JPH0346654A - Method for processing silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To prevent staining with time lapse and sulfurization of a stabilizing solution and a rinse water by incorporating a specified compound in the rinse water and/or the stabilizing solution to be used for rinsing and/or stabilizing processing. CONSTITUTION:The rinse water and/or the stabilizing solution to be used for the rinsing and/or processing contains the compound represented by formula I in which each of R1 - R4 is H, or optionally substituted alkyl or alkenyl having a carbon number of 1 - 5, preferably, 1 - 2, and a nonsubstituted group, i.e., methyl or ethyl, or in the case of alkenyl, a 2 - 5 C nonsubstituted group, i.e., vinyl or allyl, thus permitting staining with time lapse and sulfurization of the stabilizing solution and the rinse water to be prevented.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a method for processing silver halide color light-sensitive materials.

<Prior Art> Silver halide color photosensitive materials (hereinafter referred to as color photosensitive materials) are processed through steps such as color development, desilvering, water washing, and stabilization after exposure.

Color developer for color development, bleach solution for desilvering, bleach fixer, fixer, tap water or ion exchange water for washing,
A stable night is used for the stabilization process, respectively. The temperature of each processing solution is usually adjusted to 30 to 40°C, and the color photosensitive material is immersed in these processing solutions for processing.

Among these processing steps, the basic ones are a color development step and a desilvering step.

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, silver that is not 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 process and the fixing process are performed in the same bath, a method in which the process is performed in separate baths, and a method in which the bleaching process and the bleach-fixing process are performed in separate baths. Moreover, in this case, each bath may be multi-tank.

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.

<Problems to be Solved by the Invention> In recent years, with the spread of small in-store processing service systems called minilabs, there has been a strong demand for faster processing.

Under these circumstances, especially when rapid processing is performed on color photosensitive materials for photography such as color negative film, a large amount of color developing agent remains in the color photosensitive material after processing.
Therefore, there is a problem that staining occurs over time.

This aging stain is thought to be caused by the color developing agent remaining in the color light-sensitive material being oxidized in the air over time, and the oxidized agent generated reacting with the unreacted coupler to develop color in the unexposed areas.

Furthermore, if thiosulfate ions derived from thiosulfate contained as a fixing agent in a fixing solution or a bleach-fixing solution are brought into the stabilizing solution or washing solution, sulfidation occurs. This sulfidation causes a problem in that black precipitates are gradually formed in the stabilizing solution and the washing solution, and that these precipitates adhere to the color photosensitive material being processed. This sulfurization is particularly likely to occur in a stabilizing solution containing a compound (stabilizer) having the function of stabilizing a dye image.

To address this sulfidation problem, U.S. Pat.
, 786. '583 discloses a method of incorporating an alkanolamine such as triethanolamine into a stabilizing solution.

However, the above specification does not mention the problem of aging stain at all, and therefore the method disclosed therein does not solve the problem of aging staining.

Furthermore, regarding the problem of sulfurization, its prevention has not yet been sufficiently prevented, and there is still room for improvement.

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for processing a silver halide color photographic light-sensitive material, which can prevent staining over time and also prevent sulfurization of a stabilizing solution or washing wave.

<Means for solving the problem> In order to achieve the above object, the present invention has the following configuration (1).
has.

(1) After imagewise exposure of the silver halide color photographic light-sensitive material,
In a processing method in which water washing and/or stabilization treatment is performed after color development processing and desilvering processing, the washing liquid and/or stabilizing liquid used for the water washing treatment and/or stabilization treatment is expressed by the following formula ( A method for processing a silver halide color photographic material, which comprises a compound represented by I).

General formula (I) (In formula (I) above, R R2, R3 and R4 each represent a hydrogen atom, an alkyl group or an alkenyl group.) <Function> According to the present invention, water axilla and/or Alternatively, the general formula (
By containing the imidazole compound represented by I), staining and sulfurization over time in silver halide color photographic light-sensitive materials can be effectively prevented. This effect is particularly noticeable when applied to rapid processing.

<Specific configuration> Hereinafter, a specific configuration of the present invention will be explained in detail.

In the method for processing a silver halide color photographic light-sensitive material (hereinafter also referred to as light-sensitive material) of the present invention, the washing solution used in the water washing treatment and/or the stabilization treatment and/or the stabilization treatment are performed using the following general formula (I). It contains a compound represented by:

General formula (I) ■ In the above general formula (I), R,, R2, R3 and R
4 represents a hydrogen atom, an alkyl group or an alkenyl group, respectively.

The alkyl group may have a substituent and preferably has 1 to 5 carbon atoms, particularly 1 to 2 carbon atoms.
It is preferable that

Among these, unsubstituted ones are preferred, such as methyl and ethyl.

The alkenyl group may have a substituent and preferably has 2 to 5 carbon atoms, particularly 2 to 5 carbon atoms.
It is preferable that it is 3.

Among these, unsubstituted ones are preferred, such as vinyl and allyl.

Furthermore, examples of the substituent when the alkyl group or alkenyl group has a substituent include a hydroxy group, an amino group, a nitro group, and the like.

Among the above, in the present invention, it is preferable that R1 to R4 are a hydrogen atom or an unsubstituted alkyl group having 1 to 2 carbon atoms, and when an alkyl group is present, one of R1 to R4 is an alkyl group. It is preferable that R1
It is most preferred that -R4 are all hydrogen atoms.

Specific examples of the compound represented by general formula (1) are listed below, but the invention is not limited thereto.

(1) Imidazole (2) 1-methylimidazole (3) 2-methylimidazole (4) 4-methylimidazole (5) 4-hydroxymethylimidazole (6) l-ethylimidazole (7) 1-vinylimidazole (8) 4-aminomethylimidazole (9) 2.4-dimethylimidazole (10) 2.4.5-1-limethylimidazole (1
1) 2-Aminoethylimidazole (12) 2-nitroethylimidazole Among the compounds exemplified above, (1), (2), (3), (4), and (6) are particularly preferred, and most preferred. The thing is (1).

Note that these compounds have an acid dissociation constant (pKa) of 6 to 10.
, particularly preferably 6.5 to 8.5.

Compounds represented by general formula (I) (imidazole compounds) are commercially available, and they can be used as they are in the present invention.

These compounds are used by being added to at least the stabilizing bath which is the final bath immediately before drying, or the stabilizing solution or washing solution during water washing, and the content thereof is 0.001 to 0.2.
The mole content is preferably 0.01 to 0.03 mol/l. Moreover, even if these compounds are used alone,
They may be used in combination, and when used in combination, the total content may be within the above range.

In the present invention, as described above, the compound represented by the general formula (I) may be contained at least in the final stabilizing bath or washing bath. When two or more baths are used in combination with a stabilizing bath, the above compound may also be contained in the baths other than the final bath. In this case, the content is 0.001 to 0
．． The amount may be about 5 mol, preferably 0.01 to 0.01 mol.

In the present invention, as mentioned above, the final bath has the general formula (
By containing the compound represented by I), staining over time can be effectively prevented. In order to prevent this staining over time, it is most effective to include it in the final liquid.

Aging stain is mainly a stain that is produced when the developing agent remaining in the photosensitive material after processing is oxidized in the air over time, and the oxidized agent generated reacts with the unreacted coupler and develops color in the unexposed area. it is conceivable that. Therefore, this aging stain is particularly noticeable in rapid processing, and since there is currently a strong demand for faster processing, it is desirable to apply the method of the present invention in order to speed up the processing. .

In addition, by containing the above compounds, it is possible to stabilize the liquid or wash it with water. Sulfurization during the night can be prevented.

This sulfidation occurs when thiosulfate ions derived from thiosulfate, which is commonly used as a fixing agent, are carried into the stabilizing solution and washing solution by the processing wave with fixing ability used in the desilvering process, resulting in a black color. A precipitate is formed. This black precipitate adheres to the photosensitive material and causes a problem of contaminating the photosensitive material.

In particular, this sulfidation is likely to occur in stabilizing liquids.

The stabilizing solution usually contains aldehydes (for example, formalin) and their precursor compounds that release aldehydes as compounds that have the function of stabilizing dye images, and these compounds tend to cause sulfurization. Because it will be.

In the present invention, the sulfidation accelerating effect caused by aldehyde compounds can be effectively inhibited, especially by containing the compound represented by the general formula (I) in the stabilizing liquid.

Incidentally, US Pat. No. 4,786,583 discloses that sulfidation can be prevented by containing an alkanolamine (for example, triethanolamine) in a stabilizing liquid. However, according to the present inventor, it has been confirmed that the present invention is far superior to the method described in the above specification in terms of the effect of preventing sulfurization.

Therefore, the effects of the present invention are obtained by selectively applying the compound represented by formula (I). However, alkanolamines may be used as long as the effects of the present invention are achieved.

Furthermore, even if two or three washing baths and one stabilizing bath are used in a second process in which stabilization treatment is performed after washing with water, thiosulfate ions are still carried into the stabilizing bath. This has been proven, and the present invention is effective even in such cases. At that time, the general formula (
The compound represented by I) may be contained, or may be contained in the washing bath, or may be contained in the same bath.

In addition, to give an example of the amount of thiosulfate ion carried into the stabilizing solution, when the content of thiosulfate in the final bath among the processing baths having fixing ability is about 1.0 mol/l. , under the conditions after continuous treatment in the above treatment bath, in a stable bath located immediately after the above treatment bath, the amount is about 0.05 to 0.2 mol, and in a stable bath with two water washing baths, it is 1 x 10-4 ~
5 x 10. -3 mol/(approximately).

In addition, the stabilizing bath and stabilizing liquid in the above are respectively
Sometimes called stabilizing bath or stabilizing liquid, these are
They are used interchangeably.

In the present invention, washing with water is a process for ensuring post-processing performance by washing out processing liquid components that have adhered to or occluded in the color photosensitive material as well as photosensitive material constituents that are no longer needed during the processing process. .

Furthermore, stabilization is a process that improves the storage stability of images to a level that cannot be obtained by washing with water, and is a process in which a liquid containing a component that has an image stabilizing effect (a compound that has the function of stabilizing a dye image) is used. Consists of.

In the present invention, the carried-in amount refers to the volume of the pre-bath that is attached to and occluded in the photosensitive material and carried into the washing or stabilization process, and can be measured, for example, by the following method.

Method for measuring the amount brought in> Collect a 1 m sample just before entering the washing bath or stabilization bath, immediately immerse it in 1 liter of distilled water, keep it warm at 30°C, and
Stir with a magnetic cooler for 0 minutes. Next, these 7 nights were collected, and the concentration of thiosulfate ion during the night was C, (g/g/
j), and at the same time, the thiosulfate ion concentration C2 (g/j) in the fixing solution of the prebath was determined, and the carried-in amount A (m
Calculate j).

(1000+A) C, x = C2 The quantification of thiosulfate ions is performed by adding formaldehyde to mask sulfite ions, and then by acid iodometry.

Next, the water washing step and stabilization step in the present invention will be explained in detail.

In addition to tap water, the water used in the washing process and stabilization process (washing liquid, stabilizing liquid, and water for their replenishment liquids) is
Reduce Ca and Mg concentration to 5 mg using ion exchange resin etc.
It is preferable to use water that has been deionized to a concentration of /9 or less, water that has been sterilized using halogen, an ultraviolet germicidal lamp, or the like.

In the present invention, the content of calcium and magnesium in the replenisher in the washing step and/or stabilization step (hereinafter referred to as washing replenisher or stable replenisher) is preferably 5 mg/j or less, preferably 5 3 mg/j or less. /j or less, particularly preferably 1 mg/j or less.

In this way, by reducing the calcium and magnesium in the replenisher, the calcium and magnesium in the washing tank and stabilization tank will also inevitably decrease, to the extent that there is no need to use disinfectants or fungicides. This prevents the growth of mold and bacteria, and when using an automatic processor, dirt and deposits on the conveyor roller and squeeze blade can be removed at the same time.

Various known methods can be used to achieve the calcium and magnesium concentrations in the water wash or stable replenisher, but it is preferable to use an ion exchange resin and/or a reverse immersion device.

Although various cation exchange resins can be used as the ion exchange resin, it is preferable to use a Na type cation exchange resin in which Ca and Mg are replaced with Na.

G Although an H-type cation exchange resin can also be used, in this case, the pH of the treated water becomes acidic, so it is preferable to use it together with an OH-type anion exchange resin.

The ion exchange resin is preferably a strongly acidic cation exchange resin having a styrene-divinylbenzene copolymer as a base and having a sulfone group as an ion exchange group. Examples of such ion exchange resins include Mitsubishi Kasei's split product name Diaion 5K-IB or Diaion PK.
-216 and the like. The base material of these ion exchange resins is
Preferably, the amount of divinylbenzene added is 4 to 16%. Anion exchange resins that can be used in combination with H-type cation exchange resins include strongly basic anion exchange resins that have a styrene-divinylbenzene copolymer as a base and have a tertiary amine or quaternary ammonium group as an exchange group. preferable. Examples of such anion exchange resins include Diaion 5A-10A and Diaion PA-418, both manufactured by Mitsubishi Kasei.

Further, as for the reverse osmosis treatment device, any known one can be used without any limitation, but the reverse osmosis membrane has an area of 3 m" or less, a working pressure of 30 kg/m2 or less, particularly preferably 2 m" or less,
It is desirable to use an ultra-small device with a weight of 20 kg/m2 or less. When such a small device is used, workability is improved and sufficient water saving effects can be obtained. Furthermore, it is also possible to pass activated carbon or a magnetic field.

Note that as the reverse osmosis membrane included in the reverse osmosis treatment device, cellulose acetate membrane, ethyl cellulose/polyacrylic acid membrane, polyacrylonitrile membrane, polyvinylene carbonate membrane, polyether sulfone membrane, etc. can be used.

In addition, a liquid feeding pressure of 5 to 60 kg/cm2 is usually used, but a pressure of 30 kg/cm2 or less is sufficient.
A so-called low-pressure reverse osmosis device with a pressure of 10 kg/cm 2 or less is also sufficient.

As the structure of the reverse osmosis membrane, any of a spiral type, a tubular type, a hollow fiber type, a pleated type, and a rod type can be used.

In the present invention, it is further preferable to irradiate the liquid in at least one tank selected from the washing tank, the stabilization tank, and its replenishment tank with ultraviolet rays, and by doing so, the water can be sterilized. - It is possible to suppress the growth of layer mold.

Low-pressure mercury evaporation (which emits a line spectrum with a wavelength of 253.7 nm) is used as an ultraviolet lamp for sterilization.
A discharge sacrifice may also be used. q, :, 24+i1 with an output of 0.5 to 7.5 W is preferably used.

The ultraviolet lamp may be installed outside the liquid and irradiated with it, or it may be installed at night and irradiated from inside the oil.

Further, the washing liquid used in the washing step may contain known additives as necessary. For example, water softeners such as inorganic phosphoric acid, aminopolycarboxylic acid, and organic phosphoric acid, disinfectants that prevent the growth of various bacteria and algae, and fungicides (such as (intiazolone,
Organic chlorine disinfectants, benzotriazole, etc.), surfactants to prevent drying load and unevenness, etc. can be used. Or L, E, West, "Wate"
rQuality Cr1teria”, Photo,
Sci, and Bng.

vol 9. No, 6. p344-359 (1965
) etc. can also be used.

In the present invention, the disinfectant (antibacterial agent) and antifungal agent used in the washing solution and its replenisher include, for example, 5-chloro-2-methyl-4-isothiazolin-3-one, 2
- Isothiazolone antibacterial agents such as methyl-4-inchazolin-3-one, 1,2-benzisothiazoline -
Benziisothiazolone antibacterial agents represented by 3-one,
triazole derivatives such as benzotriazole, sulfamide antibacterial agents such as sulfanilamide, active halogen-releasing compounds such as sodium hypochlorite, thorium incyanurate dichloride, phenolic fungicides such as ortho-phenylphenol, 10゜10゛ -
Examples include organic arsenic fungicides such as oxybisphenoxyarsine.

In addition, as water softeners, ethylenediaminetetraacetic acid,
Aminopolycarboxylic acids such as diethylenetriaminepentaacetic acid and cyclohexanediaminetetraacetic acid; phosphonic acids and aminobosphonic acids such as 1-hydroxyethylidene-1,1-diphosphonic acid or ethylenediaminetemethylenesulfonic acid can also be mentioned. These chelating agents can be used as sodium salts, potassium salts, or ammonium salts.

Surfactants added for the purpose of preventing uneven water droplets when drying photosensitive materials after processing include polyethylene glycol type nonionic surfactants, polyhydric alcohol type nonionic surfactants, Alkylbenzene sulfonate type anionic surfactant, higher alcohol ethyl sulfate type anionic surfactant, alkylnaphthalene sulfonate type anionic surfactant, quaternary ammonium salt type cationic surfactant, amine salt type cationic surfactant There are amphoteric surfactants, amino acid-type amphoteric surfactants, and betaine-type amphoteric surfactants, but ionic surfactants combine with various ions mixed in during processing to form insoluble substances. Therefore, it is preferable to use a nonionic surfactant, and an alkylphenol ethylene oxide adduct is particularly preferable. As the alkylphenol, octyl, nonyl, dodecyl, and dinonylphenol are particularly preferred, and the number of moles of ethylene oxide added is particularly preferably 8 to 14 moles.

In addition to the above-mentioned surfactants, silicon compounds represented by the following formulas are preferred as they have the effect of preventing water droplet unevenness and defoaming.

Here, a, b, d, e are integers from 5 to 30, and C is from 2 to 5.
and R is an alkyl group having 3 to 6 carbon atoms.

The stabilizer used in the stabilization process contains a compound that has the function of stabilizing the dye image.

Examples of such compounds include aldehyde compounds as mentioned above, and during stable operation, 2 x 10-3 to 5 x 1
It is preferred that an aldehyde compound of 0-2 mo is contained, particularly preferably 5 X 10-" to 2 X
It is preferable to set it to 10-2 moj/j.

Examples of such aldehyde compounds include, but are not limited to, the following.

3 formaldehyde acetaldehyde propionaldehyde isobutyraldehyde n-butyraldehyde aldor propiolaldehyde acrolein crotonaldehyde Salicylaldehyde glyoxalic acid Mucochloric acid Mucobromic acid furfural diglycolaldehyde glyoxal succinic aldehyde glutaraldehyde α-Methylglutaraldehyde Cyclopenkundicarboxaldehyde 4 Among the above compounds, formaldehyde is particularly preferred.

These aldehyde compounds may partially form adducts with sulfite ions and bisulfite ions brought in from the previous bath in the stabilizing bath.

In addition, various buffers can be added to the stabilizing solution to adjust the membrane pH after treatment. Examples of such buffers include borate, metaborate, borax, and phosphoric acid. Salts, carbonates, potassium hydroxide, sodium hydroxide, aqueous ammonia, monocarboxylic acids, dicarboxylic acids, polycarboxylic acids, etc. can be used in combination.

Depending on the application, metal compounds such as Bi and Aβ, hardeners, optical brighteners, various ammonium salts such as ammonium chloride, ammonium sulfite, ammonium sulfate, ammonium thiosulfate, and other compounds used in water washing solutions may be added. can do.

Washing solution and stable night pH 5-10, preferably 6
It is preferable to set it to 8.5.

The total processing time of these steps is about 30 seconds to 2 minutes, preferably about 30 seconds to 1 minute.

Furthermore, the temperature of the water washing or stabilization step is in the range of 20 to 50°C, preferably 25 to 45°C, more preferably 3°C.
The temperature is 0 to 40°C.

It is preferable to combine various cleaning promotion means in the water washing or stabilization step. As such a promoting means, ultrasonic oscillation in acid, air foaming, jet impingement on the surface of the photosensitive material, compression using a roller, etc. can be used.

It is preferable to adopt a replenishment method in the water washing or stabilization step, and the preferred replenishment amount is 1 to 50 times the volume brought in from the pre-bath per unit area of the photographic material to be processed, preferably 2 to 30 times the volume brought in from the pre-bath. times, particularly preferably 3 to 20 times, more preferably 2 to 15 times.

In the present invention, the water washing and/or stabilization step may be performed in a single tank or in multiple tanks, but from the viewpoint of saving water, preferably two tanks are used.
It is preferable that the composition is composed of a plurality of tanks or more, particularly preferably two to four tanks. In a plurality of tanks, replenishment is preferably carried out in a multi-stage countercurrent system in which the final tank is supplied and the fluid is sequentially transferred to the previous tanks.

In the treatment method of the present invention, the above-mentioned water washing treatment and/or
Alternatively, prior to the stabilization treatment, desilvering treatments such as color development, bleaching, bleach-fixing, and fixing are performed.

In addition, in the present invention, as described above, a simple processing method in which a stabilization process is performed without substantially washing with water after processing with a processing liquid having a fixing ability can also be used.

The present invention is usually carried out by applying an automatic developing machine, but
The automatic developing machine used in the present invention is JP-A-60-191
No. 257, No. 60-191258, No. 60-1912
It is preferable to have the photosensitive material conveying means described in No. 59.

As described in JP-A-60-191257, such a conveying means can significantly reduce the amount of processing liquid brought into the rear bath from the front bath, and is highly effective in preventing deterioration in the performance of the processing liquid. Such effects are particularly effective in shortening the processing time in each step and reducing the amount of processing liquid replenishment.

The effect of the present invention is remarkable when the total processing time (excluding drying time) is short, and specifically, the total processing time is 88%.
This effect is clearly exhibited when the processing time is less than 7 minutes, and the difference from conventional processing methods becomes even more remarkable when the processing time is 7 minutes or less. Therefore, in the present invention, the total treatment time is preferably 8 minutes or less, particularly preferably 7 minutes or less.

The color developing solution used in the present invention contains a known aromatic primary amine color developing agent. Preferred examples are p-phenylenediamine derivatives, representative examples of which are shown below, but are not limited thereto.

D-I N,N-diethyl-p-phenylenediamine D-22-amino-5-diethylaminotoluene 8 D-10 2-amino-5-(N-ethyl-N laurylamino)toluene 4-[N-ethyl- N-(β-hydroxyethyl)aminocoaniline 2-methyl-4-[N-ethyl-N (β-hydroxyethyl)aminocoaniline 4-amino-3-methyl-N-ethylN-[β-(methane) sulfonamide) ethylcoaniline N-(2-amino-5-diethylaminophenylethyl)methanesulfonamide N,N-dimethyl-p-phenylenediamine 4-amino-3-methyl-N-ethyl N-methoxyethylaniline 4- Amino-3-methyl-N-ethyl N-β-ethoxyedylaniline D-114-amino-3-methyl-N-ethyl N-β-
Of the p-phenylenediamine derivatives described in "1-xyethylaniline", Exemplified Compound D-5 is particularly preferred.

Further, these p-phenylenediamine derivatives may be salts such as sulfates, hydrochlorides, sulfites, and p-toluenesulfonates. The amount of aromatic primary amine color developing agent used is preferably about 0.1 to 1 e per 1 e of color developer.
A concentration of about 20 g, more preferably about 0.5 to about 10 g.

In addition, sulfites such as sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, sodium metasulfite, potassium metasulfite, and carbonyl sulfite adducts may be added as preservatives after seven days of color development. can do.

The preferable amount of preservative added is 1 color developer (0.5
~log, more preferably 1 to 5 g.

Alternatively, the aromatic primary amine color developing agent may be directly applied to
Various hydroxylamines, patent application No. 1983, are used as compounds that preserve the energy. - Hydroxamic acids described in No. 1.86559, hydrazines and hydrazides described in No. 6]-170756, No. 61-188742 and No. 61-203
Phenols described in No. 253, 6], -]188
It is preferable to add α-hydroxyketones and α-aminoketones described in No. 741 and/or various saccharides described in No. 61-180616. In addition, when used in combination with the above compounds, Japanese Patent Application No. 61, No. 47823, Japanese Patent Application No. 47823, No. 6
]-166674, 61-16562], 61
-164515, 61-170789 and 6
], -] Monoamines described in No. 168159, etc.
No. 61-173595, No. 61. -164515,
Diamines described in No. 61-186560, etc., No. 61
-165621, 6], -] Polyamines described in 169789 and 61-1.88619, 6
1-19771 Nitroxy radicals described in No. 60, No. 6118656
Alcohols described in No. 1 and No. 61-197419, Oxino-ode described in No. 61-198987 and No. 6
Preferably, the tertiary amines described in No. 1-265149 are used.

Other preservatives include various metals described in JP-A-57-44148 and JP-A-57-53749;
- Salicylic acids described in No. 180588, JP-A-54-3
Alkanolamines described in No. 582, JP-A-56-9
Polyethyleneimines described in No. 4349, U.S. Patent No. 3
．． The aromatic polyhydroxy compound described in No. 746,544 and the like may be contained as necessary.

Particularly preferred is the addition of an aromatic polyhydroxy compound.

The color developing solution used in the present invention preferably has a pH of 9 to
12, more preferably 9 to 110, and the color developer may contain other known developer component compounds.

2. In order to maintain the above pH, it is preferable to use various buffers.

Specific examples of buffering agents include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, trisodium phosphate, dipotassium phosphate, sodium phonate, potassium borate, Sodium tetraborate (borax), potassium tetraborate, 0-
Sodium hydroxybenzoate (storium salicylate), potassium o-hydroxybenzoate, 5-sulfo-2
-sodium hydroxybenzoate (sodium 5-sulfosalicylate), potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate), and the like. However, the present invention is not limited to these compounds.

The amount of the slow iΦi agent added to the color developing solution is O, ] mol/e
or more, particularly O, 1 to 0.4 mol/
Particularly preferred is p.

In addition, various chelating agents can be used in the color developing solution as agents for preventing precipitation of calcium and magnesium, or for improving stability during color development.

The chelating agent is preferably an organic acid compound, such as aminopolycarboxylic acids, organic phosphonic acids, and phosphocarboxylic acids. Specific examples are shown below, but the invention is not limited to these.

Nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N,N,N-trimethylenephosphonic acid, ethylenediamine-N N N', N"-tetramethylenephosphonic acid, transcyclohexanediaminetetraacetic acid, l2-diaminopropane Tetraacetic acid, hydroxyethyliminodiacetic acid, glycol ether diamine tetraacetic acid, ethylenediamine orthohydroxyphenylacetic acid, 2-phosbobutane-12,4-1-licarboxylic acid,
1-hydroxyethylidene-1,1-diphosphonic acid, N
, N'-bis(2-hydroxybenzyl)ethylenediamine-N N'-diacetic acid.

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

The amount of these chelating agents added may be an amount sufficient to sequester metal ions in the color developing solution, and is, for example, 0.1 to Log per 1°C.

During color development, any development accelerator may be added if necessary. However, the color developing solution in the present invention has the following drawbacks in terms of pollution, liquid preparation properties, and color stain prevention.
Preferably, it does not substantially contain benzyl alcohol. Here, "substantially" means that the content is 2 mj or less per 1β of the developer, preferably not at all.

In addition, as a development accelerator, Japanese Patent Publication No. 37-16088
No. 3'l-5987, No. 387826, No. 44
-12380, 459019, U.S. Patent No. 3.8
18.24 is a thioether compound described in JP-A-52-49829 and JP-A-50-15554-d, JP-A-50-13
No. 7726, Japanese Patent Publication No. 1973-30074, Japanese Patent Publication No. 1983-
Quaternary ammonium salts described in No. 156826, No. 52-43429, etc., U.S. Patent No. 2,494,903,
No. 3,128,182, No. 4,230゜796, No. 3,253,919, Special Publication No. 11431-1973
No. 2,482°546, U.S. Patent No. 2,596
．． 926, No. 3 582.346, etc., amine compounds described in Japanese Patent Publication No. 37-16088, No. 42-25
No. 201, U.S. Patent No. 3,128,183, Special Publication No. 4
Polyalkylene oxides described in No. 1-11431, No. 42-23883, U.S. Patent No. 3,532,501, and other l-phenyl-3-pyrazolidones, imidazoles, etc. can be added as necessary. .

In the present invention, any antifoggant can be further added as required. As the antifoggant, alkali metal halides such as sodium chloride, potassium bromide, potassium iodide, and organic antifoggants can be used. As an organic antifoggant,
For example, benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, 2-thiazolylmethyl-benzimidazole. Typical examples include nitrogen-containing heterocyclic compounds such as miguzole, indazole, hydroxyazaindolizine, and adenine.

The color developing solution used in the present invention may contain a fluorescent whitening agent. As the fluorescent brightener, 4,4°-diamino-2,2′-disulfostilbene compounds are preferred. The amount added is 0 to 5 g/j, preferably 0. 1 g
~4g/i! There is.

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

In the present invention, the degree of processing with the color developer is 20 to 50°C.
, preferably 30 to 45°C. The treatment time is 20 seconds to 5 minutes, preferably 30 seconds to 3 minutes and 20 seconds. When employing the replenishment method, the replenishment amount is preferably small, but is 10 C1 to 500 mj, preferably 100 to 800 mj per m2 of photosensitive material. More preferably, it is 100 to 400 mF.

Further, the color developing bath may be divided into two or more baths as necessary, and the color developing bath may be replenished from the first bath or the last bath to shorten the developing time and reduce the amount of replenishment.

The processing method of the present invention can also be used for color reversal processing. The black-and-white developer used at this time is called a black-and-white first developer used in the commonly known reversal process of color photosensitive paulownia materials. Various well-known additives that are used in black-and-white developing solutions used in processing solutions for black-and-white silver halide light-sensitive materials can be included in the black-and-white first developing solution for color reversal light-sensitive materials.

Typical additives include developing agents such as niphenyl-3-pyrazolidone, metol and hydroquinone, preservatives such as sulfites, and alkalis such as sodium hydroxide, sulfur and lithium carbonate, and potassium carbonate. Accelerators, inorganic or organic inhibitors such as potassium bromide, 2-methylbenzimidazole, methylbenzthiazole, water softeners such as polyphosphates, and development inhibitors consisting of trace amounts of iodides and mercapto compounds. I can give it to you.

After color development, the color photosensitive material is subjected to desilvering treatment. Desilvering may be carried out simultaneously with bleaching and fixing (bleaching and fixing) or separately. Furthermore, in order to speed up the processing, the processing method described in JP-A-61-75352 may be used, in which bleaching is followed by bleach-fixing. Sad
! :1 further processing with two consecutive bleach-fixing baths as described in JP-A No. 62-91952; performing a fixing treatment before the bleach-fixing treatment as described in JP-A No. 6-51143; or Bleaching treatment after bleach-fixing treatment can also be optionally carried out depending on the purpose.

Examples of bleaching agents include iron (III), cobalt (+1
1), compounds of polyvalent metals such as chromium (Vl) and copper (TI), peracids, quinones, nitro compounds, etc. are used. Typical bleaching agents include ferricyanide; dichromate: iron (III) or cobalt (Ill)
organic complex salts such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid,
Aminopolycarboxylic acids such as methyliminodiacetic acid, 1,3-diaminopropanetetraacetic 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.

U It is preferable to use aminopolycarboxylic acid iron (III) 8M salt from the viewpoints of environmental protection, handling safety, metal corrosivity, and the like.

Specific examples of aminopolycarboxylic acid iron (III) 8M salts are listed below, but the invention is not limited thereto.
In addition, the oxidation-reduction potential is recorded.

Compound no.

Redox potential (mV vs, NHE, pH-6) 1, N-(2-acetamido)iminodiacetate iron (Ill) complex salt 2, Medyliiminodiacetate iron (Ill) complex salt 3, iminodiacetate iron (Ill) complex salt 4.1 .4-Butylenediaminetetraacetate iron(III) complex salt 5, diethylenethionityldiaminetetraacetate iron(III) complex salt 6, glycol ether diaminetetraacetate iron(III) complex salt 7.1.3-Propylenediaminetetraacetate iron(III) complex salt Ill) complex salt 00 10 30 30 40 50 8, ethylenediaminetetraacetic acid iron (Ill) complex salt 1109, diethylenetriaminepentaacetic acid iron (III) complex salt 8010, 1-Lance-1,2-cyclohexanediaminetetraacetic acid iron (Ill) complex salt 80 The redox potential of the bleach mentioned above is based on the Transactions of
The Faraday Society (Transaction
ns of the Faraday Society)
, vol. 55 (1959), 1.312-1313
It is defined by the redox potential measured by the method described on page 1.

In particular, in the present invention, in order to speed up the processing, the redox potential is 150 mV or more, preferably 180 mV or more,
More preferably, a bleaching agent j with a voltage of 200 mV or more is used.

Among these, particularly preferred are compound No.
7 of 1,3-propylenediaminetetraacetic acid iron (Ill
) complex salt (hereinafter abbreviated as 1.3-PDTA-Fe 3 (III)).

Aminopolycarboxylic acid iron (Ill) complex salts are used in the form of sodium, potassium, ammonium, etc. salts, but ammonium salts are preferred because they bleach the fastest.

Further, in the present invention, bleaching agents may be used alone or in combination of two or more kinds.

In the present invention, in addition to a bleaching agent with an oxidation-reduction potential of 150 mV or more, when a bleaching agent with an oxidation-reduction potential of less than 150 mV is used, in order to speed up the processing, it is necessary to use a bleach with an oxidation-reduction potential of 150 mV or more. The amount is preferably about 0.5 mol or less per 1 mol.

In particular, when used in combination with an aminopolycarboxylic acid iron (III) complex salt having a redox potential of 150 mV or more, preferred examples include ferric complex salts of ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, and cyclohexanediaminetetraacetic acid. I can do it.

In the present invention, preferred desilvering processes include bleach-bleach-fix, bleach-fix, and bleach-bleach-fix and fix, and in such cases, the use of a bleaching agent in a bleaching solution The amount is preferably 0.10 mol or more per 14 of the bleaching solution, and more preferably 0.15 mol or more in terms of speeding up the processing and reducing bleaching blade blur and stain. Particularly preferred is 0.25 mol or more. However, since the use of an excessively high concentration solution will actually inhibit the bleaching reaction, the upper limit of the concentration is preferably about 0.7 mol.

When two or more types are used together, the total concentration may be within the above range.

When using an aminopolycarboxylic acid iron (III) complex salt in a bleaching solution, it can be added in the form of a complex salt as described above, but if the complex-forming compound aminopolycarboxylic acid and ferric salt (e.g. , ferric sulfate, ferric chloride, ferric nitrate, ferric ammonium sulfate, ferric phosphate, and ferric acetate) to form a complex salt in the bleach solution.

In the case of this complex formation, the aminopolycarboxylic acid may be added in a slightly excess amount than the amount required for complex formation with ferric ions, and when added in excess, it is usually o, oi.
It is preferable to use an excess in the range of 10% to 10%.

Bleaching solutions as described above are used at a pH between 2 and 8. In order to speed up the processing, p + (2.5 to 4
．． 2, preferably 2.5 to 4.0, particularly preferably 2.
5 to 3.5, and the replenisher is usually 1.0 to 4.
．． It is better to use it as 0.

In the present invention, a known acid can be used to adjust the pH to the above range.

As such an acid, an acid having a pKa of 2 to 5 is preferable.

In the present invention, 1'-p Ka represents the logarithm of the reciprocal of the acid dissociation constant, and the ionic strength is 0. 1 mole 8, 25°C
Indicates the value determined by

In the present invention, it is preferable to use a bleaching solution containing 1.2 mol/C or more of an acid having a pKa in the range of 2.0 to 5.0 in the desilvering step.

By containing 12 moles or more of an acid with a pKa of 2.0 to 5.0 in the bleaching solution, it is possible to further prevent bleaching blade blur and to improve the increase in stain in uncolored areas after treatment.

The acid with a pKa of 2.0 to 5.0 may be an inorganic acid such as phosphoric acid, or an organic acid such as acetic acid, malonic acid, or citric acid.
Acids between 2.0 and 5.0 are organic acids. Among organic acids, organic acids having a carboxyl group are particularly preferred.

The organic acid having a pKa of 2.0 to 5.0 may be a monobasic acid or a polybasic acid. In the case of polybasic acids,
・) l) If K, a is in the above range of 2.0 to 5.0, it can be used as a metal salt (eg, sodium or potassium salt) or ammonium salt. Also, pKa2.0-5
．． Two or more types of organic acids may be used in combination.
However, aminopolycarboxylic acid and its F e 6M
Excludes salt.

Preferred specific examples of organic acids with a pKa of 2.0 to 5.0 used in the present invention include formic acid, acetic acid, monochloroacetic acid,
Aliphatic-basic acids such as monobromoacetic acid, glycolic acid, propionic acid, monochloropropionic acid, lactic acid, pyruvic acid, acrylic acid, butyric acid, isobutyric acid, bivaric acid, aminobutyric acid, valeric acid, isovaleric acid; asparagine, Amino acid compounds such as alanine, arginine, ethionine, glycine, glutamine, cysteine, serine, methionine, leucine; aromatic-basic acids such as benzoic acid and monosubstituted benzoic acids such as chloro and hydroxy; and nicotinic acid;
Aliphatic tribasic acids such as oxalic acid, malonic acid, succinic acid, tartaric acid, malic acid, maleic acid, fumaric acid, oxaloacetic acid, glutaric acid, adipic acid; aspartic acid, glutamic acid, glutaric acid, cystine, ascorbic acid Various organic acids can be listed, such as amino acid tribasic acids such as; aromatic tribasic acids such as phthalic acid and terephthalic acid; and polybasic acids such as citric acid.

In the present invention, among these, monobasic acids having a carboxyl group are preferred, and acetic acid and glycolic acid are particularly preferred.

In the present invention, the total amount of these acids used is 1% of the bleaching solution (
It is 1.2 mol or more per unit. Preferably 1.2-2.
It is 5 moles 8. More preferably, it is 1.5 to 2.0 mol/e.

bleaching? +)H at night to the above range, use the acid and alkali agents (e.g. aqueous ammonia, KOH, Na0H).
) may be used together. Among them, ammonia water is preferred.

Various bleaching accelerators can be added to the bleaching bath or pre-bathing bath in the present invention.

Such bleach accelerators are described, for example, in US Pat. No. 3,893,858, German Patent No. 1,290.
, No. 812, British Patent No. 1. ．． Specification No. 138,842, Japanese Unexamined Patent Publication No. 53-95630, Research Disclosure No. 17129 (July 1978 issue)
Compounds having a mercapto group or disulfide group described in JP-A-50-140129, thiazolidine derivatives described in U.S. Pat. No. 3,706,561, JP-A-58-16235 Iodides described in German Patent No. 2,748,430, polyethylene oxides described in German Patent No. 2,748,430, Japanese Patent Publication No. 1973
Polyamine compounds described in Japanese Patent Publication No.-8836 can be used. Particularly preferably British Patent Nos. 1 and 13
Mercapto compounds such as those described in US Pat. No. 8,842 are preferred.

In addition to bleaching agents and the above-mentioned compounds, the bleaching solution used in the present invention includes bromides such as potassium bromide, sodium bromide,
ammonium bromide or chloride, such as potassium chloride,
Rehalogenating agents such as sodium chloride, ammonium chloride, etc. can be included. The concentration of the rehalogenating agent is from 0.1 to 5 mol, preferably from 0.5 to 3 mol per 11 bleaching solution.

Moreover, it is preferable to use ammonium nitrate as a metal corrosion inhibitor.

In the case where the replenishment method is adopted in the present invention, the replenishment amount of the bleaching solution is 200 mj or less, preferably 140 to]Omj per m2 of the light-sensitive material.

The bleaching treatment time is 1.20 seconds or less, preferably 60 seconds or less, and more preferably 50 seconds or less. The present invention is effective in such a shortened processing time.

In addition, during the treatment, aminopolycarboxylic acid iron (Il+
) Bleach solution using complex salts is aerated,
It is preferred to oxidize the aminopolycarboxylic acid iron (IT) mW salt produced.

In the present invention, the fixing solution and bleach-fixing solution used in the desilvering process contain a fixing agent.

As fixing agents, thiosulfates such as sodium thiosulfate, ammonium thiosulfate, sodium ammonium thiosulfate, and potassium thiosulfate; thionoanate salts (rhodan salts) such as sodium thiocyanate, ammonium thiocyanate, and potassium diocyanate; Thiourea, thioether, etc. can be used.

Among them, it is preferable to use ammonium thiosulfate. The amount of the fixing agent is 0.3 to 3 mol, preferably 0.5 to 2 mol, per 1β of the fixing solution.

In addition, from the viewpoint of promoting fixation, it is also preferable to use ammonium thiocyanate (rhodan ammonium), thiourea, and thioether (for example, 3,6-dithia 1,8-octanediol) in combination, and the amounts of these compounds used in combination are , 0.01 to 0.1 per 14 of fixer or bleach-fixer
Generally, the amount is on the order of moles, but in some cases, the fixing promoting effect can be greatly enhanced by using 1 to 3 moles.

In the present invention, the fixing solution or the fixing agent in the bleach-fixing solution used in the fixing treatment or bleach-fixing treatment following the above-mentioned bleaching treatment, which is a preferred desilvering treatment step, is particularly suitable for speeding up the processing. It is preferable to use a thiosulfate and a thiocyanate in combination, and it is particularly preferable to use a combination of ammonium thiosulfate and ammonium thiocyanate.

In this case, the thiosulfate may be used at the above-mentioned 0.3 to 3 mol/j, and the thiocyanate may be used at 1 to 3 mol/j, preferably 1 to 2.5 mol/j.

Other compounds other than thiocyanate that can be used in combination with thiosulfate (particularly ammonium thiosulfate) include thiourea, thioethers (e.g. 3,6-cythia-1,8-octanediol), etc. .

The amount of these compounds used in combination is generally about 0.01 to 0.1 mol per 12 of the fixing solution or bleach-fixing solution, but in some cases, 1 to 3 mol may be used.

Established? At night or during bleach-fixing, preservatives such as sulfites (e.g. thorium sulfite, potassium sulfite, ammonium sulfite) and hydroxylamine, hydrazine, bisulfite adducts of aldehyde compounds (e.g. acetaldehyde sodium bisulfite), etc. can be contained. Furthermore, various optical brighteners, antifoaming agents, surfactants, polyvinylpyrrolidone, organic solvents such as methanol, etc. can be contained, and in particular, preservatives are described in Japanese Patent Application No. 60-283881. It is preferable to use a sulfinic acid compound of

The bleach-fix solution may contain the above-mentioned known bleaching agents.

Preferred is aminopolycarboxylic acid ferric complex salt.

In the bleach-fix solution, the amount of bleach per 11 bleach-fix solutions is 0.01 to 0.5 mol, preferably 0.015 to 0.5 mol.
The amount is 0.3 mol, particularly preferably 0.02 to 0.2 mol.

In the present invention, the bleach-fix solution (mother liquor) at the start of processing is
The bleach-fixing solution described above is prepared by dissolving the compound used in the bleach-fixing solution in water, but it may also be prepared by mixing appropriate amounts of separately prepared bleaching solution and fixing solution. The pt+ of the fixer is 5
-9 is preferable, and 7-8 is more preferable. Also,
The pH of the bleach-fix solution is preferably 6 to 85, more preferably 6.5 to 8.0.

The amount of replenishment of fixer or bleach-fixer is 1 m of photosensitive material.
2 is preferably 300 to 3000 mj, more preferably 300 to 1000 m&.

Furthermore, it is preferable to add various aminopolycarboxylic acids and organic phosphonic acids to the fixer and bleach-fixer for the purpose of stabilizing the solution.

Also, the desilvering treatment that is preferred in the present invention? The total treatment time of the fixing treatment or the bleach-in-place treatment performed after the bleaching treatment is preferably 0.5 to 2 minutes, particularly 1 to 1.5 minutes.

The present invention is effective when applied to such short processing times.

In the present invention, the effect of the water-sprinkling invention is significantly obtained in terms of the total processing time of the desilvering step, which is short.

The preferred time is 1 to 4 minutes, more preferably 1930 seconds to 3 minutes. Further, the treatment temperature is 525-50°C, preferably 35-45°C. In a preferred temperature range, the desilvering rate is improved and the occurrence of staining after processing is effectively prevented.

In the desilvering step of the present invention, it is preferable that the stirring be as strong as possible in order to more effectively exhibit the effects of the present invention.

A specific method for strengthening stirring is disclosed in Japanese Patent Application Laid-Open No. 62183460.
No. 62-183461, a method of impinging a jet of a processing liquid on the emulsion surface of a photosensitive material, and JP-A-62-18
A method of increasing the stirring effect using the rotating means of No. 3461,
Furthermore, there are methods to improve the stirring effect by moving the photosensitive material while bringing the emulsion surface into contact with a wiper blade installed in the solution to create turbulence on the emulsion surface, and methods to increase the circulation flow rate of the entire processing solution. It will be done. Such means for improving agitation is effective for all bleaching solutions, bleach-fixing solutions, and fixing solutions. It is believed that improved stirring speeds up the supply of bleaching agent and fixing agent into the emulsion film, and as a result increases the desilvering rate6.

Further, the agitation improving means is more effective when a bleach accelerator is used, and can significantly increase the bleach accelerating effect and eliminate the fixing inhibiting effect caused by the bleach accelerator.

In each of the above processing steps for color photosensitive materials, when continuous processing is performed using an automatic processor, concentration of the processing solution may occur due to evaporation, especially when the processing amount is small or the opening area of the processing solution is This becomes noticeable when is large. In order to correct such concentration of the processing liquid, it is preferable to replenish an appropriate amount of water or correction liquid.

Further, the amount of waste liquid can be reduced by using a method in which the overflow liquid from the water washing step or the stabilization step flows into a pre-bath having a fixing ability.

The light-sensitive material in the present invention only needs to have at least one silver halide emulsion layer of a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer on the support. There are no particular limitations on the number and order of the emulsion layers and non-photosensitive layers.

A typical example is a silver halide color photographic light-sensitive material that has a light-sensitive layer on a support, which is composed of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different light sensitivities. The photosensitive layer is a unit photosensitive layer that is sensitive to blue light, green light, or red light, and in multilayer silver halide color photographic light-sensitive materials, the arrangement of the unit photosensitive layers is generally A red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer are installed in this order from the body side. However, depending on the purpose, the above-mentioned installation order may be reversed, or the installation order may be such that different color-sensitive 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.

For the middle class, JP-A-61-43748 and JP-A-59-11
No. 3438, No. 59-113440, No. 61-200
No. 37, No. 61-20038, the coupler DTP compound, etc. may be included, and the compound may contain a bleaching inhibitor, an ultraviolet absorber, an anti-stinting agent, etc. as commonly used. Good too.

The plurality of silver halide emulsion layers constituting each unit photosensitive layer are
1.1.2], 470 or British Patent No. 923.045;
A two-layer structure of low-speed emulsion layers can be preferably used. Usually, it is preferable to arrange the halogen emulsion layers so that the photosensitivity decreases in order toward the support, and a non-photosensitive layer may be provided between each halogen emulsion layer.

Also, JP-A-57-], No. 12751, No. 6220
No. 0350, No. 62-206541, No. 61-206
As described in No. 543, 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 (BH) / high sensitivity green sensitive layer (GH) / low sensitivity 9 degrees green sensitive layer ( GL)/high-sensitivity red-sensitive layer (RH)/low-sensitivity red-sensitive layer (RL)/or BH/BL/G
L/GH/RH/R1- order, or BH/BL/GH
/GL/RL/RH, etc.

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 a silver halide emulsion layer with higher sensitivity than the middle layer. An example is an arrangement consisting of three layers of different photosensitivity, in which a silver halide emulsion layer with low photosensitivity is disposed, and the photosensitivity gradually decreases toward the support. Even in a case where the layer is composed of three layers with different photosensitivity, as described in JP-A No. 59-202464, the medium-sensitivity emulsion layer/ They may be arranged in the order of high-speed emulsion layer/low-speed emulsion layer.

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

Any of these layer arrangements can be used in the color photosensitive material of the present invention, but in the present invention, the dry film thickness of all the constituent layers of the color photosensitive material excluding the support and the undercoat layer and back layer of the support is 20.0μ or less. It is preferable to achieve the object of the present invention. More preferably 1
It is 8.0μ or less.

These film thicknesses are determined by the color developing agent incorporated into these layers of the color light-sensitive material during and after processing, and the amount of remaining color developing agent greatly affects the bleaching edge blur. In particular, the increase in color of magenta, which is thought to be caused by the green-sensitive color layer, is greater than the increase in color of other cyan and yellow colors.

Note that the lower limit value in the film thickness regulation is desirably reduced from the above regulation to a range that does not significantly impair the performance of the photosensitive material. The lower limit of the total dry film thickness of the constituent layers of the photosensitive material excluding the support and the undercoat layer of the support is 12.0μ, and the lower limit of the total dry film thickness of the constituent layers excluding the support and the undercoat layer of the support is 12.0 μm. The lower limit of the total dry film thickness of the constituent layers is 1.0μ
It is.

Further, the film thickness may be reduced in either the photosensitive layer or the non-photosensitive layer.

The film thickness of the multilayer color photosensitive material in the present invention is measured by the following method.

The photosensitive material to be measured is stored at 25° C. and 150% RH for 7 days after its preparation. First, add 1111 to the total thickness of this photosensitive material, then remove the coated layer on the support, measure the thickness again, and use the difference to calculate the total thickness of the photosensitive material excluding the support. The thickness of the layer. The thickness can be measured using, for example, a film thickness measuring device using a contact type electric conversion element (Anrjtus Electric).
Co, Ltd.

K-402B St, and). Note that the coating layer on the support can be removed using an aqueous sodium hypochlorite solution.

Next, using a scanning electron microscope, take a cross-sectional photograph of the photosensitive material (magnification is preferably 3,000 times or more), measure the total thickness on the support and the thickness of each layer, and calculate the previous film thickness. Measured value of total thickness by measuring device (absolute value of actual thickness)
The thickness of each layer can be calculated by comparing the

The swelling rate of the photosensitive material in the present invention [(25°C, equilibrium swelling film thickness in H2O - dry total film thickness at 25°C, 55% RH/dry total film thickness at 25°C, 155% RH) x 100] is 50 to 200% is preferable, and 70 to 150% is more preferable.

If the swelling ratio deviates from the above-mentioned value, the amount of the color development agent remaining will increase, and this will have an adverse effect on photographic performance, image quality such as desilvering properties, and film properties such as film strength.

Furthermore, the swelling rate of the photosensitive material in the present invention is defined as the saturated swelling rate, which is 90% of the maximum swollen film thickness reached when processed in a color developing solution (38°C, 13 minutes and 15 seconds).
When the time required to reach a film thickness of /2 is defined as the swelling rate T1/2, it is preferable that T1/2 is 15 seconds or less. More preferably, T1/2 is 9 seconds or less.

The preferred silver halide contained in the photographic emulsion layer of the color light-sensitive material used in the present invention is silver iodobromide, silver iodochloride, or silver iodochlorobromide, containing about 30 mol % or less of silver iodide.

Particularly preferred is silver iodobromide containing from about 2 to about 25 mole percent 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. It may have crystal defects such as, 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 include, for example, Research Disclosure (RD) No. 17.
643 (December 1978), pp. 22-23, °゛1
．． Emulsion preparation
nand types)” and the same No. 18716
(November 1979, p. 1.648, ``Physics and Chemistry of Photography'' by Graf Kide, published by Paul Montell (P, GLaf)
kids.

Chimie et Physique Photog
raphique paulmontel, 1.96
7), “Photographic Emulsion Chemistry” by Duffin, published by Focal Press (G, F, DuffinPhotograph)
ic Emulsion Chemistry (Fo
calPress, 1966), “Manufacture and Coating of Photographic Emulsions” by Zelikman et al., Focal Press Publishing Co., Ltd. (V, L
, Zelikman et al., Makjng a.
nd Coating Photographic E
mulsion, Focal Press, +9
It can be prepared using the method described in 64).

U.S. Patent No. 3,574,628, U.S. Patent No. 3,655 3
Monodisperse emulsions such as those described in No. 94 and British Patent No. 1,413.748 are also preferred.

Tabular grains having an aspect ratio of about 5 or more can also be used in the present invention. Tabular grains are described in Photographic Science and Engineering by Gutoff.

Photographic 5science and
Engineering), Volume 14, 248-257
Page (1: J70); U.S. Patent No. 4,434,226, U.S. Patent No. 4,414.310, U.S. Patent No. 4,430,048
No. 4,439,520 and British Patent No. 211
It can be easily prepared by the method described in No. 2.157.

The crystal structure may be --like, the inside and outside may have different halogen compositions, or it may have a silk-like structure. Furthermore, 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, 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. Additives used in such processes are subject to Research Disclosure N.
No. 17643 and No. 18716, 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.

7 RD No. 17643 Chemical sensitizer page 23 Sensitivity enhancer spectral sensitizer, page 23-24 Super sensitizer Brightener page 24 Anti-fogging agent, page 24-25 Stabilizer light absorber, page 25-26 Filter dye, ultraviolet absorber stain inhibitor Page 25 Right column RD No. 18716 Page 648 Right column Same as above Page 648 Right column ~ 649 Right column Page 649 Right column Page 649 Right column ~ Page 650 Left column Page 650 Left to Right column 8 Dye image stabilizer 9 Hardener 10 Binder 11 Plasticizer, lubricant 12 Coating aid, surfactant Static stopper 25 pages 26 pages 26 pages 27 pages 26-27 pages 27 pages 651 pages Same as above left column 650 pages same as above right column Same as above 8 Various color couplers can be used in the present invention, and specific examples thereof include the above-mentioned RD No. 17643, ■-C-
It is described in the patent described in G.

As a yellow coupler, for example, U.S. Patent No. 3,93
No. 3,501, No. 4,022,620, No. 4,32
No. 6,024, No. 4,401.752, No. 4,2
48,961, Japanese Patent Publication No. 58-10739, British Patent No. 1,425.020, British Patent No. 1,476.760,
U.S. Patent No. 3,973,968, U.S. Patent No. 4.314.0
No. 23, No. 4,511,649, European Patent No. 249
, No. 473A, etc. are preferred.

As magenta couplers, 5-pyrazolone and pyrazoloazole compounds are preferred, and US Pat.
No. 10,619, No. 4,351,897, European Patent No. 73,636, U.S. Patent No. 3,061,432,
No. 3.725,064, RD No. 24220 (1
June 984), JP-A No. 60-33552, RD No.
, 24230 (June 1984), JP-A-60-43
No. 659, No. 61-72238, No. 60-35730
No. 55-118034, U.S. Patent No. 60-185951, U.S. Patent No. 4,500,630, U.S. Pat.
Particularly preferred are those described in No. 88104795.

As cyan couplers, phenolic and naphtho-
U.S. Pat. No. 4,052,21
No. 2, No. 4,146,396, No. 4,228,2
No. 33, No. 4296.200, No. 2,369,9
No. 29, same No. 2,801. ．． No. 171, No. 2.772
．． No. 162, No. 2.895,826, No. 3,77
No. 2,002, No. 3,758,308, No. 4,3
34,011, 4327.173, West German Patent Publication No. 3,329.729, European Patent No. 12], 36
No. 5A1, No. 249,453A, U.S. Pat. No. 3.446.
No. 622, No. 4,333,999, No. 4,753
, No. 871, No. 4,451, . No. 559, No. 4.4
No. 27,767, No. 4,690,889, No. 4,
Preferred are those described in No. 254,212, No. 4,296,199, JP-A-61-4.2658, and the like.

Colored couplers for correcting unnecessary absorption of coloring dyes include the Vll-G term of RD No. 17643, U.S. Patent No. 4,163,670, Japanese Patent Publication No. 57-39413,
U.S. Patent No. 4,004°929, U.S. Patent No. 4,138,2
No. 58, British Patent No. 1. ．． 146,368 is preferred. Also, U.S. Patent No. 4,774,1.8
Couplers that correct unnecessary absorption of coloring dyes using fluorescent dyes released during coupling as described in No. 1, and dye precursors that react with developing agents to form dyes as described in U.S. Pat. No. 4,777.120. It is also preferred to use couplers 2 which have groups as leaving groups.

Couplers whose coloring dyes have appropriate diffusivity include U.S. Patent No. 4,366.237 and British Patent No. 2,125.
, 670, European Patent No. 96.570, and German Patent Publication No. 3,234.533 are preferred.

Typical examples of polymerized dye-forming couplers are U.S. Pat.
No. 4,576.910, British Patent No. 2,102
, No. 173, etc.

Couplers that release photographically useful residues upon coupling are also preferably used in the present invention. The DIR coupler releasing the development inhibitor has the aforementioned RD No. 17.
643, patents described in sections ■ to F, JP-A-57-15
No. 1944, No. 57-154234, No. 60-184
No. 248, No. 63-37346, U.S. Patent No. 4.24
Those described in No. 8,962 and No. 4,782.012 are preferred.

As a coupler that releases a nucleating agent or a development accelerator imagewise during development, British Patent No. 2097.140,
No. 2,131,188, JP 59-157638
No. 59-170840 is 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 and others, and U.S. Pat. '283,472,
High-selling couplers described in 4.338393, 4,310, 61.8, etc., JP-A-60-185950
DIR redox compound releasing coupler, DIR coupler releasing coupler, I
OR coupler releasing redox compound or DIR redox releasing redox compound, European Patent No. 173,30
2A, a coupler that emits a colorant after release, RD No. 11449, 24241, JP-A-61-2
No. 01247, etc.; ligand-releasing couplers, such as U.S. Pat. No. 4,553,477; leuco dye-releasing couplers, U.S. Pat. Examples include couplers that emit fluorescent dyes as described in 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 organic solvents include phthalate esters (
Dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate,
bis(2,4-di-t-amylphenyl) phthalate,
bis(2,4-di-t-amyl phenyl) isophthalate, bis(1゜1-diethylpropyl) phthalate, etc.), esters of phosphoric acid or phosphonic acid (triphenyl phosphate, 1-licresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexylbosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2-ethylhexyl phenyl phosphonate, etc.), benzoic acid esters (2-ethylhexylbenzoate, etc.) , dodecyl benzoate, 2-ethylhexyl-p-hydroxybenzoate, etc.), amides (N, N-diethyl dodecanamide, N, N-diethyl lauryl amide, N
-tetradecylpyrrolidone, etc.), alcohols or phenols (isostearyl alcohol, 2,4-di-tert-amylphenol, etc.), aliphatic carboxylic acid esters (bis(2-ethylhexyl) sebacate, dioctyl azelate, glycerol trichloride, etc.) butyrate, isostearyl lactate, trioctyl citrate, etc.), aniline derivatives (N.

'l b N-dibutyl-2-butoxy-5-tert-octylaniline, etc.), hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene, etc.), and the like. In addition, as an auxiliary solvent, those with a boiling point of about 30°C or higher,
Preferably, an organic solvent having a temperature of 50"C to about 160"C 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 steps and effects of latex dispersion methods and specific examples of latex for impregnation are described in U.S. Pat.
No. 541,230, etc.

These couplers can also be synthesized into rhodapul latex polymers (
For example, it can be emulsified and dispersed in an aqueous hydrophilic colloid solution by impregnating it with a water-insoluble and organic solvent-soluble polymer.

Preferably, the homopolymers or copolymers described on pages 12 to 30 of International Publication No. WO38100723 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. It is particularly preferable to apply the present invention to color negative films for general use or movies, and color reversal films for slides or televisions.

Suitable supports that can be used in the present invention include, for example, the above-mentioned R
D No. 17643 page 28 and same No. 18716
It is described from the right column on page 647 to the left column on page 648.

<Example> Hereinafter, the present invention will be specifically explained with reference to Examples.

Example 1 On a subbed cellulose triacetate film support,
A sample of a multilayer color photosensitive material consisting of each layer having the composition shown below was prepared.

(Composition of the photosensitive layer) The numbers for each component indicate the coating weight in g/m2. However, the amounts of silver halide, colloidal silver, and couplers are expressed in units of g/m2 of silver, and the amounts of sensitizing dyes are expressed in units of moles per mole of silver halide in the same layer. The numerical value written in parentheses at the end of each layer indicates the film thickness [unit: 2μ].

1st layer, Halesh black colloidal silver gelatin V-I V-2 pa-tolv-I olv-2 olv-3 Anti-oxidation layer Silver coating amount 0.20 1.90 0.10 0.20 0.05 0 .01 0.01 08 (20) 2nd layer: Intermediate layer fine grain silver bromide gelatin PD-2 (equivalent sphere diameter 0.07μ) Silver coating amount 0.15 0.90 0.20 (0,9) 9th 3rd layer: 1st red-sensitive emulsion layer Silver iodobromide emulsion (Ag1 10.0 mol%, internal high AgI
Type, equivalent sphere diameter 0.7 μ, coefficient of variation of equivalent sphere diameter 14%, 1
Tetrahedral grains) Silver coating amount 0.50 Silver iodobromide emulsion (AgI 4.0 mol%, internal high AgI
Type, equivalent sphere diameter 0.4 μ, coefficient of variation of equivalent sphere diameter 22%, 1
Tetrahedral particles> Silver coating amount 0.40 Gelatin 1.90E x S
-19,OX 10-'Mole Ex S -23,O
X 10-'mol ExS-30゜8X 10-'molExS-40,6X 10-'molExC-10
,33 Ex C-20,009 Ex C-30,028 ExC-60,14 (2,2) 0 4th layer: 2nd red-sensitive emulsion layer Silver iodobromide emulsion (AgI 16 mol%, internal high AgI type, equivalent sphere diameter 1.0 μ, coefficient of variation of equivalent sphere diameter 25%, plate-shaped particles, diameter/thickness ratio 4.0) Silver coating amount 0.80 Gelatin 1,20E x'S
-14,OX 10-'Mole Ex S -21,5X
10-' mol Ex S -30,4X 10-' mol Ex S -40,4X 10-' mol Ex C
-30,05 ExC-40,10 ExC-60,08 (14) 5th layer: 3rd red-sensitive emulsion layer Silver iodobromide emulsion (AgI 10.6 mol%, internal high Ag
Type I, equivalent sphere diameter 1.2μ, coefficient of variation of equivalent sphere diameter 28%,
Plate-shaped particles, diameter/thickness ratio 6.0) Silver coating amount 1.10 Gelatin 1.00E x S
-12,5X 10-'Mole Ex S -20,7
x 10-'MoleEx S-30,3X 10-'
Mol Ex C-40,07 Ex C-50,06 Solv-10,12 Solv-20,12 (1,4) 6th layer: Intermediate layer gelatin 1.30Cp d
-40,10 (1,01 7th layer: first green-sensitive emulsion layer silver iodobromide emulsion (AgI 10.0 mol%, internal high Ag
Type I, equivalent sphere diameter 0.7 μ, coefficient of variation of equivalent sphere diameter 14%,
14
Face piece particle) Silver coating amount 0. lO Gelatin 1.30ExS-5
5X1. Q-'MoleExS-62X 10-'MoleExS-71XIO-'MoleExM-] 0.2]ExM-
60,31 ExM-20,10 ExM-50,03 So 1 v -10,20 Solv-50,03 (1,81 3 8th layer/2nd green emulsion layer Silver iodobromide emulsion (AgI 10 mol %, internal high iodine type, equivalent sphere diameter 1.0 μ, coefficient of variation of equivalent sphere diameter 25%, plate-shaped particles, diameter/thickness ratio 3.0) Silver coating amount 0.50 Gelatin 0.45E x S
-54,5X 10-'Mole Ex S -61,8
X 10-'molE x S -70,9X
10-'mol ExM-10,09 ExM-30,01 Solv-10,15 Solv-50,03 (o, g) 9th layer: Intermediate layer gelatin 0.50 (0,4) 4 10th layer: Third green-sensitive emulsion layer Silver iodobromide emulsion (AgI 10.0 mol%, internal high Ag
Type I, equivalent sphere diameter 1.2μ, coefficient of variation of equivalent sphere diameter 28%,
Plate-shaped particles, diameter/thickness ratio 6.0) Silver coated jii 1.20 Gelatin l, 20E x S
-52,4X 10-'molE x S -61,O
X 10-'mol Ex S-7], OX 10''mol ExM-30, QI ExM-40,14 ExM-10,04 ExC-40,005 SoLv-1,0,2 (1, 6+ 11th layer, yellow filter layer Cpd-3 Gelatin S o 1. v -1 0,05 0,50 0,10 (0,5) 12th layer, middle layer gelatin 0.05 Cpd-2 0,10 ( 0,5) 13th layer: 1st blue-sensitive emulsion layer Silver iodobromide emulsion (AgI 10.0 mol%, internal high Ag
Type I, equivalent ball diameter Q, 7 μ, coefficient of variation of equivalent ball diameter 14%,
Tedecahedral grains) Silver coating amount 0.15 Silver iodobromide emulsion (Ag1 4.0 mol%, internal high AgI type, equivalent sphere diameter 0.4μ, coefficient of variation of equivalent sphere diameter 22%, ■4
Face piece particle) Silver coating amount 0.08 Gelatin 1.00E x S
-84,5 , internal height Ag
Type I, equivalent sphere diameter], Oμ, coefficient of variation of equivalent sphere diameter 16%,
Tedecahedral particles) Silver coating amount 080 Gelatin 0.30E x S
-83,0x 1.0-'mol ExY-10,22 So 1 v -10,07 (07) 7 15th N: Intermediate layer fine grain silver iodobromide (AgI 2 mol%, uniform type, equivalent sphere diameter 0 .13μ) Silver coating amount 0.20 Gelatin 0.26 (0,3) 16th layer: 3rd blue-sensitive emulsion layer Silver iodobromide emulsion (AgI 14.0 mol%, internal high Ag
Type I, equivalent sphere diameter 1.5 μ, coefficient of variation of equivalent sphere diameter 28%,
Plate-shaped particles, diameter/thickness ratio 5.0) Gelatin xS-8 xY-I Solv-1 Silver coating amount 1.20 0.80 1.8X 10-'mol 0.20 0.07 (1,5) 8 17th layer: 1st protective layer Gelatin V-1 V-2 Solv-I Solv-2 1,80 0,10 0,20 0,01 Olol (1,5) 18th layer: 2nd protective layer Fine particle odor Silver oxide (equivalent sphere diameter 0.07μ) Silver coating amount 0.
18 Gelatin 0.90 polymethyl methacrylate particles (diameter 1.5μ) 0.20 0.20 40 1.00 (2,0) -1 4-1 Cpd-5 U■ 1 U■ xM-3 xC xC-2 ×C xS-8 olv So], v G 2HB ■ S o L v 3 olv pd-1 pd-2 pd-3 pd C6H13(n) pd 113 1 -1 08F1□302N1(G(□CI□CI+20CH□
CH□N”(C1(313C1(2=CH3O2(1)
2CONH-Q(□CH2=CH3O□CH2C0NH
-CH29 The sample thus prepared was cut and processed into a width of 35 mm, subjected to imagewise exposure, and in the processing steps shown below, using a cine-type automatic processor, the cumulative replenishment amount of color developer was equal to the mother liquor tank capacity. Each treatment was performed until the amount was tripled.

Fu summer cloud level, fu processing time, processing temperature, amount of dough.

Color development 3 minutes 15 seconds 37.8℃ 23m Flood bleaching 40 seconds 38.0℃ 5mj fixing 1 minute 30 seconds 38.0℃ 30m
j Washing with water (1) 30 seconds Washing with water at 38.0℃ (2
) 30 seconds 38.0°0 30m1 decrease
Constant 30 seconds 38.0℃ 20m1 Drying 1 minute 55℃ *Replenishment amount is 35
The amount of washing per meter of 35 mm width is the countercurrent method from (2) to (11).The amount of developing solution carried into the bleaching process and the amount of fixing solution carried into the washing process are 1 m of photosensitive material with a width of 35 mm.
2.5mj per length.

It was 2.0mj. Further, the crossover time is 5 seconds in each case, and this time is included in the processing time of the previous step.

00 The composition of the treatment liquid is shown below.

(Color developer) Mother liquor (g) Diethylenetriaminepentaacetic acid 1.0 1-hydroxyedilideno 1.1-diphosphonic acid 3.0 Sodium sulfite 4.0 Potassium carbonate 30.0 Potassium bromide 1.4 Potassium iodide 1 .5rrIg Hydroxylamine sulfate 2.42-Methyl-4-[N-ethyl-N-(β-hydroxyethyl)amino]aniline sulfate 4.5 Add water 1.02 Replenisher (g) 3.2 4.9 30.0 3.6 6.4 1, Oe p+ (10,05 10,10 ((vote white) )], 3-propylenediaminetetraacetic acid ferric ammonium hydrate 1,3-propylene Diaminetetraacetic acid Ammonium bromide Ammonium nitrate Hydroxyacetic acid Acetic acid (98%) Add water and pll [Adjust with aqueous ammonia (27%)] Mother's night (g) 144.0 2.8 84.0 30.0 50.0 50, Oe 1,02 3,0 Replenisher (g) 206.0 4.0 120.0 41.7 70.0 70.0 1, Oe 2.4 (Fixer) Replenisher (g) g) Ethylenediaminetetraacetic acid diammonium salt 12.0 Ammonium sulfite 14.0 Ammonium thiosulfate aqueous solution (700g/j) 280.0mj
Silver bromide 15 Ammonium iodide 0.9 Add water
1.0j pH 7,0 (washing solution) Common tap water for mother liquor and replenisher was mixed with H-type strongly acidic cation exchange resin (Amberlite TR-120B manufactured by Rohm and Haas) and OH-type strongly basic anion exchange resin (Amberlite TR-120B manufactured by Rohm and Haas). IRA-
Water was passed through a mixed bed column packed with 400) to reduce the concentration of calcium and magnesium ions to below 3 +++ g/l, followed by 2
0 mg/j and 150 mg/j of sodium sulfate were added. The pH of this solution is in the range of 6.5 to 7.5.
3.

(Stabilizing solution) Common to mother solution and replenisher solution (g) Formalin (37%) 1.2mm external surfactant
0.4[C, oH2, -0+CH2CH
20-)-,,H] Ethylenediaminetetraacetic acid disodium salt 0.05 Additive compound
Table 1 Add water 1.0 ゑp)I
Processing like 7.0 or higher,
Stability used, respectively? Depending on the night, processing IA to IG (
Table 1).

After completing each continuous process under the conditions shown in Processes 1A to IG, the unexposed sample was processed using a Fuji photographic densitometer FSD104 (
The green density was measured using Fuji Photo Film ■ (manufactured by Fuji Photo Film Company).

Furthermore, the treated sample was heated at 60℃/70%RH for 20 minutes.
It was stored for several days, and the green color density after storage was measured in the same manner to determine the increase in density due to storage (stain over time).

The results are shown in Table 1.

Table Addition amount of added compound ((Le 10 LA (comparative example) IB (comparative example) 1C (invention) ID (invention) IE (invention) IF (invention) 1G (invention) Triethanolamine 2-methyl Imiguzole 4-Methylimikuzole Imidazole Imidazole Imidazole 0.02 0.02 02 0.02 0, OIO,005 0,28 0,27 0,06 0,06 05 0,06 0,08 Shown in Table 1 As can be seen, the generation of staining over time is significantly suppressed in the processed IC to IG to which the processing method of the present invention is applied.
It can be seen that the triethanolamine described in No. 3 has no effect of suppressing the occurrence of staining over time.

Example 2 142 pieces of each stable solution after the continuous treatment in Processes IA to IG of Example 1 were placed in a measuring cylinder for 112, and heated to 40°C.
The liquid state was observed over time under the conditions of /90% RH, and the number of days until a heterochromatic precipitate (sulfurization) was generated was determined.

Note that the depth of the liquid in the graduated cylinder was 30 cm.

The results are shown in Table 2.

Table IA (comparative example) IB (comparative example) IC (present invention) 10 (present invention) IE (present invention) IF (present invention) IG (present invention) Additive compound addition l amount (mol 10 Triethanolamine 2- Methylimixole 4-Methylimitazolimidazoleimidazoleimidazole 0.02 0.02 0.02 0.02 0, Ol 005 ]07 As shown in Table 2, the treatments IC to IG to which the treatment method of the present invention was applied In addition, triethanolamine (treatment IB) described in U.S. Pat. It can be seen that although this method is able to prevent this to some extent, the effect is much lower than that of the present invention.

Example 3 In the treatment process of Example 1, the stabilization process before the drying process was replaced with a water washing process, and the water washing was performed in a three-stage countercurrent system, and the water was refilled from the third stage water washing tank at a replenishment amount of 30 mj. were treated in the same way. However, for the washing liquid in the third stage washing tank,
Similar to the stabilizing liquid of Example 1, the washing liquid of Example 1 was used in which additive compounds were added to the washing liquid of Example 1.

When the stain over time was examined in the same manner as in Example 1 in such a process of washing with water for 7 nights, the same results as in Example 1 were obtained.

As a result, it was confirmed that the same effect of suppressing stain 08 over time can be obtained in the washing liquid as in the case of the stabilizing liquid.

It was also confirmed that no sulfidation occurred.

<Effects of the Invention> According to the present invention, staining over time can be significantly suppressed. Also, stabilizer or water washing? Sulfurization can be prevented at night, especially in stable liquids where sulfurization is likely to occur.

wish Reason same People Fuji Photo Film Co., Ltd. Person Patent Attorney Yo Ishii

Claims (1)

[Claims] (1) After imagewise exposure of the silver halide color photographic light-sensitive material,
In a processing method in which water washing and/or stabilization treatment is performed after color development processing and desilvering processing, the washing liquid and/or stabilizing liquid used in the water washing treatment and/or stabilization treatment has the following general formula ( A method for processing a silver halide color photographic material, which comprises a compound represented by I). General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ {In the above general formula (I), R_1, R_2, R_
3 and R_4 each represent a hydrogen atom, an alkyl group, or an alkenyl group. }