JPH04110328A - Method and apparatus for preparing functional film - Google Patents

Abstract

PURPOSE:To prepare the title film having plasma polymn. layers having uniform quality without being accompanied by staining or quality degradation by cleaning a film, conveying the cleaned film, and forming plasma polymn. layers on both surfaces of the cleaned film, each step being conducted under specified conditions. CONSTITUTION:After both surfaces of a film (e.g. a porous PP film) are cleaned simultaneously in vacuo pref. by vacuum plasma discharge, the cleaned film is conveyed in vacuo to a position, where plasma polymn. is conducted in vacuo, thus forming plasma polymn. layers (e.g. by feeding methoxyethyl acrylate under Ar plasma discharge to polymerize) on both cleaned surfaces simultaneously.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a method for producing a functional film-like material and an apparatus for producing the same, and in particular, the present invention relates to a method for producing a functional film-like material and an apparatus for producing the same. The present invention relates to a method for producing a functional film-like product formed by forming layers and an apparatus for producing the same.

[Conventional technology]

Porous polymer membranes have many advantages such as operability and economy, and are therefore used in many fields as membranes for substance separation such as filtration and dialysis.

By the way, in recent years, processing technology that improves the surface of existing porous polymer membranes by processing them using various methods, that is, technology that improves the functionality of the material surface, has become very popular. Ta. For example, a plasma polymerization device or a plasma graft polymerization device is used for hydrophilic treatment of a hydrophobic porous membrane. In plasma graft polymerization, the presence of molecules or radicals that serve as polymerization initiation sites on the outermost surface of a porous polymer membrane made of polypropylene, polyvinylidene fluoride, or the like is important. Therefore, when starting polymerization, it is necessary to remove in advance impurities that interfere with polymerization, such as adsorbed molecules contained on the membrane surface. Also, after this,
In order to react monomers capable of chain polymerization and form a plasma-quenched plasma-polymerized layer, plasma gas is supplied and vacuum plasma discharge is performed. It is necessary to suppress the generation of contaminant impurities in a vacuum, including in machinery, as much as possible. In general, porous membrane films such as polypropylene are often left in the atmosphere before treatment, and conventionally, during polymerization, they are placed in a vacuum chamber and evacuated to remove water and various other substances adsorbed in the atmosphere. Contaminants are removed.

By the way, when forming plasma polymerized layers on both sides of such a porous membrane film, the conventional method is to plasma-treat one side, then return the inside of the device to atmospheric pressure and turn the porous membrane film over. There is a method in which the other side is treated again, and a method in which two sets of electrodes for plasma polymerization are installed alternately and one side of the porous membrane film is treated at different positions.

[Problem to be solved by the invention]

However, in the conventional method described above, in the former case, the porous membrane film is once taken out of the apparatus and comes into contact with the atmosphere, which may cause the porous membrane film to deteriorate or become contaminated. In particular, base materials such as synthetic polymers and natural polymers have a large amount of dissolved impurities (gas and moisture) in the base material, and conventional methods that rely on vacuum evacuation to remove impurities are difficult to achieve in a short time. This has often been a problem as it may not be possible to remove the water sufficiently. Also,
Due to these impurities and the decomposed gas of the base material generated during sputtering, it has been difficult to form a homogeneous sputtered film efficiently and at a high speed, or to form a highly pure thin film. On the other hand, in the latter method, since the sputtering is performed at different positions, a homogeneous film may not be obtained on both surfaces. There is also the problem that it is not economical because the capacity of the device increases and the number of electrodes and power sources increases.

The present invention was made in view of these problems, and its purpose is to form a homogeneous plasma polymerized layer on both surfaces of a film-like object to be processed in a short time, and to prevent the film-like object from being processed during processing. There is no contact with the atmosphere, there is no risk of deterioration of the membrane surface or contamination with impurities, and it is possible to produce stable functional film-like materials.Moreover, there is no need to increase the capacity of the equipment, making it economical. Another object of the present invention is to provide a method for producing an excellent functional film-like material and an apparatus for producing the same.

[Means to solve the problem]

The method for producing a functional film-like material according to the present invention includes a step of simultaneously cleaning both surfaces of the film-like material to be treated in a vacuum atmosphere, and plasma polymerization in the vacuum atmosphere. A step of simultaneously forming a plasma polymerized layer on both surfaces of the treated film-like object, and a step of maintaining the film-like object to be treated in a vacuum atmosphere between the position where the cleaning is performed and the position where the plasma polymerization is performed. and a step of transferring.

In this method, the processes of cleaning, transferring, and plasma polymerization of the film-like material to be processed are performed continuously in a vacuum atmosphere, so that the film-like material to be processed does not come into contact with the atmosphere between each step. , thus causing deterioration of the membrane surface,
Not contaminated by impurities.

Moreover, since plasma polymerized layers are simultaneously formed on both surfaces of the film-like object to be treated, a homogeneous film can be obtained.

Furthermore, the method for producing a functional film-like product according to the present invention includes:
The cleaning of the film-like object to be processed is performed by vacuum plasma discharge.

According to this method, not only impurities such as adsorbed molecules on the surface of the film-like object to be treated are removed, but also surface decomposition (etching) and formation of a crosslinked structure are promoted.

Therefore, gas released due to decomposition of the substrate during plasma polymerization is reduced, and the plasma polymerization rate, purity of the plasma polymerized layer, and adhesion to the substrate are improved. Further, by simultaneously cleaning both surfaces by plasma discharge, impurities dissolved in the base material can be removed more efficiently than when cleaning is performed on one side.

Furthermore, the apparatus for producing a functional film-like product according to the present invention includes:
A vacuum chamber main body having at least a pair of preparation chambers and a plasma polymerization chamber therein, an exhaust means for evacuating each chamber in the vacuum chamber main body, and a film-like material to be processed between the preparation chamber and the plasma polymerization chamber. The present invention includes a transfer mechanism capable of reciprocating movement, and double-sided plasma polymerization means provided in the plasma polymerization chamber to simultaneously form a plasma polymerization layer on both surfaces of the film-like object to be processed.

With this device, the film-like material to be processed can be freely transferred in both directions between the preparation chamber and the plasma polymerization chamber.
Cleaning and plasma polymerization processes can be performed stably. In addition, since plasma polymerization is simultaneously performed on both surfaces of the film-like object to be treated, there is no need to alternately arrange electrodes, which reduces the capacity of the apparatus and is economical.

〔Example〕

Hereinafter, the present invention will be described in detail with reference to the drawings.

FIG. 1 shows the internal structure of a functional film manufacturing apparatus according to an embodiment of the present invention, and FIG. 2 shows its external structure. In the figure, 11 is a vacuum chamber body, and preparation chambers 12 and 13 are provided on both sides of the vacuum chamber body 11, respectively, and a plasma polymerization chamber 14 and a sputtering chamber 15 are located between these preparation chambers 12 and 13. Located adjacent to each other. Exhaust ports 16a, 16b, 17a, and 17b connected to vacuum pumps (not shown) are provided at the bottoms of the preparation chambers 12, 13, the graft polymerization chamber 14, and the sputtering chamber 15, respectively, to exhaust the inside of the vacuum chamber body 11. It looks like this. The degree of vacuum is preferably a high vacuum atmosphere of 10-6 Torr or less, and the vacuum pump is as follows:
In order to prevent contamination by hydrocarbons, it is preferable to use a dry pump such as a turbomolecular pump or a cryopump.

A plasma polymerization device 18 is provided in the plasma polymerization chamber 14 . This plasma polymerization device 18 includes a flat plate electrode 19
．． 20, which has a trigger electrode 21 and two monomer introduction ports 23 for polymerization, and generates plasma discharge between the flat electrodes 19 and 20 using power supplies 24a and 24b provided outside the vacuum chamber body 11 to produce a film to be processed. Plasma polymerized layers are formed on both surfaces of a porous membrane film 25 made of, for example, polypropylene. Note that high frequency waves are supplied from a power source 55 to the power sources 24a and 24b through matching boxes 54, respectively. The main parameters of plasma polymerization are the type and flow rate of the supply gas, the discharge operating pressure, etc., and the apparatus must be able to independently control these parameters. Precise control of these parameters is performed in the following manner.

(1) Supply gas Plasma gas inlet 2 in the spuck chamber 15 (described later)
Arbon (Ar) as an inert gas for plasma from 2.
, gas necessary for plasma polymerization, such as methoxyethyl acrylate (ME
A). The purpose of introducing argon gas is not only to dilute the supply gas for plasma polymerization, but also to expose the porous membrane film 25 to argon plasma discharge to clean the membrane surface. In addition, when changing the gas in plasma polymerization, argon plasma discharge is performed without setting the porous membrane film 25, and the walls of the vacuum chamber and various devices in the vacuum are cleaned to remove foreign gases and reaction products. To reduce interference caused by residual components of objects as much as possible.

(2) Flow rate of supply gas The flow rate of the gas used for plasma polymerization and plasma graft polymerization is controlled more accurately by a mass flow controller (MFC). The mass flow controller is the vacuum chamber body 11
A heater installed in the flow path and a gas cylinder (not shown) detects the amount of heat taken away depending on the amount of flowing gas by the change in resistance value, and adjusts the amount of gas so that this value always becomes the set value. Adjust. When plasma polymerizing both surfaces of the porous membrane film 25 at the same time, the polymerization gas is supplied from the two polymerization monomer inlets 23 simultaneously. Furthermore, by supplying different gases from the two polymerization monomer inlets 23, different functions can be imparted to both surfaces of the porous membrane film 25.

(3) Discharge operation pressure Argon is supplied from the plasma gas inlet 22, and a gas necessary for plasma polymerization, such as methoxyethyl acrylate, is supplied to the vacuum chamber body 1 from the polymerization monomer inlet 23.
It is necessary to maintain a constant pressure and perform plasma discharge while flowing into the chamber. Normally, the operating pressure is 0.01 to several To
rr, and the main pump for vacuum evacuation at this time is a mechanical booster pump (M
BP) is used. Maintaining this pressure constant is related to the gas flow rate, and the gas flow rate is adjusted by providing a variable opening valve (conductance valve) in the exhaust system and adjusting the conductance.

On the other hand, a parallel plate type sputtering device 2 is provided in the sputtering chamber 15.
6 are arranged. This sputtering device 26 has two plasma gas introduction ports 22 provided close to each other above and below the porous membrane film 25, and electrodes 27, 27b provided vertically and facing each other. These electrodes 27.
The target 27b is made of silver (Ag), for example.
．． 29 is disposed, and electrodes 30a and 30b disposed outside the vacuum chamber body 11 generate a high-frequency plasma discharge between the electrodes 27a and 27b, thereby sputtering both surfaces simultaneously by targets 28 and 29. conduct,
As a result, a thin silver film is simultaneously formed on both surfaces of the porous membrane film 25, thereby imparting antibacterial properties.

Note that high frequency waves are supplied to the electrodes 30a and 30b from a power source 57 via a matching box 56, respectively. The rest of the configuration is the same as that of the plasma polymerization chamber 14, so a description thereof will be omitted.

Each of the preparation rooms 12 and 13 has a pair of winding/unwinding mechanisms 3.
1.32 is installed. One winding/unwinding mechanism 31
is composed of a bobbin 33 made of aluminum or the like for winding the porous membrane film 25, and guide rollers 34 and 35 for guiding the porous membrane film 25. The other winding/unwinding mechanism 32 includes a bobbin 36, guide rollers 37, 38, 39, and a tension control mechanism 40.

The tension control mechanism 40 rotatably supports the guide roller 38 by a shaft 41, and a shaft 42 at the center thereof.
The tension arm 44 is rotatably supported by a support member 43, and a weight 45 is attached to the other end of the arm 44.

This tension control mechanism 40 controls the porous membrane film 2 while it is running.
5 is detected by the tension arm 44, and the torque of the pack tension motor (not shown) is automatically adjusted so that the angle of the tension arm 44 with respect to the permanent direction, that is, the tension of the porous membrane film 25, is always constant. It is to be adjusted to.

Further, the running speed of the porous membrane film 25 is an important parameter that determines the exposure time to plasma.

This running speed is arbitrarily selected within the range of 1 to lQ (mm/m1n). Detection of the traveling speed is performed by an encoder (not shown) attached coaxially with the guide roller 35. The output of this encoder and the set value of the morph drive circuit are constantly compared and fed back, so that the porous membrane film 25 is transported at a constant speed.

Partition plates 46 as partition means are provided between the plasma polymerization chamber 14 and the sputtering chamber 15, between the plasma polymerization chamber 14 and the preparation chamber 12, and between the spuck chamber 15 and the preparation chamber 13.
．． 47 and 48 are provided, and these partition plates 46 to 48 are provided.
48 prevents each process from affecting other processes. Windows 49 through which the porous membrane film 25 can pass are formed in each of these partition plates 46 to 48. The upper halves of the partition plates 47 and 48 on both sides can be opened and closed about the shaft 50 toward the preparation chamber 12 and 13 by means of air cylinders (not shown), respectively, so that the inside of the vacuum chamber body 11 can be cleaned. It's getting easier.

Further, an opening/closing door 52 is provided on the front surface of the vacuum chamber body 11 and is movable up and down along a rail 51.
is provided with an observation window 53.

In such a configuration, in the functional membrane manufacturing apparatus of this embodiment, the porous membrane film 25 is first placed in the preparation room 12.1.
After setting between the winding/unwinding mechanisms 31 and 32 of No. 3, the inside of the vacuum chamber main body 11 is evacuated to a vacuum state to remove water and contaminants adsorbed in the atmosphere. If it is necessary to further clean the surface, argon plasma treatment is performed in the sputtering chamber 15 while the porous membrane film 25 is being wound up by the winding/unwinding mechanism 31 to promote the removal of impurities. When the cleaning of the surface of the porous membrane film 25 is completed, the winding/unwinding mechanisms 31 and 32 are driven to transport the porous membrane film 25 to the sputtering chamber 15. Silver is sputtered in the sputtering chamber 15, and antibacterial silver thin films are simultaneously formed on both surfaces of the porous membrane film 25.

Subsequently, this porous membrane film 25 is placed in the plasma polymerization chamber 1.
4, where a plasma polymerized layer is simultaneously formed on both surfaces by plasma discharge. After that, this porous membrane film 25 is moved to the winding/unwinding mechanism 31 on the preparation room 13 side.
After being wound up, it is taken out to the outside.

In the functional film manufacturing apparatus of this embodiment, the porous membrane film 25 is cleaned in the preparation chamber 13 and the sputtering chamber 15, and the porous membrane film 25 is further cleaned in the sputtering chamber 15.
After simultaneously forming a thin silver film on both surfaces of the porous membrane film 25, the porous membrane film 25 is transferred to the plasma polymerization chamber 14 to simultaneously form a plasma polymerized layer on both surfaces of the porous membrane film 25. During these processes, the porous membrane film 25 is exposed to the atmosphere. It is not taken out and processed while maintaining the vacuum state. Therefore, a series of processes can be performed continuously in a short time.

In addition, there is no risk that the membrane surface will be altered or contaminated with impurities, and a multifunctional membrane that is antibacterial and hydrophilic can be stably produced.

In the above embodiment, the processing in the sputtering chamber 15 is performed first, and then the processing in the plasma polymerization chamber 14 is performed, but this order is arbitrary, and the winding/unwinding mechanism 31, 32 By controlling the advancing direction of the porous membrane film 25, it is possible to freely select, for example, performing only one process or repeating both processes alternately. Furthermore, in the above embodiment, a partition wall 46 is provided between the plasma polymerization chamber 14 and the sputtering chamber 15, but this is not essential, and the plasma polymerization and sputtering processes are performed in the same chamber. It is also possible to have a configuration in which each of these is performed.

Furthermore, in the above embodiments, an apparatus that performs plasma polymerization along with sputtering was described, but it is also possible to perform plasma graft polymerization by supplying a monomer for grafting after plasma discharge, and thereby perform sputtering and plasma polymerization. It is possible to realize an apparatus that continuously performs both plasma graft polymerization processes.

Further, in the above embodiment, the porous membrane film 25 was used as the film-like material to be treated, but other metal films such as aluminum foil or iron plate may also be used. Also, the film of the present invention.

The term “shaped objects” is not limited to film-like objects in the strict sense, but also filament-like objects,
This also includes tube-shaped items.

〔Effect of the invention〕

As explained above, according to the method for producing a functional film-like product as evidenced in claim 1, both surfaces of the film-like product to be treated are simultaneously cleaned in a vacuum atmosphere, and also Since a plasma polymerized layer is simultaneously formed on both surfaces of the film to be processed, the surface of the film to be processed will not be altered or contaminated with impurities, and moreover, the film will not be contaminated with impurities. A homogeneous plasma polymerized layer can be formed on both surfaces of the object.

Further, according to the method for producing a functional film-like material according to claim 2, since the film-like material to be processed is cleaned by vacuum plasma discharge, when the cleaning treatment is performed only by vacuum evacuation, Compared to this, gas released due to decomposition of the base material during plasma polymerization is reduced, and the plasma polymerization rate, purity of the plasma polymerized layer, and adhesion to the base material can be improved.

Also, it is more efficient (cleaning can be done) than when it is done on one side.

Furthermore, according to the apparatus for producing a functional film-like material according to claim 3, the film-like material to be processed can be freely transferred in both directions between the preparation chamber and the plasma polymerization chamber while maintaining a vacuum state. The cleaning and plasma polymerization processes can be performed stably. In addition, since plasma polymerization is performed simultaneously on both sides of the film-like object to be processed, there is no need to alternately arrange electrodes, which reduces the capacity of the apparatus and improves economic efficiency.

[Brief explanation of drawings]

The drawings show one embodiment of the present invention, and FIG. 1 is a longitudinal sectional view of a functional film manufacturing apparatus, and FIG. 2 is a perspective view thereof. 11... Vacuum chamber main body 12.13... Preparation chamber 14... Plasma polymerization chamber 15... Sputtering chamber 16a, 16b, 17a, 17b-... Exhaust port 18...
...Plasma polymerization device 24a, 24b...Electrode 25...Porous membrane film 26...Suba / evening device 28.29...Target 31.32...Wind-up - Unwinding mechanism 40... Tension control mechanism 46-48... Partition plate 49... Opening 55, 57... Power supply. Applicant Terumo Co., Ltd. Company Representative Patent Attorney Fuji
Part of Hiroshi Shima (and 1 other person)

Claims (1)

[Claims] 1. The cleaned film-like object can be cleaned by simultaneously cleaning both surfaces of the film-like object to be processed in a vacuum atmosphere, and by performing plasma polymerization in a vacuum atmosphere. A step of simultaneously forming a plasma polymerized layer on both surfaces, and a step of transporting the film-like object to be treated between the position where the cleaning is performed and the position where the plasma polymerization is performed while maintaining a vacuum atmosphere. A method for producing a functional film-like material, characterized by comprising: 2. The method for producing a functional film-like material according to claim 1, wherein the cleaning of the film-like material to be treated is performed by vacuum plasma discharge. 3. A vacuum chamber body having at least one pair of preparation chambers and a plasma polymerization chamber therein, an exhaust means for evacuating each chamber in the vacuum chamber body, and a film-like material to be processed being transferred between the preparation chamber and the plasma polymerization chamber. and a double-sided plasma polymerization means that is provided in the plasma polymerization chamber and forms a plasma polymerization layer on both surfaces of the film-like object at the same time. Manufacturing equipment for functional film products.