JPS63129343A - Development of silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To reduce the amt. of waste liquid in the development of silver halide photographic sensitive material by replenishing antimolded water to a washing tank or a stabilizing tank, and utilizing the overflowed liquid of the washing tank or the stabilizing tank for the diluting liquid of concd. fixing liquid. CONSTITUTION:The stock water treated by an antimolding means and stored in a stock tank 4 is utilized as diluting water of concd. developing liquid, and utilized at the same time as replenishing water for washing water or stabilizing water in the washing treatment requiring <=3l, pref. 50ml-1l water per 1m<2> photosensitive material. Both of the diluting water for development and the replenishing water for washing are supplied from a same stock tank. A part or whole of the overflowed liquid of the washing water contg. the stock water for replenishment is transported to a fixing liquid tank 2 and utilized further as diluting water of concd. fixing liquid. The replenishment and transportation of the stock water and the concd. treated liquid are preferably performed automatically as the progress of the treatment of the photosensitive material. By this method, the waste washing water is utilized effectively, and diluting water for fixing liquid is saved at the same time.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a method for developing silver halide photographic materials using an automatic processor.

(Prior art and its problems) Conventionally, when developing and fixing (or bleaching and fixing) silver halide photographic materials using an automatic processor, the components of the processing solution have negative effects on each other! # Multiple stock drugs that do not interact with each other, e-
When used, multiple chemical parts are mixed manually or automatically, diluted with water, and stored as developer and fixer in stock tanks attached to automatic processors. A method has been adopted in which the diluted processing solution is directly supplied as the photosensitive material is processed.However, it is cumbersome to mix multiple chemicals and put them into a stock tank. It takes time and effort.

Furthermore, since the processing solution is already diluted, the capacity of the stock tank must necessarily be large, which requires a considerable amount of space, and the diluted processing solution is susceptible to oxidative deterioration. There is a problem that there is a limit to long-term storage, and the processing solution must be replaced within a certain period of time in order to maintain photographic performance.

In order to solve one of the drawbacks of multiple chemicals as described above, a method is also known in which the number of shaving agents is reduced to reduce the effort of mixing the stock solution of the treatment liquid as only one agent. However, as in the case of multiple drugs, it must be diluted with water, so even if the stock solution is only one drug, as long as it is stored in a diluted state in the stock tank of an automatic processor, some of it may be The problem of oxidative deterioration could not be solved at all.

On the other hand, a method is also known in which the stock solution of the processing solution is diluted in advance and stored in a stock tank, but the solution is mixed and diluted with water immediately before use and then replenished into the processing tank.

However, in order to avoid adverse effects on photographic properties, finish, etc., it has been necessary to supply fresh water to the processing solution as solution dilution water. Therefore, the installation conditions for automatic processors are restricted due to the need for piping to lead tap water directly to the automatic processor, and even if dilution water is stored in a stock tank attached to the automatic processor, freshness cannot be maintained. In order to maintain this level, it was necessary to perform complicated operations such as changing the dilution water very frequently and constantly cleaning the water.

On the other hand, in the development process of silver halide photographic materials,
In the washing or stabilization treatment performed after development and fixing (or bleaching/fixing), there are known techniques for adding various antibacterial agents to the washing water or stabilizing solution in order to prevent the formation of limescale, etc. There is. In particular, the use of such antibacterial agents is very important when performing water-saving treatments such as additional flushing and extremely low-volume replenishment flushing, which have recently been in high demand from the viewpoint of environmental protection, energy saving, and speeding up of processing. However, conventionally, washing water (
At least two types of water, one for (or stabilizing liquid) and one for liquid preparation dilution water, were each used separately. This is very complicated and requires a large space, and it also requires piping to lead tap water to the automatic processor, which is a big constraint as the automatic processor cannot be operated anytime and anywhere. .

Furthermore, there is a need for an automatic processing method incorporating a system that can automatically prepare developing and fixing solutions.

On the other hand, issues of environmental conservation and conservation of silver resources are emphasized, and reduction of pollution caused by waste liquid and recovery of silver from washing water are strongly desired.

For this purpose, various methods have been proposed not only for recovering silver from the waste liquid of the processing solution, but also for recovering silver from the waste liquid of washing water. For example, the electrolytic method is described in West German Patent Application No. 2,532,018 and others, the metal substitution method is described in Japanese Patent Application Laid-Open No. 50-18318 and others, the chemical precipitation method is described in Japanese Patent Application Publication No. 53-76029 and others, and the microbial method is described in Japanese Patent Application Publication No. 53-59254. A precipitation method is disclosed. However, even when these methods are used, the concentration of soluble silver salts in the washing water waste liquid is diluted and the recovery efficiency is low.

Therefore, the first object of the present invention is to prepare a developer and a fixer,
There is no need for complicated work such as changing dilution water or cleaning stock tanks, and the stability of the developer and fixer is excellent.Furthermore, in automatic processors, there is no need for tap water piping or large space, so installation conditions are limited. It is an object of the present invention to provide a method for developing a silver halide photographic light-sensitive material.

A second object of the present invention is to share the washing water or stabilizing solution with the developer and/or fixer diluent water, thereby making it possible to save water such as washing with a very small amount of water as a tank. It is an object of the present invention to provide a method for developing a silver halide photographic light-sensitive material, which provides good stability of a developer and a fixer and good photographic performance.

A third object of the present invention is to provide a development processing method that reduces the amount of water used, that is, reduces the amount of waste liquid, and allows almost complete recovery of silver.

(Means for Solving the Problems) An object of the present invention is to develop, fix and wash silver halide photographic materials using an automatic developing machine equipped with a stock tank containing water treated with anti-mildew means. Alternatively, in a stabilizing method, a concentrated developer and water treated with the anti-mildew means are transferred to a developer tank, a concentrated fixer is transferred to a fixer tank, and the anti-mildew solution is transferred to the photosensitive material 1 - 3 liters or less of the anti-mildew material. A developing method characterized by replenishing a washing or stabilizing tank with the water treated with the method, and transferring part or all of the overflow liquid from the washing or stabilizing tank to a fixing tank and using it as a diluent for the concentrated fixer. This is achieved through a processing method.

In the present invention, the stock tank is treated with anti-mold means and the log water (hereinafter referred to as stock water) is used as dilution water for the T-concentrated developer, and at the same time, water is saved at 3 liters or less, preferably 50 to 11 liters, per one photosensitive material. It is used as a replenisher for washing water or stabilizing liquid (hereinafter simply referred to as washing water unless otherwise specified) in washing treatment. Preferably, the developer dilution water and the washing water replenisher are supplied from the same stock tank. Therefore, the core and stock water are treated with anti-mold measures, and can be stored in the stock tank without adversely affecting photographic performance or causing water stains. Since it can be used in common with a replenisher, the automatic developing machine can be simplified and further made more compact.

Further, in the present invention, part or all of the overflow liquid of the washing water supplemented with the stock water is transferred to the fixing liquid tank and further used as dilution water for the concentrated fixing liquid. The term "fixer" as used herein means a solution having a fixing ability, and specifically includes not only a fixer but also a bleach-fixer and the like. The concentrated fixer of the present invention preferably contains thiosulfate in an amount of 2 mol/1 or more.

According to the present invention, by diverting part or all of the overflow of the washing water as dilution water for the concentrated fixer, and moreover, as dilution water immediately before use in the automatic developing machine, it is possible to effectively utilize the washing water waste. At the same time, it is possible to save or eliminate dilution water for the fixer. Furthermore, the recovery rate of silver in the waste liquid from the fixer is also improved.

By adopting the method of the present invention in an automatic processor, it is possible to simplify and downsize the automatic processor, further save water, and improve the recovery rate of silver in waste liquid. In other words, it becomes possible to develop a silver halide photographic material development processing system that achieves the following, which eliminates the need for artificial liquid preparation work.

Therefore, in the present invention, it is preferable that stock water and concentrated processing liquid be replenished and transferred automatically as the photosensitive material is processed. It is preferable that the solution and the concentrated fixer are each not made up of two or more parts, but are one part.For this purpose, the photosensitive material should be sufficiently coated before processing so that there is little need for hardening during the development process. It is desirable that the membrane is hardened.

The anti-mold means for stock water in the present invention is that stock water has an adverse effect on developing and fixing performance 'J'? Although there are no particular limitations as long as the quality of the processed photosensitive material obtained can be maintained well without applying any additives, it is preferable to use ultraviolet irradiation, magnetic field irradiation, ion exchange, addition of antifungal agents, etc. One type or a combination thereof.

More preferred is the addition of an antifungal agent, which will be described later.

Magnetic field irradiation refers to passing washing water and dilution water through a magnetic field generated between a positive pole and a negative pole of a magnetic field.

The magnetic field can be obtained by using a permanent magnet made of ferromagnetic materials such as iron, cobalt, and nickel, or by passing a direct current through a coil, but is not particularly limited. All possible means can be used. In addition, the magnetic field may be 5 Kt so that lines of magnetic force are formed using one magnet, or it may be 5Kt where lines of magnetic force are formed between the opposing magnets by arranging two magnets (positive and negative poles) facing each other.

The method of passing the rinsing water and dilution water through a magnetic field is to use a permanent magnet that forms a magnetic field and move (including rotation) a permanent magnet installed in the water stock tank and/or outside the liquid.
Alternatively, there are methods such as moving the water by stirring or circulating the water. A particularly desirable method is to fix a permanent magnet to a part or all of the inside or outside of a circulation system pipe and circulate water.

The method of irradiating the washing water and dilution water with ultraviolet rays is carried out using a generally commercially available ultraviolet lamp or ultraviolet irradiation device, and preferably the output of the ultraviolet lamp is 5 W to s.
oow (tube output) is preferable, but is not limited to this. According to a preferred embodiment of the present invention, the wavelength of the ultraviolet rays is in the range of 220 nm to 35 Q nm.

The ion exchange resin treatment method involves passing water through a mixed bed column filled with a commercially available H-type strongly acidic cation exchange resin and an OH-type strongly basic exchange resin to significantly remove calcium and magnesium ions in the water. This is the way to do it.

A similar method includes using distilled water as the washing water and dilution water of the present invention.

Regarding the method using ultraviolet rays (for example, JP-A-60-2
63939, for example, Japanese Patent Application Laid-Open No. 60-263940 for a method using a magnetic field, and Japanese Patent Application No. 61-1 for a method using an ion exchange resin.
It is described in detail in the specification of No. 3l632.

Any antifungal agent known for photography can be used, but preferably it is a compound that does not have an adverse effect on the development process, specifically aminopolycarboxylic acids, phosphonic acids, etc. Specific examples of aminopolycarboxylic acids include ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid, and ethylenediamine-N-(β-oxyethyl).
-N.

N/, N/-triacetic acid, propylenediaminetetraacetic acid,
Nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, iminodiacetic acid, alkylaminoniacetic acid, dihythyl 90xethylglycine, ethyl ether diamine tetraacetic acid, glycol ether diamine tetraacetic acid, ethylenediamine tetrapropionic acid, phenylene diamine tetraacetic acid, 1,3 -Diamino-2-propatoltetraacetic acid, triethylenetetraminewood acetic acid, hydroxyethylimino vinegar f! ! , oxybis (
These include ethyleneoxynitrilo)tetraacetic acid, rinsic acid, and the sodium salts and potassium salts of these polycarboxylic acids.

As specific examples of the phosphonic acids, compounds represented by the following general formulas (IJ to (IV)) are preferred.

General formula CI) General formula (n) General formula (III) R,, N(CH2PO3M2) 2 General formula (IV) 1-0.1.2 In the formula, R1-R6 are a hydrogen atom, a hydroxyl group, an alkyl group (1 to 3 carbon atoms, e.g. methyl group, ethyl group, propyl group, etc.), amino group, alkoxy group (1 to 3 carbon atoms, such as methyl group, ethyl group, propyl group, etc.)
3), for example, methoxy group, ethoxy group, etc.), alkylamino group (preferably having 1 to 3 carbon atoms), arylamino group (preferably having 6 to 8 carbon atoms), aryloxy group (preferably having 6 carbon atoms), ~8).

R7-R13 are hydrogen atoms, human 90xyl groups, -CO
OM, -PO3M2, represents an alkyl group (having 1 to 3 carbon atoms, such as a methyl group, an ethyl group, a propyl group, etc.).

R14 represents a hydrogen atom or an alkyl group (having 1 to 3 carbon atoms, such as a methyl group, an ethyl group, a propyl group, etc.), and M represents an alkali metal such as a sodium atom or a potassium atom.

Specific compounds represented by the above general formulas (1) to -general formula IV) include the following.

Compound (1) Compound (2) Compound (3) Compound (4) CH2COONa C-CH3 ■ CH3-C-C00N a 03Na2 Compound (5) CH2COOH CH2 HOOCCH-C-Co○H 03H2 Compound (6) CF2COOH ■ Compound ( 7) CH2-Co○H ■ HOOC-C-PO3H2 CH2 CH2COOH Compound (8) Compound (9) Compound C1l Compound aυ Compound (12 Compound 03 These compounds are added in the form of sodium salt and/or potassium salt Good.

Particularly preferred among these compounds are ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid, and ethylenediamine-N-hydroxyethyl-N
, N/, N/-triacetic acid, propylenediaminetetraacetic acid, triethylenetetraminehexaacetic acid, etc., aminopolycarboxylic acids, ethylenediaminetetramethylenephosphonic acid, 1
-Hydroxyethylidene-1,1-diphosphonic acid and their sodium salts, potassium salts, ammonium salts, etc. can be mentioned.

Although it is sufficient to use one type of a specific group of compounds,
Two or more types may be used in combination.

The specific compound is preferably 0.029 to 1 part of dilution water.
-209, more preferably 0.05
g to 5 g.

Generally, the above-mentioned aminopolycarboxylic acids, phosphonic acids, etc. are known as so-called chelating agents for metals. Therefore, these compounds are used in photographic developers to sequester Ca and Mg ions contained in water.

Mason: Photographic Proc
easing Chemistry (F'ocal L
Ibrary 1975), and it is also known to use these compounds as chelating agents in fixers. However, there is no teaching about using water containing these compounds as dilution water for a developer or a fixer.

The concentrated developing solution and concentrated fixing solution that can be used in the present invention can be subjected to any processing method known in the art. In addition, it is possible to store a plurality of chemical parts in stock solution stock tanks in an automatic developing machine and use the stock water according to the present invention by automatically mixing and preparing them at the same time or before or after, but when using a concentrated developer, etc. It is better to have a smaller amount than a - agent, and the - agent is preferable because it simplifies the equipment.

From this point of view, black and white developers and fixers are more suitable for the method of the present invention than color developers, bleach-fixers, and the like.

The concentration ratio of each concentrate is not particularly limited, but is preferably in the range of 1.5 to 8 times.

There are no particular restrictions on the developing agent used in the black and white developer used in the present invention, including dihydroxy compounds (e.g. hydroquinone), 3-pyrazolyne amine phenols (e.g. N-methyl-p-aminophenol), etc. Known developing agents such as these can be used alone or in combination. It is preferable to contain dihydroxybenzenes because it is easy to obtain good performance, and dihydroxybenzenes and 1
A combination of -phenyl-3-pyrazolidones or a combination of dihydroxybenzenes and p-aminephenols may also be used.

The dihydroxybenzene developing agents used in the present invention include hydro-90 quinone, chlorohypyroquinone, bromohydroquinone, isopropyl hydro-90 quinone, methylhydroquinone, 2#3-u chlorohydroquinone, 2,
Examples include 5-dichlorohydroquinone, 2,3-dibromohydroquinone, and 2,5-dimethylhydroquinone, with hydroquinone being particularly preferred.

The 3-pyrazolide developing agent used in the present invention is 1-
Phenyl-4,4-dimethyl-3-pyrazolidone, 1-
Phenyl-4-methyl-4-hydroxymethyl-3-pyrazolibine, 1-phenyl-4,4-dihydroxymethyl-3-2 lazolidone, 1-phenyl-5-methyl-3
-pyrazolibine, 1-p-aminophenyl-4,4-dimethyl-3-pyrazolidone, 1-p-tolyl-4,4-
Examples include dimethyl-3-pyrazolidone, 1-p-)dyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, and the like.

Examples of the p-aminophenol developing agent used in the present invention include N-methyl-p-aminophenol, p-aminephenol, N-(β-hydroxyethyl)-p-aminephenol, and N-(4-hydroxyphenyl)glycine. ,
There are 2-methyk-p-7 minophenol, p-benzylaminophenol, etc., among which N-methyl-p
-Aminophenol is preferred.

The developing agent is preferably used in an amount of usually 0.01 mol/l to 0.8 mol/l. Further, when using a combination of dihydroxybenzenes and 1-phenyl-3-pyrazolidones or p-aminephenols, the former t-0.
01 mol/l to 0.5 mol/! , the latter is preferably used in an amount of 0.6 mol/l or less.

Preservatives for sulfite used in the present invention include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite,
and so on. Sulfite is 0.2 mol/1 or more, especially 0.4
It is preferably mol/1 or more.

In addition, it is preferable that the upper limit is 2.5 mol/l.
.

The pH of the developer used in the present invention is preferably in the range of 9 to 13.

Alkaline agents used to set pH include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, trisodium phosphate, and potassium triphosphate.
Contains H regulator 0 Japanese Patent Application No. 1987-28708 (Borate), Japanese Patent Application No. 1987-28708 (Borate)
Buffers such as No. 93433 (eg, sucrose, acetoxime, 5-sulfosalcylic acid), phosphates, carbonates, etc. may be used.

Additives used in addition to the above components include development inhibitors such as sodium bromide, beautifying potassium, and potassium iodide:
Organic solvents such as ethylene glycol, diethylene glycol, triethylene glycol, dimethylformamide, methyl cellosolve, hexylene glycol, ethanol, methanol: 1-phenyl-5-mercaptotetrazole, sodium 2-mercaptoinlimidazole-5-sulfonate It may contain capri-preventing agents such as mercapto compounds such as salts, indazole compounds such as 5-nitroindazole, and penztriazole compounds such as 5-methylbenztriazole, and may further contain color toning agents and surfactants as necessary. , antifoaming agent, water softener, JP-A-1983-
The amine compound described in No. 106244 may also be included.

In the present invention, a silver stain preventive agent, such as the compound described in JP-A-56-24347, can be used in the developer.

The developer of the present invention includes Japanese Patent Application Laid-Open No. 56-106244 (E
Amino compounds such as the alkanolamines described in K) can be used.

Furthermore, if a developing agent has been added to the light-sensitive material in advance, there is no problem in replacing the development treatment of the present invention with an alkali activation treatment.

The processing solution (alkali activation solution) used in the alkali activation treatment can contain any components other than the developing agent used in ordinary black and white developers. The pH of the alkaline activation solution is usually 10 to 14, preferably about 1.
1 to 14.

In addition, F', A. Meson's "Photographic
"Processin Chemistry", published by Focal Press (
1966), pp. 226-229, U.S. Patent No. 2,19
No. 3,015, No. 2,592,364, Japanese Unexamined Patent Publication No. 1973-
It may also be used with those described in No. 64933.

When a concentrated developer is refilled with water to dilute it as it is processed from a light-sensitive material in an automatic processing machine in the method of the present invention, it is advantageous for machine simplicity and replenishment that the concentrated developer is composed of one agent. It is most preferable from the viewpoint of accuracy, but 2 is preferable because of the composition of the developer.
It is also possible to prepare a drug and dilute it with water. In the case of two drugs, the number of pumps can be increased accordingly, or the packaging material can be devised to separate the two drugs until just before use, and when they are ready to use, they can be completely mixed and refilled in the same way as a single drug configuration. This also makes the method of the present invention possible.

It is virtually impossible for a concentrated developer to become a single agent if it contains a developer hardener due to its instability. Therefore, it is necessary that the photosensitive material itself has already been sufficiently hardened so that no hardening process is required. For example, JP-A-58-1
11933.

Another necessary condition for the concentrated developer to be one agent is that when using a 3-pyrazolidone developing agent, this agent must be a crude drug that is sufficiently stable to undergo hydrolysis in an alkaline solution. That is, among the above-mentioned 3-pyrazolidones, 3-pyrazolidones in which the 4-position is di-substituted with methyl and/or hibiloxymethyl are particularly preferred.

A water-diluted solution of a concentrated fixer (hereinafter simply referred to as fixer) may be used, for example, only for fixing or for fixing and bleaching.

The concentrated fixer contains thiosulfates, optionally water-soluble aluminum compounds, acetic acid, gluconic acid and dibasic acids (e.g.
5 acids, citric acid or their salts),
pf (3.8 or higher, preferably 4.0 to 5.5). More preferably, the pH is 4.65 to 5.5.

Examples of the fixing agent include sodium thiosulfate and ammonium thiosulfate, which contain thiosulfate ions and ammonium ions as essential components, and ammonium thiosulfate is particularly preferred from the viewpoint of fixing speed.

The water-soluble aluminum salt which mainly acts as a hardening agent in the fixing solution is a compound generally known as a hardening agent for acidic hardening fixing solutions, such as aluminum chloride, aluminum sulfate, and potassium alum.

As the above-mentioned dibasic acid, tartaric acid or its derivatives can be used alone or in combination of two or more kinds. It is effective to contain these compounds in an amount of 0.005 mol or more per fixer 11, especially 0.01 mol/13-0.03 mol/! ! is reasonably valid.

Specifically, there are tartaric acid, potassium tartrate, sodium w5ate, potassium sodium tartrate, and the like.

Examples of citric acid or its derivatives that are effective in the present invention include citric acid, sodium citrate, potassium citrate, lithium citrate, and ammonium citrate.

The fixer may optionally contain a preservative (eg, sulfite, bisulfite) and a pH buffer (eg, acetic acid).

boric acid), pHp! It can contain a conditioner (for example, sulfur #2), a chelating agent with water softening ability, and a compound described in Japanese Patent Application No. 60-218562. Here, the pH buffering agent is 10 to 40 g/l because the pH of the developer is high.

More preferably, about 18 to 25 g/l is used.

The fixing temperature and time are the same as for development, approximately 0°C.
10 seconds to 2 minutes at ~50°C is preferred.

When the a#J fixer is replenished into the automatic processing machine according to the method of the present invention together with the overflow solution and stock water of the present invention which are diluted as the photosensitive material is processed, this concentrated solution consists of one part. What is most preferable is the same as in the case of the developer.

The concentration fixer can exist stably as a single agent at pH 4,
The pH is 5 or higher, more preferably 4.65 or higher.

This is probably because if the pH is less than 4.5, the thiosulfate will decompose and eventually become sulfided if it is left for a long time before it is actually used. Therefore, in an environment with a pH of 4.5 or higher, less sulfur reformed gas is generated, which is good for the working environment. The upper limit of the pH is not so strict, but if the pH is too high, the pH of the membrane will be high even after washing with water, the swelling of the membrane will be large, and the drying load will be low (p)
I is up to 7 or so. In fixing solutions that use aluminum salts to harden films, the pH level is high to prevent precipitation of aluminum salts.
The limit is up to 5.5.

Of course, the present invention is not limited to one concentrated fixing solution, and may be composed of two components. In that case, it can be realized mechanically, ie, by increasing the number of pumps.

In the present invention, the concentrated developer may be a so-called working solution that does not require dilution water as described above (that is, it is replenished as an undiluted solution).

The amount of concentrated developer supplied to the developer tank and the mixing ratio with stock water which is dilution water, the amount of concentrated fixer supplied to the fixer tank and the dilution water which is the overflow liquid of the stock water and/or washing tank. The mixing ratio can be varied depending on the composition of the concentrated solution, but generally the ratio of concentrated solution to dilution water is 1:0.5 to 8, and the total amount of these is 1:1 to 0.5 to 8. On the other hand, it is preferable that the amount is from 100 mJ to 1500 ml.

In the present invention, the photosensitive material is subjected to water washing or stabilization treatment after being developed and fixed.

For water washing or stabilization treatment, any method of classification in this field can be applied.

In the present invention, by using stock water as washing water or stabilizing liquid and further using the overflow liquid as diluting water for concentrated fixer, it is possible to save water by requiring less than 3 liters of replenishment per 12 photosensitive materials. Not only this, but also the need for a separate stock tank for washing water can be reduced. In other words, the dilution water and washing water or stabilizing solution for diluting the concentrated developing solution and the concentrated fixing solution can be supplied from the stock water in a common single-layer stock tank, making the automatic processor more compact. became possible.

The present invention can effectively prevent the formation of limescale, and therefore the present invention can effectively prevent the formation of limescale, and therefore can be used in a range of 0 to 3 liters per photosensitive material. Preferably, water saving treatment of θ to 11 can be performed. Also automatic! Automatic processors with 1g system can be installed anywhere.

As a method to reduce the amount of stock water added to the washing or stabilization tank, the old
etc.) are known. If this multistage countercurrent method is applied to the present invention, the photosensitive material after fixing will gradually move in a cleaner direction.
In other words, the fixer is sequentially brought into contact with all parts of the processing solution that are not contaminated with the fixing solution (therefore, even more efficient water washing can be achieved).

In the method of the present invention, since a small amount of stock water is used as washing water, it is recommended to provide a squeeze roller washing tank as described in Japanese Patent Application No. 60-172968, which reduces the cost of the automatic processor and increases the scrubbing speed. More preferred.

Further, it is preferable that the washing tank is provided with a pre-washing bath as described in Japanese Patent Application No. 178049/1983.

The invention is particularly advantageous for roller conveyance automatic processors.

In the present invention, the stock water can contain various additives as required, or various additives can be added to the washing or stabilizing tank, the fixing tank, and the developer tank individually.

For example, JP-A-58-43452, JP-A-58-1140
Silver image stabilizers such as those described in No. 35 and No. 61-83534, and surfactants of various types can be added for the purpose of preventing unevenness of water droplets. As the surfactant, any of cationic, anionic, nonionic, and amphoteric types may be used. Specific examples of surfactants include compounds described in "Surfactant Handbook" published by Kogaku Tosho ■.

Further, these additives are particularly effective when carrying out a multistage countercurrent stabilization treatment process (so-called stabilization treatment) as described in % Japanese Patent Publication No. 57-8543.

The water washing or stabilization tank may contain, for example, an oak buffer (e.g. Hou I) to adjust the membrane pH (e.g. pH 3-8).
Addition of potassium salt, metaborate, borax, phosphate, carbonate, potassium hydroxide, sodium hydroxide, aqueous ammonia, monocarboxylic acid, dicarboxylic powder, polycarboxylic acid, etc.) I can do it. In addition, various surface additives such as chelate cutting, fungicides (thiazole type, isothiazole type, halogenated phenol, sulfonylamibi, incitriazole, etc.), surfactants, and fluorescent whitening i11? It may be used, or two or more compounds for the same or different purposes may be used in combination.

In addition, ammonium chloride,
Various ammonium salts such as ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium sulfite, and ammonium thiosulfate can also be added.

Silver halide photographic materials applicable to the method of the present invention include various color and black and white photographic materials. For example, color negative film for photography (general use, movies, etc.), color reversal film (for slides, movies, etc., and sometimes without color photographic paper),
Color photographic paper, color positive film (for movies, etc.), color reversal photographic paper, medical or industrial X-ray photographic material, duplex photographic material for X-ray, photographic material for medical CRT images, photosensitive material for printing (e.g. scanner photosensitive material) General black-and-white negative photosensitive materials. Examples include black and white photographic paper. The present invention is particularly effective when applied to black-and-white photosensitive materials.

According to the method of the invention, the developed, fixed and washed photographic material is dried. Drying is carried out at a temperature of about 0° C. to about 100° C., and the drying time can be changed as appropriate depending on the surrounding conditions, but usually it is about 5 seconds to 3 minutes and 30 seconds.

1lfF in the US for roller conveyance type automatic processors.
It is described in Specification No. 3025779, Specification No. 3545971, etc.

A silver halide photographic light-sensitive material that can be used in the method KjM of the present invention comprises a support and at least one coated material on the support.
Consists of a silver halide emulsion layer. Of course, a back layer, an antihalation layer, an intermediate layer, a top layer (for example, a protective layer), etc. can be included if necessary.

Silver halide emulsions are silver halides such as silver chloride, silver iodide, silver chloride, silver chlorobromide, silver iodobromide, silver chloroiodobromide, etc., dispersed in a hydrophilic colloid (e.g. gelatin). It is. Silver halide emulsions are usually prepared by mixing a water-soluble silver salt (e.g., silver sulfate) and a water-soluble halide salt in water using methods known in the art (e.g., single jet method, double jet method, control jet method, etc.). and a hydrophilic colloid, and undergoes physical ripening and chemical ripening such as gold sensitization and/or sulfur sensitization.

Silver halide emulsions may contain spectral sensitizers (e.g. cyanine dyes, merocyanine dyes or mixtures thereof), stabilizers (e.g. 4-hydroxy-6-methyl-LL3a+7-titrazaindene) during the manufacturing process or immediately before coating. , sensitizers (e.g., the compounds described in U.S. Pat. No. 3,619,198), anti-capri agents (e.g., benzotriazole, 5-nitrobenzimidazole, polyethylene oxide), hardeners (e.g., formalin, glyoxal, mucochlor). acid, 2-hydroxy-46-dichloro-
d-triacyl/, N,N'-ethylenebis(vinylsulfonylacetamide), coating aids (e.g., saponin, sodium lauryl sulfate, dodecylphenol borietele/oxide ether, hexadecyltrimethylammonium bromide), etc. Can be added. The silver halide emulsion produced in this manner can be coated on a support such as zeta lighter paper, resin coated paper, cellulose acetate film, polyethylene terephthalate film, etc. using the guitubing method, air knife method, bead method, extrusion doctor method, double-sided coating method, etc. It is applied and dried by

(Example) The present invention will be illustrated below with reference to Examples, but the present invention is not limited thereto.

Example 1 (1) Preparation of silver halide emulsion After adding an appropriate amount of ammonia to a container heated to 55°C containing gelatin, potassium bromide, and water, the pAg value in the reaction container was adjusted to 7. Monodisperse silver bromide emulsion grains having an average grain size of 0.55 μm were prepared by adding an aqueous solution of silver nitrate and a potassium bromide solution by a double-jet method while maintaining the temperature at 60 μm. After desalting this emulsion, the pH was adjusted to 6.2, pA
After adjusting g to 86, gold/sulfur sensitization was performed using sodium thiosulfate and chloroauric acid to obtain desired photographic properties. The (100) plane/(111) plane ratio of this emulsion was measured by the Taberka-Munk method and was found to be 98/2.

(2) Preparation of emulsion coating solution Weigh out 1llp of this emulsion, heat and dissolve at 40°C, and add a methanol solution of near-infrared sensitizing dye = structural formula A (9 x 10
'μ/1) f70cc, 4-? An emulsion coating solution was prepared by adding l-'o xy-6-methyl-113l3a, an aqueous solution of 7-titrazaindene, an aqueous solution of a coating aid dodecylbenzenesulfone rR, and an aqueous solution of a thickener p-vinylR nozenesulfonate compound. did.

Structural formula A (3) Preparation of coating solution for surface protective layer of photosensitive material layer A 1Qwt% gelatin aqueous solution heated to 40°C, a thickener polyethylene sulfone soda aqueous solution, and a matting agent polymethyl methacrylate fine particles (average particle size 3) .0 μm), hardening agent N, N'-ethylenebis-(vinylsulfonylacetamide), coating aid t-octylphenoxyethoxyethoxyethoxyethanesulfonate aqueous solution, fluorine-containing surfactant, and nonionic surfactant. A coating solution was prepared by adding a coating agent.

(41 Preparation of back coating solution 10 wt% aqueous gelatin solution I heated to 40°C
Kp is thickener polyethylene sodium sulfonate aqueous solution,
A coating solution was prepared by adding an aqueous solution of the dye of structural formula B, a hardener N, an aqueous N/-ethylenebis-(vinylsulfonylacetamide) solution, and an aqueous solution of sodium t-octylphenoxyethoxyethoxyethanesulfonate as a coating aid.

(5) Preparation of coating solution for the surface protective layer of the back layer A 10 wt% gelatin aqueous solution heated to 40°C, a thickener polyethylene 1Lf7 sodium ionate aqueous solution, and a matting agent polymethyl methacrylate fine particles (average particle size 3 .0μm
), a coating aid t-octylphenoxyethoxyethoxyethoxyethanesulfonate aqueous solution, a fluorine-containing surfactant, and a nonionic surfactant were added to prepare a coating liquid.

(6) Preparation of coating sample The above-mentioned back coating solution and the back surface protective layer coating solution were coated on one side of a polyethylene terephthalate support so that the gelatin coating amount was 41//-. Subsequently, on the opposite side of the support, an emulsion coating solution containing a near-infrared sensitizing dye and a surface protective layer coating solution for this were first coated with a silver amount of 4.
．． 097-, the sample film thus obtained was developed using the development system shown in FIG. 1 and below.

The compositions of the developer and fixer concentrates are as follows.

<Concentrated developer> Potassium hydroxide 56.6g Otrium sulfite 200, p diethylene triamine penta vinegar rt 16.79 Potassium carbonate
16.7g boric acid
10 fi human 90 quinone 83.39 diethylene glycol 40. 95-Methylbenzotriazole Adjust to 11 with 2g water (p
Adjust to H10,30).

Concentrated fixing solution> Ammonium thiosulfate 560g Sodium sulfite 60,9 water modified sodium 24g 11 with water
(Adjust the pH to 5,10Kv4 with vinegar).

Stock water〉 Ethylenediaminetetraacetic acid disodium salt dihydrate
0.5 fi/1 automatic developing machine (see Figure 1) Dry to Dry for 60 seconds Development tank (1) 6.5135℃X 12.
5 seconds fixing tank (2) 6.51 35℃
X 12.5 seconds flush tank (3) 6.51
20℃ x 7.5 seconds pre-washing bath (8) 200- Squeeze roller cleaning tank (73200wt 1 stock water tank (4) 251 Drying 60℃ Dry to Dry for 60 seconds When starting the development process, perform the following treatment on each tank. filled with liquid.

Developing tank: above concentrated developer 333R1, stock water 6
671, 2y of potassium bromide, and 1.8I of acetic acid, the pH was adjusted to 10.
．． 15 fixing tank 2 The above concentrated fixer 250IR1 and the stock water 750 resistant pre-washing bath Washing tank and washing tank: Same composition as the above stock water The above photosensitive material B4 size (25.7 cIn x 36.4 c
Wt) 20rttl of concentrated developer and 40ml of stock water are added to the developing tank every time one sheet is processed.
10IIL of concentrated fixer in the md fixing tank.3 stock water from Washing Yu through the washing tank to the pre-washing bath.
- was replenished, and about 30 - of the overflow liquid from the pre-washing bath was transferred to the fixing tank, and the running process of 15 sheets was continued on - day. During this time, if you run out of developer, fixer, or stock sailor, you can add new replenisher in the same way.

In this way/two'! Although the use continued for i-2 months, the initial photographic characteristics were maintained, and even without replacing the washing liquid in the washing tank, running could be continued without limescale formation.

During this time, the waste liquid was 38.51 for developer and 21.5 for fixer.
J, this fixer contained 7.89/l silver. Of course, the amount of waste liquid from the washing water was zero. The stock water used was 52.5 A'.

Unlike the above, the overflow liquid from the pre-washing bath was discarded and the fixing tank was directly replenished with 30 dt of stock water, but otherwise a running experiment was conducted in exactly the same manner.

The waste liquids during this period were as follows, and the developing solutions were the same as above: 3B, 51. Fixer: 25/, silver concentration: 6.41//l,
Washing water is 191, silver concentration 0.4j9/1. The total amount of stock water used was 751.

The results show that the present method is superior to the comparative method in both water saving and silver recovery efficiency.

The method of the invention has the following advantages.

■ Since it can be processed with a small supply of water, there is no need for any tap water piping, making it possible to install the machine anywhere.

■ Since there is less waste liquid, the burden of waste liquid pollution treatment is low.
S.

■ Silver recovery efficiency and recovery rate are high because it can be recovered as fixer waste liquid with high silver concentration.

■ Even with a very small amount of washing liquid, limescale does not form, making maintenance such as cleaning the roller rack unnecessary.

■ No need to prepare developer and fixer, making work easier.

(Li) A stock tank for development constant M solution is not required, and the installation space for the automatic processor is small.

[Brief explanation of the drawing]

FIG. 1 is an explanatory diagram of an embodiment of the method of the present invention. 1: Developing tank 2: Punishing tank 3: Washing tank 4 Varnish dock water tank 5: Concentrated developing stock tank 6: Concentrated fixer stock tank 7: Squeeze roller cleaning tank 8: Pre-washing bath 9: Roller P: Bump (etc.) 3 persons) Procedural Amendment January 1988 90 I? i'is'f' JT Director 6, Number of inventions increased by the amendment: 0 (1) 1.Development,” on page 4, line 15 of Specification J1, is amended to read ``developer,''. (2) "From the washing water" on page 4, lines 19-20 of the same book is amended to "also from the washing water." (3) In the first line of page 5 of the same book, ``In addition to the recovery of silver from the waste liquid of the processing liquid for this purpose'' is amended to ``For this reason, not only the recovery of silver from the waste liquid of the processing liquid.'' (4) "Stock water" on page 7, line 7 of the same book is replaced with "
"Stock water". (5) [Proceesin, page 18, line 3 of the same book]
(Correct IJ to l'PrOceQssing j. (6) Change "processin" in page 23, line 15 of the same book to "
"Prohising" is corrected. (7) "From materials" in the first line of page 24 of the same book is amended to "materials". (8) On page 24, lines 14 to 16 of the same store, "It is necessary. For example, the method described in Japanese Patent Application Laid-Open No. 58-111933."
(method described in No. 33). ” he corrected. (9) Delete "more preferably" from the 1st and 2nd lines of page 25 of Book 11. (10) Delete "It contains thiosulfate ions and ammonium ions as essential components" in lines 15 and 16 of page 25 of the same store. (11) “Known” in the first line of page 26 of the same book
be corrected to "known". (12) Delete "especially" in line 8 of page 26 of the store. (13) In the same document, page 27, line 7, ``Overflow of the invention [coe liquid''] is amended to ``Water wash overflow of the invention ``coe liquid''. (14) In the same book, page 27, lines 14-15, ``Tame derou.'' is amended to ``Tame deru.'' (15) Same book, page 28, line 18 to page 29, line 1
Delete the line ``The present invention can be applied.'' (16) l1il''iT'i, page 39, line 3, ``
Correct "odorium sulfate" to "sodium sulfite". (17) rDry to, page 40, line 4 of the same book
60 seconds processing with Dry” is deleted. (18) Similarly, on page 40, between the 8th line and 9th line from the bottom, there is a feature that says ``Cooling water is not used for humidity control in the developing tank (1) and fixing tank (2).'' do

Claims (1)

[Claims] The silver halide photographic light-sensitive material is developed using an automatic developing machine equipped with a stock tank containing anti-mildew water.
In the method of fixing and washing or stabilizing, a concentrated developer and water treated with the anti-mildew means are transferred to a developer tank, and a concentrated fixer is transferred to a fixer tank, and an amount of 3 liters or less per 1 m^2 of the photosensitive material is transferred. A washing or stabilizing tank is replenished with the water subjected to the anti-mold treatment, and part or all of the overflow liquid from the washing or stabilizing tank is transferred to the fixing tank and used as a diluent for the concentrated fixing solution. Development processing method.