JPH03194550A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To enhance color reproduction performance and image quality of the photosensitive material and to stabilize them against variation of components in a processing solution by incorporating specified nonphotosensitive silver halide fine grains and a specified coupler. CONSTITUTION:This photosensitive material contains the nonphotosensitive silver halide fine grains comprising silver chloride in an amount of >=50 mol/% having an average grain diameter of <0.15 mum and having adsorbed a compound (A) capable of forming a silver salt more difficultly soluble than silver bromide, and further contains the pyrazoloazole type coupler represented by formula I in which R1 is H or a substituent; Y is aryloxy, alkoxy, or the like; and each of Za-Zc is optionally substituted methine, =N-, or the like. The compound of formula II and the like can be used for the compound of formula I, and the compound of formula III having a mercapto group, and the like can be used for the compound A, and it is added immediatlely after forming silver halide grains.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a silver halide color photographic light-sensitive material, and more specifically, a silver halide color photographic light-sensitive material with excellent color reproduction and little variation in development process. It is related to.

(Prior Art) Various techniques have been proposed in the past not only for color reproduction of printing materials but also for color reproduction of photographic photosensitive materials. For example, silver halide grains with or without spectrally sensitized, which are photosensitive elements, exhibit favorable spectral absorption.
Not only is a yellow filter layer usually provided, but also hydroquinone derivatives, sulfonamidophenol derivatives, and the like are used as color mixture prevention agents in the intermediate layer having different spectral sensitivities. Furthermore, in order to prevent color contamination due to side absorption of coloring dyes in couplers, colored couplers such as well-known yellow colored magenta couplers and magenta colored cyan couplers have been proposed and put into practical use.

However, the inclusion of these colored couplers in color light-sensitive materials not only has disadvantages such as an increase in the thickness of the emulsion film, but also has insufficient color reproducibility.

In addition, compounds that react with the oxidized form of a developing agent to release a development inhibitor or a development + ITI inhibitor precursor (DI
There is a known technique for improving color reproducibility by emphasizing interimage effects (hereinafter referred to as IIB) using DIR compounds (DIR compounds), and various types of these DIR compounds are used. . For example, a so-called DIR coupler reacts with an oxidized form of a color developing agent to form a coloring dye and releases a development inhibitor during development; So-called DIR substances that do not form coloring dyes, those that directly release a development inhibitor by reacting with an oxidized form of a color developing agent, and those that indirectly release a development inhibitor, such as JP-A-54-145135; No. 57-154234,
No. 58-162949, No. 5B-205150, No. 59-195643, No. 59-206834, No. 5
No. 9206836, No. 59-210440, No. 60-
Timing D as described in No. 7429 etc.
(referred to as IR compound), etc.

In the present invention, those exhibiting the above-mentioned DIR effect are collectively referred to as DIR compounds.

When these DIR compounds are used in a silver halide color light-sensitive material, a development inhibitor is released from the DIR compound during development, and the effect of suppressing the development of other silver halide emulsion layers, ie, 1.1. It is known that DIR compounds which are able to obtain E and in particular release so-called diffusible inhibitory groups or diffusible development inhibitor precursors are particularly effective.

However, these glabellar effects alone are not sufficient to improve color reproducibility, and it is necessary to improve the side absorption of coloring pigments.

Therefore, as a coupler, a pyrazolotriazole type magenta coupler with low side absorption, etc.
-27411 etc.

It is true that this pyrazolotriazole type magenta coupler has a higher 44
The color reproducibility was favorable because there was little sub-absorption near 0 nm and the absorbance on the longer wavelength side of the main absorption was extremely low.

However, photosensitive materials using these magenta couplers have the disadvantage that during running processing, sensitivity, gradation, and fog vary greatly due to fluctuations in processing solution components and eluates from the photosensitive material. Ta.

(Problems to be Solved by the Invention) The first object of the present invention is to provide a high-quality color photosensitive material with excellent color reproducibility. The second objective is to provide a color photosensitive material that is stable against fluctuations in processing solutions.

(i!Means for solving the problem) An object of the present invention is to provide a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support, the average size of which is less than 0.15 μm. and contains fine grain silver halide with a silver chloride content of 50 mol% or more, which has adsorbed a compound that forms a silver salt that is less soluble than silver bromide, and contains at least one compound of the following general formula [I]. This is achieved by a silver halide color photographic light-sensitive material characterized by containing.

General Formula (1) In General Formula (1), R5 represents a hydrogen atom or a substituent. Y represents a hydrogen atom or a leaving group, and particularly preferably a halogen atom or an allyl-thio group.

Za, Zb and Zc represent methine, substituted methine, =N- or -NH-, and one of the Za-Zb bond and Zb-Zc bond is a double bond and the other is a single bond. Zb
The case where the -Zc bond is a carbon-carbon double bond includes the case where it is a part of an aromatic ring. When R8 or Y forms a dimer or more multimer, Za, Zb or Zc
When is a substituted methine, this includes the case where the substituted methine forms a dimer or more multimer.

The present invention will be explained in detail below.

The fine silver halide grains used in the present invention have an average size (
The volume equivalent sphere diameter) must be less than 0.15 μm. If it is 0.15 μm or more, the optical scattering effect cannot be ignored, resulting in deterioration of image sharpness. Furthermore, it is preferable for the present invention that the average size is less than 0.13 μm, and 0.1 μm is particularly preferable. Ultrafine particles.

The particle size can be determined by a commonly used method using an electron microscope, and the average value of the zero particle size is determined by number averaging. Although there are no particular restrictions on the particle size distribution, it is preferable for the present invention to use a so-called monodisperse emulsion having a narrow size distribution.

A preferred size distribution has a coefficient of variation of 20% or less, more preferably 15% or less, particularly preferably 10% or less. The shape of the particle is a cube consisting of (100) planes, (111
octahedron consisting of ) faces, dodecahedron consisting of (110) faces,
Furthermore, (hhffi), (hM surface (h, k,
I! , >1). Also, 1 where (100) and (111) planes coexist
Particles having multiple faces such as tetrahedral particles may also be used. Further, tabular grains having twin planes or potato-like grains having an amorphous shape may be used. The fine particles used in the present invention may have any shape, but particles having mainly the (100) plane, which is the most stable crystal plane with a halogen composition preferred in the present invention, are particularly preferred.

The silver halide fine particles used in the present invention must mainly consist of silver chloride. The silver chloride content must be 50 mol% or more, preferably 75 mol% or more, particularly preferably 90 mol%. Pure silver chloride is most preferred.

The details of why fine particles with a high silver chloride content can increase sensitivity are unknown, but the development of the photosensitive particles is suppressed by inhibitors released from the sensitive material during development or by inhibitors entering from the developer, resulting in a substantial increase in sensitivity. One possible mechanism is to prevent dead grains from occurring. The reason why particles with a high silver chloride content effectively reduce the effect of inhibitors will also become clear in the future. The composition of halogens other than silver chloride in the fine grains of the present invention is preferably silver bromide.It is undesirable to make the silver iodide content too high.Even if the inside and surface layers of the fine grains consist of a uniform phase, they are composed of different phases. It may be.

When it is composed of different phases, either a core-shell structure or an epitaxial structure may be used.

The fine grain emulsion of the present invention does not need to be subjected to chemical or spectral sensitization, but may be chemically or spectral sensitized to the extent that no adverse effects such as blurring occur.

The method of preparing fine silver halide grains having a grain size of less than 0.15μ according to the present invention involves stabilizing the generated core grains at the initial stage of grain formation, that is, at the time of nucleation at the beginning of addition. Generating a large number of particles is a fundamental issue in forming fine particles.

The more stable nuclei there are, the more the silver halide that is formed later is deposited on these nuclei (thus, the grain size becomes finer after the addition is complete).

In order to form stable nuclei, it is important to keep physical ripening to a minimum during particle formation, that is, to prevent the formed nuclei from redissolving.

Therefore, the temperature during particle formation should be as low as possible.
The temperature is preferably 45°C or lower, and the potential at the time of charging (comparison electrode: saturated calomel electrode) is preferably in the range of +80 mV to +600 mV, especially at +250 mV during nucleation.
It is preferable to set it in the range of V to +600 mV.

Further, the concentration of the binder is important for stabilizing the core particles, and it is preferably used in a range of 0.2% to 4%.

Also, in order to generate a large number of nuclei, it is important to add a highly concentrated solution in a single period of time. For this purpose, the addition time is preferably completed within 30 minutes, preferably within 20 minutes, and more preferably within 15 minutes.

Although any stirring method may be used, it is preferable to use a method that has good stirring efficiency and ensures uniform stirring.

The method of particle formation is Single Jet method, Doub
In addition to the le Jet method or a combination thereof, any method such as a controlled double jet method may be used.

Further, in order to stabilize the core, suppress particle growth, and suppress physical ripening, it is preferable to add a tetrazaindene compound before, during, or after particle formation. Preferably, it is carried out immediately after particle formation.

The amount added is 0.1 to 10 g per mole of Ag, preferably 0.
．． 2-8g is good.

In order to adsorb the tetrazaindene compound, 911 during particle formation is preferably 2.0 or more, preferably 4.0 or more.

Normally, in silver halide emulsions, in order to remove unnecessary salts after grain formation, a precipitating agent is added that interacts with gelatin to form flocs, and the pH is optimized to precipitate silver halide grains and gelatin. After removing the supernatant liquid, a precipitation washing step (also referred to as a desalting step) in which water is newly added and washed is performed two to three times.

For silver halide grains with a grain size of less than 0.15μ,
In this desalting step, physical ripening progresses, resulting in an increase in particle size or deformation of the particles, which not only makes production unstable, but also prevents the required photographic performance from being improved.

In particular, if p) (during sediment washing) is less than 3.1, the particle size and shape will change significantly.However, if the pH value is higher than that, the change will be small. If it is, the change will be even smaller.

The pH in the desalting step is preferably 3.2 to 4.8, more preferably 3.4 to 4.8.

The gelatin used in preparing the silver halide emulsion of the present invention may be any gelatin, such as lime-treated gelatin, acid-treated gelatin, or fluorinated gelatin, or a combination thereof.

Anionic surfactants,
Precipitation methods using anionic polymers (e.g. polystyrene sulfonic acid) or gelatin derivatives (e.g. acylated gelatin, carbamoylated gelatin, etc.)
It is better to use the flocculation method.

The tetrazaindene compound preferably used in the present invention is preferably a compound represented by the following general formula (n).

General formula (It) 0)1 R, , R, and R1 are hydrogen atoms, alkyl groups, amino groups, derivatives of alkyl groups, derivatives of amino groups, halogen atoms, aryl groups, derivatives of aryl groups, or -CON
H-R, (R is a hydrogen atom, an alkyl group, an amino group, a derivative of an alkyl group, a derivative of an amino group, a halogen atom,
represents an aryl group or a derivative of an aryl group).

Next, specific examples of the tetrazaindene compounds according to the present invention will be shown.

■ 1 ■ ■ ■ -9 11 11 0 ■ 0)1 H 1-5 1-6 ■ ■ l-13 R H H H Next, the compound of the present invention that forms a silver salt that is less soluble than silver bromide will be explained. do.

Examples of compounds that form poorly soluble silver salts include mercaptotetrazoles, mercaptotriazoles, mercaptothiadiazoles, and 2-1000 benzthithiones, in which sulfur atoms form bonds with silver ions to form bonds on the surface of silver halide crystals. Compounds that adsorb to are preferred.

Among the above-mentioned preferred compounds containing sulfur, compounds having a mercapto group are specifically represented by the following general formula (III).
It is a compound represented by

Z -S I-1 (III) In the formula, Z is an aliphatic group (e.g., a substituted alkyl group such as a carboxyethyl group, a hydroquinethyl group, a diethylaminoethyl group), an aromatic group (e.g., a phenyl group, etc.), or a representing a heterocyclic residue (preferably a 5- to 6-membered ring)
The total number of carbon atoms in the MFI aliphatic group and aromatic W is preferably 18 or less.

Among these, heterocyclic residues containing one or more nitrogen atoms within the region (the total number of carbon atoms is preferably 30 or less, more preferably 18 or less) are particularly preferred.

The heterocyclic residue represented by Z may be further fused, and specifically, imidazole, triazole, tetrazole, thiazole, oxazole, selenazole, benzimidazole, benzoxazole, benzthiazole, thiadiazole, oxadiazole, benz Preferred are selenazole, pyrazole, pyrimidine, triazine, pyridine, naphthothiazole, naphthoimidazole, naphthoxazole, azabenzimidazole, purine, azaindene (eg, triazaindene, tetraazaindene, pentaazaindene, etc.).

Further, these heterocyclic residues and condensed rings may be substituted with appropriate substituents.

Examples of substituents include alkyl groups (e.g. methyl, ethyl, hydroxyethyl, trifluoromethyl, sulfopropyl, di-propylaminoethyl, adamantane)
, alkenyl groups (e.g. allyl), aralkyl groups (e.g. hensyl, p-chlorophenethyl), aryol groups (
For example, phenyl, naphthyl, p-carboxy-phenyl, 35-dicarboxyphenyl, m-sulfophenyl, p-aceto7midophenyl, 3-cabramide, phenyl, p-sulfamoylphenyl, m-hydroxy-phenyl, p-nitro phenyl, 3.5-dichlorophenyl, 2-methoxyphenyl), heterocyclic residues (e.g. pyridyl), halogen atoms (e.g. chlorine, bromine), mercapto groups, cyano groups, carboxyl groups, sulfo groups, hydroxy groups, carbamoyl groups, sulfamoyl groups, amino groups, nitro groups, alkoxy groups (e.g. methoxy, ethoxy), aryloxy groups (e.g. phenoxy), asol groups (e.g. acetyl), acylamino groups (e.g. acenalamino, capramide, methylsulfonylamino) ), substituted amine groups (e.g. diethylamino, hydroxyamino), alkyl or arylthio groups (e.g.
Examples include methylthio, carboxyethylthio, sulfobutylthio), alkoxycarbonyl groups (eg, methoxycarbonyl), and aryloxycarbonyl groups (eg, phenoxycarbonyl).

It may also be a disulfide (Z-3-3-Z) that is easily cleaved into the form of general formula (In) in an emulsion.

Among sulfur-containing inhibitors, those with thioketone groups are
Specifically, it is a compound represented by the following general formula (IV).

In the formula, R represents an alkyl group, an aralkyl group, an alkenyl group, or an aryl group.

X represents an atomic group necessary to form a 5- to 6-membered ring, and may be fused.

The heterocycle formed by Examples include benzthiazoline, naphthothiazoline, tetrahydrobenzthiazoline, benzimidacilline, and benzoxazoline.

Further, these heterocycles may be substituted with the W substituent mentioned in the compound of general formula (n).

Specifically, R includes an alkyl group (e.g., methyl, propyl, sulfopropyl, hydroxyethyl), an alkenyl group (e.g., allyl), an aralkyl group (e.g., benzyl), an aryl group (e.g., eva, phenyl, p -tolyl, 0-chlorophenyl), heterocyclic groups (eg, pyridyl), and the like.

Next, typical examples of compounds represented by general formula (II) will be listed.

■ ■ 1l-6 I[1-9 Shiri UNa ■ 1 I[1-1 ■ ■ ■-1 ■-20 ■ ■-22 ■-14 ■-15 CHzCHzOH ■-16 1 ■ ■-18 ■-23 ■ ■ ■ ■-27 ■-28 ■ 9 ■-30 V-1 V-2 V-3 V-4 H H H ■ R ■ 2 ■-33 1 Nllz-C-NHi ■-34 1 CH3NH-C-NH-CH3 Next, the general formula () A typical compound represented by Give an example.

V-5 V-6 V-7 IV-8 ■-11 C11゜■-9 C:IH7 ■-12 ■-10 H3 ■-13 These compounds are E, J, Birr: W″5tabi
Li-zation of Photography
ic 5ilver HalideEmulsio
ns' Focal Press 1974, C.
G.

Barlo- et al., Rer, Prog, Appl, Che
m, vol. 59, p. 159 (1974), Re5
EARCH DISCLOSURE I 7643
(1978), Tokuko Sho 4B-34169, Sho 47-1
8008, 49-23368, Science Magazine 1 Sat. 136
5-1369 (1954), Belsteln X
It can be obtained by referring to the documents cited in I, 394, ■, No. 121.

Particularly preferred adsorption compounds for the present invention are of the general formula (V)
It is a compound represented by

General formula (V) 1 In the formula, X represents 10--NH- or -S-, R,,
R,, Rs and R1 represent a hydrogen atom or a group capable of substituting this, and at least one of Rr, Rz, Rs and R1 is substituted or unsubstituted directly or via a divalent linking group, and has 13 carbon atoms. It is the following alkyl group or aryl group.

Next, general formula (1) will be explained in detail.

X represents 10--NH- or -S-.

Particularly preferably X is -NH-.

R,, R2, R, and R4 may be the same or different and each represents a hydrogen atom or a group that can be substituted for it. Preferred examples of Rr, Rt, Rs, and R4 are a hydrogen atom, a halogen atom (F, C1, Br, etc.),
Substituted or unsubstituted alkyl groups (methyl, trifluoromethyl, ethyl, n-octyl, benzyl, etc.), substituted or unsubstituted aryl groups (phenyl group, p-chlorophenyl, etc.), substituted or unsubstituted alkoxy groups, aryl Oxy groups (methoxy, n-hexyloxy, phenoxy, n-octyloxy, 2-ethylhexyloxy, etc.), sulfonyl groups (methanesulfonyl, p-toluenesulfonyl, etc.), sulfonamide groups (n-octanesulfonamide, p- toluenesulfonamide, etc.)
, sulfamoyl group (diethylsulfamoyl, 4-chlorophenylsulfamoyl, etc.), carbamoyl group (
n-butylcarbamoyl, 4-cyanophenylcarbamoyl, 2-ethylhexylcarbamoyl, etc.), amide groups (n-hexanamide, n-decanamide, benzamide, 2-ethylhexylamino, etc.), ureido groups (
3-butylureido, morpholinocarbonylamino, etc.), aryl or alkoxycarbonylamino groups (ethoxycarbonylamino, 1so-butylcarbonylamino, phenoxycarbonylamino, etc.), aryl or alkoxycarbonyl groups (ethoxycarbonyl, phenoxycarbonyl, etc.), aryl or The carbon of these substitutable groups is an alkylaminocarbonyloxy (phenylaminocarbonyloxy, 1so-butylaminocarbonyloxy, etc.), a cyano group, an alkyl or arylthio group (n-octylthio, 2-methoxycarbonylphenylthio, etc.) The number is preferably 13 or less, particularly preferably 11 or less.

Here, at least one of Rt, Rz, Rs, and Ra is a substituted or unsubstituted alkyl group or aryl group having 13 or less carbon atoms, directly or via a divalent linking group. Preferably, it is a substituted or unsubstituted alkyl group having 5 to 11 carbon atoms. Particularly preferred divalent linking groups include amide bonds, sulfonamide bonds, ureido bonds, ether bonds, thioether bonds, sulfonyl bonds, carbonyl bonds, urethane bonds, carbamoyl bonds,
It is a sulfamoyl bond.

Xl represents a hydrogen atom or a cation (Na", K", NH, "", etc.) for making the molecule neutral.

Next, typical examples of compounds used in the present invention will be listed, but the present invention is not limited to the following compounds.

-5 -2 -6 ■ -3 -7 -4 -8 V-9 ■-10 ■ -12 -17 -18 ■ 9 ■-20 ■ ■ 3 ■ 4 ■ ■ ■ ■ -2 ■ ■ 2 ■-23 ■-24 1 ■-25 ■-29 ■ ■-26 ■-30 ■-27 -3 ■-28 ■-32 ■-33 ■-37 ■-34 ■-38 ■-39 ■-35 ■-36 ■ -410 The compound represented by the general formula (V) used in the present invention is:
J, Van A11an, B, D, Deacon, Or.
g, 5ynth.

■, 569 (1963), J, Bunner Be
r,, 9.465 (1876), L, B, 5eb
re11. C.E., Boord, Am.

Chem, Soc, +15, 2390 <1923) and JP-A-62-133448.

The fine grain emulsion with a high silver chloride content of the present invention can be used in any layer included in a color photographic light-sensitive material, such as a protective layer, a blue-sensitive layer, a yellow filter layer, a green-sensitive layer, an intermediate layer, a red-sensitive layer, and an antihalation layer. It can be included. If the photosensitive layer is divided into two or more layers, such as a high-sensitivity layer and a low-sensitivity layer, it may be contained in only one of the high-sensitivity layer, low-sensitivity layer, or intermediate sensitivity layer. It can be contained in two or more layers. In addition, a non-photosensitive layer may be included in one photosensitive layer (for example, a high-sensitivity green layer/a non-photosensitive intermediate layer/a low-sensitivity green layer). One preferred embodiment is that this non-photosensitive layer contains a fine grain emulsion. It is a particularly preferred form to contain the fine grain emulsion of the present invention in an intermediate layer between different photosensitive layers.
More preferably, it is contained in the protective layer that is the layer furthest from the support, the antihalation layer that is closest to the support, and the non-photosensitive layer adjacent thereto.

Although the layer containing the fine grain emulsion with a high silver chloride content of the present invention is sufficiently effective in just one layer, it may be contained in two or more layers. Further, a layer containing a fine grain emulsion having a high silver bromide content other than the one according to the present invention may coexist.

The amount of coated silver in the fine grain emulsion with high silver chloride content of the present invention is preferably 0.01 to 3 g/rrf, particularly preferably 0.05 to 1.5 g/rrl, and even more preferably 0.1 g/rrf. ~0.8g/rTr.

Next, the compound of the present invention represented by general formula (1) will be explained.

In the general formula ([), R1 represents a hydrogen atom or a substituent. Y represents a hydrogen atom or a leaving group, and is particularly preferably a halogen atom or an arylthio group.

Za, Zb and Zc represent methine, substituted methine, =N- or -NH-, and one of the Za-Zb bond and Zb-Zc bond is a double bond and the other is a single bond. Zb
RI when the -ZC bond is a carbon-carbon double bond, including when it is part of an aromatic ring. Alternatively, it includes the case where Y4 forms a dimer or more multimer, or when Za, Zb or Zc is a substituted methine, the case where the substituted methine forms a dimer or more multimer.

Among the pyrazoloazole couplers represented by the general formula (1), the imidazo[1,2-b) pyrazole described in U.S. Pat. Preferred are pyrazolo (1,5-b
) C1,2°4] Triazoles are particularly preferred.

In addition, a branched alkyl group as described in JP-A No. 61-65245 is directly connected to the 2.3 or 6-position of the pyrazolotriazole ring to create a pyrazolotriazole coupler, which is described in JP-A No. 61-65246. pyrazoloazole couplers containing a sulfonamide group in the molecule, pyrazoloazole couplers having an alkoxyphenylsulfonamide ballast group as described in JP-A-61-147254, European Patent Publication No. 226, Couplers described in No. 849 and No. 294,785 can be used.

Among those represented by general formula C1), particularly preferred is represented by general formula (M).

(However, R1 represents an alkyl group, an alkoxy group, or an aryloxy group, and R2 represents an acyl group or a sulfonyl group. +L+ represents an alkylene group of +C-CH~4 or a phenylene group, and in the case of an alkylene group, R, The carbon atoms substituted by ,R, are connected to the coupler core, and R,,R.

is a hydrogen atom, an alkyl group or an aryl group.

However, R1 and R4 are never hydrogen atoms at the same time. X
is an aryloxy group, an alkoxy group, an azolyl group, an alkylthio group, or an arylthio group.

R,, R, or represents a simple bond or a linking group, through which it is bonded to the vinyl group. ) Substituents R,, Rt in general formula (M)
, (IJ- and X will be explained in detail.

R8 is an alkyl group, an alkoxy group, or an aryloxy group, and more specifically, a linear or branched alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms. It is an oxy group. More specifically, methyl, ethylpropyl, isopropyl, t-butyl, 2-ethylhexyl, dodecyl, l-ethylpentyl, tridecyl, 2-methanesulfonylethyl, 3-(3
pentadecylphenoxy)propyl, 3-(4(2-(
4-(4-hydroxyphenylsulfonyl)phenoxy]dodecanamido)phenyl)propyl, 2-ethoxytridecyl, trifluoromethyl, cyclohexyl, 3
-(alkyl groups such as 2,4-di-t-amylphenoxy, methoxy, ethoxyisopropoxy, t-butoxy,
Alkoxy groups such as 2-methoxyethoxy, 2-dodecylethoxy, 2methanesulfonylethoxy, 2-phenoxyethoxy, phenoxy, 2-naphthyloxy, 2-
These are aryloxy groups such as methylphenoxy, 2-methoxyphenoxy, 4-methoxyphenoxy, 4t-butylphenoxy, 3-nitrophenoxy, 3-acetamidophenoxy, and 2-benzamidophenoxy. Among these groups, groups that can have further substituents include halogen atoms, alkyl groups, aryl groups, heterocyclic groups, cyano groups, hydroxy groups, nitro groups, carboxy groups, sulfo groups, amino groups, alkoxy groups, Aryloxy group, acylamino group, alkylamino group, anilino group, ureido group, sulfamoylamino group, alkylthio group, arylthio group, alkoxycarbonylamino group, sulfonamide group, carbamoyl group, sulfamoyl group, sulfonyl group, alkoxycarbonyl group , heterocyclic oxy group, azo group, acyloxy group, carbamoyloxy group, silyloxy group, phosphorylamino group, imide group, heterocyclic thio group, sulfinyl group, phosphonyl group,
RI is preferably an alkyl group such as methyl, ethyl, isopropyl, or t-butyl, which may further have a substituent such as an aryloxycarbonyl group, an acyl group, or an azolyl group;
An alkoxy group such as methoxy, ethoxy, isopropoxy, 2-methoxyethoxy, or 2-phenoxyethoxy, or an aryloxy group such as phenoxy, 2-methoxyphenoxy, 4-methoxyphenoxy, or 2-methylphenoxy.

R1 represents an acyl group or a sulfonyl group, specifically an acyl group such as alkanoyl or aryloyl having 8 to 40 carbon atoms, or a sulfonyl group such as alkylsulfonyl or arylsulfonyl having 10 to 40 carbon atoms. More specifically, straight-chain and branched lukanoyl groups such as 2-ethylhexinoyl, decanoyl, tetradecanoyl, pentadecanoyl, stearoyl, and isostearoyl, and straight-chain alkanoyl represented by the following general formula (A). group, 1-stearyloxybenzoyl, 3-(2-ethylhexanoylamino)benzoyl, 2.4-dioctyloxyhenzoyl, 4-(4-dodecyloxyhenzenesulfonamido)benzoyl, 1-octyloxy-2-naphthoyl aryloyl groups such as dodecylsulfonyl, alkylsulfonyl groups such as octadecylsulfonyl, 2-butyloxy-5-t-octylbenzenesulfonyl, 1
-Octyloxy-4-naphthylsulfonyl, 2-octyloxy-5-t-octylbenzenesulfonyl, 2
- (2-hexyloxyethoxy)-5-t-octylbenzenesulfonyl, 2-(2-ethoxyethoxy)
-5-(2-octyloxy-5-t-octylhenzenesulfonamide)benzenesulfonyl, 2-octyloxy-5-(2-octyloxy-5-t-octylhenzenesulfonamide)benzenesulfonyl, and other aryls It is a sulfonyl group. These are R.

R1, which may further have a substituent as shown in formula (A), is preferably a substituted alkanoyl or arylsulfonyl group represented by general formula (A).

3 +L+ represents an alkylene group of +C-CHr)- or a phenylene group. Specifically, Ri and R4 are hydrogen atoms, alkyl groups such as methyl, ethyl, propyl, isopropyl, t-butyl, octyl, phenyl, trill,
It is an aryl group such as 2-naphthyl, and R1 and R1 are not hydrogen atoms at the same time.

3 +C 4 represents a phenylene group such as 1,2-phenylene, 1,3-phenylene, 1°4-phenylene, 4-methoxy-1,3-phenylene, 5-methyl-1,3-phenylene, preferably -(L)- is an alkylene group represented by aCHrh in which R1 and R4 are a hydrogen atom, methyl or phenyl group, or a alkylene group, or a phenylene group such as 1.3-phenylene or 1.4-phenylene. X is an aryloxy group, an alkoxy group, a 1-azolyl group, an alkylthio group, or an arylthio group, and specifically phenoxy, 4-methylphenoxy, 4-cyanophenoxy, 4-methanesulfonamidophenoxy, 4-acetamidophenoxy, 4-ethoxycarbonyl phenoxy,
4-carboxyphenoxy, 3-carboxyphenoxy, 2-carboxyphenoxy, 4-((1,1-dimethyl 1-(44 droxyphenyl)) methylphenoxy,
Aryloxy groups such as 4-(4-hydroxybenzenesulfonyl)phenoxy, 4-methoxyphenoxy, 1-naphthoxy, 2-phenethyloxy, 5-phenyltetrazolyloxy, 2-benzothiazolyloxy, methoxy, ethoxy, iso Alkoxy groups such as propoxy, t-butoxy, ethoxycarbonylmethoxy, 2-ethoxycarbonylethoxy, 2-cyanoethoxy, 2-methanesulfonylethoxy, 2-benzenesulfonylethoxy, 2-phenoxyethoxy, 1-pyrazolyl, ■-
imidazolyl, 3,5-dimethyl-1,2,4-)riazol-1-yl, 5- or 6-promobenzotriazol-1-yl, 5-methyl-1,2,3,4-tetrazol-1-yl, 1-Benzimidazolyl, 4-chloro-pyrazol-1-yl, 4-nitro-pyrazole-1
-yl, 4-ethoxycarbonyl-1-yl, 3- or 5-acetamidopyrazol-1-yl, 1-azolyl groups such as 2-acetamidoimidazolyl-1-yl, alkylthio groups such as dodecylthio, 1-carboxydodecylthio, Phenylthio-2-naphthylthio, 2-butoxy-5-1-octylphenylthio, 2-pivaloylaminophenylthio, 4-dodecylphenylthio, 4-octyloxyphenylthio, 2-octyloxy-5-
These are arylthio groups such as carboxyphenylthio and 2-(3-carboxybropyloxy)-5-L-octylphenylthio. These may further have a substituent represented by R.

Preferably, X is an aryloxy group, 1-azolyl group, or arylthio group, and more preferably, X is a substituted phenoxy group, a substituted pyrazol-1-yl group, or a substituted phenylthio group.

Next, specific examples of the coupler represented by the general formula (M) of the present invention will be shown, but the present invention is not limited thereto.

(M-1) (M-8) CH.

(M-6) 4H9 C, H, Yu C6H5I C&H13 [M 9) (M 10) C1l.

(M 13) (M 14) H3 C1゜11□ (M-11) (M 12) (M 15) (M 16) zHs CB H+, (t) 6H13 (M 17) (M 18) C.H.

(M-21) (M 22) CH, CH.

Cb　H+s (M-19) CH,CH3 C4H.

(M 23) (M 24) ShilIn+vLL7 (M 25) (M 26) (M 27) (M 30) (M 31) Shi81"II7 (LJ (M-28) (M 32) (M 33) 2 Shil13ji II3 Shi@11+6(L) (M 34) (M 35) (M 38) CH3 (M 39) 0 CH.

C00C, Hs (M 36) O COOCHff (M 40) CH.

CH.

-fCH! C, CH2C# 0 C00C4Hq (M 41) CH.

CH.

fCH2Csu7-----1CHt H 0 COOCz　Hs death! Shiti=Ll (M 42) CH.

CH3 -f CH2C-h--□e CH2-C shore 0 Coo-eC)i2bcOOH CH3 (M 43) (M 4G) C! (M 47) (M 44) (M 45) (M 48) Call+, (t) (M-50) The coupler of the present invention is disclosed in JP-A-60-197,688;
It can be synthesized using the methods described in US-4540654, JP-A-61-053644, and JP-A-62-209457.

Next, a synthesis example will be shown.

Add 103 g of anhydrous potassium carbonate (0°75 moj.
Then, 150 ml of acetonitrile was added and stirred at room temperature. Here, p-cresol 54゜0g (0.5mo
After adding 1), the mixture was stirred while heating under reflux. Furthermore, 41.5 g of chloroacetonitrile (0.55 mo
f) was added dropwise over about 5 minutes while being careful not to reflux too much. After the dropwise addition, the mixture was refluxed and stirred for 2 hours, and then cooled with water until the internal temperature reached about 30°C.

This was filtered with suction to remove inorganic substances, and the filtrate was mixed with 150 mj2 of ethyl acetate, 50 m1 of saturated saline, and 1 ml of water.
The extraction operation was performed by adding 00 mf.

The obtained ethyl acetate layer was mixed with 50 mf of saturated saline and 100 mf of water.
After washing three times with a mixed solution of rr+IV, it was dried with anhydrous sodium sulfate. After removing ethyl acetate using a rotary evaporator, the residue was distilled under reduced pressure to obtain 64.9 g of target product 1 (
0.44 moN) with a yield of 88%.

Boiling point: 85-88°C10,2mmHg Melting point: 31-3
102 g (1.0 moI2.) of methyl propionate was placed in a 300 mff1 Mitsuro flask equipped with a 3°C dropping funnel, a thermometer, and a drying tube (42 g of CaC), and the mixture was stirred in a water bath. Here, 56.1g of potassium t-butoxide
(0.50 mo!!,) was added, and while stirring, 173.6 g (0.50 mol) of the compound was added until the internal temperature was 1.
The solution was added dropwise, taking care not to exceed 0°C.

After the dropping was completed, the internal temperature was kept between 5 and 10°C and stirred for 3 hours, followed by 150 mj of water! and n-hexane 150m
j2 was added and extracted. Concentrated hydrochloric acid 42.9% was added to the resulting aqueous layer.
The mixture was neutralized by adding mj2 and extracted with 200mff1 of ethyl acetate. The obtained ethyl acetate layer was diluted with 50% saturated saline solution.
It was washed twice with a mixture of mj2 and 100 mf of water, and dried with anhydrous sodium sulfate. Ethyl acetate was distilled off using a rotary evaporator to obtain 46.1 g of target compound 2 as a crude product.

300rr+4 with reflux condenser and dropping funnel set! Compound 246 in the Mitsuro flask. Lg and 100 mff1 of isopropyl alcohol were added, and the mixture was stirred while heating under reflux. Here, 19.7 g of 80% aqueous solution of hydrazine hydrate
was added dropwise while being careful not to make the reflux too intense, and then heated under reflux for 3 hours. Amide 20 (1+of) was added and stirred. 4 was completely stirred. The internal temperature was about 30
The mixture was cooled with water until the temperature reached 'C', and crystals of acetonitrile 8 and 4 precipitated while cooling in a water bath, although they did not dissolve, and the mixture was stirred at room temperature for 3 hours. After adding 100 mf of water and stirring for another 3 hours, suction filtration was performed to remove the target material 3 at 33 mf.
．． Obtained 7 g (0.16 mof) with a yield of 1 to 31%.

Melting point: 174.0-176.5°C 300 mf of dimethylacetamide was added to 3.33.7 g (0.16 moff) and heated until dissolved. Once melted, cool to about 35°C and add 60 g of methyl 2-methyl-3-phthalimidopropioimidate hydrochloride (0,
21 moj of the mixture was added and stirred at room temperature for about 24 hours. An aqueous solution of 22 g (0.32 moff) of hydroxyamine hydrochloride and 13 g (0°16 moff) of sodium acetate was added to the reaction solution and heated to 50°C. After about 1 hour, heating was stopped.
After stirring for about 10 hours while gradually returning the temperature to room temperature, the mixture was heated to room temperature while stirring.

Pour 51 into ice, filter out the precipitated crystals, wash thoroughly with water, and dry to obtain 69g of 4 (yield 96%).
I was able to get it.

4.69g (0.15mol) of dimethylaceto Om
Balatoluenesulfonyl chloride dissolved in j2 28.
After dropping 6 g over about 30 minutes, the mixture was stirred for about 1 hour, 12.1 mj2 of pyridine was added, the water bath was removed, and the mixture was further stirred for about 1 hour. Then add the reaction solution to about 1.5! The aqueous solution was removed by decantation, and 1.5 ml of methanol was added to the remaining solid, which was triturated and filtered to obtain the tosylate compound of 4 as a colorless powder.

This was immediately dispersed in methanol 1.31, and pyridine 1
2.1 mff1 was added and heated to a temperature of reflux. When the tosylate compound melted, heating was stopped and the mixture was stirred while gradually returning the temperature to room temperature. After stirring at room temperature for about 2 days, methanol was distilled off under reduced pressure and concentrated to about 300 mj2.
! M! The reaction solution was poured into water. By filtering and drying the precipitated powder crystals, 29.8 g (yield 52%) of 5 could be obtained.

5.15 g (0,039 moffi) of isopropyl alcohol, 150 ml! To the solution, add 2.5 g (0,062 mo7) of 80% salt drazinhydrade,
After heating under reflux for about 8 hours, the mixture was returned to room temperature, chloroform and saturated brine were added, and suction filtration was performed to remove precipitated phthalhydrazide. The filtrate was extracted three times with chloroform,
The extracts were combined, washed with saturated saline, dried over magnesium sulfate, filtered and evaporated to obtain the amine compound as crystals. Add this amine to 100 ml of a 1:1 mixed solvent of dimethylacetamide and acetonitrile? Bottle, add ml of toluethylamine,
16.9 g of 2-hexyloxyethoxy-4-t-octylhenzenesulfonyl chloride (0.039 mo
ffi) was added dropwise. After dropping, the mixture was stirred for about 1 hour, extracted, dried, and evaporated. The resulting oil was purified by silica gel column chromatography (n-hexane:ethyl acetate-4=1). 1
It was possible to obtain 9.5 g (yield 72%) of the exemplary coupler (M5).

Melting point, 112-114°C JP-A-64-13071 or JP-A-64-1307
1 was synthesized by the synthesis method shown in No. 2, etc., and then conversion of 6 to 7 was carried out based on the synthesis example shown in JP-A-62-209457.

20 g of 60% sodium hydride (0,5+*oI!
) was added to 300 mj2 of N,N-dimethylindazolinone, and the mixture was stirred while cooling with water. In it, 34g of pyrazole (
0.5 sol) was added in 2 to 3 portions, and the mixture was stirred until hydrogen generation stopped. After that, 76g of 7 (0, Imoj
The mixture was heated and stirred at 120 to 125°C for 6 hours. The crude product obtained by post-treatment by a conventional method was purified by silica gel column chromatography (M
-26) was able to be obtained in an amount of 49 g (yield: 65%).

The magenta coupler represented by the general formula (1) of the present invention is added to the green-sensitive emulsion layer and/or its adjacent layer, and the total amount added is 0. O1 to 1.0 g/rrf, preferably 0.05 to 0.8 g/rrf, more preferably 0.
It is 1 to 0.5 g/if.

The method for adding the magenta coupler of the present invention into a photosensitive material is similar to the method for other couplers described below, but the amount of the high boiling point organic solvent used as a dispersion solvent to the magenta coupler is O to 4.0 as a weight ratio. Yes, preferably O~2.
0, preferably 0°1 to 1.5, more preferably 0.3 to 1.0.

The light-sensitive material of the present invention only needs to have at least one silver halide emulsion layer of a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer on the support. There are no particular limitations on the number and order of layers and non-photosensitive layers. A typical example is a silver halide photographic light-sensitive material having on a support at least one photosensitive layer consisting of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different photosensitivity. The photosensitive layer is a unit photosensitive layer that is sensitive to blue light, green light, or red light, and in a multilayer silver halide color photographic light-sensitive material, generally the unit photosensitive layer is A red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer are arranged in this order from the support side. However, depending on the purpose, the above-mentioned installation order may be reversed, or the installation order may be such that different photosensitive layers are sandwiched between the same color-sensitive layer.

Non-photosensitive layers such as various intermediate layers may be provided between the above-mentioned silver halide photosensitive layers and between the uppermost layer and the lowermost layer.

The intermediate layer includes JP-A Nos. 61-43748 and 59-1.
No. 13438, No. 59-113440, No. 61-20
Coupler, DIR compound, etc. as described in No. 037 and No. 61-20038 may be included,
It may also contain a commonly used color mixing inhibitor.

A plurality of silver halide emulsion layers constituting each unit photosensitive layer are composed of a high-speed emulsion layer and a low-speed emulsion layer, as described in West German Patent No. 1.121.470 or British Patent No. 923.045. A two-layer structure can be preferably used0
Usually, it is preferable to arrange the layers so that the photosensitivity decreases toward the support, and a non-photosensitive layer may be provided between each halogen emulsion layer.
No. 12751, No. 62-200350, No. 62-20
As described in No. 6541, No. 62-206543, etc., a low-sensitivity emulsion layer may be provided on the side far from the support, and a high-sensitivity emulsion layer may be provided on the side close to the support.

As a specific example, from the side farthest from the support: low sensitivity blue sensitive layer (BL) / high sensitivity blue sensitive layer (BH) / high sensitivity green sensitive layer (GH) / low sensitivity green sensitive layer (GL) /High-sensitivity red-sensitive layer (RH) /Low-sensitivity red-sensitive layer (1?L
), or BH/RL/GL/GH/RH/RL, or 811/BL/Gll/GL/l? L/R1
It can be placed in the first ode of A.

Further, as described in Japanese Patent Publication No. 55-34932, from the side farthest from the support, the blue-sensitive layer/Gll/
They can also be arranged in the order of R11/GL/RL. Furthermore, as described in JP-A Nos. 56-25738 and 62-63936, the blue-sensitive layer/GL/RL/Gll/R1 (blue-sensitive layer/GL/RL/Gll/R1) may be arranged in this order from the farthest side from the support. can.

In addition, as described in Japanese Patent Publication No. 49-15495, the upper layer is a silver halide emulsion layer with the highest sensitivity, the middle layer is a silver halide emulsion layer with lower sensitivity, and the lower layer is more sensitive than the middle layer. An example is an arrangement consisting of three layers with different photosensitivity, in which a silver halide emulsion layer with a low density is disposed and the photosensitivity gradually decreases toward the support. Even when it is composed of three layers with different photosensitivity, as described in JP-A No. 59-202464,
In the same color-sensitive layer, medium-sensitivity emulsion layer/high-sensitivity emulsion layer/low-sensitivity emulsion layer may be arranged in this order from the side remote from the support.

In addition, high-sensitivity emulsion layer / low-sensitivity emulsion layer / medium-sensitivity emulsion layer,
Alternatively, they may be arranged in the following order: low-speed emulsion layer/medium-speed emulsion N/high-speed emulsion layer.

Furthermore, even in the case of four or more layers, the arrangement may be changed as described above.

To improve color reproduction, U.S. Patent No. 4,663゜2
No. 71, No. 4,705.744, No. 4,707,
No. 436, JP-A-62-160448, JP-A No. 63-89
The multilayer effect donor layer (C
L) is preferably arranged adjacent to or close to the main photosensitive layer.

As mentioned above, various layer structures and arrangements can be selected depending on the purpose of each photosensitive material.

The preferred silver halide contained in the photographic emulsion layer of the photographic light-sensitive material used in the present invention is silver iodobromide, silver iodochloride, or silver iodochlorobromide, containing about 30 mol% or less of silver iodide. . Particularly preferred is silver iodobromide or iodochlorobromide containing from about 2 mole percent to about 25 mole percent silver iodide.

Silver halide grains in photographic emulsions include those with regular crystals such as cubes, octahedrons, and tetradecahedrons, those with irregular crystal shapes such as spherical and plate shapes, and those with twin planes. may have crystal defects, or a composite form thereof.

The grain size of the silver halide may be fine grains of about 0.2 microns or less, or large grains with a projected area diameter of up to about 10 microns, and may be a polydisperse emulsion or a monodisperse emulsion.

Silver halide photographic emulsions that can be used in the present invention include, for example, Research Disclosure (RD) Nα17643
(December 1978), pp. 22-23, “1. Emulsion preparation and
Nα18716 (197
November 9), 648 pages, ``Physics and Chemistry of Photography'' by Grafkid, published by Paul Montell (P, GIafkid
es, Che＋＊ie et Ph1sique P
photographique, Paul Monte
1967), "Photographic Emulsion Chemistry" by Duffin, published by Focal Press (G, F, Duffi Photo
graphic Emulsion Cheo+1st
ry (Focal Press 1966)), by Zelikman et al.
Making and coating photo
graphic ellusion focal
Press, 1964).

U.S. Patent Nos. 3,574,628 and 3,655,39
Monodisperse emulsions such as those described in No. 4 and British Patent No. 1,413.7413 are also preferred.

Tabular grains having aspect ratios of about 5 or more can also be used in the present invention. Tabular grains are described by Gutoff, Photographic Science and Engineering.
ence and Engineering), Vol. 14, pp. 248-257 (197Q); U.S. Patent No. 4
．． No. 434,226, No. 4,414.310, No. 4,
433,048, 4,439.520, and British Patent No. 2.112.157.

The crystal structure may be --like, the inside and outside may have different halogen compositions, it may be a layered structure, or silver halides with different compositions may be joined by epitaxial bonding. It may also be bonded with a compound other than silver halide, such as silver rhodan or lead oxide. Also, mixtures of particles of various crystal forms may be used.

The silver halide emulsion used is usually one that has been subjected to physical ripening, chemical ripening, and spectral sensitization. Additives used in such processes are subject to Research Disclosure Nα1
7643 and Nα18716, and the relevant parts are summarized in the table below.

In the present invention, it is preferred to use non-photosensitive fine grain silver halide. Non-photosensitive fine grain silver halide is a fine silver halide grain that is not exposed to light during imagewise exposure to obtain a dye image and is not substantially developed during the development process. preferable.

The fine grain silver halide has a silver bromide content of 0 to 100 mol %, and may contain silver chloride and/or silver iodide as necessary. Preferably, it contains 0.5 to 10 mol% of silver iodide.

The fine grain silver halide preferably has an average grain size (average diameter equivalent to a circle of the projected area) of 0.01 to 0.5 μ-, and 0.01 to 0.5 μm.
02 to 0.2 μ- is more preferable.

Fine-grain silver halide can be prepared in the same manner as ordinary photosensitive silver halide. In this case, the surface of the silver halide grains does not need to be optically sensitized, nor is spectral sensitization necessary. However, prior to adding this to the coating solution, it is preferable to add a known stabilizer such as a triazole-based, azaindene-based, hendithiazolium-based, or mercapto-based compound or a zinc compound.

Known photographic additives that can be used in the present invention are also described in the above two Research Disclosures, and the relevant descriptions are shown in the table below.

Base plate plate detection plate RD17643 Other 1 Chemical sensitizer page 23 Page 648 right (material) 2 Sensitivity enhancer Same as above 3 Spectral sensitizer, 23
~Page 24 Page 648 Right column ~Supersensitizer
Page 649 right column 4 Brightener Page 24 5 Anti-fog agent Page 24-25 Page 649 right column ~ and stabilizer 6 Light absorber, page 25-26 Page 649 right column ~ Filter dye, page 650 left column Ultraviolet absorption Agent 7 Anti-stain agent Page 25 right WI page 650 left to right 8
Dye image stabilizer page 25 9 Hardener page 26 6'51 page left column 10
Binder page 26 Same as above 11 Plasticizer, lubricant Page 27 650, right column 12 Coating aid, pages 26-27 Page 650 right column Surfactant 13 Static Page 27 Same as above Patch agent Also, photographic performance improvement with formaldehyde gas In order to prevent deterioration, US Patent No. 4,411,987 and US Pat.
It is preferable to add to the light-sensitive material a compound that can be immobilized by reacting with formaldehyde as described in No. 435.503.

Various color couplers can be used in the present invention, specific examples of which can be found in the above-mentioned Research Disclosure (
RD) Sou 17643, described in the patent described in ■-C-G.

As a yellow coupler, for example, U.S. Patent No. 3.93
No. 3,501, No. 4,022,620, No. 4,3
No. 26,024, No. 4,401.752, No. 4,
248,961, Japanese Patent Publication No. 58-10739, British Patent No. 1,425,020, British Patent No. 1,476,760, U.S. Patent No. 3,973,968, British Patent No. 4,314,
No. 023, No. 4,511,649, European Patent No. 24
No. 9,473A, etc. are preferred.

As a magenta coupler other than the present invention, US Pat.
, 310.619, 4.351,897, European Patent No. 73,636, U.S. Patent No. 3,061,432
No., JP-A-60-35730, JP-A No. 55-118034
No. 60-185951, U.S. Patent No. 4,556.
Particularly preferred are those described in No. 630, International Publication No. WO38104795, and the like.

Cyan couplers include phenolic and naphthol couplers, and are described in U.S. Pat. No. 4,052°212.
No. 4,146,396, No. 4,228.23
No. 3, No. 4,296,200, No. 2,369,9
No. 29, No. 2,801゜171, No. 2,772,
No. 162, No. 2,895,826, No. 3.772
, No. 002, No. 3,758,308, No. 4,33
4.011, 4.327.173, West German Patent Publication Box 3.329.729, European Patent No. 121,365
No. A, No. 249453A, U.S. Patent Section 3,446,
No. 622, No. 4.333,999, No. 4,775
, No. 616, No. 4,451,559, No. 4.42
No. 7,767, No. 4,690,889, No. 4,
254.

No. 212, No. 4,296,199, JP-A-61-4
Those described in No. 2658 and the like are preferred.

Typical examples of polymerized dye-forming couplers are U.S. Pat.
No. 4.576910, British Patent No. 2.102.1
No. 37, European Patent No. 3411888, etc.

Couplers whose colored dyes have appropriate diffusivity include U.S. Patent Section 4.366,237 and British Patent No. 2,125
．． 570, European Patent No. 96.570 and German Patent Publication No. 3,234,533 are preferred.

Colored couplers for correcting unnecessary absorption of coloring dyes are available at Research Disclosure Floor 17643.
- Section G, U.S. Patent Section 4.163.670, 1983
-39413, U.S. Patent Section 4.004,929, U.S. Pat.
The one described in No. 8 is preferred. Also, U.S. Patent Sections 4 and 7
No. 74.181, couplers that compensate for unwanted absorption of chromogenic dyes by means of fluorescent dyes released upon coupling; and couplers that can react with developing agents to form dyes, as described in U.S. Patent No. 4.777.120. It is also preferred to use couplers having a dye precursor group as a leaving group.

Couplers that release photographically useful residues upon cambling can also be preferably used in the present invention. DIR couplers that release development inhibitors include the aforementioned RD 17643.
, Patents described in sections ■ to F, Japanese Patent Application Laid-Open No. 57-15194
No. 4, No. 57-154234, No. 60-184248
Preferred are those described in U.S. Pat. No. 63-37346, U.S. Pat.

Couplers that release a nucleating agent or a development accelerator imagewise during development include British Patent No. 2,097,140;
No. 2,131,188, JP 59-157638
No. 59470840 is preferred.

Other compounds that can be used in the light-sensitive material of the present invention include the competitive couplers described in U.S. Pat. , the multi-equivalent couplers described in JP-A-60-185950, etc.
DIR redox compound releasing couplers, DIR coupler releasing couplers, DI described in JP-A-6224252 etc.
R coupler releasing redox compound or DIR redonx releasing redox compound, European Patent No. 173°302
No. A, a coupler that releases a dye that becomes aftercolored after separation as described in No. 313,308A, R, D, Nα11449, No. 24241, a bleaching accelerator-releasing coupler described in JP-A-61-201247, etc., United States Patent Section 4,555.477
Ligand-releasing coupler described in JP-A-63-75
Examples include couplers that release leuco dyes as described in US Pat. No. 4,774,181 and couplers that release fluorescent dyes as described in US Pat.

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods.

Examples of high boiling point solvents used in oil-in-water dispersion methods are described in, for example, US Pat. No. 2,322,027.

The boiling point at normal pressure used in the oil-in-water dispersion method is 175°C.
Specific examples of the above high boiling point 8I solvents include phthalic acid esters (dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis(2,4-di-t-amylphenyl) phthalate, bis(2,4-di-t-amyl phenyl) isophthalate, bis(1, ethylprobyl) phthalate, etc.), esters of phosphoric acid or phosphonic acid (triphenyl phosphate, tricresyl phosphate,
2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2-ethylhexyl phenyl phosphonate, etc.)
, benzoic acid ester M (2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p-
hydroxybenzoate, etc.), amide g (N, N-
diethyldodecaneamide, N,N-diethyllaurylamide, N-tetradecylpyrrolidone, etc.), alcohols or phenols (isostearyl alcohol,
2.4-di-tert-amylphenol, etc.), aliphatic carboxylic acid esters (bis(2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate, etc.), aniline derivatives ( N,N-dibutyl 2-butoxy-5-tert-octylaniline, etc.), hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene, etc.), and the like.

Further, as the auxiliary solvent, an organic solvent having a boiling point of about 30°C or higher, preferably 50°C or higher and about 160°C or lower, can be used, and typical examples include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, and cyclohexanone. , 2-ethoxyethyl acetate, dimethylformamide, and the like.

Specific examples of latex dispersion processes, effects, and latex for impregnation include U.S. Pat. It is described in.

The color photosensitive material of the present invention contains phenethyl alcohol and JP-A-63-257747, JP-A-62-272248
1,2-benzisothiazolin-3-one, n-butyl p-hydroxybenzoate, phenol, 4-chloro-3,5 described in JP-A-1-80941
-dimethylphenol, 2-phenoxyethanol, 2
- It is preferable to add various preservatives or antifungal agents such as (4-thiazolyl)benzimidazole.

The present invention can be applied to various color photosensitive materials. Typical examples include color negative film for general use or movies, color reversal film for slides or television, color paper, color positive film, and color reversal paper.

Suitable supports that can be used in the present invention include, for example, the above-mentioned R
D, page 28 of Nil 17643, and 187 of the same
16, from the right column on page 647 to the left column on page 648.

In the photosensitive material of the present invention, the total thickness of all the hydrophilic colloid layers on the side having the emulsion layer is preferably 28 μm or less, more preferably 23 μm or less, even more preferably 18 μm or less, and 16 μm or less. Particularly preferred. The membrane swelling rate TI/l is preferably 30 seconds or less, more preferably 20 seconds or less, and the membrane thickness is controlled at 25°C and 55% relative humidity.
The membrane swelling rate is 71/□.
0, which can be measured according to techniques known in the art, e.g., 1, Green
Photographic Science and Engineering (Photogr, Sci, Enl!, etc.)
) + Vol. 19, No. 2, pages 124-129, it can be measured by using a swellometer (swelling membrane), and TI/□ is reached when treated with a color developer for 13 minutes and 15 seconds at 30°C. 90% of the maximum swelling film thickness is the saturated film thickness,
It is defined as the time required to reach the saturated film thickness of 172 mm.

The membrane swelling rate TI7□ can be adjusted by adding a hardening agent to gelatin as a binder or by changing the aging conditions after coating. Further, the swelling rate is preferably 150 to 400%. The swelling rate can be calculated from the maximum swollen film thickness under the above-mentioned conditions according to the formula: (maximum swollen film thickness - film thickness)/film thickness.

The color photographic material according to the present invention includes the above-mentioned RD,
Na 17643, pages 28-29, and Na 1B
Development processing can be carried out by the usual methods described in 651 left column to right column of 716.

The color developing solution used in the development of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. Aminophenol compounds are also useful as color developing agents, but p-phenylenediamine compounds are preferably used, representative examples of which are 3-methyl-4-amino-N, N-diethylaniline, 3-methyl -4-amino-N-ethyl-N-
β-Hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-Na-methanesulfonamidoethylaniline, 3-methyl-4-aminotoethyl-β-methoxyethylaniline and their sulfates, hydrochlorides or Examples include p-toluenesulfonate. Among these, especially 3-methyl-4-amino-N-ethyl-N
β-hydroxyethylaniline sulfate is preferred. These compounds can be used depending on the purpose! f! The above can also be used together.

Color developers include p11 buffers such as alkali metal carbonates, borates or phosphates, chloride salts, bromide salts, iodide salts, benzimidazoles, hendithiazoles or mercapto compounds. It is common to include inhibitors or anticapri agents. In addition, if necessary, hydroxylamine, diethylhydroxylamine, sulfites, hydrazines such as N,N-biscarboxymethylhydrazine, phenylsemicarbazides,
Various preservatives such as triethanolamine, catechol sulfonic acids, organic solvents such as ethylene glycol, diethylene glycol, development accelerators such as hensyl alcohol, polyethylene glycol, quaternary ammonium salts, amines, dye-forming couplers, competitors. Couplers, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, viscosity-imparting agents, various chelating agents such as aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, phosphonocarboxylic acids, etc. Ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid,
Cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilo-N,N,N~trimethylenephosphonic acid, ethylenediamine-N,N,N,N tetramethylenephosphonic acid, Representative examples include ethylenediamine di(0-hydroxyphenylacetic acid) and salts thereof.

Further, when performing reversal processing, black and white development is usually performed and then color development is performed. This black and white developer contains known black and white developing agents such as dihydroxyhenzenes such as hydroquinone, 3-birapritones such as 1-phenyl-3-pyrazolidone, or amine phenols such as N-methyl-p-aminophenol. It can be used alone or in combination.

These color developing solutions and black and white developing solutions generally have a pu of 9 to 12. The amount of replenishment of these developing solutions depends on the color photographic light-sensitive material to be processed, but is generally 32 or less per square meter of light-sensitive material, and by reducing the bromide ion concentration in the replenisher.
It can also be set to 0d or less. When reducing the amount of replenishment, it is preferable to reduce the area of contact with the air in the processing tank to prevent evaporation of the liquid and air oxidation.

The contact area between the photographic processing solution and air in the processing tank can be expressed by the aperture ratio defined below.

That is, the above aperture ratio is preferably 0.1 or less, more preferably 0.001 to 0.05. As a method for reducing the aperture ratio in this way, in addition to providing a shield such as a floating lid on the surface of the photographic processing liquid in the processing tank,
Method using a movable lid described in No. 033, JP-A-63
The slit development processing method described in Japanese Patent No. 216050 can be mentioned. Reducing the aperture ratio is important not only for both color development and black and white development processes, but also for subsequent processes,
For example, it is preferable to apply it to all steps such as bleaching, bleach-fixing, fixing, washing with water, and stabilization. Furthermore, the amount of replenishment can be reduced by using means for suppressing the accumulation of bromide ions in the developer.

The time for color development processing is usually set between 2 and 5 minutes, but the processing time can be further shortened by using a high temperature, high p)I, and a high concentration of color developing agent. .

After color development, the photographic emulsion layer is usually bleached.

The bleaching process may be performed simultaneously with the fixing process (bleach-fixing process), or may be performed separately. Furthermore, in order to speed up the processing, a processing method may be used in which bleaching is followed by bleach-fixing. Furthermore, treatment with two consecutive bleach-fixing baths, fixing treatment before bleach-fixing treatment, or bleaching treatment after bleach-fixing treatment can be carried out as desired depending on the purpose. Examples of bleaching agents that can be used include compounds of polyvalent metals such as iron (III), peracids, quinones, and nitro compounds. Typical bleaching agents include organic complex salts of iron (III), such as ethylenediaminetetraacetic acid, Aminopolycarboxylic acids such as diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, glycol etherdiaminetetraacetic acid, or complex salts such as citric acid, tartaric acid, malic acid, etc. can be used. . Among these, aminopolycarboxylic acid iron (I[l) complex salts, including ethylenediaminetetraacetic acid iron (I[l) complex salt and 1,3-diaminopropanetetraacetic acid iron (m) lit salt, require rapid processing and environmental pollution. Preferable from the viewpoint of prevention. In addition, iron aminopolycarboxylate (I
II) Complex salts are particularly useful both in bleach and bleach-fix solutions. These aminopolycarboxylic acid iron (I
n) The pH of the bleach or bleach-fix solution using complex salts is usually 4.
．． 0-8, but lower p for faster processing
It can also be treated with H.

A bleach accelerator may be used in the bleaching solution, bleach-fixing solution, and their prebaths, if necessary.

Specific examples of useful bleach accelerators are described in U.S. Pat. No. 3,893,858, West German Patent Section 1.
, No. 290.812, No. 2,059,988, JP-A-53-32736, No. 53-57831, No. 53-
No. 37418, No. 53-72623, No. 53-956
No. 30, No. 53-95631, No. 53-104232
No. 53424424, No. 53-141623,
Compounds having a mercapto group or disulfide group described in JP-A No. 53-28426, Research Disclosure N [No. 117129 (July 1978), etc.; Thiazolidine derivatives described in JP-A-50-140129;
Japanese Patent Publication No. 45-8506, Japanese Patent Publication No. 52-20832,
No. 53-32735, U.S. Patent No. 3,706,561
Thiourea derivatives described in West German Patent Section 1,127,7
No. 15, iodide salts described in JP-A-58-16.235;
Polyoxyethylene compounds described in No. 1973-
Polyamine compounds described in No. 8836; other JP-A-49
-40.943, 49-59,644, 53-
No. 94,927, No. 54-35,727, No. 55-2
Compounds described in No. 6,506, No. 58-163, and No. 940; bromide ions, etc. can be used. Among these, compounds having a mercapto group or a disulfide group are preferred from the viewpoint of a large promoting effect, and are particularly preferred as described in U.S. Pat. No. 3,893,858.
No., West German Patent Section No. 1.290,812, JP-A-53-9
Preference is given to the compounds described in No. 5.630. Also preferred are the compounds described in US Pat. No. 4,552,834.

These bleach accelerators may be added to the photosensitive material. These bleach accelerators are particularly effective when bleach-fixing color light-sensitive materials for photographic use.

In addition to the above-mentioned compounds, the bleaching solution and bleach-fixing solution preferably contain an organic acid for the purpose of preventing bleach staining. Particularly preferred organic acids have an acid dissociation constant (pKa) of 2.
-5, specifically acetic acid, propionic acid, etc. are preferred.

Examples of fixing agents used in fixing solutions and bleach-fixing solutions include thiosulfates, thiocyanates, 1,000-onythyl compounds, thioureas, and large amounts of iodide salts, but thiosulfates are generally used. ammonium thiosulfate is the most widely used. It is also preferable to use a combination of thiosulfate, thiocyanate, thioether compounds, thiourea, etc. As a preservative for fixing solutions and bleach-fixing solutions, sulfites, bisulfites, carbonyl bisulfite adducts, or European patented The sulfinic acid compounds described in No. 294769A are preferred. Furthermore, various aminopolycarboxylic acids and organic phosphonic acids are preferably added to the fixing solution and bleach-fixing solution for the purpose of stabilizing the solution.

The total time for the desilvering process is preferably as short as possible without causing desilvering defects.The preferred time is 1 minute to 3 minutes, more preferably 1 minute to 2 minutes. In addition, the processing temperature is 25°C to 5°C.
0°C, preferably 35°C to 45°C. In a preferred temperature range, the desilvering rate is improved and the occurrence of staining after processing is effectively prevented.

In the desilvering process, it is preferable to strengthen the stirring as much as possible.A specific method for strengthening the stirring is to impinge a jet of processing liquid on the emulsion surface of a photosensitive material as described in JP-A-62-183460. Method and JP-A-62-183
No. 461, a method of increasing the stirring effect using a rotating means, and further improving the stirring effect by moving the photosensitive material while bringing the emulsion surface into contact with a wiper blade provided in the liquid to create turbulence on the emulsion surface. Examples include a method of increasing the circulation flow rate of the entire treatment liquid. Such means for improving agitation is effective for all bleaching solutions, bleach-fixing solutions, and fixing solutions. It is believed that improved stirring speeds up the supply of bleach and fixing agent into the emulsion film, and as a result increases the desilvering rate. Further, the agitation improving means described above is more effective when a bleach accelerator is used, and can significantly increase the accelerating effect and eliminate the fixing inhibiting effect caused by the bleach accelerator.

The automatic developing machine used for the photosensitive material of the present invention is
No. 0-191257, No. 60-191258, No. 60
It is preferable to have the photosensitive material conveying means described in Japanese Patent Application No. 191259. As described in the above-mentioned Japanese Patent Application Laid-Open No. 60-191257, such a conveying means can significantly reduce the carry-over of processing liquid from the front bath to the rear bath, and is highly effective in preventing deterioration of the performance of the processing liquid. This effect is particularly effective in shortening the processing time in each step and reducing the amount of processing solution replenishment.

The silver halide color photographic light-sensitive material of the present invention is generally subjected to water washing and/or stabilization steps after desilvering treatment.

The amount of water used in the washing process depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), the application, the temperature of the washing water, the number of washing tanks (the number of stages), the replenishment method such as countercurrent flow, ) @ flow, and various other factors. It can be set over a wide range depending on the conditions. this house,
The relationship between the number of washing tanks and the amount of water in the multistage countercurrent method is J
our own of the 5ociety of
Motion Picture and Te1evi
sion Engineers Volume 64, P, 248
-253 (May 1955 issue).

According to the multi-stage countercurrent method described in the above-mentioned literature, the amount of water used for washing can be significantly reduced, but due to the increase in the residence time of water in the tank, bacteria will breed, and the generated suspended matter will adhere to the photosensitive material. In the processing of the color photosensitive material of the present invention, such problems can be solved by:
The method for reducing calcium ions and magnesium ions described in JP-A No. 62-288.838 can be used very effectively. Also, JP-A-57-8,542
Chlorinated disinfectants such as isothiazolone compounds, cyabendazole, chlorinated sodium isocyanurate, and other benzotriazoles listed in the issue, Hiroshi Horiguchi, "Chemistry of antibacterial and fungicidal agents J (1986), Sankyo Publishing, Hygiene Technical gold wire “Microbial sterilization, sterilization, and anti-mildew technology J (1982)
Industrial Technology Association, Japan Antibacterial and Mildew Society Line “Encyclopedia of Antibacterial and Antifungal Agents J (
It is also possible to use the fungicides described in (1986).

The pH of the washing water in the processing of the photosensitive material of the present invention is 4 to 4.
9, preferably 5-8. The washing water temperature and washing time can be set variously depending on the characteristics of the photosensitive material, its use, etc., but generally it is 20 seconds to 10 minutes at 15 to 45°C, preferably 30 seconds to 5 minutes at 25 to 40°C. A range is selected. Furthermore, the photosensitive material of the present invention can also be directly processed with a stabilizing solution instead of washing with water.

In such stabilization treatment, Japanese Patent Application Laid-Open No. 57-854
All known methods described in No. 3, No. 58-14834, and No. 60-220345 can be used.

Further, following the water washing treatment, a further stabilization treatment may be performed. An example of this is a stabilization bath containing a dye stabilizer and a surfactant, which is used as a final bath for color photographic materials. Examples of the dye stabilizer that can be used include aldehydes such as formalin and glutaraldehyde, N-methylol compounds, hexamethylenetetramine, and aldehyde sulfite adducts.

It is also possible to add various botanical agents and antifungal agents to this stabilizing bath.

The overflow liquid from water washing and/or replenishment of the stabilizing liquid can be reused in other processes such as the desilvering process.

When each of the above-mentioned processing liquids is concentrated by evaporation in processing using an automatic processor or the like, it is preferable to correct the concentration by adding water.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up processing. In order to incorporate the color developing agent, it is preferable to use various precursors of the color developing agent. For example, U.S. Patent No. 3,342,59
Indoaniline compound described in No. 7, No. 3,342,
No. 599, Research Disclosure 14.850
No. and Is of the same, Schiff base-type compounds described in No. 159,
Aldol compounds described in U.S. Patent No. 13,924, metal salt complexes described in U.S. Pat.
Examples include urethane compounds described in No. 135628.

The silver halide color light-sensitive material of the present invention may contain various 1-phenyl-3-
Pyrazolidones may also be incorporated.

Typical compounds are JP-A-56-64339 and JP-A No. 57-
No. 144547 and No. 58-115438.

The various processing solutions used in the present invention are used at a temperature of 10°C to 50°C. Usually, the standard temperature is 33°C to 38°C, but higher temperatures may be used to accelerate the processing and shorten the processing time. Conversely, by lowering the temperature, it is possible to improve the image quality and the stability of the processing solution.

Further, the silver halide photosensitive material of the present invention is disclosed in U.S. Patent No. 4,
No. 500,626, JP-A-60-133449, No. 5
It can also be applied to the heat-developable photosensitive materials described in No. 9-218443, No. 61-238056, European Patent No. 210,660^2, etc.

(Examples) The present invention will be explained in more detail below with reference to Examples, but the present invention is not limited thereto.

Example 1 On a subbed cellulose triacetate film support,
Sample 101, which is a multilayer color photosensitive material, was prepared by applying layers having the compositions shown below.

(Photosensitive layer composition) The numbers corresponding to each component indicate the coating amount expressed in g/rd units, and for silver halide, the coating amount is expressed in terms of silver. However, for sensitizing dyes, the coating amount is expressed in moles per mole of silver halide in the same layer.

(Sample 101) 1st layer (antihalation layer) Black colloidal silver Silver 0.1B gelatin l.40 2nd layer (intermediate layer) 2.5-di-L-pentadecylhydroquinone X-1 X-3 X-If - 1 -2 -3 B5-1 B5-2 Gelatin third layer (first red-sensitive emulsion layer) Emulsion AvA Emulsion B il Sensitizing color dye Sensitizing dye ■ Sensitizing dye ■ X-2 X-10 -1 0, 25 0, 25 6, 9X10-' 1, 8X10-' 3, lXl0-' 0.335 0, 020 0.070 -2 -3 B5-1 Gelatin 4th layer (second red-sensitive emulsion layer) Emulsion G Increase Sensitizing dye f Sensitizing dye ■ Sensitizing dye ■ 60 7 Silver 60 5, lXl0-' 1, 4X10-' 2, 3XlO-' 0.400 0.050 0.015 0.070 0.050 0.070 1, 30 vA 1.60 5.4X10-' 1 , 4XIO-'' Sensitizing dye surface E, Layer) Emulsion A Emulsion B Sensitizing dye ■ Sensitizing dye ■ Sensitizing dye ■ EX-6 EX-1 EX-7 Silver 2°4xlO-' 0,010 o, os.

O,097 0,22 0,10 1,63 0,040 020 0,80 15 0,l 5 3.0XIO-5 10XIO-' 3, 8X10-' 0, 260 0.007 0, Ol EX-8 B5 -1 B5-3 Gelatin 8th layer (second green-sensitive emulsion layer) Emulsion C Sensitizing dye ■ Sensitizing dye ■ Sensitizing dye ■ EX-6 EX-8 EX-7 B5-1 B5-3 Gelatin 9th layer (Third green-sensitive emulsion layer) Emulsion E Sensitizing dye■ Sensitizing dye■ Sensitizing dye■ Sensitizing dye■ Ginger 25 00 10 3 0° 45 2, lXl0-' 7, 0XIO-' 2, 6X10-' 0.094 0 .01B 0.009 0, 160 0.008 0, 50 1.2 3, 5xlO-' 8, 0XIO-' 3, 0XIO-' EX-6 EX-1 B5-1 B5-2 Gelatin 10th layer (yellow Filter layer) Yellow colloidal silver Silver EX-5 B5-1 Gelatin 11th layer (first blue-sensitive emulsion layer) Emulsion A Silver emulsion B Silver emulsion F Silver sensitizing dye ■ EX-9 EX-8 B5-1 Gelatin 12th Layer (second blue-sensitive emulsion layer) 0,08 0,07 0,07 3,5x+o-' 0.721 0.042 0,28 1.10 Emulsion G Silver sensitizing dye■ 2°EX-9 EX-10 B5-1 Gelatin 13th layer (third blue-sensitive emulsion N) Emulsion H Sensitizing dye V11 2°EX-9 B5-1 Gelatin 14th layer (first protective layer) Emulsion ■ Den-4 l-5 B5- 1 Gelatin 15th layer (second protection N) Fine grain silver bromide emulsion (0.07 μm) 0,45 1 0.69 Silver 0.15 Polymethyl methacrylate particles (diameter approximately 1.5 μm) 0.543-1
0.20 gelatin
1.20 In addition to the above components, a gelatin hardening agent H1 and a surfactant were added to each layer.

Sample 102 was prepared by changing the fine-grain silver bromide emulsion in the 15th layer of sample 101 to the silver chloride fine-grain emulsion of the present invention and using the same silver coating amount as sample 101.

The fine grain silver chloride emulsion of the present invention was prepared as follows.

Silver nitrate aqueous solution (A) was added to gelatin aqueous solution (A) kept at 38°C.
B) and the sodium chloride aqueous solution (C) were added by a simultaneous mixing method for 12 minutes while controlling the potential at +450 mV until the addition of the solution (B) was completed. The potential was measured using a metal silver bridge and a double junction type saturated Calomero reference electrode, and the potential was controlled by detecting the difference with respect to the set potential and automatically controlling the amount of solution (C) added.

Immediately after particle formation, compound V12 of the general formula (V) of the present invention was added in an amount of 8 x 10-' mol per 1 mol of AgNOs. After that, it was left to stand for about 10 minutes, then a formalin condensate of sodium naphthalene sulfonate was added as a precipitant, the pH was adjusted to 3.8, and desalination was performed twice, and then NaOH, gelatin, and H2O were added and dispersed. , pH6
, OpAg was adjusted to 7.2. No chemical sensitization was performed. The grain size and shape of these emulsions were then observed using an electron microscope. As a result, cubic particles of 0.07 μm were obtained.

(A) Lime-treated gelatin 10g NaC
10.2g H, 0100010 00cc(B)A 150 gH
, 300cc (C)NaCQ at O
54gH, 0300cc Samples 103 and 104 were made in the same manner as Sample 101 except that the compounds M-5 and M-26 of the present invention were used in equimolar amounts as EX6 instead of Compound EX-6 in the 7th to 9th layers of Sample 101. Ta. Furthermore, EX-6 of sample 102 was changed to M-5 and M-26 to prepare samples 105 and 106. Sample 101-1
06 was subjected to image exposure and then passed through the processing steps described below.

When passing through the processing step, the case where a newly prepared solution was used is [A], and the case where a solution that had been passed through the image-exposed sample 101 for 250 m beforehand is used (B). The image density of the processed sample was measured. The measurement results are summarized in the table below. Sensitivity is expressed as an increase or decrease in the sensitivity of treatment (B) with respect to treatment (A). For example, -0,301 means the sensitivity is 1/2.
Hail for being so desensitized. The degree of color mixing was determined by measuring the yellow density at an exposure amount that gave a magenta density of 1.5 when exposed to green light and passing through Process A, and was calculated as an increase or decrease in density with respect to the yellow density of sample 1O1. The larger the negative value, the more improved the color mixture is.

X 1 Ct tl s X H (i) C,ll-0CNI-1 1 X X X 0■ X X X CH.

X 1 C,1( 3(b) CH1 EX-10 EX ■ Sensitizing dye f Sensitizing dye ■ Sensitizing dye ■ H H3 (t) CJq 0 ■ (t) CJq -3 H -4 x : y=70 : 30 (wt%) V-5 B5-1 Tricresyl phosphate B5-2 Di-n-butyl phthalate BS-3 Sensitizing dye ■ Enhancing dye ■ Sensitizing dye ■ Table - Processing steps * Replenishment amount: 35 mm width Unit per meter length of photosensitive material (
Color developer) Diethylenetriaminepentaacetic acid mother liquor axis) Replenisher (g) Sensitizing dye■ CHz=CI-3(h-CHz-CON)I-CHzC
H2, C11-3o□-CHz-CONH-CHz Sodium sulfite Potassium carbonate Potassium bromide Potassium iodide Hydroxylamine sulfate 4-[N-Ethyl-N β-hydroxyethylamino]-2- Add methylaniline sulfate water H (Bleach solution) Ferric ammonium ethylene diamine tetranodate dihydrate (EDTA 1.3-diaminopropane tetranode ferric ammonium a4.0 30.0 1.3 1.2■ 2.0 4.7 1.0N 10.00 5.0 37.0 0.5 ■, 01 10.05 Mother liquor (g) Replenisher (g) 100 150 Fe) 3 Ammonium salt 1.3-Diaminopropanetetraacetic acid Ammonium bromide Acetate Ammonium nitrate Add water and adjust pH with acetic acid and ammonia (fixing solution) Ethylenediamine tetranodic acid disodium salt Sodium bisulfite Sodium ammonium thiosulfate aqueous solution (700 g/l) Add rhodan ammonium water and adjust acetic acid and ammonia to 3.0 5 00 0 1.0ffi pn 4.3 Mother liquor (g) 0.5 10.0 8.0 170.0d 80.0 1 ρ■6.5 4.0 20 40 0 1.01 pn 4.0 Replenisher (g) 0.7 12.0 10.0 200, f) d In addition (stabilizing solution) Common formalin (37%) for mother solution and replenisher 5-chloro-2-methyl 4-isothiazolin-3-one 2-methyl-4- Inthiazolin 3-one surfactant (C,, H 7.0 120.0 N pH 6.7 From the above results, it was found that the combination of the present invention has a remarkable effect in suppressing sensitivity fluctuations during processing and improving color mixture compared to other combinations.

Example 2 M-6, M-9, M-18, M24, M-27, M instead of coupler M-5 of the present invention in sample 105 of Example 1
-36, M-39, and M-47 were prepared using equimolar moles of M-5 and treated in the same manner as in Example 1, and the same results as in Example 1 were obtained.

Example 3 Using a silver halide color photographic light-sensitive material having the structure described below, the same operations and treatments as in Example 1 were carried out.
Almost the same results as in Example 1 were obtained.

on a subbed cellulose triacetate film support.
Sample 201, which is a multilayer color photosensitive material consisting of each layer having the composition shown below, was prepared.

(Composition of photosensitive layer) The coating amount is the amount expressed in g/rd of silver for silver halide and colloidal silver, and the amount expressed in g/rrl for coupler additives and gelatin.
Regarding the sensitizing dye, the number of moles is expressed per mole of silver halide in the same layer. Note that the symbols indicating additives have the meanings shown below. However, if a substance has multiple effects, one of them is listed as a representative.

U: Ultraviolet absorber, Solv: High-boiling organic solvent, ExF: Dye, ExS: Sensitizing dye, ExC: Cyan coupler, ExM: Magenta coupler ExY: Yellow coupler, Cpd: Additive 1st layer (halation Prevention layer) Black colloidal silver 0.15 gelatin 2.0E x M −
60,2 UV -10,03 UV -20,06 UV -30,07 Solv-10,3 Solv-20,08 Ex F -10,01 Ex F -20,01 Ex F -30 ,005 Cpd-60,001 2nd layer (low sensitivity red-sensitive emulsion N) Silver iodobromide emulsion (Agl 4 mol%, uniform Agl type, equivalent sphere diameter 0.4 μm, coefficient of variation of equivalent sphere diameter 30%, Platy grains, diameter/thickness ratio 3.0) Coated silver amount 0.37 Silver iodobromide emulsion (Agl 6 mol%, core shell ratio 2:
1 internal high Agl type, equivalent sphere diameter 0.45 μm, coefficient of variation of equivalent sphere diameter 23%, plate-shaped particles, diameter/thickness ratio 2.0) Coated silver amount 0.19 Gelatin 0.8E x
S -12,3X10-' E x S -21,4X10-' E x S -52,3X10-' E x S -74,2X10-' ExC-10,17 E x C-20,03 E x C- 30,009 Third layer (medium-sensitivity red-sensitive emulsion N) Silver iodobromide emulsion CAgI 6 mol%, core-shell ratio 2:l
internal high Agl type, equivalent sphere diameter 0.65 μm, coefficient of variation of equivalent sphere diameter 23%, plate-shaped particles, diameter/thickness ratio 2.0) Coated silver amount 0.65 Gelatin 1. OE x
S -12,3xlO-' Ex S-21,4XIO-'ExS-52,3X10-' Ex S-74,2X10-' Ex C-10,31 Ex C-20,01 ExC-30, 10 4th layer (high sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion (Ag 19.3 mol%, core shell ratio 3:
4:2 multi-structured particles, Agl content from inside to 24.0
．． 6 mol%, equivalent sphere diameter 0.75 μm, coefficient of variation of equivalent sphere diameter 23%, plate-like particles, diameter/thickness ratio 2.5) Coated silver amount 1.5 Gelatin 1.4E x
S -11,9X10-' ExS -21,2XIO-' E x S -51,9X10-' E x S -78,0X10-' E x C-10,08 E x C-40,09 Solv-10, 08 Solv-20,20 Cp d -74,6X10-' 5th layer (middle layer) Gelatin 0.6Cpd-1
0.1 Polyethyl acrylate Latinx 0.08Sol
v-10,08 6th layer (low-sensitivity green-sensitive opalescent layer) Silver iodobromide emulsion (Ag1 4 mol%, uniform-Agl type, equivalent sphere diameter 0.33 μm, coefficient of variation of equivalent sphere diameter 37%, plate shaped particles, diameter/thickness ratio 2.0) Coated silver amount 0.18 Gelatin 0.4E x S
-31,6X10-' Ex S -44,8xlO-'ExS-51XIO-' ExM-50,16 ExM-70,03 Ex Y -80,01 Solv-10,06 Solv-40,01 7th layer (Medium-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion (Agl 4 mol%, uniform Agl type, equivalent sphere diameter 0.55 μm, coefficient of variation of equivalent sphere diameter 15%, plate-like grains, diameter/thickness ratio 4. 0) Coated silver amount 0.27 Gelatin 0.6ExS-
32X10-'ExS-47X10-'ExS-51,4X10-' ExM-50,17 ExM-70,04 ExY-80,04 Solv-10,14 Solv-40,01 8th layer (high frequency green Silver iodobromide emulsion (Agl B, 8 mol%, silver ratio 3:4)
:2 multilayer structure particles, Agl content 24 mol from inside,
0 mol, 3 mol%, equivalent sphere diameter 0.75 μm, coefficient of variation of equivalent sphere diameter 23%, plate-like particles, diameter/thickness ratio 1.6) Coated silver amount 0.5 Gelatin 0.6E x
S -45,2X10-'ExS-51Xl0-' Ex S -80,3X10-' ExM-50,08 ExM-60,03 Ex Y -80,02 Ex C-10,01 ExC-,40, 01 Solv-10,23 Solv-20,05 Solv-40,01 Cpd-71xlO-' Cp d -80,01 9th layer (middle layer) Gelatin 0.6Cp d
-10,04 Polyethyl acrylate latex 0.05Sol
v-10,02 UV -40,03 UV -50,04 10th layer (donor layer for interlayer effect on red-sensitive layer) Silver iodobromide emulsion (Ag1 8 mol%, core shell ratio 2:1 internal height) Agl type, equivalent sphere diameter 0.65 μm, coefficient of variation of equivalent sphere diameter 25%, plate-like grains, diameter/thickness ratio 2.0) Coated silver amount 0.72 Silver iodobromide emulsion (Agl 4 mol%, uniform Agl type, equivalent sphere diameter 0.4 p m, coefficient of variation of equivalent sphere diameter 30%, plate-like particles, diameter/thickness ratio 3.0) Coated silver amount 0.21 Gelatin 1.0ExS-
36X10-' ExM-100,19 S o 1 v -10,30 Solv-60,03 11th layer (yellow filter layer) Yellow colloid 1iI0.06 Gelatin 0.8Cpd-
20,13 Solv-10,13 Cp d -10,07 Cp d -60,002 H-10,13 12th layer (low-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion (Ag 14.5 mol%, uniform Agl type, equivalent sphere diameter 0.7 μm, coefficient of variation of equivalent sphere diameter 15%, plate-like grains, diameter/thickness ratio 7.0) Coated silver amount 0.45 Silver iodobromide emulsion (Ag1 3 mol%, uniform Agl type, equivalent sphere diameter 0.3 pm, coefficient of variation of equivalent sphere diameter 30%, plate-shaped particles, diameter/thickness ratio 7.0) Coated silver amount 0.25 Gelatin 2. IExS-
69X10-' ExC-10,13 ExC-40,03 ExY-90,16 ExY-111,04 Solv-10,51 13th layer (middle layer) Gelatin 0.4ExY-
120,20 Solv-10,19 14th layer (high sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion (Ag1 10 mol%, internal high AgI type,
Equivalent sphere diameter 1.0 μm, coefficient of variation of equivalent sphere diameter 25%, multiple twinned plate-like particles, diameter/thickness ratio 2.0) Coated silver amount 0.
4 Gelatin 0.5ExS-
61XIO-' Ex Y-90,01 ExY-110,20 Ex C-10,01 Solv-10,10 15th layer (first protective layer) Fine grain silver iodobromide emulsion (Ag1 2 mol%, uniform Agl type, equivalent sphere diameter 0.07μm) Coated silver amount 0.12 Gelatin 0.7UV-4
0,11 UV-50,16 Solv-50,02 H-10,13 Cpd-50,10 Polyethyl acrylate latex 0.09 No. 16
Layer (second protective layer) Fine grain silver iodobromide emulsion (AgI 2 mol%, homogeneous -Agl
Mold, equivalent sphere diameter 0.07 pm) Coated silver amount 0.3
6 Gelatin 0.85 polymethylmethacrylate particles (diameter 1.5 μm) 0.2Cp
d -40,04 W-40゜02 ) 1-1 0.17 In addition to the above components, each layer contains an emulsion stabilizer Cp d-3 (
0.07g/rrr), surfactant W-1 (0°00
6g/a+”), W-2(0.33g)m
'') and W-3 (0.108/m'') were added as coating aids and emulsifying and dispersing agents.

In addition, in order to mainly improve anti-mildew and anti-bacterial properties, 1.
2-benzisothiazolin-3-one, 2-phenoxyethanol, and phenethyl alcohol were added.

V-1 H V-2 H V-3 0 ■ V 4 X: 7=70:30 (wt%) V-5 olv-1 tricresyl nonacid olv-2 Diptyl phthalate olv-5 trihexyl phosphate xS-1 xS-2 xS xS-4 xF-1 xF-3 xS xS-6 xS-7 CZFI, OSOρ xS 8 xC H xC-2 xM-5 xM-6 xC-3 xC H (i)CJqOCONH OCHzCHzSCIhCOzH 3LallLAI! L, r13 xM-7 l xM-10 I xY-8 ExY-9 ExY-11 pd-5 C14.

pd-6 pd pd-8 -1 CHt=CH-5ow CHz C0NHCHiC
ut-COSow CHg C0NHCOyoPd-
1 JI3 pd-2 spd-3 11 p d-4 -1 -3 Js C, +(.

-4

Claims (1)

[Scope of Claims] In a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support, a silver salt having an average grain size of less than 0.15 μm and being less soluble than silver bromide. A silver halide color photograph containing fine grain silver halide having a silver chloride content of 50 mol % or more, which has adsorbed a compound forming a compound, and containing at least one compound of the following general formula [I]. photosensitive material. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the general formula [I], R_1 represents a hydrogen atom or a substituent. Y represents a hydrogen atom or a leaving group, and particularly preferably a halogen atom or an arylthio group. Za, Zb and Zc represent methine, substituted methine, =N- or -NH-, and one of the Za-Zb bond and Zb-Zc bond is a double bond and the other is a single bond. Zb
The case where the -Zc bond is a carbon-carbon double bond includes the case where it is a part of an aromatic ring. When R_1 or Y forms a dimer or more multimer, Za, Zb or Z
When c is a substituted methine, it includes the case where the substituted methine forms a dimer or more multimer.