JPH04116156A - Method for using functional film producing apparatus - Google Patents

Abstract

PURPOSE:To eliminate the deterioration in the property of a film surface and the contamination by impurities and to form a stable functional film by transferring a material to be treated between a sputtering chamber and a polymerizing chamber while maintaining a vacuum state and executing sputtering and polymn. treatment. CONSTITUTION:After the base material 25 to be treated is set in transfer mechanisms 31, 32 of preparing chambers 12, 13, a vacuum chamber body 11 is evacuated and a sputtering treatment is executed to remove the impurities. The base material 25 is sputtered in the sputtering chamber 15 after the cleaning of the above-mentioned base material 25, etc., ends to form the thin film on the base material 25. the base material 25 is in succession transferred into the polymerizing chamber 14 where a plasma treatment is executed to form the polymerized film on the surface.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a method of using a functional membrane manufacturing apparatus, and in particular to a method for modifying a porous polymer membrane made of polypropylene, polyvinylidene fluoride, etc., and The present invention relates to a method of using a functional film manufacturing device to form an antibacterial film.

[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 techniques for improving the surface of such existing porous polymer membranes by processing them by various methods, that is, techniques for improving the functionality of the material surface, have become very popular. For example, a plasma graft polymerization device is used for hydrophilic treatment of hydrophobic porous membranes. 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, at the time of starting polymerization, it is necessary to remove impurities such as adsorbed molecules contained on the membrane surface that interfere with polymerization in advance. After this, in order to react monomers capable of chain polymerization to form a graft polymer layer with graft chains, plasma gas is supplied and vacuum plasma discharge is performed. Alternatively, it is necessary to suppress the generation of contaminating impurities in a vacuum, including in the machinery for transporting the film, 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. Further, plasma polymerization is also performed to form a polymerized film on a porous membrane film, and the circumstances before treatment are the same in this plasma polymerization as well.

On the other hand, in order to impart antibacterial effects to such a porous membrane film, a sputtered membrane may be formed on the surface of the porous membrane film using a sputtering device before the above-mentioned polymerization. In this sputtering as well, the circumstances before treatment are the same as in the case of graft polymerization. usually,
The order of this process is often to form a metal film, such as silver, on a porous membrane film by sputtering, and then to perform plasma graft polymerization.

[Problem to be solved by the invention]

However, conventionally, the sputtering device and the graft polymerization device are separate devices, so after sputtering, the processed porous membrane film is taken out of the sputtering device into the atmosphere, and then set in the graft polymerization device. Must be in a vacuum. For this reason, during this time, there was a risk that the surface of the porous membrane film would undergo deterioration or be contaminated with impurities. Furthermore, it takes a lot of time to take it out into the atmosphere and set it up again each time.

Furthermore, depending on the processing method, the same process may be repeated by repeating both processes alternately or by changing the parameters of each process, but in such cases, the problem of increasing these inconveniences is that there were.

The present invention was made in view of such problems, and its purpose is to transport a base material such as a porous membrane film in an arbitrary direction between a sputtering chamber and a graft polymerization chamber while maintaining a vacuum state, How to use functional film manufacturing equipment that can perform sputtering and plasma polymerization processes in a short time, and that can produce stable functional films without the risk of deterioration of the film surface or contamination with impurities. It is about providing.

[Means to solve the problem]

A method of using the functional film manufacturing apparatus according to the present invention includes a vacuum chamber body having a pair of preparation chambers inside, a polymerization chamber and a sputtering chamber, an exhaust means for evacuating each chamber in the vacuum chamber body, and a cover. a transfer mechanism that reciprocally transports the substrate to be treated between the preparation chamber, the polymerization chamber, and the sputtering chamber; A method for using a functional film manufacturing apparatus comprising a polymerization means for forming a polymerized film on the surface of a substrate, and a sputtering means provided in the sputtering chamber for forming a sputtered film on the surface of a substrate to be treated, the method comprising: After cleaning the surface of the substrate to be processed by creating a vacuum atmosphere in the preparation chamber using an exhaust means and performing plasma discharge, the substrate to be processed is transported by the transfer mechanism, and polymerization and polymerization by the polymerization device are performed. At least one of the sputtering processes is performed by the sputtering means.

According to this method, the substrate to be treated is cleaned in a preparation room with a vacuum atmosphere, and water and contaminants adsorbed in the atmosphere can be reliably removed, allowing processes such as polymerization to be carried out. It can be done stably.

Further, in the method of using the functional film manufacturing apparatus according to the present invention, before cleaning the substrate to be treated, the inside of the vacuum layer body is further cleaned by plasma discharge. It is possible to reliably prevent contamination of the base material.

〔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 this vacuum chamber body 1
Preparation chambers 12 and 13 are provided on both sides of the interior of 1, and a graft polymerization chamber 14 is provided between these preparation chambers 12 and 13.
and a sputtering chamber 15 are provided adjacent to each other. Preparation room 12.13, graft polymerization room 14 and sputtering room 1
5 are provided with exhaust ports 16a, 16b, 17a, and 17b connected to vacuum pumps (not shown), respectively, to exhaust the inside of the vacuum chamber body 11. The degree of vacuum is preferably a high vacuum atmosphere of 10-' Torr or less, and the vacuum pump is preferably a dry pump such as a turbomolecular pump or a talio pump to prevent contamination with hydrocarbons.

A graft polymerization device 18 is provided in the graft polymerization chamber 14 . This graft polymerization device 18 includes a flat plate electrode 19
．． 20, has a trigger electrode 21, a plasma gas inlet 22, and a polymerization monomer inlet 23, and generates plasma discharge between the plate electrodes 19 and 20 by a power source 24 provided outside the vacuum chamber body 11. A graft polymer film is formed on the outermost surface of a porous membrane film 25 of a substrate to be treated, for example, polypropylene. The main parameters of plasma graft 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 Argon (Ar) is supplied as an inert gas for plasma from the plasma gas inlet 22, and monomer inlet 23 for polymerization.
A gas necessary for graft polymerization, such as methoxyethyl acrylate (MEA), is supplied from the reactor. The purpose of introducing argon gas is not only to dilute the supply gas for graft polymerization, but also to expose the porous membrane film 25 to argon plasma discharge to perform plasma cleaning of the membrane surface. In addition, when changing the gas in graft 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. Reduce interference due to residual components as much as possible.

(2) Supplied gas flow rate The flow rate of the gas used for graft polymerization is accurately controlled by a mass flow controller (MFC). The mass flow controller is disposed between the vacuum chamber main body 11 and a gas cylinder (not shown), and a heater provided in the flow path detects the amount of heat taken away depending on the amount of gas flowing through a change in resistance value, and always keeps this value constant. Adjust the gas amount using methods such as

(3) Discharge operation pressure Argon is supplied from the plasma gas inlet 22, and a gas necessary for graft 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 Torr, and the main pump for vacuum evacuation at this time is a mechanical booster pump (MBP) that has a large evacuation capacity within this range. 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 an anode electrode 27 and a cathode electrode 28 opposite thereto, and a target 29 made of, for example, silver (Ag) is disposed on the cathode electrode 28 side. The installed power source 30 generates plasma discharge between the anode electrode 27 and the cathode electrode 28 to sputter the target 29, thereby forming a thin silver film on the surface of the porous membrane film 25 to provide antibacterial properties. It is intended to have the following. 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 an aluminum bobbin 33 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 includes the guide roller 3
8 rotatably supported by a shaft 41, and rotatably supported by a support member 43 at the center thereof by a shaft 42; a weight 45 attached to the other end of this arm 44; Consisted of. This tension control mechanism 40 sets the tension of the moving porous membrane film 25 using a weight 45, and detects the magnitude using a tension arm 44. The torque of a hack tension motor (not shown) is automatically adjusted so that the tension of the film 25 is always constant.

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 10 (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 motor 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 graft polymerization chamber 14 and the sputter chamber 15, between the graft polymerization chamber 14 and the preparation chamber 12, and between the sputter 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. cleaning has become 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 of the porous membrane film 25, argon plasma treatment is performed in the sputtering chamber 15 while the porous membrane film 25 is wound up by the winding/unwinding mechanism 31, 32. to accelerate 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. In the sputtering chamber 15 , silver is sputtered to form an antibacterial silver thin film on the surface of the porous film 25 . Subsequently, this porous membrane film 25 is transferred to the graft polymerization chamber 14, where a graft polymer membrane is formed on its surface by plasma discharge. Thereafter, this porous membrane film 25 is wound up by the winding/unwinding mechanism 31 on the side of the preparation room 13, and then taken out to the outside.

In the functional film manufacturing apparatus of this embodiment, the porous membrane film 25 is used in the sputtering chamber 15 as described above.
After forming a thin silver film on the surface of the porous film 25, the porous membrane film 25 can be transferred to the graft polymerization chamber 14 while maintaining a vacuum to perform graft polymerization without taking it out into the atmosphere. can be performed continuously in a short period of time.

In addition, there is no risk of deterioration of the membrane surface or contamination with impurities, and it is possible to stably produce a functional membrane that has antibacterial properties and is hydrophilic.

In the above embodiment, the processing in the sputtering chamber 15 is performed first, and then the processing in the graft polymerization chamber 14 is performed, but this order is arbitrary, and the winding/unwinding mechanism 31. 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.

Further, in the above embodiment, a partition wall 46 is provided between the graft polymerization chamber 14 and the sputtering chamber 15, but this is not essential, and the graft polymerization and sputtering processes are performed in the same room. It is also possible to have a configuration in which each of these steps is performed.

Further, in the above embodiment, the porous membrane film 25 of polymer was used as the substrate to be treated, but it is not limited to a film-like material, and may be thread-like, tube-like, etc.
Furthermore, it is also possible to use a metal film such as an aluminum foil or a steel plate.

Furthermore, in the above embodiments, an apparatus for performing sputtering and plasma graft polymerization was explained as an example.
By continuing plasma discharge during the polymerization process, it is also possible to perform plasma polymerization of propylene hexafluoride, equune tetrafluoride, ethane trifluoride, allylamine, etc., and thereby perform both sputtering and plasma polymerization processes. The device can be realized.

〔Effect of the invention〕

As explained above, according to the method of using the functional film manufacturing apparatus according to claim 1, the surface of the substrate to be treated is cleaned by creating a vacuum atmosphere in the preparation chamber by the exhaust means and by performing plasma discharge. After that, the polymerization and sputtering processes are performed, so that the water and contaminants adsorbed in the atmosphere can be reliably removed from the treated substrate before the treatment, so the polymerization and sputtering can be performed stably. be able to.

Further, according to the method for using the functional film manufacturing apparatus according to claim 2, the inside of the vacuum layer main body is further cleaned by plasma discharge before cleaning the substrate to be treated. It is possible to reliably prevent contamination of the base material.

[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 body 12.13...Preparation chamber 14...Graft polymerization chamber 15...Sputtering chamber 16a, 16b, 17a, 17b...Exhaust port 18
... Graft polymerization device 25 ... Porous membrane film 26 ... Sputtering device 31, 32 ... Winding/unwinding mechanism 40 ... Tension control mechanism 46 to 48 ... Partition plate 49 ... ·Aperture. applicant

Claims (2)

[Claims] 1. A vacuum chamber main body having a pair of preparation chambers therein, a polymerization chamber and a sputtering chamber, an exhaust means for evacuating each chamber in the vacuum chamber main body, and a substrate to be processed in the preparation chamber, polymerization chamber and sputtering chamber. a transfer mechanism that allows reciprocating movement between the two, and a polymerization means that is provided in the polymerization chamber and forms a polymer film on the surface of the substrate by irradiating the substrate with plasma and polymerizing the substrate. A method of using a functional film manufacturing apparatus including a sputtering means provided in the sputtering chamber and forming a sputtered film on the surface of a substrate to be processed, the method comprising: creating a vacuum atmosphere in the preparation chamber by an exhaust means; After cleaning the surface of the substrate to be treated by performing plasma discharge, the substrate to be treated is transported by the transfer mechanism, and at least one of polymerization by the polymerization means and sputtering by the sputtering means is performed. A method of using a functional membrane manufacturing device characterized by the following. 2. 2. The method of using the functional film manufacturing apparatus according to claim 1, further comprising cleaning the inside of the vacuum layer body by plasma discharge before cleaning the substrate to be processed.