JPS6289952A - Photographic silver halide emulsion - Google Patents

Abstract

PURPOSE:To carry out the high spectral sensitization of a silver halide emulsion and to inhibit fogging by combinedly incorporating a specified heterocyclic compound contg. N and a cyanine dye into the silver halide emulsion contg. <=12mol% silver iodide. CONSTITUTION:A heterocyclic compound contg. N represented by formula I (where R<1> is an aliphatic, aromatic or heterocyclic group having at least one -COOM or -SO3M group as a substituent and M is H, an alkali metallic atom, quat. ammonium or quat. phosphonium) and a cyanine dye are combinedly incorporated into a silver halide emulsion contg. <=12mol% silver iodide. A compound represented by formula II (where R<2> is phenyl having at least one -COOM or -SO3M group as a substituent and M is H, an alkali metallic atom, quat. ammonium or quat. phosphonium) is preferably used as the heterocyclic compound contg. N. When the silver iodide content is 1-12mol%, especially 2-10mol%, a significant sensitizing effect is produced. A compound represented by formula III [where each of Z<1> and Z<2> is a group of atoms required to form a 5- or 6-membered (condensed) heterocyclic ring, each of R<3> and R<4> is optionally substituted alkyl, each of L1 and L2 is optionally substituted methine and X1<-> is an acid anion] is preferably used as the cyanine dye. The silver halide emulsion can spectrally be sensitized as if it is hypersensitized by combinedly using the heterocyclic compound contg. N and the cyanine dye.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a spectrally sensitized silver halide photographic emulsion. More specifically, the present invention relates to a silver halide photographic emulsion containing a supersensitized cyanine dye.

[Conventional technology]

In the production technology of silver halide photographic emulsions, it is desired to further increase the sensitivity of photographic emulsions. Chemical sensitization and spectral sensitization are known as useful methods for increasing the sensitivity of silver halide photographic emulsions.

Spectral sensitization is the process of incorporating a sensitizing dye into a silver halide photographic emulsion to extend the sensitivity of the silver halide emulsion from the short wavelength range of visible light to the long wavelength range of visible light. This is a technique for increasing the sensitivity of a photographic emulsion by enlarging it, and cyanine dyes and the like are mainly used as sensitizing dyes, and many sensitizing dyes and their application methods have come to be known. In particular, by using two or more types of sensitizing dyes in combination, or by using a compound with a sensitizing dye in combination with a compound that itself has no or very poor spectral sensitization, it is possible to obtain the spectral spectral sensitization that can be obtained only with individual sensitizing dyes. A method of obtaining a greater sensitizing effect than sensitization is known and is called supersensitization.

Hereinafter, when we refer to "supersensitization", we mean only that the spectral sensitization rate (i.e., the ratio of spectral sensitization range sensitivity/intrinsic sensitivity range sensitivity) is higher than when a dye is used alone. In addition, as mentioned above, the combination of the sensitizing dye and other compounds increases the sensitivity in the spectral sensitization region by increasing the sensitivity in the spectral sensitization region. It should be understood that

Although it is well known that peterocyclic compounds having a mercapto group are useful as antifoggants for photographic emulsions, it is also known that such compounds reduce the sensitivity of photographic emulsions. This means, for example, C, E,
K., Mees, T.H.

Co-edited with James “The Theory of
The Photographic Process
ryof the Photographic Pro
cess) J 3rd edition, pages 344-346 (1967).

The spectral sensitizing effect of a cyanine dye having a pyridine nucleus in at least one of the two heterocyclic nuclei, that is, a pyridinocyanine dye (or pyridocyanine dye), can be achieved by combining a certain mercapto compound with an acidic group with the dye. The increase due to use is described in Japanese Patent Application Laid-Open No. 49-64419.
Known under No.

However, the invention disclosed in this patent application is only applicable to monomethine or trimethine cyanine dyes having a pyridine nucleus, and is not applicable to cyanine dyes having other structures. Furthermore, the sensitizing dye in this invention has significantly lower color sensitizing efficiency than other cyanine dyes when used alone. In addition, it has been disclosed in JP-A-51-1989 that heterocyclic mercapto compounds having no acidic group have a supersensitizing effect on the spectral sensitization of a wide range of trimethine cyanine dyes other than pyridinocyanine dyes. ” Known under No. 77224.

However, this method has the drawback that the application of the mercapto compound causes desensitization due to inhibition of development, which offsets the sensitizing effect of supersensitization, making it impossible to fully demonstrate the effect.

British Patent No. 1,275,701 describes a compound represented by the following general formula (A) as an antifoggant that can be stabilized without reducing sensitivity.

General formula (A): N-N R, R' represents a hydrogen atom, an alkali metal atom, or a quaternary ammonium.

However, the silver halide emulsion in the above British patent is only described in a general manner.

The present inventors have discovered that the halogen composition and structure of the silver halide emulsion are very important in bringing about the effects of the present invention.

[Problem that the invention seeks to solve]

Therefore, a first object of the present invention is to provide a silver halide photographic emulsion that is effectively sensitized by a novel means.

A second object of the present invention is to provide a silver halide photographic emulsion which has been spectrally sensitized by a novel means.

Another object of the present invention is to provide a silver halide photographic emulsion which is highly spectrally sensitized and has suppressed fogging.

Still another object of the present invention is to provide a photographic light-sensitive material using the above-mentioned silver halide photographic emulsion.

[Means for solving problems]

The present inventor has conducted studies to improve the drawback of having a supersensitizing effect with cyanine dyes and offsetting the effect of suppressing development. A silver halide emulsion containing silver has the following general formula (1)
This could be achieved using a silver halide photographic emulsion characterized by containing a combination of a nitrogen-containing heterocyclic compound represented by the formula and a cyanine dye.

General formula (1) (wherein R1 represents an aliphatic group, aromatic group or heterocyclic group substituted with at least one -COOM, -5o, M, and A is a hydrogen atom, an alkali metal atom, (Represents quaternary ammonium or quaternary phosphonium.) Furthermore, in the present invention, as the nitrogen-containing heterocyclic compound, a compound represented by the general formula (n) described below is particularly preferable.

In the present invention, the supersensitizing effect of the combination of a cyanine dye and a nitrogen-containing heterocyclic compound is influenced by the halogen composition and structure of silver halide. Silver iodide is preferred, where the silver iodide content is 12 mol% or less, preferably 1 to 12 mol%,
Particularly preferably, the effect is large when the amount is 2 to 10 mol%. Regarding the crystal structure of the silver halide, the halogen distribution within the grain may be uniform, the inside and outside may have different halogen compositions, or the crystal structure may be a layered structure, but particularly preferably It is a grain having substantially two distinct layered structures (core/shell structure) consisting of a core part of a high iodine layer and a shell part of a low iodine layer; or a tabular silver halide grain with an aspect ratio of 5 or more as described below. The effect is large in the case of particles.

Hereinafter, the nitrogen-containing heterocyclic ring (petero ring) compound represented by the general formula (I) used in the present invention will be explained in detail.

Specifically, the aliphatic group represented by R1 in the general formula (I) is a linear or branched alkyl group having 1 to 20 carbon atoms (
For example, methyl group, propyl group, hexyl group, dodecyl group, isopropyl group, etc.), cycloalkyl group having 1 to 20 carbon atoms (for example, cyclopropyl group, cyclohexyl group, etc.), and aromatic group, specifically, 6 to 20 aryl groups (e.g. phenyl group, naphthyl group, etc.), and the heterocyclic group specifically includes one or more nitrogen atoms,
A 5-, 6-, or 7-membered heterocycle containing an oxygen or sulfur atom, etc., and further forming a fused ring at an appropriate position (for example, a pyridine ring, a quinoline ring,
(pyrimidine ring, isoquinoline ring, etc.).

Further, the above-mentioned straight chain or branched alkyl group, cycloalkyl group, aryl group and heterocyclic group may have a substituent in addition to -COOM or -503M. Specifically, these substituents include halogen atoms (F,
CQ, Br, etc.), alkyl groups (methyl, ethyl, etc.), aryl groups (phenyl, p-chlorophenyl, etc.), alkoxy groups (methoxy, methoxyethoxy, etc.), aryloxy groups (phenoxy, etc.) ,
Sulfonyl groups (methanesulfonyl group, p-toluenesulfonyl group, etc.), sulfonamide groups (methanesulfonamide group, benzenesulfonamide group, etc.), sulfamoyl groups (diethylsulfamoyl group, unsubstituted sulfamoyl group, etc.), carbamoyl groups ( unsubstituted carbamoyl group, diethylcarbamoyl group, etc.), amide group (acetamido group, benzamide group, etc.), ureido group (methylureido group, phenylureido group, etc.), alkoxycarbonylamino group (methoxycarbonylamino group, etc.),
Aryloxycarbonylamino groups (phenoxycarbonylamino groups, etc.), alkoxycarbonyl groups (methoxycarbonyl groups, etc.), aryloxycarbonyl groups (
phenoxycarbonyl group, etc.), cyano group, hydroxy group, carboxy group, sulfo group, nitro group, amino group (unsubstituted amino group, dimethylamino group, etc.), alkylsulfinyl group (methoxysulfinyl group, etc.), arylsulfinyl group (phenyl sulfinyl group, etc.), alkylthio group (methylthio group, etc.), and arylthio group (phenylthio group, etc.), and these substituents may be substituted with two or more, and the substituents may be the same or different. Good too.

Among the nitrogen-containing heterocyclic compounds (mercaptotetrazole derivatives) represented by the general formula (1), those represented by the general formula (n) are particularly preferred.

General formula (II) R2 in general formula (If) represents at least one phenyl group substituted with 1000M or -So, M, and this phenyl group is may be substituted with a substituent. Specific examples of other substituents include the same substituents as those for the linear or branched alkyl group, cycloalkyl group, aryl group, and heterocyclic group represented by R1.

Here, when there are two or more -COOM and -503M, they may be the same or different. A means the same thing as expressed in general formula (1).

Preferred specific examples of the compound represented by the general formula (1) used in the present invention are listed below. However, the present invention is not limited to these specific examples.

COOM OOC As is generally well known, the compound represented by the general formula (1) can be easily synthesized by using a reaction between isothiocyanate and sodium azide. For reference, literatures and patents related to these synthesis methods are listed below.

U.S. Patent No. 3,266.897, Japanese Patent Publication No. 42-2184
No. 2, JP-A-56-111,846, British patents 1 and 2
No. 75,701, D.A.

Barges et al., Journal of Heterocyclic Chemistry
) 1aterocyclic Chemistry) Volume 15, Page 981 (1978), R.G. Dubenko, V.D., Panchenko (Pa.
'Khimia Getełczyskiv Soedinenii'
rotsiklicheskikh 5 oedinen
ii)”, Part 1.

(Azole order Jhaschie Gete
rotsikly+ 1967, pp. 199-201)
.

This compound may be added to the emulsion in accordance with the usual method for adding photographic emulsion additives. For example, methyl alcohol,
It can be dissolved in ethyl alcohol, methyl cellosolve, acetone, water, or a mixed solvent thereof and added as a solution.

Further, the compound represented by the general formula (1) can be added and used at any step of the manufacturing process of a photographic emulsion.
It can be added and used at any stage after emulsion production up to just before coating. Examples of the former include a silver halide grain formation process, a physical ripening process, and a chemical ripening process.

The cyanine dye used in the present invention is preferably one represented by the following general formula (I[I). .

General formula (m) In the formula, zl and Z2 each represent an atomic group necessary to form a 5- to 6-membered heterocycle (including a fused heterocycle);
3 and R4 represent an alkyl group which may be the same or different and may be substituted; Ll, L2 and L3 represent a methine group which may be the same or different and may be substituted; s Xiθ is Represents an acid anion.

Further, k represents 1 or 2, and m represents an integer of 1 to 4. Note that when k is 1, the above dye forms an inner salt.

Next, general formula (m) will be explained in detail.

In the general formula (m), Zl and Z2 each represent an atomic group necessary to form a 5- or 6-membered heterocycle (including a fused heterocycle), and may be the same or different. The heterocycle includes, for example, a thiazole nucleus (e.g., thiazole,
4-methylthiazole, 4-phenylthiazole, 4,
5-dimethylthiazole, 4,5-diphenylthiazole, etc.), benzothiazole nuclei (e.g., benzothiazole, 4-chlorobenzothiazole, 5-chlorobenzothiazole, 6-chlorobenzothiazole, 5-nitrobenzothiazole, 4-methyl Benzothiazole, 5-
Methylbenzothiazole, 6-methylbenzothiazole, 5-bromobenzothiazole, 6-bromobenzothiazole, 5-iodobenzothiazole, 5-phenylbenzothiazole, 5-methybenzothiazole, 6
-Ethoxybenzothiazole, 5-ethoxybenzothiazole, 5-ethoxybenzothiazole, 5
-Carpoxybenzothi, azole, 5-phenethylbenzothiazole, 5-fluorobenzothiazole, 5-chloro-6-methylbenzothiazole, 5,6-dimethylbenzothiazole, 5-hydroxy-6-methylbenzothiazole, tetrahydro benzothiazole, 4-phenylbenzothiazole, etc.), naphthothiazole nuclei (e.g., naphtho(2,1-d)thiazole, naphtho(1,
2-d) Thiazole, naphtho(2,3-d)thiazole, 5-methoxynaphtho(1,2-d)thiazole, 7-
nitronaphtho(2,1-d]thiazole, 8-methoxynaphtho(2,1-d)thiazole, 5-methoxynaphtho(2,3-d)thiazole, etc.), thiazoline core (e.g., thiazoline, 4-methylthiazoline, 4-nitrothiazoline, etc.), oxazole nuclei (e.g., oxazole, 4-methyloxazole, 4-nitrooxazole, 5-methyloxazole, 4-phenyloxazole, 4,5-diphenyloxazole, 4-ethyloxazole, etc.), benzoxazole Nucleus (benzoxazole, 5-chlorobenzoxazole, 5-methylbenzoxazole, 5-bromobenzoxazole, 5-
Fluorobenzoxazole, 5-phenylbenzoxazole, 5-methoxybenzoxazole, 5-nitrobenzoxazole, 5-trifluoromethylbenzoxazole, 5-hydroxybenzoxazole, 5
-Carboxybenzoxazole, 6-methylbenzoxazole, 6-chlorobenzoxazole, 6-nitrobenzoxazole, 6-methoxybenzoxazole, 6-hydroxybenzoxazole, 5,6-simethylbenzoxazole, 4,6-simethyl benzoxazole, 5-ethoxybenzoxazole, etc.), naphthoxazole nuclei (e.g., naphtho(2,1-d)oxazole, naphtho(:1.2-d)oxazole, naphtho(2,3-d)oxazole, 5- Nitronaftho [
2,1-d)oxazole, etc.), oxazoline nucleus (e.g., 4゜4-dimethyloxazoline, etc.), isoxazole nucleus (e.g., 5-methylisoxazole, benzisoxazole, etc.), selenazole nucleus (e.g.,
4-methylselenazole, 4-nitroselenazole, 4
-phenylselenazole), benzoselenazole core (e.g., benzoselenazole, 5-chlorobenzoselenazole, 5-nitrobenzoselenazole, 5-methoxybenzoselenazole, 5-hydroxybenzoselenazole, 6-nitrobenzo selenazole, 5-chloro-6
-nitrobenzoselenazole, etc.), naphthoselenazole cores (e.g., naphtho(2,1-d)selenazole, naphthoI:1,2-d)selenazole, etc.), tellurazole cores (e.g., penzotelllazole, 5- Methylbenzotelllazole, 5,6-dimethylbenzotelllazole,
5-methylthiobenzotelllazole, 5-methoxybenzotelllazole, 5-hydroxybenzotelllazole,
5,6-Simethoxybenzotellazole, naphtho(1,
2-d) tellurazole, 6-medoxynaphtho[:1,2-cl]tellazole, 6-methoxynaphtho[1,2-d]tellazole, etc.), 3,3-dialkylindolenine nucleus (e.g. 3° 3-dimethylindolenine, 3,3-diethylindolenine, 3,3-dimethyl-5-cyanoindolenine, 3,3-dimethyl-
6-Nitroindolenine, 3,3-dimethyl-he-=
k b) 1 no R1 no - - no 11-gufu 44 et al. 11+- to -4L 7 diindolenine, 3
, 3,5-trimethylindolenine, 3,3-dimethyl-5-chloroindolenine, etc.), imidazole core (e.g., 1-alkylimidazole, 1-alkyl-4-
Phenylimidazole, 1-alkylbenzimidazole, 1-alkyl-5-chlorobenzimidazole, 1
-alkyl-5,6-dichlorobenzimidazole, 1
-Alkyl-5-methoxybenzimidazole, 1-alkyl-5-cyanobenzimidazole, ■-alkyl-5-fluorobenzimidazole, 1-alkyl-5
-Trifluoromethylbenzimidazole, 1-alkyl-6-chloro-5-cyanobenzimidazole, ■-
Alkyl-6-chloro-5-trifluoromethylbenzimidazole, 1-alkylnaphtho(1,2-d)imidazole, 1-allyl-5,6-dichlorobenzimidazole, 1-allyl-5-chlorobenzimidazole,
1-aryl-imidazole, ■-arylbenzimidazole, 1-aryl-5-chlorobenzimidazole, 1-aryl-5,6-dichlorobenzimidazole, 1-aryl-5-methoxybenzimidazole, 1
-Aryl-5-cyanobenzimidazole, 1-arylnaphtho(1,2-d)imidazole, where the alkyl group mentioned above has 1 to 8 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, etc. Substituted alkyl groups and hydroxyalkyl groups (eg, 2-hydroxyethyl, 3-hydroxypropyl, etc.) are preferred.

Particularly preferred are methyl group and ethyl group. The aforementioned aryl groups represent phenyl, halogen (e.g. chloro) substituted phenyl, alkyl (e.g. methyl) substituted phenyl, alkoxy (e.g. MeI-xy) substituted phenyl, and the like. ), imidazo(4,5-b)quinoxaline nucleus (e.g. 1,3-diethylimidazo(4,5-b)quinoxaline, 6-chloro-1,3-diallylimidazo(4,5-
b) quinoxaline, etc.), oxadiazole nucleus, thiadiazole nucleus, tetrazole nucleus, pyrimidine nucleus, etc.

The alkyl group represented by R3 and R4 has 1 to 18 carbon atoms, preferably 1 to 7 carbon atoms, particularly preferably 1 to 7 carbon atoms.
4, specifically an unsubstituted alkyl group (
For example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, hexyl, octyl, dodecyl, octadecyl, etc.), and substituted alkyl groups, such as aralkyl groups (e.g. benzyl, 2-phenylethyl, etc.)
, hydroxyalkyl groups (e.g., 2-hydroxyethyl, 3-hydroxypropyl, etc.), carboxyalkyl groups (e.g., 2-carboxyethyl, 3-carboxypropyl, 4-carboxybutyl, carboxymethyl, etc.), alkoxyalkyl groups (e.g., , 2-methoxyethyl, 2-(2-methoxyethoxy)ethyl, etc.),
Sulfoalkyl groups (e.g. 2-sulfoethyl, 3-sulfopropyl, 3-sulfobutyl, 4-sulfobutyl,
2-[3-sulfopropoxy]ethyl, 2-hydroxy-3-sulfopropyl, 3-sulfopropoxyethoxyethyl, etc.), sulfatoalkyl groups (e.g., 3-sulfatopropyl, 4-sulfatobutyl, etc.), complex ring-substituted alkyl groups (e.g. 2-(pyrrolidin-2-one-1-yl)ethyl, tetrahydrofurfuryl, etc.),
2-acetoxyethyl, carbomethoxymethyl, 2-methanesulfonylaminoethyl, vinyl-substituted alkyl group (
For example, allyl group)). L□l LAP L3
is a methine group (unsubstituted or substituted alkyl group (e.g., methyl, ethylbenzyl, etc.), aryl group (e.g., phenyl, etc.), halogen (e.g., chloro, bromo, etc.),
Alternatively, it may be substituted with a negatively charged ketomethylene residue forming a holopolar cyanine dye. It may also form a ring with another L. ). X-E is an inorganic or organic acid anion (eg, chloride, bromide, iodine).

p-h luenesulfonate, p-21-benzenesulfonate, methanesulfonate, methylsulfate,
ethylsulfur-1, perchlorate, etc.).

In general formula (m), at least one of R3 and R4 is preferably an alkyl group substituted with an acid group such as sulfoalkyl or carboxyalkyl.

More preferably, a cyanine dye represented by the following general formula (■) is used.

General formula (■) In the formula, Z3 and Z4 may be the same or different, and each represents an atomic group necessary to form a five-shell heterocycle (including a fused heterocycle), and the heterocycle is represented by the general formula (m)
Thiazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, thiazoline nucleus, oxazole nucleus, benzoxazole nucleus, naphthoxazole nucleus, oxazoline nucleus, inoxazole nucleus, selenazole nucleus, benzoselenazole nucleus, naphthoselenazole nucleus, tellazole nucleus explained in ,
3,3-dialkylindolenine nucleus, imidazole nucleus,
It represents an imidazo(4,5-b)quinoxaline nucleus, an oxadiazole nucleus, a thiadiazole nucleus, a tetrazole nucleus, etc. R5 and R6 have the same meaning as R3 and R4, and at least one of them is an alkyl group substituted with an acid group such as sulfoalkyl or carboxyalkyl.

R4, L,, L, are synonymous with the above-mentioned L + R21R3, X2e is synonymous with xie, p is synonymous with m, and q is synonymous with k.

More preferably, a cyanine dye represented by the following general formula (V) is used.

General formula (V) In the formula, Ql and Q2 may be the same or different, and -0-1-S-1-5e-1-Te-1-N-
(R9 represents the alkyl group or aryl group described for the imidazole nucleus of the general formula (I[[)). t is O
or 1, and when t is 1, + and 1L together represent an atomic group necessary to form a naphthothiazole nucleus, a naphthoxazole nucleus, a naphthoselenazole nucleus, a naphthoterlazole nucleus, and a naphthoimidazole nucleus. U represents 0 or 1, and when U is 1, 2 represents an atomic group necessary to form a naphthothiazole nucleus, a naphthoxazole nucleus, a naphthoselenazole nucleus, a naphthoterlazole nucleus, or a naphthoimidazole nucleus. R7
and R8 are synonymous with the above R5 and R6, R7,
L and R9 are the same as L1. 'L, Andori.

is synonymous with x, 6+ is synonymous with xle, r is m
and S is synonymous with k.

In general formula (V) The heterocycles represented by may be the same or different.

The heterocycle includes, for example, a benzothiazole nucleus (e.g., benzothiazole, 4-chlorobenzothiazole, 5
-Chlorobenzothiazole, 6-chlorobenzothiazole, 5-nitrobenzothiazole.

4-Methylbenzothiazole, 5-methylbenzothiazole, 6-methylbenzothiazole, 5-bromobenzothiazole, 6-bromobenzothiazole, 5-iodobenzothiazole, 5-phenylbenzothiazole, 5
-methoxybenzothiazole, 6-methoxybenzothiazole, 5-ethoxybenzothiazole, 5-ethoxycarbonylbenzothiazolecarpoxybenzothiazole, 5-phenethylbenzothiazole, 5-fluorobenzothiazole, 5-chloro-6-methylbenzothiazole, 5,6-dimethylbenzothiazole, 5-hydroxy-6-methylbenzothiazole, tetrahydrobenzothiazole, 4-phenylbenzothiazole),
Naphthothiazole nuclei (e.g. naphtho(2.1-d)thiazole, naphtho(1.2-d)thiazole, naphtho(
2.3-d) Thiazole, 5-methoxynaphtho (1.2
-d) Thiazole, 7-nitronaphtho [2. 1-d)
Thiazole, 8-methoxynaphtho(2, l-d)thiazole, 5-methoxynaphtho(2,3-d]thiazole, etc.), benzoxazole core (benzoxazole,
5-chlorobenzoxazole, 5-methylbenzoxazole, 5-bromobenzoxazole, 5-fluorobenzoxazole, 5-phenylbenzoxazole, 5-methoxybenzoxazole, 5-nitrobenzoxazole, 5-trifluoromethylbenzoxazole, 5-hydroxybenzoxazole, 5-carboxybenzoxazole, 6-methylbenzoxazole, 6-chlorobenzoxazole, 6-nitrobenzoxazole, 6-methoxybenzoxazole, 6
-hydroxybenzoxazole, 5,6-dimethylbenzoxazole, 4,6-dimethylbenzoxazole, 5-ethoxybenzoxazole, etc.), naphthoxazole nuclei (e.g., naphtho(2.1-d)oxazole, naphtho(1 , 2-d) Oxazole, naphtho [
2.

3-d] oxazole, 5-nitronaphtho (2.1-d
)oxazole etc.), benzoselenazole core (e.g.

benzoselenazole, 5-chlorobenzoselenazole,
5-nitrobenzoselenazole, 5-methoxybenzoselenazole, 5-hydroxybenzoselenazole, 6-
21-benzoselenazole, 5-chloro-6-nitrobenzoselenazole, etc.), naphthoselenazole core (e.g., nando[2,1-d]selenazole, naphtho(1
, 2-d) selenazole), penzotelllazole core (e.g., penzotelllazole, 5-methylbenzotelllazole, 5,6-dimethylbenzotelllazole, 5-
Methylthiobenzotelllazole, 5-methoxybenzotelllazole, 5-hydroxybenzotelllazole, 5,
(e.g., naphtho[1,2-d) telllazole, 6-medoxy8-methylnaf1-(1,2-d)
tellurazole, 6-methoxynaphtho[1゜2-d]tellazole, etc.), benzimidazole core (e.g. 1-
Alkylbenzimidazole, 1-alkyl-5-chlorobenzimidazole, 1-alkyl-5,6-dichlorobenzimidazole, 1-alkyl-5-methoxybenzimidazole, 1-alkyl-5-cyanobenzimidazole, 1-alkyl- 5-fluorobenzimidazole, 1-alkyl-5-trifluoromethylbenzimidazole, 1-alkyl-6-chloro-5-cyanobenzimidazole, 1-alkyl-6-chloro-5-
Trifluoromethylbenzimidazole, 1-allyl-
5,6-dichlorobenzimidazole, 1-allyl-5
-chlorobenzimidazole, 1-arylbenzimidazole, 1-aryl-5-chlorobenzimidazole, 1-aryl-5,6-dichlorobenzimidazole, 1-aryl-5-methoxybenzimidazole,
1-aryl-5-cyanobenzimidazole, etc.),
Naphthoimidazole core (e.g. 1-alkylnaphtho(
1,2-(1) imidazole, 1-arylnaphtho(1
, 2-d) imidazole, etc.). The alkyl groups in the benzimidazole nucleus and naphthoimidazole nucleus described above have 1 to 8 carbon atoms, such as unsubstituted alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, and hydroxyalkyl groups (for example, 2-hydroxyethyl). , 3-hydroxypropyl, etc.) are preferred. Particularly preferred are methyl group and ethyl group. or,
The aryl groups in the aforementioned benzimidazole and naphthimidazole cores represent phenyl, halogen (eg, chloro) substituted phenyl, alkyl (eg, methyl) substituted phenyl, alkoxy (eg, methoxy) substituted phenyl, and the like.

In general formula (V), preferably r represents an integer of 1 to 3, more preferably r represents 2. More preferably, L7 represents =CH-, and L represents -CH= or an alkyl- or aryl-substituted methine group.

More preferably, in addition to the above, Ql and Q2 are turned by -0.

Next, specific examples of cyanine dyes that can be used in the present invention will be shown. However, the present invention is not limited to these specific examples.

e r0 r0 S-21 Br0 -3O S-A S-37 S-38 S-57 8-6O S-S-69 shi2fi, shi, MgThe cyanine dye used in the present invention is a known one. ,Also,
The Chemistry of Heterocyclic Compounders by F. M. Hamer.
Chemistry of Heterocyclic
Compounds) - The Cyanine Die &amp;
Related Compound (The Cyanin)
e Dyesand Re1ated Compound
ds) J John - Willie & Thump
Wiley & 5ons, New York.

London), pp. 86-199 (1964), and JP-A-60-78445.

The sensitizing dye used in the present invention can be directly dispersed into the emulsion. These can also be prepared using a suitable solvent, such as methyl alcohol, ethyl alcohol, methyl cellosolve,
It can also be dissolved in acetone, water, pyridine, or a mixed solvent thereof, and added to the emulsion in the form of a solution. Ultrasonic waves can also be used for dissolution. Moreover, as a method of adding this sensitizing dye, US Patent No. 3,469
A method in which a dye is dissolved in a volatile organic solvent, the solution is dispersed in a hydrophilic colloid, and this dispersion is added to an emulsion, as described in Japanese Patent Publication No. 46-2418.
5, etc., in which a water-insoluble dye is dispersed in a water-soluble solvent without dissolving it, and this dispersion is added to an emulsion; as described in US Pat. No. 3,822,135, a surface-active Dissolve the dye in the agent.

Method of adding the solution into an emulsion; JP-A-51-7462
A method of dissolving a red-shifting compound as described in No. 4 and adding the solution to an emulsion;
A method such as that described in Japanese Patent No. 80826, in which a dye is dissolved in an acid substantially free of water and the solution is added to an emulsion, is used. Other additions to emulsions include U.S. Patent 2,
No. 912,343, No. 3,342,605, No. 2,9
The methods described in No. 96,287 and No. 3,429,835 can also be used. The sensitizing dyes may also be uniformly dispersed in the silver halide emulsion before being coated on a suitable support, but can of course be dispersed at any stage of the preparation of the silver halide emulsion.

That is, it can be added and used at any step in the manufacturing process of a photographic emulsion, or it can be added and used at any stage after manufacturing the emulsion up to just before coating. Examples of the former include silver halide grain formation process, physical ripening process,
These include chemical ripening processes.

The amount of the nitrogen-containing heteroartic ring compound used in the present invention may be an amount sufficient to effectively increase the sensitivity of the emulsion. This amount varies over a wide range depending on the emulsion conditions, but is preferably from 1 x 10-s to 1 x 1 per mole of silver halide.
It is preferable to add 0-2 mol, especially 1 x 10-4 to 1 x 10-3 mol.

Similarly, the amount of cyanine dye added may be sufficient to effectively increase the sensitivity of the emulsion. This amount also varies over a wide range depending on the emulsion conditions, but is preferably from I x 10-' to 5 x 10-3 mol, preferably from 3 x 10-' to 2.5 x 10-3 mol per mol of silver halide. 'In the molar range.

Further, the addition amount of the nitrogen-containing heteroartic ring compound and the cyanine dye to exhibit a supersensitizing effect is preferably 0.05 to 10, particularly 0.05 to 10, in terms of molar ratio of the nitrogen-containing heteroartic ring compound/cyanine dye. 1
It is better to add ~3.

In the photographic emulsion of the present invention, any silver halide including silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide, and silver chloride may be used, but the preferred silver halide is 12 mol. %below,
More preferred is silver iodobromide or silver iodochlorobromide containing 1 to 12 mol % of silver iodide. Particularly preferred are silver iodobromide or silver iodochlorobromide containing from 2 mol % to 10 mol % silver iodide.

The silver halide grains in the photographic emulsion may be so-called regular grains having a regular crystal structure such as a cube, octahedron, or dodecahedron, or may have an irregular crystal shape such as a spherical shape. It may be one with crystal defects such as twin planes or a composite form thereof.

The grain size of silver halide may be fine grains of 0.1 micron or less or large grains with a projected area diameter of up to 10 microns, and may be a monodisperse emulsion with a narrow distribution or a polydisperse emulsion with a wide distribution. good.

The silver halide photographic emulsion of the present invention can be produced by a known method, such as Research Disclosure (RD),
Ha 17643 (December 1978), 22-23
Page, 'Eng.

Emulsion preparation
and types) I' and same, N018716
(November 1979), p. 648.

The photographic emulsion of the present invention is described in "Physics and Chemistry of Photography" by Glafkides, published by Beaumontel (P, Glafkides).

Chimie et Physique Photog
raphique, Paul Montel, 196
7), “Photographic Emulsion Chemistry” by Duffin, published by Focal Press (G, F, Duffin, Photograp
hicEmulsion Chemistry (Fo
cal Press, 1966), Zelikman et al.
"Production and Coating of Photographic Emulsions" published by Focal Press (V,
L., Zelikman at al., Making
andCoating Photographic
Emulsion, Focal Press.

(1964) and others. That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble silver salt with the soluble halogen salt may be any one-sided mixing method, simultaneous mixing method, or a combination thereof. good. A method of forming particles by mixing them with silver ions 'J1'@ (so-called back mixing method) can also be used. PAg in the liquid phase in which silver halide is produced as a form of simultaneous mixing method
The method of keeping constant is the so-called chondral
A double jet method can also be used. According to this method, a silver halide emulsion having a regular crystal shape and a nearly uniform grain size can be obtained.

Two or more types of silver halide emulsions formed separately may be mixed and used.

The silver halide emulsion consisting of the regular grains described above can be obtained by controlling PAg and PH during grain formation. For more information, see Photographic Science and Engineering (Photographic Science and Engineering).
5science and Engineering) Volume 6, pp. 159-165 (1962); Journal
Of Photographic Science (Journal
of Photo-graphfc 5cienc-
e), Vol. 12, pp. 242-251 (1964), U.S. Patent No. 3,655,394 and British Patent No. 1,413,7
It is described in No. 48.

Monodispersed emulsions include silver halide grains with an average grain diameter of greater than about 0.1 micron, at least 9
Emulsions in which 5% by weight are within ±40% of the average grain diameter are typical. The average particle diameter is between 0.25 and 2 microns, and at least 95% by weight or at least 9
Emulsions containing 5% silver halide grains within a range of ±20% of the average grain diameter can be used in the present invention. A method for producing such an emulsion is described in U.S. Pat. No. 3,574,628;
, 655,394 and British Patent 1,413,748
listed in the number. Also, JP-A Nos. 48-8600, 51-39027, 51-83097, 53-
No. 137133, No. 54-48521, No. 54-99
No. 419, No. 58-37635, No. 58-49938
Monodisperse emulsions such as those described in No.

Further, tabular grains having an aspect ratio of 5 or more can also be used in the present invention. Tabular grains are disclosed in U.S. Pat.
No. 4,226, No. 4,414,310, No. 4,433
, No. 048, No. 4,439,520 and British Patent 2
．． It can be easily prepared by the method described in, for example, No. 112,157. U.S. Pat.
, 434, 226, etc.

A tabular emulsion is one of the preferred silver halide emulsions used in the present invention. It is known that tabular grains can improve color sensitization efficiency, but preventing a decrease in inherent sensitivity (hereinafter referred to as "intrinsic desensitization") when adding a sensitizing dye is a critical step during color sensitization. This is thought to lead to a significant increase in sensitivity. In the present invention, it has been discovered that the combined use of a cyanine dye and a nitrogen-containing heteroartic ring compound in a tabular grain silver halide emulsion can surprisingly increase the inherent sensitivity and color sensitization sensitivity. At the same time, the inventors have also discovered that the fog that occurs during storage of photographic light-sensitive materials can be prevented without reducing the sensitivity.

The silver halide emulsion used in the present invention is a tabular grain having an aspect ratio of 5 or more, preferably an aspect ratio of 5 or more and 100 or less, more preferably an aspect ratio of 5 or more and 20 or less. be. The circular diameter of the tabular grains is preferably 0.2 μm to 30 μm, and 0.2 μm to 30 μm.
More preferably 4 μm to 10 μm.

Moreover, the thickness is preferably 0.5 μm or less, and 0.3 μm.
The following are more preferred.

The crystal structure may be uniform, the inside and outside may have different halogen compositions, or it may have a layered structure. These emulsion grains are described in British Patent No. 1,027,14
No. 6, U.S. Patent No. 3,505,068, U.S. Patent No. 4,444,
No. 877 and Japanese Unexamined Patent Publication No. 143331/1984.

Regarding the halogen distribution within the particle, it may have a uniform composition, the inside and outside may have different halogen compositions, or it may have a layered structure, but it is particularly preferable to have a core part of the high iodine layer and a low iodine layer. It is a particle having substantially two distinct layered structures (core/shell structure) consisting of shell parts. An explanation of this particle will be added below.

The clear layered structure mentioned here can be determined by an X-ray diffraction method. An example of applying the X-ray diffraction method to silver halide grains is described in H. Hirsch, Journal of Photographic Science, Vol. 10 (1962), pages 129 onwards. When the lattice constant is determined by the halogen composition, a diffraction peak occurs at a diffraction angle that satisfies Black's condition (2dsinθ=nλ).

Regarding the measurement method of X-ray diffraction, see Basic Analytical Chemistry Course 24 “X
It is described in detail in ``X-ray Analysis'' (Kyoritsu Shuppan) and ``X-ray Diffraction Guide'' (Rigaku Denki Co., Ltd.).

The standard measurement method uses Cu as a target and uses β-rays as a radiation source (tube voltage 40 kV, tube current 60 mA).
) This is a method of determining the diffraction curve of the (220) plane of silver halide. In order to increase the resolution of the measuring device, the width of the slit (divergent slit, light receiving slit, etc.), the time constant of the device,
It is necessary to appropriately select the scanning speed and recording speed of the goniometer and confirm the measurement accuracy using a standard sample such as silicon.

When the emulsion grains have two distinct layered structures, two peaks are generated in the diffraction curve due to the diffraction maximum due to the silver halide in the high iodine layer and the diffraction maximum due to the silver halide in the low iodine layer.

In the present invention, the substantially two distinct layered structures are defined by the diffraction intensity of the (220) plane of silver halide using β-rays with a diffraction angle (2θ) in the range of 38° to 42°. When obtaining the curve of the angle of diffraction, there is a diffraction peak corresponding to a high iodine layer containing 10 to 45 mol% silver iodide, and a diffraction peak corresponding to a low iodine layer containing 5 mol% or less silver iodide. When there are two diffraction maxima and one minimum between them, and the diffraction intensity corresponding to the high iodine layer is 1710 to 3/1 of the diffraction intensity of the peak corresponding to the low iodine layer. means.

More preferably, the diffraction intensity ratio is 115 to 3/1, especially 1/
This is a case of 3 to 3/1.

In the present invention, the emulsion having substantially two distinct layered structures preferably has a diffraction intensity of the minimum value between the two peaks that is 90% of the weaker one of the two diffraction maximums (peaks). It is preferable that it is below.

More preferably 80% or less, particularly preferably 6
It is 0% or less. The method of decomposing a diffraction curve made up of two diffraction components is well known, and is explained in, for example, Experimental Physics Course 11 Lattice Defects (Kyoritsu Edition).

It is also useful to assume that the curve is a function such as a Gaussian function or a Lorentzian function and to analyze it using a curve analyzer manufactured by Du Pont.

Even in the case of an emulsion in which two types of grains having different halogen compositions coexist and do not have a clear layered structure, two peaks appear in the X-ray diffraction.

Such emulsions cannot exhibit the excellent photographic performance obtained with the present invention.

In order to judge whether a silver halide emulsion is an emulsion according to the present invention or an emulsion in which two types of silver halide grains coexist as described above, in addition to the X-ray diffraction method, the EPMA method (E
Electron-Probe Micro Analysis
This is possible by using the zer method).

In this method, a well-dispersed sample is prepared so that the emulsion grains do not come into contact with each other, and then an electron beam is irradiated. Elemental analysis of extremely small parts can be performed by X-ray analysis using electron beam excitation.

By this method, the halogen composition of each particle can be determined by determining the characteristic X-ray intensities of silver and iodine emitted from each particle.

By confirming the halogen composition of at least 50 grains by the EPMA method, it can be determined whether the emulsion is an emulsion according to the present invention.

In the emulsion of the present invention, it is preferable that the iodine content among the grains is more uniform.

When the distribution of iodine content between particles is measured by the EPMA method, the relative standard deviation is 50% or less, further 35% or less,
In particular, it is preferably 20% or less. Preferred halogen compositions of silver halide grains having a clear layered structure are as follows.

A portion of the core is a high iodine silver halide, and the iodine content is preferably between 10 mol % and the solid solubility limit of 45 mol %.

Preferably it is 15 to 45 mol%, more preferably 20 to 45 mol%.

In the core part, the silver halide other than silver iodide may be either silver chlorobromide or silver bromide, but it is preferable that the proportion of silver bromide is high.

The composition of the outermost layer is silver halide containing 5 mol% or less of silver iodide, more preferably silver halide containing 2 mol% or less of silver iodide.

The silver halide other than silver iodide in the outermost layer may be silver chloride, silver chlorobromide or silver bromide, but it is preferable that the proportion of silver bromide is high.

Regarding the total halogen composition, the effect of the present invention is remarkable when the silver iodide content is 12 mol% or less, preferably 1 to 12 mol%, particularly preferably 2 to 10 mol%.

Emulsions with a well-defined layered structure can have a wide grain size distribution, but emulsions with a narrow grain size distribution are preferred. In particular, in the case of normal crystal grains, the size of the grains that account for 90% of the total weight or number of silver halide grains in each emulsion is within ±40%, and further within ±30%, of the average grain size. Dispersed emulsions are preferred.

Emulsions having a clear layered structure can be prepared by selecting and combining various methods known in the field of silver halide photographic materials.

In order to obtain favorable photographic properties in emulsions consisting of silver halide grains having a well-defined layered structure, the core high iodide silver halide must be sufficiently covered by the low iodide shell silver halide.

The required shell thickness varies depending on the particle size, but is 1.0
For large particles of μm or more, 0.1μm or more, 1.0μm
It is desirable that small-sized particles of less than m are covered with a shell thickness of 0.05 μm or more. In order to obtain an emulsion with a clear layered structure, the silver ratio between the core and shell should be 17.
The range is preferably from 5 to 5, more preferably from 175 to 3, and particularly preferably from 175 to 2.

As mentioned above, in the present invention, the silver halide grains are substantially 2
The term "having a clear layered structure" means that two regions with different halogen compositions substantially exist within one particle, with the center side of the endoton being the core portion and the surface side being the shell.

Substantially, the two are the core part and the third region (other than the shell part).
For example, λ means that there may be a layer between the central core part and the outermost shell part.

However, even if such a third region exists, when an X-ray diffraction pattern is obtained as described above, two peaks (two peaks corresponding to a high iodine portion and a low iodine portion) are obtained.
This means that it may exist within a range that does not substantially affect the shape of the .

That is, there is a core region with high iodine content, a middle region, and a shell region with low iodine content, and the X-ray diffraction pattern has two peaks and two peaks.
There is one minimum part between the two peaks, and the diffraction intensity corresponding to the high iodine part is 1710 ~
3/1. Preferably 115 to 3/1, especially 1/3 to 3/1
1, and the minimum portion is less than 90%, preferably less than 80%, especially less than 70% of the smaller of the two peaks, then such silver halide grains have substantially two distinct layered structures. They are particles with a structure.

The same applies when the third region exists inside the core portion.

Further, silver halides having different compositions may be joined by epitaxial joining, and for example, silver halides, rhodan silver,
It may be bonded with a compound other than silver halide, such as lead oxide. These emulsion grains are described in U.S. Pat.
No. 684, No. 4,142,900, No. 4.459,3
No. 53, British Patent No. 2,038,792, US Patent No. 4.
No. 349,622, No. 4,395,478, No. 4,4
No. 33,501, No. 4,463,087, No. 3,65
No. 6,962, No. 3,852,067, JP-A-59-
It is disclosed in No. 162540 and the like.

Also, mixtures of particles of various crystal forms may be used.

The emulsion of the present invention is usually subjected to physical ripening and chemical ripening. Additives used in such processes are described in Research Disclosure Nα17643 and Research Disclosure Nα18716, and the relevant parts are summarized in the table below.

Known photographic additives that can be used in the present invention are also listed in the two Research Disclosures mentioned above, and their locations are shown in the table below.

Additive type RD17643 RD187162
Sensitivity enhancer Same as above 4 Anti-fogging agent and stabilizer Pages 24-25 Page 649 Right column 6 Anti-stinting agent Page 25 Right column 650
Page left to right column 7 Hardener page 26 Page 651 left column 8 Binder
Page 26 Same as above 9 Plasticizer, lubricant
Page 27 Page 650 Right column 10 Coating aid, surfactant Pages 26-27 Same as above 11 Static inhibitor Page 27 Same as above Various color couplers can be used in the clean water invention, and specific examples thereof are mentioned above. Research Disclosure (RD) Nα1764
3. It is described in the patent described in ■-C-G. As dye-forming couplers, the three subtractive primary colors (i.e.
Couplers that give yellow, magenta, and cyan) by color development are important, and specific examples of diffusion-resistant 4-equivalent or 2-equivalent couplers are the aforementioned RD17643. In addition to the couplers described in (1)-C and the patent described in item 9, the following can be preferably used in the present invention.

Typical examples of yellow couplers that can be used in the present invention include hydrophobic acylacetamide and do couplers having a ballast group. Specific examples include U.S. Patent 2,
407,210, 2,875,057 and 3.
No. 265,506, etc. The present invention includes:
The use of two-equivalent yellow couplers is preferred, U.S. Pat.
, No. 408, 194, No. 3,447,928, No. 3,
933,501 and 4,022,620, Japanese Patent Publication No. 58-10739, U.S. Patent No. 4,401,75
No. 2, No. 4,326,024, RD18053 (1
(April 979), British Patent No. 1,425,020, West German Application No. 2,219,917, West German Patent No. 2,261,361
No. 2,329,587 and No. 2,433,81
A representative example of this is the nitrogen atom separation type yellow coupler described in No. 2. α-pivaloylacetanilide couplers have excellent color fastness, especially light fastness, while α-benzoylacetanilide couplers provide high color density.

Magenta couplers that can be used in the present invention include hydrophobic indacylon- or cyanoacetyl-based couplers, preferably 5-pyrazolone- and pyrazoloazole-based couplers, which have a ballast group. The 5-pyrazolone coupler is preferably a coupler in which the 3-position is substituted with an arylamino group or an acylamino group from the viewpoint of the hue and color density of the coloring dye.
No. 11,082, No. 2,343,703, No. 2,60
No. 0,788, No. 2,908,573, No. 3,062
, No. 653, No. 3,152,896 and No. 3,93
6. (Described in US Pat. No. 05, etc.) As a leaving group for a two-equivalent 5-pyrazolone coupler, U.S. Pat.
Particularly preferred are the nitrogen atom leaving groups described in US Pat. No. 4,351,897 or the arylthio groups described in US Pat. Further, the 5-pyrazolone couplers having a ballast group described in European Patent Nos. 73 and 636 provide high color density. Examples of pyrazoloazole couplers include pyrazolobenzimidazoles described in U.S. Pat. No. 3,369,879, preferably U.S. Pat. No. 3,725,06.
Pyrazolo (5,1-C) (1°2.4
] Triazoles, Research Disclosure 24
220 (June 1984) and JP-A-60-3355
Pyrazolotetrazoles and research described in No. 2
Examples include the pyrazolopyrazoles described in Disclosure 24230 (June 1984) and JP-A-60-43659. Imidazo(1,2-b)pyrazoles described in U.S. Pat. No. 4,500,630 are preferable from the viewpoint of low yellow side absorption and light fastness of coloring dyes, and pyrazoles described in European Patent No. 119,8604 are preferable. (1
, 5-b) (1,2°4)triazole is particularly preferred.

Cyan couplers that can be used in the present invention include hydrophobic, diffusion-resistant naphthol and phenolic couplers, such as the naphthol couplers described in U.S. Pat. No. 2,474,293, preferably U.S. Pat. 21
No. 2, No. 4,146,396, No. 4, 228, 2
Typical examples include two-equivalent naphthol couplers of the oxygen atom separation type described in No. 33 and No. 4, 296, and 200. Specific examples of phenolic couplers include U.S. Pat. Nos. 2,369,929 and 2,801,1.
No. 71, No. 2,772,162, No. 2,895,82
It is stated in issue 6 etc. A cyan coupler that is stable against humidity and temperature is preferably used in the present invention, and a typical example thereof is a cyan coupler having an alkyl group higher than ethyl group at the meta-position of the phenol nucleus described in U.S. Pat. No. 3,772,002. Phenolic cyan coupler with U.S. Patent Nos. 2,772,162, 3,758,308, and 4
, No. 126,396, No. 4,334,011, No. 4,
No. 327,173, West German Patent Publication No. 3.329,729 and European Patent No. 121,365, etc.2,
5-Diacylamino substituted phenolic couplers and U.S. Pat. No. 3,446,622, U.S. Pat. No. 4,333,999, U.S. Pat.
Examples include phenolic couplers having a phenylureido group at the 2-position and an acylamino group at the 5-position, as described in No.

In order to correct unnecessary absorption of coloring dyes, it is preferable to use a colored coupler in combination with a color photosensitive material for photographing to perform masking. Yellow-colored magenta couplers described in U.S. Pat. No. 4,163,670 and Japanese Patent Publication No. 57-39413, or U.S. Pat.
Typical examples include the magenta-colored cyan coupler described in No. 8. Other colored couplers are described in the above-mentioned RD17643, items ① to G.

Granularity can be improved by using a coupler in which the coloring dye has an appropriate diffusibility. Such a coupler is
U.S. Patent No. 4,366.237 and British Patent No. 2,12
Specific examples of magenta couplers are given in No. 5,570, and also in European Patent No. 96,570 and German Published Application No. 3, 234.
, No. 533 describes specific examples of yellow, magenta or cyan couplers.

The dye-forming couplers and the special couplers described above may form dimers or more polymers. A typical example of a polymerized dye-forming coupler is U.S. Pat. No. 3,451,820.
No. 4,080,211. Specific examples of polymerized magenta couplers are given in British Patent 2,1.
No. 02,173 and US Pat. No. 4,367.282.

Couplers that release photographically useful residues upon coupling are also preferably used in the present invention. The DIR coupler releasing the development inhibitor is the aforementioned RD17643,
The patent couplers listed in Sections .-F. are useful.

Preferred in combination with the present invention is JP-A-57-
Developer deactivated type represented by No. 151944; US Patent 4
, 248,962 and JP-A-57-154234; JP-A-60-184248
Particularly preferred are JP-A-57-151944, JP-A-58-217932,
These are developer deactivation type DIR couplers described in JP-A-60-218644, JP-A-60-225156, and JP-A-60-233650, and reactive DIR couplers described in JP-A-60-184248 and the like. .

Suitable supports that can be used in the photographic light-sensitive material having the photographic emulsion of the present invention include, for example, the above-mentioned RD, Nα17643
It is described on page 28 of , and from the right column on page 647 to the left column on page 648 of Nα18716.

Photographic materials to which the photographic emulsion of the present invention can be applied include:
Mention may be made of various color and black and white photosensitive materials.

For example, color negative film for photography (general use, movie use, etc.)
, color reversal film (for slides, movies, etc., and may or may not contain couplers), color photographic paper, color positive film (for movies, etc.), color reversal photographic paper, color photosensitive materials for heat development, Color photosensitive materials using the silver dye bleaching method, photosensitive materials for plate making (lith film, scanner film, etc.), X-ray photosensitive materials (direct/indirect medical use, industrial use, etc.), black and white negative film for photography, black and white prints Examples include paper, microphotosensitive materials (for 00M, microfilm, etc.), color diffusion transfer photosensitive materials (DTR), silver salt diffusion transfer photosensitive materials, printout photosensitive materials, and the like.

Exposure for obtaining a photographic image using a photographic light-sensitive material using the photographic emulsion of the present invention may be carried out using a conventional method.

Natural light (sunlight), tungsten electric lamps, fluorescent lamps, mercury lamps, xenon arc lamps, carbon arc lamps, xenon flash lamps, cathode ray tube flying spots, light emitting diodes, laser light (e.g. gas laser, YAG laser, dye laser, semiconductor Any of a variety of known light sources including infrared light, such as lasers, etc., can be used.

Alternatively, exposure may be performed using light emitted from a phosphor excited by electron beams, X-rays, γ-rays, α-rays, or the like. The exposure time is not only the 1/1000 second to 1 second exposure time normally used in cameras, but also the exposure time shorter than 1/1000 second,
For example, 1/10' using a xenon flash lamp or cathode ray tube.
Exposures of ~1/10' seconds can be used, or exposures longer than 1 second can be used. If necessary, the spectral composition of the light used for exposure can be adjusted using a color filter.

Photographic materials to which the photographic emulsion of the present invention can be applied include the aforementioned RD, Nα17643, pages 28-29, and the same, Nα
18716, page 651, left column to right column.

Preferred embodiments of the present invention are as follows.

1) The silver halide photographic emulsion according to claim 1, wherein the silver halide emulsion contains 12 mol% or less of silver iodide and has a core/shell structure. .

2) A silver halide photographic emulsion according to claim 1, characterized in that the silver halide emulsion is a tabular grain having an aspect ratio of 5 or more.63) The cyanine dye is represented by the following general formula (m): The silver halide emulsion according to claim 1, which is a compound represented by the formula:

General formula (In) In the formula, Zl and Z2 each represent an atomic group necessary to form a 5- to 6-membered heterocycle (including a fused heterocycle);
3 and R4 represent an alkyl group which may be the same or different and may be substituted; L□, L2 and L3 represent a methine group which may be the same or different and may be substituted; xlo is an acid Represents an anion. Also, there are 1 or 2
, and m represents an integer of 1 to 4. Note that when k is 1, the above dye forms an inner salt.

4) The silver halide emulsion according to claim 1, wherein the cyan dye is a compound represented by the following general formula (IV).

General formula (IV) In the formula, Z3 and Z4 may be the same or different, and each represents an atomic group necessary to form a 5-membered heterocycle (including a fused heterocycle), and the heterocycle includes a thiazole nucleus. , benzothiazole nucleus, naphthothiazole nucleus, thiazoline nucleus, oxazole nucleus, benzoxazole nucleus, naphthoxazole nucleus, oxazoline nucleus, isoxazole nucleus, selenazole nucleus, benzoselenazole nucleus, naphthoselenazole nucleus, tellazole nucleus, 3,3- dialkylindolenine nucleus, imidazole nucleus, imidazo[4,5-b]
Represents a quinoxaline nucleus, an oxadiazole nucleus, a thiadiazole nucleus, and a tetrazole nucleus. R5 and R6 are.

It represents an alkyl group which may be the same or different and may be substituted, and at least one of them is an alkyl group substituted with an acid group such as sulfoalkyl or carboxyalkyl. L4. L and L6 represent a methine group which may be the same or different and may be substituted, and x2e represents an acid anion. Furthermore, q represents 1 or 2, and p represents 1 to 2.
Represents an integer of 4.

Note that when q is 1, the above dye forms an inner salt.

5) The silver halide emulsion according to claim 1, wherein the cyanine dye is a compound represented by the following general formula (V).

General formula (V) R'R" (x3e), in formula 1, Q
l and Q2 may be the same or different, respectively;
-0-, -3-, -5s-, -Te-, -N- (R' represents an alkyl group or an aryl group). t is O
or 1, and when t is 1, vl together represents an atomic group necessary to form a naphthothiazole nucleus, a naphthoxazole nucleus, a naphthoselenazole nucleus, a naphthoterlazole nucleus, or a naphthoimidazole nucleus. U represents O or 1, and U represents an atomic group necessary to form a naphthothiazole nucleus, a naphthoxazole nucleus, a naphthoselenazole nucleus, a naphthoterlazole nucleus, or a naphthoimidazole nucleus together with the first group. R7
and R8 represent an alkyl group which may be the same or different and may be substituted, and at least one of them is an alkyl group substituted with an acid group such as sulfoalkyl-self-dialkyl. L7. L, and represent a methine group which may be the same or different and may be substituted, and x
, e represents an acid anion. Further, S represents 1 or 2, and r represents an integer of 1 to 4. Note that if S is 1,
The above dyes form internal salts.

6) General formula (
A silver halide photographic emulsion in which r is an integer of 1 to 3 in V).

7) General formula (
A silver halide photographic emulsion in which r is 2 in V).

8) General formula (
In V), L7 and ri are =CH-.

L8 is a silver halide photographic emulsion in which 100 = or an alkyl or aryl substituted methine group.

9) The added amount of the nitrogen-containing heterocyclic compound and the cyanine dye according to claim 1 is from 0.05 to 0.05 in molar ratio of the nitrogen-containing heterocyclic compound (mol)/cyanine dye (mol). 10
A silver halide photographic emulsion.

10) The amount of the nitrogen-containing heterocyclic compound and cyanine dye according to claim 1 is 0.1 to 0.1 in molar ratio of nitrogen-containing heterocyclic compound (mol)/cyanine dye (mol).
3. Silver halide photographic emulsion.

〔Example〕

Examples of the present invention are shown below. However, the present invention is not limited to these examples.

Example 1 On a subbed cellulose triacetate film support,
Sample 101, which is a multilayer color light-sensitive material consisting of each layer having the composition shown below, was prepared.

(Composition of photosensitive layer) The coating amount is the amount expressed in g/rrf of silver for silver halide and colloidal silver, and the amount for coupler.

The amounts of additives and gelatin are expressed in girrf1 units, and the sensitizing dyes are expressed in moles per mole of silver halide in the same layer.

1st layer (antihalation layer) Black colloidal silver ・・・・・・・・・0.2 Gelatin ・・・・・・・・・1.3 Colored coupler C-1・・・・・・・・・0.06 Ultraviolet absorber UV-1・・・・・・・・・0.1 Same as above
UV-Z ・・・・・・・・・0.2 Dispersion oil 04l-1・・・・・・・・・0.01 Same
Upper 0i1-2 ・・・・・・・・・0
．． 01 Second layer (intermediate layer) Gelatin ・・・・・・・・・1.0 Colored coupler C-2・・・・・・・・・0.02 Dispersion oil 0il-1・・・・・・・・・...0.1 Third layer (first red-sensitive emulsion layer) Gelatin ...0.6 Sensitizing dye 5-23 ...1.
OX 10-'sensitizing dye 5-34...
・Old...3. OX 10-'sensitizing dye 5-41
・・・・・・・・・I X10-5 Coupler C
-3...0.06 coupler C-4...
・・・・・・0.06 Coupler C-8・・・・・・・・・
・0.04 Coupler C-2・・・Old・・・0.03 Dispersion oil 0il-1・・・・・・・・・0.03 Same as above 0i1-3・・・・・・・・・0 ．．
012 4th layer (second red-sensitive emulsion layer) Sensitizing dye 5-23 ......I
X 10-'sensitizing dye 5-34...
...3 X 10-4 sensitizing dye 5-41
......I X 10-'Coupler C-3...0.24 Coupler C-4...
......0.24 coupler C-8...
・・0.04 Coupler C-2・・・・・・・・・0.0
4 Dispersion oil 0il-1・・・・・・・・・0.15 Same as above 0i1-3 ・・・・・・・・・
・0.02 5th layer (3rd red-sensitive emulsion layer) Gelatin 1.0 Sensitizing dye 5-23 ・・・・・・・・・I
X 10-'sensitizing dye 5-34...
...3 X 10-4 sensitizing dye 5-41
・・・・・・・・・I X 10-'Coupler C
-6...0.05 Coupler C-7...
...0.1 dispersion oil 0il-1...
...0. O1 same as above 0i1-2
・・・・・・・・・0.05 6th layer (middle layer) Gelatin ・・・・・・・・・1.0 Compound Cpd-A ・・・Old 0.0
3 Dispersion oil 0il-1...old...0.05 same
Upper 0i1-2 ・・・・・・・・・0
．． 05 7th layer (first green-sensitive emulsion layer) Sensitizing dye 5-18 ・・・・・・・・・5
X 10-'sensitizing dye 5-47...
...2 X 10-' sensitizing dye 5-20
...Old...0.3 X 10-' Gelatin ......0.1 Coupler C
-9...0.2 Coupler C-5...
Old...0.03 Coupler C-1...Old...0.03
Dispersion oil 0il-1...0.5 8th layer (second green emulsion layer) Sensitizing dye 5-18...5
×10'''4 sensitizing dye 5-47...
...2 X 10-' sensitizing dye 5-20
......0.3 X 10-' Coupler C-9...0.25 Coupler C-1.
・・・・・・・・・0.03 Coupler C-10・・・・・・
...0.015 coupler C-5...
0.01 Dispersion oil 0il-1・・・・・・・・・0.
2 9th layer (third green-sensitive emulsion layer) Silver iodobromide emulsion (silver iodide 6 mol%, average grain size 0.7 μm) ...... -0,8
5 Gelatin ・・・・・・・・・1.0
Sensitizing dye 5-17 ・・・・・・・・・3
．． 5 X 10-' sensitizing dye 5-58 ・
......1.4 X 10-' coupler C-1
1...0.01 coupler C-12...
・・・・・・0.03 Coupler C-13・・・・・・
・・0.20 Coupler C-1・・・・・・・・・0.0
2 Coupler C-15...0.02 Dispersion oil 0il-1...0.20 Same as above
0i1-2 ・・・・・・・・・・0.
05 10th layer (yellow filter single layer) Gelatin =----, -1, 2 Yellow colloidal silver 0.08 Compound Cpd-8 0. 1 dispersion oil 0il
-1...Old...0.3 11th layer (first blue-sensitive emulsion layer) Gelatin...1.0 Sensitizing dye S-5...・2 X 10-' coupler C-14...0.9 coupler C-5
......0.07 dispersion oil 0il-1...
・・・・・・・・・0.2 12th layer (second blue-sensitive emulsion layer) Gelatin ・・・・・・0.6 擢jF
AF AJ Ce
4-- <71+a Coupler C-14・・・・・・・・・0.25 Dispersion oil 0il
-1...0.07 13th layer (first protective layer) Gelatin...0.8 Ultraviolet absorber UV-1...・0.1 Same as above UV-2・・・・・・・・・0.2 Dispersion oil 0
il-1・・・・・・・・・0.01 dispersion oil 0il
-2・・・・・・・・・0.01 14th layer (second protective layer) Gelatin ・・・・・・・・・0.45
Hardener H-1...0.4 In addition to the above components, a surfactant was added as a coating aid to each layer. 1# Renkin Kaiwari and 1n1 series created as above.
1.9 Next, the chemical structural formulas or chemical names of the compounds used in this example are shown below: UV-1 UV-2: 0i1-1 tricresyl diphosphate 0i1-2: dibutyl phthalate 041-3: phthalic acid Bis(2-ethylhexyl)〇-
3= C-4: C-5: 8C-6: C-7: C-8: C-10: ShiU C-11: C-12: Shiμ C-13: C-14: C00C, H2S (n) C-15: cpct-A: Cpd-B: H-1= CH, =CH-8O2-CH2-NH-sil-12
5cav-1: 5cav-2: ■ The five photographic elements were exposed to light using a tungsten light source (color temperature adjusted to 4800'K with a filter) at a dose of 25CMS, and then heated to 38C according to the processing steps below.
Development processing was performed.

Color development 3 minutes 15 seconds Bleaching 6 minutes 30 seconds Water
Wash and fix for 2 minutes and 10 minutes
Wash with water for 4 minutes and 20 seconds 3
It was stable for 1 minute and 15 seconds. It was 1 minute and 05 seconds.

Color developer Nidethylene 1-liaminepentaacetic acid 1.0 [Sodium sulfite 4.0g Potassium carbonate 30.0g Potassium bromide
1.4g iodizing power, lium
1. Add 3mg hydroxylamine sulfate 2.4g water
1.0Q (pH 10,0) Bleach solution: Ammonium bromide 150.0g Ammonium nitrate io, og Add water 1.0Q (pH 6,0) Fixing solution: Sodium sulfite 4.0g Ammonium thiosulfate aqueous solution (70%) 175.0+nQ
Add 4.6g of sodium bisulfite water to 1.0Q (pH 6.6
) Stable liquid: Formalin (40%) 2. O
Add mQ water 1.0Q Next, samples 102 to 110 were prepared as shown in Table 1 by adding the compound of the present invention or comparative compound A to the fifth layer of sample 101, and exposed and developed in the same manner as sample 101. Processed.

The results are shown in Table 1 based on the fog value and sensitivity value of the Frere (Fresh) performance of sample 101 (immediately after sample preparation).
It was shown to. In addition, samples 101 to 110 were heated at 60°C130
After being stored at %RH for 3 days, it was exposed and developed in the same manner, and the fog and sensitivity were determined and are shown in Table 1.

From Table 1, samples 102, 103, 104, 108, 109 and 110 to which the compound of general formula (I) of the present invention was added
is sample 101 to which the compound of general formula (I) is not added.
It has lower fog, higher sensitivity, and even at 60℃ and 30℃.
It is also shown that the performance change after storage under %RH for 3 days is small. Such an effect was not obtained from samples 105, 106 and 107 to which Comparative Compound A, which was not substituted with -GOON or -803M, was added.

Example 2 Samples 111 to 119 were prepared by adding the compound of general formula (I) of the present invention or Comparative Compound A to the ninth layer of Sample 101 of Example 1, and subjected to the same conditions as Example 1. Sensitometry was carried out, and the obtained results are shown in Table 2 below.

From Table 2, samples 111, 112, 113, 117, 118 and 119 to which the compound of general formula (I) of the present invention was added
is sample 101 to which the compound of general formula (1) is not added.
It has lower fog, higher sensitivity, and improved storage stability.

Such an effect was observed in sample 114.11 to which Comparative Compound A, which was not substituted with 1000M or 13o3M, was added.
No. 5 and 116 could not be obtained.

Example 3 Sample 1202126 was prepared by adding the compound of general formula (1) of the present invention or Comparative Compound A to the 12th layer of Sample 101 of Example 1, and under the same conditions as Example 1. The results of sensitometry are shown in Table 3.

Sample 120.124.125. Samples No. 126 and No. 126 have lower fog, higher sensitivity, and improved storage stability than sample No. 101 to which the compound of general formula (1) was not added. Moreover, such an effect was not observed in Samples 121 to 123 to which Comparative Compound A was added.

Example 4 On a subbed cellulose triacetate film support,
Samples 201 to 230 were prepared by coating a silver halide emulsion layer and a gelatin protective layer having the compositions shown below.

(Emulsion layer) Gelatin 1.0
g/m cyanine dye (sensitizing dye)...
・(Listed in Table 4) Coupler C-6--0.15g/rr
i' coupler C-7...0.30g/m dispersion oil 0il-1-0.03g/rn' dispersion oil
0il-2-.=0.15g/rrl' (protective layer) Gelatin...0.
5 g/m Hardener H-1...0.4 g/rr? A tungsten light source (converted to a color temperature of 4800' by a filter) was used on the resulting photographic element, and an optical filter SC-5 manufactured by Fuji Photo Film Co., Ltd. was used at the exposure amount of IOCMS.
0 (for measuring color sensitization sensitivity) or BPN-42 (for measuring intrinsic sensitivity).

The development process was carried out in the same manner as in Example 1 except that the color development time was changed to 2 minutes and 45 seconds, and the results obtained are shown in Table 4.

Furthermore, in Table 4, fog indicates the measured value, and for the intrinsic sensitivity and color sensitization sensitivity, the sensitivity of sample 203 (log
Relatively shown based on E).

Coupler C-6, C-7, dispersion oil Oil-1, Oj, l-2 and hardener H-1 used in this example are the same as those used in Example 1. Further, the chemical structural formula of a nitrogen-containing heteroartic ring compound for comparison (comparative compound B-J) is shown below.

Comparison compound: Na○3S According to the results in Table 4, the substituent -COOM, or -803
Among the mercap l-compounds having M, it is recognized that the compound having a tetrazole nucleus of general formula (1) has a large supersensitizing effect. In particular, those corresponding to general formula (n) are preferable from the viewpoint of low fog.

Example 5 In Example 4, the tetrazaindene compound (compound X) shown in Table 5 was added to the emulsion layer of Samples 201, 203 and 206.
Samples 201', 203', and 206 further containing
' were prepared respectively.

The obtained sample was subjected to sensitometry in the same manner as in Example 4, and the obtained results are shown in Table 5.

In Table 5, fog shows the measured value, and the sensitivity of sample 203 (log
E) is shown relatively as a base type.

As shown in Table 5, the effects of the present invention are expressed even in the coexistence of tetrazaindenes (eg, compound X).

Moreover, as shown from the results in Table 5, more preferable results were obtained by using tetrazaindenes in combination.

Example 6 The silver iodide content of the silver iodobromide emulsion used in Sample 201.203.206 was 6 mol %, but the average size of the emulsion grains was adjusted to 0.7 μm to minimize the effect of the silver iodide content. Examined.

That is, the silver iodide content of the silver iodobromide emulsions used in the emulsion layers of samples 201, 203, and 206 was changed to the amount shown in Table 6,
The average particle size was adjusted to 0.7 μm, and samples 231~
245 was created.

These samples were tested in the same manner as in Example 4, and the results are shown in Table 6.

In Table 6, fog shows the measured value, and the sensitivity of sample 203 (IOg
Relatively shown based on E).

As shown in Table 6, the emulsion used in combination with the present invention preferably has a silver iodide content of 12 mole percent or less.

As the silver iodide content increases, the degree of supersensitization effect by the compounds of the invention decreases.

Example 7 Samples 246 to 256 were prepared in the same manner as in Example 4 except that in Sample 201 of Example 4, the cyanine dyes and nitrogen-containing heterocyclic compounds shown in Table 7 were used in the emulsion layer.

These samples were exposed and developed in the same manner as in Example 4, and the results obtained are summarized in Table 7.

In addition, in Table 1, fog indicates the measured value, and for the intrinsic sensitivity and color sensitization sensitivity, the sensitivity (log
Relatively shown based on E).

As shown in Table 7, compared to Samples 251 to 256 using Comparative Compounds A, D, and K as nitrogen-containing heterocyclic compounds, when the compound of the present invention was used, the fog value was maintained while maintaining the fog value.
The degree of supersensitization in the intrinsic sensitivity region and color sensitization region was significantly improved.

Example 8 The average grain size of the silver iodobromide emulsion in the emulsion layer used in Sample 201 of Example 4 was adjusted to 0.7 mμ, the grain structure was changed as shown in Table 8, and the effect was investigated. .

These samples were exposed and developed in the same manner as in Example 4, and the results are shown in Table 8.

In Table 8, fog indicates the measured value, and for the intrinsic sensitivity and color sensitization sensitivity, the sensitivity of sample 258 (log
Relatively shown based on E).

As shown in Table 8, when particles with a layered structure (core/shell structure) consisting of a core part with a high iodine content and a shell part with a low iodine content are used, strong color enhancement in the intrinsic sensitivity range and color sensitization range is achieved. The sensory effect was more pronounced.

Example 9 The grain volume of the silver iodobromide emulsion in the emulsion layer used in Sample 201 of Example 4 was kept constant, the aspect ratio was varied, and the amount of cyanine dye and the amount of nitrogen-containing heterocyclic compound were adjusted as appropriate. The effect of aspect 1 to ratio was investigated at the amount that was changed to reach the optimum value.

The aspect ratio of tabular grains was determined as follows. First, the diameter of a circle having an area equal to the projected area of the grain is determined as the diameter of the tabular silver halide grain.

Further, the distance between two parallel planes constituting a tabular silver halide grain is determined as the thickness of the grain.

The ratio of the circular phase diameter to the particle thickness is defined as Aspect 1 to Ratio.

These samples were exposed and developed in the same manner as in Example 4, and the results are shown in Table 9.

In Table 9, fog shows measured values, and intrinsic sensitivity and color sensitization sensitivity are based on the sensitivity of sample 270 (log
Relatively shown based on E).

As shown in Table 9, by using this high aspect ratio silver halide grain, the supersensitization effect in the intrinsic sensitivity range and the color sensitization range was more remarkable.

(Effect of the invention) By using the nitrogen-containing heterocyclic compound represented by the general formula (I) in combination with a cyanine dye, it has become possible to spectral sensitize a silver halide emulsion in a superchromatic sensitization manner. .

Conventional mercapto nitrogen-containing heterocyclic compounds that do not have an acidic group have a development-suppressing effect, but the compounds of the present invention do not have this phenomenon, making it possible to obtain a more pronounced supersensitizing effect. Ta.

Further, the supersensitizing effect of the present invention was sufficiently produced even after aging, and the effect was also obtained in the intrinsic sensitivity range and the color sensitization range.

Furthermore, a silver halide emulsion in the coexistence of tetrazaindenes or with a silver iodide content of 12 mol% or less, a layered structure of a high iodine core part and a low iodine shell part (core/shell structure).
This supersensitizing effect is further increased in silver halide emulsions having a high aspect ratio (aspect ratio of 5 or more).

Claims (1)

[Scope of Claims] 1) A silver halide emulsion containing 12 mol% or less of silver iodide contains a combination of a nitrogen-containing heteroartic ring compound represented by the general formula (I) and a cyanine dye. Silver halide photographic emulsion. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R^1 represents an aliphatic group, aromatic group, or heterocyclic group substituted with at least one -COOM or -SO_3M, M is a hydrogen atom, an alkali metal atom,
Represents quaternary ammonium or quaternary phosphonium. 2) The silver halide photographic emulsion according to claim (1), wherein the nitrogen-containing heteroartic ring compound is a compound represented by the following general formula (II). General formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R^2 is at least one -COOM or -
It represents a phenyl group substituted with SO_3M, and M represents a hydrogen atom, an alkali metal atom, quaternary ammonium or quaternary phosphonium. )