JP2002122953A - Silver halide photographic material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silver halide photographic material having high sensitivity and good preservability of a latent image. SOLUTION: The silver halide photographic material contains silver halide grains spectrally sensitized with a specified sensitizing dye having a thiadiazole or thiazole nucleus or the like and a benzazole nucleus or the like and further sensitized with selenium.

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 containing a specific sensitizing dye, selenium-sensitized, and having high sensitivity and good storage stability of a latent image.

[0002]

2. Description of the Related Art Hitherto, great efforts have been made to increase the sensitivity of silver halide photographic light-sensitive materials and to reduce residual coloring (residual color) after processing. German patent 19,96
No. 0,279A1, it is stated that the residual color is improved by a specific sensitizing dye having a thiadiazole nucleus or the like, but the sensitivity was not sufficiently satisfactory.

On the other hand, it is useful to selenium sensitize a silver halide emulsion to increase the sensitivity.
The selenium compounds described in JP-A-4-15748, JP-B-43-13489, JP-A-4-25832 and JP-A-4-109240 are known. However, these selenium-sensitized emulsions tend to have poor storage stability (especially storage stability of latent images), which is a problem, and a solution has been desired.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a silver halide photographic light-sensitive material having high sensitivity and good storage stability of a latent image.

[0005]

Means for Solving the Problems The object of the present invention was able to be achieved by the following (1) to (12) as a result of intensive studies. (1) In a silver halide photographic material containing at least one compound represented by the following general formula (I), silver halide grains of the silver halide photographic material are selenium-sensitized. Silver halide photographic material. General formula (I)

[0006]

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In the formula (I), X₁, X_Two, And X_ThreeIs oxygen
Atom, sulfur atom, selenium atom, nitrogen atom, or carbon atom
Represents Z₁Is a condensed aromatic hydrocarbon or aromatic heterocycle
Lists the atoms required to form a ring-containing nitrogen-containing heterocycle.
You. R₁, And R_TwoIs an alkyl group, an aryl group, or a hetero group
Represents a ring group. V₁, V_Two, And V_ThreeIs a hydrogen atom, or
Represents a substituent. X₁Is a carbon atom, q₁Is 2, a nitrogen atom
Q₁Is 1, otherwise q₁Is 0.
X_TwoIs a carbon atom, q_TwoIs 1, otherwise q
_TwoIs 0. X_ThreeIs a carbon atom, q_ThreeIs 1, otherwise
Q_ThreeIs 0. L₁, L_Two, L_Three, L_Four,
And L_FiveRepresents a methine group. n₁Is 0, 1, 2, 3, or 4
Represents p₁Represents 0 or 1. M₁Is the charge-balancing counterion
And m ₁Represents the number required to neutralize the molecular charge.
You. Preferably, the silver halide grains have the general formula (I)
Has been spectrally sensitized. Also halogen
A silver halide photographic emulsion in a silver halide photographic material has a general formula
Containing the compound of (I), wherein the emulsion is selenium-sensitized
Is preferred. (2) The compound of the general formula (I) according to (1) is
Being selected from the compounds represented by the general formula (II)
(1) The silver halide photographic material as described in (1). General formula
(II)

[0008]

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In the formula (II), Z ₂ represents an oxygen atom, a sulfur atom, a selenium atom, a nitrogen atom or a carbon atom.
V ₄ , V ₅ , V ₆ and V ₇ represent a hydrogen atom or a substituent. However, these substituents may form a ring together. X ₁ , X ₂ , X ₃ , V ₁ , V ₂ , V ₃ , q ₁ , q ₂ , q ₃ ,
R ₁ , R ₂ , L ₁ , L ₂ , L ₃ , n ₁ , M ₁ , and m ₁ have the same meanings as in the general formula (1). (3) The general formula (I) or (I) described in (1) or (2)
The silver halide photographic material as described in (1) or (2), wherein in the compound represented by I), R ₁ and R ₂ are alkyl groups substituted with an acid group. (4) The silver halide photographic material as described in (2), wherein the compound of formula (II) described in (2) is selected from the compounds represented by the following formula (III). General formula (III)

[0010]

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In the formula (III), V₁’, V_Two’And V_Three’
Represents a hydrogen atom or a non-aromatic substituent. V_Four’,
V_Five’, V₆’And V₇’Represents a hydrogen atom or a substituent
Represent. Where V_Five’And V₆’Or V₆’And V₇’Together
To form a 5- or 6-membered ring. R_TenIs hydrogen field
, Or an alkyl group,_TwoIs a nitrogen atom
R_TenRepresents a hydrogen atom. n₁'Represents 0 or 1.
R₁’And R_Two ’Represents an alkyl group substituted with an acid group.
You. X₁, X_Two, X_Three, Q₁, Q_Two, Q_Three , M₁, M₁, Z_TwoIs
It has the same meaning as in formula (II). (5) Formula (I), (II), or (III)
In the compound, X₁Is a sulfur atom, and X_TwoIs a carbon atom
And X_ThreeIs a nitrogen atom or a carbon atom.
Halogenation according to any one of (1) to (4)
Silver photographic photosensitive material. (6) Compounds represented by formula (II) or (III)
And Z_TwoIs a sulfur atom (2)
A silver halide photographic light-sensitive material according to any one of claims 1 to 5,
Fees. (7) represented by formula (I), (II) or (III)
In a compound, R₁, R _Two, R₁’And R_Two’Is a sulfo
(1) to (6) which are an alkyl group
A silver halide photographic material as described in any of the above. (8) Compounds represented by general formula (II) or (III)
Then V₆, And V₆’Is a halogen atom or an aromatic group
Described in any one of (2) to (7).
Silver halide photographic light-sensitive material. (9) The compound represented by the general formula (II) or (III)
Then, V_Four, V_Five, V₇, V_Four’, V_Five’And V₇’Is water
Elementary atom, V₆, And V₆’Is a halogen atom, or
Any of (2) to (7), which is a phenyl group
A silver halide photographic light-sensitive material according to any one of the above. (10) Compound represented by general formula (II) or (III)
At V₆And V₇, And V₆’And V₇’Together
(2) to characterized by forming an aromatic ring
The silver halide photographic light-sensitive material according to any one of (7) and (7). (11) a compound represented by the general formula (II) or (III)
At V_Four, V_Five, V_Four’And V_Five’Is a hydrogen atom
And V₆And V₇, And V₆’And V₇’Together with Benze
(2) to (7), wherein
The silver halide photographic light-sensitive material according to any one of the above. (12) represented by the general formula (I), (II) or (III)
Is characterized in that the compound is J-aggregating (1) to
Silver halide photographic light-sensitive material according to any one of (11) and (12).
Fees.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. First, the groups used in the present invention will be described in detail.

In the present invention, when a particular moiety is referred to as a "group," the moiety may be substituted with one or more (up to the maximum number of possible) substituents, even if the moiety itself is unsubstituted. Means that you can. For example, “alkyl group” means a substituted or unsubstituted alkyl group. The substituents that can be used in the compounds of the present invention include any substituents, regardless of whether they are substituted.

When such a substituent is represented by W, the substituent represented by W may be any, and is not particularly limited. Examples thereof include a halogen atom, an alkyl group [(cycloalkyl group, bicycloalkyl group and A alkenyl group (including a cycloalkenyl group and a bicycloalkenyl group), an alkynyl group,
Shall also be included. ], Aryl group, heterocyclic group (may be referred to as heterocyclic group), cyano group, hydroxyl group, nitro group, carboxyl group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyl Oxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group (including anilino group), ammonium group, acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group , Alkyl and arylsulfonylamino, mercapto, alkylthio, arylthio, heterocyclic thio, sulfamoyl, sulfo, alkyl and arylsulfinyl, alkyl and arylsulfonyl, acyl, arylo Xycarbonyl group, alkoxycarbonyl group, carbamoyl group, aryl and heterocyclic azo group, imide group, phosphino group, phosphinyl group, phosphinyloxy group, phosphinylamino group, phospho group (also called phosphono group), silyl Examples include a group, a hydrazino group, a ureido group, a boronic acid group, a phosphato group, a sulfato group, and other known substituents.

More specifically, W is a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom),
Alkyl group [[represents a linear, branched, or cyclic substituted or unsubstituted alkyl group; They are alkyl groups (preferably alkyl groups having 1 to 30 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, t-butyl, n-octyl, eicosyl, 2-chloroethyl, 2-cyanoethyl, 2-ethylhexyl). A cycloalkyl group (preferably a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, for example, cyclohexyl, cyclopentyl, 4-n-dodecylcyclohexyl), a bicycloalkyl group (preferably having 5 to 30 carbon atoms) A substituted or unsubstituted bicycloalkyl group, that is, having 5 to 3 carbon atoms
This is a monovalent group obtained by removing one hydrogen atom from a bicycloalkane of 0. For example, bicyclo [1,2,2] heptan-2-yl, bicyclo [2,2,2] octane-3-
Yl) and a tricyclo structure having more ring structures. An alkyl group (for example, an alkyl group of an alkylthio group) in the substituents described below represents an alkyl group having such a concept, and further includes an alkenyl group and an alkynyl group. And an alkenyl group [which represents a linear, branched or cyclic substituted or unsubstituted alkenyl group.
They are alkenyl groups (preferably having 2 to 30 carbon atoms).
A substituted or unsubstituted alkenyl group such as vinyl,
Allyl, prenyl, geranyl, oleyl), a cycloalkenyl group (preferably a substituted or unsubstituted cycloalkenyl group having 3 to 30 carbon atoms, that is, a monovalent obtained by removing one hydrogen atom of a cycloalkene having 3 to 30 carbon atoms) For example, 2-cyclopenten-1-yl,
2-cyclohexen-1-yl), bicycloalkenyl group (substituted or unsubstituted bicycloalkenyl group, preferably substituted or unsubstituted bicycloalkenyl group having 5 to 30 carbon atoms, ie, bicycloalkene having one double bond) It is a monovalent group with one hydrogen atom removed.
For example, bicyclo [2,2,1] hept-2-ene-1
-Yl, bicyclo [2,2,2] oct-2-ene-4
-Yl). Alkynyl group (preferably substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, for example, ethynyl, propargyl, trimethylsilylethynyl group)], aryl group (preferably substituted or unsubstituted having 6 to 30 carbon atoms) Aryl groups such as phenyl, p-tolyl, naphthyl, m-chlorophenyl, o-hexadecanoylaminophenyl), heterocyclic groups (preferably 5- or 6-membered substituted or unsubstituted aromatic or non-aromatic heterocyclic groups); A monovalent group obtained by removing one hydrogen atom from a ring compound, more preferably a 5- or 6-membered aromatic heterocyclic group having 3 to 30 carbon atoms, for example, 2-furyl, 2-thienyl , 2-pyrimidinyl, 2-benzothiazolyl, 1-methyl-2-
A cationic heterocyclic group such as pyridinio and 1-methyl-2-quinolinio may be used. ), A cyano group, a hydroxyl group, a nitro group, a carboxyl group, an alkoxy group (preferably a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, for example, methoxy, ethoxy, isopropoxy, t-butoxy, n-octyl) Oxy, 2-methoxyethoxy), aryloxy group (preferably having 6 carbon atoms)
To 30 substituted or unsubstituted aryloxy groups, for example, phenoxy, 2-methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, 2-tetradecanoylaminophenoxy), silyloxy group (preferably carbon number A silyloxy group having 3 to 20, for example, trimethylsilyloxy, t-butyldimethylsilyloxy), a heterocyclic oxy group (preferably having 2 to 3 carbon atoms);
0 substituted or unsubstituted heterocyclic oxy group, 1-phenyltetrazol-5-oxy, 2-tetrahydropyranyloxy), acyloxy group (preferably formyloxy group, substituted or unsubstituted alkyl having 2 to 30 carbon atoms) A carbonyloxy group, a substituted or unsubstituted arylcarbonyloxy group having 6 to 30 carbon atoms, for example, formyloxy, acetyloxy, pivaloyloxy, stearoyloxy, benzoyloxy, p-methoxyphenylcarbonyloxy), a carbamoyloxy group (preferably A substituted or unsubstituted carbamoyloxy group having 1 to 30 carbon atoms, for example, N, N-dimethylcarbamoyloxy, N, N-diethylcarbamoyloxy,
Morpholinocarbonyloxy, N, N-di-n-octylaminocarbonyloxy, Nn-octylcarbamoyloxy), alkoxycarbonyloxy group (preferably substituted or unsubstituted alkoxycarbonyloxy group having 2 to 30 carbon atoms, for example, Methoxycarbonyloxy, ethoxycarbonyloxy, t-butoxycarbonyloxy, n-octylcarbonyloxy), an aryloxycarbonyloxy group (preferably a substituted or unsubstituted aryloxycarbonyloxy group having 7 to 30 carbon atoms, for example, phenoxy Carbonyloxy, p-
Methoxyphenoxycarbonyloxy, pn-hexadecyloxyphenoxycarbonyloxy), amino group (preferably amino group, substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, substituted or unsubstituted having 6 to 30 carbon atoms) A substituted anilino group, for example, amino, methylamino, dimethylamino, anilino, N-methyl-anilino, diphenylamino), an ammonio group (preferably an ammonio group, substituted or unsubstituted alkyl having 1 to 30 carbon atoms, aryl, An ammonium group substituted with a heterocyclic ring, for example, trimethylammonio, triethylammonio, diphenylmethylammonio), an acylamino group (preferably a formylamino group, a substituted or unsubstituted alkylcarbonylamino group having 1 to 30 carbon atoms, With 6 to 30 carbon atoms A substituted or unsubstituted arylcarbonylamino group, for example, formylamino, acetylamino, pivaloylamino, lauroylamino, benzoylamino, 3,4,5-tri-n-octyloxyphenylcarbonylamino), aminocarbonylamino group (preferably A substituted or unsubstituted aminocarbonylamino having 1 to 30 carbon atoms, for example, carbamoylamino,
N, N-dimethylaminocarbonylamino, N, N-diethylaminocarbonylamino, morpholinocarbonylamino), alkoxycarbonylamino group (preferably substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms, for example, methoxycarbonylamino,
Ethoxycarbonylamino, t-butoxycarbonylamino, n-octadecyloxycarbonylamino, N-
Methyl-methoxycarbonylamino), an aryloxycarbonylamino group (preferably a substituted or unsubstituted aryloxycarbonylamino group having 7 to 30 carbon atoms, for example, phenoxycarbonylamino, p-chlorophenoxycarbonylamino, mn- Octyloxyphenoxycarbonylamino), a sulfamoylamino group (preferably a substituted or unsubstituted sulfamoylamino group having 0 to 30 carbon atoms, for example, sulfamoylamino, N, N-dimethylaminosulfonylamino, N −
n-octylaminosulfonylamino), alkyl and arylsulfonylamino groups (preferably substituted or unsubstituted alkylsulfonylamino having 1 to 30 carbon atoms, substituted or unsubstituted arylsulfonylamino having 6 to 30 carbon atoms, for example, methyl Sulfonylamino,
Butylsulfonylamino, phenylsulfonylamino,
2,3,5-trichlorophenylsulfonylamino, p
-Methylphenylsulfonylamino), a mercapto group,
An alkylthio group (preferably a substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms such as methylthio,
Ethylthio, n-hexadecylthio), an arylthio group (preferably substituted or unsubstituted arylthio having 6 to 30 carbon atoms, for example, phenylthio, p-chlorophenylthio, m-methoxyphenylthio), a heterocyclic thio group (preferably carbon number 2 to 30 substituted or unsubstituted heterocyclic thio groups, for example, 2-benzothiazolylthio,
1-phenyltetrazol-5-ylthio), a sulfamoyl group (preferably a substituted or unsubstituted sulfamoyl group having 0 to 30 carbon atoms, for example, N-ethylsulfamoyl, N- (3-dodecyloxypropyl) sulfamoyl, N , N-dimethylsulfamoyl, N-acetylsulfamoyl, N-benzoylsulfamoyl,
N- (N′-phenylcarbamoyl) sulfamoyl), sulfo group, alkyl and arylsulfinyl group (preferably substituted or unsubstituted alkylsulfinyl group having 1 to 30 carbon atoms, substituted or unsubstituted arylsulfinyl having 6 to 30 carbon atoms) Groups such as methylsulfinyl, ethylsulfinyl, phenylsulfinyl, p
-Methylphenylsulfinyl), alkyl and arylsulfonyl groups (preferably substituted or unsubstituted alkylsulfonyl groups having 1 to 30 carbon atoms, substituted or unsubstituted arylsulfonyl groups having 6 to 30 carbon atoms, for example, methylsulfonyl, ethylsulfonyl) Phenylsulfonyl, p-methylphenylsulfonyl), acyl group (preferably formyl group, substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms, carbon atom Number 4 to 3
A heterocyclic carbonyl group bonded to the carbonyl group at 0 substituted or unsubstituted carbon atoms, for example, acetyl,
Pivaloyl, 2-chloroacetyl, stearoyl, benzoyl, p-n-octyloxyphenylcarbonyl,
2-pyridylcarbonyl, 2-furylcarbonyl), an aryloxycarbonyl group (preferably a substituted or unsubstituted aryloxycarbonyl group having 7 to 30 carbon atoms, for example, phenoxycarbonyl, o-chlorophenoxycarbonyl, m-nitrophenoxy) Carbonyl, p
-T-butylphenoxycarbonyl), an alkoxycarbonyl group (preferably a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms, for example, methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl, n-octadecyloxycarbonyl), carbamoyl Groups (preferably substituted or unsubstituted carbamoyl having 1 to 30 carbon atoms such as carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N,
N-di-n-octylcarbamoyl, N- (methylsulfonyl) carbamoyl), aryl and heterocyclic azo groups (preferably substituted or unsubstituted arylazo groups having 6 to 30 carbon atoms, substituted or unsubstituted having 3 to 30 carbon atoms) Substituted heterocyclic azo groups, for example, phenylazo, p-chlorophenylazo, 5-ethylthio-1,3,4-thiadiazol-2-ylazo), imide group (preferably N
Succinimide, N-phthalimido), a phosphino group (preferably a substituted or unsubstituted phosphino group having 2 to 30 carbon atoms, for example, dimethylphosphino, diphenylphosphino, methylphenoxyphosphino), a phosphinyl group (preferably, A substituted or unsubstituted phosphinyl group having 2 to 30 carbon atoms, for example, phosphinyl,
Dioctyloxyphosphinyl, diethoxyphosphinyl), phosphinyloxy group (preferably substituted or unsubstituted phosphinyloxy group having 2 to 30 carbon atoms,
For example, diphenoxyphosphinyloxy, dioctyloxyphosphinyloxy), a phosphinylamino group (preferably a substituted or unsubstituted phosphinylamino group having 2 to 30 carbon atoms, for example, dimethoxyphosphinylamino , Dimethylaminophosphinylamino), a phospho group, a silyl group (preferably a substituted or unsubstituted silyl group having 3 to 30 carbon atoms, for example, trimethylsilyl, t-butyldimethylsilyl, phenyldimethylsilyl), a hydrazino group ( Preferably, a substituted or unsubstituted hydrazino group having 0 to 30 carbon atoms, such as trimethylhydrazino, a ureido group (preferably a substituted or unsubstituted ureido group having 0 to 30 carbon atoms, such as N, N
-Dimethylureido).

Further, two Ws are taken together to form a ring (aromatic or non-aromatic hydrocarbon ring or heterocyclic ring. These can be further combined to form a polycyclic fused ring.
For example, benzene ring, naphthalene ring, anthracene ring, quinoline ring, phenanthrene ring, fluorene ring, triphenylene ring, naphthacene ring, biphenyl ring, pyrrole ring,
Furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, indolizine ring, indole ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinolidine ring, quinoline ring , A phthalazine ring,
Naphthyridine ring, quinoxaline ring, quinoxazoline ring,
A quinoline ring, a carbazole ring, a phenanthridine ring, an acridine ring, a phenanthroline ring, a thianthrene ring, a chromene ring, a xanthene ring, a phenoxatiin ring, a phenothiazine ring, and a phenazine ring. ) May have a condensed structure.

Among the above substituents W, those having a hydrogen atom may be removed and further substituted with the above group. Examples of such substituents include -CONHS
O ₂ - group (sulfonylcarbamoyl group, a carbonyl sulfamoyl group), - CONHCO- group (carbonylation carbamoyl group), - SO ₂ NHSO ₂ - group (sulfonylsulfamoyl group), and the like. More specifically, an alkylcarbonylaminosulfonyl group (eg, acetylaminosulfonyl), an arylcarbonylaminosulfonyl group (eg, benzoylaminosulfonyl group),
Examples thereof include an alkylsulfonylaminocarbonyl group (for example, methylsulfonylaminocarbonyl) and an arylsulfonylaminocarbonyl group (for example, p-methylphenylsulfonylaminocarbonyl).

Z ₁ represents an atomic group necessary for forming a nitrogen-containing heterocyclic ring in which an aromatic hydrocarbon or an aromatic heterocyclic ring is condensed, and preferably represents an aromatic hydrocarbon or an aromatic heterocyclic ring. It represents an atomic group necessary for forming a condensed 5- or 6-membered nitrogen-containing heterocyclic ring.

An aromatic hydrocarbon condensed in Z ₁ ,
Or as an aromatic heterocycle, any of which may be
They can be further combined to form a polycyclic fused ring. For example, benzene ring, naphthalene ring, anthracene ring, quinoline ring, phenanthrene ring, fluorene ring, triphenylene ring, naphthacene ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring,
Thiazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, indolizine ring, indole ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinolidine ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinoxazoline ring Quinoline ring, carbazole ring, phenanthridine ring, acridine ring, phenanthroline ring, thianthrene ring, chromene ring, xanthene ring, phenoxatiin ring, phenothiazine ring, phenazine ring. Preferably, a benzene ring, a naphthalene ring, a pyrrole ring, a furan ring, a thiophene ring, an indole ring, a benzofuran ring, a benzothiophene ring, more preferably a benzene ring, a naphthalene ring, and most preferably a naphthalene ring .

In Z ₁ , the nitrogen-containing heterocycle includes thiazole nucleus, oxazole nucleus, selenazole nucleus, tellurazole nucleus, pyrrole nucleus, imidazole nucleus, 2-pyridine nucleus, 4-pyridine nucleus, oxadiazole nucleus, thiadiazole nucleus, pyrimidine Although nuclei and the like can be mentioned, preferably a thiazole nucleus, an oxazole nucleus, a selenazole nucleus, a tellurazole nucleus, a pyrrole nucleus, an imidazole nucleus, more preferably a thiazole nucleus, an oxazole nucleus,
An imidazole nucleus, particularly preferably a thiazole nucleus or an oxazole nucleus, and most preferably a thiazole nucleus.

The aromatic hydrocarbon represented by Z ₁ or the nitrogen-containing heterocyclic ring in which the aromatic heterocyclic ring is condensed may be substituted with a substituent (for example, the aforementioned W).

Specific examples of the heterocyclic ring formed by Z ₁ include US Pat. No. 5,340,694, Nos. 23-24.
Among the examples of Z ₁₁ , Z ₁₂ , Z ₁₃ , Z ₁₄ , and Z _{16 in} the column, those satisfying the necessary conditions for Z ₁ can be mentioned.

R ₁ and R ₂ are an alkyl group, an aryl group, and a heterocyclic group, and specifically include, for example, carbon atoms 1 to 18, preferably 1 to 7, particularly preferably 1 to 7.
To 4 unsubstituted alkyl groups (eg, methyl, ethyl,
Propyl, isopropyl, butyl, isobutyl, hexyl, octyl, dodecyl, octadecyl), 1 carbon atom
To 18, preferably 1 to 7, particularly preferably 1 to 4, substituted alkyl groups such as the above-mentioned W-substituted alkyl groups as substituents. In particular, the above-described alkyl group having an acid group is preferable. Preferably, an aralkyl group (e.g., benzyl, 2-phenylethyl), an unsaturated hydrocarbon group (e.g., an allyl group, a vinyl group, that is, the substituted alkyl group also includes an alkenyl group and an alkynyl group), hydroxy Alkyl group (for example,
2-hydroxyethyl, 3-hydroxypropyl), carboxyalkyl group (for example, 2-carboxyethyl,
3-carboxypropyl, 4-carboxybutyl, carboxymethyl), an alkoxyalkyl group (for example, 2-
Methoxyethyl, 2- (2-methoxyethoxy) ethyl), aryloxyalkyl group (eg, 2-phenoxyethyl, 2- (1-naphthoxy) ethyl), alkoxycarbonylalkyl group (eg, ethoxycarbonylmethyl, 2-benzyloxycarbonylethyl) ), An aryloxycarbonylalkyl group (eg, 3-phenoxycarbonylpropyl), an acyloxyalkyl group (eg,
-Acetyloxyethyl), acylalkyl group (eg, 2-acetylethyl), carbamoylalkyl group (eg, 2-morpholinocarbonylethyl), sulfamoylalkyl group (eg, N, N-dimethylsulfamoylmethyl), sulfoalkyl group (eg, , 2-sulfoethyl, 3-sulfopropyl, 3-sulfobutyl, 4-sulfobutyl, 2- [3-sulfopropoxy] ethyl, 2-
Hydroxy-3-sulfopropyl, 3-sulfopropoxyethoxyethyl), sulfoalkenyl group, sulfatoalkyl group (for example, 2-sulfatoethyl group, 3-sulfatopropyl, 4-sulfatobutyl), heterocyclic-substituted alkyl Group (for example, 2- (pyrrolidin-2-one-1)
-Yl) ethyl, tetrahydrofurfuryl), alkylsulfonylcarbamoylalkyl group (eg, methanesulfonylcarbamoylmethyl group), acylcarbamoylalkyl group (eg, acetylcarbamoylmethyl group), acylsulfamoylalkyl group (eg, acetylsulfamoylmethyl group) ), An alkylsulfonylsulfamoylalkyl group (eg, a methanesulfonylsulfamoylmethyl group)}, an unsubstituted aryl group having 6 to 20, preferably 6 to 10, and more preferably 6 to 8 carbon atoms (eg, Phenyl group, 1 naphthyl group),
A substituted aryl group having 6 to 20 carbon atoms, preferably 6 to 10 carbon atoms, and more preferably 6 to 8 carbon atoms (for example, an aryl group substituted by W described above as an example of a substituent. Is a p-methoxyphenyl group, p
-Methylphenyl group, p-chlorophenyl group and the like. ), An unsubstituted heterocyclic group having 1 to 20 carbon atoms, preferably 3 to 10 carbon atoms, more preferably 4 to 8 carbon atoms (eg, 2-furyl group, 2-thienyl group, 2-pyridyl group, 3-pyrazolyl, 3-iso Oxazolyl, 3-isothiazolyl, 2-imidazolyl, 2-oxazolyl, 2-thiazolyl, 2-pyridyl, 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, the above-mentioned W-substituted heterocyclic group mentioned as an example of the substituent). Specific examples include a 5-methyl-2-thienyl group and a 4-methoxy-2-pyridyl group.

The substituent represented by R ₁ and R ₂ is preferably an unsubstituted alkyl group or a substituted alkyl group. More preferably, it is an alkyl group having an acid group.

Here, the acid group will be described. An acid group is a group having a dissociable proton. Specifically, for example, a sulfo group, a carboxyl group, a sulfato group, -CO
NHSO ₂ - group (sulfonylcarbamoyl group, a carbonyl sulfamoyl group), - CONHCO- group (carbonylation carbamoyl group), - SO ₂ NHSO ₂ - group (sulfonylsulfamoyl group), a sulfonamido group, a sulfamoyl group, a phosphato group , Phosphono groups, boronic acid groups, phenolic hydroxyl groups, etc.
Some groups include groups from which protons are dissociated. For example, a proton dissociable acidic group capable of dissociating 90% or more between pH 5 and 11 is preferable. More preferably a sulfo group,
Carboxyl group, -CONHSO ₂ - group, -CONHC3H6N
O- group, -SO ₂ NHSO ₂ - a group.

As the alkyl group having an acid group, those mentioned above as specific examples are preferably used. Preferred are a 3-sulfopropyl group, a 4-sulfobutyl group,
A 3-sulfobutyl group, a 2-sulfoethyl group, a carboxymethyl group, a carboxyethyl group, a carboxypropyl group, and a methanesulfonylcarbamoylmethyl group.

Further, as preferred R ₁ and R ₂ , the following 1, 2
There are two cases. More preferably, the case of 2. When both R ₁ and R ₂ are sulfoalkyl groups, preferably a 3-sulfopropyl group, a 4-sulfobutyl group, a 3-sulfobutyl group, a 2-sulfoethyl group,
More preferably, it is a 3-sulfopropyl group. 2. At least one of R ₁ and R ₂ is an alkyl group having a sulfo group, and the other is an alkyl group having an acid group other than a sulfo group. Preferably, at least one of R ₁ and R ₂ is a sulfo group The other is a carboxyl group, -CO
NHSO ₂ — group, —CONHCO— group, or —SO ₂ NH
This is the case when the alkyl group has an SO ₂ — group. The alkyl group having a sulfo group is preferably a 3-sulfopropyl group, a 4-sulfobutyl group, a 3-sulfobutyl group,
-Sulfoethyl group, more preferably a 3-sulfopropyl group. Particularly preferred as the alkyl group having an acid group other than the sulfo group are a carboxymethyl group and a methanesulfonylcarbamoylmethyl group.

X₁, X_Two, And X_ThreeIs an oxygen atom, a sulfur atom
Represents a selenium atom, a nitrogen atom, or a carbon atom.
X₁, X_Two, And X_ThreeIs preferably X₁Is a sulfur atom
Yes, X _TwoIs a carbon atom and X_ThreeIs a nitrogen atom or carbon
This is the case when it is an atom. V₁, V_Two, And V_ThreeIs a hydrogen source
Represents a substituent or a substituent. Where V₁, V_Two, And V_ThreeIs
They cannot combine with each other to form an aromatic ring.
No. Examples of the substituent include the aforementioned W. V
₁, V_Two, And V_ThreeIs preferably a hydrogen atom, or
An aromatic substituent, more preferably a hydrogen atom, carbon
It is a substituted or unsubstituted alkyl group of Formulas 1 to 4. X₁But
Q for carbon atom₁Is 2, in the case of a nitrogen atom q₁Is 1, it
Q for atoms other than₁Is 0. X_TwoIs a carbon atom
q_TwoIs 1, otherwise q_TwoIs 0. X_ThreeBut
Q for carbon atom_ThreeIs 1, otherwise q_ThreeIs 0
It is. q₁Is 2 when V₁Are repeated but are identical
Need not be.

L ₁ , L ₂ , L ₃ , L ₄ and L ₅ each independently represent a methine group. The methine groups represented by L _{1 to} L ₅ may have a substituent, and examples of the substituent include the aforementioned W. For example, substituted or unsubstituted carbon atoms of 1 to 1
5, preferably an alkyl group having 1 to 10 carbon atoms, particularly preferably 1 to 5 carbon atoms (eg, methyl, ethyl,
-Carboxyethyl), a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, preferably 6 to 15 carbon atoms, more preferably 6 to 10 carbon atoms (eg, phenyl, o-
Carboxyphenyl), a substituted or unsubstituted heterocyclic group having 3 to 20 carbon atoms, preferably 4 to 15 carbon atoms, more preferably 6 to 10 carbon atoms (eg, N, N-dimethylbarbituric acid group), a halogen atom , (Eg, chlorine, bromine, iodine, fluorine), an alkoxy group having 1 to 15 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms (eg, methoxy, ethoxy), 0 to 15 carbon atoms, An amino group having preferably 2 to 10 carbon atoms, more preferably 4 to 10 carbon atoms (eg, methylamino, N,
N-dimethylamino, N-methyl-N-phenylamino, N-methylpiperazino), an alkylthio group having 1 to 15, preferably 1 to 10, more preferably 1 to 5 carbon atoms (eg, methylthio, ethylthio) , Having 6 to 20 carbon atoms, preferably 6 to 1 carbon atoms
2, more preferably an arylthio group having 6 to 10 carbon atoms (eg, phenylthio, p-methylphenylthio) and the like. It may also form a ring with another methine group, or another group (for example, Z ₁ , Z ₂ , R ₁ , R _2, etc.)
And may form a ring together.

L ₄ and L ₅ are preferably unsubstituted methine groups.

N ₁ represents 0, ₁ , 2, 3 or 4. It is preferably 0, 1, 2, 3, and more preferably 0,
1, 2, particularly preferably 0, 1 and most preferably 1. When n ₁ is 2 or more, the methine group is repeated but need not be the same.

When n ₁ is 0, L ₃ is preferably an unsubstituted methine group. When n ₁ is 1, L ₁ and L ₃ are preferably unsubstituted methine groups, and L ₄ is preferably an unsubstituted methine group or an alkyl-substituted methine group.

P ₁ represents 0 or 1. Preferably it is 0.

M ₁ is included in the formula to indicate the presence of a cation or an anion when necessary to neutralize the ionic charge of the dye. Typical cations include inorganic cations such as hydrogen ion (H ⁺ ), alkali metal ions (eg, sodium ion, potassium ion, lithium ion), alkaline earth metal ions (eg, calcium ion), and ammonium ions (eg, Organic ions such as ammonium ion, tetraalkylammonium ion, triethylammonium ion, pyridinium ion, ethylpyridinium ion, and 1,8-diazabicyclo [5.4.0] -7-undecenium ion. The anion may be either an inorganic anion or an organic anion, and may be a halogen anion (for example, a fluorine ion, a chloride ion, an iodine ion), a substituted arylsulfonate ion (for example, p-toluenesulfonic acid ion, p-toluene ion). Chlorobenzenesulfonate ion), aryldisulfonate ion (for example, 1,
3-benzenesulfonic acid ion, 1,5-naphthalenedisulfonic acid ion, 2,6-naphthalenedisulfonic acid ion), alkyl sulfate ion (eg, methyl sulfate ion), sulfate ion, thiocyanate ion, perchlorate ion, tetrafluoro ion Borate ion, picrate ion,
An acetate ion and a trifluoromethanesulfonic acid ion are mentioned. Further, another dye having a charge opposite to that of the ionic polymer or the dye may be used. Moreover, CO ₂ ^-, SO
₃ ^- is, when having a proton as a counter ion CO
_It can also be described as ₂ H or SO ₃ H.

M ₁ represents a number of 0 or more necessary for balancing the electric charges, preferably a number of 0 to 4, more preferably a number of 0 to 1 when forming a salt in the molecule. Is 0.

Z ₂ represents an oxygen atom, a sulfur atom, a selenium atom, a nitrogen atom (NR ₁₁ ), or a carbon atom (CR
₁₂ R ₁₃ ). Here, R ₁₁ , R ₁₂ , and R ₁₃ are a hydrogen atom or a substituent (for example, the aforementioned W), and are preferably a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. Examples of the alkyl group, the aryl group, and the heterocyclic group include the same as those described above for R ₁ and R ₂ . More preferably, it is an alkyl group.

Z ₂ is preferably an oxygen atom, a sulfur atom, or a nitrogen atom, more preferably an oxygen atom or a sulfur atom, and particularly preferably a sulfur atom.

V ₄ , V ₅ , V ₆ and V ₇ are each a hydrogen atom,
Or a substituent. However, these substituents may form a ring together. For example, the aforementioned W (for example, a hydrogen atom, an alkyl group, an aromatic group, a halogen atom, an acylamino group, a carbamoyl group, a carboxyl group, an alkoxy group, or a ring formation) can be mentioned.

As V ₄ , V ₅ , V ₆ and V ₇ , it is preferable to form the following ring (1) or to substitute the halogen atom or aromatic group (2).

(1) When a ring is formed. It is preferred that V ₆ and V ₇ , or V ₅ and V ₆ together form a ring, more preferably V ₆ and V ₇ together form a ring . 5 for the ring
A 6-membered or 6-membered ring is preferred, and an aromatic ring is more preferred.
Note that when V ₆ and V ₇ form an aromatic ring together, V ₄ and V ₅ are preferably hydrogen atoms, and when V ₅ and V ₆ form an aromatic ring together Is preferably V ₄ and V ₇ is preferably a hydrogen atom.

The aromatic ring may be either an aromatic hydrocarbon or an aromatic heterocyclic ring, and these can be further combined to form a polycyclic fused ring. For example, benzene ring, naphthalene ring, anthracene ring, quinoline ring, phenanthrene ring, fluorene ring, triphenylene ring, naphthacene ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring,
Pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, indolizine ring, indole ring, benzofuran ring,
Benzothiophene ring, isobenzofuran ring, quinolidine ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinoxazoline ring, quinoline ring, carbazole ring, phenanthridine ring, acridine ring, phenanthroline ring, thianthrene ring, chromene ring, xanthene Ring, phenoxathiin ring, phenothiazine ring, phenazine ring. Preferred are a benzene ring, a pyrrole ring, a furan ring, and a thiophene ring, and more preferred is a benzene ring. The above aromatic ring may be further substituted with a substituent (for example, the above-mentioned substituent W). However, it is preferable that the above aromatic ring is unsubstituted. (2) When a halogen atom or an aromatic group is substituted. It is preferred that V ₆ is a halogen atom or an aromatic group. In this case, V ₄ , V ₅ and V ₇ are preferably hydrogen atoms. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and preferably a chlorine atom, a bromine atom and an iodine atom. Examples of the aromatic group include a hydrocarbon aromatic group and a heteroaromatic group. These are groups having a polycyclic fused ring in which a hydrocarbon aromatic ring and a heteroaromatic ring are fused together, or a polycyclic fused ring structure in which an aromatic hydrocarbon ring and an aromatic heterocycle are combined. Is also good. As the aromatic ring contained in the aromatic group, preferably, benzene, naphthalene, anthracene, phenanthrene, fluorene, triphenylene, naphthacene, biphenyl, pyrrole, furan, thiophene, imidazole, oxazole, thiazole, pyridine, pyrazine,
Pyrimidine, pyridazine, indolizine, indole,
Benzofuran, benzothiophene, isobenzofuran,
Examples include quinolidine, quinoline, phthalazine, naphthyridine, quinoxaline, quinoxazoline, quinoline, carbazole, phenanthridine, acridine, phenanthroline, thianthrene, chromene, xanthene, phenoxatiin, phenothiazine, phenazine and the like.
More preferred are benzene, pyrrole, furan, and thiophene, and particularly preferred is benzene (that is, a phenyl group). The above-mentioned aromatic group may be further substituted by a substituent (for example, the aforementioned substituent W). However, it is preferable that the above aromatic group is unsubstituted.

V ₁ ′, V ₂ ′ and V ₃ ′ are a hydrogen atom,
Or a non-aromatic substituent. However, V ₁ ′, V ₂ ′, and V ₃ ′ do not combine with each other to form an aromatic ring. Examples of the substituent include the aforementioned W. More preferred are a hydrogen atom and a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, and particularly preferred are a hydrogen atom and a methyl group.

V_Four’, V_Five’, V₆’And V₇’Is hydrogen
Represents an atom or a substituent. Where V _Five’And V₆’Or V
₆’And V₇′ Together form a 5- or 6-membered ring
good. V_Four’, V_Five’, V₆’And V₇’
V_Four, V_Five, V₆, And V₇Similar to (eg, hydrogen
Atom, alkyl group, aromatic group, halogen atom, acyl group
Mino group, carbamoyl group, carboxyl group, alkoxy
Group or ring formation), and the same is preferable.

R ₁₀ represents a hydrogen atom or an alkyl group. When Z ₂ is a nitrogen atom, R ₁₀ represents a hydrogen atom. The alkyl group may be substituted or unsubstituted, but is preferably an unsubstituted alkyl group, more preferably a methyl group, an ethyl group, or a propyl group, and particularly preferably an ethyl group.

N ₁ ′ represents 0 or 1, and preferably 1
It is.

R ₁ ′ and R ₂ ′ represent an alkyl group substituted with an acid group. Examples of R ₁ ′ and R ₂ ′ are the same as the alkyl group substituted with the acid group described for R ₁ and R ₂ , and the same is preferable.

Next, specific examples of the compound (sensitizing dye) represented by the general formula (I), (II) or (III) described in detail in the description of the embodiment of the invention are shown below. Of course, the present invention is not limited to these.

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The dye of the present invention is FM Hammer.
(FMHarmer), Heterocyclic Compounds
Cyanine soybeans and related compounds
(Heterocyclic Compounds-Cyanine Dyes and Related C
ompounds) ", John Willy and Sons
n Wiley & Sons)-New York, London, 1
964, DMSturmer, Heterocyclic Compounds-Special Topics in Heterocyclic Chemistry (H
eterocyclic Compounds-Special topics in heterocycl
ic chemistry ", Chapter 18, Section 14, 482-515, John Wiley and Sons (John Wi
ley & Sons)-New York, London, 197
7th year, "Rodd's Chemistry of Carbon Compounds"
2nd.Ed.vol.IV, partB, 1977, Chapter 15, Chapter 369
422, Elsevier Science Public
Company Inc. (Elsevier Science Publishing Com
pany Inc.), New York, German patent 19,96
It can be synthesized based on the method described in Japanese Patent No. 0,279A1.

In the present invention, not only the sensitizing dye of the present invention but also other sensitizing dyes other than the present invention may be used or used in combination. Preferred examples of the dye used include a cyanine dye, a merocyanine dye, a rhodocyanine dye, a trinuclear merocyanine dye, a tetranuclear merocyanine dye, an allopolar dye, a hemicyanine dye, and a styryl dye. More preferred are cyanine dyes, merocyanine dyes and rhodacyanine dyes, and particularly preferred are cyanine dyes. For more information on these dyes, see FMHarmer, Heterocyclic Compounds-Cyanine Soybeans and Related.
Compounds (Heterocyclic Compounds-Cyanine Dyes a
nd Related Compounds), John Wiley & Sons-New York,
London, 1964, D.M.
M. Sturmer), Heterocyclic Compounds-Special topics in Heterocyclic Compounds-Special topics i
n heterocyclic chemistry) ", Chapter 18, Section 14,
Nos. 482 to 515. Preferred dyes include US Pat. No. 5,994,051 No. 32
And sensitizing dyes represented by the general formulas and specific examples described in US Pat. No. 5,747,236, pages 30 to 39. The general formulas of preferred cyanine dyes, merocyanine dyes and rhodacyanine dyes are described in U.S. Pat. No. 5,340,694, columns 21 to 22, (XI),
(XII), (XIII) (where n1
The number of 2, n15, n17, and n18 is not limited and is an integer of 0 or more (preferably 4 or less). ).

Although these sensitizing dyes may be used alone,
Two or more types may be used, and two or more types (often used for supersensitization) are described in U.S. Pat. No. 2,688,5.
No. 45, No. 2,977,229, No. 3,397,06
No. 0, 3,522,052, 3,527,641
No. 3,617,293 and 3,628,964
No. 3,666,480, 3,672,898
No. 3,679,428 and 3,303,377
Nos. 3,769,301 and 3,814,609
No. 3,837,862, No. 4,026,707
No. 1,344,281 and 1,507,8
No. 03, JP-B-43-49336, JP-B-53-1237
5, JP-A-52-110618 and JP-A-52-11099.
No. 25, etc.

In addition to the sensitizing dye, the emulsion may contain a dye which does not itself have a spectral sensitizing effect or a substance which does not substantially absorb visible light and exhibits supersensitization.

Supersensitizers useful for spectral sensitization in the present invention (for example, pyrimidylamino compounds, triazinylamino compounds, azolium compounds, aminostyryl compounds, aromatic organic acid formaldehyde condensates, azaindene compounds, cadmium salts) And combinations of supersensitizers and sensitizing dyes are described, for example, in US Pat. No. 3,511,66.
No. 4, No. 3,615,613, No. 3,615,632
Nos. 3,615,641, 4,596,767
Nos. 4,945,038 and 4,965,182
Nos. 4,965,182 and 2,933,390
Nos. 3,635,721 and 3,743,510
Nos. 3,617,295, 3,635,721, etc., and the method described in the above-mentioned patents is preferred for the use thereof.

It has been recognized that the timing at which the sensitizing dye of the present invention (and other sensitizing dyes and supersensitizers) is added to the silver halide emulsion of the present invention has been useful. During the preparation of the emulsion. For example, US Pat. Nos. 2,735,766 and 3,6
28,960, 4,183,756, 4,22
5,666, JP-A-58-184142, 60-
As disclosed in, for example, Japanese Patent No. 196749, the stage before silver halide grain formation step and / or before desalting, the period during and / or after desalting and before the start of chemical ripening,
As disclosed in JP-A-58-113920 and the like, any time during or immediately before chemical ripening, during a process, or after chemical ripening and before coating, the emulsion may be added at any time before the coating. May be. Also, U.S. Pat.
As disclosed in US Pat. No. 5,666, JP-A-58-7629, etc., the same compound may be used alone or in combination with a compound having a different structure, for example, during the particle forming step and during the chemical ripening step or during the chemical ripening step. It may be added separately after completion, or before or after chemical ripening or during the process and after completion, and may be added by changing the kind of compound and compound combination to be added separately. May be.

The addition amount of the sensitizing dye of the present invention (the same applies to other sensitizing dyes and supersensitizers) differs depending on the shape and size of silver halide grains, and any addition amount may be used. Is preferably 1 × 10 ^-8 to 1 × 10 ^-1 mol, more preferably 1 × 10 ^-1 mol, per mol of silver halide.
× can be used in 10 ^-6 to 8 × 10 ^-3 mol. For example, when the silver halide grain size is 0.2 to 1.3 μm, 2 × 10 ^{−6 to} 3 × 3 per mol of silver halide.
An addition amount of 5 × 10 ⁻³ mol is preferable, and 7.5 × 10 ⁻⁶ to
An addition amount of 1.5 × 10 ⁻³ mol is more preferred.

The sensitizing dye of the present invention (the same applies to other sensitizing dyes and supersensitizers) can be directly dispersed in an emulsion. These can be first dissolved in an appropriate solvent, for example, methyl alcohol, ethyl alcohol, methyl cellosolve, acetone, water, pyridine or a mixed solvent thereof, and added to the emulsion in the form of a solution. At this time, additives such as a base, an acid, and a surfactant can be made to coexist. Also, ultrasonic waves can be used for dissolution. As a method for adding the compound, as described in US Pat. No. 3,469,987, the compound is dissolved in a volatile organic solvent, and the solution is dispersed in a hydrophilic colloid. As described in JP-B-46-24185, and a method of dispersing in a water-soluble solvent and adding this dispersion to the emulsion, described in U.S. Pat. No. 3,822,135. A method of dissolving a compound in a surfactant and adding the solution to an emulsion, and dissolving using a compound that causes a red shift as described in JP-A-51-74624, and dissolving the solution in the emulsion. As described in JP-A-50-80826, a method in which a compound is dissolved in an acid substantially free of water and the solution is added to an emulsion is used. In addition, US Pat.
No. 2,343, No. 3,342,605, No. 2,99
Nos. 6,287, 3,429,835 and the like can also be used.

The silver halide emulsion used in the present invention is usually chemically sensitized. As the chemical sensitization method, a gold sensitization method using a so-called gold compound (for example, US Pat. No. 2,448,06)
0, 3,320,069), iridium, platinum,
Sensitization with metals such as rhodium and palladium (for example, U.S. Pat. Nos. 2,448,060 and 2,566,245)
No. 2,566,263) and a sulfur sensitization method using a sulfur-containing compound (for example, US Pat. No. 2,222,264).
), Selenium sensitization using a selenium compound, tellurium sensitization using a tellurium compound, or reduction sensitization using a tin salt, thiourea dioxide, polyamine or the like (for example, US Pat. Nos. 2,487,850 and 2,518). , 698 and 2,521, 925). These sensitization methods can be used alone or in combination. In the present invention, it is more preferable to use selenium sensitization, sulfur sensitization, and gold sensitization in combination.

In the emulsion of the present invention, selenium sensitization is used as a sensitization method. When the sensitizing dye of the present invention is used in combination with selenium sensitization, a silver halide photographic light-sensitive material having specifically high sensitivity and good latent image preservability can be provided.

The silver halide emulsion used in the present invention is preferably chemically sensitized with a selenium sensitizer. In the present invention, at least the selenium-sensitized emulsion containing the compound of the formula (I) is preferably used. It must be contained in one silver halide emulsion layer. As the selenium sensitizer, a selenium compound disclosed in a conventionally known patent can be used. That is, the emulsion is usually used by adding an unstable selenium compound and / or a non-unstable selenium compound and stirring the emulsion at a high temperature, preferably at 40 ° C. or higher for a certain period of time. Examples of unstable selenium compounds include, for example, U.S. Pat. Nos. 3,297,446 and 3,297,448.
No., JP-B-43-13489, and JP-A-44-15748
No., JP-A-4-25832, JP-A-4-109240,
4-147250, 4-271341, 5-
No. 40324, No. 5-224332, No. 5-2243
Nos. 33, 5-11385, 6-43576, 6-75328, 6-175258, 6-17
No. 5259, No. 6-180478, No. 6-20818
It is preferable to use the compounds described in JP-A Nos. 4 and 6-208186. Specific labile selenium sensitizers include:
Isoselenocyanates (eg, aliphatic isoselenocyanates such as allyl isoselenocyanate), selenoureas (eg, N, N-dimethylselenourea, N-acetyl-N, N ′, N′-trimethylselenourea, N -Trifluoroacetyl-N, N ', N'-trimethylselenourea), selenoketones, selenoamides (e.g. N,
N-dimethylselenobenzamide, N, N-diethylselenobenzamide), dicarbamoyl selenides (eg, bis (N, N-dimethylcarbamoyl) selenide), bis (alkoxycarbonyl) selenides (eg, bis (n-butoxy) Carbonyl) selenide, bis (benzyloxycarbonyl) selenide), triselenane (eg, 2,4,6-tris (p-methoxyphenyl) triselenane), diselenides, polyselenides, selenium sulfide, selenocarboxylic acids (eg, 2- Selenopropionic acid, 2-selenobutyric acid), selenoesters (for example, p-methoxyselenobenzoic acid O-
Isopropyl ester, p-methoxyselenobenzoic acid
Se- (3′-oxocyclohexyl) ester), diacyl selenides (for example, bis (2,6-dimethoxybenzoyl) selenide, bis (2,4-dimethoxybenzoyl) selenide, bis (3-chloro-2,6-dimethoxybenzoyl) ) Selenides), selenophosphates (e.g., tri-p-tolylselenophosphate), phosphine selenides (e.g., triphenylphosphine selenide, pentafluorophenyl-diphenylphosphine selenide), selenophosphinic esters, selenophosphonic acid Esters and colloidal metal selenium. Preferably, phosphine selenides, selenoamides, dicarbamoyl selenides, bis (alkoxycarbonyl) selenides, and selenoesters are used.

The preferred types of unstable selenium compounds have been described above, but these are not limiting. Skilled artisans say that an unstable selenium compound as a sensitizer for a photographic emulsion is not very important as long as selenium is unstable, and the organic part of the selenium sensitizer molecule is not important. It is generally understood that selenium has no role except to carry it in an unstable form in the emulsion. In the present invention, an unstable selenium compound having such a broad concept is advantageously used.

The non-labile selenium compounds used in the present invention include JP-B-46-4553 and JP-B-52-34.
No. 492 and JP-B-52-34491 are used. Examples of the non-labile selenium compound include selenous acid, potassium selenocyanide, selenazoles, quaternary salts of selenazoles, diaryl selenide, diaryl diselenide, dialkyl selenide, dialkyl diselenide, 2-selenazolidinedione, 2-selenooxazolidinethione and derivatives thereof. Of these selenium compounds, those of the following general formulas (V) and (VI) are preferably used.

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In the formula, Q ¹ and Q ² may be the same or different and each have a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms (eg, methyl, ethyl, t-butyl, adamantyl, t-octyl), A substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms (eg, vinyl, propenyl),
A substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms (eg, benzyl, phenethyl); a substituted or unsubstituted aryl group having 6 to 30 carbon atoms (eg, phenyl, pentafluorophenyl, p-chlorophenyl, m-nitrophenyl, p-octylsulfamoylphenyl, 1-
Naphthyl), a substituted or unsubstituted Hajime Tamaki having from 1 to 30 carbon atoms (for example, pyridyl, thienyl, furyl, ^{imidazolyl), - NR a R b,} -OR c, represents a -SR ^d. R ^a ,
R ^b , R ^c , and R ^d may be the same or different and each represents an alkyl group, an aralkyl group, an aryl group, or a heterocyclic group, and includes the same examples as in Q ¹ . However, ^Ra and ^Rb are a hydrogen atom or a substituted or unsubstituted acyl group having 1 to 30 carbon atoms (for example, acetyl, propanoyl, benzoyl, heptafluorobutanoyl, difluoroacetyl, p-nitrobenzoyl, 1-naphthoyl,
4-trifluoromethylbenzoyl).
Among the compounds represented by the general formula (V), preferred are N, N-dialkylselenourea, N, N, N′-trialkyl-N′-acylselenourea, tetraalkylselenourea, and N, N-dialkyl An arylselenoamide,
N-alkyl and N-aryl-arylselenoamides, specifically, the following compounds.

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In the formula, Q ³ , Q ⁴ and Q ⁵ may be the same or different, and represent a hydrogen atom, a halogen atom (for example, fluorine, chlorine, bromine, iodine), a substituted or unsubstituted C 1-30 carbon atom. Alkyl groups (eg, methyl, ethyl, t-
Butyl, adamantyl, t-octyl), having 2 to 3 carbon atoms
0 substituted or unsubstituted alkenyl groups (for example, vinyl and propenyl), 7 to 30 carbon atoms of a substituted or unsubstituted aralkyl group (for example, benzyl and phenethyl), and 6 to 30 carbon atoms of a substituted or unsubstituted aryl group ( For example, phenyl, pentafluorophenyl, p-chlorophenyl, m-nitrophenyl, p-octylsulfamoylphenyl, 1-naphthyl), a substituted or unsubstituted heterocyclic group having 1 to 30 carbon atoms (eg, pyridyl, thienyl,
Furyl, ^{imidazolyl), - NR e R f,} -OR g, -S
R ^h represents —SeR ⁱ . R ^e , R ^f , R ^g , R ^h , and R
ⁱ may be the same or different and each represents an alkyl group, an aralkyl group, an aryl group or a heterocyclic group,
Similar examples and Q ³ can be mentioned. Among the compounds represented by the general formula (VI), preferred are a trialkylphosphine selenide, a triarylphosphine selenide, a trialkylselenophosphate or a triarylselenophosphate, and specific examples include the following compounds. .

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In addition, it can be preferably selected from selenium compounds 1 to 40 of JP-A-11-15115. More preferably, it is a compound of the above general formula (VI), and further preferably a triarylphosphine selenide or a triarylselenophosphate.

These selenium sensitizers are dissolved in water or an organic solvent such as methanol or ethanol, alone or in a mixed solvent, and added during chemical sensitization. Preferably, it is added before the start of chemical sensitization. The selenium sensitizer used is not limited to one kind, and two or more kinds of the above selenium sensitizers can be used in combination. It is preferable to use a combination of an unstable selenium compound and a non-unstable selenium compound. The amount of the selenium sensitizer to be added varies depending on the activity of the selenium sensitizer to be used, the type and size of silver halide, the ripening temperature and the time, and is preferably 1 × / mol of silver halide in the emulsion. It is at least 10 ^-8 mol. More preferably, it is 1 × 10 ^{−7 to} 5 × 10 ⁻⁵ mol. The temperature of chemical ripening when using a selenium sensitizer is preferably 45 ° C. or higher. More preferably 50 to 8
0 ° C. pAg and pH are arbitrary. For example, p
The effect of the present invention can be obtained in a wide range of H from 4 to 9.

It is sometimes preferable to use selenium sensitization in combination with sulfur sensitization or noble metal sensitization (especially gold sensitization), or a combination thereof. Is preferably used in combination with selenium sensitization, sulfur sensitization and gold sensitization.

The light-sensitive material of the present invention may have at least one light-sensitive layer provided on a 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 and the like described below. As described in DE 1,121,470 or GB 923,045, a plurality of silver halide emulsion layers constituting each unit light-sensitive layer are formed by sequentially exposing two layers of a high-speed emulsion layer and a low-speed emulsion layer toward a support. It is preferable to arrange them so that the degree is low. Also, JP-A-57-112751, 62-200350, 62-2
As described in JP-A Nos. 06541 and 62-206543, a low-speed emulsion layer may be provided on the side farther from the support, and a high-speed emulsion layer may be provided on the side closer to the support. As specific examples, from the farthest side from the support, a low-sensitivity blue-sensitive layer (BL) / a high-sensitivity blue-sensitive layer (BH) / a high-sensitivity green-sensitive layer (GH) / a low-sensitivity green-sensitive layer (GL) / High-sensitivity red-sensitive layer (RH) / low-sensitivity red-sensitive layer (RL), or BH / BL / GL / GH / RH / RL, or BH / BL / GH / GL / RL / RH And so on. Further, as described in JP-B-55-34932, the blue-sensitive layer / GH / RH / GL is arranged from the side farthest from the support.
/ RL can be arranged in this order. JP-A-56-2573
8, as described in JP-A-62-63936, the layers may be arranged in the order of blue-sensitive layer / GL / RL / GH / RH from the side farthest from the support. Also, as described in JP-B-49-15495, the upper layer is the most sensitive silver halide emulsion layer, the middle layer is the silver halide emulsion layer of lower sensitivity, and the lower layer is more sensitive than the middle layer. An example is an arrangement in which a low silver halide emulsion layer is disposed and three layers having different sensitivities are sequentially reduced in sensitivity toward a support. Even when such three layers having different sensitivities are used, as described in JP-A-59-202464, the medium-sensitive emulsion layer / high The layers may be arranged in the order of a light-sensitive emulsion layer / a light-sensitive emulsion layer. In addition, a high-speed emulsion layer / low-speed emulsion layer / medium-speed emulsion layer, or a low-speed emulsion layer / medium-speed emulsion layer / high-speed emulsion layer may be arranged in this order. The arrangement may be changed as described above even in the case of four or more layers. In order to improve color reproducibility, BL, GL, described in US 4,663,271, 4,705,744, 4,707,436, JP-A-62-160448 and 63-89850, are described.
It is preferred that a donor layer (CL) having a multilayer effect having a spectral sensitivity distribution different from that of the main photosensitive layer such as RL is disposed adjacent to or close to the main photosensitive layer.

Preferred silver halides for use in the present invention are silver iodobromide, silver iodochloride, or silver iodochlorobromide containing up to about 30 mole percent 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 crystalline forms such as spheres and plates, twin planes, etc. Or a composite form thereof. Even if the grain size of silver halide is about 0.2 μm or less, the projected area diameter is about
Large-sized grains of up to 10 μm may be used, and polydisperse emulsions or monodisperse emulsions may be used. Silver halide photographic emulsions that can be used in the present invention include, for example, Research Disclosure (hereinafter abbreviated as RD) No. 17643 (December 1978), 22 to 23.
Page, “I. Emulsion preparation and type
s) "and No. 18716 (November 1979), p. 648, ibid.
o.307105 (November 1989), pp.863-865, and Grafkid, "Physics and Chemistry of Photography", published by Paul Montell (P.Gl.
afkides, Chimie et Phisique Photographiques, Paul
Montel, 1967), Duffin, Photographic Emulsion Chemistry, published by Focal Press (GF Duffin, Photographic Emulsion).
Chemistry, Focal Press, 1966), "Production and Coating of Photographic Emulsions", by Zerikman et al., Published by Focal Press (VL
Zelikman, et al., Making and Coating Photographic
Emulsion, Focal Press, 1964). US 3,574,628, 3,65
Monodisperse emulsions described in 5,394 and 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 Gatoff, Photographic Science and Engineering (Gutoff, Photographic Science and Engin).
eering), Vol. 14, pp. 248-257 (1970); US 4,434,22
6, 4,414,310, 4,433,048, 4,439,520 and G
B can be easily prepared by the method described in 2,112,157. The crystal structure may be uniform, the inside and outside may have 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 that Among the internal latent image type emulsions, core / shell type internal latent image type emulsions described in JP-A-63-264740 may be used.
-133542. The thickness of the shell of this emulsion varies depending on the development process and the like, but is preferably 3 to 40 nm,
-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. 187.
16 and No. 307105, and the relevant portions are summarized in the table below. In the light-sensitive material of the present invention, two or more types of emulsions having at least one characteristic different from each other in the grain size, grain size distribution, halogen composition, grain shape and sensitivity of the photosensitive silver halide emulsion are mixed in the same layer. Can be used. U.S. Pat.No.4,082,553.
The silver halide grains covered with the grains according to 4852,
It is preferred to apply colloidal silver to the photosensitive silver halide emulsion layer and / or to the substantially light-insensitive hydrophilic colloid layer. The term “silver halide particles having a fogged inside or surface” refers to silver halide grains that can be uniformly (non-imagewise) developed regardless of the unexposed portions and exposed portions of the photosensitive material. Its preparation is described in US Pat. No. 4,626,498, 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 μm,
Particularly, the thickness is preferably 0.05 to 0.6 μm. The grains may be regular grains or polydisperse emulsions, but may be monodisperse (at least 95% of the weight or the number of silver halide grains).
% Having a particle diameter within ± 40% of the average particle diameter).

In the present invention, it is preferable to use non-photosensitive 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. Fine grain silver halide has an average grain size (average value of projected area equivalent circle diameter)
Is preferably 0.01 to 0.5 μm, more preferably 0.02 to 0.2 μm. 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, benzothiazolium-based, or mercapto-based compound or a zinc compound in advance. Colloidal silver can be contained in the layer containing fine silver halide grains. Coated silver amount of the light-sensitive material of the present invention is preferably 6.0 g / m ² or less, 4.5 g / m ² or less is most preferred.

The photographic additives which can be used in the present invention are also described in the RD, and the relevant places are shown in the following table. Type of additive RD17643 RD18716 RD307105 Chemical sensitizer page 23, page 648, right column, page 866 2. 2. Sensitivity enhancer, page 648, right column 3. Spectral sensitizer, pages 23 to 24, page 648, right column, pages 866 to 868 Super sensitizer, page 649, right column Brightener page 24 page 647 page right column page 868 5. 5. Light absorbers, pages 25 to 26, page 649, right column, page 873 Filters, page 650, left column, dyes, ultraviolet absorbers Binder page 26 page 651 left column pages 873 to 874 7. 7. Plasticizer, page 27 page 650, right column, page 876 Lubricant Coating aid, pages 26 to 27, page 650, right column, pages 875 to 876 Surfactant 9. Static 27 pages 650 pages right column pages 876-877 Inhibitors 10. Matsuto 878-879.

Although various dye-forming couplers can be used in the light-sensitive material of the present invention, the following couplers are particularly preferred. Yellow couplers: couplers represented by formulas (I) and (II) of EP 502,424A; couplers represented by formulas (1) and (2) of EP 513,496A (especially Y-28 on page 18); EP 568,037A A coupler of the formula (I) of claim 1; a coupler of the general formula (I) in column 1, lines 45 to 55 of US 5,066,576;
Couplers represented by general formula (I) in paragraph 0008 of JP-A-4-274425; couplers described in claim 1 on page 40 of EP 498,381A1 (especially D-35 on page 18); formulas on page 4 of EP 447,969A1
Couplers represented by (Y) (especially Y-1 (page 17), Y-54 (41
P.)); US Pat. No. 4,476,219, column 7, lines 36-58, formulas (II)-(I
V) (especially II-17, 19 (column 17), II
-24 (column 19)). Magenta coupler; JP-A-3-39737 (L-
57 (page 11, lower right), L-68 (page 12, lower right), L-77 (page 13, lower right); EP
456,257 A-4 -63 (p.134), A-4 -73, -75 (p.139); EP
486,965 M-4, -6 (p. 26), M-7 (p. 27); EP 571,959A M-4
5 (page 19); JP-A-5-204106 (M-1) (page 6); JP-A-4-36263
Paragraph 0237 of the M-22. Cyan coupler: CX-1,3,4,5,11,12,1 of JP-A-4-204843
4,15 (pages 14 to 16); JP-A-4-43345, C-7,10 (page 35), 3
4, 35 (page 37), (I-1), (I-17) (pages 42 to 43); JP-A-6-67385
A coupler represented by the general formula (Ia) or (Ib) according to claim 1. Polymer couplers: P-1, P-5 in JP-A-2-44345 (page 11).

Examples of couplers in which the coloring dye has a suitable diffusibility include US Pat. No. 4,366,237, GB 2,125,570, EP 96,873B,
Those described in DE 3,234,533 are preferred. Couplers for correcting unnecessary absorption of color-forming dyes are yellow colored cyan couplers represented by the formulas (CI), (CII), (CIII) and (CIV) described on page 5 of EP 456,257A1 (especially on page 84). YC-86), the EP
Yellow colored magenta coupler ExM-7 (202
), EX-1 (page 249), EX-7 (page 251), US 4,833,069
Magenta colored cyan coupler CC-9 (column
8), CC-13 (column 10), (2) of US 4,837,136 (column 8),
Colorless masking couplers of formula (A) in claim 1 of WO 92/11575 (especially the exemplified compounds on pages 36 to 45) are preferred. Examples of couplers that release a photographically useful group include the following. Development inhibitor releasing compound: EP 378,2
Compounds represented by formulas (I), (II), (III) and (IV) described on page 11 of 36A1 (especially T-101 (page 30), T-104 (page 31), T-113 (36 page),
T-131 (p. 45), T-144 (p. 51), T-158 (p. 58)), EP 436,938A2
Compounds of the formula (I) described on page 7 (particularly D-49 (5
1)), a compound represented by formula (1) of EP 568,037A (especially (23) (page 11)), and a compound described in EP 440,195 A2 on pages 5 to 6.
Compounds represented by (I), (II) and (III) (especially I- (1) on page 29)
); Bleaching accelerator releasing compound: Formula on page 5 of EP 310,125A2
Compounds represented by (I), (I ') (especially (60), (61) on page 61)
And a compound represented by formula (I) of claim 1 of JP-A-6-59411 (especially (7) (page 7)); Ligand releasing compound: US 4,55
A compound represented by LIG-X described in claim 1 of 5,478 (especially a compound on line 21 to 41 of column 12); a leuco dye releasing compound: compounds 1 to 6 of columns 3 to 8 of US 4,749,641;
Fluorescent dye releasing compound: Claim 4, COUP of US 4,774,181
-DYE (especially compound 1 in columns 7 to 10)
11); Development accelerator or fog release compound: US 4,65
Compounds represented by formulas (1), (2) and (3) in column 3 of column 6,123 (especially (I-22) in column 25) and EP 450,637A2, page 75
ExZK-2 at line 36-38; Compound which releases a group which becomes a dye only after leaving: Compound represented by formula (I) in claim 1 of US Pat. No. 4,857,447 (particularly, Y-1 to Y- of columns 25 to 36) 19).

As the additives other than the coupler, the following are preferable. Dispersion medium for oil-soluble organic compound: JP-A-62-2
15272 P-3,5,16,19,25,30,42,49,54,55,66,81,85,86,
93 (pp. 140-144); Latex for impregnation of oil-soluble organic compound: latex described in US Pat. (Especially I-, (1), (2), (6), (12)
(Columns 4-5), formulas in rows 5-10 of column 2 of US 4,923,787 (especially compound 1 (column 3); stain inhibitor: EP
Formulas (I) to (III) on page 4, lines 30 to 33 of 298321A, especially I-47, 72,
III-1, 27 (pages 24 to 48); Anti-fading agent: A-6 of EP 298321A,
7,20,21,23,24,25,26,30,37,40,42,48,63,90,92,94,164
(Pp. 69-118), II-5-II of columns 25-38 of US 5,122,444
I-23, especially III-10, I-1 to III- on pages 8 to 12 of EP 471347A
4, especially II-2, US 5,139,931 columns 32 to 40, A-1 to 48,
In particular, A-39, 42; a material that reduces the amount of a color-enhancing agent or color-mixing inhibitor used: EP 411324A, pages 5 to 24, I-1 to II-15,
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-
Compounds (H-1 to 54) represented by formulas (VII) to (XII) of 23, compounds represented by the formula (6) at the lower right of page 8 of JP-A-2-214852 (H
-1 to 76), especially compounds described in claim 1 of H-14, US Pat. No. 3,325,287; development inhibitor precursors: disclosed in JP-A-62-168139.
P-24, 37, 39 (pages 6 to 7); compounds described in claim 1 of US Pat. No. 5,019,492, in particular, 28, 29 of column 7;
US 4,923,790, columns 3-15, I-1 to III-43, especially II-
1,9,10,18, III-25; stabilizer, antifoggant: US 4,923,
793 columns 6 to 16 I-1 to (14), especially I-1,60, (2), (13),
Compounds 1-65, especially 3 in columns 25-32 of US 4,952,483
6: Chemical sensitizer: triphenylphosphine selenide, compound 50 of JP-A-5-40324; dye: 15-1 of JP-A-3-156450
A-1 to b-20 on page 8, especially a-1,12,18,27,35,36, b-5,27 to 2
V-1 to 23 on page 9, especially FI on page 33 to 55 of V-1, EP 445627A
-1 to F-II-43, especially FI-11, F-II-8, 17 to 2 of EP 457153A
III-1 to 36 on page 8, especially III-1,3, 8 to 26 in WO 88/04794
A microcrystalline dispersion of Dye-1 to 124, compounds 1 to 22 on pages 6 to 11 of EP 319999A, in particular compounds D-1 to 87 (compounds 1 and 519306A represented by formulas (1) to (3)). (Pages 3 to 28), US 4,2
Compounds 1 to 22 represented by the formula (I) of 68,622 (columns 3 to
10), compounds (1) to (4) of the formula (I) of US Pat.
(31) (Columns 2 to 9); UV absorber: Formula of JP-A-46-3335
Compounds (18b) to (18r), 101 to 427 (6 to
9), and the compounds (3) to (6) represented by the formula (I) in EP 520938A.
6) (Pages 10 to 44) and compound HBT-1 represented by formula (III)
~ 10 (page 14), a compound represented by formula (1) in EP 521823A
(1) to (31) (columns 2 to 9).

The present invention can be preferably applied to various color photographic materials such as color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films and color reversal papers. . In addition, 2-32615
This is suitable for a film unit with a lens described in JP-B-3-39784. Suitable supports that can be used in the present invention are described in, for example, RD. No. 17643, p.
o.18716 right column on page 647 to left column on page 648, and No.3071
05, p. 879. The photosensitive material of the present invention is
The sum of the thicknesses of all the hydrophilic colloid layers on the side having the emulsion layer is
It is preferably at most 28 μm, more preferably at most 23 μm, further preferably at most 18 μm, particularly preferably at most 16 μm. Further, the film swelling speed T _1/2 is preferably 30 seconds or less, more preferably 20 seconds or less. T _1/2 is a color developer
Maximum swelling film thickness of 90 reached at 30 ° C for 3 minutes 15 seconds
When% is defined as the saturated film thickness, it is defined as the time until the film thickness reaches 1/2. The film thickness means a film thickness measured at 25 ° C. 55% relative humidity (2 days), T _1/2 is er -
Photographic Science and Engineering by A. Green et al. (Photogr.Sci.Eng.), 19
Vol. 2, pages 124 to 129. T _1/2 can be adjusted by adding a hardening agent to gelatin as a binder or by changing the aging conditions after coating. The swelling ratio is preferably from 150 to 400%.
The swelling ratio can be calculated from the maximum swelling film thickness under the conditions described above by the following formula: (maximum swelling film thickness-film thickness) / film thickness. In the light-sensitive material of the present invention, a hydrophilic colloid layer (referred to as a back layer) having a total dry film thickness of 2 μm to 20 μm is preferably provided on the side opposite to the side having the emulsion layer. The back layer preferably contains the above-described 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 obtained by using the above-mentioned RD.
No. 18716, No. 18716, 651 left column to right column, and No. 18716
No. 307105, pages 880 to 881 can be used for development. Next, a processing solution for a color negative film used in the present invention will be described.
The compounds described in JP-A-4-21739, page 9, upper right column, line 1 to page 11, lower left column, line 4 can be used in the color developing solution used in the present invention. Particularly as a color developing agent for performing rapid processing, 2-methyl-4- [N-ethyl-
N- (2-hydroxyethyl) amino] aniline, 2-
Methyl-4- [N-ethyl-N- (3-hydroxypropyl) amino] aniline and 2-methyl-4- [N-ethyl-N- (4-hydroxybutyl) amino] aniline are preferred. These color developing agents are preferably used in an amount of 0.01 to 0.08 mol per liter of the color developing solution (hereinafter, also referred to as "L"), particularly preferably 0.015 to 0.1 mol.
It is preferably used in an amount of 06 mol, more preferably 0.02 to 0.05 mol. Also, the replenisher of the color developing solution has this concentration.
It is preferable to contain 1.1 to 3 times the color developing agent, particularly preferably 1.3 to 2.5 times.

As a preservative for the color developing solution, hydroxylamine can be used widely. However, when higher preservation is required, substitution with an alkyl group, a hydroxyalkyl group, a sulfoalkyl group, a carboxyalkyl group, or the like is required. A hydroxylamine derivative having a group is preferable, and specifically, N, N-di (sulfoethyl) hydroxylamine, monomethylhydroxylamine, dimethylhydroxylamine, monoethylhydroxylamine, diethylhydroxylamine, N, N-di (carboxyethyl) Hydroxylamines are preferred. Among the above, N, N-di (sulfoethyl) hydroxylamine is particularly preferred. These may be used in combination with hydroxylamine, but it is preferable to use one or more of them instead of hydroxylamine. The preservative is preferably used in an amount of 0.02 to 0.2 mol per liter, particularly preferably 0.03 to 0.15 mol, and more preferably 0.04 to 0.1 mol. As in the case of the color developing agent, the replenisher preferably contains a preservative at a concentration of 1.1 to 3 times the concentration of the mother liquor (processing tank solution). In the color developer,
Sulfite is used as an anti-tarring agent for the oxide of the color developing agent. The sulfite is preferably used in the range of 0.01 to 0.05 mol per liter, particularly preferably in the range of 0.02 to 0.04 mol. In replenishers, these 1.1 to 3
Preferably, it is used at twice the concentration. Further, the pH of the color developer is preferably in the range of 9.8 to 11.0, and particularly preferably in the range of 10.0 to 11.0.
It is preferably 10.5, and the replenisher is preferably set to a higher value in the range of 0.1 to 1.0 from these values. To maintain such a pH stably, carbonate,
Known buffers such as phosphates, sulfosalicylates, borates and the like are used.

The replenishment amount of the color developing solution is preferably from 80 to 1300 mL per m ² of the light-sensitive material, but is preferably smaller from the viewpoint of reducing the environmental pollution load, specifically from 80 to 600 m 2.
L, more preferably 80 to 400 mL. The bromide ion concentration in the color developing solution is usually 0.01 to 0.06 mol per liter. It is preferable to set the amount to 0.015 to 0.03 mol per liter. When the bromide ion concentration is set in such a range, the replenisher may contain bromide ions calculated by the following formula. However, when C becomes negative, it is preferred that the replenisher does not contain bromide ions. C = A−W / V C: Bromide ion concentration in the color developing replenisher (mol / L) A: Target bromide ion concentration in the color developing solution (mol / L) W: Coloring of 1 m ² photosensitive material Amount (mol) of bromide ion eluted from the light-sensitive material to the color developer when developed. V: Replenishment amount (L) of the color-developing replenisher for 1 m ² of the light-sensitive material. When the replenishment amount is reduced or when the bromide ion concentration is set to a high value, 1-phenyl-3-pyrazolidone or 1-phenyl-2-methyl-2 may be used as a method for increasing the sensitivity.
It is also preferable to use development accelerators such as pyrazolidones represented by -hydroxymethyl-3-pyrazolidone and thioether compounds represented by 3,6-dithia-1,8-octanediol.

The compounds and processing conditions described in JP-A-4-125558, page 4, lower left column, line 16 to page 7, lower left column, line 6 can be applied to the processing solution having bleaching ability in the present invention. . The bleaching agent preferably has an oxidation-reduction potential of 150 mV or more, and specific examples thereof include JP-A-5-72694 and JP-A-5-7333.
The compounds described in No. 12 are preferred, and 1,3-diaminopropanetetraacetic acid, particularly, a ferric complex salt of the compound of Specific Example 1 on page 7 of JP-A-5-73312 is preferred. Further, in order to improve the biodegradability of the bleach, JP-A-4-218845, JP-A-4-268552, EP588,
289, 591,934 and JP-A-6-208213 are preferably used as a bleaching agent. The concentration of these bleaching agents is from 0.05 to 1 per liter of a solution having bleaching ability.
0.3 mol is preferable, and in particular, it is preferable to design 0.1 mol to 0.15 mol for the purpose of reducing the amount discharged to the environment. When the liquid having bleaching ability is a bleaching liquid, it preferably contains 0.2 mol to 1 mol of bromide per liter, particularly preferably 0.3 to 0.8 mol. The replenisher of the solution having the bleaching ability basically contains the concentration of each component calculated by the following formula. This allows
The concentration in the mother liquor can be kept constant. CR = CT × (V1 + V2) / V1 + CP CR: Concentration of component in replenisher CT: Concentration of component in mother liquor (processing tank solution) CP: Concentration of component consumed during processing V1: 1 m ² for photosensitive material Replenishment amount of replenisher having bleaching ability (mL) V2: Amount (mL) brought in from a prebath by a photosensitive material of 1 m ² . In addition, the bleaching solution preferably contains a pH buffer, particularly preferably a dicarboxylic acid having a low odor, such as succinic acid, maleic acid, malonic acid, glutaric acid, and adipic acid. Also, JP-A-53-95630, RDN
It is also preferable to use known bleaching accelerators described in O. 17129, US Pat. No. 3,893,858. The bleaching solution is preferably replenished bleach replenisher 50~1000mL per photosensitive material 1 m ^2,
In particular, it is preferable to replenish 80 to 500 mL, more preferably 100 to 300 mL. Further, it is preferable to perform aeration on the bleaching solution.

The processing solution having a fixing ability is disclosed in
The compounds and processing conditions described on page 7, lower left column, line 10 to page 8, lower right column, line 19 of 4-125558 can be applied. Particularly, in order to improve the fixing speed and the preservability, the compounds represented by the general formulas (I) and (II) of JP-A-6-301169 are contained alone or in combination in a processing solution having a fixing ability. Is preferred. In addition to p-toluenesulfinic acid salts, it is also possible to use the sulfinic acid described in JP-A-1-2224762.
It is preferable from the viewpoint of improvement in preservation. It is preferable to use ammonium as a cation in the solution having the bleaching ability or the solution having the fixing ability from the viewpoint of improving the desilvering property, but from the viewpoint of reducing environmental pollution, it is preferable to reduce or eliminate ammonium. . In the bleaching, bleach-fixing, and fixing steps, it is particularly preferable to perform jet stirring described in JP-A-1-309590. The replenishment amount of the replenisher in the bleach-fixing or fixing step is 100 to 1000 mL per 1 m ² of the light-sensitive material,
Preferably 150 to 700 mL, particularly preferably 200 to 600 mL
It is. In the bleach-fixing or fixing step, it is preferable to install various silver recovery devices in-line or off-line to recover silver. By installing in-line, the processing can be carried out with a reduced silver concentration in the solution, so that the replenishment amount can be reduced. It is also preferable to recover silver off-line and reuse the remaining liquid as a replenisher. The bleach-fixing step and the fixing step can be composed of a plurality of processing tanks, and each tank is preferably a cascade pipe to have a multistage countercurrent system. In general, 2
The tank cascade configuration is efficient, and the ratio of the processing time in the former tank and the latter tank is 0.5: 1 to 1:
It is preferred to be in the range of 0.5, especially 0.8: 1 to 1
A range of 1: 0.8 is preferred. For bleach-fix or fixer,
From the viewpoint of improving preservation, it is preferable to use a free chelating agent which is not in the form of a metal complex. As these chelating agents, it is preferable to use the biodegradable chelating agents described for the bleaching solution.

Regarding the washing and stabilizing steps, see JP-A-4-125558, page 12, lower right column, line 6 to page 13, lower right column, column 16.
The contents described in the line can be preferably applied. In particular, EP 504,60 replaces formaldehyde in stabilizers.
9. Use of the azolylmethylamines described in 519,190 and N-methylolazoles described in JP-A-4-362943, and the use of an interface free of image stabilizers such as formaldehyde by dimerizing a magenta coupler. It is preferable to use a liquid of the activator from the viewpoint of preserving the working environment. Further, in order to reduce the adhesion of dust to the magnetic recording layer applied to the photosensitive material, a stabilizer described in JP-A-6-289559 can be preferably used. The amount of washing and replenishment of the stabilizing solution is preferably 80 to 1000 mL per 1 m ² of the light-sensitive material, and particularly preferably 100 to 500 m 2.
L, and more preferably 150 to 300 mL, is a preferable range in terms of both securing a washing or stabilizing function and reducing waste liquid for environmental protection. In the process performed with such a replenishment amount,
Known antifungal agents such as thiabendazole, 1,2-benzisothiazolin-3-one, 5-chloro-2-methylisothiazolin-3-one and antibiotics such as gentamicin for preventing the growth of bacteria and molds; It is preferable to use water deionized with an ion exchange resin or the like. It is more effective to use a combination of deionized water and a bactericide or antibiotic. Further, the liquid in the washing or stabilizing liquid tank is disclosed in JP-A-3-46652, JP-A-3-53246, JP-355542,
It is also preferable to reduce the replenishment amount by performing the reverse osmosis membrane treatment described in 3-112448 and 3-126030. In this case, the reverse osmosis membrane is preferably a low-pressure reverse osmosis membrane.

In the process of the present invention, it is particularly preferable to carry out the correction of evaporation of the processing solution disclosed in Hatsumei Kyokai Disclosure No. 94-4992. In particular, a method of performing correction using temperature and humidity information of a developing machine installation environment based on (Equation 1) on page 2 is preferable. The water used for evaporation correction is preferably collected from a replenishment tank for washing,
In that case, it is preferable to use deionized water as the washing replenishing water.

As the treating agent used in the present invention, those described in the above-mentioned published technical report, page 3, right column, line 15 to page 4, left column, line 32 are preferable. In addition, as a developing machine used for this,
The film processor described on page 3, right column, lines 22 to 28 is preferred. Specific examples of preferred processing agents, automatic developing machines, and evaporation correction methods for carrying out the present invention are described in the above-mentioned published technical report from page 5, right column, line 11 to page 7, right column, last line. .

The supply form of the treating agent used in the present invention is as follows.
It may be in any form, such as a liquid preparation in the form of a liquid used or a concentrated form, or granules, powders, tablets, pastes, and emulsions. As an example of such a treating agent, JP-A-63-1
7453 discloses a liquid agent contained in a container having low oxygen permeability,
19655, 4-230748, vacuum-packed powders or granules, 4-221951, granules containing a water-soluble polymer,
JP-A-51-61837 and JP-A-6-102628 describe tablets and JP-A-57-5
Discloses a paste-like treating agent, which can be preferably used, but from the viewpoint of simplicity at the time of use,
It is preferable to use a liquid that has been prepared in advance in a concentration for use. In the container for storing these treatment agents, polyethylene, polypropylene, polyvinyl chloride, polyethylene terephthalate, nylon, or the like is used alone or as a composite material. These are selected according to the required level of oxygen permeability. For an easily oxidizable liquid such as a color developing solution, a material having low oxygen permeability is preferable, and specifically, a polyethylene terephthalate or a composite material of polyethylene and nylon is preferable. These materials are used in containers having a thickness of 500 to 1500 μm, and preferably have an oxygen permeability of 20 × 10 ⁵ mL / m ² · 24 hrs · Pa or less.

Next, the processing solution for the color reversal film used in the present invention will be described. For the processing for the color reversal film, see page 6, line 5 to page 10, line 5 and page 15, line 8 to page 24, 2 of the publicly known technique No. 6 (April 1, 1991) issued by Aztec Co., Ltd. Each row is described in detail, and any of the contents can be preferably applied. In processing a color reversal film, the image stabilizer is contained in a conditioning bath or a final bath. Examples of such an image stabilizer include, in addition to formalin, sodium formaldehyde sodium sulfite and N-methylolazoles.
From the viewpoint of working environment, sodium formaldehyde sodium bisulfite or N-methylolazole is preferable, and N-methyloltriazole is particularly preferable as N-methylolazole. Further, the contents relating to the color developing solution, the bleaching solution, the fixing solution, the washing water and the like described in the processing of the color negative film can be preferably applied to the processing of the color reversal film. A preferred color reversal film treating agent having the above-mentioned content is E-manufactured by Eastman Kodak Company.
6 processing agents and CR-56 processing agents of Fuji Photo Film Co., Ltd.

The color photographic light-sensitive material of the present invention is also suitable as a negative film for an advanced photo system (hereinafter, referred to as an AP system). NEXI
Films processed into the AP system format such as AF and NEXIA H (in order, ISO 200/100/400) and stored in a special cartridge can be mentioned. These AP system cartridge films are used by being mounted on an AP system camera such as an Epion series (Epion 300Z or the like) manufactured by Fuji Film. Further, the color photographic light-sensitive material of the present invention is also suitable for a film with a lens such as a super slim, which is a Fujicolor photograph run made by Fuji Film.

The film photographed by the above is printed in the minilab system through the following steps. (1) Reception (exposed cartridge film received from customer) (2) Detach process (transfer film from cartridge to intermediate cartridge for development process) (3) Film development (4) Retouch process (developed negative (Return the film to the original cartridge.) (5) Print (C / H / P3 type prints and index prints on color paper (preferably made by Fujifilm)
SUPER FA8]) (6) Collation and shipping (cartridge and index print
Check with ID number and ship with print).

These systems include Fujifilm Minilab Champion Super FA-298 / FA-278 / FA-258 / F
A-238 and Fujifilm Digital Lab System Frontier are preferred. FP922AL / FP562B / FP562B, AL / FP362B / FP as minilab champion film processors
362B, AL, and the recommended treatment chemicals are Fujicolor Justit CN-16L and CN-16Q. As a printer processor, PP3008AR / PP3008A / PP1828AR / PP1828A / PP12
58AR / PP1258A / PP728AR / PP728A, and the recommended treatment chemicals are Fujicolor Justit CP-47L and CP-40FAII. For Frontier System, Scanner & Image Processor SP-1000 and Laser Printer & Paper Processor LP-1000P or Laser Printer L
P-1000W is used. The detacher used in the detaching step and the reattacher used in the rear attaching step are preferably DT200 / DT100 and AT200 / AT100 of Fujifilm, respectively.

The AP system can also be enjoyed by a photo joy system centered on Fujifilm's Aladdin 1000 digital image workstation. For example, you can directly load a developed AP system cartridge film into the Aladdin 1000, or transfer image information from negative film, positive film, and print to a 35mm film scanner FE.
The digital image data obtained by inputting using the -550 or PE-550 flat head scanner can be easily processed and edited. The data are stored in a digital color printer NC-550AL using a light fixing type thermal color printing system and a pictograph 3000 using a laser exposure thermal development transfer system.
Or as a print by existing laboratory equipment through a film recorder. The Aladdin 1000 can also output digital information directly to a floppy (registered trademark) disk or Zip disk, or to a CD-R via a CD writer.

On the other hand, at home, a developed AP system cartridge
You can enjoy photos on TV just by loading it in -1,
By loading it onto a Fujifilm AS-1 photo scanner, image information can be continuously and rapidly captured on a personal computer. To enter a film, print, or three-dimensional object into a computer, use Fujifilm PhotoVision FV-10 / FV.
-5 is available. Furthermore, image information recorded on a floppy disk, Zip disk, CD-R, or hard disk can be variously processed and enjoyed on a personal computer using Fujifilm's application software Photo Factory. In order to output high-quality prints from a personal computer, a digital color printer NC-2 / NC-2D manufactured by Fujifilm of a light fixing type thermal color print system is suitable. To store the developed AP system cartridge film, use the Fujicolor Pocket Album AP-5 POP L, A
P-1 pop L, AP-1 pop KG or cartridge file 16
Is preferred.

[0099]

Next, the present invention will be described in more detail with reference to the following Examples, but it should not be construed that the present invention is limited thereto.

Example 1 (Preparation of seed emulsion a) KBr 0.017 g, average molecular weight 2
Aqueous solution 11 containing 0.4 g of 0000 oxidized gelatin
64 ml was kept at 35 ° C. and stirred. AgNO ₃ (1.6
g) An aqueous solution, an aqueous KBr solution, and an aqueous solution of oxidized gelatin (2.1 g) having an average molecular weight of 20,000 were added over 48 seconds by a triple jet method. At this time, the silver potential was kept at 13 mV with respect to the saturated calomel electrode. After an aqueous KBr solution was added to adjust the silver potential to −66 mV, the temperature was raised to 60 ° C. 21 g of succinated gelatin having an average molecular weight of 100,000
Was added, and an aqueous solution of NaCl (5.1 g) was added. An aqueous solution of AgNO ₃ (206.3 g) and an aqueous solution of KBr were added over 61 minutes while accelerating the flow rate by the double jet method. At this time, the silver potential was kept at -44 mV with respect to the saturated calomel electrode. After desalting, the average molecular weight is 1000
Succinated gelatin at pH 5.8 at 40 ° C.
The pAg was adjusted to 8.8 to prepare a seed emulsion. This seed emulsion contains 1 mol of Ag and 80 g of gelatin per kg of emulsion.
It was tabular grains having an average equivalent circle diameter of 1.46 μm, a coefficient of variation of equivalent circle diameter of 28%, an average thickness of 0.046 μm, and an average aspect ratio of 32.

(Formation of core) 134 g of the above seed emulsion a was prepared.
Succinated KBr 1.9 g, average molecular weight 100000
Keep 1200 ml of aqueous solution containing 22 g of rat at 75 ° C
Stirred. AgNO _Three(43.9g) aqueous solution and KBr aqueous solution
Solution and an aqueous gelatin solution having a molecular weight of 20,000
No. 43570, a magnetic coupling induction type stirrer.
Mixing just before addition in another chamber with 25 minutes
Was added. At this time, the silver potential is applied to the saturated calomel electrode.
On the other hand, it was kept at -40 mV.

(Formation of First Shell) After the formation of the core particles, an aqueous solution of AgNO ₃ (43.9 g), an aqueous solution of KBr, and an aqueous solution of gelatin having a molecular weight of 20,000 were mixed immediately before the addition in another chamber in the same manner as above, to form a solution. Added over minutes.
At this time, the silver potential was set to -40 mV with respect to the saturated calomel electrode.
Kept.

(Formation of Second Shell) After the formation of the first shell, an aqueous solution of AgNO ₃ (42.6 g), an aqueous solution of KBr, and an aqueous solution of gelatin having a molecular weight of 20,000 were mixed immediately before addition in another chamber of the same type. Added over 17 minutes. At this time, the silver potential was set to -20 with respect to the saturated calomel electrode.
mV. Thereafter, the temperature was lowered to 55 ° C.

(Formation of Third Shell) After the formation of the second shell, the silver potential was adjusted to -55 mV, and AgNO ₃ (7.1
g) Aqueous solution, KI (6.9 g) aqueous solution and molecular weight 2000
The gelatin aqueous solution was mixed immediately before the addition in another chamber as above and added over 5 minutes.

(Formation of Fourth Shell) After the formation of the third shell, an aqueous solution of AgNO ₃ (66.4 g) and an aqueous solution of KBr were added at a constant flow rate over 30 minutes by a double jet method. On the way, iridium potassium hexachloride and yellow blood salt were added. At this time, the silver potential was set to 30 m with respect to the saturated calomel electrode.
Kept at V. Perform normal water washing, add gelatin,
The pH was adjusted to 5.8 and the pAg to 8.8 at 0 ° C. This emulsion was designated as emulsion b. Emulsion b was tabular grains having an average equivalent circle diameter of 3.3 μm, a coefficient of variation of the equivalent circle diameter of 21%, an average thickness of 0.090 μm, and an average aspect ratio of 37. Further, 70% or more of the total projected area has a circle equivalent diameter of 3.3 μ or more and a thickness of 0.0
It was occupied by tabular grains of 90μ or less.

(Sulfur-sensitized emulsion) Emulsion b was heated to 56 ° C., and the sensitizing dyes shown in Table 1 were added in an amount of 1.1 × 10 ⁻³ mol / mol A
After the addition of g, C-5, potassium thiocyanate, chloroauric acid and sodium thiosulfate were added for optimal chemical sensitization, and the mixture was further stirred for 60 minutes. (Selenium-sensitized emulsion) Emulsion b was heated to 56 ° C., and the sensitizing dyes shown in Table 1 were added at 1.1 × 10 ⁻³ mol / mol Ag, and then C-5, potassium thiocyanate, chloroauric acid, Sodium sulfate and N, N-dimethylselenourea were added for optimal chemical sensitization, and the mixture was further stirred for 60 minutes.

The sensitizing dye is described in JP-A-11-52507.
Was used as a solid fine dispersion prepared by the method described in No. That is, 0.8 parts by weight of sodium nitrate and 3.2 parts by weight of sodium sulfate are dissolved in 43 parts of ion-exchanged water,
13 parts by weight of the sensitizing dye was added, and the mixture was dispersed at 2,000 rpm for 20 minutes at 60 ° C. using a Solver blade to obtain a solid dispersion of the sensitizing dye.

Further, a gelatin hardener and a coating aid were added to the obtained emulsion, and a gelatin protective layer was formed on a cellulose acetate film support so that the coated silver amount was 3.0 g-Ag / m ^2. At the same time. The resulting film was exposed to a tungsten bulb (color temperature 2854K) for 1 second through a continuous wedge color filter.
Using a minus gelatin exposure SC-40 (manufactured by FUJIFILM Corporation) that excites the dye side as a color filter, light of 400 nm or less was blocked and the sample was irradiated. The exposed sample was the following surface developer MAA
Developing at -20 ° C. for 10 minutes. Next, the following fixing was performed, followed by washing with water and drying. After exposing the film in the same manner as described above,
After storage for 1 month, development and fixing were performed in the same manner as described above.

Surface developer MAA-1 formulation Metol 2.5 g L-ascorbic acid 10 g Navox (Fuji Film Co., Ltd.) 35 g Potassium bromide 1 g Water is added to 1 liter pH 9.8

After development, fixing was performed at 20 ° C. with the following fixing solution. Fixing solution formulation Ammonium thiosulfate 170 g Sodium sulfite (anhydrous) 15 g Boric acid 7 g Glacial acetic acid 15 ml Potassium alum 20 g Ethylenediaminetetraacetic acid 0.1 g Tartaric acid 3.5 g Add water 1 liter

The optical density of the processed film was measured by a Fuji automatic densitometer.
The relative value when the fresh sensitivity of Sample 1 was set to 100, and the relative values when the fresh sensitivity of Sample 19 was 100 were set for Samples 19 to 22.

[0112]

[Table 1]

[0113]

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Table 1 shows the results. From Table 1, the comparative dyes
In SS-1 and SS-2, the selenium sensitized emulsion is more sensitive than the sulfur sensitized emulsion, but the storage stability of the latent image is worse in the selenium sensitized emulsion. On the other hand, in the sensitizing dye of the present invention, the selenium sensitized emulsion not only sensitizes the selenium sensitized emulsion as compared with the sulfur sensitized emulsion, but also has a latent image preservability. It turns out that it improves. In sample 14, the sensitizing dye contained almost 620 n
A J-aggregate having a maximum at m was formed, and showed a spectral sensitivity distribution similar to that of absorption.

Example 2 1) Support The support used in this example was produced by the following method. 1) First layer and undercoat layer For a polyethylene naphthalate support having a thickness of 90 μm, a treatment atmosphere pressure of 2.66 × 10
Pa, H ₂ O partial pressure of 75% in the atmosphere gas, a discharge frequency 3
0 kHz, output 2500 W, processing intensity 0.5 kV ・ A ・
A glow discharge treatment was performed at a rate of min / m ² . On this support,
For the first layer, a coating solution having the following composition was used.
The coating was performed at a coating amount of 5 mL / m ² by using the bar coating method described in Japanese Patent Application Laid-Open No. H10-260,036. Conductive fine particle dispersion (SnO ₂ / Sb ₂ O ₅ particle concentration 50 parts by mass 10% aqueous dispersion. Secondary aggregate having a primary particle diameter of 0.005 μm and an average particle diameter of 0.05 μm) Gelatin 0. 5 parts by mass Water 49 parts by mass Polyglycerol polyglycidyl ether 0.16 parts by mass Poly (degree of polymerization 20) oxyethylene 0.1 part by mass Sorbitan monolaurate. Further, after coating the first layer, it is wound around a stainless steel core having a diameter of 20 cm, and is heated to 110 ° C. (Tg of PEN support: 119).
C) for 48 hours, heat-histored and annealed, followed by a bar coating method using a coating solution of the following composition as an undercoat layer for emulsion on the side opposite to the first layer side with the support interposed therebetween.
Coating was performed at a coating amount of 10 mL / m ² . Gelatin 1.01 part by mass Salicylic acid 0.30 part by mass Resorcin 0.40 part by mass Poly (polymerization degree 10) oxyethylene nonylphenyl ether 0.11 part by mass Water 3.53 parts by mass Methanol 84.57 parts by mass n-propanol 10 0.08 parts by mass. Further, a second layer and a third layer described later are sequentially coated on the first layer, and finally, a color negative photosensitive material having a composition described later is overlaid on the opposite side to form a transparent magnetic recording with a silver halide emulsion layer. A medium was prepared.

2) Second layer (transparent magnetic recording layer) Dispersion of magnetic material Co-coated γ-Fe ₂ O ₃ magnetic material (average major axis length: 0.25 μm)
m, SBET: 39 m ^{2 /} g, Hc: 6.56 × 10 ⁴ A
/ M, σs: 77.1 Am ² / kg, σr: 37.4 A
m ² / kg) 1,100 parts by mass, 220 parts by mass of water and a silane coupling agent [3- (poly (degree of polymerization 10) oxyethynyl) oxypropyl trimethoxysilane] 165
The resulting mixture was kneaded with an open kneader for 3 hours. The coarsely dispersed viscous liquid was dried at 70 ° C. for 24 hours to remove water, and then heated at 110 ° C. for 1 hour to produce surface-treated magnetic particles. Further, the mixture was kneaded again with an open kneader for 4 hours according to the following formulation. The above-mentioned surface-treated magnetic particles 855 g Diacetyl cellulose 25.3 g Methyl ethyl ketone 136.3 g Cyclohexanone 136.3 g Further, the mixture was finely dispersed in a sand mill (1/4 G sand mill) at 2000 rpm for 4 hours according to the following formulation. As the medium, glass beads having a diameter of 1 mm were used. The kneading liquid 45 g Diacetyl cellulose 23.7 g Methyl ethyl ketone 127.7 g Cyclohexanone 127.7 g Further, a magnetic substance-containing intermediate liquid was prepared according to the following formulation. Preparation of Magnetic Substance-Containing Intermediate Solution 674 g of the above magnetic substance fine dispersion liquid 24280 g (solid content: 4.34%, solvent: methyl ethyl ketone / cyclohexanone = 1/1) cyclohexanone 46 g And stirred to produce a “magnetic substance-containing intermediate liquid”. An α-alumina abrasive dispersion was prepared according to the following formulation. (A) Preparation of Sumicorundum AA-1.5 (average primary particle size 1.5 μm, specific surface area 1.3 m ² / g) particle dispersion Sumicorundum AA-1.5 152 g Silane coupling agent KBM903 (Shinetsu Silico 0.48 g Diacetyl cellulose solution 227.52 g (solid content 4.5%, solvent: methyl ethyl ketone / cyclohexanone = 1/1) Sand mill (1 /
(4G sand mill) at 800 rpm for 4 hours. As the media, zirconia beads having a diameter of 1 mm were used. (B) Colloidal silica particle dispersion (fine particles) "MEK-ST" manufactured by Nissan Chemical Industries, Ltd. was used. This is a dispersion liquid of colloidal silica having an average primary particle diameter of 0.015 μm using methyl ethyl ketone as a dispersion medium,
The solids content is 30%. Preparation of the second layer coating solution 19053 g of the above magnetic substance-containing intermediate solution 264 g of diacetyl cellulose solution (solid content: 4.5%, solvent: methyl ethyl ketone / cyclohexanone = 1/1) Colloidal silica dispersion "MEK-ST" [dispersion b] 128 g (solid content 30%) AA-1.5 dispersion [dispersion a] 12 g Millionate MR-400 (manufactured by Nippon Polyurethane Co., Ltd.) Diluent 203 g (solid content 20%, diluent solvent: methyl ethyl ketone / cyclohexanone = 1 / 1) 170 g of methyl ethyl ketone 170 g of cyclohexanone The coating solution obtained by mixing and stirring the above was applied with a wire bar so as to have an application amount of 29.3 mL / m ² . Drying is 1
Performed at 10 ° C. The thickness as a magnetic layer after drying is 1.0
μm.

3) Third layer (layer containing a higher fatty acid ester slip agent) Preparation of a stock solution of a slip agent The following solution A was heated and dissolved at 100 ° C, added to the solution A, dispersed with a high-pressure homogenizer, and dispersed. Was prepared. Solution A The following compound 399 parts by mass C ₆ H ₁₃ CH (OH) (CH ₂ ) ₁₀ COOC ₅₀ H _{101 The following} compound 171 parts by mass nC ₅₀ H ₁₀₁ O (CH ₂ CH ₂ O) ₁₆ H cyclohexanone 830 parts by mass. Solution A Cyclohexanone 8600 parts by mass. Preparation of Spherical Inorganic Particle Dispersion A spherical inorganic particle dispersion [c1] was prepared according to the following formulation. 93.54 parts by mass of isopropyl alcohol Silane coupling agent KBM903 (manufactured by Shin-Etsu Silicone) Compound 1-1: 5.53 parts by mass of (CH ₃ O) ₃ Si— (CH ₂ ) ₃ —NH ₂ Compound 1 2. 93 parts by mass

[0118]

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88.00 parts by mass of Sea Hosta KEP50 (amorphous spherical silica, average particle size 0.5 μm, manufactured by Nippon Shokubai Co., Ltd.). After stirring for 10 minutes with the above formulation, the following is further added. 252.93 parts by mass of diacetone alcohol While cooling the above solution with ice and stirring, an ultrasonic homogenizer “SONIFIER450 (BRANSON CORPORATION)
)) For 3 hours to obtain a spherical inorganic particle dispersion c1.
Was completed. Preparation of Spherical Organic Polymer Particle Dispersion A spherical organic polymer particle dispersion [c2] was prepared according to the following formulation. XC99-A8808 (Toshiba Silicone Corporation)
60 mass parts methyl ethyl ketone 120 mass parts cyclohexanone 120 mass parts (solid content 20%, solvent: methyl ethyl ketone / cyclohexanone = 1/1) Ultrasonic homogenizer "SONIFIER450 (BRANSON
(Manufactured by K.K.) for 2 hours to obtain a dispersion liquid c2 of spherical organic polymer particles. Preparation of Third Layer Coating Solution The following was added to 542 g of the slip agent dispersion stock solution to prepare a third layer coating solution. Diacetone alcohol 5950 g Cyclohexanone 176 g Ethyl acetate 1700 g Dispersion [c1] of the Seahosta KEP5 53.1 g Dispersion [c2] of the spherical organic polymer particles 300 g FC431 2.65 g (manufactured by 3M Corporation, solid 5.3% BYK310 (manufactured by BYK Chemi Japan, solid content 25%).

The above third layer coating solution was applied on the second layer by 10.3
It was applied at a coating amount of 5 mL / m ² , dried at 110 ° C., and further dried at 97 ° C. for 3 minutes. 4) Coating of photosensitive layer Next, on the opposite side of the back layer obtained above, each layer having the following composition was applied in a multilayer manner to prepare a color negative film. (Composition of photosensitive layer) The number corresponding to each component indicates the coating amount in g / m ² , and the coating amount in terms of silver is shown for silver halide. (Specific compounds are described below.
Symbols are followed by a number followed by a chemical formula).

First Layer (First Antihalation Layer) Black Colloidal Silver Silver 0.070 Gelatin 0.608 ExM-1 0.035 F-8 0.001 HBS-1 0.050 HBS-2 0.002 Second Layer (second antihalation layer) Black colloidal silver Silver 0.089 Gelatin 0.632 ExF-1 0.002 F-8 0.001 Third layer (intermediate layer) Cpd-1 0.082 HBS-1 0.043 Gelatin 0.422 4th layer (low-sensitivity red-sensitive emulsion layer) Em-D silver 0.577 Em-C silver 0.347 ExC-1 0.263 ExC-2 0.015 ExC-3 0.155 ExC-4 0.144 ExC-5 0.035 ExC-6 0.015 ExC-8 0.020 Cpd-4 0.025 UV-2 0.047 UV-3 0.086 UV-4 0.0 8 HBS-1 0.245 HBS-5 0.038 Gelatin 0.994

Fifth Layer (Medium Speed Red Sensitive Emulsion Layer) Em-B Silver 0.431 Em-C Silver 0.432 ExC-1 0.110 ExC-2 0.027 ExC-3 0.007 ExC-40 0.075 ExC-5 0.007 ExC-6 0.021 ExC-8 0.010 ExC-9 0.005 Cpd-2 0.032 Cpd-4 0.020 HBS-1 0.098 Gelatin 0.802 Sixth Layer (high-sensitivity red-sensitive emulsion layer) Em-A silver 1.214 ExC-1 0.070 ExC-3 0.005 ExC-6 0.026 ExC-8 0.109 ExC-9 0.020 Cpd-20 .068 Cpd-4 0.020 HBS-1 0.231 Gelatin 1.174 7th layer (intermediate layer) Cpd-1 0.073 Cpd-6 0.002 HBS-1 0.037 polyethyl Acrylate latex 0.088 Gelatin 0.683 Eighth layer (layer giving a multilayer effect to red-sensitive layer) Em-J silver 0.153 Em-K silver 0.153 ExM-2 0.086 ExM-3 0.002 ExM -4 0.025 ExY-4 0.041 ExC-7 0.026 HBS-1 0.218 HBS-3 0.003 Gelatin 0.649 9th layer (low-sensitivity green-sensitive emulsion layer) Em-H silver 0. 329 Em-G silver 0.333 Em-I silver 0.088 ExM-2 0.360 ExM-3 0.055 ExY-1 0.012 ExC-7 0.008 HBS-1 0.362 HBS-3 0.03 010 HBS-4 0.200 Gelatin 1.403

Tenth Layer (Medium Speed Green Sensitive Emulsion Layer) Em-F Silver 0.394 ExM-2 0.024 ExM-3 0.034 ExM-4 0.023 ExY-3 0.007 ExC-7 012 ExC-8 0.010 HBS-1 0.060 HBS-3 0.002 HBS-4 0.020 Gelatin 0.474 Eleventh layer (high-sensitivity green-sensitive emulsion layer) Em-E silver 0.883 ExC-6 0.007 ExC-8 0.011 ExM-1 0.021 ExM-2 0.059 ExM-3 0.015 ExM-4 0.030 Cpd-3 0.005 Cpd-5 0.010 HBS-1 176 HBS-4 0.070 HBS-5 0.037 Polyethyl acrylate latex 0.099 Gelatin 0.916 12th layer (yellow filter layer) Cpd-1 0.092 solid disperse dye ExF-2 0.088 HBS-1 0.049 gelatin 0.603 13th layer (low-sensitivity blue-sensitive emulsion layer) Em-O silver 0.112 Em-M silver 0.320 Em-N silver 0.240 ExC-1 0.049 ExC-7 0.013 ExY-1 0.002 ExY-2 0.693 ExY-4 0.058 HBS-1 0.231 Gelatin 1.553 14th layer (high sensitivity blue Emulsion-sensitive layer) Em-L silver 0.858 ExY-2 0.357 ExY-4 0.068 HBS-1 0.124 Gelatin 0.949

Fifteenth layer (first protective layer) 0.07 μm silver iodobromide emulsion Silver 0.245 UV-1 0.313 UV-2 0.156 UV-3 0.222 UV-4 0.022 F -18 0.007 S-1 0.068 HBS-1 0.175 HBS-4 0.020 Gelatin 1.950 Sixteenth layer (second protective layer) H-1 0.356 B-1 (1.7 μm in diameter) ) 0.050 B-2 (diameter 1.7 μm) 0.150 B-3 0.050 S-1 0.200 Gelatin 0.675

Further, in order to improve the storability, processability, pressure resistance, fungicide / antibacterial property, antistatic property and coatability of each layer, W-1 to W-6, B-4 to B -6, F
-1 to F-17 and lead salts, platinum salts, iridium salts, and rhodium salts. Preparation of Dispersion of Organic Solid Disperse Dye ExF-2 of the twelfth layer was dispersed by the following method. ExF-2 wet cake (containing 17.6 wt% water) 2.800 kg Sodium octylphenyldiethoxymethanesulfonate (31 wt% aqueous solution) 0.376 kg F-15 (7% aqueous solution) 0.011 kg water 4 0.020 kg Total 7.210 kg (adjusted to pH = 7.2 with NaOH) After the slurry having the above composition was coarsely dispersed by stirring with a dissolver, the peripheral speed was 10 m / s and the discharge rate was 0, using an agitator mill LMK-4. 6k
g / min, filling rate of zirconia beads of 0.3 mm diameter 8
At 0%, the dispersion is dispersed until the absorbance ratio of the dispersion becomes 0.29,
A solid fine particle dispersion was obtained. The average particle size of the fine dye particles is 0.
It was 29 μm.

[0126]

[Table 2]

In Table 2, in emulsions A to C, spectral sensitizing dyes 1, 2, and 3 were added in an optimal amount at a ratio of 69: 30: 1, and gold sensitization, sulfur sensitization, and selenium sensitization were performed optimally. ing.
Emulsions E to G were optimally added with spectral sensitizing dyes 4 to 6 and optimally sensitized with gold, sulfur, and selenium. Emulsion J
Are optimally added with spectral sensitizing dyes 7 and 8 and optimally sensitized with gold, sulfur and selenium. Emulsion L was added with optimal amounts of spectral sensitizing dyes 9 to 11 and optimally sensitized with gold, sulfur and selenium. Emulsion O is spectral sensitizing dye 1
Optimum amounts of 0 to 12 are added, and gold sensitization and sulfur sensitization are optimally performed. Emulsions D, H, I, K, M, and N were added with optimal amounts of the spectral sensitizing dyes shown in Table 2 and optimally sensitized with gold, sulfur, and selenium.

[0128]

[Table 3]

The sensitizing dyes shown in Table 3 are shown below.

[0130]

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[0131]

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[0132]

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[0133]

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[0134]

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[0135]

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[0136]

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[0137]

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The preparation of tabular grains is described in JP-A-1-15884.
According to the example described in No. 26, low molecular weight gelatin is used. Emulsions A to K contain optimum amounts of Ir and Fe. Emulsions L to O were reduction sensitized during grain preparation. When a high-pressure electron microscope is used for tabular grains, see JP-A-3-2.
Dislocation lines as described in No. 37450 are observed. Emulsions A to C and J were subjected to dislocation introduction using an iodide ion releasing agent in accordance with the examples described in JP-A-6-11782. Emulsion E was introduced into a separate chamber having a magnetic coupling induction type stirrer described in JP-A-10-43570, using silver iodide fine particles adjusted immediately before addition, to introduce dislocation. The compounds used for each layer are shown below.

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The above silver halide color photographic light-sensitive material is referred to as Sample 001. Next, sensitizing dyes 1, 2, and 3 in the fourth layer (low-sensitivity red photosensitive layer) and sensitizing dyes 1, 2, 3, and 6 in the fifth layer (medium-sensitivity red photosensitive layer) of Sample 001. A sample was prepared in which, among the sensitizing dyes-1, 2, and 3 of the layer (high-sensitivity red-sensitive layer), only sensitizing dye-1 was changed to the sensitizing dye described in Table 4. In the emulsions A, B, C, and D of the fourth, fifth, and sixth layers, gold sensitization, sulfur sensitization, and selenium sensitization (specifically,
Chemically sensitized with potassium thiocyanate, chloroauric acid, pentafluorophenyl-diphenylphosphine selenide and sodium thiosulfate. In addition, pentafluorophenyl-
SE obtained by diphenylphosphine selenide and sodium thiosulfate at a ratio of 38:62 was used, and instead gold sensitization and sulfur sensitization (specifically, potassium thiocyanate, chloroauric acid, What was chemically sensitized with sodium sulfate) was designated as S. These are shown in Table 4.

[0157]

[Table 4]

Each of the samples thus produced was subjected to continuous wedge exposure with white light, and the exposed samples were subjected to the following developing treatment, and the cyan density was measured. The sensitivity was relatively evaluated by the reciprocal of the exposure amount giving a density 0.2 higher than the minimum value (fog) of the cyan density. Further, after exposing the above sample in the same manner as described above, after storing it at 40 ° C. and 80% for one month, development processing was performed in the same manner as above, and the sensitivity was evaluated. Here, the fresh sensitivity of Sample 21 was set to 100.

Development was performed by an automatic developing machine F manufactured by Fuji Photo Film Co., Ltd.
Performed as follows using P-360B. 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-360B is equipped with the evaporation correction means described in Publication Technique No. 94-4992 (issued by the Invention Association). The processing steps and the composition of the processing solution are shown below. (Processing process) Process Processing time Processing temperature Replenishment amount * Tank capacity Color development 3 minutes 5 seconds 37.8 ° C 20 mL 11.5L Bleaching 50 seconds 38.0 ° C 5 mL 5L Fixing (1) 50 seconds 38.0 ° C ── 5L fixing (2) 50 seconds 38.0 ℃ 8 mL 5 L Rinse with water 30 seconds 38.0 ℃ 17 mL 3 L stable (1) 20 seconds 38.0 ℃ ── 3 L stable (2) 20 seconds 38.0 ℃ 15 mL 3 L drying 1 minute 30 seconds 60.0 ℃ For 35 mm photosensitive material and 1.1 m width (equivalent to one shot per 24 shots).

The stabilizing solution and the fixing solution were of a countercurrent type from (2) to (1), and the overflow of the washing water was all introduced into the fixing bath (2). The amount of the developer brought into the bleaching step, the amount of the bleaching liquid brought into the fixing step, and the amount of the fixing liquid brought into the washing step were 35 mm in width of the photosensitive material and 1.1 m in width.
2.5 mL, 2.0 mL, and 2.0 mL, respectively. The crossover time is 6 seconds in each case, 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 treatment liquid is shown below.

(Color developing solution) Tank solution (g) Replenisher (g) Diethylenetriaminepentaacetic acid 3.0 3.0 Disodium catechol-3,5-disulfonate 0.3 0.3 Sodium sulfite 3.9 3 Potassium carbonate 39.0 39.0 Disodium-N, N-bis (2-sulfonatoethyl) hydroxylamine 1.5 2.0 Potassium bromide 1.3 0.3 Potassium iodide 1.3mg-4-Hydroxy -6-methyl-1,3,3a, 7-tetrazaindene 0.05-hydroxylamine sulfate 2.4 3.3 2-methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino Aniline sulfate 4.5 6.5 Add water 1.0 L 1.0 L pH (adjusted with potassium hydroxide and sulfuric acid) 10.05 10.18.

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

(Fixing (1) Tank Liquid) A mixture of the bleaching tank liquid and the following fixing tank liquid in a ratio of 5 to 95 (volume ratio). (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 L 1.0 L pH [adjusted with ammonia water and acetic acid] 7.4 7.45 (Washing water) Tap water is replaced with H-type strongly acidic cation exchange resin (Amberlite manufactured by Rohm and Haas Company) IR-120B)
And water through a mixed-bed column filled with an OH-type strongly basic anion exchange resin (Amberlite IR-400) to treat the calcium and magnesium ion concentrations to 3 mg / L or less, followed by isocyanuric dichloride Sodium acid 2
0 mg / L and 150 mg / L sodium sulfate were added. The pH of this solution was in the range of 6.5 to 7.5.

(Stabilizer) Common to tank liquid and replenisher (unit: g) Sodium p-toluenesulfinate 0.03 Polyoxyethylene-p-monononylphenyl ether 0.2 (Average degree of polymerization: 10) 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, 1.0 L pH 8.5

From the results of Samples 21 to 24 shown in Table 4, in Samples 21 and 22 containing the comparative dye SS-1, although the selenium-sensitized emulsion was more sensitized than the sulfur-sensitized emulsion, the storage of the latent image was It can be seen that the selenium-sensitized emulsion deteriorates in properties.
On the other hand, Sample 2 containing the sensitizing dye (1) of the present invention
In Nos. 3 and 24, it is surprisingly found that the selenium sensitized emulsion not only sensitizes the selenium sensitized emulsion in comparison with the sulfur sensitized emulsion but also improves the storage stability of the latent image.

As described above, it was found that when the sensitizing dye of the present invention and the selenium-sensitized emulsion were used in combination, they were specifically excellent.

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

Claims (10)

[Claims] Claims: 1. A compound represented by the following general formula (I):
At least one silver halide photographic light-sensitive material
The silver halide grains of the silver halide photographic material
Silver halide photography characterized by being selenium sensitized
True photosensitive material. General formula (I)In the formula (I), X₁, X_Two, And X_ThreeIs an oxygen atom, a sulfur atom
Represents a selenium atom, a nitrogen atom, or a carbon atom. Z₁
Is nitrogen containing aromatic hydrocarbon or aromatic heterocyclic ring
Represents an atom group necessary for forming a heterocyclic ring. R₁,as well as
R_TwoRepresents an alkyl group, an aryl group, or a heterocyclic group
You. V₁, V_Two, And V_ThreeRepresents a hydrogen atom or a substituent
You. X₁Is a carbon atom, q₁Is 2, in the case of a nitrogen atom q₁
Is 1, otherwise q₁Is 0. X_TwoIs carbon
Q for an atom_TwoIs 1, otherwise q_TwoIs 0
You. X_ThreeIs a carbon atom, q_ThreeIs 1, the field of other atoms
Combination q_ThreeIs 0. L₁, L_Two, L_Three, L_Four, And L_FiveIs meth
Represents a group. n₁Represents 0, 1, 2, 3, or 4. p₁
Represents 0 or 1. M₁Represents a charge-balancing counter ion, m ₁
Represents the number required to neutralize the molecular charge. 2. The silver halide photographic material according to claim 1, wherein the compound of the general formula (I) according to claim 1 is selected from the compounds represented by the following general formula (II). General formula (II) In the formula (II), Z ₂ represents an oxygen atom, a sulfur atom, a selenium atom, a nitrogen atom, or a carbon atom. _{V 4, V 5, V 6} ,
And V ₇ represent a hydrogen atom or a substituent. However, these substituents may form a ring together. X ₁ , X ₂ , X
_{3, V 1, V 2,} V 3, q 1, q 2, q 3, R 1, R 2, L 1, L
₂ , L ₃ , n ₁ , M ₁ , and m ₁ have the same meanings as in formula (I). 3. The compound represented by the general formula (I) or (II) according to claim ₁ , wherein R ₁ and R ₂ are an alkyl group substituted with an acid group. 3. The silver halide photographic light-sensitive material according to claim 1, wherein 4. The silver halide photographic light-sensitive material according to claim 2, wherein the compound of the general formula (II) according to claim 2 is selected from the compounds represented by the following general formula (III). General formula (III) In the formula (III), V ₁ ′, V ₂ ′ and V ₃ ′ are a hydrogen atom,
Or a non-aromatic substituent. V ₄ ′, V ₅ ′, V ₆ ′, and V ₇ ′ represent a hydrogen atom or a substituent. However, V ₅ '
And V ₆ ′, or V ₆ ′ and V ₇ ′ together form 5 members or 6 members
A member ring may be formed. R ₁₀ represents a hydrogen atom or an alkyl group. When Z ₂ is a nitrogen atom, R ₁₀ represents a hydrogen atom. n ₁ ′ represents 0 or 1. R ₁ ′ and R ₂ ′ represent an alkyl group substituted with an acid group. X ₁ , X ₂ , X ₃ ,
q ₁ , q ₂ , q ₃ , M ₁ , m ₁ , and Z ₂ have the same meanings as in formula (II). 5. The compound represented by the general formula (I), (II) or (III), wherein X ₁ is a sulfur atom, X ₂ is a carbon atom, and X ₃ is a nitrogen atom or a carbon atom. 5. The silver halide photographic material according to claim 1, wherein the material is an atom. 6. The silver halide photographic light-sensitive material according to claim ₂ , wherein in the compound represented by formula (II) or (III), Z ₂ is a sulfur atom. material. 7. The compound represented by the general formula (I), (II) or (III), wherein R ₁ , R ₂ , R ₁ ′ and R ₂ ′ are sulfoalkyl groups. Claims 1 to 6
A silver halide photographic material as described in any one of the above. 8. A compound represented by the general formula (II) or (III)
In the compound, V_Four, V _Five, V₇, V_Four’, V_Five',as well as
V₇’Is a hydrogen atom and V₆, And V₆’Is a halogen field
Or a phenyl group.
7. The silver halide photographic light-sensitive material according to any one of items 7. 9. A compound represented by the general formula (II) or (III)
In the compound, V_Four, V _Five, V_Four’And V_Five’Is a hydrogen atom
And V₆And V₇, And V₆’And V₇’Together
8. A zeolite ring is formed.
A silver halide photographic light-sensitive material according to any one of the above. 10. The silver halide photograph according to claim 1, wherein the compound represented by formula (I), (II) or (III) is J-aggregating. Photosensitive material.