JP3436733B2 - Liquid treatment device, sterilization device using the same, cleaning treatment method using the same, surface treatment method, and sterilization method - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a liquid treating apparatus for a novel article having a vibration stirring mechanism, and in particular, a series of surface treatments such as washing or electroless plating of porous or complex shaped articles such as semiconductors. TECHNICAL FIELD The present invention relates to a liquid treatment apparatus suitable for being carried out by one apparatus, a cleaning treatment method and a surface treatment method using the same.

[0002]

2. Description of the Related Art The applicant of the present invention has disclosed Japanese Patent No. 1941498 (Japanese Patent Laid-Open No. 3-275130) and Japanese Patent No. 2762388.
(Japanese Patent Laid-Open No. 6-312124) and Japanese Patent No. 285287.
No. 8 (JP-A-8-173785) and JP-A-10-43.
569, Japanese Patent Application Nos. 10-76702 and 11
No. 127830 has proposed a new technique for a series of vibration stirring.

As described above, in the vibration agitation that the applicant has proposed so far, one or a large number of blades inserted in the liquid are oscillated by the vibration motor at an amplitude of 1 to 20 at 200 times or more per minute.
This is a stirring technique that utilizes the surprising phenomenon that a liquid flows when it is vibrated slightly to about mm.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a liquid processing apparatus for sufficiently contacting a liquid such as a cleaning liquid or an electroless plating liquid with an article having fine holes or a complicated shape such as a semiconductor, Another object is to provide a sterilization apparatus using the above, 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 (A)
Liquid treatment tank, (B) vibration motor, an inverter for adjusting the vibration frequency of the vibration motor, a vibration rod connected to the vibration motor, a vibration agitation mechanism having vibration blades fixed to the vibration rod, (C) liquid treatment A porous rotatable container for storing articles and (D) the porous rotatable container of (C) above are used in (a) liquid at 500 r.p.m. p. m, preferably 10-200 r.m. p. Low speed inverter to rotate the rotation axis vertically at a low speed of m and (b) 500r. p. m or more, preferably 5
00-2000r. p. A rotary motor, which is switchably connected to a high-speed specification inverter for centrifuging the processing liquid by rotating the rotary shaft at a high speed of m, (E) (a) rubber plate or soft rubber A plate-like body selected from the group consisting of a laminated body of a rubber plate and a hard metal, and (b) a laminated body of a rubber plate and a metal plate, the vibration absorbing means covering the entire upper surface of the liquid treatment tank. The present invention relates to a liquid treatment device.

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

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

A fourth aspect of the present invention relates to the liquid treatment 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 of (C).

In a fifth aspect of the present invention, at least a part of the vibrating blade and / or the vibrating blade fixing member used for fixing the vibrating blade to the vibrating rod is (i) at least one sterilizing property. A metal and / or bactericidal metal compound-containing surface layer, and /
Alternatively, (ii) the sterilizer, which is the liquid processing apparatus according to any one of claims 1 to 4, wherein the vibrating blade and / or the fixing member for the vibrating blade generates magnetic force. In addition, it is preferable to use the above (i) and (ii) together.

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

A seventh aspect of the present invention relates to the sterilizer according to claim 5, wherein the bactericidal metal compound is a metal oxide selected from the group consisting of TiO ₂ and ZnO.

An eighth aspect of the present invention is characterized in that the liquid treatment apparatus according to any one of claims 1 to 4 is used to continuously carry out a series of respective steps for washing treatment of articles. Regarding the method.

A ninth aspect of the present invention is characterized in that the liquid treatment apparatus according to any one of claims 1 to 4 is used to continuously carry out a series of steps for subjecting an article to a surface treatment. Regarding processing method. In a series of steps, repeated steps such as water washing-centrifugal dehydration-water washing-centrifugal dehydration can be set.

In a tenth aspect of the present invention, the surface treatment includes cleaning [pretreatment for plating (such as degreasing), posttreatment and washing], electroplating, electroless plating, anodic oxidation, chemical polishing, electrolysis. The surface treatment method according to claim 9, which is any one of polishing, etching, chemical conversion film formation treatment, and fiber processing (dying of the fiber itself, its woven fabric or nonwoven fabric, resin processing, fireproofing, etc.).

In an eleventh aspect of the present invention, the oscillating blade of the sterilizer according to any one of claims 5 to 7 causes a desired vibration of 10 to 500 Hz in an oscillating motor by an inverter, and the oscillating stress is dispersed. By transmitting to the vibrating blade through the means and the vibrating rod, the vibrating blade has an amplitude of 0.1 to 15
The present invention relates to a method of sterilizing an article to be sterilized, which is characterized by vibrating at a frequency of 200 mm to 1,000 times / minute.

In the twelfth aspect of the present invention, the water in the treatment tank has a flow velocity of 1
The fluidized material is a fluidized material having a flow rate of 00 mm / sec or more.
It relates to the described sterilization method.

In the liquid treatment tank of (A), for example, as shown in FIG. 1, the vibration stirring mechanism of (B) is installed on the right side in the diagram of the liquid treatment tank, and the porous tank of (C) is on the left side. The structure is such that a container that can rotate freely is installed.

As the vibrating and stirring mechanism (B), all the vibrating and stirring means proposed by the applicant of the present invention and mentioned in the section of the prior art can be adopted. One example is Patent No. 19
No. 41498, No. 2707530, No. 276
No. 2388, No. 2852878, No. 2988
624 and so on.

The basic technique of the vibrating and agitating mechanism of the above (B) comprises a vibrating agitating means including a vibrating means including a vibrating motor and vibrating blades fixed to a vibrating rod that vibrates in association with the vibrating rod in one or more stages. Is.

The vibration motor is driven by an inverter to have a frequency of 10 to 500 Hz, preferably 30 to 200 Hz,
It is particularly preferable that it can generate an arbitrary vibration between 30 and 60 Hz, but the output and the stirring capacity have a slightly larger output than the relationship described by the applicant in JP-A-8-173785. Is preferable in order to rotate the container in the present invention.

It is preferable to provide a vibration stress dispersion means at the connecting portion between the vibration generating means and the vibrating rod. As the vibration stress dispersing means, one in which a rubber ring is inserted around the vibrating rod below the vibration generating means in the connecting portion, or the vibrating rod is divided in the connecting portion, and a metal wire bundle is inserted between them. Can be used.

The vibrating blades are arranged at 0 ° in the direction perpendicular to the vibrating rod.
In such a case, it is preferable to incline in the (+) or (-) direction by 5 to 30 °. As a result, the liquid flow can be made more efficient.

For details of the other vibrating stirring mechanism, see Japanese Patent Laid-Open No. 8-
As described in Japanese Patent No. 173785, the vibrating rod may be a single axis type or a biaxial type.

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

The vibration absorbing means (E) is (a) a rubber plate (plate-shaped rubber) provided at the connecting portion between the vibration generating means and the liquid processing tank, a laminated body of soft rubber and hard rubber, or (B) A laminated body of a rubber plate and a metal plate, which absorbs vibration of a vibration generating means including a vibration motor,
In addition, the weight of the vibration generating means including the vibration motor is received, and the unnecessary vibration is absorbed so that the vibration is not transmitted to other than the vibration rod. Laminates of metal plate and rubber plate are rubber / metal / rubber, metal / rubber / metal or rubber /
A laminated body such as metal / rubber / metal may be used, and each of these laminated bodies may be bonded with an adhesive.
It may be in a state of simply overlapping.

The vibration absorbing means of the above (E) covers the entire upper surface of the liquid processing tank, and the tank is hermetically or semi-hermetically closed by covering the tank.

In the case of the completely sealed type, it is necessary to seal the portion where the vibrating rod penetrates the rubber plate or the laminated body thereof with the deformable seal member. Such a seal is particularly advantageous in agitating the reaction system where toxic gas is generated. Soft rubber can be used as the deformable seal member. Even if such a deformable seal member is not used, the main component of the rubber plate or its laminated body is rubber, and the vertical vibration of the vibrating rod is usually 30 mm or less,
It is preferably 20 mm or less, particularly preferably 15 mm or less, and the lower limit is 2 mm or more, preferably 5 mm or more,
Particularly preferably, the length is 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 unexpected frictional heat does not occur and the rubber plate or its laminated plate is simply generated. By simply making a hole in the body that is approximately the same diameter as the outer diameter of the vibrating rod and inserting the vibrating rod into this hole, it is possible to form a satisfactory sealed state. Also,
The above-described semi-hermetically sealed state can also be formed into a hermetically sealed state that is substantially similar to this. Further, as a closed type commercial product in which a seal member and a vibrating rod are integrated, NHK CO. , LT
D. NS-A type [compact type] linear motion and NS type [heavy load type] linear motion can also be adopted.

The porous rotatable container for accommodating the liquid-processed article of (C) is a polygonal columnar container [see FIG.
(See (A) in FIG. 4) or a cylindrical container [see (B) in FIG. 4]. Also, if this container is configured to be detachable and the next processed product is set in another container beforehand,
When various kinds of processed products are processed one after another, the working time as a whole can be shortened.

The (C) porous rotatable container can be made of plastics or metal, but lightweight plastics are preferable from the viewpoint of improving rotation efficiency. Usually, it can be made by making a desired hole in a plate-shaped plastic plate or metal plate, but if you want to increase the ratio of the opening area to the side wall, use a metal mesh side wall, but a resin-coated metal wire Alternatively, the side wall may be made of wire mesh. The open area of the side wall can be about 10 to 98%. The rotation speed of the container at low speed varies depending on the vibration stirring force, the weight and size of the container, etc.
r. p. m, preferably 10-200 r.m. p. m,
Particularly preferably, it is 20 to 150 r. p. It is preferably m. When the product to be treated is not fixed, this number of revolutions is the number of revolutions that allows uniform contact with the treatment liquid in all directions within the range where the products do not come into contact with each other and are not damaged by the rotation. It is preferable.

The large number of holes provided in the container (C) are selected in accordance with the size and shape of the article filled in the container and subjected to the liquid treatment, and the shape and number of the holes having the highest treatment efficiency. Generally, the open area 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 on which the porous rotatable container of (C) is provided should not disturb the flow of the liquid by vibration stirring as much as possible. It is preferable to make the shape different. For that purpose, it is preferable to use a structure in which the corner portion is not a 90 ° corner portion as seen in FIG. 4A, rather than a square corner portion.

The device of the present invention is preferably provided with means for automatically switching the polarity of the vibration motor between positive and negative at regular intervals. By doing so, the liquid in the liquid treatment tank of (A) flows rightward or leftward in the premises, so that the contact between the liquid in the container of (C) and the liquid is more uniform. Therefore, the reproducibility and uniformity of the processing are improved.

In order to wash or sterilize articles using the apparatus of the present invention, for example, after washing semiconductors or sterilizing dishes, the treatment liquid is discharged from the liquid treatment apparatus and then attached to the semiconductors. Centrifugal deliquoring can be performed in order to sufficiently remove the treated liquid and the like. The high-speed rotation speed of the container at this time is usually 500 rpm. p. m or more, preferably 500 to 2000 r.m. p. m, particularly preferably 10
00-2000r. p. m. In order to stabilize and secure the rotation of the container (C) at the time of high speed rotation,
A guide can be attached to the upper part of the container (C).

Examples of the article are not particularly limited, but the article to be cleaned includes a glass substrate,
Examples thereof include ceramic substrates, general printed circuit 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 drink, parts for producing food and drink, various bottles and containers for food and drink, medical instruments such as surgical tools, clothing, bedding, fancy goods, makeup tools, foods (vegetables). , Fruit, etc.) and the like.

Examples of the bactericidal metal include Ag, Pd, A
Metals such as u, Pt, Ni, Cu, Zn, Mg, Sn and Pb, which may be single metals, alloys of these metals (eg brass) or alloys of these metals with other metals. It 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 (such as metal oxide) is formed by using the bactericidal metal or its alloy on the vibrating blade or the fixing member for the vibrating blade. It can be achieved by plating or by composite plating of particles containing these metal components or particles of a bactericidal metal compound (such as metal oxide). There is no limit to the thickness of the surface layer,
Usually, about 5 to 20 μm is sufficient. Further, if necessary, a sterilizing metal can be used for the entire vibrating blade, or a sterilizing metal particle dispersed in an arbitrary metal can be used.

In the present invention, bactericidal metal compound (eg, metal oxide) particles can be used in place of the bactericidal metal. TiO ₂ as a germicidal metal oxide
And ZnO. The size of the particles is not particularly limited, but it is preferable that the particles have a larger surface area, and it is preferably 5 μm or less if possible. A layer is formed on the surface of the vibrating blade by composite plating of fine particles of such a bactericidal metal compound (for example, a 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, etc., which generate magnetic force are used,
It was found that water was activated and, when the treated water was used for washing, the water was activated so that the amount of detergent used could be reduced to 1/5.

As described above, in order to generate the magnetic force on the vibrating blade, the fixing member for the vibrating blade, and the accessory parts thereof, such as the stopper ring, the bolt, and the nut, all magnetic force generating means are adopted. can do.
A permanent magnet (hard magnetic material) can be used, an electromagnet can be used, or a soft magnetic material can be used depending on the case. Examples of hard magnetic materials include ferrite magnetic materials, rare earth magnetic materials, and magnetic steel.
Specifically, Alnico magnets, samarium cobalt magnets,
Examples include neodymium magnets, iron magnets, and boron magnets. Further, in the case of a soft magnetic material, a coil may be wound around the material, and an electric current may be passed through the coil to give a necessary magnetic force to the soft magnetic material by the principle of an electromagnet before use. Examples of soft magnetic materials include soft iron, silicon steel, and permalloy. When imparting magnetism based on the principle of the electromagnet, the polarity is changed from (1) plus to minus, (2) minus to plus,
(3) All negative, (4) All positive,
Alternatively (5), for example, a specific blade may be positively provided, another specific blade may be negatively provided, and positive and negative may be selectively provided. Further, as these magnetic materials, the flexible thin plate magnets described in Japanese Utility Model Publication No. 53-21438 can also be used. The strength of the magnetic force is preferably 500 Oersted or more. It is particularly preferable to use these magnetic materials for the fixing member for the vibrating blade and its auxiliary parts such as stopper rings, bolts and nuts. The bacterium to be sterilized in the present invention is not particularly limited, but at least the coliform group (Escherichia coli, pathogenic Escherichia coli, O-157), Salmonella, Vibrio parahaemolyticus, Campylobacter, Yersinia bacterium, Clostridium perfringens, Nagvibrio bacterium. , Enterococci, Pseudomonas aeruginos
a), Burkholderia cep
acia), Staphylococcus aureus
cus aureus), Staphylococcus epidermidis (Taph)
ylococcus epidermidis, Streptococcus pne
umoniae), Serratia spp.
a), genus Proteus, genus Enterobacter, genus Enterobacter, genus Citrobacterium, genus Enterococcus, genus Klebsiella, genus Bacteroides
Acteoides), Legionella spp. (Legio)
nella), Mycobacterium (Mycoba)
cterium), Pneumocystis carini (Pne)
umocystis carinii), fungus
gus), pathogenic viruses, etc.

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

The surface layer is formed by a bactericidal metal or a bactericidal metal compound (for example, a metal oxide) by an ordinary plating method or bactericidal metal-containing particles or a bactericidal metal compound (for example, metal oxide) particles. There is a method of using composite plating using. The formation of such a surface layer is
It is also possible for vibrating blades and vibrating blade fixing members made of plastic, and on the plastic material beforehand,
July 25, 1972, published by Nikkan Kogyo Shimbun Co., Ltd., "Handbook of Plating Technology", pp. 650-664, followed by a surface treatment to improve normal adhesion, and then plating such as silver plating or composite Plating can be performed.

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

[0043]

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 is 450 mm,
In a liquid processing tank 1 having a width (inside dimension) of 900 mm and a height (inside dimension) of 500 mm, a vibration stirring mechanism is provided on the right side of FIG. In the vibration stirring mechanism, a vibration motor (Yasukawa Electric,
150W × 200V × 3P) 2, two vibration rods 3 and 3 are provided under the vibration transmission section as shown in FIG.
Five vibrating blades 4, 4, ... Are attached between the two vibrating rods, the lower one is set to be tilted downward by 15 °, and the other four are set to be tilted upward at 15 °. 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 was performed using a solenoid valve, and the operation of the solenoid valve and the device was automated by setting a timer. For the rotary motor, Fuji Electric inverter FVR-C11S (0.75k
w) was used.

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

Usage mode A printed circuit board (200 × 200 × 1.
As shown in FIG. 5, 17 mm (6 mm) are set up in parallel with each other at an interval of 5 mm, and 17 sheets are set in parallel and fixed in a porous rotary container. The holes of the porous rotary container had a diameter of 16 mm, and the surface area occupied by the holes was 30% of the total side wall surface area of the porous rotary container. A cross-sectional view of the porous rotary container is shown in FIG.
It has a shape of (B), and has a height of 430 mm and a diameter of 35.
It is 0 mm. The stirring tank has the shape shown in FIGS.

A naphthene-based petroleum solvent [Techno Clean S700, manufactured by Nippon Techno Co., Ltd.] at 70 ° C. was added to the treatment tank 1 from the auxiliary tank through a line 5 to a valve 7 for rough cleaning.
Open the tank and pour it into the processing tank 1, and control it to a constant volume with a level meter. Vibration motor 45Hz by inverter
By vibrating the vibrating blades 4, the naphthene-based petroleum solvent is caused to vibrate and flow. On the other hand, in the porous rotary container, a low speed inverter (FVR-C11S) is used to control the rotary motor, and the rotary rotary container is moved horizontally in the direction of 15 r. p. m
Gives rotation in one direction. After continuing vibration stirring for 5 minutes, stirring and rotation are stopped, the drain valve 8 is opened, and the naphthene-based petroleum solvent is discharged (recovered and returned to the auxiliary tank).
It should be noted that the drainage and the liquid supply are forcibly performed by using a pump, and the operation time can be shortened. After draining, the porous rotary container 11 was replaced with a high-speed inverter (FVR-C11S).
Using a rotary motor of 1000 r. p. The printed circuit board in the porous rotary container 11 was centrifugally drained by rotating it horizontally at m. Next, the precision cleaning process was repeated using the isobutanol solvent, whereby the desired cleaning result could be achieved in a short time. When a flammable solvent is used, it is preferable that the motors are explosion-proof.

Example 2 A printed circuit board (200 × 200 × 1.6) having a large number of small holes was formed in the same manner as in Example 1 using the same apparatus as in Example 1.
(mm) using a 5 wt% aqueous solution of hydrochloric acid, pickling treatment (2 minutes) -drainage-centrifugal deliquoring (3 minutes) -distilled water (pH 6.
8) Washing (time shown in Table 1) -drainage-centrifugal dehydration (3 minutes) -70 ° C hot air drying. The results of measuring the surface pH value of the printed circuit board are shown in Table 1. In the table, (A) shows a case where the apparatus is used for only pickling treatment accompanied by low speed rotation and distilled water washing without centrifugal dehydration treatment, and (B) is pickling treatment without low speed rotation. In this case, only distilled water was washed and centrifugal dehydration was not performed.

[0049]

[Table 1]

From the results shown in Table 1, it can be seen that the rinsing time required for the surface pH value of the printed circuit board to reach the pH of the distilled water for cleaning is shorter in Example 2 than in (A) and (B). .
Further, when the appearance of the printed circuit board after washing for 10 minutes was inspected, in the cases of (A) and (B), water spots were generated, whereas in Example 2, water spots were generated. Absent.

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

[0052]

[Table 2]

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

[0054]

[Table 3]

Example 5 Using the same apparatus as used in Example 1, a copper plate (200 × 200 × 1 m) having a large number of small holes (hole diameter 50 μ) 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 / liter Sodium hypophosphite 20 g / liter Sodium acetate 10 g / liter Sodium citrate 10 g / liter pH adjusted to 4.8 to 5.0 Adjusted temperature to 88 to 90 ° C. while replenishing the plating solution Using liquid, 40 minutes, vibration motor 45Hz
The mixture was vibrated and agitated with a rotating container for 15 r. p. m is the degreasing treatment (2 minutes) -drainage-centrifugal dehydration (800
r. p. m, 3 minutes) -Washing (3 minutes) -Drainage-Centrifugal dehydration (800 rpm, 3 minutes) -70 ° C warm air drying. 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 values of the respective measurement points.

[Table 5] When the container was rotated at a low speed, the film thickness was more uniform than when the container was not rotated at a low speed, and no defective plating occurred in the small holes. In addition, the appearance of the product was about 5% of defective products when it was not rotated at low speed, whereas no defective product was generated when it was rotated at low speed.

Example 6 Using the apparatus of Example 1, 20 shirts were washed. 45H in 70 ° C washing liquid containing 50g of powder detergent
z vibration agitation and 120 r. p. 1 washing with rotation of m
Performed for 5 minutes, drained, 600 r. p. After centrifugal deliquoring at m, washing with water and centrifugal dehydration were performed under the same conditions. The time required for washing was shortened to about 1/3, and the cleanliness of washing was as good as that of conventional washing machines.

Example 7 The same apparatus as in Example 1 was used, but the vibration motor was 15
The vibrating blade of the vibrating fluid stirrer is made of horizontal steel, and the surface thereof has a 10 μm thick silver plating layer. Further, a horizontal neodymium magnet, which is a ferromagnetic material, was used for the vibrating blade fixing member that presses and fixes the vibrating blade from above and below, and a portion of the vibrating blade that does not overlap with the blade is plated with 10 μm thick silver. A wire mesh basket was used as the porous rotatable container. Tableware was sterilized and washed using this apparatus. The tableware used was made of glass, aluminum, or alumite, and was fixed in the wire mesh basket. Device usage conditions are 4
0 Hz, rotation rate of porous container 120 r. p. m, centrifuge rotation speed 800 r. p. m and the treatment time was 5 minutes. As the treated water, a test was conducted using only sterilized distilled water and sterilized distilled water containing 0.25 wt% of a dish detergent. As a result, no bacteria could be detected in any tableware. On the other hand, when a normal dishwasher was used, the presence of a considerable amount of bacteria was recognized.

Example 8 In Example 7, instead of the tableware, cabbage or strawberries were placed in a wire netting basket and treated. No bacterium was detected in the cabbage or strawberry after treatment with any of the treated waters. When a commercial continuous washer was used, some bacteria remained.

Example 9 In Example 7, instead of tableware, a white robe worn for a normal time in a hospital was put in a wire netting basket and only distilled water sterilized and 0.25 wt% laundry detergent sterilized distilled water were used. I did a test. As a result, no bacterium was detected in the treated white coat in any of the treated waters. On the other hand, in the case of using an ordinary washing machine, the presence of a considerable amount of bacteria was recognized, and the bleaching step was necessary to reduce the number to almost zero.

[0062]

EFFECTS OF THE INVENTION (1) The present invention is characterized in that a series of processing steps can be carried out 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 water washing tank, a plating tank, and a water washing tank to perform the treatment. Therefore, the treatment liquid in the previous stage is mixed in the next washing tank and contaminates the water in the washing tank.
There was a need to provide a plurality of individual items. In this way, in the conventional method, by arranging many tanks,
Although the time required for changing the liquid can be saved, a large number of tanks must be provided, so that the installation area becomes large and the cost is inevitable. On the other hand, in the present invention, the combined use of vibration stirring and rotation requires much shorter processing times (for example, the number of washings) and processing time than the conventional method, and therefore, the liquid replacement time is added in the present invention. However, the overall processing time is rather shortened. Moreover, since the number of tanks is one, the cost of the apparatus is low, and the area occupied by the apparatus is significantly smaller than that of the conventional method, so that the economic effect is extremely large. Furthermore, since it is small and can be a closed type or a semi-closed type, it is advantageous when it is installed in a clean room. (2) In the present invention, when an article having very fine recesses or holes such as a semiconductor is treated with a liquid, the treatment liquid can make uniform contact with any of the fine recesses or holes. Processing can be achieved uniformly. (3) In particular, since the container containing the articles gently rotates (20 to 150 revolutions per minute) during vibration stirring, the articles do not collide with each other by dropping as in the case of barrel plating. It is possible to bring each article into contact with the treatment liquid more evenly. (4) The present invention is useful for cleaning parts having small holes such as semiconductors and electric parts, electroless plating, fireproofing of thick and finely woven fabrics, and washing. (5) The sterilizer of the present invention exhibits the following effects. (I) It was possible to provide a new sterilizing and cleaning means that does not use any chemicals. (Ii) In the present invention, when a magnetic material is used, it is convenient to remove iron powder, iron colloid, etc. mixed in water. (Iii) When a magnetic material is used, a large circulation amount of water passes through a strong magnetic field, resulting in finer water clusters and improved cleaning effect. (Iv) E. coli present in water due to the use of magnetic material,
Bacteria such as O-157, Salmonella, and Streptococcus can be captured very effectively. (V) It is extremely effective for sterilizing tableware and other related equipment in cafeterias and school lunches, and greatly contributes to the 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 in sterilization and extremely effective in preventing nosocomial infections. (Vii) Since the present invention can be carried out at room temperature, it is a technique that is extremely friendly to the global environment because it is a sterilizing means that does not deteriorate the object by heat and substantially does not use chemicals. is there. (Viii) The amount of water required for treatment can be significantly reduced.

[Brief description of drawings]

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.

FIG. 4 shows a 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 rotating shaft, (B) is a circular porous rotatable container and its rotating shaft. 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 boards in parallel at predetermined intervals.

[Explanation of symbols]

1 liquid treatment tank 2 vibration motor 3 vibrating rod 4 vibrating blades 5 lines (liquid supply system) 6 lines (drainage system) 7 Liquid supply valve 8 drain valve 9 Liquid level control switch 10 Vibration stir mechanism mounting table 11 Porous rotatable container 12 rotation motor 13 rotation axis 14 Shaft seal part (oil seal) 15 gearbox 16 Overflow mechanism 17 Printed circuit board 18 Printed circuit board fixing cradle 19 Printed circuit board fixing holder 20 Printed circuit board holder 21 Printed circuit board holder

─────────────────────────────────────────────────── ─── Continued Front Page (51) Int.Cl. ⁷ Identification Code FI 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 (58) Fields investigated (Int. Cl. ⁷ , DB name) C23G 3/00 B08B 3/10 C23C 18/16 C23C 22/73 C23F 1/08 101 C25D 17/00 C25D 21/10 H01L 21 / 304 651

Claims (12)

(57) [Claims] 1. A vibrating stirring mechanism having (A) a liquid treatment tank, (B) a vibrating motor, an inverter for adjusting the frequency of the vibrating motor, a vibrating rod connected to the vibrating motor, and vibrating blades fixed to the vibrating rod. , (C) a porous rotatable container for containing an article to be treated with a liquid, and (D) the porous rotatable container of (C) above, in (a) a liquid containing 500 r.p.m. p. Inverter for low speed specification to rotate the rotation axis vertically at a low speed of less than m and (b) 500 r. p. A rotary motor, which is connected in a switchable manner to a high-speed specification inverter for centrifuging the processing liquid by rotating the rotary shaft at a high speed of m or more, (E) (a) rubber plate or soft A vibration absorbing means which is a plate-like body selected from the group consisting of a laminated body of rubber and hard rubber and (b) a laminated body of a rubber plate and a metal plate, and which covers the entire upper surface of the liquid treatment tank; A liquid processing apparatus having: 2. A liquid introduction valve, a liquid discharge valve, a valve for switching the type of liquid, a vibration stirring mechanism of the (B) and a porous rotatable container of the (C) at a low rotational speed,
The liquid treatment apparatus according to claim 1, further comprising a timer for operating a switching mechanism for switching between three stages of high speed and stop 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 comprises (i) at least one sterilizing metal and / or The liquid according to any one of claims 1 to 4, which has a sterilizing metal compound-containing surface layer, and / or (ii) the vibrating blade and / or the fixing member for the vibrating blade generates a magnetic force. A sterilizer, which is a processing device. 6. The sterilizer according to claim 5, wherein the bactericidal metal contains an element selected from the group consisting of Ag, Au and alloys thereof. 7. The sterilizer according to claim 5, wherein the bactericidal metal compound is a metal oxide selected from the group consisting of TiO ₂ and ZnO. 8. A surface treatment method, wherein a series of respective steps for cleaning treatment of an article are continuously carried out by using the liquid treatment apparatus according to any one of claims 1 to 4. 9. A surface treatment method using the liquid treatment apparatus according to any one of claims 1 to 4, wherein a series of respective steps for subjecting an article to surface treatment are continuously carried out. 10. The surface treatment includes cleaning [including pretreatment for plating (such as degreasing), posttreatment and washing], electroplating, electroless plating, anodic oxidation, chemical polishing, electrolytic polishing,
The surface treatment method according to claim 9, which is one of etching, chemical conversion film formation treatment, and fiber processing. 11. A vibrating blade of the sterilizer according to claim 5, which is connected to a vibrating motor by an inverter.
A desired vibration between 500 Hz is generated, and this vibration is transmitted to the vibrating blade through the vibration stress dispersion means and the 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, which comprises vibrating at 0 to 1000 times / minute. 12. The sterilization method according to claim 11, wherein the water in the treatment tank is flowing at a flow rate of 100 mm / sec or more.