JPH0450940A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To enhance color reproduction performance, especially, that of blue- green color by spectrally sensitizing silver halide grains contained in a green- sensitive silver halide emulsion layer with each of at least 3 kinds of specified sensitizing dyes. CONSTITUTION:The silver halide grains contained in at least one of the green- sensitive silver halide emulsion layers are spectrally sensitized with each of at least 3 kinds of sensitizing dyes represented by formulae I-III in which each of R1-R7 except R3 is alkyl or alkenyl; each of R3 and R8 is H, alkyl, or the like; each of X1-X3 is an electric charge balancing counter ion; each of n1-n3 is a number of >0 necessary to neutralize the total charges of each molecule; each of Z1 and X2 is an atomic group necessary to form a benzoxazole ring; each of Z3 and Z4 is an atomic group necessary to form a pyrroline ring or a pyridine ring; and each of Z5 and Z6 is an atomic group necessary to form a naphthoxazole ring, thus permitting color reproduction performance, especially, that of the blue-green color to be enhanced.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a spectrally sensitized silver halide color photographic light-sensitive material. The present invention relates to a silver halide color photographic light-sensitive material which has excellent color reproducibility with respect to a light source including a light source and which has excellent storage stability over time of the produced light-sensitive material.

[Background of the invention]

In recent years, the image quality of silver halide multilayer color photographic materials has significantly improved.

That is, in recent color photographic materials, the three major elements of image quality, namely graininess, sharpness, and color reproducibility, have all reached considerably high levels. For example, when it comes to general color photographs, it is believed that there are usually no major complaints regarding the color prints and slide photographs that users receive.

However, among the three factors mentioned above, in particular regarding color reproducibility, although color purity has improved, the situation has not changed much even today with respect to colors, which have traditionally been said to be difficult to reproduce in photographs. That is, there are still many deficiencies in hue reproducibility. For example, violet colors such as violet and blue-violet that reflect light with wavelengths longer than 600 nm, or green colors such as blue-green and yellow-green, will be reproduced as completely different colors from the actual colors, which will disappoint the user. Sometimes.

Spectral sensitivity distribution and interlayer effect (interimage effect, hereinafter referred to as rlE) are major factors related to color reproducibility.
There is.

Regarding IIE, the following is known. That is, it is known to add a compound that couples with the oxidized form of a color developing agent to form a development inhibitor or its precursor in a silver halide multilayer color photographic light-sensitive material. It is known that by inhibiting the development of other color forming layers using a development inhibitor, 11E is produced and the effect of improving color reproducibility is produced.

Furthermore, in a color negative film, it is possible to provide the same effect as IIE by using a colored coupler in an amount greater than the amount that offsets unnecessary absorption.

However, if you use a lot of colored couplers,
As the minimum density of the film increases, the colors and
Density correction becomes very difficult to judge and often results in poor color quality in the resulting print.

Incidentally, these techniques particularly contribute to improving color purity among color reproducibility. The so-called diffusible D i R, which has been frequently used recently and whose precursor has a high mobility, greatly contributes to the improvement of color purity. However, IIE has the drawback that it is difficult to control its directionality, and although it can achieve high color purity, it changes the hue. (Directional control of IIE is described in US Pat. No. 4,725,529, etc.).

On the other hand, regarding the spectral sensitivity distribution, US Patent No. 3.672.
No. 898 discloses an appropriate spectral sensitivity distribution for reducing variations in color reproducibility due to differences in light sources during photographing.

However, this is not a means to improve the aforementioned poor color reproducibility.

In JP-A No. 61-34541, which also discloses a technology that combines spectral sensitivity distribution and IIE, an attempt has been made to improve the colors that are difficult to reproduce with the aforementioned color film, and some results have been achieved. It seems that it will be possible. A typical example of this is not only the conventional IIE from the center wavelength of each of the blue, green, and red sensitive layers, but also the IIE from a wavelength other than the center of gravity of each color-sensitive layer. .

This technology seems to be effective to some extent in improving the hue reproducibility of specific colors, but specifically, in order to express IIH, in addition to the original blue-sensitive, green-sensitive, and red-sensitive photosensitive layers, I
An IE expression layer and another type of photosensitive silver halide are required,
It has the disadvantage that production costs are high due to an increase in the amount of silver and an increase in the number of production steps.
Moreover, the effect could not be said to be sufficient.

For the above reasons, conventional silver halide color photographic materials have been insufficient in terms of color reproduction. In particular, it was difficult to faithfully reproduce blue-green colors, and the hues were sometimes far removed from the actual colors.

The present inventors focused particularly on this blue-green hue reproducibility, and as a result of intensive study, the spectral sensitivity distribution of the green-sensitive silver halide emulsion layer was shifted to the shorter wavelength side than before, and the wavelength λG giving the highest sensitivity was It has been discovered that the above problems can be improved by designing the device so that nlax is 530 to 550 nm. However, it has been found that even with the combination of the above techniques, only very unsatisfactory color reproducibility can be obtained when photographing under fluorescent lighting, which has recently become common, or under mixed light of strobe light and fluorescent lighting. That is, even if only a fluorescent light source or a strobe light is used, if there is an influence from the fluorescent light, the color reproduction will be greenish.

Furthermore, when the sensitivity at 560 to 570 nm becomes low, color reproducibility for orange and skin colors deteriorates. Therefore, it is also necessary to maintain spectral sensitivity in these wavelength ranges.

Furthermore, when spectrally sensitized with the sensitizing dyes used in the above techniques, storage stability under high temperature and high humidity conditions is not satisfactory, and improvement in storage stability has also been desired.

[Purpose of the invention]

An object of the present invention is to provide a silver halide color photographic sensitizer that has excellent color reproducibility, particularly for blue-green, and color reproducibility for light sources including fluorescent lamps, and that has excellent storage stability over time for the produced photosensitive materials. The goal is to provide materials.

[Structure of the invention]

In order to develop a silver halide photographic light-sensitive material that satisfies such demands, the present inventors have conducted intensive research and found that at least one layer of a silver halide emulsion layer, a green-sensitive emulsion layer, and a green-sensitive silver halide emulsion layer are formed on a support. In a silver halide color photographic light-sensitive material having a red-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer, at least one of the green-sensitive silver halide emulsion layers
The silver halide grains contained in the layer have at least one sensitizing dye represented by the following general formula (i) and the following general formula (If).
At least one sensitizing dye represented by the following general formula [
It has been found that the above object can be achieved by a silver halide color photographic material which is spectrally sensitized with at least one sensitizing dye represented by (nl).

General formula CI) General formula (II) General formula (I[[) In the formula, R1, R2, R3, Ra, Rs, Ra and R7 each represent an alkyl group or an alkenyl group. Re
, Re represents an alkyl group, an alkenyl group or an aryl group.

R,, R, represents a hydrogen atom, an alkyl group or an aryl group.

Xl, X, ,X, each represent a charge-balanced counterion, nl
, R2, and n each represent a value of 0 or more necessary to neutralize the charge of the entire molecule. 2. ．． 2. each represents a group of atoms necessary to complete the benzoxazole nucleus.

Z and Z4 are respectively viroline nucleus, pyridine nucleus, quinoline nucleus, indolenine nucleus, benzimidazole nucleus, oxazole nucleus, benzoxazole nucleus, naphthoxazole nucleus, thiazoline nucleus, thiazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, and selenazole. Represents a group of atoms necessary to complete a nucleus, benzoselenazole nucleus, or naphthoselenazole nucleus. Z6 and Z each represent an atomic group necessary to complete the naphthoxazole nucleus.

The present invention will be explained in more detail below.

General formulas CI), [I[) and CN3 used in the present invention
In the compound represented by R+, R2, RaRs, R
a and R7 each have 1 to 10 carbon atoms, and the branching region is a straight-chain alkyl group (e.g., methyl, ethyl, propyl, butyl pendel, l-pentyl, 2-ethyl-hexyl,
octyl, decyl, etc.) or alkenyl groups having 3 to 10 carbon atoms (e.g., 2-propenyl, 3-phthynyl, ■-
methyl-3-propenyl, 3-pentenyl, -methyl-3-butenyl, 4-hexenyl, etc.). These groups include halogen atoms (e.g. fluorine, chlorine, bromine, etc.),
Alkoxy groups (e.g. methoxy, ethoxy, etc.), aryloxy groups (e.g. phenoxy, p-tolyloxy, etc.)
, cyan group, carbamoyl group (e.g. carbamoyl, N
-methylcarbamoyl, N,N-tetramethylenecarbamoyl, etc.), sulfamoyl groups (e.g. sulfamoyl, N,N-3-oxapentamethyleneaminosulfonyl, etc.), methanesulfonyl groups, alkoxycarbonyl groups (
For example, ethoxycarbonyl, butoxycarbonyl, etc.)
aryl groups (e.g. phenyl, carboxyethyl, etc.),
Acyl groups (e.g. acetyl, benzoyl, etc.), acylamino groups (e.g. acetylamino, benzoylamino, etc.), sulfonamide groups (e.g. methanesulfonamide,
butanesulfonamide, etc.), and is preferably substituted with a water-soluble group (for example, a sulfo group, a carboxyl group, a phosphono group, a sulfato group, a hydroquine group, a sulfino group, etc.).

Examples of the alkyl group substituted with a water-soluble group represented by Rl, R2, Ra, Rs, R6 and R7 include carboxymethyl, sulfoethyl, sulfopropyl, sulfobutyl, sulfopentyl, 3-sulbutyl, hydroxyethyl, Carboxyethyl, 3-sulfinobutyl, 3
Examples of the alkenyl group substituted with a water-soluble group include 4-phosphonopropyl, p-sulfobenzyl, 0-hydroxybenzyl, and 4-sulfo-3-butenyl, 2-phosphonopropyl,
-Ruboxy-2-propenyl group and the like.

The alkyl groups represented by R1 and R8 are each a branched or straight chain group having 1 to 10 carbon atoms (for example, methyl, ethyl, propyl, butyl, i-pentyl, etc.), and the aryl group is, for example, Examples include phenyl and naphthyl groups. These groups include R1゜Rx, R4, Rs, Rs
The substituents explained for and R7 can be substituted at any position.

In the general formulas CI), 1:II) and (III), it is preferred that one of R2 and R2, R6 and R6, and R6 and Ra has a water-soluble group.

Ions that cancel out the charges within the molecule represented by X l+X 2 and X are selected from anions and cations. Anions include inorganic and organic ones, specifically halogen ions (e.g. chlor, bromine, iodine, etc. ions), organic acid anions (e.g. p-toluenesulfoner), N
Examples include ions such as P-chlorobenzenesulfonate and methanesulfonate), tetrafluoroboron ion, perchlorate ion, methylsulfate ion, and ethylsulfate ion.

Cations include inorganic and organic ones, specifically hydrogen ions, alkali metal ions (e.g. lithium, sodium, potassium, cesium, etc.), alkaline earth metal ions]/(e.g. magnesium, calcium, strontium, etc.). ), ammonium ions, organic ammonium ions (for example, trimethylammonium, triethylammonium, tripropylammonium, triethanolammonium ions, etc.), and pyridinium ions.

2. 2. 2 and the benzoxazole nucleus and naphthoxazole nucleus represented by Z6 include those having a substituent. Specifically, the substituent is a halogen atom (
For example, chloro atom, bromine atom, fluorine atom, etc.) Alkyl group having 6 or less carbon atoms (for example, methyl group, ethyl group,
Propyl group, butyl group, cyclohexyl group, etc.) Aryl group (e.g. phenyl group, etc.) Alkoxy group with 4 or less carbon atoms (e.g. methoxy group, ethoxy group, butoxy group, etc.) Aryloxy group (e.g. phenoxy group, etc.) 6 or less carbon atoms Acyl group (e.g. acetyl group, propionyl group, benzoyl group, etc.), alkoxycarbonyl group having 8 or less carbon atoms (e.g. methoxycarbonyl group, ethoxycarbonyl group, phenoxycarbonyl group, benzyloxycarbonyl group, etc.), hydroxy group, n-ano group, Examples include trifluoromethyl group.

2. 2. The naphthoxazole nucleus represented by
There are [1,2-d]naphthoxazole, [2,1-d]naphthoxazole, and [2,3-a]naphthoxazole nuclei, but either Zi or Za has a [2,id conaphthoxazole nucleus. It is preferable that

Z, and 24 are respectively a picoline nucleus, a pyridine nucleus, a quinoline nucleus, an indolenine nucleus, a benzimidazole nucleus, an oxazole nucleus, a benzoxazole nucleus, a naphthoxazole nucleus, a thiazoline nucleus, a thiazole nucleus, a benzothiazole nucleus,
It represents a naphthothiazole nucleus, a selenazole nucleus, a benzoselenazole nucleus, or an atomic part necessary to complete a naphthoselenazole nucleus, or the above-mentioned heterocyclic nucleus includes those having a substituent.

Specifically, thiazole type (e.g. thiazole; 4-methylthiazole; 4-phenylthiazole; 5-methylthiazole; 5-phenylthiazole; 4,5-dimethylthiazole; 4,5-diphenylthiazole; benzothiazole: 5- Fluoropentthiazole: 5-chlorobenzothiazole; 6-chloropentthiazole: 5
-Methylbenzothiazole; 6-methylbenzothiazole: 5-bromobenzothiazole, 5-carboxybenzothiazole, 5-ethoxycarbonylbenzothiazole, 5-hydroxybenzothiazole, 5-phenylbenzothiazole: 6-7enylbenzothiazole; 5- Methoxybenzothiazole; 6-Medoxybenzothiazole: 5-Iodobenzothiazole; 6-Nitoxybenzothiazole: Tetrahydropenzothiazole: 5,6-
dimethylbenzothiazole; 5.6-simethoxybenzothiazole; 5.6-cyoxymethylenebenzothiazole; 6-nitoxy5-methylbenzothiazole; 5-
Phenethylbenzothiazole; Naphtho [1,2-dl
Thiazole; 7to[2,1-dlthiazole; naphtho[2,3-d]thiazole; 5-methoxynaphtho[
1,2-dl thiazole; methoxynaphtho[2,1
-d] Thiazole; 7-methoxynaphtho [2,1-d
l Thiazole; 5-methoxythionaphtheno [6,7
-dl thiazole; 8,9-dihydronaphtho [1,
2-clJ thiazole; 4,5-dihydro[2
, 1-d]thiazole, etc.), oxazole type (e.g.,
4-methyloxazole; 5-methyloxazole; 4
-Phenyloxazole; 4,5-dimethyloxazole; 5-7enyloxazole; 5゜6-diphenyloxazole; benzoxazole; chlorobenzoxazole; 5-methylbenzoxazole; 5,6-dimethylbenzoxazole; 5-methoxybenzoxazole; 5-ethoxybenzoxazole; 5-phenethylbenzoxazole; 5-hydroxybenzoxazole, 5-ethoxycarbonylbenzoxazole, 5-bromobenzoxazole: 5-methyl- 6-chlorobenzoxazole; naphtho [1,2
-dl oxazole; su7to[2,1-a]oxazole; su7to[2,3-d]oxazole, etc.), selenazole series (e.g., 4-methylselenazole; 4-phenylselenazole: benzoselenazole) ;5-chlorobenzoselenazole;5-methoxybenzoselenazole;5-methylbenzoselenazole;tetrahydrobenzoselenazole:naphtho[1,2-dlselenazole;su7[2,1-d]selenazole, etc.), Pyridine (
For example, 2-pyridine; 5-methyl-2-pyridine; 4
-pyridine; 3-methyl-4-pyridine, etc.), quinoline series (e.g., 2-quinoline; 6-methyl-2-quinoline; 5-ethyl-2-quinoline; 6-chloro-2-quinoline; 8-chloro- 2-quinoline; 6-medoxy 2-quinoline: 6-nitoxy 2-quinoline; 8-ethoxy-
2-quinoline; 6-methyl-2-quinoline; 8-fluoro-2-quinoline; 6-dimethylamino-2-quinoline; 4-quinoline; 6-medoxy 4-quinoline; 7-methyl-4-quinoline; 8-chloro- 4-quinoline, etc.)
, 3.3-dialkylindolenine series (e.g. 3.3
-dimethylindolenine; 3.3.5-trimethylindolenine; 3,3-dimethyl-5-(dimethylamino)indolenine; 3.3-diethylindolenine, etc.)
, imidazole series (e.g. l-alkylbenzimitazole; l-7enyl-5,6-dichlorobenzimidazole: 1-alkyl-5-cyanobenzimidazole:
l-Alkyl-dichlorobenzimitazole; l-alkyl-5,6-cyclopenzimidazole; l-alkyl-5-chloro-6-dianobenzimidazole;
-Alkyl-5-trifluoromethylbenzimidazole; l-alkyl-5-methylsulfonylbenzimidazole; 1-alkyl-5-methoxycarponylbenzimidazole; 1-alkyl-5-acetylbenzimidazole; l-alkyl-5-( N,N-dimethylamino)sulfonylbenzimidazole, etc.).

Among these, quinoline-based, benzoxazole-based, naphthoxazole-based, benzothiazole-based, naphthothiazole-based, benzoselenazole-based, and nathoselenazole-based nuclei are particularly preferably used.

Specific examples of the sensitizing dyes represented by the general formula [I], the general formula [■], and the general formula [■] are shown below, but the sensitizing dyes used in the present invention are limited to these compounds. isn't it.

■-21 [I[) ■ ■ ■ ■ l-11 ■ 1]7 ■-18 [■] (xz)nz ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ CI[) (xz)nz CCO, θ CI[[) [111) ■-22 ShiF, Shitl? .

[l11) ■-24 The general formulas CI), (II) and CI[) according to the present invention
Examples of sensitizing dyes represented by (J, Am, Chem, S
oc, 67°1875-1899 (1945)), The Chemistry of Heterocyclic Compounders, by F.M. Palmer.
try of I(eterocyclicC□mpo
unds) Volume 18, The Cyanine Soybean and...
Related Compounder (The Cyanina)
Dyes and Re1ated Compound
s) (Aleissherger ed.

Published by Interscience, New York 1
964), U.S. Pat. No. 3,483.196, U.S. Pat.
No. 41.089, No. 3,541,089, No. 3,59
No. 8.595, No. 3,598.596, No. 3,632
, No. 808, No. 3,757,663, JP-A-60-7
Those skilled in the art can easily synthesize it by referring to the method described in No. 8445 and the like.

The optimum concentration of the sensitizing dyes of the general formulas CI), (II) and (III) can be determined by methods known to those skilled in the art. For example, a method may be used in which the same emulsion is divided, each emulsion contains a different concentration of sensitizing dye, and the performance of each emulsion is measured.

The amount of the sensitizing dye added in the present invention is not particularly limited, but it ranges from 2 X, 10-' mol to 1 mol per mol of silver halide.
Preferably, 10-' moles of X are used, and even 5
Preference is given to using X 10-' mol - 5X 10-3 mol.

Methods well known in the art can be used to add the sensitizing dye to the emulsion. For example, these sensitizing dyes can be dispersed directly in the emulsion or dissolved in a water soluble solvent such as pyridine, methyl alcohol, ethyl alcohol, methyl cellosolve, acetone, fluorinated alcohol, dimethylformamide or mixtures thereof. Alternatively, it can be diluted or dissolved in water and added to the emulsion in the form of a solution. Ultrasonic vibrations can also be used during the dissolution process.

Furthermore, as described in U.S. Pat. No. 3,469,987, dyes can be prepared by dissolving the dye in a volatile organic solvent, dispersing this solution in a hydrophilic colloid, and adding this dispersion to an emulsion. , Japanese Patent Publication No. 46-24185, a method is also used in which a water-insoluble dye is dispersed in a water-soluble solvent without being dissolved, and this dispersion is added to an emulsion.

The dye can also be added to the emulsion in the form of a dispersion by an acid dissolution and dispersion method. Other additions to emulsions include U.S. Pat.
．． The methods described in No. 996,287 and No. 3,425,835 can also be used.

The sensitizing dye can be added to the emulsion at any time during the manufacturing process from the time of silver halide grain formation to just before coating on the support. Specifically, before the formation of silver halide grains, during the formation of silver halide grains, after the completion of silver halide grain formation until the start of chemical sensitization, at the start of chemical sensitization, during chemical sensitization, and during chemical sensitization. Any time selected from the end of chemical sensitization and the time of application may be used. Alternatively, it may be added in multiple portions.

Although the order in which the stabilizer and antifoggant are added does not matter, they are preferably added at the time of silver halide grain formation or chemical ripening, that is, before the coating solution is prepared.

The method for adding dyes represented by the general formulas CI), (n) and CI[[) is to dissolve each sensitizing dye in the same or different solvents and mix these solutions before adding them to the emulsion. Alternatively, they may be added separately to the emulsion.

A preferred method is to mix a solution of the sensitizing dye represented by the general formula (1) and the general formula [I[) before adding it to the emulsion. A part of the sensitizing dye can be added individually or in a mixture with a sensitizing dye represented by the general formula [■]. Also preferred is a method in which the sensitizing dyes represented by the general formulas CI), (I[) and CIII) are added to the emulsion as a mixed solution.

The sensitizing dye used in the present invention can also be used in combination with a compound that provides a supersensitizing effect.

The silver halide grains contained in the silver halide photographic light-sensitive material of the present invention may be any of silver bromide, silver chloride, silver chlorobromide, silver iodobromide, and silver chloroiodobromide.

In particular, silver iodobromide is preferred from the standpoint of obtaining high sensitivity.

In the case of silver iodobromide, the average silver iodide content in the silver halide grains is preferably 0.5 to 10 mol%, more preferably 1
Al at ~8 mol%.

The crystals of the silver halide emulsion used in the present invention may have a uniform internal silver halide composition, but may have a structure in which a core inside the grain is covered with a shell having a composition different from that of the core. What you have is preferable.

In the grains having a core/shell structure, the shell may be uniform, but it is particularly preferable that the coated shell is further coated with shells having different silver halide compositions, so that the shell has a multilayer structure.

In the silver halide crystal of the present invention having a core/shell structure made of silver iodobromide (silver chloroiodobromide), the silver iodide content of the shell is preferably 2 to 40 mol%. The content is more preferably 10 to 40 mol%, and even more preferably 15 to 40 mol%.

In the silver halide crystal of the present invention made of silver iodobromide (silver chloroiodobromide), the legal ions may be added as an ionic solution such as a potassium iodide solution, or they may be added to the silver halide grains during growth. Although silver halide particles may be added as grains with a small solubility product, it is more preferable to add them as silver halide grains with a small solubility product.

The silver halide grains used in the present invention have a shape such as cubic, octahedral, tetradecahedral, or spherical.
It may be a so-called normal crystal or a crystal containing twin planes.

The method for producing normal crystal silver halide grains is known, for example J
, Phot, Sci., 5, 332 (1961), B
ar, Bunsenges.

Phys, Chem, 67.949 (1963), In
tern, Congress Photo.

Sci, Tokyo (1967), etc.

Further, tabular grains having an aspect ratio of 5 or more can also be used in the present invention. Tabular grains are described in U.S. Patent 4,434
, No. 226, No. 4,414,310, No. 4,433,
No. 048, No. 4,439,520 and British Patent 2.1
It can be easily prepared by the method described in No. 12.157.

As tabular grains with an aspect ratio of 5 or more,
Preferable ones have an aspect ratio of 5 to 100, more preferably an aspect ratio of 5 to 20. The equivalent circle diameter of the flat plate grains is preferably 0.2 μm to 30 μm, and 0.2 μm to 30 μm.
More preferably 4 μm to 10 μm.

Moreover, the thickness is preferably 0.5 μm or less, and 0.3 μm.
The following are more preferred.

The silver halide emulsion used in the present invention includes:
Although polydisperse emulsions can be used, monodisperse emulsions are more preferred.

The monodisperse emulsion referred to here is, for example, The Photo
-Graphic Journal, 79.330-3
Trivelli in 38 (1939).

When the average particle diameter is measured by the method reported by Smlth et al., at least 95% of the particles by number or weight are within ±40% of the average particle diameter, preferably ±30%.
% of silver halide emulsion.

The above-mentioned silver halide grains used in the silver halide photographic material of the present invention include, for example, T and H grains.

James, “The Theory of the
Photographic Process'' 4th edition, published by Macmillan (1977) 38-10
Neutral method, acidic method, ammonia method, forward mixing, back mixing, double jet method, Chondral double jet method, conversion method, core/
It can be manufactured by applying a method such as the shell method.

Known photographic additives can be used in the silver halide photographic emulsion of the present invention.

Examples of known photographic additives include compounds described in Research Disclosure (RD) RD-17643 and RD-18716 shown in the table below.

AdditivesChemical sensitizersDevelopment acceleratorsAntifoggantsStabilizing agentsColor stain inhibitorsImage stabilizersUltraviolet absorbersFiltersDye enhancersWhitening agentsHardening agentsCoating aidsSurfactantsPlasticizersSliding agentsStatic inhibitors Cloak Agent RD-17643 Page Classification Page 23 1 [[648- 29XXI 648 24 Vl 649- // /1RD-
18716 Classification Upper right upper right Lower right ■ 650 Left - Right ■ ■ 649 Right ~ 650 Left 26 ~ 27 26 ~ 27 651 Left 650 Right 650 Right ■ N 650 Right The photosensitive material according to the present invention has a first-class aromatic compound in the processing. A dye-forming coupler that forms a dye by performing a coupling reaction with an oxidized product of an amine developer (eg, p-) unilene diamine derivative, aminophenol derivative, etc.) can be used. The dye-forming couplers are typically selected for each emulsion layer such that a dye is formed that absorbs light in the light-sensitive spectrum of the emulsion layer, with a yellow dye-forming coupler for the blue-sensitive emulsion layer and a dye for the green-sensitive emulsion layer. A magenta coupler is used in the sensitive emulsion layer, and a cyan dye-forming coupler is used in the red-sensitive emulsion layer. However, depending on the purpose, silver halide color photographic materials may be produced using different combinations from the above combinations.

These dye-forming couplers preferably have a group called a ballast group in the molecule, which makes the coupler non-diffusive and has 8 or more carbon atoms. In addition, even if these dye-forming couplers are 4-equivalent, in which 4 molecules of silver ions need to be reduced in order to form 1 molecule of dye, only 2 molecules of silver ions need to be reduced. Either equivalence is acceptable. Dye-forming couplers include colored couplers that have a color correction effect and, by coupling with oxidized forms of developing agents, can be used as development inhibitors, development accelerators, bleaching accelerators, developers, silver halide solvents, and toning agents. Compounds that release photographically useful fragments such as hardeners, fogging agents, antifoggants, chemical sensitizers, spectral sensitizers, and desensitizers are included. Among these, couplers that release a development inhibitor during development and improve image sharpness and image graininess are called DIR couplers. In place of the DIR coupler, a DIR compound which undergoes a coupling reaction with the oxidized form of the developing agent to produce a colorless compound and at the same time releases a development inhibitor may be used.

The DIR couplers and DIR compounds used include those with an inhibitor directly attached to the coupling position and those with an inhibitor attached to the coupling position.
It is bonded to the coupling position via a valence group, and the inhibitor is bonded in such a way that the inhibitor is released by an intramolecular nucleophilic reaction or an intramolecular electron transfer reaction at the base circle separated by the coupling reaction ( (referred to as timing DIR couplers and timing DIR compounds).

Also, depending on the purpose, inhibitors that can be dispersed after release and those that are not diffusible can be used alone or in combination, depending on the purpose. Colorless couplers (also referred to as competitive couplers) that undergo a coupling reaction with the oxidized product of the aromatic primary amine developer but do not form dyes can be used in combination with dye-forming couplers.

In the present invention, a compound (hereinafter referred to as DIR of the present invention) that is released as a result of a reaction with an oxidized form of a developing agent from a development inhibitor or its precursor that can be converted into a compound with weak development inhibitory properties is used.
It is preferable to use a compound (hereinafter referred to as "compound") because it further improves the storage stability over time of the produced photosensitive material, which is an effect of the present invention.

The DIR compound of the present invention will be explained in more detail below.

The DIR compound of the present invention releases the development inhibitor or its precursor immediately or through an intramolecular nucleophilic substitution reaction as a result of a reaction with an oxidized form of a developing agent, such as a coupling reaction or a redox reaction.

The development inhibitor or its precursor changes into a compound with weaker development inhibitory properties through a hydrolysis reaction, etc.; however, in the case of the precursor, after becoming a development inhibitor, it becomes a compound with weaker development inhibitory properties. Changes to weaker compounds.

The change may occur in the photosensitive material or in a processing solution such as a developer.

In the DIR compound of the present invention, it is preferable that the development inhibitor produced by separation is changed into a compound with weaker development inhibitory property through a hydrolysis reaction, and in particular, it is a compound of the general formula (
A compound represented by DIR-I) is preferred.

General formula CDIR-I) CiT Takeshi Z-(L-Y).

In the general formula [DIR-I:l, Cp represents a coupler residue, T represents a linking group in which the bond between T and Z is broken after the bond between Cp and T is broken by reaction with the oxidized developing agent, Preferably, it binds to the coupling position of the coupler.

Z represents a development inhibitor residue, and L is a linking group containing a chemical bond that is cleaved by components in the developer after the compound containing Z exhibits a development inhibitory effect.

Y represents a substituent. m represents O, l or 2, preferably 0 or 1. n represents l or 2, and when n represents 2, Y may be the same or different.

The coupler residues represented by cp include yellow image-forming coupler residues, magenta image-forming coupler residues, cyan image-forming coupler residues, and coupler residues that do not substantially form image-forming coloring dyes.

The yellow image-forming coupler residue represented by Cp includes acylacetanilide type (for example, pivaloylacetanilide type, penzoylacetanilide type, 1 type), malondiester type, malondiamide type, dibenzoylmethane type, and benzoylacetanilide type. thiazolyl acetamide type, malone ester monoamide type, benzothiazolylacetate type, benzoxacylylacetamide type, benzoxacylylacetate type, benzimidazolylacetamide type or benzimidazolylacetate type coupler residue,
coupler residues derived from heterocycle-substituted acetamides or heterocycle-substituted acetates contained in U.S. Pat. No. 3,841,880 or U.S. Pat. No. 3,770°446;
British Patent No. 1,459,171, West German Patent (OLS)
2,503.099, JP-A-50-139738, Research Disclosure No. 15737, etc., coupler residues derived from anruamotoamides, or heterocyclic type described in U.S. Pat. No. 4,046,574. Coupler residues and the like are preferred.

The magenta image-forming coupler residue represented by cp includes a coupler residue having a 5-oxo-2-pyrazoline nucleus, a pyrazoloazole nucleus (e.g., a 5-oxo-2-pyrazoline nucleus, a pyrazolotriazole nucleus); Cyanoacetophenone type coupler residues are preferred.

The cyan image-forming coupler residue represented by cp is preferably a coupler residue having a phenol nucleus or a σ-7toll nucleus.

Further, the effect as a DIR coupler is the same even if the coupler does not substantially form an image-forming coloring dye after coupling with the oxidized form of the developing agent and releasing the development inhibitor. Examples of this type of coupler residue represented by Cp include, for example, U.S. Pat.
No. 1, No. 3,632,345, No. 3,958,993
For example, coupler residues that do not form coloring dyes and so-called effluent dye-forming couplers in which coloring dyes flow out from the light-sensitive material into the processing solution. Examples include so-called bleaching dye-forming coupler residues that are bleached by reacting with residues and components in the processing solution.

Particularly preferably, Cp is a pivaloylacetanilide-type and benzoylacetanilide-type yellow color image-forming coupler residue, a 5-oxo-2-pyrazoline core magenta color image-forming coupler residue, a σ-7toline core cyan color image forming coupler residue. Examples include forming coupler residues and efflux dye-forming coupler residues of the α-naphthol nucleus substituted with hydrophilic groups.

Examples of the group represented by T include (1) a group that causes a cleavage reaction using an electron transfer reaction along a conjugated system;
) a group that causes a cleavage reaction using an intramolecular nucleophilic substitution reaction, (3) a group that uses a hemiacetal cleavage reaction, (
4) A group using an iminoketal cleavage reaction, and (5) a group using an ester hydrolysis cleavage reaction.

Regarding the group (1), for example, JP-A-56-11494
No. 6, No. 57-154234, No. 57-188035
No. 58-98728, No. 58-160954,
No. 58-209736, No. 58-209737, No. 58-209738, No. 58-209739, No. 5
No. 8-209740, No. 62-86361 and No. 62
-87958, the group (2) is described in, for example, JP-A No. 57-56837 and U.S. Pat. No. 4,248,962, and the group (3) is described in, e.g.
No. 148, No. 60-249149, U.S. Patent No. 4,14
No. 6,396, for the group (4), see, for example, U.S. Pat.
No. 26,315 describes this in detail.

Furthermore, after the bond between Cp and T is broken, the bond between T and Z may be further broken by a reaction with the oxidized developing agent. For example, when the bond between the oxidized developing agent and the cup Examples include a coupler component that undergoes a ring reaction and a redox component that undergoes a redox reaction with an oxidized form of a developing agent.

When T is a coupler moiety, examples thereof include each of the coupler residues listed for Cp.

When T is a redox component, examples include hydroquinones, catechols, pyrogallols, aminephenols (e.g. p-aminophenols, 0-
amine phenols), naphthalene diols (e.g. 1,2-naphthalene diols,
1,4-aminonaphthols, 2,6-aminonaphthols), etc.

Among the groups represented by T, the following are preferred. In the structure, *1 indicates a site that binds to Cp, and *2 indicates a site that binds to Z.

R3 represents a substituent, R2 and R3 represent a hydrogen atom or a substituent, Q represents 0, 1 or 2, and when Q is 2, R1 may be the same or different from each other, and R1 may be fused with each other. It may form a ring. p represents 0.1 or 2.

Examples of the substituent represented by R1 include a halogen atom,
Alkyl group, alkenyl group, alkoxy group, alkoxycarbonyl group, anilino group, acylamino group, ureido group, cyan group, nitro group, sulfonamide group, sulfamoyl group, carbamoyl group, aryl group, carboxyl group, sulfo group, cycloalkyl group , an alkanesulfonyl group, an arylsulfonyl group, or an acyl group, including those having further substituents.

Examples of the substituent represented by R2 and R1 include an alkyl group, an alkenyl group, a cycloalkyl group, and an aryl group, including those having further substituents.

L in the general formula (DIR-I) is a divalent linking group, and contains a chemical bond that is cleaved by a component in the developer, for example, a nucleophilic reagent such as a hydroxy ion or hydroxylamine.

Examples of such chemical bonds include -C0O-N-C
OCOO- is mentioned, and these chemical bonds are connected to 2 directly or via an alkylene group or/and a phenylene group, and the other is directly bonded to Y. When connecting to Z through an alkylene group or a phenylene group, the intervening divalent group may contain an ether bond, an amide bond, a carbonyl group, a thioether bond, a sulfo group, a sulfonamide bond, a urea bond, etc. good.

W represents a hydrogen atom or a substituent. The substituent represents a halogen atom, nitro group, alkoxy group or alkyl group.

As the linking group represented by L, the following examples are preferable.

In the structure, book 3 represents a site that binds to 2, and book 4 represents a site that binds to Y.

Zero 3-(CH2)COO-Zero 4
*3 -(CHz)doOc-zero4-N-COO-,-
5o20-, -○CH2CH25O2-, -0COO tree 3 (CL)aNHcOo *4
*3 (CHz), 0CONH-book 4
W, , W, and W,' represent a hydrogen atom or a substituent.

d represents an integer of 0 to 10, preferably O to 5.

Examples of the substituent represented by Wl include a halogen atom, an alkyl group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, an alkanamide group, an alkoxy group, an alkoxycarbonyl group, an alkanesulfonamide group, and an alkylcarbamoyl group.
It is selected from an aryloxycarbonyl group, an aryl group, a carbamoyl group, a nitro group, a cyan group, an arylsulfonamide group, a sulfamoyl group, an imide group, and the like.

Examples of the substituent represented by W2 include an alkyl group, an aryl group, an alkenyl group, etc., W3 is exemplified as a substituent having the same meaning as W, and q represents an integer of O to 6.

In the general formula [DIR-I], examples of the substituent represented by Y include an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an aryl group, or a heterocyclic group, and further substituents Including those with.

The alkyl group, cycloalkyl group, or alkenyl group represented by Y has 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms.
represents a straight chain, branched chain alkyl group, alkenyl group or cycloalkyl group, preferably having a substituent, and the substituent is a halogen atom, a nitro group, a carbon number 1
-4 alkoxy group, C6-10 aryloxy group, C1-4 alkanesulfonyl group, C6-4
lO noarylsulfonyl group, C2-5 alkanamide group, anilino group, benzamide group, C2-6
alkylcarbamoyl group, carbamoyl group, carbon number 7
-10 arylcarbamoyl group, C1-4 alkylsulfonamide group, C6-1O arylsulfonamide group, C1-4 alkylthio group, C6-10 arylthio group, phthalimide group, Succinimide group, imidazolyl group, 1,2.44 riazolyl group, pyrazolyl group, benzotriazolyl group, 7lyl group,
Benzothiazolyl group, alkylamino group having 1 to 4 carbon atoms, alkanoyl group having 2 to 4 carbon atoms, benzoyl group, alkanoyloxy group having 2 to 4 carbon atoms, benzoyloxy group, perfluoroalkyl group having 1 to 4 carbon atoms, cyan group,
Tetrazolyl group, hydroxyl group, carboxyl group, mercapto group, sulfo group, amino group, alkylsulfamoyl group having 1 to 4 carbon atoms, arylsulfamoyl group having 6 to 10 carbon atoms, morpholino group, 6 to 10 carbon atoms aryl group, pyrrolidinyl group, ureido group, oxyamide group,
Alkoxycarbonyl group having 2 to 6 carbon atoms, 7 to 1 carbon atoms
0 aryloxycarbonyl group, imidazolidinyl group, or alkylidene amino group having 1 to 6 carbon atoms.

The aryl group represented by Y represents a phenyl group or a naphthyl group, etc., and these include those having a substituent. Examples of the substituent include the substituents listed above for the alkyl group or alkenyl group or carbon atoms 1 to 4. selected from alkyl groups, etc.

The heterocyclic group represented by Y includes a diazolyl group (2-imidazolyl group, 4-pyrazolyl group, etc.), a triazolyl group (
1,2,4-triazol-3-yl group, etc.), thiazolyl group (2-benzothiazolyl group, etc.), oxasilyl group (1,3-oxazol-2-yl group, etc.), pyrrolyl group, pyridyl group, diazinyl group (1,4-diazine-
2-yl group, etc.), triazinyl group (1,2,4-triazine-fanyl group, etc.), furyl group, diazolinyl group (
(imidacillin-2-yl group, etc.), pyrrolinyl group, thienyl group, etc.

Examples of Z in the general formula (DIR-I) include a divalent nitrogen-containing heterocyclic group or a nitrogen-containing heterocyclic thio group, and examples of the heterocyclic thio group include a tetrazolylthio group and a benzothiazolylthio group. , benzimidazolylthio group, triazolylthio group, imidazolylthio group, etc.

Specific examples of Z in the general formula [DIR-■) are shown below.

In the structure, *5 is Cp-(T-)-t-, and N6 is ÷L-
Y) Represents the binding site with n.

However, X represents a hydrogen atom or a substituent, and the general formula CDI
In R-I), it is contained in the part Z, and examples of the substituent include a halogen atom, an alkyl group, an alkenyl group, an alkanamide group, an alkenamide group, an alkokene group, a sulfonamide group, or an aryl group. .

The alkyl group or alkenyl group represented by X has the general formula C
It has the same meaning as the alkyl group or alkenyl group represented by Y in DIR-I).

Specifically, the alkanamide group, cycloalkanamide group, or alkenamide group represented by X has a carbon number of 2 to 101
Preferably 2 to 5 linear or branched alkanamide groups,
Represents a cycloalkanamide group or an alkenamide group,
In addition, the alkoxy group or cycloalkoxy group represented by X specifically represents a straight chain or branched alkoxy group or cycloalkoxy group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms,
These also include those having the same substituent as the alkyl group or alkenyl group represented by Y in general formula (DIR-1).

Among the DIR couplers of the present invention represented by the general formula (DIR-I), particularly preferred ones are shown below.

-Y R+ has the same meaning as R1, R2 has the same meaning as R2, and R5' has the same meaning as R3, Q' has the same meaning as α, and X' has the same meaning as X. Moreover, Cp, -L-Y has the general formula CDIR-
It has the same meaning as Cp and -LY in I).

Specific examples of the DIR compound of the present invention are shown below.
-2 DIR DIR-9 Shih3 DIR-12 Zhan H, C00C, H,.

DIR-13 D.I.R. DI R-20 DI R-21 IR DIR-18 IR IR IR D.I.R. D.I.R. D.I.R. DIR-30 D.I.R. DIR-36 DIR-37 D.I.R. ShiriLLtl.

CH2C00C5HI I D.I.R. D.I.R. DI R-47 H DIR-50 DIR-55 D　R　R-52 H DIR-53 CH, C00C, H.

DIR The development inhibitor of the DIR coupler of the present invention is required to have a certain decomposition rate constant. That is, the half-life of the development inhibitor at pH 1O, o is 4 hours or less,
Preferably it is 2 hours or less, more preferably 1 hour or less.

In the present invention, the half-life of the development inhibitor can be easily measured by the following method. That is, a development inhibitor is added to a developer having the following composition to a concentration of 1 x 10-' mol/Q, maintained at 38°C, and the concentration of the remaining development inhibitor is determined by liquid chromatography. I can do it.

Diethylenetriaminepentaacetic acid 0.8g 1-Hydroquinethylidene-1,13,3g Sodium sulfite diphosphonate 4.0g Potassium carbonate 30.0g Potassium bromide 1.4g Potassium iodide
1.3 mg hydroxylamine sulfate 2.4 g 4-(N-ethyl-N-β
-Hydroxy 4.5gethylamino)-2-
Add methylaniline sulfate solution
1.0Q (pH 10.0) The DIR coupler used in the present invention is a known compound, for example, disclosed in JP-A-57-151944 and JP-A-58-20.
No. 5150, No. 60-218644, No. 60-221
No. 750, No. 60-233650, No. 61-1174
It can be easily synthesized by the method described in No. 3.

These DIR couplers may be added to either a light-sensitive emulsion layer or a non-light-sensitive emulsion layer in a light-sensitive material. The amount added is l x 10-' to l x 10 of the total coated silver amount.
-'mol% is preferred.

When the compound represented by the general formula CDrR-I of the present invention is added to a photosensitive material, an antihalation layer, an intermediate layer (between different color-sensitive layers, between the same color-sensitive layer, between a photosensitive layer and a non-photosensitive layer), (between photosensitive layer, etc.), photosensitive silver halide emulsion layer, non-photosensitive silver halide emulsion layer, yellow filter layer, protective layer, etc., or it may be added to two or more layers. You may.

Two or more of these compounds may be mixed into the light-sensitive material, and the total amount added is 0.01 to 50 mol % per mol of silver halide, preferably 0.01 to 50 mol %, when included in the emulsion layer. It is 1 to 5 mol%. When it is contained in a non-photosensitive hydrophilic colloid layer, the coating amount is preferably l.
o-7 to 10-' mol/m2, more preferably lo-6
~101 mol/m2.

As the yellow dye-forming coupler, known acylacetanilide couplers can be preferably used.

Among these, benzoylacetanilide and pivaloylacetanilide compounds are advantageous.

Specific examples of yellow couplers that can be used include U.S. Pat. No. 2,875,057, U.S. Pat.
, 408° No. 194, No. 3,551.155, No. 3,
No. 582.322, No. 3,725゜072, No. 3,8
91.445, West German Patent No. 1,547.868, West German Application No. 2,219.917, West German Patent Application No. 2,261.361
No. 2゜414.006, British Patent No. 1,425,0
No. 20, Special Publication No. 51-10783, Japanese Patent Publication No. 47-26
No. 133, No. 48-73147, No. 50-6341, No. 50-87650, No. 50-123342, No. 50-130442, No. 51-21827, No. 51
-102636, 52-82424, 52-1
There are those described in No. 15219, No. 58-95346, etc.

Magenta coloring couplers include brassylon compounds,
Intazolone compounds, cyanoacetyl compounds, etc. can be used, and pyrazolone compounds are particularly advantageous.

A specific example of a magenta color-forming coupler that can be used is disclosed in U.S. Pat.
, No. 600.788, No. 2,983.608, No. 3,
No. 062,653, No. 3,127.269, No. 3,3
No. 11.476, No. 3,419,391, No. 3,51
No. 9,429, No. 3,558,319, No. 3,582
No. 322, No. 3,615,506, No. 3,834,
No. 908, No. 3.891445, West German Patent No. 1,810
, No. 464, West German Patent Application (OLS) 2.408,66
No. 5, No. 2,417.945, No. 2,418.959
No. 2,424,467, Japanese Patent Publication No. 40-6031, Japanese Patent Publication No. 20826-1982, Japanese Patent Publication No. 52-58922,
No. 49-129538, No. 49-74027, No. 5
No. 0-159336, No. 52-42121, No. 49-
No. 74028, No. 50-60233, No. 51-265
No. 41, No. 53-55122, No. 59-171956
No. 60-33552, No. 60-43659, No. 60-172982, No. 60-190779, etc.

As the cyan coloring coupler, phenol compounds, naphthol compounds, etc. can be used. Specific examples are U.S. Patent Nos. 2,369.929 and 2,434.2.
No. 72, No. 2,474.293, No. 2,521.90
No. 8, No. 2゜895.826, No. 3,034,892
No. 3,311.476, No. 3458.315, No. 3,476.563, No. 3,583,971,
3゜591.383, 3,767.411, 4,004,929, West German patent application (0LS) 2,
No. 414.830, No. 2,454,329, Japanese Unexamined Patent Publication No. 4
No. 8-59838, No. 51-26034, No. 48-5
No. 055, No. 51-146828, No. 52-6962
There are those described in No. 4 and No. 52-90932.

Hardening agents that can be used in the photographic material of the present invention include aldehyde-based, aziridine-based, inoxazole-based, epoxy-based, vinylsulfone-based, acryloyl-based, carbodiimide-based, triazine-based, polymer-based, maleimide-based, and acetylene-based hardeners. , methanesulfonic acid ester, etc.
These can be used alone or in combination.

Among these, for example, U.S. Patent No. 3,539,64
No. 4, JP-A-48-74832, JP-A No. 49-24435
No. 52-21059, No. 52-77076, No. 53-41221, No. 53-57257, No. 63-
When a hydrophilic water-soluble vinyl sulfone compound described in No. 241539 is used, better storage stability can be obtained and it is preferably used.

The silver halide photographic material of the present invention is produced by coating it on a support that has good flatness and good dimensional stability and little dimensional change during the manufacturing process or processing. Supports in this case include, for example, cellulose nitrate film, cellulose ester film, polyhinyl acetal film, polystyrene film, polyethylene terephthalate film, polycarbonate film, glass, paper, metal, paper coated with polyolefin such as polyethylene, polypropylene, etc. etc. can be used. These supports can be subjected to various surface treatments such as hydrophilic treatment for the purpose of improving adhesion with the photographic (emulsion) layer, such as saponification treatment, corona discharge treatment, sewage treatment, and setting. Processing, etc. is performed.

The silver halide color photographic light-sensitive material of the present invention can be processed using the known photographic processing method and processing solution described, for example, in Research Disclosure No. 176, pages 20-30 (RD-17643). The processing temperature applied to photographic processing is usually 18°C to 50°C, but processing is possible at temperatures lower than 18°C or at temperatures above 50°C.

Examples of light-sensitive materials to which the silver halide color photographic light-sensitive material of the present invention can be applied include color negative film for photography, color reversal film, color photographic paper, color positive film, color reversal photographic paper, direct positive film, heat development film, silver It can be used for dive bleaching, etc.

〔Example〕

Specific examples of the present invention will be described below, but the embodiments of the present invention are not limited thereto.

In the following examples, the amount added in the silver halide photographic material is expressed in grams per 1 m2 unless otherwise specified. Furthermore, silver halide and colloidal silver are shown in terms of silver. Sensitizing dyes are expressed in moles per mole of silver.

Example 1 Each layer having the composition shown below was sequentially formed on a triacetyl cellulose film support from the support side.
Species multilayer color photographic element sample (No.

101-115) were created.

1st layer: Antihalation layer (IC) Black colloidal silver UV absorber (UV-1) Colored coupler (CG-1) High boiling point solvent (Oil-1) High boiling point solvent (Oil-2) Gelatin 2nd layer: Intermediate layer (IL-1) Third gelatin layer: Red-sensitive emulsion layer (R) Silver iodobromide emulsion (Em-1) Silver iodobromide emulsion (Em-2) Sensitizing dye (S-4) Sensitizing dye (S-5) Uncoupler (C-1) Cyan coupler (C-2) Colored cyan coupler (CC DIR compound (D-1) DIR compound (D-2) High boiling point solvent (Oil-1) 0.15 0 .20 0.02 0.20 0.20 1.6 1.3 0.4 0.3 3.4XlO-'3.2X10-' 0.50 0.13 1) 0.07 0.006 0, OI O055 Gelatin 1.0 4th layer: Intermediate layer (IL-2) Gelatin 0.8 5th layer digreen-sensitive emulsion layer (G) Silver iodobromide emulsion (Em-1) 0.6 Silver iodobromide emulsion ( Em-2) 0.2 sensitizing dye (listed in Table-1) Magenta coupler (listed in Table-1) (M-1)
0.6 color magenta coupler (CM-1
)0.10DIR compound (DIR-19) 0
．． 02 High boiling point solvent (〇51-2) 0.7
0 Gelatin 1.0 6th layer: Yellow filter (YC) Yellow colloidal silver 0.05 Additive (MS
-1) 0.07 additive (H3-2)
0.07 additive (SC-1)
0.12 High boiling point organic solvent (Oil2)
0.15 gelatin 1.0
7th layer: Blue-sensitive emulsion layer (B) 8th layer: 9th layer: 0.25 0.25 5.8XlO-' 0.38 0.003 0.006 0.18 1.3 Silver iodobromide emulsion (Em-1) Silver iodobromide emulsion (Em-2) Sensitizing dye (S-6) Yellow coupler (Y-2) DIR compound (D-1) DIR compound (D-2) High boiling point solvent (Oil- 2) Gelatin first protective layer (PRO-1) Silver iodobromide (Em-4) Ultraviolet absorber (UV-1) Ultraviolet absorber (UV-2) Additive (H3-1) Additive (H5-2) ) High boiling point solvent (Oi 1-1) High boiling point solvent (Oi 1-3) Gelatin second protective layer (PRO-2) Alkali-soluble matting agent 0.13 (average particle size
2 μm) 0.3 0.07 0.1 0.2 0.1 0.07 0.07 0.8 Polymethyl methacrylate 0.02 (average particle size
3 μm) Gelatin 0.5 In each layer,
In addition to the above composition, coating aids, dispersion aids, and hardening agents were appropriately added. The emulsion used in the above sample was a highly internally dispersed monodisperse emulsion shown below.

Em-1: Average Agl content 7.5 mol% Octahedron 0
．． 55,17111Em-2: Average Agl content 2.5
Mol% Octahedron 0.36. umEm-3: Average Agl
Content 7.5 mol% Octahedron 0.65/1 rnEm
-4: Average AgI content 2.0 mol% Octahedron 0.0
Each 8-μm sample was wedge-exposed through an interference filter with a transmitted light maximum of 530 nm, and processed in the following processing steps.

Processing process Color development 3 minutes 15 seconds Bleach White 6 minutes 30 seconds Water Wash 3 minutes 15 seconds Fixed arrival time: 6 minutes 30 seconds Water Wash 3 minutes 15 seconds Stabilization 1 minute 30 seconds drying drying The composition of the treatment liquid used in each treatment step is shown below.

(Color developer) 4-Amino-3-methyl-N-(β-hydroxyethyl)aniline sulfate 4.75g Anhydrous sodium sulfite 4.25g Hydroxylamine 1/2 sulfate 2.0g Anhydrous potassium carbonate 37.5 g potassium bromide
1.3g nitrilotriacetic acid trisodium salt (l hydrate) 2.5g potassium hydroxide 1.0g Add water and 1
(Bleach solution) Ethylenediaminetetraacetic acid iron (II [) ammonium salt 100.0 g Ethylenediaminetetraacetic acid 2 Ammonium salt 10.0 g Ammonium bromide 150.0 g Glacial acetic acid 10.0 g Add water to make 1a , pH 6.01: Adjust using aqueous ammonia.

(Fixer) Ammonium thiosulfate 175.0 g Anhydrous ammonium sulfite 8.6 g Sodium metasulfite 2.3 g Add water to IQ
and adjust the pH to 6.0 using acetic acid.

(Stabilizing liquid) Formalin (37% aqueous solution) 1.5 m
Q Konidax (manufactured by Konica Corporation) 7.5 m
The sensitivity and storage stability over time of each treated sample were evaluated by adding Q water to obtain lQ. Sensitivity is the sensitivity at the point of fog + 0.1 on the characteristic curve, and sample N
It is expressed as a relative sensitivity with the sensitivity of o and lOI set as 100.

Preservability over time〉 Sample left for 18 hours (A) and temperature 50°C
For the sample (B) that was forced to deteriorate by being left under a constant temperature eye at a relative temperature of 80% for 18 hours, the sensitivity of the sample (A) to light transmitted through an interference filter with a maximum transmitted light of 530 nm to (B) was measured. It is expressed as a relative value when the sensitivity is set to 100.

The larger the value, the better the storage stability over time.

Table 1 As is clear from Table 1, the samples of the present invention have high sensitivity to green short wavelength light and are excellent in storage over time under high temperature and high humidity.

Example 2 (Preparation of Sample No. 201) Multilayer color photographic material sample No. 201 was prepared by sequentially forming each layer having the composition shown below on a triacetyl cellulose film support from the support side.

11th l: Antihalation layer (HC) black colloidal silver 0.15 UV absorber (UV-1)
0.20 colored coupler (CC-1
) 0.02 high boiling point solvent (Oil-1)
0.20 high boiling point solvent (Oil-2)
0.20 gelatin 1
．． 6 Second layer: Intermediate layer (IL-1) Gelatin 1.3 Third layer: Low sensitivity red-sensitive emulsion layer (RL) Silver iodobromide emulsion (Em-1) 0.4 Silver iodobromide emulsion (Em- 2) Sensitizing dye (S-1) Sensitizing dye (s-2) Sensitizing dye (S-3) Cyan coupler (C-J) Uncoupler (C-2) Colored cyan coupler (CC-1) DIR compound ( D-1) DIR compound (D-2) High boiling point solvent (Oil-1) Gelatin layer 4: High sensitivity red-sensitive emulsion layer (R+() Silver iodobromide emulsion (
Em-3) Sensitizing dye (S-1) Sensitizing dye (S-2) Sensitizing dye (S-3) Cyan coupler (C-2) Colored cyan coupler (CC-1) DIR compound (D-2) High boiling point solvent (Oil-1) 0.9 1.7XIO-'1.6XIO-'0.1X10-' 0.23 0.03 0.02 0.25 0.3 3.2X10-' 3.2X10 0 .2XIO information 0.50 0.13 0.07 0.006 0.01 0.55 1.0 Gelatin 1.0 5th layer: Intermediate layer (IL-2) Gelatin 0.8 6th layer: Low sensitivity green Sensitive emulsion layer (GL) Silver iodobromide emulsion (Em-1) 0.6 Silver iodobromide emulsion (Em-2) 0.2 Sensitizing dye (S
R-4) 4.5XlO-' sensitizing dye (P
a-20) 3.0XlO-' Magenta coupler (T1) 0.17 Magenta coupler (
M-2) 0°43 colored magenta coupler (CM-1) O-1°DIR compound (D-3)
0.02 high boiling point solvent (Oil-2)
0.70 gelatin 1.0 7th
Layer: High-sensitivity green-sensitive emulsion layer (GI() silver iodobromide emulsion (Em
-3) Sensitizing dye (SR-4) Sensitizing dye (II [-20) Magenta coupler (M-1) Magenta coupler (M-2) 0.9 3.1XlO-'0.3X10-' 0.03 0.13 Colored magenta coupler (CM DIR compound (D-3) High boiling point solvent (oi+-2) Seratin 8th layer: Ye O-filter (yc) Yellow colloidal silver additive (HS-1) Additive (MS- 2) Additive (SC-1) High-boiling organic solvent (Oil-2) Gelatin 9th layer: Low-sensitivity blue-sensitive emulsion layer (Bl) Silver iodobromide emulsion (
Em-1) Silver iodobromide emulsion (Em-2) Sensitizing dye (S-9) Yellow coupler (Y-1) Yellow coupler (Y-2) DIR compound (D-1) DIR compound (D-2) High boiling point solvent (Oil2) 1) 0.04 0.004 0.35 1.0 0.1 0.07 0.07 0.12 0.15 1.0 0.25 0.25 5.8X10-' 0 .60 0.32 0.003 0.006 0.18 Gelatin high sensitivity blue sensitive emulsion layer (BH) Silver iodobromide (Em-4) Sensitizing dye (s-10) tt (S-11) Yellow coupler ( y-1) Yellow coupler (y-2) High boiling point solvent (Oil-2) Gelatin 11th layer: 1st protective layer (PRO-1) Silver iodobromide (Em-5) Ultraviolet absorber (UV-1) Ultraviolet absorber (UV-2) Additive (MS-1) Additive (I (S-2) High boiling point solvent (oil-1) High boiling point solvent (Oil-3) Gelatin second protective layer (PRO-2) Alkali-soluble matting agent 1st θ layer: 12th layer: ■, 3 0.5 3.0XlO-'1.2X10-' 0.18 0.10 0.05 1.0 0.3 0.07 0. 1 0.2 0.1 0.07 0.07 0.8 0.13 (Average particle size 2μm) Toughlylate 0.02 (Average particle size 3μm) Gelatin 0.5In addition, each layer contains:
In addition to the above composition, coating aid SU2, dispersion aid 5U-1,
Hardeners H-1 and H-2 and dyes Al-1 and Al-2 were added as appropriate.

The emulsions used in the above samples were as follows.

Both are monodisperse emulsions with high internal density.

Em-1: Average AgI content 7.5 mol% Octahedron 0
．． 55μmEm-2: Average Agl content 2.5 mol%
Octahedron 0.36. umEm-3: Average Agl content 8
．． 0 mol% Octahedron 0.84μmEm-4: Average Ag
L content 8.5 mol% Octahedron 1.02 μm Em-5
: Average Agl content 2.0 mol% 0.08 μm
(Creation of Sample Nos. 02 to 206) Sample No. 201, sensitizing dyes 5R-4, I[[-20 were replaced with the dyes listed in the columns of Table 2, sensitizing dyes I, n, I[[], etc. was prepared in exactly the same manner as sample No. 201.

(Creation of Sample Nos. 207 to 215) Sensitizing dyes 5R-4 and m-20 of Methyl Melipo sample No. 201 are shown in Table 2.
The sensitizing dyes I, n, and II [are replaced with the dyes listed in the column, and the DIR compound D3 contained in the 6th layer and the 7th layer is added.
Sample No. 201 was prepared in exactly the same manner as Sample No. 201, except that the compound described in the DIR compound column of Table 2 was substituted in equimolar amounts.

Each sample was wedge exposed using the following light source and processed in the same manner as in Example 1.

Light source A: A white light source that passes through an interference filter with maximum transmission of 530 nm.

Light source B: a white light source that passes through an interference filter with maximum transmission of 560 nm.

Light source C: white light source.

Light source: Uni-wavelength fluorescent light source (National EX-D fluorescent light, manufactured by Matsushita Electric Industrial Co., Ltd.) Table 2 summarizes the results regarding sensitivity, storage stability, and suitability for fluorescent light.

However, the sensitivity is based on the sensitivity of sample No. 201 as 100.Amount addedAmount of sensitizing dye added to the 6th layer and TA7 layer (Amount added to the 6th layer/Amount added to the 7th layer) It is expressed as mol/mol of silver.

*Sensitivity When using light source A and light source B, the sensitivity is 130 nm each.
The sensitivity to light, the sensitivity to 560 nm light, is shown as a relative value with Sample No. 201 set as 100.

When the sensitivity to 530 nm light is low, the color reproducibility for blue-green colors tends to be poor, and when the sensitivity to 560 nm light is low, the color reproducibility for orange and skin colors tends to be poor.

Shows the difference in sensitivity at a point of fog +0.3 against the harsh light source and sensitivity at a point of fog +0.3 against light weight C when the amount of light from the Kimoto Fluorescent Light Suitable Light Source C and the light source are made equal. -ta. If this value becomes large, the color reproducibility will be greenish when shooting under a fluorescent light source.

Preservability over time It was determined in the same manner as in Example 1.

Table 2 shows that the sample of the present invention has increased sensitivity to 530 nm light while maintaining sensitivity to 560 nm light, suggesting that it is a sample with good color reproducibility for both blue-green and orange colors. .

In addition, the sample of the present invention has little sensitivity variation with respect to a fluorescent lamp light source, and is excellent in photographing suitability with the same light source. Furthermore, it can be seen that the samples of the present invention have excellent storage stability over time under high temperature and high humidity conditions.

Sample No. 204-208 and Sample No. 207-209
From the comparison, it can be seen that by using the DIR compound of the present invention in the sample of the present invention, the storage stability over time is further improved, and this is a preferred embodiment of the present invention.

Example 3 (Preparation of Samples Nos. 301 to 310) Each layer having the following composition was sequentially applied from the support side onto a subbed triacetyl cellulose film support to prepare reversal color photographic materials Samples Nos. 301 to 307. It was created.

1st layer (antihalation layer) UV absorber U-10,3 UV absorber U-20,4 High boiling point solvent 0il-11,0 Black colloidal silver 0.24 Gelatin 2.0 2nd layer (intermediate layer) Addition Agent S C-20,1'; 45 slag point solution @0il-10,2 Gelatin 1.0 wafer 3 layers (low sensitivity red-sensitive silver halide emulsion layer) Red sensitizing dye (S-
9, S-10) spectrally sensitized by AgBrl (A
gr4. Q% le%, average particle size 0.25/1lffl
) 0.5 Coupler C-30,1 mol High boiling point solvent Oil -30,6 Gelatin 1.3 4th layer (high sensitivity red-sensitive silver halide emulsion layer) Red sensitizing dye (S -
AgBrl (A
gl 2 mol%, average particle size 0.6 μm) 0.8 Coupler C-30,2 High boiling point solvent 0i1-31-2 Gelatin 1.8 5th layer (intermediate layer) Additive S C-20,1 High boiling point 04l-10,2 Gelatin 0.9 6th layer (low sensitivity green-sensitive silver halide emulsion layer) AgBrl (Agl 4 mol%,
Average particle size o, 25μa+) 0.6 coupler M-1
0.04 mol coupler M -30.01 mol High boiling point solvent 0i1-20.5 Gelatin 1.4 7th layer (high sensitivity green-sensitive silver halide emulsion layer) AgBrl spectrally sensitized with the sensitizing dyes listed in Table 3 (Agl 2 mol%
, average particle size 0.6 μm) 0.9 coupler M-1
0,10 molar coupler M -30,02 molar high dregs point solvent 0il -21,0 gelatin 1.5 8th layer (intermediate layer) 9th layer (yellow filter layer) same as 5th layer Yellow colloidal silver 0.1 gelatin
0.93 C-20,1 High boiling point solvent Oi! -10,2 10th layer (low sensitivity blue-sensitive silver halide emulsion layer) AgBrl (A
gl 4 mol%, average particle size 0.35 μm) 0.6 coupler Y -20.3 mol High boiling point solvent 0i1-20.6 Gelatin 1, 3 11th layer (
High sensitivity sensitive silver halide emulsion layer) Blue sensitizing dye (s-
11) Spectrally sensitized AgBrl (Agl 2 mol%, average particle size 0.9 μm) 0.9 coupler Y
-20.5 mol High boiling point solvent Oil -21.4 Gelatin 2.1$12 layers (
1st protective layer) Ultraviolet absorber U -10,3 Ultraviolet absorber U -20,4 High boiling point solvent 0i1-20.6 Gelatin 1.2 Additive
SC-20,1 13th layer (second protective layer) Non-photosensitive fine-grain silver halide emulsion consisting of silver iodobromide with an average grain size (r) of 0.08 μm and containing 1 mol% of silver iodide.
Silver content: 0.3 Polymethyl methacrylate particles (diameter: 1.5 μm) Surfactant: 5U-3 Gelatin: 0.7 In addition to the above composition, gelatin hardener H-1 and a surfactant were added to each layer. Added.

The samples thus obtained were evaluated in the same manner as in Example 2 for sensitivity and storage stability over time of coated fluorescent lamp suitability coated samples.

The results are shown in Table-3.

Note that the sensitivity is calculated by drawing a tangent to the high density side of the characteristic curve from a density point T that is 0.2 higher than the lowest density value, and setting the tangent point to S. The exposure amounts corresponding to points T and S are respectively Ht, H
When s is the reciprocal of the exposure amount Hm obtained by the following formula, it is expressed as a relative value when sample No. 301 is taken as 100.

Regarding storage stability over time, I met.

Each sample is Processing process First development Water washing Reversal color development Adjustment bleaching white fixed arrival Water washing stability drying drying Obtained in the same manner as in Example 1. It was processed according to the following processing steps.

Processing time Processing temperature 6 minutes 38℃ 2 minutes 2 minutes 6 minutes 2 minutes 6 minutes 4 minutes / 4 minutes 1 minute, room temperature The composition of the physical solution used in the above treatment step is as follows.

First developer Sodium tetrapolyphosphate 2g Sodium sulfite 20g Haodoroquinone monosulfonate 30g Sodium carbonate (l hydrate)
30 gl-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone
2g potassium bromide 2.5g
Potassium thiocyanate 1.2g Potassium iodide (0.1% solution) 2 Add RNA water and invert 1000 mR Liquid Nitrilotrimethylenephosphonic acid hexasodium salt 3g 1st chloride
Tin (dihydrate) Igp-aminophenol 111g Sodium hydroxide
8g glacial acetic acid
Add 15ml12 water and color developer Sodium tetrapolyphosphate Sodium sulfite Sodium tertiary phosphate (dihydrate) Potassium bromide Potassium iodide (0.1% solution) Sodium hydroxide N-ethyl citrazate-N-β-methane Sulfonamidoethyl-3-methyl-4-aminoaniline/Wc
#Salt 2. Adjust by adding 2-ethylenedithiogetanol water Liquid sodium sulfite Sodium ethylenediaminetetraacetate (dihydrate) Thioglycerin glacial acetic acid 1000 mff g g 6 g g 0IIIa g 1.5g I g g 1000 ■a 2 g g 0.4m (1 mQ Add water and Q Bleach Liquid stabilized Sodium ethylenediaminetetraacetate (dihydrate) Iron ethylenediaminetetraacetate (I[[) Ammonium (dihydrate) Add potassium bromide water and soak Add ammonium thiosulfate, sodium sulfite, sodium bisulfite, and prepare a constant solution of formalin (37% by weight).Conidax (manufactured by Konica Corp.), add water] 000 Q m (2 Q). The sample is 560nm
The sensitivity to 530 nm light is increased while maintaining the sensitivity to light, and the color reproducibility for both blue-green and orange is good. In addition, the sample of the present invention has little sensitivity variation with respect to a fluorescent lamp light source, and is excellent in photographing suitability with the same light source. Furthermore, the samples of the present invention have excellent storage stability over time under high temperature and high humidity conditions.

The structures of the compounds used in the examples are shown below.

CC ■ M-1 M ■ S-11 [(CL -CH302CHz) 5CCHzsOz
cHzcHz]! NCHICH! 5O3KU-1 U-2 C-1 mixture (2: C-2 R- ■ R- S-1 S i Js ≧lJ3+1 [Effects of the Invention] The present invention improves color reproducibility, especially color reproducibility for blue-green. It was possible to provide a silver halide color photographic light-sensitive material which has excellent color reproducibility with respect to a light source including a fluorescent lamp, and excellent storage stability over time of the produced light-sensitive material.

Claims (1)

[Scope of Claims] A silver halide color photographic light-sensitive material having at least one blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a red-sensitive silver halide emulsion layer on a support,
The silver halide grains contained in at least one of the green-sensitive silver halide emulsion layers contain at least one sensitizing dye represented by the following general formula [I] and a sensitizing dye represented by the following general formula [II]. 1. A silver halide color photographic material characterized in that it is spectrally sensitized with at least one sensitizing dye and at least one sensitizing dye represented by the following general formula [III]. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ General formula [II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ General formula [III] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R_1 , R_2, R_3, R_4, R_6, R
_8 and R_7 each represent an alkyl group or an alkenyl group. R_3 and R_8 each represent a hydrogen atom, an alkyl group, or an aryl group. X_1, X_2, and X_3 each represent a charge-balanced counterion, and n_1, n_2, and n_3 each represent a value of 0 or more necessary to neutralize the charge of the entire molecule. Z_1 and Z_2 each represent an atomic group necessary to complete the benzoxazole nucleus. Z_3 and Z_4 are pyrroline nucleus, pyridine nucleus, quinoline nucleus, indolenine nucleus, respectively.
benzimidazole nucleus, oxazole nucleus, benzoxazole nucleus, naphthoxazole nucleus, thiazoline nucleus, thiazole nucleus, benzothiazole nucleus, naphthothiazole nucleus,
Represents the atomic group necessary to complete the selenazole nucleus, benzoselenazole nucleus, or naphthoselenazole nucleus. Z_5
, Z_6 each represent an atomic group necessary to complete the naphthoxazole nucleus. ]