JPH06186222A - Silver detector and silver detecting method - Google Patents

Abstract

PURPOSE:To provide a silver detector and a silver detecting method using the silver detector which can simply and readily detect the remaining silver in waste liquid from which silver has been collected, immediately before disposing of the waste liquid, i.e., treated liquid of photosensitive material. CONSTITUTION:A silver detector has a photography waste-liquid storing part 1. A dithizone carrying part 5 is provided so that the carrying part can be brought into contact with the photography waste liquid in the storing part. In the silver detecting method, chelate agent is added into the photography waste liquid, the above described waste liquid is made to pass through the dithizone carrying part 5 and the silver in the waste liquid is detected.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention collects silver from a silver-containing photographic processed liquid produced by photographic processing of a silver halide photographic light-sensitive material (hereinafter referred to as "light-sensitive material"), and then collects silver-collected waste liquid The present invention relates to a silver detector that detects the presence or absence of silver in a waste liquid when it is discarded, and a silver detection method using the same.

[0002]

2. Description of the Related Art In recent years, regulations on the emission standard of silver that can be discharged into sewers have become stricter year by year from the viewpoint of environmental protection.
In photographic processing of light-sensitive materials, silver components such as silver complex salts in light-sensitive materials are washed out to a considerable concentration in photographic-processed solutions such as fixing solution, rinse solution and washing water (including stabilizing solution). It exists and cannot be directly discharged to the sewer from the viewpoint of environmental protection.

As described above, there are several methods for collecting silver from a silver-containing photographic processed liquid (a liquid subjected to photographic processing). In these methods, it is difficult to completely collect the silver in the waste liquid, and silver having a concentration above the emission standard remains in the waste liquid, or the ability to collect silver from the photographic processed liquid decreases. The silver concentration in the waste liquid may increase. In order to cope with such a case, when discharging the waste liquid after the silver collection, it is necessary to detect the silver concentration to confirm that the concentration of the residual silver in the waste liquid is within the silver emission standard.

[0004]

However, since the emission standard of silver is strict as described above, the concentration of silver in the waste liquid after the collection of silver is as low as 0.1 ppm or less, which is very low. In order to confirm the presence or absence of silver in the concentration, the method of confirming silver by the precipitation formation of silver and halogen is insufficient. Also,
As the silver detector, one that is sensitive to a slight amount of silver and can visually determine the presence or absence of silver is desired. And such a thing leads to the complication of the silver detection apparatus and the complication of operation. For this reason, the burden of discarding the photographic processing solution reduces the efficiency of the work, and therefore it is desired to simplify the silver detector and the detection method.

Therefore, an object of the present invention is to collect residual silver in a silver-collected waste liquid easily and easily after collecting silver from a processed liquid of a light-sensitive material and immediately before discarding the silver. A detector and a silver detection method using the same are provided.

[0006]

The above object of the present invention can be achieved by the following items (1) to (8). (1) A silver detector which has a photographic waste liquid storage portion and is provided so that the photographic waste liquid in the storage portion can contact the dithizone carrying portion. (2) A photographic waste liquid storage part, a flow rate adjusting means for adjusting a flow rate in the liquid transfer, and a liquid transfer part through which liquid flows out from the storage part, and a dithizone carrier in a liquid transfer direction in the liquid transfer part. A silver detector with a holding part that allows liquid to pass through. (3) A photographic waste liquid storage part is provided, and a liquid transfer part capable of moving the photographic waste liquid by a capillary phenomenon is clothed from the storage part, and the liquid can pass through the dithizone carrying part in the liquid transfer direction in the liquid transfer part. Silver detector installed in. (4) It has a photographic waste liquid storage part, and has a liquid moving part from which the photographic waste liquid can move by using an air pressure difference, and the dithizone carrying part in the liquid moving direction in the liquid moving part A silver detector that can be passed through. (5) The dithizone carrying unit is replaceable.
4. The silver detector according to any one of 4 above. (6) The silver detector according to any one of (1) to (5) above, wherein the carrier of the dithizone supporting unit is yellow or white. (7) In any one of (1) to (6) above, a chelate-carrying part is provided on the upstream side in the liquid moving direction in the liquid-moving part, and a dithizone-carrying part is provided on the downstream side so that the liquid can pass therethrough. Silver detector. (8) Silver for detecting silver in the waste liquid by adding a chelating agent to a test liquid consisting of at least one of washing with water, rinsing, and stable waste liquid for photographic processing, and passing the test liquid through a dithizone carrying part. Detection method.

The flow rate adjusting means of the present invention may be any means capable of adjusting the flow rate of the waste liquid and temporarily stopping the movement of the liquid, such as a cock. The liquid moving part of the present invention is preferably one that can move the liquid due to gravity, capillarity, air pressure difference or the like.

[0008]

[Operation] The silver detector configured as described above is provided with at least a portion capable of storing photographic waste liquid and a dithizone carrying portion that develops color in response to silver, and means for allowing the photographic waste liquid to pass through the dithizone carrying portion. Should be provided. When the silver concentration in the waste liquid is equal to or higher than the emission standard, silver reacts with dithizone to develop color, and a waste liquid that does not meet the silver emission standard can be detected.

Although it has been known that dithizone forms a complex with silver and develops a color, it has hitherto been performed simply as a silver extraction colorimetric test in a beaker in a solution state. For this reason, if this is used for silver detection, it is not possible to cope with the emission standard of silver, fluctuations in concentration, etc., and the operation becomes complicated. On the other hand, the present invention is provided as a dithizone-carrying unit having a carrier carrying dithizone so as to block the liquid in the liquid moving unit, and the waste liquid passes through the dithizone-carrying unit. The coloring sensitivity of silver and dithizone can be easily changed by adjusting the amount of dithizone in the dithizone-carrying part or adjusting the flow rate of the waste liquid passing through the dithizone-carrying part.

Since the present invention is for detecting silver in photographic waste liquid, the waste liquid may contain heavy metals other than silver, such as copper, lead and zinc, and these heavy metals are silver. Similarly to, forms a complex with dithizone and develops color. In the silver detector of the present invention in which it is desirable to evaluate only the color development of silver, the presence of heavy metals other than silver becomes a problem.

The present invention makes it possible to obtain only the coloration of silver by providing the chelate-carrying portion on the upstream side in the liquid-moving direction and the dithizone-carrying portion on the downstream side in the liquid-moving portion. It is considered that this is because there is a difference in the stability constant of the complex between dithizone and the heavy metal chelating agent. The stability constant of the chelate complex of the heavy metal other than silver is higher than that of the dithizone complex because the heavy metal other than silver that has once formed a complex with the chelating agent does not react even after passing through the dithizone supporting part. It is estimated to be.

On the other hand, since silver has a stability constant of a complex formed with dithizone higher than that of a complex formed with a chelate, it is considered that silver reacts with dithizone to develop a color. The chelating agent is a chelate other than dithizone, and preferably includes EDTA, PDTA, and NTA. In the present invention, in the dithizone carrying part, dithizone is carried on the carrier of the carrying part, and replacement of the dithizone carrying part becomes easy,
Further, the color change of the dithizone carrier part due to the formation of the complex of dithizone and silver is large, and it is sufficient that the color change can be visually observed, and the detector can be simplified. When the carrier carrying dithizone is yellow or white, the color development of silver and dithizone can be observed more effectively.

In the present invention, it is preferable that the dithizone-carrying unit is exchanged every one detection. Further, the dithizone carrying unit is preferably replaced for each detection, but it can be used for multiple detections.
Also, regarding the reuse of silver, it is preferable that the Zison carrying unit can be replaced. Since dithizone has sufficient color development with 0.1 mg of silver, in order to check whether the silver concentration is 0.01 ppm or less, 100 ml of the waste liquid was passed through the dithizone-supporting part and the presence or absence of color development was observed. Is 0.001p
In order to check whether it is pm or less, flow 1000 ml and observe the presence or absence of color development.

In the silver detector of the present invention, due to gravity,
A liquid moving part due to a capillary phenomenon or an air pressure difference is preferable, and a silver detector that enables liquid moving based on such a natural law has a simple structure. Capillary phenomena include TLC (thin layer chromatography) and pH test paper, and air pressure differences include gas concentration detectors and burettes.

In addition, a chelating agent is added to a test solution for photographic processing, and a detection method in which a dithizone carrier is allowed to pass through is used to suppress color development with dithizone, a heavy metal other than silver (concealment of heavy metal by a chelating agent), and to develop silver color. You can get mine. In this case, it is preferable that the silver detector has only the dithizone-carrying unit in the liquid moving unit.

Further, the present invention will be described in detail. In the present invention, the carrier is a porous substance, a fibrous material,
Any substance that can carry dithizone can be used. Therefore, it may be either an inorganic substance or an organic substance (natural or synthetic). Examples of the porous carrier include a) sponge-like one, b) porous resin, and c) porous ceramic.

A) The sponge may be made of any material, but urethane, polyester, polyamide, polyethylene, melamine, vinyl chloride, polypropylene are preferred, and among them, urethane, polyethylene, cellulose, cellulose ester, modified polysaccharide, polyvinyl alcohol, modified polyvinyl alcohol. , Plastic foam and the like are preferable.

As the plastic foam, polyurethane foam, polystyrene foam, ABS foam, vinyl chloride resin foam, polyethylene foam,
Examples include polypropylene foam, phenol resin foam, urea resin foam, etc. [Synthetic polymer (Shunsuke Murahashi et al .; published by Asakura Shoten, reprinted at 50.3.30, Showa) No. 3
55 to 359].

The density of the sponge is 10 kg / m ^{3 to} 300
Preferably ^{Kg / m 3, 15Kg / m} 3 ~100Kg /
m ³ is more preferable. These sponges are commercially available as industrial foams and are available, for example, from Inoac Corporation, Kokugo. b) The porous resin is called a giant network resin,
Made from polystyrene, polyester, polyamide, etc. Some have an exchange group, such as an ion exchange resin. The pore size is distributed from 0.001 μm to 0.5 μm.

Amber light XAD is a typical example.
(Rohm and Haas Company) and Diaion HP (Mitsubishi Kasei). c) Various porous ceramics sold by Kyocera Corporation can be used as the porous ceramics. The compound may be alumina, zircon, cordierite, silicon carbide or the like, and may have a porous filter-like shape, a honeycomb structure or a pleated structure.

Other porous materials include Engineering Material Handbook (author Saichi Hatano 1982. Nikkan Kogyo Shinkaisha) No. 322.
Those described on the page and synthetic zeolites such as Munters Zeol manufactured by Tosoh Zeol Co., Ltd. can also be used. The fibrous material has various forms such as a thread form, a cloth form, a cotton form, and a mat form, depending on the processing conditions, but any form may be used. As the material, synthetic fibers such as polypropylene and polyester are preferable to natural fibers, and further, cellulose fibers, vinyl chloride polymer fibers, vinylon fibers, saran fibers, polyester fibers and the like are preferable.

Typical materials include Mitsubishi Diamond Marssorb (Mitsubishi Rayon Engineering Co., Ltd.) and Toughnel Oil Blotter (Mitsui Petrochemical Industry Co., Ltd.). What is preferably used as the carrier of the present invention is
It is a) and b) that the liquid can pass through the carrier. Further, the method for supporting dithizone is more preferably the synthetic fiber of a), because it uses a hydrophobic bond.

As a method for supporting dithizone of the present invention, it is necessary to firmly support dithizone and the carrier so that the dithizone does not flow out even when the test liquid comes into contact with the test solution. Therefore, as the mechanism of carrier, 1) adsorption by hydrophobic interaction, 2) adsorption by polar interaction (for example, hydrogen bond), and in some cases, dithizone and carrier each have 3) reaction group and react It may be carried by. However, 1) is most preferable in order to keep the cost low and to prevent dithizone from eluting into the aqueous phase when used in the aqueous phase. To adsorb dithizone to a carrier, dithizone is dissolved in an organic solvent, the solution is permeated into the carrier or the carrier is immersed in the solution, and then the organic solvent is evaporated from the carrier. Any organic solvent may be used as long as it can dissolve dithizone, but chloroform or carbon tetrachloride having a large solubility of dithizone is preferable.

To carry dithizone on a carrier, the following method is convenient. That is, 0.01 mmol / liter to 1 mmol / liter of an organic solvent solution of dithizone,
Preferably 0.1 mmol / liter to 100 mmol
Dip the carrier in 1 / liter and stir. After 5 minutes or more, the carrier is taken out from the solution and dried. Usually, by this operation, 0.01 mmol or more of dithizone is adsorbed per 1 g of the carrier, and the carrier becomes usable.

As a method for supporting the chelating agent of the present invention, a method in which the chelating agent is uniformly dispersed and released into the liquid to be treated when the test liquid comes into contact is preferable. For that purpose, there is a method in which a chelating agent is dispersed and carried on a carrier occupying the same volume as the test liquid, or a chelating agent is carried on an ion exchanger. The method is preferable in order that the chelating agent is promptly dissolved in the test liquid.

To prepare the chelating agent-supporting carrier of
An aqueous solution of a chelating agent saturated or at a concentration close to it may be uniformly permeated into the carrier and then dried. As the chelating agent of the present invention, the chelating agent described in Dautite reagent (Dotai Reagent, 10th edition, S.49, Dojin Pharmaceutical Institute) can be used. Specific examples of the water-soluble chelating agent that can be used in the present invention are shown below.

The following compounds are acids and salts (Li ⁺ , N
a ^+, K ^+, an NH ₄ ^+).

(1) Carboxylic acid type (abbreviation) CyDTA: cyclohexanediaminetetraacetic acid trans type DHEG: dihydroxyethylglycine DTPA: diethylenetriaminepentaacetic acid DPTA-OH: diaminopropanol tetraacetic acid EDAPDA: ethylenediaminediacetic acid dipropionic acid EDDA: ethienedidiene Amine diacetic acid EDDHA: Ethylenediamine diorthohydroxyphenylacetic acid EDDP: Ethylenediamine dipropionic acid EDTA-OH: Hydroxyethyl ethylenediamine triacetic acid GEDTA: Glycol ether diamine tetraacetic acid HIDA: Hydroxyethyliminodiacetic acid IDA: Iminodiacetic acid methyl-EDTA: Diamino Propane tetraacetic acid NTA: Nitrilotriacetic acid NTP: Nitrilotripropionic acid m-PHDTA: Metaph Nirenjiamin tetraacetate TTHA: triethylenetetraminehexaacetic acid m-XDTA: metaxylylene over diamine tetraacetic acid EDTA: ethylenediaminetetraacetic acid Ani hepcidin blue; Chromazurol S; full oxine;
Methyl thymol blue; methyl xylenol blue; circus syncresol red; stilbene fluor blue S; N, N-bis (2-hydroxyethyl) glycine

(2) Phosphonic acid-based, phosphoric acid-based ethylenediaminetetrakismethylenephosphonic acid nitrilotrimethylenephosphonic acid 1-hydroxyethylidene-1,1-diphosphonic acid 1,1-diphosphonoethane-2-carboxylic acid 2-phosphonobutane-1,2 , 4-Tricarboxylic acid 1-hydroxyethylidene-1,1-diphosphonic acid 1-hydroxy-1-phosphonopropane-1,2,3-
Tricarboxylic acid Catechol-3,5-diphosphonic acid Sodium pyrophosphate Sodium tetrapolyphosphate Sodium hexametaphosphate α-Alkylphosphonosuccinic acid 1-Hydroxyorgano-1,1-dicarboxylic acid 1-Aminoalkane-1,1-diphosphonic acid 2 -Phosphonobutane-1,2-dicarboxylic acid

(3) Hydroxyl group Alizarin complexone; Arsenazo-III; Berylone-II; Bispyrazolone; n-benzoyl-N-
Phenylhydroxylamine; Bromopyrogallol red; Eriochrome black T; 1- (1-hydroxy-2-naphthylazo) -6-nitro-2-naphthol-4-sulfonic acid calcein; calcein blue; calcyclome;
Chalcone; Calmagite; Carboxyarsenazo;
Chlorophosphonazo-III; chloranilic acid; chromotropic acid; dimethylsulfonazo-III; dihydroxyazobenzene; dinitrohydroxyazo-III; dinitrosulfonazo-III; 2-furyldioxime; glycine resole red; glyoxal-bis (2
-Hydroxyanil); naphthylazoxin; naphthylazoxin S; 2-hydroxy-1- (2-hydroxy-4-sulfo-)
1-naphthylazo) -3-naphthoic acid 2- (2-pyridylazo) chromotropic acid; 1-
(2-pyridylazo) 2-naphthol; 4- (2-pyridylazo) resorcinol; phenazo; pyrocatechol violet; Tyrone; acetylacetone;
Fluoryltrifluoroacetone; Hexafluoroacetylacetone; Pivaloyltrifluoroacetone;
Trifluoroacetylacetone; N, N-bis (2-hydroxyethyl) -2-aminoethanesulfonic acid; triethanolamine

(4) Nitrogen-based and sulfur-based acemates; bathocuproine; bathocuproine sulfonic acid; bathophenanthroline; bathophenanthroline sulfonic acid; bismuthiol-II; 3,3'-diaminobenzidine; diantipyril Methane; Monopyrazolone; Murexide; O-phenanthroline; Thioxine

[0032]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS An embodiment of the present invention will be described below with reference to the accompanying drawings. However, the present invention is not limited to this embodiment. FIG. 1 is a schematic diagram of a silver detector according to an embodiment of the present invention. 1A and 1B show a silver detector utilizing gravity, wherein FIG. 1A is a sectional view and FIG. 1B is a perspective view.

The silver detector shown in FIG. 1 (a) has a waste liquid storage portion 1
A flow pipe 2 which has a liquid and is capable of moving the liquid to the bottom of the waste liquid storage portion 1.
Is provided, and the chelate-carrying part 4, the dithizone-carrying part 5, and the cock 8 are respectively provided in the order in which the waste liquid passes from the waste liquid storage portion 1 side (upper part) of the flow pipe 2. Figure 1
The silver detector shown in (a) is for detecting silver by flowing the waste liquid into the flow pipe by using gravity. Since the liquid naturally falls, a device such as a pump for circulating the liquid is not required. It becomes a simple detector.

The shapes of the waste liquid storage portion 1 and the flow pipe 2 are not particularly limited, and the liquid can be stored in the waste liquid storage portion 1, and the flow pipe 2 moves by utilizing gravity to flow the waste liquid. It only has to pass the dithizone filled in the tube. Into the waste liquid storage portion 1, the waste liquid in which silver is collected from the photo-processed liquid is put, and the waste liquid is caused to flow through the flow pipe by controlling the flow rate of the cock 8, and the waste liquid is the chelate carrying part 4 and the dithizone carrying part 5 in this order. It passes through the carrying unit. A chelating agent is added to the chelate carrier 4 and a dithizone carrier 5
Each has dithizone.

The chelating agent is attached to a sponge-like material and dried, and dithizone is soaked in the sponge-like material and dried by blowing air. Moreover, the chelating agent is eluted by the passage of the liquid, and the dithizone remains fixed. The heavy liquid in the waste liquid forms a chelate complex when the waste liquid passes through the chelate-supporting part 4, and the liquid that has passed through the chelate-supporting part 4 passes through the dithizone-supporting part 5 to form a silver chelate complex. Only forms a color with dithizone.

Heavy metals other than silver react with dithizone to develop color similarly to silver, but the chelate-carrying part 4 is replaced with the dithizone-carrying part 5
The heavy metal other than silver that forms the chelate complex in the chelate-supporting portion passes through without reacting with dithizone, and only silver forms a complex with dithizone and develops a color by being provided in the upstream portion of. This means that for heavy metals other than silver, the stability constant of the complex with the chelating agent is higher than the stability constant of the complex of dithizone, while the stability constant of the complex of silver is the stability constant of the complex formed with dithizone. It is considered to be higher.

When the chelate-carrying section 4 and the dithizone-carrying section 5 are installed in the distribution pipe, the distance between the two carriers should be such that the color of the dithizone-carrying section can be confirmed well, especially within a diameter of 50 mm. A certain distance within the pipe (for example, 5 mm or more 20
It is preferable to set them apart (within 0 mm). When exchanging the chelate carrying part 4 and the dithizone carrying part 5 of the distribution pipe,
When exchanging used carriers, when exchanging carriers with different sensitivities due to changes in emission standards, or when collecting silver. As exchange standard,
It is preferable to replace it after each detection, and it may be used multiple times.

FIG. 2 is a schematic view of a silver detector which is another embodiment of the present invention. The silver detector shown in FIG. 2A is a detector that moves a liquid by utilizing a capillary phenomenon. The silver detector of this embodiment comprises a sponge 10 having a chelating agent-loaded layer 15 and a dithizone-loaded layer 14. When the sponge 10 is dipped in the photographic waste liquid storage portion 12, the waste liquid in the photographic waste liquid storage portion 12 moves by a capillary phenomenon. That is, the sponge 10 is capillarity due to the container 1
By sucking up the waste liquid put in 2, the waste liquid is moved to detect silver. Such a device of the present invention utilizing the capillary phenomenon does not require a device such as a pump for pumping the liquid, and is a simple detector.

The sponge 10 is provided with respective carrier portions so that the waste liquid can pass through the chelate carrier portion and the dithizone carrier portion in this order when the waste liquid moves. The setting of this carrier is to prevent the adverse effect of silver detection due to the reaction of heavy metals other than silver with dithizone to develop color. Heavy metal in the waste liquid forms a complex in the chelate-supporting portion, and when the waste liquid having the complex passes through the dithizone-supporting portion, only silver forms a complex with dithizone and develops a color. This allows the detection of silver.

In order to efficiently suck up the waste liquid, the upper part of the sponge 10 is made into a highly water-absorbing polymer, and the sponge 1
It is preferable that the volume is gradually increased from the portion in contact with the waste liquid of 0 to the upper portion. In the device of FIG. 2 (a) that utilizes the capillary phenomenon, the movement of the liquid is slow, so
A sufficient amount of silver color can be obtained without the need for a liquid reservoir to provide sufficient color formation due to the formation of a complex between dithizone and silver and without providing a means for controlling the flow rate.

In FIG. 2B, the sponge 10 of FIG.
An exploded view of is shown. The chelate-carrying part 15 and the dithizone-carrying part 14 provided in the sponge 10 are supported (impregnated in the sponge) with a chelating agent or dithizone in a state where they are separated from each other, and then they are bonded again. In order to bond the separated sponges, they are mechanically bonded without using an adhesive or the like.

The shape of the sponge 10 used in the present invention is not particularly limited, and it can be used if the liquid can be moved by the capillary phenomenon.

[0043]

Examples Example 1 White polyurethane (manufactured by INOAC, trade name: CF-17, density: about 30 Kg / m ³ , tensile strength:
A carrier was prepared by adsorbing dithizone on an open-cell sponge (0.8 <Kg / cm ² ) in the following manner. That is, 50 mg (0.2 mmol) of dithizone was dissolved in 500 ml of carbon tetrachloride, 0.5 g of sponge cut into 5 mm square was immersed and stirred in the solution, and after 5 minutes, the sponge was taken out,
It was blown dry. By this operation, the sponge that was white became green due to the adsorbed dithizone.

FIG. 1 shows five green sponges of 5 mm square.
One is installed at the bottom of the detector shown in (1) (however, the chelate carrying part is not installed), and the test liquid 2 shown below is provided there.
ml was poured and the color change was observed. A: Silver 1 ppm silver thiosulfate solution B: Add EDTA to the solution of A (36 as EDTA concentration)
Cu, Pb, and Zn are added to the C: B solution at 100 ppm each [CuSO ₄ .5H ₂ O and Pb (NO ₃ ) as metal salts.
₂ , using ZnSO ₄ · H ₂ O] D: Cu, Pb, and Zn solution of 100 ppm each (the metal salt used is the same as C) E: Add EDTA to the solution (36 as EDTA concentration)
0 ppm) As a result of the above, discoloration to light red color was recognized: A, B,
C and D, which did not discolor: E.

Usually, Cu, Pb and Zn discolor the dithizone, but the results show that these metals are hidden by EDTA and only the desired silver can be detected. That is, a remarkable effect of selective detection of silver was recognized.

Example 2 Similar to Example 1, upon adsorbing dithizone to the sponge, the background color of the sponge used was changed to white, yellow, orange, red, pink, gray, and light blue. Each of the 5 mm square sponges, which became green after the adsorption of dithizone, was placed one at the bottom of each of the seven detectors shown in FIG. 1 (however, the chelate carrying part was not provided), and silver 0.1
1 ml of a ppm silver thiosulfate solution was added. 0.1p
For pm and dilute silver, sponges with white and yellow backgrounds gave superior results in detecting discoloration than others, as shown below.

Sponge background color Discoloration is easy to see Discoloration is easy to see Time to color after discoloration White 5 minutes ○ Light red yellow 5 minutes ◎ Orange orange 6 minutes ○ Red red 6 minutes ○ Red pink 7 minutes ○ Red gray 7 minutes △ Gray red light blue 7 minutes △ Purple red Especially yellow sponge was easy to detect because it changed from green to its complementary orange color.

Example 3 A synthetic fiber mat (manufactured by Mitsubishi Rayon Engineering Co., Ltd., trade name: Mitsubishi Diamalth Sorb thickness about 8 mm) was cut into a width of 8 mm and a length of 10 cm, and 5 ml of a 10% aqueous solution of EDTA / 2Na was cut. Allow to soak evenly and then dry. A glass tube having an inner diameter of 7 mm and a length of 20 mm is vertically fixed, and 250 mg of the sponge having the dithizone used in Example 1 adsorbed therein is pressed down. On top of that, a mat in which the above-mentioned EDTA.2Na is dispersed is packed. Three detectors produced in this way were arranged, 10 ml of the test solution shown below was flown from the upper part of the tube, and the change in color of the sponge was observed. A: Silver thiosulfate solution of 0.5 ppm of silver B: Cu, Pb, Zn of 50 ppm each was added to the solution of A (the salt used was the same as in Example 1) C: Cu, Pb, Zn of each 50 ppm solution ( The salt used is the same as B) The results are shown below.

Light red discoloration was observed: A, B No discoloration: C From these results, the detector of the present invention was used to conceal Cu, Pb and Zn which interfere with the detection of silver, It can be seen that only silver can be detected. That is, a remarkable selective detection effect of silver is recognized.

[0050]

INDUSTRIAL APPLICABILITY According to the present invention, after collecting silver from a processed solution of a light-sensitive material and immediately before discarding the silver, residual silver in the silver-collected waste solution can be easily detected by a simple method. A detection device and a silver detection method using the detection device can be provided.

[Brief description of drawings]

FIG. 1 is a schematic diagram of a silver detector.

FIG. 2 is a perspective view of a silver detector.

[Explanation of symbols]

 1, 12 Waste liquid storage part 2 Distribution pipe 4 Chelate carrier part 5 Dithizone carrier part 8 Cock 10 Sponge 14 Dithizone carrier layer 15 Chelating agent carrier layer

Claims (8)

[Claims] 1. A silver detector having a photographic waste liquid storage part and having a dithizone carrier part capable of contacting the photographic waste liquid in the storage part. 2. A photographic waste liquid storage part, a flow rate adjusting means for adjusting a flow rate in the liquid transfer, and a liquid transfer part through which liquid flows out from the storage part, and a dithizone carrier part in the liquid transfer part. Is a silver detector that allows liquid to pass through. 3. A silver detector having a liquid moving part capable of moving the photographic waste liquid by capillarity upon contact with the photographic waste liquid, and having a dithizone-carrying part through which the liquid can pass. 4. A photographic waste liquid storage part, and a liquid transfer part capable of moving the photographic waste liquid from the storage part by using an air pressure difference, wherein the liquid can pass through a dithizone carrier part in the liquid transfer part. The silver detector provided. 5. The silver detector according to claim 1, wherein the dithizone carrying unit is replaceable. 6. The silver detector according to claim 1, wherein the carrier of the dithizone carrying part is yellow or white. 7. The chelate-carrying part is provided on the upstream side in the liquid-moving direction in the liquid-moving part, and the dithizone-carrying part is provided on the downstream side so that the liquid can pass therethrough. Silver detector. 8. A silver detection method, wherein a chelating agent is added to a waste liquid containing at least one of washing, rinsing, and stabilizing liquids for photographic processing, and the waste liquid is passed through a dithizone carrier to detect silver in the waste liquid. Method.