JP2627255B2 - Processing equipment for photographic processing waste liquid - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photographic processing waste liquid which evaporates a waste liquid (hereinafter abbreviated as photographic processing waste liquid or waste liquid) generated during the development processing of a photographic photosensitive material by an automatic photographic developing machine. The present invention relates to a processing apparatus, and more particularly, to a processing apparatus for a photographic processing waste liquid suitable for being disposed in or near an automatic developing machine for processing.

[0002]

2. Description of the Related Art Generally, photographic processing of a silver halide photographic light-sensitive material is performed by developing, fixing and washing with black-and-white light-sensitive materials, and color development and bleach-fixing (or bleaching and fixing) with color light-sensitive materials. , Water washing, stabilization, and other functions are performed in combination.

[0003] In photographic processing for processing a large amount of light-sensitive material, components consumed by the processing are replenished, while components that are eluted in the processing solution by the processing or concentrated by evaporation (for example, bromide ion in the developing solution). In order to maintain the performance of the processing solution at a constant level by removing the silver complex salt in the fixing solution and keeping the components of the processing solution constant, a replenisher is added to the processing solution for the above-mentioned replenishment. A part of the processing solution is discarded for replenishment and removal of the thickening component in the photographic processing.

In recent years, replenishers have been changing to systems in which the amount of replenishment is greatly reduced for pollution and economic reasons, including washing water as a replenisher for washing. It is guided from a processing tank by a waste liquid pipe, diluted with a waste liquid of washing water, cooling water of an automatic developing machine, and the like, and disposed of in a sewer.

[0005] However, due to recent tightening of pollution regulations, it is possible to dispose of washing water and cooling water in sewers and rivers. However, other photographic processing solutions [eg, developing solutions, fixing solutions, color developing solutions, Bleach-fix solution (or bleach solution, fix solution),
It is practically impossible to dispose of the stabilizing solution. For this reason, each photographic processing company asks a specialized waste liquid processing company to collect the waste liquid by paying a collection fee, and installs pollution treatment equipment. However, the method outsourced to a wastewater treatment company requires a considerable amount of space to store the wastewater, and is extremely expensive in terms of cost.In addition, the initial investment (initial cost) of the pollution treatment equipment is extremely high. It is large and has drawbacks such as requiring a fairly large area for maintenance. More specifically, as a pollution treatment method for reducing the pollution load of the photographic processing waste liquid, an activated sludge method (for example, JP-B-51-12943 and JP-B-51-7952)
), Evaporation method (JP-A-49-89437 and JP-A-56-33996, etc.), electrolytic oxidation method (JP-A-48-84462, JP-A-49-119458)
No., JP-B-53-43478, JP-A-49-119457, etc.), ion exchange method (JP-B-51-37704, JP-A-53-383, JP-B-53-383)
53-43271, etc.), reverse osmosis method (JP-A-50-22463, etc.), chemical treatment method (JP-A-49-64257, JP-B-57-37396, JP-A-53-12152, No. 49-58833, No. 53-63763, Nobuaki Tokuno
Nos. 57-37395) are known, but not enough.

On the other hand, in recent years, a stabilization process which replaces water washing has been used in recent years because of a limitation in water resources, an increase in supply / drainage costs, simplicity in automatic developing machine facilities, and a work environment around the automatic developing machine. Automatic developing machine that does not require piping for water supply and drainage for washing outside the developing machine (so-called anhydrous washing automatic developing machine)
Photographic processing is becoming widespread. In such processing, it is desired that the cooling water for controlling the temperature of the processing liquid is also omitted. In such photographic processing that does not substantially use washing water or cooling water, the photographic processing waste liquid from the automatic processor is not diluted by water as compared with the case where there is a rinsing processing, so that the pollution load is extremely large, and the effluent is one side. There is a feature that the amount is small. Therefore, since the amount of the waste liquid is small, it is possible to omit the piping outside the machine for the supply and the waste liquid, which is considered to be a disadvantage of the conventional automatic developing machine. The foot space is narrow,
All the drawbacks, such as the large cost of piping work during installation and the cost of energy for hot water supply, are eliminated, and the extremely large advantage of achieving compactness and simplicity until it can be used as an office machine is demonstrated. Is done.

[0007] However, on the other hand, the waste liquid has an extremely high pollution load, and the disposal of rivers and even sewers is impossible at all in light of the pollution regulations. Furthermore, although the amount of waste liquid in such photographic processing (processing using a large amount of running water and not washing with water) is small, even a relatively small-scale processing, for example, processing of 10 liters / day for X-ray photosensitive material, The processing of the photosensitive material for printing plate making is 30 liters per day, and the processing of the color photographic material is about 50 liters per day, and the processing of the waste liquid is becoming an increasingly serious problem in recent years.

For the purpose of facilitating the processing of photographic processing waste liquid, an apparatus for heating the photographic processing waste liquid to evaporate and dry the water is disclosed in Japanese Utility Model Laid-Open No. 60-70841. However, since the vapor generated when the photographic processing waste liquid is evaporated and concentrated to dryness is released to the atmosphere, there is a problem in that pollution remains and the working environment is deteriorated due to odor.

Further, since this apparatus treats a photographic processing waste liquid until it is dried, a part of the photographic processing waste liquid becomes tar and adheres to a heat source or an evaporating vessel wall, thereby causing a decrease in thermal efficiency or a photographic processing waste liquid. The presence of a surfactant that is added to the solution or elutes and accumulates from the light-sensitive material may cause foaming, bumping may occur, the odor may be significant, excessive decomposition may occur, and damage to the evaporator may occur. There were drawbacks such as the possibility of occurrence.

[0010]

The above-mentioned prior art discloses, as an embodiment, a method of absorbing and removing harmful substances and the like in steam by using activated carbon. This is not sufficient, and since the activated carbon absorbs up to steam, the activated carbon is frequently exchanged, which is very uneconomical. In addition, in the above-mentioned technology, since steam in a hot state is released into the atmosphere, it cannot be used in a small room,
For this purpose, a means for discharge to the outside of the room is required.

The present invention further develops the concept of an evaporating apparatus for photographic waste liquid as disclosed in Japanese Utility Model Application Laid-Open No. Sho 60-70814, and clarifies various improvements for practical use of the apparatus. In particular, it is an object of the present invention to provide a photographic processing waste liquid processing apparatus optimal for processing photographic processing waste liquid in a photographic processing facility provided with a single or a small number of automatic developing machines. Is what you do. Still another object of the present invention is to provide a processing apparatus for photographic processing waste liquid which does not have the above-mentioned drawbacks or inconveniences and which can easily process steam generated during processing of photographic processing waste liquid. Further, the present invention provides an apparatus for treating a photographic processing waste liquid which improves the adhesion of tar substances, enables efficient operation without a decrease in thermal efficiency, and can be operated stably for a long time without corrosion of metal parts. With the goal.

[0012]

The above objects of the present invention have been attained by the following constitutions.

1. In a photographic processing waste liquid processing apparatus of a photographic processing apparatus for processing a silver halide photosensitive material with at least a color developing solution, a bleaching solution, and a fixing processing solution, the waste liquid in a processing tank that heats the photographic processing waste solution is evaporated. In this case, a photographic processing waste liquid processing apparatus is characterized in that a surface in contact with the waste liquid is provided with a sticking preventing means in which a fluororesin processing or an inorganic fiber is disposed.

2. 2. The apparatus for treating waste photographic processing liquid according to claim 1, wherein the evaporation processing of the waste photographic processing liquid is performed in a reduced-pressure atmosphere.

3. The photographic processing waste liquid according to claim 1 or 2, further comprising a control unit that stops operation of the photographic processing waste liquid processing unit or switches to a low-energy operation when the photographic processing waste liquid is concentrated to a certain concentration. Processing equipment.

The photographic processing waste liquid processing method is a photographic processing waste liquid processing method for evaporating and concentrating or drying the photographic processing waste liquid.
The waste liquid may be evaporated by heating, and the vapor generated by the evaporation may be cooled to obtain a distillate and / or solidified by absorbing a concentrated liquid of the treated waste liquid to a carrier. The processing apparatus has means for heating the photographic processing waste liquid and means for cooling the steam generated by the heating, and the cooling processing means has a configuration for directly or indirectly receiving the steam generated from the heating means. Is also good.

In the present specification, the term "distillate" means a distilled liquid, which includes a concentrated liquid and includes components other than water.

The photographic processing waste liquid may be treated by (1) at least one cooling treatment selected from the following (A) to (G) for the steam: (A) a baffle plate or a radiator plate Treatment, (B) using waste liquid before evaporative concentration or drying treatment as a cooling heat medium, (C) cooling treatment is performed in a tank for storing waste liquid, (D) a stock tank in the above (C) (E) that the waste liquid before being subjected to evaporative concentration or dryness treatment is introduced into the cooling processing unit and used for cooling, (F) using an air-cooling fan, and (G) cooling processing is performed. (2) The photographic processing waste liquid may include a waste liquid of a washing-substituting stable liquid, or
(3) A gas adsorption process may be performed before the cooling process.

In the present invention, the concentrated liquid may be subjected to solidification treatment. The solidification treatment means that (A) the solidification treatment is a liquid absorption treatment to a liquid absorbing resin, and (B) the solidification treatment is (C) liquid-absorbing resin, solidifying agent,
One or two or more of the desiccant is stored in a waste liquid pack, and the concentrated liquid of the photographic processing waste liquid is absorbed and solidified in the pack, and the solid matter is stored in the pack.
(D) At least one of a liquid-absorbent resin and a solidifying agent
One of them may be charged and solidified.

In the present invention, the photographic processing waste liquid is processed in a method in which a photographic processing waste liquid overflowing from a photographic processing tank of an automatic developing machine is stored in a stock tank, and the amount and / or amount of the photographic processing waste liquid is increased.
Alternatively, according to the photographic processing waste liquid information obtained by detecting the amount of photographic processing waste liquid in the processing means, the photographic processing waste liquid is supplied from the stock tank to the processing means, the photographic processing waste liquid is evaporated by the heating means, and the vapor is energy-saving and efficient. It may be cooled by a typical heat exchange method to obtain distilled water.

The photographic processing waste liquid processing apparatus includes a processing tank for heating the photographic processing waste liquid, a means for discharging the concentrated liquid of the photographic processing waste liquid, and a collecting tank for the concentrated liquid. The apparatus may include a cooling unit, a recovery tank for the distillate generated by the cooling process, and a control unit that controls the heating unit according to the degree of progress of the waste liquid treatment.

Further, the present invention further develops the idea of a photographic processing waste liquid evaporating apparatus as disclosed in Japanese Utility Model Application Laid-Open No. 60-70841 and clarifies various improvements for practical use of the apparatus. In particular, the purpose of the present invention is to clarify the most suitable photographic processing liquid evaporating apparatus for processing photographic processing liquid in a photographic processing facility equipped with a single or a small number of automatic processors. It is intended for. A photographic processing waste liquid processing apparatus which does not have the above-mentioned disadvantages or disadvantages, can easily recover silver resources from the photographic processing waste liquid, and can easily process the photographic processing waste liquid.

Further, in the processing apparatus of the present invention, the solidification processing means is a waste liquid pack containing one or two or more of a liquid absorbent resin, a solidifying agent, and a desiccant. A configuration may be adopted in which the concentrated solution of wastewater is introduced into the concentrated solution of wastewater, or the concentrated solution of photographic processing wastewater is introduced into the wastewater pack.

Further, the processing apparatus of the present invention stores the photographic processing waste liquid in a stock tank and detects the amount of the photographic processing waste liquid in the processing means and / or the amount of the photographic processing waste liquid in the processing means, and according to the photographic processing waste liquid information obtained. From the stock tank (evaporative concentration)
The photographic processing waste liquid is supplied to the processing means and evaporated by the heating means to concentrate the photographic processing waste liquid, and the concentrated liquid is discharged into the processing means or to the outside to be solidified, and the steam is cooled and distilled water to form distilled water in the photographic processing step. It may be reused.

In the present invention, before the heat treatment, silver may be recovered by means such as an electrolysis method, a precipitation method, a substitution method, and a reduction method.

(A) silver recovery processing is silver recovery processing by electrolysis, (B) silver recovery processing is silver recovery processing by precipitation,
(C) The silver recovery treatment may be a recovery method such as a silver recovery treatment by a substitution method or a reduction method, and (D) the photographic processing waste liquid may contain a bleach-fixing solution and a waste solution instead of a washing substitute stable solution.

Further, the apparatus for processing a photographic processing waste liquid according to the present invention, which achieves the above object, may have means for recovering silver from the photographic processing waste liquid and means for evaporating and concentrating the photographic processing waste liquid to dryness. The silver recovery means may have a structure for directly or indirectly receiving the overflow of the automatic processor.

In the processing apparatus of the present invention, (E) the silver recovery processing means may be an apparatus for performing at least one of an electrolysis method, a precipitation method and a substitution reduction method, and (F) the overflow solution is bleach-fixed. It may contain a liquid and a waste liquid of the washing substitute stable liquid.

Further, the photographic processing waste liquid overflowing from the photographic processing tank of the automatic developing machine used in the present invention is collected in a stock tank and obtained by detecting the amount thereof and / or the amount of photographic processing waste liquid in the processing means. According to the photographic processing waste liquid information, the photographic processing waste liquid is stored in the stock tank through the silver recovery means, supplied from the stock tank to the (evaporation and concentration) processing means, and evaporated by the heating means to concentrate the photographic processing waste liquid.
The concentrate may be solidified in or out of the processing means and the vapor may be cooled and recycled as a liquid component, preferably distilled water, in photographic processing. In the above, it is also a preferable embodiment to provide the silver collecting means not before the stock tank but between the stock tank and the (evaporative concentration) processing means. Further, the silver collecting means may also serve as the stock tank.

Hereinafter, the present invention will be described in detail.

The silver recovery treatment by electrolysis which may be used in the present invention includes (1) pre-reduction electrolysis, (2) diaphragm method, (3) electrodialysis method, and (4) diaphragm-free flow method. And the like, and as the technique of the above (1), JP-A-48-18191,
U.S. Pat.No. 4,036,715 can be referred to, and as the technique of the above (2), JP-A Nos. 52-26315, 52-102724, and 53-3553
No. 4, JP-B-43-30167, etc., and as the technique of (3), JP-A-53-60371 can be referred to. As the technique of (4), JP-A-50-98837, Reference can be made to U.S. Pat. No. 4,021,319. Further control techniques such as current control JP-A-53-32869, U.S. Pat.No. 3,875,032, 3,925,1
No. 84, No. 4,006,071, French Patent No. 2,299,667, West German Patent No. 2,552,069, Belgian Patent No. 780,623, etc., and U.S. Pat.
4,049,512, 4,054,503, West German Patent 2,333,018
No. 2,507,123, No. 2,729,567, JP-A-52-294
No. 23, etc., and, regarding the apparatus and liquid feeding technology, JP-A-49-59727, JP-A-52-72227, JP-A-53-65218, U.S. Pat.No. 3,926,768, U.S. Pat. ,twenty two
No. 6, No. 2,515,314 and the like.

In addition to the techniques described above, techniques for recovering electrolytic silver include JP-B-55-3183 and JP-B-55-13343, Research Disclosure (RD) Nos. 18,354, 18,926, and 17,959,
U.S. Pat.Nos. 4,149,756, 4,186,067, and 4,213,
No. 600, etc., and as a precipitation method, JP-A-55-131141
No., JP-B No. 54-27830, U.S. Pat.No. 4,129,441, RD No. 1
No. 8,017 and the like.
No. 62133, No. 55-161035, Japanese Patent Publication No. 54-2848, No. 55-2805
No. 8, U.S. Pat.Nos. 4,110,109, 4,202,771, RD 1
8,140, etc., and as an adsorption method, JP-A-54-1949
No. 6, No. 55-161034, U.S. Pat.No. 4,157,730, No. 4,2
27,681, 4,228,013 and RD 19,425.

The silver recovery treatment by the precipitation method which may be used in the present invention includes (1) silver sulfide precipitation method, (2) radiation,
Any of a sulfurization method using an alternating current, (3) a germicidal precipitation method, and (4) a method of collecting precipitated silver may be used.
-111765, 52-73033, 53-76029, U.S. Patent No.
No. 3,832,453 and the like, and as the technique of the above (2), JP-A No. 52-49984, U.S. Pat. Nos. 4,088,552 and 4,129,4
No. 41, RD No. 18,017, etc., for the technique (3), JP-A-53-59254, etc., and for the technique (4), JP-A-49-36161 and JP-A-49-36161. -54297, 51-63431
And U.S. Pat. No. 3,829,549.

The silver recovery treatment by a substitution method or a reduction method that may be used in the present invention includes (1) a metal substitution method and (2)
Any of ion exchange methods and the like may be used. Examples of the technique (1) include JP-A-48-44124, JP-A-49-31153, JP-A-50-18318,
Japanese Patent Publication No. 54-2848, U.S. Patent No. 4,008,077, French Patent No.
No. 2,106,962 and the like, and as the technique of the above (2), JP-A-49-70823, JP-A-51-17114, U.S. Pat.
No. 2,468,471, 2,497,054, 3,817,74
No. 5, etc. can be referred to.

Further, as a technique relating to a reducing agent and an iron compound, JP-A-48-22031, JP-B-51-24822, and West German Patent No. 1
No. 353,805, U.S. Pat.Nos. 3,082,079 and 4,035,181
No. 4,038,080 and French Patent No. 2,216,232.

The silver recovery processing technology that may be used in the present invention is not limited to the above. (1) Silver recovery processing using activated sludge
(See JP-B-52-10839), (2) Silver recovery treatment with metal periodate (see US Pat. No. 4,078,983), (3) [Co
Other silver recovery techniques such as (NH ₃ ) ₄ ] Cl ₃ silver recovery processing (see RD No. 16,437) may be used.

The silver recovery processing techniques that may be used in the present invention include electrolysis (described in French Patent No. 2,299,667), precipitation method (described in Japanese Patent Application Laid-Open No. 52-73037, and German Patent No. 2,331,220).
Ion exchange method (JP-A-51-17114, German Patent No. 2,548,23)
No. 7) and a metal substitution method (described in British Patent No. 1,353,805).

As shown in Examples described later, each photographic processing tank C
D, BF, and Sb have different components in the photographic wastewater,
All photographic processing waste liquids may not be collectively subjected to silver recovery processing, but may be collected in each photographic processing tank or divided into two or more groups, and only photographic processing waste liquids containing silver complex salts may be subjected to silver recovery processing. Separate the waste liquid in tank CD from the waste liquid in bleach-fixing tank BF and alternative washing tank Sb for the latter bleach-fixing tank BF and alternative washing tank Sb for washing.
Only the waste liquid may be subjected to silver recovery processing by the silver recovery means 80, and may be put into the stock tank 30 together with the waste liquid in the color developing tank CD. Furthermore, after the silver recovery, the evaporating concentration or drying treatment is also separately performed, and the distilled water from the former color developing tank CD is used for the color developing tank CD, and the distilled water from the bleaching / fixing tank BF and the washing alternative stabilizing tank Sb are used. Distilled water may be used for the bleach-fix tank BF and / or the stabilization tank Sb instead of washing (see FIG. 2).

Hereinafter, the present invention will be described in detail.

First, the cooling means 60 which may be used in the present invention shown in FIG. 1 will be described.

Any type of heat exchange means can be used to cool the vapor generated by the evaporation of the photographic processing waste liquid. (1) Shell-and-tube type (multi-tube type, sleeve type) (2) Double-tube type ( 3) Coil type (4) Spiral type (5) Plate type (6) Fin tube type (7) Trombone type (8) Air-cooled type

Heat exchange type reboiler technology can also be used. (1) Vertical thermosiphon type (2) Horizontal thermosiphon type (3) Overflow tube bundle type (kettle type) (4) Forced circulation type (5) Interpolation A mold or the like may be adopted.

Further, a condenser type heat exchange technology may be employed, and any of (1) a direct condenser type, (2) a tower built-in type, (3) a tower top installation type, and (4) a separation type may be used.

It is also possible to use a cooler, and the type of the cooler is arbitrary.

It is also advantageous to employ an air-cooled heat exchanger, and any of (1) forced ventilation type and (2) blow ventilation type may be used.

A specific example of the cooling means 60 which may be used in the present invention will be described below.

(1) As shown in FIG. 3, a large number of air cooling fins
A structure in which the vapor Q generated by evaporating the photographic processing waste liquid P is passed through a radiating plate device 62 having 61.

(2) As shown in FIG. 4, steam generated by evaporating the photographic processing waste liquid P to the cooling section 66 such as the coil 63 for performing heat exchange with the photographic processing waste liquid P in the stock tank 30. A configuration to pass Q.

(3) As shown in FIG. 5, the photographic processing waste liquid P is evaporated in a cooling section 66 such as a multi-stage coil 64 for exchanging heat with the photographic processing waste liquid P in the plurality of stock tanks 30 and 31. Through which the steam Q generated by the heating is passed.

(4) As shown in FIG. 6, steam Q generated by evaporating the photographic processing waste liquid P is applied to a cooling section 66 such as a coil 63 (or 64) for spraying the photographic processing waste liquid P from the spraying member 65. Configuration to pass.

(5) As shown in FIG. 7, blowing means such as a fan
A configuration in which steam Q generated by evaporating the photographic processing waste liquid P passes through a cooling section 66 such as a coil 63 (or 64) to which the wind is applied by the 67.

(6) As shown in FIG. 8, a color developing tank CD, a bleach-fixing tank BF, a washing alternative stabilizing tank Sb, and a photographic processing solution or replenisher used in at least one of these tanks CD, BF and Sb. A configuration in which steam Q generated by evaporating the photographic processing waste liquid P is passed through a cooling section 66 such as a coil 63 for performing heat exchange with one or more liquids in a tank S.

(7) As shown in FIG. 9, a structure in which vapor Q generated by evaporating the photographic processing waste liquid P is passed through a heat exchanger 69 containing heat exchange particles 68 formed of a large number of glass balls or the like.

(8) Other cooling means using a baffle plate include a structure in which steam Q generated by evaporating a photographic processing waste liquid P is passed between baffle plates as described in, for example, JP-A-53-125600.

In the present invention, one or more of these (1) to (8) and other heat exchange cooling means may be used in combination.

When the gas adsorption treatment used when heating and distilling the photographic processing waste liquid is desulfurization treatment, the desulfurization treatment may be dry desulfurization or wet desulfurization. As the former dry desulfurization, various desulfurization methods such as an iron oxide method, a soda-iron method, and a catalytic adsorption or oxidative desulfurization method using activated carbon, silica gel, molecular sieve, or the like can be used.On the other hand, in the latter case, The wet desulfurization method may be a non-regeneration method or a regeneration method. For example, any of a method of absorbing in an alkaline solution, a method of utilizing the reducing property of hydrogen sulfide, a method of forming a compound of hydrogen sulfide, etc. may be used, and the operation method is also a seaboard method, a cyclox method, a vacuum carbonate method, and a garbottle method. Any method such as the method may be adopted.

The gas adsorption treatment that may be used in the present invention is not limited to the above desulfurization treatment, and zeolite adsorption treatment, activated carbon treatment and the like may be carried out for the purpose of removing ammonia gas and sulfur gas.

Gas adsorbing means 50 using filters, adsorbents and the like and vapor cooling means which may be used in the present invention.
This is a reference example in which a means for reusing distilled water R containing 60 is added.

In the figure, gas adsorbing means 50 removes harmful gas such as hydrogen sulfide, sulfur oxide or ammonia gas (H ₂ S, SO ₂ , NH _3, etc.) contained in the vapor of the photographic processing waste liquid as described above. Separation and recovery may be performed using various desulfurization / adsorption technologies such as a zeolite adsorbent and activated carbon.

The concentrated liquid of the photographic processing waste liquid may be absorbed by a carrier, solidified, and recovered.

As the carrier, a liquid absorbing resin and a solidifying agent are considered.

The carrier which may be used in the present invention is a carrier capable of absorbing a concentrated solution of a photographic processing waste liquid. The carrier may have the liquid-absorbed carrier which has already been absorbed or may not drip. May be used.

As the liquid absorbing resin, for example, those listed below can be used.

Seed polysaccharide, seaweed polysaccharide, resin polysaccharide, fruit polysaccharide, rhizome polysaccharide.

Further, Xanthan gum, Zanflo, Gardlan, Succinoglucan, Schizophyllan, Pullulan, Gelatin, Casein, Albumin, Shellac and the like.

Starch derivatives, guar gum, locust bean gum derivatives, cellulose derivatives, alginic acid derivatives, vinyl compounds, acrylic compounds.

In addition, polyethylene oxide and the like.

Next, examples of the superabsorbent resin which may be used in the present invention will be described.

(A) Grafted starch system (A-1) Starch-acrylonitrile graft polymer (A-2) Starch-acrylic acid graft polymer The above (A-1) is disclosed in JP-A-49-43395 and U.S. Pat. No. 4,134,
It can be produced by the method described in No. 863,
(A-2) can be produced by the method described in JP-B-53-46199.

(B) Acrylic acid type (B-1) Sodium polyacrylate type (B-2) Vinyl alcohol-acrylic acid copolymer type The above (B-2) is repeatedly used by natural drying and / or forced drying. You can also.

(C) A polymer having a repeating unit having the structural formula represented by the following (I) or (II), more preferably
A polymer having 10 to 70% by weight of (I) and / or (II) and copolymerized with another ethylenically unsaturated monomer.

[0072]

Embedded image

In the formula, R is a hydrogen atom, a methyl group or a halogen atom, Z is an oxy group or an imino group, and n is 0
Or R ¹ is an alkylene group having ¹ to 6 carbon atoms (including a substituted alkylene group), a cycloalkylene group having 5 to 6 carbon atoms or an arylene group, an arylene alkylene group or an arylene bisalkylene. Wherein said alkylene moiety has 1 to 6 carbon atoms and said arylene moiety (optionally substituted) has 6 to 10 carbon atoms, and

[0074]

Embedded image

Wherein R ⁵ is an alkylene group having 1 to 4 carbon atoms, and R ² , R ³ and R ⁴ are each hydrogen. Is an atom or an alkyl group having 1 to 6 carbon atoms, or together with N forms a heterocyclic group which may optionally contain a sulfur or oxygen atom, M is a hydrogen atom, a soluble cation Or an ammonium group, including a quaternary ammonium cation having an alkyl group with 6 or fewer carbon atoms, and X is an acid anion.

[0076] Halogen substituents R can be a bromine or chlorine, an alkylene group having 1 to 6 carbon atoms in R ¹ may be substituted by a hydroxyl group, R ¹
Arylenealkylene groups include phenylenemethylene, phenyleneethylene, phenylenepropylene, and phenylenebutylene groups, and the arylenebisalkyl group for R ¹ includes phenylenemethylene groups.

[0077] Soluble cations of M include sodium and potassium.

Heterocyclic groups formed from R ² , R ³ and R ⁴ , and the N atom to which they are bonded, include pyridinium, imidazolium, oxazolium, thiazolium and morpholium.

The acid anion of X includes chloride, bromide, acetate, p-toluenesulfonate, methanesulfonate,
There are ethanesulphonate, methylsulphate, ethylsulphate and perchlorate.

The ethylenically unsaturated monomer copolymerized with the monomer (I) and / or the monomer (II) is preferably one or more monomers having a crosslinkable group. Monomers such as 2-hydroxyethyl methacrylate,
It consists of 2-hydroxyethyl acrylate and a monomer containing an active methylene group. This type of polymerized copolymerizable ethylenically unsaturated monomer is described, for example, in U.S. Pat.
No. 0, 3,488,708, 3,554,987, 3,658,8
No. 78, No. 3,929,482 and No. 3,939,130.

Preferred polymers for use in the above are from 10 to 70% by weight of one or more of the monomers listed below or having repeating units thereof: 2-amino Ethyl methacrylate hydrochloride, N- (2-methacryloyloxyethyl) -N, N, N-trimethylammonium chloride, N- (2-methacryloyloxyethyl) -N, N, N-trimethylammonium methosulfate, sodium 2-methacryloyl Oxyethyl-1
-Sulfonates and 2- (N, N-dimethylamino) ethyl methacrylate hydrochloride.

The acid addition salt corresponding to the above structural formula (I) can be converted to a free amine when it is neutralized with a base.

The above-mentioned polymer can be prepared by subjecting a suitable monomer to a polymerization reaction in an aqueous solution according to a conventional method.

The monomer represented by the structural formula (I) may be selected from R.H.Yokum and EB Niquist.
(EBNyquist), “Functional Monomers” (Fu
nctional Monomers), Marcel Dekke
r), Inc., New York (1974) and U.S. Pat. No. 2,780,604. The monomers of the structural formula (II) are described in U.S. Pat.Nos. 3,024,221 and 3,5,
It can be prepared by the method described in JP-A-06,707.

In some cases, the polymer may be prepared by (a) quaternizing the polymer having an amine group with an alkylating agent, or (b) converting the amine into a group reactive with the amine. For example, by reacting with a polymer having an active halogen group. Such techniques are known in the art and are described in U.S. Pat.
Nos. 488,706 and 3,709,690, and Canadian Patent No. 601,958.

The resins mentioned above are also available as commercial products. Examples of the commercially available products include Sumikagel N-100, Sumikagel SP-520, Sumikagel S-50, and Sumikagel NP-102.
0, Sumikagel F-03, Sumikagel F-51, Sumikagel F-
75, Sumikagel R-30 (trade name, manufactured by Sumitomo Chemical Co., Ltd.), Sunwet IM-300, Sunwet IM-100
0 (trade name, manufactured by Sanyo Chemical Co., Ltd.), Aquakeep IOSH-P (trade name, manufactured by Iron and Steel Chemical Co., Ltd.), Langier F (trade name, manufactured by Nippon Exlan Co., Ltd.) and the like.

The liquid-absorbent resin which may be used in the present invention preferably has a shape in which it easily absorbs liquid, and a powdery or granular one having a diameter of about 0.01 to 3 mm can be advantageously used in handling. .

The solidifying agent used as a carrier which may be used in the present invention may be any solidifying agent capable of solidifying a concentrated solution of photographic processing waste liquid, and may or may not involve a chemical reaction. Is also good. As may solidifying agent be employed in the present invention, for example _{CaO, Ca (OH) 2,} CaCO 3, silica gel, calcium chloride, aluminum oxide, calcium sulfate, magnesium oxide, barium oxide, granular soda lime, phosphorus pentoxide, etc. Is preferably used.

As shown in the following embodiment, the present invention
In the processing chamber 42, a photographic processing waste solution to be processed or a concentrated solution that has been processed is stored so as to form an inner pot or an insole 44 with metal, ceramic, synthetic resin, or the like.
Using a separation means such as a bag filter or a pack, the treated concentrated liquid may be solidified and taken out together with the inner pot or the insole 44 or the whole bag filter or the pack and discarded or treated. In addition to using the above-mentioned inner pot or insole 44, as the discharging means 43, a concentrated liquid of the photographic processing waste liquid is discharged from a bottom of the processing chamber 42 or a known discharging device using a rotary screw pump through a valve. Various designs can also be used, such as those that naturally fall into a container having one or more of a liquid-absorbing resin, a solidifying agent, and a desiccant and solidify.

The insole 44 or pack is heat-resistant,
Chemical resistant materials, for example, carbon fiber, aramid fiber, Teflon resin fiber, hemp, glass fiber, polyethylene foam, polypropylene foam and the like can be mentioned.

Next, in the method for treating a photographic processing waste liquid which may be used in the present invention, the method of obtaining distilled water from steam generated by evaporation and using the distilled water as a photographic processing liquid will be described below.

In order to use distilled water for the photographic processing solution, (1) the distilled water may be subjected to at least one secondary treatment selected from the following (A) to (I): (A) activated carbon treatment , (B)
UV irradiation treatment, (C) reverse osmosis treatment, (D) oxidizing agent treatment,
(E) electrolytic oxidation treatment, (F) aeration treatment, (G) electrodialysis treatment, (H) redistillation treatment, (I) ion exchange resin treatment, and (2) distilled water dissolved in photographic processing solution (3) performing a gas adsorption treatment together with distillation, preferably one or two or more of desulfurization treatment, zeolite adsorption treatment, and activated carbon treatment.

The present invention also relates to a photographic processing solution obtained by storing a photographic processing waste liquid overflowing from a photographic processing tank of an automatic processor in a stock tank and detecting the amount thereof and / or the amount of the photographic processing waste liquid in the processing means. According to the waste liquid information, the photographic waste liquid is supplied from the stock tank to the processing means, evaporated by the heating means to concentrate or dry the photographic waste liquid, and the vapor is cooled and reused as distilled water in the photographic processing step. Good.

The activated carbon used in the activated carbon treatment which may be used in the present invention may be any activated carbon capable of adsorbing at least one substance of benzyl alcohol, ammonium compound and sulfur compound.

The activated carbon which may be used in the present invention can be used regardless of the raw material and the method of activation, and can be any of powdered and granular activated carbon, preferably granular activated carbon, particularly preferably coconut shell activated carbon. Activated carbon with molecular sieving ability. Here, the activated carbon having molecular sieve ability has slit-like pores, and the size of the pores is preferably 6A or more and 15A or less in width. For the activated carbon having such molecular sieving ability, the description in JP-A-58-14831 can be referred to.

The distilled water obtained from the photographic processing waste liquid of the present invention may be subjected to an adsorption treatment. As the adsorbing substance used, the following substances can be used in addition to the above-mentioned activated carbon.

(1) Clay substance (2) Polyamide polymer compound (3) Polyurethane polymer compound (4) Phenol resin (5) Epoxy resin (6) Polymer compound having hydrazide group (7) Polytetrafluoro Ethylene-containing polymer compound (8) Monohydric or polyhydric alcohol methacrylic acid monoester
-Polyhydric alcohol methacrylic acid (9) Polyester copolymer For details of these substances (1) to (9), refer to Japanese Patent Application No.
24639 (especially pages 62 to 66) can be referred to.

The distilled water obtained from the photographic processing waste liquid of the present invention may be subjected to an ultraviolet irradiation treatment. The ultraviolet light used can be obtained by a commercially available ultraviolet lamp, an ultraviolet irradiation device, a halogen lamp or the like. It is not limited. Outputs of this ultraviolet lamp and the like are known to have an output of 5 W to 1 kW, but are not limited to this. The ultraviolet lamp that may be used in the present invention may generate electromagnetic waves and light having a wavelength outside the range of 190 nm to 400 nm, and may irradiate distilled water obtained from photographic processing waste liquid. Also, a combination of infrared rays and the like may be used.

The ultraviolet lamp or the like that may be used in the present invention may be a double tube.

The above-mentioned ultraviolet irradiation means that the distilled water obtained from the photographic processing waste liquid is irradiated with ultraviolet rays using an ultraviolet lamp or the like, and these ultraviolet rays are continuously applied to the distilled water. It may be performed intermittently as needed.

In the above reverse osmosis treatment, various reverse osmosis membranes and desalting / concentrating methods and apparatuses using the reverse osmosis membrane can be used without limitation. As the reverse osmosis membrane, cellulose acetate, aromatic polyamide, polyvinyl alcohol, and polysulfone are preferable, and cellulose acetate is particularly preferably used.

[0102] Reverse osmosis apparatus, it is operated at a pressure of 40Kg / cm ² ~55Kg / cm ² is separation performance, from the viewpoint of throughput.

The oxidizing agent used in the oxidizing agent treatment that may be used in the present invention includes metals, nonmetal oxides, oxide oxyacids and salts thereof, peroxides, compounds containing organic oxygen, and the like. Belong. Nitric oxide NOx, chromic anhydride CrO ₃ , selenium dioxide SeO ₂ , manganese dioxide MnO ₂ , lead dioxide PbO ₂ , osmium tetroxide OsO ₄ , silver oxide Ag ₂ O, copper oxide as oxides
CuO and mercury oxide HgO are exemplified. Examples of the oxyacid include HNO ₃ such as hot concentrated sulfuric acid H ₂ SO ₄ , nitrous acid HNO ₂ and nitric acid. As salts, sodium hypochlorite NaOCl, bleached powder CaOC
l ₂ , potassium dichromate K ₂ Cr ₂ O ₇ , potassium chromate K ₂ C
r ₂ O ₄ , potassium permanganate KMnO ₄ , potassium chlorate KCl
O ₃ and potassium perchlorate KClO ₄ . Representative peroxides include hydrogen peroxide H ₂ O ₂ , sodium peroxide Na ₂ O ₂ , benzoyl peroxide (C ₆ H ₅ COO) _{2 and the} like. A substance capable of taking two or more valences, for example, trivalent iron ion Fe
³⁺ , divalent copper ion Cu ²⁺ , lead tetraacetate Pb (CH ₃ CO ₂ ) _{4 and the} like are also included. Other Fenton's reagent ^{_{(Fe ++ + H 2 O 2}} ), dehydrogenation catalyst (Pt, Se, Zn) or the like can also be used as the oxidizing agent.

The electrolytic oxidation treatment which may be used in the present invention is a method of oxidizing a substance at an anode by electrolysis.
Any method of increasing the positive charge of the cation, decreasing the negative charge of the anion, polymerizing the anion, increasing the oxygen atoms in the atomic group and decreasing the hydrogen atoms may be used. The advantages over oxidation are that very strong oxidation can take place and that there are few by-products.

The aeration treatment that may be used in the present invention is to promote oxidation by blowing air into distilled water of photographic processing waste liquid, and it is preferable to make air bubbles finer using a distributor or the like. Thereby, the bubbling effect can be improved, and the removal efficiency of the organic solvent or the like can be increased.

The electrodialysis treatment that may be used in the present invention means that the cathode and anode of an electrodialysis tank are separated by a diaphragm,
Distilled water of the photographic processing waste liquid is put into a partitioned chamber, and a direct current is passed through the electrode.

Preferably, the diaphragm is an ion-exchange membrane, and more preferably, the cathode and the anode are separated by an anion-exchange membrane and a cation-exchange membrane, and a cathode chamber, a plurality of concentrating chambers (the cathode side being An anion exchange membrane, a chamber whose anode side is partitioned by a cation exchange membrane), a plurality of desalting chambers (a chamber where the cathode side is partitioned by a cation exchange membrane, the anode side is partitioned by an anion exchange membrane), and an anode chamber It is. The distilled water of the photographic processing waste liquid is put into the desalting chamber, but may be put into the concentrating chamber. Concentration room,
The electrolyte solution to be put into the anode chamber is not particularly limited, and for example, 0.1% of sodium sulfite, sodium sulfate, sodium chloride, potassium sulfate, sodium thiosulfate, etc.
~ 2N solution can be preferably used. At this time,
It is very preferable to use a processing solution having a fixing ability (bleach-fixing solution or fixing solution) or a waste liquid thereof as an electrolyte solution to be placed in a concentration chamber or an anode chamber, since no electrolyte solution is required.

The redistillation treatment that may be used in the present invention means that a concentrated solution obtained from a photographic processing waste liquid is subjected to a distillation treatment, and is one of so-called rectification operations. Batch distillation
(Including simple distillation and batch rectification) or continuous distillation, and a continuous equilibrium distillation method for continuous rectification can also be employed. Obtaining pure water (a substance having a remarkably small fraction other than water) by the redistillation process can effectively supply water to the photographic processing solution. It is also advantageous to use suitable separating agents in azeotropic distillation and extractive distillation. In the present invention, the secondary treatment effect can also be obtained by so-called steam distillation. The operating pressure may be any of high-pressure distillation, atmospheric distillation, vacuum distillation, and molecular distillation.

The ion exchange resin treatment which may be used in the present invention can be carried out by bringing various kinds of ion exchange resins into contact with a photographic processing waste liquid. A cation exchange resin and an anion exchange resin with a functional group bonded to the substrate,
There are chelating resins and adsorption resins.

For examples of the chemical structure and usage of the ion exchange resin, reference can be made to the contents described in Japanese Patent Application No. 59-124639 (especially pages 54 to 57).

Next, representative examples of the photographic processing waste liquid which can be processed according to the present invention will be described in detail. However, the following mainly describes photographic processing solutions when the photographic material to be processed is for color. The photographic processing waste liquid overflows when processing a silver halide color photographic material using these photographic processing solutions. Most liquids.

The color developing solution is used in a color developing process (a process for forming a color image, specifically, a process for forming a color image by a coupling reaction between an oxidized color developing agent and a color coupler). Processing solution to be used,
Therefore, in the color development processing step, it is usually necessary to include a color developing agent in the color developing solution, but the color developing agent is incorporated in the color photographic material, and the color developing solution containing the color developing agent or Treatment with an alkali solution (activator solution) is also included. The color developing agent contained in the color developing solution is an aromatic primary amine color developing agent, and includes aminophenol-based and p-phenyleneamine-based derivatives.

Examples of the above-mentioned aminophenol-based developer include o-aminophenol, p-aminophenol, 5-amino-2-oxy-toluene, 2-amino-3-oxy-toluene, 2-oxy-3-amino Includes -1,4-dimethyl-benzene.

The color developing solution may contain an alkali agent usually used in the developing solution, and may further contain various additives such as benzyl alcohol, an alkali metal halide, or a preservative for a development control agent. Furthermore, various antifoaming agents and surfactants, and organic solvents such as methanol, dimethylformamide and dimethylsulfoxide may be appropriately contained. Further, the color developing solution may contain an antioxidant as needed. Further, in the color developing solution, various chelating agents may be used in combination as a sequestering agent.

The bleach-fixing solution is used in a bleach-fixing step (a step of oxidizing metallic silver produced by development to replace silver halide, and then forming a water-soluble complex and coloring undeveloped portions of the color former). The bleaching agent used in the bleach-fixing solution is a processing solution, regardless of its type.

Incidentally, the bleach-fixing solution may contain various pH buffers alone or in combination of two or more. Furthermore, various fluorescent whitening agents, defoaming agents or surfactants may be contained. Further, it may contain a preservative such as a bisulfite adduct, an organic chelating agent such as aminopolycarboxylic acid, a stabilizer such as nitro alcohol and nitric acid, an organic solvent, and the like. Further, the bleach-fixing solution is disclosed in JP-A-46-280, JP-B-45-8506, JP-B-46-556, Belgian Patent No. 770,910, JP-B-45-8836, JP-B-53-9854, Various bleaching accelerators described in JP-A-54-71634 and JP-A-49-42349 may be added.

In the present invention, it may be combined with the washing stabilizing treatment.

As the stabilizing solution, there is a stabilizing solution having a function of stabilizing a color image and a function of a draining bath function for preventing contamination such as unevenness in washing. In addition, these stabilizers also include a color adjustment liquid for coloring a color image and an antistatic liquid containing an antistatic agent. When the bleach-fixing component is brought into the stabilizing solution from the pre-bath, it is neutralized, desalted, and inactivated to prevent the storage stability of the dye from being deteriorated.

As a component contained in such a stabilizing solution, there is a chelating agent having a chelate stability constant with iron ions of 6 or more (particularly preferably 8 or more). These chelating agents include an organic carboxylic acid chelating agent, an organic phosphoric acid chelating agent, a polyhydroxy compound, an inorganic phosphoric acid chelating agent, etc., and particularly preferably diethylenetriaminepentaacetic acid, 1-hydroxyethylidene-, for the effect of the present invention. 1,1-diphosphonic acid and salts thereof. These compounds are generally used at a concentration of about 0.1 g to 10 g per liter of stabilizer, more preferably at a concentration of about 0.5 g to 5 g per liter of stabilizer.

As the compound added to the stabilizing solution, there is an ammonium compound. These are supplied by ammonium salts of various inorganic compounds, specifically, ammonium hydroxide, ammonium bromide, ammonium carbonate,
Ammonium chloride, ammonium hypophosphite, ammonium phosphate, ammonium phosphite, ammonium fluoride, ammonium acid fluoride, ammonium fluoroborate, ammonium arsenate, ammonium hydrogen carbonate, ammonium hydrogen fluoride, ammonium hydrogen sulfate, ammonium sulfate, Ammonium iodide, ammonium nitrate, ammonium pentaborate, ammonium acetate, ammonium adipate, ammonium lauryl tricarboxylate, ammonium benzoate, ammonium carbamate, ammonium citrate, ammonium diethyldithiocarbamate, ammonium formate, ammonium hydrogen malate, oxalic acid Ammonium hydrogen, ammonium hydrogen phthalate, ammonium bitartrate, ammonium lactate, ammonium malate Ammonium maleate, ammonium oxalate, ammonium phthalate, ammonium picrate, pyrrolidine ammonium dithiocarbamate, ammonium salicylate, ammonium succinate,
Ammonium sulfanilate, ammonium tartrate, ammonium thioglycolate, ammonium 2,4,6-trinitrophenol, and the like. The addition amount of these ammonium compounds is used in the range of 0.05 to 100 g, preferably 0.1 to 20 g, per liter of the stabilizing solution.

Compounds added to the stabilizing solution include pH
Modifier, 5-chloro-2-methyl-4-isothiazolin-3-one, 2-octyl-4-isothiazolin-3-one, 1,2-benzisothiazolin-3-one and other Japanese Patent Application No. 59-146325 (No. 26-3
(Page 0) Anti-binders, preservatives such as water-soluble metal salts, dispersants such as ethylene glycol, polyethylene glycol, polyvinylpyrrolidone (PVP K-15, Rubiscol K-17, etc.),
Hardening agents such as formalin, fluorescent whitening agents and the like can be mentioned.

When using a washing substitute stabilizer containing the above-mentioned anti-binder, the generation of tar in the evaporator is small.

When the photosensitive material to be processed is a negative material,
An aldehyde derivative may be added to the negative stabilizing solution in order to improve photographic image preservability.

The negative stabilizing solution may optionally contain various additives such as a water drop unevenness inhibitor, a pH adjuster, a hardening agent, an organic solvent, a humectant, and other color tone agents to improve the processing effect. Additives for expansion may be added.

In the present invention, the washing alternative stabilization treatment which may be carried out using a washing alternative stabilizing solution is a process in which a large amount of ordinary running water is used to wash away the processing solution of the preceding stage which has adhered or permeated the photographic light-sensitive material. rather, per unit area slightly 30ml / m ² ~9000ml / m ² of photographic material in stabilizing bath, the effect of equal to or more than the above by the more preferably ^{60ml / m 2 ~3000ml / m 2} l supplemented Specifically, it refers to image stabilization processing as described in JP-A-58-134636.

Therefore, when a washing-replacement alternative liquid is used, there is no need to provide a supply / discharge pipe to the outside of the automatic processing machine for water flow unlike the prior art.

Further, a stilbene-based fluorescent whitening agent may be used in a color developing solution or a stabilizing solution for color paper.

The components contained in the waste color developing solution are as follows:
These are the above-mentioned various components and additives, and components which elute and accumulate from the photographic material to be processed.

The components contained in the bleach-fixing solution and the waste solution of the stabilizing solution are the above-mentioned various components or additives, and components which elute and accumulate from the photographic material to be processed.

Next, an example of an apparatus for evaporating photographic processing waste liquid according to the present invention will be described with reference to the accompanying drawings.

A Automatic Developing Machine The automatic developing machine to which the present invention is applied is designated by reference numeral 10 in FIG. 1. In the illustrated developing machine, a roll-shaped photographic light-sensitive material F is loaded into a color developing tank CD and a bleach-fixing tank BF. , Washing alternative stabilization tank Sb
The photographic processing is continuously performed by guides, and after drying D, the film is wound up (not shown, but as an automatic developing machine,
Color developing tank CD, bleaching tank BL, fixing tank FIX, washing alternative stabilizing tank Sb to guide photographic light-sensitive material to short reader, second
There are various types such as a mode having a stabilization tank, but representative ones are shown in the drawings).

Reference numeral 11 denotes a replenisher tank for detecting the amount of photographic processing of the photographic material F by a sensor 21 which will be described later, and replenishing a replenisher to each processing tank by the controller 20 according to the detected information.

The photographic processing method, the constitution of the photographic processing tank, and the method of replenishing the replenisher are not limited to those described above. For example, JP-A-58-14834, JP-A-58-34448, and JP-A-57-34448 132
No. 146 and Nos. 58-18631, Nos. 60-263941, No. 61-2153, etc. It is possible.

Although the apparatus for treating photographic processing waste liquid of the present invention may be provided in an automatic processor, the apparatus for processing photographic processing waste liquid according to the present invention is used when a large amount of photographic processing waste liquid is to be processed collectively. (FIG. 10).

Since the description in FIG. 10 is essentially the same as that of the automatic developing machine in the specification of the present application, it will be described below simultaneously.

B. Recovery of waste liquid for photographic processing and silver recovery When replenisher is supplied to each processing tank, it is discharged from the processing tank as overflow waste liquid and collected in stock tank 30. At this time, the waste liquid of the color developing tank CD is put into the stock tank 30 without passing through the silver collecting means 80 according to the silver collecting processing technology of the present invention, but the waste liquid of the bleach-fixing tank BF and the washing alternative stabilizing tank Sb is the present invention. After silver recovery processing by silver recovery means 80 using silver recovery processing technology, the stock tank 30
Can be put in. In the illustrated automatic developing machine, the portion that overflows from the upper portion of the processing tank due to the replenishment of the replenisher is processed as photographic processing waste liquid.

A plurality of silver recovery means 80 and a plurality of stock tanks 30 are provided, and a plurality of processing means 40 are provided.
Use of the above as a stock tank (for example, alternate use of the stock tank and the processing means) is also included in the present invention. If a certain amount is processed at once using the stock tank 30, the concentrated or dried photographic processing waste liquid can be homogenized, and the stock tank 30 is useful as a buffer from the photographic processing tank to the processing means. .

As a means for transferring the overflowed photographic processing waste liquid to the silver recovery means or the stock tank 30, a simple method is to allow the photographic processing waste liquid to fall naturally through a guide tube. Silver recovery means by collecting the thermal energy possessed or by using the thermal energy of an automatic developing machine or the evaporation processing device described later.
A means for preheating the photographic processing waste liquid or evaporating the water before it is collected in the storage tank 80 or the stock tank 30 may be provided, or may be forcibly transferred by the pump 23 or the like.

Further, since there is a difference in the components in the photographic processing waste liquid in each of the photographic processing tanks CD, BF, and Sb, all the photographic processing waste liquids are not batch-processed, and each photographic processing tank has two or more photographic processing waste liquids. The case where the stock tank 30 is prepared for each waste liquid in the treatment tank divided into groups and treated separately is also included. In particular, it is advantageous to separate the waste liquid in the color developing tank CD from the waste liquid in the bleach-fixing tank BF and the washing alternative stabilizing tank Sb from the viewpoint of silver recovery.

Alternatively, the waste liquid may be forcibly transferred to a stock tank by a pump by piping to a waste liquid tank in an existing automatic developing machine or the like. Further, the waste liquid tank itself of the automatic developing machine can be used as a stock tank. in this case,
It is preferable to detect the weight of the stock tank and operate the pump to forcibly transfer the waste liquid through a pipe. Floating a float in a waste liquid tank to detect a liquid level above a certain level and operating a pump is also easy to install in an existing automatic developing machine.

C Processing Means The processing means 40 includes a heating means 41, a processing chamber 42 including means for storing a processed or processed photographic processing waste liquid (concentrated liquid), and discharges a processed photographic processing waste liquid (concentrated liquid) from the processing chamber 42. Means of doing 43
Is included.

Further, preferably, a reference example may be provided in which a gas adsorbing means 50 and 51 using a filter, an adsorbent or the like, and a means for reusing distilled water 60 including steam cooling means are added.

As the heating means 41, there are a heat source and a heating (evaporation) method, but there is no reason why the present invention is not limited to a specific one, and the heating means 41 is effective for electricity, gas, solar heat and the like. Includes those which use one or more heat sources to heat photographic processing waste liquid and evaporate and concentrate the photographic processing waste liquid. In addition, the photographic processing waste liquid is stored in the processing chamber 42 and the whole is heated. For example, the photographic processing waste liquid is dropped or dropped on a heating element such as an overheated metal plate.
It can be configured in various ways, including those that evaporate (including spraying) and those that are continuously supplied and supplied to a heat source in fixed amounts, and furthermore, the photographic processing waste liquid is sprayed into the processing chamber 42 in the form of mist. Alternatively, the photographic processing waste liquid may be evaporated by applying heated air. The heated air may be introduced into the waste photographic processing liquid.

[0144] In the case of spraying, the photographic processing waste liquid may be put in a heated swirling airflow, and a spray drying apparatus can be used.

The position of the heating means 41 is arbitrary such as above, inside, or outside the processing chamber 42 of the stored photographic processing waste liquid.

In the method of evaporating the photographic processing waste liquid which may be used in the present invention, particularly when the heating means 41 directly contacts the photographic processing waste liquid such as a quartz tube with a built-in heat source such as a nichrome wire or an electric heating plate, the photographic processing waste liquid is During the process of concentration or drying, it has been found that the waste photographic processing solution sticks to the surface of the photographic processing solution, and the thermal efficiency is significantly reduced. Further, it has been found that the photographic processing waste liquid tends to adhere to a heat conducting member that conducts heat from the heat source to the photographic processing waste liquid, and that even in a part unrelated to heating, corrosion is liable to occur when the waste liquid or steam is in direct contact. .

The present inventors conducted various experiments and obtained the following preferred examples.

In the case where the photographic processing waste liquid or vapor is in direct contact with the heat source, the heat source is not in direct contact with the heat source and the photographic processing waste liquid as shown in FIG. An example of performing Teflon processing (coating of a fluororesin) was attempted. In this embodiment, two quartz tubes with a built-in 750 W nichrome wire are used, a metal vessel is provided above the quartz tube, a photographic processing waste liquid is put therein, and the surface of the metal is treated with Teflon as a means 44 for preventing the photographic processing liquid from sticking. After processing (fluororesin coating), it was placed in a photographic processing waste liquid to be processed directly, and a processing experiment of photographic processing waste liquid was performed. No sticking phenomenon of tar in the concentrated waste liquid was observed. In the case where no processing was performed, tar was fixed, and it took time to concentrate the photographic waste liquid from the second time onward. Not only was there a significant decrease in thermal efficiency, but also corrosion of metal parts was observed. .

Experiments were performed on each of Teflon processing means other than the fluororesin coating, for example, a binder type, a plating type and an oil-mixing type, and a heat treatment type and a normal temperature compress type. Good results were obtained.

In the same manner, “Composite material technology integration”
(1976, Industrial Technology Center, pp.213-219), "New Materials 1984" (1984, Toray Research Center, pp.287-31)
5) When an experiment was performed using inorganic fibers described in "Composite Materials" (1984, published by The University of Tokyo Press), the same results as above were obtained.

As shown in FIG. 1, in the case of using an inner pot, the above-mentioned means for preventing the photographic processing waste liquid from being fixed are provided on the inside thereof, particularly on the portion where the heat of the heating means 41 is conducted.
From the standpoint of preventing damage to the equipment due to corrosion or the like, it is preferable to provide a means for preventing photographic processing waste liquid from sticking to all the equipment inside the processing chamber.

Next, in FIG. 1, a heating means 41 having a quartz tube with a built-in nichrome wire as a heat source is provided at the bottom of the processing chamber 42, and a liquid layer 44 made of, for example, silicon oil is formed as a means for preventing adhesion to a slightly upper portion thereof. An experiment was conducted on an example in which the photographic processing waste liquid was pooled thereon and subjected to heat treatment. As a result, no sticking phenomenon of the waste liquid to the heat source was observed, and good results similar to those obtained by Teflon processing were obtained.

The structure of the processing chamber 42 is determined in accordance with the structure of the heating means 41 described above. However, it is preferable to set a reduced pressure atmosphere to lower the boiling point to promote the evaporation of water.

The processing chamber 42 is configured to store a photographic processing waste liquid to be processed or a processed concentrated liquid, and forms an inner pot or insole 44 with metal, ceramic, synthetic resin, etc., a bag filter or a pack, etc. Using the separation means of
The treated concentrate may be solidified and taken out together with the inner pot or the insole 44 or the whole bag filter or the pack and discarded or treated. The above-mentioned inner pot or insole 44
In addition to the above-described method, the discharging means 43 includes a known discharging device using a rotary screw pump or a concentrated liquid of the photographic processing waste liquid through a valve from the bottom of the processing chamber 42 through a valve. Alternatively, various designs can be used, such as those that naturally fall into a container having two or more and solidify.

The insole 44 or pack is heat resistant.
Chemical resistant materials such as carbon fiber, aramid fiber, Teflon resin fiber, hemp, glass fiber, polyethylene foam and polypropylene foam are preferred.

The photographic processing waste liquid processing apparatus of the present invention may be controlled mainly by (1) discharging the photographic processing waste liquid to the silver recovery means 80 and the stock tanks 30 and 31 (2) from the stock tank 30 Supply of waste photographic processing liquid to processing means 40 (3) Each operation of the processing means 40 will be sequentially described below.

(1) Discharge of the photographic processing waste liquid to the silver recovery means 80 and the stock tank 30 The amount and temperature of the photographic processing waste liquid in the silver recovery means 80 and the stock tank 30 are detected by the sensor 22.
It is sequentially stored in the storage unit of the control device 20. Therefore, when it is detected that the photographic processing waste liquid in the silver recovery means 80 and the stock tank 30 is full, replenishment of the replenisher is prohibited or replenishment is performed so that the photographic processing waste liquid is not newly discharged. Emergency discharge by the pump 23 from the silver recovery means 80 or the stock tank 30 to the processing means 40 is performed according to the liquid replenishment instruction information. In order to prevent a malfunction, it is preferable that the silver collecting means 80 and the stock tank 30 have a sufficient capacity, or a plurality of silver collecting means 80, the stock tank 30 and a spare tank are provided. Further, in a system in which the photographic processing waste liquid is not batch-processed but is separately processed in accordance with the type of the photographic processing waste liquid, the silver collecting means 80 and the stock tank 30 are not used.
Each time, the amount of liquid, temperature, etc. are detected.

The detection of the temperature of the photographic processing waste liquid in the stock tank 30 is information of the photographic processing waste liquid for controlling the operation of the processing means 40 described later, particularly for controlling the heating temperature.

(2) Processing means from stock tanks 30 and 31
Supply of photographic processing waste liquid to 40: The supply control of the photographic processing waste liquid from the stock tanks 30 and 31 to the waste liquid processing means 40 includes a single waste liquid processing means 40 and a plurality of waste liquid processing means. In the latter case, a plurality of waste liquid treatment means 40 are provided, and one or more of them may also serve as a stock tank. In such a case, the photographic processing waste liquid is transferred to the above-mentioned stock tank. Similarly to the discharge, the waste liquid is divided into a plurality of waste liquid processing means 40 prepared for each waste liquid in the photographic processing tank, discharged, and evaporated in principle by the waste liquid processing means 40 supplied.

When the waste liquid processing means 40 is singular, another photographic processing waste liquid is supplied after the processing of the previous liquid is completed so that the photographic processing waste liquid which is divided and stored in the stock tanks 30 and 31 is not mixed. I will do it.

The supply of the photographic processing waste liquid from the stock tank 30 to the processing means 40 is carried out at a fixed amount (the amount that can be stored at one time in the waste liquid processing means 40) at one time, or at a fixed amount or a variable amount continuously. There is a system to supply the power. In the former case, the supply of the photographic processing waste liquid from the stock tank 30 to the processing means 40 in accordance with the information on the reduction amount of the photographic processing waste liquid in the stock tank 30 by the sensor 22 and / or the detection information of the amount of the photographic processing waste liquid in the processing means 40 by the sensor 24 Control. In addition,
In this case, the control may be performed in accordance with detection information from a flow meter provided in a photographic processing waste liquid supply pipe from the stock tank 30 to the processing means 40.

In the case of a system in which a fixed amount or a variable amount is continuously supplied, the temperature of the photographic processing waste liquid to be supplied and the processing means 40
The amount of the photographic processing waste liquid to be supplied is adjusted according to the temperature of the heating means 41 or the processing chamber. Further, the amount of the photographic processing waste liquid to be supplied is always kept constant, and the amount of the photographic processing waste liquid in the processing means 40 is detected by the sensor 24, and the heating means 41, for example, the heating temperature by the heater is controlled to increase or decrease by the amount, Alternatively, the heating time may be controlled to increase or decrease.

(3) Operation of the processing means 40: The control of the operation of the processing means 40 is also described in the previous section, but the difference between the amount of the supplied photographic processing waste liquid and the amount of the processed photographic processing waste liquid, or
This is done according to the amount of residual photographic processing waste or the amount of processed and concentrated photographic processing waste.

In the system in which the photographic processing waste liquid is supplied to the processing means 40 by a predetermined amount at a time, the temperature of the supplied photographic processing waste liquid and the temperature of the heating means 41 or the processing chamber 42 are detected. In this case, the operation of the processing means 40 can be controlled by controlling the processing time.

The supply of the photographic processing waste liquid to be processed and the operation of the processing means (control of the heating means and the discharge of the processed waste liquid) include stopping the operation at the time of discharging, operating the heating means at the time of discharging at low energy, and processing at the time of supply. Various designs such as simultaneous discharge are possible.

In the above, the processing progress of the photographic processing waste liquid in the processing means is controlled by the processing time, the viscosity of the photographic processing waste liquid, the lower limit level of the photographic processing waste liquid in the processing chamber 42, the steam temperature,
It is controlled by detecting pressure, weight, conductivity, turbidity or temperature outside the transmittance device, etc., and stops the operation of the photographic processing waste liquid processing means 40 when the photographic processing waste liquid is concentrated to a certain concentration or low energy. Switch to driving.

The supply, processing (evaporation / concentration), and discharge of the photographic processing waste liquid are controlled by various items as described above, and the time, viscosity, temperature, pressure liquid level, concentration, Various sensors to detect electric resistance, weight, etc.
24 and the like are used, and mounting positions of the sensor 24 and the like are various.

In the case of the time control, the time differs between the batch processing and the continuous charging processing, and the time varies depending on the temperature of the supplied photographic processing waste liquid.

In order to measure the degree of processing by detecting the viscosity of the photographic processing waste liquid, various viscometers such as a capillary viscometer may be used. For example, a load on a stirring propeller or a rod may be detected or discharged. When a bar screw is used as the means, the viscosity is detected by the load applied to the drive motor.
In order to detect the viscosity by using the rotating screw or the propeller in this manner, a processing completion signal may be generated by increasing the rotation load or decreasing the number of rotations in accordance with the increase in the viscosity.

For detecting the concentration, for example, a light emitting device, a reflecting plate, a light receiving device, etc. are arranged at a certain height in the processing chamber, and a measuring device for measuring the light transmittance (attenuation rate) and the refractive index is used. Used.
It can also be detected by a change in electric resistance accompanying a change in concentration.

The steam temperature in the processing chamber 42 is not shown,
For example, if the device is configured so that the heating part is exposed above the liquid level when the liquid level of the waste liquid falls as the evaporation process decreases and falls below a certain position, the overheating phenomenon occurs from the stage where the heating part is exposed. Since the steam temperature in the processing chamber rises sharply, the degree of progress of the waste liquid processing can be detected.

The level of the liquid can also be detected by installing a sensor at a predetermined height of the inner wall of the processing chamber 42, the electric resistance of which changes depending on the presence or absence of the liquid. The liquid level can also be detected by mechanical means using a float or the like.

In order to measure the weight, for example, an electric or mechanical weighing scale is arranged on the lower surface of the inner pot placed in the processing chamber 42 to detect the weight.

The amount of generated steam can be detected, for example, by disposing a flow meter in front of the gas adsorbing means. When the cooling means 60 is provided, the amount (weight, It can also be detected by measuring the liquid level).

In the latter case, the operation of the waste liquid treatment means 40 may be stopped or switched to low-energy operation by detecting the steam temperature, weight, and temperature outside the apparatus. In addition,
In the present invention, the term "concentration" means that the volume of the waste liquid is reduced to one half or less of the volume when discharged from the photographic processing tank. From the viewpoint of disposal, the concentration is preferably one quarter or less, more preferably five minutes or less. 1 or less, and optimally 1/10 or less. When concentrated, precipitates or tar may be generated. It suffices if the whole liquid has fluidity, and there may be precipitate or sludge.

[0176]

EXAMPLES The present invention will be described below in detail with reference to examples, but the embodiments of the present invention are not limited thereto.

After image exposure of Sakura Color SR paper (manufactured by Konishi Roku Kogyo Co., Ltd.), continuous processing was performed using the following processing steps and processing solutions.

Reference processing step (1) Color development 38 ° C. 3 minutes 30 seconds (2) Bleaching and fixing 38 ° C. 1 minute 30 seconds (3) Stabilization processing 25 ° C. to 35 ° C. 3 minutes (4) Drying 75 ° C. to 100 About 2 minutes Processing solution composition [Color developing tank solution] Benzyl alcohol 15 ml Ethylene glycol 15 ml Potassium sulfite 2.0 g Potassium bromide 1.3 g Sodium chloride 0.2 g Potassium carbonate 24.0 g 3-Methyl-4-amino-N-ethyl-N- (β-methanesulfonamidoethyl) aniline sulfate 4.5 g fluorescent whitening agent (4,4′-diaminostilbene disulfonic acid derivative) (trade name: Keikol PK-Conk (manufactured by Nippon Sanka Chemical Co., Ltd.)) 1.0 g hydroxylamine sulfate Salt 3.0 g 1-Hydroxyethylidene-1,1-diphosphonic acid 0.4 g Hydroxyethyliminodiacetic acid 5.0 g Magnesium chloride hexahydrate 0.7 g 1,2-Hydroxybenzene-3,5-disulfonic acid-disodium salt 0.2 g Add water to make 1 liter, And pH10.20 in potassium and sulfuric acid.

[Color developing replenisher] benzyl alcohol 20 ml ethylene glycol 20 ml potassium sulfite 3.0 g potassium carbonate 30.0 g hydroxylamine sulfate 4.0 g 3-methyl-4-amino-N-ethyl-N- (β-methanesulfonamidoethyl ) Aniline sulfate 6.0 g Optical brightener (4,4'-diaminostilbene disulfonic acid derivative) (trade name: Keicoll PK-Conc (manufactured by Shin Nisso Chemical Industries, Ltd.)) 2.5 g 1-hydroxyethylidene-1,1-II Phosphonic acid 0.5 g Hydroxyethyl iminodiacetic acid 5.0 g Magnesium chloride hexahydrate 0.8 g 1,2-Hydroxybenzene-3,5-disulphonic acid-disodium salt 0.3 g Add water to make 1 liter, and adjust to pH 10 with potassium hydroxide. .70.

[Bleaching-fixing tank solution] Ethylenediaminetetraacetic acid ferric ammonium dihydrate 60.0 g Ethylenediaminetetraacetic acid 3.0 g Ammonium thiosulfate (70% solution) 100.0 ml Ammonium sulfite (40% solution) 27.5 ml Adjust to 1 l and adjust to pH 7.1 with potassium carbonate or glacial acetic acid.

[Bleaching-fixing replenisher A] Ferric ammonium ethylenediaminetetraacetate dihydrate 260.0 g Potassium carbonate 42.0 g Water is added to make the total volume 1 liter.

The pH of this solution is 6.7 ± 0.1.

[Bleaching and Fixing Replenisher B] Ammonium thiosulfate (70% solution) 500.0 ml Ammonium sulfite (40% solution) 250.0 ml Ethylenediaminetetraacetic acid 17.0 g Glacial acetic acid 85.0 ml The total volume is adjusted to 1 liter by adding water.

The pH of this solution is 5.3 ± 0.1.

[Washing Alternative Stable Tank Solution and Replenisher] Ethylene glycol 1.0 g 1-hydroxyethylidene-1,1-diphosphonic acid (60% aqueous solution) 1.0 g Ammonia water (25% ammonium hydroxide aqueous solution) 2.0 g With water The pH is adjusted to 7.0 with sulfuric acid.

An automatic developing machine is filled with the above-mentioned color developing tank solution, bleach-fixing tank solution and stabilizing tank solution, and the above-described color developing replenisher and bleach-fixing are processed every three minutes while processing the Sakura Color SR paper sample. A running test was performed while replenishing the replenishers A and B and the stable replenisher using a quantitative cup. The replenishment amount is 190 ml as a replenishment amount to the color developing tank per 1 m ² of color paper, the replenishment amount to the bleach-fixing tank is 50 ml for each of the bleach-fix replenishers A and B, and the replenishment amount to the stabilization tank is a washing replenishment stable replenisher. Was supplemented with 250 ml. The stabilizing tank of the automatic developing machine is a stabilizing tank that becomes the first to third tanks in the direction of the sample flow, replenishment is performed from the last tank, and the overflow liquid from the last tank flows into the preceding tank. In addition, a multi-tank countercurrent system was used in which the overflow liquid was allowed to flow again into the preceding tank.

Continuous processing was carried out until the total replenishment amount of the washing-replacement stable liquid became three times the stabilization tank capacity.

An overflow solution generated by the above processing, wherein [overflow solution of color developing solution]: [overflow solution of bleach-fixing solution]: [overflow solution of stabilizing solution instead of washing] = 3: 3: 5. The following processing was performed on the photographic processing waste liquid (A). Further, an insole 44 made of carbon fiber fabric is placed on the bottom of the evaporator in advance, and after evaporating and concentrating as in Reference Example 1, 200 g of a highly absorbent resin (Sumikagel N-100, trade name, manufactured by Sumitomo Chemical Co., Ltd.)
Was added and the entire insole 44 made of the woven fabric was removed, so that all the adhered substances and the like attached to the insole 44 could be easily removed. Looking at the inside of the evaporator, it was beautiful without so-called sticking or jumping marks.

Reference Example 1 The photographic processing waste liquid (A) was subjected to an evaporating process using an evaporating pot containing two 750 W quartz tubes with a built-in nichrome wire, and the resulting steam Q was produced as shown in FIG.
When cooled using the heat sink device 62 shown in FIG.
was gotten. Also, the odor was extremely small as compared with the case where the heat sink device was not used.

Reference Examples 2 to 7 When the steam Q obtained by the evaporation treatment of Reference Example 1 was subjected to cooling treatment using the cooling means shown in FIGS. 4 to 9, the cooling means was the same as in Reference Example 1 in any case. The odor was extremely small as compared with the case where no was used, and the distilled liquid R was obtained without any problem. 4 to 6, the photographic processing waste liquid was preheated, and the evaporating process in the evaporator was faster than that without preheating under the same conditions. 8 was suitable for controlling the temperature of the color developing tank. When I looked inside the kettle, I could see no so-called sticking or jumping traces,
It was beautiful. In addition, when the highly absorbent resin was discharged to a container provided therein using the discharging means 43, good processing was performed.

Reference Example 8 After 2 l of the photographic processing waste liquid (A) was evaporated to dryness, the lid 45 was removed, and the dried matter was taken out of the evaporator.
The dried matter stuck to the bottom of the evaporator and scattered on the wall, and it was difficult to remove all of the dried matter.

Reference Example 9 After evaporation and concentration as in Reference Example 1, 200 g of a superabsorbent resin (Sumikagel N-100, trade name, manufactured by Sumitomo Chemical Co., Ltd.) was added. As a result, the waste liquid was successfully taken out.

Reference Example 10 Photoprocessing waste liquid to be processed first supplied into the processing chamber 42
(A) is 2 liters, the heating capacity of the heater is 1.5 KW, and evaporation is performed. When the viscosity at the evaporation temperature is increased by 10% by a rotational viscometer, the photographic processing waste liquid in the processing means 40 is examined. Was.

Reference Example 11 Waste photographic processing liquid to be processed first supplied into the processing chamber 42
(A) is 2 liters, the heating capacity of the heater is 1.5 KW, the evaporation process is carried out, and when the viscosity is increased by 10% by a rotational viscometer, the photographic processing waste liquid (A) to be processed is newly supplied several times. When the photographic processing waste liquid in the processing means 40 was examined, it was found to be about three times as concentrated as in Reference Example 3.

Reference Example 12 When the liquid level in the processing chamber 42 was detected and the level was reduced to one-tenth, the concentrated waste liquid was taken out.
Further, when the liquid level in the processing chamber 42 is detected and the level is reduced to one fifth, the photographic processing waste liquid to be processed (A)
Was newly supplied, and when the liquid level was lowered to 1/5 again, the concentrated waste liquid was taken out.

Reference Example 13 The photographic processing waste liquid (A) was subjected to desilvering treatment using an electrolytic silver recovery apparatus (manufactured by San Seiki Seisakusho Co., Ltd., Model BN-10) until the silver complex salt became 0.2 g / l, and then the stock was recovered. It was allowed to flow into the tank 30. The mixed solution (3: 8) of the desilvered photographic processing waste solution and the color developing solution overflow solution was transferred from the stock tank 30 to the processing means 40. Here 750W2 quartz tube with built-in nichrome wire
Evaporation was carried out using an evaporator with books. When this process was performed continuously, when the photographic processing waste liquid that was not desilvered was evaporated, silver sulfide was fixed to the bottom of the evaporator, the evaporation efficiency was reduced, and after one month, the evaporator was corroded. occured. On the other hand, these disadvantages were not found at all in the evaporation treatment of the photographic processing waste liquid of the present invention.

Reference Example 14 In place of the electrolytic silver recovery apparatus BN-10 of Reference Example 1, sodium sulfide was added to precipitate silver as silver sulfide, separated by decantation, and the filtrate was flowed into the stock tank 30. . Other than that, when the same experiment as in Reference Example 1 was performed, the same good results were obtained.

Reference Example 15 When the silver recovery operation of Reference Example 1 was performed after the heat treatment of the processing solution, silver sulfide was fixed to the bottom of the evaporator, and after one month, not only corrosion of the evaporator occurred but also Even if the silver-concentrated liquid is used in the same volume, the electrodeposited silver is about 20% less than when silver was collected before evaporation.
Can be obtained, and furthermore, the electrodeposition state of the electrodeposited silver is extremely poor,
It peeled off easily.

REFERENCE EXAMPLE 16 The photographic processing waste liquid (A) was evaporated to 1/10 at the liquid level using an evaporator containing two 750 W quartz tubes with a built-in nichrome wire, and the resulting vapor was cooled to obtain a distillation. When a bleach-fix solution was prepared using the liquid as dissolved water and used in the development processing, no problem was observed in photographic performance. No bumping occurred.

Reference Example 17 The distilled liquid obtained by the evaporation treatment of Reference Example 1 was treated with a column filled with Calgon granular activated carbon TYPE SGL (manufactured by Toyo Calgon Co., Ltd.), and color development was performed using the obtained secondary treatment liquid. When a developing solution was prepared and processed, no problem was observed in photographic performance.

Reference Example 18 The distilled liquid obtained by the evaporation treatment of Reference Example 1 was
After irradiation for 4 hours under a high-pressure mercury lamp, a bleach-fixing solution was prepared using the obtained secondary processing liquid, followed by development processing. No problems were found in photographic performance.

REFERENCE EXAMPLE 19 The distilled liquid obtained by the evaporation treatment of Reference Example 1 was processed in an electrolysis apparatus, and a stable liquid was prepared using the obtained secondary processing liquid and developed. I didn't see it.

REFERENCE EXAMPLE 20 The distilled liquid obtained by the evaporation treatment of Reference Example 1 was fed with air by an air pump, and after 1 hour, a secondary washing liquid was prepared by using the obtained secondary treatment liquid, followed by development processing. As a result, there was no problem in photographic performance.

REFERENCE EXAMPLE 21 In Reference Example 1, the case where the overflow of the washing alternative stabilizer was not used as the photographic processing waste liquid, and the case where the same amount of water was used instead of the overflow of the washing alternative stabilizer was used as reference. The same experiment as in Example 1 was performed.

As a result, in each case, sticking or sticking to the evaporator was slightly observed.

From the comparison with Reference Example 1, it can be seen that when the overflow of the washing-substituting stable liquid is used, the sticking and sticking to the evaporator are extremely small, which is favorable.

Reference Example 22 In Reference Example 1, the gas adsorbing means 50 shown in FIG.
Otherwise, the same experiment as in Reference Example 1 was performed. However, the gas adsorption means 51 includes granular activated carbon (TSURUMI C
OAL CO) (a mixture of granular activated carbon AX type and SX type). After 10 hours of continuous processing, gas detector tube
The amount of ammonia gas and the amount of hydrogen sulfide gas in the exhaust part were measured using (manufactured by Gastec). Next, the cooling means 60 was removed, and a similar comparative experiment was performed for 10 hours to measure gas.

As a result, in the case of the present invention using the cooling means 60, the ammonia gas concentration was 5 ppm, and the hydrogen sulfide gas concentration was 0 ppm. Both are U.S. 1985 ACG
IH (American Conference of Governmental Industrial
Hygienists) is below the recommended concentration limit (ammonia 25 ppm, hydrogen sulfide 10 ppm), and almost no odor was observed. However, when the cooling means 60 was removed, the ammonia gas concentration and the hydrogen sulfide concentration were both 0 ppm immediately after the start of the evaporating process, but after one hour the ammonia gas concentration was 160 ppm and the hydrogen sulfide concentration was 240 ppm. Was. A bad smell was built around the evaporator.

[0209]

The photographic processing waste liquid processing apparatus of the present invention further develops the idea of the photographic processing waste liquid processing apparatus disclosed in Japanese Utility Model Application Laid-Open No. Sho 60-70814, and various devices for practical use of the apparatus. It can be improved, especially in the case of heat treatment of photographic waste liquid, the power consumption is small and efficient waste liquid processing is possible, and the maintenance such as cleaning can be simplified by the anti-sticking means,
In addition, it is most suitable for a photographic processing waste liquid in a photographic processing facility provided with a single or a small number of automatic developing machines, and can easily process steam generated when processing the photographic processing waste liquid. Also, the adhesion of tars is significantly improved. Further, efficient operation can be performed without a decrease in thermal efficiency. Furthermore, excellent results such as stable operation for a long period without corrosion of metal parts are obtained.

[Brief description of the drawings]

FIG. 1 is a schematic view showing an apparatus for treating a photographic processing waste liquid of the present invention.

FIG. 2 is a flowchart illustrating an embodiment of the present invention.

FIG. 3 is a schematic view showing an embodiment of a cooling means used in the processing apparatus.

FIG. 4 is a schematic view showing an embodiment of a cooling means used in the processing apparatus.

FIG. 5 is a schematic view showing an embodiment of a cooling means used in the processing apparatus.

FIG. 6 is a schematic view showing an embodiment of a cooling means used in the processing apparatus.

FIG. 7 is a schematic view showing an embodiment of a cooling means used in the processing apparatus.

FIG. 8 is a schematic view showing an embodiment of a cooling means used in the processing apparatus.

FIG. 9 is a schematic view showing an embodiment of a cooling unit used in the processing apparatus.

FIG. 10 is a schematic view showing a processing apparatus for photographic processing waste liquid of the present invention.

[Explanation of symbols]

 10 Automatic developing machine 11 Replenisher tank 12 Controller 21,22,24 Sensor 23 Pump 30 Stock tank 40 Processing unit 41 Heating means 42 Processing chamber 43 Discharge means 44 Inner pot or insole 45 Collection container 50,51 Gas adsorption means 52 Exhaust part 60 Reuse means of distilled water including cooling means

 ────────────────────────────────────────────────── ─── Continuation of the front page (56) References: Real Opening Shogun 57-47289 (JP, U) Irrigation Wastewater Handbook Handbook Editing Committee, “Revised Second Edition Irrigation Wastewater Handbook”, published by Maruzen Co., Ltd. on June 15, 1976, Pages 656-658

Claims (3)

(57) [Claims] Claims: 1. A color developing solution, a bleaching solution and a color developing solution.
Photographing silver halide photosensitive material with a deposition solution
In the photographic processing waste liquid processing apparatus of the processing apparatus, the waste liquid in the processing tank for heating the photographic processing waste liquid is steamed.
Fluorine resin is added to the surface that comes into contact with this waste liquid during
An apparatus for treating a photographic processing waste liquid, which is provided with an anti-sticking means provided with a process or an inorganic fiber . 2. The method according to claim 1, wherein the evaporation of the photographic processing waste liquid is performed under reduced pressure.
2. The photographic processing according to claim 1, wherein the photographic processing is performed in an atmosphere.
Waste liquid treatment equipment. 3. The photographic processing waste liquid is concentrated to a certain concentration.
Operation of the photographic processing waste liquid processing means is stopped or
Must have control means to switch to low energy operation
The photographic processing waste liquid according to claim 1 or 2,
Processing equipment.