JP2003029366A - Methine dye and silver halide photographic sensitive material containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new methine dye compound and a high sensitivity silver halide photographic sensitive material containing the compound. SOLUTION: The silver halide photographic sensitive material contains a compound of formula (1), wherein L1 is a linking group; m1 and m2 are each an integer of 1-5; Dye1 is a first chromophore of formula (2); and Dye2 is a second chromophore. In the formula (2), X1 and X2 are each -O-, -S-, -NR6 - or -CR7 R8 -; R1 , R2 and R6 -R8 are each H, an alkyl, alkenyl, aryl or a heterocyclic group; M1 -M3 are each methine; n1 is an integer of 0-3; V1 and V2 are each a substituent; n2 and n3 are each an integer of 0-4, in the case of n2, n3>=2, symbols V1 are mutually the same or different and may link to each other to form a ring, and in the case of n3>=2, symbols V2 are mutually the same or different and may link to each other to form a ring but at least one of V1 and V2 is a substituent containing a group attracted to silver halide.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel methine dye compound, particularly a linked methine dye compound in which two chromophores are linked, and a silver halide photographic light-sensitive material containing the same.

[0002]

2. Description of the Related Art Methine compounds have hitherto been used as spectral sensitizing dyes for silver halide photographic light-sensitive materials. The following are known techniques for improving the light absorption rate of silver halide grains. In order to improve the light absorptance per grain, it is necessary to increase the adsorption density of the sensitizing dye to the silver halide grains, but the ordinary spectral sensitizing dye is a nearly monolayer in a monolayer. Adsorbs, no more. Several proposals have been made to solve this problem. PBGilman, Jr. et al., Phot
ographic Science and Engineering, Volume 20, Volume 3
No. 97 (1976), a cationic dye was adsorbed on the first layer and an anionic dye was adsorbed on the second layer by using electrostatic force. GB Bird et al., U.S. Pat.
In No. 316, multiple dyes were adsorbed on silver halide grains in multiple layers and sensitized by the contribution of Forster-type excitation energy transfer. Sugimoto et al., JP-A-63-138,341, 64-84,
No. 244, spectral sensitization was performed by energy transfer from the luminescent dye. However, all of these were attempts to adsorb a dye in an amount equal to or more than the saturated adsorption amount on silver halide grains, but none of them had the effect of increasing the sensitivity and had a problem such as an increase in intrinsic desensitization. It was On the other hand, two or more unconjugated dye chromophores are linked by a covalent bond.
For component-linked dyes, U.S. Pat.
2,425,772, 2,518,732, 2,521,944, 2,59
2,196 or European Patent 565,083. However, these were not intended to improve the light absorption rate. As those aiming to positively improve the light absorptivity, GB Bird et al. In U.S. Pat. We tried to sensitize by moving, but the sensitivity was not significantly improved. Ukai et al., In JP-A-64-91134, bind at least one substantially non-adsorptive dye containing at least two sulfo or carboxy groups to a spectral sensitizing dye capable of being adsorbed on silver halide. Is proposed. Bishwa Karma et al. In JP-A-6-27,578 discloses a two-component linking dye in which an adsorptive cyanine dye and a non-adsorptive oxonol are linked to silver halide, and Patton et al. In EP 887700A1. The two-component linked dyes, which are a cyanine dye and a non-adsorptive merocyanine dye linked by using a specific linking group, are spectrally sensitized by using the dyes. It cannot be said that there is. As described above, sufficient sensitivity enhancement cannot be achieved by any of the methods of patents and documents, and further technical development is required.

[0003]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a novel methine-linked dye and a highly sensitive silver halide photographic light-sensitive material containing the same.

[0004]

The above objects of the present invention have been achieved by the following means. (1) In a silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support,
A silver halide photographic light-sensitive material comprising the emulsion layer containing a compound represented by the following general formula (1). General formula (1)

[0005]

[Chemical 5]

In the formula, L ₁ represents a linking group, m 1 represents an integer of 1 to 5 and m 2 represents an integer of 1 to 5. CI ₁ represents an ion that neutralizes charge, and y 1 represents the number necessary for neutralizing charge. Dy
e1 represents the first chromophore represented by the general formula (2), and Dye2
Represents the second chromophore. General formula (2)

[0007]

[Chemical 6]

X ₁ and X ₂ are independently --O-- and --S.
_{-, - NR 6 -, -} CR 7 R 8 - represents, R ₆ to R ₈ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, ant - represents a group or a heterocyclic group. R ₁ and R ₂ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group. M _{1 to} M ₃ each independently represent a methine group, and n 1 represents an integer of 0 to 3. V ₁ and V ₂
Represents a substituent, and n2 and n3 each represent an integer of 0-4. When n2 and n3 are 2 or more, V ₁ and V ₂ may be the same or different and may be connected to each other to form a ring. However, V
_At least one of _{1 and} V ₂ represents a substituent containing an adsorptive group to silver halide. Linking group L in formula (1)
₁ is linked to Dye1 at R ₁ , R ₂ , V ₁ or V ₂ . (2) The silver halide photographic light-sensitive material according to (1), wherein the adsorptive group is a group containing a sulfur atom. (3) In the compound represented by the general formula (1), the substituent containing an adsorptive group to at least one of the substituents V _{1 and} V ₂ in Dye1 is a thienyl group, an alkylthio group, The silver halide photographic light-sensitive material as described in (1) or (2), which represents a substituent containing a mercapto group or a thiocarbonyl group. (4) In the compound represented by the general formula (1), the substituent containing an adsorptive group to at least one of the substituents V _{1 and} V ₂ in Dye1 is a thienyl group or an alkylthio group. Characterized by representing a substituent containing (1)
The silver halide photographic light-sensitive material described in (2) or (3). (5) The compound represented by the general formula (1) is characterized in that the adsorptive power to silver halide grains is Dye1> Dye2, (1) to (4) Silver halide photographic light-sensitive material. (6) The compound represented by the general formula (1) is characterized in that both of the substituents V _{1 and} V ₂ in Dye ₁ represent a substituent containing an adsorptive group to silver halide (1) The silver halide photographic light-sensitive material described in any one of (5) to (5). (7) In the compound represented by the general formula (1), Dye2 is any one of a cyanine chromophore, a merocyanine chromophore, and an oxanol chromophore, (1) to (6) The silver halide photographic light-sensitive material described in. (8) The silver halide photographic light-sensitive material described in (7), wherein in the compound represented by the general formula (1), Dye2 is a cyanine chromophore. (9) The silver halide photographic light-sensitive material as described in (7), wherein in the compound represented by the general formula (1), Dye2 is an oxanol chromophore. (10) The silver halide photographic light-sensitive material as described in (7), wherein in the compound represented by the general formula (1), Dye2 is a merocyanine chromophore. (11) In the general formula (1) compounds represented by, -SO ₃ M on _{Dye2, -OSO 3 M, -PO 3} M 2, -OPO 3 M 2, a group containing any of -COOM substituted And M represents a proton or a cation. (12) A methine dye compound represented by the general formula (1) described in (1) to (11). (13) In the silver halide photographic light-sensitive material, the general formula (1)
The compound represented by is adsorbed to silver halide grains at Dye1 to form a J-association, and when Dye2 not adsorbed to silver halide grains is photoexcited, electron transfer or energy transfer to Dye1 is performed. The silver halide photographic light-sensitive material as described in any one of (1) to (11), which is characterized. (14) A silver halide photographic emulsion containing a compound represented by the general formula (1) is an emulsion in which tabular grains having an aspect ratio of 2 or more are present in an amount of 50% (area) or more of all silver halide grains in the emulsion. The silver halide photographic light-sensitive material as described in any one of (1) to (11) and (13), characterized by being present. (15) The silver halide photographic emulsion containing the compound represented by the general formula (1) is selenium-sensitized, which is characterized in that (1) to (11), (13), and (14) The silver halide photographic light-sensitive material as described in any one of items

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The compound of the present invention represented by the general formula (1) is described in detail below.

When the compound of the present invention has an alkyl group, an alkylene group, an alkenyl group or an alkenylene group, they may be linear or branched and may be substituted, unless otherwise specified. It may be replaced. Further, when the compound of the present invention has a cycloalkyl group, an aryl group, a heterocyclic group, a cycloalkenylene group, an arylene group, and a heterylene group, they may be a single ring or a condensed ring unless otherwise specified. May be present or may be substituted or unsubstituted.

In the present invention, when a specific moiety is referred to as a "group", the moiety is substituted with one or more (up to the maximum possible number) of substituents even if the moiety is not itself substituted. It means that it may be done. For example, "alkyl group" means a substituted or unsubstituted alkyl group. Further, the substituent that can be used in the compound of the present invention includes any substituent regardless of the presence or absence of substitution. For example, the substituent group W described below may be mentioned. The substituent represented by W may be any one, and is not particularly limited,
For example, a halogen atom, an alkyl group (including a cycloalkyl group, a bicycloalkyl group and a tricycloalkyl group), an alkenyl group (including a cycloalkenyl group, a bicycloalkenyl group), an alkynyl group, an aryl group, a heterocyclic group ( Heterocyclic group), cyano group, hydroxyl group, nitro group, carboxyl group, alkoxy group,
Aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group (including anilino group), ammonio group,
Acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl and arylsulfonylamino group, mercapto group, alkylthio group,
Arylthio group, heterocyclic thio group, sulfamoyl group,
Sulfo group, alkyl and aryl sulfinyl group, alkyl and aryl sulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, aryl and heterocyclic azo group, imide group, phosphino group , Phosphinyl groups, phosphinyloxy groups, phosphinylamino groups, phospho groups, silyl groups, hydrazino groups, ureido groups, and other known substituents. More specifically, W is a halogen atom (eg, fluorine atom, chlorine atom, bromine atom, 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, for example, 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, ie, having 5 to 3 carbon atoms
It 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-
And a tricyclo structure having many ring structures. The alkyl group in the substituents described below (for example, an alkyl group of an alkylthio group) represents an alkyl group having such a concept, and further includes an alkenyl group and an alkynyl group. ], An alkenyl group [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 group in which one hydrogen atom of a cycloalkene having 3 to 30 carbon atoms is removed. A group of, for example, 2-cyclopenten-1-yl,
2-cyclohexen-1-yl), a bicycloalkenyl group (a substituted or unsubstituted bicycloalkenyl group, preferably a substituted or unsubstituted bicycloalkenyl group having 5 to 30 carbon atoms, that is, a 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). ], An alkynyl group (preferably a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, for example, ethynyl, propargyl, trimethylsilylethynyl group), an 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). It is a monovalent group obtained by removing one hydrogen atom from a group heterocyclic compound, and more preferably a 5- or 6-membered aromatic heterocyclic group having 3 to 30 carbon atoms, such as 2-furyl. 2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl, 1-methyl-2-
It may be a cationic heterocyclic group such as pyridinio or 1-methyl-2-quinolinio. ), 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, such as phenoxy, 2-methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, 2-tetradecanoylaminophenoxy), silyloxy groups (preferably carbon). A silyloxy group having 3 to 20 carbon atoms, 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), an acyloxy group (preferably formyloxy group, substituted or unsubstituted with 2 to 30 carbon atoms) Substituted alkylcarbonyloxy group, substituted or unsubstituted arylcarbonyloxy group having 6 to 30 carbon atoms, for example, formyloxy, acetyloxy, pivaloyloxy, stearoyloxy, benzoyloxy, p-methoxyphenylcarbonyloxy), carbamoyl An oxy 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), an alkoxycarbonyloxy group (preferably a substituted or unsubstituted alkoxycarbonyloxy group having 2 to 30 carbon atoms, for example, Methoxycarbonyloxy, ethoxycarbonyloxy, t-butoxycarbonyloxy, n-octylcarbonyloxy), aryloxycarbonyloxy group (preferably substituted or unsubstituted aryloxycarbonyloxy group having 7 to 30 carbon atoms) , For example, phenoxycarbonyloxy, p-
Methoxyphenoxycarbonyloxy, pn-hexadecyloxyphenoxycarbonyloxy), an amino group (preferably an amino group, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted carbon atom 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, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, an aryl group). And an ammonio group substituted with a heterocycle, for example, trimethylammonio, triethylammonio, diphenylmethylammonio), an acylamino group (preferably a formylamino group, a carbon number of 1 to 30)
A substituted or unsubstituted alkylcarbonylamino group,
A substituted or unsubstituted arylcarbonylamino group having 6 to 30 carbon atoms, for example, formylamino, acetylamino, pivaloylamino, lauroylamino, benzoylamino, 3,4,5-tri-n-octyloxyphenylcarbonylamino) An aminocarbonylamino group (preferably a substituted or unsubstituted aminocarbonylamino having 1 to 30 carbon atoms, for example, carbamoylamino, N, N-dimethylaminocarbonylamino, N, N
-Diethylaminocarbonylamino, morpholinocarbonylamino), an alkoxycarbonylamino group (preferably a substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms, for example, methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino, n- Octadecyloxycarbonylamino,
N-methyl-methoxycarbonylamino), aryloxycarbonylamino group (preferably having 7 to 3 carbon atoms)
A substituted or unsubstituted aryloxycarbonylamino group of 0, for example, phenoxycarbonylamino, p-chlorophenoxycarbonylamino, m-n-octyloxyphenoxycarbonylamino), a sulfamoylamino group (preferably having a carbon number) 0 to 30 substituted or unsubstituted sulfamoylamino groups, for example, sulfamoylamino, N, N-dimethylaminosulfonylamino, Nn-octylaminosulfonylamino), alkyl and arylsulfonylamino groups ( Preferably, a substituted or unsubstituted alkylsulfonylamino having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfonylamino having 6 to 30 carbon atoms, for example, methylsulfonylamino, butylsulfonylamino, phenylsulfonylamino, 2, 3,5-to Chlorophenyl sulfonylamino, p- methylphenyl sulfonylamino), a mercapto group, an alkylthio group (preferably having 1 to 30 carbon atoms
A substituted or unsubstituted alkylthio group such as methylthio, ethylthio, n-hexadecylthio), an arylthio group (preferably a substituted or unsubstituted arylthio having 6 to 30 carbon atoms such as phenylthio, p-chlorophenylthio, m-methoxyphenylthio), a heterocyclic thio group (preferably a substituted or unsubstituted heterocyclic thio group having 2 to 30 carbon atoms, 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 groups (preferably substituted or unsubstituted with 1 to 30 carbon atoms) An alkylsulfinyl group, a substituted or unsubstituted 6 to 30 arylsulfinyl group, for example, 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 carbon atom having 7 to 30 carbon atoms) Arylcarbonyl group, having 4 to 3 carbon atoms
A heterocyclic carbonyl group linked to a carbonyl group at 0 substituted or unsubstituted carbon atoms, for example acetyl,
Pivaloyl, 2-chloroacetyl, stearoyl, benzoyl, pn-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-nitrophenoxycarbonyl, 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. A group (preferably a substituted or unsubstituted carbamoyl having 1 to 30 carbon atoms, for example, 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, 3 to 30 carbon atoms). Substituted or unsubstituted heterocyclic azo group, for example, phenylazo, p-chlorophenylazo, 5-ethylthio-1,3,4-thiadiazol-2-ylazo), imide group (preferably N
-Succinimide, N-phthalimide), 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 a 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, for example, trimethylhydrazino, a ureido group (preferably a substituted or unsubstituted ureido group having 0 to 30 carbon atoms, for example, N, N).
-Dimethylureido). In addition, a ring (aromatic or non-aromatic hydrocarbon ring or heterocycle, which can be further combined to form a polycyclic condensed 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, oxazo-
Ring, thiazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, indolizine ring, indol ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinolidine ring, quinoline ring, phthalazine ring,
Naphthyridine ring, quinoxaline ring, quinoxazoline ring,
Examples thereof include 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 phenoxathiin ring, a phenothiazine ring and a phenazine ring. It is also possible to adopt a structure in which) is condensed.

Of the above-mentioned substituents W, those having a hydrogen atom may be substituted with the above-mentioned substituent after removing the hydrogen atom. Examples of such a functional group include an alkylcarbonylaminosulfonyl group, an arylcarbonylaminosulfonyl group, an alkylsulfonylaminocarbonyl group, and an arylsulfonylaminocarbonyl group. Examples thereof include methylsulfonylaminocarbonyl, p-methylphenylsulfonylaminocarbonyl, acetylaminosulfonyl and benzoylaminosulfonyl groups.

In the formula, m1 represents an integer of 1 to 5, preferably 1 or 2, more preferably 1, and m2 is 1.
It represents an integer of from 5 to 1, preferably 1 or 2, and more preferably 1.

Dye1 represents the first chromophore represented by the general formula (2). X ₁ and X ₂ are each independently -O-, -S-,
Represents —NR ₆ — and —CR ₇ R ₈ —, and R _{6 to} R ₈ are each independently a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group (specifically described below. Examples of R ₁ and R ₂ include the preferable examples of a hydrogen atom, an alkyl group, a sulfoalkyl group and an aryl group.
Group, more preferably a hydrogen atom or an alkyl group. ), R ₆ is preferably a hydrogen atom, an alkyl group or a sulfoalkyl group, more preferably an alkyl group or a sulfoalkyl group. R ₇ and R ₈ preferably represent an alkyl group. It is preferable that X ₁ and X ₂ are each —O— or —S—.

In the formula, R ₁ and R ₂ are each independently a hydrogen atom or an alkyl group (preferably having 1 to 18 carbon atoms (hereinafter referred to as C number), more preferably 1 to 7, and particularly preferably 1 to 4). Unsubstituted alkyl groups (eg, methyl, ethyl, propyl, isopropyl, butyl, isobutyl,
Hexyl, octyl, 2-ethylhexyl, dodecyl,
Octadecyl), a substituted alkyl group having a C number of 1 to 18, preferably 1 to 7, and particularly preferably 1 to 4 (for example, an alkyl group substituted with the above W (excluding an alkyl group) as a substituent can be mentioned. Preferably, an aralkyl group (eg, benzyl, 2-phenylethyl), a hydroxyalkyl group (eg, 2-hydroxyethyl, 3-hydroxypropyl, 6-hydroxyhexyl), a carboxyalkyl group (eg, 2-carboxyethyl, 3-). Carboxypropyl, 4-carboxybutyl, carboxymethyl, 5-carboxypentyl), alkoxyalkyl group (eg, 2-methoxyethyl, 2- (2-methoxyethoxy) ethyl), aryloxyalkyl group (eg, 2-phenoxy). Ethyl, 2- (1-naphthoxy) ethyl), alkoxycarbonylalkyl group (eg ethoxycarbonylmethyl, 2-benzyloxycarbonylethyl), aryloxycarbonylalkyl group (eg 3-phenoxycarbonylpropyl), acyl Oxyalkyl group (eg 2-acetyloxyethyl), acylalkyl group (eg 2-acetylethyl), carbamoylalkyl group (eg 2-morpholinocarbonylethyl), sulfamoylalkyl group (eg N, N-dimethylsulfamoyl) Methyl), a sulfoalkyl group (for example, 2-sulfobenzyl, 3-sulfo-3-phenylpropyl, 2-sulfoethyl, 3-sulfopropyl, 3-sulfobutyl, 4-sulfobutyl, 2- [3-sulfopropoxy] ethyl, 2-hydroxy-3-sulfopropyl, 3-sulfopropoxyethoxyethyl), 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 (for example, methanesulfonylcarbamoylmethyl group) ), An acylcarbamoylalkyl group (eg, acetylcarbamoylmethyl group), an acylsulfamoylalkyl group (eg, acetylsulfamoylmethyl group), an alkylsulfonylsulfamoylalkyl group (eg, methanesulfonylsulfamoylmethyl group), a halogen substitution Alkyl group (for example, 2-chloroethyl, 2,2,2-trifluoroethyl)]}, alkenyl group (preferably having a C number of 2 to 20, for example, vinyl, allyl, 3-butenyl, oleyl, and W described above are substituted. An alkenyl group, In example sulfoalkenyl group (such as 3-sulfo-2-propenyl), etc.), ant -
Group (a C 6-20, preferably C 6-10, more preferably C 6-8 substituted or unsubstituted ar-
Group (for example, the aryl group substituted with W described above as an example of the substituent. Specific examples include phenyl group, 1-naphthyl group, 2-naphthyl, p-methoxyphenyl group, p- Methylphenyl group, p-chlorophenyl group, etc.)), heterocyclic group (C number 1 to 2).
A substituted or unsubstituted heterocyclic group having 0, preferably 3 to 10, and more preferably 4 to 8 C is a heterocyclic group substituted with W described above as an example of the substituent. Include 2-furyl group, 2-thienyl group, 2-
Pyridyl group, 3-pyrazolyl, 3-isoxazolyl,
3-isothiazolyl, 2-imidazolyl, 2-oxazolyl, 2-thiazolyl, 2-pyridazyl, 2-pyrimidyl, 3-pyrazyl, 2- (1,3,5-triazolyl), 3
-(1,2,4-triazolyl), 5-tetrazolyl, 5-
Examples thereof include a methyl-2-thienyl group and a 4-methoxy-2-pyridyl group. )). R ₁ and R ₂ are preferably a hydrogen atom, an alkyl group, a sulfoalkyl group or an aryl group, and more preferably an alkyl group or a sulfoalkyl group.

M _{1 to} M _{3 each} independently represent a methine group and may have a substituent, and the substituent is the above-mentioned substituent group W.
However, preferably, for example, an alkyl group having a C number of 1 to 20 (eg, methyl, ethyl, i-propyl), a halogen atom (eg, chlorine, bromine, iodine, fluorine), a nitro group, a C number of 1 to 1 20 alkoxy groups (eg methoxy, ethoxy), C 6-26 aryl groups (eg phenyl, 2-naphthyl), C 0-20 heterocyclic groups (eg 2-pyridyl, 3- Pyridyl), C
An aryloxy group of the number 6 to 20 (for example, phenoxy,
1-naphthoxy, 2-naphthoxy), C1-20 acylamino groups (eg acetylamino, benzoylamino), C1-20 carbamoyl groups (eg N, N-
Dimethylcarbamoyl), a sulfo group, a hydroxy group, a carboxy group, an alkylthio group having 1 to 20 C atoms (for example, methylthio), a cyano group and the like. Further, it may form a ring with another methine group, or may form a ring with an auxochrome. Preferred are unsubstituted, ethyl group-substituted, and methyl group-substituted methine groups. n1 represents an integer of 0 to 3, preferably an integer of 0 to 2, and more preferably 1 or 2. When n1 is 2 or more, M ₁ and M ₂ may be the same or different. Also, when n1 is 0, X ₁ ,
It is preferred that both X ₂ are -S-.

V ₁ and V ₂ represent a substituent, n2 and n3 each represent an integer of 0 to 4, preferably 1 or 2 respectively.
Is. When n2 and n3 are 2 or more, V ₁ and V ₂ may be the same or different and may be connected to each other to form a ring. However, at least one of V _{1 and} V ₂ represents a substituent containing an adsorptive group to silver halide. Preferably, both V ₁ and V ₂ represent a substituent containing an adsorptive group to silver halide. V _1, or more V ₁ was when V ₂ there are a plurality, or V ₂ is be the same as each other, it may be different, a plurality of V _1, or at least one halogenated Of V ₂ If it is a substituent containing an adsorptive group to silver,
There are effects of the present invention.

The adsorptive group to silver halide means that the adsorptive power of the molecule to the silver halide grain is empirically or theoretically increased by including the substituent in the molecule. Means any known substituent.
Preferred substituents include those containing a sulfur atom. Examples of the substituent containing an adsorptive group include a thienyl group, an alkylthio group, a mercapto group, or a thiocarbonyl group, and a substituent containing these. Specifically preferred are 2-thienyl, 3-thienyl,
Examples thereof include methylthio, ethylthio, propylthio, methylthiomethyl, thioacetyl, thioacetyloxy, methoxythiocarbonyl, thioacetylamino, mercapto, methylthioacetyl, and substituents containing these. Of these, more preferred are 2-thienyl, 3-thienyl, methylthio, ethylthio, thioacetyl, thioacetyloxy, methoxythiocarbonyl, thioacetylamino, and methylthioacetyl, and more preferred.
It is 2-thienyl, 3-thienyl, methylthio or ethylthio, more preferably 2-thienyl or 3-thienyl, most preferably 2-thienyl.

When V ₁ and V ₂ are other than the above-mentioned substituent containing an adsorptive group to silver halide, the above-mentioned substituent group W
However, preferably, for example, an alkyl group having a C number of 1 to 20 (a preferred example is the same as R ₁ and R ₂ ), a halogen atom (eg, chlorine, bromine, iodine, fluorine), a nitro group, a C number of 1 ~ 20 alkoxy groups (eg, methoxy,
Ethoxy), C 6-20 aryl groups (eg phenyl, 2-naphthyl), C 0-20 heterocyclic groups (eg 2-pyridyl, 3-pyridyl, 1-pyrrolyl, 2-thienyl) ), An aryloxy group having a C number of 6 to 20 (for example,
Phenoxy, 1-naphthoxy, 2-naphthoxy), C number 1
˜20 acylamino group (eg acetylamino, benzoylamino), C 1-20 carbamoyl group (eg N, N-dimethylcarbamoyl), sulfo group, C 0-20 sulfonamide group (eg methanesulfonamide) ), A sulfamoyl group having a C number of 0 to 20 (for example, N-
Methylsulfamoyl), a hydroxyl group, a carboxyl group, an alkylthio group having a C number of 1 to 20 (for example, methylthio), a cyano group and the like. V ₁₁ is preferably an alkyl group, a halogen atom (especially chlorine or bromine), an aryl group, an acylamino group, a carbamoyl group, an alkoxy group, a hydroxyl group, a sulfo group or a carboxyl group.

L ₁ is R ₁ , R ₂ , V ₁ or V _{2 and is} Dye
Connect with 1. It is preferably linked to V ₁ or R _1, and more preferably linked to R ₁ . At that time, L
_The groups in which one hydrogen atom is withdrawn from the respective ends of ₁ , R ₁ and V ₁ are connected to each other, but this does not necessarily mean that such production is performed by a synthetic method.

L ₁ represents a linking group (including a single bond), which may be any linking group, but preferably a single bond or an alkylene group (preferably having 1 to 2 carbon atoms (hereinafter referred to as C number)).
0, for example, methylene, ethylene, propylene, butylene, pentylene, hexylene, octylene, an arylene group (preferably having a C number of 6 to 26, such as phenylene, naphthylene), an alkenylene group (preferably having a C number of 2 to 2).
0, for example, ethenylene, propenylene), an alkynylene group (preferably having a C number of 2 to 20, for example, ethynylene, propynylene), an amide group, an ester group, a sulfamide group,
Sulfonate group, ureido group, sulfonyl group, sulfinyl group, thioether group, ether group, carbonyl group, -NR51- (R51 is a hydrogen atom or a monovalent substituent, and the substituent is preferably W. ), A heterylene group (preferably having a C number of 1 to 26, for example, 6-chloro-1,3,5-triazyl-2,4-diyl group, pyrimidine-2,4-diyl group, quinoxaline-2,3). -Diyl group) composed of one or more combinations of 0 to 100 carbon atoms, preferably 1 or more or 20 carbon atoms.
The following linking groups are represented. L ₁ is preferably -G _1- (A _1-
G ₂ -) represented by tl -. A ₁ is -O-, regardless of orientation
_{-S -, - SO 2 -,} - NR 3 -, - COO -, - CON
R ₄ − or —SO ₂ NR ₅ — is represented, and R _{3 to} R ₅ are each independently a hydrogen atom, an alkyl group, an alkenyl group,
It represents an aryl group or a heterocyclic group (the above preferred examples are the same as R ₁ and R ₂ ). R ₃ is preferably a hydrogen atom or an alkyl group, more preferably an alkyl group, and R ₄ and R ₅ are preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom. A ₁ is preferably —O—, —SO ₂ —, —COO—,
It represents —CONR ₄ —, more preferably —CONR ₄ —.

G ₁ and G ₂ are each independently an alkylene group (preferably having 1 to 20 carbon atoms (hereinafter referred to as C number),
For example, methylene, ethylene, propylene, butylene, hexylene, octylene, 2-methylbutylene, 3-phenylpentylene), alkenylene group (preferably having a C number of 2 to 2).
20, for example, ethenylene, propenylene, 2-butenylene), an arylene group (preferably having a C number of 6 to 26, such as 1,4-phenylene, 1,4-naphthylene), and these groups each having the above-mentioned substituents. The group W may be replaced. G ₁ and G ₂ preferably represent an alkylene group, and more preferably represent a linear unsubstituted alkylene group having a C number of 1 to 8.

T1 represents an integer of 1 to 10, preferably 1
Alternatively, it represents 2, more preferably 1. t1 is 2 or more
When multiple A₁And G₂May be the same or different. t1
When is 1, A₁Is -COO-, -CONR_Four-, -SO₂
NR_FiveIt is preferable that any one of-, and -COO-
Or-CONR_FourIt is more preferable that it is-, and
R_FourIt is more preferable that it is −. When t1 is 2 or more,
A₁At least one of -COO- and -CONR_Four-,-
SO ₂NR_FiveIt is preferable that any one of −,
O- or -CONR_FourMore preferably, it is -C
ONR_FourIt is more preferable that it is −. Also in that case
Rino A₁For -COO-, -CONR_Four-, -SO
₂NR_Five-, -O-, -SO₂Be one of
More preferably, -O- or -CONR_FourBe −
Is more preferable.

Dye2 represents the second chromophore. The chromophore represented by Dye2 may be any, but for example, cyanine dye, styryl dye, hemicyanine dye, merocyanine dye, trinuclear merocyanine dye, tetranuclear merocyanine dye, rhodacyanine dye, complex cyanine dye,
Complex merocyanine dye, allopolar dye,
Oxonol dye, hemioxonol dye, squarylium dye, croconium dye, azamethine dye, coumarin dye, allylidene dye, anthraquinone dye, triphenylmethane dye, azo dye, azomethine dye, spiro compound, metallocene dye, fluorenone dye, Frugide dye, perylene dye, phenazine dye, phenothiazine dye, quinone dye, indigo dye, diphenylmethane dye, polyene dye, acridine dye, acridinone dye, diphenylamine dye, quinacridone dye, quinophthalone dye, phenoxazine dye, phthaloperylene dye, porphyrin dye, chlorophyll Examples thereof include dyes, phthalocyanine dyes, and metal complex dyes. Preferred are cyanine dyes, styryl dyes, hemicyanine dyes, merocyanine dyes, trinuclear merocyanine dyes, tetranuclear merocyanine dyes, rhodacyanin dyes, complex cyanine dyes, complex merocyanine dyes, allopolar dyes, oxonol dyes, hemioxonol. Examples thereof include polymethine chromophores such as dyes, squarylium dyes, croconium dyes, azamethine dyes, and oxonol dyes. For more details on these dyes, please see F.M.
(FM Harmer) "Heterocyclic Compounds-
Cyanine soybean and related compounds
(Heterocyclic Compounds-Cyanine Dyes and Related
Compounds), John Willy & Sons (Joh
Wiley & Sons) -New York, London, 196
4th edition, DMS Turmer, "Heterocyclic Compounds-Special Topics in Heterocyclic Chemistry" (Heter
ocyclic Compounds-Special topics in heterocyclic
chemistry) ", Chapter 18, Section 14, 482-51
It is described in page 5, etc. Examples of preferable general formulas of dyes include general formulas described in US Pat. No. 5,994,051 on pages 32 to 36 and general formulas described on US Pat. No. 5,747,236 on pages 30 to 34. Further, general formulas of preferable cyanine dyes, merocyanine dyes, and rhodacyanine dyes are described in U.S. Pat. No. 5,340,694, Nos. 21 to 21.
Those shown in (XI), (XII), and (XIII) of column 22 (however, the number of n12, n15, n17, and n18 is not limited, and an integer of 0 or more (preferably 4 or less)) To be Dye2 is preferably a cyanine chromophore, a merocyanine chromophore, or an oxanol chromophore, a cyanine chromophore,
It is more preferably any of the merocyanine chromophores, and most preferably the cyanine chromophore.

Dye2 is preferably substituted with a group containing a water-soluble, non-adsorptive substituent. The water-soluble, non-adsorptive substituent is a hydrophilic group compared to an alkyl group, such as a positively or negatively charged group or a group containing an atom having an electronegativity larger than carbon and having a lone electron pair. Any group can be used as long as it is highly functional. Particularly preferred -SO ₃ as _{M, -OSO 3 M, -PO 3} M 2, -OPO 3 M 2, include groups -COOM is substituted. However, M represents a proton or a cation.

The cyanine chromophore preferably represents a chromophore represented by the following general formula (4). General formula (4)

[0027]

[Chemical 7]

In the formula, Za ₁ and Za ₂ each represent an atomic group forming a 5-membered or 6-membered nitrogen-containing heterocycle, which are further represented by a benzene ring, a benzofuran ring, a pyridine ring, a pyrrole ring and an indole ring. It may be condensed with a ring or thiophene ring. Ra ₁ and Ra ₂ each represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group (the above preferred examples are the same as R ₁ and R ₂ ), preferably a hydrogen atom,
It represents an alkyl group or a sulfoalkyl group, more preferably an alkyl group or a sulfoalkyl group. Ma _{1 to} Ma ₇ each represent a methine group and may have a substituent, and the substituent may be any of the above-mentioned substituent groups W, but is preferably, for example, an alkyl group having a C number of 1 to 20 ( For example, methyl, ethyl, i-propyl), a halogen atom (eg,
Chlorine, bromine, iodine, fluorine), nitro group, C number 1-2
An alkoxy group of 0 (eg methoxy, ethoxy), C
Formula 6-26 aryl group (eg, phenyl, 2-naphthyl), C number 0-20 heterocyclic group (eg, 2-pyridyl, 3-pyridyl), C number 6-20 aryloxy group (For example, phenoxy, 1-naphthoxy, 2-naphthoxy), C1-20 acylamino group (eg acetylamino, benzoylamino), C1-20 carbamoyl group (eg N, N-dimethylcarbamoyl), sulfo. Examples thereof include a group, a hydroxy group, a carboxy group, an alkylthio group having 1 to 20 C (eg methylthio), a cyano group and the like. It may also form a ring with another methine group,
Alternatively, a ring can be formed with the auxochrome. Preferred are unsubstituted, ethyl group-substituted, and methyl group-substituted methine groups. na ¹ and na ² are 0 or 1, and preferably 0. ka ¹ represents an integer of 0 to 3. Preferably 0
Is an integer from 1 to 2, more preferably 0 or 1. When ka ¹ is 2 or more, Ma ₃ and Ma ₄ may be the same or different. CI represents an ion that neutralizes charge, and y represents the number necessary for neutralizing charge. The linking group L ₁ may be linked at any position, but it is preferably linked to Ra ₁ or Ra ₂ .

The merocyanine chromophore preferably represents a chromophore represented by the following general formula (5). General formula (5)

[0030]

[Chemical 8]

In the formula, Za ₃ represents an atomic group forming a 5- or 6-membered nitrogen-containing heterocyclic ring, and these are further a benzene ring, a benzofuran ring, a pyridine ring, a pyrrole ring, an indole ring and a thiophene ring. It may be condensed with a ring or the like. Za
₄ represents an atomic group forming an acidic nucleus. Ra ₃ represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group (the above preferred examples are the same as Ra ₁ and Ra ₂ ). Ma ₈ ~ M
a ₁₁ each represents a methine group (preferred examples are the same as Ma ₁ to Ma ₇ ). na ³ is 0 or 1. ka ² represents an integer of 0 to 3, preferably an integer of 0 to 2, and more preferably 1 or 2. When ka ² is 2 or more, Ma ₁₀ ,
Ma ₁₁ may be the same or different. CI represents an ion that neutralizes charge, and y represents the number necessary for neutralizing charge. Dye
When 2 represents a group other than oxabarbiturdimethine merocyanine, it may be linked to the linking group L ₁ at any position, but is preferably linked to a substituent on Za ₄ .
However, for the reason of controlling the orientation of the second layer, when Dye2 represents oxabarbitu-ludimethine merocyanine, barbitz-
It is necessary that the substituent on the acid be linked to L ₁ .

The oxanol chromophore preferably represents a chromophore represented by the following general formula (6). General formula (6)

[0033]

[Chemical 9]

In the formula, Za ₅ and Za ₆ each represent an atomic group forming an acidic nucleus. Ma _{12 to} Ma ₁₄ each represent a methine group (the above preferred examples are the same as Ma ₁ to Ma ₇ ). ka ³ represents an integer of 0 to 3, preferably an integer of 0 to 2. ka ³
When is 2 or more, Ma ₁₂ and Ma ₁₃ may be the same or different.
CI represents an ion that neutralizes charge, and y represents the number necessary for neutralizing charge. The linking group L ₁ may be linked at any position.

Za ₁ , Za ₂ and Za _{3 each} have 3 to 25 carbon atoms.
An oxazole nucleus (for example, 2-3-methyloxazolyl, 2-3-ethyloxazolyl, 2-3,4-diethyloxazolyl, 2-3-methylbenzoxazolyl,
2-3-ethylbenzoxazolyl, 2-3-sulfoethylbenzoxazolyl, 2-3-sulfopropylbenzoxazolyl, 2-3-methylthioethylbenzoxazolyl, 2-3-methoxyethylbenzo Oxazolyl, 2-3-sulfobutylbenzoxazolyl, 2-3
-Methyl-β-naphthoxazolyl, 2-3-methyl-
α-naphthoxazolyl, 2-3-sulfopropyl-β
-Naphthoxazolyl, 2-3-sulfopropyl-γ-
Naphthoxazolyl, 2-3- (3-naphthoxyethyl) benzoxazolyl, 2-3,5-dimethylbenzoxazolyl, 2-6-chloro-3-methylbenzoxazolyl, 2-5-bromo -3-Methylbenzoxazolyl, 2-3-Ethyl-5-methoxybenzoxazolyl, 2-5-phenyl-3-sulfopropylbenzoxazolyl, 2-5- (4-bromophenyl) -3 -Sulfobutylbenzoxazolyl, 2-3-dimethyl-5,
6-dimethylthiobenzoxazolyl and the like), a thiazole nucleus having 3 to 25 carbon atoms (for example, 2-3).
-Methylthiazolyl, 2-3-ethylthiazolyl, 2-
3-sulfopropylthiazolyl, 2-3-sulfobutylthiazolyl, 2-3,4-dimethylthiazolyl, 2-
3,4,4-trimethylthiazolyl, 2-3-carboxyethylthiazolyl, 2-3-methylbenzothiazolyl, 2-3-ethylbenzothiazolyl, 2-3-butylbenzothiazolyl , 2-3-sulfopropylbenzothiazolyl, 2-3-sulfobutylbenzothiazolyl, 2-
3-methyl-β-naphthothiazolyl, 2-3-sulfopropyl-γ-naphthothiazolyl, 2-3- (1-naphthoxyethyl) benzothiazolyl, 2-3,5-dimethylbenzothiazolyl, 2-6-chloro-3- Methylbenzothiazolyl, 2-6-iodo-3-ethylbenzothiazolyl, 2-5-bromo-3-methylbenzothiazolyl,
2-3-ethyl-5-methoxybenzothiazolyl, 2-
5-phenyl-3-sulfopropylbenzothiazolyl,
2-5- (4-bromophenyl) -3-sulfobutylbenzothiazolyl, 2-3-dimethyl-5,6-dimethylthiobenzothiazolyl and the like), and a carbon number of 3 to 3.
25 imidazole nuclei (e.g., 2-1,3-diethylimidazolyl, 2-1,3-dimethylimidazolyl, 2
-1-methylbenzimidazolyl, 2-1,3,4-triethylimidazolyl, 2-1,3-diethylbenzimidazolyl, 2-1,3,5-trimethylbenzimidazolyl, 2-6-chloro-1,3-dimethylbenzimidazolyl, 2-5,6-dichloro-1,3-diethylbenzimidazolyl, 2-1,3-disulfopropyl-5
-Cyano-6-chlorobenzimidazolyl and the like), an indolenine nucleus having 10 to 30 carbon atoms (for example,
3,3-dimethylindolenine and the like), quinoline nucleus having 9 to 25 carbon atoms (for example, 2-1 -methylquinolyl, 2-1 -ethylquinolyl, 2-1 -methyl 6-
Chloroquinolyl, 2-1,3-diethylquinolyl, 2-
1-methyl-6-methylthioquinolyl, 2-1-sulfopropylquinolyl, 4-1-methylquinolyl, 4-1
(Sulfoethylquinolyl, 4-l-methyl-7-chloroquinolyl, 4-1,8-diethylquinolyl, 4-l-methyl-6-methylthioquinolyl, 4-l-sulfopropylquinolyl and the like can be mentioned.) , A C3-25 selenazole nucleus (for example, 2-3-methylbenzoselenazolyl, etc.), a C5-25 pyridine nucleus (for example, 2-pyridyl, etc.), and the like. Other examples include thiazoline nuclei, oxazoline nuclei, selenazoline nuclei, tellurazoline nuclei, tellurazol nuclei, benzotelrazol nuclei, imidazoline nuclei, imidazo [4,5-quinoxalin] nuclei, oxadiazole nuclei, thiadiazole nuclei. , A tetrazole nucleus, and a pyrimidine nucleus. These may be substituted, and examples of the substituent include the above-mentioned Substituent Group W, but preferably, for example, an alkyl group (eg, methyl, ethyl, propyl), a halogen atom (eg, chlorine, bromine, iodine, fluorine). , Nitro group,
Alkoxy group (eg, methoxy, ethoxy), aryl-
Group (for example, phenyl), a heterocyclic group (for example, 2-pyridyl, 3-pyridyl, 1-pyrrolyl, 2-thienyl),
Aryloxy group (eg, phenoxy), acylamino group (eg, acetylamino, benzoylamino), carbamoyl group (eg, N, N-dimethylcarbamoyl), sulfo group, sulfonamide group (eg, methanesulfonamide), sulfamoyl group (eg, N-methylsulfamoyl), a hydroxy group, a carboxy group, an alkylthio group (for example, methylthio), a cyano group and the like. Preferably, an oxazole nucleus, an imidazole nucleus,
It is a thiazole nucleus. These heterocycles may be further condensed. Examples of the condensed ring include a benzene ring, a benzofuran ring, a pyridine ring, a pyrrole ring, an indol ring and a thiophene ring.

Za ₄ , Za ₅ and Za ₆ each represent an atomic group necessary for forming an acidic nucleus, and are edited by James, The Theory of the P.
hotographic Process, 4th edition, Macmillan, 197
7 years, page 198. Specifically, 2-
Pyrazolone-5-one, pyrazolidine-3,5-dione, imidazolin-5-one, hydantoin, 2 or 4-thiohydantoin, 2-iminooxazolidine-4
-One, 2-oxazoline-5-one, 2-thiooxazoline-2,4-dione, isolo-danine, rhodanine, indan-1,3-dione, thiophen-3-one, thiophen-3-one- 1,1-dioxide, indoline-2-one, indoline-3-one, 2-oxoindazolium, 5,7-dioxo-6,7-dihydrothiazolo [3,2-a] pyrimidine, 3,4 -Dihydroisoquinolin-4-one, 1,3-dioxane-4,6-dione, barbituric acid, 2-thiobarbituric acid, coumarin-2,4-dione, indazoline-2-one, pyrido [1, Examples include nuclei of 2-a] pyrimidine-1,3-dione, pyrazolo [1,5-b] quinazolone, pyrazolopyridone, and the like. Preferred are hydantoin, rhodanine, barbituric acid and 2-oxazolin-5-one. Preferably as Za ₄ is Barubitsu - a le acid.

Specific examples of the cyanine chromophore, the merocyanine chromophore or the oxanol chromophore include FM Harmer
Written by Heterocyclic Compounds-Cyanine Dyes and Relat
ed Compounds, John & Wiley & Sons, New York, London,
The one described in 1964 can be mentioned.

The general formulas of cyanine dyes and merocyanine dyes are described in US Pat. No. 5,340,694, pages 21 and 22, (X
Those shown in I) and (XII) are preferable.

CI represents an ion that neutralizes the charge. Whether a compound is a cation, an anion, or has a net ionic charge depends on its substituents. Typical cations are ammonium and alkali metal ions, while anions can be either inorganic or organic ions. Examples of the cation include sodium ion, potassium ion, triethylammonium ion, diethyl (i-propyl) ammonium ion, pyridinium ion, and 1-ethylpyridinium ion, and examples of the anion include:
Halogen anion (for example, chloride ion, bromide ion,
Fluorine ion, iodine ion), substituted aryl sulfonate ion (for example, paratoluene sulfonate ion),
Examples thereof include alkylsulfate ion (for example, methylsulfate ion), sulfate ion, perchlorate ion, tetrafluoroborate ion, acetate ion and the like. y represents the number required to neutralize the charge.

In the compound of the present invention represented by the general formula (1), preferable examples of Dye1 are as follows. However, the present invention is not limited to this. Note that the structural formulas of the compounds of the present invention described below are only one limiting structure among a number of possible resonance structures, and other structures that can be obtained by resonance may be used.

[0041]

[Chemical 10]

[0042]

[Chemical 11]

[0043]

[Chemical 12]

[0044]

[Chemical 13]

In the compound of the present invention represented by the general formula (1), preferable examples of Dye2 are as follows. However, the present invention is not limited to this.

[0046]

[Chemical 14]

[0047]

[Chemical 15]

[0048]

[Chemical 16]

[0049]

[Chemical 17]

[0050]

[Chemical 18]

In the compound of the present invention represented by the general formula (1), preferable examples of the linking group —L ₁ — are as follows. However, the present invention is not limited to this.

[0052]

[Chemical 19]

[0053]

[Chemical 20]

[0054]

[Chemical 21]

Specific examples of the compound represented by formula (1) of the present invention are shown below, but the present invention is not limited thereto.

[0056]

[Chemical formula 22]

[0057]

[Chemical formula 23]

The compounds of the present invention can be synthesized, for example, according to the methods described in the following documents. FMHarmer
Written by Heterocyclic Compounds-Cyanine Dyes and Relat
ed Compounds, John & Wiley & Sons, New York, London,
1964, DMSturmer, Heterocyclic Compound
s− Special Topics in Heterocyclic Chemistry, 18th
Chapter, section 14, pages 482-515, John & Wiley & Son
s, New York, London, 1977, European patent 887700A
No. 1.

In the compound represented by the general formula (1),
The adsorption power to the silver halide grains is preferably Dye1> Dye2. At least one or more -SO ₃ M In that regard the _{Dye2, -OSO 3 M, -OPO 3} M 2, -PO 3
It is preferable that M ₂ and -COOM are contained, and it is more preferable that at least one or more -SO ₃ M is contained.
In addition, M represents a proton or a cation. The adsorptivity to silver halide grains can be achieved by using each model compound.

Further, Dy of the compound represented by the general formula (1)
When e2 is photoexcited, electron transfer or energy to Dye1
It is preferably movable. Further, in the silver halide photographic emulsion and the silver halide light-sensitive material, the compound represented by the general formula (1) is adsorbed to the silver halide grains at Dye1, and Dye2 not adsorbed to the silver halide grains is photoexcited. It is preferable that electrons or energy transfer to Dye1 when performed. Further, in the silver halide photographic emulsion and the silver halide light-sensitive material, it is preferable that the compound represented by the general formula (1) is adsorbed to silver halide grains by Dye1 to form a J association.

Next, the silver halide photographic light-sensitive material of the present invention will be described in detail.

The methine dye compound of the present invention is mainly used as a sensitizing dye in a silver halide photographic emulsion and a silver halide photographic light-sensitive material. The compounds of the present invention can be used alone or in combination of the compounds of the present invention, or can be used in combination with other sensitizing dyes in a silver halide photographic emulsion or a silver halide light-sensitive material. In that case, the dyes used are preferably cyanine dyes, merocyanine dyes, rhodacyanine dyes, trinuclear merocyanine dyes, tetranuclear merocyanine dyes, allopola dyes, hemicyanine dyes and styryl dyes. Cyanine dyes, merocyanine dyes and rhodacyanine dyes are more preferred, and cyanine dyes are particularly preferred. For details of these dyes, see FM Harmer, "Heterocyclic Compounds-Cyanine and Relative Compounds (Heterocyclic Comp.
Sounds-Cyanine Dyesand Related Compounds '', John Wiley & Son
s) -New York, London, 1964, published
"Heterocyclic Compou-Special Topics in Heterocyclic Chemistry" by DM Sturmer
nds-Special topics in heterocyclic chemistry)
”, Chapter 18, Section 14, pp. 482-515. Preferred dyes are the sensitizations described in the general formulas and the specific examples described in U.S. Pat. No. 5,994,051, pages 32 to 44, and U.S. Pat. Examples include dyes. Further, preferable general formulas of cyanine dyes, merocyanine dyes, and rhodacyanine dyes are described in US Pat. No. 5,340,694.
Nos. 21 to 22 columns (XI), (XII), and (XIII) are shown (however, the number of n12, n15, n17, and n18 is not limited, and an integer of 0 or more (preferably 4 or less) ).)
Is mentioned.

One kind of these sensitizing dyes may be used,
Two or more kinds may be used, and a combination of sensitizing dyes is often used particularly for the purpose of supersensitization. Typical examples thereof are US Pat. Nos. 2,688,545 and 2,977,229.
Issue No. 3,397,060 Issue 3,522,052
Issue 3, Issue 3,527,641, Issue 3,617,293
No. 3,628,964, 3,666,480
Issue 3, Issue 3,672,898, Issue 3,679,428
No. 3,303,377, No. 3,769,301
Nos. 3,814,609 and 3,837,862
No. 4,026,707, British Patent 1,344,2
No. 81, No. 1,507, 803, Japanese Patent Publication No. 43-493
No. 36, No. 53-12375, JP-A No. 52-1106.
18 and 52-109925.

Along with the sensitizing dye, a dye having no spectral sensitizing effect itself or a substance which does not substantially absorb visible light and exhibits supersensitization may be contained in the emulsion.

Supersensitizers useful in spectral sensitization in the present invention (eg, pyrimidylamino compounds, triazinylamino compounds, azolium compounds, aminostyryl compounds, aromatic organic acid formaldehyde condensates, azaindene compounds, cadmium salts). , And a combination of a supersensitizer and a sensitizing dye are described in, for example, US Pat. No. 3,511,66.
No. 4, No. 3,615, 613, No. 3, 615, 632
Issue No. 3,615,641 Issue No. 4,596,767
No. 4,945,038, 4,965,182
No. 4,965,182, 2,933,390
Issue No. 3,635,721 Issue 3,743,510
No. 3,617,295, No. 3,635,721, etc., and the method described in the above-mentioned patent is also preferable for the usage thereof.

It has been recognized that the timing of adding the sensitizing dye of the present invention (and other sensitizing dyes and supersensitizers) to the silver halide emulsion of the present invention has been useful so far. Any of the known emulsion preparation steps may be performed. 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 196749 and the like, the period before the grain forming step or / and desalting of the silver halide, the period during and / or after the desalting process and before the start of chemical ripening,
As disclosed in JP-A-58-113920, it is added at any time or step immediately before or during the chemical ripening, at any time before the emulsion is coated before the coating after the chemical ripening and before the coating. May be. Also, US Pat.
No. 5,666, JP-A-58-7629, etc., the same compound alone or in combination with a compound having a different structure, for example, during the grain formation step and the chemical ripening step or the chemical ripening step. It may be added in divided portions such as after completion or before chemical aging or during the process and after completion, and the compound and the combination of compounds added in different portions may also be added in different types. May be.

The sensitizing dye of the present invention (and other sensitizing colors
The same applies to the base and supersensitizers).
Depending on the shape and size of the silver rogenide grains,
The addition amount may be sufficient, but it is preferably 1 mol equivalent of silver halide.
Or 1 × 10^-8~ 8 × 10 ^-1Can be used in moles
It For example, the silver halide grain size is 0.2 to 1.3.
In the case of μm, 2 × 10 1 per mol of silver halide
^-6~ 3.5 x 10^-3The molar addition amount is preferably 7.5 ×
10^-6~ 1.5 × 10^-3More preferably, the amount added is molar.

The sensitizing dye of the present invention (and other sensitizing dyes and supersensitizers) can be directly dispersed in the emulsion. Further, these may be first dissolved in a suitable solvent such as 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. it can. At this time, additives such as a base, an acid, and a surfactant can be coexistent. Ultrasonic waves can also be used for dissolution. As a method of adding this 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 to prepare a dispersion of this compound. No. 3,822,135, a method of adding the compound to an emulsion, a method of dispersing the compound in a water-soluble solvent and adding the dispersion to the emulsion, as described in JP-B-46-24185. A method of dissolving a compound in a surfactant and adding the solution to the emulsion, as described in JP-A-51-74624, using a compound for red-shifting to dissolve the solution into the emulsion. A method of addition, a method of dissolving the compound in an acid containing substantially no water and adding the solution to the emulsion, as described in JP-A-50-80826, is used. In addition, US Pat.
2,343, 3,342,605, 2,99
The methods described in 6,287, 3,429,835 and the like can also be used.

In the present invention, the photographic emulsion controlling the light-sensing mechanism contains any of silver bromide, silver iodobromide, silver chlorobromide, silver iodide, silver iodochloride, silver iodobromochloride, and silver chloride as silver halide. Although the halogen composition on the outermost surface of the emulsion may be 0.1 mol% or more, more preferably 1 mol% or more, and particularly preferably 5 mol% or more, a stronger multilayer adsorption structure can be constructed. . The particle size distribution may be wide or narrow, but narrower is more preferable. The silver halide grains of a photographic emulsion are those having regular crystal grains such as cubes, octahedra, tetradecahedrons and rhombic dodecahedrons, and irregular grains such as spheres and plates. (Irregular) crystal form,
It may have a higher-order plane ((hkl) plane) or a mixture of grains of these crystal forms, but it is preferably a tabular grain, and the tabular grain will be described in detail below. For particles with higher surface, see Journal of I
Reference may be made to pages 247 to 254 of maging Science, Vol. 30, (1986). Further, the silver halide photographic emulsion used in the present invention may contain the above-mentioned silver halide grains alone or as a mixture of plural grains.
The silver halide grains may have different phases in the inside and the surface, may have a multi-phase structure having a junction structure, may have a localized phase on the grain surface, or may have a uniform grain as a whole. It may consist of phases. Moreover, they may be mixed. These various emulsions may be either a surface latent image type which forms a latent image mainly on the surface or an internal latent image type which is formed inside the grain.

In the present invention, tabular silver halide grains having a halogen composition of silver chloride, silver bromide, silver chlorobromide, silver iodobromide, silver chloroiodobromide and silver iodochloride are preferably used. The tabular grains preferably have a major surface of (100) or (111). Tabular grains having a (111) major surface, hereinafter referred to as (111) tabular grains, usually have triangular or hexagonal faces. Generally, the more uniform the distribution, the higher the proportion of tabular grains with more hexagonal faces. A hexagonal monodisperse flat plate is described in JP-B-5-61205.

Tabular grains having a (100) plane as a main surface,
Hereinafter referred to as (100) flat plate also has a rectangular or square shape. In this emulsion, grains having an adjacent edge ratio of less than 5: 1 are called tabular grains rather than acicular grains. In tabular grains containing a large amount of silver chloride or silver chloride, the (100) tabular grains originally have higher main surface stability than the (111) tabular grains. In the case of a (111) flat plate, it is necessary to stabilize the (111) main surface.
-80660, JP-A-9-80656, and US Pat. No. 5,298,388.

The silver chloride or the (111) plate having a high content of silver chloride used in the present invention is disclosed in the following patents. U.S. Pat. No. 4,414,306, U.S. Pat. No. 4,400,463, U.S. Pat. No. 4,713,323.
U.S. Pat. No. 4,783,398, U.S. Pat. No. 4,962.
491, US Pat. No. 4,983,508, US Pat. No. 4
804621, US Pat. No. 5,389,509, US Pat. No. 5,217,858, US Pat. No. 5,460,934.

The high silver bromide (111) tabular grains used in the present invention are described in the following patents. U.S. Pat. No. 4,425,425, U.S. Pat. No. 4,425,426,
US Pat. No. 443426, US Pat. No. 4,439,520
U.S. Pat. No. 4,414,310, U.S. Pat. No. 4,433.
048, US Pat. No. 4,647,528, US Pat. No. 4
665012, US Pat. No. 4,672,027, US Pat. No. 4,678,745, US Pat. No. 4,684,607,
U.S. Pat. No. 4,593,964, U.S. Pat. No. 472288.
6, US Pat. No. 4,722,886, US Pat. No. 475.
5617, US Pat. No. 4,755,456, US Pat. No. 4,806,461, US Pat. No. 4,801,522, US Pat. No. 4,835,322, US Pat. No. 4839268,
U.S. Pat. No. 4,914,014, U.S. Pat. No. 4,96201.
5, US Pat. No. 4,977,074, US Pat. No. 498.
5350, US Pat. No. 5,061,609, US Pat. No. 5061616, US Pat. No. 5,068,173, US Pat. No. 5,132,203, US Pat.
U.S. Pat. No. 5,334,469, U.S. Pat. No. 5,334.
495, US Pat. No. 5,358,840, US Pat. No. 5
No. 372927.

The (100) plate used in the present invention is described in the following patents. US Patent 438
6156, US Pat. No. 5,275,930, US Pat. No. 5,292,632, US Pat. No. 5,314,798, US Pat. No. 5,320,938, US Pat. No. 5,319,635.
U.S. Pat. No. 5,356,764, European Patent 5699.
71, European Patent No. 737887, JP-A-6-308.
648, JP-A-9-5911.

The silver halide emulsion used in the present invention has a higher surface area / area in which the sensitizing dye disclosed in the present invention is adsorbed.
A tabular silver halide grain having a high volume ratio is preferable, the aspect ratio is preferably 2 or more, more preferably 5 or more,
Particularly preferably, it is 8 or more. There is no particular upper limit, but it is preferably 1000 or less, more preferably 500 or less. The thickness of the tabular grains is preferably less than 0.2 μm,
More preferably less than 0.1 μm, even more preferably 0.0
It is less than 7 μm.

Here, the aspect ratio of 2 or more means that the silver halide grains having an aspect ratio (circular equivalent diameter of silver halide grains / grain thickness) of 2 or more are projections of all silver halide grains in the emulsion. It means that 50% or more of the area exists. Preferably 70% or more, particularly preferably 85
% Emulsion is present.

The following techniques are applied to prepare thin tabular grains having such a high aspect ratio. The tabular grains of the present invention preferably have a uniform dislocation dose distribution between grains. The emulsion of the present invention contains 100 to 50% of all silver halide grains containing 10 or more dislocation lines per grain.
(Number) is preferable, and more preferably 10
0 to 70%, particularly preferably 100 to 90%
Occupy When it is less than 50%, it is not preferable in terms of homogeneity between particles.

In the present invention, when determining the proportion of grains containing dislocation lines and the number of dislocation lines, it is preferable to directly observe the dislocation lines for at least 100 grains,
More preferably 200 particles or more, particularly preferably 300 particles.
Observe for more than particles and obtain.

Gelatin is advantageously used as a protective colloid used in the preparation of the emulsion of the present invention and as a binder for other hydrophilic colloid layers, but other hydrophilic colloids can also be used. . For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; hydroxyethyl cellulose, carboxymethyl cellulose.
Cellulose, cellulose derivatives such as cellulose sulfates, soda alginate, sugar derivatives such as starch derivatives;
Polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinyl imidazole, polyvinyl pyrazole, single or co-weight A wide variety of synthetic hydrophilic polymeric substances such as coalesced can be used. Examples of gelatin include lime-processed gelatin, acid-processed gelatin and Bull. Soc. Sci.
Photo. Japan. No. 16. P30 (196
The enzyme-treated gelatin as described in 6) may be used, or a hydrolyzed product or an enzymatically decomposed product of gelatin can also be used. The emulsion of the present invention is preferably washed with water for desalting and dispersed in a newly prepared protective colloid.
The temperature of water washing can be selected according to the purpose, but it is preferably selected in the range of 5 ° C to 50 ° C. The pH at the time of washing with water can also be selected according to the purpose, but it is preferably selected between 2 and 10. More preferably, it is in the range of 3-8. The pAg at the time of washing with water can also be selected according to the purpose, but it is preferably selected between 5 and 10. As a method of water washing, Noodle water washing method, dialysis method using a semipermeable membrane,
It can be selected and used from a centrifugal separation method, a coagulation sedimentation method, and an ion exchange method. In the case of the coagulation sedimentation method, a method using a sulfate, a method using an organic solvent, a method using a water-soluble polymer, a method using a gelatin derivative and the like can be selected.

During preparation of the emulsion of the present invention, for example, during grain formation,
In the desalting step, during chemical sensitization, it is preferable to allow a salt of a metal ion to exist before coating, depending on the purpose. When it is doped into the grains, it is preferably added at the time of grain formation, after the grain formation or before the end of chemical sensitization when the grain surface is modified or when it is used as a chemical sensitizer. A method of doping the entire particle, a method of doping only the core portion of the particle, or a method of doping only the shell portion can be selected. For example, Mg, Ca, Sr, Ba, Al,
Sc, Y, La, Cr, Mn, Fe, Co, Ni, C
u, Zn, Ga, Ru, Rh, Pd, Re, Os, I
r, Pt, Au, Cd, Hg, Tl, In, Sn, P
b and Bi can be used. These metals can be added in the form of salts such as ammonium salts, acetates, nitrates, sulfates, phosphates, hydroxides or hexacoordinated complex salts and tetracoordinated complex salts which can be dissolved at the time of grain formation. For example,
CdBr ₂ , CdCl ₂ , Cd (NO ₃ ) ₂ , Pb (N
O ₃ ) ₂ , Pb (CH ₃ COO) ₂ , K ₃ [Fe (C
N) ₆ ], (NH ₄ ) ₄ [Fe (CN) ₆ ], K ₃ IrC
Examples include l ₆ , (NH ₄ ) ₃ RhCl ₆ , and K ₄ Ru (CN) ₆ . The ligand of the coordination compound can be selected from halo, aco, cyano, cyanate, thiocyanate, nitrosyl, thionitrosyl, oxo and carbonyl. These may use only one type of metal compound, but may use two types or a combination of three or more types.

The metal compound is preferably added after being dissolved in water or a suitable organic solvent such as methanol or acetone. In order to stabilize the solution, a method of adding a hydrogen halide aqueous solution (eg, HCl, HBr) or an alkali halide (eg, KCl, NaCl, KBr, NaBr) can be used. If necessary, acids and alkalis may be added. The metal compound may be added to the reaction vessel before grain formation or during grain formation. In addition, a water-soluble silver salt (eg AgNO ₃ ) or an aqueous alkali halide solution (eg NaCl, K)
It is also possible to add it to Br, KI) and continuously add it during the formation of silver halide grains. Further, a solution independent of the water-soluble silver salt and the alkali halide may be prepared and continuously added at an appropriate time during grain formation. It is also preferable to combine various addition methods.

The method of adding a chalcogen compound as described in US Pat. No. 3,772,031 during emulsion preparation may be useful in some cases. In addition to S, Se and Te, cyanate, thiocyanate, selenocyanic acid, carbonate, phosphate and acetate may be present.

The silver halide grain of the present invention is subjected to at least one of sulfur sensitization, selenium sensitization, gold sensitization, palladium sensitization, noble metal sensitization and reduction sensitization in any step of the process for producing a silver halide emulsion. Can be applied with. It is preferable to combine two or more sensitizing methods. Various types of emulsions can be prepared depending on which step is chemically sensitized. There are a type in which chemically sensitized nuclei are embedded inside a grain, a type in which a chemical sensitized nucleus is embedded at a shallow position from the grain surface, and a type in which a chemically sensitized nucleus is formed on the surface. In the emulsion of the present invention, the location of the chemically sensitized nuclei can be selected depending on the purpose, but generally preferred is the case where at least one chemically sensitized nucleus is formed near the surface. One of the chemical sensitizations which can be preferably carried out in the present invention is chalcogen sensitization and noble metal sensitization, either alone or in combination, by TH James, The Photographic Process, 4th Edition. , Published by Macmillan,
1977, (TH James, The Theo
ry of the Photographic Pr
access, 4th ed, Macmillan, 19
77) using active gelatin as described on pages 67-76, and Research Disclosure, 120, April 1974, 12008; Research Disclosure. -Ja, 34, 1975, 6
Mon, 13452, U.S. Pat. Nos. 2,642,361, 3,297,446, 3,772,031,
No. 3,857,711, No. 3,901,714,
No. 4,266,018 and No. 3,904,4
15 and pAg 5-10, pH 5-8 and temperature 30-as described in British Patent 1,315,755.
It can be sulfur, selenium, tellurium, gold, platinum, palladium, iridium or combinations of these sensitizers at 80 ° C. In the noble metal sensitization, noble metal salts such as gold, platinum, palladium and iridium can be used, and among them, gold sensitization, palladium sensitization and a combination of both are preferable. In the case of gold sensitization, chloroauric acid, potassium chloroorate, potassium olythiocyanate
Well-known compounds such as gold, gold sulfide, and gold selenide can be used. The palladium compound means a divalent or tetravalent palladium salt. A preferred palladium compound is represented by R ₂ PdX ₆ or R ₂ PdX ₄ . Where R
Represents a hydrogen atom, an alkali metal atom or an ammonium group. X represents a halogen atom and represents a chlorine, bromine or iodine atom.

Specifically, K ₂ PdCl ₄ , (NH ₄ ) ₂ P
dCl ₆ , Na ₂ PdCl ₄ , (NH ₄ ) ₂ PdCl ₄ , Li
₂ PdCl ₄ , Na ₂ PdCl ₆ or K ₂ PdBr ₄ are preferred. The gold compound and the palladium compound are preferably used in combination with thiocyanate or selenocyanate. As sulfur sensitizers, hypo, thiourea compounds,
Rhodanine compounds and US Pat. No. 3,857,711
No. 4,266,018 and 4,054.
The sulfur-containing compounds described in No. 457 can be used. It is also possible to carry out chemical sensitization in the presence of a so-called chemical sensitization aid. Useful chemical sensitization aids include azaindene, azapyridazine, azapyrimidine, and other compounds known to suppress fog and increase sensitivity during the chemical sensitization process. Examples of chemical sensitization aid modifiers are disclosed in US Pat. Nos. 2,131,038 and 3,4.
No. 11,914, No. 3,554,757, JP-A-5
No. 8-126526 and the above-mentioned "Photographic Emulsion Chemistry" by Duffin, pp. 138-143. The emulsion of the present invention is preferably combined with gold sensitization. The preferred amount of gold sensitizer is 1 × 10 ⁻⁴ to 1 × per mol of silver halide.
It is 10 ^-7 mol, and more preferably 1 × 10 ^{-5 to} 5 mol.
× 10 ⁻⁷ mol. The preferable range of the palladium compound is 1 × 10 ⁻³ to 5 × 10 ⁻⁷ . The preferable range of the thiocyan compound or the selenocyan compound is 5 × 10 5.
^{It is} from ^-2 to 1 x 10 ^-6 . The preferred amount of sulfur sensitizer used for the silver halide grains of the present invention is silver halide 1
It is 1 × 10 ⁻⁴ to 1 × 10 ⁻⁷ mol per mol, and more preferably 1 × 10 ^{−5 to} 5 × 10 ⁻⁷ mol. Selenium sensitization is a preferred sensitizing method for the emulsion of the present invention. In the selenium sensitization, a known unstable selenium compound is used, and specifically, colloidal metal selenium and selenoureas (eg, N, N-dimethylselenourea, N,
Selenium compounds such as N-diethylselenourea), selenoketones, and selenoamides can be used. In some cases, selenium sensitization is preferably used in combination with sulfur sensitization, precious metal sensitization, or both.

During grain formation of the silver halide emulsion of the present invention,
It is preferable to carry out reduction sensitization after grain formation and before or during chemical sensitization or after chemical sensitization. Here, reduction sensitization refers to a method of adding a reduction sensitizer to a silver halide emulsion, a method of growing or aging in a low pAg atmosphere of pAg 1 to 7 called silver ripening, and a pH of 8 to 8 called high pH ripening. Any of 11 methods of growing or aging in a high pH atmosphere can be selected. Also, two or more methods can be used in combination. The method of adding a reduction sensitizer is a preferable method because the level of reduction sensitization can be finely adjusted. Examples of reduction sensitizers include stannous salts, ascorbic acid and its derivatives, amines and polyamines, hydrazine derivatives, formamidinesulfinic acid,
Silane compounds and borane compounds are known. For the reduction sensitization of the present invention, these known reduction sensitizers can be selected and used, or two or more kinds of compounds can be used in combination. As reduction sensitizers, stannous chloride, thiourea dioxide,
Dimethylamine borane, ascorbic acid and its derivatives are preferred compounds. Since the addition amount of the reduction sensitizer depends on the emulsion production conditions, it is necessary to select the addition amount, but the range of 10 ^-7 to 10 ^-3 mol is suitable per mol of silver halide. The reduction sensitizer is dissolved in water or an organic solvent such as alcohols, glycols, ketones, esters and amides and added during grain growth. It may be added to the reaction vessel in advance, but a method of adding it at an appropriate time during grain growth is preferred. Further, a reduction sensitizer may be added in advance to the water solubility of the water-soluble silver salt or the water-soluble alkali halide, and the silver halide grains may be precipitated using these aqueous solutions. Further, it is also a preferable method to add the solution of the reduction sensitizer in several times as the grains grow, or to continuously add the solution for a long time.

During the process of producing the emulsion of the present invention, acid for silver is used.
It is preferable to use an agent. What is an oxidizing agent for silver?
Has the effect of acting on metallic silver and converting it to silver ions
Refers to a compound. Especially the formation process of silver halide grains and
Very small silver particles by-produced during the chemical sensitization process
Compounds that can convert the above into silver ions are effective. here
The silver ions generated in are, for example, silver halide and sulfide.
You may form a sparingly soluble silver salt such as silver or silver selenide.
You may also form a silver salt that is easily soluble in water, such as silver nitrate.
Yes. The oxidizing agent for silver may be an inorganic substance or an organic substance.
It may be. Examples of the inorganic oxidant include azo.
Hydrogen peroxide, hydrogen peroxide and its adducts (eg NaBO₂
・ H₂O₂・ 3H₂O, 2NaCO₃・ 3H₂O₂, Na_FourP₂
O₇・ 2H₂O₂2Na₂SO_Four・ H₂O₂・ 2H₂O), Bae
Luoxylate (eg, K₂S₂O₈, K₂C₂O₆, K₂P₂
O₈), A peroxy complex compound (for example, K₂[Ti (O
₂) C₂O _Four] ・ 3H₂O, 4K₂SO_Four ・ Ti (O₂) OH
・ SO_Four・ 2H₂O, Na₃[VO (O₂) (C₂H_Four)₂]
・ 6H₂O), permanganate (eg, KMnO_Four),
Chromate (eg K₂Cr₂O₇) Oxygen acid like
Salts, halogen elements such as iodine and bromine, perhalogenates
(Eg potassium periodate), high valent metal salts
(Eg potassium hexacyanoferrate) and thio
There is a sulfonate.

As organic oxidants, quinones such as p-quinone, organic peroxides such as peracetic acid and perbenzoic acid, and compounds that release active halogen (for example, N-
Bromsuccinimide, chloramine T, chloramine B)
Is given as an example.

Preferred oxidizing agents of the present invention are ozone, hydrogen peroxide and its adducts, halogen elements, inorganic oxidizing agents of thiosulfonate and organic oxidizing agents of quinones.
It is a preferable embodiment to use the reduction sensitization and the oxidizing agent for silver in combination. It can be selected from the method of using an oxidant and then the reduction sensitization, the reverse method thereof, or the method of coexisting both. These methods can be selectively used in the grain forming step and the chemical sensitization step.

The photographic emulsion used in the present invention may contain various compounds for the purpose of preventing fog during the manufacturing process of the light-sensitive material, during storage or during photographic processing, or stabilizing photographic performance. . That is, thiazoles (for example, benzothiazolium salt), nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercapto. Benzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles
, Aminotriazoles, benzotriazoles,
Nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole
), Mercaptopyrimidines, mercaptotriazines, for example, thioketo compounds such as oxadrinethione, azaindenes, for example, triazaindenes, tetraazaindenes (especially 4-hydroxy-substituted (1,
Many compounds known as antifoggants or stabilizers such as 3,3a, 7) chitraazaindenes), pentaazaindenes can be added. For example, U.S. Pat. Nos. 3,954,474 and 3,982,94
No. 7 and Japanese Patent Publication No. 52-28660 can be used. JP-A-63-63 is one of the preferred compounds.
There are compounds described in No. 212932. Antifoggants and stabilizers can be used at various times before particle formation, during particle formation, after particle formation, in the washing step, during dispersion after washing, before chemical sensitization, during chemical sensitization, after chemical sensitization, and before coating. It can be added depending on the purpose. In addition to adding the effect of preventing fog and stabilizing during the preparation of the emulsion, the crystal wall of the grain is controlled, the grain size is reduced, the solubility of the grain is reduced, and the chemical sensitization is controlled. It can be used for various purposes such as controlling the arrangement of dyes.

The silver halide emulsion prepared according to the present invention can be used in both color photographic light-sensitive materials and black-and-white photographic light-sensitive materials. As the color photographic light-sensitive material, especially color photographic paper, color photographic film, color reversal film, color diffusion transfer film, and black-and-white photographic light-sensitive material general photographic film, X-ray film, medical Examples thereof include a diagnostic film, a film for printing sensitive material, and a diffusion transfer film.

In the field of films for medical diagnosis and films for printing light-sensitive materials, laser imagers or lasers.
The image can be exposed efficiently by the imager. For the technology in these fields, see Japanese Patent Application Laid-Open No. 7-28
7,337, JP-A-4-335,342, JP-A-5
-313,289, JP-A-8-122,954, JP-A-8-292,512 and the like. Also, a photothermographic material can be used. For example, a catalytically active amount of a photocatalyst (eg, silver halide), a reducing agent,
Known materials include a reducible silver salt (for example, an organic silver salt) and, if necessary, a photosensitive layer in which a color tone controlling agent for controlling the color tone of silver is dispersed in a binder matrix. For these, see, for example, US Pat.
4, U.S. Pat. No. 3,457,075, U.S. Pat. No. 2910377.
U.S. Pat. No. 4,500,626, Japanese Patent Publication No. 43-4924
No. 11-24200, No. 11-24201, No. 11-30832
No. 11-84574, No. 11-65021, No. 11-109547,
11-125880, 11-129629, 11-133536-
11-133539, 11-133542, 11-133543, 11
-223898, 11-352627, 6-130607,
6-332134, 6-332136, 6-
347970, 7-261354, and Japanese Patent Application 2000
-89436, etc. can be mentioned.

The compound of the present invention can also be preferably used in a diffusion transfer photosensitive material. Of these, Japanese Patent Application No. 10-265273 (using preformed dye) and Japanese Patent Application No. 2000-89436 (using coupling forming dye) for the thermal development diffusion transfer method, and Japanese Patent Application No. The method described in No. 11-89801 can be referred to.

The method of preparing the photographic emulsion used in the present invention can be applied from JP-A-10-239789, column 63 line 36 to column 65 line 2. Regarding the type of photosensitive material to which the present invention is applied, such as additives such as color couplers and additives for photographic photosensitive materials, and the processing of photosensitive materials, column 65, item 3 of JP-A-10-239789. Lines to column 73, line 13 can be applied.

The silver halide photographic light-sensitive material of the present invention comprises
Although the various additives described above are used, various additives other than the above can be used depending on the purpose. These additives are described in more detail in Research Disclosure Item 1
7643 (December 1978), Item 18716 (November 1979) and Item 308119 (December 1989), and the corresponding parts are summarized in the table below.

[0095]   Additive type RD17643 RD18716 RD308119 1 Chemical sensitizer Page 23 Page 648 Right column Page 996 2 Sensitivity enhancer Same as above 3 Spectral sensitizer, pages 23-24, page 648, right column-996 right-998 right     Supersensitizer, page 649, right column 4 Whitener 24 pages 998 Right 5 Antifoggant page 24 to 25 page 649 right column 998 right to 1000 right     And stabilizers 6 Light absorber, fill page 25-26 page 649 right column-1003 left-1003 right     , UV absorber, page 650, left column 7 Anti-stain agent Page 25 Right column 650 Left to right column 1002 Right 8 Dye image stabilizer 25 pages 1002 right 9 Hardener 26 pages 651 left column 1004 right to 1005 left 10 Binder-page 26 Same as above 1003 right to 1004 right 11 Plasticizer, Lubricant Page 27 Page 650 Right column 1006 Left to 1006 Right 12 Coating aid, pages 26-27 Same as above 1005 left to 1006 left     Surfactant 13 Antistatic agent Page 27 Same as above 1006 right to 1007 left 14 Matting agent 1008 left to 1009 left

Techniques such as layer arrangement which can be used for the emulsion of the present invention and photographic light-sensitive materials using the emulsion, silver halide emulsions, functional couplers such as dye-forming couplers and DIR couplers, various Regarding additives and the like, and development processing, European Patent No. 0565096A1 (1993)
(October 13, 2013) and the patents cited therein. Below, each item and the corresponding description location are listed.

[0097] 1. Layer composition: p. 61, lines 23 to 35, p. 41 to p. 62, line 14 2. Middle layer: p. 61, lines 36-40 3. Multilayer effect imparting layer: p. 62, lines 15-18 4. Silver halide halogen composition: p. 62, lines 21-25 5. Crystal Habit of Silver Halide Grains: p. 62, lines 26-30 6. Silver halide grain size: p. 62, lines 31-34 7. Emulsion manufacturing method: Page 62, lines 35-40 8. Silver halide grain size distribution: p. 62, lines 41-42 9. Tabular grains: p. 62, lines 43-46 Ten. Internal structure of particles: p. 62, lines 47-53 11. Emulsion latent image forming type: p. 62 line 54 to p. 63 line 5 12. Physical ripening and chemical sensitization of emulsion: Page 63, lines 6-9 13. Mixed use of emulsion: Page 63, lines 10-13 14. Fogging emulsion: p. 63, lines 14-31 15. Non-photosensitive emulsion: page 63, lines 32 to 43 16. Silver coating amount: Page 63, lines 49-50

[0098] 17. Formaldehyde Scavenger: Page 64, lines 54-57 18. Mercapto-based antifoggant: Page 65, lines 1-2 19. Release agents such as fogging agents: Page 65, lines 3-7 20. Dye: Page 65, lines 7-10 twenty one. Color couplers in general: Page 65, lines 11-13 twenty two. Yellow, Magenta and Cyan Couplers: Page 65, lines 14-25 twenty three. Polymer Coupler: Page 65, lines 26-28 twenty four. Diffusible dye-forming coupler: p. 65, lines 29-31 twenty five. Color coupler: Page 65, lines 32 to 38 26. Functional couplers in general: Page 65, lines 39-44 27. Bleach accelerator releasing coupler: page 65 lines 45-48. 28. Development accelerator releasing coupler: p. 65, lines 49-53 29. Other DIR couplers: page 65, line 54 to page 66, line 4 30. Coupler Dispersion Method: Page 66, lines 5 to 28

[0099] 31. Antiseptic / antifungal agent: Page 66, lines 29-33 32. Type of sensitive material: Page 66, lines 34-36 33. Photosensitive layer film thickness and swelling speed: Page 66, line 40 to Page 67, line 1 34. Back layer: Page 67, lines 3-8 35. General development processing: Page 67, lines 9-11 36. Developer and developer: Page 67, lines 12-30 37. Developer additive: Page 67, lines 31-44 38. Inversion processing: Page 67, lines 45-56 39. Treatment liquid opening ratio: Page 67, line 57 to Page 68, line 12 40. Development time: Page 68, lines 13-15 41. Bleaching / Bleaching / Fixing: Page 68, line 16 to Page 69, line 31 42. Automatic processor: Page 69, lines 32-40 43. Washing / rinsing / stabilization: Page 69, line 41 to Page 70, line 18 44. Replenishment / reuse of processing liquid: Page 70, lines 19-23 45. Built-in developer sensitive material: Page 70, lines 24 to 33 46. Development processing temperature: Page 70, lines 34-38 47. Use for film with lens: Page 70, lines 39-41

The exposure method of the silver halide photographic light-sensitive material of the present invention will be described. The exposure for obtaining a photographic image may be performed using a usual method. That is, any of various known light sources such as natural light (sunlight), tungsten electric lamp, fluorescent lamp, mercury lamp, xenon arc lamp, carbon arc lamp, xenon flash lamp, laser, LED and CRT can be used. . Further, it may be exposed by light emitted from a phosphor excited by an electron beam, an X-ray, a γ (gamma) ray, an α (alpha) ray, or the like.

In the present invention, a laser light source may be preferably used. The laser light uses helium-neon gas, argon gas, krypton gas, carbon dioxide gas, or the like as a laser oscillation medium, and a laser using a solid such as ruby or cadmium as an oscillation medium.
Lasers, other liquid lasers, semiconductor lasers, and the like. Since these laser lights are coherent lights having a sharp directivity with a uniform phase at a single frequency, unlike the lights used for ordinary illumination, they are exposed as a light source. The silver halide photographic light-sensitive material for achieving this requires that it has spectral characteristics that match the emission wavelength of the laser used. Of the above-mentioned lasers, the case where a semiconductor laser is used is preferable.

In addition to the sensitizing dye, the compound of the present invention is used as various filter dyes, anti-irradiation dyes or antihalation dyes for the purpose of improving sharpness and color resolution. You can This compound is a silver halide photographic light-sensitive material layer in a conventional manner,
It may be contained in a coating solution such as a filter layer and / or an antihalation layer. The amount of the dye used may be an amount sufficient for coloring the photographic layer, and those skilled in the art can easily select this amount appropriately according to the purpose of use. Generally, the optical density is in the range of 0.05 to 3.0. Is preferably used. The addition time may be any step before coating.

A polymer having a charge opposite to that of the dye ion may coexist in the layer as a mordant, and the dye may be localized in the specific layer by interacting with the dye molecule. As the polymer mordant, for example, US Pat.
548,564, 4,124,386, 3,6
25,694, 3,958,995, 4,16
Examples thereof include those described in Nos. 8,976 and 3,445,231. The compound of the present invention can be added to a desired layer such as an intermediate layer, a protective layer and a back layer in addition to the photosensitive emulsion layer.

Further, the compound of the present invention can be used as a photosensitizer (photocharge separating agent) in various non-silver salt type photoimage forming methods, and can also be used in photocatalysts, photohydrogen generators and the like. it can.

In the present invention, the light absorption intensity is the light absorption area intensity by the sensitizing dye per unit grain surface area,
Optical density Log where I _{0 is} the amount of light incident on the unit surface area of the grain and I is the amount of light absorbed by the sensitizing dye on the surface
(I ₀ / (I ₀ −I)) is defined as a value obtained by integrating the wave number (cm ⁻¹ ). The integration range is 5000 cm ^-1 to 35
Up to 000 cm ^-1 .

The silver halide photographic emulsion according to the present invention has a light absorption intensity of 100 or more and a spectral absorption maximum wavelength of 500 in the case of grains having a spectral absorption maximum wavelength of 500 nm or more.
In the case of grains having a size of less than nm, it is preferable that the silver halide grains having a light absorption intensity of 60 or more are contained in an amount of 1/2 or more of the projected area of all silver halide grains. The maximum wavelength of spectral absorption is 50
In the case of particles of 0 nm or more, the light absorption intensity is preferably 150 or more, more preferably 170 or more, particularly preferably 200 or more, and the spectral absorption maximum wavelength is 500 n.
In the case of particles less than m, the light absorption intensity is preferably 90
Or more, more preferably 100 or more, particularly preferably 1
20 or more. There is no particular upper limit, but it is preferably 200.
It is 0 or less, more preferably 1000 or less, and particularly preferably 500 or less. The maximum wavelength of spectral absorption is 500n.
For particles smaller than m, the spectral absorption maximum wavelength is 350 n
It is preferably m or more.

As an example of the method for measuring the light absorption intensity
Can include a method using a microspectrophotometer
It Microspectrophotometer measures the absorption spectrum of a small area
It is a device that can measure the transmission spectrum of one particle.
Noh. Of the absorption spectrum of a particle by microspectroscopy
Regarding the measurement, the report of Yamashita et al.
6th Annual Conference Lecture Collection, page 15)
You can From this absorption spectrum, the absorption per particle
Concentration intensity is required, but the light passing through the particles is
Since it is absorbed by two surfaces, the unit surface area of the particle surface
The absorption strength of the particles is the absorption value per particle obtained by the above method.
It can be obtained as 1/2 of the harvest intensity. At this time,
The interval where the absorption spectrum is integrated is defined by the light absorption intensity.
5000 cm ^-1From 35000 cm^-1But on the experiment
Is 500 cm before and after the section where there is absorption by the sensitizing dye^-1Degree
The integration of the interval including degrees may be used. Also, the light absorption intensity is increased.
It is determined by the oscillator strength of the dye and the number of adsorbed molecules per unit area.
It is a value that is determined positively, and the oscillator strength and color of the sensitizing dye.
Converted to light absorption intensity by obtaining the elementary adsorption amount and particle surface area
You can do it. The oscillator strength of the sensitizing dye is
Absorption area intensity of solution (optical density x cm^-1) Proportional to
Can be obtained experimentally as
The absorption area intensity of the dye is A (optical density × cm^-1), Sensitized color
B (mol / molAg) is the amount of elementary adsorption, and the particle surface area is
C (m² / MolAg), light absorption by the following formula
The intensity can be obtained within an error range of about 10%. 0.156 x A x B / C Even if the light absorption intensity is calculated from this equation, it is based on the above definition.
Light absorption intensity (Log (I₀ / (I₀ −
I))) is the wave number (cm^-1) And the actual
The same value is obtained.

As a method of increasing the light absorption intensity, there are a method of adsorbing the dye chromophore on the surface of the particle more, a method of increasing the molecular extinction coefficient of the dye, and a method of decreasing the area occupied by the dye. Any method may be used, but a method in which the dye chromophore is more adsorbed on the particle surface is preferable. Here, the state in which the dye chromophore is more adsorbed on the surface of the grain means that there is more dye bound to the vicinity of the silver halide grain, including the dye present in the dispersion medium. Absent. The term "more than one layer" as used herein also includes the case where the dye chromophore is covalently linked to a compound such as a dye adsorbed on the particle surface as in the present invention. In those cases, it is necessary that spectral sensitization be caused by the dye that is not directly adsorbed on the grain surface, and for that purpose, the excitation energy from the dye that is not directly adsorbed on the silver halide to the dye that is directly adsorbed on the grain is Need to be communicated. Therefore, when it is necessary to transfer the excitation energy in more than 10 steps, the final transfer efficiency of the excitation energy becomes low, which is not preferable. One example of this is the case where most of the dye chromophore is present in the dispersion medium as in the case of polymer dyes such as those disclosed in JP-A-2-113239, and the transfer of excitation energy is required in 10 steps or more. The adsorption of the dye chromophore on the silver halide grains is preferably 1.5 layers or more, more preferably 1.7 layers or more, and particularly preferably two layers.

In the present invention, the state in which more chromophores are adsorbed on the surface of silver halide grains means that among the sensitizing dyes added to the emulsion, the dye having the smallest dye occupying area on the surface of silver halide grains. The saturated adsorption amount per unit surface area that is reached is defined as a further saturated coating amount, and the adsorption amount per unit area of the dye chromophore is larger than the more saturated coating amount. Further, the number of adsorption layers means the adsorption amount when the one-layer saturated coating amount is used as a reference. Here, in the case of a dye in which dye chromophores are linked by a covalent bond, the area occupied by each dye in the unlinked state can be used as a reference.
The area occupied by the dye can be obtained from the adsorption isotherm showing the relationship between the free dye concentration and the amount of the adsorbed dye, and the particle surface area. The adsorption isotherm is, for example, A. Hertz (A. Her)
z) et al. Adoption from aqua solutions (Adsorption from Aqua)
eous Solution) Advances in
Chemistry Series (Advances in C
chemistry series) No. 17,173
It can be obtained by referring to the page (1968).

The amount of the sensitizing dye adsorbed on the emulsion particles was determined by separating the emulsion adsorbed with the dye by centrifuging into emulsion particles and a supernatant gelatin aqueous solution, and determining the unadsorbed dye concentration from the spectral absorption measurement of the supernatant. Method to determine the amount of adsorbed dye by subtracting the amount of added dye from the amount of dye added, and drying the precipitated emulsion particles, dissolving a certain amount of the precipitate in a 1: 1 mixture of sodium thiosulfate aqueous solution and methanol, and measuring the spectral absorption. By doing so, two methods of determining the amount of adsorbed dye can be used. When a plurality of types of sensitizing dyes are used, the amount of adsorption of each dye can be determined by a method such as high performance liquid chromatography. The occupied area of the dye can be determined experimentally, but the molecular occupied area of the commonly used sensitizing dyes is around 80Å ² , so for all the dyes, the occupied area of the dye is 80Å ² and the approximate adsorption layer You can also estimate the number.

In the silver halide photographic emulsion containing the compound of the present invention as a sensitizing dye, the shortest wavelength showing 50% of the maximum value Amax of the spectral absorptance by the sensitizing dye and 50% of the maximum value Smax of the spectral sensitivity, respectively. The longest wavelength interval is preferably 120 nm or less, more preferably 10 nm.
It is 0 nm or less. Further, the interval between the shortest wavelength and the longest wavelength showing 80% of Amax and Smax is preferably 20 nm or more, preferably 100 nm or less, and more preferably 8 nm.
It is 0 nm or less, particularly preferably 50 nm or less. Also
The distance between the shortest wavelength and the longest wavelength showing 20% of Amax and Smax is preferably 180 nm or less, more preferably 150 nm or less, particularly preferably 120 nm or less, and most preferably 100 nm or less. The longest wavelength showing a spectral absorption of 50% of Amax or Smax is preferably 46.
0nm to 510nm, or 560nm to 610n
m, or 640 nm to 730 nm.

In the present invention, when the dye chromophores are adsorbed in multiple layers on the silver halide grains, the so-called first layer dye chromophore and the second or more layer dye chromophores which are directly adsorbed on the silver halide grains are used. The reduction potential and the oxidation potential of the chromophore may be any, but the reduction potential of the dye chromophore in the first layer is higher than the value obtained by subtracting 0.2 v from the value of the reduction potential of the dye chromophore in the second or more layers. Is preferable from the viewpoint of promoting electron transfer from the dye in the second layer or more to the dye in the first layer and preventing reverse electron transfer, and the reduction potential of the dye chromophore in the first layer is less than that of the dye chromophore in the second layer or more. It is preferable that the value is noble.

Various methods can be used to measure the reduction potential and the oxidation potential, but it is preferable to use the phase discrimination type second harmonic alternating current polarography, and it is possible to obtain accurate values. it can. The above method of measuring the potential by the phase discrimination type second harmonic alternating current polarography is described in Journal of Imaging Science (Journ).
al of Imaging Science), No. 3
0, page 27 (1986).

The dye chromophores of the second and higher layers are preferably luminescent dyes. As the type of the luminescent dye, those having a skeleton structure of the dye used for the dye laser are preferable. These include, for example, Mitsuo Maeda, Laser Research, Vol. 8, p. 694, p. 803, p. 958 (1980) and vol. 9, p. 85 (1981), and F. Sehaefer.
Organized in "Dye Lasers", Springer (1973).

Further, the absorption maximum wavelength of the dye chromophore of the first layer in the silver halide photographic light-sensitive material is longer than the absorption maximum wavelength of the dye chromophore of the second or more layers, and further the second or more layers. It is preferable that the emission of the dye chromophore of (1) overlaps with the absorption of the dye chromophore of the first layer from the viewpoint of energy transfer efficiency from the dyes of the second or more layers to the dye of the first layer. Further, the dye chromophore in the first layer preferably forms a J-aggregate.
Furthermore, in order to have absorption and spectral sensitivity in a desired wavelength range, it is preferable that the dye chromophores in the second and higher layers also form a J-aggregate. The energy transfer efficiency of the excitation energy of the second layer dye to the first layer dye is preferably 30.
% Or more, more preferably 60%, particularly preferably 90%
% Or more. Here, the excitation energy of the second layer dye refers to the energy of the dye in the excited state generated by absorbing the light energy of the second layer dye. When the excitation energy of a certain molecule is transferred to another molecule, the excitation electron transfer mechanism, the Forster-type energy transfer mechanism (For
It is considered that the excitation energy is transferred through a ster model), a Dexter energy transfer mechanism (Dextor Model), etc., so that even in the multilayer adsorption system of the present research, efficient excitation energy transfer that can be considered from these mechanisms. It is preferable that the condition for causing Further, it is particularly preferable to satisfy the conditions for causing the Forster-type energy transfer mechanism. The energy transfer efficiency from the second layer dye to the first layer dye can be determined as the spectral sensitization efficiency when the second layer dye is excited / the spectral sensitization efficiency when the first layer dye is excited.

The meanings of the terms used in the present invention are described below. Dye occupied area: The occupied area per dye molecule. It can be experimentally determined from the adsorption isotherm. In the case of a dye in which the dye chromophores are linked by a covalent bond, the area occupied by each dye in the unlinked state is used as a reference. 80 Å ^{2 for} simplicity. Single-saturated coating amount: The amount of dye adsorbed per unit particle surface area during single-saturated coating. The reciprocal of the smallest dye footprint of the added dyes. Multilayer adsorption: A state in which the adsorption amount of the dye chromophore per unit particle surface area is higher than the saturated coating amount. In the present invention, the multilayer adsorption means a state in which the adsorption amount of the dye chromophore per unit particle surface area is more than the saturated coating amount. In the case of partial adsorption, it means that two layers are adsorbed. Number of adsorbed layers: The amount of dye chromophore adsorbed per unit particle surface area based on the one-layer saturated coating amount. In the case of a compound in which two dye chromophores are covalently linked, the above adsorption amount × 2 is defined as the number of adsorption layers. For example, when a dye in which two dye chromophores are covalently linked has the same dye occupancy area and the same adsorption amount as a certain non-linked model dye, the number of adsorption layers is 2.

[0117]

EXAMPLES The present invention will now be described based on examples, but the present invention is not limited thereto.

Example 1 Synthesis example of compound D-23 of the present invention

[0119]

[Chemical formula 24]

Cyanine dye [1], 0.54 g (0.8 mmol), and merocyanine dye [2], 0.50 g (0.8 mmol), 1-hydroxybenzotriazol 0.12 synthesized by referring to the method of European Patent 887700A. g (0.88 mmol) was dissolved in 30 ml of dimethyl sulfoxide, and the mixture was stirred at 60 ° C. for 10 minutes. Uronium salt [3], 0.30 g (0.96 mmol) and diisopropylethylamine 0.37 g (2.9 mmol) were added, and the mixture was stirred at 60 ° C. for 3 hours. After cooling, 300 ml of acetone was added, and the precipitated crystals were separated by filtration. The crystals were dissolved in methanol, 0.065 g (0.8 mmol) of sodium acetate was added, isopropyl alcohol was added and the resulting crystals were separated by filtration and washed with isopropyl alcohol. After vacuum drying, the desired yellow crystals of D-23.
47 g (yield 47%) was obtained. The structure is NMR spectrum,
It was confirmed by MS spectrum and elemental analysis. Other compounds of the present invention can be synthesized by the same method as described above.

Example 2 (Preparation of seed emulsion a) 0.017 g of KBr, average molecular weight of 2
Aqueous solution containing 0.4 g of oxidised gelatin of 0000 11
64 ml was kept at 35 ° C. and stirred. AgNO ₃ (1.6
g) An aqueous solution, a KBr aqueous solution, and an oxidation-treated gelatin (2.1 g) aqueous solution having an average molecular weight of 20,000 were added by the triple jet method over 48 seconds. At this time, the silver potential was kept at 13 mV against the saturated calomel electrode. An aqueous KBr solution was added to adjust the silver potential to -66 mV, and then the temperature was raised to 60 ° C. 21 g of succinated gelatin with an average molecular weight of 100,000
Was added, followed by an aqueous solution of NaCl (5.1 g). An AgNO ₃ (206.3 g) aqueous solution and a KBr aqueous solution 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, average molecular weight 100
000 succinated gelatin was added and the pH was adjusted to 5.
8, pAg was adjusted to 8.8 to prepare a seed emulsion. This seed emulsion contains 1 mol of Ag and 8 mol of gelatin per kg of emulsion.
It was a tabular grain containing 0 g, an average equivalent circle diameter of 1.46 μm, a variation coefficient of an 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,
KBr 1.9g, average molecular weight 100,000
Keep 1200 ml of an aqueous solution containing 22 g of ratin at 75 ° C
It was stirred. AgNO ₃(43.9 g) aqueous solution and KBr water
A solution and an aqueous gelatin solution having a molecular weight of 20,000 are disclosed in Japanese Patent Laid-Open No.
Coupling Induction Type Stirrer
25 minutes before mixing just before addition in another chamber with
Added over time. At this time, adjust the silver potential to the saturated calomel electrode.
To -40 mV.

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

(Formation of Second Shell) After the formation of the first shell, an AgNO ₃ (42.6 g) aqueous solution, a KBr aqueous solution, and a gelatin aqueous solution having a molecular weight of 20000 are mixed in a separate chamber just before the addition. Added over 17 minutes. At this time, the silver potential was set to −20 with respect to the saturated calomel electrode.
kept at mV. Then, 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 and KI (6.9 g) aqueous solution and molecular weight 200
A gelatin aqueous solution of No. 00 was mixed just before the addition in another chamber in the same manner and added over 5 minutes.

(Formation of Fourth Shell) After the formation of the third shell, an AgNO ₃ (66.4 g) aqueous solution and a KBr aqueous solution were added at a constant flow rate for 30 minutes by the double jet method. On the way, potassium iridium hexachloride and yellow blood salt were added. At this time, the silver potential was set to 30 with respect to the saturated calomel electrode.
kept at mV. Wash with normal water, add gelatin,
The pH was adjusted to 5.8 and pAg 8.8 at 40 ° C. This emulsion was designated as emulsion b. Emulsion b has an average equivalent circle diameter of 3.3 μm,
21% variation coefficient of equivalent circle diameter, 0.090 μm average thickness,
It was a tabular grain having 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.
It was occupied by tabular grains of 090 μm or less. When the area occupied by the dye is set to 80Å ² , the layer saturation coverage is 1.4.
It was 5 × 10 ⁻³ mol / molAg.

Emulsion b was heated to 56 ° C., 1.2 × 10 ⁻³ mol / mol Ag of the following comparative dye S-1 was added, and then C-5, potassium thiocyanate, chloroauric acid and sodium thiosulfate were added. And N, N-dimethylselenourea were added for optimum chemical sensitization. Furthermore, S-1 is 2.5 × 1
An emulsion for Comparative Example 1 was prepared by adding 0 ^-4 mol / mol Ag and stirring for 60 minutes.

(2) Measurement of light absorption intensity and adsorption amount To measure the light absorption intensity per unit area, use the obtained emulsion.
Apply it thinly on a slide glass and use the Calutz Ice Stock Association
Using the Microspectrophotometer MSP65 manufactured by K.K.
Transmission spectrum and reflection spectrum of each particle
Was measured to obtain an absorption spectrum. Transmission spectrum
The reference of the
Tol measures silicon carbide with known reflectance
I used it as a reference. The measuring part is a circular 1 μm diameter
It is the aperture part, and the aperture part overlaps the outline of the particle.
Adjust the position so as not to^-1(714
nm) to 28000 cm^-1Wavenumber up to (357 nm)
Measure the transmission spectrum and reflection spectrum in the region, and
-T (transmittance) -R (reflectance) as absorption rate A
I asked for a vector. Absorb by subtracting the absorption of silver halide
The yield is A ', and -Log (1-A') is the wave number (cm^-1)
Halved the value integrated for
It was defined as the light absorption intensity. Integration range is 14000 cm^-1From 2
8000 cm ^-1Up to. At this time, the light source is
Lamp was used and the light source voltage was set to 8V. By light irradiation
To minimize dye damage, the primary side monochrome
The wavelength spacing is 2 nm and the slit width is 2.5 n.
set to m. The absorption spectrum and
And the light absorption intensity were determined.

The amount of dye adsorbed on the obtained liquid emulsion was 10,
After centrifugation at 000 rpm for 10 minutes and freeze-drying the precipitate, 0.05 g of the precipitate was added to 25 ml of 25% aqueous sodium thiosulfate solution and methanol to make 50 ml. This solution was analyzed by high performance liquid chromatography, and the dye concentration was determined quantitatively. The number of adsorbed layers of the dye was determined from the amount of adsorbed dye and the amount of one-layer saturated coating thus obtained.

(3) Preparation of coating sample An emulsion layer and a protective layer as shown in Table 1 were coated on a triacetyl cellulose film support provided with an undercoat layer. Further, Comparative Compound S-1 was changed to the compound of the present invention in an equimolar amount to prepare Samples 101 to 113.

[0131]

[Table 1]

These samples were exposed for sensitometry (1/100 second) and subjected to the following color development processing. Treatment method Treatment time Treatment temperature Replenishment amount Tank capacity Color development 2 minutes 45 seconds 38 ° C. 33 ml 20 liters Bleach 6 minutes 30 seconds 38 ° C. 25 ml 40 liters Washing 2 minutes 10 seconds 24 ° C. 1200 ml 20 liters Fixing 4 minutes 20 seconds 38 ° C. 25 ml 30 liters Water washing 1 1 min 05 sec 24 ° C (2) to (1) 10 liter countercurrent piping system Water washing 2 1 min 00 sec 24 ° C 1200 ml 10 liters Stable 1 min 05 sec 38 ° C 25 ml 10 liters Dry 4 min 20 Second 55 ° C. Replenishment amount per 35 mm width 1 m length Next, the composition of the treatment liquid is described. (Color developer) Mother liquor (g) Replenisher (g) Diethylenetriamine pentaacetic acid 1.0 1.1 1-Hydroxyethylidene-1,1-diphosphonic acid 3.0 3.2 Sodium sulfite 4.0 4.0 Potassium carbonate 30.0 37.0 Potassium bromide 1.4 0.7 Potassium iodide 1.5 mg-hydroxylamine sulfate 2.4 2.8 4- [N-ethyl-N-β-hydroxyethylamino] -2- Methylaniline sulfate 4.5 5.5 Add water 1.0 liter 1.0 liter pH 10.05 10.05 (bleaching solution) Mother liquor (g) Replenisher (g) Ethylenediaminetetraacetic acid ferric sodium trihydrate 100.0 120.0 Ethylenediaminetetraacetic acid 2 Sodium salt 10.0 11.0 Ammonium bromide 140.0 160.0 Ammonium nitrate 30.0 35.0 Ammonia water (27%) 6.5 ml 4.0 ml Add water 1.0 liter 1.0 liter pH 6 .0 5.7 (Fixer) Mother liquor (g) Replenisher (g) Ethylenediaminetetraacetic acid sodium salt 0.5 0.7 Sodium sulfite 7.0 8.0 Sodium bisulfite 5.0 5.5 Ammonium thiosulfate water (70%) 170.0 ml 200.0 ml Water added 1.0 liter 1.0 liter pH 6.7 6.65 (Stabilizer) Mother liquor (g) Replenisher (g) Formalin 2.0 ml 3.0 ml Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.3 0.45 Ethylenediaminetetraacetic acid disodium salt 0.05 0.08 Add water 1.0 liter 1.0 liter pH 5.8-8.0 5.8-8.0

The density of the treated sample was measured with a blue filter to evaluate sensitivity and fogging. Sensitivity is 0 than fog density.
2 Defined by the reciprocal of the exposure amount that gives a high density, and the sensitivity of each sample was expressed as a relative value with the value of Sample 101 as 100. Table 2 shows the results of the emulsions and comparative examples used for each sample, the light absorption intensity of the compound of the present invention, and the sensitivity of each sample. The light absorption intensity is an average value of 200 particles obtained by the microspectroscopic method. Both the light absorption intensity and the sensitivity were based on the values of Comparative Example 101. The light absorption intensity of Comparative Example 101 was 59.

[0134]

[Table 2]

[0135]

[Chemical 25]

From Table 2, the compounds of the present invention are comparative compounds S
As compared with -1, it is clear that the light absorption rate is improved due to the multilayer structure, resulting in higher sensitivity. Furthermore, it is also clear that the effect is superior to that of the comparative compound S-2 described in European Patent 887700A1. Further, the compound D of the present invention
The number of adsorption layers of the sample 110 using −23 is 1.98, which is almost a two-layer structure. From the above results, it is clear that when the second-layer dye is photoexcited, it contributes to higher sensitivity through energy transfer or electron transfer to the first-layer dye.

Example 3 The same comparison as in Example 2 was carried out using Example 5 in JP-A-8-29904.
Comparative Example S-
When the sensitivity of the blue sensitive layer of the photosensitive material using No. 1 was 100 (reference), the sensitivity of the photosensitive material using D-33 of the present invention was 166, which was high. A similar comparison was made in the instant photosensitive material system of Example 1 of Japanese Patent Application No. 11-89801. The sensitivity of the blue sensitive layer of the photosensitive material of Comparative Example S-1 was 100.
Based on (reference), the sensitivity of the light-sensitive material using D-3 of the present invention was as high as 164. Furthermore, JP-A-7-92601,
No. 11-160828, Example 1 color reversal sensitive material system, JP-A-6-347944, Example 1 color paper system, JP-A-8-122954, Example 1 X-ray. Sensitive material, Japanese Patent Application 2000-894
In the heat-developable light-sensitive material system of Example 36 of JP-A No. 36-90, and the print-sensitive material system of Example 1 of JP-A-8-292512, the light-sensitive material using the compound of the present invention is highly sensitive to the comparative compound. I understood it. Furthermore, in any of these systems, high light absorption intensity,
It has a large number of chromophore adsorption layers and has been found to be equally useful.

[0138]

EFFECT OF THE INVENTION By using the methine dye-linking compound of the present invention, a multilayer structure is formed and the light absorption rate is improved, and a highly sensitive silver halide photographic light-sensitive material can be obtained.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 2H023 CA06 CA07 CA08                 4H056 CA01 CA05 CB06 CC08 CE03                       CE06 DD19 DD23

Claims (5)

[Claims] 1. A silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support, wherein the emulsion layer contains a compound represented by the following general formula (1). A silver halide photographic light-sensitive material characterized by the above. General formula (1) In the formula, L ₁ represents a linking group, m 1 represents an integer of 1 to 5, and m 2 represents an integer of 1 to 5. CI ₁ represents an ion that neutralizes electric charge, and y 1 represents a number necessary for neutralizing electric charge. Dye1 represents the first chromophore represented by the general formula (2), and Dye2 represents the second chromophore. General formula (2) X ₁ and X ₂ are each independently -O-, -S-, -NR.
₆ -, - CR ₇ R ₈ - represents each R ₆ to R ₈ are independently a hydrogen atom, an alkyl group, an alkenyl group, ant - represents a group or a heterocyclic group. R ₁ and R ₂ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group. M _{1 to} M ₃ each independently represent a methine group, and n 1 represents an integer of 0 to 3. V _1, V ₂ represents a substituent, n2, n3 each represents an integer of 0 to 4. When n2 and n3 are 2 or more, V ₁ and V ₂ may be the same or different and may be connected to each other to form a ring. However, at least one of V _{1 and} V ₂ represents a substituent containing an adsorptive group to silver halide. The linking group L ₁ in the general formula (1) is R ₁ ,
Connect with Dye1 at R ₂ , V ₁ or V ₂ . 2. The silver halide photographic light-sensitive material according to claim 1, wherein the adsorptive group is a group containing a sulfur atom. 3. A compound represented by the general formula (1):
3. The silver halide photographic light-sensitive material according to claim 1, wherein Dye2 is independently a cyanine chromophore, a merocyanine chromophore, or an oxanol chromophore. 4. A compound represented by the general formula (1):
4. The silver halide photographic light-sensitive material according to claim 1, 2 or 3, wherein Dye2 is a merocyanine chromophore. 5. A methine dye compound represented by the following general formula (1). General formula (1) In the formula, L ₁ represents a linking group, m 1 represents an integer of 1 to 5, and m 2 represents an integer of 1 to 5. CI ₁ represents an ion that neutralizes charge, and y 1 represents the number necessary for neutralizing charge. Dye1 represents the first chromophore represented by the general formula (2), and Dye2 represents the second chromophore. General formula (2) X ₁ and X ₂ are each independently -O-, -S-, -NR.
₆ -, - CR ₇ R ₈ - represents each R ₆ to R ₈ are independently a hydrogen atom, an alkyl group, an alkenyl group, ant - represents a group or a heterocyclic group. R ₁ and R ₂ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group. M _{1 to} M ₃ each independently represent a methine group, and n 1 represents an integer of 0 to 3. V _1, V ₂ represents a substituent, n2, n3 each represents an integer of 0 to 4. When n2 and n3 are 2 or more, V ₁ and V ₂ may be the same or different and may be connected to each other to form a ring. However, at least one of V _{1 and} V ₂ represents a substituent containing an adsorptive group to silver halide. The linking group L ₁ in the general formula (1) is R ₁ ,
Connect with Dye1 at R ₂ , V ₁ or V ₂ .