JPH08122985A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE: To enhance the hue, coupling activity, heat fastness, and light fastness and to reduce fluctuation of color development density due to fluctuation of a processing solution composition by incorporating a specified cyan coupler in at least one layer on a support. CONSTITUTION: The silver halide color photographic sensitive material having on a support at least one layer containing at least one kind of cyan coupler represented by the formula in which Za is a -C(R3 )= or -N= group, and when it is -N=, Zb is -C(R3 )= and when it 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 of 0.20-1.0; Q is an optionally substituted nonmetallic atomic group necessary to form an unsaturated carbon ring or a hetero ring.

Description

Detailed Description of the Invention

[0001]

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

[0002]

2. Description of the Related Art In a silver halide color photographic light-sensitive material, a dye such as azomethine is formed by reacting an oxidized aromatic primary amine type color developing agent with a coupler using exposed silver halide as an oxidizing agent. It is well known that a color image is formed. 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 problem in color reproducibility, 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 Nos. 491197A1, 488248, and 545, 545
Pyrroloazoles described in No. 300 have been proposed.
These couplers are excellent in hue, coupling activity and heat fastness. 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.

[0004]

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.

[0005]

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 was achieved by a silver halide color photographic light-sensitive material characterized in that at least one layer on a support contains at least one cyan coupler represented by the following general formula (I).

[0006]

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(In the formula, Za is -C (R ₃ ) = or-
Represents N =, and when Za is -N =, Zb is -C
Represents (R ₃ ) =, and when Za is -C (R ₃ ), Z
b represents -N =. R ₃ represents a substituent. R ₁ and R ₂ each have 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. Q represents a group of non-metal atoms necessary for forming an unsaturated carbocycle or a heterocycle. The non-metal atomic group forming Q may be further substituted with a substituent. )

The compound of the present invention is described in detail below. The couplers of the present invention each have a Hammett's substituent constant σ _p value of R ₁ and R ₂ (hereinafter referred to as σ _p value) of 0.
It is an electron-withdrawing group of 20 or more and 1.0 or less, and R ₁ and R
_It is desirable that the sum of the σ _p values of ₂ is 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.
It is 70 or more, and the upper limit is about 1.8. R ₁
And R ₂ each preferably have a σ _p value of 0.30 or more.
It is an electron-withdrawing group of 8 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. A rule of thumb put forward by Hammett, 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 ed. "Lange's
Handbook of Chemistry "12th Edition, 1979 (Mc G
raw-Hill) and "Special Issue on Chemistry", No. 122, 96-
103 pages, 1979 (Nankodo), Chemical Reviews,
91, 165-195, 1991.
The σ _p value does not mean that it is limited only to the substituents described in these publications, and that it is included as long as it falls within the range when measured based on Hammett's rule even if the value is unknown in the literature. Of course.

Specific examples of R ₁ and R ₂ include acyl group, acyloxy group, carbamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, cyano group, nitro group, dialkylphosphono group and diarylphosphono group. , A diarylphosphinyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, a sulfonyloxy group,
Acylthio group, sulfamoyl group, thiocyanate group,
Thiocarbonyl group, alkyl group at least substituted with two or more halogen atoms, alkoxy group at least substituted with two or more halogen atoms, aryloxy group at least substituted with two or more halogen atoms, two or more An alkylamino group at least substituted with a halogen atom, an alkylthio group at least substituted with two or more halogen atoms, an aryl group substituted with another electron-withdrawing group having a σ _{p of} 0.20 or more, a heterocyclic group, Examples thereof include chlorine atom, bromine atom, azo group, and selenocyanate group. Among these substituents, the group capable of further having a substituent may further have a substituent as mentioned below for R ₃ .

[0010] 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), pyrazolyl group (0.37),
Methanesulfonyloxy group (0.36), dimethoxyphosphoryl group (0.60), sulfamoyl group (0.5
7) etc.

As an example of the substituent of R _1, 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) are preferable. Group, a cycloalkoxycarbonyl group, a cycloalkenyloxycarbonyl group, and more specifically, for example, methoxycarbonyl, ethoxycarbonyl, dodecyloxycarbonyl, octadecyloxycarbonyl, 2-ethylhexyloxycarbonyl,
sec-butyloxycarbonyl, oleyloxycarbonyl, benzyloxycarbonyl, propargyloxycarbonyl, cyclopentyloxycarbonyl, cyclohexyloxycarbonyl, 2,6-di-t-butyl-
4-methylcyclohexyloxycarbonyl), dialkylphosphono group (dialkylphosphono group having 2 to 36 carbon atoms, for example, diethylphosphono, dimethylphosphono), sulfonyl group (alkyl or arylsulfonyl having 1 to 36 carbon atoms) Group, for example, methanesulfonyl group, butanesulfonyl group, benzenesulfonyl group, p-
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 an aliphatic oxycarbonyl group, a carbamoyl group (a carbamoyl group having 1 to 36 carbon atoms, for example, diethylcarbamoyl, dioctylcarbamoyl), a sulfamoyl group (a sulfamoyl group having 1 to 36 carbon atoms, for example, Dimethylsulfamoyl, dibutylsulfamoyl), dialkylphosphono groups and diarylphosphono groups (having 12 to 50 carbon atoms) as described for R _1.
Is a diarylphosphono group, and represents, for example, diphenylphosphono or di (p-toluyl) phosphono). The substituent of R ₂ is particularly preferably an aliphatic oxycarbonyl group represented by the following general formula (II).

[0013]

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In the formula, R ₁ 'and R ₂ ' represent an aliphatic group, for example, a linear or branched alkyl group having 1 to 36 carbon atoms, 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 ′.

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.
Preferred non-metal atoms include nitrogen atom, oxygen atom, sulfur atom and carbon atom, and more preferably carbon atom. The ring formed by Z is preferably a saturated carbon 6-membered ring.

R ₃ represents a substituent, for example, a halogen atom (eg, fluorine atom, chlorine atom, bromine atom), an aliphatic group (eg, a linear or branched alkyl group having 1 to 36 carbon atoms, an aralkyl group, Alkenyl group, alkynyl group,
A cycloalkyl group or a cycloalkenyl group, more 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 (an aryl group having 6 to 36 carbon atoms, for example, phenyl, 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), a cyano group, a hydroxyl 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, for example, Methoxy, ethoxy, butoxy,
2-methoxyethoxy, 2-dodecylethoxy, 2-methanesulfonylethoxy), an aryloxy group (an aryloxy group having 6 to 36 carbon atoms, such as phenoxy, 2-methylphenoxy, 4-t-butylphenoxy, 3- Nitrophenoxy, 3-t-butyloxycarbamoylphenoxy, 3-methoxycarbamoyl), acylamino group (acylamino group having 1 to 36 carbon atoms, such as acetamide, benzamide, tetradecanamide, 2- (2,4-di-t) -Amylphenoxy) butanamide, 4- (3-t-butyl-4-hydroxyphenoxy) butanamide, 2- {4- (4-hydroxyphenylsulfonyl) phenoxy} decanamide), alkylamino group (alkyl having 1 to 36 carbon atoms) An amino group such as methylami , Butylamino, dodecylamino, diethylamino, methylbutylamino), and 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 1 to 36 carbon atoms, for example, phenylureido, methylureido, N, N-). Dibutyl ureido), sulfamoylamino group (sulfamoylamino group having 1 to 36 carbon atoms, for example, N, N-dipropylsulfamoylamino, N-methyl-N-decylsulfamoylamino), alkylthio group (This is an alkylthio group having 1 to 36 carbon atoms, such as 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-methyl-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 1 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, for example, dodecanesulfinyl, 3-pentadecylphenylsulfinyl, 3-phenoxypropylsulfinyl), phosphonyl group (C1-C36 phosphonyl group, for example, phenoxyphosphonyl, octyloxyphosphonyl, phenyl Phosphonyl), aryloxycarbonyl group (7 to 36 carbon atoms)
An aryloxycarbonyl group of, for example, phenoxycarbonyl), an acyl group (an acyl group having 1 to 36 carbon atoms, such as acetyl, 3-phenylpropanoyl,
Benzoyl, 4-dodecyloxybenzoyl), azolyl group (for example, imidazolyl, pyrazolyl, 3-chloro-
Pyrazol-1-yl, triazolyl). Among these substituents, those substitutable may be further substituted with the substituents listed here.

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

Q represents a group of non-metal atoms necessary for forming a 5- to 8-membered unsaturated carbocycle or heterocycle. The non-metal atomic group forming Q may be further substituted with the substituents listed for R ₃ . The ring formed by Q is preferably an aromatic ring or a hetero ring.

The aromatic ring formed by Q is preferably a substituted or unsubstituted benzene ring or naphthalene ring, which may be substituted by the substituents mentioned for R ₃ . Q represents a non-metal atom necessary for forming a heterocycle, and the non-metal atom is preferably a nitrogen atom, an oxygen atom, a sulfur atom or a carbon atom. The heterocycle is preferably a 5-membered or 6-membered ring, which may be condensed. Examples of heterocycles include pyridine, quinoline,
Isoquinoline, phenanthridine, pyridazine, pyrazine, pyrimidine, triazine, tetrazine, quinazoline, 1,5-naphthyridine, pteridine, pyrrole, indole, furan, pyrrolidine, pyrazole, imidazole, 1,2,4-triazole, 1,2,2. 3-triazole, tetrazole, benzimidazole, indazole, purine, perimidine, oxazole, benzoxazole, isoxazole, thiazole, benzothiazole, 1,3,4-oxadiazole, 1,2,5-
Oxadiazole, 1,3,4-thiadiazole, 1,
2,5-thiadiazole is mentioned. The heterocycles mentioned here may be substituted by the substituents mentioned for R ₃ . Examples of particularly preferred heterocycles include pyridine,
Pyrrole, pyrrolidine, furan and indole.

The couplers of the present invention are particularly characterized in that Za is -N =
A is Zb is -C (R ₃₎ = a is more preferable. R
₁ , R ₂ and R ₃ have the above-mentioned preferred substituents applied thereto, and the ring formed by Q has the above-mentioned preferred rings applied thereto.

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 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.

[0022]

[Chemical 4]

[0023]

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[0024]

[Chemical 6]

[0025]

[Chemical 7]

[0026]

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[0027]

[Chemical 9]

[0028]

[Chemical 10]

[0029]

[Chemical 11]

[0030]

[Chemical 12]

[0031]

[Chemical 13]

[0032]

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[0033]

[Chemical 15]

[0034]

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[0035]

[Chemical 17]

The compound represented by formula (I) of the present invention can be prepared by a known method, for example, JCS, 1961, 518.
P., JCS, 1962, p. 5149, Angew. Chem.,
Volume 72, page 956 (1960), Berichte, 9th.
Volume 7, page 3436 (1964) and the like and the literature cited therein or a similar method. The triazole compound represented by the following general formula (III) can be easily used as a starting material, for example, by the method shown in the following synthesis examples.

[0037]

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(R represents a hydrogen atom or an alkyl group,
R ₃ represents a substituent. ) Specific synthesis examples of the compound of the present invention are shown below. Synthesis example 1. Synthesis of Exemplified Compound (53) Exemplified compound (a) was synthesized by the following route.

[0039]

[Chemical 19]

Synthesis of compound b 2,6-di-t-butyl-4-methylcyclohexanol (17 g, 75 mmol) in acetonitrile 200 m
1 solution at 0 ° C., trifluoroacetic anhydride (10.6 m
1, 75 mmol) was added dropwise, and then compound a (11
g, 60.4 mmol) was added slowly. 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). The crude compound b (14 g) was used in the next step without purification.

Synthesis of compound c Crude compound b (14 g) tetrahydrofuran 200 ml
Pyridinium bromide perbromide (12.7 g, 40 mmol) was added to the solution at room temperature, and the mixture was stirred for 8 hours.
200 ml of a 2 g aqueous solution of sodium sulfite was added to the reaction solution, followed by extraction 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). The 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). A solution of the crude compound c (15 g) in 100 ml of tetrahydrofuran was added to the solution s at 0 ° C.
Was added dropwise and stirred at room temperature for 1 hour. 200 ml of 1N hydrochloric acid and 200 ml of ethyl acetate were added to the reaction solution 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 d was obtained by purifying the obtained residue by column chromatography.
(12.1 g) was obtained.

Synthesis of Compound e Compound d (12.1 g, 24.8 mmol) in 100 ml of methanol was added with 5 g of sodium hydroxide and 50 m of aqueous solution.
1 was added, and the mixture was stirred at 50 ° C. for 2 hours. 200 ml of 1N hydrochloric acid and 200 ml of ethyl acetate were added to the reaction solution for extraction. The organic phase was washed with water and brine, dried over sodium sulfate, and the solvent was distilled off under reduced pressure. 100 ml of hexane was added to the obtained oil to crystallize. Compound e (11.2 g) was obtained by filtering and drying the crystals.

Synthesis of Compound (53) Compound (e) (3.0 g, 6.3 mmol) in pyridine (2)
Benzoyl chloride (1.7 ml) at 0 ° C.
3 g, 12.3 mmol) was added dropwise. After stirring at room temperature for 2 hours, the mixture was poured into 200 ml of diluted hydrochloric acid water, and ethyl acetate 10 was added.
Extracted with 0 ml. The organic layer was washed with water (4 times) and then dried over sodium sulfate. After being concentrated under reduced pressure, it was purified by column chromatography (developing solvent: ethyl acetate / n-hexane = 1/7) and recrystallized from n-hexane to give the target exemplified compound (53) (1.49 g,
2.7 mmol, mp 151-155 ° C) was obtained.

Synthesis Example 2. Synthesis of Exemplified Compound (54) Exemplified Compound (54) was synthesized according to the following scheme.
(Compound (e) was synthesized in the same manner as in Synthesis Example 1.)

[0046]

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Synthesis of Compound (54) 4-dodecyloxybenzoyl chloride (12.0 g, 21 mmol) in dichloromethane (10 ml) was added to a solution of compound (e) (5.0 g, 10.5 mmol) in pyridine (50 ml) at 0 ° C. ) The solution was added dropwise. The mixture was stirred at room temperature for 30 minutes, poured into 200 ml of diluted hydrochloric acid water, and extracted with 100 ml of ethyl acetate. After washing the organic layer with water (3 times),
It was dried over sodium sulfate. After concentration under reduced pressure, column chromatography (developing solvent: ethyl acetate / n-
It was purified with hexane = 1/5) and recrystallized from methanol to give the target exemplified compound (17) (4.5 g,
(6.0 mmol, mp 88-94 ° C) was obtained.

Synthesis Example 3. Synthesis of Exemplified Compound (55) Exemplified Compound (55) was synthesized according to the following scheme.
(Compound (e) was synthesized in the same manner as in Synthesis Example 1.)

[0049]

[Chemical 21]

Synthesis of compound (55) 2,6-Dichlorobenzoyl chloride (5.5 g, 26.3 mmol) was added to a solution of compound (e) (5.0 g, 10.5 mmol) in pyridine (50 ml) at 0 ° C. Dropped. The mixture was stirred at room temperature for 2 hours, poured into 200 ml of diluted hydrochloric acid water, and extracted with 100 ml of ethyl acetate. The organic layer is washed with water (three times), purified by column chromatography (developing solvent: ethyl acetate / n-hexane = 1/5), and recrystallized from ethyl acetate- (n) -hexane to give the target compound. Compound (55) (4.6 g, 7.3 mmol, mp
225-235 ° C) was obtained.

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 invention may be a hydrophilic colloid layer on a support, but a photosensitive silver halide emulsion layer is preferred. 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 coloring hue of the photosensitive emulsion layer and the color coupler is
It is also possible to adopt a configuration that does not have the above correspondence. In the present invention, it is particularly preferable to use the coupler of the present invention 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
Is a 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 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 organic 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. , Ibid 2,541
No. 230, Japanese Patent Publication No. 53-41091, European Patent Publication No. 029104, and the like, and regarding dispersion with an organic solvent-soluble polymer, PCT International Publication No. W.
O88 / 00723.

As the high-boiling point organic solvent that can be used in the above-mentioned oil-in-water dispersion method, phthalic acid esters (eg, dibutyl phthalate, dioctyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate) can be used. , 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 and the like) and photographic constituent layers (layer arrangement and the like) applied in the present invention, and processing methods and processing additions applied for processing the 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. 6-218196, 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 grains used in the present invention may have any halogen composition such as silver chloride, silver bromide, silver chlorobromide, silver iodochlorobromide and silver iodobromide. , 90 mol% or more, particularly 95 mol% or more is silver chloride, silver chlorobromide, or silver chloroiodobromide grains. In particular, in the present invention, in order to accelerate the development processing time, a silver chlorobromide or silver chloride containing substantially no silver iodide can be preferably used. The term "substantially free of silver iodide" as used herein means that the silver iodide content is 1 mol% or less, preferably 0.2 mol% or less. on the other hand,
For the purpose of increasing the sensitivity of high illuminance, the sensitivity of spectral sensitization, or the stability of a light-sensitive material over time, JP-A-3-84
No. 545 on the emulsion surface as described in No. 545
High silver chloride grains containing 3 mol% of silver iodide may be preferably used. The halogen composition of the emulsion may be different or the same between grains, but if an emulsion having the same halogen composition among grains is used, it is easy to make the properties of each grain uniform. Regarding the halogen composition distribution inside the silver halide emulsion grains, the so-called uniform structure grains having the same composition in any portion of the silver halide grains, or the core inside the silver halide grains and the shell surrounding it. (Shell) [a single layer or a plurality of layers] particles having a so-called laminated structure having a different halogen composition, or a structure having a portion having a different halogen composition in the inside or the surface of the particle (in the case of being on the surface of the particle, the edge of the particle, It is possible to appropriately select and use particles having a structure in which parts having different compositions are bonded to a corner or a surface. In order to obtain high sensitivity, it is advantageous to use either of the latter two rather than the particles having a uniform structure, and it is also preferable from the viewpoint of pressure resistance. When the silver halide grains have the structure as described above, the boundary between different portions in the halogen composition is an unclear boundary because a mixed crystal is formed due to the composition difference even if the boundary is clear. It may also be one that positively has a continuous structural change.

The high silver chloride emulsion used in the present invention preferably has a structure having a silver bromide localized phase inside and / or on the surface of the silver halide grain in the form of layer or non-layer as described above. The halogen composition of the localized phase preferably has a silver bromide content of at least 10 mol%, more preferably more than 20 mol%. The silver bromide content of the localized layer of silver bromide is analyzed using an X-ray diffraction method (for example, described in “The Chemical Society of Japan, New Experimental Chemistry Course 6, Structural Analysis”, Maruzen) or the like. can do. And these localized phases are the inside of the particle, the edge of the particle surface,
It can be on a corner or on a surface, but one preferred example is one that is epitaxially grown on the corner of the grain. It is also effective to further increase the silver chloride content of the silver halide emulsion for the purpose of reducing the replenishment amount of the developing solution. In such a case, an almost pure silver chloride emulsion having a silver chloride content of 98 mol% to 100 mol% is also preferably used.

The average grain size of silver halide grains contained in the silver halide emulsion used in the present invention (the grain size is defined by the diameter of a circle equivalent to the projected area of the grain and the number average thereof is taken) is 0. 1 μm to 2 μm is preferable. Further, the particle size distribution thereof is preferably a so-called monodisperse coefficient of variation of 20% or less (standard deviation of particle size distribution divided by average particle size), preferably 15% or less, more preferably 10% or less. . At this time, for the purpose of obtaining a wide latitude, it is also preferable to use the above monodispersed emulsion by blending it in the same layer, or to perform multi-layer coating. The shape of silver halide grains contained in a photographic emulsion is regular, such as cubic, tetradecahedral or octahedral.
Those having a (regular) crystal form, those having an irregular (eg regular) crystal form such as spheres and plates, or those having a composite form thereof can be used. It may also be a mixture of materials having various crystal forms. In the present invention, 50% or more, preferably 7% or more of the particles having the above-mentioned regular crystal form are used in the present invention.
It is preferable to contain 0% or more, more preferably 90% or more. In addition to these, an emulsion in which tabular grains having an average aspect ratio (diameter in terms of circle / thickness) of 5 or more, preferably 8 or more exceeds 50% of all grains as a projected area can also be preferably used.

The silver salt (bromide) bromide emulsion used in the present invention is P.Gl.
afkides Chimie etPhisique Photographique (Paul
Montel, 1967), by GF Duffin Photographi
c Emulsion Chemistry (Focal Press, 1966
,) By VL Zelikman et al Making and Coating Phot
It can be prepared using the method described in ographic Emulsion (Focal Press, 1964) and the like. That is, any of an acidic method, a neutral method, an ammonia method and the like may be used, and a method of reacting a soluble silver salt and a soluble halogen salt may be any one of a one-sided mixing method, a simultaneous mixing method, and a combination thereof. You may use. It is also possible to use a method of forming grains in an atmosphere in which silver ions are excessive (so-called reverse mixing method). As one form of the simultaneous mixing method, a method of keeping pAg in a liquid phase where silver halide is formed constant, that is, a so-called controlled double jet method can be used. According to this method, a silver halide emulsion having a regular crystal form and a nearly uniform grain size can be obtained.

The localized phase of the silver halide grain of the present invention or its substrate preferably contains a different metal ion or a complex ion thereof. The preferred metal is selected from metal ions or metal complexes belonging to Group VIII and Group IIb of the Periodic Table, and lead ions and thallium ions. Ions or their complex ions mainly selected from iridium, rhodium, iron etc. in the localized phase, and metal ions selected mainly from osmium, iridium, rhodium, platinum, ruthenium, palladium, cobalt, nickel, iron etc. as the substrate. Alternatively, the complex ions can be used in combination. Further, the type and concentration of the metal ion can be changed depending on the localized phase and the substrate. Plural kinds of these metals may be used. In particular, iron and iridium compounds are preferably present in the silver bromide localized phase.

These metal ion-providing compounds are used in a gelatin aqueous solution which becomes a dispersion medium at the time of silver halide grain formation,
Of the silver halide grains of the present invention by means such as adding in an aqueous solution of a halide, in an aqueous solution of silver salt or other aqueous solution, or in the form of silver halide fine particles containing metal ions in advance and dissolving the fine particles. It is contained in the localized phase and / or other particle portion (matrix). The metal ions used in the present invention can be contained in the emulsion grains either before, during or immediately after grain formation. This can be changed depending on the position of the metal ion contained in the particle.

The silver halide emulsion used in the present invention is
It is chemically and spectrally sensitized. Regarding the chemical sensitization method, chemical sensitization using a chalcogen sensitizer (specifically, sulfur sensitization represented by the addition of an unstable sulfur compound, selenium sensitization with a selenium compound, tellurium sensitization with a tellurium compound is performed. Noble metal sensitization typified by gold sensitization, reduction sensitization and the like can be used alone or in combination. As the compound used for the chemical sensitization, those described in JP-A-62-215272, page 18, lower right column to page 22, upper right column are preferably used. The emulsion used in the present invention is a so-called surface latent image type emulsion in which a latent image is mainly formed on the grain surface.

In the silver halide emulsion grains in the silver halide emulsion layer containing a cyan coupler, at least 70% or more of the grains in which development silver is observed in the suppressed development are developed in the corners or near the corners of the grains. Is preferred. Here, the vicinity of the corner means that it is within a range of 1/4 of the diameter of the projected area of the particle centered on the corner. In the present invention, the development starting point can be observed according to the following procedure. First, a sample prepared by coating a silver halide emulsion on a transparent support is exposed through an optical wedge and a red filter, developed with the following black and white developer for 5 minutes at 20 ° C., fixed, and washed with water. The sample after this treatment was subjected to uniform exposure at an exposure amount that gave a half density of the maximum density determined from the characteristic curve obtained by measurement, and developed with the following inhibitor developer at 20 ° C. for 6 minutes, and then 3 The development is stopped with an aqueous solution of acetic acid and washed with water. Gelatin is decomposed and removed from this sample using actinase, and only silver halide grains are separated. The position of developed silver on the silver halide grains is observed using a scanning electron microscope. At this time, in order to prevent generation of printout silver, observation at −170 ° C. or lower is preferable.

Black and white developer Metol 2.5 g Ascorbic acid 10 g Nabox 35 g NaCl 0.5 g H ₂ O 1 liter

Suppressing developer Metol 0.1 g Ascorbic acid 0.4 g Nabox 1.4 g NaCl 0.02 g H ₂ O 1 liter

The silver halide emulsion used in the present invention contains various compounds or precursors thereof for the purpose of preventing fog during the production process of the light-sensitive material, storage or photographic processing, or stabilizing photographic performance. Can be added. Specific examples of these compounds are described in JP-A-62-2.
Those described on pages 39 to 72 of the specification of Japanese Patent No. 15272 are preferably used. Further European patent EP 0447
5-arylamino-1,2,
A 3,4-thiatriazole compound (having at least one electron-withdrawing group in the aryl residue) is also preferably used.

The support used in the present invention may be any support which can be coated with a photographic emulsion layer such as glass, paper and plastic film, but a reflection type support is most preferred. The "reflective support" used in the present invention refers to one which enhances the reflectivity to make the dye image formed on the silver halide emulsion layer clear, and such a reflective support is a support. Those coated with a hydrophobic resin containing a light-reflecting substance such as titanium oxide, zinc oxide, calcium carbonate, or calcium sulfate dispersed therein, or those using the hydrophobic resin itself containing a dispersed light-reflecting substance as a support. Is included. For example, polyethylene-coated paper, polyethylene-terephthalate-coated paper, polypropylene-based synthetic paper, a transparent support provided with a reflective layer, or using a reflective substance together,
Examples thereof include glass plates, polyethylene terephthalate, polyester films of cellulose triacetate or cellulose nitrate, polyamide films, polycarbonate films, polystyrene films, vinyl chloride resins and the like. The reflective support used in the present invention is a paper support whose both surfaces are coated with a water resistant resin layer, and it is preferable that at least one of the water resistant resin layers contains white pigment fine particles. The white pigment particles are preferably contained in a density of 12% by weight or more, more preferably 14% by weight or more. As the light-reflecting white pigment particles, it is preferable to sufficiently knead the white pigment in the presence of a surfactant, and it is preferable to use pigment particles whose surfaces are treated with a divalent to tetravalent alcohol. It is preferable that the white pigment fine particles are uniformly dispersed in the reflective layer without forming an aggregate of particles, and the size of the distribution depends on the occupied area ratio (%) (Ri) of the fine particles projected on a unit area. It can be measured and obtained. The variation coefficient of the occupied area ratio (%) can be obtained by the ratio s / R of the standard deviation s of Ri to the average value (R) of Ri. In the present invention, the coefficient of variation of the occupied area ratio (%) of the fine particles of the pigment is preferably 0.15 or less, more preferably 0.12 or less. 0.08 or less is particularly preferable. In the present invention, a support having a surface of diffuse reflection of the second kind is preferably used. The second-class diffuse reflectivity was obtained by giving unevenness to a surface having a mirror surface and dividing it into fine mirror surfaces facing different directions, and dispersing the directions of the divided fine surfaces (mirror surface). Refers to diffuse reflectivity. The unevenness of the surface of the second type diffuse reflection has a three-dimensional average roughness of 0.1 to 2 μm, preferably 0.1
Is about 1.2 μm. The frequency of the surface irregularities has a roughness of 0.
0.1 to 2000 cycles for unevenness of 1 μm or more /
mm is preferable, and more preferably 50 to 600 cycles / mm. Details of such a support are described in JP-A-2-239244.

The light-sensitive material of the present invention is used not only in a printing system using a general negative printer, but also in a non-linear solid laser using a gas laser, a light emitting diode, a semiconductor laser, a semiconductor laser or a semiconductor laser as an excitation light source. It is preferably used for digital scanning exposure using monochromatic high-density light such as a second harmonic generation light source (SHG) combined with an optical crystal. Compact system,
In order to make it inexpensive, it is preferable to use a semiconductor laser, or a second harmonic generation light source (SHG) that is a combination of a semiconductor laser or a solid-state laser and a nonlinear optical crystal. In particular, in order to design an apparatus which is compact, inexpensive, has a long life and high stability, it is preferable to use a semiconductor laser, and it is desirable to use a semiconductor laser as at least one of the exposure light sources. A solid-state laser using a semiconductor laser as an excitation light source or an SHG light source obtained by combining a semiconductor laser and a nonlinear optical crystal can halve the oscillation wavelength of the laser, so that blue light and green light can be obtained. Therefore, the maximum spectral sensitivity of the photosensitive material is normal blue, green,
It is possible to have three areas in red. In order to use a semiconductor laser as a light source in order to make the device inexpensive, highly stable and compact, it is preferable that at least two layers have a spectral sensitivity maximum at 670 nm or more. This is an inexpensive and stable III-V available
This is because the emission wavelength range of group-based semiconductor lasers is currently only in the red to infrared range. On the other hand, in order to favorably express the shade of the red high density portion of the present invention, the blue sensitivity and / or the blue sensitivity contained in the cyan coupler-containing silver halide emulsion layer
Alternatively, it is necessary to have at least one laser emission wavelength range in the wavelength range spectrally sensitized by the green-sensitizing dye. However, at the laboratory level,
The oscillation of II-VI group semiconductor lasers has been confirmed, and it is fully expected that these semiconductor lasers can be stably used at low cost if the manufacturing technology of the semiconductor lasers is developed. In such a case, it becomes less necessary for at least two layers to have a spectral sensitivity maximum at 670 nm or more.

In such scanning exposure, the time for which the silver halide in the light-sensitive material is exposed is the time for exposing a certain minute area. As this minute area, the minimum unit for controlling the light quantity from each digital data is generally used and is called a pixel. Therefore, the exposure time per pixel changes depending on the size of this pixel. The size of this pixel depends on the pixel density and is practically 50 to 2000 dpi. When the exposure time is defined as the time for exposing the pixel size when the pixel density is 400 dpi, the preferable exposure time is 10 ^-4 seconds or less, more preferably 10 ^-6 seconds or less.
In the light-sensitive material according to the present invention, a hydrophilic colloid layer is added in order to prevent irradiation and halation and to improve safety of safelight, etc.
It is preferable to add a dye (in particular, an oxonol dye or a cyanine dye) which can be decolorized by the treatment, which is described on pages 27 to 76 of the specification of 490A2. Some of these water-soluble dyes deteriorate the color separation and safelight safety when the amount used is increased. As the dyes that can be used without deteriorating color separation, water-soluble dyes described in EP0539978A1, JP-A-05-127325 and JP-A-05-127324 are preferable.

In the present invention, a colored layer which can be decolorized by treatment is used instead of the water-soluble dye or in combination with the water-soluble dye. The colored layer that can be decolorized by the processing used may be in direct contact with the emulsion layer, or may be arranged so as to be in contact with an intermediate layer containing a processing color mixture inhibitor such as gelatin or hydroquinone. This colored layer is preferably provided in the lower layer (support side) of the emulsion layer that develops a primary color of the same kind as the colored color. It is possible to install all the colored layers corresponding to each primary color individually, or to selectively install only a part of them. It is also possible to provide a colored layer that is colored corresponding to a plurality of primary color gamuts. The optical reflection density of the colored layer is in the wavelength range used for exposure (from 400 nm to 700 in normal printer exposure).
The optical density value at a wavelength having the highest optical density in the visible light region of nm, the wavelength of the scanning exposure light source used in the case of scanning exposure) is preferably 0.2 or more and 3.0 or less. More preferably, it is 0.5 or more and 2.5 or less, especially 0.
It is preferably 8 or more and 2.0 or less.

A conventionally known method can be applied to form the colored layer. For example, Japanese Patent Laid-Open No. 2-282244-3
The dyes described on page 8 from the upper right column of the page, and JP-A-3-79
No. 31, page 3, upper right column to page 11, lower left column, a method of incorporating a solid fine particle dispersion in a hydrophilic colloid layer, a method of mordanting an anionic dye with a cationic polymer, a method of halogenating the dye Examples thereof include a method of adsorbing to fine particles such as silver and fixing in a layer, a method of using colloidal silver as described in JP-A-1-239544, and the like. As a method for dispersing a fine powder of a pigment in a solid state, for example, a method of containing a fine powder dye which is substantially water-insoluble at least at pH 6 or less, but is substantially an aqueous solution at least at pH 8 or more is disclosed in Japanese Patent Laid-Open No. HEI-2. -30824
No. 4, pages 4-13. Also, for example,
A method of mordanting an anionic dye on a cationic polymer is described in JP-A-2-84637, pages 18 to 26. For the preparation method of colloidal silver as a light absorber, see US Pat. Nos. 2,688,601 and 3,45.
No. 9,563. Among these methods, the method of incorporating a fine powder dye and the method of using colloidal silver are preferable. As the binder or protective colloid that can be used in the light-sensitive material of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can be used alone or together with gelatin. A preferred gelatin has a calcium content of 8
It is preferable to use low calcium gelatin of 00 ppm or less, more preferably 200 ppm or less. Further, in order to prevent various molds and bacteria which propagate in the hydrophilic colloid layer and deteriorate the image, it is preferable to add an antifungal agent as described in JP-A-63-271247.

When the light-sensitive material of the present invention is exposed to a printer, it is preferable to use the band stop filter described in US Pat. No. 4,880,726. As a result, light color mixture is removed, and color reproducibility is significantly improved. The exposed light-sensitive material can be subjected to a conventional color development process, but in the case of the color light-sensitive material of the present invention, it is preferable to perform bleach-fixing after color development for the purpose of rapid processing.
Particularly when the above high silver chloride emulsion is used, the pH of the bleach-fixing solution is preferably about 6.5 or less, more preferably about 6 or less for the purpose of promoting desilvering. Silver halide emulsions and other materials (additives etc.) and photographic constituent layers (layer arrangement etc.) applied to the light-sensitive material according to the present invention, and processing methods and processings applied for processing this light-sensitive material. As additives, the following patent publications, particularly European patent EP 0,35
Those described in the specification of 5,660A2 (JP-A-2-139544) are preferably used.

[0073]

[Table 1]

[0074]

[Table 2]

[0075]

[Table 3]

[0076]

[Table 4]

[0077]

[Table 5]

The cyan, magenta, or yellow coupler is impregnated with a loadable latex polymer (eg, US Pat. No. 4,203,716) in the presence (or absence) of the high boiling organic solvents described in the table above. It is preferable that the polymer is dissolved or dissolved with a water-insoluble polymer and an organic solvent-soluble polymer to be emulsified and dispersed in a hydrophilic colloid aqueous solution. Water-insoluble and organic solvent-soluble polymers that can be preferably used are described in U.S. Pat. No. 4,857,449, columns 7 to 15 and International Publication WO88 / 007.
The homopolymers or copolymers described on pages 12 to 30 of the No. 23 specification can be mentioned. It is more preferable to use a methacrylate-based or acrylamide-based polymer, especially an acrylamide-based polymer in terms of color image stability and the like.

In the light-sensitive material according to the present invention, it is preferable to use a color image storability improving compound as described in European Patent EP 0,277,589A2 together with the coupler of the present invention. It is also preferable to use it in combination with a pyrazoloazole coupler or an acylacetamide type yellow coupler.
That is, the compound and / or the color development treatment in the above-mentioned European Patent Specification which chemically bonds with an aromatic amine-based developing agent remaining after the color development treatment to form a chemically inactive and substantially colorless compound. Use of the compounds in the above-mentioned European patent specification simultaneously or alone to form a chemically inert and substantially colorless compound by chemically bonding with an oxidized product of an aromatic amine type color developing agent which remains afterwards. However, it is preferable to prevent the occurrence of stains and other side effects due to the formation of a coloring dye due to the reaction of the residual color developing agent in the film or the oxidant thereof with the coupler during storage after processing.

Examples of magenta couplers include 5-pyrazolone type magenta couplers as described in the known documents in the above table. Examples of 5-pyrazolone-based magenta couplers include WO92 / 18901 and WO
Arylthio-eliminating 5-pyrazolone-based magenta couplers described in WO92 / 18902 and WO92 / 18903 are preferable in terms of image storability and little change in image quality due to processing. Known pyrazoloazole couplers are used in the present invention. Among them, secondary or tertiary alkyl groups as described in JP-A-61-65245 in view of hue, image stability, color developability and the like. Is a pyrazolotriazole coupler directly linked to the 2, 3 or 6 position of the pyrazolotriazole ring, a pyrazoloazole coupler containing a sulfonamide group in the molecule as described in JP-A-61-65246, Pyrazoloazole couplers having an alkoxyphenyl sulfonamide ballast group as described in JP-A No. 61-147254 and an alkoxy group or aryloxy group at the 6-position as described in EP 226,849A and EP 294,785A. The use of pyrazoloazole couplers with groups is preferred.

As the yellow coupler, known acylacetanilide type couplers are preferably used, but among them, a pivaloylacetanilide type coupler having a halogen atom or an alkoxy group at the ortho position of the anilide ring,
European Patent EP 044969A, JP-A-5-1077
No. 01, JP-A-5-113642 and the like, acylacetanilide type couplers in which the acyl group is a 1-substituted cycloalkanecarbonyl group, European Patent EP-042525.
The malondianilide type couplers described in 52A, EP-0524540A and the like are preferably used. As the method for processing the color light-sensitive material of the present invention, in addition to the methods described in the above table, page 1 of the JP-A-2-207250, lower right column 1
The processing materials and processing methods described in line 9 to page 34, upper right column, line 9 and JP-A-4-97355, page 5, upper left column, line 17 to page 18, lower right column, line 20 are preferable.

[0082]

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 in an amount of 50% by weight to dissolve each coupler. This solution was emulsified and dispersed in 33 g of a 14% gelatin aqueous 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. 0
8 and 0.10. For each size emulsion, 0.3 mol% of silver bromide was locally contained on a part of the surface of grains based on silver chloride. The chemical ripening of this emulsion was carried out by adding a sulfur sensitizer and a gold sensitizer so as to optimize the chemical sensitization. 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 number indicates the coating amount per m ^{2, but} for silver chlorobromide emulsions, it means the amount of silver.)

[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% by weight based on coupler) Trioctyl phosphate (50% by weight based on coupler) Gelatin 5.5 g [Protective layer] Gelatin 2.5 g Polyvinyl alcohol acrylic modified copolymer (modification degree 17%) 0.15 g Liquid paraffin 0.03 g

The structure of the comparative coupler used in this example is shown below. (Refer to the above compound examples for the structure of the coupler of the present invention.)

[0085]

[Chemical formula 22]

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
No. 26 was produced. 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 process) Processing process Temperature Time Color development 35 ℃ 40 seconds Bleach fixing 35 ℃ 60 seconds Water washing 35 ℃ 120 seconds

(Processing solution 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-aminoaminoline 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 iron (III) ethylenediaminetetraacetate ammonium (55.0 g) sodium ethylenediaminetetraacetate 5.0 g water 1000 ml pH 6.70

The red light optical density of the processed sample was measured,
The maximum color density Dmax was determined. Also, the cyan density is 1.0
The yellow density at the point of giving a value was measured with an X-Rite 310 densitometer (made by X-Rite Company). The lower the yellow density, the smaller the secondary absorption and the better the hue.
Next, these samples were irradiated with light for 5 days through a sharp cut filter capable of cutting about 50% at 390 nm under a 200,000 lux Xe 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 residual ratio of the color image is shown in Table A as a percentage when the initial density is set to 100% by evaluating two points of the Dmax area and the low density area showing the color density of ⅕ of Dmax.

[0091]

[Table 6]

As is clear from Table A, Samples 102 to 126 are superior in hue to Sample 101. However, Samples 102 to 104 are significantly inferior to Comparative Sample 101 in light fastness in the low density part. On the other hand, Samples 105 to 1 using the coupler of the present invention in which only the leaving group is changed from the couplers of Samples 102 to 104
It is obvious that 07 has an excellent hue, but the light fastness in the low density part is improved and is almost the same as the residual ratio in the high density part. Samples 108-12
Similar results were obtained for No. 6, and it can be said that the coupler of the present invention is clearly superior in terms of hue and light fastness.

Samples 101 to 126 were exposed and processed in the same manner as above, and then stored for 10 days at 100 ° C. to evaluate the residual ratio of color image at the maximum color density. The results are shown in Table B.

[0094]

[Table 7]

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, 126 has 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 then provided with a gelatin subbing layer containing sodium dodecylbenzenesulfonate, and then various photographic constituent layers were 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 Fifth Layer Coating Liquid 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) 100 g, ultraviolet absorber (UV-2) 100 g Solvent (Solv-2) 250 g, solvent (Solv-4) 250 g And dissolved in 360 ml of ethyl acetate.
An emulsified dispersion C was prepared by emulsifying and dispersing in 2000 g of a 16% gelatin aqueous solution containing 60 ml of sodium dodecylbenzenesulfonate and 10 g of citric acid. On the other hand, silver chlorobromide emulsion C (cubic, 1: 4 of large size emulsion C having an average grain size of 0.50 μm and small size emulsion C of 0.41 μm)
Mixture (silver molar ratio). Coefficients of variation of particle size distribution are 0.09 and 0.11. For each size emulsion, silver bromide 0.1.
8 mol% was locally contained on a part of the grain surface, and the rest was composed of silver halide grains containing silver chloride). In this emulsion, the red sensitizing dyes G and H shown below are silver 1
1.0 × for large emulsion C per mole
10 ^-4 mol and 5.0 × 10 ^-5 mol, small size emulsion C
For 1.2 × 10 ^-4 mol and 6.0 × 1 respectively
0 ^-5 are moles 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.

[0099]

[Table 8]

[0100]

[Table 9]

[0101]

[Table 10]

For the blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer, 1- (5-methylureidophenyl) is used.
-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.

[0103]

[Chemical formula 23]

(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.

[0105]

[Table 11]

[0106]

[Table 12]

[0107]

[Table 13]

[0108]

[Table 14]

[0109]

[Chemical formula 24]

[0110]

[Chemical 25]

[0111]

[Chemical formula 26]

[0112]

[Chemical 27]

[0113]

[Chemical 28]

[0114]

[Chemical 29]

[0115]

Embedded image

The same procedure as in Sample 201 was carried out 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.

Then, continuous processing (running test) was performed using a printer processor PP1820V manufactured by Fuji Photo Film Co., Ltd. in the following processing steps until the tank capacity for color development was doubled. 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 counter-current system from (3) to (1))

The composition of each processing liquid is as follows. [Color developer] [Tank solution] [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 (sulfo) Natoethyl) hydroxylamine 5.0 g 10.0 g Sodium triisopropylnaphthalene (β) sulfone 0.1 g 0.1 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline / 3/2 sulfuric acid / 1 Water salt 5.0 g 11.5 g Add water 1000 ml 1000 ml pH (25 ° C / hydroxy acid Adjusted with potassium and 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 12.5 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] (The tank solution and the replenisher are the same) Sodium chlorinated isocyanurate 0.02 g Deionized water (conductivity 5 μs / cm or less) 1000 ml pH 6.5 Next, for samples 201 to 210 Grayscale exposure with red light using an optical wedge and treatment with the treatment liquid. The color image fastness was evaluated for each sample under the conditions of 100,000 lux Xe light source (5 hours light / 1 hour dark intermittent irradiation) for 14 days and 100 ° 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. Regarding the heat fastness, the change in the amount of coloring in the white background portion was measured by the blue optical density, and is also shown in Table C as ΔDmin.

[0121]

[Table 15]

From Table C, Samples 205 to 210 using the coupler of the present invention are particularly fast to the sample 201 in terms of heat fastness, and particularly fast to the sample 202 in terms of light fastness in the low density part. Further, it can be seen that Samples 203 and 204 are superior in light fastness and thermal stain, and are clearly superior in total performance. Next, samples 201 to 21
In order to investigate the change in photographic performance due to processing variation of 0, the photographic performance when 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 was described as the bleach-fix solution. It was compared with the case where was not added. The evaluation is shown by the change in red light density at a density of 2.0.

[0123]

[Table 16]

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-fixing 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 a photographic light-sensitive material which is excellent in hue, light fastness, heat fastness and stability of photographic properties against processing variations.

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 of Example 2 was changed as follows.

[0126]

[Table 17]

[0127]

[Chemical 31]

The same evaluations as in Example 2 were carried out on the above samples, and a photosensitive material using the coupler of the present invention showed the same hue, light fastness and lightness as those in Example 2.
It was revealed that they are excellent in terms of heat fastness and processing dependence.

Example 4 Samples 401 to 410 were produced 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.

[0130]

[Table 18]

[0131]

Embedded image

The same evaluation as in Example 2 was carried out on the above sample, and it was found that the light-sensitive material using the coupler of the present invention showed the same hue, light fastness and light-sensitive property as in Example 2.
It was revealed that they are excellent in terms of heat fastness and 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.

[0134]

[Chemical 33]

The sample prepared as described above was imagewise exposed and subjected to the developing treatment described in Example 1 of the above-mentioned JP-A-6-3779. After the above treatment, each sample was exposed to 100,000 lux Xe light source (5 hours light / 1 hour dark intermittent irradiation) under 1
The color image fastness was evaluated under conditions of 0 days and 100 ° 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 E.

[0136]

[Table 19]

From Table E, Samples 505 to 510 using the coupler of the present invention have a particularly high heat fastness with respect to Sample 501, and light fastness in the low density part with respect to Samples 502 to 504. It can be seen that the total performance is clearly superior.

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

[0139]

Embedded image

The couplers (14), (8), and
Samples 601 to 605 were prepared in the same manner except that (5), (16), (23) and (28) were replaced with equimolar amounts. Photosensitizer (FWH type,
Light source color temperature 3200K, made by Fuji Photo Film Co., Ltd.
Was subjected to 250 CMS for 1 second for sensitometric exposure, and then the treatment described in Example 1 of JP-A-6-208196 was performed. Also, a cyan coupler used in the third layer of Sample 101 of Example 1 of JP-A-6-118546.

[0141]

Embedded image

The couplers (14), (8), and
Samples 606 to 610 were prepared in the same manner except that (5), (16), (23) or (28) was replaced with an equimolar amount. Each sample was exposed and developed by the method described in Example 4 of JP-A-6-118546 to prepare a color proof. 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 has become clear that

[0143]

According to the present invention, hue, coupling activity,
Excellent in heat fastness and light fastness (especially in the foot), and there is little change in color density caused by changes in processing liquid composition,
It is also possible to provide a silver halide photographic light-sensitive material containing a cyan coupler which is excellent in stability of the coupler itself.

Front Page Continuation (72) Inventor Yasuhiro Yoshioka 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture Fuji Photo Film Co., Ltd.

Claims (3)

[Claims] 1. A silver halide color photographic light-sensitive material characterized in that at least one layer on a support contains a cyan coupler represented by the following general formula (I). Embedded image (Wherein, Za is -C (R ₃₎ = or represents -N =,
When Za is -N =, Zb is -C (R ₃₎ = represents, Zb when Za is -C (R ₃₎ = a 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. Q represents a group of non-metal atoms necessary for forming an unsaturated carbocycle or a heterocycle. The non-metal atomic group forming Q may be further substituted with a substituent. ) 2. Za in the general formula (I) is —N.
= Represents, Zb is -C (R ³⁾ = represents, R ³ is a silver halide color photographic material as claimed in claim 1, characterized by containing a coupler which is an aliphatic group or an aryl group. 3. The coupler according to claim 1, wherein the unsaturated carbocycle represented by Q in the above general formula (I) contains a substituted or unsubstituted benzene ring or a naphthalene ring. Silver halide color photographic light-sensitive material.