JPH11218872A - Silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a silver halide photographic sensitive material high in sensitivity and superior in storage stability by incorporating a compound having plural styryl bases combined through covalent bonds. SOLUTION: This photographic sensitive material contains a compound having >=2 styryl bases combined through covalent bonds and represented by formula I: A1 -L-A2 in which each of A1 and A2 has a styryl base structure; and L is a simple bond or a divalent bonding group; or formula I is selected from groups of formula II and the like, and in formula II, each of Z1 and Z2 is an atomic group necessary to form a 5- or 6-membered N-containing hetero ring; each of L1 -L8 is a methine group; each of V1 and V2 is a univalent bonding group; each of l1 and l2 is 0, 1, 2, 3, or 4; each of p1 and p2 is 0 or 1; each of n1 and n2 is 0, 1, 2, or 3; each of R1 and R<2> is an H atom or an alkyl group or the like; M1 is a charge balancing counter ion; m1 is a number of 0-10 necessary to neutraliz the molecular charge; and La is same as L in formula I.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic material, and more particularly, to a high-sensitivity silver halide photographic material.

[0002]

2. Description of the Related Art Hitherto, great efforts have been made to increase the sensitivity of silver halide photographic materials. Also,
In particular, high sensitivity of spectrally sensitized silver halide photographic materials has been strongly desired. Spectral sensitization technology is a very important and essential technology for producing a photosensitive material having high sensitivity and excellent color reproducibility. The spectral sensitizer has a function of absorbing light in a long wavelength range, which is essentially not absorbed by the silver halide photographic emulsion, and transmitting the light to the silver halide. Therefore, an increase in the amount of light supplemented by the spectral sensitizer is advantageous for increasing photographic sensitivity. For this reason, attempts have been made to increase the amount of light captured by increasing the amount of addition to the silver halide emulsion. However, attempts have been made to increase the amount of light trapped by increasing the amount added to silver halide. However, if the addition amount of the spectral sensitizer to the silver halide emulsion exceeds the optimum amount, a large desensitization is brought about. This is generally referred to as dye desensitization, and is a reduction that causes desensitization in a photosensitive region unique to silver halide, which has substantially no light absorption by a sensitizing dye. If the dye desensitization is large, the overall sensitivity will be low although there is a spectral sensitizing effect. In other words,
As the dye desensitization decreases, the spectral sensitivity increases accordingly. Therefore, in spectral sensitization technology, improvement of dye desensitization is a major problem.

[0003] In addition, T. Tani et al.
Journal of Physica
As described in Chemistry, Vol. 94, p. 1298 (1990), it is known that a sensitizing dye having a reduction potential nobler than -1.25 v has a low relative quantum yield of spectral sensitization. I have. In order to increase the relative quantum yield of the spectral sensitization of such dyes, the “Theory of the Photogragh process”
Phonic Process) pp. 259-265 (1966), super sensitization by hole capture has been proposed.

A compound having a lower oxidation potential than a sensitizing dye may be used in combination as a supersensitizer for eliminating the above desensitization. For example, U.S. Pat. No. 2,313,922
No. 2,075,046 and 2,448,858
No. 2,680,686; British Patent No. 1,230,
No. 449, Belgian Patent No. 771,168 and the like are known. However, the effect of increasing the sensitivity by these methods is insufficient, and there has been a demand for further increasing the sensitivity.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a silver halide photographic material having high sensitivity and excellent storage stability.

[0006]

The object of the present invention has been achieved by the following means as a result of intensive studies. That is,

(1) A silver halide photographic light-sensitive material comprising a compound having two or more styryl bases linked by a covalent bond. (2) The silver halide photographic material as described in (1), wherein the compound as described in (1) is a compound represented by the following general formula (I). General formula (I)

[0008]

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In the formula (I), A ₁ and A ₂ represent a styryl-based structure. L represents a single bond or a divalent linking group. (3) The silver halide photographic material as described in (2), wherein the general formula (I) described in (2) is selected from the following general formulas (II) and (III). General formula (II)

[0010]

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In the formula, Z ₁ and Z ₂ represent a group of raw materials necessary for forming a 5- or 6-membered nitrogen-containing heterocyclic ring.
_{L 1, L 2, L 3} , L 4, L 5, L 6, L 7, and L ₈
Represents a methine group. V ₁ and V ₂ represent a monovalent substituent, and l ₁ and l ₂ are integers from 0 to 4. p ₁ and p ₂
Represents 0 or 1. n ₁ and n ₂ represent 0, 1, 2, or 3. R ₁ and R ₂ represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. M ₁ represents a charge-balancing counter ion, and m ₁ is 0 or more and 1 necessary to neutralize the charge of the molecule.
Represents a number of 0 or less. La has the same meaning as L in formula (I). General formula (III)

[0012]

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Where Z_Three, And Z_FourIncludes 5 or 6 members
Represents an atom group necessary for forming a nitrogen heterocycle.
L₉, L_Ten, L₁₁, L₁₂, L₁₃, L₁₄, L_Fifteen, And L₁₆
Represents a methine group. V_Three, And V_FourRepresents a monovalent substituent
Then l_Three, And l_FourIs an integer from 0 to 4. p_Three, And p_FourIs
Represents 0 or 1. n_Three, And n_FourRepresents 0, 1, 2, or 3
You. R_Three, R_Four, R_Five, And R₆Is a hydrogen atom,
Represents an aryl group, an aryl group, or a heterocyclic group. M_TwoIs the charge uniformity
Represents the counter ion, m_TwoIs required to neutralize the molecular charge
Represents a number from 0 to 10 inclusive. Lb is L of the general formula (I)
Is synonymous with (4) R described in (3)₁Or R_TwoAt least one of
And R_Three, R_Four, R _FiveOr R₆At least
One is L₁−Q (L₁Is a methylene group, Q is CO_Two ^-, M
R_Three, M is Si, Sn, Ge, B^-, R is an alkyl group,
An aryl group or a heterocyclic group. )
(3) The silver halide photographic material as described in (3) above.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The compounds used in the present invention will be described below in detail.

As the 5- or 6-membered nitrogen-containing heterocyclic ring represented by Z ₁ , Z ₂ , Z ₃ and Z ₄ , an aromatic ring may be condensed. The aromatic ring may be a benzene ring, a naphthalene ring or the like, or a heteroaromatic ring such as a pyrazine ring or a thiophene ring.

Preferably, thiazoline nucleus, thiazole nucleus, benzothiazole nucleus, oxazoline nucleus, oxazole nucleus, benzoxazole nucleus, selenazoline nucleus, selenazole nucleus, benzoselenazole nucleus, 3,3-dialkylindolenine nucleus (for example, 3,3 -Dimethylindolenin), imidazoline nucleus, imidazole nucleus, benzimidazole nucleus, 2-pyridine nucleus, 4-pyridine nucleus, 2-quinoline nucleus, 4-quinoline nucleus, 1-isoquinoline nucleus, 3-isoquinoline nucleus, imidazo [4 5-b] quinoxaline nucleus, oxadiazole nucleus, thiadiazole nucleus, tetrazole nucleus, and pyrimidine nucleus.

Preferred are a benzoxazole nucleus, a benzothiazole nucleus, a benzimidazole nucleus and a quinoline nucleus, and more preferred are a benzoxazole nucleus and a benzothiazole nucleus. Particularly preferred is a benzothiazole nucleus.

Assuming that the substituent on Z ₁ , Z ₂ , Z ₃ and Z ₄ is V, the substituent represented by V is not particularly limited. For example, a halogen atom (for example, chlorine, bromine, iodine,
Fluorine), mercapto group, cyano group, carboxyl group,
Phosphoric acid group, sulfo group, hydroxy group, carbon number 1 to 1
0, preferably a carbamoyl group having 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 1 to 10 carbon atoms 8 alkoxy groups (eg, methoxy, ethoxy, 2-methoxyethoxy, 2-phenylethoxy), and aryloxy groups having 6 to 20, preferably 6 to 12, more preferably 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); 0 to 15, preferably 3 to 10 carbon atoms, more preferably 3 to 6 carbon atoms (for example, trimethylammonium group, triethylammonium group), 0 to 15 carbon atoms, preferably 1 to 10 carbon atoms, more preferably Is a hydrazino group having 1 to 6 carbon atoms (eg, trimethylhydrazino group), a ureido group having 1 to 15 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms (eg, ureido group, N, N -Dimethylureido group), having 1 to 15 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably Ku imido group having 1 to 6 carbon atoms (e.g., succinimido group), from 20 1 carbon atoms, preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms
Alkyl or arylthio groups such as methylthio,
Ethylthio, carboxyethylthio, sulfobutylthio, phenylthio, etc.), an alkoxycarbonyl group having 2 to 20 carbon atoms, preferably 2 to 12 carbon atoms, more preferably 2 to 8 carbon atoms (for example, methoxycarbonyl,
Ethoxycarbonyl, benzyloxycarbonyl), an aryloxycarbonyl group having 6 to 20 carbon atoms, preferably 6 to 12 carbon atoms, more preferably 6 to 8 carbon atoms (eg, 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). Further, a structure in which a benzene ring, a naphthalene ring, or an anthracene ring is condensed can be employed. Further, V may further substitute on these substituents.

Preferred substituents on Z ₁ , Z ₂ , Z ₃ and Z ₄ are the above-mentioned alkyl, aryl, alkoxy, halogen, acyl, cyano, sulfonyl and benzene ring condensation. And more preferably an alkyl group, an aryl group, a halogen atom, an acyl group, a sulfonyl group, and a benzene ring condensation, and particularly preferably a methyl group, a phenyl group, a methoxy group, a chlorine atom, a bromine atom, an iodine atom, and a benzene ring. It is a ring condensation. Most preferred are a phenyl group, a chlorine atom, a bromine atom and an iodine atom.

R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆
Each represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group, for example, an unsubstituted alkyl group 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), a substituted alkyl group having 1 to 18, preferably 1 to 7, and particularly preferably 1 to 4 carbon atoms {for example, a heterocyclic group substituted by V mentioned as a substituent 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), carboxyalkyl group (for example, 2-carboxyethyl,
3-carboxypropyl, 4-carboxybutyl, carboxymethyl), an alkoxyalkyl group (for example, 2-
Methoxyethyl, 2- (2-methoxyethoxy) ethyl), aryloxyalkyl group (for example, 2-phenoxyethyl, 2- (1-naphthoxy) ethyl), alkoxycarbonylalkyl group (for example, ethoxycarbonylmethyl, 2-benzyloxycarbonyl) Ethyl), an aryloxycarbonylalkyl group (for example, 3-phenoxycarbonylpropyl), an acyloxyalkyl group (for example, 2
-Acetyloxyethyl), acylalkyl group (eg, 2-acetylethyl), carbamoylalkyl group (eg, 2-morpholinocarbonylethyl), sulfamoylalkyl group (eg, N, N-dimethylcarbamoylmethyl), sulfoalkyl group (eg, , 2-sulfoethyl,
3-sulfopropyl, 3-sulfobutyl, 4-sulfobutyl, 2- [3-sulfopropoxy] ethyl, 2-hydroxy-3-sulfopropyl, 3-sulfopropoxyethoxyethyl), sulfoalkenyl group (for example, sulfopropenyl group) , A sulfatoalkyl group (for example, 2-
Sulfatoethyl group, 3-sulfatopropyl, 4-sulfatobutyl), heterocyclic-substituted alkyl group (for example, 2-
(Pyrrolidin-2-one-1-yl) ethyl, tetrahydrofurfuryl), alkylsulfonylcarbamoylmethyl group (for example, methanesulfonylcarbamoylmethyl group)}, having 6 to 20 carbon atoms, preferably 6 to 1 carbon atoms.
0, more preferably an unsubstituted aryl group having 6 to 8 carbon atoms (eg, phenyl group, 1-naphthyl group), 6 to 20, preferably 6 to 10, more preferably 6 to 8 carbon atoms An aryl group (for example, Z ₁ described above)
And aryl groups substituted by V mentioned as substituents. Specific examples include a p-methoxyphenyl group, a p-methylphenyl group, and a p-chlorophenyl group. ), Having 1 to 20 carbon atoms, preferably 3 to 1 carbon atoms.
0, more preferably an unsubstituted heterocyclic group having 4 to 8 carbon atoms (for example, 2-furyl, 2-thienyl, 2-pyridyl, 3-pyrazolyl, 3-isoxazolyl, 3-isothiazolyl, 2-imidazolyl, -Oxazolyl, 2
-Thiazolyl, 2-pyridazyl, 2-pyrimidyl, 3-
Pyrazyl, 2- (1,3,5-triazolyl), 3- (1,2,4-
Triazolyl), 5-tetrazolyl), having 1-2 carbon atoms
0, preferably from 3 to 10 carbon atoms, more preferably include heterocyclic group V mentioned as substituents such as Z ₁ substituted Hajime Tamaki (e.g., the aforementioned 8 from 4 carbon atoms is substituted. Specifically Represents a 5-methyl-2-thienyl group, a 4-methoxy-2-pyridyl group, etc.).

R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆
Are preferably an alkyl group, an aryl group, and a heterocyclic group. More preferably, the above-mentioned unsubstituted alkyl group (for example, methyl, ethyl, butyl), substituted alkyl group (for example, 2-sulfoethyl, 3-sulfopropyl,
-Sulfobutyl, carboxymethyl, 2-carboxyethyl), an unsubstituted aryl group (eg, phenyl, naphthyl), and an unsubstituted heterocyclic group (eg, 2-pyridyl, 2-thiazolyl), particularly preferably substituted or unsubstituted Is an alkyl group. Most preferably, it is an unsubstituted alkyl group.

L ₁ , L ₂ , L ₃ , L ₄ , L ₅ , L ₆ , L
_{7, L 8, L 9,} L 10, L 11, L 12, L 13, L 14,
L ₁₅ and L ₁₆ each independently represent a methine group. L ₁
Methine group represented by ~L ₁₆ may have a substituent, 15 and examples of the substituent include substituted or unsubstituted 1 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 carbon atoms To 5 alkyl groups (e.g., methyl, ethyl, 2-carboxyethyl), substituted or unsubstituted aryl groups having 6 to 20 carbon atoms, preferably 6 to 15 carbon atoms, more preferably 6 to 10 carbon atoms (e.g., phenyl , O-carboxyphenyl), substituted or unsubstituted C 3-20, preferably C 4-15,
More preferably, it is a heterocyclic group having 6 to 10 carbon atoms (for example, N, N-, diethylbarbituric acid group), a halogen atom (for example, chlorine, bromine, fluorine, iodine), and having 1 to 1 carbon atoms.
5, preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon atom alkoxy groups (eg methoxy, ethoxy), 1 to 15 carbon atoms, preferably 1 to 1 carbon atoms
0, more preferably an alkylthio group having 1 to 5 carbon atoms (eg, methylthio, ethylthio);
0, preferably an arylthio group having 6 to 15 carbon atoms, more preferably 6 to 10 carbon atoms (eg phenylthio), 0 to 15 carbon atoms, preferably 2 to 1 carbon atoms
0, more preferably an amino group having 4 to 10 carbon atoms (eg, N, N-diphenylamino, N-methyl-N-phenylamino, N-methylpiperazino) and the like. Further, a ring may be formed with another methine group. Alternatively, a ring can be formed with other parts. Preferably, it is an unsubstituted methine group.

N ₁ , n ₂ , n ₃ and n ₄ are preferably 1, 2 and more preferably 1. n ₁ , n ₂ , n ₃ and n ₄ are 2
At this point, the methine groups are repeated but need not be the same.

M ₁ and M ₂ 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 hydrogen ions (H ⁺ ), inorganic cations such as 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 (for example, a fluorine ion, a chloride ion, or an iodine ion), or a substituted arylsulfonate ion (for example, p-toluenesulfonic acid ion, p-toluene ion). Chlorobenzenesulfonate ion), aryldisulfonic acid ion (for example, 1,3-benzenesulfonic acid 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. For example, in the present invention, a sulfo group is SO ₃ ⁻ , and a carboxy group is
CO ₂ ^- and although expressed, when having a proton as a counter ion can be expressed with each SO ₃ H, CO ₂ H. m ₁ and m ₂ represent the numbers required to balance the charges,
It is 0 when a salt is formed in the molecule. p ₁ , p ₂ , p ₃ , p ₄
Each independently represents 0 or 1. Preferably it is 0.

V ₁ , V ₂ , V ₃ , and V ₄ may be any monovalent substituents, and include, for example, the substituents represented by V described above. Preferably, it is a substituted or unsubstituted alkyl group or a halogen atom, a substituted or unsubstituted alkoxy group, and more preferably an unsubstituted alkyl group.

L ₁ , l ₂ , l ₃ , and l ₄ represent 0, ₁ , ₂ , ₃ , and ₄ , preferably 0, and more preferably 0.
It is.

L, La and Lb represent a divalent linking group. The 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, sulfoamide group, sulfonic ester group, ureido group, sulfonyl group, sulfinyl group, thioether group, ether group, carbonyl group, -N (Ra)-(Ra is a hydrogen atom, a substituted or unsubstituted alkyl group , Represents 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)
Represents a divalent linking group having 1 or more and 20 or less carbon atoms, which is constituted by combining one or more.

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. Particularly preferred is an alkylene group.

These divalent linking groups may have a substituent. Examples of the substituent include a substituted or unsubstituted C 1 to C 15, preferably C 1 to C 10, more preferably C 1 to C 10 carbon atom. An alkyl group of 1 to 5 (eg, methyl, ethyl, 2-carboxyethyl), substituted or unsubstituted C6 to C20, preferably C6 to C1
5, more preferably an aryl group having 6 to 10 carbon atoms (eg, phenyl, o-carboxyphenyl), substituted or unsubstituted 3 to 20 carbon atoms, preferably 4 carbon atoms
To 15, more preferably a C6 to C10 heterocyclic group (e.g., N, N-, diethylbarbituric acid group), a halogen atom (e.g., chlorine, bromine, fluorine, iodine), and a C1 to C15, preferably C1 to C10, more preferably C1 to C5 alkoxy group (for example, methoxy, ethoxy), C1 to C15, preferably C1 to C10, more preferably C1 to C5 alkylthio group ( For example, methylthio, ethylthio), carbon number 6
To 20, preferably 6 to 15 carbon atoms, more preferably 6 to 10 carbon atoms, for example, phenylthio, 0 to 15 carbon atoms, preferably 2 to 10 carbon atoms, more preferably 4 to 10 carbon atoms. Amino groups (eg, N, N-diphenylamino, N-methyl-N
-Phenylamino, N-methylpiperazino) and the like.

[0034] CO is bonded to La ₂ ^- is, pH of the system
Can be in a non-dissociated state, in which case it can be expressed as CO ₂ H.

Of the general formulas (I), (II) and (III), preferred are (II) and (III), and more preferred is (II)
It is.

Next, specific examples of the general formulas (I), (II) and (III) are shown, but the present invention is not limited thereto.

[0037]

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[0038]

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[0039]

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[0040]

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The compounds represented by the general formulas (I), (II) and (III) of the present invention can be prepared by using FM Harmer.
Heterocyclic Compounds-Heterocycli-Cyanine Soybeans and Related Compounds
c Compounds-Cyanine Dyes and Related Compound
s) ", Chapter 13, pp. 433-437, John Wiley & Sons, Inc.-New York, London, 1964, DMSturmer, Heterocyclic. Heterocyclic Compounds-Special Topics in Heterocyclic Compounds-Special
topics in heterocyclic chemistry), Chapter 18, Section 14, pages 482-515, John Wiley & Sons, Inc.-New York,
London, 1977, "Rodd's Chemistry of Car Compounds
bon Compounds) "2nd.Ed.vol.IV, partB, 1977, Chapter 15, pages 369 to 422, Elsevier Scienc Inc.
e Publishing Company Inc.), New York, and the like.

Synthesis Example (Synthesis of Compound (1)) Compound (1) can be synthesized according to the scheme shown below.

[0043]

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(A) 6 g (30 mmol), (b) 3.
1 g (10 mmol), in ^t-butanol 40 ml, ^t-butoxy potassium 3.36g of (30 mmol) was added, after which the heated and stirred for 3 hours on an oil bath at an external temperature of 100 ° C., methanol 50 ml, 100ml of water was added, to give The obtained crystals were separated by suction filtration and washed with water. Further, using silica chromatography, ethyl acetate / hexane = 1
The mixture was developed and purified with a mixed solvent of / 2. After evaporating the solvent of the target substance and dissolving it in 50 ml of chloroform, 50 ml of methanol was added and the solvent was distilled off at about 50 ml under normal pressure.
The obtained crystals are separated by suction filtration, and methanol 5
After washing with 0 ml, it was dried to obtain 0.67 g of (1). (Yield 10%, λmax = 407 nm (ε = 7470
0) (methanol / chloroform = 9/1)

The compounds represented by formulas (I), (II) and (III) of the present invention may be used alone, but are more preferably used in combination with other spectral sensitizing dyes.

The timing at which the compound of the present invention (and the same applies to other sensitizing dyes) is added to the silver halide emulsion of the present invention at any stage in the emulsion preparation which has been recognized to be useful. It may be inside. For example, U.S. Pat. Nos. 2,735,766, 3,628,960, 4,183,756, 4,225,666, JP-A-58-184142, and JP-A-60-196749. As disclosed, 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, JP-A-58-113.
As disclosed in Japanese Patent No. 920 or the like, the compound may be added at any time before the chemical ripening or during the process, or at any time before the application of the emulsion after the chemical ripening until coating. Further, as disclosed in U.S. Pat. No. 4,225,666, JP-A-58-7629 and the like, the same compound may be used alone or in combination with a compound having a different structure.
For example, it may be divided and added during the particle formation step and during the chemical ripening step or after the completion of the chemical ripening, or may be divided and added before or during the chemical ripening and after the completion of the chemical ripening. The type of the compound to be added and the combination of the compounds may be changed and added.

The addition amount of the compound of the present invention varies depending on the shape and size of silver halide grains, but 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.
In the case of 2 to 1.3 μm, the addition amount is preferably 2 × 10 ^{−6 to} 3.5 × 10 ⁻³ mol, and 7.5 × 10 ^{−6 to} 1.5 × 10 per mol of silver halide. An addition amount of ^-3 mol is more preferred.

The compounds of the present invention can be dispersed directly in the emulsion. These can be first dissolved in an appropriate solvent, for example, 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 compound, as described in US Pat. No. 3,469,987, the compound is dissolved in a volatile organic solvent, and the solution is dispersed in a hydrophilic colloid. As described in JP-B-46-24185, and a method of dispersing in a water-soluble solvent and adding this dispersion to the emulsion, described in U.S. Pat. No. 3,822,135. A method of dissolving a compound in a surfactant and adding the solution to an emulsion, and dissolving using a compound that causes a red shift as described in JP-A-51-74624, and dissolving the solution in the emulsion. As described in JP-A-50-80826, a method in which a compound is dissolved in an acid substantially free of water and the solution is added to an emulsion is used. In addition, US Pat.
No. 2,343, No. 3,342,605, No. 2,99
Nos. 6,287, 3,429,835 and the like can also be used.

The compounds of the present invention can be used as various filter dyes, irradiation prevention dyes or antihalation dyes for the purpose of improving sharpness and color resolution. This compound is prepared by a conventional method using a silver halide photographic material layer, a filter layer and / or
Alternatively, it can be contained in a coating solution such as an antihalation layer. 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. Examples of the polymer mordant include U.S. Pat. Nos. 2,548,564, 4,124,386, 3,625,694, 3,958,995, 4,168,976, and 3,445. , No. 231, and the like.

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 are regular, such as cubic, tetradecahedral, and rhombodecahedral.
It may have an irregular crystal form, may have an irregular crystal form such as a sphere or a plate, or may have a complex form 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 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. 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.
It is 12 or less. Tabular grains are described in Gaft, Photographic Science and Engineering,
14, 248-257 (1970); US Pat.No. 4,434,226, 4,41
4,310, 4,433,048, 4,439,520 and GB 2,112,157
Can be easily adjusted by the method described in (1). In the photographic light-sensitive material of the present invention, its abundance is at least 70%, particularly preferably at least 85%.

The compounds of the present invention are used for the following applications for sensitizers, 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 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, Photosensitive materials for plate making (for example, squirrel 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), photosensitive materials used in a silver salt diffusion transfer process, Photo-sensitive material used in color diffusion transfer process, die transfer process (imhibition pro
cess), 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 Chimie et Physiqu by P. Glafkides.
e Photograhique "(Paul Montel, 1967), GF Deffein (GFDuff
in) "Photographic Emulsion Chemistry" (The FocalPress, 1966); Making and Coating by VLZelikman et al.・ Photographic ・
Emulsion (Making and Coating Photographic Emul
sion) "(The Focal Press)
Ed., 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, rodankari, 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, mercaptobenzimidazole , Mercaptothiadiazoles, mercaptotetrazole (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 can 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 an ether, ester or amine, a thioether compound, a thiomorpholine, or a quaternary ammonium, for the purpose of increasing sensitivity, increasing contrast, or accelerating 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 various purposes such as prevention of irradiation. 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 diffusion of the dye. 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, etc.
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 by 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 is converted into a print through back printing and front printing on color paper by the method described in JP-A-2-184835, JP-A-4-186335, and JP-A-6-79968. Is also 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.

[0066]

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 (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. After that, 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 the usual flocculation method, and a sensitizing dye and the compound of the present invention were added to 1 mol of silver, and gold, sulfur and selenium sensitization was optimally performed in the presence of the sensitizing dye and the compound of the present invention. .

(2) Preparation of Coated Samples Emulsion layers and protective layers as shown in Table 1 were coated on a triacetylcellulose film support provided with an undercoat layer to prepare Samples 101 to 122.

[0072]

[Table 1]

These samples were exposed to sensitometry (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 Fixing 4 minutes 20 seconds 38 ° C 25ml 30 liters Rinse with water (1) 1 minute 05 seconds 24 ° C 10 liter countercurrent piping 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 per 35 mm width 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) Ethylenediaminetetraacetic acid sodium 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 salt of ethylenediaminetetraacetic acid 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. In addition, the sensitivity and the fogging when the prepared sample was aged for 4 days at 50 ° C. and 80% RH are also shown. The emulsion and compound species used for each sample and the sensitivity results for each sample are shown in Table 2 below.

[0076]

[Table 2]

[0077]

Embedded image

Table 2 shows that the compound of the present invention has lower fog and higher fresh sensitivity than the comparative compound. In addition, there is little desensitization and increase in fogging after thermo.

Example 2 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 multi-layer color light-sensitive 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, and 3 are sensitizing dyes (S-4) (5.0 × 10 ⁻⁴ )
mol / Agmol) or sensitizing dye (S-4) (5.0 × 10
^-4 mol / Agmol) and (1) (0.5 × 10 ^-4 mol / Agmol) to obtain Sample 201 and Sample 202, respectively. To examine the sensitivity of the sample thus obtained, light from a Fuji FW type sensitometer (Fuji Photo Film Co., Ltd.) was exposed for 1/100 second through an optical wedge and a red filter.
Color development was performed using the same processing steps and processing solution as in Example 1 of No. 4 to measure cyan density. The sensitivity was indicated by a relative value of fog density + 0.2. As a result, the sample 2 of the present invention was compared with the sensitivity 100 (reference) of the comparative sample 201.
02 had a high sensitivity of 155, and there was little increase in fogging during aging.

Example 3 Emulsion 1 of Example 1 in JP-A-7-92601 was prepared by changing the spectral sensitizing dye to sensitizing dye (S-3) (8 × 10 ⁻⁴ mol / Agmol) or sensitizing dye ( S-3) (8 × 10 ^-4 mol / Agmol) and (33)
(0.8 × 10 ⁻⁴ mol / Agmol), and a tetrahedral silver iodobromide emulsion was prepared.
1 and 302. The emulsion 1 of Example 1 of JP-A-7-92601 was different from the emulsion 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 a sensitizing dye (S-3). (8 × 10 ^-4 mol / Agmol)
Alternatively, a cubic silver iodobromide emulsion differing only in that the sensitizing dyes (S-3) (8 × 10 ⁻⁴ mol / Agmol) and (33) (0.8 × 10 ⁻⁴ mol / Agmol) were used was prepared. And this is emulsion 3
03 and 304. Multilayer color photosensitive material
It was prepared in the same manner according to Sample 401 of Example 4 of No. 7-92601. Samples 311 and 312 were prepared by replacing emulsion 1 of the ninth layer of sample 401 of Example 4 of JP-A-7-92601 with emulsion 301 or emulsion 302. Similarly, the emulsion 9 of the ninth layer in the same Example was replaced with the emulsion 303 or the emulsion 304
Samples 313 and 314 were used as samples.
The sample thus obtained was evaluated for sensitivity. JP 7-9260
As in Example 4 of No. 1, magenta density measurement was performed by 1/50 second exposure and color reversal development processing. 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 172, which was high. Similarly, when the sensitivity of the comparative sample 313 is set to 100,
The sensitivity of Sample 314 of the present invention was 175, which was high.
Furthermore, the increase in fog after storage at 50 ° C. and 80% RH for 3 days was small.

Example 4 Same as Emulsion 1 and Emulsion 5 in Example 1 of JP-A-5-313297.
Octahedral silver bromide internal latent image type direct positive emulsion and hexagonal flat
A tabular silver bromide internal latent image type direct positive emulsion was prepared and
Emulsions 401 and 402 were obtained. Color diffusion transfer
The true film was sample 101 of Example 1 of JP-A-5-313297.
In the same manner. Example 1 of JP-A-5-313297
Emulsion-2 of the 16th layer of sample 101 and sensitizing dye (2) were milked.
Agent 401 and sensitizing dye (S-2) (9 × 10^-Fourmol / Agmol)
Alternatively, sensitizing dye (S-2) (9 × 10^-Fourmol / Agmol) and
(2) (0.9 × 10 ^-Fourmol / Agmol)
411 and 412. Similarly, the sample of the same example
Emulsion No. 101 of the eleventh layer and sensitizing dye (2) in emulsion 4
02 and sensitizing dye (S-2) (9 × 10^-Fourmol / Agmol)
Or sensitizing dye (S-2) (9 × 10^-Fourmol / Agmol) and
(3) (0.9 × 10^-Fourmol / Agmol)
413 and sample 414. The feeling of the sample thus obtained
To check the degree, the same as in Example 1 of JP-A-5-313297
Exposure and processing steps and processing using a processing solution to reduce the transfer density
It was measured with a color densitometer. Sensitivity is a relative value of density 1.0
displayed. When the sensitivity of the comparative sample 411 is set to 100
The sensitivity of the sample 412 of the present invention is 151, which is high.
In addition, the increase in fogging in 2 days at 40 ° C and 80% RH is also small.
Was. When the sensitivity of the comparative sample 413 is set to 100,
The sensitivity of the sample 414 of the invention is as high as 161.
In addition, the increase in fog at 40 ° C. and 80% RH for 2 days was also small.

Example 5 Emulsion F of Example 2 of JP-A-4-42536 was prepared by adding no red-sensitive sensitizing dye (S-1) before sulfur sensitization, and In addition, chloroauric acid was used in combination to optimize gold-sulfur sensitization, and after gold-sulfur sensitization, sensitizing dye (S-2) (2 × 10 ⁻⁴ mol / Agmol) (the dye shown in the present invention) ) Or sensitizing dye (S-2) (2 × 10 ⁻⁴ mol / Agmo
Silver chlorobromide emulsions differing only in that l) and (6) (0.2 × 10 ⁻⁴ mol / Agmol) were added were prepared as emulsions 501 and 502. Multi-layer color printing paper is disclosed in JP-A-6-347944.
In the same manner, the sample was prepared according to the sample 20 of Example 1 of the item No. JP
Samples 511 and 512 were obtained by changing the emulsion of the first layer in Sample 20 of Example 1 of No. 6-347944 to Emulsion 501 or Emulsion 502. In order to examine the sensitivity of the sample thus obtained, the light of a Fuji FW type sensitometer (Fuji Photo Film Co., Ltd.) was exposed for 1/10 second through an optical wedge and a blue filter, and Example 1 of JP-A-6-347944 was used. A color development process was performed using the same processing steps and processing solution as described above. As a result, when the sensitivity of the comparative sample 511 was set to 100, the sensitivity of the sample 512 of the present invention was 151, which was high, and the increase in fog at 60 ° C. and 60% RH for 3 days was small.

Example 6 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-4) (2 × 10 ⁻⁴ mo
l / Agmol) or sensitizing dye (S-4) (2 × 10 ⁻⁴ mol /
(Agmol) and (35) (0.2 × 10 ⁻⁴ mol / Agmol). Chemical sensitization was carried out, and these were designated 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, an X-ray orthoscreen HGM manufactured by Fuji Photo Film Co., Ltd.
After exposure for 2 seconds, the film was processed using an automatic developing machine and a processing solution in the same manner as in Example 1 of Japanese Patent Application No. 7-232036. Sensitivity +
The logarithm of the reciprocal of the exposure required to give a density of 0.1 was expressed as the logarithm of the sensitivity of Sample 611, and the others were expressed as relative values. As a result, the sensitivity of the sample 612 of the present invention was as high as 151, and there was little increase in fog at 40 ° C. and 80% RH for 4 days. X-ray orthoscreen H used during exposure
The same effect was obtained by exposing with HR-4 or HGH instead of GM.

Example 7 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 used as emulsion 701 and sensitizing dye (S-3).
(5 × 10 ^-4 mol / Agmol) or sensitizing dye (S-3)
(5 × 10 ⁻⁴ mol / Agmol) and (10) (0.5 × 10 ⁻⁴ mol / Agmol)
(Agmol) and Sample 711 and Sample 712. To check the sensitivity of the sample thus obtained, Fuji FW
A 1/100 second exposure was given to light from a sensitometer (Fuji Photo Film Co., Ltd.) 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 148, which was high, and the increase in fog at 60 ° C. and 50% RH for 3 days was small.

Example 8 An octahedral silver chloride emulsion was prepared in the same manner as in Emulsion F of Example 3 of Japanese Patent Application No. 74-168991, and this was used as an emulsion layer 801. 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. 7-146891 were prepared by combining emulsion 801 with sensitizing dye (S-3) (5 × 10 ^-4 mol / Agmol) or sensitizing dye. (S-3) (5 × 10 ⁻⁴ mol / Agmol) and (36) (0.5 ×
10 ^-4 mol / Agmol) to obtain Sample 811 and Sample 812. In order to examine the sensitivity of the sample thus obtained, the light of a Fuji FW type sensitometer (Fuji Photo Film Co., Ltd.) was passed through an optical wedge and a green filter to be 1/100.
Second exposure was performed, and Fuji Photo Film CN16 processing was performed to compare 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 811 was set to 100. The sensitivity of Sample 812 of the present invention was as high as 145, and the increase in fog at 40 ° C. and 80% RH for 3 days was small.

Example 9 A silver iodobromide emulsion was prepared in the same manner as in Emulsion E of Example 1 of JP-A-7-159950 to prepare 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
With sensitizing dye (S-3) (9.8 × 10 ^-4 mol / Agmol) or (S-3) (9.8 × 10 ^-4 mol / Agmol) and (38)
(0.98 × 10 ⁻⁴ mol / Agmol) to obtain Sample 901 and Sample 902. In order to examine the sensitivity of the sample thus obtained, the light of a Fuji FW type sensitometer (Fuji Photo Film Co., Ltd.) was passed through an optical wedge and a green filter.
Exposure was performed for 100 seconds, color development was performed using the same processing steps and processing solution as in Example 1 of JP-A-7-159950, and 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 as high as 138 with respect to the sensitivity of the comparative sample 901 of 100 (reference), and the increase in fog at 50 ° C. and 60% RH for 3 days was small.

[0088]

According to the present invention, a silver halide photographic light-sensitive material having high sensitivity and excellent storage stability can be obtained.

Claims (4)

[Claims] 1. A silver halide photographic material comprising a compound having two or more styryl bases linked by a covalent bond. 2. The silver halide photographic material according to claim 1, wherein said compound according to claim 1 is a compound represented by the following general formula (I). General formula (I) In the formula (I), A ₁ and A ₂ represent a styryl-based structure. L represents a single bond or a divalent linking group. 3. The silver halide photographic material according to claim 2, wherein the general formula (I) according to claim 2 is selected from the following general formula (II) or (III). General formula (II) In the formula, Z ₁ and Z ₂ represent an atomic group necessary for forming a 5- or 6-membered nitrogen-containing heterocyclic ring. L ₁ , L ₂ ,
L ₃ , L ₄ , L ₅ , L ₆ , L ₇ and L ₈ represent a methine group. V ₁ and V ₂ represent a monovalent substituent, and l ₁ and l ₂ are integers from 0 to 4. p ₁ and p ₂ represent 0 or 1. n ₁ and n ₂ represent 0, 1, 2, or 3. R ₁ and R ₂ represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. M ₁ represents a charge-balancing counter ion, and m ₁ represents 0 or more and 1 necessary to neutralize the charge of the molecule.
Represents a number of 0 or less. La has the same meaning as L in formula (I). General formula (II) In the formula, Z ₃ and Z ₄ represent an atom group necessary for forming a 5- or 6-membered nitrogen-containing heterocyclic ring. L ₉ , L ₁₀ ,
L ₁₁ , L ₁₂ , L ₁₃ , L ₁₄ , L ₁₅ and L ₁₆ represent a methine group. V _3, and V ₄ represents a monovalent substituent, l _3, and l ₄ is an integer from 0 to 4. p ₃ and p ₄ represent 0 or 1. n ₃ and n ₄ represent 0, 1, 2, or 3. R ₃ ,
R ₄ , R ₅ , and R ₆ represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. M ₂ represents a charge-balancing counter ion, and m ₂ represents 0 to 1 required to neutralize the charge of the molecule.
Represents a number of 0 or less. Lb has the same meaning as L in formula (I). 4. The method according to claim 3, wherein at least one of R ₁ or R ₂ and at least one of R ₃ , R ₄ , R ₅ or R ₆ are L ₁ -Q (L ₁ is a methylene group. , Q is C
O ₂ ⁻ , MR ₃ , and M are Si, Sn, Ge, B ⁻ , and R are an alkyl group, an aryl group, or a heterocyclic group. 4. The silver halide photographic light-sensitive material according to claim 3, wherein