JPH10254108A - Silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a silver halide photographic sensitive material having satisfactory shadow representability, flesh color reproducibility with a slight change in color balance to an exposure region and improved gray reproducibility. SOLUTION: This silver halide photographic sensitive material has at least one silver halide emulsion layer on the substrate. The γratio of a magenta color image formed by exposing the silver halide emulsion layer with monochromatic light is 100-135 and the max. density of the magenta dye image is >=1.90. The γ ratio is represented by the equation (γ ratio)=γA/γB×100 [where γA=1.0/ log10 (E1 /E2 ), γB=1.0/log10 (E3 /E4 ), E1 is exposure required to give a reflection density of Dmin+0.8, E2 is exposure required to give a reflection density of Dmin+1.8, E3 is exposure required to give a reflection density of Dmin+0.3, E4 is exposure required to give a reflection density of Dmin+0.8 and Dmin is the reflection density of the unexposed part].

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a silver halide color improved in shadow depiction, skin color reproducibility with a small change in color balance with respect to the exposure range, and gray reproducibility. It relates to a photosensitive material.

[0002]

2. Description of the Related Art With the spread of silver halide color photographic light-sensitive materials, there has been an increasing demand for silver halide color photographic light-sensitive materials capable of obtaining excellent descriptiveness and natural skin color.
Under such circumstances, in color print photosensitive materials, particularly, color print photosensitive materials having high shadow reproducibility, skin color reproducibility with little change in color balance, and high gray reproducibility are required. In particular, it is an important characteristic in the field of business photography. As a technique for improving shadow depiction, a technique for increasing a differential gradation ratio in a specific exposure area is described in JP-A-8-36247. Further, a technique having excellent color reproducibility by using a single color gradation and a specific magenta coupler is described in JP-A-62-173664. Further, Japanese Patent Application Laid-Open No. 1-128847 suggests improvement in color reproducibility and gradation reproducibility based on a gradation ratio obtained by monochromatic exposure and a gradation ratio obtained by white exposure. Also, Japanese Patent Application Laid-Open No. Sho 62-15
No. 0343 describes a technique for improving the resolving power by a specific gradation. Japanese Patent Application Laid-Open No. 8-1222984 describes a technique for improving skin color reproducibility by coloring. However, in reality, sufficient improvement cannot be obtained due to coloring problems. As described above, it is conventionally known that gradation is a characteristic that affects color reproducibility and shadow depiction. However, in the prior art, sufficient shadow depiction has not been obtained, and it has been extremely difficult to simultaneously improve the stable skin color reproducibility and the gray reproducibility in the exposure area. However, in the field of business photography, improvement of these properties is particularly strongly desired. Particularly, it is very difficult to reproduce the fine gradation of the shade of the black tuxedo and the faithful reproduction of the difference in the skin color between a woman and a man as in a wedding photograph, and it has been impossible with the prior art.

[0003]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a silver halide light-sensitive material having satisfactory shadow depiction, improved skin color reproducibility with a small change in color balance over the exposure area, and improved gray reproducibility. Is to do.

[0004]

The above objects of the present invention have been attained by the following constitutions.

(1) In a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, a magenta image formed by monochromatic exposure of the silver halide emulsion layer is represented by the following formula: Is a silver halide photographic light-sensitive material having a gamma ratio in the range of 100 to 135 and a maximum density of the magenta image of 1.90 or more.

Γ ratio = γA / γB × 100 wherein γA = 1.0 / log ₁₀ (E ₁ / E ₂ ) γB = 1.0 / log ₁₀ (E ₃ / E ₄ ) E ₁ and E ₂ Are Dmin + 0.8 and Dmin +
It represents the exposure required to give a reflection density of 1.8. E
₃ and E ₄ are Dmin + 0.3, Dmin + 0.
8 represents the exposure required to give a reflection density of 8. However,
Dmin is the reflection density of the unexposed portion. (2) The silver halide photographic material according to (1), wherein ΔλL _0.2 represented by the following formula for forming a magenta color image is 90 or less.

ΔλL _0.2 = λL _0.2 -λmax [where, λmax is the maximum peak wavelength when the maximum color density of the spectral absorption spectrum of the color dye formed from the magenta coupler on paper is set to 1.0. λL
_0.2 is the wavelength at which the concentration 0.2 of the spectral absorption spectrum is given. (3) The silver halide photograph according to (1), wherein the high-boiling organic solvent contained in the color forming dye forming the magenta image has a compound represented by the following general formula (A). Photosensitive material.

[0008]

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[Wherein, R ^a1 represents a substituent, R ^a2 represents a hydrogen atom or a substituent, and m represents an integer of 0-4. When m is 2 or more, a plurality of R ^a2 may be the same or different, and the total number of carbon atoms of R ^a1 and R ^a2 is 12
It is 36 or less. That is, as a result of investigations by the present inventors to achieve the above object of the present invention, particularly excellent shadow depiction and stable skin color reproduction can be achieved by selecting a color balance of a specific gradation formed by monochromatic exposure and selecting a maximum density. And gray balance were obtained. Further, a more remarkable effect has been found with a specific magenta coupler and a high boiling point solvent.

Hereinafter, the present invention will be described in detail.

An object of the present invention is to provide a silver halide photographic light-sensitive material having at least one silver halide emulsion on a support, wherein a magenta color image formed by monochromatic exposure of the silver halide emulsion layer is formed. A silver halide photographic material having a γ ratio in the range of 100 to 135 and a maximum density of the color image of 1.90 or more. Furthermore, it is achieved by the following three items. That is, the gamma ratio of the magenta image formed by monochromatic exposure of the silver halide emulsion layer according to the present invention is 100 to 100.
135 and the maximum density of the color image is 1.90.
This is achieved with the silver halide photographic light-sensitive material described above. The γ ratio of the other layer is not particularly limited, but the monochromatic γ ratio of magenta to yellow is preferably 85 to 115. Although there is no particular limitation on the monochromatic γA and γB, γA for forming a magenta monochromatic image is preferably from 1.80 to 2.50, and more preferably from 1.90 to 2.40.

The γ ratio of a magenta image formed by monochromatic exposure of a silver halide emulsion layer of a silver halide photographic light-sensitive material according to the present invention will be described.

In the present invention, the γ ratio is a color temperature of 3300.
A sample subjected to the following monochromatic exposure through a neutral step tablet using a K halogen lamp for 1.0 second is subjected to normal color development, and the developed samples are subjected to maximum transmission wavelengths of 644 nm, 546 nm and 436 nm, respectively.
densitometer (nm Konica PDA)
The reflection density is measured using a -84 type reflection densitometer, and the γ ratio is calculated by the following equation.

Γ ratio = γA / γB × 100 where γA = 1.0 / log ₁₀ (E ₁ / E ₂ ) γB = 1.0 / log ₁₀ (E ₃ / E ₄ ) Expressing reflection density at Dmin, E ₁ and E ₂ each Dmin + 0.8, Dmin + 1.8
Represents the amount of exposure required to give a reflection density of E ₃ and E ₄ represent exposure amounts required to give reflection densities of Dmin + 0.3 and Dmin + 0.8, respectively.

In the present invention, the maximum density of a magenta color image means a Kodak Wratten gelatin filter N06 as green exposure using a halogen lamp having a color temperature of 3300K.
Monochromatic exposure is performed for 1.0 second through a neutral step tablet using one green filter, and after color development, the maximum reflection density is determined by a Konica PD84 densitometer to determine the maximum density of the magenta color image.

When obtaining the maximum density of the magenta color image, instead of using the Kodak Wratten gelatin filter N061 green filter as the green exposure, Kodak Wratten gelatin filter N047B blue filter as the blue exposure and Kodak Wratten as the red exposure. Except for using the gelatin filter N029 red filter, the maximum density of the yellow image and the maximum density of the cyan image can be obtained in the same manner as in the case of obtaining the maximum density of the magenta image.

In the present invention, the maximum density of the magenta color image is 1.90 or more, and the upper limit is not particularly limited, but is 2.30.
The following is preferred. If the ratio is 2.31 or more, the obtained effect is not changed but rather disadvantageous in the production cost.

A description will be given of ΔλL _0.2 in the present invention.

The maximum peak wavelength when the maximum color density of the spectral absorption spectrum of the color dye formed from the magenta coupler used in the present invention on paper is 1.0 is λmax. When the wavelength at which the concentration 0.2 of the spectral absorption spectrum is given is λL _0.2 , ΔλL
_0.2 is represented by the following equation.

ΔλL _0.2 = λL _0.2 −λmax In the present invention, ΔλL _0.2 is preferably 90 or less, and there is no particular lower limit, but it is preferably 60 or more. If it is less than 59, the spectral absorption characteristic becomes too sharp, and the visual color change due to the viewing light source becomes large.

In order to obtain the γ ratio and the maximum concentration of the present invention,
A technique for adjusting the gradation of the silver halide emulsion layer is required. As the gradation adjusting technique, a method conventionally used in the art can be applied. For example, the γ ratio and the maximum density can be adjusted by the amount of coated silver and the amount of coated coupler. Preferred conditions are shown below.

Emulsion layer Silver coated g / m ² Coated coupler mole / m ² Cyan coupler-containing layer 0.1 to 0.35 1 × 10 ^{-4 to} 5 × 10 ^-3 Magenta coupler-containing layer 0.1 to 0 0.35 1 × 10 ^{-4 to} 5 × 10 ^-3 Yellow coupler-containing layer 0.1 to 0.45 More preferable condition than 1 × 10 ^{-4 to} 5 × 10 ^-3 Emulsion layer Cyan coupler-containing layer 0.1 to 0. 255 5 × 10 ^{-4 to} 2 × 10 ^-3 Magenta coupler containing layer 0.1 to 0.25 4 × 10 ^-4 to 2 × 10 ^-3 Yellow coupler containing layer 0.15 to 0.35 2 × 10 ^-4 particular restriction on the magenta coupler used in to 2 × 10 ^-3 present invention contains a free but silver halide layer, a magenta coupler DerutaramudaL _0.2 is 90 or less after color on a support is preferably used. A magenta coupler is disclosed in
Couplers represented by the following general formulas [MI] and [M-II] described in the upper right column of page 14 of JP-A No. 14154 are described.

[0023]

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In the formula, Z _M represents a group of nonmetal atoms necessary for forming a nitrogen-containing heterocyclic ring, and the ring formed by Z _M may have a substituent. X _M represents a hydrogen atom or a group capable of leaving by reaction with an oxidized form of a color developing agent. R _M represents a hydrogen atom or a substituent.

[0025]

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In the formula, Ar _M represents an aryl group, X represents a halogen atom, an alkoxy group or an alkyl group, and R represents a group that can be substituted on a benzene ring. n represents 1 or 2. When n is 2, R may be the same group or different groups. Y represents a group which can be removed by a coupling reaction with an oxidized form of an aromatic primary amine color developing agent.

Specific examples of the magenta coupler preferably used in the present invention are shown below, but are not limited thereto.

[0028]

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[0029]

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[0030]

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More preferred among the above magenta couplers are the couplers represented by the above general formula MI, wherein the coupler of the above general formula [MI] wherein R _M is a tertiary alkyl group is a light-fast coupler. Excellent in properties and particularly preferred. MC above
-8 to MC-12 are preferable because they are excellent in reproducing colors from blue to purple and red, and are also excellent in detail description power.

There are several methods for adjusting ΔλL _0.2 , which can be achieved by a combination of the above-mentioned magenta coupler and a high-boiling organic solvent used for dissolving and dispersing the coupler. As a preferably used high boiling organic solvent, a high boiling organic solvent having a dielectric constant of 3.5 to 7.0 is used. For example, phthalic acid esters such as dioctyl phthalate, diisodecyl phthalate, dibutyl phthalate, and butyl benzyl phthalate; phosphate esters such as tricresyl phosphate and trioctyl phosphate; and the general formula (A) of the present invention. Compounds are preferably used. These compounds may be used alone or in combination.

The compound represented by formula (A), which is preferably used as a high-boiling organic solvent in the present invention, will be described.

In the formula (A), the substituent represented by R ^a1 is not particularly limited, and is preferably an alkyl group, an alkenyl group, an aryl group, an alkoxyl group, an aryloxy group, an acyl group, an acylamino group. A carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group, a sulfonyl group, a hydroxyl group, a halogen atom and the like, and more preferably an alkyl group,
Examples thereof include an aryl group, an alkoxyl group and a halogen atom, and most preferably an alkyl group.

[0035] In the general formula (A), but as the substituent represented by R ^a2 is synonymous with the substituents represented by the foregoing R ^a1, when the R ^a1 represents a halogen atom R ^a2 represents an alkyl group ,
Aryl groups and alkoxyl groups are preferred. R ^a1 and R ^a2 may be fused to each other to form a ring, and when m is 2 or more, R ^a2 may be fused to each other to form a ring.

The total number of carbon atoms of R ^a1 and R ^a2 is 12 or more and 36
The number is preferably 12 or more and 28 or less.

The following are typical examples of the compound represented by the formula (A), but are not limited thereto.

[0038]

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[0039]

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[0040]

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[0041]

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[0042]

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[0043]

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General formula (A) preferably used in the present invention
Are represented by Japanese Patent Application No. 8-85156, 7-17.
Page.

In the present invention, the coupler and the compound represented by the formula (A) of the present invention are contained in at least one of the photosensitive silver halide emulsion layers.

In order to incorporate the coupler and the compound represented by the general formula (A) into the silver halide emulsion layer, a conventionally known method, for example, a solvent having a high boiling point such as a known dibutyl phthalate or tricresyl phosphate may be used. A coupler and an alcohol are dissolved alone or in combination in a mixture of a low-boiling solvent such as butyl acetate and ethyl acetate, or a solvent containing only a low-boiling solvent, and then mixed with an aqueous gelatin solution containing a surfactant. Then, after emulsifying and dispersing using a high-speed rotary mixer, a colloid mill or an ultrasonic dispersing machine, a method of directly adding the resulting emulsion to the emulsion can be adopted. Further, after the emulsified dispersion is set, the emulsion may be cut, washed with water, and then added to the emulsion.

In the present invention, the coupler and the compound represented by formula (A) may be separately dispersed by the above-mentioned dispersion method and added to the silver halide emulsion, but both may be dissolved simultaneously. A method of dispersing and adding to an emulsion is preferred.

The amount of the compound represented by formula (A) of the present invention is preferably 0.01 to 1 g of the coupler.
20 g, more preferably 0.1 to 8.0 g.

For the silver halide emulsion according to the present invention, a known method is used.

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. Quick processing,
From the standpoint of processing stability, a silver halide emulsion containing preferably 97 mol% or more, more preferably 98 to 99.9 mol%, of silver chloride is preferred.

For obtaining the silver halide emulsion according to the present invention, a silver halide emulsion having a portion containing silver bromide at a high concentration is particularly preferably used. In this case, the portion containing a high concentration of silver bromide may be epitaxy-bonded to silver halide emulsion grains, a so-called core-shell emulsion, or may be formed only partially without forming a complete layer. May simply have regions with different compositions. Further, the composition may change continuously or 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 order to obtain the silver halide emulsion according to the present invention, it is advantageous to include heavy metal ions. Heavy metal ions that can be used for such purposes include iron,
Iridium, platinum, palladium, nickel, rhodium,
Examples include Group 8 to 10 metals such as osmium, ruthenium, and cobalt; Group 12 transition metals such as cadmium, zinc, and mercury; and ions of lead, rhenium, molybdenum, tungsten, gallium, and chromium. 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, its ligand or ion may be cyanide ion, thiocyanate ion, isothiocyanate ion, chloride ion, bromide ion, iodide ion, nitrate ion, carbonyl ion. , Ammonia and the like.
Among them, cyanide ion, thiocyanate ion, isothiocyanate ion, chloride ion, bromide ion and the like are preferable.

In order for the silver halide emulsion according to the present invention to contain heavy metal ions, the heavy metal compound is physically added before, during, and after the formation of silver halide grains. What is necessary is just to add in arbitrary places of each process during ripening. In order to obtain a silver halide emulsion satisfying the above conditions, a heavy metal compound can be dissolved together with a halide salt and added continuously over the whole or a part of the grain forming step.

The amount of the heavy metal ion added to the silver halide emulsion is 1 × 10 ^-9 per mol of silver halide.
Mol or more and 1 × 10 ^-2 mol or less, particularly preferably 1 × 10 ⁻² mol or less.
It is preferably at least 10 ^-8 mol and not more than 5 10 ^-5 mol.

The silver halide grains according to the present invention may have any shape. One preferred example is
It is a cube having a (100) plane as a crystal surface. U.S. Pat. Nos. 4,183,756 and 4,225,666;
JP-A-55-26589, JP-B-55-42737, and The Journal of Photographic Science (J. Photogr. Sci.) 21, 39.
(1973), etc., particles having an octahedral, tetradecahedral, dodecahedral shape or the like can be prepared and used. Further, particles having a twin plane may be used.

As the silver halide grains according to the present invention, grains having a single shape are preferably used, but it is particularly preferred to add two or more monodispersed silver halide emulsions to the same layer.

The grain size of the silver halide grains according to the present invention is not particularly limited, but is preferably 0.1 to 1.2 μm in consideration of other photographic properties such as rapid processing and sensitivity.
m, more preferably in the range of 0.2 to 1.0 μm.

The particle size can be measured using the projected area of the particle or the approximate diameter. If the particles are substantially uniform in shape, the particle size distribution can represent this quite accurately as diameter or projected area.

The particle size distribution of the silver halide grains of the present invention is preferably a monodispersed silver halide grain having a coefficient of variation of 0.22 or less, more preferably 0.15 or less, and particularly preferably 0. .15 or less are added to the same layer. Here, the coefficient of variation is a coefficient representing the width of the particle size distribution, and is defined by the following equation.

Coefficient of variation = S / R (where, S is the standard deviation of the particle size distribution, and R is the average particle size.) The particle size here is the diameter of a spherical silver halide particle. In the case of a particle having a shape other than a cube or a sphere, it 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 according to the present invention may be obtained by any of an acidic method, a neutral method and an ammonia method. The particles may be grown at one time or may be grown after seed particles have been made. The method of producing the seed particles and the method of growing them may be the same or different.

The form in which the soluble silver salt and the soluble halide salt are reacted may be any of a forward mixing method, a reverse mixing method, a simultaneous mixing method, a combination thereof, and the like. Is preferred. Further, as one type of the double jet method, a pAg controlled double jet method described in JP-A-54-48521 can be used.

Further, JP-A-57-92523 and JP-A-57-92523 describe the same.
No.-92524, etc., a device for supplying an aqueous solution of a water-soluble silver salt and a water-soluble halide salt from an addition device arranged in a reaction mother liquor, and a water-soluble silver salt and a water-soluble solution described in German Patent Publication No. 292,164. Apparatus for continuously changing the concentration of an aqueous halide salt solution, JP-B-56-50
The reaction mother liquor was taken out of the reactor described in No. 1776, etc.
An apparatus that forms grains while keeping the distance between silver halide grains constant by concentrating by ultrafiltration may be used.

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 according to the present invention 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 according to the present invention, a sulfur sensitizer, a selenium sensitizer, a tellurium sensitizer and the like can be used, but a sulfur sensitizer is preferable. Thiosulfates as sulfur sensitizers,
Allyl thiocarbamide thiourea, allyl isothiocyanate, cystine, p-toluene thiosulfonate, rhodanine, inorganic sulfur and the like can be mentioned.

The addition amount of the sulfur sensitizer according to the present invention is preferably changed depending on the kind of the silver halide emulsion to be applied and the size of the expected effect. ^In the range of ^{-10 to} 5 × 10 ^-5 mol,
Preferably, it is in the range of 5 × 10 ^{−8 to} 3 × 10 ⁻⁵ mol.

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

The chemical sensitization of the silver halide emulsion according to the present invention may be a reduction sensitization.

The silver halide emulsion according to the present invention is intended to prevent fogging that occurs during the preparation process of the silver halide photographic material, reduce performance fluctuation during storage, and prevent fogging that occurs during development. A known antifoggant,
Stabilizers can be used. Examples of preferred compounds that can be used for such a purpose are described in JP-A No. 2-14 / 1990.
The compound represented by the general formula (II) described in the lower column of page 7 of JP-A-6036 can be mentioned, and a more preferred specific compound is (IIa-1) described on page 8 of the same publication. )-(IIa-8), (IIb-1)-(II
b-7) or 1- (3-methoxyphenyl)-
Compounds such as 5-mercaptotetrazole and 1- (4-ethoxyphenyl) -5-mercaptotetrazole can be mentioned. These compounds may be used, depending on the purpose, in a step of preparing silver halide emulsion grains, a step of chemical sensitization,
At the end of the chemical sensitization step, it is added in a step such as a coating liquid preparation step. When chemical sensitization is performed in the presence of these compounds, 1 × 10 ⁻⁵ mol to 5 ×
It is preferably used in an amount of about 10 ^-4 mol. When added at the end of chemical sensitization, 1 × per mole of silver halide
An amount of about 10 ⁻⁶ mol to 1 × 10 ⁻² mol is preferable, and 1 ×
The amount is more preferably from 10 ⁻⁵ mol to 5 × 10 ⁻³ mol. In the step of preparing a coating solution, when added to the silver halide emulsion layer, 1 × 10 ⁻⁶ mol to 1 × 10 ⁶ mol per mol of silver halide is used.
An amount of about ^-1 mol is preferred, and 1 × 10 ^-5 mol to 1 × 10
^-2 mol is more preferred. When added to a layer other than the silver halide emulsion layer, the amount in the coating film is preferably about 1 × 10 ^-9 mol to 1 × 10 ^-3 mol per 1 m ² .

In the silver halide photographic light-sensitive material according to the present invention, dyes having absorption in various wavelength ranges can be used for the purpose of preventing irradiation and halation. For this purpose, any of the known compounds can be used. In particular, as dyes having absorption in the visible region,
A described on page 308 of JP-A-3-251840
The dyes I-1 to 11 and the dyes described in JP-A-6-3770 are preferably used. As the infrared absorbing dye, the general formula (I) described in the lower left column of page 2 of JP-A-1-280750 is used. ), (II) and (III) have preferable spectral characteristics, do not affect the photographic characteristics of the silver halide photographic emulsion, and are preferable because there is no contamination due to residual color. As a specific example of a preferred compound, see Japanese Patent Publication No.
Exemplary compounds (1) to (45) listed in the lower left column of page 5 to the lower left column of page 5 can be exemplified.

In order to improve the sharpness, the amount of these dyes added is 680 nm for an unprocessed sample of a light-sensitive material.
Is preferable to make the spectral reflection density 0.7 or more, more preferably 0.8 or more.

It is preferable to add a fluorescent whitening agent to the light-sensitive material according to the present invention because the white background can be improved. Preferred examples of the compound include a compound represented by the general formula II described in JP-A-2-232652.

When the silver halide photographic light-sensitive material according to the present invention is used as a color photographic light-sensitive material, it is spectrally sensitized to a specific region in a wavelength region of 400 to 900 nm in combination with a yellow coupler, a magenta coupler and a cyan coupler. It has a layer containing a silver halide emulsion. The silver halide emulsion contains one kind or a combination of two or more kinds of sensitizing dyes.

As the spectral sensitizing dye for use in the silver halide emulsion according to the present invention, any known compounds can be used.
BS-1 to 8 described on page 28 of JP-A-251840 can be preferably used alone or in combination. As the green photosensitive sensitizing dye, GS-1 to GS-5 described on page 28 of the same publication are preferably used. RS-1 to 8 described on page 29 of the same publication are preferably used as red-sensitive sensitizing dyes. In the case of performing image exposure with infrared light using a semiconductor laser or the like, it is necessary to use an infrared-sensitive sensitizing dye. The dyes of IRS-1 to 11 described in JP-A No. 6-8 are preferably used. These infrared, red, green, and blue photosensitive sensitizing dyes may be added to supersensitizers SS-1 to SS-9 described in JP-A-4-285950, pp. 8-9, and JP-A-5-66515. Nos. S-1 to S-17 described on pages 15 to 17
Are preferably used 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.

The coupler used in the silver halide photographic light-sensitive material according to the present invention is formed by a coupling reaction with an oxidized form of a color developing agent to form a coupling product having a spectral absorption maximum wavelength in a wavelength region longer than 340 nm. Any compound that can be used can be used, and particularly typical examples include a yellow dye-forming coupler having a spectral absorption maximum wavelength in a wavelength range of 350 to 500 nm, a wavelength range of 500.
Typical examples are magenta dye-forming couplers having a spectral absorption maximum wavelength in the range of -600 nm and cyan dye-forming couplers having a spectral absorption maximum wavelength in the wavelength range of 600 to 750 nm.

Cyan couplers that can be preferably used in the silver halide photographic light-sensitive material of the present invention include:
Couplers represented by general formulas (C-I) and (C-II) described in the lower left column of page 5 of JP-A-4-114154 can be exemplified. Specific compounds are described in the same publication, page 5, lower right column to page 6, lower left column, CC-1 to CC.
-9 may be mentioned.

The yellow coupler which can be preferably used in the silver halide photographic light-sensitive material according to the present invention is represented by the general formula (Y-I) described in the upper right column of page 3 of JP-A-4-114154. Couplers. Specific compounds include those described as YC-1 to YC-9 in the lower left column of page 3 of the same publication. Above all, a coupler in which RY1 of the general formula [Y-1] of the same publication is an alkoxy group or a coupler represented by the general formula [I] described in JP-A-6-67388 can reproduce yellow having a preferable color tone. preferable. Of these, particularly preferred examples of the compounds include YC-8 and YC-9 described in the lower left column of page 4 of JP-A-4-114154, and
-67388, page 13-14
o (1) to (47). The most preferred compound is described in JP-A-4-8184.
It is a compound represented by the general formula [Y-1] described in JP-A-7-page 1 and JP-A-11-page 11-17.

When an oil-in-water emulsion dispersion method is used to add the couplers and other organic compounds used in the silver halide photographic light-sensitive material according to the present invention, a water-insoluble emulsion having a boiling point of 150 ° C. or higher is usually used. If necessary, a low-boiling point and / or water-soluble organic solvent is used in combination in the boiling point organic solvent, and the mixture is dissolved 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 at the same time as the dispersion, a step of removing the low boiling organic solvent may be added. Examples of high boiling organic solvents that can be used to dissolve and disperse the coupler include dioctyl phthalate, diisodecyl phthalate, phthalic acid esters such as dibutyl phthalate, tricresyl phosphate, and phosphoric acid esters such as trioctyl phosphate; Is 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 compound preferable as a surfactant used for dispersing a photographic additive or adjusting the 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 are preferable. Containing. Specifically, A- described in JP-A-64-26854 is described.
1 to A-11. Also, a surfactant in which a fluorine atom is substituted for an alkyl group is preferably used. These dispersions are usually added to a coating solution containing a silver halide emulsion, and the time until the addition to the coating solution after the dispersion and the time from the addition to the coating solution to the coating are preferably as short as 10 hours each. Preferably within 3 hours, more preferably 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 on page 3 of JP-A-2-66541 and phenolic compounds represented by general formula B described in JP-A-3-174150. Amine compounds represented by the general formula A described in JP-A-64-90445,
General formulas XII, XIII, XIV described in 2-182741 JP
The metal complex represented by XV is particularly preferred for magenta dyes. Further, compounds represented by the general formula I 'described in JP-A-1-19649 and compounds represented by the general formula II described in JP-A-5-11417 are particularly preferable for yellow and cyan dyes.

For the purpose of shifting the absorption wavelength of the coloring dye, the compound (d-11) described in the lower left column of page 9 of JP-A-4-114154 and the compound described in the lower left column of page 10 of the same specification are disclosed. Compounds such as (A'-1) can be used. In addition, U.S. Pat.
No. 74,187 can also be used.

In the silver halide light-sensitive material according to the present invention, a compound which reacts with an oxidized developing agent is added to a layer between the light-sensitive layers to prevent color turbidity or to add a compound to the silver halide emulsion layer. It is preferable to improve fog and the like by adding.
The compound for this purpose is preferably a hydroquinone derivative, more preferably a dialkylhydroquinone such as 2,5-di-t-octylhydroquinone.
Particularly preferred compounds are those represented by the general formula II described in JP-A-4-133,056, and compounds II-1 to II-14 described on pages 13 to 14 and compound 1 described on page 17 of the same publication are described. No.

It is preferable to add an ultraviolet absorber to the light-sensitive material according to the present invention to prevent static fog or to improve the light fastness of a dye image. Preferred examples of the ultraviolet absorber include benzotriazoles. Particularly preferred compounds are those represented by the formula III-3 described in JP-A-1-250944 and JP-A-64-666.
No. 46, a compound represented by the general formula III, and JP-A-63-187240, UV-1L to UV-2.
7L, compounds represented by the general formula I described in JP-A-4-1633, 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 silver halide photographic light-sensitive material according to the present invention. If necessary, other gelatins, gelatin derivatives, graft polymers of gelatin and other high polymers, gelatin Other than these, hydrophilic colloids such as proteins, sugar derivatives, cellulose derivatives, and synthetic hydrophilic polymer substances such as homopolymers and copolymers can also be used.

As the hardener of these binders, it is preferable to use a vinyl sulfone hardener or a chlorotriazine hardener alone or in combination. JP-A-61-24
It is preferable to use the compounds described in JP-A Nos. 9054 and 61-245153. Further, it is preferable to add a preservative and an antifungal agent as described in JP-A-3-157646 to the colloid layer in order to prevent the growth of mold and bacteria which adversely affect photographic performance and image storability. It is preferable to add a slipping agent or matting agent described in JP-A-6-118543 or JP-A-2-73250 to the protective layer in order to improve the physical properties of the surface of the photosensitive material or the processed sample.

As the support used in the silver halide photographic light-sensitive material of the present invention, any material may be used, such as paper coated with polyethylene or polyethylene terephthalate, paper support made of natural pulp or synthetic pulp, A vinyl chloride sheet, polypropylene which may contain a white pigment, a polyethylene terephthalate support, baryta paper, and the like can 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, alkaline earth metal sulfates such as barium sulfate, alkaline earth metal carbonates such as calcium carbonate, finely divided silica, silica such as synthetic silicate, calcium silicate, alumina, alumina hydrate, oxidation Examples include titanium, zinc oxide, talc, and clay. 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 was 13% by weight for improving sharpness.
The above is preferred, and more preferably 15% by weight.

The degree of dispersion of the white pigment in the water-resistant resin layer of the paper support according to the present invention 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 coefficient of variation described in the above publication.

It is more preferred that the value of the center plane average roughness (SRa) of the support is 0.15 μm or less, more preferably 0.12 μm or less, because the effect of good gloss is obtained. In addition, trace amounts of ultramarine, oil-soluble dyes, etc. to adjust the spectral reflection density balance of the white background after treatment in the white pigment-containing water-resistant resin of the reflective support or in the applied hydrophilic colloid layer to improve whiteness It is preferable to add a bluing agent or a reddish agent.

The silver halide photographic light-sensitive material according to the present invention may be subjected to corona discharge, ultraviolet irradiation, flame treatment, or the like, if necessary, to the surface of the support directly or in a subbing layer (adhesion on the surface of the support, (1 or 2 or more subbing layers for improving antistatic properties, dimensional stability, friction resistance, hardness, antihalation properties, friction properties and / or other properties) Good.

In coating a photographic 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 silver halide photographic light-sensitive material according to the present invention, an image recorded on a negative is optically formed on a silver halide photographic light-sensitive material to be printed. The image may be printed and printed, or once the image is converted into digital information, the image is formed on a CRT (cathode ray tube), and this image is formed on a silver halide photographic material to be printed. Alternatively, the image may be printed by scanning while changing the intensity of the laser beam based on digital information.

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. For example, color paper, color reversal paper, a photosensitive material for forming a positive image, a photosensitive material for a display, and a photosensitive material for a color proof can be used. It is particularly preferable to apply the invention to a photosensitive material having a reflective support.

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-laurylamino) toluene CD-4) 4- (N-ethyl-N- (β-hydroxyethyl) amino) aniline CD-5) 2-Methyl-4- (N-ethyl-N- (β
-Hydroxyethyl) amino) aniline CD-6) 4-Amino-3-methyl-N-ethyl-N
-(Β- (methanesulfonamido) ethyl) aniline CD-7) N- (2-amino-5-diethylaminophenylethyl) methanesulfonamide 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- (γ-hydroxypropyl) aniline In the present invention, the above color developer can be used in an arbitrary pH range, but from the viewpoint of rapid processing, the pH is 9.5 to 13.0.
And more preferably pH 9.8-1.
It is used in the range of 2.0.

The processing temperature of color development according to the present invention is 35
The temperature is preferably from 70 ° C to 70 ° C. The higher the temperature, the shorter the processing time is possible, which is preferable. However, from the viewpoint of the stability of the processing solution, the higher the temperature, the more preferable.

Conventionally, the color development time is generally about 3 minutes and 30 seconds, but in the present invention, it is preferably 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, alkaline agents having a pH buffering action, chloride ions, development inhibitors such as benzotriazoles, preservatives,
A chelating agent or the like is used.

The silver halide photographic light-sensitive material of the present invention is subjected to bleaching and fixing after color development. The bleaching process may be performed simultaneously with the fixing process. After the fixing process,
Usually, a water washing process is performed. Further, as an alternative to the water washing treatment, a stabilization treatment may be performed. The developing apparatus used for the development of the silver halide photographic light-sensitive material of the present invention may be a roller transport type in which the light-sensitive material is conveyed between rollers disposed in a processing tank, and the belt may be provided with the light-sensitive material. The processing tank may be formed in a slit shape, and the processing liquid may be supplied to the processing tank and the photosensitive material may be transported, or the processing liquid may be sprayed. Spray method,
A web method by contact with a carrier impregnated with the processing solution,
A method using a viscous treatment liquid can also be used. In the case of processing a large amount, it is usual to perform a running process using an automatic developing machine, but at this time, the smaller the replenishment amount of the replenisher, the more preferable, and the most preferable processing form from environmental suitability, etc.
As a replenishment method, a processing agent is added in the form of a tablet, and the method described in JP-A-94-16935 is most preferable.

[0108]

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 paper support was prepared by laminating high-density polyethylene on both sides of a paper pulp having a basis weight of 180 g / m ² . However, on the side to be coated with the emulsion layer, a molten polyethylene containing surface-treated anatase-type titanium oxide dispersed at a content of 15% by weight was laminated to produce a reflective support. After subjecting this reflective support to a corona discharge treatment, a gelatin undercoat layer was provided, and further, each layer having the following constitution was provided thereon.
13 was produced. The coating solution was prepared as described below.

First layer coating solution Yellow coupler (Y-1) 23.4 g, dye image stabilizer (ST-1) 3.34 g, (ST-2) 3.34
g, (ST-5) 3.34 g, fog inhibitor (Z-48)
8) 0.67 g, stain inhibitor (HQ-1) 0.34
g, image stabilizer A 5.0 g, high boiling point organic solvent (DBP)
3.33 g and 1.67 g of high boiling organic solvent (DNP)
60 ml of ethyl acetate was added to the solution to dissolve the solution.
Using an ultrasonic homogenizer, the mixture was emulsified and dispersed in 220 ml of a 10% aqueous gelatin solution containing 7 ml of a surfactant (SU-1) to prepare a yellow coupler dispersion. This dispersion was mixed with a blue-sensitive silver halide emulsion prepared under the following conditions to prepare a first layer coating solution.

The coating liquids for the second to seventh layers also have the coating amounts shown in Tables 1 and 2 in the same manner as the coating liquid for the first layer. Each coating solution was prepared in such a manner as to be variously changed as described above.

Further, (H-1), (H-2)
Was added. Surfactants (SU-
2) and (SU-3) were added to adjust the surface tension. Further, F-1 was added to each layer so that the total amount became 0.04 g / m ² .

[0113]

[Table 1]

[0114]

[Table 2]

SU-1: sodium tri-i-propylnaphthalenesulfonate SU-2: di (2-ethylhexyl) sodium sulfosuccinate sodium salt SU-3: di (2,2,3,3,4) sulfosuccinate , 4,
5,5-octafluoropentyl) · sodium salt DBP: dibutyl phthalate DNP: dinonyl phthalate DOP: dioctyl phthalate DIDP: di-i-decyl phthalate PVP: polyvinylpyrrolidone H-1: tetrakis (vinylsulfonylmethyl) methane H-2 : 2,4-dichloro-6-hydroxy-s-triazine sodium HQ-1: 2,5-di-t-octylhydroquinone HQ-2: 2,5-di-sec-dodecylhydroquinone HQ-3: 2 5-di-sec-tetradecylhydroquinone HQ-4: 2-sec-dodecyl-5-sec-tetradecylhydroquinone HQ-5: 2,5-di (1,1-dimethyl-4-hexyloxycarbonyl) butylhydroquinone Image stabilizer A: Pt-octylph Enol

[0116]

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[0117]

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[0118]

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[0119]

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(Preparation of Blue-Sensitive Silver Halide Emulsion) 40 ° C.
In a liter of a 2% aqueous gelatin solution kept warm in
Solution) 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 added at pAg = 8.0, pH = 5.5 and added simultaneously over 180 minutes. At this time, pAg was controlled by the method described in JP-A-59-45437.
H was controlled using sulfuric acid or an aqueous solution of sodium hydroxide.

(Solution A) 3.42 g of sodium chloride 0.03 g of potassium bromide 200 ml with addition of water (Solution B) 10 g of silver nitrate 200 ml with addition of water (Solution C) 102.7 g of sodium chloride 102.7 g of 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, the addition time of (Solution A) and (Solution B) and (C) and (D)
Except that the addition time of the solution was changed, the average particle size was 0.64 μm, the variation coefficient of the particle size distribution was 0.07,
Monodisperse cubic emulsion EMP having a silver chloride content of 99.5 mol%
-1B was obtained.

The above 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 stabilizer STAB- 33 × 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 (Preparation of green-sensitive silver halide emulsion) (Solution A) and (Solution B)
The average particle diameter was 0.40 μm in the same manner as in EMP-1 except that the addition time of (C) and (C solution) and (D solution) were changed.
m, a coefficient of variation 0.08, and a monodispersed cubic emulsion EMP-2 having a silver chloride content of 99.5%. Next, average particle size 0.5
A monodisperse cubic emulsion EMP-2B having a thickness of 0 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 in the amounts shown in Table 3 in terms of silver amount, and photosensitive material Nos. Various green-sensitive silver halide emulsions for 101 to 113 were obtained.

Sodium thiosulfate 1.5 mg / mol AgX chloroauric acid 1.0 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 GS-1 4 × 10 ⁻⁴ mol / mol AgX (Preparation of red-sensitive silver halide emulsion) (solution A) and (solution B)
The average particle diameter was 0.40 μm in the same manner as in EMP-1 except that the addition time of (C) and (C solution) and (D solution) were changed.
m, a coefficient of variation 0.08 and a monodisperse cubic emulsion EMP-3 having a silver chloride content of 99.5%. The average particle size is 0.38
A monodisperse cubic emulsion EMP-3B having a particle size of 0.08, a coefficient of variation of 0.08 and a silver chloride content of 99.5% was obtained.

The above EMP-3 was optimally chemically sensitized 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 ratio 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 In the red-sensitive emulsion, SS-1 was used per mole of silver halide. 2.0 × 10 ^{-3 was} added.

[0127]

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[0128]

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Thus, the following photosensitive material sample No. 1
01 to 113 were created.

[0130]

[Table 3]

[0131]

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[0132]

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The photosensitive material sample no. The following evaluation was performed about 101-113.

<< Magenta Color Image Maximum Density (Dmax) >>
The above photosensitive material sample No. For 101 to 113, using a halogen lamp having a color temperature of 3300K, monochromatic exposure was performed for 1.0 second through a neutral step tablet using a Kodak Wratten gelatin filter N061 green filter as green exposure, and Konica after color development was performed by the following development processing. The maximum reflection density is obtained by a PD84 densitometer manufactured by the Company and is set as the maximum density of the magenta color image.

<< γ ratio >> The above photosensitive material sample No. 101-
About 113, through a neutral step tablet using a halogen lamp with a color temperature of 3300K, 1.0
The sample subjected to the monochromatic exposure shown below is subjected to normal color development using the following developing treatment, and the developed sample is subjected to a maximum transmission wavelength of 644 nm, 546 nm, and 436 n, respectively.
densitometer with an interference filter of m (Konica's PDA-
The reflection density is measured using a 84-type reflection densitometer, and the γ ratio is calculated by the following equation.

Γ ratio = γA / γB × 100 where γA = 1.0 / log ₁₀ (E ₁ / E ₂ ) γB = 1.0 / log ₁₀ (E ₃ / E ₄ ) Expressing reflection density at Dmin, E ₁ and E ₂ each Dmin + 0.8, Dmin + 1.8
Represents the amount of exposure required to give a reflection density of E ₃ and E ₄ represent exposure amounts required to give reflection densities of Dmin + 0.3 and Dmin + 0.8, respectively.

<< ΔλL _0.2 >> The above photosensitive material sample No. 1
For 01 to 113, using a halogen lamp having a color temperature of 3300K, monochromatic exposure was performed for 1.0 second through a neutral step tablet using a Kodak Wratten gelatin filter N061 green filter as green exposure, and color development was performed by the following development processing. The spectral reflection density was measured with Hitachi's H-207 type spectral reflection density analyzer,
The maximum peak wavelength (λmax) when the maximum color density of the spectral absorption spectrum of the coloring dye formed from the magenta coupler on paper is set to 1.0 is measured. further,
Wavelength λ at a point giving a concentration of 0.2 in the spectral absorption spectrum
The L _0.2 was measured, the following formula to determine the ΔλL _0.2.

ΔλL _0.2 = λL _0.2 −λmax << Shadow Depth, Skin Color Reproducibility, Gray Reproducibility >> A wedding scene was photographed using a Konica professional 160 negative film, and a negative image obtained by color development was obtained. The above photosensitive material sample Nos. For 101 to 113, 6-cut size (203
× 254 mm) to obtain a color positive print. The following evaluation was performed on these color positive prints.

<< Shadow Depth >> X: The shading of the male black morning folds is not depicted. ；: The shading of the male black morning folds is somewhat depicted. ；: The shading of the male black morning folds is clearly understood. ◎ The shading of the folds of the male black morning is described in detail << Skin color reproducibility >> The hue shift between the male skin color and the female skin color of the above color positive print was visually evaluated.

×: strong color deviation Δ: color deviation and not the same hue (directions in which the deviation moves strongly are indicated by B (blue), G (green), and R (red)) ○: color偏: The same hue is seen without color bias << Gray Reproducibility >> Density of Konica gray chart plate (gray chart with reflection density of 0.05 to 2.50) 1.
The color deviation was visually evaluated for 0 to 2.0.

×: Strong color deviation Δ: Color deviation from the reference gray (directions of deviation are indicated by B (blue), G (green), and R (red)) ○: To the reference gray Color deviation is small ◎: There is no color deviation from the reference gray and it is close to the reference gray << Development processing >> Development processing step Processing step Processing temperature Time Replenishment amount Color development 38.0 ± 0.3 ° C. 45 seconds 80 cc bleach-fix 35.0 ± 0.5 ° C. 45 seconds 120 cc Stabilization 30-34 ° C. 60 seconds 150 cc drying 60-80 ° C. 30 seconds The composition of the developing solution is shown below.

Color developer 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 diethylenetriamine 5 Sodium acetate sodium salt 2.0 g 2.0 g Fluorescent whitening agent (4,4'-diaminostil benzyldisulfonic acid derivative) 2.0 g 2.5 g Potassium carbonate 30 g 30 g Water was added to make the total volume 1 liter, and the tank solution was pH = 1
Adjust the replenisher to pH = 10.60 to 0.10.

Bleach-fix solution tank solution and replenisher diethylenetriaminepentaacetate 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 0.0g ammonium sulfite (40% aqueous solution) 27.5ml Water is added to make up to 1 liter, and the pH is adjusted to 5.0 with potassium carbonate or glacial acetic acid.

Stabilizing solution tank solution and replenisher solution o-phenylphenol 1.0 g 5-chloro-2-methyl-4-isothiazolin-3-one 0.02 g 2-methyl-4-isothiazolin-3-one 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 1 0.0 g ammonia water (25% aqueous solution of ammonium hydroxide) 2.5 g nitrilotriacetic acid / trisodium salt 1.5 g Water was added to make the total volume 1 liter, and the pH was adjusted to 7.5 with sulfuric acid or ammonia water.

Table 4 shows the results.

[0146]

[Table 4]

The magenta γ of the above samples 101 to 112
A was 2.60. Sample 113 had a magenta γA of 2.1. Y / of the monochromatic γ ratio of samples 101 to 113
The M ratio was 1.2. The C / M ratio of the monochromatic γ ratio of Samples 101 to 113 was 1.0.

As is clear from Table 4, Comparative Sample 101
It can be seen that the sample 104 of the present invention is excellent in shadow depiction, skin color reproducibility in dark areas, and gray reproducibility, as compared with 103. In addition, it can be seen that Sample 107 in which ΔM L _0.2 of the M coupler was changed had excellent skin color reproducibility in the light part. Sample 1 with further reduced ΔλL _0.2 of M coupler
In No. 11, the gray reproducibility was unexpectedly greatly improved. In the sample 113 in which the magenta γ ratio was adjusted, favorable results were obtained in the shadow depiction, the flesh color reproducibility (bright and dark), and the gray reproducibility.

Example 2 In the same manner as in the sample 113 of Example 1, except that the first layer was changed as shown in Table 5, and the Y / M ratio of the monochromatic γ ratio was changed as shown in Table 5, went.

Table 6 shows the results.

[0151]

[Table 5]

[0152]

[Table 6]

As is clear from Table 6, the monochromatic γ ratio Y /
By changing and adjusting the M ratio, shadow drawing and skin color reproducibility were more than expected.

Example 3 A developing process was carried out in the same manner as in Example 1 except that the developing process was changed as follows.

<< Development Processing >> Development Processing Step Processing Step Processing Temperature Time Replenishment Color Development 38.0 ± 0.3 ° C. 22 seconds 81 ml Bleaching and Fixing 35.0 ± 0.5 ° C. 22 seconds 54 ml Stabilization 30 ３４34 ° C. for 25 seconds 150 ml Drying 60-80 ° C. for 30 seconds The composition of the developing solution is shown below.

Color developer tank liquid and replenisher tank liquid Replenisher Pure water 800 ml 800 ml 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 6.5 g 10.5 g N, N-diethylhydroxylamine 3.5 g 6.0 g N, N-bis (2-sulfoethyl) hydroxyamine 3.5 g 6.0 g Triethanolamine 10.0 g 10.0 g Diethylenetriaminepentaacetic acid sodium salt 2.0 g 2.0 g Fluorescent whitening agent (4,4'-diaminostilbendisulfonic acid derivative) 2.0 g 2.5 g Potassium carbonate 30 g 30 g Add water to make the total volume 1 liter, PH =
At 10.10, the replenisher is adjusted to pH = 10.60.

Bleach-fix solution tank solution and replenisher tank solution Replenisher diethylenetriaminepentaacetate ammonium ammonium dihydrate 100 g 50 g diethylenetriaminepentaacetic acid 3 g 3 g ammonium thiosulfate (70% aqueous solution) 200 ml 100 ml 2-amino-5-mercapto- 1,3,4-thiadiazole 2.0 g 1.0 g Ammonium sulfite (40% aqueous solution) 50 ml 25 ml Add water to make the total volume 1 liter, adjust the tank solution to pH = 7.0 with potassium carbonate or glacial acetic acid, and replenish it. Is pH = 6.
Adjust to 5.

Stabilizing solution tank solution and replenisher solution o-phenylphenol 1.0 g 5-chloro-2-methyl-4-isothiazolin-3-one 0.02 g 2-methyl-4-isothiazolin-3-one 0.02 g Diethylene glycol 1.0 g Optical brightener (Tinopearl SFP) 2.0 g 1-hydroxyethylidene-1,1-diphosphonic acid 1.8 g PVP 1.0 g Aqueous ammonia (25% aqueous ammonium hydroxide) 2.5 g Ethylenediaminetetraacetic acid 1 0.0 g Ammonium sulfite (40% aqueous solution) 10 ml Water is added to make the total volume 1 liter, and the pH is adjusted to 7.5 with sulfuric acid or aqueous ammonia.

Evaluation was made in the same manner as in Example 1, and it was confirmed that the effects of the present invention could be effectively obtained.

Example 4 In Example 3, an automatic developing machine was manufactured by Konica Corporation.
PS-868J, ECOJET-P as processing chemical
And a running process was performed according to the process name CPK-2-J1. Evaluation was performed in the same manner as in Example 1, and it was confirmed that the effects of the present invention were obtained.

[0161]

According to the present invention, sufficient shadow depiction and skin color reproducibility with a small change in color balance with respect to the exposure area can be obtained.
And a silver halide photosensitive material having improved gray reproducibility.

Claims (3)

[Claims] In a silver halide photographic material having at least one silver halide emulsion layer on a support, a magenta image formed by monochromatic exposure of the silver halide emulsion layer is represented by the following formula: A silver halide photographic light-sensitive material having a represented γ ratio in the range of 100 to 135 and a maximum density of the magenta image of 1.90 or more. γ ratio = γA / γB × 100 [where γA = 1.0 / log ₁₀ (E ₁ / E ₂ ) γB = 1.0 / log ₁₀ (E ₃ / E ₄ ) E ₁ and E ₂ are each Dmin + 0 .8, Dmin +
It represents the exposure required to give a reflection density of 1.8. E
₃ and E ₄ are Dmin + 0.3, Dmin + 0.
8 represents the exposure required to give a reflection density of 8. However,
Dmin is the reflection density of the unexposed portion. ] 2. A color dye for forming a magenta image, wherein ΔλL _0.2 represented by the following formula is 90 or less.
The silver halide photographic light-sensitive material as described above. ΔλL _0.2 = λL _0.2 -λmax wherein, .lambda.max is the maximum peak wavelength of when the maximum color density of the absorption spectrum on the paper of a colored dye formed from the magenta coupler to 1.0. λL
_0.2 is the wavelength at which the concentration 0.2 of the spectral absorption spectrum is given. ] 3. The silver halide according to claim 1, wherein the high-boiling organic solvent contained in the color forming dye for forming a magenta image has a compound represented by the following general formula (A). Photosensitive material. Embedded image [Wherein, R ^a1 represents a substituent, R ^a2 represents a hydrogen atom or a substituent, and m represents an integer of 0 to 4. When m is 2 or more, a plurality of R ^a2 may be the same or different, and the total number of carbon atoms of R ^a1 and R ^a2 is 12 or more and 36
It is as follows. ]