JPH06258796A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain the silver halide color photographic sensitive material excellent in resistance to light, coloring property, biological preservable property and resistance to swearing 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 is a tertiary alkyl group except tert. butyl group, R2 is a substd. group, X is hydrogen atom or a group capable of leaving by the reaction with the oxide of a coloring developing agent, and the sum total of the carbon atom member of the substd. group expressed by R1, R2 and X is 8 to 20. In formula II, R<1> is a secondary alkyl group or a secondary substd. alkyl group, R<2> is a substd. group, and the sum total of the carbon atom member of the substd. group expressed by R<1> and R<2> is 8 to 20. Further, as the substd. group expressed by R2 in formula I, there is no limitation, and the group such as alkyl, aryl, anilino, acylamino, sulfonamide, alkylthio and arylthio, alkulene and cycroalkyl group is exemplified.

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, by containing a novel pyrazoloazole-based magenta coupler, it is excellent in light resistance and color development. The present invention relates to a silver halide color photographic light-sensitive material having excellent surface physical properties and a storage stability when not processed.

[0002]

2. Description of the Related Art In a silver halide color photographic light-sensitive material (hereinafter sometimes simply referred to as a color photographic light-sensitive material),
As couplers generally used, there are known yellow couplers composed of open-chain ketomethylene compounds, magenta couplers composed of pyrazolone compounds, pyrazoloazole compounds, cyan couplers composed of phenol compounds and naphthol compounds, and the like. Conventionally, 5-pyrazolone compounds are often used as magenta couplers.

Known pyrazolone magenta couplers include US Pat. Nos. 2,600,788 and 3,519,429, and JP-A-49-1.
11631, 57-35858, etc. But,
The Theory of the Photographic Process,
Macmillan, 4th edition (1977), pp. 356-358, Fine Chemicals, CMC, Vol. 14, No. 8, 38-41
Page, Proceedings of the Annual Meeting of the Photographic Society of Japan, 1985, 10
As described on pages 8 to 110, the dye formed from the pyrazolone magenta coupler has an undesired side absorption, and its improvement is desired.

As described in the above-mentioned literature, the dye formed from the pyrazoloazole type magenta coupler has no side absorption. That this coupler is a good coupler, U.S. Pat.
No. 3,810,761 etc.

However, the fastness to light of the azomethine dyes formed from these couplers is extremely low, and the performance of color photographic light-sensitive materials, especially print color photographic light-sensitive materials, is markedly impaired.

[0006] Conventionally, research has been conducted to improve light fastness. For example, JP-A Nos. 59-125732 and 6
1-282845, 61-292639, and 61-279855 disclose a technique of using a pyrazoloazole-based magenta coupler in combination with a phenol compound or a phenyl ether compound.
61-72246, 62-208048, 62-157031, 63-163
No. 351 discloses a technique of using an amine compound in combination.

However, also in the above technique, the fastness to light of a magenta dye image is insufficient, and improvement thereof has been strongly desired.

Further, in JP-A-4-140742, a magenta coupler (particularly 1H-pyrazolo [1,5-b] [1,2,4] triazole type magenta coupler) of 4.5 times (weight ratio) or more is used. Although a technique using a high boiling point organic solvent is disclosed, in this case, although the light resistance is certainly greatly improved, the film thickness becomes thicker due to the increase in the amount of oil and the sharpness is lowered, The aging stability of the coupler dispersion deteriorates during the production of the photographic light-sensitive material, and the quality of the dispersion varies, and various problems are likely to occur during mass production. The undesirable phenomenon of gradually bleeding out on the surface of the photosensitive material (perspiration phenomenon) occurs simultaneously.

Separately from this, as means for improving the light fastness of a magenta dye image, there are disclosed in JP-A-61-65245 and JP-A-61-1.
20146, 61-120147, 61-120148, 61-120149
No. 61-120150, etc. 1H-pyrazolo
[1,5-c] [1,2,4] triazole and 1H-pyrazolo [1,5-b] [1,
A technique is known in which a coupler in which a secondary or tertiary bulky alkyl group is introduced at the 6-position (adjacent to the coupling position) of 2,4] triazole is used. This technique certainly improves the light fastness as the 6-position substituent is bulky in any of the mother nuclei, but on the other hand, the coloring property is deteriorated, and especially 1H-pyrazolo [1,5-b] [1 , 2,4] Triazole mother nucleus has a significant effect, and 1H-pyrazolo [1,5-b], which has a secondary or tertiary bulky alkyl group at the 6-position.
In the [1,2,4] triazole coupler, when a highly lipophilic substituent is introduced at the 2-position of the mother nucleus, the photographic performance (eg sensitivity, gradation, The fluctuation (fogging, etc.) of the coupler (raw storage stability) becomes large, or the color developability rather deteriorates. Also, as a problem different from this, since the melting point of the coupler is below room temperature (oil), It has been found that there are various drawbacks in that it becomes difficult to produce in large quantities (especially during purification).

The inventors of the present invention have conducted further research on the above points, and as a result, have excellent raw storability, color development, sweat resistance and light resistance without increasing the amount of the high boiling point organic solvent. In addition, the inventors have discovered a 1H-pyrazolo [1,5-b] [1,2,4] triazole coupler and have completed the present invention.

[0011]

SUMMARY OF THE INVENTION It is, therefore, an object of the present invention to provide a silver halide color photographic light-sensitive material which is excellent in light resistance, color development, raw storage stability and sweat resistance.

[0012]

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".

(3) In the magenta coupler represented by the general formula [MB], R ¹ is an isopropyl group, R ² is a secondary or tertiary alkyl group, or R ² is a secondary or tertiary substituted alkyl group. The silver halide color photographic light-sensitive material according to the item (2), which is characterized by being present. The present invention will be described in more detail below.

The magenta coupler represented by the general formula [MA] will be described first.

In the general formula [MA], the substituent represented by R ₂ is not particularly limited, but is typically alkyl, aryl, anilino, acylamino, sulfonamide, alkylthio, arylthio, alkenyl, cycloalkyl. Other groups such as halogen atom and cycloalkenyl, alkynyl, heterocycle, sulfonyl, sulfinyl, phosphonyl, acyl, carbamoyl, sulfamoyl, cyano, alkoxy, aryloxy, heterocycleoxy, siloxy, acyloxy, and the like. Each group of carbamoyloxy, amino, alkylamino, imide, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, heterocyclic thio, etc., and Pyro compound residue, bridged hydrocarbon compound residue and the like are also mentioned.

The alkyl group represented by R ₂ has 1 to 15 carbon atoms (hereinafter simply referred to as carbon number), and may be linear or branched.

The aryl group is preferably a phenyl group, and the acylamino group includes an alkylcarbonylamino group, an arylcarbonylamino group and the like.

Examples of the sulfonamide group include an alkylsulfonylamino group and an arylsulfonylamino group.

The alkylthio group represented by R _2, the alkyl moiety in the arylthio group, the aryl moiety wherein R ₂
And an alkyl group and an aryl group represented by.

The alkenyl group represented by R ₂ is preferably one having 2 to 15 carbon atoms, and the cycloalkyl group is preferably one having 3 to 12 carbon atoms, particularly 5 to 7 carbon atoms. But it's okay.

The cycloalkenyl group has 3 to 10 carbon atoms.
12, especially 5 to 7, are preferred. Examples of the sulfonyl group represented by R ₂ include an alkylsulfonyl group, an arylsulfonyl group, and the like; a sulfinyl group, an alkylsulfinyl group, an arylsulfinyl group, and the like; and a phosphonyl group, an alkylphosphonyl group, an alkoxyphosphonyl group, and aryl. An oxyphosphonyl group, an arylphosphonyl group, etc .; an acyl group, an alkylcarbonyl group, an arylcarbonyl group, etc .; a carbamoyl group, an alkylcarbamoyl group, an arylcarbamoyl group, etc .; a sulfamoyl group, an alkylsulfamoyl group, Arylsulfamoyl group, etc .; Acyloxy group, alkylcarbonyloxy group, arylcarbonyloxy group, etc .; Carbamoyloxy group, alkylcarbamoyloxy group, arylcarbamoyloxy group, etc. The ureido group is preferably an alkylureido group, an arylureido group, or the like; the sulfamoylamino group is preferably an alkylsulfamoylamino group, an arylsulfamoylamino group, or the like; and the heterocyclic group is preferably a 5- to 7-membered group. ,
Specifically, a 2-furyl group, a 2-thienyl group, a 2-pyrimidinyl group, a 2-benzothiazolyl group and the like; a heterocyclic oxy group having a 5- to 7-membered heterocycle is preferable, 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; Examples of the imide group include succinimide group, 3-heptadecylsuccinimide group, phthalimide group, glutarimide group and the like.

Each group represented by R ₂ also includes those further having a substituent.

Preferred among the substituents represented by R ₂ are an alkyl group and a substituted alkyl group, particularly —O—,
_{-SO 2 -, - NHCO -,} - NHSO 2 -, - CONH
Substituted alkyl groups having a linking group such as-, -COO-, and -OC (O)-are preferable.

The tertiary alkyl group other than the tert-butyl group represented by R ₁ is preferably t-amyl, t-octyl,
Examples include tertiary alkyl groups such as t-dodecyl, substituted alkyl groups such as 2-phenyl-1,1-dimethylethyl, 2-hydroxy-1,1-dimethylethyl, 2-methoxy-1,1-dimethylethyl and the like. To be

Examples of the group represented by X which can be split off by the reaction with the oxidized 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, aryloxycarbonyl, alkyl oxalyloxy, alkoxy oxalyloxy, alkylthio, arylthio, heterocyclic thio, alkyloxythiocarbonylthio, acylamino, sulfonamide, N Examples thereof include nitrogen-containing heterocycles bound by atoms, alkyloxycarbonylamino, aryloxycarbonylamino, carboxyl, and other groups, with halogen atoms being preferred, and chlorine atoms being particularly preferred.

The total number of carbon atoms of the substituents represented by R ₁ , R ₂ and X is 8 or more and 20 or less.

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

[0030]

[Chemical 3]

[0031]

[Chemical 4]

[0032]

[Chemical 5]

The magenta couplers of the present invention represented by the general formulas [MA] and [MB] are disclosed in JP-A-61-6524 and 63-2392.
No. 72, No. 64-6274, JP-A No. 2-201443 and the like can be used for the synthesis.

Next, the magenta coupler represented by the general formula [MB] will be described.

In the above general formula [MB], the secondary alkyl group represented by R ¹ is preferably i-propyl,
Examples thereof include groups such as i-pentyl and cyclohexyl, and examples of the secondary substituted alkyl group include groups such as 1-ethoxytridecyl and 1-methoxypentyl.

In the general formula [MB], the substituent represented by R ² is not particularly limited, and a typical group thereof is the substituent represented by R ₂ in the general formula [MA]. Each group described as a typical example can be mentioned.

Of these, the alkyl group has 1 to 20 carbon atoms and may be linear or branched, and the alkenyl group may have 2 to 20 carbon atoms.

Preferred among the substituents represented by R ² are an alkyl group and a substituted alkyl group, particularly -O-,
_{-SO 2 -, - NHCO -,} - NHSO 2 -, - CONH
Substituted alkyl groups having a linking group such as-, -COO-, and -OC (O)-are preferable.

In the magenta coupler represented by the general formula [MB], the total number of carbon atoms of the substituents represented by R ¹ and R ² is 8 or more and 20 or less, but represented by the general formula [MB]. The magenta coupler is not the monomer (repeating unit) forming the magenta color image forming polymer coupler.

In the general formula [MB], it is particularly preferable that R ¹ is an i-propyl group and R ² is a secondary or tertiary alkyl group, or a secondary or tertiary substituted alkyl.

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

[0042]

[Chemical 6]

[0043]

[Chemical 7]

Next, synthesis examples of the magenta coupler of the present invention will be shown.

Synthesis Example Synthesis of MB-8 i) Synthesis route

[0046]

[Chemical 8]

Ii) Synthesis of intermediate 2 4.7 g (14.8 mmol) of intermediate 1 was added to 150 g of ethyl acetate and 50 c of water.
c., 1.70 g (20.7 mmol) of sodium acetate were further added, and the mixture was vigorously stirred in an ice bath. After adjusting the temperature of the solution to 5 ℃, 2.53g of 2-ethylhexanoic acid chloride (15.5mmo
l) in ethyl acetate 20cc. under stirring (5 ℃)
It was dripped at. After completion of dropping, the mixture was stirred at 5 ° C. for 30 minutes and then at room temperature for 1 hour, and then separated. The organic phase was washed twice with 50 cc. Of 2% sodium hydrogen carbonate solution and then 100 cc. Of water. The obtained organic phase was dried over anhydrous magnesium sulfate, ethyl acetate as a solvent was distilled off under reduced pressure, and then recrystallized from acetonitrile to obtain 5.1 g (11.5 m) of white crystalline intermediate 2.
mol) was obtained.

(The structure was confirmed by ¹ HNMR, FD mass spectrum and IR spectrum.) Iii) Synthesis of MB-8 5.1 g (11.5 mmol) of intermediate 2 was dissolved in 40 cc of chloroform and then ice-cooled. To the place where the temperature was 3 ° C., 1.58 g (11.8 mmol) of N-chlorosuccinimide (NCS) was added in a small amount as a solid. The reaction solution was stirred at room temperature for 1 hour, washed 3 times with 100 cc. Of water, and the chloroform phase was dried over anhydrous magnesium sulfate. After chloroform was distilled off under reduced pressure, it was recrystallized from acetonitrile to obtain MB-84.7 g (9.8 mmol) of white crystals.

(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, and in order to contain it.
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, Nos. 11 to 1
Exemplified Compounds A-1 to A-28 and 61-1455 described on page 3
Exemplary compounds PH-1 to PH described in No. 52, pages 8 to 10
-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-listed 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 to 1
Exemplified compounds II-1 to II-33 described on page 1, JP-A 2-1
67543 Compounds B-1 to B-6 described on pages 8 to 11
5, Exemplified compounds (1) to (120) described on pages 4 to 7 of JP-A-63-95439 can 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 type magenta coupler of the present invention. It is 250 mol.

Although the pyrazoloazole-based magenta coupler of the present invention and the image stabilizer are preferably used in the same layer, 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, an inhibitor is directly bound to the coupling position and an inhibitor is bound to the coupling position via a divalent group. 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 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 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 color negative films, color papers, color reversal films and the like.

The color photographic light-sensitive material using the coupler of the present invention is subjected to bleach-fixing 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.

[0074]

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

Example 1 On a support having a polyethylene support laminated on one side of a paper support and a polyethylene containing titanium oxide on the other side, titanium oxide was applied to each layer having the constitution shown in Tables 1 and 2 below. By coating on the side of the contained polyethylene layer, a multilayer silver halide color photographic light-sensitive material sample 101 was prepared.

[0076]

[Table 1]

[0077]

[Table 2]

The coating liquid was prepared as follows.

First layer coating solution Yellow coupler (EY-1) 26.7 g, dye image stabilizer (ST-1) 10.0 g, dye image stabilizer (ST-2)
Ethyl acetate (60 cc.) Was added to 6.67 g, stain inhibitor (HQ-1) (0.67 g) and high boiling point organic solvent (DNP) (6.67 g) to dissolve, and this solution was dissolved in 20% surfactant (SU-2) aqueous solution (7 c).
220% of 10% gelatin aqueous solution containing c. A yellow coupler dispersion was prepared by emulsifying and dispersing with an ultrasonic homogenizer.

This dispersion was mixed with a blue-sensitive silver halide emulsion (containing 8.67 g of silver) shown below, and an anti-irradiation 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.

[0083]

[Chemical 9]

[0084]

[Chemical 10]

[0085]

[Chemical 11]

[0086]

[Chemical 12]

[0087]

[Chemical 13]

[0088]

[Chemical 14]

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-1 4 × 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, variation coefficient = 0.08, silver chloride content 99.5
Mol% monodispersed cubic silver chlorobromide emulsion Sodium thiosulfate 1.5 mg / mol AgX chloroauric acid 1.0 mg / mol AgX stabilizer STAB-1 6 × 10 ⁻⁴ mol / mol AgX sensitizing dye GS-1 4 × 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.

[0090]

[Chemical 15]

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 the high boiling point organic solvent (HBS) amount and dye image stabilizer were also replaced as shown in Table 3 to prepare Samples 102 to 140.

[0092]

[Table 3]

The magenta coupler E used for the comparative sample
Structural formulas of M-2, EM-3, EM-4, EM-5, EM-6 and EM-7 are shown together with EM-1 described above.

In addition, ST-4 and ST- used as comparative samples
The structural formula of 5 is shown together with ST-3 described above.

The sample thus prepared 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 cc. Per 1 m ^{2 of} silver halide color photographic light-sensitive material.

Color developing solution tank solution Replenishing solution Pure water 800 cc. 800cc. 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'-diaminostilbene sulfonic acid derivative) 1.0g 1.8g Potassium carbonate 27g 27g Add water to bring the total volume to 1000cc. pH
Is adjusted to 10.10 and the pH of the replenisher is adjusted to 10.60.

Bleach-fixing solution (tank solution and replenisher are the same) Ethylenediaminetetraacetic acid ammonium ferric dihydrate 60g Ethylenediaminetetraacetic acid 3g Ammonium thiosulfate (70% aqueous solution) 100cc. Ammonium sulfite (40% aqueous solution) 27.5cc. Water To 1000 cc. And adjust the pH to 5.7 with potassium carbonate or glacial acetic acid.

Stabilizing solution (tank solution and replenisher 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 1000 cc. And adjust the pH with sulfuric acid or potassium hydroxide. Adjust to 7.0.

(Photographic performance) The Dmax and the minimum density Dmin of the sample obtained by processing according to the above processing steps were determined. Furthermore, the same evaluation was performed using a sample which was stored under high temperature conditions (55 ° C.) for 6 days as an unexposed sample, and the fluctuation range (Δγ) a of the gradation γ due to the storage of the unexposed sample was determined.

(Δγ) a = | γ after high temperature storage−γ before high temperature storage | Also, the sample exposed to wedge by green light is processed according to the above processing steps to obtain the minimum density Dmin and the gradation γ. Immediately after the start of running, and after the running process until replenishing the color developing solution replenisher with an amount twice the tank capacity of the color developing solution, the variation (ΔDmin) b in Dmin and γ due to running was determined.

(ΔDmin) b = Dmin after running−Dmin immediately after running (Δγ) b = | γ immediately after starting running where γ is the exposure required to obtain densities of 0.5 and 1.5. It is the value expressed by the reciprocal of the logarithmic difference of the quantity.

(Perspiration) The obtained sample was stored under conditions of 85 ° C. and 60% RH for 10 days, and the deterioration of gloss due to the perspiration of the oil agent on the surface of the sample was visually evaluated.

◎ No "sweat" is seen ○ Almost no "sweat" is seen △ Some "sweat" is seen, but acceptable as a product × "Sweat" is not seen as a product (lightfastness) The obtained sample was irradiated with a xenon fade meter of 70,000 lux for 320 hours, and the residual ratio (%) of the magenta dye image at the initial density of 1.0 was obtained.

The results are shown in Table 4.

[0107]

[Table 4]

As is apparent from Table 4, the coupler (EM-1) in which the 6-position of the coupler is a methyl group has a high boiling point organic solvent / coupler ratio (HBS / Cp) of usually (1.0) ( Sample 101) has a storage stability (Δγ) a of an unexposed sample under high temperature storage and a running process fluctuation resistance (ΔDmin) b.
And (Δγ) b and sweat resistance are very good, while maximum color density (Dmax) and light fastness are considerably low. On the other hand, in Sample 102 in which only (HBS / Cp) is changed to 5.0, the light resistance and the color development which are the drawbacks of Sample 101 are improved, but the sweat resistance is considerably deteriorated.

Further, E in which the 6-position is a tertiary-substituted alkyl group
The sample 103 using M-2 and the sample 107 using EM-6 in which the 6-position is an isopropyl group have good light resistance and perspiration resistance under the normal condition (HBS / Cp) (1.0). However, (Δγ) a, (ΔDmin) b, and (Δγ) b are greatly deteriorated, and (Dmax) is considerably lowered, so that all the performances cannot be satisfied.

Furthermore, in sample 104 using EM-3, which has a larger number of carbons and a larger molecular weight than EM-2, the deterioration of (Δγ) b and (Dmax) is more remarkable, and the sweat resistance is slightly deteriorated. .

EM-5 in which the leaving group is a fluorine atom
Sample 106 according to No. 1 was very good in light resistance and sweat resistance but inferior in color developability, and (Δγ) a and (Δγ) b could not be measured.

Samples 105 and 6 by EM-4 having a tert-amyl group at the 6-position and an ethyl group at the 2-position (sum of carbon numbers 7)
Having an isopropyl group at the 2-position and an isobutyl group at the 2-position
Sample 108 based on −7 (the sum of carbon numbers 7) did not develop color at all, and therefore items other than sweat resistance could not be evaluated.

On the other hand, Samples 133 and MB-15 (6 with the magenta coupler MA-23 (6-position-tert-amyl group, 2-position-isopropyl group: sum of carbon numbers 8) of the present invention were used.
In the sample 120 using the position-isopropyl group, the 2-position-tert-amyl group: the sum of carbon numbers 8), no defective coloring was observed unlike the sample 105, and (Dmax), (Δγ) a, (ΔDmi
Satisfactory results were obtained for all items such as n) b, (Δγ) b, light resistance and sweat resistance.

The same can be said for all of Samples 109 to 119. In all of them, in the system of (HBS / Cp) = 1.0, color development, preservability of unexposed sample, running process fluctuation resistance, light resistance and It showed good performance in all aspects such as sweat resistance.

In more detail, a secondary or tertiary compound was obtained as compared to Sample 115 according to MB-3 in which the 2-position is a primary substituted alkyl.
Sample 116 and MB according to MB-4 which is a quaternary substituted alkyl
It can be seen that the sample 117 according to −5 is slightly superior in Dmax, preservability of the unexposed sample, and running process variation resistance. Comparing Sample 116 and Sample 119, MB-4 having an isopropyl group at 6-position is slightly better in overall performance than MB-11 having a long-chain alkyl group at 6-position. I understand.

Dye image stabilizers from ST-3 to ST-4
121-132 and 134-140 changed to combined use system of ST-5 and ST-5
It was found that the same result as above was obtained in the above, and the light resistance was slightly improved.

[0117]

EFFECT OF THE INVENTION 1H-Pyrazolo [1,5-b] [having a secondary alkyl group or a tertiary alkyl group other than t-butyl group at the 6-position and a substituent having a relatively small number of carbon atoms at the 2-position. Silver halide color photographic light-sensitive material containing 1,2,4] triazole magenta coupler is excellent in color development, light resistance, storage stability of unexposed sample under high temperature storage, fluctuation resistance during running processing and sweat resistance. I found that it has the effect.

Claims (3)

[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 represents a tertiary alkyl group other than a tert-butyl group, and R ₂ represents a substituent. X represents a hydrogen atom or a group capable of splitting off upon reaction with an oxidant of a color developing agent, R ₁ ,
The total number of carbon atoms of the substituents represented by R ₂ and X is 8 or more and 20 or less. ] 2. A silver halide color photographic light-sensitive material containing at least one magenta coupler represented by the following general formula [MB]. [Chemical 2] [In the formula, R ¹ represents a secondary alkyl group or a secondary substituted alkyl group, and R ² represents a substituent. The total number of carbon atoms of the substituents represented by R ¹ and R ² is 8 or more and 20 or less. ] 3. A magenta coupler represented by the general formula [MB], wherein R ¹ is an isopropyl group, R ² is a secondary or tertiary alkyl group, or R ² is a secondary or tertiary substituted alkyl group. 3. A silver halide color photographic light-sensitive material according to claim 2, wherein