JPH08325767A - Washing method and washing device - Google Patents

Abstract

PURPOSE: To reuse a rinsing liquid by heating and evaporating waste rinsing liquid and separating the rinsing liquid from detergents, then subjecting the rinsing liquid to cooling and condensing and recovering the condensate at the time of subjecting metallic products contaminated with oil, etc., to degreasing and washing, then to a rinsing treatment to remove the detergents sticking thereto. CONSTITUTION: The metallic products 2 stuck with the machining oil, etc., are immersed into the detergents 22 in an immersion washing tank 21, where the oil, etc., sticking thereto are removed. The products are then successively moved from 31c toward 31a reverse from the flow of the rinsing liquid 32 by rinsing means 30 having the plural rinsing tanks 31a to 31c, by which the detergents sticking to the surfaces of the metallic products 2 are rinsed away. The rinsing liquid overflows from the rinsing tank 31a to 31c and is once stored in the storage tank 41 by a liquid drain pipe 35 and thereafter, the liquid is moved into a reduced pressure type heating vessel 42,where a silicone defoaming agent 61 is added to the liquid and the liquid is evaporated by heating with an attached heater 51. The concd. waste liquid as the residual liquid after the evaporation is discharged by a drain pipe 52. The vapor is cooled and condensed by a cooling pipe 53 in a condenser 43, by which the liquid is regenerated. The liquid is again returned to the rinsing tank 31a of the rinsing means 30 and is used as the rinsing liquid.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cleaning drainage regenerating method and a cleaning drainage regenerating apparatus using a cleaning agent and a rinsing liquid, and further to a cleaning method and a cleaning apparatus to which they are applied.

[0002]

2. Description of the Related Art Various kinds of parts such as metal parts, plated parts, painted parts, electronic parts, semiconductor parts, etc. are attached with various stains such as processing oil and dust in the manufacturing process and assembly process. To do. Conventionally, the cleaning of various parts having such stains has been generally performed with a fluorocarbon solvent, a chlorine solvent, or the like. However, since these CFC-based solvents and chlorine-based solvents contain chlorine, and it has become clear that compounds containing this chlorine destroy the ozone layer, the use of CFC-based solvents and chlorine-based solvents is restricted, and even if they are completely abolished. Correspondence will be taken. For this reason, the cleaning process is also under review.

As one of the alternative cleaning agents for the CFC-based solvent and the chlorine-based solvent as described above, an aqueous cleaning agent, that is, an aqueous solution of a saponifying agent, a surfactant or the like has been studied. In the case of water-based cleaning agents, unlike cleaning using organic solvents, a non-flammable cleaning system can be constructed, and depending on the choice of alkali or surfactant, it exhibits high degreasing power, so various cleaning methods can be performed. high. However, since rinsing with water is required, washing with a solvent or the like cannot avoid the problem of unnecessary wastewater treatment.

By the way, as a conventional wastewater treatment method,
Known methods include an activated sludge method, an activated carbon adsorption method, an ion exchange method, a membrane separation method, and the like, or a combination thereof. However, these conventional wastewater treatment methods have a problem that enormous equipment investment and complicated maintenance are required. Furthermore, all of the above wastewater treatment methods are BO
D, COD, n-hexane extract, pH, SS, etc. exhibiting high values, it is difficult to directly treat so-called high-load wastewater, and in such a case, more water than is required for rinsing is used. It must be diluted with and the load reduced before processing. This is a big problem because it is not possible to be an effective wastewater treatment means for cleaning wastewater under the current situation where it is difficult to take a large amount of dilution water and the total amount of wastewater is being regulated. There is. As described above, the conventional general wastewater treatment method cannot efficiently process the high-load washing wastewater at low cost.

In addition, although the fields of application are different, in the fields of treatment of concentrated wastewater such as washing wastewater after plating treatment or washing wastewater after pickling and concentration treatment of photographic processing wastewater, distillation treatment is required. Considered (Japanese Patent Laid-Open No. 50-12847)
Japanese Patent Laid-Open No. 3-229688). However, these distillation treatments are not required
Even if it is applied directly to regeneration, the cleaning effluent contains surfactants and the like, and the cleaning operation using the cleaning agent is usually continuous, and especially the effluent from the rinsing process is discharged in large amounts. Therefore, due to foaming and insufficient processing capacity,
Distillation cannot be virtually continuous. Therefore, in order to apply distillation to the continuous treatment of cleaning drainage, it is necessary to reduce the amount of drainage itself and to eliminate the factors that reduce the processing efficiency such as foaming. No method has been found for treating and regenerating the cleaning effluent that satisfies these conditions.

On the other hand, in the electric and electronic industries, high density mounting of circuit boards is being promoted along with miniaturization and high integration of elements. If you try to clean these substrates with a water-based cleaning agent, there is a great risk of causing leaks, Ag migration, poor drying of the connector part, etc., so that chlorine, such as alcohol, hydrocarbon-based solvents, silicone-based solvents, etc. It has been studied to use an organic solvent that does not contain the organic solvent or a solvent obtained by adding a surfactant or the like as the cleaning agent.

When such a solvent-based cleaning agent is used, the above-mentioned problems relating to cleaning and wastewater treatment can be solved, but the problems relating to the treatment and regeneration of the solvent, which has reached the limit of use, still remain. There is. Here, as the simplest treatment / regeneration method of the solvent-based cleaning agent, there is a so-called simple distillation method in which heating / condensation is performed under atmospheric pressure, but the solvent-based cleaning agent having flammability is heated to the boiling point. This is extremely dangerous. Further, even when using a solvent-based cleaning agent, since the rinsing liquid (solvent-based) is used in a relatively large amount, as in the case of using the water-based cleaning agent described above,
It is required to continuously process and regenerate the rinse effluent.

[0008]

As described above, a water-based cleaning agent and a non-chlorine-based solvent-based cleaning agent have been studied as alternative cleaning agents for CFC-based solvents and chlorine-based solvents. When it comes to practical use, treatment of cleaning wastewater is a problem, and regarding solvent-based cleaning agents, treatment and regeneration of cleaning agents and solvent-based rinsing solutions that have reached their limits of use have become a problem.

The present invention has been made in order to solve the above-mentioned problems, and it is stable and efficient in large quantities without diluting a high-load cleaning drainage containing a dirt component and a cleaning agent component. It is an object of the present invention to provide a cleaning drainage reclaiming method and a cleaning drainage reclaiming apparatus that enable treatment and regeneration. Another object of the present invention is to enable efficient treatment of cleaning drainage when using a water-based cleaning agent or a non-chlorine-based solvent-based cleaning agent as an alternative cleaning agent for CFC-based solvents or chlorine-based solvents. Another object of the present invention is to provide a cleaning method and a cleaning device that effectively utilize the rinse liquid.

[0010]

A first cleaning drainage regeneration method according to the present invention comprises a cleaning step for removing dirt components adhering to an object to be cleaned with a cleaning agent, and the cleaning agent adhering to the object to be cleaned. In regenerating the cleaning effluent discharged from at least one of the rinsing steps for removing the components by the rinsing solution, the cleaning effluent is subjected to vacuum distillation using a silicone antifoaming agent, and the resulting condensate is subjected to the rinsing step. It is characterized by circulating supply to. In addition, the second cleaning drainage regeneration method includes a cleaning step of removing a dirt component adhering to the object to be cleaned with a cleaning agent and a rinsing step of removing the cleaning agent component adhering to the object to be cleaned with a rinsing liquid. In regenerating the cleaning effluent discharged from at least one, at least one of the cleaning agent and the rinse liquid containing a silicone-based defoaming component is used, and the cleaning effluent is distilled under reduced pressure, and the resulting condensate is It is characterized by circulating supply to the rinsing process.

Further, in the third cleaning drainage regeneration method, a cleaning step for removing dirt components adhering to the object to be cleaned with a cleaning agent, and a rinse for removing the cleaning agent adhering to the object to be cleaned with a rinsing liquid. In regenerating the cleaning effluent discharged from at least one of the steps, the cleaning effluent is caused to flow down along a heated wall surface, and the cleaning effluent is distilled under reduced pressure while forming a thin film, whereby the cleaning is performed. It is characterized by regenerating drainage.

The cleaning and drainage regenerating apparatus of the present invention comprises a decompression container having a thin film forming section, a liquid storage section into which cleaning drainage is introduced at least, and a thin film from the liquid storage section along the wall surface of the thin film forming section. It is characterized by comprising a mechanism for heating and evaporating the cleaning effluent that flows down while forming the water under reduced pressure, and a mechanism for cooling and condensing the evaporated components to recover the regenerated liquid.

In the first cleaning method of the present invention, a cleaning step for removing dirt components adhering to an object to be cleaned by a cleaning tank containing a cleaning agent and a rinse liquid are contained to transfer the object to be cleaned. A multi-tank connection type rinsing tank connected so that the rinsing liquid is sequentially fed in the opposite direction, and a rinsing step for removing the cleaning agent component adhering to the object to be cleaned, the multi-tank connection type The cleaning wastewater discharged from the rinse tank located on the most downstream side of the rinse tank is distilled under reduced pressure using a silicone antifoaming agent, and the resulting condensate is circulated and supplied to the rinse tank located on the most upstream side. The rinsing step is performed.

In the second cleaning method, a cleaning tank containing a cleaning agent removes dirt components adhering to the object to be cleaned, and a rinsing liquid is contained to transfer the object to be cleaned. And a rinsing step of removing the cleaning agent component adhering to the object to be cleaned by a multi-tank connection type rinsing tank connected so that the rinsing liquid is sequentially sent in the opposite direction. While using at least one of the cleaning agent and the rinse liquid containing, the cleaning waste liquid discharged from the rinse tank located on the most downstream side of the multi-tank connection type rinse tank is distilled under reduced pressure, and the resulting condensate is on the most upstream side. It is characterized in that the rinsing step is performed while circulatingly supplying it to the rinsing tank located.

Further, in the third cleaning method, a cleaning step of removing a dirt component adhering to the object to be cleaned by a cleaning tank containing a cleaning agent and a rinsing liquid are accommodated, and the transfer direction of the object to be cleaned. And a rinsing step of removing the cleaning agent component adhering to the object to be cleaned by a multi-tank connection type rinsing tank connected so that the rinsing liquid is sequentially sent in the opposite direction, and the multi-tank connection rinsing The cleaning effluent discharged from the rinse tank located on the most downstream side of the tank is caused to flow down along the heated wall surface and distilled under reduced pressure while forming a thin film of the cleaning effluent. The rinsing step is performed while circulatingly supplying the rinsing tank located on the upstream side.

The first cleaning apparatus according to the present invention has a cleaning tank containing a cleaning agent, and contains cleaning means for removing dirt components adhering to an object to be cleaned by the cleaning agent and a rinsing liquid. It has a multi-tank connection type rinsing tank connected so that the rinse liquid is sequentially sent in a direction opposite to the transfer direction of the object to be cleaned, and the cleaning agent component adhering to the object to be cleaned is removed by the rinse liquid. A rinsing means and at least cleaning effluent discharged from the rinsing tank located on the most downstream side of the multi-tank rinsing tank are introduced, and a decompression heating mechanism for heating and evaporating the cleaning effluent under reduced pressure, and A cleaning waste liquid regenerating unit having a condensing mechanism for condensing vapor obtained by the reduced pressure heating mechanism, and a silicone antifoaming agent that suppresses foaming in the reduced pressure heating mechanism are supplied to the cleaning waste liquid or the rinse liquid. Antifoam And feeding means, a condensate obtained by the condensation mechanism is characterized by comprising a circulating system for supplying a rinsing tank located at the most upstream side of the multi-tank articulated rinse bath.

Further, the second cleaning device has a cleaning tank containing a cleaning agent, and a cleaning means for removing dirt components adhering to an object to be cleaned by the cleaning agent and a rinsing liquid are contained. Rinsing for removing the cleaning agent component adhering to the object to be cleaned by the rinsing liquid, having a multi-tank connection type rinsing tank connected so that the rinsing liquid is sequentially sent in a direction opposite to the direction of transferring the object to be cleaned. Means and a decompression heating mechanism for introducing at least cleaning effluent discharged from the rinsing tank located on the most downstream side of the multi-tank rinsing tank, heating and evaporating the cleaning effluent under reduced pressure, and the decompression A cleaning waste liquid regenerating unit having a condensing mechanism for condensing the vapor obtained by the heating mechanism, and the condensate obtained by the condensing mechanism are supplied to the rinse tank located on the most upstream side of the multi-tank connection type rinse tank. With a circulatory system, At least one of the serial detergent and rinse solutions is characterized in that it contains a silicone-based defoaming component.

Further, the third cleaning device has a cleaning tank containing a cleaning agent, and a cleaning means for removing dirt components adhering to the object to be cleaned by the cleaning agent and a rinsing liquid are contained, and Rinsing for removing the cleaning agent component adhering to the object to be cleaned by the rinsing liquid, having a multi-tank connection type rinsing tank connected so that the rinsing liquid is sequentially sent in a direction opposite to the direction of transferring the object to be cleaned. Means, a decompression container having a thin film forming part, a liquid storage part into which at least cleaning waste liquid discharged from the rinse tank located on the most downstream side of the multi-tank connection type rinse tank is introduced, and the liquid storage part A cleaning drain having a heating mechanism for heating and evaporating the cleaning drainage flowing down while forming a thin film along the wall surface of the thin film forming part under reduced pressure, and a condensing mechanism for cooling and condensing the evaporated component. Liquid regeneration means and the condensation The condensate obtained in the configuration, is characterized by comprising a circulating system for supplying a rinsing tank located at the most upstream side of the multi-tank articulated rinse bath.

[0019]

BEST MODE FOR CARRYING OUT THE INVENTION By using a multi-tank rinsing tank, the rinsing liquid is made to flow down in the direction opposite to the transfer direction of the object to be cleaned, so that the liquid can be replenished at about 1/10 to 1/100 of the conventional one. It is possible to maintain the cleanliness of the final rinse tank. However,
The cleaning waste liquid discharged has a high load and a high concentration. In the present invention, the high-load washing effluent containing the above-mentioned detergent component is treated and regenerated by vacuum distillation. Here, although the vacuum distillation is suitable for high-load, high-concentration drainage treatment and regeneration, when treating a cleaning drainage containing a detergent component such as a surfactant as in the present invention, A large amount of foaming occurs when simply distilled under reduced pressure. As a result, the stock solution is taken out, and the processing efficiency is significantly reduced.

Therefore, in the present invention, by using a silicone-based defoaming agent under reduced pressure, or by using a detergent or rinsing solution containing the silicone-based defoaming component, the cleaning containing the silicone-based defoaming component in advance is performed. The effluent is distilled under reduced pressure, or the cleaning effluent is caused to flow down along a heated wall surface to form a thin film of the cleaning effluent, which is then distilled under reduced pressure. By applying the cleaning drainage treatment / regeneration method as described above, it is possible to suppress foaming of the cleaning drainage containing a detergent component such as a surfactant without diluting the highly loaded cleaning drainage. Therefore, it becomes possible to process continuously and accurately and efficiently. In this way, it becomes possible to directly process the high-load cleaning drainage liquid, and thus a closed system can be constructed.

As described above, according to the present invention, when a water-based cleaning agent or a non-chlorine-based solvent-based cleaning agent is used as an alternative cleaning agent for a CFC-based solvent, a chlorine-based solvent, etc. Since various treatments can be performed and the rinse liquid can be effectively used, the cleaning cost can be reduced while maintaining the cleaning quality.

[0022]

Embodiments of the present invention will be described below with reference to the drawings.

FIG. 1 is a diagram schematically showing the construction of a cleaning apparatus of one embodiment to which the cleaning drainage regeneration method and cleaning method of the present invention are applied. The cleaning device 1 shown in FIG.
For example, the basket transport mechanism 10 is provided as the transport means of 1., and each step of the cleaning means 20 and the rinsing means 30 is sequentially arranged along the transport route of the basket transport mechanism 10. Further, the cleaning apparatus 1 has a cleaning drainage regenerating unit 40 that processes and recycles the cleaning drainage discharged from at least one of the cleaning unit 20 and the rinsing unit 30. An antifoaming agent supply means 60 is provided in association with the cleaning and drainage regeneration means 40.

The cleaning means 20 has an immersion cleaning tank 22 containing a cleaning agent 21.

The object to be cleaned 2 is immersed in the immersion cleaning tank 22 to remove the oil-based or water-based adhering material and dirt such as dust. The immersion cleaning tank 22 can use ultrasonic waves, shaking, mechanical stirring, and the like together, if necessary. The cleaning means 20 is used in combination with shower cleaning,
Alternatively, it is possible to use shower washing alone.
As the immersion cleaning tank in the cleaning means 20, a multi-tank connected cleaning tank can be used. In this case, the transport mechanism 10
It is preferable to adopt a structure in which the cleaning agent 21 sequentially overflows in the direction opposite to the transport route of (1).

The rinsing means 30 has a multi-tank rinsing tank 31. This multi-tank connection type rinsing tank 31 is designed so that the rinsing liquid 32 overflows sequentially in the direction opposite to the transfer route of the transfer mechanism 10, that is, from the third rinsing tank 31a to the second rinsing tank 31b, and also to the second rinsing tank.
The height of the partition wall 33 is adjusted so that the rinsing liquid 32 sequentially overflows from the rinsing tank 31b to the first rinsing tank 31c. An overflow pipe 34 is installed in the first rinse tank 31c located on the most downstream side of the liquid flow, and the cleaning drainage regeneration is performed via the rinse drainage pipe 35 connected to the overflow pipe 34. Means 4
The rinse liquid 32 is configured to be delivered to the 0 cleaning drainage storage tank 41.

The number of the multi-tank rinsing tanks 31 is not limited to three, and may be selected appropriately depending on the cleaning accuracy required for the object to be cleaned 2 and the degree of contamination of cleaning waste liquid. Good. When processing high-load cleaning drainage,
Running cost can be suppressed by setting a large number of rinsing tanks.

In the above-mentioned cleaning device 1, only the cleaning drainage from the rinsing means 30 is sent to the cleaning drainage regenerating means 40, but the immersion cleaning tank 22 of the cleaning means 20 is also used for cleaning. The drainage may be sent to the cleaning drainage regeneration means 40.

The cleaning drainage regenerating means 40 is used as a cleaning drainage storage tank 4.
1, a decompression type heating can 42, a condenser 43, a regenerant liquid storage tank 44 and the like. The cleaning drainage storage tank 41 and the decompression-type heating can 42 are connected via an automatic valve 46 that operates in conjunction with a liquid level sensor 45 installed in the decompression-type heating can 42. A steam pipe 47 is connected to the upper portion of the decompression-type heating can 42, and the decompression-type heating can 42 and the condenser 43 are connected by the steam piping 47. A regenerant liquid collecting pipe 48 is provided below the condenser 43, and the regenerant liquid collecting pipe 48 is a regenerant liquid storage tank 44.
It is connected to the. A decompression pump 49 is connected to the regenerant storage tank 44, and the decompression pump 49 brings the regenerant storage tank 44 to the decompression-type heating can 42 into a predetermined decompression state. When the liquid level in the decompression-type heating can 42 decreases, the automatic valve 46 opens, and the cleaning drainage 50 stored in the cleaning drainage storage tank 41 is heated by the decompression-type heating can 42 due to the suction force accompanying decompression in the decompression-type heating can 42. It is introduced into the can 42.

A heater 51 is provided around the depressurizing heating can 42.
Is installed. The heater 51 heats the cleaning waste liquid 50 introduced into the decompression-type heating can 42 under reduced pressure to vaporize the components to be recovered. A drain valve 52 is connected to the lower portion of the decompression-type heating can 42, and the concentrated waste liquid is discharged from here. The decompression-type heating can 42 preferably has a structure that prevents entrainment of droplets, and a demister, a baffle, or the like can be installed on the upper part of the heating can 42 if necessary. Further, a plurality of decompression type heating cans 42 can be installed in parallel according to the amount of treated waste liquid.

The steam generated by heating at a temperature lower than the atmospheric pressure is sent to the condenser 43 via the steam pipe 47. Inside the condenser 43, a cooling pipe 53 connected to a cooling water supply device (not shown) is installed. The vapor supplied into the condenser 43 is condensed by the cooling pipe 53, and the condensate is stored in the regenerant liquid storage tank 44 as the regenerator rinse liquid 54. In this way, in the regenerant storage tank 44,
Regenerated rinse 54 treated by distillation operation under reduced pressure
Is housed.

Further, a temperature sensor is installed at the top of the depressurization type heating can 42 or at the steam pipe 47 to observe the temperature change of the distillate steam to monitor the purity of the distillate (regenerated rinse 54). can do. In addition, the purity of the regeneration rinse liquid 54 is monitored by installing an electric conductivity meter (conductivity meter) or the like in the lower part of the condenser 43 or in the regeneration liquid storage tank 44 and observing the electric conductivity of the condensate liquid. be able to. These may be used alone or in combination to efficiently control the purity of the regenerated rinse liquid 54.

An antifoaming agent supplying means 60 is attached to the above-mentioned cleaning and drainage regenerating means 40. Defoaming agent supply means 60
Is a defoaming agent storage tank 6 containing a silicone-based defoaming agent 61.
Have two. A defoaming agent supply pipe 64 is connected to the defoaming agent storage tank 62 via an addition amount adjusting valve 63. The defoaming agent supply pipe 64 is inserted into the decompression-type heating can 42, and an appropriate amount of the silicone-based defoaming agent 61 is supplied into the decompression-type heating can 42 from the defoaming agent supply pipe 64. The addition of the silicone-based defoaming agent 61 is performed, for example, by the suction force that accompanies the reduced pressure in the reduced pressure heating can 42.

That is, the vacuum distillation of the cleaning waste liquid 50 in the vacuum heating can 42 described above is performed by the silicone-based defoaming agent 61.
Is added. By adding the silicone antifoaming agent 61, it is possible to continuously and efficiently perform vacuum distillation while suppressing foaming of the cleaning waste liquid containing a surfactant and the like.

By the drainage treatment regenerating means 40 described above,
The regenerated rinsing liquid 54 that has been subjected to the vacuum distillation treatment is regenerated liquor storage tank 4
4 is supplied to the third rinse tank 31a located on the most upstream side of the liquid flow of the multi-tank connection type rinse tank 31 by the circulation pump 71 serving as a circulation system via the circulation system pipe 72, and the rinse liquid 32 is supplied. Be reused as. In this manner, since the rinse liquid 32 is always treated and circulated, the cleanliness of the rinse liquid 32 is maintained without discharging the treated water to the outside of the system. It should be noted that the cleaning agent 21 can also be treated as necessary and can be prevented from being discharged to the outside of the system.

Next, a method of cleaning the object to be cleaned and a method of treating and regenerating the cleaning waste liquid by the cleaning apparatus 1 will be described.

The object to be cleaned 2 is first immersed in the immersion cleaning tank 22 to remove various stains such as oil-based and water-based adhered to the surface thereof. Examples of the cleaning agent 21 used in the immersion cleaning tank 22 include water-based cleaning agents, semi-water-based cleaning agents, solvent-based cleaning agents, and the like.
Various cleaning agents can be used. Examples of the water-based cleaning agent include aqueous solutions of inorganic acids, organic acids, alkalis, detergents containing a surfactant as a main component and their aqueous solutions, and those obtained by adding various additives to them. Examples of the solvent-based cleaning agent include silicone-based solvents, hydrocarbon-based solvents, perfluorocarbon-based solvents, terpene-based solvents, and the like, to which cleaning effective ingredients such as surfactants and alcohols and various additives are added. Further, it was washed with a composition containing a solvent as a main component, such as an alkylamine oxide-based solvent, a polyglycol-based solvent, a terpene-based solvent, a hydrocarbon-based solvent, and a cleaning agent containing these and a surfactant as components. After that, a semi-aqueous cleaning agent capable of rinsing the cleaning composition with water can also be used. The boiling point of the cleaning active ingredient or additive in these detergents is preferably higher than the boiling point of the ingredient recovered by vacuum distillation, and the boiling point of the contaminant to be washed is also the same.

When the general cleaning agent as described above is used, at least the cleaning drainage of the silicone antifoaming agent, which will be described in detail later, is treated from the antifoaming agent supplying means 60 by the cleaning drainage regenerating means 40. Add before. However, the above cleaning agent 21
The rinsing liquid 32 is not limited to this when a liquid containing a silicone defoaming component is used.

The silicone defoaming component is not particularly limited, but for example, the general formula: R ¹ _n SiO _{(4-n) / 2} (1) (wherein R ¹ is carbon The same or different monovalent groups selected from the substituted or unsubstituted monovalent hydrocarbon groups of the formulas 1 to 10 and polyoxyalkylene groups, and n has an average value of 1.9.
.About.2.2). Here, R ¹ is an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group or an octyl group, an alkenyl group such as a vinyl group or an allyl group, an aryl group such as a phenyl group or a tolyl group, and β-phenyl. Ethyl group,
an aralkyl group such as γ-phenylpropyl group, a group in which at least a part of hydrogen atoms bonded to carbon of these groups is substituted with a halogen atom, a cyano group, a hydroxyl group, a carboxyl group, a carbonyl group, an amino group, an alkoxy group, or the like, Examples thereof include polyoxyalkylene groups. Of these, a methyl group, a phenyl group and a polyoxyalkylene group are preferable. Also,
In addition to R ¹ , a hydrolyzable group such as a silicon-bonded hydroxyl group or an alkoxy group may be contained. The polyorganosiloxane represented by the formula (1) has an average value of n of 1.9 to 2.2.
And has a substantially linear or cyclic structure, but may partially have a branched structure.

Among the silicone-based defoaming components represented by the above formula (1), those particularly effective for water-based detergents include:

Embedded image A polyoxyalkylene group-containing polyorganosiloxane having at least one siloxane unit represented by Since such a polyoxyalkylene group-containing polyorganosiloxane has a defoaming action and shows an affinity for water, it also functions as a component for forming a stable aqueous dispersion or aqueous solution. It also has a function of penetrating the interface between the object to be cleaned and the dirt and peeling off the dirt. Therefore, the polyoxyalkylene group-containing polyorganosiloxane, water, a surfactant, and the like can form an aqueous detergent.

The polyoxyalkylene group of A in the above formula (2) is

Embedded image The monovalent group represented by is exemplified.

The siloxane forming the main skeleton of the polyoxyalkylene group-containing polyorganosiloxane is not particularly limited. The organic group bonded to the silicon atom of this siloxane is basically a methyl group, but as long as the effect is not impaired, it is a monovalent hydrocarbon group such as ethyl, propyl, butyl, or phenyl. Alternatively, it may contain a monovalent substituted hydrocarbon group such as a trifluoromethyl group. Further, the molecular weight and the molecular weight per one polyoxyalkylene group are not particularly limited. However,
Practically, the molecular weight per polyoxyalkylene group is
It is preferably about 100 to 5,000. The amount of the polyoxyalkylene group is not particularly limited, but it is 5 mol% based on all the organic groups bonded to the silicon atom of the polyorganosiloxane.
The above is more preferable from the viewpoint of system stability.

Specific examples of the detergent containing the polyoxyalkylene group-containing polyorganosiloxane as described above include the polyoxyalkylene group-containing polyorganosiloxane represented by the formula (2), a surfactant, and water. There are things. In addition, these three-component composition,

Embedded image A linear polydiorganosiloxane represented by,

[Chemical 4] You may mix | blend low molecular weight polyorganosiloxanes, such as cyclic polydiorganosiloxane represented by these. R ⁷ in the above formulas (4) and (5) is a substituted or unsubstituted monovalent organic group, for example, a methyl group, an ethyl group, a propyl group,
Examples include alkyl groups such as butyl groups, monovalent unsubstituted hydrocarbon groups such as phenyl groups, and monovalent substituted hydrocarbon groups such as trifluoromethyl groups. A methyl group is most preferred for maintenance and the like. Note that these low molecular weight polyorganosiloxanes are included in the polyorganosiloxane of the above formula (1), and have a defoaming function by themselves.

The composition ratio of each of the above components is not particularly limited, but the surfactant is 10 to 10 parts by weight with respect to 100 parts by weight of the polyoxyalkylene group-containing polyorganosiloxane.
It is preferable to mix in the range of 1000 parts by weight. The low molecular weight polyorganosiloxane is preferably added in an amount of 1000 parts by weight or less based on 100 parts by weight of the total amount of the surfactant and the polyoxyalkylene group-containing polyorganosiloxane. If the content of the surfactant is too small, the detergency will be weak, and if it is too large, the permeability will be weak. If the amount of the low molecular weight polyorganosiloxane is too large, it will be difficult to disperse in the system, and the stability as an aqueous composition will be reduced. The amount of water to be added is not particularly limited, but from the viewpoint of stability of the detergent, it is preferably 40% by weight or more in the entire composition.

As the above-mentioned surfactant, various kinds such as cationic type, anionic type, nonionic type, amphoteric type and composite type of these can be used. Also, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether,
Polyhydric alcohols such as diethylene glycol monobutyl ether and derivatives thereof, and

Embedded image It is represented by

[Chemical 6]

[Chemical 7] Polyoxyethylene-polyoxypropylene copolymers and the like, for example, can be used in the same manner as the surfactant.

However, considering the effect of the combination with the above polyoxyalkylene group-containing polyorganosiloxane, it is preferable to use any of anionic, nonionic and amphoteric surfactants, particularly anionic / nonionic surfactants. The synergistic effect on the detergency by the surfactant and the permeability by the low molecular weight polyorganosiloxane or the polyoxyalkylene group-containing polyorganosiloxane described above is obtained by using the surfactant of the combination of the above or the combination of the amphoteric system / nonionic system. Is obtained.

The low molecular weight polyorganosiloxane represented by the above formulas (4) and (5) functions as a silicone-based solvent which is one of the main components of solvent-based detergents. Therefore, even when a detergent containing a silicone solvent as a main component is used, distillation under reduced pressure can be performed without adding a silicone defoaming agent.

Since the cleaning agent 21 is attached to the surface of the object 2 to be cleaned which has been pulled up from the immersion cleaning tank 22 of the cleaning means 20, each rinsing tank 31c of the multi-tank rinsing tank 31 is
Immersion in the order of 31b and 31a is performed for rinsing and cleaning. As the rinsing liquid 32, water is used when the cleaning agent 21 is a water-based or semi-water-based cleaning agent, and in the case of a solvent-based cleaning agent, a base solvent thereof, such as a silicone-based solvent or a hydrocarbon-based solvent. Is used. These rinse liquids 32
It is processed and regenerated by the cleaning drainage regenerating means 40 described above.

In the cleaning apparatus 1 of this embodiment, a multi-tank connection type rinsing tank 31 in which three tanks are connected by overflow is used, and the rinsing liquid 32 is made to flow down in the direction opposite to the transfer direction of the object to be cleaned 2. ing. Here, the immersion cleaning tank 22 having a volume of 50,000 g and the multi-tank connection type rinsing tank 31 (each rinsing tank 31
A cleaning experiment (1 tact: 5 minutes) was performed by using 20 A4 substrates with stain components attached as cleaning target 2 using a, 31b, and 31c). An aqueous cleaning agent was used as the cleaning agent 21, and water was used as the rinsing liquid 32. Also, the amount of liquid brought in and out by the item to be cleaned 2 is 50 g,
The load values of BOD, COD, and n-hexane in the immersion cleaning tank 22 were set to 10000 mg / l. Under such conditions, the amount of new liquid (rinse liquid) added to the third rinse tank 31a was changed to perform cleaning, and the load state of each rinse tank 31c, 31b, 31a was measured.

As a result, each rinsing tank 31c, 31b, 31a when 800 g (9.6 l / hr) of new solution was replenished per tact
The load of was 6000 mg / l in the first rinse tank 31c, 360 mg / l in the second rinse tank 31b, and 19 mg / l in the third rinse tank 31a. The above value of 19 mg / l is close to city water, and even 360 mg / l is a sufficient level of cleanliness for general cleaning. That is, the rinsing liquid 32 is made to flow down in the direction opposite to the transfer direction of the object to be cleaned 2 so that
It is possible to maintain the cleanliness of the final rinsing tank 31a by replenishing about 1/100 of new solution.

In addition, a multi-tank rinsing tank (two tank type) having respective tank volumes of 42 liters and 90 liters was used,
A cleaning experiment was conducted by using 20 A4 substrates to which the flux adhered as the cleaning object 2 (flux adhesion amount: 5 g). The cleaning agent 21 is a solvent-based cleaning agent (FRW-17: trade name, manufactured by Toshiba Corporation) in which alcohol is added as a cleaning active ingredient to a silicone-based solvent, and the rinsing liquid 32 is a silicone-based solvent. (FRW-1: trade name, manufactured by Toshiba Corporation) was used. FIG. 2 shows the change in the concentration of the cleaning component (alcohol) in each rinse tank as a relationship with the number of times of cleaning. Also, 3
Fig. 3 shows the result when a tank-type multi-tank rinsing tank is used.
Shown in From these, by making the rinsing tank multi-tank type, the rinsing liquid is less contaminated in the rinsing tank located on the downstream side in the conveying direction of the object to be cleaned 2 and the rinsing liquid is increased as the number of rinsing tanks is increased. It can be seen that the condition decreases. Fig. 4 shows the results when the final rinse tank was replenished with a new solution at 2 kg / hr when a two-tank multi-tank rinsing tank was used. From Fig. 4, the control limit of the liquid is the alcohol concentration.
It can be seen that if the rinsing liquid circulation rate can be set to 2 kg / hr in the case of 20%, semipermanent cleaning is possible.

Further, under the same conditions as in the above-mentioned experimental example, when the number of the multi-tank coupled rinsing tanks is 1 using the solvent type cleaning agent FRW-17 and the solvent rinsing solution FRW-1 The number of cleanings for two tanks and three tanks were compared.
The results are shown in Tables 1 and 2. The results in Tables 1 and 2 show cases where the control limits of alcohol in the final rinse tank were 15% and 20%, respectively. Further, the column of the number of times of cleaning with the new liquid shows the number of times of cleaning when the cleaning agent and the rinse liquid are all new liquids. The column for the number of washings after liquid exchange shows that after the alcohol concentration in the final rinsing tank reaches the control limit, for example, in the case of the three-tank type, the rinsing liquid in the third rinsing tank is fed to the second rinsing tank, Two
The number of times of rinsing when the rinsing solution in the rinsing tank is transferred to the first rinsing tank and the third rinsing tank is replenished with a new solution is shown. The same is true for the two-tank type, and the results for the one-tank type are shown after the rinsing solution is simply replaced.

[0053]

[Table 1]

[Table 2] From Tables 1 and 2, it can be seen that the number of washings can be increased by increasing the number of rinsing baths, and the number of washings can be further increased by circulating the rinse liquid.

From the above-mentioned various experimental results, by using the multi-tank type rinsing tank 31, the rinsing liquid 32 is made to flow down in the direction opposite to the transfer direction of the object to be cleaned 2, and the rinsing liquid 32 is slightly smaller than the conventional one. It can be seen that the circulation can maintain the cleanliness of the final rinse tank 31a. Furthermore, it can be seen that the number of times of cleaning can be increased and the cleaning cost can be reduced. However, when the liquid circulation as described above is performed, the discharged cleaning waste liquid has a high load and a high concentration. If such a high-load cleaning drainage can be directly treated, a closed system can be constructed. However, the conventional high-load cleaning wastewater cannot be directly treated by the conventional wastewater treatment methods such as the activated carbon adsorption method, the ion exchange method and the membrane separation method.

Therefore, in the cleaning apparatus 1 of this embodiment, a vacuum distillation treatment is applied as the cleaning drainage regenerating means 40. Although the object of the present invention can be achieved if the pressure in the decompression-type heating can 42 is lower than the atmospheric pressure, it is preferable to reduce the pressure to about 5 to 200 Torr, although it depends on the treatment liquid. According to such a vacuum distillation process, it is possible to directly process and regenerate the high-load washing drainage liquid without diluting it, and since the heat treatment temperature can be set low, it is possible to improve the thermal efficiency. Becomes Also, the risk is reduced when treating a flammable solvent. The vacuum distillation not only enhances treatment efficiency and thermal efficiency, but also suppresses evaporation and thermal decomposition of various substances contained in the cleaning effluent and prevents scale from adhering to the piping system and the like.

However, since the treatment liquid is a cleaning effluent containing a surfactant and the like, foaming occurs simply by performing vacuum distillation, and continuous treatment cannot be performed at all. Foaming is more likely to occur in vacuum distillation than in atmospheric distillation, and a large amount of foaming occurs in vacuum distillation even for a treatment liquid in which foaming does not occur in atmospheric distillation. Further, addition of an antifoaming agent is effective for suppressing foaming in vacuum distillation, but continuous treatment, 30
It must be taken into consideration that it is used at a high temperature of up to about 100 ° C, and the pH of the treatment liquid ranges from strong acid to strong alkali. Therefore, in the cleaning apparatus 1 of this embodiment, the silicone antifoaming agent 61 is used during vacuum distillation.

As the above-mentioned silicone type defoaming agent 61, the polyorganosiloxane represented by the above-mentioned formula (1) is exemplified. Here, as a part of R ¹ in equation (1),
Containing a polyoxyalkylene group, i.e.
The polyoxyalkylene group-containing polyorganosiloxane having at least one siloxane unit represented by the formula (2) in one molecule can be used alone as an antifoaming agent.

Further, the general formula: R ² _n SiO _{(4-n) / 2} (7) (wherein R ² is the same or different and is a substituted or unsubstituted monovalent group having 1 to 10 carbon atoms). Hydrocarbon group, n has an average value of 1.9
When a general silicone oil such as a polyorganosiloxane represented by the formula (1 to 2.2) is used, it is preferably used together with an inorganic filler. Such fillers include fumed silica, wet silica, fused silica, alumina, titanium dioxide, talc, calcium carbonate, silicon nitride, silica-alumina, zeolite, ground quartz, aluminum hydroxide, polyorganosilsesquioxane powder. Examples thereof include powders such as silicone rubber powders, and those obtained by treating the surface of these powders with alcohol, silane, silazane, siloxane, or the like. Among these, silica powder is preferable because a good defoaming effect can be obtained.

The above-mentioned silicone oil is the main component of the defoaming agent and has a foam suppressing property. The inorganic filler improves the dispersibility of the silicone oil and also functions as an auxiliary component for defoaming and suppressing foam.

As the silicone antifoaming agent 61,
A polyoxyalkylene group-containing polyorganosiloxane having at least one siloxane unit represented by the above-mentioned formula (2) in the molecule, in a mixture of the silicone oil represented by the above formula (7) and the inorganic filler. It is preferable to blend the above. The polyoxyalkylene group-containing polyorganosiloxane contributes to the improvement of dispersibility and foam-suppressing property, and particularly to the improvement of dispersibility of silicone oil.

[0061] In addition to the components described above, the silicone-based defoaming agent 61 consists essentially of the (CH _{3) 3} SiO _1/2 units and SiO _{2 units, (CH 3) 3 Si O} 1/2 A siloxane resin having a ratio of units to SiO ₂ units in the range of 0.4 to 1.2,
It is also possible to incorporate a surfactant. The copolymerized siloxane resin improves the dispersibility of the silicone oil and exhibits a foam suppressing property. In addition, the surfactant is
It acts as an auxiliary component of the above-mentioned various components and contributes to improvement of dispersibility and formation of an emulsified state. As the surfactant, various types as described above can be used.

The mixing ratio of the above-mentioned various components is preferably 1 to 99% by weight of silicone oil, 0.1 to 22% by weight of inorganic filler, and 99% by weight or less of polyoxyalkylene group-containing polyorganosiloxane. In addition, the copolymerized siloxane resin is in the range of 33% by weight or less, and the surfactant is 22% by weight.
It is preferable to blend in the following range. If the compounding amount of silicone oil is less than 1% by weight, the fast-acting effect will decrease and
When it exceeds the weight%, it becomes difficult to prepare a composition having good dispersibility. The more preferable blending amount of silicone oil is in the range of 5 to 50% by weight. The amount of inorganic filler compounded
When it is less than 0.1% by weight, it becomes difficult to prepare a composition having good dispersibility, and when it exceeds 22% by weight, it becomes difficult to prepare a stable composition in an emulsified state, and in the system, Dispersibility deteriorates. The more preferable blending amount of the inorganic filler is in the range of 0.5 to 10% by weight. Also, the amount of polyoxyalkylene group-containing polyorganosiloxane blended
If it exceeds 99% by weight, the quick-acting property and the foam-suppressing property are deteriorated. Further, if the content of the copolymerized siloxane resin exceeds 33% by weight, it becomes difficult to prepare a stable composition in an emulsified state, and the dispersibility in the system deteriorates.

The silicone type defoaming agent 61 as described above is added so as to be 0.01 ppm or more with respect to the cleaning waste water to be treated. Addition amount of silicone type defoamer 61 is 0.01pp
If it is less than m, a sufficient effect cannot be obtained. The more preferable amount of the silicone type defoaming agent 61 added is in the range of 0.1 to 10000 ppm, and more preferably 1 to 1000 ppm. The silicone antifoaming agent 61 may be added continuously or intermittently within the range of the above addition amount depending on the treatment amount. In addition, the cleaning device 1 of this embodiment
Then, when the cleaning wastewater 50 is supplied into the decompression-type heating can 42, at the same time, the silicone-based defoaming agent 6 is introduced into the decompression-type heating can 42.
1 was added, but the silicone-based defoaming agent 6
1 may be added before the distillation under reduced pressure. For example,
When foaming occurs in the decompression-type heating can 42, the silicone-based defoaming agent 61 may be sprinkled in the decompression-type heating can 42. The silicone antifoaming agent 61 may be supplied into the cleaning drainage storage tank 41. Furthermore, the silicone-based defoaming agent 61 may be applied to the demister, baffle, etc. of the strip 42 of the depressurized heating can.

When the cleaning agent 21 or the rinse liquid 32 containing the silicone type defoaming component as described above is used, the vacuum distillation can be carried out without adding the silicone type defoaming agent 61. It is more preferable to use the silicone antifoaming agent 61 in combination.

Silicone defoamer 61 as described above
By using (or a silicone-based defoaming component), it is possible to effectively suppress foaming during vacuum distillation of a cleaning effluent containing a cleaning component such as a surfactant.
Therefore, it is possible to directly and accurately perform the vacuum distillation treatment of the cleaning drainage 50 having a wide range of pH from a strong acid to a strong alkali under a high load without performing dilution or the like.

As described above, according to the cleaning apparatus 1 having the above-mentioned configuration, the rinsing liquid 32 is caused to flow down in the direction opposite to the transfer direction of the article to be cleaned 2 by using the multi-tank rinsing tank 31. It is possible to reduce the usage amount (circulation amount) of the rinse liquid 32. As a result, the discharged cleaning effluent 50 has a high concentration and a high load, but the cleaning effluent regeneration means 4 to which the vacuum distillation using a silicone-based defoaming agent or a defoaming component is applied is applied.
Since it has 0, the cleaning drainage liquid 50 as described above is
It can be directly processed and regenerated. Therefore, it is possible to maintain the cleanliness of the rinsing liquid after the rinsing liquid is circulated, and it is possible to perform the cleaning and rinsing under such a condition, so that the cost is much lower than that of the conventional method. Advanced cleaning can be performed with. In the conventional drainage treatment method, it was impossible to perform drainage treatment in such a closed system. Next, a specific example of a method for cleaning the object to be cleaned 2 and a method for treating cleaning drainage using the cleaning apparatus 1 having the above configuration will be described. First, a production example of the silicone-based defoaming agent used in the following examples will be described. (Production Example 1 of silicone antifoaming agent) A trimethylsilyl group end-capped dimethyl silicone oil (viscosity at 25 ° C: 50 cSt) was added to a 3-neck flask with a capacity of 1000 cc equipped with a stirrer, a thermometer, a nitrogen purge and a dropping funnel. g and silica powder (Cyroid 266 (trade name, manufactured by Fuji Davison)) 1.
5 g was added, and the mixture was heated with stirring at a temperature of 160 ° C. for 4 hours. After cooling to room temperature, (CH ₃ ) ₃ SiO _1/2 / SiO ₂
8 g of a copolymer ((CH ₃ ) ₃ Si O _1/2 / SiO ₂ = 0.4),

Embedded image 70 g of polyoxyethylene-modified silicone represented by
Polyoxyethylene (20 mol addition) sorbitan monooleate (5 g) was added, and the mixture was uniformly dispersed using a homomixer. Thus, a viscous pale yellow silicone antifoam composition A-1 was obtained.

(Production Example 2 of Silicone Defoamer) Capacity equipped with stirrer, thermometer, nitrogen purge and dropping funnel
In a 1000 cc 3-neck flask, 15 g of trimethylsilyl group-blocked dimethyl silicone oil (viscosity at 25 ° C: 50 cSt)
And dimethylsilyl group end-blocked dimethyl silicone oil (viscosity at 25 ° C .: 2000 cSt) 15 g, and silica powder Syloid 266 (trade name, manufactured by Fuji Davison) 1.6 g,
Heated at a temperature of 160 ° C. for 4 hours with stirring. After cooling to 60 ℃, 2 g of polyoxyethylene (5 mol addition) nonylphenyl ether and polyoxyethylene (20 mol addition)
Stearyl ether (1 g) was added, and the mixture was stirred at 60 ° C for 10 minutes. Then, 65.4 g of water adjusted to 60 ° C. was added, and the mixture was cooled to 30 ° C. while continuing stirring. This was emulsified with a colloid mill (mill interval: 30 mil) to obtain a silicone antifoam composition A-2.

(Production Examples 3 to 5 of Silicone Defoamer) Silicone defoamer compositions A-3 to A- whose compositions are shown in Table 3 in the same manner as in Production Example 1 or Production Example 2 described above.
Got 5

[Table 3] Example 1 As cleaning agent 21, monoethanolamine myristic acid
An aqueous cleaning agent comprising an aqueous solution containing 20 parts by weight of a cleaning composition comprising 10 parts by weight, 5 parts by weight of polyoxyethylene lauryl ether, 10 parts by weight of sodium silicate, and 75 parts by weight of city water is used as a rinse liquid 32. Using, press oil 8g
The shadow mask made of amber, which remains in No. 3, was washed using the above washing apparatus 1 (the number of rinsing baths = 3). As the silicone-based defoaming agent 61, those according to Production Examples 1 to 5 shown in Table 3 were used, respectively, and 200% of the active ingredient was used for the cleaning drainage.
It was added to be ppm. Circulation amount from the regenerant liquid storage tank 44 to the third rinse tank 31a of the multi-tank connected rinse tank 31,
That is, the vacuum distillation treatment amount of the cleaning effluent is 2 liters / hr.
Set to. In addition, the vacuum distillation conditions for the cleaning effluent are:
The temperature inside the heating can was 25 to 30 ° C. at 25 Torr.

After operating for 200 hours under the above conditions, the pH, BOD, COD, and n- of the cleaning effluent (sampled from the cleaning effluent storage tank 41) and the regenerated rinse water (sampled from the regenerated solution storage tank 44), respectively. The amount of hexane extracted substance and SS were measured. The results are shown in Table 4.

Comparative Example 1 Example 1 above except that no silicone antifoam was used.
A washing test was conducted under the same conditions as in Example 1, and the pH, BOD, COD, amount of n-hexane extract substance, and SS of washing drainage and regenerated rinse water were measured. The results are also shown in Table 4.

Comparative Example 2 The same drainage treatment as in Example 1 was carried out by applying the drainage treatment using both ultrafiltration, activated carbon adsorption and ion exchange, and then the washing drainage was performed. The water quality of the regenerated rinse water was measured. The results are also shown in Table 4. In the drainage treatment according to Comparative Example 2, if the rinse drainage is treated as it is, it will be clogged in a short time and it will be impossible to process it. Therefore, the rinse drainage is diluted about 5 times with city water. Processed. The measurement result of the cleaning drainage is the value after dilution. The details of the drainage treatment are as follows.
Ultrafiltration is a polyolefin-based filtration membrane (removal rate: oil content
= 100%, surfactant = 0%). Activated carbon adsorption was performed under the conditions of a particle size of 0.9 mm, a filling amount of 54 liters, and a sv0.2 / hr. Ion exchange was performed using a mixed bed cartridge (25 liters x 2) of a strongly acidic resin and a strongly basic resin.

[0072]

[Table 4] As is clear from Table 4, according to the method of the present invention, it is possible to treat and recycle a high-load, high-concentration cleaning wastewater with high precision and efficiency, and the silicone antifoaming agent can withstand continuous treatment. I understand. The cleaning quality was also good. On the other hand, in Comparative Example 1 (without using the defoaming agent), a large amount of foaming occurred during distillation under reduced pressure, and the treatment effluent was mixed into the condensate due to this foaming, so that the water quality of the regenerated rinse solution was improved. It has deteriorated significantly. Further, in Comparative Example 2, it was not possible to sufficiently process the cleaning drainage, even though it was diluted with city water. In addition, the water quality of general city water is pH = 6.9,
BOD = 0.8 mg / l, COD = 0.7 mg / l, SS = (not detected),
n-hexane extract amount = (not detected).

Comparative Example 3 The shadow mask was washed in the same manner as in Example 1 while the cleaning waste liquid was distilled under normal pressure. However, the atmospheric distillation treatment was performed without using an antifoaming agent. Distillation conditions are as follows: the temperature inside the heating can is 135 ° C, and the amount of distillation is 0.8 liter / h.
It was r. After performing the above-mentioned cleaning and drainage, COD _{1 of the} cleaning drainage sampled from the cleaning drainage storage tank,
COD of regenerated rinse water sampled from regenerant tank
₂ and the COD residual rate (COD ₂ / COD ₁ × 100
(%)) Was calculated. As a result, the COD residual rate was 1.9%.

Although the COD removal efficiency (other water quality measurement items show a correlation with the COD value) is not sufficient,
Since the distillation is carried out under normal pressure, the treated effluent was not mixed in a large amount with the regeneration liquid due to foaming as in Comparative Example 1, for example. However, due to the small amount of processing,
It was confirmed that the water quality of the third rinse tank deteriorated with time and could not be used continuously. Further, since the raw water heating temperature reaches 135 ° C., the raw water is easily deteriorated by heating and decomposed, and soap scum (soap dregs) and the like adhere to the can wall. To increase the processing capacity,
If the heating temperature is further raised, the above-mentioned problem becomes more serious, and it becomes impossible to continuously use it.

Example 2 As the cleaning agent 21, 10 parts by weight of sodium myristate,
10 parts by weight of polyoxyethylene nonyl phenyl ether,
A die containing 5 g of a sodium silicate salt and 75 parts by weight of city water as an aqueous cleaning agent containing an aqueous solution containing 20% by weight of a cleaning composition. The cast gear was washed using the same washing device as the washing device 1 (the number of rinsing baths = 2). As the silicone-based defoaming agent 61, Production Examples 1 to 1 shown in Table 3
No. 5 was used, and the active ingredient was added to the cleaning effluent so as to be 200 ppm. Distillation throughput is 5
Set to l / hr. The vacuum distillation conditions of the cleaning waste liquid were a vacuum degree of 150 Torr and a heating can internal temperature of 75 ° C.

When 500 gears were washed under the above conditions, the COD _{1 of the} cleaning drainage sampled from the cleaning drainage storage tank and the COD _{2 of the} recycled rinse water sampled from the regeneration liquid storage tank were used to determine the COD residual rate. (COD ₂ /
COD ₁ × 100 (%)) was determined. The results are shown in Table 5. Table 5 also shows the COD reduction rate in Example 1.

Example 3 As the cleaning agent 21, 5 parts by weight of sodium myristate,
As a rinse liquid 32, an aqueous cleaning agent comprising an aqueous solution containing 10% by weight of a cleaning composition comprising 5 parts by weight of sodium gluconate, 5 parts by weight of sodium hydroxide, 20 parts by weight of sodium silicate, and 65 parts by weight of city water. A 42 alloy lead frame in which 1 g of punching oil was transferred and remained using water was washed using the above-mentioned washing device 1 (the number of rinsing baths = 3). As the silicone-based defoaming agent 61, Production Examples 1 to 1 shown in Table 3
No. 5 was used, and the active ingredient was added to the cleaning effluent so as to be 200 ppm. Distillation throughput is 10
Set to l / hr. In addition, the vacuum distillation conditions of the cleaning effluent were such that the degree of vacuum was 40 Torr and the temperature inside the heating can was 50 ° C.

Then, after washing 50000 lead frames under the above conditions, COD was performed in the same manner as in Example 2.
The residual rate was calculated. The results are shown in Table 5.

Comparative Examples 4 and 5 Examples 2 and 3 except that the silicone antifoaming agent was not used.
After performing cleaning and drainage treatment in the same manner as above, the COD residual rate was determined in the same manner as in Example 2. The results are shown in Table 5 including the COD residual rate according to Comparative Example 1.
Shown in

Comparative Examples 6 to 8 Washing and drainage treatments were carried out in the same manner as in Examples 1, 2 and 3 except that various antifoaming agents (other than silicone type) shown in Table 5 were used. COD as in Example 2
The residual rate was calculated for each. The results are shown in Table 5.

Defoaming agents other than silicone-based antifoaming agents were added in an amount necessary for exhibiting a foaming prevention degree of 50% or more with respect to cleaning drainage. The degree of foaming prevention is obtained from the following formula. Anti-frothing degree = a _{((t s) 0 -t s} ) / (t s) 0 ( wherein, t _s is the average life span of the end 1ml bubbles when adding defoamer (sec), (t _s ) ₀ is 1 when defoamer is not added
Shows the average life (sec) of the foam powder in ml)

[Table 5] As is clear from Table 5, according to the method of the present invention, a high-load, high-concentration cleaning drainage liquid can be continuously treated (Example 1) at high temperature (Example 2) and efficiently regenerated. It can be seen that it is possible to cope with high pH (Example 3) cleaning drainage as well. The cleaning quality was also good.

On the other hand, when antifoaming agents other than the silicone type were used (Comparative Examples 6 to 8), continuous distillation (distillation time 2.5 hours: Comparative Example 6) and high temperature distillation (75 ° C .: Comparative Example 7), due to the high pH drainage (Comparative Example 8), most of the defoaming agents lost their effect during the distillation process, and the treatment efficiency was low due to entrainment due to foaming.

Example 4 First, as the cleaning agent 21,

[Chemical 9] 5 parts by weight of polyoxyethylene-modified silicone represented by, 10 parts by weight of monoethanolamine stearate, 10 parts by weight of sodium silicate, and 75 parts by weight of city water from an aqueous solution containing 20% by weight of a cleaning composition. An aqueous cleaning agent was prepared.

An Amber shadow mask was washed under the same conditions as in Example 1 except that the above water-based cleaning agent was used and a silicone-based defoaming agent was not used. Then, after cleaning for 200 hours under the above conditions, COD _{1 of the} cleaning drainage sampled from the cleaning drainage storage tank and COD _{2 of the} recycled rinse water sampled from the regeneration liquid storage tank
Then, the COD residual rate was obtained. Table 6 shows the results.

Example 5 Under the same conditions as in Example 4 (water-based detergent having the same composition), except that the same silicone-based defoaming agent as in Example 1 was used,
The Amber shadow mask was washed. Then, after washing for 200 hours under the above conditions, the COD residual rate was obtained. The results are shown in Table 6.

Example 6 First, as the cleaning agent 21,

[Chemical 10] A cleaning composition comprising 10 parts by weight of polyoxyethylene-modified silicone represented by, 10 parts by weight of sodium myristate, 5 parts by weight of sodium silicate, and 75 parts by weight of city water.
An aqueous detergent containing an aqueous solution containing 20% by weight was prepared.

The die-cast gear was washed under the same conditions as in Example 2 except that the above water-based detergent was used and that the silicone antifoaming agent was not used. Then, after cleaning 500 gears under the above conditions, the COD residual rate was obtained. The results are shown in Table 6.

Example 7 Under the same conditions as in Example 6 (water-based detergent having the same composition), except that the same silicone antifoaming agent as in Example 2 was used,
The die-cast gear was washed. Then, after cleaning 500 gears under the above conditions, the COD residual rate was obtained. The results are shown in Table 6.

Example 8 First, as the cleaning agent 21,

[Chemical 11] A cleaning composition comprising 5 parts by weight of a polyoxyethylene-modified silicone represented by, 5 parts by weight of sodium myristate, 20 parts by weight of sodium silicate, and 70 parts by weight of city water.
An aqueous detergent containing an aqueous solution containing 10% by weight was prepared.

The 42 alloy lead frame was cleaned under the same conditions as in Example 3 except that the above water-based cleaning agent was used and that the silicone antifoaming agent was not used. Then, the COD residual rate was obtained when the 50,000 lead frames were washed under the above conditions. The results are shown in Table 6.

Example 9 Under the same conditions as in Example 8 (water-based detergent having the same composition), except that the same silicone-based defoaming agent as in Example 3 was used,
42 The lead frame made of alloy was cleaned. Then, after cleaning 50,000 lead frames under the above conditions, the COD residual rate was obtained. The results are shown in Table 6.

[0092]

[Table 6] Next, another embodiment of the cleaning drainage regeneration method of the present invention and the cleaning drainage regeneration apparatus to which the method is applied will be described with reference to the drawings.

FIG. 5 is a diagram schematically showing the construction of a cleaning and drainage regenerating apparatus of an embodiment to which the cleaning and drainage regenerating method of the present invention is applied. A cleaning drainage regenerating apparatus 101 shown in the same drawing has a cleaning drainage storage tank 110 that temporarily stores the cleaning drainage, a cleaning drainage heating unit 120 that heats and evaporates the cleaning drainage under reduced pressure, and condenses the obtained vapor. It mainly comprises a condenser 130 for collecting the regenerated liquid.

A drainage raw water supply pipe 111 connected to a cleaning tank or a rinsing tank of a cleaning device (not shown) is inserted in the cleaning drainage storage tank 110, and the cleaning drainage is continuously or intermittently supplied. A is supplied. In addition, the cleaning drainage storage tank 11
0 and the decompression container 121 of the cleaning drainage heating unit 120 are connected via a cleaning drainage supply pipe 114 in which an automatic valve 113 interlocking with a liquid level gauge 112 installed in the decompression container 121 is inserted. There is. The cleaning drainage heating unit 120 has the decompression container 121 as described above. This decompression container 1
At the center of 21, a thin film forming pipe 122 is erected as a thin film forming portion. The number of the thin film forming pipes 122 is set according to the amount of cleaning drainage to be processed. A heat medium 123 such as water or silicone oil is arranged around the thin film forming pipe 122.
A heater 124 is installed as a heating mechanism on the outer peripheral side of the decompression container 121 so as to surround the. The thin film forming pipe 122 is heated by the heater 124 via the heating medium 123.

On the upper side of the thin film forming pipe 122, there is provided a liquid storage section 125 having its upper end projectingly arranged. The cleaning drainage supply pipe 114 described above is opened toward the liquid reservoir 125. The processing liquid B once stored in the liquid storage portion 125 overflows from the liquid storage portion 125 as shown in FIG.
While forming the inner wall surface 122a of the thin film forming pipe 122
It flows down and flows down. At that time, the treatment liquid B is heated in a thin film state under reduced pressure, and the components to be recovered are vaporized. The evaporation residual liquid D is stored in the evaporation residual liquid storage part 121 a below the decompression container 121. Evaporation residual liquid storage section 121
In a, a liquid circulation pipe 1 in which a circulation pump 126 is inserted
27 is connected. The other end of the liquid circulation pipe 127 is opened toward the liquid reservoir 125. As a result, the cleaning waste liquid is circulated and continuously heated.

A steam recovery pipe 131 is connected to the upper portion of the decompression container 121, and the steam E generated by heating is sent to the condenser 130 through the steam recovery pipe 131. In addition, the drain pipe 1 is provided below the decompression container 121.
28 is connected.

As described above, the thin film C of the processing liquid B is formed by causing the processing liquid B stored in the liquid storage portion 125 to overflow and flow down along the inner wall surface 122a of the thin film forming pipe 122. . Thin film forming pipe 12
In order to uniformly form the thin film C on the inner wall surface 122a of the second container 2, the treatment liquid B in the liquid storage portion 125 is preferably kept in a stationary state. Therefore, for example, as shown in FIG. 7, a cleaning drainage supply pipe 114 and a liquid circulation pipe 127,
It is preferable that a shielding plate 129 be provided between the thin film forming pipe 122 and the thin film forming pipe 122 so that the liquid flow is isolated so as not to directly affect the thin film forming pipe 122. Further, as shown in FIG. 8, it is also effective to dispose the cleaning drainage supply pipe 114 and the liquid discharge parts 114 a and 127 a of the liquid circulation pipe 127 below the liquid storage part 125.

By the way, in forming the thin film C of the treatment liquid B, ordinary liquids may aggregate due to their respective aggregating forces, which may make it difficult to form a uniform film on the surface of glass or stainless material, for example. Therefore, in order to obtain an effective evaporation area, a vast heat transfer surface is required, and an increase in the size of the device cannot be avoided. Here, (a) a method of forcibly forming a thin film by using a blade or wiper, or (b) a method of increasing the film thickness to prevent agglomeration can be considered, but the method of (a) drives Problems such as in the maintenance of the section are likely to occur, and the advantage of thin film distillation is largely sacrificed by the method (b).

To such a point, the surface tension of the liquid is
When it is 35 dyn / cm or less, it becomes possible to easily form a thin film on the surface of, for example, glass or a stainless material without using a forcing means. The cleaning and drainage regenerating apparatus of this embodiment utilizes such a property of a liquid having a surface tension of 35 dyn / cm or less to uniformly form a thin film of the treatment liquid B. The surface tension of the cleaning waste liquid is more preferably 30 dyn / cm or less. Since the cleaning agent is generally designed so that the surface tension of the liquid becomes low, thin film distillation can be applied.

Here, examples of the liquid having a surface tension of 35 dyn / cm or less include aromatic hydrocarbons such as benzene, toluene and xylene, linear hydrocarbons such as heptane, hexane and dodecane, methanol, ethanol and isopropanol. Alcohols, acetone, ketones such as methyl ethyl ketone, esters such as methyl acetate and ethyl acetate, ethers such as ethyl ether and dioxane, polyhydric alcohols such as diethylene glycol monobutyl ether and their derivatives, d-limonene, d-pinene Examples include terpenes such as pile oil, silicones, aqueous solutions of fluorochemical surfactants, polyorganosiloxanes, perfluorocarbon compounds, hydrofluorocarbon compounds, and compositions containing these. That is, any of the water-based cleaning agent, the semi-water-based cleaning agent, the solvent-based cleaning agent, and the like exemplified in the above-mentioned examples can be applied. Further, thin-film distillation can be applied to solvent-based rinsing liquid and rinsing water containing a cleaning agent component.

Further, the upper end surface 12 of the thin film forming pipe 122
Although 2b may be flat as shown in FIG. 9, when the pipe upper end surface 122b is flat, the liquid surface rises due to the surface tension of the liquid, and depending on the state of the end face and the type of liquid,
There is a risk that the flow of the liquid will be non-uniform and that the formation of the thin film will be defective. In such a case, as shown in FIG. 10, it is effective to make at least a part of the upper end surface 122b of the thin film forming pipe 122 a curved surface. By forming the pipe upper end surface 122b into a curved shape, the surface tension of the liquid is apparently relaxed, and the thin film C can be formed more uniformly. In this case, the upper end surface of the thin film forming pipe 122 may have an R shape on the entire end surface, or may have a shape in which the top is formed as a smooth surface and slopes are provided on both sides thereof. Further, as shown in FIG. 11, the thin film forming pipe 1
It is also effective to form a notch 122c on the upper end surface 122b of 22.

Further, the material of the thin film forming pipe 122 is
It is preferably selected in consideration of the wettability with the cleaning waste liquid and the thermal conductivity. The cleaning effluent to be treated can basically be treated if its surface tension is 35 dyn / cm or less. However, depending on the material of the pipe, the wettability with the cleaning drainage may be low, and when the pipe 122 made of such a material is used, it becomes impossible to form a good thin film C, which leads to a decrease in evaporation efficiency. Becomes Therefore, as the material of the thin film forming pipe 122, it is preferable to use a material having a high wettability with the cleaning drainage and a high thermal conductivity so that heat can be sufficiently transmitted to the cleaning drainage. . Specifically, a metal pipe or a ceramic pipe is preferable. The shape of the thin film forming pipe 122 is not limited to the circular tube shape, and may be any shape as long as the inner wall surface is curved so that the thin film C is uniformly formed. Also, the thin film C
The liquid supply amount (circulation amount and new cleaning waste liquid supply amount) has a great influence on the forming ability of the liquid, but this point will be described later.

The condensing unit 130 has a condensing tank 132 to which the other end of the vapor recovery pipe 131 is connected. Inside the condensing tank 132, a cooling coil 134 connected to a chiller 133 is installed. Has been done. A vacuum pump 135 is connected to the condensing tank 132,
The inside of the condensation tank 132 and thus the inside of the decompression container 121 is depressurized to a predetermined pressure. Further, the decompression container 121 is decompressed, so that the cleaning drainage liquid A is supplied from the cleaning drainage storage tank 110 into the decompression container 121. The vapor E cooled by the cooling coil 134 is condensed, and the condensed liquid is stored as the regenerated liquid F in the regenerated liquid collection tank 136. In the regenerant collection tank 136, a regenerant supply pipe 13 in which a pump 137 for resupplying the regenerant F to the cleaning device is inserted.
8 are connected.

In the above-mentioned cleaning drainage regenerating apparatus 101, the cleaning drainage can be continuously processed without using a defoaming agent. Can be more efficiently processed and reproduced.

Next, a method of processing and regenerating the cleaning drainage A by the cleaning drainage regenerator 101 described above will be described. First, the vacuum pump 135 is operated to reduce the pressure inside the decompression container 121 to a predetermined pressure, and at the same time, the cleaning drainage liquid A is drawn from the cleaning drainage storage tank 110 into the decompression container 121. Decompression container 12
If the pressure in 1 is lower than the atmospheric pressure, the purpose will be achieved, but it depends on the composition of the cleaning effluent to be treated.
It is preferable to reduce the pressure to about Torr to 200 Torr. As a result, the component to be recovered in the cleaning waste liquid A can be evaporated at a lower temperature.

The cleaning waste liquid A once stored in the liquid storage part 125 overflows from the liquid storage part 125, flows down the inner wall surface 122a of the thin film forming pipe 122, and then flows down to the inner wall surface 122a. A thin film C of the cleaning drainage liquid A is formed along it. Since the thin film forming pipe 122 is heated to a predetermined temperature by the heater 124,
The cleaning waste liquid A is heated in a thin film C state, in other words, in a wet wall state under reduced pressure, and the component to be recovered is vaporized. The steam E generated by heating at a temperature lower than this atmospheric pressure state passes through the steam recovery pipe 131 to the condenser 130.
Sent to In this way, since the treatment / regeneration is performed by the boiling point difference of each component including the dirt component in the cleaning effluent, the degree of pressure reduction and the heating temperature depend on the components to be recovered and the other components to be separated. It is important to set the temperature according to the boiling point, and further considering the liquid supply amount and the like.

Here, the cleaning drainage A to be treated in the present invention can be treated and regenerated with various cleaning drainages regardless of the drainage by the water-based detergent and the drainage by the solvent-based detergent. it can. For example, in the case of treating a solvent type cleaning agent or a solvent type rinsing liquid, the solvent which is the basic component will be recovered. In particular, since the rinse liquid is used in a large amount, it can be effectively regenerated and reused. In the case of regenerating a solvent-based cleaning agent or rinsing liquid, the regenerating liquid F is mainly used as a rinsing liquid in both cases. Further, when regenerating the water-based cleaning agent, water is obtained as the regenerating liquid F.

As described above, the cleaning drainage A is heated under reduced pressure when flowing down along the inner wall surface 122a of the thin film forming pipe 122 as the thin film C, water and solvent are vaporized, and other The components are stored in the evaporation residual liquid storage section 121a. Since the water and the solvent that cannot be completely evaporated remain in the evaporation residual liquid D, the evaporation residual liquid D is retransmitted to the liquid storage section 125 by the circulation pump 126 and is processed again as the processing liquid B, and the cleaning drainage A. Is continuously heated and evaporated.
When the heating / evaporating operation is repeated and the liquid level in the evaporation residual liquid storage portion 121a is lowered, the automatic valve 113 which is interlocked with the liquid level gauge 112 is opened, and a new cleaning waste liquid A is added to the decompression container 121 (liquid It is supplied to the storage part 125) and heated.
The evaporation operation is continuously performed.

The shape and number of the thin film forming pipes 122 and the liquid supply amount can be adjusted so that the evaporation is completed only by one flow down. In this case, the circulation pump 126 and the like become unnecessary, and the evaporation residual liquid D may be discarded as it is.

The steam E generated by heating, that is, the steam of water or solvent, is passed through the steam recovery pipe 131 to the condensing tank 1
It is sent to 32 and is cooled and condensed in this condensing tank 132. This condensate is recovered as the regenerated liquid F in the regenerated liquid collection tank 136. The regeneration liquid F is reused, for example, as a rinse liquid. The evaporation residual liquid concentrated by the heating operation is discharged through the drain pipe 128.

By the way, in the wet wall type cleaning drainage regenerating apparatus 101 according to this embodiment, it is important to adjust the overflow amount from the liquid storage section 125 (the circulation amount by the circulation pump 126 and the cleaning drainage A supply amount). Is. That is, if a too large amount of liquid is made to flow down, defective formation of the thin film C will occur, resulting in a decrease in evaporation efficiency, in other words, a decrease in the amount of liquid recovery. Therefore, the thin film forming pipe 1
The overflow amount is adjusted in consideration of the inner wall area of 22 (x number), the degree of pressure reduction, the heating temperature, and the like.

FIG. 12 shows the results of examining the relationship between the recovery amount and the processing time when the liquid supply amount was changed. FIG.
3000 ml of a mixed liquid (W1 = 70 wt% + alcohol 30 wt%) of Technocare W1 (trade name, manufactured by Toshiba Corporation), which is a silicone-based solvent, as treatment liquid (simulated cleaning drainage liquid)
The recovery amount (vs. time) by each liquid supply amount (circulation amount) when heated to 80 ° C. under a reduced pressure of 20 Torr is shown. The thin film forming pipe 122 is made of a stainless steel material, and has an inner diameter of 30 mm, a wall thickness of 2 mm, and a length of 600 mm. From FIG. 12, it can be seen that when the liquid supply amount is too large, the recovery amount decreases. Therefore, it is important to optimize the treatment by controlling the thickness of the thin film C (thickness of the wetting wall liquid).

However, as is clear from the result when two pipes shown in FIG. 13 are used, the thin film forming pipe 122
It is possible to deal with an increase in the liquid supply amount by increasing the number of This means that it is possible to efficiently process a large amount of cleaning waste liquid without increasing the number of the thin film forming pipes 122, that is, without increasing the size of the apparatus body itself. On the other hand, in the tank-type distillation as used in the above-mentioned embodiment, the treatment amount largely depends on the tank capacity (internal area), and in order to increase the treatment amount (recovery amount), the tank capacity ( The amount of heat applied must be increased as well as the internal area).

FIG. 14 shows a comparison between the amount recovered by the wet wall distillation and the amount recovered by the tank distillation. The wet-wall distillation was carried out in the same manner as in the above-mentioned test example, and the tank-distillation was carried out under the same conditions with the inner area of the tank being the same as the inner wall area of the thin film forming pipe 122. Table 7 shows the results of comparison between the wet-wall vacuum distillation and ordinary vacuum distillation and atmospheric distillation.

[0115]

[Table 7] As is clear from FIG. 14 and Table 7, it is understood that the regenerated liquid can be highly efficiently recovered by the wet wall distillation. Further, it is possible to easily increase the processing amount only by increasing the number of pipes. That is, according to the wet-wall distillation, it is possible to provide a small-sized and highly efficient cleaning and drainage regeneration device.

Incidentally, FIG. 15 shows the relationship between the shape of the upper end surface of the thin film forming pipe and the amount of recovery. In addition, this test uses the same simulated cleaning effluent as the above test example, under reduced pressure of 20 Torr at 80 ° C.
Liquid was supplied at a rate of 1 liter / hour and heated, and a pipe material with an inner diameter of 9.5 mm, a wall thickness of 1.5 mm and a length of 400 mm was used. As is clear from FIG. 15, it is understood that the thin film forming pipe having the curved end face and the notch contributes to the improvement of the processing efficiency.

Table 4 shows the experimental results when the material of the thin film forming pipe was changed. Regarding the conditions etc.,
The experiment was the same as the experiment whose results are shown in Table 8.

[0118]

[Table 8] As is clear from Table 8, there is no great difference in the recovery rate and the recovery purity depending on the material of the thin film forming pipe, and it can be seen that various materials can be applied. However, when the iron pipe is used, if the heating medium is water or the treatment liquid is water-based, there is a risk of rusting. Therefore, in such a case, it is preferable to use another material.

As described above, in the cleaning and drainage regenerating apparatus 101 of this embodiment, the cleaning drainage A (or the treatment liquid B) is made to flow down to form the thin film C. The entire inner wall surface 122a can function as a heat transfer surface. Furthermore, the number of thin film forming pipes 122 installed allows the heat transfer surface to be easily increased according to the amount of processing. Therefore, the size of the device can be reduced without reducing the processing amount or the processing efficiency. In addition, the thin film forming pipe 122 allows the thin film C of the cleaning drainage liquid A.
Since the above is formed, a large amount of cleaning drainage liquid A can be easily and continuously processed. By heating the cleaning waste liquid A in a thin film state under reduced pressure, a large amount of high-load cleaning waste liquid is distilled (regenerated) at low temperature (at low cost) with high efficiency and accuracy without diluting. be able to.

In the above-mentioned embodiments, the pipe is used as the thin film forming portion, but the present invention is not limited to this. As the thin film forming portion, various shapes can be used as long as the thin film can be formed by flowing the cleaning waste liquid and the thin film forming surface can be heated. For example, the outer surface of the circular tube or the cylinder can be the thin film forming surface. In such a case, the cleaning drainage may be flowed down from the upper part of the thin film forming portion having a circular tube or cylindrical shape using a nozzle or the like. Further, in order to increase the contact area with the cleaning drainage, a collar or the like can be provided on the way. Further, various materials such as a plate-shaped thin film forming portion and a bellows-shaped thin film forming portion can be used.

The above-mentioned cleaning drainage regenerating device 101 can be used when the cleaning drainage from the cleaning device is processed in a batch method, and is also incorporated into the cleaning device 1 shown in FIG. It is also possible to continuously treat the cleaning effluent discharged from the rinsing means 30 of the apparatus 1 and continuously recycle the regenerated rinsing liquid.

When the cleaning drainage regenerating device 101 is applied to the cleaning drainage device 1 shown in FIG. 1, the cleaning drainage regeneration device 1 is replaced with the cleaning drainage regeneration device 40 shown in FIG.
01 should be incorporated.

Next, a specific example of cleaning using the cleaning apparatus 1 incorporating the cleaning drainage regenerating apparatus 101 and its evaluation result will be described.

Example 10 Using a cleaning device (the number of rinsing tanks = 2 tanks) incorporating a cleaning drainage regenerating device 101 to which wet-wall type vacuum distillation was applied, a die cast gear was prepared in the same manner as in Example 2. It was washed. As the cleaning agent, the same composition as in Example 2 was used, and the silicone antifoaming agent was also the same. The processing conditions for the wet-wall vacuum distillation are a processing speed of 15 l / hr and a vacuum degree of 140 To.
rr and heating temperature were 50 ° C. Further, even when the silicone antifoaming agent was not used, the washing and drainage treatments were similarly performed.

When 500 gears were washed under the above conditions, the COD _{1 of the} cleaning drainage sampled from the cleaning drainage storage tank 110 and the COD _{2 of the} regenerated rinse water sampled from the regenerant liquid collection tank 136 The residual rate (COD ₂ / COD ₁ × 100 (%)) was determined. The results are shown in Table 9.

[0126]

[Table 9] As is clear from Table 9, the wet-wall distillation has a higher heating effect than the tank-type distillation of the same scale, so that the distillation can be sufficiently performed despite the low heating temperature of 50 ° C. I know there is. Also, regarding the processing speed,
It was confirmed that the distillation process could be performed with high accuracy, even though the rate was as high as liter / hr. These are the same as Example 2 shown in Table 5 (treatment rate: 5 liter / hr, pressure reduction degree).
The comparison is clear with the results of 150 Torr and heating temperature of 75 ° C). As described above, according to the wet-wall vacuum distillation, the processing speed can be increased, the distillation can be performed in a short time, and the distillation can be performed at a lower temperature. By these, for example, the cleanliness of the rinse liquid can be further enhanced, and the load on the silicone-based defoaming agent can be reduced.

[0127]

As described above, according to the method for reclaiming cleaning waste water of the present invention, the high-load cleaning waste water containing the cleaning agent component can be directly continuously supplied at low cost without dilution. It becomes possible to reproduce efficiently. Further, according to the cleaning method and the cleaning apparatus of the present invention, after reducing the supply circulation amount of the rinse liquid, it is possible to maintain the cleanliness of the rinse liquid, so if the above cleaning drainage regeneration method is applied to these, For example, rinsing liquid can be used efficiently, and therefore, as an alternative cleaning agent for freon-based solvents and chlorine-based solvents,
When using a water-based cleaning agent or a solvent-based cleaning agent, highly accurate cleaning can be performed at low cost.

[Brief description of drawings]

FIG. 1 is a diagram schematically showing a configuration of a cleaning apparatus according to an embodiment of the present invention.

FIG. 2 is a diagram showing experimental results showing the relationship between the number of multi-tank rinsing tanks and the degree of soiling of the rinse liquid.

FIG. 3 is a diagram showing another experimental result showing the relationship between the number of multi-tank rinsing tanks and the degree of soiling of the rinse liquid.

FIG. 4 is a diagram showing experimental results showing the degree of soiling of the rinse liquid when the rinse liquid in the multi-tank connection type rinse tank is sequentially flowed down.

FIG. 5 is a diagram schematically showing the configuration of a wet-wall type cleaning drainage regenerator according to an embodiment of the present invention.

FIG. 6 is an enlarged view showing a main part of the wet-wall-type cleaning drainage regenerating apparatus shown in FIG.

FIG. 7 is a diagram showing an improved example relating to liquid supply in the wet wall type cleaning drainage regeneration device shown in FIG.

FIG. 8 is a diagram showing another example of improvement relating to liquid supply in the wet wall type cleaning drainage regeneration device shown in FIG.

FIG. 9 is a diagram showing an example of a thin film forming pipe in the wet wall type washing and drainage regenerating apparatus of the present invention.

FIG. 10 is a diagram showing another example of a thin film forming pipe.

FIG. 11 is a view showing still another example of the thin film forming pipe.

FIG. 12 is a diagram showing the relationship between the amount of reclaimed liquid recovered and the processing time when the amount of liquid supplied in the wet-wall cleaning drainage regenerator is changed.

FIG. 13 is a diagram showing the amounts of regenerated liquid collected by the wet-wall vacuum distillation method and the tank vacuum distillation method in comparison.

FIG. 14 is a diagram showing the relationship between the amount of reclaimed liquid collected and the processing time when the shape of the upper end of the thin film forming pipe in the wet wall type cleaning drainage reclaimer is changed.

[Explanation of symbols]

 1 Cleaning device 2 Cleaning object 20 Cleaning device 21 Cleaning agent 22 Immersion cleaning tank 30 Rinsing device 31 Multi-tank connected rinsing tank 32 ……… Rinse solution 40 ………… Cleaning drainage regenerating means 42 ………… Decompression type heating can 43 ………… Condenser 49 ………… Decompression pump 60 ………… Defoaming agent supply means 61 ………… Silicone type Defoaming agent 71 ... Circulation pump 120 ... Wash drainage heating section 121 ... Decompression container 122 ... Thin film forming pipe 125 ... Liquid storage section 130 ... Condensing section A ... Wash drain C ... ……… Thin film E ………… Steam

Continuation of the front page (51) Int.Cl. ⁶ Identification number Office reference number FI technical display location C11D 3/37 C11D 3/37 C23G 3/00 C23G 3/00 Z 5/04 5/04 (72) Inventor Minoru Inada 1-1-1 Shibaura, Minato-ku, Tokyo Toshiba Head Office Co., Ltd. (72) Inventor Noriaki Yagi No. 8 Shinsugita-cho, Isogo-ku, Yokohama-shi, Kanagawa Stock Company Toshiba Yokohama Office (72) Inventor Hiromi Shizu Kanagawa prefecture, Yokohama, Isogo-ku, 8 Shinsugita-machi, Toshiba Corporation Yokohama office (72) Inventor Nobuhiro Saito 6-31, Roppongi, Minato-ku, Tokyo Toshiba Silicone Co., Ltd. (72) Inventor Shigeo Yamato Tokyo 6-23-1, Roppongi, Minato-ku, Toshiba Silicon Co., Ltd. (72) Takashi Takahashi 6-23-31, Roppongi, Minato-ku, Tokyo, Toshiba Toshiba (72) Inventor, Akitsugu Kurita Minato-ku, Tokyo 6th 2-31, Roppongi Toshiba Toshiba Corporation

Claims (7)

[Claims] 1. A cleaning step of removing dirt components adhering to an object to be cleaned by a cleaning tank containing a non-aqueous cleaning agent, and a transfer direction of the object to be cleaned containing a non-aqueous rinsing liquid. A multi-tank connection type rinsing tank connected so that the rinsing liquid is sequentially sent in the reverse direction, and a rinsing step of removing the cleaning agent component adhering to the object to be cleaned, the multi-tank connecting rinsing tank The cleaning effluent discharged from the rinse tank located on the most downstream side is subjected to vacuum distillation, while the resulting condensate is circulated and supplied to the rinse tank located on the most upstream side, the rinsing step is performed. How to wash. 2. A cleaning step of removing dirt components adhering to an object to be cleaned by a cleaning tank containing a non-aqueous cleaning agent, and a transfer direction of the object to be cleaned containing a non-aqueous rinsing liquid. A rinsing step of removing the cleaning agent component adhering to the object to be cleaned by a multi-tank connection type rinsing tank connected so that the rinsing liquid is sequentially fed in the opposite direction, and a silicone-based defoaming component is included. While using at least one of a cleaning agent and a rinsing liquid, the cleaning effluent discharged from the rinse tank located on the most downstream side of the multi-tank connection type rinsing tank is distilled under reduced pressure, and the resulting condensate is located on the most upstream side. A rinsing method, wherein the rinsing step is performed while circulatingly supplying the rinsing tank. 3. A cleaning unit having a cleaning tank containing a non-aqueous cleaning agent, wherein the cleaning means removes dirt components adhering to the object to be cleaned by the cleaning agent, and a non-aqueous rinsing liquid is contained. Rinsing means for removing the cleaning agent component adhering to the object to be cleaned by the rinsing liquid, having a multi-tank connection type rinsing tank connected so that the rinsing liquid is sequentially sent in the direction opposite to the direction in which the cleaning product is transferred. And at least cleaning effluent discharged from the rinsing tank located on the most downstream side of the multi-tank connection rinsing tank is introduced, and the decompression heating mechanism for heating and evaporating the cleaning effluent under reduced pressure, and this decompression heating A cleaning drainage regenerating means having a condensing mechanism for condensing vapor obtained by a mechanism, and a defoaming agent supplying means for supplying a silicone defoaming agent that suppresses foaming in the decompression heating mechanism to the cleaning drainage, Obtained by the condensation mechanism Condensate, said multi-tank articulated rinse bath cleaning apparatus characterized by comprising a circulation system for supplying a rinsing tank located at the most upstream side of the. 4. A cleaning unit having a cleaning tank containing a non-aqueous cleaning agent, wherein the cleaning means removes dirt components adhering to the object to be cleaned by the cleaning agent, and a non-aqueous rinsing liquid is contained. Rinsing means for removing the cleaning agent component adhering to the object to be cleaned by the rinsing liquid, having a multi-tank connection type rinsing tank connected so that the rinsing liquid is sequentially sent in a direction opposite to the direction in which the cleaning product is transferred. And at least cleaning effluent discharged from the rinsing tank located on the most downstream side of the multi-tank connection rinsing tank is introduced, and the decompression heating mechanism for heating and evaporating the cleaning effluent under reduced pressure, and this decompression heating A cleaning drainage regenerating unit having a condensing mechanism for condensing the vapor obtained by the mechanism, and a condensate obtained by the condensing mechanism are supplied to a rinse tank located on the most upstream side of the multi-tank connection type rinse tank. And a system, At least one of the cleaning agent and rinse, cleaning apparatus which comprises a silicone-based defoaming component. 5. The cleaning method according to claim 2, wherein the silicone-based defoaming component is the same as the component that constitutes the cleaning agent. 6. The cleaning device according to claim 3, wherein the silicone-based defoaming agent is the same as the component that constitutes the cleaning agent. 7. The cleaning device according to claim 4, wherein the silicone-based defoaming component is the same as the component constituting the cleaning agent.