JPH10206996A - Silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a silver halide photosensitive material having high sensitivity with little fog and excellent storage stability by incorporating at least one kind of methine compd. having at least a specified crosslinked polymethine structure. SOLUTION: This photosensitive material contains at least one kind of methine compd. having at least one crosslinked polymethine structure expressed by formula. In the formula, La is a methine group, Qa, Qb are methylene groups, Ra, Rb are hydrogen atoms or univalent substituents, and it is not allowed both of Ra and Rb are methyl groups. Any methine compds. except for pentamethine cyanine can be used. For example, a cyanine dye (except for pentamethine cyanine), merocyanine dye, rhodacyanine dye and tricyclic merocyanine dye can be used. Preferably a merocyanine dye or rhodacyanine dye is used. Therefore, the obtd. silver halide photographic sensitive material has high sensitivity and excellent storage stability.

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 light-sensitive material, and more particularly, to a silver halide photographic light-sensitive material having high sensitivity, less fogging and excellent storage stability.

[0002]

2. Description of the Related Art Hitherto, great efforts have been made to increase the sensitivity of silver halide photographic light-sensitive materials and to reduce residual color after processing. It is known that sensitizing dyes used for spectral sensitization greatly affect the performance of silver halide photographic materials. Slight differences in the structure of sensitizing dyes greatly affect photographic performance such as sensitivity, fogging and storage stability, but it is difficult to predict the effects in advance, and many studies Have tried to synthesize many sensitizing dyes and examine their photographic performance.
However, it is still impossible to predict the photographic performance.

For the above reasons, there is still a need for a technique for spectrally sensitizing silver halide grains with high sensitivity and without causing adverse effects such as fogging.

[0004]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a silver halide light-sensitive material having high sensitivity, less fogging and excellent storage stability.

[0005]

The object of the present invention has been achieved by the following (1) to (4) as a result of intensive studies. (1) A silver halide photographic material comprising at least one methine compound having a crosslinked polymethine structure represented by the following general formula (A): However, the methine compound is not pentamethine cyanine. General formula (A)

[0006]

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In the formula (A), La represents a methine group. Q
a and Qb represent a methylene group. Ra and Rb represent a hydrogen atom or a monovalent substituent. However, Ra and Rb are not methyl groups at the same time. (2) A silver halide photographic material containing a methine compound represented by the following general formula (I) or (II). General formula (I)

[0008]

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In the formula (I), L ₁ , L ₂ , L ₃ and L ₄
Represents a methine group. p ₁ represents 0 or 1. n ₁ is 2,
Represents 3 or 4. Z ₁ and Z ₂ each represent an atom group necessary for forming a 5- or 6-membered nitrogen-containing heterocyclic ring. M ₁ represents a charge balancing counter ion, and m ₁ represents a number of 0 or more necessary to neutralize the charge of the molecule. R ₁ represents an alkyl group;
₂ represents an alkyl group, an aryl group, or a heterocyclic group. General formula (II)

[0010]

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In the formula (II), L ₅ , L ₆ , L ₇ , L ₈ , L
₉ , L ₁₀ , L ₁₁ , L ₁₂ and L ₁₃ represent a methine group. p ₂
And p ₃ is 0 or 1. n ₂ and n ₃ are 0, 1,
Represents 2, 3 or 4. However, when n ₂ is 0 or 1, n
₃ is 1 or more, and when n ₃ is 0, n ₂ is 2 or more. Z ₃ , Z ₄ and Z ₅ each represent an atom group necessary for forming a 5- or 6-membered nitrogen-containing heterocyclic ring. M ₂ represents a charge balancing counter ion, and m ₂ represents a number of 0 or more necessary to neutralize the charge of the molecule. R ₃ and R ₅ represent an alkyl group.
R ₄ represents an alkyl group, an aryl group, or a heterocyclic group.
However, the polymethine chain formed by L ₃ and L ₄ has at least one crosslinked polymethine structure represented by the general formula (A) described in (1). In addition, at least one of a polymethine chain formed by L ₇ and L ₈ and a polymethine chain formed by L ₉ , L ₁₀ and L ₁₁ is represented by at least one of the general formula (A) according to claim 1. It has a cross-linked polymethine structure. (3) In the polymethine chain represented by the general formula (A) of the methine compound represented by the general formulas (I) and (II) described in (2), Ra is a hydrogen atom, Rb is an alkyl group, The silver halide photographic material according to (2), which is represented by an aryl group or a heterocyclic group. (4) In the polymethine chain represented by the general formula (A) of the methine compound represented by the general formulas (I) and (II) described in (2), Ra is a hydrogen atom, and Rb is a cyclopropyl group. (2) The silver halide photographic material as described in (2) above.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The compounds used in the present invention will be described below in detail. The methine compound of the present invention may be any other than pentamethine cyanine. For example,
Examples thereof include cyanine dyes (other than pentamethine cyanine), merocyanine dyes, rhodacyanine dyes, trinuclear merocyanine dyes, allopolar dyes, hemicyanine dyes, and styryl dyes. For more information on these dyes, see
Heterocyclic Compounds-Cyanin, by FM Harmer, Heterocyclic Compounds-Cyanin
eDyes and Related Compounds), John Wiley & Sons, New York, London, 1964, D.M.
(DMSturmer), Heterocyclic Compounds-Special Topics in Heterocyclic Compounds-Special topi
cs in heterocyclic chemistry) ", Chapter 18, Chapter 14
Sections 482-515. Preferred are merocyanine dyes and rhodocyanine dyes.

In the general formulas (I) and (II),
As the 5- or 6-membered nitrogen-containing heterocyclic ring represented by Z ₁ , Z ₃ , and Z ₅ ,

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-dimethylindone) Renin), 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 A quinoxaline nucleus, an oxadiazole nucleus, a thiadiazole nucleus, a tetrazole nucleus, and a 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.

If the substituent on Z ₁ , Z ₃ and Z ₅ 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, a carboxyl group, a phosphoric acid group, a sulfo group, a hydroxy group, a carbamoyl group (hereinafter, “carbamoyl group” has a substituent) Is also used in the meaning of a carbamoyl group).
Preferably it has 2 to 8 carbon atoms, more preferably 2 carbon atoms
To 5 carbamoyl groups (eg, methylcarbamoyl,
Ethylcarbamoyl, morpholinocarbonyl), sulfamoyl group (optionally substituted), for example, a sulfamoyl group having 0 to 10, preferably 2 to 8, more preferably 2 to 5 carbon atoms (eg, methylsulfamoyl, Ethylsulfamoyl, piperidinosulfonyl), nitro group, alkoxy group (optionally substituted), for example, having 1 to 20 carbon atoms, preferably 1 to 1 carbon atoms
0, more preferably an alkoxy group having 1 to 8 carbon atoms (for example, methoxy, ethoxy, 2-methoxyethoxy,
2-phenylethoxy), an aryloxy group (optionally substituted), for example, an aryloxy group having 6 to 20, preferably 6 to 12, and more preferably 6 to 10 carbon atoms (eg, phenoxy, p- Methylphenoxy, p-chlorophenoxy, naphthoxy),

Acyl group (optionally substituted), for example, an acyl group having 1 to 20, preferably 2 to 12, more preferably 2 to 8 carbon atoms (eg, acetyl, benzoyl, trichloroacetyl), acyloxy A group (optionally substituted), for example, having 1 to 20 carbon atoms, preferably 2 to 12 carbon atoms, and more preferably 2 carbon atoms
To 8 acyloxy groups (eg, acetyloxy, benzoyloxy), acylamino groups (optionally substituted)
For example, it has 1 to 20 carbon atoms, preferably 2 to 1 carbon atoms.
2, more preferably an acylamino group having 2 to 8 carbon atoms (eg, acetylamino), a sulfonyl group (which may be substituted), for example, 1 to 20 carbon atoms, preferably 1 carbon atom
To 10, more preferably a sulfonyl group having 1 to 8 carbon atoms (eg, methanesulfonyl, ethanesulfonyl, benzenesulfonyl, etc.), a sulfinyl group (optionally substituted), for example, 1 to 20 carbon atoms, preferably 1 carbon atom
To 10, more preferably a sulfinyl group having 1 to 8 carbon atoms (for example, methanesulfinyl, benzenesulfinyl), a sulfonylamino group (which may be substituted), for example, 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably Is a sulfonylamino group having 1 to 8 carbon atoms (for example, methanesulfonylamino, ethanesulfonylamino, benzenesulfonylamino, etc.),

Amino group, substituted amino group (optionally substituted) For example, 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), ammonium group (optionally substituted), for example, an ammonium group having 0 to 15, preferably 3 to 10, more preferably 3 to 6 carbon atoms (eg, trimethylammonium Group, triethylammonium group), hydrazino group (optionally substituted), for example, a hydrazino group having 0 to 15, preferably 1 to 10, and more preferably 1 to 6 carbon atoms (eg, a trimethylhydrazino group) A ureido group (which may be substituted), for example, having 1 to 1 carbon atoms
5, preferably a ureido group having 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms (for example, ureido group, N, N
-Dimethylureido group), imide group (optionally substituted), for example, an imide group having 1 to 15 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms (eg, succinimide group), alkyl or Arylthio group (optionally substituted), for example, having 1 to 2 carbon atoms
0, preferably an alkyl or arylthio group having 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms (eg, methylthio, ethylthio, carboxyethylthio, sulfobutylthio, phenylthio, etc.), and an alkoxycarbonyl group (which may be substituted) ) For example, carbon 2 to 20,
An alkoxycarbonyl group (e.g., methoxycarbonyl, ethoxycarbonyl, benzyloxycarbonyl) preferably having 2 to 12 carbon atoms, more preferably 2 to 8 carbon atoms, an aryloxycarbonyl group (which may be substituted), for example, having 6 to 12 carbon atoms 20, preferably an aryloxycarbonyl group having 6 to 12 carbon atoms, more preferably 6 to 8 carbon atoms (for example, phenoxycarbonyl);

An alkyl group (optionally substituted);
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 carbon atom To 10, more preferably a substituted alkyl group having 1 to 5 carbon atoms (hydroxymethyl, trifluoromethyl, benzyl, carboxyethyl, ethoxycarbonylmethyl, acetylaminomethyl, and also preferably 2 to 18 carbon atoms, more preferably Represents that unsaturated hydrocarbon groups having 3 to 10 carbon atoms, particularly preferably 3 to 5 carbon atoms (for example, vinyl group, ethynyl group, 1-cyclohexenyl group, benzylidene group and benzylidene group) are also included in the substituted alkyl group. ), An aryl group (optionally substituted), for example, having 6 to 20 carbon atoms, preferably A substituted or unsubstituted aryl group having 6 to 15, more preferably 6 to 10 carbon atoms (for example, phenyl, naphthyl, p-carboxyphenyl, p-nitrophenyl, 3,5-dichlorophenyl, p-cyanophenyl, m- Fluorophenyl, p-
Toril),

Heterocyclic group (optionally substituted) For example, 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, tetrahydrofurfuryl). 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 are the above-mentioned alkyl group, aryl group, alkoxy group, halogen atom, acyl group, cyano group, sulfonyl group and benzene ring condensed, and more preferably alkyl group, aryl group Groups, 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 condensation. Most preferably, a phenyl group,
These are chlorine atom, bromine atom, iodine atom and benzene ring condensation.

L ₁ , L ₂ , L ₅ , L ₆ , L ₁₂ and L ₁₃
The methine group represented by may have a substituent, and examples of the substituent include the substituents represented by V described above. Preferably it is an unsubstituted methine group. p ₁ , p ₂ and p ₃ are 0 or 1, and preferably 0.

Z ₂ represents the group of atoms required to form an acidic nucleus, but can take the form of an acidic nucleus of any common merocyanine dye. The acidic nucleus referred to here is, for example, “The Theory of Japan” edited by James.
The Photographic Process "(The The
ory of the Photographic Pr
ocess) 4th edition, Macmillan Publishing Co., 1977,
198. Specifically, U.S. Pat. Nos. 3,567,719, 3,575,869, 3,804,634, 3,837,862, 4,002,480, 4, 925, 777, and JP-A-3-167546. Preferred when the acidic nucleus forms a 5- or 6-membered nitrogen-containing heterocycle consisting of carbon, nitrogen and chalcogen (typically oxygen, sulfur, selenium and tellurium) atoms,
The following nuclei include: 2-pyrazolin-5-one, pyrazolidine-3,5-dione, imidazolin-5-one,
Hydantoin, 2 or 4-thiohydantoin, 2-iminooxazolidin-4-one, 2-oxazoline-5
-One, 2-thiooxazoline-2,4-dione, isoxazolin-5-one, 2-thiazolin-4-one,
Thiazolidine-4-one, thiazolidine-2,4-dione, rhodanine, thiazolidine-2,4-dithione, isorhodanine, indane-1,3-dione, thiophen-3-one, thiophen-3-one-1,1- Dioxide, indoline-2-one, indoline-3-one, 2
-Oxoindazolinium, 3-oxoindazolinium, 5,7-dioxo-6,7-dihydrothiazolo [3,
2-a] pyrimidine, cyclohexane-1,3-dione,
3,4-dihydroisoquinolin-4-one, 1,3-dioxane-4,6-dione, barbituric acid, 2-thiobarbituric acid, chroman-2,4-dione, indazolin-2-one, pyrido [ 1,2-a] pyrimidine-
1,3-dione, pyrazolo [1,5-b] quinazolone,
Pyrazolo [1,5-a] benzimidazole, pyrazolopyridone, 1,2,3,4-tetrahydroquinoline-
2,4-dione, 3-oxo-2,3-dihydrobenzo [d] thiophene-1,1-dioxide, 3-dicyanomethine-2,3-dihydrobenzo [d] thiophene-
The core of 1,1-dioxide.

Z ₅ is preferably hydantoin, 2 or 4-thiohydantoin, 2-oxazolin-5-one, 2-thiooxazoline-2,4-dione, thiazolidine-2,4-dione, rhodanine, thiazolidine-.
2,4-dithione, barbituric acid, and 2-thiobarbituric acid, and more preferably, hydantoin, 2 or 4-thiohydantoin, 2-oxazolin-5-one, rhodanine, barbituric acid, and 2-thiobarbitic acid. Tool acid. Particularly preferred are 2 or 4-thiohydantoin, 2-oxazolin-5-one and rhodanine.

The 5- or 6-membered nitrogen-containing heterocyclic ring formed by Z _{4 is obtained} by removing an oxo group or a thioxo group from the heterocyclic ring represented by Z ₂ . Preferably hydantoin, 2 or 4-thiohydantoin, 2-oxazolin-5-one, 2-thiooxazoline-2,4-
Dione, thiazolidine-2,4-dione, rhodanine,
Thiazolidine-2,4-dithione, barbituric acid, 2
-Thiobarbituric acid is obtained by removing an oxo group or a thioxo group, more preferably hydantoin,
2 or 4-thiohydantoin, 2-oxazoline-5
-One, rhodanine, barbituric acid, 2-thiobarbituric acid from which an oxo group or a thioxo group has been removed, particularly preferably 2 or 4-thiohydantoin;
It is obtained by removing an oxo group or a thioxo group from 2-oxazolin-5-one or rhodanine.

R ₁ , R ₃ and R ₅ each represent an alkyl 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 (eg, 2-phenoxyethyl, 2- (1-naphthoxy) ethyl), alkoxycarbonylalkyl group (eg, 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), a heterocyclic-substituted alkyl group (for example, 2-
(Pyrrolidin-2-one-1-yl) ethyl, tetrahydrofurfuryl), alkylsulfonylcarbamoylmethyl group (for example, methanesulfonylcarbamoylmethyl group).

The alkyl group of R ₁ , R ₃ and R ₅ is preferably the above-mentioned carboxyalkyl group, sulfoalkyl group, sulfoalkenyl group or unsubstituted alkyl group, more preferably sulfoalkyl group or unsubstituted alkyl group. It is an alkyl group.

Examples of the alkyl group represented by R ₂ and R ₄ include the unsubstituted alkyl group and the substituted alkyl group mentioned above as examples of R ₁ and the like, and similar ones are preferable. Further, 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 to 20 carbon atoms, preferably 6 to 10, more preferably a substituted aryl group having 6 to 8 carbon atoms (for example, an aryl group substituted by V mentioned as a substituent such as Z ₁ described above. Specific examples include a p-methoxyphenyl group and p
-Methylphenyl group, p-chlorophenyl group and the like. ), An unsubstituted heterocyclic group having 1 to 20 carbon atoms, preferably 3 to 10 carbon atoms, and more preferably 4 to 8 carbon atoms (eg, 2-furyl, 2-thienyl, 2-pyridyl, 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), a substituted heterocyclic group having 1 to 20, preferably 3 to 10, more preferably 4 to 8 carbon atoms (for example, Z
Examples of the substituent include a heterocyclic group substituted with V as the substituent such as ₁ . Specifically, a 5-methyl-2-thienyl group, 4
-Methoxy-2-pyridyl group and the like. ).

Preferred as R ₂ and R ₄ are methyl, ethyl, 2-sulfoethyl, 3-sulfopropyl,
3-sulfobutyl, 4-sulfobutyl, carboxymethyl, phenyl, 2-pyridyl, 2-thiazolyl,
More preferably, they are ethyl, 2-sulfoethyl, carboxymethyl, phenyl, and 2-pyridyl.

L ₃ , L ₄ , L ₇ , L ₈ , L ₉ , L ₁₀ and L ₁₁ each independently represent a methine group. These methine groups may have a substituent. Examples of the substituent include a substituted or unsubstituted alkyl group having 1 to 15 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 5 carbon atoms. (Eg, 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 (eg, phenyl, o-carboxyphenyl) ), Substituted or unsubstituted C 3-20,
Preferably, the heterocyclic group has 4 to 15 carbon atoms, more preferably 6 to 10 carbon atoms (for example, N, N-, diethyl barbituric acid group), a halogen atom (for example, chlorine, bromine, fluorine, iodine), and 1 carbon atom. To 15, preferably 1 carbon
To 10, more preferably an alkoxy group having 1 to 5 carbon atoms (for example, methoxy, ethoxy),
5, preferably 1 to 10 carbon atoms, more preferably 1 to 5 alkylthio groups (eg methylthio, ethylthio), 6 to 20 carbon atoms, preferably 6 to 15 carbon atoms, more preferably 6 to 10 carbon atoms. Arylthio group (for example, phenylthio), having 0 to 15 carbon atoms, preferably 2 to 10 carbon atoms, and more preferably 4 carbon atoms
To 10 amino groups (eg, N, N-diphenylamino, N-methyl-N-phenylamino, N-methylpiperazino) and the like. It may also form a ring with other methine groups, or Z ₁ , Z ₂ , Z ₃ , Z ₄ , Z ₅
And may form a ring together.

N ₁ represents 2, 3, or 4. Preferably, it is two or three, and more preferably two. n ₂ and n ₃ represent 0, 1, 2, 3 or 4. However, when n ₂ is 0 or 1, n ₃ is 1 or more, and when n ₃ is 0, n ₂ is 2 or more. n ₂ is preferably 2, 3 and more preferably 2. n ₃ is preferably 2, 3 and more preferably 2. n ₁ , ₂ ,
_{When 3} is 2 or more, the methine group is repeated but need not be the same.

At least one of the polymethine chains formed by L ₃ and L ₄ has a crosslinked polymethine structure represented by the general formula (A). In addition, at least one of a polymethine chain formed by L ₇ and L ₈ and a polymethine chain formed by L ₉ , L ₁₀ and L ₁₁ is a crosslinked polymethine represented by at least one general formula (A). It has a polymethine structure.

[0033] As La is include those similar to the such as the aforementioned L _3, like it is preferable. More preferred are an unsubstituted methine group, a methyl-substituted methine group and a phenyl-substituted methine group, and particularly preferred is a methyl-substituted methine group.

Qa and Qb are methylene groups (in the present invention, "methylene group" is used to mean a methylene group which may be substituted), and is an unsubstituted methylene group or a substituted methylene group (for example, V Methylene group.
Specific examples include a methylene group substituted with a methyl group, a methylene group substituted with an ethyl group, a methylene group substituted with a phenyl group, a methylene group substituted with a hydroxy group, and a methylene group substituted with a halogen atom (for example, a chlorine atom or a bromine atom). ). Preferably, it is an unsubstituted methylene group.

Ra and Rb are not both methyl groups at the same time, but may be any other hydrogen atoms or monovalent substituents. The above-mentioned V is mentioned as a monovalent substituent. In addition, Ra and Rb may form a ring together.

Preferably, Ra is a hydrogen atom and Rb is
A kill group, an aryl group, or a heterocyclic group.
If it has 1 to 16 carbon atoms, preferably 1 to 8 carbon atoms,
Preferably an unsubstituted alkyl group having 1 to 4 carbon atoms (eg,
For example, methyl, ethyl, propyl, cyclopropyl,
Chill, pentyl, allyl, vinyl, here unsaturated carbon
Hydrogen groups are also included in the alkyl groups. ), Having 1 to 20 carbon atoms,
Preferably 2 to 10, more preferably carbon number
2 to 6 substituted alkyl groups (for example, Z ₁Such as
An alkyl group substituted by V mentioned as a substituent;
You. Also, specifically, benzyl, hydroxyethyl,
Ruboxyethyl and the like. )

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), 6 to 20 carbon atoms, preferably 6 to 10, more preferably an aryl group V is substituted cited as substituents, such as Z ₁ of the substituted aryl group (e.g., above 8 to 6 carbon atoms. Specifically p- methoxyphenyl group, p
-Methylphenyl group, p-chlorophenyl group and the like. ), An unsubstituted heterocyclic group having 1 to 20 carbon atoms, preferably 3 to 10 carbon atoms, and more preferably 4 to 8 carbon atoms (eg, 2-furyl, 2-thienyl, 2-pyridyl, 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), a substituted heterocyclic group having 1 to 20, preferably 3 to 10, more preferably 4 to 8 carbon atoms (for example, Z
Examples of the substituent include a heterocyclic group substituted with V as the substituent such as ₁ . Specifically, a 5-methyl-2-thienyl group, 4
-Methoxy-2-pyridyl group and the like. ).

More preferably, Ra is a hydrogen atom, Rb
Is a cyclopropyl group or a heterocyclic group. Particularly preferably, Ra is a hydrogen atom and Rb is a cyclopropyl group.

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 compound. 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, aryldisulfonate ion (for example, 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 compound may be used. Note that in the present invention in a sulfo group SO ₃ ^- but is indicated as, when having a proton as a counter ion can be expressed as SO ₃ H. m ₁ and m ₂ represent the numbers required to balance the charges, and are 0 when a salt is formed in the molecule. Preferably, the number is 0 or more and 4 or less.

Of the general formulas (I) and (II), preferred is (II).

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.

[0042]

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[0043]

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[0044]

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[0045]

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[0046]

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[0047]

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[0048]

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The compounds represented by the general formulas (I) and (II) of the present invention can be prepared by the method 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 Compounds-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 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 methine compound used in the present invention (hereinafter, the methine compound of the present invention) can be used alone or in combination with other sensitizing dyes in a silver halide photographic material.

The timing at which the methine compound of the present invention (and the same applies to other sensitizing dyes) is added to the silver halide emulsion of the present invention 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 and 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 and 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 and compound combination to be divided and added. .

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, irradiation prevention 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.

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 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 aspect ratio of the silver halide grains forming the emulsion layer is 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 written by Gatoff, Photographic Science and Engineering,
14, 248-257 (1970); US 4,
434,226, 4,414,310, 4,43
3,048, 4,439,520 and GB 2,11
2,157 can be easily adjusted. In the photographic light-sensitive material of the present invention, its abundance is at least 70%, particularly preferably at least 85%.

The methine compound of the present invention is used 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 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 transfer proces
s), photosensitive material used in the color diffusion transfer process, die transfer process (im
It is used as a light-sensitive material used for the inhibition process, a light-sensitive material used for the silver dye bleaching method, a light-sensitive material for heat development, and the like.

The silver halide photographic emulsion used in the present invention is described in Chimie et Ph.D., by P. Glaflkides.
ysique Photograhique "(Paul Montel
l) Publisher, 1967), GF Deffein (GF
Duffin), "Photographic Emulsion Chemistry" (The Focal Press, 1966),
Making and Coating Photographic 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 can contain a color coupler such as a cyan coupler, a magenta coupler and a yellow coupler, and a compound dispersing the coupler. That is, in the color development processing, aromatic 1
It may contain a compound capable of 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 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, UK Patent No. 1,278,621, JP-A Nos. 1-134447 and 1-183652, and UK 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 types of interfaces for various purposes such as coating aids, antistatic properties, improvement of slipperiness, emulsification / dispersion, prevention of adhesion and improvement of photographic properties (eg, development acceleration, high contrast, sensitization). 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.

The 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.

[0071]

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. Then, 366.5 ml of a 1.9 MAg NO ₃ aqueous solution and a KBr aqueous 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 tabular grains having an aspect ratio of 3 or more. The ratio to the total projected area was 26%. The coefficient of variation of the particle size was 7%, and the average of the particle size was 0.98 μm in sphere equivalent diameter.

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

(2) Preparation of Coated Samples Emulsion layers and protective layers as shown in Table 1 were applied to a triacetyl cellulose film support provided with an undercoat layer to prepare Samples 101 to 108.

[0077]

[Table 1]

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

Processing method Step Processing time Processing temperature Replenishment tank capacity Color development 2 minutes 45 seconds 38 ° C 33 ml 20 liter Bleaching 6 minutes 30 seconds 38 ° C 25 ml 40 liters Rinse 2 minutes 10 seconds 24 ° C 1200 ml 20 liters 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 Lithium salt 0.5 0.7 Sodium sulfite 7.0 8.0 Sodium bisulfite 5.0 5.5 Ammonium thiosulfate aqueous solution (70%) 170.0ml 200.0ml Add water 1.0 liter 1.0 liter pH 6.7 6.6 (stable solution) Mother liquor (g) Replenisher (g) Formalin ( 37%) 2.0ml 3.0ml Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.3 0.45 Disodium ethylenediaminetetraacetate 0.05 0.08 Add water 1.0 liter 1.0 liter pH 5.8-8.0 5.8-8.0

The density of the treated sample was measured with a green filter, and the fresh sensitivity and fogging were evaluated. Sensitivity is defined as the reciprocal of the exposure that gives a density 0.2 higher than the fog density,
The sensitivity of each sample was expressed as a relative value with the value of sample 101 taken as 100. The emulsion and methine compound species used for each sample and the sensitivity results for each sample are shown in Table 2 below. In addition, after the unexposed film was aged at 60% relative humidity for 60 days at 60% relative humidity, the film was similarly exposed and developed, and the sensitivity was similarly evaluated.

[0081]

[Table 2]

[0082]

Embedded image

From Table 2, it can be seen that the compounds of the present invention have lower fog, higher fresh sensitivity and less decrease in sensitivity after storage than the comparative compounds.

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, 3 were replaced with sensitizing dye (S-1) or sensitizing dye (1), and 5.0 × 1 per mol of silver halide.
Samples to which ^0-4 mol was added were designated as Sample 201 and Sample 202. To examine the sensitivity of the sample thus obtained, Fuji F
The light of a W-type photometer (Fuji Photo Film Co., Ltd.) is exposed to light for 1/100 second through an optical wedge and a red filter, and color development is performed using the same processing steps and processing liquid as in Example 1 of JP-A-8-29904. After the treatment, the cyan density was measured. The sensitivity was indicated by a relative value of fog density + 0.2. As a result, the sample 202 of the present invention had a high sensitivity of 145 with respect to the sensitivity of the comparative sample 201 of 100 (reference).

Example 3 Emulsion 1 of Example 1 of JP-A-7-92601 was obtained by replacing the spectral sensitizing dye with the sensitizing dye (S-2) or the sensitizing dye (3), and per mole of silver halide. A tetrahedral silver iodobromide emulsion was prepared which was different only in that 8 × 10 ^-4 mol was added, and these were used as emulsions 301 and 302. In addition, JP-A-7-92
Emulsion 1 of Example 1 of Example No. 601 was prepared by changing the silver potential in the second double jet from +65 mV to +115 mV, and changing the spectral sensitizing dye to sensitizing dye (S-2) or sensitizing dye (3 8) per mole of silver halide
Cubic silver iodobromide emulsions differing only in the addition of 10 ^-4 mole were prepared and used as emulsions 303 and 304. The multilayer color photosensitive material was prepared in the same manner as in Sample 4 of Example 4 of JP-A-7-92601. Samples 311 and 3 were prepared by replacing emulsion A of the fourth layer of sample 401 of Example 4 of JP-A-7-92601 with emulsion 301 or emulsion 302.
It was set to 12. Similarly, a sample in which the emulsion A of the fourth layer in the same example was changed to the emulsion 303 or the emulsion 304 was used as a sample 313.
And Sample 314. The sample thus obtained was evaluated for sensitivity. As in Example 4 of JP-A-7-92601, 1 /
Exposure for 50 seconds and color reversal processing were performed to measure cyan density. The sensitivity was calculated as the reciprocal of the amount of exposure required to give a density of +0.2 of the minimum density obtained by giving sufficient exposure, and was shown as a relative value with the sensitivity of Comparative Sample 311 being 100. As a result, the sensitivity of the sample 312 of the present invention was 152
And high sensitivity. Similarly, when the sensitivity of the comparative sample 313 is set to 100, the sensitivity of the sample 314 of the present invention is 15
5 and high sensitivity.

Example 4 An octahedral silver bromide internal latent image type direct positive emulsion and a hexagonal tabular silver bromide internal latent image type direct positive were prepared in the same manner as in Emulsions 1 and 5 of Example 1 of JP-A-5-313297. Emulsions were prepared and used as Emulsion 401 and Emulsion 402. The color diffusion transfer photographic film is a sample 101 of Example 1 of JP-A-5-313297.
In the same manner. Emulsion-2 and sensitizing dye (2) in the sixth layer of sample 101 of Example 1 of JP-A-5-313297 were combined with emulsion 401 and sensitizing dye (S-3) or sensitizing dye (17).
Were replaced with Samples 411 and 412. Similarly, the sample 413 and the sample 413 were prepared by replacing the emulsion-2 and the sensitizing dye (2) in the sixth layer of the sample 101 of the same example with the emulsion 402 and the sensitizing dye (S-3) or the sensitizing dye (17). 4
It was set to 14. The replaced sensitizing dyes (S-3), (1
7) was added in an amount of 9 × 10 ^-4 mol per mol of silver halide. To examine the sensitivity of the sample thus obtained, see
The same exposure and processing steps as in Example 1 of JP-A-313297 were performed, and processing was performed using a processing solution, and the transfer density was measured with a color densitometer. The sensitivity was expressed as a relative value at a density of 1.0. Comparative sample 411
The sensitivity of sample 412 of the present invention was as high as 141 when the sensitivity was 100, and the sensitivity of sample 414 of the present invention was as high as 143 when the sensitivity of comparative sample 413 was 100.

Example 5 Emulsion F of Example 2 of JP-A-4-42536 was compared with red-sensitive sensitizer
Do not add dye (S-1) before sulfur sensitization,
In addition to sulfur sensitization of tilthiourea, chloroauric acid is also used
Optimal gold-sulfur sensitization, sensitizing dye after gold-sulfur sensitization
(S-4) (Comparative dye of the present invention) or sensitizing dye (2
5) 2 × 10 5 per mole of silver halide ^-FourMole added
A silver chlorobromide emulsion that differs only in that
501 and 502. Multilayer color printing paper is
A sample was prepared in the same manner according to Sample 20 of Example 1 of No. 6-347944.
Was. Japanese Patent Application Laid-Open No. 6-347944
The emulsion of five layers was changed to emulsion 501 or emulsion 502
The samples were Sample 511 and Sample 512. Thus obtained
Fuji FW sensitometer (Fuji
Photo film Co., Ltd.)
Exposure through a filter for 1/10 second.
Color development using the same processing steps and processing solution as in Example 1
Processing was performed. As a result, the sensitivity of the comparative sample 511 was 1
The sensitivity of the sample 512 of the present invention is 142 as high as
Sensitivity.

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 dyes 1 and 2 were replaced with sensitizing dye (S-3) or sensitizing dye (17), and 2 × 1 per mol of silver halide
Chemical sensitization was performed only by adding ^0-4 mol, and these were used as emulsion 601 and emulsion 612. The coating sample was prepared by replacing the emulsion of Example 1 of Japanese Patent Application No. 7-232036 with Emulsion 601 or Emulsion 602, and combining an emulsion layer and a surface protective layer on a support in the same manner as in Example 1 by simultaneous extrusion. This was used as Sample 611 and Sample 612.
The amount of silver applied per side was 1.75 g / m ² . In order to examine the sensitivity of the sample thus obtained, exposure was performed for 0.05 seconds from both sides using an X-ray orthoscreen HGM manufactured by Fuji Photo Film Co., Ltd. Processing was carried out in the same manner as in Example 1, using an automatic developing machine and a processing solution. The sensitivity was represented by the logarithm of the reciprocal of the exposure required to give a density of fog +0.1, and the sensitivity of sample 611 was set to 100, and the other values were represented by relative values. As a result, the sensitivity of Sample 612 of the present invention was 143, which was high. The same effect was obtained by exposing with HR-4 or HGH instead of the X-ray orthoscreen HGM used at the time of exposure.

Example 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 added to emulsion 701 and sensitizing dye (S-1).
Alternatively, Sample 711 and Sample 712 were used instead of the sensitizing dye (1). The replaced sensitizing dyes (S-1) and (1) were 5 × 1 per mol of silver halide.
^0-4 moles were added. To check the sensitivity of the sample thus obtained, a Fuji FW type sensitometer (Fuji Photo Film Co., Ltd.)
Light through optical wedge and green filter to 1/10
A 0-second exposure was given, 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 711 was set to 100. The sensitivity of the sample 712 of the present invention is 143.
And high sensitivity.

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. 7-146891. The coated sample was prepared in the same manner as in the coated sample F of Example 3 of Japanese Patent Application No. 74-168991. Sample 811 and Sample 811 were obtained by replacing Emulsion F and Sensitizing Dye-1 of Coating Sample F in Example 3 of Japanese Patent Application No. 74-168991 with Emulsion 801 and Sensitizing Dye (S-4) or Sensitizing Dye (25). Sample 812 was obtained. The replaced sensitizing dyes (S-4) and (25) were added in an amount of 5 × 10 ⁻⁴ mol per mol of silver halide. In order to examine the sensitivity of the sample thus obtained, light from a Fuji FW type sensitometer (Fuji Photo Film Co., Ltd.) was exposed to light for 1/100 second through an optical wedge and a red filter.
6 treatments were performed and the photographic properties were compared. Sensitivity is +0.2
The sensitivity of sample 811 was defined as 100, expressed as the logarithm of the reciprocal of the amount of exposure required to give the density. The sensitivity of Sample 812 of the present invention was 146, which was high.

[0091]

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

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[Procedure amendment]

[Submission date] March 17, 1997

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Claim 2

[Correction method] Change

[Correction contents]

Embedded image In the formula (I), L ₁ , L ₂ , L ₃ and L ₄ represent a methine group. p ₁ represents 0 or 1. n ₁ represents 2, 3 or 4. Z ₁ and Z ₂ each represent an atom group necessary for forming a 5- or 6-membered nitrogen-containing heterocyclic ring. M ₁ represents a charge balancing counter ion, and m ₁ represents a number of 0 or more necessary to neutralize the charge of the molecule. R ₁ represents an alkyl group, and R ₂ represents an alkyl group, an aryl group, or a heterocyclic group. General formula (II)

Embedded image In the formula (II), L ₅ , L ₆ , L ₇ , L ₈ , L ₉ , L ₁₀ , L
₁₁ , L ₁₂ and L ₁₃ represent a methine group. p ₂ and p ₃ are 0
Or represents 1. n ₂ and n ₃ represent 0, 1, 2, 3 or 4. However, when n ₂ is 0 or 1, n ₃ is 1 or more, and when n ₃ is 0, n ₂ is 2 or more. Z ₃ , Z ₄ and Z ₅ each represent an atom group necessary for forming a 5- or 6-membered nitrogen-containing heterocyclic ring. M ₂ represents a charge balancing counter ion;
₂ represents a number of 0 or more necessary to neutralize the electric charge of the molecule. R ₃ and R ₅ represent an alkyl group. R ₄ represents an alkyl group, an aryl group, or a heterocyclic group. However, L ₃ , L
_The polymethine chain formed in ₄ has at least one crosslinked polymethine structure represented by the general formula (A). In addition, at least one of a polymethine chain formed by L ₇ and L ₈ and a polymethine chain formed by L ₉ , L ₁₀ and L ₁₁ is represented by at least one of the general formula (A) according to claim 1. It has a cross-linked polymethine structure.

Claims (4)

[Claims] 1. A silver halide photographic light-sensitive material comprising at least one methine compound having a crosslinked polymethine structure represented by the following general formula (A). However, the methine compound is not pentamethine cyanine. General formula (A) In the formula (A), La represents a methine group. Qa and Qb represent a methylene group. Ra and Rb represent a hydrogen atom, or 1
Represents a valent substituent. However, Ra and Rb are not methyl groups at the same time. 2. A silver halide photographic material comprising a methine compound represented by the following formula (I) or (II). General formula (I) In the formula (I), L ₁ , L ₂ , L ₃ and L ₄ represent a methine group. p ₁ represents 0 or 1. n ₁ represents 2, 3 or 4. Z ₁ and Z ₂ each represent an atom group necessary for forming a 5- or 6-membered nitrogen-containing heterocyclic ring. M ₁ represents a charge balancing counter ion, and m ₁ represents a number of 0 or more necessary to neutralize the charge of the molecule. R ₁ represents an alkyl group, and R ₂ represents an alkyl group, an aryl group, or a heterocyclic group. General formula (II) In the formula (II), L ₅ , L ₆ , L ₇ , L ₈ , L ₉ : L ₁₀ , L _9
11: L ₁₂ and L ₁₃ each represents a methine group. p ₂ and p ₃ are 0
Or represents 1. n ₂ and n ₃ represent 0, 1, 2, 3 or 4. However, when n ₂ is 0 or 1, n ₃ is 1 or more, and when n ₃ is 0, n ₂ is 2 or more. Z ₃ , Z ₄ and Z ₅ each represent an atom group necessary for forming a 5- or 6-membered nitrogen-containing heterocyclic ring. M ₂ represents a charge balancing counter ion;
₂ represents a number of 0 or more necessary to neutralize the electric charge of the molecule. R ₃ and R ₅ represent an alkyl group. R ₄ represents an alkyl group, an aryl group, or a heterocyclic group. However, L ₃ , L
_The polymethine chain formed in ₄ has at least one crosslinked polymethine structure represented by the general formula (A). Further, at least one of a polymethine chain formed by L ₇ and L ₈ and a polymethine chain formed by L ₉ , L ₁₀ and L ₁₁ is represented by at least one of the general formula (A) according to claim 1. It has a cross-linked polymethine structure. 3. The compound of the general formula (I) or (I) according to claim 2,
In the polymethine chain represented by the general formula (A) of the methine compound represented by I), Ra is a hydrogen atom;
3 is an alkyl group, an aryl group, or a heterocyclic group. 4. The compound represented by the general formula (I) according to claim 2,
In the polymethine chain represented by the general formula (A) of the methine compound represented by I), Ra is a hydrogen atom;
3. The silver halide photographic material according to claim 2, wherein is represented by a cyclopropyl group.