JP2002090929A - 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 the formula Dye1-[L2-(-Dye2-(-L-R1)m1)m2]m3 (where Dye1 is a first chromophore; Dye2 is a second chromophore; R1 is a dissociable group having a pKa of <=5; L and L2 are each a linking group; m1 is an integer of 1-4; m2 is an integer of 1-5; and m3 is an integer of 1-5).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel methine dye compound, and more particularly to a linked methine dye compound in which two chromophores are linked, and a silver halide photographic material containing the same.

[0002]

2. Description of the Related Art Methine compounds have been conventionally used as spectral sensitizing dyes for silver halide photographic materials. Techniques which have heretofore been known as techniques for improving the light absorption of silver halide grains are described below. In order to improve the light absorptivity per grain, it is necessary to increase the adsorption density of the sensitizing dye to the silver halide grains. Adsorb, no more. Several proposals have been made to solve this problem. PBGilman, Jr. et al.
ographic Sciece and Engineering, Volume 20, Volume 3
No. 97, p. 97 (1976), a cationic dye was adsorbed on the first layer, and an anionic dye was adsorbed on the second layer using electrostatic force. GBBird et al. In U.S. Pat.
In 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, JP-A-64-84,
In No. 244, spectral sensitization was performed by energy transfer from the luminescent dye. However, all of these attempts have attempted to adsorb the dye in an amount equal to or greater than the saturated adsorption amount on the silver halide grains, but none of them has a high sensitivity effect and has problems such as an increase in intrinsic desensitization. Was. On the other hand, two or more unconjugated dye chromophores are linked by a covalent bond.
Regarding the component-linked dye, U.S. Pat.
2,425,772, 2,518,732, 2,521,944, 2,59
No. 2,196 or EP 565,083. However, these were not intended to improve the light absorption. GBBird et al. In U.S. Pat.Nos. 3,622,317 and 3,976,493 increased the light absorption by adsorbing linked sensitizing dye molecules having multiple cyanine chromophores, aiming to positively improve the light absorption. Sensitization, but no remarkable increase in sensitivity was obtained. Ukai et al., In JP-A-64-91134, combine at least one substantially non-adsorbable dye containing at least two sulfo or carboxy groups with a spectral sensitizing dye that can be adsorbed on silver halide. Has been proposed. Also, Bishwa Karma et al. In Japanese Patent Application Laid-Open No. 6-27,578 describe a binary linked dye in which an adsorbable cyanine dye and a non-adsorbable oxonol are linked to silver halide, and Parton et al. Spectral sensitization is performed using two-component linked dyes in which non-adsorbable merocyanine dyes and the like are linked using a specific linking group. However, it cannot be said that the enhancement of sensitivity due to energy transfer has occurred sufficiently. . As described above, no sufficient sensitivity has been achieved by any of the methods of the patents and literatures, and further technical development needs to be performed.

[0003]

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

[0004]

The above objects of the present invention have been attained by the following means. (1) A silver halide photographic material having at least one photosensitive silver halide emulsion layer on a support, characterized in that the emulsion layer contains a compound represented by the following general formula (1). Silver halide photographic light-sensitive material. General formula (1)

[0005]

Embedded image

Where Dye1 is the first chromophore and Dye2 is the second chromophore.
Represents a chromophore. R ₁ represents a dissociable group having a pKa of 5 or less;
L and L ₂ each independently represent a linking group. m1 is 1 to 4
M2 represents an integer of 1 to 5, and m3 represents an integer of 1 to 5. (2) The silver halide photographic material as described in (1), wherein in the compound represented by the formula (1), the linking group L is represented by -A ₁ -L _1- . Here, L ₁ represents any _one of an alkylene group, an alkenylene group, and an arylene group, and A1 represents -O-, -S-, -NR
_{2 -, - COO -, -} CONR 3 -, - SO 2 NR 4 - represents one of, R ₂ to R ₄ represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group . However, L ₁ is on the R ₁ side. (3) In the compound represented by the general formula (1), R ₁
There _{-SO 3 M, -OSO 3 M,} -PO 3 M 2, -OPO
₃ represents either M ₂ or —COOM, and M represents a proton or a cation (1) or (2)
The silver halide photographic light-sensitive material as described above. (4) In the compound represented by the general formula (1), Dye
(1) The silver halide photographic material as described in any of (1) to (3) above, wherein Dye2 is independently any one of a cyanine chromophore, a merocyanine chromophore, and an oxonol chromophore. (5) In the compound represented by the general formula (1), Dye
1, wherein Dye2 is independently any one of a cyanine chromophore and a merocyanine chromophore (1) to
The silver halide photographic light-sensitive material according to any one of (4) and (4). (6) In the compound represented by the general formula (1), Dye1
Is a cyanine chromophore, and Dye2 is either a cyanine chromophore or a merocyanine chromophore. The silver halide photographic light-sensitive material according to any one of (1) to (5), (7) In the compound represented by the general formula (1), Dye
(1) The silver halide photographic light-sensitive material as described in any of (1) to (6) above, wherein Dye2 is a co-cyanine chromophore. (8) In the compound represented by the general formula (1), L ₂
Is represented by -G _1- (A ₂ -G ₂ ) t 1-, wherein the silver halide photographic light-sensitive material according to any one of (1) to (7), Here, G _1, G ₂ are each independently an alkylene group, an alkenylene group, an arylene group, A ₂ is regardless the orientation -O -, - S -, - SO 2 -, - NR 2 -,
Represents any of —COO—, —CONR ₃ —, and —SO ₂ NR ₄ —, and t1 represents an integer of 1 to 10. (9) The silver halide photographic material according to any one of (1) to (8), wherein the compound represented by the general formula (1) is represented by the following general formula (2).

[0007]

Embedded image

Where L₁, A₁Is synonymous with general formula (1)
G₁, G_Two, A_Two, T1 have the same meaning as in claim 4. R₁Is
-SO_ThreeM, -OSO_ThreeM, -PO_ThreeM_Two, -OPO_ThreeM_Two,
-COOM, where M is proton or positive
Represents on, and n7 and n8 each independently represent an integer of 0 to 2.
However, they do not both become zero. X₁~ X_FourAre independent
To -O-, -S-, -NR_Five-, -CR₆R₇Represents-
R_Five~ R₇Are each independently a hydrogen atom, an alkyl group,
Represents a kenyl group, an aryl group, or a heterocyclic group. R ₁₁~ R₁₄
Are each independently a hydrogen atom, an alkyl group, an alkenyl
Represents an aryl group, a heterocyclic group. M₁~ M₆Each
Each independently represents a methine group, and n1 and n2 are each independently 0 to
Represents an integer of 3. V₁~ V_FourRepresents a substituent, and n3 to n6 represent 0
Represents an integer of from 4 to 4. When n3 to n6 is 2 or more, V_Three~ V₆Is the same
And may be linked together to form a ring
good. CI represents an ion that neutralizes the charge, and y
Represents the number needed to sum. Note that G₁Is R₁₁Or V₁
Connect with Dye1 at_TwoIs R₁₃Or V_ThreeWith Dye2 at
Tie. (10) Compound represented by general formula (1) or (2)
In, R₁Is -SO_ThreeCharacterized by M
(3) The silver halide photographic sensitivity according to any one of (9) to (9).
Light material. (11) Compound represented by general formula (1) or (2)
Wherein L1 is an alkylene group
The silver halide photograph according to any one of (1) to (10).
Photosensitive material. (12) Compound represented by general formula (1) or (2)
In A₁Is -O-, -COO-, -CONR_ThreeIn
The method described in any of (1) to (11),
Silver halide photographic light-sensitive material. (13) Compound represented by general formula (1) or (2)
In A₁Is -O- (1
2) The silver halide photographic material as described in the above. (14) Compound represented by general formula (1) or (2)
At G₁, G_TwoIs an alkylene group,
The silver halide according to any one of (8) to (13),
Photosensitive material. (15) Compound represented by general formula (1) or (2)
In, A_TwoIs -O-, -SO_Two-, -COO-,-
CONR_Three(8)-(14)
A silver halide photographic light-sensitive material according to any one of the above. (16) In the compound represented by the general formula (2), X
₁~ X_FourIs -O- or -S-
The silver halide photograph according to any one of (9) to (13)
Photosensitive material. (17) In the compound represented by the general formula (2), X
₁~ X_FourIs -S-.
Silver halide photographic material. (18) In the compound represented by the general formula (2), G
₁Is R₁₁And G_TwoIs characterized by being linked to R13.
Silver halide according to any one of (8) to (17)
Photosensitive material. (19) Compound represented by general formula (1) or (2)
, The adsorption force on silver halide grains is Dye1> Dye2
Any of (1) to (18), characterized in that
A silver halide photographic light-sensitive material according to any one of the above. (20) In a silver halide photographic emulsion, the general formula (1)
Or the compound represented by (2) is halogenated by Dye1
Adsorbed on silver particles and further adsorbed on silver halide particles
Electron transfer or energy to Dye1 when no Dye2 is photoexcited
Any of (1) to (19), characterized in that
A silver halide photographic light-sensitive material according to any one of the above. (21) In a silver halide photographic emulsion, the general formula (1)
Or the compound represented by (2) is halogenated by Dye1
Adsorbed on silver particles to form J-association
Dye2 not adsorbed to particles also forms J-association.
Silver halide photographic light-sensitive material. (22) The general formula (1) described in (1) to (21) or
Silver halide photographic emulsion containing the compound represented by (2)
But tabular grains having an aspect ratio of 2 or more
Emulsion in which 50% (area) or more of silver gemide grains are present
Silver halide according to (1) to (21),
Photosensitive material. (23) The general formula (1) described in (1) to (22) or
Silver halide photographic emulsion containing the compound represented by (2)
Is characterized by being selenium sensitized (1) to
The silver halide photographic light-sensitive material according to any one of (22) and (22).
Fees. (24) A color represented by the general formula (2) described in (9).
Elementary.

[0009]

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

When the compound of the present invention has an alkyl group, an alkylene group, an alkenyl group, or an alkenylene group, unless otherwise specified, they may be linear or branched, and may be substituted or unsubstituted. 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, unless otherwise specified, they may be monocyclic or condensed. May be substituted or unsubstituted.

In the present invention, when a particular moiety is referred to as a "group", the moiety may be substituted with one or more (up to the maximum number of possible) substituents, even if the moiety is not itself substituted. Means that it may be. For example, “alkyl group” means a substituted or unsubstituted alkyl group. The substituents that can be used in the compounds of the present invention include any substituents, regardless of whether they are substituted or not. For example, a substituent group W described below is mentioned. The substituent represented by W may be any, and is not particularly limited.
For example, *, halogen atom, alkyl group [(including cycloalkyl group, bicycloalkyl group * and tricycloalkyl group), and alkenyl group (cycloalkenyl group,
Bicycloalkenyl group), and alkynyl group. ], Aryl group, heterocyclic group (may be referred to as heterocyclic group), cyano group, hydroxyl group, nitro group, carboxyl group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyl Oxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group (including anilino group), ammonium group, acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group , Alkyl and arylsulfonylamino, mercapto, alkylthio, arylthio, heterocyclic thio, sulfamoyl, sulfo, alkyl and arylsulfinyl, alkyl and arylsulfonyl, acyl, arylo Xycarbonyl group, alkoxycarbonyl group, carbamoyl group, aryl and heterocyclic azo group, imide group, phosphino group, phosphinyl group, phosphinyloxy group, phosphinylamino group, phospho group, silyl group, hydrazino group, ureido group , And other known substituents.
More specifically, W is a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), an alkyl group
[[Indicates a linear, branched, or cyclic substituted or unsubstituted alkyl group. They are alkyl groups (preferably having 1 carbon atom).
To 30 alkyl groups such as methyl, ethyl, n-propyl, isopropyl, t-butyl, n-octyl, eicosyl, 2-chloroethyl, 2-cyanoethyl, 2-
Ethylhexyl), a cycloalkyl group (preferably a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, for example, cyclohexyl, cyclopentyl, 4-n
-Dodecylcyclohexyl), a bicycloalkyl group (preferably a substituted or unsubstituted bicycloalkyl group having 5 to 30 carbon atoms, that is, a monovalent group obtained by removing one hydrogen atom from a bicycloalkane having 5 to 30 carbon atoms) For example, bicyclo [1,2,2] heptane-2-yl, bicyclo [2,2,2] octan-3-yl), and a tricyclo structure having many ring structures are also included. An alkyl group (for example, an alkyl group of an alkylthio group) in the substituents described below represents an alkyl group having such a concept, and further includes an alkenyl group and an alkynyl group. And an alkenyl group [which represents a linear, branched or cyclic substituted or unsubstituted alkenyl group. They are,
An alkenyl group (preferably a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, for example, vinyl, allyl, prenyl, geranyl, oleyl), a cycloalkenyl group (preferably a substituted or unsubstituted 3 to 30 carbon atoms); A cycloalkenyl group, that is, a monovalent group obtained by removing one hydrogen atom from a cycloalkene having 3 to 30 carbon atoms, for example, 2-cyclopenten-1-yl, 2-cyclohexen-1-yl), a bicycloalkenyl group (Substituted or unsubstituted bicycloalkenyl group, preferably
It is a substituted or unsubstituted bicycloalkenyl group having 5 to 30 carbon atoms, that is, a monovalent group obtained by removing one hydrogen atom from a bicycloalkene having one double bond. For example,
Bicyclo [2,2,1] hept-2-en-1-yl,
Bicyclo [2,2,2] oct-2-en-4-yl)
Is included. Alkynyl group (preferably substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, for example, ethynyl, propargyl, trimethylsilylethynyl group)], aryl group (preferably substituted or unsubstituted having 6 to 30 carbon atoms) Aryl groups such as phenyl, p-tolyl, naphthyl, m-chlorophenyl, o
-Hexadecanoylaminophenyl), a heterocyclic group (preferably 5- or 6-membered substituted or unsubstituted, aromatic *
Alternatively, it is a monovalent group obtained by removing one hydrogen atom from a non-aromatic heterocyclic compound, and more preferably has 3 carbon atoms.
To 30 to 5 or 6-membered aromatic heterocyclic group.
For example, cationic heterocyclic groups such as 2-furyl, 2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl, and 1-methyl-2-pyridinio and 1-methyl-2-quinolinio may be used. ), A cyano group, a hydroxyl group, a nitro group, a carboxyl group, an alkoxy group (preferably a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, for example, methoxy, ethoxy, isopropoxy, t-butoxy, n-octyl) Oxy, 2-methoxyethoxy), aryloxy group (preferably having 6 carbon atoms)
To 30 substituted or unsubstituted aryloxy groups, for example, phenoxy, 2-methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, 2-tetradecanoylaminophenoxy), silyloxy group (preferably carbon number A silyloxy group having 3 to 20, for example, trimethylsilyloxy, t-butyldimethylsilyloxy), a heterocyclic oxy group (preferably having 2 to 3 carbon atoms);
0 substituted or unsubstituted heterocyclic oxy group, 1-phenyltetrazol-5-oxy, 2-tetrahydropyranyloxy), acyloxy group (preferably formyloxy group, substituted or unsubstituted alkyl having 2 to 30 carbon atoms) A carbonyloxy group, a substituted or unsubstituted arylcarbonyloxy group having 6 to 30 carbon atoms, for example, formyloxy, acetyloxy, pivaloyloxy, stearoyloxy, benzoyloxy, p-methoxyphenylcarbonyloxy), a carbamoyloxy group (preferably A substituted or unsubstituted carbamoyloxy group having 1 to 30 carbon atoms, for example, N, N-dimethylcarbamoyloxy, N, N-diethylcarbamoyloxy,
Morpholinocarbonyloxy, N, N-di-n-octylaminocarbonyloxy, Nn-octylcarbamoyloxy), alkoxycarbonyloxy group (preferably substituted or unsubstituted alkoxycarbonyloxy group having 2 to 30 carbon atoms, for example, Methoxycarbonyloxy, ethoxycarbonyloxy, t-butoxycarbonyloxy, n-octylcarbonyloxy), an aryloxycarbonyloxy group (preferably a substituted or unsubstituted aryloxycarbonyloxy group having 7 to 30 carbon atoms, for example, phenoxy Carbonyloxy, p-
Methoxyphenoxycarbonyloxy, pn-hexadecyloxyphenoxycarbonyloxy), amino group * (preferably, amino group, substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, substitution of 6 to 30 carbon atoms or An unsubstituted anilino group, for example, amino, methylamino, dimethylamino, anilino, N-methyl-anilino, diphenylamino), an ammonio group (preferably an ammonio group, substituted or unsubstituted alkyl or aryl having 1 to 30 carbon atoms) An ammonium group substituted with a heterocyclic ring, for example, trimethylammonio, triethylammonio, diphenylmethylammonio), an acylamino group (preferably formylamino group, having 1 to 30 carbon atoms).
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), amino A carbonylamino group (preferably a substituted or unsubstituted aminocarbonylamino having 1 to 30 carbon atoms such as carbamoylamino, N, N-dimethylaminocarbonylamino, N, N
-Diethylaminocarbonylamino, morpholinocarbonylamino), alkoxycarbonylamino group (preferably substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms, for example, methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino, n- Octadecyloxycarbonylamino,
N-methyl-methoxycarbonylamino), an aryloxycarbonylamino group (preferably having 7 to 3 carbon atoms)
0 substituted or unsubstituted aryloxycarbonylamino group, for example, phenoxycarbonylamino, p-chlorophenoxycarbonylamino, mn-octyloxy * phenoxycarbonylamino), sulfamoylamino group (preferably 0 carbon atoms) To 30 substituted or unsubstituted sulfamoylamino groups, for example, sulfamoylamino, N, N-dimethylaminosulfonylamino,
Nn-octylaminosulfonylamino), alkyl and arylsulfonylamino groups (preferably having 1 carbon atom)
To 30 substituted or unsubstituted alkylsulfonylamino, C6 to C30 substituted or unsubstituted arylsulfonylamino such as methylsulfonylamino, butylsulfonylamino, phenylsulfonylamino, 2,3,5-trichlorophenylsulfonyl Amino, p-methylphenylsulfonylamino), mercapto group, alkylthio group (preferably having 1 to 30 carbon atoms)
A substituted or unsubstituted alkylthio group such as methylthio, ethylthio, n-hexadecylthio) and an arylthio group (preferably substituted or unsubstituted arylthio having 6 to 30 carbon atoms such as phenylthio, p-chlorophenylthio, m-methoxyphenyl) Thio), a heterocyclic thio group (preferably a substituted or unsubstituted heterocyclic thio group having 2 to 30 carbon atoms, for example, 2-benzothiazolylthio, 1-phenyl * tetrazol-5-ylthio), a sulfamoyl group ( Preferably 0 to 30 carbon atoms
A substituted or unsubstituted sulfamoyl group such as N
-Ethylsulfamoyl, N- (3-dodecyloxypropyl) sulfamoyl, N, N-dimethylsulfamoyl, N-acetylsulfamoyl, N-benzoylsulfamoyl, N- (N'-phenylcarbamoyl) sulfamoyl ), A sulfo group, an alkyl and arylsulfinyl group (preferably a substituted or unsubstituted alkylsulfinyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfinyl group having 6 to 30 carbon atoms, 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 group) Nyl, ethylsulfonyl, phenylsulfonyl, p-methylphenylsulfonyl), acyl group (preferably formyl group, substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, 7 to 3 carbon atoms)
0 substituted or unsubstituted arylcarbonyl group, a heterocyclic carbonyl group having 4 to 30 carbon atoms and a substituted or unsubstituted carbon atom bonded to a carbonyl group, for example,
Acetyl, pivaloyl, 2-chloroacetyl, stearoyl, benzoyl, pn-octyloxyphenylcarbonyl, 2-pyridylcarbonyl, 2-furylcarbonyl), aryloxycarbonyl group (preferably having 7 to 30 carbon atoms or no substitution) Substituted aryloxycarbonyl groups, for example, phenoxycarbonyl, o-chlorophenoxycarbonyl, m-nitrophenoxycarbonyl, pt-butylphenoxycarbonyl), alkoxycarbonyl group (preferably substituted or unsubstituted having 2 to 30 carbon atoms) An alkoxycarbonyl group, for example,
Methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl, n-octadecyloxycarbonyl),
A carbamoyl 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, substituted or unsubstituted heterocyclic azo groups having 3 to 30 carbon atoms, 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), phosphinyl Group (preferably having 2 carbon atoms)
To 30 substituted or unsubstituted phosphinyl groups such as phosphinyl, dioctyloxyphosphinyl, diethoxyphosphinyl) and phosphinyloxy groups (preferably substituted or unsubstituted phosphinyl groups having 2 to 30 carbon atoms); Oxy group, for example, diphenoxyphosphinyloxy, dioctyloxyphosphinyloxy), phosphinylamino group (preferably, a substituted or unsubstituted phosphinylamino group having 2 to 30 carbon atoms, for example, dimethoxy Phosphinylamino, dimethylaminophosphinylamino), phospho group, silyl group (preferably substituted or unsubstituted silyl group having 3 to 30 carbon atoms, for example, trimethylsilyl, t-butyldimethylsilyl, phenyldimethylsilyl) A hydrazino group (preferably having a carbon number of 0 to 30) Substituted or non-substituted hydrazino group,
For example, trimethylhydrazino) and a ureido group (preferably a substituted or unsubstituted ureido group having 0 to 30 carbon atoms, such as N, N-dimethylureido). Further, W is bonded to each other to form a ring (aromatic or non-aromatic hydrocarbon ring or heterocycle. These can be further combined to form a polycyclic fused ring. For example, a benzene ring, a naphthalene Ring, anthracene ring, quinoline ring, phenanthrene ring, fluorene ring, triphenylene ring, naphthacene ring, biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, pyrazine ring, pyrimidine ring, Pyridazine ring, indolizine ring, indole ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinolidine ring, quinoline ring, phthalazine ring, naphthyridine ring,
A quinoxaline ring, a quinoxazoline ring, a quinoline ring, a carbazole ring, a phenanthridine ring, an acridine ring, a phenanthroline ring, a thianthrene ring, a chromene ring, a xanthene ring, a phenoxatiin ring, a phenothiazine ring, and a phenazine ring. ) May be condensed.

Among the above substituents * W, those having a hydrogen atom may be removed and further substituted with the above group. Examples of such substituents * include 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, R1 represents a dissociable group having a pKa of 5 or less. The pKa here is a value in 25 ° C. water. The values of pKa are described in "Chemical Handbook" Basic Edition II-316 to II-321,
The values described in Hideo Iwamura, “Graduate School of Organic Chemistry, Top,” p. R ₁ is preferably -SO
_{3 M, -OSO 3 M, -PO} 3 M 2, -OPO 3 M 2, -CO
OM represents a proton or a cation (preferred examples are the same as the examples of the CI cation described below). R ₁ more preferably represents —SO ₃ M.

L represents a linking group, and may be any linking group, preferably an alkylene group (preferably having 1 to 20 carbon atoms (hereinafter referred to as C number), for example, methylene, ethylene, propylene, butylene, pentylene, hexylene; ,
Octylene), an arylene group (preferably having 6 to 2 carbon atoms)
6, for example, phenylene, naphthylene), alkenylene group (preferably having 2 to 20 carbon atoms, such as ethenylene and propenylene), alkynylene group (preferably having 2 to 20 carbon atoms)
For example ethynylene, propynylene), an amido group, an ester group, a sulfonamide group, a sulfonic acid ester group, a ureido group, a sulfonyl group, a sulfinyl group, a thioether group, an ether group, a carbonyl group, -NR ₅₁ - (R ₅₁ is a hydrogen atom or a Heterylene group (preferably having 1 to 1 carbon atoms)
26, for example, 6-chloro-1,3,5-triazyl-
2,4-diyl group, pyrimidine-2,4-diyl group, and quinoxaline-2,3-diyl group) in combination with one or more of 0 to 100 carbon atoms, preferably 1 or more or 20 or less. The following linking groups are represented. The linking group L is preferably represented by -A ₁ -L _1- . However, L ₁ is on the R ₁ side. Here, L ₁ is 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), an alkenylene group (Preferably C 2-20, for example, ethenylene, propenylene, 2-butenylene) and an arylene group (preferably C 6-26, for example, 1,4-phenylene, 1,4-naphthylene). May be substituted by the aforementioned substituent group W. Preferably, L ₁ represents an alkylene group, more preferably a linear unsubstituted alkylene group having 1 to 8 carbon atoms.

A ₁ represents -O-, -S-,-
NR ₂ —, —COO—, —CONR ₃ —, —SO ₂ NR ₄ —
R2 to R4 each independently represent a hydrogen atom, an alkyl group (preferably 1 to 18, more preferably 1 to 7, particularly preferably 1 to 4, unsubstituted carbon atom (hereinafter referred to as C number) Alkyl groups (eg, methyl,
Ethyl, propyl, isopropyl, butyl, isobutyl, hexyl, octyl, 2-ethylhexyl, dodecyl, octadecyl), a substituted alkyl group having 1 to 18, preferably 1 to 7, particularly preferably 1 to 4, C, such as a substituent The above-mentioned W-substituted alkyl group is exemplified. Preferably an aralkyl group (eg benzyl, 2-
Phenylethyl), a hydroxyalkyl group (eg, 2
-Hydroxyethyl, 3-hydroxypropyl, 6-hydroxyhexyl), carboxyalkyl group (for example, 2-carboxyethyl, 3-carboxypropyl,
4-carboxybutyl, carboxymethyl, 5-carboxypentyl), an alkoxyalkyl group (for example, 2-methoxyethyl, 2- (2-methoxyethoxy) ethyl), an aryloxyalkyl group (for example, 2-phenoxyethyl, 2- ( 1-naphthoxy) ethyl), alkoxycarbonylalkyl group (eg, ethoxycarbonylmethyl, 2-benzyloxycarbonylethyl), aryloxycarbonylalkyl group (eg, 3-phenoxycarbonylpropyl), acyloxyalkyl group (eg, 2-acetyloxyethyl) , An acylalkyl group (eg, 2-acetylethyl), a carbamoylalkyl group (eg, 2-morpholinocarbonylethyl), a sulfamoylalkyl group (eg, N, N-dimethylsulfamoylmethyl), a sulfoa Kill group (e.g., 2-sulfobenzyl, 3-sulfo-3-phenylpropyl, 2-sulfoethyl, 3-sulfopropyl, 3-sulfobutyl, 4-sulfobutyl, 2- [3-sulfopropoxy] ethyl, 2
-Hydroxy-3-sulfopropyl, 3-sulfopropoxyethoxyethyl), a sulfatoalkyl group (eg, 2-sulfatoethyl group, 3-sulfatopropyl, 4-sulfatobutyl), a heterocyclic-substituted alkyl group (eg, 2- (pyrrolidin-2-one-1-yl) ethyl, tetrahydrofurfuryl), alkylsulfonylcarbamoylalkyl group (for example, methanesulfonylcarbamoylmethyl group), acylcarbamoylalkyl group (for example, acetylcarbamoylmethyl group), acylsulfamoyl Alkyl group (eg, acetylsulfamoylmethyl group), alkylsulfonylsulfamoylalkyl group (eg, methanesulfonylsulfamoylmethyl group), halogen-substituted alkyl group (eg, 2-chloroethyl, 2,2,2-trifluoroethyl) Le)}, an alkenyl group (preferably having a C number of 2 to 20, for example, vinyl, allyl, 3-butenyl, oleyl, alkenyl groups W described above is substituted,
For example, a sulfoalkenyl group (for example, 3-sulfo-2-propenyl) and the like, an aryl group (an unsubstituted aryl group having 6 to 20, preferably 6 to 10, and more preferably 6 to 8 C, such as phenyl) Group, 1-naphthyl group,
2-naphthyl,), a substituted aryl group having 6 to 20, preferably 6 to 10, and more preferably 6 to 8 C (for example, the above-mentioned W-substituted aryl group exemplified as the substituent is Specific examples include a p-methoxyphenyl group, a p-methylphenyl group, and a p-chlorophenyl group.)), A heterocyclic group (C number of 1 to 2).
0, preferably 3 to 10 C, more preferably 4 to 8 unsubstituted heterocyclic group (for example, 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), C number 1 to 20, preferably C 3 to 1
0, more preferably a substituted heterocyclic group having 4 to 8 carbon atoms (for example, the above-mentioned heterocyclic group substituted by W mentioned as an example of the substituent; specifically, a 5-methyl-2-thienyl group, 4-methoxy-2-pyridyl group etc.))). R ₂ is preferably a hydrogen atom or an alkyl group, and more preferably an alkyl group. R ₃ and R ₄ are preferably a hydrogen atom or an alkyl group, and more preferably a hydrogen atom.
A ₁ is preferably —O—, —COO—, —CONR ₃ —, and more preferably —O—.

M1 represents an integer of 1 to 4, preferably 1 to
Represents an integer of 4, more preferably 1 or 2. m1
Is 2 or more, a plurality of -LR ₁ may be the same or different. m2 represents an integer of 1 to 5, preferably 1 or 2
And more preferably 1, and m3 represents an integer of 1 to 5, preferably 1 or 2, more preferably 1
It is.

L ₂ represents a linking group, and may be any linking group as described for L, for example, an alkylene group or alkenylene group which may be substituted by the aforementioned substituent group W, but is preferably- It is represented by G _1- (A ₂ -G _2- ) t _1- . A ₂ is -O-, -S-, -SO _2- ,
-NR _2- , -COO-, -CONR _3- , -SO ₂ NR ₄
And R _{2 to} R ₄ represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group. A
₂ preferably _{-O -, - SO 2 -,} - COO -, - CO
NR ₃ —, more preferably —CONR ₃ —.
G ₁ and G ₂ each independently represent an alkylene group, an alkenylene group, or an arylene group (preferable examples are the same as L ₁ ), and the substituent group W described above may be substituted, but G ₁ and G are preferably ₂ is more preferably an alkylene group,
More preferably, it is an unsubstituted linear alkylene group having 1 to 8 carbon atoms. t1 represents an integer of 1 to 10, preferably 1
Or represents 2, more preferably 1. When t1 is 2 or more, a plurality of A ₂ and G ₂ may be the same or different. t1
When A is 1, A ₂ represents -COO-, -CONR _3- , -SO ₂
NR ₄ - is preferably either, -COO-
Or -CONR ₃ - and more preferably, -CON
More preferably, R ₃ —. When t1 is 2 or more,
At least one of A ₂ is -COO-, -CONR ₃ -,-
SO ₂ NR ₄ — and preferably —CO 2
O- or -CONR ₃ - and more preferably, -C
More preferably, it is ONR ₃ —. At that time, for the remaining A ₂ , -COO-, -CONR _3- , -SO
It is more preferably any one of ₂ NR ₄ —, —O— and —SO ₂ —, and even more preferably —O— or —CONR ₃ —.

The chromophores represented by Dye1 and Dye2 may be any chromophores. Complex merocyanine dye, allopolar dye, oxonol dye,
Hemioxonol dye, squarium dye, croconium dye, azamethine dye, coumarin dye, arylidene dye, anthraquinone dye, triphenylmethane dye,
Azo dye, azomethine dye, spiro compound, metallocene dye, fluorenone dye, fulgide 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 dye, phthalocyanine dye, and metal complex dye. Preferably, 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, squarium dye, Polymethine chromophores such as croconium dyes, azamethine dyes, and oxonol dyes are exemplified. For a detailed description of these dyes, see FM Harmer, Heterocyclic Compounds-Cyanine Soybean and Related Compounds.
nds-Cyanine Dyes and Related Compounds), John Wiley & Sons, New York, London, 1964, D.M.
DMSturmer, Heterocyclic Compounds-Special Topics in Heterocyclic Compounds-Sp
ecial topics in heterocyclic chemistry), 18
Chapters, section 14, 482-515, etc. The general formula of a preferred dye is described in US Pat.
And the general formulas described in U.S. Pat. No. 5,747,236, pp. 30-34. The general formulas of preferred cyanine dyes, merocyanine dyes and rhodacyanine dyes are described in U.S. Pat. No. 5,340,694, columns 21-22 (XI), (XI
I), (XIII) (where n12, n15,
The number of n17 and n18 is not limited, and is an integer of 0 or more (preferably 4
Below)). Dye1 and Dye2 are cyanine chromophores,
It is preferably one of a merocyanine chromophore and an oxonol chromophore, and more preferably one of a cyanine chromophore and a merocyanine chromophore. At that time Dye1
Is more preferably a cyanine chromophore, Dye1,
Most preferably, Dye2 is a cyanine chromophore.

The cyanine chromophore preferably represents a chromophore represented by the following general formula (3).

[0020]

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In the formula, Za ¹ and Za ² each represent an atom group forming a 5- or 6-membered nitrogen-containing heterocyclic ring, and further include 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. Ra ₁ and Ra ₂ each represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group (the preferred examples are the same as R _{2 to} R ₄ ), and preferably represent a hydrogen atom, an alkyl group, or a sulfoalkyl group. And 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-described substituent group W, but is preferably, for example, an alkyl group having 1 to 20 C atoms ( For example, methyl,
Ethyl, i-propyl), halogen atom (eg, chlorine, bromine, iodine, fluorine), nitro group, C 1-20
An alkoxy group (e.g., methoxy, ethoxy), an aryl group having 6 to 26 C atoms (e.g., phenyl, 2-naphthyl), a heterocyclic group having 0 to 20 C atoms (e.g., 2-pyridyl, 3-pyridyl), An aryloxy group having 6 to 20 C atoms (eg, phenoxy, 1-naphthoxy, 2-naphthoxy), an acylamino group having 1 to 20 C atoms (eg, acetylamino, benzoylamino), and a carbamoyl group having 1 to 20 C atoms (eg, N, N-dimethylcarbamoyl), a sulfo group, a hydroxy group, a carboxy group, an alkylthio group having 1 to 20 carbon atoms (eg, methylthio), a cyano group, and the like. Also, a ring may be formed with another methine group,
Alternatively, a ring can be formed with an auxiliary chromophore. Preferred are unsubstituted, ethyl-substituted and methyl-substituted methine groups. na ¹ and na ² are 0 or 1, and preferably 0. ka ¹ represents an integer from 0 to 3. Preferably it is an integer from 0 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 for neutralizing the charge, and y represents a number required for neutralizing the charge.

The merocyanine chromophore is preferably a chromophore represented by the following general formula (4).

[0023]

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In the formula, Za ³ represents a group of atoms forming a 5- or 6-membered nitrogen-containing heterocyclic ring, which is further condensed with a benzene ring, a benzofuran ring, a pyridine ring, a pyrrole ring, an indole ring, a thiophene ring or the like. It may be ringed. Za
⁴ represents an atomic group forming an acidic nucleus. Ra ₃ is a hydrogen atom,
Represents an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group (preferred examples are the same as Ra ₁ and Ra ₂ ). Ma _{8 to} M
a ₁₁ each represents a methine group (preferred examples are the same as Ma ₁ ~Ma _7). na ³ is 0 or 1. ka ² represents an integer from 0 to 3, preferably an integer from 0 to 2, and more preferably 1 or 2. When Ka ² is 2 or more, Ma
₁₀ and Ma ₁₁ may be the same or different. CI represents an ion for neutralizing the charge, and y represents a number required for neutralizing the charge.

The oxonol chromophore is preferably a chromophore represented by the following formula (5).

[0026]

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In the formula, Za ⁵ and Za ⁶ each represent an atomic group forming an acidic nucleus. Ma ₁₂ to Ma ₁₄ each represents a methine group (preferred examples are the same as in Ma ₁ ~Ma _7). ka ³ is from 0 to 3
And preferably an integer from 0 to 2. When ka ³ is 2 or more, Ma ₁₂ and Ma ₁₃ may be the same or different. CI represents an ion for neutralizing the charge, and y represents a number required for neutralizing the charge.

Za ¹ , Za ₂ and Za ^{3 each} have 3 to 25 carbon atoms.
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-naphthooxazolyl, 2-3-sulfopropyl-β
-Naphthooxazolyl, 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-dimethylthiobenzooxazolyl), having 3 to 2 carbon atoms
5 thiazole nucleus (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), an imidazole nucleus having 3 to 25 carbon atoms (for example, 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, etc.), an indolenine nucleus having 10 to 30 carbon atoms (e.g., 3,3-dimethylindolenine), a quinoline nucleus having 9 to 25 carbon atoms (e.g., 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, 4-1
-Methyl-7-chloroquinolyl, 4-1, 8-diethylquinolyl, 4-1-methyl-6-methylthioquinolyl,
4-1-sulfopropylquinolyl and the like),
A selenazole nucleus having 3 to 25 carbon atoms (for example, 2-3-methylbenzoselenazolyl and the like), and a carbon number of 5
To 25 pyridine nuclei (e.g., 2-pyridyl and the like); and thiazoline nucleus, oxazoline nucleus, selenazoline nucleus, tellrazoline nucleus, tellurazole nucleus, benzotellurazole nucleus, imidazoline nucleus, and the like.
Examples thereof include an imidazo [4,5-quinoxalin] nucleus, an oxadiazole nucleus, a thiadiazole nucleus, a tetrazole nucleus, and a pyrimidine nucleus. These may be replaced,
Examples of the substituent include the above-described substituent group W. Preferably, for example, an alkyl group (eg, methyl, ethyl, propyl), a halogen atom (eg, chlorine, bromine, iodine,
Fluorine), a nitro group, an alkoxy group (eg, methoxy, ethoxy), an aryl group (eg, phenyl), a heterocyclic group (eg, 2-pyridyl, 3-pyridyl, 1-pyrrolyl, 2-thienyl), an aryloxy group ( For example, phenoxy), acylamino group (eg, acetylamino, benzoylamino), carbamoyl group (eg, N, N-dimethylcarbamoyl), sulfo group, sulfonamide group (eg, methanesulfonamide), sulfamoyl group (eg, N-methylsulfa Moyl), a hydroxy group, a carboxy group, an alkylthio group (eg, methylthio), a cyano group, and the like. Preferred are an oxazole nucleus, an imidazole nucleus and 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 indole ring, and a thiophene ring.

Za ₄ , Za ₅ , and Za ₆ each represent an atomic group necessary for forming an acidic nucleus.
Photographic Process, 4th Edition, Macmillan, 19
77, p. 198. Specifically, 2
Pyrazolone-5-one, pyrazolidin-3,5-dione, imidazolin-5-one, hydantoin, 2 or 4-thiohydantoin, 2-iminooxazolidine-4
-One, 2-oxazoline-5-one, 2-thiooxazoline-2,4-dione, isorhodanine, 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-dihydroisoquinoline- 4-one, 1,3-dioxane-4,6-dione, barbituric acid, 2-thiobarbituric acid, coumarin-2,4-dione, indazolin-2-one, pyrido [1,2-a] pyrimidine- Examples include nuclei such as 1,3-dione, pyrazolo [1,5-b] quinazolone and pyrazolopyridone. Preferably, they are hydantoin, rhodanine, barbituric acid, and 2-oxazolin-5-one. Za ⁴ is preferably barbituric acid.

Specific examples of the cyanine chromophore, merocyanine chromophore or oxonol chromophore include FMHarmer
Author, Heterocyclic Compounds-Cyanine Dyes and Relat
ed Compounds, John & Wiley & Sons, New York, London,
Those described in a 1964 publication can be mentioned.

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

The compound represented by the general formula (1) of the present invention is more preferably represented by the general formula (2). Where L ₁ ,
A ₁ has the same meaning as in general formula (1), and G ₁ , G ₂ , A ₂ , t1
Has the same meaning as in claim 4. R ₁ is -SO ₃ M, -OSO _{3
M, -PO 3 M 2, -OPO} 3 M 2, represents one of -COOM, M represents a proton or a cation, preferably a -SO ₃ M. R ₁ may be substituted at any position on the benzene ring. n7 and n8 each independently represent an integer of 0 to 2, preferably 0 or 1, but not both 0.

X _{1 to} X ₄ each independently represent -O-, -S
—, —NR ₅ —, —CR ₆ R ₇ —, wherein R _{5 to} R ₇ are each independently a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group (the preferred examples are R _{2 to} R ₄ R ₅ is preferably a hydrogen atom, an alkyl group,
Represents a sulfoalkyl group, and more preferably represents an alkyl group or a sulfoalkyl group. R ₆ and R ₇ preferably represent an alkyl group. X _{1 to} X ₄ are preferably -O- or -S-, and more preferably -S-.

R _{11 to} R ₁₄ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group (the preferred examples are the same as Ra ₁ and Ra ₂ ); An acid-substituted alkyl group (for example, an acid base is a carboxy group, a sulfo group, a phosphato group, a sulfonamide group, a sulfamoyl group, an acylsulfonamide group)
And the acid-substituted alkyl group is preferably a sulfoalkyl group.

M _{1 to} M ₆ each independently represent a methine group (preferred examples are the same as Ma ₁ to Ma ₁₄ ), and are preferably unsubstituted, ethyl-substituted, or methyl-substituted methine groups. n
1 and n2 each independently represent an integer of 0 to 3, preferably an integer of 0 to 2, and more preferably represent 0 or 1. n1, when n2 is 2 or _{more, M 1, M 2, M} 4, M 5 may be the same or different. Preferably, n1 and n2 are the same. Further, when n1 is 0, it is preferable that X _1, X ₂ are both -S-, when n1 is 1, X _1, X ₂ are both -O-
It is preferable that

V _{1 to} V ₄ each represent a substituent, and may be any of the above-mentioned substituent groups W.
(Preferred examples are the same as R _{2 to} R ₄ ), a halogen atom (eg, chlorine, bromine, iodine, fluorine), a nitro group, an alkoxy group having 1 to 20 C (eg, methoxy, ethoxy), C Aryl groups of the number 6 to 20 (for example,
Phenyl, 2-naphthyl), a C-20 heterocyclic group (for example, 2-pyridyl, 3-pyridyl, 1-pyrrolyl, 2-thienyl), a C6-C20 aryloxy group (for example,
Phenoxy, 1-naphthoxy, 2-naphthoxy), C number 1
20 acylamino groups (for example, acetylamino, benzoylamino), a carbamoyl group having 1 to 20 C (for example, N, N-dimethylcarbamoyl), a sulfo group, and 0 C atoms
-20 sulfonamide groups (e.g., methanesulfonamide), C-20-C sulfamoyl groups (e.g., N-methylsulfamoyl), hydroxyl groups, carboxyl groups, C1-C20 alkylthio groups (e.g., methylthio), And a cyano group. V1 to V4 are preferably an alkyl group, a halogen atom (particularly chlorine or bromine), an aryl group, an acylamino group, a carbamoyl group,
An alkoxy group, a hydroxyl group, a sulfo group, and a carboxyl group are preferred.
They are 5'-position and 6'-position.

N3 to n6 each represent an integer of 0 to 4, preferably 0 to 2. n3~n6 is 2 or more, V ₁ ~V ₄ may be the same or different, may form a ring. The ring to be formed is preferably a benzene ring, a pyridine ring, a benzofuran ring, a thiophene ring, a pyrrole ring,
Examples include an indole ring, and more preferred are a benzene ring and a benzofuran ring. At that time, A ₁ -L ₁ -R ₁ may be substituted at any position on the ring including the condensed ring.

It should be noted, G ₁ is connected with Dye1 at R ₁₁ or V _1, G ₂ is linked to Dye2 at R ₁₃ or V _3. At this time, the groups obtained by removing one hydrogen atom from the terminal of each of G ₁ , G ₂ , R ₁₁ , R ₁₃ , V ₁ , and V ₃ are connected to each other. It does not mean to manufacture. Preferred examples of V ₁ and V ₃ when linking to G ₁ and G ₂ include a carboxy group, an alkoxy group, an acylamino group, a carbamoyl group, a sulfonamide group, a sulfamoyl group, a hydroxy group, and an alkylthio group. More preferred are an acylamino group and a carbamoyl group. G ₁ is preferably linked to R ₁₁ , and G ₂ is preferably linked to R _{13. In} this case, it is preferable that R ₁₁ and R ₁₃ are both hydrogen atoms.

CI represents an ion for neutralizing 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. Examples of the cation include sodium ion, potassium ion, triethylammonium ion, diethyl (i-propyl) ammonium ion, pyridinium ion, and 1-ethylpyridinium ion. Examples of the anion include:
Halogen anions (eg, chloride ions, bromide ions,
Fluorine ion, iodine ion), substituted aryl sulfonate ion (eg, paratoluene sulfonate ion),
Examples thereof include alkyl sulfate ions (for example, methyl sulfate ions), sulfate ions, perchlorate ions, tetrafluoroborate ions, and acetate ions. y represents the number required to neutralize the charge.

In the compound of the present invention represented by the general formula (1) or (2), preferred examples of Dye1 are as follows. However, the present invention is not limited to this. In addition,
The structural formula of the compound of the present invention described below is only one of the possible resonance structures, and another structure that can be formed by resonance may be employed.

[0041]

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[0042]

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[0043]

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[0044]

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[0045]

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In the compound of the present invention represented by the general formula (1) or (2), preferred examples of Dye2- (A ₁ -L ₁ -R ₁ ) m1 are as follows. However, the present invention is not limited to this.

[0047]

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[0048]

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[0049]

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[0050]

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In the compound of the present invention represented by formula (1) or (2), preferred examples of the linking group -L _2- are as follows. However, the present invention is not limited to this.

[0052]

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[0053]

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[0054]

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The general formula (1) or (2) of the present invention is described below.
Specific examples of the compound represented by are shown below, but the present invention is not limited thereto.

[0056]

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[0057]

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As the compound of the present invention, preferably, in the general formula (2), X ₁ , X ₂ , X ₃ and X ₄ are -S-,
R ₁₃ is an alkyl group, R ₁₁ , R ₁₂ , and R ₁₄ are sulfoalkyl groups, A ₁ is —O—, L ₁ is an alkylene group, and R ₁ is —SO ₃ M There are cases. The compound of the present invention can be synthesized, for example, according to the method described in the following literature. Heterocycl by FMHarmer
ic Compounds-Cyanine Dyes and Related Compound
s, John & Wiley & Sons, New York, London, 1964, DMSturmer, Heterocyclic Compounds-Specia
l Topics in Heterocyclic Chemistry, Chapter 18, Chapter 14
Verses, 482-515, John & Wiley & Sons, New Yor
k, London, 1977, European Patent 887700A1.

In the compound represented by the general formula (1), it is preferable that the adsorptivity to silver halide grains satisfies Dye1> Dye2. The adsorptivity to silver halide grains can be determined using the respective model compounds.

Further, the compound represented by the general formula (1)
When Dye2 is photoexcited, it is preferable that electron transfer or energy transfer to Dye1 is possible. further,
In a silver halide photographic emulsion and a silver halide photosensitive material, when the compound represented by the general formula (1) is adsorbed to silver halide grains by Dye1, and Dye2 not adsorbed to silver halide grains is photoexcited. Electron transfer or energy transfer to Dye1 is preferred. In the silver halide photographic emulsion and the silver halide photosensitive material, the compound represented by the general formula (1) is adsorbed on the silver halide grains at Dye1 to form a J association, and further adsorbed on the silver halide grains. It is preferable that Dye2 not formed also forms a J association.

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

The compound of the present invention is mainly used as a sensitizing dye in silver halide photographic emulsions and silver halide photographic materials. The compounds of the present invention can be used alone, in combination with the compounds of the present invention, or in combination with other sensitizing dyes in a silver halide photographic emulsion or a silver halide photosensitive material. At that time, as the dye used, preferably a cyanine dye, a merocyanine dye, a rhodocyanine dye, a trinuclear merocyanine dye, a tetranuclear merocyanine dye,
Allopolar dyes, hemicyanine dyes, styryl dyes and the like can be mentioned. More preferred are cyanine dyes, merocyanine dyes and rhodacyanine dyes, and particularly preferred are cyanine dyes. For more information on these dyes, see FM Harmer, Heterocyclic Compounds-Cysteine Soybeans and Related Compounds.
anine Dyes and Related Compounds), John Wiley &amp; Sons, Inc.-New York, London, 1964, DMSturmer, Heterocyclic Compounds-Special Topics・ In Heterocyclic Compounds-Spec
ial topics in heterocyclic chemistry) ", No. 18,
Chapter 14, section 14, pages 482-515. Preferred dyes include U.S. Patent No. 5,994,994.
051, pages 32 to 44, and U.S. Pat.
7,236, pages 30 to 39, and sensitizing dyes represented by specific examples. Preferred general formulas of cyanine dyes, merocyanine dyes and rhodacyanine dyes are those shown in (XI), (XII) and (XIII) in U.S. Pat. No. 5,340,694, columns 21-22. , N12, n15, n17, and n18 are not limited, and may be an integer of 0 or more (preferably 4 or less).

Although these sensitizing dyes may be used alone,
Two or more types may be used, and a typical example (for supersensitization) used in two or more types is US Pat. No. 2,688,545.
No. 2,977,229 and 3,397,060
No. 3,522,052, No. 3,527,641
No. 3,617,293 and 3,628,964
No. 3,666,480, 3,672,898
No. 3,679,428 and 3,303,377
Nos. 3,769,301 and 3,814,609
No. 3,837,862, No. 4,026,707
No. 1,344,281 and 1,507,8
No. 03, JP-B-43-49336, JP-B-53-1237
5, JP-A-52-110618 and JP-A-52-11099.
No. 25, etc.

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

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

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

The sensitizing dye of the present invention (and other sensitizing colors)
And the supersensitizer).
Depending on the shape and size of silver
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 mole
You. For example, when the silver halide grain size is 0.2 to 1.3.
In the case of μm, 2 × 10
^-6~ 3.5 × 10^-3The molar amount is preferably 7.5 ×
10^-6~ 1.5 × 10^-3A molar addition amount is more preferred.

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

In the present invention, the photographic emulsion which controls the photosensitive mechanism includes any of silver bromide, silver iodobromide, silver chlorobromide, silver iodide, silver iodochloride, silver iodochlorobromide and silver chloride. Although a halogen composition on the outermost surface of the emulsion may contain iodine of 0.1 mol% or more, more preferably 1 mol% or more, 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 crystals such as cubic, octahedral, tetradecahedral, or rhombic dodecahedron, or irregular such as spherical, plate-like, etc. (Irregular) crystal form,
It may have a higher-order plane ((hkl) plane) or a mixture of grains of these crystal forms, but is preferably a tabular grain, and the tabular grain will be described in detail below. Journal of I for particles with higher planes
See 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 singly or in combination.
The silver halide grains may have different phases between the inside and the surface layer, may have a multiphase structure having a bonding structure, may have a localized phase on the grain surface, or may have a uniform grain as a whole. May consist of phases. They may be mixed. These various emulsions may be either a surface latent image type in which a latent image is mainly formed on the surface or an internal latent image type in which a latent image is formed inside a 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 main surface of (100) or (111). Tabular grains having a (111) major surface, hereinafter referred to as (111) tabular, usually have triangular or hexagonal faces. Generally, the more uniform the distribution, the higher the proportion of tabular grains having more hexagonal faces. The hexagonal monodispersed flat plate is described in Japanese Patent Publication No. 5-61205.

Tabular grains having a (100) plane as a main surface,
The (100) flat plate also has a rectangular or square shape. In this emulsion, grains having an adjacent side ratio of less than 5: 1 are called tabular grains. In silver chloride or tabular grains containing a large amount of silver chloride, (100) tabular grains originally have higher stability on the main surface than (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 U.S. Pat. No. 5,298,388.

The following patent discloses the silver chloride or the (111) flat plate having a high silver chloride content used in the present invention. U.S. Patent No. 4,414,306, U.S. Patent No. 4,400,463, U.S. Patent No. 4,713,323
No. 4,783,398; U.S. Pat.
No. 491, U.S. Pat. No. 4,983,508, U.S. Pat.
No. 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,
U.S. Pat. No. 4,443,426; U.S. Pat. No. 4,439,520
No. 4,414,310; U.S. Pat.
048, U.S. Pat. No. 4,647,528, U.S. Pat.
No. 6,650,012, U.S. Pat. No. 4,672,027, U.S. Pat. No. 4,678,745, U.S. Pat. No. 4,684,607,
U.S. Pat. No. 4,593,964, U.S. Pat.
6, U.S. Pat. No. 4,722,886, U.S. Pat.
5617, U.S. Patent No. 4,755,456, U.S. Patent No. 4,806,461, U.S. Patent No. 4,801,522, U.S. Patent No. 4,835,322, U.S. Patent No. 4,839,268,
U.S. Pat. No. 4,914,014, U.S. Pat.
5, U.S. Pat. No. 4,977,074, U.S. Pat.
No. 5,350, U.S. Pat. No. 5,061,609, U.S. Pat. No. 5,061,616, U.S. Pat. No. 5,068,173, U.S. Pat. No. 5,132,203, U.S. Pat.
No. 5,334,469, U.S. Pat.
No. 495, US Pat. No. 5,358,840, US Pat.
372927.

The (100) flat plate used in the present invention is described in the following patents. US Patent No. 43
No. 86156, 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.
No. 5,356,764, European Patent No. 5699.
No. 71, EP 737887, JP-A-6-308
648, JP-A-9-5911.

The silver halide emulsion used in the present invention has a higher surface area / absorbing sensitizing dye disclosed in the present invention.
Tabular silver halide grains having a high volume ratio are preferred, and the aspect ratio is preferably 2 or more, more preferably 5 or more, and particularly preferably 8 or more. There is no upper limit,
Preferably it is 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 less than 0.07 μm.

Here, the expression that the aspect ratio is 2 or more means that silver halide grains having an aspect ratio (equivalent diameter of silver halide grains / grain thickness) of 2 or more are obtained by projecting all silver halide grains in the emulsion. It means that 50% or more of the area exists. Preferably at least 70%, particularly preferably at least 85
% Of the emulsion.

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

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

Gelatin is advantageously used as a protective colloid used in preparing 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; cellulose derivatives such as hydroxyethylcellulose, carboxymethylcellulose and cellulose sulfates, sugar derivatives such as sodium alginate and starch derivatives ;
Polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylimidazole, etc. Can be used. Examples of gelatin include lime-processed gelatin, acid-processed gelatin and Bull. Soc. Sci.
Photo. Japan. No. 16. P30 (196
Enzyme-treated gelatin as described in 6) may be used, and hydrolysates or enzymatic degradation products 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 is preferably selected in the range of 5 ° C to 50 ° C. The pH at the time of washing can be selected according to the purpose, but is preferably selected from 2 to 10. More preferably, it is in the range of 3 to 8. The pAg at the time of washing can be selected according to the purpose, but is preferably selected from 5 to 10. Noodle washing method, dialysis method using semi-permeable membrane,
The method can be selected from centrifugal separation, coagulation sedimentation, and ion exchange. 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.

When preparing the emulsion of the present invention, for example, during grain formation,
In the desalting step, at the time of chemical sensitization, the presence of a metal ion salt before coating is preferable depending on the purpose. In the case of doping the grains, it is preferable to add them at the time of grain formation, when modifying the grain surface or when using as a chemical sensitizer, after grain formation and before the end of chemical sensitization. A method of doping the entire grain and a method of doping only the core part or only the shell part of the grain 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 ammonium salts, acetates, nitrates, sulfates, phosphates, hydroxides, or salts that can be dissolved at the time of particle formation, such as six-coordinate complex salts and four-coordinate complex salts. 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
_{l 6, (NH 4) 3} RhCl 6, K 4 Ru (CN) 6 and the like. The ligand of the coordination compound can be selected from halo, aquo, cyano, cyanate, thiocyanate, nitrosyl, thionitrosyl, oxo, and carbonyl. These may be used alone or in combination of two or more metal compounds.

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

A method of adding a chalcogen compound during the preparation of an emulsion as described in US Pat. No. 3,772,031 is sometimes useful. In addition to S, Se, and Te, cyanide, thiocyanate, selenocyanic acid, carbonate, phosphate, and acetate may be present.

The silver halide grains of the present invention may be subjected to at least one of sulfur sensitization, selenium sensitization, gold sensitization, palladium sensitization or noble metal sensitization and reduction sensitization at any step in the production process of a silver halide emulsion. Can be applied. It is preferable to combine two or more sensitization methods. Various types of emulsions can be prepared depending on the step of chemical sensitization. There are a type in which a chemical sensitizing nucleus is embedded in the grain, a type in which the chemical sensitizing nucleus is embedded in a position shallow from the grain surface, and a type in which a chemical sensitizing nucleus is formed on the surface. In the emulsion of the present invention, the location of the chemical sensitization nucleus can be selected according to the purpose. Generally, the case where at least one type of chemical sensitization nucleus is formed near the surface is preferred. One of the chemical sensitizations that can be preferably performed in the present invention is chalcogen sensitization and noble metal sensitization alone or in combination, and is described by TH James, The Photographic Process, Fourth Edition, Macmillan. Published by the company
1977, (TH James, The Theo)
ry of the Photographic Pr
ocess, 4th ed, Macmillan, 19
77) can be carried out using active gelatin as described on pages 67-76, and can also be performed by Research Disclosure, 120, April 1974, 12008; Research Disclosure, 34, 6 June 1975.
Moon, 13452, U.S. Patent Nos. 2,642,361, 3,297,446, and 3,772,031,
Nos. 3,857,711 and 3,901,714,
Nos. 4,266,018 and 3,904,4
No. 15, and pAg 5-10, pH 5-8 and temperature 30-30 as described in GB 1,315,755.
At 80 ° C., it can be sulfur, selenium, tellurium, gold, platinum, palladium, iridium or a combination of these sensitizers. 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, known compounds such as chloroauric acid, potassium chloroaurate, potassium aurithiocyanate, gold sulfide, and gold selenide can be used. The palladium compound means a divalent palladium salt or a tetravalent salt. Preferred palladium compounds are represented by R ₂ PdX ₆ or R ₂ PdX ₄ . Here, 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
PdCl ₆ , Na ₂ PdCl ₄ , (NH ₄ ) ₂ PdCl
₄ , Li ₂ PdCl ₄ , Na ₂ PdCl ₆ or K ₂ Pd
Br ₄ is preferred. The gold compound and the palladium compound are preferably used in combination with a thiocyanate or a selenocyanate. As sulfur sensitizers, hypo, thiourea compounds, rhodanine compounds and US Pat.
No. 7,711, 4,266,018 and 4,054,457 can be used. Chemical sensitization can also be performed in the presence of a so-called chemical sensitization aid. Useful chemical sensitization aids include compounds known to suppress fog and increase sensitivity during chemical sensitization, such as azaindene, azapyridazine and azapyrimidine. Examples of chemical sensitization aid modifiers are described in US Pat. No. 2,131,038.
No. 3,411,914, No. 3,554,75
No. 7, JP-A-58-126526 and the aforementioned "Emulsion Chemistry" by Duffin, pp. 138-143. The emulsion of the present invention is preferably used in combination with gold sensitization.
The preferred amount of the gold sensitizer is 1 per mole of silver halide.
The amount is from × 10 ^-4 to 1 × 10 ^-7 mol, more preferably from 1 × 10 ^{-5 to} 5 × 10 ^-7 mol. The preferred range of the palladium compound is from 1 × 10 ⁻³ to 5 × 10 ⁻⁷ . The preferred range of the thiocyan compound or selenocyan compound is from 5 × 10 ⁻² to 1 × 10 ⁻⁶ . The preferred amount of sulfur sensitizer used for the silver halide grains of the present invention is from 1 × 10 ^-4 to 1 × 10 ^-7 mol, more preferably from 1 × 10 ^-5 to 1 × 10 ^-7 mol per mol of silver halide. It is 5 × 10 ^-7 mol. Selenium sensitization is a preferred sensitization method for the emulsion of the present invention. In the selenium sensitization, a known unstable selenium compound is used, and specifically, colloidal metal selenium, selenoureas (for example, N, N-dimethylselenourea, N, N-diethylselenourea), selenoketones And selenium compounds such as selenoamides. It may be preferable to use selenium sensitization in combination with sulfur sensitization and / or noble metal sensitization.

During the grain formation of the silver halide emulsion of the present invention,
It is preferable to perform 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 ripening in a pAg 1 to 7 low pAg atmosphere called silver ripening, or a pH 8 to 10 called high pH ripening. Either a method of growing or ripening in a high pH atmosphere of 11 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 the reduction sensitizer include stannous salts, ascorbic acid and derivatives thereof, amines and polyamines, hydrazine derivatives, formamidine sulfinic 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, and two or more 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 an appropriate range is from 10 ^-7 to 10 ^-3 mol 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 at an appropriate time during the particle growth is preferable. Alternatively, a reduction sensitizer may be added in advance to the water solubility of a water-soluble silver salt or a water-soluble alkali halide, and silver halide grains may be precipitated using these aqueous solutions. It is also a preferred method to add the solution of the reduction sensitizer in several portions as the grains grow, or to add the solution continuously for a long time.

During the production process of the emulsion of the present invention, an acid for silver is used.
It is preferable to use an agent. The oxidizing agent for silver is
Has the effect of converting to silver ions by acting on metallic silver
Refers to a compound. Especially the formation process of silver halide grains and
Extremely small silver particles by-produced during chemical sensitization
Is a compound that can be converted into a silver ion. here
The silver ions generated in, for example, silver halide, sulfide
May form silver salts that are hardly soluble in water such as silver and silver selenide.
And may form a silver salt easily soluble in water such as silver nitrate.
No. The oxidizing agent for silver can be inorganic or organic.
There may be. As the inorganic oxidizing agent, for example, Ozo
Hydrogen peroxide and its adducts (eg, NaBO)_Two
・ H_TwoO_Two・ 3H_TwoO, 2NaCO_Three・ 3H_TwoO_Two, Na_Four
P_TwoO₇・ 2H_TwoO _Two, 2Na_TwoSO_Four・ H_TwoO_Two・ 2H
_TwoO), peroxyacid salts (eg, K_TwoS_TwoO₈, K_TwoC_TwoO
₆, K_TwoP_TwoO₈), Peroxy complex compounds (eg, K_Two
[Ti (O_Two) C_TwoO_Four] ・ 3H_TwoO, 4K_TwoSO_Four・ Ti
(O_Two) OH ・ SO_Four・ 2H_TwoO, Na_Three[VO (O_Two)
(C_TwoH_Four)_Two] ・ 6H_TwoO), permanganate (e.g.
For example, KMnO_Four), Chromates (eg, K_TwoCr_TwoO₇)
Oxyacid salts like, halogen elements like iodine and bromine,
Perhalates (eg, potassium periodate), high atoms
Salts of divalent metals (eg potassium hexacyanoferric acid)
) And thiosulfonates.

Examples of the organic oxidizing agent include quinones such as p-quinone, organic peroxides such as peracetic acid and perbenzoic acid, and compounds which release active halogen (for example, N-
Bromsuccinimide, chloramine T, chloramine B)
Is given as an example.

Preferred oxidizing agents of the present invention are inorganic oxidizing agents such as ozone, hydrogen peroxide and its adducts, halogen elements, thiosulfonates, and organic oxidizing agents such as quinones.
It is a preferred embodiment to use the above-described reduction sensitization and an oxidizing agent for silver in combination. The method can be selected from a method of performing reduction sensitization after using an oxidizing agent, a method reverse thereto, or a method of coexisting the two simultaneously. These methods can be selectively used in both the grain formation 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 production process, storage or photographic processing of the photographic material, or stabilizing photographic performance. . That is, thiazoles, for example, benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, amino Triazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazole (especially 1-phenyl-5-mercaptotetrazole);
Mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxadrinethione; azaindenes such as triazaindenes, tetraazaindenes (especially 4-hydroxy-substituted (1,3,3
a, 7) known as antifoggants or stabilizers, such as titraazaindenes) and pentaazaindenes;
Many compounds can be added. For example, U.S. Patent Nos. 3,954,474 and 3,982,947,
Those described in JP-B-52-28660 can be used. One of the preferred compounds is disclosed in JP-A-63-21.
2932. Antifoggants and stabilizers are used at various times before, during and after particle formation, during the water washing step, during dispersion after water washing, before chemical sensitization, during chemical sensitization, after chemical sensitization, and before coating. It can be added according to the purpose. In addition to exhibiting the original antifogging and stabilizing effects by adding during emulsion preparation, it controls the crystal wall of the grains, reduces the grain size, reduces the solubility of the grains, controls the chemical sensitization, 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 for both color photographic materials and black-and-white photographic materials. Color photographic light-sensitive materials include color photographic paper, color photographic films, color reversal films, color diffusion transfer films, and black-and-white photographic light-sensitive materials include general photographic films, X-ray films, medical diagnostic films, and printing photographic materials. Film, diffusion transfer film and the like.

In the field of medical diagnostic films and films for printed light-sensitive materials, exposure can be efficiently performed by a laser imagesetter or laser imager. The technology in these fields is described in Japanese Patent Application Laid-Open No. 7-28.
7,337, JP-A-4-335342, JP-A-5
-313,289, JP-A-8-122,954, JP-A-8-292,512 and the like. Further, a photothermographic material can also be used. For example, a catalytically active amount of a photocatalyst (eg, silver halide), a reducing agent,
A material having a photosensitive layer in which a reducible silver salt (for example, an organic silver salt) and, if necessary, a color tone controlling silver tone is dispersed in a binder matrix is known. These are described, for example, in US Pat.
4, U.S. Pat. No. 3,457,075, U.S. Pat.
No. 4,500,626, JP-B-43-4924
No., JP-A-11-24200, JP-A-11-24201, JP-A-11-30832,
11-84574, 11-65021, 11-109547, 11-12
No. 5880, No. 11-129629, No. 11-133536 to No. 11-133539
No. 11-133542, No. 11-133543, No. 11-223898,
11-352627, 6-130607, 6-332
No. 134, No. 6-332136, No. 6-347970
No. 7-261354, Japanese Patent Application 2000-89436
No. and the like.

The compound of the present invention can be preferably used also for a diffusion transfer light-sensitive material. Among these, the thermal development diffusion transfer method is described in Japanese Patent Application No. 10-265273 (using a preformed dye) and Japanese Patent Application No. 2000-89436 (using a coupling forming dye), and the instant photographic method is disclosed in Japanese Patent Application No. Hei. The method described in JP-A-11-89801 can be referred to.

For the preparation of the photographic emulsion used in the present invention, column 63, line 36 to column 65, line 2 of JP-A-10-239789 can be applied. The types of photosensitive materials to which the present invention is applied, such as additives such as color couplers and photographic photosensitive material additives, and the processing of photosensitive materials, are described in JP-A-10-239789, column 65, line 3 to Column 73, line 13, etc. can be applied.

The silver halide photographic light-sensitive material of the present invention includes:
Although the various additives described above are used, other various additives can be used according to 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 portions are summarized in the table below.

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, page 23-24, page 648, right column-996 right-998 right Super strong Sensitizer page 649 right column 4 Brightener 24 page 998 right 5 Antifoggant 24-25 page 649 right column 998 right-1000 right and stabilizer 6 Light absorber, fill 25-26 page 649 right column 1003 left to 1003 right tar, UV absorber page 650 left column 7 Stain inhibitor 25 page right column 650 left to right column 1002 right 8 Dye image stabilizer 25 page 1002 right 9 Hardener 26 page 651 left column 1004 right 1005 left to 1006 right Same as above 1003 right to 1004 right 11 Plasticizer, lubricant page 27 650 page right column 1006 left to 1006 right 12 Coating aid, page 26 to 27 same 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 in the emulsion of the present invention and photographic materials using the emulsion, silver halide emulsions, dye-forming couplers, functional couplers such as DIR couplers, various additives, etc. And development processing are described in EP 056596 A1 (1993).
And published patents cited therein. The following is a list of each item and the corresponding descriptions.

1. 1. Layer structure: page 61, lines 23 to 35, line 41 to page 62, line 14 2. Intermediate layer: page 61, lines 36 to 40 3. Multilayer effect imparting layer: page 62, lines 15 to 18 4. Silver halide composition: page 62, lines 21 to 25 5. Silver halide grain habit: page 62, lines 26 to 30 6. Silver halide grain size: page 62, lines 31 to 34 7. Emulsion production method: page 62, lines 35 to 40 8. Silver halide grain size distribution: page 62, lines 41 to 42 Tabular grains: page 62, lines 43 to 46 10. 10. Internal structure of particle: page 62, lines 47 to 53 11. Emulsion latent image formation type: page 62, line 54 to page 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. Fogged emulsion: page 63, lines 14 to 31 Non-light-sensitive emulsion: page 63, lines 32 to 43 Silver coating amount: 63 pages 49-50 lines

17. Formaldehyde scavenger: page 64, lines 54 to 57 18. Mercapto antifoggant: page 65, lines 1 and 2 19. Release agent such as fogging agent: page 65, lines 3-7 20. Dye: page 65, lines 7 to 10 21. General color couplers: page 65, lines 11 to 13 Yellow, magenta and cyan couplers: page 65, lines 14-25 23. Polymer coupler: page 65, lines 26-28 24. Diffusible dye-forming coupler: page 65, lines 29-31 25. Colored coupler: page 65, lines 32-38 26. Functional couplers in general: p. 65, lines 39-44 27. Bleach accelerator releasing coupler: page 65, lines 45-48 28. Development accelerator releasing coupler: page 65, lines 49 to 53 29. Other DIR couplers: page 65, line 54 to page 66, line 4 Coupler dispersion method: page 66, lines 5-28

31. Preservatives / fungicides: page 66, lines 29-33 32. Type of photosensitive material: page 66, lines 34-36 33. Photosensitive layer thickness and swelling speed: page 66, line 40 to page 67, line 1 34. Back layer: page 67, lines 3-8 35. Overall development processing: page 67, lines 9 to 11 Developer and developer: page 67, lines 12-30 37. Developer additive: page 67, lines 31 to 44 38. Inversion processing: page 67, lines 45 to 56 39. Processing solution opening ratio: page 67, line 57 to page 68, line 12 Developing time: page 68, lines 13 to 15 41. Bleaching / fixing / bleaching / fixing: page 68, line 16 to page 69, line 31 Automatic developing machine: page 69, lines 32 to 40 43. Rinsing, rinsing, stabilization: page 69, line 41 to page 70, line 18 Processing solution replenishment and reuse: page 70, lines 19 to 23 45. Built-in photosensitive material for developer: Page 70, lines 24 to 33 46. Developing temperature: page 70, lines 34-38 47. Use for film with lens: 70 pages 39-41

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

In the present invention, a laser light source may be preferably used. Examples of laser light include those using helium-neon gas, argon gas, krypton gas, carbon dioxide gas, etc. as a laser oscillation medium, lasers using a solid such as ruby, cadmium as an oscillation medium, other liquid lasers, and semiconductor lasers. is there. Unlike laser light used for ordinary illumination, these laser lights are coherent light with a single frequency and the same phase and sharp direction, so halogen light for exposing them as a light source is used. Silver photographic light-sensitive materials need to have spectral characteristics that match the emission wavelength of the laser used. Among these lasers, a semiconductor laser is preferably used.

In addition to the sensitizing dye, the compound of the present invention can be used as various filter dyes, irradiation prevention dyes or antihalation dyes for the purpose of improving sharpness and color resolution. . This compound is prepared by a conventional method using a silver halide photographic material layer,
It can be contained in a coating solution such as a filter layer and / or an antihalation layer. The dye may be used in an amount sufficient to color 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. It is preferable to use it. The timing of addition may be any step before coating.

Further, a polymer having a charge opposite to that of the dye ion may coexist as a mordant in the layer, and the dye may be localized in the specific layer by the interaction 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
Nos. 8,976 and 3,445,231. The compound of the present invention can be added to desired layers such as an intermediate layer, a protective layer, and a back layer in addition to the photosensitive emulsion layer.

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 the like, and can also be used in a photocatalyst, a photohydrogen generator 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 particle surface area,
The optical density Log when the amount of light incident on the unit surface area of the particles is I ₀ and the amount of light absorbed by the sensitizing dye on the surface is I.
(I ₀ / (I ₀ −I)) is defined as a value obtained by integrating the wave number (cm ⁻¹ ). Integration range from 5000 cm ^-1 to 3
Up to 5000 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 a particle having a particle diameter of less than nm, it is preferable that the silver halide particle having a light absorption intensity of 60 or more contains at least 1/2 of the total projected area of the silver halide particle. In addition, the spectral absorption maximum wavelength 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, and particularly preferably 200 or more, and the spectral absorption maximum wavelength is 500 n.
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 preferably 200
0 or less, more preferably 1000 or less, particularly preferably 500 or less. Also, the spectral absorption maximum wavelength is 500n
m, the spectral absorption maximum wavelength is 350 n
m or more.

As an example of a method for measuring the light absorption intensity,
Can use a microspectrophotometer.
You. Microspectrophotometer measures the absorption spectrum of a small area
Device that can measure the transmission spectrum of a single particle.
Noh. Of the absorption spectrum of one particle by microspectroscopy
For the measurement, see Yamashita et al.'S report (The Photographic Society of Japan, 199
6th Annual Meeting Abstracts, p. 15)
Can be. From this absorption spectrum, the absorption per particle
Although light intensity is required, the light passing through the particles is
Absorbed on two sides of the surface
Absorption intensity per particle obtained by the method described above.
It can be obtained as の of the yield strength. At this time,
The interval for integrating the absorption spectrum is
5000cm ^-1From 35000cm^-1But on the experiment
Is 500 cm before and after the section with absorption by the sensitizing dye^-1About
It may be the integral of the section including the degree. Also, the light absorption intensity increases.
The strength of the dye and the number of adsorbed molecules per unit area
These values are determined uniquely, and the oscillator strength and color of the sensitizing dye
Converted to light absorption intensity by calculating the amount of element adsorbed and particle surface area
You can do it. The oscillator strength of the sensitizing dye is
Solution area intensity (optical density x cm^-1Is proportional to
Can be obtained experimentally as a value.
The absorption area intensity of the dye of A (optical density × cm^-1), Sensitization
The amount of dye adsorbed is B (mol / mol Ag), particle surface area
To C (m^Two/ MolAg), the light absorption is calculated by the following equation.
The yield strength can be determined within an error range of about 10%. 0.156 × A × B / C Even if the light absorption intensity is calculated from this equation, it is based on the above-mentioned definition.
Light absorption intensity (Log (I₀/ (I₀−
I))) is the wave number (cm^-1 )) And
Substantially the same values are obtained.

As a method of increasing the light absorption intensity, there are a method of adsorbing the dye chromophore more on the particle surface, a method of increasing the molecular extinction coefficient of the dye, and a method of reducing the dye occupation area. Any of these methods may be used, but is preferably a method in which the dye chromophore is further adsorbed on the particle surface. Here, the state in which the dye chromophore is more adsorbed on the grain surface means that more bound dye is present in the vicinity of the silver halide grains, and includes the dye present in the dispersion medium. Absent. The expression “more than one” as used herein includes a 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. At that time, it is necessary that spectral sensitization is caused by a dye that is not directly adsorbed on the grain surface. Communication is required. Therefore, if the transmission of the excitation energy needs to occur in more than 10 steps, the final transmission efficiency of the excitation energy becomes low, which is not preferable. One example is a case where most of the dye chromophore is present in a dispersion medium, such as a polymer dye as disclosed in JP-A-2-113239, and transmission of excitation energy is required in 10 or more steps. The adsorption of the dye chromophore to the silver halide grains is preferably 1.5 layers or more, more preferably 1.7 layers or more, and particularly preferably 2 layers.

In the present invention, the state in which the chromophore is further adsorbed on the surface of the silver halide grain is defined as the sensitizing dye added to the emulsion, the dye having the smallest area occupied by the dye on the surface of the silver halide grain. The reached saturated adsorption amount per unit surface area is defined as a more saturated coating amount, and a state in which the amount of adsorption of the dye chromophore per unit area is larger than the one more saturated coating amount. The number of adsorbed layers means the amount of adsorption based on the amount of one-layer saturated coating. Here, in the case of a dye in which dye chromophores are linked by a covalent bond, the dye occupied area of each dye in a non-linked state can be used as a reference.
The dye occupied area can be determined from an adsorption isotherm indicating the relationship between the concentration of free dye and the amount of adsorbed dye, and the particle surface area. Adsorption isotherms are described, for example, by A. Hers.
z) et al. Adsorption from Aquas Solution
eous Solution) Advances Inn
Chemistry Series (Advances in C
Chemistry Series) No. 17,173
Page (1968).

The amount of the sensitizing dye adsorbed on the emulsion particles was determined by separating the emulsion adsorbed with the dye into a centrifugal separator to separate the emulsion particles and the supernatant aqueous gelatin solution, and measuring the unadsorbed dye concentration by measuring the spectral absorption of the supernatant. Subtracting from the amount of dye added to determine the amount of adsorbed dye, and drying the precipitated emulsion particles, dissolving a certain weight of the precipitate in a 1: 1 mixture of aqueous sodium thiosulfate and methanol, and performing spectral absorption measurement Can be used to determine the amount of adsorbed dye. When a plurality of types of sensitizing dyes are used, the adsorption amount of each dye can be determined by a technique such as high performance liquid chromatography. Although the dye occupation area can be determined empirically, since the molecular area of the sensitizing dye used normally is in the vicinity of approximately 80 Å ^2, approximate adsorption layer a dye occupation area as 80 Å ² for simple all dyes You can also estimate the number.

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

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

The reduction potential and the oxidation potential can be measured by various methods, but preferably by a phase discrimination type second harmonic AC polarography, and accurate values can be obtained. . The method for measuring the potential by the phase discrimination type second harmonic AC polarography is described in Journal of Imaging Science (Journ).
al of Imaging Science), 3rd
0, page 27 (1986).

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

Further, the maximum absorption wavelength of the dye chromophore of the first layer in the silver halide photographic material is longer than the maximum absorption wavelength of the dye chromophore of the second layer or more. It is preferable that the above emission of the dye chromophore overlaps with the absorption of the dye chromophore in the first layer from the viewpoint of energy transfer efficiency from the dye in the second or higher layer to the dye in the first layer. Further, the dye chromophore in the first layer preferably forms a J-aggregate. Further, in order to have absorption and spectral sensitivity in a desired wavelength range, it is preferable that the dye chromophores of the second layer or more also form J-aggregates. 1 of the excitation energy of the second layer dye
The energy transfer efficiency to the layer dye is preferably 30%
Above, more preferably 60%, particularly preferably 90%
That is all. Here, the excitation energy of the second layer dye is
It refers to the energy of the dye in the excited state generated by the absorption of light energy by the second-layer dye. When the excitation energy of a certain molecule is transferred to another molecule, an excited electron transfer mechanism, a Forster type energy transfer mechanism (Forst)
er Model), the Dexter energy transfer mechanism (Dextor Model), and the like, it is considered that the excitation energy is transferred. Therefore, even in the multilayer adsorption system of this study, it is necessary to cause the efficient excitation energy transfer considered from these mechanisms. Preferably, the condition is satisfied. Furthermore, it is particularly preferable to satisfy the conditions for causing a Forster type energy transfer mechanism. The efficiency of energy transfer from the second-layer dye to the first-layer dye can be determined as spectral sensitization efficiency when the second-layer dye is excited / 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: occupied area per dye molecule. It can be determined experimentally from the adsorption isotherm. In the case of a dye in which a dye chromophore is linked by a covalent bond, the area occupied by the dye in an unlinked state is used as a reference. 80Å ^{2 for} simplicity. Single-saturated coating amount: The amount of dye adsorbed per unit particle surface area at the time of single-saturated coating. Reciprocal of the smallest dye occupied area among the added dyes. Multilayer adsorption: A state in which the amount of dye chromophore adsorbed per unit particle surface area is even larger than the saturated coating amount. In the present invention, the multilayer adsorption means a state in which the amount of dye chromophore adsorbed per unit particle surface area is larger than the saturated coating amount. When the layers are adsorbed, 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 amount of one-layer saturated coating. In the case of a compound in which two dye chromophores are linked by a covalent bond, the above-mentioned adsorption amount × 2 is defined as the number of adsorption layers. For example, if a dye in which two dye chromophores are covalently linked has the same dye occupation area and the same amount of adsorption as a certain non-linked model dye, the number of adsorption layers is 2.

[0117]

Next, the present invention will be described based on examples, but the present invention is not limited to these examples.

Example 1 Synthesis Example of Compound D-2 of the Present Invention

[0119]

Embedded image

2-methylbenzothiazole [1], 3.24 g
(10 mmol), bromohexanoic acid [2], 3.90 g (20 mmo
l) was stirred without solvent at 140 ° C. for 6 hours. After cooling, acetone was added to obtain 4.0 g of crystals of 2-methylbenzotriazole quaternary salt [3] (96% yield).

4-Methylbenzotriazole quaternary salt [3], 4.0 g (4.8 mmol), 2-mercaptobenzothiazole quaternary salt [4], 4.11 g (10 mmol), and triethylamine 4.04 g (40 mmol) were added to acetonitrile 40 ml. Dissolve 60 ° C
For 1 hour. After cooling, the crystals were separated by filtration, dissolved in methanol, added with 0.81 g (10 mmol) of sodium acetate, further added with acetonitrile, and the resulting crystals were separated by filtration and washed with acetonitrile. After vacuum drying, 3.80 g (yield 52%) of the cyanine dye [5] was obtained.

Cyanine dye [5], 0.56 g (0.8 mmol),
0.50 g (0.8 mmol) of cyanine dye [6] and 0.12 g (0.88 mmol) of 1-hydroxybenzotriazole synthesized with reference to the method of European Patent No. 887700A were added to dimethyl sulfoxide 3
It was dissolved in 0 ml and stirred at 60 ° C. for 10 minutes. 0.30 g (0.96 mmol) of uronium salt [7] and 0.37 g (2.9 mmol) of diisopropylethylamine 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. Dissolve the crystals in methanol and add sodium acetate 0.06
4 g (0.8 mmol) was added, and isopropyl alcohol was added. The resulting crystals were separated by filtration and washed with isopropyl alcohol. After vacuum drying, 0.68 g (68% yield) of the target yellow crystal of D-2 was obtained. The structure was confirmed by NMR spectrum, MS spectrum and elemental analysis. Other compounds of the present invention can be synthesized in the same manner as described above.

Example 2 (Preparation of seed emulsion a) KBr 0.017 g, average molecular weight 2
Aqueous solution 11 containing 0.4 g of 0000 oxidized gelatin
64 ml was kept at 35 ° C. and stirred. AgNO ₃ (1.6
g) An aqueous solution, an aqueous KBr solution, and an aqueous solution of oxidized gelatin (2.1 g) having an average molecular weight of 20,000 were added over 48 seconds by a triple jet method. At this time, the silver potential was kept at 13 mV with respect to the saturated calomel electrode. After an aqueous KBr solution was added to adjust the silver potential to −66 mV, the temperature was raised to 60 ° C. 21 g of succinated gelatin having an average molecular weight of 100,000
Was added, and an aqueous solution of NaCl (5.1 g) was added. An aqueous solution of AgNO ₃ (206.3 g) and an aqueous solution of KBr were added over a period of 61 minutes while accelerating the flow rate by the double jet method. At this time, the silver potential was kept at -44 mV with respect to the saturated calomel electrode. After desalting, the average molecular weight is 100
000 succinated gelatin and pH 5 at 40 ° C.
The pAg was adjusted to 8, and a seed emulsion was prepared. This seed emulsion contains 1 mol of Ag and 8 gelatin per kg of emulsion.
0 g, tabular grains having an average equivalent circle diameter of 1.46 μm, a coefficient of variation of equivalent circle diameter of 28%, an average thickness of 0.046 μm, and an average aspect ratio of 32.

(Formation of core) 134 g of the above seed emulsion a was prepared.
Succinated KBr 1.9 g, average molecular weight 100000
Keep 1200 ml of aqueous solution containing 22 g of rat at 75 ° C
Stirred. AgNO _Three(43.9 g) aqueous solution and KBr water
Solution and an aqueous gelatin solution having a molecular weight of 20,000
-43570 Magnetic coupling induction type stirrer
25 minutes mixing just before addition in another chamber with
Added over time. At this time, the silver potential is changed to a saturated calomel electrode.
-40 mV.

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

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

(Formation of Third Shell) After the formation of the second shell, the silver potential was adjusted to -55 mV, and AgNO ₃ (7.
1 g) aqueous solution, KI (6.9 g) aqueous solution and molecular weight 200
00 gelatin aqueous solution was mixed immediately before addition in another chamber as above and added over 5 minutes.

(Formation of Fourth Shell) After the formation of the third shell, an aqueous solution of AgNO ₃ (66.4 g) and an aqueous solution of KBr were added at a constant flow rate over 30 minutes by a double jet method. On the way, iridium potassium hexachloride and yellow blood salt were added. At this time, the silver potential is set at 30 with respect to the saturated calomel electrode.
mV. Perform normal water washing, add gelatin,
PH was adjusted to 5.8 and pAg to 8.8 at 40 ° C. This emulsion was designated as emulsion b. Emulsion B had an average equivalent circle diameter of 3.3 μm,
Coefficient of variation of equivalent circle diameter 21%, average thickness 0.090μm,
The tabular grains had 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 0.3 μm.
Occupied by tabular grains of 090 μm or less. When the dye occupied area is 80 色素² , the one-layer saturation coverage is 1.4.
It was 5 × 10 ⁻³ mol / mol Ag.

The temperature of the emulsion b was increased to 56 ° C., and 1.2 × 10 ⁻³ mol / mol Ag of the following comparative dye S-1 was added. And N, N-dimethylselenourea were added for optimal chemical sensitization. Furthermore, S-1 is 2.5 × 1
The 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 of the light absorption intensity per unit area was measured by applying the obtained emulsion thinly on a slide glass and using a microspectrophotometer MSP65 manufactured by Carl Zeiss Co., Ltd. The absorption spectrum was determined by measuring the transmission spectrum and reflection spectrum of each particle by the following method. As a reference of the transmission spectrum, a portion where no particles exist was used, and as a reflection spectrum, silicon carbide of which reflectance was known was measured and used as a reference. The measurement part is a circular aperture part having a diameter of 1 μm, and the position is adjusted so that the aperture part does not overlap the contour of the particle, and is adjusted to 14000 cm ⁻¹ (714
nm) to 28000 cm ⁻¹ (357 nm), the transmission spectrum and the reflection spectrum were measured.
The absorption spectrum was determined by taking -T (transmittance) -R (reflectance) as the absorbance A. The absorption of silver halide is subtracted to obtain an absorption rate A ′, and −Log (1-A ′) is converted to a wave number (c).
The value integrated with respect to m.sup.- ¹ ) was set to 1/2 to determine the light absorption intensity per unit surface area. The integration range is 14000 cm ^-1
To 28,000 cm ^-1 . At this time, a tungsten lamp was used as the light source, and the light source voltage was 8V. In order to minimize damage to the dye due to light irradiation, a monochromator on the primary side was used, the wavelength interval was set to 2 nm, and the slit width was set to 2.5 nm. The absorption spectrum and light absorption intensity were determined for 200 particles.

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

(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, Samples 101 to 128 were prepared by changing the comparison compound S-1 to the compound of the present invention in an equimolar amount.

[0133]

[Table 1]

These samples were exposed to sensitometry (1/100 second), and subjected to the following color development processing. Processing method Step Processing time Processing temperature Replenishment amount Tank capacity Color development 2 min 45 sec 38 ° C 33 ml 20 liter Bleaching 6 min 30 sec 38 ° C 25 ml 40 liter Washing 2 min 10 sec 24 ° C 1200 ml 20 liter Fixing 4 min 20 sec 38 ° C 25 ml 30 liter water washing 1 1 minute 05 seconds 24 ° C Counterflow piping system from (2) to 10 liters (1) 10 liters water washing 2 1 minute 00 seconds 24 ° C 1200ml 10 liters stable 1 minute 05 seconds 38 ° C 25ml 10 liters drying 4 minutes 20 Seconds 55 ° C Replenishment rate per 35 mm width 1 m length Next, the composition of the processing solution is described. (Color developing solution) Mother liquor (g) Replenisher (g) Diethylenetriaminepentaacetic acid 1.0 1.1 1-hydroxyethylidene-1,1-diphosphonic acid 3.0 3.2 Sodium sulfite 4.0 4.4 Potassium carbonate 30.0 37.0 Potassium bromide 1.4 0.7 Potassium iodide 1.5 mg-hydroxylamine sulfate 2.4 2.8 4- [N-ethyl-N-β-hydroxyethylamino] -2- Methylaniline sulfate 4.5 5.5 Add water 1.0 liter 1.0 liter pH 10.05 10.05 (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 (Fixing solution) 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 Ammonia thiosulfate (70%) 170.0 ml 200.0 ml Add water 1.0 liter 1.0 Liter pH 6.7 6.65 (stabilizing solution) 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 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, and the sensitivity and fog were evaluated. Sensitivity is 0 from fog density.
2 Defined as 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 being 100. Table 2 shows the results of the emulsion used in each sample, the comparative example, 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 a microspectroscopy method. Both the light absorption intensity and the sensitivity were based on the value of Comparative Example 101. The light absorption intensity of Comparative Example 101 was 58.

[0136]

[Table 2]

[0137]

Embedded image

From Table 2, it can be seen that the compound of the present invention is comparative compound S
Compared to -1, the light absorption rate is improved due to the multilayer structure,
It is clear that the sensitivity is increased as a result. Dye2
Ni-A ₁-L₁-R₁Than the linked dye S-2 having no
Excellent light absorption intensity and sensitivity due to an ideal multilayer structure
It is clear that. Furthermore, the compound D-2 of the present invention
In the sample 110 using 0, the number of adsorbed layers was 1.93, which was almost 2
It has a layered structure. The interval of 50% of Amax is 55 nm.
Relatively narrow and preferred, both the first and second layer dyes
Form a union. From the above results, the color of the second layer
When the element is photoexcited, the energy transfer to the first-layer dye
Or through electron transfer to increase sensitivity.
It is easy.

Example 3 A comparison similar to that of Example 2 was made in Example 5 of JP-A-8-29904.
Of the color negative photosensitive material of Comparative Example S-
Assuming that the sensitivity of the blue-sensitive layer of the light-sensitive material using No. 1 was 100 (reference), the sensitivity of the light-sensitive material using D-20 of the present invention was 166, which was high. A similar comparison was also made with the instant light-sensitive material system of Example 1 of Japanese Patent Application No. 11-89801, and the sensitivity of the blue-sensitive layer of the light-sensitive material using Comparative Example S-1 was 100%.
As a reference, the sensitivity of the light-sensitive material using D-20 of the present invention was 164, which was high. Further, JP-A-7-92601,
JP-A-11-160828, Example 1 of color reversal photosensitive material, JP-A-6-347944, Example 1 of color paper system, JP-A-6-347944.
In the system of the X-ray sensitive material of Example 1 of JP-A-8-122954, the system of the thermally developed photosensitive material of Example 1 of Japanese Patent Application No. 2000-89436, and the system of the printed photosensitive material of Example 1 of JP-A-8-292512. The light-sensitive material using the compound of the present invention was found to be highly sensitive to the comparative compound. Furthermore, all of these systems have a large light absorption intensity and a large number of chromophore-adsorbed layers, and were found to be similarly useful.

[0140]

By using the methine dye-linked compound of the present invention, a multilayer structure is formed, the light absorption is improved, and a silver halide photographic material having high sensitivity can be obtained.

Claims (8)

[Claims] 1. A silver halide photographic material having at least one photosensitive silver halide emulsion layer on a support, wherein the emulsion layer contains a compound represented by the following general formula (1). Characteristic silver halide photographic material. General formula (1) Wherein Dye1 represents the first chromophore and Dye2 represents the second chromophore. R ₁ represents a dissociable group having a pKa of 5 or less, and L and L ₂ each independently represent a linking group. m1 is an integer of 1 to 4, m2
Represents an integer of 1 to 5, and m3 represents an integer of 1 to 5. 2. A compound represented by the general formula (1):
The silver halide photographic material as claimed in claim 1, characterized by being represented by - linking group L is -A ₁ -L _1. Where L ₁
Represents an alkylene group, alkenylene group, or arylene group, and A ₁ represents -O-, -S-,-
NR ₂ —, —COO—, —CONR ₃ —, —SO ₂ NR ₄ —
And R _{2 to} R ₄ represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group. However, L ₁ is on the R ₁ side. 3. The compound represented by the general formula (1), wherein R ₁ is —SO ₃ M, —OSO ₃ M, —PO ₃ M ₂ , —O
_{3. The} silver halide photographic material according to claim 1, wherein PO ₃ M ₂ represents —COOM, and M represents a proton or a cation. 4. The compound according to claim 1, wherein in the compound represented by the general formula (1), Dye1 and Dye2 are independently any one of a cyanine chromophore, a merocyanine chromophore and an oxonol chromophore. A silver halide photographic light-sensitive material described in any of the above. 5. The compound represented by the general formula (1)
And L_TwoIs -G₁-(A _Two-G_Two)
The silver halide according to any one of claims 1 to 4,
Photosensitive material. Where G₁, G_TwoAre each independently
A kylene group, an alkenylene group or an arylene group,
A_TwoIs -O-, -S-, -SO
_Two-, -NR_Two-, -COO-, -CONR_Three-, -SO_Two
NR_FourAnd t1 represents an integer of 1 to 10. 6. A compound represented by the general formula (1):
The method according to claim 1, wherein the general formula (2) is used.
The silver halide photographic light-sensitive material according to any one of the above. Embedded imageWhere L₁, A₁Is synonymous with general formula (1),₁,
G_Two, A_Two, T1 have the same meaning as in claim 4. R₁Is -SO
_ThreeM, -OSO_ThreeM, -PO_ThreeM_Two, -OPO_ThreeM_Two, -CO
OM represents any one of OM, and M represents a proton or a cation.
And n7 and n8 each independently represent an integer of 0 to 2,
Is never zero. X₁~ X_FourAre each independently -O
-, -S-, -NR_Five-, -CR₆R₇-Represents R_Five~ R
₇Are each independently a hydrogen atom, an alkyl group, an alkenyl
Represents an aryl group, a heterocyclic group. R ₁₁~ R₁₄Is it
Each independently represents a hydrogen atom, an alkyl group, an alkenyl group,
And a heterocyclic group. M₁~ M₆Are independently
Represents a methine group, n1 and n2 are each independently an integer of 0 to 3
Represents V₁~ V_FourRepresents a substituent, and n3 to n6 represent an integer of 0 to 4.
Represents a number. When n3 to n6 is 2 or more, V_Three~ V₆Are the same but different
And may be connected to each other to form a ring. CI
Represents a charge neutralizing ion, and y represents a charge neutralizing ion.
Represents the number required for. Note that G₁Is R₁₁Or V₁At Dye
Connect with 1, G_TwoIs R₁₃Or V_ThreeConnect with Dye2 at. 7. The compound represented by the general formula (1) or (2), wherein the adsorption force on silver halide grains is Dye1> Dy.
The silver halide photographic material according to any one of claims 1 to 6, wherein the material is e2. 8. A dye represented by the general formula (2) according to claim 6.