JPS62164043A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide high sensitivity to a silver halide photographic sensitive material and to prevent the desensitization during storage with the lapse of time by incorporating a specified compound into the red-sensitive silver halide emulsion layer and carrying out color sensitization with a sensitizing dye. CONSTITUTION:This silver halide photographic sensitive material has at least a red-sensitive silver halide emulsion layer on the support. The emulsion layer contains a compound represented by formula I and the silver halide in the emulsion layer has been color-sensitized with at least one kind of sensitizing dye selected among sensitizing dyes represented by formula II-IV. In the formulae I-IV, each of R1 and R2 is -CH or the like, each of R3 and R4 is an aliphatic group or the like, L is methine, each of R5 and R6 is alkyl or the like, each of L1-L5 is methine, each of Z1 and Z2 is a group of atoms, Z3 is a group of hydrocarbon atoms, X<-> is an acid anion and each of m1, m2, n and l1 is 0 or 1. The sensitive material has high sensitivity and does not cause desensitization during storage with the lapse of time.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a silver halide photographic light-sensitive material, and more specifically, the present invention relates to a silver halide photographic light-sensitive material, and more specifically, a silver halide photographic light-sensitive material that has high sensitivity and is hardly desensitized even when a sample changes over time. This invention relates to a silver halide color photographic material with excellent sharpness.

[Background of the Invention] Conventionally, silver halide color photographic materials for printing have been subjected to image exposure and R color development, whereby an oxidized product of an aromatic primary amine developing agent and a color former undergo a coupling reaction. However, dyes such as indophenol, indoaniline, indamine, azomedine, phenazine, and phenazine are produced, and a dye image is formed.

In such photographic methods, a subtractive color reproduction method is usually adopted, and blue-, green-, and red-sensitive light-sensitive silver halide emulsions contain couplers that produce yellow, magenta, and cyan colors, respectively. A silver halide color photographic light-sensitive material is used.

These blue-, green-, and red-sensitive silver halide emulsion layers are spectrally sensitized using blue-, green-, and red-sensitizing dyes, respectively. A silver emulsion is used.

Among these, useful sensitizing dyes used in red-sensitive silver halide emulsions include, for example, U.S. Pat.
No. 234, No. 2,270,378, No. 2,442
．． 7iO No. 2,454,629, No. 2.776,
No. 280, 2,213. '195, 2.4'13
．． No. 748, No. 2.519.001, West German Patent No. 929
．． Cyanine dyes, merocyanine dyes, or complex cyanine dyes such as those described in 080@ etc. are used. In particular, photosensitive 'tJ Xi, which has a red-sensitive silver halide emulsion sensitized using a cyanine dye, has high sensitivity,
Moreover, although it has a desirable spectral sensitization distribution, it has the disadvantage that it accompanies desensitization over time of the light-sensitive material.

Particularly in recent years, high-speed printing processing has been desired, and in this case, shortening the exposure time for printing is important for high-speed printing processing. This exposure time is determined by the sensitivity of the red-sensitive emulsion layer, and therefore it is necessary to increase the sensitivity of the red-sensitive emulsion layer and to take measures to prevent desensitization during storage over time.

On the other hand, silver halide photographic materials (hereinafter referred to as photographic materials)
In this method, a hydrophilic colloid layer is colored with a dye that is included in a photographic material for the purpose of absorbing light of a specific wavelength for filtering, antihalation, antiirradiation, or to adjust the sensitivity of a photographic emulsion. Things are well done.

In addition, for the purpose of improving the sharpness of photographic images, an antihalation layer is provided between the emulsion layer and the support or on the surface of the support to prevent harmful effects at the interface between the emulsion layer and the support or the back surface of the support. It is often done to prevent halation by absorbing reflected light, or to prevent irradiation by coloring the emulsion layer to absorb harmful reflected light or scattered light from silver halide grains, etc. ing.

Dyes used for such purposes must have good absorption spectrum characteristics depending on the purpose of use, be completely decolorized in photographic solutions, be easily eluted from photographic materials, and be free from residual color due to dyes after processing. There is no contamination, there is no adverse effect on the photographic emulsion such as fogging or desensitization, there is no diffusion from the dyed material to other descendants, and there is
Alternatively, it must satisfy conditions such as excellent stability over time in photographic materials and no discoloration or fading.

To date, many efforts have been made and a large number of dyes have been proposed with the aim of finding dyes that satisfy the above conditions. For example, British Patent No. 1506,385, US Patent No. 3.247.127, Japanese Patent Publication No. 39 Sho.
-22069, Japanese Patent Publication No. 43-13168, etc., oxonol dyes, U.S. Patent Nos. 1 and 8
styryl dye represented by No. 45.404, merocyanine dye represented by U.S. Patent No. 2,493,747,
There are cyanine dyes (such as 31, typified by U.S. Pat. No. 2.843.486, and anthraquinone dyes typified by U.S. Pat. No. 2.865.752).

These dyes have excellent decolorization properties during development processing and have desirable absorption spectra, but on the other hand, light-sensitive materials containing these dyes have the drawback of desensitization during storage over time.

Therefore, it is difficult to increase the sensitivity of photographic materials containing the above red-sensitive sensitizing dyes and dyes during use.
As a result, the exposure time for prints 1 to 1 becomes long, which does not meet the recent demands for high-speed printing processing.

[Object of the invention] The present invention was made in view of the above circumstances, and as a result of intensive research on red-sensitive sensitizing dyes and dyes,
By combining a specific red-sensitive sensitizing dye and a first dye, high sensitivity and high-speed printing processing of a red-sensitive emulsion layer and, by extension, a silver halide photographic light-sensitive material containing the red-sensitive emulsion layer have been achieved.

Therefore, the first object of the present invention is to develop a red-sensitizing dye that has high sensitivity by using a specific red-sensitizing dye in combination with dye No. An object of the present invention is to provide a silver halide photosensitive material having an emulsion.

A second object of the present invention is to provide a silver halide photographic light-sensitive material that can shorten the exposure time particularly during printing and enable high-speed printing processing.

A third object of the present invention is to provide a silver halide photographic material with improved sharpness of photographic images.

[Structure of the Invention] The above object of the present invention is to provide a silver halide photographic material having at least a red-sensitive silver halide emulsion layer on a support, in which the red-sensitive silver halide emulsion layer has the following general formula [ The silver halide contained in the red-sensitive silver halide emulsion layer has the following general formula [U].

This is achieved by using a silver halide photographic material color sensitized with at least one sensitizing dye selected from the sensitizing dyes represented by [I[] and [IV].

General formula [1] In the formula, R1 and R2 are respectively -CN or -○F
R'R'', and R' and R'' each represent a hydrogen atom, a fluorine atom, or a fluorinated alkyl group having 1 to 4 carbon atoms.

R3 and J: and R4 each represent an aliphatic group, an aromatic group or a heterocyclic group. General formula [11] General formula [111] In the formula, R5 and R6 each represent an alkyl group or an aryl group, Ll, L2, L3, L4 and L5
represents a methine group. zl and Z2 each represent an atom or atomic group necessary to complete the oxazole ring, thiazole ring or selenazole ring. Z3 represents a group of hydrocarbon atoms necessary to form a 6-membered ring. xe represents an acid anion. ml, m2, n and 21 each represent O or 1. However, when the compound forms an inner salt, 2 is O.

General formula [IV] In the formula, Z4 is a non-metallic atomic group necessary to constitute a quinoline ring, and Z5 is a thiazole ring, benzothiazole ring, naphthothiazole ring, benzoxazole ring, naphthoxazole ring, benzoselenazole. Represents an atomic group necessary to constitute a ring or a def1 to selenazole ring. R7
, Ra and R9 each represent an alkyl group, and Xθ
represents an acid anion. m3 and 22 are each O
Or represents 1.

[Specific Constitution of the Invention] The red-sensitive silver halide emulsion layer of the present invention has the general formula [II
], [I [[] or [IV]] spectrally sensitized.

In the general formulas [II], J: and [I[], the alkyl groups represented by R5 and R6 may be branched or have an unsaturated bond. More preferably, it has 10 or less carbon atoms, and atoms such as sulfo, aryl, carboxy, amine (-class, secondary, tertiary), alkoxy, aryloxy, hydroxy, alkoxycarbonylxy, halogen, etc. may have. Specific examples include methyl group, ethyl group, sulfobupur group, benzyl group, phenethyl group, carboxymethyl group, dimethylaminopropyl group, methoxyedyl group, phenoxypropyl group, methylsulfonylethyl group, cyclohexyl group, octyl group, decyl group. , carbamoylethylphenethyl group, sulfobenzyl group, 2-hydroxy-3
-sulfopropylthyl group, sulfobroboxyethoxyethyl group, trifluoroethyl group, carboxybenzyl group, cyanpropyl group,
p-carboxyphenethyl group, ethoxycarbanylmethylpropionylethyl group, anisyl group, acetoxyethyl group, benzoyloxypropyl group, chloroethyl group, N
-ethylaminocarbonylprobyl group, allyl group, 2-
These include butynyl group, cyanoethyl group, etc.

Furthermore, the aryl group represented by R5 and R6 is, for example, a phenyl group, a carboxyphenyl group, a sulfophenyl group, or the like.

When the methine group represented by Ll, L2, and L3 has a substituent, it is represented by the formula (-CR=), and the substituent R is a linear or branched alkyl group having about 1 to 8 carbon atoms (
Examples include methyl group, ethyl group, carboxymethyl group (eg, methoxy group, ethoxy group), and aryl group (eg, phenyl group, tolyl group).

Specific examples of the thiazole nucleus, selenazole nucleus or oxazole nucleus completed by 71 and z2 in general formulas [II] and [I[I] are: thiazole, 4-methylthiazole, 5-phenylthiazole, 4.5 -dimethylthiazole, benzothiazole, 5-chlorobenzothiazole, 6-chlorobenzothiazole, 3-methylbenzothiazole, 6-methylbenzothiazole, 5
-bromobenzothiazole, 5-carboxybenzothiazole, 5-ethoxycarbonylbenzothiazolebenzothiazole, 5-pivaloylaminobenzothiazole, 6-benzoylaminobenzothiazole, 5-acetylbenzothiazole, 6. -acetylaminobenzothiazole, 5-phenylbenzothiazole, 6-methylbenzothiazole, 5-iodobenzothiazole, 5-
Methoxy-6-methylbenzothiazole, tetrahydrobenzothiazole, 5-phenoxybenzothiazole,
5-phenethylbenzothiazole, 5-cyanobenzothiazole, naphtho[1.2-d]thiazole, naphthyl
-[2.1-dl thiazole, naphtho[2.3-d]
Thiazole, 5-ethoxynaphtho[1.2-d]thiazole, 8-methoxynaphtho[2.1-d]thioxazole, naphtho[1.

2-d]oxazole, naphtho[2.1-d]oxazole, naphtho[2.3-d]oxazole, and the like.

The acid anion represented by Examples include acid ions and nitrate ions.

Further, among the sensitizing dyes represented by the above general formulas [II] and [I[[], particularly useful sensitizing dyes are the following general formulas [
IIa] and [II[a].

General formula [11al (Xθ)1 General formula [I[JI] (Xθ)x+ In the formula, Yl and Y2 each represent an oxygen atom, a sulfur atom, or a selenium atom, and Rho and R11 represent a lower alkyl group. .

A1, A2, B1, B2, C1, C2, Dl and B2
each represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a phenyl group, a cyano group, a nitro group or an alkoxycarbonyl group.

Also, A1 and B1, B1 and C1, C1 and Dl, A2 and 3
2, at least one of the combinations of B2 and C2 and C2 and B2 may be condensed to form a benzene ring.

A+ of one F9 formulas [IIa] and [IIa]
, A2, B1, B2, C1, C2, Dl and B2 are linear or branched lower alkyl groups having about 1 to 5 carbon atoms (e.g. methyl group, ethyl group, butyl group, trifluoromethyl group), and the alkoxy group is a straight or branched alkylamino group having about 1 to 5 carbon atoms (e.g., methoxy group, ethoxy group)
, the halogen atom is fluorine, chlorine, bromine or iodine, the phenyl group is, for example, a phenyl group without a substituent, a hydroxyphenyl group, a carboxyphenyl group, and the alkoxycarbonyl group is, for example, a methoxycarbonyl group, an ethoxycarbonyl group. It is.

Rs, Rs, L+ to L2・L3SL4\L5, x
e, n and 11 each represent the aforementioned general formula [II] J3
and has the same meaning as explained in [1]. However, it is more preferable that n is 1.

In the present invention, when the quinoline ring having 74 in the general formula [TV] has a substituent, examples of the substituent include a halogen atom, an alkyl group, an alkoxy group,
Examples include hydroxy group, cyano group, carboxy group, alkoxycarbonyl group, alkylamino group, acylamino group, acyl group, phenyl group, and cyclohexyl group. A specific example of a quinoline ring with Z4 as a constituent is:
2-quinoline, 6-chloro-2-quinoline, 6-methyl-2-quinoline, 6-medoxy-2-quinoline, 7-methyl-2-quinoline, 8-methyl-2-quinoline, 6-
Hydroxy-2-quinoline, 4-quinoline, 6-methyl-4-quinoline, 6-ethyl-4-quinoline, 6-medoxy4-quinoline, 6-nitoxy4-quinoline, 6
-chloro-4-quinoline, 6-hydroxy-4-quinoline, 6-phenyl-4-quinoline, 7-methyl-4-quinoline, 8-methyl-4-quinoline and the like.

Z5 is (111) When the thiazole ring, benzothiazole ring, naphthothiazole ring, benzoxazole ring, naphthoxazole ring, benzoselenazole ring or naphthoselenazole ring having a substituent, this position &
Examples of W include a halogen atom, an alkyl group, an alkoxy group, a hydroxy group, a cyan group, a carboxy group, an alkoxycarbonyl group, an alkylamino group, an acylamino group, an acyl group, a phenyl group, and a cycloalkyl group.

Specific examples of the thiazole ring containing Z5 as the (1) component include thiazole, 4-phenylthiazole, 4°5-diphenylthiazole, 4-methyldeazole, 5-methylthiazole, 4-chlorothiazole, and 4-methylthiazole. 1-xideazole, etc., and the benzothiazole ring is benzothiazole, 5-chlorobenzothiazole, 5-phenylbenzothiazole, 5-methylbenzothiazole, 5-
methylbenzothiazole, etc., and the naphthodeazole ring is α-naphthothiazole, β-naphthothiazole, 5
-methoxy-β-naphthothiazole, 5-methyl-β-
These include naphthodeazole, 8-methoxy-α-naphthothiazole, 8-chloro-α-naphthodiazole, and the like. The benzoxazole ring containing z5 as a constituent is benzoxazole, 5-chlorobenzoxazole, 5-phenylbenzoxazole, 5-phenylbenzoxazole, 5-methylbenzoxazole, 5-methoxybenzoxazole, etc., and naphthoxazole The ring is α-naphthoxazole, β-naphthoxazole, 5-methoxy-β-naphthoxazole, 5-methyl-β-naphthoxazole, 8-methoxy-α-naphthoxazole
-oxazole, 8-chloro-α-naph; and oxazole.

The benzoselenazole ring containing Z5 as a constituent is benzoselenazole, 5-chlorobenzoselenazole, 5-phenylbenzoselenazole, -]enylbenzoselenazole, 5-methylbenzoselenazole, 5-methoxybenzo selenazole, etc., and the naphthoselenazole ring includes α-naphthoselenazole, β-naphthoselenazole,
5-methoxyβ-naphthoselenazole, 5-methyl-
These include β-naphthoselenazole, 8-me1-xyα-naphthoselenazole, 8-chloro-α-naphthoselenazole, and the like.

The alkyl groups represented by R7, Ra and R9 in the general formula [TV] are substituted or branched, such as methyl group, ethyl group, n-propyl group, i-propyl group, n
-butyl group, etc.

The acid anions represented by ions, nitrate ions, etc.

When the compound represented by the general formula [rV] forms an inner salt, R2 is 0.

Specific examples of sensitizing dyes represented by general formulas [II], [Iff] and [TV] are shown below.
■Work e Iθ I○ B, θ B, θ Work θ Below margin D-12 D-13 e Below margin D-25 I)-26 Below margin D-39 D-40 Below margin Below margin The above-mentioned general according to the present invention Formula [II], [I[[] or [
The sensitizing dye represented by rV ] may be added at any time during the emulsion manufacturing process, but is preferably added during or after chemical ripening, most preferably during chemical ripening. Addition M is from 10-7 per mole of silver halide
10-311-yl, preferably 5X 10-6 to 5X1
0-" mole.

The silver halide grains constituting the silver halide emulsion used in the present invention may be polydisperse silver halide grains or monodisperse silver halide grains. However, monodisperse silver halide grains are preferable from the viewpoint of achieving high sensitivity without adding fog, and moreover, the red-sensitive silver halide emulsion layer contains monodisperse silver halide grains in an amount of 50% or more. , preferably 75% by weight or more.

The monodisperse silver halide grains used in the present invention have a uniform shape and a uniform grain size when the emulsion is observed using an electron microscope, and are defined by the following formula. It has a particle size distribution. That is, the average grain size r of the grain size molecule 5 (T quasi-difference S
The value divided by 0.20 or less is 8, preferably 0.
．． It is less than 15% (orthogonal diameter distribution is less than 15%).

τ≦0.20 In the case of spherical silver halide grains, the average grain size refers to the diameter of the grain, and in the case of grains with shapes other than spherical, the projected times; The average diameter f& when converted into a circular image of area, and the particle size in use is rt
, and the number is ni, then r
is defined.

The above particle diameter can be measured by various methods commonly used in the technical field for the above purpose. A typical method is Loveland's "Particle Size Analysis Table jA.

S, T, M, Symposium on Light Microscopy 1955, pp. 94-122, or "Theory of the Photographic Process" by Mies and James, 3rd edition, published by Macmillan (1966), 2Q. has been done. The particle size can be measured using the 19 shadow area of the particle or an approximate diameter.

If the particles are of substantially uniform shape, the particle size distribution can be described fairly accurately as diameter or projected area.

The relationship between grain size distribution is described in "Empirical relationship between grain size distribution and sensitometric distribution in photographic emulsions," The Fuji Graphic Journal, LXXIXI, (1949) 3.
This can be determined by the method described in the article by 1-Ribery and Smith on pages 30-338.

Although the silver halide grains constituting the silver halide emulsion used in the present invention may have a cubic, octahedral, dodecahedral, or tetradecahedral crystal habit, the effect of the present invention is
It is more effective when using facepiece particles.

The silver halide fL agents used in the silver halide photographic light-sensitive material of the present invention include silver halide such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, and silver chloride f! Any material used in silver halide emulsions can be used. Preferably, 50 Iζ% or more of the silver halide used in 1 mol of red-sensitive silver halide is silver chlorobromide,
More preferably, it is 75% or more.

The silver halide grains constituting the red-sensitive silver halide emulsion of the present invention are preferably substantially j'' bromide ffR, and firstly j
Substantial silver chlorobromide grains have a silver chloride content of 25 mol % or more, more preferably 70 to 30 mol %.

In this case, the silver chlorobromide grains may contain 5 mol% or less of silver iodide.

Next, the lower LiJ-
(12) The compound represented by formula [1] (hereinafter referred to as the dye of the present invention) will be explained.

General formula [11 In the formula, R+J5 and R2 are respectively -〇N or -CF
R'R'', and R' and Rh each do not represent a hydrogen atom, a fluorine atom, or a fluorinated alkyl group having 1 to 4 carbon atoms.

R3J5 and R4 each represent an aliphatic group, an aromatic group or a heterocyclic group.

In the above general formula CI], R1 and R2 are each -
〇N or -〇FR'R'', and -〇FR'R
Examples of the fluorinated alkyl group represented by R' or R'' include difluoromethyl group, trifluoromethyl group, 1,1゜2.2-tetrafluoroethyl group, i, 1,2゜2 .3.3.4.4-octafluorobutyl group, 1.1.2,2.3.3-hexafluoropropyl group, etc.

R3 and R4 each represent an aliphatic group, an aromatic group, or a heterozygous group, and among these, as the aliphatic group,
Alkyl groups (e.g. methyl, ethyl, propyl,
butyl group, hexyl group, octyl group, dodecyl group, etc.), cycloargyl group (eg, cyclohexyl group, etc.), alkenyl group (eg, butenyl group, etc.). Furthermore, typical aromatic groups include aryl groups such as phenyl and naphthyl groups. Furthermore, representative examples of the heterocyclic group include a benzthiazolyl group and a benzoxasilyl group.

The aliphatic group, aromatic group, and heterocyclic group represented by R3 and R4 further include a hydroxy group, an amino group, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.),
Alkoxy M (e.g., methoxy group, ethoxy group, etc.),
It may be substituted with a carboxy group, a carbamoyl group, a sulfo group, a sulfamoyl group, an aryl group (eg, phenyl group, 4-sulfophenyl group, etc.), an aryloxy group (eg, phenoxy group, 4-sulfophenoxy group, etc.), or the like. In addition, an aryl group is an alkyl group having 1 to 4 carbon atoms (
For example, it may be substituted with a methyl group, an ethyl group, etc.).

Furthermore, examples of the aryl groups represented by R3 and R4 being substituted with a sulfo group include 4-sulfophenyl di, 3-sulfophenyl group, 2-methyl-4-sulfophenyl group, 2-chloro-4 -sulfophenyl group, 4-
Chloro-3-sulfophenyl group, 2-chloro-5-sulfophenyl group, 2-me]-xy-4-sulfophenyl group, 2-hydroxy-4-sulfophenyl group, 2.5-dichloro-4-sulfophenyl group , 2,6-cymethyl-4
-sulfophenyl group, 2,5-disulfophenyl group, 3
．． 5-disulfophenyl group, 4-phenoxy-3-sulfophenyl group, 2-chloro-6-methyl-4-sulfophenyl group, 3-carboxy-2-hydroxy-5-sulfophenyl group, 3,6-disulfophenyl group α-naphdyl group, 8-
Hydroxy-3,6-disulfo-α-naphthyl group, 5-
Examples include hydroxy-7-sulfo-β-naphthyl group and 6,8-disulfo-β-naphthyl group.

Examples of the heterocyclic groups R3 and R4 substituted with a sulfo group include a 2-(6-sulfo)benzthiazolyl group and a 2-(6-sulfo)benzoxasilyl group.

The sulfo group may also be bonded to an aryl group via a divalent organic group, such as 4-(4-sulfophenoxy)phenyl group, 4-(2-sulfonidel)phenyl group, 3-(sulfonidel)phenyl group, bomedylamino)phenyl group, 4-(2-
Mention may be made of the phenyl group (sulfoethoxy).

Of the above R1 and R2, preferably 10N group, CF
There are 3 units. Furthermore, among R3 and R4, an aromatic group is preferred, and a 4-sulfophenyl group and a 2.5-di-sulfophenyl group are particularly preferred.

Typical examples of the dye of the present invention represented by the general formula EII are shown below, but the dye of the present invention is not limited by these.

The following margin exemplified dye NaO: +S
Contains SOlNa5U
SO,KSO2N
H2S (to J 2 N M 2bU3
So, the dye represented by the general formula [1] is prepared by combining a 3-cyano-5-lasolone compound represented by the following general formula [V] and a compound represented by the following general formula [■] with a base. can be synthesized by reacting in the presence of

General formula [V] R3 General formula [VI] In the blank formulas below, R3 represents the same meaning as the above general formula [I],
○ indicates hydrogen atom, halogen atom (e.g. fluorine atom,
(chlorine atom, bromine atom), -valent organic group, trifluoromethyl group, ethoxycarbonyl group, etc. X is
Anions (e.g. chloride, bromide, iodide, verchlorate, p-toluenesulfonate,
methylsulfone-1-, ethylsulfonate, etc.), and m represents O or 1.

The bases to be present include pyridine, piperidine,
Trinibulamine, triethanolamine, heptulfoline, ammonia, etc. are used.

Solvents for the compounds include alcohols (e.g., methanol, ethanol, etc.), ethylene glycol, ethylene glycol monoalkyl ethers (e.g., ethylene glycol monomethyl ether, ethylene glycol monoethyl alcohol, etc.), acetonitrile, dimethyl sulfoxide, amide. (eg dimethylformamide, dimethylace1-amide, ace1-amide, etc.).

The reaction is suitably carried out at a temperature from 0°C to the boiling point of the solvent used, and the reaction reagent, general formula [V]
The 3-cyano-5-pyrazolone compound represented by the general formula [
VI], approximately twice the molar F
It is appropriate to use it once.

Further, the 3-cyano-5-pyrazolone compound represented by the general formula [v] can be synthesized using the manufacturing method described in British Special Edition No. 585.780.

Examples of synthesis of the dye of the present invention are shown below.
I will explain in detail.

Synthesis Example 1 (Synthesis of Exemplary Dye 4(1)) 1-(4'-sulfophenyl)-3-cyano-5-pyrazolone 10.0
g and glutacondialdehyde cyanyl salt M m 5 ,
7 g into dimethyl formaldehyde (10 h12), and further added 6.1 g of trinibulamine,
The mixture was stirred at air temperature for 4 hours. Next, 1501g of methanol
5.9 g of MI IV potassium dissolved in was added and stirred. Collect the precipitated dye crystals and ace! 9.79 dye to 17
is. The aqueous solution of this dye had a λmax of 645 nm.

Furthermore, dyes 15 to 26 used in the silver halide photographic material of the present invention can be produced by conventional methods. For example, 3-trifluoromethylpyrazolone and a suitable methane chain donor can be condensed in the presence of ml to synthesize 7-no, tri-, and penta-methine oxonol. 3-trifluoromethylpyrazolone is J
analof American Chemical
5ociety (Journal of the American Chemical Society), Vol. 68, page 42G, it can be easily synthesized by condensing trifluoroacetoacetate and the necessary hydrazine derivative. The manufacturing method of representative compounds among these dyes is shown below.

Synthesis example (synthesis of exemplified dye (15)) 1-(4'-sulfophenyl)-3-trifluorostyl-5 pyrazolone 6.170 and penta-1,3-diene-
3.54 m (l) of di-metachloroanyl hydrochloride was placed in 30*(2) of dimethyl formaldehyde, and an additional 4.05 (l) of triethylamine was added and stirred at 20-25°C for 3 hours.

Next, a 30% aqueous potassium acetate solution was added, and 2.4 liters of wood vinegar was added, followed by stirring for 30 minutes. 200 cc of acetonitrile was added to the reaction solution, and after stirring for 4 hours, it was stirred overnight. The precipitated crystals were collected by filtration. The crude crystals were then washed with acetotrile and dried.Then, the crude crystals were dissolved in 30 g of water and ethanol was added.
A mixed solution of oo, g and 100 d of acetonitrile was added, stirred, and left overnight. The precipitated crystals were collected by filtration, washed with acetonitrile and ethanol, and dried to obtain 3.24 (l) of dye.

The aqueous solution of this dye had a λmax of 627 nm.

The methanol solution of this dye had a λmax of 546 nm.

In the silver halide photographic light-sensitive material of the present invention, the dye represented by the general formula [I] can be incorporated into the silver halide photographic emulsion and used as an irradiation-preventing dye, or it can be used as an anti-irradiation dye. It can also be incorporated into hydrophilic colloid β and used as a filter dye or antihalation dye. Furthermore, depending on the purpose of use, two or more types of Dye No. 31 may be used in combination, or other dyes described below may be used in combination. The dye according to the present invention can be easily incorporated into a silver halide photographic emulsion layer or other hydrophilic colloid layer by a conventional method.

Generally, dyes or organic/inorganic alkali salts of dyes are dissolved in an aqueous solution or a low-temperature solvent (e.g., alcohols, glycols, cellosolves, dimethyl formaldehyde, dibutyl phthalate, tribrezyl phosphate, etc.), and if necessary, The dye can be incorporated into a silver halide photographic material by emulsifying and dispersing the dye and adding it to a coating solution for coating. The content of these dyes varies depending on the purpose of use, but in general, the content of these dyes per area on the photosensitive material
It is applied and used so that it becomes 0.01 to 301 B per Tl'.

The dye used in the present invention can be used in combination with dyes other than those of the present invention, and particularly preferably anthraginone dyes having the following general formula shown in US Pat. No. 2,865,752 and the like.

General formula [VII] In general formula [VII], R+, R4, R5 and R8 represent an aryl group, and R' and RII are a hydrogen atom or an alkyl group or aryl group having at least one sulfonic acid group or carbon II. , R2, Rs
, Rs and R7 are each a hydrogen atom, a carbon Ia group, a sulfone I! Or at least one carvone? a
W or an alkyl group or aryl group having a sulfonic acid group.

The alkyl group represented by R in the -OR group represented by R+, R4, Rs, and R8 in the formula -42 [)1] is, for example, a methyl group, an ethyl group, or a butyl group, and the aryl group represented by R is, for example, a phenyl group. It is. Also -R of the NR'R'' group
The alkyl group having at least one sulfonic acid group or carboxylic acid group represented by ' and R'' is, for example, -〇l-1
2303H.

-(CH2)2 SOa H, -OH2C00H1-(
CI-12) 2C○OH or its sodium salt, potassium salt or ammonium salt. Further, the aryl group represented by R' and R'' is, for example.

Further, the alkyl group or aryl group having at least one carboxylic acid group or sulfonic acid group in R2, R3, Rs, and R7 may be the same as those represented by R' and Rn. can.

The compound represented by the general formula [VII] is usually used after being dissolved in water or alcohol, and the amount of the compound added is 1 to 100 m! II/f, preferably 5~
50 meters! If/v' is added to the sphere.

Furthermore, the chemistry used for the above anthraquinone dyes, such as the dye o'1 of the present invention when used in rough combination with the dye of the present invention, is m
Fli is preferably 1:05 to 1:4.

Next, typical examples of the compound represented by the above general formula [VII] will be given.

Below margin [VII-11 [VII-2] ○ [VII-3] NaO:+5-HzC-N ONHCHzSO:+
Na [VII-4] [VII-51 [VII-61 OHONH M251J, INIL [VII-7] [VII-8] [VII-9] [VII-10] [VII-11] A [VII-12] N a O) S -82CN ON FIC;
M2b(JzNa[VII-13]CH.

CH.

[VII-14] [VII-151 [VII-16] [VII-171 [VII-181 Fuki] [VII-191 The following general cyan couplers are used in the diluted, 1-dipped silver halide emulsion of the present invention. Formulas [Vffi] and [
IX] is preferred.

General formula [V! ILI In the formula, R7 represents an alkyl group or an aryl group. R
8 represents an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group. R9 represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group. Also, R3 is R7
It may be combined with to form a ring. zl represents a hydrogen atom or a group that can be demultiplexed by reaction with an oxidized product of an aromatic primary amine color-forming Q main agent.

General Formula MX] In the formula, R+o represents a linear or branched alkyl group having 1 to 4 carbon atoms, and R11 represents a ballast group.

Zl has the same meaning as 71 in the general formula [V]. Particularly preferred R+o is a straight chain or branched alkyl group having 2 to 4 carbon atoms.

In the present invention, the alkyl group represented by R7 in the general formula [7M] is linear or branched, for example,
Methyl group, ethyl group, 1so-propyl group, butyl group,
Examples of the aryl group include a pentyl group, an octyl group, a nonyl group, and a tridecyl group. Examples of the aryl group include a phenyl group and a naphthyl group.

These groups represented by R7 may have a single substituent or a plurality of substituents. For example, substituents introduced into the phenyl group include halogen atoms (e.g., fluorine, chlorine, each atom such as bromine), alkyl group (e.g., methyl group, ethyl group, propyl group, butyl group, doacyl group, etc.), hydroxyl group, cyan group, nitro group,
Alkoxy groups (e.g., methoxy groups, ethoxy groups), alkylsulfonamide groups (e.g., methylsulfonamide groups, octylsulfonamide groups, etc.), arylsulfonamide groups (e.g., phenylsulfonamide groups, naphthylsulfonamide groups, etc.), Alkylsulfamoyl group (e.g., butylsulfamoyl group, etc.), arylsulfamoyl group (e.g., phenylsulfamoyl group, etc.)
, alkyloxycarbonyl M (e.g., methyloxycarbonyl group, etc.), aryloxycarbonyl group (e.g., phenyloxycarbonyl group, etc.), aminosulfonamide group (e.g., N,N-dimethylaminosulfonamide group, etc.), acylamino group, carbamoyl group, sulfonyl group, sulfinyl group, sulfoxy group, sulfo group,
Examples include an aryloxy group, an alkoxy group, a carboxyl group, an alkylcarbonyl group, and an arylcarbonyl group.

Two or more of these substituents may be introduced into the phenyl group.

The halogen atom represented by R9 is, for example, each atom such as fluorine, chlorine, or bromine, and the alkyl group is, for example, a methyl group, ethyl group, propyl group, butyl group, dodecyl group, or an alkoxy group. is, for example, a methoxy group,
These include ethoxy group, propyloxy group, butoxy group, etc.

R9 may combine with R7 to form a ring.

In the present invention, the alkyl group represented by R8 in the general formula [v plate] is, for example, a methyl group, an ethyl group, a butyl group,
These include a hexyl group, a tridecyl group, a pentadecyl group, a heptadecyl group, and a so-called polyfluoroalkyl group substituted with a fluorine atom.

The aryl group represented by R8 is, for example, a phenyl group or a naphthyl group, preferably a phenyl group. R8
The heterocyclic group represented by is, for example, a pyridyl group or a furan group. The cycloalkyl group represented by R8 is, for example, a cyclopropyl group or a cyclohexyl group. These groups represented by R3 may have a single or a plurality of substituents. For example, a typical substituent introduced into a phenyl group is a halogen atom (e.g. fluorine, chlorine, etc.). , each atom such as bromine), an alkyl group (e.g. methyl group, ethyl group, propyl group, butyl group, dodecyl group, etc.), a hydroxyl group, a cyan group, a nitro group, an alkoxy group (e.g. methoxy group, ethoxy group, etc.), Alkylsulfonamide group (e.g. methylsulfonamide group,
octylsulfonamide group, etc.), arylsulfonamide group (e.g., phenylsulfonamide group, naphthylsulfonamide group, etc.), alkylsul group (e.g., butylsulfamoyl group, etc.), arylsulfamoyl group (e.g., phenylsulfonamide group, etc.) moyl group, etc.), alkyloxycarbonyl group (e.g., methyloxycarbonyl group, etc.)
, aryloxycarbonyl group (e.g., phenyloxycarbonyl group, etc.), aminosulfonamide group, acylamino group, carbamoyl group, sulfonyl group, sulfinyl group, sulfoxy group, sulfo group, aryloxy group,
Examples include an alkoxy group, a carboxylalkylcarbonyl group, and an arylcarbonyl group. Two or more of these substituents may be introduced into the phenyl group.

Preferred groups represented by R8 include polyfluoroalkyl groups, phenyl groups or halogen atoms, alkyl groups, alkoxy groups, alkylsulfonamide groups, arylsulfonamide groups, alkylsulfamoyl groups, arylsulfamoyl groups, and alkylsulfonyl groups. arylsulfonyl group, alkylcarbonyl group, arylcarbonyl group, or cyano group as a substituent.

More preferably, the cyan coupler represented by the general formula [VJI] used in the present invention is a compound represented by the following general formula [V]-11.

General Formula [VIIl-1] In General Formula [VII-1], R 12 represents a phenyl group. This phenyl group may have a single or multiple substituents, and typical examples of the substituents introduced are halogen atoms (e.g. fluorine, chlorine, bromine, etc.).
, alkyl groups (e.g. methyl group, ethyl group, propyl group, butyl group, octyl group, dodecyl group, etc.), hydroxyl group, cyano group, nitro group, alkoxy group (e.g. methoxy group, ethoxy group, etc.), alkylsulfonamide group (
For example, methylsulfonamide group, octylsulfonamide group, etc.), arylsulfonamide group (for example, phenylsulfonamide group, naphthylsulfonamide group, etc.), alkylsulfamoyl M (for example, butylsulfamoyl group, etc.), arylsulfamoyl group (e.g. phenylsulfamoyl group etc.), alkyloxycarbonyl u(f
(e.g., methyloxycarbonyl N, etc.), aryloxycarbonyl group (e.g., phenyloxycarbonyl group, etc.)
etc. can be mentioned. Two or more of these substituents may be attached to the phenyl group. Preferred groups represented by R12 include phenyl, a halogen atom (preferably fluorine, chlorine, and bromine), and an alkylsulfonamide group (preferably is 〇-methylsulfonamide group, p-octylsulfonamide group, O-dodecylsulfonamide group), arylsulfonamide group (preferably phenylsulfonamide group), alkylsulfamoyl group (preferably butylsulfamoyl group) , one or two arylsulfamoyl groups (preferably phenylsulfamoyl groups), alkyl groups (preferably methyl groups, trifluoromethyl groups), alkoxy groups (preferably methoxy groups, ethoxy groups) as substituents. It is a phenyl group having the above.

R13 is an alkyl group or an aryl group. The alkyl group or aryl group may have a single or multiple substituents, and typical examples of these substituents include:
Halogen atoms (e.g. fluorine, bromine, etc.), hydroxyl groups, carboxyl groups, alkyl groups (e.g. methyl, ethyl, propyl, butyl, octyl, dodecyl, etc.), aralkyl groups, cyano groups, ~Ro group,
Alkoxy groups (e.g. methoxy groups, oxy groups), aryloxy groups, alkylsulfonamide groups (e.g. methylsulfonamide groups, octylsulfonamide groups, etc.)
, arylsulfonamide group (e.g. phenylsulfonamide group, naphthylsulfonamide group, etc.), alkylsulfamoyl group (e.g. butylsulfamoyl group, etc.),
Arylsulfamoyl group (e.g. phenylsulfamoyl group etc.), alkyloxycarbonyl group (e.g. methyloxycarbonyl group etc.), aryloxycarbonyl group (e.g. phenyloxycarbonyl group etc.), aminosulfonamide group (e.g. dimethylaminosulfone etc.) amide group, etc.), an alkylsulfonyl group, an arylsulfonyl group, an alkylcarbonyl group, an arylcarbonylamide group, a carbamoyl group, a sulfinyl group, and the like. 211ii or more of these substituents may be introduced.

Preferred groups represented by RI3 include n. When nl = 0, it is an alkyl group, and when nl -1 or more, it is an aryl group. A more preferable group represented by R+3 is an alkyl group having 1 to 22 carbon atoms (preferably a methyl group, ethyl group, propyl group, butyl group, octyl group, or dodecyl group) when +1+=O. When n1=1 or more, phenyl group or alkyl group (preferably t~
butyl group, °C-amyl group, octyl group), alkylsulfonamide group (preferably butylsulfonamide group, octylsulfonamide group, dodecylsulfonamide group)
, arylsulfonamide group (preferably phenylsulfonamide group), aminosulfonamide group (preferably dimethylaminosulfonamide group), alkyloxycarbonyl group (preferably methyloxycarbonyl group, butyloxycarbonyl group) as a substituent 1 one or two
It is a phenyl group having one or more.

R+4 represents an alkylene group. It represents a linear or branched alkylene group having 11 to 20 carbon atoms, and furthermore 1 to 12 carbon atoms.

R 15 represents a hydrogen atom or a halogen atom (fluorine, chlorine, bromine or iodine). Preferably it is a hydrogen atom.

nl is O or a positive integer, preferably O or 1
It is.

X bar Q-, -CO-, -COO-, -OCO-,
-SO2NR-, -NR'302NR''-, -S-,
Represents a divalent group of -SO- or -SO2-. Here, (R', R'' represent an alkyl group, R r , R
rr may each have a substituent. ). X is preferably -0-, -S-, -SO-, -SO2-.

Zl represents a hydrogen atom or a group which is removed by a reaction with an aromatic primary amine-based color developing agent, and is decomposed.

Preferred are chlorine atom and fluorine atom.

In the present invention, the linear or branched argyl group having 1 to 4 carbon atoms represented by R10 in the general formula [[x] is, for example, an ethyl group, a propyl group, a butyl group, a 1so-propyl group, a 1so- A butyl group, a 5ec-butyl group, or a tert-butyl group, which may have a substituent. Examples of the substituent include an acylamino group (eg, acetylamino group), an alkoxy group (eg, methoxy group), and the like.

R10 is preferably an alkyl group having 2 to 4 carbon atoms.

A ballast group, represented by RI+, is an organic group having a size and shape that imparts sufficient bulk to the coupler molecule to substantially prevent the coupler from diffusing from the layer to which it is applied to other layers.

Typical ballast groups include alkyl or aryl groups having 8 to 32 total carbon atoms.

These alkyl groups or aryl groups may have a substituent. Examples of substituents for the aryl group include an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a carboxy group, an acyl group, an ester group, a hydroxy group, a cyan group, a nitro group, a carbamoyl group, a carbonamide group, an alkylthio group, Examples thereof include an arylthio group, a sulfonyl group, a sulfonamide group, a sulfamoyl group, and a halogen atom. Furthermore, examples of substituents for the alkyl group include the substituents listed above for the aryl group except for the alkyl group.

Particularly preferred as the ballast group are those represented by the following general formula [X].

General formula [×] -CH-0-Ar R12 represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, Ar represents an aryl group such as a phenyl group, and this aryl group may have a substituent. good. Examples of the substituent include an alkyl group, a hydroxy group, an alkylsulfonamide group, and the most preferred is a branched alkyl group such as [-butyl group.

In the general formulas [■■ By modifying the reactivity of the coupler, or separating from the coupler, it performs functions such as development inhibition, bleaching inhibition, and color correction in the coating layer or other layers containing the coupler in silver halide color photographic light-sensitive materials. This is something that works advantageously. As a typical example,
For example, halogen atoms such as chlorine and fluorine, substituted
Examples include an unsubstituted alkoxy group, aryloxy group, arylthio group, carbamoyloxy group, acyloxy group, sulfonyloxy group, sulfonamide group, heteroylthio group, heteroyloxy group, and the like. Particularly preferred Zl is a hydrogen atom or a chlorine atom.

More specifically, JP-A-50i0135 and JP-A-50-1
No. 20334, No. 50-130441, No. 54-4
No. 8237, No. 51-146828, No. 54-14
No. 736, No. 47-37425, No. 5O-1233
No. 41, No. 58-95346, Special Publication No. 48-3689
No. 4, U.S. Pat. No. 3,476.563, U.S. Pat. No. 3.737.
No. 316 and No. 3,227.551.

Typical specific examples of cyan couplers represented by the general formula rVll[J are shown below in the margins, but are not limited to these (n)
CtzLs 502NI((n)C+6HasSOzNl(C4Hs(n)(,:t2MzsLnJ) Next, specific examples of the coupler represented by the general formula [l×] will be shown, but the coupler is not limited thereto.

In order to incorporate the cyan coupler of the present invention into an emulsion, for example, phthalate esters (dibubuur phthalate, dibubuur phthalate, etc.), phosphoric acid esters (tricresyl bosphate, triphenyl phosphate, trioctyl phosphate) or High boiling point organic solvents such as N,N-dialkyl exchange amides (N,N-diedylauramide etc.) and low boiling point non-solvents such as ethyl acetate, butyl acetate or butyl pionate, respectively. After dissolving the cyan coupler of the present invention alone or in a mixture in a solvent or a mixture of those solvents as necessary,
It is possible to prepare a silver halide emulsion by mixing it with an aqueous gelatin solution containing a surfactant and then emulsifying and dispersing it using a high-speed rotary mixer, colloid mill, or ultrasonic disperser, and then adding it to silver halide. can.

On the other hand, in the present invention, a hardening agent can be used to improve the physical properties of the film.

The hardeners preferably used in the present invention are chlorotriazine hardeners represented by the following general formulas [XI] and [XI[].

The general formula [represents a group or an aryl group], N HCORs” (Rs
represents a hydrogen atom, an alkyl group, an aryl group or an alkylthio group) or -0MQ (M is a monovalent metal atom), and R4O replaces a chlorine atom and has the same meaning as R9.

General formula [XIl] In general formula [XII], R++ and R12 are chlorine atom, hydroxyl group, alkyl group, alkoxy group or 10M
represents a group (M is a monovalent metal atom). Q.

Q' represents a linking group representing 10-1-S-1-NH-, and L represents an alkylene group or an arylene group.

2 and m do not represent 0 or 1.

Next, the alkyl group represented by R9 and R+o in the general formula [XI] is, for example, a methyl group, an ethyl group, a butyl group, etc., and specific examples of the alkoxy represented by these groups are taken, T
M in bar NHCOCH3 and -NHCO-○MW is, for example, a sodium atom, a potassium atom, or the like.

Regarding the chlorotriazine hardeners represented by the general formula [XI], US Pat.
No. 9607, JP-A-48-19220, JP-A No. 51-78
No. 788, No. 52-60612, Zhou 52-1281
No. 30, No. 52130326, No. 5B-1043
There are descriptions in the above-mentioned standards, and any of them can be used in accordance with the above standards.

Next, the alkyl group represented by R11 and R+2 in the general formula [Xn] is, for example, a methyl group, ethyl group, butyl group, etc., the alkoxy group is a methoxy group, ethoxy group, butoxy group, etc., and M in -0M W is For example, 1-lium atom, potassium atom, etc.

Further, the alkylene group represented by L is, for example, -CH2-1-
(CH2)2-1-(CH2)s- group, etc., and the arylene group is, for example, p-10- or m-phenylene group.

Regarding the chloroI'l)-riazine hardener represented by the general formula [XII], Canadian Patent No. 895,808,
They are described in Japanese Patent Publication No. 58-33542 and Japanese Patent Application Laid-Open No. 57-40244, and can be selected and used based on the above criteria.

The compounds represented by the general formulas [XI] and [XI[] are present in at least 10 of the emulsion layers or auxiliary layers according to the present invention.
Alternatively, multiple layers may be selected and added.

The additive is dissolved in water or alcohol (e.g. methyl alcohol, ethyl alcohol, etc.) and added at a concentration of 1 g per 1 g of gelatin.
~100mg, preferably 5-5011g is added.

The addition method may be either a batch method or an in-line method.

Next, typical examples of compounds represented by the general formula [XI] or [XII] will be listed, but the present invention is not limited thereto.

The following margin is 1428 [Xll core is
1) (te-2) (XI-3
) (n-4)(
XI-5) (X
I-6) (XI-7) (
XI-8) (XI-9) (
XI-10) (XI-11)
(XI-12) (X'l-13) Below, in the margin Ichitsu formula rx'u is shown. 4) (■-5) (■-6) (■-7) (X[[-8) (■-9) (■-1o) The following margins The silver halide photographic light-sensitive material of the present invention is, for example, Although it is possible to use color negative and positive films, color photographic paper, etc., the effect of the method of the present invention is effectively exhibited when color photographic paper used for Toriwa (2018) Direct Photography 1:x is used. be done.

The silver halide photographic material of the present invention, including this color photographic paper, may be one for monochrome use or one for multicolor use. If 1 silver cogenide photographic exposure for multicolor <4 size,
In order to perform subtractive color reproduction, a silver halide emulsion layer containing magenta, yellow, and cyan couplers as photographic couplers and a non-light-sensitive layer are usually formed on a support in an appropriate number and order. Although it has an IR structure with VJ layers, the number of months and the order of the layers may be changed as appropriate depending on the river fish performance and purpose of use.

The silver halide photographic material (■) of the present invention has 0 multicolor color sensitivity.
In the case of a dye, the specific composition includes a support A, a dye A-dye image forming layer on water from the support side, an intermediate layer, a magenta dye image forming layer of the present invention, an intermediate layer,
Particularly preferred are those arranged with a cyan dye image forming layer, an intermediate layer and a protective layer.

The silver halide emulsion used in the silver halide photographic light-sensitive material of the present invention includes conventional halides such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, and silver chloride. Any of those used in silver emulsions can be used.

The silver halide grains used in the silver halide emulsion of the present invention may be obtained by any of the acid method, neutral method, and ammonia method. The particles may be grown all at once, or may be grown after seed particles are created. The method of creating and growing the seed particles may be the same or different.

In the silver halide emulsion, halide ions and silver ions may be mixed simultaneously, or one may be mixed in the presence of the other. In addition, while considering the critical growth rate of silver halide crystals, we added halide ions and silver ions to
)(, 1) A(I) may be produced by controlling and sequentially adding I at the same time. After growth, a conversion method may be used to change the halogen composition of the particles.

When producing the silver halide emulsion of the present invention, the grain size, grain shape, grain size distribution, and grain growth rate of silver halide grains can be controlled by using a silver halide solvent as necessary.

The silver halide grains used in the silver halide emulsion of the present invention are prepared in the process of forming and/or growing the grains such as cadmium salt, zinc salt, lead salt, thallium salt, iridium salt or complex salt, rhodium salt or complex salt. , iron salts or complex salts, can be incorporated into the interior of the particles and/or on the surface of the particles, and by placing them in an excessively reducing atmosphere, they can be incorporated into the interior of the particles and/or on the particle surfaces. It is possible to add reduction-sensitized nuclei to.

In the silver halide emulsion of the present invention, unnecessary soluble salts may be removed after the growth of silver halide grains is completed, or they may be left contained. In the case of removing the salts, it can be carried out based on the method described in Research Disclosure No. 17643.

The silver halide grains used in the silver halide emulsion of the present invention may consist of a uniform layer inside and on the surface, or
It may consist of different layers.

The silver halide grains used in the silver halide emulsion of the present invention may be grains in which a latent image is mainly formed on the surface, or grains in which a latent image is mainly formed inside the grains.

The silver halide grains used in the silver halide emulsion of the present invention may have a regular crystal shape or may have an irregular crystal shape such as a spherical shape or a plate shape. In these particles, any ratio of the (100) plane to the (111) plane can be used.

Further, the particles may have a composite form of these crystal forms, or particles of various crystal forms may be mixed.

The silver halide emulsion of the present invention may be a mixture of two or more separately formed silver halide emulsions.

The silver halide emulsion of the present invention is chemically sensitized by a conventional method. That is, compounds containing sulfur that can react with silver ions,
The sulfur sensitization method using activated gelatin, the selenium sensitization method using selenium compounds, the reduction sensitization method using reducing substances, the total sensitization method using gold or other negative metal compounds, etc. can be used alone or in combination. I can do it.

Sensitivity 4-・L9 Totsuhe Pan silver emulsion is produced using dyes known as sensitizing dyes in the photographic industry.
Can be optically sensitized to a desired wavelength range. The sensitizing dyes may be used alone or in combination of two or more. Along with the sensitizing dye, the emulsion contains a dye that itself does not have a spectral sensitizing effect, or a supersensitizer, which is a compound that does not substantially absorb visible light and enhances the sensitizing effect of the sensitizing dye. Also good.

The silver halide emulsion of the present invention may be used during chemical ripening and/or for the purpose of preventing fog during the 3B process of manufacturing, storage, or photographic processing of light-sensitive materials, and/or to maintain stable photographic performance. At the end of the process and/or after chemical ripening and before coating the silver halide emulsion, compounds known in the photographic industry as antifoggants or stabilizers can be added.

Gelatin is advantageously used as a binder (or protective colloid) for the silver halide emulsion of the present invention, but
In addition, hydrophilic colloids such as gelatin derivatives, graft polymers of gelatin and other polymers, proteins, sugar derivatives, cellulose derivatives, and synthetic hydrophilic polymeric substances such as monopolymers or copolymers can also be used. .

The photographic emulsion layer and other hydrophilic colloid layers of the light-sensitive material using the silver halide emulsion of the present invention can be formed by using, alone or in combination, a hardening agent that crosslinks binder (or protective colloid) molecules and increases film strength. It is hardened. It is desirable to add the hardening agent to the extent that the photosensitive material can be hardened to the extent that it is not necessary to add the hardening agent to the processing solution, but it is also possible to add the hardening agent to the processing solution.

A plasticizer can be added for the purpose of increasing the flexibility of the silver halide emulsion layer and/or other hydrophilic colloid layer of a light-sensitive material using the silver halide emulsion of the present invention.

A dispersion (latex) of a water-insoluble or sparingly soluble synthetic polymer is added to the photographic emulsion layer or other hydrophilic colloid layer of a photosensitive material using the silver halide emulsion of the present invention for the purpose of improving the stability by one degree. It can be included.

In the emulsion layer of the silver halide color photographic light-sensitive material of the present invention, an aromatic primary amine developer (
For example, a dye-forming coupler is used that forms a dye by performing a coupling reaction with an oxidized product of p-phenylenediamine derivatives, aminophenol derivatives, etc.). The dye-forming coupler is usually selected for each emulsion layer so that a dye is formed that absorbs light from 1 to 10% of the emulsion layer's light sensitivity, and a yellow light-absorbing dye is formed for the blue light-sensitive emulsion layer. A magenta dye-forming coupler is used in the green light-sensitive emulsion layer, and a cyan dye-forming coupler is used in the red light-sensitive emulsion layer.

However, depending on the purpose, silver halide color photographic materials may be produced using different combinations of the above.

Examples of yellow dye-forming couplers include acylacetamide couplers (e.g., benzoylacetanilides, pivaloylat-anilides), and magenta dye-forming couplers include, in addition to the couplers of the present invention, 5-pyrazolone couplers and pyrazolobenzimidazole couplers. , pyrazolotriazole, open-chain acylacetonitrile couplers, etc. These dye-forming couplers preferably have a group called a ballast group in the molecule, which makes the coupler non-diffusive and has 8 or more carbon atoms. In addition, even if these dye-forming couplers are 4-functional, in which 4 silver ions need to be reduced in order to form one molecule of dye, only 2 silver ions need to be reduced. Either of the two motherhoods is fine.

For hydrophobic compounds such as dye-forming couplers that do not need to be adsorbed onto the silver halide crystal surface, various methods such as solid dispersion, latex dispersion, and oil-in-water emulsion dispersion can be used. It can be appropriately selected depending on the chemical structure of the hydrophobic compound. The oil-in-water emulsion dispersion method can be applied to a method of dispersing hydrophobic additives such as couplers, and is usually mixed with a high-boiling point solvent with a boiling point of about 150°C or higher, and if necessary with a low-boiling point solvent and/or Dissolve using a water-soluble aqueous solution, add a surfactant to a hydrophilic binder such as an aqueous gelatin solution, and use a dispersion device such as a stirrer, homogenizer, colloid mill, flow jib 1 to mixer, or ultrasonic device. After emulsification and dispersion, the desired hydrophilic colloid may be added to Fuchu. A step of removing the low boiling point solvent may be included simultaneously with the dispersion or dispersion.

Examples of high boiling point oils include phenol H31 which does not react with the oxidized form of the developing agent, phthalate esters, phosphate esters,
Boiling point 15 of citric acid ester, benzoic acid ester, alkyl amide, fatty acid ester, trimesic acid ester, etc.
A modified solvent having a temperature of 0° C. or higher is used.

Anionic surfactants, nonionic surfactants, A cationic surfactant can be used.

Between the emulsion layers of the color photographic light-sensitive material of the present invention (between the same color-sensitive layers and/or between different color-sensitive layers), the oxidized form of the developing agent or the electron transfer agent may migrate, causing color blurring or sharpness. Color antifogging agents are used to prevent deterioration in quality and noticeable graininess.

The color antifoggant may be used in the emulsion layer itself, or in an intermediate layer provided between adjacent emulsion layers.

In the color light-sensitive material using the silver halide emulsion of the present invention, an image stabilizer can be used to prevent deterioration of the dye image.

A UV absorber is added to the hydrophilic colloid layers such as the protective layer and intermediate layer of the photosensitive material of the present invention in order to prevent fogging due to discharge caused by charging of the photosensitive material due to friction, etc., and to prevent image deterioration due to UV light. It may be included.

The silver halide emulsion layer and/or other hydrophilic colloid layer of the silver halide photosensitive material using the silver halide emulsion of the present invention reduces the gloss of the photosensitive material, increases the writeability, and sticks the photosensitive materials together. Pine 1~ agent can be added for the purpose of prevention etc.

A lubricant can be added to reduce the sliding friction of the light-sensitive material using the silver halide emulsion of the present invention.

An antistatic agent for the purpose of preventing static electricity can be added to a light-sensitive material using the silver halide emulsion of the present invention.

Antistatic agents are sometimes used in the antistatic layer on the side of the support on which the emulsion is not laminated, or they are used to protect the emulsion layer and/or the side other than the emulsion layer on which the emulsion layer is laminated with respect to the support. It may also be used in a colloid layer.

The photographic emulsion layer and/or other hydrophilic colloid layer of the light-sensitive material using the silver halide emulsion of the present invention may include improved coatability,
Various surfactants are used for the purposes of preventing static electricity, improving slipperiness, dispersing emulsions, preventing adhesion, and improving photographic properties (such as accelerating development, increasing contrast, and sensitization).

The light-sensitive material using the silver halide emulsion of the present invention has a photographic emulsion layer, and other layers include a flexible reflective support such as baryta paper, paper laminated with α-olephne polymer, synthetic paper, cellulose acetate, nitric acid, etc. cellulose, polystyrene,
It can be applied to films made of semi-synthetic or synthetic polymers such as polyvinyl chloride, polyethylene terephthalate, polycarbonate, and polyamide, as well as to rigid bodies such as glass, composite materials, and ceramics.

The monthly silver halide yield of the present invention is obtained by subjecting the surface of the support to corona discharge, S11 external ray irradiation, flame treatment, etc. as necessary.
Direct or (support surface adhesion, antistatic properties, usage stability, abrasion resistance, hardness, antihalation properties, friction properties,
and/or to improve its characteristics) 1 or 2
It may be applied through the above undercoat layer.

When coating a photographic light-sensitive material using the silver halide emulsion of the present invention, a thickener may be used to improve coating properties. Particularly useful coating methods are ex-dulsion coating and curtain coating, which allow two or more types of coating to be applied simultaneously.

In the photosensitive material of the present invention, the photosensitive material S1 of the present invention can be exposed using electromagnetic waves in a spectral range to which the emulsion layer constituting B1 has sensitivity.As a light source, natural light (sunlight), tungsten electric lamp, etc. , fluorescent lamps, mercury lamps, Gisenon arc lamps,
Known light sources such as carbon arc lamps, xenon flash lamps, cathode ray tube flying spots, various laser lights, light emitting diode lights, electron beams, X-rays, gamma rays, alpha rays, etc. Either can be used.

Exposure times include not only exposure times of 1 millisecond to 1 second commonly used in cameras, but also exposure times shorter than 1 microsecond, such as exposure times of 100 microseconds to 1 microsecond using cathode ray tubes and xenon flash lamps.
Microsecond exposures can be used, and exposures longer than 1 second are also possible. The exposure may be carried out continuously or intermittently.

The silver halide photographic JJ material of the present invention can be used to form an image by color development as known in the art.

The aromatic primary amine color developing agents used in the color developing solution of the present invention include known ones that are widely used in various color photographic processes. These developers include aminophenol and p-phenylenediamine derivatives. These compounds are %1
Since it is more stable than the flJ state, it is generally used in the form of a salt, such as a hydrochloride or a sulfate. Additionally, these compounds are generally used at a concentration of about 100 to about 300 per color developer solution 12, preferably about 1 g to about 1 g per 1 r of color developer solution.
Use at a concentration of about 150.

Examples of amine phenol-based liquids include 0-amine phenol, p-aminophenol, 5-amino-2-
These include oxy-1-toluene, 2-amino-3-oxy-1-toluene, 2-71xy-3-amino-1,4-dimethylbenzene, and the like.

Particularly useful aromatic primary amine color developers are N, N'
-Dialkyl-p-phenylenediamine compound, and the alkyl group and phenyl group may be substituted with any substituent. Among them, an example of a particularly useful compound is N,N'-diethyl-p-phenylenediamine [
i salt, N-methyl-p-phenylenediamine hydrochloride, N
, N'-dimedylu-p-phenylenediamine hydrochloride, 2-amino-5-(N-ethyl-N-dodecylamino)-toluene, N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4- aminoaniline sulfate,
N-ethyl-N-β-hydroxyedylaminoaniline, 4-amino-3-methyl-N.

N'-diethylaniline, 4-amino-N-(2-methyl
-xyethyl)-N-ethyl-3-methylaniline-〇-toluenesulfonate and the like.

In addition to the above-mentioned primary aromatic amine color developer, the color developer used in the process of the present invention contains various components normally added to color developers, such as sodium hydroxide, Optionally contain alkaline agents such as sodium carbonate and potassium carbonate, alkaline residual pressure sulfites, alkali metal bisulfites, alkali metal thiocyanates, alkali metal halides, benzyl alcohol, water coloring agents, CP coloring agents, etc. You can also do that. The pH value of this color developer is usually 7 or higher, most commonly about 10
〜about 13.

In the present invention, after color development processing, processing is performed with a processing liquid having a fixing ability, but if the processing liquid having a fixing ability is a fixing liquid, a bleaching treatment is performed before that. A metal complex salt of an organic acid is used as a bleaching agent in the bleaching process, and the metal complex salt has the effect of oxidizing the metallic silver produced during development and converting it into silver halide, and at the same time coloring the uncolored areas of the coloring agent. It has a structure in which a total ion of iron, cobalt, copper, etc. is coordinated with an aminopolycarboxylic acid or an organic acid such as oxalic acid or citric acid. The most preferable halogen acid used to form such a metal complex salt of sulfuric acid includes polycarboxylic acid or aminopolycarboxylic acid. These polycarboxylic acids or aminopolycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts.

Specific representative examples of these include the following.

[1] Ethylenediaminetetraacetic acid [2] Nitrilotriacetic acid [3] Iminodiacetic acid [4] Ethylenediaminetetraacetic acid disodium salt [5] Nigelenediaminetetraacetic acid tetra(1-limethylammonium) salt [6] Ethylenediaminetetraacetic acid tetrana 1-Rium salt [7] Sodium salt of 21-lilotriacetate The bleaching agent used contains the above-mentioned total complex salt of isoic acid as a bleaching agent, and may also contain various additives. can. As additives, it is particularly desirable to include rehalogenating agents such as alkali halides or ammonium halides, such as potassium bromide, sodium bromide, sodium chloride, and ammonium bromide, gold mud salts, and chelating agents.

Also, the pH of borates, oxalates, acetates, carbonates, phosphates, etc.
Those known to be added to ordinary bleaching solutions, such as lj softening agents, alkylamines, and polyethylene A oxides, can be added as appropriate.

Further, the fixing solution and the bleach-fixing solution contain ammonium sulfite,
Potassium sulfite, ammonium bisulfite, potassium bisulfite, sodium thyanite, ammonium metabisulfite, potassium metabisulfite, sulfites such as cum, sodium metabisulfite, boric acid, borax, sodium hydroxide, potassium hydroxide, It may contain one or more pl-1 buffers consisting of various salts such as sodium carbonate, potassium carbonate, sodium bisulfite, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, and ammonium hydroxide.

When carrying out the process of the present invention while replenishing the bleach-fix solution (bath) with a bleach-fix replenisher, thiosulfur R is added to the bleach-fix solution (bath).
Salts, thiocyanates, sulfites, etc. may be contained, or the bleach-fixing replenisher may contain these salts and be replenished into the processing bath.

In the present invention, in order to increase the activity of the bleach-fix solution, air or oxygen may be blown into the bleach-fix bath and the storage tank for the bleach-fix replenisher, if desired (or as appropriate). An oxidizing agent such as hydrogen peroxide, bromate, persulfate, etc. may be added as appropriate.

[Specific Effects of the Invention FA] According to the present invention, by using a specific red-sensitizing dye in combination with a dye, high sensitivity can be achieved, and the sensitivity can be maintained even when the sample is stored over time with little desensitization and sharpness. A silver halide photographic material with excellent properties can be obtained.

[Specific Examples of the Invention] The present inventors conducted various experiments to confirm the effects of the present invention, and representative examples thereof are shown below.

Example 1 A total of 10 types of samples were prepared by coating the following first and second layers on a reflective support made of polyethylene-coated paper.

First plate... Red-sensitive silver chlorobromide emulsion layer' 5 x 10-5 per mole of silver halide shown in Table 2
30 moles of silver chloride sensitized using a red-sensitive sensitizing dye
Mol% containing average particle size 0.4 μm, monodispersity S=0.
Silver chlorobromide emulsion No. 12, an emulsion dispersion prepared by dissolving the cyan coupler (C-1> and 2.5-di-t-octylhydroquinone shown below in dioctyl phthalate), and the dyestuff shown in Table 2. It was applied using a 3% aqueous solution.

2nd layer: Protective layer gelatin and H-1 applied as hardener m100C
It was applied at a concentration of 0.4 mg per B+.

Table-1 Table-2 SR-I R-1 COCH=CH2 CH25O2CH=CH2 H2C=HCO2S142CC-CH2SO2CH=C
) 12inside CH25O2CH=CH2 H-2 is methyl alcohol H-3 was dissolved in acetone and added.

The margin below is a total of 10 types of samples created in this way (sample numbers 1 to 1)
The performance of 0) was evaluated using the method shown below, and the results are summarized in Table 3.

(1) Sensitivity After the sample was exposed to optical calibration and subjected to the standard processing shown below, the red density of the obtained cyan dye image was measured using a Sakura color depth meter PDΔ-60 to determine the relative sensitivity.

Standard processing steps (processing temperature and processing time) [1] Color development 38°C 3 minutes 30 seconds [2 bleach-fixing 33°C 1 minute 30 seconds [3] Washing process 25
~30℃ 3 minutes [4] Drying 75~80℃ approximately 2 minutes Processing solution composition (color development tank solution) Benzyl alcohol 15v12 ethylene glycol 15'NiQ potassium sulfite 2.0g Potassium bromide
0.7g sodium chloride
0.2g potassium carbonate 3o,
og hydroxylamine sulfate 3.0g polyphosphoric acid (TPPS) 2.5 (+3-methyl-4-amino-N-edyl-N-(β-methanesulfonamidoethyl)aniline sulfate JP
5,50 Fluorescent brightener (4,4'-diaminostilbenzsulfonic acid derivative) i,og Potassium hydroxide 2.0g Add water to bring the total amount to 12, and adjust the pH to 10.20.

(Bleach-fix tank solution) Ethylenediaminetetraacetic acid ferric ammonium dihydrate 60g Ethylenediaminetetraacetic acid 3g Ammonium diA sulfate (70% solution) 100d Ammonium sulfite (40% solution) 27.5. , Q Adjust the pH to 7.1 with potassium carbonate or glacial acetic acid, and add water to bring the total volume to 11.

(2) Raw sample storage desensitization Sample stored at 25°C and 160% relative humidity for 3 months (A
) and the fresh comparative sample (B), respectively, relative sensitivities SA, S[3 were determined according to the method of (1) sensitivity.

Raw sample storage desensitization (%) = 100 (1-'-bar)B (3) Sharpness A resolution test chart was printed on each sample with red exposure, and after processing according to the above processing steps, The density of the image was measured using a microphotometer, and the value expressed by the following formula was defined as the sharpness.

The larger this value is, the better the sharpness is.

Margin below Table-3 *Mark: Sample of the present invention A relative sensitivity of 90 or less is a practical problem.

``If the raw storage desensitization is not less than 5%, a large loss will occur during printing.

A sharpness of 0.4 or less is a practical problem.

In light of the above criteria, (1) Relative sensitivity (2) Raw sample storage desensitization (3) It is the sample of the present invention (Test was confirmed.

Example 2 A total of 19 types of samples were prepared by coating the following 1st to 7th layers on a reflective support made of polyethylene 11Fa paper.

First layer: Blue-sensitive silver chlorobromide emulsion layer A silver chlorobromide emulsion containing 5 mol% of silver chloride and the following yellow couplers (Y-1> and 2.5-di(1)-octylhydroquinone) was applied using an emulsified dispersion prepared by dissolving it in dioctyl phthalate.

Second layer: First intermediate β 2.5-G t-Octylhydroquinone was dissolved in dioctyl phthalate-1. An emulsified dispersion prepared by dissolving it was coated.

Third layer...Green-sensitive silver chlorobromide emulsion layer A silver chlorobromide emulsion containing 30 mol% of silver chloride, the following magenta coupler (M-1) and 2゜5-di(t)-
An emulsified dispersion prepared by dissolving 73 ctyl hydroquinone in dioctyl phthalate was used for coating.

4th layer...Second intermediate layer The following ultraviolet absorber (LIV-1) and 2.5-G
t-octylhydroquinone to dioctyl phthalate 1~
It was applied using an emulsified dispersion prepared by dissolving it in

5th group... Red-sensitive silver chlorobromide emulsion layer Containing silver chloride shown in Table 5, average grain size 0.4 μm!
An emulsion obtained by sensitizing a silver chlorobromide emulsion with monodispersity S = 0.14 using the red-sensitive sensitizing dye shown in Table 5, and the following cyan coupler (C-2') and 2°5-di [-An emulsified dispersion prepared by dissolving octylhydroquinone in dioctyl phthalate 1-, and 3 of the dyes shown in Table-5.
% aqueous solution.

6th layer...Third intermediate layer The following ultraviolet absorbers (LJV-1> and 2,5-G
t-octylhydroquinone to dioctyl phthalate-1~
A 3% aqueous solution of a dye not shown in Table 5 was used for coating.

No. 7: A pox was applied using Latin and the hardening agent (T1-1) as a protective mouthpiece.

Below is the margin V-1 ffi of the main components of each layer (ma per 100cat
ffl) are shown in Table-4.

Table 4 Table 5 [VII-1] The above 19 types of samples (sample numbers 811 to 29) were evaluated in the same manner as in Example (1), and the results are summarized in Table 6.

Margin Table-6 Below: Based on the same criteria as Margin Example (1), (1) Relative sensitivity,
It was confirmed that only the samples of the present invention (sample n numbers 15 to 29) satisfied all of (2) raw sample storage desensitization and (3) sharpness.

Patent Applicant Roku Konishi 7 True Any 2'' (Type 5 Company Representative Patent Attorney Ichino Noguo Capuichi 911 ↑ 2 2 4 μ ra Practitioner Procedure: ?T1) Posted (Voluntary) July 11, 1987 Japanese Patent M f: A3537 No. 2, Title of the invention: Silver halide photographic light-sensitive material 3, Relationship with the case of the person making the amendment Patent applicant address: 26-2 Nishi-Shinjuku 1-chome, Shinjuku-ku, Tokyo Name ( 1
27) Roku Konishi Photo Industry Co., Ltd. Representative Director Benko Oshijo 4, Agent 102 Address 1-1 Kudan Kita 4-chome, Chiyoda-ku, Tokyo Kudan-Roj
Sections ``2. Claims'' and ``3. Detailed Description of the Invention'' of Anti-Bill Telephone 263-9524 Specification (1) Attachment amending the detailed description of the invention section of Akira MRA as follows. 1. In a silver halide photographic material having at least a red-sensitive silver halide emulsion layer on a support, the red-sensitive silver halide emulsion layer contains a compound represented by the following general formula [I]. , and the silver halide contained in the red-sensitive silver halide emulsion layer has the following general formula [I[], [
1] and [rV].

[In the formula, R1 and R2 are respectively -〇N or -〇F]
R'R'', and R' and Rn each represent a hydrogen atom, a fluorine atom, or a fluorinated alkyl group having 1 to 4 carbon atoms.

R3 and R4 each represent an aliphatic group, an aromatic group or a heterocyclic group. L represents a methine group, which may be substituted with an alkyl group or an aryl group. ] General formula [■] General formula [111] [In the formula, R5 and R6 each represent an alkyl group or an aryl group, and L1, L2, L3, L4 and 5 each represent a methine group.

Zl and z2 each represent an atom or atomic group necessary to complete the oxazole ring, thiazole ring or selenazole ring. z3 represents a group of hydrocarbon atoms necessary to form a 6-membered ring. XQ represents an acid anion. ml
, +n2, n and yl each represent O or 1. However, if the compound forms an inner salt, it is O. ]General formula 11YI-2,.

[In the formula, z4 is a nonmetallic atom group necessary to constitute a quinoline ring, z5 is a thiazole ring, a benzothiazole ring,
naphthothiazole ring, benzoxazole ring, def1-
Represents an atomic group necessary to constitute an oxazole ring, benzoselenazole ring or naphthoselenazole ring. R
? , Ra and R9 each represent an alkyl group,
XQ represents an acid anion. l113 and 12 each represent O or 1. 2. The silver halide photographic material according to claim 1, wherein the red-sensitive silver halide emulsion layer contains a monodisperse silver halide emulsion.

3. The red-sensitive silver halide emulsion layer contains substantial silver chlorobromide grains having a silver chloride content of 30 to 70 mol%, or 2. Silver halide photographic material according to item 2.

4. The compound represented by the above general formula [I] has the following general formula [
The silver halide photographic material according to claim 1, 2 or 3, which is used in combination with a compound represented by VI].

General formula [VII] [wherein R+, R-), Rs and R8 each represent an alkyl group or an aryl group having at least one sulfonic acid Jj or carboxylic acid group, R2,
R3, RG and J: and 7 each represent a hydrogen atom, a norboxylic acid group, a sulfonic acid group, or an alkyl group containing at least one carboxylic acid group or sulfonic acid group JJ
Rashi< does not represent an aryl group. ]

Claims (1)

[Scope of Claims] 1. In a silver halide photographic material having at least a red-sensitive silver halide emulsion layer on a support, the red-sensitive silver halide emulsion layer has a compound represented by the following general formula [I]. The silver halide compound contained in the red-sensitive silver halide emulsion layer has the following general formula [II], [
A silver halide photographic light-sensitive material characterized in that it is color sensitized with at least one sensitizing dye selected from the sensitizing dyes shown in [III] and [IV]. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R_1 and R_2 are -CN or -, respectively]
CFR'R'' and R' and R'' each represent a hydrogen atom, a fluorine atom, or a fluorinated alkyl group having 1 to 4 carbon atoms. R_3 and R_4 each represent an aliphatic group, an aromatic group or a heterocyclic group. ] General formula [II] ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ General formula [III] [In the formula, R_5 and R_6 each represent an alkyl group or an aryl group, and L_1, L_2, L_3, L_
4 and L_5 each represent a methine group. Z_1 and Z_2 each represent an atom or atomic group necessary to complete the oxazole ring, thiazole ring or selenazole ring. Z_3 represents a group of hydrocarbon atoms necessary to form a 6-membered ring. X^■ represents an acid anion. m_1, m_2, n and l_1 each represent 0 or 1. However, when the compound forms an inner salt, l is 0. ] General formula [IV] ▲ Numerical formulas, chemical formulas, tables, etc. are included. Represents an atomic group necessary to constitute a benzoxazole ring, naphthoxazole ring, benzoselenazole ring, or naphthoselenazole ring. R_7, R_8 and R_9 each represent an alkyl group, and X^■ represents an acid anion. m_3 and l_
2 represents 0 or 1, respectively. 2. The silver halide photographic material according to claim 1, wherein the red-sensitive silver halide emulsion layer contains a monodisperse silver halide emulsion. 3. The red-sensitive silver halide emulsion layer contains substantial silver chlorobromide grains having a silver chloride content of 30 to 70 mol%, or 2. Silver halide photographic material according to item 2. 4. Claims 1, 2 or 3, characterized in that the compound represented by the general formula [I] is used in combination with the compound represented by the following general formula [VII]
The silver halide photographic material described in Section 1. General formula [VII] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R_1, R_4, R_5 and R_8 are each a hydrogen atom, hydroxy group, -OR group, or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ groups represent Here, R' represents an alkyl group or an aryl group, and R' and R''
represents a hydrogen atom or an alkyl group or aryl group having at least one sulfonic acid group or carboxylic acid group, and R_2, R_3, R_6 and R_7 each represent a hydrogen atom, a carboxylic acid group, a sulfonic acid group or at least one carboxylic acid group. represents an alkyl group or an aryl group having a group or a sulfonic acid group. ]