JPH0444028A - Spectrally sensitized silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To enhance the spectral sensitivity of a green light wavelength region and to improve the preservable stability of the photosensitive material with lapse of time by spectrally sensitizing the photosensitive material with at least one kind of specific sensitizing dyes stuff and further at least one kind of specific sensitizing dyes stuff. CONSTITUTION:The silver halide particles of green sensitive silver halide emulsion layers are spectrally sensitized by at least one kind of the sensitizing dyes stuff expressed by formula I and at least one kind of the sensitizing dyes stuff expressed by formula II. The max. wavelength of the spectral absorption is so set as to be apart by >=5nm from any of theabsorption max. wavelengths of the reflection spectra in the emulsions. In the formulas I and II, R1, R2, R4, and R5 respectively denote an alkyl group or alkenyl group; R3 denotes a hydrogen atom or alkyl group, etc. X1, X2 denote charge balance ions; Z1, Z2 respectively denote the atom group necessary for completing a benzoxazole nucleus or naphthoxazole nucleus; Z3, Z4 respectively denote the atom group necessary for completing a pyroline nucleus, pyridine nucleus, etc. The spectral sensitivity of the green short wavelength region is enhanced in this way and the preservable stability is improved; further, the color reproducibility is improved.

Description

[Detailed Description of the Invention] R+ (L)r++ R2 [Industrial Application Field] The present invention relates to a spectrally sensitized silver halide photographic light-sensitive material. The present invention relates to a silver halide photographic material which also has excellent storage stability over time.

[Background of the invention]

It is well known that certain cyanine dyes and merocyanine dyes are extremely effective as means for spectrally sensitizing silver halide emulsions. Furthermore, it is also known that by using the sensitizing dye in combination with certain other sensitizing dyes or organic compounds, it is possible to impart a sensitivity to the emulsion that is greater than the sum of the sensitivities that each compound can impart alone. This effect is called supersensitization, and many combinations have already been reported.

Incidentally, it is known that human vision has the highest sensitivity to green light, and that the delicate balance of green light sensitivity has a large effect on color.

Therefore, especially in the green light sensitivity of color photographic light-sensitive materials, it is required that the sensitivity is not only sufficiently high but also that the spectral sensitivity is appropriate.

In photosensitive materials for photography, the spectral sensitivity of the green photosensitive layer to achieve good color reproducibility is 500 to 600.
It is said that it is preferable that the spectral sensitization is carried out over the nm range, and that the center of gravity wavelength of the spectral maximum is in the range of 530 to 540 nm.

Conventionally, many patents have been disclosed regarding green spectral sensitization, and for dyes alone, for example, U.S. Patent No. 2,647
．． No. 053, No. 2,521,705, No. 2,072,
Oxacarbocyanine dye described in No. 908, British Patent No. 1,012,825, etc., Japanese Patent Publication No. 38-782
No. 8, No. 43-14497, British Patent No. 815,172
No. 2,778,823, U.S. Pat. No. 2,739,149
Benzimidazolocarbocyanine dyes described in Japanese Patent No. 2,912,329, No. 3, No. 656959, and oxathiacarbocyanine described in British Patent No. 1,012,825 are known.

Furthermore, for example, Japanese Patent Publication Nos. 43-4936 and 43-228
No. 84, No. 44-32753, No. 4611627,
JP-A-48-25652, JP-A-46-38694, JP-A-57-14834, etc. disclose techniques in which oxacarbocyanine dyes are combined with other dyes for supersensitization. However, although these methods increase the green sensitivity, the spectral sensitivity region shifts to long wavelengths, making it impossible to obtain good color reproduction.

Sensitizing dyes that spectrally sensitize wavelengths shorter than 550 nm include, for example, Japanese Patent Publication No. 44-14030 and Japanese Patent Application Laid-Open No. 1983-14030.
Carbonanine dyes described in US Pat. No. 31228, cyanine dyes described in US Pat. No. 2,072,908, US Pat. Old name, same 3. Dimethine merocyanine dyes such as those described in No. 180,439 are known, but when these dyes are used alone, photographic emulsions with high green sensitivity cannot be obtained, and attempts to increase the sensitivity result in fogging. There has been a problem in that it tends to occur more easily and storage stability also tends to deteriorate.

For example, Special Publication No. 50-40662, No. 48-4120
No. 5, JP-A-46-7782, JP-A No. 51-107127
No. 51-115820, No. 52-18311,
No. 52-37422, etc., discloses a technique that uses a dye that spectrally sensitizes wavelengths shorter than 550 nm, but it is insufficient to efficiently spectral sensitize the region with a center wavelength of 530 to 540 nm. Furthermore, the storage stability under high temperature and high humidity environments was not good.

[Purpose of the invention]

Therefore, the first object of the present invention is to provide a silver halide photographic material with increased spectral sensitivity in the green short wavelength region, and the second object is to provide a silver halide photographic material with increased spectral sensitivity in the green short wavelength region. The object of the present invention is to provide a silver halide color photographic material having excellent storage stability and good color reproducibility.

[Structure of the invention]

The inventors of the present invention have conducted intensive research to develop a silver halide photographic material that satisfies these demands, and have discovered that the objects of the present invention can be achieved as follows. It's arrived. That is, in a silver halide photographic light-sensitive material having at least one green-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 are formula(
The emulsion is spectrally sensitized by at least one sensitizing dye represented by T) and at least one sensitizing dye represented by the following general formula CII), and is The maximum spectral absorption wavelength of the emulsion is 5 nm or more away from the maximum absorption wavelength of the reflection spectrum of an emulsion in which the sensitizing dye contained in the emulsion is solely adsorbed to the silver halide grains. This was achieved using a silver halide photographic material characterized by the following.

General Formula [I] General Formula [II] In the formula, R, , R, , R, and R5 each represent an alkyl group or an alkenyl group, and R3 represents a hydrogen atom, an alkyl group, or an aryl group.

X,,X,represent charge balance ions, and n++''2 represents the value necessary to neutralize the charge of the entire molecule of 0 or more.

Zl and Z2 each represent an atomic group necessary to complete a benzoxazole nucleus or a naphthoxazole nucleus. 28,
2. are pyrroline nucleus, pyridine nucleus, quinoline nucleus, indolenine nucleus, benzimidazole nucleus, oxazole nucleus, benzoxazole nucleus, naphthoxazole nucleus, respectively.
Represents the atomic group necessary to complete the thiazoline nucleus, thiazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, selenazole nucleus, benzoselenazole nucleus, and naphthoselenazole nucleus.

The present invention will be explained in more detail below.

In the compounds represented by the general formulas [I] and [II] used in the present invention, RI+ Rx, R and R5 are each a straight-chain alkyl group (
For example, methyl, ethyl, propyl, butyl, pentyl,
1-pentyl, 2-ethyl-hexyl, octyl, decyl, etc.) or alkenyl M having 3 to 10 carbon atoms (e.g.
tff, 2-propenyl, 3-butenyl, l-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.), cyano groups, carbamoyl groups (e.g., carbamoyl, N -methylcarbamoyl, N,N-tetramethylenecarbamoyl, etc.), sulfamoyl group (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.) , an acylamino group (e.g., acetylamino, benzoylamino, etc.), a sulfonamide group (e.g., methanesulfonamide, butanesulfonamide, etc.), and preferably a water-soluble group (e.g., a sulfo group, carboxyl group, phosphono group, sulfato group, hydroxyl group,
sulfino group, etc.). Examples of the alkyl group substituted with a water-soluble group represented by R and R2 include carboxymethyl, sulfoethyl, sulfopropyl 3-sulfobutyl, hydroxyethyl, carboxyethyl, 3-sulfinobutyl, 3-phosphonopropyl, p
Examples of the alkenyl group substituted with a water-soluble group include 4-sulfo-3-butenyl and 2-carboxy-2-propenyl.

In general formula CI), it is preferred that either RI or R2 has a water-soluble group.

Ions that cancel out the charges within the molecule represented by X and X2 are selected from anions and cations. Anions include inorganic and organic ones, and specifically include halogen ions (e.g., chlor, bromine, iodine, etc.), organic acid anions (e.g., p-toluenesulfonate, p-chlorobenzenesulfonate, methanesulfonate, etc.), and tetrafluorocarbon anions. Examples include boron ion, perchlorate ion, methyl sulfate ion, and ethyl sulfate ion.

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

2. The benzoxazole nucleus or naphthoxazole nucleus represented by 22 includes those having a substituent on the ring. Specifically, substituents on the ring include halogen atoms (e.g. chlorine atom, bromine atom, fluorine atom, etc.)
Alkyl groups with up to 6 carbon atoms (e.g. methyl group, ethyl group, propyl group, butyl group, cyclohexyl group, etc.) aryl groups (e.g. phenyl group, etc.) Alkoxy groups with up to 4 carbon atoms (e.g. methoxy group, ethoxy group, butoxy group) etc.) Aryloxy groups (e.g., phenoxy groups, etc.) Acyl groups with 6 or less carbon atoms (e.g., acetyl, propionyl, benzoyl, etc.) Alkoxycarbonyl groups with 8 or less carbon atoms (e.g., methoxycarbonyl, ethoxycarbonyl, phenoxycarbonyl) hydroxyl group, benzyloxycarbonyl group, etc.), cyano group, trifluoromethyl group, etc.

Z, and 2. are respectively pyridine nucleus, pyridine nucleus, quinoline nucleus, indolenine nucleus, benzimidazole nucleus, oxazole nucleus, benzoxazole nucleus, naph; oxazole nucleus, thiazoline nucleus, thiazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, selenazole nucleus, It represents an atomic part necessary to complete a benzoselenazole nucleus or a toselenazole nucleus, but the above-mentioned heterocyclic nucleus also includes those having a substituent on the ring.

Specifically, thiazole series (e.g. thiazole; 4-methylthiazole; 4-phenylthiazole; 5-methylthiazole; phenylthiazole; 4,5-dimethylthiazole; 4,5-diphenylthiazole; benzothiazole; 5-fluoro Benzothiazole; 510 penzothiazole: 6-chloropensothiazole; 5-methylbenzothiazole; 6-methylbenzothiazole:
5-bromobenzothiazole, 5-carpoxypenzothiazole, 5-ethoxycarbonylbenzothiazole,
5-Hydroxybenzothiazole, 5-phenylbenzothiazole; 6-phenylbenzothiazole: 5-methoxybenzothiazole; 6-medoxypenzothiazole; 5-iodobenzothiazole: 6-ethoxybenzothiazole; Tetrahydrobenzothiazole: 5, 6-Simethylbenzothiazole; 5.6-Simethoxypenzothiazole; 56-Sioxymethylenebenzothiazole;
6-Nitoxy 5-methylbenzothiazole: 5-phenethylbenzothiazole; naphtho [1,2-dl thiazole; naphtho [2,1-dl thiazole]: naphtho [2,3-dl thiazole; 5-me] xinaphtho N
, 2-d1 Thiazole: 8-methoxynaphtho[2,1
-dl Thiazole: 7-methoxynaphtho[2,1-d
l Thiazole: 5-methoxythionaphtheno [6,7
-d] Thiazole: 8,9-dihydronaphtho [1,2
-dl thiazole; 4,5-dihydronaphtho[2,1
-d]thiazole, etc.), oxazole type (e.g., 4-
Methyloxazole; 5-methyloxazole; 4-phenyloxazole; 4,5-dimethyloxazole;
5-phenyloxazole; 5゜6-diphenyloxazole; benzoxazole; 5-chlorobenzoxazole; 5-methylbenzoxazole; 5-phenylbenzoxazole; 6-methylbenzoxazole;
5,6-dimethylbenzoxazole; 5-methoxybenzoxazole; 5-ethoxybenzoxazole;
5-7enethylbenzoxazole; 5-hydroxybenzoxazole, 5-nidoxycarbonylbenzoxazole, 5-bromobenzoxazole; 5-methyl-6-chlorobenzoxazole; naphtho [1,2-
dl oxazole; naphtho[2,1-d]oxazole; su7to[2,3-a]oxazole, etc.), selenazole series (e.g., 4-methylselenazole; 4-phenylselenazole; benzoselenazole; 5- Chlorobenzoselenazole: 5-methoxybenzoselenazole: 5
-Methylbenzoselenazole: tetrahydride penzoselenazole: naphtho[1,2-al selenazole; naph1-[2,1-d]selenazole, etc.), pyridine series (e.g., 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-〇-chloro-2-gynoline; 8-chloro-2-quinoline-〇-methoxy/-2-quinoline; 6-nitoxy-2-quinoline; 8-ethoxy-2-
Quinoline; 6-methyl-2-quinoline; 8-fluoro-
2-quinoline: 6-dimethylamine-2-quinoline; 4
-quinoline: 6-medoxy 4-quinoline; 7-methyl-4-quinoline: chloro-4-quinoline, etc.), 3
．． 3~Dialkylindole = 7 series (e.g. Eva, 3.3
-dimethylindolenine; 3.3.5-trimethylindolenine: 3.3-dimethyl-5-(dimethylamino)
Indolenine: 3.3-diethylindolenine, etc.), imidazole type (e.g. 1-alkylbenzimidazole; l-phenyl-56-ditalolopenzimidazole;
l-Alkyl-5-cyanobenzimidazole: 1-alkyl-5-chlorobenzimidazole; l-alkyl-5,6-cyclopenzimidazole; I-alkyl-chloro-6-diatubenzimidazole: l-alkyl -5-trifluoromethylbenzimidazole; 1
-alkyl-5methylsulfonylbenzimidazole;
1-alkyl-5-methoxycarbonylbenzimidazole; 1-alkyl-5-acetylbenzimidazole; 1-alkyl-5-(N,N-dimethylamino)sulfonylbenzimidazole.

Among the above heterocyclic nuclei, preferred are benzthiazole, saft(2,1-d)thiazole, and nando(2,
3-d) Thiazole series, benzoxazole series, nut (2,1-d) oxazole series, nut (2,3-d)
Oxazole series, benzoselenazole series, nuts (2,
1-d) Selenazole type, nut (2゜3-d) Selenazole type, quinoline type nucleus.

Specific examples of the sensitizing dyes represented by the general formulas CI) and [II] are shown below, but the sensitizing dyes used in the present invention are not limited to these compounds.

■ ■ (I[) ■ ■ ■ ■ ■ (1,t12)3:)LI3Na (II) (Ill cQo,.

[II]

The sensitizing dyes represented by the general formulas [I] and [II] according to the present invention are, for example, (J, Am, Chem, Soc, 67
, 18751899 (1945)), F.M. Palmer, The Chemistry of Heterocyclic Compounders.
Heterocyclic Compounds Volume 18, The Cyanine Dyesa and Related Compounders
nd Re1ated Compounds) (A
, Weissberger 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 optimal concentration of the sensitizing dyes of general formulas (1) and (II) 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 is 2XlO-6 mol-lXl per mol of silver halide.
Preferably, 0-2 mol is used, and even 5X 10-
Preferably, 'mol-5X 10-3 moles are used.

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. Nos. 2,912,345 and 3,342.
No. 605, No. 2,996,287 and No. 3,425,
The method described in No. 835 and the like can also be used.

The timing of adding the sensitizing dyes represented by the general formulas CI) and (II) used in the present invention to the emulsion is during the manufacturing process from the time of silver halide grain formation to just before coating on the support. It can be added at any time.

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, it is preferable to add the stabilizers and antifoggants at the time of silver halide grain formation or chemical ripening, that is, before the preparation of the coating solution.
The dyes represented by I] may be added by dissolving each dye in the same or different solvents and mixing the solutions before adding them to the emulsion, or adding them separately to the emulsion. However, it is more preferable to mix the dye solution before adding it to the emulsion.

The sensitizing dye according to the present invention may further be used in combination with other sensitizing dyes other than the present invention or compounds that provide supersensitizing action.

The silver halide emulsion of the present invention is spectrally sensitized by combining at least one dye selected from the dyes represented by the general formula (I) and at least one selected from the dyes represented by the general formula [II]. According to the general formula (1) or (If)
Compared to when each of the dyes represented by these dyes is used alone, the sensitization is enhanced due to the supersensitizing effect. However, not all the dyes represented by general formula CI) or general formula (II) of the present invention have a supersensitizing effect when combined, and the dyes mentioned above in the present invention do not have a supersensitizing effect when used alone or in combination. The present inventors have discovered that the spectral absorption maximum wavelength depends on the movement of time.

That is, the dye represented by general formula CI) or general formula CI+) according to the present invention has a characteristic that the single absorption maximum wavelength in the emulsion shifts by 5 nm or more when used in combination in the same emulsion system. The only dye with excellent green light sensitivity according to the present invention is the dye shown in FIG. In the present invention, the reflection spectrum of an emulsion is measured, for example, by the following method.

A coating solution is prepared by adding common photographic additives such as surfactants and hardeners to the emulsion of the present invention, and the coating solution is coated onto a subbed triacetyl cellulose support and dried to form a coated sample. create. The reflection spectrum of the prepared sample can be measured using an ordinary spectrophotometer (for example, Hitachi Automatic Recording Spectrophotometer Model U-3210 manufactured by Hitachi Seisakusho) equipped with an integrating sphere.

In the present invention, the absorption maximum of the reflection spectrum of the emulsion of the present invention and the sensitizing dye represented by the general formula CI) or CI+) contained in the emulsion have the same halogen composition and crystal habit as those contained in the emulsion. The absorption maxima of the reflection spectra of the emulsions adsorbed on the silver halide grains (hereinafter referred to as the absorption maxima of the dye alone) are separated by 5 nm or more, preferably 7 nm or more.
m or more, and more preferably 10% m or more. The emulsion of the present invention may or may not have an absorption maximum at or near the absorption maximum wavelength of the dye alone;
The present inventors have discovered that the use of such an emulsion further improves the storage stability over time of the produced photographic material.

Note that the term "around the absorption maximum wavelength of the dye alone" as used herein refers to a wavelength range in which the difference from the absorption maximum wavelength is less than 5 nm.

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 state-altering ions may be added as an ionic solution such as a potassium iodide solution, and the silver halide grains during growth may be added as an ionic solution such as a potassium iodide solution. Although it may be added as a grain with a smaller solubility product than the silver halide grain, it is more preferable to add it as a silver halide grain with a smaller solubility product.

The silver halide grains used in the present invention have a shape such as a cube, a regular octahedron, a tetradecahedron, or a spherical shape.
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, 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 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,
Preferably, the aspect ratio is from 5 to 100, more preferably from 5 to 20. The equivalent circle diameter of the flat plate grains is preferably 0.2 μm to 30 μm, and 0.4 μm.
μI is more preferably 11 to 10 μm. Also, its thickness is 0
, 5 μm or less is preferable, and 0.3 μm or less is more preferable.

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 means, for example, Th6 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 Pro-c e s s
” 4th edition, published by Macmillan (1977) 3
Neutral method, acidic method, ammonia method, forward mixing, back mixing, double jet method, described in literature such as pages 8-104,
It can be manufactured by applying a method such as a controlled daughter pull jet method, a conversion method, or a core/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.

Additive RD-17643RD-1
Page 8716 Classification Page Classification Chemical sensitizer 23 III 648- Upper right development accelerator 29 X-eye 648- Upper right blade blur prevention agent 24 V'f 649- Lower right stabilizer
11 colors anti-staining agent 25 ■ 650
Left-Right Image Stabilizer 25 ■ Ultraviolet Absorber 25 ~ 26 ■ 649 Right ~ 650
Left filter dye // // increase
Whitening agent 24V hardening agent
26 X 651 left coating aid 2
6-27XI650 right surfactant 26-27XII650 right plastic
agent 27 III t
t Slip agent ll Static prevention agent 27 )] I
tt matte agent 28
XVI 650 right binder 26 f
f 651 left In the photosensitive material according to the present invention, a dye is produced by a coupling reaction with an oxidized form of an aromatic primary amine developer (e.g., p-)22-diamine derivative, aminophenol derivative, etc.) during processing. Dye-forming couplers that form 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 power = 39 = The puller has a color correction effect, and by coupling with the oxidized form of the developing agent, the puller can be used as a development inhibitor, a development accelerator, a bleaching accelerator, a developer, and a silver halide solvent. Compounds that release photographically useful fragments such as toning agents, 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 ( Timing old R coupler and timing D
(referred to as IR 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 (
A compound represented by DIR-I) is preferred.

General formula (DIR-I) CiT uterus ZyunL-Y).

In the general formula (DIR-1: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 0.1 or 2, preferably 0 or 1. When n represents 1 or 2, and 0 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, benzoylacetanilide type), malondiester type, malondiamide type, dibenzoylmethane type, penzthiazolyl acetamide type. , malone ester monoamide type, benzothiazolylacetate type, benzoxacylylacetamide type, benzoxacylylacetate type, benzimidazolylacetamide type or benzimidazolylacetate type coupler residue, US Pat. No. 3,841,880 Coupler residues derived from heterocycle-substituted acetamides or peterocycle-substituted acetates contained in or U.S. Pat.
Coupler residues derived from acylacetamides described in No. 3.099, JP-A-50-139738, Research Disclosure No. 15737, etc., or heterozygous coupler residues described in U.S. Pat. No. 4,046,574. etc. 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 (for example, 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 α-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
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 image-forming coupler residue, a 5-oxo-2-pyrazoline core magenta image-forming coupler residue, an α-naphthol core cyan image-forming coupler residue. and efflux dye-forming coupler residues of α-su7thole 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 hemi-secure cleavage reaction, (
Examples include 4) a group using an iminoketal cleavage reaction, and (5) a group using an ester hydrolysis cleavage reaction.

For the group ([), 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. 62-8636] and No. 62
-87958, the group (2) is described in, for example, JP-A No. 57-56837 and U.S. Pat.
No. 148, No. 60-249149, U.S. Patent No. 4,14
No. 6,396, for the group (4), see, for example, U.S. Pat.
6.315 describes 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 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-
aminophenol M), naphthalene diols (e.g. 1,2-naphthalene diols, 1,71-naphthalene diols, 2,6-naphthalene diols), or aminonaphthols (e.g. 1,2-naphthalene diols, 1,4-aminophels, 2,6-aminonaphthols), and the like.

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

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

Examples of the substituent represented by R1 include) \rogen atom, alkyl group, alkenyl group, alkoxy group, alkoxycarbonyl group, anilino group, acylamino group, ureido group, cyano group, nitro group, sulfonamide group, and sulfamoyl group. , carno(moyl group, aryl group, nonorpoxyl group, sulfo group, cycloalkyl group, alkanesulfonyl group, arylsulfonyl group, or acyl group, and these include those having further substituents.

Examples of the substituent represented by R2 and R3 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-■] is a divalent linking group, and contains a chemical bond that is cleaved by a component in the developer, such as a nucleophile such as hydroxy ion or hydroxylamine.

Examples of such chemical bonds include -COON-Co
o --5O20-, -0CH2CH,5O2-, -o
co.

-N-COCOO-, and these chemical bonds are:
W co-Z is connected directly or via an alkylene group and/or 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.

W3 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, book 3 represents a site that binds to 2, and book 4 represents a site that binds to Y.

*3 -(CH2)dCoo-Book 4
*3 -(CH2)dOOC-*4W + , W
2 and W3' represent a hydrogen atom or a substituent.

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

Examples of the substituent represented by W 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 carnocumoyl group, a nitro group, a cyano 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, and the like.

is synonymous with W3, the same substituents are exemplified, and q is 0 to
Represents an integer of 6.

In the general formula [DIR-■], 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.
It represents a straight chain, branched chain alkyl group, alkenyl group or cycloalkyl group, preferably having a substituent, and examples of the substituent include a norylogen atom, a nitro group, an alkoxy group having 1 to 4 carbon atoms, Aryloxy group having 6 to 10 carbon atoms, alkanesulfonyl group having 1 to 4 carbon atoms, 6 carbon atoms
~10 noarylsulfonyl group, alkanamide group having 2 to 5 carbon atoms, anilino group, benzamide group, having 2 to 5 carbon atoms
6 alkylcarbamoyl group, carbamoyl group, arylcarbamoyl group having 7 to 10 carbon atoms, alkylsulfonamide group having 1 to 4 carbon atoms, arylsulfonamide group having 6 to IO carbon atoms, alkylthio group having 1 to 4 carbon atoms, Arylthio group having 6 to 0 carbon atoms, phthalimide group, succinimide group, imidazolyl group, 1,2.4-)riazolyl group, pyrazolyl group, benzotriazolyl group, furyl group, benzothiazolyl group, having 1 to 4 carbon atoms alkylamino group, 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, amine group, 1 to 4 carbon atoms 4 alkylsulfamoyl group, arylsulfamoyl group having 6 to 10 carbon atoms, morpholino group, aryl group having 6 to 10 carbon atoms, pyrrolidinyl group, ureido group, oxyamide group, alkoxycarbonyl group having 2 to 6 carbon atoms , carbon number 7
~IO, an aryloxycarbonyl group, an imidazolidinyl group, or an alkylidene amino group having 1 to 6 carbon atoms.

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

The heterocyclic group represented by Y is a diazolyl group (2 imidazolyl group, 4-pyrazolyl group, etc.), a triazolyl group (1
, 2,4-)lyazol-3-yl group, etc.), thiazolyl group (2-benzothiazolyl group, etc.), oxasilyl group (l,3-oxazol-2-yl group, etc.), pyrrolyl group, pyridyl group, diazinyl group ( l,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.

Examples of 2 in the general formula CDIR-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, a benzothiazolylthio group, Examples include benzimidazolylthio group, triazolylthio group, and imidazolylthio group.

General formula (D I R ■ The following is a specific example of Z in Shown below.

In the structure, *5 represents the binding site between Cp (T→1- and *6 is ItoLY)n.

However, X represents a hydrogen atom or a substituent, and the general formula f:D
In IR-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 alkoxy group, a sulfonamide group, or an aryl group. It will be done.

The alkyl group or alkenyl group represented by
) IR-I: ] has the same meaning as the alkyl group or alkenyl group represented by Y.

Specifically, the alkanamide group, cycloalkanamide group, or alkenamide group represented by X has 2 to 10 carbon atoms.
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 the 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.

D　I　R ■ ■ -Y IR is R3 and is R2 and R3/ is R3, They are synonymous, a′ is a is synonymous with X' is synonymous with X.

or, Cp.

Y is general ceremony Cp and Synonymous with Y It is.

D of the present invention is described below. ■ Specific examples of R compounds are shown below, IR IR ShiR5 IR and 11. C00C5H1 ]]R IR IR IR-14 IR IR IR lR IR IR IR 1R ShiQ IR ShiU IR IR IR Dou--N-Ichiban Shi61113 IR IR IR IR IR IR CH2COOC,H.

lR IR IR IR C112COOC31 (7 IR IR-55 The development inhibitor of the DIR coupler of the present invention must have a certain decomposition rate constant. That is, the half-life of the development inhibitor at pH 10.0 is , less than 4 hours,
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 can be 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 can be determined by liquid chromatography. can.

Diethylenetriaminepentaacetic acid 0.8g 1-hydroxyethylidene-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 Add 4.5g edylamino)-2-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 IX10-' to lXl0-' of the total coated silver amount.
Mol% is preferred.

When the compound represented by the general formula (DTR-I) of the present invention is added to a light-sensitive material, anti/runyong layers, interlayers (between different color-sensitive layers, between the same color-sensitive layers, between light-sensitive layers, and a non-photosensitive layer), a photosensitive silver halide emulsion layer, a non-photosensitive silver halide emulsion layer, a yellow filter layer, a protective layer, etc. It may be added in amounts above.

Two or more of these compounds may be mixed into the photosensitive dye, and the total amount added is 0.01 to 50 mol % per mol of silver halide when contained in the emulsion layer, preferably 0.01 to 50 mol % per mol of silver halide. ~5 mol%. When included in the non-photosensitive hydrophilic colloid layer, the coating amount is preferably 10
-7 to 10-3 mol/m2, more preferably 10-6 to
10-'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. 1.94, No. 3,551,155, No. 3
, No. 582,322, No. 3, No. 725072, No. 3,
No. 891,445, West German Patent No. 1,547,868, West German Application No. 2,219,917, West German Patent No. 2,261.36
No. 1, No. 2414.006, 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., 58
2゜322, 3,615,506, 3,834
, No. 908, No. 3,891゜445, West German patent],
No. 810.464, West German Patent Application (OLS) 2.408
, No. 665, No. 2,417,945, No. 2.4189
No. 59, No. 2,424,467, Special Publication No. 40-603
No. 1, JP-A-51-20826, JP-A No. 52-58922
No. 49-129538, No. 49-74027,
No. 50-159336, No. 52-42121, No. 4
No. 9-74028, No. 50-60233, No. 51-2
No. 6541, No. 53-55122, No. 59-1719
No. 56, No. 60-33552, No. 60-43659, No. 60-172982, No. 60-190779, etc.

As the cyan color-forming coupler, a phenol compound, a naphthol compound, etc. may 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,
3,476.563, 3,583,971, 3゜591.383, 3,767.411, 4
, 004, No. 929, West German Patent Application (OLS) 2
, No. 414,830, No. 2,454,329, JP-A-48-59838, No. 51-26034, No. 48-
No. 5055, No. 5]-146828, No. 52-696
There are those described in No. 24 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, good dimensional stability and little dimensional change during the production process or processing. Examples of the support in this case include 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. 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 m 2 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 (Preparation of Sample No. 101) A silver iodobromide emulsion with an average grain size of 0.65 μm and an internal silver iodide core of 8 mol % and an average silver iodide content of 8 mol % was coated. Sulfur sensitization was carried out and sensitizing dye I-4 was added at 2.0% per mole of silver. 10-' mol of OX was added to spectral sensitize to green sensitivity. Then 4-hydroxy-6-methyl 1.3.3a
, 7-chitradesign and l-phenyl-5-mercaptotetrazole were added for stabilization.

Furthermore, a dispersion in which the following magenta coupler (M-1) is dissolved in ethyl acetate and a high boiling point solvent (Oil-2) and emulsified and dispersed in an aqueous solution containing gelatin, and general photographic additives such as a spreading agent and a hardening agent. was added to prepare a coating solution, which was coated on a subbed triacetyl cellulose support by a conventional method and dried to prepare light-sensitive material samples No. 1 and I old.

(Creation of sample No., 102-No., l19) Sample No.
1Ol of sensitizing dye ■-4 was replaced with the dye listed in the sensitizing dye r column of Table 1 in equimolar amounts, and further the dye listed in the sensitizing dye column of Table 1 was added per mole of silver], 3X 10- 'It was prepared in exactly the same manner as sample No. 1Ol except that molar addition was made. Note that the sensitizing dye was added to the emulsion as a mixed solution.

(Preparation of Sample No. I20) A chemically sensitized emulsion similar to that used in the preparation of Sample No. 1OI was dissolved at 50°C, and sensitizing dye ■1 was added at 1.3X per mole of silver. 10-' mol was added and the conversion was made properly.

Thereafter, sensitizing dye I-4 was added at 2.0 x 10-
' mol added and spectrally sensitized to green sensitivity. Then, 4-hydroxy-6-methyl-1,3,3a-7-titrazaindene and l-phenyl-5-mercaptotetrazole were added for stabilization.

Sample No. 101 was prepared in exactly the same manner as Sample No. 101 except that the silver iodobromide emulsion thus prepared was used.

Each sample was wedge exposed through an interference filter with a transmitted light maximum of 530 nm and processed through 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 l/2 sulfate 2.0g Anhydrous potassium carbonate 37.5 g potassium bromide
1.3 g di].lilotriacetic acid trisodium salt (l hydrate) 2.5 g potassium hydroxide 1.0 g Add water to make 1a (bleach solution) Ethylenediaminetetraacetic acid iron (III) ammonium salt 100. , Og ethylenediaminetetraacetic acid diammonium salt 10.0 g Ammonium bromide 150.0 g Glacial acetic acid 10.0 g Add water to make IQ, and adjust to pH 6.0 using aqueous ammonia.

(Fixer) Ammonium thiosulfate 175.0 g Anhydrous ammonium sulfite 8.6 g Sodium metasulfite 2.3 g Add water to 1Q
and adjust the pH to 6.0 using acetic acid.

(Stabilizing liquid) Formalin (37% aqueous solution) 1.5ml
2 Konidax (manufactured by Konica Corporation) 7.5 m
Q Add water to obtain IQ *Temporary storage test sample left naturally for 18 hours (A) and temperature 50°C
For the sample (B) that was forced to deteriorate by leaving it in a constant temperature laboratory 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.

As a method for measuring the maximum absorption value, the reflection spectrum of each sample after coating was measured using a spectrophotometer model U-320 (manufactured by Hitachi, Ltd.) equipped with an integrating sphere.

* * Δ λ max Difference (Δ) between the maximum absorption wavelength of the reflection spectrum observed for a sample using two or more types of sensitizing dyes and the maximum absorption wavelength when the sensitizing dye contained in the sample is used alone The smaller value is shown. When two absorption maxima were observed, the respective absorption maxima were shown.

The value indicated by ΔA max is 5 nm or more,
This is a sample according to the present invention.

As is clear from the results in Table 1, it can be seen that the samples of the present invention have enhanced spectral sensitivity in the short wavelength region of green and also have improved storage stability over time.

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

1st layer: Antihalation layer (IC) Black colloidal silver UV absorber (UV-1) Colored coupler (CC-], ) High boiling point solvent (Oil-1) High boiling point solvent (Oil-2) Gelatin 2nd layer : Intermediate layer (IL-1) Gelatin third layer: Low sensitivity red-sensitive emulsion Ill (RL) Silver iodobromide emulsion (Em-1) 0.15 0.20 0.02 0.20 0.20 1.6 1.3 0.4 // (E m -2) Sensitizing dye (S-1) 3.2XIO Sensitizing dye (S-2) 3.2XIO Sensitizing dye (S-3) 0.2X]0 Cyan Coupler (C-1) Cyan coupler (C-2) Colored cyan coupler (CC DIR compound (D-1) tt (D-2) High boiling point solvent (Oil-1) Gelatin 4th layer: High sensitivity red-sensitive emulsion layer (RH) Silver iodobromide emulsion (Em-3) Sensitizing dye (s-1) 1.7XIO Sensitizing dye (S-2) 1.6XIO Sensitizing dye (S-3) O,1XIO Cyan coupler (C -2) Colored cyan coupler (CC DIR compound CD-2) High boiling point solvent (Oil-1) '(tt 1 (mol/silver 0.9 4 (mol/silver 1 mol) '(// ) '(// ) 0.23 1) 0.03 0.02 0.25 '(/1 0.3 1 mol) 0.50 1) 0.07 0.006 0.01 O955 1,0 Gelatin 5th layer: intermediate layer (IL-2) Gelatin 6th layer/Low-sensitivity green-sensitive emulsion layer (GL) Silver iodobromide emulsion (Em-1) 0.6tt
(Em-2) 0.2 sensitizing dye (I
-4) 4.5X10-' (-F: 1 mole of silver) //
(SR-1)3.0XIO-'(//'
) Magenta coupler = (M-1) 0.17//
(M-2) 0.43 Colored magenta coupler (CM-1) 0.10 DIR compound listed in Table 2 0.02 High boiling point solvent (oI+-2)
0.70 Geradin 1.
0 No. 7N Highly sensitive green-sensitive emulsion layer (Gl+) Silver iodobromide emulsion (Em-3) Sensitizing dye (I-37)3. lX1O-' (mol/silver 1
mol)// (SR-1)0.3XlO-'(//
) Magenta coupler (M-1) // (M-2) 0.03 0.9 1.0 0.8 0.13 Colored magenta coupler (CM) DIR compound listed in Table 2 High boiling point solvent (Oil-2) Gelatin 8th layer: Yellow filter Yellow colloidal silver additive (H3-1) Additive (H5-2) Additive (SC-1) High melting point organic solvent (Oil-2) Gelatin 9th layer: Low sensitivity blue-sensitive emulsion Layer (BL) Silver iodobromide emulsion (E+n-1) Silver iodobromide emulsion (Em-2) Sensitizing dye (S-4) 5.8XlO Yellow coupler (Y // (Y DIR compound (D-1) // (D-2) High boiling point solvent (Oil-2) (yc) 0.25 0.25 4 (mol/silver 1 mol) ]) 0.60 2) 0.32 0.003 0.006 0. 18 1) 0.04 0.004 0.35 1.0 0.1 0.07 0.07 0.12 0.15 1.0 Gelatin 1.3 10th layer: High-speed blue-sensitive emulsion layer (BH) Silver iodobromide (Em-4)
0.5 sensitizing dye (S-5) 3.0xlO'(
mole/1 mole of silver) // (S-6)1.2XlO-'
(// ) Yellow coupler (Y-1)
0.18// (Y-2) 0.1
0 High boiling point solvent (Oil-2) 0.05
Zeradine 1.0 1st protective layer (P
RO-1) Silver iodobromide (Em-5) 0.3 Ultraviolet absorber (UV-1) 0.07tt
(UV-2) 0-1 additive (H5-1)
0.2 additive (H3-2)
0.1 high boiling point solvent (Oil-1)
0.07 high point solvent (Oi 1-3)
0.07 Zeradine 0.
8 Second protective layer (PRO-2) Alkali-soluble matting agent 0.13 1st layer: 12th layer: (Average particle size 2 μm) Polymethyl methacrylate 0.02 (Average particle size
3 μm) Gelatin 0.5 In addition, each layer has
In addition to the above composition, coating aid SU2, dispersion aid SU-],
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 internal height deformation.

Em-1: Average AgI content 7.5 mol% Octahedron 0
．． 55μmEm-2: Average Agl content 2.5 mol%
Octahedron 0.36μmEm-3: Average Agl content 8,
0 mol% Octahedron 0.84μmEm-4: Average Agl
Content 8.5 mol% Octahedron 1.02 μm Em-5:
Average Agl content 2.0 mol% 0.08 μm (
Preparation of Sample Nos. 202 to 220) Sample No. 201 except that the sensitizing dyes I-4 and 5R-1 of Sample No. 201 were replaced with equimolar amounts of the sensitizing dyes I and 5R-1 in Table 2, respectively, with the dyes listed in the It column. Created in exactly the same way. Each sample obtained was subjected to self-exposure and development in the same manner as in Example 1, and its sensitivity and storage stability over time were evaluated. Further, the absorption maximum was also expressed as Δλmax as in Example 1.

The results obtained are shown in Table 2 below.

Table 2 As is clear from the results in Table 2, the samples of the present invention have enhanced spectral sensitivity in the short wavelength region of green, and are also excellent in storage stability over time.

Furthermore, it can be seen that when a DIR compound is used in the sample of the present invention, the storage stability over time is improved, which is a more preferred embodiment of the present invention.

Example 3 (Preparation of Sample No. 30]-309) Each layer having the following composition was sequentially applied from the support side onto a subbed triacetyl cellulose film support to prepare sample No. 30 as a comparative sample of a multilayer color photosensitive material. 301 to 309 were created. Application amount of each component is g/m unless otherwise specified.
Shown as 2. Furthermore, silver halide and colloidal silver are shown in terms of silver.

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 High boiling point solvent 0il-10,2 Gelatin 1.0 Third layer (low sensitivity red-sensitive silver halide emulsion layer) Red sensitizing dye (S-
7, S-8) spectrally sensitized AgBrl (Ag
l 4.0 mol%, average particle size 0.25 μm) 0.5 Coupler C-30, 1 mol High boiling point solvent 0i1-30.6 Gelatin 1.3 4th layer (high sensitivity red-sensitive silver halide emulsion layer) Red sensitizing dye (S~7
, S-8) spectrally sensitized by AgBrl (Ag
12 mol%, average particle size 0.6 μm) 0.8 Coupler C-30,2 High boiling point solvent Oil -31,2 Gelatin 1.8 5th layer (intermediate layer) Additive SC 0,1 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 grain 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 (highly sensitive 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-10,
10 mole coupler M -30.02 mole High boiling point solvent 0i1-21.0 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 0il-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 Cobbler Y -2Q, 3 mol High boiling point solvent 0i1-20.6 Gelatin 1.3 11th layer (
High-speed blue-sensitive silver halide emulsion layer) Blue sensitizing dye (S
AgBrl spectrally sensitized by -9) (Agl 2 mol%, average particle size 0.9 μm) 0.9 coupler Y
-20.5 mol High boiling point solvent 0i1-21.4 Gelatin 2.1 12th layer (
1st protective layer) Ultraviolet absorber U -I Q,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.

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

The results are shown in Table-3.

Note that the sensitivity and storage stability over time refer to the sensitivity to light transmitted through an interference filter with maximum transmitted light of 530 nm. For sensitivity, draw a tangent to the high concentration side of the characteristic curve from the concentration point T, which is 0.2 higher than the lowest concentration value, and set the contact point to S.
The exposure amount corresponding to point T and point S is HLXHs, respectively.
The reciprocal of the exposure i Hm obtained by the following formula is expressed as a relative value when sample No. 301 is taken as 100.

The storage stability over time was determined in the same manner as in Example 1.
child .

Each sample was processed through the following processing steps.

Processing process Processing time Processing temperature 1st development 6 minutes 38°C Water washing 2 minutes
Transfer 2 minutes // Color development 6 minutes 11 Adjustment 2 minutes
White 6 minutes ll fixed
Arrival: 4 minutes Wash with water: 4 minutes // Stable
Dry at room temperature for 1 minute 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 (l hydrate) 1-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 Color developer with water g 2.5 g 1.2 g mo 1000 mQ g g o, 1 g g 5 mQ 1000 mQ Sodium tetrapolyphosphate Sodium sulfite Sodium tertiary phosphate (dihydrate) Potassium bromide Potassium iodide (0 , 1% solution) Sodium hydroxide citrazate N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-amine g g 6 g g 0 mo g 1.5 g Aniline sulfate 2.2- Adjust by adding 1 g of ethylene dithiodiethanol and water.Liquid Sodium sulfite Sodium ethylenediaminetetraacetate (dihydrate) Add dioglycerin and glacial acetic acid water to bleach Solution 1000 mu 2 g g 0.4 m12 mo 1000 m (2 ethylenediamine Sodium tetraacetate (dihydrate) Ethylenediamine iron (III) tetraacetate Ammonium (dihydrate) Fixed by adding aqueous potassium bromide Liquid ammonium thiosulfate Sodium sulfite Stabilized by adding aqueous sodium bisulfite Liquid formalin (37% by weight) ) Konidax (manufactured by Konica (a)) Add water g 20 g 00 g 1000 mQ mQ 5 m+2 1000 mQ Table 3 As is clear from Table 3, the reversal color photographic light-sensitive material sample No. 303 of the present invention It can be seen that Sample No. 308 has higher sensitivity on the short wavelength side of green light than the comparative sample and has excellent storage stability over time.

Example 4 Each layer having the composition shown below was sequentially formed on both sides of an undercoated polyethylene terephthalate support from the support side to obtain X-ray photosensitive material sample No.

401 to 408 were obtained.

Additives other than silver halide are shown in amounts per mole of silver halide unless otherwise specified.

1st layer: Crossover cut layer dye (A I-3) 3 mg/m2 Mordant (Cpd-1) 0.2 g/m2 Geradine 0.2 g/m2: Emulsion layer average grain size 0.57 μm, containing 12 mol% Ag AgBr
Emulsion coating amount consisting of I: 4.5 g/m2 Sensitizing dye (listed in Table 4): 4-Hydroxy-6-methyl-1,3,3a-7-tetrazaindene: 3.0 gL-
Butyl-catechol 400mg polyvinylpyrrolidone (molecular weight 10,000) 1.0g styrene-maleic anhydride copolymer 2.5g trimedylolpropane 10g diethylene glycol
5g 2nd layer p-nitrophenyltriphenylphosphonium chloride 1.3-dihydroxybenzene-4 Ammonium sulfonate 2-mercaptobenzimidazole 5-Sodium sulfonate 0mg g 1.5mg 5O,Na 3rd layer: Su 11 1 .1-dimethylol-1-bromo-1-nitromethane gelatin protective layer polymethyl methacrylate-1 (average particle size 5 μm) Colloidal silica (average particle size 0.013 μm) 1.0 g 2 g/m2 7 mg/m2 70 mg /m2 (n is a mixture of 2 to 5) Gelatin 1g/m2 Hardener t
(2C=CH3O2CHzOCf(2so□CH=CI
.

Each sample was exposed to light through an interference filter with a transmitted light maximum of 540 nm and subjected to the following processing, and sensitivity and fog were measured. Sensitivity is expressed as the reciprocal of the exposure amount that gives a density of fog + 0.5, and the sensitivity of sample No. 401, which was left at 40°C and 50% relative humidity for 2 days after coating, is 100.
; Shown as relative sensitivity.

(Processing process) insert Development + Transfer 35°C Fixation → - Transition 33°C Water washing + crossing 25°C Squeeze 40°C Drying 45°C (Developer) hydroquinone Phenidone potassium sulfite l1llllll acid hydroxide sulfur/lium 1-Liyylene glycol 5-nitroimidazole 5-Nitrobenzimidazole glutaraldehyde bisulfite glacial acetic acid potassium bromide 1.2 seconds 14.6 seconds 8.2 seconds 7.2 seconds 5.7 seconds 8.1 seconds 25.0g 1.2g 55.0g 10.0g 21.0g 17.5g O, 10g 0.10g 1, 5, 0 g 16.0g 4.0g triethylenetetraminehexaacetic acid Add water to make 112.

(Fixer) ammonium thiosulfate Anhydrous sulfite, sodium boric acid Acetic acid (90wt%) Sodium acetate (trihydrate) Aluminum sulfate (18 hydrate) Sulfuric acid (50wt%) Add water to make 1a.

The results are shown in Table 4.

2.5g 130.9g 7.3g 7.0g 5.5g 25.8g 14.6g 6.77g *Δλmax + Similarly to Example 2, as is clear from the results of Evaluation Table-4, the compound of the present invention In the X-ray photosensitive material containing the additive, almost no increase in fog was observed, and high sensitivity was obtained.

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

CM (comparative dye) R R S H5 mixture (2:3) C [(CH2= CH302CH2)3CCH2SO2C
H2CH, ] 2NCH2CH2SO3KC14('1 (CH2-CH302CH2) 20 C, ++.

U- U NaO3S Ct(COOCat(+7CH2C0
0C8) 117 Cpd Example 5 (Preparation of Samples 501 to 507) On a subbed cellulose triacetate film support,
Samples 501 to 507, which are multilayer color photosensitive materials each having each layer having the composition shown below, were prepared.

(Composition of photosensitive layer) The coating amount is g of silver for silver halide and colloidal silver.
/m2, and for couplers, additives and gelatin in g/m'', and for sensitizing dyes in moles per mole of silver halide in the same layer. The symbols indicating additives have the meanings shown below.However, if the additive has multiple effects, one of them will be listed as a representative.

UV; ultraviolet absorber, Solv H high-temperature organic solvent,
ExF: Dye, ExS: Sensitizing dye, ExC: Cyan coupler ExM: Magenta coupler ExY: Yellow coupler Cpd: Additive 1st layer (antihalation layer) Black colloidal silver...0.15
x:y=20:80 Gelatin UV-4 v-2 UV-3 olv-2 ExF-] ExF-2 2nd layer (low sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion (Agl 4 mol% 0.4μ , Number of fluctuations in equivalent sphere diameter 37% / Thickness ratio 3.0) ...2.9 ...0.03 ...0.06 ...0.07 ...0.08 ...0, Ol ...0,01 Uniform Equivalent sphere diameter plate-like particle diameter Gelatin ExS-I ExS-2 ExS-5 ExS-7 xC-I xC-2 xC-3 Coated silver amount...0.4 ...0. 8...2.3X 10th...1.4X 10-4...2.3X 10-'...8. OX 10-' ...0.17 ...0.03 ...0.13 Third layer (medium-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion (Agl 6 mol%, core-shell ratio 2:1
Internal height Agl: equivalent sphere diameter 0.65μ, coefficient of variation of equivalent sphere diameter 25%, plate-like grains, diameter/thickness ratio 2.0) Coated silver amount: 0.65 Silver iodobromide emulsion (Ag 14 mol%) , uniform Agl type, equivalent sphere diameter 0.4 μ, coefficient of variation of equivalent sphere diameter 37%, plate-like particles,
Diameter/thickness ratio 3.0) Coated silver amount...0.1 Gelatin...1.0ExS-
1...2 X 10-' ExS-2-1, 2X 10-'ExS-5--
・2x1o-'ExS-7-...7xlo-' ExC-1-0,31 ExC-2...0,0I ExC-3...0.06 4th layer (high sensitivity red-sensitive emulsion layer ) Silver iodobromide emulsion (Ag+6 mol%, internal high Agl type with core-shell ratio of 2.1, equivalent sphere diameter 0.7μ, coefficient of variation of equivalent sphere diameter 25%, plate-like grains, diameter/thickness ratio 2.5) Gelatin ExS-1 ExS-2 ExS-5 ExS-7 xC-1 xC-4 olv-1 0IV-2 pd-7 5th layer (middle layer) Gelatin UV-4 v-5 pa-1 Polyethyl acrylic olv -1 6th layer (low-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion (Agl 4 mol% Toratex coated silver amount...0.9...0.8...1.6X 10 information...・1.6X 10-' ...1.6X 10-' ...6.OX 10-4 ...0.07 ...0.05 ...0.07 ...0.20 ...4.6X 10-' ...0.6 ...0.03 ...0.04 ...0.1 ...0.08 ...0.05 Uniform type.

Ball equivalent diameter 0.4μ, ball equivalent diameter 0.7μ1, coefficient of variation of ball equivalent diameter 3
7%, plate-like particles, diameter/thickness ratio 2.0) Coated silver amount...
0.18 Gelatin...0.4Ex
S-3...2. OX 10-' ExS-4 (dye listed in the sensitizing dye I column of Table 5)-5,
OX 10-' ExS-5 (dye listed in the sensitizing dye column ■ in Table 5)...
3. OX 10-' ExM-5...0.11 ExM-7...0.03 ExY -8-0,01 Solv -1-0,09 Solv -4-0,01 7th layer (medium sensitivity Green-sensitive emulsion layer) Silver iodobromide emulsion (Agl 4 mol%, core shell ratio l:]
Surface height Agl type, law equivalent type, equivalent sphere diameter 0.5μ1, coefficient of variation of equivalent sphere diameter 20%, plate-like particles, diameter/thickness ratio 4.0
) Coated silver amount...0.27 Gelatin...0.6ExS
-3-2, OX 10-' ExS-4 (dye listed in the sensitizing dye I column of Table 5)...
5. OX 10-' ExS-5 (dye listed in the sensitizing dye column ■ in Table 5)...
3. OX 10-' ExM -5-0,17 ExM-7-0,04 ExY -8-0,02 soIV-1...o, +4 Solv-4-0,02 8th layer (high sensitivity Green-sensitive emulsion layer) Silver iodobromide emulsion (Ag+8.7 mol%, silver ratio 3:4+2
Multi-layer structured particles, Ag + content from inside 24 mol 0 mol, 3 mol% 1 sphere equivalent diameter 0.7μ, coefficient of variation of sphere equivalent diameter 2
5%, plate-like particles, diameter/thickness ratio 1.6) Coated silver amount...
0.7 Gelatin...0.8E
xs -4-5,2X 10-' E xS-5-i, ox 10-' ExS-8...0.3X 10 information xM-5 ExM -6 ExY -8 EXC-1 EXC-4 SOLv-1 SOLv-2 SOLv-4 pd-7 9th layer (middle layer) Gelatin...0.6Cp
d-1...0.04 Polyethyl acrylate latex...0.12
S olv -1-0,02 1st O layer (donor layer for interlayer effect on red-sensitive layer) Silver iodobromide emulsion (Agl 6 mol%, internal high Agl type with core-shell ratio 2:1, equivalent sphere diameter 0.7μ , coefficient of variation of equivalent sphere diameter 2
5%, plate-like particles, diameter/thickness ratio 2.0) Coated silver amount...
0.68 Silver iodobromide emulsion (Agl 4 mol% uniform type, equivalent to sphere...
・0.1 ...0.03 ...0.02 ...0.02 ...0. Ol...0.25...0.06...0.01 1XIO-' Coefficient of variation in diameter 37%, plate-shaped particles, diameter/thickness ratio 3.0)
Coated silver amount...0.19 Gelatin...1.0Ex
S-3...6. OX 10-4 10-4Ex...0.
19Solv-1...0.20 11th layer (yellow filter layer) Yellow colloidal silver gelatin pd-2 SOLv pd pd 12th layer (low sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion (Agl 4.5 mol% , uniform-Agl type,
Equivalent sphere diameter 0.7μ, coefficient of variation of equivalent sphere diameter 15%, plate-like particles, diameter/thickness ratio 9.0) Coated silver amount...0.3
Silver iodobromide emulsion (Agl 3 mol%, uniform Agl type, equivalent sphere diameter 0.3μ, coefficient of variation of equivalent sphere diameter 30%, plate shape...
0.06 ...0.8 ...0.13 ...0.13 ...0.07 ...0.002 ...0.13 ■ Particles, diameter/thickness ratio 9.0) Coated silver amount...0.
15 Gelatin...0.
9ExS-6...9. OX 10-' ExC-1...0.06 ExC-4...0.03 ExY -9-0,14 EXY-11...0.89 Solv 1 -0.4
2 13th layer (middle layer) Gelatin...0.7Ex
Y -12-0,20 Solv 1 -0-3
4 14th layer (high sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion (Ag 110 mol%, internal Agl type, equivalent sphere diameter 1.0μ, coefficient of variation of equivalent sphere diameter 25%, multi-twinned plate-like grains, diameter /thickness ratio 2.0) Coated silver amount...0.5 Gelatin...0.5Ex
S -6・= 1 xto-' ExY-9...0.01 ExY -11 ExC-1 olv-1 15th layer (first protective layer) Fine grain silver bromide emulsion sphere equivalent diameter 0.07μ) Gelatin V -4 V-5 olv-5 pd-5 Polyethyl acrylate - 16th layer (second protective layer) Fine grain silver bromide emulsion (Agl 2 mol%, homogeneous Agl type,
Equivalent sphere diameter 0.07μ) Coated silver amount...0.
36 gelatin...0.
45 polymethyl methacrylate particle diameter 1.5μ...
0.2H-1...0.17 In addition to the above components, each layer contains an emulsion stabilizer cpa...
0.02 ...0.20 ...0.10 (Agl 2 mol%, uniform Agl type, coated silver amount...0.12 ...0.7 ...0.11 ...0. 16 ...0.02 ...0.13 ...0.10 Toratex ...0.09 (0.07g/m2) Surfactant cpa (0.03 V ■ olv-1 Tricresyl phosphate olv Dibutyl phthalate olv V olv Trihexyl phosphate XF V V

ExS ExS ExS ExS xC xC xM C,H.

H mo44t, approx. 20,000 xM xY pd xY xY pd- Regarding the upper sample, Example 1 Similarly, green Sensitivity of the sensitive layer, The storage stability over time was evaluated.

Conclusion show the fruit It was summarized in 5.

Note that the sensitivity is expressed as a relative value with sample No. 0.501 set as loo.

table

[Brief explanation of drawings]

FIG. 1 shows the spectral reflection spectra of samples of the present invention and comparative samples, with the vertical axis representing Absorption (=-Log (reflected light from sample/reflected light from reference)) and the horizontal axis representing wavelength. In FIG. 1, the curve ■ is for sample No. 101, the curve ■ is for sample No. 118, the curve ■ is for sample No. 104, the curve ■ is for sample No. 105, and the curve ■ is for sample No. 119.
represents each spectral reflection spectrum. *Δλmax: Evaluated in the same manner as in Example 2. As is clear from the results in Table 5, the samples of the present invention have enhanced spectral sensitivity in the green short wavelength range and are also excellent in green storage stability. [Effects of the present invention] According to the present invention, a silver halide photographic material is provided which has enhanced spectral sensitivity in the short wavelength region of green, has excellent storage stability over time, and has excellent color reproducibility. Ta.

Claims (1)

[Scope of Claims] In a silver halide photographic light-sensitive material having at least one green-sensitive silver halide emulsion layer on a support, silver halide contained in at least one of the green-sensitive silver halide emulsion layers. The grains are spectrally sensitized with at least one sensitizing dye represented by the following general formula [I] and at least one sensitizing dye represented by the following general formula [II], and the reflection of the emulsion is The maximum spectral absorption wavelength observed when the spectrum is measured is relative to the maximum absorption wavelength of the reflection spectrum of an emulsion in which the sensitizing dye contained in the emulsion is adsorbed solely to the silver halide grains. A silver halide photographic material, characterized in that the two are separated by 5 nm or more. General formula [I] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ General formula [II] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ In the formula, R_1, R_2, R_4 and R_5 each represent an alkyl group or an alkenyl group. , R_3 represents a hydrogen atom, an alkyl group, or an aryl group. X_1, X_2 represent charge-balanced ions, n_1, n_
2 represents the value necessary to neutralize the charge of the entire molecule of 0 or more. Z_1 and Z_2 each represent an atomic group necessary to complete a benzoxazole nucleus or a naphthoxazole nucleus. Z
_3 and Z_4 are pyrroline 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 nucleus, respectively. , represents the atomic group necessary to complete the benzoselenazole nucleus and naphthoselenazole nucleus.