JPH03209242A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a sensitive material having superior color reproducibility with respect to every hue and sufficiently low min. density by holding a specified yellow coupler and a specified pyrazoloazole type magenta coupler on a substrate. CONSTITUTION:A yellow coupler represented by formula I and a pyrazoloazole type magenta coupler represented by formula II are held on a substrate. In the formula I, R1 is aryl or tert. alkyl, R2 is F, alkyl, etc., L is a divalent org. group, R3 is halogen, alkyl, etc., X is H or a group releasable by a coupling reaction with the oxidized body of an arom. prim. amine color developing agent and l is an integer of 0-4. In the formula II, R10 is H or a substituent, Y4 is H or a releasable group and each of Za-Zc is methine, substd. methine, etc. A sensitive material improving the spectral absorption characteristics of formed dyestuff and having superior color reproducibility and sufficiently low min. density is obtd.

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, the spectral absorption characteristics of the dye formed are improved, resulting in improved color reproducibility in all hues. The present invention relates to a silver halide color photographic material that is immersible and has a sufficiently low minimum density.

(Prior Art) Coloring dyes based on cyan, magenta, and yellow couplers used in conventional silver halide color photographic materials have unnecessary sub-absorption, and therefore their color reproducibility tends to be impaired. Therefore, couplers that form image dyes with low side absorption have been studied.

For example, JP-A No. 63-123047 discloses a yellow coupler that exhibits a sharp absorption subtractor of coloring dyes, has excellent coloring properties, has little fog, and has little variation in coloring properties depending on the pH of the color developer. ing.

It is also known that the coloring dye of the pyrazoloazole magenta coupler has a sharper visible absorption spectrum than that of the 5-pyrazolone magenta coupler.

A report on improving color reproducibility by combining these yellow and macenta couplers is disclosed in JP-A-63-231451; (Dmin) could not be considered to be 1 minute lower.

(Problems to be Solved by the Invention) An object of the present invention is to provide a silver halide color photographic material in which the spectral absorption characteristics of the dye formed are improved, color reproducibility is improved, and the band density is sufficiently low. It is about providing.

(Means for Solving the Problems) As a result of research, the present inventors have discovered that the following - general formula (1
) and at least one pyrazoloazole magenta coupler represented by the following general formula (M-〇). found that it can be achieved.

General formula (1) [wherein, R1 is an aryl group or a tertiary alkyl group,
, represents a fluorine atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a dialkylamino group, an alkylthio group, or an arylthio group, L represents a divalent organic group, R3 represents a halogen atom, an alkyl group, an aryl group, An alkoxy group, an aryloxy group, an arylalkyl group, an alkylaryl group, an alkoxyaryl group, an aryloxyalkyl group, an alkylaryloxy group, or an arylalkyloxy group, and X is a hydrogen atom or an aromatic primary amine color developer. l represents a group that can be separated by a coupling reaction with an oxidized form of the drug, and l represents an integer of 0 to 4, respectively. However, when l is plural, the plural L-R3s may be the same or different. ] General formula [M-■] [In the formula, R1° represents a hydrogen atom or a substituent. Y.

represents a hydrogen atom or a leaving group. Za, Zb and Zc represent methine, substituted methine, =N- or -NH-, and Za
One of the -Zb bond and the Zb-Zc bond is a double bond, and the other is a single bond.

The case where the Zb-Zc bond is a carbon-carbon double bond includes the case where it is a part of an aromatic ring. This includes the case where R1° or Y4 forms a dimer or more multimer, and when Za, Zb or Zc is a substituted methine, the case where the substituted methine forms a dimer or more multimer. ] The compound represented by general formula (1) used in the present invention will be explained in more detail.

In general formula CI), R1 preferably has 6 carbon atoms
~24 aryl groups (e.g. phenyl, p-tolyl, 0
- tolyl, 4-methquinphenyl, 2-methoxyphenyl, 4-butoxyphenyl, 4-octyloxyphenyl, 4-hexadecyloxydiphenyl, l-naphthyl) or tertiary alkyl groups having 4 to 24 carbon atoms (e.g. t-butyl, t-pentyl, t-hexyl, 1.I
, 3. 3-tetramethylbutyl, l-adamantyl, 1. 1=dimethyl-2-chloroethyl, 2-phenoxy-2-propyl, bicycloC2,2,2)octan-1-yl).

In general formula (1), R2 is preferably a fluorine atom,
Alkyl groups having 1 to 24 carbon atoms (e.g. methyl, ethyl, isopropyl, t-butyl, cyclopentyl, n-
octyl, n-hexadecyl, benzyl), C6-24 aryl groups (e.g. phenyl, p-)lyl,
0-tolyl, 4-methoxyphenyl), carbon number 1 -
24 alkoxy groups (e.g. methoxy, ethoxy, butoxy, n-octyloxy, n-tetradecyloxy,
benzyloxy, methoxyethoxy), carbon atoms 6~
24 aryloxy groups (e.g. phenoxy, p-tolyloxy, O-)lyloxy, p-methoxyphenoxy, p-dimethylaminophenoxy, m-pentadecylphenoxy), dialkylamino groups having 2 to 24 carbon atoms (e.g. dimethylamino , diethylamino, pyrrolidino, piperidino, morpholino), alkylthio groups having 1 to 24 carbon atoms (e.g. methylthio, butylthio, n-octylthio, n-hexadecylthio) or arylthio groups having 6 to 24 carbon atoms (e.g. phenylthio, 4.
-methoxyphenylthio, 4-1-butylphenylthio, 4-dodecylphenylthio).

or dimethylamino group is most preferred.

In general formula [1], L is -NHCO-NHCOCH
--NHCO(CHt);"R4 -0--N)(SO2--COO--502N-R1-(CI()-=, or -NH3O2(CHt)- in the amount R7.

[In the formula, R represents a hydrogen atom or an alkyl group, and m represents O~
Each represents an integer of 4. ] In the general formula [■], R
1 is a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an arylalkyl group, an alkylaryl group, an alkoxyaryl group, an aryloxyalkyl group, an alkylaryloxy group, or an arylalkyloxy group.

In general formula N), l is preferably an integer of 1 or 2.

In the general formula (1), X is preferably a group that can be separated (referred to as a leaving group) by a coupling reaction with an oxidized product of an aromatic primary amine color developer, and specifically, a halogen atom (fluorine, chlorine, bromine, iodine), number of carbon atoms: 1
A heterocyclic group bonded to the coupling active position with ~24 nitrogen atoms, an aryloxy group having 6 to 24 carbon atoms, an arylthio group having 6 to 24 carbon atoms (e.g., phenylthio,
p-t-butylphenylthio, p-chlorophenylthio, p-carboxyphenylthio), number of carbon atoms 1 to 24
acyloxy groups (e.g. acetoxy, benzoyloxy, dodecanoyloxy), alkylsulfonyloxy groups having 1 to 24 carbon atoms (e.g. methylsulfonyloxy, butylsulfonyloquine, dodecylsulfonyloxy), aryl having 6 to 24 carbon atoms A sulfonyloxy group (e.g. benzenesulfonyloxy, p-chlorophenylsulfonyloxy) or a heterocyclic oxy group having 1 to 24 carbon atoms (e.g. 3-pyridyloxy, -phenyl-1.2.3.4-tetrazole-5- yloxy), and more preferably a heterocyclic group or an aryloxy group bonded to the coupling active position through a nitrogen atom.

When X represents a nitrogen ring group bonded to the coupling active position with a nitrogen atom, X may contain a heteroatom selected from oxygen, sulfur, nitrogen, phosphorus, selenium, and tellurium in addition to the nitrogen atom. A 5- to 7-membered optionally substituted monocyclic or fused heterocyclic ring, examples of which include succinimide, maleimide, phthalimide, diglycolimide, virol, pyrazole, imidazole,
■.

2.4-triazole, tetrazole, indole, indazole, benzimidazole, benzotriazole, imidazolidine-2,4-dione, oxazolidine-
2,4-dione, thiazolidine 2,4-dione, imidazolidin-2-one, oxazolin-2-one, thiazolin-2-one, benzimidacillin-2-one, benzoxazolin-2-one, benzothiazoline -2-one, 2-virolin-5-one, 2-imidacillin-5-one, indoline-2,3-dione, 2,6-cyoxypurine, parabanic acid, l, 2. Examples include 4-triacyridine-3,5-dione, 2-pyridone, 4-pyridone, 2-pyrimidone, 6-pyridazone, and 2-pyrazone, and these heterocyclic groups may be substituted. Examples of substituents include hydroxyl group, carboxyl group, sulfo group, amine group (e.g. amino, N-methylamino, N, N-
dimethylamino, N,N-diethylamino, anilino,
pyrrolidino, piperidino, morpholino), as well as the above R
There is a substituent mentioned as an example of No. 1.

When X represents an aryloxy group, X has 6 carbon atoms
-24 aryloxy groups, and when X is a heterocyclic group, it may be substituted with a group selected from the above-mentioned substituent groups. Substituents include carboxyl group, sulfo group,
Preferred are a cyano group, a nitro group, an alkoxycarbonyl group, a halogen atom, a carbonamide group, a sulfonamide group, a carbamoyl group, a sulfamoyl group, an alkyl group, an alkylsulfonyl group, an arylsulfonyl group, or an acyl group.

Next, examples of particularly preferably used substituents in the present invention will be described for each of the above-mentioned substituents R, R, LR, and X.

In general formula [I), R5 is particularly preferably a 2 or 4-alkoxyaryl group (e.g. 4-methoxyphenyl, 4-butoxyphenyl, 2-methoxyphenyl)
or t-butyl group, most preferably t-butyl group.

In general formula [1), R2 is particularly preferably a methyl group, ethyl group, alkoxy group, aryloxy group or dialkylamine group, most preferably a methyl group, ethyl group, alkoxy group, aryloxy group or dimethylamino group. .

In general formula [I], L is -NHCO -NHCOCH- -NHCO(CH,)';, 4 -O--NHSO, --COO--8o□N-4 -(CH)-1;, or - NH3O2 (on the CHt floor).

[In the formula, R4 is a hydrogen atom or an alkyl group, m is O~
Each represents an integer of 4. ] In general formula 1), R
1 is a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an arylalkyl group, an alkylaryl group, an alkoxyaryl group, an aryloxyalkyl group, an alkylaryloxy group, or an arylalkyloxy group.

In the general formula [I], X is particularly preferably a heterocyclic group or an aryloxy group bonded to the coupling active position through a nitrogen atom.

When X represents the above-mentioned heterocyclic group, X is preferably represented by the following general formula [ll].

General formula ([1) In general formula (■), Z represents a -0-C-R6 elementary atom, an alkyl group, an aryl group, an alkylsulfonyl group, an arylsulfonyl group, or an alkoxycarbonyl group, and Rlo and R11 are hydrogen Represents an atom, alkyl group or aryl group. R16 and R71 may be combined with each other to form a benzene ring. R1 and R,,R,
and R, , R, and R1 or R4 and R1 may be bonded to each other to form a ring (eg, cyclobutane, cyclohexane, cyclohebutane, cyclohexene, pyrrolidine, piperidine).

Among the heterocyclic groups represented by the general formula (III), a particularly preferred one is represented by Z in the general formula [II]. Here, R,, R,, R, and R are hydrogen atoms, alkyl groups,
It represents an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkylsulfonyl group, an arylsulfonyl group or an amino group, and R6 and R7 are a heterocyclic group which is water.

The total number of carbon atoms in the heterocyclic group represented by the general formula [■] is 2
~24, preferably 4-20, more preferably 5-1
It is 6. Examples of the heterocyclic group represented by general formula (II) include succinimide group, maleimide group, phthalimide group, l-methylimidazolidine-2,4-dione-3
-yl group, l-benzylimidazolidine-2,4-dione-3-yl group, 5,5-dimethyloxazolidine-2
゜4-dione-3-yl group, 5-methyl-5-propyloxazolidine-2,4-dione-3-yl group, 5,5
-dimethylthiazolidine-2,4-dione-3-yl group, 5,5-dimethylimidazolidine-2,4-dione-
3-yl group, 3-methylimidazalidinetrione-l-
yl group, 1,2゜4-triacylidin-3,5-dione-4-yl group, ■-methyl-2-phenyl group 1.2.4
-triacylidin-3,5-dione-4-yl group, 1-
Benzyl-2-phenyl-1,2,4-triacylidin-3,5-dione-4-yl group, 5-hexyloxy-
1-methylimidazolidine-2゜4-dione-3-yl group, l-benzyl-5-ethoxyimidazolidine-2,
There are 4-dione-3-yl group and 1-benzyl-5-dodecyloxyimidazolidine-2,4-dione-3-yl group.

Among the above heterocyclic groups, imidazolidine-2,4-dione-3-yl group (e.g. 1-benzyl-imidazolidine-
2,4-dione-3-yl group) is the most preferred group.

When X represents an aryloxy group, 4-carboxyphenoxy group, 4-methylsulfonylphenoxy group, 4-
(4-Benzyloxyphenylsulfonyl) phenoxy group, 4-(4-hydroxyphenylsulfonyl) phenoxy group, 2-chloro-4-(3-chloro-4-hydroxyphenylsulfonyl) phenoxy group, 4-methoxycarbonylphenoxy group, 2-chloro-4-methoxycarbonylphenoxy group, 2-acetamido-4-methoxycarbonylphenoxy group, 4-isopropoquine carbonylphenoxy group, 4-cyanophenoxy group, 2-(N
-(2-hydroxyethyl)carbamoyl]phenoxy group, 4-nitrophenoxy group, 2,5-dichlorophenoxy group, 2,3゜5-trichlorophenoxy group, 4-methoxycarbonyl-2-methoxyphenoxy group, 4-(
3-carboxypropanamido) phenoxy group is the most preferred example.

The coupler represented by the general formula [r] may form a dimer or a multimer of more than two molecules bonded to each other via a substituent R2 or a divalent or higher valence group. In this case, the number of carbon atoms in each substituent group may be outside the range specified above.

When the coupler represented by the general formula (1) forms a multimer, a typical example is a single or copolymer of an addition polymer ethylenically unsaturated compound (yellow color-forming monomer) having a yellow dye-forming coupler residue. . In this case, the multimer contains a repeating unit represented by the following general formula (III), and the multimer may contain one or more types of yellow coloring repeating units represented by the general formula [■], and the copolymer It may also be a copolymer containing one or more non-color-forming ethylene type monomers as a component.

General formula [■] In the formula, R represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a chlorine atom, A represents -CONH--COO- or a substituted or unsubstituted phenylene group, and B represents a substituted or unsubstituted phenylene group. Represents an unsubstituted alkylene group, phenylene group or aralkylene group, L is -CONH'--NHCONH-
-NHCOO-1-NHCO--0CONH--NH- -coo--oco--co--o- -3--3o, ---NH8O2- or -3o□NH
- represents. a, b, and c represent 0 or l. Q represents a yellow coupler residue in which two atoms are removed from the compound represented by the general formula (1).

As the multimer, a copolymer of a yellow color-forming heptamer represented by a coupler unit of the general formula [1] and the following non-color-forming ethylene-like monomer is preferred.

Examples of non-color-forming ethylene monomers that do not couple with the oxidation products of aromatic-grade amine developers include acrylic acid,
α-Chloroacrylic acid, α-alkylacrylic acid (e.g. methacrylic acid, etc.) Amides or esters derived from these acrylic acids (e.g. acrylamide, methacrylamide, n-butylacrylamide, t-
Butyl acrylamide, diacetone acrylamide, methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, t-butyl acrylate, 1so-butyl acrylate, 2-ethylhexyl acrylate, n-t-cutyl acrylate,
Lauryl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate and β-
hydroxymethacrylate), vinyl esters (e.g. vinyl acetate, vinyl propionate and vinyl laurate), acrylonitrile, methacrylaterile, aromatic vinyl compounds (e.g. styrene and its derivatives, e.g. vinyltoluene, divinylbenzene, vinylacetophenone and sulphostyrene) , itaconic acid,
Citraconic acid, crotonic acid, vinylidene chloride, vinyl alkyl ether (e.g. vinyl ethyl ether)
, maleic acid ester, N-vinyl-2-pyrrolidone,
Examples include N-vinylpyridine and 2- and -4-vinylpyridine.

Particularly preferred are acrylic esters, methacrylic esters, and maleic esters. Two or more kinds of the non-color-forming ethylene monomers used here can also be used together. For example, methyl acrylate and butyl acrylate, butyl acrylate and styrene, butyl methacrylate and methacrylic acid, methyl acrylate and diacetone acrylamide, etc. can be used.

As is well known in the field of polymer couplers, the general formula (III
The ethylenically unsaturated monomers to be copolymerized with the vinyl monomers corresponding to I may be used depending on the physical and/or chemical properties of the copolymer formed, such as solubility, binder of the photographic colloidal composition, etc. For example, it can be selected so that its compatibility with gelatin, its flexibility, thermal stability, etc. are favorably influenced.

The yellow polymer coupler used in the present invention is obtained by dissolving a lipophilic polymer coupler obtained by polymerizing a vinyl monomer to provide a coupler unit represented by the above general formula (III) in an organic solvent, and adding the latex solution to an aqueous gelatin solution. It may be made by emulsion dispersion in the form of , or it may be made by direct emulsion polymerization method.

U.S. Patent No. 3,45 describes a method for emulsifying and dispersing a lipophilic polymer coupler in an aqueous solution of seratin in the form of latex.
No. 1.820, and U.S. Pat. No. 4,08 for emulsion polymerization.
The methods described in No. 0,211 and No. 3,370.952 can be used.

Specific examples of LR and X of the yellow dye-forming coupler represented by the general formula [I] are shown below, but the present invention is not limited thereto.

A specific example of X is shown below.

(7) (8) (9) (lO) CH.

(II) (12) (13) A specific example of LR is shown below.

(20) (21) (31) (22) (32) (33) (23) (34) (CHri2 CHCH2C+ He-tCH.

(35) NH3Ox C+tHzs-n NH3O2C+aH3+-n (24) (25) (36) (37) (38) -CONHC,,H,.

-OC+ Hu-n (40) (41) CONH(CHri10CItH2s -NHCOC+tHts-n (43) (44) Specific examples of the yellow dye-forming coupler represented by the general formula [1] are represented by the respective substituents in the following structural formula. List each.

In the table, the numbers in parentheses represent the numbers assigned to the specific examples of X and L Rs, and the numbers in parentheses represent the substitution positions on the anilide group.

The coupler of the present invention may be used alone, or may be used in combination of two or several kinds, or may be used in combination with a known yellow dye-forming coupler.

The couplers of the present invention can be used in any layer of the light-sensitive material, but are preferably used in the light-sensitive silver halide emulsion layer or a layer adjacent thereto, most preferably in the light-sensitive silver halide emulsion layer.

The coupler of the present invention can be synthesized by conventionally known synthesis methods.
The synthesis method described in No. 23047 can be mentioned.

The amount of the coupler of the present invention used in the photosensitive material is 1X10-' mol to 10-' mol per ld, preferably 1
Xl0-'mol-5XIO-''mol, more preferably 2
X10-'mol-101mol.

Next, the compound represented by the general formula [M-■] will be explained in detail below.

General formula CM-II) In formula (M-IN), R1° represents a hydrogen atom or a substituent. Y4 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-Zc bond and Zb-Zc bond is a double bond and the other is a single bond. The case where the Zb-Zc bond is a carbon-carbon double bond includes the case where it is a part of an aromatic ring. This includes the case where a dimer or more multimer is formed with RIO or Y, and when Za, Zb or Zc is a substituted methine, the case where a dimer or more multimer is formed with the substituted methine.

The compound represented by the general formula CM-11) is known as a pyrazoloazole coupler. Among the pyrazoloazole couplers of the present invention, U.S. Patent No. 4,500,63
The imidazo[1<2-b]pyrazoles described in US Pat.

In addition, a branched alkyl group as described in JP-A-61-65245 is 2.3% of the pyrazolotriazole ring.
or a pyrazolotriazole coupler directly linked to the 6-position, or a pyrazoloazole coupler having an alkoxyphenylsulfonamide ballast group containing a sulfonamide group in the molecule as described in JP-A No. 61-65246. and European Patent (Publication) No. 226,849 and European Patent No. 2
Preference is given to using pyrazolotriazole couplers having an alkoxy group or an alkoxy group in the 6-position as described in No. 94.785.

Specific examples of the pyrazoloazole coupler represented by the general formula CM-II) are listed below, but the present invention is not limited thereto.

430 431- The color photographic light-sensitive material of the present invention is constructed by coating at least one blue-sensitive silver halide emulsion layer, one green-sensitive silver halide emulsion layer, and one red-sensitive silver halide emulsion layer on a support. I can do it. In general color photographic paper, the layers are usually coated on the support in the above order, but they may be applied in a different order. Furthermore, an infrared-sensitive silver halide emulsion layer can be used in place of at least one of the above-mentioned emulsion layers. These light-sensitive emulsion layers contain a silver halide emulsion sensitive to each wavelength range, and dyes having complementary colors to the light to which the light is sensitized, i.e., yellow of the present invention for blue, magenta of the present invention for green, and Subtractive color reproduction can be achieved by derivatizing a so-called color coupler that forms cyan for red. However, the coloring hues of the photosensitive layer and the coupler may not correspond as described above.

As the silver halide emulsion used in the present invention, one consisting of silver chlorobromide or silver chloride that does not substantially contain silver iodide can be preferably used. Here, "substantially free of silver iodide" means that the silver iodide content is 1 mol% or less, preferably 0.2 mol% or less. The halogen composition of the emulsion may be different or the same among the grains, but if an emulsion having the same halogen composition among the grains is used, it is easy to make the properties of each grain uniform. In addition, regarding the halogen composition distribution inside silver halide emulsion grains, there are grains with a so-called uniform structure in which the composition is the same in every part of the silver halide grain, and grains with a core inside the silver halide grain and a shell surrounding it. (shell) [-layer or multiple layers] Particles with a so-called layered structure in which the halogen composition is different, or
Particles with a structure that has parts with different halogen compositions in a non-layered manner inside or on the particle surface (if on the particle surface, parts with different compositions are joined on the edge, corner, or surface of the particle) are appropriately selected and used. be able to. In order to obtain high sensitivity, it is more advantageous to use one of the latter than particles with a uniform structure, and it is also preferable from the viewpoint of pressure resistance. When the silver halide grains have the above structure, the boundaries between the parts that differ in halogen composition are
The boundaries may be clear, or may be unclear due to the formation of mixed crystals due to compositional differences, or may have continuous structural changes.

Regarding the halogen composition of these silver chlorobromide emulsions, any silver bromide/silver chloride ratio can be used. Although this ratio can vary widely depending on the purpose, a silver chloride ratio of 2% or more is preferably used.

Furthermore, so-called high-silver chloride emulsions having a high silver chloride content are preferably used in light-sensitive materials suitable for rapid processing. The silver chloride content of these high silver chloride emulsions is preferably 90 mol% or more,
More preferably 95 mol% or more.

Such a high silver chloride emulsion preferably has a structure in which the localized silver bromide layer is provided inside and/or on the surface of the silver halide grains in a layered or non-layered manner as described above. The halogen composition of the localized layer has a low silver bromide content (preferably 10 mol%, more preferably more than 20 mol%). The grain may be grown on the edge, corner, or surface of the grain, but one preferred example is epitaxial growth on a part of the corner of the grain.

On the other hand, in order to minimize the decrease in sensitivity when a photosensitive material is subjected to pressure, even in high silver chloride emulsions with a silver chloride content of 90 mol% or more, grains with a uniform structure with a small distribution of halogen composition within the grains are used. It is also preferable to use

Furthermore, it is also effective to further increase the silver chloride content of the silver halide emulsion for the purpose of reducing the amount of replenishment of the development processing solution.

In such cases, the silver chloride content is 98 mol% to 10
Emulsions of almost pure silver chloride, such as 0 mol %, are also preferably used.

Average grain size of the silver halide grains contained in the silver halide emulsion used in the present invention (the grain size is defined as the diameter of a circle equivalent to the projected area of the grain, and the number average thereof is taken)
is preferably 0.1μ to 2μ.

In addition, their particle size distribution has a coefficient of variation (standard deviation of particle size distribution divided by average particle size) of 20%.
Hereinafter, a so-called monodisperse material having a content of 15% or less is preferable. At this time, in order to obtain a wide latitude, it is preferable to blend the above monodispersed emulsions in the same layer or to apply multilayer coating.

The shape of silver halide grains contained in photographic emulsions is regular (cubic, tetradecahedral, or octahedral).
lar) those with crystal shapes, those with irregular crystal shapes such as spherical, plate-like, etc.
Alternatively, a composite form of these can be used. Moreover, it may be made of a mixture of crystals having various crystal forms. In the present invention, among these particles, it is preferable to contain particles having the above-mentioned regular crystal shape in an amount of 50% or more, preferably 70% or more, and more preferably 90% or more.

In addition to these, the average aspect ratio (yen equivalent diameter/
Emulsions in which the projected area of tabular grains having a thickness of 5 or more, preferably 8 or more, exceeds 50% of the total grains can also be preferably used.

The silver chlorobromide emulsion used in the present invention is P, Glafkid
Chimie at Ph1sique Pho by es
tographique (Pau114onta1, 1967), by G. F. Duffin, Ph.
oto-graphic 8mulsion Chem
istry (Published by Focal Press 11966
Making and Coating Photo by V. L. Zelikman at al.
rapic [1muldion (Focal
Press, 1964). i.e. acid method,
Any method such as a neutral method or an ammonia method may be used, and any method such as a one-sided mixing method, a simultaneous mixing method, or a combination thereof may be used to react the soluble silver salt and the soluble halogen salt. A method in which particles are formed in an atmosphere containing excess silver ions (so-called back mixing method) can also be used. As one type of simultaneous mixing method, a method in which 9Ag in the liquid phase in which silver halide is produced can be kept constant, that is, the so-called Chondrold double jet method. According to this method, a silver halide emulsion having a regular crystal shape and a nearly uniform grain size can be obtained.

Various polyvalent metal ion impurities can be introduced into the silver halide emulsion used in the present invention during the process of emulsion grain formation or physical ripening.

Examples of compounds used include cadmium, zinc, lead,
Examples include salts of copper, thallium, etc., and salts or complex salts of group (I) elements such as iron, ruthenium, rhodium, palladium, osmium, iridium, and platinum. In particular, the above-mentioned Group Ⅰ elements can be preferably used. The amount of these compounds added varies widely depending on the purpose, but is preferably from 10@-9 to 101 moles relative to silver halide.

The silver halide emulsion used in the present invention is usually subjected to chemical sensitization and spectral sensitization.

Regarding the chemical sensitization method, sulfur sensitization typified by the addition of unstable sulfur compounds, noble metal sensitization typified by gold sensitization, or reduction sensitization can be used alone or in combination. Regarding compounds used for chemical sensitization, see the lower right column on page 18 of the specification of JP-A-62-215272.
Those described in the upper right column of page 22 are preferably used.

Spectral sensitization is carried out for the purpose of imparting spectral sensitivity in a desired light wavelength range to the emulsion of each layer in the light-sensitive material of the present invention. In the present invention, it is preferable to add a dye-spectral sensitizing dye that absorbs light in a wavelength range corresponding to the desired spectral sensitivity. Spectral sensitizing dyes used at this time include, for example, 1 et
erocyclic compounds-Cyani
na dies and related cottonp
aundg (John Wiley & 5ons l
"New York, London II) Publishing, 196
4) can be mentioned.

Examples of specific compounds include the above-mentioned Japanese Patent Application Laid-Open No. 62-21527.
Those described in the upper right column of page 22 to page 38 of the specification of Publication No. 2 are preferably used.

The silver halide emulsion used in the present invention has the following properties:
Alternatively, various compounds or their precursors can be added for the purpose of stabilizing photographic performance. As specific examples of these compounds, those described on pages 39 to 72 of the specification of JP-A-62-215272 mentioned above are preferably used.

The emulsion used in the present invention may be either a so-called surface latent image type emulsion in which a latent image is mainly formed on the grain surface or a so-called internal latent image type emulsion in which a latent image is mainly formed inside the grain. Although surface latent image type emulsions are preferred.

Cyan couplers preferably used in the present invention are:
It is represented by the general formula (C-1) or (C-■).

General formula (C-1) 1 General formula (C-11) In general formula (C-1) and (C-fr), R,,
R and R1 represent a substituted or unsubstituted aliphatic, aromatic or heterocyclic group;

and R8 represents a hydrogen atom, a halogen atom, an aliphatic group, an aromatic group, or an acylamino group, and R1 may represent a group of nonmetallic atoms forming a nitrogen-containing 5- or 6-membered ring together with R2. Y, Y2 represents a hydrogen atom or a group that can be separated during a coupling reaction with an oxidized form of a developing agent.

n represents 0 or l.

R1 in general formula (C-II) is preferably an aliphatic group, such as methyl group, ethyl group, propyl group, butyl group, pentadecyl group, tert-butyl group, cyclohexyl group, cyclohexylmethyl group, phenyl group. Examples include thiomethyl group, dodecyloxyphenylthiomethyl group, butanamidomethyl group, and methoxymethyl group.

Preferred examples of the cyan coupler represented by the general formula (C-1) or (C-11) are as follows.

In the general formula (C1), R1 is preferably an aryl group or a heterocyclic group, such as a halogen developable group, an alkyl group, an alkoxy group, an aryloxy group, an acylamino group, an acyl group, a carbamoyl group, a sulfonamide group, a sulfamoyl group,
Sulfonyl group, sulfamide group, oxycarbonyl group,
More preferably, it is an aryl group substituted with a cyano group.

When R2 and R2 do not form a ring in general formula (C-1), R2 is preferably a substituted or unsubstituted alkyl group or aryl group, particularly preferably a substituted aryloxy-substituted alkyl group, and R1 is Preferably it is a hydrogen atom.

In general formula (C-II), R4 is preferably a substituted or unsubstituted alkyl group or aryl group, and particularly preferably a substituted aryloxy-substituted alkyl group.

In general formula (C-11), R6 preferably has 2 to 2 carbon atoms.
It is a methyl group having 15 alkyl groups and a substituent having 1 or more carbon atoms, and the substituent is preferably an arylthio group, an alkylthio group, an acylamino group, an aryloxy group, or an alkyloxy group.

In general formula (C-II), R5 is more preferably an alkyl group having 2 to 15 carbon atoms, particularly preferably an alkyl group having 2 to 4 carbon atoms.

In the general formula (C-If), preferred R2 is a hydrogen atom,
A halogen atom, with chlorine and fluorine atoms being particularly preferred. Preferred Y and Y2 in general formulas (C-I) and (C-II) are a hydrogen atom, a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group, and a sulfonamide group, respectively.

Specific examples of couplers represented by general formulas (C-1) and (C-11) are listed below.

(C-1) (C-5) (C-7) α (C-4) (C-8) 11 (C-9) (C-10) (C-12) (C-17) (C- 18) (C-19) ■ (C-13) (C-14) (C-15) (C-20) (C-21) (C-22) LIL: Yellow coupler and magenta coupler of the present invention The cyan coupler represented by the above general formulas (C-r) and (C-ri) is contained in the silver halide emulsion layer constituting the photosensitive layer, usually in an amount of 0.1 to 1.0 per mole of silver halide. Mol,
It is preferably contained in an amount of 0.1 to 0.5 mol.

In the present invention, various known techniques can be applied to add the coupler to the photosensitive layer. Usually, it can be added by the oil-in-water dispersion method known as the oil protection method, and after being dissolved in a solvent, it is emulsified and dispersed in an aqueous gelatin solution containing a surfactant. Alternatively, water or an aqueous gelatin solution may be added to a coupler solution containing a surfactant to form an oil-in-water droplet dispersion with phase inversion.

Alkali-soluble couplers can also be dispersed by the so-called Fischer dispersion method. From the coupler dispersion,
The low-boiling organic solvent may be removed by distillation, noodle washing, ultrafiltration, or the like, and then mixed with the photographic emulsion.

As a dispersion medium for such a coupler, the dielectric constant (25℃)
It is preferable to use a high-boiling organic solvent and/or a water-insoluble polymer compound having a refractive index (25° C.) of 2 to 20 and a refractive index (25° C.) of 1.5 to 1.7.

As the high boiling point organic solvent, preferably the following general formula (A) ~
A high boiling point organic solvent represented by (E) is used.

General formula (A) Stomach.

electric Stomach, -〇-F=0 mouth W.

General formula (B) a, -COlow 1 General formula (E) w, -o-at (wherein, 'b' and 'b' are substituted or unsubstituted alkyl groups, cycloalkyl groups, alkenyl groups, respectively) ,
Represents an aryl group or a heterocyclic group, w4 is wl, OL
or S-W, where n is an integer from 1 to 5, and when n is 2 or more, W may be the same or different from each other, and in the general formula (E), stomach and stomach, may form a fused ring).

The high boiling point organic solvent used in the present invention has a melting point of 100°C or less and a boiling point of 140°C, even if other than those of general formula (A) or E).
Any of the above water-immiscible compounds can be used as long as they are good solvents for couplers. The melting point of the high boiling point organic solvent is preferably 8
The temperature is below 0°C. The boiling point of the high boiling point organic solvent is preferably 160°C or higher, more preferably 170°C or higher.

For details on these high boiling point organic solvents, please refer to JP-A-62
-215272 Publication Specification, page 137, lower right column ~ 14
It is written in the upper right column of page 4.

These couplers can also be synthesized with rhodapul latex polymers (
For example, it can be emulsified and dispersed in an aqueous hydrophilic colloid solution by impregnating it with a water-insoluble but organic solvent-soluble polymer.

Homopolymers or copolymers described on pages 12 to 30 of International Publication No. WO 88100723 are preferably used, and acrylamide polymers are particularly preferred from the viewpoint of color image stabilization.

The light-sensitive material produced using the present invention may contain a hydroquinone derivative, an aminophenol derivative, a gallic acid derivative, an ascorbic acid derivative, etc. as a color antifoggant.

Various anti-fading agents can be used in the photosensitive material of the present invention. That is, hydroquinones, 6
-Hydroxychromans, 5-hydroxycoumarans,
Spirochromans, p-alkoxyphenols, hindered phenols centered on bisphenols, gallic acid derivatives, methylenedioxybenzenes, aminophenols, hindered amines, and silylation and alkylation of the phenolic hydroxyl groups of these compounds. Typical examples include ether or ester derivatives. Further, metal complexes such as (bissalicylaldoximado)nickel complex and (bis-N,N-dialkyldithiocarbamado)nickel complex can also be used.

Specific examples of organic antifade agents are described in the following patent specifications:

Hydroquinones are U.S. Patent No. 2.360.290,
Same No. 2.418.613, Same No. 2.700゜453, Same No. 2,701, 197, Same No. 2.728.659
No. 2.732.300, No. 2.735.76
No. 5, No. 3.982.944, No. 4.430, 4
25, British Patent No. 1.363.921, U.S. Pat. No. 2,710.801, U.S. Patent No. 2.816.028, etc. U.S. Patent No. 3.432.30
No. 0, No. 3.573.050, No. 3.574.6
No. 27, No. 3.698°909, No. 3.764.
No. 337, JP-A-52-152225, etc., and spiroindanes are described in U.S. Pat. No. 4.360.589, p-
Alkoxyphenols are covered by U.S. Patent No. 2.735.76.
No. 5, British Patent No. 2.066, 975, Japanese Unexamined Patent Publication No. 1983-
No. 10539, Japanese Patent Publication No. 57-19765, etc., and hindered phenols are described in U.S. Patent No. 3. TOo, 45
No. 5, JP-A No. 52-72224, U.S. Patent No. 4.228
．． Gallic acid derivatives, methylenedioxybenzenes, and aminophenols are disclosed in U.S. Patent No. 3.457.079, U.S. Pat. No. 21144, etc., and hindered amines are disclosed in U.S. Patent No. 3.336.13.
No. 5, No. 4.268.593, British Patent No. 1.32
No. 6.889, No. 1.354.313, No. 1, 4
No. 10.846, JP 51-1420, JP 58
-114036, 59-53846, 59
-78344 etc., metal complexes are disclosed in U.S. Patent No. 4.05.
0.938, British Patent No. 4,241°155, British Patent No. 2.027.731(^), etc., respectively. The purpose of these compounds can be achieved by co-emulsifying them with a coupler and adding them to the photosensitive layer, usually in an amount of 5 to 100% by weight based on the corresponding color coupler. In order to prevent the cyan dye image from deteriorating due to heat and especially light, it is more effective to introduce an ultraviolet absorber into the cyan coloring layer and the layers on both sides adjacent to it.

As ultraviolet absorbers, benzotriazole compounds substituted with aryl groups (for example, U.S. Pat. No. 3,533.7
94), 4-thiazolidone compounds (e.g., U.S. Pat. No. 3.314.794, U.S. Pat. No. 3.352;
681), benzophenone compounds (e.g., those described in JP-A No. 46-2784), cinnamic acid ester compounds (e.g., those described in U.S. Pat. ), butadiene compounds (as described in U.S. Pat. No. 4,045,229), or benzoxidole compounds (e.g., U.S. Pat. 271.307) can be used. An ultraviolet absorbing coupler (for example, an α-naphthol cyan dye-forming coupler) or an ultraviolet absorbing polymer may be used. These ultraviolet absorbers may be mordanted in specific layers.

Among these, benzotriazole compounds substituted with the aforementioned aryl group are preferred.

In addition to the above-mentioned couplers, it is particularly preferable to use the following compounds. Particularly preferred is the combination with a pyrazoloazole coupler.

That is, a compound (F) that chemically bonds with the aromatic amine developing agent remaining after color development processing to produce a chemically inert and substantially colorless compound and/or an aroma remaining after color development processing. For example, in storage after processing, the compound (G) that chemically bonds with the oxidized form of a group amine color developing agent to produce a chemically inert and substantially colorless compound may be used simultaneously or singly. This is preferable in order to prevent staining and other side effects caused by the formation of coloring dyes due to the reaction between the color developing agent or its oxidized product remaining in the film and the coupler.

A preferred compound (F) has a second-order reaction rate constant with p-anisidine (in trioctyl phosphate at 80°C) of 1. Oj! /mol ・sec ~l
It is a compound that reacts in the range of xlo-'l/mol-sec.

Incidentally, the second-order reaction rate constant can be measured by the method described in JP-A-63-158545.

When k is larger than this range, the compound itself becomes unstable and may react with gelatin or water and decompose. On the other hand, if k is smaller than this range, the reaction with the remaining aromatic amine developing agent will be slow, and as a result, side effects of the remaining aromatic amine developing agent may not be prevented.

A more preferable compound (F) can be represented by the following general formula (FI) or (FII).

General formula (FI) R1-(^), -X General formula (FII) R, -C=Y In the formula, R1 and R2 each represent an aliphatic group, an aromatic group, or a heterocyclic group. n represents 1 or 0.

A represents a group that reacts with the aromatic amine developer to form a chemical bond, and X represents a group that reacts with the aromatic amine developer and leaves. B represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, or a sulfonyl group,
Y represents a group that promotes addition of an aromatic amine developing agent to the compound of general formula (FII). Here R3
and XSY and R or B may be combined with each other to form a cyclic structure.

Among the methods of chemically bonding with the residual aromatic amine developing agent, the typical ones are substitution reaction and addition reaction.

For specific examples of compounds represented by general formulas (Fl) and (FII), see JP-A-63-158545 and JP-A-62-
283338, European Patent Publication No. 298321, European Patent Publication No. 27
Those described in specifications such as No. 7589 are preferred.

On the other hand, a more preferable compound (G) that chemically bonds with the oxidized aromatic amine developing agent remaining after color development processing to produce a chemically inert and colorless compound is the following general formula (GI ).

General formula (GI) -Z In the formula, R represents an aliphatic group, an aromatic group or a heterocyclic group. Z represents a nucleophilic group or a group that decomposes in the photosensitive material to release a nucleophilic group. In the compound represented by the general formula (CI), Z is Pearson's nucleophilic property "CI (, 1 value (R, G, Pearson, at at, J,
^m.

Chem, Sac, 90.319 (196B)
) is preferably 5 or more, or a group derived therefrom.

For specific examples of compounds represented by the general formula (Gl), see European Patent Publication No. 255722, Japanese Patent Application Laid-Open No. 1430-1980
No. 48, No. 62-229145, patent application No. 63-136
No. 724, No. 62-214681, European Patent Publication 29
Those described in No. 8321, No. 277589, etc. are preferred.

Further, details of the combination of the above-mentioned compound (G) and compound (F) are described in European Patent Publication No. 277589.

The photosensitive material produced using the present invention contains a water-soluble dye or a dye that becomes water-soluble through photographic processing as a filter dye in the hydrophilic colloid layer or for various purposes such as preventing irradiation or halation. You can leave it there. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Among them, oxonol dyes, hemioxonol dyes and merocyanine dyes are useful.

As the binder or protective colloid that can be used in the emulsion layer of the light-sensitive material of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can be used alone or together with gelatin.

In the present invention, the gelatin may be either lime-treated or acid-treated. The details of the method for producing gelatin are described in Arthur Vuis' book, Macromolecule Chemistry: Gelatin (Academic Press, published in 1964).

As the support used in the present invention, transparent films such as cellulose nitrate film and polyethylene terephthalate, which are usually used in photographic materials, and reflective supports can be used. For purposes of the present invention, the use of reflective supports is more preferred.

The "reflective support" used in the present invention is one that enhances the reflectivity and makes the dye image formed in the silver halide emulsion layer clearer. Examples include those coated with a hydrophobic resin containing a dispersed light-reflecting substance such as titanium oxide, zinc oxide, calcium carbonate, and calcium sulfate, and those using a hydrophobic resin containing a dispersed light-reflecting substance as a support. For example, baryta paper, polyethylene-coated paper, polypropylene synthetic paper, transparent supports with a reflective layer or a reflective material, such as glass plates, polyester films such as polyethylene terephthalate, cellulose triacetate or cellulose nitrate, polyamide film, polycarbonate film,
Examples include polystyrene film and vinyl chloride resin.

As other reflective supports, supports having a specular reflective or second type diffuse reflective metal surface can be used. The metal surface has a spectral reflectance of 0.5 in the visible wavelength range.
The above is preferable, and it is also preferable to roughen the metal surface or use metal powder to make it diffusely reflective. The metal may be aluminum, tin, silver, magnesium, or an alloy thereof, and the surface may be a surface of a metal plate, metal foil, or thin metal layer obtained by rolling, vapor deposition, plating, or the like.

Among these, it is preferable to obtain the metal by vapor-depositing the metal onto another substrate. Preferably, a layer of water-resistant resin, particularly thermoplastic resin, is provided on the metal surface. It is preferable to provide an antistatic layer on the side of the support of the present invention opposite to the side having the metal surface. For details of such a support, see, for example, JP-A-61-210
No. 346, No. 63-24247, No. 63-24251
No. 63-24255, etc.

These supports can be appropriately selected depending on the purpose of use.

As a light-reflecting substance, it becomes white in the presence of a surfactant!
It is preferable to thoroughly knead the i-ingredient, and it is also preferable to use pigment particles whose surfaces have been treated with a di- to tetrahydric alcohol.

The occupied area ratio (%) of white pigment fine particles per defined unit area is calculated by dividing the observed area into adjacent unit areas of 6#x6- and projecting onto that unit area. It can be determined by measuring the occupied area ratio (%) (R+) of fine particles. The coefficient of variation of the occupied area ratio (%) is the ratio s of the standard side difference S of R1 to the average value (R) of R+
/H can be obtained. The number (II) of target unit areas is preferably 6 or more. Therefore, the coefficient of variation S/π can be found as follows.

In the present invention, the coefficient of variation of the occupied area ratio (%) of the pigment fine particles is preferably 0.15 or less, particularly 0.12 or less. If it is 0.08 or less, the dispersibility of the particles can be said to be "substantially uniform."

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-phinidine diamine compounds are preferably used, representative examples of which include 3-methyl-4-amino-N, N-diethylaniline. , 3-methyl-4-amino-N-ethyl-
N-β-hydroxyethylaniline, 3-methyl-4-
Amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-
N-β-methoxyethylaniline and their sulfates,
Examples include hydrochloride or p-)luenesulfonate. Two or more of these compounds can be used in combination depending on the purpose.

The color developer may contain pl (buffers) such as alkali metal carbonates or phosphates, development inhibitors or antifoggants such as bromide salts, iodide salts, benzimidazoles, benzothiazoles or mercapto compounds, etc. It generally contains hydroxylamine, diethylhydroxylamine, sulfite, N,
Hydrazines such as N-biscarboxymethylhydrazine, various preservatives such as phenyl semicarbazides, triethanolamine, and catechol sulfonic acids, organic solvents such as ethylene glycol and diethylene glycol,
Development accelerators such as benzyl alcohol, polyethylene glycol, quaternary ammonium salts, amines, dye-forming couplers, auxiliary developing agents such as the competing coupler 1-phenyl-3-pyrazolidone, tackifying agents, aminopolycarboxylic acids, amino polyphosphonic acid, alkylphosphonic acid,
Various calcinants such as phosphonocarboxylic acids, such as ethylene diamine acetic acid, nitrilotriacetic acid,
diethylenetriaminepentaacetic acid, cyclohexanediaminehexacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilo-N,
N, N-)rimethylenephosphonic acid, ethylenediamine-N,N,N'N'-tetramethylenephosphonic acid, ethylene glycol (0-hydroxyphenylacetic acid)
and their salts are representative examples.

Further, when performing reversal processing, color development is usually performed after black and white development and reversal processing. This black and white developer contains known black and white developing agents such as dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone, or aminophenols such as N-methyl-p-aminophenol. Alternatively, they can be used in combination.

The pH of these color developing solutions and black and white developing solutions is generally 9 to 12. The amount of replenishment of these developing solutions depends on the color photographic light-sensitive material to be processed, but it is generally less than 31 per square meter F of the light-sensitive material, and by reducing the bromide ion concentration in the replenisher, 5QO
ml! You can also do the following: When reducing the amount of replenishment, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the area of contact with the air in the processing tank. 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, aperture ratio=contact area between processing liquid and air (cm')/capacity of processing liquid (cm')
) The 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 solution in the processing tank, methods using a movable lid as described in Japanese Patent Application No. 62-241342, Examples include the slit development method described in Japanese Patent No. 63-216050.

It is preferable to reduce the aperture ratio not only in both color development and black-and-white development, but also in all subsequent steps, such as bleaching, bleach-fixing, fixing, washing, 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 high temperature, high pH, and high concentration of color developing agent.

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

The bleaching process may be carried out simultaneously with the fixing process (bleach-fixing process) or separately. Furthermore, in order to speed up the processing, a processing method may be used in which bleaching is followed by bleach-fixing. Furthermore, depending on the purpose, treatment may be carried out in two consecutive bleach-fixing baths, fixing treatment before bleach-fixing treatment, or bleaching treatment after bleach-fixing treatment. As the bleaching agent, for example, a compound of a polyvalent metal such as iron (I[[) is used. Typical bleaching agents include organic complex salts of iron (I), such as aminopolymers such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, and glycol ether diaminetetraacetic acid. Carboxylic acids or complex salts of citric acid, tartaric acid, malic acid, etc. can be used. Among these, aminopolycarboxylic acid iron (■) complex salts, including ethylenecyaminetetraacetic acid iron (II[) complex salt, are preferable from the viewpoint of rapid processing and prevention of environmental pollution. Additionally, aminopolycarboxylic acid iron (DI) complexes are particularly useful in both bleach and bleach-fix solutions. The pl+ of bleaching solutions or bleach-fixing solutions using these aminopolycarboxylic acid iron (III) complex salts is usually 4.0 to 8.0, but in order to speed up the processing, processing can be performed at an even lower pH. You can also do it.

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, German Pat.
．． No. 290.812, JP-A-53-95630, Research Disclosure IT, No. 129 (197
Compounds having a mercapto group or disulfide bond as described in J.P. 1987); thiazolidine derivatives as described in JP-A-50-140129; U.S. Patent No. 3.706.5
Thiourea derivatives described in No. 61; JP-A-58-1623
Iodide salt described in No. 5; West German Patent No. 2.748.43Q
Polyoxyethylene compounds described in No. 1973-
Polyamine compounds described in No. 8836; bromide ions, etc. can be used. However, 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 US Patent No. 3. Preferred are the compounds described in No. E193.858, West German Patent No. 1.290.812, and JP-A-53-95630. Additionally, U.S. Patent No. 4.55
Also preferred are the compounds described in No. 2.834. These bleach accelerators may be added to the light-sensitive material. These bleach accelerators are particularly effective when bleach-fixing color light-sensitive materials for photography.

Examples of fixing agents include thiosulfates, thiocyanates, thioether compounds, thioureas, and large amounts of iodide salts, but thiosulfates are commonly used, with ammonium thiosulfate being the most widely used. Can be used for Preservatives for bleach-fix solutions include sulfites, bisulfites, and p-
) Sulfinic acids such as luenesulfinic acid or carbonyl bisulfite adducts are preferred.

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 (number of stages), the replenishment method such as countercurrent or forward flow, and various other conditions. Can be set over a wide range. Among these, the relationship between the number of washing tanks and the amount of water in the multistage countercurrent method is
Urnalof the 5ociety of Mo
tion Picture and Te1e-vis
ion engineers vol. 64, p. 248~
253 (May 1955 issue).

According to the multi-throw countercurrent method described in the above-mentioned document, 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 propagate and the generated suspended matter will adhere to the photosensitive material. The problem arises. In the processing of the color photosensitive material of the present invention, as a solution to such problems,
The method of reducing calcium ions and magnesium ions described in JP-A-62-288838 can be effectively used. In addition, inthiazolone compounds and thiabendazoles described in JP-A No. 57-8542,
Chlorine-based disinfectants such as chlorinated sodium isocyanurate,
Others, such as benzotriazole, Hiroshi Horiguchi, "Chemistry of antibacterial and antifungal J (1986), Sankyo Publishing, complete edition of sanitary technology, "sterilization of microorganisms, sterilization, antifungal technology J (1982), Society of Industrial Technology, Japan antibacterial and antifungal “Encyclopedia of antibacterial and antifungal agents” edited by the academic society (198
The fungicides described in 6) can also be used.

The pH of the washing water used for processing 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 20 minutes.
A range of 30 seconds to 5 minutes is selected at 5 to 40°C. Furthermore,
The light-sensitive 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 carried out, such as a stabilizing bath containing formalin and a surfactant, which is used as a final bath for color photosensitive materials for photography. .

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

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

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 compounds described in No. 7, No. 3.342.
No. 599, Research Disclosure 14.850
Schiff base-type compounds described in No. 15.159 and aldol compounds described in No. 13.924, U.S. Patent No. 3
．． Metal complex described in No. 719.492, JP-A-53-13
Examples include urethane compounds described in No. 5628.

The silver halide color light-sensitive material of the present invention may optionally contain various 1-phenyl-3
- Pyrazolidones may be incorporated. Typical compounds are JP-A-56-64339, JP-A-57-144547,
and No. 58-115438.

Various processing liquids in the present invention are used at IO'C to 50'C. Normally, a temperature of 33°C to 38°C is the standard, but higher temperatures can be used to accelerate processing and shorten processing time, or lower temperatures can be used to improve image quality and stability of the processing solution. can be achieved. Further, in order to save silver on the photosensitive material, a treatment using cobalt intensification or hydrogen peroxide intensification as described in German Patent No. 2,226,770 or US Pat. No. 3,674,499 may be carried out.

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

Example 1 Comparative multilayer color photographic paper A having the layer structure shown below was prepared on a paper support laminated on both sides with polyethylene.

The coating solution was prepared as follows.

19.1 g of yellow coupler (ExY-1), 4.4 g of color image stabilizer (Cpd-1) and color image stabilizer (Cpd)
-7) 067g, 27°2cc of ethyl acetate and solvent (
Solv-3) 8.2g was added and dissolved, and this solution was
The mixture was emulsified and dispersed in 185 cc of a 10% aqueous gelatin solution containing 8 cc of sodium dodecylbenzenesulfonate. On the other hand, silver chlorobromide emulsion (cubic, average grain size 0.88 μm
and 0.70 μm (silver molar ratio).

The coefficient of variation of particle size distribution is 0.08 and 0.08. IO1 (Each emulsion contains 0.2 mol % of silver bromide locally on the grain surface) and the following blue-sensitive sensitizing dye was added per mol of silver to 2.0 x 10-4 for large-sized emulsions, respectively. For small size emulsions, sulfur sensitization was prepared after addition of 2.5XIO-' moles. The above emulsified dispersion and this emulsion were mixed and dissolved to prepare a first coating solution having the composition shown below.

The coating solutions for the second to seventh layers were also coated with mIII in the same manner as the coating solution for the first layer. The gelatin hardening agent for each layer is 1
-oxy-3,5-dichloro-5-) riazine sodium salt was used.

The following spectral sensitizing dyes were used in each layer.

Blue sensitive emulsion layer owe SO3) 1-N(CJs) - Green sensitive emulsion layer (per mole of silver halide, 4.0X10-' moles for large size emulsions, 5.6 for small size emulsions)
XlO-'mol) and (CL)nso,e (CL).

SO, NH (C, H5).

(2.OX 10-' mol each for large size emulsions and 2.5X 10-' mol each for small size emulsions per mole of silver halide) so, e SOsH' N(C2tls) 3 (per mole of silver halide, 7.OX 10-' mole for large size emulsions and 1.0XIQ-' mole for small size emulsions) per mole of silver layered red-sensitive emulsion. F) 8.5X10-'-t-ru,?
, 7 x 1.0-' mol, 2.5 x 10-' mol were added.

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

(per mole of silver halide, 0.9X10-' mole for large emulsions and 1 mole for small emulsions)
．． For the red-sensitive emulsion layer, 2.6 x 10-3 mol of the following compound was added per mol of silver genide.

Furthermore, 1-(5-methylureidophenyl)-5-mercaptotetrazole was added to each of the blue-sensitive emulsion layer, edge-sensitive emulsion layer, and red-sensitive emulsion layer (layer structure) The composition of each layer is shown below. The number is the coating amount (g/rn')
represents. The silver halide emulsion represents the coated amount in terms of silver.

Support polyethylene laminate paper [white pigment (TiOx) and bluish dye (contains clusters in the polyethylene on the first layer side)] -th layer (blue-sensitive layer) The above-mentioned silver chlorobromide emulsion 0.30 Gelatin 1.86 Yellow Coupler (BXY) 0.82 Color image stabilizer (Cpd-1) 0.19 Solvent (
Solv-3) 0.35
Color image stabilizer (Cpd-7) 0.
06 Second layer (color mixing prevention layer) Gelatin 0°99 Color mixing prevention agent (Cpd-5) 0.08 Solvent (Solv-1) 0.
16 solvent (Solv-4)
0.08 Fifth layer (II sensitive layer) Silver chlorobromide emulsion (cubic, 1=3 mixture (hg molar ratio) of average grain size of 0.55- and 0.39- grains. The coefficient of variation of the size distribution is 0.10 and 0.08,
Each emulsion contained ^gBrO, 8 mol% locally on the grain surface) 0.12 Gelatin
1.24 magenta coupler (day x M)
0.25 color image stabilizer (Cpd-2
) 0.03 color image stabilizer (Cpd
-3) 0.15 color image stabilizer (C
pd-4) 0.02 color image stabilizer (Cpd-9) 0.02 solvent (
SoIV-2) 0.4
0 Fourth layer (ultraviolet absorption layer) Gelatin 1.58 Ultraviolet absorber (tlV-1) 0.471
Color inhibitor (Cpd-5)' 0.
05 solvent (SOIV-5)
0.24 Fifth layer (red sensitive layer) Silver chlorobromide emulsion (cubic, average grain size 0.58711
A 1:4 mixture of 1 and 0.45tmO (^
g molar ratio). The coefficient of variation of particle size distribution is 0.09 and 0.
．． 11. Each emulsion contained ^gBr0.6 mol% locally on a part of the grain surface> 0.23 gelatin
l, 34 cyan coupler (E
b+C) 0.32 color image stabilizer (
Cpd-6) 0.17 color image stabilizer (Cpd-7) Color image stabilizer (Cpcl-8) Solvent (SOIV-6) Sixth layer (ultraviolet absorption layer) Gelatin ultraviolet absorber ([IV-1) Color mixture Inhibitor (Cpd-5) Solvent (Solv-5) Seventh layer (protective layer) Gelatin polyvinyl alcohol scum (denaturation degree 17%) Liquid paraffin 0.40 0.04 0.15 0.53 0.16 0, 02 0.08 1.33 Lyle-modified copolymer 0゜17 0.03 4:4 mixture (Cpd-1) Color image stabilizer (Cpd-6) 2:4:4 mixture (weight ratio) of color image stabilizer (Cpd-7) Color image stabilizer -(CH, -CH) -- (Cpd-8) Color image stabilizer (Cpd-2> Color image stabilizer (Cpd-3) Color image stabilizer (Cpd-4) Color image stabilizer (Cpd-5) Color mixing prevention agent (Cpd-9 ) 4:2:4 mixture (weight ratio) of color image stabilizer (UV-1) ultraviolet absorber (Solv-1) solvent (Solv-5) solvent (Solv-2) solvent cooc.

(CH,).

cooc.

(Solv-6) 2:1 mixture of solvents (volume ratio) (Solv-3) Solvent (ExY 2) (Solv-4) Solvent Creation of color photographic paper B-L Yellow coupler of color photographic paper A for comparison Alternatively, photographic papers B-L were prepared in exactly the same manner as photographic paper A except that the magenta coupler was replaced with an exemplified compound. The amount of each coupler added in each of the photographic papers B-L was made equal to the amount of each coupler in each layer of the photographic paper A. Table 1 shows the composition of photographic paper B-L.

First, attach a photosensitive needle (manufactured by Fuji Photo Film Co., Ltd.,
A FWH type (light source color temperature: 3200°K) was used to provide gradation exposure of a three-color separation filter for sensitometry. The exposure at this time was 250 CMS with an exposure time of 0.1 seconds.
The exposure amount was set to .

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

Processing process ■ Dragon plate with five bottoms 9>9 each member color development 356C45 seconds 161 d l 7
1 Bleach room wear 30-35℃ 45 seconds 215 d
l 71 Rinse ■ 30-35℃ 20 seconds -101
Rinse■ 30-35℃ 20 seconds -1 (1 rinse■
30~35℃ 20 seconds 350 wd! 101 drying 7
0 to 80°C for 60 seconds *The amount of replenishment was per rrr of photosensitive material (3-tank countercurrent force type from rinsing ■ to ■). The composition of each processing solution was as follows.

Yuji Niri Eiji Tank Liquid Saratenkasui
800 d 80
0 d ethylenediamine-N,N.

N,N-tetramethylenephosphonic acid 1.5g 2.0g Potassium bromide 0.015g Triethanolamine 8.0g 12.0g Sodium chloride 1.4g Potassium carbonate
25g25gN-ethyl-N-(β-methanesulfonamidoethyl)-3-methyl-4-amine aniline sulfate 5.0g 7.0gN
, N-bis(carboxymethyl)hydrazine 5.5g 7.0g Optical brightener (WHITEX 4B.

(manufactured by Sumitomo Chemical) 1.0 2.0 Add water 10001r11000
+nA'pH (25°C) +0.05
10.45 page Huangfeng trip (tank fluid and refill fluid are the same)
water 400m
lAmmonium thiosulfate (70%) 100rr+
j! Sodium sulfite 17g Iron(I) ethylenediaminetetraacetate Ammonium 553 Disodium ethylenediaminetetraacetate 5g Ammonium bromide
Add 40g 1
000ml pH (258C) 6
．． 0 Rinse solution (tank solution and replenishment solution are the same) Ion exchange water (calcium, magnesium 3pp each)
m or less) Each sample treated as described above was measured with a Fuji photographic film (TCD type densitometer manufactured by Kikusha Co., Ltd.) to measure the reflection density, and the lowest density (D
min ) was calculated. In addition, each sample was exposed to light from a color negative photographed with fabrics of various colors, and the color reproducibility of the similarly processed samples was evaluated.

The evaluation was based on the quality of color reproduction (hue, saturation) when compared to Sample A for comparison.

As is clear from Table 1, the color photographic paper of the present invention has excellent color reproducibility in all hues and has a sufficiently low minimum density.

(Effects of the Invention) According to the present invention, a silver halide color photographic light-sensitive material can be obtained which has excellent color reproducibility in all hues and has a sufficiently low minimum density.

Claims (1)

[Scope of Claims] At least one yellow coupler represented by the following general formula (I) and at least one pyrazoloazole magenta coupler represented by the following general formula (M-II) are disposed on a support.
A silver halide color photographic material characterized by containing seeds. General formula [I] ▲Mathematical formulas, chemical formulas, tables, etc. are available▼ [In the formula, R_1 is an aryl group or a tertiary alkyl group,
R_2 is a fluorine atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a dialkylamino group, an alkylthio group, or an arylthio group, and L is -NHCO
-, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, -O-, -NHS
O_2-, -COO-, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, or ▲There are mathematical formulas, chemical formulas, tables, etc.▼. R_4
represents a hydrogen atom or an alkyl group, and m represents an integer of 0 to 4, respectively. R_3 is a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an arylalkyl group, an alkylaryl group, an alkoxyaryl group, an aryloxyalkyl group, an alkylaryloxy group, or an arylalkyloxy group. X is a hydrogen atom or a group that can be separated by a coupling reaction with an oxidized product of an aromatic primary amine color developer;
each represents an integer from 0 to 4. However, when l is plural, the plural L-R_3 may be the same or different. ] General formula [M-II] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R_1_8 represents a hydrogen atom or a substituent. Y_
4 represents a hydrogen atom or a leaving group. Za, Zb and Zc
represents methine, substituted methine, =N- or -NH-, Z
One of the a-Zb bond and the Zb-Zc bond is a double bond, and the other is a single bond. The case where the Zb-Zc bond is a carbon-carbon double bond includes the case where it is a part of an aromatic ring. R_1_8 or Y_4
When forming a dimer or more multimer, Za, Zb
Alternatively, when Zc is a substituted methine, this includes the case where the substituted methine forms a dimer or more multimer. ]