JPH03296048A - Method and device for processing silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To prevent the dissolution of an electrode member and to improve the shelf stability of an image by using a carbon-contg. material as the material of the electrode member brought into contact with a processing soln. contg. an aminopolycarboxylic acid compd. when photographic processing is carried out with prescribed processing solns. CONSTITUTION:When an exposed silver halide photographic sensitive material is subjected to photographic processing with prescribed processing solns. such as a black-and-white developing soln., a bleaching soln. and a fixing soln., a carbon contg. material is used as the material of an electrode member brought into contact with a processing soln. contg. an aminopolycarboxylic acid compd. The carbon-contg. material is concretely graphite, glassy carbon or carbon fibers. The dissolution of the electrode member is prevented even by contact with the processing soln. in continuous processing over a long period of time and an image having superior photographic performance such as shelf stability is obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a processing method and a processing apparatus for silver halide photosensitive materials (hereinafter referred to as photosensitive materials).

<Prior art> Black and white photosensitive materials are processed through steps such as black and white development, fixing, and water washing after exposure, while color photosensitive materials are processed through steps such as color development and water washing after exposure.
It is processed through processes such as desilvering, water washing, and stabilization.

Black and white developer for black and white development, fixer for fixing, color developer for color development, bleach, bleach-fix, fixer for desilvering, tap water or ion exchange water for washing, Stabilizing solutions are used in each stabilization process. 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.

Under these circumstances, in the case of color photosensitive materials, the basic processing steps mentioned above 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, 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-mentioned desilvering step includes a method in which the bleaching step and the fixing step are performed in the same bath, a method in which the steps are performed in separate baths, and a method in which the bleaching step and the bleach-fixing step are performed in separate baths. Moreover, in this case, each bath may be multi-tank.

In addition to this basic process mentioned above, we also introduce the photographic process of dye images.
Various auxiliary processes are performed to maintain physical quality or improve storage stability. Such a step is carried out using, for example, a hardening bath, a stopping bath, a stabilizing bath, a washing bath, and the like.

In addition, the above processing is generally performed using an automatic processor, and in order to maintain the performance of the processing solution constant, the continuous processing using this automatic processor is usually done in accordance with the amount of color photosensitive material processed. A replenishment method is used to replenish the replenisher.

Each processing solution or replenisher used in each of the above processing steps contains an aminopolycarboxylic acid compound added as an anti-settling agent for calcium or magnesium, that is, as a water softener, or for the purpose of improving the stability of the solution. many.

Examples of processing solutions containing such compounds include black and white developers, color developers, bleaching solutions, bleach-fixing solutions, fixing solutions, adjustment solutions, stabilizing solutions, and washing water.

By the way, in processing liquids that have bleaching ability, such as bleaching liquids and bleach-fixing liquids, in order to express the essential functions of this processing liquid,
An oxidizing agent is added. As this oxidizing agent, aminopolycarboxylic acid ferric complex salts are often used from the viewpoint of environmental protection, handling safety, and the like.

Such an oxidizing agent is typically ethylenediaminetetraacetic acid ferric complex salt [EDTA/Fe(III)]
, ]1.3-diaminopropanetetraacetic acid ferric complex salt [1,
3-PDTA-Fe(III)], which is not only added in the form of a complex salt, but also an aminopolycarboxylic acid and a ferric salt are respectively added to form a complex salt in the liquid. In some cases.

Electrode members are installed for various purposes in a processing tank containing a processing liquid containing the above-mentioned aminopolycarboxylic acid compound or a replenishment tank containing its replenisher.

For example, it is an electrode for a level sensor, a ground electrode rod, etc.

These electrode members are generally made of Mo-added stainless steel, such as 5US316, in consideration of cost, workability, etc., or corrosion resistance such as pitting corrosion since they are used in contact with processing liquids. It is something that

An electrode member made of such 5U3316 or the like comes into contact with a processing solution containing an aminopolycarboxylic acid compound over a long period of time during continuous processing, and is gradually dissolved by the flow of a minute current.

In particular, in order to speed up the desilvering process, please use the above 1.
When an oxidizing agent having high oxidizing power such as 3-PDTA-Fe (II+) is used, dissolution proceeds even when no current flows.

In the worst case, when the electrode member melts as described above, it loses its function as a sensor and ground.
Before this happens, components of the stainless steel are eluted into the liquid, deteriorating photographic performance.

For example, bleaching solutions mainly cause deterioration in image storage stability, and color developing solutions mainly cause an increase in fog density.

<Problems to be Solved by the Invention> The purpose of the present invention is to prevent troubles caused by dissolution of electrode members during processing using a processing solution containing an aminopolycarboxylic acid compound, and to improve photographic performance such as image storage stability. An object of the present invention is to provide a method and apparatus for processing a silver halide photographic material, which can produce excellent images.

<Means for Solving the Problems> The above object is achieved by the present invention having the following configurations (1) to (3).

(1) When photographically processing a silver halide photographic light-sensitive material after exposure using a predetermined processing liquid, an electrode member that comes into contact with a processing liquid containing an aminopolycarboxylic acid compound among the processing liquids contains carbon. 1. A method for processing a silver halide photographic material, the method comprising using a silver halide photographic material to prevent deterioration of photographic properties.

(2) A processing apparatus for a silver halide photographic light-sensitive material, in which a sensor having a sensing electrode member is disposed at a position in contact with a processing solution containing an aminopolycarboxylic acid compound stored therein, the sensing electrode member being a carbon 1. A processing device for a silver halide photographic material, characterized in that it is formed from a containing material.

(3) A processing apparatus for silver halide photographic materials, in which a ground electrode is disposed at a position in contact with a processing solution containing an aminopolycarboxylic acid compound stored therein, wherein the ground electrode member is formed from a carbon-containing material. A processing apparatus for silver halide photographic materials, characterized in that:

<Function> Conventionally, stainless steel has been used for electrode members that come into contact with processing liquids containing aminopolycarboxylic acid compounds.
It has been discovered that the electrode member dissolves when a minute current flows in the presence of an aminopolycarboxylic acid compound.

In addition, the dissolution of the electrode member can be achieved using a high-potential oxidizing agent, 1,3-
It has also been confirmed that this phenomenon occurs in processing solutions such as bleaching solutions containing diaminopropanetetraacetic acid ferric complex salts, regardless of the presence or absence of electric current.

This melting of the electrode member may cause damage to the electrode member used as a sensor or ground, and some kind of reaction may occur between the metals such as iron dissolved in the liquid and the above compounds, which adversely affects photographic performance. This will affect the

Deterioration in photographic performance manifests as, for example, deterioration in image storage stability and increase in minimum density (fog density).

The present invention solves the above problems and eliminates the negative impact on photographic performance.

Conventionally, in a processing liquid having a fixing ability such as a fixing liquid, a pair of electrodes is installed in the liquid to perform electrolysis, thereby depositing silver on the cathode and recovering the silver. In this method, carbon may be used as an electrode material, primarily an anode material.

However, unlike the present invention, this method involves installing electrodes for the purpose of recovering silver, and does not prevent deterioration of photographic performance. For this reason, in this method, the carbon electrode is sometimes used in a circulation system, but is mainly carried out in the treated waste liquid.

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

In the present invention, the silver halide photographic light-sensitive material after exposure (hereinafter also referred to as light-sensitive material) includes a black-and-white developer, a color developer, a bleach solution, a bleach-fix solution, a fixer, washing water, a stabilizer, Photographic processing is performed using a predetermined processing solution such as a conditioning solution.

The above processing is usually performed using an automatic processor.

In this case, a carbon-containing material is used for the electrode member that comes into contact with the processing liquid containing the aminopolycarboxylic acid compound.

Here, representative examples of the processing solution containing the above g2 compound include a black-and-white developer, a color developer, a bleach solution, a bleach-fix solution, a fixer, a washing water, a stabilizer, an adjustment solution, and the like. It also includes replenishers for each processing solution. Furthermore, it includes not only those contained by adding the above-mentioned compounds, but also those contained by bringing in the photosensitive material during processing.

Moreover, the aminopolycarboxylic acid compound refers to a compound containing aminopolycarboxylic acid, and specifically includes aminopolycarboxylic acid, a salt thereof, a metal complex salt thereof, and the like.

Furthermore, aminopolycarboxylic acids include not only those having an amino group itself, but also those having a nitrogen atom-containing group (for example, an imino group) derived from an amine group.

These processing liquids will be described later.

In the present invention, the carbon-containing material used for the electrode member is not particularly limited as long as it conducts electricity through carbon, and has a volume resistivity lXl0-' to IX10'
Ωε■, preferably 1×10−4 to lXl0−”ΩC−
You can use the one below.

Specifically, graphite, glassy carbon, carbon fiber, carbon fiber reinforced resin (CFRP), etc. may be mentioned.

Among these, isotropic high-density carbon materials, carbon fiber reinforced resins, and the like are preferred in the present invention from the viewpoint of processability, mechanical strength, and the like.

These materials are commercially available, and can be made into predetermined shapes and
For example, it may be used in a plate shape, screw shape, or rod shape. In order to form a predetermined shape, various molding methods such as injection molding and various processing methods such as cutting may be used.

In the present invention, preferred isotropic high-density carbon materials include special carbon material T-6, ET-10 (manufactured by IBIDEN), and special carbon material IG-11 (Toyo Tanso).
), etc.

This material has a bulk density of 1.7 to 2.0 gcm-'' and is particularly preferred in terms of processability.

The volume resistivity of T-6 above is 1.6XIO-"Ωc1, and ET-10 is 1.2X10-"Ωc+a, IG-1
1 is 1. lX10-"ΩcI11.

Further, examples of the carbon fiber reinforced resin include carbon fiber reinforced PPS resin CZ-1030 (manufactured by Dainippon Ink Chemicals), liquid crystal polymer "Vectra J A230" (manufactured by Polyplastics), and the like.

The above CZ-1030 is made of polyphenylene sulfide (
PPS) is used as the base material (matrix) resin and contains 30 wt% of carbon fiber, and has a volume resistivity of 103 to 1.
It is 0'Ωcm. In addition, A230 uses liquid crystal polymer as a base resin and contains 30 wt% carbon fiber, and has a volume resistivity of 4000 ΩCm and a surface resistance of 60.
It is 0Ω.

In addition, a conductive material made by adding and dispersing graphite, carbon black, etc. into a suitable base material can also be used.

Moreover, these carbon-containing materials may be coated on a base material.

Examples of the electrode member in the present invention include a liquid level sensor that detects the liquid level by installing an electrode pair in a replenishment tank or a processing tank, and a conductivity sensor that detects the conductivity of the liquid by installing it in a processing tank. Specific examples include those used in various sensors, and those installed in sub-tanks and used as ground electrodes for heaters and the like.

Among these, it is preferable to use it for a liquid level sensor installed in a replenishment tank or the above-mentioned earth electrode.

This is because such an electrode member is likely to have problems with dissolution due to contact with a treatment liquid containing an aminopolycarboxylic acid compound.

Note that the electrode shape, size, etc. may be appropriately selected depending on the application.

FIG. 1 shows a typical configuration example of a processing apparatus of the present invention.

The processing device 1 has a processing tank (tank) 11.
1 is filled with a processing liquid 100.

This treatment liquid 100 contains an aminopolycarboxylic acid compound, and specific examples thereof include those mentioned above.

A sub-tank 12 is installed in the processing tank 11, and the processing liquid 100 is configured to communicate between both tanks.

A heater 21 is installed in the sub-tank 12 to maintain the temperature of the processing liquid 100 at a constant temperature, and further,
For the purpose of preventing electric leakage of this heater 21, the earth electrode 25
is located.

This earth electrode 25 is made of the carbon-containing material mentioned above.

The processing apparatus 1 also includes a replenishment tank (tank) 13 , the replenishment tank 13 is filled with a processing replenisher 110 , and the processing replenisher 110 is supplied to the processing tank 11 via a replenishment pump 14 . It is configured to

This processing replenisher 110 corresponds to the processing liquid 100 and contains aminopolycarboxylic acid.

A liquid level sensor 35 is arranged in the replenishment tank 13. The liquid level sensor 35 detects the liquid level of the processing replenisher 110 and warns of a drop in the liquid level of the processing replenisher 110.

The liquid level sensor 35 is composed of two electrodes.
The electrodes are arranged at regular intervals on the tank wall. This electrode member is made of a carbon-containing material, and the liquid level is detected by detecting the electrical resistance between both electrodes.

The processing apparatus of the present invention is not limited to the illustrated example, and may be of various types, and the electrode member formed of a carbon-containing material is not limited to the illustrated member.

The present invention can be applied to the processing of various photosensitive materials, and is particularly preferably applied to the processing of color photosensitive materials.

In the processing of color photosensitive materials, deterioration of photographic performance due to the dissolution of the electrode members has conventionally been a particular problem, and the present invention effectively solves this problem.

Examples of such treatment steps include color development, bleaching, bleach-fixing, fixing, first washing, second washing, and stabilization.

In the above, when the development process is a reversal development process, color development may be performed in combination with a reversal bath or the like after the first black and white development.

In addition to the above-mentioned bleaching-bleach-fixing and fixing steps, typical desilvering steps include the following.

■Continuous bleaching■Bleach-bleach fixing■Bleach-constant washing with water ■Continuous bleaching and fixing ■Washing→bleach-fixing■Bleach-fixing■Fixing→bleach-fixing Among these, for step
No. 75352.

In addition, the treatment baths such as bleaching baths and fixing baths used in the above steps may have one tank or two or more tanks (for example, 2 to 4 tanks, in which case a countercurrent system is preferable). good.

Many of the processing solutions used in the desilvering process contain aminopolycarboxylic acid compounds. In particular, bleaching solutions contain iron 1,3-propylenediaminetetraacetate (1,3-propylenediaminetetraacetate) to speed up the processing as an oxidizing agent. III) High potential oxidizing agents such as complex salts are often used.

Therefore, the application of the present invention is particularly effective for such processing liquids.

In addition, bleaching solutions containing aminopolycarboxylic acid compounds as high-potential oxidizing agents are used for rapid processing of color photosensitive materials composed of silver halide containing silver iodide, such as color negative films and color reversal films. Because it is used as a
, ■It is preferable to apply.

In the treatment process of the present invention, a water washing or stabilization process is usually performed in combination after the desilvering process, but it is also possible to use only the water washing process, or to perform the stabilization process without actually washing with water. This can be a simple processing method.

The processing liquid in the present invention will be described.

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.

-1 N,N-diethyl-p-phenylenediamine-2 2-amino-5-diethylaminotoluene-3 -4 2-amino-5-(N-ethyl-N-laurylamino)toluene 4-[N-ethyl- N-(β-hydroxyethyl)aminocoaniline-5 2-methyl-4-[N-ethyl-N- (β-hydroxyethyl)aminocoaniline-6 4-amino-3-methyl-N-ethyl-N -[β-(methanesulfonamide)ethylcoaniline-7 N-(2-amino-5-diethylaminophenylethyl)methanesulfonamide-8 N,N-dimethyl-p-phenylenediamine-9 4-amino-3- Methyl-N-ethyl-N-methoxyethylaniline D-104-amino-3-methyl-N-ethyl-N-β
-Ethoxyethylaniline D-114-amino-3-methyl-N-ethyl-N-β
-Butoxyethylaniline Among the above-mentioned -phenylenediamine derivatives, Exemplified Compound D-5 is particularly preferred.

Further, these p-phenylenediamine derivatives may be salts such as sulfates, hydrochlorides, sulfites, p-h luenesulfonates, and the like. The amount of the aromatic primary amine color developing agent used is preferably about 0.1 to 11 per 11 color developing solutions.
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 are added to the color developing solution as preservatives as necessary. be able to.

The preferable amount of preservative added is 0.5 per 1j of color developer.
-10g, more preferably 1-5g.

Alternatively, the aromatic primary amine color developing agent may be directly applied to
Examples of the preserving compound include various hydroxylamines, hydroxamic acids described in JP-A-63-43138, and JP-A No. 63-43138.
Hydrazines and hydrazides described in No. 3-146041, phenols described in No. 63-44657 and No. 63-58443, α-hydroxyketones and α-aminoketones and/or α-aminoketones described in No. 63-44656, It is preferable to add various saccharides described in No.-36244. In addition, in combination with the above compounds, JP-A-63-
No. 4235, No. 63-24254, No. 63-2164
Monoamines described in No. 7, No. 63-146040, No. 63-27841 and No. 63-25654, etc.
No. 63-30845, No. 63-14640, No. 63
Diamines described in No.-43139 etc., No. 63-216
No. 47, No. 63-26655 and No. 63-4465
Polyamines described in No. 5, nitroxy radicals described in No. 63-53551, alcohols described in No. 63-43140 and No. 63-53549, No. 63-56
Oximes described in No. 654 and No. 63-239447
It is preferable to use the tertiary amines described in No.

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.

An aminopolycarboxylic acid compound is added to the color developing solution of the present invention.

These compounds are used as chelating agents for the purpose of sequestering metal ions, and are added as anti-settling agents for calcium and magnesium, or to improve the stability of color developing solutions.

Specifically, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, triethylenetetraminehexaacetic acid, transcyclohexanediaminetetraacetic acid, 1,2-diaminopropanetetraacetic acid, glycol ether diaminetetraacetic acid, N
, N'bis(2-hydroxybenzyl)ethylenediamine-N,N'-diacetic acid, nitrilotriacetic acid, hydroxyethyliminodiacetic acid, and the like.

These compounds may be used alone or in combination of two or more.

Further, the amount added is I x 10-' to 5 x 10-'' mol/l, preferably I x 10-'' to I x 10
-"mol/l.

The color developing solution in the present invention thus contains an aminopolycarboxylic acid compound, but as described above, since a carbon-containing material is used for the electrode member, conventional electrode members are unlikely to dissolve. It is possible to avoid troubles caused by.

Further, in the present invention, the above aminopolycarboxylic acid compound and other chelating agents may be used together.

Examples of such chelating agents include organic phosphonic acids and phosphonocarboxylic acids.

Specifically, N,N,N-trimethylenephosphonic acid, ethylenediamine-N,N,NN'-tetramethylenephosphonic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, 1-hydroxyethylidene-1, l-diphosphonic acid and the like.

Furthermore, ethylenediamine orthohydroxyphenylacetic acid or the like may be used in combination.

The color developer used in the present invention is preferably pl(9
-12, more preferably 9-11.0, and the color developer may contain other known developer components.

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, disodium phosphate, dipotassium phosphate, sodium phonate, potassium borate, Sodium tetraborate (borax), potassium tetraborate, 0-
Sodium hydroxybenzoate (sodium salicylate), potassium 0-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 buffering agent added to the color developing solution is preferably 0.1 mol/j or more, particularly preferably 0.1 to 0.4 mol/j.

Any development accelerator can be added to the color developing solution if necessary. However, the color developing solution in the present invention preferably does not substantially contain benzyl alcohol from the viewpoints of pollution, liquid preparation properties, and prevention of color staining. Here, "substantially" means that the developer contains 2 mN or less per developer II2, preferably not at all.

In addition, as a development accelerator, Japanese Patent Publication No. 37-16088
No. 37-5987, No. 38-7826, No. 44
-12380, 45-9019, U.S. Patent No. 3,
818,247, etc.; p-phenylenediamine compounds described in JP-A-52-49829 and JP-A-50-15554;
No. 137726, Japanese Patent Publication No. 44-30074, Japanese Patent Publication No. 1977
Quaternary ammonium salts described in No. 6-156826, No. 52-43429, etc., U.S. Patent No. 2,494,903
No. 3,128,182, No. 4,230゜79
No. 6, No. 3.253,919, Special Publication No. 41-114
No. 31, U.S. Patent No. 2,482゜546, U.S. Patent No. 2,546
96,926, 3.582,346, etc.; Japanese Patent Publication No. 37-16088, 42-
25201, U.S. Patent No. 3,128,183, Japanese Patent Publication No. 11431-1983, Japanese Patent Publication No. 42-23883, U.S. Patent No. 3,532.501, etc., and other 1-phenyl-3-pyrazolidones. kind,
Imidazole and the like can be added as necessary.

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

The color developing solution used in the present invention may contain a fluorescent whitening agent. As the optical brightener, a 4.4°-diamino-2,2°-disulfostilbene compound is preferable, and the amount added is 0 to 5 g/l, preferably 0.11 g to 4 g/l.
It is j.

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

In such a color developing solution, as mentioned above, 0.01
By using a treatment tank with a liquid opening ratio of 5 or less and by replenishing water, treatment performance can be maintained constant.

The processing temperature in the color developing solution in the present invention 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.

Further, the color development bath may be divided into two or more baths as necessary, and the color development replenisher may be replenished from the first bath or the last bath to shorten the development 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 a so-called black-and-white first developer used in the commonly known reversal processing of color photosensitive 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 1-phenyl-3-pyrazolidone, metol and hydrochloride, preservatives such as sulfites, and alkalis such as sodium hydroxide, sodium 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. can be mentioned.

Furthermore, in the present invention, an aminopolycarboxylic acid compound may be added as a water softener in place of or in combination with the above-mentioned polyphosphate. Specifically, they are ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, etc. When used alone, 1X10-' to 5X10-2 mol/j, and when used together, 1X10-' to 1x10 -2 mol/l may be added.

When an aminopolycarboxylic acid compound is added, a carbon-containing material may be used for the electrode member as described above, and by doing so, it is possible to prevent the electrode member from dissolving.

In the present invention, the bleaching solution used for desilvering treatment contains an oxidizing agent.

As the oxidizing agent, an aminopolycarboxylic acid iron(III) complex salt is used from the viewpoint of environmental protection and handling safety.

Below, aminopolycarboxylic acid iron (II) in the present invention will be described.
I) #! Here are some specific examples of salt.

(1) 1,4-butylenediaminetetraacetate iron(In) complex salt (2) diethylenethioetherdiaminetetraacetate iron(II)
I) Complex salt (3) Glycol ether diamine tetraacetate iron (III)
Complex salt (4) 1,3-propylenediaminetetraacetic acid iron(III)
Complex salt (5) Ethylenediaminetetraacetic acid iron (I[l) complex salt (6)
Diethylenetriaminepentaacetate iron(III) complex salt (7) trans-1,2-cyclohexanediaminetetraacetic acid iron(m) salt (8) N-(2-acetamido)iminodiacetic acid iron(II)
I) Complex salt (9) Iron(III) methyliminodiacetate complex salt (10) Iron(m) iminodiacetate complex salt Among these aminopolycarboxylic acid iron(III) i salts, oxidation is recommended for rapid bleaching. It is preferable to use a so-called high potential oxidizing agent having a reduction potential of L 50 +mV or more, preferably 180 mV or more, more preferably 200 mV or more.

That is, (1) to (4), (8) in the above specific examples
~(lO) corresponds to this.

Among them, (4) 1,3-propylenecyaminetetraacetic acid iron(III) complex salt (redox potential 250 mV) is preferable.

In the above, the redox potential of an oxidizing agent is determined by the Transactions of the Faraday Society (Tr.
answers of the Faraday
Society) 55@(1959), 1312
It is defined by the oxidation-reduction potential measured by the method described on pages 13-13.

The redox potential in this case was obtained by the above-mentioned method under the condition of pH 6.0.

The reason why the potential determined at pH 6.0 is employed is that pH around 6.0 is a guideline for the occurrence of bleaching fog.

That is, in reality, when the color development process is completed and the photosensitive material enters the bleaching solution, the pH in the film of the photosensitive material decreases, but if the pH decreases quickly at this time, the bleaching edge blur will be small;
It has been confirmed that if the pH decreases slowly or if the pH of the bleaching solution is high, the bleaching blade will become thicker, and based on these facts, pH 6.0 is used as the standard.

Aminopolycarboxylic acid iron (III) n salts are used in the form of sodium, potassium, ammonium, etc. salts, but ammonium salts are preferred because they are the most rapid in bleaching.

The amount of aminopolycarboxylic acid iron (III) complex salt added in the present invention may be 1X10-'' to 0.5 mol/1, preferably 0.1 to 0.4 mol/E.

Further, in the present invention, the oxidizing agent may be used alone or in combination of two or more.

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

When using an aminopolycarboxylic acid iron (In) 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) may be present in the bleach solution to form a complex salt.

In the case of this complex formation, the aminopolycarboxylic acid may be added in a slightly excess amount compared to the amount required for complex formation with ferric ions, and when added in excess, it is usually 0.01.
It is preferable to use an excess in the range of 10% to 10%.

As described above, the bleaching solution in the present invention contains an aminopolycarboxylic acid compound, but since a carbon-containing material is used for the electrode members that come into contact with this solution, problems caused by dissolution of the electrode members can be avoided. .

In particular, bleaching solutions containing a high-potential oxidizing agent such as 1,3-propylenediaminetetraacetic acid iron (III) complex salt have conventionally caused significant dissolution of electrode members, which has caused problems with deterioration of image storage stability. However, the present invention solves this problem.

Bleaching solutions as described above are used at a pH of 2 to 8 for boat fishing. In order to speed up the treatment, the pH should be adjusted to between 2.5 and 4.
2, preferably 2.5 to 4.0, particularly preferably 2.5
It is best to set it to 3.5 to 3.5 (the replenisher is usually 1.0 to 4.
It is better to use it as 0.

In the present invention, known acids can be used to adjust pl() to the above range.

As such an acid, an acid having a pKa of 2 to 5.5 is preferable. In the present invention, pKa represents the logarithm of the reciprocal of the acid dissociation constant, and indicates the value determined at an ionic strength of 0.1 mol/i and 25°C.

In the present invention, it is preferable to use a bleaching solution containing 1.2 mol/j or more of an acid having a pKa in the range of 2.0 to 5.5. By containing 1.2 mol/P or more of an acid with a pKa of 2.0 to 5.5 in the bleaching solution, it is possible to further eliminate bleaching fog and to improve the increase in staining in uncolored areas after processing.

The acid with a pKa of 2.0 to 5.5 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 5.5 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 55 may be a monobasic acid or a polybasic acid. In the case of polybasic acids, their p
If Ka is in the above range of 2.0 to 5.5, it can be used as a metal salt (eg, sodium or potassium salt) or ammonium salt. In addition, organic acids with pKa of 2.0 to 5.5 are
It is also possible to use a mixture of more than one species. However, aminopolycarboxylic acids and their Fe complex salts are excluded (.

Preferred specific examples of organic acids with a pKa of 2.0 to 5.5 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, and leucine; Aromatic-basic acids such as benzoic acid and monosubstituted benzoic acid 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 such as amino acid-based tribasic acids such as acids; aromatic dibasic acids such as phthalic acid and terephthalic acid; and polybasic acids such as citric acid can be enumerated.

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 suitably 0.5 mol or more per 1j of bleaching solution. Preferably it is 1.2 to 2.5 mol/2. More preferably, it is 1.5 to 2.0 mol/j.

When adjusting the pH of the bleaching solution to the above range, the above acid and an alkaline agent (for example, aqueous ammonia, KOH% NaOH, imidazole, monoethanolamine, jetanolamine) may be used in combination. Among them, ammonia water is preferred. Further, as the alkaline agent used in the bleach starter when preparing the mother liquor of the bleach solution from the bleach replenisher, it is preferable to use imidazole, monoethanolamine or jetanolamine.

In the present invention, various bleaching accelerators can be added to the bleaching solution or its pre-bath. Such bleach accelerators are described, for example, in U.S. Pat. No. 3,893,858.
Specification of German Patent No. 1,290,812,
British Patent No. 1,138,842, JP-A-53-
Publication No. 95630, Research Disclosure No. 1
Compounds having a mercapto group or a disulfide group described in No. 7129 (July 1978 issue), JP-A-1988-1
Thiazolidine derivatives described in US Pat. No. 40129, thiourea derivatives described in US Pat. No. 3,706,561, iodides described in JP-A-58-16235, German Patent No. 2,748,430. Polyethylene oxides described in the specification, polyamine compounds described in Japanese Patent Publication No. 45-8836, etc. can be used.
Particularly preferred are mercapto compounds as described in GB 1,138,842.

In addition to the oxidizing agent (bleaching agent) and the above-mentioned compounds, the bleaching solution used in the present invention may contain bromides such as potassium bromide, sodium bromide, ammonium bromide, or chlorides such as potassium chloride, sodium chloride, ammonium chloride, etc. A rehalogenating agent may be included. The concentration of the rehalogenating agent is 0.1 to 5 mol per 1j in the bleaching solution.
Preferably it is 0.5 to 3 mol.

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

In the present invention, it is preferable to adopt a replenishment method, and the amount of replenishment of the bleaching solution is 200 m1 or less per m'' of light-sensitive material, preferably 140 to 10+++j.

Further, the bleaching treatment time is 120 seconds or less, preferably 50 seconds or less, and more preferably 40 seconds or less.

In addition, during the treatment, iron(III) aminopolycarboxylate
Bleach solutions using complex salts are aerated,
It is preferable to oxidize the aminopolycarboxylic acid iron (II) complex salt produced.

This regenerates the oxidizing agent and maintains extremely stable photographic performance.

The fixing solution or bleach-fixing solution in the present invention contains a fixing agent.

As fixing agents, thiosulfates such as sodium thiosulfate, ammonium thiosulfate, sodium ammonium thiosulfate, potassium thiosulfate, thiocyanates (rodan salts) such as sodium thiocyanate, ammonium thiocyanate, potassium thiocyanate, thiourea, Thioether etc. can be used.

Among them, it is preferable to use ammonium thiosulfate. The amount of fixer is 0 per 1β of fixer or bleach-fixer.
．． The amount is 3 to 3 mol, preferably 0.5 to 2 mol.

In addition, from the viewpoint of promoting fixation, the above-mentioned ammonium thiocyanate (rhodan ammonium), thiourea, thioether (for example, 3,6-cythia-1,8-octanediol)
It is also preferable to use these compounds in combination, and the amount of these compounds used in combination is 0.01 to 0 per IJ2 of the fixer or bleach-fixer.
．． The amount is generally about 1 mol, but in some cases, the fixing promotion effect can be greatly enhanced by using 1 to 3 mol.

As the fixing agent in the fixing solution or bleach-fixing solution, in order to speed up the processing, it is particularly preferable to use thiosulfate and thiocyanate in combination, especially ammonium thiosulfate and ammonium thiocyanate. is preferred.

In this case, the thiosulfate may be used at the above-mentioned 0.3 to 3 mol/l, and the thiocyanate may be used at 1 to 3 mol/j1, preferably 1 to 2.5 mol/l.

Other compounds other than thiocyanate that can be used in combination with thiosulfate (particularly ammonium thiosulfate) include thiourea, thioether (for example, 3,6-cythia-1,8-octanediol), and the like.

The amount of these compounds used in combination is generally about 0.01 to 0.1 mol per 11 of the fixing solution or bleach-fixing solution, but depending on the case, it may be used in an amount of 1 to 3 mol.

The fixer or bleach-fixer contains sulfites (e.g. sodium sulfite, potassium sulfite, ammonium sulfite) as preservatives, hydroxylamine, hydrazine,
Bisulfite adducts of aldehyde compounds (eg, acetaldehyde sodium bisulfite) and the like can be included. 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

Like the bleaching solution, the bleach-fixing solution contains an aminopolycarboxylic acid iron (III) complex salt as an oxidizing agent. Specifically, compounds similar to those added to bleaching solutions can be mentioned, and ethylenediaminetetraacetic acid iron (III) complex salt is commonly used.

In the bleach-fix solution, the amount of bleach, which is an oxidizing agent, per 11 parts of the bleach-fix solution is 0. O1 to 0.5 mol, preferably 0.015 to 0.3 mol, particularly preferably 0.0
It is 2 to 0.2 mol.

Furthermore, an aminopolycarboxylic acid compound is added to the fixer and bleach-fixer for the purpose of stabilizing the solution.

Specific examples thereof are the same as the aminopolycarboxylic acids mentioned in the color developing solution, and ethylenediaminetetraacetic acid or its salts (sodium salts, ammonium salts, etc.) are used.

The amount of the above compound added in the fixing solution is 1X10-”~
0.6 mol/L preferably 1 x 104 to 0.2 mol/j
It is.

Further, the amount of the above compound added in the bleach-fix solution is 0.01 to 0.5 mol/j, preferably 0.0 mol/j, separately from the bleaching agent.
It is 5 to 0.3 mol/j.

In this way, in bleach-fixing solutions and fixing solutions containing aminopolycarboxylic acid compounds, since a carbon-containing material is used for the electrode members that come into contact with these processing solutions, dissolution of the electrode members can be avoided. The deterioration of image stability caused by this is resolved.

It is particularly effective when aminopolycarboxylic acid iron (III) II salt, which is a high-potential oxidizing agent, is used as an oxidizing agent in the bleach-fix solution.

Further, in addition to the aminopolycarboxylic acid compound, organic phosphonic acids may be added to the fixing solution and the bleach-fixing solution as a chelating agent to stabilize the solution.

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 pH of the fixer is 5~
The pH of the bleach-fix solution is preferably 9, more preferably 7 to 8. The pH of the bleach-fix solution is preferably 6 to 8.5, and more preferably 6.5 to 8.0.

When the replenishment method is adopted, the amount of replenishment of the fixing solution or bleach-fixing solution is preferably 300 to 3,000 x 1 per 1 m of photosensitive material, more preferably 300 to 1,000 x 1.
It is.

In addition, in the present invention, when fixing processing or bleach-fixing processing is performed after bleaching processing, the total processing time is 0.
．． It is preferably 5 to 2 minutes, particularly 1 to 1.5 minutes.

The total processing time of the desilvering step is preferably short, preferably 1 to 4 minutes, more preferably 1 minute.
It is 0 seconds to 3 minutes. In addition, the processing temperature is 25-50℃,
Preferably it is 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 treatment steps such as bleaching, bleach-fixing, and fixing of the present invention, it is preferable that stirring be as strong as possible in order to more effectively exhibit the effect of evaporation correction according to the present invention.

A specific method for strengthening stirring is disclosed in JP-A-62-18346.
No. 0, No. 62-183461, the method of impinging a jet of processing liquid on the emulsion surface of a photosensitive material, and the method of colliding a jet of a processing liquid on the emulsion surface of a photosensitive material, as described in JP-A No. 62-183-1.
No. 83461, a method of increasing the stirring effect using a rotating means, and further improving the stirring effect by moving the photosensitive material while bringing the emulsion surface into contact with a wiper blade provided in the liquid to create turbulence on the emulsion surface. method, and a method of increasing the circulation flow rate of the entire treatment liquid. 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 rate.

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.

As described above, the present invention is carried out by continuous processing using an automatic developing machine.
It is preferable to have a photosensitive material conveying means described in No. 60-191259. Said Japanese Unexamined Patent Publication No. 60-19
As described in No. 1257, such a conveying means can significantly reduce the amount of processing liquid brought into the post bath from the front bath, and is highly effective in preventing deterioration in the performance of the processing liquid. This is particularly effective in shortening time and reducing the amount of processing liquid replenishment.

The present invention is effective when applied when the total processing time (excluding drying time) is short, and specifically, it becomes clear when the total processing time is 8 minutes or less, and when the total processing time is 7 minutes or less, it is effective. Furthermore, the difference from conventional processing methods is significant. Therefore, in the present invention, the total treatment time is preferably 8 minutes or less, particularly preferably 7 minutes or less.

In the present invention, the washing water used in the washing step may contain known additives, if necessary.

Among these, there are water softening agents, and aminopolycarboxylic acid compounds can be added as chelating agents.

Specific examples include compounds similar to those mentioned in the color developing solution, with ethylenediaminetetraacetic acid being particularly preferred.

The amount added is lX10-' to 5X10-' mol/i,
Preferably it is lXl0-' to lXl0-'' mol/l.

Furthermore, the aminopolycarboxylic acid compound is not only added and contained, but also contained when the photosensitive material is brought in from a pre-bath such as a fixing bath.

The content at this time is usually 1X10-' to 0.1 mol/step.

However, in such a case, since the above-mentioned compound is not contained in the replenishing solution, dissolution of the electrode member for the liquid level sensor in the replenishing tank is not a problem, but it becomes a problem in the processing tank.

In any case, in the present invention, since a carbon-containing material is used for the electrode member that comes into contact with the washing water containing the aminopolycarboxylic acid compound, troubles due to dissolution of the electrode member do not occur.

In addition, inorganic or organic phosphoric acid or the like can be used as the water softener.

In addition to water softening and hardening agents, the washing water should also contain disinfectants and fungicides (such as isothiazolone, organochlorine disinfectants, benzotriazole, etc.) that prevent the growth of various bacteria and algae, drying loads, A surfactant or the like can be used to prevent unevenness. Or L, E,
West, “Water Quality Cr1t
eria”, Phot, Sci, andEng,,
vol, 9. No, 6. p344-359
(1965) and the like can also be used.

As the stabilizing liquid used in the stabilizing step, a processing liquid that stabilizes the dye image is used. For example, a liquid having a buffering capacity of DH3 to 6, a liquid containing an aldehyde (for example, formalin), etc. can be used.

The stabilizing liquid may contain an aminopolycarboxylic acid compound as a chelating agent, similarly to the washing water.

The specific examples, amount of addition, and bringing in of the sensitive material are the same as in the case of washing water, and the same effects can be obtained.

Furthermore, examples of chelating agents that can be used in combination with the above compounds include 1-hydroxyethylidene-1,1-diphosphonic acid.

In addition, the stabilizing solution may contain ammonium compounds,
Bi, A! Metal compounds such as, optical brighteners, bactericides, fungicides, hardeners, surfactants, alkanolamines, etc. can be used.

Further, the water washing step and the stabilization step are preferably performed by a multistage countercurrent method, and the number of stages is preferably 2 to 4 stages. The amount of replenishment is 1 to 50 times, preferably 2 to 30 times, more preferably 2 to 15 times the amount brought in from the previous bath per unit area.

The water used in these washing steps or stabilization steps includes tap water, as well as Ca
, water that has been deionized to have a Mg concentration of 5 mg/j or less,
It is preferable to use water that has been sterilized using halogen or ultraviolet germicidal lamps.

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 large. It becomes noticeable. 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 of the present invention has at least one silver halide emulsion layer, such as a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer, on the support. There is no particular restriction on the number and order of the silver oxide emulsion layer and the non-light-sensitive layer.A typical example is a support having a plurality of halogens having substantially the same color sensitivity but different light sensitivities. It is a silver halide color photographic light-sensitive material having a light-sensitive layer consisting of a silver emulsion layer, and the light-sensitive layer is a unit light-sensitive layer having sensitivity to blue light, green light, or red light. In silver halide color photographic light-sensitive materials, the unit photosensitive layers are generally arranged in order from the support side: a red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer. Accordingly, even if the above-mentioned order of installation is reversed, the order of installation may be such that different color-sensitive layers are sandwiched between the same color-sensitive layer.

Any of these layer arrangements can be used in the color photosensitive material of the present invention, but in the present invention, the support of the color photosensitive material and the subbing layer and back layer of the support are excluded (
In order to achieve the object of the present invention, it is preferable that the dry film thickness of all the constituent layers is 20.0μ or less, more preferably 1
It is 8.0μ or less. These film thickness regulations are determined by the color developing agent incorporated into these layers of the color photosensitive material during and after processing. By influencing. In particular, the increase in magenta color, 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.

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 50% RH for 7 days after its preparation. First, measure the total thickness of this photosensitive material, then remove the coated layer on the support, measure the thickness again, and use the difference to determine the total thickness of the photosensitive material excluding the support. The film thickness shall be . The thickness can be measured using, for example, a film thickness measuring device using a contact type piezoelectric transducer (Anritus Electric Co., Lt.
d.

K-402B 5tand). Note that the coating layer on the support can be removed using an aqueous sodium hypochlorite solution.

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

Swelling rate of the photosensitive material in the present invention [(25°C, equilibrium swelling film thickness in H, O - dry total film thickness at 25°C, 55% RH/dry total film thickness at 25°C, 55% RH)] X100] is 5
0 to 200% is preferable, and 70 to 150% is more preferable.

If the swelling ratio deviates from the above value, the amount of color developing 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, 3 minutes 15 seconds).
When defined as the swelling rate T1/2, which is the time required to reach a film thickness of 2, it is preferable that T1/2 is 15 seconds or less. More preferably, T1/2 is 9 seconds or less.

As mentioned above, the color photosensitive material used in the present invention is
In such a color photosensitive material, it is preferably a color photosensitive material composed of silver halide containing silver iodide, such as a color negative film for general use or movies, or a color reversal film for slides or television. The preferred silver halide contained in the photographic emulsion layer is silver iodobromide, silver iodochloride, or silver iodochlorobromide, containing from about 0.1 to less than 30 mole percent silver iodide. Particularly preferred is about 2 mol% to about 25 mol%.
Silver iodobromide or silver iodochlorobromide containing silver iodide up to.

In the present invention, it is possible to particularly speed up the desilvering process by using it in the processing of such color photosensitive materials.
The effects of the present invention are exhibited.

Furthermore, in the present invention, color photographic paper may be used as the color photosensitive material, and in the case of color photographic paper, the silver halide contained in the photographic emulsion layer does not substantially contain silver iodide. Those consisting of silver chlorobromide or silver chloride can be preferably used. Here, "substantially free of silver iodide" means that the silver iodide content is 1 mol% or less, preferably 0.2 mol% or less. Regarding the halogen composition of these silver chlorobromide emulsions, any silver bromide/silver chloride emulsion can be used. This ratio can vary widely depending on the purpose, but it means that the silver chloride ratio is 2 mol% or less. Regarding the halogen composition of these silver chlorobromide emulsions, any silver bromide/silver chloride emulsion can be used. This ratio can be set within a wide range depending on the purpose, but those having a silver chloride ratio of 2 mol % or more can be preferably used. For color light-sensitive materials suitable for rapid processing, so-called high silver chloride emulsions with a high silver chloride content are preferably used. The silver chloride content of these high silver chloride emulsions is preferably 90 mol % or more, more preferably 95 mol % or more. Emulsions of nearly pure silver chloride, such as those having a 100% silver chloride content, are also preferably used.

Silver halide grains in photographic emulsions include those with regular crystal shapes such as cubes, octahedrons, and tetradecahedrons, those with irregular crystal shapes such as spherical and plate shapes, and those with twin planes. It may be one having 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).

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 No.
, 17643, same No. 18716 and same No.
307105, 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 three Research Disclosures mentioned above, and the relevant descriptions are shown in the table below.

1 Ihi Naka r Shisotsu Fortress H1 2 Sensitivity increasing agent 4 Brightening agent 5 Anti-capri agent, DiS = Nisu color reinforcement door n Jitae r 4 Sozu Hyakufu ■ Su 6 Piri [Rebinder variable Finished, lubricant 12 Coating aid, surface activated 13 Static prevention finished I) 14 Matte 23 pages 648 pages right column 648 pages right side 24 pages 24-25 pages 647 pages right column 649 pages right column 25 pages 26 pages 26 pages 27 pages 26-27 pages 650 pages left column 651 pages left column 651 pages left column 650 pages right column 65 D page right column 2 section 650 pages right column 866 pages 868 pages 868-870 pages 872 pages 874-875 pages 873- 874 pages 876 pages 875-876 pages 11176-877 pages 878-879 Various color couplers can be used in the present invention, specific examples of which can be found in the above-mentioned Research Disclosure.
(RD) No. 17643, ■-C-G, same No. 30
No. 7105, ■-C-G. As dye-forming couplers, couplers that provide the three primary colors (i.e., yellow, magenta, and cyan) in subtractive color development are important.Specific examples of diffusion-resistant 4-equivalent or 2-equivalent couplers include the aforementioned RD17643, ■-
In addition to the couplers described in the patents C and 0,
The following can be preferably used in the present invention.

Typical examples of yellow couplers that can be used include known oxygen atom elimination type yellow couplers and nitrogen atom elimination type yellow couplers. α
- Pivaloylacetanilide couplers have excellent color fastness, especially light fastness, while α-benzoylacetanilide couplers provide high color density.

Magenta couplers that can be used in the present invention include hydrophobic 5-pyrazolone and pyrazoloazole couplers that have a ballast group. As the 5-pyrazolone coupler, a coupler in which the 3-position is substituted with an arylamino group or an acylamino group is preferable from the viewpoint of the hue and coloring density of the coloring dye.

Cyan couplers that can be used in the present invention include hydrophobic and diffusion-resistant naphthol couplers and phenol couplers, and representative examples include preferably oxygen atom-eliminating two-equivalent naphthol couplers. In addition, couplers that form cyan dyes that are stable against humidity and temperature are preferably used, and a typical example is the one described in U.S. Pat. Phenolic cyan coupler having an alkyl group 2.5-Diacylamino substituted phenolic coupler A phenolic coupler having a phenylureido group at the 2-position and an acylamino group at the 5-position, 5 described in European Patent No. 161626A - Amidonaphthol cyan couplers, etc.

Granularity can be improved by using a coupler in which the coloring dye has an appropriate diffusibility. Specific examples of such couplers include magenta couplers in US Pat. No. 4,366.237, and specific examples of yellow, magenta or cyan couplers in European Patent No. 96,570.

The dye-forming couplers and the special couplers described above may form dimers or more polymers.

Typical examples of polymerized dye-forming couplers are described in, for example, US Pat. No. 3,451,820. Specific examples of polymerized magenta couplers are described in U.S. Patent No. 4.
367.282, etc.

Couplers that release photographically useful residues upon coupling are also preferably used in the present invention. DIR couplers that release development inhibitors include the aforementioned RD17643,
The patented couplers described in sections (1) to (F) are useful.

In the light-sensitive material of the present invention, a coupler that releases a nucleating agent, a development accelerator, or a precursor thereof in an image form during development can be used. Specific examples of such compounds are given in British Patent Nos. 2,097,140 and 2,097,140;
131°188. In addition, DIR redox compound releasing couplers described in JP-A-60-185950 and the like, couplers that release a dye that produces color upon separation as described in European Patent No. 173.302A, etc. can be used.

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods. An example of a high boiling point organic solvent used in the oil-in-water dispersion method is U.S. Pat. No. 2,322,02.
It is stated in issue 7 etc. Further, the process and effects of latex dispersion method as one of the polymer dispersion methods, and specific examples of latex for impregnation are disclosed in U.S. Patent No. 4.199.363.
Dispersion methods using organic solvent-soluble polymers are described in PCT application no.
It is described in the specification of No. 87100492.

Examples of organic solvents used in the above-mentioned oil-in-water dispersion method include phthalic acid alkyl esters (e.g., dibutyl phthalate, dioctyl phthalate), phosphoric acid esters (e.g., diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, dioctyl butyl). phosphates), citric acid esters (e.g. acetyl tributyl citrate), benzoic acid esters (e.g. octyl benzoate), alkylamides (e.g. diethyl laurylamide), fatty acid esters (e.g. dibutoxyethyl succinate, diethyl azelate), trimesic acid esters (e.g. tributyl trimesate), etc., or organic solvents with a boiling point of about 30 to 150°C, e.g. lower alkyl acetates such as ethyl acetate, butyl acetate, ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone, β - Ethoxyethyl acetate, methyl cellosolve acetate, etc. may be used in combination.

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.

Although the processing of color light-sensitive materials has been described above, the present invention can also be applied to the processing of black and white light-sensitive materials.

Therefore, by using a carbon-containing material for the electrode member that comes into contact with a processing solution containing an aminopolycarbonate compound for black-and-white sensitive materials, troubles caused by dissolution of the electrode member can be eliminated. Specifically, the effect on photographic performance is to prevent an increase in development fog when the processing liquid is a developer, and to prevent the occurrence of staining over time when other processing liquids are used.

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

Example 1 On a subbed cellulose triacetate film support,
Sample 101, which is 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, for silver halides, colloidal silver and couplers, g/ of silver,! The quantity expressed in units,
The sensitizing dyes are expressed in mole units 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: Black colloidal silver gelatin V-1 V-2 pa-i olv-I olv-2 olv-3 Silver coating amount 0.20 1.90 0.10 0.20 0.05 0. 01 0.01 O2O3 (2,0) 2nd layer: Intermediate layer fine grain silver bromide (equivalent sphere diameter 0.07μ) Silver coating amount 0.15 Gelatin 0.90Cp d
-20,20 (0,9) Third layer: First red-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%,
(Tedecahedral 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-'Mole Ex S-3o, gx 1o-'
Mol Ex C-40,6X 10-'Mole ExC-
10,33 ExC-20,009 ExC-30,028 ExC-60,14 4th layer: 2nd red-sensitive emulsion layer Silver iodobromide emulsion (AgI 16 mol%, internal high AgI type, sphere equivalent) Diameter 1.0 μ, coefficient of variation of equivalent sphere diameter 25%, plate-like particles, diameter/thickness ratio 4.0) Gelatin xS-I xS-2 xS-3 xS-4 xC-3 xC-4 xC-6 Silver coating Amount 0.80 1.20 4, OX 10-' mole 1.5X 10-' mole 0.4X 10-' mole 0.4X 10-' mole 0.05 0.10 0.08 (1,41 5th Layer: Third 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) Gelatin xS-I xS-2 xS-3 xC-4 xC-5 olv-I olv-2 Silver coating amount 1.10 1.00 2.5X 10-' mol 0.7X 10-' mole 0.3X 10-' mole 0.07 0.06 0.12 0.12 (1,41 ) 7th layer: 1st 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%,
(Tedecahedral grains) Silver coating amount 0.20 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 0.10 Gelatin 1.30E x S
-55X 10-'mol ExM-62x 10-'molExM-10,21 ExM-60,31 ExM-20,10 ExM-50,03 S o 1 v -10 ,20 S o l v -50,03 8th layer: 2nd green-sensitive emulsion layer Silver iodobromide emulsion (Ag1 10 mol%, internal high iodine type, equivalent sphere diameter 1.0μ, coefficient of variation of equivalent sphere diameter 25 %, plate-shaped particles, diameter/thickness ratio 3.0) Gelatin xS-5 xS-6 xS-7 xM-I xM-3 olv-I olv-5 Silver coating amount 0.50 0.45 4, 5X 10” 'Mole 1.8X 10-'Mole 0.9X 10-'Mole 0.09 0.01 0.15 0.03 (0,8) 9th layer: Intermediate layer gelatin 0.50 (0,4) 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) Gelatin xS-5 xS-6 xS-7 xM-3 xM-4 xM-I xC-4 olv-1 Silver coating amount 1.20 1.20 2.4X 10 -' mol 1, OX 10-' mol 1, OX 10-' mol 0.01 0.14 0.04 0, 005 0.2 (1,6) 11th layer: Yellow filter layer pd-3 Gelatin olv- 1 12th layer: Intermediate layer gelatin pd-2 0,05 0,50 0,1O (0,5) 0.05 0.10 (0,5) 13th layer: 1st blue-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%,
(Tedecahedral grains) Silver coating amount 0.15 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 0.08 Gelatin ExS-8 xY-I xY-2 olv-1 1,00 4,5X 10-'mol 0.62 0.02 0.20 (1,71 14th layer: Second blue-sensitive emulsion layer Silver iodobromide emulsion (AgI 19.0 mol%, internal high Ag
Type I, equivalent sphere diameter 1.0 μ, coefficient of variation of equivalent sphere diameter 16%,
Tedecahedral particles) Silver coating amount 0.80 Gelatin 0.30E x S
-83,OX 10-'molExY-10,22S o 1v -10,07 (0,7) 15th layer: 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: Third 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) Silver coating amount 1.20 Gelatin 0.80E x S
-81,8 10 0,20 0,01 0,01 (1,51 V-2 18th layer: 2nd protective layer fine grain silver iodobromide (equivalent sphere diameter 0.07μ) Silver coating amount 0.
18 Gelatin 0.90 Polymethyl methacrylate particles (diameter 1.5μ) 0.20 W-10,20 H-10,40 Cp d -51,00 (2,0) xM-3 ExC-1 ExC- 2 ExC-3 n■ xM-1 xM-2 ~aUsb ExC-4 ExC-5 ExC-6 xM-4 xM-5 xM-6 YoC+Jis ExY-1 ExY-2 xS-1 xS-6 xS-7 xS -8 olv-1 olv-2 Js xS-2 xS-3 xS-4 xS-5 olv-3 olv-5 pd-1 pd-2 l UI′I pa-3 C2H.

Cabinet C2H.

Cpd-4 cpa-s -1 C, F, , SO, NI (C82012 part 2 ■ blade 2 CH
-N Responsibility α, ) 3 Cut the above sample 101 into a width of 35a+i.
After processing and imagewise exposure, continuous processing was carried out using an automatic processor for 50 days at a throughput of 30 m of sensitive material per day according to the following processing steps.

Treatment process Treatment time Treatment temperature Replenishment amount °
Tank capacity color development 2 minutes 3 sounds 38℃
20m1 1ON bleach 258
) 38℃ 4.5a+l 4
j bleach constant 14 mj 38℃ 4j constant W 0 seconds 38℃ 14mj
4j Washing with water (1) 3 Zheng 38℃
21 Washing (2) 20e 3
8℃ 30mj 21 stable
2) 38℃ 21) mj 21 Drying 1 minute 55℃ *Replenishment amount is 1012” per 35mm width and 1m length C) I SO2LJit LJJN H-
L, 112 water washing was carried out in a countercurrent manner from (2) to (1), and all overflows from each of the bleaching tank and fixing tank were allowed to flow into the bleaching and fixing tank. In addition, all the overflow from the paddle of water washing (1) was allowed to flow into the fixing tank.

The bleaching tank, bleach-fixing tank, and fixing tank each had an aperture ratio of 0.02.

The composition of the treatment liquid is shown below.

(Color developer) Mother solution (g) Replenisher (g) Diethylenetriaminepentaacetic acid 1.0 1.11-Hydroxyethylidene 1.1-diphosphonic acid 3.0 3.2 Sodium sulfite 4.0 4.9 Potassium carbonate 30.0 30.0 Potassium Bromide
1.4 Potassium Iodide 1.5+og Hydroxylamine Sulfate 2.4
3. Add 62-methyl-4-[N-ethyl-N-(β-hydroxyethyl)aminocoaniline sulfate solution and u (bleach solution) 1.3-Propylenediaminetetraacetic acid ferric ammonium hydrate ammonia Water (28%) Ammonium bromide Ammonium nitrate Hydroxyacetic acid Acetic acid (98%) Add water to pH [Adjust with jetanolamine] 4.5 1.0j 10, [l15 Mother liquor (g) 138.0 3.4 80. 0 20.0 50.0 50.0 1, Oi 3.3 6.0 1.01 10.15 Replenisher (g) 207.0 5.1 12Q, 0 30.0 75.0 75.0 1, Oj 2.8 (Fixer) Mother liquor (g) Replenisher (g) Ethylenediaminetetraacetic acid ammonium salt 12.0 36 Ammonium sulfite 20.0 60 Imidazole
3090 Ammonium thiosulfate aqueous solution f700g/j) 2g0. Omj
Add 840mj water 1. Oj
1.0j pH 7,47,45 (bleach-fix solution) <Mother liquor> Prepared by mixing a bleach solution and a fix solution at a ratio of 1=8 (volume) (pH 6, 8).

(Washing water) Mother liquor and replenisher common tap water was mixed with H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) and OH-type strongly basic anion exchange resin (Amberlite IRA-4 manufactured by Rohm and Haas).
Water was passed through a mixed bed column packed with 00) to reduce the concentration of calcium and magnesium ions to 3 mg # or less,
followed by sodium incyanurate dichloride 20 mg/
J and 150 rag/l of sodium sulfate were added.
The pH of this liquid was in the range of 6.5 to 7.5.

(Stabilizing solution) Common to mother solution and replenisher solution (unit: g) Formalin (37%) 2.1) ++j Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.3 Ethylenediaminetetraacetic acid disodium salt 0. 05 Add water
1.0ApH5.8~8.0 The automatic developing machine has a tank capacity of 12 for replenishing each processing solution.
A β replenishment tank is installed, and 10ρ of replenishment liquid is prepared each time.

In this case, each replenishment tank is equipped with a liquid level sensor, as in the replenishment tank shown in FIG.
However, the electrode member of the liquid level sensor is made of stainless steel (
It is made of SUS316) and has two electrodes (10+o+aX
10 x 1 mm) on the same tank wall with a gap of 1
They are fixed at the same height position with a distance of 0 cm (distance between center positions), and are configured to detect the presence or absence of the replenisher by detecting the electrical resistance between the electrodes.

The electrical resistance is detected by applying a measurement voltage of 12 V for 1 second at intervals of 5 minutes to measure the change in resistance.

Further, each processing tank is provided with a sub-tank, and as shown in FIG. 1, a grounding rod is provided within this sub-tank. However, this ground rod is made of stainless steel (SUS316).

Note that the electrode members of this automatic developing machine are only the above-mentioned liquid level sensor and a grounding rod.

This is called a conventional automatic processor.

First, before performing the actual continuous processing, the following test processing was performed.

(1) The above-mentioned conventional processor was modified to remove the grounding rod. Furthermore, only the liquid level sensor for the replenishment tank for the bleach solution was left, and the rest were removed, and continuous processing was performed using this under the above processing conditions. Test this 1
shall be.

Further, in Test 1, the material of the liquid level sensor was changed to special carbon material T-6, and other treatments were carried out in the same manner. This is called test 2.

Further, in Test 1, a liquid level sensor made of 5US316 was installed in each replenishment tank for the fixing liquid, washing water, and stabilizing liquid, and the other processes were the same as in Test 3.

Furthermore, in Test 2, a liquid level sensor made of special carbon material T-6 was installed in each replenishment tank for constant @ liquid, washing water, and stabilizing liquid, and the other treatments were the same as in Test 4. shall be.

The storage stability of these samples was evaluated as follows.

After measuring the magenta transmission density of the unexposed area of each sample of the Ho1takui22 finish treatment agent using a photographic densitometer FSD103 manufactured by Fuji Photo Film Co., Ltd., it was measured at 60°C and relative humidity of 70%. The concentration was measured again after one week.

The storage stability was evaluated by determining the concentration increase (ΔD) over time.

The results are shown in Table 1.

Table 1 Test level sensor ΔD1
Stainless steel (bleached) 0.1
32 Carbon (bleaching) 0.023
Stainless steel (bleached, fixed, 0.24
(washed with water, stable) 4 carbon (bleached, fixed, washed with 0.02 water, stable) (2) As in Tests 1 to 4, an automatic processor with the earth rod removed was used. In this automatic processing machine, a liquid level sensor made of 5U8316 was installed only in the replenishment tank for the color developer, and the same process was carried out. This is called test 5. In Test 5, the same process was carried out except that the material of the liquid level sensor was special carbon material T-6.
This is called Testro.

In addition, in Test 5.6, the same process was carried out except that diethylenetriaminepentaacetic acid was not added to the color developer mother liquor and replenisher. Test this in order 7
．． 8.

Regarding these, the storage stability (ΔD) was examined in the same manner as above, and the yellow density (ΔD, . . .) was evaluated as follows.

Yellow' △DF11 Measure the yellow density of each sample immediately after treatment, and use the one in test 2 as the standard value, and calculate the difference (ΔD□)
I asked for

The results are shown in Table 2.

Table 2 Test level sensor Aminopolycarboxylic acid
Δ DFll △ D5 Stainless steel
A ri 0.11 0.
106 Carbon present 0.0
0 0.027 Stainless steel
0.01 0.028 Charcoal
Plain None 0.01 0.02 In Test 7.8, a white precipitate was generated in the color developing solution, which caused a problem in the stability of the solution.

The above results show that only when a carbon-containing material is used as the material for the level sensor electrode, the stability of the processing liquid can be ensured in the presence of aminopolycarboxylic acid and good photographic performance can be obtained.

Next, using the conventional automatic processor described above, 50
Continuous treatment was carried out for several days.

This is called processing IA.

In process IA, process IB is a process in which the liquid level sensor and ground rod of an automatic developing machine are all made of special carbon material T-6 (manufactured by IBIDEN ■) (see FIG. 1).

In processing IA, all liquid level sensors and grounding rods are made of special carbon material T-6 (manufactured by IBIDEN ■), except for the liquid level sensor of the replenishment tank for the color developer of the automatic processor and the grounding rod in the sub-tank. Processing using this is called a processing IC.

In process IA, process ID is a process in which only the liquid level sensor for the color developer of the automatic processor and the earth rod are made of special carbon material T-6 (manufactured by IBIDEN ■).

In process IA, process IE is a process in which only the liquid level sensor for the bleaching solution of the automatic processor and the ground rod are made of special carbon material T-6 (manufactured by IBIDEN ■).

In each of the above treatments IA to IE, the storage stability (Δ'D) and yellow density (ΔD F,) were examined in the same manner as above using each sample at the end of the continuous treatment.

The results are shown in Table 3.

In addition, in the table, △D and ΔD78 are respectively ○
, Δ, and ×, which comply with the following criteria.

l Rising ○...ΔD is 0.03 or less (good storage stability) △...Δ
D is 0.04 to 0.07 (slightly poor storage) ×...△D is 0.08 or more (poor storage) L and Uni 1
1 0...ΔDF+t is 0.03 or less (no fog) △・
...ΔD Fll is 0.04 to 0.07 (slight fogging) ×...ΔD Fll is 0.08 or more (severe fogging) Table 3
From the results, it can be seen that only the process IB of the present invention enables liquid level detection and grounding while maintaining good photographic performance.

This corresponds to the result of the test process described above.

In addition, in the above processing, if a color developer, fixer, and stabilizer without the addition of an aminopolycarboxylic acid compound as a chelating agent are used, a white precipitate will form as in the case of the color developer in the test process. A problem has arisen.

Incidentally, in the above processing, the washing water is not added with an aminopolycarboxylic acid compound, but due to the bringing in of the sensitive material, the amount of the above compound contained in the washing water in the first washing tank is in the running equilibrium state. It was about 4×10-” mole/j.

Example 2 Sample 201, which is a multilayer color photographic paper having the layer structure shown below, was prepared on a paper support laminated on both sides with polyethylene. The coating solution was prepared as follows.

” = 1 Yellow coupler (ExY) 19.1g, color image stabilizer (Cpd-1) 4.4g and color image stabilizer (Cpd-1)
7) Add 27.2 cc of ethyl acetate and solvent (S
Add and dissolve 8.2g of olv-1), and dilute this solution to 10%
1 containing 8 cc of sodium dodecylbenzenesulfonate
It was emulsified and dispersed in 185 cc of 0% gelatin aqueous solution.

-Force-field silver bromide emulsion (cubic; average grain size 0.88-
A 3-nea mixture (silver molar ratio) of 0.70- and 0.70-. The coefficient of variation of particle size distribution is 0.08 and 0.10.
; Each emulsion contains 0.2 mol % of silver bromide locally on the grain surface), and the following blue-sensitive sensitizing dyes are added per mol of silver, 2.0 x 10-' mol for large emulsions. ,
For small size emulsions, 2.5X10-
A sample was prepared in which sulfur sensitization was carried out after adding 'mol.
The above emulsified dispersion and this emulsion were mixed and dissolved to prepare a first coating solution having the composition shown below.

Coating solutions for the second to seventh layers were also prepared in the same manner as the coating solution for the first layer. The gelatin hardening agent for each layer is 1-
Oxy-3,5-dichloro-S-triazine sodium salt was used.

The following spectral sensitizing dyes were used in each layer.

Blue-sensitive emulsion layer Green-sensitive emulsion layer (4.0XIO-' moles each for large size emulsions and 5.6X10-' moles for small size emulsions per mole of silver halide) and (halogenated 2.0X10-' moles each for large size emulsions and 2.5X10-' moles each for small size emulsions per mole of silver (per mole of silver halide for large size emulsions) are each 7.0X10-' mole,
and 1.0 x 10-' mol for small-sized emulsions) red-sensitive emulsion layer (per 1 mol of silver halide, respectively 0.9 x 1 O-' mol for dog-sized emulsions; For the red-sensitive emulsion layer, the following compound was added in an amount of 2.6 x 10-'' mol per mol of silver halide.

7.7 x 10-' moles, 2.5 x lO-' moles were added.

Also, 4-hydroxy-6-methyl-1,3,3a for the blue-sensitive emulsion layer and the green-sensitive emulsion layer.

1X10-' mol and 2X10-' mol of 7-chitrazaindene were added per mol of silver halide, respectively.

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

In addition, 1-(5-methylureidophenyl)-5-mercaptotetrazole was added to each of the blue-sensitive emulsion layer, green-sensitive emulsion layer, and red-sensitive emulsion layer at a concentration of 8% per mole of silver halide.
．． 5X10-'Mo and (Layer Structure) The composition of each layer is shown below. The number indicates the coating amount (g/m''). Silver halide emulsion indicates the coating amount in terms of silver.

Support polyethylene laminate paper [The polyethylene on the first layer side contains a white pigment (TiOa) and a blue-tinged dye (ulmarine blue)] -th layer (blue-sensitive layer) Said silver chlorobromide emulsion 0.30 Gelatin 1.86 Yellow Coupler (ExY) 0.82 color image stabilizer (Cpd
-1) 0.19 solvent (Solv-L
) 0.35 color image stabilizer (Cpd
-7) 0.06 Second layer (color mixing prevention layer) Gelatin 0.99 Color mixing prevention layer agent (Cpd-5) 0.08 Solvent (S
olv-1) 0.16 solvent fs
olv-4) 0.08 third layer (
Green sensitive layer) Silver chlorobromide emulsion (cubic; 1=3 mixture (Ag molar ratio) of one with an average grain size of 0.554 and one with an average grain size of 0.39-. The coefficient of variation of grain size distribution is 0.10 and 0.08
．． Each emulsion contained 0.8 mol% of AgBr locally on the grain surface) 0.12 Gelatin 1.24 Magenta power puller ExM) 0.20 Color image stabilizer (Cp
d-2) 0.03 color image stabilizer (Cp
d-3) 0.15 color image stabilizer (Cp
d-40,02 Color image stabilizer (Cpd-9) 0.02
Solvent (Solv-2) 0.40
Fourth layer (ultraviolet absorption layer) Gelatin 1.58 Ultraviolet absorber (UV-1) 0.47 Color mixing inhibitor (Cpd-5) 0.05 Solvent (So
lv-5) 0.24 Fifth layer (red sensitive layer) Silver chlorobromide emulsion (cubic; 1=4 mixture of average grain size of 0.58- and 0.45-) (Ag molar ratio ). The coefficient of variation of particle size distribution is 0.09 and 0.11.
0.23 Gelatin 1.34 Cyan coupler (ExC) 0.32 Color image stabilizer (C
pd-6) 0.17 color image stabilizer (C
pd-7) o, 40 color image stabilizer (
Cpd-8) 0.04 Solvent (Sol
v-6) 0.15 6th layer (ultraviolet absorption layer) Gelatin 0.53 ultraviolet absorber (UV-1) 0.16 color mixture prevention agent (
Cpd-5) 0.02 Solvent (Sol
v-5) 0.08 Seventh layer (protective layer) Acrylic modified copolymer of gelatin polyvinyl alcohol (degree of modification 17%) Liquid paraffin (ExY) 1.1 mixture with yellow coupler (mole ratio) 1.33 0.17 0.03 (ExM) M, zenta coupler - (ExC) 2+4:4 mixture by weight of cyan coupler and R=C, H, and C4He, respectively (Cpd-1) 1=1 with color image stabilizer Mixture (molar ratio) (Cpd-2) Color image stabilizer 1 (cpa 3) Color image stabilizer (Cpd-4) Color image stabilizer (Cpd-5) Color mixture prevention agent (Cpd 9) Color image stabilizer (UV -1) 4:2:4 mixture of UV absorbers (Solv-1) Solvent (Cpd-6') 2:4:4 mixture of color image stabilizers (Cpd-7) Color image stabilizer (Cpd- 8) 1:l mixture of color image stabilizer nμ (Solv-2) 2:1 mixture (volume ratio) of solvent (Solv-4) solvent (Solv-5) solvent CDDC,H,.

(Solv-6) Solvent After the sample 201 was imagewise exposed, it was continuously processed for 30 days at a processing rate of 61 per day using the following processing steps and processing composition using an automatic paper processor.

Explosive L1 Company Color development 38℃ Bleach constant @ 30-36℃ Stable■　3t 37℃ Stable■　3[)-37℃ Stable■　3()-37℃ Dry 7 to 85℃ *Replenishment amount is per 1m” (3-tank countercurrent flow method from stable ■ to ■) 5mj review of poems 4th floor 4 呵小　　215a+j 2 liters in seconds 2m less 364111j 60f small The composition of each treatment liquid is as follows.

Water ethylene diamine tetraphosphonic acid diethylene triamine pentaacetic acid 1-hydroxyethylidene 1.1-diphosphonic acid triethanolamine potassium chloride potassium bromide potassium carbonate N-ethyl-N-(β-methanesulfonamidoethyl)-3-methyl-4 = Aminoaniline sulfate hydrazinoniacetic acid 800 mj 800 mA 9.4g 9.4g 3.0g 3.0g 0.6g 11.6g 5.0g 0.02g 5g 0.6g 11.6g 5g 5.0g 12.0g 0 .04mol 0.06mol Sodium sulfite 0.1g 0.2g
Fluorescent brightener (Sumitomo Chemical WHITEX-4) 1.0g Add 3.5g water 10100O1000mjp10
0O℃) 10.00 10.8On
(Tank fluid and refill fluid are the same) Water
400mj amnium thiosulfate (70%) 1
00mj Sodium sulfite 17g Ethylenediaminetetraacetate Iron(III) Ammonium 55g Ethylenediaminetetraacetate Ninatrilum 5g Glacial acetic acid
Add 9g water
1000mjp100℃)
5.40Ll! (Tank fluid and replenisher fluid are the same) Formalin (37%) 0.1g Ethylenediaminetetraacetic acid 0.2g Formalin-sulfite adduct 0.7g 5-chloro-2-methyl-4-idithiazolin-3-one 0. 02g 2-Methyl-4-inchazolin-3-one 0.01g Copper sulfate
0.005g ammonia water (28%) Add 2.0g water
1000mjp1000℃) 4.0 In addition, in the above-mentioned automatic processor, color developing solution, bleach-fixing solution,
When the stabilizing liquid was treated in the same manner as in Processes IA to IE of Example 1 using a liquid level sensor and a grounding rod, the same results as in Example 1 were obtained.

<Effects of the Invention> According to the present invention, in the treatment using a stable treatment liquid containing an aminopolycarboxylic acid compound, there is no problem of dissolution even if the treatment liquid and the electrode member come into contact with each other during long-term continuous treatment. It is possible to obtain images with excellent photographic performance such as image storage stability.

[Brief explanation of drawings]

FIG. 1 is a schematic configuration diagram showing an example of the configuration of a processing device of the present invention. Explanation of symbols 1... Processing device 11... Processing tank 12... Sub tank 13... Replenishment tank 21... Heater 25... Earth electrode 35... Liquid level sensor request doujin Fuji Photo Film Hito Co., Ltd. Patent Attorney Yo Ishii

Claims (3)

[Claims] (1) When photographically processing a silver halide photographic light-sensitive material after exposure using a predetermined processing liquid, an electrode member that comes into contact with a processing liquid containing an aminopolycarboxylic acid compound among the processing liquids contains carbon. 1. A method for processing a silver halide photographic material, the method comprising using a silver halide photographic material to prevent deterioration of photographic properties. (2) A processing apparatus for a silver halide photographic light-sensitive material, in which a sensor having a sensing electrode member is disposed at a position in contact with a processing solution containing an aminopolycarboxylic acid compound stored therein, the sensing electrode member being a carbon 1. A processing device for a silver halide photographic material, characterized in that it is formed from a containing material. (3) A processing apparatus for silver halide photographic materials, in which a ground electrode is disposed at a position in contact with a processing solution containing an aminopolycarboxylic acid compound stored therein, wherein the ground electrode member is formed from a carbon-containing material. A processing apparatus for silver halide photographic materials, characterized in that: