JPH04282636A - Method for processing black-and-white silver halide photographic sensitive material and automatic developing machine using same - Google Patents

Abstract

PURPOSE:To reduce a space and a cost needed to process a waste processing solution, to improve operation efficiency, and to prevent occurrence of malodor from a waste solution tank by controlling the pH of the waste solution in a prescribed range and separating solid matter from water. CONSTITUTION:A primary waste solution tank 1 receiving the waste processing solution flowing out of the processing device of the black-and-white silver halide photosensitive material is connected with a developing tank 2 and a fixing tank 3 to allow a waste developing solution and a waste fixing solution to flow into the tank 1 which is provided with a stirrer 5 to uniformize the composition of the waste processing solution inside the tank 1, and a constant feed rate pump P1 or P2 is driven to feed acid or alkali from an acid tank 9 or an alkali tank 10 to always control the pH of the waste processing solution in the tank 1 within 6.5+ or -1.0 in accordance with the pH value measured by the pH meter 6, and the pH controlled waste solution is processed by the pH control means 11 and a waste solution separation means to separate the solid matter from the water.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method and apparatus for treating photographic processing waste liquid for black-and-white light-sensitive materials.

0002

BACKGROUND OF THE INVENTION Generally, photographic processing of silver halide black-and-white photographic materials includes at least a development process, and in addition, typically fixing and washing (or stabilization) processes are performed to obtain a photographic image. There is.

[0003] In each step of such photographic processing,
Waste liquid from the processing liquid inevitably occurs.

[0004] For example, processing waste liquid is generated in the following system. That is, in photographic processing in which a large amount of light-sensitive material is processed, components consumed by processing are replenished, and on the other hand,
The performance of the processing solution is improved by keeping the processing solution components constant by removing components that are eluted into the developer during processing or concentrated by evaporation (such as bromide ions in the developer and silver complex salts in the fixer). In order to replenish the processing liquid, a replenisher is added to the processing liquid, and a part of the processing liquid is discarded to remove the thickening components in the photographic processing. Become.

[0005] Among treated waste liquids, low-pollution substances such as washing water can sometimes be disposed of into sewers or rivers, but due to recent tightening of pollution regulations under the Water Pollution Control Act and the ordinances of each prefecture, For example, it has become virtually impossible to dispose of developer, fixer, stabilizer, and the like. For this reason, each photo processing company pays a collection fee to a specialized waste liquid processing company to collect the waste liquid, or installs pollution treatment equipment. However, the method of outsourcing to a waste liquid treatment company requires a considerable amount of space to store the waste liquid, and is also extremely expensive. Furthermore, if you try to install your own pollution treatment equipment, it has drawbacks such as extremely large initial investment (initial cost) and the need for a fairly large space for maintenance.

For this reason, it is possible to make the treated waste liquid non-polluting (specifically, activated sludge method (for example, Japanese Patent Publication No. 51-12943).
and Japanese Patent Publication No. 51-7952, etc.), evaporation method (Japanese Patent Publication No. 4
9-89437 and 56-33996, etc.), electrolytic oxidation method (JP-A-48-84462, JP-A-49-1194, etc.)
No. 58, JP 53-43478, JP 49-11
9457 etc.), ion exchange method (Special Publication No. 51-3770)
No. 4, JP-A-53-383, JP-A-53-43271
), reverse osmosis method (JP-A No. 50-22463, etc.), chemical treatment method (JP-A No. 49-64257, Patent Publication No. 57-Sho.
No. 37396, JP-A-53-12152, JP-A No. 49-5
No. 8833, No. 53-63763, Special Publication No. 57-37
395, etc.), or techniques to reduce the amount or make it easier to dispose of, but none of them can be said to be sufficient.

[0007] In order to facilitate the treatment of waste liquid from silver salt photographic light-sensitive materials, an apparatus for heating the waste liquid to evaporate water to dryness is disclosed in Japanese Utility Model Application Publication No. 70841/1983. Since the waste liquid is directly evaporated and concentrated or dried to dryness, when applied to the treatment of waste liquid of non-silver salt photosensitive materials, solids stick to the inside of the evaporator and the heat source, reducing the evaporation processing efficiency. There are disadvantages such as troublesome maintenance work for removing objects. Inventions intended to solve these technical problems have been proposed in Japanese Patent Application No. 63-217410, etc., and although this technology can solve the technical problems, it is difficult to treat the processing waste liquid discharged from automatic processors. When this technology is applied, odor from the waste liquid tank that temporarily stores the treated waste liquid becomes a problem, and a solution to this problem is required.

[0008]

OBJECTS OF THE INVENTION It is an object of the present invention to reduce the space and cost required for processing waste liquid from processing of black and white silver halide photographic light-sensitive materials, to improve the workability of processing waste liquid, and to eliminate odors from the waste liquid tank. It is an object of the present invention to provide a processing method and a processing device that do not cause such occurrence.

[0009]

[Structure of the Invention] In order to achieve the above object, the processing method of the present invention comprises a process of developing a black and white silver halide photographic light-sensitive material using an automatic processor, a black and white developer, a fixer, and water washing produced in the process. At least one of each waste water and stabilizing liquid
In the method for processing black and white silver halide photographic materials, which includes a step of treating solids and separating them into solids and water, the pH in the waste liquid tank of an automatic processor is always controlled to 6.5±1.0. The processing apparatus of the present invention is an automatic development system for black-and-white silver halide photographic light-sensitive materials, which has a device for processing at least one type of processing waste liquid discharged from an automatic processor and separating it into solid matter and water. In the machine, at least a primary waste liquid tank in which a waste liquid of a black and white developer and a waste liquid of a fixer are mixed and contained, a control means for adjusting the pH of the waste liquid in the primary waste liquid tank to a predetermined range, and the control means. It is characterized by having a device that sends the pH-adjusted waste liquid in the primary waste liquid tank to a treatment tank and separates it into solid matter and water.

The present invention will be explained in detail below.

[0011] The present invention can be used to treat waste liquids by mixing acidic and alkaline processing waste liquids, for example, when developing waste liquids and fixing waste liquids are mixed in a waste liquid tank. This technology generates harmful gases such as ammonia gas and sulfur dioxide gas, which impairs safety. This is because the pH moves to a higher or lower range due to the mixing of the developing waste solution and the fixing waste solution. According to the present invention, since the pH inside the waste liquid tank is always maintained at 6.5±1.0, the generation of harmful gases is suppressed, and safety is extremely excellent.

An apparatus for carrying out the method of the present invention is constructed as shown in FIGS. 1 and 2, for example. Note that in the following drawings, the same components are denoted by the same reference numerals, and repeated explanations will be omitted.

FIG. 1 is a schematic diagram showing a device for controlling the pH of waste liquid in a waste liquid tank in an automatic developing machine so that it is maintained within the above range, and FIG. 1 is a schematic diagram of a waste liquid treatment device that separates solid matter and water.

In FIG. 1, a primary waste liquid tank 1 contains processing waste liquid discharged from a processing apparatus for black and white silver salt photosensitive materials.
are connected so that a developing waste liquid flows from the developing tank 2, a fixing waste liquid flows from the fixing tank 3, and a washing waste liquid flows from the washing tank 4, respectively. 5 is a stirrer provided in the waste liquid tank 1 to make the composition of the treated waste liquid in the tank uniform. The pH of the treated waste liquid in the tank is controlled using a pH meter 6.
The metering pump P1 or P2 is immediately driven to add the acid or alkali solution based on the value measured in . 9 is an acid tank that holds acid solution, 1
0 is an alkaline liquid tank that holds alkaline liquid, 11 is pH
The CPU controls the operation of pumps P1 and P2 based on the measurement results of the meter 6, and is configured to operate pump P1 when pH>7.5, and operate pump P2 when pH<5.5. In this way, the pH of the treated waste liquid in the waste liquid tank is always controlled to 6.5±1.0, and the generation of harmful gases is minimized. The treated waste liquid adjusted to the above pH range is sent to the waste liquid treatment device by the waste liquid pump P3.

[0015] The waste liquid treatment device for pH-adjusted waste liquid is the second one.
It is configured as shown in the figure.

In FIG. 2, 1 is a primary waste liquid tank;
Although not shown in the figure, as shown in Figure 1,
Processing waste liquids from the developing tank, fixing tank, and washing tank flow into the tank, and the pH is controlled to a predetermined pH range using an acid or alkaline solution.

A waste liquid tank 1 that contains waste liquid discharged from a processing apparatus for black and white silver halide photographic light-sensitive materials and performs pH adjustment is a cylindrical portion 31 of an evaporator 30 that is a waste liquid processing tank.
A pump P4 and a filter F1 are connected and piped in series to the injection port 39 of the pump. Further, the overflow liquid from the evaporator 30 is collected into the waste liquid tank 21 through a silicon tube from an overflow port 38 provided in the conical wall portion 32 of the evaporator.

The evaporator 30, which constitutes a container with a cylindrical portion 31, a conical wall portion 32 on the upper side, and a liquid reservoir portion 46 having a constricted portion 25 on the lower side, is connected to the sludge receiving port 31 of the sludge separator 50 from the lower sludge discharge port 34. A connecting part 5 which is piped and is located at the bottom of the sludge separator 50.
5 to the lower sludge tank 60.

A liquid circulation device 65 is installed between the evaporator 30, the sludge separator 50, and the sludge tank 60 so that the liquid is returned and circulated by the pump P2.
is piped.

The evaporator 30 is also provided with a heat generating member 35 filled with a fired semiconductor that generates heat and ultrasonic waves when energized, and mesh members 36 and 37. This net-like member may be either one. Also, liquid level gauge 4
2 is provided.

The evaporated gas of the waste liquid passes through the heat exchanger 92 from the outlet 33, passes through the cooler 72, and is connected to the lower part of the absorption tank 82, and the condensed liquid (water) passes from the outlet 85 to the filter F2.
It is piped to a collection container 88 through the.

Non-condensable gas is circulated from the upper part of the absorption tank 82 to the lower part, and a part of the gas passes through the heat exchanger 92 to the evaporator 30.
A reflux device 90 is provided to facilitate reflux of the condensate into the collection vessel 58 and the delivery of the condensate to the collection vessel 58.

[0023] Inside the evaporator 30, it is preferable to provide one or both of the mesh members 36, 37 near the outlet for the evaporated gas and in the path of the evaporated gas to the outlet. This net-like member can prevent the inconvenience that the waste liquid droplets scattered from the surface of the waste liquid together with air bubbles generated in the waste liquid are mixed with the evaporated gas and discharged from the discharge port. The mesh members 36 and 37 have a mesh opening of 0.5 to 1.3.
A diameter of about mm is appropriate. Specifically, for example, 0
．． A stainless steel wire mesh having a diameter of 2 mm and a pitch of about 1.0 mm can be used. Further, it is preferable to provide this net-like member in two layers as shown in the figure in order to achieve the above-mentioned effect. In the evaporator 30, it is preferable that the evaporated gas outlet 33 is provided at the center of the upper end of the conical wall portion 32, and the sludge outlet 34 is provided at the lower end. In such an embodiment, the inner wall surface between the cylindrical portion 31 of the main body of the evaporator 30 and the evaporated gas outlet 33 is 20 mm with respect to the vertical direction.
It is preferable to have the conical wall portion 32 having an angle of 40° to 40°, since waste liquid droplets adhering to the inner wall surface that scatter from the waste liquid surface as the waste liquid evaporates can easily flow downward. It is desirable to provide a liquid level gauge 42 inside the evaporator 30. By providing a device that controls the operation of the pump P4 that supplies the waste liquid so as to maintain the liquid level of the waste liquid inside the evaporator at a predetermined level based on the result detected by the liquid level gauge, the waste liquid evaporator This simplifies the work of supplying the parts. The volume of the portion of the evaporator 30 where waste liquid is accommodated varies depending on the heat generating member, but is suitably 1 to 10 liters per 1 kW of power supplied to the heat generating member, preferably 1.
It is 5 to 5 liters. In addition, the volume of the upper void part to prevent bubbles from flowing out and bumping is 0.5 to 4 of the volume of the waste liquid storage part.
A suitable value is 0.7 to 2.5 times, more preferably 0.7 to 2.5 times.

In the apparatus shown in FIG. 2, the sludge separator 50 is a device for separating and storing the sludge generated by the treatment of waste liquid in the evaporator 30, and a sludge tank 60 can be freely engaged with the lower end of the sludge separator 50. At the same time, the sludge tank 60 and the evaporator 30 and/or the sludge separator 50 are connected by piping so that the liquid inside the sludge separator 50 flows from the sludge separator 50 through the connection part 35 to the sludge tank 60. It is preferable to add a liquid circulation device 65 for circulating liquid. By adding such a liquid circulation device 65, the workability of the sludge discharge work is improved. If the waste liquid to be treated with the evaporator contains a dispersion of a polymer compound, it is preferable to remove these in advance using the filter F1 before introducing it into the evaporator. By adding such a waste liquid treatment step, it is possible to avoid the solid matter generated from the waste liquid from becoming viscous due to heating by the heat generating member inside the evaporator, and it is possible to generate a smooth and easy-to-handle solid substance. The evaporator 30 includes the following evaporated gas processing device 7.
By adding 0, harmful gases (for example, ammonia gas, sulfur dioxide gas, various organic solvents, etc.) contained in the evaporated gas can be removed very effectively. This evaporated gas processing device 70 includes a cooler 72, an absorption tank 82, and an evaporated gas outlet 3 of the evaporator 30.
3 and a cooler 72, and the cooler 72 and an absorption tank 82, and the absorption tank 82 has an absorbent storage section 6 inside.
4. A condensate discharge port 85 and a piping device 91 for circulating non-condensable gas from the upper part to the lower part of the absorption tank 82 are provided at the lower end. As the cooling means in the cooler 72, for example, a device in which cooling water is passed through a large number of thin tubes inside the cooler is used. The absorption tank 82 usually has a vertical cylindrical shell, and the absorbent may be activated carbon or other appropriate absorbent depending on the purpose. The size of the absorbent storage section 84 may be selected as appropriate depending on the amount of waste liquid to be processed, the type of waste liquid, etc., but as a guide, 10 liters of processing waste liquid of a developer of a normal black-and-white silver halide photographic light-sensitive material can be used.
When processing at a rate of /24 hours, the inner diameter is 20 to 100 m.
m, and a height of about 200 to 1000 mm is appropriate. It is preferable to add a non-condensable gas reflux pipe 93 as described below to the evaporated gas processing device 70. According to this aspect, harmful gases in the non-condensable gas can be absorbed even better. The reflux device 90 including the piping device 91 and the reflux piping 93 is a reflux piping that pumps non-condensable gas into the evaporator 30 from the middle of the piping of the piping device 91 that sends gas from the upper part of the absorption tank 82 to the bottom thereof. 93, and a heat exchanger 9 that exchanges heat between the non-condensable gas before being introduced into the evaporator 30 and the evaporated gas discharged from the evaporator 30.
2. Further, it is preferable that the absorption tank 82 has its condensate outlet connected to the filter device F2. By passing through this filter device F2, the impurity content of the condensate can be further reduced.

As a preferable embodiment of the heat generating member 35 used in the present invention, as described above, the inner diameter is 5 to 30 mm, and the wall thickness is 1 to 5 mm.
A pipe made of a corrosion-resistant, heat-resistant, and thermally conductive material (e.g., stainless steel) on the order of 1.5 mm, whose inside is insulated with silicone resin, etc., has a semiconductor composition inside at least a part of the part that enters the waste liquid. Examples include a member filled with a sintered body of semiconductor powder, which has a shape such that the required length of the semiconductor-filled part can be immersed in waste liquid (for example, the submerged part is coiled). Both ends of the semiconductor member 35 are connected to a connector 43 provided on the evaporator wall surface 32 or 44 above the waste liquid level, and connected to an external power source. In such an embodiment, the length of the semiconductor filling part in the waste liquid of the semiconductor member 35 is 4 to 4 per 1 g/min of waste liquid treatment capacity.
Approximately 20m is appropriate. The fired semiconductors used in the present invention that generate heat and ultrasonic waves when energized include CuO, Cu2O, ZnO, and Ni.
O, Ni2O3, CdO, BaO,, WO2, WO3,
MoO2, Yb2O3, Y2O3, Fe2O3, Fe3
O4, FeO, C, Si, Ga, Ge, Se, TiO2
, TiO, Ti2O3, CoO, Co2O3, Co3O
4, Al2O3, CrO, P, As, Cr2O3, Cr
Examples include fired products of mixtures selected from metal oxides or elements such as O3, MnO, MnO2, Mn2O3, and components such as SiC. Metal elements of the metal oxides or other elements (Ag
, Au, Pt, etc.) or SiO2, Na2O, K2
O, CaO, MgO, etc. may be added. Preferred embodiments include those having the following composition. As a preferred embodiment of treating waste liquid with the fired semiconductor in the present invention, granular fired semiconductor is filled inside a corrosion-resistant, heat-resistant, and thermally conductive hollow pipe, and the pipe is immersed in the waste liquid to be treated and energized. Examples include an embodiment in which heat and ultrasonic waves are generated.

In this embodiment, the particle size of the granular semiconductor mixture is about 0.01 to 0.2 mm, and the granular semiconductor mixture is made of, for example, a stainless steel hollow pipe with an inner diameter of 5 to 30 mm and a wall thickness of about 1 to 5 mm, the inside of which is insulated. It is possible to use a device filled with granular fired semiconductor such that the length of the filled part is about 4 to 20 mm per 1 g/min of waste liquid treatment capacity. In the present invention, when it is necessary to treat two or more types of waste liquids, it is preferable from the viewpoint of workability and other aspects that they are treated together.

Next, an embodiment of the automatic processor of the present invention will be described with reference to the drawings. FIG. 3 is a schematic sectional view of an embodiment of the automatic processor of the present invention. In the same figure, 1
00 is the main body of the automatic processor, which includes an insertion table 101 for inserting a photosensitive material, a developing tank 2 for performing development, a developer replenishing tank 2a for storing developer replenisher, a fixing tank 3 for fixing, and a fixing replenisher tank for storing fixer replenisher. 3a, a washing tank 4 for washing, a primary washing replenishment tank 4a for storing washing water, a drying section 105 for drying, an air conditioner 106 for drying air,
The main components include a primary waste liquid tank 1 containing waste liquid from each process of development, fixing, and water washing, a pH meter 6, an acid tank 9, an alkaline liquid tank 10, and a CPU 11. P3 is a pump, and P7, P8, and P9 are metering pumps. 110
2 is a waste liquid processing section that processes waste liquid and separates it into solid matter and water, and the waste liquid processing device shown in FIG. 2 is incorporated therein.

The flow of treated waste liquid into the primary waste liquid tank 1 is as follows:
Each time a black and white photosensitive material is processed, a metering pump P7 is supplied from the developer replenishment tank 101a according to the area of the processed photosensitive material.
The developer replenisher is sent to the developer tank 101, and the overflow solution thereby enters the waste solution tank 108, and the respective overflow solutions for fixing and washing also enter the waste solution tank 1.

[0029] In the present invention, the waste liquid whose pH has been adjusted in the primary waste liquid tank is sent to the treatment tank for treatment, but this treatment is a batch process, and during this treatment, there is no further water in the treatment tank. Do not add waste liquid, and the waste liquid generated during that time will be 1
Next, the liquid shall be stored in the waste liquid tank.

The first reason is the generation of harmful gases. When new waste liquid is added to waste liquid that is being treated at high temperatures, a large amount of toxic gas is generated at that moment, which is extremely dangerous.

[0031] Second, energy can be saved. Adding low-temperature waste liquid to waste liquid during high-temperature treatment results in a large energy loss and is extremely inefficient. Online processing requires the processing tank to be kept running at all times.
Batch processing is also more advantageous in terms of energy conservation (in the case of batch processing, it is operated only when necessary). For these reasons, batch processing is advantageous over continuous processing, and embodiments of the present invention allow for stable batch processing.

[0032] Methods of waste liquid treatment include heating evaporation to dryness,
Any known means such as distillation under reduced pressure or layer separation using a polymer absorber may be used. In addition, in these processes,
A heat pump method may be used to increase energy efficiency.

In the present invention, the pH in the primary waste liquid tank
Adjustment may be performed using a developing waste solution and/or a fixing waste solution. In this case, it is preferable to provide a sub-tank for developing waste liquid and/or fixing waste liquid between the first waste liquid tank and the first waste liquid tank.

[0034] There are no restrictions on the processing liquid that produces the processing waste liquid that is processed in the processing method and processing apparatus of the present invention, and on the photosensitive materials that are processed with the processing liquid, and those that are commonly used are included. Specifically, the processing liquids and photosensitive materials described in JP-A-2-64628, page 5, upper right column, line 2 to page 7, lower right column are included.

In the present invention, the water separated by treating the waste liquid may be used as dilution water for the concentrated developer. As a result, water resources can be saved, the amount of waste can be extremely reduced, and water and drainage piping equipment associated with the installation of an automatic developing machine can also be omitted. As a method of using the separated water, for example, a dilution tank installed in an automatic processing machine that holds dilution water for concentrated developer solution is connected with a collection container that holds water separated from waste liquid, and the dilution tank is connected with piping. An example of this method is to control the amount of liquid in the water tank and automatically send the water in the collection container to the dilution tank.

[0036]

EXAMPLE A waste liquid pH control apparatus having the embodiment shown in FIG. 1 was used as a waste liquid pH control apparatus. In this apparatus, the capacity of the primary waste liquid tank 1 was 20 liters, and the capacity of the acid tank 9 and alkaline liquid tank 10 was 5 liters.

As the waste liquid treatment apparatus, a waste liquid treatment apparatus of the embodiment shown in FIG. 2 was used. In this device, the capacity of the evaporator 30 is 1.6 liters of waste liquid, and the volume of the gap is 2 liters,
As a heat generating member, a semiconductor component (main components are Fe2O3, C
oO, Cr2O3, WO2, Al2O3, Ni, Na2
O, SiO2, CaO) powder (average particle size approximately 50 μm
) into a stainless steel pipe (10 mmφ) whose inside is baked and painted with silicone resin, with a length of 200 mm.
100 VAC, 10 A for 5 minutes and sintered.
And so. Further, the capacity of the waste liquid tank 21 was 20 liters, and the capacity of the recovery container 88 was 10 liters.

[0038] Filter F1 is TC-1 (manufactured by Tocel)
The absorbent in the absorption tank 82 contains about 10% of coconut grain activated carbon.
00g, and an activated carbon cartridge AP-117 manufactured by Kyuno Co., Ltd. was used for the filter F2.

[0039] As an automatic developing machine, one of the embodiment shown in Fig. 3 was used.

The capacity of the developing tank 2 was 30 liters, the capacity of the fixing tank 3 was 30 liters, and the capacity of the washing tank 4 was 15 liters. The developer and fixer used had the following compositions, and tap water was used for washing.

Developer formulation Pure water

Approximately 800ml sodium sulfite

60g Ethylenediaminetetraacetic acid disodium salt
2g potassium hydroxide
10.5g
5-methylbenzotriazole
300
mg triethylene glycol

25g 1-phenyl-4,4-dimethyl-3
-pyrazolidone
300mg 1-phenyl-5-methylcaptotetrazole
60mg potassium bromide

3.5g hydroquinone

20g
potassium carbonate

Add 15g of pure water to make 1000ml. The pH was adjusted to 10.7 with sodium hydroxide.

Fixer formulation (composition A) Ammonium thiosulfate (72.5% w/v aqueous solution) 240 ml
sodium thiosulfate

10g sodium sulfite

17g Sodium acetate trihydrate
6.5g boric acid


6g tartaric acid

2g acetic acid (90%
w/w aqueous solution)
13.6ml (
Composition B) Pure water

17ml sulfuric acid (50% w/w
aqueous solution)
4.7g Sodium aluminum sulfate decahydrate (aqueous solution with Al2O3 equivalent content of 8.1% w/w)

50% pure water when using 30g fixer
The above composition A and composition B were dissolved in 0 ml in this order, and the total volume was made up to 1 liter for use.

The pH of this fixer was 4.3.

First, a silver chlorobromide emulsion (30 mol % silver bromide) was prepared using a simultaneous mixing method. Average particle size is 0.28μm
This emulsion was washed with water and desalted according to a conventional method, and then gold-sulfur sensitized. After sensitization, 1 g of hydroquinone, 2 g of resorcinaldoxime and 4-hydroxy-6-
1.5 methyl-1,3,3a,7-tetrazaindene
g per mole of silver halide, and 1-(hydroxyethoxyethyl)-3 as an ortho-sensitizing dye.
-(Pyridin-2-yl)-5-[(3-sulfobutyl-5-chloro-benzoxazolinindene)ethylidene-2-thiohydantoin] compound is added in an amount of 0.4 g per mole of silver halide to suppress fogging. As an agent, 1-phenyl-5-mercaptotetrazole was used at a concentration of 0.00% per mole of silver.
1 g of polyethylene glycol with 30 ethylene oxide chains (one end group is dodecylbenzene) was added per mole of silver as a development regulator, saponin was added as a coating aid, and polyethyl acrylate was added as a physical property improver. 3g per mole, styrene as thickener
An emulsion was prepared by adding a copolymer of maleic acid.

Next, a protective film coating solution was prepared as follows. That is, 10 liters of pure water is added to 1 kg of gelatin, heated to 40° C. after swelling, and 30 g of amorphous silica with an average particle size of 3 μm is dispersed in the gelatin as a matting agent. was prepared.

A silver halide photosensitive material was prepared using the above emulsion and protective film coating solution in the following manner.

The emulsion coating solution and protective film coating solution prepared above were combined on a polyethylene terephthalate support with a thickness of 100 μm that had been subbed, and the amount of silver was 3.5 g.
/m2, the amount of gelatin applied to the emulsion layer was 1.5 g/m2, and the amount of gelatin applied to the protective layer was 0.8 g/m2, and a light-sensitive material sample was prepared. During multilayer coating, hardening was performed by adding three types of hardening agents, formaldehyde, glyoxal, and ethyleneimine, to the protective film coating solution.

[0048] The photosensitive material sample prepared above was placed in a 30cm x 2
After cutting into 5 cm pieces and exposing them to light using a commercially available plate-making camera (50% blackening), they were processed in an automatic processor shown in FIG. 3 using a developer and a fixer having the above composition. The development processing conditions were: development at 38° C. for 20 seconds, fixing at 35° C. for 20 seconds, and washing with water at room temperature for 15 seconds. The photosensitive material was processed while replenishing the developer, fixer, and washing water at a rate of 15 ml per sheet, and 2000 samples were continuously processed. 15 liters each of the developer, fixer, and washing water waste generated during this process are transferred to waste tank 1 (
(See Figure 1 for pH control equipment), and
After controlling H within the range of 6.5±1.0, waste liquid treatment section 1
10 (see Figure 2 for details).

As a result, no odor gas was generated from the primary waste liquid tank 1, and the recovered liquid was about 40 liters of water, which was clear, colorless, odorless, and similar to distilled water. The recovered sludge was a smooth, non-adhesive granular material with an apparent volume (bulk) of approximately 1.2 liters. In this embodiment, the separated and collected water is connected to the washing water replenishment tank 4a by piping so that the water is automatically sent from the collection container 88 to the washing water replenishment tank 4a. Further, there was no difference in performance between the developer replenisher using separated and recovered water as dilution water and the developer replenisher using distilled water as dilution water. Further, the ratio of the amount of recovered water (40 liters) to the consumed amount of processing liquid (45 liters) was 89% (by weight). Note that the amount that the filter F1 could process until reaching the allowable limit for use was 1,600 liters, and the amount that the absorption tank 82 could also process was 1,700 liters. In addition, the time required to replace the filter used in the filter F1 and the activated carbon used in the absorption tank 82 is short (about 5 minutes for the former and about 7 minutes for the latter), and the work is easy. Ta. The cooling water in the cooler 72 was circulated and used, passing through a not-shown heat exchanger to exchange heat with the atmosphere.

[0050]

Effects of the Invention According to the present invention, it is possible to reduce the space and cost required for processing the processing waste liquid of black and white silver halide photographic light-sensitive materials, improve the workability of processing the processing waste liquid, and eliminate odor from the waste liquid tank etc. Provided are a processing method and a processing device that do not cause the occurrence of.

[Brief explanation of the drawing]

Fig. 1 is a schematic diagram showing the configuration of the main parts of the automatic processor of the present invention, Figure 2 is a schematic diagram of a waste liquid treatment device, and Figure 3 is a schematic sectional view of an embodiment of the automatic processor of the present invention. be.

[Explanation of symbols] 1. Waste liquid tank 2. Developing tank 3. Fixing tank 4. Washing tank 6. pH meter
9. Acid tank 10. Alkaline liquid tank 100. Main body of automatic developing machine 110. Waste liquid processing section.

Claims (2)

[Claims] 1. A step of developing a black and white silver halide photographic light-sensitive material using an automatic processor, and treating at least one of the waste liquids of a black and white developer, a fixer, a washing water and a stabilizing solution generated in the step. In a method for processing a black and white silver halide photographic material, the method includes a step of separating solid matter and water by
The pH in the waste liquid tank of the automatic processor is always 6.5±1.0.
A processing method characterized by being controlled by. 2. An automatic developing machine for black-and-white silver halide photographic light-sensitive materials, which has a device for treating at least one type of processing waste liquid discharged from the automatic developing machine and separating it into solid matter and water, wherein at least a black-and-white developing solution is provided. a primary waste liquid tank in which the waste liquid of the waste liquid and the waste liquid of the fixer are mixed and contained; a control means for adjusting the pH of the waste liquid in the primary waste liquid tank to a predetermined range; and a primary waste liquid tank whose pH is adjusted by the control means. An automatic developing machine characterized by having a device for sending waste liquid in a waste liquid tank to a processing tank and separating it into solid matter and water.