JPH1152508A - Silver halide photosensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the silver halide photographic sensitive material high in photographic sensitivity by incorporating at least one of specified compounds in an emulsion layer containing silver halide grains having a specified aspect ratio. SOLUTION: The silver halide emulsion comprising the silver halide grains having an aspect ratio of 3-100 contains at least one of the compounds represented by formulae I and II in which each of L1 -L9 is an optionally substituted methine group; each of n1 -n3 is 0-4; each of R1 -R10 is an alkyl or aryl or heterocyclic group; each of M1 and M2 is a charge balancing counter ion; each of m1 and m2 is a number of 0-10 necessary to balance a molecular charge; and Q is a divalent bonding group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a silver halide light-sensitive material, and more particularly to a silver halide light-sensitive material containing a streptocyanine dye.

[0002]

2. Description of the Related Art Hitherto, great efforts have been made to increase the sensitivity of silver halide photographic materials. The sensitivity of the silver halide photographic light-sensitive material is determined by the latent image forming efficiency including the light absorptivity of the grains and the spectral sensitization, and the minimum latent image size. Among them, some of the techniques that have hitherto been known regarding techniques for improving the light absorptivity of particles are shown below. The high aspect ratio tabular grain emulsion technology disclosed in U.S. Pat. No. 5,494,789 and the like can be used to increase the amount of dye adsorbed per grain due to the increase in grain area, thereby improving the light absorption rate. Can be. However, there is a limit to the increase in the particle surface area due to an increase in the aspect ratio or the like, and development of a technique for improving the light absorption rate of one particle has been desired. On the other hand, if the light absorption of the sensitizing dye is increased, it is expected that the transmission of light energy to the silver halide will increase and the spectral sensitivity will increase. However, conventional dyes were still at unsatisfactory levels.

[0003]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a silver halide light-sensitive material having high photographic sensitivity.

[0004]

The object of the present invention has been attained by the following (I) to (II). (1) The silver halide grains containing at least one compound represented by the general formula (I) or (II) and forming an emulsion layer containing the compound have an aspect ratio of 3 to 100. A silver halide photosensitive material characterized by the following. General formula (I)

[0005]

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In the formula, L1, L2 and L3 each represent a methine group. n1 represents 0, 1, 2, 3 or 4. R1,
R2, R3 and R4 each represent an alkyl group, an aryl group or a heterocyclic group. M1 represents a charge-balancing counter ion, and m1 represents a number from 0 to 10 required to neutralize the charge of the molecule. General formula (II)

[0007]

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In the formula, L4, L5, L6, L7, L8 and L9 each represent a methine group. n2 and n3 are each 0,
Represents 1, 2, 3 or 4. Q represents a divalent linking group.
R5, R6, R7, R8, R9 and R10 each represent an alkyl group, an aryl group or a heterocyclic group. M2 represents a charge balancing counter ion, and m2 represents a number from 0 to 10 required to neutralize the charge of the molecule. (2) The methine compound described in (1) is a compound represented by the general formula (I)
A compound represented by I) and having an aspect ratio of 10
(1) The silver halide photographic material as described in (1) above, wherein the silver halide grains have a particle size of 50 or more.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the general formulas (I) and (II) of the present invention will be described in detail.

In the general formulas (I) and (II), L
The methine groups represented by 1, L2, L3, L4, L5, L6, L7, L8, and L9 may have a substituent,
Assuming that the substituent is V, the substituent represented by V is not particularly limited. For example, a halogen atom (eg, chlorine, bromine, iodine, fluorine), a mercapto group, a cyano group,
Carboxyl group, phosphate group, sulfo group, hydroxy group,
A carbamoyl group having 1 to 10 carbon atoms, preferably 2 to 8 carbon atoms, more preferably 2 to 5 carbon atoms (eg, methylcarbamoyl, ethylcarbamoyl, morpholinocarbonyl), 0 to 10 carbon atoms, preferably 2 to 8 carbon atoms More preferably, a sulfamoyl group having 2 to 5 carbon atoms (eg, methylsulfamoyl, ethylsulfamoyl, piperidinosulfonyl), a nitro group, 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably An alkoxy group having 1 to 8 carbon atoms (for example, methoxy, ethoxy, 2-methoxyethoxy, 2-phenylethoxy), having 6 to 20 carbon atoms, preferably 6 to 1 carbon atoms;
2, more preferably an aryloxy group having 6 to 10 carbon atoms (eg, phenoxy, p-methylphenoxy, p-
Chlorophenoxy, naphthoxy),

An acyl group having 1 to 20 carbon atoms, preferably 2 to 12 carbon atoms, more preferably 2 to 8 carbon atoms (eg, acetyl, benzoyl, trichloroacetyl), 1 to 20 carbon atoms, preferably 2 to 20 carbon atoms 1
2, more preferably an acyloxy group having 2 to 8 carbon atoms (eg, acetyloxy, benzoyloxy), an acylamino group having 1 to 20, preferably 2 to 12, and more preferably 2 to 8 carbon atoms (eg, acetyl Amino), a sulfonyl group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms (for example, methanesulfonyl, ethanesulfonyl, benzenesulfonyl and the like), 1 to 20 carbon atoms, preferably 1 carbon atom To 10, more preferably a sulfinyl group having 1 to 8 carbon atoms (eg, methanesulfinyl, benzenesulfinyl), a sulfonylamino group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms (eg, Methanesulfonylamino, ethanesulfonylamino, ben Such emission sulfonylamino)

An amino group, a substituted amino group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms (eg, methylamino, dimethylamino,
Benzylamino, anilino, diphenylamino), an ammonium group having 0 to 15 carbon atoms, preferably 3 to 10 carbon atoms, more preferably 3 to 6 carbon atoms (for example, trimethylammonium group, triethylammonium group);
A hydrazino group having 0 to 15 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms (for example, trimethylhydrazino group), 1 to 15 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms
(E.g., ureido group, N, N-dimethylureido group), an imide group having 1 to 15 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms (e.g., succinimide group), An alkyl or arylthio group having 1 to 20, preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms (eg, methylthio, ethylthio, carboxyethylthio, sulfobutylthio, phenylthio, etc.), 2 to 20 carbon atoms, preferably 2 to 12 carbon atoms, more preferably 2 to 8 carbon atoms
An alkoxycarbonyl group (e.g., methoxycarbonyl, ethoxycarbonyl, benzyloxycarbonyl) having 6 to 20 carbon atoms, preferably 6 to 12 carbon atoms;
More preferably, an aryloxycarbonyl group having 6 to 8 carbon atoms (for example, phenoxycarbonyl),

An unsubstituted alkyl group having 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms (eg, methyl, ethyl, propyl, butyl), and 1 to 18 carbon atoms, preferably 1 to 1 carbon atoms
0, more preferably a substituted alkyl group having 1 to 5 carbon atoms (hydroxymethyl, trifluoromethyl, benzyl,
Carboxyethyl, ethoxycarbonylmethyl, acetylaminomethyl, and here, preferably, an unsaturated hydrocarbon group having 2 to 18 carbon atoms, more preferably 3 to 10 carbon atoms, and particularly preferably 3 to 5 carbon atoms (for example, vinyl group Ethynyl group, 1-cyclohexenyl group, benzylidine group, benzylidene group) are also included in the substituted alkyl group. ), A substituted or unsubstituted aryl group having 6 to 20 carbon atoms, preferably 6 to 15 carbon atoms, more preferably 6 to 10 carbon atoms (eg, phenyl, naphthyl, p-carboxyphenyl, p-nitrophenyl,
3,5-dichlorophenyl, p-cyanophenyl, m-
Fluorophenyl, p-tolyl),

An optionally substituted heterocyclic group having 1 to 20 carbon atoms, preferably 2 to 10 carbon atoms, more preferably 4 to 6 carbon atoms (eg, pyridyl, 5-methylpyridyl, thienyl, furyl, morpholino, tetrahydro Furfuryl).

Preferred examples of the substituent include the above-mentioned alkyl group, aryl group, alkoxy group, halogen atom, acyl group, cyano group, sulfonyl group and benzene ring condensation, and more preferably alkyl group, aryl group, halogen atom. , An acyl group and a sulfonyl group, particularly preferably a methyl group, a phenyl group, a methoxy group, a chlorine atom, a bromine atom and an iodine atom. Most preferably,
A phenyl group, a chlorine atom, a bromine atom and an iodine atom. L
Each of 1 to L9 is preferably an unsubstituted methine group. n
1, 1, 2 and n3 are preferably 0, 1, 2, and 3, more preferably 0, 1, and 2, and particularly preferably 2. When n1, n2 and n3 are 2 or more, the methine group is repeated but need not be the same.

In the general formula (II), Q represents a divalent linking group or a single bond, and is preferably a divalent linking group. The divalent linking group preferably comprises 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, ethylene, propylene, butylene, pentylene), an arylene group (eg, phenylene, naphthylene), an alkenylene group (eg, ethenylene, propenylene), an alkynylene group (eg, ethinylene, propynylene), amide Group, ester group, sulfonamide group, sulfonic acid ester group, ureido group, sulfonyl group, sulfinyl group, thioether group, ether group, carbonyl group, -N (Ra)-(Ra is a hydrogen atom,
Represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. ), A heterocyclic divalent group (for example, 6-chloro-
1,3,5-triazine-2,4-diyl group, pyrimidine-2,4-diyl group, quinoxaline-2,3-diyl group) having 1 to 20 carbon atoms. Represents a divalent linking group. These divalent linking groups may be further substituted, and examples of the substituent include the aforementioned V.

More preferably, an alkylene group having 1 to 4 carbon atoms (eg, methylene, ethylene, propylene, butylene), an arylene group having 6 to 10 carbon atoms (eg, phenylene, naphthylene), 1 to 4 carbon atoms
A divalent linkage having 1 to 10 carbon atoms formed by combining one or more of the following alkenylene groups (eg, ethenylene, propenylene) and alkynylene groups having 1 to 4 carbon atoms (eg, ethynylene, proopinylene). Group.

R1 in the general formulas (I) and (II),
R2, R3, R4, R5, R6, R7, R8, R9, and R10 each represent an alkyl group, an aryl group, or a heterocyclic group. Examples of the alkyl group include unsubstituted alkyl groups having 1 to 18, preferably 1 to 7, and particularly preferably 1 to 4 carbon atoms (eg, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, hexyl, octyl, dodecyl, Octadecyl), 1 to 1 carbon atoms
8, preferably 1 to 7, particularly preferably 1 to 4, substituted alkyl groups, such as the alkyl groups substituted by V mentioned as substituents such as Z ₁ described above. Preferably, an aralkyl group (eg, benzyl, 2-phenylethyl), an unsaturated hydrocarbon group (eg, an allyl group), a hydroxyalkyl group (eg, 2-hydroxyethyl, 3-hydroxypropyl), a carboxyalkyl group (eg,
2-carboxyethyl, 3-carboxypropyl, 4-
Carboxybutyl, carboxymethyl), alkoxyalkyl groups (eg, 2-methoxyethyl, 2- (2-methoxyethoxy) ethyl), aryloxyalkyl groups (eg, 2-phenoxyethyl, 2- (1-naphthoxy) ethyl), Alkoxycarbonylalkyl group (for example, ethoxycarbonylmethyl, 2-benzyloxycarbonylethyl), aryloxycarbonylalkyl group (for example, 3-phenoxycarbonylpropyl), acyloxyalkyl group (for example, 2-acetyloxyethyl), acylalkyl group (for example, -Acetylethyl), a carbamoylalkyl group (eg, 2-morpholinocarbonylethyl), a sulfamoylalkyl group (eg, N, N-dimethylcarbamoylmethyl), a sulfoalkyl group (eg, 2-sulfoethyl) , 3-sulfopropyl, 3-sulfobutyl, 4-sulfobutyl, 2- [3-
Sulfopropoxy] ethyl, 2-hydroxy-3-sulfopropyl, 3-sulfopropoxyethoxyethyl),
A sulfoalkenyl group (for example, a sulfopropenyl group),
Sulfatoalkyl groups (eg, 2-sulfatoethyl group, 3-sulfatopropyl, 4-sulfatobutyl), heterocyclic-substituted alkyl groups (eg, 2- (pyrrolidin-2-one-1-yl) ethyl, tetrahydro Furfuryl), an alkylsulfonylcarbamoylmethyl group (for example, a methanesulfonylcarbamoylmethyl group)}.

The aryl group includes, for example, an unsubstituted aryl group having 6 to 20 carbon atoms, preferably 6 to 10 carbon atoms, more preferably 6 to 8 carbon atoms (eg, phenyl group, 1-naphthyl group), and 6 carbon atoms. To 20, preferably 6 to 10, more preferably 6 to 8 substituted aryl groups (for example, the aryl group substituted by V mentioned as a substituent such as Z1 described above. Specific examples include p. -Methoxyphenyl group, p-methylphenyl group, p
-Chlorophenyl group and the like. ).

The heterocyclic group is, for example, one having 1 to 2 carbon atoms.
0, preferably an unsubstituted heterocyclic group having 3 to 10 carbon atoms, more preferably 4 to 8 carbon atoms (for example, a 2-furyl group,
2-thienyl group, 2-pyridyl group, 3-pyrazolyl, 3
-Isoxazolyl, 3-isothiazolyl, 2-imidazolyl, 2-oxazolyl, 2-thiazolyl, 2-pyridazyl, 2-pyrimidyl, 3-pyrazyl, 2- (1,3,5-
Triazolyl), 3- (1,2,4-triazolyl), 5-tetrazolyl), having 1 to 20 carbon atoms, preferably 3 carbon atoms
10, even more preferably include the heterocyclic group V mentioned is substituted as a substituent, such as Z ₁ substituted Hajime Tamaki (e.g., the aforementioned 8 from 4 carbon atoms. Specifically 5-methyl-2- Thienyl group, 4-methoxy-2-pyridyl group, etc.).

Preferred are the above-mentioned unsubstituted alkyl, sulfoalkyl, carboxyalkyl, unsubstituted aryl and unsubstituted heterocyclic groups, more preferably methyl,
Ethyl, 2-sulfoethyl, 3-sulfopropyl, 3-
Sulfobutyl, 4-sulfobutyl, carboxymethyl,
Phenyl, 2-pyridyl and 2-thiazolyl.

Further, R7 and R8 can be combined to form the same divalent linking group as Q described above.

M1 and M2 are included in the formula to indicate the presence of a cation or an anion when necessary to neutralize the ionic charge of the dye. Typical cations include inorganic cations such as hydrogen ion (H ⁺ ), alkali metal ions (eg, sodium ion, potassium ion, lithium ion), alkaline earth metal ions (eg, calcium ion), and ammonium ions (eg, Organic ions such as ammonium ion, tetraalkylammonium ion, pyridinium ion, and ethylpyridinium ion. The anion may be either an inorganic anion or an organic anion, such as a halogen anion (eg, a fluorine ion, a chloride ion, an iodine ion), a substituted arylsulfonate ion (eg, p-toluenesulfonic acid ion, p-chloroion). Benzenesulfonate ion, aryldisulfonate ion (eg, 1,3-benzenesulfonate ion, 1,5
-Naphthalenedisulfonic acid ion, 2,6-naphthalenedisulfonic acid ion), alkyl sulfate ion (for example, methyl sulfate ion), sulfate ion, thiocyanate ion,
Examples include perchlorate ion, tetrafluoroborate ion, picrate ion, acetate ion, and trifluoromethanesulfonate ion. Further, another dye having a charge opposite to that of the ionic polymer or the dye may be used. In the present invention, the sulfo group is described as SO ₃ ^— , but when it has a hydrogen ion as a counter ion, it can be described as SO ₃ H. m1 and m2 represent the numbers required to balance the charges, and are 0 when a salt is formed in the molecule.

The general formulas (I) and (II) of the present invention are described below.
Specific examples of the compound represented by are shown below, but this does not limit the present invention.

[0025]

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[0026]

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[0027]

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[0028]

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[0029]

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[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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The compounds represented by the general formulas (I) and (II) of the present invention are described in FM Harmer, "Heterocyclic Compounds-Cyanine Soybeans and Related Compounds (Heterocyclic Compounds)".
Compounds-Cyanine Dyes and Related Compounds)
John Wiley & Sons
s) Company-New York, London, 1964, DMSturmer, Heterocyclic Compound Special Topics in
Heterocyclic chemistry
(ounds-Special topics in heterocyclic chemistry)
Chapter 18, Section 14, 482-515 Tribute, John Wiley & Sons
-New York, London, 1977, "Rod's Chemistry of Carbon Compounds (Rodd's
s Chemistry of Carbon Compounds) '' 2nd.Ed.vol.IV, pa
rtB, 1977, Chapter 15, Chapters 369-422, published by Elsevier Science Publishing Company Inc.,
It can be synthesized based on the method described in New York and the like.

Next, the silver halide photographic material of the present invention will be described in detail. The general formulas (I) and (I)
Compound represented by I) (hereinafter, methine compound of the present invention)
Can be used alone or in combination with other sensitizing dyes in a silver halide photographic light-sensitive 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 in any of the emulsion preparations which have been recognized to be useful. It may be during the process. For example,
U.S. Pat. Nos. 2,735,766 and 3,628,960
Nos. 4,183,756 and 4,225,666
JP-A-58-184142 and JP-A-60-19674.
As disclosed in No. 9, 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, 58
As disclosed in, for example, JP-A-113920, it may be added at any time during the process immediately before or during the process of chemical ripening, or at any time before the application of the emulsion after the chemical ripening and before coating. No. 4,225,666.
As disclosed in JP-A-58-7629 or the like, the same compound may be used alone or in combination with a compound having a different structure, for example, during the particle forming step, during the chemical ripening step, or after the completion of the chemical ripening. Or may be divided and added before or during chemical ripening or during and after the process, or may be added by changing the kind of compound to be divided and added and the combination of compounds. .

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, water, pyridine 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, as described in US Pat. No. 3,469,987, the compound is dissolved in a volatile organic solvent,
This solution is dispersed in a hydrophilic colloid, and this dispersion is added to the emulsion. As described in JP-B-46-24185, the dispersion is dispersed in a water-soluble solvent, and this dispersion is added to the emulsion. Dissolving a methine compound in a surfactant, as described in US Pat. No. 3,822,135;
A method of adding the solution to an emulsion, JP-A-51-7462.
4, a method of dissolving with a compound that causes a red shift and adding the solution to an emulsion;
As described in JP-A-80826, a method of dissolving a methine compound in an acid substantially free of water and adding the solution to an emulsion is used. Other additions to emulsions include U.S. Pat. Nos. 2,912,343 and 3,342,605.
Nos. 2,996,287 and 3,429,835 can also be used.

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

The supersensitizers useful in the spectral sensitization of the present invention include, for example, US Pat. Nos. 3,511,664, 3,615,613, 3,615,632, and 3,615, Nos. 641, 4,596,767, 4,945,038, 4,965,182, 4,965,182, etc., pyrimidylamino compounds, triazinylamino compounds, azolium compounds, etc. The method described in the above-mentioned patent is also preferable as to its use.

The silver halide which can be used in the silver halide 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. Also, JP-A-63-2
The constitution and processing described in No. 64743 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 fogged (For example, a direct positive photosensitive material). Silver halide grains having the various halogen compositions, crystal habits, intragrain structures, shapes and distributions described above,
Used in photosensitive photographic materials (elements) for various uses.

The silver halide grains in the photographic light-sensitive material of the present invention have a tabular crystal form. The aspect ratio of the particles is 3 or more, preferably 3 or more and 100 or less. Here, the aspect ratio of 3 or more and 100 or less means that the 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 the silver halide grains in the emulsion. 50% of projected area
This means that it exists. Preferably at least 70%,
More preferably, it is at least 85%.

The aspect ratio is preferably 3 or more and 50 or less, more preferably 10 or more and 50 or less, and particularly preferably 10 or more and 30 or less. Tabular grains are by Gatoff, Photographic Science and Engineering (Gutoff, Photographic Scien
ce and Engineering), Vol. 14, pp. 248-257 (1970
Years); US Pat. No. 4,434,226 and 4,414,310
Nos. 4,433,048 and 4,439,520
No., GB2,112,157 and WO96 / 30808
Can be adjusted by the method described on page 16, line 5 to page 20, line 19. The methine compound of the present invention is used in the following photographic materials for the purpose of sensitizing agents, sensitizing dyes, filters, antihalation or irradiation prevention. These dyes can be added to desired layers such as an intermediate layer, a protective layer and a back layer in addition to the photosensitive emulsion layer. The methine compound of the present invention is used for various color and black-and-white silver halide photographic materials. More specifically, a photosensitive material for color positive, a photosensitive material for color paper, a photosensitive material for color negative, a photosensitive material for color reversal (with or without a coupler), a silver halide photographic photosensitive material for direct positive , Photosensitive materials for plate making (eg lith film, lith dupe film, etc.), photosensitive materials for cathode ray tube displays, photosensitive materials for X-ray recording (especially materials for direct and indirect photography using a screen), silver salt diffusion transfer process (Silver Salt diffusion
photosensitive material used in the transfer process), photosensitive material used in the color diffusion transfer process, photosensitive material used in the die transfer process (imhibition process),
It is used for a photosensitive material used in a silver dye bleaching method, a photosensitive material for thermal development, and the like.

The silver halide photographic emulsion used in the present invention is described in P. Glaflkides, "Simmy.
Chimie et Phys
iquePhotograhique "(Paul Montel)
Publisher, 1967), GF Deffein (GFDu
ffin), "Photographic Emulsion Chemistry" (The Focal Press, 1966),
Making and Coating Photographic Emulsion by VLZelikman et al.
Emulsion) "(The Focal Pres
s), 1964) and the like.

In the formation of silver halide grains, in order to control the growth of the grains, silver halide solvents such as ammonia, rodancali, rhodamonmon, and thioether compounds (for example, US Pat. No. 3,271,157)
Nos. 3,574,628 and 3,704,130
Nos. 4,297,439 and 4,276,374) and thione compounds (for example, JP-A-53-14431).
9, No. 53-82408 and No. 55-77737), amine compounds (for example, JP-A-54-100717).
Number 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 salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt may be coexisted. As the internal latent image type silver halide emulsion used in the present invention, for example, US Pat. No. 2,592,250,
Conversion-type silver halide emulsions described in 3,206,313, 3,447,927, 3,761,276, and 3,935,014, etc., core / shell type halides Silver emulsions and silver halide emulsions containing different types of metals are included.

The silver halide emulsion is usually chemically sensitized. For chemical sensitization, see, for example, H. Frieser, “Die Grundlagen der Photographische”, edited by D. Grundlagen der Photographischen.
n Prozesse mit Silberhalogeniden) ", Akademische Verlagsgesellsch
aft), (1968) pp. 675-734 can be used. That is, sulfur sensitization using a compound containing sulfur (e.g., thiosulfate, thioureas, mercapto compounds, rhodanines) that can react with active gelatin or silver; selenium sensitization; ,
Reduction sensitization method using stannous salts, amines, hydrazine derivatives, formamidinesulfinic acid, silane compounds); noble metal compounds (for example, gold complex salts, Pt, I
A noble metal sensitization method using a complex group VIII metal of the periodic table such as r or Pd) can be used alone or in combination.

The photographic light-sensitive material used in the present invention may contain various compounds for the purpose of preventing fog during the production process, storage or photographic processing of the light-sensitive material, or stabilizing photographic performance. it can. That is, thiazoles such as benzothiazolium salts described in U.S. Pat. Nos. 3,954,478 and 4,942,721, JP-A-59-191332, and JP-B-59-26731. Ring-opened products thereof, nitroindazoles, triazoles, benzotriazoles, benzimidazoles (especially nitro- or halogen-substituted); heterocyclic mercapto compounds such as mercaptothiazoles, mercaptobenzothiazoles, mercaptobenz Imidazoles, mercaptothiadiazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole), mercaptopyrimidines; the above heterocyclic mercapto compounds having a water-soluble group such as a carboxyl group or a sulfone group; thioketonization Compounds such as oxazolinethione; azaindenes such as tetraazaindenes (especially 4-hydroxy-substituted (1,3,3a, 7) tetraazaindenes); benzenethiosulfonic acids; benzenesulfinic acid; and JP-A-62-87957. Many compounds known as antifoggants or stabilizers can be added, such as the acetylene compounds described, and the like.

The silver halide photographic light-sensitive material of the present invention may contain a color coupler such as a cyan coupler, a magenta coupler and a yellow coupler, and a compound which disperses the coupler. That is, in the color development processing, aromatic 1
It may contain a compound capable of developing color by oxidative coupling with a secondary amine developing agent (for example, a phenylenediamine derivative or an aminophenol derivative). For example,
Examples of magenta couplers include 5-pyrazolone couplers, pyrazorobenzimidazole couplers, cyanoacetylcoumarone couplers, open-chain acylacetonitrile couplers, and yellow couplers include acylacetamide couplers (eg, benzoylacetoanilides, pivaloylacetoanilides). Some cyan couplers include 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 that releases a development inhibitor during development (a so-called DIR coupler) may be used. Also DI
In addition to the R coupler, a colorless DIR coupling compound which is colorless and releases a development inhibitor may be contained.

The photographic light-sensitive material of the present invention may be, for example, polyalkylene oxide or a derivative thereof such as ether, ester, or amine, a thioether compound, thiomorpholines, or quaternary ammonium for the purpose of increasing sensitivity, increasing contrast, or promoting development. It may contain salt compounds, urethane derivatives, urea derivatives, imidazole derivatives, 3-pyrazolidones, and the like. The silver halide light-sensitive material of the present invention may contain various dyes other than the methine compound of the present invention as a filter dye or for the purpose of preventing irradiation or other various purposes. Such dyes include, for example, British Patent Nos. 506,385 and 1,17.
7,429, 1,311,884, 1,33
8,799, 1,385,371, 1,46
7,214, 1,433,102, 1,55
3,516, JP-A-48-85130, and JP-A-49-1
No. 14420, No. 52-117123, No. 55-16
No. 1233, No. 59-111640, Japanese Patent Publication No. 39-2
No. 2069, No. 43-13168, No. 62-2735
No. 27, U.S. Pat. Nos. 3,247,127 and 3,46.
Oxonol dyes having a pyrazolone nucleus or a barbituric acid nucleus described in US Pat. Nos. 9,985 and 4,078,933; U.S. Pat. Nos. 2,533,472 and 3,37;
Other oxonol dyes described in JP-A No. 9,533, British Patent No. 1,278,621, JP-A Nos. 1-134447 and 1-183652, and British Patent No. 575,6
Nos. 91, 680, 631, 599, 623, 786, 907, 907, 125, and 1,04
No. 5,609, U.S. Pat. No. 4,255,326, Japanese Patent Publication No. Sho 59-211043, azo dyes described in JP-A Nos. 50-100116 and 54-118247, and British Patent No. 2,014, Azomethine dyes described in US Pat. No. 2,865,598 and US Pat.
No. 752, 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 No. 7303, etc.
Nos. 8-3082, 44-16594, 59-28
No. 898 and the like, British Patent No. 44
Nos. 6,583 and 1,335,422;
Triarylmethane dyes described in U.S. Pat. No. 2,228,250 and the like, British Patent Nos. 1,075,653 and 1,153,
No. 341, No. 1, 284, 730, No. 1, 475, 2
No. 28, No. 1,542,807, etc .; merocyanine dyes described in U.S. Pat.
294, 539 and JP-A-1-291247.

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 and the like. Further, a method of dyeing a specific layer using a dye solid insoluble in water is disclosed in
-12639, 55-155350, 55-1
No. 55351, No. 63-27838, No. 63-197
943, European Patent No. 15,601 and the like. Further, a method of dyeing a specific layer by using metal salt fine particles to which a dye is adsorbed is disclosed in U.S. Pat. Nos. 2,719,088, 2,496,841, and 2,496,843; No. 45237 and the like.

The photographic light-sensitive material of the present invention has various interfaces for various purposes such as coating aid, antistatic, improvement of slipperiness, emulsification / dispersion, prevention of adhesion and improvement of photographic properties (eg, acceleration of development, high contrast, sensitization). An active agent may be included. In practicing the present invention, other additives are used together with the silver halide emulsion or other hydrophilic colloid, for example, an anti-fading agent, an inorganic or organic hardening agent, an anti-fog agent,
UV absorbers, mordants, plasticizers, latex polymers,
Matting agents and the like can be mentioned. Specifically, Research Disclosure Vol.
176 (1978, 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. Finished silver halide emulsions 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 bases or glass plates.

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 (daylight), 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 1/1 which is usually used in cameras
Exposure time from 000 seconds to 1 second, of course, 1/1000
Exposure shorter than one second, for example, exposure of 1/10 ⁴ to 1/10 ⁶ seconds using a xenon flashlight or a cathode ray tube, or 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. Further, exposure may be performed by light emitted from a phosphor excited by an electron beam, X-ray, γ-ray, α-ray, or the like. Photographic processing of photosensitive materials made using the present invention includes, for example, Research Disclosure (Research Disclosure).
Disclosure) 176, pp. 28-30 (RD-1764)
As described in 3), any of a known method and a known processing solution 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. Processing temperature is usually 1
The temperature is selected between 8 ° C and 50 ° C, but may be lower than 18 ° C or higher than 50 ° C.

A silver halide photographic light-sensitive material carrying magnetic recording which may be used in the present invention (hereinafter also referred to as "light-sensitive material")
Are disclosed in JP-A-6-35118 and JP-A-6-17528.
No., a thin layer support of a pre-heat treated polyester described in detail in Hatsumei Kyokai Disclosure No. 94-6023, for example,
Polyethylene aromatic dicarboxylate polyester support, 50 μm to 300 μm, preferably 50 μm
Heat treatment (annealing) at a temperature of 40 ° C. or more and a glass transition temperature or less at a temperature of 40 to 200 μm, more preferably 80 to 115 μm, and particularly preferably 85 to 105 μm.
No. 43-2603, No. 43-2604
U.S. Pat. No. 5,326,689 by ultraviolet irradiation described in JP-B-45-3828, surface treatment such as corona described in JP-B-48-5043 and JP-A-51-131576.
No. described in US Pat. No. 2,761, if necessary
No. 791 described in JP-A-59-23.
No. 505, JP-A-4-195726, JP-A-6-59
357 may be applied. In addition,
The magnetic layer described above is disclosed in JP-A-4-124462,
It may be in the form of a stripe described in JP-A-124645.
Further, if necessary, an antistatic treatment described in JP-A-4-62543 is used, and finally a product coated with a silver halide emulsion is used. The silver halide emulsion used here is described in JP-A-4-166.
No. 932, JP-A-3-41436, JP-A-3-414
No. 37 is used. Sensitive materials made in this way are Tokuho 4-868
No. 17 manufactured by the manufacturing control method described in
Preferably, the production data is recorded by the method described in No. 46. Thereafter or before that, Japanese Patent Application Laid-Open No. 4-125560.
According to the method described in No. 5, the film is cut into a narrower film than the conventional 135 size, and the perforations are perforated with two holes per side per the small format screen to match the smaller format screen. The film thus formed is a cartridge package of Japanese Patent Application Laid-Open No. 4-157559, a cartridge shown in FIG. 9 of Japanese Patent Application Laid-Open No. 5-210202, or US Pat. No. 4,221,479.
Film Patrone and USP 4,834,306, U
S4,834,366, USP 5,226,613
No. 4,846,418. The film cartridge or film cartridge used here is USP 4,848,693.
No. 5, US Pat. No. 5,317,355 are preferred from the viewpoint of light shielding properties. Furthermore, US
It is preferable to use a cartridge having a lock mechanism as described in P5,296,886, a cartridge in which a use state described in US Pat. No. 5,347,334 is displayed, or a cartridge having a double exposure prevention function. Further, Japanese Patent Laid-Open No. 6-85
As described in No. 128, a cartridge to which a film can be 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, JP-A-6-8886, JP-A-6-999
08-No. 08-573, No. 08
No. 98, JP-A-6-101135 and JP-A-6-205690, which are capable of taking out and changing the type of film during photographing, JP-A-5-293138 and JP-A-5-283382. , For example, a camera capable of magnetically recording on a film the panoramic photography, the high-vision photography, and the normal photography (magnetic recording capable of selecting the print aspect ratio), and the dual recording described in JP-A-6-101194. The function of a film cartridge (patrone) can be sufficiently exhibited by using a camera having an exposure preventing function or a camera having a use state display function such as a film described in JP-A-5-150577. The film photographed in this way is disclosed in
Magnetic recording on a film described in JP-A-6-95265 and JP-A-4-123054, by processing with an automatic processing machine described in JP-A-222514 and JP-A-6-222545, or before, during or after the processing. Or the aspect ratio selection function described in JP-A-5-19364 may be used. In the case of cine-type development, the film is spliced and processed according to the method described in JP-A-5-119461. Further, when or after the development processing,
Attachment described in No. 48805, detach processing is performed. After processing in this manner, the film information can be converted to print through back printing on color paper and front printing by the methods described in JP-A-2-184835, JP-A-4-186335, and JP-A-6-79968. good. Further, JP-A-5-11353, JP-A-5-23
The index print and return cartridge described in No. 2594 may be returned to the customer.

Further, at least one layer is provided on each of the supports.
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 In a color light-sensitive material having at least one silver halide emulsion layer which gives a multilayer effect to the entire red-sensitive silver halide emulsion layer, the silver halide emulsion layer which gives the multilayer effect is a compound represented by formula (I): A silver halide color photographic light-sensitive material containing a compound represented by formula (VII) is preferably used. For details of such a light-sensitive material, see JP-A-7-159950 (U.S. Pat.
8,838).

[0057]

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

Example 1 Emulsions 1, 2, and 3 were prepared by the following method. (1) Preparation of Emulsion 1 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 is a triple structure grain having a region having the highest silver iodide content in the intermediate shell, having 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.

After desalting Emulsion 1 by the usual flocculation method, a sensitizing dye was added in an amount of 4.1 × 10 ^-4 mol per mol of silver to 1 mol of silver, and gold, sulfur and
Selenium sensitization was performed optimally.

(2) Preparation of Emulsion 2 An aqueous solution containing gelatin having an average molecular weight of 15,000 (water 12
1.9 M AgNO ₃ aqueous solution and 1.9 M KBr aqueous solution were added at 25 ml / min by a double jet method at 25 ml / min for 70 sec while stirring at 30 ° C. while maintaining the mixture at 00 ° C., containing 7.0 g of gelatin and 4.5 g of KBr. As a result, nuclei of tabular grains were obtained. 350 ml of this emulsion was used as seed crystals, and 650 ml of an inert gelatin aqueous solution (gelatin 20 g, KBr1.
(Including 2 g), and the mixture was heated to 75 ° C. and aged for 40 minutes. Then, an AgNO ₃ aqueous solution (including 1.7 g of AgNO ₃ ) was added over 1 minute and 30 seconds, and then NH ₄ NO
6.2 ml of ₃ (50 wt%) aqueous solution and NH ₃ (25 wt%)
6.2 ml were 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 M aqueous solution of AgNO ₃ and an aqueous solution of KBr were added thereto, followed by a 1.9 M aqueous solution of AgNO _3.
3.6 ml of an aqueous solution of KBr (containing 33.3 mol% of KI) and 160.5 ml of a 1.9 M aqueous solution of AgNO ₃
And an aqueous KBr solution were added while maintaining the pAg at 8.3 to obtain Emulsion 2. Emulsion 2 obtained is a triple structure grain having a region with the highest silver iodide content in the intermediate shell, an average aspect ratio of 6.7, and the total projected area of tabular grains having an aspect ratio of 6 or more. And the proportion of tabular grains having an aspect ratio of 3 or more and 100 or less to the total projected area was about 95%. The coefficient of variation of the particle size is 11%, and the average of the particle size is 1.0 in sphere equivalent diameter.
It was 0 μm. Emulsion 2 was desalted by the usual flocculation method, and 5.4 × 10 ⁻⁴ mol of 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. Was.

(3) Preparation of Emulsion 3 0.5 M of a 0.8% low molecular weight (molecular weight 10,000) gelatin solution having 0.05 mol of potassium bromide was stirred by a double jet method with a 0.5 M solution. 15 cc of a silver nitrate solution and a 0.5 M potassium bromide solution are added for 15 seconds. During this time, the gelatin solution was kept at 40 ° C.
At this time, the pH of the gelatin solution was 5.0. After the addition,
The temperature was raised to 75 ° C. After addition of 220 cc of a 10% solution of trimellitized gelatin (95% trimellitization), the emulsion was ripened for 20 minutes. Thereafter, 80 cc of a 0.47 M silver nitrate solution was added. After further aging for 10 minutes,
Controlled at an accelerated flow rate of a potassium bromide solution containing 5 mol% of potassium iodide to keep 150 g of silver nitrate and pBr at 2.55 for 60 minutes (the flow rate at the end is 19 times the flow rate at the start). It was added while being kept at 0 mV by the double jet method. After the addition, 30 cc of 10% KI solution
Was added. Thereafter, 1N NaOH was added to the emulsion to obtain p.
After adjusting the H to 7.2, 327 cc of a 0.5 M silver nitrate solution and 327 cc of a 0.5 M potassium bromide solution to which 16.4 cc of a 10 ^-2 M solution of yellow blood salt were added were controlled at a potential of 0 mV for 20 minutes. Added by the double jet method. (Shell formation) Thereafter, the emulsion was cooled to 35 ° C., washed with water by an ordinary flocculation method, and 80 g of deionized alkali-treated bone gelatin and 4% of 2% Zn (NO ₃ ) ₂ were added at 40 ° C.
After adding 0 cc and dissolving to adjust the pH to 6.5 and the pAg to 8.6, the mixture was stored in a cool and dark place. The tabular grains have a projected area equivalent circle diameter (hereinafter referred to as circle equivalent diameter) variation coefficient of 15%, an equivalent circle diameter of 2.5 μm, and an average thickness of 0.1%.
0 μm (aspect ratio 25) and 5.7 in silver iodide.
It was a silver iodobromide emulsion containing mol%. Emulsion 3 was desalted by a usual flocculation method, and 9.3 × 10 ^-4 mol of sensitizing dye was added to 1 mol of silver, and sodium thiosulfate, potassium chloroaurate and thiocyanic acid were added in the presence of silver. Optimal chemical sensitization at 60 ° C. with potassium. (2) Preparation of Coated Sample A triacetyl cellulose film support provided with an undercoat layer was coated with an emulsion layer and a protective layer as shown in Table 1 to prepare a sample.

[0064]

[Table 1]

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

Processing method Step Processing time Processing temperature Compensation 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 each of the samples 1-1, 2-1 and 3-1 being 100. The emulsion and methine compound species used for each sample and the sensitivity results for each sample are shown in Table 2 below.
Shown in

[0068]

[Table 2]

[0069]

Embedded image

From Table 2, it can be seen that the compounds of the present invention are only slightly more sensitive in Emulsion 1 with a low aspect ratio than in Comparative Dye S-1, but in Emulsions 2 and 3 with a high aspect ratio, It can be seen that the sensitivity is significantly higher than that of the comparative dye.

Example 2 (Preparation of Normal Silver Chloride Normal Crystal Particles) 4.8 g of sodium chloride and 3.0 g of inert gelatin were added to 1 liter of water.
While stirring into a container maintained at 0 ° C., an aqueous silver nitrate solution 600
cc (21.3 g of silver nitrate) and an aqueous solution of sodium chloride 600
cc (7.74 g of sodium chloride) was added over 20 minutes by the dazzle jet method. Five minutes after the completion of the addition, the crystal habit controlling agent described in Table 3 was added. Then, 5 minutes after the addition of the crystal habit controlling agent, 300 cc of an aqueous silver nitrate solution (112.5 g of silver nitrate) and 300 cc of an aqueous sodium chloride solution (40.
4g) was added over 60 minutes. After completion of addition, 60 ° C
At a concentration of 4.0 × 10 ⁻³ mol /
Molar silver was added. After 10 minutes, the sensitizing dyes shown in Table 3 were added, the temperature was raised to 75 ° C., and stirring was continued for another 10 minutes. After the temperature was lowered to 40 ° C., an aqueous solution containing the precipitant-1 was added to make the total volume 3.5 liters, and then the pH was lowered using sulfuric acid until the silver halide precipitated (pH = 3.
8). Next, 83% of the supernatant (supernatant 1 (S1)) was removed (first washing). Further, the same amount of distilled water as that removed was added, and then sulfuric acid was added until silver halide precipitated. 83% of the supernatant (supernatant 2 (S2)) was removed again (second washing with water). Further, the same amount of distilled water as that removed was added, and then sulfuric acid was added until silver halide precipitated. 83% of the supernatant liquid again (supernatant liquid 3 (S3))
Was removed (third water washing) to complete the desalting step.

[0072]

Embedded image

67 g of gelatin and 8% of phenol (5%)
0 cc and 150 cc of distilled water were added. The pH was adjusted to 6.2 and the pAg to 7.5 with sodium hydroxide and silver nitrate solutions. Thus, emulsions R1 to R16 containing pure silver chloride and containing grains having an average sphere equivalent diameter of 0.55 μm were obtained.

[0074]

[Table 3]

[0075]

Embedded image

(Preparation of pure silver chloride tetradecahedral grains) Emulsions R17 to R2 were prepared in the same manner as described above except that the crystal habit controlling agent shown in Table 1 was added when 50 g of silver nitrate was added.
0 was prepared. The obtained particles were tetrahedral particles having an equivalent sphere diameter of 0.55 μm, and 60% of the outer surface was {111} planes.

(Chemical sensitization) Emulsions R1 to R20 were prepared at 60 ° C.
Wherein 4-hydroxy-6-methyl-1,3,3
Optimally chemically sensitized with a, 7-tetraazaindene, sodium thiosulfate and chloroauric acid.

(Preparation of Pure Silver Chloride {100} Tabular Grains) pH 4.3 containing 25 g of deionized alkali-treated bone gelatin having a methionine content of about 40 μmol / g, 1 g of sodium chloride and 4.5 ml of 1N nitric acid. Gelatin aqueous solution 12
00 ml was placed in a reaction vessel and heated to 40 ° C. An aqueous solution 100 g containing 20 g of silver nitrate is added to this solution while stirring vigorously.
(A) solution, 0.71 g of potassium bromide and 6.67 g of sodium chloride in 100 ml of an aqueous solution (B) were mixed with 36
Each ml was added simultaneously for 45 seconds. After stirring for 3 minutes after completion of the addition, an aqueous solution 1 containing 1.1 g of potassium bromide was added.
43.4 ml of 00 ml of solution (C) were added in 30 seconds.
After that, the temperature was lowered to 30 ° C. in 3 minutes, and the temperature was kept constant. Then, the solution (A) and the solution (D) of 100 ml of an aqueous solution containing 7.02 g of sodium chloride were simultaneously mixed and added for 2 minutes and 15 seconds. did. After stirring for 1 minute, 10%
20 ml of a sodium chloride solution and 7 ml of a 1N aqueous solution of sodium hydroxide were added to adjust the pH to 6.5 and the silver potential to a saturated calomel electrode at 80 mV. Then, 2 ml of a hydrogen peroxide solution (35%) was added.
Was added. Thereafter, the temperature was raised to 75 ° C., and the mixture was aged for 5 minutes. Thereafter, a silver bromide content of average side length 0.06 μm 5
1086 g of an emulsion containing 10 mol% of silver chlorobromide cubic grains (containing 108.7 g of silver) was added while maintaining the silver potential at 140 mV.
Minutes. After the completion of the addition, 1% of potassium thiocyanate was 27 cc and the sensitizing dyes shown in Table 4 were added in an amount of 4.0% per mole of silver.
5 × 10 ^-4 mol was added and stirring was continued for 10 minutes. Thereafter, the temperature was lowered to 35 ° C., and desalting was performed according to a conventional method. The resulting emulsion had an average grain size of 0.92 expressed as a sphere-equivalent diameter.
This emulsion was composed of silver chlorobromide {100} tabular grains having an average grain diameter of 0.128 μm, an average grain thickness of 0.128 μm, an aspect ratio of 15.9, and a silver bromide content of 5 mol%. These are referred to as emulsions # 1 to # 4.

[0079]

[Table 4]

(Preparation of Pure Silver Chloride {111} Tabular Grains) 2.0 g of sodium chloride and 2.4 g of inert gelatin were added to 1.2 liters of water, and stirred in a container kept at 35 ° C. with an aqueous solution of silver nitrate. 60 cc (9 g of silver nitrate) and 60 cc of an aqueous sodium chloride solution (3.2 g of sodium chloride) were added in one minute by a double jet method. One minute after the completion of the addition, 1 mmol of the crystal habit controlling agent 1 was added. One minute later, 3.0 g of sodium chloride was added. During the next 25 minutes, the temperature of the reaction vessel was raised to 60 ° C. After aging at 60 ° C. for 16 minutes, 290 g of a 10% aqueous solution of phthalated gelatin was added. Thereafter, 754 cc of an aqueous solution of silver nitrate (113
g) and 768 cc of sodium chloride aqueous solution (41.3 g of sodium chloride) were added at an accelerated flow rate over 40 minutes. During this period, 34 cc of a 10% aqueous KBr solution was added when 37 minutes had elapsed. Further, over 30 to 40 minutes, 30 cc of a 0.25 M aqueous sodium chloride solution containing 11 mg of yellow blood salt was added. After completion of the addition, 27 cc of 1% potassium thiocyanate and 4.5 × 10 ^-4 mol of the sensitizing dye described in Table 4 were added per mol of silver. Thereafter, the temperature was raised to 75 ° C., and stirring was continued for 10 minutes. After lowering the temperature to 40 ° C., an aqueous solution containing 0.3 g of the precipitant-1 was added, and the total amount was 3.5.
After making the liter, a water washing step was performed by the same flocculation method. After washing with water, 67 g of gelatin, 80 cc of phenol (5%) and 150 cc of distilled water were added. The pH was adjusted to 6.2 and the pAg to 7.5 with sodium hydroxide and silver nitrate solutions. Thus, the average sphere equivalent diameter is 0.85μ with pure silver chloride
emulsion containing tabular grains having an average thickness of 0.14 μm
I got $ 8.

(Preparation of Pure Silver Chloride {111} Tabular Grains) Emulsion (9) was prepared in the same manner as in the preparation of tabular grains except that 1.44 mmol of crystal habit controlling agent 31 was added instead of crystal habit controlling agent 1. # 12 was prepared. The average sphere equivalent diameter of the grains in the emulsion was 0.85 μm and the average thickness was 0.12 μm.

The above tabular grain emulsion was prepared at 60 ° C.
Optimized chemical sensitization using 4-hydroxy-6-methyl-1,3,3a, 7-tetraazaindene, sodium thiosulfonate, sodium thiosulfate, selenium compound-1, chloroauric acid and compound-1 . Thus emulsion # 1
~ 12 were obtained.

[0083]

Embedded image

(Preparation of Coated Sample) Emulsion R chemically sensitized
The photographic characteristics were evaluated using 1 to R20. First, R1
The following were added to 1300 g of R20 (containing 1 mol of silver) to prepare a coating solution. -756 g of 14% aqueous solution of inert gelatin-0.129 g of sodium salt of 1- (3-sulfophenyl) -5-mercaptotetrazole-1.44 g of sodium dodecylbenzenesulfonate-Sodium polystyrenesulfonate (average molecular weight 600,000) 1 .44g · H ₂ (to be a total volume of 4860cc) O coating amount of silver was coated so as to be 1.60 g / m ² in the coating solution and surface protective layer coating solution and a co-extrusion method, a coating sample Rt
1 to Rt20 were prepared. (Evaluation of Photographic Properties) The coated samples Rt1 to Rt2 were exposed to a light source having a color temperature of 2854K for 1 second through a filter transmitting light having a wavelength longer than 420 nm. Thereafter, the film was developed with the following developer D19 at 20 ° C. for 5 minutes, and then fixed with Fuji Photo Film Super Fujifix Fixer for 30 seconds, followed by washing and drying. D19 developer • 2.2 g of metol • 96 g of Na ₂ SO ₃ • 8.8 g of hydroquinone • 56 g of NaCO ₂ • H ₂ O • 5 g of KBr The results of sensitometry are shown in Table 5. The sensitivity was expressed as a difference in exposure amount required to obtain a density of 0.1 in addition to fog, and was expressed as a relative value with the value of sample Rt1 being 100.

[0085]

[Table 5]

(Preparation of Coating Sample for Thermal Development) A sample for thermal development was prepared using the chemically sensitized emulsions # 1 to # 12 obtained above. First, a dispersion of zinc hydroxide used as a base precursor during thermal development was prepared. 31 g of zinc hydroxide powder having a primary particle size of 0.2 μm, 1.6 g of carboxymethylcellulose and 0.4 g of sodium polyacrylate as a dispersant, 8.5 g of lime-treated ossein gelatin, and 158.5 ml of water were mixed. This mixture was dispersed in a mill using glass beads for 1 hour. After dispersion, the glass beads were filtered to obtain 188 g of a dispersion of zinc hydroxide. Further, a magenta coupler was prepared. 10.7 g of cyan coupler a, 5.45 g of developing agent b, 2 mg of antifoggant c, 8.21 g of high boiling organic solvent d and 24 ml of ethyl acetate were dissolved at 60 ° C. The above solution was mixed with 150 g of an aqueous solution in which 12 g of lime-processed gelatin and 0.6 g of sodium dodecylbenzenesulfonate were dissolved.
It was emulsified and dispersed over a period of minutes. After the dispersion, distilled water was added so that the total amount became 300 g, and the mixture was mixed at 2,000 rpm for 10 minutes.

[0087]

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Coatings having the contents shown in Table 6 were prepared by combining these compounds with the silver halide emulsions (# 1 to # 12) prepared above, and were used as heat development samples # t1 to # t2. Each layer was applied on a transparent pet base having a thickness of 120 μm.

[0089]

[Table 6]

[0090]

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Further, a processing material P-1 as shown in Table 7 was prepared.

[0092]

[Table 7]

[0093]

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These materials were exposed for 1/100 second through an optical wedge and a blue filter. 15 ml / m ² of 40 ° C. hot water was applied to the surface of the exposed photosensitive material, and the processing material and the respective film surfaces were overlapped with each other, and then heat-developed at 83 ° C. for 30 seconds using a heat drum. When the photosensitive material was peeled off after the processing, a wedge-shaped image of cyan color was obtained. These colored samples were subjected to a stabilization treatment using a treatment material P-2 shown in Table 8.

[0095]

[Table 8]

Table 9 shows the structure of the support A of the processing material P-2.

[0097]

[Table 9]

The stabilizing treatment is performed by adding 10 cc /
m ² of water, and adhered to the color sample.
Heated for 2 seconds.

The transmission density of the obtained color sample was measured to obtain a so-called characteristic curve. The reciprocal of the exposure for a density 0.15 higher than the fog density was measured as the sensitivity. The results are shown in Table 10. In Table 10, the sensitivity of sample Δt1 was 1
The relative sensitivity was set to 00. Fog is shown as a relative value when the maximum density is 1.

[0100]

[Table 10]

From the results, when the sensitizing dye of the present invention was used,
It can be seen that the sensitivity is high while maintaining a low fog.

[0102]

According to the present invention, a silver halide photographic material having high sensitivity can be obtained.

Claims (2)

[Claims] An aspect ratio of a silver halide grain containing at least one compound represented by the general formula (I) or (II) and forming an emulsion layer containing the compound is 3 to 100. A silver halide photosensitive material characterized by the following. General formula (I) In the formula, L1, L2 and L3 each represent a methine group. n1
Represents 0, 1, 2, 3 or 4. R1, R2, R3 and R4 each represent an alkyl group, an aryl group or a heterocyclic group. M1 represents a charge-balancing counter ion, and m1 represents a number from 0 to 10 required to neutralize the charge of the molecule. Formula (II) In the formula, 4, L5, L6, L7, L8 and L9 each represent a methine group. n2 and n3 each represent 0, 1, 2, 3 or 4. Q represents a divalent linking group. R5, R6, R
7, R8, R9 and R10 each represent an alkyl group, an aryl group or a heterocyclic group. M2 represents a charge balancing counter ion,
m2 represents a number of 0 or more and 10 or less necessary for neutralizing the electric charge of the molecule. 2. The method according to claim 1, wherein the methine compound is a compound represented by the general formula (II) and silver halide grains having an aspect ratio of 10 to 50. Item 6. The silver halide light-sensitive material according to Item 1.