JP2963215B2 - Processing method of silver halide photographic material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a silver halide photographic material (hereinafter, simply referred to as a photographic material or a photographic material).
The present invention relates to a method for processing a silver halide photographic light-sensitive material which is processed using a light-sensitive material processing apparatus such as an automatic processor.

[0002]

2. Description of the Related Art For example, a silver halide black-and-white photographic light-sensitive material is processed in a process of developing, fixing and washing with water after exposure. However, such a process has recently caused problems of environmental conservation and water resources. It is considered important.

For this reason, various methods have been proposed for reducing the amount of washing water used in large quantities.

[0004] Among them, for example, as a technique for countercurrent water washing with a water washing tank having a multi-tank structure, SRGoldwasser, "Water
flow rate in immersion-Washing or motion picture
film, "J. SMPTE, 64 , 248-253, May (1955)", and this method is generally applied to automatic processing machines for color photographic light-sensitive materials.

In an automatic developing machine for X-ray photosensitive material and photosensitive material for printing, an energy-saving type is used, in which a solenoid valve of a washing water supply pipe is opened for a processing time to supply the washing water, and even a little water saving. Devices to be used are being generalized.

However, in an automatic developing machine for processing a sheet-like photosensitive material such as an X-ray photosensitive material or a printing photosensitive material, when the above-described multi-tank countercurrent washing method is applied, the number of washing tanks depends on the number of washing tanks. Rollers and racks must be installed, which increases the initial cost of the automatic processor and increases the size of the automatic processor and requires a large installation space. Impossible.

Therefore, an automatic developing machine for processing these sheet-like black-and-white photosensitive materials by transporting them with rollers is a one-tank type or a type provided with a preliminary washing tank, or at most two types.
In order to increase the washing capacity, a so-called large-scale washing method in which the washing water replenishment amount is more than 0.6 liter per 1 m ² of the photosensitive material is unavoidable.

[0008] By the way, if the washing water stays in the washing tank, the scale is generated, and after two to three weeks, the water rots and the odor is generated. In addition, when the automatic processor is stopped and left for several days, floating substances are generated, which adhere to the photosensitive material,
It also causes clogging of filters, drains and distribution pipes.

Therefore, in order to remove them, the washing tank must be periodically cleaned.

In particular, in the roller transport system, once the scale is generated, since there are many transport mechanism components, cleaning the rollers, racks and the like is an extremely difficult operation.

Therefore, in order to improve such disadvantages,
Various methods have been proposed as follows.

LEWest, "Water Quality Criteria" Pho
t.Sci. and Eng., vol. 9, No. 6,398 pages (1965), ME B
each, "Microbiological Growth in Motion-Picture Pr
ocessing "SMPTE Journal, vol. 85, Mar. (1976) and RO Deegan," Photoprocessing Wash Water Biocid
es "J. Imaging Tech. vol. 10, No. 6, p. 239 Dec (198
4) describes the addition of a chelating agent or a bactericide to the washing water.

Further, JP-A-57-8542 and JP-A-58-8542.
No. 105145, No. 57-157244, No. 62-2
No. 20951 and the like describe the addition of various thiazolyl benzimidazole compounds and isothiazolone compounds.

Also, a method of purifying pure water using an ion exchange resin described in JP-A-61-131632,
Japanese Patent Application Laid-Open No. Sho 60-263940 discloses a method of irradiating ultraviolet rays, a method of applying a magnetic field, and a method of applying ultrasonic waves.

Recently, Japanese Patent Application No. 01-91533 has been proposed.
It is described in Japanese Patent Application Publication No. 2000-146139 that an Ag ⁺ ion releasing means for eluting Ag ⁺ ions into washing water is provided.

However, each of the above-mentioned techniques does not provide a sufficient scale-preventing effect even when used alone, and some of them are not practical in terms of long-term continuity and the like. Some additives have toxicity problems and are not suitable for use.

[0017]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned drawbacks of the prior art, and has as its object the processing of a silver halide photographic light-sensitive material having a simple structure and generating very little scale. It is to provide a method.

[0018]

This and other objects are achieved by the present invention which is defined below as (1) to (7).

(1) When processing a silver halide photographic light-sensitive material using a light-sensitive material processing apparatus for processing at least a developing process, a desilvering process, and a washing process, a porous material is used as a carrier. A method for processing a silver halide photographic material, characterized by using water, which has been brought into contact with a material having soil bacteria carried on the carrier, in at least the washing treatment.

(2) The silver halide according to the above (1), wherein water brought into contact with a material having soil bacteria carried on the carrier is used for replenishing the processing solution for the development and / or desilvering. Processing method of photographic photosensitive material.

(3) The method according to the above (1) or (2), wherein the water contacted with the material having the soil bacteria carried on the carrier is used for washing a transport mechanism component for transporting the silver halide photographic light-sensitive material. The method for processing a silver halide photographic light-sensitive material described in the above.

(4) The method for processing a silver halide photographic light-sensitive material according to any one of the above (1) to (3), wherein the soil bacteria are aerobic bacteria.

(5) The method for processing a silver halide photographic light-sensitive material according to any one of the above (1) to (4), wherein the soil fungus is an actinomycete or an algae.

(6) The method for processing a silver halide photographic light-sensitive material according to any one of the above (1) to (5), wherein radioactive bacteria and algae are used in combination.

(7) The halogenation according to any one of the above (1) to (6), wherein the replenishing amount of the washing water in the washing process is ^{2 to} 20 liters per 1 m ^{2 of the} silver halide photographic material to be processed. Processing method of silver photographic photosensitive material.

[0026]

According to the present invention, a porous material is used as a carrier, and water that has been brought into contact with a material (hereinafter referred to as a scale inhibitor) carrying soil bacteria on the carrier is subjected to a water washing treatment and a development treatment. By replenishing the processing solution for the desilvering process and / or washing the components of the transport mechanism, the decomposing action of the soil bacteria can decompose substances that become nutrient sources of microorganisms such as bacteria and bacteria that cause scales. And lose its function as a nutrient source. As a result, the growth of the microorganism is suppressed, and thus the generation of scale is prevented.

[0027]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The processing method of a silver halide photographic light-sensitive material of the present invention will be described below in detail with reference to preferred embodiments shown in the accompanying drawings.

FIG. 1 shows a configuration example of a photosensitive material processing apparatus used in the method of the present invention.

The photosensitive material processing apparatus 1 shown in FIG. 1 is, for example, a roller transport type automatic developing machine that transports a sheet-like photosensitive material by a roller, and the replenishing amount of washing water for washing the photosensitive material with water is relatively large. It employs a large volume washing method. Hereinafter, these will be sequentially described.

In the present invention, the type and form of the photosensitive material to be processed are not particularly limited.
It is preferably applied to the processing of black-and-white light-sensitive materials such as ray light-sensitive materials and printing light-sensitive materials. For this reason, the illustrated apparatus is for processing black-and-white light-sensitive materials.

In the photosensitive material processing apparatus 1 shown in FIG. 1, a developing tank 2, a fixing tank 3 and a washing tank 4 in which a developing solution, a fixing solution and washing water are respectively placed are arranged in a main body case in this order from the right side in the figure. It is juxtaposed.

In the developing tank 2, a transport roller 51 for transporting the photosensitive material S along a predetermined path in the tank is arranged. Further, in the fixing tank 3 and the washing tank 4, similar transport rollers 52 and 53 are disposed, respectively.

A crossover roller 6 is provided between each of the processing tanks 2 to 4 and a squeeze section 8 described later.
1, 62 and 64 are provided. These crossover rollers 61, 62, and 64 squeeze out the processing liquid adhering to the surface of the photosensitive material when the photosensitive material S is sandwiched, and suppress the carry-in of the processing liquid from the previous tank to the next tank.

These crossover rollers are:
For example, it is preferable to adopt a configuration in which the roller is washed with water from a stock tank 180 described later to prevent the roller from being stained by the adhesion of the developing solution component and the fixing solution component.
That is, after the processing operation of one day, water is sprayed on the crossover roller (Japanese Patent Application No. 62-18636).
Alternatively, it is preferable that a rinsing tank is provided so that the crossover roller is always immersed in the water in the rinsing tank.

A guide 7 for guiding the photosensitive material S to the next roller is provided between rollers such as near the bottom of each of the processing tanks 2 to 4 and on both sides of the crossover rollers 61 and 62.

The transport rollers 51 to 53 and the guide 7 are preferably loaded in a state where they are assembled in a rack for each processing tank.

The photosensitive material S introduced into the main body case is
The rollers 51 to 53, 61, 62, and 64 successively transport the developer tank 2, the fixing tank 3, and the washing tank 4 while being immersed in each processing liquid to perform development, fixing, and washing.

In each of the processing tanks 2 to 4, replenishment and drainage of the processing liquid in accordance with the processing tank are performed, and preferably, the processing liquid is circulated.

It is preferable to replenish the developing tank 2 and the fixing tank 3 by diluting the concentrated developing solution (or plural kinds of parts) and the concentrated fixing solution with water to obtain a replenisher having a desired concentration, respectively.

In the developing tank 2 and the fixing tank 3, it is preferable to circulate the processing solution, and these are circulated by circulating pumps 10 and 11, respectively.

At the bottom of the washing tank 4, a scale inhibitor 40 described later is put.

The supply of the washing water to the washing tank 4 and the supply of the water for diluting the concentrated liquid are performed from a stock tank 180. Water is supplied to the stock tank 180 through a pipe 185 from a water source (water tap) 187, and the flow rate is adjusted by a valve 186.

A squeeze section 8 is provided on the upper left side of the washing tank 4 in FIG. A plurality of pairs of squeeze rollers 81 are installed in the squeeze section 8 along the conveyance path of the photosensitive material S. The squeeze rollers 81 pinch and convey the washed photosensitive material S, and Remove moisture.

A drying section 9 is provided below the squeeze section 8 in FIG.
Is provided. The drying unit 9 includes a casing 91
And hot air supply means 94 for supplying hot air for drying into the casing 91.
A transport roller 92 and a guide 93 are provided along the transport path of the photosensitive material S.

The hot air supply means 94 includes a blowing fan 95.
A warm air heated to preferably about 35 to 100 ° C. (more preferably, about 40 to 80 ° C.) is supplied into the casing 91 through a duct 97 having a built-in heater 96 and communicating with the casing 91. In the casing 91, the photosensitive material S having passed through the squeeze unit 8 is transported by the transport rollers 92, and is dried by contacting the supplied hot air.

Specific examples of such a photosensitive material processing apparatus 1 include an automatic developing machine, a wet type copier, a printer processor, a video printer processor, a photo print making coin machine, and a color paper processing machine for plate inspection. .

In such a photosensitive material processing apparatus 1,
FIG. 2 shows a configuration example of a supply system for the processing liquid (replenisher).

As shown in FIG. 2, a developing solution is contained in the developing tank 2, a fixing solution is contained in the fixing tank 3, and a washing water is contained in the washing tank 4. Both ends of the developing solution in the developing tank 3 communicate with the bottom of the developing tank, and are circulated through a pipe 12 provided with a circulation pump 10 on the way. The fixing solution in the fixing tank 3 is also circulated by a pipe 13 in which a circulation pump 11 is provided in the middle similarly to the developing solution. Although not shown, such a circulating system of the processing liquid can be provided in the washing tank 4 as well. In this case, the better effect of the present invention is exhibited in the washing tank 4.

Further, the washing tank 4 may be provided with a drain pipe and a valve (both not shown) provided in the middle of the pipe.

The temperature of the developing solution, the fixing solution and the washing water in each of the processing tanks 2 to 4 is controlled by a heater or the like (not shown) to a temperature as described later.

The exposed photosensitive material S is the photosensitive material processing apparatus 1
After the rollers 51 to 53, 61, 6
The developer is transported sequentially to the developing tank 2, the fixing tank 3, the rinsing tank 4, the squeezing section 8 and the drying section 9 by a transport means composed of 2, 63, etc., where development, fixing (desilvering), rinsing, draining and drying are performed. Done.

Next, the replenisher supply system (replenisher) will be described.

As shown in FIG. 2, the replenishing solution supply system 200 includes three replenishing parts 151, 152 and 153 for storing three kinds of parts A, B and C constituting the developing solution, respectively. And a stock tank 15 for replenishing the fixer for storing the concentrate of the fixer.
4 are provided.

On the upper part of the stock tank 150, a medicine container 14 in which partial containers 141, 142 and 143 containing three kinds of parts agents A, B and C, respectively, are integrated.
0 is set, and a medicine container 144 containing a concentrated solution of the fixing solution is set above the stock tank 154.

Each partial container 141 to 14 of the medicine container 140
3, the parts agents A to C are supplied to the corresponding parts agent storage units 151 to 153 of the stock tank 150, and the concentrated solution of the fixing solution is supplied to the stock tank 154 from the medicine container 144.

From the part agent storage sections 151 to 153 of the stock tank 150, liquid feed pipes 161 to 163 are respectively provided.
Are extended to the developing tank 2, and the parts agents A to C are supplied to the developing tank 121 by the operation of the pumps 171 to 173 installed in the middle of the liquid sending pipes 161 to 163. Further, from the stock tank 154, a liquid feed pipe 164 is extended to the fixing tank 3, and a pump 17 installed in the middle of the liquid feed pipe 164 is provided.
By the operation of 4, a concentrated solution of the fixing solution is supplied to the fixing tank 3.

The fixing solution may be supplied as a plurality of (for example, two) types of parts. In this case, the same composition as the medicine container 140 and the stock tank 150 is used.

The replenisher supply system 200 is provided with a stock tank 180 for washing water as a supply source of dilution water.

The rinsing water stock tank 180 has pipes 181 and 1 extending to the rinsing tank 4, the crossover rollers 61 and 62, the fixing tank 3 and the developing tank 2, respectively.
82, 183, and 184 are provided, and pumps 191, 192, 193, and 194 are provided in the middle of these pipes, respectively.

By the operation of the pump 191, the water in the stock tank 180 is supplied to the washing tank 4 through the pipe 181.

By the operation of the pump 192, the water in the stock tank 180 is blown through the pipe 182 to the crossover rollers 61 and 62, which are components of the photosensitive material, in a shower shape, for example. 6
Wash 2 As described above, when the rinsing tank for the crossover rollers 61 and 62 is provided, the water from the stock tank 180 is supplied to the rinsing tank.

By the operation of the pump 193, the water in the stock tank 180 is supplied to the fixing tank 3 and dilutes the concentrated solution of the fixing solution sent through the liquid sending pipe 164 to obtain a fixing solution having a desired concentration. .

By the operation of the pump 194, the water in the stock tank 180 is supplied to the developing tank 2, and the liquid supply pipes 171 to 171 are supplied.
Each of the parts agents A to C or a mixture thereof sent through 173 is diluted to become a developer having a desired composition and concentration.

It should be noted that the water supply from the stock tank 180 to the washing tank 4 and the like is not limited to the operation by the pump as shown in the figure, but may be a water supply method by a head, for example. In this case, a valve for adjusting the timing and flow rate of water supply may be provided in the middle of the pipe connecting the stock tank 180 and the washing tank 4 or the like.

The water source 1 is supplied to the washing water stock tank 180.
Tap water is supplied from the pipe 87 through the pipe 185 by the opening and closing of the valve 186 in a timely manner (for example, when the amount of liquid in the washing water stock tank 180 is detected and becomes less than a predetermined amount).

In the photosensitive material processing apparatus 1 having such a configuration, the washing tank 4 and the stock tank 180 have
A anti-scale agent 40 is provided.

Hereinafter, the structure of the anti-scale agent 40 will be described.

The anti-scale agent 40 is obtained by supporting soil bacteria (soil microorganisms) on a carrier.

As the soil fungi, actinomycetes or algae are preferable. Examples of actinomycetes include ammonia oxidizing bacteria, nitric acid bacteria, sulfur oxidizing bacteria, cellulolytic bacteria,
Pseudomonas, Streptomyces, Penicillium, Nocardia and the like. Examples of the algae include a cyanobacterium, a micrococcus, and the like.

Specific examples of such soil bacteria include:
Ammonia oxidizing bacteria (nitrite bacteria); nitric acid bacteria; sulfur oxidizing bacteria (bacteria using hydrogen sulfide as a hydrogen donor, green sulfur bacteria / e.g., Aerobic bacteria such as Beggiatoa and Thiobacillus) Cellulose-degrading bacteria (aerobic and anaerobic bacteria); manganese oxidizing bacteria (organotrophic bacteria); manganese-reducing bacteria (Black mold genus-protozoa); nitrifying bacteria; actinomycetes (chitin-degrading bacteria);
Methane-oxidizing bacteria; spore-forming bacteria; cellulosic filamentous fungi; lignin-degrading bacteria; iron-oxidizing bacteria; iron-reducing bacteria;

In the present invention, among these, genus ammonia oxidizing bacteria (nitrite), nitrate bacteria, sulfur oxidizing bacteria (sulfur bacteria), cellulolytic bacteria, pseudomonas genus,
Actinomycetes such as Streptomyces and Penicillium, and algae such as cyanobacteria and Micrococcus are preferably used.

Among these, the aerobic bacteria and the anaerobic bacteria are preferably the former. The reason is that aerobic bacteria have a higher effect of preventing water scale, and do not generate substances (eg, methanated ammonia) that cause malodor, and are advantageous for the growth of bacteria in an environment where water is replaced. That's why.

Actinomycetes have properties located between filamentous fungi and bacteria, and both aerobic bacteria and anaerobic bacteria are present.

Ammonia oxidizing bacteria (nitrite bacteria) and nitrate bacteria change ammonia nitrogen to nitrate nitrogen. This action is called a nitrification action, and is known to be performed through the following two steps. NH ₃ + 3O = HNO ₂ + H ₂ O HNO ₂ + O = HNO ₃

The ammonia-oxidizing bacteria (nitrite) contribute to the action of oxidizing the ammonia at the former stage to nitrite, and the nitrate bacteria contribute to the action of further converting the produced nitrite into nitrate at the latter stage.

Sulfur oxidizing bacteria (sulfur bacteria) oxidize solid sulfur, sulfurous acid, thiosulfuric acid, and hydrogen sulfide and proliferate.

Cellulose-decomposing bacteria act as follows to produce glucose by using fiber as a nutrient. (C ₆ H ₁₀ O ₅ ) n + nH ₂ O = n (C ₆ H ₁₂ O ₆ )

Further, this glucose changes as follows. _{C 6 H 12 O 6 = C} 4 H 8 O 2 + 2CO 2 + 2H 2 C 6 H 12 O 6 = 3C 2 H 4 O 2 C 6 H 12 O 6 = 3CO 2 + 3CH 4

Cyanobacteria, which is a kind of algae, is also called cyanobacteria and forms a single cell or a fibrous cell chain. The cyanobacteria perform O ₂ -generating photosynthesis. The principle of preventing the occurrence of scale by such soil bacteria is as follows.

That is, soil bacteria decompose, oxidize, or reduce substances serving as nutrients (eg, nitrogen-based, carbon-based, and sulfur-based substances) of microorganisms that cause scales to lose their function as nutrient sources. Therefore, the propagation of the microorganisms is suppressed, and the occurrence of scales is prevented.

Soil bacteria, especially actinomycetes, have an phagocytic action, thereby killing the microorganisms that cause the scale generation and coagulating or precipitating the nutrient sources. To effectively reduce the amount of nutrients.

In the present invention, one or more of the above soil fungi can be used.

In the present invention, it is particularly preferable to use actinomycetes and algae together. The reason is that the carbonic acid assimilation effect accompanying the generation of algae supplies oxygen to the aerobic actinomycetes and promotes the propagation of the actinomycetes.

In this sense, algae directly contribute to the prevention of scale formation and also have an auxiliary function of increasing the activity of actinomycetes.

In this case, the ratio of the amount of actinomycete to the amount of algae used is not particularly limited.
It is preferably about 05 to 2, particularly about 0.1 to 0.5.

[0086] As the carrier for carrying the soil bacteria, a carrier having a large bacteria holding capacity and being easy to regenerate is preferable. The material is rock (for example, perlite) or a crushed product thereof, gravel, sand, plastic, or the like. And ceramics (for example, alumina, silica, natural zeolite, synthetic zeolite) and the like. Porous materials having porous pores such as porous ceramics and porous plastics are used. . For example, a fine powder (trade name: perlite), which is obtained by holding a ground perlite at a high temperature and a high pressure and then rapidly reducing the pressure to make it porous, is preferable because it has a property of forming a colony of fungi.

In such a porous material, the diameter of the vent hole is preferably about 0.5 to 10 μm, particularly preferably about 1 to 5 μm.

The carrier may be in any form such as a lump, a granule, a powder, a fine powder or a plate, a needle or the like, but preferably has an average particle diameter of 2 mm or less, particularly 50 μm or less.
A powder of about μm to 1 mm is preferred.

As a method of supporting the soil bacteria on such a carrier, the soil bacteria (original bacteria) and the carrier are mixed and cultured (fermentation and propagation), or the soil bacteria are cultured in a liquid medium and then It can be performed by mixing with a carrier.

The culture of soil bacteria is carried out by, for example, a carbon source such as glucose, sucrose, maltose, dextrin, glycerin, starch, a nitrogen source such as peptone, meat extract, yeast extract, malt extract, casein, NaC
1, aeration and agitation in a neutral liquid medium using an inorganic salt or the like such as K ₂ HPO ₄ , MgSO ₄ and CuSO ₄ .

At this time, the pH of the medium is preferably about 5 to 8, particularly about 6.5 to 7.5, and more preferably about 7.2.
The culturing temperature is usually about 20 to 35 ° C, particularly 30 ° C.
Before and after is preferred.

The amount of soil bacteria carried on the carrier depends on the above-mentioned supporting method, particularly on the conditions of culture and the components of the culture medium, but the amount carried is 500 to 200 billion per cm ³ , preferably 10 to 20 million.
It is good to be 100 million to 100 billion.

The details of such soil bacteria are described in the following documents.

1) Microorganisms and their applications No. 5, Proposals for antibiotic production, Yoshiro Okami and Satoshi Omura, Kyoritsu Shuppan (Showa 54)

2) Fungi Illustration Book, lower volume P1195, Shunichi Udagawa et al., Kodansha Scientific (1977)

3) Microbiology for environmental purification, Ryuichi Sudo, Kodansha (1982)

In the present invention, when the anti-scaling agent 40 is put into the washing tank 4 and the stock tank 180, the anti-scaling agent 40 is placed in a predetermined container, bag, net, cloth, etc. having liquid permeability. It is preferable to be in a housed state.

One example is, for example, 0.1 to 1
g of the anti-scale agent 40 is filled in a container (for example, made of polyethylene) having a volume of about 5 to 20 cm ^3.
In order to fix 0 and prevent scattering, a holding member such as a 100-400 mesh nylon cloth or urethane foam plate is provided on the lid or bottom of the container.

The nylon cloth includes, for example, nylon cloth bolting cloth and golden cloth sold by Toray Industries, Inc., Teijin Co., Ltd., NBC Corporation, Noguchi Sieve Silk Co., Ltd. Etc. can be suitably used.

Further, the container containing the anti-scale agent 40 can be placed in a frame made of, for example, stainless steel or plastic, and can be submerged in the bottom of the washing tank 4 or the stock tank 180.

As another method of sinking the container,
For example, a stainless steel or glass weight may be put in the container.

In the present invention, with the above-described structure, the generation of scale in the washing tank 4 and the stock tank 180 is of course prevented, and as shown in FIG. Water is supplied to the developing tank 2 and the fixing tank 3.
Since the cleaning tank 62 is used for washing, the development tank 2, the fixing tank 3, the crossover rollers 61, 62, and the piping system for supplying water thereto are also prevented from generating and adhering scale. In particular, in the piping system, clogging of the inside of a pipe or a filter due to water scale is prevented, and in the crossover rollers 61 and 62, water scale adheres to the roller surface, which adheres to the photosensitive material S to generate dirt. This is prevented.

In the present invention, the use amount of the anti-scale agent 40 in the washing tank 4 is preferably 2 to 500 mg, more preferably 5 to 200 mg, and still more preferably 1 liter of the capacity (liquid volume) of the washing tank 4. 10 to 100 mg.

The amount of the anti-scaling agent 40 used in the stock tank 180 is preferably 2 mg to 10 g per liter of the capacity (liquid amount) of the stock tank 180.
More preferably 2 mg to 5 g, even more preferably 2 to 3 g
It is.

It is to be noted that, if such a scale inhibitor 40 is used after being replaced with a new one after a certain period (for example, 8 to 20 weeks), a more excellent scale prevention effect can be maintained.

The replenishing amount of the washing water from the stock tank 180 to the washing tank 4 is ^{2 to} 20 per m ^{2 of} the photosensitive material to be processed.
Liters is preferred, more preferably 4 to 15 liters.

When the replenishment amount is less than 2 liters, the water exchange rate in the washing tank is low and the residence time is long, so that the scale is easily generated. On the other hand, if it exceeds 20 liters, waste will increase from the viewpoint of resource saving and economy.

In the present invention, if an effective amount of the anti-scale agent 40 is added, it goes without saying that the replenishing amount of the washing water may be outside the above range (for example, no replenishment).

The timing for replenishing such washing water is as follows.
Generally, the processing is performed in synchronization with the processing of the photosensitive material S.

In practice, the frequency of processing of the photosensitive material S may be low. In this case, every time a predetermined time elapses (for example, once a day), all of the washing water in the washing tank 4 is removed. Or some can be replaced. For example, when the processing amount of the photosensitive material S is 0.5 m ² or less in one hour,
The amount of the washing water in the washing tank 4 is
Replace 100% (refill new wash water and drain existing wash water).

By performing such a process, the effect of preventing the generation of scale is further exhibited.

In the photosensitive material processing apparatus 1, the amount of the fixing solution brought into the washing tank 4 varies depending on conditions such as the type of the photosensitive material to be processed and the temperature of the processing solution, but it is 5 to 50 ml per m ^{2 of} the photosensitive material to be processed. In particular, 7 to 30 ml is preferable.

In order to reduce the amount of the developer brought into the fixing tank 3 and the amount of the fixing liquid brought into the washing tank 4, a preliminary washing tank is provided between the adjacent processing tanks 2 and 3 and between the processing tanks 3 and 4. It is also possible to provide a configuration in which a pre-wash is performed by providing a shower or a washing water.

Note that, unlike FIG. 2, in the present invention, the pipe 182 and the pump 192 for supplying water to the crossover rollers 61 and 62 may be omitted.

In the present invention, the anti-scaling agent 40 comprises
A configuration in which only one of the washing tank 4 and the stock tank 180 is inserted may be employed.

In addition, the replenishment of the washing water into the washing tank 4 may be performed by directly piping from the water source 187 to the washing tank. In this case, the anti-scale agent 40 may be provided in the middle of the piping. .

Next, the processing solutions typically used in the present invention include a developing solution, a fixing solution, and a washing water (stabilizing solution).
Will be described.

In the present invention, the developing agent used in the developer is preferably a combination of dihydroxybenzenes and 1-phenyl-3-pyrazolidones or a combination of dihydroxybenzenes and p-aminophenol in that good performance is easily obtained. Combinations of classes are preferred.

Further, ascorbic acids may be used as a substitute for hydroquinones.

The dihydroxybenzene developing agents used in the present invention include hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, 2,5-dichlorohydroquinone, 2,3-dipromhydroquinone, Although there are 2,5-dimethylhydroquinone and the like, hydroquinone is particularly preferred.

The p-aminophenol-based developing agents used in the present invention include N-methyl-p-aminophenol,
p-aminophenol, N- (β-hydroxyethyl)
-P-aminophenol, N- (4-hydroxyphenyl) glycine, 2-methyl-p-aminophenol, p
-Benzylaminophenol and the like, among which N-
Methyl-p-aminophenol is preferred.

The 3-pyrazolidone-based developing agents used in the present invention include 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl -3-pyrazolidone, 1-phenyl-4,4-dihydroxymethyl-3-pyrazolidone, 1-phenyl-5-methyl-3-
Pyrazolidone, 1-p-aminophenyl-4,4-dimethyl-3-pyrazolidone, 1-p-tolyl-4,4-dimethyl-3-pyrazolidone, 1-p-tolyl-4-methyl-4-hydroxymethyl- 3-pyrazolidone and the like.

The developing agent is preferably used usually in an amount of 0.001 to 1.2 mol / l.

Examples of the sulfite preservative used in the development include:
Sodium sulfite, potassium sulfite, lithium sulfite,
Examples include ammonium sulfite, sodium bisulfite, and potassium metabisulfite. The sulfite is preferably at least 0.2 mol / l, particularly preferably at least 0.4 mol / l.
The upper limit is preferably set to 2.5 mol / liter.

The pH of the developer used in the development is 8.5 to 13
And more preferably in the range of pH 9 to 12.
Range.

The alkaline agent used for setting the pH includes:
Sodium hydroxide, potassium hydroxide, sodium carbonate,
Contains pH adjusters such as potassium carbonate, sodium phosphate tribasic, potassium phosphate tribasic.

Using buffers such as JP-A-62-186259 (borate) and JP-A-60-93433 (eg, saccharose, acetoxime, 5-sulfosalicylic acid), phosphates and carbonates. Is also good.

Further, a hardener may be used in the developer.

As the hardening agent, a dialdehyde hardening agent or a bisulfite adduct thereof is preferably used. Specific examples thereof include glutaraldehyde and a bisulfite adduct thereof.

Additives other than the above-mentioned components include development inhibitors such as sodium bromide, potassium bromide and potassium iodide: ethylene glycol, diethylene glycol, triethylene glycol, dimethylformamide, methyl cellosolve, hexylene glycol, and the like. Organic solvents such as ethanol and methanol: 1-phenyl-5-
Mercaptotetrazole, a mercapto-based compound such as 2-mercaptobenzimidazole-5-sulfonic acid sodium salt, an indazole-based compound such as 5-nitroindazole, and a benztriazole-based compound such as 5-methylbenztriazole may also include an antifoggant such as Well, Re
search Disclosure Vol. 176, No. 17643, X
Development accelerator described on page XI (December, 1978), and if necessary, a color tone agent, a surfactant, an antifoaming agent, a water softener, an amino compound described in JP-A-56-106244. And the like.

In the present invention, a silver stain inhibitor, for example, a compound described in JP-A-56-24347 can be used in the developer.

Further, a developer is disclosed in JP-A-56-1062.
No. 44, and an amino compound such as an alkanolamine described in EP-A-0136582 can be used.

The fixing solution is an aqueous solution containing a thiosulfate as a fixing agent, and has a pH of 3.8 or more, preferably pH 4.0 to 4.0.
7.0. More preferably, the pH is 4.2 to 5.5.

Examples of the fixing agent include sodium thiosulfate and ammonium thiosulfate, and ammonium thiosulfate is particularly preferable from the viewpoint of fixing speed. The amount of the fixing agent can be appropriately changed, and is generally about 0.1 to about 3 mol /
Liters.

The fixing agent may contain a water-soluble aluminum salt acting as a hardening agent, and examples thereof include aluminum chloride, aluminum sulfate and potassium alum.

In the fixing solution, tartaric acid, citric acid, gluconic acid or derivatives thereof can be used alone or in combination of two or more. It is effective that these compounds contain 0.005 mol or more per liter of fixing solution.
01 to 0.03 mol / liter is particularly effective.

The fixing solution may contain a preservative (for example,
It can contain a sulfite, a bisulfite), a pH buffer (for example, acetic acid or boric acid), a pH adjuster (for example, sulfuric acid), a chelating agent capable of softening water, or a compound described in JP-A-62-78551. .

The washing water in the present invention is a concept including not only the washing water in a narrow sense but also a so-called stabilizing liquid.

Tap water, ion-exchanged water,
Distilled water or the like can be used, but the washing water may be provided with the following deodorizing means in addition to the contact with the anti-scale agent 40.

[0140] As means for prevention, see JP-A-60-263.
No. 939, No. 60-26394.
Method using magnetic field described in No. 0, 61-13163
No. 2, JP-A-62-115154 and JP-A-62-15395.
No. 2, No. 62-220951, No. 62-209532
The method using the antibacterial agent described in the above item is applicable.

Further, LFWest. "Water Quality C"
riteria "Photo. Sci. & Eng. Vol.9 No.6 (1965), MW
Beach, "Microbiological Growths in Motion-picture
Processing "SMPTE Journal Vol.85, (1976), RODeeg
an, "Photo Processing WashWater Biocides" J. Imagi
ng Tech 10, No. 6 (1984) and JP-A-57-8542.
No. 57-58143, No. 58-105145,
57-132146, 58-18631, 5
Antibacterial agents, antibacterial agents, surfactants and the like described in JP-A-7-97530, JP-A-57-157244 and the like can be used in combination, if necessary.

Further, the washing tank (or stabilizing tank) 4 and the stock tank 180 may be provided with RTKreiman as required.
Authors, J. Image.Tech 10, (6) p. 242 (1984), isothiazoline compounds, Research Disclosure 205
Vol., No. 20526 (May, 1981), isothiazoline compounds, Vol. 228, No. 22845 (1983)
, April issue), the compounds described in JP-A-62-209532, and the like.
It can also be used as a bacteriostatic agent (Microbiocide).

In addition, Hiroshi Horiguchi, “Chemistry of antibacterial and antibacterial measures”,
Compounds such as those described in Sankyo Shuppan (Showa 57), "Handbook of Bacterial Prevention and Prevention Technology", Hakuhodo, Japan Society of Bacterial Prevention and Prevention (Showa 61) may be included.

Needless to say, the additives to the washing water are not limited to those described above.

In the present invention, JP-A-63-1835
A squeeze roller washing tank described in No. 0 can also be provided. It is also preferable to adopt a configuration of a washing step as disclosed in JP-A-63-143548.

Further, as described in JP-A-60-235133, part or all of the overflow liquid from the washing tank caused by replenishing such washing water is used in the preceding treatment step. It can also be used for certain fixers.

In the present invention, the term "development time" refers to the time from when the leading end of the photosensitive material to be processed is immersed in the developing solution to the time when it is immersed in the next fixing solution. The time from immersion to immersion in the next washing water (stabilizing solution), "washing time" means the time of immersion in washing water. The “drying time” refers to the time during which the photosensitive material has entered the drying section.

The above development time is 5 seconds to 3 minutes, preferably 8 seconds to 2 minutes, and the development temperature is 18 ° C. to 50 ° C.
Is preferable, and 20 ° C to 40 ° C is more preferable.

The fixing temperature and time are preferably from about 18 ° C. to about 50 ° C. for 5 seconds to 3 minutes, more preferably from 20 ° C. to 40 ° C. for 6 seconds to 2 minutes. Within this range, sufficient fixing can be performed, and the sensitizing dye can be eluted to such an extent that no residual color is generated.

The temperature and time for washing (stable) are from 0 to 50 ° C.
For 6 seconds to 3 minutes, and more preferably 10 to 40 ° C. for 6 seconds to 2 minutes.

In the present invention, as described above, the photosensitive material that has been developed, fixed and washed with water is dried through a squeeze roller for squeezing the washing water. Drying is preferably performed at about 35 to 100 ° C., and the drying time may be appropriately changed depending on the surrounding conditions, but may be usually about 5 seconds to 3 minutes, more preferably 40 to 80 ° C. for about 5 seconds to 2 minutes.

In the present invention, when developing processing for 100 seconds or less by dry to dry, a rubber material such as that described in JP-A-63-151943 is used in order to prevent development unevenness peculiar to rapid processing. Is applied to the roller at the outlet of the developing tank, and JP-A-63-151944.
As described in the specification, the discharge flow rate for stirring the developer in the developer tank is set to 10 m / min or more,
Further, as described in JP-A-63-264758, it is more preferable to perform stronger stirring at least during the development processing than during the standby.

Examples of the photosensitive material S applicable to the present invention include:
There is no particular limitation, and the present invention can be applied to general black-and-white or color photographic materials. Among them, black-and-white photographic materials are mainly used.

In particular, photographic materials for laser printers and photographic materials for medical images, and X-ray photographic materials for direct medical imaging, X-ray photographic materials for indirect medical use, photographic materials for CRT image recording, microfilms And so on.

Hereinafter, specific examples of the present invention will be described.

(Example 1) Medical X-ray sensitive material RX, Super HR-S, Super HR-A, Super HR manufactured by Fuji Photo Film Co., Ltd.
-L in order of 30%, 50%, 10%,
A running experiment was performed with 10%.

The average processing amount of the photosensitive material per day is about 200 sheets in terms of the size of four slices.

The automatic processing equipment, processing liquid, etc. used in this experiment are as follows.

These are all made by Fuji Photo Film Co., Ltd. Automatic processing machine: FPM-5000 type Processing solution: Developer / RD-3 Starter / RD-3S Fixer / Fuji F

The processing steps were as shown in Table 1 below, and tap water was used as the washing water.

[0161]

[Table 1]

The amount of the starter used was 20 ml per liter of the developing replenisher.

20 liters of a developing replenisher was stored in the developing tank of the above-mentioned automatic developing machine. Next, 440 ml of the starter was weighed and added to the developing tank. Thereafter, a development replenisher was further added to a point just before overflowing, and this was used as a development start solution.

On the other hand, the fixing tank was filled with the fixing replenisher just before overflowing.

The developing replenisher is 45 m per one sheet of the quarter size.
l, 60 ml of fixing replenisher was replenished.

The washing tank was filled with tap water, and the developing water was replenished with washing water at a rate of 5 liters per minute (0.65 liters per one piece of the cut-off size).

After the completion of the treatment for one day, the washing water in the washing tank was completely drained, and this was repeated daily.

In the washing tank and the like, a scale inhibitor shown in Table 2 below was added.

[0169]

[Table 2]

As shown in Table 2, in each of Examples 1 and 2 of the present invention, the effect of preventing scales was excellent, the safety was secured without toxicity, and the handling was easy.

In particular, the effect of Example 2 of the present invention using actinomycetes and algae is remarkable.

(Example 2) X-ray medical materials Super HR-S, Super HR-A, Super HR-L, MI manufactured by Fuji Photo Film Co., Ltd.
-NM, MI-Dup, and LI-FM in order of processing amount (area) ratio of about 60
%, 10%, 10%, 5%, 5%, and 10% of the running experiment.

The average processing amount per day of the photosensitive material is about 200 sheets in terms of the size of the four slices.

The automatic machine used in this experiment was a modification of the automatic machine FPM-9000 manufactured by Fuji Photo Film Co., Ltd. and was configured as shown in FIG. 2. The processing steps were as shown in Table 3 below. is there.

[0175]

[Table 3]

The processing liquid and its replenishment are as follows.

Preparation of concentrated solution for development processing

<Developer> Parts agent A Potassium hydroxide 330 g Potassium sulfite 630 g Sodium sulfite 255 g Potassium carbonate 90 g Boric acid 45 g Diethylene glycol 180 g Diethylenetriaminepentaacetic acid 30 g 1- (N, N-diethylamino) ethyl-5-mercaptotetrazole 0.75 g Add hydroquinone 450g water and add 4125ml

[0179] Part agent B Diethylene glycol 525 g 3-3'-dithio-bis hydrocinnamic acid 3g glacial acetic 102.6 g 5-nitroindazole 3.75 g 1-phenyl-3-pyrazolidone 34.5g Water to make 750ml

Parts agent C Glutaraldehyde (50 wt / wt%) 150 g Potassium bromide 15 g Potassium metabisulfite 105 g Water was added to 750 ml

[0181] <fixer> Ammonium thiosulfate (70wt / vol%) 3000ml ethylenediaminetetraacetic acid disodium, dihydrate 0.
45 g sodium sulphite 225 g boric acid 60 g 1- (N, N-dimethylamino) -ethyl-5-mercaptotetrazole 15 g tartaric acid 48 g glacial acetic acid 675 g sodium hydroxide 225 g sulfuric acid (36N) 58.5 g aluminum sulfate 150 g water was added 6000 ml pH 4.68

Preparation of Processing Solution The above-mentioned concentrated solution of the developing solution was filled into the following containers for each part. In this container, the respective partial containers of the parts agents A, B, and C are connected together by the container itself.

The above-mentioned fixing solution concentrate was also filled in the same type of container.

First, 300 ml of an aqueous solution containing 54 g of acetic acid and 55.5 g of potassium bromide was placed in a developing tank as a starter.
Was added.

The treatment agent-containing container is turned upside down and inserted into the perforation blade of the treatment liquid stock tank mounted on the side surface of the automatic processing machine to break the sealing film of the cap and to remove each treatment agent in the container. Filled the stock tank.

Each of these treating agents was filled in the developing tank and the fixing tank of the automatic processing machine at the following ratios by operating the pumps provided in the automatic processing machine.

In addition, every time the photosensitive material was processed into eight pieces in terms of a quarter size, the processing solution stock solution and water were mixed at this ratio and replenished into the processing tank of the automatic processing machine.

Developer Parts agent A 55 ml Parts agent B 10 ml Parts agent C 10 ml water 125 ml pH 10.50

Fixer concentrate 80ml Water 120ml pH 4.62

The washing tank was filled with tap water.

As a scale inhibitor, 0.4 g of actinobacteria supported on perlite having an average particle diameter of 100 μm and an average pore diameter of 3 μm was covered with a polyethylene bottle (the bottle opening was covered with a 300 mesh nylon cloth. 3 pieces of water and bacteria can be distributed from the cloth), two of them are placed at the bottom of the washing tank and one is placed at the bottom of the washing tank (0.2 liter). Each sunk.

The photosensitive material is exposed to X-rays, and is developed using the above-mentioned automatic processing machine and the respective processing solutions mixed in the above-mentioned ratios, in the above-mentioned process time, for each four-piece size (10 × 12 inches). The processing was performed while replenishing 25 ml of the solution and 25 ml of the fixing solution.

Into the washing tank, washing water is supplied at a rate of 5 liters per minute from the stock tank (0.5 liters per sheet), and a ball valve type solenoid valve is synchronized with the processing time of the photosensitive material. Supplied open.

The time during which the photosensitive material is not processed (standby time) is 1
When the time was reached, the solenoid valve was automatically opened for 2 minutes, and the washing water was supplied to the washing tank.

After the completion of the treatment for one day, the solenoid valve installed in the drain pipe was opened to drain all the washing water in the washing tank, and this was repeated daily.

Further, once when the self-developing machine is started (every morning),
When the automatic developing machine is stopped, 40 ml of water in the stock tank in contact with the anti-scale agent is sprayed onto the crossover roller between the developing tank and the fixing tank and between the fixing tank and the washing tank twice to wash the crossover roller. did.

Under the conditions described above, a running experiment was performed for three times.
After months of operation, there is almost no adhesion of scale on each treatment tank, especially on the inner wall of the washing tank, transport rollers including crossover rollers, and other transport mechanism parts such as roller shafts and gears. No clogging occurred.

[0198]

As described above, according to the present invention, an extremely excellent effect of preventing the generation of scale is obtained in the washing tank of the photosensitive material processing apparatus and other places, and the structure is simple. In addition, the structure of the device is not complicated and the device is not enlarged.

[Brief description of the drawings]

FIG. 1 is a sectional side view showing a configuration example of a photosensitive material processing apparatus used in the present invention.

FIG. 2 is a schematic structural view for explaining a processing method for a silver halide photographic light-sensitive material of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Photosensitive material processing apparatus 2 Developing tank 3 Fixing tank 4 Rinse tank 40 Anti-scaling agent 51, 52, 53 Transport roller 61, 62, 64 Crossover roller 7 Guide 8 Squeeze section 81 Squeeze roller 9 Drying section 91 Casing 92 Transport roller 93 Guide 94 Hot air supply means 95 Blower fan 96 Heater 97 Duct 10, 11 Circulation pump 12, 13 Tube 140, 144 Drug container 141, 142, 143 Partial container 150, 154 Stock tank 151, 152, 153 Parts agent storage section 161, 162, 163, 164 Liquid supply pipes 171, 172, 173, 174 Pump 180 Rinse water stock tank 181, 182, 183, 184, 185 Pipe 186 Valve 187 Water source 191, 192, 193, 194 Pump 200 Replenisher supply system S photosensitive Fee

Continuation of the front page (56) References JP-A-63-187243 (JP, A) JP-A-63-129343 (JP, A) JP-A-63-88548 (JP, A) JP-A-2-100700 (JP, A) , U) (58) Fields studied (Int. Cl. ⁶ , DB name) G03C 11/00

Claims (7)

(57) [Claims] 1. A silver halide photographic light-sensitive material is processed using at least a photographic material processing apparatus for developing, desilvering and washing with a silver halide photographic light-sensitive material. A method for processing a silver halide photographic light-sensitive material, wherein water brought into contact with a material having soil bacteria supported on the carrier is used at least for the water washing treatment. 2. The silver halide photographic light-sensitive material according to claim 1, wherein water brought into contact with a material having soil bacteria carried on the carrier is used for replenishing the processing solution for the development process and / or the desilvering process. Material treatment method. 3. The halogenation method according to claim 1, wherein water brought into contact with the material having soil bacteria carried on the carrier is used for washing a transport mechanism component for transporting the silver halide photographic light-sensitive material. Processing method of silver photographic photosensitive material. 4. The soil fungus according to claim 1, wherein said soil fungus is an aerobic fungus.
4. The method for processing a silver halide photographic light-sensitive material according to any one of items 1 to 3. 5. The method for processing a silver halide photographic light-sensitive material according to claim 1, wherein said soil bacteria are actinomycetes or algae. 6. The method for processing a silver halide photographic light-sensitive material according to claim 1, wherein a radioactive bacterium and an algae are used in combination. 7. The replenishing amount of the washing water in the washing process is ² per 1 m ^{2 of the} silver halide photographic light-sensitive material to be processed.
7. The method for processing a silver halide photographic material according to claim 1, wherein the amount is from 20 to 20 liters.