JP2000098555A - Silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a black-and-white silver halide photographic sensitive material which can be treated by color development process, showing good neutrality in black-and-white images and a good whiteness degree even in running treatment. SOLUTION: This silver halide photographic sensitive material has silver halide emulsion layers containing three couplers, namely a yellow coupler, magenta coupler, cyan coupler, or a black forming coupler, and a green sensitive layer is formed in a farther position from the supporting body than a blue sensitive layer or a red sensitive layer. Or, the photographic material has silver halide emulsion layers containing three kinds of couplers, namely a yellow coupler, magenta coupler and cyan coupler, and a black color forming coupler, and contains a fluorescent whitening agent. Or, the photographic material has silver halide emulsion layers containing three kinds of couplers, namely a yellow coupler, magenta coupler and cyan coupler, and a black color forming coupler, and contains an oil-soluble dye or a color pigment which does not substantially decolor in the treatment.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a silver halide photographic material, and more particularly, to a black-and-white silver halide photographic material which can be processed with a color developer.

[0002]

2. Description of the Related Art Conventionally, a black-and-white photographic image is formed by developing a silver halide with a black-and-white developing solution to form a silver image. In this black-and-white developer, a reducing agent such as hydroquinone or ascorbic acid is used to reduce the exposed silver halide to metallic silver.

[0003] Therefore, in order to develop color prints and monochrome prints in a developing lab, different developers and processors for color and black and white are required. For this reason, the profitability of the developing laboratory is deteriorated, and a problem occurs in securing the installation space.

In order to solve such a problem, there has been a demand for a proposal of a black-and-white photosensitive material which can be processed with a color developer. In order to meet such a demand, a method of obtaining a black-and-white image by mixing three types of couplers, a yellow coupler, a magenta coupler, and a cyan coupler, and incorporating the same in a single layer is disclosed in, for example, JP-A-6-505580. Has been described.

However, when such a method is adopted, there is a problem that the neutrality of a black image is easily deteriorated and the hue is likely to be shifted from black. Then, in order to solve this problem, the present inventors have conducted studies and found that the adjustment can be made to some extent by adjusting the coupler to be used and the silver halide emulsion. However, it is still insufficient, and in particular, a new problem has been found that the neutrality of a highlight portion having a reflection density of about 0.1 is liable to fluctuate due to the running process.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a black-and-white silver halide photographic material capable of color processing,
An object of the present invention is to provide a silver halide photographic light-sensitive material having good neutrality of a black-and-white image even when running. Another object of the present invention is to provide a black-and-white silver halide photographic light-sensitive material which has good whiteness and can be color-processed.

[0007]

The above object has been attained by the following constitutions.

[0008] 1. A silver halide photographic light-sensitive material having, on a support, a green-sensitive silver halide emulsion-containing layer and a plurality of silver halide emulsion-containing layers including a layer containing a blue-sensitive silver halide emulsion or a red-sensitive silver halide emulsion. In at least one of the plurality of silver halide emulsion-containing layers
The layer contains three couplers of a yellow coupler, a magenta coupler and a cyan coupler or a black-forming coupler, and the green-sensitive silver halide emulsion layer is formed on the support with respect to the blue-sensitive silver halide emulsion or the black-sensitive silver halide emulsion. A silver halide photographic material characterized by being located farther from a layer containing a red-sensitive silver halide emulsion.

[0009] 2. In a silver halide photographic light-sensitive material having a photographic component layer including at least one silver halide emulsion-containing layer on a support, the at least one silver halide emulsion-containing layer includes a yellow coupler, a magenta coupler, and a cyan coupler. A silver halide photographic light-sensitive material containing three types of couplers or a black-forming coupler, and further comprising a fluorescent whitening agent in the support or the photographic component layer.

[0010] 3. In a silver halide photographic light-sensitive material having a photographic component layer including at least one silver halide emulsion-containing layer on a support, the at least one silver halide emulsion-containing layer includes a yellow coupler, a magenta coupler, and a cyan coupler. A silver halide photograph containing three couplers of a coupler or a black-forming coupler and containing, in the support or the photographic component layer, an oil-soluble dye or a colored pigment which does not substantially decolorize in the processing. Photosensitive material.

Hereinafter, the present invention will be described in detail.

In the present invention, at least one layer containing a silver halide emulsion contains three couplers of a yellow coupler, a magenta coupler, and a cyan coupler or a black-forming coupler. This is a coupler necessary for obtaining a black and white image in a color development process. Any of the three types of couplers may be used, but it is preferable to use a combination of couplers separately described below. When combined, adjustment is made so that the hue becomes substantially black and white. As a black-forming coupler,
A compound having a single color-forming portion and capable of obtaining a black or black-like color (for example, 4- (isopropylcarbamoylmethoxy) -3-N-octadecylaminophenol)
And a compound having a plurality of color-forming portions and capable of obtaining a black or black-like color (for example, a copolymer having yellow, magenta, and cyan color-forming portions).

It is more preferable to obtain a black or black approximate image by combining and mixing three types of yellow coupler, magenta coupler and cyan coupler, because the desired color adjustment can be easily performed.

According to the first aspect of the present invention, there are provided a green-sensitive silver halide emulsion-containing layer and at least one blue-sensitive silver halide emulsion or a red-sensitive silver halide emulsion-containing layer. It is necessary that the light-sensitive silver halide emulsion layer is located farther from the support than the layer containing the blue-sensitive silver halide emulsion or the red-sensitive silver halide emulsion.

This green-sensitive silver halide emulsion-containing layer comprises:
It is necessary that the layer is far from the support from any of the blue-sensitive silver halide emulsion-containing layer and the red-sensitive silver halide emulsion-containing layer. The blue-sensitive silver halide emulsion and the red-sensitive silver halide emulsion may be added to the same layer. By employing such a configuration, a black-and-white image having good neutrality can be obtained even in the running process. It was also found that an image having good whiteness was obtained.

In the invention of claim 2, it is necessary that the silver halide photographic light-sensitive material contains a fluorescent whitening agent.

The fluorescent whitening agent of the second aspect of the present invention is not particularly limited as long as it is a compound capable of absorbing ultraviolet rays and emitting visible light fluorescence, but preferably has at least a sulfonic acid group in the molecule. It is a fluorescent whitening agent having one or more, and a preferable compound is a diaminostilbene-based fluorescent whitening agent having four or more sulfonic acid groups in one molecule. Compounds represented by the general formula II described in the upper right of page 5 of JP-A-4-1633 can be mentioned as preferred compounds.

Specific examples of the fluorescent whitening agent which can be used in the invention of claim 2 include compounds 1 to 23 described in JP-A-4-1633, page 5, lower right to page 7, upper left. Fluorescent whitening agent may be added to any layer such as a photosensitive silver halide emulsion layer, a photographic component layer such as a non-photosensitive layer, and a support, but is preferably a photosensitive layer or a non-photosensitive layer, More preferably, it is a non-photosensitive layer. The addition amount of the fluorescent whitening agent is preferably 0.01 to ² g / m ² , and more preferably 0.02 to 1 g / m ² .

According to the third aspect of the present invention, it is necessary that the silver halide photographic light-sensitive material contains an oil-soluble dye or a colored pigment which does not substantially decolor during processing.

An oil-soluble dye or colored pigment which does not substantially decolorize in the treatment means that at least 70% of the spectral absorption after the treatment remains with respect to the spectral absorption caused by the oil-soluble dye or the colored pigment before the treatment. A thing.

The oil-soluble dye which can be preferably used in the present invention refers to a solubility in water at 20 ° C. [g / 100
g] (weight of a substance soluble in 100 g of water) is 1 × 10 ⁻²
The following organic dyes are mentioned, and typical compounds include anthraquinone compounds and azo compounds.

The oil-soluble dye according to the present invention has a wavelength of 400
The molecular absorption coefficient (solvent chloroform) of the maximum absorption wavelength at nm or more is preferably 5,000 or more, and 200
More preferably, it is not less than 00.

The oil-soluble dye which can be preferably used in the light-sensitive material of the present invention is 0.01 mg / m ^{2 to} 10 mg / m ^2.
It is preferably used in a coating amount of m ² , more preferably 0.05
It is more preferable that the amount be from mg / m ^{2 to} 5 mg / m ² .

The oil-soluble dye used in the present invention can be used in either a photographic constituent layer or a support.
More preferably, it is added to a non-photosensitive layer other than the coupler-containing layer.

A particularly preferred method of using the oil-soluble dye according to the present invention is to use an oil-soluble dye having a maximum absorption wavelength at a wavelength of 400 nm or more and a molecular extinction coefficient of 20,000 or more.
05MG / m ² to is to be contained in the non-light-sensitive layer other than coupler-added layer at a coverage of from 5 mg / m ^2.

Preferred oil-soluble dyes in the present invention are compounds represented by the following general formula (1) or (2).

[0027]

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In the formula, R ^{1 to} R ⁸ each represent a hydrogen atom, a hydroxy group, an amino group or a halogen atom.

[0029]

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In the formula, R ^{9 to} R ²⁰ each represent a hydrogen atom,
Represents a halogen atom, a nitro atom, a hydroxy atom, an alkyl group, an alkoxy group, an aminocarbonyl group, an amino group or a -N = NR group (where R is an aryl group).

Examples of the halogen atom represented by R ^{1 to} R ⁸ in the general formula (1) include a chlorine atom and a bromine atom. Alternatively, the amino group represented by R ^{1 to} R ⁸ may have a substituent. Examples of the substituent include an alkyl group (for example, a methyl group and a butyl group), an aryl group (for example, a phenyl group), an acyl group and the like. Groups (for example, methoxy group, benzoyl group, etc.) and the like.

Examples of the halogen atom represented by R ^{9 to} R ²⁰ in the general formula (2) include a chlorine atom and a bromine atom, and examples of the alkyl group include a methyl group, an ethyl group and a propyl group. And as the alkoxy group,
Examples thereof include a methoxy group, an ethoxy group, and a propoxy group. Examples of the aminocarbonyl group include a methylaminocarbonyl group and a phenylaminocarbonyl group. Further, the amino group represented by R ^{9 to} R ²⁰ may have the same substituent as in the general formula (1).

The following are typical specific examples of the oil-soluble dye used in the present invention, but the present invention is not limited thereto.

[0034]

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[0035]

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[0036]

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[0037]

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The oil-soluble dye which does not decolor in the treatment according to the present invention has a solubility in water at 20 ° C. of 1 × 10 ⁻² or less,
In order to more effectively exert the effects of the present invention, an organic dye containing no carboxylic acid group or a salt thereof, or a sulfonic acid group or a salt thereof in a molecule is preferable. More preferably,
In the molecule, a carboxylic acid group or a salt thereof, or a sulfonic acid group or a salt thereof, or a hydroxy anion (—O— group)
Organic dyes containing no are more preferred.

The colored pigments according to the present invention include lakes,
Pigments, organic pigments such as metal complex pigments, etc., and inorganic pigments are particularly preferably used in the present invention. Typical examples thereof include cobalt pigments such as cobalt green and cobalt violet, iron pigments such as red iron and Prussian blue. Pigment, chromium oxide, chromium pigment such as viridian,
Manganese pigments such as mineral violet, copper pigments such as emerald green, vanadium pigments such as vanadium blue, and sulfide pigments such as cadmium yellow and ultramarine blue can be preferably used.

The colored pigments preferably used in the present invention include:
It is preferably used at a coating amount of 0.01 mg / m ^{2 to} 10 mg / m ² , more preferably 0.05 mg / m ^{2 to} 5 m
g / m ² is more preferable.

It is also preferable to use an oil-soluble dye and a coloring pigment in combination to obtain the effects of the present invention. At this time, each of the additional layers is preferably a different layer.

The composition of the silver halide photographic emulsion according to the present invention has an arbitrary halogen composition such as silver chloride, silver bromide, silver chlorobromide, silver iodobromide, silver chloroiodobromide and silver chloroiodide. However, silver chlorobromide containing 95 mol% or more of silver chloride and containing substantially no silver iodide is preferred. From the viewpoint of rapid processing property and processing stability, the silver halide emulsion preferably contains 97 mol% or more, more preferably 98 to 99.9 mol%, of average silver chloride.

In order to obtain the above silver halide emulsion, a silver halide emulsion having a portion containing silver bromide at a high concentration is particularly preferably used. In this case, the portion containing silver bromide at a high concentration may be epitaxy-bonded to silver halide emulsion grains, may be a so-called core-shell emulsion, or may be only partially formed without forming a complete layer. May simply have regions with different compositions. The composition may change continuously or may change discontinuously. It is particularly preferable that the portion where silver bromide exists at a high concentration is the top of crystal grains on the surface of silver halide grains.

In the present invention, it is advantageous to include a heavy metal ion. Heavy metal ions that can be used for such purposes include Group 8 to 10 metals such as iron, iridium, platinum, palladium, nickel, rhodium, osmium, ruthenium, and cobalt; and twelfth metals such as cadmium, zinc, and mercury. Group transition metals, and ions of lead, rhenium, molybdenum, tungsten, gallium, chromium, and the like. Among them, metal ions of iron, iridium, platinum, ruthenium, gallium and osmium are preferred.

These metal ions can be added to the silver halide emulsion in the form of a salt or a complex salt.

When the heavy metal ion forms a complex,
Examples of the ligand or ion include cyanide ion, thiocyanate ion, isothiocyanate ion, cyanate ion, chloride ion, bromide ion, iodide ion, nitrate ion, carbonyl, and ammonia. Among them, cyanide ion, thiocyanate ion,
Preferred are isothiocyanate ion, chloride ion, bromide ion and the like.

In order to make the silver halide emulsion contain heavy metal ions, the heavy metal compound is added to the silver halide emulsion during the physical ripening before the formation of silver halide grains, during the formation of silver halide grains, and during the physical ripening after the formation of silver halide grains. It may be added at any place in the process. In order to obtain a silver halide emulsion satisfying the above conditions, the heavy metal compound may be dissolved together with the halide salt and added continuously over the whole or a part of the grain forming step.

The amount of heavy metal ions added to the silver halide emulsion is from 1 × 10 ^-9 to 1 × 1 per mol of silver halide.
It is preferably from 0 to ² mol, and particularly preferably from 1 × 10 ^{−8 to} 5 × 10 ⁻⁵ mol.

The silver halide grains may have any shape. One preferable example is a cube having a (100) plane as a crystal surface. Also, U.S. Pat. Nos. 4,183,756 and 4,225,666, JP-A-55-26589, JP-B-55-42737,
Octahedrons, tetradecahedrons, dodecahedrons, etc., by methods described in documents such as The Journal of Photographic Science (J. Photogr. Sci.) 21, 39 (1973). Can be produced and used. Further, particles having a twin plane may be used.

As the silver halide grains, grains having a single shape are preferably used, but it is particularly preferable to add two or more kinds of monodispersed silver halide emulsions to the same layer.

The grain size of the silver halide grains is not particularly limited, but is preferably 0.1 to 1.2 μm, and more preferably 0.2 to 1.2 μm, in consideration of other photographic properties such as rapid processing and sensitivity. The range is 1.0 μm. This particle size can be measured using the projected area or diameter approximation of the particle. If the particles are substantially uniform in shape, the particle size distribution can represent this quite accurately as diameter or projected area.

The grain size distribution of the silver halide grains is preferably a monodispersed silver halide grain having a coefficient of variation of preferably 0.05 to 0.22, more preferably 0.05 to 0.15.
Particularly preferably, two or more monodispersed emulsions of 0.05 to 0.15 are added to the same layer. Where the coefficient of variation is
This is a coefficient indicating the width of the particle size distribution, and is defined by the following equation.

Coefficient of variation = S / R (S is the standard deviation of the particle size distribution, and R is the average particle size.) The particle size referred to here is the diameter of spherical silver halide grains, In the case of particles having a shape other than a cubic or a spherical shape, the diameter represents a diameter when the projected image is converted into a circular image having the same area.

As the apparatus and method for preparing a silver halide emulsion, various methods known in the art can be used.

The silver halide emulsion may be obtained by any of an acidic method, a neutral method and an ammonia method. The particles may be grown at a time, or may be grown after seed particles have been produced. The method for producing the seed particles and the method for growing the seed particles may be the same or different.

The form of reacting the soluble silver salt with the soluble halide may be any of a forward mixing method, a reverse mixing method, a simultaneous mixing method, a combination thereof, and the like, but the method obtained by the simultaneous mixing method is preferable. . Further, as one form of the simultaneous mixing method, pA described in JP-A-54-48521 and the like are described.
g The controlled double jet method can also be used.

Also, JP-A-57-92523 and JP-A-57-92523.
No. 92524, etc., a device for supplying a water-soluble silver salt and a water-soluble halide aqueous solution from an addition device arranged in a reaction mother liquor, and a water-soluble silver salt described in DE 2,921,164. And an apparatus for continuously adding an aqueous solution of a water-soluble halide while changing its concentration, Japanese Patent Publication No. 56-5017.
No. 76, etc., a reaction mother liquor may be taken out of the reactor and concentrated by an ultrafiltration method to form grains while keeping the distance between silver halide grains constant.

If necessary, a silver halide solvent such as thioether may be used. Further, a compound having a mercapto group, a nitrogen-containing heterocyclic compound or a compound such as a sensitizing dye may be added at the time of forming silver halide grains or after the completion of grain formation.

The silver halide emulsion can be used in combination with a sensitization method using a gold compound and a sensitization method using a chalcogen sensitizer.

As the chalcogen sensitizer applied to the silver halide emulsion, a sulfur sensitizer, a selenium sensitizer, a tellurium sensitizer, and the like can be used, and a sulfur sensitizer is preferable.

Examples of the sulfur sensitizer include thiosulfate, allylthiocarbamide, thiourea, allylisothiocyanate, cystine, p-toluenethiosulfonate, rhodanine, inorganic sulfur and the like.

The amount of the sulfur sensitizer to be added is preferably changed depending on the kind of the silver halide emulsion to be applied, the expected effect, and the like.
10 ^{-10 to} 5 × 10 ^-5 mol, preferably 5 × 10 ^{-8 to} 3
A range of ^10-5 mol is desirable.

As a gold sensitizer, various gold complexes such as chloroauric acid and gold sulfide can be added. Examples of the ligand compound used include dimethyl rhodanine, thiocyanic acid, mercaptotetrazole, mercaptotriazole and the like. The amount of the gold compound used is not uniform depending on the type of silver halide emulsion, the type of compound to be used, the ripening conditions, etc., but usually 1 × 10 ^-4 to 1 × 10 ^-8 mol per mol of silver halide. Is preferably
More preferably, it is 1 × 10 ⁻⁵ to 1 × 10 ⁻⁸ mol.

The chemical sensitization of a silver halide emulsion includes:
A reduction sensitization method may be used.

The silver halide emulsion may contain a known antifoggant for the purpose of preventing fog generated during the preparation of the light-sensitive material, reducing performance fluctuation during storage, and preventing fog generated during development. Agents can be used. Examples of preferred compounds used for such purposes include the compounds represented by the general formula [II] described in the lower column of page 7 of JP-A-2-14636, and more preferred specific compounds include: II described on page 8 of the publication
a-1 to IIa-8, IIb-1 to IIb-7, 1
Compounds such as-(3-methoxyphenyl) -5-mercaptotetrazole and 1- (4-ethoxyphenyl) -5-mercaptotetrazole can be mentioned.

These compounds are added according to the purpose in the steps of preparing silver halide emulsion grains, chemical sensitizing step, finishing the chemical sensitizing step, and preparing a coating solution. When chemical sensitization is performed in the presence of these compounds, 1 × 10 ^{−5 to} 5 × 10 ⁻⁴ per mol of silver halide is used.
It is preferably used in a molar amount. When added at the end of chemical sensitization, 1 × 10
^-6 to 1 × 10 ⁻² mol is preferable, and 1 × 10 ^-5 to
5 × 10 ⁻³ mol is more preferred. When added to the silver halide emulsion layer in the coating solution preparation step, the amount of 1 × 10 ^-6 to 1 × 10 ^-1 mol per mol of silver halide is preferred, 1 × 10 ^-5 ~ × 10 ^{- Two} moles are more preferred.
Further, when added to a layer other than the silver halide emulsion layer,
The amount in the coating film is 1 × 10 ⁻⁹ to 1 × 10 ⁻³ per m ^2.
Molar amounts are preferred.

For the light-sensitive material, dyes having absorption in various wavelength ranges can be used for the purpose of preventing irradiation and halation. For this purpose, any of known compounds can be used. In particular, as dyes having absorption in the visible region, dyes of AI-1 to 11 described in JP-A-3-251840, p. The dyes described in JP-A-3770 are preferably used, and as the infrared absorbing dye, compounds represented by the general formulas (I), (II) and (III) described in the lower left column of page 2 of JP-A-1-280750 are preferable. It is preferable because it has spectral characteristics, does not affect the photographic characteristics of the photographic emulsion, and does not stain due to residual color. Specific examples of preferred compounds include the exemplified compounds (1) to (45) listed in the lower left column of page 3 to the lower left column of page 5 of the same publication. For the purpose of improving sharpness, the amount of these dyes added is preferably such that the spectral reflection density at 680 nm of an unprocessed sample of the light-sensitive material is 0.7 to 3.0, and more preferably 0.8 to 3.0. More preferably, it is 3.0.

As the spectral sensitizing dye used in the silver halide emulsion of the present invention, any known compounds can be used. As the blue-sensitive sensitizing dye, JP-A-3-251 can be used.
BS-1 to BS-8 described in page 840, page 28, can be preferably used alone or in combination. Examples of the green photosensitive sensitizing dye include GS-1 to GS described on page 28 of the same publication.
S-5 is preferred, and as the red-sensitive sensitizing dye, RS-1 to RS-8 described on page 29 of the same publication are preferably used. When performing image exposure with infrared light using a semiconductor laser or the like, it is necessary to use an infrared-sensitive sensitizing dye. No., pages 6-8, IRS-1
A dye of IRS-11 is preferably used. These infrared, red, green, and blue photosensitive sensitizing dyes are described in JP-A-4-285.
No. 950, pages 8-9, supersensitizers SS-1 to SS
It is preferable to use compounds S-1 to S-17 described in JP-A-5-9665 and JP-A-5-66515, pages 15 to 17 in combination.

The sensitizing dye may be added at any time from the formation of silver halide grains to the end of chemical sensitization.

The sensitizing dye may be added by dissolving it in a water-miscible organic solvent such as methanol, ethanol, fluorinated alcohol, acetone, dimethylformamide or the like or water, or adding it as a solid dispersion. It may be added.

As the coupler used in the light-sensitive material of the present invention, any compound capable of forming a coupling product having a spectral absorption maximum wavelength in a wavelength region longer than 340 nm by coupling reaction with an oxidized form of a color developing agent is used. Although it is also possible to use, particularly typical couplers include a yellow dye-forming coupler having a spectral absorption maximum wavelength in a wavelength range of 350 to 500 nm, a magenta dye-forming coupler having a spectral absorption maximum wavelength in a wavelength range of 500 to 600 nm,
Examples include those known as cyan dye-forming couplers having a spectral absorption maximum wavelength in a wavelength range of 600 to 750 nm.

Examples of cyan couplers that can be preferably used include couplers represented by general formulas [C-I] and [C-II] described in JP-A-4-114154, page 5, lower left column. As a specific compound, the publication 5
There can be mentioned those described as CC-1 to CC-9 in the lower right column of page 6 to the lower left column of page 6.

Examples of the magenta coupler that can be preferably used include couplers represented by general formulas [MI] and [M-II] described in the upper right column of page 4 of JP-A-4-114154. Specific compounds include those described as MC-1 to MC-11 in the lower left column of page 4 to the upper right column of page 5 of the publication. Among the above magenta couplers, more preferred are those represented by the general formula [MI]
A coupler represented by the general formula [M-
The coupler of the formula (I) wherein R _M is a tertiary alkyl group is particularly preferred because of its excellent light resistance. M described in the upper column on page 5 of the publication
C-8 to MC-11 are preferable because they are excellent in reproduction of colors ranging from blue to purple and red, and are also excellent in detail description.

As a yellow coupler which can be preferably used, a coupler represented by the general formula [YI] described in the upper right column of page 3 of JP-A-4-114154 can be mentioned. YC on the lower left column of page 3
-1 to YC-9. Among them, a coupler of the formula [Y-I] in which R _Y1 is an alkoxy group or a coupler represented by the formula [I] described in JP-A-6-67388 is preferable because it can reproduce yellow having a preferable color tone. Of these, YC-8 and YC-9 and JP-A-6-673881 described in the upper left column of page 4 of JP-A-4-114154 are particularly preferred.
Compounds represented by Nos. (1) to (47) on pages 3 to 14 can be exemplified. The most preferred compound is a compound represented by the general formula [Y-1] described in JP-A-4-81847, pages 1 and 11-17.

When an oil-in-water emulsion dispersion method is used to add a coupler or other organic compound used in a light-sensitive material, it is usually added to a water-insoluble high-boiling organic solvent having a boiling point of 150 ° C. or higher, if necessary. Then, a low boiling point or water-soluble organic solvent is used in combination to dissolve, and emulsified and dispersed in a hydrophilic binder such as an aqueous gelatin solution using a surfactant. As a dispersing means, a stirrer, a homogenizer, a colloid mill, a flow jet mixer, an ultrasonic disperser, or the like can be used. After or simultaneously with the dispersion, a step of removing the low-boiling organic solvent may be included.

High-boiling organic solvents which can be used for dissolving and dispersing the coupler include phthalic acid esters such as dioctyl phthalate, di-i-decyl phthalate and dibutyl phthalate, tricresyl phosphate and trioctyl phosphate. And the like are preferably used. The high-boiling organic solvent preferably has a dielectric constant of 3.5 to 7.0. Further, two or more kinds of high-boiling organic solvents can be used in combination.

In place of the method using a high-boiling organic solvent or in combination with a high-boiling organic solvent, a water-insoluble and organic solvent-soluble polymer compound may be added, if necessary, to a low-boiling and / or water-soluble organic solvent. In a hydrophilic binder such as an aqueous gelatin solution by using a surfactant and emulsifying and dispersing by various dispersing means. Examples of the water-insoluble and organic solvent-soluble polymer used at this time include poly (Nt-butylacrylamide).

As a preferred compound used as a surfactant for dispersing a photographic additive or adjusting a surface tension at the time of coating, a hydrophobic group having 8 to 30 carbon atoms and a sulfonic acid group or a salt thereof in one molecule. Containing. Specifically, A-1 to A-1 described in JP-A-64-26854.
1 is mentioned. Further, a surfactant in which a fluorine atom is substituted for an alkyl group is also preferably used. These dispersions are
Usually, it is added to a coating solution containing a silver halide emulsion, but it is better that the time until the addition to the coating solution after dispersion and the time from the addition to the coating solution to the coating are shorter, each being preferably within 10 hours. More preferably, within 3 hours and within 20 minutes.

It is preferable to use an anti-fading agent in combination with each of the above couplers in order to prevent fading of the formed dye image due to light, heat, humidity and the like. Particularly preferred compounds include phenyl ether compounds represented by general formulas [I] and [II] described in JP-A-2-66541, page 3, and phenols represented by general formula [IIIB] described in JP-A-3-174150. Amine compounds represented by the general formula [A] described in JP-A-64-90445;
General formulas (XII), (XIII) and (XI) described in No. 182741
V] and metal complexes represented by [XV] are particularly preferred for magenta dyes. Also, a compound represented by the general formula [I] described in JP-A-1-19649 and JP-A-5-1141.
The compound represented by the general formula [II] described in No. 7 is particularly preferable for yellow and cyan dyes.

Compounds such as compound d-11 described in the lower left column of page 9 of JP-A-4-114154 and compound A'-1 described in the upper left column of page 10 are used for shifting the absorption wavelength of the coloring dye. be able to. In addition, the fluorescent dye releasing compounds described in U.S. Pat. No. 4,774,187 can also be used.

In the light-sensitive material, a compound which reacts with an oxidized developing agent is added to a layer between the light-sensitive layers to prevent color turbidity, or is added to a silver halide emulsion layer to prevent fog or the like. Is preferably improved. As the compound for this, a hydroquinone derivative is preferred, and more preferably
Dialkylhydroquinones such as 5-di-t-octylhydroquinone. Particularly preferred compounds are those represented by the general formula [II] described in JP-A-4-133056, and the compounds II-1 to II-14 described on pages 13 to 14 of the same publication.
Compounds-1 described on pages II-14 and 17 are mentioned.

It is preferable to add an ultraviolet absorber to the light-sensitive material to prevent static fog or to improve the light fastness of the dye image. Preferable ultraviolet absorbers include benzotriazoles, and particularly preferable compounds are those represented by the general formula [III-] described in JP-A-1-250944.
3], a compound represented by the general formula [III] described in JP-A-64-66646, and a compound represented by JP-A-63-18
No. 7240, UV-1L to UV-27L;
Compounds represented by the general formula [I] described in JP-A-1633 and compounds represented by the general formulas (I) and (II) described in JP-A-5-165144.

It is advantageous to use gelatin as a binder in the light-sensitive material of the present invention. If necessary, a gelatin derivative, a graft polymer of gelatin and another polymer, a protein other than gelatin, a sugar derivative, a cellulose derivative, A hydrophilic colloid such as a single or a synthetic hydrophilic polymer such as a copolymer can also be used.

As the hardener of these binders, it is preferable to use a vinyl sulfone hardener, a chlorotriazine hardener or a carboxyl group-active hardener alone or in combination. JP-A-61-249054, 61-
It is preferable to use the compounds described in US Pat. Further, in order to prevent the growth of molds and bacteria which adversely affect the photographic performance and image storability, JP-A-3-15764 is incorporated in the colloid layer.
It is preferable to add a preservative and an antifungal agent as described in No. 6. In order to improve the physical properties of the surface of the light-sensitive material or the processed sample, it is preferable to add a slipping agent or a matting agent described in JP-A-6-118543 or JP-A-2-73250 to the protective layer.

As the support used for the light-sensitive material, any material may be used, including paper coated with polyethylene or polyethylene terephthalate, paper support made of natural pulp or synthetic pulp, vinyl chloride sheet, and white pigment. For example, polypropylene, polyethylene terephthalate support, baryta paper, etc. may be used. Among them, a support having a water-resistant resin coating layer on both sides of the base paper is preferable.

As the water resistant resin, polyethylene, polyethylene terephthalate or a copolymer thereof is preferable.

As the white pigment used for the support, inorganic and / or organic white pigments can be used, and preferably, inorganic white pigments are used. For example, sulfates of alkaline earth metals such as barium sulfate, carbonates of alkaline earth metals such as calcium carbonate, silicas such as fine silica powder, synthetic silicates, calcium silicate, alumina, alumina hydrate, titanium oxide, oxide Zinc, talc, clay and the like can be mentioned. The white pigment is preferably barium sulfate or titanium oxide.

The amount of the white pigment contained in the water-resistant resin layer on the surface of the support is preferably 13% by weight or more, and more preferably 15% by weight, in order to improve sharpness.

The degree of dispersion of the white pigment in the water-resistant resin layer of the paper support can be measured by the method described in JP-A-2-28640. When measured by this method, the degree of dispersion of the white pigment is preferably 0.20 or less, more preferably 0.15 or less, as the variation coefficient described in the publication.

Further, it is more preferable that the value of the center surface average roughness (SRa) of the support is 0.15 μm or less, more preferably 0.12 μm or less, since the effect of good gloss is obtained.
Also, in the white pigment-containing water-resistant resin of the reflective support or in the applied hydrophilic colloid layer, to improve the whiteness by adjusting the spectral reflection density balance of the white background after treatment, ultramarine blue, oil-soluble dyes, etc. It is preferable to add a small amount of a bluing agent or a reddish agent.

The light-sensitive material may be subjected to corona discharge, ultraviolet irradiation, flame treatment, etc. on the surface of the support, if necessary, and then directly or to an undercoat layer (adhesion, antistatic property, dimensional stability of the support surface). , One or more undercoat layers for improving friction resistance, hardness, antihalation property, friction characteristics or other properties).

In coating a light-sensitive material using a silver halide emulsion, a thickener may be used to improve coatability. Extrusion coating and curtain coating, in which two or more layers can be applied simultaneously, are particularly useful as a coating method.

In order to form a photographic image using the photosensitive material of the present invention, the image recorded on the negative may be optically formed on the photosensitive material to be printed and printed. Is once converted into digital information, the image is formed on a CRT (cathode ray tube), and this image may be formed on a photosensitive material to be printed and printed, or a laser based on the digital information may be used. Printing may be performed by scanning while changing the light intensity.

The present invention is preferably applied to a light-sensitive material in which a developing agent is not incorporated in the light-sensitive material, and particularly preferably to a light-sensitive material which directly forms an image for viewing.

As the aromatic primary amine developing agent used in the present invention, known compounds can be used. The following compounds can be mentioned as examples of these compounds.

CD-1: N, N-diethyl-p-phenylenediamine CD-2: 2-amino-5-diethylaminotoluene CD-3: 2-amino-5- (N-ethyl-N-lauryl) aminotoluene CD-4: 4- (N-ethyl-N-β-hydroxyethyl) aminoaniline CD-5: 2-Methyl-4- (N-ethyl-N-β-hydroxyethyl) amino) aniline CD-6: 4 -Amino-3-methyl-N-ethyl-N-
(Β-methanesulfonamido) ethylaniline CD-7: 4-amino-3-β-methanesulfonamidoethyl-N, N-diethylaniline CD-8: N, N-dimethyl-p-phenylenediamine CD-9: 4-amino-3-methyl-N-ethyl-N-
Methoxyethylaniline CD-10: 4-amino-3-methyl-N-ethyl-N
-(Β-ethoxyethyl) aniline CD-11: 4-amino-3-methyl-N-ethyl-N
-([Gamma] -hydroxypropyl) ethylaniline In the present invention, the use of the above compound is adjusted to pH 9.5 to 13.0, more preferably pH 9.5, from the viewpoint of rapid processing.
Used in the range of 8 to 12.0.

The processing temperature for color development in the present invention is 3
5-70 ° C is preferred. The higher the temperature, the shorter the processing time is possible, which is preferable. However, it is preferable that the temperature is not too high from the viewpoint of the stability of the processing solution.

Conventionally, the color development time is generally 3 minutes 30 minutes.
Although it is performed in about seconds, in the present invention, it is preferably performed within 40 seconds, and more preferably within 25 seconds.

To the color developing solution, known developing component compounds can be added in addition to the above color developing agents. Usually, an alkali agent having a pH buffering action, a development inhibitor such as chloride ion and benzotriazole, a preservative, a chelating agent and the like are used.

After color development, the light-sensitive material is subjected to bleaching and fixing. The bleaching process may be performed simultaneously with the fixing process. After the fixing process, a water washing process is usually performed. Further, as an alternative to the washing process, a stabilizing process may be performed.

[0101]

EXAMPLES The present invention will be described below with reference to examples, but the embodiments of the present invention are not limited thereto.

Example 1 A high-density polyethylene was laminated on both sides of a paper pulp having a basis weight of 180 g / m ² to prepare a paper support. However, on the side to be coated with the emulsion layer, a molten polyethylene containing a surface-treated anatase type titanium oxide dispersed at a content of 15% by weight was laminated,
A reflective support was made. After the reflective support was subjected to corona discharge treatment, a gelatin undercoat layer was provided thereon, and each layer having the following constitution was further provided thereon to prepare a silver halide photographic light-sensitive material.

Fifth layer (protective layer) Addition amount g / m ² Gelatin 0.7 Fourth layer (ultraviolet absorbing layer) Gelatin 1.5 Ultraviolet absorber UV-1 4.0 Ultraviolet absorber UV-2 1.3 UV absorber UV-3 5.0 Third layer (red-sensitive layer) Gelatin 2.0 Yellow coupler Y-1 0.38 Magenta coupler M-1 0.14 Cyan coupler C-1 0.09 Cyan coupler C-2 0.26 Dye image stabilizer ST-1 0.04 Dye image stabilizer ST-2 0.02 DBP 0.83 Red-sensitive silver halide emulsion (Em-R) 0.39 AI-1 0.05 Second layer (Green-sensitive layer) Gelatin 2.0 Yellow coupler Y-1 0.26 Magenta coupler M-1 0.09 Cyan coupler C-1 0.06 Cyan coupler C-2 0.18 Dye image stabilizer ST-10. 03 colors Image stabilizer ST-2 0.01 DBP 0.57 Green-sensitive silver halide emulsion (Em-G) 0.26 AI-2 0.01 First layer (blue-sensitive layer) Gelatin 0.5 Yellow coupler Y-1 0.05 Magenta coupler M-1 0.02 Cyan coupler C-1 0.01 Cyan coupler C-2 0.03 Dye image stabilizer ST-1 0.004 Dye image stabilizer ST-2 0.002 DBP 07 Blue-sensitive silver halide emulsion (Em-B) 0.05 AI-2 0.03 Support Polyethylene laminated paper The amount of silver halide emulsion added was expressed in terms of silver. (H-1) and (H-2) were added as hardeners. Surfactants (SU-1), (S
U-2) was added to adjust the surface tension. Further, an antifungal agent (F-1) was added to each layer so that the total amount was 0.04 g / m ² .

SU-1: di (2-ethylhexyl) sulfosuccinate sodium salt SU-2: di (2,2,3,3,4,4, sulfosuccinate)
5,5-octafluoropentyl) sodium salt DBP: dibutyl phthalate H-1: tetrakis (vinylsulfonylmethyl) methane H-2: 2,4-dichloro-6-hydroxy-s-triazine sodium

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<Preparation of Blue-Sensitive, Green-Sensitive and Red-Sensitive Silver Halide Emulsions> (Preparation of Blue-Sensitive Silver Halide Emulsion Em-B) The following (Solution A) was placed in 1 liter of a 2% aqueous gelatin solution kept at 40 ° C.
And (Solution B) were added simultaneously over 30 minutes while controlling pAg = 7.3 and pH = 3.0, and the following (Solution C) and (Solution D) were further pAg = 8.0, pH = 5. And added simultaneously over 180 minutes. At this time, pAg was controlled by the method described in JP-A-59-45437, and pH was controlled.
Was controlled using sulfuric acid or an aqueous solution of sodium hydroxide.

(Solution A) Sodium chloride 3.42 g Potassium bromide 0.03 g Water was added to 200 ml (Solution B) Silver nitrate 10 g Water was added to 200 ml (Solution C) Sodium chloride 102.7 g K ₂ IrCl ₆ 4 × 10 ^-8 mol / mol Ag K ₄ Fe (CN) ₆ 2 × 10 ^-5 mol / mol Ag Potassium bromide 1.0 g Add water 600 ml (Solution D) Silver nitrate 300 g Add water 600 ml after completion of addition, Kao Atlas After desalting using a 5% aqueous solution of Demol N and 20% aqueous solution of magnesium sulfate, the mixture was mixed with an aqueous gelatin solution to give an average particle size of 0.71 μm.
m, coefficient of variation of particle size distribution 0.07, silver chloride content 99.
A 5 mol% monodispersed cubic emulsion EMP-1 was obtained.

Next, EMP was performed except that the addition time of (solution A) and (solution B) and the addition time of (solution C) and (solution D) were changed.
As in the case of -1, the average particle diameter is 0.64 μm, and the coefficient of variation is 0.1.
07, a monodispersed cubic emulsion EMP-1B having a silver chloride content of 99.5 mol% was obtained.

The above-mentioned EMP-1 was optimally subjected to chemical sensitization at 60 ° C. using the following compounds. Also, EMP-1B
Similarly, after the optimal chemical sensitization, the sensitized E
MP-1 and EMP-1B were mixed at a silver ratio of 1: 1 to obtain a blue-sensitive silver halide emulsion (Em-B).

Sodium thiosulfate 0.8 mg / mol AgX Chloroauric acid 0.5 mg / mol AgX Stabilizer STAB-1 3 × 10 ⁻⁴ mol / mol AgX Stabilizer STAB-2 3 × 10 ⁻⁴ mol / mol AgX stability Agent STAB-3 3 × 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 Preparation of Em-G) Except for changing the addition time of (Solution A) and (Solution B) and the addition time of (Solution C) and (Solution D), the average particle diameter was adjusted in the same manner as in EMP-1.
40 μm, coefficient of variation 0.08, silver chloride content 99.5%
To obtain a monodispersed cubic emulsion EMP-2.

Next, a monodisperse cubic emulsion EMP-2B having an average particle size of 0.50 μm, a coefficient of variation of 0.08, and a silver chloride content of 99.5% was obtained.

The above-mentioned EMP-2 was optimally subjected to chemical sensitization at 55 ° C. using the following compounds. Also, EMP-2B
Similarly, after the optimal chemical sensitization, the sensitized E
MP-2 and EMP-2B were mixed at a silver amount of 1: 1 to obtain a green-sensitive silver halide emulsion (Em-G).

Sodium thiosulfate 1.5 mg / mole AgX Chloroauric acid 1.0 mg / mole AgX Stabilizer STAB-1 3 × 10 ⁻⁴ mol / mole AgX Stabilizer STAB-2 3 × 10 ⁻⁴ mol / mole AgX Stable Agent STAB-3 3 × 10 ^-4 mol / mol AgX sensitizing dye GS-1 4 × 10 ^-4 mol / mol AgX (Preparation of red-sensitive silver halide emulsion Em-R) (solution A) and (solution B) Except that the addition time of (C) and (C solution) and (D solution) were changed.
40 μm, coefficient of variation 0.08, silver chloride content 99.5%
Was obtained as a monodispersed cubic emulsion EMP-3. The average particle size was 0.38 μm, the coefficient of variation was 0.08, and the silver chloride content was 99.
A 5% monodisperse cubic emulsion EMP-3B was obtained.

The above-mentioned EMP-3 was optimally subjected to chemical sensitization at 60 ° C. using the following compounds. Also, EMP-3B
Similarly, after the optimal chemical sensitization, the sensitized E
MP-3 and EMP-3B were mixed at a silver amount of 1: 1 to obtain a red-sensitive silver halide emulsion (Em-R).

Sodium thiosulfate 1.8 mg / mol AgX chloroauric acid 2.0 mg / mol AgX stabilizer STAB-1 3 × 10 ⁻⁴ mol / mol AgX stabilizer STAB-2 3 × 10 ⁻⁴ mol / mol AgX stability Agent STAB-3 3 × 10 ⁻⁴ mol / mol AgX sensitizing dye RS-1 1 × 10 ⁻⁴ mol / mol AgX sensitizing dye RS-2 1 × 10 ⁻⁴ mol / mol AgX STAB-1: 1- ( 3-acetamidophenyl) -5-mercaptotetrazole STAB-2: 1-phenyl-5-mercaptotetrazole STAB-3: 1- (4-ethoxyphenyl) -5-mercaptotetrazole -1 was added in an amount of 2.0 × 10 ^-3 mol per mol of silver halide.

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The sample prepared as described above was used as the sample 101.
And Next, each sample was prepared in the same manner as the sample 101 except that the sample 101 was changed as shown in Table 1.
These samples were subjected to white light wedge exposure and developed according to a standard method.

Processing step Processing temperature Time Replenishment amount Color development 38.0 ± 0.3 ° C 45 seconds 80ml Bleaching and fixing 35.0 ± 0.5 ° C 45 seconds 120ml Stabilization 30-34 ° C 60 seconds 150ml Dry Drying 60 to 80 ° C. for 30 seconds The composition of the developing solution is shown below.

<Color developing solution tank solution and replenisher> Tank solution replenisher pure water 800 ml 800 ml triethylenediamine 2 g 3 g diethylene glycol 10 g 10 g potassium bromide 0.01 g-potassium chloride 3.5 g-potassium sulfite 0.25 g 0.5 g N -Ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 6.0 g 10.0 g N, N-diethylhydroxylamine 6.8 g 6.0 g Triethanolamine 10.0 g 10.0 g Diethylenetriaminepentaacetic acid sodium salt 2.0 g 2.0 g Optical brightener (4,4'-diaminostilbene disulfonic acid derivative) 2.0 g 2.5 g Potassium carbonate 30 g 30 g Add water to make the total volume 1 liter. When pH = 10.10, replenisher is p = Adjusted to 10.60.

<Bleaching and Fixing Solution Tank Solution and Replenisher> Diethylenetriaminepentaacetic acid ammonium ferric dihydrate 65 g Diethylenetriaminepentaacetic acid 3 g Ammonium thiosulfate (70% aqueous solution) 100 ml 2-amino-5-mercapto-1,3,4- Thiadiazole 2.0 g Ammonium sulfite (40% aqueous solution) 27.5 ml Add water to make the total volume 1 liter, and adjust the pH to 5.0 with potassium carbonate or glacial acetic acid.

<Stabilizing Solution Tank Solution and Replenisher> o-phenylphenol 1.0 g 5-chloro-2-methyl-4-isothiazolin-3-one 0.02 g 2-methyl-4-isothiazolin-3-one 0 0.02 g Diethylene glycol 1.0 g Optical brightener (Tinopearl SFP) 2.0 g 1-hydroxyethylidene-1,1-diphosphonic acid 1.8 g Bismuth chloride (45% aqueous solution) 0.65 g Magnesium sulfate heptahydrate 0.2 g PVP (polyvinylpyrrolidone) 1.0 g ammonia water (25% ammonium hydroxide aqueous solution) 2.5 g nitrilotriacetic acid / trisodium salt 1.5 g water was added to make a total volume of 1 liter, and the pH was 7.7 with sulfuric acid or aqueous ammonia. Adjust to 5.

After running 5 m ^{2 of} each sample every day for 7 days by the above-described processing, the following measurement was performed on the sample of the black and white image formed last.

1) The hue of each sample at a reflection density of 0.1 was measured by a method of JIS Z-8729 and Z-8730 using a 607 type color analyzer (manufactured by Hitachi, Ltd.). b *) = color difference E from (0,0)
Was calculated as a measure of neutrality.

2) The white portion was visually observed and used as a measure of white background.

Table 1 shows the results. With the black-and-white image sample of the present invention, a sample with good neutrality was obtained and could not be predicted. An image having good whiteness was obtained.

[0130]

[Table 1]

(Example 2) In Example 1, QDP-1500 manufactured by Konica Corporation was used as a printer processor.
A, Konica ECOJET-HQA-
A test was conducted in the same manner as in Example 1 except that B was used and a running treatment was performed according to the process name CPK-HQA-1. With the sample of the present invention, the effects of the present invention were obtained.

[0132]

According to the constitution of the present invention, it is possible to provide a black-and-white silver halide photographic light-sensitive material which can be color-processed and which has good neutrality of a black-and-white image even after running processing. . Further, a black-and-white silver halide photographic light-sensitive material capable of performing color processing and having good whiteness was provided.

Claims (3)

[Claims] 1. A halogen having, on a support, a green-sensitive silver halide emulsion-containing layer and a plurality of silver halide emulsion-containing layers including a blue-sensitive silver halide emulsion or a layer containing a red-sensitive silver halide emulsion. In silver halide photographic materials,
At least one of the plurality of silver halide emulsion-containing layers contains three couplers of a yellow coupler, a magenta coupler and a cyan coupler or a black-forming coupler, and the green-sensitive silver halide emulsion layer is formed on a support. On the other hand, a silver halide photographic light-sensitive material is located farther from a layer containing the blue-sensitive silver halide emulsion or the red-sensitive silver halide emulsion. 2. A silver halide photographic light-sensitive material having a photographic component layer comprising at least one silver halide emulsion-containing layer on a support, wherein said at least one silver halide emulsion-containing layer comprises a yellow coupler. A silver halide photographic light-sensitive material comprising three types of couplers, a magenta coupler and a cyan coupler or a black-forming coupler, and a fluorescent brightener in the support or the photographic constituting layer. 3. A silver halide photographic light-sensitive material having a photographic component layer comprising at least one silver halide emulsion-containing layer on a support, wherein said at least one silver halide emulsion-containing layer comprises a yellow coupler. Containing three types of magenta couplers and cyan couplers or a black-forming coupler, and wherein the support or the photographic component layer contains an oil-soluble dye or a colored pigment which does not substantially decolorize during processing. Silver halide photographic light-sensitive material.