JPH04130431A - Processing method for silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To decrease the stains (after colors) after processing of the photosensitive material having a high iodine content by incorporating mesoionic compds. as a fixer into a bath having fixability and specifying the content thereof. CONSTITUTION:At least one kind of the mesoionic compds. are incorporated as the fixer into the bath having the fixability and the content thereof is confined to >=0.2mol/l. The problems of stains arises with thiosulfate which is the conventional fixer if the content of the average silver iodide over the entire part of the emulsion layer of the color photosensitive material increases to >=3mol% but this problems are solved by using the mesoionic compds. as the fixer. The bath having the fixability signifies a fixing bath and bleach-fixing bath. The stains (after colors) after processing of the photosensitive material having the high iodine content are decreased in this way.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a method for processing silver halide color photographic light-sensitive materials, and more specifically to a processing method with less stain (residual color) after processing. .

(Prior Art) After exposure, color photosensitive materials are processed through steps such as color development, desilvering, washing, and stabilization.

A color developing solution is used for color development, a bleach solution, a bleach-fix solution, and a fixing solution are used for desilvering treatment, tap water or ion exchange water is used for washing, and a stabilizing solution is used for stabilization treatment.

The temperature of each processing solution is usually adjusted to 30 to 40°C, and the photosensitive material is immersed in these processing solutions to be processed.

The basics of the above color development process are:
These are a color development process and a desilvering process.

In the color development step, exposed silver halide is reduced by a color developing agent to yield silver, and the oxidized color developing agent reacts with a color former (coupler) to provide a dye image.

In addition, in the desilvering step that follows this color development step, the silver produced in the color development step is oxidized by the action of a bleaching agent, which is an oxidizing agent, and then dissolved by a fixing agent, which is a complex ion forming agent for silver ions. Only a dye image is formed.

The above desilvering process includes a method in which the bleaching step and the fixing step are carried out in the same bath, a method in which they are carried out in separate baths, and a method in which the bleaching step and the bleach-fixing step are carried out in separate baths. Also, in this case,
Each bath may have multiple baths.

In addition to the above-mentioned basic steps, various auxiliary steps are performed for the purpose of maintaining the photographic and physical quality of the dye image or improving its shelf life. Such a step is carried out using, for example, a hardening bath, a stopping bath, a stabilizing bath, a washing bath, and the like.

Ferric (I[[) ion complex salts (e.g., aminopolycarboxylic acid-iron(II[) complex salts]) are mainly used as bleaching agents, and thiosulfates are usually used as fixing agents. There is. However, when a silver iodobromide light-sensitive material is processed using thiosulfate, a phenomenon is observed in which as the iodine content increases, staining (residual color) after processing becomes worse. This is thought to be caused by poor desilvering or poor desorption of the sensitizing dye from silver.

For this reason, materials for improving residual color have been studied, but satisfactory results have not been obtained.

on the other hand,! , 2. Examples of fixing agents using 4-triazolium-3-thiolate are disclosed in U.S. Pat. No. 4,378,424;
It is described in Japanese Patent Application Laid-Open No. 57-150842. However, in the present invention, when a fixing agent of a certain concentration or more is used,
The higher the iodine content in the photosensitive material, the more the stain (
It was discovered that this method improves the residual color (residual color), and such effects have not been studied at all.

Furthermore, JP-A No. 1201659 and JP-A No. 2-44355 disclose that a meso ionic compound is added as a bleach accelerator to a bleach bath or a bleach-fixing bath, but as in the present invention, a meso ionic compound is used as a fixing agent. This is very different from the point of view of using it at a high concentration, and the purpose and effects of the present invention have not been studied.

In addition, as meso ion compounds, there are also US Pat. No. 4,003,910, US Pat.
-217237, No. 64-3641, etc., but all of them are added to photographic materials or developers, and as in the present invention, they are used as fixing agents in processing baths. No studies have been conducted on its use.

It can be said that the technology for improving the residual color of photosensitive materials with such a high iodine content has not yet reached a satisfactory state at present.

(Problem to be Solved by the Invention) Accordingly, an object of the present invention is to provide a method for processing silver halide color photographic light-sensitive materials with less staining (residual color) after processing for light-sensitive materials with a high iodine content. .

(Means for Solving the Problem) The above object is a process in which a silver halide color photographic light-sensitive material in which the average silver iodide content of silver halide is 3 mol % or more is processed with a bath having a fixing ability after color development. In the method,
The bath having fixing ability contains at least one meso ion compound as a fixing agent, and the content thereof is 0. This was achieved by a method for processing silver halide color photographic materials characterized by a silver halide content of 2 mol/l or more.

As described above, when the average silver iodide content of the entire emulsion layer of a color light-sensitive material exceeds 3 mol %, the problem of staining occurs when using thiosulfate, which is a conventional fixing agent, but mesoionic compounds are used as a fixing agent. It was unexpected that such a problem was resolved.

Here, the term "bath having fixing ability" means a fixing bath or a bleach-fixing bath. Other additives used in these baths are commonly used. The details will be described later.

The mesoionic compound represented by the present invention is W.

Baker and W. D. 01lis in Fortary Review'-(Quart, Rev.) 11.
15 (1957), Advances in Heterocyclic Chemistry
in Heterocyclic Chemist
ry) 19.1 (1976) [5- or 6-membered heterocyclic compounds that cannot be represented satisfactorily with a single covalent structural formula or polar structural formula; π associated with all atoms comprising
Describes a compound with an electron sextad in which the ring is partially positively charged, balanced by an equal negative charge on an extra-ring atom or group.

Among these mesoionic compounds, General formula (1) is given.

General formula (1) or the following X - 0° se or -N"-R. R represents an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group or a heterocyclic group.

Next, general formula (I) will be explained in detail.

The 5-membered heterocycle represented by Z includes imidazoliums, pyrazoliums, oxacilliums, thiazoliums, triazoliums, tetrazoliums, thiadiazoliums, oxadiazoliums, thiatriazoliums, and oxatriazoliums. Examples include the following.

R is a substituted or unsubstituted alkyl group (e.g. methyl group, ethyl group, n-propyl group, n-butyl group, isopropyl group, n-octyl group, carboxyethyl group, ethoxycarbonylmethyl group, dimethylaminoethyl group), Substituted or unsubstituted cycloalkyl groups (e.g. cyclohexyl group, 4-methylcyclohexyl group, cyclopentyl group), substituted or unsubstituted alkenyl groups (e.g. propenyl group, 2-methylpropenyl group), substituted or unsubstituted alkynyl groups ( For example, propargyl group, butynyl group, -methylpropargyl group), substituted or unsubstituted aralkyl group (e.g. benzyl group, 4-methoxybenzyl group), substituted or unsubstituted aryl group (e.g. phenyl group, naphthyl group, 4-methoxybenzyl group), Methylphenyl group, 3-
methquinphenyl group, 4-ethoxycarbonylphenyl group), substituted or unsubstituted heterocyclic group (eg, pyridyl group, imidazolyl group, morpholino group, triazolyl group, tetrazolyl group, thienyl group).

In addition, the heterocycle represented by Z includes a nitro group, a /\rogen atom (e.g., chlorine atom, bromine atom, etc.), a mercapto group, a cyano group, a substituted or unsubstituted alkyl group (e.g., a methyl group, an ethyl group, a propyl group, etc.). group, t-butyl group, metquinethyl group, methylthioethyl group, dimethylaminoethyl group, morpholinoethyl group, dimethylaminoethylthioethyl group, diethylaminoethyl group, dimethylaminopropyl group, dipropylaminoethyl group, dimethylaminohexyl group , methylthiomethyl group, methoxyethoxyethoxyethyl group, trimethylammonioethyl group, cyanoethyl group, carboxymethyl group, carboxyethyl group, carboxypropyl group, sulfoethyl group, sulfomethyl group, phosphonomethyl group, phosphonoethyl group)
, aryl group (e.g. phenyl group, 4-methanesulfonamidophenyl group, 4-methylphenyl group, 3-methoxyphenyl group, 4-dimethylaminophenyl group, 3.4
-dichlorophenyl group, naphthyl group), alkenyl group (
For example, allyl group), cycloalkyl group (for example, cyclohexyl group, cyclopentyl group, etc.), alkynyl group (for example, propargyl group), aralkyl group (for example, benzyl group, 4-methylbenzyl group, phenethyl group, 4-methoxybenzyl group), Alkoxy groups (e.g. methoxy, ethoxy, methoxyethoxy, methylthioethoxy, dimethylaminoethoxy), aryloxy groups (e.g. phenoxy, 4-methoxyphenoxy), alkylthio groups (e.g. methylthio, ethylthio, propylthio) group, methylthioethyl group, dimethylamineethylthio group, methoxyethylthio group, morpholinoethylthio group, dimethylaminopropylthio group, piperidinoethylthio group, pyrrolidinoethylthio group, morpholinoethylthioethylthio group, imidazolylethyl thio group, 2-pyridylmethylthio group, diethylaminoethylthio group),
Arylthio groups (e.g. phenylthio group, 4-dimethylaminophenylthio group), heterocyclic oxy groups (e.g. 2
-pyridyloxy group, 2-imidazolyloxy group), heterocyclic thio group (e.g. 2-benzthiazolylthio group, 4
-virazolylthio group), sulfonyl group (e.g. methanesulfonyl group, ethanesulfonyl group, p-toluenesulfonyl group, methoxyethylsulfonyl group, dimethylaminoethylsulfonyl group), carbamoyl group (e.g. unsubstituted carbamoyl group, methylcarbamoyl group, dimethylamino ethylcarbamoyl group, methoxyethylcarbamoyl group, morpholinoethylcarbamoyl group, methylthioethylcarbamoyl group, phenylcarbamoyl group), sulfamoyl group (e.g. unsubstituted sulfamoyl group, methylsulfamoyl group, imidazolylethylsulfamoyl group, phenylsulfamoyl group) group), carbonamide group (e.g. acetamide group, benzamide group, methoxypropionamide group, dimethylaminepropionamide group),
Sulfonamide groups (e.g. methanesulfonamide group, benzenesulfonamide group, p-toluenesulfonamide group), acyloxy groups (e.g. acetyloxy group, benzoyloxy group), sulfonyloxy groups (e.g. methanesulfonyloxy group), ureido groups ( For example, unsubstituted ureido group, methylureido group, ethylureido group, methoxyethylureido group, dimethylaminopropylureido group, methylthioethylureido group, morpholinoethylureido group, phenylureido group), thioureido group (
For example, unsubstituted thioureido group, methylthioureido group, methoxyethylthioureido group), sulfamoylamino group (e.g., unsubstituted sulfamoylamino group, dimethylsulfamoylamino group, etc.), acyl group (e.g., acetyl group, benzoyl group, 4-methoxybenzoyl group)
, heterocyclic groups (e.g. 1-morpholino group, l-piperidino group, 2-pyridyl group, 4-pyridyl group, 2-thienyl group, l-pyrazolyl group, 1-imidazolyl group, 2-tetrahydrofuryl group, tetrahydrothienyl group) ), oxycarbonyl groups (e.g. methoxycarbonyl group, phenoxycarbonyl group, methoxyethoxycarbonyl group, methylthioethoxycarbonyl group, methoxyethoxyethoxyethoxycarbonyl group, dimethylaminoethoxycarbonyl group, morpholinoethoxycarbonyl group), oxycarbonylamino group (e.g. methoxycarbonylamino group, phenoxycarbonylamino group, 2-ethylhexyloxycarbonylamino group, etc.), amino group (e.g. unsubstituted amino group, dimethylamino group, methoxyethylamino group, anilino group, etc.), carboxylic acid or the salt,
It may be substituted with sulfonic acid or its salt, hydroxyl group, etc.

Furthermore, the compound represented by the general formula (I) can be used as a salt (e.g. acetate, nitrate, salicylate, hydrochloride, iodate,
bromate, etc.).

In general formula (I), preferably Xo represents -80.

Among the mesoionic compounds used in the present invention, the following general formula (II) is more preferred.

General Formula (n) In the formula, R R2 represents an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group, or a heterocyclic group.

However, R2 may be a hydrogen atom. Y is -O--3
--N-, and R8 represents an alkyl group, a cycloalkynyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an amino group, an acylamino group, a sulfonamido group, a ureido group, or a sulfamoylamino group.

R1 and R2, and R2 and R3 may be bonded to each other to form a ring.

The compound represented by the above general formula (II) will be explained in detail.

In the formula, R1 and R2 are substituted or unsubstituted alkyl groups (e.g., methyl group, ethyl group, n-propyl group, t-butyl group, methoxyethyl group, methylthioethyl group, dimethylaminoethyl group, morpholinoethyl group, Dimethylaminoethylthioethyl group, diethylaminoethyl group, aminoethyl group, methylthiomethyl group, trimethylammonioethyl group, carboxinmethyl group, carboxinethyl group, carboxypropyl group, sulfoethyl group, sulfomethyl group, phosphonomethyl group, phosphonoethyl group ) Substituted or unsubstituted 7-chloroalkyl group (e.g. cyclohexyl group, cyclopentyl group, 2-methylcyclohexyl group), substituted or unsubstituted alkenyl group (e.g. allyl group, 2-methylallyl group), substituted or unsubstituted alkenyl group (e.g. allyl group, 2-methylallyl group) Alkynyl groups (e.g. propalkyl group), substituted or unsubstituted aralkyl groups (e.g. pencil group, phenethyl group, 4-methoxypencyl group), aryl groups (e.g. phenyl group, naphthyl group, 4-methylphenyl group, 4-methoxy phenyl group, 4-carboxyphenyl group, 4-sulfophenyl group), or substituted or unsubstituted heterocyclic group (e.g., 2-pyridyl group, 3-pyridyl group, 4-
Pyridyl group, 2-thienyl group, 1-pyrazolyl group, ■-
(imidazolyl group, 2-tetrahydrofuryl group).

However, R2 may be a hydrogen atom.

R3 is a substituted or unsubstituted alkyl group (e.g., methyl group, ethyl group, n-propyl group, t-butyl group, methoxyethyl group, methylthioethyl group, dimethylaminoethyl group, morpholinoethyl group, dimethylaminoethylthioethyl group) , diethylaminoethyl group, aminoethyl group,
Methylthiomethyl group, trinotylammonioethyl group,
carboxymethyl group, carboxyethyl group, carboxypropyl group, sulfoethyl group, sulfomethyl group, phosphonomethyl group, phosphonoethyl group), substituted or unsubstituted cycloalkyl group (e.g., cyclohexyl group, cyclopentyl group, 2-methylcyclohexyl group), Substituted or unsubstituted alkenyl groups (e.g. allyl group, 2-methylallyl group), substituted or unsubstituted alkynyl groups (
(e.g., propargyl group), substituted or unsubstituted aralkyl groups (e.g., benzyl group, phenethyl group, 4-methoxybenzyl group), aryl groups (e.g., phenyl group,
naphthyl group, 4-methylphenyl group, 4-methoxyphenyl group, 4-carboxyphenyl group, 4-sulfophenyl group, etc.), or substituted or unsubstituted heterocyclic group (
For example, 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, 2-thienyl group, ■-pyrazolyl group, 1-imidazolyl group, 2-tetrahydrofuryl group), substituted or unsubstituted amine group (e.g. unsubstituted amino group, dimethylamino group, methylamino group), acylamide group (e.g. acetylamino group, benzoylamino group, methoxypropionylamino group), sulfonamide group (e.g. methanesulfonamide group, benzenesulfonamide group, 4-toluenesulfone) amide group), ureido group (e.g., unsubstituted ureido group, 3-methylureido group), sulfamoylamino group (e.g., unsubstituted sulfamoylamino group, 3-methylureido group),
methylsulfamoylamino group).

In the general formula (I[), preferably Y represents -N-, R5 and R1 and R8 are substituted or unsubstituted alkyl groups, substituted or unsubstituted alkenyl groups, substituted or unsubstituted alkynyl groups, or substituted or unsubstituted alkynyl groups. Represents an unsubstituted heterocyclic group. R2 is preferably a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, or a substituted or unsubstituted heterocyclic group.

Specific examples of the compounds of the present invention are shown below, but the compounds of the present invention are not limited thereto.

CH3 CH, CH2C00NH.

CH2CH2Sot Na ■ CH.

CH.

HCOOH CH2COOH (CH2CH20), CH3 CH,CC00 HCHSOx Na CH.

CHg CH=CL CH, CH20H CH.

CH.

CH2 CH2CH25CH2CH,0H 24° CH.

￥ N.H.

N.H. -N 38° CH3 CH.

CH.

・HNO.

CH.

NH-HCl2 CH.

CH,CoOH CH3 CH2CH2COOH CH2CH2H CH,C0OH The compound represented by formula (1) or (II) of the present invention is described in the Journal of Heterocyclic Chemistry (J, Heterocyclic Ch
em, ) 2.105 (1965L Journal of Organic Chemistry (J, Org, Che
m, ) 32.2245 (1967), Journal
of Chemical Society (J, Chem, So
c,) 3799 (1969), Journal of the American Chemical Society (J, Am, Ch.
em, Soc, )-Shadow”-11895 (1958), Chemical Communication (Chem, Commun
) 1222 (1971), Tetrahedron
Letters CTetrahedron Lett,) 293
9 (1972), JP-A-60-87322, Berichte der Deutschen Hemitschen Gesellschaft.
Chemischen Ge5ellschaft)3
8.4049 (1905), Journal of Chemical Society Chemical Communication (J
, Chem, Soc, Chem, Common,)
1224 (1971), JP-A-60-122936, JP-A-60-117240, Advance is in Heterocyclic Chemistry
s 1nHeterocyclic Chemistry
y) l 9.1 (1,976), Tetrahedron・
Letters (Tetrahedron Letters)
5881 (1968), Journal of Heterocyclic Chemistry (J.
clicChem, ) 5.277 (1968),
Journal of Chemical Society Parkin Transactions I (J, Chem, Soc,
Perkin Trans, I) 627 (1
974), Tetrahedron Letters (Tetrah)
edron Letters) 1809 (196
7), 157B (1971), Journal of the Chemical Society (J, Chem, Soc,
) 899 (1935), 2865 (1959), Journal of Organic Chemistry (J.

Org, Chem, ) 30 567 (1965).

The amount of the compound of the present invention used is suitably 0.2 mol/j2 or more, preferably 0.2 mol/j2 or more. 3 mol/l-2,0
Mol/! More preferably, it is used in an amount of 0.5 mosif 1 to 1.5 mol/l.

Here, by using 0.2 mol/l or more, it was possible to unexpectedly reduce staining of a color sensitive material made of a silver iodobromide emulsion.

As mentioned above, thiosulfate (mainly ammonium thiosulfate) is usually used as a fixing agent, but when processing sensitive materials containing excessive amounts, it is difficult to wash out the sensitizing dye (residual color) after processing. Especially, the higher the iodine content is, the greater this tendency is.This is thought to be caused by the formation of a ternary complex between the sensitizing dye, silver ion, and iodine ion.Also, the accumulation of silver increases. Along with this, the desilvering performance also deteriorates.

As a result of various studies, the present inventors found that when using 0.2 mol/l or more of a mesoionic compound as a fixing agent, there is a fixing ability without using any other fixing agent, and there is no stain (residual color) after processing. I found that it improved. From the viewpoint of complex formation with silver ions, thiosulfate has a larger stability constant, so it was unexpected that the fixing agent of the present invention showed good results, especially when the iodine content was high. It was about.

The reason for this is thought to be that when the fixing agent of the present invention is used, the desorption property of the sensitizing dye is improved because a ternary complex is stably formed with the fixing agent, either silver ion or iodide ion. is currently being analyzed).

It has also been found that similar effects can be obtained even when a fixing agent other than thiosulfate is used in combination, as long as the amount of the fixing agent of the present invention is 0.2 mol/l or more.

Note that adding the compound of the present invention to the washing bath or stabilizing bath is also effective in reducing stain (remaining color) after treatment. Here, the concentration in these baths is preferably 10<-8> to 0.5 times the fixer concentration in the previous bath.

Next, silver halide color photographic materials and processing methods using them will be described in detail.

The silver halide color photographic light-sensitive material of the present invention may be provided with at least one silver halide emulsion layer of a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer on a support. There are no particular limitations on the number and order of the silver halide emulsion layers and non-photosensitive layers. A typical example is a silver halide photographic light-sensitive material having on a support at least one photosensitive layer consisting of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different photosensitivity. The photosensitive layer is a unit photosensitive layer that is sensitive to blue light, green light, or red light, and in a multilayer silver halide color photographic light-sensitive material, the arrangement of the unit photosensitive layers is generally A red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer are provided in this order from the support side. However, depending on the purpose, the order of installation may be reversed, or the order of installation may be such that different photosensitive layers are sandwiched between the same color-sensitive layer.

Non-photosensitive layers such as various intermediate layers may be provided between the silver halide photosensitive layers and between the uppermost layer and the lowermost layer.

The intermediate layer includes JP-A Nos. 61-43748 and 59-1.
No. 13438, No. 59-113440, No. 61-20
Coupler, DIR compound, etc. as described in No. 037 and No. 61-20038 may be included,
It may also contain a commonly used color mixing inhibitor.

A plurality of silver halide emulsion layers constituting each unit photosensitive layer are composed of a high-speed emulsion layer and a low-speed emulsion layer, as described in West German Patent No. 1,121,470 or British Patent No. 923,045. A two-layer configuration can be preferably used.

Usually, it is preferable to arrange the layers so that the photosensitivity decreases toward the support, and a non-photosensitive layer may be provided between each halogen emulsion layer. −
No. 112751, No. 62-200350, No. 62-2
As described in No. 06541, No. 62-206543, etc., a low-sensitivity emulsion layer may be provided on the side far from the support, and a high-sensitivity emulsion layer may be provided on the side close to the support.

As a specific example, from the side farthest from the support, low sensitivity blue sensitive layer (BL) / high sensitivity blue sensitive layer (B H) / high sensitivity green sensitive layer (GH) / low sensitivity green sensitive layer (GL ) / high-sensitivity red-sensitive layer (RH) / low-sensitivity red-sensitive layer (RL),
Alternatively, they can be installed in the order of BH/BL/GL/GH/RH/RL, or in the order of BH/BL/GH/GL/RL/RH.

Further, as described in Japanese Patent Publication No. 55-34932, from the side farthest from the support, the blue-sensitive layer/GH/R
They can also be arranged in the order of H/GL/RL. Alternatively, as described in JP-A-56-25738 and JP-A-62-63936, the blue-sensitive layer/GL/RL/GH/RH can be arranged in this order from the farthest side from the support. .

In addition, as described in Japanese Patent Publication No. 49-15495, the upper layer is a silver halide emulsion layer with the highest sensitivity, the middle layer is a silver halide emulsion layer with lower sensitivity, and the lower layer is more sensitive than the middle layer. An example is an arrangement consisting of three layers with different photosensitivity, in which a silver halide emulsion layer with a low density is disposed and the photosensitivity gradually decreases toward the support. Even when it is composed of three layers with different photosensitivity, as described in JP-A No. 59-202464,
In the same color-sensitive layer, medium-sensitivity emulsion layer/high-sensitivity emulsion layer/low-sensitivity emulsion layer may be arranged in this order from the side remote from the support.

As mentioned above, various layer structures and arrangements can be selected depending on the purpose of each photosensitive material.

The preferred silver halide contained in the photographic emulsion layer is about 30
Silver iodobromide, silver iodochloride, or silver iodochlorobromide containing less than mol% of silver iodide. Particularly preferred are silver iodobromide or silver iodochlorobromide containing from about 3 mole percent to about 25 mole percent silver iodide.

Silver halide grains in photographic emulsions include those with regular crystals 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. Further, the present invention is effective for color photosensitive materials having a relatively high coating silver amount, such as 4 to 8 g/m.

Silver halide photographic emulsions that can be used in the present invention include, for example, Research Disclosure (hereinafter referred to as RD) Nα
17643 (December 1978).

pp. 22-23, “1. Emulsion production (Emulsionp.
8716 (November 1979), 64
8 pages, graphic "Physics and Chemistry of Photography", published by Beaumontel (P.

Glafkides, Chemic et Ph1
sique Photography+que.

Paul Mantel, 1967), "Photographic Emulsion Chemistry" by Duffin, published by Focal Press (G,
F, Duffi mouth.

Photographic Emulsion Che
Mistry (Focal Press.

1966)), Zelikman [Manufacturing and Coating of Photographic Emulsions]
, Published by Focal Press (V, L, Zelik
Manet al, Making and C
oatingPhotographicEmulsio
It can be prepared using the method described in, for example, 1964).

U.S. Patent No. 3,574,628, U.S. Patent No. 3,655.39
Monodisperse emulsions such as those described in No. 4 and British Patent No. 1,413,748 are also preferred.

Tabular grains having aspect ratios of about 5 or more can also be used in the present invention. Tabular grains are described in Gutoff, Photographic Science and Engineering.
engineering), 1st
4, pp. 248-257 (1970), U.S. Patent No. 4,
434゜226, 4,414,310, 4,4
33.048, British Patent No. 4,439,520, and British Patent No. 2,112,157.

The crystal structure may be --like, the inside and outside may have different halogen compositions, it may be a layered structure, or silver halides with different compositions may be joined by epitaxial bonding. It may also be bonded with a compound other than silver halide, such as silver rhodan or lead oxide.

Also, mixtures 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. During the physical ripening process, various polyvalent metal ion impurities (cadmium, zinc,
It is also possible to introduce salts or complex salts of lead, copper, thallium, iron, ruthenium, rhodium, palladium, osmium, iridium, platinum, etc.). Compounds used for chemical sensitization include those described in the lower right column on page 18 to the upper right column on page 22 of the specification of JP-A-62-215272. Further, additives used in such a process are described in RDkl 7643 and RDkl Na18716, 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 RDs, and the relevant descriptions are shown in the table below.

Additive type RD 17643 RD 1871
61 Chemical sensitizers Page 23 Page 648 Right column 2
Sensitivity enhancer Same as above 3 Spectral sensitizers, pages 23-24 Page 648 right column - Super sensitizers
Page 649 Right Column 4 Brightener Page 24 5 Antifog Agent Pages 24-25 Page 649 Right Column ~
and stabilizer 6 light absorber, fu pages 25-26 page 649 right column ~
Ilter dye, page 650 left column UV absorber 7 Stain inhibitor page 25 right column page 650 left to right column 8
Dye image stabilizer page 25 9 Hardener page 26 page 651 left column 10 Binder page 26 Same as above 11 Plasticizer, lubricant page 27 page 650 right column 12 Coating aid,
Pages 26 to 27 Page 650 Right column Surfactant 13 Static inhibitor Page 27 Same as above In addition, in order to prevent deterioration of photographic performance due to formaldehyde gas, U.S. Pat.
It is preferable to add to the photosensitive material a compound that can be immobilized by reacting with formaldehyde as described in No. 5,5.03.

Various color couplers can be used in the present invention, and specific examples thereof include Maebata's RDNα17643, ■-C-G
It is described in the patent described in .

As a yellow coupler, for example, U.S. Patent No. 3.93
No. 3,501, No. 4,022,620, No. 4,326
, No. 024, No. 4,401,752, No. 4,248,
No. 961, Special Publication No. 58-10739, British Patent No. 1,
No. 425,020, No. 1.476.760, U.S. Patent No. 3,973°968, No. 4,314,023, No. 4,511.6.49, European Patent No. 249,473A
Preferably, those described in No.

As macenta couplers, 5-pyrazolone and pyrazoloazole compounds are preferred, and U.S. Patent No. 4,31
No. 0,619, 4. 351. No. 897, European Patent No. 73,636, U.S. Patent No. 3,061,432,
No. 3,725,064, RDNα24220 (19
June 1984), JP-A-60-33552, RDNα2
4230 (June 1984), JP-A-60-4365
No. 9, No. 6172238, No. 60-35730, No. 55-118034, No. 60-185951, U.S. Pat. No. 4,500,630, No. 4. 540. 65
No. 4, No. 4,556,630, WO (PCT) 881
Particularly preferred are those described in No. 04795 and the like.

Cyan couplers include phenolic and naphthol couplers, and are described in U.S. Pat. No. 4,052,212.
No. 4,146,396, No. 4,228,233, No. 4,296,200, No. 2,369,929,
2,801.171, 2,772,16.2,
Same 2. 895. No. 826, No. 3,772,002, No. 3,758°308, No. 4,334,011,
No. 4,327.173, West German Patent Publication No. 3. 329
．． 729, European Patent No. 121.365A, European Patent No. 24
9゜453A, U.S. Pat. No. 3,446,622, U.S. Pat. No. 4,333,999, U.S. Pat.
, No. 451,559, No. 4.427.767, No. 4,
No. 690,889, No. 4,254゜212, No. 4,2
Those described in No. 96,199, JP-A No. 61-42658, etc. are preferred.

Colored couplers for correcting unnecessary absorption of coloring dyes are disclosed in RD No. 17643, Section ■-G, U.S. Patent No. 4.
．． Preferred are those described in Japanese Patent Publication No. 163,670, Japanese Patent Publication No. 57-39413, U.S. Pat. In addition, couplers that correct unnecessary absorption of coloring dyes using fluorescent dyes released during coupling as described in U.S. Patent No. 4,774,181, and couplers that react with developing agents as described in U.S. Patent No. 4,777°120. It is preferable to use a coupler having as a leaving group a dye precursor group capable of forming a dye.

Couplers whose coloring 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 polymerized dye-forming couplers are U.S. Pat.
It is described in 4,367.282, 4,409.320, 4,576.910, British Patent 2,102,173, etc.

Couplers that release photographically useful residues upon coupling are also preferably used in the present invention. DIR couplers releasing development inhibitors include the aforementioned RD17643,
Patents listed in Sections ■-F, Japanese Patent Application Laid-Open No. 57-151944
No. 57-154234, No. 60-184248, No. 63-37346, U.S. Patent No. 4,248.926
No. 4782.012 is preferred.

Couplers that release a nucleating agent or a development accelerator imagewise during development include British Patent No. 2,097.140;
Those described in JP-A No. 2,131,188, JP-A-59-157638, and JP-A-59-170840 are preferred.

Other couplers that can be used in the photosensitive material of the present invention include competitive couplers described in U.S. Pat. No. 4,130,427, U.S. Pat. 4.310,618, etc. DIR redox compound releasing couplers, DIR couplers releasing couplers, DIR described in JP-A-60-185950, JP-A-62-24252, etc.
Coupler-releasing redox compound or DIR redox-releasing redox compound, European Patent No. 173.302A
R
DNα11449, DNα24241, JP-A-61-201
Bleach accelerator releasing couplers such as those described in US Pat. No. 247, Box 4. 553. Examples thereof include the ligand-releasing couplers described in No. 477, the leuco dye-releasing couplers described in JP-A-63-75747, and the fluorescent dye-releasing couplers described in US Pat. No. 4,774,181.

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 U.S. Patent No. 2,322,027, etc.; Specific examples of boiling point organic solvents include phthalate esters (dibutyl phthalate, cyclohexyl phthalate,
Di-2-ethylhexyl phthalate, decyl phthalate, bis(2゜4-di-t-amylphenyl) phthalate, bis(2,4-di-t-amylphenyl) isophthalate), bis(1,1-ene ethylpropyl) ) phthalates, etc.), esters of phosphoric or phosphonic acids (triphenyl phosphate, triphrenol phosphate, 2-
ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2-ethylhexylphenyl phosphonate, etc.), benzoic acid esters (2-ethylhexyl Henshade,
dodecyl benzoate, 2-ethylhexyl-p-hydroxybenzoate, etc.), amides (N, N-diethyl dodecanamide, N, N diethyl laurylamide, N-tetradecyl pyrrolidone, etc.), alcohols or phenols (isostearyl Alcohol, 2
, 4-sitert-amylphenol, etc.), aliphatic carboxylic acid esters (bis(2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate, etc.), aniline derivatives (N , N-dibutyl-2
-butoxy-5-tert-octylaniline, etc.),
Examples include hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene, etc.). In addition, as an auxiliary solvent, the boiling point is about 30°C or higher, preferably 50°C.
Any organic solvent having a temperature above about 160°C or below can be used, and typical examples thereof include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, dimethylformamide, and the like.

The process and effects of latex dispersion methods and specific examples of latex for impregnation are described in U.S. Patent No. 4. 199. No. 363, West German Patent Application (OLS) No. 2,541°274 and OLS No. 2,541.
, No. 541, 230, etc.

These couplers can also be impregnated into rhodapuru latex polymers (e.g., U.S. Pat. No. 4,203,716) in the presence or absence of high-boiling organic solvents as described above, or in water-insoluble and organic solvent-soluble polymers. It can be emulsified and dispersed in a hydrophilic colloid aqueous solution.

Preferably, the homopolymers or copolymers described on pages 12 to 30 of International Publication No. W08810 O723 are used. In particular, the use of acrylamide-based polymers is preferred from the viewpoint of color image stabilization.

The present invention can be applied to various color photosensitive materials. Typical examples include color negative film for general use or movies, color reversal film for slides or television, color paper, direct positive color photosensitive materials, color positive film, and color reversal paper.

Suitable supports that can be used in the present invention include, for example, the above-mentioned R
D, NQ, page 28 of 17643, and page 647 right column to page 648 left column of k18716.

In the light-sensitive material of the present invention, the total thickness of all the hydrophilic colloid layers on the side having the emulsion layer is 25 μm or less, preferably 20 μm or less.
m or less, and the membrane swelling rate in section 1 is preferably 30 seconds or less (preferably 15 seconds or less). The film thickness means the film thickness measured at 25° C. and 55% relative humidity (2 days), and the film swelling rate T'A can be measured according to a method known in the art. For example, Knee Green (A
Photographic Science and Engineering Link (Photogr., Green) et al.

Sci, Eng, ), Volume 19, No. 2, 124-12
It can be measured by using a swellometer (swelling membrane) of the type described on page 9, and outside T is heated at 30°C for 3 minutes and 15 minutes using a color developer.
The saturated film thickness is defined as 90% of the maximum swollen film thickness reached when the film is processed for seconds, and is defined as the time it takes to reach each film thickness.

The membrane swelling rate TVz can be adjusted by adding a hardening agent to seratin as a binder or by changing the aging conditions after coating.

Further, the swelling rate is preferably 150 to 400%. The swelling rate is calculated from the maximum swollen film thickness under the conditions mentioned above, using the formula;
It can be calculated according to (maximum swelling film thickness - film thickness)/film thickness.

The above-mentioned color photographic light-sensitive material is the above-mentioned RDNα1764.
3, pp. 28-29, and Nα18716, 615, left column to right column.

The color developing solution used for developing the photosensitive material is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. Aminophenol compounds are also useful as color developing agents, but p-phinidinediamine compounds are preferably used, representative examples of which include 3-methyl-4-amino-N, N-diethylaniline, 3-Methyl-4-amino-N-ethyl-N-1β-
Hydroxyethylaniline, 3-methyl-4-amino-
Examples include N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-β-methoxyethylaniline, and their sulfates, hydrochlorides, or p-toluenesulfonates. . Two or more of these compounds can be used in combination depending on the purpose.

The color developer may contain pH buffering agents such as alkali metal carbonates, borates or phosphates, bromide salts, iodide salts,
Development inhibitors or antifoggants such as benzimidazoles, benzothiazoles or mercapto compounds are generally included. In addition, if necessary, hydroxylamine, diethylhydroxylamine, sulfite hydrazines, phenyl semicarbazides, triethanolamine, catechol sulfonic acids, triethylenediamine (1,4-diazabicyclo[2゜2.2]octane), various preservatives such as ethylene glycol, organic solvents such as diethylene glycol, development accelerators such as benzyl alcohol, polyethylene glycol, quaternary ammonium salts, amines, dye-forming couplers, fogging agents such as competing couplers sodium boron hydride. , an auxiliary developing agent such as 1-phenyl-3-pyrazolidone, a viscosity imparting agent, various calcinates such as aminopolycarboxylic acid, aminopolyphosphonic acid, alkylphosphonic acid, and phosphonocarboxylic acid, for example, Ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,
1-diphosphonic acid, nitrilo-N,N,N-trimethylenephosphonic acid, ethylenediamine-N, N, NN-
Tetramethylene phosphonic acid, ethylene glycol (○-
hydroxyphenylacetic acid) and their salts), 4.4'
- Fluorescent brighteners such as diamino-2,2'-disulfostilbene compounds, various surfactants such as alkylsulfonic acids, arylsulfonic acids, aliphatic carboxylic acids, and aromatic carboxylic acids may be added. good.

Further, when performing reversal processing, black and white development is usually performed and then color development is performed. In this black and white developer, known black and white developing agents such as dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as -phenyl-3-pyrazolidone, or aminophenols such as N-methyl-p-aminophenol are used alone or Can be used in combination.

The pH of these color developing solutions and black and white developing solutions is generally 9 to 12. The amount of replenishment of these developing solutions depends on the color photographic light-sensitive material being processed, but in general it is 31 or less per square meter of light-sensitive material, and by reducing the bromide ion concentration in the replenisher, it can be increased to 500 or less.
It can also be less than ml. In particular, when using so-called high silver chloride light-sensitive materials, by lowering the bromide ion content and relatively increasing the chloride ion content in the color developing solution, it is possible to achieve excellent photographic properties and processability, and to suppress fluctuations in photographic properties. This is particularly preferable because it allows The amount of replenishment in such cases can be reduced to about 20 -/m2 of photosensitive material where overflow in the color developing bath is substantially eliminated. When reducing the amount of replenishment, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the area of contact with the air in the processing tank. Furthermore, the amount of replenishment can be reduced by using means for suppressing the accumulation of bromide ions in the developer.

The processing temperature of the color developing solution of the present invention is 20 to 50°C, preferably 30 to 45°C. The processing time is 20 seconds to 5 minutes, preferably 30 seconds to 3 minutes, but the processing time can be further shortened by using high temperature, high pH, and high concentration of color developing agent. .

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

The bleaching process may be carried out simultaneously with the fixing process (bleach-fixing process) or separately. Furthermore, in order to speed up the processing, a processing method may be used in which bleaching is followed by bleach-fixing. Furthermore, treatment with two consecutive bleach-fixing baths, fixing treatment before bleach-fixing treatment, or bleaching treatment after bleach-fixing treatment can be carried out as desired depending on the purpose. The process is ■bleach → fixing, ■bleach-fix, ■bleach→
There are bleach-fixing, ■ bleaching → bleach-fixing → fixing, etc. Examples of bleaching agents that can be used include compounds of polyvalent metals such as iron (■), cobal l-(III), chromium (■), and copper (II), peracids, quinones, and nitro compounds.

Typical bleaching agents include ferricyanide; dichromate: organic complex salts of iron (III) or cobalt (III); for example, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, l,3-diamino Aminopolycarboxylic acids such as propanetetraacetic acid, glycol ether diamine tetraacetic acid, or complex salts of citric acid, tartaric acid, malic acid, etc.; persulfates; bromates; permanganates; nitrobenzenes, etc. can be used. Among these, aminopolycarboxylic acid iron (I[I) complex salts and persulfates, including ethylenediaminetetraacetic acid iron (I[I) complex salts] are preferred from the viewpoint of rapid processing and prevention of environmental pollution. Furthermore, aminopolycarboxylic acid iron(II[) complex salts are particularly useful in both bleach and bleach-fix solutions.

In particular, from the viewpoint of bleaching ability, so-called high-potential oxidizing agents having an oxidation-reduction potential of 150 mV or more are preferred as bleaching agents for negative photographic materials. These aminopolycarboxylic acid iron (I
II) The pH of the bleaching solution or bleach-fixing solution using a complex salt is usually 5.5 to 8, or it can be processed at an even lower pH for speeding up the processing.

A bleach accelerator may be used in the bleaching solution, bleach-fixing solution, and their prebaths, if necessary.

Specific examples of useful bleach accelerators are described in the following specification. US Patent No. 3,893,858, West German Patent No. 1
, No. 290,812, No. 2,059°988, JP-A No. 53-32736, No. 53-57831, No. 53-
No. 37418, No. 53-72623, No. 53-956
No. 30, No. 5395631, No. 53-104232, No. 53-124424, No. 53-141623,
No. 53-28426, RD No. 17129 (1
Compounds having a mercapto group or disulfide group as described in JP-A No. 50-140129, JP-A No. 45-8506, JP-A No. 52-20832, JP-A No. 53-32735 issue,
Thiourea derivatives described in U.S. Patent No. 3,706゜561; West German Patent No. 1゜127.715, JP-A-58-1
Iodide salt described in No. 6,235: West German patent tube 966.4
10, polyoxyethylene compounds described in JP-A No. 2,748,430; polyamine compounds described in JP-A No. 45-8836; and other JP-A-49-42434 and JP-A-49
-59644, 53-94927, 54-35
No. 727, No. 55-26506, No. 5B-16394
Compounds described in No. 0; bromide ions, etc. can be used. Among them, compounds having a mercapto group or a disulfide group are preferable from the viewpoint of a large promoting effect, and in particular, compounds having a mercapto group or a disulfide group are preferred.
, No. 893.858, West German Patent No. 1,290,812, and JP-A-53-95630 are preferred. Furthermore, compounds described in US Pat. No. 4,552,834 are also preferred. These bleach accelerators may be added to the photosensitive material. These bleach accelerators are particularly effective when bleach-fixing color light-sensitive materials for photography.

Known additives such as rehalogenating agents such as ammonium bromide and ammonium chloride, pH buffering agents such as ammonium nitrate, and metal corrosion inhibitors such as ammonium sulfate can also be added to the bleach-fixing solution of the present invention.

In addition to the compound of the present invention, known fixing agents may be used in the fixing bath of the present invention. For example, fixing agents include thiosulfate, thiocyanate, thioether compounds, thioureas, and large amounts of iodide salts, but thiosulfate is commonly used, and ammonium thiosulfate is particularly It is preferable from the viewpoint of solubility and fixing speed, and may be used in combination with other fixing agents. As the preservative for the bleach-fix solution, sulfites, bisulfites, carbonyl bisulfite adducts, and sulfinic acid compounds are preferred. The fixer contains aminopolycarboxylic acids and organic phosphonic acid chelating agents (preferably 1-hydroxyethylidene-1,1-diphosphonic acid and N, N, N') to improve the stability of the fixer.
, N'-ethylenediaminetetraphosphonic acid).

The fixing solution may further contain various fluorescent brighteners, antifoaming agents, surfactants, polyvinylpyrrolidone, methanol, and the like.

From the viewpoint of shortening the desilvering treatment time, it is preferable that the stirring of each treatment solution in the desilvering step be as strong as possible. As a stirring means, JP-A-62-183460 and JP-A-62-183460 are used.
-183461, etc.
In the case of means for colliding jets, it is preferable that the collision be performed within 15 seconds after the photosensitive material is introduced into the processing liquid.

In the present invention, the crossover time from the color developer to the bleach solution (the time in the air from when the photosensitive material leaves the color developer to when it enters the bleach solution) is important in improving bleach fog and dirt adhesion on the surface of the photosensitive material. Preferably within 10 seconds. In addition, the cross-over time from the bleaching solution to the processing solution having fixing ability according to the present invention is 10% from the viewpoint of improving the defective color restoration of cyan dye.
Preferably within seconds.

Here, the amount of replenishment of the fixing solution and bleach-fixing solution is based on the color photosensitive material for photography (for example, the amount of coated silver is 4 to 12 g/rr?
), preferably 800 J,/m or less.

The silver halide color photographic material used in the present invention is generally subjected to a water washing and/or stabilization process after desilvering treatment. The amount of water used in the washing process is determined by the characteristics of the photosensitive material (
For example, it can be set over a wide range depending on the material used (for example, a coupler), the purpose, the temperature of the washing water, the number of washing tanks (the number of stages), the replenishment method such as counterflow or forward flow, and various other conditions. Among these, the relationship between the number of flushing tanks and the amount of water in the multistage countercurrent method is described in the Journal of the 5ociety.
of Motion Picture and Te
1evision Engineers Volume 64, P.
248-253 (May 1955 issue).

According to the multistage countercurrent method described in the above-mentioned document, the amount of water used for washing can be significantly reduced, but due to the increase in the residence time of water in the tank, bacteria may breed, and the resulting floating substances may adhere to the photosensitive material. The problem arises. In the processing of the color photosensitive material of the present invention, as a solution to such problems,
Ca ion, Mg described in JP-A No. 62-288838
Ion reduction methods can be used very effectively. In addition, chlorine-based disinfectants such as isothiazolone compounds, cyabendazole, chlorinated sodium isocyanurate, and other benzotriazoles described in JP-A No. 57-8542, "Chemistry of Antibacterial and Antifungal Agents" by Hiroshi Horiguchi It is also possible to use disinfectants described in ``Microbial sterilization, sterilization, and anti-mold technology'', a complete collection of sanitary techniques, and ``Encyclopedia of anti-bacterial and anti-mold agents'' edited by the Japanese Society of Anti-bacterial and Anti-fungal agents.

The pH of the washing water in the processing of the photosensitive material of the present invention is 4 to 4.
9, preferably 5-8. The washing water temperature and washing time can also be set variously depending on the characteristics of the photosensitive material, its use, etc., but generally it is 20 seconds to 10 minutes at 15 to 45°C, preferably 2
A range of 30 seconds to 5 minutes at 5 to 40°C is selected. Furthermore, the photosensitive material of the present invention can also be directly processed with a stabilizing solution instead of washing with water. In such stabilization treatment, Japanese Patent Application Laid-Open Nos. 57-8543 and 58-1483
All known methods described in No. 4 and No. 60-220345 can be used.

Further, following the water washing treatment, a further stabilization treatment may be carried out, such as formalin, hexamethylenetetramine, hexahydrotriane, or N-methylol compounds, which are used as a final bath for color photosensitive materials for photography. Stabilizing baths containing dye stabilizers typified by: This stabilizing bath may also contain ammonium compounds, metal compounds such as Bi and Aβ, optical brighteners, various bleaching agents, membrane pH regulators, hardeners, bactericidal agents, antifungal agents, etc.
Alkanolamines and surfactants (preferably silicone-based) may also be added. In addition to tap water, the water used in the washing process or stabilization process has a Ca ion and Mg ion concentration of 5 ■/l using an ion exchange resin, etc.
It is preferable to use deionized water or water sterilized with halogen or ultraviolet germicidal lamps.

The replenishment amount of the washing and/or stabilizing solution is 1 to 50 times, preferably 2 to 30 times, more preferably 2 to 15 times the amount brought in from the bath per unit area of the photosensitive material. The overflow liquid accompanying this replenishment can also be reused in other processes such as the desilvering process.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up processing. In order to incorporate the color developing agent, it is preferable to use various precursors of the color developing agent. For example, U.S. Patent No. 3,342,59
Indoaniline compound described in No. 7, No. 3,342.5
No. 99, RDN (No. 114,850 and No. 15,159)
Schiff base type compounds described in No. 13,924, metal salt complexes described in U.S. Pat. No. 3,719.492, and urethane compounds described in JP-A-53-135628. .

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

Various treatment liquids in the present invention are used at 10°C to 50°C. Normally, the standard temperature is 33°C to 38°C, but higher temperatures can be used to accelerate processing and shorten processing time, or lower temperatures can be used to improve image quality and stability of the processing solution. can do. Further, in order to save silver on the photosensitive material, a treatment using cobalt intensification or hydrogen peroxide intensification as described in German Patent No. 2,226,770 or US Pat. No. 3,674,499 may be carried out.

One example of a silver halide color light-sensitive material is one using direct positive silver halide. Processing using this photosensitive material will be explained below.

After imagewise exposure of a silver halide color photographic light-sensitive material, after or while subjecting it to fogging treatment with light or a nucleating agent,
Contains aromatic primary amine color developing agent pH 11,5
It is also preferable to directly form a positive color image by color development, bleaching and fixing using the following surface developer.

It is more preferable that the pH of this developer is in the range of 11.0 to 10.0.

The fogging treatment in the present invention is the so-called [light fogging method].
Either of a method called "chemical fogging method" in which the entire surface of the photosensitive layer is exposed to second light, and a method called "chemical fogging method" in which development is performed in the presence of a nucleating agent may be used. Development may be carried out in the presence of a nucleating agent and fogging light. Further, a photosensitive material containing a nucleating agent may be fog-exposed.

Regarding the light fogging method, the above-mentioned Japanese Patent Application Laid-Open No. 61-25371
6 specification, page 47, line 4 to page 49, line 5, and the nucleating agent that can be used in the present invention is described in the same specification, page 49, line 6 to page 67, line 2, and in particular - Formula (N-
The use of compounds represented by 1) and [N-2] is preferred. Specific examples of these include [N-1-1) to (N-1-10) described on pages 56 to 58 of the same specification and [N-11-1] described on pages 63 to 66 of the same specification. 1: ] ~ [N −l
1-12] is preferably used.

Regarding the nucleation accelerator that can be used in the present invention, see the same specification No. 6.
It is described on page 8, line 11 to page 71, line 3, and specific examples include (A-1) to page 69 to page 70 of the same.
(A-13) is preferably used.

The color developer used in the development of the light-sensitive material of the present invention is described in the same specification from page 71, line 4 to page 72, line 9, and in particular aromatic primary amine color developer. As a specific example, p-phinidinediamine type compounds are preferable, and a representative example thereof is 3-methyl-4-amino-N-ethyl N-(β-methanesulfonamidoethyl).
Aniline, 3-methyl-4-amino-N-ethyl-N-
(β-hydroxyethyl)aniline, 3-methyl-4-
Examples include amino-N-ethyl-N-methoxyethylaniline and salts thereof such as sulfates and hydrochlorides.

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

Example 1 On a subbed cellulose triacetate film support,
Sample 101, which is a multilayer color light-sensitive material consisting of each layer having the composition shown below, was prepared.

(Composition of the photosensitive layer) The coating amount is the amount expressed in g/r+ (units of silver) for silver halide and colloidal silver, and the amount expressed in g/% for coupler additives and ceratin. The number of moles of sensitive dyes is expressed per mole of silver chloride (in the same layer).

1st layer (antihalation layer) Black colloidal silver ceratin ExY-8 2nd layer (intermediate layer) Ceratin V-1 V-2 V-3 xF-1 olv-2 3rd layer (low-sensitivity red-sensitive emulsion layer) Silver bromide emulsion (AgI 1 mol%, internal high AgI type,
Equivalent sphere diameter: 0.3 μm, Equivalent sphere diameter: ■.

0゜2, 10 0×1O-2 0XIO-'0XIO-' Coating amount 0.50 Gelatin 1.50ExS-
11,0xlO'ExS-23,0XIO-'ExS-31,0XIO-" ExC-30,22 ExC-43,0xlO"5olv-17,0XIO-' 4th layer (mid-sensitivity red-sensitive emulsion layer) Iodobromide Silver emulsion (AgI 2 mol%, internal high AgI type,
Equivalent sphere diameter 0.55 μm 1 sphere equivalent diameter variation coefficient 28%, normal crystal, twin crystal mixed particles, diameter/thickness ratio 1.0) Gelatin ExS-I ExS-2 ExS-3 Silver coating amount 0.85 2.00 1.0XlO-'3.0X10-' 1.0XlO-5 ExC-28,0XIO-" ExC-30,33 ExY-132,0XIO-2 ExY-141,oxto-2 Cpd-101,0XIO-' 5olv- 10,10 5th layer (high sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion (AgI 5 mol%, internal high Agl type,
Equivalent sphere diameter 0.7 μm, coefficient of variation of equivalent sphere diameter 20%, twinned mixed particles, diameter/thickness ratio 2.0) Silver coating amount 0.50 Gelatin 1.60ExS-
11,0xlO-'ExS-23,0XIO-"ExS-31,0XIO"ExC-57,0xlO-' ExC-68,,Ox 10-2 Solv-10,15 Solv-28,0XIO-2 6th layer ( Intermediate layer) Ceratin l, 10P-20
,17 Cpd-1o, 10 Cpd-40,17 Solv-15,0XIO-' 7th layer (low-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion (Agl 1 mol%, internal high Agl type,
Equivalent sphere diameter 0.3 μm, coefficient of variation of equivalent sphere diameter 22%, normal crystal, twin crystal mixed particles, diameter/thickness ratio 2.5) Silver coating amount 0.30 Ceratin 0.50ExS-
45,0xlO-'ExS-52,0xlO-'ExS-60,3xlO-' ExM-83,OXIO-2 ExM-90,20 ExY-133,0XIO-2 Cpd-117,0xlO-' 5olv-10,20 8th layer (medium-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion (Ag1 2 mol%, internal high AgI type, equivalent sphere diameter 0.55 μm, coefficient of variation of equivalent sphere diameter 24%, normal crystal, twin mixed grains , diameter/thickness ratio 4.0) Silver coating amount 0.70 Gelatin 1.00ExS-
45,0XIO-'ExS-52,0XIO-'ExS-63,0XIO" ExM-83,0XIO-! ExM-90,25 ExM-101,5XIO-2 ExY-134,0XIO-2 Cpd-119,0XIO- '5olv-10,2'0 9th layer (high-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion (Ag1 5 mol%, internal high Agl type, equivalent sphere diameter 0.7 μm, coefficient of variation of equivalent sphere diameter 20% , normal crystal, twinned mixed particles, diameter/thickness ratio 2.0) Silver coating amount 0.40 Gelatin 0.90ExS-
42,oxto-'ExS-52,0xlO'ExS-62,0xLO"ExS-73,0xlO' ExM-82,oxto-2 ExM-116,Ox 10" ExM-122,0xlO-2 Cpd-21,0XIO- "Cpd-92,0xlO-'Cpd-102,0xlO-' 5olv-10,20 Solv-25,0xlO-" 1st O layer (yellow filter layer) Gelatin 0.90 yellow colloidal silver 5.0X10-"Cpd-10 ，
20 Solv-10,15 11th layer (low sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion (AgI 2 mol%, internal high AgI type,
(equivalent sphere diameter 0.5 μm, coefficient of variation of equivalent sphere diameter 22%, octahedral particles) Silver coating amount 0.40 Gelatin 1.00ExS-8
2,0xlO-' ExY-139,0xlO-2 ExY-150,90 Cpd-21,0XIO-2 Solv-10,30 12th layer (high sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion (AgI 5 mol% , internal high AgI type,
Equivalent sphere diameter 1.3 μm Coefficient of variation of equivalent sphere diameter 29%, normal crystal, twin crystal mixed particles, diameter/thickness ratio 4.5) Silver coating amount 0.40 Gelatin 0.60ExS-8
1,0xlO-'' ExY-150,12 Cpd-21,0XIO-' 5o1v-14゜0XIO-2 13th layer (first protective layer) Fine grain silver iodobromide (average grain size 0.07 μm, Ag1 1 mol% ) 0.20 gelatin
0,80UV-20,10 UV-30,10 UV-40,20 Solv-34,oxto-2 P-29,0XIO-2 14th layer (second protective layer) Gelatin 0.90B-1 (
Diameter 1. 5μm) 01lOB-2 (diameter 1.5μm) 0.10B-32,0xl
O-” H-10,40 Furthermore, in order to improve storage stability, processability, pressure resistance, anti-fungal and anti-bacterial properties, antistatic properties, and applicability, the following Cpd-
3, Cpd-5, Cpd-6, Cpd-7, Cpd-8
, P-1, W-1, W2, and W-3 were added.

In addition to the above, n-butyl-p-hydroxybenzoate was added. Furthermore, B-4, F-1, F-4, F-5
, F-6, F-7, F"-8, F9, F-10, F-1
1, F-13, and iron salts, lead salts, gold salts, platinum salts, iridium salts, and rhodium salts.

Next, the chemical structural formulas or chemical names of the compounds used in the present invention are shown below.

V-1 V-2 V-3 V-4 olv-1 Non-acid trichloride olv-2 Futanoq yo dibutyl olv-3 Nonacid tri(2-ethylhexyl) EχF-1 zHs Js cz++5osoxEl xC-2 H EχC-3 H (1) LhHqOUNH mouth xC-4 C1l.

xC-5 xC-6 H ExM-8 ExM-9 ExM-10 ExM-11 ExM-42 xY-13 xY-14 xY-15 M8 pd-1 pd-2 0M p d-3 pd-4 pd-5 pd-6 Cpd-1 cp d-9 Pd-11 Cpd-8 Cpd-10 Eχ5-1 EχS-2 xS-3 xS-4 Eχ5-5 EχS-6 xS-7 xS-8 C,H.

C,F+tSO! N (CJJCHzCOOKp-t Copolymer of vinyl vicritone and vinyl alcohol (copolymerization ratio -70:30 [weight ratio]) Polyethyl acrylate CH÷5OtNa Next, 3.4.5.7.8.9.11 Samples 102 and 103 were prepared in a similar manner, with the emulsion of .12 layers and the amount of silver coated changed as follows.

Third layer (low-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion (Agl 2 mol%, internal high Agl type,
Equivalent ball diameter 0. 3 μm, coefficient of variation of equivalent sphere diameter 29%, normal crystal, twin crystal mixed grain, diameter/thickness ratio 2.5) Silver coating amount 0.50 g/r & 4th layer (medium-sensitivity red-sensitive emulsion layer) Silver iodobromide Emulsion (AgI 4 mol%, internal cylinder AgI type,
Equivalent sphere diameter 0.55 μm, coefficient of variation of equivalent sphere diameter 20%, normal crystal, twin crystal mixed grain, diameter/thickness ratio 1.0) Silver coating amount 0.85 g/n (5th layer (high sensitivity red-sensitive emulsion) Layer) Silver iodobromide emulsion (Agl IQ mol%, internal cylinder AgI type, equivalent sphere diameter 0.7 μm, coefficient of variation of equivalent sphere diameter 30%, twinned mixed grains, diameter/thickness ratio 2.0) Silver coating amount 0.70g/rr? 7th layer (low-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion (AgI 2 mol%, internal cylinder AgI type,
Equivalent sphere diameter 0.3 μm, coefficient of variation of equivalent sphere diameter 28%, normal crystal, twin crystal mixed grains, diameter/thickness ratio 2.5) Silver coating amount 0.30 g/A 8th layer (medium-sensitivity green-sensitive emulsion layer) ) Silver iodobromide emulsion (AgI 4 mol%, internal cylinder AgI type,
Equivalent sphere diameter 0.55 μm, coefficient of variation of equivalent sphere diameter 20%, normal crystal, twin crystal mixed grains, diameter/thickness ratio 4.0) Silver coating amount 0.70 g/r & 9th layer (high-sensitivity green-sensitive emulsion layer) ) Silver iodobromide emulsion (AgI 10 mol%, internal high Agl type, equivalent sphere diameter 0.7 μm, coefficient of variation of equivalent sphere diameter 30%,
Normal crystal, twin crystal mixed grains, diameter/thickness ratio 2.0) Silver coating amount 0.50 g/G 11th layer (low-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion (AgI 4 mol%, internal AgI type) ,
Equivalent sphere diameter 0.5 μm, coefficient of variation of equivalent sphere diameter 15%, octahedral grains) Silver coating amount 0.40 g/m 12th layer (highly sensitive blue-sensitive emulsion layer) Silver iodobromide emulsion (Ag7 10 mol%, Inter-internal AgI type,
Equivalent sphere diameter 1.3 μm, coefficient of variation of equivalent sphere diameter 25%, normal crystal, twinned mixed particles, diameter/thickness ratio 4.5) Silver coating amount 0.50 g/rd Sample 103 3rd layer (low sensitivity red sensitivity Emulsion layer) Silver iodobromide emulsion (AgI 2 mol%, internal high Agl type,
Equivalent sphere diameter 0.3 μm, coefficient of variation of equivalent sphere diameter 29%, normal crystal, twin crystal mixed grain, diameter/thickness ratio 2.5) Silver coating amount 0.40 g/m 4th layer (medium-sensitivity red-sensitive emulsion layer) ) Silver iodobromide emulsion (AgI 4 mol%, internal high Agl type,
Equivalent sphere diameter 0.55 μm, coefficient of variation of equivalent sphere diameter 20%, normal crystal, twin crystal mixed grains, diameter/thickness ratio 1.0) Silver coating amount 0.85 g/A 5th layer (high sensitivity red-sensitive emulsion layer) ) Silver iodobromide emulsion (AgI 10 mol%, internal AgI type, equivalent sphere diameter 0.7 μm, coefficient of variation of equivalent sphere diameter 30%, twinned mixed grains, diameter/thickness ratio 2.0) Silver coating amount 0 .85g/7th layer (low-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion (AgI 2 mol%, internal AgI type,
Equivalent sphere diameter 0.3 μm, coefficient of variation of equivalent sphere diameter 28%, normal crystal, twin crystal mixed grains, diameter/thickness ratio 2.5) Silver coating amount 0.20 g/Bo 8th layer (medium-sensitivity green-sensitive emulsion layer) ) Silver iodobromide emulsion (AgI 4 mol%, internal AgI type,
Equivalent sphere diameter 0.55 μm, coefficient of variation of equivalent sphere diameter 20%, normal crystal, twin crystal mixed grains, diameter/thickness ratio 4.0) Silver coating amount 0.70 g/9th layer (high sensitivity green-sensitive emulsion layer) ) Silver iodobromide emulsion (AgI 10 mol%, internal high Agl type, equivalent sphere diameter 0.7 μm, coefficient of variation of equivalent sphere diameter 30%, normal crystal, mixed twin grains, diameter/thickness ratio 2.0) Silver Application amount 0. 70g/rr? 11th layer (low sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion (AgI 4 mol%, internal high Agl type,
Equivalent sphere diameter 065 μm, coefficient of variation of equivalent sphere diameter 15%, octahedral grains) Silver coating amount 0.30 g/12th resistant layer (highly sensitive blue-sensitive emulsion layer) Silver iodobromide emulsion (AgI 10 mol%, internal height Agl type, equivalent sphere diameter 1.3 μm, coefficient of variation of equivalent sphere diameter 25%, normal crystal, twin crystal mixed particles, diameter/thickness ratio 4.5) Silver coating amount 0.60 g/resistant sample 101.102.103 The average normality content of silver halide is 2.7 mol%, 5.7 mol%, and 6.3 mol%, respectively.

After these samples were cut and subjected to imagewise exposure, continuous processing (running test) was performed on each sample until twice the tank capacity of the fixing bath was replenished in the processing steps described below.

Processing process Processing time Processing temperature Replenishment amount 4 Color development 3
Minutes 15 seconds 38.0°c 23- Bleaching
50 seconds 38.0℃ 511T! bleach fixing
50 seconds 38.0°C fixation 50 seconds
38.0°C water washing (1130 seconds 38.0°
C water washing (2120 seconds 38.0°C stable)
20 seconds 38.0°c drying 1 minute 55
℃ *Replenishment amount is 35iILI! The amount of water submerged per meter of width is (
It was a countercurrent method from 2) to (1), and all the overflow of the washing water was introduced into the fixing bath. Refill the bleach-fixing bath at the top of the bleach tank of the automatic processor (16 y+! 20- and the bottom of the bleach-fixing tank, and the top of the fixing tank and the bottom of the bleach-fixing tank are connected with pipes, so that all the overflow liquid generated by supplying replenisher to the bleaching tank and fixing tank flows into the bleach-fixing bath. It was to so. The amount of developing solution carried into the bleaching process, the amount of bleaching solution carried into the fixing process, and the amount of fixing solution carried into the washing process are 2.35% each per 1 meter length of 35III11 width of photosensitive material. 5mI! ,2.0m
1, 2.0 ml. Further, the crossover time is 5 seconds in each case, and this time is included in the processing time of the previous step.

The composition of the treatment liquid is shown below.

(Developer) Diethylenetriaminepentaacetic acid l-hydroxyacetic acid lidene-1,l-diphosphonic acid sodium sulfite mother solution (g) Replenisher (g) 2.0 2.2 3.3 3.3 3.9 5.2 Potassium carbonate Potassium bromide potassium iodide hydroxylamine sulfate 2-methyl-4-CN-ethyl-N-(β-hydroxyethyl)amino]aniline sulfate and pH (bleach solution) 1, 3-propylenediaminetetraacetic acid Diferric ammonium hydrate Ammonium bromide Ammonium nitrate Hydroxyacetic acid Acetic acid 37.5 1.4 1.3■ 2.4 4.5 1.01 10,05 Mother liquor (g) 144,0 84.0 17.5 63. 0 33.2 39.0 1.01 10, 15 Replenisher (g) 206, 0 120, 0 25.0 90.0 47.4 Water tJlO,tTe1.01 1.01pH [A:/%
(Adjusted with water) 3.20 2.80 (Bleach-fixing solution mother liquor) A 15:85 mixture of the above bleaching solution mother liquor and the following fixing solution mother liquor (fixing solution) Mother liquor (g) Replenisher solution (g) Ammonium sulfite 19. 0 57.0Ammonium thiosulfate 280ml aqueous solution (700g
/47) or the compound of the present invention 1.32 mole imidazole
28.5 Ethylenediaminetetraacetic acid 12.5 Add water to 1.0f pH 7,40 [Adjusted with ammonia water and acetic acid] (Washing water) Mother liquor and replenisher common tap water to H-type strongly acidic cation exchange resin (Rohm and Haas Mixed bed type filled with Amberlite IR-120B) and OH type strong basic anion exchange resin (01 7.45 8401n! Amberlite IRA-400) Water was passed through the column to reduce the concentration of calcium and magnesium ions to 3 μ/l or less, and then 20 μ/l of sodium isocyanurate dichloride and 150 μ/l of sodium sulfate were added.

The pH of this solution was in the range of 6.5-7.5.

(Stabilizing solution) Common to mother solution and replenisher solution (Unit: g) Formalin (37%) 2. 0ml polyoxyethylene-p-0,3 Seventylenyl phenyl ethyl (average degree of polymerization 10) Ethylenediaminetetraacetic acid di 0,05 Add sodium brine to give 1.01pI (5,
0-8,0 Then, for the processed sample at the end of the running process, the transmission density of magenta in the unexposed area was measured using an X-rite densitometer and compared.

The results are shown in Table-1.

It can be seen from Table 1 that when the compounds of the present invention are used, good results with less staining (residual color) after processing are obtained even if the silver halide content is high.

Example 2 Compound-1 of Example 1 was converted into compound-2, 3, 5, 11, 2
A test similar to that of Example 1 was conducted except that the samples No. 3, 41, and 62 were used instead.

As a result, as in Example 1, when the fixing agent of the present invention was used for the stain after running treatment, good results were obtained for the sample with a high content.

Table 2± Example 3 Samples 101, 102, and 103 similar to those in Example 1 were subjected to imagewise exposure, and each was continuously processed in the following processing steps until twice the tank capacity of the bleach-fix bath was refilled. (running processing) was performed.

Processing process Processing time Processing temperature Replenishment amount Tank capacity Color development 3 minutes 15 seconds 38.0°C23J 1
! ! Bleach fixing 2 minutes 30 seconds 38.0°C20m1
51 Water washing (1) 30 seconds 38.0°C-
31 Wash (2) 20 seconds 38.0°03
4m/3A stable 20 seconds 38.0°C
20td31 Drying 1 minute 55°C *The amount of replenishment is per 1 meter of 35mm width Water submergence is countercurrent method from (2) to (1), and the amount of developer brought into the bleaching process and fixation of bleaching solution The amount carried into the process and the amount of fixer carried into the washing process is 35 mm.
2.5r+1.2 per 1m length of photosensitive material in width
．． Oml, 2. It was Oml.

Further, the crossover time is 5 seconds in each case, and this time is included in the processing time of the previous step.

The composition of the treatment liquid is shown below.

(Developer) Diethylenetriaminepentaacetic acid -Hydroxyethythene-1,1-diphosphonic acid Sodium sulfite Potassium carbonate Potassium bromide Potassium iodide Hydroxylamine sulfate 2-Methyl-4-(N- Ethyl-N-(β-hydroxy Ethyl)amine]aniline sulfate mother liquor (g) Replenisher (g) 2.0 2.2 3.3 3.3 3.9 37.5 1.4 1.3■ 2.4 5.2 39.0 0.4 3.3 4.5 6.1 Add water 1, oj7 1, Ol H (bleach-fix solution) 10.85 10.15 Replenisher (g) 56〇- Mother liquor (g) Ammonium thiosulfate 28〇 - (700 g/n) or the compound of the present invention Ammonium sulfite ■, Ferric ammonium 3-propylene diamine tetraacetate - Ammonium chloride bromide 40.0 Ammonium nitrate 20.0 Add water to 1.0 pH (25°C ) 5.8 (Adjusted with acetic acid and aqueous ammonia) (Wash water) Common tap water for mother liquor and replenisher was mixed with H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) and OH-type strong base. Mixed bed filled with aqueous anion exchange resin (80.0 2.65 mol 40.0 1.32 mol 80.0 40.0 1.0! 5.6 288, 0 144, 0 Amberlite IRA-400) Water was passed through the column to reduce the concentration of calcium and magnesium ions to 3 μ/l or less, and then 20 μ/l of sodium isocyanurate dichloride and 150 μ/l of sodium sulfate were added.

The pH of this solution was in the range of 6.5-7.5.

(Stabilizing solution) Common to mother solution and replenisher solution (Unit: g) Formalin (37%) 2.0 ml 1 Polyoxyethylene-p-0,3 Monononylphenyl ethyl (Average degree of polymerization 10) Sodium ethylenediaminetetraacetic acid di〇,05 Add salt water to 1.01 pH 5.0
-8,0 Then, for the processed sample at the end of the running process, the transmission density of magenta in the unexposed area was measured using an X-rite densitometer and compared.

The results are shown in Table-2.

It can be seen from Table 2 that when the compounds of the present invention are used, good results with less staining (residual color) after processing are obtained even if the silver halide content is high.

Example 4 Compound-1 of Example 3 was converted into compound-2, 3, 5, 11, 2
A test similar to that in Example 3 was conducted except that Samples No. 3, 26, 41, and 59 were used instead.

As a result, as in Example 3, when the fixing agent of the present invention was used for the stain after running treatment, good results were obtained for the sample with a high content.

Example 5 On a subbed cellulose triacetate film support,
Each layer having the composition shown below was coated in a multilayer manner to prepare a sample as a multilayer color photosensitive material.

(Photosensitive layer composition) The numbers corresponding to each component indicate the coating amount expressed in g/rrr units, and for silver halide, the coating amount is expressed in terms of silver. However, for sensitizing dyes, the coating amount is expressed in moles per mole of silver halide in the same layer.

1st layer (antihalation layer) Black colloidal silver Silver 0.18 Gelatin 1.40 2nd layer (intermediate layer) 2.5-di-t-pentadecylhydroquinone 0.18EX-10
,070 EX-30,020 EX-122,0xlO-'' U-10,060 B5-1 B5-2 Third layer of gelatin (first red-sensitive emulsion layer) Emulsion A Emulsion B Sensitizing dye I Sensitizing dye ■ Sensitizing dye Sensitive dye ■ EX-2 EX-10 B5-1 Gelatin 4th layer (second red-sensitive emulsion layer) Emulsion G 0,080 0,10 0, l 0 0,020 1,04 Silver 0.25 Silver 0.25 6.9X10-'1.8X10-'3.1X10-' 0, 34 0, 020 0, 070 0, 050 0, 070 0, 060 0, 87 Silver 1.00 Sensitizing dye ■ Sensitizing dye ■ Sensitizing Dye ■ X-2 X-3 X-10 Ceratin 5th layer (third red-sensitive emulsion layer) Emulsion D Sensitizing dye I Sensitizing dye ■ Sensitizing dye ■ X-2 X-3 X-4 B5-1 B5 -2 5, lX1O-5 1,4X10-'' 2, 3X10-' 0,40 0,0 5 0 0.015 0,070 0,050 0,070 1,30 Silver 1.60 5.4XlO-' 1 .4X10-"2.4X10-" 0,0 97 0.010 0,080 0,22 0,10 Gelatin 6th layer (intermediate layer) X-5 B5-1 Gelatin 7th layer (first green-sensitive emulsion layer) ) Emulsion A Emulsion B Sensitizing dye■ Sensitizing dye V Sensitizing dye■ X-1 X-6 X-7 X-18 B5-1 B5-3 Gelatin 8th layer (second green-sensitive emulsion layer) Emulsion C 0 , 040 0, 020 Silver 0.15 Silver 0.15 3.0X10-'1.0X10-'3.8X1.0-' 0, 02 1 0, 26 0, 030 0, 025 0, 10 0, Ol 0 0,63 Sensitizing dye ■ Sensitizing dye V Sensitizing dye ■ X-6 X-7 X-8 B5-1 HB S -3 Seratin 9th layer (third green emulsion layer) Emulsion E Sensitizing dye ■ Increase Sensitizing dye V Sensitizing dye■ X-1 X-11 8.0X10-' 0,50 Silver 1.20 3.5X10-"8.0XIO-'3.0X10-" 0,025 0, Giant 0,0 15 0,25 0,10 1,54 1st O layer ( Yellow filter layer) Yellow colloidal silver Silver 0.050EX-
50,080 8BS-10,030 Gelatin 0.95 No. 11
Layer (first blue-sensitive emulsion layer) Emulsion A Silver o, o s.

Emulsion B Silver 0.070 emulsion
F Silver 0.070 sensitizing dye■
3.5X10-'EX-80,042 EX-90,72 8BS-10,28 Gelatin 1. IO 12th layer (second blue-sensitive emulsion layer) Emulsion G Silver 0.45 Sensitizing dye■ 2. lX10-'EX-90,1
S EX-107,0XIO-' HBS-10,050 Gelatin 13th layer (third blue-sensitive emulsion layer) Emulsion H Sensitizing dye ■ X-9 B5-1 Gelatin 14th layer (first protective layer) Emulsion I B5 -1 Gelatin 15th layer (second protective layer) B-1 (diameter 1.7 μm) B-2 (diameter 1°7 μm) -t Gelatin 0,78 Silver 0.77 2.2XlO-' 0,20 0, 070 0,69 Silver 0,20 0.11 0, I7 5.0X10-" 1,00 0,40 5.0X10-" 0,10 0,10 0,20 1,20 In addition, all layers have preservability, W-mW-
2, W-3, B-4, B-5, F-1, F-2, F-3
, F-4, F-5, F-6, F-7, F-8, F-9,
F-10, F-11, F-12, F-13 and iron salt,
Contains lead salts, gold salts, platinum salts, iridium salts, and rhodium salts.

X-1 X-2 X-3 ff 0 matter Shil EX-4 EX-5 EX-6 EX-7 EX-8 EX-9 EX-10 EX-12 czHSoso, e EX-13 (shi)shi4fil U-5 B5-1 tricresyl phosphate B5-2 Di-n-butyl phthalate Exacerbating pigment! Exacerbating pigment■ Exacerbating pigment■ Exacerbating pigment■ Exacerbating pigment■ Exacerbating pigment■ Exacerbating pigment■ 1':M.

B-2 'l, V-3 n Proverbs 2-4 The average legality content of silver halide in this sample is 12.0 mol %. After the sample was cut and subjected to imagewise exposure, processing was carried out by changing the amount of fixing agent in the fixing bath in the following processing steps.

Process Processing time Processing temperature Color development
3 minutes 15 seconds 38℃ bleaching 6 minutes 30 seconds 38℃ water washing 2 minutes 10 seconds
24℃ fixation 6 minutes 20 seconds 38℃
Washing with water (1) 1 minute 05 seconds 24°C washing (2)
1 minute 00 seconds 24°C stable 1 minute 05
Seconds 38°C drying 4 minutes 20 seconds
55°C Next, the composition of the processing solution is shown.

(Color developer) Mother liquor (g) Diethylenetriaminepentaacetic acid 1.01-Hydroxyethylidene-3,0 1,1-diphosphonic acid Sodium sulfite 4.0 Potassium carbonate Potassium bromide Potassium iodide Hydroxylamine sulfate 4-(N- Ethyl-N-β hydroxyethylamino) Add 2-methylaniline sulfate and H (bleach solution) 10° mother liquor (g) Ethylenediaminetetraacetic acid ferric sodium trihydrate Ethylenediaminetetraacetic acid disodium salt Ammonium bromide Ammonium nitrate Ammonia Water (27%) Add water to H 100゜IOl ■ 40゜30゜6゜l.

6゜(Fixer) Mother liquor (g) Ethylenediaminetetraacetic acid disodium salt Sodium sulfite Sodium bisulfite Add water and H 10) Add ethylenediaminetetraacetic acid disodium salt solution to make the mother liquor (g) 2,0-p)(5,0-8,0) Then, after processing, measure the transmission density of magenta in the unexposed area of the sample using an X-rite densitometer. The results are shown in Table-3.

It is clear from Table 3 that when the compound of the present invention is used at a concentration higher than the concentration of the present invention, the effect on post-treatment stain (residual color) becomes greater.

Example 6 Compound-1 of Example 5 was converted into compound-2, 3, 5, 23, 2
A test similar to that in Example 5 was conducted except for using 6, 41, and 61, respectively.

As a result, as in Example 5, good results were obtained when the configuration of the present invention was followed.

Table 3 (Effect of the invention) 0.2 mol/f of the compound of the present invention! When used above, the stain (
It is possible to obtain a processing liquid with good fixing ability and little residual color.

Patent Applicant: Fuji Photo Film Co., Ltd. Procedural Amendment 1991 // Month μ day

Claims (1)

[Claims] In a processing method in which a silver halide color photographic light-sensitive material having an average silver iodide content of 3 mol % or more is processed with a bath having a fixing ability after color development, the bath having a fixing ability is a fixing agent. 1. A method for processing a silver halide color photographic light-sensitive material, which comprises at least one meso ion compound as a meso ion compound, and the content thereof is 0.2 mol/l or more.