JP2001271189A - Liquid treatment apparatus, sterilizing apparatus and cleaning method using it, surface treatment method, and sterilizing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a liquid treatment apparatus which brings a small article having small holes such as a semi conductor article into full contact with the liquid, for example, the cleaning solution and the electloless plating solution, a sterilizing apparatus and a cleaning method using it, a surface treatment method, and a sterilizing method. SOLUTION: The liquid treatment apparatus comprises (A) a liquid treatment tank 1, (B) a vibrating and agitating mechanism having a vibrating motor 2, an inverter to adjust the frequency of the vibrating motor, a vibrating bar 3 connected to the vibrating motor and a vibrating blade 4 fixed to the vibrating bar, (C) a porous rotatable container 11 to store the articles to be treated, and (D) a rotating motor 12 which connects the porous rotatable container in (C)able to switch to (1) a low-speed inverter of to rotate container in the liquid at the lower speed of <500 r.p.m with the axis of rotation perpendicularly, or to (2) a high-speed inverter to centrifugally separate the treatment solution by rotating the container at the high speed of >=500 r.p.m. after the solution is removed with the axis of rotation perpendicularly, and the sterilizing apparatus and the cleaning method using it, the surface treatment method, and the sterilizing method are also provided.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel liquid processing apparatus for articles having a vibration stirring mechanism, and more particularly to a series of surface treatments such as cleaning of porous or complicated shaped articles such as semiconductors or electroless plating. The present invention relates to a liquid processing apparatus suitable for being implemented by one apparatus, a cleaning method using the same, and a surface processing method.

[0002]

2. Description of the Related Art Applicants have filed Japanese Patent No. 1941498 (Japanese Unexamined Patent Publication No. 3-275130) and Japanese Patent No. 2762388.
No. (JP-A-6-312124), Japanese Patent No. 285287.
No. 8 (JP-A-8-173785), JP-A-10-43
No. 569, Japanese Patent Application No. 10-76702 and Japanese Patent Application No. 11
No. 127830 has proposed a new technique relating to a series of vibration stirring.

[0003] As described above, the vibration agitation proposed by the applicant has been known in which one or many blades inserted into a liquid are subjected to an amplitude of 1 to 20 at a rate of 200 or more per minute by a vibration motor.
This is a stirring technique utilizing a surprising phenomenon that a liquid flows by finely vibrating to about mm.

[0004]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a liquid processing apparatus for bringing a fine hole or an article having a complicated shape such as a semiconductor into sufficient contact with a liquid, for example, a cleaning liquid or an electroless plating liquid. An object of the present invention is to provide a sterilization apparatus using the same, a cleaning treatment method, a surface treatment method and a sterilization method using the same.

[0005]

Means for Solving the Problems The first aspect of the present invention is that (A)
A liquid processing tank, (B) a vibration motor, an inverter for adjusting the frequency of the vibration motor, a vibration rod connected to the vibration motor, a vibration stirring mechanism having a vibration blade fixed to the vibration rod, and (C) liquid processing. The porous rotatable container for storing the article and (D) the porous rotatable container of (C) in (a) 500 r. p. m, preferably 10 to 200 r. p. m and a low-speed inverter for vertical rotation at a low speed of 500 m. p. m or more, preferably 5
00 to 2000 r.p. p. a liquid processing device, comprising: a rotary motor switchably connected to a high-speed inverter for centrifuging the processing liquid by rotating the rotation axis vertically at a high speed of m. .

A second aspect of the present invention is a liquid introducing valve, a liquid discharging valve, a valve for switching the type of liquid, the vibration stirring mechanism of (B), and the porous rotatable container of (C). 2. The liquid processing apparatus according to claim 1, further comprising a timer for operating a switching mechanism for switching the rotation speed among three stages of low speed, high speed, and stop at predetermined time intervals.

A third aspect of the present invention relates to a liquid processing apparatus according to claim 2, further comprising a control circuit for controlling setting of a timer. According to the time required for each process,
Set the timer freely.

A fourth aspect of the present invention relates to the liquid processing apparatus according to any one of claims 1 to 3, further comprising means for fixing a large number of articles with a desired gap in the porous rotatable container (C).

A fifth aspect of the present invention is that at least one part of the vibrating blade and / or the vibrating blade fixing member used for fixing the vibrating blade to the vibrating rod is provided with (i) at least one kind of sterilizing property. And / or having a surface layer containing a metal and / or a bactericidal metal compound, and / or
Or (ii) The sterilization apparatus according to any one of claims 1 to 4, wherein the vibrating blade and / or the fixing member for the vibrating blade generate magnetic force. It is preferable that (i) and (ii) are used in combination.

A sixth aspect of the present invention is that the bactericidal metal is A
The sterilization apparatus according to claim 5, which contains an element selected from the group consisting of g, Au, and an alloy thereof.

[0011] Seventh of the present invention, the biocidal metal compound is about sterilization apparatus according to claim 5, wherein a metal oxide selected from the group consisting of TiO ₂ and ZnO.

According to an eighth aspect of the present invention, there is provided a surface treatment wherein a series of steps for cleaning an article is continuously performed using the liquid processing apparatus according to any one of claims 1 to 4. About the method.

According to a ninth aspect of the present invention, a liquid processing apparatus according to any one of claims 1 to 4, wherein a series of steps for performing a surface treatment on an article is continuously performed. Regarding the processing method. In a series of steps, for example, repeated steps such as water washing-centrifugal dehydration-water washing-centrifugal dehydration can be set.

A tenth aspect of the present invention is that the surface treatment includes washing (including pretreatment for plating (such as degreasing), post-treatment, and washing), electroplating, electroless plating, anodizing, chemical polishing, and electrolytic polishing. The surface treatment method according to claim 9, which is any one of polishing, etching, chemical conversion film forming treatment, and fiber processing (dyeing the fiber itself, its woven or nonwoven fabric, resin processing, fire protection processing, and the like).

According to an eleventh aspect of the present invention, the vibrating blade of the sterilizer according to any one of claims 5 to 7 generates a desired vibration of 10 to 500 Hz in a vibrating motor by an inverter, and disperses the vibration to a vibration stress distribution. By transmitting the vibration blade to the vibration blade through the means and the vibration bar, the vibration blade has an amplitude of 0.1 to 15
The present invention relates to a method of sterilizing an article to be sterilized, characterized in that the article is vibrated at a frequency of 200 to 1000 times / min.

A twelfth aspect of the present invention is that the water in the treatment tank has a flow rate of 1
12. The fluid flowing at a speed of at least 00 mm / sec.
It relates to the sterilization method described.

In the liquid processing tank of (A), for example, as shown in FIG. 1, when viewed from the view of the liquid processing tank, the vibration stirring mechanism of (B) is installed on the right side, and the porous stirring mechanism of (C) on the left side. The structure is such that a rotatable container is installed.

As the vibration stirring mechanism of the above (B), all the vibration stirring means proposed by the present applicant as mentioned in the section of the prior art can be adopted. Japanese Patent No. 19
No. 41498, Patent No. 2707530, Patent No. 276
No. 2388, Japanese Patent No. 2852878, Japanese Patent No. 2988
No. 624.

The basic technology of the vibration stirring mechanism of the above (B) comprises a vibration generation means including a vibration motor and a vibration stirring means comprising one or more vibration blades fixed to a vibrating rod vibrating in conjunction therewith. It is.

The vibration motor is driven by an inverter at 10-500 Hz, preferably 30-200 Hz.
It is particularly preferable that an arbitrary vibration between 30 and 60 Hz be generated. The relationship between the output and the stirring capacity is slightly larger than the relationship described by the applicant in JP-A-8-173785. Is preferable from the viewpoint of rotating the container in the present invention.

It is preferable that a vibration stress dispersing means is provided at a connection between the vibration generating means and the vibrating rod. As the vibration stress dispersing means, a rubber ring is inserted around the vibrating rod below the vibration generating means at the connection part, or the vibration rod is divided at the connection part, and a metal wire bundle is inserted therebetween. Can be used.

The vibrating blade is arranged so that the direction perpendicular to the vibrating rod is 0 °.
In this case, it is preferable to install the camera at an angle of 5 to 30 degrees in the (+) or (-) direction. Thereby, the flow of the liquid can be made more efficient.

Other details of the vibration stirring mechanism are described in
As described in Japanese Patent No. 173785, the vibrating rod may be a single axis type or a biaxial type.

In addition, instead of or in addition to the above-described vibration stress dispersing means, the applicant's Japanese Patent Application No. 11-12783 is disclosed.
The vibration absorbing means described in No. 0 can also be used.

The vibration absorbing means includes: (a) a rubber plate (plate-like rubber), a laminate of soft rubber and hard rubber, or (b) rubber provided at a connection between the vibration generating means and the liquid processing tank. It consists of a laminated body of a plate and a metal plate, and absorbs the vibration of the vibration generating means including the vibration motor, receives the weight of the vibration generating means including the vibration motor, and prevents the vibration from being transmitted to any part other than the vibration rod. It functions to absorb useless vibration. The laminate of a metal plate and a rubber plate is rubber / metal / rubber, metal / rubber / metal or rubber / metal / rubber /
A laminate such as a metal may be used, and a space between each of these laminates may be bonded with an adhesive or may be simply overlapped.

The vibration absorbing means may cover the entire upper surface of the liquid processing tank and cover or close the tank so that the tank is sealed or semi-closed. It may be installed around. Alternatively, it is sufficient to provide the vibration absorbing means only in the portion of the liquid processing tank where the vibration stirring mechanism is installed, and to simply cover the porous rotatable container side.

In the case of a completely hermetic type, it is necessary to seal a portion where the vibrating rod penetrates the rubber plate or the laminate thereof with a deformable seal member. Such a seal is particularly advantageous in stirring the reaction system in which toxic gas is generated. Soft rubber can be used as the deformable seal member. Even when such a deformable seal member is not used, the main component of the rubber plate or its laminate is rubber, and the vertical vibration of the vibrating rod is usually 30 mm or less,
Preferably 20 mm or less, particularly preferably 15 mm or less, the lower limit is 2 mm or more, preferably 5 mm or more,
Especially preferably, it is about 10 mm or more, so that the expansion and contraction of the rubber plate or its laminated plate can considerably follow the vertical movement of the vibrating rod, so that frictional heat is not generated unexpectedly, and the rubber plate or its laminated A hole that is almost the same diameter as the outer diameter of the vibrating rod can be formed in the body, and the vibrating rod can be passed through the hole. Also,
The above-mentioned semi-closed type sealed state can be formed in a substantially similar closed state. NHK CO., Ltd. is a commercially available sealed type product in which the seal member and the vibrating rod are integrated. , LT
D. NS-A [compact type] for linear motion and NS [heavy load type] for linear motion can also be used.

The porous rotatable container (C) for storing the article to be liquid-treated is a polygonal column-shaped container [for example, FIG.
(A) or a cylindrical container (for example, see FIG. 4 (B)). Also, if this container is configured to be detachable and the next processed product is set in another container in advance,
When various processed products are processed one after another, the working time as a whole can be reduced.

The porous rotatable container (C) can be made of plastics or metal, but lightweight plastics is preferable in view of improving the rotation efficiency. Usually, a desired hole can be formed in a plate-shaped plastic plate or a metal plate, but if it is desired to increase the ratio of the hole area to the side wall, a wire mesh side wall is used, but a resin wire coated metal wire is used. Can be used as the side wall made of wire mesh. The opening area for the side wall can be about 10 to 98%. The number of rotations of the container at low speed varies depending on the vibration stirring force and the weight and size of the container, but is usually 500
r. p. m, preferably 10 to 200 r. p. m,
Particularly preferably, 20 to 150 r. p. m is preferable. When the product to be processed is not fixed, the number of rotations is a number of rotations that can uniformly contact the processing liquid in all directions within a range where the products do not touch each other with the rotation and are not damaged. Is preferred.

For the large number of holes provided in the container (C), the number and the number of holes having the highest processing efficiency are selected in accordance with the size and shape of the article to be filled in the container and subjected to liquid processing. Usually, the opening ratio is preferably 20% or more with respect to the side wall. Below this, the processing efficiency decreases.

The shape of the liquid treatment tank of (A) is not particularly limited, but the side provided with the porous rotatable container of (C) should not obstruct the flow of the liquid by vibrating stirring as much as possible. It is preferable to make the shape as simple as possible. For this purpose, it is preferable to adopt a structure that does not form a 90 ° corner as shown in FIG.

Preferably, the apparatus of the present invention is provided with means for automatically switching the polarity of the vibration motor between plus and minus at regular intervals. In this case, the liquid in the liquid processing tank (A) flows clockwise in the premises or counterclockwise in the premises, so that the liquid in the container (C) is more evenly in contact with the liquid. And the reproducibility and uniformity of the process are improved.

In order to clean or sterilize articles using the apparatus of the present invention, for example, after cleaning semiconductors or sterilizing dishes, the processing liquid is discharged from the liquid processing apparatus and then adhered to the semiconductors. Centrifugal dewatering can be performed in order to sufficiently remove the processing solution and the like that have been used. The high-speed rotation speed of the container at this time is usually 500 r. p. m or more, preferably 500 to 2000 r. p. m, particularly preferably 10
00 to 2000 r.p. p. m. In order to stabilize and secure the rotation of the container (C) during high-speed rotation,
A guide can be attached to the upper part of the container (C).

Examples of the articles include, but are not limited to, glass articles,
Examples include ceramic substrates, general printed boards, wafers, semiconductor chips, small electronic components, hard disks, hard disk components, special precision components, and other electronic devices. Items to be sterilized include food and drinks, food and beverage manufacturing parts, various food and beverage and medical bottles and containers, medical equipment such as surgical tools, clothing, bedding, haberdashery, cosmetic tools, and food (vegetables). , Fruits, etc.).

The germicidal metals include Ag, Pd, and A.
u, Pt, Ni, Cu, Zn, Mg, Sn, Pb, etc., which may be a single metal, an alloy of these metals (for example, brass), or an alloy of these metals with other metals. There may be. Examples of the bactericidal metal compound include metal oxides such as titanium oxide, zinc oxide, and silver oxide.

The surface layer made of the bactericidal metal or the bactericidal metal compound (metal oxide or the like) is formed by using the bactericidal metal or its alloy on the vibrating blade or the fixing member for the vibrating blade. This can be achieved by plating or by composite plating of particles containing these metal components or particles of a bactericidal metal compound (such as a metal oxide). There is no restriction on the thickness of the surface layer,
Usually, about 5 to 20 μm is sufficient. In addition, a sterilizing metal can be used for the entire vibrating blade as needed, or a metal in which sterilizing metal particles are dispersed in an arbitrary metal can be used.

In the present invention, germicidal metal compound (eg, metal oxide) particles can be used instead of the germicidal metal. TiO ₂ as a germicidal metal oxide
And ZnO. There is no particular limitation on the size of the particles, but it is advantageous because the surface area is preferably larger as the fine particles are, and preferably 5 μm or less. A layer is formed on the surface of the vibrating blade by composite plating of fine particles of such a bactericidal metal compound (eg, metal oxide). In this case, the thickness of the surface layer is not limited, and is usually 5 to 20 μm.

When a vibrating blade, a fixing member for the vibrating blade, a stopper ring, or the like, which generates a magnetic force is used,
The water was activated, and it was found that when the laundry was washed with the treated water, the water was activated so that the amount of detergent used could be reduced to 1/5.

As described above, in order to generate magnetic force on the vibrating blade, the fixing member for the vibrating blade, and the accessory parts such as the stopper ring, the bolt, the nut, etc., any magnetic force generating means is employed. can do.
A permanent magnet (hard magnetic material) can be used, an electromagnet can be used, and in some cases, a soft magnetic material can be used. Hard magnetic materials include ferrite magnetic materials, rare earth magnetic materials, magnetic steel, etc.
Specifically, alnico magnets, samarium cobalt magnets,
Neodymium magnets, iron magnets, boron magnets and the like can be mentioned. In the case of a soft magnetic material, a coil may be wound around the material, a current may be passed through the material to give a necessary magnetic force to the soft magnetic material according to the principle of an electromagnet, and the material may be used. Examples of the soft magnetic material include soft iron, silicon steel, and permalloy. When imparting magnetism by the principle of the electromagnet, the polarity is changed from (1) plus to minus, (2) minus to plus,
(3) All negative, (4) All positive,
Or (5) For example, specific blades can be selectively given plus and minus, and other specific blades can be given plus and minus. Further, as these magnetic materials, flexible thin plate magnets described in Japanese Utility Model Publication No. 53-21438 can be used. The strength of the magnetic force is preferably at least 500 Oe. These magnetic materials are preferably used for fixing members for vibrating blades and their attached parts such as stopper rings, bolts, nuts, and the like. The bacteria to be sterilized in the present invention are not particularly limited, but are at least coliforms (Escherichia coli, pathogenic Escherichia coli, O-157), Salmonella, Vibrio parahaemolyticus, Campylobacter, Yersinia, Welsh, Nagvibrio. , Enterococci, Pseudomonas aeruginosa (Psevdomonas aeruginos)
a), Burkholderia cep
acia), Staphylococcus
cus aureus, Staphylococcus epidermidis (Staph)
ylococcus epidermidis, Streptococcus pne
umoniae), Serratia sp.
a), Plateus, Proteus, Enterobacter, Citrobacter, Enterococcus, Klebsiella, Bacteroides
acteroides), Legionella spp. (Legio)
nella), Mycobacterium sp. (Mycoba)
cterium), Pneumocystis carini (Pne)
umocystis carinii), fungi (fun
gus), pathogenic viruses and the like.

The base material of the vibrating blade and the fixing member for the vibrating blade used in the present invention may be a magnetic material as described above. However, when a magnetic material is not required, any metal material or plastics may be used. Can be. Further, a magnetic powder such as a rare earth magnetic powder can be contained in these materials.

The formation of the surface layer with a bactericidal metal or a bactericidal metal compound (eg, a metal oxide) is carried out by a usual plating method or germicidal metal-containing particles or germicidal metal compound (eg, a metal oxide) particle. There is a method of using a composite plating using the method. The formation of such a surface layer,
Vibration blades made of plastic and vibration blade fixing members are also possible.
July 25, 1971, published by The Nikkan Kogyo Shimbun, “Plating Technique Handbook”, pages 650 to 664, after performing a base treatment for improving normal adhesion, and then plating or composite such as silver plating. Plating can be performed.

It is preferable that the water in the treatment tank has a flow rate of 100 mm / sec or more as measured by a three-dimensional electromagnetic current meter (ALEC Electronics Co., Ltd., trade name: ACM300-A) by vibrating stirring.

[0043]

EXAMPLES The present invention will be described below with reference to examples.
The present invention is not limited thereby.

Example 1 As shown in FIGS. 1 to 3, the height from the bottom upper surface was 450 mm.
In the liquid processing tank 1 having a horizontal width (inner dimension) of 900 mm and a vertical width (inner dimension) of 500 mm, a vibration stirring mechanism is provided on the right side of FIG. A vibration motor (manufactured by Yaskawa Electric,
Under 150 W × 200 V × 3 P) 2, two vibrating rods 3 are provided via a vibration transmitting unit as shown in FIG.
The five vibrating blades 4, 4,... Were mounted between the vibrating rods, and one of the lower vibrating blades was set at an angle of 15 ° downward, and the other four were set at an angle of 15 ° upward. The position of the vibrating rod was set at a position 137 mm away from the right side wall of the liquid processing tank. The supply and discharge of the liquid were performed using a solenoid valve, and the operation of the solenoid valve and the device was automated by setting a timer. The rotary motor has a Fuji Electric inverter FVR-C11S (0.75k
w) was used.

On the other hand, the container 11 of FIG.
(B) has a columnar shape whose top view is shown,
The side wall is provided with a large number of holes with a diameter of 16 mm,
The surface area occupied by the holes was 30% of the total side wall surface area of the porous rotating container. The container (C) is made of polyvinyl chloride.

Usage mode Printed circuit boards requiring cleaning (200 × 200 × 1.
6) are set up in a state where 17 sheets are arranged in parallel at 5 mm intervals as shown in FIG. 5, and this is fixed in a porous rotating container. The hole of the porous rotating container was 16 mm in diameter, and the surface area occupied by the hole was 30% of the total side wall surface area of the porous rotating container. FIG. 4 is a cross-sectional view of the porous rotating container.
(B), having a height of 430 mm and a diameter of 35
0 mm. The stirring tank has the shape shown in FIGS.

A naphthenic petroleum solvent (Technoclean S700, manufactured by Nippon Techno Co., Ltd.) at 70 ° C. was supplied from the auxiliary tank to the treatment tank 1 through line 5 for rough cleaning.
Is opened and injected into the processing tank 1, and the volume is controlled to a constant value by a level meter. 45Hz vibration motor by inverter
By vibrating the vibrating blades 4 with the above, a vibrating flow is generated in the naphthenic petroleum solvent. On the other hand, the porous rotating container controls the rotating motor using a low-speed inverter (FVR-C11S), and outputs 15 r. p. m
Gives one-way rotation. After continuing the vibration stirring for 5 minutes, the stirring and rotation are stopped, the drain valve 8 is opened, and the naphthenic petroleum solvent is discharged (collected and returned to the auxiliary tank).
In addition, drainage and liquid supply are forcibly performed using a pump, and the operation time can be shortened. After draining, the porous rotary container 11 is connected to a high-speed inverter (FVR-C11S).
And the rotating motor at 1000 r. p. The printed circuit board in the porous rotating container 11 was centrifugally drained by rotating the printed circuit board in the horizontal direction at m. Next, by repeating the precision cleaning step using an isobutanol solvent, a desired cleaning result could be achieved in a short time. When a flammable solvent is used, it is preferable to use explosion-proof motors.

Example 2 A printed circuit board having a large number of small holes (200 × 200 × 1.6) was manufactured in the same manner as in Example 1 using the same apparatus as in Example 1.
pickling treatment (2 minutes), drainage, centrifugal elimination (3 minutes), and distilled water (pH 6.0).
8) Washing (time shown in Table 1)-Drainage-Centrifugal dehydration (3 minutes)-70 ° C hot air drying. Table 1 shows the results of measuring the surface pH value of the printed circuit board. In the table, (A) shows a case where only the pickling treatment with low-speed rotation and washing with distilled water are performed using this apparatus, and the centrifugal dehydration treatment is not performed. (B) is a pickling treatment without low-speed rotation. In this case, only the washing with distilled water is performed, and the centrifugal dehydration treatment is not performed.

[0049]

[Table 1]

From the results shown in Table 1, it can be seen that the washing time required for the embodiment 2 to be shorter until the surface pH value of the printed circuit board becomes the pH of the distilled water for washing is shorter than that of (A) or (B). .
Inspection of the appearance of the printed circuit board after washing for 10 minutes revealed that a water spot was generated in the cases of (A) and (B), whereas a water spot was generated in the case of the second embodiment. Absent.

Example 3 Electronic components were placed in a porous rotating container of the same apparatus as in Example 1, and Technoclean # 2000 [manufactured by Nippon Techno Co., Ltd.
Alkaline (sodium carbonate) degreaser] In a degreaser consisting of an aqueous solution containing 10%, the vibration motor was turned on for 45 minutes.
Hz, and the rotating container is rotated at 15 r. p. After cleaning as m, the degreasing solution is discharged and returned to the auxiliary tank. Then, at 1000 r. p. After centrifugal dehydration at m for 3 minutes, distilled water was supplied from the line 5 and washed by vibration stirring at 45 Hz for 5 minutes in the same manner, followed by drainage and centrifugal dehydration (3 minutes). . Table 1 shows the results obtained by examining the relationship between the amount of liquid attached to the electronic component thus obtained ((weight of attached liquid / weight of electronic component) × 100%) and the time of the hot air drying treatment at 70 ° C. In the table, (A) shows a case in which only degreasing with low-speed rotation and washing with distilled water are performed using this apparatus and centrifugal dewatering is not performed, and (B) only degreasing and washing with low-speed rotation is performed without using this device. In this case, centrifugal dehydration is not performed.

[0052]

[Table 2]

Example 4 Using the same apparatus as in Example 1, a kitchen filter (250
× 180 × 25mm, filter hole diameter 8mmφ, stainless steel cotton is filled in 10mm thickness, oil and fat adhesion amount is 40g) 4 pieces are put in a porous rotary container and fixed as in Example 1. , Techno Clean # 300
0 (manufactured by Nippon Techno Co., Ltd., strong alkaline (caustic soda-based) detergent) In a 70 ° C. washing solution containing 10%, the vibration motor was vibrated and stirred at 45 Hz for a predetermined time shown in Table 3, and the rotating container was removed. Rotation is 20r. p. After washing as m, the washing solution was discharged and returned to the auxiliary tank, and then centrifuged and drained. Further, using water, vibration stirring, washing with rotation, and centrifugal dehydration were repeated. Table 3 shows the relationship between the decontamination rate (%) and the cleaning time. In addition, (C) in Table 3 is the case where the vibration stirring was performed, but the low-speed rotation of the porous rotary container was not performed during that time.

[0054]

[Table 3]

Example 5 Using the same apparatus as used in Example 1, a copper plate (200 × 200 × 1 m) having a number of small holes (hole diameter 50 μm) was used.
m) 17 sheets were set as in Example 1 and electroless nickel plating was performed. The composition of the electroless nickel plating solution is as follows. Copper nickel sulfate 25 g / L Sodium hypophosphite 20 g / L Sodium acetate 10 g / L Sodium citrate 10 g / L Adjusted to pH 4.8-5.0 Temperature Adjusted while replenishing plating solution to 88-90 ° C. The plating Using liquid, vibration motor 45Hz for 40 minutes
At 15 r. p. m, degreasing treatment (2 minutes)-drainage-centrifugal dehydration (800
r. p. m, 3 minutes)-washing with water (3 minutes)-drainage-centrifugal dehydration (800 rpm, 3 minutes)-hot air drying at 70 ° C. As a result, the thickness and appearance of the electroless plating layer are as shown in Table 4.

[0056]

[Table 4]

The following table shows the average value of each measurement point.

[Table 5] When the container was rotated at a low speed, the film thickness became more uniform than when the container was not rotated at a low speed, and no plating failure in the small holes occurred. When the product did not rotate at a low speed, about 5% of defective products were produced. On the other hand, when the product was rotated at a low speed, no defective products were produced.

Example 6 Using the apparatus of Example 1, 20 shirts were washed. 45H in a washing liquid of 70 ° C containing 50g of powder detergent
z and 120 r. p. washing with rotation of m
Minutes, drain, and 600 r. p. After centrifugal dewatering at m, water washing and centrifugal dehydration were performed under the same conditions. The time required for washing was reduced to about 1/3, and the cleanliness by washing was not inferior to that of a conventional washing machine.

Example 7 The same apparatus as in Example 1 was used except that the vibration motor
The vibrating blade of the 0W × 200V × 3P, vibrating fluidized stirrer is made of horizontal steel, and its surface has a silver plating layer having a thickness of 10 μm. Further, a neodymium magnet, which is a horizontal ferromagnetic material, was used for the fixing member for the vibrating blade which holds the vibrating blade by pressing it from above and below, and a portion which does not overlap with the blade was plated with silver having a thickness of 10 μm. A wire mesh basket was used as the porous rotatable container. Tableware was sterilized and washed using this apparatus. Tableware was made of glass, aluminum, or alumite, and was fixed in the wire basket. Conditions for using the device are 4
0 Hz, the number of rotations of the porous container is 120 r. p. m, centrifuge rotation speed 800r. p. m and the processing time was 5 minutes. The test was carried out using only sterilized distilled water and sterilized distilled water containing 0.25 wt% of dishwashing detergent. As a result, no bacteria could be detected from any of the dishes. On the other hand, when a normal dishwasher was used, the presence of considerable bacteria was recognized.

Example 8 In Example 7, cabbage or strawberries were placed in a wire mesh basket instead of tableware and processed. No bacteria could be detected from the treated cabbage or strawberry in any of the treated waters. When a commercial continuous washing machine was used, some residual bacteria were observed.

Example 9 In Example 7, instead of tableware, a white coat worn in a hospital for a normal time was put in a wire mesh basket and sterilized distilled water alone and sterilized distilled water containing 0.25% by weight of a laundry detergent were used. I did the test. As a result, no bacteria could be detected from the white coat after the treatment in any of the treated waters. On the other hand, when a conventional washing machine was used, the presence of a considerable amount of bacteria was recognized, and a bleaching step was required to reduce this to almost zero.

[0062]

(1) The present invention is greatly characterized in that a series of processing steps can be performed by one apparatus. On the other hand, in the conventional method, for example, in the case of plating, it is necessary to arrange a large number of tanks, such as a degreasing tank, a washing tank, a plating tank, and a washing tank, and perform centrifugal dewatering between the tanks. As a result, the treatment liquid of the previous stage is mixed into the next washing tank, and contaminates the water in the washing tank.
It was necessary to provide a plurality of such as pieces. Thus, in the conventional method, by arranging a large number of tanks,
Although the time required for replacing the liquid can be saved, a large number of tanks must be provided, so that the installation area becomes large and the cost is unavoidable. On the other hand, in the present invention, the required number of treatments (for example, the number of times of water washing) and the treatment time are much shorter than in the conventional method due to the combined use of the vibration stirring and the rotation. However, the overall processing time is rather shortened. In addition, the cost of the apparatus is reduced because the number of tanks is one, and the area occupied by the apparatus is much smaller than that of the conventional method, so that the economic effect is extremely large. Furthermore, since it can be made small and hermetically sealed or semi-hermetically sealed, it is advantageous when installed in a clean room. (2) According to the present invention, when an article or the like having a very small concave portion or hole such as a semiconductor is treated with a liquid, the treatment liquid can uniformly contact any small concave portion or hole. Processing can be achieved uniformly. (3) In particular, the container in which the articles are placed is gently rotated during vibration stirring (20 to 150 rotations per minute), and the articles do not collide with each other due to dropping as in the case of barrel plating. Without this, each article can be more uniformly contacted with the processing liquid. (4) The present invention is useful for cleaning and electroless plating of components having small holes, such as semiconductors and electric components, or for fireproofing and washing thick and finely woven fabrics. (5) The sterilizer of the present invention exhibits the following effects. (I) A new sterilization and cleaning means that does not use any chemicals can be provided. (Ii) In the present invention, when a magnetic material is used, it is convenient for removing iron powder, iron colloid, and the like mixed in water. (Iii) When a magnetic material is used, a large circulating amount of water passes through a strong magnetic field, whereby water clusters become finer and the cleaning effect is improved. (Iv) Escherichia coli present in water,
Bacteria such as O-157, Salmonella and Streptococcus can be captured very effectively. (V) It is extremely effective in sterilizing tableware and other related equipment in cafeterias and school lunches, and greatly contributes to prevention of food poisoning. In addition, washing and sterilization can be completed in one step only by applying the method of the present invention to vegetables and fruits. (Vi) cleaning medical equipment, bedding, clothing or hospital equipment;
It is effective for sterilization and extremely effective for preventing nosocomial infections. (Vii) Since the present invention can be carried out at normal temperature, the object is not deteriorated by heat and is a sterilization means that does not substantially use chemicals. is there. (Viii) The amount of water required for treatment is significantly reduced.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view of one embodiment of the device of the present invention.

FIG. 2 is a plan view of only the processing tank of FIG.

FIG. 3 is a side view showing a combined state of the vibrating rod and the vibrating blade of FIG. 1;

FIG. 4 shows the porous rotatable container of the present invention and one of its rotating shafts.
It is a top view which shows an example, (A) is a top view which shows an example of a square-shaped porous rotatable container and its rotation axis, (B) is a circular porous rotatable container and its rotation axis. It is a top view which shows an example.

FIG. 5 is a cross-sectional view of the printed circuit board according to the first embodiment and a fixing device for fixing the printed circuit board in parallel at predetermined intervals.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Liquid processing tank 2 Vibration motor 3 Oscillating rod 4 Oscillating blade 5 Line (liquid supply system) 6 Lines (drainage system) 7 Liquid supply valve 8 Drainage valve 9 Liquid level control switch 10 Vibration stir mechanism mounting table 11 Porous Rotatable container 12 Rotary motor 13 Rotary shaft 14 Shaft seal (oil seal) 15 Gear box 16 Overflow mechanism 17 Printed circuit board 18 Printed circuit board fixing pedestal 19 Printed circuit board fixing holder 20 Printed circuit board holder 21 Printed circuit board holder

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (reference) C23F 1/08 101 C23F 1/08 101 C25D 17/00 C25D 17/00 E 21/10 21/10 H01L 21/304 651 H01L 21/304 651A

Claims (12)

[Claims] 1. A vibration stirring mechanism having (A) a liquid treatment tank, (B) a vibration motor, an inverter for adjusting the frequency of the vibration motor, a vibration bar connected to the vibration motor, and a vibration blade fixed to the vibration bar. , (C) a porous rotatable container for storing an article to be liquid-treated, and (D) a porous rotatable container of (C) in (a) 500 r. p. m and a low-speed inverter for rotating the rotating shaft vertically at a low speed of less than 500 m. p. a liquid processing apparatus, comprising: a rotary motor switchably connected to a high-speed inverter for centrifuging the processing liquid by rotating the rotation axis vertically at a high speed of m or more. . 2. A liquid introduction valve, a liquid discharge valve, a valve for switching the kind of liquid, a vibration stirring mechanism of (B), and a rotation speed of the porous rotatable container of (C), wherein the rotation speed is low.
2. The liquid processing apparatus according to claim 1, further comprising a timer for operating a switching mechanism for switching between high speed and stoppage at predetermined time intervals. 3. The liquid processing apparatus according to claim 2, further comprising a control circuit for controlling the setting of the timer. 4. The liquid processing apparatus according to claim 1, further comprising means for fixing a large number of articles with a desired gap in the porous rotatable container of (C). 5. The vibrating blade and / or at least a part of the vibrating blade fixing member used for fixing the vibrating blade to the vibrating rod includes: (i) at least one kind of bactericidal metal and / or The liquid according to any one of claims 1 to 4, wherein the liquid has a bactericidal metal compound-containing surface layer, and / or (ii) the vibrating blade and / or the fixing member for the vibrating blade generates magnetic force. A sterilization device, which is a processing device. 6. The sterilization apparatus according to claim 5, wherein the germicidal metal contains an element selected from the group consisting of Ag, Au, and alloys thereof. 7. The sterilizer according to claim 5, wherein the germicidal metal compound is a metal oxide selected from the group consisting of TiO ₂ and ZnO. 8. A surface treatment method using the liquid treatment apparatus according to claim 1, wherein a series of steps for cleaning an article is continuously performed. 9. A surface treatment method, wherein a series of steps for subjecting an article to surface treatment are continuously performed using the liquid treatment apparatus according to claim 1. Description: 10. The surface treatment includes washing (including pretreatment for plating (such as degreasing), post-treatment, and washing), electroplating, electroless plating, anodizing, chemical polishing, electrolytic polishing,
The surface treatment method according to claim 9, which is any one of etching, a chemical conversion film forming treatment, and fiber processing. 11. The sterilizing device according to claim 5, wherein the vibrating blade is connected to a vibrating motor by an inverter.
A desired vibration between 500 Hz is generated, and the vibration is transmitted to the vibrating blade through a vibration stress dispersing means and a vibrating rod, so that the vibrating blade has an amplitude of 0.1 to 15 mm and a frequency of 20.
A method for sterilizing an article to be sterilized, wherein the article is vibrated at 0 to 1000 times / minute. 12. The sterilization method according to claim 11, wherein the water in the treatment tank flows at a flow rate of 100 mm / sec or more.