JPH06322585A - Device and method for producing metallic film laminated high polymer composite film - Google Patents

Abstract

PURPOSE:To provide a device and a method, by which a smooth, thin metallic film having strength sufficient to withstand the tension in the post process can be produced and also a composite film consisting of the metallic film and a high polymer film can be stably produced at a low cost. CONSTITUTION:In the device for producing the metallic film laminated high polymer composite film, the high polymer film 1 coated with the electrically conductive thin film 9 is fed through between the first current applying roll 2 and the rotating drum roll 3 and the surface of the conductive thin film 9 is allowed to contact with and pass through the first current applying roll 2 and then the high polymer film 1 passes through the plating solution 5 while allowing the surface of the high polymer film 1 to contact with the rotating drum roll 3. Thereafter the surface of the above conductive thin film 9 is allowed to contact with the second current applying roll 2' and then the high polymer film 1 is delivered. At the time of allowing the high polymer film 1 to pass through the device, the temp. of the film 1 is adjusted to <=50 deg.C by blowing air with the air cooling device 11 on the film 1 at a position in each of the spaces between the above electrode rolls 2 and 2' and the liquid level of the plating solution 5. At the same time, the electrolytic plating is performed on the surface of the conductive thin film 9 by applying a voltage between the above current applying rolls 2 and 2' and the anode plate 4, which is disposed in the plating solution 5 and under the above rotating drum roll 3, to laminate the metallic film 10 on the surface of the high polymer film 1.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an apparatus for manufacturing a composite film of a metal film and a polymer film used in various electronic devices and industrial equipment by an electrolytic plating method and a manufacturing method thereof.

[0002]

2. Description of the Related Art A laminated composite film of a metal and a polymer is manufactured by adhering a metal film and a polymer film manufactured by some method such as electrolytic plating or rolling. For example, Japanese Patent Application No. 53-95135 discloses a technique for producing a composite film of a metal and a polymer film by electrolytic plating.
Further, when manufacturing an extremely thin metal-polymer composite film, a dry plating method such as a sputtering method, a vacuum deposition method, an ion plating method, or the like is adopted, and generally, the thickness of the metal film is 0. 0.01 to 0.5 μm.

[0003]

As a method for producing a composite film of a metal film and a polymer film, the metal film and the polymer film obtained by the rolling method or the electrolytic plating method as described above are adhered to each other. Although there is a manufacturing method, a dedicated device is required for that purpose.

A drum roll is used when the electrolytic plating method is adopted as a method for obtaining a metal film, but in this method, the metal film is peeled immediately after deposition, and therefore the peeling force is applied to the metal film itself at the time of peeling. Not only that, tension is naturally applied in the subsequent process. Therefore, in order to obtain a thin metal film, the tension at the time of peeling should be made as small as possible in order to avoid breakage, but on the contrary, if the tension is made small, peeling itself becomes impossible. Become. From this point of view, the thickness of the metal film obtained by this conventional method has a limit of about 20 μm and cannot be further reduced.

Further, even if a metal drum roll which is stable to the electrolytic solution is used, there is a possibility that salt in the electrolytic solution, surface stains such as the residue of the metal film after peeling, and some corrosion on the surface of the drum roll. Therefore, the surface of the drum roll becomes rough every time plating is repeated. As a result, the surface roughness of the metal film as a product is increased, or the metal film cannot be peeled off. Therefore, as disclosed in Japanese Patent Application No. 53-95135, a polishing device for polishing the drum is generally arranged on the peripheral surface of the drum roll.

On the other hand, electrolytic deposition of an amorphous alloy magnetic layer on a polymer film having one or both surfaces coated with a conductive thin film is introduced, for example, in Japanese Patent Application No. 3-45186. According to the method, the electric resistance of the conductive thin film causes the polymer film to melt or deteriorate due to heat generation in the energized portion outside the plating solution, and a stable composite film cannot be obtained.

Other methods for obtaining a composite film of a metal film and a polymer film include a dry plating method such as a sputtering method, a vapor deposition method and an ion plating method. However, not only the productivity is poor but also a special apparatus is used. It becomes necessary and leads to an increase in cost.

[0008]

According to the method for producing a metal film by using a rotating drum roll as described above, not only is it necessary to adjust tension with high precision for the metal film deposited on the drum surface, but also the drum surface. It requires a polishing device for polishing, which requires extra maintenance and management. According to the above method of coating a conductive thin film on the surface of a polymer film and energizing the conductive thin film to electrolytically deposit an amorphous alloy magnetic layer, the conductive thin film outside the plating solution was coated. Heat is generated in the energized part,
There is a problem that a polymer film is melted and deteriorated, and a stable composite film cannot be obtained.

The present invention was developed in view of such circumstances, and a composite of a metal film and a polymer film, which can endure tension in the subsequent process, can obtain a smooth and thin metal film, and has a low manufacturing cost. An apparatus and method for stably producing a membrane are provided.

[0010]

In order to solve the above problems, the first gist of the present invention is to provide a metal film on a conductive thin film of a polymer film coated with a conductive thin film by a plating method. In the apparatus for producing a composite film for continuously coating, a pair of parallel energizing rolls arranged before and after the running path of the polymer film, and a large-diameter rotating drum roll installed between the energizing rolls. A plating solution tank for containing a plating solution for immersing the lower part of the rotating drum roll, a plate-like anode plate arranged in the plating solution tank so as to face the immersion circumferential surface of the rotating drum roll, and the thin film surface While contacting the pair of energizing roll surfaces, the film surface is a portion present between the energizing rolls of the polymer film and the liquid surface of the plating liquid that the film surface runs in contact with the lower peripheral surface of the rotating drum roll. Temperature below 50 ° C There to be equipped with a control means.

As a preferred mode of the temperature control means, a facing distance adjusting mechanism for adjusting the facing distance between the liquid tank and the energizing roll can be adopted, and in another form, it exists between the energizing roll and the plating liquid surface. A cooling mechanism for cooling the polymer film is used.

Further, the second gist of the present invention is that the conductive thin film surface of the polymer film coated with the conductive thin film is made to contact with the first current-carrying roll, and the film surface is then rotated. After being supplied through the plating solution while being in contact with the roll, the conductive thin film is brought into contact with the second energizing roll to be discharged, and the high film existing between the electrode roll and the surface of the plating solution when the polymer film is running. While keeping the molecular film at 50 ° C. or lower, a voltage is applied between the anode plate and the energizing roll arranged in the plating solution below the rotating drum roll to perform electroplating, and a metal film is formed on the surface of the polymer film. And a method for producing a metal film laminated polymer film composite film, which comprises laminating

[0013]

EXAMPLES Examples of the apparatus and method for producing a metal film laminated polymer film composite film of the present invention will be specifically described below with reference to the drawings.

First, referring to FIG. 1, an explanation will be given of an apparatus for producing a metal film laminated polymer film composite film of the present invention. The apparatus is provided on the surface of the conductive thin film 9 of the polymer film 1 covered with the conductive thin film 9. It is an apparatus for producing a composite film 8 that continuously coats a metal film 10 by a plating method, and a polymer film 1
First and second energizing rolls 2 and 2'before and after the traveling path of
Are arranged in parallel, and a large-diameter rotary drum roll 3 is provided between the pair of energizing rolls 2, 2 '.
It is installed in parallel with. A plating liquid tank 6 is disposed below the rotary drum roll 3, and the lower portion of the rotary drum roll 3 is immersed in the plating liquid 5 contained in the plating liquid tank 6.

An anode plate 4 is arranged inside the plating liquid tank 6 so as to face the peripheral surface of the immersed portion of the rotary drum roll 3. The anode plate 4 is a plate material provided over substantially the entire length of the rotary drum roll 3, and its shape has an arc cross section or a rectangular cross section that is concentric with the rotary drum roll 3. It is not limited to this. Then, the space between the first and second pair of energizing rolls 2 and 2'and the anode plate 4 is connected to a DC power supply 7, respectively.

When the metal film-laminated polymer film composite film 8 having the above-mentioned structure is manufactured, the polymer film 1 coated with the conductive thin film 9 is first contacted and run on the conductive thin film surface of the first conductive roll 2. Then, after supplying the film surface through the plating liquid tank 6 while contacting the peripheral surface of the rotary drum roll 3 in the portion immersed in the plating liquid 5,
The conductive thin film 9 is brought into contact with the second energizing roll 2'and discharged. While the polymer film 1 is running, the portion of the polymer film 1 running between each of the energizing rolls 2 and 2'and the liquid surface of the plating solution 5 is controlled to 50 ° C. or less,
Electrolytic plating is performed by applying a DC voltage between the anode plate 4 disposed in the plating solution 5 below the rotating drum roll 3 and the energizing rolls 2 and 2 ', and the surface of the polymer film is subjected to electrolytic plating. A metal film is laminated.

Here, when the polymer film 1 is running, the point that the polymer film 1 running between each of the energizing rolls 2 and 2'and the liquid surface of the plating solution 5 is controlled to 50 ° C. or lower is as follows. This is the most important point for the present invention. for that reason,
The metal film laminated polymer film composite film manufacturing apparatus,
Between each of the energizing rolls 2 and 2'and the liquid surface of the plating liquid 5, there is provided a temperature control means for keeping the temperature of the polymer film 1 running in the same portion at 50 ° C. or lower. As an example of the preferable temperature control means, the plating liquid tank 6 and the energizing roll 2,
A facing position adjusting mechanism (not shown) for adjusting the facing distance of 2 ', and air is directly jetted to the polymer film 1 existing between the energizing rolls 2 and 2'and the plating liquid surface for positive cooling. An air cooling mechanism can be adopted.

With respect to the polymer film 1 coated with the conductive thin film 9 supplied to the present invention having the above-mentioned structure, various materials can be selected according to the use. For example, as versatile polymers, polyolefins such as polyethylene, polypropylene, poly-4-methylpentene-1; polyvinyl chloride, polyvinyl alcohol, polyvinyl such as polyacrylonitrile, polyethers such as polyoxymethylene and polyethylene oxide. In addition, any polymer material such as polyester, polyamide, and cellulose can be used. Particularly when the metal film laminated polymer film composite film 8 produced by the present invention is used at high temperature, an aromatic polyester such as polyethylene terephthalate, an aromatic amide such as poly-p-phenylene terephthalamide, and the like. Polyimide, polysulfone, polyoxadiazole, polyether ketone, polyparabanic acid, polyphenylene sulfide, etc. are used. Further, as the low induction polymer, a fluorine-based polymer such as polyvinyl fluoride, polytetrafluoroethylene or polyvinylidene fluoride can be used. Further, in such organic polymer, glass fiber, carbon fiber,
Also included are those containing fillers such as inorganic minerals and ceramics.

The material of the conductive thin film 9 of the polymer film 1 coated with the conductive thin film supplied to the present invention is preferably stable to the plating solution. As the material, Au,
Any material such as Ag, Pt, Cu, or Ni that is stable to the plating solution may be used. The coating method is a dry plating method such as a sputtering method, a vapor deposition method and an ion plating method.
Alternatively, there is an electroless plating method which is a wet plating method, but it is not specified. However, its surface resistance is 6
Ω / cm ² or less is preferable. The thickness of the conductive thin film 9 coated with a specific polymer film varies depending on the material of the conductive thin film 9, but is 0.5 μm or less, preferably 0.
It is 1 μm or more.

As the plating solution 5 used in the present invention, various commercially available plating solutions can be used. Further, in order to form a magnetic material film of an amorphous alloy of Co, Fe, and P in the metal part, a thin and smooth amorphous alloy is prepared by using the plating solution as the solution disclosed in Japanese Patent Application No. 1-118591. A thin film can be obtained.

The material of the energizing rolls 2 and 2'used in the present invention is not particularly limited. The rotation may be free rotation or drive. The installation positions of the energizing rolls 2 and 2'need to be a sufficient distance from the plating liquid surface to suppress the temperature rise due to heat generation due to the electric resistance of the conductive thin film 9 and the metal film laminated polymer film 8 to 50 ° C or less. There is. Therefore, it is necessary to employ a facing position adjusting mechanism that can move the installation position of the energizing rolls 2, 2'or the installation position of the plating liquid tank 6.

The rotating drum roll 3 used in the present invention is driven at a constant rotation. The material of the rotating drum roll 3 is
It is preferable to use a metal or resin that is stable to the plating solution.

The temperature control means in the present invention is installed between the energizing rolls 2 and 2'and the liquid level of the plating solution 5 as shown in FIG. 1 in addition to the facing position adjusting mechanism. There is an air cooling device 11 that blows air toward the polymer film 1 running in the same portion. In the temperature control means of the present invention, the facing position adjusting mechanism or the air cooling device 11 can be adopted independently, but it is also possible to install both of them together.

The manufacturing apparatus and the manufacturing method of the metal film laminated polymer film composite film according to the present invention will be described in more detail with reference to the illustrated examples.

The conductive thin film surface 9 of the polymer film 1 coated with the conductive thin film 9 is brought into contact with the upper surface of the first energizing roll 2, and the drum roll 3 is rotated at a constant rotation speed.
The film surface is continuously brought into contact with the lower surface of the sheet to run.
Subsequently, the polymer film 1 is immersed in the plating solution 5 having a desired metal composition for a certain period of time by rotating the drum roll 3 in which a part of the peripheral surface is immersed in the plating solution 5, and the anode plate A voltage is applied to 6 and a pair of energizing rolls 2 and 2'to stack the target metal on the surface of the conductive thin film.

The metal film laminated polymer film composite film 8 from which the plating solution 5 has been discharged is discharged to the outside of the apparatus while coming into contact with the upper surface of the second energizing roll 2'again. At this time, both electrode rolls 2,
The electrode rolls 2 and 2'positions are set so that the temperature of the polymer film existing between 2'and the plating liquid surface is 50 ° C or lower, or the temperature is controlled to 50 ° C or lower by the air cooling device 11. There is. The thickness of the metal laminated film of the metal film laminated polymer film composite film 8 can be set to an arbitrary thickness by controlling the processing speed and the electrolytic plating current. The discharged composite film 8 of the metal film and the polymer film is supplied to a subsequent process such as a cleaning process, if necessary. If the metal film 10 of the composite film 8 is used alone,
The polymer film portion can be peeled off chemically or physically.

Next, the present invention will be described in more detail with reference to specific examples. (Specific Example 1) A 12 μm-thick PET film coated with Ag at 350 angstrom by the vapor deposition method was supplied to the apparatus shown in FIG. 1 for processing. The outer diameter of the rotary drum roll 3 was 240 mm, the outer diameter of each energizing roll 2, 2 ′ was 15 mm, and the arc-shaped anode plate placed on the concentric circle of the rotary drum roll 3 was made of Co. The plating solution was an aqueous solution containing Co, Fe, and P shown in Japanese Patent Application No. 1-118591, and the treatment time was 6 minutes and the current amount was 0.05 A / cm ² . The polymer film 1 existing between the liquid surface of the plating liquid 5 and each of the current-carrying rolls 2 and 2'was set to a position where the polymer film 1 was run at 50 ° C. or lower. was gotten. The thickness of the amorphous alloy thin film was 3 μm.

(Specific Example 2) PET having a thickness of 12 μm coated with Ag by vapor deposition at 350 Å
The film was fed and processed in the apparatus shown in FIG. The outer diameter of the rotating drum roll 3 is 240 mm, each energizing roll 2,
The outer diameter of 2'is 15 mm, and the material of the arc-shaped anode plate installed on the concentric circle of the rotating drum roll 3 is Co. The plating solution is Co, Fe, which is disclosed in Japanese Patent Application No. 1-118591.
Aqueous solution containing P, processing time 6 minutes, current amount 0.05
A / cm ² . Liquid level of plating solution 5 and energizing roll 2,
An air cooling device 11 was adopted so that the polymer film 1 between 2'and 50 'could be run at 50 ° C or below, and when positively cooled with cooling air, a smooth amorphous alloy thin film and PET composite film was obtained. Was given. The thickness of the amorphous alloy thin film is 3 μm.
Met.

Comparative Example Under the same conditions as in Example 1, the temperature of the polymer film 1 between the plating liquid surface and the current-carrying roll was 50 ° C.
When the traveling position was set as described above, the polymer film 1 was in a melted state and a good amorphous alloy thin film could not be obtained.

[0030]

As is clear from the above description, by using the apparatus for producing a metal film laminated polymer film laminate film of the present invention, it is possible to obtain a high productivity in spite of the production of the laminate film using a rotating drum roll. It is possible to continuously produce a thin and smooth laminated composite film of a metal film and a polymer film without damaging the molecular film.

[Brief description of drawings]

FIG. 1 is a cross-sectional view showing a schematic configuration example of an apparatus for producing a metal film laminated polymer film laminated film according to the present invention.

[Explanation of symbols]

 1 polymer film coated with conductive thin film 2 first energizing roll 2'second energizing roll 3 rotating drum roll 4 anode plate 5 plating solution 6 plating tank 7 direct current power supply 8 metal film laminated polymer film composite film 9 conductivity Thin film 10 Metal film 11 Air cooling device

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[Procedure amendment]

[Submission date] June 22, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] 0002

[Correction method] Change

[Correction content]

[0002]

2. Description of the Related Art A laminated composite film of a metal and a polymer is manufactured by adhering a metal film and a polymer film manufactured by some method such as electrolytic plating or rolling. For example, a technique for producing a composite film of a metal and the polymer film by electrolytic plating is disclosed in JP-A-53-95135.
Further, when manufacturing an extremely thin metal-polymer composite film, a dry plating method such as a sputtering method, a vacuum deposition method, an ion plating method, or the like is adopted, and generally, the thickness of the metal film is 0. 0.01 to 0.5 μm.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Name of item to be corrected] 0005

[Correction method] Change

[Correction content]

Further, even if a metal drum roll that is stable against the electrolytic solution is used, salt in the electrolytic solution, surface stains such as residuals of the metal film after peeling, and slight corrosion of the drum roll surface Therefore, the surface of the drum roll becomes rough every time plating is repeated. As a result, the surface roughness of the metal film as a product is increased, or the metal film cannot be peeled off. Therefore, as is also disclosed in JP Sho 53-95135 are arranged generally to a polishing apparatus for polishing the drum peripheral surface of the drum roll.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0019

[Correction method] Change

[Correction content]

The material of the conductive thin film 9 of the polymer film 1 coated with the conductive thin film supplied to the present invention is preferably stable to the plating solution. The material is A
Any material, such as u, Ag, Pt, Cu, or Ni, that is stable to the plating solution may be used. The coating method includes a dry plating method such as a sputtering method, a vapor deposition method and an ion plating method, or a non-electrolytic plating method that is a wet plating method, but is not specified. But its surface resistance is
It is preferably 6Ω / □ or less. The thickness of the conductive thin film 9 coated with a specific polymer film varies depending on the material of the conductive thin film 9, but is 0.5 μm or less, preferably 0.
It is 1 μm or more.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yoshihiro Sako 20-1 Miyuki-cho, Otake-shi, Hiroshima Mitsubishi Rayon Co., Ltd. Central Research Laboratory

Claims (4)

[Claims] 1. An apparatus for producing a composite film, wherein a metal film is continuously coated on a conductive thin film of a polymer film coated with the conductive thin film by a plating method, which is before and after a running path of the polymer film. And parallel first and second energizing rolls, a large-diameter rotating drum roll installed between the energizing rolls, and a plating solution tank containing a plating solution for immersing the lower part of the rotating drum roll. And a plate-shaped anode plate arranged in the plating solution tank so as to face the immersion peripheral surface of the rotating drum roll, and the thin film surface contacts the pair of current-carrying roll surfaces, and the film surface is rotated. A temperature control means for controlling the temperature of the polymer film existing between each energizing roll of the polymer film running in contact with the lower peripheral surface of the drum roll and the liquid surface of the plating solution to 50 ° C. or less. Metal film laminated polymer film Film composite film manufacturing equipment. 2. The apparatus for producing a film composite film according to claim 1, wherein the temperature control means is a facing distance adjusting mechanism that adjusts a facing distance between the liquid tank and the energizing roll. 3. The apparatus for producing a film composite film according to claim 1, wherein the temperature control means is a cooling mechanism for cooling the polymer film existing between the energizing roll and the plating liquid surface. 4. The electroconductive thin film surface of the polymer film coated with the electroconductive thin film is brought into contact with a first energizing roll, and then the film surface is fed while being brought into contact with a rotating drum roll. The conductive thin film is discharged by contacting it with a second energizing roll, and the polymer film existing between the electrode roll and the plating liquid surface is kept at 50 ° C. or lower while the polymer film is running. 2. A metal film laminated polymer film characterized by laminating a metal film on the surface of a polymer film by applying a voltage between an anode plate arranged in the plating solution and the energizing roll to perform electroplating. Method for manufacturing composite membrane.