JPH06258794A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain the silver halide color photographic sensitive material which is improved in the light resistance of a dye image and excellent in a dye preservable property and a color developing property by incorporating at least one of specified magenta coupler. CONSTITUTION:At least one magenta coupler expressed by formula I and II is incorporated. In formula I, R1-R3 is a substd. group, L is an alkylene group, R4 is an aliphat. group, X1 is hydrogen atom or a group capable of leaving by the reaction with the oxide of a coloring developing agent. In formula II, R<1> is hydrogen atom or a substd. group, R<2> and R<3> is a substd. group, R<4> is a substd. group and the substd. group is incorporated at least one -COOM or -SO3M, M is hydrogen atom or a cation, X<1> is hydrogen atom or a group capable of leaving by the reaction with the oxide of the coloring developing agent. There is no limitation as the substd. group expressed by R1-R3 in formula I, the substd. group such as alkyl, aryl, anilino, acylamino, sulfonamide, alkylthio and arylthio group is exemplified typically.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide color photographic light-sensitive material containing a magenta coupler, and more specifically, it contains a novel pyrazolotriazole-based magenta coupler so that the coloring property is excellent, The present invention relates to a silver halide color photographic light-sensitive material capable of obtaining a dye image stable to light (especially light).

[0002]

2. Description of the Related Art It is desirable that a dye image obtained from a silver halide color photographic light-sensitive material should not be discolored even if it is exposed to light for a long time or stored at high temperature and high humidity. It is desired that the uncolored portion of the silver color photographic light-sensitive material does not turn yellow (hereinafter referred to as Y-stain) due to light or wet heat.

Known examples of magenta dye image forming couplers include 5-pyrazolone type, pyrazolotriazole type, imidazopyrazole type, pyrazolopyrazole type, pyrazolotetrazole type, pyrazolobenzimidazole type and indazolone type couplers. There is.

However, in the case of magenta couplers,
Y-stain due to wet heat in the uncolored portion and fading due to light in the dye image portion are extremely large and often cause problems as compared with the yellow coupler and the cyan coupler.

Widely used couplers for forming magenta dyes are the 5-pyrazolones. The dye formed from this 5-pyrazolone magenta coupler is 55
In addition to the main absorption around 0 nm, it is a big problem to have a secondary absorption around 430 nm, and various studies have been made to solve this problem.

Magenta couplers having an anilino group at the 3-position of 5-pyrazolones described in, for example, US Pat. No. 2,343,703 and British Patent No. 1,059,949 have a small amount of the above-mentioned sub-absorption and are particularly useful for obtaining a color image for printing. Useful for.

However, the above-mentioned magenta coupler has a drawback that the image storability, particularly the fastness of a dye image to light, is extremely poor, and the Y-stain in the uncolored portion is large.

As another means for reducing the side absorption near 430 nm of the above magenta coupler, British Patent No.
Pyrazolobenzimidazoles described in 1,047,612, indazolones described in U.S. Pat.No. 3,770,447, or 3,725,067, British Patent 1,252,418, 1,
1H-pyrazolo [5,1-c] -1,2,4-triazole couplers described in 334,515, 1H-pyrazolo [1 described in JP-A-59-171956, Research Disclosure No. 24,531. ,Five
-b] -1,2,4-Triazole type coupler, 1H-pyrazolo [5,1- described in Research Disclosure No. 24,626
c] -1,2,3-triazole type coupler, JP-A-59-162548
Issue, Research Disclosure No. 24, 531
1H-imidazo [1,2-b] pyrazole type coupler, JP-A-60
-43659, 1H-pyrazolo [1,5-b] pyrazole type couplers described in Research Disclosure Nos. 24 and 230, JP-A-60-33552, Research Disclosure No. 2
Magenta couplers such as 1H-pyrazolo [1,5-d] tetrazole type couplers described in 4,220 have been proposed. Among these, 1H-pyrazolo [5,1-c] -1,2,4-triazole type couplers, 1H-pyrazolo [1,5-b] -1,2,4-triazole type couplers, 1H-pyrazolo [ 5,1-c] -1,2,3-triazole type coupler, 1H-imidazo [1,2-b] pyrazole type coupler, 1H-pyrazolo [1,5-d] pyrazole type coupler and 1H
-Dyes formed from pyrazolo [1,5-d] tetrazole type couplers have a significantly smaller side absorption near 430 nm than dyes formed from 5-pyrazolones having an anilino group at the 3-position described above, and thus color This is preferable in terms of reproduction, and further, Y-stain generation in the uncolored portion against heat and humidity is extremely small, which is a preferable advantage.

However, the fastness to light of the azomethine dyes formed from these couplers is remarkably low, and in addition, the dyes are prone to discoloration by light, particularly impairing the performance of print silver halide color photographic light-sensitive materials. It was a thing.

To this end, many improved techniques have been proposed. For example, JP-A-56-159644 and 59-125732.
Nos. 61-145552, 60-262159, 61-90155, and phenol or phenyl ether compounds described in JP-A-3-39956, JP-A-61-73152, JP-A-61-72246.
No. 61-189539, No. 61-189540, No. 63-95439, and the like amine compounds, JP-A-61-140941, No. 61-
Examples thereof include the metal complexes described in 145554, 61-158329, 62-183459, etc., and the inclusion compounds, heterocyclic compounds, etc. described in JP-A No. 2-100048 and the like. However, when these compounds are used, the color density of the coupler is lowered, color contamination occurs during storage over time, color contamination occurs due to coloring of the added compound itself, and an undesirable change in color tone is caused. Or, the dispersibility of the dispersion containing the coupler may deteriorate, and the stability over time may deteriorate. Further, the above-mentioned improved technique shows a great effect in improving the light resistance, but the light resistance of the magenta dye is nevertheless improved. Is currently inferior to the light resistance of yellow dyes and cyan dyes, and as a result, the color balance of the image is disrupted during the fading process, causing the colors of the photograph to shift toward yellow and cyan, causing unnatural discoloration. There is a problem that it ends up. Further, JP-A-61-65245, 61-120146, 61-12
0147, 61-120148, 61-120149, 61-120150
6-position of 1H-pyrazolo [5,1-c] -1,2,4-triazole and 1H-pyrazolo [5,1-b] -1,2,4-triazole described in No. A coupler in which a secondary or tertiary bulky alkyl group is introduced (adjacent to the position), the light resistance is significantly improved as the 6-position substituent is bulky in any mother nucleus, but on the other hand, color development Sex, especially
In the 1H-pyrazolo [5,1-b] -1,2,4-triazole nucleus,
It was found that the effect was significant.

Therefore, as a result of further research on the above points, the present inventor has found that 1H-pyrazolo [5,1-b] -1,2,4-triazole having high light fastness without impairing color development. The present invention was completed by discovering a system coupler.

[0012]

SUMMARY OF THE INVENTION A first object of the present invention is to provide a silver halide color photographic light-sensitive material which improves the light resistance of a dye image and is excellent in image storability.
A second object of the present invention is to provide a silver halide color photographic light-sensitive material excellent in color developability.

[0013]

The above objects of the present invention are achieved by the following silver halide color photographic light-sensitive materials.

(1) A silver halide color photographic light-sensitive material containing at least one magenta coupler represented by the general formula [MA] "Chemical formula 1".

(2) A silver halide color photographic light-sensitive material containing at least one magenta coupler represented by the general formula [MB] "Chemical Formula 2".

The present invention will be described in more detail below.

In the above general formula [MA], the substituents represented by R ₁ , R ₂ and R ₃ are not particularly limited, but are typically alkyl, aryl, anilino, acylamino, sulfonamide, alkylthio. , Arylthio, alkenyl, cycloalkyl, etc., but also halogen atom and cycloalkenyl, alkynyl, heterocycle, sulfonyl, sulfinyl, phosphonyl,
Acyl, carbamoyl, sulfamoyl, cyano, alkoxy, aryloxy, heterocyclic oxy, siloxy, acyloxy, carbamoyloxy, amino, alkylamino, imide, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, Each group such as aryloxycarbonyl and heterocyclic thio, and a spiro compound residue,
Examples include bridged hydrocarbon compound residues.

The alkyl group represented by R ₁ , R ₂ and R ₃ preferably has 1 to 32 carbon atoms and may be linear or branched.

The aryl group represented by R ₁ , R ₂ and R ₃ is preferably a phenyl group.

Examples of the acylamino group represented by R ₁ , R ₂ and R ₃ include an alkylcarbonylamino group and an arylcarbonylamino group.

Examples of the sulfonamide group represented by R ₁ , R ₂ and R ₃ include an alkylsulfonylamino group and an arylsulfonylamino group.

The alkylthio group represented by R ₁ , R ₂ and R ₃ and the alkyl component and aryl component in the arylthio group include the alkyl group and aryl group represented by R ₁ , R ₂ and R ₃ .

The alkenyl group represented by R ₁ , R ₂ and R ₃ is preferably one having 2 to 32 carbon atoms, and the cycloalkyl group is preferably one having 3 to 12 carbon atoms, particularly 5 to 7 carbon atoms. The group may be linear or branched.

The cycloalkenyl group represented by R ₁ , R ₂ and R ₃ is preferably one having 3 to 12 carbon atoms, particularly 5 to 7 carbon atoms.

The sulfonyl group represented by R ₁ , R ₂ and R ₃ is an alkylsulfonyl group, an arylsulfonyl group, etc .; The sulfinyl group is an alkylsulfinyl group, an arylsulfinyl group, etc .; The phosphonyl group is an alkylphosphonyl group. A nyl group, an alkoxyphosphonyl group,
Aryloxyphosphonyl group, arylphosphonyl group, etc .; Acyl group, alkylcarbonyl group, arylcarbonyl group, etc .; Carbamoyl group, alkylcarbamoyl group, arylcarbamoyl group, etc .; Sulfamoyl group, alkylsulfamoyl group , An arylsulfamoyl group, etc .; an acyloxy group, an alkylcarbonyloxy group, an arylcarbonyloxy group, etc .; a carbamoyloxy group, an alkylcarbamoyloxy group, an arylcarbamoyloxy group, etc .; an ureido group, an alkylureido group, Aryl ureido group, etc .; Sulfamoylamino group, alkylsulfamoylamino group, arylsulfamoylamino group, etc .; Heterocyclic group preferably having 5 to 7 members, specifically 2-furyl group 2-thienyl, 2-pyrimidinyl group, a 2-benzothiazolyl group and the like; preferably those having a 5- to 7-membered heterocyclic ring as a heterocyclic oxy group, for example 3,4,
5,6-tetrahydropyranyl-2-oxy group, 1-phenyltetrazole-5-oxy group, etc .; as a heterocyclic thio group, 5
7 to 7-membered heterocyclic thio groups are preferred, for example, 2-pyridylthio group, 2-benzothiazolylthio group, 2,4-diphenoxy- group.
1,3,5-triazole-6-thio group; as a siloxy group,
Trimethylsiloxy group, triethylsiloxy group, dimethylbutylsiloxy group and the like; imide group, succinimide group, 3-heptadecyl succinimide group, phthalimide group, glutarimide group, etc .; spiro compound residue, spiro compound 3.3] heptan-1-yl, etc .; as the bridged hydrocarbon compound residue, bicyclo [2.2.1] heptan-1-yl,
Tricyclo [3.3.1.1 ³⁷ ] decan-1-yl, 7,7-dimethyl
-Bicyclo [2.2.1] heptan-1-yl and the like can be mentioned.

The groups represented by R ₁ , R ₂ and R ₃ include those having a substituent. In addition, R ₁ and R ₂ , R
₂ and R ₃ and R ₁ and R ₃ may cooperate with each other to form a _3- to 7-membered ring.

The alkylene group represented by L may be branched, linear, or cyclic, and may have a substituent.

The alkylene group represented by L is specifically represented by the following general formula [MA-I].

[0029]

[Chemical 3]

[In the formula, * ¹ represents a connecting position with the pyrazolotriazole ring, and * ² represents a connecting position with the sulfonyl group. R ₅ , R ₆ , R ₇ and R ₈ represent a hydrogen atom or a substituent. n represents an integer from 0 to 20, and when n is 2 or more, a plurality of R ₇ and R ₈ may be the same or different, and a plurality of R ₇ or R ₈ or Any one of a plurality of R ₇ may be condensed with R ₅ to form a 3- to 7-membered ring. The substituents represented by R ₅ , R ₆ , R ₇ and R ₈ have the same meanings as R ₁ , R ₂ and R ₃ described above. n is preferably an integer of 0 to 4, more preferably 1 or 2.

In the general formula [MA], examples of the aliphatic group represented by R ₄ include the alkyl groups, alkenyl groups, cycloalkenyl groups and the like explained for R ₁ , R ₂ and R ₃ , and these are further included. It may have a substituent, and examples of the substituent include the groups described for R ₁ , R ₂ and R ₃ .

Examples of the group represented by X ₁ which can be released by the reaction with the oxidation product of the color developing agent include, for example, a halogen atom (chlorine atom, bromine atom, fluorine atom, etc.) and alkoxy,
Aryloxy, heterocyclic oxy, acyloxy, sulfonyloxy, alkoxycarbonyloxy, aryloxycarbonyloxy, alkyl oxalyloxy, alkoxy oxalyloxy, alkylthio, arylthio, heterocyclic thio, alkyloxythiocarbonylthio,
Examples thereof include acylamino, sulfonamide, a nitrogen-containing heterocycle bonded by an N atom, alkyloxycarbonylamino, aryloxycarbonylamino, carboxyl, and the like, but a halogen atom, particularly a chlorine atom is preferable.

The typical examples of the magenta coupler represented by the general formula [MA] are shown below, but the invention is not limited thereto.

[0034]

[Chemical 4]

[0035]

[Chemical 5]

The synthesis examples of the magenta coupler represented by the general formula [MA] are shown below.

[Synthesis Example] Synthesis of Exemplified Compound MA-3 I) Synthesis Route

[0038]

[Chemical 6]

II) Synthesis of Intermediate 4 To 30.3 g (74.9 mmol) of Intermediate 1 was added 16.3 ml of thionyl chloride, and the mixture was heated under reflux for 2 hours. After completion of the reaction, excess thionyl chloride was distilled off under reduced pressure, and this was dissolved in 100 ml of ethyl acetate, and then cooled to 5 ° C in 29% aqueous ammonia (150 m
It was dripped into l) over about 1 hour. Then, after stirring at room temperature for an additional 1 hour, the precipitated solid is filtered off, washed with water, and the obtained solid is recrystallized using a mixed solvent of 200 ml of tetrahydrofuran and 200 ml of methanol.
29.1 g (72.0 mmol) of an intermediate 3 of white scaly crystals was obtained.

Next, 300 ml of toluene and 9.5 ml of thionyl chloride were added to 26.5 g (65.7 mmol) of intermediate 3, and the mixture was heated under reflux for 2 hours. The reaction solution was cooled to room temperature, 100 ml of water was added, and the solution was neutralized with sodium hydroxide (pH = 8) and then separated, and the solvent toluene was distilled off under reduced pressure. The obtained white solid was recrystallized from 80 ml of acetonitrile to give a white scaly crystal intermediate 4 23.7.
g (64.1 mmol) was obtained.

(The structure was confirmed by ¹ HNMR, FD mass spectrum and IR spectrum.) III) Synthesis of Intermediate 5 To 19.3 g (50.0 mmol) of Intermediate 4 was added 100 ml of ethyl acetate, 150 ml of chloroform and 12.4 g of ethanol. After dissolution, the mixture was cooled in an ice-salt bath to -10 ° C. Hydrogen chloride gas was bubbled in for 2 hours while cooling this solution, and the mixture was further stirred at −2 ° C. or lower for 8 hours. After distilling off the solvent under reduced pressure (18 ° C. or lower), 100 ml of cold ethyl acetate was added to the obtained solid, and the mixture was stirred under ice cooling, and crystals were filtered. Then, the obtained crystals were vacuum dried to obtain 22.0 g (4
7.0 mmol) was obtained.

(Structure was confirmed by ¹ HNMR, FD mass spectrum and IR spectrum.) IV) Synthesis of Intermediate 8 8.5 g (40.2 mmol) of Intermediate 6 was added to 140 ml of acetonitrile.
6.2 ml of triethylamine and 20.7 g of intermediate 5 (44.3 mmo
l) was added and the mixture was stirred at room temperature for 3 hours. The precipitated crystals were separated by filtration and washed with cold acetonitrile to obtain 11.3 g (19.0 mmol) of white crystalline intermediate 7.

Next, to 11.3 g of intermediate 7, 150 ml of methanol,
Hydroxylamine monohydrochloride 1.48 g (21.2 mmol) sodium acetate 1.74 g (21.2 mmol) and water 90 ml were added, and the mixture was heated under reflux for 3 hours. After completion of the reaction, the solvent methanol was distilled off under reduced pressure, the mixture was extracted with ethyl acetate, the ethyl acetate phase was washed with water and dried, and then the solvent was distilled off under reduced pressure to obtain 89.0 g (15.7 mmol) of a pale yellow oily intermediate. ) Got.

(Structure was confirmed by ¹ H NMR, FD mass spectrum and IR spectrum.) V) Synthesis of Exemplified Compound MA-3 Intermediate compound 8 9.0 g (15.7 mmol) was added with N, N-dimethylacetamide 10 ml, acetonitrile 40 ml and Pyridine (1.34 g) was added and the mixture was stirred under ice-cooling, and the solution temperature was adjusted to 5 ° C.
About 2.99 g (15.7 mmol) of toluenesulfonyl chloride
Added over 30 minutes. After stirring the mixture at 5 ° C for 30 minutes and then at room temperature for 2 hours to complete the reaction, 150 ml of methanol
And pyridine (1.34 g) were added, and the mixture was heated under reflux for 5 hours. After cooling the reaction solution to room temperature, the reaction solution was poured into 500 ml of water, and the precipitated solid was collected by filtration. 20 ml of this product in acetonitrile
-By recrystallizing with a mixed solvent of 5 ml of methanol,
5.3 g (9.5 mmol) of MA-3 as white crystals was obtained.

(The structure was confirmed by ¹ H NMR, FD mass spectrum and IR spectrum.) Next, the magenta coupler represented by the general formula [MB] will be described.

In the general formula [MB], R ¹ , R ² , R ³
Examples of the substituent represented by R ⁴ and R ⁴ and specific examples thereof include the same groups as those described for R ₁ , R ₂ and R ₃ in the general formula [MA]. However, R ⁴
In the group represented by at least one carboxyl group,
Sulfonic acid groups or their metal salts, ammonium salts, or cations other than these are contained.

In the general formula [MB], R ¹ , R ² , R ³
And each group represented by R ⁴ includes one having a substituent.

Further, R ¹ and R ² , R ² and R ^3, and R ¹ and R ³
And may be condensed with each other to form a 3- to 7-membered ring.

As the group capable of splitting off by the reaction with the oxidation product of the color developing agent represented by X ¹ in the general formula [MB], the same group and atom as X ₁ described in the general formula [MA] can be mentioned. Can be mentioned.

In the general formula [MB], the cation represented by M is an alkali metal (for example, Na, K, Li).
Etc.), alkaline earth metals (eg Be, Mg, Ca, Ba)
Etc.), Group IIIA (eg B, Al, etc.), rare earth metals (S
c, Y, La, Ce, Nd, etc.), ammonium cations and the like.

The typical examples of the magenta coupler represented by the general formula [MB] are shown below, but the invention is not limited thereto.

[0052]

[Chemical 7]

[0053]

[Chemical 8]

[0054]

[Chemical 9]

[0055]

[Chemical 10]

The synthesis examples of the magenta coupler represented by the general formula [MB] of the present invention are shown below. [Synthesis example]

[0057]

[Chemical 11]

Synthesis of Exemplified Compound MB-16 I) Synthesis of Intermediate 2 4.25 g (15.0 mmol) of Intermediate 1 was dissolved in 50 ml of N, N-dimethylformamide, and the solution was stirred at 3 ° C. under ice cooling. did. Here, 2.00 g of N-chlorosuccinimide (NCS)
(15.0 mmol) was added as a solid little by little over about 30 minutes, and then the mixture was stirred for 30 minutes at 3 ° C. The reaction solution was poured into 300 ml of water, and the precipitated solid was collected by filtration.

The product was recrystallized from ethanol to obtain 24.00 g of a light brown crystalline intermediate 2.

(Structure was confirmed by ¹ H NMR, FD mass spectrum and IR spectrum.) II) Synthesis of Exemplified Compound MB-16 Into 4.00 g (12.6 mmol) of Intermediate 2, 100 ml of ethyl acetate and 4.41 g of Intermediate 3 (12.6). mmol) was added and the mixture was heated under reflux for 3 hours. After the reaction was completed, the reaction solution was cooled to room temperature, and then ethyl acetate was distilled off under reduced pressure to obtain a light brown oily substance. After purification by silica gel column chromatography, by recrystallizing with a mixed solvent of ethyl acetate-hexane,
5.22 g (7.81 mmol) of MB-16 as white crystals was obtained.

(The structure was confirmed by ¹ HNMR, FD mass spectrum and IR spectrum.) The magenta coupler used in the present invention is preferably contained in the silver halide emulsion.
For example, a conventionally known method may be followed. For example, the boiling point of tricresyl phosphate, dibutyl phthalate, etc. is 175
° C or higher high-boiling organic solvent or ethyl acetate, after each of the low-boiling solvents such as butyl propionate alone or as a mixture thereof, the magenta coupler of the present invention alone or in combination, after dissolving, It can be added to a silver halide emulsion after being mixed with an aqueous gelatin solution containing a surfactant and then emulsified with a high speed rotary mixer or a colloid mill.

The coupler of the present invention is usually 1 × 10 ^-3 to 1 mol, preferably 1 × 10 ^-2 to 8 ×, per mol of silver halide.
It can be used in the range of 10 ^-1 mol.

The magenta coupler of the present invention can also be used in combination with other types of couplers.

The couplers of this invention can be used in combination with various image stabilizers. Preferable image stabilizers include phenol compounds, phenyl ether compounds, amine compounds, chelate compounds, and the like. Exemplified compounds GG described on pages 133 to 137 of JP-A No. 62-215272. -1 to GG-54, the exemplified compounds (a-1) to (a- described in JP-A-4-95952, pages 23 to 29)
8), (b-1) to (b-6), (C-1) to (c-
7), IIIa-1 to IIIa-15, IV-1 to IV-22, V-1
To V-10 and VI-1 to VI-5, JP-A-60-262159, No. 11 to
Exemplified Compounds A-1 to A-28 and 61-145 described on page 13
Exemplary compounds PH-1 to P described in No. 552, pages 8 to 10
H-29, exemplary compounds B-1 to B-21 described on pages 6 to 7 of JP-A-1-306846, and exemplary compounds I-1 to I described on pages 10 to 18 of 2-958. -13, I'-1 to I'-8, II-
1 to II-12, II'-1 to II'-21, III-8 to III-14,
IV-1 to IV-24, V-13 to V-17, No. 3-39956 No. 10-11
Exemplified compounds II-1 to II-33 described on page, JP-A 2-16
7543, compounds B-1 to B-65 described on pages 8 to 11;
Exemplified compounds (1) to (120) described on pages 4 to 7 of JP-A-63-95439 may be mentioned.

The amount of the image stabilizer used in combination with the coupler of the present invention is preferably 5 to 400 mol%, and more preferably 10 to 10 mol% based on the pyrazoloazole-based magenta coupler of the present invention. It is 250 mol.

The pyrazoloazole-based magenta coupler of the present invention and the image stabilizer are preferably used in the same layer, but the image stabilizer is used in a layer adjacent to the layer in which the coupler is present. Good.

The silver halide composition preferably used in the present invention is silver chloride, silver chlorobromide or silver chloroiodobromide. Further, it may be a combination mixture such as a mixture of silver chloride and silver bromide.

The silver halide emulsion used in the present invention contains, as silver halide, silver bromide, silver iodobromide, silver iodochloride,
Any of silver chlorobromide, silver chloroiodobromide, silver chloride, and the like used in ordinary silver halide emulsions can be used.

The silver halide grain may be a grain having a uniform silver halide composition distribution within the grain, or a core / shell grain having a different silver halide composition between the inside of the grain and the surface layer.

The silver halide grain may be a grain in which a latent image is mainly formed on the surface, or may be a grain in which a latent image is mainly formed inside the grain.

The silver halide grains may have a regular crystal form such as a cube, octahedron or tetradecahedron,
It may have an irregular crystal shape such as a sphere or a plate. In these grains, any ratio of {100} plane to {111} plane can be used. Further, it may have a composite form of these crystal forms, and particles of various crystal forms may be mixed.

The grain size of silver halide grains is preferably 0.05 to 30 μm, more preferably 0.1 to 20 μm.

The silver halide emulsion having any grain size distribution can be used. An emulsion having a wide grain size distribution (referred to as a polydisperse emulsion) may be used, or an emulsion having a narrow grain size distribution (referred to as a monodisperse emulsion) may be used alone or in combination of several kinds. Further, a polydisperse emulsion and a monodisperse emulsion may be mixed and used. The coupler used in the present invention includes a development inhibitor, a development accelerator, a bleaching accelerator, a developer, a silver halide solvent, a toning agent by coupling with a colored coupler having an effect of color correction and an oxidation product of a developing agent. Included are compounds that release photographically useful fragments such as agents, hardeners, antifoggants, antifoggants, chemical sensitizers, spectral sensitizers and desensitizers. Of these, a so-called DIR compound which releases a development inhibitor with development and improves the sharpness of images and the graininess of images may be used.

In this DIR compound, the one in which the inhibitor is directly bonded to the coupling position and the one in which the inhibitor is bonded to the coupling position via the divalent group, are A compound (referred to as a timing DIR compound) that is bound so as to release the inhibitor by an intramolecular nucleophilic reaction or an intramolecular electron transfer reaction is included. Further, as the inhibitor, one that is diffusible after withdrawal and one that is not so diffusible can be used alone or in combination depending on the application.

A colorless coupler (also referred to as a competing coupler) which undergoes a coupling reaction with an oxidized product of an aromatic primary amine developer but does not form a dye can also be used in combination with the dye-forming coupler.

Examples of yellow couplers preferably used in the present invention include known acylacetanilide type couplers. Among these, benzoylacetanilide compounds and pivaloylacetanilide compounds can be advantageously used.

Examples of cyan couplers preferably used in the present invention include phenol or naphthol type couplers.

Between the emulsion layers of the light-sensitive material (the same color-sensitive layers and / or different color-sensitive layers), the oxidant of the developing agent or the electron transfer agent moves to cause color turbidity or deterioration of sharpness. Also, a color antifoggant can be used to prevent the graininess from being conspicuous.

An image stabilizer which prevents deterioration of a dye image can be used in the light-sensitive material of the present invention. Compounds which can be preferably used are those described in Item VII J of RD17643.

The hydrophilic colloid layers such as the protective layer and the intermediate layer of the light-sensitive material contain a UV inhibitor in order to prevent fogging due to discharge caused by charging of the light-sensitive material due to friction and the like and to prevent deterioration of the image by UV rays. You can leave.

A formalin scavenger can be used in the light-sensitive material in order to prevent deterioration of the magenta dye-forming coupler and the like due to formalin during storage of the light-sensitive material.

The present invention can be preferably applied to a color negative film, a color paper, a color reversal film and the like.

The color photographic light-sensitive material using the coupler of the present invention is subjected to bleaching treatment and fixing treatment after color development.
The bleaching process may be performed simultaneously with the fixing process.

After the fixing process, a washing process is usually performed. Further, a stabilizing treatment may be performed as an alternative to the water washing treatment, or both may be used in combination.

[0085]

EXAMPLES The present invention will now be described based on examples, but the embodiments of the present invention are not limited thereto.

Example 1 A paper support was laminated with polyethylene on one side and polyethylene containing titanium oxide was laminated on the other side. By coating on the side of the contained polyethylene layer, a multilayer silver halide color photographic light-sensitive material sample 101 was prepared.

[0087]

[Table 1]

[0088]

[Table 2]

The coating solution was prepared as follows.

First layer coating liquid 26.7 g of yellow coupler (EY-1), 10.0 g of dye image stabilizer (ST-1), dye image stabilizer (ST-2)
To 6.67 g, stain inhibitor (HQ-1) 0.67 g and high boiling organic solvent (DNP) 6.67 g, ethyl acetate 60 ml was added and dissolved, and this solution was dissolved in 20% surfactant (SU-2) aqueous solution 7
A yellow coupler dispersion was prepared by emulsifying and dispersing 220 ml of a 10% gelatin aqueous solution containing 10 ml using an ultrasonic homogenizer.

This dispersion was mixed with a blue-sensitive silver halide emulsion (containing 8.67 g of silver) shown below, and an irradiation preventing dye (AIY-1) was further added to prepare a coating solution for the first layer.

The coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. Also, as a hardener, the second layer and the fourth layer
(HH-1) was added to the layer and (HH-2) was added to the seventh layer. As the coating aid, surfactants (SU-1), (S
U-3) was added to adjust the surface tension.

The structural formulas of the compounds used in the above layers are shown below.

[0094]

[Chemical 12]

[0095]

[Chemical 13]

[0096]

[Chemical 14]

[0097]

[Chemical 15]

[0098]

[Chemical 16]

[0099]

[Chemical 17]

Blue-sensitive silver halide emulsion (Em-B) Average grain size 0.85 μm, coefficient of variation = 0.07, silver chloride content 99.5
Mol% monodisperse cubic silver chlorobromide emulsion sodium thiosulfate 0.8 mg / mol AgX chloroauric acid 0.5 mg / mol AgX stabilizer STAB-1 6 × 10 ⁻⁴ mol / mol AgX sensitizing dye BS-14 × 10 ^-4 mol / mol AgX sensitizing dye BS-2 1 × 10 ^-4 mol / mol AgX green-sensitive silver halide emulsion (Em-G) average particle size 0.43 μm, coefficient of variation = 0.08, silver chloride content 99.5
Mol% monodisperse cubic silver chlorobromide emulsion Sodium thiosulfate 1.5 mg / mol AgX chloroauric acid 1.0 mg / mol AgX stabilizing agent STAB-1 6 × 10 ^-4 mol / mol AgX sensitizing dye GS-14 × 10 ^-4 mol / mol AgX Red-sensitive silver halide emulsion (Em-R) Average grain size 0.50 μm, coefficient of variation = 0.08, silver chloride content 99.5
Mol% monodisperse cubic silver chlorobromide emulsion Sodium thiosulfate 1.8 mg / mol AgX chloroauric acid 2.0 mg / mol AgX stabilizer STAB-1 6 × 10 ⁻⁴ mol / mol AgX sensitizing dye RS-1 1 × 10 shows the structural formulas of the compounds used in each monodispersed cubic emulsion ^-4 mol / mol AgX.

[0101]

[Chemical 18]

Next, the third layer coupler EM-1 of Sample 101 was used.
Were replaced with equimolar couplers of the present invention shown in Table 3 below, and dye image stabilizers were further replaced as shown in Table 3 to prepare Samples 102 to 128.

The magenta coupler E used for the comparative sample
The structural formulas of M-2, EM-3, and EM-4 are EM described above.
Shown with -1.

The thus-prepared sample was wedge-exposed with green light according to a conventional method, and then processed according to the following processing steps.

Processing process Temperature Time Color development 35.0 ± 0.3 ℃ 45 seconds Bleach fixing 35.0 ± 0.5 ℃ 45 seconds Stabilization 30-34 ℃ 90 seconds Dry 60-80 ℃ 60 seconds Composition of each processing solution is as follows. Show.

The replenishing amount of each processing solution is 80 ml per 1 m ^{2 of} silver halide color photographic light-sensitive material.

Color developer tank solution Replenisher Pure water 800ml 800ml Triethanolamine 10g 18g N, N-diethylhydroxylamine 5g 9g Potassium chloride 2.4g 1-Hydroxyethylidene-1,1-diphosphonic acid 1.0g 1.8g N-ethyl -N-β-Methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate 5.4g 8.2g Optical brightener (4,4'-diaminostilbenesulfonic acid derivative) 1.0g 1.8g Potassium carbonate 27g 27g Water In addition, the total volume is 1 liter,
Adjust the pH to 10.10 and the replenisher to 10.60.

Bleach-fixing solution (tank solution and replenisher are the same) Ethylenediaminetetraacetic acid ammonium ferric dihydrate 60 g Ethylenediaminetetraacetic acid 3 g Ammonium thiosulfate (70% aqueous solution) 100 ml Ammonium sulfite (40% aqueous solution) 27.5 ml Add water Bring the total volume to 1 liter and adjust the pH to 5.7 with potassium carbonate or glacial acetic acid.

Stabilizing liquid (tank liquid and replenishing liquid are the same) 5-chloro-2-methyl-4-isothiazolin-3-one 1.0 g ethylene glycol 1.0 g 1-hydroxyethylidene-1,1-diphosphonic acid 2.0 g ethylenediamine Tetraacetic acid 1.0 g Ammonium hydroxide (20% aqueous solution) 3.0 g Optical brightener (4,4'-diaminostilbene sulfonic acid derivative) 1.5 g Add water to bring the total volume to 1 liter and adjust the pH with sulfuric acid or potassium hydroxide. Adjust to 7.0.

The following evaluations were performed using the sample after the continuous treatment.

<Dmax> The maximum color density was measured.

<Light resistance> The obtained sample was irradiated with a xenon fade meter of 70,000 lux for 320 hours, and the residual ratio (%) of the dye image at the initial density of 1.0 was determined.

The results are shown in Table 3.

[0114]

[Table 3]

As can be seen from Table 3, the coupler 6
Substituents at the primary position are primary (EM-1, sample 101) and secondary (EM
-2, sample 103), third grade (EM-3, sample 105 and EM-
4, sample 107), the color development (Dm
ax) tends to decrease and light resistance tends to improve. However, when the coupler of the present invention is used, even if the 6-position substituent is tertiary (Samples 109, 111, 113, 115, 117, 119, 121), sufficient color development is obtained and the light resistance is also very good. And
It was also found that when the 6-position substituent is secondary (Samples 123, 125, 127), sufficiently good light resistance can be obtained and, at the same time, extremely high color developability is exhibited.

Further, it was found that the coupler of the present invention showed higher light resistance than Sample 101 without using a dye image stabilizer.

Example 2 Sample No. 2 was prepared by replacing the dye image stabilizer of the third layer of Sample No. 101 of Example 1 with the combinations shown in Tables 4 and 5 below.
01-239 were produced. Incidentally, the dye image stabilizer ST-4,
Structural formulas of ST-5 and ST-6 are shown together with ST-3 described above.

The same evaluation as in Example 1 was performed using the obtained sample. The results are shown in Tables 4 and 5.

[0119]

[Table 4]

[0120]

[Table 5]

As is apparent from the table, the magenta coupler of the present invention and the dye image stabilizer ST-3 used in Example 1 were used.
Sample Nos. 221, 224 and 227 using S.
Compared with the sample Nos. 201, 212 and 218 using T-1, both the color development and the light resistance are remarkably improved.

Further, the dye image stabilizer ST-3 was added to ST-
4, sample Nos. 230-232 and 235-containing the magenta coupler of the present invention prepared by changing to ST-5 or ST-6.
237 is also a sample No. combining the comparative coupler and ST-4 to ST-6. It can be seen that as compared with 202 to 204, 207 to 209, and 213 to 215, the color development and the light resistance are excellent.

Further, even in the sample in which the magenta coupler and the two kinds of dye image stabilizers (ST-4, ST-5) are used in combination, the sample using the coupler of the present invention has excellent coloring property and high light fastness. Shows.

[0124]

Industrial Applicability The present invention has an alkyl group containing a sulfonyl group at the 2-position and a tertiary substituent at the 6-position, or a secondary or tertiary substituent at the 6-position and a 2- or 6-position. Having at least one carboxyl group or sulfonic acid group among the substituents
A silver halide color photographic light-sensitive material of the present invention containing a 1H-pyrazolo [1,5-b] -1,2,4-triazole coupler is
It was found that, compared with the conventional one, the light resistance of the dye image was dramatically improved, and the dye image had an excellent image storability and an excellent color development property.

Claims (2)

[Claims] 1. A silver halide color photographic light-sensitive material comprising at least one magenta coupler represented by the following general formula [MA]. [Chemical 1] [In the formula, R ₁ , R ₂ , and R ₃ represent a substituent, and L represents an alkylene group. R ₄ represents an aliphatic group, and X ₁ represents a hydrogen atom or a group capable of splitting off upon reaction with an oxidized product of a color developing agent. ] 2. A silver halide color photographic light-sensitive material containing at least one magenta coupler represented by the following general formula [MB]. [Chemical 2] [Wherein R ¹ represents a hydrogen atom or a substituent, and R ² and R ³
Represents a substituent. R ⁴ represents a substituent, and the substituent contains at least one —COOM or —SO ₃ M. M represents a hydrogen atom or a cation. X ¹ represents a hydrogen atom or a group capable of splitting off upon reaction with an oxidized product of a color developing agent. ]