JPH08110619A - 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 contains at least one kind of coupler represented by the formula 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=; R3 is a substituent; each of R1 and R2 is an electron withdrawing group having a Hammett's substituent constant σp of 0.20-1.0; and Het is a 6-membered N- containing heterocyclic group. It is necessary only that this photosensitive material has at least one hydrophilic colloidal layer containing this coupler on the support.

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 have a problem in light fastness, and particularly, the light fastness in a low color density portion is remarkably poor. 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.

Further, these patents disclose a leaving group which leaves via an oxygen atom, but this type of coupler was inferior in color forming property and was not practical.

[0005]

Therefore, an object of the present invention is not only excellent in hue, coupling activity, and heat fastness, but also excellent in light fastness and color development caused by fluctuations in processing liquid composition. It is an object of the present invention to provide a silver halide color photographic light-sensitive material containing a coupler, in which density fluctuation is small.

[0006]

DISCLOSURE OF THE INVENTION The inventors of the present invention have diligently studied the leaving group of pyrrolotriazole couplers, and have 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)

[0007]

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(In the general formula (I), Za represents -C (R ₃ ) = or -N =, and when Za is -N =, Zb is -C (R
₃ ) =, and when Za is -C (R ₃ ) =, Zb is
Represents -N =. R ₃ represents a substituent. R ₁ and R
₂ has a Hammett's substituent constant σ _p value of 0.20.
It represents an electron-withdrawing group of 1.0 or more and 1.0 or less. Het represents a 6-membered nitrogen-containing heterocyclic group. )

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

[0010]

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(In the formula, R ₁ , R ₂ , R ₃ and Het have the same meanings as in the general formula (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.
The sum of the σ _p values of ₁ and R ₂ is preferably 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.

R ₁ and R ₂ are Hammett's substituent constants σ _p
The value (hereinafter simply referred to as σ _p value) is an electron-withdrawing group having a value of 0.20 to 1.0. Preferably, the σ _p value is 0.3
It is an electron-withdrawing group of 0 or more and 0.80 or less. Hammett's rule was published in 1935 in order to quantitatively discuss the effect of substituents on the reaction or equilibrium of benzene derivatives. P. Hammett
It is a rule of thumb advocated by, which is widely accepted today. Substituent constants determined by the Hammett's rule include σ _p values and σ _m values, and these values are described in many general textbooks. A. Dean
Volume "Lange's Handbook of Chemistry" 12th edition, 19
1979 (Mc Graw-Hill) and “Special Issue on Chemistry”, 122
Issue, pages 96-103, 1979 (Nankodo), Chemical
Reviews, Vol. 91, pp. 165-195. 1991. In the present invention, R ₁ and R ₂ are defined by the Hammett's substituent constant σ _p value, but it does not mean that the values known in the literatures described in these publications are limited only to certain substituents, and their values are Needless to say, even if the document is unknown, it is included as long as it is included in the range when measured based on the Hammett's rule.

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. , Alkoxycarbonyl, cycloalkoxycarbonyl, alkenyloxycarbonyl, alkynyloxycarbonyl, cycloalkenyloxycarbonyl and the like.

[0015] 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.

Preferred examples of the substituent of R ₁ include a cyano group and an aliphatic oxycarbonyl group (eg, methoxycarbonyl, ethoxycarbonyl, iso-propyloxycarbonyl, sec-butyloxycarbonyl, dodecyloxycarbonyl, octadecyloxycarbonyl). ),
Dialkylphosphono group (eg diethylphosphono), diarylphosphono group (eg diphenylphosphono), alkylsulfonyl group (eg methanesulfonyl, butanesulfonyl), arylsulfonyl (eg toluenesulfonyl), fluorinated alkyl (eg trifluoromethane) ) Is represented. 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.

Preferred examples of the substituent of R ₂ include an aliphatic oxycarbonyl group, a carbamoyl group, a sulfamoyl group, a dialkylphosphono group and a diarylphosphono group, and a substituent of R ₂ is particularly preferably the following. It is an aliphatic oxycarbonyl group represented by the general formula.

[0018]

[Chemical 4]

[0019] 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 such as methyl, ethyl, propyl, isopropyl, t-butyl, t
-Amyl, t-octyl, tridecyl, cyclopentyl, cyclohexyl. R ₃ ', R ₄ ', R
₅ 'is a hydrogen atom or represents an aliphatic group. Examples of the aliphatic group include the groups mentioned above for R ₁ ′ and R ₂ ′.

Z is necessary for forming a 5- to 8-membered ring,
It represents a non-metal atom group, and these rings may be substituted with a substituent, may be a saturated ring, or may have an unsaturated bond. The nonmetal atom is preferably a nitrogen atom, an oxygen atom, a sulfur atom or a carbon atom, and more preferably a carbon atom. The ring formed by Z is preferably a saturated carbon 6-membered ring. A particularly preferred combination of the substituents of R ₁ and R ₂ is when R ₁ is a cyano group and R ₂ is an aliphatic oxycarbonyl group.

Het represents a 6-membered nitrogen-containing heterocyclic group, which may be monocyclic or condensed. A 6-membered nitrogen-containing aromatic heterocyclic group is preferred. As Het, a 6-membered nitrogen-containing aromatic heterocyclic group represented by the following general formula (H) is preferable.

[0022]

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In the formula, W represents a nonmetallic atom group necessary for forming a 6-membered nitrogen-containing aromatic heterocycle which may be condensed.

Examples of the 6-membered nitrogen-containing aromatic heterocycle include pyridine, quinoline, isoquinoline, phenanthridine, pyridazine, pyrimidine, pyrazine, triazine, tetrazine, quinazoline, 1,5-naphthyridine,
Examples include pteridine.

The 6-membered nitrogen-containing aromatic heterocycle mentioned here is
It may have a substituent, and examples of the substituent include R ₃
And the groups listed in. Examples of particularly preferable nitrogen-containing aromatic heterocycles are pyridine, pyrimidine, triazine and pyrazine.

R ₃ is a halogen atom (eg, fluorine atom, chlorine atom, bromine atom), an aliphatic group (eg, a linear or branched alkyl group having 1 to 32 carbon atoms, an aralkyl group, an alkenyl group, an alkynyl group, Cycloalkyl group,
A 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 to 36 carbon atoms (for example, phenyl, 4-t-butylphenyl, 2,4-di-t-amylphenyl, 4-tetradecanamidophenyl, 2-methoxyphenyl), a heterocyclic group (for example, 2
-Furyl, 2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl), cyano group, hydroxy group, nitro group,
Carboxy group, amino group, alkoxy group having 1 to 32 carbon atoms (for example, methoxy, ethoxy, butoxy, 2-methoxyethoxy, 2-dodecylethoxy, 2-methanesulfonylethoxy), aryloxy group having 6 to 36 carbon atoms ( For example, phenoxy, 2-methylphenoxy, 4-t
-Butylphenoxy, 3-nitrophenoxy, 3-t-
Butyloxycarbamoylphenoxy, 3-methoxycarbamoyl), an acylamino group having 2 to 32 carbon atoms (for example, acetamide, benzamide, tetradecanamide, 2- (2,4-di-t-amylphenoxy) butanamide, 4- (3- t-butyl-4-hydroxyphenoxy) butanamide, 2- {4- (4-hydroxyphenylsulfonyl) phenoxy} decanamide), an alkylamino group having 1 to 32 carbon atoms (for example, methylamino,
Butylamino, dodecylamino, diethylamino, methylbutylamino), an anilino group having 6 to 36 carbon atoms (for example, 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 having 2 to 32 carbon atoms (for example, phenylureido, methylureido, N, N-dibutylureido),
A sulfamoylamino group having 1 to 32 carbon atoms (for example,
N, N-dipropylsulfamoylamino, N-methyl-N-decylsulfamoylamino), C1-C32
Alkylthio groups (eg, methylthio, octylthio, tetradecylthio, 2-phenoxyethylthio, 3
-Phenoxypropylthio, 3- (4-t-butylphenoxy) propylthio, an arylthio group having 6 to 36 carbon atoms (for example, phenylthio, 2-butoxy-5-t-octylphenylthio, 3-pentadecylphenylthio,
2-carboxyphenylthio, 4-tetradecanamidophenylthio), alkoxycarbonylamino group (eg, methoxycarbonylamino, tetradecyloxycarbonylamino), sulfonamide group having 1 to 32 carbon atoms (eg, methanesulfonamide, butanesulfone) Amide, octane sulfonamide, hexadecane sulfonamide, benzene sulfonamide, p-toluene sulfonamide, octadecane sulfonamide, 2-methoxy-
5-t-butylbenzenesulfonamide), for example 1 to
36 carbamoyl groups (eg, N-ethylcarbamoyl, N, N-dibutylcarbamoyl, N- (2-dodecyloxyethyl) carbamoyl, N-methyl-N-dodecylcarbamoyl, N- {3- (2,4-dicarboyl). -T-amylphenoxy) propyl} carbamoyl), carbon number 1 to
36 sulfamoyl groups (eg, N-ethylsulfamoyl, N, N-dipropylsulfamoyl, N- (2
-Dodecyloxyethyl) sulfamoyl, N-ethyl-N-dodecylsulfamoyl, N, N-diethylsulfamoyl), a sulfonyl group having 1 to 32 carbon atoms (for example, methanesulfonyl, octanesulfonyl, benzenesulfonyl, toluenesulfonyl). ), An alkoxycarbonyl group having 2 to 32 carbon atoms (for example, methoxycarbonyl, butyloxycarbonyl, dodecyloxycarbonyl, octadecyloxycarbonyl), and 6 to 36 carbon atoms.
A heterocyclic oxy group (for example, 1-phenyltetrazole-5-oxy, 2-tetrahydropyranyloxy),
An azo group having 6 to 36 carbon atoms (eg, phenylazo, 4-
Methoxyphenylazo, 4-pivaloylaminophenylazo, 2-hydroxy-4-propanoylphenylazo), an acyloxy group having 2 to 32 carbon atoms (for example, acetoxy), a carbamoyloxy group having 1 to 32 carbon atoms ( For example, N-methylcarbamoyloxy, N-phenylcarbamoyloxy), a silyloxy group having 3 to 36 carbon atoms (eg, trimethylsilyloxy, dibutylmethylsilyloxy), an aryloxycarbonylamino group having 6 to 36 carbon atoms (eg, phenoxy). Carbonylamino), an imide group having 1 to 32 carbon atoms (for example, N-succinimide, N-phthalimide, 3-octadecenylsuccinimide), a heterocyclic thio group having 6 to 36 carbon atoms (for example, 2-benzothiazoli). Luthio, 2,4-di-phenoxy-1,3,5-tria Lumpur-6-thio, 2-pyridylthio), a sulfinyl group having 1 to 32 carbon atoms (e.g.,
Dodecanesulfinyl, 3-pentadecylphenylsulfinyl, 3-phenoxypropylsulfinyl), phosphonyl group having 3 to 36 carbon atoms (for example, phenoxyphosphonyl, octyloxyphosphonyl, phenylphosphonyl), aryloxy having 7 to 36 carbon atoms Carbonyl group (eg, phenoxycarbonyl), acyl group having 2 to 32 carbon atoms (eg, acetyl, 3-phenylpropanoyl, benzoyl, 4-dodecyloxybenzoyl), azolyl group having 1 to 32 carbon atoms (eg, imidazolyl, Pyrazolyl, 3-chloro-pyrazol-1-yl, triazolyl).

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

In the present invention, R ₁ represents a cyano group, R ₂ represents an aliphatic oxycarbonyl group, R ₃ represents an aliphatic group or an aryl group, and Het is represented by the general formula (H). This is the case of a 6-membered nitrogen-containing aromatic heterocyclic group.

The coupler represented by the general formula (I) is
The R ₂ or R ₃ group contains a coupler residue represented by the general formula (I) to form a dimer or higher multimer, or the R ₂ or R ₃ group forms a polymer chain. It may be contained to form a homopolymer or a copolymer. The homopolymer or copolymer containing a polymer chain is a typical example is 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 acrylic acid ester, methacrylic acid ester, maleic acid may be used as a copolymerization component. 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.

[0030]

[Chemical 6]

[0031]

[Chemical 7]

[0032]

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[0033]

[Chemical 9]

[0034]

[Chemical 10]

[0035]

[Chemical 11]

[0036]

[Chemical 12]

[0037]

[Chemical 13]

The intermediate of the compound of the present invention can be synthesized by a known method. J. Chem. Soc., 51
49 (1962), J. Amer. Chem., 81, 2452 (1959) and Heterocyclic., 27, 2301 (1988), IZV. Akad,
Nauk SSSR, Ser. Khim., Page 582 (1970) and the like, or the literature cited therein or a similar method. The triazole compound represented by the general formula (V) can be used as a starting material.

[0039]

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Next, a specific synthesis example will be shown. Synthesis Example 1 Synthesis of Exemplified Compound (1) Exemplified Compound (1) was synthesized by the following route.

[0041]

[Chemical 15]

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 compound a (11 g, 6
0.4 mmol) was added slowly. The reaction solution was stirred at room temperature for 2 hours, 300 ml of water was added, and ethyl acetate 3
It was extracted with 00 ml. 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 crude compound b (14 g). Crude compound b (14
g) was used in the next step without purification.

Synthesis of compound c Pyridinium bromide perbromide (1) was added to a solution of crude compound b (14 g) in 200 ml of tetrahydrofuran at room temperature.
(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 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 the solvent was distilled off under reduced pressure. Hexane 1 in the obtained oil
Crystallization occurred upon addition of 00 ml. The crystals were filtered and dried to obtain 11.2 g of compound e.

Synthesis of Compound (1) 2-chloro-4,6-dimethoxy-1,3,5-triazine (8.) was added to a solution of compound e (11.2 g, 23.6 mmol) in 110 ml of pyridine at 0 ° C. 3 g, 47.2 mmol) was added. After stirring at 0 ° C. for 1 hour, the temperature was gradually raised to room temperature. After the reaction, 120 ml of 36% hydrochloric acid aqueous solution was added, and after neutralization, 100 ml of ethyl acetate was added. The organic phase was washed with water and brine, dried over sodium sulfate, and the solvent was evaporated. By purifying the obtained residue by column chromatography, the target Exemplified Compound (1) was 6.7.
g was obtained.

Synthesis Example 2 Synthesis of Exemplified Compound (6) Up to compound (f) was synthesized in the same manner as in Synthesis Example 1.

[0048]

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To a solution of the compound (f) (7.0 g, 10.1 mmol) in 70 ml of pyridine was added 2,4,6-trichloropyrimidine (3.7 g, 20.2 mmol) at 0 ° C. The temperature was gradually raised and the mixture was stirred at room temperature for 20 hours. After the reaction, 90 ml of 36% hydrochloric acid aqueous solution was added, and after neutralization, 100 ml of ethyl acetate was added. The organic phase was washed with water and brine, dried over sodium sulfate, and the solvent was evaporated.
The residue thus obtained was purified by column chromatography to obtain 2.7 g of the desired exemplary compound (6).

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 organic solvent (if necessary, a low-boiling organic solvent is also used), 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 (for example, 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 (for example, 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-cyte).
rt-aminophenol, 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 processing methods and processing additions 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.

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

[0056]

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 (above) 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 structure of the comparative coupler used in this example is shown below.

[0059]

[Chemical 17]

For sample 101 prepared as described above, the cyan coupler was replaced with the coupler shown in Table A in a 1/2 molar amount, and the silver halide was also changed to 1/2. Samples 102 to 110 were prepared in the same manner. After gradation exposure was performed on 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 Bleach fixing 35 ° C 60 seconds Water washing 35 ° C 120 seconds

(Processing liquid composition) [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 red light optical density of the processed sample was measured,
The maximum color density Dmax was determined. In addition, the yellow density at the point of giving a cyan density of 1.0 is measured with an X-Rite 310 densitometer (X-Ri
te Company). The lower the yellow density, the less the secondary absorption and the better the hue.

Next, these samples were subjected to 200,000 lux Xe.
Light irradiation was carried out for 5 days through a sharp cut filter capable of cutting about 50% at 390 nm under a light source (5 hours light / 1 hour dark irradiation). 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 rate was evaluated at two points, the Dmax part and the low density part showing a color density of 1/5 of Dmax, and shown in Table A as a percentage when the initial density was 100%.

[0066]

[Table 1]

As is clear from Table A, Samples 102 to 110 are superior in hue to Comparative Sample 101. Among them, Samples 102 to 104 are excellent in hue, but are poor in light fastness in the low density portion and are clearly inferior to Comparative Sample 101. On the other hand, it can be seen that Samples 105 to 110 using the coupler of the present invention are excellent in hue and color development, have improved light fastness in the low density portion, and are almost the same as the residual ratio in the high density portion.

Next, the samples 101 to 110 were exposed and processed in the same manner as above, and then stored at 100 ° C. for 10 days to evaluate the residual ratio of the color image at the maximum color density. The results are shown in Table B.

[0069]

[Table 2]

From Table B, it can be seen that Samples 105 to 110 using the coupler of the present invention are superior in heat fastness to Sample 101 using the comparative coupler Ex-1.

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.

Fifth layer Preparation of coating solution Cyan coupler (ExC) 310 g, color image stabilizer (Cpd-1)
100 g, color image stabilizer (Cpd-5) 100 g, color image stabilizer
(Cpd-6) 10 g, color image stabilizer (Cpd-8) 10 g, color image stabilizer (Cpd-9) 100 g, color image stabilizer (Cpd-10) 1
00g, UV absorber (UV-2) 100g, Solvent (Solv
-2) Dissolved in 250 g, solvent (Solv-4) 250 g and ethyl acetate 360 ml, this solution was emulsified and dispersed in 2000 g of a 16% gelatin aqueous solution containing 60 ml of 10% sodium dodecylbenzenesulfonate and 10 g of citric acid, and an emulsified dispersion. C was prepared. On the other hand, silver chlorobromide emulsion C (cubic, 1: 4 mixture of large size emulsion C having an average grain size of 0.50 μm and small size emulsion C having a grain size of 0.41 μm (silver molar ratio). Coefficient of variation of grain size distribution is 0.09 each
And 0.11. 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, the red sensitizing dyes G and H shown below were respectively 1.0 × 10 ⁻⁴ and 5.
0 × 10 ⁻⁵ mol, and to the small-sized emulsion C, 1.2 × 10 ⁻⁴ and 6.0 × 10 ⁻⁵ mol were added, respectively. The chemical ripening of this emulsion was optimally performed by adding sulfur sensitization and gold sensitization. The above emulsified dispersion C and this silver chlorobromide emulsion C were mixed and dissolved to prepare a coating solution for the fifth layer having the composition shown below.

Coating solutions for the first to seventh layers other than the fifth layer were prepared in the same manner as the coating solution for the fifth layer. 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.

[0075]

[Table 3]

[0076]

[Table 4]

[0077]

[Table 5]

1- (5-methylureidophenyl) is added to the blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer.
-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 in order to prevent irradiation.

[0079]

Embedded image

(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.

[0081]

[Table 6]

[0082]

[Table 7]

[0083]

[Table 8]

[0084]

[Table 9]

[0085]

[Chemical 19]

[0086]

Embedded image

[0087]

[Chemical 21]

[0088]

[Chemical formula 22]

[0089]

[Chemical formula 23]

[0090]

[Chemical formula 24]

[0091]

[Chemical 25]

A cyan coupler was added to the sample 201.
Samples 201 to 210 were prepared in exactly the same manner as Sample 201, except that the amount of silver halide emulsion was changed to 1/2 and the coating amount of silver halide emulsion was reduced to 1/2. First, the sample 201 was exposed using a sensitometer (FWH type manufactured by Fuji Photo Film Co., Ltd., color temperature of light source: 3200 ° K) to develop about 35% of the coated silver amount and give a gray color.

Thereafter, imagewise exposure was performed using a printer processor PP1820V manufactured by Fuji Photo Film Co., Ltd.
In the following processing steps, continuous processing (running test) was carried out until the tank was replenished with twice the capacity of the color developing tank. 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 sec − Rinse (2) 35 ° C 30 sec − 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 countercurrent 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 12.0 g Potassium chloride 6.5 g-Potassium bromide 0.03 g-Potassium carbonate 27.0 g 27.0 g Optical brightener (WHITEX 4 Sumitomo Chemical Co., Ltd.) 1.0 g 3.0 g Sodium sulfite 0.1 g 0.1 g Disodium-N, N-bis (sulfona Ethyl) hydroxylamine 5.0 g 10.0 g Sodium triisopropylnaphthalene (β) sulfonate 0.1 g 0.1 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaminoline 3/2 sulfuric acid Monohydrate 5.0g 11.5g Add water 1000ml 1000ml pH (25 ℃ / 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 Ethylenediamine Tetraacetic acid 5 g 12.5 g Nitric acid (67%) 30 g 65 g Water added 1000 ml 1000 ml pH (25 ° C / adjusted with acetic acid and ammonia water) 5.8 5.6

[Rinse solution] (tank solution and replenisher are the same) 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 gradation-exposed with red light using an optical wedge and treated with the treatment liquid. For each sample, 14 days and 1 under 100,000 lux Xe light source (5 hours light / 1 hour dark intermittent irradiation)
The color image fastness was evaluated under the conditions of 00 ° C. for 14 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. Further, regarding the heat fastness, the change in the amount of coloration of the white background portion was measured by the blue optical density, and is also shown in Table C as ΔDmin.

[0098]

[Table 10]

From Table C, it can be said that Samples 205 to 210 using the coupler of the present invention are excellent in color developability, image fastness and stain.

Next, in order to examine the change in photographic performance of Samples 201 to 210 due to processing variations, the bleach-fixing solution was added to the color developing solution at a ratio of 0.5 cc of the bleach-fixing solution to 1 liter of the above-mentioned color developing solution. 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.

[0101]

[Table 11]

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

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

Example 3 The same sample 501 as the sample 101 of Example 1 of JP-A-6-3779 was prepared. Also, in the sample 301,
Samples 302 to 310 were prepared in exactly the same manner as Sample 301, 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.

[0105]

[Table 12]

[0106]

[Chemical formula 26]

The sample prepared as described above was imagewise exposed and subjected to the developing treatment described in Example 1 of JP-A-6-3779. When the samples 301 to 310 were evaluated in the same manner, it was confirmed that the sample of the present invention was an excellent photographic light-sensitive material having excellent hue and image fastness and small process variation.

Example 4 No. 2 of the sample 101 of Example 1 of JP-A-6-208196
Cyan coupler used for the 1st and 3rd layers

[0109]

[Chemical 27]

The couplers (1), (2), (3), and
Samples 401 to 406 were prepared in the same manner except that (6), (9) or (21) was replaced with an equimolar amount. Photosensitizer (FWH type, light source color temperature 3200 °
250 CM using K, Fuji Photo Film Co., Ltd.
After exposure for S for 1 second for sensitometry, the treatment described in Example 1 of JP-A-6-208196 was performed. When the samples 401 to 406 were evaluated in the same manner, it was confirmed that the hue and the image fastness were excellent, and the variation in the color density due to the variation in the composition of the treatment liquid was small.

Example 5 No. 3 of the sample 101 of Example 1 of JP-A-6-118546
Cyan coupler used for layers

[0112]

[Chemical 28]

Is an equimolar amount of the couplers (1), (2) of the present invention.
, (3), (6), (9) or (21) were replaced with Samples 501 to 506 in the same manner. Each sample is disclosed in JP-A-6
A color proof was prepared by exposing and developing by the method described in Example 4 of -118546. Samples 501-506
In the same manner as above, it was confirmed that the hue and the image fastness were excellent, and the variation in color density due to the variation in the composition of the treatment liquid was small.

[0114]

According to the present invention, the hue and the image fastness are excellent, and it is possible to suppress the variation of the color density due to the variation of the processing liquid composition.

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 the general formula (I), Za represents -C (R ₃ ) = or -N =, and when Za is -N =, Zb represents -C (R ₃ ) =,
When Za is -C (R ₃₎ = a, Zb represents -N =. R ₃
Represents a substituent. 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. Het represents a 6-membered nitrogen-containing heterocyclic group. )