JPH03209470A - Color image forming method - Google Patents

Abstract

PURPOSE:To reduce variation of photographic characteristics by incorporating a specified yellow coupler in a blue-sensitive emulsion layer and replenishing a color developing solution in an amount of <=200ml/m<2> of the silver halide color photographic sensitive material to execute its successive processing. CONSTITUTION:The silver halide color photographic sensitive material contains the yellow coupler represented by formula I in the blue-sensitive emulsion layer and the total silver halide coating amount on the support is regulated to <=0.78g/m<2> in terms of silver, and this photosensitive material undergoes succes sive processing by replenishing a color developing solution in an amount of <=200ml/m<2> of the silver halide color photographic sensitive material. In formula I, R1 is aryl or tertiary alkyl; R2 is F, alkyl, aryl, or the like; R3 is a group substitutable on the benzene ring; X is H or a group to be released by coupling reaction with the oxidation product of an aromatic primary amine color develop ing agent; and l is an integer of 0 - 4, thus permitting variation of photographic characteristics.

Description

Detailed Description of the Invention (Industrial Field of Application) The present invention relates to a color image forming method, and more specifically, the present invention relates to a color image forming method that has excellent color reproducibility and that continuously processes a silver halide photosensitive material using a low replenishment color developer. The present invention relates to a color image forming method in which changes in photographic properties during processing are significantly reduced.

(Prior art) A silver halide color photographic light-sensitive material has a silver halide emulsion layer that is sensitive to each of the three primary colors of -a, green, and red, and develops colors of yellow, magenta, and cyan, respectively, thereby achieving so-called color reduction. Reproduce the color image using the method. Therefore, the reproduced color image largely depends on the color sensitivity characteristics of each layer and the spectral absorption characteristics of color development.

Therefore, various improvements have been made to improve color reproducibility.
It has been done.

For example, improvements in magenta couplers are described in RF Publication No. 49-74027, RF Publication No. 49-111631, and U.S. Patent No. 3.725.067.

Furthermore, to improve the yellow coupler, the maximum absorption wavelength of the coloring dye formed was moved to the shorter wavelength side, and
JP-A-63-123047 and JP-A-63-123047 and JP-A-63-123047 are known as couplers whose absorption at long wavelengths exceeding nrn sharply decreases.
No. 3-231451.

There is a description in Tokuzan Hei 1-213648. However, when photosensitive materials using these yellow couplers were subjected to continuous processing, it was discovered that there was a problem in that the photographic properties changed significantly before and after the continuous processing, which seriously impeded the finished quality of color prints.

In addition, in the processing method of silver halide color photographic light-sensitive materials, it is desired to reduce developer replenishment for the purpose of saving resources and reducing pollution.
It is described in No. 106655, etc. It has been found that when photographic materials using the above-mentioned yellow coupler were continuously processed with these low-replenishment developing solutions, the change in photographic properties before and after the continuous processing was so large that it could not be used in practical applications.

(Problems to be Solved by the Invention) As mentioned above, the yellow coupler described in item 1, which has excellent color reproducibility, has a large change in photographic properties when processed with a color developer with low replenishment. It has not been possible to put it into practical use in the current situation where there is a strong demand for it. As a result of extensive research, the inventors of the present invention have discovered that by regulating the amount of silver halide emulsion contained in a color light-sensitive material, this change in photographic properties can be significantly reduced.

Therefore, an object of the present invention is to provide a color image forming method which has excellent color reproducibility and which causes significantly less change in photographic properties when a silver halide photosensitive material is continuously processed with a low replenishment color developer. be.

(Means for Solving the Problems) The above object of the present invention is to provide a silver halide color photographic light-sensitive material having at least one wild-sensitive emulsion layer, one green-sensitive emulsion layer, and one red-sensitive emulsion layer on a support. In a color image forming method in which processing is performed using a color developer containing a type of aromatic primary amine color developing agent, the blue-sensitive emulsion layer contains at least one yellow coupler represented by the following maximum [I]. , and a silver halide color photographic light-sensitive material in which the total amount of silver halide emulsion on the support is 0.78 g/durability or less as a silver equivalent coating amount, and the replenishment amount is 200 ml or less per 1 d of silver halide color photographic light-sensitive material. This was effectively achieved by a color image forming method characterized by continuous processing using a color developer.

General formula (1) [wherein, R represents an aryl group or a tertiary alkyl group,
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, R1 is a group that can be substituted on the benzene ring, and X is a hydrogen atom or an aromatic group. l represents a group that can be separated by a coupling reaction with an oxidized product of a primary amine developer, and l represents an integer of 0 to 4, respectively. However, when l is plural, the plural R1s may be the same or different.] The compound [■] used in the present invention will be explained in more detail.

In the general formula CI), R preferably has 6 carbon atoms.
~24 aryl groups (e.g. phenyl, P-)lyl, 0
-) lyle, 4-methoxyphenyl, 2-methoxyphenyl, 4-butoxyphenyl, 4-octyloxyphenyl, 4-hexatecyloxyphenyl, 1-naphthyl)
or a tertiary alkyl group having 4 to 24 carbon atoms (e.g., butyl, t-pentyl, t-hexyl, l, L, 3.
3-tetramethylbutyl, l-7 damantyl, 1.1-
dimethyl-2-chloroethyl, 2-phenoxy-2-propyl, bicyclo(2,2,2)octan-1-yl)
It is.

In the general formula (13), R1 is preferably a fluorine atom,
Alkyl groups having 1 to 24 carbon atoms (e.g. methyl, ethyl, impropyl, t-butyl, cyclopentyl, n-
octyl, n-hexadecyl, benzyl), C6-24 aryl groups (e.g. phenyl, P-)lyl,
o-tolyl, 4-methoxyphenyl), from 1 carbon atom
The proverbial alkoxy group (e.g. methoxy, ethoxy, butoxy, n-octyloxy, n-tetradecyloxy, benzyloxy, methoxyethoxy), having 6 to 2 carbon atoms
4 aryloxy group (for example) enoxy, r)-tolyloxy, o-1-lyloxy, p-me(.xifuninoxy, p-dimethylaminophenoxy, m-bentadenorpheno 4'-cy), number of carbon atoms 2 -24 dialkylamino group (e.g. dimethylamino, diethylamino, pyrrolidino, piperidino, morpholino), alkylthio group having 1 to 24 carbon atoms (e.g. methylthio, butylthio, n-octylthio, n-hexadecylthio) or 6 carbon atoms = 24 "aryl-ruthio (for example) S nylthio, 4-methoxyphenylthio, 4t-1
tylphenylthio, 4-dodecylphenylthio).

In the general formula ([), R8 is preferably a halogen atom (fluorine atom, chlorine atom, odor atom, iodine atom), an alkyl group having 1 to 24 r atoms (for example, methyl, t-butyl, n-dodecyl ), aryl groups having 6 to 24 carbon atoms (e.g. phenyl, p-tolyl, p-dodecyloxyphenyl), alkoxy groups having 1 to z4 carbon atoms (e.g. methoxy, n-butoxy, n-octyloxy, n- Tetradecyloxy, benzyloxy, -me[, xietogishi), carbon atom number 6-=2benaryloxy group (
For example) ni, phenoxy, p-1-phenoxy,
4-but]-xyhumunoxy), 7-number 2,24 ``1-rukokidicarbonyl group (e.g., 1-dicarbonyl, dodecyloxycarbonyl, 1-(dodecyloxycarbonyl)ethoxycarbonyl) ], carbon source: F number 7
=24 aryloxycarbonyl group (e.g. phenoxycarbonyl, 4-octylphenoxycarbonyl, 2,4-di-t-pentylphenoxycarbonyl)
, carbonamides having 1 to 24 carbon atoms [e.g., acetamide, pivaloylamino, benzamide, 2-ethyl chizanamide, tetradecaneamide, 1(2,4-
Z-bentylphenoxy)butanamide, 3-(
2,4-di-pentylphenoxy)butanamide,
3-Fdecylsulfonyl-2-methylpropanamide 1'
], a sulfuramide group having 1 to 24 carbon atoms (e.g. methanesulfonamide, p-toluenesulfonamide,
hexadecane sulfonamide), carbon number 1. =
240) h Ruhamo4 Ruhaji ([4,j ha N-methylcarbamoyl, N-tetradecylcarbamoyl, N, N-
dihexylcarbamoyl, N-octadecyl-N-methylcarbamoyl, N-7enylcarbamoyl) alkylsulfonyl group having 1 to 24 carbon atoms (e.g. evamethylsulfonyl, benzylsulfonyl, hexadecylsulfonyl), carbon atom number G to 24 arylsulfonyl s cf
For example, phenylsulfonyl, p-tolylsulfonyl, p
-Fdecylsulfonyl, p-methoxysulfonyl),
Carbon'fj: N-1k 1-24 (7) Ureido group (e.g. 3-methylureido, 3-phenylureido, 3.3
-dimethylamino, 3-tetradecylureido), sulfamoylamino groups having 0 to 24 carbon atoms (e.g. N,
N-'; methylsulfatylamino) 5 carbon atoms 2
-・24 alkoxyamyl levonyl amino number (e.g. methoxycarbonylamino, isobutoxycarbonylamino, dodecyloxycarbonylamino), nitro group,
A heterocyclic ring having 1=24 carbon atoms (e.g. 4-pyridyl,
2-thienyl, phthalimide, octadecylsuccinimide), 977, acyl group having 1 to 24 carbon atoms (e.g. acetyl, benzoyl, dodecanoyl), acyloxy group having 1 to 24 carbon atoms (e.g. acetoxy, benzoyloxy, dodecanoyloxy) ), number of carbon atoms 1~
・24 alkylsulfonyloxy groups (e.g. methylsulfonyloxy, heisubylsulfonyloxy) or arylsulfonyloxy groups having 6 to 24 carbon atoms (
For example, p-1-luenesulfonyloxy, p-dodecylphenylsulfonyloxy).

In general formula (1), j is preferably an integer of 1 or 2.

In the general formula (1), X is preferably an atom that can be removed by a coupling reaction with an oxidized product of an aromatic primary amine developer (referred to as M degrouping), and specifically, a halogen atom (fluorine, chlorine, bromine, iodine), carbon atoms 1-24
a heterocyclic group bonded to the coupling active position at the nitrogen atom of
Aryloxy group having 6 to 24 carbon atoms, 6 carbon atoms
~24 arylthio groups (e.g. phenylthio, p-t
-butylphenylthio, p-chlorophenylthio, p-
carboxyphenylthio), acyloxy groups having 1 to 24 carbon atoms (e.g. acetoxy, benzoyloxy, dodecanoyloxy), alkylsulfonyloxy groups having 1 to 24 carbon atoms (e.g. methylsulfonyloxy, butylsulfonyloxy, dodecylsulfonyloxy) ),
Arylsulfonyloxy groups having 6 to 24 carbon atoms (e.g. benzenesulfonyloxy, p-chlorophenylsulfonyloxy) or heterocyclic oxy groups having 1 to 24 carbon atoms (e.g. 3-pyridyloxy, 1-phenyl-1
, 2,3,4-tetrazol-5-yloxy), and more preferably a heterocyclic group or 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,
1゜2.4-triazole, tetrazole, indole, benzopyrazole, penzimitazole, benzotriazole, imidazolidine-2,4-dione, oxazolidine-2,4-dione, thiazolidine-2,4-dione, imidazolidine -2-one, oxazolin-2-one, thiazolin-2-one, benzimidacillin-2-
one, benzoxazolin-2-one, benzothiazolin-2-one, 2-pyrrolin-5-one, 2-imidacillin-5-one, indoline-2,3-dione, 2.6
-cyoxypurine, parabanic acid, 1,2゜4-triacyridine-3,5-dione, 2-pyridone, 4-pyridone, 2-pyrimidone, 6-pyridazone, 2-pyrazone, etc., and these heterocyclic groups are substituted. Examples of substituents that may be substituted include hydroxyl group, carboxyl group, sulfo group, amino group (e.g. amino, N-methylamino, N-methylamino,
.

In addition to N-dimethylamino, N,N-diethylamino, anilino, pyrrolidino, piperidino, morpholino), there are substituents listed as examples of R3 above.

When X represents an aryloxy group, X has 6 carbon atoms
-24 7-aryloxy, and when X is a heterocyclic group, it may be substituted with a group selected from the above-mentioned substituent group. Examples of the substituent include a carboxyl group, a 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, Rt, R, and X.

In -shell formula (1), Rt is particularly preferably a 2- or 4-alkoxyaryl group (e.g. 4-methoxyphenyl, 4-butoxyphenyl, 2-methoxyphenyl) or a t-butyl group; Most preferred.

In general formula (1), R1 is particularly preferably a methyl group, ethyl group, alkoxy group, aryloxy group or dialkylamino group, most preferably a methyl group, ethyl group, alkoxy group, 71J-ruoxy group or dimethylamino group. preferable.

In general formula (I), R2 is particularly preferably an alkoxy group, a carbonamide group or a sulfonamide group.

In general formula (1), 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 preferably represents F-
It is represented by the binding margin Cl11).

- Tsuzuriyo [kawa] In the general formula (lli), Z represents. Here, Rs, R-, Riz and R13 represent a hydrogen atom, an alkyl group, 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 R1
0 and R8 represent a hydrogen atom, an alkyl group, an aryl group, an alkylsulfonyl group, an allylsulfonyl group, or an alkoxycarbonyl group, and R14 and 1 represent a hydrogen atom, an alkyl group, or an aryl group.
l and R1 may be bonded to each other to form a Hensen ring, RlI and R, R, and R111, R111 and R11, or RlI and RI.

If the rings are bonded to each other (e.g. cyclobutane, cyclohexane, cycloheptane, cyclohexene, pyrrolidine,
piperidine).

- Particularly preferred among the heterocyclic groups represented by (l[i) are the heterocyclic groups in which Z is in the J-knee binding (II).

The total number of carbon atoms in the heterocyclic group represented by general formula (Ill) is 2 to 24, preferably 4 to 2o, and more preferably 5 to 1G. Examples of the heterocyclic group represented by (III) are succinimide group, maleimide group, phthalimide group, 1-methylimidazolidine-2,4-dione-3-yl group, 1-benzylimidazolidine-2,4
-dione-3-yl group, 5,5-dimethylimidazolidine-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-methylimidazolidinetrion-1-yl group, 1,2.4-triacylidine-3,5
-dione-4-yl group, 1-methyl-2-phenyl-1
, 2,4-triacylidin-3,5-dion-4-yl group, l-benzyl-2-phenyl-1,2,4-)lyacylidin-3,5-dion-4-yl group, 5-hexyloxy -1-methylimidazolidine-2,4-dione-
3-yl group, 1-benzyl-5-ethoxyimidazolidine-2,4-dione-3-yl group, ■-benzyl-5-
Dodecyloxyimidazolidine-2,4-dione-3-
There is an yl group.

Among the above heterocyclic groups, an imidazolidine-2,4-dione-.3-yl group (for example, a 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-chloroc1-4-hydroxyphenylsulfonyl)phenoxy group, 4-methoxycarbonylphenoxy group, 2-chloro-4-methoxycarbonylphenoxy group, 2-acetamido-4-methoxycarbonylphenoxy group, 4-isopropoxycarbonylphenoxy 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 -S formula (1) may form a dimer or a multimer of more than two molecules bonded to each other via a substituent R in = a group with a valence of 2 or more; in this case, each of the above 1
The number of carbon atoms may be outside the range shown in the conversion.

-i When the coupler represented by formula (1) forms a multimer, a single or copolymer of an addition polymer ethylene-type unplated compound (yellow color-forming 7-mer) having a yellow dye-forming coupler residue is used. This is a typical example. In this case, the multimer contains repeating units of the general formula (mV) and - binding margin (
One or more kinds of yellow color-forming repeating units represented by 'ff) may be contained in the multimer, and the copolymer contains one or more than 281 non-color-forming ethylene monomers as a copolymerization component. Good too.

General formula (ff) In the formula, R represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a chlorine atom, human represents -CONH-1-COO- or a substituted or unsubstituted phenylene group, and B represents a substituted or unsubstituted alkylene group, phenylene group or aralkylene group, L is -CONI4-1-NHCON
II-1-NHCOO-, -NHCO-5-0CONI
I-, -Nl(-1-coo-, -oco-, -co-
5-0-,-5-,-50! -1-Nl (represents SO, - or -5O, NH-; a, b, and c represent 0 or 1; Q is represented by the general formula (1); W;

The yellow coupler residue is shown with its offspring removed.

As the multimer, a yellow color-forming monomer represented by a coupler unit of the general formula [■] and the following non-color-forming ethylene type copolymer are preferred.

Examples of non-color-forming ethylene monomers that do not cuff with the oxidation products of aromatic-grade amine developers include acrylic acid,
α-chloroacrylic acid, α-alkyl acrylic! (e.g. methacrylic acid) 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-octyl acrylate, lauryl acrylate, methyl methacrylate , ethyl methacrylate, n-butyl methacrylate and β-hydroxy methacrylate), vinyl esters (e.g. vinyl acetate, vinyl propionate and vinyl laurate), acrylonitrile, methacrylatrile,
Aromatic vinyl compounds (such as styrene and its derivatives, such as vinyltoluene, divinylbenzene, vinylacetophenone and sulfostyrene) itaconic acid, citraconic acid, crotonic acid, vinylidene chloride,
Vinyl alkyl ethers (eg vinyl ethyl ether), maleic esters, N-vinyl-2-pyrrolidone, N-vinylpyridine and 2- and -4-vinylpyridine.

Particularly preferred are acrylic esters, methacrylic esters, and maleic esters. Two or more 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 binding margin CI'v
) to be copolymerized with vinyl monomers corresponding to vinylic monomers corresponding to vinylic monomers. The binder of the product can be selected such that its compatibility with, for example, gelatin, its potential, thermal stability, etc. are favorably influenced.

The yellow polymer cuff collar used in the present invention is a vinyl type cuff collar that provides a coupler unit represented by the binding margin (IV') above! , the lipophilic borine′ obtained with X-= of the mer
- It may be prepared by emulsifying a coupler dissolved in an organic solvent in the form of a latex in an aqueous solution of Ze5-tin, or it may be prepared directly by emulsion polymerization.

U.S. Pat.
, 451.820, and U.S. Pat.
, No. 080,211 and No. 3,370,952 can be used.

Below is the general formula [! ] Specific examples of the yellow dye-forming couplers Rs and X represented by the formulas are shown below. l is these 1
．． It is not limited to M.

Two specific examples of X are shown below. (1) (2) (5) (6) I, K (11) (12) (13) (14) (15) (17) C.O.

(18) (20) (21) (22) (23) (24) A specific example of R3 is shown below.

(25) CH.

J13 (36) (CHz) zcHcHxc-Hv-Li (37) CH.

C,, [l.

-NHCOC1hCHCOOCH.

-NH5OzCtJzs-n (38) (39) (41) -COOCI! H□ at -COOCHCOOC+zH□ -CONHC+-Ht* (42) (43) (44) -CONH(CHx)sOc+zHzs (47) -NHCOC+sL+-11 (48) In the yellow coupler represented by the general formula ([), preferably , below - is a chemical compound represented by Tsuzuriyo (II).

General formula (II) (wherein R4 represents an alkyl group, cycloalkyl group, acyl group or aryl group, R3 represents a group that can be substituted on the benzene ring, n represents O or l, Rh is carbonyl or sulfonyl represents an organic group containing one bonding group having a unit, J represents an alkyl group, an aryl group, or a heterocyclic group; ) R1 and X are the same as in general formula (1). )-In the alkyl group and cycloalkyl group represented by R4, the same alkyl group as R2 can be mentioned, and the aryl group can be, for example, a phenyl group. These alkyl groups, cycloalkyl groups, and aryl groups represented by R4 include those having the same W and substituent groups as R. In addition, examples of the acyl group include an acetyl group, a propiol group, a butyryl group, a hexanoyl group,
Examples include hendiyl group. Preferably 2 as R4
, an alkyl group, and an alkyl group, most preferably an alkyl group.

In the general formula (TI), the groups that can be replaced with I on the benzene ring represented by Rs include halogen atoms (e.g. chlorine atom), alkyl groups (e.g. ethyl group, i-propyl group, t
-butyl group), alkoxy group (e.g. methoxy group), aryloxy group (e.g. phenyloxy group), acyloxy group (e.g. methylcarbanyloxy group, benzoyloxy group), acylamino group (e.g. acetamido group, phenylcarbabonylamino group) , carbamoyl group (e.g. N-methylcarbamoyl group, N-phenylcarbamoyl group), alkylsulfonamide FM (e.g. ethylsulfonylamino group), arylsulfonamide group (e.g. phenylsulfonylamino group), sulfamoyl l1i
(for example, N-propylsulfamoyl L N-)T2nylsulfamoyl group) and imide groups (for example, succinimide group, glutarimide group), etc., and n does not represent 0 or l.

In general formula (II), carbonyl for R- represents an organic group containing one bonding group having a sulfonyl unit. Groups having carbonyl units include ester groups, amide groups,
Examples of the group include a carbamoyl group, a ureido group, and a urethane group. Examples of the group having a sulfonyl unit include a sulfone group, a sulfonamide group, a sulfamoyl group, and an aminosulfonamide F group.

represents a hydrogen atom, an alkyl group, an alkyl group, an aryl group or a monocyclic group.

Examples of the alkyl group represented by R7 include a methyl group, an ethyl group, an isopropyl group, a t-butyl group, and a dobusyl group. Further, the aryl group represented by R7 includes a phenyl group or a naphthyl group. These R,
The alkyl group, aryl group or heterocycle represented by the above also includes those having a substituent.

R1 and X are of the general formula (same as N).

Specific examples of the dye-forming coupler represented by the binding margin [1] are shown below.

In the table, the numbers in parentheses represent the numbers assigned to the specific examples of X and R3, 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.
There is a synthesis method described in the specification of No. 23047.

The amount of the coupler of the present invention used in the photosensitive material is 1XLO-' mol-104 mol per 1, preferably 1X
10-' mol-5×10-1 preferably 2X1O-' mol-104 mol.

The total amount of silver halide emulsion contained in the color photographic light-sensitive material of the present invention is 0.78 g7'M as a coating amount in terms of silver.
It is as follows. Preferably it is 0.70g/rrf or less. The total silver halide emulsion contained in the green-sensitive emulsion layer and the red-sensitive emulsion layer is 0.50 g as a silver equivalent coating amount.
/rrr or less is preferable.

More preferably 0-4'5z/'tr? It is as follows.
Further, the total amount of silver halide emulsion contained in the blue-sensitive emulsion layer is preferably 0.35 g/rrr or less in terms of silver coating amount. More preferably 0.27g/rr? It is as follows.

Next, the color development process applied to the color photosensitive material of the present invention will be explained.The amount of replenishment of the color developer of the present invention is 200 ml or less per 1 d of photosensitive material. Preferably it is 120 ml or less. More preferably 100m
Preferably, l is less than or equal to 70 m! It is as follows. The amount of replenishment referred to here includes a portion of the developer that is added to the developer after being subjected to a treatment such as ion exchange.

The color photographic material of the present invention is preferably subjected to color development, bleach-fixing, and water washing treatment (or stabilization treatment). Bleaching and fixing may be carried out separately instead of in one bath as described above.

The color developer used in the present invention contains a known aromatic primary amine color developing agent.

Preferred examples are p-phenylenediamine derivatives, representative examples of which are shown below, but are not limited thereto.

D-IN,N-diethyl-p-phenylenediamine D-2 2-amino-5-diethylaminotriene D-3 2-amino-5-(N-ethyl-N-laurylamino)toluene D-4 4-CN- Ethyl-N-(β-hydroxyethyl)amino]Tniline D-5 2-methyl-4-[N-ethyl-N-(β-hydroxyethyl)aminocoaniline D-6 4-amino-3-methyl- N-ethyl-N-[
β-(methanesulfonamido)ethyl]-aniline D-7 N-(2-amino-5-diethylaminophenylethyl)methanesulfonamide D-8 N,N-dimethyl-p-phenylenediamine D-9 4-amino-3- Methyl-N-ethyl-N-methoxyethylaniline D-10 4-amino-3-methyl-N-ethyl-N
-β-ethoxyethylaniline D-11 4-amino-3-methyl-N-ethyl-N
-β-phthoxyethylaniline Among the above p-phenylenediamine derivatives, 4-amino-3-methyl-N-ethyl-N- (β-
(methanesulfonamido)ethyl]-aniline (exemplified compound D-6).

Salts of these p-phenylenediamine derivatives such as sulfates, hydrochlorides, sulfites, and p-)luenesulfonate may also be used. The amount of the aromatic primary amine developing agent used is preferably about 0.1 g to about 20 g per developer solution 11.
, more preferably at a concentration of about 0.5 g to about Log.

In practicing the present invention, it is preferred to use a developer solution that is substantially free of benzyl alcohol. Here, "substantially free" means preferably 2 dll or less,
More preferably, the benzyl alcohol concentration is 0.5 d/1 or less, and most preferably, no benzyl alcohol is contained at all.

It is more preferable that the developer used in the present invention does not substantially contain sulfite ions. The sulfite ion functions as a preservative for the developing agent, and at the same time has the effect of dissolving silver halide and reacting with the oxidized product of the developing agent to reduce the dye formation efficiency.

Such an effect is presumed to be one of the causes of increased fluctuations in photographic characteristics due to continuous processing. Here, "substantially not containing" preferably means a sulfite ion concentration of 3.0 x 10 -' mol/i or less, and most preferably no sulfite ions at all.

However, in the present invention, a very small amount of sulfite ion used to prevent oxidation in a processing agent kit in which the developing agent is sll-filled before being mixed into a solution for use is excluded.

The developer used in the present invention preferably does not substantially contain sulfite ions, and more preferably does not substantially contain hydroxylamine. This is because hydroxylamine functions as a preservative for the developing solution and also has silver developing activity itself, and it is thought that fluctuations in the concentration of hydroxylamine greatly affect photographic properties.

The expression "substantially not containing hydroxylamine" as used herein means preferably a hydroxylamine concentration of 5.0 x 10-' mol/i or less, and most preferably no hydroxylamine at all.

It is more preferable that the developer used in the present invention contains an organic preservative instead of the hydroxylamine or sulfite ion.

The term "organic preservative" as used herein refers to any organic compound that reduces the rate of deterioration of an aromatic primary amine color developing agent when added to a processing solution for a color photographic light-sensitive material. That is, organic compounds that have the function of preventing color developing agents from being oxidized by air, among others, hydroxylamine derivatives (excluding hydroxylamine; the same shall apply hereinafter), hydroxamic acids, hydrazines, hydrazides, phenols, Especially α-hydroxyketones, α-aminoketones, sugars, monoamines, diamines, polyamines, quaternary ammonium salts, nitroxy radicals, alcohols, oximes, diamide compounds, fused cyclic amines, etc. It is an effective organic preservative. These are JP-A-63
-4235, 63-30845, 63-216
No. 47, No. 63-44655, No. 63-53551, No. 63-43140, No. 63-56654, No. 6
No. 3-58346, No. 63-43138, No. 63-1
No. 46041, No. 63-44657, No. 63-446
No. 56, U.S. Patent No. 3.615.503, 2, 49
No. 4.903, JP-A No. 52-143020, Special Publication No. 4
No. 8-30496 and the like.

Other preservatives include various metals described in JP-A-57-44148 and JP-A-57-53749;
Salicylic acids described in No. 180588, JP-A-54-35
Alkanolamines described in No. 32, JP-A-56-94
Polyethyleneimines described in No. 349, U.S. Pat.
．． If necessary, aromatic polyhydroxy compounds described in No. 746.544 and the like may be contained. In particular, it is preferable to add alkanolamines such as triethanolamine, dialkylhydroxylamines such as diethylhydroxylamine, hydrazine derivatives, or aromatic polyhydroxy compounds.

Among the above-mentioned organic preservatives, hydroxylamine derivatives and hydrazine derivatives (hydrazines and hydrazides) are particularly preferred.
It is described in No. 5270, No. 63-9713, No. 63-9714, No. 63-11300, etc.

Further, it is more preferable to use the above-mentioned hydroxylamine derivative or hydrazine derivative in combination with amines from the viewpoint of improving the stability of the color developer and further improving the stability during continuous processing.

Examples of the above-mentioned amines include cyclic amines as described in JP-A-63-239447 and JP-A-63-128.
Amines such as those described in No. 340 and other *H
Examples include amines such as those described in No. 3-9713 and No. 63-11300.

In the present invention, 3.5% of chloride ions are added to the color developer.
It is preferable to contain XIG'' to 1.5
10-'mol/l. Chlorine ion concentration is 1.5xl
If the amount is more than O-' to 10-1 mol/l, it has the disadvantage of delaying development, which is not preferable in achieving the object of the present invention of rapid development and high maximum density. Also, 3.5xi
If the amount is less than o-'' mole/1 drop, it is not preferable in terms of preventing fogging.

In the present invention, 3. bromine ions are added to the color developer.
Q OX10
-3% II'/1 is preferably contained. More preferably, it is 5.0×10 −′ to 5×10 −′ mol/1. If the bromide ion concentration is greater than IXIQ-'mol/i, development will be delayed and maximum density and sensitivity will be reduced;3.
If it is less than 0 x 10-' mol/i, fogging cannot be sufficiently prevented.

Here, the chlorine ions and bromine ions may be added directly to the developer, or may be eluted from the photosensitive material into the developer during the development process.

When added directly to a color developer, examples of the chloride ion supplying substance include sodium chloride, potassium chloride, ammonium chloride, lithium chloride, nickel chloride, magnesium chloride, manganese chloride, calcium chloride, and cadmium chloride, among which preferred ones are preferred. are sodium chloride and potassium chloride.

Alternatively, it may be supplied from an optical brightener added to the developer.

As a supply material for bromide ions, sodium bromide, potassium bromide, ammonium bromide, lithium bromide, calcium bromide, magnesium bromide, manganese bromide, nickel bromide, cadmium bromide, cerium bromide, thallium bromide Among these, preferred are potassium bromide and sodium bromide.

When eluted from the light-sensitive material during the development process, both chloride ions and bromine ions may be supplied from the emulsion, or may be supplied from a source other than the emulsion.

The color developer used in the present invention preferably has a pH of 9
-12, more preferably 9-11.0, and the color developer may contain other known developer component compounds.

In order to maintain the above pH, it is preferable to use various buffers. Buffers include carbonate, phosphate, borate, tetraborate, hydroxybenzoate, glycyl salt,
N,N-dimethylglycine salt, leucine salt, norleucine salt, guanine salt, 3゜4-dihydroxyphenylalanine salt, alanine salt, aminobutyrate, 2-amino-2-
Methyl-1°3-propanediol salt, valine salt, proline salt, trishydroxyaminomethane salt, lysine salt, etc. can be used. In particular, carbonates, phosphates, tetraborates, and hydroxybenzoates are soluble at pH 9.0.
These buffers have the advantages of excellent t11 buffering ability in the above high 98 range, no adverse effects on photographic performance (fogging, etc.) even when added to color developers, and are inexpensive. is particularly preferred.

Specific examples of these tIItf agents include carbonic acid) I
Jum, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate,
Potassium borate, sodium tetraborate (borax), potassium tetraborate, sodium 0-hydroxybenzoate (sodium salicyl), potassium o-hydroxybenzoate, sodium 5-sulfo-2-hydroxybenzoate (
5-sulfosalicylate), 5-sulfo-2-
Examples include potassium hydroxybenzoate (potassium 5-sulfosalicylate). However, the present invention is not limited to these compounds.

The amount of the buffer added to the color developer is 0.1 mol/1
It is preferably 0.1 mol/l to 0.1 mol/l or more.
Particularly preferred is 4 mol/1.

In addition, various chelating agents can be used in the color developer as an anti-settling agent for calcium or magnesium or to improve the stability of the color developer. For example, nitrilotriacetic acid, diethylenetriaminepentaacetic acid,
Ethylenediaminetetraacetic acid, N,N,N-trimethylenephosphonic acid, ethylenediamine-N,N,N',N'-
Tetramethylene sulfonic acid, transsilohexanediaminetetraacetic acid, 1. 2-diaminopropane tetraacetic acid, glycol ether diamine tetraacetic acid, ethylenediamine orthohydroxyphenylacetic acid, 2-phosphonobutane-1,
2,4-tricarboxylic acid, 1-hydroxyethylidene-
Examples include 1,1-diphosphonic acid%NIN'-bis(2-hydroxybenzyl)ethylenediamine-N, N'-diacetic acid, and the like.

Two or more of these chelating agents may be used in combination, if necessary.

These chelating agents may be added in an amount sufficient to sequester metal ions in the color developer. For example 11
It is about 0.1g to IGg per serving.

Any development accelerator can be added to the color developer if necessary.

As a development accelerator, Japanese Patent Publication No. 37-16088 and No. 3
No. 7-5987, No. 38-7826, No. 44-123
No. 80, No. 45-9019 and U.S. Patent No. 3.813
．． thioether compounds shown in JP-A No. 247, p-phinidine diamine compounds shown in JP-A-52-49829 and JP-A-50-15554;
No. 137726, Japanese Patent Publication No. 44-30074, Japanese Patent Publication No. 1977
Quaternary ammonium salts shown in No. 6-156826 and No. 52-43429, etc., U.S. Patent No. 2゜494,
No. 903, No. 3.128.182, No. 4.230.7
No. 96, No. 3.253.919, Special Publication No. 41-114
No. 31, U.S. Pat. No. 2,482.546, U.S. Pat.
Amine compounds described in 6.926 and 3.582.346, etc., Japanese Patent Publication No. 37-16088, 42-2
5201, U.S. Patent No. 3.128.183, Japanese Patent Publication No. 41-11431, Japanese Patent Publication No. 42-23883, and U.S. Patent No. 3.532゜501, and other 1-phenyl-3-pyrazolidones. etc., imidazoles, etc. can be added as necessary.

In the present invention, any antifoggant can be added if necessary. As antifoggants, alkali metal halides such as sodium chloride, potassium bromide, potassium iodide, and organic antifoggants can be used. Examples of organic antifoggants include benzotriazole, 6-nidropenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitropenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, Typical examples include nitrogen-containing heterocyclic compounds such as 2-thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine, and adenine.

The bright color developer used in the present invention preferably contains an optical brightener. As an optical brightener, 4,4'
-Diamino-2,2'-disulfostilbene compounds are preferred. The amount added is 0-5g/1, preferably 0.1
g~4/1.

Furthermore, various surfactants such as alkylsulfonic acids, arylsulfonic acids, aliphatic carboxylic acids, and aromatic carboxylic acids may be added as necessary.

The processing temperature of the vine color phenomenon liquid applied to the present invention is 20~
The temperature is 50°C, preferably 30 to 40°C. Processing time is 20
The time is from seconds to 5 minutes, preferably from 30 seconds to 2 minutes. It is preferable that the amount of replenishment is small, but it is 20 to 60 per rn' of photosensitive material.
0m! ! is appropriate, preferably 50 to 300 Wdl
It is. More preferably 60 to 200 d1, most preferably 60 to 150 d.

Next, a desilvering process that can be applied to the present invention will be explained.

The desilvering step may generally include any process such as a bleaching step-fixing step, a fixing step-bleach-fixing step, a bleaching step-bleach-fixing step, or a bleach-fixing step.

The bleaching solution, bleach-fixing solution and fixing solution applicable to the present invention will be explained below.

As the bleaching agent used in the bleach or bleach-fix solution, any bleaching agent can be used, but especially iron (
III) organic complex salts (e.g. ethylenediaminetetraacetic acid,
Preferred are aminopolycarboxylic acids such as diethylenetriaminepentaacetic acid, complex salts of aminopolyphosphonic acid, phosphonocarboxylic acid, and organic phosphonic acid) or organic acids such as citric acid, tartaric acid, and malic acid; persulfates; hydrogen peroxide, etc. .

Among these, organic complex salts of iron ([) are particularly preferred from the viewpoint of rapid processing and prevention of environmental pollution. Aminopolycarboxylic acids, aminopolyphosphonic acids, organic phosphonic acids, or salts thereof useful for forming organic complex salts of iron (I[[) include ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, ■, 3- Examples include diaminopropanetetraacetic acid, acetic acid, lopylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, iminodiacetic acid, glycol ether diaminetetraacetic acid, and the like. These compounds may be sodium, potassium, thium or ammonium salts. Among these compounds, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, 1. Iron (I [[) complex salts of 3-diaminopropanetetraacetic acid and methylimino diacetate are preferred because they have a high bleaching edge.

These ferric ion complex salts may be used in the form of complex salts, or ferric salts such as ferric sulfate, ferric chloride, ferric nitrate, ferric ammonium sulfate, and ferric phosphate. and chelating agents such as aminopolycarboxylic acid, aminopolybosphonic acid, and phosphonocarboxylic acid in a solution.
Ionic complex salts may also be formed. Further, the chelating agent may be used in excess of the amount required to form the ferric ion complex.

Among the iron complexes, aminopolycarboxylic acid iron complexes are preferred, and the amount added is 0.01 to 1.0 mol/i, preferably 0.05 to 0.50 mol/j! It is.

Various compounds can be used as bleach accelerators in the bleaching solution, bleach-fixing solution, and final bath or their pre-bath. For example, U.S. Pat.
Publication No. 630, Research Disclosure No. 1712
No. 9 (July 1978 issue), compounds having a mercapto group or disulfide bond, and
No. 06, JP-A-52-20832, JP-A No. 53-3273
Thiourea compounds described in No. 5 and US Pat. No. 3,706,561, or 710 genides such as iodine and bromide ions are preferable because they have excellent bleaching properties.

In addition, bromides (e.g., potassium bromide, sodium bromide,
Rehalogenating agents such as ammonium bromide) or chlorides (eg, potassium chloride, sodium chloride, ammonium chloride) or iodides (eg, ammonium iodide) can be included. If necessary, one or more types of borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, citric acid, etc. with p++ buffering capacity, such as borax, sodium metaborate, tartaric acid, etc. Inorganic acids, organic acids, alkali metal or ammonium salts thereof, or corrosion inhibitors such as ammonium nitrate and guanidine can be added.

The fixing agents used in the bleach-fix solution or fixing solution are known fixing agents, namely thiosulfates; Water-soluble silver halide solubilizers such as thioglycol, thioether compounds such as 3,6-dithiT-1,8-octanediol, and thioureas;
A species or a mixture of two or more kinds can be used.

It is also possible to use a special bleach-fix solution made of a combination of a fixing agent and a large amount of a halide such as potassium iodide as described in JP-A-55-155354. In the present invention, the use of thiosulfates, particularly ammonium thiosulfates, is preferred. The amount of fixing agent per 11 is
Preferably 0.3 to 2 mol, more preferably 0.5 to 1 mol
．． It is in the range of 0 mol. The pH range of the bleach-fixing solution or fixing solution is preferably 3 to 10, more preferably 5 to 9.

Further, the bleach-fix solution may contain various other optical brighteners, antifoaming agents, surfactants, and organic solvents such as polyvinylpyrrolidone and methanol.

Bleach-fix solutions and fixing solutions contain sulfites (e.g., sodium sulfite, potassium sulfite, ammonium sulfite, etc.), bisulfites (e.g., ammonium bisulfite, bisulfite), IJium, bisulfite, etc. as preservatives. potassium, etc.), metabisulfites (e.g., potassium metabisulfite,
Sodium metabisulfite, ammonium metabisulfite,
It is preferable to contain a sulfite ion releasing compound such as ).

These compounds are approximately 0.02 to 0.02 in terms of sulfite ion.
The content is preferably 0.05 mol/l, more preferably 0.04 to 0.40 mol/l.

As a preservative, sulfite is commonly added, but other preservatives include T-scorbic acid, carbonyl bisulfite adducts,
Alternatively, a carbonyl compound or the like may be added.

Furthermore, buffering agents, optical brighteners, chelating agents, antifoaming agents, antifungal agents, etc. may be added as necessary.

After desilvering treatment such as fixing or bleach-fixing, washing with water and/or stabilization treatment is generally performed.

The amount of water used in the washing process varies widely depending on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), the purpose, 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. Among these, the relationship between the number of flushing tanks and the amount of water in the multistage countercurrent method is described in the Journal of Motion Picture and Television Engineers (Journal of Society of Motion Picture and Television Engineers).
nalof the 5ociety of Moti
on Picture and Ta1evi-sio
n Engineers) Volume 64, p. 248-2
53 (May 1955 issue).

Generally, the number of stages in the multistage countercurrent system is preferably 2 to G, particularly preferably 2 to 4.

According to the multi-throw countercurrent method, the amount of washing water can be greatly reduced, for example, to 0.51 to 11 or less per 1 m+ of photosensitive material, and the effect of the present invention is remarkable. The increased residence time causes problems such as bacteria propagation and the resulting floating matter adhering to the photosensitive material. As a solution to this problem, the method of reducing calcium and magnesium described in JP-A No. 62-288838,
It can be used very effectively. Also, JP-A-57-
Isothiazolone compounds and cyabendazoles described in JP-A No. 8542, chlorinated isocyanuric acids described in JP-A No. 61-120145, chlorine-based disinfectants such as IJum, benzotriazole and copper described in JP-A-61-267761. Aeon and others, Hiroshi Horiguchi, “Chemistry of antibacterial and antifungal J” (198
6th year) Sankyo Publishing, complete hygiene technology “Sterilization and sterilization of microorganisms,
It is also possible to use the fungicides described in "Mildewproofing Technology" (1982), Japan Society of Industrial Science and Technology, Japan Society for Bacterial and Mildew Prevention, "Encyclopedia of Antibacterial and Antifungal Agents J (1986)".

Further, in the washing water, a surfactant as a draining agent and a chelating agent typified by EDTA as a water softener can be used.

The above-mentioned water washing step can be followed or the stabilizing solution can be directly treated without going through the water washing step. A compound having an image stabilizing function is added to the stabilizing liquid, such as an aldehyde compound represented by formalin, or a film 9 suitable for dye stabilization.
Examples include buffering agents for hydrogen and ammonium compounds. Further, in order to prevent the proliferation of bacteria in the liquid and to impart anti-mold properties to the photographic material after processing, the various disinfectants and anti-mold agents described above can be used.

Furthermore, surfactants, optical brighteners, and hardeners can also be added. In the processing of the photosensitive material of the present invention, when stabilization is performed directly without passing through a water washing step,
No. 8543, No. 58-14834, No. 60-2203
All known methods described in No. 45 and the like can be used.

In addition, it is also preferable to use chelating agents such as 1-hydroxyethylidene-1,1-diphosphonic acid and ethylenediaminetemethylenephosphonic acid, and magnesium and bismuth compounds! ! It's like that.

A so-called rinsing solution is also used as a washing solution or stabilizing solution used after desilvering treatment.

The preferred pH of the water washing step or stabilization step is 4 to 10, more preferably 5 to 8. The temperature can be set in various ways depending on the use and characteristics of the photosensitive material, but generally it is 15 to 45°C.
Preferably it is 20-40°C. Although the time can be set arbitrarily, a shorter time is preferable from the viewpoint of reducing processing time. Preferably 15 seconds to 1 minute 45 seconds, more preferably 30 seconds to 1 minute
It is minute 30 seconds. The smaller the amount of replenishment, the better from the viewpoints of running costs, reduced emissions, ease of handling, and the like.

The liquid used in the water washing and/or stabilization step can also be used in the previous step. An example of this is reducing the amount of waste liquid by reducing the overflow of washing water by using a multi-throw countercurrent system to flow into a bleach-fixing bath as a pre-bath, and replenishing the bleach-fixing bath with concentrated liquid.

The color photographic light-sensitive material of the present invention can be 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. 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 photosensitive emulsion layers contain a silver halide emulsion sensitive to each wavelength range, and dyes that are complementary colors to the sensitizing light - yellow for blue, magenta for green, and cyan for red.
By containing a so-called color coupler that forms a color, subtractive color reproduction can be performed. 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 structures having parts with different halogen compositions in a non-layered manner inside or on the particle surface (if it is on the surface of the particle, the edge of the particle , a structure in which portions of different compositions are joined on a corner or surface) can be appropriately selected and used. In order to obtain high sensitivity, it is more advantageous to use either of the latter than particles with a uniform structure, and it is also preferable from the viewpoint of pressure resistance. When silver halide grains have the above-mentioned structure, even if the boundaries between parts with different halogen compositions are clear boundaries, the boundaries may be unclear due to the formation of mixed crystals due to compositional differences. It is also possible to actively 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 preferably has a silver bromide content of at least 10 mol%, more preferably more than 20 mol%. These localized layers can be located inside the grains or on the edges, corners, or surfaces of the grain surfaces, and one preferred example is one in which they are epitaxially grown on a part of the corner of the grains.

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-mentioned 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 (Pau1Monta1, 1967), G, F, []uffinll
Photo-graphic E! LIIulsion
Che II listry (Focal Press
Publishing, 1966), V, L, Zelikman
Making and Coating by et at
Photographic Bmuldion (Fo
Cal Press, 1964). That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble antisalt with the soluble halogen salt may be any method such as one-sided mixing method, simultaneous mixing method, or a combination thereof. May be used. 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 PAg in a liquid phase in which silver halide is produced can be kept constant, that is, a so-called Chondrald double jet method can also be used. 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,
Salts such as copper and thallium, or iron, which is a group II element,
Examples include salts or complex salts of ruthenium, rhodium, palladium, osmium, iridium, platinum, and the like. 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-' to 10-2 mol 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 corner of page 18 of the specification of JP-A-62-215272.
The one described in the upper column of the 22nd purchase method is 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, F. M. Tfarmer) 1
etarocyclic compounds-Cya
nine dies and related com
pounds (John Wilay & 5ons
[New York, London] Publishing, 1964
2013). Examples of specific compounds and spectral sensitization methods are described in the above-mentioned Japanese Patent Application Laid-open No. 6
2-215272 specification, page 22, upper right column to 3rd page
The one described on page 8 is 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. Also good.

When the present invention is applied to a color photosensitive material, the color photosensitive material includes a yellow coupler, a magenta coupler, and a cyan coupler that form yellow, magenta, and cyan colors respectively by coupling with an oxidized product of an aromatic amine color developer. is usually used.

The cyan coupler and magenta coupler preferably used in the present invention have the following binding margin % formula % (general formula (C-I) H general formula % formula %) general formula (M-I) R3 general formula % formula % ) In general formulas (C-I) and (C-II), R1,
R3 and R4 represent a substituted or unsubstituted aliphatic, aromatic or heterol group, R8, R3 and R6 represent a hydrogen atom, halogen atom, aliphatic group, aromatic group or acylamino group, R5 together with R2 It may also represent a group of nonmetallic atoms forming a nitrogen-containing 5-membered ring or 6-membered groove. L%
Y2 represents a hydrogen atom or a vine group that is released during a coppling reaction with an oxidized product of a developing agent. n represents O or 1.

R in general formula (C-II) is preferably an aliphatic group, such as a methyl group, ethyl group, propyl group, butyl group, pentadecyl group, tart-butyl group, cyclohexyl group, cyclohexylmethyl group, Examples include phenylthiomethyl group, dodecyloxyphenylthiomethyl group, butanamidomethyl group, and methoxymethyl group.

Preferred examples of the cyan coupler represented by (C-I) or (C-II) are as follows.

In general formula (C-I), preferable R1 is an aryl group,
A heterocyclic group, such as a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, an acylamino group, an acyl group,
More preferably, it is an aryl group substituted with a carbamoyl group, a sulfonamide group, a sulfamoyl group, a sulfonyl group, a sulfamide group, an oxycarbonyl group, or a cyano group.

- When R1 and R2 do not form a ring in the binding margin (C-I), R2 is preferably a substituted or unsubstituted alkyl group or aryl group, particularly preferably a substituted aryloxy-substituted alkyl group, and % Rff is preferably 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 the general formula (C-II), preferably Rs 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 the binding margin (C-II), R3 is more preferably an alkyl group having 2 to 15 carbon atoms, particularly preferably an alkyl group having 2 to 4 carbon atoms.

- Preferred R6 in the binding margin (C-n) is a hydrogen atom or a halogen atom, with a chlorine atom and a fluorine atom being particularly preferred. - Preferred Yl and Y2 in binding margins (C-I) and (C-n) are a hydrogen atom, a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group, and a sulfonamide group, respectively.

In the general formula (M-I), R7 and R represent an aryl group, R6 represents a hydrogen atom, an aliphatic or aromatic acyl group, an aliphatic or aromatic sulfonyl group, and Y represents a hydrogen atom or Represents a leaving group.

Aryl group (preferably phenyl group) of R1 and R,
The substituents allowed for are the same as the substituents allowed for the substituent R, and when there are two or more substituents, they may be the same or different. R8 is preferably a hydrogen atom, an aliphatic acyl group or a sulfonyl group, particularly preferably a hydrogen atom.

Preferred Y is of the type that leaves off with either sulfur, oxygen or nitrogen atoms, for example as described in US Pat. No. 4.3.
Particularly preferred are sulfur atom separation types as described in No. 51□897 and International Publication No. WO88104795.

In general formula (M-II), R1° represents a hydrogen atom or a substituent. Y represents a hydrogen atom or a leaving group, and particularly preferably a halogen atom or an arylthio group. Za,
Zb# and Zc are methine, substituted methine, :N- or -N
)I-, one of the Za-1 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. When forming a dimer or more multimer with La or Y4, also Za.

When zb or Zc is a substituted methine, this includes the case where the substituted methine forms a dimer or more multimer.

Among the pyrazoloazole couplers represented by the general formula (M-II), imidazo (1,2 -bl pyrazoles are preferred;
Pyrazolo I as described in U.S. Pat. No. 4,540,654:
1.5-b) (1,2,4] ) riazoles are particularly preferred.

In addition, a branched alkyl group as described in JP-A No. 61-65245 is directly connected to the 2.3 or 6-position of the pyrazolotriazole ring to create a pyrazolotriazole coupler, which is described in JP-A No. 61-65246. pyrazoloazole couplers containing a sulfonamide group in the molecule, pyrazoloazole couplers having an alkoxyphenylsulfonamide ballast group as described in JP-A No. 147254, and European Patent Publication No. 226. It is preferred to use pyrazolotriazole couplers having an alkoxy group or aryloxy group at the 6-position, such as those described in No. 849 and No. 294.785.

General formulas (C-[), (C-■), (M-1) and (M
Specific examples of couplers represented by -■) are listed below.

(C-1) 1 (C-4) α (C-7) (C-9) (C-13) (C-14) (C-15) (C-17) (C-18) (C-19) (C-20) (C-21) (C-22) lls (M-1) (M-2) Ko I (M-6) Ko L (M-7) (M-8) CH.

Ko CH.

The above-mentioned couplers represented by (C-r) to (+-U) are usually present at 0.1 to 1.0 mol per 1 mol of silver halide in the silver halide emulsion layer constituting the photosensitive layer. , preferably 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-ice 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-ice 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 point organic solvent and/or a water-insoluble polymer compound having a refractive index (25°C) of 1.5 to 1.7.

As a high boiling point organic solvent, preferably the following general formula () () High boiling point organic solvents represented by It will be done.

General formula () % formula % General formula (B) W+-CDOL General formula () % formula %) (In the formula, wl, w2 and - are each substituted or unsubstituted alkyl group, cycloalkyl group, alkenyl group,
Represents an aryl group or a heterocyclic group;
l Also C5-I11. , nlt is an integer from 1 to 5, and when n is 2 or more, stomach may be the same or different from each other, - in the binding margin (E), ! 11 and I
12 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 in cases other than -Tsuriyo (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
-Page 137 bottom right of published specification No. 215272--14
The purchase method is listed on the upper right corner 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,
Cyclization and alkylation of spirochromans, p-alkoxyphenols, hindered phenols, mainly bisphenols, gallic acid derivatives, methylenedioxybenzenes, aminophenols, hindered amines, and 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,
2.418.613, 2.700.453, 2.701, 197, jK2.728.65
No. 9, No. 2.732.300, No. 2.735.7
No. 65, No. 3.982.944, No. 4,430,
425, British Patent No. 1.363.921, U.S. Patent No. 2,710.801, U.S. Pat. U.S. Patent No. 3.432.3
No. 00, No. 3.573.050, No. 3.574.
No. 627, No. 3.698゜909, No. 3.764
．． No. 337, JP-A-52-152225, etc., and spiroindanes are described in U.S. Patent No. 4.360.589, p.
-Alkoxyphenols are U.S. Patent No. 2.735.7
No. 65, British Patent No. 2.066, 975, JP-A-59
-10539, Japanese Patent Publication No. 57-19765, etc., and hindered phenols are disclosed in U.S. Pat.
No. 52-72224, U.S. Pat. No. 4.228.
No. 235 and Japanese Patent Publication No. 52-6623, etc., and gallic # derivatives, methylenedioxybenzenes, and aminophenols are disclosed in U.S. Patent Nos. 3.457.079 and 4, respectively.
．． No. 332.886, Japanese Patent Publication No. 56-21144, etc., disclose hindered amines (US Pat. 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, Japanese Patent Publication No. 51-1420, Japanese Patent Publication No. 1983
-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, and British Patent No. 2.027.731 (^), 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. No. 3,406,070, U.S. Pat. 271.307) can be used. An ultraviolet-absorbing coupler (for example, an α-naphthol-based cyan dye-forming coupler), an ultraviolet m-absorbing polymer, or the like 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 ki (in trioctyl phosphate at 80°C) with p-anisidine of 1. O1/1ol-9ec~lX10-
It is a compound that reacts in the range of ' 1 /mol-sec.

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

When R2 is larger than this range, the compound itself becomes unstable and may react with gelatin or water and decompose. On the other hand, if R2 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 formula (FI) or (FIG).

General formula (FI) R1-(^), -X General formula (FIG) R2-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 (Fn). Here, R1, XSY, and R2 or B may be bonded to 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 (FI) 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, more preferable compounds (G) that chemically bond with the oxidized aromatic amine developing agent remaining after color development processing to produce a chemically inert and colorless compound include the following - Tsuzuriyo ( 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. - Compounds represented by GI (Z) have Pearson's nucleophilicity "CLI value (R
, G., Pearson, et al., J.A.
a+.

Chew, Sac, 90.319 (1968))
is preferably 5 or more, or a group derived therefrom.

-Specific examples of compounds represented by G I
No. 3048, No. 62-229145, Patent Application No. 1983-1
Those described in European Patent Publication No. 36724, European Patent Publication No. 62-214681, European Patent Publication No. 298321, European Patent Publication No. 277589, etc. are preferred.

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

In the photosensitive material produced using the present invention, water-soluble dyes or dyes that become water-soluble through photographic processing may be added to the hydrophilic colloid layer as filter dyes or for various purposes such as preventing irradiation and Halley radiation. May contain. 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. Details of the method for producing gelatin are described in The Macromolecule Chemistry of Gelatin, written by Arthur Vuis (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 is best to thoroughly knead a white pigment in the presence of a surfactant, and also coat the surface of the pigment particles with
It is preferable to use one treated with a tetrahydric alcohol.

The occupied area ratio (%) of white pigment fine particles per defined unit area is calculated by dividing the observed area into adjoining unit areas of 6 tm x 6- and projecting onto that unit area. It can be determined by measuring the occupied area ratio (%) (R1) of the fine particles. The coefficient of variation of the occupied area ratio (%) can be determined by the ratio s/H of the standard deviation S of Rt to the average value (R) of R1. 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."

<Example> Next, the present invention will be explained in detail based on examples.

Example 1 A multilayer color photographic paper sample (1) having the layer structure shown below was prepared on a paper support which was laminated on both sides with polyethylene and whose surface was subjected to corona discharge treatment. The coating solution was prepared as follows.

Preparation of coating solution for the first layer: 60.0 g of yellow coupler (Y-6) and 28.0 g of anti-fading agent (Cpd-1), 150 cc of ethyl acetate, 1.0 cc of solvent (So 1v-3), and 1.0 cc of solvent (Sol
v-4) Add and dissolve 3.0 cc, add this solution to 450 cc of a 10% gelatin aqueous solution containing sodium dodecylbenzenesulfonate, and then disperse with an ultrasonic homogenizer. A first layer coating solution was prepared by mixing and dissolving this in 420 g of a silver chlorobromide emulsion (90.7 mol % bromide) containing a sensitizing dye.

Coating solutions for the second to seventh layers were also prepared in the same manner as the coating solution for the first layer. The gelatin hardening agent for each layer is 1.2-
Bis(vinylsulfonyl)ethane was used.

The following spectral sensitizing dyes were used in each layer.

Blue-sensitive emulsion layer; anhydro-5,5'-dichloro-3,
3'-disulfoethyl thiacyanine hydroxide green-sensitive emulsion layer: anhydro-9-ethyl-5,5'-diphenyl-3,3'-disulfoethyl oxacarbocyanine hydroxide red-sensitive emulsion layer; 3.3'- diethyl-5-methoxy-9
, 11-neopentylthiazidylupocyanine iodide The following substances were used as stabilizers for each emulsion layer.

In addition, the following dyes were used as irradiation prevention dyes.

[3-carboxy-5-hydroxy-4-(3-(3-
Carboxy-5-year-old xo-1-(2,5-bisulfonatophenyl)-2-pyrazolin-4-ylidene)-1-propenyl)-1-pyrazolyl]benzene-2,5-disulfonate-disodium salt N,N' -(4,8-dihydroxy-9,10-dioxo-3,7-cissulfonatoanthracene-1,5-diyl)bis(aminomethanesulfonate)-tetrasodium salt [3-cyano-5-hydroxy-4- (3-(3-cyano-5-oxo-1-(4-sulfonatophenyl)-
2-pyrazolin-4-ylidene)-1-pentanyl)-
1-pyrazolyl]benzene-4-sulfonate-sodium salt (layer structure) The composition of each layer is shown below. The numbers represent the coating amount (g/g). The silver halide emulsion represents the coated amount in terms of silver.

Support Paper support laminated on both sides with polyethylene and corona discharge treated on the surface Layer (blue sensitive layer) Silver chlorobromide emulsion described above (AgBr O, 7 mol χ, cubic, average grain size 0.9 μm) 0 .33 Gelatin 1.80 Yellow coupler (Y-6) 0.60 Anti-fading 1 (Cpd-1) 0.28 Solvent (Solv-3) 0.0
1 Solvent (Solv-4) 0
．． 03 Second layer (color mixing prevention agent) Gelatin 0°80 Color mixing prevention agent (Cpd-2) 0.055 Solvent (Solv-1) 0.0
3 Solvent (Solv-2) 0
．． 15 Third layer (green-sensitive layer) Above-mentioned silver chlorobromide emulsion (AgBr 0.7 mol χ, cubic, average grain size 0.45 tt m) 0
．． 20 gelatin 1.86 magenta coupler (8xM) Anti-fading agent (Cpd-3) Anti-fading agent (Cpd-4) Solvent (Satmer 1) Solvent (Salt-2> Fourth layer (color mixing prevention layer) Gelatin color mixing prevention agent (Cpd-2) Ultraviolet absorber (tlV-1) Ultraviolet absorber (IJV-2) Solvent (Satmer 1) Solvent (Solmer 2) Fifth layer (red sensitive layer) The above-mentioned silver chlorobromide emulsion (8 gBr Average particle size 0.5JllI) Gelatin cyan coupler (BxC-1) Cyan coupler (BxC-2) Antifading agent (Cpd-1) Solvent (Solv-1) 0.27 0.17 0.10 0.2 0 .03 1.70 0, 065 0.45 623 Q, 05 0.05 4 mol%, cube, 0.2S 1.80 0.26 0.12 0.20 0.16 Solvent (Soly-2) Color development promotion Agent (Cpd-5) Sixth layer (ultraviolet IIi absorption layer) Gelatin ultraviolet absorber ([IV-1) Ultraviolet absorber (UV-2) Solvent (Solv-1) Solvent (SOTV-2) Seventh layer ( Protective layer) Gelatin 0.09 0.15 0.70 0.26 0.0T O030 0.09 1,07 (8xM) Magenta coupler 7-chloro-6-ituprobyl-3- (3-[(2-
butoxy-5-tart-octyl)benzenesulfonyl]propyl)-IH-pyrazolo[5,1-C1-1,
2,4-) Riazole (BxC-1) Cyan coupler 2-pentafluorobenzamide-4-chloro-5(2
-(2,4-di-tart-amylphenoxy)-3-
Methylbutyramidephenol (BxC-2) Cyan coupler 2,4-dichloro-3-methyl-6-[α-(2,4-
tart-amylphenoxy)butyramide]phenol (Cpd-1) anti-fade agent -(CH,-C)I)-=- C0NHC,H, ■ Average molecular weight 80.000 (Cpd
-2) Color mixing inhibitor 2.5-di-tart-octylno-hydroquinone (C
pd-3) Anti-fade agent 7.7'-dihydroxy-4,4,4',4'-tetramethyl-2,2'-spirochroman (Cpd-4) Anti-fade agent N-(4-dodecyloxyphenyl) -Morpholine (Cpd-5) color accelerator p-(p-)luenesulfonamide) phenyl-dodecane (Solv-1) solvent di(2-ethylhexyl) phthalate (SOIV-2) solvent dibutyl phthalate (Solv-3) solvent Di(i-nonyl)phthalate (Solv-4) solvent N, N-diethylcarbonamide-methoxy-2,
4-di-t-amylbenzene (UV-1) UV absorber 2-(2-hydroxy-3,5-di-tert-amylphenyl)benzotriazole (UV-2) UV absorber 2-(2-hydroxy- 3,5-Di-tert-butylphenyl) benzotriazole
2) to (5) were created.

Table 1 *Yellow coupler A for comparison is Y-6 is a compound in which X is -C1.

Using a sensitometer (FWH model manufactured by Fuji Photo Film Co., Ltd., color density of light source: 3200 K) on the coating sample, by appropriately changing the filter density of blue, green, and red, color development at a density of 1.0 was determined. , I performed gradation exposure under conditions that turned the image into a grayish gray. At this time, the exposure was carried out at an exposure time of 1/10 seconds, and the following processing solution before continuous processing was used as the processing solution.

The exposed sample was processed using a paper processing machine.
In the following processing steps, continuous processing was performed until twice the tank capacity of the color developer was replenished.

The composition of the replenisher is shown in Table 2. The composition of the replenisher was determined to be such that the concentration of the chemicals used in the preparation in the tank solution was the same for all solutions.

Basic science and engineering! i! Jl Toyorei I light 19? Solution 1 color development 38℃ 45 seconds See Table 2 41 Bleach fixing 30-36℃ 45 seconds 61ml 4g water washing ■ 30-37℃ 30 seconds -211 Water washing
■ 30~37℃ 30 seconds -22 water washing ■
30~37℃ 30 seconds 364I1124! Drying 7
0 to 85°C for 60 seconds Replenishment amount per 1 nf of photosensitive material The composition of each treatment solution is as follows.

Sadate Niri 1 hill [Tank liquid] water Ethylenediamine-N,N.

N', N', tetramethidinephosphonic acid triethanolamine sodium chloride potassium bromide sodium carbonate N-ethyl-N-(β-methanesulfonamidoethyl)-3-methyl-4-aminoaniline sulfate diethylhydroxylamine fluorescence Brightener (WHITEX-4 manufactured by Sumitomo Chemical) Add water and p) I (25°C) 001d 3, 0g 8, 0g 4, 1g 0.03g 5g 80g 4, 2g 1.0g GOOd 10.05 Above continuous treatment Blue, green,
The density was measured through a red filter, and changes in sensitivity and gradation before and after continuous processing were investigated. Regarding the sensitivity change, the change in exposure amount required to obtain a density of 0.5 before and after continuous processing ΔS0. ．． For the gradation change, it is expressed as
The difference in exposure amount required to give a density of 1.0 and 0°5 (Δ
It was expressed as Δ(IogE) before and after continuous treatment of logE). In other words, when ΔS@,5 is positive, it indicates that the continuous processing has resulted in a high sensation, and when it is negative, it indicates a low sensation.
When ogE) is positive, it indicates that the gradation has become softer due to continuous processing, and when it is negative, it indicates that the gradation has become higher.

The results are shown in Table 3, however, changes in sensitivity gradation are shown only for the blue-sensitive layer.

As is clear from Table 3, only in the present invention, even when continuously processed with a color developer with a low replenishment amount of 200111 or less per m2 of light-sensitive material, the sensitivity and gradation changes of the blue-sensitive layer are extremely small. I understand that.

Furthermore, it was confirmed that the yellow coupler of the present invention has excellent color reproducibility of so-called lemon yellow.

Example 2 Samples (7) to θ0 were prepared by changing the yellow coupler in sample (1) used in Example 1.

These samples were exposed, processed, and measured in the same manner as in Example 1, and changes in sensitivity and gradation before and after continuous processing were examined. However, as for the replenisher, 0 of the replenisher used in Example 1 was used, and continuous processing was performed with a replenishment amount of 100 m.

The results are shown in Table 5. Regarding changes in sensitivity and gradation, only changes in the blue-sensitive layer are shown.

Table 4 Comparison coupler B.

C is Y-1, respectively -2 is a compound where X is -C2.

LooIl only in the present invention in Keyaki that is clear from Table 5 No. 5 wheat
It can be seen that the changes in sensitivity and gradation during continuous processing with a low replenishment color developer of 1 were extremely small. These samples of the present invention also had excellent color reproducibility.

(Effect of the invention) The present invention effectively suppresses changes in sensitivity and gradation that occur when a color photographic material using a yellow coupler with excellent color reproducibility is continuously processed with a color developer with a small amount of replenishment. This problem was resolved and it became possible to switch to color printing, which has stable photographic properties.

This has made it possible to stably obtain color prints with excellent color reproducibility using a processing method that saves resources and reduces pollution.

Claims (4)

[Claims] (1) A silver halide color photographic light-sensitive material having at least one blue-sensitive emulsion layer, one green-sensitive emulsion layer, and one red-sensitive emulsion layer on a support, and containing at least one aromatic primary amine color developing agent. In a color image forming method in which processing is performed using a color developer, the blue-sensitive emulsion layer contains at least one yellow coupler represented by the following general formula (I), and the silver halide emulsion on the support is Silver halide color photographic light-sensitive materials with a total coating amount of 0.78 g/m^2 or less in terms of silver are continuously coated with a color developer whose replenishment amount is 200 ml or less per 1 m^2 of silver halide color photographic light-sensitive materials. A color image forming method characterized by processing. General formula [I] [In the formula, R_1 is an aryl group or a tertiary alkyl group,
R_2 is a fluorine atom, alkyl group, aryl group, alkoxy group, aryloxy group, dialkylamino group, alkylthio group, or arylthio group, R_3 is a group that can be substituted on the benzene ring, and X is a hydrogen atom or an aromatic group. l represents a group that can be separated by a coupling reaction with an oxidized product of a primary amine developer, and l represents an integer of 0 to 4, respectively. However, when l is plural, the plural R_3 may be the same or different. ] (2) In the color photographic light-sensitive material, the total amount of silver halide emulsions contained in the green-sensitive emulsion layer and the red-sensitive emulsion layer is 0.50 g/m^2 or less as a silver equivalent coating amount (1) The color imaging method described. (3) In the yellow coupler represented by the above general formula (I), l is 1, and R3 is a halogen atom,
Alkyl group, aryl group, alkoxy group, aryloxy group, alkoxycarbonyl group, aryloxycarbonyl group, carbonamide group, sulfonamide group, carbamoyl group, alkylsulfonyl group, arylsulfonyl group, ureido group, sulfamoylamino group, Alkoxycarbonylamino group, nitro group, heterocyclic group, cyano group,
The color image forming method according to claim 1, wherein the group is an acyl group, an acyloxy group, an alkylsulfonyloxy group, or an arylsulfonyloxy group. (4) General formula ( I
2. The color image forming method according to claim 1, wherein the structure of at least one of the yellow couplers in (1) is defined by the following general formula (II). General Formula (II) ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ {In the formula, R_4 represents an alkyl group, cycloalkyl group, acyl group, or aryl group, and R_5 represents a group that can be substituted on the benzene ring. n represents 0 or 1. R_6 represents an organic group containing one bonding group having a carbonyl or sulfonyl unit, and J represents ▲a mathematical formula, a chemical formula, a table, etc.▼or ▲a mathematical formula, a chemical formula, a table, etc.▼(R_7 is a hydrogen atom, an alkyl represents a group, an aryl group, or a heterocyclic group.)R
_1 and X are the same as in general formula (I). }