JPH0451040A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To enhance color reproduction performance and storage stability for a long period by spectrally sensitizing, by a specified sensitizing dye,silver halide grains contained in at least one of green-sensitive silver halide emulsion layers. CONSTITUTION:The silver halide color photographic sensitive material is pro vided on a support with blue-, green-, and red-sensitive silver halide emulsion layers and at least on of the green sensitive emulsion layer contains the silver halide grains spectrally sensitized by the sensitizing dyes represented by formu lae I - III in which each of R1 - R7 except R3 is alkyl or alkenyl; R3. or aryl; each or R8 and R9 is alkyl, alkenyl, or aryl; each of Z1 and Z3 is an atomic group necessary to form a benzoxazole ring; each of Z3 and Z4 is an atomic group necessary to form a pyrroline or pyridine ring or the like; Z5 and Z6 is an atomic group necessary to from a benziidazole ring, thus permitting color reproduction performance and storage stability for a long period to be enhanced.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a spectrally sensitized/-silver halide color photographic light-sensitive material, and more specifically, the present invention relates to a spectrally sensitized /-silver halide color photographic light-sensitive material, which has excellent color reproducibility and storage stability of the produced light-sensitive material. The present invention relates to a silver/10-genide color photographic 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 terms of color reproducibility in particular, although color purity has improved, the situation has not changed much 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 IIE) are major factors related to color reproducibility.
There is.

[The following things are known about IH. That is, it is known that in silver halide multilayer color photographic light-sensitive materials, a compound is added which forms a development inhibitor or its precursor by force/knobbling with the oxidized form of a color developing agent, and the release from this so-called DIR compound is known. It is known that by inhibiting the development of other coloring layers using a development inhibitor, 11E is produced and the effect of improving color reproducibility is produced.

Furthermore, in color negative films, it is possible to provide the same effect as IIE by using colored couplers in an amount greater than that which 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 diffusive DIR, in which the mobility of inhibitor groups and their precursors, which have been frequently used recently, is high, 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 IIH 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 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-mentioned problems can be improved by designing the device so that max 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, if only a fluorescent light source or a strobe light is used, but there is an influence from the fluorescent light, the color reproduction will be greenish.

Furthermore, when the sensitivity at 560 to 570 nra 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 these demands, the present inventors have conducted extensive research and found that at least IN blue-, green-, and red-sensitive silver halide emulsions are coated on a support. In a silver halide color photographic light-sensitive material having a layer, the silver halide grains contained in at least one layer of the green-sensitive silver halide emulsion layer are sensitized particles represented by the following general formula [:I]. It is spectrally sensitized by at least one kind of dye, at least one kind of sensitizing dye represented by the following general formula [11], and at least one kind of sensitizing dye represented by the following general formula (III). It has been found that the above object can be achieved by a silver halide color photographic material having the following characteristics.

General formula (I) General formula (I[) General formula (II[) In the formula, Rl, Rz, Rs, R4, R1Rs
and R7 each represent an alkyl group or an alkenyl group,
R8 represents a hydrogen atom, an alkyl group, or an aryl group;
, and R9 each represent an alkyl group, an alkenyl group, or an aryl group.

Zl and 2. each represents an atomic group necessary to complete a benzoxazole nucleus, and Z and Z4 respectively represent a pyridine nucleus, a pyridine nucleus, a quinoline nucleus, an indolenine nucleus, a benzimidazole nucleus, an oxazole nucleus, a benzoxazole nucleus, and a naphtho. Represents an atomic group necessary to complete an oxazole nucleus, thiazoline nucleus, thiazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, selenazole nucleus, benzoselenazole nucleus, or naphthoselenazole nucleus; 2. and Z,
each represents a group of atoms necessary to complete the benzimidazole nucleus.

The present invention will be explained in more detail below.

General formula (1), [It] and (Il) used in the present invention
In the compound represented by l), R1, Rz, R4R
, , Rs and R2 each have 1 to 1 o carbon atoms and the branching region is a straight chain alkyl group (e.g. methyl, ethyl, propyl, butyl, pentyl, i-pentyl, 2-ethyl-hexyl, octyl, decyl, etc.) or an alkenyl group having 3 to 10 carbon atoms (e.g., 2-propenyl, 3-phthynyl, l-methyl-3-propenyl, 3-pentenyl, l-
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.), anano groups, carbamoyl groups (e.g., carbamoyl, N-methylcarbamoyl, N,N-tetramethylenecarbamoyl, etc.), sulfamoyl groups (e.g., sulfamoyl, N,N-3- oxapentamethyleneaminosulfonyl, etc.), methanesulfonyl group, alkoxycarbonyl group (e.g., ethoxycarbonyl, butoxycarbonyl, etc.), aryl group (e.g., phenyl, carboxyphenyl, etc.), acyl group (e.g., acetyl, benzoyl, etc.), acylamino group ( For example, acetylamino, benzoylamino, etc.), sulfonamide groups (for example, methanesulfonamide, butanesulfonamide, etc.). group, sulfato group,
hydroxyl group, sulfino group, etc.).

Examples of the alkyl group substituted with a water-soluble group represented by R1, R2, R-, Rs, Ra, and R7 include carboxymethyl, sulfoethyl, sulfopropyl, sulfobutyl, sulfopentyl, 3-sulfobutyl, hydroquinethyl, and carboquine. Ethyl, 3-sulfinobutyl, 3-
Examples include phosphonopropyl, p-sulfobenzyl, 0-carboxybenzyl, etc., and examples of alkenyl groups substituted with water-soluble groups include 4-sulfo-3-butenyl, 2
-carboxy-2-phenyl group and the like.

In the general formula [I], (I[[), each R3
It is preferable that one of R2, R6 and R7 has a water-soluble group.

Ions that cancel out the charges in the molecules represented by X 2 , 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.), organic acid anions (e.g. p-toluenesulfonate, p-chlorobenzenesulfonate-1, methanesulfonate, etc.), Examples include tetrafluoroboron ion, perchlorate ion, methyl sulfate ion, and ethyl sulfate ion.

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

2. The benzoxazole nucleus represented by 2 includes those having a substituent. Specifically, the substituent 7 includes a halogen atom (e.g., chlorine atom, bromine atom, fluorine atom, etc.), an alkyl group having 6 or less carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, cyclohexyl group, etc.). Aryl groups (e.g. phenyl groups, etc.) Alkoxy groups having up to 4 carbon atoms (e.g. methoxy, ethoxy, butoxy groups, etc.) Aryloxy groups (e.g. phenokine groups) Acyl groups having up to 6 carbon atoms (e.g. acetyl groups) group, propionyl group, benzoyl group, etc.) alkoxycarbonyl group having 8 or less carbon atoms (for example, methanesulfonyl group,
Examples include ethoxycarbonyl group, fenoquinecarbonyl group, benzyloxycarbonyl group, etc.) hydroquine group, cyano group, trifluoromethyl group, etc.

Z3 and 2. 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, and the above-mentioned heterocyclic nucleus also includes those having a substituent.

Specifically, thiazole type (for example, thiazole: 4-methylthiazole; 4-phenylthiazole: 5-methylthiazole; 5-phenylthiazole: 4,5 dimethylthiazole: 4,5-diphenylthiazole; benzothiazole; 5-70 Penzothiazole; 5-chlorobenzothiazole; 6-chlorobenzothiazole; 5-methylbenzothiazole; 6-methylbenzothiazole:
5-bromobenzothiazole, 5-carboxybenzothiazole, 5-ethoxycarbonylbenzothiazole,
Hydroxybenzothiazole, 5-phenylbenzothiazole; 6-phenylbenzothiazole; 5-methoxybenzothiazole; 6-medoxybenzothiazole;
5-iodobenzothiazole; 6-nitoxybenzothiazole; tetrahydrobenzothiazole; 5,6-dimethylbenzothiazole; 5,6-simethoxybenzothiazole: 5,6-cyoxymethylenebenzothiazole:
6-nitoxy5-methylbenzothiazole; 5-7enethylbenzothiazole; naphtho[1,2-dl thiazole; naphtho[2,1-d]thiazole; naphtho[
2,3-dl thiazole: 5-methoxynaphtho[1,2
-dl Thiazole: 8-methoxynaphtho [2,1-
d] Thiazole; 7-methoxynaphtho [2,1-dl
Thiazole: 5-methquinthionaphtheno [6,7-
cl] Thiazole; 8,9-dihydronaphtho [1,
2-dl thiazole; 4,5-dihydronaphtho[2,
1-d]thiazole, etc.), oxazole series (e.g., 4
-Methyloxazole; 5-methyloxazole; 4-
Phenyloxazole; 4,5-dimethyloxazole: 5-7enyloxazole: 5゜6-cyphenyloxazole: Benzoxazole; 5-chlorobenzoxazole; 5-methylbenzoxazole: 5-phenylbenzoxazole; 6-methylbenzoxazole : 5.6-dimethylbenzoxazole; 5-methoxybenzoxazole; 5-ethoxybenzoxazole; 5-7 dioxybenzoxazole; 5-hydroxybenzoxazole, 5-ethoxycarbonylbenzoxazole, 5-bromobenzoxazole; 5-Methyl-6-chlorobenzoxazole; 7) [1,
2-dl oxazole; naphtho[2,1-d]oxazole; naphtho[2,3-d]oxazole, etc.), selenazole series (e.g., 4-methylselenazole; 4-phenylselenazole: benzoselenazole; 5- chlorobenzoselenazole; 5-methoxybenzoselenazole; 5-methylbenzoselenazole; tetrahydrobenzoselenazole: naphtho[1,2-dl selenazole, etc.; naphtho[2,1,-d]selenazole, etc.), pyridine-based ( For example, 2-pyridine: 5-methyl-2-pyridine; 4-pyridine; 3-methyl-4-pyridine, etc.), quinoline series (for example, 2-quinoline: 6-methyl-2-quinoline; 5-ethyl-2 -quinoline: 6-chloro-2-quinoline; 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; chloro-4-quinoline, etc.)
, 3,3-dialkylindolenine series (e.g. 3,3
-dimethylindolenine; 3゜3.5-trimethylindolenine; 3,3-dimethyl-5-(dimethylamino)
Indolenine i 3.3-diethylindolenine, etc.),
Imidazole series (e.g. 1-alkylbenzimidazole; ]-]phenyl-5,6-cyclopenzimidazole 1-alkyl-5-cyanohenguimidazole; 1
-Alkyl-5-chlorobenzimidazole; 1-alkyl-5,6-cyclopenzimidazole: l-alkyl-5-chloro-6-dianobenzimidazole; 1
-Alkyl-5-trifluoromethylbenzimidazole: 1-alkyl-5-methylsulfonylbenzimidazole; 1-alkyl-5-methoxycarbonylbenzimidazole: 1-alkyl-5-acetylbenzimidazole: l-al+ Ru5- (N,N-'; methylamino)sulfonylbenzimidazole, etc.).

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

Also in the general formulas [I] and (I[+), R,, Ra
Examples of the alkyl groups represented by R9 and R9 include methyl, ethyl, butyl, pentyl, carbamoylethyl, methoxycarbonylpropyl, hydroxyethyl, 2,
2,3.3-tetrafluoropropyl, perfluoroethyl, hydroxyethoxyethyl, methoxyethyl, 2
-phenyl and other groups, and R.

and R9 each represent 2-propenyl as an alkenyl group,
Examples include groups such as 3-butenyl, l-methyl-3-propenyl, 3-pentenyl, l-methyl-3-butenyl, and 4-hexenyl.

The aryl group each represented by 4 in Rs, Ra and R9 is preferably a phenyl group, and may have a substituent.

The benzimidazole nucleus represented by Z , , Z I also includes those having a substituent. Specific examples of the substituent include the following.

Acyloxy groups (e.g. acetoxy, propionoxy, etc.), alkoxycarbonyl groups (e.g. methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, etc.)
, aryloxycarbonyl groups (e.g., phenoxycarbonyl, tolyloquinecarbonyl, β-naphthoki7carponyl, etc.), halogen atoms (e.g., chlorine, bromine, iodine,
fluorine, etc.), acyl groups (e.g. acetyl, propionyl,
benzoyl, etc.), alkylsulfonyl groups (e.g. methylsulfonyl, difluoromethylsulfonyl, trifluoromethylsulfonyl, ethylsulfonyl, etc.), arylsulfonyl groups (e.g. phenylsulfonyl, p-tolylsulfonyl, etc.), carbamoyl groups (e.g. carbamoyl,
N-methylcarbamoyl, etc.), sulfamoyl groups (eg, sulfamoyl, N-methylsulfamoyl, morpholinosulfonyl, piperidinosulfonyl, etc.), and perfluorohydrocarbon groups (eg, perfluorobutyl, perfluorophenyl, etc.).

Specific examples of sensitizing dyes represented by general formulas [■], general formulas [I], and CIII) are shown below, but the sensitizing dyes used in the present invention are limited to these compounds. ) ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ (II) (xz)nz ■ ■ ■ ■ ■ -29 ■ ■ ■ ■ ■ ■ ■ (n) [■] d CaO,.

■-26 The above general formulas [I], (II) and [111] according to the present invention
), for example, (J, A+w, Chsw
, Soc, 67°1875/1899 (1945))
The Chemistry of Heterocyclic Compounders (The Ch.
e+m1stry of HeterocyclicC
oBounds) Volume 18, The Cyan Soybean and Related Compounder
ineDyes and Re1ated Compo
unds) (A, Weissherger ad.

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, Japanese Patent Application Publication No. 1986/7
Those skilled in the art can easily synthesize it by referring to the method described in No. 8445 and the like.

The optimal concentration of the sensitizing dyes of the general formulas (13, (II) and [m]) can be determined by methods known to those skilled in the art.For example, an identical emulsion is divided and each emulsion is given a different concentration. Examples include a method of determining the performance of each sensitizing dye by incorporating them therein.

The amount of the sensitizing dye added in the present invention is not particularly limited, but is from 2×10 −′ mol to 1×l per mol of silver halide.
Preferably, O-2 moles are used, and even s x io
Preference is given to using −5×10 −′ moles.

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.

Alternatively, the dye 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, as described in U.S. Pat. No. 3,469.987. As described in 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 general formulas [1), (II) and (III) 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 solutions of the sensitizing dyes represented by the general formula [I] and the general formula (If) before adding them to the emulsion. A part of the sensitizing dye can be added alone or in a mixture with the sensitizing dye represented by the general formula (I[I). Also preferred is a method in which the sensitizing dyes represented by formulas [I], (I[) and (III) 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
~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), Be
r, Bunsangas.

Phys, Che+n, 67.949 (1963),
Intern, 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 No. 2,1
It can be easily prepared by the method described in, for example, No. 12,157.

As tabular grains with an aspect ratio of 5 or more,
Preferred ones have an aspect ratio of 5 to 1001, more preferably 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.
4 μm-10 gm is more preferred. Also, its thickness is 0.
The thickness is preferably 5 μm or less, more preferably 0.3 μm or less.

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).

reported by S+n1th et al.
% of particles within ±40% of the average particle diameter, preferably ±
A silver halide emulsion with a content of 30% or less.

The silver halide grains as described above used in the silver halide photographic light-sensitive material of the present invention are, for example, T, )l.

“The Theory of the” by James
Photographic Process” 4th edition, published by Macmi11an (1977) 38-104
Manufactured by applying methods such as the neutral method, acid method, ammonia method, forward mixing, back mixing, double jet method, Chondral double jet method, conversion method, core/shell method, etc. described in the literature such as P. can do.

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.

Additives RD-17643 page Classification Chemical sensitizers 23 III Development accelerators 2Q XXI Antifoggants 24 Vl Stabilizers Color stain inhibitors 25 ■ Image stabilizers 25 ■ Ultraviolet absorbers 25-26 ■ Filter dyes Enhancers Whitening agent 24 V dura mater
Agent 26 X Coating aid 26-27]
[I Surfactant 26-27 11 Plasticizer 27 n Slip agent
〃 Static inhibitor 27 III Ma
Agent 28
1fRD-18716 page Classification 648- Upper right 648- Upper right 649- Lower right left-right 649 right to 650 left 651 left 650 right 650 right 650 right The photosensitive material according to the present invention has aromatic first
A dye-forming coupler that forms a dye by performing a coupling reaction with an oxidized product of a class amine developer (for example, a p-] dinylene diamine derivative or an aminophenol derivative) 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. Furthermore, 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, 2 molecules of silver ions need to be reduced. Either one with good 2-equivalence may be used. 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 so dispersible can be used alone or in combination. 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"), since the storage stability of the produced photosensitive material, which is an effect of the present invention, is further improved.

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

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 (
DIR-I] is preferred.

General formula (DIR-I) CiT-Z-(L-Y).

In the general formula [:DIR-1), 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 O or l. 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 (e.g. pivaloylacetanilide type, benzoylacetanilide type), malondiester type, malondiamide type, dibenzoylmethane type, benzothiazolylacetamide type. , malone ester monoamide type, benzothiazolylacetate type, benzoxacylylacetamide, benzoxacylylacetate type, benzimidazolylacetamide type or benzimidazolylacetate type coupler residue, petero ring included in U.S. Pat. No. 3,841,880. Coupler residues derived from substituted acetamides or heterocyclic substituted acetates or US Pat. No. 3,770.

No. 446, British Patent No. 1,459,171, West German Patent (
OLS) No. 2,503.099, Japanese Patent Publication No. 50-139
No. 738 or Research Disclosure 1573
Coupler residues derived from acylacetamides as described in No. 7, etc., or heterocyclic coupler residues as described in US Pat. No. 4,046,574 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 an a-naphthol 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
No. 3,961.959, etc., such as coupler residues that do not form coloring dyes, and so-called run-off 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, an α-s7toline core cyan color image forming coupler residue. Examples include efflux dye-forming coupler residues of forming coupler residues and hydrophilic group-substituted σ-naphthol nuclei.

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, (
Examples include 4) a group using an iminoketal cleavage reaction, and (5) a t; 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,
No. 148, No. 60-249149, U.S. Patent No. 4,14
For the group (4), see, for example, US Pat. No. 4,546.073, and for the group (5), see, for example, West German Published Patent No.
No. 26.315 describes this in detail.

Furthermore, after the bond between Cp and T is cleaved, the bond between T and Z may be further cleaved by reaction with the oxidized developing agent. For example, when 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, aminophenols (e.g. p-aminophenols, 0-
aminophenols), naphthalene diols (e.g. 1,2-naphthalene diols, 1,4-su7talediols, 2,6-su7talediols), or aminonaphthols (e.g. 1.2-naphthalene diols), -aminonaphthols,
1, 4-aminonaphthols, 2,6-aminonaphthols), and the like.

Among the groups represented by T, the following are preferred. In the structure, book 1 shows the site that binds to cp, and book 2 shows the site that binds to Z.

R1 represents a substituent, and R! +RM represents a hydrogen atom or a substituent, g represents 0.1 or 2, and when a is 2, R may be the same or different from each other, or R may form a fused ring with each other. . p represents 0.1 or 2.

Examples of the substituent represented by R+ include a halogen atom,
Alkyl group, alkenyl group, alkoxy group, alkoxycarbonyl group, anilino group, anruamino group, ureido group, cyano 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 R1 and R1 include an alkyl group, an alkenyl group, a cycloalkyl group, and an aryl group, including those having further substituents.

L in 8 in general formula (DIR-1) 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 -C00--N
-Coo -, -So□O, OCHzCHtSOz-1
OCOO--N-COCOO- is mentioned, and these chemical bonds are connected to W32 directly or via an alkylene group or/and a phenylene group, and the other is directly bonded to Y. When linked to 2 through an alkylene group or phenylene group, the intervening bivalent group may contain an ether bond, amide bond, carbonyl group, thioether bond, sulfo group, sulfonamide bond, 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, for example, the following examples are preferable.

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

Book 3 -(CL)acOo-*4
Book 3 (CL)doOc *4*3 -
(CHz), NHCOO-book 4 $3
-(CHz)aOcONH-*4W, , W, and W,
' represents a hydrogen atom or a substituent.

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

Examples of the substituent represented by Wl include a hydrogen atom and a carbon number of 1 to 10. Preferably 1 to 5 alkyl groups, alkanamido groups, alkoxy groups, alkoxycarbonyl groups, alkanesulfonamido groups, such as alkylcarbamoyl groups, aryloxycarbonyl groups, aryl groups, carbamoyl groups, nitro groups, cyano groups, arylsulfones. Selected from amide group, sulfamoyl group, imide group, etc.

Examples of the substituent represented by W include an alkyl group, an aryl group, an alkenyl group, etc., W3 has the same meaning as W, and examples thereof include the same substituents, and q represents an integer of θ 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.

Specifically, 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
1O arylsulfonyl group, C2-5 alkanamide group, anilino group, benzamide group, C2-6
alkylcarbamoyl group, carbamoyl group, carbon number 7
-1O arylcarbamoyl group, C1-4 alkylsulfonamide group, C6-IO arylsulfonamide group, C1-4 alkylthio group, C6-1O arylthio group, phthalimide group, succinimide group, imidazolyl group, 1,2.4-)riazolyl group, pyrazolyl group, benzotriazolyl group, furyl 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, cyano group, tetrazolyl group, hydroxyl group, carboxyl group,
Mercapto group, sulfo group, amino group, alkylsulfamoyl group having 1 to 4 carbon atoms, arylsulfamoyl group having JR prime number 6 to IO, morpholino group, aryl group having 6 to 10 carbon atoms, pyrrolidinyl group, ureido group , oxyamide group, alkoxycarbonyl group having 2 to 6 carbon atoms, 7 carbon atoms
-10 aryloxycarbonyl groups, imidazolidinyl groups, or alkylidene amino groups having 1 to 6 carbon atoms.

The aryl group represented by Y represents a phenyl group or a 7-tyl group, and these also include those having a substituent, and examples of the substituent include the substituents listed above for the alkyl group or alkenyl group or those having 1 carbon number. -4 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-triazin-5-yl group, etc.), furyl group, diazolinyl group (imidacillin-2-yl group, etc.), pyrrolinyl group, thienyl group, etc.

Z in the general formula [)IR-I) includes, for example, a divalent nitrogen-containing heterocyclic group or a nitrogen-containing heterocyclic thio group, and examples of the heterocyclic thio group include a tetrazolylthio group, benzo, and thiazolylthio group. , benzimidazolylthio group, triazolylthio group, imidazolylthio group, etc.

Specific examples of 2 in general formula 1:DIR-I) are shown below.

In the structure, *5 is Cp-(T+IP-, *6 is +L-Y
) represents the binding site with n.

However, X represents a hydrogen atom or a substituent, and the general formula (DI
In R-I), it is included 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 alkoxy group, a sulfonamide group, or an aryl group. .

The alkyl group or alkenyl group represented by X has the general formula (
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 2 to 10 carbon atoms,
Preferably 2 to 5 linear, branched steel alkanamide groups,
Represents a cycloalkanamide group or an alkenamide group,
In addition, the alkoxy group or cycloalkoxy group represented by X specifically represents a linear or branched alkoxy group or cycloalkoxy group having 1 to 101 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-I).

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

-Y DIR-1 ■ -Y DIR-2 R,l is R□, R,/ is R8, R,/ is R
1, respectively, Q' is synonymous with a, and X
' is synonymous with X. In addition, Cp, -L-Y is represented by the general formula (
It has the same meaning as Cp and -LY in DIR-I).

Specific examples of the DIR compound of the present invention are shown below.
-3 DIR-8 DIR-9 and H2C0OC5HI+ DIR-12 DIR-16 DIR-18 IR-13 IR DIR-15 DIR-20 DIR-21 DIR DIR-23 DIR DIR DIR-30 DIR-25 DIR KE D I R-27 D I R-31 D I R-32 D I R-33 Outer-1113 DIR-34 DIR-36 DIR D IR-42 DIR-37 DIR-44 CHzCOOCsH+ + 1R 1R 1R 1R I CHICOOC,H.

DI R-50 1R The development inhibitor for 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 10.0 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 1X10-' mol/Q, maintained at 38°C, and the concentration of the remaining development inhibitor can be determined by liquid chromatography.

Diethylenetriaminepentaacetic acid 0.8 gl-
Hydroquine ethylidene-1,1-3,3g 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. Off (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 lX10-' to lXl0-' of the total coated silver amount.
Mol% is preferred.

When the compound represented by the general formula (DIR-I) of the present invention is added to a photosensitive material, an anti-resicon 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 included in the non-photosensitive hydrophilic colloid layer, the coating amount is preferably 1.
0-7 to 10-' mol/kaku2, more preferably lO-.
~10-'mol/m''.

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
No. 91.445, West German Patent No. 1,547.868, West German Application No. 22'19,917, West German Patent 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
゜322, 3,615.506, 3,834,
No. 908, No. 3,891°445, West German Patent No. 1,81
No. 0,464, West German Patent Application (OLS) 2408665
No. 2,417,945, No. 2,418,959, No. 2,424,467, Special Publication No. 40-6031,
JP 51-20826, JP 52-58922, JP 49-129538, JP 49-74027, JP 50
-159336, 52-42121, 49-7
No. 4028, No. 50-60233, No. 51-2654
No. 1, No. 53-55122, No. 59-171956, No. 60-33552, No. 60-43659, No. 6
No. 0-172982, No. 60-190779, etc.

As the cyan coloring coupler, phenol compounds, naphthol compounds, etc. can be used. Specific examples thereof include 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 t: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, good dimensional stability and little dimensional change during the production process or processing. In this case, the support can be made of, for example, cellulose nitrate film, cellulose ester film, polyvinyl acecool 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 all the examples below, the amount added in the silver 10genide photographic light-sensitive material is expressed in grams per m2 unless otherwise specified. In addition, /10 silver genide 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.
Seed multilayer color photographic element sample (NO9101-115)
It was created.

J-th layer: Anti-haline layer () IC) Black colloidal silver UV absorber (UV-1) Colored coupler (CC-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) Cyan coupler (c-1) Cyan coupler (C-2) Colored cyan coupler (CC-1) DIR compound (D-1) DIR compound (D-2) High boiling point solvent (Oil-1) 0 .4 0.3 3.4XIO-'3.2XIO-' 0.50 0.13 0.07 0.006 0.01 O155 0,15 0,20 0,02 0,20 0,20 1,6 1 , 3 Gelatin 4th layer: Intermediate layer (IL-2) Gelatin 5th digreen-sensitive emulsion layer (G) Silver iodobromide emulsion (Em-1) y (Em-2) Sensitizing dye (Table-1 ) Magenta coupler (M-1) Colored magenta coupler (CM DIR compound (DIR-19) High boiling point solvent (Oil-2) Gelatin 6th layer: Yellow filter (yc) Yellow colloidal silver additive (H5-1) ) Additive (H5-2) Additive (SC-1) High boiling point organic solvent (Oil-2) Gelatin 7th layer: Blue-sensitive emulsion layer (B) 1.0 0.8 0.6 0.2 To 1 Description 0.6 1) 0.10 0.02 0.70 1.0 0.05 0.07 0.07 0.12 0.15 1.0 8th layer: 9th layer: Silver iodobromide emulsion ( Em-1) Silver iodobromide emulsion (Em-2) Sensitizing dye (S-6) Yellow coupler (Y) DIR compound (D-1) DIR compound (D-2) High boiling point solvent (Oil-2) Gelatin First protective layer (PRO Silver iodobromide (Em-4) Ultraviolet absorber (UV-1) Ultraviolet absorber (IIV-2) Additive (H3-1) Additive (H3-2) High boiling point solvent (Oil -1) High boiling point solvent (Oil-3) Gelatin second protective layer (PRO-2) Alkali-soluble matting agent (average particle size 2 μm) 0.25 0.25 5.8XIO-' 0.38 0. 003 0.006 0.18 1.3 0.3 0.07 0.1 0.2 0.1 0.07 0.07 0.8 0.13 Polymethyl methacrylate 0.02 (average particle size
3 μm) Gelatin 0.5 In addition, each layer has
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
．． 55μmEm-2: average AgI content 2.5 mol%
Octahedron 0.36μiEm-3: Average Agl content 7.
5 mol% octahedron 0.6577111Em-4: Average Agl content 2.0 mol% octahedron 0.08 μm Each sample was wedge exposed through an interference filter with maximum transmitted light 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 developing solution) Amount of 4-amino-3-methyl-N-(β-hydroxyethyl)aniline Sulfate Anhydrous sodium sulfite Hydroquinylamiso l/2 sulfate Anhydrous potassium carbonate Potassium bromide Nitrilotriacetic acid trisodium salt ( 1 hydrate) Add potassium hydroxide water to make 112 (bleaching solution) Iron (III) ethylenediaminetetraacetate Ammonium salt ethylenediaminetetraacetic acid 2 Ammonium salt Ammonium bromide glacial acetic acid 150.0 1,OO,0 4,75g 4 .25g 2, Og 37.5 g 1.3 g 2.5 1.0 10.0 l000 Add water to make IQ, and use ammonia water to adjust pH to 6.0
Adjust to.

(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 of each treated sample, which was adjusted to 112 by adding Q water, were evaluated. Sensitivity is the sensitivity at the point of fog + 0.1 on the characteristic curve, and sample N
The relative sensitivity is expressed with the sensitivity of o, lOl as 100.

Preservability over time〉 Sample left for 18 hours (A) and temperature 50°C
For sample CB), which was forced to deteriorate by being left in a constant temperature and humidity environment with a relative temperature of 80% for 18 hours, the sensitivity of sample (A) to light transmitted through an interference filter with a maximum transmitted light of 530 nm relative 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.

The unit of the amount of sensitizing dye added is expressed in moles of silver.

From Table 1, it can be seen that the samples of the present invention have high sensitivity to green short wavelength light and are also excellent in storage over time.

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.

1st layer: 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) f1313 sensitization (S
-1) 3.2X10-' sensitizing dye (S
-2) 3.2X 10 sensitizing dye (S-
3) 0.2XIO-'un coupler (C-1) 0.50 cyan coupler (C
-2) 0.13 colored cyan coupler (cc-1) (1,07DIR compound (D-1)
0.006DIR compound (D-2)
0.01 High boiling point solvent (Oill)
0.55 Gelatin 1.0 4th
Layers: High sensitivity red-sensitive emulsion layer (RH) Silver iodobromide emulsion (Em-3) 0.9 sensitizing dye (s-1) 1.7xtO" sensitizing dye (S-2) 1.6XIO-' sensitizing dye Sensitive dye (S-3) 0.1XlO-' cyan coupler (C-2) 0.23 colored cyan coupler (CC-1) 0.03 DIR compound (D
-2) 0.02 high boiling point solvent (Oil-1
) 0.25 gelatin 1slc5 layer: Intermediate layer (IL-2) Gelatin 6th layer: Low-sensitivity green-sensitive emulsion layer (GL) Silver iodobromide emulsion (Em-1) Silver iodobromide emulsion (Ea+-2) Sensitizing dye (SR-4) Sensitizing dye (SR-5) Magenta coupler (M-1) Magenta coupler (M-2) Colored magenta coupler DIR compound (D-3) High boiling point solvent (Oil-2) Gelatin No. 7 layers: High-sensitivity green-sensitive emulsion layer (GH) Silver iodobromide emulsion (Em-3) Sensitizing dye (SR-4) Sensitizing dye (SR-5) Sensitizing dye (I-10) Magenta coupler (M -1) 1.0 0.8 0.6 0.2 4.5X10-'3.0X10-' 0.17 0.43 (CM-1) 0.10 0.02 0.70 1.0 0. 9 2.0XlO-'1.1XlO-'0.3XlO-' 0.03 Magenta coupler (M-2) Colored magenta coupler (CM DIR compound (D-3) High boiling point solvent (Oil-2) Gelatin yellow filter ( YC) Yellow colloidal silver additive (MS-1) Additive (H5-2) Additive (5C-1) High boiling point organic solvent (Oil-2) Gelatin 9th layer: Low sensitivity blue-sensitive emulsion layer (BL) Iodine Silver bromide 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) 8th layer: 0.13 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 5.8XlO-' 0.60 0.32 0.003 0.006 High boiling point solvent (Oil-2) Gelatin 10th layer: High sensitivity blue-sensitive emulsion layer (BH) Silver iodobromide (Em
-4) Sensitizing dye (S-10) Sensitizing dye (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 (IIV-1) Ultraviolet absorber (UV-2) Additive (H3-1) Additive (MS-2) High boiling point solvent (Oil- 1) High boiling point solvent (Oil-3) Gelatin 12th layer: 2nd protective layer (PRO-2) 0.18 1.3 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 Alkali-soluble matting agent 0.13 (average particle size
2 μm) Polymethyl methacrylate 0.02 (average particle size
3 μm) Gelatin 0.5 In each layer,
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 are as follows.

Both are monodisperse emulsions with high internal density.

Em-1: Average AgI content 7.5 mol% Octahedron 0
．． 55 μm Em-2 + average Agl content 2.5 mol%
Octahedron 0.36μ+aEm-3: Average Agl content 8
．． 0 mol% Octahedron 0.84μ+1Em-4: Average A
gl content 8.5 mol% Octahedron 1.02μvnEm
-5: Average AgI content 2.0 mol% 0.08
．． um (Preparation of Sample Nos. 202 to 208) The sensitizing dyes 5R-4 and 5R-5 of sample No. 201 were replaced with the sensitizing dyes 1. It was prepared in exactly the same manner as Sample No. 201 except that the dyes listed in columns I[ and III were replaced.

(Creation of sample No. 209-215) The sensitizing dyes 5R-4 and 5R-5 of sample No. 201 are shown in the table.
DIR compound D-3, which is substituted with the dyes listed in the columns of sensitizing dyes I, n, and m in No. 2, and further contained in the sixth and seventh layers.
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 D = three-wavelength fluorescent light source (National EX-D fluorescent light, manufactured by Matsushita Electric Industrial Co., Ltd.) Summary I of sensitivity, storage stability, and suitability for fluorescent light; the results are shown in Table 2.

However, the sensitivity was expressed as a relative value when the sensitivity of sample No. 201 was set as 100.

Addition amount The amount of the sensitizing dye added to the sixth layer and the seventh layer is expressed as (addition amount to the sixth layer/addition amount to the seventh layer) in mole/silver 1 mole.

** Sensitivity Sensitivity when using light source A and light source B is 530 nm each.
Sensitivity to light and sensitivity to 560 nm light are shown as relative values 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 deteriorate, and when the sensitivity to 560 nm light is low, the color reproducibility for orange and skin colors tends to deteriorate.

This book shows the difference between the sensitivity at the point of fog +0.3 to light source C and the sensitivity at the point of fog +0.3 to light source C when the amount of light from light source C and light source is the same. . If this value becomes large, color reproducibility becomes greenish when photographing 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. 206-208 and Sample No. 209-211
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 309) On a subbed triacetyl cellulose film support, each layer having the following composition was sequentially applied from the support side to prepare reversal color photographic materials Samples Nos. 301 to 307. It was created.

1st layer (antihalation layer) Ultraviolet absorber U-1,0,3 Ultraviolet absorber U-20,4 High boiling point solvent 0il-11,0 Black colloidal silver 0.24 Gelatin 2. Oa$2 layer (intermediate layer) Additive S C-20,1 High boiling point solvent 041--10.2 Gelatin 1.0 Third layer (low sensitivity red-sensitive silver halide emulsion layer) Red sensitizing dye (S-
9, S-10) spectrally sensitized by AgBrl (A
gl 4.0 mol%, average particle size 0.25 μm) 0.5 Coupler C-30, 1 mol High boiling point solvent 041-30.6 Gelatin 1.3 4th layer (high sensitivity red-sensitive silver halide emulsion layer) Red sensitizing dye (S-
9, S-10) spectrally sensitized by AgBrl (A
gl 2 mol%, average particle size 0.6 μm) 0.8 Coupler C-30,2 High boiling point solvent O-31,2 Gelatin 1.8 5th layer (intermediate layer) Additive S C-20,1 High Boiling point 0il-10-2 Gelatin 0.9 6th layer (low-sensitivity green-sensitive silver halide emulsion layer) AgBrl spectrally sensitized with the sensitizing dye listed in Table 3 (Agl 4 mol%
, average particle size 0.25 μm) 0.6 coupler M −
10,04 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 grain size 0.6 μn+) 0.9 coupler M
-1' 0.10 molar coupler M
-30.02 mol High boiling point solvent 041-21.0 Gelatin 1.5 8th layer (intermediate layer) 9th layer (yellow filter layer) same as 5th layer Yellow colloidal silver 0.1 Gelatin
0.95 C-20-1 High boiling point solvent Oil -10,2 10th layer (low sensitivity blue sensitivity/\silver halogenide emulsion layer) AgBrl spectrally sensitized with blue sensitizing dye (s-11)
Agl 4 mol%, average particle size 0.35 μm) 0.6 coupler Y-20,3 mol High boiling point solvent Oil -20,6 Gelatin 1/3 11th layer (high sensitivity blue-sensitive silver halide emulsion layer) Blue enhancement Sensitive dye (S
-11) spectrally sensitized by 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 12th layer (
1st protective layer) Ultraviolet absorber U-I O,3 Ultraviolet absorber U-20,4 High boiling point solvent 0i1-20.6 Gelatin 1/2 Additive
S C-20,1 13th layer (second protective layer) Average grain size (r) 0.08 μm 1 Non-photosensitive fine grains made of silver iodobromide containing 1 mol% of silver iodide/10 Silver Genide emulsion
Silver content: 0.3 Polymethyl methacrylate particles (diameter: 1.5 μm) Surfactant: 5U-3 Gelatin: 0.7 In addition to the above composition, gelatin hardening agent H-1 and surfactant were added to each layer. Added.

Regarding the sample obtained in this way, the sensitivity and the storability over time of the coated sample were evaluated in the same manner as in Example 2.

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.

Each sample was processed through the following processing steps.

Processing process Processing time Processing temperature 1st development 6 minutes 38℃ Washing with water 2 minutes // Reversing 2 minutes // Color development 6 minutes // Adjustment 2 minutes Bleaching 6 minutes Fixing
4 minutes // Washing with water 4 minutes Stability 1 minute Drying at room temperature The composition of the treatment liquid used in the above treatment step is as follows.

First developer Sodium tetrapolyphosphate Sodium sulfite Haodoroquinone monosulfonate Sodium carbonate (monohydrate) ■-Phenyl-4-methyl-4-hydroxymethyl-3
- Pyrazolidone Potassium bromide Potassium thiocyanate Potassium iodide (0.1% solution) Add water and invert Liquid Nitrilotrimethylenephosphonic acid hexasodium salt Stannous chloride (dihydrate) p-Aminophenol Sodium hydroxide Glacial acetic acid Add water and g 2.5g 1.2g 2 m+2 1000 mQ g g , O,1g g 5 mo 1000 m (1 Color developer Sodium tetrapolyphosphate Sodium sulfite Sodium tertiary phosphate (dihydrate) Potassium bromide iodide Potassium (0.1% solution) Sodium hydroxide N-ethyl citrazate-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate 2.2-ethylenedithiogetanol Add water Adjustment Liquid sodium sulfite Sodium ethylenediaminetetraacetate (dihydrate) Add thioglycerin glacial acetic acid water g g 6 g g 0 mo g 1.5 g 1 g g 1000 mQ 2 g g O,4mQ mm 1.000 mQ White Liquid Sodium ethylenediaminetetraacetate (dihydrate) 2g Iron ethylenediaminetetraacetate (m) Ammonium (dihydrate) 120g Potassium bromide 100g Add water to 1000 mo Fixation Liquid ammonium thiosulfate 80g Sodium sulfite 5g Sodium bisulfite Add 5g water
1000 mo stable liquid formalin (37% by weight) 5 mQ
Konidax (manufactured by Konica Corporation) 5m12 table-
As is clear from Figure 3, the sample of the present invention has increased sensitivity to 530n+n light while maintaining sensitivity to 560nm light, and has 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, 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.

sidi C M M R R R- S S [(CH2 CH5O□CHI) 3CCH, 5o2CH2CH2]
, NC) I2C) 1250. KU U Shirisushi + 12 Shirisushi 8i11 C 5C mixture (2:3) C2H.

〔Effect of the invention〕

The present invention provides silver halide color photographic sensitizers that have excellent color reproducibility, particularly for blue-green colors, excellent color reproducibility for light sources including fluorescent light sources, and excellent storage stability over time of the produced photosensitive materials. We were able to provide the materials.

Claims (1)

[Scope of Claims] A silver halide color photographic light-sensitive material having at least one blue-sensitive, green-sensitive and red-sensitive silver halide emulsion layer on a support, at least one of the green-sensitive silver halide emulsion layers. The silver halide grains contained in the following general formula [
I], at least one sensitizing dye represented by the following general formula [II], and at least one sensitizing dye represented by the following general formula [III]. A silver halide color photographic material characterized by being spectrally sensitized. 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_5, R
_6 and R_7 each represent an alkyl group or an alkenyl group, R_3 represents a hydrogen atom, an alkyl group or an aryl group, and R_8 and R_9 each represent an alkyl group, an alkenyl group or an aryl group. Z_1 and Z_2 each represent an atomic group necessary to complete a benzoxazole nucleus, and Z_3 and Z_4 each represent a pyrroline nucleus, a pyridine nucleus, a quinoline nucleus, an indolenine nucleus, a benzimidazole nucleus, an oxazole nucleus, and a benzoxazole nucleus. , naphthoxazole nucleus, thiazoline nucleus,
Z_
5 and Z_6 each represent a group of atoms necessary to complete the benzimidazole nucleus. ]