JPH04346342A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To enhance graininess and lessen variation in quality at the time of application to printers by containing at least one kind of a specific Magenta coupler in a silver halide emulsion layer. CONSTITUTION:At least one kind of a Magenta coupler expressed by a formula I and at least one kind of a Magenta coupler expressed by a formula II are contained in a silver halide emulsion layer. Here, R1, R2, R3, and R4 respectively represent a hydrogen atom or substituent; X1, X2 respectively represent a hydrogen atom, or a group separable due to reaction with an oxidant of a color developing agent. For substituents represented by R1, R2, R3, and R4, respective groups of alkyl, aryl, anilino, acylamino, sulfonamide, alkylthio, allylthio, alkenyl, cycloalkyl, and the like are listed as representatives.

Description

[Detailed description of the invention]

0001

[Field of Industrial Application] The present invention relates to a silver halide color photographic light-sensitive material, and more particularly to a silver halide color photographic light-sensitive material that has high sensitivity, high color development, excellent graininess, and excellent print reproducibility. .

0002

[Background of the invention] Silver halide color photographic materials include
Usually, yellow couplers, cyan couplers, and magenta couplers are used in combination. Among these, 5-pyrazolone magenta couplers are widely used as magenta couplers. 5-pyrazolone magenta couplers have various problems in color reproduction because the dye formed by development has sub-absorption near 430 nm. In order to solve this problem, new magenta couplers have been researched, such as U.S. Pat.
No. 0,761, No. 3,758,309, No. 3,725
Pyrazolotriazole couplers have been developed, such as those disclosed in US Pat.

These couplers have little side absorption and are advantageous in terms of color reproducibility. In addition, pyrazolotriazole magenta couplers have superior coloring properties compared to 5-pyrazolone magenta couplers, so they have the advantage of reducing the amount of coupler used; however, on the other hand, these pyrazolotriazole magenta couplers The problem arose of deterioration of graininess.

Furthermore, when these pyrazolotriazole couplers are used in color negative films and printed on paper, the hue of the finished color paper may vary depending on the printer equipment (hereinafter referred to as printer) used. It was found that there was a discrepancy between printers (hereinafter referred to as inter-printer variation).

[0005] Although this phenomenon has been observed in other conventional couplers, the degree of the phenomenon was extremely small and was not a problem. However, it has been found that when a pyrazolotriazole coupler is used, the difference in hue of the finished color paper due to differences in printers becomes a non-negligible level.

[0006] This phenomenon is thought to be mainly due to the following reasons. That is, when printing from color negative film to color paper using a printer, the printer first measures (1) the blue density, green density, and red density of the color negative film, and (2) measures the blue density, green density, and red density of the color negative film.
) These measured values are then converted into an exposure amount for the color paper, and (3) the color paper is exposed with this exposure amount. Various printers are commercially available and in use on the market, and depending on the model of these printers, the spectral sensitivity of the detector used for photometry (1) may differ, and due to the spectral absorption characteristics of the coloring dye in the color negative film, For example, a hue shift may occur because the half-width is too small or the spectral absorption characteristics vary depending on the concentration.

Many of the above-mentioned pyrazolotriazole magenta couplers have spectral absorption characteristics that vary greatly depending on concentration, and this is one of the reasons why the variation between printers increases when pyrazolotriazole magenta couplers are used for negative films. It is thought that there is one.

For this reason, there has been a desire to develop a technique that provides excellent graininess and reduces printer-to-printer variation in silver halide color photographic materials containing pyrazolotriazole-based magenta couplers.

[0009]

OBJECTS OF THE INVENTION It is an object of the present invention to solve the above problems. That is, the first object of the present invention is to provide a silver halide color photographic light-sensitive material with high sensitivity and excellent graininess. A second object of the present invention is to provide a silver halide color photographic material with little variation between printers.

0010

[Structure of the Invention] These objects of the present invention are to provide a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support. This is achieved by a silver halide color photographic light-sensitive material characterized by containing at least one magenta coupler represented by [I] and at least one magenta coupler represented by the following general formula [M-II]. Ta.

[0011]

embedded image [In the formula, R1, R2, R3 and R4 represent a hydrogen atom or a substituent.

[0012] X1 and X2 represent a hydrogen atom or a group that can be separated by reaction with an oxidized product of a color developing agent. ] The magenta couplers represented by the general formulas [M-I] and [M-II] according to the present invention will be explained in detail.

General formula [M-I] and general formula [M-II]
In, R1, R2, R3 and R4 represent a hydrogen atom or a substituent.

The substituents represented by R1, R2, R3 and R4 are not particularly limited, but typically include alkyl, aryl, anilino, acylamino, sulfonamide, alkylthio, arylthio, alkenyl, cycloalkyl and the like. In addition, halogen atoms and cycloalkenyl, alkynyl, heterocycle, sulfonyl, sulfinyl, phosphonyl, acyl, carbamoyl, sulfamoyl, cyano, alkoxy, aryloxy, heterocycleoxy, siloxy, acyloxy, carbamoyloxy, amino , alkylamino, imide, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, heterocyclic thio groups, as well as spiro compound residues, bridged hydrocarbon compound residues, etc. can also be mentioned.

The alkyl groups represented by R1, R2, R3 and R4 preferably have 1 to 32 carbon atoms, and may be linear or branched.

The aryl group represented by R1, R2, R3 and R4 is preferably a phenyl group.

[0017] Examples of the acylamino group represented by R1, R2, R3 and R4 include an alkylcarbonylamino group and an arylcarbonylamino group.

The sulfonamide groups represented by R1, R2, R3 and R4 include alkylsulfonylamino groups,
Examples include arylsulfonylamino groups.

Examples of the alkyl component and aryl component in the alkylthio group and arylthio group represented by R1, R2, R3 and R4 include the alkyl group and aryl group represented by R1, R2, R3 and R4 above.

The alkenyl group represented by R1, R2, R3 and R4 preferably has 2 to 32 carbon atoms, and the cycloalkyl group preferably has 3 to 12 carbon atoms, particularly 5 to 7 carbon atoms. may be linear or branched.

The cycloalkenyl group represented by R1, R2, R3 and R4 has 3 to 12 carbon atoms, especially 5 to 7 carbon atoms.
Preferably.

Sulfonyl groups represented by R1, R2, R3 and R4 include alkylsulfonyl groups and arylsulfonyl groups; sulfinyl groups include alkylsulfinyl groups and arylsulfinyl groups; phosphonyl groups include alkylphosphonyl groups; groups, alkoxyphosphonyl groups, aryloxyphosphonyl groups, arylphosphonyl groups, etc.; Acyl groups include alkylcarbonyl groups, arylcarbonyl groups, etc.; carbamoyl groups include alkylcarbamoyl groups, arylcarbamoyl groups, etc.; sulfamoyl groups teeth,
Alkylsulfamoyl group, arylsulfamoyl group, etc.; Acyloxy group includes alkylcarbonyloxy group, arylcarbonyloxy group, etc.; Carbamoyloxy group includes alkylcarbamoyloxy group, arylcarbamoyloxy group, etc.; ureido group includes , an alkylureido group, an arylureido group, etc.; Examples of the sulfamoylamino group include an alkylsulfamoylamino group, an arylsulfamoylamino group; examples of the heterocyclic group include 5- to 7-membered ones; 2-furyl group, 2-thienyl group, 2-pyrimidinyl group, 2-benzothiazolyl group, etc.; As the heterocyclic oxy group, one having a 5- to 7-membered heterocycle is preferable, such as 3, 4, 5, 6-tetrahydropyranyl-2-oxy group, 1-phenyltetrazole-5
-oxy group, etc.; As the heterocyclic thio group, a 5- to 7-membered heterocyclic thio group is preferable, such as 2-pyridylthio group, 2-benzothiazolylthio group, 2,4-diphenoxy-1,3,5- Triazole-6-thio group, etc.; Siloxy group includes trimethylsiloxy group, triethylsiloxy group, dimethylbutylsiloxy group, etc.; imide group includes succinimide group, 3-heptadecylsuccinimide group, phthalimide group, glutarium group. Imide group, etc.; spiro compound residues include spiro[3.3]heptan-1-yl, etc.; bridged hydrocarbon compound residues include bicyclo[2.2.
1] Heptan-1-yl, tricyclo[3.3.1.1
3,7]decane-1-yl, 7,7-dimethyl-bicyclo[2.2.1]heptan-1-yl, and the like.

Groups that can be separated by reaction with the oxidized product of the color developing agent represented by X1 and X2 include, for example, halogen atoms (chlorine atom, bromine atom, fluorine atom, etc.), alkoxy, aryloxy, heterocyclic oxy, acyloxy. , sulfonyloxy, alkoxycarbonyloxy, aryloxycarbonyl, alkyloxalyloxy, alkoxyoxalyloxy, alkylthio, arylthio, heterocyclic thio, alkyloxythiocarbonylthio, acylamino, sulfonamide, nitrogen-containing heterocycle bonded by N atom , alkyloxycarbonylamino, aryloxycarbonylamino, carboxyl, and the like.

Typical specific examples of the magenta coupler represented by the general formula [M-I] of the present invention are shown below.

[0025]

[Chemical formula 3]

[0026]

[C4]

[0027]

[C5]

[0028]

[C6]

[0029]

[C7]

[0030]

[Chemical formula 8]

[0031]

[Chemical formula 9]

[0032]

[Chemical formula 10]

[0033]

[Chemical formula 11]

[0034]

embedded image Next, typical specific examples of the magenta coupler represented by the general formula [M-II] of the present invention will be shown.

[0035]

[Chemical formula 13]

[0036]

[Chemical formula 14]

[0037]

[Chemical formula 15]

[0038]

embedded image Magenta coupler (hereinafter referred to as
magenta coupler [M-I]) and the general formula [M-I
The magenta coupler represented by I] (hereinafter referred to as magenta coupler [M-1I]) was published in the Journal of the Chemical Society.
Perkin I (1977), 2047-20
52, U.S. Patent No. 3,725,067, JP-A-59-9
No. 9437, No. 58-42045, No. 59-1625
No. 48, No. 59-171956, No. 60-33552
No. 60-43659, No. 60-172982,
It can be synthesized by referring to No. 60-190779, No. 62-209457, No. 63-307453, etc.

The magenta coupler [M-I] of the present invention is
Usually, it can be used in a range of 1.times.10@-3 mol to 1 mol, preferably 1.times.10@-2 mol to 8.times.10@-1 mol per mol of silver halide.

Furthermore, the magenta coupler of the present invention [M-II
] can be used in a range of 1 x 10-3 mol to 1 mol, preferably 1 x 10-2 mol to 8 x 10-1 mol, per mol of silver halide. In the present invention, magenta coupler [M-I] and magenta coupler [M-II] are used together, and the molar ratio of magenta coupler [M-I] and magenta coupler [M-II] is 10:1 to 1:5. The ratio is good, preferably 5:1 to 1:3. The couplers of the invention can be used in conjunction with other types of magenta couplers.

In the present invention, magenta coupler [M-
I] and magenta coupler [M-II] are contained in at least one of the green-sensitive silver halide emulsion layers.

In order to incorporate magenta coupler [M-I] and magenta coupler [M-II] into the silver halide emulsion layer, conventionally known methods such as known dibutyl phthalate, tricresyl phosphate, etc. After dissolving magenta coupler [M-I] and magenta coupler [M-II] alone or in combination in a mixture of a high-boiling point solvent and a low-boiling point solvent such as butyl acetate or ethyl acetate, the surface activation A method can be adopted in which the agent is mixed with an aqueous gelatin solution containing the agent, then emulsified and dispersed using a high-speed rotary mixer, a colloid mill, or an ultrasonic disperser, and then directly added to the emulsion. Alternatively, after setting the emulsified dispersion, it may be shredded, washed with water, and then added to the emulsion.

In the present invention, the magenta coupler [M-I] and the magenta coupler [M-II] according to the present invention may be separately dispersed by the above-mentioned dispersion method and added to the silver halide emulsion. , a method in which both compounds are simultaneously dissolved, dispersed, and added to an emulsion is preferred.

As the silver halide emulsion used in the light-sensitive material of the present invention, any conventional silver halide emulsion can be used. The emulsion can be chemically sensitized by conventional methods, and can be optically sensitized to a desired wavelength range using a sensitizing dye.

Antifoggants, stabilizers and the like can be added to the silver halide emulsion. Gelatin is advantageously used as binder for the emulsion.

The emulsion layer and other hydrophilic colloid layers can be hardened and can contain a plasticizer and a dispersion (latex) of a water-insoluble or sparingly soluble synthetic polymer. Couplers are used in the emulsion layer of color photographic materials.

Furthermore, by coupling with a colored coupler having a color correction effect, a competitive coupler, and an oxidized form of a developing agent, a development accelerator, a bleach accelerator, a developer, a silver halide solvent, a toning agent, a hardener, etc. Compounds that release photographically useful fragments such as film agents, fogging agents, antifogging agents, chemical sensitizers, spectral sensitizers, and desensitizers can be used.

The photosensitive material can be provided with auxiliary layers such as a filter layer, an antihalation layer, and an antiirradiation layer. In these layers and/or in the emulsion layer,
Dyes that are washed out or bleached from the light-sensitive material during processing may also be included. Photosensitive materials include formalin scavengers, fluorescent whitening agents, matting agents, lubricants, image stabilizers, surfactants, color fog preventive agents, development accelerators,
Development retarders and bleach accelerators can be added.

As the support, paper laminated with polyethylene or the like, polyethylene terephthalate film, baryta paper, cellulose triacetate, etc. can be used.

To obtain a dye image using the light-sensitive material of the present invention, commonly known color photographic processing can be performed after exposure.

[0051]

EXAMPLES Specific examples of the present invention will be described below, but the embodiments of the present invention are not limited thereto. Example 1 In the Examples, the amount added to the silver halide photographic light-sensitive material is shown per 1 m2 unless otherwise specified. Further, silver halide is shown in terms of silver, and sensitizing dyes and couplers are shown in moles per mole of silver in the same layer.

A multilayer color photographic material (Sample 1) was prepared by sequentially forming each layer having the composition shown below on a triacetyl cellulose film support from the support side. Sample 1 (comparison) First layer; antihalation layer (HC) Gelatin layer containing black colloidal silver.

[0053] Dry film thickness 3 μm 2nd
Layer; Interlayer (IL) Gelatin layer containing an emulsified dispersion of 2,5-di-t-octylhydroquinone.

[0054] Dry film thickness 1.0 μm third layer;
Low-sensitivity red-sensitive silver halide emulsion layer (RL) Monodispersed emulsion consisting of AgBrI with an average grain size of 0.3 μm and containing 3 mol% of AgI (Emulsion I: width of distribution 12%)
1.8
g Sensitizing dye I
6.0×10-4
Mol sensitizing dye II
1.0×
10-4 mol cyan coupler (C-1)
0.06
Mol colored cyan coupler (CC-1)
0.003 mol DIR compound (D-1)
0.0015 mol DIR compound (D-2)

0.002mol dioctyl phthalate

0.6g Dry film thickness 3
．． 5μm 4th layer; high sensitivity red-sensitive silver halide emulsion layer (R
H) A containing 3 mol% AgI with an average particle size of 0.5 μm
Monodispersed emulsion consisting of gBrI (emulsion II: distribution width 12%)
1.3g Sensitizing dye I

3.0 x 10-4 mol Sensitizing dye II

1.0 x 10-4 mol cyan coupler (
C-1)
0.02 mol colored cyan coupler (
CC-1) 0.0015 mol DIR compound (D-2)
0.001 mol dioctyl phthalate
0.2g Dry film thickness 2.5μm 5th layer; intermediate layer (
IL) Same as second layer, gelatin layer.

[0055] Dry film thickness 1.0 μm 6th layer;
Low-sensitivity green-sensitive silver halide emulsion layer (GL) Emulsion
I
1.5
g Sensitizing dye III
2.5×10−
4 mol sensitizing dye IV
1.2
×10-4 mol Magenta coupler (M-a)
0.070 mol colored magenta coupler (CM-1)
0.009 mol DIR compound (D
-1)
0.0010 mol DIR compound (D-3)
0.0
030 mole tricresyl phosphate
0.
5g Dry film thickness 3.5μm 7th
Layer: High-sensitivity green-sensitive silver halide emulsion layer (GH) Emulsion II

1.4g Sensitizing dye III
1.5×
10-4 mol Sensitizing dye IV
1.
0x10-4 mol magenta coupler (M-a)
0.025
Mol Colored Magenta Coupler (CM-1)
0.002 mol DIR compound (
D-3)
0.0010mol tricresyl phosphate
0.3g Dry film thickness 2
．． 5 μm 8th layer; Yellow filter layer (YC) A gelatin layer containing yellow colloidal silver and an emulsified dispersion of 2,5-di-t-octylhydroquinone.

[0056] Dry film thickness: 1.2 μm 9th layer;
Low-speed blue-sensitive silver halide emulsion layer (BL) Monodispersed emulsion consisting of AgBrI with an average grain size of 0.48 μm and containing 3 mol% of AgI (Emulsion III: width of distribution 12%)
0.
9g Sensitizing dye V
1.3×10-
4 mol yellow coupler (Y-1)
0.29 mol
tricresyl phosphate
0.5g Dry film thickness 3.5μm 10th layer; High sensitivity blue-sensitive silver halide emulsion layer (BH) Average grain size 0.8μ
Monodisperse emulsion consisting of AgBrI containing m, AgI 3 mol% (Emulsion IV: distribution width 12%)
0.5g
Sensitizing dye V
1.0 x 10-4 mol yellow coupler (Y-1)
0.08mol DI
R compound (D-2)
0.0015mol tricresyl phosphate
0.1g dry film thickness
2.5μm 11th layer; 1st protective layer (PRO-1
) Silver iodobromide (AgI 2 mol%, average grain size 0.07 μm
)0.5g Ultraviolet absorber (UV-1), (UV-
2) a gelatin layer containing.
Dry thickness: 2.0 μm Twelfth layer; Second protective layer (PRO-2) Gelatin layer containing polymethyl methacrylate particles (1.5 μm in diameter) and formalin scavenger (HS-1).

[0057] Dry film thickness 1.5 μm
In addition to the above composition, each layer contains a gelatin hardener (H-
1) and a surfactant were added.

The compounds contained in each layer of sample 1 are as follows. Sensitizing dye I anhydro-5,5'-dichloro-9-
Ethyl-3,3'-di-(3-sulfopropyl)thiacarbocyanine hydroxide sensitizing dye II anhydro-9-ethyl-3,3'-
Di-(3-sulfopropyl)-4,5,4',5'-dibenzothiacarbocyanine hydroxide sensitizing dye III Anhydro-5,5'-diphenyl-9-ethyl-3,3'-di-( 3-sulfopropyl)
Oxacarbocyanine hydroxide sensitizing dye IV anhydro-9-ethyl-3,3'-
Di-(3-sulfopropyl)-5,6,5',6'-dibenzoxacarbocyanine hydroxide sensitizing dye V anhydro-3,3'-di-(3-sulfopropyl)-4,5-benzo -5'-methoxythiacyanine hydroxide

[0059]

[Chemical formula 17]

[0060]

[Chemical formula 18]

[0061]

embedded image Next, in Sample 1, the magenta couplers (M-a) in the sixth and seventh layers were replaced as shown in Table 1 to prepare Samples 2 to 18.

The photographic material prepared as described above was subjected to wedge exposure using a conventional method, and then developed according to the following steps.

<Color developer> 4-amino-3-methyl-N-ethyl-N-(
β-hydroxyethyl) Aniline sulfate

4.75g anhydrous sodium sulfite
4.25g Hydroxylamine・
1/2 sulfate
2.0g anhydrous potassium carbonate

37.5g Sodium Bromide

1.3g Nitrilotriacetic acid trisodium salt (monohydrate) 2.5g
potassium hydroxide
1.
Add 0g water to make 1 liter and adjust the pH to 10.0. <Bleach solution> Ethylenediaminetetraacetic acid iron(III) ammonium salt 100g Ethylenediaminetetraacetic acid diammonium salt
10.0g ammonium bromide
1
50.0g glacial acetic acid

Add 10.0g water to make 1 liter and adjust the pH to 6.0. <Fixer> Ammonium thiosulfate (50% aqueous solution)
162ml anhydrous sodium sulfite
Add 12.4g water to make 1 liter and adjust the pH to 6.5. <Stabilizing liquid> Formalin (37% aqueous solution)
5.0ml
Konidax (manufactured by Konica Corporation)
Add 7.5ml water to make 1 liter.

The sensitivity and graininess of the green-sensitive layers of Samples 1 to 18 treated as described above were measured.

After treatment, the green light sensitometric properties of each sample were measured. Sensitivity is fog +0.
The relative sensitivities are calculated from the reciprocal of the exposure amount required to give a density of 3, and are shown in Table 1 below as relative sensitivities, taking the sensitivity of sample 1 as 100. In addition, the graininess was evaluated by the RMS value, and the RMS value was determined by measuring the minimum density + 0.5 part of the green density at 250 μm2 using a Konica microdecintometer model PDM-5 type AR (manufactured by Konica Corporation). It was calculated from the standard deviation of the variation in concentration value when sample 1 was taken as 100, and the relative values are shown in Table 1 below. The smaller the value, the better the graininess of the image.

[0066]

[Table 1] As can be seen from the results in Table 1, samples 7 to 18 of the present invention were
It has high sensitivity and excellent graininess. Example 2 Samples 1 to 18 prepared in Example 1 were each exposed to uniform white light and subjected to the same development process as in Example 1. Samples 1A to 18A were printed from the developed samples using Printer A so as to have a gray color with a reflectance of 18%.

Next, use printer B, which has a green area detector different from printer A, and
Samples 1B to 18B printed under the printing conditions used in
was created and the variation between different types of printers was visually determined. The results are shown in Table 2.

[0068]

[Table 2] From the results in Table 2, compared to comparative samples 2 to 6 using pyrazolotriazole couplers, samples 7 to 18 of the present invention
In both cases, the variation between different types of printers is small,
The effects of the improvements can be seen.

[0069]

According to the present invention, it is possible to provide a silver halide color photographic light-sensitive material that has high sensitivity, excellent graininess, and improved variation between different types of printers.

Claims (1)

[Claims] Claim 1. In a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support, the silver halide emulsion layer has the following general formula [M-I
] A silver halide color photographic light-sensitive material comprising at least one magenta coupler represented by the formula [M-II] below. embedded image In the formula, R1, R2, R3 and R4 represent a hydrogen atom or a substituent. X1 and X2 represent a hydrogen atom or a group that can be separated by reaction with an oxidized product of a color developing agent. ]