JPH11315217A - Methine compound and silver halide photosensitive material containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel disulfide-group-containing methine compound which can give a highly sensitive silver halide photographic material. SOLUTION: The methine compound is exemplified by a streptocyanine pigment, a cyanine pigment, a hemicyanine pigment, a merocyanine pigment, a rhodacyanine pigment, a trinuclear merocyanine pigment, an oxonol pigment, a hemioxonol pigment, an allopolar pigment, a styryl pigment, or a cyanine base. It is desirably a hemicyanine pigment, a cyanine pigment, a merocyanine pigment, or an oxonol pigment, and is particularly desirably a hemicyanine pigment. It may be bonded pigment composed of least two covalently bonded chromophores. It is exemplified by a compound of the formula (wherein Z1 is a five- or six-membered nitrogen-containing heterocyclic ring; A is a bonding group; R1 is an alkyl; R2 and R3 are each an alkyl, an aryl, or a heterocyclic ring; L1 to L4 are each (substituted) methine; p1 is 0 or 1; and M1 is a charge- neutralizing ion).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a silver halide light-sensitive material containing a novel methine compound and a novel compound.

[0002]

2. Description of the Related Art Methine compounds have been conventionally used as sensitizing dyes for silver halide photographic light-sensitive materials. However, their photographic sensitivity is low due to their low adsorption power to silver halide grains, and they may not be suitable for practical use. The improvement was desired.

[0003]

Accordingly, an object of the present invention is to provide a high-sensitivity silver halide light-sensitive material containing a novel methine compound.

[0004]

The above objects of the present invention have been attained by the following means. (1) A methine compound containing a disulfide group. However, this methine compound excludes a cyanine dye. (2) A cyanine dye (methine compound), wherein a substituent containing a disulfide group is substituted on a nitrogen atom of a nitrogen-containing heterocyclic ring. (3) A hemicyanine dye, which contains a disulfide group among the compounds described in (1). (4) Among the compounds described in (1), a compound represented by the general formula (1). General formula (1)

[0005]

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In the formula, Z1 represents a 5- or 6-membered nitrogen-containing heterocyclic ring. However, this heterocyclic ring may be further condensed. A represents a divalent linking group. R1 represents an alkyl group. R2 and R3 each represent an alkyl group, an aryl group or a heterocyclic group, and R2 and R3 may form a ring. L1, L2, L3 and L4 each represent an optionally substituted methine group. n1 represents 0, 1, 2, 3 or 4. p1 represents 0 or 1. M1 represents a charge neutralizing ion. m1 represents the number required to neutralize the charge. (5) A merocyanine dye containing a disulfide group, among the compounds described in (1). (6) An oxonol dye, which contains a disulfide group among the compounds described in (1). (7) A silver halide photosensitive material comprising the methine compound according to (1) or (2). (8) A silver halide photosensitive material comprising a compound represented by the general formula (1) described in (4).

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the methine compound of the present invention will be described in detail. Examples of the methine compound include streptocyanine dyes, cyanine dyes, hemicyanine dyes, merocyanine dyes, rhodacyanine dyes, trinuclear merocyanine dyes, oxonol dyes, hemioxonol dyes, allopolar dyes, styryl dyes, and cyanine bases.

The cyanine dye represents a chromophore represented by the following general formula (2). General formula (2)

[0009]

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In the formula, Z2 and Z3 each represent a 5- or 6-membered nitrogen-containing heterocyclic ring. However, this heterocyclic ring may be further condensed. R4 and R5 each represent an alkyl group. However, at least one of R4 and R5 represents an alkyl group containing a disulfide group. L5, L6, L7, L8,
L9, L10 and L11 each represent an optionally substituted methine group. n2 represents 0, 1, 2, 3 or 4. p2
And p3 represent 0 or 1. M2 represents a charge neutralizing ion. m2 represents the number necessary to neutralize the charge.

The hemicyanine dye represents a chromophore represented by the following general formula (3). General formula (3)

[0012]

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In the formula, Z4 represents a 5- or 6-membered nitrogen-containing heterocyclic ring. However, this heterocyclic ring may be further condensed. R6 represents an alkyl group. R7 and R8 each represent an alkyl group, an aryl group or a heterocyclic group;
And R8 may form a ring. L12, L13, L14
And L15 each represent an optionally substituted methine group. n
3 represents 0, 1, 2, 3 or 4. p4 is 0 or 1
Represents M3 represents a charge neutralizing ion. m3 represents the number required to neutralize the charge.

The merocyanine dye represents a chromophore represented by the following general formula (4). General formula (4)

[0015]

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In the formula, R9 and R10 represent an atom group necessary for forming a basic nucleus, and R9 and R10 may form a ring. R11 represents an atom group necessary for forming an acidic nucleus, and R11 and L17 may form a ring. L16
And L17 each represents an optionally substituted methine group. n
4 represents 1, 2, 3 or 4. Acidic and basic nuclei are described in H. James ed., The Theoryof
the Photographic Procedures
s, 4th edition, pages 198 to 200, (1977
Year).

The oxonol dye represents a chromophore represented by the following general formula (5). General formula (5)

[0018]

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In the formula, R12 and R13 represent an atom group necessary for forming an acidic nucleus, and R12 and L18 and R13 and L20 may form a ring, respectively. L18, L19 and L20 each represent an optionally substituted methine group. n5 represents 1, 2, 3 or 4.

For other definitions of chromophores, see
M. Hummer, The Chemistry of Heterocyclic Compounds, The Cyanine Soy and Related Compounds, John Wiley and Sons, New York (1964). Cyanine dyes are described in the same book, pages 11 to 35.
On page 0, the hemicyanine dye is described in the same book, pages 448 to 4
On page 63, the merocyanine dye is the same, from page 511 to page 611, the oxonol dye is the same, page 463 to page 482, and the hemioxonol dye is the same, page 485.
From page 488 to page 488, styryl dyes are described in the same title, pages 398 to 433, and cyanine bases are described in the same title, pages 351 to 374. Streptocyanin dyes include M.P. Okawara, T .; Kitao,
T. Hirashima, M .; By Matsuoka, Or
ganic Colorants, A Handboo
k of Data of Selected Dye
for Electro-optical Appl
ications, Elsevier, New York
k., 1988, pp. 306-308.
61021 to 61074. The methine compound of the present invention is preferably a hemicyanine dye, a cyanine dye, a merocyanine dye, or an oxonol dye, and particularly preferably a hemicyanine dye. Alternatively, a linked dye in which two or more chromophores are linked by a covalent bond may be used.

A is a divalent linking group, and the linking group is
Preferably, it is composed of an atom or an atomic group containing at least one of a carbon atom, a nitrogen atom, a sulfur atom and an oxygen atom. Preferably, an alkylene group (eg, methylene,
Examples include ethylene, propylene, butylene, and pentylene, which may be further substituted. Examples of the substituent include a halogen atom (eg, chlorine atom, bromine atom, iodine atom, fluorine atom), a nitro group, an alkoxy group (eg, methoxy, ethoxy), an aryl group (eg, phenyl), an aryloxy group (eg, Phenoxy), an amide group, a carbamoyl group, a sulfo group, a hydroxy group, a carboxy group, an alkylthio group, a cyano group, and the like. Hereinafter, these are referred to as a substituent group X. ), An arylene group (eg, 1,2-phenylene, 1,3-phenylene, 1,4-phenylene, 1,4-naphthylene, 1,5
-Naphthylene, 1,8-naphthylene, 2,6-naphthylene and the like, which may be further substituted. Examples of the substituent include the above-described substituent group X), alkenylene groups (e.g., ethenylene, 1-propenylene, and the like, which may be further substituted. Examples of the substituent include the above-described substituent group X), Alkynylene groups (for example, ethynylene, 1-propynylene and the like, which may be further substituted; examples of the substituent include the above-mentioned substituent group X), and alkyleneoxyalkylene groups (for example, ethyleneoxyethylene and the like; Examples of the substituent include the above-mentioned substituent group X), an amide group, an ester group, a sulfamide group, a sulfonic ester group, a ureido group, a sulfonyl group, a sulfinyl group, a thioether group, and a carbonyl group. ,
-N (Ra)-(Ra represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group),
A heterocyclic divalent group (for example, a 6-chloro-1,3,5-triazine-2,4-diyl group, a pyrimidine-2--4-diyl group, a quinoxaline-2,3-diyl group,
It may be further substituted. The substituents include the above-mentioned substituent group X), or a divalent linking group having 1 to 20 carbon atoms, which is formed by combining one or more thereof. Preferably, an alkylene group having 1 to 10 carbon atoms, 6 to 20 carbon atoms
, An alkenylene group having 1 to 10 carbon atoms, and an alkynylene group having 1 to 10 carbon atoms.

As Z1, Z2, Z3 and Z4, an oxazole nucleus having 3 to 25 carbon atoms (eg, 2-1-methyloxazolyl, 2-1-ethyloxazolyl, 2-1,3
-Diethyloxazolyl, 2-1-methylbenzoxazolyl, 2-1-ethylbenzoxazolyl, 2-1
Sulfoethylbenzoxazolyl, 2-1-sulfopropylbenzoxazolyl, 2-1-methylthioethylbenzoxazolyl, 2-1-methoxyethylbenzoxazolyl, 2-1-sulfobutylbenzoxazolyl ,
2-1-methyl-β-naphthoxazolyl, 2-1-methyl-α-naphthoxazolyl, 2-1-sulfopropyl-β-naphthoxazolyl, 2-1-sulfopropyl-γ-naphtho Oxazolyl, 2-1- (1-naphthoxyethyl) benzoxazolyl, 2-1,5-dimethylbenzoxazolyl, 2-6-chloro-1-methylbenzoxazolyl, 2-5-bromo- 1-methylbenzoxazolyl, 2-1-ethyl-5-methoxybenzoxazolyl, 2-5-phenyl-1-sulfopropylbenzoxazolyl, 2-5- (4-bromophenyl) -1-
Sulfobutylbenzoxazolyl, 2-1-dimethyl-
5,6-dimethylthiobenzoxazolyl, and the like; 2-oxazolyl having another substituent;
Benzoxazolyl is also included. Examples of the substituent include an alkyl group (eg, methyl, ethyl, propyl), a halogen atom (eg, chlorine atom, bromine atom, iodine atom, fluorine atom), a nitro group, an alkoxy group (eg,
Methoxy, ethoxy), an aryl group (eg, phenyl), an aryloxy group (eg, phenoxy), an amide group, a carbamoyl group, a sulfo group, a hydroxy group, a carboxy group, an alkylthio group, a cyano group, and the like. ), A thiazole nucleus having 3 to 25 carbon atoms (for example, 2-
3-methylthiazolyl, 2-3-ethylthiazolyl, 2
-3-sulfopropylthiazolyl, 2-3-sulfobutylthiazolyl, 2-3,4-dimethylthiazolyl, 2-
3,4,4-trimethylthiazolyl, 2-3-carboxyethylthiazolyl, 2-3-methylbenzothiazolyl, 2-3-ethylbenzothiazolyl, 2-3-butylbenzothiazolyl , 2-3-sulfopropylbenzothiazolyl, 2-3-sulfobutylbenzothiazolyl, 2-
3-methyl-β-naphthothiazolyl, 2-3-sulfopropyl-γ-naphthothiazolyl, 2-3- (1-naphthoxyethyl) benzothiazolyl, 2-3,5-dimethylbenzothiazolyl, 2-6-chloro-3- Methylbenzothiazolyl, 2-6-iodo-3-ethylbenzothiazolyl, 2-5-bromo-3-methylbenzothiazolyl,
2-3-ethyl-5-methoxybenzothiazolyl, 2-
5-phenyl-3-sulfopropylbenzothiazolyl,
2-5- (4-bromophenyl) -3-sulfobutylbenzothiazolyl, 2-3-dimethyl-5,6-dimethylthiobenzothiazolyl, etc.), having 3 to 3 carbon atoms
25 imidazole nuclei (for example, 2-1, 3-diethylimidazolyl, 2-1, 3-dimethylimidazolyl, 2
-1-methylbenzimidazolyl, 2-1, 3,4-triethylimidazolyl, 2-1, 3-diethylbenzimidazolyl, 2-1, 3,5-trimethylbenzimidazolyl, 2-6-chloro-l, 3-dimethylbenzimidazolyl, 2-5,6-dichloro-1,3-diethylbenzimidazolyl, 2-1,3-disulfopropyl-5
-Cyano-6-chlorobenzimidazolyl), a quinoline nucleus having 9 to 25 carbon atoms (for example, 2-1)
-Methylquinolyl, 2-1-ethylquinolyl, 2-1
Methyl 6-chloroquinolyl, 2-1, 3-diethylquinolyl, 2-1-methyl-6-methylthioquinolyl, 2-
1-sulfopropylquinolyl, 4-1-methylquinolyl, 4-1-sulfoethylquinolyl, 4-1-methyl-
7-chloroquinolyl, 4-1,8-diethylquinolyl,
4-1-methyl-6-methylthioquinolyl, 4-1-sulfopropylquinolyl, etc.), having 3 to 3 carbon atoms.
Examples thereof include 25 selenazole nuclei (for example, 2-1-methylbenzoselenazolyl and the like), and a pyridine nucleus having 5 to 25 carbon atoms (for example, 2-pyridyl and the like). Preferred are an oxazole nucleus, an imidazole nucleus and a thiazole nucleus. These heterocycles may be further condensed. A benzo group can be given as an example of a condensed group.

R1 and R6 each represent an alkyl group having 1 to 20 carbon atoms (eg, methyl, ethyl, n-propyl, n-
Butyl, n-pentyl, n-hexyl, n-heptyl,
n-nonyl, i-propyl, i-butyl, i-pentyl, t-butyl and the like. These may be substituted. Examples of the substituent include the above-described substituent group X.
Preferred substituent groups include a sulfo group, a carboxy group,
An alkoxy group, an alkenyl group, and an amide group. When the substituent is a sulfo group, examples of the counter ion include alkali metals and quaternary ammonium compounds, such as sodium, potassium, pyridinium,
-Ethylpyridinium, triethylammonium and the like. Preferably, a methyl group, an ethyl group, a propyl group,
Sulfoethyl group, sulfopropyl group, sulfobutyl group,
A carboxyethyl group, a methoxyethyl group, a phenethyl group, a phenoxyethyl group, a naphthoxyethyl group, an o-sulfonatobenzyl group, and a 3-phenyl-3-sulfopropyl group. R4 and R5 are each an alkyl group having 1 to 20 carbon atoms, and at least one of R4 and R5 is an alkyl group containing a disulfide group. Specific examples include a methyl group, an ethyl group, a propyl group, a sulfopropyl group, a sulfobutyl group, a methyldisulfideethyl group, and a phenyldisulfideethyl group. Preferred are an ethyl group, a sulfopropyl group, and a methyldisulfideethyl group.

R2, R3, R7 and R8 each have 1 carbon atom
To 20 alkyl groups (e.g., methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-
-Heptyl, n-nonyl, i-propyl, i-butyl,
i-pentyl, t-butyl and the like. These may be substituted. Examples of the substituent include the above-described substituent group X. Preferred substituent groups are a sulfo group, a carboxy group, an alkoxy group, an alkenyl group, and an amide group. When the substituent is a sulfo group, examples of the counter ion include alkali metals and quaternary ammonium compounds, such as sodium, potassium, pyridinium, 1-ethylpyridinium, and triethylammonium. ), An aryl group having 1 to 20 carbon atoms (for example, phenyl, 1-naphthyl, 2-naphthyl, and the like, and may be substituted, and the substituent includes the above-mentioned substituent group X excluding aryl) , Carbon number 1-2
0 heterocyclic group (for example, 2-pyridyl, 3-pyridyl, 2-thienyl, 3-thienyl, 2-furyl, 3-furyl, 2-quinolyl, etc., and may be substituted, Is the substituent group X). R2 is preferably a methyl group, an ethyl group, or a phenyl group. R3 is preferably a methyl group, an ethyl group, or a phenyl group. Preferably, a lower alkyl group,
A phenyl group and a 2-pyridyl group. R2 and R3 are R
7 and R8 may be connected to each other to form a ring. Preferably, the ring is formed by an alkylene group. Particularly preferred is an ethylene linkage.

L1, L2, L3, L4, L5, L6, L
7, L8, L9, L10, L11, L12, L13, L
14, L15, L16, L17, L18, L19 and L
20 represents a methine group. Examples of the substituted methine group which may be substituted include a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a halogen atom, a substituted or unsubstituted alkoxy group, an amino group, and the like. And may form a ring with an auxochrome. Preferably it is an unsubstituted methine group. Preferred combinations are L1
L4 is an unsubstituted methyl group, R1 is an alkyl group, A is an ethylene group, R2 and R3 are mutually connected ethylene groups, Z1 is a thiazole nucleus and a benzothiazole nucleus.

N1, n2 and n3 are respectively 0, 1, 2, 3
Or represents 4. n4 and n5 represent 1, 2, 3 or 4, respectively. It is preferably 1, 2, or 3. Particularly preferably, it is 2.

P1, p2, p3 and p4 each represent 0 or 1. Preferably it is 0.

M1, M2 and M3 each represent a charge neutralizing ion. Whether a compound is a cation, an anion, or has a net ionic charge depends on its substituents. Typical cations are ammonium and alkali metal ions, while anions can be either inorganic or organic. Examples of the cation include sodium ion, potassium ion, triethylammonium ion, pyridinium ion, and 1-ethylpyridinium ion. Examples of the anion include halogen anion (eg, chloride ion, bromide ion, fluorine ion, Iodine ion),
Examples include a substituted arylsulfonic acid ion (for example, paratoluenesulfonic acid ion), an alkyl sulfate ion (for example, methyl sulfate ion), a sulfate ion, a perchlorate ion, a tetrafluoroborate ion, and an acetate ion. m1, m2 and m3 each represent a number required to neutralize the charge.

The specific examples of the compounds of the present invention are shown below.
The present invention is not limited to this.

[0030]

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[0031]

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[0032]

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[0033]

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[0034]

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[0035]

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[0036]

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The compounds of the present invention can be carried out, for example, according to the methods described in the following documents. Dee
Heterocyclic Compound Special Topics in Heterocyclic Chemistry, John Willie and Sons,
New York (1977).

Next, the silver halide photographic material of the present invention will be described in detail. The methine compound of the present invention and the compound represented by the formula (1) (hereinafter, the methine compound of the present invention) can be used alone or in combination with other sensitizing dyes in a silver halide photographic material.

The timing at which the methine compound of the present invention (and the same applies to other sensitizing dyes) is added to the silver halide emulsion of the present invention. It may be during the process. For example, U.S. Pat. Nos. 2,735,766 and 3,628,9
No. 60, 4,183,756, 4,225,66
No. 6, JP-A-58-184142 and JP-A-60-1967.
As disclosed in JP-A No. 49/49, etc., the timing before silver halide grain forming step and / or before desalting, the timing during and / or after desalting and before the start of chemical ripening, As disclosed in 58-113920 and the like,
It may be added at any time in the process, just before chemical ripening or during the process, or at any time before the application of the emulsion until the coating after the chemical ripening. Also, U.S. Pat.
As disclosed in US Pat. No. 5,666, JP-A-58-7629, etc., the same compound alone or in combination with a compound having a different structure may be used, for example, during the particle formation step, during the chemical ripening step, or when the chemical ripening is completed. Separately, or may be added dividedly, such as before chemical ripening or during the process and after completion, and may be added by changing the type of compound and compound combination to be added separately. Is also good.

The addition amount of the methine compound of the present invention is
Although it depends on the shape and size of the silver halide grains, it can be used in an amount of 1 × 10 ⁻⁶ to 8 × 10 ⁻³ mol per mol of silver halide. For example, when the silver halide grain size is 0.2 to 1.3 μm, the addition amount is preferably 2 × 10 ^{−6 to} 3.5 × 10 ⁻³ mol per mol of silver halide, and is preferably 7.5. An addition amount of × 10 ^{−6 to} 1.5 × 10 ⁻³ mol is more preferable.

The methine compound of the present invention can be directly dispersed in an emulsion. Also, these are first suitable solvents,
For example, it can be dissolved in methyl alcohol, ethyl alcohol, methyl cellosolve, acetone, pitidine, water or a mixed solvent thereof and added to the emulsion in the form of a solution. At this time, additives such as a base, an acid, and a surfactant can be made to coexist. Also, ultrasonic waves can be used for dissolution. As a method for adding the methine compound, the compound is dissolved in a volatile organic solvent as described in US Pat. No. 3,469,987, and the like. The solution is dispersed in a hydrophilic colloid, and the dispersion is added to the emulsion. As described in JP-B-46-24185, the dispersion is dispersed in a water-soluble solvent, and the dispersion is added to the emulsion. US Patent No. 3,822,13
No. 5, as disclosed in JP-A-51-74, a method of dissolving a methine compound in a surfactant and adding the solution to an emulsion.
No. 624, a method of dissolving with a compound which causes a red shift, and adding the solution to an emulsion; an acid substantially free of water containing a methine compound as described in JP-A-50-80826. And adding the solution to the emulsion. Other additions to emulsions include U.S. Pat. Nos. 2,912,343 and 3,342,60.
No. 5, 2,996,287 and 3,429,835
The method described in the item is also used.

The methine compound of the present invention has sharpness,
It can be used as various filter dyes, anti-irradiation dyes or anti-halation dyes for the purpose of improving color resolution. This methine compound can be contained in a coating solution such as a silver halide photographic material layer, a filter layer and / or an antihalation layer by a conventional method. The dye may be used in an amount sufficient to color the photographic layer, and those skilled in the art can easily select this amount appropriately according to the purpose of use. Generally, the optical density is in the range of 0.05 to 3.0. It is preferable to use it. The timing of addition may be any step before coating. Alternatively, a polymer having a charge opposite to that of the dye ion may coexist in the layer as a mordant, and the dye may be localized in a specific layer by the interaction with the dye molecule. As the polymer mordant, for example, US Pat.
48,564, 4,124,386, 3,62
5,694, 3,958,995, 4,16
Nos. 8,976 and 3,445,231.

Useful supersensitizers for spectral sensitization in the present invention include, for example, US Pat. No. 3,511,664,
3,615,613, 3,615,632, 3,615,641, 4,596,767, 4,945,038, 4,965,182, and 4 , 965, 182 and the like, and a pyrimidylamino compound, a triazinylamino compound, an azolium compound, and the like.

The silver halide which can be used in the silver halide photographic light-sensitive material of the present invention may be any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride. .
Preferred silver halides are silver bromide, silver chlorobromide, silver iodochlorobromide, or high silver chloride described in JP-A-2-42. The composition and processing of the light-sensitive material will be described below. The composition and processing described in JP-A-2-42 are preferably used particularly in high silver chloride. The constitution and processing described in JP-A-63-264743 are particularly preferably used for silver chlorobromide.

The silver halide grains may have different phases between the inside and the surface layer, or may consist of a uniform phase. Also, particles whose latent image is mainly formed on the surface (for example, a negative photosensitive material), particles that are mainly formed inside the particle (for example, an internal latent image photosensitive material), or particles that have been previously covered Particles (for example, a direct positive photosensitive material) may be used. Silver halide grains having the above-described various halogen compositions, crystal habits, grain internal structures, shapes and distributions are used in photosensitive photographic materials for various uses.

The silver halide grains in the photographic light-sensitive material may have a regular crystal form such as cubic, tetradecahedral or rhombodecahedral, or an irregular crystal form such as spherical or tabular. Or a compound having a combination of these crystal forms. It may consist of a mixture of particles of different crystal forms.

In the photographic light-sensitive material of the present invention, the silver halide grains forming the emulsion layer have an aspect ratio of 3 or more and 1 or more.
The case where it is 00 or less is preferable. Here, the expression that the aspect ratio is 3 or more and 100 or less means that silver halide grains having an aspect ratio (equivalent circle diameter of silver halide grains / grain thickness) of 3 or more and 100 or less correspond to all silver halide grains in the emulsion. It means that there is at least 50% of the projected area. The aspect ratio is preferably 3 or more and 20 or less, and most preferably 4 or more and 12 or less. Tabular grains are described by Gatov, Photographic Science and Engineering, Vol. 14, pp. 248-257 (1970), U.S. Pat. Nos. 4,434,226 and 4,414,310.
No. 4,433,048, 4,439,520 and GB 2,112,157. In the photographic light-sensitive material of the present invention, its abundance is at least 70%, particularly preferably at least 85%.

The methine compound of the present invention is used in photographic materials for the following applications for the purpose of sensitizers, sensitizing dyes, filters, antihalation or prevention of irradiation. These dyes are used in addition to the photosensitive emulsion layer. , Middle layer,
It can be added to desired layers such as a protective layer and a back layer. The methine compound of the present invention is used in various color and black-and-white silver halide photographic materials. More specifically, a light-sensitive material for color positive, a light-sensitive material for color paper, a light-sensitive material for color negative, a light-sensitive material for color reversal (with or without a coupler), a silver halide photographic light-sensitive material for direct positive, Photographic materials for plate making (eg, lith film, risupe film, etc.), photographic materials for cathode ray tubes and sprays, photographic materials for X-ray recording (especially materials for direct and indirect photography using a screen), used in silver salt diffusion transfer processes Photosensitive material used in a color diffusion transfer process, a die, transfer, a photosensitive material used in a process, a photosensitive material used in a silver dye bleaching method, a photosensitive material for thermal development, and the like.

The silver halide emulsion used in the present invention is:
P. Grafkiddes, Chimmy e Physique Photography, Paul Montell, 1967, GF Deffein, Photographic Emulsion Chemistry, The Focal Press, 196
For 6 years, it can be prepared by the method described in V.L.T.Erikmann Making and Coaching Photographic Emulsion, The Focal Press, 1964.

When silver halide grains are formed, a solvent such as ammonia, rodankari, rodanammon, thioether compound (eg, US Pat. No. 3,271,1) may be used as a silver halide solvent in order to control grain growth.
Nos. 57, 3,574,628 and 3,704,13
Nos. 0, 4,297,439 and 4,276,374
No. 3,078,098), thione compounds (for example, JP-A-53-144).
No. 319, No. 53-82408, No. 55-77737
And amine compounds (for example, JP-A-54-1007).
No. 17, etc.) can be used. In the course of silver halide grain formation or physical ripening, a cadmium salt, a zinc salt, a thallium salt, an iridium salt or a complex thereof, a rhodium salt or a complex salt thereof, an iron salt or a complex salt thereof, and the like may coexist. As the internal latent image type silver halide emulsion used in the present invention, for example, US Pat.
2,250, 3,206,313, 3,44
7,927, 3,761,276 and 3,9
Examples thereof include a conversion type silver halide emulsion, a core / shell type silver halide emulsion described in JP-A No. 35,014, and a silver halide emulsion incorporating a different metal.

The silver halide emulsion is usually chemically sensitized. For chemical sensitization, see, for example, H. Freezer, Day Grandlage der Photography Prosthesis Mitt Silberhalogeniden Academic, Fairlags, 1968, No. 6,
The method described on pages 75 to 734 can be used.
That is, a sulfur sensitization method using a compound containing a sulfur capable of reacting with active gelatin or silver (eg, thiosulfate, thioureas, mercapto compounds, rhodanines), a selenium sensitization method, a reducing substance (for example, Stannous salts, amines, hydrazine derivatives, formamidinesulfinic acid,
A reduction sensitization method using a silane compound), a noble metal sensitization method using a noble metal compound (for example, a complex salt of a metal of Group VIII of the periodic table such as Pt, Ir, or Pd in addition to a gold complex salt) alone or in combination. Can be.

The photographic light-sensitive material used in the present invention may contain various compounds for the purpose of preventing fogging during the manufacturing process, storage or photographic processing of the light-sensitive material, or stabilizing photographic performance. it can. That is, thiazoles such as U.S. Pat.
No. 942,721, JP-A-59-191032 and the like, and benzothiazolium salts described in
Ring-opened compounds, nitroindazoles, triazoles, benzotriazoles, benzimidazoles (especially nitro- or halogen-substituted), heterocyclic mercapto compounds such as mercaptothiazoles, mercaptobenzothiazoles described in US Pat. Mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole), mercaptopyrimidines, the above heterocyclic mercapto compounds having a water-soluble group such as a carboxy group or a sulfone group, thioketone compounds such as oxazolinethione, azaindenes such as tetraaza Indenes (especially 4-hydroxy substitution (1,3,3a,
7) Many compounds known as anti-fogging agents or stabilizers, such as tetraazaindenes), benzenethiosulfonic acids, benzenesulfinic acid, acetylene compounds described in JP-A-62-287957, and the like. Can be added.

The silver halide light-sensitive material of the present invention can contain a color coupler such as a cyan coupler, a magenta coupler and a yellow coupler, and a compound dispersing the coupler. That is, in the color development processing, aromatic 1
It may contain a compound capable of forming a color by oxidative coupling with a secondary amine developing agent (for example, a phenylenediamine derivative arrow, an aminophenol derivative, etc.). For example,
Examples of magenta couplers include 5-pyrazolone couplers, pyrazolobenzimidazole couplers, cyanoacetylcoumarin couplers, open-chain acylacetonitrile couplers, and yellow couplers include acylacetamide couplers (eg, benzoylacetoanilides, pivaloylacetoanilides). And cyan couplers such as naphthol couplers and phenol couplers. These couplers are preferably non-diffusible couplers having a hydrophobic group called a ballast group in the molecule. The coupler may be either 4-equivalent or 2-equivalent to silver ion. Further, a colored coupler having a color correcting effect or a coupler which releases a development inhibitor during development (a so-called DIR coupler) may be used. In addition to the DIR coupler, a colorless DI in which the product of the coupling reaction is colorless and releases a development inhibitor
R coupling compounds may be included.

The photographic light-sensitive material of the present invention may be, for example, polyalkylene oxide or a derivative thereof such as an ether, ester or amine, a thioether compound, a thiomorpholine or a quaternary ammonium, for the purpose of increasing sensitivity, increasing contrast, or promoting development. It may contain a salt compound, a urethane derivative, a urea derivative, an imidazole derivative, a 3-pyrazolidone derivative, or the like. In the photographic light-sensitive material of the present invention, as a filter dye, or for various purposes such as prevention of irradiation, other than the methine compound of the present invention,
Various dyes may be included. Such dyes include:
For example, British Patent Nos. 506,385 and 1,177,4
29, 1,311,884, 1,338,79
No. 9, No. 1, 385, 371, No. 1, 467, 214
No. 1,433,102, 1,553,516
JP-A-48-85130 and JP-A-49-114420
No. 52-117123, No. 55-161233
No. 59-11640, JP-B-39-22069
No. 43-13168, No. 62-273527,
U.S. Pat. Nos. 3,247,127 and 3,469,98
Oxonol dyes having a pyrazolone nucleus or a barbituric acid nucleus described in Nos. 5,078,933 and the like;
U.S. Pat. Nos. 2,533,472 and 3,379,53
No. 3, British Patent No. 1,278,621, JP-A-1-1-1
Other oxonol dyes described in JP-A-34447, JP-A-1-183652 and the like, British Patent No. 575,691
Nos. 680,631, 599,623, 78
6,907, 907,125, 1,045,6
09, U.S. Pat. No. 4,255,326, JP-B-59
Azo dyes described in JP-A-211043 and the like;
Azomethine dyes described in U.S. Pat. Nos. 2,865,7 and 0-100116, 54-118247, and British Patent Nos. 2,014,598 and 750,031;
52, anthraquinone dyes described in U.S. Pat. Nos. 2,533,009, 2,688,541 and 2,538,008, British Patent 584,609,
No. 1,210,252, JP-A-50-40625,
No. 51-3623, No. 51-10927, No. 54-
118247, JP-B-48-3286, and 59-3
Arylidene dyes described in JP-A-7303 and the like, JP-B-28-3082, JP-B-44-16594, and JP-B-59-2.
8898 and the like; British Patent Nos. 446,583 and 1,335,422;
Triarylmethane dyes described in JP-A-9-228250 and the like; British Patent Nos. 1,075,653 and 1,15;
No. 3,341, No. 1,284,730, No. 1,47
Merocyanine dyes described in U.S. Pat. No. 2,843,486 described in US Pat.
No. 3,294,539, JP-A-1-291247
And the like.

The following method can be used to prevent such dye diffusion. For example, a method of coexisting a hydrophilic polymer having a charge opposite to that of a dissociated anionic dye in a layer as a mordant and localizing the dye in a specific layer by interaction with dye molecules is disclosed in U.S. Pat.
8,564, 4,124,386, 3,62
No. 5,694. Further, a method of dyeing a specific layer using a dye solid insoluble in water is disclosed in
Nos. 6-12639, 55-155350, 55-
155351, 63-27838, 63-19
No. 7943 and European Patent No. 15,601. A method of dyeing a specific layer using metal salt fine particles having a dye adsorbed thereto is disclosed in U.S. Pat. No. 2,719,088.
Nos. 2,496,841 and 2,496,843
And JP-A-60-45237.

The photographic light-sensitive material of the present invention has various interfaces for various purposes such as coating aids, antistatic properties, improvement of slipperiness, emulsification / dispersion, prevention of adhesion, and improvement of photographic properties (eg, development acceleration, high contrast, sensitization). Activators may be included. In practicing the present invention, other additives are used together with the silver halide emulsion or other hydrophilic colloid. For example, a discoloration inhibitor, an inorganic or organic hardener, an anti-coloring agent, an ultraviolet absorber, a mordant, a plasticizer, a latex polymer, a matting agent and the like can be mentioned. Specifically, Research Disclosure, Volume 176, (1
978, XI), D-17643, and the like. In the photographic light-sensitive material used in the present invention, a hydrophilic polymer such as gelatin is used as a protective colloid. The finished silver halide emulsion and the like are coated on a suitable support such as baryta paper, resin-coated paper, synthetic paper, triacetate film, polyethylene terephthalate film, other plastic base or glass plate.

Exposure for obtaining a photographic image may be performed using a usual method. That is, any of various known light sources such as natural light, tungsten electric lamp, fluorescent lamp, mercury lamp, xenon arc lamp, carbon arc lamp, xenon flash lamp, and cathode ray tube flying spot can be used. Exposure time is not limited to exposure time of 1/1000 second to 1 second usually used in cameras, but also exposure shorter than 1/1000 second, for example, exposure of 1/10000 to 1 / 1,000,000 second using a xenon flashlight or a cathode ray tube. Exposure longer than 1 second can be used. If necessary, the spectral composition of light used for exposure can be adjusted by a color filter. Laser light can also be used for exposure. Alternatively, the exposure may be performed using light emitted from a phosphor excited by an electron beam, X-ray, γ-ray, α-ray, or the like. Photographic processing of photosensitive material made using the present invention is described, for example, in Research Disclosure, Vol. 176, pp. 28-30 (RD1764).
Any of the known methods and known processing solutions as described in 3) can be applied. This photographic processing may be either photographic processing for forming a silver image (black-and-white photographic processing) or photographic processing for forming a dye image (color photographic processing), depending on the purpose. The processing temperature is usually selected between 18 ° C and 50 ° C, but may be lower than 18 ° C or higher than 50 ° C.

The silver halide photographic light-sensitive material carrying magnetic recording which may be used in the present invention is disclosed in JP-A-6-35118.
No. 6-17528, Invention Association Open Technical Report 94-60
23. A thin layer support of a pre-heat-treated polyester described in 23, for example, a polyethylene aromatic dicarboxylate-based polyester support, having a thickness of 50 μm to 300 μm, preferably 50 μm to 200 μm, and more preferably 80 μm.
m to 115 μm, particularly preferably 85 μm to 105 μm
At a temperature not lower than 40 ° C. and not higher than the glass transition temperature.
Heat treated (annealed) for 0 hour
Irradiation described in JP-A Nos. 43-2604 and 45-3828, JP-B-48-5043, JP-A-51-13.
No. 1576 etc., surface treatment such as corona, USP
No. 5,326,689 and an undercoat layer described in US Pat. No. 2,761,791 is provided if necessary.
6, ferromagnetic particles described in JP-A-6-59357 may be applied. The above magnetic layer is described in JP-A-4-124.
The stripe shape described in JP-A Nos. 642 and 4-124645 may be used. Further, as required, Japanese Patent Application Laid-Open No. 4-625
No. 43 is subjected to an antistatic treatment, and a silver halide emulsion is finally coated. The silver halide emulsions used herein are described in JP-A-4-16693, JP-A-3-41436, and JP-A-3-41436.
No. 41437 is used. The silver halide photographic light-sensitive material thus produced is preferably produced by the production control method described in JP-B-4-86817, and the production data is preferably recorded by the method described in JP-B-6-87146. Thereafter or before that, according to the method described in JP-A-4-125560, the film is cut into a narrower film than the conventional 135 size, and the perforations are reduced per small format screen so as to match the smaller format screen. Punch two holes per side. The film thus produced is the cartridge package of JP-A-4-157559, the cartridge shown in FIG. 9 of the embodiment of JP-A-5-210202, or the film cartridge described in U.S. Pat. No. 4,221,479; , 4,
834,366, 5,226,613, 4,8
Use in a cartridge described in No. 46,418.
The film cartridge or film cartridge used here is disclosed in US Pat. No. 4,848,693, US Pat.
A type capable of accommodating a tongue, such as No. 355, is preferable from the viewpoint of light shielding properties. Further, a cartridge having a lock mechanism such as USP 5,296,886 or USP 5,
No. 347,334 are preferable, and a cartridge having a double exposure prevention function is preferable. Further, as described in JP-A-6-85128, a cartridge in which the film is easily mounted by simply inserting the film into the cartridge may be used. The film cartridge thus produced can be used for various purposes such as photographing, developing, and enjoying various photographs by using a camera, a developing machine, and laboratory equipment described below. For example, a camera of a simple mounting type described in JP-A-6-8886 and JP-A-6-99908, and a camera described in JP-A-6-57398 and 6-10
No. 1135, an automatic winding camera,
No. 05690, a camera capable of taking out and changing the type of film in the middle of shooting, and information on shooting described in JP-A-5-293138 and JP-A-5-283382, for example,
A camera capable of magnetically recording panoramic photography, high vision photography, and normal photography (magnetic recording capable of selecting a print aspect ratio) on a film, a camera having a double exposure prevention function described in JP-A-6-101194, 5
The function of a film cartridge (patrone) can be sufficiently exhibited by using a camera or the like having a function of displaying the use state of a film or the like described in -150577. The film photographed in this way is disclosed in JP-A-6-222514,
JP-A-6-9526, by processing with an automatic developing machine described in JP-A-6-222545, or before, during or after the processing.
5 and 4-123054, and the method of utilizing magnetic recording on a film described in JP-A-5-19364.
The aspect ratio selection function described in the reference number may be used. At the time of development processing, if it is a cine development,
Splicing is performed by the method described in No. 61. At the time of or after the development processing, the wafer is subjected to the detachment and detachment processing described in JP-A-6-148805. After processing in this way,
Film information may be converted to print through back printing and front printing on color paper by the methods described in JP-A-2-184835, JP-A-4-186335, and JP-A-6-79968. Further, JP-A-5-11
It may be returned to the customer together with the index print and return cartridge described in JP-A Nos. 353 and 5-232594.

In addition, at least one layer of
A blue-sensitive silver halide emulsion layer containing a yellow color coupler, a green-sensitive silver halide emulsion layer containing a magenta color coupler, and a red-sensitive silver halide emulsion layer containing a cyan color coupler, and A color light-sensitive material having at least one silver halide emulsion layer that gives a sodium bicarbonate effect to the entire red-sensitive silver halide emulsion layer is preferably used. Details of such a light-sensitive material are described in JP-A-7-159950.

[0060]

Next, the present invention will be described based on examples, but the present invention is not limited to these examples.

Example 1 (Synthesis of Dye No. 1) Dye No. 1 was synthesized according to the following scheme.

[0062]

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Maximum absorption wavelength (methanol) 430 nm Absorption coefficient 99000

Example 2 (1) Preparation of Emulsion An aqueous solution containing gelatin having an average molecular weight of 15,000 (water 12
100 ml, gelatin 7.0 g, while stirring keeping the containing KBr4.5G) to 30 ° C., tabular added by 1.9MAgNO ₃ solution and 1.9MKBr aqueous double jet of 70 seconds at 25 ml / min Particle nuclei were obtained.
400 ml of this emulsion was used as a seed crystal, and 650 ml of an inert gelatin aqueous solution (containing 20 g of gelatin and 1.2 g of KBr) was added thereto, and the temperature was raised to 75 ° C., followed by ripening for 40 minutes.
And AgNO ₃ aqueous solution (including 1.7 g of AgNO ₃ )
Is added over 1 minute and 30 seconds, followed by NH ₄ NO ₃ (5
(0 wt%) aqueous solution (7.0 ml) and NH ₃ (25 wt%).
0 ml was added and aged for an additional 40 minutes.

Next, the emulsion was adjusted to pH 7 with HNO ₃ (3N), and 1.0 g of KBr was added. Then, 366.5 ml of a 1.9 MAg NO ₃ aqueous solution and an aqueous KBr solution were added, followed by 1.9 MAg NO ₃ aqueous solution.
gNO ₃ aqueous solution (53.6 ml) and KBr (KI 33.3 mol)
An aqueous solution of 1.9 MAgNO ₃ and an aqueous solution of KBr were added while maintaining the pAg at 7.9 to obtain Emulsion 1.

Emulsion 1 obtained was a triple structure grain having a region having the highest silver iodide content in the intermediate shell, an average aspect ratio of 2.8, and a tabular grain having an aspect ratio of 3 or more. The ratio to the total projected area was 26%. The coefficient of variation of the particle size was 7%, and the average of the particle size was 0.98 μm in sphere equivalent diameter.

Emulsion 1 was desalted by a conventional flocculation method, and a sensitizing dye was added to 1 mol of silver, and gold, sulfur and selenium sensitization was optimally performed in the presence of the sensitizing dye.

(2) Preparation of Coated Samples Emulsion layers and protective layers as shown in Table 1 were applied to a triacetyl cellulose film support provided with an undercoat layer to prepare Samples 101 to 107.

[0069]

[Table 1]

These samples were exposed to sensitometric exposure (1/100 second) and subjected to the following color development processing.

Processing method Step Processing time Processing temperature Replenishment tank capacity Color development 2 minutes 45 seconds 38 ° C 33 ml 20 liter Bleaching 6 minutes 30 seconds 38 ° C 25 ml 40 liter Rinse 2 minutes 10 seconds 24 ° C 1200 ml 20 liter 4 minutes 20 seconds 38 ° C 25ml 30 liters Rinse with water (1) 1 minute 05 seconds 24 ° C Counterflow piping system of 10 liters from (2) to (1) Rinse with water (2) 1 minute 00 seconds 24 ° C 1200ml 10 liters Constant 1 minute 05 seconds 38 ° C 25 ml 10 liter Drying 4 minutes 20 seconds 55 ° C Replenishment amount is 35 mm width per 1 m length Next, the composition of the processing solution is described. (Color developing solution) Mother liquor (g) Replenisher (g) Diethylenetriaminepentaacetic acid 1.0 1.1 1-hydroxyethylidene-1,1-diphosphonic acid 3.0 3.2 Sodium sulfite 4.0 4.4 Potassium carbonate 30.0 37.0 Potassium bromide 1.4 0.7 Potassium iodide 1.5 mg -Hydroxylamine sulfate 2.4 2.8 4- [N-ethyl-N-β-hydroxyethylamino] -2-methylaniline sulfate 4.5 5.5 Add water 1.0 liter 1.0 liter pH 10.05 10.05 (bleach solution) Mother liquor (g ) Replenisher (g) Sodium ferric ethylenediaminetetraacetate trihydrate 100.0 120.0 Disodium ethylenediaminetetraacetate 10.0 11.0 Ammonium bromide 140.0 160.0 Ammonium nitrate 30.0 35.0 Ammonia water (27%) 6.5ml 4.0ml Add water and 1.0L 1.0 liter pH 6.0 5.7 (Fixer) Mother liquor (g) Replenisher (g) NaEthylenediaminetetraacetate Salt 0.5 0.7 Sodium sulfite 7.0 8.0 Sodium bisulfite 5.0 5.5 Ammonium thiosulfate aqueous solution (70%) 170.0 ml 200.0 ml Add water 1.0 liter 1.0 liter pH 6.7 6.6 (stable solution) Mother liquor (g) Replenisher (g) Formalin ( 37%) 2.0ml 3.0ml Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.3 0.45 Disodium ethylenediaminetetraacetate 0.05 0.08 Add water 1.0 liter 1.0 liter pH 5.8-8.0 5.8-8.0

The density of the treated sample was measured with a green filter, and the fresh sensitivity and fogging were evaluated. Sensitivity is defined as the reciprocal of the exposure that gives a density 0.2 higher than the fog density,
The sensitivity of each sample was expressed as a relative value with the value of sample 101 taken as 100. The emulsion and methine compound species used for each sample and the sensitivity results for each sample are shown in Table 2 below.

[0073]

[Table 2]

[0074]

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Table 2 shows that the compounds of the present invention have lower fog and higher fresh sensitivity than the comparative compounds.

Example 3 A tabular silver iodobromide emulsion was prepared in the same manner as in Emulsion D of Example 5 of JP-A-8-29904 to prepare Emulsion 2. The multilayer color photographic material was prepared in the same manner as in Sample 5 of Example 5 of JP-A-8-29904. Sample 1 of Example 5 of JP-A-8-29904
01 was replaced with Emulsion 2,
S-1, 2, 3 were replaced with a sensitizing dye (S-1) or a sensitizing dye (No. 1), and 2.5 to 2.5 moles per mole of silver halide.
The sample to which × 10 ⁻⁴ mol was added was used for Sample 201 and Sample 20.
And 2. In order to examine the sensitivity of the sample thus obtained, light from a Fuji FW type sensitometer (Fuji Photo Film Co., Ltd.) was exposed to light for 1/100 second through an optical wedge and a red filter, and Example 1 of JP-A-8-29904 was used. Color development was performed using the same processing steps and processing solution as described above, and cyan density was measured. The sensitivity was indicated by a relative value of fog density + 0.2. As a result, the sample 202 of the present invention had a high sensitivity of 188 with respect to the sensitivity 100 (reference) of the comparative sample 201.

Example 4 Emulsion 1 of Example 1 of JP-A-7-92601 was the same as the emulsion 1 except that the spectral sensitizing dye was replaced with the sensitizing dye (S-1) or the sensitizing dye (No. 1). A tetradecahedral silver iodobromide emulsion was prepared which was different only in that 8 × 10 ^-4 mol was added per mol, and these were designated as emulsions 301 and 302. The emulsion 1 of Example 1 of JP-A-7-92601 was different from the emulsion 1 of Example 1 in that the silver potential in the second double jet was changed from +65 mV to +115 mV and the spectral sensitizing dye was changed to the sensitizing dye (S-1). Alternatively, cubic silver iodobromide emulsions were prepared which were different from the sensitizing dye (No. 1) only in that 4 × 10 ^-4 mol was added per 1 mol of silver halide. The multilayer color photosensitive material is described in Example 4 of JP-A-7-92601.
Was prepared in the same manner according to Sample 401. Emulsion J of the fifteenth layer of Sample 401 of Example 4 of JP-A-7-92601
Samples 1 or 312 were used as Samples 311 and 312, respectively. Similarly, Samples 313 and 314 were obtained by changing the emulsion J of the fifteenth layer in the same Example to the emulsion 303 or the emulsion 304. The sample thus obtained was evaluated for sensitivity. In the same manner as in Example 4 of JP-A-7-92601, 1/50 second exposure and color reversal development were performed to measure yellow density. The sensitivity was calculated as the reciprocal of the amount of exposure required to give a density of +0.2 of the minimum density obtained by giving sufficient exposure, and was shown as a relative value with the sensitivity of Comparative Sample 311 being 100. As a result, the sensitivity of Sample 312 of the present invention was 226, which was high. Similarly, when the sensitivity of the comparative sample 313 is set to 100, the sample 314 of the present invention is used.
Was 156, which was a high sensitivity.

Example 5 An octahedral silver bromide internal latent image type direct positive emulsion and a hexagonal tabular silver bromide internal latent image type direct positive were prepared in the same manner as in Emulsions 1 and 5 of Example 1 of JP-A-5-313297. Emulsions were prepared and used as Emulsion 401 and Emulsion 402. The color diffusion transfer photographic film is a sample 101 of Example 1 of JP-A-5-313297.
In the same manner. Emulsion-2 and sensitizing dye (2) in the eleventh layer of sample 101 of Example 1 of JP-A-5-313297 were prepared by using emulsion 401 and sensitizing dye (S-1) or sensitizing dye (No.
Sample 411 and sample 412 were used instead of 1). The replaced sensitizing dye was added in an amount of 4.5 × 10 ^-4 mol per mol of silver halide. In order to examine the sensitivity of the sample thus obtained, the same exposure and processing steps as in Example 1 of JP-A-5-313297 were performed, and the processing was performed using the processing solution, and the transfer density was measured with a color densitometer. The sensitivity was expressed as a relative value at a density of 1.0. When the sensitivity of the comparative sample 411 was set to 100, the sensitivity of the sample 412 of the present invention was 193, which was high.

Example 6 Emulsion F in Example 2 of JP-A-4-42536 was different from Example 2 in that no red-sensitive sensitizing dye (S-1) was added before sulfur sensitization. In addition, gold sulfur sensitization was optimally performed by using chloroauric acid in combination. After gold sulfur sensitization, the sensitizing dye (S-1) (comparative dye) or sensitizing dye (No. 1) was replaced with silver halide. 2 × 10 ^-4 mole or 1 × per mole
Silver chlorobromide emulsions differing only in the addition of 10 ^-4 moles were prepared and used as emulsions 501 and 502. A multilayer color printing paper was prepared in the same manner as in Sample 1 of Example 1 of JP-A-6-347944. The emulsion of the first layer in Sample 20 of Example 1 of JP-A-6-347944 was replaced with Emulsion 501 or Emulsion 5
The samples changed to 02 were designated as Sample 511 and Sample 512. To check the sensitivity of the sample thus obtained, Fuji FW
Exposure to 1/10 second exposure to light of a type sensitometer (Fuji Photo Film Co., Ltd.) through an optical wedge and blue filter,
A color development process was performed using the same processing steps and processing solution as in Example 1 of JP-A-6-347944. As a result, Comparative Sample 5
When the sensitivity of No. 11 was set to 100, the sensitivity of Sample 512 of the present invention was 156, which was high.

Example 7 A tabular silver chloride emulsion was prepared in the same manner as in Emulsion A of Example 1 of JP-A-8-122954.
Sensitizing dye-1 and sensitizing dye (S-1) or sensitizing dye (No. 1) were substituted for sensitizing dyes 1 and 2 at 1 ×
Chemical sensitization was carried out only by adding 10 ^-4 mol, and these were used as emulsion 601 and emulsion 612. The coating sample was prepared by replacing the emulsion of Example 1 of Japanese Patent Application No. 7-232036 with Emulsion 601 or Emulsion 602, and combining an emulsion layer and a surface protective layer on a support in the same manner as in Example 1 by simultaneous extrusion. This was used as Sample 611 and Sample 612. The amount of silver applied per side was 1.75 g / m ² . In order to examine the sensitivity of the sample thus obtained, exposure was performed for 0.05 seconds from both sides using an X-ray orthoscreen HGM manufactured by Fuji Photo Film Co., Ltd. Processing was carried out in the same manner as in Example 1, using an automatic developing machine and a processing solution. The sensitivity was represented by the logarithm of the reciprocal of the exposure required to give a density of fog +0.1, and the sensitivity of sample 611 was set to 100, and the other values were represented by relative values. As a result, the sensitivity of Sample 612 of the present invention was 202, which was high. The same effect was obtained by exposing with HR-4 or HGH instead of the X-ray orthoscreen HGM used at the time of exposure.

Example 8 Emulsion D of Example 2 of Japanese Patent Application No. 7-146891 was a sensitizing dye-
A tabular silver chloride emulsion was prepared, the only difference being that no 2 and 3 were added. The coated sample was prepared in the same manner as in the coated sample F of Example 3 of Japanese Patent Application No. 74-168991. Emulsion F and sensitizing dye-1 of coating sample F of Example 3 of Japanese Patent Application No. 74-168991 were added to emulsion 701 and sensitizing dye (S-1).
Alternatively, replace sensitizing dye (No. 1) with sample 711.
And Sample 712. The replaced sensitizing dye was added in an amount of 2.5 × 10 ^-4 mol per mol of silver halide. To examine the sensitivity of the sample thus obtained, Fuji F
The light of a W-type photometer (Fuji Photo Film Co., Ltd.) was exposed to light for 1/100 second through an optical wedge and a green filter, and processed by Fuji Photo Film CN16 to compare the photographic properties. The sensitivity is represented by the logarithm of the reciprocal of the exposure amount required to give a density of fog + 0.2, and the sensitivity of sample 711 was set to 100. The sensitivity of Sample 712 of the present invention was 144, which was high.

Example 9 An octahedral silver chloride emulsion was prepared in the same manner as in Emulsion F of Example 3 of Japanese Patent Application No. 7-146891. The coated sample was prepared in the same manner as in the coated sample F of Example 3 of Japanese Patent Application No. 74-168991. The emulsion F and the sensitizing dye-1 of the coating sample F of Example 3 of Japanese Patent Application No. 74-168991 were replaced with the emulsion 801 and the sensitizing dye (S-1) or the sensitizing dye (No. 1).
Samples 811 and 812 were obtained. The replaced sensitizing dye was added in an amount of 5 × 10 ^-4 mol per mol of silver halide. In order to examine the sensitivity of the sample thus obtained,
The light of a Fuji FW type photometer (Fuji Photo Film Co., Ltd.) was exposed to light for 1/100 second through an optical wedge and a green filter, and processed by Fuji Photo Film CN16 to compare the photographic properties. The sensitivity is represented by the logarithm of the reciprocal of the exposure required to give a density of fog + 0.2, and the sensitivity of sample 811 is 1
00. The sensitivity of Sample 812 of the present invention was 155, which was high.

Example 10 A silver iodobromide emulsion was prepared in the same manner as in Emulsion E of Example 1 of JP-A-7-159950 to obtain Emulsion 9. The multilayer color photographic material was prepared in the same manner as in Sample 1 of Example 1 of JP-A-7-159950. The emulsion E of the tenth layer in the sample 101 of Example 1 of JP-A-7-159950 was replaced with Emulsion 9 and ExS-3
Was replaced with the sensitizing dye (S-1) or (No. 1) to obtain Samples 901 and 902 in which 9.8 × 10 ^-4 mol was added per 1 mol of silver halide. To examine the sensitivity of the sample thus obtained, the light of a Fuji FW type sensitometer (Fuji Photo Film Co., Ltd.) was exposed to light for 1/100 second through an optical wedge and a green filter. Color development was performed using the same processing steps and processing solution as described above, and the magenta density was measured.

The sensitivity was indicated by a relative value of fog + 0.2. As a result, the sensitivity of the sample 902 of the present invention was 161 as high as 100 (reference) of the comparative sample 901. Further, the color reproducibility (green discrimination) was sensorially evaluated in the same manner as in Example 1 of JP-A-7-159950.
01 was 31, whereas Sample 902 of the present invention was 5.1, which was excellent.

[0085]

By using the novel compound of the present invention, a silver halide photographic material having high sensitivity can be obtained.

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[Procedure amendment]

[Submission date] June 16, 1998

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0036

[Correction method] Change

[Correction contents]

[0036]

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[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0062

[Correction method] Change

[Correction contents]

[0062]

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Claims (8)

[Claims] 1. A methine compound comprising a disulfide group. However, this methine compound excludes a cyanine dye. 2. A cyanine dye, wherein a substituent containing a disulfide group is substituted on a nitrogen atom of a nitrogen-containing heterocyclic ring. 3. A hemicyanine dye comprising the compound according to claim 1, which contains a disulfide group. 4. A compound represented by the general formula (1) among the compounds according to claim 1. General formula (1) In the formula, Z1 represents a 5- or 6-membered nitrogen-containing heterocyclic ring. However, this heterocyclic ring may be further condensed. A represents a divalent linking group. R1 represents an alkyl group. R2 and R
3 represents an alkyl group, an aryl group or a heterocyclic group, and R2 and R3 may form a ring. L1, L
2, L3 and L4 each represent an optionally substituted methine group. n1 represents 0, 1, 2, 3 or 4. p1 represents 0 or 1. M1 represents a charge neutralizing ion. m1 represents the number required to neutralize the charge. 5. A merocyanine dye comprising the compound according to claim 1 and having a disulfide group. 6. An oxonol dye comprising the compound according to claim 1 and containing a disulfide group. 7. A silver halide photographic material comprising the methine compound according to claim 1 or 2. 8. A silver halide photosensitive material comprising the compound represented by the general formula (1) according to claim 4.