JPH05181240A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain the silver halide color photographic sensitive material enhanced in sharpness, color reproducibility, and sensitivity, and reduced in fog by using a combination of a silver halide emulsion high in sensitivity containing a specified yellow coupler and a specified dye. CONSTITUTION:One of silver halide emulsion layers contains the silver halide emulsion having a silver chloride content as high as >=95mol% and containing the yellow coupler represented by formula I and at least one of silver halide emulsion layers or hydrophilic colloidal layers contains the dye represented by formula II, and in formulae I and II, R1 is halogen, alkyl, aryl, alkoxy, or the like; R2 is H or a substituent on the benzene; B is an organic group: X is H or a group to be released by coupling with the oxidation product of a color developing agent; each of R4 and R5 is H, alkyl, aryl, or a heterocyclic group; each of Z<1> and Z<2> is a nonmetallic atomic group necessary to form a 5- to 7-membered hetero ring; and each of L1-L5 is a methine group.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide color photographic light-sensitive material, and more particularly to a silver halide color photographic light-sensitive material having excellent sharpness and color reproducibility, high sensitivity and less fog.

[0002]

BACKGROUND OF THE INVENTION In recent years, in the photographic industry, a high-quality silver halide photographic light-sensitive material capable of rapid processing, excellent in sharpness, color reproducibility and the like has been demanded, and fog is small and sufficient sensitivity is obtained. It is an important performance required for a silver halide photographic light-sensitive material.

In achieving rapid processing, it has been known that the shape, size and composition of silver halide grains of a silver halide emulsion used for a light-sensitive material have a great influence on the development speed and the like, and particularly the halogen composition. Has a large influence, and it has been found that when a high chloride silver halide is used, a significantly high development rate is exhibited.

On the other hand, improving the sharpness is one of the most important performances for improving the image quality. As a means for improving the sharpness, the optical characteristics of the support or the halation prevention or In order to prevent irradiation, there is known a method of coloring a silver halide photographic emulsion layer or other hydrophilic colloid layer with a dye that absorbs light of a specific wavelength.

The dye used in the light-sensitive material mainly plays the following role and usage. (1) A support for a photographic emulsion layer on a light-sensitive material in order to make the spectral composition of incident light reaching the photographic emulsion layer more preferable or to adjust the sensitivity by changing the amount of incident light, that is, to cut unnecessary light. A colored layer is provided on the farther side. Such a colored layer is called a filter layer, and when there are multiple emulsion layers, it is provided between the emulsion layers and between the emulsion layers.

(2) An image in which light transmitted through the photographic emulsion layer is reflected at the interface between the emulsion layer and the support or at the surface of the support opposite to the emulsion layer and is incident on the emulsion layer again. A color layer is provided between the emulsion layer and the support or on the back surface of the support when viewed from the emulsion layer in order to prevent the blurring, that is, halation. Such a coloring layer is called an antihalation layer, and when there are a plurality of emulsions, it may be provided in the intermediate layer between the emulsion layers.

(3) The photographic emulsion layer is colored in order to prevent light scattering (generally called irradiation) due to silver halide grains in the photographic emulsion layer. Dyes used for such purposes have good spectral absorption characteristics according to their intended use, are completely decolorized in the photographic processing solution, and are easily eluted from the light-sensitive material to leave residual color due to the dye after processing. No contamination, no adverse effect such as sensitivity increase or decrease or fog on the spectrally sensitized photographic emulsion,
Further, it is necessary to satisfy various conditions such as excellent stability over time in a solution or in a light-sensitive material and not causing discoloration.

[0008] A lot of research has been carried out with the aim of finding dyes satisfying the above-mentioned conditions, and a large number of dyes have been proposed so far, for example, British Patent 506,385.
No. 3, U.S. Pat. No. 3,247,127, Japanese Patent Publication No. 39-22
Oxonol dyes described in 069 and 43-13168, styryl dyes represented by U.S. Pat. No. 1,845,404, U.S. Pat. No. 2,493,747, British Patent 1,542,807, etc. Merocyanine dye,
US Pat. Nos. 2,843,486 and 3,294,539
Cyanine dyes described in U.S. Pat.
There are anthraquinone dyes represented by 865 and 752.

Of these dyes, oxonol type dyes and anthraquinone type dyes have relatively few adverse effects on photographic emulsions and have been conventionally favored for use in silver halide photographic light-sensitive materials for direct viewing. ..

Particularly, among these dyes, as a dye suitable for use in a light-sensitive material, which uses a high-processing silver halide capable of rapid processing, European Patent 246,553
JP-A-64-26850, JP-A-63-2440
No. 34, JP-A Nos. 1-13447 and 1-196033.
The compounds described in JP-A No. 2-97940 and the like were useful as those relatively satisfying the performance required for the dye.

On the other hand, in a silver halide color photographic light-sensitive material, silver halide is spectrally sensitized with a sensitizing dye by a commonly used subtractive method, and a yellow color-forming coupler is formed in a blue-sensitive silver halide emulsion layer. , A green-sensitive silver halide emulsion layer contains a magenta color forming coupler and a red-sensitive silver halide emulsion layer contains a cyan color forming coupler, and after imagewise exposure,
A dye image is obtained by performing development processing using an aromatic primary amine type color developing agent (hereinafter, simply referred to as color developing agent) and then bleach-fixing processing.

The dye image thus obtained has good hue and excellent color reproducibility.
It is desired that it does not discolor even when it is stored under high temperature and high humidity for a long time or exposed to light (hereinafter, these are referred to as image storability). Among these, various compounds have been used as the yellow coupler, but among them,
Acyl acetylianide couplers have been used as relatively preferable compounds to satisfy the above performance.

However, in order to respond to the user's demand for higher image quality and higher sensitivity in recent years, the sharpness and color reproducibility are improved and the silver halide emulsion is increased in sensitivity. It turned out to be problematic.

(1) When a yellow coupler excellent in various properties such as hue and color developability is used together with a silver halide emulsion having a high sensitivity, a phenomenon of sensitivity decrease occurs, and a sufficiently high sensitivity cannot be achieved. I knew that.

(2) A silver halide color photographic light-sensitive material containing the above yellow coupler and a sensitized silver halide emulsion is excellent in the above-mentioned spectral absorption characteristics and is decolorized in a photographic processing solution, which adversely affects photographic performance. It was found that the use of a dye which does not satisfy the above requirement has a drawback that the reduction in sensitivity is promoted and the fog is increased.

(3) The above undesired phenomenon is more likely to occur as the sensitivity of the photographic emulsion itself is increased, and is satisfactory in a high-sensitivity silver halide color photographic light-sensitive material using a yellow coupler and a dye having good basic characteristics. There is a dilemma that it is not possible to achieve both high sensitivity and the effect of reducing fog.

(4) Among the above-mentioned unfavorable phenomena, the decrease in sensitivity is more remarkable as the processing time is shorter, and the increase in fog is more remarkable as the replenishing amount of the color developing solution is small. As a result, the photosensitive material deteriorates.

(5) In the market, there has been a tendency for a short replenishment amount of developer in recent years due to improvement in environmental suitability and a small replenishment amount from a large-scale developing station to a so-called minilab or compact lab. However, in an increasing trend,
As the daily processing amount decreases, the replenishment amount further decreases, and the problems (1) to (3) are likely to become more serious problems in the future.

[0019]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a silver halide photographic light-sensitive material which is excellent in sharpness and color reproducibility, has high sensitivity and has less fog. Another object of the present invention is to use with a high-sensitivity silver halide photographic light-sensitive material containing a yellow dye-forming coupler having a high silver chloride emulsion and having a good hue, excellent color developability and excellent image storability. Another object of the present invention is to provide a silver halide photographic light-sensitive material containing a novel dye that does not adversely affect photographic performance such as increased fog and does not cause residual color stain even in short-time processing.

[0020]

The above objects of the present invention are as follows: (1) In a silver halide photographic light-sensitive material comprising at least one photosensitive silver halide emulsion layer provided on a support, at least one of the silver halide emulsion layers is One layer contains a silver halide emulsion having a silver chloride content of 95 mol% or more, and at least one layer of the silver halide emulsion layer contains a yellow coupler represented by the general formula [I]. A silver halide photographic light-sensitive material characterized by containing a compound represented by the general formula [II] or [III] in at least one of the silver halide emulsion layer and other hydrophilic colloid layers.

[0021]

[Chemical 5]

[Wherein R ₁ represents a halogen atom, an alkyl group, an aryl group, an alkoxy group or an aryloxy group, R ₂ represents a hydrogen atom or a group capable of substituting for a benzene ring, and m is 1 or 2 Represents the integer. B represents an organic group, and X represents a hydrogen atom or a group capable of splitting off upon reaction with an oxidized product of a color developing agent. ]

[0023]

[Chemical 6]

[Wherein R ₄ and R ₅ represent a hydrogen atom, an alkyl group, an aryl group, an alkenyl group or a heterocyclic group, and Z
¹ and Z ² represent a non-metal atom group for forming a 5-membered, 6-membered or 7-membered heterocycle. L _{1 to} L ₅ represent a methine group, and n
₁ , n ₂ represents an integer of 0, ₁ , ₂ . ]

[0025]

[Chemical 7]

[In the formula, R ₆ and R ₇ have the same meanings as R ₄ and R _5, and Z ³ has the same meaning as Z ¹ and Z ² . L
_{6 to} L ₁₀ have the same meanings as L _{1 to} L _5, and n ₃ and n ₄
Represents an integer of 0, 1, 2. ]

(2) A silver halide photographic light-sensitive material characterized in that the yellow coupler contained in the silver halide emulsion layer described in the above item 1 is a compound represented by the general formula [I] -a.

[0028]

[Chemical 8]

[R ₃ represents an alkyl group, an aryl group, a cycloalkyl group or an acyl group, R ₂ represents a hydrogen atom,
Alternatively, it represents a group capable of substituting on the benzene ring, and m is 1 or 2
Represents the integer. B represents an organic group, and X represents a hydrogen atom or a group capable of splitting off upon reaction with an oxidized product of a color developing agent. ]

(3) The ratio of the spectral sensitivities at the wavelength of 470 nm of the emulsion having the maximum spectral sensitivity of the shortest wavelength among the wavelengths of the maximum spectral sensitization sensitivity of each photosensitive layer is 0.5 or less. 2. The silver halide photographic light-sensitive material as described in the above item 1.

(4) Of the wavelengths of maximum spectral sensitization sensitivity of each photosensitive layer, 720n with respect to the spectral sensitivity at the wavelength of 700 nm of the emulsion having the longest wavelength spectral sensitivity maximum.
The silver halide photographic light-sensitive material as described in the above item 1, wherein the spectral sensitivity ratio at a wavelength of m is 0.7 or less.

The present invention will be described in more detail below. First, the compound of the general formula [I] used in the present invention will be explained. In the above general formula [I], R
Examples of the halogen atom represented by ₁ include a fluorine atom and a chlorine atom, and examples of the alkyl group include methyl, ethyl, isopropyl, t-butyl, cyclopentyl and n-.
Examples of the aryl group include phenyl and 4-methoxyphenyl group, and examples of the alkoxy group include methoxy, ethoxy, butoxy, n-octyloxy, benzyloxy group and the like, and aryloxy. Examples of the group include phenoxy and p-methoxyphenoxy groups.

In the above general formula [I], the group capable of substituting the benzene ring represented by R ₂ is a halogen atom,
(Eg chlorine atom), alkyl group (eg ethyl, i
-Propyl, t-butyl group etc.), alkoxy group (eg methoxy group etc.), aryloxy group (eg phenoxy group etc.), acyloxy group (eg methylcarbonyloxy, benzoyloxy group etc.), acylamino group (eg acetamide, Benzamide group, etc.), carbamoyl group (eg N-methylcarbamoyl group, N-phenylcarbamoyl group etc.), alkylsulfonamide group (eg ethylsulfonamide group etc.), arylsulfonamide group (eg phenylsulfonamide group etc.), sulfamoyl group (For example, N-propylsulfamoyl group, N-phenylsulfamoyl group and the like) and imide group (for example, succinimide, glutarimide group and the like) and the like.

In the general formula [I], the organic group represented by B is, for example, acylamino, alkoxycarbonyl, aryloxycarbonyl, alkylsulfamoyl, arylsulfamoyl, alkylsulfonamide, arylsulfonamide or alkyl. Each group such as ureido, arylureido, succinimide, alkoxy, aryloxy, alkoxycarbonylamino, alkylcarbamoyl, arylcarbamoyl, alkylsulfamoylamino, arylsulfamoylamino, alkyl, alkenyl, acyloxy and the like can be mentioned.
In particular, the total number of carbon atoms is preferably 8-30.

In the above general formula [I], X represents a group represented by the following general formula [X-1] or [X-2].

[0036] In the formula [X-1] -OR ₆ formula, R ₆ represents an aryl group or a heterocyclic group may have a substituent.

[0037]

[Chemical 9]

In the formula, Z'is a 5-membered ring in cooperation with the nitrogen atom.
It represents a group of non-metal atoms necessary for forming a 6-membered ring. Here, as the atomic group necessary to form the non-metallic atomic group,
For example, methylene, methine, substituted methine, = C = O, = N
R _A (R _A has the same meaning as R ₅ ) -N =, -O-,
-S-, SO ₂ -, and the like.

Preferred yellow couplers for use in the present invention are compounds represented by the following general formula [I] -a.

[0040]

In the formula, R ₂ , B and X are represented by the general formula [I]
Represents the same groups as R ₂ and B in. R ₃ represents an alkyl group, a siloalkyl group, or an aryl group, and examples of the alkyl group represented by R ₃ include methyl, ethyl, and
Examples include isopropyl, t-butyl and dodecyl groups. The alkyl group represented by R ₃ also includes those having a substituent, and examples of the substituent include a halogen atom, an aryl group, an alkoxy group, an aryloxy group,
Examples thereof include an alkylsulfonyl group, an acylamino group, an alkoxy group and a hydroxyl group.

Examples of the cycloalkyl group represented by R ₃ include a cyclopropyl group, a cycloxyl group and an adamantyl group. Examples of the aryl group represented by R ₃ include a phenyl group and a p-methoxyphenyl group. Examples of the acyl group represented by R ₃ include an acetyl group, a propionyl group, a butyryl group, a hexanoyl group and a benzoyl group.

R ₃ is preferably an alkyl group or an aryl group, and more preferably a lower alkyl group having 5 or less carbon atoms. Further, in the general formula [I] -a,
Preferred organic groups represented by B are those represented by the following general formula [B
-I] is a group.

General formula [BI]-(J) _p -R ₈

In the formula, J is --NR ₉ CO-- or --CO
It represents R ₉ N-, R ₉ represents a hydrogen atom, an alkyl group, an aryl group or Fukumotowa group, R ₈ represents a linear or branched alkyl group, in particular, be a C6-20 preferable. Typical specific examples of the yellow coupler represented by the general formula [I] and the general formula [I] -a are shown below, but the present invention is not limited thereto.

[0046]

[Chemical 11]

[0047]

[Chemical 12]

[0048]

[Chemical 13]

[0049]

[Chemical 14]

[0050]

[Chemical 15]

General formula [II] used in the present invention
The compound will be described. In the general formula [II],
Examples of the alkyl group represented by R ₄ and R ₅ include a methyl group, an ethyl group, a propyl group, an isopropyl group, and n-
Butyl group, tert-butyl group, n-pentyl group, cyclopentyl group, n-hexyl group, cyclohexyl group, n
Examples include -octyl group and n-dodecyl group. These alkyl groups further include halogen atoms (eg, chlorine atom, bromine atom, fluorine atom, etc.), alkoxy groups (eg, methoxy group, ethoxy group, 1,1-dimethylethoxy group, n-hexyloxy group, n-dodecyl group). Oxy group etc.), aryloxy group (eg phenoxy group, naphthyloxy group etc.), aryl group (eg phenyl group, naphthyl group etc.), alkoxycarbonyl group (eg methoxycarbonyl group, ethoxycarbonyl group, n-butoxycarbonyl group) Group, 2-ethylhexylcarbonyl group, etc., aryloxycarbonyl group (eg, phenoxycarbonyl group, naphthyloxycarbonyl group, etc.), alkenyl group (eg, vinyl group, allyl group, etc.), heterocyclic group (eg, 2-pyridyl group) Group, 3-pyridyl group, 4-pyridyl group, molyfolyl group Piperidyl group, piperazyl group, pyrimidyl group, pyrazolyl group, furyl group etc.), alkynyl group (eg propargyl group etc.), amino group (eg amino group, N, N-dimethylamino group, anilino group etc.), hydroxy group , Cyano group, sulfo group, carboxyl group, sulfonamide group (eg, methylsulfonylamino group, ethylsulfonylamino group, n-butylsulfonylamino group, n-octylsulfonylamino group, phenylsulfonylamino group, etc.) May be.

Examples of the alkenyl group represented by R ₄ and R ₅ include a vinyl group and an allyl group. These groups can be substituted with an alkyl group represented by R ₄ or R ₅ , and a group similar to the group shown as the substituent of the alkyl group.

Examples of the aryl group represented by R ₄ and R ₅ include a phenyl group and a naphthyl group.
These groups can be substituted with an alkyl group represented by R ₄ or R ₅ , and a group similar to the group shown as the substituent of the alkyl group.

The heterocyclic group represented by R ₄ and R ₅ is
For example, pyridyl group (for example, 2-pyridyl group 3-pyridyl group, 4-pyridyl group, etc.), thiazolyl group, oxazolyl group, imidazolyl group, furyl group, pyrrolyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, selenazolyl group, Examples thereof include a sulforanyl group, a piperidinyl group, a pyrazolyl group, and a tetrazolyl group. These groups are R
It can be substituted with an alkyl group represented by ₁ or R ₂ and a group similar to the group shown as the substituent of the alkyl group.

Z ₁ and Z ₂ represent a non-metal atom group for forming a 5-, 6- or 7-membered ring, and examples of the 5-, 6- or 7-membered ring include a pyrrole ring, Imidazole ring, pyrazole ring, isoindole ring, indole ring, indazole ring, purine ring, carbazole ring, carboline ring, perimidine ring, phenothiazine ring, phenoxazine ring, triazole ring, benzimidazole ring, benztriazole ring, pyridone ring, pyrazolone Examples thereof include a ring, a quinolone ring, an isoquinolone ring, a pyrrolidone ring, a piperidone ring, a thiazolidone ring, a thiazoline thio ring, a thiohydantoin ring, a rhodanin ring, and a dithiohydantoin ring. These groups are alkyl groups represented by R ₁ and R ₂ ,
And a group similar to the group shown as the substituent for the alkyl group.

The methine group represented by L ₁ , L ₂ , L ₃ , L ₄ and L ₅ may have a substituent, and as the substituent, an alkyl group represented by R ₁ and R ₂ , and The same group as the group shown as a substituent of the alkyl group is represented.

[0057]

[Chemical 16]

[0058]

[Chemical 17]

[0059]

[Chemical 18]

[0060]

[Chemical 19]

[0061]

[Chemical 20]

[0062]

[Chemical 21]

[0063]

[Chemical formula 22]

[0064]

[Chemical formula 23]

[0065]

[Chemical formula 24]

The dye used in the present invention may be contained in any layer of the silver halide emulsion layer on the support and the other hydrophilic colloid layer, but it may be contained in the layer adjacent to the red-sensitive emulsion layer. It is preferably contained. However,
When the dye diffuses to another layer, the same effect as that added to the adjacent layer can be obtained even if it is added to the intermediate layer or the protective layer other than the adjacent layer.

The addition amount of the dye used in the present invention is not particularly limited, but preferably 1 to 200 mg / each.
m ² and more preferably 3 to 100 mg / m ² so as to be applied. In order to incorporate the dye used in the present invention into the photographic emulsion layer or other hydrophilic colloid layer, generally, the dye or an organic or inorganic alkali salt of the dye is in an aqueous solution or an organic solvent (for example, alcohols, glycols). , Cellosolves, dimethylformamide, dibutyl phthalate, tricresyl phosphate, etc.), if necessary emulsified and dispersed, and added to a coating solution for coating, to be contained in the photosensitive material.

At least one of the silver halide emulsion layers in the present invention contains silver halide grains having a silver chloride content of 95 mol% or more, but also contains a trace amount of silver bromide. Preferably. The silver chloride content of the silver halide grains used in the present invention is preferably 98 mol% or more, and the silver bromide content is preferably 0.05 mol% or more, more preferably 0.1 mol% or more. It is 2 mol%.

The grain size of the silver halide grains used in the present invention is preferably 0.4 to 1.0 μm. The silver halide grains used in the present invention may be used alone or in combination with other silver halide grains having different compositions.

In the silver halide emulsion layer containing silver halide grains having a silver chloride content of 95 mol% or more used in the present invention, all silver halide grains contained in the emulsion layer are The proportion of silver halide grains having a silver chloride content of 95 mol% or more is 80 wt% or more, preferably 90 wt% or more.

The composition of silver halide grains may be uniform from the inside to the outside of the grain, or the composition inside and outside the grain may be different. Further, when the composition inside and outside the particle is different, the composition may continuously change or may be discontinuous.

The grain size of the silver halide grains is not particularly limited, but in view of other photographic properties such as rapid processing property and sensitivity, it is preferably 0.2 to 1.6 μm, more preferably 0.25 to 1 μm. It is in the range of 0.2 μm. The particle size can be measured by various methods generally used in the technical field. As a typical method, Loveland's "particle size analysis method" (ASTM.
Symposium on Right Microscopy, 19
55, pp. 94-122) or "The logic of the photographic process"
(Co-written by Mies and James, Third Edition, Chapter 2 published by Macmillan, Inc. (1966)).

The particle diameter can be measured by using the projected area of the particle or an approximate diameter. If the particles are of substantially uniform shape, the particle size distribution can be fairly accurately expressed as a diameter or projected area. The grain size distribution of the silver halide grains used in the present invention may be polydisperse or monodisperse. In the grain distribution of silver halide grains, monodisperse silver halide grains having a coefficient of variation of 0.22 or less, more preferably 0.15 or less are preferable.

Here, the coefficient of variation is a coefficient indicating the breadth of the particle size distribution and is represented by (standard deviation of particle size distribution) / (average particle size). The grain size referred to here is the diameter of a spherical silver halide grain, or the diameter of a cubic image or a grain of a shape other than spherical when the projected image is converted into a circular image of the same area. Represent

The silver halide grains used in the emulsion according to the invention may be those obtained by any of the acidic method, the neutral method and the ammonia method. The particles may be grown at one time,
The seed particles may be grown and then grown. The method of making seed particles and the method of growing seed particles may be the same or different.

The silver halide grains used in the present invention 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 4,22.
5,666, JP-A-55-26589, JP-B-55
-42737, etc. and The Journal of Photographic Science (J. Photo., Sc
i. ), 21 , 39 (1973) and the like, particles having a shape such as an octahedron, a tetrahedron and a dodecahedron can be prepared and used. Further, grains having twin planes may be used. As the silver halide grains, grains having a single shape may be used, or grains having various shapes may be mixed.

The silver halide grains are cadmium salt, zinc salt,
A metal ion may be added using a lead salt, a thallium salt, an iridium salt (including a complex salt), a rhodium salt (including a complex salt), and an iron salt (including a complex salt) to be contained inside and / or on the surface of the particle. In addition, reduction sensitizing nuclei can be imparted to the inside of the grain and / or the grain surface by placing in an appropriate reducing atmosphere.

The silver halide grain may be a grain in which a latent image is mainly formed on the surface, or may be a grain mainly formed inside the grain. Grains whose latent image is mainly formed on the surface are preferable. Silver halide emulsion,
It is chemically sensitized by a conventional method. That is, a compound containing sulfur capable of reacting with silver ions, a sulfur sensitization method using active gelatin, a selenium sensitization method, a reduction sensitization method, a noble metal sensitization method using gold or other noble metal compounds, etc. are used alone or in combination. be able to.

The silver halide emulsion of the present invention can be spectrally sensitized to a desired wavelength region by using a dye known as a sensitizing dye in the photographic industry. As the sensitizing dye, a cyanine dye, a merocyanine dye, a complex cyanine dye, a complex merocyanine dye, a holopolar cyanine dye, a hemicyanine dye, a styryl dye and a hemioxonol dye can be used.

The silver halide emulsion contained in the blue-sensitive silver halide emulsion of the light-sensitive material of the present invention is, for example, Japanese Patent Application No. 2-
Exemplified Compounds BS-1 to 1 described in the specification of No. 76278
BS-9 and the like can be cited, and the silver halide emulsion contained in the green-sensitive silver halide emulsion layer is, for example, Japanese Patent Application No.
-Exemplary compound GS-1 described in the specification of No. 76278
~ GS-5 etc. can be mentioned.

The silver halide emulsion contained in the red-sensitive silver halide emulsion layer of the light-sensitive material of the present invention has the following general formula [RS
I] or the sensitizing dye represented by the general formula [RSII] is preferably spectrally sensitized.

[0082]

[Chemical 25]

In the formula, R ₁ and R ₂ each represent an alkyl group or an aryl group, and L ₁ , L ₂ , L ₃ , L ₄ , and L ₅
Each represents a methine group. Y ₁ and Y ₂ are each an oxygen atom,
It represents a sulfur atom or a selenium atom, and R ₃ and R ₄ each represent a lower alkyl group.

A ₁ , A ₂ , B ₁ , B ₂ , C ₁ , C ₂ , D
₁ and D ₂ each represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a phenyl group, a cyano group, a nitro group or an alkoxycarbonyl group. Also, A ₁ and B ₁ , B
₁ and C ₁ , C ₁ and D ₁ , A ₂ and B ₂ , B ₂ and C ₂ and C
_At least one of the combination of ₂ and D ₂ may be condensed to form a benzene ring. X ⁻ represents an acid anion. n and k each represent 0 or 1. However, when the compound forms an inner salt, k is 0.

Details of the above substituents are described in Japanese Patent Application No. 2-3055.
It has the same meaning as the specific description of the substituents of [RS1] and [RS2] described in No. 32, page 32, line 3 to page 34, line 19. Specific examples of the sensitizing dyes represented by the general formula [RSI] and the general formula [RSII] are shown below.

[0086]

[Chemical formula 26]

[0087]

[Chemical 27]

[0088]

[Chemical 28]

[0089]

[Chemical 29]

[0090]

[Chemical 30]

[0091]

[Chemical 31]

[0092]

[Chemical 32]

[0093]

[Chemical 33]

The sensitizing dyes may be used alone, or may be a combination of two or more kinds, or a dye having no spectral sensitizing effect with the sensitizing dye itself, or a compound which does not substantially absorb visible light. Therefore, a supersensitizer that enhances the sensitizing action of the sensitizing dye may be contained in the emulsion.

The addition amount of the sensitizing dye of the present invention is not particularly limited, but is generally from 1 × 10 ⁻⁷ to 1 × per mol of silver halide.
It is preferably used in the range of 10 ⁻³ mol, and more preferably 5 × 10 ^{−6 to} 5 × 10 ⁻⁴ mol.

As a method for adding a sensitizing dye, a method well known in the art can be used. For example, these sensitizing dyes are dissolved in a water-soluble solvent such as pyridine, methyl alcohol, ethyl alcohol, methyl cellosolve, acetone, etc. (or a mixture of such solvents), and in some cases diluted with water, In some cases they can be dissolved in water and added in the form of these solutions. It is also advantageous to use ultrasonic vibration for this dissolution.

The sensitizing dye used in the present invention is prepared by dissolving the dye in a volatile organic solvent and dispersing the solution in a hydrophilic colloid as described in US Pat. No. 3,469,987. Method of adding this dispersion, JP-B-46-2418
As described in No. 5, etc., a method of dispersing a water-insoluble dye in a water-soluble solvent without dissolving it, and adding the dispersion is also used.

The sensitizing dye used in the present invention can be added to the emulsion in the form of an acid dissolution dispersion method. Other,
The method of addition is US Pat. Nos. 2,912,345 and 3,3,3.
42, 605, 2, 2, 996, 287, 3, 42
The method described in No. 5,835 is also used.

The sensitizing dye contained in the silver halide emulsion of the present invention is dissolved in the same or different solvent, and these solutions are mixed or added separately prior to addition to the silver halide emulsion. You may add. When they are added separately, the order, time, and interval can be arbitrarily determined according to the purpose.

The sensitizing dye used in the present invention may be added to the emulsion at any time during the emulsion production process.
It is preferably added before, during or after the chemical ripening, and more preferably before or during the chemical ripening. Regarding the spectral sensitization sensitivity of each light-sensitive layer of the silver halide color light-sensitive material of the present invention, 47 of the emulsion having the maximum spectral sensitivity maximum of a single wavelength among wavelengths having the maximum spectral sensitivity value.
The ratio of the spectral sensitivity at the wavelength of 490 nm to the spectral sensitivity at the wavelength of 0 nm is preferably 0.5 or less, and more preferably 0.4 or less.

Further, it is preferable that the ratio of the spectral sensitivity at the wavelength of 720 nm to the spectral sensitivity at the wavelength of 700 nm of the emulsion having the spectral sensitivity maximum of the longest wavelength among the wavelengths of the spectral sensitivity maximum is 0.7 or less. And more preferably 0.6 or less. In the present invention, a magenta dye-forming coupler and a cyan dye-forming coupler are used in addition to the yellow coupler used in the present invention.

In the present invention, as the magenta dye forming coupler, known couplers such as 5-pyrazolone type couplers, pyrazoloazole type couplers and pyrazolobenzimidazole type couplers can be used. Specific examples of the magenta coupler preferably used in the present invention will be given below, but the present invention is not limited to these examples.

[0103]

[Chemical 34]

[0104]

[Chemical 35]

[0105]

[Chemical 36]

[0106]

[Chemical 37]

In addition to the above representative examples, magenta couplers that can be used in the present invention are disclosed in JP-A-62-
Among the compounds described on page 18, upper right column to page 32, upper right column of No. 166339, No. 1-4, 6, 8-1
7, 19-24, 26-43, 45-59, 61-10
4, 106-121, 123-162, 164-233
And a compound represented by No. 5 of JP-A No. 2-100048.
Examples thereof include compounds represented by M-1 to M-29 described on page 6.

In the present invention, as the cyan dye forming coupler, a naphthol type coupler and a phenol type coupler can be preferably used. Particularly, when it is used as a light-sensitive material for direct appreciation such as color photographic paper, it is described in, for example, US Pat.
No. 5,826, JP-A Nos. 50-112038 and 53-
109630, 55-163537, 63-9.
2,5-diacylaminophenol cyan couplers disclosed in US Pat. No. 6,656, and U.S. Pat. No. 3,772,0.
Phenol cyan couplers having an alkyl group having 2 or more carbon atoms at the 5-position described in No. 02, No. 4,443,536, etc. are advantageously used.

An example of the former is, for example, Japanese Patent Laid-Open No. 63-9.
Exemplified compounds C-1 to C-2 described in No. 6656.
5 and the like. Examples of the latter include, for example, Exemplified Compound IV-described in JP-A No. 1-196048.
1 to IV-19 and the like. Specific examples of the cyan coupler used in the present invention are shown below, but the present invention is not limited thereto.

[0110]

[Chemical 38]

[0111]

[Chemical Formula 39]

[0112]

[Chemical 40]

[0113]

[Chemical 41]

The compound such as the dye-forming coupler of the silver halide photographic light-sensitive material of the present invention is usually a high-boiling organic solvent having a boiling point of about 150 ° C. or higher or a water-insoluble polymer, if necessary, a low-boiling and / or water-soluble organic compound. It is dissolved together with a solvent, emulsified and dispersed in a hydrophilic binder such as an aqueous gelatin solution with a surfactant, and then added to the desired hydrophilic colloid layer. A step of removing the low boiling point organic solvent and rubbing may be added at the same time as the dispersion liquid or the dispersion.

The high-boiling organic solvent is preferably a compound having a dielectric constant of 6.5 or less, for example, esters such as phthalic acid ester and phosphoric acid ester having a dielectric constant of 6.5 or less, organic acid amides, ketones and hydrocarbons. Compounds and the like. The high boiling point organic solvent may be a mixture of two or more kinds. The high-boiling point organic solvent, which means a dielectric constant at 30 ° C., is generally used in a proportion of 0 to 400% by weight with respect to the coupler. Preferably 10 to 10 for coupler
It is 0% by weight.

Gelatin is preferably used as the binder used in the silver halide photographic light-sensitive material of the present invention. The gelatin used in the light-sensitive material of the present invention may be lime-processed gelatin, acid-processed gelatin, or gelatin produced from any of cow bone, cow hide, pig skin, etc., but is preferably Is a lime-processed gelatin produced from cow bone.

The photographic emulsion layer and other hydrophilic colloid layers of the light-sensitive material of the present invention are hardened by using a hardener which cross-links binder (or protective layer colloid) molecules and enhances film strength, either alone or in combination. It A UV absorber for preventing fog due to discharge caused by charging of the photosensitive colloidal layer such as a protective layer or a hydrophilic colloidal layer to the photosensitive material of the present invention due to friction or the like, and preventing deterioration of an image by ultraviolet light. May be included.

The light-sensitive material of the present invention may be provided with auxiliary layers such as a filter layer, an antihalation layer and / or an antiirradiation layer. These layers and / or emulsion layers may contain dyes other than the dyes used in the present invention, which are bleached or bleached from the color light-sensitive material during development processing.

Further, the light-sensitive material of the present invention contains a fluorescent whitening agent as described in JP-A-59-71049 and 59-71050 in order to obtain a visually clear image. Alternatively, when the optical brightener is water-soluble, a fluorescent whitening agent scavenger can be contained for the purpose of preventing the outflow from the light-sensitive material.

As the scavenger, any compound can be used as long as it is a compound capable of scavenging the fluorescent whitening agent, but a particularly useful one is a hydrophilic polymer, for example, polyvinylpyrrolidone and vinylpyrrolidone are repeatedly used. A copolymer contained as a unit, a hydrophilic polymer containing a cationic nitrogen-containing active group described in JP-A-48-42732.
The copolymer of vinyl alcohol and vinylpyrrolidone described in JP-B-47-20738 can be mentioned.

A matting agent is used in the silver halide emulsion layer and / or other hydrophilic colloid layers of the light-sensitive material of the present invention for the purpose of reducing the gloss of the light-sensitive material, enhancing the writing property, and preventing sticking between the light-sensitive materials. Can be added.

A lubricant may be added to the light-sensitive material of the present invention to reduce sliding friction. An antistatic agent can be added to the light-sensitive material of the present invention. The antistatic agent may be used in the antistatic layer on the side of the support on which the emulsion is not laminated, and may be used for protection of the emulsion layer and / or the support other than the emulsion layer on the side on which the emulsion layer is laminated. It may be used for the colloid layer.

In the photographic emulsion layer and / or other hydrophilic colloid layer of the light-sensitive material of the present invention, coating property is improved, antistatic property, slipperiness is improved, emulsion dispersion, adhesion prevention and (development acceleration, hardening, enhancement). Various surfactants can be used for the purpose of photographic characteristics (such as feeling).

The photographic emulsion layers and other layers of the light-sensitive material of the present invention are baryta paper or paper laminated with α-olefin polymer and the like, and a paper support on which the α-olefin layer can be easily peeled from the paper support, synthetic. Flexible reflective support such as paper,
Cellulose acetate, cellulose nitrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, a reflective support coated with a film made of a semi-synthetic or polymer such as polyamide and a white pigment, and glass,
It can be applied to rigid bodies such as metal and pottery. Or 120-1
It is also possible to use a thin reflective support of 60 μm.

The support used in the light-sensitive material of the present invention is
It may be either a reflective support or a transparent support, and a white pigment may be contained in the support for imparting reflectivity, and the white pigment is preferably barium sulfate or titanium oxide.

The light-sensitive material of the present invention may be directly or undercoated (adhesiveness, antistatic property, It may be applied via one or more subbing layers) to improve stability, abrasion resistance, hardness, antihalation, friction properties and / or other properties. In the processing of the light-sensitive material of the present invention, the color-developing agent used in the color-developing solution includes known ones widely used in various color photographic processes.

These developers include aminophenol-based and p-phenylenediamine-based derivatives. Since these compounds are more stable than the free state, they are generally used in the form of salts, for example, hydrochlorides or sulfates. Also, these compounds are generally used at a concentration of preferably 0.1 to 30 g per liter of color developing solution, preferably about 3 g to about 15 g per liter of color developing solution.

Particularly useful primary aromatic amine-based color developing agents are N, N-dialkyl-p-phenylenediamine-based compounds, and the alkyl group and phenyl group may be substituted with any substituents. .. Known compounds can be used as the aromatic primary amine developing agent used in the present invention. The following compounds can be mentioned as an example 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
-(Β-Butoxyethyl) aniline

When used in the image forming method according to the present invention, a compound represented by the following general formula [CD-1] is more preferably used, particularly from the viewpoint of development processing for a short time.

[0131]

[Chemical 42]

In the general formula [CD-1], R is a linear or branched alkylene group having 3 carbon atoms, m and n are each an integer of 1 to 4, and HA represents an inorganic or organic acid. , For example, hydrochloric acid, sulfuric acid, nitric acid, p-toluenesulfonic acid and the like. These color developing agents are described in Journal of American Chemical Society, Volume 73, 31.
00 (1951). Specific examples of the compound represented by the general formula [CD-1] are shown below.

[0133]

[Chemical 43]

[0134]

[Chemical 44]

For the color developing solution applied to the processing of the light-sensitive material of the present invention. In addition to the above primary aromatic amine-based color developing agent, a known developer component compound can be added. For example, an alkali agent such as sodium hydroxide, sodium carbonate or potassium carbonate, an alkali metal sulfite salt, an alkali metal bisulfite salt, an alkali metal thiocyanate salt, an alkali metal halide, benzyl alcohol, a water softening agent and a thickening agent are optional. It can also be contained in.

The pH value of the color developing solution is usually 7 or more,
Most commonly about 10-13. The color development temperature is usually 15 ° C. or higher, and generally 20 ° C. to 50 ° C. For rapid development, it is preferably carried out at 30 ° C. or higher. The color development time is generally 15 seconds to 60 seconds.
It is preferable to be performed in the range of seconds, more preferably 20 seconds.
The range is from seconds to 50 seconds.

The light-sensitive material of the present invention is subjected to bleaching treatment and fixing treatment after color development. The bleaching process may be performed simultaneously with the fixing process. After the fixing process, a washing process is usually performed. Further, as an alternative to the water washing treatment, a stabilizing treatment may be performed, or both may be used together. The stabilizing solution used for the stabilizing treatment may contain a pH adjusting agent, a chelating agent, a fungicide, and the like. These specific conditions are
Reference can be made to JP-A-58-134636.

[0138]

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

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

First layer coating solution Yellow coupler (Comparative YC-A) 24.4 g, dye image stabilizer (ST-1) 10.0 g, dye image stabilizer (ST-2) 6.67 g, stain prevention Agent (HQ-1)
To 0.67 g and 6.67 g of a high boiling organic solvent (DNP), 60 ml of ethyl acetate was added and dissolved, and this solution was added to 220 ml of 10% gelatin aqueous solution containing 7 ml of 20% surfactant (SU-1). A yellow coupler dispersion was prepared by emulsifying and dispersing using a sonic homogenizer. This dispersion was mixed with a blue-sensitive silver halide emulsion (containing 10 g of silver) prepared under the following conditions,
A layer coating solution was prepared.

The coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. Further, as a hardening agent, (H-1) was added to the second and fourth layers, and (H-2) was added to the seventh layer. Surfactants (SU-1) and (SU-2) were added as coating aids to adjust the surface tension.

[0142]

[Table 1]

[0143]

[Table 2]

[0144]

[Chemical 45]

[0145]

[Chemical 46]

[0146]

[Chemical 47]

[0147]

[Chemical 48]

(Preparation method of blue-sensitive silver halide emulsion) 4
In 1000 ml of a 2% gelatin aqueous solution kept at 0 ° C., the following (solution A) and (solution B) were pAg = 6.5,
Simultaneously added over 30 minutes while controlling pH = 3.0, and further the following (solution C) and (solution D) were pAg = 7.3, pH =
Simultaneous addition was carried out over 180 minutes while controlling at 5.5. At this time, pAg was controlled by the method described in JP-A-59-45437, and pH was controlled by using an aqueous solution of sulfuric acid or 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 Potassium bromide 1. 0 g Water is added to 600 ml (D liquid) Silver nitrate 300 g Water is added to 600 ml

After the addition is completed, Demol N manufactured by Kao Atlas Co., Ltd.
Of 5% aqueous solution of magnesium sulfate and 20% aqueous solution of magnesium sulfate, and then mixed with an aqueous solution of gelatin to have an average particle size of 0.85 μm, a coefficient of variation of particle size distribution of 0.07, and a silver chloride content of 99. 5 mol% of monodisperse cubic emulsion EMP-1 was obtained.

The EMP-1 was optimally chemically sensitized with the following compounds at 50 ° C. 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 6 × 10 ⁻⁴ mol / mol AgX sensitizing dye BS-1 4 × 10 ⁻⁴ mol / mol AgX sensitizing dye BS-2 1 × 10 ^-4 mol / mol AgX

(Preparation method of green-sensitive silver halide emulsion)
(A solution) and (B solution) addition time and (C solution) and (D solution)
A monodisperse cubic emulsion EMP-2 having an average particle size of 0.43 μm, a coefficient of variation of 0.08 and a silver chloride content of 99.5% was obtained in the same manner as in EMP-1 except that the addition time was changed.

The above-mentioned EMP-2 was optimally chemically sensitized with the following compound at 55 ° C. to obtain a green-sensitive silver halide emulsion (Em-G). Sodium thiosulfate 1.5 mg / mol AgX chloroauric acid 1.0 mg / mol AgX stabilizer STAB-1 6 × 10 ⁻⁴ mol / mol AgX sensitizing dye GS-1 4 × 10 ⁻⁴ mol / mol AgX

(Preparation method of red-sensitive silver halide emulsion)
(A solution) and (B solution) addition time and (C solution) and (D solution)
A monodisperse cubic emulsion EMP-3 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 in the same manner as in EMP-1, except that the addition time was changed. or,
The following metal compounds were added to the (C liquid). K ₂ IrC1 ₆ 3.8 × 10 ⁻⁸ mol / mol AgX K ₄ Fe (CN) ₆ 1.2 × 10 ⁻⁵ mol / mol AgX

The above-mentioned EMP-3 was optimally chemically sensitized at 60 ° C. using the following compounds 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 6 × 10 ⁻⁴ mol / mol AgX sensitizing dye RS-17 1 × 10 ⁻⁴ mol / mol AgX

[0156]

[Chemical 49]

Sample No. 1 having the same structure except that the yellow coupler of the first layer and the dye of the fourth layer of the sample prepared as described above were replaced as shown in Table 1. 1-20 were produced.

[0158]

[Chemical 50]

[0159]

[Chemical 51]

The sample thus obtained was exposed according to a conventional method and then processed according to the following processing steps.

Processing step Temperature Time Color development 35.0 ± 0.3 ° C. 45 seconds Bleach fixing 35.0 ± 0.5 ° C. 45 seconds Stabilization 30-34 ° C. 90 seconds Dry 60-80 ° C. 60 seconds

[Color developer] Pure water 800 ml Triethanolamine 10 g N, N-diethylhydroxylamine 5 g Potassium bromide 0.02 g Potassium chloride 2 g Potassium sulfite 0.3 g 1-Hydroxyethylidene-1,1-diphosphonic acid 1 0.0 g Ethylenediaminetetraacetic acid 1.0 g Catechol-3,5-disulfonic acid disodium salt 1.0 g N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate 4.5 g Fluorescence enhancement Whitening agent (4,4'-diaminostilbenedisulfonic acid derivative) 1.0 g Potassium carbonate 27 g Water is added to bring the total volume to 1 liter, and the pH is adjusted to 10.10.

[Bleach-fixing solution] ethylenediaminetetraacetic acid ammonium ferric dihydrate 60 g ethylenediaminetetraacetic acid 3 g ammonium thiosulfate (70% aqueous solution) 100 ml ammonium sulfite (40% aqueous solution) 27.5 millitorr Liter, pH = 5 with potassium carbonate or glacial acetic acid. Adjust to 7.

[Stabilizing Solution] 5-chloro-2-methyl-4-isothiazolin-3-one 1.0 g ethylene glycol 1.0 g 1-hydroxyethylidene-1,1-diphosphonic acid 2.0 g ethylenediaminetetraacetic acid 1. 0 g Ammonium hydroxide (20% aqueous solution) 3.0 g Optical brightener (4,4'-diaminostilbenedisulfonic acid derivative) 1.5 g Water was added to make the total volume 1 liter, and pH was adjusted to 7 with sulfuric acid or potassium hydroxide. Adjust to 0. Next, the following evaluation was performed on each of the obtained samples.

(Sensitometry) PD for each treated sample
The sensitivity and gradation were determined using an A-65 densitometer (manufactured by Konica Corporation). Sensitivity (S) = reciprocal of exposure amount giving reflection density 0.8 Gradation (γ) = slope of straight line connecting points of reflection density 0.5 and 1.5 in HD curve obtained by conventional method

(Sharpness) A resolution test chart was printed on each sample with red light and after the above treatment, the obtained cyan image was subjected to density measurement with a microdensitometer PDM-5 (manufactured by Konica Corporation). Then, the value represented by the following formula was defined as the sharpness. Sharpness (%) = (5m / mm Dm of dense line print image
ax-Dmin) / (Dmax-Dmi in large area part
n) Here, Dmax: maximum density, Dmin: minimum density, the larger this value, the better the sharpness.

(Whiteness) For each sample, Konica Color Printer Processor CL-PP1701QA (manufactured by Konica Corporation) was used in accordance with the above-mentioned processing prescription without being exposed.
The continuous replenishment process is performed until the accumulated replenishment amount exceeds the liquid amount at the start, and the
Blue, green and red light reflection densities (Dmin ^B , Dm
in ^G , Dmin ^R ) was measured. Each Dmin
The smaller the, the better the whiteness. The value of Dmin is
If it is 0.02 or less, it is an allowable level, but 0.
When it exceeds 020, the whiteness is visually deteriorated, and when it exceeds 0.025, the photographic quality is seriously deteriorated. The above results are shown in Table 3 together with the constitution of the sample.

[0168]

[Table 3]

As is clear from the results of Table 3, only in the combination of the yellow coupler and the novel dye as in the present invention, in terms of sharpness, sensitivity and whiteness,
It can be seen that satisfactory photographic performance can be obtained and the advantages of the silver halide emulsion with high sensitivity can be fully utilized.

Example 2 Chemical sensitization was carried out in the same manner as in EM-B, except that the sensitizing dye BS-1 used in the chemical sensitization of the emulsion EM-B of Example 1 was changed to BS-a. As a result, a blue-sensitive silver halide emulsion (EM-Ba) was obtained. Also, the EM-R of Example 1
The sensitizing dye RS-17 used for the chemical sensitization of
Chemical sensitization was carried out in the same manner as in EM-R except that it was replaced with, and as a result, red-sensitive silver halide emulsion (EM-R-a)
Got

[0171]

[Chemical 52]

As shown in Table 5, except that the blue-sensitive silver halide emulsion of the first layer, the red-sensitive silver halide emulsion of the fifth layer, the yellow coupler of the first layer, and the dye of the fourth layer are changed as shown in Table 5, Samples 21 to 48 were manufactured in exactly the same manner as in Example 1. Sample 40 using EM-B silver halide emulsion
And a sample 48 using the silver halide emulsion of EM-B-a
Table 2 shows the ratio of the spectral sensitivity at the wavelength of 490 nm to the spectral sensitivity at the wavelength of 470 nm.

For each of the sample 40 using the silver halide emulsion of EM-R and the sample 48 using the silver halide emulsion of EM-R-a, the wavelength at 720 nm with respect to the spectral sensitivity at the wavelength of 700 nm. When the ratio of the spectral sensitivities is obtained, it is as shown in Table 4. The spectral sensitivity at each wavelength was measured by using an interference filter and a colored glass filter manufactured by Toshiba Corporation in accordance with the evaluation method of (sensitometry) in Example 1.

[0174]

[Table 4]

[0175]

[Table 5]

[0176]

[Chemical 53]

Each of the obtained samples was processed in the same manner as in Example 1 after exposure or without exposure, and the sharpness, relative sensitivity, whiteness and color reproducibility were evaluated.

(Color Reproducibility) A color chart (manufactured by Macbeth) was photographed and developed with Konica Color DD100 (manufactured by Konica), and the tone of the gray scale portion was adjusted using a negative film. The color reproducibility (yellow, magenta, cyan, red, blue, green) of each hue of the print obtained by the processing was visually evaluated comprehensively. ◯ ・ ・ ・ ・ ・ Good color reproducibility close to the original 〇 △ ・ ・ ・ ・ Slightly cloudy and slightly insufficient color reproduction △ ・ ・ ・ ・ ・ Slightly cloudy and insufficient color reproduction 6 shows.

[0178]

[Table 6]

As is clear from the results shown in Table 6, the combination of the yellow coupler of the present invention and the dye used in the present invention is excellent in sharpness, sensitivity and whiteness and is also excellent in color reproducibility. I understand.

With regard to color reproducibility, particularly, EM-B and red-sensitive silver halide emulsions in which the ratio of the spectral sensitivity at the wavelength of 490 nm to the spectral sensitivity at the wavelength of 470 nm of the blue-sensitive silver halide emulsion is 0.5 or less. 700 nm
The ratio of the spectral sensitivity of 720 nm to the spectral sensitivity at the wavelength of 0.7 is EM-R of 0.7 or less, contains the yellow coupler of the general formula [I] -a, and has the general formula [II]. Alternatively, it was found that the sample using the dye of the general formula [III] was the most excellent.

Example 3 In the preparation of the color developer of Example 1, the color developing agent was replaced with N, N-diethylhydroxylamine by equimolar exemplified compounds (I-2) and (CD-6), respectively. A color developing solution was prepared in the same manner as above, except that the processing temperature and processing time in the processing step were changed as follows, and each sample of Example 1 was processed in the same manner as in Example 1. An evaluation was made. (Processing process) Processing process Temperature time Color development 35.0 ± 0.3 ° C. 45 seconds Bleach fixing 35.0 ± 0.5 ° C. 45 seconds Stabilization 30-34 ° C. 90 seconds Dry 60-80 ° C. 60 seconds

As a result, the effect of the sample of the present invention on the comparative sample was found to be equal to or higher than that of Example 1, particularly in the sensitivity (S _B ), and the combination of the present invention indicated that high sensitivity was obtained. Regarding the point, it was found that the effect was particularly great in the short-time treatment.

[0183]

According to the present invention, a high-sensitivity silver halide emulsion containing a yellow coupler represented by the general formula [I] is combined with a dye represented by the general formula [II] or the general formula [III] to obtain a sharp image. Both surname and color reproduction are excellent,
Moreover, not only a silver halide photographic light-sensitive material having high sensitivity and less fog can be obtained, but this dye also has excellent effects such as no adverse effect on photographic performance such as fog and no residual color contamination even in a short time processing. Have.

The ratio of the spectral sensitivity at the wavelength of 490 nm to the spectral sensitivity at the wavelength of 470 nm is 0.5.
When the ratio is less than or equal to 0.7 and the ratio of the spectral sensitivity at the wavelength of 720 nm to the spectral sensitivity at the wavelength of 700 nm is 0.7 or less, excellent color reproducibility is obtained.

Claims (4)

[Claims] 1. A silver halide photographic light-sensitive material comprising at least one photosensitive silver halide emulsion layer provided on a support, wherein at least one of the silver halide emulsion layers has a silver chloride content of 95. At least one mol% of the silver halide emulsion, at least one of the silver halide emulsion layers contains a yellow coupler represented by the general formula [I], and the silver halide emulsion layer or other hydrophilic colloid A silver halide photographic light-sensitive material characterized in that at least one layer contains a compound represented by the general formula [II] or the general formula [III]. [Chemical 1] [In the formula, R ₁ represents a halogen atom, an alkyl group, an aryl group, an alkoxy group, or an aryloxy group, and R ₂ represents
Represents a hydrogen atom or a group capable of substituting for a benzene ring, m is 1
Or represents an integer of 2. B represents an organic group, and X represents a hydrogen atom or a group capable of splitting off upon reaction with an oxidized product of a color developing agent. ] [Chemical 2] [In the formula, R ₄ and R ₅ represent a hydrogen atom, an alkyl group, an aryl group, an alkenyl group or a heterocyclic group, and Z ¹ and Z ² are 5
Represents a non-metallic atomic group for forming a 6-, 7-, or 7-membered heterocycle. L _{1 to} L ₅ represent a methine group, and n ₁ and n ₂ represent integers of 0, ₁ and ₂ . ] [Chemical 3] [In the formula, R ₆ and R ₇ have the same meanings as R ₄ and R ₅ ,
Z ³ has the same meaning as Z ¹ and Z ² . L _{6 to} L ₁₀ are L
₁ has the same meaning as L ₅ and n ₃ , n ₄ are 0, 1, 2
Represents the integer. ] 2. A silver halide photographic light-sensitive material characterized in that the yellow coupler contained in the silver halide emulsion layer according to claim 1 is a compound represented by the general formula [I] -a. [Chemical 4] [R ₃ represents an alkyl group, an aryl group, a cycloalkyl group or an acyl group, R ₂ represents a hydrogen atom or a group capable of substituting for a benzene ring, and m represents an integer of 1 or 2. B represents an organic group, and X represents a hydrogen atom or a group capable of splitting off upon reaction with an oxidized product of a color developing agent. ] 3. An emulsion having the maximum spectral sensitivity of the shortest wavelength among the wavelengths of the maximum spectral sensitization sensitivity of each photosensitive layer.
2. The silver halide photographic light-sensitive material according to claim 1, wherein the spectral sensitivity ratio at a wavelength of 70 nm is 0.5 or less. 4. The emulsion having the maximum spectral sensitivity of the longest wavelength among the wavelengths of the maximum spectral sensitization sensitivity of each photosensitive layer.
2. The silver halide photographic light-sensitive material according to claim 1, wherein the ratio of the spectral sensitivity at the wavelength of 720 nm to the spectral sensitivity at the wavelength of 00 nm is 0.7 or less.