JPH02234157A - Method for processing silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To enable rapid development processing freed of occurrence of stains and superior in sharpness by processing a photosensitive material containing a silver halide emulsion high in silver chloride content, and a specified dyestuff with a color developing solution containing chlorine ions and bromine ions each in a specified concentration. CONSTITUTION:The photosensitive material to be used contains the silver halide emulsion composed substantially of silver chloride, i.e., containing silver chloride in an amount of >=80mol% of the total silver halide in at least one layer, and contains the dyestuff having an absorption maximum wavelength in the range of 680 - 720nm in a gelatin film in at least one layer. This photosensitive material is processed with the color developing solution containing an aromatic primary amine color developing agent and chlorine ions in a concentration of 3.5X10<-2> - 1.5X10<-1>mol/l and bromine ions in a concentration of 3.0X10<-5> - 1.0X10<-3>mol/l, thus permitting the obtained rapid developing method to be improved in restraining stains and enhanced in sharpness.

Description

Detailed Description of the Invention (!Field of Industrial Application) The present invention relates to a method K for processing silver halide color photographic materials.
In more detail, it relates to a development process using a high silver chloride silver halide photographic light-sensitive material with excellent developability and excellent desilvering performance.

At the same time, the present invention relates to a development processing method K for obtaining a halogenated steel color photographic material with improved white background (stain) and excellent sharpness despite rapid processing.

(Prior Art) In recent years, in the photographic processing of color photosensitive materials, it has been desired to shorten the processing time due to the shortening of the finishing delivery time and the reduction of the processing work.

Increasing the temperature and increasing the amount of replenishment are common methods to shorten the time of each treatment step, but many other methods have been proposed, such as increasing stirring or adding various accelerators. Ta. In particular, for the purpose of speeding up color development and/or reducing the amount of replenishment, color photographic sensitizers containing silver chloride emulsions instead of silver iodide emulsions have been widely used. Methods of processing materials are known. For example, International Publication (WO) a7-04534
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 rapid processing is performed using the above method, stains (coloring of the white background) occur in the non-color developing areas (hereinafter referred to as white background) of the color photographic light-sensitive material during continuous processing, resulting in a white background. It has been found that serious problems occur, such as contamination and desilvering failure in the image area (coloring area), resulting in a decrease in color reproducibility and saturation.

The main causes of staining as described above are: ■ Silver development of unexposed areas, so-called cut 17K.
Attributable stain.

■ Color contamination caused by oxides (tar components, etc.) of color developing agents adhering to photosensitive materials.

■ After the color development process, the developing agent is brought into the oxidation bath (bleach solution or bleach-fix solution), where it is oxidized and indiscriminately couples with couplers to form dyes, a so-called bleaching agent.

■ So-called residual color that remains even after processing due to insufficient washing of anti-irradiation dyes and sensitizing dyes.

etc., but K to prevent contamination on white backgrounds is to comprehensively improve and prevent contamination caused by the above ■~■K.
It is achieved for the first time.

Special K In order to improve the stain caused by the residual color of the irradiation-preventing dye mentioned in (1) above, it has been proposed to use the dyes described in JP-A-62-273527 and JP-A-63-48550. However, although the residual color was improved, sufficient sharpness could not be obtained.

On the other hand, defective desilvering due to high silver chloride emulsions is presumed to occur due to the following reasons.

In other words, compared to silver iodobromide and silver chlorobromide emulsions, silver chloride emulsions have higher silver ion solubility (as a result, dissolution physical development is significantly accelerated and development is completed in a short period of time, but silver ions are not formed). The developed silver is difficult to form into filaments, and large developed silver with a small surface area and almost a spherical shape is produced. It is thought that as a result, the desilvering speed is delayed.

As a means of solving the above-mentioned problems, in a rapid processing method using high silver chloride color photographic light-sensitive materials, JP-A-58 was proposed as a method for reducing fluctuations in photographic properties (especially capri) caused by continuous processing. -95345, JP-A-59-
No. 232,342 discloses the use of an organic anti-fouling agent. However, it has been found that the use of an organic anti-capri agent tends to cause a decrease in the maximum concentration and also tends to cause desilvering failure, so it cannot be said to be a preferred method.

Furthermore, in JP-A No. 61-70552, a highly chlorinated silver halide color photographic light-sensitive material is used, and during development, a replenishment amount is added in an amount that does not cause overflow into the developing bath, in order to reduce developer replenishment. The method is described in JP-A No. 63-106655.
For the purpose of stabilizing processing, the publication describes that a silver halide color photographic light-sensitive material in which the silver halide emulsion layer has a high silver chloride content is treated with a color developing solution containing a droxyamine compound and chloride at a predetermined concentration or higher. A method of processing is disclosed.

However, none of these methods was sufficiently effective in preventing the occurrence of staining, and the improvement in desilvering performance K was not satisfactory, either.

(Problems to be Solved by the Invention) Accordingly, the first object of the present invention is to use a highly compacted silver color photographic light-sensitive material to produce a halogen-free film that is quick, prevents staining, and has excellent sharpness. An object of the present invention is to provide a development processing method for obtaining a Kasen color photographic light-sensitive material.

A second object of the present invention is to use a high-silver chloride color photographic light-sensitive material, to have excellent photographic properties with high maximum density and low minimum density in rapid processing, and to improve photographic properties due to continuous processing. It is an object of the present invention to provide a development processing method in which fluctuations (especially minimum density) are significantly suppressed.

A third object of the present invention is to provide a developing method that uses a high-silver chloride color photographic light-sensitive material, has a small amount of residual silver, and has improved desilvering properties.

(Means for Solving the Problems) The above object is achieved by processing a silver octalogonide color photographic light-sensitive material with a color developer containing at least one type of aromatic primary amine color developing agent. A silver halide having at least one layer of a high silver chloride silver halide emulsion consisting of chloride scissors of molten or higher, and at least one dye having a maximum absorption wavelength in the range of 680 to 720 nm in the gelatin film. The color photosensitive material contains 3.5 X 10-2 to 1.5 X 10-1 mol/t of chlorine ions and 3.5 X 10-1 mol/t of bromine ions. OX10～
1. It has been found that ζ can be effectively achieved by a method for processing a silver halide color photographic light-sensitive material, which is characterized by processing with a color developer containing OX10 mol/t.

Chlorine ions are well known as one of the anti-capri agents, but their effect is small, and even when used in large quantities, fog increases with continuous processing and occurs when processed with automatic processors. K was not able to completely prevent streaky capri, but had the adverse effect of delaying reverse K development and lowering the maximum density.

Bromine ion is also well known as one of the anti-capri agents, but depending on the amount K added, it can prevent capri caused by continuous processing K, that is, capri caused by development, but it may inhibit development. The maximum density and sensitivity were lowered and could not withstand practical use.

On the other hand, in silver halide color photographic light-sensitive materials, in order to prevent irradiation during exposure or printing, and to increase safety against so-called safelights, it is necessary to reduce sensitivity and deteriorate latent image storage. Various dyes are used that do not adversely affect photographic properties or degrade quality as stains (remaining colors) after processing.

During rapid processing, these dyes may be insufficiently washed, or they may be eluted into the washing water of the color developer and/or the stabilizing processing solution, causing the processing solution to be colored, or the processed color photographic light-sensitive material may be damaged. In some cases, undesirable stains such as coloring may occur, which is an important problem especially in rapid processing K. In order to prevent staining (color contamination) caused by such dyes, it is preferable to use general K dye, which is decomposed with an alkali or reducing agent in a color developer and becomes colorless K. However, in rapid processing, In particular, cleaning and decoloring of dyes in color developers are important techniques.

In the present invention, by using specific amounts of chlorine ions and bromide ions in the color developer, it is possible to suppress the development power blur without reducing the maximum density, and furthermore, the rapid processing K Nevertheless, it promotes the washing effect of the aforementioned dye in the color developer, and at the same time it can prevent the detachment of the sensitizing dye, resulting in suppression of staining and, for example, an excellent white background can be obtained. Ta.

At the same time, the use of the chloride ion concentration and bromide ion concentration of the present invention and the above-mentioned dyes significantly improved the desilvering properties, and moreover, the sharpness was improved! K-worthy. In particular, it is noteworthy that such an effect could be achieved by the structure of the dye used in this way.

The present invention will be explained in detail below.

The silver halide emulsion of the present invention consists essentially of silver chloride.

Here, the term "substantial K" means that the content of silver chloride relative to the total amount of silver halide K is 80 molti or more, preferably 95 molti or more, and more preferably 98 molti or more. From the viewpoint of rapidity, the higher the silver chloride content, the more preferable.

The coating amount of the silver halide photosensitive material of the present invention is 0. Bog
/m'' or less is preferable in terms of speed, desilvering performance, and stain prevention.This is thought to be due to the effect of reducing the K and # thicknesses in addition to simply reducing the amount of silver.The amount of coated silver is 0.
75. ! It is more preferably iI/m'' or less, particularly preferably 0.659/m' or less, and preferably 0.3011/m'' or more from the viewpoint of image density etc.

In the present invention, 3 to 5 chloride ions are added to the color developer.
It is necessary to contain X10 to 1.5X10 moh/t. Preferably << is 4 X 1 0-2 to IXI
O mol/t. Chlorine ion concentration is 1.5×10
If the amount is more than mol/t, it has the disadvantage of retarding development and does not achieve the object of the present invention of rapid development and high maximum density. In addition, staining cannot be prevented with 3.5 x 10 mol/t uncoated, and the change in photographic properties (especially the minimum density) due to continuous processing is large, and the amount of residual silver is also low. However, the purpose of the present invention is not achieved.

In the present invention, K bromine ions in the color developer are added to 3. O
X10 mol/t~1. It is necessary to contain OX10 mol/t. Preferably << is 5.0×10″″5
~5×lO mol/t. Bromine ion concentration is IXI
If it is more than O mol/t, development will be delayed, maximum density and sensitivity will be reduced; 3. If O x is less than 10-5 mol/t, staining cannot be prevented and furthermore, photographic property fluctuations (%K minimum density) due to continuous processing and
Desilvering defects cannot be prevented, and the object of the present invention cannot be achieved.

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

When added directly to a color developer, chlorine ion supplying substances include sodium chloride, potassium chloride, ammonium chloride, nickel chloride, ltX-r/' nesium, manganese chloride, calcium chloride, and cadmium chloride. Among them, preferred are sodium chloride and potassium chloride.

Further, K may be supplied in the form of a counter salt of a fluorescent brightener added to the developer. As a supply material for bromide ions, sodium bromide, potassium bromide, ammonium bromide, lithium bromide, calcium bromide, magnesium A, manganese bromide, nickel bromide, cadmium bromide, cerium bromide,
Examples include thallium bromide, of which potassium bromide and sodium bromide are preferred.

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

The details of the dye used in the present invention will be explained below.

The dye of the present invention can be selected by measuring the maximum spectral absorption in a gelatin film using the method described below. That is,
Add 0 dye to a 5% aqueous solution of alkali-treated ossein gelatin.
．． Melt the gelatin so that it is 0.1%, then add 5% gelatin.
1/m' and dye coating amount is 10 μi/m' on a transparent support, and after drying, the spectral absorption density is measured and the maximum absorption wavelength is determined. Maximum absorption wavelength is 680
The irradiation prevention effect is small in the case of nm-free 《, 72
For dyes with a diameter of 0 nm or more, desensitization due to salmon exposure is large.

The following general (Im) preferably used in the present invention
) and (Ib).

General formula (■1) (In the formula, x and x' are each a hydrogen atom, a hydroxyl group, a carpoxyl group, -COOR -COR -CONH2
, 1-1-CONR1R2 represents an alkyl group, an aryl group or an amino group, Y and Y' each represent a hydrogen atom, an alkyl group, an aryl group or an amino group, and 2 and 2' each represent a hydrogen atom or a cyano group. , carboxyl group, sulfo group,
Amino group, -COOR5, -COR3, R4 R
4 -CONR3R4 represents an alkyl group or an aryl group. R1 + R5 each represents an alkyl group or an aryl group, R2 r R4 each represents a hydrogen atom, an alkyl group, or an aryl group a L1 + L2
, L3, L4, L5 each represent a methine group, n is 1,
2 or 3, and M"+ represents an n-valent cation.) X%X', Y%Y', Z%Z', R,, R2, R
3, the alkyl group represented by R4 is an unsubstituted alkyl group (for example, methyl, ethyl, n-butyl, imbrovir, cyclohexyl), a t-substituted 7-alkyl group {F. Ct. Halogen atoms such as Br (e.g. 2-chloroethyl, tri7fluoromethyl, 1,1,2.2-tetrafluoroethyl), phenyl & (e.g. G?penzyl, phenethyl, 4-chlorobenzyl, 2-sulfopenzyl,
4-sulfopensol, 4-sulfophenethyl, 4-(3
-sulfobrovir)oxypenzyl), hydroxyl group (example *-
(2-hydroxyethyl, 3-hydroxyglobil),
Cyano group (e.g. 2-cyanoethyl), caldenic acid group (
For example, carboxymethyl, 2-carxyethyl, 4-
caldexybutyl, 1-carpoxyethyl), sulfonic acid groups (e.g. sulfomethyl, 2-sulfoethyl, 3-sulfoglovir, 4-sulfobutyl), alkoxy groups (e.g. 2-methoxyethyl, 2-(2-hydroxyethoxy)ethyl), Amine groups (eg 2-dimethylaminoethyl, 2-diethylaminoethyl) or ester groups (eg ethoxylponylmethyl, methoxycargenylmethyl, 2-hydroxyethoxycargenylmethyl) are preferred.

X, X', Y%Y', Z, Z', R, R2, R,
, R4 is an unsubstituted aryl group (e.g., phenyl, naphthyl) or a substituted aryl group {as a substituent, a halogen H group such as F, CL, Br (e.g., 2.5-dichlorophenyl, 4-chlorophenyl)
, hydroxyl group (e.g. 4-hydroxy 7enyl), cargenic acid group (e.g. 2-carpoxyphenyl, 3.5-dicarboxyphenyl), sulfonic acid group (4fiJ Eha 3-
sulfophenyl, 4-sulfofenyl, 2,5-disulfophenyl), alkoxy groups (e.g. 4-methoxyphenyl, 4-(3-sulfofuropyloxy)phenyl, 4
(methoxy-3-sulfophenyl), alkyl groups (e.g. 4-cyanophenyl) or a haester group (flJ 4-ethoxycardenyl 7enyl)} is preferred.

Methi expressed as LLLLL 1% 2' 3% 4%
The pentan group is preferably a methine group with no i° substitution, but it may have a substituent (for example, methyl, ethyl, 2-sulfoethyl).

M”+ is an n-valent (n represents 1, 2, or 3) cation (
For example, H, Na, K+, Ca2++ + (eg, inorganic salts such as sodium, potassium, ammonium, etc., or organic amine salts such as triethylammonium, pyridinium, etc.) may be formed.

Among the general formulas (Im), preferred are X%K1Y, Y
'． If Z or 2' is a sulfonic acid group, << represents a carboxylic acid group, or at least one sulfonic acid group or carboxylic acid group. It represents a group having a soluble acid group, and more preferably 2 and 2' are cyano groups, or << represents a substituted or unsubstituted carpamoyl group, and Y and Y' are less <<
Both represent a group having one sulfonic acid group or carboxylic acid group.

Specific examples of the dye represented by general formula (Ia) are shown below.

(HOCH2) represents 4P+>.

When the general formula (l1) has caldicic acid or smoked sulfonic acid, these acids can be used as free acids or as salts (Ia-1 1 a-2 !a-3 I 1-5 I ■&-8 lm-15 1m-18 lm-16 Ljl2L-fl25%)5N&? ■〇H280,Na The dye represented by the general formula (I&) is
7 8,6 2 1, 1,5 1 2,8 6
It can be synthesized by the method described in No. 3, No. 1,579,89゜9K. Hydroxypyridones used in the synthesis of dyes represented by the general formula (Im) are also described in "Heterocyclic Compounds - Pyridine and Its Derivatives - Part 3" edited by Talinsberg (Interscience Publishing, 1962).
, Journal of the American Chemical Society (J. Am. Ch@w.S (If!.)
1943, Volume 65, Page 449, Journal of Chemical Technology and Biotechnology (J.Chew.Teeh.Biot@ehnol)
1986, volume 36, page 410, Tetrahe No.
y (T@trahedron) 1966, vol. 122, p. 445, Japanese Patent Publication No. 61-52827, West German Patent No. 2.162, 612, No. 2,349,
It can be synthesized by the method described in No. 709, No. 2.9 G 2,48 6, US 5% Permit No. 3,763.170, etc.

The following general formula (Ib) will be explained in detail.

(Ib) R? In the formula, R1 and R4 each represent an alkyl group, an aryl group, or a heterocyclic group, R and R each represent an alkyl group, an aryl group, a heterocyclic group, COR7 or SO2R7, and R3 and R6 each represent a hydrogen atom. , cyano group, hydroxyl group, calgenic acid group, alkyl group, aryl group, 1000R'
-OR'-NR8R' -N(R8)C
OR', -so■R7, -COR', -N(R')So
2R'-CONR8R' or 1N(R')CONR'R
'(R' represents an alkyl group or an aryl group, R
, R each represent a hydrogen atom, an alkyl group or an aryl group. ), and L, , L2 and L3 each represent a methine group. However, R, R. R,R%R,R,L,,L
Or is at least one of L equal to at least one force? represents a group having a phosphoric acid group or a sulfonic acid group] R%R%R%R
The alkyl group represented by %R, R, R, R and 9 may be a straight chain, branched or cyclic alkyl group [, y substituent [e.g. halogen atom (e.g. F, Cl, Br, etc.), hydroxyl group, cyano] group, caldenic acid group, sulfonic acid group, alkoxy group (e.g. methoxy group, impropoxy group, etc.), aryloxy group (e.g. phenoxy group, 4-sulfophenoxy group, etc.), amine group (e.g. unsubstituted amine group, dimethylamino group) , N-(
3-sulfoprobyl)-N-methylamino group, acetylamino group, methanesulfonylamino group, methylcarbamoylamino group, methylamino group, anilino group, etc.), aryl group (e.g. phenyl group, naphthyl group, etc.) It's okay. Specifically, methyl, ethyl, n-provil, improvil, t-butyl, 2-ethylhexyl,
Penzyl, cyclohexyl, 2-sulfoethyl, 3-sulfofurovir, 4-sulfoptyl, 6-sulfohexyl, 2-sulfopenzyl, 2.4-disulfopenzyl, 2
-Cal? xyethyl, carboxymethyl, 4-calgexypenzyl, 2,4-di(3-sulfoproboxy)penzyl, 2-chloroethyl%}ly7fluoromethyl, dimethylamineethyl, 2-(:N-methyl-N-(4- Examples include groups such as sulfobutyl)amine]ethyl, 2-methanesulfonylaminoethyl, 2-acetylaminoethyl, 2-biverazinoethyl, and 2-hydroxyethyl.

Examples of the aryl group represented by R1, R2, R3, R4, R5, R6, R7 R8 and R9 include a phenyl group and a naphthyl group. These include substituents [for example, halogen atoms (e.g., F, Ct, Br, etc.), alkyl groups (
(e.g. methyl group, ethyl group, etc.), hydroxyl group, carboxylic acid group, sulfonic acid group, cyan group, alkoxy group (e.g. methoxy group, ethoxy group, 2-hydroxyethoxy group, 4-
Sulfobutoxy group, 3-calgexyprodexy group, n-
(e.g., poxy group), amino group (e.g., unsubstituted amine group,
Dimethylamino group, diethylamino group, acetylamino group, methanesulfonylamino group, N-methyl-N-(4
-sulfoptyl) amino group, carbamoyl group (e.g., methylcarbamoyl group, 3-sulfopropylcarpamoyl group, etc.), sulfamoyl group (e.g., methylsulfamoyl group, etc.). Specifically, 4-sulfophenyl, 2.5-disulfophenyl, 2-meth-fk-
4-sulfophenyl, 3-sulfophenyl, 3,5-disulfophenyl, 4-caldexyphenyl, 5,7-disulfo-3-naphthyl, 4-dimethylaminophenyl,
4-{N-ethyl-N-(2-sulfoethyl)amino}
Phenyl, 3-acetylaminophenyl, 3-(2-sulfoethylrupamoyl)phenyl, 4-hydroxyphenyl, 3-methoxyphenyl, pilyl, 4-cy7/
Examples thereof include groups such as 7enyl, 2.4-mono(4-sulfoptoxy)phenyl, 4-/rolophenyl, 2-chloro4-1tylphenyl, and 3.5-dicardexyphenyl.

The heterocyclic group represented by R R R, R is
5 or Fi represents a 6-membered nitrogen-containing heterocyclic group (including fused rationales), and substituents [e.g. carboxylic acid group, sulfonic acid group, hydroxyl group, halogen atom (e.g. F, C, Br, etc.), alkyl group (e.g. methyl group, ethyl group, etc.). Specifically, 5-sulfobiridin-2-yl,
5-cardexypyridin-2-yl, 5-sulfopyridin-2-yl, 5-carpoxypyridin-2-yl,
5-Sulfobenzothiazol-2-yl, 2-piIJ-
/l, 2-penzooxazolyl, 6-caldexymethylpyridin-2-yl, and the like.

The acyl group represented by R and R is preferably a lower alkylcarbonyl group such as an acetyl group or a propionyl group.

The methyl group represented by LL and L is a substituent [for example, an alkyl group (e.g., methyl group, ethyl group, benzyl group, 2-sulfoethyl group, 2-hydroxyethyl group, etc.), an aryl group (e.g., phenyl group, p monotolyl group, etc.)
, calgenic acid group, sulfonic acid group, cyanogen group, amine group (
For example, dimethylamino group, etc.), halogen atom (for example, F
, CL, Br% r, etc.)], methine groups may be connected to each other to form a ring (for example, in general formula (Ib), R and R4 may have at least one ring). Calanoic acid group << represents an alkyl group or aryl group having a sulfonic acid group.

The caldenic acid group and the sulfonic acid group may be either free acids or salts (for example, inorganic salts such as Na salt, K salt, NH4 salt, organic salts such as triethylammonium salt, etc.).

Specific examples of the dye (Ib) used in the present invention are shown below, but the present invention is not limited thereto.

The dye represented by the general formula (Ib) is
No. 069, No. 43-3504, No. 52-38056, No. 54-38129, riff! 55-10059
No. 49-99620, No. 59-16834, No. 63-316853 or U.S. Patent No. 4,18
It can be synthesized using the method described in, for example, No. 1,225.

The amount of the dye of general formula (I1) or (Ib) to be used is as follows: color photographic material 1. Preferably 00001g to 1g per serving
, more preferably 0.0005g70.1g.

The dye of general formula (1) or (Ib) is usually used as an irradiation-preventing dye. It is usually used in a halogenated emulsion layer, but it is particularly preferably added to a green-sensitive emulsion layer or a red-sensitive emulsion layer.

In the present invention, from the viewpoint of processing stability during continuous processing and prevention of streaky pressure fog, it is preferable that the color developer contains substantially no K sulfite ions, but in order to suppress deterioration of the developer, Do not use the developer for a long time, use physical means such as using a floating pig to suppress the effects of air oxidation, or reducing the opening degree of the developer barrel, reduce the developer temperature, or use organic preservatives. Chemical means such as adding . 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, it is an organic compound that has the function of preventing the oxidation of color developing agents due to air, etc. Among them, hydroxylamine conductors (excluding hydroxylamine, hereinafter referred to as macro 1), hydroxamic acids, hydrazines, and hydrazides. , phenols, α-hydroxyketones, α-aminoketones, sugars, monoamines, diamines, polyamines, quaternary ammonium salts, nitroxy radicals, alcohols, oximes, diamide compounds, fused cyclic amines are particularly effective organic preservatives. These are Japanese Patent Application No. 61-147823 and Japanese Patent Application No. 61-173.
No. 595, No. 61-165621, No. 61-1886
No. 19, No. 61-197760, No. 61-18656
No. 1, No. 61-198987, No. 61-201861
No. 61-186559, No. 61-170756, No. 61-188742, No. 61-188741,
U.S. Patent No. 3.615,503, U.S. Patent No. 2.4
9 4, 9 0 3, JP-A-52-143020,
It is disclosed in Japanese Patent Publication No. 48-30496.

Regarding the preferred organic preservative K, 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 at a concentration of 5 mol/t to 0.5 mol/1, preferably 0.03 mol/t to 0.1 mol/t.

Particularly preferred is the addition of a hydroxylamine rust conductor and/or a hydrazine derivative.

The hydroxylamine derivative is preferably one represented by the following general formula (II).

General formula (II) R2 1 -N- R2 2 0H In the formula, u2 1 and R22 are a hydrogen atom, unsubstituted or << is a t-substituted alkyl group, unsubstituted or substituted alkenyl group, unsubstituted or << is a substituted Represents an aryl group or a heteroaromatic group. R and R cannot become hydrogen atoms at the same time《
, may be linked to each other to form a heterocycle together with a nitrogen atom. The ring structure of the heterocycle is a 5- to 6-membered ring composed of carbon atoms, hydrogen atoms, halogen atoms, oxygen atoms, nitrogen atoms, sulfur atoms, etc., and may be saturated or unsaturated.

R2 1 , R22 is preferably an alkyl group or an alkenyl group, and 1 to 10 carbon atoms are preferable, and 1 to 5 carbon atoms are particularly preferable. Examples of the nitrogen-containing heterocycle formed by linking R21 and R22 include a piperidine group, a pyrrolidylyl group, an N-alkylpiperazyl group, a morpholyl group, an indolinyl group, and a penztriazole group.

Preferred substituent groups for R21 and 822 are a hydroxy group, an alkoxy group, an alkyl or arylsulfonyl group, an amide group, a caldexy group, a cyano group, a sulfo group, a nitro group and an amino group.

Compound Example n-1 C2T{5-N-C2H5 0H CH,QC2H4-N-C2H4-OCH30H It-3 0H I1-4 0H ■C 5 It-8 NHOH As the hydrazines and hydrazides, the following are preferred.

General formula (m) In the formula, R31, R32, and R35 represent a hydrogen atom, a substituted or unsubstituted alkyl group, an aryl group, or a heterocyclic group, and R represents a hydroxy group, a hydroxyamino group, or a heterocyclic group. It represents a substituted or unsubstituted alkyl group, aryl group, heterocyclic group, alkoxy group, aryloxy group, carbamoyl group, or amine group. The heterocyclic group is a 5- to 6-membered ring composed of C, H, 0, N, S, and halogen atoms, and may be either saturated or unsaturated. X31 is -C
O- represents a divalent group selected from -SO2-, NH or -C-, and n is 0 or l. In particular, when K n = O, R54Vi represents a group selected from an alkyl group, an aryl group, and a heterocyclic group,
R35 and R54 may jointly form a petero ring.

-I [In (m), R51, R32, and R33 are preferably hydrogen atoms or C1 to C1o alkyl groups, and most preferably R31 and R32 are hydrogen atoms.

In general formula (III), R34 is preferably an alkyl group, an aryl group, an alkoxy group, a carbamoyl group, or an amine group. Particularly preferred are alkyl groups and substituted alkyl groups. Preferred substituents for the alkyl group here include a caldexyl group, a sulfo group, a nitro group, an amino group, and a sulfono group. X31 is preferably -co- or -SO2-, and most preferably -co-.

(Compound example) In-1 m-2 NH 2NH{-CFI2+2So 3HIl1-3 NH2NH+CH2370H m m-7 I11-8 ■III-10 NH2NHCOCH3 NH2NHC00C2H5 NH2N'}ICONH2 mix 1 ■- 1 8 NH 2NHC}1 2CH 2COOH■- 1 9 ■- 1 2 NH2 dish So, H m- 1 3 W NH2NHCNI{2 m- 20 m-1 4 NH2NHCOCONHNH2 m-1 m- 21 NH2NHCH2CH2CH2So, H ■- 1 6 Iml - 2 2 m- B2 ■CHC OO} t c4n, (n) l-23 NH2N(CM2CH280,H) 2 General formula (n
) or (m) and amines represented by the following general formula (F/) or (V) can improve the stability of the color developer and improve the stability during continuous processing. is more preferable in terms of improving stability.

General formula (IV) (Compound example) IV-1 N+cH2CH20H)3 IV-2 H2NCH2C}120H I1/-3 HN+cH2CI{20H) 2IV-4 R -N-R" In the formula, R71, H72, R73 are It represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group, or a heterocyclic group. Here, R71 and R72, R71 and n75, or R72 and H73 may be connected to form a nitrogen-containing heterocycle.

Here, n71, R72 and R73 may have a t substituent. R71, R72, and R73 are particularly preferably a hydrogen atom or an alkyl group. Examples of the substituent include a hydroxyl group, a sulfo group, a xyl group, a halogen atom, a nitro group, and an amino group.

If/-5 ■-6 fV-7 C, H15N(CH2CHCH20H)21'l/-8 ■- 1 5 IV-9 ■- 1 6 ■- 1 7 a2N-c+cH2oH)3 ■-10 (HOCH2CH2+2NCH2CH2SO2CH3■
- 1 1 HN4CH 2COOH ) 2 ■- 1 2 HOOCCH2C}T2CHCOOH ■-13 H2HCH2CH2SO2NH2 ■ - 1 4 ■- 1 8 ■- 1 9 0CH3 General formula (V) In the formula, X is K necessary to complete the fused ring. It represents a trivalent atomic group, and R and R represent an alkylene group, an arylene group, an alkenylene group, or an aralkylene group.

Here, R+ and R2 may be the same or different.

Among general formulas (V), particularly preferred are general formulas (V-
These are compounds represented by a) and (vb).

R2 is defined as in general formula (V), and R represents the same group as RR or +1 CH2C.

In the general formula (V-a), it is preferable that X1 is LaN. The number of carbon atoms in R1 R2 R is preferably 6 or less, more preferably 3 or less, and most preferably 2.

RRR is preferably an alkylene group or an arylene group, and most preferably an alkylene group.

In the formula, X represents N or "9CH.R in the formula, RR is defined as in the general formula (V).

In general formula (v-b), the number of carbon atoms in R1R2 is preferably 6 or less. n 1R2 is preferably an alkylene group or an arylene group, and most preferably an alkylene group.

(1-5) Among the compounds represented by the general formula (V-a) and (v-b), the compound represented by the special formula (V-a) is preferable. CM20H V-1 V-6 V-2 V-7 v-4 C-8) ■-8 V-9 V-14 V-10 V-11 v-1 V-1 ■- 1 7 V-1 V-18 The organic preservatives mentioned above can be obtained as commercially available products;
It can also be synthesized by the method described in No. 74 and the like.

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

The color developer used in the present invention contains a known aromatic primary amine color developing agent. A preferred example is p-7 enylene diamine, and representative examples are shown below, but the invention is not limited thereto.

D-I N. N-diethyl-p-phenyl diamine D-2 4-(N-ethyl-N-(β-hydroxyethyl)amino)aniline D-3 2-methyl-4-[N-ethyl-N-(β-hydroxyethyl ) Amino] Aniline D-4 4-Amino-3-methyl-N-ethyl-N-(
β-methanesulfonamidoethyl)-aniline These p-phenylenediamine derivatives may also be salts such as sulfate, hydrochloride, p-}luenesulfonate, and the like. The amount of the aromatic primary amine developing agent used is preferably about 0.1 g to 20 g, more preferably about 0.5 to about 10 g, per ton of developing solution.

The color developer used in the present invention is preferably
to 12, more preferably 9 to ILO, and the color developer may contain other known developer component compounds.

In order to maintain the above condition, it is preferable to use various buffering agents. Buffers include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate, potassium borate, tetraborate. Sodium (borax), potassium tetraborate, 0-
Sodium hydroxybenzoate (sodium salicylate), potassium O-hydroxybenzoate, 5-sulfo-2
-sodium hydroxybenzoate (sodium 5-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 mol/t.
It is preferable that the value is not less than 《, especially 0. 1 mol/t~0
Particularly preferred is 4 mol/t.

In addition, various free chelating agents can be used in the color developer as an agent for preventing precipitation of calcium or magnesium, or to improve the stability of the color developer.

Specific examples of K will be shown below, but the invention is not limited to these. Nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, triethylenetetraminehexaacetic acid,
N,N. N-}rimethylenephosphonic acid, ethylenediamine-N. N. N'N'-tetramethylenephosphonic acid, 1
．． 3-diamine-2-propanoltetraacetic acid, transcyclohexanediaminetetraacetic acid, nitrilotribropionic acid, 1,2-diaminopropanetetraacetic acid, hydroxyethyliminodiacetic acid, glycol etherdiaminetetraacetic acid, hydroxyethylenediaminetriacetic acid, ethylenediamineorthohydroxyf enyl acetic acid, 2-phosphonobutane-1
．． 2.4-}ricargonic acid, l-hydroxyethylidene-1,1-sophosphonic acid, N. N'-bis(2-
hydroxypenzyl) ethylenediamine-N, N'
- diacetic acid, catechol-3.4.6-trisulfonic acid,
Catechol-3.5-disulfonic acid, 5-sulfo? lJ
F-ruic acid, 4-sulfosalicylic acid, and two or more of these chelating agents may be used in combination as necessary.

These chelating agents may be added in an amount sufficient to sequester metal ions in the color developer. For example, 1t
It is about 0.19 to 10 g 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. 3g-7826, No. 44-123
No. 80, No. 45-9019 and U.S. Patent No. 3,81
3,247, etc., JP-A-52-49829 and JP-A-50-1555
p-phenylenediamine type compounds represented by No. 4, JP-A-50-137726, JP-A-44-30074, JP-A-56-15'6826 and JP-A-5
Quaternary ammonium salts represented by K such as No. 2-43429, U.S. Pat.
, 119,462, U.S. Pat. No. 2,494,903, U.S. Pat. No. 3,12
8,1 8 2, 4,230.796, 3.2
5 3.9 1 9, Special Publication No. 41-11431,
U.S. Patent No. 2.4 8 2.5 4 6, U.S. Patent No. 2,59
6,926 and 3,582,346, etc., Japanese Patent Publication No. 37-16088,
No. 42-25201, U.S. Patent No. 3,128.1
8 No. 3, Special Publication No. 41-11431, Mukai 42-23
No. 883 and U.S. Patent No. 3.5 3 2.5 0 1
Polyalkylene oxide represented by number K, etc. 1
-7enyl-3-virazolidones, hydrazines, mesoionic compounds, ionic compounds, imidazoles, etc. can be added as necessary. Preferably, the color developer contains substantially no pendyl alcohol. Substantially means color developer 11592.01 or less.
Preferably, it does not contain any. When it is not substantially contained, fluctuations in photographic properties during continuous processing, especially increases in stain, are smaller, and more favorable results can be obtained.

In the present invention, in addition to chloride ions and bromide ions K, any anti-capri agent can be added as required. As anti-capri agents, alkali metal halides such as potassium iodide and organic anti-capri agents can be used. Examples of organic anti-capri agents include penzotriazole, 6-
Nitrobenzimidazole, 5-nitroisoindazole, 5-methylpenzotriazole, 5-nitrobenzotriazole, 5-chlorobenzotriazole, 2-
Typical examples include nitrogen-containing heterocyclic compounds such as thiazolylpenzimidazole, 2-thiazolylmethylpenzimidazole, indazole, hydroxyadeindolizine, and adenine.

The color developer K used in the present invention preferably contains a fluorescent brightener. As a fluorescent brightener, 4,4'-
Diamino-2,2'-disulfostirpene compounds are preferred. The amount added is O to 10 El/t, preferably 0.1
~ag7t.

Furthermore, various surfactants such as alkyl sulfonic acid, aryl phosphonic acid, aliphatic carboxylic acid, and aromatic carboxylic acid may be added depending on the K required.

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 when the temperature is 20 seconds to 60 seconds. In addition, the treatment temperature is 33 to 45°C, preferably <3
At 6 to 40°C, the stain prevention effect is particularly remarkable.

The replenishment amount of the color developer during continuous processing is preferably 20 to 220, particularly 40 to 140, per 12 of the photosensitive material, since the effects of the present invention can be effectively exhibited.

In the present invention K, desilvering treatment is performed after color development. The desilvering process generally consists of a bleaching process and a fixing process, but at the same time K
It is especially preferable if this is done.

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).

Depending on the required K, boric acid, borax, sodium metaborate} One type with a buffering capacity such as IJum, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate, tartaric acid, etc. The above inorganic acids, organic acids, alkali metal or ammonium salts thereof, or corrosion inhibitors such as ammonium nitrate and guanidine can be added.

The fixing agent used in the bleach-fixing solution or fixing solution related 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-dithia-1,8-octanediol These silver halide solubilizers can be used in combination of 1s or 2a or more. It is also possible to use a special bleach-fix solution made of a combination of a fixing agent and a large amount of a halide such as potassium iodide as described in JP-A-55-155354. In the present invention, preference is given to using thiosulfates, especially ammonium thiosulfates. The amount of fixing agent per 1 ton is preferably 0.3 to 2 moles, and more preferably 05 to 1.0 moles.

One area of the bleach-fix solution or fixer solution in the present invention is 3
-8 is preferable, and 4-7 is especially preferable. If the ratio is lower than this, the desilvering property is improved, but the deterioration of the solution and the leucoization of the cyan dye are promoted. On the other hand, if the value of 1 is higher than this, desilvering is delayed and stains are more likely to occur.

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

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

The bleach-fix solution and fixer 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 002 in terms of sulfite ion.
It is preferable to contain ~0.50 mol/t《, further K
#f is 0.04 to 0.40 mol/t. Special K
The addition of amsonium sulfite is preferred.

Sulfites are commonly added as preservatives, but other preservatives include ascorbic acid, cartilage bisulfite adducts,
Sulfinic acids, a carbonyl compound, sulfinic acids, etc. may be added to (1), and a buffering agent, a fluorescent brightener, a chelating agent, a fungicide, etc. may be added to K as necessary. Good too.

The processing time of the bleach-fix solution of the present invention is preferably 10 seconds to 120 seconds, and preferably 20 seconds to 60 seconds. Also, the replenishment amount is 1 photosensitive material.
, 30111j to 250mJ per S, preferably << is 4.
01-1501. Generally, an increase in staining and poor desilvering tend to occur as the amount of replenishment is reduced, but according to the present invention, such problems can be avoided by reducing the amount of bleach-fix replenishment. 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 washing water in the washing process depends on the characteristics of the photosensitive material (for example, depending on the material used such as coupler), the application, the washing water temperature, the number of washing tanks (number of stages), the replenishment method such as countercurrent or forward flow, and various other factors. It can be set over a wide range depending on the conditions. this house,
The relationship between the number of flushing tanks and the amount of water in the multistage countercurrent method is described in the Journal Op des Society Op Motion.
Picture and Telegraphy Engineers (
Journal of the Society of
Motlon Picture and Televi
sion Engtn@er@) Volume 64, p. 248
-253 (May 1955 issue) K.

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 propagate and the generated suspended matter adheres to the photosensitive phase material. Problems such as this arise. In the processing of the color photosensitive material of the present invention, as a solution to such problems,
Calcium described in Japanese Patent Application No. 61-13 1632,
Methods of reducing magnesium can be used very effectively. In addition, chlorine-based disinfectants such as inthiazolone compounds, thiabendazoles, chlorinated sodium incyanurate, and other penzotriazole described in JP-A No. 57-8542, "Chemistry of Antibacterial and Antifungal Agents" by Hiroshi Horiguchi
, "Sterilization, sterilization, and anti-mildew technology of microorganisms" edited by the Sanitation Technology Society, and "Encyclopedia of antibacterial and anti-fungal agents" edited by the Japanese Dental and Mildew Prevention Society can also be used.

The amount of washing water in the processing of the photosensitive material of the present invention is 4 to 9
and preferably << is 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 general K is 20 seconds to 2 minutes at 15 to 45°C, and preferably 25 to 4
A range of 30 seconds to 1 minute and 30 seconds at 0°C is selected.

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

Furthermore, the photosensitive material of the present invention can also be directly processed with Stabilizing Solution K instead of the above-mentioned 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, fim60-238832, fim60-23
No. 9784, No. 60-239749, No. 61-405
All known methods described in K, such as No. 4 and No. 61-118749, can be used. %Kl-hydroxyethylidene-1,1-diphosphonic acid, 5-chloro2
A stabilizing bath containing -methyl-4-inchazolin-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.

Next, details of the silver halide color photographic material used in the present invention will be explained.

The silver halide emulsion of the present invention consists essentially of silver chloride.

Here, "substantially" means that the content of silver chloride based on the total amount of silver halide is 80 mol % or more, preferably 95 mol % or more, and more preferably 98 mol % or more. From the viewpoint of rapidity, the higher the silver chloride content, the more preferable. Further, the high silver chloride composition of the present invention may contain a small amount of silver bromide or silver iodide. In terms of photosensitivity, this can be useful in many ways, such as increasing the amount of light absorption, strengthening the adsorption of spectral sensitizing dyes, or weakening the desensitization caused by spectral sensitizing dyes.

The silver octalogonide contained in the photographic emulsion layer of the photographic light-sensitive material used in the present invention may have different phases in the interior and surface, or may be made of multi-phase cypress with a bonded structure, or the entire grain may be It may also consist of a homogeneous phase. Moreover, they may be mixed.

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

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

Silver halide photographic emulsions that can be used in the present invention are, for example, Research Disclosure (RD), ▲17643 (
December 1978), pp. 22-23, '! ．． Emulsion manufacturing (
Emulsion preparation
It can be prepared using the method described in ``typ@s)''.

U.S. Patent No. 3.574,628, U.S. Patent No. 3,65
No. 5,394 and British Patent No. 1,4 1 3.7
Monodispersed emulsions such as those described in No. 48 are also preferred.

Tabular grains having an asquid ratio of about 5 or more can also be used in the present invention. Tabular grains are described in Gutoff's book, Photographic Science and Engineering (Gutoff PhotographicSe1).
snce and Engine*rlng), No. 14
Vol. 248-257 (1970); U.S. Patent No. 4,434,226, 4,414,310
No. 4,433.048, No. 4,439,520 and British Patent No. 2,112,157.

The crystal structure may be uniform, the inside and outside may have different halogen compositions, or it may have a layered structure. Further, silver halides having different compositions may be bonded by epitaxial bonding, or compounds other than silver halide such as silver rhodan or lead oxide may be bonded.

Also, a mixture of particles of various crystal forms may be used. The silver halide emulsion used is usually one that has been subjected to physical ripening, chemical ripening, and spectral sensitization. Additives used in such processes are listed in Research Disclosure A17.
643 and A18716, and the relevant parts are summarized in the table below.

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

1. Fu 4. 5. 6. Types of additives Chemical sensitizers Sensitivity enhancers Spectral sensitizers, pages 23-24 Super sensitizers Brighteners Antifoggants pages 24-25 and stabilizers Light absorbers, filter dyes Ultraviolet absorbers page 24 RD17643 23 Pages 2 5-2 6 Dye Image Stabilizer Hardener Binder Plasticizer, Lubricant Coating Aid, Surface Active Agent 13. Static inhibitor 25 pages 26 pages 26 pages 27 pages 26-27 pages 27 pages RD18716 648 pages right column Same as above 648 pages right column ~ 649 right column 649 pages right column ~ 649 pages right column ~ 650 pages left column 651 pages left Column Same as above Page 650 Right column Same as above Same as above Invention K The sensitizing dye used is a continuous color photographic light-sensitive material made of high silver chloride developed with a color developer containing a certain concentration of chloride ions and bromine ions. Further improves the degree of staining that occurs during or after treatment,
Further, from the viewpoint of further improving the stability of photographic properties, those represented by the following general formulas (■a) and (Wb) are preferable.

General formula (Ma) (X-)m In the formula, L represents a methine group or a substituted methine group, and B 1
1 and R each represent an alkyl group or a substituted alkyl group, 2 and z2 each represent an atomic group forming a nitrogen-containing 5- to 6-membered heterocyclic nucleus, and represent an X anion. n represents a numerical value of 1, 3 or 5, n
1 and n2 are O or 1, respectively, and rs =
When n = 5, both n1 and n2 are 0, and when n = 3, either n1 or n2 is O. m
Id Represents O or l, and is O when forming an inner salt. Further, when n is 5, LI'ilrl may be linked to form a substituted or unsubstituted 5- or 6-membered ring.

The cyanine dye K represented by the general formula (M a.) will be explained in detail below.

Examples of the substituent of the substituted methine group represented by L include lower alkyl groups (eg, methyl group, ethyl group, etc.) and aralkyl groups (eg, penzyl group, phenethyl group, etc.).

The alkyl residue represented by H 11 and R12 may be linear, branched, or cyclic. The number of carbon atoms is not limited, but is preferably 1 to 8, and particularly preferably 1 to 4. Examples of substituents for substituted alkyl groups include sulfonic acid groups, carboxyl groups, hydroxyl groups, alkoxy groups, acyloxy groups, and aryl groups (for example, 7
enyl group, dispersed phenyl group, etc.).

These groups may be bonded to the alkyl group alone or in combination of two or more. Further, the sulfonic acid group or the calcarboxylic acid group may form a salt with an alkali metal ion or a quaternary ion of an organic amine. Here, the expression "two or more in combination" includes cases in which these groups each form an independent K-alkyl group K-bond, and cases in which these groups are connected to form an alkyl K-bond.

Examples of the latter include a sulfoalkoxyalkyl group, a sulfoalkoxyalkoxyalkyl group, a carpoxyalkoxyalkyl group, and a sulfophenylalkyl group.

True examples of R and B12 are methyl group, ethyl group, n-propyl group, n-butyl group, vinylmethyl group, 2-hydroxyethyl group, 4-hydroxybutyl group,
2-acetoxyethyl group, 3-acetoxypropyl group,
2-methoxyethyl group, 4-methoxybutyl group, 2-cargoxyethyl group, 3-cal? Xyprovir group, 2-(
2-cal&+ethoxy)ethyl group% 2-sulfoethyl group, 3-sulfoprobyl group, 3-sul*pfk group, 4
-sulfoptyl group, 2-hydroxy-3-sulfopropyl 12-(3-sulfopropoxy)ethyl group, 2-acetoxy-3-sulfopyl group, 3-methoxy-2-(
3-sulfopro I xy)probyl group, 2-(2-(3-
These include sulfopropoxy)ethoxy]ethyl group, 2-hydroxy-3-(3'-sulfopropoxy)probyl group, and the like.

Specific examples of the nitrogen-containing heterop ring nucleus formed by 2 or z2 include an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a pyridine nucleus, an oxazoline nucleus,
Examples include a thiazoline nucleus, a selenazoline nucleus, an imidazoline nucleus, and those condensed with a benzene ring, a naphthalene ring, or other saturated or unsaturated carbocycles, and these nitrogen-containing heterocycles K are further substituents. (For example, alkyl groups, tri7-fluoromethyl groups, alkoxycarginyl groups, cyano groups, caldic acid groups, carpamoyl groups, alkoxy groups, aryl groups, acyl groups, hydroxyl groups,
halogen atoms, etc.) may be bonded.

Anions represented by X include Ct″″, Br″″
, ■″″ SO″″− NO, − CLO4−
Children can list things like ``''. Among the cyanine dyes represented by the general formula (Ma), preferred examples of yellow layer and cyan NIK are shown below.

(Ma-]) C M&-3) (　Ma-　4　) (Ma-2) (　Ma-　5　) (Ma-6 (Ma-7 (Ma-8 (■a-12) (Ma-1 (■-1 (Ma-9) (Ma-10) (Ma-1 (Ia-17) (Ma-18) (Ma-19) (Ma-23) (Ma-24) (Ma-25) (cH2), S03″″ (CH2)3S03H-NEt, (Mu-20) (Ma-21) (Ma-22) (Ml-26) (Ma-27) (CM2), So3K (Vla-29 doctor (■a-30) S03 So3}{-NEt3 (VI&-31 (Ml-35) (Ma-36 (Ma-37) (■a-32) (Ml-33) (Ma-34) SO, So,}{-? Most, (■a-38) (■a-39) (Ma-40 (CH2)4SO3- (CH2) 4So3H-匪t, (Wm-41 Preferred sensitizing dyes for the K green-sensitive emulsion layer are shown below.

General formula (:Mb) In the formula, 2 and z2 each represent an atomic group necessary for forming a benzene ring or a naphthalene ring condensed to a heterocyclic ring.The heterocyclic nucleus formed is not substituted with a substituent. R and R2 each represent an alkyl group, an alkenyl group, or an aryl group, and R3 is a hydrogen atom or a carbon atom having 1 to 1 carbon atoms.
3 represents an alkyl group. X and e represent anions, and p represents O or 1. Y and Y2 are oxygen atoms, sulfur atoms,
Represents a selenium atom, a nitrogen atom, and a terium atom.

Among the substituents for the heterocyclic nucleus formed above, preferred substituents are a halogen atom, an aryl group, an alkenyl group, an alkyl group, and an alkoxy group.

More preferred substituent groups are the no-location atom, phenyl group and methoxy group, and the most preferred substituent is the 7-enyl group.

Preferably, z1 and z2 are both a benzene ring or a thiazole ring fused to an oxazole ring, and at least one of these benzene rings is substituted with a phenyl group at the 5-position, or one benzene ring is The 5th position of the penzene ring is a phenyl group, and the 5th position of the other penzene ring is replaced with a halogen atom. R1 and R2 are each a group selected from an alkyl group, an alkenyl group, and an aryl group, and preferably each is an alkyl group substituted with a carboxyl group or a sulfo group, and most preferably a group having 1 to 4 carbon atoms. is a sulfoalkyl group, most preferably a sulfoethyl group. R3 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, preferably a hydrogen atom or an ethyl group. The sensitizing dye represented by the general formula (v+b) used in the present invention can also be used in combination with other sensitizing dyes as a so-called supersensitizing combination. In this case, K dissolves each sensitizing dye in the same or different solvent K,
These solutions may be mixed prior to addition to the emulsion or may be added separately to the emulsion. When adding them separately, the order and time interval can be arbitrarily determined depending on the purpose K.

Specific compounds of the sensitizing dye represented by the general formula CMb are shown below, but the sensitizing dye used in the present invention is not limited to these compounds.

(Mb-1 (Mb-2) (Mb-3) (Mb-4) (■b-6) ('?Ib-t (■b-1 (Mb-tz) (Mb-7) (Mb-8 ) (Mb-9 (Vlb-13) (■b (Mb-15 (vib-16 (Mb-17 (Mb- l (M.b-22) (Mb-z3) (Mb-24) (Mb- ( Mb-20) (Vlb-21) lb-25) (Mb-26) (■b-27) (CH2), So, K (■b-28) (■b-29) (Mb-30) Et ( *b-34) (■b-35) (Wb-36) (■b-31 (■b-32) (Mb-33) Normally, in order to spectrally sensitize a silver halide emulsion, the grains must be completely formed. A method is used in which a spectral sensitizing dye is adsorbed onto the surface of the silver halide grains after the grains are precipitated. A method of adding merocyanine dye is disclosed, and it is stated that it is possible to reduce the amount of dye that is not adsorbed.
No. 5-26589 discloses a method in which a spectral sensitizing dye is added and adsorbed during the addition of an aqueous silver salt solution or an aqueous halodan salt solution to form silver halide crystal grains.

In this way, the spectral sensitizing dye may be added during the formation of the non-logonized steel crystal grains, after the formation is completed, or even before the formation begins. Specifically, "before the formation starts" means that the spectral sensitizing dye is introduced into the reaction vessel in advance before starting the reaction to form the silver crystals, and during the grain formation. refers to the method described in the above-mentioned patent, and "after the particle formation is completed" means that K is added and adsorbed after the substantial particle formation process is completed●
Although the silver halide emulsion of the present invention is chemically sensitized after the completion of grain formation, the addition of a spectral sensitizing dye after the completion of grain formation is not suitable for chemical sensitization even before the start of chemical sensitization. Even during sensitization or after chemical sensitization, emulsion can be applied.
It doesn't matter if it's when you're offering it. In the present invention,
It is preferable that the above-mentioned spectral sensitizing dye is added and adsorbed in at least one step after the step in which the formation of silver halide grains is substantially completed. It may be added over two or more steps or in parts. Further, within one step, the addition may be carried out intensively over a short period of time, or may be added continuously over a period of time. Moreover, several such addition methods may be combined.

The spectral sensitizing dye to be added may be added as it is in the form of crystals or powder, but it is preferably added after being dissolved or dispersed by some method. For K to be dissolved, an alcohol having 1 to 3 carbon atoms, a water-soluble solvent such as acetone, pyridine, methyl cellosol, or a mixed solvent thereof may be used. It is also possible to perform micelle dispersion or other dispersion using a surfactant.

The amount of spectral sensitizing dye added depends on the purpose of spectral sensitization and the content of the silver halide emulsion, but it is usually from IXIO mol to 1×lθ per 1 mol K of silver halide.
moles, more preferably I x 10-5 moles to 5 x
10-'mol is added.

Various color couplers can be used in the present invention, specific examples of which can be found in the above-mentioned Research Disclosure (
RD) ▲17643, ■1 C to GK described in the patents described.

Cyan couplers include phenolic and naphthol couplers, and are described in U.S. Pat. No. 4,052,212.
No. 4.1 4 6.3 9 6, No. 4, 22
8. 2 3 3, 4, 2 9 6, 2 0
No. 0, No. 2.369,929, No. 2,801
, 17 No. 1, No. 2,772,162, No. 2,
8 9 5, 8 2 6, 3,772,002, 3.7 5 8, 3 0 8, 4,334
, No. 4,327,173, West German Patent Publication No. 3.329,729, European Patent No. 121.365λ, US Patent No. 3.446,622, 4.33 3,99 9, 4.4 5 1
, No. 559, No. 4,427,767, European Patent No. 161.626A, etc. are preferred. As magenta couplers, 5-pyrazolone and virazoloazole compounds are preferred, and U.S. Pat.
1 0,6 1 9, 4,3 5 1,8 9
No. 7, European Patent No. 73.636, US Patent No. 3.06
No. 1.432, No. 3,7 2 5,0 6 7, Research Disclosure I624220 (1984
(June 1984), JP 60-33552, Research Disk 41 Jar 424230 (June 1984), JP 60-43659, U.S. Patent No. 4,500,630
Particularly preferred are those described in No. 4,540.654, etc. As a yellow coupler, for example, U.S. Patent Nos. 3 and 9
3 3.5 0 1, 4.0 2 2, 6 2
No. 0, No. 4, 3 2 6, 0 2 4, No. 4, 4
0 1,7 5 2, Special Publication No. 58-10739,
British Patent No. 1.425,020, British Patent No. 1.4 7 6
, 760, etc. are preferred.

The cyan coupler, magenta coupler and yellow coupler preferably used in the present invention have the following general formulas (C-1), (C-2), (M-1), (M-2) and (Y). It is what is shown.

X1 General formula (C-2) 0H General formula (M-2) General formula (Y) However, in general formulas (C-1) and (C'-2),
R,, R2 and R4 are substituted or unsubstituted aliphatic,
Represents an aromatic or heterocyclic group, R, R and R6 represent a hydrogen atom, a hydrogen atom, an aliphatic group, an aromatic group or an acylamino group, R3 together with R2 represents a 5-membered ring of a subatomic If << may represent a nonmetallic atomic group forming a 6jj ring, R5 may form a 6-negative aromatic ring together with R6. Y1Y2 represents a hydrogen atom or a group that can be separated during a coupling reaction with an oxidized product of a developing agent.

R5 in general formula (C-2) is preferably an aliphatic group, such as a methyl group, ethyl group, proyl group, butyl group, pentadecyl group, tart-butyl group, cyclohexyl group, cyclohexylmethyl group, Examples include nylthiomethyl group, dodecyloxyphenylthiomethyl group, butanamidomethyl group, and methoxymethyl group.

Preferred examples of the cyan coupler represented by the general formula (C-1) or (C-2) are as follows.

In general formula (C-1)K, R1 is preferably an aryl group,
It is a heterocyclic group, including an atom, an alkyl group, an alkoxy group, an aryloxy group, an acylamino group, an acyl group, a carbamoyl group, a sulfonamide group, a sulfamoyl group, a sulfonyl group, a sulfamide group, an oxycarbonyl group, and a cyano group. If R3 and R2 do not form a ring in the general formula (C-1), R2 is preferably an unsubstituted alkyl group, and is preferably an aryl group substituted with an aryl group. R5 is a group, particularly preferably a diaryloxy-substituted alkyl group, and R5 is preferably a hydrogen atom.

In the general formula (C-2), R4 is preferably a presubstituted or unsubstituted alkyl group or an aryl group, and particularly preferably a partially substituted aryloxy-substituted alkyl group.

In general formula (C-2), R5 preferably has 2 to 1 carbon atoms.
It is a methyl group having an alkyl group of 5 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-2), R5 is more preferably an alkyl group having 2 to 15 carbon atoms, and particularly preferably an alkyl group having 2 to 4 carbon atoms.

In general formula (C-2)K, R6 is preferably a hydrogen atom or a halogen atom, with chlorine and fluorine atoms being particularly preferred. Preferred Y and Y2 in general formulas (C-1) and (C-2) are each a hydrogen atom, a halodane atom, an alkoxy group, an aryloxy group, an acyloxy group, and a sulfonamide group.

In general formula (M-1), R and R represent an aryl group, R8 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 on the aryl group (preferably << phenyl group) of R7 and R, are the same as the substituents allowed on the substituent R1, and when there are two or more 5" may be the same or different. R8 is preferably a hydrogen atom, an aliphatic acyl group or a sulfonyl group, and particularly preferably a hydrogen atom. Preferably Y3 is sulfur, oxygen or a nitrogen atom. It is a type that detaches at either point, such as U.S. Patent No. 4,351.897 and International Publication (WO).
Particularly preferred is the sulfur atom dissociative type as described in No. 88/04795.

In general formula (M-2), R1o represents a hydrogen atom or a substituent. Y4 represents a hydrogen atom or a leaving group, and is particularly preferably a halogen atom or an arylthio group. Za, Zb
and Ze is methine, substituted methine 7=N1 or -NH-
, one of the Za-Zb bond and the Zb-Ze 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 R1G 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 lazoloazole couplers represented by the general formula (M-2), U.S. Patent No. 4.500 is known for its low yellow side absorption of coloring dyes and light fastness. The imidazo(1.2-b)virazoles described in No. 630K are preferred, and the pyrazolo[1,s-b)[1.2 .4] Triazoles are particularly preferred.

In addition, the branched alkyl group as described in JP-A No. 61-65245 is birazolotriazole? Birazolotriazole couplers directly linked to the 2, 3 or 6 position of Virazoloazole couplers with an alkoxyphenylsulfonamidopalast group as described in the patent, and birazolotriazole couplers with an alkoxy group or aryloxy group in the 6-position as described in European Patent Publication No. 226.849. It is preferable to use

In the general formula (Y)K, R11 represents a halogen atom or an alkoxy group, and R1■ represents a hydrogen atom, a halodane atom or an alkoxy group. Ake-NHCOR ,3,-NT
{So −R, −So■NHR13, −COOR,
, , R14 each represents an alkyl group. Y5 represents a leaving group.

The vortex substituents for ``42, R15, and R14 are the same as the substituents allowed for R1, and the leaving group Y5 is preferably one that leaves at either an oxygen atom or a nitrogen atom. Yes, and the nitrogen atom detachment type is particularly preferred.

Specific examples of couplers represented by general formulas (C), (M), and (Y) are listed below.

(C-1) 0H (C-4) 0H Ct (C-5) Ct (C-2) Ct (C-6) (C-7) OR (C-8 (C-14) n Sweet (C- lS (C- (C-12) (c-16) Ct (C-1 (C-18) OcH20iC4H, C2H5 (t)C5H,, (-C-19) Ct (C-20) (C-21 ) (″c-2B 0■ c, u,, (t) (C-25 OH (C-26) 0H OCH2CFI, So2CH, (C-22 0■ OcH3 (C-23) ?HCOCH2CH■Cool (C- 27 OH (C-28 OH (C-29) 0H (C-30) (C-31 (C-32) 0H OR ('C-36) OH (C-37) N}ICocH2α2C■H (C-33 ) Ct (C-34) (C-35 0H (M-1) (M-2 Ct ('M-4) (M-5) (M-9) (M-6) Ct (M-10) ( M-11 Ct (M-12) (t)C,}!,, (1;!I-13) C8H, (t) CH3 (M-15) (M- 1 8 '1 0I3 (Y-1) C! (M-16) (Y-2) (Y-3 (Y-7) Ct (Y-5) (Y-8) Ct (Y-6) Colored dye to correct unnecessary absorption of coloring dye The coupler is from Research Disclosure ▲17643■
Class 1G, U.S. Patent No. 4,163.670, Special Publication No. 1983
-39413, U.S. Patent No. 4,004,929, U.S. Patent No. 4,138,258, British Patent No. 1,146,36
The one described in No. 8 is preferred.

Couplers whose colored dyes have appropriate diffusivity include U.S. Patent No. 4,366,237 and British Patent No. 2,125.
, 570, European Patent No. 96,570, and West German Patent (Publication) No. 3.234,533 are preferred.

Typical examples of /IJ merized dye-forming couplers are U.S. Pat.
No. 0,211, British Patent No. 4,367,282, British Patent No. 2.102,173, etc.

Couplers that release photographically K-useful residues upon coupling are also preferably used in the present invention. DIR couplers releasing development inhibitors include the aforementioned RD17643,
■ - Patent listed in Section F K, Japanese Patent Application Laid-Open No. 57-151944
No., r8U57-154234, 60-18424
No. 8, US Pat. No. 4,248,962 are preferred.

British Patent No. 2,097,140,
Same No. 2.1 3 1, 1 8 8, JP-A-59-15
Those described in No. 7638 and No. 59-170840 are preferred.

Other couplers that can be used in the light-sensitive material of the present invention include competitive couplers described in U.S. Pat. No. 4,130.427 and U.S. Pat. No. 4,283.472.
No. 4,338,393, No. 4.310.

Multi-equivalent coupler described in No. 618 etc., JP-A-60-18
Examples thereof include a DIR redox compound-releasing puller described in European Patent No. 173.302AK and the like, and a coupler that releases a dye that restores color after separation, as described in European Patent No. 173.302AK.

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

Examples of high boiling point solvents used in the oil-in-water dispersion method are described in US Pat. No. 2.322.027 and the like.

The process, effects, and specific examples of latex for impregnation are described in US Pat. No. 4,199,363, West German Pat. tl (OLS) No. 2,541.274 and OLS No. 2.541,230.

In the present invention, it is preferable to use the following compounds together with the above-mentioned couplers. Particularly preferred is the combination with a virazoloazole coupler.

That is, a compound (F) that chemically bonds with the aromatic amine developing agent remaining after the color development process to produce a chemically inert and substantially colorless compound and/or a compound that remains after the color development process. For example, the use of a compound (G) that chemically bonds with the oxidized product of an aromatic amine color developing agent to produce a chemically inert and substantially colorless compound may be used simultaneously or singly, for example, during storage after processing. This is preferable in order to prevent stain generation and other side effects caused by the reaction K between the color developing agent or its oxidized product remaining in the film and the coupler.

A preferable compound (F') has a second-order reaction rate constant k2 (in trioctyl phos7ate at 80°C) with p-aningine of 1. OL/mol-asc~I
It is a compound that reacts in the range of X 10 L/mol-see. Note that the second-order reaction rate constant is based on JP-A-63
It can be measured by the method described in No.-158545.

When k2 is larger than this range, the compound itself becomes unstable and may react with gelatin or water and decompose. However, if k2 is smaller than this range, the reaction with the remaining aromatic amine developing agent is slow, and as a result, it is not possible to prevent the side effects of the remaining aromatic amine developing agent, which is the objective of the present invention. Sometimes.

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

General formula (F'l) R, -(A)n-X General formula (Fn) B In the formula, R, , and R2 each represent an aliphatic group, an aromatic group, or a heterocyclic group. n represents 1 or 0. A represents a group that reacts with the aromatic amine developer to form a chemical bond, and X represents a group that reacts with the aromatic amine developer and leaves. B represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, or a sulfonyl group, and Y promotes the addition of an aromatic amine developing agent to the compound of general formula (Fn). represents a group that Here R1 and 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.

Regarding specific examples K of compounds represented by general formulas (Fl) and (Fil), see JP-A-63-158545 and JP-A-62-2.
No. 83338, Japanese Patent Application No. 158342, No. 1983, Japanese Patent Application No. 1983
Preferably, those described in specification κ, such as No. 3-18439.

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

General Formula (Gl) R-2 In the formula, R represents an aliphatic group, an aromatic group or a heterocyclic group. 2 represents a nucleophilic group or a group that decomposes in the photosensitive material to release a nucleophilic group. The compound represented by the general formula (Gl) has the nucleophilicity "CH, I value (
R. G. Psmrson. @tal. lJ.
Am. Ch@m. Soc. ．． 90.319 (1968
) is preferably 5 or more, or a group derived therefrom.

For specific examples of compounds represented by the general formula (Gl), see European Patent Publication No. 255722, Japanese Patent Application Laid-Open No. 1430-1980
No. 48, No. 62-229145, patent application No. 63-184
No. 39, No. 63-136724, No. 62-21468
Preferably, those described in No. 1, No. 62-158342, etc. In addition, the above-mentioned compound (G) and compound (
For details on the combination with
No. 9K is listed. Suitable supports that can be used in the present invention include, for example, the above-mentioned R
D. A17643, page 28, and the same cliff, 18716, 6
It is described from the right column on page 47 to the left column on page 648.

The photosensitive materials to which the present invention is applied include, for example, color negative films, color reversal films (inner and outer molds), color reversal films, color reversal films, color diffusion transfer processes, and direct positive color photosensitive materials. Any color photographic material may be used as the material, but it is preferable to use special K color negative film, color reversal film, color paper, and color reversal paper K.

(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 laminated on both sides with I-lyethylene. The coating solution was prepared as follows.

First layer coating solution preparation Yellow coupler (ExY) 19.1F, color image stabilizer (Cpd-1) 4.41i and color image stabilizer (Cpd-1)
7) 27.2cc of 0.7.9K ethyl acetate and solvent (
Add and dissolve 8.2p of Sol▼-3), and dilute the solution with 10
%rSodium decylbenzenesulfonate 1 containing 8 flashes
The mixture was emulsified and dispersed in 185 cc of a 0-gelatin aqueous solution.

On the other hand, silver chlorobromide emulsion (cubic average grain size 0.85μ,
Cubic particle size distribution coefficient of variation 0.07. Silver bromide 1.
(containing 0 mole locally on a part of the grain surface), two kinds of back-sensitive sensitizing dyes shown below were added at 2.0 mole of silver per mole of silver.
A sample was prepared in which sulfur sensitization was performed after adding 10 moles of OX. Mixing and dissolving the emulsified dispersion and this emulsion,
A first layer coating solution was prepared to have the composition shown below.

Coating solutions for the second to seventh layers were also prepared in the same manner as the first layer coating solution. The gelatin hardening agent for each layer is 1-oxy-3.5-? /Chlorozenichi triazine sodium salt was used.

The following spectral sensitizing dyes were used in each layer.

Back-sensitive emulsion layer (Ma-33, Vlm-34) SO3- (capital), H -N (C2H5), (2.0 x 1 each of the above two types per mole of silver halide)
0 mole) Green-sensitive emulsion layer (Vlb-31) (Halo r(1 mole of IJ) 4.Ox10
mole) and (■a-26) I (cH2)4 SO, - heat (cH2)4 blind So, H-N (C2H,), S03'''' So,! I-N(C2H5), (7-OXIG""5 moles per 1 mole of silver oxide) Red-sensitive emulsion layer (■a-42) C2H5 1-csHt, (")(
OJ x 10-' mol per mol of silver halide)
To the red-sensitive emulsion layer, the following compound was added in an amount of 2.6 x 10-3 moles per mole of silver halide.

lO mol, 2.5 Irazoesho Added dye.

(D-1) ×10 mol was added.

In order to prevent dyeing, the following (4 Da/,?) and (Im-1) (dye of the present invention) 17'j were added to the emulsion layer for the blue-sensitive emulsion layer, the green-sensitive emulsion layer, and the red-sensitive emulsion layer. 1-(
g.5-methylureido-7enyl)-5-mercaptotetrazole per mole of silver halide. 5XI
O mol, 7.7X (layer structure) The composition of each layer is shown below. The numbers represent the coating amount U/n/). The silver halide emulsion represents the coated amount in terms of silver.

Support polyethylene laminate paper [The polyethylene on the first layer side contains a white pigment (T102) and a bluish dye (ulmarine blue)] First layer (blue-sensitive layer) The above-mentioned silver chlorobromide emulsion 0.30 Gelatin 1.86 Yellow coupler (EzY) 0.82 color' my stabilizer (Cpd
-1) 0.19 color stabilizer (Cpd-7
) 0.03 solvent (Solv-3)
0.35 Second layer (color mixing prevention layer) Gelatin 0.99 Color mixing prevention agent (CPd-5) 0.08 Solvent (Sol
v-1) 0.16 solvent (Solv-
4) 0.08 third layer (green-sensitive layer) silver chlorobromide emulsion (grain size 0.40μ, coefficient of variation 0.0
0.25 zeratin magenta coupler (E: cM) Color image stabilizer (cpci-3) Color image stabilizer (Cpd) -4) Solvent (Sol▼-2) Solvent (Sol▼-7.) Fourth layer (ultraviolet absorption layer) Gelatin ultraviolet absorber (UV-1) Color mixing inhibitor (Cpd-5) Solvent (Sol▼-5) Fifth layer (red-sensitive layer) Silver chlorobromide emulsion (cubic grain size 0.3 to 0.11, silver bromide 1.6 locally contained on a part of the surface) Gelatin cyan coupler (EzC) Color image Stabilizer (Cpd-6) Color image stabilizer (Cpd-7) Color image stabilizer (Cpd-9) 1.24 0.29 0.09 0.06 0.32 0.16 1.58 0.47 0 .05 0.24 6μ, coefficient of variation Morch particle table 0.21 1.3 4 0,34 0.17 0,34 0.04 Solvent (Sol▼-4 0.37 Sixth layer (ultraviolet absorbing layer) Gelatin 0.53 Ultraviolet absorber (UV-1) 0.16 Color mixing inhibitor (cpa-s) 0.02 Solvent (8ol▼-5 0.08 Seventh layer (protective layer) Gelatin 1.33 /9 Vinyl alcohol acrylic Modified copolymer (Degree of modification 1 7s 0.17 Fluid graphite 0.03 ELM) Magenta coupler (cpa-1) Color image stabilizer (cpa-3) Color image stabilizer α (ExC) Cyankazoller CH3CH, (cpa-4) 1:3:6 mixture (weight ratio) of color image stabilizer α R=H, C2H5嘱04H, (cpd-5) 2::4 mixture (weight ratio) of color mixture inhibitor 0H ( cpa-7) Color image stabilizer (cpa-6) Color image stabilizer-+CH2- CH+YCONHC4H, (t) Average molecular weight 60,000 (UV-1) Ultraviolet absorber C4H, (t) 0H (Set▼- 3) Solvent o = p + O C9H19 (Lso))3(So
l▼-4) Solvent c4a, (t) OH (Sol▼-5) Solvent COOC8H,, (CH2)8 cooc8u,, 4:2:4 mixture (weight ratio) (Sol▼-6) Solvent (Sol▼ -1) 3:7 mixture (volume ratio) of solvent (Sol▼-2) solvent (Se1▼-7) The sample obtained as above was designated as I-A.

Samples 1-B to 1-E were prepared by replacing the next K irradiation prevention dye (D-IXI-1) with the following dye.

In order to investigate the photographic characteristics of the above coated sample 1-A-1-E (
, conducted the following experiments.

First, using a sensitometer (FWH model manufactured by Fuji Photo Film Co., Ltd., color temperature of light source 3200K) on the coated sample,
Provided gradation exposure for sensitometry. At this time, the exposure time was 1/10 seconds, and the exposure amount was 250 CMS.

The above-mentioned coated sample was processed using an automatic treatment machine using the following processing steps and the following processing composition. However, the composition of the color developer was changed as shown in Table 1 (1).

Processing process Temperature Time Color development 38℃ 45 seconds bleach fixing
30-36℃ 30 seconds/s ■ 30-37℃ 20 seconds rinse■
30-37℃ 20 seconds rinse ■ 30-37
℃ Dry for 20 seconds 70-80℃
The composition of each treatment solution for 60 seconds is as follows.

Color developer water ethylene diamine - N, N, N/. N/-tetramethylenephosphonic acid preservative ■-19 Sodium chloride Potassium bromide Potassium carbonate N-ethyl-N-(β-methanesulfonamidoethyl) -3-Methyl-4-aminoaniline sulfate Triethanolamine Fluorescence enhancement Whitening agent (manufactured by Sumitomo Chemical, WHI〒EX4) Add water to pH (25℃) Bleach-fix solution water Ammonium thiosulfate (701 800g 3.0g 5.0g See Table 1 See Table 1 25g 5.0g 10. 0,!9 2.0g 10001Ll 10.05 40(lj lQQd Sodium sulfite 17g Ethylenediaminetetraacetic acid iron(III) ammonium 55g Disodium ethylenediaminetetraacetate 5g Glacial acetic acid
Add 9g water
1000mPH (25℃)
5.40 Rinse liquid ion exchange water (3 pp each of calcium and magnesium
m or less) The above sample was processed, and the minimum and maximum concentrations (DBmin XDHmax) of cyan (R) were measured using a McPeth densitometer. Furthermore, the amount of residual silver at the maximum density was measured using fluorescent X-rays. The results are shown in Table 1 (1).

Furthermore, in order to measure resolution, each sample surface was exposed to red light using a rectangular wave pattern for CTF measurement. Subsequently, the color development process was performed, and the cyan density was measured using a microdensitometer. The results are shown in Table 1 (2).

Table 1 Samples of the invention using treatments 3, 4, 5 and 6 of the invention
It has been found that by processing -A, B, and C, good photographic properties with small cyan stain, high maximum density, excellent sharpness, and small amount of residual silver can be obtained.

Material E containing anti-irrazoation dyes other than those of the present invention I
-D and I-E, the above effects could not be obtained even in the treatment of the present invention.

(Example 2) In treatment 4 of sample example 1, preservative I in the color solution
Instead of fi-19, equimolar amount of preservative [. -1, 11-
2, II-11, II-21, and κ were changed to sample 1A.
When processed, it was possible to obtain similarly excellent photographic properties.

(Example 3) The anti-irrazoation dye glue of Sample 1-A of Example 1. Rini, I&-3,! a-8, I&-13, Ia-i
6, Ib-4, Ib-6, Ib-17 and Ib-20
When samples containing 8η/1 of each were prepared and processed in the same manner as in Example 1, excellent photographic properties were obtained in Processes 3 to 6 of the present invention.

(Example 4) Sample 4-A using a silver chlorobromide emulsion in the same manner as Example 1 Sample 1-A, except that the silver bromide-containing wheel was changed as follows.
, B, C, and D were prepared and processed in Example 1 Processes 2, 4, and 7, and the results are shown in Table 2.

If Samples 1-A, 4, 4-B1 and 4-C of the present invention are treated with Process 4 of the present invention, the stain is low, the maximum density is high, the sharpness is excellent, and the amount of residual silver is low. This effect is particularly remarkable in Samples 1-A and 4-A, which used silver chlorobromide emulsions containing chloride ions of 95 mole or more.

Example 5 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.

First layer coating solution preparation Yellow coupler (1:r:Y) 19.1. ! i' and 4.4 g of color stabilizer (Cpd-1) and color weight stabilizer (
Add and dissolve 27.2 cc of ethyl acetate and 8.2 Ii of solvent (Set▼-3) to 0.7 Il of cpd-7), and add 1 osy of sodium decylpenzene sulfonate to 8.2 Ii of the solution.
The mixture was emulsified and dispersed in 185 cc of an iogb gelatin aqueous solution containing rice. On the other hand, silver chlorobromide emulsion (cubic average grain size 0.
88μ, particle size distribution coefficient of variation 0.08.

silver bromide (containing 0.2 mole of silver bromide on the grain surface) and the following blue-sensitive sensitizing dyes per mole of silver. OX1
A sample was prepared in which sulfur sensitization was performed after adding 0"" mole. The above emulsified dispersion and this emulsion were mixed and dissolved, and the following κ
A first layer coating solution was prepared to have the composition shown. Coating solutions for the second to seventh layers were also prepared in the same manner as the first layer coating solution. The gelatin hardening agent for each layer is 1-oxy-
For 3.5-dichloride, Rho-S triazone sodium salt was used.

The following spectral sensitizing dyes were used in each layer.

Blue sensitive emulsion layer (■a-33, Ma-34) 80,H
-N(C21{5), (CH2)4 I SO, - (cH2)4 p go, H -N(C2H,), (1 mole of silver halide a9 each 2.o X 1 0-'
mole) Green-sensitive emulsion layer (■b-31) Ma-26 80, - 80,H -N(C2}[,), (7.Ox10'' per mole of silver halide mol) Red-sensitive emulsion layer (Ma-42) (4.0 x 10-' mol per 1 mol of silver halide) C2Hs ■1 CS horse 1 (0.9 x 1 0-' mol per 1 mol of silver halide) ) The following compound was added to the red-sensitive emulsion layer κ in an amount of 2.6 x 10-' mol per mol of silver halide.

and (I凰-1) (dye of the present invention) In addition, 1-(5-medelureiP-phenyl)-5-mercaptotetrazole was added to silver halide for the blue-sensitive emulsion layer, the green-sensitive emulsion layer, and the red-sensitive emulsion layer, respectively. B per mole
．． 5 X 1 0-5 mol, 7.7 x 10-4 mol, 2
．． ．． 5XIO=moles were added.

The following dyes were added to the K emulsion layer to prevent insolation.

? Layer composition) The composition of each layer is shown below. The numbers represent the coating amount (g/1). The silver halide emulsion represents the coated amount in terms of silver.

Support polyethylene laminate paper [The polyethylene on the first layer side contains white pigment (T10■) and real taste dye (group growth)] First layer (sensitivity layer) Silver chlorobromide emulsion 0.30 Gelatin 1.86 Yellow Kaptu (ExY) 0.82 color image stabilizer (Cpd-
1) 0.19 solvent (Sat▼-3)
0.35 color image stabilizer (Cpd-7)
0.06 Second layer (color mixing prevention layer) Gelatin 0.99 Color mixing prevention agent (CPd-5) (108 Solvent (So
l▼-1) 0.16 Solvent (Sol
v-4) 0.08 Third layer (green sensitive layer) Silver chlorobromide emulsion (1:3 mixture (Ag mole) ratio of one with a cubic average grain size of 0.55A and one with a cubic average grain size of 0.39μ).

Coefficient of variation of particle size distribution 0.1 0, 0.0 8, respectively
AgBr OJ mortar was locally contained on the particle surface.

Gelatin magenta coupler (EXM) Color image stabilizer (Cpd-3) Color image stabilizer (Cpd-8) Color image stabilizer (Cpd-9) Solvent (Sol▼-2) 0.12 1.24 0.27 0.15 0.02 0.03 0.5 4 Fourth layer (ultraviolet absorption layer) Ze2tin 1.58 Ultraviolet absorber (UV-1) 0.47 Color mixing inhibitor (
cpa-s) o. os solvent (SOIY
-5) 0.2 4 Fifth layer (red sensitive layer) Silver chlorobromide emulsion (1:4 mixture of cubic average grain size of 0.58μ and 0.45μ (Ag molar ratio), grain size distribution Coefficient of variation of 0.09, 0.1 1, Ag
0.6 mol of Br was locally contained on a part of the particle surface.

Gelatin Cyankazolar (EXC) Color stabilizer (Cpd-6) Color image stabilizer (Cpd-10) Color image stabilizer (Cpd-7) Solvent (Sol▼-6) 6th layer (ultraviolet absorption turbidity) Gelatin 0.23 1.34 0.32 0.1 7 0.04 0.40 0.15 0.53 Ultraviolet absorber (t7V-1) 0.1 (IxM) Mazey Takazo 2- Color mixing inhibitor (Cpd - 5) 0.02 Solvent (8o1▼-5 0.08 Seventh layer (protective layer) Gelatin 1.33 Acrylic modified copolymer of irivinyl alcohol (degree of modification 174s) 0.1 C6H17 Flow Δ rough-in 0.03 (Ext) Yellow Cap 2- (ExC) Cyan Cap 2- α R Snow C,}I,, 04H, OH (cpa-5) A mixture of 2:4:4 by weight of each color inhibitor α 0H (Cpd -1) Color image stabilizer (cpa-6) Color image stabilizer (Cpd-3) 2:4:4 mixture (weight ratio) of color image stabilizer cH3cH3 (cpa-7) Color image stabilizer + CH2- CH+1 cOPtHc4H , (t) average molecular weight (cpa-8) color image stabilizer 60,000 (UV-1) ultraviolet absorber C4H, (t) (cpa-9) 4:2:4 mixture (weight ratio) of color image stabilizer ) (Sol▼-1) Solvent (Sol▼-2) Solvent (Sol▼-6) 2:1 mixture of solvents (volume ratio) (Sol▼-3) Solvent o = p4 o - C, H,, (llG ))3
(S(It▼-4) solvent The sample obtained in the above manner was combined with Sample 5.Next, a sample using the same nonradiation-preventing dye as in Example 1 Sample 1-K was prepared with Sample 5- It was set as B.

After imagewise exposure of Samples 5-A and 5-B, continuous processing was performed in the following processing steps until three times the amount of the color developing tank was replenished.

(8o1▼-5) Solvent COOC, H,, (CII2), l cooc8m,, Color development 38℃ 45 seconds 10911L Bleach fixing 3T 36℃ 45 seconds 61M Water washing ■ 3T 37
℃ 30 seconds washing ■ 3 to 37℃ 30 seconds washing ■ 30-37℃ 30 seconds 364d drying
70 to 85°C for 60 seconds *Amount of replenishment per 1 photosensitive material (3 tank countercurrent system from washing ■ to ■.Washing solution ■ to bleach-fixing was refilled 122 times per 1 photosensitive material.) Each The composition of the treatment liquid is as follows.

Color current liquid water ethylene dian-N, N, N', N'-tetramethylenephosphonic acid triethanolamine sodium chloride sodium bromide potassium carbonate N-ethyl-N-(β-methanesulfonamyl ethyl)-3 -Methyl-4-aelectronoaniline sulfate organic preservative (DI-19) Tank fluid Replenisher 80011j $QQd 3.0II 8. Og 4.2X10-2M 1.3X10-4M 3.0! 1 11.09 25g 5, OIi9.5,9 2.7X10-2M 5.4X10''2M fluorescent whitening agent (
Sumitomo Chemical WRITEX-4 ) Add water (25℃) Bleach-fix solution 1.25! i iooo* 10.0 5 Tank liquid water 400d Ammonium thiosulfate (70%) lQQd Ammonium sulfite 38g Ethylenediaminetetraacetic acid iron(II) ammonium 55J Ammonium bromide 30g Ethylenediamine/tetraacetic acid disodium 5g Glacial acetic acid 9lI Add water 1 '000jljpH(2
5℃) 5.4 0 Washing liquid (tank liquid and replenishment liquid are the same) 2.59 1000Hl 10.60 Replenishment liquid 250d 95p 138. ! 9 lOy 20p 1000wLl 5.40 Ion exchange water (calcium and magnesium are each 3
ppm or less) In addition, the color developing solution, bleach-fixing solution, and washing solution (in contrast, distilled water was added in an evaporated amount, and continuous processing was performed while correcting the evaporation concentration.

After continuous processing, the chloride ion and bromide ion concentrations in each color developer were analyzed and were equally as follows.

Ct″″ Br″″ After 5-person continuous treatment 5.5 cutting 0”-2M 2.O
After continuous treatment of X10-'M5-B 5.5 mowing 0-2M
2. O
When ax, residual silver amount, and resolving power were determined, κ was obtained as shown below.

According to the invention K, excellent photographic properties such as low stain, high maximum density, excellent sharpness, and small amount of residual silver were obtained.

(Example 6) Next, Example 5, Sample 5-A's anti-irrazoation dye was changed as shown in Table 3, and Sample 6, B, C, DS
E and F were created.

After each of the above samples was subjected to sensitometric exposure, it was treated with the treated solution of Example 5 and Sample 5, and Dlmin
Dlrnin, Dlmax, residual silver amount and resolution were measured. The results are shown in Table 4.

According to the present invention, not only an excellent white background with low yellow and cyan stains can be obtained, but also excellent sharpness,
The maximum density is high and the amount of residual silver is low.

Claims (2)

[Claims] (1) In 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, a high silver chloride silver halide comprising 80 mol% or more of silver chloride is used. A silver halide color photosensitive material having an emulsion in at least one layer and a dye having a maximum absorption wavelength in the range of 680 to 720 nm in the gelatin film was prepared by adding 3.5 x 10^- chloride ions to the material. Contains ^2~1.5 x 10^-^1 mol/, and bromine ions at 3.0 x 10^-^5~1.
1. A method for processing a silver halide color photographic material, comprising processing with a color developer containing 0×10^-^3 mol/l. (2) The absorption maximum wavelength in the gelatin film is 68
The dye in the range of 0 to 720 nm has the following general formula (I a
) or (Ib), the method for processing a silver halide color photographic light-sensitive material according to claim 1. General formula (Ia) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, X and X' are hydrogen atoms, hydroxyl groups, carboxyl groups, -COOR_1, -COR_1, -CONH_2,
-CONR_1R_2 represents an alkyl group, an aryl group, or an amino group, Y and Y' each represent a hydrogen atom, an alkyl group, an aryl group, or an amino group, and Z and Z' each represent a hydrogen atom, a cyano group, a carboxyl group, or a sulfonate group. Group, amino group, -COOR_3, -COR_3, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, -SO_2R_3, -CONH_2, -CONR
_3R_4 represents an alkyl group or an aryl group. R_1 and R_3 each represent an alkyl group or an aryl group, and R_2 and R_4 each represent a hydrogen atom, an alkyl group,
Or represents an aryl group. L_1, L_2, L_3,
L_4 and L_5 each represent a methine group, n represents 1, 2 or 3, and M^n^+ represents an n-valent cation. ) ( I b) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R^1 and R^4 each represent an alkyl group, aryl group, or heterocyclic group, and R^2 and R^5 each group, aryl group, heterocyclic group, COR^7 or SO_2R
^7, R^3 and R^6 are each a hydrogen atom, a cyano group, a hydroxyl group, a carboxylic acid group, an alkyl group, an aryl group,
-COOR^7, -OR^7, -NR^8R^9, -N
(R^8)COR^9, -SO_2R^7, -COR^
7, -N(R^8)SO_2R^9, -CONR^8R
^9, or -N(R^8)CONR^8R^9(R^7
represents an alkyl group or aryl-, R^8, R^9
each represents a hydrogen atom, an alkyl group or an aryl group. ), and L_1, L_2, and L_3 each represent a methine group. However, R^1, R^2, R^3, R^4, R^5
, R^6, L_1, L_2 or L_3 represents a group having at least one carboxylic acid group or sulfonic acid group. ]