JP2585744B2 - Processing method and processing apparatus for black-and-white silver halide photographic materials - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a method and an apparatus for processing black-and-white silver halide photographic light-sensitive materials (hereinafter, referred to as light-sensitive materials). The present invention relates to a processing method and apparatus for utilizing waste heat discharged when processing a processed waste liquid for processing a photosensitive material.

[Background of the Invention]

Conventionally known methods for processing photographic materials include a method of collecting the processing waste liquid by a collection company or creating a waste liquid processing facility at a large cost and treating the waste liquid. There is a problem that a great burden is imposed on work and cost.

Regarding the processing method of the processing waste liquid of the photosensitive material, several methods have been proposed in which the processing waste liquid is heated and separated into water and solid content (sludge). However, when these methods are performed, a large amount of waste heat is generated, and particularly when an air-cooled condenser is used, there is also a problem in the work environment that the temperature of the work room rises above an appropriate temperature, and the above-described waste heat is generated. It is desired to make effective use of heat. In particular, when the waste liquid processing machine is operated simultaneously with the automatic developing machine, there is a particularly serious problem in the working environment.

[Object of the invention]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a method and an apparatus for processing a photosensitive material in which the workability of processing the waste liquid of the photosensitive material is improved.

It is another object of the present invention to provide a method and an apparatus for processing a photosensitive material which does not lower the working environment even when an automatic developing machine and a waste liquid processing apparatus are operated simultaneously.

Still another object of the present invention is to provide a method for processing a photosensitive material,
An object of the present invention is to provide a method and an apparatus for processing a photosensitive material which can greatly reduce the total energy cost.

[Configuration of the invention]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a method of processing a photosensitive material including a method of separating a processing waste liquid of the photosensitive material into a solid content and water by a process including a heating step, wherein the steam generated in the processing including the heating step is cooled and liquefied. A method for processing a photosensitive material, wherein the waste heat discharged in the liquefaction step is used in a processing step for the photosensitive material (however, in the heating step,
Means excluding the case where the processing waste liquid is evaporated by blowing heated air containing the waste heat air from the drying section onto the processing waste liquid), and means for separating the processing waste liquid of the photosensitive material into solids and water by processing including a heating step In a photosensitive material processing apparatus having
A photosensitive material processing apparatus, characterized in that it has means for utilizing the exhaust heat discharged in the step of cooling and liquefying the water vapor generated in the processing including the heating step in the processing step of the photosensitive material. (Excluding the case where the treatment waste liquid is blown with heated air containing waste heat air in the drying section to evaporate the treatment waste liquid).

The “water” includes not only pure water but also a liquid containing an organic solvent and the like contained in the treatment waste liquid.

Examples of the processing steps used for the processing of the exhaust heat and photosensitive material of the present invention include development, keeping the temperature of the fixing solution, and increasing the temperature of the drying air. These can be used directly or indirectly by hot exhaust air (in the case of air cooling) or hot exhaust water (in the case of water cooling).

 Hereinafter, the present invention will be described with reference to embodiments shown in the drawings.

FIG. 1 shows a waste liquid processing apparatus and an apparatus for utilizing exhaust heat discharged from the apparatus for supplying hot air to a drying step in a processing step of a photosensitive material, and FIG. 2 shows a photosensitive material incorporating the apparatus. Is shown.

Waste tank 1 was placed a waste liquid discharged from the processing apparatus of the photosensitive material is piping connecting the pump P ₁ to the inlet 12 of the tubular portion 11 of the evaporator 10. The waste liquid tank 1 is provided with a liquid level gauge (not shown) so that the liquid level can be detected.

An evaporator 10 constituting a container is connected to a lower sludge tank 16 from a lower sludge discharge port 15 by a liquid reservoir 14 having a cylindrical portion 11 and an upper conical wall portion 13.

The evaporator 10 has a heating member 17 and a net-like member 1 filled with a baked semiconductor which generates heat and ultrasonic waves when energized.
8, 19 are provided. This mesh member may be either one. Further, a liquid level gauge 20 is provided.

Evaporated gas of the waste liquid is cooled and liquefied by an air-cooled cooler 22 from an outlet 21, and is piped to enter a collection container 24 via a filter 23.

The mesh members 18 and 19 preferably have an opening of about 0.5 to 1.3 mm. Specifically, for example, 0.2mmφ, pitch
A stainless steel wire mesh of about 1.0 mm can be used.

A level gauge 20 is provided inside the evaporator 10, and the level gauge 20 is provided.
In the detected result, by providing a device for controlling the operation of the pump P ₁ for supplying waste to maintain the liquid level of the waste liquid inside the evaporator 10 to a predetermined height,
The operation of supplying the waste liquid to the evaporator 10 is simplified.

The volume of the waste liquid storage portion of the evaporator 10 varies depending on the heat-generating member.
1 to 10 is appropriate per 1 Kw, preferably 1.5 to 5
It is. The volume of the upper void portion for preventing the outflow of bubbles and bumping is suitably 0.5 to 4 times, more preferably 0.7 to 2.5 times the volume of the waste liquid storage portion.

When the waste liquid to be treated by the evaporator 10 contains a dispersion of a polymer compound, it is preferable that the waste liquid be removed in advance by a filter and then put into the evaporator.

The cooling air heated by the air cooling cooler 22 is
And blows it from the drying air outlets 26 and 26 'to the front and back of the photosensitive material being conveyed. 27 is a blower.

As a preferred embodiment of the heat generating member 17 used in the present invention, a pipe made of a corrosion-resistant, heat-resistant and heat-conductive material (for example, stainless steel) having an inner diameter of 5 to 30 mm and a thickness of about 1 to 5 mm is used. A member in which at least a part of a portion which is insulated and coated in a waste liquid is filled with a sintered body of a semiconductor composition powder and has a shape such that a required length of a semiconductor filled portion can be immersed in the waste liquid ( For example, a coil in the submerged portion is used. Both ends of the semiconductor member 15 are connected from the waste liquid level to a connector 27 provided on the conical wall 13 of the upper evaporator, and connected to an external power supply. In such an embodiment, the length of the semiconductor filling portion in the waste liquid of the semiconductor exterior 17 is 4 g / min of waste liquid treatment capacity.
About 20 mm to 20 mm is appropriate.

Examples of the fired semiconductor that generates heat and ultrasonic waves by energization include CuO, Cu ₂ O, ZnO, NiO, Ni ₂ O ₃ , CdO, BaO,
_{WO 2, WO 3, MoO 2} , Yb 2 O 3, Y 2 O 3, Fe 2 O 3, Fe 3 O 4, FeO,
C, Si, Ga, Ge, Se, TiO ₂ , TiO, Ti ₂ O ₃ , CoO, Co ₂ O ₃ ,
Co ₃ O ₄ , Al ₂ O ₃ , CrO, P, As, Cr ₂ O ₃ , CrO ₃ , MnO, Mn
Examples include a fired product of a mixture selected from metal oxides or elements such as O ₂ and Mn ₂ O ₃ and components such as SiC. Metallic elements of the above metal oxides or other elements (Ag, Au, Pt, etc.) or SiO ₂ , Na ₂ O,
K ₂ O, CaO, MgO or the like may be added.

Preferred embodiments include those having the following composition.

_{Fe 2 O 3 50~90%; MnO} , CoO, NiO, FeO, CuO, CdO, ZnO
At least one selected from the group consisting of 2 to 30%; Na ₂ O, K
_A preferred semiconductor composition is a composition in which at least one selected from ₂ O, SiO ₂ , CaO, and Al ₂ O ₃ contains a total of 5 to 30%.

As a preferred use form of the fired semiconductor, a granular semiconductor mixture is filled inside a corrosion-resistant, heat-resistant and thermally conductive hollow pipe whose inside is insulated with a silicon resin or the like,
An example is a mode in which a fired semiconductor heater made by sintering the granular material by energization is used as the semiconductor member 17, and is immersed in a waste liquid to be treated and energized to generate heat and ultrasonic waves.

In such an embodiment, the particle diameter of the granular semiconductor mixture is about 0.01 to 0.2 mm, the inner diameter is 5 to 30 mm, and the thickness is 1 to 5 mm.
For example, it is possible to use a stainless steel hollow pipe of about mm in which the inside is insulated and filled with the granular fired semiconductor so as to have a filling section length of about 4 to 20 mm per 1 g of waste liquid treatment capacity.

In the method of the present invention, it is preferred that the waste liquid is treated and separated together with the solid matter, and the separated water is preferably used as dilution water for concentrated developer, washing water and the like. In this way, by circulating and reusing the active ingredient (solvent) contained in the waste liquid, it is possible to save water resources and extremely reduce the amount of waste. Further, it is possible to omit piping facilities for water supply and drainage accompanying the installation of the automatic developing machine.

As an embodiment utilizing the separated water, for example, there is an embodiment in which water in the recovery container is automatically sent to a washing replenisher tank 13 provided in an automatic developing machine.

In FIG. 2, 2 is a waste liquid treatment device, 3 is a developing tank, 4 is a fixing tank, 5 is a washing tank, and 6 is a drying unit.

Since the present invention utilizes the waste heat discharged in the processing of the processing waste liquid for processing the photosensitive material, the waste liquid processing method and apparatus include a step of heating the processing waste liquid and cooling and liquefying the generated steam. In addition to the above examples, for example, JP-A-62-118346, JP-A-62-118347,
No. 62-118348 and the like.

In the present invention, an embodiment in which an air-cooled cooler is used as a means for cooling and liquefying the steam generated in the heating step in the treatment of the processing waste liquid is preferable. This aspect is advantageous in utilizing the waste heat generated in the waste liquid processing for heating and keeping the temperature of the processing liquid used in the processing step, and is advantageous in reducing the total energy cost required for processing the photosensitive material.

As the air-cooled cooler, in addition to the cylindrical fin type as shown in FIG. 1, a finned tube is spirally formed as shown in FIGS. 3 and 4 (only some of the fins are not shown). Those arranged in a shape or meandering shape are used. FIG. 4 is a cross-sectional view as seen from a direction parallel to the blowing direction. As a mode corresponding to the conditions of the examples described later, for example, a finned tube is
A tube with an outer diameter of 12 mm and an inner diameter of 10 mm with fins of an outer diameter of 40 mm and a plate thickness of 1 mm. In FIG. 3, a is 200 mm, b is 100 mm,
The cross-sectional size of the air-cooled cooler in Fig. 4 is 400mm long and 3mm wide.
Those having a size of about 00 mm are used.

In the present invention, it is preferable that the waste heat generated in the waste liquid treatment is used for heating the drying air in the drying step of the photosensitive material processing step. According to this aspect, in addition to being advantageous in reducing the total energy cost required for processing the photosensitive material,
The problem that the working environment is impaired by the waste heat discharged in the waste liquid treatment is improved more highly.

It is preferable that the apparatus that implements such an aspect has means for selectively using both the exhaust heat generated in the waste liquid treatment and another heat source, for example, a heater using electric heat, for heating the drying air. According to such an apparatus, it is easy to adjust the imbalance between the calorific value of the waste heat of the waste liquid treatment and the heat load to be supplied to the drying air.

〔Example〕

Example 1 Using the waste liquid treatment apparatus of the embodiment shown in FIG. 1, the volume of the evaporator 17 was set to 1.6 for the waste liquid, and the volume of the void was set to 2. Semiconductor components (main components were Fe ₂ O ₃ , CoO, Cr ₂₎ O
₃ , a stainless steel pipe (10 mmφ) in which each powder (average particle size 50 μm) of WO ₂ , C, Al ₂ O ₃ , Ni, Na ₂ O, SiO ₂ and CaO) is baked and coated with a silicon resin. Filled to a filling part length of 200 mm, 100 V AC, 10 A, and a current was passed through for 5 minutes and sintered, and the power supplied at that time was 100 V AC, 10 A.

A cylindrical fin-type heat exchanger is used for the condenser 14a of the air-cooled cooler 14, and the pipe inner diameter is 10mm, the pipe outer diameter is 12mm, and the fin outer diameter is 40m.
m, and the fin plate thickness was 1 mm. The blower 27 was blown using an axial fin. The duct 20 was provided with a 400 W nichrome wire heater 30 as a heating element, and was operated by controlling the temperature of the drying air by a temperature controller (not shown).

An automatic developing machine having the waste liquid processing apparatus shown in FIG. 1 and having the configuration shown in FIG. 2 is used. The developing liquid is supplied from a developer supplying member 34 to the photosensitive material. The developer supplied to the photosensitive material flows into the developing tank 3, and the liquid overflowing from the tank enters the waste tank 1 as a waste liquid.

 The following compositions were used as the developer and the fixer.

Developing solution formulation (D-1) Pure water Approx. 800 ml Sodium sulfite 60 g Ethylenediaminetetraacetic acid disodium salt 2 g Potassium hydroxide 10.5 g 5-Merylbenzotriazole 300 mg Triethylene glycol 25 g 1-Phenyl-4-dimethyl- 3-pyrazolidone 300 m
g 1-phenyl-5-methylcaptotetrazole 60 mg Potassium bromide 3.5 g Hydroquinone 20 g Potassium carbonate 15 g Add pure water to make 1000 ml. With sodium hydroxide
The pH was adjusted to 10.7.

Fixer formulation (F-1) (Composition A) Ammonium thiosulfate (72.5% w / v aqueous solution) 240 ml Sodium thiosulfate 10 g Sodium sulfite 17 g Sodium acetate trihydrate 6.5 g Boric acid 6 g Tartaric acid 2 g Acetic acid ( 90% w / w aqueous solution) 13.6 ml (aqueous composition B) pure water 17 ml sulfuric acid (50% w / w aqueous solution) 4.7 g sodium aluminum sulfate dodecahydrate (Al ₂ O ₃ in terms of content of 8.1% w / w The above composition A and composition B in 500 ml of pure water when using 30 g fixer
And finished to 1 before use.

 The pH of the fixing solution was about 4.3.

First, a silver chlorobromide emulsion (30 mol% of silver bromide) was prepared by a double jet method. The emulsion has an average particle size of 0.28 μm, and is washed with water and desalted in a conventional manner, sensitized with gold-sulfur, and after sensitization, 1 g of hydroquinone as a stabilizer, 2 g of resorcinaldoxime and 4 g of hydroxy-6-methyl. 1.5 g of -1,3,3a, 7-tetrazaindene was added per mole of silver halide, and 1- (hydroxyethoxyethyl) -3- (pyridin-2-yl) -5--5 was added as an ortho-sensitizing dye.
0.4 g of [(3-sulfobutyl-5-chloro-benzooxazolininden) ethylidene-2-thiohydantoin] compound was added per 1 mol of silver halide, and 1-phenyl-5-mercaptotetrazole was added to silver as a fog inhibitor. Per mole, ethylene oxide chain as development regulator
30 g of polyethylene glycol (one of the terminal groups is dodecylbenzene) was added in an amount of 0.05 g per mole of silver, saponin was used as a coating aid, polyethyl acrylate was used as a physical property improver in an amount of 3 g per mole of silver, and styrene was used as a thickener. −
An emulsion was prepared by adding a maleic acid copolymer.

Next, a protective film coating solution was prepared as follows. That is, pure water 10 is added to 1 kg of gelatin, and after swelling, the mixture is heated to 40 ° C., and as a matting agent, amorphous silica having an average particle diameter of 3 μm is used.
30 g was decomposed in gelatin and finished to 20 to prepare a coating solution for a protective film.

Using the emulsion and the coating solution for the protective film, a silver halide photosensitive material was prepared as follows.

The emulsion coating solution and the protective film coating solution prepared as described above were combined on a 100 μm-thick polyethylene terephthalate support having been subjected to an undercoating process, the silver amount was 3.5 g / m ² , and the gelatin amount of the emulsion layer was 1.5 g / m ² . m ² , the gelatin weight of the protective layer is 0.8 g / m ²
To obtain a photosensitive material sample. At the time of multi-layer coating, three types of hardeners of formaldehyde, glyoxal and ethyleneimine were added to the coating solution for the protective film to form a hardening.

The prepared photosensitive material sample was cut into a size of 30 cm × 25 cm, exposed to a commercially available plate-making camera (50% blackening), and then processed with an automatic developing machine using a developing solution and a fixing solution having the above-mentioned composition. Developing conditions are 38 ° C for 20 seconds for development and 35 ° C for 20 seconds for fixing
The washing time was 15 seconds at room temperature. Processing of photosensitive material
The processing was carried out while replenishing the developing solution, the fixing solution and the washing water at a rate of 25 ml per sheet, and 1000 sheets of the sample were continuously processed. The waste liquid of the developing solution, the fixing solution and the washing water generated during this processing was put into the waste liquid tank 1.

A waste liquid treatment device 2 shown in FIG.
Is sent to the evaporator 17 and treated by the waste liquid treatment device 2. During the operation of the device, the drying air at 50 ° C. and the air volume of 3 m ³ / min is used as the cooling air of the air-cooled cooler at 20 ° C. and 40% relative humidity. was gotten. The recovered liquid was about 70 water, colorless, transparent and odorless, similar to distilled water. The recovered sludge was a slightly sticky solid, and its apparent volume (bulk) was about 1.5.

〔The invention's effect〕

According to the present invention, the following effects can be obtained in a method for processing a photosensitive material, including a method in which a processing waste liquid is subjected to a heat treatment to separate it into a solid content and water.

(1) Since the heat generated in the processing of the processing waste liquid is used for heating the liquid or gas used in the processing, the total energy generated in the processing of the photosensitive material can be reduced.

(2) In addition to the heat generated in the processing of the photosensitive material, the heat generated in the waste liquid processing can improve the deterioration of the working environment due to the excessive rise in the temperature of the room for processing the photosensitive material.

(3) Workability of photosensitive material processing including waste liquid processing is generally improved.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view showing a main part of an example of a processing apparatus of a photosensitive material according to the present invention, FIG. 2 is a cross-sectional view of an example of a processing apparatus of the present invention,
3 and 4 are cross-sectional views of the air-cooled cooler. Reference Signs List 1 waste liquid tank 2 waste liquid treatment section 3 developing section tank 4 fixing tank 5 washing section tank 6 drying section 17 evaporator 23 sludge tank 24 heat generation Member, 14 Air-cooled cooler 14a Condenser, 15 Filter 16 Recovery container 29 Duct 31 Blower

Claims (8)

(57) [Claims] 1. A method for processing a black-and-white silver halide photographic light-sensitive material comprising a method of separating a processing waste liquid of a black-and-white silver halide photographic light-sensitive material into a solid content and water by a treatment including a heating step. A method for processing a black-and-white silver halide photographic light-sensitive material, wherein the generated steam is cooled and liquefied, and the waste heat discharged in the cooling-liquefaction step is used in a processing step of the black-and-white silver halide photographic light-sensitive material. (However, in the heating step, a case where the treatment waste liquid is heated by blowing heated air including waste heat air in the drying section onto the treatment waste liquid) 2. The processing method according to claim 1, wherein the steam is cooled and liquefied by an air-cooled cooler. 3. The processing method according to claim 1, wherein the exhaust heat is used for supplying hot air in a drying step in the processing step of the black-and-white silver halide photographic material. 4. A black-and-white silver halide photographic light-sensitive material processing apparatus having a waste liquid processing apparatus including means for separating a processing waste liquid of the black-and-white silver halide photographic light-sensitive material into a solid content and water by a treatment including a heating step. An apparatus for processing a black-and-white silver halide photographic light-sensitive material, wherein the waste heat discharged in the step of cooling and liquefying the steam generated in the heating step is used in the processing step of the black-and-white silver halide photographic light-sensitive material.
(However, in the heating step, a case where the treatment waste liquid is heated by blowing heated air including waste heat air in the drying section onto the treatment waste liquid) 5. The processing apparatus according to claim 4, wherein the steam is cooled and liquefied by an air-cooled cooler. 6. The processing apparatus according to claim 4, further comprising means for using the exhaust heat for heating the drying air in the drying step in the processing step of the black-and-white silver halide photographic material. 7. The processing apparatus according to claim 6, further comprising means for selectively using both exhaust heat and a heater by another heat source for heating the drying air. 8. The processing apparatus according to claim 4, wherein said waste liquid processing apparatus is incorporated in a processing apparatus for processing a black-and-white silver halide photographic material.