JPS59193904A - Apparatus for forming thin film of polymer - Google Patents

Abstract

PURPOSE:To provide the titled apparatus consisting of a reaction vessel furnished with a plurality of discharge plasma generation tubes under specific condition and having an inlet of a plasma-polymerizable monomer attached to each generation tube, and capable of forming multilayered thin polymer film in high productivity by plasma polymerization technique. CONSTITUTION:The reaction vessel 1 is evacuated with the vacuum pump 3 attached to the evacuation port 4, and carrier gases 9 are introduced into the discharge plasma generation tubes 2A-2C attached to the reaction vessel 9 inserting their open ends into the vessel. Electric potential is applied to the electrodes 7 by the high-frequency power sources 6 to generate glow discharge in the tubes, and without delay, plasma-polymerizable monomers 10A-10C are introduced into the plasma generation tubes 2A-2C through the monomer gas inlet ports 5A- 5C opened in the plasma generation tubes. At the same time, the specimen tape 13 is traversed to form thin polymer films continuously on the surface of the specimen tape in multilayers by the polymerization of the monomers 10A-10C.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to an apparatus for forming a thin polymer film using a plasma polymerization method.

Prior art A conventional plasma polymerization apparatus has a special opening/closing mechanism.
As shown in the publication, a discharge plasma generation tube (2) is installed at one end of the reaction vessel (), and a vacuum pump (3) is installed at the other end.
), and the polymerizable monomer gas inlet (5) is connected to the discharge plasma generating tube (2).
) on the outer wall of the reaction vessel (1) near the opening (see Figure 1). In this type of equipment, a high frequency power source (6)
Apply voltage to the electrode (7) from the carrier gas inlet (
A carrier gas such as argon (9) introduced from 8)
is turned into plasma, monomer gas 00) is introduced, and a thin polymer film is formed by plasma polymerization on the surface of sample 01) placed inside the reaction vessel (1), but there is only one plasma generation area. Therefore, it takes time to form a film of a certain thickness, resulting in poor productivity.

Another device is a device that forms a multilayer thin film in which each layer is made of a different monomer.
This is shown in Publication No. 03. With this equipment, it is possible to introduce multiple monomers into the 1110th reaction vessel from one introduction vibrator, or only one discharge plasma generation tube and monomer gas inlet are installed in each reaction vessel. There was no change in the fact that polymerization took a long time.

The 1/1 misfire +114 of the invention eliminates the shortcomings of the conventional apparatus as described above, and allows multilayer polymer thin films to be formed with high productivity using plasma attraction θ, regardless of the difference in mowers. The purpose is to provide a device that can be formed.

Structure of the Invention The apparatus of the non-explosion IJIj is capable of generating two or more discharge plasmas.
J'j' were placed in the reaction vessel several times so that the open IJ part of the plasma generation tube was positioned toward the inside of the reaction vessel, and each plasma generation tube was provided with a plasma polymerizable monomer gas inlet. It is characterized by this.

It is preferable that the discharge plasma generating tubes are arranged in line at regular intervals from one end of the reaction vessel toward the exhaust port at the other end. It is preferable that moving means be provided for moving the discharge plasma generating tube facing the opening of each discharge plasma generating tube.

Next, an example of the apparatus of the present invention is shown in FIG. 2, and the configuration of the present invention will be explained in more detail according to this apparatus.

In this device, an exhaust port (
4), and three discharge plasma generating tubes (2A) (2B) (2C) are provided above the reaction vessel (1).
They are installed horizontally in parallel at equal intervals.

A carrier gas inlet (8) is present at the top of each discharge plasma generating tube (2A) (2B) (2C),
) is the monomer gas inlet (5A) near the opening facing the
(5B) (5C) are provided, a carrier gas inlet (8) and a monomer gas inlet (5A) (513).
Between (5C), there is an electrode (7) connected to a high frequency power source (6). Next, inside the reaction chamber (1), there are 11 discharge plasma tubes (2A) (2F3) (2C) that are continuously moved under each discharge plasma tube (2A) (2F3) (2C) by a winding device (12). Sample Arp (13) is arranged jrx, L
has been done.

In this device, first, the inside of the reaction vessel () is brought to a pressure of 10 mm or less using the vacuum pump (3) connected to the exhaust D (4), and the gear rear gas is pumped into the discharge plasma generating tube (2A). (214) Add 10 people to each of (2C). Next, a voltage is applied from the high frequency power supply (J) to the electrode (7) to cause a glow discharge to occur. Immediately thereafter,
First, second and third plasma polymerizable monomers (IOA
) (1013) (,10C) to the inlet (5A) (5B
) (5C) respectively through the discharge plasma generating tube (
, 2A) (2B) (2C). At the same time, by winding the tape (13) with the winding device i (/ (12)), each thousand marks (IOA) are formed on the surface of the tape θ3.
(IOB) A multilayer polymer thin film can be continuously formed by polymerizing (IOC).

As IOA, IOB, and IOC, different monomers or the same monomer may be used. In the former case, three different plateaus are formed, and in the latter case, a polymer thin film of a predetermined thickness can be obtained at a rate three times faster than in the case of one 7% raw tube. It will be done. This effect can be further enhanced by increasing the number of discharge plasma generating tubes (2) in the reaction vessel (1).

In addition, discharge plasma generating tubes (2A) (2B) (2C
), no plasma polymerizable monomer gas was introduced, and an inert gas or N2.
It is also possible to plasma-treat the sample by introducing a gas such as N2.02 and generating plasma.

Furthermore, when using a sample other than a tape-shaped sample, a conveyor is provided in the reaction vessel to transfer the sample to each discharge plasma generating tube (2
It is preferable to move along A) (2B) and (2C) to form a desired polymer thin film.

As the carrier gas, an inert gas such as helium, argon, or neon can be used, and as the plasma polymerizable monomer, saturated hydrocarbons such as methane, ethane, propane, and butane, ethylene, propylene, and butene can be used. , butadiene, unsaturated hydrocarbons, tetrafluoroethylene, hexafluoropropylene, perlolocyclobutane, difluoroethane, trifluoroethylene
J-1 Nitan'! Fluorine compounds of j, paratoluidine, pyridine, vinylpyridine (, suno, ';, nitrogen compounds, isocyanate compounds such as tolylene-2,4-diisocyanate, hexamethylene diisocyanate,
Compounds with ethylenically unsaturated bonds such as styrene, α-methylstyrene, acrylonitrile, methyl acrylate, methyl methacrylate, glycidyl methacrylate-1.
, 2-hydroxymethacrylate, n-butyl acrylate, acrylic compounds, vinyltrimethoxysilane, tetramethylsilane, tetraethoxysilane, tetramethoxysilane, hexylmethyldisilane, octamethyltridiV-nocan-taku orcassilane compounds, etc. 1: IJIf or i; t 2 , iJl or -1
A fjj11 compound of Yu can be used.

Example A Ni-Co vapor deposition tape (1
3) as a sample, and after reducing the pressure inside the reaction vessel () to 10°C using the vacuum pump (3), the argon gas was poured into three discharge plasma generating tubes (2A) (2B) (2).
C) 20 ml (STP)/min each
The pressure inside the reaction vessel (1) was maintained at 0.3 mHP. Next, a high frequency voltage of 1'3.56 MHz was applied to each electrode (A) to cause glow discharge. Immediately thereafter, 30 ml (STP)/mi of vinyltrimethoxysilane was added to the first discharge plasma generating tube (2A).
20 rue (STP
)/min Tetrafluoroethylene was introduced into the third discharge plasma generating tube (2C).
TP)/minte was introduced. At the same time, the vapor deposition tape 03) is rolled up at 2 c1n/m using the winding device (12).
A thin polymer film was formed on the vapor deposition surface of the tape (13) by winding it up at a speed of i n. The dynamic M friction coefficient of the vapor-deposited tape on which the polymer thin film was formed in this way was as small as 0.4, and the running properties of the tape were significantly improved compared to the untreated tape (dynamic friction coefficient of 0.7).

Moreover, vinyltrimethoxysilane is used to form a base film with good adhesion, and tetrafluoroethylene is plasma polymerized on top of the base film to form a protective film! i = When forming, in order to improve the adhesion between the base film and the protective film, an intermediate layer is formed by plasma polymerizing a mixture of both gases, so the distance between the base film and the protective film + I) 11 is excellent. Moreover, it was possible to obtain a vapor-deposited tape having a thin polymer film with a small coefficient of dynamic friction and less wear. In this example, compared to the case where a conventional apparatus (FIG. 1) was used, the time for forming a polymer film could be shortened to about 1, and production costs could be reduced by a portion.

In addition, in the examples, the pressure inside the reaction container was 0.3 mm,
H9 was used, but polymerization is possible in the range of 0.05 to 5 vulb L (p. In addition, the flow rate of argon gas or the flow rate ffi of plasma polymerizable monomers is shown in the example (limited to 11:j). It can be adjusted according to the output power and the winding speed of the vaporized 1:t1 tape.For plasma generation 4'4, use 2 or more tapes by adding 1+j1 to the size of the reaction vessel. Any number of wires can be attached, and each can have a different size and shape.

Different carrier gases can be used to introduce each discharge plasma generating tube, and it is also possible to introduce only plasma polymerizable monomer gas without introducing carrier gas into some of the multiple discharge plasma generating tubes. It is.

Effects of the Present Invention In the present invention, two or more discharge plasma generation tubes are attached to the reaction vessel, and each discharge plasma generation tube is provided with a plasma polymerizable monomer gas inlet. It becomes possible to form a thin polymer film, significantly shortening the time for forming a polymer film, and lowering production costs. Further, the apparatus of the present invention is suitable for automation of production processes, and enables the formation of thin films with good productivity and performance, particularly in the formation of multilayer polymer thin films using different types of monomers.

[Brief explanation of the drawing]

Figure 1 is an explanatory diagram of the conventional device ζ[, Figure 2 is the unexploded
It is an explanatory view showing an example of the device. C))・・・・・・・・・・・・Reaction container (2)
(2A) (zn) (2C)・・・・・・・・・・・・
・・・・・・Plasma generation tube (:8)・・・・・・・・・
・・・・・・Vacuum pump (4)・・・・・・・・・・・・
...Exhaust port (5) (5A) (511) (5C)...
・・・・・・・・・・・・・・・ Monomarcus inlet (1j) ・・・・・・・・・・・・・・・High frequency radio waves (
7)・・・・・・・・・・・・ Electrode (8)・・・
......Carrier gas introduction IIJ (!
) Door・・・・・・・・・・・・・・・Gear rear gas (+o
) (1oA) (1on) (toc)・・・・・・・・・
......Monomer gas (1))...
......Sample (12)...
... Winding device (13) ......
... Tape patent applicant Matsushita Electric Industrial Co., Ltd. Representative Ken Minoru Arata 1 external person

Claims (2)

[Claims] (1) Place two or more discharge plasma generation tubes into the reaction vessel so that the openings of the plasma generation tubes are positioned toward the inside of the reaction vessel, and place the plasma inside each plasma generation tube. A polymer thin film forming apparatus characterized in that a polymerizable monomer gas introduction [21] is provided. (2) %J1 characterized in that several moving means are provided inside the reaction vessel for moving the sample on which the polymer thin film is to be formed through the opening of each discharge plasma generation shield.
Scope of Purpose Item 1. The polymer thin film forming apparatus according to item 1.