JPH03219233A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve the spectral sensitivity in the wavelength region of green light by spectrally sensitizing the silver halide particles incorporated into photosensitive silver halide emulsion layers by specific sensitizing dyes and incorporating specific compds. into these layers. CONSTITUTION:The silver halide particles contained in the photosensitive silver halide emulsion layers are spectrally sensitized by the sensitizing dyes expressed by formula I and at least one kind of the compds. expressed by formulas I to V are incorporated into these layers. In the formulas I to V, R11, R12, R21, R22, and R46, R57 denote an alkyl group; R13, R23 denote a hydrogen atom, alkyl group, etc. X1, X2 and X4 denote charge balance paired ions; n1, n2 and n4 denote the numerical values for adjusting the charges of the entire part of the molecules; R14, R24 denote a hydrogen atom or substituent. W11, W12, W21, W22 denote a hydrogen atom or substituent; R31 to R35, R41 to R45, R51 to R55 denote a hydrogen atom, etc.; R56 denotes a hydrogen atom, aryl group, etc. The spectral sensitivity of the wavelength region of the green light is enhanced in this way.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a spectrally sensitized silver halide photographic light-sensitive material, and more specifically, it relates to a silver halide photographic light-sensitive material that has been produced and has an increased spectral sensitivity in the green light wavelength region. This invention relates to a silver halide color photographic light-sensitive material that has excellent storage stability over time.

[Background of the invention]

Conventionally, oxacarbocyanine, benzimidazolocarbocyanine, etc. have been known as means for spectral sensitization of silver halide emulsions in the green wavelength range (for example, JP-A-61-1999).
286845 etc.). However, when these dyes are used alone, the sensitivity is insufficient, and by using the dye in combination with certain other sensitizing dyes or organic compounds, the sensitivity that can be imparted by each compound alone can be increased. Higher sensitivity is achieved by imparting sensitivity to the emulsion that exceeds the sum of the sum. Such an effect is known as supersensitization.

In general, the addition of a second dye or the addition of an organic substance often does not increase the sensitivity or even reduces the sensitivity, so supersensitization is a unique phenomenon. Extremely strict selectivity is required for the compound and the second sensitizing dye. Therefore, what appears to be a subtle difference in chemical structure significantly affects this supersensitizing effect, and it is difficult to obtain a supersensitizing combination simply by predicting from the chemical structural formula.

When applying supersensitization to silver halide photographic emulsions, the sensitizing dye used is required to provide high spectral sensitivity.

Examples of using two or more types of sensitizing dyes in combination to achieve higher sensitivity include combinations of two types of oxacarbocyanine, such as Japanese Patent Publication Nos. 44-32753 and 52-23931.
or a combination of oxacarbocyanine and benzimidazolocarbocyanine, such as the technology described in JP-A-59-16646, or a combination of oxacarbocyanine and oxathiacarbocyanine, e.g. Techniques described in JP-A-60-42750 and JP-A-63-167348 are known.

However, the sensitivity obtained by these techniques is still not satisfactory, and a silver halide photographic material with higher green sensitivity has been desired.

Furthermore, the color photographic materials produced using the above-mentioned techniques still have insufficient stability in photographic performance during storage, and there has been a demand for improvement in storage stability over time.

[Purpose of the invention]

The purpose of the present invention is to improve the spectral sensitivity in the green light wavelength range,
Another object of the present invention is to provide a silver halide color photographic material having excellent storage stability over time.

[Structure of the invention]

In order to develop a silver halide photographic light-sensitive material that satisfies these demands, the present inventors have conducted intensive research and have developed a silver halide photographic material having at least one light-sensitive silver halide emulsion layer on a support. In the light-sensitive material, the silver halide grains contained in at least one of the light-sensitive silver halide emulsion layers contain at least one sensitizing dye represented by the following general formula [, ■] and the following general formula (n). It is characterized by being spectrally sensitized by at least one of the sensitizing dyes shown below, and containing at least one compound represented by the following general formula (Iff), (IV), or [V] in the core layer. It has been found that the above object can be achieved by a silver halide photographic light-sensitive material.

General formula [I] General formula (n) General formula (I[r) General formula CIV) General formula (V) In the formula, RIIIR121R211Rxz and R, , R
sy represents a substituted or unsubstituted alkyl group, R, , R
2 represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. X , , X , and X
.

represents the charge-balanced counterion, nl+n! and n represents a numerical value for adjusting the charge of the entire molecule.

R, , R, represents a hydrogen atom or a substituent.

w,,,w,2. w2. , w, , represent a hydrogen atom or a substituent, and W r l+ W l 21 W ! +
1 W x x may be connected to form a condensed ring.

In addition, a, , a, , a is an integer of O or l, and in the formula 2
,． 2, and 2. each represents an atomic group necessary to form a 5- to 6-membered nitrogen-containing heterocycle.

R3,,R3,,R,,,R,,,R,,,R,,,R
,! ,R43°R4,,R,,,R,1,R5TIRi
! 1Rsa and R,s represent a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group, an alkoxy group, an aryl group represents an optionally substituted amino group, or adjacent substituents are condensed to form a 5- to 6-membered ring. Represents a group that can be formed.

Rsa represents a hydrogen atom, a substituted or unsubstituted alkyl group, an alkenyl group, or an aryl group.

R57 represents a substituted or unsubstituted alkyl group or aryl group.

General formula [:M-1) In the formula, Z represents a group of nonmetallic atoms necessary to form a nitrogen-containing heterocycle, and the ring formed by 2 may have a substituent.

X represents a hydrogen atom or a group that can be separated by reaction with an oxidized product of a color developing agent. Further, R represents a hydrogen atom or a substituent.

The present invention will be explained in more detail below.

The sensitizing dyes of the present invention represented by general formulas [I] and (If) will be explained.

The substituted or unsubstituted alkyl group represented by R, , R1, R2, and R1 is an alkyl group having 1 to 18 carbon atoms, preferably 1 to 7 carbon atoms, particularly preferably 1 to 4 carbon atoms (unsubstituted alkyl groups (e.g., methyl, ethyl, propyl, isopropyl, butyl, isobutyl, hexyl, octyl, dodecyl, octadecyl, etc.), substituted alkyl groups, such as aralkyl groups (e.g., benzyl, 2-phenylethyl, etc.), hydroquine alkyl groups (e.g. , 2-hydroxyethyl, 3-hydroxypropyl, etc.), carboxyalkyl groups (e.g., 2-carboxyethyl, 3-hydroxypropyl, 4-carboxybutyl, carboxymethyl, etc.), alkoxyalkyl groups (e.g., 2-methoxyethyl, 2-(2-methoxyethoxy)ethyl, etc.), sulfoalkyl groups (e.g., 2-sulfoethyl,
3-sulfopropyl, 3-sulfobutyl, 4-sulfobutyl, 2-[3-sulfopropoxy]ethyl, 2-hydroxy-3-sulfopropyl, 3-sulfopropoxyethoxyethyl, etc.), sulfatoalkyl group (example t I
f, 3-sul7atogropyl, 4-sul7atoptyl, etc.), heterocyclic-substituted alkyl groups (e.g. 2-(pyrrolidin-2-one-1-yl)ethyl, tetrahydrofurfuryl, etc.), 2-acetoxyethyl, carboxyl methoxymethyl, 2-methanesulfonylaminoethyl) or an allyl group.

Either one of R1□, R, 2, R, or R2□ is preferably a sulfoalkyl group or a carboxyalkyl group.

R, , R, represents a hydrogen atom, an optionally substituted alkyl group (e.g., methyl group, ethyl group, benzyl group, etc.), an optionally substituted aryl group (e.g., phenyl group, p-tolyl group, etc.) ).

Particularly preferred is ethyl group.

Specific examples of R, 4, and R2 include a hydrogen atom, an / ethoxy group, etc.), alkoxycarbonyl group (eg, ethoxycarbonyl group, etc.).

Wr, W! , Ws and W4 are each a hydrogen atom, an alkyl group (e.g. methyl group, ethyl group, etc.), a phenyl group, or a benzene ring, a cyclohexene ring, a thiophene ring formed by connecting Wl and W2 and/or W3 and W, respectively. ring, naphthalene ring, preferred embodiments are:
This is a case where W, and W2 and/or W, and W are connected to each other to form a benzene ring, a cyclohexene ring, a thiophene ring, or a naphthalene ring, and in this case, these rings may have a substituent. Specifically, halogen atoms (e.g. fluorine atom, chlorine atom, bromine atom, etc.), alkyl groups (e.g. methyl group, ethyl group, etc.), alkoxy groups (e.g. methoxy group, ethoxy group, etc.), aryl groups (e.g. phenyl group) etc.) Trifluoromethyl group, cyanogen group, alkoxycarbonyl group (e.g. methoxycarbonyl group, butoxycarbonyl group, etc.), carbamoyl group (e.g. carbamoyl group, N,N-dimethylaminocarbonyl group, etc.), sulfonyl group (e.g. methanesulfonyl group) , benzenesulfonyl group, etc.), sulfamoyl group (eg, sulfamoyl group, N,N-dimethylaminosulfonyl group, etc.), and the like.

(x +)n+, cX z)nz is included in the formula to indicate the presence or absence of a cation or anion when necessary to neutralize the ionic charge of the dye. Therefore, Xl and X2 can take appropriate values of 0 or more as necessary.

Whether a dye is cationic, anionic, or has no net ionic charge depends on its auxochrome and substituents. Typical cations include inorganic or organic ammonium ions (e.g. triethylammonium ion, pyridinium ion, etc.), alkali metal ions (
Examples include sodium ions, potassium ions, etc.), alkaline earth metal ions (e.g. calcium ions, strontium ions, etc.), while anions include, for example, halogen anions (e.g. chloride ions, bromide ions, iodide ions, etc.). ), substituted arylsulfonate ions (e.g. p-)luenesulfonate ion, p-chlorobenzenesulfonate ion, etc.), aryldisulfonate ions (e.g. 1,3-benzenedisulfonate ion, 1,5-s7thalene disulfonate), acid ions, etc.), alkyl sulfate ions (e.g. methyl sulfate ions, etc.), sulfate ions, thiocyanate ions, perchlorate ions, tetrafluoroborate ions, picrate ions, acetate ions, trifluoromethanesulfonate ions, etc. .

The sensitizing dyes used in the present invention are F, M, Hamer (F
, M. Hamer), ``Heterocyclic Con+po Cyanine Soybean and Related 0 Combines''
undsCyanine Days and Re1
atad Co+npounds)”Chapter 4, Chapter 5,
Chapter 6, pp. 86-119, John Wiley and 5ons
) Publishing (1964), D.M. Starmer (D.M.
Heterocyclic Compounds - Special Topics in Heterocyclic Chemistry
Compounds 5special 1nH
It can be easily synthesized based on the method described in "Eterocyclic Chemistry", Chapter 8-482, page 9515, published by John Wiley & Sons (1977).

Below, general formula (I) or Cl0) used in the present invention
Specific examples of the sensitizing dye represented by are shown below, but the present invention is not limited thereto.

[I]

(1) (1) -C (II) -a ■ -83 ■ -84 ■-85 -36 ■ -87 ■ -80 -81 ■ -82 ■-88 ■-90 )υkoflN(shi2IIS)3 The optimal concentration of the sensitizing dye of general formula [I] can be determined by methods known to those skilled in the art.

For example, a method may be used in which the same emulsion is divided, each emulsion contains a different concentration of sensitizing dye, and the performance of each emulsion is measured.

The amount of the sensitizing dye added in the present invention is not particularly limited, but ranges from %2XlO-' mol to 1Xl mol per mol of silver halide.
Preferably, 0-" moles are used, and even 5 X 10
Preference is given to using −5×10 −′ moles.

Methods well known in the art can be used to add the sensitizing dye to the emulsion.

For example, these sensitizing dyes can be dispersed directly in the emulsion or dissolved in a water soluble solvent such as pyridine, methyl alcohol, ethyl alcohol, methyl cellosolve, acetone, fluorinated alcohol, dimethylformamide or mixtures thereof. Alternatively, it can be diluted or dissolved in water and added to the emulsion in the form of a solution. Ultrasonic vibrations can also be used during the dissolution process.

In addition, the dye can be prepared by dissolving the dye in a volatile organic solvent, as described in U.S. Pat. No. 3,469.987, etc.
A method of dispersing this solution in a hydrophilic colloid and adding this dispersion to an emulsion, as described in Japanese Patent Publication No. 46-24185, etc., disperses the water-insoluble dye in a water-soluble solvent without dissolving it. A method of adding this dispersion to an emulsion is also used.

The dye can also be added to the emulsion in the form of a dispersion by the acid dispersion method.

For addition to other emulsions, U.S. Patent 2,912.345
It is also possible to use the methods described in the specifications of No. 3,342.605, No. 2,996,287, and No. 3,425.835.

The timing of adding the sensitizing dyes represented by the general formulas [I] and (II) used in the present invention to the emulsion is during the manufacturing process from the time of silver halide grain formation to just before coating on the support. It can be added at any time.

Specifically, before the formation of silver halide grains, during the formation of silver halide grains, after the completion of silver halide grain formation until the start of chemical sensitization, at the start of chemical sensitization, during chemical sensitization, and during chemical sensitization. Any time selected from the end of chemical sensitization and the time of application may be used. Alternatively, it may be added in multiple portions. Although the order in which the stabilizer and antifoggant are added does not matter, they are preferably added at the time of particle formation or chemical ripening, that is, before the coating liquid is prepared.

The sensitizing dyes represented by the general formulas [I] and (II) can also be used in combination with other sensitizing dyes.

In this case, each sensitizing dye may be dissolved in the same or different solvents, and these solutions may be mixed or separately added to the emulsion prior to addition to the emulsion. When adding them separately, the order and time interval can be arbitrarily determined depending on the purpose.

Next, general formulas (If), (III), and [IV] will be explained in detail.

2. Compounds represented by general formulas (II), [II), and (IV). ．． 2. The heterocycle formed by each of z5 and z5 is a 5- to 6-membered heterocycle commonly used in cyanine dyes, or a condensed ring of these and a benzene ring or a 7-talene ring. That is, for example, cyanine heterocyclic nuclei consisting of a thiazole ring, selenazole ring, oxazole ring, tetrazole ring, pyridine ring, biroline ring, or imidazole ring and having a substituent on the ring are also included.

Specifically, thiazole type (e.g. thiazole, 4-methylthiazole, 4-phenylthiazole, 5-methylthiazole, 5-phenylthiazole, 4.5-dimethylthiazole, 4.5-diphenylthiazole, benzothiazole, 5- Chlorobenzothiazole, 5-chlorobenzothiazole, 6-chlorobenzothiazole, 5-
Methylbenzothiazole, 6-methylbenzothiazole, 5-bromobenzothiazole, 5-carboxybenzothiazole, 5-ethoxycarbonylbenzothiazole, 5-hydroxybenzothiazole, 5-phenylbenzothiazole, 6-7 enylbenzothiazole, 5-methoxybenzothiazole, 6-methoxybenzothiazole, 5-iodobenzothiazole, 6-nidoxybenzothiazole, tetrahydrobenzothiazole, 5.6-
dimethylbenzothiazole, 5.6-simethoxybenzothiazole, 5.6-cyoxymethylenebenzothiazole, 6-nitoxy5-methylbenzothiazole, 5-
7-enethylbenzothiazole, na[1,2-d]
Thiazole, Naphtho[2,1-d]thiazole, Naphtho[2,3-dlthiazole, 5-methoxynaphtho[1,
2-d]thiazole, 5-methoxy/su7to[2,1-d
]thiazole, 8-methoxynaphtho[2,1-d]thiazole, 7-methoxynaphtho[2°1-d]thiazole, 5-methoxythiona7theno[6,7-dlthiazole, 5-methoxythionaphtheno[6, 7-d], 8.9-
dihydronaphtho[1,2-d]thiazole, 4,5-dihydronaphtho[2,1-d]thiazole, etc.), oxacyls (for example, 4-methyloxazole, 5-methyloxazole, 4-phenyloxazole, 4. 5-dimethyloxazole, 5-7enyloxazole, 5.6
-diphenyloxazole, benzoxazole, 5-
Chlorobenzoxazole, 5-methylbenzoxazole, 5-phenylbenzoxazole, 6-methylbenzoxazole, 5.6-dimethylbenzoxazole, 5-methoxybenzoxazole, 5-ethoxybenzoxazole, 5-phenethylbenzoxazole, 5-hydroxybenzoxazole, ethoxycarbonylbenzoxazole, 5-bromobenzoxazole, 5-methyl-6-chlorobenzoxazole, natu[1,2-d]oxazole, naphtho[2,1-d]
Oxazole, nuts [2,3-dl oxazole, etc.]
, selenazole series (e.g. 4-methylselenazole,
4-7enyl selenazole, benzselenazole, 5-
Chlorobenzoselenazole, 5-methoxybenzoselenazole, 5-methylbenzoselenazole, tetrahydrobenzoselenazole, nand[1,2-d]selenazole, napf1-[2,1-d]selenazole, etc.), tetrazole type (e.g. 4-phenyltetrazole, 4-
Methyltetrazole, benzotetrazole, 5-methylbenzotetrazole, 5-methoxybenzotetrazole, 5゜6-dimethylbenzotetrazole, naphtho[2,
1-d]tetrazole, natu[1,2-d]tetrazole, etc.), pyridine series (e.g., 2-pyridine, 5-methyl-2-pyridine, 4-pyridine, 3-methyl-4-
pyridine, etc.), quinoline series (e.g., 2-quinoline, 6-quinoline, etc.),
-methyl-2-quinoline, 5-ethyl-2-quinoline,
6-chloro-2-quinoline, 8-chloro-2-quinoline, 6-medoxy-2-quinoline, 8-ethoxy-2-quinoline, 6-methyl-2-quinoline, 8-fluoro-2
-quinoline, 6-dimethylamino-2-quinoline; 4-
Quinoline, 6-medoxy-4-quinoline, 7-methyl-
4-quinoline, 8-chloro-4-quinoline, etc.), 3.3
-Dialkylindolenine type (e.g., 3,3-dimethylindolenine, 3.3.5-trimethylindolenine, 3.3-dimethyl-5-(dimethylamino)indolenine, 3.3-diethylindolenine, etc.) , imidazole type (e.g. imidazole, l-alkylimitasol, l-alkyl-4-phenylimidazole, l-alkyl-4,5-dimethylimidazole, ■-alkylbenzimidazole, l-phenyl-5,6-cyclo Penzimidazole, ■-alkyl-5-cyanohenzimidazole, l-alkyl-5-chlorobenzimidazole, ■-alkyl-5,6-cyclopenzimidazole, l-alkyl-5-chloro-6-diatubenzimidazole, l -Alkyl-5-trifluoromethylbenzimidazole, 1-alkyl-5-methylsulfonylbenzimidazole, l-alkyl-5-methoxycarbonylbenzimidazole, l-alkyl-5-acetylbenzimidazole, l-alkyl-5-( N, N-
dimethylamino)sulfonylbenzimidazole, l-
Alkylnaphtho[1,2-d]imidazole, l-alkynando[2,1-d]imidazole, l-alkylnaphtho[2,3-d]imidazole, etc.).

The 1-alkyl group is an alkyl group having 1 to 10 carbon atoms (
When it has a substituent, the number of carbon atoms of the substituent is not included. ), an alkoxy group having 1 to 6 carbon atoms, an alkoxycarbonyl group having an alkoxy group having 1 to 4 carbon atoms,
It also includes those substituted with a carboxy group, carbamoyl group, cyan group, halogen atom, sulfo group, phenyl group, substituted phenyl group, vinyl group, etc. (Specific examples of substituents include methyl group, ethyl group, cyclohexyl group, etc.) group, butyl group, decyl group, 2-methoxyethyl group, 3-butoxypropyl group, 2-hydroxy-ethoxyethyl group, ethoxycarbonylmethyl group, carboxymethyl group, 2-
Carboxyethyl group, 2-cyanoethyl group, 2-carbamoylethyl group, 2-hydroxyethyl group, 2-fluoroethyl group, 2.2.2-trifluoroethyl group, 2-
Examples include sulfoethyl group, 3-sulfopropyl group, 4-sulfobutyl group, phenethyl group, penzyl group, sulfophenethyl group, carboxybenzyl group, and allyl group.

) Zl, Zl, 2! and 2. The nuclei formed by each of the following are further oxazoline-based (e.g., oxazoline, 4,4-dimethyloxazoline), thiazoline-based (e.g., thiazoline, 4-methylthiazoline), inoxazole-based (e.g., inoxazole, benzisoxazole, 5
-chlorobenzisoxazole, 6-methylbenzisoxazole, 7-methylbenzisoxazole, 6-
medoxybenzoxazole, 7-medoxybenzisoxazole, etc.), 1,3,4-thiadiazole series (e.g. 5-methyl-1,3,4-thiadiazole, 5-methylthio-1,3,4-thiodiazole, etc.) , chenothiazole series (e.g., cheno[2,3-dl thiazole, thieno[3,2-d]thiazole, cheno[2,3
-e]benzothiazole, cheno[3°2-e]benzothiazole, thiazo-[4,5-bl benzothiophene, etc.), tetrazole (e.g. 1-alkyltetrazole), imidazoquinoxaline type (e.g. l-alkyl- imidazo[4,5-bl quinoxaline, 6,7-dichloro-1-alkyl-imidazo[4,5-bl quinoxaline, 6-dichloro-1-arylimidazo[4,5-
bl-quinoxaline, etc.), imidazoquinoline series (e.g.,
l-alkyl-imidazo[4,5-b]quinoline, 6.
7-dichloro-1-alkylimidazo[4,5-bl quinoline, etc.), pyrrolopyridine series (e.g. 3,3-dialkyl-3H-pyrrolo[2,3-b]pyridine), pyrrolopyrazine series (e.g. pyrrolo -[2,3-b]pyrazine), pyridopyridine series (e.g. pyrido[2,3-b]
) pyridine) and the like.

R3I, R3□, R33, R34, R3B, R++,
R-2, R4 Yu.

Preferred substituents for R441R4SIRs+, Rsz+R5srRsa and R55 are halogen atoms (for example, chlorine atoms, etc.), hydroxy groups,
An alkyl group (e.g. methyl group, ethyl group, etc.), an alkoxy group (e.g. methoxy group, etc.), a substituted amino group (e.g. diethylamino group, etc.) having 1 to 4 carbon atoms, and two adjacent substituents are condensed. It is also preferable to form a ring (fused benzene ring, methylenedioxy group, etc.).

The group represented by R57 is preferably an alkyl group having 1 to 6 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, etc.), and the alkyl group includes those having a substituent.

Examples of the substituent include an alkoxy group, an alkylthio group, an aryloxy group, an aryl group, a hydroxy group, a cyano group, a vinyl group, a halokene atom, a carbamoyl group, a sulfamoyl group, a sulfonyl group, an alkoxycarbonyl group, and a carboxy group. .

R4, is synonymous with R11, and X, , n, are each X,
.

It is synonymous with n.

Preferred examples of Rs include a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and a phenyl group.

General formula CI[[], general formula (
Specific examples of compounds represented by IV) or (V) are shown below,
The present invention is not limited to these [I[[] −
a (I[[)-b III-28 ■-29 ■-54 ■ 62 ■-63 ll-71 ll-72 ■-73 ■-75 (rV) -a ■ 16 ■ 5 ■ 6 (IV) b ■ -43 C, Hl Js ■e ■-46 ■-47 ■-48 ■-49 ■-50 (V) -a CI.

C,H.

−51 1 C,H.

f13 General formula (I[[), general formula (IT) used in the present invention
It is preferable to use the compound represented by the general formula (V) in an amount capable of supersensitizing the silver halide 1 in the emulsion.
Preferably, it is used in a proportion of 1X10-'' mol to IX10-'' mol per mole.

A sensitizing dye represented by the general formula [I] and the general formula (If),
The ratio (molar ratio) of the compound represented by the general formula [lI[), the general formula (IV) or the general formula (V) to the dye represented by the general formula (I), the compound represented by the general formula (If), dyes, or compounds represented by general formulas (III), [IV], and general formulas (V) - A range of 10/1-1/100 is advantageously used, particularly a range of 2/1-1/10. is preferably used.

General formula [III] and general formula [IV] used in the present invention
Alternatively, the compound represented by the general formula (V) can be directly dispersed in an emulsion, or can be dissolved in a suitable solvent (for example, methyl alcohol, ethyl alcohol, methyl cellosolve, water, etc.) or a mixed solvent thereof. It can also be added to the emulsion. In addition, it can be added to the emulsion in the form of a solution or a dispersion in a colloid according to the method of adding sensitizing dyes.

A sensitizing dye represented by general formula [■] or general formula (II) can be added to the compound represented by general formula [III], general formula (IV) or general formula (V) at the same time, and Although they can be added separately, the coupler represented by the general formula [M-I] according to the present invention is preferable, and will be further explained below.

In the general formula [M-I], 2 represents a group of nonmetallic atoms necessary to form a nitrogen-containing heterocycle, and the ring formed by 2 may have a substituent.

X represents a hydrogen atom or a group that can be separated by reaction with an oxidized product of a color developing agent.

Moreover, R represents a hydrogen atom or a substituent.

The substituent represented by R is not particularly limited, but typically includes alkyl, aryl, anilino, acylamino, sulfonamide, alkylthio, arylthio, alkenyl, cycloalkyl, etc. In addition, halogen Atoms and cycloalkenyl, alkynyl, heterocycle, sulfonyl, sulfinyl, phosphonyl, acyl, carbamoyl, sulfamoyl, cyano, alkoxy, aryloxy, heterocycleoxy, siloxy, acyloxy, carbamoyloxy, amino, alkylamino, imide, ureido, sulfonyl Also included are famoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, heterocyclic thio polygroups, spiro compound residues, bridged hydrocarbon compound residues, and the like.

The alkyl group represented by R preferably has 1 to 32 carbon atoms, and may be linear or branched.

The aryl group represented by R is preferably a phenyl group.

Examples of the acylamino group represented by R include an alkylcarbonylamino group and an arylcarbonylamino group.

Examples of the sulfonamide group represented by R include an alkylsulfonylamino group and an arylsulfonylamino group.

Examples of the alkyl component and aryl component in the alkylthio group and arylthio group represented by R include the alkyl group and aryl group represented by R above.

The alkenyl group represented by R preferably has 2 to 32 carbon atoms, and the cycloalkyl group preferably has 3 to 12 carbon atoms, particularly 5 to 7 carbon atoms, and the alkenyl group may be linear or branched.

The cycloalkenyl group represented by R has 3 to 3 carbon atoms.
12, especially those of 5 to 7 are preferred.

Sulfonyl groups represented by R include alkylsulfonyl groups, arylsulfonyl groups, etc.; sulfinyl groups include alkylsulfinyl groups, arylsulfinyl groups, etc.; phosphonyl groups include alkylphosphonyl groups, alkoxyphosphonyl groups, and aryloxyphosphonyl groups. , arylphosphonyl group, etc.; Acyl group includes alkylcarbonyl group, arylcarbonyl group, etc.; carbamoyl group, arylcarbamoyl group, etc.; sulfamoyl group includes alkylsulfamoyl group,
Arylsulfamoyl groups, etc.; As acyloxy groups, alkylcarbonyloxy groups, arylcarbonyloxy groups, etc.; carbamoyloxymoyloxy groups, arylcarbamoyloxy groups, etc.; As ureido groups, alkylureido groups, arylureido groups, etc.; sulfamoyl The amino group is preferably an alkylsulfamoylaminomino group; the heterocyclic group is preferably a 5- to 7-membered one, specifically a 2-furyl group, 2-thienyl group, 2-pyrimidinyl group, or 2-benzothiazolyl group. etc.; As the heterocyclic oxy group, those having a 5- to 7-membered heterocycle are preferable, such as 3.
4.5.6-tetrahydropyranyl-2-oxy group, ■
-Phenyltetrazole-5-oxy group, etc.; The heterocyclic thio group is preferably a 5- to 7-membered heterocyclic thio group, such as 2-pyridylthio group, 2-penzothiazolylthio group, 2,4-diphenoxy-1 .3.5-triazole-6 monothio group, etc.; as a siloxy group, trimethylsiloxy group, triethylsiloxy group, dimethylbutylsiloxy group, etc.; as an imide group, succinimide group, 3-heptadecylsuccinimide group, phthalimide group and glutarimide groups, spiro [3,31hebutan-■-yl, etc.; as bridged hydrocarbon compound residues, bicyclo [2゜2.
11 Hebutan-1-yl, tricyclo [3°3.1.
l.7]decane-1-yl, 7,7-dimethyl-bicyclo[2,2,1]hebutan-1-yl, and the like.

Groups that can be separated by reaction with the oxidized product of the color developing agent represented by X include, for example, halogen atoms (chlorine atom, bromine atom, fluorine atom, etc.), alkoxy, aryloxy, heterocyclic oxy, acyloxy, sulfonyloxy, alkoxy Carbonyloxy, aryloxycarbonyl, alkyloxalyloxy, alkoxyoxalyloxy, alkylthio, arylthio, heterocyclic thio, alkyloxythiocarbonylthio, acylamino, sulfonamide, nitrogen-containing heterocycle bonded via N atom, alkyloxycarbonylamino , aryloxycarbonylamino,
Carboxyl, (R□' has the same meaning as R above, z' has the same meaning as 2 above, and R' and R1' represent a hydrogen atom, an aryl group, an alkyl group, or a heterocyclic group). Among these groups, a halogen atom, particularly a chlorine atom is preferable.

Examples of the nitrogen-containing heterocycle formed by 2 or 2' include a pyrazole ring, an imidazole ring, a triazole ring, or a tetrazole ring, and examples of the substituents that the ring may have include those described for R above. can be mentioned.

More specifically, what is represented by the general formula [M-Il is represented by, for example, the following general formulas [M-[1 to [M-■]].

General formula [M-I[] General formula [M-I[[] In the general formula [M-[1 to [M-■]], R.

~R6 and X have the same meanings as R and X above.

Also, preferred among the general formulas [M-Il are those represented by the following general formula [M-■].

General formula [M-IV] General formula [M-V] General formula [M-VT] General formula [M-■] -N-N In the formula, R, , X and Zl are the general formula [R in M-IF,
It is synonymous with X and Z.

Among the magenta couplers represented by the general formulas [M-n] to [M-■], particularly preferable ones are those represented by the general formula [M-■].
-n ] is a magenta coupler.

Substituents that the ring formed by 2 in general formula [M-Il and the ring formed by zl in general formula [M-■] may have, and general formulas [M-1[] to [M
-VI], R8 to R in the following general formula [M
-ff ] is preferable.

General formula [M-II] -R''-SO, -R'' In the formula, R1 represents an alkylene group, and %R'' represents an alkyl group, a cycloalkyl group, or an aryl group.

The alkylene group represented by R1 preferably has 2 or more carbon atoms in the straight chain portion, more preferably 3 to 6 carbon atoms, and it does not matter whether the straight chain has one branch or not.

The cycloalkyl group represented by R2 is preferably a 5- to 6-membered one.

In addition, when used for positive image formation, the substituent R on the heterocycle
and R+ are most preferably represented by the following general formula [M −
X ].

General formula [M-Xl R.

Rlo -C- ・R,□ In the formula, R,,R,. and R11 each have the same meaning as R above.

Also, the above R,,R,. and R1, for example R1
and R1° may be bonded to form a saturated or unsaturated ring (e.g., cycloalkane, cycloalkene, heterocycle), and R1, may be bonded to the ring to form a bridged hydrocarbon compound residue. You may.

Among the general formula [M −X ], (i) is preferable.
When at least two of RS to R1□ are alkyl groups, (i) one of Re-R11, for example R11, is a hydrogen atom, and the other two are R9 and Ro. is combined with the root carbon atom to form a cycloalkyl.

Furthermore, in (i), it is preferable that two of R and to R11 are alkyl groups and the other one is a hydrogen atom or an alkyl group.

In addition, when used for negative image formation, the substituent R on the heterocycle
and R8 are most preferably represented by the following general formula [M-
III.

General formula [M-n] R1□-CH2 ~ R12 in the formula
has the same meaning as R above.

R1 is particularly preferably a hydrogen atom or an alkyl group.

Typical specific examples of the compounds according to the present invention are shown below.

C,,H,.

CH.

1A CH.

H3 9 39 0 CH.

Ca　Hli Ct　H+　s CH.

Hs *-Cs H+ + (t) 1 CH.

C,,H,.

1 Hs CI-13NMkoLJ2LzB1'133= CH2Hs *= In addition to the above representative examples of compounds according to the present invention, specific examples of compounds according to the present invention include Japanese Patent Application No. 61-9791.
Among the compounds described on pages 66 to 122 of the specification, No. 1 to 4.6.8 to l 7°19 to 24.
26-43.45-59.61-104, 106-1
21. 123-162. Compounds represented by 164 to 223 can be mentioned.

Also, the coupler is described in the Journal of the Chemical
Society ((Journal of the Che
mical Society), Perkin (Perkin)
kin) I (1977), 2047-2052,
U.S. Patent No. 3,725.067, JP 59-9943
No. 7, No. 58-42045, No. 59-162548, No. 59-171956, No. 60-33552, No. 60-43659, No. 60-172982, and No. 6
It can be synthesized by referring to No. 0-190779 and the like.

The couplers of the invention typically contain 1Xl per mole of silver halide.
0-” mol-1 mol, preferably lXl0-2 mol-8
It can be used in the range of X 10-' moles.

The couplers of the present invention can also be used in combination with other types of magenta couplers.

The silver halide grains contained in the silver halide photographic light-sensitive material of the present invention may be any of silver bromide, silver chloride, silver chlorobromide, silver iodobromide, and silver chloroiodobromide.

In particular, silver iodobromide is preferred from the standpoint of obtaining high sensitivity.

In the case of silver iodobromide, the average silver iodide content in the silver halide grains is preferably 0.5 to 10 mol%, more preferably 1
~8 mol%.

In the present invention, the object of the present invention can be more effectively achieved by using silver halide grains contained in the photosensitive silver halide emulsion layer as silver halide grains having a core/shell structure. A particle having a core/shell structure as referred to above is one having a structure in which a core inside the particle is covered with a shell having a composition different from that of the core.

In grains having a core/shell structure, the shell may be uniform, but it is particularly preferable that the coated shell is further coated with shells having different silver halide compositions to form a multilayer structure.

In the silver halide crystal of the present invention having a core/shell structure made of #i (silver chloroiodobromide), the silver iodide content of the shell is preferably 2 mol % to 40 mol %. More preferably 10 mol% to 40 mol%, 15 mol%
-40 mol% is more preferable.

In the silver halide crystal of the present invention made of silver iodobromide (silver chloroiodobromide), the legal ions may be added as an ionic solution such as a potassium iodide solution, and the silver halide grains during growth may be added as an ionic solution such as a potassium iodide solution. Although it may be added as a grain with a smaller solubility product than the silver halide grain, it is more preferable to add it as a silver halide grain with a smaller solubility product.

The shape of the silver halide grains used in the present invention may be a so-called normal crystal having a cubic, octahedral, tetradecahedral, or spherical shape, or may be a crystal containing twin planes.

The method for producing normal crystal silver halide grains is known, for example J
, Phot, Sci., 5, 332 (1961)
,Ber,Bunsenges,Phys,chem,
67, 949 (1963), Intern, Cong.
ressPhoto, Sei, Tokyo (1967)
It is described in etc.

Further, tabular grains having an aspect ratio of 5 or more can also be used in the present invention. Tabular grains are described in U.S. Patent 4,434
．． No. 226, No. 4,414,310, No. 4,433.
No. 048, No. 4,439,520 and British Patent No. 2,1
It can be easily prepared by the method described in No. 12.157.

As tabular grains with an aspect ratio of 5 or more,
Preferably, the aspect ratio is 5 or more and 100 or less, more preferably 5 or more and 20 or less.

The circular diameter of the tabular grains is preferably 0.2 μm to 30 μm, more preferably 0.4 μm to 10 μm. Further, the thickness thereof is preferably 0.5 μm or less, more preferably 0.3 μm or less.

The silver halide emulsion used in the present invention includes:
Although polydisperse emulsions can be used, monodisperse emulsions are more preferred.

The monodisperse emulsion referred to here is, for example, The Photo
-grapbic Journal, 79.330~
338 (1939), Tri velli, Sm1
Silver halide in which at least 95% of the grains in terms of number or weight are within ±40%, preferably within ±30% of the average grain diameter when the average grain diameter is measured by the method reported by th et al. It is made of emulsion.

The silver halide grains described above used in the silver halide photographic material of the present invention include, for example, T and H grains.

James, “The Theory of the
Photographic Pro-Ce5S” No. 4
Edition, published by Macmi 1lan (1977) 38-1
Apply methods such as the neutral method, acidic method, ammonia method, forward mixing, back mixing, double jet method, Chondrold-'l pull jet method, conversion method, core/shell method, etc. described in literature such as page 04. It can be manufactured by

Known photographic additives can be used in the silver halide photographic emulsion of the present invention.

Examples of known photographic additives include compounds described in Research Disclosure (RD) RD-17643 and RD-18716 shown in the table below.

AdditivesChemical sensitizersDevelopment acceleratorsAntifoggantsStabilizersColor stain inhibitorsImage stabilizersUV absorbersFiltersDye enhancersWhitenersHardenersCoating aidsSurfactantsPlasticizersSlip agentsStatic inhibitorsMattes Agent Binder RD-17643 Page Classification 23 nl 29 Ill 24 Vl 25 ■ 25 ■ 25-26 ■ 〃 24 V 26 648 - Upper right 649 - Lower right 50 Left - Right 649 Right ~ 650 Left 651 Right 650 Right 650 Right // 650 Right 651 Right In the photosensitive material according to the present invention, aromatic first
A dye-forming coupler that forms a dye by performing a coupling reaction with an oxidized product of a class amine developer (for example, a p-) unilene diamine derivative or an aminophenol derivative) can be used. The dye-forming couplers are typically selected for each emulsion layer such that a dye is formed that absorbs light in the light-sensitive spectrum of the emulsion layer, with a yellow dye-forming coupler for the blue-sensitive emulsion layer and a dye for the green-sensitive emulsion layer. A magenta coupler is used in the sensitive emulsion layer, and a cyan dye-forming coupler is used in the red-sensitive emulsion layer. However, depending on the purpose, a silver halogen color photographic light-sensitive material may be produced using a different combination from the above combination.

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-equivalent, in which 4 molecules of silver ions need to be reduced in order to form 1 molecule of dye, only 2 molecules of silver ions need to be reduced. Either equivalence is acceptable. Color-forming grays are produced by coupling with colored couplers, which have a color correction effect, and oxidized forms of developing agents, and are then combined with development inhibitors, development accelerators, bleaching accelerators, developers, silver halide solvents, and preparations. Compounds that release photographically useful fragments such as colorants, hardeners, fogging agents, antifoggants, chemical sensitizers, spectral sensitizers, and desensitizers are included.

Among these, couplers that release a development inhibitor during development and improve image sharpness and image graininess are called DIR couplers. In place of the DIR coupler, a DIR compound which undergoes a coupling reaction with the oxidized form of the developing agent to produce a colorless compound and at the same time releases a development inhibitor may be used.

The DIR couplers and DIR compounds used include those in which the inhibitor is directly bonded to the coupling position, and those in which the inhibitor is bonded to the coupling position via a divalent group, and the group is separated by the coupling reaction. Intramolecular nucleophilic reaction,
Included are compounds in which the inhibitor is bonded such that it is released by an intramolecular electron transfer reaction or the like (referred to as timing DIR couplers and timing old R compounds). Also, depending on the purpose, inhibitors that can be dispersed after release and those that are not so dispersible can be used alone or in combination. Colorless couplers (also referred to as competitive couplers) that undergo a coupling reaction with the oxidized product of the aromatic primary amine developer but do not form dyes can be used in combination with dye-forming couplers. As the yellow dye-forming coupler, known acylacetanilide couplers can be preferably used. Among these, benzoylacetanilide and pivaloylacetanilide compounds are advantageous.

Specific examples of yellow couplers that can be used include U.S. Pat. No. 2,875,057, U.S. Pat.
, 408° No. 194, No. 3,551.155, No. 3,
No. 582.322, No. 3,725゜072, No. 3,8
No. 91.445, West German Patent No. 1,547,868, West German Application No. 2,219,917, West German Patent No. 2,261.361
No. 2゜414.006, British Patent No. 1,425,0
No. 20, Special Publication No. 51-10783, Japanese Patent Publication No. 47-26
No. 133, No. 48-73147, No. 50-6341, No. 50-87650, No. 50-123342, No. 50-130442, No. 51-21827, No. 51
-102636, 52-82424, 52-1
No. 15219, No. 58-95346, etc.

Magenta coloring couplers include pyrazolone compounds,
Indacylon compounds, cyanoacetyl compounds, etc. can be used, and pyrazolone compounds are particularly advantageous.

A specific example of a magenta color-forming coupler that can be used is disclosed in U.S. Pat.
, No. 600,788, No. 2,983,608, No. 3,
No. 062,653, No. 3,127,269, No. 3,3
No. 11.476, No. 3,419.391, No. 3,51
No. 9,429, No. 3,558,319, No. 3.582
No. 322, No. 3,615,506, No. 3,834.
No. 908, No. 3,891°445, West German Patent No. 1,81
No. 0.464, West German Patent Application (OLS) 2.408.6
No. 65, No. 2,417,945, No. 2,418.95
No. 9, No. 2,424.467, Special Publication No. 40-6031
No. 51-20826, No. 52-58922, No. 49-129538, No. 49-74027, No. 50-159336, No. 52-42121, No. 49
-74028, 50-60233, 51-26
No. 541, No. 53-55122, No. 59-17195
No. 6, No. 60-33552, No. 60-43659,
These are those described in No. 60-172982, No. 60-190779, etc.

As the cyan coloring coupler, phenol compounds, naphthol compounds, etc. can be used.

Specific examples include U.S. Patent No. 2,369,929;
434゜272, 2,474.293, 2,5
21.90. ! No. 1, No. 2,895゜826, No. 3,
No. 034,892, No. 3,311,476, No. 3,4
58゜315, 3,476.563, 3,58
No. 3,971, No. 3,591゜383, No. 3,767
．． No. 411, No. 4,004,929, West German patent application (
0LS) 2.414.830, 2,454,329
No. 48-59838, 51-26034, 48-5055, 51-146828, 5
There is one described in No. 2-69624.

The silver halide photographic material of the present invention is produced by coating it on a support that has good flatness, good dimensional stability and little dimensional change during the production process or processing. Supports in this case include, for example, cellulose nitrate film, cellulose ester film, polyvinyl acetal film, polystyrene film, polyethylene terephthalate film, polycarbonate film, glass, paper, metal, paper coated with polyolefin, such as polyethylene, polyglopylene, etc. etc. can be used. These supports can be subjected to various surface treatments such as hydrophilic treatment for the purpose of improving adhesion with the photographic (emulsion) layer, such as halogenation treatment, corona discharge treatment, subbing treatment, and setting. Processing, etc. is performed.

The silver halide color photographic light-sensitive material of the present invention is described, for example, in Research Disclosure No. 176, 20-30.
The processing can be carried out using the known photographic processing method and processing solution described on page RD-17643. The processing temperature applied to photographic processing is usually 18°C to 50°C, but processing is possible at temperatures lower than 18°C or at temperatures above 50°C.

Examples of light-sensitive materials to which the silver halide color photographic light-sensitive material of the present invention can be applied include color negative film for photography, color reversal film, color photographic paper, color positive film, color reversal photographic paper, direct positive film, heat development film, silver It can be used for die bridges, etc.

〔Example〕

Specific examples of the present invention will be described below, but the embodiments of the present invention are not limited thereto.

In the following examples, the amount added in the silver halide photographic material is 1I11! unless otherwise specified. Shows the number of grams per serving. Furthermore, silver halide and colloidal silver are shown in terms of silver. Sensitizing dyes are expressed in moles per mole of silver.

[Example 1] (Preparation of sample No. 101) Ideal for a silver iodobromide emulsion with an average grain size of 0.4 μ and an internal silver iodide core of 8 mol % and an average silver iodide content of 8 mol % was subjected to total sulfur sensitization, sensitizing dyes ■-27 and 5R-1 were added at 4.5X 10-' mol and 3X 10-' mol per mol of silver, respectively, and compound lll-61 was added at 7 mol per mol of silver. Spectrally sensitized to green sensitivity by adding .5XlO'mol.

Then, 4-hydroxy-6-methyl-1,3,3a,
Stabilization was achieved by adding 7.tetrazaindene and 1-phenyl-5-mercaptotetrazole.

Furthermore, a dispersion in which magenta coupler [MR-1] was dissolved in ethyl acetate and dinonyl 7-thalerate (DNP) and emulsified and dispersed in an aqueous solution containing gelatin, and general photographic additives such as a spreading agent and a hardening agent were added. In addition, a coating solution was prepared, coated on a subbed triacetyl cellulose support by a conventional method, and dried to prepare photosensitive material sample No. 101.

(Creation of sample No., IO2~No., 110) Sample No.
101 sensitizing dye 5R-1 and compound I[-61]
Sample No. 10, except that the dye described in 1 was replaced in an equimolar amount.
It was created in exactly the same manner as 1.

(Creation of sample No. 111=No, 115) Sample No.
Sample No. 110, tt, except that the magenta coupler MR-1 in No. 110 was replaced with the coupler listed in Table 1 in equimolar amounts.

Created in exactly the same way.

The samples thus obtained were evaluated for sensitivity and stability over time of the coated samples. Each sample was exposed to wedge light according to a conventional method and processed through the following processing steps. The evaluation results of the samples are shown in Table-1.

Sensitivity is the reciprocal of the exposure amount required to provide a density of minimum density + 0.1, and is expressed as a relative value when sample No. 101 is taken as 100.

The storage stability of the coated samples over time was determined for the samples obtained by leaving them naturally for 3 days (A) and the samples forced to deteriorate by leaving them at a constant temperature of 50°C and 80% relative humidity for 3 days (B). The sensitivity of (B) to sample (A) is shown as a relative value when the sensitivity of sample (A) is set to 100. Therefore, the larger the value, the better the storage stability over time.

Processing process (38°C) Processing time Color development
3 minutes 15 seconds bleach, 6 minutes 30 seconds water
Wash for 3 minutes and 15 seconds
Arrive: Wash for 6 minutes and 30 seconds
Stabilized for 3 minutes and 15 seconds
The composition of the treatment liquid used in each treatment step for 1 minute and 30 seconds is as follows.

Color developer composition 4-amino-3-methyl-N-ethyl-N-(β-hydroxyethyl)aniline sulfate 4.75g anhydrous sodium sulfite 4.25g hydroxylamine 1/2 sulfate 2.0g anhydrous potassium carbonate
37.5 g potassium bromide
1.3 g Nitrilotriacetic acid trisodium salt (monohydrate) 2.5 g
Add 1.0 g of potassium hydroxide and water to prepare II2.

Bleach composition Ethylenediaminetetraacetic acid iron ammonium salt 100.0g Ethylenediaminetetraacetic acid diammonium salt 10.0g Ammonium bromide 150.0g Glacial acetic acid
-10rrr (1 Add water to make 1ffi, and use ammonia water to pH 6.
, adjust to 0.

Fixer composition Ammonium thiosulfate 175.0g Anhydrous sodium sulfite 8.6g Sodium metasulfite 2.3g Add water and iff
and adjust the pH to 6.0 using acetic acid.

Stabilizing liquid composition Formalin (37% aqueous solution) 1.5a
+ (2 Konidax (manufactured by Konica Corporation) 7.
Add 5 mQ water to make la.

The samples obtained in this way were evaluated for fogging sensitivity and the storage stability of the coated samples over time.As is clear from the results in Table 1, the samples of the present invention had high sensitivity and the storage stability of the coated samples over time. It can be seen that this has been improved. Effect of the present invention when a coupler represented by the general formula [M-1] is further used in the present invention Example 2 (Preparation of sample No. 201) The following is applied on a subbed triacetyl cellulose film support Multilayer color photosensitive material No. 1 was prepared by sequentially forming each layer having the composition shown in the following from the support side.

201 was created.

The coating weight is expressed in g/m2 for silver halides and colloidal silver, and in g/m2 for additives and gelatin; , compound lll-1, coupler and
The DIR compound is expressed in moles per mole of silver halide in the same layer. The emulsions contained in each color-sensitive emulsion layer were optimally sensitized using sodium thiosulfate and chloroauric acid.

1st layer; antihalation layer (HC) Black colloidal silver 0.20 UV absorber (UV-1) 0.10 UV absorber (UV-2) 0.20 dioctyl 7-talate (D OP) 0.03 2nd Layer: Intermediate layer (IL-1) Gelatin 2.0 Anti-staining agent (AS-1) 0.1D OP
0.1 Third layer; low sensitivity red-sensitive emulsion layer (R-L) silver iodobromide emulsion (Em-2)
0.6911 (Em-3) 0.
51 sensitizing dye (S-1) 3.2X 10-' (mol/
1 mole of silver) // (s-2)3.2xlO-'(//
)// (S-3)0.2X10-'(//
) Cyan coupler (C-1)
0.085 colored cyan coupler (CC-1)
0.005DIR compound (D-1)
0.0015tt (D-2)
0.002D OP
0.6 gelatin 1.
1 4th layer; High sensitivity red-sensitive emulsion layer (R-H) Silver iodobromide emulsion (Em-1), 1.3 Sensitizing dye (S
-1) 1.6X 10-' (mol/1 mole of silver)//
(S-2)1.7X10-'(// )//
(S-3) 0.1XlO-' (// ) Cyan coupler (C-2) 0.07 Cyan coupler (C-3) 0.027 Colored cyan coupler (CC-1) 0.001
5DIR compound (D-2) 0.0
01D OP O,
2 Gelatin 1.1 5th layer; Intermediate layer (IL-2) Gelatin 0.8A S
-10,03 0OP 0.2 6th layer; low-sensitivity green-sensitive emulsion layer (G-1) silver iodobromide emulsion (E
m −2) 0.98// (Em
-3) 0.32 sensitizing dye (SR-4)
6.7X 10-'// (S
R-5) 0.8X1
0 Ichiban magenta coupler [MR-1] 0
．． 09 Colored Magenta Coupler ([M-1) 0.
004DIR compound (D-1) 0
．． 001// (D-3) 0.
003 Tricresyl phosphate (T CP ) 0
．． 5 Gelatin 1.2 7th layer: High-sensitivity green-sensitive emulsion layer (GH) Silver iodobromide emulsion (
Em-1) 1.4 sensitizing dye (n-27
) 2.3X 10-'// (
SR-1) 1.1X
10-4 Compound lll-13,4X 10'-' Magenta Coupler [M-4) 0.03 Colored Magenta Coupler ([M-1) 0.002DIR
Compound CD-3') 0.001T
CP O,3 gelatin 0.8 8th layer; yellow filter layer (YC) yellow colloidal silver
0.08Δ5-1
0.1D OP
0.3 Gelatin 0.6 9th layer - low sensitivity blue sensitive emulsion layer (BL) Silver iodobromide emulsion (
Em-2) 0.25tt (Em
-3) 0.25 sensitizing dye (S -4)
5.8x 10-' yellow coupler (
Y-1) CP gelatin 1st O layer; high-sensitivity blue-sensitive emulsion layer (B-H) silver iodobromide (
Em-4) Sensitizing dye (S-5) //(S-6) Yellow coupler (Y-1) CP Gelatin 11th layer; 1st protective layer (PRO-1) Silver iodobromide (Em-5) Ultraviolet absorber (UV-1) tt (UV-2) CP Gelatin 12th layer: 2nd protective layer (PRO-=2) Polymethyl methacrylate 0.29 0.2 1.1 0.5 3, OX 10- ' 1.2X 10-' 0.08 0.1 1.2 0.5 0.1 0.2 0.03 0.55 0.2 (Average particle size 1.5 μsm) Formalin scavenger 3.0 Hard Membrane agent (H-1) 0.4 Gelatin 0.5 In addition, each layer contains:
In addition to the above composition, a surfactant was added as a coating aid.

The emulsions used in the above samples are as follows.

All of them are high-internal monodisperse emulsions.

Em-1 + average AgI content 8.0 mol% octahedral average grain size 0.55 μm Em-2: average AgI content 7.5 mol% octahedral average grain size 0.46 μm Em-3・average AgI content 2 .5 mol% Octahedral average grain size 0.30 μm Em-4: Average AgI content 8.5 mol% Octahedral average grain size 0.85 μI Em-5: Average Agl content 1.0 mol% 8.0 mol% Average particle size 0.07 μm (Creation of sample No. 202-221) Sample No. 201 except that the sensitizing dye and compound DI-1 in the seventh layer were replaced with the compounds shown in Table 2.
It was created in exactly the same manner as 0201.

(Creation of sample No. 222) The sensitizing dye added in sample No. 207 was l-15.
, ■-45, ■-27 each 1.13X10□4 mol/silver 1
It was prepared in exactly the same manner as Sample No. 207 except that the mole was used.

(Creation of sample No. 223, No. 224) Sample No.
Sample No. 222 was prepared in exactly the same manner as Sample No. 222, except that Compound I[[-2 was replaced by the compound listed in Table 2 in an equimolar manner.

Regarding the sample thus obtained, sensitivity and storage stability of the coated sample over time were evaluated in the same manner as in Example 1. The results for the green photosensitive layer are shown in Table 2. In addition, the sensitivity is sample No. 201
It is expressed as a relative value with 100.

As is clear from Table 2, it can be seen that the samples of the present invention are excellent in sensitivity and storage stability of coated samples over time, which are the effects of the present invention.

Table 2 Example 3 (Preparation of Sample No. 301) Multilayer color photographic element sample No. 301 was prepared by sequentially forming each layer having the composition shown below on a triacetyl cellulose film support from the support side. I-ko.

1st layer: antihalation layer (HC) black colloidal silver 0.2 UV absorber (UV-1) 0.3 high boiling point solvent (Oi Q-1) 0.3 gelatin 0.4 2nd layer; intermediate layer (
IL-1) Gelatin 1.0 Third layer; First red-sensitive emulsion layer Silver iodobromide emulsion (E m-6) 0.6 Sensitizing dye (S-1) 5. OX 10-
'// (S-2)8. OX 10-'// (S
-3)3. OX 10-'Cyan coupler (C-1)
0.101/ (C-4)
0.25 colored cyan coupler (CC-
1 DIR compound (D-2) High boiling point solvent (Oi12-1) Gelatin 4th layer; 2nd red-sensitive emulsion layer Silver iodobromide emulsion (Em-7) Sensitizing dye (S-1) tt(S- 2) tt (S 3) Cyan coupler (C-1) tt (C-4) Colored cyan coupler (CC DIR compound (D-2) High boiling point solvent (OiQ-1) Gelatin 5th layer; 3rd red-sensitive emulsion Layered silver iodobromide emulsion (Em-8) Sensitizing dye (S-1) tt (S-2) tt (S 3) ) 0.04 0.05 0.45 1.2 1.0 3, OX 10 -' 2, OX 10 Ichiban 2, OX 10-' 0.10 0.30 ) 0.03 0.07 0.50 1.3 1.0 1, OX 10-' i, ox io-' 1, OX 10-' Cyan coupler (, C-1) 0.20
// (C-2) 0.10 colored cyan coupler (CG-1) 0.02DI
R compound (D-2) 0.05 High boiling point solvent (Oi Q-1) 0.40 Gelatin 1.6 6th layer; intermediate layer (IL-2) Gelatin 0.83 C-
10,03 3C-20,02 High boiling point solvent (Oi Q-2) 0.0
5 7th layer; 1st green-sensitive emulsion layer Silver iodobromide emulsion (Em-9) 0.4 Sensitizing dye (u-27) 6.7x 10-'/
/ (SR-1) 0.8X
10-'// (SR-6)
8. Mouth X 10-' Compound (III-2)
8.8xlO' magenta coupler [MR-1]
0.25// [MR-2)
(LO5 Colored Magenta Coupler ([M
-2) 0.04DIR compound (D -3)
0.06 high boiling point solvent (Oiff-2)
0.4 Gelatin 0
．． 8 Eighth layer; second green-sensitive emulsion layer Silver iodobromide emulsion (E m -10) 0.
8 sensitizing dye (S-27) 3. Ox 1
0-'tt (SR-1) 1.0x
lO-'/I (SR-6) 4.0X
10-6 Compound (III-2) 4.4
X 10-' Magenta coupler [MR-1]
0.20// [MR-2)
0.05 Colored Magenta Cabra = (, [M -2)0
．． 03DIR compound (D-3')
0-05 high boiling point solvent (Oi Q-2)
0.30 gelatin 1.
1 9th layer; 3rd green-sensitive emulsion layer Silver iodobromide emulsion (E m -11) 1.
2 sensitizing dye (S-27) 2. Ox 1
0-'// (SR-1) 7.0xlO
-'Compound (m-2) 3-Ox 1
0-'0.10 0.05 2) 0.02 0.02 0.30 1.1 Magenta coupler [MR-1) tt, [MR2] Colored magenta coupler ([M-DIR compound (D-3”) High boiling point solvent C04Q 2) Gelatin 1st O layer; Yellow filter layer (yc) Yellow colloidal silver additive (SC-1) // (SC2) High boiling point solvent (OiQ-2) Gelatin 11th layer: 1st blue sensitive emulsion Layer Silver iodobromide emulsion (E m -12) Sensitizing dye (S-4) Yellow coupler (Y-1) DIR compound (D -2'') High boiling point solvent <or, ci 2) Gelatin 12th layer; 2 Blue-sensitive emulsion layer 0.05 0.03 0.02 0.05 1.0 0.20 1, OX 10-3 0.80 0.10 0.28 1.3 Iodobromide #j (Em-13 ) Sensitizing dye (S-4) Yellow coupler (Y-1) DIR compound (D-2) High boiling point solvent (Ojff-2) Gelatin 13th layer; 3rd blue-sensitive emulsion layer Silver iodobromide (E m- I4) Sensitizing dye (s-4) Yellow coupler (y-1) DIR compound (D-2) High boiling point solvent (O412-2) Gelatin 14th layer; 1st protective layer (PRO-1) Silver iodobromide (,E m -15) Ultraviolet absorber (UV-3) // (UV 2) Additive (I5-1) Additive (HS -2) High boiling point solvent (OiQ-1) 0.5 5, OX 10 -' 0.60 0.08 0.25 0.5 0.7 2, OX 10-' 0.20 0.0I O907 0,70 0,3 0,10 0,10 0,5 0,2 0, 10 tt (Off-3)
0.10 gelatin
1.0 12th layer; second protective layer (PRO-2) Alkali-soluble matting agent 0.12 (average particle size 2 μm) Polymethyl methacrylate 0.02 (average particle size 3 μm) Slip agent (WAX-1) 0. 04 Gelatin 0.7 In addition to the above composition, each layer also contains 5U-2 coating aid and 5U-5 dispersion aid.
2,5U-3, hardener H-1 stabilizer 5tab-1, antifoggant AF-1AF-2, and preservative DI-1 were added.

The emulsions used in the above samples are as follows.

All of them are high-internal monodisperse emulsions.

Em-6: Average AgI content 7.0 mol%, octahedral average grain size 0.3 μm Em-7: Average AgI content 8.0 mol%, octahedral average grain size 0.7 μm Em-8: Average AgI content 6.0 mol% Octahedral average particle size 1. θμ theory Em-9: average AgI content 7.0 mol% octahedral average grain size 0.3 μm Em-10 + average Agl content 8.0 mol% 8.0 mol% octahedral average grain size 0.7 μm E m -11 : Average AgI content 6.0 mol% Octahedral average particle size 1. θμ times Em-12 Bi-average Agl content 7.0 mol% Octahedral average grain size 0.70 μm Em-13: Average Agl content 8.0 mol% Octahedral average grain size 0.7 μl Em-14: Average Ag ? Content rate 6.0 mol% Octahedral average particle size 1.0 μm Em-15: Average Agl content 1.0 mol% 8.0 mol% Average octahedral particle size 0.08 μm (Creation of sample No. 302-No. 315) Sample N
Sample No. 301 was prepared in exactly the same manner as Sample No. 301, except that the sensitizing dye of No. 301 and Compound m-2 were replaced with the compounds listed in Table 4. (Creation of sample No. 316) Sample No.
Sample No. 305 except that the sensitizing dyes contained in the 7th layer, 8th layer, and 9th layer were changed as shown in Table 3.

It was created in exactly the same manner as 305.

Table 3 Amount of dye added (XIO''-4) Color! l-15l-45ll-27 7th layer
2.9 2.9 2.9 8th layer 1.5
1.5 1.5 9th layer 1.0 1.0
1.0 (Preparation of Samples No. 317 to No. 320) Sample No. 316 was prepared in exactly the same manner as Sample No. 316, except that Compound I-2 was replaced with the compound listed in Table 4 in equimolar amounts.

Each sample was wedge exposed according to a conventional method and processed in the same manner as in Example 1.

The thus obtained sample was evaluated in the same manner as in Example 1 for fogging, sensitivity, and storage stability of the coated sample over time.

The results are shown in Table 4. Note that the sensitivity is a relative value when sample No. 301 is taken as 100, and the sensitivity and storage stability are for blue light sensitivity.

As is clear from Table 4, it can be seen that the samples of the present invention are excellent in sensitivity and storage stability over time of coated samples.

Example 4 On an undercoated triacetyl cellulose film support, each layer having the composition shown below was sequentially formed from the support side to prepare sample No. 3, which is a multilayer color photographic material.
01 was created.

1st layer; antihalation layer (HC) black colloidal silver 0.18 gelatin 0.4 2nd layer; intermediate layer (IL-1) 2.5-di-pentadecylhydroquinone 0.18 [M-40
,07 CC-20,02 5-100,002 UV -40,06 UV -30,08 UV -50,10 0iff-20,10 0iQ-30,02 Gelatin 1.04 Third layer; 1st Red-sensitive emulsion layer Silver iodobromide emulsion (Em-A) // (Em-B) Sensitizing dye (S-1) tt (S-8) // (S7) //(S3) Cyan coupler ( C-5') DIR compound (D-4) Gelatin 4th layer: 2nd red-sensitive emulsion layer Silver iodobromide emulsion (EmC) Sensitizing dye (S-1) //C8-7) tt(S-3 ) Cyan coupler (C-5) Colored cyan coupler (CC DIR compound (D-4) Gelatin 5th layer; 3rd red-sensitive emulsion layer Silver iodobromide emulsion (Em-D) 0.25 0.25 6.9X 10-' L6X 10-6 1.8X 10-' 3, IX 10-' 0.335 0.020 0.87 1.0 5, IX 10-' 1.4X 10-' 2.3X 10-most 0 .40 2) 0.05 0.015 1.3 1.60 Sensitizing dye (S-1) tt('Es-7) //(S-3) //(S-8) Cyan coupler CC-5 ) // (C-6) Colored cyan coupler (CC- High boiling point solvent (O4(1-1) 〃 (O1α-2) Gelatin 5.4X 10-' 1.4X 10-' 2.4X10-1. 2X10' 0.08 0.097 2) 0.01 0.22 0.10 1.63 6th layer: Intermediate layer (IL-2) Gelatin-4 High boiling point solvent (Oi12-4) 7th layer: 1st Green-sensitive emulsion layer Silver iodobromide emulsion (Em-A) // (Em-B) Sensitizing dye (I-69) tt (SR-3) Compound (III-1,) 0.4 0.04 0 .02 0.4 0.15 1, OX 10-' 3.8X 10-' 5, lXl0-' Magenta coupler [MR-4] Colored magenta coupler ([M tt ([M DIR compound (D-5) Boiling point solvent (Oiff-2) tt (04121) Gelatin 8th layer; 2nd green-sensitive emulsion layer Silver iodobromide emulsion (Em-C) Sensitizing dye (SR-7) // (I 69) tt (SR3) Compound (III-1) Magenta coupler [MR-4) tt [MR2] Colored magenta coupler ([M DIR compound (D-6) High boiling point solvent (Oiff 3) tt (O4ff5) Gelatin 0.26 4) 0.21 3) 0.03 0.025 (Ll OoOl 1.54 0.45 2, IX 10-' 7, OX 10-' 2.6X 10-' 3.5X 10-' 0.094 0.05 3) 0 .026 0.018 0.16 0.008 0.50 9th layer: Third green-sensitive emulsion layer Silver iodobromide emulsion (E m -D) 1.
2 sensitizing dye (SR-3) 3. OX1
0-'// (I-69) 8. O
X 10-' compound (I[I-1)
4.2X 10-' Magenta Coupler [MR-4]
0.015// [MR-5]
0.10 colored magenta coupler ([M
-3) 0.025 high boiling point solvent (Oi (1-2
) 0.25〃 (O1β-1,)
0.10 gelatin
l, 54 first O layer; yellow filter layer (YC
) Yellow colloidal silver 0.05 Additive (A S-2) 0.08 High boiling point solvent (Oi Q-1) 0.03 Gelatin 0.60 11th layer; 1st blue-sensitive emulsion layer Silver iodobromide emulsion ( E m −A ) 0.
08t/ (Em-B) 0.0
711 (Em-F) 0.07 sensitizing dye (
S-7) Yellow coupler (Y-2) DIR compound (D-4) tt (D-6) High boiling point solvent (Oiα-2) Gelatin 12th layer; 2nd blue-sensitive emulsion layer Silver iodobromide (Em- G) Sensitizing dye (S-7) Yellow coupler (Y-2) DIR compound (D-4) tt (D-5) High boiling point solvent (O4(2-4) Gelatin 13th layer; 3rd blue-sensitive emulsion Layer Silver iodobromide (Em-H) Sensitizing dye (S-7) Yellow coupler (Y-2) DIR compound (D-4) High boiling point solvent (O4ff-2) 3.5X 10-' 0.721 0 .02 0.015 0.28 1.1 0.45 9.5X 10-' (L154 0.007 0.010 0.05 0.78 0.77 2.2X 10 0.20 0.005 0, O7 Gelatin 0.70 1st
4 layers; 1st protective layer (PRO-1) Silver iodobromide (Em-1) 0.5 Ultraviolet absorber (UV-6) 0.11t
t (UV-7) 0.17 High boiling point solvent (Oi (21) 0.05 Gelatin 1.0 1st'5 layer; 2nd
Protective layer (PRO-2) polymethyl methacrylate
0.54 (average particle size 1.5 μm) Additive (HS-3) 0.10/
/ [MS-4) 0.10 Gelatin 1.20 In addition to the above composition, gelatin hardening agent H-2 and a surfactant were added to each layer.

The emulsions used in the above samples are shown in Table 5 (preparation of samples No. 402 to No. 407) and sample No. 4.
Sample No. 401 was prepared in the same manner as Sample No. 401 except that the sensitizing dye No. 01 and Compound II [-1 were replaced with the compounds listed in Table 6.

(Creation of sample No. 408 to No. 410) Sample No.
Coupler M included in the 7th layer, 8th layer, and 9th layer of 404
Sample No. 4 except that R-4 was changed as shown in Table 6.
It was created in exactly the same manner as 04.

Each sample was wedge exposed according to a conventional method and processed in the same manner as in Example 1.

The thus obtained sample was evaluated in the same manner as in Example 1 for fogging, sensitivity, and storage stability of the coated sample over time. In this case, the following saturation step B was used for the treatment.

The results are shown in Table-6. Note that the sensitivity is a relative value when sample No. 401 is taken as 100.

Processing step B (38°C) Processing time Color development
Bleach for 3 minutes and 15 seconds
1 minute bleach fix
Wash with water for 3 minutes and 15 seconds■
40 seconds〃 ■ 1 minute stabilization 40 seconds drying (50° C.) 1 minute 15 seconds In each treatment process, water washing (■) and (2) were conducted in a countercurrent manner from (■) to (■). The composition of the treatment liquid used is as follows. The replenishment amount of each processing solution is 1 for color development per 1 m2 of color photosensitive material.
200■a1 and others were all set to 800aQ including water washing. Also, the amount of pre-bath brought into the washing process is 1 for color photosensitive materials.
It was 50+++ffi per m2.

Color developer composition Mother liquor Replenishment solution diethylenetriamine 5 acetic acid ■-Hydroxyethyl Dan-1,1-diphosphonic acid sodium sulfite Hydroxylamine・ sulfate 1.0g 1.1g 2.0g 2.2g 4.0g 4.4g 2.4g 2.6g potassium carbonate potassium bromide 4-(N-ethyl-NJ-hi roxiamino)-2 Luaniline sulfate add water tl Bleach solution composition Mother liquor, ethylenethia mince ammonium salt Ethylenediami 2 sodium ammonium bromide ammonium nitrate bleach accelerator Add water to make if, Adjust to 6.3.

Bleach-fix composition Ethylene diammonium salt methine tetraacetic acid mother liquor, replenisher common ferric tetraacetate 30.0g 32.0g 1.4g 0.7g 4.5g 1.0a 10.0 common replenisher ferric triacetate Iron 5.0g 1.0ff 10.05 120.0g 1 (LOg 100.0g 10.0g 5X1G-” pH using aqueous ammonia 50.0g Disodium ethylenediaminetetraacetate 5.0g Ammonium thiosulfate aqueous solution (70%) 240++12 Sodium sulfite 12.0g Add aqueous ammonia to make 1 (2), and adjust to pH 7.3 using acetic acid.

Washing water composition Tap water containing 32 tags of calcium ions/Q and 7.3 mg/Q of magnesium ions was passed through a column filled with H-type strongly acidic cation exchange resin and 01-type anion exchange resin, and calcium ions 1.2+g/Q 2 per ix in water treated with C magnesium ion 0.4 rrrg/Q
0 mg was added and used.

Stable liquid composition Mother liquid and replenisher common polymarin (37% W/D 2.0g polyoxyethylene-p-7nononylphenyl ether (average degree of polymerization 10) 0.3g ethylenediaminetetraacetic acid 2.sodium salt 0.05g water In addition, the drying temperature of lQH 5,8 was set to so''c.

It can also be seen from the results in Table 6 that the samples of the present invention have improved sensitivity and storage stability over time of coated samples.

Further, in the present invention, when a coupler represented by the general formula [M-1] is used in combination, the effects of the present invention become more remarkable.

The structural formulas of the compounds used in the examples of the present invention are shown below. α (weight ratio) i a S S-2 (IHS JI3 ■ ■ CHx -CHSOx CH2C0NHCH2CH!
-CHSOx CHzCONHCH.

■ Na0sS CC00CHz (CFzCFx)sHC
C00CHz (CFzCFz)sH 2 Na03S CC00CJ+y CHz C00CaH+y ■ = 2 AX-1 MW : 30.000 - 5 2H6 CJ* R Dye used for comparison R R-2 (shiH!)4bυ1g 1h R R- [Invention Effects] According to the present invention, a silver halide color photographic light-sensitive material is provided which has enhanced spectral sensitivity in the green light wavelength region and has excellent storage stability over time of the produced light-sensitive material.

Claims (2)

[Claims] (1) In a silver halide photographic material having at least one light-sensitive silver halide emulsion layer on a support, the silver halide grains contained in at least one of the light-sensitive silver halide emulsion layers have the following general formula: Spectrally sensitized with at least one sensitizing dye represented by [I] and at least one sensitizing dye represented by the following general formula [II], and the layer contains the following general formula [III], [ A silver halide color photographic material containing at least one compound represented by IV] or [V]. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ General formula [II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ General formula [III] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ General formula [IV] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ General formula [V] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R_1_1, R_1_2, R_2_1, R_2
_2, R_4_6, R_5_7 represent substituted or unsubstituted alkyl groups, R_1_3, R_2_2 are hydrogen atoms,
Represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. X_1, X_2, and X_4 represent charge-balancing counterions, and n_1, n_2, and n_4 represent numerical values for adjusting the charge of the entire molecule. R_1_4 and R_2_4 represent a hydrogen atom or a substituent. W_1_1, W_1_2, W_2_1, W_2_2 represent a hydrogen atom or a substituent, but W_1_1, W_1_2,
W_2_1 and W_2_2 may be connected to form a condensed ring. Also, l_3, l_4, l_5 are integers of 0 or 1,
In the formula, Z_3, Z_4 and Z_5 each represent an atomic group necessary to form a 5- to 6-membered nitrogen-containing heterocycle. R_3_1, R_3_2, R_3_3, R_3_4, R
_3_5, R_4_1, R_4_2, R_4_3, R_
4_4, R_4_5, R_5_1, R_5_2, R_5
_3, R_5_4 and R_5_5 represent a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group, an alkoxy group, an aryl group represents an optionally substituted amino group, or adjacent substituents are condensed to form a 5- to 6-membered ring. Represents a group that can be formed. R_5_6 is a hydrogen atom, a substituted or unsubstituted alkyl group,
Represents an alkenyl group or an aryl group. R_5_7 represents a substituted or unsubstituted alkyl group or aryl group. ] (2) The silver halide color according to claim (1), wherein at least one of the green-sensitive silver halide emulsion layers contains at least one kind of coupler represented by the following general formula [M-I]. Photographic material. General formula [M-I] ▲ Numerical formulas, chemical formulas, tables, etc. It may have a group. X represents a hydrogen atom or a group that can be separated by reaction with an oxidized product of a color developing agent. Further, R represents a hydrogen atom or a substituent. ]