JPH08110622A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE: To enhance hue and coupling activity and the fastness of a part low in color development density and to reduce the fluctuation of a color develop ment density due to the fluctuation of the composition of a processing solution. CONSTITUTION: Couplers to be contained are represented by formula I or II in which when Za is -N=, Zb is -C(R3 )=, and when Za is -C(R3 )=, Zb is -N=; each of Ra and Rc is a substituent; each of Rb and Rd is an H atom or a substituent; Z is a 5-∼8 membered ring; each of R2 and R'2 is a substituent; (n) is 1 or 2; and X is H atom or a releasable group.

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 silver halide color light-sensitive materials,
Using the exposed silver halide as an oxidizing agent, the oxidized aromatic primary amine-based color developing agent and the coupler react to give indophenol, indoaniline, indamine,
It is well known that azomethine, phenoxazine, phenazine and dyes related thereto are formed and color images are 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 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. Pyrroloazoles described in European Patent Publication Nos. 491197A1, 488248, and 545,300 have been proposed as couplers that overcome these problems. These couplers are excellent in hue and coupling activity. However, the dyes produced from the couplers described in these patents have a problem that the color density is changed due to the change in the composition of the processing solution, which is caused by the thiosulfate ion in the processing solution especially by continuous processing. It was a phenomenon that appeared remarkably when the concentration of sulphite and sulphite varied. Further, also in terms of the fastness of the dye image after processing, the fastness of the portion giving a relatively low color density is inferior to that of the high color density portion, and practical improvement is desired.

[0004]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a pyrrolotriazole type cyan coupler excellent in hue and coupling activity, in which the fluctuation of the color density caused by the fluctuation of the composition of the processing liquid is small and the low color density part is low. Another object of the present invention is to provide a silver halide color light-sensitive material containing a cyan coupler having improved fastness.

[0005]

Means for Solving the Problems The present inventors have made diligent studies on a pyrrolotriazole-based coupler,
It has been found that the object of the present invention can be achieved by the following means. That is, it was 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) or (II).

[0006]

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(In the formula, Za is -C (R ₃ ) = or-
When N = represents and Za represents -N =, Zb represents -C.
(R ₃ ) = represents, when Za represents -C (R ₃ ) =, Zb represents -N =. R ₃ represents a substituent. R
a and Rc each represent a substituent, and Rb and Rd
Each represent a hydrogen atom or a substituent, and Z represents a non-metal atom group necessary for forming a saturated or unsaturated 5- to 8-membered ring. X represents a hydrogen atom or a group capable of leaving by a coupling reaction with an oxidized product of a color developing agent. R ₂ and R ₂ ′ each represent a substituent and may be bonded to each other to form a ring. n represents an integer value of 1 or 2. )

The present invention will be described in detail below. In the present invention, Zb represents -C especially Za is in -N = (R ₃₎
A coupler represented by = is preferred.

Each substituent will be described in detail below. R ₃ is a halogen atom (eg, fluorine atom, chlorine atom, bromine atom), an aliphatic group (eg, having 1 to 32 carbon atoms).
A linear or branched alkyl group, aralkyl group, alkenyl group, alkynyl group, cycloalkyl group, cycloalkenyl group of, 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), 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), an 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), C1-C32
Alkylamino group (eg, methylamino, butylamino, dodecylamino, diethylamino, methylbutylamino), an anilino group having 6 to 36 carbon atoms (eg, phenylamino, 2-chloroanilino, 2-chloro-5-tetradecaneaminoani). Rino, 2-chloro-5-dodecyloxycarbonylanilino, N-acetylanilino, 2
-Chloro-5- {2- (3-t-butyl-4-hydroxyphenoxy) dodecanamide} anilino), carbon number 2
To 32 ureido groups (for example, phenylureido, methylureido, N, N-dibutylureido), and carbon atoms of 1 to
32 sulfamoylamino group (eg, N, N-dipropylsulfamoylamino, N-methyl-N-decylsulfamoylamino), an alkylthio group having 1 to 32 carbon atoms (eg, methylthio, octylthio, tetradecyl) Thio, 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 (for example, methoxycarbonylamino, tetradecyloxycarbonyl). Amino), a sulfonamide group having 1 to 32 carbon atoms (for example,
Methanesulfonamide, butanesulfonamide, octanesulfonamide, hexadecanesulfonamide, benzenesulfonamide, p-toluenesulfonamide, octadecanesulfonamide, 2-methoxy-5-t-butylbenzenesulfonamide), having 1 to 36 carbon atoms Carbamoyl group (for example, N-ethylcarbamoyl, N, N
-Dibutylcarbamoyl, N- (2-dodecyloxyethyl) carbamoyl, N-methyl-N-dodecylcarbamoyl, N- {3- (2,4-di-t-amylphenoxy) propyl} carbamoyl), 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), a hetero group having 6 to 36 carbon atoms. Ring oxy group (for example, 1-phenyltetrazole-5-oxy, 2-tetrahydropyranyloxy), carbon number 6 to
36 azo groups (for example, phenylazo, 4-mexoxyphenylazo, 4-pivaloylaminophenylazo, 2-hydroxy-4-propanoylphenylazo), 2 carbon atoms
To 32 acyloxy groups (eg acetoxy), C1 to C2 carbamoyloxy groups (eg N-methylcarbamoyloxy, N-phenylcarbamoyloxy), C3 to C36 silyloxy groups (eg trimethylsilyloxy, Dibutylmethylsilyloxy),
Aryloxycarbonylamino group having 7 to 36 carbon atoms (for example, phenoxycarbonylamino), 1 to 1 carbon atoms
32 imide group (for example, N-succinimide, N-phthalimide, 3-octadecenylsuccinimide), a heterocyclic thio group having 6 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 32 carbon atoms (for example, dodecanesulfinyl, 3-pentadecylphenylsulfinyl, 3-phenoxypropylsulfinyl), phosphonyl group having 3 to 36 carbon atoms (for example, Phenoxyphosphonyl, octyloxyphosphonyl, phenylphosphonyl), 7 carbon atoms
36 aryloxycarbonyl group (for example, phenoxycarbonyl), an acyl group having 2 to 32 carbon atoms (for example,
Acetyl, 3-phenylpropanoyl, benzoyl, 4
-Dodecyloxybenzoyl) and an azolyl group having 1 to 32 carbon atoms (for example, 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.

X represents a hydrogen atom or a group which leaves when the coupler reacts with an oxidation product of an aromatic primary amine color developing agent, and when X represents a leaving group, the leaving group is a halogen atom. Atom, aryloxy group, alkyl or heterocyclic acyloxy group, alkylaryl or heterocyclic sulfonyloxy group, dialkyl or diarylphosphonooxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, heterocyclic oxycarbonyloxy group, carbamoyl Oxy group, alkyl / aryl or heterocyclic sulfonyl group, alkyl / aryl or heterocyclic sulfinyl group, alkyl /
Examples thereof include an aryl or heterocyclic thio group, an imide group, an azo group, and a 5- or 6-membered nitrogen-containing heterocyclic group bonded to the coupling position at a nitrogen atom. The alkyl moiety, aryl moiety or heterocyclic moiety contained in these leaving groups may be substituted with the substituents listed for R ₃ , and when these substituents are two or more, they may be the same or different. Of course, these substituents may have the substituents listed for R ₃ .

Specific examples of the leaving group include the following.
Fluorine atom, chlorine atom, bromine atom, aryloxy group having 6 to 30 carbon atoms (for example, 4-methylphenoxy, 4-
Chlorophenoxy, 4-methoxyphenoxy, 2-methoxyphenoxy, 4-ethoxycarboxyphenoxy,
3-acetylaminophenoxy), an alkyl or heterocyclic acyloxy group having 2 to 30 carbon atoms (for example, acetoxy, tetradecanoyloxy, morpholinocarbonyloxy), an alkyl aryl having 1 to 30 carbon atoms or a heterocyclic sulfonyloxy group ( For example, methanesulfonyloxy, toluenesulfonyloxy), having 1 to 3 carbon atoms
A dialkyl or diarylphosphonooxy group having 0 (eg, diethylphosphonooxy, diphenylphosphonooxy), an alkoxycarbonyloxy group having 2 to 30 carbon atoms (eg, ethoxycarbonyloxy, (i)-
Butoxycarbonyloxy), an aryloxycarbonyloxy group having 7 to 30 carbon atoms (for example, phenoxycarbonyloxy), a carbamoyloxy group having 1 to 30 carbon atoms (for example, diethylcarbamoyloxy), and 1 carbon atom.
To an alkyl-aryl or heterocyclic sulfonyl group (for example, methanesulfonyloxy, toluenesulfonyloxy), a C1-C30 alkyl aryl or heterocyclic sulfinyl group (for example, phenylsulfinyl), a C1-C30 Alkyl / aryl or heterocyclic thio groups (eg ethylthio, 2-butoxy-
5-t-octylphenylthio, tetrazolylthio),
Examples thereof include imidazolyl, pyrazolyl, triazolyl, 2-dihydro-2-oxo-1-pyridyl, phenylazo and 4-methoxyphenylazo. The leaving group may contain a photographically useful group such as a development inhibitor or a development accelerator.

Preferred X is a hydrogen atom, a halogen atom,
It is an aryloxy group, a heterocyclic acyloxy group, a dialkylphosphonooxy group, an arylsulfonyloxy group, an alkoxycarbonyloxy group or a carbamoyloxy group.

In the formula, Ra and Rc represent a substituent, and R
b and Rd represent a hydrogen atom or a substituent, Ra,
Examples of the substituent for Rb, Rc, and Rd include the substituent for R ₃ , and among them, an aliphatic group having 1 to 20 carbon atoms is preferable, and examples thereof include methyl, ethyl, propyl, i-propyl, butyl, sec-butyl, Particularly preferred is t-butyl, octyl, cyclohexyl. Z represents a group of non-metal atoms necessary for forming a 5- to 8-membered ring, and the non-metal atom is preferably a nitrogen atom, an oxygen atom, a sulfur atom or a carbon atom, and more preferably a carbon atom. Is an atom. The ring formed by Z is preferably a saturated or unsaturated 5-membered or 6-membered ring, and more preferably substituted cyclohexane or benzene. Z
The ring formed by may have a substituent, and examples of the substituent include the examples of R ₃ . In the present invention, in the general formula (I), Za is -N = and Zb is -C.
(R ₃ ) = and Ra and Rc each have 1 to 1 carbon atoms.
Particularly preferred is an aliphatic group of 20, Rb and Rd are hydrogen atoms, and Z represents an atomic group forming a saturated or unsaturated 5- to 8-membered hydrocarbon ring.

R ₂ and R ₂ ′ represent a substituent, and examples of the substituent in R ₃ include: Examples of preferable substituents include an aliphatic group, an aryl group and a heterocyclic group. Specifically, the aliphatic group is preferably a linear or branched alkyl group having 1 to 36 carbon atoms, an aralkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group or a cycloalkenyl group, and examples thereof include methyl, propyl, butyl, Hexyl, octyl, decyl, 2-ethoxyethyl, 2-ethyl-hexyl, cyclohexyl, cyclohexenyl, cycloheptyl, cyclooctyl can be mentioned.

The aryl group is preferably a substituted or unsubstituted monocyclic or condensed ring having 6 to 36 carbon atoms, and examples of the aryl group include phenyl, naphthyl, 4-t-butylphenyl and 2,4-diphenyl. -T-amylphenyl, 2,6
-Dimethylphenyl, 2-tetradecanamidophenyl, 2- (2,4-di-t-amylphenoxyacetamido) phenyl, 2-acetamidophenyl.

The heterocyclic group includes a nitrogen atom, an oxygen atom and a sulfur atom as a hetero atom forming a ring.
The number of ring members is preferably 5 to 8 members. Examples of the heterocyclic group include, for example, 2-pyridyl, 3- (2,4-di-t
-Amylphenoxyacetamido) pyridyl, 2-pyrimidinyl, 2-benzoxazolyl, 2-benzothiazolyl, 2-furyl, 2-cenyl. Also,
R ₂ and R ₂ ′ may combine with each other to form a ring.
When R ₂ and R ₂ ′ form a ring, it is preferably a 5- to 8-membered ring, and these rings may be substituted with a substituent or may be a saturated ring having an unsaturated bond. Good. The number of ring members is preferably 5 or 6 members.

R ₂ and R ₂ ′ are preferably an aliphatic group or an aryl group.

[0019] In general formula (II) in the present invention, Za is -N =, Zb is -C (R ₃₎ a =, R ₂ and R ₂ 'is an aliphatic group or an aryl group, respectively ( R ₂
And R ₂ ′ may combine with each other to form a ring. ), N
Is particularly preferred.

The coupler represented by the general formula (I) or (II) is a dimer or more dimer containing a coupler residue represented by the formula (I) or (II) in the R ₃ group. It may form a multimer, or the group of R ₃ may contain a polymer chain to form a homopolymer or a copolymer. The homopolymer or copolymer containing a polymer chain is represented by the general formula (I)
A typical example is a homopolymer or copolymer of an addition polymer ethylenically unsaturated compound having a coupler residue represented by
In this case, one or more kinds of cyan color-forming repeating units having a coupler residue represented by the general formula (I) or (II) may be contained in the polymer, and an acrylic acid ester or a methacrylic 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 and maleic acid esters. Specific examples of the coupler of the present invention are shown below, but the present invention is not limited thereto.

[0021]

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[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]

The intermediate of the compound of the present invention can be synthesized by a known method. J. Chem. Soc.,
5149 (1962), J. Amer. Chem., 81,
2452 (1959) and Heterocyclic., 27,
2301 (1988), IZV. Akad, Nauk SSSR, Se
r. Khim., p. 582 (1970), etc.,
It can be synthesized by the literature cited therein or a similar method. That is, from the general formula (V) which can be synthesized according to the above-mentioned literature, the intermediate general formulas (V) to (IIIV) of the compound of the present invention can be synthesized according to the following route.

[0031]

[Chemical 12]

In the general formula, Ra to Rd, R ₂ ,
R ₂ 'and R ₃ have the same meanings as in formulas (I) and (II). 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.

[0033]

[Chemical 13]

Synthesis of Compound (d) A solution of 33.5 g of iron, 2.1 g of ammonium chloride in 160 ml of isopropanol and 10 ml of water was heated under reflux for 30 minutes, and then 16 g of compound (b) was slowly added under reflux,
Reflux for an additional 2 hours. After the reaction, the mixture was filtered to remove iron, 200 ml of ethyl acetate was added to the filtrate, and the mixture was washed with water. The ethyl acetate layer was dried over magnesium sulfate and then evaporated under reduced pressure. To the residue was added 75 ml of dimethylacetamide and 75 ml of ethyl acetate, and 13.5 g of (A) was added. After stirring at room temperature for 2 hours, 200 ml of ethyl acetate was added and the mixture was washed with water. After drying the ethyl acetate layer with magnesium sulfate,
Ethyl acetate was distilled off under reduced pressure to obtain compound (d).

Synthesis of Compound (e) Tequilahydrofuran 200 of Crude Compound (d) (18g)
Pyridinium bromide perbromide (12.7 g, 40 mmol) was added to the ml 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 (e) (20 g). The crude compound (e) (20 g) was used in the next step without purification.

Synthesis of Compound (f) 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). Crude compound (e) (20 g)
Solution in 100 ml of tetrahydrofuran 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 obtained residue was purified by column chromatography to obtain 12.5 g of compound (f).

Synthesis of Compound (g) A solution of the compound (g) (12.1 g, 16.5 mmol) in 100 ml of methanol was added with 50 g of sodium hydroxide in 50 ml of water.
ml 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. The compound (g) (10.7 g, 92%) was obtained by filtering and drying the crystal.

Synthesis of Compound (1) Morpholinocarbonyl chloride (4.0 g, 28.4 mmol) was added to a solution of the compound (g) (10.7 g, 14.2 mmol) in 110 ml of pyridine at 0 ° C. 0 ° C
After stirring for 1 hour at room temperature, 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. The residue obtained was purified by column chromatography to obtain 9.1 g of the desired exemplary compound (1). (Yield 80
%)

Synthesis Example 2. Synthesis of Exemplified Compound 15 Up to compound (h) was synthesized by the same method as in Synthesis Example 1.

[0040]

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Diethylaminocarbonyl chloride (2.7 g, 20.2 mmol) was added to a solution of the compound (h) (7.9 g, 10.1 mmol) in 70 ml of pyridine 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. Washing the organic phase with water and brine,
After drying over sodium sulfate, the solvent was distilled off. The residue obtained was purified by column chromatography to obtain 6.2 g of the desired Exemplified Compound (15).
(Yield 78%)

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

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

As the high-boiling organic solvent which can be used in the above-mentioned 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 (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 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 additives applied to process the light-sensitive material. European Patent EP
0,355,660 A2, JP-A-5-34889,
No. 4-359249, No. 4-313753, No. 4-
270344, 5-66527, 5-3454.
No. 8, No. 4-145433, No. 2-854, No. 1-
158431, 2-90145, 3-1945.
No. 39, No. 2-93641, No. 6-43611, No. 6-3779, No. 6-208196, No. 6-118.
The silver halide color photographic light-sensitive material and its processing method described in, for example, 546 and European Patent EP 0520457A2 are also preferable.

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

[0048]

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

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

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

[0051]

[Chemical 15]

Sample 101 was prepared in the same manner as sample 101 except that the cyan coupler was replaced by 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
10 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 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

[Bleaching 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 Next, each sample was subjected to gradation exposure through a color separation filter using the sensitometer, and color development processing was performed using the liquid after the continuous processing. The following evaluations were performed on these samples.

Evaluation 1. Hue (Y / C): In the cyan color-forming layer, the yellow density at a point giving a cyan density of 1.0 is measured by an X-Rite 310 densitometer (X-Rite Comp).
(manufactured by any). The lower the yellow density, the smaller the secondary absorption and the better the hue. Evaluation 2. Changes in color density due to changes in Blix solution composition: In the processing solution after the above continuous processing, a bleach-fix solution having a tank solution composition before continuous processing and a composition having an ammonium thiosulfate content and an ammonium sulfite content doubled Two
Treated in the street. The decrease in the maximum color density of cyan caused by changing the bleach-fix solution is shown in percentage. Evaluation 3. Image fastness: The treated sample was stored at 100 ° C. for 2 days and at 80 ° C. and 70% relative humidity for 6 days, and the decrease in density before and after storage was measured at an initial density of 0.6. The decrease in concentration is shown as a percentage. Evaluation 4. Color cast: X is the reflection density of cyan in the unexposed area
-Measured with Rite 310 densitometer. Samples 101-11
The evaluation results for 0 are shown in Table A.

[0057]

[Table 1]

Table A shows that according to the present invention, a light-sensitive material excellent in hue and image fastness and in which cyan color cast is suppressed can be obtained.

Example 2 On the surface of a paper support laminated on both sides with polyethylene, a corona discharge treatment was applied, and then a gelatin subbing layer containing sodium dodecylbenzenesulfonate was provided, and various photographic constituent layers were further coated. 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 310 g of cyan coupler (ExC), color image stabilizer (Cp
d-1) 100 g, color image stabilizer (Cpd-5) 100
g, color image stabilizer (Cpd-6) 10 g, color image stabilizer (C
pd-8) 10 g, color image stabilizer (Cpd-9) 100
g, color image stabilizer (Cpd-10) 100 g, ultraviolet absorber (UV-2) 100 g, solvent (Solv-2) 250
g, dissolved in 250 g of solvent (Solv-4) and 360 ml of ethyl acetate, and emulsified and dispersed in 2000 g of 16% gelatin aqueous solution containing 60 ml of 10% sodium dodecylbenzenesulfonate and 10 g of citric acid to prepare Emulsion Dispersion C. did. 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 and 0.11, respectively. For 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 containing silver chloride. . In this emulsion, the red sensitizing dyes G and H shown below were respectively added to the large-sized emulsion C per mol of silver in an amount of 1.0 × 1.
0 ^-4 , 5.0 x 10 ^-5 mol, and to the small size emulsion C, 1.2 x 10 ^-4 and 6.0 x 10 ^-5 mol, 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 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.

[0063]

[Table 2]

[0064]

[Table 3]

[0065]

[Table 4]

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 to prevent irradiation.

[0067]

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.

[0069]

[Table 5]

[0070]

[Table 6]

[0071]

[Table 7]

[0072]

[Table 8]

[0073]

[Chemical 17]

[0074]

Embedded image

[0075]

[Chemical 19]

[0076]

Embedded image

[0077]

[Chemical 21]

[0078]

[Chemical formula 22]

[0079]

[Chemical formula 23]

A sample was prepared in the same manner as in sample 201 except that the cyan coupler shown in Table B was replaced with 1/2 mol amount of sample 201 and the coating amount of silver halide emulsion was reduced to 1/2. 202-210 were produced.

[0081]

[Table 9]

First, as a sample 201, a sensitometer (FWH type manufactured by Fuji Photo Film Co., Ltd., color of light source, temperature of 3200 °) was used.
About 35% of the coated silver amount was developed using K) and exposed so as to give a gray color.

Thereafter, continuous processing (running test) was carried out using a printer processor PP1820V manufactured by Fuji Photo Film Co., Ltd. until the tank capacity for color development was replenished by twice in the following processing steps. Processing 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) sulfonate 0.1 g 0.1 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline / 3/2 sulfuric acid・ 1 hydrate 5.0g 11.5g Add water 1000ml 1000ml pH (25 ℃ / potassium hydroxide and sulfur At adjustment) 10.00 11.00

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

[Rinse Solution] [The same as the tank solution and the replenisher solution] Sodium chlorinated isocyanurate 0.02 g Deionized water (conductivity of 5 μs / cm or less) 1000 ml pH 6.5 Using Samples 201 to 210, Example 1 It was confirmed that the sample of the present invention was excellent in hue and image fastness and had low cyan color fog due to the treatment.

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,
The couplers C-1, C-2 and C-3 of 5 and 6 layers are replaced by the couplers (1), (2), (4), (8), (14),
(18) Samples 302 to 307 were prepared in exactly the same manner as the sample 301 except that it was replaced with an equimolar amount.

[0088]

[Chemical formula 24]

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.

Further, Example 1 of JP-A-6-208196
Cyan coupler used in the second and third layers of Sample 101 of

[0091]

[Chemical 25]

An equimolar amount of coupler (1) of the invention,
Samples 308 to 313 were prepared in the same manner, except that they were replaced with (2), (4), (8), (14) or (18). Each sample was exposed to 250 CMS for 1 second for sensitometry using a sensitometer (FWH type, color temperature of light source: 3200K, manufactured by Fuji Photo Film Co., Ltd.) through an optical wedge, and then exposed to Japanese Patent Application Laid-Open No. 6-58242. No.-208196 The treatment described in Example 1 was performed.

A cyan coupler used in the third layer of Sample 101 of Example 1 of JP-A-6-118546.

[0094]

[Chemical formula 26]

Is an equimolar amount of coupler (1) of the present invention,
Samples 314 to 319 were prepared in the same manner, except that (2), (4), (8), (14) or (18) was substituted. Each sample was exposed and developed by the method described in Example 4 of JP-A-6-118546 to prepare a color proof. When each sample was evaluated in the same manner, it was confirmed that the sample of the present invention was excellent in hue and image fastness and had low cyan color fog due to processing.

[0096]

According to the present invention, the hue and the image fastness are excellent, and the cyan color fog due to the processing can be reduced.

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) or (II). Embedded image (Wherein, Za is -C (R ₃₎ = or represents -N =, when the Za represents -N =, Zb is -C (R ₃₎ =
The stands, when Za is -C (R ₃₎ = represent, Zb represents -N =. R ₃ represents a substituent. Ra and Rc
Each represents a substituent, Rb and Rd each represent a hydrogen atom or a substituent, and Z represents a group of non-metal atoms necessary for forming a saturated or unsaturated 5- to 8-membered ring. X represents a hydrogen atom or a group capable of leaving by a coupling reaction with an oxidized product of a color developing agent. R ₂ and R ₂ ′ each represent a substituent and may be bonded to each other to form a ring. n represents an integer value of 1 or 2. )