JPH0396946A - Automatic developing device having excellent water saving efficiency and method for processing silver halide black and white photosensitive material - Google Patents

Abstract

PURPOSE:To improve the water saving efficiency of the automatic developing device by adding an oxidizing agent to the contaminated washing water to regenerate the water and using the washing water after removing the reaction products with the oxidizing agent therefrom by a filter. CONSTITUTION:The unused washing water is filled in a washing tank 1 and a water storage part 2 and the fixed photosensitive material is washed in the tank 1. The washing water is replenished from the tank 2 according to the processing amt. The overflow water of the tank 1 is sent into the tank 2 and is stored therein. The washing water in the tanks 1, 2 is contaminated by the carry-over liquid component from the photosensitive material and the eluted component from the photosensitive material and, therefore, the oxidizing agent (e.g.: hydrogen peroxide water) is supplied from an oxidizing agent supplying tank 5 to the tank 2 at proper times to regenerate the washing water. Further, the reaction products by the oxidizing agent are removed by the filter unit 4 consisting of the filters 4a, 4b of different pore sizes (e.g.: 7mu, 10mu mesh hole sizes) and thereafter, the washing water is used.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial field in Icheon] The present invention relates to an automatic developing device for black-and-white photosensitive materials made of silver chloride and a processing method using the device, and more specifically, to The present invention relates to a silver halide black-and-white photosensitive Torikawa automatic developing device that provides superior finishing performance, and a processing method using the device.

[Prior Art] Currently, the development of silver halide photosensitive materials is generally carried out using an automatic developing machine. After the development and fixing process, the photosensitive printing plate is washed with water (the processing liquid components of the previous process included in the printing plate, 1
The fixer solution is removed by washing with water. If this washing with water is insufficient, performance problems such as deterioration of the image over time due to residual fixer in the material will occur in the first black and white silver halide photosensitive separation of R. Therefore, photosensitive + A It
In order to sufficiently remove the residual seedling fixer components in the seedlings, it is necessary to perform sufficient washing with water, but it is not possible to perform sufficient washing as described above with the washing water mother housed in the washing tank of the automatic developing machine. there were. For this reason, water is constantly supplied during the washing process.
The current situation was to drain the water directly into the sewer system.

Under the above circumstances, in recent years, there has been an increasing demand for saving water when washing automatic processors from the viewpoint of saving resources and reducing production costs, and the demand for technological improvements has accordingly increased. In other words, problems such as land subsidence in urban areas, increases in water and sewage charges due to capital investment due to delays in sewage treatment facilities compared to countries in Europe and the United States, and increases in
The demand for saving washing water in order to cope with water outages caused by the unique weather conditions of the summer [well, the demand for saving water during washing has become increasingly strong in recent years, coupled with the increase in processing volume at plate making plants in Tokyo and the problem of total drainage regulations. It's coming.

In order to meet the water-saving requirements as described above, a chemical treatment is performed instead of the conventionally proposed water-washing process. For materials, especially for printing, plate making, and automatic development equipment, the number of processing tanks has increased, and the installation has become more complicated and larger.As a result, the processing line has become longer, and the processing time for photosensitive materials has increased. From the viewpoint of speeding up the process by 4"P compared to the main process, this is completely contrary to the general process and cannot be applied.

[The problem solved by the invention] For this reason, one method is to install a water storage tank for storing washing water separately from the washing cypress which undergoes washing treatment, near the washing cypress.
One possible method is to circulate the washing water between the water storage tank and the washing cypress, but this method reduces the amount of exposure to light that is not processed.
: Photosensitivity of the developer, fixer, dye, pigment, surfactant, pyradine, etc. in the previous process brought into the washing water +4
The concentration of eluted components etc. from II increases as the treatment level increases, and especially in recent years, the concentration of iodine consumption levels as a legally established water quality standard has increased.
As a result, -Ll re-1 occurs in a short period of time, and problems regarding drainage remain.

The present inventors previously addressed the above problem in Japanese Patent Application No. 1-65
No. 440, Japanese Patent Application No. 1-65442, proposes to install an oxidizing agent supply means as a regeneration means for producing 7Jj from the washed water.

However, in the method of circulating the washing water as described above, the occurrence of water scale, mold, etc. increases due to the long stagnation time of the washing water in the system. The technology of adding chemicals such as bactericides and anti-mold agents has been known for a long time, but there is a method that can simultaneously solve the conventional problems of water-saving efficiency and wastewater treatment as well as the generation of limescale etc. had not yet been realized.

Furthermore, when an oxidizing agent supplying means is used as a regenerating means as described above, the products generated in the reaction of washing water regeneration by the oxidizing agent become precipitates, which adversely affects the performance of the photosensitive material after processing. Problems are also occurring.

Accordingly, a first object of the present invention is to provide an automatic developing device that enables the recycling of washing water and, as a result, improves water-saving efficiency, and a method for processing silver halide black and white light-sensitive materials using the device. be.

A second object of the present invention is to provide an automatic developing device and a processing method capable of removing limescale, mold, etc. generated by circulating washing water.

A third object of the present invention is to provide an automatic developing device and a processing method that can efficiently remove precipitates such as reaction products generated when an oxidizing agent supply means is used as a washing water regenerating means. There is a particular thing.

Furthermore, the object of M4 of the present invention is to provide an automatic JA imaging device capable of purifying contaminated wash water to the point where it can be drained, and a method for treating waste water of contaminated wash water produced by improving water saving efficiency.
There are many things.

[Means for Solving the Problem] In view of the above-mentioned problems, the inventors of the present invention have conducted intensive research and found that the object of the present invention is to solve at least a developing section, a fixing section, and In the silver halide black and white photosensitive automatic developing apparatus comprising a water washing section, the water washing section includes at least a washing means for washing a photosensitive material, and a water containing used washing water discharged from the washing means for washing the photosensitive material. a water storage means for temporarily storing washing water to be supplied to the means; a regeneration means for adding an oxidizing agent to regenerate the used washing water;
A filter means comprising at least two types of filters having different pore diameters is provided between the water storage means and the water washing means, and the washing water in the washing means and the washing water in the water storage means are transferred between the washing means and the water storage means. A circulation means for circulating between the
An automatic developing apparatus for silver halide black-and-white photosensitive materials, characterized in that the washing section further includes a method for applying a purifying agent to the water storage means when the concentration of contamination in the washing water being recycled by the circulation means exceeds a predetermined value. An automatic developing apparatus for silver halide black-and-white photosensitive materials, characterized in that it has a purifying agent supply means, and a drainage means for draining at least a part of the washing water in the water storage means after supplying the purifying agent, and It has been found that the present invention can be achieved by a method for processing a silver halide black-and-white light-sensitive material, which is characterized by processing using any automatic developing device.

The present invention will be explained in more detail below based on the drawings.

FIG. 1 is a schematic view schematically showing an example of a water washing section of an automatic developing device of the present invention.

According to FIG. 1, the washing section of the developing device of the present invention includes a washing tank 1 for processing the photosensitive material, washing water for replenishing the washing camellia 1, and washing water overflowing from the washing tank 1 due to the above-mentioned collection. A water storage tank 2 provided near the washing tank 1 for storing water, and a circulation means for replenishing washing water from the water storage tank 2 to the washing tank 1 and sending overflow water from the washing tank 1 to the water storage tank 2. 3. For example, water storage! A filter unit section 4 with different pore diameters is provided in the middle of the path from 2 to the washing tank 1.
The filter means 4 consisting of a and 4b and the circulation stage 3
NiJ: An oxidizing agent supply ffl5 for automatically supplying an oxidizing agent to the water storage tank 2 based on the sensitive material processing area information as a regeneration means to the circulating washing water, and at least 1 in the water storage tank 2. It consists of 1,000 discharge stages 6 from which the parts exit one by one.

That is, at the start of the development process, the washing tank 1 and the water storage tank 2 are filled with unused washing water, and then the developed and fixed photosensitive material is washed in the washing tank 1, and the water is stored according to the processing level of the photosensitive material. Rinsing water is automatically replenished from 12, and as a result, the used washing water that overflows from the washing tank 1 is sent to the water storage MJ2 instead of being drained as it is in the past, and is temporarily stored in the W tank.
? Watered.

As the amount of processing increases, this cycle is repeated, whereby the washing water in the washing tank 1 and the water storage tank 2 is absorbed by the photosensitive material, fixing solution components, dyes, pigments, surfactants, etc.
Components eluted from photosensitive materials such as geladine are contaminated with J:, and as a result, the washing efficiency is reduced and the finish of the photosensitive material after washing is affected.

Therefore, by providing an oxidizing agent supply tank 5 as a regeneration means and supplying the oxidizing agent to the water storage tank 2 at appropriate times, it is possible to regenerate the washing water. However, in this case, J
Products generated in the washing water regeneration reaction become precipitates and have a negative effect on the images obtained. Therefore, it is necessary to efficiently remove this decomposed product and remove the silver compounds contained in the decomposed product. In order to efficiently remove the Improved water purification.

In the present invention, the products produced as a result of the use of an oxidizing agent are mainly inorganic products, mainly silver, but decomposition products such as dye marks and pigments caused by children are also produced by repeated circulation of washing water. Therefore, by using two or more types of filters with different pore sizes, it is possible to remove the products of the various glue sizes mentioned above.

The filter used in the present invention will be explained below. Materials for filter fibers include paper-like fibers with cellulose composition, carbon fibers, aramid fibers, Teflon resin fibers, hemp, glass fibers 1, poly]niburene foam A, and polypropylene foam A in terms of heat resistance and chemical resistance. In particular, in order to extend the life of the filter, epoxy resin is coated on the surface of the filter, and polypropylene products are used in close contact with the surface of the filter. In order to prevent clogging of the gelled product and extend its life time, it is preferable to use a solid filter made of charcoal fiber or the like, for example.

In addition, as for the filter of at least 2 scales used in conjunction with J5 in the present invention, at least one type of b is commercially available as a paper for general industrial use. Using the processed one, at least one other type is i1! It is preferable to use boronate 7J lath fiber navy blue as a prefilter in order to have a quick overspeed and extend the filter life.

In particular, it is preferable to use at least one type having a pore diameter of 0.5 μ to 7 tl and at least one type having a pore size of 7 μ to 20 μ in combination.

11 Also, in d3 of the present invention, it is preferable that at least 02 types of filters used have a difference in pore diameter of 3 μ or more, and further preferably a difference of 3 to 20 μ.

The filter means interposed in the circulation section of the present invention includes:
It is particularly preferable that the filter elements 1 to 1 are assembled in a housing and connected to each other by a vibrating line so that complete filtration can be achieved, and it is preferable that the right-effect filtration area per element 1 to 1 is large. Further, it is particularly preferable to use wrinkles A5 and pleats on the filter paper so that the installation volume is small relative to the required filtration amount.

Further, two or more types of filters having different pore diameters may be used by being connected in series, or may be used by being connected in parallel.

In the present invention, it is preferable that at least one of the filters constituting the filter means is a filter that has a bactericidal effect. After processing, polyethylene terephthalate and a polymer with carboxyl groups are spun into fibers.Metal elements such as copper and silver with antibacterial properties are kneaded into the fibers, and the antibacterial fiber is used as a filter material. Preferably used are silica fibers made of silica anolemina-based fibers, which are made by adhering them to polyethylene resin, and fibers made by adhering them to polypropylene resin. It is also preferable to use as the filter part a filter made from Ishiga 1 dog which has a mechanism for trapping 7J B. bacterium in its pores.

Examples of the oxidizing agent that can be used as a regeneration means in the present invention include metal or nonmetal oxides, oxide acids or their salts, peroxides, and compounds containing the acid type listed on the right. Since the main purpose is to decompose the fixer components brought into the used washing water in the water storage tank, the above-mentioned acids include sulfuric acid, nitrous acid, nitric acid, hypothermic acid, etc.
7';n:L<, As the peroxide, hydrogen peroxide solution, phenylene reagent, etc. are particularly preferred, and ozone is also preferably used.

These oxidizers are diluted with water, etc., and then stored in the oxidizer supply tank 5, which is arranged adjacent to the water storage tank 2. l 2, but usually (:L from the supply cypress 5 as necessary,
Water is added automatically at a constant rate, preferably once every few hours, and automatically dropped into the water storage tank 2 by listening to the supply valve.
added to. The amount added can be arbitrarily selected depending on the type of photosensitive material, amount of processing, type of processing solution, etc., but since it is considered to be related to the amount of fixer to be added, the amount can be adjusted by setting the timer as described above. In J5, which automatically adds the required amount on an hourly basis, 172 mol to several {(; in the current molar range, especially 172 to several It is preferable to add it in the range of 3 times the molar equivalent.In fact, since the fixer component itself to be brought in is proportional to the amount of processed light-sensitive material, it is possible to determine the amount added depending on the processing sensitivity 11Jffi. In addition, the water storage tank 2 can be provided with a known stirring means in order to perform the regeneration efficiently.

As the amount of water to be treated further increases and the degree of contamination progresses, it becomes necessary to drain all or at least a portion of the washing water in the water storage cypress 2 to IJl water and replace it with fresh washing water.

However, especially when the degree of contamination exceeds the above-mentioned wastewater standards, l. : In case (because the water supply to the sewage system becomes inefficient, it is necessary to constantly detect contamination of flush water and keep its concentration within the permissible range. For this reason, contamination of flush water The concentration is measured by any method, preferably by measuring the washing water in the water storage tank 2 using a contamination degree measuring means, and based on the measured value, the concentration is measured in the oxidizing agent supply tank 5 and the oxidizing agent supply tank 5, or separately installed 1. A purifying agent is automatically supplied from the purified purifying agent supply tank to purify the flushing water in the water storage cypress 2 to an acceptable level.After this, at least a part of the purified flushing water is drained at the drainage stage 6. All of the flushing water in the water storage tank 2 may be flushed with water, but only a portion may be drained and replaced with fresh flushing water for mixed use.

In the present invention, the contamination concentration of the washing water refers to the fixer component that is considered to have the most influence on the iodine consumption, since it is necessary to satisfy the iodine consumption regulations because it is discharged into the sewage. It can be thought of as the concentration of thiioic acid ions such as ammonium thiosulfate and sodium diosilicate.

As the purification agent used in the present invention, an oxidizing agent similar to that used as the regeneration means (16) is used. It is preferable to use this in combination.

These purifying agents are used, for example, when the concentration of dionitric acid ions in the washing water in the water storage tank 2 exceeds a value corresponding to the standard value for iodine consumption. It can be added to the water storage tank 2 by diluting it with water or the like and adding it to the water storage tank 2 from a purifying agent supply jam placed adjacent to the water storage tank 2, but usually a constant amount of purification agent is added from the supply jamb as needed. It is automatically added in small amounts, preferably once every few hours, into the water storage cypress 2 by listening to the supply valve and letting it fall automatically. The amount to be added can be determined experimentally depending on the concentration of diosulfate ions in the washing water.

In the present invention, as a means for automatically purifying by supplying a purifying agent in a fixed amount according to the depth of thiosilicate ions, OR
It is possible to measure the ORP value using a P (oxidation-reduction potential) electrode and automatically add the purifying agent based on the ORP value.

Specifically, sodium hypochlorite solution is adjusted to pt-14 or Il+-17 at a predetermined temperature of 81 degrees.
The amount of purifying agent added can be determined by adding ~lium and measuring the iodine consumption, KMn 04 consumption, and ○R P tffj. That is, for example, 0.03 NNa
2 When adding borium hypochlorite to each of pi-14 and DI-17 in the S2 03 solution, the oR of the first wave in the solution of ρ order 7 at a certain addition point.
A sharp rise in the P value was observed, and this point coincided with the lowest value of urin consumption. This indicates that the entire amount of S2032- was oxidized. When sodium hypochlorite is further added, a second wave rise of the p7 solution and a rapid rise of the pH 4 solution are observed.

In this way, purification can be carried out automatically by adding sodium hypochlorite until the voltage reaches 500 to 800 mV using the rising of the 011P value in the neutral or acidic range. By this method, it is possible to determine the extent of addition of purifying agents by measuring the RP value in various cases.

The above ORP? ! ! The electrode may be installed in a water tank and measured continuously or as needed, or it may be pushed into the water tank at any time for measurement.

Alternatively, the head may be installed in the circulation system outside the water tank, inside the water wash Wj, etc., and the measured value may be used as a substitute for the measurement height inside the water tank.

This measured value can be automatically or artificially fed back to the purification agent supply means to operate, for example, an electromagnetic on-off valve, etc., to supply the required amount of purification agent to the flush water of the water tank. can. Conventional and well-known agitation means can also be placed in the reservoir to facilitate purification.

Another method for measuring contamination concentration is a method in which the area of the processed light-sensitive material is measured and used as a substitute. That is, since the thionitrate ion, which is the main contaminant, is a component brought in by the processed sensitive material, it is thought that its base corresponds approximately to the initial size of the processed material, that is, the total area. Therefore, in an experiment, it is necessary to determine in advance the contamination concentration when a predetermined amount of photosensitive material is processed and the amount of purifying agent required to purify it to a predetermined value. Using the results, the total area of the processed photosensitive material can be measured and calculated, and a corresponding amount of cleaning agent can be supplied.

Specifically, such a method involves detecting the photosensitive material with a sensor installed near the photosensitive material feeder of the automatic processor.
Based on the information from this sensor, a counter connected to the sensor counts the total area of the processed sensitive material. If the counted total area exceeds a value corresponding to a predetermined contamination concentration, a predetermined amount of purification agent is added to the water tank based on the experimental value.
(Supplied. At this time, a system may be installed in the device that inputs the experimental values in advance, calculates the appropriate purification agent corresponding to the total area value, and automatically supplies it.
Further, when the total area counter exceeds a predetermined value, an alarm sounds, and in response to this, the supply may be performed artificially based on experiments. The reservoir can also include conventional agitation means to facilitate purification.

By adding the purifying agent 1 as described above, at least a portion of the washing water purified to a predetermined value, at least a value satisfying the drainage standard, is drained through the drainage stage 6. The drainage means may include, for example, a solenoid valve20 that can be opened and closed automatically, but the valve may also be configured to open automatically after the purifying agent is supplied, or automatically or automatically after the purifying agent is supplied or purification is confirmed. It may be opened artificially to drain water.

As the water washing means of the automatic developing apparatus of the present invention, various conventionally known water washing methods and methods can be used.

Additionally, water containing various additives known in the art can be used as the rinsing water.

Washing water treated with mold-proofing means is effectively used to prevent the formation of limescale in water stored in a water tank.

This J: As a fungal prevention measure, please refer to the special appendix 6 (+ -
The ultraviolet irradiation QJ method described in No. 2 6 3 939, li
The method using the fli field described in lil60-2G3940, the method of purifying water using an ion exchange resin described in lil67-731832, and the method described in Japanese Patent Application No. 60-253807, No. 60-295804, same 6
Methods using antibacterial agents described in No. 1-63030 and No. 64-51396 can be used.

Furthermore, L. E. West “Water Qu”
alityCriteria” pl+oto 3
ci&Eng. V (11.9 NO6 (196
! i), N. W. 3 cacb” Micro
biologicalGrowtl1s in M
tion-picture Processing
“SMPTE Journal Vol.
85, (1976). R. 0. l)e
egall, “photo proc
essino WashWater 3iocid
es” J.Imaging Tech
, Vol. 10, No. 6 (1984)EI
．． and Special Bulletin No. 57-8542, No. 57-58143,
No. 58-105145, No. 57-132146, No. 58-18631, No. 57-97530, No. 57-
Antibacterial agents, anti-inflammatory agents, surfactants, etc. described in No. 157244 and the like can also be used in combination.

Furthermore, R. T. Written by K. Reiman d. I maoe, Tech 10, (6) 2
42 (1984), IIESEARCII DISCLOSIII SEF
Volume 205, IteIll2052G' (198
Isodiazoline compounds described in 1st year, May issue
Volume 228, I tell 22845 (1
Isodiazoline compounds described in 1983, April issue, compounds described in Japanese Patent Application No. 61-51396, etc. can also be used in combination as microbiocides.

Furthermore, specific examples of anti-pissing agents include phenol, 4-chlorophenol, pentachlorophenol, cresol,
0-phenylphenol, chlorophene, dichlorophene, formaldehyde, glutaraldehyde, chloracetate, 1) monohydroxybenzoic acid ester, 2
-(4-thiazoline)-benzimidazole, penzisothiazolin-3-one, dodecylpendyludimethylammonium chloride, N-(fluorodichloromethylthio)-7talimide, 2,4.4'trichloro2'-hydro Examples include oxydiphenyl ether.

In addition, methods such as processing with various types of agitation, use of washing accelerators, supply of washing water according to the treated area of photosensitive forest materials, and use of a squeeze tool to reduce carryover to the washing tank are also combined. It can be used as

The water storage 41!2 according to the present invention may be made of vinyl chloride containing an antibacterial agent or the like from the viewpoint of preventing limescale and corrosion, or may be made of nylon-treated material on the inside of the tank.

23 As a circulation means suitable for the present invention, water storage I! To replenish the washing water from the water storage tank 2 to the washing tank 1, for example, when the photosensitive material is pushed into the automatic developing machine, it is detected by a sensor, and thereby washing water is automatically supplied from the water storage tank 2 to the washing tank 4rj1. A solenoid valve design may be used in which the supply of rinsing water is stopped when the photosensitive tJ dye is not detected. At this time, it is preferable to forcibly transfer the washing water using a high-pressure bomb, and the amount of replenishing washing water is 1 per 112 areas of the treated shrine.
0 to 30 l is preferable, and 15 to 25 ffi is more preferable.

Also, the flushing water that overflows from the flushing tank 1 due to the above-mentioned replenishment is directly sent to the water storage tank 2 through the pipe connected to the water storage 4fl2 and is temporarily stored therein.

As described above, as in the present invention, a water tank is provided.
By recycling the washing water and reusing the washing water, water saving efficiency is increased, and furthermore, 1!
I! The inventors have made extensive research into the concept of treating wastewater by purifying the contaminated wash water that occurs due to an increase in ffi. This is something that was discovered for the first time as a result of research and has never been found in the prior art24.

Silver halide photosensitive materials applicable to the automatic developing device of the present invention are black and white photosensitive materials, and particularly include black and white negative films, black and white reversal films, X-ray films, copying films, printing films, and gravure films.

Furthermore, all of the various conventionally known systems can be used for the developing section, fixing section, and drying section of the automatic developing device of the present invention.

A combination of dihydroxybenbins and 1-phenyl-3-virazolidones is preferably used as a developing agent in the black-and-white developer applied to the present invention.

Of course, a p-amine phenol-based developer may also be included.

The dihydroxybenzene developing agents used in the present invention include hydroquinone, chlorohydroquinone, promhydroquinone, isobrobylhydroquinone, medylhydroquinone, 2,3-dichlorohydroquinone, 2,5-
Examples include dichlorohydroquinone, 2,3-dibromohydroquinone, and 2,5-dimedylhydroquinone, but hydro[J-quinone is particularly preferred.

As a developing crude drug for 1-phenyl-3-pyrazolin 1zone or its derivatives, 1-7enyl-4,4-dimedyl-3-
Virazolidone, 1-7enyl-4-4-hydroxymethyl-3-virazolidone, 1-phenyl-4,4
-dihydroxymedyl-3-virazolidone and the like.

In p-aminophenol-based developing agents, N-methyl-p
-aminephenol, p-aminophenol, N-(β
-Hydroxydiyl)-1) Monoaminophenol, N-
(4-hydroxyphenyl)glycine, 2-medylu p
Among them, N-aminophenol is preferred.

The developing agent is usually 0. 01 mol/ffi-L2 mol/i
It is preferable to use the same amount of water.

01-1 of the developer used in the present invention preferably falls within the range of 9 to 13. More preferably, pl-l 1 is in the range of 0 to 12.

1] The alkaline agents used for setting 1-1 include sodium hydroxide, potassium hydroxide, sodium helium carbonate, potassium carbonate, sodium triphosphate, and potassium triphosphate. Contains p l-1 modulator.

JP-A-61-28708 rock (boric acid basin), special I7iI
No. 1986-93^39 (e.g. Zaccharose, AL
Any buffering agent may be used, such as l-J xime, 5-sulpo'lyruthylic acid), phosphate, carbonate (T).

Additives used in addition to the above ingredients include sodium sulfite, potassium sulfite, ridium sulfite, ammonium subate, and 1il bicarbonate! IS sodium, sodium metabisulfite, formaldehyde ta. qt ti
silicate salts such as q-sodium; phenomenon inhibitors such as helium bromide, potassium bromide, and potassium iodide; ,
Organic solvents such as hexylene glycol, ethanol, methanol: 1-phenyl 5-menorecab 1 ~ te 1 ~ razonore, 2-merkab 1 to penzimidazole-5-sulfonic acid sodium salt 2'? Even if it contains an anti-fog agent such as Merkab 1 mono-based products such as 5-2110 indazole, indazole-based compounds such as 5-methylbenz I-riazole, and Benz 1 heliazole-based products. Also, if necessary, color toning agent, W surface activation↑I1 cutting, antifoaming agent, water softener, JP-A-56-106
It is also possible to include the amine compounds described in No. 244.

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

The developer used in the present invention includes Japanese Patent Application Laid-Open No. 56-106244
Amine compounds such as alkanolamines described in No. 1 can be used.

Besides this, L. F. A. ``Futographic Processing Chemistry 1-1'' by Meng, published by Fucal Press (
1966<L), pages 226-229, U.S. Patent No. 2,
Those described in No. 193,015, No. 2,592,364, Tokoku No. 1101, No. 48-64933, etc. may be used.

The fixer used in the present invention is Diolil! It is an aqueous solution containing an acid salt, and has an or-+ of 3.8 or more, preferably 4.
Fixing agents include sodium diosulfate and ammonium diosulfate, which contain thiasulfate ion and ammonium ion as essential components, and the fixing speed is From this point of view, Dio{iWi Iv ammonium is particularly 9T2L.

The amount of fixing agent to be used can be changed as appropriate, and is generally about 0.01 to about 6 mol/i.The fixing solution may also contain a water-soluble aluminum salt that acts as a hardening agent. Examples include aluminum chloride, ammonium sulfate, and alum.

Tartaric acid, citric acid, or conductors thereof can be used alone or in combination of two or more kinds in the fixer. Those containing 0,005 mol or more of these compounds per fixer are effective, especially 0.01 mol/~0.03 mol/
l is particularly right-handed.

Specifically, tartaric acid, hydrium tartrate, sodium tartrate, potassium sodium 1-lium tartrate, citric acid, sodium 1 helium citrate, hydrium citrate, lithium citrate,
There are things like ammonium citrate.

The fixer may optionally contain preservatives (e.g. sulfites, bisulfites), buffers (e.g. acetic acid, nitric acid), p1
-1 regulator (for example, sulfuric acid), a chelating agent with water softening ability, and the compound described in Japanese Patent Application No. 60-213562.

[Example] EXAMPLES The present invention will be explained in more detail with reference to Examples below.

Experimental Example 1 Assuming that fixer components were brought into the washing water for photosensitive materials, Konica Fix υ-851 was added to 62ffi of water as a fixer.
(Made by Konica ■) (1) 300cc, (2) 5
By mixing 00cc or (3) 700CC and adding a 6% hydrogen peroxide solution as an oxidizing agent to each of these, the iodine is removed from the diosilic acid component in the mixed fixer.
A substitution test was conducted to determine the amount of purifying agent added to reduce i&m to below the regulatory standard value of 220 mg/1. This result is shown in (1), (2) and (3) above.
) is shown in Figure 2. However, the amount of iodine consumed is determined based on the sewage test method -b after adjusting the sample to be almost neutral.
A constant amount of iodine-potassium iodide solution was added to this sample, and after leaving it for 2 to 3 minutes at room temperature, the remaining iodine was reduced to 1
/100 normal sodium thiosulfate solution.

Figure 2 J: Add 22011 m of water to each of the three fixing solutions
In order to avoid reducing the iodine consumption to less than 1/1 (1/1), the molar ratio of hydrogen peroxide to ammonium thioate should be 0.
It can be seen that if it is added in a range of about 9 to 1.25, j: Similarly, the amount of hydrogen peroxide solution to be added can be determined for various thiosulfate ion A concentrations.

Example 1 The present invention was carried out using the water washing section shown in FIG. 1 and under the following experimental conditions.

Automatic developing machine; Printing film/paper processing equipment Konica Automatic Brochuts 1NA GR-27 Developer: Konica Daibel Tuber Type 651K Fixer:
Konica Fikuri-1 Type 8513↓ Processed sensitive material: Konica RST Clear Light Contact Film CRI-1, CRHE, RHG. R l-1 1-1 (all manufactured by Konica A-Ko) Konica Clear Light Contact] ~ The film was sent to Dainippon Screen {Kiki-made plate-making printer P-607 (light source: ultra-high pressure mercury lamp URT-CI-IM-1000). Large paper size 508mmx with a blackening rate of approximately 50% exposed to light.
I used one from eiomm. First, Konica Automatic Proselli-GR-27 (hereinafter GR-27) including water washing 11
Cut off the tap water supply valve to -27 and 50f
It is connected to a vinyl chloride water tank 2 with a volume of fi, and the water tank is filled with 40ffi of water, and the washing tank 1 of the GR-27 is also
1 of rinsing water, so that a total of 62ffi of water was being circulated. Furthermore, a 6% hydrogen peroxide solution containing a certain amount of melon determined according to Experimental Example 1 according to the processing amount of the photosensitive material was added to the OR port. OR
An oxidizing agent supply tank 5 that can be automatically added every 3 m of +-1 and R l-I G treatment is provided, and a filter unit 4a, 4b made of polypropylene is installed in the middle of the circulation path. Figure 1 shows two types of v4-filtration YJ-type cartridge filters with pore diameters of 2μ and 20μ, which are made by bundling fibers with cilia and rolling them up so that water passes through them in a spiral shape from a central cylinder. They were connected and installed in parallel as shown. Similarly, two types of tubes with pore diameters of 7 μm and 10 μm were connected in parallel and installed.

The amount of precipitate in the circulating water after processing 135 human-sized shrines per day using the water washing section as described above for two days while adding hydrogen peroxide as an oxidizing agent. The finishing performance of the kidnapping and the conversion status of the filter when continuous processing was performed for one month under the above-mentioned condition f1 were investigated. The results are shown in Table 1.

In addition, we measured the water quality at each treatment point when using the above-mentioned 7μ and 10μ filters in combination, that is, the amount of iodine consumed and the washing water pll, and also measured the residual hypoglycium in the shrine at each time. Shown in FIGS. 3 and 4.

From Figures 3 and 4, hydrogen peroxide decomposes Hybo,
At the same time as water regeneration, iodine removal Ftffi value is 220m
It can be seen that the washing water has been purified to the point that it can be drained because the navy blue color is below A/Q.

In addition, the residual hyperbolism was measured using a method of measuring 81 liters (j: 3L1 or less).

<Remaining closed hypo measurement method> Drop one drop of detection solution F on the minimum depth area (fogged area) of the processed film and leave it as is for 3 minutes. Absorb the dripped liquid with blotting paper (filter paper) and leave it to dry. The permeability (D) of the area contaminated with the detection liquid was measured using a depth meter through a blue filter, and the fog density (D(1)) of the area where the detection liquid was not dropped was measured in the same way. )
- 1) Calculate O and use it as the net contamination level of the residual gray matter,
, Check this net contamination degree using the FFI line and read the high degree.

Ittan Kei Pure Water 750cc28%
Acetic acid (3:8) 125cc
Silver nitrate 7.5g Purified water finish 1000cc Comparative example 43 in the water washing section of Example 1, filter unit] ~ was made by bundling Boristel fibers and winding it to polypropylene = 17 with a force of 1 - 1 ~ ridge filter. Those with a pore diameter of 75 μm, and those with a pore diameter of 10 μm (similar to those with a pore diameter of 10
The same evaluation as in Example 1 was conducted for the two types of μ. We also conducted a similar evaluation for a system that does not use a filter. The results are shown in Table 1.

Also, for systems that do not use the above filter. ll3 and
Furthermore, iodine 8 according to the number of sheets processed without adding hydrogen peroxide solution! l Expenses were measured. The results are shown in Figure 5 of my younger brother. Table 1 *1 Capturing finish performance ◎: As with normal processing, there was no deposit, dust, etc. on the image.

○: When 135 sheets were processed, very slight adhesion of dust, sediment, etc. was observed on about 1 to 2 sheets out of the 135 sheets from about the first sheet onwards.

X: Precipitate adhesion was observed on several sheets during processing of 735 sheets.

*2 Filter replacement status ○: Requires replacement once a month △: Requires replacement approximately twice a month 35 In systems that do not use filters, from the time the number of treated walls exceeds 30, the treated grains will be eluted into the circulating water. Geradin 19
It was observed that the water was colored due to the influence of silver precipitates and slightly suspended sulfur compound precipitates. It was done. For this reason, if the circulating water was recycled and reused as it was, the silver precipitate and the like would be deposited on the treated surface, and this would have a significant negative effect on the finishing performance of the shrine.

When using a filter with a pore size of 75μ,
The precipitates in the circulating water could not be removed, and the finished quality of the photosensitive material did not improve.

In addition, when similar circulation was performed using a 10 μ car ridge filter, the effect of removing sediment was observed, but the extraction ability was too much improved, so the appearance of the water was too rapid, and the washing water became oxidized. Okine-sized photosensitive materials are processed every day while adding chemicals and regenerating them. 13
Processed 5 sheets, each time the iodine consumption value was 220mg/
If the process of discharging water into the sewer is repeated while confirming that the p value is around 7.0, the car 1
Replacement of the Herridge fino letters also became more frequent and became less efficient in terms of operation.

On the other hand, when two types of filters with different pore diameters are used in combination as in the present invention, the above-mentioned precipitation is efficiently promoted, the removal performance is good, and the number of filter changes is small. It was very efficient in terms of operation.

Example 2 A tridge filter made of cellulose fibers with a pore size of 5 μm, which is made from filter paper specifically designed for the tridge filter, treated with epoxy resin for strength reinforcement, and molded into a pleated shape, and a tridge filter with a pore diameter in which fine copper powder is kneaded. 8 in Example 1 except that two types of activated carbon fiber filters with a diameter of 20μ were used in combination.
Example 2 was carried out using the same water washing section as 3' = pull water washing section. While regenerating water by adding 6% hydrogen peroxide as an oxidizing agent, 135 sheets of Daikin size photosensitive material were continuously processed in one day.

This work was carried out continuously for one month, and after one month, the number of bacteria etc. in the circulating water was evaluated.

In addition, the treatment and evaluation were performed in the same manner as above, except that an activated carbon fiber filter in which fine copper powder was not kneaded was used as a filter having a pore size of 20 μm.

The results are also shown in Table 2.

Evaluation of the number of bacteria, etc. was performed as follows.

That is, in order to count the number of bacteria, prepare an agar medium for bacteria and an agar medium for mold, sprinkle the collected water LOCC on each culture medium and spread it evenly. Medium IJ 3 7℃'C: /1
The mold was cultured at 20°C to 25°C for 3 to 113 days. After that, take out the rimble and 1. The number of bacterial masses (210 nee) was counted for the OCC water.

Table 2 Unit: Viable number of microorganisms (number/d) 39 Table 2 shows that when filters with different pore sizes are used together, if one filter has antibacterial properties, the number of bacteria in the circulating water can be reduced. significantly decreased. It can be seen that the present invention has a remarkable effect on the growth of limescale and the like.

[Effects of the Invention] As explained in detail above, the automatic developing apparatus and processing method of the present invention greatly improves water saving efficiency in processing silver halide black and white photosensitive materials, and further improves water circulation. It is possible to efficiently remove lime scale, mold, etc. generated by use, as well as precipitates of reaction products generated by the oxidizing agent used as a water regeneration means. In addition, the circulation makes it possible to purify contaminated wash water to the point where it can be drained.

[Brief explanation of drawings]

Figure 1 is a '1J' schematic diagram schematically showing an example of the water washing section of the automatic developing device of the present invention, and Figure 2 shows the relationship between the molar ratio of hydrogen peroxide to ammonium thiosulfate and the amount of iodine consumed. Figure WX3 is a graph showing the relationship between the number of processed sheets and iodine consumption and pl-1 in Example 1, and Figure 4 is a graph for Example 1 and Comparative Example. 5 is a graph showing the relationship between the number of sensitive material processed and the residual hygrovalue in J3G filtered hydrogen oxide water addition, and FIG. It is. Main reference numbers> 1...Washing tank 2...Water tank 3...Circulation means...Filter unit 1-4a, 4b...Filter 5...Oxidizer supply tank 6...・Drainage means

Claims (7)

[Claims] (1) In an automatic developing device for silver halide black-and-white photosensitive materials, which includes at least a developing section, a fixing section, and a water washing section, the washing section includes at least a water washing means for washing the photosensitive material, and a water discharger discharged from the water washing means. a water storage means for temporarily storing water including used washing water as washing water to be supplied to the washing means; a regeneration means for adding an oxidizing agent to regenerate the used washing water; and the water storage means and the washing water. A filter means consisting of at least two types of filters having different pore sizes provided between the means, and circulation for circulating the washing water in the washing means and the washing water in the water storage means between the washing means and the water storage means. 1. An automatic developing device for silver halide black and white photosensitive materials, comprising: means. (2) In an automatic developing device for silver halide black-and-white photosensitive materials comprising at least a developing section, a fixing section, and a water washing section, the washing section at least includes a water washing means for washing the photosensitive material with water;
a water storage means for temporarily storing water including used washing water discharged from the washing means as washing water to be supplied to the washing means; and a regeneration means for adding an oxidizing agent to regenerate the used washing water. and a filter means comprising at least two types of filters having different pore diameters provided between the water storage means and the water washing means, and a filter means for distributing the washing water in the washing means and the washing water in the water storage means to the washing means and the water storage means. a purification agent supply means for supplying a purification agent to the water storage means when the contaminant concentration of the flush water being circulated by the circulation means exceeds a predetermined value; 1. An automatic developing apparatus for silver halide black and white photosensitive materials, comprising a drainage means for draining at least a portion of washing water within the means. (3) The filter means is at least one 0.5-7μ
and at least one filter having a pore size of 7 to 2
and a filter having a pore size of 0μ.
) or the automatic developing device described in (2). (4) The automatic developing device according to claim 1 or 2, wherein the filter means includes at least one filter having a sterilizing effect. (5) A method for processing a silver halide black and white photosensitive material using the automatic developing apparatus according to claim (1). (6) A method for processing a silver halide black and white photosensitive material using the automatic developing apparatus according to claim (2). (7) Claim (5) in which hydrogen peroxide is used as the oxidizing agent.
Or the processing method described in (6).