]

[0021] In the formula, R ₁ ', R _2' represents an aliphatic group, for example a carbon number of 1 to 36, straight chain or branched chain alkyl group, an aralkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, A cycloalkenyl group is, for example, methyl, ethyl, propyl, isopropyl, t-butyl, t-amyl, t-octyl, tridecyl, cyclopentyl or cyclohexyl. R ₃ ′, R ₄ ′,
R ₅ 'represents a hydrogen atom or an aliphatic group. Examples of the aliphatic group include the groups mentioned above for R ₁ ′ and R ₂ ′. R ₃ ′, R ₄ ′ and R ₅ ′ are preferably hydrogen atoms.

Z is necessary for forming a 5- to 8-membered ring,
It represents a group of non-metal atoms, and this ring may be substituted, may be a saturated ring, or may have an unsaturated bond. The non-metal atom is preferably a nitrogen atom, an oxygen atom, a sulfur atom or a carbon atom, and more preferably
It is a carbon atom.

Examples of the ring formed by Z include a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a cyclohexene ring, a piperazine ring, an oxane ring and a thian ring, and these rings will be described later. It may be substituted with a substituent represented by R ₃ . The ring formed by Z is preferably a cyclohexane ring which may be substituted, and particularly preferably, the 4-position is an alkyl group having 1 to 24 carbon atoms (which is substituted with a substituent represented by R ₃ described later). May also be substituted) with a cyclohexane ring.

R ₃ represents a substituent, for example, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom), an aliphatic group (for example, a linear or branched alkyl group having 1 to 36 carbon atoms, an aralkyl group, an alkenyl). Group, alkynyl group, cycloalkyl group, cycloalkenyl group, specifically, for example, methyl, ethyl, propyl, isopropyl, t-butyl, tridecyl, t-amyl, t-octyl, 2-methanesulfonylethyl, 3- (3- Pentadecylphenoxy) propyl, 3- {4- {2- [4- (4-hydroxyphenylsulfonyl) phenoxy] dodecanamide}
Phenyl} propyl, 2-ethoxytridecyl, trifluoromethyl, cyclopentyl, 3- (2,4-di-t
-Amylphenoxypropyl), an aryl group (having 6 carbon atoms)
To 36 aryl groups such as phenyl and 4-t-
Butylphenyl, 2,4-di-t-amylphenyl, 4
-Tetradecanamidophenyl, 2-methoxyphenyl), heterocyclic group (heterocyclic group having 1 to 36 carbon atoms, for example, 2-furyl, 2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl), cyano group, hydroxy group , A nitro group, a carboxy group, an amino group, an alkoxy group (a linear, branched or cyclic alkoxy group having 1 to 36 carbon atoms, such as methoxy, ethoxy, butoxy, 2
-Methoxyethoxy, 2-dodecyloxyethoxy, 2
-Methanesulfonylethoxy), an aryloxy group (an aryloxy group having 6 to 36 carbon atoms, for example, phenoxy, 2-methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, 3-t-butyloxycarbamoyl). Phenoxy, 3-methoxycarbamoyl),
Acylamino group (acylamino group having 2 to 36 carbon atoms, such as acetamide, benzamide, tetradecanamide, 2- (2,4-di-t-amylphenoxy) butanamide, 4- (3-t-butyl-4-hydroxy) Phenoxy) butanamide, 2- {4- (4-hydroxyphenylsulfonyl) phenoxy} decanamide), an alkylamino group (an alkylamino group having 1 to 36 carbon atoms, such as methylamino, butylamino, dodecylamino, diethylamino, methyl Butylamino), anilino groups (anilino groups having 6 to 36 carbon atoms, such as phenylamino, 2-chloroanilino, 2-chloro-5-tetradecaneaminoanilino, 2-chloro-5-dodecyloxycarbonylanilino, N -Acetylanilino, 2
-Chloro-5- {2- (3-t-butyl-4-hydroxyphenoxy) dodecanamide} anilino), a ureido group (a ureido group having 2 to 36 carbon atoms, for example, phenylureido, methylureido, N, N). -Dibutylureido), a sulfamoylamino group (a sulfamoylamino group having 1 to 36 carbon atoms, for example, N, N-dipropylsulfamoylamino, N-methyl-N-decylsulfamoylamino), alkylthio A group (an alkylthio group having 1 to 36 carbon atoms, for example, methylthio, octylthio, tetradecylthio, 2-phenoxyethylthio, 3
-Phenoxypropylthio, 3- (4-t-butylphenoxy) propylthio), an arylthio group (having 6 to 6 carbon atoms)
36 arylthio groups such as phenylthio, 2
-Butoxy-5-t-octylphenylthio, 3-pentadecylphenylthio, 2-carboxyphenylthio,
4-tetradecanamidophenylthio), an alkoxycarbonylamino group (an alkoxycarbonylamino group having 2 to 36 carbon atoms, such as methoxycarbonylamino, tetradecyloxycarbonylamino), a sulfonamide group (an alkyl group having 1 to 36 carbon atoms and An aryl sulfonamide group, for example, methane sulfonamide, butane sulfonamide, octane sulfonamide, hexadecane sulfonamide, benzene sulfonamide, p-
Toluenesulfonamide, octadecanesulfonamide, 2-methoxy-5-t-butylbenzenesulfonamide), carbamoyl group (carbamoyl group having 1 to 36 carbon atoms, such as N-ethylcarbamoyl, N, N-
Dibutylcarbamoyl, N- (2-dodecyloxyethyl) carbamoyl, N-ethyl-N-dodecylcarbamoyl, N- {3- (2,4-di-t-amylphenoxy) propyl} carbamoyl), sulfamoyl group (carbon number) 1-36 sulfamoyl groups, for example, N-
Ethylsulfamoyl, N, N-dipropylsulfamoyl, N- (2-dodecyloxyethyl) sulfamoyl, N-ethyl-N-dodecylsulfamoyl, N, N
-Diethylsulfamoyl), a sulfonyl group (having 1 carbon atom)
To 36 alkyl and arylsulfonyl groups, for example, methanesulfonyl, octanesulfonyl, benzenesulfonyl, toluenesulfonyl), alkoxycarbonyl groups (alkoxycarbonyl groups having 2 to 36 carbon atoms, such as methoxycarbonyl, butyloxycarbonyl, dodecyl). Oxycarbonyl, octadecyloxycarbonyl), a heterocyclic oxy group (a heterocyclic oxy group having 1 to 36 carbon atoms, for example, 1-phenyltetrazole-5-oxy, 2-tetrahydropyranyloxy), an azo group (for example, phenylazo). , 4-methoxyphenylazo, 4-pivaloylaminophenylazo, 2-hydroxy-4-propanoylphenylazo), acyloxy group (acyloxy group having 2 to 36 carbon atoms, for example, acetoxy), carba An yloxy group (a carbamoyloxy group having 1 to 36 carbon atoms, for example, N-methylcarbamoyloxy, N-phenylcarbamoyloxy), a silyloxy group (a silyloxy group having 3 to 36 carbon atoms, for example, trimethylsilyloxy, dibutylmethylsilyl Oxy), an aryloxycarbonylamino group (an aryloxycarbonylamino group having 7 to 36 carbon atoms, for example, phenoxycarbonylamino), an imide group (an imide group having 4 to 36 carbon atoms, for example, N-succinimide, N- Phthalimide, 3-octadecenylsuccinimide), heterocyclic thio group (heterocyclic thio group having 1 to 36 carbon atoms, for example, 2-benzothiazolylthio, 2,4
-Di-phenoxy-1,3,5-triazole-6-thio, 2-pyridylthio), sulfinyl group (having 1 to 1 carbon atoms)
36 sulfinyl groups such as dodecanesulfinyl, 3-pentadecylphenylsulfinyl, 3-phenoxypropylsulfinyl), phosphonyl groups (alkyl and arylphosphonyl groups having 1 to 36 carbon atoms, such as phenoxyphosphonyl, octyloxy). Phosphonyl, phenylphosphonyl), an aryloxycarbonyl group (an aryloxycarbonyl group having 7 to 36 carbon atoms such as phenoxycarbonyl), an acyl group (an acyl group having 2 to 36 carbon atoms such as acetyl, 3- Phenylpropanoyl, benzoyl, 4-dodecyloxybenzoyl), and an azolyl group (eg, imidazolyl, pyrazolyl, 3-chloro-pyrazol-1-yl, triazolyl). The group capable of further having a substituent among these substituents may further have a substituent as described here.

R ₃ is preferably an aliphatic group or an aryl group, and more preferably a branched chain alkyl group or a cycloalkyl group.

R ₄ represents an alkyl group, an alkoxy group or an aryloxy group. The alkyl group represented by R ₄ represents a straight chain, branched chain or cyclic alkyl group having 1 to 36 carbon atoms, and may further have a substituent as described for R ₃ . For example, methyl, ethyl, propyl, isopropyl, 1-ethyl-pentyl, t-butyl, t-amyl, cyclopentyl, cyclohexyl, 1,1-bis (chloromethyl) ethyl, tris (chloromethyl) methyl, 1,1-bis. (Methoxymethyl) ethyl and the like can be mentioned.

The alkoxy group represented by R ₄ has 1 carbon atom.
To 36 linear, branched or cyclic alkoxy groups, each of which may further have a substituent as described for R ₃ . For example, methoxy, ethoxy, isopropoxy, sec
-Butoxy, 1,1,1-trichloroethoxy, chloromethoxy, benzyloxy, octyloxy, t-butoxy, 2-ethylhexyloxy, hexadecyloxy, 2,6-di-t-butyl-4-methylcyclohexyloxy, etc. Can be given.

The aryloxy group represented by R ₄ represents an aryloxy group having 6 to 36 carbon atoms and may further have a substituent as described for R ₃ . Examples thereof include phenoxy, 2-methylphenoxy, 4-methylphenoxy, 3-methylphenoxy, 2,4,6-trimethylphenoxy, 2-methoxyphenoxy and 2,4-dimethoxyphenoxy.

R ₅ represents an alkyl group or an aryl group. The alkyl group represented by R ₅ represents a linear, branched or cyclic alkyl group having 1 to 36 carbon atoms, and may further have the substituent as described for R ₃ . Examples thereof include methyl, ethyl, propyl, isopropyl, butyl, octyl, hexadecyl, trifluoromethyl, trichloromethyl, 2-chloroethyl, 2,2,2-trifluoroethyl, 3-chloroethyl and the like.

The aryl group represented by R ₅ has 6 to 6 carbon atoms.
It represents an aryl group of 36, and may further have a substituent as described for R ₃ . For example, phenyl, 2,
4,6-trimethylphenyl, 2,4,6-triisopropylphenyl, 2-methoxycarbonylphenyl, 2
-Chlorophenyl, pentafluorophenyl, 4-methoxyphenyl, 2-nitrophenyl and the like can be mentioned.

R ₆ and R ₇ each represent an alkyl group, an aryl group, an alkoxy group or an aryloxy group. The alkyl group represented by R ₆ and R ₇ has 1 carbon atom.
To 36 linear, branched, or cyclic alkyl groups, each of which may further have a substituent as described for R ₃ . For example, methyl, ethyl, propyl, isopropyl,
Examples include cyclohexyl.

The aryl group represented by R ₆ and R ₇ represents an aryl group having 6 to 36 carbon atoms and may further have a substituent such as those mentioned for R ₃ . Examples thereof include phenyl and 2-methylphenyl.

The alkoxy group represented by R ₆ and R ₇ represents a linear, branched or cyclic alkoxy group having 1 to 36 carbon atoms and may further have a substituent as mentioned for R _3. . For example, methoxy, ethoxy, octyloxy, 2-ethylhexyloxy, cyclohexyloxy, 2,6-di-t-butyl-4-methylcyclohexyloxy and the like can be mentioned.

The aryloxy group represented by R ₆ and R ₇ represents an aryloxy group having 6 to 36 carbon atoms and may further have a substituent as mentioned for R ₃ . For example, phenoxy, 2-methylphenoxy, 3-methylphenoxy, 4-methylphenoxy and the like can be mentioned.

X represents an oxygen atom or a sulfur atom, preferably an oxygen atom. In the present invention, the general formula (I)
Particularly preferred embodiments of the coupler represented by are represented by the following general formulas (V-1), (V-2) and (V-3). Among them, the general formulas (V-1) and (V-2) are preferable, and the general formula (V-1) is the most preferable.

[0036]

[Chemical 7]

In the formula, R _{4 to} R ₇ , R ₁ ′ to R ₅ ′, and Z have the same meanings as described above, and R ₃ ″ represents an aliphatic group or an aryl group.

Preferably R ₃ ″ represents a branched chain alkyl group or a cycloalkyl group. R ₃ ′, R ₄ ′ and R ₅ ′.
Each represent a hydrogen atom, and the ring represented by Z represents a cyclohexane ring.

The coupler represented by the general formula (I) has R ₂
Or the group of R ₃ contains a coupler residue represented by the general formula (I) to form a dimer or higher multimer,
The group of R ₂ or R ₃ may contain a polymer chain to form a homopolymer or a copolymer. The homopolymer or copolymer containing a polymer chain is a typical example of an addition polymer having a coupler residue represented by the general formula (I), a homopolymer or copolymer of an ethylenically unsaturated compound. . In this case, one or more kinds of cyan color-forming repeating units having a coupler residue represented by the general formula (I) may be contained in the polymer, and as a copolymerization component, acrylic acid ester, methacrylic acid ester, maleic acid are used. It may be a copolymer containing one or more non-color-forming, ethylene-type monomers that do not couple with the oxidation products of aromatic primary amine developers such as esters. Specific examples of the coupler of the present invention are shown below, but the present invention is not limited thereto.

[0040]

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[0041]

[Chemical 9]

[0042]

[Chemical 10]

[0043]

[Chemical 11]

[0044]

[Chemical 12]

[0045]

[Chemical 13]

[0046]

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[0047]

[Chemical 15]

[0048]

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[0049]

[Chemical 17]

[0050]

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[0051]

[Chemical 19]

The compound represented by the general formula (I) of the present invention can be prepared by a known method, for example, Angew. Chem., Vol. 72, No. 95.
6 (1960), Berichte, 97, 3436 (1964).
, Etc. and the literature cited therein or a similar method, and a triazole compound such as the below-mentioned compound a can be used as a starting material. Synthesis Example 1 Synthesis of Exemplified Compound (1) Exemplified Compound (1) was synthesized by the following route.

[0053]

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Synthesis of Compound b 200 ml of 2,6-di-t-butyl-4-methylcyclohexanol (17 g, 75 mmol) in acetonitrile
Add trifluoroacetic anhydride (10.6 ml,
75 mmol) was added dropwise, and then compound a (11 g,
60.4 mmol) was added slowly. After the reaction solution was stirred at room temperature for 2 hours, 300 ml of water was added, and the mixture was extracted with 300 ml of ethyl acetate. The organic phase was washed with aqueous sodium bicarbonate, water and brine. After drying over sodium sulfate, the solvent was distilled off under reduced pressure to obtain a crude compound e (14 g). Crude compound b (14
g) was used in the next step without purification.

Synthesis of Compound c To a solution of crude compound b (14 g) in 200 ml of tetrahydrofuran was added pyridinium bromide perbromide (1
(2.7 g, 40 mmol) and stirred for 8 hours. After adding 200 ml of 2 g aqueous solution of sodium sulfite to the reaction solution,
Extracted with 300 ml of ethyl acetate. The organic phase was washed with water and brine, and dried over sodium sulfate. The solvent was distilled off under reduced pressure to obtain a crude compound c (15 g). Crude compound c (15
g) was used in the next step without purification.

Synthesis of Compound d To a solution of methyl cyanoacetate (9.5 g, 96 mmol) in 50 ml of tetrahydrofuran was slowly added sodium hydride (3.2 g, 80 mmol) at 0 ° C., and the mixture was stirred at room temperature for 30 minutes. (Solution s). The solution s was added dropwise to a solution of the crude compound c (15 g) in 100 ml of tetrahydrofuran at 0 ° C., and the mixture was stirred at room temperature for 1 hour. 1N hydrochloric acid 20 in the reaction solution
0 ml and 200 ml of ethyl acetate were added for extraction. The organic phase was washed with water and brine, dried over sodium sulfate, and the solvent was distilled off under reduced pressure. The compound d12.1 was obtained by purifying the obtained residue by column chromatography.
g was obtained.

Synthesis of Compound e To a solution of the compound d (12.1 g, 16.5 mmol) in 100 ml of methanol was added 50 g of an aqueous solution of 5 g of sodium hydroxide, and the mixture was stirred at 50 ° C. for 2 hours. 1N hydrochloric acid 2 in the reaction solution
00 ml and 200 ml of ethyl acetate were added for extraction. The organic phase was washed with water and brine, dried over sodium sulfate, and then the solvent was distilled off under reduced pressure to obtain 11.2 g of compound e.
I got

Synthesis of Compound (1) A solution of compound e (5.0 g, 10.5 mmol) in pyridine (50 ml) was added with diethyl chlorophosphate (4.
5 g, 26.3 mmol) was added dropwise. After stirring at room temperature for 2 hours, pour into 200 ml of dilute hydrochloric acid and add ethyl acetate 1
Extracted with 50 ml. The organic layer was washed with water (3 times), dried over sodium sulfate, and then concentrated under reduced pressure. The residue was purified by column chromatography to obtain 4.0 g of the desired exemplary compound (1). Melting point 195-197 ° C

Synthesis Example 2 Synthesis of Exemplified Compound (13) Compound (f) synthesized in the same manner as in Synthesis Example 1 was synthesized by the following route.

[0060]

[Chemical 21]

Methanesulfonyl chloride (0.92 g, 8 mmol) was added dropwise at 0 ° C. to a solution of the compound (f) (2.0 g, 3.2 mmol) in pyridine (30 ml). After stirring at 0 ° C for 2 hours, the mixture was poured into 150 ml of diluted hydrochloric acid water and extracted with 100 ml of ethyl acetate. The organic layer was washed with water (3 times) and then dried over sodium sulfate. After concentration under reduced pressure, purification by column chromatography yielded 1.2 g of the desired Exemplified Compound (13). Melting point 147-148 ° C

Synthesis Example 3 Synthesis of Exemplified Compound (19) By the same method as Synthesis Example 2, except that diethylphosphoryl chloride (1.38 g, 8 mmol) was used in place of methanesulfonyl chloride, the desired Exemplified Compound (1
9 g of 9) was obtained. Melting point 167-169 ° C

[0063]

[Chemical formula 22]

Synthesis Example 4 Synthesis of Exemplified Compound (37) Compound (g) synthesized in the same manner as in Synthesis Example 1 was synthesized by the following route.

[0065]

[Chemical formula 23]

Isobutyl chlorocarbonate (3.7 ml, 28 mmol) was added to a solution of the compound (g) (11.8 g, 12.8 mmol) in 100 ml of ethyl acetate at 0 ° C., followed by triethylamine (4.0 ml). , 28 mmol) was added dropwise. After stirring at 0 ° C for 30 minutes, dilute hydrochloric acid water 100
ml was added. The organic layer was washed with water (3 times) and then dried over sodium sulfate. After concentrating under reduced pressure, purification by column chromatography yielded 9.5 g of the desired exemplary compound (37). Melting point 110-112 ° C

Synthesis Example 5 Synthesis of Exemplified Compound (7) Compound (h) synthesized in the same manner as in Synthesis Example 1 was synthesized by the following route.

[0068]

[Chemical formula 24]

Pivaloyl chloride (4.39 g, 36.4 mmol) was added dropwise to a solution of the compound (h) (7.5 g, 12.1 mmol) in pyridine (75 ml) at 0 ° C.
After stirring at 0 ° C for 2 hours, the mixture was poured into 500 ml of diluted hydrochloric acid water and extracted with 300 ml of ethyl acetate. Wash the organic layer with water (3 times)
After that, it was dried over sodium sulfate. After concentration under reduced pressure and purification by column chromatography, 4.5 g of the desired exemplary compound (7) was obtained. Melting point 25
2-254 ° C. Other compounds can be similarly synthesized.

The light-sensitive material of the present invention may have at least one layer containing the coupler of the present invention on a support,
The layer containing the coupler of the present invention may be a hydrophilic colloid layer on a support. A general light-sensitive material can be constructed by coating at least one blue-sensitive silver halide emulsion layer, at least one green-sensitive silver halide emulsion layer and at least one red-sensitive silver halide emulsion layer on a support in this order. However, the order may be different from this. An infrared-sensitive silver halide emulsion layer can also be used in place of at least one of the above-mentioned photosensitive emulsion layers. Color reproduction of the subtractive method is performed by incorporating a silver halide emulsion having sensitivity in each wavelength range and a color coupler forming a dye having a complementary color relationship with the light to be exposed in these light-sensitive emulsion layers. be able to. However, the photosensitive emulsion layer and the coloring hue of the color coupler may not have the above correspondence. In the present invention, it is particularly preferably used as a cyan coupler in the red-sensitive silver halide emulsion layer. The content of the coupler of the present invention in the light-sensitive material is appropriately 1 × 10 ⁻³ mol to 1 mol, preferably 2 × 10 ⁻³ mol to 3 × 10 1 mol per mol of silver halide in the same layer. ^-1 mole.

The coupler of the present invention can be introduced into a light-sensitive material by various known dispersion methods, is dissolved in a high-boiling point organic solvent (a low-boiling point organic solvent is optionally used in combination), and is emulsified and dispersed in a gelatin aqueous solution to be halogenated. The oil-in-water dispersion method of adding to a silver emulsion is preferred. Examples of the high boiling point solvent used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027. Further, steps of latex dispersion method as one of polymer dispersion methods, effects, and specific examples of latex for impregnation are described in US Pat. No. 4,199,363 and West German Patent Application (OLS) 2,541,274. , The same 2,541,23
No. 0, Japanese Patent Publication No. 53-41091 and European Patent Publication No. 0.
29104 and the like, and regarding the dispersion by an organic solvent-soluble polymer, PCT International Publication No. WO88.
/ 00723.

As the high boiling point organic solvent which can be used in the above oil-in-water dispersion method, phthalic acid esters (eg, dibutyl phthalate, dioctyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis ( 2,4-di-tert
-Amylphenyl) isophthalate, bis (1,1-di-ethylpropyl) phthalate), esters of phosphoric acid or phosphonic acid (eg diphenyl phosphate, triphenyl phosphate, tricresyl phosphate,
2-ethylhexyl diphenyl phosphate, dioctyl butyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, di-2-ethylhexyl phenyl phosphate), benzoic acid esters (for example, 2-ethylhexyl benzoate, 2,4-) Dichlorobenzoate, dodecylbenzoate, 2-ethylhexyl-p-
Hydroxybenzoate), amides (eg, N, N
-Diethyldodecane amide, N, N-diethyllaurylamide), alcohols or phenols (isostearyl alcohol, 2,4-di-tert-amylphenol, etc.), aliphatic esters (e.g., dibutoxyethyl succinate, Di-2-ethylhexyl succinate, 2-hexyldecyl tetradecanoate, tributyl citrate, diethyl azelate, isostearyl lactate, trioctyl citrate), aniline derivative (N, N-dibutyl-2-butoxy-5-tert-) Octylaniline etc.),
Chlorinated paraffins (paraffins having a chlorine content of 10% to 80%), trimesic acid esters (eg, tributyl trimesate), dodecylbenzene, diisopropylnaphthalene, phenols (eg, 2,4-di-te).
rt-amylphenol, 4-dodecyloxyphenol, 4-dodecyloxycarbonylphenol, 4-
(4-dodecyloxyphenylsulfonyl) phenol), carboxylic acids (for example, 2- (2,4-di-tert)
-Amylphenoxybutyric acid, 2-ethoxyoctanedecanoic acid), alkylphosphoric acids (for example, di-2 (ethylhexyl) phosphoric acid, diphenylphosphoric acid) and the like.
Further, as an auxiliary solvent, an organic solvent having a boiling point of 30 ° C. or higher and about 160 ° C. or lower (eg, ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone,
2-ethoxyethyl acetate, dimethylformamide) may be used in combination.

The high boiling point organic solvent can be used in an amount of 0 to 10.0 times, preferably 0 to 5.0 times, and more preferably 0.5 to 4.5 times the weight ratio of the coupler.

The silver halide emulsion and other materials (additives, etc.) and photographic constituent layers (layer arrangement, etc.) applied in the present invention, and the processing method and processing addition applied for processing this light-sensitive material. European Patent EP
0,355,660 A2, JP-A-5-34889,
No. 4-359249, No. 4-313753, No. 4-
No. 270344, No. 5-66527, No. 4-3454.
No. 8, No. 4-145433, No. 2-854, No. 1-
158431, 2-90145, 3-1945.
No. 39, No. 2-93641, No. 6-43611, No. 6-3779, No. 6-208196, No. 6-118.
The silver halide color photographic light-sensitive material and its processing method described in, for example, 546 and European Patent EP 0520457A2 are also preferable.

The silver halide used in the present invention may have any halogen composition such as silver chloride, silver bromide, silver chlorobromide, silver iodochlorobromide and silver iodobromide. For the purpose of rapid processing, the content of silver chloride substantially free of silver iodide is 90 mol% or more and 100 mol% or less, more preferably 95 mol% or more and 100 mol% or less, and particularly 98 mol% or more and 100 mol% or less. The use of silver chlorobromide or pure silver chloride emulsions is preferred.

[0076]

EXAMPLES The present invention will be specifically described below with reference to examples, but of course the present invention is not limited thereto. Example 1 Using an undercoated polyethylene terephthalate support, a single-layer photosensitive material 101 for evaluation of the following layer constitution was prepared. (Preparation of coating solution for emulsion layer) 1.85 mmol of coupler, 10 ml of ethyl acetate, dibutyl phthalate (solvent), and trioctyl phosphate (solvent) were added to the coupler at 5 parts each.
0% by weight was added and dissolved. This solution was emulsified and dispersed in 33 g of a 14% aqueous gelatin solution containing 3 ml of 10% sodium dodecylbenzenesulfonate. On the other hand, a silver chlorobromide emulsion (cubic, 3: 7 mixture of a large size emulsion having an average grain size of 0.88 μm and a small size emulsion having a grain size of 0.70 μm (silver molar ratio). The variation coefficient of grain size distribution is 0. 08
And 0.10. In each size emulsion, 0.3 mol% of silver bromide was locally contained on a part of the grain surface). Chemical ripening of this emulsion was performed by adding a sulfur sensitizer and a gold sensitizer. The emulsified dispersion and this emulsion were mixed and dissolved to prepare an emulsion layer coating solution having the following composition. In addition, sodium 1-oxy-3,5-dichloro-s-triazinate was used as a hardening agent. (Layer constitution) The layer constitution of the sample used in this experiment is shown below. (The numbers indicate the coating amount per m ^2. )

[Support] Polyethylene terephthalate support [Emulsion layer] Silver chlorobromide emulsion (previously described) 3.0 mmol Coupler (coupler described in Table A) 1.0 mmol Tricresyl phosphate (50 parts by weight relative to coupler) %) Trioctyl phosphate (50% by weight with respect to the coupler) Gelatin 5.5 g [Protective layer] Gelatin 2.5 g Polyvinyl alcohol acrylic modified copolymer (17% conversion) 0.15 g Liquid paraffin 0.03 g

The structures of the comparative coupler used in this example and the coupler of the present invention are shown below.

[0079]

[Chemical 25]

Sample 101 was prepared in the same manner as sample 101 except that the cyan coupler was replaced with the coupler shown in Table A in a 1/2 molar amount and the silver halide amount was changed to 1/2. Samples 102 to 1 in exactly the same manner
12 was produced. After gradation exposure was applied to the above sample using an optical wedge, the sample was processed using the following processing steps and processing solutions.

(Processing step) Processing step Temperature Time Color development 35 ° C. 40 seconds Bleaching fixing 35 ° C. 60 seconds Water washing 35 ° C. 120 seconds

(Composition of processing liquid) [Color developer] Distilled water 800 ml Triethanolamine 8.1 g Diethylhydroxylamine 4.2 g Potassium bromide 0.05 g Sodium chloride 0.5 g Sodium hydrogen carbonate 3.9 g Sodium sulfite 0.13 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 5.0 g potassium carbonate 18.7 g Water was added to 1000 ml pH 10.15

Bleach-fixing solution Distilled water 400 ml Ammonium thiosulfate (700 g / l) 150 ml Sodium sulfate 18.0 g Ethylenediaminetetraacetic acid iron (III) ammonium 55.0 g Sodium ethylenediaminetetraacetate 5.0 g Water was added to 1000 ml pH 6. 70

The optical density of red light of the processed sample was measured,
The maximum color density Dmax was determined. Also, the cyan density is 1.0
X-Rite 310 densitometer (X
-Made by Rite Company). The lower the yellow density, the less the secondary absorption and the better the hue. Next, these samples were subjected to light irradiation for 5 days under a 200,000 lux Xe light source (5 hours light / 1 hour dark intermittent irradiation) through a sharp cut filter capable of cutting about 50% at 390 nm. The optical density of red light of the sample after the light irradiation was measured again to obtain the residual ratio of the color image after the light irradiation. The color image residual ratio was evaluated at two points, the Dmax part and the low density part showing a color density of ⅕ of Dmax, and shown in Table A as a percentage when the initial density was 100%.

[0085]

[Table 1]

As is clear from Table A, Samples 102 to 112 are superior in hue to Sample 101. However, Samples 102 to 104 are markedly inferior to Comparative Sample 101 in light fastness in the low density part.
On the other hand, Samples 105 to 105 using the coupler of the present invention in which only the leaving group is changed from the couplers of Samples 102 to 104
It goes without saying that 107 has an excellent hue, but the light fastness in the low density portion is improved, and it is almost the same as the residual ratio in the high density portion. Samples 108-1
Similar results were obtained for No. 12, and it can be said that the coupler of the present invention is clearly superior in terms of hue and light fastness.

Next, the samples 101 to 112 were exposed and processed in the same manner as described above, and then stored at 100 ° C. for 10 days,
The color image residual rate at the maximum color density was evaluated. The results are shown in Table B.

[0088]

[Table 2]

From Table B, it is obvious that Samples 105 to 107 using the coupler of the present invention are superior in heat fastness to Sample 101 using the comparative coupler Ex-1, but the corresponding chlorine atom-eliminating couplers. Sample 10 using
It can be seen that the robustness is further improved for 2 to 104. Sample 108 using the coupler of the present invention
Similarly, 112 also shows excellent thermal fastness.

Example 2 A surface of a paper support laminated on both sides with polyethylene was subjected to a corona discharge treatment, and thereafter provided with a gelatin subbing layer containing sodium dodecylbenzenesulfonate, and various photographic constituent layers were further coated thereon. A multilayer color photographic printing paper (201) having the layer structure shown in was prepared. The coating liquid was prepared as follows.

Preparation of coating solution for fifth layer Cyan coupler (ExC) 310 g, color image stabilizer (Cp
d-1) 100 g, color image stabilizer (Cpd-5) 100
g, color image stabilizer (Cpd-6) 10 g, color image stabilizer (C
pd-8) 10 g, color image stabilizer (Cpd-9) 100
g, color image stabilizer (Cpd-10) 100 g, ultraviolet absorber (UV-2) 100 g, solvent (Solv-2) 250
g, solvent (Solv-4) 250 g and ethyl acetate 36
Dissolve in 0 ml, and add this solution to 60 ml of 10% sodium dodecylbenzenesulfonate and 10 g of citric acid.
% Gelatin aqueous solution 2000 g to emulsify and disperse to prepare Emulsified Dispersion C. On the other hand, silver chlorobromide emulsion C (cube, large-sized emulsion C having an average grain size of 0.50 μm and 0.41 μm
1: 4 mixture with m small size emulsion C (silver molar ratio). Coefficients of variation of particle size distribution are 0.09 and 0.1 respectively
One. In each size emulsion, 0.8 mol% of silver bromide was locally contained in a part of the grain surface, and the rest was composed of silver halide grains in which silver chloride was contained. In this emulsion, red-sensitive sensitizing dyes G and H shown below were 1.0 × 10 ⁻⁴ and 5.0 × 10 ⁴ , respectively, for large-sized emulsion C per mol of silver.
^-5 mol, and for small size emulsion C, 1.
2 × 10 ⁻⁴ and 6.0 × 10 ⁻⁵ mol are added. The chemical ripening of this emulsion was optimally performed by adding sulfur sensitization and gold sensitization. The emulsified dispersion C and the silver chlorobromide emulsion C were mixed and dissolved to prepare a fifth layer coating solution having the following composition.

Coating solutions for the first to seventh layers other than the fifth layer were prepared in the same manner as the fifth layer coating solution. 1-oxy-3,5-dichloro-s-as a gelatin hardening agent for each layer
Triazine sodium salt was used. Also, each layer has Cpd
-14 and Cpd-15 in a total amount of 25.0 mg / m ^2.
And 50.0 mg / m ² were added.

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

[0094]

[Table 3]

[0095]

[Table 4]

[0096]

[Table 5]

For the blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer, 1- (5-methylureidophenyl)
-5-Mercaptotetrazole was added in an amount of 8.5 x 10 ^-5 mol, 7.7 x 10 ^-4 mol and 2.5 x 10 ^-4 mol per mol of silver halide, respectively. Further, 4-hydroxy-6-methyl- was added to the blue-sensitive emulsion layer and the green-sensitive emulsion layer.
1,3,3a, 7-Tetrazaindene was added in an amount of 1 × 10 ⁻⁴ mol and 2 × 10 ⁻⁴ mol per mol of silver halide, respectively. Further, the following dyes (the amount in parentheses represents the coating amount) were added to the emulsion layer to prevent irradiation.

[0098]

[Chemical formula 26]

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

[0100]

[Table 6]

[0101]

[Table 7]

[0102]

[Table 8]

[0103]

[Table 9]

[0104]

[Chemical 27]

[0105]

[Chemical 28]

[0106]

[Chemical 29]

[0107]

Embedded image

[0108]

[Chemical 31]

[0109]

Embedded image

[0110]

[Chemical 33]

The same procedure as in Sample 201 except that the cyan coupler shown in Table C was replaced with 1/2 mol amount of the above Sample 201 and the coating amount of the silver halide emulsion was reduced to 1/2. Samples 202 to 210 were produced. First, the sample 201 was processed into a roll having a width of 127 mm, and about 35% of the coated silver amount was developed by using a sensitometer (FWH type manufactured by Fuji Photo Film Co., Ltd., color temperature of the light source was 3200 ° K), and gray was developed. It was exposed to give.

The above light-sensitive material was subjected to continuous processing (running test) of 200 m ^{2 in the following} processing steps using a printer processor PP1820V manufactured by Fuji Photo Film Co., Ltd. Treatment process Temperature Time Replenishment amount * Color development 38.5 ° C 45 seconds 73 ml Bleach-fix 35 ° C 45 seconds 60 ml ** Rinse (1) 35 ° C 30 seconds-Tance (2) 35 ° C 30 seconds-Rinse (3) 35 ° C 30 Second 360 ml Dry 80 ° C. 60 sec * Replenishment amount per 1 m ^{2 of} light-sensitive material ** In addition to the above 60 ml, 120 ml per 1 m ^{2 of} light-sensitive material was poured from the rinse (1). (Rinse was a three-tank counter-current system from (3) to (1))

The composition of each processing liquid is as follows. [Color developer] [Tank liquid] [Replenisher] Water 800 ml 800 ml Ethylenediaminetetraacetic acid 3.0 g 3.0 g 4,5-Dihydroxybenzene-1,3-disulfonic acid disodium salt 0.5 g 0.5 g Triethanolamine 12.0 g 12.0g Potassium chloride 6.5g-Potassium bromide 0.03g-Potassium carbonate 27.0g 27.0g Optical brightener (WHITEX 4 manufactured by Sumitomo Chemical Co., Ltd.) 1.0g 3.0 Sodium sulfite 0.1g 0.1g Disodium-N, N-bis (sulfo Natoethyl) hydroxylamine 5.0 g 10.0 g Triisopropylnaphthalene (β) sodium sulfonate 0.1 g 0.1 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline.3 / 2 Sulfuric acid monohydrate 5.0 g 11.5 g Add water 1000 ml 1000 ml pH (25 ° C / potassium hydroxide And adjusted with sulfuric acid) 10.00 11.00

[Bleach-fixing solution] [Tank solution] [Replenishing solution] Water 600 ml 150 ml Ammonium thiosulfate (750 g / liter) 93 ml 230 ml Ammonium sulfite 40 g 100 g Ethylenediaminetetraacetic acid iron (III) ammonium 55 g 135 g Ethylenediaminetetraacetic acid 5 g 12.5g Nitric acid (67%) 30g 65g Add water 1000ml 1000ml pH (25 ° C / adjusted with acetic acid and ammonia water) 5.8 5.6

[Rinse solution] (same as tank solution and replenisher solution) Sodium chlorinated isocyanurate 0.02 g Deionized water (conductivity 5 μs / cm or less) 1000 ml pH 6.5

Next, the samples 201 to 210 were subjected to gradation exposure with red light using an optical wedge, and the developing treatment was performed. For each sample, under 100,000 lux Xe light source (5 hours light / 1 hour dark intermittent irradiation) for 14 days and 100 ° C. 1
The color image fastness was evaluated under the condition of 4 days. The light fastness was evaluated at two points of initial density of 2.0 and 0.5, and the heat fastness was evaluated at initial density of 2.0. The results are shown in Table C. For the heat fastness, the change in the amount of coloration in the white background was measured at a blue optical density and is shown in Table C together with ΔDmin.

[0117]

[Table 10]

From Table C, Samples 205 to 210 using the coupler of the present invention have a particularly high heat fastness with respect to Sample 201, and have a light fastness especially at a low density portion with respect to Sample 202. Further, it can be seen that the samples 203 and 204 are superior in light fastness and thermal stain, and are clearly superior in total performance.

Next, in order to examine the change in the photographic performance of Samples 201 to 210 due to the processing variation, the bleach-fix solution was added to the color developer at a ratio of 0.5 cc of the bleach-fix solution to 1 liter of the color developer. The photographic performance in this case was compared with that without the bleach-fix solution. The evaluation is shown by the change in red light density at a density of 2.0.

[0120]

[Table 11]

From Table D, it can be seen that Samples 205 to 210 using the coupler of the present invention are excellent photographic materials with a small change in color density when a bleach-fixing solution is mixed in the color developing solution. Such mixing of the processing liquid is often found in the market in today's processing form, and the photosensitive material of the present invention can exhibit stable performance in such market.

As described above, by using the coupler of the present invention,
It is possible to provide an excellent photographic light-sensitive material having excellent hue, light fastness, heat fastness, and small processing fluctuation.

Example 3 Samples 301 to 310 were prepared in exactly the same manner as Samples 201 to 210 except that the composition of the first layer of Samples 201 to 210 in Example 2 was changed as follows.

[0124]

[Table 12]

[0125]

Embedded image

The above samples were evaluated in exactly the same manner as in Example 2. As a result, the light-sensitive material using the coupler of the present invention had the same hue, light fastness and heat fastness as those in Example 2. , And it became clear that it was excellent in processing dependence.

Example 4 Samples 401 to 410 were prepared in exactly the same manner as Samples 201 to 210 except that the composition of the first layer of Samples 201 to 210 of Example 2 was changed as follows.

[0128]

[Table 13]

[0129]

Embedded image

The above samples were also evaluated in exactly the same manner as in Example 2. As a result, the light-sensitive material using the coupler of the present invention had the same hue, light fastness and heat fastness as those in Example 2. , And it became clear that it was excellent in processing dependence.

Example 5 The same sample 501 as the sample 101 of Example 1 of JP-A-6-3779 was prepared. In the sample 501, the fourth,
Samples 502 to 510 were prepared in exactly the same manner as the sample 501 except that the coupler C-3 of the 5th and 6th layers was replaced with the coupler shown in Table E in an equimolar amount.

[0132]

Embedded image

The sample prepared as described above was imagewise exposed and subjected to the developing treatment described in Example 1 of JP-A-6-3779.

After the development processing, each sample was evaluated for color image fastness under the conditions of 100,000 lux Xe light source (5 hours light / 1 hour dark intermittent irradiation) for 10 days and 100 ° C. for 14 days. The light fastness was evaluated at initial concentrations of 2.0 and 0.5.
The heat fastness was performed at an initial concentration of 2.0. The results are shown in Table E.

[0135]

[Table 14]

From Table E, Samples 505 to 510 using the couplers of the present invention have a particularly high heat fastness to Sample 501, and light fastness in the low density part to Samples 502 to 504. Therefore, it is clear that the total performance is clearly superior.

Example 6 Second sample No. 101 of Example 1 of JP-A-6-208196
Cyan coupler used for the 1st and 3rd layers

[0138]

Embedded image

The couplers (22), (27), and
Samples 601 to 606 were prepared in the same manner except that (37), (42), (43) or (44) was replaced with an equimolar amount. Photosensitizer (FWH type,
Light source color temperature 3200K, made by Fuji Photo Film Co., Ltd.
Was subjected to sensitometric exposure of 250 CMS for 1 second, and then the treatment described in Example 1 of JP-A-6-208196 was performed. Cyan coupler used in the third layer of sample 101 of Example 1

[0140]

[Chemical 38]

The couplers (22), (27), and
Samples 607 to 612 were prepared in the same manner except that (37), (42), (43) or (44) was replaced with an equimolar amount. Each sample was tested as Example 4 of JP-A-6-118546.
A color proof was prepared by exposing and developing by the method described in 1. When the above sample was evaluated in exactly the same manner as in Example 2, the light-sensitive material using the coupler of the present invention showed the same hue, light fastness, heat fastness and processing dependence as those shown in Example 2. It became clear that it was excellent in terms of sex.

[0142]

INDUSTRIAL APPLICABILITY According to the present invention, it contains a cyan coupler which is excellent in hue, coupling activity, heat fastness and light fastness (particularly in the toe) and has little variation in color density caused by variation in processing solution composition. It has become possible to provide a silver halide photographic light-sensitive material.

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

Claims (1)

[Claims] 1. A silver halide color light-sensitive material characterized in that at least one layer on a support contains a coupler represented by the following general formula (I). General formula (I) In formula (I), Za is -C (R ₃₎ = or represents -N =, when the Za represents -N =, Zb is -C (R ₃₎
= Represents, when Za is -C (R ₃₎ = represent, Zb represents -N =. R ₁ and R ₂ each represent an electron-withdrawing group having a Hammett's substituent constant σ _p value of 0.20 or more and 1.0 or less. R ₃ represents a substituent. Y is the following Or it represents a -SO ₂ R _5. R ₄ represents an alkyl group, an alkoxy group or an aryloxy group. R ₅ represents an alkyl group or an aryl group. R ₆ and R ₇ may be the same or different and each represents an alkyl group, an aryl group, an alkoxy group or an aryloxy group, and R ₆ and R ₇ may combine with each other to form a ring. X represents an oxygen atom or a sulfur atom.