JPH0915778A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE: To provide the silver halide photographic sensitive material high in sensitivity and low in fog and superior in storage stability. CONSTITUTION: The silver halide photographic sensitive material contains silver halide grains subjected to reduction sensitization and at least one kind of compound represented by the general formula in which La is a methylene group; V1 is a monovalent substituent; q1 is 1, 2, 3, or 4; q2 is 0 or same as q1 ; each of L1 and L2 is a methine group; p1 is 0 or 1; Z1 is an atomic group necessary to form an N-containing 5- or 6-membered hetero ring; M1 is a charge balancing counter ion: m1 is an integer of >=0 necessary to neutralize an intramolecular charge; and Q is a methine or polymethine group substituted by a heterocyclic or aromatic group.

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. More specifically, the present invention relates to a silver halide photographic material having high sensitivity, little fog, 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 materials. 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. For example, as described in U.S. Pat. No. 4,975,362, photographic performance is greatly improved only by having a methylthio group. Of the sensitizing dyes, those having a nitrogen-containing heterocycle having a sulfoalkyl group as a partial structure are often used. Well-known examples of the sulfoalkyl group include a 2-sulfoethyl group, a 3-sulfopropyl group, a 4-sulfobutyl group, and a 3-sulfobutyl group. However, sulfoalkyl groups other than these have been scarcely studied, and it is currently impossible to predict what kind of photographic performance various sulfoalkyl groups other than these will show. Further, reduction sensitization attempts have been studied for a long time in order to increase the sensitivity of silver halide photographic light-sensitive materials. For example, tin compounds are useful as reduction sensitizers in US Pat. No. 2,487,850, polyamine compounds are useful in US Pat. No. 2,512,925, and thiourea dioxide compounds are useful as reduction sensitizers in British Patent 789,823. Was disclosed. Furthermore, Photographic Science and Engineeri
23, page 113 (1979), the properties of silver nuclei produced by various reduction sensitization methods are compared, and include dimethylamine borane, stannous chloride, hydrazine, high p.
The methods of H aging and low pAg aging were adopted. The method of reduction sensitization is further described in U.S. Patent Nos. 2,518,698, 3,201,254, 3,411,917, 3,779,777, and 3,930, No. 867. Regarding the improvement of the reduction sensitization method as well as the selection of the reduction sensitizer, JP-B-57-33572 and 5
8-1410.

However, according to the research conducted by the inventors, when spectral sensitization is carried out by adsorbing a sensitizing dye to reduction-sensitized silver halide grains, particularly when spectral sensitization in green and red regions is performed. It was found that it was extremely difficult to obtain sufficient spectral sensitivity without causing an undesirable effect on photographic performance (for example, increase in fog).

Further, a method of adsorbing the sensitizing dye at a high temperature (50 ° C. or higher) or a high sensitivity in order to prevent desorption of the sensitizing dye from the silver halide grains in the light-sensitive material (especially at high humidity) Methods for adsorbing a sensitizing dye before chemical sensitization are widely known for the purpose of chemical conversion.However, when adsorbing a spectral sensitizing dye in the green range or red range to a reduction sensitized emulsion, these methods are widely known. When applied, it significantly increases fog.

For the above reasons, there has been a demand for a technique for spectrally sensitizing reduction-sensitized silver halide grains with high sensitivity and without causing adverse effects such as fogging.

[0006]

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

[0007]

As a result of intensive studies, the object of the present invention is to provide a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support.
A silver halide photographic light-sensitive material characterized in that silver halide grains in at least one of the emulsion layers have been subjected to reduction sensitization and contain at least one compound represented by the following general formula (I). Could be achieved by General formula (I)

[0008]

[Chemical 6]

In the formula (I), La represents a methylene group, and V
₁ represents a monovalent substituent. q ₁ represents ₁ , 2, 3 or 4 and q ₂ represents 0, 1, ₂ , 3 or 4. L ₁ and L ₂
Represents a methine group. p ₁ represents 0 or 1. Z ₁ represents 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. Q represents a methine group or a polymethine group substituted with a heterocyclic group or an aromatic group. Further, the compound represented by the general formula (I) is
A compound selected from the following general formula (II), general formula (III) or general formula (IV) is more preferable. General formula (II)

[0010]

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In the formula (II), L ₃ , L ₄ , L ₅ , L ₆ and L
₇ , L ₈ and L ₉ represent a methine group. p ₂ and p ₃ represent 0 or 1. n ₁ represents 0, 1, 2, or 3. Z
₂ and Z ₃ represent an atomic group necessary for forming a 5- or 6-membered nitrogen-containing heterocycle. M ₂ represents a charge-balancing counterion, and m ₂ represents a number of 0 or more and 6 or less required to neutralize the charge of the molecule. R ₁ and R ₂ represent an alkyl group. However, at least one of R ₁ and R ₂ is Rz below.
Is an alkyl group represented by

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In Rz, La ₁ has the same meaning as La. V _1a has the same _meaning as V ₁ . q _1a has the same meaning as q _1, q _2a has the same meaning as q _2. General formula (III)

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In the formula (III), L ₁₀ , L ₁₁ , L ₁₂ and L ₁₃ represent a methine group. p ₄ is 0 or 1. n ₂ is 0,
Represents 1, 2, or 3. Z ₄ and Z ₅ represent an atom group necessary for forming a 5- or 6-membered nitrogen-containing heterocyclic ring. M ₃
Represents a charge balancing counter ion, and m ₃ represents a number of 0 or more and 6 or less necessary for neutralizing the charge of the molecule. R ₃ and R ₄ represent an alkyl group. However, at least one of R ₃ and R ₄ is the alkyl group represented by Rz. General formula (IV)

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In the formula (IV), L ₁₄ , L ₁₅ , L ₁₆ , L ₁₇ , L
₁₈ , L ₁₉ , L ₂₀ and L ₂₁ represent a methine group. p ₄ and p
₅ represents 0 or 1. n ₃ and n ₄ represent 0, 1, 2, or 3. Z ₅ , Z ₇ and Z ₈ each represent an atom group necessary for forming a 5- or 6-membered nitrogen-containing heterocyclic ring. M ₄ represents a charge-balancing counter ion, and m ₄ represents a number from 0 to 6 required to neutralize the charge of the molecule. R ₅ , R ₆ and R ₇ represent an alkyl group. However, at least one of R ₅ , R ₆ and R ₇ is an alkyl group represented by Rz.

The compounds used in the present invention will be described in detail below.

The general formula (I) can be represented by the following resonance formula when a cyanine dye is formed by Q.

[0020]

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In the general formulas (I), (II), (III) and (IV), a 5- or 6-membered nitrogen-containing compound represented by Z ₁ , Z ₂ , Z ₃ , Z ₄ , Z ₆ and Z ₈ is used. As a heterocycle,

Thiazoline nucleus, thiazole nucleus, benzothiazole nucleus, oxazoline nucleus, oxazole nucleus, benzoxazole nucleus, selenazoline nucleus, selenazole nucleus, benzoselenazole nucleus, 3,3-dialkylindolenine nucleus (eg 3,3-dimethylindoinucleus) 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 Examples thereof include a quinoxaline nucleus, an oxadiazole nucleus, a thiadiazole nucleus, a tetrazole nucleus, and a pyrimidine nucleus.

Benzoxazole nucleus, benzothiazole nucleus, benzimidazole nucleus and quinoline nucleus are preferred, and benzoxazole nucleus and benzothiazole nucleus are more preferred. Particularly preferably, Z ₁ and Z ₂ in the general formula (II) are benzoxazole nuclei.

Assuming that the substituent on Z ₁ , Z ₂ , Z ₃ , Z ₄ , Z ₆ and Z ₈ is V, the substituent represented by V is not particularly limited. ,
Bromide, iodine, fluorine), mercapto group, cyano group, carboxyl group, phosphate group, sulfo group, hydroxy group, carbamoyl having 1 to 10, preferably 2 to 8, more preferably 2 to 5 carbon atoms Groups (eg, methylcarbamoyl, ethylcarbamoyl, morpholinocarbonyl), sulfamoyl groups having 0 to 10, preferably 2 to 8, more preferably 2 to 5 carbon atoms (eg, methylsulfamoyl, ethylsulfamoyl, Piperidinosulfonyl), nitro group, alkoxy group having 1 to 20, preferably 1 to 10, more preferably 1 to 8 carbon atoms (eg, methoxy, ethoxy, 2-methoxyethoxy, 2-phenylethoxy) , Having 6 to 20 carbon atoms, preferably 6 to 1 carbon atoms
2, more preferably an aryloxy group having 6 to 10 carbon atoms (for example, phenoxy, p-methylphenoxy, p-
Chlorophenoxy, naphthoxy), carbon number 1 to 20,
Preferably, it is an acyl group having 2 to 12 carbon atoms, more preferably 2 to 8 carbon atoms (eg, acetyl, benzoyl, trichloroacetyl), 1 to 20 carbon atoms, preferably 2 to 12 carbon atoms, more preferably 2 to 12 carbon atoms. 8 acyloxy groups (eg, acetyloxy, benzoyloxy), having 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 having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms (eg, methanesulfonyl, ethane Sulfonyl, benzenesulfonyl, etc.), having 1 to 2 carbon atoms
0, preferably a sulfinyl group having 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms (for example, methanesulfinyl, benzenesulfinyl), 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 10 carbon atoms
To 8 sulfonylamino groups (eg, methanesulfonylamino, ethanesulfonylamino, benzenesulfonylamino, etc.), amino groups, 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, and more preferably 1 to 8 carbon atoms.
A substituted amino group of (eg, methylamino, dimethylamino, benzylamino, anilino, diphenylamino),
Ammonium group having 0 to 15 carbon atoms, preferably 3 to 10 carbon atoms, more preferably 3 to 6 carbon atoms (eg trimethylammonium group, triethylammonium group), 0 to 15 carbon atoms, preferably 1 to 1 carbon atoms
0, more preferably a hydrazino group having 1 to 6 carbon atoms (eg, trimethylhydrazino group), 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, a ureido group, N, N
-Dimethylureido group), having 1 to 15 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 6 carbon atoms.
An imide group (for example, a succinimide group), an alkyl or arylthio group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, and more preferably 1 to 8 carbon atoms (for example, methylthio, ethylthio, carboxyethylthio, sulfobutylthio, Phenylthio, etc.), 2 to 2 carbon atoms
0, preferably 2 to 12 carbon atoms, more preferably 2 to 8 carbon alkoxycarbonyl groups (eg methoxycarbonyl, ethoxycarbonyl, benzyloxycarbonyl), 6 to 20 carbon atoms, preferably 6 to 12 carbon atoms, and Preferably an aryloxycarbonyl group having 6 to 8 carbon atoms (for example, phenoxycarbonyl),

An unsubstituted alkyl group having 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms (eg, methyl, ethyl, propyl, butyl), 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 an unsaturated hydrocarbon group having 2 to 18 carbon atoms, preferably 3 to 10 carbon atoms, more 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. ), Having 6 to 20 carbon atoms, preferably 6 to 1 carbon atoms.
5, more preferably a substituted or unsubstituted aryl group having 6 to 10 carbon atoms (for example, phenyl, naphthyl, p-carboxyphenyl, p-nitrophenyl, 3,5-dichlorophenyl, p-cyanophenyl, m-fluorophenyl, p-tolyl),

Heterocyclic groups having 1 to 20 carbon atoms, preferably 2 to 10 carbon atoms, and more preferably 4 to 6 carbon atoms, which may be substituted (eg pyridyl, 5-methylpyridyl, thienyl, furyl, morpholino, tetrahydro). Furfuril). Further, a structure in which a benzene ring or a naphthalene ring is condensed can be employed. Further, V may be further substituted on these substituents.

Preferred as the substituents on Z ₁ , Z ₂ , Z ₃ , Z ₄ , Z ₆ and Z ₈ are the above-mentioned alkyl group, aryl group, alkoxy group, halogen atom, acyl group, cyano group and sulfonyl group. , And benzene ring condensation, more preferably an alkyl group, an aryl group, a halogen atom,
An acyl group, a sulfonyl group, and a benzene ring fused,
Particularly preferred are methyl group, methoxy group, phenyl group, chlorine atom, bromine atom, iodine atom, and benzene ring condensation. Most preferred are a phenyl group, a chlorine atom, a bromine atom and an iodine atom.

V ₁ and V _1a in the general formula (I) and the substituent Rz have the same meanings as the above-mentioned substituent represented by V, and the same ones are preferable.

Examples of La and La ₁ include an unsubstituted methylene group and a substituted methylene group (for example, a V-substituted methylene group mentioned above as a substituent for Z _{1 and the} like).
Specific examples include a methyl group-substituted methylene group, an ethyl group-substituted methylene group, a phenyl group-substituted methylene group, and a hydroxy group-substituted methylene group. ) Preferably, it is an unsubstituted methylene group. q ₁ and q _1a represent 1, 2, 3 or 4. When q ₁ and q _1a are 2 or more, La and La ₁
Are repeated, but need not be identical. q ₁ and q
_1a is preferably 1. q ₂ and q _2a are 0,
Represents 1, 2, 3 or 4. When q ₂ and q _2a are 2 or more, V ₁ and V _1a are repeated, but need not be the same. q ₂ and q _2a are preferably 0.

Examples of the general formula (I) or Rz are shown below.
The most preferable is Rz ₂ .

[0031]

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R ₁ and R in the general formulas (II), (III) and (IV)
₂ , R ₃ , R ₅ and R ₇ each represent an alkyl group. Examples of the alkyl group represented by R ₁ and R ₂ include unsubstituted alkyl groups having 1 to 18, preferably 1 to 7 and particularly preferably 1 to 4 carbon atoms (eg, methyl, ethyl, propyl, isopropyl, butyl, Isobutyl, hexyl, octyl, dodecyl, octadecyl), a substituted alkyl group having 1 to 18 carbon atoms, preferably 1 to 7, and particularly preferably 1 to 4 carbon atoms {for example, Z as described above.
_The alkyl group substituted with V mentioned as the substituent such as ₁ may be mentioned. Preferably, an aralkyl group (eg, benzyl, 2-phenylethyl), an unsaturated hydrocarbon group (eg, allyl group), a hydroxyalkyl group (eg, 2-hydroxyethyl, 3-hydroxypropyl), a carboxyalkyl group (eg, 2- Carboxyethyl, 3-carboxypropyl, 4-carboxybutyl, carboxymethyl), alkoxyalkyl group (for example, 2-methoxyethyl, 2- (2-methoxyethoxy) ethyl), aryloxyalkyl group (for example, 2-phenoxyethyl, Two
-(1-naphthoxy) ethyl), an alkoxycarbonylalkyl group (eg, ethoxycarbonylmethyl, 2-benzyloxycarbonylethyl), an aryloxycarbonylalkyl group (eg, 3-phenoxycarbonylpropyl), an acyloxyalkyl group (eg, 2-acetyloxy). Ethyl), acylalkyl groups (eg 2-acetylethyl), carbamoylalkyl groups (eg 2-morpholinocarbonylethyl), sulfamoylalkyl groups (eg N, N-dimethylcarbamoylmethyl), sulfoalkyl groups (eg 2- Sulfoethyl, 2-sulfopropyl, 3-sulfobutyl, 4-sulfobutyl, 2-
[3-Sulfopropoxy] ethyl, 2-hydroxy-3
-Sulfopropyl, 3-sulfopropoxyethoxyethyl), a sulfatoalkyl group (eg, 3-sulfatopropyl, 4-sulfatobutyl), a heterocyclic-substituted alkyl group (eg, 2- (pyrrolidin-2-one-1-) Ill)
Ethyl, tetrahydrofurfuryl), methanesulfonylcarbamoylmethyl group, and the like}.

The alkyl group of R ₁ , R ₂ , R ₃ , R ₅ and R ₇ is preferably the above-mentioned carboxyalkyl group or sulfoalkyl group, more preferably sulfoalkyl group.

Z ₅ represents the atomic group necessary for forming an acidic nucleus, but can take the form of the acidic nucleus of any general merocyanine dye. The acidic nucleus referred to here is, for example, "The Theory of the Photographic Process" edited by James.
tographic Process) 4th edition, Macmillan Publishing Company, 197
7 years, defined by 198 pages. Specifically, U.S. Patent Nos. 3,567,719, 3,575,869,
Nos. 3,804,634, 3,837,862, 4,002,480, 4,925,777, and JP-A-3-167546. 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 nucleus is mentioned. 2-pyrazolin-5-one, pyrazolidine-3,5-dione, imidazolin-5-one, hydantoin, 2 or 4-thiohydantoin, 2-iminooxazolidin-4-one, 2-oxazolin-5-one, 2- Thiooxazoline-2,4-dione, isoxazoline-5-one, 2-thiazolin-4-one, thiazolidin-4-one, thiazolidine-2,4-dione,
Rhodanine, thiazolidine-2,4-dithione, isorhodanine, indane-1,3-dione, thiophene-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, indazoline-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-
1,1-Dioxide core.

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

The 5- or 6-membered nitrogen-containing heterocycle formed by Z ₇ is the heterocycle represented by Z ₅ from which an oxo group or a thioxo group has been removed. Preferably hydantoin, 2 or 4-thiohydantoin, 2-oxazoline-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.

Examples of the alkyl group represented by R ₄ and R ₆ include the unsubstituted alkyl groups and substituted alkyl groups 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 carbon atoms, preferably 3 to 10 carbon atoms, and more preferably 4 to 8 carbon atoms (for example, a heterocyclic group substituted with V mentioned above as a substituent of Z _{1 and the} like). And a cyclic group, specifically 5-methyl-2.
-Thienyl group, 4-methoxy-2-pyridyl group and the like. ). Preferred as R ₄ and R ₆ are methyl, ethyl, 2-sulfoethyl, 3-sulfopropyl, 3-sulfobutyl, 4-sulfobutyl, carboxymethyl, phenyl, 2-pyridyl, 2-thiazolyl, more preferably ethyl, 2-sulfoethyl, carboxymethyl, phenyl and 2-pyridyl.

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 , L ₁₆ , L ₁₇ , L ₁₈ , L ₁₉ , L ₂₀ , L ₂₁ and L ₂₂ each independently represent a methine group. The methine group represented by L _{1 to} L ₂₂ 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 carbon An alkyl group of the formulas 1 to 5 (for example, methyl, ethyl, 2-carboxyethyl), a substituted or unsubstituted C 6 to C 20,
An aryl group having preferably 6 to 15 carbon atoms, more preferably 6 to 10 carbon atoms (eg, phenyl, o-carboxyphenyl), substituted or unsubstituted 3 to 2 carbon atoms
0, preferably 4 to 15 carbon atoms, more preferably 6 to 10 carbon heterocyclic groups (eg N, N-diethylbarbituric acid group), halogen atoms (eg chlorine, bromine,
(Fluorine, iodine), C1 to C15, preferably C1 to C10, more preferably C1 to C5 alkoxy groups (eg methoxy, ethoxy), C1 to C1.
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 (for example, N, N-diphenylamino, N-methyl-N-phenylamino, N-methylpiperazino) and the like. Further, a ring may be formed with another methine group, or an auxochrome may be formed with a ring.

N ₁ , n ₂ , and n ₃ are preferably 0, 1
And more preferably 1. n ₄ is preferably 0 or 1, and more preferably 0. n ₁ ,
_{When 2} , ₃ , ₄ are 2 or more, the methine group is repeated but does not have to be the same.

M ₁ , M ₂ , M ₃ and M ₄ are included in the formula to indicate the presence of a cation or anion when required to neutralize the ionic charge of the dye. .
Typical cations include inorganic cations such as alkali metal ions (eg sodium ion, potassium ion, lithium ion), alkaline earth metal ions (eg calcium ion), ammonium ions (eg ammonium ion, tetraalkylammonium ion). , Pyridinium ion, ethylpyridinium ion) and the like. The anion may be either an inorganic anion or an organic anion,
Halogen anions (for example, fluorine ions, chlorine ions,
Iodine ion), substituted aryl sulfonate ion (for example, p-toluene sulfonate ion, p-chlorobenzene sulfonate ion), aryl disulfonate ion (for example, 1,3-benzene sulfonate ion, 1,5-naphthalenedisulfonate ion) , 2,6-naphthalenedisulfonate ion), alkylsulfate ion (for example, methylsulfate ion), sulfate ion, thiocyanate ion, perchlorate ion, tetrafluoroborate ion, picrate ion, acetate ion, trifluoromethanesulfonate ion. Ions are mentioned. Further, another dye having a charge opposite to that of the ionic polymer or the dye may be used. m ₁ , m ₂ ,
m ₃ and m ₄ represent the numbers required to balance the charge, and are 0 when forming a salt in the molecule. m ₁ ,
Each of m ₂ , m ₃ and m ₄ is preferably a number of 0 or more and 6 or less, more preferably a number of 0 or more and 4 or less, particularly preferably a number of 0 or more and 2 or less. p ₁ , p ₂ , p ₃ , p ₄ ,
p ₅ and p ₆ each independently represent 0 or 1. It is preferably 0.

Of the general formulas (II), (III) and (IV), the most preferable one is (II). Further, most preferably of the general formula (II), Z ₂ is a 5-phenylbenzoxazole nucleus, Z ₃ is a 5-chlorobenzoxazole nucleus, R ₁
Is an o-sulfobenzyl group, and R ₂ is a mercapto-substituted oxacarbocyanine in which R ₂ represents a sulfoalkyl group. That is, II-9 and II-1 of (Chemical Formula 14) described later
3, II-15, II-18 and the like.

The general formulas (I), (II) and (I of the present invention will be described below.
Specific examples of the compounds of II) and (IV) are shown below, but the present invention is not limited thereto. The general formula (I
Since I), (III) and (IV) are subordinate concepts of the general formula (I), specific examples of the general formula (I) include compounds excluding these subordinate concepts. Specific examples of the compound of the general formula (II)

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Specific examples of compounds of general formula (III)

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Specific examples of compounds of general formula (IV)

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Specific Examples of Compounds of Formula (I)

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The compound represented by the general formula (I) of the present invention is a compound described by "FM Harmer", "Heterocyclic Compounds-Cyrinized and Related Compounds".
anine Dyes and Related Compounds ", John Wiley & Sons-New York, London, 1964, DMSturmer," Heterocyclic Compounds-Special Topics. " In Heterocyclic Compounds-Special
topics in heterocyclic chemistry ", Chapter 18, Section 14, 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, Chapters 369-422, Elsevier Science Public Company, Inc.
Science Publishing Company Inc.), published in New York, and the like.

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

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(Synthesis of (3)) (1) 4 g (0.019 mol)
(2) 3.6 g (0.021 mol) was heated and stirred on a 150 ° C. oil bath for 2 hours. 100 ml of ethyl acetate was added to the reaction solution while stirring, and after the reaction solution reached room temperature, the obtained crystals were filtered by suction filtration and dried. (3) (Colorless powder, yield 7.21 g, yield 100%, melting point 155-16
(0 ° C.) (2) was synthesized by the method described in Ann., 562.23 (1949).

(Synthesis of (II-1)) (3) 7 g (0.01
84 mol), (4) 17 ml, acetic acid 11 ml, pyridine 11 ml
Was heated and stirred on an oil bath at 140 ° C., and 5.2 ml of triethylamine was added dropwise. After heating and stirring for 2 hours, 100 ml of ethyl acetate was added and the mixture was left for 5 hours. The precipitated crystals were separated by suction filtration, 100 ml of methanol was added to the obtained crystals, and the mixture was heated under reflux to complete dissolution. After natural filtration, the filtrate was cooled with water, and the precipitated crystals were separated by suction filtration. This recrystallization operation was repeated once, and the obtained crystals were dried. (II-1) (red powder, yield 0.8
3 g, yield 11%, melting point 232-235 ° C., λ max = 5
04 nm, ε = 146000 (in methanol))

The addition amount of the spectral sensitizing dye represented by the general formula (I) is 0.5 × 10 ^-6 mol to 1 mol of silver halide.
A range of 1.0 × 10 ⁻² mol is preferred. More preferably,
It is in the range of 1.0 × 10 ⁻⁵ mol to 5.0 × 10 ⁻³ mol. It is preferably used as a spectral sensitizer for reduction-sensitized emulsions. The sensitizing dye may be added during the formation of silver halide grains or during the chemical sensitization, or may be added during coating. In particular, US Pat. No. 4,225,666 discloses a method of adding a sensitizing dye during the formation of silver halide emulsion grains.
No. 4,828,972, JP-A-61-103,149.
Issue can be referred to. Further, as a method of adding a sensitizing dye in the desalting step of a silver halide emulsion, EP-A-291,339-A and JP-A-64-52,13
No. 7 can be referred to. A method of adding a sensitizing dye in the chemical sensitization step is disclosed in JP-A-59-488.7.
No. 56 can be referred to.

As a method of increasing the spectral sensitizing sensitivity with a sensitizing dye, a method of using two or more sensitizing dyes in combination is known. When two or more kinds of sensitizing dyes are used in combination, the spectral sensitivity often becomes an intermediate effect when each sensitizing dye is used alone or decreases, but when a certain special combination is used. , The spectral sensitivity may be remarkably increased as compared with the case where each sensitizing dye is used alone. This phenomenon is usually called the supersensitizing action of the sensitizing dye. TH Jam for supersensitization
It is summarized in Chapter 10 (co-authored by W. West and PB Gilman) of es edition "The Theory of the Photographic Process" (4th edition, Macmillan, New York, 1977).
When such a combination is used, the spectral sensitizing wavelength may be in the middle of the spectral sensitizing wavelength obtained when each sensitizing dye is used alone, or may be a simple bond.
In some cases, the spectral sensitization shifts to a wavelength that cannot be predicted from the spectral sensitization characteristics of the single use. By using the sensitizing dyes in combination as described above, it is possible to obtain a spectral sensitivity higher than that when each of the sensitizing dyes is used alone, and to set the sensitizing wavelength range suitable for the purpose of use of the photographic light-sensitive material. Finding a combination of sensitizing dyes has become a major problem in the spectral sensitization technology of silver halide photographic emulsions. The combination of sensitizing dyes used to obtain supersensitization requires remarkable selectivity between the dyes, and it seems that a slight difference in chemical structure is apparent in the supersensitizing action. It has a significant effect. That is, the combination of sensitizing dyes that bring about a supersensitizing effect is
It is difficult to predict simply from the chemical structural formula.

As the supersensitizer, it is possible to use a dye which does not have a spectral sensitizing effect by itself or a substance which does not substantially absorb visible light. For example, anomistyryl compounds substituted with a nitrogen-containing heterocyclic group (for example, those described in US Pat. Nos. 2,933,390 and 3,635,721) and aromatic organic acid formaldehyde condensates (for example, US Pat. , 743, 510), a cadmium salt, an azaindene compound, and the like.
U.S. Patents 3,615,613 and 3,615,641
The combinations described in Nos. 3,617,295 and 3,635,721 are particularly useful.

The process for producing a silver halide emulsion is roughly divided into processes such as grain formation, desalting, and chemical sensitization. Particle formation is divided into nucleation, ripening and growth. These steps are not performed uniformly, but the order of the steps is reversed or the steps are repeatedly performed. The reduction sensitization used in the present invention is basically performed at any step during the production step of the silver halide emulsion. Reduction sensitization may be performed during nucleation, which is the initial stage of grain formation, during physical ripening, or during growth, and may be performed prior to chemical sensitization other than reduction sensitization or after this chemical sensitization. . When performing chemical sensitization in combination with gold sensitization, reduction sensitization is preferably performed prior to chemical sensitization so as not to cause undesirable fog. Most preferred is a method of reduction sensitization during growth of silver halide grains. The term "during growth" here also refers to a method in which the silver halide grains are physically ripened or subjected to reduction sensitization while they are growing by the addition of a water-soluble silver salt and a water-soluble alkali halide, and the growth is temporarily stopped during the growth. It means that the method also includes a method of performing reduction sensitization in the above state and then further growing.

For reduction sensitization preferably used in the present invention, a method of adding a known reducing agent to a silver halide emulsion,
A method of growing or ripening in an atmosphere of low pAg of pAg 1 to 7 called silver ripening, called high pH ripening
Methods of growing or ripening in a high pH atmosphere of pH 8 to 11 are known, and two or more methods can be used in combination. The method of adding a reduction sensitizer is a preferable method because the level of reduction sensitization can be finely adjusted.

Known reduction sensitizers are stannous salts, amines and polyamic acids, hydrazine derivatives, formamidinesulfinic acid, silane compounds and borane compounds. In the present invention, these known compounds can be selected and used. Two or more compounds can be used in combination. Stannous chloride, thiourea dioxide as reduction sensitizer,
Dimethylamine borane (US Pat. No. 5,389,510
Are preferred compounds. More preferably, it is thiourea dioxide. The addition amount of the reduction sensitizer is the addition amount needs to be selected depends on emulsion manufacturing conditions, per mol of silver halide 10 ^-7 to 1
A range of 0 ^-3 mol is suitable.

Ascorbic acid and its derivatives can also be used as the reduction sensitizer of the present invention. Ascorbic acid and its derivatives (hereinafter, “ascorbic acid compound”
That. The following can be mentioned as specific examples of ()). (A-1) L-ascorbic acid (A-2) Sodium L-ascorbate (A-3) Potassium L-ascorbate (A-4) DL-ascorbic acid (A-5) D-sodium ascorbate (A -6) L-ascorbic acid-6-acetate (A-7) L-ascorbic acid-6-palmitate (A-8) L-ascorbic acid-6-benzoate (A-9) L-ascorbic acid-5,6 -Diacetate (A-10) L-ascorbic acid-5,6-O-isopropylidene

The ascorbic acid compound used in the present invention is preferably used in a large amount as compared with the addition amount in which a reduction sensitizer is conventionally used. For example,
No. 33572, "The amount of reducing agent usually does not exceed 0.75 × 10 ^-2 milliequivalent (8 × 10 ^-4 mol / AgX mol) per g of silver ion. Amount of 0.1-10 mg per kg of silver nitrate. (As ascorbic acid, 10 ^-7 to 10 ^-5 mol / AgX mol)
Is often effective. (The converted value is based on the inventors). U.S. Pat. No. 2,487,850
In the publication, "the addition amount of the tin compound that can be used as the reduction sensitizer is 1 × 10 ^{-7 to} 44 × 10 ^-6 mol" is described. Further, in JP-A-57-179835, the addition amount of thiourea dioxide is about 0.1 per mol of silver halide.
01 mg to about 2 mg, as stannous chloride about 0.01 mg to about 3 mg
Is said to be suitable. Ascorbic acid compound used in the present invention the particle size of the emulsion, the halogen composition, the temperature of emulsion preparation, pH, depends preferably amount by factors such as pAg, per mole of silver halide 5 × 10 ^-5 to 1 It is desirable to select from the range of × 10 ^-1 mol. More preferably 5 × 10 ⁻⁴ mol to 1 × 10
It is preferable to select from the range of ^-2 mol. It is particularly preferable to select from the range of 1 × 10 ⁻³ mol to 1 × 10 ⁻² mol. Among the reduction sensitizers, thiourea dioxide is particularly preferable.

The reduction sensitizer can be dissolved in water or a solvent such as alcohols, glycols, ketones, esters and amides and added during grain formation, before or after chemical sensitization. The compound may be added during any step of the emulsion production process, but a particularly preferable method is to add the compound during grain growth. It may be added to the reaction vessel in advance, but it is more preferable to add it at an appropriate time during particle formation. Alternatively, a reduction sensitizer may be added to an aqueous solution of a water-soluble silver salt or a water-soluble alkali halide in advance, and particles may be formed using these aqueous solutions. It is also a preferred method to add the solution of the reduction sensitizer in several portions as the grains are formed, or to add the solution continuously for a long time.

It is preferable to use an oxidizing agent for silver during the production process of the emulsion of the present invention. The oxidizing agent for silver is
It refers to a compound that acts on metallic silver to convert it into silver ions. In particular, the extremely fine silver particles produced as a by-product in the process of forming silver halide grains and the chemical sensitization process,
Compounds that can be converted to silver ions are effective. The silver ions generated here may form a poorly soluble silver salt such as silver halide, silver sulfide and silver selenide, or may form a readily soluble silver salt such as silver nitrate. Is also good. The oxidizing agent for silver may be an inorganic substance or an organic substance. Examples of the inorganic oxidant include ozone, hydrogen peroxide and its adducts (for example, NaBO ₂ · H ₂ O ₂ · 3H ₂ O, 2Na ₂ CO ₃ · 3H ₂ O ₂ and Na ₄ P
₂ O ₇・ 2H ₂ O ₂ , 2Na ₂ SO ₄・ H ₂ O ₂・ 2H ₂ O), peroxy acid salt (for example, K ₂ S ₂ O ₈ , K ₂ C ₂ O ₆ , K ₂ P ₂ O ₈ ), A peroxy complex compound (for example, K ₂ (Ti (O ₂ ) C ₂ O ₄ ) .3H ₂ O, 4K ₂ SO ₄ .Ti
(O ₂ ) OH ・ SO ₄・ 2H ₂ O, Na ₃ (VO (O ₂ ) (C ₂ H ₄ ) ₂・ 6H ₂ O}, permanganate (eg, KMnO ₄ ), chromate (eg, ,
K ₂ Cr ₂ O ₇ ) and other oxyacid salts, iodine and bromine and other halogen elements, perhalogenates (eg potassium periodate),
High-valent metal salts (eg, potassium hexacyanoferrate) and thiosulfonates. Also,
Examples of organic oxidants include quinones such as p-quinone, organic peroxides such as peracetic acid and perbenzoic acid, and compounds that release active halogen (for example, N-bromosuccinimide,
Chloramine T, chloramine B) are mentioned as examples.
As a more preferable oxidizing agent, the disulfide compound described in EP06267657A2 is used.

Preferred oxidizing agents of the present invention include ozone, hydrogen peroxide and its adducts, halogen elements, inorganic oxides of thiosulfonates, and organic oxidizing agents of quinones. It is a preferable embodiment to use the reduction sensitization and the oxidizing agent for silver in combination. The method can be selected from the method of performing reduction sensitization after using an oxidizing agent, the reverse method, or the method of coexisting both methods. These methods can be selectively used in both the grain formation step and the chemical sensitization step. The silver halide photographic light-sensitive material of the present invention preferably has the following general formula (XX) or (XX
It contains at least one compound selected from the compounds represented by I) or (XXII). General formula (XX) R ₁₀₁ -SO ₂ SM ₁₀₁ General formula (XXI) R ₁₀₁ -SO ₂ SR ₁₀₂ General formula (XXII) R ₁₀₁ -SO ₂ S- (E) _a -SSO ₂ -R ₁₀₃ where R ₁₀₁ , R ₁₀₂ and R ₁₀₃ represent an alkyl group, an aryl group or a heterocyclic group; M ₁₀₁ represents a cation;
Represents a divalent linking group, and a is 0 or 1.

The compounds of the general formula (XX), (XXI) or (XXII) will be described in more detail. R ₁₀₁ , R ₁₀₂ and R ₁₀₃
When is an aliphatic group, it is preferably an alkyl group having 1 to 22 carbon atoms, an alkenyl group having 2 to 22 carbon atoms, or an alkynyl group, which may have a substituent.
Examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, 2-ethylhexyl, decyl, dodecyl, hexadecyl, octadecyl, cyclohexyl, isopropyl and t-butyl. Examples of the alkenyl group include allyl and butenyl. Examples of the alkynyl group include propargyl and butynyl. The aromatic group for R ₁₀₁ , R ₁₀₂ , and R ₁₀₃ preferably has 6 to 20 carbon atoms, and examples thereof include a phenyl group and a naphthyl group. These may be substituted.

The heterocyclic group of R ₁₀₁ , R ₁₀₂ , and R ₁₀₃ is a 3- to 15-membered ring having at least one element selected from nitrogen, oxygen, sulfur, selenium, and tellurium, for example, a pyrrolidine ring, Piperidine ring, pyridine ring, tetrahydrofuran ring, thiophene ring, oxazole ring, thiazole ring, imidazole ring, benzothiazole ring, benzoxazole ring, benzimidazole ring,
Examples thereof include selenazole ring, benzoselenazole ring, tellurazole ring, triazole ring, benzotriazole ring, tetrazole ring, oxadiazole ring and thiadiazole ring.

Substituents for R ₁₀₁ , R ₁₀₂ , and R ₁₀₃ include, for example, alkyl groups (eg, methyl, ethyl, hexyl), alkoxy groups (eg, methoxy, ethoxy,
Octyloxy), aryl groups (phenyl, naphthyl,
Tolyl), hydroxy group, halogen atom (eg fluorine, chlorine, bromine, iodine), aryloxy group (eg phenoxy), alkylthio group (eg methylthio, butylthio), arylthio group (eg phenylthio), acyl group (eg acetyl, propionyl, Butyryl, valeryl), sulfonyl group (eg methylsulfonyl, phenylsulfonyl), acylamino group (eg acetylamino, benzamino), sulfonylamino group (eg methanesulfonylamino, benzenesulfonylamino),
Examples thereof include an acyloxy group (eg acetoxy, benzoxy), a carboxyl group, a cyano group, a sulfo group, an amino group and the like. E is preferably a divalent aliphatic group or a divalent aromatic group. Examples of the divalent aliphatic group of E include-(C
H ₂ ) _n- (n = 1 to 12), -CH ₂ -CH = CH-CH _2- ,

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Examples thereof include a xylylene group. Examples of the divalent aromatic group of E include phenylene and naphthylene. These substituents may be further substituted with the substituents such as V _{1 to} V ₄ described above. M
₁₀₁ is preferably a metal ion or an organic cation. Examples of the metal ion include a lithium ion, a sodium ion, and a potassium ion. As the organic cation, ammonium ions (for example, ammonium,
Examples thereof include tetramethylammonium, tetrabutylammonium), phosphonium ions (tetraphenylphosphonium), and guanidine groups.

Specific examples of the compounds represented by formula (XX), (XXI) or (XXII) are shown below, but the invention is not limited thereto.

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The compound of the general formula (XX) is described in JP-A-54-1.
It can be easily synthesized by the method described in 019 and British Patent No. 972,211. The compound represented by formula (XX), (XXI) or (XXII) is preferably added in an amount of 10 ^-7 to 10 ^-1 mol per mol of silver halide. Further, the addition amount of 10 ⁻⁶ to 10 ⁻² mol, particularly 10 ⁻⁵ to 10 ⁻³ mol is preferable. The addition of the compound represented by the general formula (XX), (XXI) or (XXII) during the production process can be applied by a method usually used when adding an additive to a photographic emulsion. For example, a water-soluble compound is made into an aqueous solution having an appropriate concentration, and a water-insoluble or sparingly-soluble compound is a suitable organic solvent miscible with water, such as alcohols, glycols, ketones, esters, amides, etc. At home,
It can be added as a solution by dissolving it in a solvent that does not adversely affect the photographic characteristics.

The compound represented by the general formula (XX), (XXI) or (XXII) may be added at any stage during grain formation of the silver halide emulsion, before or after chemical sensitization. . Preferred is a method in which a compound is added before or during reduction sensitization. Particularly preferred is a method of adding during the grain growth. It may be added to the reaction vessel in advance, but it is more preferable to add it at an appropriate time during particle formation. Alternatively, the compound of the general formula (XX), (XXI), or (XXII) may be added in advance to an aqueous solution of a water-soluble silver salt or a water-soluble alkali halide, and particles may be formed using these aqueous solutions. It is also a preferable method to add the solution of the compound of the general formula (XX), (XXI), or (XXII) in several batches or continuously for a long time as the particles are formed. General formula (XX), (X
Among the compounds represented by XI) or (XXII), the most preferable compound for the present invention is the compound represented by the general formula (XX).

The light-sensitive material of the present invention is not particularly limited, and examples thereof include a color negative, a color positive, a white / black sensitive material, a movie negative, and a movie positive. That is, at least one photosensitive layer may be provided on the support. A typical example is a silver halide photographic light-sensitive material having at least one light-sensitive layer comprising a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities on a support. It is. The photosensitive layer is a unit photosensitive layer having color sensitivity to any of blue light, green light, and red light, and in a multilayer silver halide color photographic material, the arrangement of the unit photosensitive layers is generally A red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer are provided in this order from the support side.
However, depending on the purpose, the order of installation may be reversed, or the order of installation may be such that different photosensitive layers are sandwiched between layers of the same color sensitivity. A non-light-sensitive layer may be provided between the silver halide light-sensitive layers and as the uppermost layer and the lowermost layer. These may contain a coupler, a DIR compound, a color mixing inhibitor, etc. described later. A plurality of silver halide emulsion layers constituting each unit photosensitive layer is DE 1,121,470 or GB923,
As described in 045, it is preferable to arrange two layers, a high-speed emulsion layer and a low-speed emulsion layer, so that the photosensitivity becomes lower toward the support. In addition, JP-A-57-112751,
As described in 62-200350, 62-206541 and 62-206543, a low-sensitivity emulsion layer may be provided on the side farther from the support and a high-sensitivity emulsion layer may be provided on the side closer to the support.

As a specific example, from the side farthest from the support,
Low sensitivity blue photosensitive layer (BL) / High sensitivity blue photosensitive layer (BH) / High sensitivity green photosensitive layer (GH) / Low sensitivity green photosensitive layer (GL) / High sensitivity red photosensitive layer (RH) / Low sensitivity red photosensitive layer (RL) order, or BH / BL / GL / GH / RH / RL order, or BH / BL / GH /
They can be installed in the order of GL / RL / RH. Also Tokunoaki
As described in JP-A-55-34932, the blue-sensitive layer / GH / RH / GL / RL may be arranged in this order from the side farthest from the support. Further, as described in JP-A-56-25738 and JP-A-62-63936, blue-sensitive layers / GL / RL / GH / RH may be arranged in this order from the side farthest from the support. Further, as described in JP-B-49-15495, the upper layer is the silver halide emulsion layer having the highest sensitivity, the middle layer is the silver halide emulsion layer having a lower sensitivity, and the lower layer is a silver halide emulsion layer having a higher sensitivity than the middle layer. An example is an arrangement in which low silver halide emulsion layers are arranged and three layers having different sensitivities are sequentially lowered toward the support. Even when it is composed of such three layers having different sensitivities, as described in JP-A-59-202464, in the same color-sensitive layer, the medium-sensitivity emulsion layer / high-sensitivity layer is separated from the side distant from the support. You may arrange in order of a speed emulsion layer / a low speed emulsion layer. In addition, the layers may be arranged in the order of high-speed emulsion layer / low-speed emulsion layer / medium-speed emulsion layer, or low-speed emulsion layer / medium-speed emulsion layer / high-speed emulsion layer. The arrangement may be changed as described above even in the case of four or more layers. U.S. Patent (US) 4,66 to improve color reproduction
3,271, 4,705,744, 4,707,436, JP 62-16044
8, Donor layer (CL) with a multilayer effect, which has a spectral sensitivity distribution different from that of the main photosensitive layers such as BL, GL and RL described in the specification of 63-89850.
Is preferably disposed adjacent to or close to the main photosensitive layer.

The preferred silver halide for use in the present invention is silver iodobromide, silver iodochloride, or silver iodochlorobromide containing about 30 mol% or less of silver iodide. Particularly preferred is silver iodobromide or silver iodochlorobromide containing from about 2 mol% to about 10 mol% silver iodide. Silver halide grains in photographic emulsions include those having regular crystals such as cubic, octahedral and tetradecahedral, those having irregular crystal forms such as spheres and plates, twin planes, etc. Or a composite form thereof. The silver halide may be fine grains having a grain size of about 0.2 μm or less or large grains having a projected area diameter of about 10 μm, and may be a polydisperse emulsion or a monodisperse emulsion. The silver halide photographic emulsion that can be used in the present invention is described, for example, in Research Disclosure (hereinafter abbreviated as RD) No. 17643 (December 1978).
Mon., pp. 22-23, "I. Emulsion preparati
on and types) ", and No. 18716 (November 1979), 6
Page 48, ibid.No. 307105 (November 1989), pages 863-865,
And Graphide, "Physics and Chemistry of Photography," published by Paul Montel (P. Glafkides, Chemie et PhisiquePhotogra.
Phique, Paul Montel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (GF Duffin. Photog.
raphic Emulsion Chemistry, Focal Press, 1966), "Production and Coating of Photographic Emulsions" by Zelikman et al., published by Focal Press (VL Zelikman, et al., Making and Coati
ng Photographic Emulsion, Focal Press, 1964) and the like.

Monodisperse emulsions described in US Pat. Nos. 3,574,628, 3,655,394 and British Patent (GB) 1,413,748 are also preferred.
Tabular grains having an aspect ratio of about 3 or more can also be used in the present invention. Tabular grains are described in Gutoff, Photographic Science and Engineering.
Vol. 14, pp. 248-257 (1970); US 4,434,226, ibid.
4,414,310, 4,433,048, 4,439,520 and GB 2,1
It can be easily prepared by the method described in 12,157. The crystal structure may be uniform, the inside and the outside may be composed of different halogen compositions, or may have a layered structure. Silver halides having different compositions may be joined by epitaxial joining, or may be joined to a compound other than silver halide, such as, for example, silver rhodanate or lead oxide. Also, a mixture of particles of various crystal forms may be used. The above emulsion may be either a surface latent image type in which a latent image is mainly formed on the surface, an internal latent image type in which the latent image is formed inside the grains, or a type having a latent image on both the surface and the inside. It is necessary to be. Among the internal latent image type emulsions, core / shell type internal latent image type emulsions described in JP-A-63-264740 may be used, and the preparation method thereof is described in JP-A-59-1.
33542. Although the thickness of the shell of this emulsion varies depending on the development process and the like, it is preferably 3 to 40 nm, and 5
-20 nm is particularly preferred.

As the silver halide emulsion, usually, those subjected to physical ripening, chemical ripening and spectral sensitization are used. Additives used in such a process are RD No. 17643 and RD No. 17643.
18716 and No. 307105, and the relevant parts are summarized in the table below. The light-sensitive material of the present invention includes a light-sensitive silver halide emulsion having a grain size, a grain size distribution,
Two or more kinds of emulsions having different characteristics of at least one of halogen composition, grain shape, and sensitivity can be mixed and used in the same layer. US Pat. No. 4,082,553, the surface of which is covered with a silver halide grain, US Pat.
It is preferable to apply the internally fogged silver halide grains and colloidal silver described in -214852 to the photosensitive silver halide emulsion layer and / or the substantially non-photosensitive hydrophilic colloid layer. The fogged silver halide grain inside or on the surface means a silver halide grain which enables uniform (non-imagewise) development regardless of the unexposed area and exposed area of the light-sensitive material. , Its preparation method is described in US 4,626,498 and JP-A-59-214852. The silver halide forming the internal nucleus of the core / shell type silver halide grain having the inside of the grain fogged may have a different halogen composition. As the silver halide having the inside or surface of the grain fogged, any of silver chloride, silver chlorobromide, silver iodobromide and silver chloroiodobromide can be used. The average grain size of these fogged silver halide grains is 0.01 to 0.75.
.mu.m, especially 0.05 to 0.6 .mu.m is preferred. The grain shape may be regular grain or polydisperse emulsion, but monodispersity (at least 95% of the weight or number of silver halide grains has a grain size within ± 40% of the average grain size). It is preferable that

In the present invention, it is preferable to use non-light-sensitive fine grain silver halide. Non-photosensitive fine grain silver halide is silver halide fine grains that are not exposed during imagewise exposure to obtain a dye image and are not substantially developed in the developing process, and are preferably not fogged in advance. . The fine grain silver halide has a silver bromide content of 0 to 100 mol%, and may contain silver chloride and / or silver iodide as needed. Preferably, it contains 0.5 to 10 mol% of silver iodide. The fine grain silver halide preferably has an average grain size (average diameter of circles equivalent to the projected area) of 0.01 to 0.5 μm, and 0.02 to 0.2 μm.
Is more preferred. Fine grain silver halide can be prepared by the same method as that for ordinary photosensitive silver halide. The surface of the silver halide grains does not need to be optically sensitized, and no spectral sensitization is required. However, prior to adding this to the coating solution, it is preferable to add a known stabilizer such as a triazole-based, azaindene-based, benzodiazolium-based, mercapto-based compound or zinc compound in advance. Colloidal silver can be contained in the layer containing fine silver halide grains. The silver coating amount of the light-sensitive material of the present invention is preferably 6.0 g / m ² or less, and 4.5 or less.
Most preferred is g / m ² or less.

The photographic additives that can be used in the present invention are also described in the RD, and the relevant portions are shown in the following table.

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[Table 1]

Although various dye-forming couplers can be used in the light-sensitive material of the present invention, the following couplers are particularly preferable. Yellow couplers: couplers represented by formulas (I) and (II) of EP 502,424A; couplers represented by formulas (1) and (2) of EP 513,496A (particularly Y-28 on page 18); EP 568,037A A coupler represented by the formula (I) of claim 1; a coupler represented by the general formula (I) in columns 45 to 55 of column 1, US 5,066,576; represented by the general formula (I) in paragraph 0008 of JP-A-4-274425. Coupler; coupler described in claim 1 of EP 498,381A1 on page 40 (especially D-35 on page 18); coupler represented by formula (Y) on page 4 of EP 447,969A1 (especially Y-1 (page 17), Y-54 (41
)); US 4,476,219, column 7, lines 36-58, formulas (II)-(I
V) couplers (especially II-17, 19 (column 1
7), II-24 (column 19)). Magenta coupler: JP-A-3-39737 (L-57 (page 11, lower right),
L-68 (bottom right of page 12), L-77 (bottom right of page 13); [A-4] -63 (page 134), [A-4] -73, -75 (page 139) of EP 456,257; E
P 486,965, M-4, -6 (p. 26), M-7 (p. 27); EP 571,95
9A, M-45 (page 19); JP-A-5-204106, (M-1) (page 6); JP-A-4-362631, paragraph 0237, M-22. Cyan coupler: CX-1, 3, 4, 5 of JP-A-4-204843,
11, 12, 14, 15 (pages 14 to 16); JP-A-4-43345, C-7,
10 (page 35), 34, 35 (page 37), (I-1), (I-17) (42 to 43)
Page); a coupler represented by formula (Ia) or (Ib) of claim 1 of JP-A-6-67385. Polymer coupler: P-1 and P-5 of JP-A-2-44345 (page 11)
.

Examples of couplers in which the color forming dye has an appropriate diffusibility include US 4,366,237, GB 2,125,570, EP 96,873B,
Those described in DE 3,234,533 are preferred. The coupler for correcting the unnecessary absorption of the coloring dye is a yellow color cyan dye represented by the formulas (CI), (CII), (CIII) and (CIV) described on page 5 of EP 456,257A1 (especially on page 84). YC-8
6), the yellow colored magenta coupler Ex described in the EP
M-7 (page 202), EX-1 (page 249), EX-7 (page 251), US
Magenta colored cyan coupler CC described in 4,833,069
-9 (column 8), CC-13 (column 10), US 4,837,136
(2) (column 8), a colorless masking coupler represented by the formula (A) in claim 1 of WO92 / 11575 (especially the exemplified compounds on pages 36 to 45) are preferred. Examples of the compound (including a coupler) which releases a photographically useful compound residue by reacting with an oxidized developing agent include the following. Development inhibitor-releasing compounds: Formulas (I), (II), described in EP 378,236A1, page 11
(III), a compound represented by (IV) (especially T-101 (page 30)),
T-104 (page 31), T-113 (page 36), T-131 (page 45), T-144 (51
Page), T-158 (page 58)), and the formula described on page 7 of EP 436,938A2.
Compounds represented by (I) (especially D-49 (page 51)), EP 568,0
Compounds represented by formula (I) of 37A (particularly (23) (page 11)),
Formulas (I), (II) and (III) described on pages 5 and 6 of EP 440,195A2
A compound represented by formula (I- (1) on page 29); a bleaching accelerator releasing compound: a compound represented by formula (I) or (I ') on page 5 of EP 310,125A2 (particularly (60) on page 61) , (61)) and a compound represented by the formula (I) of claim 1 of JP-A-6-59411 (particularly (7) (page 7); a ligand-releasing compound: LIG-X described in claim 1 of US Pat. No. 4,555,478. Compounds represented (especially compounds in columns 12, lines 21-41); Leuco dye releasing compounds:
Compounds 1-6 of columns 3-8 of US 4,749,641; Fluorophore releasing compounds: compounds represented by COUP-DYE of claim 1 of US 4,774,181 (especially compounds 1-11 of column 7-10);
Development accelerator or fogging agent releasing compound: Compounds represented by the formulas (1), (2) and (3) of column 3, US Pat. No. 4,656,123 (particularly (I-22) of column 25) and EP 450, 637 A2, p. 75 36 ExZK-2 on line -38; compounds that release a dye group for the first time after leaving; compounds represented by formula (I) of claim 1 of US Pat. No. 4,857,447 (especially Y-1 to Y-19 in columns 25 to 36) ).

The following additives are preferable as additives other than the coupler. Dispersion medium of oil-soluble organic compound: P-3 in JP-A-62-215272,
5, 16, 19, 25, 30, 42, 49, 54, 55, 66, 81, 85, 8
6, 93 (pages 140 to 144); Latex for impregnation of oil-soluble organic compounds: Latex described in US 4,199,363; Oxidizing agent scavenger: US 4,978,606, column 2, 54 to 62.
Compounds represented by formula (I) in the row (especially I-, (1), (2),
(6), (12) (columns 4-5), column 2, US 4,923,787
5-10 lines (especially compound 1 (column 3); stain inhibitor: EP 298321A, page 4, lines 30-33 formulas (I)-(III),
Especially I-47, 72, III-1, 27, (pages 24-48); Anti-fading agent: EP298321A, A-6, 7, 20, 21, 23, 24, 25, 26, 3
0, 37, 40, 42, 48, 63, 90, 92, 94, 164 (pages 69 to 118)
, US 5,122,444 columns 25-38 II-1 to III-23, especially I
II-10, EP 471347A, pages 1-12, I-1 to III-4, especially II-
2, US 5,139,931 columns 32-40 A-1 to 48, especially A-3
9, 42; Materials that reduce the amount of color-enhancing agent or color-mixing inhibitor used: I-1 to II-15 on pages 5 to 24 of EP 411324A, especially
I-46; Formalin Scavenger: 24 of EP 477932A
SCV-1 to 28 on page 29, especially SCV-8; Hardener: JP-A 1-21
4845, page 17, H-1, 4, 6, 8, 14, US 4,618,573, columns 13 to 23, compounds represented by formulas (VII) to (XII) (H-
1 to 54), compounds represented by the formula (6) at the lower right of page 8 of JP-A-2-214852 (H-1 to 76), particularly H-14, the compound described in claim 1 of US 3,325,287; Agent precursor: P-24, 37, 39 of JP-A-62-168139 (pages 6 to 7); US 5,019,4
Compound as claimed in claim 1 of 92, especially column 7, 28, 2
9; Antiseptic, antifungal agent: US 4,923,790 column 3 to 15 I-1
~ III-43, especially II-1, 9, 10, 18, III-25; stabilizers,
Antifoggant: US 4,923,793, columns 6-16, I-1 ~
(14), in particular I-1, 60, (2), (13), compounds 1 to 65 in columns 25 to 32 of US 4,952,483, especially 36: chemical sensitizer: triphenylphosphine selenide, JP-A-5-40324. Compound 50; dyes: a-1 to b-2 on pages 15 to 18 of JP-A-3-156450
0, especially a-1, 12, 18, 27, 35, 36, b-5, V on pages 27-29
-1 to 23, especially V-1, FI-1 to F on pages 33 to 55 of EP 445627A
-II-43, in particular FI-11, F-II-8, EP 457153A, pages 17-28 III-1 to 36, especially III-1, 3, WO 88/04794 8-26.
Dye-1 to 124 microcrystalline dispersions, compounds 31 to 22 on page 6 to 11 of EP 319999A, particularly compound 1, compounds D-1 to 87 () represented by formulas (1) to (3) of EP 519306A. 3 to 28), US
Compounds 1 to 22 (columns 3 to 10) represented by formula (I) of 4,268,622, compounds represented by formula (I) of US 4,923,788
(1) to (31) (columns 2 to 9); UV absorber: JP-A-46-333
Compounds (18b) to (18r) represented by formula (I) of 5 and 101 to
427 (pages 6 to 9), compounds (3) to (66) (pages 10 to 44) represented by formula (I) of EP 520938A and compounds HBT-1 to 10 (page 14) represented by formula (III). , Compounds (1) to (31) represented by the formula (1) of EP 521823A (columns 2 to 9).

Suitable supports that can be used in the present invention are, for example, those described in RD. No. 17643, page 28, No. 18716, 64
Right column from page 7 to left column on page 648, and 879 of the same No. 307105
Page. In the light-sensitive material of the present invention, the total thickness of all hydrophilic colloid layers on the emulsion layer side is preferably 28 μm or less, more preferably 23 μm or less, further preferably 18 μm or less, particularly preferably 16 μm or less. Further, the film swelling speed T _1/2 is preferably 30 seconds or less, and more preferably 20 seconds or less. T _1/2 is the time until the film thickness reaches 1/2 when 90% of the maximum swollen film thickness reached when the film is processed with a color developer at 30 ° C. for 3 minutes and 15 seconds is a saturated film thickness. It is defined as The film thickness means a film thickness measured under a humidity condition of 25 ° C. and a relative humidity of 55% (2 days), and T _1/2
Is a member of A. Green et al.'S Photographic Science and Engineering (Photogr.
Sci. Eng.), Vol. 19, pages 2, 124-129. T _1/2 can be adjusted by adding a hardening agent to gelatin as a binder or changing the aging condition after coating. In addition, the swelling ratio is 150 ~
400% is preferred. The swelling ratio is calculated from the maximum swelling film thickness under the conditions described above by the formula: (maximum swelling film thickness−film thickness) /
It can be calculated by the film thickness. The light-sensitive material of the present invention has a total dry film thickness of 2 μm to 20 μm on the side opposite to the side having the emulsion layer.
It is preferable to provide a hydrophilic colloid layer (referred to as a back layer). The back layer preferably contains the above-mentioned light absorber, filter dye, ultraviolet absorber, antistatic agent, hardener, binder, plasticizer, lubricant, coating aid, and surfactant. The swelling ratio of the back layer is preferably from 150 to 500%.

The light-sensitive material of the present invention is the same as RD. No. 17
Development can be carried out by a usual method described on pages 28 to 29 of 643, page 651, left column to right column of No. 18716, and pages 880 to 881 of No. 307105. The color developing solution used in the development of the light-sensitive material of the present invention is preferably an alkaline aqueous solution mainly containing an aromatic primary amine color developing agent. Although aminophenol compounds are also useful as the color developing agent, p-phenylenediamine compounds are preferably used. Typical examples and preferred examples thereof are the compounds described on page 28, lines 43 to 52 of EP 556700A. Is mentioned. These compounds can be used in combination of two or more depending on the purpose. The color developing solution may be a pH buffer such as an alkali metal carbonate, borate or phosphate, a chloride salt, a bromide salt, an iodide salt, a benzimidazole, a benzothiazole or a mercapto compound. It generally contains an inhibitor or an antifoggant. If necessary, hydroxylamine,
Diethylhydroxylamine, sulfite, hydrazines such as N, N-biscarboxymethylhydrazine, various preservatives such as phenylsemicarbazides, triethanolamine and catechol sulfonic acids, organic solvents such as ethylene glycol and diethylene glycol, benzyl alcohol , Polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, competing couplers, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, tackifiers, amino polycarboxylic acids, amino poly Various chelating agents represented by phosphonic acid, alkylphosphonic acid and phosphonocarboxylic acid, for example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyl Iminodiacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilo -N, N,
N-trimethylene phosphonic acid, ethylenediamine-N,
Add N, N, N-tetramethylenephosphonic acid, ethylenediamine-di (o-hydroxyphenylacetic acid) and salts thereof.

When the reversal process is carried out, black and white development is usually carried out and then color development is carried out. A known black-and-white developing agent such as dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone or aminophenols such as N-methyl-p-aminophenol is used alone in the black-and-white developer. Alternatively, they can be used in combination. The pH of these color developing solution and black-and-white developing solution is generally 9 to 12.
The replenishment amount of these developing solutions depends on the color photographic light-sensitive material to be processed, but is generally 3 liters or less per square meter of the light-sensitive material. You can also. When the replenishment rate is reduced, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the contact area of the processing tank with the air. The processing effect of the contact between the photographic processing liquid and air in the processing tank can be evaluated by the aperture ratio (= [contact area between processing liquid and air cm ² ] / [volume of processing liquid cm ³ ]). The aperture ratio is preferably 0.1 or less, and more preferably 0.001 to 0.05. As a method of reducing the aperture ratio, in addition to providing a cover such as a floating lid on the photographic processing liquid surface of the processing tank, a method using a movable lid described in JP-A-1-82033 and JP-A-63-216050 are disclosed. The slit development processing method described can be mentioned.
The aperture ratio is not limited to both color development and black and white development,
Subsequent steps such as bleaching, bleach-fixing, fixing, washing,
It is preferable to reduce it in all steps such as stabilization. Further, the amount of replenishment can be reduced by using a means for suppressing the volume of bromide ion in the developer. The time for the color development processing is usually set between 2 and 5 minutes, but the processing time can be further reduced by using a high temperature, a high pH and using a high concentration of the color developing agent.

The photographic emulsion layer of the color developing solution is usually bleached. The bleaching process may be performed simultaneously with the fixing process (bleach-fixing process), or may be performed individually. In order to further speed up the processing, a processing method of performing bleach-fixing after bleaching may be used. Further, processing in two successive bleach-fixing baths, fixing before bleach-fixing, or bleaching after bleach-fixing can be arbitrarily performed according to the purpose. As the bleaching agent, for example, compounds of polyvalent metals such as iron (III), peracids, quinones, nitro compounds and the like are used. Typical bleaching agents are organic complex salts of iron (III),
For example, aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, and glycol ether diaminetetraacetic acid, or complex salts such as citric acid, tartaric acid, and malic acid. Etc. can be used. Of these, aminopolycarboxylic acid iron (III) complex salts including ethylenediaminetetraacetic acid iron (III) complex salts and 1,3-diaminopropanetetraacetic acid iron (III) complex salts are preferable from the viewpoint of rapid treatment and prevention of environmental pollution. . Further, the aminopolycarboxylic acid iron (III) complex salt is particularly useful in a bleaching solution and a bleach-fixing solution. The pH of a bleaching solution or a bleach-fixing solution using these aminopolycarboxylic acid iron (III) complex salts is usually 4.0 to 8, but a lower pH can be used for speeding up the processing.

In the bleaching solution, the bleach-fixing solution and the prebath thereof, a bleaching accelerator can be used if necessary.
Specific examples of useful bleaching accelerators are described in the following specifications: US 3,893,858, DE 1,290,812, 2,059,988, JP-A-53-32736, 53-57831, 53-37418, 53-72623. ,
53-95630, 53-95631, 53-104232, 53-12442
4, ibid 53-141623, ibid 53-28426, RD No. 17129 (1978
July)) having a mercapto group or a disulfide group; a thiazolidine derivative described in JP-A-50-140129; JP-B-45-8506, JP-A-52-20832, and JP-A-53-3273.
5, thiourea derivatives described in US 3,706,561; DE 1,127,71
5, iodide salts described in JP-A-58-16,235; DE 966,410,
Polyoxyethylene compounds described in JP-A-2,748,430; polyamine compounds described in JP-B-45-8836;
49-40,943, 49-59,644, 53-94,927, 54-35,72
7, the compounds described in 55-26,506 and 58-163,940; bromide ions can be used. Among them, compounds having a mercapto group or a disulfide group are preferable from the viewpoint of a large accelerating effect, and in particular, US 3,893,858, DE 1,290,812, JP-A-53-9.
The compounds described in 5,630 are preferred. In addition, US 4,552,834
The compounds described in 1 are also preferable. These bleaching accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when bleach-fixing a color photographic material for photography. The bleaching solution and the bleach-fixing solution preferably contain an organic acid in order to prevent bleaching stain in addition to the above compounds. Particularly preferred organic acid has an acid dissociation constant (pKa) of 2 to 5
Specifically, acetic acid, propionic acid, hydroxyacetic acid and the like are preferable.

Examples of the fixing agent used in the fixing solution and the bleach-fixing solution include thiosulfates, thiocyanates, thioether compounds, thioureas, and a large amount of iodide salts. Use of thiosulfates is preferred. It is common and in particular ammonium thiosulfate can be used most widely. It is also preferable to use a combination of a thiosulfate and a thiocyanate, a thioether-based compound, or thiourea. As a preservative for the fixing solution and the bleach-fixing solution, sulfites, bisulfites, carbonyl bisulfite adducts or sulfinic acid compounds described in EP 294769A are preferable. Furthermore, for the purpose of stabilizing the solution, it is preferable to add aminopolycarboxylic acids or organic phosphonic acids to the fixing solution or the bleach-fixing solution. In the present invention, the fixer or the bleach-fixer contains a compound having a pKa of 6.0 to 9.0 for pH adjustment,
Preferably, imidazole, 1-methylimidazole,
It is preferable to add 0.1-10 mol of imidazole such as 1-ethylimidazole and 2-methylimidazole per liter.

The total time of the desilvering process is preferably as short as possible so long as no desilvering failure occurs. Preferred time is 1 minute to 3
Minutes, more preferably 1 to 2 minutes. Further, the processing temperature is 25 ° C to 50 ° C, preferably 35 ° C to 45 ° C.
In a preferable temperature range, the desilvering speed is improved, and generation of stain after processing is effectively prevented. In the desilvering step, it is preferable that the stirring is strengthened as much as possible. As a specific method of strengthening stirring, see JP-A-62-183.
460, a method of impinging a jet of a processing solution on the emulsion surface of the light-sensitive material, a method of improving the stirring effect by using the rotating means of JP-A-62-183461, and a wiper blade and emulsion provided in the solution. Move the photosensitive material while contacting the surfaces,
Examples include a method of further improving the stirring effect by making the emulsion surface turbulent, and a method of increasing the circulation flow rate of the entire processing solution. Such a stirring improving means is effective for any of the bleaching solution, the bleach-fixing solution and the fixing solution. It is considered that the improvement of the stirring speeds up the supply of the bleaching agent and the fixing agent into the emulsion film, and consequently increases the desilvering speed. Further, the above-mentioned means for improving the stirring is more effective when a bleaching accelerator is used, and can significantly increase the accelerating effect or eliminate the fixing inhibiting effect of the bleaching accelerator. The automatic processor used for the light-sensitive material of the present invention is disclosed in JP-A-60-191257.
60-191258 and 60-191259. JP-A-60-191
As described in 257, such a transfer means can significantly reduce the carry-in of the processing solution from the front bath to the post-bath, and is highly effective in preventing the deterioration of the performance of the processing solution. It is particularly effective in reducing the liquid replenishment amount.

The light-sensitive material of the present invention is generally washed with water and / or stabilized after the desilvering process. The amount of rinsing water in the rinsing step depends on the characteristics of the photosensitive material (for example, the material used such as a coupler), the intended use, the rinsing water temperature, the number of rinsing tanks (number of stages), the replenishment method such as countercurrent, forward flow, and other various conditions. Can be set widely. Of these, the relationship between the number of washing tanks and the amount of water in the multi-stage countercurrent system is described in the Journal of t
he Society of MotionPicture and Television Enginee
rs, Vol. 64, pages 248-253 (May 1955). According to the multi-stage countercurrent method described in this document, the amount of washing water can be significantly reduced, but bacteria increase due to the increase in the residence time of water in the tank, and the generated suspended matter adheres to the photosensitive material. Problem arises. As a solution to this problem, the method of reducing calcium and magnesium ions described in JP-A-62-288,838 is extremely effective. Further, isothiazolone compounds and siabendazoles described in JP-A-57-8,542, chlorine-based germicides such as chlorinated sodium isocyanurate, and other benzotriazoles, Hiroshi Horiguchi, "Chemistry of antifungal agents"
(1986) Sankyo Publishing, Sanitary Technology Association, "Microbial Sterilization, Sterilization, and Antifungal Technology" (1982) Industrial Technology Association, Japan Society of Antimicrobial and Antifungal Activities, "Encyclopedia of Antimicrobial and Antifungal Agents" (1986) The bactericides described can also be used. The pH of the washing water in the processing of the light-sensitive material of the present invention is from 4 to 9, preferably from 5 to 8.
The washing water temperature and washing time can also be set depending on the characteristics of the light-sensitive material and the application, but generally 15 to 45 ° C. and 20 seconds to 10 seconds.
Minutes, preferably in the range of 30 seconds to 5 minutes at 25-40 ° C. Further, the light-sensitive material of the present invention can be processed directly with a stabilizing solution instead of the above-mentioned washing. In such stabilization treatment, JP-A-57-8543 and JP-A-58-148
The publicly known method described in 34, 60-220345 can be applied. Further, there is a case where further stabilization treatment is carried out after the water washing treatment, and an example thereof is a stabilizing bath containing a dye stabilizer and a surfactant used as a final bath of a color light-sensitive material for photographing. You can Aldehydes such as formalin and glutaraldehyde, N
Mention may be made of methylol compounds, hexamethylenetetramine or aldehyde sulfite adducts. Various chelating agents and fungicides can also be added to this stabilizing bath.

The overflow solution accompanying the above washing with water and / or supplementation of the stabilizing solution can be reused in other steps such as the desilvering step. In the processing using an automatic developing machine or the like, when each of the above processing solutions is concentrated by evaporation,
It is preferable to correct the concentration by adding water. The light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up the processing. In order to incorporate the color developing agent, it is preferable to use a precursor of a color developing agent. For example US 3,34
2,597 described indoaniline compounds, the same 3,342,599,
Research Disclosure No. 14,850 and No. 1
The Schiff base type compounds described in 5,159, the aldol compounds described in 13,924, the metal salt complexes described in US 3,719,492, and the urethane compounds described in JP-A-53-135628 can be mentioned. The light-sensitive material of the present invention may contain various 1-phenyl-3-pyrazolidones in order to accelerate color development, if necessary. A typical compound is JP-A-56-643.
39, 57-144547, and 58-115438. The processing liquid used for processing the light-sensitive material of the present invention is 10
Used at temperatures between 50 ° C and 50 ° C. Usually 33 ° C to 38 ° C
The temperature is standard, but it can be raised to a higher temperature to accelerate the processing and shorten the processing time, or to a lower temperature to improve the image quality and improve the stability of the processing solution.

The present invention can be preferably applied to a silver halide photographic light-sensitive material having a transparent magnetic recording layer. A silver halide photographic material carrying magnetic recording used in the present invention is disclosed in JP-A-6-
35118, a thin-layer support of a polyester which has been preliminarily heat-treated, for example, a polyethylene aromatic dicarboxylate-based polyester support described in JP-A-6-17528 and Hatsumei Kyokai Kokai Giho 94-6023.
300 μm, preferably 50 μm to 200 μm, more preferably 80 to 115 μm, particularly preferably 85 to 10
5 μm at a temperature above 40 ° C and below the glass transition temperature 1
Heat treated (annealed) for ~ 1500 hours,
603, JP-B-43-2604, JP-B-45-3828
UV irradiation, JP-B-48-5043, JP-A-51
-131576, etc., corona discharge, JP-B-35-7
No. 578, Japanese Patent Publication No. 46-43480, surface treatment such as glow discharge, undercoating described in US Pat. 23505, Japanese Patent Laid-Open No. 4-1
95726, ferromagnetic particles described in JP-A-6-59357 may be applied. The magnetic layer described above is disclosed in
126442 and a stripe shape described in JP-A-4-124645.

Furthermore, if necessary, Japanese Patent Application Laid-Open No. 4-62543.
, And finally coated with a silver halide emulsion. The silver halide emulsions used here are those disclosed in JP-A-4-166932, JP-A-3-41436, and JP-A-3-14336.
41437 is used. The sensitivity of the material is 4-8
Manufactured by the manufacturing control method described in 6817, Japanese Patent Publication No. 6-87
It is preferable to record the manufacturing data by the method described in 146. Thereafter or before that, Japanese Patent Application Laid-Open No. 4-125560.
According to the method described in (1), the film is cut to a width narrower than the conventional 135 size, and the perforations are perforated with 2 holes per side for the small format screen to match the smaller format screen.

The film thus produced is described in JP-A-4-15.
7459 cartridge package or JP-A-5-21020
The cartridge shown in FIG. 9 of the second embodiment, or US 4,2
21,479 film patrone and US4,834,
306, US 4,834,366, US 5,226,6
13. Used in a cartridge described in US Pat. No. 4,846,418. The film cartridge or film cartridge used here is US 4,848,693, US
5, 317, 355 are preferred from the viewpoint of light shielding properties. Furthermore, US 5,296,
Cartridge with lock mechanism like 886 or US
5, 347 and 334 are preferable, and a cartridge having a double exposure prevention function is preferable. Further, as described in JP-A-6-85128, a cartridge in which the film is easily mounted by simply inserting the film into the cartridge may be used.

The film cartridge thus manufactured can be used for the purpose of photographing, developing, and enjoying various photographs by using a camera, a developing machine, and a laboratory device described below.
For example, a simple loading camera described in JP-A-6-8886 and JP-A-6-99908, an automatic winding camera described in JP-A-6-57398 and JP-A-6-101135, and a photographing camera described in JP-A-6-205690 are disclosed. Camera that can take out and replace the type of film with
8. A camera capable of magnetically recording information on photographing, such as panoramic photographing, high-vision photographing, and normal photographing (magnetic recording with selectable print aspect ratio), as described in JP-A-5-283382, and JP-A-6-1011.
If the camera having the double exposure prevention function described in 94 or the camera having the use state display function of the film described in JP-A-5-150577 is used, the function of the film cartridge (patrone) can be sufficiently exhibited.

The film thus photographed is processed by the automatic developing machine described in JP-A-6-222514 and JP-A-6-222545, or before or during the processing or in JP-A-6-95265. The method of utilizing magnetic recording on a film described in JP-A-4-123054 may be used, or the aspect ratio selection function described in JP-A-5-19364 may be used. In the case of cine-type development during development processing,
And splicing according to the method described in -119461.
Further, when or after the development processing,
5. Attach and detach as described in 5. After processing in this manner, Japanese Patent Application Laid-Open Nos. 2-184835 and 4-1863.
35, the method described in JP-A-6-79968 may be used to convert film information into a print through back printing and front printing on color paper. Further, it may be returned to the customer together with the index print and return cartridge described in JP-A-5-11353 and JP-A-5-232594.

[0125]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. Example 1 (1) Preparation of Emulsion An aqueous solution prepared by dissolving 6 g of potassium bromide and 30 g of inactive gelatin having an average molecular weight of 15,000 in 3.7 liters of distilled water was stirred well, and an odor of 14% was obtained by the double jet method. Aqueous potassium iodide and 20% aqueous silver nitrate were added at a constant flow rate over 1 minute at 55 ° C. and pBr 1.0 (this addition consumed 2.4% of the total silver).

An aqueous gelatin solution (17%, 300 cc) was added, and after stirring at 55 ° C., a 20% aqueous silver nitrate solution was added at a constant flow rate until pBr reached 1.4 (this addition of 5. 0% consumed). Then, thiourea dioxide was added in an amount of 1.2 × 10 ^-5 mol per mol of silver, and further, 20% potassium iodobromide solution (KBr _1-x I _x : x = 0.04) and 33% silver nitrate aqueous solution were added. 4 by the double jet method
Added over 3 minutes (this addition consumed 50% of the total silver). After adding 2.5 × 10 ⁻⁴ mol of sodium ethylthiosulfonate per mol of silver, an aqueous solution containing 8.3 g of potassium iodide was added, and 0.001 / wt% K ₃ IrCl ₆ aqueous solution was added. 0.5 ml was added and 20% potassium bromide solution and 33% aqueous silver nitrate solution were added by the double jet method over 39 minutes (this addition consumed 42.6% of the total silver). The amount of silver nitrate used in this emulsion was 425 g. Then, after desalting by a usual flocculation method, the pAg was adjusted to 8.2 and the pH was adjusted to 5.8 at 40 ° C.
Average aspect ratio 6.5, coefficient of variation 18%, sphere equivalent diameter 0.
A tabular silver iodobromide emulsion (Em-1) having a size of 8 μm was prepared. Observation with a 200 kV transmission electron microscope at a liquid N ₂ temperature revealed that, on average, 50 or more dislocation lines per grain exist near the outer periphery of the tabular grain.

Emulsion Em-1 thus prepared is shown in Table 3.
After the addition of the sensitizing dyes shown in Table 3 in the amounts shown in Table 3, gold-selenium-sulfur sensitization was optimally performed using sodium thiosulfate, chloroauric acid, N, N-dimethylselenourea and potassium thiocyanate. To prepare emulsions 151 to 172. Further, the sensitizing dyes shown in Table 2 were added to the tabular silver iodobromide emulsion (Em-2) prepared from the above emulsion preparation except that the step of adding thiourea dioxide and sodium ethyl thiosulfonate was omitted. Emulsions 101 to 122 were prepared. Samples 1001 to 1072 were prepared by coating the emulsion layer and the protective layer on the triacetyl cellulose support provided with the undercoat layer in the coating amounts shown in Table 4.

[0128]

[Table 2]

[0129]

[Table 3]

[0130]

[Table 4]

[0131]

Embedded image

[0132]

Embedded image

These samples were subjected to sensitometric exposure for 1/100 seconds through a continuous wedge and a gelatin filter SC-50 manufactured by Fuji Photo Film Co., Ltd. at a color temperature of 4800 ° K, and the following color development processing was performed. The developing treatment used here was performed at 38 ° C. under the following conditions.

Treatment Method Process Treatment time Treatment temperature Replenishment amount Tank capacity Color development 2 minutes 45 seconds 38 ° C. 33 ml 20 liters Bleach 6 minutes 30 seconds 38 ° C. 25 ml 40 liters Water wash 2 minutes 10 seconds 24 ° C. 1200 ml 20 liters Fixing 4 minutes 20 seconds 38 ℃ 25 ml 30 liters Water wash (1) 1 minute 05 seconds 24 ℃ From (2) to (1) 10 liter countercurrent piping system Water wash (2) 1 minute 00 seconds 24 ℃ 1200 ml 10 liters Stable (3) 1 minute 05 Second 38 ℃ 25ml 10L Dry 4 minutes 20 seconds 55 ℃ Replenishment amount is 35mm width 1m per length

Next, the composition of the processing liquid will be described. (Color developer) Mother liquor (g) Replenisher (g) Diethylenetriaminepentaacetic acid 1.0 1.1 1-hydroxyethylidene-3.0 3.2 1,1-diphosphonic acid sodium sulfite 4.0 4.4 Potassium carbonate 30.0 37.0 Potassium bromide 1.4 0.7 Potassium iodide 1.5 mg Hydroxylamine sulphate 2.4 2.8 4- [N-Ethyl-N-β-4.5 5.5 Hydroxy Ethylamino] -2-methylaniline sulphate Add water 1.0 liters 1.0 liters pH 10.05 50.10 (bleaching solution) Mother liquor (g) Replenisher (g) Ethylenediaminetetraacetic acid second 100.0 120.0 Sodium iron trihydrate Diamine ethylenediaminetetraacetate 10.0 11.0 Thorium salt Ammonium bromide 140.0 160.0 Ammonium nitrate 30.0 35.0 Ammonia water (27%) 6.5ml 4.0ml Water Add 1.0 liters 1.0 liters pH 6.0 5.7

(Fixer) Mother liquor (g) Replenisher (g) Ethylenediaminetetraacetic acid 0.5 0.7 Sodium salt Sodium sulfite 7.0 8.0 Sodium bisulfite 5.0 5.5 Ammonium thiosulfate aqueous solution 170.0 ml 20 ml (70%) Add water 1.0 liter 1.0 liter pH 6.7 6.6 (Stabilizer) Mother liquor (g) Replenisher (g) Formalin (37%) 2.0 ml 3.0 ml Polyoxyethylene-p-mono 0.3 0.45 nonyl phenyl ether (average degree of polymerization: 10) ethylenediaminetetraacetic acid diamine 0.05 0.05 0.08 Sodium salt Water is added to 1.0 liters 1.0 liters pH 5.8 -8.0 5.8-8.0 The concentration of the treated sample was measured.

Regarding the sensitivity, the relative value of the reciprocal of the exposure amount required for the optical density to be higher than the fog by 0.2 was shown as the fresh sensitivity. Also, after exposing the unexposed film to a relative humidity of 60%, 60 ° C. for 3 days, the same exposure,
After development, sensitivity and fogging were evaluated in the same manner. The results thus obtained are shown in Tables 5 and 6. The sample number 1001 was used as the sensitivity standard (100).

[0138]

[Table 5]

[0139]

[Table 6]

As is clear from Tables 5 and 6, the o of the present invention
It can be seen that the dye having a -sulfoaralkyl group is remarkably high in reduction sensitized emulsion, has less fog, and is excellent in storage stability. This will be described in more detail. In the unreduced sensitized emulsions of Table 5, the dyes having the o-sulfoaralkyl group of the present invention and the dyes having the comparative sulfoalkyl group or p-sulfobenzyl group have the same sensitivity and storage stability, In the reduction sensitized emulsions shown in Table 6, surprisingly, the dye of the present invention is specifically high in sensitivity, less fog and good in storage stability. Further, among the o-sulfoaralkyl groups of the present invention, it is preferable that the number of methylene groups is 4, 2 and 1 in that order (Sample No. 1052 → 1053 → 105).
4), and an unsubstituted o-sulfobenzyl group is preferable (Sample No. 1065 → 1066).

Example 2 On a subbed cellulose triacetate film support,
Each layer having the composition shown below was applied in multiple layers to prepare a multilayer color light-sensitive material. (Photosensitive layer composition) The main materials used for each layer are classified as follows: ExC: Cyan coupler UV: UV absorber ExM: Magenta coupler HBS: High boiling organic solvent ExY: Yellow coupler H: Gelatin Hardener ExS: Sensitizing dye The numbers corresponding to the respective components indicate the coating amount expressed in g / m ² unit, and for silver halide, the coating amount in terms of silver. However, for the sensitizing dye, the coating amount is shown in mol units with respect to 1 mol of silver halide in the same layer.

First Layer (Antihalation Layer) Black Colloidal Silver Silver 0.09 Gelatin 1.60 ExM-1 0.12 ExF-1 2.0 × 10 ^-3 Solid Disperse Dye ExF-2 0.030 Solid Disperse Dye ExF-3 0.040 HBS-1 0.15 HBS-2 0.02

Second Layer (Intermediate Layer) Silver Iodobromide Emulsion M Silver 0.065 ExC-2 0.04 Polyethylacrylate Latex 0.20 Gelatin 1.04

Third Layer (Low Sensitivity Red Sensitive Emulsion Layer) Silver iodobromide Emulsion A Silver 0.25 Silver Iodobromide Emulsion B Silver 0.25 ExS-1 6.9 × 10 ^-5 ExS-2 1.8 × 10 ^-5 ExS-3 3.1 × 10 ^-4 ExC-1 0.17 ExC-3 0.030 ExC-4 0.10 ExC-5 0.020 ExC-6 0.010 Cpd-2 0.025 HBS-1 0.10 Gelatin 0.87

Fourth Layer (Medium-Sensitivity Red Milk-Sensitive Layer) Silver Iodobromide Emulsion C Silver 0.70 ExS-1 3.5 × 10 ⁻⁴ ExS-2 1.6 × 10 ⁻⁵ ExS-3 5.1 × 10 ^-4 ExC-1 0.13 ExC-2 0.060 ExC-3 0.0070 ExC-4 0.090 ExC-5 0.015 ExC-6 0.007 Cpd-2 0.023 HBS-1 0 .10 gelatin 0.75

Fifth layer (high-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion D silver 1.40 As shown in Table 8, the dye of emulsion 117 [(SD-3) (4.6 × 10
^-4 ) + (SD-6) (0.5 × 10 ^-4 )] or the dye of Emulsion 118 [(II-39) (4.6 × 10 ^-4 ) + (II-33) (0.5 × 10 ^-4 )] use. ExC-1 0.10 ExC-3 0.045 ExC-6 0.020 ExC-7 0.010 Cpd-2 0.050 HBS-1 0.22 HBS-2 0.050 Gelatin 1.10

6th layer (intermediate layer) Cpd-1 0.090 Solid disperse dye ExF-4 0.030 HBS-1 0.050 Polyethyl acrylate latex 0.15 Gelatin 1.10

Seventh Layer (Low Sensitivity Green Sensitive Emulsion Layer) Silver iodobromide Emulsion 0.15 Silver Iodobromide Emulsion F Silver 0.10 Silver Iodobromide Emulsion G Silver 0.10 ExS-4 3.0 × 10 ^-5 ExS-5 2.1 × 10 ^-4 ExS-6 8.0 × 10 ^-4 ExM-2 0.33 ExM-3 0.086 ExY-1 0.015 HBS-1 0.30 HBS- 3 0.010 Gelatin 0.73

Eighth Layer (Medium-Sensitivity Green Sensitive Emulsion Layer) Silver Iodobromide Emulsion H Silver 0.80 ExS-4 3.2 × 10 ⁻⁴ ExS-5 2.2 × 10 ⁻⁴ ExS-6 8.4 × 10 ^-4 ExC-8 0.010 ExM-2 0.10 ExM-3 0.025 ExY-1 0.018 ExY- ⁴ 0.010 ExY-5 0.040 HBS-1 0.13 HBS-3 4 0.0 × 10 ^-3 gelatin 0.80

9th layer (high-sensitivity green-sensitive emulsion layer) Silver iodobromide Emulsion I Silver 1.25 As shown in Table 8, the dye (SD-1) of emulsion 101 and emulsion 10 were used.
4 dye (II-2), emulsion 107 dye (SD-7), emulsion 109
Dyes (II-9) of (4.6 × 10 ⁻⁴ ) were used. ExC-1 0.010 ExM-1 0.020 ExM-4 0.025 ExM-5 0.040 Cpd-3 0.040 HBS-1 0.25 Polyethyl acrylate latex 0.15 Gelatin 1.33

10th layer (yellow filter layer) Yellow colloidal silver Silver 0.015 Cpd-1 0.16 Solid disperse dye ExF-5 0.060 Solid disperse dye ExF-6 0.060 Oil-soluble dye ExF-7 0. 010 HBS-1 0.60 Gelatin 0.60

11th layer (low-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion J Silver 0.09 Silver iodobromide emulsion K Silver 0.09 ExS-7 8.6 × 10 ^-4 ExC-8 7.0 × 10 ^-3 ExY-1 0.050 ExY-2 0.22 ExY-3 0.50 ExY-4 0.020 Cpd-2 0.10 Cpd-3 4.0 × 10 ^-3 HBS-1 0.28 Gelatin 1.20

12th layer (high-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion L Silver 1.00 ExS-7 4.0 × 10 ^-4 ExY-2 0.10 ExY-3 0.10 ExY-4 0 0.010 Cpd-2 0.10 Cpd-3 1.0 × 10 ^-3 HBS-1 0.070 Gelatin 0.70

13th layer (first protective layer) UV-1 0.19 UV-2 0.075 UV-3 0.065 HBS-1 5.0 × 10 ^-2 HBS-4 5.0 × 10 ^-2 Gelatin 1.8

14th layer (second protective layer) Silver iodobromide emulsion M Silver 0.10 H-1 0.40 B-1 (diameter 1.7 μm) 5.0 × 10 ^-2 B-2 (diameter 1 0.7 μm) 0.15 B-3 0.05 S-1 0.20 Gelatin 0.70

Further, in order to improve the storability, processability, pressure resistance, antifungal / antibacterial property, antistatic property and coating property of each layer, W-1 to W-3, B-4 to B are appropriately added. -6, F
-1 to F-17, and iron salts, lead salts, gold salts, platinum salts,
It contains a palladium salt, an iridium salt, and a rhodium salt.

[0157]

[Table 7]

In Table 7, (1) Emulsions D and I to L were prepared according to the examples of JP-A-2-191938 in the form of thiourea dioxide and thiosulfonic acid (XX-1).
6) was used for reduction sensitization during grain preparation. Also,
An emulsion prepared in the same manner except that p-quinone was used instead of (XX-16) was also prepared. (2) Emulsions A to L were subjected to gold sensitization, sulfur sensitization and selenium sensitization in the presence of the spectral sensitizing dye described in each photosensitive layer and sodium thiocyanate according to the examples of JP-A-3-237450. ing. (3) For the preparation of tabular grains, low molecular weight gelatin is used according to the examples of JP-A-1-158426. (4) Dislocation lines as described in JP-A-3-237450 are observed in the tabular grains by using a high voltage electron microscope. (5) Emulsion L is a double structure grain containing an internal high iodine core described in JP-A-60-143331.

Preparation of Dispersion of Organic Solid Disperse Dye ExF-2 shown below was dispersed by the following method. That is, 21.7 ml of water and 3 ml of 5% aqueous solution of sodium p-octylphenoxyethoxyethanesulfonate and 5%
% Aqueous p-octylphenoxypolyoxyethylene ether (degree of polymerization 10) 0.5g into a 700ml pot mill, add dye ExF-2 5.0g and zirconium oxide beads (diameter 1mm) 500ml. The contents were dispersed for 2 hours. This dispersion is made by Chuo Koki
A BO type vibration ball mill was used. After the dispersion, the contents were taken out, 8 g of a 12.5% gelatin aqueous solution was added, and the beads were removed by filtration to obtain a gelatin dispersion of the dye. The average particle size of the fine dye particles was 0.44 μm.

Similarly, solid dispersions of ExF-3, ExF-4 and ExF-6 were obtained. The average particle size of the fine dye particles is
They were 0.24 μm, 0.45 μm and 0.52 μm. ExF-5
Is the microprecipitation (Micropreci) described in Example 1 of EP 549,489A.
It was dispersed by the dispersion method. Average particle size is 0.06
μm.

[0161]

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[0162]

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[0163]

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[0164]

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[0165]

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[0166]

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[0167]

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[0168]

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[0169]

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[0170]

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[0171]

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[0172]

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[0173]

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[0174]

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[0175]

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[0176]

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Samples using the dye of the fifth layer, the dye of the ninth layer and (XX-16) and p-quinone shown in Table 8 were prepared and exposed in the same manner as in Example 1 (except that the SC50 filter was used). Processing was performed). The sensitivity was shown by the relative value of the reciprocal of the exposure amount required for the optical density to be higher than the fog by 0.1.

[0178]

[Table 8]

As is clear from Table 8, the samples using the dyes of the emulsions 104, 109 and 118 of the present invention have higher sensitivity than the samples using the dyes of the comparative emulsions 101, 107 and 117 even in the multilayer color film. And it was low. As an oxidizing agent for preparing the reduction sensitized emulsion, p-
It turns out that thiosulfonic acid (XX-16) is more preferable than quinone.

Example 3 1) Support The support used in this example was prepared by the following method. Polyethylene-2,6-naphthalate polymer 10
After drying 0 part by weight and 2 parts by weight of Tinuvin P.326 (manufactured by Ciba-Geigy) as an ultraviolet absorber,
After melting at 300 ℃, extrude from T-die, 140 ℃
The film was longitudinally stretched 3.3 times at 130 ° C., then laterally stretched 3.3 times at 130 ° C., and further heat-set at 250 ° C. for 6 seconds to obtain a PEN film having a thickness of 90 μm. The PEN film contains blue dye, magenta dye, and yellow dye (I-1 and I-in Public Technical Report No. 94-6023).
4, I-6, I-24, I-26, I-27, II-5)
Was added in an appropriate amount. Furthermore, by winding it around a stainless steel core with a diameter of 20 cm, and giving it a thermal history of 110 ° C. for 48 hours,
The support is one that does not tend to curl.

2) Coating of undercoat layer The above-mentioned support was subjected to corona discharge treatment, UV discharge treatment and glow discharge treatment on both sides thereof, and then gelatin 0.1 g / m ² and sodium α-on each side. Sulfodi-2-ethylhexyl succinate 0.01 g / m ² , salicylic acid 0.04 g /
m ² , p-chlorophenol 0.2 g / m ² , (CH ₂ = CHSO ₂ CH ₂ CH ₂
NHCO) ₂ CH ₂ 0.012 g / m ² , polyamide-epichlorohydrin polycondensate 0.02 g / m ²
m ² , using a bar coater), an undercoat layer was provided on the high temperature side during stretching. Drying was performed at 115 ° C. for 6 minutes (all rollers and transport devices in the drying zone were at 115 ° C.).

3) Coating of Back Layer After the undercoating, an antistatic layer having the following composition, a magnetic recording layer and a sliding layer were coated as back layers on one surface of the support. 3-1) Application of antistatic layer A tin oxide-antimony oxide composite having an average particle size of 0.005 μm has a specific resistance of 5 Ω · cm, and a dispersion of fine particle powder (secondary agglomerated particle size of about 0.08 μm) is used. .2 g / m ² , gelatin 0.05 g /
m ² , (CH ₂ = CHSO ₂ CH ₂ CH ₂ NHCO) ₂ CH ₂ 0.02 g / m ² , poly (degree of polymerization 10) oxyethylene-p-nonylphenol 0.0
05 g / m ² and resorcin were applied. 3-2) Coating of magnetic recording layer 3-Cobalt-γ-iron oxide coated with poly (degree of polymerization 15) oxyethylene-propyloxytrimethoxysilane (15% by weight) (specific surface area 43 m ² / g, Long axis 0.14
μm, minor axis 0.03 μm, saturation magnetization 89emu / g, Fe ^{+ 2} / Fe
⁺³ = 6/94, the surface is aluminum oxide, silicon oxide, and iron oxide is 2
0.06 g / m ² of diacetyl cellulose 1.2 g / m ² (iron oxide was dispersed in an open kneader and a sand mill), and C ₂ H ₅ C (CH ₂ OCONH) as a curing agent. -C
₆ H ₃ (CH ₃ ) NCO) ₃ 0.3 g / m ² was applied with a bar coater using acetone, methyl ethyl ketone and cyclohexanone as a solvent to obtain a magnetic recording layer having a thickness of 1.2 μm. Silica particles (0.3 μm) and 3-poly (degree of polymerization 1 as matting agent)
5) Aluminum oxide (0.15 μm) as an abrasive, which was treated and coated with oxyethylene-propyloxytrimethoxysilane (15% by weight), was added so as to be 10 mg / m ² . Drying was performed at 115 ° C. for 6 minutes (all rollers and transport devices in the drying zone were at 115 ° C.). The increase in D ^B color density of the magnetic recording layer by X-light (blue filter) is about 0.1, and the saturation magnetization moment of the magnetic recording layer is 4.2.
The emu / g, coercive force was 7.3 × 10 ⁴ A / m, and the squareness ratio was 65%. A sample without a magnetic recording layer was also prepared for comparison.

3-3) Preparation of sliding layer Diacetyl cellulose (25 mg / m ² ), C ₆ H ₁₃ CH (OH) C ₁₀
H ₂₀ COOC ₄₀ H ₈₁ (Compound a, 6 mg / m ² ) / C ₅₀ H ₁₀₁ O (CH ₂ CH
_{A 2} O) ₁₆ H (compound b, 9 mg / m ² ) mixture was applied. In addition,
This mixture was melted in xylene / propylene monomethyl ether (1/1) at 105 ° C. and poured into propylene monomethyl ether (10 times volume) at room temperature to prepare a dispersion, which was then dispersed in acetone (average particle size). The diameter was adjusted to 0.01 μm) before adding. Silica particles as matting agent (0.3 μm
) And an abrasive 3-poly (degree of polymerization of 15) oxyethylene-propyloxytrimethoxysilane (15% by weight of aluminum oxide (0.15 μm) coated at 15 mg / each)
It was added so as to be m ² . Drying was carried out at 115 ° C for 6 minutes (all the rollers and conveying devices in the drying zone were 115 ° C).
° C). The sliding layer has a dynamic friction coefficient of 0.06 (stainless steel ball of 5 mmφ, load 100 g, speed of 6 cm / min), static friction coefficient of 0.07 (clip method), and the dynamic friction coefficient of the emulsion surface and the sliding layer described later is 0.12. It had excellent characteristics.

4) Coating of photosensitive layer Next, exactly the same as in Example 2 except that the dyes of the fifth and ninth layers were changed as shown in Table 9 on the side opposite to the back layer obtained above. Sample 3 shown in Table 10 after applying each layer of the composition in multiple layers
001 to 3004 were created. The light-sensitive material prepared as described above is cut into a width of 24 mm and 160 cm, and two perforations of 2 mm square are provided at a distance of 5.8 mm at a position 0.7 mm from one side width direction of the light-sensitive material. I made a set of these two sets with a 32mm interval and
It was stored in the plastic film cartridge described in FIGS. 1 to 7 of 6,887. On this sample, from the coated side of the magnetic recording layer, head gap 5 μm, number of turns
FM signals were recorded at a feed rate of 1,000 / s during the above perforations of the light-sensitive material using a head capable of inputting / outputting 2,000. After recording the FM signal, the emulsion surface was uniformly exposed for 1,000 cms, and each processing was performed by the methods described below, and then the emulsion was stored again in the original plastic film cartridge. The samples 3001 to 3002 were exposed in the same manner as in Example 1 (excluding the SC50 filter), and then subjected to the following treatment (running treatment), and evaluated in the same manner as in Example 2. Each processing was carried out by the following using an automatic processor FP-360B manufactured by Fuji Photo Film Co., Ltd. The remodeling was performed so that the overflow solution of the bleaching bath was not discharged to the post-bath but was entirely discharged to the waste liquid tank. This FP-3
The 60B is equipped with the evaporation correction means described in JIII Journal of Technical Disclosure No. 94-4992. The treatment process and the treatment liquid composition are shown below.

(Processing step) Step Processing time Processing temperature Replenishment amount ^* Tank capacity Color development 3 minutes 5 seconds 37.8 ° C. 20 ml 11.5 l Bleaching 50 seconds 38.0 ° C. 5 ml 5 l Fixing (1) 50 seconds 38.0 ° C-5 liters Fixing (2) 50 seconds 38.0 ° C 8 ml 5 liters Water wash 30 seconds 38.0 ° C 17 ml 3 liters Stable (1) 20 seconds 38.0 ° C-3 liters Stable (2) 20 Seconds 38.0 ° C 15 ml 3 liters Dry 1 minute 30 seconds 60 ° C * Replenishment amount per 35 m width of photosensitive material 1.1 m width (equivalent to 24 Ex. 1) Stabilizer and fixer from (2) to (1) It was a countercurrent system, and the overflow liquid of washing water was all introduced into the fixing bath (2). The amount of developing solution brought into the bleaching process, the amount of bleaching solution brought into the fixing process, and the amount of fixing solution brought into the washing process were 2.
5 ml, 2.0 ml, and 2.0 ml. The crossover time is 6 seconds in all cases, and this time is included in the processing time of the previous step. Open area 100 cm ² in the color developing solution in the processing machine, 120 cm ² in the bleaching solution, the other processing solutions was about 100 cm ^2.

The composition of the processing liquid is shown below. (Color developer) Tank solution (g) Replenisher (g) Diethylenetriaminepentaacetic acid 3.0 3.0 Disodium catechol-3,5-disulfonate 0.3 0.3 Sodium sulfite 3.9 5.3 Potassium carbonate 39.0 39.0 Disodium-N, N-bis (2-sulfonateethyl) hydroxylamine 1.5 2.0 Potassium bromide 1.3 0.3 Potassium iodide 1.3 mg-4-hydroxy-6- Methyl-1,3,0.05-3a, 7-tetrazaindene hydroxylamine sulfate 2.4 3.3 2-Methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline sulfate Salt 4.5 6.5 Add water 1.0 liter 1.0 liter pH (adjusted with potassium hydroxide and sulfuric acid) 10.05 10.18

(Bleaching solution) Tank solution (g) Replenishing solution (g) 1,3-Diaminopropanetetraacetic acid Ferric ammonium ammonium monohydrate 113 170 Ammonium bromide 70 105 Ammonium nitrate 14 21 Succinic acid 34 51 Maleic acid 28 42 Add water to 1.0 liter 1.0 liter pH [Prepared with ammonia water] 4.6 4.0

(Fixing (1) Tank Liquid) A 5:95 (volume ratio) mixture of the above bleaching tank liquid and the following fixing tank liquid. (PH
6.8) (Fixing (2)) Tank solution (g) Replenisher (g) Ammonium thiosulfate aqueous solution 240 mL 720 mL (750 g / L) Imidazole 721 Ammonium methanethiosulfonate 515 Ammonium methanesulfinate 10 30 Ethylenediamine4 Acetic acid 13 39 Add water 1.0 liter 1.0 liter pH [prepared with aqueous ammonia and acetic acid] 7.4 7.45

(Washing water) Tap water was used as an H-type strongly acidic cation exchange resin (Amberlite IR-120 manufactured by Rohm and Haas).
B) and OH-type strongly basic anion exchange resin (Amberlite IR-400) are passed through a mixed bed column to treat calcium and magnesium ions at a concentration of 3 mg / liter or less, followed by dichloride. Sodium isocyanurate 20
mg / l and sodium sulfate 150 mg / l were added. The pH of this liquid was in the range of 6.5 to 7.5.

(Stabilizing Solution) Common to Tank Solution and Replenishing Solution (Unit g) Sodium p-toluenesulfinate 0.03 Polyoxyethylene-p-monononylphenyl ether (Average degree of polymerization: 10) 0.2 1,2-benzo Isothiazolin-3-one sodium 0.10 Ethylenediaminetetraacetic acid disodium salt 0.05 1,2,4-triazole 1.3 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine 0.75 Add water to 1.0 liter pH 8.5

The evaluation results are shown in Table 10. As is clear from Table 10, the samples 3002 and 3004 of the present invention had higher sensitivity and lower fog than the comparative samples 3001 and 3003. Further, comparing the presence / absence of the magnetic recording layer, there is almost no difference between the comparative samples 3001 and 3003, whereas in the samples 3002 and 3004 using the dye of the present invention, the magnetic recording layer 3002 is more preferable. It had high sensitivity and low fog.

[0192]

[Table 9]

[0193]

[Table 10]

[0194]

According to the present invention, a silver halide photographic light-sensitive material having high image quality, high sensitivity and excellent storability, in which fog is suppressed, can be obtained.

────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] March 18, 1996

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Claim 2

[Correction method] Change

[Correction contents]

Embedded image In formula (II), L ₃ , L ₄ , L ₅ , L ₆ , L ₇ , L ₈ and L ₉ represent a methine group. p ₂ and p ₃ represent 0 or 1. n ₁ represents 0, 1, 2, or 3. Z ₂ and Z ₃ each represent an atom group necessary for forming a 5- or 6-membered nitrogen-containing heterocyclic ring. M ₂ represents a charge-balancing counterion, and m ₂ represents a number of 0 or more and 6 or less required to neutralize the charge of the molecule.
R ₁ and R ₂ represent an alkyl group. However, R ₁ and R ₂
At least one of them is an alkyl group represented by Rz below.

Embedded image In Rz, La ₁ has the same meaning as La. V _1a is V ₁
Is synonymous with q _1a has the same meaning as q _1, q _2a has the same meaning as q _2. General formula (III)

Embedded image In formula (III), L ₁₀ , L ₁₁ , L ₁₂ , and L ₁₃ represent a methine group. p ₄ is 0 or 1. n ₂ represents 0, 1, 2, or 3. Z ₄ and Z ₅ represent an atom group necessary for forming a 5- or 6-membered nitrogen-containing heterocyclic ring. M ₃ represents a charge balancing counter ion, and m ₃ represents a number of 0 or more and 6 or less necessary for neutralizing the charge of the molecule. R ₃ has the same _meaning as R _z . R
₄ represents an alkyl group, an aryl group, or a heterocyclic group. General formula (IV)

Embedded image In the formula (IV), L ₁₄ , L ₁₅ , L ₁₆ , L ₁₇ , L ₁₈ , L ₁₉ , L
₂₀ and L ₂₁ represent a methine group. p ₄ and p ₅ are 0 or 1
Represents n ₃ and n ₄ represent 0, 1, 2, or 3. Z
₅ , Z ₇ and Z ₈ represent an atomic group necessary for forming a 5- or 6-membered nitrogen-containing heterocycle. M ₄ represents a charge-balancing counter ion, and m ₄ represents a number from 0 to 6 required to neutralize the charge of the molecule. R ₅ and R ₇ represent an alkyl group. However, at least one of R ₅ and R ₇ is the alkyl group represented by Rz. R ₆ represents an alkyl group, an aryl group or a heterocyclic group.

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0015

[Correction method] Change

[Correction contents]

In the formula (III), L_Ten, L₁₁, L₁₂And L₁₃Is
Represents a methine group. p_FourRepresents 0 or 1. n_TwoIs 0,
Represents 1, 2, or 3. Z_FourAnd Z_FiveContains 5 or 6 members
Represents an atom group necessary for forming a nitrogen heterocycle. M_Three
Represents a charge-balancing counter ion, m _ThreeNeutralizes the molecular charge
Represents a number from 0 to 6 necessary for R_ThreeIs R_zSame as
Righteous. R_FourRepresents an alkyl group or a heterocyclic group. General formula (IV)

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0017

[Correction method] Change

[Correction contents]

In the formula (IV), L ₁₄ , L ₁₅ , L ₁₆ , L ₁₇ , L
₁₈ , L ₁₉ , L ₂₀ and L ₂₁ represent a methine group. p ₄ and p
₅ represents 0 or 1. n ₃ and n ₄ represent 0, 1, 2, or 3. Z ₅ , Z ₇ and Z ₈ each represent an atom group necessary for forming a 5- or 6-membered nitrogen-containing heterocyclic ring. M ₄ represents a charge-balancing counter ion, and m ₄ represents a number from 0 to 6 required to neutralize the charge of the molecule. R ₅ and R ₇ represent an alkyl group. However, at least one of R ₅ and R ₇ is the alkyl group represented by Rz. R ₆
Represents an alkyl group, an aryl group or a heterocyclic group.

Claims (6)

[Claims] 1. A silver halide photographic material having at least one silver halide emulsion layer on a support,
A silver halide photographic light-sensitive material characterized in that the silver halide grains in the emulsion layer have been subjected to reduction sensitization and contain at least one compound represented by the following general formula (I). General formula (I) In formula (I), La represents a methylene group, and V ₁ represents a monovalent substituent. q ₁ represents ₁ , 2, 3 or 4 and q ₂ represents 0, 1, ₂ , 3 or 4. L ₁ and L ₂ represent a methine group. p ₁ represents 0 or 1. Z ₁ represents an atom group necessary for forming a 5- or 6-membered nitrogen-containing heterocyclic ring. M ₁
Represents a charge-balancing counterion, and m ₁ represents a number of 0 or more necessary for neutralizing the charge of the molecule. Q represents a methine group or a polymethine group substituted with a heterocyclic group or an aromatic group. 2. The compound represented by the general formula (I) according to claim 1 is a compound selected from the following general formula (II), general formula (III) or general formula (IV). The silver halide photographic light-sensitive material according to claim 1. General formula (II) In formula (II), L ₃ , L ₄ , L ₅ , L ₆ , L ₇ , L ₈ and L ₉ represent a methine group. p ₂ and p ₃ represent 0 or 1. n ₁ represents 0, 1, 2, or 3. Z ₂ and Z ₃ each represent an atom group necessary for forming a 5- or 6-membered nitrogen-containing heterocyclic ring. M ₂ represents a charge-balancing counterion, and m ₂ represents a number of 0 or more and 6 or less required to neutralize the charge of the molecule.
R ₁ and R ₂ represent an alkyl group. However, R ₁ and R ₂
At least one of them is an alkyl group represented by Rz below. Embedded image In Rz, La ₁ has the same meaning as La. V _1a is V ₁
Is synonymous with q _1a has the same meaning as q _1, q _2a has the same meaning as q _2. General formula (III) In formula (III), L ₁₀ , L ₁₁ , L ₁₂ , and L ₁₃ represent a methine group. p ₄ is 0 or 1. n ₂ represents 0, 1, 2, or 3. Z ₄ and Z ₅ represent an atom group necessary for forming a 5- or 6-membered nitrogen-containing heterocyclic ring. M ₃ represents a charge balancing counter ion, and m ₃ represents a number of 0 or more and 6 or less necessary for neutralizing the charge of the molecule. R ₃ and R ₄ represent an alkyl group. However, at least one of R ₃ and R ₄ is the alkyl group represented by Rz. General formula (IV): In the formula (IV), L ₁₄ , L ₁₅ , L ₁₆ , L ₁₇ , L ₁₈ , L ₁₉ , L
₂₀ and L ₂₁ represent a methine group. p ₄ and p ₅ are 0 or 1
Represents n ₃ and n ₄ represent 0, 1, 2, or 3. Z
₅ , Z ₇ and Z ₈ represent an atomic group necessary for forming a 5- or 6-membered nitrogen-containing heterocycle. M ₄ represents a charge-balancing counter ion, and m ₄ represents a number from 0 to 6 required to neutralize the charge of the molecule. R ₅ , R ₆ and R ₇ represent an alkyl group. However, at least one of R ₅ , R ₆ and R ₇ is an alkyl group represented by Rz. 3. The silver halide photographic light-sensitive material according to claim 1, wherein q ₁ in the compound represented by formula (I) according to claim 1 is 1. 4. The compound represented by the general formula (I) according to claim 1, wherein q ₁ is 1 and q ₂ is 0,
2. The silver halide photographic light-sensitive material according to claim 1, wherein La is an unsubstituted methylene group. 5. The silver halide photographic light-sensitive material according to claim 1, wherein the following general formula (XX), general formula (XXI), or (X
The silver halide photographic light-sensitive material according to claim 1, containing at least one of the compounds represented by XII). General formula (XX) R ₁₀₁ -SO ₂ S-M ₁₀₁ General formula (XXI) R ₁₀₁ -SO ₂ S-R ₁₀₂ General formula (XXII) R ₁₀₁ -SO ₂ S- (E) _a -SSO
_2- R _{103 In the} formula, R ₁₀₁ , R ₁₀₂ , and R ₁₀₃ represent an alkyl group, an aryl group, or a heterocyclic group, M ₁₀₁ represents a cation,
E represents a divalent linking group, and a is 0 or 1. 6. The silver halide photographic light-sensitive material according to claim 1, further comprising a transparent magnetic recording layer.