JPS62123458A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain the titled material having a less tendency for reducing a cyan coloring density even if in case of using a bleaching (fixing) solution which is easy to be fatigued and has a weak oxidizing force by incorporating a specific coupler to a red color sensitive layer having a max. sensitivity and an another red color sensitive layer respectively. CONSTITUTION:The titled material comprises >=2 layers having different kinds of the sensitivities respectively. The cyan forming coupler shown by formula I is incorporated to the red color sensitive layer having the max. sensitivity, and the cyan forming coupler shown by formula II is incorporated to the another red color sensitive layer. In the formula, R1 is an aromatic group, R2 is an aliphatic, an aromatic or a heterocyclic group, R3 is an aromatic group, X and Y are each H or a group capable of cleaving with a coupling reaction of the oxidant of an aromatic primary amine developer. Thus, the change of a hue due to the coupler shown by formula II is controlled, and a low color development is supplemented with the coupler shown by formula I respectively. Even if in case of treating the titled material with the bleaching (fixing) solution which is fatigued and has the weak oxidizing force, the titled material having the less depression of the cyan coloring density is obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of application in the industry) The present invention relates to a silver halide color photographic light-sensitive material, and more particularly to a 2-alinyl-rubamoyl/-naphthol-based cyan dye-forming coupler and a dye-forming coupler in the second position. The present invention relates to a silver halide color photographic light-sensitive material having a phenolic cyan dye-forming coupler having a ureido group and a carbonamide group at the 5-position, and having excellent processing suitability and sensitivity and image quality.

(Conventional Technique #) When a silver halide photographic material is exposed to light and then subjected to color development, an oxidized aromatic-grade amine developer and a dye-forming coupler react to form a color image. Generally, this method uses a subtractive color reproduction method, and in order to reproduce blue, green, and red, yellow is used as a complementary color.

Magenta and cyan color images are formed.

Phenol derivatives or naphthol derivatives are often used as horn pigments to form cyan images. In color photography, color-forming couplers are added to the developer solution or incorporated into the light-sensitive photographic emulsion layer or other color-aging layer, and react with the oxidized form of the color developer formed by development. This forms a non-diffusible dye.

The reaction between the coupler and the color developing agent takes place at the active site of the coupler, and the coupler having a hydrogen atom at this active site is
This is a coupler, which stoichiometrically requires 4 moles of silver halide to form 1 mole of dye.

On the other hand, those that have a group that can be separated as a divalent ion at the active site are divalent couplers, that is, couplers that chemically require only 1 mole of a halogenated plane having a development nucleus to form 1 mole of dye. Therefore, the amount of silver halide in the photosensitive layer can be reduced and the film thickness can be made thinner by adding 7J to the casoler, which makes it possible to shorten the processing time of the photosensitive material, and furthermore, the color image formed can be made thinner. Sharpness is improved.

The performance required for a coupler is that it has excellent stability, that the hue of the coloring dye is favorable for color reproduction, and that the current fl! It has a high conversion efficiency from touge to dye and a fast dye formation speed, that is, it has excellent color development, excellent processing suitability, light for color images,
It has excellent fastness against heat, humidity, etc.

Conventionally, phenolic couplers and naphthol couplers have been used as cyan couplers.

In particular, /-naphthol couplers have a long-wavelength absorption maximum (umax) of the coloring dye produced, and have low side absorption in the edge region, which is excellent for color reproduction. However, the phenolic couplers and naphthol couplers that have been widely used in the past cannot be bleached or bleached in the bleaching or bleach-fixing process of color development processing. If the fixing process is fatigued or the oxidizing power is weak, sufficient color images cannot be obtained.This phenomenon is caused by ferrous ions produced during the bleaching or bleach-fixing process. This is believed to be due to the reduced color of the cyan dye.Also, the cyan images formed by these couplers had the disadvantage of low fastness.

Among the phenolic couplers and naphthol couplers known as cyan dye-forming couplers, they have a phenylureido group at the 2-position and an acylamino group at the j-position. It has been reported in JP-A-56-63-/j that the phenolic cyan coupler has excellent fastness to heat or light of color images produced by color development compared to other cyan couplers. -2071j4t3, Li
l j 7-. 204LjIA≠, same! 7-20≠j Hiro, same 6! -332≠ and is disclosed in Ig-33260 and the like.

These couplers have a favorable color image and are fast.2.They have the advantage that there is almost no decrease in color density even when processed with a bleaching solution with weak oxidizing power or a bleaching solution that is tired. The absorption in the edge region of the dye is relatively large and at a high dye concentration, the absorption maximum (2m a x ) is at a sufficiently long wavelength, but at a low dye concentration, λ1111X shifts to the short wavelength side. Disadvantages of deteriorating color reproducibility and failure to obtain sufficiently high color development even with a 2-win coupler.
It had drawbacks.

In order to eliminate the drawbacks in hue of this coloring pigment,
9-IAtA<z has a phenylureido group at the 2nd position, j
A silver halide color photographic light-sensitive material is disclosed in which a phenolic cyan coupler and a naphthol cyan coupler, each of which has a carbonamide group at the position thereof, are used in combination. Since this method uses a naphthol-based cyan coupler in combination, it has the disadvantage that sufficient color density cannot be achieved when using a bleaching or bleach-fixing solution that is tired or has weak oxidizing power. .

(Objective of the present invention) The first object of the present invention is to provide silver halide with extremely small decrease in cyan color Ia/Je even when a bleaching or bleach-fixing solution that is tired or has weak oxidizing power is used during bleaching or bleach-fixing processing. The aim is to provide color photographic materials.

A second object of the present invention is to provide a silver halide color photographic material with high sensitivity or high image quality by using a coupler with excellent color development.

(Means for solving the problems) These objects of the present invention are to reduce the number of red-sensitive emulsion layers with different sensitivities on a support (to obtain the highest sensitivity red-sensitivity in a silver halide color photographic light-sensitive material having two layers). The following general formula (
J) at least a cyan dye-forming coupler represented by -?
The following general formula [■
1. General formula (1,) General formula [■] In the formula, RI is an aromatic compound. group, R2 is an aliphatic group, an aromatic group or a heterocyclic group, R3 is an aromatic group, X and Y are a hydrogen atom or a cup 1 of an oxidized aromatic primary amine developer.
Each represents a group that can be separated by a 1-ring reaction. However, X and Y are not photographically useful groups.

Here, the aliphatic group refers to a linear, branched or cyclic alkyl group, alkenyl group or alkynyl^(,
Either 1 replacement or no replacement may be used. The aromatic group refers to a substituted or unsubstituted aryl group, and may be a condensed ring. Heterocyclic group refers to substituted or unsubstituted,
Indicates a monocyclic or fused ring heterocyclic group.

The substituents in general formulas CI) and (II) will be described in detail below. May be replaced. There may be a plurality of substituents. Representative examples of substituents include halogen atoms, hydroxyl groups, amino groups, carboxyl groups, sulfonic acid groups, cyanide groups, aromatic groups, heterocyclic groups, carbonyl groups, sulponamide groups, carbamoyl groups, sulfuryl groups, and ureido groups. group, anlu group, syloxy group, aliphatic oxy group, aromatic oxy group, aliphatic thio group, aromatic thio group, aliphatic sulfonyl group, aromatic sulfonyl group, nulfamoylamino group, nitro group, imido group , an aliphatic IS group, an aliphatic oxycarbonyl group, and the like. When substituted with a plurality of substituents, the plurality of substituents may be bonded to each other to form a ring, and examples of Iflj include a dioxymethylene group and the like.

R2 represents an aliphatic group having 1 to 3 carbon atoms, an aromatic group having 6 to 3 carbon atoms, or a heterocyclic group having 1 to 3 carbon atoms, preferably a tertiary alkyl group having 1 to 3 carbon atoms, or Carbon number 7
~3 B is a group represented by the following general formula (1).

General formula [Kashi] In the formula, R4 and R5 may be the same or different, and are a hydrogen atom, an aliphatic group having /~2 carbon atoms, or a C6-2 aliphatic group.
R6 represents a heptavalent group, and Z represents 10-1-s-1-90- or -502-.

2 is a numerical expression of 0-1.When 2 is plural, it is plural (hard n
s may be the same or different. Preferred substituents include I'L4 and R5, which are linear chains with tQ:X number of 7 to/g.
or a branched alkyl group, R6 is a halogen atom, an aliphatic group, an aliphatic okyne group, a carphonamide group, a sulfonamide group, a carboxyl group, a sulfo group, a cyan group, a hydroxy group, a carbamoyl group, a sulfamoyl group, an aliphatic oxycarbonyl group. group and an aromatic sulfonyl group, Z can each include 10-.

Here, the number of carbon atoms in R6 is 0 to 2, and preferably / to 3.

R3 is an aryl group having 6 to 30 carbon atoms, and may be a fused ring or substituted. Typical substituents ff1J for R3 include a halogen atom, a nitro group, a cyan group,
trifluoromethyl group, hydroxy group, carboxy group,
Sulfo group, aliphatic oxycarbonyl group, acyl group, carbamoyl group, sulfamoyl group, carbonamyl group,
Sulfonamide group, aliphatic oxysulfonyl group, aliphatic oxy group, aliphatic sulfonyl group, aromatic sulfonyl group,
An aliphatic sulfinyl group, an aromatic nurfinyl group, an acyloxy-7 group, etc. can be used.

X and Yl - represents a hydrogen atom or a coupling-off group (including a leaving atom; the same applies hereinafter). Typical examples of coupling jmt degrouping include halogen atoms, sulfo groups, aliphatic oxy groups, aromatic oxy groups, heterocyclic oxy groups, aliphatic thio groups, aromatic thio groups, acyloxy groups, carbonamide groups, aliphatic Examples include a thiocarbonylamino group, an aliphatic oxycarbonyloquine group, a carbamoyloxy group, and a polycyclic group that is bonded to the coupling active position of the coupler through a nitrogen atom. The carbon numbers of X and Y are each 0 to 36
It is. , , X and Y are not photographic properties. A photographically useful group is a group that is released by a coupling reaction and exerts a post-photographic effect (for example, a 13i inhibitor, a development accelerator, a silver halide solvent, a developer, a fogging agent, a reducing agent, a coupler, an antifoggant, Aromatic azo used in so-called colored couplers that have absorption in a specific visible head by combining with bleach additives, bleach inhibitors, etc. and their precursors), photographic dyes, and coupler residues. , )f:, etc.

In the present invention, aliphatic groups include saturated/unsaturated, 11t1
It may be negative or non-negative, linear, branched, or cyclic. Typical examples include methyl group, ethyl group, butyl group, cyclohexyl group, allyl group, tert-butyl group, tert-butyl group, tert-butyl group, tert-butyl group, -amyl group, tert-hexyl group, t
ert-octyl group, adamantyl group, \endyl group,
2-ethylhegycyl group 1.2-/\xyldenyl group, propargyl group, methoxyethyl group, n-decyl group, n-
Dotenlu group, n-hexadecyl group, trifluoromethyl group, 7\pukufluoropropyl group, dodenluoginepropyl group,! .

≠-di-tert-amylphenoxyzolopyl group, 2.
4t-di-tcrt-amylphenoquine butyl group, etc. are included.

Further, the aromatic group may be substituted or unsubstituted,
Typical examples include phenyl group, tolyl 2-tetradenyloxyphenyl group, hantafluorophenyl group,
2-Chloro-yo-dodecyloquine carbonylphenyl group, l-chlorophenyl group, μm-anophenyl group, schichtroxyf x-n, - group, ≠-mel-quinphenyl group, ≠-fcrt-octylphenyl group, naphthyl group etc. should be included.

The heterocyclic group may also be substituted or unsubstituted, and typical examples include 2-pyridyl group, ≠-pyridyl group, 2-furyl group, gouchenyl group, quinolinyl group,
etc. are included.

Two preferred examples of substitution in the present invention will be explained below.

Is R1 a phenyl group, a naphthyl group, and an aliphatic oxy group or a halogen atom at the 2-position? phenyl group [e.g. 2
-butoxyphenyl group, 2-hexyloxyphenyl group, 2-dodecyloxyphenyl group,! -tetradecyloxyphenyl group 1.2-(2-hequinlutecyloxy)
phenyl group, 2-chloro-j-dodecyloxyphenyl group, etc.] are preferred.

l'L2 is preferably a tertiary alkyl group or a group represented by the general formula [厘], and specific examples include Icrt-butyl group, /17-dimethylbutyl group, /-ethyl-/-methylpropyl group, /, /-dimethyl-J-chloroethyl group, /-acmantyl group, /-(j, <z-sheet tert
-amylphenoxy)propyl group, /-(,2,4t-
di-tert-amylphenoxy)amyl group, /-(,
! , ≠-di-tcrt-amylfe/xy)hedityl group, / -(,?,≠-ctert-o'Itylfenoquine)heptyl group.

Examples include /-(,2-chloro-≠-tert-octylphenogysi)heptyl group, /-[gu(1,t-hydroxyphenylsulfonyl)phenoxy]tridecyl group, and the like.

R3 is preferably a j-cyanophenyl group, ≠-alkylsulfonylphenyl group (e.g. methanesulfonyl group, propanesulfonyl group, butanesulfonyl group, etc.), 4t-
1-I+fluoromethylphenyl group, 3-sulfonemidophenyl group (e.g., 3-mexnesulfonemidophenyl group, etc.) and halogen-substituted phenyl group (I'll t
-Fluorophenyl group, t-chlorophenyl L3. ≠−
Dichlorophenyl group 1.2. IA, j-M+chlorophenyl group, etc.).

X is preferably a hydrogen atom, a chlorine atom, an aliphatic oxy group (
Examples of 1ul are 2-hydroxyethoxy group, 2-chloroethoxy group, carboxymethyloxy group, /-nonorpoxy group, 2-methnosulfonylethoxy group, 3
-carboxyp1copyloxy group,! -Methquinethoxyruhamoylmethyloxy group, /-Calphoquinodripcyl group, J-(/-Sulfoxytrideneruthio)ethyloxy group, 1,2-Calfoxymethylthioethylloquine group, Nomethanesulfonamidoethyloxy group], aromatic oxy group [e.g. ≠-acetamidophenoquine group, 2
-acetamidophenoxy group, ≠-(3-carboquinepro-t-amito)phenoxy group, etc.] and carhamoyluo+7N ([+lI is ethyl group! lebamoyloxy group, phenylcarhamoyluoquine group, etc.].

Y is preferably a hydrogen atom, a []'r atom, and an aromatic group [e.g., q-chlorophenoxy group, ≠-methoxyphenoxy group, <z-tert-octylphenoxy group, 2-acetamidophenoxy group, p -(J-carboxypropanamide) phenoxy group, ≠-carboxyphenoxy group, ta-(4L-hydroxyphenylsulfonyl) phenoxy group, etc.).

The coupler represented by the general formula [I] has a substituent RI or
, and the coupler represented by the general formula [■] has a divalent or divalent substituent R2, R3 or Y, respectively.
It is also possible to form 1-1 or more multimers that interact with each other via groups with higher valence. In this case, the carbon number range shown in each of the above-mentioned substituents may be outside the specified range.

When the coupler represented by the general formula [I] or (It) forms a multimer, an addition-polymerizable ethylenically unsaturated monomer having a cyan dye-forming coupler residue (cyan color-forming upper layer) is used alone. Or maybe a copolymer! ! ! This is an example. In this case, the multimer contains a repeating unit of the general formula [Iv], and develops a cyan color represented by the general formula [Iv] (the repeating unit may contain up to 7 rods in one multimer,
It may be a copolymer containing seven or more non-color-forming ethylene-like monomers as a synergistic component.

General formula (+V) In the formula, R represents a hydrogen atom, an alkyl group with carbon number/~4'll4, or a chlorine atom, and A represents -C□Nfr-1-CO
O- or a substituted or silent 1 negative phenylene group, B represents a substituted or regularly substituted alkyl group, phenylene group or aralkylene group, L is -CONTI-1-
N II CON ll-1-NIICOO-1-N
II C0-1-0CONH-1-N Ll-1-CO
O-1-OCO-1-CO-1-o-1-8O2-1-
NI[represents 5O2- or -8O2Nlr-. a,
and C represents 0 or /. Q represents the general formula [I] and [I
1] shows a cyan coupler residue from which a hydrogen atom other than the hydrogen atom of the 7-position hydroxyl group has been removed.

As the multimer, a copolymer of a cyan color-forming monomer having a coupler unit of the general formula (IV) and the following non-color-forming ethylene-like heptamer is preferred.

Non-color-forming ethylene-like 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.) Esters or amides derived from these acrylic acids (e.g. acrylamide, methacrylamide, n-butylacrylamide, 1
-butyl acrylic acid, diacetone acrylamide, methyl acrylate, ethyl acrylate, n-propylacryl-1, lobutyl acrylate, i5o-butyl acrylate, 2-ethylhexyl acrylate, n- Octyl acrylate, lauryl acrylate, methyl acrylate, ethyl methacrylate, n-butyl methacrylate and β-
hydroxy methacrylate), vinyl esters (e.g. vinyl acetate, vinyl propionate and vinyl laurate), rylonitrile, methacrylonitrile
1, aromatic vinyl compounds (e.g. styrene and its derivatives, vinyl 1-cyan, divinylbenzene,
vinylacetophenone 16 and sulphostyrene), itaconic acid, citraconic acid, crotonic acid, vinylidene chloride, vinyl alkyl ethers (e.g. vinyl ethyl ether), maleic esters, N-vinyl-J-pyrrolidone, N-vinylpyridine-J and 2 − and −≠−
Examples include hinylpyrinone.

Particularly preferred are acrylic esters, methacrylic esters, and maleic esters. Two or more of the non-color-forming ethylene-like monomers used herein may 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.

Bo117 - As well known in the coupler field (the above general formula [■]
The ethylenically unsaturated monomers to be copolymerized with vinylic monomers corresponding to the corresponding vinylic monomers are determined by the physical and/or chemical properties of the copolymer formed, such as the solubility, the binder of the photographic colloidal composition, etc. It can be selected so that its compatibility with gelatin, its flexibility, thermal stability, etc. are favorably influenced.

A lipophilic polymer coupler obtained by polymerization of a vinyl monomer is dissolved in an organic solvent to give gelatin. It can be made by emulsifying and dispersing it in the form of latex in an aqueous solution (or it can be made by direct emulsification method).

U.S. Pat.
4tj/,! -20, and U.S. Pat.

The method described in No. 370, No. 52 can be used.

Next, specific examples of couplers represented by general formulas [I] and [I1] will be shown, but the couplers used in the present invention are not limited to these. In the following structural formula ( t
) C5rr,, c mark c (Cf13)2 C2
T■s, (t)C811H is 1C(CH3hC■I
2C (each representing CII3h).

Specific examples of the coupler represented by general formula (1) are shown below.

l c6■t,,.

t-t: C611+3OCTI
2C1l 20H o3 0C112COOII OCII2CII2SO2C4[3 OCI■2CTI2SC■l2CoO■I■ C121125 C+21125 CIOII21 0C02CONINC] 12CIh○CI[3 General formula [
Specific examples of couplers represented by I1] are shown below.

Cs IIu[tl (II-/
)S No(tl (I
I--2)0"5r-fa"
(II-4')Cs fl++(tl
(If -6)C5I(u(t) 0°11゛λ” (t10)NT IC
0CI I 2Cl 12 C(X)I I([1-,
2,2) C11-, 2μ] In the silver halide color photographic material of the present invention, the red-sensitive layer is composed of two or more layers, and these emulsion layers may be adjacent to each other or It may be surrounded by other photosensitive silver halide emulsion layers having different wave-receiving areas, or non-photosensitive hydrophilic colloid layers, and auxiliary layers having a specific purpose.

Further, the red-sensing layer may be composed of three layers or three or more layers.

In the present invention, the change in hue due to the color density of the color image of the cyan coupler represented by the general formula (II) is suppressed by using the cyan coupler represented by the general formula [l] in which λmax of the color image is a long wavelength. In addition, the drawback of low color development of the coupler represented by the general formula CI+) can be compensated for by using the coupler represented by the general formula [l) with high color development 1, and the fatigue or oxidation power of the cyan color image can be compensated for. The main idea is to improve the poor color development during processing with weak bleaching or bleach-fix solutions, and to obtain a photographic material f') with high sensitivity or high image quality by using a coupler that has poor color development. .

The term "tired bleaching bath or bleach-fixing bath" as used herein refers to one whose redox potential is 700 mV or less, and particularly zomv or less. It is essential to use the coupler represented by the formula ([) in the highest red sensitivity layer, and it is preferable that the coupler represented by the general formula (1) is a 2-equivalent coupler having a substituent at the active site.

In addition, in the present invention, it is possible to use a coupler represented by the general formula (1,1) and a coupler represented by the general formula [■] together in the same red-sensitive layer, but when they are used together in the highest red-sensitivity layer, For every 1 mole of the coupler represented by the general formula [I], the coupler represented by the general formula C[I] is 0. It is preferable that the amount is not more than j moles.

The cyan coupler according to the present invention is disclosed in US Pat.

Similar to the method described in No. 32.2,027, it can be added by dissolving and dispersing it in a high boiling point solvent. It can also be dissolved in alkaline water or hydrophilic organic solvents (methanol, ethanol, acetone, etc.) and added, but the general formula (
The coupler represented by 1) is preferably dispersed in a phosphoric acid ester (for example, 1-ricrenulfophosphate, etc.), and the coupler represented by the general formula
Phthalate esters (5 examples include dibutyl phthalate, etc.)
It is preferable to dissolve and disperse in. Therefore, from this point of view, it is preferable to use the coupler represented by the general formula [I] in the highest red sensitivity layer and the coupler represented by the general formula CI+) in the red sensitivity layers other than this layer.

The coupling device of the coupler of general formula [I] according to the present invention is /×
706~/X/0-1 mol/m2, preferably/
×10-5 to /×10-2 mol/m2, and the general formula (
The coating strength of coupler II) is /×10-6~/X/
0=mol/m”, preferably /X70-5~/
X/0-2 morph rn2. Also, general formula [
The molar ratio of the coupler of formula (I) to the coupler of general formula (11)') is (1)/(If)-o, o/~10, more preferably o, or-r, o. , more preferably 0.0. r~7.0.

The present invention includes U.S. Patent No. 2, ≠7 as a cyan coupler.
≠, naphthol couplers described in US Pat. No. 273, preferably US Pat.

, No. 233 and No. ψ, ! #,,! U.S. Pat. No. 2,36, 727, U.S. Pat.
It is also possible to use in combination the phenolic couplers described in 0/, No. 171, No. 2,772,162, No. 2.193;, No. 126, and the like. The coupler used in combination is preferably 015 mol or less per 1 mol of the coupler of the general formula (1) in the highest sensitivity r-, and in the red-sensitive layer other than this layer, the coupler of the general formula (n) 1 It is preferably 0.15 mol or less per mole.

The couplers represented by general formulas (1) and [■] are colored couplers for color correction (hereinafter referred to as colored couplers).
and development inhibitor-releasing couplers (hereinafter referred to as DrR couplers) are not included. This is because, in the former case, if the amount of l required to obtain the optimal masking effect is added, the desired effect of the present invention is hardly achieved, and if the amount of lubricant required to obtain the effect of the strength wood invention is added, the coloring This is because color reproducibility is adversely affected.

In the latter case, DIrt having a coupler skeleton of general formula (1)
The coupler is disclosed in U.S. Patent No. 3.227.331, US Pat. ,2
．． 27. Although it is described in No. 62 of the same G, Z≠g, and RI No. 62, etc., when these couplers are added in the amount necessary to obtain the optimum phenomenon suppressing effect, the original development Due to the use of a chromogenic pickled coupler which is the object of fJ2 of the present invention due to its suppression effect. This is because it goes against the improvement of sensitivity and image quality. Examples of using the latter coupler include JP-A-5G-1J≠gct4L example≠ and JP-A-S'
Examples include p-'yi Hiro9L1 fruit, @Siri2, etc., but the latter coupler, that is, the coupler represented by the general formula [II] of the D[t coupler] having a coupler skeleton represented by the general formula []] These ratios are extremely small, and it cannot be said that they satisfy the purpose of the present invention.

In the photographic emulsion layer of the photographic or light-sensitive material of the present invention, any of the halogenated GIJk such as silver bromide, silver iodobromide, silver iodide, silver chlorobromide, and silver chloride may be used. The preferred silver halide is silver iodobromide or silver iodochlorobromide containing less than about 30 moles of silver iodide. Particularly preferred is about! Silver iodobromide containing silver iodide from 1 molti to about 2J molti.

The seven silver halogen grains in the photographic emulsion may be so-called regular grains having a regular crystal structure such as a cube, octahedron, or dodecahedron, or may have an irregular crystal shape such as a spherical shape. It may be one with crystal defects such as twin planes or a composite form thereof.

The grain size of the silver halide may be fine grains of about 70 microns or less, large grains with a projected area diameter of up to about 70 microns, monodisperse emulsions with a narrow distribution, or polydisperse emulsions with a wide distribution.

An emulsion powder may also be used.

The silver halide photographic emulsion that can be used in the present invention can be produced by a known method, for example, as described in Research Disclosure (
r (D), Δ5/7 Otsu q3 (/ri7g February), 22
〜23 pages, °゛1. Emulsion production
"reparation and types)" and 1st Tsukasa, Bian/g7/Otsu (/97 year//month), OtsutA
The method described on page g can be followed.

The photographic emulsion used in the present invention is described in "Physics and Chemistry of Photography" by Grafkide, published by Beaumontel (P.

Qlaffides, Chimie et phy
siquePhotographique Paul
Montel.

Guffin, "Photographic Emulsion Chemistry", published by Focal Press (G, F. Duffin, T'hoto)
-graphic Emulsion Chemises
try (1;'ocal Press, /ri6 Otsu),
"Production and Coating of Photographic Emulsions" by Zelikman et al., published by Focal Press (V.L., Zelikman et a.
l、Makingand Coating Photo
graphic emulsion.

It can be prepared using the method described in Pocal Press, /Riot≠). That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble silver salt with the soluble chloride salt may be a one-sided mixing method, a simultaneous mixing method, or a combination thereof. It's okay. It is also possible to use a method in which grains are formed under an excess of silver ions (so-called back mixing method)2.As a form of simultaneous mixing method, there is a method in which pAg in the liquid phase in which silver halide is formed is kept constant, i.e. It is also possible to use the so-called Chondrold-Tabrenoet method. According to this method, a silver lodenide emulsion with a regular crystal shape and a nearly uniform grain size can be obtained.

Two or more silver halide emulsions formed separately may be mixed and used.

The 10-gen ratio silver emulsion consisting of the regular grains described above is
It is obtained by controlling pAg and pII during particle formation. For more information, please refer to the 1st Graphic Science Ant Engineering Link (Photograp
hic 3science and Engineer
ing)IT,lp-'? '5,/! ; 9～
/ A 6 pages (/Riotsu 2); Journal of Photographic Science (Journal of P
photographicScience), /2jf
15. ．． 21A2~. 23/page (/9'6≠), US Patent No. 3. Otsujj, No. 39 and British Patent No. 1. ll-
It is described in No. 73,7≠g.

A representative example of a monodispersed emulsion is an emulsion in which silver halide grains have an average grain diameter larger than about 0.7 microns, and at least the diameter of the grains is within ±1.10 inches of the average grain diameter. It is true. Average particle diameter is approximately 0.2 to 2
microns, with at least about 7J% by weight or several liters of halogenated anchor particles having an average particle diameter ±
Emulsions such as those within the 20% range can be used in the present invention. A method for making such an emulsion is described in U.S. Pat. No. 3,57≠.

No. 1.2g', No. 3.1.3! ;, No. 32 and British Patent No. 1. 3゜ described in Hiro 13, 7 Hirog No. 3 and JP Kokai Akihiro r-gzOO No. j/-370.27,
No. 31-43097, No. J3-/37/33, No. 5
tA-4Llta 2/No., IJj4! Monodisperse emulsions such as those described in IPgl No. 3; I-37A33 and Jzaihiro No. 23g can also be preferably used in the present invention.

Also, tabular grains having an ascent ratio of about 5 or more can be used in the present invention. Tabular grains are described by Gutoff, Photographic Science and Engineering.
ence and Engineering),
Volume 1 ILL, pages 4-2j7 (/970): U.S. Patent No.≠, 4t3≠, 22 Otsu, same≠, ≠/≠, 310
No. 4≠, lA33,0411, μ, 13ri, j,
! No. 0 6M and British Patent No. 2. It can be easily prepared by the method described in, for example, No. 2,137. When tabular grains are used, improvement of color sensitization efficiency by sensitizing dye,
Advantages such as improved graininess and increased sharpness are described in detail in the aforementioned US Pat.

The crystal groove structure may be uniform, the inside and outside may be composed of different halogen 18'i, or it may be a layered structure. These emulsion grains are described in British Patent No. 1,0.
27. /≠Otsu No. 3, U.S. Patent No. 3. JOj, No. 06g, same p, tplA, No. 177, rd and patent application 1972-. 21
111tl, No. 7, etc.

Further, silver halides having different compositions may be joined by epitaxial joining, and for example, rotane halides,
It may be bonded with a compound other than silver oxide, such as lead oxide. These emulsion grains are described in U.S. Patent No. G,07
≠, 6g≠ issue, 4g, /≠2.700 issue, same≠, lA
,3'? , 3. ! ;3, British Patent No. 2,03g;
? ';'2, U.S. Patent No. 11.3μ7. Otsu No. 22, same≠, 39, ≠7g, same≠.

't33.3; 0j No., same μ, μ Otsu No. 3, 0♂ No. 7, same 3
, Otsu j Otsu, 2 Otsu No. 2, 3. r! No. 2,067, Tokukai Sho Star/Otsu, 2! ≠Disclosed in No. 0, etc.

It is also possible to use a mixture of particles of various crystal forms.

The emulsion of the present invention is usually used which has been subjected to physical ripening, chemical ripening and spectral sensitization. The additives used in such factories are Research Disc O-Shear IF6/
71r p3 oyohi same, ttx i I 7,,'
lrK, and the relevant locations are summarized in the table below.

Known photographic additives that can be used in the present invention are also listed in the above two Research Disclosures, and one of them is listed below.

1 Chemical sensitizer, page 23, page O & f, right column 2
, Sensitivity enhancer Same as above 3 Spectral sensitizer, , ? Page 3-2≠ Otohiro♂ Page right column ~ Super sensitizer Page 647 Right column 4, Brightener
24L page 5 Anti-fog agent, 2tft-, 2J' page Otsu 41
．． Page right column and stabilizer 6, light absorber, 7 2.3'~L page O≠R right column ~ Ilter dye Otsu J'0 left column Ultraviolet absorber 7 Anti-stain agent,! Page j right column tSO page left to right column 8 Shiroishi image stabilizer, lA page 9 Hardener page -2 page 657 left column 10
, Binder, 2 pages, same as above +1
．． Plasticizers, lubricants, page 27 Otsu SO right column 1
2. Coating aid, Tables 26-J7 Pages Same as above Surface activator 13. Static anti-static, Page 27 Same as above Various color couplers can be used in the present invention. ), 46/71p≠3, ■, -C-G. As a dye-forming coupler,
Couplers that provide the three subtractive primary colors (i.e., yellow, agenta, and cyan) through color development are important, and specific examples of diffusion-resistant, Hiroto 1 or 2 light couplers include the aforementioned RD/7 Otsu 4t3, Vll- In addition to the couplers described in the patents listed in Sections C and D, the following may be preferably used in the present invention:

Typical examples of yellow couplers that can be used in the present invention include hydrophobic couplers having a balas group and a hydrophobic ester group. Specific examples of f-chili are described in U.S. Pat. No. 1, No. 4tQ7,210, U.S. Pat. The use of a two-way 14 yellow coupler is preferred for the present invention, as described in U.S. Pat.
．． ≠≠7. 2g issue, 3rd issue. 33, 30j and the same No. ≠, 0.22゜620, etc. or Tokko Sho! j? -10
No. 7,3, U.S. Pat.

British 111iI Patent No. 7. ri2j, 0 no θ, West German Application Publication No. r, ziri, ri 77, same? lc, 2, 21. /
, No. 36/, No. 2,327,6j7 and No. 2'433. A typical example thereof is the nitrogen atom separation type yellow coupler described in No. 2, No. 2, etc. α
- Vivaloylacetanilide F-based couplers have different fastness of color dyes, especially light fastness, while α-henzoylacetanilide couplers can provide high color density.

Magenta couplers that can be used in the present invention include hydrophobic intazolone-based or cyanoacetyl-based couplers having a ballast group, preferably j-pyrazolone-based and pyrazo-O
Examples include azole couplers. ! - The pyrazolone coupler is a coupler in which the 3-position is replaced with an arylamino group or a cylamino group, and the hue of the coloring dye is JP.
It is preferable from the viewpoint of color development + 11th order, and a typical example is
Wait n, ¥, 2, 3//, 0g2 No. 2, 3≠3.
No. 703, No. J, Too, No. 711, No. 2, 7
01, No. 573, same No. 3,062. Otsu No. 53, Otsu No. 3
．． /jco, No. 196 and No. 3. ri3 otsu, 0/! It is written in No. R, etc. As a leaving group for a two-equivalent pyrazolone coupler, a nitrogen atom leaving group described in U.S. Pat.
T,! ! /,! The arylthio group described in No. 77 is particularly preferred. Furthermore, a pyrazolone coupler having a balanute group as described in European Patent No. 73゜Otsu 3O can provide high color density. Examples of pyrazoloazole couplers include pyrazolobenzimidazoles described in U.S. Pat. No. 3,367, f7, preferably U.S. Pat. No. 3,723.
, pyrazolo (j,/-c) (/.

l,≠]To11 Ryozoles, Research Disclosure, 211220 (/rig≠June) and pyrazolotetrazoles and Research Disclosure lμ230 (/g≠June 2003) and pyrazolotetrazoles described in JP-A-1.0-33!62 9
Examples include pyrazolopyrazoles described in Japanese Patent Application Laid-Open No. 2003-120001 (June 2010) and JP-A No. 2003-041000-4T3. U.S. Patent No. 4 due to the low yellow side absorption of the coloring dye and light fastness.
1: , ! 00, imidazo (/
,,2-b) Pyrazole order is preferred and European Patent No. 1/
Pyrazolo [/,! -b)(/,
, 2. ≠] Triazoles are particularly preferred.

In order to correct unnecessary absorption due to color build-up, it is preferable to use a colored coupler in combination with a color photosensitive material for photographing to perform manukink. The 1st row coloring magenta coupler described in U.S. Pat.
231 and British Patent No. 1
．． A typical example is the magenta-colored cyan coupler described in No. 16, 3 Otsu. Other colored couplers are described in 1'tD/76≠3 and N41 to 0 above.

Granularity can be improved by using a coupler in which the coloring dye has an appropriate diffusibility. Such a coupler is
U.S. Patent No. 11. Specific examples of magenta couplers are found in El,t, 237 and British Patent No. 2,/23.370, and in European Patent No. 76.570 and West German Application No. Ml,23≠,j33, yellow, magenta Or a specific example of a cyan coupler is described.

The dye-forming couplers and the special couplers described above may form dimers or more polymers. Typical examples of polymerized dye-forming couplers are disclosed in U.S. Pat. No. 3.4/, j/
, Za 20 and Dodai Hiromu, ogo.

,! It is described in the // issue. Specific examples of polymerized magenta cazolers are given in British Patent No. 1, 102, /73.
and US Pat. No. 31r7,212.

Couplers that release photographically useful residues upon coupling are also preferably used in the present invention. DIR cazolers that release development inhibitors are the aforementioned RD/71. tA
3. The patented couplers described in Sections 1-F are useful.

A preferred combination with the present invention is JP-A-Sho! ;7
-/! /Developer deactivation type represented by T4L; U.S. Patent No. V, 24#, Ri Otsu No. 2 and JP-A! )17-
The timing type represented by /O-34; Tokuhan Shojter 37 Otsu! The reaction type represented by No. 3 is particularly preferred, and the particularly preferred one is JP-A-57-/J/RI-1. LIA, same jf
-J/7ta No. 3-, patent application No. 73 μ7, 1973, 1
Moderator f, 2j/4! Same issue! Developer-deactivating type DIR couplers described in Targ, Zri≠ No. 6 and Kenj9-Ta 0'1-31, etc. and reactive DIR couplers described in Japanese Patent Application No. 53, Patent Application No. 59-37 Otsu, etc. It is.

In the light-sensitive material of the present invention, a coupler that releases a nucleating agent, a development accelerator, or a precursor thereof in an image form during development can be used. Specific examples of such compounds are given in British Patent No. 2. Ori7゜/μθ No., same No.-, /3/,
It is described in /♂g issue. Couplers that release 5 nucleating agents that have an adsorption effect on silver halide are particularly preferred.
1 and same! 9-/701≠θ etc.

Suitable supports that can be used in the present invention include, for example.

The aforementioned RD, A/7A≠2 of 3? Page and same, Tsuta xr
'yit's t≠t from the right column of the 7th picture! It is written in the negative left column.

The color photographic light-sensitive material of the present invention is the above-mentioned RD.

&/ 7 A≠3 co-r-cota page and the same, ya/17/
2/,! / It can be developed by the usual methods described in the left column to right column.

The color photographic material of the present invention is usually subjected to a water washing treatment or a stabilization treatment after one development, bleach-fixing or fixing treatment.

However, if water is saved by 1, a new problem arises in that the amount of remaining processing liquid components in the film after processing increases.

(per unit area of the photosensitive material processed by the water rinser)
30 (If γ1 or less, residual thiosulfate or sulfite in the film - and if a bleach or bleach-fix solution with fatigue 17 is used, residual ferrous salts will act synergistically) and heating <i: (At the time of heating, the cyan dye is faded 1
As a result of doing so, you will be in charge of the money. For this reason, it has not been possible to save sufficient water in the past, but the Ichiki invention shows excellent dye stability even under such conditions, making it possible to save sufficient water.

Such effects of the present invention are not limited to mere water saving, but are equally exhibited in the stabilization treatment described in US Pat. No. 33, 324/.

Adding a compound of perilla to the stabilization treatment solution 1. Examples include various buffering agents (e.g., borate-metaborate-borax-phosphate, carbonate, salt, potassium hydroxide - hydroxide) II...mu.

Typical examples include ammonia water (using a combination of monocarboxylic acid, dicarboxylic acid, polycarboxylic acid, etc.) and formalin. Others - Water softeners (inorganic phosphoric acid - aminopolycarboxylic acid, organic phosphoric acid, aminopolyphosphonic acid, phosphonocarboxylic acid, etc.), sterilizing agents [dlC benzisothiazolinone, illithiazolone, tA-thiazoline benzimidazole] as necessary , halogenated phenol, etc.) - surfactants, fluorescent brighteners, hardeners, and other various additives may be used, and two or more compounds for the same or different purposes may be used in combination. The present invention can be applied to various color photosensitive materials. Typical examples include color negative film for general use or one-screen use, color reversal film for slides or television, color, R-, color positive film, and color reversal film. . The present invention also relates to Research Disclosure/7/
It can also be applied to black-and-white light-sensitive materials using a mixture of three color couplers as described in, 23 (/7g, July 2013).

Preferred embodiments of the present invention are listed as follows: 1. The highest sensitivity red-sensitive emulsion layer contains at least one coupler represented by the general formula (1), and the red-sensitive layers other than this layer contain a coupler of general formula (1); A saponified button color photographic material containing at least one coupler represented by formula [II].

2. The highest sensitivity red-sensitive emulsion layer contains at least one dichromatic coupler represented by the general formula CI), and the red-sensitive layer other than the core layer contains at least one coupler represented by the general formula [I]. Silver halide color photographic material.

3. In Embodiment 2, the coupler of general formula [I] is contained in an amount of 0.05 to 7.0 moles per 1 mole of coupler of general formula (II) contained in the entire red-sensitive silver halide emulsion layer. Silver halide color photographic material.

Hereinafter, the present invention will be described in more detail with reference to examples.
The present invention is not limited thereby.

Example/Photosensitive material consisting of each layer having the composition shown below on one cellulose triacetate support, trial 1') / 0 /~/
0 was created. The couplers contained in the first layer and the second layer are shown in Table 1.

1st layer: 1st red-sensitive emulsion layer (low-sensitivity emulsion layer) Silver iodobromide emulsion (Iodide ≠ Morch) Coating information /, ≠ 4' y/ m
2 Sensitizing dye 1 ≠, j x 10 mol per 1 mol of silver Sensitizing dye Il ≠, j x 10 mol per 1 mol of silver Coupler 0.0 mol per 7 mol of silver (Table 7
) 2nd layer, 2nd red-sensitive emulsion layer (high-sensitivity emulsion layer) Silver iodobromide emulsion (silver iodide 10 molti)...Silver coating amount /,
ll-ll-ta/m 2 sensitized color accumulation]...
・・・3×10 mol per 1 mol of sensitizing dye ・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・×70 mol coupler per 1 mol of silver ・・・・・・・・・・1 /mol (listed in table/) 0゜03mol 3rd layer:
Protective layer polymethyl methacrylate particles (diameter approx./.

In addition to the above composition, a gelatin hardening agent H-/ and a surfactant were added to each gelatin layer containing jAm).

Compound sensitizing dye 1 used to prepare the sample: anhydro-j,j'-dichloro-3,3
'-di(γ-sulfopropyl)-terethyl-thiacarbocyanine hydroxide pyridinium salt sensitizing dye ■: Anhydro-7-ethyl-3,3'-di(γ-sulfopropyl)-μs, p/-j ′−
Dibenzothiacarbocyanine hydroxyte/triethylamine salt The couplers used in the low-sensitivity layer are coupler 20y, dibutyl fuculate 20rxl, and eyl acetate jO1! In addition to the mixed solution of e, completely dissolve in O0C and mix with 20 ml of 10% water iJ solution of Alcatol B (alkylnaphthalene nulphonate manufactured by Dubon) and 100 ml of 10% Seratin aqueous solution. The mixture was emulsified and dispersed in a colloid mill.

All of the couplers used in the high-speed layer were emulsified and dispersed under the same conditions as the couplers used in the low-speed layer, except that tricrene sulfate was used instead of dibutyl fuculate.

1-■-/ (C112-Cll5O,, CH2CONI-ICH2
+2 centome for obtained samples 70/~/20)
After the exposure for II-, the following development process (A
) was performed in J['C.

1 Color development ・・・・・・・・・・・・・・・・・・
・3 minutes/j seconds 2 bleaching ・・・・・・・・・・・
・・・・・・・・・ 6 minutes 30 seconds 3 Wash with water ・・・・
・・・・・・・・・・・・・・・ 3 minutes/j seconds 4, constant
Arrival ・・・・・・・・・・・・・・・ μ minutes! 0
Second 5 Wash with water ・・・・・・・・・・・・・・・・・・
・ 3 minutes/j seconds 6 Stable ・・・・・・・・・・・
7 minutes 5 seconds The composition of the treatment liquid used in each step is as follows.

Color developer 2l, sodium lylotriacetate /, Oy sodium sulfite 11um ≠, Oy sodium carbonate 3o, oy potassium helide
/, ≠ Nohytroxylamine sulfate,! , 4y≠-(N-ethyl-N-β-hydroxyethylamine) -2-methylaniline sulfate ≠, jy add water / 2 bleaching solution ammonium bromide / 1.0.0y aqueous ammonia (1'%) 2! ;, Occ ethylenediamine-tetraacetic acid sodium iron salt /30. OF glacial acetic acid
/≠, add OCG water
/ 2 Fixer Sodium Tetrapolyphosphate 2.0y Sodium Sulfite ≠,oy Ammonium Thiosulfate (70T) /7! ;, OCC sodium biphosphite ≠, add 6 water
/ Q stabilizer formalin f, add Occ water / It then develop (
Development processing (B) was carried out in the same manner as development processing (A) except that the bleaching processing solution in A) was changed to the following processing solution formulation. This bleaching solution is a schematic representation of a state in which a large amount of photosensitive material has been processed and is exhausted.

Treatment step [B] Bleaching solution composition (D-/)... Redox stereotaxic/IOmV/D
-, 21 CD-, 2), put steel wool in it, leave it with a tightly stopper, and then perform Fe (m l -EDTA iF e (I[l
After EDTA, the bleaching solution (redox potential of about jo
The treatment was carried out in the same manner as in treatment step CA) except that the mVl was changed.

Sample 10/treated in treatment steps CA) and CB)
Measure the density with red light for ~lO and compare the couplers.
[A] 0CH2C) hschchH3 ([3) CG) [E] In the table -/, relative sensitivity is the relative value of the exposure amount required to give a density equivalent to [minimum density 10°2], expressed as an antilog. It is expressed as

Dye residual rate - Defined as maximum a degree in treatment (I3)/maximum density in treatment (A) x 100.

Table/Samples using comparative couplers (A) to [E] (1
0/~l10) had a poor dye residual rate in a tired bleaching solution, whereas 1 sample using the coupler of the present invention (///~/
It is clear that Sample No. 20) has a very good dye residual rate and is highly sensitive compared to the comparative sample.

Sample 10/~10! is a combination of couplers shown in Example 1 of Japanese Patent Application Laid-Open No. 2003-120002, and the effects of the present invention are obvious.

Example 2 The following “
A multilayer color photosensitive material consisting of each layer having the composition shown in
207~, 2.20 were produced.

(Sample, 20/) First layer; antihalation layer, black colloidal silver-containing ceratin layer; first layer; intermediate layer; 2. Seratin layer 3rd layer containing an emulsified dispersion of j-di-t-octylhydroquinone; First red-sensitive emulsion layer Silver iodobromide emulsion (iodide button; /, 1.17m2 Sensitizing dye 1・・・・・・・・・・・・Button ≠, j × 10 mol Sensitizing dye■・・・・・・・・・・・・Button per mole/,!×70 mole coupler 11-b...0.0 per mole of silver
3 mole coupler EX-/...0.003 mole coupler EX- per mole of silver,!・・・・・・O, ooor moles per mole of silver layer; Second red-sensitive emulsion layer Silver iodobromide emulsion (Silver iodide: 10 moles...Silver coating amount /, 4]/ m 2 Sensitizing dye 1・・・・・・・・・3×70 mol sensitizing dye per 1 mol of silver■・・・・・・・・・・・・S1 per mole / Teo
, ooib mole j-th layer; 6th layer same as the 2nd intermediate layer; 1st green-sensitive emulsion layer Silver iodobromide emulsion (iodide scissors; ≠ mol %)...Silver coating amount /, - 2917m2 Sensitizing dye■・・・・・・・・・J×70 per mole of silver Sensitizing dye■・・・・・・・・・・・・2 per mole of silver ×70 Molar coupler Ex-3・・・・・・・・・0.0j for 1 mole of silverMolar coupler EX-≠・・・・・・・・・O for 1 mole of silver , oog mole coupler EX-j...0.007 g mol per mol of silver 7th layer; second green-sensitive emulsion layer silver iodobromide emulsion (iodide; g mol) %)・・・・・・・・・
Planer coating amount / , 3jil/m2 Sensitized color accumulation...3 per mole of silver
X10 molar sensitizing dye ■・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・them/, 2x10 mol coupler .0/7 mole coupler EX-7...0.003 mole to 7 moles of silver G layer; Yellow filter 1 layer Yellow colloidal silver and 2.0 moles in gelatin aqueous solution. j-gee 1-
Gelatin layer containing an emulsified dispersion of octylhydroquinone; Second layer; first blue-sensitive emulsion layer; silver iodobromide emulsion (silver iodide; mole %)...
Coating amount of silver 0,7 y/m2 Coupler EX-4・・・・・・・・・0, . 0 mole coupler EX-ta......0.0/3 per 7 moles of silver; 10th mole layer; 2nd blue-sensitive emulsion layer silver iodobromide (silver iodide; Mol%)・・・・・・Amount of silver coating 0. Coupler EX-,!'・・・・・・・・・・・・0.0 mol per 1 mol of silver 1st/layer; 1st protective layer silver iodobromide (iodide 7 molten silver, average particle size 0.07μ)...
・・・・・・・・・＠Amount of application 0, j y
/m2 Gelatin layer 72nd layer containing an emulsified dispersion of ultraviolet absorber UV-/; Protective layer: Apply a gelatin layer containing 11 methyl methacrylate particles (diameter approx. /, jμ).

In addition to the above composition, a gelatin hardening agent H-/ and a surfactant were added to each layer.

The sample prepared as described above was designated as sample 20/.

Compounds used to prepare the sample Sensitizing dyes: Anhydroter ethyl j, 5'-cyclo3,3'-di(r-sulfozolovir) oxacarbocyanine/strium salt sensitizing dye ■: Anhydro j ,+,j',6'-tetrachloro/,7'-diethyl-3,3'-di-1β-[β-(γ-sulfopropoxy)ethoxy]ethylimidazolocarbocyanine hydroxide sodium salt EX-/○H EX-j EX-J α Coupler EX-≠ EX-5 α Coupler EX-Otsu C4H9 Coupler EX-7 Samples 202 to 2.20 were prepared by performing equimolar substitution as shown in Table 2.

Centomet 1 for the obtained samples 207-2.20
After the exposure for 1-, development treatment (A
) and CB), and the concentrations of the treated samples were measured using red light.

The results are shown in Table 1.

From Table 2, it is clear that compared to Comparative Examples 207 to 210, the samples of the present invention, 2//~, 2.20, showed extremely little decrease in concentration in treatment 1) using fatigue bleaching solution and had high sensitivity. It is. Samples 207-206 are from JP-A Shoj? −≠1. A
This is the combination of couplers shown in Example tA4t, and the effects of the present invention are obvious.

Example 3! , 14 examples/sample/θ/->3t'! ;; After 7 days, a standard wl shadow of the subject was performed outdoors.

This was processed using an automatic processor using the processing steps shown in Table 1-3 and a lower temperature processing solution.

Table 3 Processing process ★: Photosensitive material 3j1 width/m length In the above processing process, water washing (■) and (2) were performed using a countercurrent water washing method from ■ to ■. Next, the composition for each treatment will be described.

Color developer> Mother solution (7) Replenisher (
9) Diethylenetriaminepentaacetic acid HaOha/ /-Hydroxyethylidene-//-Diphosphonic acid co, 0 +2.2 Sodium sulfite ≠, O≠, Potassium carbonate 30.0 3.2.0 Potassium bromide Haμ 0. 7 potassium iodide
Ha3m9- Hydroxyamine No, ≠ 2.6ge (N-
Ethyl-N-β monohydroxy/ethylamino)-2-methylaniline sulfate <z, t j, .

Add water lt 1L pH 10,
oo 10. os <Bleach solution> Mother solution (7) Replenisher solution (7)
Ethylenediaminetetraacetic acid di-ammonium salt Ethylenediaminetetraacetic acid disodium salt 10 // Ammonia water j m 4tmJ Ammonium nitrate 10.0 /2. Of? Ammonium bromide 1roy i”yoy with water /l 1tpH3-, t
t, t Fixer> Mother solution (y) Replenisher (?
) Ethylenediaminetetraacetic acid disodium salt /, θ /1.2rai
i Sodium sulfate Hiro, 0 5.0 Sodium bisulfite Hiro, t! r, rAmmonium thiosulfate aqueous solution (70'fy) /7! ml 200
rn! water/metal plus /l 1t
pH/,,A,! :, A <Stabilizing liquid> Mother liquid (7) Replenishing liquid (f
I formalin (37% w/v) 2.0ml 3.0
ml, -'' Seven oxyethylene-p-monononylphenyl ether (average degree of polymerization lol, 3o, t, t, r with water added /l <Washing water, supplementary washing water>) Tap water was used.

The above processing steps and contents carried out in the processing are as shown in Table V.

In addition, in the bleaching solution after the treatment shown in Table 1-≠, 3 to r% of the total iron salts contained were reduced to the state of ferrous salt (ethylenediaminetetraacetic acid iron(II) salt).

Yo Sehe - * * After carrying out each of the above runs, the color temperature ≠ goo 0 for the test t+ shown in Table 1 of the examples/T+
The film was processed using a 20 CMS wedge exposure. [Processing C] Next, the bleaching solution, fixing solution, and washing water were all replaced with new solutions and the same treatment was carried out.[Processing D] The above samples were treated with
+i) was measured, and the dye residual rate was calculated for the sample after running.

Color bottle residual rate = [maximum density in treatment C/ Maximum concentration in treatment B) x io.

As can be seen from Table 1, even when the amount of replenishing water in the washing step of the five-sensitivity light-sensitive material of the present invention is extremely low, the decrease in the dye residual rate is extremely small.

Claims (1)

[Scope of Claims] In a silver halide color photographic light-sensitive material having at least two red-sensitive emulsion layers with different sensitivities on a support, the red-sensitive emulsion layer with the highest sensitivity contains a cyan dye represented by the following general formula [I]. A silver halide color photographic light-sensitive material containing at least one type of forming coupler, and containing at least one cyan dye-forming coupler represented by the following general formula [II] in a red-sensitive layer other than the above layer. . General formula [I] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ General formula [II] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ In the formula, R_1 is an aromatic group, R_2 is an aliphatic group, an aromatic group, or R_3 represents an aromatic group, and X and Y represent a hydrogen atom or a group capable of being separated by a coupling reaction with an oxidized aromatic primary amine developer. However, X and Y are not photographically useful groups.