JP2767490B2 - Silver halide emulsion - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a silver halide emulsion, and more particularly to a silver halide emulsion in which the fluctuation of sensitivity due to natural preservation is improved.

(Prior Art) Conventionally, when a silver halide photosensitive material is produced, a technique of adding a sensitizing dye to a silver halide emulsion and expanding the photosensitive wavelength region of the silver halide emulsion to optically sensitize is well known. Have been.

Numerous compounds have been known as spectral sensitizing dyes used for such purposes.
"The Theory of the Photographic Process," edited by James (THJames) (The Theory o
f the Photographic Process (Third Edition), 1966, Macmillan, N, Y, pp. 198-228, cyanine dyes, merocyanine dyes, xanthene dyes, and the like. be able to.

When these sensitizing dyes are usually applied to silver halide emulsions, they must not only broaden the photosensitive wavelength range of the silver halide emulsion but also satisfy the following conditions.

(1) The spectral sensitization range is appropriate.

(2) The sensitization efficiency is good and a sufficiently high sensitivity can be obtained.

(3) No fogging occurs.

(4) Variation in sensitivity due to temperature change during exposure is small.

(5) Other additives, such as stabilizers, antifoggants,
No adverse interaction with coating aids, color formers, etc.

(6) Sensitivity does not change when a silver halide emulsion containing a sensitizing dye is stored. The sensitivity should not fluctuate especially when stored under high temperature and high humidity.

(7) The added sensitizing dye does not diffuse into other photosensitive layers and does not cause color smear (color mixture) after development processing.

The above conditions are important when preparing a silver halide emulsion in a silver halide color photographic light-sensitive material.

However, despite various attempts, it is not easy to prevent a decrease in sensitivity during storage of a raw sample to a sufficiently satisfactory level. In particular, the oxidation potential of a sensitizing dye having an oxidation potential of 0.60 (V _VS S
When a polymethine dye (CE) or a lower base was used, the sensitivity was greatly reduced during storage of a raw sample, and it was difficult to obtain sufficient performance.

A methine dye containing at least one nitrogen atom and having a saturated or unsaturated 5- to 7-membered ring as a substituent has been reported in European Patent Application Publication (EP) 0372573. The membered ring acts as an antifogging agent in the silver halide light-sensitive material, and at least one of the nitrogen atoms contained in the 5- to 7-membered ring has a tautomerism. Only the structure having the following structure is disclosed.

In the nitrogen-containing aromatic polycyclic compound represented by Ar of the present invention described below, the nitrogen atom is formed by tautomerism. It does not act as an antifoggant.

(Problems to be Solved by the Invention) Accordingly, an object of the present invention is to provide a high-sensitivity and less fog increase and a small change in sensitivity during storage under high temperature and / or high humidity (that is, excellent raw preservability). Further, it is to provide a silver halide photographic light-sensitive material.

(Means for Solving the Problems) The above object of the present invention has been achieved by a silver halide emulsion comprising at least one methine dye represented by the following general formula (I).

In the formula, MET represents an atom group having a methine dye structure, Q represents a divalent linking group consisting of an atom or an atomic group containing at least one of a carbon atom, a nitrogen atom, a sulfur atom, and an oxygen atom; ₁ is 1 or 2, l ₂ is 0 or 1,
l ₃ represents 1, 2, 3 or 4.

Ar represents an aromatic group having a polycyclic compound composed of eight or more atoms including at least one nitrogen atom. However, the nitrogen atom is subject to tautomerism. Represents a structure that does not.

Particularly preferably, the oxidation potential of the methine dye represented by the general formula (I) is 0.60 (V _VS SCE) or lower, and more preferably, the MET has a hexamethine merocyanine structure or a heptamethine cyanine structure. is there.

 Hereinafter, the present invention will be described in more detail.

In the general formula (I), the group represented by MET is usually
A cyanine structure formed by connecting a nitrogen-containing heterocycle called a basic nucleus and another nitrogen-containing heterocycle by a conjugated double bond so that they can be conjugated to each other, or a heterocycle called an acidic nucleus and a base In a sex nucleus, a merocyanine structure formed by connecting a carbonyl group in an acidic nucleus and a nitrogen atom in a basic nucleus with a conjugated double bond so as to be conjugated to each other, or a rhodacyanine structure having these structures in combination, Further, it represents an oxonol structure, a hemicyanine structure, a styryl structure, a benzylidene structure and the like.

Examples of these polymethine dyes include, for example, TH
James, “Theory of Photographic Process,” 1977 Ma
cmillan, Chapter 8, DMSturmer “The Chemistry o
f Heterocyclic Compounds "ed.A.Weissberger and E.
C. Taylor, 1977, John Wiley and Sons (New York)
And so on.

Q represents a divalent linking group consisting of an atom or an atomic group including at least one of a carbon atom, a nitrogen atom, a sulfur atom, and an oxygen atom.

Preferably, an alkylene group (eg, methylene group, ethylene group, propylene group, butylene group, pentylene group), an arylene group (eg, phenylene group, naphthylene group), an alkenylene group (eg, ethylene group, propenylene group), a sulfonyl group , A sulfinyl group, a thioether group, an ether group, a carbonyl group, (R ¹ represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group.), A heterocyclic divalent group (for example, 6-chloro-1,3,5-triazine-2,4- Diyl group, pyrimidine-2,4-diyl group, quinoxaline-2,3
-Diyl group) represented by a divalent linking group having 20 or less carbon atoms.

l ₁ represents 1 or 2, l ₂ represents 0 or 1, and l ₃ represents 1, 2, 3 or 4.

Preferably, l ₁ is 1, l ₂ is 0 or 1, and l ₃ is 1 or 2.
Represents

Next, Ar will be described. The definition of aromaticity is described in “Iwanami Physical and Chemical Dictionary, 3rd Edition, Supplemented Edition”, published by Iwanami Shoten (19
1981) P-1258, 1259.

Next, specific examples of the nitrogen-containing polycyclic compound constituting Ar are shown below.

Preferred are the compounds (a) to (h) having a naphthalene skeleton.

 More preferred are the compounds (a) and (b).

As a substituent of these polycyclic compounds, a substituted or unsubstituted alkyl group (for example, methyl, ethyl, propyl, butyl, hydroxyethyl, trifluoromethyl,
Benzyl, sulfopropyl, diethylaminoethyl, cyanopropyl, adamatyl, p-chlorophenethyl, ethoxyethyl, ethylthioethyl, phenoxyethyl,
Carbamoylethyl, carboxyethyl, ethoxycarbonylmethyl, acetylaminoethyl), unsubstituted or substituted alkenyl groups (eg, allyl, styryl), unsubstituted or substituted aryl groups (eg, phenyl, naphthyl, p-carboxyphenyl, 3,5 -Dicarboxyphenyl, m-sulfophenyl, p-acetamidophenyl, 3-caprylamidophenyl, p-sulfamoylphenyl, m-hydroxyphenyl, p-nitrophenyl, 3,5-dichlorophenyl, p-anisyl, o- Anisyl, p-cyanophenyl, pN-methylureidophenyl, m-fluorophenyl, p-tolyl, m-tolyl), an optionally substituted heterocyclic residue (for example, pyridyl, 5-methyl-2-pyridyl, Thienyl), halogen atoms (eg, chlorine, bromine, Element), a cyano group, a carboxyl group, a sulfo group, a carbamoyl group, a sulfamoyl group, a nitro group, an optionally substituted alkoxy group (e.g. methoxy, ethoxy, 2-methoxyethoxy, 2-
Phenylethoxy), an optionally substituted aryloxy group (eg, phenoxy, p-methylphenoxy, p-
Chlorophenoxy), acyl groups (eg, acetyl, benzoyl), sulfonyl groups (eg, methanesulfonyl,
Benzenesulfonyl), an alkyl or arylthio group (eg, methylthio, carboxyethylthio, sulfobutylthio, phenylthio), an alkoxycarbonyl group (eg, methoxycarbonyl), and an aryloxycarbonyl group (eg, phenoxycarbonyl). May be further bonded to MET by a divalent linking group Q or a single bond. Further, a condensed ring (for example, a benzo, naphtho, pyrido condensed ring) may be further condensed to the polycyclic compound.

Further, on these substituents, further, an alkyl group, an alkenyl group, an aryl group, a hydroxy group, a carboxyl group, a sulfo group, a nitro group, a cyano group, a halogen atom, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an acyl group, An acylamino group, a sulfonamino group, a carbamoyl group, a sulfamoyl group, etc. may be substituted.

Further, at least one of these substituents may be bonded to MET by a divalent linking group Q or a single bond. Ar
Is at least one substituent or single bond (Q
_l2 (MET) Combined with ₁ .

The oxidation potential was measured by phase discrimination type second harmonic AC polarography. The details are described below.
Acetonitrile (spectral grade) dried in 4A-1 / 16 molecular sieves was used as a solvent, and normal tetrapropylammonium perchlorate (a special reagent for polarography) was used as a supporting electrolyte. The sample solution is prepared by dissolving the sensitizing dye in acetonitrile containing 0.1 M supporting electrolyte at 10 ^-3 to 10 ^-5 mol / l,
Prior to measurement, a highly alkaline aqueous solution of pyrogallol and ultra-high purity argon gas (99.999
%) For more than 15 minutes. A rotating platinum electrode was used as a working electrode, a saturated calomel electrode (SCE) was used as a reference electrode, and platinum was used as a counter electrode. The reference electrode and the sample solution were connected by a Lugin tube filled with acetonitrile containing 0.1 M supporting electrolyte, and Vycor glass was used for the liquid junction. 25 ° C with the tip of the lugine tube and the tip of the rotating platinum electrode separated from 5mm to 8mm
Was measured. The measurement of the oxidation potential by the above-mentioned phase discrimination oni harmonic AC voltammetry is described in “Journal of Imaging Science” (Journal of I
maging Science), Vol. 30, pages 27-35 (1986).

The hexamethine merocyanine structure preferably used as MET in the present invention is represented by the general formula (II), and the heptamethine cyanine structure is represented by the general formula (III).

In the formula, Z ₁ , Z ₂ and Z ₃ represent an atomic group necessary for forming a 5- or 6-membered nitrogen-containing heterocyclic ring.

D and D 'represent a group of atoms necessary to form an acyclic or cyclic acidic nucleus.

R ₁ , R ₂ and R ₃ represent an alkyl group.

_{L 1, L 2, L 3} , L 4, L 5, L 6, L 7, L 8, L 9, L 10, L 11, L
_{12, L 13, L 14,} L 15, L 16, L 17, L 18, L 19, L 20 and L
₂₁ represents a methine group or a substituted methine group. Further, a ring may be formed with another methine group, or a ring may be formed with an auxochrome.

n ₁ , n ₂ , n ₃ and n ₄ represent 0 or 1.

M ₁ and M ₂ represent a charge neutralizing counter ion, and m ₁ and m ₂ are zero or more required to neutralize the charge in the molecule.

In the general formulas (II) and (III), at least one Ar is substituted via a divalent linking group Q or via a single bond.

Hereinafter, the general formulas (II) and (III) will be described in more detail.

As R ₁ , R ₂ and R ₃ , preferably an unsubstituted alkyl group having 18 or less carbon atoms (eg, methyl, ethyl, propyl, butyl, pentyl, octyl, decyl, dodecyl, octadecyl) or a substituted alkyl group ｛substituent For example, a carboxy group, a sulfo group, a cyano group, a halogen atom (for example, fluorine, chlorine, and bromine), a hydroxy group, an alkoxycarbonyl group having 8 or less carbon atoms (for example, methoxycarbonyl, ethoxycarbonyl, phenoxycarbonyl, Benzyloxycarbonyl), an alkoxy group having 8 or less carbon atoms (eg, methoxy, ethoxy, benzyloxy, phenethyloxy), a monocyclic aryloxy group having 10 or less carbon atoms (for example, phenoxy, p-tolyloxy), Acyloxy groups (eg, acetyloxy, propionyl C), an acyl group having 8 or less carbon atoms (eg, acetyl, propionyl, benzoyl, mesyl), a carbamoyl group (eg, carbamoyl, N, N-dimethylcarbamoyl, morpholinocarbonyl, piperidinocarbonyl), a sulfamoyl group (eg, sulfamoyl) , N, N-dimethylsulfamoyl, morpholinosulfonyl, piperidinosulfonyl), an aryl group having 10 or less carbon atoms (eg, phenyl, 4-chlorophenyl, 4-methylphenyl, α-naphthyl) and having 18 or less carbon atoms Alkyl group.

Preferably, an unsubstituted alkyl group (for example, methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group), a carboxyalkyl group (for example, 2-carboxyethyl group, carboxymethyl group) ) And sulfoalkyl groups (eg, 2-sulfoethyl group, 3-sulfopropyl group, 4-sulfobutyl group, 3-sulfobutyl group). (M ₁ ) m ₁ and (M ₂ ) m ₂ are included in the formula to indicate the presence or absence of a cation or an anion when necessary to neutralize the ionic charge of the dye. Have been. Whether a dye is a cation, an anion, or has a net ionic charge depends on its auxochrome and substituents. Typical cations are inorganic or organic ammonium and alkali metal ions, while the anion can be specifically an inorganic or organic anion, such as a halogen anion (eg, a fluoride ion, Chlorine ion, bromide ion, iodine ion, substituted arylsulfonate ion (for example, p-toluenesulfonic acid ion, p-chlorobenzenesulfonate ion), aryldisulfonate ion (for example, 1,3-benzenedisulfonate ion, 5−
Naphthalene disulfonic acid ion, 2,6-naphthalene disulfonic acid ion), alkyl sulfate ion (for example, methyl sulfate ion), sulfate ion, thiocyanate ion, perchlorate ion, tetrafluoroborate ion, picrate ion, acetate ion, Trifluoromethanesulfonate ion.

Preferably, ammonium ion, iodine ion, p
-Toluenesulfonate ion.

Z _1, as the nuclei by connexion formed on Z ₂ and Z _3, a thiazole nucleus {thiazole nucleus (e.g. thiazole, 4-methylthiazole, 4-phenylene thiazole, 4,5-dimethylthiazol-4,5-diphenyl Enylthiazole), benzothiazole nucleus (for example, benzothiazole, 4-chlorobenzothiazole, 5-chlorobenzothiazole, 6-
Chlorobenzothiazole, 5-nitrobenzothiazole, 4-methylbenzothiazole, 5-methylbenzothiazole, 6-methylbenzothiazole, 5-bromobenzothiazole, 6-bromobenzothiazole, 5-iodobenzothiazole, 5-phenyl Benzothiazole, 5-methoxybenzothiazole, 6-methoxybenzothiazole, 5-ethoxybenzothiazole, 5-ethoxycarbonylbenzothiazole, 5-carboxybenzothiazole, 5-phenethylbenzothiazole, 5
-Fluorobenzothiazole, 5-chloro-6-methylbenzothiazole, 5,6-dimethylbenzothiazole,
5,6-dimethoxybenzothiazole, 5-hydroxy-
6-methylbenzothiazole, tetrahydrobenzothiazole, 4-phenylbenzothiazole), a natotothiazole nucleus (for example, naphtho [2,1-d] thiazole, naphtho [1,2-d] thiazole, naphtho [2,3- d] thiazole, 5-methoxynaphtho [1,2-d] thiazole, 7
-Ethoxynaphtho [2,1-d] thiazole, 8-methoxynaphtho [2,1-d] thiazole, 5-methoxynaphtho [2,3-d] thiazole)｝ thiazoline nucleus (for example, thiazoline, 4-methylthiazoline) , 4-nitrothiazoline), oxazole nucleus ｛oxazole nucleus (eg, oxazole, 4-methyloxazole, 4-nitrooxazole, 5-methyloxazole, 4-phenyloxazole, 4,5-diphenyloxazole, 4-ethyloxazole ), A benzoxazole nucleus (e.g., 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-dimethylbenzothiazole, 5-ethoxybenzoxazole), naphthooxazole nucleus (for example, naphtho [2,1-d] oxazole, naphtho [1,2-d] oxazole, naphtho [2, Three
-D] oxazole, 5-nitronaphtho [2,1-d] oxazole)}, oxazoline nucleus (for example, 4,4-dimethyloxazoline), selenazole nucleus {selenazole nucleus (for example, 4-methylselenazole, 4-nitroselena) Sol, 4-phenyl selenazole), benzo selenazole nucleus (for example, benzo selenazole, 5-chlorobenzo selenazole, 5-nitrobenzo selenazole, 5-
Methoxy benzo selenazole, 5-hydroxy benzo selenazole, 6-nitro benzo selenazole, 5-chloro-6-nitro benzo selenazole, 5,6-dimethyl benzo selenazole), naphtho selenazole nucleus (for example,
Naphtho [2,1-d] selenazole, naphtho [1,2-d] selenazole)}, selenazoline nucleus (eg, selenazoline, 4-methylselenazoline), tellurazole nucleus {terrazole (eg, tellurazole, 4-methyltellurazole) , 4-phenyltellurazole), benzotellurazole nucleus (for example, benzotellurazole, 5-chlorobenzotellurazole, 5-methylbenzotellurazole, 5,6-
Dimethylbenzotellurazole, 6-methoxybenzotellurazole), naphthotellurazole nucleus (for example, naphtho [2,1-d] tellurazole, naphtho [1,2-d] tellurazole)}, tellurazoline nucleus (for example, tellurazoline,
-Methyltellrazoline), a 3,3-dialkylindolenine nucleus (eg, 3,3-dimethylindolenine, 3,3-diethylindolenine, 3,3-dimethyl-5-cyanoindolenine, 3,3-dimethyl -6-nitroindolenine, 3,3
-Dimethyl-5-nitroindolenin, 3,3-dimethyl-5-methoxyindolenine, 3,3,5-trimethylindolenine, 3,3-dimethyl-5-chloroindolenine), imidazole nucleus and indazole nucleus ( For example, 1-
Alkylimidazole, 1-alkyl-4-phenylimidazole, 1-arylimidazole), benzimidazole nucleus (for example, 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), naphthoimidazole nucleus (for example, -alkylnaphtho [1,2- d] imidazole, 1-arylnaphtho [1,2-d] imidazole), wherein the alkyl group has 1 to 8 carbon atoms, for example, methyl, ethyl,
Unsubstituted alkyl groups such as propyl, isopropyl, butyl and the like, and hydroxyalkyl groups (eg, 2-hydroxyethyl, 3-hydroxypropyl) are preferred. Particularly preferred are a methyl group and an ethyl group. The aforementioned aryl group is
Represents phenyl, halogen (eg chloro) substituted phenyl, alkyl (eg methyl) substituted phenyl, alkoxy (eg methoxy) substituted phenyl. ｝, A pyridine nucleus (for example, 2-pyridine, 4-pyridine, 5-methyl-
2-pyridine, 3-methyl-4-pyridine), quinoline nucleus ｛quinoline nucleus (for example, 2-quinoline, 3-methyl-
2-quinoline, 5-ethyl-2-quinoline, 6-methyl-2-quinoline, 6-nitro-2-quinoline, 8-fluoro-2-quinoline, 6-methoxy-2-quinoline, 6
-Hydroxy-2-quinoline, 8-chloro-2-quinoline, 4-quinoline, 6-ethoxy-4-quinoline, 6-
Nitro-4-quinoline, 8-chloro-4-quinoline, 8
-Fluoro-4-quinoline, 8-methyl-4-quinoline, 8-methoxy-4-quinoline, 6-methyl-4-quinoline, 6-methoxy-4-quinoline, 6-chloro-4
-Quinoline), isoquinoline nucleus (for example, 6-nitro-
1-isoquinoline, 3,4-dihydro-1-isoquinoline, 6-nitro-3-isoquinoline)}, imidazo [4,
5-d] quinoxalin nucleus (for example, 1,3-diethylimidazo [4,5-d] quinoxalin, 6-chloro-1,3-diallylimidazo [4,5-d] quinoxalin), oxadiazole nucleus, thiadiazole Examples include a nucleus, a tetrazole nucleus, and a pyrimidine nucleus.

The nucleus formed by Z ₁ , Z ₂ and Z ₃ is preferably a benzothiazole nucleus, a naphthothiazole nucleus, a benzoxazole nucleus, a naphthoxazole nucleus, a benzimidazole nucleus, a 2-quinoline nucleus or a 4-quinoline nucleus. .

D and D 'represent the atoms required to form an acidic nucleus, but can take the form of the acidic nucleus of any common merocyanine dye. In a preferred form, D is a thiocarbonyl group or a carbonyl group, and D 'represents the remaining group of atoms necessary to form an acidic nucleus.

D and D 'together form carbon, nitrogen and chalcogen (typically oxygen, sulfur, selenium, and tellurium)
A 5- or 6-membered heterocyclic ring of atoms can be formed. Preferably, the next core is completed.

2-pyrazolin-5-one, pyrazolidine-3.5-dione, imidazolin-5-one, hydantoin, 2 or 4-thiohydantoin, 2-iminooxazolidine-
4-one, 2-oxazolin-5-one, 2-thiooxazolidin-2,4-dione, isoxazolin-5-one, 2-thiazolin-4-one, thiazolidine-4-one, thiazolidine-2,4- Dione, rhodanine, thiazolidine-2,4-dithione, isorhodanine, indan-
1,3-dione, thiophen-3-one, thiophen-3
-One-1,1-dioxide, indoline-2-one, indoline-3-one, indazolin-3-one, 2-oxoindazolinium, 3-oxoindazolinium,
5,7-dioxo-6,7-dihydrothiazolo [3,2-a] pyrimidine, cyclohexane-1,3-dione, 3,4-dihydroisoquinolin-4-one, 1,3-dioxane-4,6 -The core of dione, barbituric acid, 2-thiobarbituric acid, chroman-2,4-dione, indazolin-2-one or pyrido [1,2-a] pyrimidin-1,3-dione.

More preferably, 3-alkyl rhodanine, 3-alkyl-2-thiooxazolidine-2,4-dione,
It is an alkyl-3-thiohydantoin.

The substituent bonded to the nitrogen atom contained in the nucleus is a hydrogen atom, an alkyl group having 1 to 18, preferably 1 to 7, and particularly preferably 1 to 4 carbon atoms (eg, methyl, ethyl, propyl, isopropyl, butyl) , Isobutyl, hexyl, octyl, dodecyl, octadecyl), substituted alkyl groups (eg, aralkyl groups (eg, benzyl, 2-phenylethyl), hydroxyalkyl groups (eg, 2-hydroxyethyl, 3-hydroxypropyl), carboxyalkyl groups (eg, , 2-carboxyethyl, 3-carboxypropyl, 4-carboxybutyl, carboxymethyl), alkoxyalkoxy groups (eg, 2-methoxyethyl, 2- (2-methoxyethoxy) ethyl), sulfoalkyl groups (eg, 2- Sulfoethyl, 3-sulfopropyl, 3-sulfo Chill, 4-sulfobutyl, 2-
[3-Sulfopropoxy] ethyl, 2-hydroxy-3
-Sulfopropyl, 3-sulfopropoxyethoxyethyl), sulfatoalkyl group (for example, 3-sulfatopropyl, 4-sulfatobutyl), heterocyclic-substituted alkyl group (for example, 2- (pyrrolidin-2-one-1-) Ill)
Ethyl, tetrahydrofurfuryl, 2-morpholinoethyl), 2-acetoxyethyl, carbomethoxymethyl,
2-methanesulfonylaminoethyl｝, an allyl group, an aryl group (eg, phenyl, 2-naphthyl), a substituted aryl group (eg, 4-carboxyphenyl, 4-sulfophenyl, 3-chlorophenyl, 3-methylphenyl),
Heterocyclic groups (eg, 2-pyridyl, 2-thiazolyl) are preferred.

More preferably, an unsubstituted alkyl group (for example, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl), a carboxyalkyl group (for example,
Carboxymethyl, 2-carboxyethyl, and sulfoalkyl groups (eg, 2-sulfoethyl).

_{L 1, L 2, L 3} , L 4, L 5, L 6, L 7, L 8, L 9, L 10, L 11, L
_{12, L 13, L 14,} L 15, L 16, L 17, L 18, L 19, L 20 and L
₂₁ is a methine group or a substituted methine group such as a substituted or unsubstituted alkyl group (eg, a methyl group, an ethyl group,
Carboxyethyl group), substituted or unsubstituted aryl group (for example, phenyl group, o-carboxyphenyl group), heterocyclic group (for example, barbituric acid), halogen atom (for example, chlorine atom, bromine atom), alkoxy group ( For example, methoxy group, ethoxy group), amino group (eg, N, N
-Diphenylamino group, N-methyl-N-phenylamino group, N-methylpiperazino group), alkylthio group (for example, methylthio group, ethylthio group), and the like; and を represents a ring with another methine group. May be formed, or may form a ring with the auxochrome.

L ₂ and L _4, L ₃ and either of the L ₅ represents preferably formed from each other ring. Further, L ₁₂ and L _14, L ₁₃ and L _15, L ₁₄
And one of L ₁₆ is preferably together form a ring.

Particularly preferred ring structures for L ₂ and L ₄ , L ₁₂ and L ₁₄ , and L ₁₄ and L _{16 are} as follows.

Particularly preferred ring structures for L ₃ and L ₅ and L ₁₃ and L _{15 are} as follows.

That is, when L ₃ and L ₅ , L ₁₃ and L ₁₅ form a ring structure, L ₄ and L ₁₄ are preferably an unsubstituted methine group, an unsubstituted alkyl group (eg, methyl), an alkoxy group (eg, Methoxy), an amino group (eg, N, N-diphenylamino), a methine group substituted with a halogen atom (eg, chlorine), or a methine group substituted with an acidic nucleus represented by D and D ′.

 The other L is preferably an unsubstituted methine group.

Further, in general formula (II) and (III), at least one of Q _l2 Ar each is substituted, the substitution position, for example, Z _1, Z ₂ and of the general formula (II) and (III) A 5- or 6-membered nitrogen-containing heterocyclic ring represented by Z ₃ , an acidic nucleus represented by D and D ′, an alkyl group represented by R ₁ , R ₂ and R ₃ , or a methine group represented by L _{1 to} L ₂₁ Either may be used.

Preferably, it is a substitution at the nitrogen atom of the acidic nucleus represented by R ₁ , R ₂ and R ₃ , or D and D ′.

As the spectral sensitizing dye used in the present invention, other cyanine dyes, merocyanine dyes, composite merocyanine dyes, and the like are used. In addition, complex cyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes are used. As the cyanine dye, a simple cyanine dye, a carbocyanine dye, a dicarbocyanine dye, and a tricarbocyanine dye are used.

Typical examples of the polymethine dye represented by the general formula (I) are shown below.
It is not limited to this.

(A) A polymethine dye having an oxidation potential (E _OX (V _VS SCE)) of more than 0.60 (V _VS SCE) (B) Polymethine dye having an E _OX of 0.60 (V _VS SCE) or lower The polymethine dye represented by the general formula (I) used in the present invention can be synthesized based on the method described in the following literature.

a) Heterocyclic Compounds by FM Hamer, Heterocyclic Compo-Cyanine Dye and Related Compounds
unds-Cyanine dyes and related compounds-) "(John Wiley & Sons
(New York, London-1964) b) DMSturmer-
"Heterocyclic Compounds-Special Topics in Heterocyclic Chemistry-
(Heterocyclic Compounds-Special topics in hetero
cyclic chemistry-) ", Chapter 8, Section 4, pp. 482-515 (John Wiley & Sons John Wiley & S
ons-New York, London-, 1977) c) Jurunal Organichi Eskoy Himmy (Zh.O.
rg.Khim.) Vol. 17, No. 1, pp. 167-169 (1981), No. 15
Vol. 2, No. 400-407 (1979), Vol. 14, No. 10, 2214
Pp. 2221 (1978), Vol. 13, No. 11, pp. 2440-2443 (19
77), Vol. 19, No. 10, pp. 2134-2142 (1983), Ukrainsky Himichiesky Jurunal (UKr.Kh
im.Zh.) Vol. 40, No. 6, pp. 625-629 (1974), Himiya Geterotikritieskiv Soedenaini (Khim.G
eterotsikl.soedin.) No. 2, pp. 175-178 (1976),
Russian Patent No. 420643, No. 341823, JP-A-59-217761,
U.S. Patent Nos. 4334000, 3716648, 36283881, 357
3921, European Patents 288261A1, 102781A2, 102781
A2, Tokiko 49-46930.

Also, Q _l2 Ar moiety of an ether bond formation reactions, bond-forming reactions including amide bond forming reactions and ester bond forming reactions can be utilized a method known in organic chemistry. That is, a method of linking the polycyclic moiety represented by Ar with MET, a method of linking the polycyclic moiety represented by Ar to the raw material for synthesis of the polymethine dye and the intermediate, and then performing the dyeing reaction. Any method such as a method of synthesizing a polycyclic moiety represented by Ar after linking a synthesis material and an intermediate of the ring moiety to the polymethine dye moiety may be used, and may be appropriately selected and synthesized. For the synthesis reactions for these linkages,
For example, The Chemical Society of Japan, New Experimental Chemistry Course 14, Synthesis and Reaction of Organic Compounds, Volumes I to V, Maruzen, Tokyo (1977), Yoshiro Ogata, Organic Reaction Theory, Maruzen, Tokyo (1962), LFFieser
You can refer to many books on organic synthesis reactions, such as and M. Fieser, Advanced Organic Chemistry, Maruzen, Tokyo (1962).

(Synthesis Example 1) Synthesis of (1) 0.5 g of 3- (2-carboxymethyl) -3'-ethylthiocyanine iodide and 0.5 g of 4-hydroxyquinoline were added to 50 ml of pyridine, and N, N-dicyclohexylcarbodiimide was added thereto. After adding 1 g and stirring at room temperature for 24 hours, 200 ml of ethyl acetate was added and the precipitated crystals were collected by filtration.

Then, it was purified by silica gel chromatography (eluent: methanol-chloroform: 1/4), and further recrystallized from methanol to obtain 45 mg of yellow crystal (1).

(Synthesis Example 2) Synthesis of (46) Synthesis of 3- (4-quinolyloxycarbonylethyl) rhodanine 3 g of 4-hydroxyquinoline and 2 g of 3-carboxyethylrhodanine were added to 200 ml of tetrahydrofuran, and N, N
-2 g of dicyclohexylcarbodiimide are added and
After stirring for an hour, the resulting insolubles were removed by filtration. Ethyl acetate 1 was added to the filtrate, and the precipitated crystals were collected by filtration.
2.2 g of (4-quinolyloxycarbonylethyl) rhodanine
I got

0.5 g of the rhodanin compound obtained in the synthesis of (46) and 2- {6- (N-acetyl-N-phenylamino) -1,3,5-hexatrienyl} -3-ethyl [1,2-d] 100 ml of methanol and 0.5 ml of triethylamine were added to 0.6 g of naphthothiazolium iodide, and the mixture was refluxed for 1 hour. After cooling, the precipitated crystals were collected by filtration, dissolved in N, N-dimethylformamide, diluted with methanol and precipitated, and then subjected to silica gel column chromatography (eluent: ethyl acetate-chloroform 9: 1). And purified as 35 mg dark blue crystals (4
6) got.

The sensitizing dye used in the present invention is used in an amount of 5 × 10 ^-4 mol to 5 × 10 ^-3 mol, preferably 1 × 10 ^-6 mol, per mol of silver halide.
Mol to 1 × 10 ^-3 mol, particularly preferably 2 × 10 ^-6 mol to 5 mol
It is contained in the silver halide photographic emulsion at a ratio of × 10 ^-4 mol.

The sensitizing dye used in the present invention can be directly dispersed in an emulsion. These can be first dissolved in a suitable solvent, for example, methyl alcohol, ethyl alcohol, methyl cellosolve, acetone, water, pyridine or a mixed solvent thereof, and added to the emulsion in the form of a solution. Also, ultrasonic waves can be used for dissolution.
As a method for adding the infrared sensitizing dye, US Pat.
No. 3,469,987, a method in which a dye is dissolved in a volatile organic solvent, the solution is dispersed in a hydrophilic colloid, and the dispersion is added to an emulsion.
85, etc., a method of dispersing a water-insoluble dye in a water-soluble solvent without dissolving it and adding this dispersion to an emulsion, as described in U.S. Pat. A method in which a dye is dissolved and the solution is added to the emulsion, as described in JP-A-51-74624. As described in JP-A-80826, a method in which a dye is dissolved in an acid substantially free of water and the solution is added to an emulsion is used. In addition, U.S. Pat.Nos. 2,912,343, 3,342,605, and 2,996,287
No. 3,429,835 and the like. The infrared sensitizing dye may be uniformly dispersed in the silver halide emulsion before being coated on a suitable support. It is preferable to add it before the chemical sensitization or in the latter half of the formation of silver halide grains.

Among the polymethine dyes of the present invention, among the dyes that sensitize to red or infrared, the M-band sensitization is preferably performed using the following general formulas (IV), (V), (VI), (VII), (VIII)
Supersensitization by the compound represented by a), [VIIIb], or [VIIIc] is useful.

The supersensitizer represented by the general formula (IV) includes the general formulas (V), (VI), (VII), (VIIIa), (VIIIb),
In combination with a supersensitizer represented by (VIII-c),
The supersensitizing effect can be specifically increased.

General formula (IV) In the formula, A ₁ represents a divalent aromatic residue. R ₉ , R ₁₀ , R ₁₁ and R ₁₂ are each a hydrogen atom, a hydroxyl group, an alkyl group,
Represents an alkoxy group, an aryloxy group, a halogen atom, a heterocyclic nucleus, a heterocyclylthio group, an arylthio group, an amino group, an alkylamino group, an arylamino group, an aralkylamino group, an aryl group or a mercapto group, and these groups are substituted. Is also good.

However, at least one of A ₁ , R ₉ , R ₁₀ , R ₁₁ and R ₁₂ has a sulfo group. X ₁ and Y ₁ and X ₁ ′
And Y ₁ 'represent -CH = and -N =, respectively, and X ₁ and Y ₁ and
At least one of X ₁ 'and Y ₁ ' represents -N =.

More specifically, in the general formula [IV], -A _1- represents a divalent aromatic residue, which is a -SO ₃ M group [where M is a hydrogen atom or a cation providing water solubility (for example, sodium, potassium, etc.) ). As for -A _1- , for example, those selected from the following -A ₂ -or -A _3- are useful. Provided that R ₉ , R ₁₀ , R ₁₁ or R ₁₂ has --SO ₃
When M ₃₁ group is not included, -A ₁ - is -A ₂ - is selected from the group of.

Such. Here, M represents a hydrogen atom or a cation providing water solubility.

R ₉ , R ₁₀ , R ₁₁ and R ₁₂ each represent a hydrogen atom, a hydroxyl group, an alkyl group (preferably having 1 to 8 carbon atoms; for example, methyl, ethyl, n-propyl, n-butyl), an alkoxy group ( The number of carbon atoms is preferably 1 to 8. For example, methoxy, ethoxy, propoxy, butoxy), an aryloxy group (for example, phenoxy, naphthoxy, o-tolyloxy, p-sulfophenoxy), a halogen atom (for example, chlorine or bromine), a heterocyclic nucleus (For example,
Morpholinyl, piperidyl), alkylthio groups (eg, methylthio, ethylthio), heterocyclylthio groups (eg, benzothiazolylthio, benzimidazolylthio,
Phenyltetrazolylthio), an arylthio group (eg, phenylthio, tolylthio), an amino group, an alkylamino group or a substituted alkylamino group (eg, methylamino, ethylamino, propylamino, dimethylamino,
Diethylamino, dodecylamino, cyclohexylamino, β-hydroxyethylamino, di- (β-hydroxyethyl) amino, β-sulfoethylamino), an arylamino group, or a substituted arylamino group (eg, anilino, o-sulfoanilino, m- Sulfoanilino, p-
Sulfoanilino, o-toluidino, m-toluidino, p
-Toluidino, o-carboxyanilino, m-carboxyanilino, p-carboxyanilino, o-chloroanilino, m-chloroanilino, p-chloroanilino, p-
Aminoanilino, o-anisidino, m-anisidino, p
-Anisidino, o-acetaminoanilino, hydroxyanilino, disulfophenylamino, naphthylamino, sulfonaphthylamino), heterocyclylamino group (for example, 2-benzothiazolylamino, 2-pyridyl-amino), substitution Or an unsubstituted aralkylamino group (eg, benzylamino, o-anisylamino, m-anisylamino, p-anisylamino), an aryl group (eg, phenyl), and a mercapto group.

R ₉ , R ₁₀ , R ₁₁ and R ₁₂ may be the same or different from each other. When -A ₁ -is selected from the group of -A _2- ,
At least one of R ₉ , R ₁₀ , R ₁₁ and R ₁₂ needs to have the above sulfo group (which may be a free acid group or may form a salt). X ₁ and Y ₁ and X ₁ , Y ₁ ′ are −
CH = or -N =, preferably X ₁ , X ₁ ′ is -CH
=, Y ₁ , Y ₁ ′ are -N =.

Next, specific examples of the compound included in the general formula [IV] used in the present invention will be described. However, the present invention is not limited only to these compounds.

(IV-1) 4,4'-bis [2,6-di (2-naphthoxy) pyrimidin-4-ylamino] stilbene-2,2'-disulfonate disodium salt (IV-2) 4,4'- Bis [2,6-di (2-naphthylamino)
Pyrimidin-4-ylamino] stilbene-2,2'-disulfonate disodium salt (IV-3) 4,4'-bis (2,6-dianilinopyrimidine-4
-Ylamino) stilbene-2,2'-disulfonate disodium salt (IV-4) 4,4'-bis [2- (2-naphthylamino)-
6-anilinopyrimidin-4-ylamino] stilbene-2,2'-disulfonic acid disodium salt (IV-5) 4,4'-bis [2,6-diphenoxypyrimidine-
4-ylamino] stilbene-2,2'-disulfonic acid ditriethylammonium salt (IV-6) 4,4'-bis [2,6-di (benzimidazolyl-
2-thio) pyrimin-4-ylamino] stilbene-2,
Disodium salt of 2'-disulfonate (IV-7) 4,4'-bis [4,6-di (benzothiazolyl-2
-Thio) pyrimidin-2-ylamino] stilbene-2,
Disodium salt of 2'-disulfonate (IV-8) 4,4'-bis [4,6-di (benzothiazolyl-2
-Amino) pyrimidin-2-ylamino] stilbene-
Disodium 2,2'-disulfonate (IV-9) 4,4'-bis [4,6-di (naphthyl-2-oxy) pyrimidin-2-ylamino] stilbene-2,2 '
Disodium disulfonate (IV-10) 4,4'-bis (4,6-diphenoxypyrimidin-2-ylamino) stilbene-2,2'-disulfonate disodium salt (IV-11) 4, 4'-bis (4,6-diphenylthiopyrimidin-2-ylamino) stilbene-2,2'-disulfonate disodium salt (IV-12) 4,4'-bis (4,6-dimethylcaptopyrimidine) -2-ylamino) biphenyl-2,2'-disulfonic acid disodium salt (IV-13) 4,4'-bis (4,6-dianilino-triazin-2-ylamino) stilbene-2,2'-disulfonic acid Disodium salt (IV-14) 4,4'-bis (4-anilino-6-hydroxy-triazin-2-ylamino) stilbene-2,2'-
Disodium disulfonate (IV-15) 4,4'-bis [4,6-di (naphthyl-2-oxy) pyrimidin-2-ylamino] bibenzyl-2,2 '
Disodium disulfonate (IV-16) 4,4'-bis (4,6-dianilinopyrimidine)
2-ylamino) stilbene-2,2'-disulfonic acid disodium salt (IV-17) 4,4'-bis [4-chloro-6- (2-naphthyloxy) pyrimidin-2-ylamino] biphenyl-
Disodium 2,2'-disulfonate (IV-18) 4,4'-bis [4,6-di (1-phenyltetrazolyl-5thio)) pyrimidin-2-ylamino] stilbene-2, Disodium salt of 2'-disulfonate (IV-19) Disodium salt of 4,4'-bis [4,6-di (benzimidazolyl-2-thio) pyrimidin-2-ylamino] stilbene-2,2'-disulfonate (IV-20) 4,4'-bis (4-naphthylamino-6-anilino-triazin-2-ylamino) stilbene-2,
2'-Disulfonate disodium salt Among these specific examples, (IV-1) to (IV-6) are preferable, and particularly (IV-1), (IV-2), (IV-4), (IV -Five),
(IV-9), (IV-15) and (IV-20) are preferred.

The compound represented by the general formula [IV] is used in an amount of 0.01 to 5 g per mol of silver halide, and it is 1/1 to 1/100, preferably 1/2 to 1/100 by weight ratio to the sensitizing dye. There are advantageous usages in the 50 range. Further, it is preferable to use the compound represented by the general formula [V] in combination.

Next, the compound represented by formula (V) will be described.

General formula (V) In the formula, Z ₁₁ represents a non-metallic atomic group necessary for completing a 5- or 6-membered nitrogen-containing heterocyclic ring. This ring may be fused with a benzene or naphthalene ring. For example, thiazoliums {eg, thiazolium, 4-methylthiazolium, benzothiazolium, 5-methylbenzothiazolium, 5-chlorobenzothiazolium, 5-methoxybenzothiazolium, 6-methylbenzothiazolium , 6-
Methoxybenzothiazolium, naphtho [1,2-d] thiazolium, naphtho [2,1-d] thiazolium}, oxazoliums {eg oxazolium, 4-methyloxazolium, benzoxazolium, 5-chlorobenzoxa Zolium, 5-phenylbenzoxazolium, 5
-Methylbenzoxazolium, naphtho [1,2-d] oxazolium}, imidazoliums {e.g., 1-methylbenzimidazolium, 1-propyl-5-chlorobenzimidazolium, 1-ethyl-5,6-si Chlorobenzimidazolium, 1-allyl-5-trifluoromethyl-
6-chloro-benzimidazolium), selenazoliums [e.g. benzoselenazolium, 5-chlorobenzoselenazolium, 5-methylbenzoselenazolium, 5-
Methoxybenzoselenazolium and naphtho [1,2-d] selenazolium]. R ₁₃ represents a hydrogen atom, an alkyl group (preferably having 8 or less carbon atoms, for example, methyl, ethyl, propyl, butyl, pentyl) or an alkenyl group (for example, an allyl group). R ₁₄ represents a hydrogen atom or a lower alkyl group (eg, a methyl or ethyl group).
R ₁₃ and R ₁₄ may be substituted alkyl groups. X ₂ ^— represents an acid anion (eg, Cl ⁻ , Br ⁻ , I ⁻ , ClO ₄ ⁻ ). Preferably in the Z ₁₁ are thiazolium compounds are advantageously used. More preferably, substituted or unsubstituted benzothiazolium or naphthothiazolium is advantageously used. These groups and the like include those substituted even if not specifically mentioned.

Specific examples of the compound represented by the general formula [V] are shown below. However, the present invention is not limited to only these compounds.

The compound represented by formula [V] used in the present invention is advantageously used in an amount of about 0.01 to 5 grams per mole of silver halide in the emulsion.

A polymethine dye represented by the general formula (I),
The ratio (weight ratio) to the compound represented by the general formula [V] is preferably in the range of 1/1 to 1/300 of the dye represented by the general formula [I] / the compound represented by the general formula [V]. In particular, the range of 1/2 to 1/50 is advantageously used.

The compound represented by the general formula [V] used in the present invention can be directly dispersed in the emulsion, or a suitable solvent (eg, water, methyl alcohol, ethyl alcohol, propanol, methyl cellosolve, acetone, etc.)
Alternatively, these solvents can be dissolved in a mixed solvent using a plurality of solvents and added to the emulsion. The sensitizing dye can be added to the emulsion in the form of a solution or a dispersion in a colloid according to the method of adding the sensitizing dye.

The compound represented by the general formula [V] may be added to the emulsion before or after the addition of the sensitizing dye represented by the general formula [I]. Further, the compound of the general formula [V] and the sensitizing dye represented by the general formula [I] may be separately dissolved and added separately and simultaneously to the emulsion, or they may be mixed and then added to the emulsion. You may.

Advantageously, the combination of the infrared sensitizing dye represented by the general formula [I] of the present invention and the compound represented by the general formula [V] is preferably combined with a compound represented by the general formula [IV]. Can be

In the infrared-sensitized high silver chloride emulsion of the present invention, when a heterocyclic mercapto compound is used together with a supersensitizer represented by the general formula [IV] or [V], in addition to sensitization and suppression of fog, In addition, the stabilization of the latent image and the dependence of the gradation linearity on the development processing are remarkably improved.

For example, the heterocyclic compound contains a thiazole ring, an oxazole ring, an oxazine ring, a thiazole ring, a thiazoline ring, a selenazole ring, an imidazole ring, an indoline ring, a pyrrolidine ring, a tetrazole ring, a thiadiazole ring, a quinoline ring or an oxadiazole ring. It is a compound having a substituted mercapto group. Particularly, a compound into which a carboxyl group, a sulfo group, a carbamoyl group, a sulfamoyl group, or a hydroxyl group is introduced is preferable. Japanese Patent Publication No. 43-2883 discloses that a mercaptoheterocyclic compound is used as a supersensitizer. In the present invention, a remarkable antifogging effect and a supersensitizing effect are exhibited particularly when used in combination with the compound represented by the general formula [V]. Among them, mercapto compounds represented by the following general formulas [VI] and [VII] are particularly preferred.

General formula (VI) In the formula, R ₁₅ represents an alkyl group, an alkenyl group or an aryl group. X ₃ represents a hydrogen atom, an alkali metal atom, an ammonium group or a precursor. The alkali metal atom is, for example, a sodium atom, a potassium atom,
The ammonium group is, for example, a tetramethylammonium group or a trimethylbenzylammonium group. The precursor is a group that can be X ₆₁ ＨH or an alkali metal under alkaline conditions, and represents, for example, an acetyl group, a cyanoethyl group, or a methanesulfonylethyl group.

Among the above R _15, an alkyl group and the alkenyl group comprises unsubstituted body and substitutions, including further cycloaliphatic group. Examples of the substituent of the substituted alkyl group include a halogen atom, a nitro group, a cyano group, a hydroxyl group, an alkoxy group, an aryl group,
Acylamino group, alkoxycarbonylamino group, ureido group, amino group, heterocyclic group, acyl group, sulfamoyl group, sulfonamide group, thioureido group, carbamoyl group, alkylthio group, arylthio group, heterocyclic thio group, and even carboxylic acid Groups, sulfonic acid groups or salts thereof, and the like.

The above-mentioned ureido group, thioureido group, sulfamoyl group, carbamoyl group and amino group each include unsubstituted, N-alkyl-substituted and N-aryl-substituted ones. Examples of the aryl group include a phenyl group and a substituted phenyl group. Examples of the substituent include an alkyl group and substituents of the above-listed alkyl groups.

General formula (VII) In the formula, Y ₂ is an oxygen atom, a sulfur atom, ＝ NH, _NN- (L ₅₇ ) _n14
-R ₁₇ , L ₅₆ and L ₅₇ represent a divalent linking group, and R ₁₆ and R
₁₇ represents a hydrogen atom, an alkyl group, an alkenyl group or an aryl group. The alkyl group, alkenyl group and aryl group represented by R ₁₆ and R _{17 have} the same meaning as R _{15 in} formula [VI]. X ₄ has the same meaning as X _{3 in} formula [VI].

Specific examples of the divalent linking group represented by L ₅₆ and L ₅₇ above include: Combinations of these can be mentioned.

n ₁₃ and n ₁₄ represents 0 or _{1, R 18, R 19,} R 20, R 21, R
₂₂ , R ₂₃ , R ₂₄ , R ₂₅ and R ₂₆ each represent a hydrogen atom, an alkyl group or an aralkyl group.

Any layer in the silver halide photographic material, that is,
It is contained in photosensitive and non-photosensitive hydrophilic colloid layers.

When the compound represented by the general formula [VI] or the general formula [VII] is contained in a silver halide photographic light-sensitive material, the amount thereof is 1 × 10 ^{−5 to} 5 × per mol of silver halide.
It is preferably 10 ^-2 mol, more preferably 1 × 10 ^-4 to 1 × 10 ^-2 mol. Also, as an antifoggant in a color developer,
1 × 10 ^-6 to 1 × 10 ^-3 mol / 1, further 5 × 10 ^{-6 to} 5 × 10 ^-4
It is possible to add about mol / 1.

Specific examples of the compounds represented by the general formulas [VI] and [VII] are listed below, but the invention is not limited thereto. The compounds described in JP-A-62-269957, pages 4 to 8 of the specification can be mentioned, and the following compounds are particularly preferred.

Further, the polymethine dye according to the present invention may be used as a supersensitizer by condensation of a substituted or unsubstituted polyhydroxybenzene represented by the following general formulas (VIIIa), (VIIIb) and (VIIIc) with formaldehyde. Condensates of 2 to 10 units are useful. Further, there is an effect that the regression of the latent image with the passage of time is prevented, and a decrease in the gradation is also prevented.

In the formula, R ₂₇ and R ₂₈ are each OH, OM ′, OR ₃₀ , NH ₂ , N
_{HR 30, -N (R 30)} 2, represent -NHNH ₂ or -NHNHR _30.

However R ₃₀ represents an alkyl group (1-8 carbon atoms), an allyl group or an aralkyl group.

M 'represents an alkali metal or an alkaline earth metal.

R ₂₉ represents OH or a halogen atom.

n ₁₅ and n ₁₆ each represent 1, 2 or 3.

Next, specific examples of the substituted or unsubstituted polyhydroxybenzene, which is a condensation component of the aldehyde condensate used in the present invention, will be shown, but the present invention is not limited thereto.

(VIII-1) β-resorcinic acid (VIII-2) γ-resorcinic acid (VIII-3) 4-hydroxybenzoic acid hydrazide (VIII-4) 3,5-hydroxybenzoic acid hydrazide (VIII-5) p-chloro Phenol (VIII-6) sodium hydroxybenzenesulfonate (VIII-7) p-hydroxybenzoic acid (VIII-8) o-hydroxybenzoic acid (VIII-9) m-hydroxybenzoic acid (VIII-10) p-dioxy Benzene (VIII-11) Gallic acid (VIII-12) Methyl p-hydroxybenzoate (VIII-13) O-hydroxybenzenesulfonic acid amide (VIII-14) N-ethyl-o-hydroxybenzoic acid amide (VIII-15) N-diethyl-o-hydroxybenzoic acid amide (VIII-16) o-Hydroxybenzoic acid-2-methylhydrazide More specifically, it can be selected from derivatives of the compounds represented by formulas (IIa), (IIb) and (IIc) described in JP-B-49-49504.

(Silver Halide Emulsion) The silver halide emulsion that can be used in the present invention may contain any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride. .

Silver halide grains are cubic, octahedral, tetrahedral, diamond 12
It may have a regular crystal such as a facet, or may have an irregular crystal such as a sphere or plate.
lar) crystalline form or a compound form of these crystalline forms. It may consist of a mixture of particles of different crystal forms.

As the plate-like particles, the thickness is 0.5 microns or less,
Tabular grains having a grain size of preferably 0.3 μm or less, preferably 0.6 μm or more, and having an average aspect ratio of 5 or more occupy 50% or more of the total projected area.

The silver halide grains may have different phases between the inside and the surface layer, or may consist of a uniform phase. Also, the grains may be such that a latent image is mainly formed on the surface (for example, a negative emulsion), or the grains may be mainly formed inside the grains (for example, an internal latent image type emulsion).

Hereinafter, preferred silver halide emulsions in the invention will be described in detail.

The silver halide emulsion according to the present invention has a high sensitivity and a particularly high latent sensitivity by spectrally sensitizing an infrared wavelength region by providing a structure of silver halide grains, particularly, a localized phase on the surface thereof. Image stability can be obtained. In particular, the use of supersensitization techniques can provide latent image stability to an acceptable degree even in high silver chloride emulsions. This is a surprising feature.

The silver halide used in the present invention includes silver chloride,
Silver bromide, silver (iodo) chlorobromide, silver iodobromide and the like can be used, but particularly for the purpose of rapid processing, the silver chloride content substantially not containing silver iodide is 90 mol% or more, More than 95%,
Particularly, it is preferable to use a silver chlorobromide or silver chloride emulsion of 98% or more.

The photosensitive material according to the present invention has a hydrophilic colloid layer for the purpose of improving the sharpness and the like of an image.
No. 337,490A2, pp. 27-76, a dye capable of being decolorized by treatment (among others, an oxonol dye) is used as the photosensitive material.
Titanium oxide surface-treated with dihydric alcohol (for example, trimethylolethane) or the like is added to the water-resistant resin layer of the support so that the optical reflection density at 0 nm becomes 0.70 or more. Wt% or more (more preferably 14 wt%
Above).

Further, in the light-sensitive material according to the present invention, it is preferable to use a color image preservability improving compound as described in European Patent EP 0,277,589A2 together with a coupler. In particular, combination use with a pyrazoloazole coupler is preferred.

That is, the compound (F) which forms a chemically inert and substantially colorless compound by chemically bonding with the aromatic amine-based developing agent remaining after the color developing process and / or the aromatic compound remaining after the color developing process. The compound (G) which forms a chemically inert and substantially colorless compound by chemically bonding with an oxidized form of an aromatic amine color developing agent can be used simultaneously or alone, for example, in storage after processing. It is preferable in order to prevent the generation of stains and other side effects due to the formation of a coloring dye due to the reaction between the color developing agent or its oxidized product and the coupler remaining in the film.

Further, to the photosensitive material according to the present invention, a fungicide such as that described in JP-A-63-271247 is added in order to prevent various molds and bacteria that propagate in the hydrophilic colloid layer and deteriorate the image. Is preferred.

Further, as the support used in the light-sensitive material according to the present invention, a white polyester-based support for a display or a support in which a layer containing a white pigment is provided on a support having a silver halide emulsion layer is used. May be used. In order to further improve the sharpness, an antihalation layer is preferably provided on the support on the side where the silver halide emulsion layer is coated or on the back surface. In particular, the transmission density of the support is preferably set in the range of 0.35 to 0.8 so that the display can be viewed with both reflected light and transmitted light.

The photosensitive material according to the present invention may be exposed to visible light or infrared light. The exposure method may be low-illuminance exposure or high-illuminance short-time exposure. In the latter case, a laser scanning exposure method in which the exposure time per pixel is shorter than 10 ^-4 seconds is preferred.

In the exposure, it is preferable to use a band stop filter described in US Pat. No. 4,880,726.
As a result, light color mixing is removed, and color reproducibility is significantly improved.

The exposed light-sensitive material can be subjected to conventional black-and-white or color development processing. In the case of a color light-sensitive material, bleach-fix processing is preferably performed after color development for the purpose of rapid processing. Particularly when the high silver chloride emulsion is used, the pH of the bleach-fixing solution is preferably about 6.5 or less, more preferably about 6 or less, for the purpose of accelerating desilvering.

Silver halide emulsions and other materials (additives, etc.) and photographic constituent layers (layer arrangement, etc.) applied to the light-sensitive material according to the present invention, and processing methods and processing applied to process this light-sensitive material As the additives, those described in the following patent publications, in particular, EP 0,355,660 A2 (Japanese Patent Application No. 1-107011) are preferably used.

Hereinafter, the dye will be described in more detail.

In a silver halide photographic material, a photographic emulsion layer and other hydrophilic colloid layers are often colored in order to absorb light in a specific wavelength range.

When it is necessary to control the spectral composition of the light to be incident on the photographic emulsion layer, a colored layer is usually provided on the side farther from the support than the photographic emulsion layer. Such a colored layer is called a filter layer. When there are a plurality of photographic emulsion layers, the filter layer may be located between them.

An image based on light scattered when passing through or after transmission through the photographic emulsion layer is reflected at the interface between the emulsion layer and the support or at the surface of the photosensitive material opposite to the emulsion layer and re-enters the photographic emulsion layer. For the purpose of preventing blurring or halation, a colored layer called an antihalation layer is provided between the photographic emulsion layer and the support or on the surface of the support opposite to the photographic emulsion layer. When there are a plurality of photographic emulsion layers, an antihalation layer may be provided between the layers.

Coloring of the photographic emulsion layer is also performed to prevent a reduction in image sharpness due to light scattering in the photographic emulsion layer (this phenomenon is generally called irradiation).

These hydrophilic colloid layers to be colored usually contain a dye. This dye must satisfy the following conditions.

(1) To have appropriate spectral absorption according to the purpose of use.

(2) Photochemically inert. That is, the performance of the silver halide photographic emulsion layer is adversely affected in a chemical sense,
For example, do not give a decrease in sensitivity, regression of latent images, or fog.

(3) No decoloration during the photographic processing or elution into the processing solution or washing water, leaving no harmful coloring on the processed photographic light-sensitive material.

(4) Do not diffuse from the dyed layer to other layers.

(5) It is excellent in stability over time in a solution or a photographic material and does not discolor.

In particular, when the coloring layer is a filter layer or an antihalation layer on the same side of the support as the photographic emulsion layer, those layers are selectively colored, and the other layers are colored. Often need to be substantially below. This is because otherwise, not only does it have a detrimental spectral effect on other layers, but it also diminishes its effect as a filter layer or antihalation layer. However, when the layer containing the dye and the other hydrophilic colloid layer come into contact with each other in a wet state, a part of the dye often diffuses from the former to the latter. The following method is effective for preventing such dye diffusion.

For example, U.S. Pat.No. 2,548,564 discloses a method in which a hydrophilic polymer having a charge opposite to that of a dissociated anionic dye coexists in a layer as a mordant, and the dye is localized in a specific layer by interaction with a dye molecule. 4,124,386, 3,625,
No. 694 and the like.

Further, a method of dyeing a specific layer using a water-insoluble dye solid is described in JP-A-56-12639, JP-A-55-155350, and JP-A-55-15.
No. 5351, No. 63-27838, No. 63-197943, European Patent 15,60
It is disclosed in No. 1.

Further, a method of dyeing a specific layer using metal salt fine particles having a dye adsorbed thereto is disclosed in U.S. Pat.Nos. 2,719,088 and 2,496,841.
No. 2,496,843 and JP-A-60-45237.

Dyes used for such purposes include, for example, British Patent Nos. 506,385, 1,177,429, 1,311,884,
38,799, 1,385,371, 1,467, 214, 1,433,1
No. 02, No. 1,553,516, JP-A-48-85,130, No. 49-114,4
No. 20, 52-117, 123, 55-161, 233, 59-111, 640
No., Japanese Patent Publication No. 39-22,069, No. 43-13,168, No. 62-273527
No. 3,247,127, U.S. Pat.No. 3,469,985, U.S. Pat.
Oxonol dyes having a pyrazolone nucleus or a barbituric acid nucleus described in US Pat. No. 2,533,472
No. 3,379,533; British Patent No. 1,278,621;
13447, other oxonol dyes described in 1-183652, etc., British Patent Nos. 575,691, 680,631, 59
9,623, 786,907, 907,125, 1,045,609,
U.S. Pat.No. 4,255,326, azo dyes described in JP-A-59-211,043 and the like, JP-A-50-100,116, JP-A-54-118,247
No. 2,014,598, azomethine dyes described in 750,031, etc., anthraquinone dyes described in U.S. Pat.No. 2,865,752, U.S. Pat.Nos. 2,538,009, 2,6
88,541, 2,538,008, UK Patent No.584,609, 1,
No. 210,252, JP-A-50-40,625, JP-A-51-3,623, JP-A-51-1
0,927, 54-118,247, JP-B-48-3,286, 59-3
Arylidene dyes described in No. 7,303, etc., JP-B-28-3,
No. 082, No. 44-16,594, Styryl dyes described in No. 59-28,898 and the like, UK Patent No. 446,583, No. 1,335,422,
Triarylmethane dyes described in JP-A-59-228,250 and the like, British Patent Nos. 1,075,653, 1,153,341 and 1,28
Nos. 4,730, 1,475,228 and 1,542,807, merocyanine dyes described in U.S. Pat.Nos. 2,843,486 and 3,29
And cyanine dyes described in JP-A-4,539 and JP-A-1-91247.

Particularly, as the near-infrared light absorbing dye, a compound having the structure of the general formula (A) is preferable.

General formula (A) ^{(Wherein, R 51, R 52, R} 53, R 54, R 55 and R ⁵⁶ may be the same or different, each represents a substituted or unsubstituted alkyl group, two Z ⁵¹ and Z ⁵² each Non-metallic atoms required to form a naphtho-fused ring having the above sulfonic acid group, or non-metallic atoms necessary to form a benzo-fused ring each having at least one sulfonic acid group Wherein Z ⁵³ represents a group of non-metallic atoms necessary for forming a 5- or 6-membered ring, Y represents a hydrogen atom or a monovalent group, X represents an anion, and n represents 1 or 2. 1 when the dye molecule forms an inner salt.

As the cyan coupler, in addition to the diphenylimidazole cyan coupler described in JP-A-2-33144,
The 3-hydroxypyridine cyan couplers described in European Patent EP 0,333,185 A2 (among others, couplers (42) listed as specific examples, 4-equivalent couplers having a chlorine leaving group to give two equivalents, couplers ( (6) and (9) are particularly preferable) and cyclic active methylene cyan couplers described in JP-A-64-32260 (coupler examples 3, 8, and 34 are particularly preferable). Is also preferred.

Exposure for obtaining a photographic image may be performed using a usual method. That is, any of a variety of known light sources such as natural light (daylight), a tungsten lamp, a fluorescent lamp, a mercury lamp, a xenon arc lamp, a carbon arc lamp, a xenon flash lamp, and a cathode ray tube flying spot can be used. Exposure time is 1/1000 second, usually used for cameras, to 1
Exposure time of 1 second, of course, exposure shorter than 1/1000 second, for example, exposure of 1/10 ⁴ to 1/10 ⁶ second using xenon flashlight or cathode ray tube, or exposure longer than 1 second can be used. You can also. If necessary, the spectral composition of light used for exposure by the color filter can be adjusted. Laser light can also be used for exposure. Electron beam, X
It may be exposed to light emitted from a phosphor excited by rays, gamma rays, alpha rays, and the like.

When a laser beam is used, a semiconductor laser is preferable, and specific examples thereof include In _1-x G _ax P (（700 nm),
GaAs _1-x Px (610 to 900 nm), G _a1 - _x Al _x As (690 to 900 n
m), InGaAsP (1100-1670 nm), AlGaAsSb (1250-1400
nm) and the like. In addition to the above-mentioned semiconductor laser, Nb: YAG crystal
A YAG laser (1064 nm) excited by a GaAs _x P _(1-x) light emitting diode may be used. Preferably, 670, 680, 75
It is preferable to select and use a semiconductor laser beam of 0, 780, 810, 830, or 880 nm.

Further, a nonlinear optical effect may be used. The second harmonic generation element (SHG element) converts the wavelength of laser light to half by applying the nonlinear optical effect. For example, CD ^* A and KD ^* P are used as nonlinear optical crystals. (See Laser Handbook, edited by The Laser Society of Japan, published December 15, 1982, pages 122 to 139). In addition, a LiNbO ₃ optical waveguide device in which an optical waveguide in which Li ⁺ is ion-exchanged with H ⁺ in LiNbO ₃ crystal can be used (NIKKEI ELECTRONICS 1986.7.14 (no.399) Nos. 89 to 90).
page).

The output device described in Japanese Patent Application No. 63-226552 can be used in the present invention.

The light-sensitive material of the present invention comprises a yellow material on a support.
Photosensitive layer containing coupler (YL), Photosensitive layer containing magenta coupler (ML), Photosensitive layer containing cyan coupler (CL), Protective layer (PL), Intermediate layer (IL) A decolorizable colored layer, particularly an antihalation layer (AH), may be provided between them. YL, ML and CL have spectral sensitivities suitable for at least three types of light beams having different main wavelengths. The main sensitivity wavelengths of YL, ML and CL are each 30 nm or more, preferably 50 nm to 100 nm apart. At the main sensitivity wavelength of one photosensitive layer, at least 0.8 Log. There is a sensitivity difference of 1.0 or more. At least one of the photosensitive layers has a sensitivity in a wavelength region longer than 670 nm, and more preferably, at least one layer is more sensitive.
It is preferable to have a sensitivity in the long wave region from 750 nm.

For example, as shown in the following table, an arbitrary photosensitive layer may be used. In the table, R is red sensitized and IR-1
And IR-2 indicate that they were spectrally sensitized to different infrared wavelength ranges, respectively.

In the present invention, the photosensitive layer having a spectral sensitivity in a wavelength region longer than 670 nm can be subjected to image exposure using a laser beam. Therefore, the spectral sensitivity distribution should be within the wavelength range of the main sensitivity wavelength ± 25 nm, preferably the main sensitivity wavelength ± 15 nm. The other 67
The spectral sensitivity of the present invention in the wavelength region longer than 0 nm, particularly in the infrared wavelength region, tends to be relatively broad. Therefore, the spectral sensitivity distribution of the photosensitive layer may be corrected by using a dye, preferably by fixing and including the dye in a specific layer. For this purpose, a dye is contained in the colloid layer in a diffusion-resistant state, and is used so that it can be decolorized during the development process. The first is to use a solid fine particle dispersion of a dye which is substantially insoluble in water of pH 7 and insoluble in water of pH 7 or more. Second, the use of acid dyes with polymers or polymer latexes that provide cationic sites. The first and second methods are described in JP-A-63-197947, the general formula (V
The dyes represented by I) and (VII) are useful. In particular, a dye having a carboxyl group is useful for the first method.

The photographic light-sensitive material of the present invention may be, for example, a color negative film for photography (for general use, for movies, etc.), a color reversal film (for slides, for movies, etc.), a color photographic paper, a color positive film (for movies, etc.), a color direct positive film. , Color reversal photographic paper, color photosensitive material for thermal development, color photographic photosensitive material for plate making (ris film, scanner film, etc.), color X-ray photographic photosensitive material (direct / indirect medical use, industrial use, etc.), color diffusion transfer Applicable to photosensitive materials (DTR).

Example 1 A tabular silver iodobromide emulsion sensitized with gold and sulfur prepared according to the method disclosed in Example 1 of JP-A-60-131,533 (average diameter: 0.82 μm, average diameter / Thickness 11.2, pAg8.2
pH 6.5) at 40 ° C., and the sodium salt of 2,4-dichloro-6-hydroxy-1,3,5-triazine was added as a gelatin hardener, and cellulose was added. Coated on triacetate support. At this time,
A protective layer containing gelatin as a main component and containing a surfactant and the above-mentioned gelatin hardener was simultaneously coated on the upper layer of this emulsion layer.

The sample thus prepared was divided into three parts, one set was stored at -30 ° C, the other set was stored under natural conditions for one year each, and the other set was stored at -30 ° C and three days before exposure. From 80% R
H, after storing at 50 ° C, these three sets of samples are transmitted with light longer than 520nm by FWH photometer (UV absorption filter device, tungsten light source, color temperature 2854 ° K) manufactured by Fuji Photo Film Co., Ltd. Exposure for sensitometry was performed through a shear cut filter, developed with a developer described below, bleached, washed with water, and dried.

The processed sample was measured for fogging density and sensitivity using a densitometer manufactured by Fuji Photo Film Co., Ltd. Sensitivity depends on fog density
Table 1 shows the reciprocal of the required amount of light to give a concentration obtained by adding 0.2, and Table 1 shows each sample stored at -30 ° C as 100%.
The relative value of the sensitivity of the corresponding sample in the case of "." Table 1 also shows the increase and decrease of the fog density based on the fog of each sample stored at -30 ° C.

As shown in Table 1, in the present invention, there is little change in sensitivity over time. In particular, the polymethine dyes A-4, A-5, (29) and (31), whose E _ox is lower than 0.60 V _vs SCE, have an E _ox of
Polymethine dyes A-1, A- nobler than 0.60V _vs SCE
This desensitization tends to be larger than that of 2, A-3 and (11). This tendency is particularly remarkable in A-4 and A-5. However, the polymethine dye of the present invention has a smaller desensitization than A-4 and A-5, and is a very useful technique.

Example 2 A cubic silver bromide emulsion was prepared according to the method disclosed in Example 1 of JP-A-1-223441. The silver bromide grains of the obtained silver bromide emulsion were monodisperse grains having an average side length of 0.74 μm (coefficient of variation 10.6%). This emulsion was prepared at pH 6.3, pAg8.4 at 40 ° C.
And ripened at 55 ° C. with chloroauric acid and sodium thiosulfate to give gold and sulfur sensitization for optimum.

Then, at 40 ° C., the compounds shown in Table 2 were added, and the emulsion was further added with 2-hydroxy-4,6-dichloro-1,3,3 / kg of emulsion.
After 0.1 g of sodium salt of 5-triazine and 0.1 g of sodium acid of dodecylbenzenesulfonic acid were added, a protective layer was formed and applied on a polyethylene terephthalate film base in the same manner as in Example-8.

The prepared coating sample was divided into three parts, one set at -30 ° C, another set at 80% RH and 50 ° C for 3 days, and the other set at oxygen partial pressure.
After each storage at room temperature under 10 atm for 3 days, sensitometric exposure was carried out, development was carried out and sensitivity was determined in exactly the same manner as in Example 8. Sensitivity is 0.2
It was expressed as the reciprocal of the amount of light required to give the added density. Table 2 shows the results.
The relative values of the sensitivities of the other samples corresponding to the respective sensitivities when the sensitivities of the respective samples stored at a temperature of 100 ° C. were set to 100 are shown.

From the results shown in Table 2, it can be understood that the sensitivity of the present invention is little reduced even under such storage conditions. Further, when compound V-6 or V-3, which is a compound represented by the general formula V as in sample numbers 2-3 and 2-7, is used in combination, it is placed under high temperature and high humidity of 80% RH and 50 ° C. In this case, the sensitivity is reduced. On the other hand, Sample No. 2-11 using a combination of one of the compounds represented by the general formula IV, IV-1, was 80% RH, 50 ° C. under high temperature and high humidity as compared with 2-10 without adding it. Even in the case where the oxygen partial pressure is set at 10 atm, the decrease in sensitivity is further suppressed in each case. The effects of these compounds are similarly expressed for polymethine dyes outside the present invention, but when combined with the polymethine dye of the present invention, even under these storage conditions, it is assumed that the decrease in sensitivity is significantly suppressed. be able to.

Example 3 (Preparation of emulsion) Sodium chloride was added to a 3% aqueous solution of lime-treated gelatin.
3 g was added, and 3.2 ml of N, N'-dimethylimidazolidin-2-thione (1% aqueous solution) was added. To this aqueous solution, an aqueous solution containing 0.2 mol of silver nitrate and an aqueous solution containing 0.2 mol of sodium chloride and 15 μg of rhodium trichloride were added and mixed at 56 ° C. with vigorous stirring. Subsequently, an aqueous solution containing 0.780 mol of silver nitrate and an aqueous solution containing 0.780 mol of sodium chloride and 4.2 mg of potassium ferrocyanide were added and mixed at 56 ° C. with vigorous stirring. Five minutes after the addition of the aqueous silver nitrate solution and the aqueous alkali halide solution was completed, an aqueous solution containing 0.020 mol of silver nitrate, 0.015 mol of potassium bromide,
An aqueous solution containing 0.005 mol of sodium chloride and 0.8 mg of potassium hexachloroiridate (IV) was added and mixed at 40 ° C. with vigorous stirring. Thereafter, desalting and washing were performed. In addition, add 90.0 g of lime-processed gelatin,
Triethylthiourea was added for optimal chemical sensitization.

With respect to the obtained silver chlorobromide (A), the shape, the particle size and the particle size distribution of the particles were determined from an electron micrograph. All of these silver halide grains were cubic, and the grain size was 0.52 μm and the coefficient of variation was 0.08. The particle size was represented by the average value of the diameter of a circle equivalent to the projected area of the particle, and the particle size distribution was obtained by dividing the standard deviation of the particle size by the average particle size.

Next, the halogen composition of the emulsion grains was determined by measuring the X-ray diffraction from the silver halide crystals. The diffraction angle from the (200) plane was measured in detail using a monochromatic CuKα ray as a radiation source. A diffraction line from a crystal having a uniform halogen composition gives a single peak, whereas a diffraction line from a crystal having a localized phase having a different composition gives a plurality of peaks corresponding to those compositions. By calculating the lattice constant from the diffraction angle of the measured peak, the halogen composition of the silver halide constituting the crystal can be determined. The measurement results of this silver chlorobromide emulsion (A) show that, in addition to the main peak of silver chloride of 100%, silver chloride has a center at 70% of silver chloride (30% of silver bromide).
% (40% silver bromide).

(Preparation of photosensitive material) A multilayer color photographic paper having the following layer constitution was prepared on a paper support laminated on both sides with polyethylene. The coating solution was prepared as follows.

Preparation of first layer coating solution 19.1 g of yellow coupler (ExY) and color image stabilizer (Cp
d-1) Ethyl acetate 2 in 4.4 g and 1.4 g of color image stabilizer (Cpd-7)
7.2 cc and a solvent (Solv-1) 8.2 g were added and dissolved, and this solution was emulsified and dispersed in 185 cc of a 10% aqueous gelatin solution containing 8 cc of 10% sodium dodecylbenzenesulfonate. On the other hand, a red-sensitive sensitizing dye (Dye-
An emulsion to which 1) was added was prepared. The above-mentioned emulsified dispersion and this emulsion were mixed and dissolved to prepare a first coating solution having the following composition.

Coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. The gelatin hardener for each layer is 2,4
-The sodium salt of dichloro-6-hydroxy-1,3,5-triazine was used.

The following were used as spectral sensitizing dyes for the first layer of the red-sensitive yellow coloring layer.

(First layer: red-sensitive yellow coloring layer) 1.0 × 10 ⁻⁴ mol per mol of silver halide 1.0 × 10 ⁻⁴ mol The third layer infrared-sensitive magenta coloring layer and the fifth layer infrared-sensitive cyan coloring layer are shown in Tables 3 and 4. 2.5 × 10 ⁻⁵ per mole of silver halide in the third layer
In the fifth layer, 0.6 × 10 ^-5 mol was added, and when these polymethine dyes were used, compound IV-1 was added in an amount of 1.8 × 10 ^-3 mol per mol of silver halide.

Further, 1- (5-methylureidophenyl) -5-mercaptotetrazole was added to each of the yellow, magenta and cyan coloring emulsion layers in an amount of 8.0 × 10 ^-4 mol per mol of silver halide.

The following dyes were added to the emulsion layer to prevent irradiation.

(Layer Configuration) The composition of each layer is shown below. The numbers represent the coating amount (g / m ² ). The silver halide emulsion represents a coating amount in terms of silver.

Support Polyethylene laminated paper [Polyethylene on first layer side contains white pigment (TiO ₂ ) and blue dye (ultra blue)] First layer (red-sensitive yellow coloring layer) Silver chlorobromide emulsion (A) 0.30 gelatin 1.86 Yellow coupler (ExY) 0.82 Color image stabilizer (Cpd-1) 0.19 Solvent (Solv-1) 0.35 Color image stabilizer (Cpd-7) 0.06 Second layer (color mixture prevention layer) Gelatin 0.99 Color mixture inhibitor (Cpd- 5) 0.08 Solvent (Solv-1) 0.16 Solvent (Solv-4) 0.08 Third layer (infrared-sensitive magenta coloring layer) Silver chlorobromide emulsion (A) 0.12 Gelatin 1.24 Magenta coupler (ExM) 0.20 Color image stabilizer (Cpd-2) 0.03 Color image stabilizer (Cpd-3) 0.15 Color image stabilizer (Cpd-4) 0.02 Color image stabilizer (Cpd-9) 0.02 Solvent (Solv-2) 0.40 Fourth layer (ultraviolet absorbing layer) ) Gelatin 1.58 UV absorber (UV-1) 0.47 Color mixing inhibitor (Cpd-5) 0.05 Solvent (Solv-5) 0.24 Fifth layer (infrared-sensitive cyan coloring layer) Silver halide emulsion (A) 0.23 Gelatin 1.34 Cyan coupler (ExC) 0.32 Color image stabilizer (Cpd-6) 0.17 Color image stabilizer (Cpd-7) 0.40 Color image stabilizer (Cpd-8) 0.04 Solvent (Solv-6) 0.15 6th layer (ultraviolet absorbing layer) Gelatin 0.53 Ultraviolet absorber (UV-1) 0.16 Color mixture inhibitor (Cpd-5) 0.02 Solvent (Solv-5) 0.08 7th layer (protective layer) Gelatin 1.33 Polyvinyl alcohol acrylic Modified copolymer (modification degree 17%) 0.17 Liquid paraffin 0.03 Then, each sample was divided into three parts, one set was sealed at room temperature for 3 days at an oxygen partial pressure of 10 atm, and the other set was sealed at 80% RH and 50 ° C for 3 days. After storage at -30 ° C in a sealed container, the semiconductor laser AlGaInP
(Oscillation wavelength, about 670 nm), semiconductor laser GsAlAs (oscillation wavelength, about 750 nm), GsAlAs (oscillation wavelength, about 830 nm), and laser light is moved by a rotating polyhedron in the direction perpendicular to the scanning direction. A device capable of sequentially scanning and exposing was assembled on paper, and these photosensitive materials were exposed using this device. For the exposure amount, the exposure time and light emission amount of the semiconductor laser were electrically controlled.

The exposed sample was subjected to color development processing in the next processing step using a paper processing machine.

The composition of each processing solution is as follows.

Rinse solution (same as tank solution and replenisher) Deionized water (Calcium and magnesium are each 3ppm
The samples after the development were measured for cyan, magenta, and yellow densities, respectively. Concentration 0.5 for each overlay density
The reciprocal of the amount of exposure necessary to form a color with the added density was determined as the sensitivity, and their relative comparisons were made.

Table 3 shows the results of the magenta coloring layer (third layer) and Table 4 shows the results.
The table shows the results of the cyan coloring layer (fifth layer). The relative sensitivity of the sample stored at -30 ° C. with the replacement of argon gas is the relative sensitivity when each sample number 3-1 is set to 100 for each coloring layer. Indicated by value. Samples stored at 80% RH, 50 ° C for 3 days and oxygen partial pressure 1
The relative sensitivities of the samples stored at 0 atm and room temperature for 3 days were shown as relative values when the relative sensitivities of the samples stored at -30 ° C with the replacement of argon gas for each color-forming layer were each set to 100.

As can be seen from Tables 3 and 4, the sensitivity of the present invention is significantly lower than that of the corresponding non-inventive polymethine dye having a similar structure even when stored under such severe conditions. Until now, infrared-sensitive polymethine dyes have extremely poor stability, and silver halide light-sensitive materials using such dyes are commercially available only if they can maintain sensitivity for only a few months even when stored at low temperatures such as freezers. I haven't been. The reason that the sensitivity can be maintained for only several months even when stored at a low temperature is that such a polymethine dye is easily susceptible to air oxidation. The present inventor has studied the phenomenon of undergoing air oxidation, and as a result, the polymethine dye is more likely to be oxidized as the oxidation potential (E _ox ) becomes lower, and is more easily oxidized when the oxidation potential becomes lower than 0.60 V _vs SCE. It turned out to be. The dye of the present invention was extremely stable even though it had an oxidation potential much lower than 0.60 V _vs SCE.

If the technique of the present invention is used, even if it is a silver halide light-sensitive material for infrared light sensitivity, as in the case of a normal silver halide light-sensitive material, the sensitivity is extremely reduced even when left for a long time at room temperature. A small number of photosensitive materials can be provided.

Example 4 A silver chloride emulsion was prepared according to the method disclosed in Example 1 of JP-A-63-239,449. The prepared emulsion was pH 6.2, pAg
Monodisperse cubic silver chloride grains having a side length of 0.46 μm at 7.2 (coefficient of variation: 9.1%) and were optimally chemically sensitized with sodium thiosulfate.

To this emulsion, the compounds shown in Table 5 were added, and then combined with the same coupler emulsified dispersion as the cyan coupler emulsified dispersion containing the cyan coupler for the fifth layer cyan coloring shown in Example 10 and the like. Application samples shown in Table 5 were prepared. Sample Nos. 4-6 in the table are compounds shown in Table 5, (1-8) to which sodium thiosulfate was added and added 2 minutes before chemical sensitization. 1 was added 15 minutes after the addition of sodium thiosulfate, and the rest was added 45 minutes after the addition.

As the support, a paper support laminated on both sides with polyethylene was used. Coating liquid amount was set so that the amount is 0.35 g / m ² of silver, the amount is 0.45 g / m ² and the gelatin amount of the coupler is 1.50 g / m ^2, the upper protective gelatin 1.50 g / m ² Layers were provided. As a gelatin hardener, 2,4-dichloro-6
The sodium salt of -hydroxy-1,3,5-triazine was used.

Next, the coated sample was divided into three parts, and one set was replaced with an oxygen-impermeable bag after replacing it with argon gas, and then sealed.
Stored for years. The other set was stored in the same manner, opened three days after one year, and stored at 80% RH and 50 ° C. for three days. The other set was left indoors naturally for one year.

Using a tungsten sensitometer, these three sets of samples were passed through a shear cut filter that transmits light having a wavelength longer than 660 nm from sample numbers 4-1 to 4-7.
Samples Nos. 8 to 4-15 pass through a sharp cut filter that transmits light longer than 720 nm.
Exposure was performed through a sharp cut filter that transmits light having a wavelength longer than 0 nm.

The exposed sample was subjected to continuous processing (running test) using a paper processor until the replenishment was twice the tank capacity for color development in the next processing step.

The composition of each processing solution is as follows.

Rinse solution (same as tank solution and replenisher) Deionized water (Calcium and magnesium are each 3ppm
Hereinafter, the cyan density of each sample after the development processing was measured. Sensitivity was defined as the reciprocal of the exposure required for color development at a density obtained by adding the overlay density to the cyan density of 0.5, and the relative comparison of each sample was made. The obtained results are shown in Table 5. In Table 5, samples stored at −30 ° C. have sample values 4-1 to 4-7 in which the relative values of the relative sensitivity of 4-1 are set to 100. The sample numbers 4-8 to 4-15 show relative values with the relative sensitivity of 4-8 as 100, and the sample numbers 4-16 to 4-26 show relative values with the relative sensitivity of 4-16 as 100, The one that is stored at 80% RH and 50 ° C for 3 days and the one that is left naturally for one year respectively correspond to-
The relative values when the relative sensitivity of the sample stored at 30 ° C. was set to 100 are shown.

From the results shown in Table 5, it can be understood that the samples using the polymethine dye of the present invention show little decrease in sensitivity even when stored at 80% RH and 50 ° C. or when left for a long period of time. . Further, it can be understood that the use of the compound represented by any of the general formulas IV, V, VI and VII can increase the sensitivity and further improve the storage stability.

(Effects of the Invention) According to the present invention, a silver halide photographic light-sensitive material having high sensitivity, less increase in fog even during storage under high temperature and / or high humidity (long-term natural aging), and little change in sensitivity Is obtained.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int.Cl. ⁶ , DB name) G03C 1/12 G03C 1/28 G03C 1/34

Claims (3)

(57) [Claims] 1. A silver halide emulsion comprising at least one methine dye represented by the following general formula (I). _{(I) (MET 1 (Q} ) l2 -Ar] in _l3 formula, MET represents an atomic group having a methine dye structure,
Q represents a divalent linking group comprising an atom or an atomic group containing at least one of a carbon atom, a nitrogen atom, a sulfur atom, and an oxygen atom, and l ₁ is 1 or 2, l ₂ is 0 or 1, l ₃ Represents 1, 2, 3 or 4. Ar represents an aromatic group having a polycyclic compound composed of eight or more atoms including at least one nitrogen atom. However, the nitrogen atom is subject to tautomerism. Represents a structure that does not. 2. The silver halide emulsion according to claim 1, wherein the methine dye represented by formula (I) has an oxidation potential of 0.60 (V _VS SCE) or lower. 3. The general formula (I) according to claim 1
Characterized in that it contains at least one methine dye represented by the formula (I) and at least one compound represented by the following formulas (IV), (V), (VI) and (VII): emulsion. General formula (IV) In the formula, A ₁ represents a divalent aromatic residue. R ₉ , R ₁₀ , R ₁₁ and R ₁₂ are each a hydrogen atom, a hydroxyl group, an alkyl group,
Represents an alkoxy group, an aryloxy group, a halogen atom, a heterocyclic nucleus, a heterocyclylthio group, an arylthio group, an amino group, an alkylamino group, an arylamino group, an aralkylamino group, an aryl group or a mercapto group, and these groups are substituted. Is also good. However, at least one of A ₁ , R ₉ , R ₁₀ , R ₁₁ and R ₁₂ has a sulfo group. X ₁ and Y ₁ and X ₁ ′
And Y ₁ 'represent -CH = and -N =, respectively, and X ₁ and Y ₁ and
At least one among X ₁ and Y ₁ represents -N =. General formula V [V] In the formula, Z ₁₁ represents an atom group necessary for completing a 5- or 6-membered nitrogen-containing heterocyclic ring. This ring may be fused with a benzene or naphthalene ring. R ₁₃ represents a hydrogen atom or an alkyl group. R ₁₄ represents a hydrogen atom or an alkyl group. X ₂ ^- represents an anion. General formula (VI) In the formula, R ₁₅ represents an alkyl group or an aryl group. X
₃ represents a hydrogen atom, an alkali metal atom, an ammonium group or a precursor. General formula (VII) In the formula, Y ₂ is an oxygen atom, a sulfur atom, NHNH, ＮN- (L ₅₇ ) n
_14- R ₁₇ , L ₅₆ and L ₅₇ represent a divalent linking group,
R ₁₆ and R ₁₇ represent a hydrogen atom, an alkyl group, or an aryl group. X ₄ represents a hydrogen atom, an alkali metal atom, an ammonium group or a precursor. n ₁₃ and n ₁₄ represents 0 or 1.