JP2003057777A - Silver halide photographic sensitive material - 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 at least one compound having three, four or five dye chromophores.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a linking dye compound in which 3 to 5 chromophores are linked, and a silver halide photographic light-sensitive material containing the same.

[0002]

2. Description of the Related Art Methine dye compounds have hitherto been used as spectral sensitizing dyes for silver halide photographic light-sensitive materials.
The following are known techniques for improving the light absorption rate of silver halide grains. In order to improve the light absorptance per grain, it is necessary to increase the adsorption density of the sensitizing dye to the silver halide grains, but the ordinary spectral sensitizing dye is a nearly monolayer in a monolayer. Adsorbs, no more. Several proposals have been made to solve this problem. PBGilman, Jr. et al.
In Photographic Science and Engineering, Vol. 20, No. 3, p. 97 (1976), a cation dye was adsorbed on the first layer and an anion dye was adsorbed on the second layer by using electrostatic force. GB Bird et al., US Pat. No. 3,62
In No. 2,316, multiple dyes were adsorbed in multiple layers on silver halide grains and sensitized by the contribution of Forster-type excitation energy transfer. Sugimoto et al. JP-A 63-138,341, 64-8
No. 4,244, spectral sensitization was performed by energy transfer from the luminescent dye. However, all of these were attempts to adsorb a dye in an amount equal to or more than the saturated adsorption amount on silver halide grains, but none of them had the effect of increasing the sensitivity and had a problem such as an increase in intrinsic desensitization. It was On the other hand, for a two-component linked dye in which two or more unconjugated dye chromophores are linked by a covalent bond, see US Pat. No. 2,393,351,
2,425,772, 2,518,732, 2,521,944, 2,5
92,196 or European Patent 565,083. However, these were not intended to improve the light absorption rate. In order to positively improve the light absorptivity, GB Bird et al. Increase energy absorption by adsorbing a linked sensitizing dye molecule having a plurality of cyanine chromophores in U.S. Pat.Nos. 3,622,317 and 3,976,493 to increase energy absorption. However, no significant increase in sensitivity has been obtained. Ukai et al., In JP-A-64-91134, bind at least one substantially non-adsorptive dye containing at least two sulfo or carboxy groups to a spectral sensitizing dye capable of being adsorbed on silver halide. Is proposed. Also, in Bishwa Karma et al. In JP-A-6-27,578, a two-component linking dye in which an adsorptive cyanine dye and a non-adsorptive oxonol are linked to a silver halide, and Parton et al. Spectral sensitization is performed using two-component linked dyes, which are non-adsorptive merocyanine dyes linked using a specific linking group, but it cannot be said that the sensitivity enhancement due to energy transfer has occurred sufficiently. . As described above, sufficient sensitivity enhancement cannot be achieved by any of the methods of patents and documents, and further technical development is required.

[0003]

Therefore, an object of the present invention is to provide a highly sensitive silver halide photographic light-sensitive material containing a methine-linked dye.

[0004]

The above objects of the present invention have been achieved by the following means. (1) A silver halide photographic light-sensitive material having at least one photosensitive silver halide emulsion layer on a support, wherein the emulsion layer has 3, 4, or 5 dye chromophores A silver halide photographic light-sensitive material comprising at least one compound. (2) In a silver halide photographic light-sensitive material having at least one photosensitive silver halide emulsion layer on a support, at least one compound represented by the following general formula (1) is contained in the emulsion layer. A silver halide photographic light-sensitive material as described in (1) above, which contains. General formula (1)

[0005]

[Chemical 3]

In the formula, L ₁ represents a linking group, and D 1 and D 2 represent chromophores. q1, r1 and r2 each represent an integer of 1 to 4, and (q1 × r1 + r2) represents an integer of 3 to 5. qa is 1 to 4
Represents the integer. CI represents an ion that neutralizes charge, and y represents the number necessary for neutralizing charge. (3) In a silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support, the emulsion layer contains a compound represented by the following general formula (2). (2) The silver halide photographic light-sensitive material as described in (2) above. General formula (2)

[0007]

[Chemical 4]

In the formula, La and Lb represent a linking group. Dye1, Dye
2 and Dye3 may be the same or different and each represents a chromophore. CI represents an ion that neutralizes charge, and y represents the number necessary for neutralizing charge. (4) In the compound represented by the general formula (2), Dye1,
The silver halide photographic light-sensitive material as described in (3), wherein Dye2 and Dye3 are each independently a cyanine chromophore, a merocyanine chromophore, or an oxonol chromophore. (5) In the compound represented by the general formula (2), Dye
At least one of 1, Dye2, and Dye3 is a cyanine chromophore, and the silver halide photographic light-sensitive material according to (3) or (4). (6) In the compound represented by the general formula (1), only one of the three to five D1 and D2 is a cyanine chromophore, and the other two to four dye chromophores. The silver halide photographic light-sensitive material described in (2), wherein the group is a chromophore other than a cyanine dye. (7) In the compound represented by the general formula (1), only one of the three to five D1 and D2 is a cyanine chromophore, and the other two to four dye chromophores. Is a merocyanine chromophore or an oxonol chromophore, and the silver halide photographic light-sensitive material as described in (2) or (6) above. (8) In the compound represented by the general formula (2), Dye1,
Or one of Dye3 is a cyanine chromophore, and the other one and Dye2 are a merocyanine chromophore or an oxonol chromophore (4), or (5) according to the silver halide Photographic material. (9) In the compound represented by the general formula (2), Dye1,
When the connected portion of Dye2 and Dye3 is replaced by a hydrogen atom, the strength of the adsorptive power to silver halide grains is Dye1>
(Dye2 and Dye3), or Dye3> (Dye2 and Dye1) (3), (4), (5), or
The silver halide photographic light-sensitive material described in (8). (10) The compound represented by the general formula (1) described in (6) and (7), and the general compound described in (3), (4), (5), (8) and (9) A compound represented by the formula (2). (11) In the silver halide photographic light-sensitive material, the compound represented by the general formula (2) is adsorbed to the silver halide grains at Dye1 to form a J-association, and further not adsorbed to the silver halide grains at Dye2. , And / or Dy3 when Dye3 is photoexcited
The silver halide photographic light-sensitive material as described in any one of (3), (4), (5), (8), and (9), which is characterized by electron transfer or energy transfer to e1. (12) In a silver halide photographic light-sensitive material, a cyanine chromophore having one compound represented by the general formula (1) in (8) is adsorbed to silver halide grains to form a J-association. In addition, the silver halide photographic light-sensitive material according to (8), characterized in that when other chromophores other than cyanine that are not adsorbed on the silver halide grains are photoexcited, they transfer electrons or energy to Dye1. (13) In a silver halide photographic emulsion containing a compound represented by the general formula (1) or (2), tabular grains having an aspect ratio of 2 or more account for 50% (area) of all silver halide grains in the emulsion. ) The emulsion is characterized by the above (1) ~
The silver halide photographic light-sensitive material according to any one of (9), (11), and (12). (14) A silver halide photographic emulsion containing a compound represented by the general formula (1) or (2) is selenium-sensitized (1) to (9), (11) The silver halide photographic light-sensitive material as described in any of (12) and (13). (15) Spectral sensitization containing a compound represented by the general formula (1) or (2) in a silver halide photographic light-sensitive material containing a compound represented by the general formula (1) or (2) (1) to (9), (11), (12), characterized in that the dye comprises at least one silver halide photographic emulsion layer in which more than two layers are adsorbed on the silver halide grains. The silver halide photographic light-sensitive material as described in any of (13) and (14).

[0009]

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

When the compound of the present invention has an alkyl group, an alkylene group, an alkenyl group or an alkenylene group, they may be linear or branched and may be substituted, unless otherwise specified. It may be replaced. Further, when the compound of the present invention has a cycloalkyl group, an aryl group, a heterocyclic group, a cycloalkenylene group, an arylene group, a heterylene group, unless otherwise specified, they may be monocyclic or condensed. , May be substituted or may not be substituted.

In the present invention, when a specific moiety is referred to as a "group", the moiety is substituted with one or more (up to the maximum possible number) of substituents even if the moiety is not itself substituted. It means that it may be done. For example, "alkyl group" means a substituted or unsubstituted alkyl group. Further, the substituent that can be used in the compound of the present invention may be any substituent. For example, the following substituent group W may be mentioned. The substituent represented by W may be any, and is not particularly limited, and examples thereof include a halogen atom, an alkyl group (including a cycloalkyl group, a bicycloalkyl group and a tricycloalkyl group), an alkenyl group (a cycloalkenyl group). , A bicycloalkenyl group), an alkynyl group, an aryl group, a heterocyclic group (may be referred to as a heterocyclic group), a cyano group, a hydroxyl group, a nitro group, a carboxyl group, an alkoxy group, an aryloxy group, a silyloxy group, Heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group (including anilino group), ammonio group, acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxy Carbonyl amino , A sulfamoylamino group,
Alkyl and aryl sulfonylamino groups, mercapto groups, alkylthio groups, arylthio groups, heterocyclic thio groups, sulfamoyl groups, sulfo groups, alkyl and arylsulfinyl groups, alkyl and arylsulfonyl groups, acyl groups, aryloxycarbonyl groups, alkoxycarbonyl groups , Carbamoyl group, aryl and heterocyclic azo group, imide group, phosphino group, phosphinyl group,
Examples thereof include a phosphinyloxy group, a phosphinylamino group, a phospho group, a silyl group, a hydrazino group, a ureido group, and other known substituents. For more details,
W is a halogen atom (for example, a fluorine atom, a chlorine atom,
Bromine atom, iodine atom), alkyl group [[linear, branched,
It represents a cyclic substituted or unsubstituted alkyl group. They are alkyl groups (preferably alkyl groups having 1 to 30 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, t-butyl, n-octyl, eicosyl, 2-chloroethyl, 2-cyanoethyl, 2-ethylhexyl). , A cycloalkyl group (preferably having 3 to 3 carbon atoms)
0 substituted or unsubstituted cycloalkyl group, for example, cyclohexyl, cyclopentyl, 4-n-dodecylcyclohexyl, bicycloalkyl group (preferably a substituted or unsubstituted bicycloalkyl group having 5 to 30 carbon atoms, that is, carbon A monovalent group obtained by removing one hydrogen atom from the bicycloalkane of the numbers 5 to 30. For example, bicyclo [1,2,2] heptan-2-yl, bicyclo [2,2,2] octane-3-yl. ), And further includes a tricyclo structure having many ring structures. The alkyl group in the substituents described below (for example, an alkyl group of an alkylthio group) represents an alkyl group having such a concept, and further includes an alkenyl group and an alkynyl group. ], An alkenyl group [represents a linear, branched, or cyclic substituted or unsubstituted alkenyl group. They are an alkenyl group (preferably a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms such as vinyl, allyl, prenyl, geranyl, oleyl), a cycloalkenyl group (preferably a substituted or unsubstituted C 3 to 30 carbon atom, or An unsubstituted cycloalkenyl group, that is, a monovalent group obtained by removing one hydrogen atom of a cycloalkene having 3 to 30 carbon atoms, for example, 2-cyclopenten-1-yl, 2-cyclohexen-1-yl), Bicycloalkenyl group (substituted or unsubstituted bicycloalkenyl group, preferably having 5 carbon atoms
To 30 substituted or unsubstituted bicycloalkenyl groups, that is, monovalent groups obtained by removing one hydrogen atom from a bicycloalkene having one double bond. For example, bicyclo [2,2,1] hept-2-en-1-yl and bicyclo [2,2,2] oct-2-en-4-yl) are included. ], An alkynyl group (preferably a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, for example, ethynyl, propargyl, trimethylsilylethynyl group)], an aryl group (preferably a substituted or unsubstituted C 6 to 30 carbon atom) Aryl groups such as phenyl, p
-Tolyl, naphthyl, m-chlorophenyl, o-hexadecanoylaminophenyl), a heterocyclic group (preferably 5)
Or a monovalent group obtained by removing one hydrogen atom from a 6-membered substituted or unsubstituted aromatic or non-aromatic heterocyclic compound, and more preferably a 5- or 6-membered group having 3 to 30 carbon atoms. It is an aromatic heterocyclic group. For example, 2
-Furyl, 2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl, 1-methyl-2-pyridinio, 1
It may be a cationic heterocyclic group such as -methyl-2-quinolinio. ), A cyano group, a hydroxyl group, a nitro group, a carboxyl group, an alkoxy group (preferably a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, for example, methoxy, ethoxy, isopropoxy, t-butoxy, n-octyl. Oxy, 2-methoxyethoxy),
Aryloxy group (preferably a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, for example, phenoxy, 2-methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, 2-tetradecanoylaminophenoxy. ), A silyloxy group (preferably a silyloxy group having 3 to 20 carbon atoms, for example, trimethylsilyloxy, t-butyldimethylsilyloxy), a heterocyclic oxy group (preferably a substituted or unsubstituted hetero group having 2 to 30 carbon atoms). Ring oxy group, 1-phenyltetrazole-5-oxy, 2-tetrahydropyranyloxy), acyloxy group (preferably formyloxy group,
A substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms, 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,
A substituted or unsubstituted alkoxycarbonyloxy group having 2 to 30 carbon atoms, for example, methoxycarbonyloxy, ethoxycarbonyloxy, t-butoxycarbonyloxy, n-octylcarbonyloxy), an aryloxycarbonyloxy group (preferably having 7 carbon atoms) 30 substituted or unsubstituted aryloxycarbonyloxy groups, for example, phenoxycarbonyloxy, p-methoxyphenoxycarbonyloxy, pn-hexadecyloxyphenoxycarbonyloxy), amino group (preferably amino group, carbon number 1) To 30 substituted or unsubstituted alkylamino group, a substituted or unsubstituted anilino group having 6 to 30 carbon atoms, for example, amino, methylamino, dimethylamino, anilino, N-methyl-anilino,
Diphenylamino), an ammonio group (preferably an ammonio group, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, an aryl group, an ammonio group substituted with a heterocycle, for example, trimethylammonio, triethylammonio,
Diphenylmethylammonio), acylamino group (preferably formylamino group, substituted or unsubstituted alkylcarbonylamino group having 1 to 30 carbon atoms, and 6 carbon atoms)
To 30 substituted or unsubstituted arylcarbonylamino groups such as formylamino, acetylamino, pivaloylamino, lauroylamino, benzoylamino, 3,4,5-tri-n-octyloxyphenylcarbonylamino), aminocarbonylamino groups (Preferably a substituted or unsubstituted aminocarbonylamino having 1 to 30 carbon atoms, for example, carbamoylamino, N,
N-dimethylaminocarbonylamino, N, N-diethylaminocarbonylamino, morpholinocarbonylamino), an alkoxycarbonylamino group (preferably a substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms, for example, methoxycarbonylamino, ethoxycarbonyl). Amino, t-butoxycarbonylamino, n-octadecyloxycarbonylamino, N-methyl-methoxycarbonylamino), an aryloxycarbonylamino group (preferably a substituted or unsubstituted aryloxycarbonylamino group having 7 to 30 carbon atoms, For example, phenoxycarbonylamino, p-chlorophenoxycarbonylamino, m-n-octyloxyphenoxycarbonylamino), sulfamoylamino group (preferably having 0 carbon atoms or 30 substituted or unsubstituted sulfamoylamino groups, for example, sulfamoylamino, N, N-dimethylaminosulfonylamino, N-
n-octylaminosulfonylamino), alkyl and arylsulfonylamino groups (preferably substituted or unsubstituted alkylsulfonylamino having 1 to 30 carbon atoms, substituted or unsubstituted arylsulfonylamino having 6 to 30 carbon atoms, for example, methyl Sulfonylamino,
Butylsulfonylamino, phenylsulfonylamino,
2,3,5-trichlorophenylsulfonylamino, p
-Methylphenylsulfonylamino), a mercapto group,
An alkylthio group (preferably a substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms, such as methylthio,
Ethylthio, n-hexadecylthio), arylthio group (preferably substituted or unsubstituted arylthio having 6 to 30 carbon atoms, for example, phenylthio, p-chlorophenylthio, m-methoxyphenylthio), heterocyclic thio group (preferably having carbon number) 2 to 30 substituted or unsubstituted heterocyclic thio groups, for example 2-benzothiazolylthio,
1-phenyltetrazol-5-ylthio), a sulfamoyl group (preferably a substituted or unsubstituted sulfamoyl group having 0 to 30 carbon atoms, for example, N-ethylsulfamoyl, N- (3-dodecyloxypropyl) sulfamoyl, N , N-dimethylsulfamoyl, N-acetylsulfamoyl, N-benzoylsulfamoyl,
N- (N′-phenylcarbamoyl) sulfamoyl), sulfo group, alkyl and arylsulfinyl group (preferably a substituted or unsubstituted alkylsulfinyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfinyl group having 6 to 30 carbon atoms) Groups such as methylsulfinyl, ethylsulfinyl, phenylsulfinyl, p
-Methylphenylsulfinyl), an alkyl and arylsulfonyl group (preferably a substituted or unsubstituted alkylsulfonyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfonyl group having 6 to 30 carbon atoms, for example, methylsulfonyl, ethylsulfonyl) , Phenylsulfonyl, p-methylphenylsulfonyl), acyl group (preferably formyl group, substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms, carbon Number 4 to 3
A heterocyclic carbonyl group linked to a carbonyl group at 0 substituted or unsubstituted carbon atoms, for example acetyl,
Pivaloyl, 2-chloroacetyl, stearoyl, benzoyl, pn-octyloxyphenylcarbonyl,
2-pyridylcarbonyl, 2-furylcarbonyl), an aryloxycarbonyl group (preferably a substituted or unsubstituted aryloxycarbonyl group having 7 to 30 carbon atoms, for example, phenoxycarbonyl, o-chlorophenoxycarbonyl, m-nitrophenoxy). Carbonyl, p
-T-butylphenoxycarbonyl), an alkoxycarbonyl group (preferably a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms, for example, methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl, n-octadecyloxycarbonyl), carbamoyl. A group (preferably a substituted or unsubstituted carbamoyl having 1 to 30 carbon atoms, for example, carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N,
N-di-n-octylcarbamoyl, N- (methylsulfonyl) carbamoyl), aryl and heterocyclic azo groups (preferably a substituted or unsubstituted arylazo group having 6 to 30 carbon atoms, a substituted or unsubstituted carbon atom having 3 to 30 carbon atoms) Substituted heterocyclic azo group such as phenylazo, p-chlorophenylazo, 5-ethylthio-1,3,4-thiadiazol-2-ylazo), imide group (preferably N)
-Succinimide, N-phthalimide), a phosphino group (preferably a substituted or unsubstituted phosphino group having 2 to 30 carbon atoms, for example, dimethylphosphino, diphenylphosphino, methylphenoxyphosphino), a phosphinyl group (preferably, A substituted or unsubstituted phosphinyl group having 2 to 30 carbon atoms, for example, phosphinyl,
Dioctyloxyphosphinyl, diethoxyphosphinyl), phosphinyloxy group (preferably a substituted or unsubstituted phosphinyloxy group having 2 to 30 carbon atoms,
For example, diphenoxyphosphinyloxy, dioctyloxyphosphinyloxy, a phosphinylamino group (preferably a substituted or unsubstituted phosphinylamino group having 2 to 30 carbon atoms, for example, dimethoxyphosphinylamino). , Dimethylaminophosphinylamino), a phospho group, a silyl group (preferably a substituted or unsubstituted silyl group having 3 to 30 carbon atoms, for example, trimethylsilyl, t-butyldimethylsilyl, phenyldimethylsilyl), a hydrazino group ( Preferably, a substituted or unsubstituted hydrazino group having 0 to 30 carbon atoms, for example, trimethylhydrazino, a ureido group (preferably a substituted or unsubstituted ureido group having 0 to 30 carbon atoms, for example, N, N).
-Dimethylureido). In addition, a ring (aromatic or non-aromatic hydrocarbon ring or heterocycle, which can be further combined to form a polycyclic condensed ring).
For example, benzene ring, naphthalene ring, anthracene ring, quinoline ring, phenanthrene ring, fluorene ring, triphenylene ring, naphthacene ring, biphenyl ring, pyrrole ring,
Furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, indolizine ring, indole ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinolidine ring, quinoline ring , Phthalazine ring,
Naphthyridine ring, quinoxaline ring, quinoxazoline ring,
Examples thereof include a quinoline ring, a carbazole ring, a phenanthridine ring, an acridine ring, a phenanthroline ring, a thianthrene ring, a chromene ring, a xanthene ring, a phenoxathiin ring, a phenothiazine ring and a phenazine ring. It is also possible to adopt a structure in which) is condensed.

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

D1, D2, Dye1, Dye2, and Dye3 represent chromophores (synonymous with dye chromophores) which may be the same or different. The "dye chromophore" according to claim 1.
And, the chromophore represented by D1, D2, Dye1, Dye2, and Dye3 may be any, for example, cyanine dye, styryl dye, hemicyanine dye, merocyanine dye, trinuclear merocyanine dye, tetranuclear merocyanine dye, Rhodocyanine dye, complex cyanine dye, complex merocyanine dye, allopolar dye, oxonol dye, hemioxonol dye, squarylium 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 color Examples include elemental dyes, acridinone dyes, diphenylamine dyes, quinacridone dyes, quinophthalone dyes, phenoxazine dyes, phthaloperylene dyes, porphyrin dyes, chlorophyll dyes, phthalocyanine dyes, and metal complex dyes. 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, squarylium dye, Examples include polymethine chromophores such as croconium dye, azamethine dye, and oxonol dye. For more information on these dyes, see FM Harmer.
(FM Harmer) "Heterocyclic Compounds, Cyanine and Relative Compounds
(Heterocyclic Compounds-Cyanine Dyes and Related C
ompounds), John Willie and Sons (John
Wiley & Sons) -New York, London, 1964
Annual publication, DMSturmer, "Heterocyclic Compounds Special Topics in Heterocyclic Chemistry (Heteroc
yclic Compounds-Special topics in heterocyclic che
mistry) ", Chapter 18, Section 14, 482-515
Page, John & Wiley & Sons, New York, London, 1977 etc. Preferred general formulas for dyes include general formulas described in U.S. Pat. No. 5,994,051, pages 32 to 36, and U.S. Pat. No. 5,747,236.
General formulas described on pages 0 to 34 are mentioned. Further, preferred general formulas of cyanine dyes, merocyanine dyes, and rhodacyanine dyes are described in US Pat. No. 5,340,694, Nos. 21 and 2
The ones shown in (XI), (XII), and (XIII) of column 2 (however, the number of n12, n15, n17, and n18 are not limited, and an integer of 0 or more (preferably 4 or less)) To be

In the compound having 3 to 5 dye chromophores according to claim 1, one of the 3 to 5 dye chromophores is a cyanine dye, and all other dye chromophores are other than cyanine dyes. Is preferably a chromophore. As an example of the chromophore other than the cyanine dye, any one may be used as long as it excludes the cyanine dye from the dye structures cited as examples of the above-mentioned chromophore, but is preferably a merocyanine chromophore or an oxonol chromophore. is there. More preferably, it is a merocyanine chromophore. 3 to 5 according to claim 1
The number of dye chromophores in a compound having one dye chromophore is
The number is preferably 3 or 4, and more preferably 3.

3 to 5 D1 and D2 in the general formula (1) are
It is preferably any one of a cyanine chromophore, a merocyanine chromophore and an oxonol chromophore, and 3 to 5 D1,
More preferably, one of C2 and D2 is a cyanine dye, and the other is a chromophore other than the cyanine dye. As an example of the chromophore other than the cyanine dye, any one may be used as long as it excludes the cyanine dye from the dye structures cited as examples of the above-mentioned chromophore, but is preferably a merocyanine chromophore or an oxonol chromophore. is there. More preferably, it is a merocyanine chromophore. Further, at least one or more -SO is contained in the chromophore other than the cyanine dye.
_{3 M, -OSO 3 M, -OPO} 3 M 2, -PO 3 M 2, -CO
OM is preferably contained, and at least one or more-
More preferably, SO ₃ M is included.

Dye1, Dye2, and Dye3 are cyanine chromophores,
It is preferably either a merocyanine chromophore or an oxonol chromophore, more preferably a cyanine chromophore or a merocyanine chromophore, and Dye1, Dye
More preferably, at least one of 2 and Dye3 is a cyanine chromophore. Also, of Dye1 or Dye3,
One of them is a cyanine chromophore, the other one and Dye
More preferred is when 2 is a merocyanine chromophore or an oxonol chromophore.

In another preferred embodiment, Dye1 and Dy
Regardless of what chromophore e2 and Dye3 represent,
The strength of the adsorptive power to silver halide grains when the connected portion of Dye1, Dye2, and Dye3 is replaced by a hydrogen atom is
e1> (Dye2 and Dye3) or Dye3> (Dye2 and Dye
1) is preferred. In other words, it can be said that it is preferable that the terminal chromophore among the three linked chromophores has the strongest adsorption force to the silver halide grain.

When the connected portion of each chromophore is replaced with a hydrogen atom, the strength of the adsorptive power to silver halide grains is determined by synthesizing a chromophore molecule in which the actually connected portion is replaced with a hydrogen atom, and Adsorption isotherm on silver halide (T. James, The Photographic.
Process, 4th edition, published by Macmillan, 1977,
(TH James, The Theory of
the Photographic Process,
4th ed, Macmillan, 1977) Chapter 9) for comparison.

Each of q1, r1 and r2 represents an integer of 1 to 4, and q1 × r1 + r2 satisfies an integer of 3 to 5. q1 × r1 + r2 is an integer of 3 to 5, preferably 3 or 4, and more preferably 3. When q1 × r1 or r2 is 2 or more,
D1 or D2 is repeated, but a plurality of D1 or D2 need not be the same.

Qa represents an integer of 1 to 4. Note that qa is 2
The above means that each of D1 and D2 or D2 and D2 is linked by a plurality of linking groups. That is, D1 and D
2, or D2 and D2 may be connected at each one location or at a plurality of locations (2 to 4 locations, preferably 2 locations). When qa is 2 or more, a plurality of L ₁ may be the same or different. The case where they are the same is preferable.

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

[0022]

[Chemical 5]

In the formula, Za ₁ and Za ₂ each represent an atomic group forming a 5-membered or 6-membered nitrogen-containing heterocycle, which are further represented by a benzene ring, a benzofuran ring, a pyridine ring, a pyrrole ring, 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, preferably a hydrogen atom, an alkyl group or a sulfoalkyl group, more preferably an alkyl group or a sulfoalkyl group. . Ma _{1 to} Ma ₇ each represent a methine group. na ¹ and na ²
Is 0 or 1, preferably 0. ka ¹ represents an integer of 0 to 3. It is preferably an integer from 0 to 2, and more preferably 0 or 1. When ka ¹ is 2 or more, Ma ₃ and Ma ₄ may be the same or different. CI represents an ion that neutralizes charge, and y represents the number necessary for neutralizing charge. The linking group La or Lb may be linked at any position, but is preferably. Connect with Ra ₁ or Ra ₂ .

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

[0025]

[Chemical 6]

In the formula, Za ₃ represents a group of atoms forming a 5- or 6-membered nitrogen-containing heterocycle, which are further condensed with a benzene ring, a benzofuran ring, a pyridine ring, a pyrrole ring, an indole ring, a thiophene ring, etc. It may be ringed. Za
₄ represents an atomic group forming an acidic nucleus. Ra ₃ represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or a heterocyclic group. Ma _{8 to} Ma ₁₁ each represent a methine group. na ³ is 0 or 1. ka ² represents an integer of 0 to 3, preferably an integer of 0 to 2, and more preferably 1 or 2. When ka ₂ is 2 or more, Ma ₁₀ and Ma ₁₁ may be the same or different. CI represents an ion that neutralizes the charge, y
Represents the number required for charge neutralization. When Dye2 represents other than oxabarbiturdimethine merocyanine, it may be linked to the linking group La or Lb at any position.
However, for the reason of controlling the orientation of the second layer, when Dye2 represents oxabarbitur dimethine merocyanine, it is preferable that the substituent on the barbituric acid is linked to La or Lb.

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

[0028]

[Chemical 7]

In the formula, Za ₅ and Za ₆ each represent an atomic group forming an acidic nucleus. Ma _{12 to} Ma ₁₄ each represent a methine group. k
a ³ represents an integer of 0 to 3, preferably an integer of 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 that neutralizes the charge, y
Represents the number required for charge neutralization. The linking group La or Lb
May be linked at any position, but it is preferable that the substituent on the acidic nucleus is linked to La or Lb.

Za ₁ , Za ₂ and Za _{3 each} have _{3 to 2} carbon atoms.
5 oxazole nuclei (eg 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-methoxyethylbenzoxazolyl, 2-3-sulfobutylbenzoxazolyl, 2-
3-methyl-β-naphthoxazolyl, 2-3-methyl-α-naphthoxazolyl, 2-3-sulfopropyl-
β-naphthoxazolyl, 2-3-sulfopropyl-γ
-Naphthoxazolyl, 2-3- (3-naphthoxyethyl) benzoxazolyl, 2-3,5-dimethylbenzoxazolyl, 2-6-chloro-3-methylbenzoxazolyl, 2-5- Bromo-3-methylbenzoxazolyl, 2-3-ethyl-5-methoxybenzoxazolyl, 2-5-phenyl-3-sulfopropylbenzoxazolyl, 2-5- (4-bromophenyl)- 3-sulfobutylbenzoxazolyl, 2-3-dimethyl-5,
6-dimethylthiobenzoxazolyl), having 3 to 2 carbon atoms
5 thiazole nuclei (eg 2-3-methylthiazolyl, 2-3-ethylthiazolyl, 2-3-sulfopropylthiazolyl, 2-3-sulfobutylthiazolyl, 2-
3,4-dimethylthiazolyl, 2-3,4,4-trimethylthiazolyl, 2-3-carboxyethylthiazolyl, 2-3-methylbenzothiazolyl, 2-3-ethylbenzothiazolyl 2-3-butylbenzothiazolyl,
2-3-sulfopropylbenzothiazolyl, 2-3-sulfobutylbenzothiazolyl, 2-3-methyl-β-naphthothiazolyl, 2-3-sulfopropyl-γ-naphthothiazolyl, 2-3- (1- Naphthoxyethyl) benzothiazolyl, 2-3,5-dimethylbenzothiazolyl,
2-6-chloro-3-methylbenzothiazolyl, 2-6
-Iodo-3-ethylbenzothiazolyl, 2-5-bromo-3-methylbenzothiazolyl, 2-3-ethyl-5
-Methoxybenzothiazolyl, 2-5-phenyl-3-
Sulfopropylbenzothiazolyl, 2-5- (4-bromophenyl) -3-sulfobutylbenzothiazolyl, 2
-3-dimethyl-5,6-dimethylthiobenzothiazolyl and the like), 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 and the like), an indolenine nucleus having 10 to 30 carbon atoms (for example, 3,3-dimethylindolenine), a quinoline nucleus having 9 to 25 carbon atoms (for example, 2-1 -methylquinolyl, 2-1- Ethylquinolyl, 2-1 -methyl 6-chloroquinolyl, 2-1,3-
Diethylquinolyl, 2-1 -methyl-6-methylthioquinolyl, 2-1 -sulfopropyl quinolyl, 4-1 -methyl quinolyl, 4-1 -sulfoethyl quinolyl, 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), 5 carbon atoms
To 25 pyridine nuclei (for example, 2-pyridyl and the like), and the like, and further thiazoline nuclei, oxazoline nuclei, selenazoline nuclei, tellrazoline nuclei, tellurazole nuclei, benzotelrazole nuclei, imidazoline nuclei,
Examples thereof include imidazo [4,5-quinoxaline] nucleus, oxadiazole nucleus, thiadiazole nucleus, tetrazole nucleus, and pyrimidine nucleus. These may be replaced,
Examples of the substituent include the above-mentioned Substituent Group W, and preferably, for example, an alkyl group (eg, methyl, ethyl, propyl), a halogen atom (eg, chlorine, bromine, iodine,
Fluorine), nitro group, alkoxy group (eg methoxy, ethoxy), aryl group (eg phenyl), heterocyclic group (eg 2-pyridyl, 3-pyridyl, 1-pyrrolyl, 2-thienyl), 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-methylsulfagroup). Moyl), a hydroxy group, a carboxy group, an alkylthio group (for example, 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, and are edited by James, The Theory of the
Photographic Process, 4th Edition, Macmillan, 19
1977, page 198. Specifically, 2
-Pyrazolone-5-one, pyrazolidine-3,5-dione, imidazolin-5-one, hydantoin, 2 or 4-thiohydantoin, 2-iminooxazolidine-4
-One, 2-oxazoline-5-one, 2-thiooxazoline-2,4-dione, 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, indazoline-2-one, pyrido [1,2-a] pyrimidine- Examples include nuclei of 1,3-dione, pyrazolo [1,5-b] quinazolone, pyrazolopyridone, and the like. Preferred are hydantoin, rhodanine, barbituric acid, and 2-oxazolin-5-one. Preferably as Za ₄ is a barbituric acid.

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

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

In the formula, Ra ₁ , Ra ₂ and Ra ₃ are each independently a hydrogen atom, an alkyl group (preferably having a carbon atom number (hereinafter referred to as C number) 1 to 18, more preferably 1 to 7,
Particularly preferably, 1 to 4 unsubstituted alkyl groups (eg,
Methyl, ethyl, propyl, isopropyl, butyl, isobutyl, hexyl, octyl, 2-ethylhexyl, dodecyl, octadecyl), a C number 1 to 18, preferably 1 to 7, particularly preferably 1 to 4 substituted alkyl group {eg, substituted Examples of the group include the above-mentioned W-substituted alkyl groups. Preferably, an aralkyl group (eg, benzyl, 2-phenylethyl), a hydroxyalkyl group (eg, 2-hydroxyethyl, 3-hydroxypropyl, 6-hydroxyhexyl), a carboxyalkyl group (eg, 2-carboxyethyl, 3-). Carboxypropyl, 4-carboxybutyl, carboxymethyl, 5-
Carboxypentyl), 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), an acyloxyalkyl group (eg 2-acetyloxyethyl), an acylalkyl group (eg 2-acetylethyl), a carbamoylalkyl group (eg 2-morpholinocarbonylethyl), a sulfamoylalkyl group (eg N, N-dimethylsulfamoylmethyl), sulfoalkyl group (for example, 2-sulfobenzyl, 3-sulfo-3-phenylpropyl, 2-sulfoethyl, 3-sulfopropyl, 3-sulfobutyl, 4-sulfobutyl, 2- [3 -Sulfopropoxy] ethyl, 2-hydroxy-3-sulfopropyl,
3-sulfopropoxyethoxyethyl), a sulfatoalkyl group (for example, 2-sulfatoethyl group, 3-sulfatopropyl, 4-sulfatobutyl), a heterocyclic-substituted alkyl group (for example, 2- (pyrrolidin-2-one) -1
-Yl) ethyl, tetrahydrofurfuryl), an alkylsulfonylcarbamoylalkyl group (for example, methanesulfonylcarbamoylmethyl group), an acylcarbamoylalkyl group (for example, acetylcarbamoylmethyl group), an acylsulfamoylalkyl group (for example, acetylsulfamoylmethyl group) ), An alkylsulfonylsulfamoylalkyl group (for example, a methanesulfonylsulfamoylmethyl group), a halogen-substituted alkyl group (for example, 2-
Chloroethyl, 2,2,2-trifluoroethyl)}, an alkenyl group (preferably having a C number of 2 to 20, for example, vinyl, allyl, 3-butenyl, oleyl, the aforementioned W-substituted alkenyl group, for example, a sulfoalkenyl group. (Eg, 3-sulfo-2-propenyl) and the like, aryl group (C number 6 to 2)
0, preferably C 6-10, more preferably C 6-8 unsubstituted aryl groups (eg phenyl, 1-
A naphthyl group, 2-naphthyl, a substituted aryl group having a C number of 6 to 20, preferably a C number of 6 to 10, and more preferably a C number of 6 to 8 (for example, W described above as an example of the substituent is substituted) And an aryl group, specifically p-
Examples thereof include a methoxyphenyl group, a p-methylphenyl group, a p-chlorophenyl group and the like. )), A heterocyclic group (C
An unsubstituted heterocyclic group having a number of 1 to 20, preferably a C number of 3 to 10, and more preferably a C number of 4 to 8 (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), a C number of 1 to 20, preferably a C number of 3 to 10, and more preferably a C number of 4 to 8 Substituted heterocyclic group (for example, the aforementioned W mentioned as an example of the substituent)
A heterocyclic group substituted with. Specific examples thereof include a 5-methyl-2-thienyl group and a 4-methoxy-2-pyridyl group. )). Ra ₁ , Ra ₂ and Ra ₃ are preferably a hydrogen atom, an alkyl group, a sulfoalkyl group or an aryl group, and more preferably an alkyl group or a sulfoalkyl group.

Ma _{1 to} Ma _{14 each} independently represent a methine group and may have a substituent, and the substituent may be any of the above-mentioned substituent groups W, but preferably has a C number of 1 to 2, for example.
0 alkyl group (eg, methyl, ethyl, i-propyl), halogen atom (eg, chlorine, bromine, iodine, fluorine), nitro group, C 1-20 alkoxy group (eg, methoxy, ethoxy), C Aryl group of 6 to 26 (eg, phenyl, 2-naphthyl), heterocyclic group of 0 to 20 C (eg, 2-pyridyl, 3-pyridyl), C number of 6
To 20 aryloxy groups (eg phenoxy, 1-naphthoxy, 2-naphthoxy), C1-20 acylamino groups (eg acetylamino, benzoylamino), C
Examples thereof include a carbamoyl group having 1 to 20 (eg, N, N-dimethylcarbamoyl), a sulfo group, a hydroxy group, a carboxy group, an alkylthio group having 1 to 20 C (eg, methylthio), and a cyano group. Further, it may form a ring with another methine group, or may form a ring with an auxochrome. Preferred are unsubstituted, ethyl group-substituted, and methyl group-substituted methine groups.

L ₁ , La and Lb each represent a linking group (including a single bond) and may be any linking group, but preferably a single bond or an alkylene group (preferably having carbon atoms (hereinafter referred to as C number)). 1-20, for example methylene, ethylene, propylene, butylene, pentylene, hexylene, octylene), arylene group (preferably C number 6-26, for example phenylene, naphthylene), alkenylene group (preferably C number 2-20, for example ethenylene). , Propenylene),
Alkynylene group (preferably having a C number of 2 to 20, for example, ethynylene, propynylene), amide group, ester group, sulfamido group, sulfonate group, ureido group, sulfonyl group, sulfinyl group, thioether group, ether group, carbonyl group,- NR51- (R51 is a hydrogen atom or 1
It is a valent substituent and preferably W is mentioned as the substituent. Heterylene group (preferably having a C number of 1 to 26, for example, 6-chloro-1,3,5-triazyl-2,4-diyl group, pyrimidine-). 2,4-diyl group, quinoxaline-
2,3-diyl group), which represents a linking group having 0 to 100 or less, preferably 1 or more or 20 or less carbon atoms, which is formed by combining one or more. L ₁ , La, and Lb are preferably each represented by -G _1- (A ₁ -G _2- ) t _1- .
A ₁ is -O-, -S-, -SO _2- , -N regardless of the orientation.
R ₃ −, —COO—, —CONR ₄ —, or —SO ₂ NR ₅ — is represented, and R _{3 to} R ₅ are each independently a hydrogen atom,
It represents an alkyl group, an alkenyl group, an aryl group or a heterocyclic group (the above preferred examples are the same as Ra ₁ to Ra ₃ ). R ₃
Is preferably a hydrogen atom or an alkyl group, more preferably an alkyl group, and R ₄ and R ₅ are preferably a hydrogen atom or an alkyl group, and more preferably a hydrogen atom. A ₁ is preferably -O-,-
It represents SO ₂ —, —COO—, or —CONR ₄ —, more preferably —CONR ₄ —.

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

T1 represents an integer of 1 to 10, preferably 1
Alternatively, it represents 2, more preferably 1. t1 is 2 or more
When multiple A₁And G₂May be the same or different. t1
When is 1, A₁Is -COO-, -CONR_Four-, -SO₂
NR_FiveIt is preferable that any one of-, and -COO-
Or-CONR_FourIt is more preferable that it is-, and
R_FourFurther, it is preferably-(preferably -CONH-)
preferable. When t1 is 2 or more, A₁At least one of-
COO-, -CONR_Four-, -SO ₂NR_FiveOne of −
Is preferred, and -COO- or -CONR_Four-In
More preferably, -CONR_Four-(Preferably
-CONH-) is more preferred. Also that
Remaining A₁For -COO-, -CONR_Four-,-
SO₂NR_Five-, -O-, -SO₂-It must be one of
And more preferably, -O- or -CONR_Four-(Preferred
Or more preferably -CONH-).

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

Preferred examples of the compound of the present invention represented by the general formula (1) or the general formula (2) are as follows. However, the present invention is not limited to this. Note that the structural formulas of the compounds of the present invention described below are only one limiting structure among a number of possible resonance structures, and other structures that can be obtained by resonance may be used.

[0041]

[Chemical 8]

[0042]

[Chemical 9]

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

In the compound represented by the general formula (2),
Adsorption power to silver halide grains is Dye1> (Dye2, and Dy2
It is preferable that e3) or Dye3> (Dye2 and Dye1). At least one -SO ₃ In this respect the Dye2
_{M, -OSO 3 M, -OPO 3} M 2, -PO 3 M 2, -CO
OM is preferably included, and at least one --SO
More preferably ₃ M is included. Also, Dye1, Dye3
Of, even chromophores towards weak adsorption, at least one _{-SO 3 M, -OSO 3 M,} -OPO 3 M 2, -PO 3 M 2,
It is preferable to include -COOM, it is more preferable to contain at least one -SO ₃ M. In addition, M represents a proton or a cation. The evaluation of the adsorptivity to silver halide grains can be carried out using each model compound.

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

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

The compound of the present invention is mainly used as a sensitizing dye in a silver halide photographic emulsion and a silver halide photographic light-sensitive material. The compounds of the present invention can be used alone or in combination of the compounds of the present invention, or can be used in combination with other sensitizing dyes in a silver halide photographic emulsion or a silver halide light-sensitive material. At that time, the dyes used are preferably cyanine dyes, merocyanine dyes, rhodacyanine dyes, trinuclear merocyanine dyes, tetranuclear merocyanine dyes,
Examples include allopolar dyes, hemicyanine dyes, styryl dyes, and the like. Cyanine dyes, merocyanine dyes and rhodacyanine dyes are more preferred, and cyanine dyes are particularly preferred. For more information on these dyes, see FM Harmer, “Heterocyclic Compounds-Cy.
anine Dyes and Related Compounds ", John Wiley & Sons-New York, London, 1964, DMSturmer," Heterocyclic Compounds-Special Topics "・ Heterocyclic Compounds-Spec
ial topics in heterocyclic chemistry) ", 18th
Chapter, Section 14, 482-515, John & Wiley & Son
s, New York, London, 1977, etc. Preferred dyes include US Pat. No. 5,994,
No. 051, pages 32-44, and US Pat. No. 5,74
The sensitizing dyes shown in the general formulas described in Nos. 7,236, pp. 30 to 39, and specific examples are mentioned. Further, general formulas of preferable cyanine dyes, merocyanine dyes, and rhodacyanine dyes are shown in U.S. Pat. No. 5,340,694, columns 21 to 22 (XI), (XII), and (XIII) (however, , N12, n15, n17, and n18 are not limited, and may be an integer of 0 or more (preferably 4 or less).

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

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

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

It has been recognized that the timing of adding the sensitizing dye of the present invention (and other sensitizing dyes and supersensitizers) to the silver halide emulsion of the present invention has been useful so far. Any of the known emulsion preparation steps may be performed. For example, US Pat. Nos. 2,735,766 and 3,6.
28,960, 4,183,756, 4,22
5,666, JP-A-58-184142, 60-
As disclosed in 196749 and the like, the period before the grain forming step or / and desalting of the silver halide, the period during and / or after the desalting process and before the start of chemical ripening,
As disclosed in JP-A-58-113920, it is added at any time or step immediately before or during the chemical ripening, at any time before the emulsion is coated before the coating after the chemical ripening and before the coating. May be. Also, US Pat.
No. 5,666, JP-A-58-7629, etc., the same compound alone or in combination with a compound having a different structure, for example, during the grain formation step and the chemical ripening step or the chemical ripening step. It may be added in divided portions such as after completion or before chemical aging or during the process and after completion, and the compound and the combination of compounds added in different portions may also be added in different types. May be.

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

The sensitizing dye of the present invention (also for other sensitizing dyes and supersensitizers) can be directly dispersed in the emulsion. Further, these may be first dissolved in a suitable solvent such as methyl alcohol, ethyl alcohol, methyl cellosolve, acetone, water, pyridine or a mixed solvent thereof, and added to the emulsion in the form of a solution. At this time, additives such as a base, an acid, and a surfactant can be coexistent. Ultrasonic waves can also be used for dissolution. As a method of adding this compound, as described in US Pat. No. 3,469,987, the compound is dissolved in a volatile organic solvent, and the solution is dispersed in a hydrophilic colloid to prepare a dispersion of this compound. No. 3,822,135, a method of adding the compound to an emulsion, a method of dispersing the compound in a water-soluble solvent and adding the dispersion to the emulsion, as described in JP-B-46-24185. A method of dissolving a compound in a surfactant and adding the solution to the emulsion, as described in JP-A-51-74624, using a compound for red-shifting to dissolve the solution into the emulsion. A method of addition, a method of dissolving the compound in an acid containing substantially no water and adding the solution to the emulsion, as described in JP-A-50-80826, is used. In addition, US Pat.
2,343, 3,342,605, 2,99
The methods described in 6,287, 3,429,835 and the like can also be used.

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

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

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

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

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

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

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

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

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

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

As the protective colloid used in the preparation of the emulsion of the present invention and as the binder of the other hydrophilic colloid layers, it is advantageous to use gelatin, 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 hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfates, sugar derivatives such as sodium alginate and starch derivatives. ;
Various synthetic hydrophilic polymeric substances such as polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, and other single or copolymers. Can be used. Examples of gelatin include lime-processed gelatin, acid-processed gelatin and Bull. Soc. Sci.
Photo. Japan. No. 16. P30 (196
The enzyme-treated gelatin as described in 6) may be used, or a hydrolyzed product or an enzymatically decomposed product of gelatin can also be used. The emulsion of the present invention is preferably washed with water for desalting and dispersed in a newly prepared protective colloid.
The temperature for washing with water can be selected according to the purpose, but it is preferably selected within the range of 5 ° C to 50 ° C. The pH at the time of washing with water can also be selected according to the purpose, but it is preferably selected between 2 and 10. More preferably, it is in the range of 3-8. The pAg at the time of washing with water can also be selected according to the purpose, but it is preferably selected between 5 and 10. As a method of washing with water, a noodle washing method, a dialysis method using a semipermeable membrane, a centrifugation method, a coagulation sedimentation method, or an ion exchange method can be selected and used. In the case of the coagulation sedimentation method, it can be selected from 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.

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

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

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

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

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

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

During the manufacturing process of the emulsion of the present invention, acid for silver is used.
It is preferable to use an agent. What is an oxidizing agent for silver?
Has the effect of acting on metallic silver and converting it to silver ions
Refers to a compound. Especially the formation process of silver halide grains and
Very small silver particles by-produced during the chemical sensitization process
Compounds that can convert the above into silver ions are effective. here
The silver ions generated in are, for example, silver halide and sulfide.
You may form a sparingly soluble silver salt such as silver or silver selenide.
You may also form a silver salt that is easily soluble in water, such as silver nitrate.
Yes. The oxidizing agent for silver may be an inorganic substance or an organic substance.
It may be. Examples of the inorganic oxidant include azo.
Hydrogen peroxide, hydrogen peroxide and its adducts (eg NaBO₂ 
・ H₂O₂ ・ 3H₂O, 2NaCO₃・ 3H₂O₂ , Na_Four
P₂O₇・ 2H₂O ₂ 2Na₂SO_Four ・ H₂O₂ ・ 2H
₂O), peroxyacid salts (eg K₂S₂O₈, K₂C₂O
₆, K₂P₂O₈), A peroxy complex compound (for example, K₂
[Ti (O₂) C₂O_Four] ・ 3H₂O, 4K₂SO_Four ・ Ti
(O₂) OH / SO_Four・ 2H₂O, Na₃[VO (O₂)
(C₂H_Four)₂] ・ 6H₂O), permanganate (eg,
KMnO_Four), Chromates (eg, K₂Cr₂O₇ )of
Oxygenates, halogen elements such as iodine and bromine,
Halogenates (eg potassium periodate), high valence
Metal salts (eg potassium hexacyanoferrate)
And thiosulfonate.

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

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

The photographic emulsion used in the present invention may contain various compounds for the purpose of preventing fog during the production process of the light-sensitive material, storage or photographic processing, or stabilizing photographic performance. . That is, thiazoles, for example, benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, amino Triazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole),
Mercaptopyrimidines, mercaptotriazines, for example thioketo compounds such as oxadrinethione, azaindenes, for example triazaindenes, tetraazaindenes (especially 4-hydroxy-substituted (1,3,3
a, 7) Tetraazaindenes), known as antifoggants or stabilizers such as pentaazaindenes,
Many compounds can be added. For example, U.S. Pat. Nos. 3,954,474 and 3,982,947,
Those described in Japanese Examined Patent Publication No. 52-28660 can be used. One of the preferable compounds is JP-A-63-21.
There are compounds described in 2932. Antifoggants and stabilizers can be used at various times before particle formation, during particle formation, after particle formation, in the washing step, during dispersion after washing, before chemical sensitization, during chemical sensitization, after chemical sensitization, and before coating. It can be added depending on the purpose. In addition to adding the effect of preventing fog and stabilizing during the preparation of the emulsion, the crystal wall of the grain is controlled, the grain size is reduced, the solubility of the grain is reduced, and the chemical sensitization is controlled. It can be used for various purposes such as controlling the arrangement of dyes.

The silver halide emulsion prepared according to the present invention can be used in both color photographic light-sensitive materials and black-and-white photographic light-sensitive materials. As color photographic light-sensitive materials, in particular, color photographic paper, color photography films, color reversal films, color diffusion transfer films, and black-and-white photographic light-sensitive materials are general photography films, X-ray films, medical diagnostic films, printing materials. Film, diffusion transfer film and the like.

In the fields of medical diagnostic films and films for printing light-sensitive materials, exposure can be efficiently performed by a laser imagesetter or a laser imager. For the technology in these fields, see Japanese Patent Application Laid-Open No. 7-28
7,337, JP-A-4-335,342, JP-A-5
-313,289, JP-A-8-122,954, JP-A-8-292,512 and the like. Also, a photothermographic material can be used. For example, a catalytically active amount of a photocatalyst (eg, silver halide), a reducing agent,
Materials having a photosensitive layer in which a reducible silver salt (for example, an organic silver salt) and, if necessary, a toning agent for controlling the color tone of silver are dispersed in a binder matrix are known. For these, see, for example, US Pat.
4, U.S. Pat. No. 3,457,075, U.S. Pat. No. 2910377.
U.S. Pat. No. 4,500,626, Japanese Patent Publication No. 43-4924
No. 11-24200, No. 11-24201, No. 11-30832,
11-84574, 11-65021, 11-109547, 11-12
No. 5880, No. 11-129629, No. 11-133536 ~ No. 11-133539
No. 11, 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 No. 2000-89436.
No., etc.

The compound of the present invention can also be preferably used in a diffusion transfer photosensitive material. Among them, the heat development diffusion transfer method is disclosed in JP-A-2000-98562 (Japanese Patent Application No.
No. 265273) (using preformed dye) and Japanese Patent Application No. 2000-89436 (using coupling-forming dye), and Japanese Patent Application Laid-Open No. 2000-2000.
The method described in -284442 (Japanese Patent Application No. 11-89801) can be referred to.

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

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

[0080]   Additive type RD17643 RD18716 RD308119 1 Chemical sensitizer Page 23 Page 648 Right column Page 996 2 Sensitivity enhancer Same as above 3 Spectral sensitizer, pages 23-24, page 648, right column-996 right-998 right     Supersensitizer, page 649, right column 4 Whitener 24 pages 998 Right 5 Antifoggant page 24 to 25 page 649 right column 998 right to 1000 right     And stabilizers 6 Light absorber, fill page 25-26 page 649 right column-1003 left-1003 right     , UV absorber, page 650, left column 7 Anti-stain agent Page 25 Right column 650 Left to right column 1002 Right 8 Dye image stabilizer 25 pages 1002 right 9 Hardener 26 pages 651 left column 1004 right to 1005 left 10 Binder page 26 Same as above 1003 right to 1004 right 11 Plasticizer, Lubricant Page 27 Page 650 Right column 1006 Left to 1006 Right 12 Coating aid, pages 26-27 Same as above 1005 left to 1006 left     Surfactant 13 Antistatic agent Page 27 Same as above 1006 right to 1007 left 14 Matting agent 1008 left to 1009 left

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

[0082] 1. Layer composition: p. 61, lines 23 to 35, p. 41 to p. 62, line 14 2. Middle layer: p. 61, lines 36-40 3. Multilayer effect imparting layer: p. 62, lines 15-18 4. Silver halide halogen composition: p. 62, lines 21-25 5. Crystal Habit of Silver Halide Grains: p. 62, lines 26-30 6. Silver halide grain size: p. 62, lines 31-34 7. Emulsion manufacturing method: Page 62, lines 35-40 8. Silver halide grain size distribution: p. 62, lines 41-42 9. Tabular grains: p. 62, lines 43-46 Ten. Internal structure of particles: p. 62, lines 47-53 11. Emulsion latent image forming type: p. 62 line 54 to p. 63 line 5 12. Physical ripening and chemical sensitization of emulsion: Page 63, lines 6-9 13. Mixed use of emulsion: Page 63, lines 10-13 14. Fogging emulsion: p. 63, lines 14-31 15. Non-photosensitive emulsion: page 63, lines 32 to 43 16. Silver coating amount: Page 63, lines 49-50

[0083] 17. Formaldehyde Scavenger: Page 64, lines 54-57 18. Mercapto-based antifoggant: Page 65, lines 1-2 19. Release agents such as fogging agents: Page 65, lines 3-7 20. Dye: Page 65, lines 7-10 twenty one. Color couplers in general: Page 65, lines 11-13 twenty two. Yellow, magenta and cyan couplers: page 65, lines 14-25. twenty three. Polymer Coupler: Page 65, lines 26-28 twenty four. Diffusible dye-forming coupler: p. 65, lines 29-31. twenty five. Colored coupler: Page 65, lines 32 to 38 26. Functional couplers in general: Page 65, lines 39-44 27. Bleach accelerator releasing coupler: page 65 lines 45-48. 28. Development accelerator releasing coupler: p. 65, lines 49-53 29. Other DIR couplers: page 65 line 54 to page 66 line 4 30. Coupler dispersion method: Page 66, lines 5 to 28

[0084] 31. Antiseptic / antifungal agent: Page 66, lines 29-33 32. Type of sensitive material: Page 66, lines 34-36 33. Photosensitive layer film thickness and swelling speed: Page 66, line 40 to Page 67, line 1 34. Back layer: Page 67, lines 3-8 35. General development processing: Page 67, lines 9-11 36. Developer and developer: Page 67, lines 12-30 37. Developer additive: Page 67, lines 31-44 38. Inversion processing: Page 67, lines 45-56 39. Treatment liquid opening ratio: Page 67, line 57 to Page 68, line 12 40. Development time: Page 68, lines 13-15 41. Bleaching / Bleaching / Fixing: Page 68, line 16 to Page 69, line 31 42. Automatic processor: Page 69, lines 32-40 43. Washing / rinsing / stabilization: Page 69, line 41 to Page 70, line 18 44. Replenishment / reuse of processing liquid: Page 70, lines 19-23 45. Built-in developer sensitive material: Page 70, lines 24 to 33 46. Development processing temperature: Page 70, lines 34-38 47. Use for film with lens: Page 70, lines 39-41

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

In the present invention, a laser light source may be preferably used. As the laser light, helium-neon gas, argon gas, krypton gas, carbon dioxide gas or the like is used as a laser oscillation medium, or a laser using a solid oscillation medium such as ruby or cadmium, or a liquid laser or a semiconductor laser. is there. Since these laser lights are coherent lights with sharp directivity in phase at a single frequency, unlike the lights used for ordinary illumination, halogenated light for exposing them as a light source is used. The silver photographic light-sensitive material is required to have spectral characteristics that match the emission wavelength of the laser used. Among the above 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, anti-irradiation dyes or antihalation dyes for the purpose of improving sharpness and color resolution. . This compound is a silver halide photographic light-sensitive material layer in a conventional manner,
It may be contained in a coating liquid such as a filter layer and / or an antihalation layer. The amount of the dye used may be an amount sufficient for coloring the photographic layer, and those skilled in the art can easily select this amount appropriately according to the purpose of use. Generally, the optical density is in the range of 0.05 to 3.0. Is preferably used. The addition time may be any step before coating.

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

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

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

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

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

As a method of increasing the light absorption intensity, there are a method of adsorbing the dye chromophore on the surface of the particle more, a method of increasing the molecular extinction coefficient of the dye, and a method of reducing the area occupied by the dye. Any method may be used, but a method in which the dye chromophore is more adsorbed on the particle surface is preferable. Here, the state in which the dye chromophore is more adsorbed on the surface of the grain means that there is more dye bound to the vicinity of the silver halide grain, including the dye present in the dispersion medium. Absent. The term "more than one layer" as used herein also includes the case where the dye chromophore is covalently linked to a compound such as a dye adsorbed on the particle surface as in the present invention. In those cases, it is necessary that the dye not directly adsorbed on the surface of the grain causes spectral sensitization. For that purpose, the excitation energy from the dye not directly adsorbed on the silver halide to the dye directly adsorbed on the grain is changed. Communication is required. Therefore, when the transfer of the excitation energy needs to occur in more than 10 steps, the final transfer efficiency of the excitation energy becomes low, which is not preferable. One example of this is the case where most of the dye chromophores are present in the dispersion medium, such as the polymer dyes of JP-A-2-113239, and the transfer of excitation energy is required in 10 or more steps. The adsorption of the dye chromophore on the silver halide grains is preferably 1.5 layers or more, more preferably 2 layers.
It is more than one layer, particularly preferably 2.5 layers.

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

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

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

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

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

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

Further, the absorption maximum wavelength of the dye chromophore of the first layer in the silver halide photographic light-sensitive material is longer than the absorption maximum wavelength of the dye chromophore of the second or more layers, and further, the second layer It is preferable that the emission of the dye chromophore described above overlaps the absorption of the dye chromophore of the first layer from the viewpoint of energy transfer efficiency from the dyes of the second or more layers to the dye of the first layer. Further, the dye chromophore in the first layer preferably forms a J-aggregate. Furthermore, in order to have absorption and spectral sensitivity in a desired wavelength range, it is preferable that the dye chromophores in the second and higher layers also form a J-aggregate. 1 of excitation energy of the second layer dye
Energy transfer efficiency to the layer dye is preferably 30%
Or more, more preferably 60%, particularly preferably 90%
That is all. Here, the excitation energy of the second layer dye is
It means the energy of the dye in the excited state, which is generated by the second layer dye absorbing the light energy. When the excitation energy of a molecule is transferred to another molecule, the excited electron transfer mechanism, the Forster energy transfer mechanism (Forst
er Model), Dexter energy transfer mechanism (Dextor Model), etc., the excitation energy is considered to be transferred. It is preferable to satisfy the condition. Further, it is particularly preferable to satisfy the conditions for causing the Forster type energy transfer mechanism. The efficiency of energy transfer from the dye in the second layer to the dye in the first layer can be determined as the spectral sensitization efficiency when exciting the dye in the second layer / the spectral sensitizing efficiency when exciting in the dye in the first layer.

The meanings of the terms used in the present invention are described below. Dye occupied area: The occupied area per dye molecule. It can be experimentally determined from the adsorption isotherm. In the case of a dye in which the dye chromophores are linked by a covalent bond, the area occupied by each dye in the unlinked state is used as a reference. 80 for simplicity
Å ² . 1-layer saturated coating amount: Dye adsorption amount per unit particle surface area when 1-layer saturated coating. The reciprocal of the smallest dye footprint of the added dyes. Multilayer adsorption: A state in which the adsorption amount of the dye chromophore per unit particle surface area is larger than the saturated coating amount of one layer. In the present invention, multilayer adsorption means a state in which the adsorption amount of the dye chromophore per unit particle surface area is larger than the one-layer saturated coating amount. Therefore, as a dye in which two dye chromophores are linked by a covalent bond, When one layer is adsorbed, it means that two layers are adsorbed. Number of adsorbed layers: Adsorption amount of dye chromophore per unit particle surface area based on the saturated coating amount of one layer. In the case of a compound in which two dye chromophores are covalently linked, the above adsorption amount x
2 is defined as the number of adsorption layers. For example, when a dye in which two dye chromophores are covalently linked has the same dye occupancy area and the same adsorption amount as a certain non-linked model dye, the number of adsorption layers is 2.

[0102]

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

Example 1 Synthesis example of compound No. 4 of the present invention

[0104]

[Chemical 10]

7.9 g of 1,2-bis (2-aminoethoxy) ethane (4a) was dissolved in acetonitrile, 15 g of isocyanate 4b was added at room temperature, and the mixture was stirred at room temperature for 5 hours. By collecting the precipitated crystals by filtration and drying under reduced pressure,
15 g (yield 69%) of 4c was obtained. 9.0 g of 4c is dissolved in dichloromethane at room temperature, and 4.74 g of malonyl chloride (4d) is added dropwise thereto. Then, after heating under reflux for 2 hours, it was cooled to room temperature, and this dichloromethane solution was added with water,
It was washed with saturated saline and separated. The organic phase was dried and filtered with anhydrous magnesium sulfate, and the composition obtained by distilling off the solvent under reduced pressure was purified by silica gel column chromatography to obtain 2.61 g of bisbarbituric acid (4e).
(Yield 22%) was obtained. A mixed solution of 2.5 g of 4e, 30 ml of acetic acid, and 15 ml of concentrated hydrochloric acid was heated under reflux at an external temperature of 130 ° C. for 1.5 hours. 4f obtained by concentrating and drying the reaction solution under reduced pressure was used as an ethanol solution, and separately synthesized compound 4g 4.2g, triethylamine 5.2m.
1, and acetic anhydride (1.74 ml) were sequentially added, and an external temperature of 110
The mixture was stirred at 0 ° C for 30 minutes. The reaction mixture was concentrated under reduced pressure to dryness, methanol was added to this, and the mixture was stirred at room temperature.
A methanol solution of 0.8 g of sodium acetate dissolved in advance was added, the mixture was stirred at room temperature for 10 minutes, ethanol was further added, and the mixture was stirred at room temperature for 1 hour. The precipitated crystals were collected by filtration and dried to obtain 4.85 g (yield 89%) of bis-type merocyanine dye (4h). 0.42 g of the bis-type merocyanine dye (4h), 0.2 g of the cyanine dye (4i) separately synthesized by a conventional method, and 0.2 g of 1-hydroxybenzotriazole were mixed with DMSO, and the mixture was heated and stirred at an external temperature of 60 ° C to obtain a uniform solution. And To this, 0.3 g of 1H-benzotriazol-1-yloxytri (dimethylamino) phosphonium hexafluorophosphate and 1.5 ml of diisopropylethylamine were added, and the external temperature was 60 ° C.
And stirred for 30 minutes. The reaction solution was diluted with acetone and ethyl acetate, and the precipitated crystals were collected by filtration and separated with Sephadex.
LH-20 was purified by column chromatography with a solvent of methanol, and compound No. 4 mg was obtained. The structure was confirmed by NMR, absorption and FAB / MS.

Example 2 (Preparation of seed emulsion a) 0.017 g of KBr, average molecular weight of 2
Aqueous solution containing 0.4 g of oxidised gelatin of 0000 11
64 ml was kept at 35 ° C. and stirred. AgNO ₃ (1.6
g) An aqueous solution, a KBr aqueous solution, and an oxidation-treated gelatin (2.1 g) aqueous solution having an average molecular weight of 20,000 were added by the triple jet method over 48 seconds. At this time, the silver potential was kept at 13 mV against the saturated calomel electrode. An aqueous KBr solution was added to adjust the silver potential to -66 mV, and then the temperature was raised to 60 ° C. 21 g of succinated gelatin with an average molecular weight of 100,000
Was added, followed by an aqueous solution of NaCl (5.1 g). An AgNO ₃ (206.3 g) aqueous solution and a KBr aqueous solution were added over 61 minutes while accelerating the flow rate by the double jet method. At this time, the silver potential was kept at -44 mV with respect to the saturated calomel electrode. After desalting, average molecular weight 100
000 succinated gelatin was added and the pH was adjusted to 5.
8, pAg was adjusted to 8.8 to prepare a seed emulsion. This seed emulsion contains 1 mol of Ag and 8 mol of gelatin per kg of emulsion.
It was a tabular grain containing 0 g, an average equivalent circle diameter of 1.46 μm, a variation coefficient of an equivalent circle diameter of 28%, an average thickness of 0.046 μm, and an average aspect ratio of 32.

(Formation of Core) 134 g of the above seed emulsion a,
KBr 1.9g, average molecular weight 100,000
Keep 1200 ml of an aqueous solution containing 22 g of ratin at 75 ° C
It was stirred. AgNO ₃(43.9 g) aqueous solution and KBr water
A solution and an aqueous gelatin solution having a molecular weight of 20,000 are disclosed in Japanese Patent Laid-Open No.
Coupling Induction Type Stirrer
25 minutes before mixing just before addition in another chamber with
Added over time. At this time, adjust the silver potential to the saturated calomel electrode.
To -40 mV.

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

(Formation of Second Shell) After the formation of the first shell, an AgNO ₃ (42.6 g) aqueous solution, a KBr aqueous solution, and a gelatin aqueous solution having a molecular weight of 20000 are mixed in another chamber just before the addition and immediately before the addition. Added over 17 minutes. At this time, the silver potential was set to −20 with respect to the saturated calomel electrode.
kept at mV. Then, the temperature was lowered to 55 ° C.

(Formation of Third Shell) After the formation of the second shell, the silver potential was adjusted to -55 mV and AgNO ₃ (7.
1 g) aqueous solution and KI (6.9 g) aqueous solution and molecular weight 200
A gelatin aqueous solution of No. 00 was mixed just before the addition in another chamber in the same manner and added over 5 minutes.

(Formation of Fourth Shell) After the formation of the third shell, an AgNO ₃ (66.4 g) aqueous solution and a KBr aqueous solution were added at a constant flow rate for 30 minutes by the double jet method. On the way, potassium iridium hexachloride and yellow blood salt were added. At this time, the silver potential was set to 30 with respect to the saturated calomel electrode.
kept at mV. Wash with normal water, add gelatin,
The pH was adjusted to 5.8 and pAg 8.8 at 40 ° C. This emulsion was designated as emulsion b. Emulsion b has an average equivalent circle diameter of 3.3 μm,
21% variation coefficient of equivalent circle diameter, 0.090 μm average thickness,
It was a tabular grain having an average aspect ratio of 37. Further, 70% or more of the total projected area was occupied by tabular grains having an equivalent circle diameter of 3.3 μm or more and a thickness of 0.090 μm or less. The saturated coating amount for one layer was 1.45 × 10 ⁻³ mol / mol Ag when the area occupied by the dye was 80 Å ² .

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

(2) Measurement of adsorption amount The dye adsorption amount was 10,000 rpm for the obtained liquid emulsion.
The precipitate was lyophilized by centrifugation for 10 minutes, and 0.05 g of the precipitate was added to 25 ml of 25% sodium thiosulfate aqueous solution and methanol to make 50 ml. This solution was analyzed by high performance liquid chromatography, and the dye concentration was quantified and determined. The number of adsorbed layers of the dye was determined from the amount of adsorbed dye and the saturated coating amount of one layer thus obtained.

(3) Preparation of coating sample An emulsion layer and a protective layer as shown in Table 1 were coated on a triacetyl cellulose film support provided with an undercoat layer. Further, Comparative Compound S-1 was changed to the compound of the present invention in an equimolar amount to prepare Samples 101 to 104.

[0115]

[Table 1]

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

The density of the treated sample was measured with a blue filter, and the sensitivity and fog were evaluated. Sensitivity is 0 than fog density.
2 Defined by the reciprocal of the exposure amount that gives a high density, and the sensitivity of each sample was expressed as a relative value with the value of Sample 101 as 100.

[0118]

[Table 2]

[0119]

[Chemical 11]

From Table 2, the compounds of the present invention are comparative compounds S
It is clear that compared with -1, more than two layers are adsorbed and the sensitivity is significantly increased. From the above results, it is clear that when the dyes in the second and subsequent layers are photoexcited, they contribute to higher sensitivity through energy transfer or electron transfer to the dyes in the first layer.

Example 3 The same comparison as in Example 2 was carried out using Example 5 of JP-A-8-29904.
Comparative example S-1
When the sensitivity of the blue sensitive layer of the sensitive material using is set to 100 (reference),
The sensitivity of the light-sensitive material using No. 4 of the present invention was as high as 219. In addition, Japanese Patent Application Laid-Open No. 2000-284442 (Japanese Patent Application No. 11-
No. 89801), the same comparison was made in the system of the instant photosensitive material of Example 1, and when the sensitivity of the blue sensitive layer of the photosensitive material using Comparative Example S-1 was 100 (reference), The sensitive material using No. 4 had a high sensitivity of 248.
Furthermore, the color reversal sensitizer system of Example 1 of JP-A-7-92601 and JP-A-11-160828, the color paper system of Example 1 of JP-A-6-347944, and the JP-A-8-122954 Example. The compound of the present invention is also used in the X-ray sensitive material system of No. 1, the heat-developable photosensitive material system of Example 1 of Japanese Patent Application No. 2000-89436, and the print sensitive material system of Example 1 of JP-A-8-292512. The sensitive material was found to be highly sensitive to the comparative compound. Further, it has been found that any of these systems has a large light absorption intensity and a large number of chromophore adsorption layers, and is similarly useful.

[0122]

By using the methine dye-linking compound of the present invention, a highly sensitive silver halide photographic light-sensitive material can be obtained.

Continued front page    F-term (reference) 2H023 CA06 CA08                 4H056 CA01 CA04 CA05 CB05 CB06                       CC02 CC08 CE03 CE07 DD07                       DD19 DD23 DD29

Claims (5)

[Claims] 1. A silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support, wherein the emulsion layer contains at least a compound represented by the following general formula (1). A silver halide photographic light-sensitive material characterized by containing one. General formula (1) In the formula, L ₁ represents a linking group, and D 1 and D 2 represent chromophores. q1,
r1 and r2 each represent an integer of 1 to 4 and (q1 × r1 +
r2) represents an integer of 3 to 5. qa represents an integer of 1 to 4. CI represents an ion that neutralizes charge, and y represents the number necessary for neutralizing charge. 2. The silver halide photographic light-sensitive material according to claim 1, wherein the compound is a compound represented by the following general formula (2). General formula (2) In the formula, La and Lb represent a linking group. Dye1, Dye2, and Dye3 may be the same or different and each represents a chromophore. CI represents an ion that neutralizes charge, and y represents the number necessary for neutralizing charge. 3. A compound represented by the general formula (2):
3. The silver halide photographic light-sensitive material according to claim 2, wherein at least one of Dye1, Dye2 and Dye3 is a cyanine chromophore. 4. A compound represented by the general formula (2):
4. The silver halide photographic light-sensitive material according to claim 3, wherein one of Dye1 and Dye3 is a cyanine chromophore, and the other one and Dye2 are a merocyanine chromophore or an oxonol chromophore. 5. A compound represented by the general formula (2):
The strength of the adsorptive power to silver halide grains when the connected portion of Dye1, Dye2, and Dye3 is replaced by a hydrogen atom is
e1> (Dye2 and Dye3), or Dye3> (Dye2 and Dye1)
5. The silver halide photographic light-sensitive material according to claim 2, claim 3, or claim 4.