JPH11237706A - Silver halide photosensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the silver halide photosensitive material having a nonvisible light sensitive silver halide emulsion layer high in sensitivity and low in fog by incorporating a specified compound and a specified image quality enhancer in this emulsion layer. SOLUTION: This silver halide photosensitive material is provided on a support with red-, green-, and blue-sensitive silver halide emulsion layers each containing a coupler and the nonvisible light sensitive silver halide emulsion layer containing one of the image quality enhancers and one of the compounds represented by formulae I-IV in which each of Z11 , Z12 , Z21 , Z22 , Z31 , Z41 , and Z42 is a nonmetallic atomic group necessary to form a 5- or 6-membered N- containing monocyclic or its condensed ring; each of Q31 , Q32 , and Q33 is an 0 or S atom or the like; each of R11 , R12 , R22 , R23 , R41 , and R43 is an aliphatic group; each of R32 , R33 , and R42 is an aliphatic or aryl group or the like; each of R13 -R17 , R23 -R29 , R34 -R39 , and R44 -R49 is an H atom or an alkyl group or the like; and X11 , X21 , and X41 is an ion necessary to cancel charge in the molecule.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide light-sensitive material, and more particularly, to a silver halide color photographic light-sensitive material having an invisible light-sensitive silver halide emulsion layer having high sensitivity and low fog.

[0002]

2. Description of the Prior Art Since the release of Kodachrome by Eastman Kodak Company in 1935, various improvements have been made in color photography using silver halide color photographic light-sensitive materials, and the performance has been continuously improved. Improvements in the performance of color photographs include finer image structures, so-called graininess, sharpness, and color reproducibility. In the past, there have been several techniques for improving color reproducibility in the past, in which reproducibility has been dramatically improved. One of them is a colored coupler having an automatic mask function (described in U.S. Pat. No. 2,455,170).

[0003] Colored couplers are mainly used to improve the color reproducibility of negative films. Colored couplers have the effect of correcting unnecessary absorption of the three primary color dyes used in color films, yellow, magenta and cyan. With this colored coupler, unnecessary absorption of the coloring dyes of the color negative film can be corrected imagewise in the imagewise manner, and the color reproducibility can be greatly improved.

Further, more vivid color reproducibility is required,
Particularly in the case of a negative film, a development effect, a so-called multilayer effect, is proposed as a technique for improving color purity (Belgian Patent No. 710,34).
No. 4, German Patent No. 2,043,934).

Further, a DIR coupler (described in US Pat. No. 3,277,554) has been developed as an application of the multilayer effect. This DIR coupler greatly improved color purity reproducibility.

As described above, while aiming for higher color reproducibility, several techniques have been proposed for more faithfully reproducing colors as seen by humans. One of them is control of the spectral sensitivity distribution of a blue photosensitive layer, a green photosensitive layer, and a red photosensitive layer of a color film (described in JP-A-5-150411).

There have also been proposed some techniques for improving color reproducibility, focusing on the fact that the spectral sensitivity distribution of the cones of the human eye differs from the spectral sensitivity distribution of the color film. In general, the spectral sensitivity distribution of a color film is higher than that of the human eye in that the blue-sensitive layer has a maximum in sensitivity to long waves, the green-sensitive layer has a maximum in sensitivity to long waves, and the red-sensitive layer has considerable sensitivity. Has maximum sensitivity to long waves. The red cone of the human eye is 50
There is a region having a negative sensitivity near 0 nm. In this way, in order to match the spectral sensitivity distribution of the color film with the spectral sensitivity distribution of the human eye, it is possible to reproduce the spectral sensitivity distribution by the sensitizing dye and the so-called donor layer by skillfully controlling the layering effect. The difficult intermediate colors can be faithfully reproduced to some extent (Japanese Patent Laid-Open No. 61-3454).
No. 1).

With these techniques, the color reproducibility of the color film can reproduce the hue of the subject more faithfully.

As described above, the color reproducibility of color photographs has been steadily developed. However, it is a fact that next-generation silver halide color photographic light-sensitive materials are required to have a completely different dimension and to be further improved in color reproducibility.

As a new method for improving color reproduction in a silver halide color photographic light-sensitive material, there is a technique in which a non-visible light-sensitive silver halide emulsion layer is further provided on a usual red-sensitive layer, green-sensitive layer and blue-sensitive layer. It is proposed in Japanese Patent Application No. 9-179656. This patent utilizes the infrared light reflected from the chlorophyll of the plant, contains a magenta color coupler in the invisible light-sensitive silver halide emulsion layer, and significantly enhances the color reproducibility of the plant by imparting infrared sensitivity. An improved approach is described. To achieve this technique, a silver halide emulsion provided with high infrared sensitivity is required.

However, in general, infrared-sensitive dyes, unlike visible-sensitive dyes commonly used in the art, are difficult to achieve high sensitivity and low fog. This is because infrared-sensitive dyes have low adsorptivity to silver halide grains.Especially when color couplers, high concentrations of surfactants and organic solvents coexist, the dissolution of emulsions and the decrease in sensitivity and fog over time This is because it is easy to cause.

Accordingly, a silver halide emulsion which has high sensitivity and low fog even when sensitized with an infrared-sensitive dye is desired.

[0013]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a silver halide light-sensitive material having a non-visible light-sensitive silver halide emulsion layer having high sensitivity and low fog, and in particular, having a high sensitivity. It is an object of the present invention to provide a silver halide color photographic light-sensitive material having a non-visible light-sensitive silver halide emulsion layer having high sensitivity and low fog.

[0014]

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

1. The support has at least one red-sensitive silver halide emulsion layer containing a coupler, a green-sensitive silver halide emulsion layer containing a coupler and a blue-sensitive silver halide emulsion layer containing a coupler. And an invisible light-sensitive silver halide emulsion layer, wherein the invisible light-sensitive silver halide emulsion layer has the following general formulas [Ia] to [I-
d) a silver halide light-sensitive material comprising at least one compound represented by formula (d) and at least one image quality improver.

[0016]

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[In the general formulas [Ia] to [Id], Z ₁₁ , Z ₁₂ , Z ₂₁ , Z ₂₂ , Z ₃₁ , Z ₄₁ and Z ₄₂ are
Each represents a nonmetallic atom group necessary to complete a 5- or 6-membered monocyclic ring or a fused nitrogen-containing heterocyclic ring, and Q ₃₁ and Q
₃₂ and Q ₄₁ each represent an oxygen atom, a sulfur atom, a selenium atom or> NR, wherein R represents an alkyl group, an aryl group or a heterocyclic group. R ₁₁ , R ₁₂ , R ₂₁ , R ₂₂ ,
R _31, R ₄₁ and R _43, each represent an aliphatic group, R _32,
R ₃₃ and R ₄₂ each represent an aliphatic group, an aryl group or a heterocyclic group. _{R 13, R 14, R 15} , R 16, R 17, R 23, R
_{24, R 25, R 26,} R 27, R 28, R 29, R 34, R 35,
R ₃₆ , R ₃₇ , R ₃₈ , R ₃₉ , R ₄₄ , R ₄₅ , R ₄₆ , R ₄₇ , R
₄₈ and R ₄₉ each represent a hydrogen atom, an alkyl group, an alkoxy group, an aryloxy group, an aryl group, -N <W ₁ W ₂ ,
Represents -SR or a heterocyclic group. Here, R represents an alkyl group, an aryl group or a heterocyclic group, W ₁ and W ₂ each represent an alkyl group or an aryl group, and W ₁ and W ₂ are connected to each other to form a 5- or 6-membered group. A nitrogen heterocycle can also be formed. R ₁₁ and R _13, R ₁₄ and R _16, R ₁₇ and R _12, R ₂₁ and R _23, R ₂₄ and R _26, R ₂₅ and R _27, R ₂₆ and R _28, R ₂₂ and R
_29, R ₃₁ and R _34, R ₃₅ and R _37, R ₃₆ and R _38, R ₄₁ and R _44, R ₄₅ and R ₄₇ and R ₄₉ and R ₄₃ 5 membered linked to each other or 6-membered ring or a Condensed rings can be formed.
X ₁₁ , X ₂₁ and X ₄₁ each represent an ion required to cancel the charge in the molecule, and m ₁₁ , m ₂₁ and m ₄₁ each represent the number of ions required to cancel the charge in the molecule. n ₁₁ , n
_{12, n 21, n 22,} n 31, n 41 and n ₄₂ each represents 0 or _{1, l 31, l 32,} l 33, l 41, l 42 and l ₄₃ each 0
Or represents 1. However, when l ₄₂ is 0, l ₄₁ and l ₄₃ are numbers that become 0. ] 2. 2. The silver halide photosensitive material according to 1, wherein the compounds represented by the general formulas [Ia] to [Id] form a J-aggregate.

3. The general formula [Ia] or [I-
b) a compound represented by R ₁₄ and R ₁₆ , R ₂₄ and R
The silver halide photographic material according to 1 or 2, characterized in _{that 26} or R ₂₆ and R ₂₈ form a linked 5- or 6-membered ring.

4. The compound according to any one of claims 1 to 3, wherein the compound represented by the general formula [Ia] is a compound represented by the following general formula [Ie] or [If]. The silver halide photosensitive material as described in the above.

[0020]

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[General formula [Ie] and general formula [If]]
In the formula, Y ₅₁ , Y ₅₂ , Y ₆₁ and Y ₆₂ each represent an oxygen atom, a sulfur atom, a selenium atom or> NR, wherein R represents an alkyl group, an aryl group or a heterocyclic group. R ₅₁
And R ₅₂ each represents an aliphatic group, and R ₆₁ represents an aliphatic group or R
Represents a group of nonmetallic atoms necessary for bonding with ₆₅ to complete a 5- or 6-membered ring. Each R ₅₃ and R ₅₄ represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, R ₅₅ and R
₆₂ represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, a halogen atom, an alkoxy group, an alkylthio group, or an amino group, and R ₆₃ and R ₆₄ each represent a hydrogen atom, an alkyl group, or R ₆₃ and R ₆₄ Represents a group of nonmetallic atoms necessary to form a 5- or 6-membered ring by bonding between R ₆₅ represents a hydrogen atom or a bond to R ₆₁ . A _{51 to} A ₅₈ and A ₆₁ to
A ₆₈ represents a hydrogen atom or a substitutable group, and A _{51 to} A
_{54, A 55 ~A 58, A} 61 ~A 64, coupled between the A ₆₅ to A ₆₈ may form a ring. M ₅₁ and M ₆₁ each represent an ion required to cancel the charge in the molecule, and m ₅₁ and m ₆₁ each represent the number of ions required to cancel the charge in the molecule.
p represents 2 or 3. ] 5. In the compound represented by the general formula [Ie] or [If], at least one of A _{51 to} A ₅₈ and A _{61 to} A ₆₈ is a chlorine atom, or A ₅₁ and A ₅₂ , A ₅₂ and A _{52 53} ,
A ₅₃ and A _54, A ₅₅ and A _56, A ₅₆ and A _57, A ₅₇ and A ₅₈ and A ₆₁ and A _62, A ₆₂ and A _63, A ₆₃ and A _64, A ₆₅ and A _66, A
5. The silver halide light-sensitive material as described in any one of items 1 to 4, wherein at least one of ₆₆ and A ₆₇ and A ₆₇ and A ₆₈ are connected to each other to form a condensed naphthol ring.

6. 6. The silver halide photosensitive material according to any one of 1 to 5, wherein the photosensitive material contains at least two or more compounds selected from the compounds represented by formulas [Ia] to [If]. material.

Hereinafter, the present invention will be described in detail.

In the present invention, the invisible light-sensitive silver halide emulsion layer (invisible light-sensitive color reproduction improving layer) is a silver halide emulsion having a sensitivity maximum at a wavelength other than 400 to 680 nm of light in the visible region. Layer. The maximum photosensitive wavelength of the invisible light-sensitive silver halide emulsion layer is 690 nm to 850 nm.
m is preferable, and 730 nm to 780 n is more preferable.
m.

The coating position of the invisible light-sensitive silver halide emulsion layer is preferably farther from the exposure light source than the layer for forming a dye image for the purpose of improving image quality.

The image improver contained in the invisible light-sensitive silver halide emulsion layer refers to a compound which produces or releases a substance useful for improving image quality in an imagewise manner according to the amount of exposure. Those that form a dye image according to the exposure amount, such as colored couplers, DIR couplers, bleach accelerator releasing couplers, and development accelerator releasing couplers, form a dye image according to the exposure amount and color correction dyes, Development inhibitors, bleaching accelerators, those which produce a substance useful for improving the image quality such as a development accelerator in an imagewise manner, and furthermore, such as a development inhibitor without forming a dye image like a development inhibitor releasing compound A substance which generates a substance useful for improving the image quality in an imagewise manner can be used. Of these, couplers are preferred.

The compounds of the present invention represented by the general formulas [Ia] to [Id] (hereinafter referred to as general formulas [Ia] to [Id]]
Is also referred to as a sensitizing dye represented by
Band adsorption is preferred. The formation of J aggregates
W. E. FIG. Knapp, Chem. Phys. , 85,7
3 (1984); Kemnitz, K .; Yoshi
hara, T .; Tani, J .; Phys. Chem. ,
94, 3099 (1990). Further, as described in the same book, it can be confirmed from the difference (spectral shift) between the absorption wavelength of the sensitizing dye monomer and the absorption wavelength of the aggregate formed by adsorption to silver halide.

The compounds (sensitizing dyes) represented by formulas [Ia] to [Id] will be described.

In the above general formulas [Ia] to [Id], a 5- or 6-membered unit completed by Z ₁₁ , Z ₁₂ , Z ₂₁ , Z ₂₂ , Z ₃₁ , Z ₄₁ and Z ₄₂ is used. Examples of the ring or the condensed nitrogen-containing heterocyclic ring include benzothiazole, naphthothiazole, benzoselenazole, naphthoselenazole, quinoline, benzoxazole, naphthooxazole, phenanthrothiazole, thiadiazole, naphthopyridine and the like.

The aliphatic group represented by R ₁₁ , R ₁₂ , R ₂₁ , R ₂₂ , R ₃₁ , R ₄₁ and R ₄₃ includes, for example, a methyl group,
Ethyl group, propyl group, pentyl group, sulfopropyl group, hydroxyethyl group, phenethyl group, sulfobutyl group, diethylaminosulfopropyl group, methoxyethyl group, naphthoxyethyl group, carboxymethyl group, carboxyethyl group and other alkyl groups, propenyl group, etc. Alkenyl group.

An aliphatic group represented by R ₃₂ , R ₃₃ and R ₄₂ ;
Examples of the aryl group and the heterocyclic group include, for example, an alkyl group such as a methyl group, an ethyl group, and a carboxymethyl group; an alkenyl group such as a propenyl group; a phenyl group; a tolyl group;
Examples include an aryl group such as a naphthyl group, and a heterocyclic group such as a pyridyl group, a furyl group, and a thienyl group.

R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇ , R ₂₃ , R
_{24, R 25, R 26,} R 27, R 28, R 29, R 34, R 35,
R ₃₆ , R ₃₇ , R ₃₈ , R ₃₉ , R ₄₄ , R ₄₅ , R ₄₆ , R ₄₇ , R
₄₈ and the hydrogen atom represented by R _49, an alkyl group, an alkoxy group, an aryloxy group, an aryl group, -N <W ₁ W _2,
Examples of -SR or a heterocyclic group include a hydrogen atom, an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group and a benzyl group, an alkoxy group such as a methoxy group and an ethoxy group, a phenoxy group, and a p-methylphenoxy group. an aryloxy group such as a group, aryl groups such as phenyl and tolyl group, a diethylamino group, an anilino group, a piperidino group, -N such furyl amino group <W ₁ W ₂ group, methylthio group, phenylthio group, such as thienylthio group And heterocyclic groups such as —SR group, thienyl group and furyl group.

Examples of the alkyl group, aryl group and heterocyclic group represented by R in the NR group and -SR group include, for example, methyl group, ethyl group, carboxymethyl group, phenyl group, tolyl group, pyridyl group , A furyl group, a thienyl group and the like.

R ₁₁ and R ₁₃ , R ₁₄ and R ₁₆ , R ₁₇ and R ₁₂ , R
₂₁ and R ₂₃ , R ₂₄ and R ₂₆ , R ₂₅ and R ₂₇ , R ₂₆ and R ₂₈ , R ₂₂
And R ₂₉ , R ₃₁ and R ₃₄ , R ₃₅ and R ₃₇ , R ₃₆ and R ₃₈ , R ₄₁ and R ₄₄ , R ₄₅ and R _47, R ₄₉ and R _43, and a 5-membered or 6-membered bond formed. Examples of the membered ring or its condensed ring include cyclohexene, cyclopentene, cyclohexecyclohexene, pyrroline, 1,2,3,4-tetrahydropyridine, piperidine and the like.

The ions represented by X ₁₁ , X ₂₁ and X ₄₁ include F ⁻ , Cl ⁻ , Br ⁻ , I ⁻ , BF ₄ ⁻ , ClO ₄ ⁻ , P
F ₆ ^- other, trifluoromethanesulfonate ion, p-
Toluenesulfonate ion and the like can be mentioned.

In the compounds (sensitizing dyes) represented by the general formulas [Ia] to [Id], the compounds represented by the general formulas [Ie] and [If] (sensitized dyes) Dye) is more preferably used.

The compounds (sensitizing dyes) represented by the general formulas [Ie] and [If] will be described.

The general formula [Ie] and the general formula [I-
f), examples of the alkyl group, aryl group and heterocyclic group represented by R include those represented by the general formulas [Ia] to [I-
In d), the same as the examples of the alkyl group, the aryl group and the heterocyclic group represented by R can be mentioned.

Examples of the aliphatic group represented by R ₅₁ R ₅₂ and R ₆₁ are the same as the examples of the aliphatic group represented by R ₁₁ in the general formula [Ia].

[0040] Examples of 5-membered ring or 6-membered and R ₆₁ and R ₆₅ is completed bonded to are the compounds of formula [I-a] R ₁₁
The same thing can be mentioned as examples of the ring and R ₁₃ is completed combines with.

Among the hydrogen atoms, alkyl groups, aryl groups and heterocyclic groups represented by R ₅₃ and R ₅₄ , examples of the alkyl group, aryl group and heterocyclic group include those represented by the general formula [I-
Examples of the alkyl group, the aryl group and the heterocyclic group represented by R ₁₃ in a) are the same as those described above.

Of the hydrogen atom, alkyl group, aryl group, heterocyclic group, halogen atom, alkoxy group, alkylthio group and amino group represented by R ₅₅ and R ₆₂ , alkyl group, aryl group, heterocyclic group, alkoxy group Examples of the group, alkylthio group and amino group include the same as the examples of the alkyl group, aryl group, heterocyclic group, alkoxy group, alkylthio group and amino group represented by R ₁₃ in the general formula [Ia]. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

Among the hydrogen atoms and alkyl groups represented by R ₆₃ and R ₆₄ , examples of the alkyl group include those represented by the general formula [Ia]
And the same as the examples of the alkyl group represented by R ₁₃ in the above.

Examples of the 5- or 6-membered ring formed by bonding between R ₆₃ and R ₆₄ include R 5 in the general formula [Ia].
_The same examples of the ring formed by bonding between ₁₄ and R ₁₆ can be mentioned.

Among the hydrogen atoms or the substitutable groups represented by A _{51 to} A ₅₈ and A _{61 to} A ₆₈ , the substitutable groups include a halogen atom such as a chlorine atom, a bromine atom and an iodine atom, and a methyl group. And alkyl groups such as ethyl group, butyl group, trifluoromethyl group and isopropyl group, alkoxy groups such as methoxy group, aryl groups such as phenyl group and tolyl group, and carboxyl group.

A _{51 to} A ₅₄ , A _{55 to} A ₅₈ , A _{61 to} A ₆₄ , A
The ring formed by bond between the ₆₅ to A _68, benzene, 2H-1,3-dioxole and the like.

Examples of the ions represented by M ₅₁ and M ₆₁ are the same as the examples of X _{11 in} the general formula [Ia].

In the compound (sensitizing dye) represented by the general formula [Ie] or [If], at least one of A _{51 to} A ₅₈ and A _{61 to} A ₆₈ is a chlorine atom or A ₅₁
And A _52, A ₅₂ and A _53, A ₅₃ and A _54, A ₅₅ and A _56, A ₅₆ and A _57, A ₅₇ and A ₅₈ and A ₆₁ and A _62, A ₆₂ and A _63, A ₆₃ and A ₆₄ , A ₆₅ and A ₆₆ , A ₆₆ and A ₆₇ , and A ₆₇ and A ₆₈ are preferably linked to each other to form a condensed naphthol ring.

The following formulas [Ia] to [I-
f]], the present invention is not limited to these compounds (sensitizing dyes) (the general formulas [Ia] and [Ib] Specific examples of the compound (sensitizing dye) represented by
No. 289, Compounds A-1 to A-14, B1 to B25 and Chemical No. The compound described as 13 can be mentioned. ).

[0050]

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[0051]

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[0052]

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[0053]

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[0054]

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[0055]

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[0056]

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[0057]

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[0058]

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[0059]

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[0060]

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[0061]

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[0062]

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[0063]

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[0064]

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[0065]

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[0066]

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[0067]

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[0068]

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[0069]

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[0070]

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[0071]

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[0072]

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[0073]

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The above-mentioned infrared-sensitive sensitizing dyes are described, for example, in FM Chemer, The Chemistry
f Heterocyclic Compounds No. 1
8, The Cyanine Dyes and R
elite Compounds (A. Weish
erger ed. Published by Interscience, N
ew York 1964).

The sensitizing dye of the present invention may be used alone, but it is desirable to use two or more sensitizing dyes in combination. As the combination of the sensitizing dyes, two or more dyes may be selected from a dye that adsorbs the J band and a dye that does not adsorb the J band, or a dye that adsorbs the J band and a dye that does not adsorb the J band may be used.

When the sensitizing dyes of the present invention are used alone or in combination, the total amount is preferably 1 × 10 ⁻⁶ mol to 5 × 10 ⁻³ mol, more preferably 1 mol / mol of silver halide. Is contained in the silver halide emulsion at a ratio of 1 × 10 ⁻⁵ mol to 2.5 × 10 ⁻³ mol, particularly preferably 4 × 10 ⁻⁵ mol to 1 × 10 ⁻³ mol.

When two or more sensitizing dyes are used in combination in the present invention, the sensitizing dyes can be contained in the silver halide emulsion in any ratio.

The sensitizing dye of the present invention can be directly dispersed in an emulsion. These may be first dissolved in an appropriate solvent, for example, methyl alcohol, ethyl alcohol, n-propanol, methyl cellosolve, acetone, water, pyridine or a mixed solvent thereof, and added to the emulsion in the form of a solution. it can. Ultrasound can also be used for lysis. Further, as a method for adding the sensitizing dye, as described in US Pat. No. 3,469,987,
Dissolving a dye in a volatile organic solvent, dispersing the solution in a hydrophilic colloid, and adding the dispersion to an emulsion;
As described in JP-B-46-24185, the water-insoluble dye is dispersed in a water-soluble solvent without dissolving,
A method of adding this dispersion to an emulsion; US Pat. No. 3,82
No. 2,135, a method in which a dye is dissolved in a surfactant and the solution is added to an emulsion;
No. 624, a method of dissolving with a compound that shifts to a longer wavelength side and adding the solution to an emulsion; a dye containing substantially water as described in JP-A-50-80826. For example, a method of dissolving in a non-acidic acid and adding the solution to the emulsion is preferably used. Other additions to emulsions include U.S. Pat. Nos. 2,912,343 and 3,34.
No. 2,605, No. 2,996,287, No. 3,4
The method described in JP-A-29,835 or the like is used. The sensitizing dye may be dispersed uniformly in the silver halide emulsion before it is coated on a suitable support, but may be dispersed in any step of the preparation of the silver halide emulsion.

When two or more sensitizing dyes of the present invention are used in combination, the sensitizing dyes can be dispersed in a silver halide emulsion independently or in advance by mixing them in advance by the method described above.

In addition to the sensitizing dye of the present invention, a dye having absorption in the visible region for the purpose of supersensitization, a dye having no spectral sensitizing effect by itself, or a substance which does not substantially absorb visible light. A substance exhibiting supersensitization may be contained in the emulsion. Useful sensitizing dyes, combinations of dyes exhibiting supersensitization and substances exhibiting supersensitization are described in Research Disclosure 176.
Volume 17643 (Issued December 1978) Page 23 IV J
Item, or JP-B-49-25500, 43-493
No. 3, JP-A-59-19032 and JP-A-59-19224.
No. 2, JP-A-3-15049, JP-A-62-1234
No. 54.

In the present invention, the couplers contained in the red, green, and blue light-sensitive silver halide emulsion layers preferably have a spectral absorption maximum of a coloring dye formed from the coupler contained therein at least 20 nm away. Further, it is preferable to use a yellow coupler, a magenta coupler, and a cyan coupler.As the combination of the emulsion layer and the coupler, a yellow coupler and a blue photosensitive layer, a magenta coupler and a green photosensitive layer, and a cyan coupler and a red photosensitive layer are used. It is not limited, and other combinations may be used.

DIR that can be used in the present invention
Specific examples of the compound include, for example, JP-A-4-11415.
D-1 to D-34 described in the specification of JP-A No. 3 can be mentioned, and these compounds can be preferably used in the present invention.

Specific examples of the diffusible DIR compound which can be used in the present invention are, for example, US Pat. Nos. 4,234,678, 3,227,554, 3,647,291, and 3 958,993, 4,419,886, 3,933,500, JP-A-57-56837, JP-A-51-1239, U.S. Pat. Nos. 2,072,363, 2,070, No. 266, Research Disclosure, December 212, 1981
No. 28 and the like.

In the present invention, Research Disclosure No. 1 may be used as the silver halide emulsion. 30811
9 (hereinafter abbreviated as RD308119) can be used.

The following shows the places to be described.

[Items] [Page RD308119] Iodine composition 993 IA Section Manufacturing method 993 IA and 994 E Crystal wall Normal crystal 999 IA Twin crystal 933 IA Section Epitaxial 933 IA Section A Halogen composition uniform 993 IB Section Not uniform 993 IB Section Halogen conversion 994 IC Halogen substitution 994 IC Section Metal content 994 ID Monodispersion 990 IF Section Solvent addition 996 Item IF Latent image formation position Surface 995 I-G Inside 995 I-G Applicable photosensitive material negative 995 I-H Positive (including internal fog particles) 995 I-H Item Emulsion mixed 995 I- Section J Desalting 995 II-A In the present invention, a silver halide emulsion which has been subjected to physical ripening, chemical ripening and spectral sensitization is used. Additives used in such a process are described in Research Disclosure No. 17643, no. 18716 and no. 3
08119 (hereinafter RD17643, RD18, respectively)
716 and RD308119). The places to be described are shown below.

[Item] [Page RD308119] [RD17643] [RD18716] Chemical sensitizer 996 III-A section 23 648 Spectral sensitizer 996 IV-AA, B, C, D, 23-24 648- 649 H, I, J section Supersensitizer 996 IV-AE, J section 23 to 24 648 to 649 Antifoggant 998 VI 24 to 25 649 Stabilizer 998 VI 24 to 25 649 Known methods usable in the present invention Are also described in Research Disclosure, supra. The relevant sections are described below.

[Item] [Page RD308119] [RD17643] [RD18716] Anti-turbidity agent 1002 VII-I 25 650 Dye image stabilizer 1001 VII-J 25 Brightener 998 V 24 UV absorber 1003 VIII- Section I, XIII-C Section 25-26 Light absorber 1003 VIII 25-26 Light scattering agent 1003 VIII Filter dye 1003 VIII 25-26 Binder 1003 IX 26 651 Static inhibitor 1006 XIII 27 650 Hardener 1004 X 26 651 Plasticizer 1006 XII 27 650 Lubricant 1006 XII 27 650 Activator / Coating aid 1005 XI 26-27 650 Matting agent 1007 XVI Developer (contained in light-sensitive material) 1001 XXB The present invention may be used by adding various couplers. The example of the research It is listed on the closure. The relevant sections are described below.

[Item] [Page RD308119] [RD17643] Yellow coupler 1001 VII-D Section VIIC-G Magenta coupler 1001 VII-D VIIC-G Cyan coupler 1001 VII-D VIIC-G Colored coupler 1002 VII-G Section VIIG DIR coupler 1001 VII-F Section VIIF BAR coupler 1002 VII-F Other useful residue release 1001 VII-F Coupler Alkali-soluble coupler 1001 VII-E Additives used in the present invention are described in RD308119XIV It can be added by a dispersion method or the like.

In the present invention, the aforementioned RD17643
Page 28, RD18716 pages 647 to 648, and RD3
The support described in XIX of 08119 can be used.

The light-sensitive material of the present invention includes the aforementioned RD3081
An auxiliary layer such as a filter layer or an intermediate layer described in the section 19VII-K can be provided.

The light-sensitive material of the present invention can be obtained by using the above-mentioned RD30811.
Various layer configurations such as a normal layer, a reverse layer, and a unit configuration described in section 9VII-K can be employed.

To develop the silver halide color light-sensitive material of the present invention, for example, T.I. H. James, Theory of the Photographic Process 4th Edition (T
he Theory of The Photograph
ic Process Forth Edition)
Pages 291-334 and Journal of the American Chemical Society (Journal of the American Chemical Society)
the American Chemical So
city), vol. 73, p. 3, 100 (1951), a developer known per se can be used, and the aforementioned RD17643, pages 28 to 29,
Development can be carried out by a usual method described in RD18716, page 615 and RD308119XIX.

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

Example 1 << Preparation of Multilayer Color Photosensitive Material / Sample 101 >> The following composition was coated on a cellulose triacetate film support provided with an undercoat layer, and a multilayer color photosensitive material, Sample 10
1 was produced.

In all of the following examples, the addition amount in the silver halide photographic light-sensitive material was 1 m ² unless otherwise specified.
Indicates the number of grams per unit. Silver halide and colloidal silver were expressed in terms of silver, and sensitizing dyes were expressed in moles per mole of silver halide.

First layer: Antihalation layer Black colloidal silver 0.18 Ultraviolet absorber (UV-1) 0.30 High boiling organic solvent (Oil-2) 0.17 Gelatin 1.59 Second layer: Intermediate layer High Boiling point organic solvent (Oil-2) 0.01 Gelatin 1.27 Third layer: Invisible photosensitive layer Silver iodobromide emulsion E 0.15 Silver iodobromide emulsion G 0.70 Sensitizing dye (DYE-1) 2.0 × 10 ^-4 magenta coupler (M-1) 0.20 High boiling point solvent (Oil-1) 0.34 Gelatin 0.90 Fourth layer: low-sensitivity red-sensitive layer Silver iodobromide emulsion A 0.80 Sensitizing dye (SD-1) 5.0 × 10 ^-5 sensitizing dye (SD-2) 9.0 × 10 ^-5 sensitizing dye (SD-3) 1.9 × 10 ^-5 sensitizing dye (SD -4) 2.0 × 10 ^-4 sensitizing dye (SD-5) 2.8 × 10 ^-4 cyan coupler (C-1) 0.42 color Dosian coupler (CC-1) 0.02 High boiling point solvent (Oil-1) 0.35 Gelatin 1.02 Fifth layer: Medium sensitivity red-sensitive layer Silver iodobromide emulsion E 0.40 Sensitizing dye (SD- 3) 1.8 × 10 ^-5 sensitizing dye (SD-4) 2.4 × 10 ^-4 sensitizing dye (SD-5) 4.5 × 10 ^-4 cyan coupler (C-1) 0.26 colored Cyan coupler (CC-1) 0.05 DIR compound (D-1) 0.01 High boiling solvent (Oil-1) 0.31 Gelatin 0.78 6th layer: Highly sensitive red-sensitive layer Silver iodobromide emulsion G 1.51 sensitizing dye (SD-3) 1.8 × 10 ^-5 sensitizing dye (SD-4) 3.1 × 10 ^-4 sensitizing dye (SD-5) 2.7 × 10 ^-4 cyan coupler (C-2) 0.11 Colored cyan coupler (CC-1) 0.02 DIR compound (D-2) 0.04 High boiling point solvent (Oi 1-1) 0.17 Gelatin 1.15 7th layer: Intermediate layer Yellow coupler (Y-1) 0.02 Yellow coupler (Y-2) 0.06 High boiling organic solvent (Oil-2) 0.02 High Boiling point organic solvent (Oil-1) 0.17 Gelatin 0.69 Eighth layer: Intermediate layer Gelatin 0.80 Ninth layer: Low-sensitive green-sensitive layer Silver iodobromide emulsion B 0.21 Sensitizing dye (SD-1) ) 5.9 × 10 ^-5 sensitizing dye (SD-6) 3.1 × 10 ^-4 sensitizing dye (SD-9) 1.8 × 10 ^-4 sensitizing dye (SD-11) 5.6 × 10 ^-5 Magenta coupler (M-1) 0.20 Colored magenta coupler (CM-1) 0.05 DIR compound (D-1) 0.02 High boiling organic solvent (Oil-2) 0.27 Gelatin 1.34 10th layer: middle-sensitive green-sensitive layer silver iodobromide emulsion E 0.82 sensitizing dye (SD-1) 5 0 × 10 ^-5 Sensitizing dye (SD-6) 2.7 × 10 -4 Sensitizing dye (SD-9) 1.7 × 10 -4 Sensitizing dye (SD-11) 4.8 × 10 -5 Magenta coupler (M-1) 0.21 Colored magenta coupler (CM-1) 0.05 DIR compound (D-4) 0.02 High boiling organic solvent (Oil-2) 0.33 Gelatin 0.89 Eleventh layer : High-sensitivity green-sensitive layer silver iodobromide emulsion D 0.99 sensitizing dye (SD-6) 3.6 × 10 ^-4 sensitizing dye (SD-7) 7.0 × 10 ^-5 sensitizing dye (SD -8) 4.8 × 10 ^-5 sensitizing dye (SD-11) 6.2 × 10 ^-5 magenta coupler (M-1) 0.05 magenta coupler (M-2) 0.06 Colored magenta coupler (CM) -2) 0.03 High boiling organic solvent (Oil-2) 0.25 Gelatin 0.88 12th layer: Intermediate layer High boiling organic solvent (Oil-1) 0.25 gelatin 0.50 13th layer: yellow filter layer yellow colloidal silver 0.11 color stain inhibitor (SC-1) 0.12 high boiling solvent (Oil-2) 0.16 gelatin 1 0.000 14th layer: Intermediate layer Gelatin 0.36 15th layer: Low-sensitivity blue-sensitive layer Silver iodobromide emulsion B 0.37 Sensitizing dye (SD-10) 5.6 × 10 ^-4 sensitizing dye (SD -11) 2.0 × 10 ^-4 sensitizing dye (SD-13) 9.8 × 10 ^-5 Yellow coupler (Y-1) 0.39 Yellow coupler (Y-2) 0.14 DIR compound (D- 5) 0.03 High boiling organic solvent (Oil-2) 0.11 Gelatin 1.02 Sixteenth layer: Medium-sensitivity blue-sensitive layer Silver iodobromide emulsion D 0.46 Silver iodobromide emulsion F 0.10 Sensitization dye (SD-10) 5.3 × 10 -4 sensitizing dye (SD-11) 1. × 10 ^-4 Sensitizing dye (SD-13) 1.1 × 10 -5 Yellow coupler (Y-1) 0.28 Yellow coupler (Y-2) 0.10 DIR compound (D-5) 0.05 High Boiling organic solvent (Oil-2) 0.08 Gelatin 1.12.

17th layer: Highly sensitive blue-sensitive layer Silver iodobromide emulsion D 0.04 Silver iodobromide emulsion G 0.28 Sensitizing dye (SD-11) 8.4 × 10 ^-5 sensitizing dye (SD -12) 2.3 × 10 ^-4 Yellow coupler (Y-1) 0.04 Yellow coupler (Y-2) 0.12 High boiling organic solvent (Oil-2) 0.03 Gelatin 0.85 18th layer: First protective layer Silver iodobromide emulsion (average particle size 0.04 µm, silver iodide content 4.0 mol%) 0.30 UV absorber (UV-2) 0.03 UV absorber (UV-3) 0.015 UV absorber (UV-4) 0.015 UV absorber (UV-5) 0.015 UV absorber (UV-6) 0.10 High boiling organic solvent (Oil-1) 0.44 High boiling point Organic solvent (Oil-3) 0.07 Gelatin 1.35 19th layer: Second protective layer Alkali Soluble matting agent (average particle size: 2 μm) 0.15 Polymethyl methacrylate (average particle size: 3 μm) 0.04 Slip agent (WAX-1) 0.02 Gelatin 0.54 In addition to the above composition, compound SU-1 , SU-2, SU
-3, SU-4, viscosity modifier V-1, hardener H-1, H
-2, stabilizer ST-1, antifoggant AF-1, AF-
2. Two kinds of AF-3 having a weight average molecular weight of 10,000 and a weight average molecular weight of 1,100,000, dye AI-
1, AI-2, AI-3, compounds FS-1, FS-2,
The preservative DI-1 was appropriately added to each layer.

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The emulsions used in the above samples are as follows. The average particle size is shown as a particle size converted into a cube. Each emulsion was optimally subjected to gold, sulfur, and selenium sensitization.

Emulsion name Average AgI content Average particle size Crystal habit Diameter / thickness ratio (mol%) (μm) Silver iodobromide emulsion A 2.0 0.32 Normal crystal 1.0 Silver iodobromide emulsion B 0 0.42 Twin flat plate 4.0 Silver iodobromide emulsion D 8.0 0.70 Twin flat plate 5.0 Silver iodobromide emulsion E 6.0 0.60 Twin flat plate 4.0 Silver iodobromide Emulsion F 2.0 0.42 Twin flat plate 4.0 Silver iodobromide emulsion G 8.0 0.90 Twin flat plate 3.0 Silver iodobromide emulsions A, B and F contain iridium at 1 × 10 ^−7. mo
It contains 1/1 molAg.

<< Preparation of Samples 102 to 135 >> Sample 1
Samples 102 to 102 were prepared in exactly the same manner as Sample 101 except that the sensitizing dye DYE-1 (Comparative sensitizing dye) used in the third layer of Sample No. 01 was replaced with an equimolar sensitizing dye shown in Table 1. 13
5 was produced.

<Evaluation Method><Evaluation of Relative Sensitivity, Fog, and Spectrum Shift of Color Negative> Each of the obtained photosensitive material samples 101 to 135 was evaluated as 1
Cut to 35 standards, Kodak Wratten Filter 89B
Was used to perform 1/100 second infrared exposure, color development treatment (CNK-4 manufactured by Konica), and drying to obtain a sample for evaluation. Each of the obtained evaluation samples was evaluated for relative sensitivity, fog, and spectrum shift as described below.

<< Fog Density >> The fog density was determined by Konica P
Table 1 shows the values of the green light transmission density obtained using the D transmission densitometer as fog density.

<< Relative Sensitivity >> The relative sensitivity is defined as fog density + 0.
It is a relative value of the reciprocal of the exposure amount that gives a density of 15 and is shown in Table 1 with the sensitivity of sample 105 being 100.

<< Adsorption Shape (Monomer Adsorption, J Aggregate Adsorption) >> First, a spectrum shift (Δλ) is obtained by the following equation.

Δλ = (maximum absorption wavelength of dye in coating film) −
(Maximum Absorption Wavelength of Dye Solution (ie, Dye Monomer))
The absorption waveform at 690 to 850 nm for each of No. 5 was measured using a Hitachi UV2200 integrating sphere spectrophotometer, and the wavelength showing the maximum absorbance was defined as the maximum absorption wavelength of the dye in the coating film.

The absorption maximum wavelength of the dye solution was as follows:
The dyes used in Sample 135 (described in Table 1) were each dissolved in methanol, and the absorption waveform at 400 to 850 nm was measured using a Hitachi UV2200 integrating sphere spectrophotometer. The maximum absorption wavelength of the dye was used.

. When Δλ <70 nm, the dye is evaluated as having adsorbed monomer, and when Δλ ≧ 70 nm,
It was evaluated that a J-aggregate was formed and adsorbed.

Table 1 shows the above results.

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[Table 1]

*: The usage ratio is a molar ratio.

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As is evident from Table 1, the silver halide photographic light-sensitive material obtained according to the present invention has significantly improved relative sensitivity without significantly increasing fog, and shows excellent performance.

[0127]

According to the present invention, there is provided a non-visible light-sensitive material having a high sensitivity and low fog and also a non-visible light-sensitive silver halide emulsion layer, particularly a non-visible light sensitive material having high sensitivity and low fog. Thus, a silver halide color photographic light-sensitive material having a neutral silver halide emulsion layer could be provided.

Claims (6)

[Claims] 1. A coupler comprising at least one red-sensitive silver halide emulsion layer containing a coupler, a green-sensitive silver halide emulsion layer containing a coupler and a blue-sensitive halide containing a coupler. Having a silver emulsion layer, and having an invisible light-sensitive silver halide emulsion layer, wherein the invisible light-sensitive silver halide emulsion layer has the following general formulas [Ia] to [Id]
A silver halide light-sensitive material comprising at least one compound represented by formula (I) and at least one image quality improver. Embedded image [In the general formulas [Ia] to [Id], Z ₁₁ ,
Z ₁₂ , Z ₂₁ , Z ₂₂ , Z ₃₁ , Z ₄₁ and Z ₄₂ each represent a non-metallic atom group necessary to complete a 5- or 6-membered monocyclic ring or a fused nitrogen-containing heterocyclic ring thereof; Q _31, Q ₃₂ and Q ₄₁
Is an oxygen atom, a sulfur atom, a selenium atom or> N-
Represents R, wherein R represents an alkyl group, an aryl group, or a heterocyclic group. R ₁₁ , R ₁₂ , R ₂₁ , R ₂₂ , R ₃₁ , R ₄₁ and R ₄₃ each represent an aliphatic group, and R ₃₂ , R ₃₃ and R
₄₂ represents an aliphatic group, an aryl group or a heterocyclic group, respectively. _{R 13, R 14, R 15} , R 16, R 17, R 23, R 24,
R ₂₅ , R ₂₆ , R ₂₇ , R ₂₈ , R ₂₉ , R ₃₄ , R ₃₅ , R ₃₆ , R
₃₇ , _R38 , _R39 , _R44 , _R45 , _R46 , _R47 , _R48 and R
₄₉ represents a hydrogen atom, an alkyl group, an alkoxy group, an aryloxy group, an aryl group, —N <W ₁ W ₂ , —SR or a heterocyclic group, respectively. Here, R represents an alkyl group, an aryl group or a heterocyclic group, W ₁ and W ₂ each represent an alkyl group or an aryl group, and W ₁ and W ₂ are connected to each other to form a 5- or 6-membered group. A nitrogen heterocycle can also be formed. R ₁₁ and R _13, R ₁₄ and R _16, R ₁₇ and R _12, R ₂₁ and R _23, R ₂₄ and R
_26, R ₂₅ and R _27, R ₂₆ and R _28, R ₂₂ and R _29, R ₃₁ and R _34, R ₃₅ and R _37, R ₃₆ and R _38, R ₄₁ and R _44, R ₄₅ and R
₄₇ and R ₄₉ and R ₄₃ can be linked together to form a 5- or 6-membered ring or a fused ring thereof. X ₁₁ , X ₂₁ and X ₄₁ each represent an ion necessary to cancel the charge in the molecule, and m ₁₁ , m ₂₁ and m ₄₁ each represent the number of ions required to cancel the charge in the molecule. n ₁₁ , n ₁₂ , n ₂₁ ,
n ₂₂ , n ₃₁ , n ₄₁ and n ₄₂ each represent 0 or 1,
l ₃₁ , l ₃₂ , l ₃₃ , l ₄₁ , l ₄₂ and l ₄₃ are each 0 or 1
Represents However l ₄₁ and l ₄₃ when l ₄₂ is 0 is a number zero. ] 2. The silver halide photosensitive material according to claim 1, wherein the compounds represented by the general formulas [Ia] to [Id] form a J-aggregate. 3. The compound represented by the formula [Ia] or [Ib]
Wherein R ₁₄ and R ₁₆ , R ₂₄ and R ₂₆ or R ₂₆ and R ₂₈ are linked to each other to form a 5- or 6-membered ring. The silver halide photosensitive material as described in the above. 4. The compound represented by the general formula [Ia] is a compound represented by the following general formula [Ie] or [If]. 4. The silver halide light-sensitive material according to any one of the above items 3. Embedded image [In the general formula [Ie] and the general formula [If], Y
₅₁ , Y ₅₂ , Y ₆₁ and Y ₆₂ each represent an oxygen atom, a sulfur atom,
Represents a selenium atom or> NR, wherein R represents an alkyl group, an aryl group or a heterocyclic group. R ₅₁ and R ₅₂ each represent an aliphatic group, and R ₆₁ represents a non-metallic atomic group necessary for bonding to the aliphatic group or R ₆₅ to complete a 5- or 6-membered ring. R ₅₃ and R ₅₄ each represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and R ₅₅ and R ₆₂ each represent a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, a halogen atom, an alkoxy group, R ₆₃ and R ₆₄ represent a hydrogen atom, an alkyl group or R
Represents a group of non-metallic atoms necessary for bonding between ₆₃ and R ₆₄ to form a 5- or 6-membered ring. R ₆₅ is a hydrogen atom or R ₆₁
Represents a bond with A _{51 to} A ₅₈ and A _{61 to} A ₆₈ each represent a hydrogen atom or a substitutable group, and A _{51 to} A ₅₄ and A _{55 to} A
₅₈ , A _{61 to} A ₆₄ , and A _{65 to} A ₆₈ may combine to form a ring. M ₅₁ and M ₆₁ each represent an ion required to cancel the charge in the molecule, and m ₅₁ and m ₆₁ each represent the number of ions required to cancel the charge in the molecule. p is 2 or 3
Represents ] 5. The formula [Ie] or [If]
In the compound represented by the formula, A _{51 to} A ₅₈ and A _{61 to} A ₆₈
At least one of which is a chlorine atom, or A ₅₁ and A ₅₂ , A
₅₂ and A ₅₃ , A ₅₃ and A ₅₄ , A ₅₅ and A ₅₆ , A ₅₆ and A ₅₇ , A ₅₇
And A ₅₈ and A ₆₁ and A _62, A ₆₂ and A _63, A ₆₃ and A _64, A ₆₅
And at least one of A ₆₆ and A ₆₆ , A ₆₆ and A ₆₇ , and A ₆₇ and A ₆₈ are linked together to form a fused naphthol ring. Silver halide photosensitive material. 6. The method according to claim 1, comprising at least two compounds selected from the compounds represented by the general formulas [Ia] to [If].
Item.