JPH03211548A - Processing method for silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To stabilize photographic characteristics by processing a silver halide color photographic sensitive material contg. a yellow coupler represented by a specified formula in the blue-sensitive layer with a specified color developing soln. CONSTITUTION:A silver halide color photographic sensitive material contg. a silver chloride-rich silver halide emulsion having >=90mol% silver chloride content and a yellow coupler represented by formula I in the blue-sensitive layer is processed with a color developing soln. contg. 3X10<-2>-1.5X10<-1>mol/l chlorine ions. In the formula I, R1 is aryl or tert. alkyl, R2 is F, alkyl, aryl, etc., R3 is a group substitutable on the benzene ring, X is H or a group releasable by a coupling reaction with the oxidized body of an arom. prim. amine developing agent and l is an integer of 0-4. A photographic characteristic stabilizing effect can be produced.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to a method for processing a silver halide color photographic light-sensitive material, and more specifically, it relates to a method for processing a silver halide color photographic light-sensitive material, and more specifically, it uses a high-silver chloride silver halide photographic light-sensitive material, and a development processing method with excellent stability.

(Prior art) In recent years, in the photographic processing of color photographic materials,
: It has been desired to shorten the processing time to shorten delivery times and reduce laboratory work.

Increasing the temperature and increasing the amount of replenishment are common methods for shortening the time of each treatment step, but many other methods have been proposed, such as increasing stirring or adding various accelerators.

In particular, for the purpose of speeding up color development and/or reducing the amount of replenishment, color photographic materials containing silver chloride emulsion in place of the conventionally widely used silver bromide thread emulsion or silver iodide emulsion are processed. How is it known? for example,
International Publication No. WO 3704534 describes a method for rapidly processing a high silver chloride silver halide color photographic light-sensitive material with a color developer substantially free of sulfite ions and benzyl alcohol.

However, when developing according to the above method, there are large fluctuations in photographic characteristics (especially sensitivity changes and gradation changes) due to continuous processing and aging of the developer, which poses a major problem in practice. There was found.

For the purpose of stabilizing the photographic properties of high-silver chloride color light-sensitive materials, JP-A-63-106655 discloses that high-silver chloride light-sensitive materials containing hydroxylamine compounds and chloride at a predetermined concentration or higher are used as color light-sensitive materials. A method of processing with a developer is disclosed.

However, although the stabilizing effect of photographic properties by the above method is recognized for cyan and magenta color development, fluctuations in the photographic properties (especially sensitivity and gradation of low exposure areas) of the yellow coloring layer further increase. It was found that the above problem was not solved.

(Problems to be Solved by the Invention) Therefore, the first object of the present invention is to use a high-silver chloride color photographic light-sensitive material, to develop it quickly and with a maximum of 1 degree (maximum 1 degree), and to stabilize the photographic properties. The purpose is to provide a method.

(Means for Solving the Problems) An object of the present invention is to provide a method for processing a silver halide color photographic material with a color developer containing at least one type of aromatic primary amine color developing agent. A silver chloride color light-sensitive material having a high silver chloride silver halide emulsion consisting of the above silver chloride and a yellow coupler represented by the following general formula (I) in the blue-sensitive layer was prepared by adding chloride ions to 3 x 10-2 to 3 x 10-2. This was achieved by a method for processing a silver halide color photographic light-sensitive material, which is characterized by processing with a color developer containing 1.5XIO'mol/l.

General formula [■] [In the formula, R1 is an aryl group or a tertiary alkyl group,
2 is a fluorine atom, an alkyl group, an aryl group, an alkoxy group, an arylthio group, a dialkylamino group, an alkylthio group, or an arylthio group, R5 is a group that can be substituted on the benzene ring, and X is a hydrogen atom or an aromatic group. 1 represents a group that can be separated by a coupling reaction with an oxidized product of a class amine developer, and l represents an integer of O to 4, respectively. However, when l is plural, the plural R2's may be the same or different. ] As a result of various studies aimed at stabilizing photographic properties, the present inventors found that the yellow coupler of general formula (1) and the chloride ion concentration of 3×10 −2 to 1.5×10 −′ mol/1 It has been found that by using a color developer in combination, stabilization of photographic properties can be achieved even when using a high-silver chloride photosensitive material. The effect of the combination of the yellow coupler of the present invention and chloride ions was completely unexpected and surprising.

In the present invention, the chloride ion concentration of the color developer is 3.
It is necessary that the amount is between X10-2 and 5X10-' mol/l. Preferably 4×10−2 to 1.3×1O−
'mol/l, more preferably 5 x 10-2 to lX
10-'mol/l.

If the chloride ions are less than 3X10-' mol/l,
The variation in photographic properties is large, and the object of the present invention cannot be achieved. Chlorine ion is 1.5 X I O mol/I!
If the amount is more than that, the maximum concentration will be lowered, speediness will be impaired, and the purpose of the present invention will not be achieved.

Here, chlorine ions may be added directly to the color developer, or may be eluted from the photosensitive material in the developer. When eluting from the amount of photosensitive material, it is preferable to reduce the amount of replenishment of the color developer in order to achieve the concentration of the present invention, and to regenerate and reuse the color developer. Further, when eluting from the light-sensitive material, it may be supplied from the emulsion or from a source other than the emulsion.

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

It may also be supplied in the form of a salt-resistant fluorescent brightener added to the developer.

In the present invention, the light-sensitive material must have a high silver chloride emulsion containing 90 mol % or more of silver chloride in the blue layer. From the viewpoint of rapidity and reduction in the amount of color developer replenishment, it is more preferable that it consists of 95 mol% or more of silver chloride,
Particularly preferred is 98% or more. Silver chloride content is 90 mol%
If the amount is less than that, the maximum concentration will be lowered, speediness will be impaired, and the object of the present invention will not be achieved.

In the present invention, the photosensitive material must contain at least one yellow coupler represented by general formula (1).

The yellow coupler represented by the general formula (1) will be explained in detail.

In general formula (1), R1 preferably has 6 carbon atoms
~24 aryl groups (e.g. phenyl, p-tolyl, o
-tolyl, 4-methquinophenyl, 2-methoxyphenyl, 4-butoxyphenyl, 1-octyloquinphenyl, 4-hexadecyloxyphenyl, l-naphthyl)
or a tertiary alkyl group having 4 to 24 carbon atoms (for example, t
-butyl, t-pentyl, t-hexyl, l, l,
3. 3-tetramethylbutyl, ■-adamantyl, 1. 1dimethyl-2-chloroethyl, 2-phenoxy2-propyl, bicycloC2,2,2]octane-1
-il).

In general formula: I], R is preferably a fluorine atom,
Alkyl groups having 1 to 24 carbon atoms (e.g. methyl, ethyl, isopropyl, t-butyl, ncrobentyl, n-
octyl, n-hexadecyl, benzyl), aryl groups having 6 to 24 carbon atoms (e.g. phenyl, 1)-tolyl, o-tolyl, 4-methoxyphenyl), 1 carbon atom
~14 alkoxy groups (e.g. methquine, ethoxy, butoxy, n-octyloxy, n-tetradecyloxy, hensyloxy, methquinethoxy), 6 carbon atoms
~24 arylthio groups (e.g. phenoxy, p-tolyluoquine, O-tolyluoquine, p-methoxyphenoxy, p-dimethylaminophenoxy, m-pentadecylphenoquine), dialkylamino groups having 2 to 24 carbon atoms (e.g. dimethylamino , diethylamino, pyrrolidino, piperidino, morpholino), alkylthio groups having 1 to 24 carbon atoms (e.g. methylthio, butylthio, n-octylthio, n-hexadecylthio) or arylthio groups having 6 to 24 carbon atoms (e.g. phenylthio, 4-
Methoxyphenylthio, 4t-butylphenylthio, 4
-dodecylphenylthio).

In general formula [1], R5 is preferably a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), an alkyl group having 1 to 24 carbon atoms (e.g. methyl, t-butyl, n-dodecyl), carbon Aryl groups having 6 to 24 atoms (e.g. phenyl, p-tolyl, p-totyloxyphenyl), alkoxy groups having 1 to 24 carbon atoms (e.g. methoxy, n-butoxy, n-octyloxine, n-
tetradecyloxy, benzyloxy, methoxyethquine), aryloxy groups having 6 to 24 carbon atoms (e.g. fenoquine, pt-butylphenoquino, 4-butoxyphenoxy), alkoxycarbonyl groups having 2 to 24 carbon atoms [For example, ethoxycarbonyl, dodecyloxycarbonyl, l-(dodecyloxycarbonyl)ethoxycarbonyl], aryloxycarbonyl groups having 7 to 24 carbon atoms (for example, phenoxycarbonyl, 4-t-octylphenoxycarbonyl, 2,4- di-t-pentylphenoxycarbonyl), carbonamide groups having 1 to 24 carbon atoms [e.g. acetamide, pivaloylamino,
Benzamide, 2-ethylhexanamide, tetradecanamide, 1(2,4-di-t-pentylphenoxy)
butanamide, 3-(2,4-di-t-pentylphenoxy)butanamide, 3-dodecylsulfonyl-2-methylpropanamide], sulfonamide groups having 1 to 24 carbon atoms (e.g. methanesulfonamide, p-toluenesulfone amide, hexadecanesulfonamide), carbamoyl groups having 1 to 24 carbon atoms (e.g. N-methylcarbamoyl, N-tetradecylcarbamoyl, N,N-dihexylcarbamoyl, N-octadecyl-N-methylcarbamoyl, N-phenylcarbamoyl) Alkylsulfonyl group having 1 to 24 carbon atoms (e.g. methylsulfonyl, benzylsulfonyl, hexadecylsulfonyl)
, an arylsulfonyl group having 6 to 24 carbon atoms (e.g. phenylsulfonyl, p-tolylsulfonyl, p-dodecylsulfonyl, p-methoxysulfonyl), a ureido group having 1 to 24 carbon atoms (e.g. 3-methylureido,
3-phenylureido, 3,3-dimethylureido, 3-
tetradecylureido), sulfamoylamino groups having 0 to 24 carbon atoms (e.g. N, N-dimethylsulfamoylamino), alkoxycarbonylamino groups having 2 to 24 carbon atoms (e.g. methoxycarbonylamino, isobutoxycarbonyl), amino, dodecyloxycarbonylamino), nitro group, heterocyclic group having 1 to 24 carbon atoms (e.g. 4-pyridyl, 2-thienyl, phthalimide,
octadenolsuccinimide), cyanide groups, acyl groups having 1 to 24 carbon atoms (e.g. acetyl, benzoyl, dodecanoyl), annyloxy groups having 1 to 24 carbon atoms (
(e.g. acetoxy, benzoyloxy, dodecanoyloxy), alkylsulfonyloxy groups having 1 to 24 carbon atoms (e.g. methylsulfonyloxy, heisubylsulfonyloxy) or arylsulfonyloxy groups having 6 to 24 carbon atoms (e.g. p -toluenesulfonyloxy, p-dodecylphenylsulfonyluoquine).

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

In the general formula CIE, X is preferably a group (referred to as a leaving group) that can be separated by a coupling reaction with an oxidized product of an aromatic primary amine developer, and specifically a halogen atom (fluorine, chlorine, bromine, etc.). , iodine), carbon number 1 to 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), anluoxy 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, l-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 condensed heterocycle, examples of which include scunnimide, maleimide, phthalimide, diglycolimide, pyrrole, pyrazole, imidazole,
1゜2.4-triazole, tetrazole, indole, benzopyrazole, benzimidazole, 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-virolin-5-one, 2-imidacillin-5 -one, indoline-2,3-dione, 2,6-
Cyoxypurine, parabanic acid, ■, 2゜4-triacyridine-3,5-dione, 2-pyridone, 4-pyridone,
Examples include 2-pyrimidone, 6-pyridazone, 2-pyrazone, etc., and these heterocyclic groups may be substituted. Examples of substituents include hydroxyl group, carboxyl group, sulfo group, amino group (e.g. amino, N-methylamino, N.

In addition to N-dimethylamine, N,N-diethylamino, anilino, pyrrolidino, piperidino, morpholino, there are the substituents listed as examples of R1 above.

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

Next, examples of substituents particularly preferably used in the present invention will be described for each of the above-mentioned substituents R, R1, R, and X.

In general formula [1), R1 is particularly preferably a 2- or 4-alkoxyaryl group (e.g. 4-methoxyphenyl, 4-butquinphenyl, 2-methoxyphenyl) or a t-butyl group; Most preferred.

In the general formula CII, R2 is particularly preferably a methyl group, an ethyl group, an alkoxy group, an aryloxy group or a dialkylamino group, most preferably a methyl group, an ethyl group, an alkoxy group, an aryloxy group or a dimethylamino group. .

In general formula [I], R1 is particularly preferably an alkoke group, a carbonamide group or a sulfonamide group.

In general formula C1), X is particularly preferably a heterocyclic group or an aryloxy group bonded to the coupling active position via a nitrogen atom.

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

General formula [11] In general formula [II], Z represents 0-C-5. Here, R4, Ri, Ro and Ro 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 Ro and R6 Hydrogen atom, alkyl group, aryl group, alkylsulfonyl group, arylsulfonyl group,
or represents an alkoxycarbonyl group, R1° and R
11 represents a hydrogen atom, an alkyl group or an aryl group. R and R11 may be combined with each other to form a benzene ring. R4 and R,, R, and R,, R, and R7 or R1
and R may be bonded to each other to form a ring (eg, cyclobutane, cyclohexane, cyclohebutane, cyclohexene, pyrrolidine, piperidine).

Among the heterocyclic groups represented by the general formula (If), particularly preferred are those represented by the general formula (III) in which Z is R or R.

is a heterocyclic group.

The total number of carbon atoms in the heterocyclic group represented by the general formula [■] is 2
~24, preferably 4-20, more preferably 5-1
It is 6. Examples of the heterocyclic group represented by general formula (I1) are succinimide group, maleimide group, phthalimide group, ]-methylimidazolidine-2,4-dione-3
-yl group, l-benzylimidazolidine-2,4-dione-3yl group, 5,5-tumethyloxazolidine-2°4-dione-3-yl group, 5-methyl-5-propyloxazolidine-2, 4-dione-3-yl group, 5.5-
trimethylthiazolicin-2,4-dione-3-yl group,
5,5-dimethylimidazolidine-2,4-dione-3
-yl group, 3-methylimidazolidinetrion-1-yl group, l, 2゜4-triacylidine-3,5-dione-
4-yl group, 1-methyl-2-phenyl-1,2,4-
triacylidin-3,5-dione-4-yl group, 1-benzyl-2-phenyl-1,2,4-triacylidin-
3,5-dione-4-yl group, 5-hexyloxy-1
-methylimidazolidine-2゜4-dione-3-yl group, l-benzyl-5-ethoxyimidazolidine-2,4
-dione-3-yl group, and ■-henn-5-dodenyloxyimidazoline-2,4-dione-3-yl group.

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

When X represents an aryloxy group, 4-carboquinphenoxy group, 4-methylsulfonylphenoquine group, 4-
(4-benzyloxyphenylsulfonyl) phenoxy group, 4-(4-hydroxyphenylsulfonyl) phenoxy group, 2-chloro-4-(3-chloro-4-hydroxyphenylsulfonyl) phenoxy group, 4-methoxycarbonylphenoquine group , 2-chloro-4-methoxycarbonylphenoxy group, 2-acetamido-4-methoxycarbonylphenoxy group, 4-isopropoquine carbonylphenoxy group, 4-cyanophenoxy7 group, 2-rN
-(2-hydroxyethyl)carbamoyl]phenoxy group, 4-nitrophenoxy group, 2,5-dichlorophenoxy group, 2,3゜5-trichlorophenoxy group, 4-methoxycarbonyl-2-methoxyphenoxy group, 4-(
3-carboxypropanamido) phenoxy group is the most preferred example.

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

When the coupler represented by the general formula C1) forms a multimer, a typical example is a single or copolymer of an addition polymer ethylenically unsaturated compound (yellow color-forming monomer) having a yellow dye-forming coupler residue. In this case, the multimer contains repeating units of the general formula [■], and has the general formula CI
One or more types of yellow color-forming repeating units represented by [1) may be contained in the polymer, and the copolymer may contain one or more non-color-forming ethylene type monomers as a copolymerization component. You can.

General formula [I[1] -11-CH.

■ In formula 10, R represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a chlorine atom, A represents -CONHCO〇- or a substituted or unsubstituted phenylene group, and B represents a substituted or unsubstituted alkylene group. group, phenylene group or aralkylene group, L is -CONH---NHCONH--N
) ICOO-1-NHCO--0CONH--NH--coo--oco--co---.

-3--3O, --NH3O2- or So, NH-. a, b, and c represent 0 or 1. Q is the general formula (
In the compound represented by I), 2 represents a detached yellow coupler residue.

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

Examples of non-color-forming ethylene monomers that do not couple with the oxidation products of aromatic-grade amine developers include acrylic acid,
α-Chloroacrylic acid, α-alkylacrylic acid (e.g. methacrylic acid, etc.) Amides or esters derived from these acrylic acids (e.g. acrylamide, methacrylamide, n-butylacrylamide, t-
Butyl acrylamide, diacetone acrylamide, methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, t-butyl acrylate, 1so-butyl acrylate, 2-ethylhequinyl 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 (e.g. styrene and its derivatives, e.g. vinyltoluene, divinylhensen, vinylacetophenone and sulfostyrene), itaconic acid, ntraconic acid, crotonic acid, vinylidene chloride, vinyl alkyl ethers (e.g. vinyl ethyl ether),
Maleic acid ester, N-hinyl-2-pyrrolidone,
Examples include N-vinyl bilysine and 2- and -4-vinyl pyridine.

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

As is well known in the field of polymer couplers, the general formula JIII
] The ethylenically unsaturated monomer to be copolymerized with the vinyl monomer corresponding to The agent can be selected so as to favorably influence its compatibility with, for example, seratin, its flexibility, thermal stability, etc.

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

U.S. Patent No. 3,45 describes a method for emulsifying and dispersing a lipophilic polymer coupler in an aqueous solution of seratin in the form of latex.
No. 1,820, and U.S. Pat. No. 4,08 for emulsion polymerization.
The methods described in No. 0,211 and No. 3,370.952 can be used.

Specific examples of the yellow dye-forming couplers R3 and X represented by the general formula [11] are shown below, but the present invention is not limited thereto.

A specific example of X is shown below.

(I) (2) (3) (4) (5) (6) (7) (9) (I1) (I2) (8) (I3) (I4) (I5) (I7) H3 (I8) (20) (21) (22) (23) (24) A specific example of R is shown below.

(25) C6H13 (36) (CH1)tCI(CHtCt4-t (37) CH.

,H□ -N)ICOC)IzC)ICOOCH! -HH5Oz
C+ zFIzs-n (3 days) (39) (41) CHI -COOC+ Jts -COOCRCOOC tlzs -CONHC+tHx* (42) (43) (44) -CON)I(CHx)sOc+Jzs-NHCOC+
5Hz (47) (48) Specific examples of the yellow dye-forming coupler represented by the general formula (I) 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 light-sensitive material is 1X10-' mol-10-2 mol, preferably 1
Xl0-' mole to 5X10-' mole, more preferably 2
xto-' moles to lO-' moles.

The color developer used in the present invention will be explained in detail.

In the present invention, the color developer contains 3X10 bromide ions.
-' to lX1O-' mole/1 is preferably contained from the viewpoint of preventing fluctuations in photographic properties. 5×10-5~5X1
Particularly preferred is 0-' mol/l.

In the present invention, in terms of processing stability during continuous processing,
It is preferable that the color developer does not substantially contain sulfite ions, but in order to suppress the deterioration of the developer, do not use the developer for a long time, use a floating pig to suppress the effects of air oxidation, or Physical means such as reducing the opening degree of the bath can be used, and chemical means such as suppressing the developer temperature or adding an organic preservative can be used. Among these, the method using an organic preservative is advantageous in terms of simplicity.

The organic preservative according to the present invention refers to any organic compound that reduces the deterioration rate of an aromatic primary amine color developing agent when added to a processing solution for a color photographic light-sensitive material. In other words, organic compounds that have the function of preventing color developing agents from being oxidized by air, etc., include hydroxylamine derivatives (excluding hydroxylamine; the same applies hereinafter), hydroxamic acids, hydrazines, hydrazides, phenols, α-hydroxyketones, α-aminoketones, sugars, monoamines, diamines, polyamines, quaternary ammonium salts, nitroxy radicals,
Particularly effective organic preservatives include alcohols, oximes, diamide compounds, and fused ring amines. These are Japanese Patent Application No. 61-147823 and Japanese Patent Application No. 61-1735.
No. 95, No. 61-165621, No. 61-18861
No. 9, No. 61-197760, No. 61-186561
No. 61-198987, No. 61-201861, No. 61-186559, No. 61-170756,
No. 61-1.88742, No. 61188741, U.S. Patent No. 3,615,503, U.S. Patent No. 2,494,903
No., JP-A No. 52-143020, JP-A No. 48-304
It is disclosed in No. 96, etc.

Regarding the preferred organic preservative, its general formula and specific compounds are listed below, but the present invention is not limited thereto.

In addition, the amount of the following compounds added to the color developing solution is 0.00
It is desirable to add it at a concentration of 5 mol/β to 0.5 mol/l, preferably 0.03 mol/1 to 0.1 mol/l.

Particularly preferred is the addition of hydroxylamine derivatives and/or hydrazine derivatives.

The hydroxylamine derivative is preferably one represented by the following general formula (A-1).

General formula (A-1) R11N R+1 CH In the formula, R11, R1! represents a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkenyl group, an unsubstituted or substituted aryl group, or a heteroaromatic group. R'' and Rt2 do not become hydrogen atoms at the same time, and may be linked to each other to form a heterocycle with a nitrogen atom.The ring structure of the heterocycle is a 5- to 6-membered ring, with carbon atoms , hydrogen atoms, halogen atoms, oxygen atoms, nitrogen atoms, sulfur atoms, etc., and may be saturated or unsaturated.

It is preferable that R11 and R11 are an alkyl group or an alkenyl group, and the number of carbon atoms is preferably 1 to 10, particularly 1 to 10.
5 is preferred. The nitrogen-containing heterocycle formed by linking Rl and R'' includes a piperidyl group, a pyrrolysilyl group,
Examples include N-alkylpiperazyl group, morpholyl group, indolinyl group, and benztriazole group.

Preferred substituents for Rl and R'' are a hydroxy group, an alkoxy group, an alkyl or arylsulfonyl group, an amide group, a carboxy group, a cyano group, a sulfo group, a nitro group and an amino group.

Compound A I I C2Hs N C,
HsH A -I -2 CH.

OC7 4 N-C2 4 -OCH.

CH -3 2 5 C2 4 -N-CH.

CH CH.

CH CH HOH As the hydrazines and hydrazides, the following are preferred.

In the formula, R11, R1', and R'' represent a hydrogen atom, a substituted or unsubstituted alkyl group, an aryl group, or a heterocyclic group, and R11 represents a hydroxy group, a hydroxyamino group, or a substituted or unsubstituted alkyl group. , aryl group, heterocyclic group,
Represents an alkoxy group, aryloxy group, carbamoyl group, or amiki group. The heterocyclic group is a 5- to 5-membered ring and is composed of CXH, OlN, S and halogen atoms,
It may be either saturated or unsaturated. X" represents a divalent group selected from -C〇-H-SO, ~, or -〇-,
n is 0 or l. In particular, when n=0, R″ represents a group selected from an alkyl group, an aryl group, and a heterocyclic group,
R3j and R31 may jointly form a petero ring.

In general formula (A-I1), R3l, Rl2, and R1'' are preferably hydrogen atoms or 01-C3° alkyl groups, and most preferably R'' and R32 are hydrogen atoms.

In general formula (A-n), Ri+ is preferably an alkyl group, an aryl group, an alkoxy group, a carbamoyl group, or an amino group. Particularly preferred are alkyl groups and substituted alkyl groups. Preferred substituents for the alkyl group here include a carboxyl group, a sulfo group, a nitro group, an amino group, a phosphono group, and the like. X3 is preferably -C〇- or -SO□-, most preferably C〇-.

(Compound example) ■ NH2NHtcHzk 5O3H F-3 NH, NH I CH2 valve OH -6 NH, NHCOCR.

■ NH2NHCOOC2H.

A-low 1O NH, Nf IC0NH.

A-n-12 NH, NH30I H -n-13 N.H. 1 NH, NHCNH.

A~■ 4 NH2NHCOCONHNH2 -n 5 NH2NHCH, CH2CH, So, HA-If-17 NH2NHCHCOOH C+ I(e(n) -18 NH, NHCH2CH, C0OH Represented by the above general formula (A-4) or (A-I1) The use of a compound represented by the following general formula (A-111) in combination with the amines represented by the following general formula (A-111) improves the stability of the color developer,
Therefore, it is more preferable from the viewpoint of improving development stability in continuous processing.

General formula (A-m; R"R"-N-R'3 where R-', R", and R" represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group, or a heterocyclic group) Here, R+l and R?!R'' and R'' or R72 and R'' may be connected to form a nitrogen-containing heterocycle.

Here, R? l, RTf and R'' may have a substituent. R'', R=2, and R++ are particularly preferably a hydrogen atom or an alkyl group. Substituents include hydroxyl group, sulfo group, carboxyl group, halogen atom,
Examples include a nitro group, an amine group, and the like.

(Compound example) A-Ill-1 A-1ff-2 A-II[-3 -m-4 N6CH2CH,0H)3 H2NCH, CH20H HN6CH2CH20H)z C, H,, N (CH, CHCH, OH)zA ■-8 A-I-1,0 (HOCH2CH, left NCH2CH25o□CH.

-In 1 NH ICH2C00H)2 I[l-12 HOOCCH2CH2CHCOOH N.H.

■ 3 H, NCH2CH25O, NH2 A-[[-15 2N C-(CH,OH)! A-II[-16 HOCH, CHCOOH H2 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-22-amino-5-diethylaminotoluene / / / /' -3 -4 -5 -6- 7- -9 -10 2-amino-5-(N -ethyl-N-laurylamino)toluene 4-[N-ethyl-N-(β-hydroxyethyl)amino]aniline 2-methyl-4-[N-ethyl-N-(β-hydroxyethyl)aminocoaniline 4 -Amino-3-methyl-N-ethyl-N-[β-(methanesulfonamido)ethyl]-aniline N-(2-amino-5-diethylaminophenylethyl)methanesulfonamide N,N-dimethyl-P-phenylenediamine 4-amino-3-methyl-N-ethyl-N-methoxyethylaniline 4-amino-3-methyl-N-ethyl-N-β-ethoxyethylaniline D-114-amino-3-methyl-N-ethyl- N-β
-Ethoxyethylaniline Among the above-mentioned -phenylenediamine derivatives, 4-amino-3-methyl-N-ethyl-N-(β-(
methanesulfonamido)ethyl]-aniline (exemplified compound D-6) and 2-methyl-4-[N-ethyl-N-
(β-Hydrobovine legethylaminocoaniline (Exemplary Compound D-5).

Furthermore, these p-phenylenediamine derivatives may be salts such as sulfate, hydrochloride, sulfite, and p-toluenesulfonate.The amount of aromatic-grade amine developing agent used is determined per developer IJ. Preferably the concentration is from about 0.1 to about 20 g, more preferably from about 0.5 g to about 15 g.

The color developing solution according to the present invention has the following general formula (B-■) and CB-
A compound represented by n) is more preferably used.

General formula (B-1) General formula (B-I[] a In the formula, Rlm, RIS, Ro and R17 are each a hydrogen atom, a halogen atom, a sulfonic acid group, or a carbon atom number of 1 to
7 alkyl group, -0R0, and RI1%RI9, R2゜ and R□ each represent a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, provided that R11 represents -OH or a hydrogen atom In this case, R14 represents a halogen atom, a sulfonic acid group, an alkyl group having 1 to 7 carbon atoms, OR+m.

The alkyl groups represented by R+a, RIS, Ro and RIS include those having substituents, such as methyl group, ethyl group, 1so-propyl group, n-propyl group, [-butyl group, n-butyl group, hydroxymethyl The alkyl group represented by Rlm, RIS, R20 and RzI is as defined above, and further includes octyl group.

Further, examples of the phenyl group represented by RI4, Rl 5 s RI & and Rlm include a phenyl group, a 2-hydroxyphenyl group, and a 4-aminophenyl group.

Typical specific examples of the chelating agent of the present invention are listed below, but the invention is not limited thereto.

(B-1-1) 4-isopropyl-1,2-dihydroxybenzene (B-1-2) 1.2-dihydroxybenzene-35-disulfonic acid (B-1-3) 1.2.3-trihydroxy Benzene-5-carboxylic acid (B-1-4) 1.2.3-Trihydroxybenzene-5-carboxymethyl ester (B-1-5) l.

2゜ 3-trihydroxybenzene-5= Carboxy-n-butyl ester (B-1-6) 5-[-butyl-1゜ 2゜ trihydroxy benzene (B-1-7) ■.

2-dihydroxybenzene-3゜4゜-trisulfonic acid (B-11-1) 2゜3-dihydroxynaphthalene-6-sulfonic acid (B-11-2) 2゜3゜8-trihydroxynaphthalene-6 - Sulfonic acid (B-It-3) 2゜3-dihydroxynaphthalene-6-carboxylic acid (B-11-4) 2゜3-dihydroxy-8-isopro and lunaphthalene (B-11-5) 2.3- Dihydroxy-8-chloro-naphthalene-6-
Among the above sulfonic acid compounds, compounds particularly preferably used in the present invention include 1,2-dihydroxybenzene-3,
Examples include 5-disulfonic acid, and it can also be used as alkali metal salts such as sodium salts and potassium salts. (Specific exemplary compound (Br-2)).

In the present invention, the general formulas (B, -13 and (B-I
The compound represented by [) is the color developer 1j! Hit 5~
Can be used in the range of 15g, preferably 15m
It is desirable to use the amount in the range of g-10g, more preferably in the range of 251g to 7g.

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, various things must be done! 1! Preferably, a balancing agent is used; as a buffering agent, sodium carbonate, 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 salicylate), potassium o-hydroxybenzoate, sodium 5-sulfo-2-hydroxybenzoate (5- Examples include sodium sulfosalicylate), potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate), and the like.

The amount of the buffer added to the color developer is 0. 1 mole/
j! It is preferable that it is more than 0. 1 mole/2
Particularly preferred is ~0°4 mol/l.

In addition, various caloric acid agents can be used in the color developer as agents for preventing precipitation of calcium and magnesium, or for improving the stability of the color developer.

Specific examples are shown below, but are not limited to, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenedi7minetetraacetic acid, triethylenetetraminehexaacetic acid,
Nitrilo N, N, N-1 lith (methylene phosphonic acid),
Ethylenediamine-N,N,N',N'-tetrakis (methylenephosphonic acid), 1,3-diamino-2-propatoltetraacetic acid, transcyclohedrindiaminetetraacetic acid, nitrilotripropionic acid, l,2- Diaminopropane tetraacetic acid, hydroxyethyliminodiacetic acid, glycol ether diamine tetraacetic acid, hydroxyethylene diamine triacetic acid, ethylene diamine orthohydroxyphenylacetic acid, 2-phosphonobutane-1,2,4-)licarboxylic acid, 1-hydroxyethylidene-1, 1-diphosphonic acid,
N,N'-bis(2-hydroxybenzyl)ethylenediamine-N,N'-diacetic acid, catechol-3,4,6
-trisulfonic acid, catechol-3,5-disulfonic acid, 5-sulfosalicylic acid, 4-sulfosalicylic acid.

Among these chelating agents, ethylenediaminetetraacetic acid, ethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, 1,3-diaminopropanoltetraacetic acid, ethylenediamine-N, N, N', N'-
Tetrakis (methylenephosphonic acid) and hydroxyethyliminodiacetic acid are good.

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

The amount of these chelating agents added may be sufficient to sequester the metal ions in the color developer. For example, 11
It is about 0.1g to 10g 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. 3B-7826, No. 44-123
No. 80, No. 45-9019 and U.S. Patent No. 3,813
, p-phenylenediamine compounds shown in JP-A-52-49829 and JP-A-50-15554, JP-A-Sho 50
-137726, Japanese Patent Publication No. 44-30074, Japanese Patent Publication No. 56-156826 and Japanese Patent Publication No. 52-43429, etc., U.S. Patent No. 2,61
p- described in No. 0,122 and No. 4,119゜462
Aminophenols, U.S. Patent Nos. 2,494,903, 3.128,182, 4,230,796,
No. 3,253゜919, Special Publication No. 11431-1973,
U.S. Patent No. 2,482.546, U.S. Patent No. 2,596,92
Amine compounds described in No. 6 and No. 3,582,346, etc., Japanese Patent Publication No. 37-16088, No. 42-2520
No. 1, U.S. Patent No. 3,128.183, Special Publication No. 1973-
11431, 42-23883, and U.S. Pat. No. 3', 532,501, etc., other 1-phenyl-3-pyrazolidones, hydrazines, meso-ionic compounds, ionic compounds, imidazoles, etc. can be added as necessary.

Preferably, the color developer contains substantially no benzyl alcohol, by substantially 2 parts per 1 part color developer.
．． 0ml! More preferably, it is not contained at all. When it is not substantially contained, fluctuations in photographic properties during continuous processing, particularly increases in staining, are smaller, and more favorable results can be obtained.

In the present invention, in addition to chlorine ions and bromide ions, any antifoggant can be added as necessary. As antifoggants, alkali metal halides such as potassium iodide and organic antifoggants can be used. Examples of organic antifoggants include benzotriazole, 6-
Nidropenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-
Representative examples include nitrogen-containing heterocyclic compounds such as thiazolyl-benzimidazole, 2-thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine, and adenine.

The color developer used in the present invention preferably contains a fluorescent whitening agent.
Diamino-2,2'-disulfostilbene compounds are preferred, and the amount added is 0 to 10 g/J! , preferably 0.1
~6g/2.

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

The processing time of the color developer of the present invention is 10 seconds to 120 seconds,
Preferably, the effect of the present invention is significant in 20 seconds to 60 seconds. Further, the treatment temperature is 33 to 45°C, preferably 3
The effect of the present invention is particularly remarkable at 6 to 40°C.

The replenishment amount of the color developer during continuous processing is 20 to 220111 d per lnf of the light-sensitive material, preferably 25 to 160 d.
Particularly preferred is 30d to 110d, since the effects of the present invention can be effectively exhibited.

In addition, the color developer of the present invention has relatively superior performance in its liquid aperture ratio (air contact area (e)/liquid volume (d)) than combinations other than those of the present invention under any conditions. From the viewpoint of the stability of the developer, the opening ratio of the solution should be 0 to 0. I
Cll-' is preferred, and in continuous processing, the range of O,OOl cm-' to 0.05 cm-' is preferred from a practical standpoint, and more preferably the range of 0,002+am-' to 0.002 cm-'.
03C11-'.

Generally, when hydroxylamine etc. are used as a preservative, even if the aperture ratio of the color developer is reduced,
It is widely known that decomposition occurs due to heat or trace metals. However, in the color developer of the present invention,
These decompositions are extremely small, and the color developer can be sufficiently put to practical use even when the color developer is stored or used for a long period of time. Therefore, in this case, it is preferable that the liquid aperture ratio is small, and 0-0. 002 cm-' is most preferred.

On the other hand, there are cases where processing is performed with a wide aperture ratio under the condition that the processing amount is discarded after processing a certain amount, but even in such a processing method, if the structure of the present invention is followed, excellent performance can be achieved. can.

In the present invention, desilvering treatment is performed after color development. The derailing step generally consists of a bleaching step and a fixing step, but it is particularly preferable that they be carried out simultaneously.

The bleach or bleach-fix solutions used in the present invention may contain bromides (e.g., potassium bromide, sodium bromide, ammonium bromide), or chlorides (e.g., potassium chloride, sodium chloride, ammonium chloride), or iodides. (eg, ammonium iodide).

If necessary, one or more inorganic substances having a pH 1l binding capacity such as boric acid, borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate, tartaric acid, etc. Acids, organic acids and alkali metal or ammonium salts thereof, or corrosion inhibitors such as ammonium nitrate, guanidine, etc. can be added.

The fixing agent used in the bleach-fixing solution or fixing solution according to the present invention is a known fixing agent, namely sodium thiosulfate,
Thiosulfates such as ammonium thiosulfate; thiocyanates such as sodium thiocyanate and ammonium thiocyanate; water-soluble such as thioether compounds and thioureas such as ethylene bisthioglycolic acid and 3,6-cythia-1,8-octanediol Halogenation! ! These are solubilizing agents, and these can be used alone or in combination of two or more. In addition, a special bleach-fixing solution consisting of a combination of a fixing agent described in JP-A-55-155354 and a large amount of a halide such as potassium iodide can also be used.In the present invention, thiosulfate ,
Particularly preferred is ammonium thiosulfate salt.The amount of fixing agent per 12 moles is preferably 0.3 to 2 moles, more preferably 0.5 to 1. It is in the range of 0 mol.

The pH range of the bleach-fix solution or fixer solution in the present invention is as follows:
3 to 8 are preferred, and 4 to 7 are particularly preferred, p
If H is lower than this, the desilvering property will be improved, but the deterioration of the solution and the leucoization of the cyan dye will be promoted. On the other hand, if 9H is higher than this, desilvering is delayed and staining is more likely to occur.

In order to adjust the pH, hydrochloric acid, sulfuric acid, nitric acid, acetic acid, bicarbonate, ammonia, caustic potash, caustic soda, sodium carbonate, potassium carbonate, etc. can be added as necessary.

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

The bleach-fix solution and fixer solution used in the present invention contain sulfites (e.g., sodium sulfite, potassium sulfite,
ammonium sulfite, etc.), bisulfites (e.g. ammonium bisulfite, sodium bisulfite, potassium bisulfite, etc.), metabisulfites (e.g. potassium metabisulfite, sodium metabisulfite, ammonium metabisulfite, etc.) ) and other sulfite ion-releasing compounds. These compounds are approximately 0.0 in terms of sulfite ion.
The content is preferably 2 to 0.50 mol/l, more preferably 0.04 to 0.40 mol/2. Particularly preferred is the addition of ammonium sulfite.

Sulfites are commonly added as preservatives, but other preservatives include ascorbic acid, carbonyl bisulfite adducts,
Sulfinic acids, carbonyl compounds, sulfinic acids, etc. may be added.

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

The bleach-fix solution of the present invention has a processing time of 10 seconds to 120 seconds, preferably 20 seconds to 60 seconds. Also, the replenishment amount is 1r of photosensitive material.
1 to 250111 in 30 per rf, preferably 40d to
It is 150111. Generally, an increase in staining and poor desilvering tend to occur as the amount of replenishment is reduced, but according to the present invention, the amount of replenishment of bleach-fix solution can be reduced without causing such problems. be able to.

The silver halide color photographic light-sensitive material of the present invention is generally subjected to a water washing and/or stabilization process after fixing or desilvering treatment such as bleach-fixing.

The amount of water used in the washing process depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), the application, the temperature of the washing water, the number of washing tanks (the number of stages), the replenishment method such as countercurrent or forward flow, and various other conditions. Can be set over a wide range. this house,
The relationship between the number of flushing tanks and the amount of water in the multistage countercurrent method is described in the Journal on the Society on Motion.
Picture and Television Engineers (J
our own of the 5ociety of
Motion Picture and Televfs
ion Engtneers) Volume 64, p. 248~
253 (May 1955 issue).

According to the multi-stage countercurrent method described in the above-mentioned literature, the amount of water used for washing can be significantly reduced, but due to the increase in the residence time of water in the tank, bacteria will breed, and the generated suspended matter will adhere to the photosensitive material. In the processing of the color photosensitive material of the present invention, as a solution to such problems,
The method for reducing calcium and magnesium described in Japanese Patent Application No. 61-131632 can be used very effectively. In addition, chlorine-based disinfectants such as isothiazolone compounds, cyabendazole, chlorinated sodium isocyanurate, and other benzotriazoles described in JP-A No. 57-8542, "Chemistry of Antibacterial and Antifungal Agents" by Hiroshi Horiguchi , "Microbial tam, sterilization, and anti-mildew technology" edited by the Sanitation Technology Society, and "Encyclopedia of anti-bacterial and anti-mold agents" edited by the Japanese Society of Anti-bacterial and Anti-fungal agents can also be used.

The pH of the washing water in the processing of the photosensitive material of the present invention is 4 to 9.
and preferably 5 to 8. The washing water temperature and washing time can also be set variously depending on the characteristics of the photosensitive material, its use, etc., but generally it is 20 seconds to 2 minutes at 15 to 45°C, preferably 25 to 2 minutes.
A range of 30 seconds to 1 minute and 30 seconds at 40°C is selected.

Even in such short-time water washing, according to the present invention, there is no increase in staining and good photographic characteristics can be obtained.

Furthermore, the photosensitive material of the present invention can also be directly processed with a stabilizing solution instead of washing with water. In such stabilization treatment, Japanese Patent Application Laid-open Nos. 57-8543 and 58-1
No. 4834, No. 59-184343, No. 60-220
No. 345, No. 60-238832, No. 60-2397
All known methods described in No. 84, No. 60-239749, No. 61-4054, No. 61-118749, etc. can be used. Especially 1-hydroxyethylidene-1,1-diphosphonic acid, 5-chloro-2-methyl-
A stabilizing bath containing 4-isothiazolin-3-one, a bismuth compound, an ammonium compound, etc. is preferably used.

Further, following the water washing process, a further stabilization process may be performed, such as a stabilizing bath containing formalin and a surfactant, which is used as a final bath for color photosensitive materials for photography. .

The processing time of the present invention is defined as the time from when the photosensitive material comes into contact with the color developer until it exits the final bath (generally water washing or stabilization bath).
The effects of the present invention can be significantly exhibited in a rapid treatment process in which the processing time is 30 seconds or less, preferably 3 minutes or less.

The photosensitive material used in the present invention will be explained in detail.

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.

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] A particle with a so-called layered structure in which the halogen composition is different, or a structure having a non-layered portion with a different halogen composition inside or on the surface of the particle (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 one 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.

In high silver chloride emulsions, the silver bromide localized layer is formed in the layered or non-layered form as described above inside the silver halide grains and/or
Alternatively, those having a structure on the surface are preferable. The halogen composition of the localized layer is at least 1 in terms of silver bromide content.
It is preferably 0 mol%, and 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 better achieve the effects of the present invention, it is also preferable to use grains with a uniform structure in which the distribution of halogen composition within the grains is small in a high silver chloride emulsion with a silver chloride content of 90 mol% or more. .

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.

The amount of coated silver in the silver halide emulsion used in the present invention is preferably 0.75 g or less per photosensitive material in terms of speed and prevention of processing fluctuations.

In particular, the amount is preferably 0.70 g or less, more preferably 0.65 g or less per 1rrl' of the photosensitive material.

The average grain size of the 710 silver germide 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 0.1 μ to 2μ is preferred.

The particle size distribution thereof is preferably so-called monodisperse, with a coefficient of variation (standard deviation of particle size divided by average particle size) of 20% or less, preferably 15% or less. 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), irregular crystal shapes such as spherical or plate-like, or a combination of these shapes 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, Glafkide.
Written by Chimie et Ph1sique Photo
ographique (Paul Mont e 1
Publishing, 1967), Photographic Emulsion Che by G. F. Duffin
mistry (published by Focal Press, 19
66), V. L., Zelikman et a.
Making and Coating P
Photographic Emulsion (Foc
Al Press, 1964). That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble silver salt with the soluble halogen salt is as follows:
Any method such as a one-sided mixing method, a simultaneous mixing method, or a combination thereof may be used. A method of forming particles in an atmosphere containing excess silver ions (so-called back mixing method)
You can also use As one type of simultaneous mixing method, a method in which the pAg in the liquid phase in which silver halide is produced can be kept constant, that is, the so-called Chondrald double jet method can also be used. According to this method, a silver halide emulsion with a regular crystalline shape and nearly uniform grain size can be obtained.

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

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

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

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

Spectral sensitization is carried out for the purpose of imparting spectral sensitivity in a desired light wavelength range to the emulsion of each layer in the light-sensitive material of the present invention. In the present invention, it is preferable to add a dye-spectral sensitizing dye that absorbs light in a wavelength range corresponding to the desired spectral sensitivity. Spectral sensitizing dyes used at this time include, for example, Het.
erocyclic compoundsCyanin
e dies and related compo
unds (John Wiley & 5ons C
New York, London], 1964). Examples of specific compounds and spectral sensitization methods are described in the above-mentioned JP-A-62
-215272 Publication Specification, page 22, upper right column to 38th page
Those described on page 1 are preferably used.

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

The emulsion used in the present invention is 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 surface latent image type emulsion in which a latent image is mainly formed inside the grains. Also good.

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

In the present invention, the following general formulas (C-1), (C-I1) (M-1) are used as cyan couplers and macenta couplers.
, (M-I1) is preferably used because the effects of the present invention are better exhibited.

General formula (C-■) General formula (C-n) H 2 General formula (M ■) R8 General formula (M-11) In general formula (C-1) and (C ■), 2 and R1 are substituted or represents an unsubstituted aliphatic, aromatic or heterocyclic group, R8 and R6 represent a hydrogen atom, a halogen atom, an aliphatic group, an aromatic group or an acylamino group, and R1, together with R2, represents a nitrogen-containing 5-membered ring or It may also represent a group of nonmetallic atoms forming a 6-membered ring. Yl and Y represent a hydrogen atom or a group that can be separated during a coupling reaction with an oxidized product of a developing agent.

n represents 0 or 1.

R6 in general formula (C-n) is preferably an aliphatic group, such as methyl group, ethyl group, propyl group, butyl group, pentadecyl group, tert-butyl group, cyclohexyl group, cyclohexylmethyl group, phenyl group Examples include thiomethyl group, dodecyloxin phenylthiomethyl group, butanamidomethyl group, and methoxymethyl group.

Preferred examples of the cyan coupler represented by the general formula (C-1) or (C-I1) are as follows.

In general formula (C-1), 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 anlu 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 cyan group.

In general formula (C-1), when R and R2 do not form a ring, R2 is preferably a substituted or unsubstituted alkyl group or aryl group, particularly preferably a substituted aryloxy-substituted alkyl group, and R8 is preferably a hydrogen atom.

In general formula (C-I1), R6 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-It), R6 preferably has 2 to 2 carbon atoms.
It is a methyl group having 15 alkyl groups and a substituent having 1 or more carbon atoms, and the substituent is preferably an arylthio group, an alkylthio group, an acylamino group, an aryloxy group, or an alkyloxy group.

In general formula (C-I1), R1 is more preferably an alkyl group having 2 to 15 carbon atoms, particularly preferably an alkyl group having 2 to 4 carbon atoms.

In general formula (C-11), preferable R8 is a hydrogen atom,
A halogen atom, with chlorine and fluorine atoms being particularly preferred. Preferred Yl and Y2 in general formulas (C-1) and (C-I1) 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-■), R1 and R represent an aryl group, R3 represents a hydrogen atom, an aliphatic or aromatic acyl group, an aliphatic or aromatic sulfonyl group,
Y represents a hydrogen atom or a leaving group. The substituents allowed for the aryl group (preferably the phenyl group) of R1 and R2 are the same as the substituents allowed for the substituent R4, and when there are two or more substituents, they may be the same or different. You can. R8 is preferably a hydrogen atom, an aliphatic acyl group or a sulfonyl group, particularly preferably a hydrogen atom. Preferred Y3 is of the type that leaves off with either sulfur, oxygen or nitrogen atoms, such as those described in US Pat. No. 4,351.897 and International Publication WO 3810479.
The sulfur atom detachment type as described in No. 5 is particularly preferred.

In general formula (Mn), RIO 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 is methine, substituted methine, =N- or -NH-
, one of the Za-Zb bond and the Zb-Zc bond is a double bond, and the other is a single bond. The case where the Zb-Zc bond is a carbon-carbon double bond includes the case where it is a part of an aromatic ring. This includes the case where R1° or Y4 forms a dimer or more multimer, and when Za, Zb or Zc is a substituted methine, the case where the substituted methine forms a dimer or more multimer.

Among the pyrazoloazole couplers represented by the general formula (M-n), imidazo [l, 2 -b) Pyrazoles are preferred, pyrazolo (I,5
-b] l:1°2.4) I-lyazole is 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. Pyrazolotriazole couplers containing a sulfonamide group in the molecule, pyrazoloazole couplers having an alkoxyphenylsulfonamide ballast group as described in JP-A-61-147254, and European Patent Publication No. 226, It is preferred to use pyrazolotriazole couplers having an alkoxy or aryloxy group at the 6-position, such as those described in No. 849 and No. 294,785.

The couplers represented by the above general formulas (C-1) to (M-I1) are contained in the silver halide emulsion layer constituting the photosensitive layer, usually in an amount of 0.00% per mole of silver halide. 1 to 1.0 mol, preferably 0. It is contained in an amount of 1 to 0.5 mol.

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

Furthermore, alkali-soluble Ropler 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℃)
2-20, refractive index (25°C) 1. It is preferable to use a high boiling point organic solvent and/or a water-insoluble polymer compound of 5 to 1.7.

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

In particular, the general formula (C-1) (C- ■), (M-1) (M-■) represented by It is particularly preferred for couplers that

General formula (A) 2 -o-p=.

W.

General formula (D) General formula (E) OW+ (In the formula, , W2 and W.

each represents a substituted or unsubstituted alkyl group, cycloalkyl group, alkenyl group, aryl group, or heterocyclic group, and W represents W
, , OW, maf: represents s-W, n is an integer from 1 to 5, and when n is 2 or more, W may be the same or different from each other, and - general formula (E ), Wl
and W2 may form a fused ring).

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

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

These couplers can also be synthesized with rhodapul latex polymers (
For example, U.S. Patent No. 4. 203. No. 716) or dissolved in a water-insoluble but organic solvent-soluble polymer to disperse an emulsion in an aqueous hydrophilic colloid solution.

Homopolymers or copolymers described on pages 12 to 30 of International Publication No. WO 38100723 are preferably used, and acrylamide polymers are particularly preferred from the viewpoint of color image stabilization.

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

Various anti-fading agents can be used in the photosensitive material of the present invention. That is, hydroquinones, 6
-Hydroxychromans, 5-hydroxycoumarans,
Spirochromans, p-alcoquine phenols, hindered phenols centered on bisphenols, gallic acid derivatives, methylenedioxybenzenes, aminophenols, hindered amines, and the phenolic hydroxyl groups of these compounds are silylated and alkyl 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 disclosed in U.S. Patent No. 2,360,290;
Same No. 2,418.613, Same No. 2,700.453, Same No. 2,701,197, Same No. 2,728,659
No. 2. 732. No. 300, No. 2,735.
No. 765, No. 3,982.944, No. 4,430
, 425, British Patent No. 1,363,921, U.S. Patent No. 2,710.801, U.S. Patent No. 2,816,028, etc., 6-hydroxychromans, 5-hydroxycoumarans, spirochromans is U.S. Patent No. 3°432.
No. 300, No. 3,573,050, No. 3,574
, No. 627, No. 3. 698. No. 909, same No. 3,
No. 764,337, JP-A No. 52-152225, spiroindanes are described in U.S. Patent No. 4,360,589, and p-alkoxyphenols are described in U.S. Patent No. 2,73.
No. 5,765, British Patent No. 2,066.975, Japanese Unexamined Patent Publication No. 10539/1982, and Japanese Patent Publication No. 19765/1983, and hindered phenols are described in US Patent No. 3.700.
No. 455, JP-A-52-72224, U.S. Patent No. 4,2
No. 28,235 and Japanese Patent Publication No. 52-6623, etc., and gallic acid derivatives, methylenedioxybenzenes, and aminophenols are disclosed in U.S. Patent No. 3,457.079, respectively.
No. 4,332.886 and Japanese Patent Publication No. 56-21144, hindered amines are disclosed in U.S. Patent No. 3. 336
．． 135, British Patent No. 4,268,593, British Patent No. 1,326,889, British Patent No. 1,354,313, British Patent No. 1,410,846, Japanese Patent Publication No. 51-1420, Japanese Patent Publication No. No. 58-114036, No. 59-53846,
No. 59-78344, etc., metal complexes are disclosed in U.S. Patent No. 4,050,938, U.S. Patent No. 4,241,155, British Patent No. o27.731(A), etc., respectively. The purpose of these compounds can be achieved by co-emulsifying them with the respective color couplers and adding them to the photosensitive layer, usually in an amount of 5 to 1 ec% by weight, based on the respective color couplers. 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. Nos. 3,705,805 and 3,707,395), ), butadiene compounds (such as those described in U.S. Pat. No. 4.045.229), or benzoxidol compounds (such as those described in U.S. Pat. No. 3.406.070, 3,6
77.672 and 4,271°307) can be used.

An ultraviolet absorbing coupler (for example, an α-naphthol cyan dye-forming coupler) or an ultraviolet absorbing polymer may be used. These ultraviolet absorbers may be mordanted in specific layers.

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

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

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

Preferred compounds (F) have a second-order reaction rate constant kz with p-anisidine (in trioctyl phosphate at 80°C) of 1. Of/mol・5ec-IXIO-'
It is a compound that reacts within the range of A'/mol-sec.

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

When k2 is larger than this range, the compound itself becomes unstable and may react with gelatin or water and decompose. On the other hand, if ki is smaller than this range, the reaction with the remaining aromatic amine developing agent will be slow, and as a result, side effects of the remaining aromatic amine developing agent may not be prevented.

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

General formula (Fl) R, -(A). -X General formula (Fn) R2-C=Y In the formula, R-1Rz each represents an aliphatic group, an aromatic group, or a heterocyclic group. n represents 1 or O. 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 anol group, or a sulfonyl group, and Y represents the addition of an aromatic amine developing agent to the compound of general formula (F n). Represents a promoting group. Here R1, X, Y
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 (F1) and (FI1), see JP-A-63-158545 and JP-A-63
-283338, European Patent Publication No. 298321, 2
Those described in specifications such as No. 77589 are preferred.

On the other hand, a more preferable compound (G) that chemically bonds with the oxidized aromatic amine developing agent remaining after color development processing to produce a chemically inert and colorless compound is the following general formula (G1 ).

General formula (Gl) -Z In the formula, R represents an aliphatic group, an aromatic group or a heterocyclic group. Z represents a nucleophilic group or a group that decomposes in the photosensitive material to release a nucleophilic group. In the compound represented by the general formula (G1), Z has Pearson's nucleophilicity 'CH,I value (
R.G., Pearson, et al.

J, Am, Chem, Soc,,90. 319
A group in which (I968) ) is 5 or more, or a group derived therefrom is preferred.

Specific examples of compounds in which - is represented by formula (G1) are disclosed in European Patent Publication No. 255722 and Japanese Patent Application Laid-open No. 62-1430.
No. 48, No. 62-229145, patent application No. 63-136
No. 724, No. 62-214681, European Patent Publication 29
Those described in No. 8321, No. 277589, etc. are preferred.

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

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

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

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 Macromolecular 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. It is preferable to provide a layer of water-resistant resin, particularly thermoplastic resin, 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. 6124247, 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 μm x 6 μm, and dividing the area of fine particles projected onto that unit area. It can be determined by measuring the occupied area ratio (%) (R,). The coefficient of variation of the occupied area ratio (%) can be determined by the ratio S/''R of the standard deviation S of R1 to the average value (R) of R1.The number of target unit areas (n) must be 6 or more. Preferably. Therefore, the coefficient of variation s/R can be determined by s/R.

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) Examples of the present invention will be specifically shown below, but the present invention is not limited thereto.

Example 1 A multilayer color photographic paper 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 (ExY) and 28.0 g of anti-fading agent (Cpd-1), 150 cc of ethyl acetate and 1.0 g of solvent (Solv-3). Occ and solvent (Solv)
-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 (silver bromide 0.7 mol %) containing a sensitive dye.

The 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. 3'-disulfoethylthiacyanine hydroxide green-sensitive emulsion layer; anhydro-9-ethyl-5°5'-diphenyl-3,3'-disulfoethyloxacarphonoanine hydroxide red-sensitive emulsion layer; 3. 3'-ethyl-5-methoxy-9
, 11-neopentylthiazidylupocyanine iodide The following substances were used as stabilizers for each emulsion layer.

■-(2-acetaminopheny7yl)-5-
Mercaptotetrazole and the following were used as anti-irradiation dyes.

[3-carboxy-5-hydroxy-4-(3-(3-
Carboxy-5-oxo-1-(2,5bisulfonatophenyl)-2-biraprin-4ylidene)-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 number is the coating amount (g/rr?)
represents. 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) The above-mentioned silver chlorobromide emulsion (AgBrO, 7 mol %, cubic,
Average particle size 1.02 μm) 0.25 1.80 0.60 0.28 0.01 0.03 Ceratin Yellow Coupler (ExY) Anti-fading agent (Cpd-1) Solvent (Solv-3) Solvent (Solv- 4) Second layer (color mixing prevention layer) Gelatin color mixing prevention agent (Cpd-2) Solvent (Solv-1) Solvent (Solv-2) Third layer (green-sensitive layer) The above-mentioned silver chlorobromide emulsion (AgBr cube, Average particle size O.

Ceratin magenta coupler (ExM) Anti-fading agent (Cpd-3) 0, 80 0, 055 0, 03 0, l5 0.7 mol%, 58 μm) 0, 26 1, 86 0, 27 0, 17 Anti-fading Agent (Cpd-4) 0.10 solvent (
Solv-1) 0.2 Solvent (So 1
v-2) 0. 03 Fourth layer (color mixing prevention layer) Gelatin 1.70 Color mixing prevention agent (Cpd-2) 0.065 Ultraviolet absorber (UV-1) 0.45 Ultraviolet absorber (UV
-2) 0.23 solvent (Solv-1)
0.05 solvent (So 1v-2)
0. 05 Fifth layer (red-sensitive layer) The aforementioned silver chlorobromide emulsion (AgBr 4 mol%, cubic, average grain size 0.59 μm) 0, 21 Gelatin 1.80 Cyan coupler (ExC-1) 0126 Cyan coupler (ExC- 2) 0.12 anti-fading agent (Cpd
-1) 0.20 solvent (Solv-1)
0.16 solvent (Solv-2)
0.09 Color accelerator (Cpd-5) Sixth layer (ultraviolet absorption layer) Gelatin ultraviolet absorber (UV-1) Ultraviolet absorber (UV-2) Solvent (Solv-1) Solvent (Solv-2) Seventh layer Layer (protective layer) Gelatin (ExY) Yellow coupler (Y-6) (ExM) Magenta coupler 1 (ExC ■) Cyan coupler I (ExC-2) Cyan coupler (Cpd-1) Anti-fading agent 2CH.

-CHsu- CONHC.

He(n) Average molecular weight 0 00 (Cpd 2) Color mixing inhibitor 2゜5-di-tert-octylhydroquinone (Cpd=3) Fading inhibitor 7.7'-dihydroxy-4,4,4',4'tetramethyl -2,2'-spirochroman (Cpd-4) Color inhibitor N-(4-dodecyloxyphenyl)-morpholine (Cpd-5) Color accelerator p-(p-toluenesulfonamide) phenyldodecane (Sol~. -■) Solvent (2-ethylhexyl) phthalate (Solv-2) Solvent dibutyl phthalate (Solv-3) Solvent (I-nonyl) phthalate (Sol~.-4) Solvent N, N-diethylcarbonamide-methoxy 4 -G-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-butyl Phenyl)benzotriazole Coated sample 101 was prepared in the same manner as above, except that the silver chloride content of the silver halide emulsion in the blue-sensitive layer and the yellow coupler (molar concentration equivalent to Y-6) were changed as shown in Table 1. ~10
No. 6 was prepared, and its photographic properties were examined using the following method.

First, using a photosensitive needle (FWH type manufactured by Fuji Photo Film Co., Ltd., color temperature of light source 3200K) on the coated sample,
Provided gradation exposure for sensitometry. The exposure at this time was carried out at an exposure time of 1/10 second and an exposure amount of 250 CMS.

The above sample was processed using the following processing steps and the following processing composition. However, the composition of the color developer was changed as shown in Table 1.

Processing process Hoshi-Rin Machine-Ku Color development 38℃ 45 seconds Bleach fixing 30-36℃ 45 seconds Rinse ■ 30-37°C 30 seconds Rinse ■ 30-37°C 30 seconds Rinse ■ 30-37°C 30 seconds Drying 70-80°C 60 seconds The composition of each treatment liquid is as follows.

Color developer water 800ml! Ethylenediamine-N, N.

N,N-tetramethylenephosphonic acid 3.0g preservative (A-
11-19) 0. 03tnol Potassium chloride See Table 1 Potassium bromide
See Table 1 Potassium carbonate
25g N-ethyl-N-(β-methanesulfonamidoethyl) = 3-methyl-4-amine aniline sulfate 5.0g triethanolamine 10.0g fluorescent brightener (4,4'-
Diaminostilbene type) 2.0g Sodium sulfite 0.1g Add water
1000ml pH (256C)
10.05 hours fixed rich liquid water 400mA
Ammonium thiosulfate (70%) 100mf Sodium sulfite 17g Iron ethylenediaminetetraacetate (I
Add 9g water 1
000ml pH (25°C) 5.
40 Rinse solution (tank solution and replenishment solution are the same) Ion exchange water (calcium, magnesium 3pp each)
m or less) The color developer is applied to the contact area with air,
It was kept at a constant temperature of 40° C. for 2 weeks with an opening area of 20 cd. The sensitometry is processed at the start and end of the time-lapse of the color developer, and the yellow sensitivity change (density change in the exposure amount showing a density of 0.5 at the time-lapse start) and the change in yellow sensitivity due to the time-lapse of the color developer. Measure the change in gradation in the low exposure area (density difference from the point indicating a density of 0.5 to the density point on the high exposure side of 0.3 in fogE) and the maximum density of yellow after aging using a Macbeth densitometer. The results are shown in Table 1.

R, E l E E / As is clear from Table 1, when the constituent requirements of the present invention are met, the variation in photographic properties over time of the color developer is extremely small, the maximum density is high, and the photographic properties are stable. A rapid development process was achieved. (■~■, ■~■, 0~[phase], [phase]~0) If the silver chloride content of the emulsion in the blue-sensitive layer is less than 90 mol%, the maximum density will be low, impairing the speed, and It does not accomplish the purpose of the invention. (■ and ■ for ■ to ■) If the yellow coupler is not a compound of the present invention, even if the silver chloride content and chloride ion concentration are according to the present invention, the photographic properties will vary greatly and the object of the present invention will not be met. It's not something to achieve. (■~ [phase] for ■, ■, The variation is large and the purpose of the present invention is not achieved. (■, ■, 0 for 0 to [phase]) Among the present invention, when the bromine ion concentration in the color developer is 3X10-' to lXl0□3, the fluctuation in photographic properties is smaller and even better. The results were obtained.

(■, [phase] to 0 for [phase]) Example 2 A multilayer color photographic paper having the layer structure shown below was prepared on a paper support laminated on both sides with polyethylene. The coating solution was prepared as follows.

19.1 g of yellow coupler (ExY), 4.4 g of color image stabilizer (Cpd-1) and color image stabilizer (Cpd-7)
) to 0.7 g of ethyl acetate 27.2 CC and solvent (So
lv-1) 8.2g was added and dissolved, and this solution was mixed with 10% sodium dodecylbenzenesulfonate containing 8cc.
% gelatin aqueous solution (185 cc). On the other hand, in a block silver bromide emulsion (cubic, average grain size 0.82 μm, coefficient of variation of grain size distribution 0.08, containing 032 mol% silver bromide locally on the grain surface), the blue-sensitive sensitizing dye shown below is used. was prepared by adding 2.0×10 −' moles per mole of silver followed by sulfur sensitization. The above emulsified dispersion and this emulsion were mixed and dissolved to prepare a first coating solution having the composition shown below.

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

The following spectral sensitizing dyes were used in each layer.

/ / / / / Blue sensitive emulsion layer (per mole of silver halide, 2゜ 0XIO-'mol) Green sensitive emulsion layer oh Yo Beauty (per mole of silver halide) ■.

0XIO-' mol) red-sensitive emulsion layer (per mol of silver halide, 0.9 x 10-N mol for large size emulsions and 1 for small size emulsions)
．． For the 1X10-' mono red-sensitive emulsion layer, the following compound was added in an amount of 2.6X10-' mol per 1 mol of silver halide.

For the blue-sensitive emulsion layer, green-sensitive emulsion layer, and red-sensitive emulsion layer, 1-(5-methylureidophenyl)5-mercaptotetrazole was added at 8.0% per mole of silver halide, respectively.
5×10-'mol, 7°7xto-'mol, 2.5X1
0-'mol was added.

In addition, for the blue-sensitive emulsion layer and the green-sensitive emulsion layer, 4-hydroxy-6-methyl-1,3,3a,7-titrazaindene was added per mole of silver halide to lXl0-'
mol and 2X10-' mol were added.

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

and (14° 7 cm per 1 d of photosensitive material) and (36° 2 cm per 1 d of photosensitive material) (Layer structure) The composition of each layer is shown below. The numbers represent the coating amount (g/m'). The silver halide emulsion represents the coated amount in terms of silver.

Support polyethylene laminated paper [The polyethylene on the first layer side contains titanium oxide and a blue dye (ulmarine blue)] -th layer (blue-sensitive layer) The above-mentioned silver chlorobromide emulsion 0.25 gelatin 1.86 yellow coupler (ExY ) 0.82 color image stabilizer (Cpd-
1) 0.19 solvent (Solv-1)
0.35 color image stabilizer (Cpd-7)
0.06 Fifth layer (color mixing prevention layer) Ceratin 0.99 Color mixing prevention agent (Cpd-5) 0.08 Solvent (Solv-
1) 0.16 solvent (Solv-4)
0.08 Fifth layer (green sensitive layer) Silver chlorobromide emulsion (cubic, average grain size 0.40 μm,
The coefficient of variation of particle size distribution is 0.08, AgBr0.8
mol% was locally contained on the particle surface)
0.12 gelatin 1,
24 macenta coupler (BxM) 0.20
Color image stabilizer (CM-2) 0.03 Color image stabilizer (Cpd-3) 0.15 Color image stabilizer (C
pd-4) 0.02 color image stabilizer (Cpd-
9) 0.02 solvent (Solv-2)
0.40 Fourth layer (ultraviolet absorption layer) Gelatin 1.58 Ultraviolet absorber (UV-1) 0.47 Color mixture prevention agent (C
pd-5) 0.05 solvent (Solv-5)
0.24 Fifth layer (red sensitive layer) Silver chlorobromide emulsion (cubic, average grain size 0.60 μm,
The coefficient of variation of particle size distribution is 0.09 A g B r
(0.6 mol% was locally contained in a part of the particle surface)
0.20 Seratin
1.34 cyan coupler (BxC)
0.32 color image stabilizer (Cpd-6)
0.17 Color image stabilizer (Cpd-7) 0.
40 Color image stabilizer (Cpd-8) 0.04 Solvent (Solv-6) 0.15 Sixth layer (
Ultraviolet absorbing layer) Ceratin 0.53 Ultraviolet absorber (UV-1) 0.16 Color mixing prevention agent (C
pd-5) 0.02 solvent (Solv-5)
0.08 Seventh layer (protective layer) Ceratin 1.33 Acrylic modified copolymer of polyvinyl alcohol (degree of modification 17%)
0.17 liquid paraffin
0.03 (BxY) Yellow coupler (Y 1) (BxM) 1 1 mixture of magenta coupler (molar ratio) (BxC) Cyan coupler C1 R=C,H.

and C,H.

and l 2 for each quadruple I: :Mixture of 4 (cpci 1) color image stabilizer (Cpd-2) color image stabilizer C00C,H.

(Cpd-3) color image stabilizer (Cpd-4) color image stabilizer May (t) shst'i ([) (Cpd 5) Color mixing prevention agent (Cpd 6) color image stabilizer C4Hl(t) C4Hs(t) c, Hs(t) 2:4:4 mixture (weight ratio) of (Cpd-7) color image stabilizer Zu CH2 CHgeT CONHC, Hem average molecular weight 60° 00 (Cpd 8) color image stabilizer CH CH 1 1 mixture (weight ratio) (Cpd 9) color image stabilizer CH CH.

CH.

(UV ■) UV absorber C,H (I) C,Ha(t) 4:2 4 mixture (weight ratio) (Solv l) melt Medium (Solv-2) melt Medium 2 1 mixture (volume ratio) (Solv-4) melt Medium (Solv-5) melt Medium C00C,H,.

(CH1).

C00C,H,.

\1 (95:5 mixture) Capacity ratio The sample obtained as described above was designated as 201.

Next, Samples 201 to 210 were prepared in the same manner as Sample 301, except that the yellow coupler (mole concentration equivalent to Y-1) and the amount of coated silver in each layer were changed as shown in Table 2.

After the above sample was imagewise exposed, it was continuously processed (running test) using an automatic paper processor using the following processing steps and processing composition until twice the capacity of the color development tank was refilled.
was carried out.

The composition of the color developer was changed as shown in Table 3.

Processing process ■ Leech plate Container filling ° Tank capacity Color development 39°C 45 seconds 701n14 f Bleach fixing 30-368C 45 seconds 215d 41am
Stable■ 30~37°C 20 seconds -21 Stable■ 30~
37°C 20 seconds -21 stable■ 30~37°C 20
seconds 36W 2jl+drying 70~85
°C for 60 seconds * 1 rr of photosensitive material (replenishment amount per 3 tank countercurrent flow from stable ■ to ■) The composition of each processing solution is as follows.

Color developer tank liquid water 80〇-Ethylenediaminetetraphosphonic acid 9.4g Diethylenetriamine Five dishes Five trips 80〇- 9.4g Acetic acid 1.2g 1.2g1
-Hydroxyethylidene 1,1-diphosphonic acid 0.6g 0.6
g Triethanolamine 15.0g 15
゜Og Sodium chloride Potassium bromide (see Table 3) Potassium carbonate (see Table 3)
25g 25gN-ethyl-N-(β
-methanesulfonamidoethyl) 3-methyl-4-aminoaniline sulfate 5.0g 15.0g
Organic preservative (A-1-10) 0.05mol 0.08m
ol Sodium sulfite 0.1g 0.
2g fluorescent whitening agent (WRITEX-4 manufactured by Sumitomo Chemical) 1. Add 3.5g water 1000 d 1000 JpH
(25°C) 11.00 11.30 Bleach-fix solution (tank solution and replenisher are the same) water Ammonium thiosulfate (70%) Sodium sulfite Iron ethylenediaminetetraacetate (II1) Add ammonium ethylenediaminetetraacetic acid dinatrirum glacial acetic acid water pH (25℃) Support solution (tank solution and replenisher solution are the same) Formalin (37T6) Formalin-sulfite adduct 5-chloro-2-methyl-4 Isothiazolin-3-one 2-methyl-4-isothiazoline -3-one copper ammonia sulfate water (28%) Add water to 400ml 100mn 7g 5g g g 1000ml! 5,40 0.1g 0,7g 0.02g 0.01g 0,005g 2,0g 1 000ml pH (25°C) 4.0
In the color developer, the replenisher composition was set so that the chlorine ion and bromide ion concentrations in the tank solution were maintained until the end of the run.

The coated sample was subjected to gradation exposure for sensitometry using a sensitometer (Model FWH manufactured by Fuji Photo Film Co., Ltd., color temperature of light source: 3200 K). The exposure at this time was carried out so that the exposure time was 1/10 second and the exposure amount was 250 CMS.

The sensitometry is processed at the start and end of the running test, and changes in sensitivity of yellow due to running (density change in exposure amount that shows a density of 0.5 at the start of running) and gradation (density 0.5) are processed. Density difference from the point representing 0°3 at 1 ogE to the density point on the high exposure side)
The amount of change in is measured using a Macbeth densitometer, and the results are
Shown in the table.

E 1 E E-3 / / As is clear from Table 3, when the constituent requirements of the present invention are met, fluctuations in photographic properties due to running are extremely small, and rapid processing with stabilized photographic properties is achieved. Ta. (■〜■
, ■~[Phase], 0~0) If the chloride ion concentration of the color developer is not according to the present invention, even if the yellow coupler is according to the present invention, the photographic properties will vary greatly and the object of the present invention will not be achieved. It's not something you do. (for ■〜■■
, ■) If the yellow coupler is not according to the present invention, even if the chlorine ion concentration of the color developer is according to the present invention, the photographic properties will vary greatly and the object of the present invention will not be achieved. (■,■,■~@ for [phase]) Among the present invention, the bromide ion concentration in the color developer is 3
×10-' to lX10-' (■ vs. ■, ■,
rr? In the following cases (@ for ■, ■, [phase], and [phase]), the variation in photographic properties was smaller and even better results were obtained.

Claims (1)

[Scope of Claims] 1) A method of processing a silver halide color photographic light-sensitive material with a color developer containing at least one aromatic primary amine color developing agent, wherein Silver chloride silver halide emulsion and the following general formula (
I) A silver halide color photosensitive material having a yellow coupler represented by
A method for processing a silver halide color photographic light-sensitive material, characterized in that it is processed with a color developer containing ^-^2 to 1.5 x 10^-^1 mol/l. General formula [I] ▲Mathematical formulas, chemical formulas, tables, etc. are available▼ [In the formula, R_1 is an aryl group or a tertiary alkyl group,
R_2 is a fluorine atom, 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) Bromine ion from 3×10^-^5 to 1×10^-^3
The processing method according to claim 1, characterized in that the processing is carried out with a color developer containing mol/l. 3) The processing method according to claim 1, wherein the amount of coated silver on the silver halide color light-sensitive material is 0.75 g or less per 1 m^2 of the light-sensitive material.