WO1999062990A1

WO1999062990A1 - Method and apparatus for producing plasma-treated sheet

Info

Publication number: WO1999062990A1
Application number: PCT/JP1999/002772
Authority: WO
Inventors: Yoshihisa Higashida; Nobuyuki Kuroki; Kazuhiro Fukushima
Original assignee: Toray Industries, Inc.
Priority date: 1998-05-29
Filing date: 1999-05-26
Publication date: 1999-12-09

Abstract

A running sheet is treated for surface modification in a device comprising a plasma-processing region formed of an electrical discharge electrode, another electrode, and an atmosphere between these electrodes. Either or both of the two electrodes are covered with dielectric that creates capacitance per unit area in a range of 0.13-20 νF/m2. Another device comprises such a plasma processing region, and a chamber having a vent through which compressed gas is ejected to a running sheet. The chamber is provided outside the entrance to the plasma chamber that also includes an exit. Either of the above devices or the combination of the two achieves a sheet treatment speed of 20 m/min or greater, which cannot be achieved by the conventional devices.

Description

Description Plasma processing sheet manufacturing apparatus and manufacturing method Technical field

The present invention relates to an apparatus for manufacturing a plasma-processed sheet and a method for manufacturing a plasma-processed sheet manufactured using the apparatus. Background technology

Conventionally, in order to modify the surface of a resin sheet, for example, to improve the adhesiveness, hydrophilicity, or printability of the surface of the sheet, the sheet is treated in a plasma atmosphere. ing.

This processing method and processing apparatus are disclosed in Japanese Patent Application Laid-Open No. 11-38242, Japanese Patent Application Laid-Open No. 4-74525, and Japanese Patent Application Laid-Open No. 5-1160. These documents disclose the following apparatus for manufacturing a plasma processing sheet. A sheet traveling path having a discharge electrode and a counter electrode facing each other, and a sheet traveling continuously passing through a plasma processing area formed by a discharge between the discharge electrode and the counter electrode; Alternatively, a plasma processing sheet manufacturing apparatus in which at least one electrode of the counter electrode is coated with a dielectric.

Although these conventional plasma processing sheet manufacturing apparatuses continuously process a running resin sheet, Japanese Patent Application Laid-Open No. Hei 4-74525 merely shows the continuous processing apparatus in FIG. And no specific continuous processing conditions are disclosed. Japanese Unexamined Patent Publication Nos. 1-138182 and 5-1160 disclose continuous processing conditions, but only teach the traveling speed of the resin sheet as 15 m / min. .

In these conventional plasma processing sheet manufacturing apparatuses, there is a demand for improving the surface modification effect by the plasma processing and reducing the production cost by increasing the running speed of the sheet during the plasma processing.

To improve the reforming effect, the discharge used to generate the plasma It is desirable to increase the power (input power) acting between the electrode and the counter electrode. When plasma processing is performed in a specific gas atmosphere, for example, in an inert gas atmosphere, it is also desirable that the gas atmosphere be stably maintained.

To increase the running speed of the seat, it is desirable to increase the input power and maintain a stable gas atmosphere.

However, an increase in input power causes a spread of discharge, and as a result, a problem that a short circuit to a metal member near the discharge electrode is likely to occur. Under some conditions, an increase in input power has the problem that the required glow discharge state may shift to the arc discharge state.

If such a short circuit or arc discharge occurs, the processing of the sheet in a desired plasma state cannot be performed, or the discharge current generating power supply provided for adjusting the discharge current supplied to the discharge electrode is provided. An obstacle will occur, making it impossible to continue producing plasma treated sheets.

In some cases, a resonance-type power supply is used as the power supply for generating the discharge current.In such a case, the matching between the discharge part and the power supply may change depending on the discharge state. Maintenance becomes difficult. Conventional devices have this problem.

When the plasma treatment is performed in a specific gas atmosphere, the gas used is limited by itself in order to obtain the desired sheet surface modification effect and from the viewpoint of cost. Maintaining the desired gas atmosphere (concentration) is achieved by increasing the gas supply, but there is a limit to reducing the amount of gas used to reduce costs.

When the sheet is run and processed continuously, the gas flows between the inside and outside of the processing chamber to maintain a stable atmosphere inside the processing chamber at the inlet and outlet of the processing chamber where plasma processing is performed. A sealing device for minimizing the pressure is provided.

However, with the conventional sealing device, it is difficult to slightly suppress the air (entrained air) brought into the processing chamber by the high-speed sheet whose traveling speed is lower than before, and the processing chamber has a predetermined concentration of gas. It ’s difficult to keep the atmosphere You. Conventional devices have this problem. Disclosure of the invention

An object of the present invention is to solve the problems of conventional devices.

The present invention provides a plasma processing sheet manufacturing apparatus that is less likely to cause a spread of electric discharge, a short circuit, an arc discharge, and a decrease in performance in a gas atmosphere even when the input power is increased.

By the apparatus according to the present invention, it is possible to increase the processing strength of the surface modification of the sheet and to increase the production speed of the sheet whose surface has been modified.

A first aspect of a plasma processing sheet manufacturing apparatus according to the present invention for solving the above problems is as follows.

A sheet running path having a discharge electrode and a counter electrode facing each other, and a sheet running path through which a sheet continuously running in a plasma processing region formed by the discharge between the discharge electrode and the counter electrode passes; Alternatively, in a plasma processing sheet manufacturing apparatus in which the surface of at least one of the counter electrode is coated with a dielectric, the capacitance per unit area of the dielectric is from 0.13 ^ FZm ^2. 2 0 plasma-treated one Bok manufacturing apparatus is in a range of u FZm ^2.

The definition and measurement method of the capacitance per unit area C s (F / m ² ) are as follows.

Definition: C s = C / S (I)

Here, C is the capacitance (F) when a conductive plate is attached to both surfaces of the dielectric layer, and S is the area (m ² ) of the conductive plate.

Measurement method: The capacitance C with the conductive plates adhered to both sides of the dielectric layer is measured using an LCR meter (Hewlett-Packard 4284A, measurement frequency around 100 kHz). The measured capacitance C and the area S of the conductive plate used are used, and the capacitance C s per unit area is obtained by Equation I.

Electrodes coated with a dielectric having a capacitance per unit area in the range of 0.13 ^ FZm ² to 20 zF / m ² are selected according to the above definition and measurement method. The capacitance C s per unit area is preferably in the range of 0.16 zFZm ² to 4 [IFZm ² .

If the capacitance C s exceeds 20 FZm ² , concentrated discharge is likely to occur, and the discharge becomes non-uniform. When the capacitance C s is less than 0.13 zFZm ² , the spread of discharge increases, and as a result, a short circuit to a metal member near the discharge electrode is likely to occur.

The relative permittivity ε s of the dielectric covering the electrode is preferably 10 or more.

The definition and measurement method of the relative permittivity ε s of the dielectric are as follows.

Definition: ε s = D / (ε · Ε) (Π)

Here, D is the electric flux density (CZm ^2), ε is the dielectric constant in vacuum ^{(8. 85 4X 10- 12 FZm)} , E is the electric field (vzm).

The relationship between the relative permittivity ε s and the capacitance C is as follows.

ε s = Cd / (εS) (Π)

Here, d is the distance between the conductive plates (m).

Measuring method: Capacitance C of the dielectric is measured by LCR measurement (4284A, Hewlett-Packard). Measured capacitance C, the conductive plate spacing (dielectric thickness) d, the dielectric constant in vacuum ^{(8. 854 X 10 12 FZm)} , conductive plate area S is used, by the equation m, the dielectric constant epsilon s Is required. Dielectrics having a relative dielectric constant of 10 or more are selected according to the above definition and measurement method.

Preferably, the dielectric constant ε s of the dielectric ranges from about 15 to about 200. The thickness d of the dielectric is preferably in the range of 0.5 mm or more and 5 mm or less.

The dielectric is preferably barium titanate, titania, zirconia, magnesia, or yttria.

The dielectric may have a single-layer structure of barium titanate alone, but has a two-layer structure composed of an alumina layer having a relative permittivity of about 7 and a barium titanate layer having a relative permittivity of about 200. Dielectrics are preferred, and the relative permittivity of this composite dielectric is It is even more preferred to blend these dielectrics so as to be about 20 to about 25.

The counter electrode is preferably composed of one rotating roll electrode which is supported by a fixed rotating shaft and rotates in the sheet traveling direction on the traveling path, for supporting and feeding the traveling resin sheet. In this case, the running resin sheet is supported by the surface of the dielectric covering the peripheral surface of the rotating roll electrode.

In this case, the discharge electrodes are preferably arranged in a plurality of rows, and are arranged at intervals in the direction of curvature of the peripheral surface of the rotating roll electrode. It is preferable that these discharge electrodes have no coating with the dielectric.

The counter electrode is preferably connected to a grounded non-resonant power supply because the waveform of the discharge current is stable without depending on the load during plasma processing. A non-resonant power supply is a power supply that does not include a load (discharge portion) circuit in the power supply oscillation circuit, that is, a power supply that is not easily affected by the resonance frequency of the load circuit. As this non-resonant power supply, there is, for example, LF-30 manufactured by RF Power Products.

The discharge electrode may be connected to a variable frequency power supply whose frequency can be arbitrarily selected. Preferably, the frequencies used are in the range from about 5 kHz to about 10 MHz.

In the discharge electrodes provided in a plurality of columns, it is preferable that each discharge power can be controlled independently for each column.

According to the first aspect, as a dielectric for covering the discharge electrode or counter electrode, the capacitance per unit area, 0. 1 3 i the range of F Zm ² from 2 m ² is the dielectric is used In addition, since a dielectric having a relative permittivity of 10 or more is used, even if the power supplied to the discharge electrode increases, the spread of the discharge is suppressed, and the metal member near the electrode can be spread. Is prevented from being short-circuited. As a result, a larger amount of power can be supplied to the discharge electrode than in the conventional device.

In addition, when increasing the input power represented by the product of the voltage value and the current value, it is better to suppress the voltage value and increase the current value. As a result, it affects plasma processing Current density can be increased. This increase in current density results in an increase in the number of electrons. This means that the number of active particles acting on the sheet increases. This increase in the active particles increases the efficiency of sheet surface modification, and makes it possible to increase the sheet traveling speed, that is, the production efficiency of the plasma-treated sheet.

Further, in this case, since the current easily flows, arc discharge is unlikely to occur even if the input power is large, and it becomes possible to perform a good process using a single-discharge plasma.

A second aspect of the plasma processing sheet manufacturing apparatus according to the present invention for solving the above problems is as follows.

A sheet traveling path having a discharge electrode and a counter electrode facing each other, and a sheet traveling continuously passing through a plasma processing area formed by a discharge between the discharge electrode and the counter electrode; Alternatively, in a plasma processing sheet manufacturing apparatus in which the surface of at least one of the counter electrode is coated with a dielectric, a plasma chamber for substantially shielding the plasma processing area from the outside is provided. A gas supply port for supplying a gas containing a rare gas element into the chamber; and an entrance and an exit of the sheet traveling path, wherein the traveling path is provided outside the entrance of the sheet traveling path. A plasma processing sheet manufacturing apparatus provided with a gas chamber having a pressurized gas supply port for supplying a pressurized gas toward the sheet traveling path in the vicinity of an inlet of the sheet. . The rare gas elements supplied into the plasma chamber and the gas containing the same are disclosed in the above-mentioned Japanese Patent Application Laid-Open No. Hei 11-13842 or Japanese Patent Application Laid-Open No. Hei 5-116. The concentration of the rare gas element is preferably at least 20 mol%. It is preferable that argon gas be used and the oxygen concentration be kept in the range from 200 ppm to 2000 ppm.

The gas supplied from the gas supply port may be air. The flow rate is preferably in the range of about 2 m // sec to 20 m / sec.

By the flow of pressurized gas injected from the gas supply port to the surface of the resin sheet, the flow of air toward the plasma chamber accompanying the resin sheet with a high running speed This is substantially shut off.

The gas chamber having a gas supply port is provided with a gas suction port on the front side of the gas supply port with respect to the entrance of the plasma chamber traveling path, that is, on the upstream side in the traveling direction of the sheet toward the plasma chamber. Preferably, the gas suction port and the gas supply port are connected via a gas circulation means, for example, a gas blower. As a result, the flow of air toward the plasma chamber accompanying the resin sheet having a high running speed is more effectively blocked, and the gas ejected from the gas supply port is reused.

According to the second aspect, since the pressurized gas supply port for supplying pressurized gas to the traveling sheet is provided adjacent to the entrance of the traveling path, the traveling speed of the sheet is high. Air entrained by the resulting sheet into the plasma chamber is substantially prevented. As a result, even if the sheet is moving at a high speed, the inside of the plasma chamber is maintained at a desired gas atmosphere, and a stable discharge state is maintained. This means that plasma processing of a sheet traveling at a high speed is possible, that is, the productivity of the plasma processing sheet can be improved.

The object of the present invention is further achieved by the combination of the second embodiment and the first embodiment. As a result, the running speed of the resin sheet can be doubled or higher than in the past. For example, good plasma processing is stably performed while the traveling speed of the resin sheet of about 60 mZmin is maintained.

A third aspect of the plasma processing sheet manufacturing apparatus according to the present invention for solving the above problems is as follows.

In the aspect in which the rotating roll electrode is provided in the first aspect or the second aspect, in the traveling direction of the traveling sheet, the discharge electrode located at the most upstream side of the discharge electrodes in the plurality of rows is arranged. On the upstream side, and on the downstream side of the discharge electrode located at the most downstream side, a plasma confinement electrode having a discharge power smaller than that of the discharge electrode adjacent to the discharge electrode is provided on the roll of the rotating roll electrode. Plasma treatments are provided to face the surface. Production equipment for processing sheets.

The discharge power of the plasma confinement electrode is preferably in the range of about 1Z2 to about 110 of the discharge power of the discharge electrode.

The plasma confinement electrodes are provided on the upstream side and the downstream side, and further along a traveling direction of the traveling sheet along both ends in a width direction of the traveling path of a plurality of discharge electrodes. May be provided.

According to the third aspect, since the plasma confinement electrode is provided, even if the power supplied to the discharge electrode increases, the spread of the discharge is suppressed, and the short circuit to the metal member near the electrode is prevented. . As a result, a larger amount of power can be supplied to the discharge electrode than in a conventional device. ,

A method for manufacturing a plasma processing sheet according to the present invention for solving the above-mentioned problems is as follows.

A method for producing a plasma-treated sheet, wherein the sheet is run on a traveling path of the apparatus for producing a plasma-treated sheet according to the present invention, and the sheet is plasma-treated in a plasma treatment area.

In this manufacturing method, the pressure of the atmosphere in the plasma processing region may be substantially atmospheric pressure.

This production method is preferably used for producing a resin sheet subjected to plasma treatment. A specific example of the resin sheet subjected to the plasma treatment is disclosed in the above-mentioned JP-A-1-138242. This production method is particularly preferably applied to the polyimide resin sheet disclosed in the above-mentioned Japanese Patent Application Laid-Open No. 5-1160.

In this manufacturing method, the current density Cd of the plasma treatment zone is preferably at 0. l [alpha] · min eta ² or more. The definition and measurement method of this current density Cd are as follows.

Definition: Cd = I (wXv) (IV)

Here, I is the current (A) flowing through the discharge part, w is the sheet width (m), and V is the running speed of the sheet (mZ).

Measurement method: Discharge by current detection probe (CMS 25A manufactured by TDK) Current is detected by a high-speed oscilloscope (Hewlett-Packard

The current value I is measured at 5 4 5 4 0 C). The measured current value I, the sheet width w, and the running speed V of the sheet are used, and the current density C d is obtained by Equation IV. BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 is a longitudinal sectional view of one embodiment of a plasma processing sheet manufacturing apparatus according to the present invention.

FIG. 2 is a partial perspective view of one embodiment of a discharge electrode in the device shown in FIG.

FIG. 3 is a partial perspective view of another embodiment of the discharge electrode in the device shown in FIG.

FIG. 4 is a partial perspective view of still another embodiment of the discharge electrode in the device shown in FIG.

FIG. 5 is a partial sectional view of a rotating roll electrode in the apparatus shown in FIG.

FIG. 6 is a longitudinal sectional view of one embodiment of the gas chamber in the apparatus shown in FIG.

FIG. 7 is a longitudinal sectional view of another embodiment of the gas chamber in the apparatus shown in FIG.

FIG. 8 is a cross-sectional view of an embodiment of a sealing means between the side surface of the rotating roll electrode and the plasma chamber in the apparatus shown in FIG.

FIG. 9 is a longitudinal sectional view of another embodiment of the plasma processing sheet manufacturing apparatus according to the present invention.

FIG. 10 is a plan view of one embodiment of the plasma confinement electrode in the apparatus shown in FIG.

FIG. 11 is a plan view of another embodiment of the plasma confinement electrode in the apparatus shown in FIG. Best shape bear for carrying out the invention

The best mode for carrying out the present invention will be described with reference to the drawings.

In FIG. 1, this device has a metal rotary drum 1 rotatably supported on a drum rotation support shaft (not shown) attached to a machine base (not shown). The rotating drum 1 has a predetermined width, and its peripheral surface has a capacitance per unit area in the range of 0.13 F Zm ² to 20 F Zm ² and a relative dielectric constant of 10 or more dielectrics 2 are adhered. The rotating drum 1 on which the dielectric 2 is adhered forms a counter electrode (rotating roll electrode) 3. The rotating roll electrode 3 is rotated in a direction indicated by an arrow 4 by a rotating drive source (not shown).

Above the rotating roll electrode 3, at a certain distance from the surface of the rotating roll electrode 3, a discharge electrode 5 is provided fixed to a machine base, facing the width direction of the rotating roll electrode 3. Although the number of the discharge electrodes 5 may be one, it is preferable that a plurality of discharge electrodes 5 (six in the figure) are provided in the rotating direction of the rotating roll electrode 3 at intervals. The discharge electrode 5 in this device is a metal electrode having no dielectric coating.

Between the rotating roll electrode 3 and the discharge electrode 5, there is a traveling path 7 through which a continuously traveling sheet 6 passes along a part of the peripheral surface of the rotating roll electrode 3. In this apparatus, the sheet 6 comes into contact with the dielectric 2 coated on the peripheral surface of the rotating roll electrode 3 and substantially at the same speed as the peripheral surface speed of the rotating roll electrode 3 in the direction indicated by the arrow 8. To run.

The sheet 6 has a predetermined width, for example, 600 mm. The width of the rotating roll electrode 3 and the length of the discharge electrode 5 are set so as to correspond to the width of the sheet 6.

A plasma processing zone 9 exists between the discharge electrode 5 and the rotating roll electrode 3 A part of the peripheral surface of the rotating roll electrode 3 and the discharge electrode 5 are included and fixed to the machine base. A defined plasma chamber 10 is provided. The plasma chamber 10 has a traveling path entrance 11 on the upstream side in the traveling direction of the sheet 6 and has a traveling path outlet 12 on the downstream side in the traveling direction of the seat 6. The atmosphere inside the plasma chamber 10 is substantially closed to the outside atmosphere except for the entrance 11 and the exit 12 of these running paths.

The plasma chamber 10 is provided with a gas supply port 13 for supplying a gas containing a rare gas element (plasma processing gas) into the plasma chamber 10. The gas supply port 13 is connected to a plasma processing gas supply source (cylinder) 14 via a supply pipe 15.

A plasma processing power supply 16 for applying a predetermined voltage between the discharge electrode 5 and the rotating roll electrode 3 as a counter electrode and flowing a predetermined current is provided. The discharge electrode 5 of each column and the plasma processing power supply 16 are connected by a first power line 17, and the rotating roll electrode 3 and the plasma processing power supply 16 are connected by a second power line 18. ing.

The second power line 18 is grounded at a grounding section 19, and the plasma processing power supply 16 forms a grounded low impedance non-resonant power supply.

When there are a plurality of discharge electrodes 5, a plurality of plasma processing power supplies 16 are used, and one discharge electrode 5 is connected to one plasma processing power supply 16. A type in which the plasma processing power supplies 16 are controlled independently of each other may be adopted.

When a non-resonant power supply is used, a matching circuit is preferably provided between the plasma processing power supply 16 and the discharge electrode 5.

FIGS. 2, 3, and 4 show examples of the discharge electrode 5. FIG. The tip (the lower end in the figure) of the discharge electrode 5a shown in FIG. 2 has a knife edge shape. The tip (the lower end in the figure) of the discharge electrode 5b shown in FIG. 3 has a shape in which a large number of square pyramids are arranged in a staggered manner. The distal end (the lower end in the figure) of the discharge electrode 5c shown in FIG. 4 has a dome shape. The shape of the projection at the tip of the discharge electrode 5 is described in the above-mentioned Japanese Patent Application Laid-Open No. 5-116. In this device, a large number of pyramids shown in Fig. 3 are formed. The discharge electrode 5b having the form is preferably used.

FIG. 5 shows a cross-sectional view of a part of the rotating roll electrode 3. The rotating roll electrode 3 has a first dielectric layer 21 made of alumina formed on its peripheral surface and a second dielectric layer 22 made of barium titanate formed thereon. . A composite dielectric is formed from these two layers. By adjusting the thickness of each layer of the composite dielectric, the relative permittivity of the dielectric covering the rotating roll electrode 3 is set to 10 or more.

The rotating roll 1 itself is well known in the industry. Although not shown in FIG. 1, a rotary roller 1 is provided inside the rotary roll 1 for removing heat generated in the rotary roll 1 during the plasma processing. Cooling water is supplied from outside the Laje overnight.

The plasma processing of the sheet 6 is performed by the plasma processing sheet manufacturing apparatus having the configuration described above.

The front end of the seat 6 is inserted into the plasma chamber 10 from the entrance 11 of the traveling path in the direction indicated by the arrow 8 and is led out from the exit 12 of the traveling path. The sheet 6 is wound around the peripheral surface of the rotary roller electrode 3 at least between the entrance 11 and the exit 12 of the traveling path.

In this state, the plasma processing gas is supplied into the plasma chamber 10 from the supply source (bomb) 14 of the plasma processing gas via the supply pipe 15 and the gas supply port 13. On the other hand, the plasma processing power supply 16 is operated, and plasma is formed in the plasma processing region 9 by the electric action of the discharge electrode 5 and the rotating roll electrode 3 due to the glow discharge phenomenon.

In this state, the running of the sheet 6 is started, the surface of the sheet 6 which is run and carried into the plasma chamber 10 is subjected to the plasma treatment, and the continuous production of the plasma-treated sheet is started.

In this apparatus, even if the traveling speed of the sheet 6 exceeds the processing speed of the conventional apparatus, the plasma processing is stably performed at a high speed. The reason why the plasma processing at this high speed has become possible is that the surface of the rotating roll electrode 3 which is the counter electrode in this apparatus has a capacitance per unit area of 0. This is because it is covered with a dielectric in the range of 13 F Zm ² to 20 F Zm ² .

On the other hand, as the traveling speed of the seat 6 increases, the amount of external air entering the plasma chamber 10 accompanying the seat 6 increases. As a result, a phenomenon appears in which the glow discharge state of the plasma processing region 9 becomes unstable. In order to prevent this phenomenon, this device is further equipped with the following means.

In FIGS. 1 and 6, a pressurized gas supply port for supplying a pressurized gas toward the surface of a running sheet 6 outside the plasma chamber 10 and adjacent to the entrance 11 of the traveling path. A gas chamber 32 having 31 is provided. The gas chamber 32 is fixed to the machine base.

The pressurized gas supply port 31 is open in a slit shape in the width direction of the traveling path 7 of the sheet 6. It is preferable that the pressurized gas supply port 31 is provided with a rectifying means for injecting the supplied pressurized gas uniformly in the width direction, for example, a rectifying plate made of a perforated plate.

The gas (air) jetted from the pressurized gas supply port 31 is jetted toward the surface of the seat 6 at an angle in the direction opposite to the running direction of the seat 6 (arrow 8). Is good.

By providing this means, the amount of external air that the sheet 6 brings into the plasma chamber 10 is drastically reduced, and the plasma processing in the plasma processing area 9 is stable even if the running speed of the sheet 6 is increased. And continue. The gas chamber 32 also has a gas suction port 33 and a gas circulating means (blower) 3 so that the gas (air) injected from the pressurized gas supply port 31 is collected and reused. 4, and a second gas connecting the gas suction port 33 and the gas circulation means 34 to the first gas flow passage 35 and the gas circulation means 34 and the pressurized gas supply port 31 Preferably, a flow passage 36 is provided. FIG. 7 is a longitudinal sectional view of a modification of the gas chamber 32 shown in FIG. The gas chamber 32 shown in FIG. 7 further includes nip means 41 for nipping the sheet 6 with respect to the surface of the rotating roll electrode 3 on the upstream side in the running direction of the sheet 6. The nip means 4 1 rotates the sheet 6 with the rotating roll electrode 3 A nip roll 42 that nips the surface of the nip and a nip chamber 43 that contains it.

Nippuro Ichiru 4 2, _c Nippuro Ichiru 4 2 which is rotatably supported by the nip chamber 4 3 be of the driven type which is rotated by the travel of the sheet 6 or, the rotation driving means are provided on the outside It may be of the positive drive type combined with. '

By providing the nip means 41, the amount of air accompanying the traveling seat 6 is further reduced.

A variant of this nip means 41 is shown in FIG. This variant is indicated by the variant nip means 41a. The deformed nip means 41a includes a deformed nip roll 42a, a deformed nip chamber 43a containing the deformed nip roll 42a, and a deformed nip auxiliary roller 42b.

The deformed nip roller 42a is brought into contact with the surface of the rotating roll electrode 3 only at both ends thereof, and the diameter of the intermediate portion is smaller than the diameter of both ends. The traveling sheet 6 comes into contact with the peripheral surface of the rotating deformed nip auxiliary roller 42b, and then contacts the peripheral surface of the rotating deformed nip roller 42a, and then contacts the peripheral surface of the rotating roll electrode 3. Contact.

In this manner, the air accompanying the traveling seat 6 is eliminated. In this embodiment, the running sheet 6 does not completely nip as in the embodiment of the nip means 41 shown in FIG. 7, so that the surface is easily damaged by the nip. In case (6), this embodiment is preferably applied.

It is preferable that a gas flow preventing plate 51 extending from the plasma chamber 10 be provided outside the outlet 12 of the traveling path of the plasma chamber 10. Thereby, the gas in the plasma chamber 10 is substantially prevented from flowing out to the outside accompanying the sheet 6. The surface (lower surface) of the gas flow prevention plate 51 facing the sheet 6 is preferably of a labyrinth structure.

FIG. 8 is a cross-sectional view of one embodiment of the sealing means between the side surface of the rotating roll electrode 3 and the plasma chamber 10 in the apparatus shown in FIG. Praz To improve the hermeticity of the chamber 10 against the outside world, the lower ends (skirts) 10a of both side walls along the running direction of the sheet 6 of the plasma chamber 10 are formed on the outer periphery of both sides of the rotating roll electrode 3. A member having good slidability fixed to either the lower end 10a or the outer peripheral end 3a is formed so as to face the end 3a with a gap. It is good that it is made to be closed to the outside world by the one consisting of 6 1.

In the apparatus shown in FIG. 9, the same elements as those in the apparatus shown in FIG. 1 have the same reference numerals. The device shown in FIG. 9 has plasma confinement electrodes 71 a and 71 b outside the discharge electrode 5. The device shown in FIG. 9 differs from the device shown in FIG. 1, especially in this configuration. In FIG. 9, the plasma confinement electrodes 71a are provided at intervals along the width direction of the foremost discharge electrode 5 in the traveling direction of the sheet 6 at the entrance 11 side of the traveling path. I have. The plasma confinement electrodes 71 b are provided at intervals on the exit 12 side of the traveling path along the width direction of the innermost discharge electrode 5 in the traveling direction of the sheet 6. The length in the width direction of these plasma confinement electrodes 71a and 7lb is the same as or slightly longer than that of the discharge electrode 5. The overall size is smaller than the discharge electrode 5.

This relationship is also shown in FIG. 10 showing a bottom view of the arrangement of the discharge electrode 5 and the plasma confinement electrodes 71a and 71b.

In order to form a discharge phenomenon between the plasma confinement electrodes 71a and 71b and the rotating roll electrode 3 as a counter electrode, a plasma confinement power supply 72 is provided.

The plasma confinement electrodes 7 1 a and 7 1 b and the plasma confinement power supply 72 are coupled by a third power line 73, and the rotating roll electrode 3 and the plasma confinement power supply 72 are coupled by a fourth power line 74. Have been. The fourth power line 74 is grounded at a grounding section 19.

The discharge power of the plasma confinement electrodes 71a and 71b is It is controlled by the plasma confinement power supply 72 so that it becomes smaller than that of 5.

By driving the plasma confinement electrodes 71 a and 71 b during the plasma processing, the spread of the discharge by the discharge electrode 5 is suppressed. Since the spread of the discharge is suppressed, it is possible to prevent the discharge electrode 5 from short-circuiting with a nearby metal member. Since the discharge power of the plasma confinement electrodes 71a and 71b is smaller than the discharge power of the discharge electrode 5, the plasma confinement electrodes 71a and 71b do not short-circuit with nearby metal members.

By providing the plasma confinement electrodes 71a and 71b, the power supplied to the discharge electrode 5 can be further increased. Therefore, according to this apparatus, the processing strength and the processing speed of the surface modification of the sheet 6 can be further increased, and the productivity of the plasma processing sheet is further improved. FIG. 11 is a bottom view showing another mode of providing a plasma confinement electrode with respect to the discharge electrode 5. In this embodiment, the discharge electrode 5 is surrounded by a series of plasma confinement electrodes 75. This embodiment prevents the occurrence of the short-circuit phenomenon when the discharge of the discharge electrode 5 easily causes a short circuit with the metal members near both ends in the width direction of the discharge electrode 5.

In the device shown in FIG. 9, the gas flow preventing plate 51 of the device shown in FIG. 1 is replaced with a gas chamber 32 provided on the entrance 11 side of the traveling path and a deformation nip. A gas chamber 82 and a modified nip chamber 93a having the same structure as the chamber 43a are provided. The provision of the gas chamber 82 and the deformed nip chamber 93a prevents the atmospheric gas in the plasma chamber 10 from flowing out to the outside.

In the above, the plasma processing sheet manufacturing apparatus and the plasma processing sheet manufacturing method according to the present invention have been described.

Also in the conventional apparatus, the discharge electrode or the counter electrode is coated with a dielectric. As this dielectric, glass, mica, silicon rubber, polyimide resin, polyester resin, and alumina are specifically used. However, the relative permittivity of these dielectrics is less than 10. In this conventional device The running speed of the sheets used ranges from about 15 minutes to about 20 mZ.

In this conventional apparatus, when the running speed of the sheet is increased to increase the productivity of the plasma-treated sheet, the effect of the plasma treatment in the plasma treatment area, that is, The effect was observed to begin to decline. .

When the input power during plasma processing was increased to prevent this effect from dropping, it was observed that abnormal discharge phenomena occurred in the plasma processing area. The plasma processing sheet manufacturing apparatus and the plasma processing sheet manufacturing method using the same have succeeded in preventing the occurrence of these phenomena occurring when the processing speed of the sheet is increased.

The present invention has enabled plasma processing under glow discharge of a sheet at a sheet traveling speed of about 2 OmZ minutes or more, which could not be achieved by the conventional apparatus. At present, it has been confirmed that processing is possible even when the running speed of the polyimide sheet is about 45 mZ. Industrial applicability

Advantageous Effects of Invention According to the present invention, there are provided a plasma processing sheet manufacturing apparatus and a manufacturing method capable of maintaining stable plasma required for surface modification of a sheet even when the running speed of the sheet is 2 OmZ minutes or more.

Claims

Claim range ffl

1. A sheet traveling path having a discharge electrode and a counter electrode facing each other, and having a sheet traveling path through which a sheet continuously traveling through a plasma processing area formed by the discharge between the discharge electrode and the counter electrode passes. In a plasma processing sheet manufacturing apparatus in which the surface of at least one of the electrode and the counter electrode is covered with a dielectric, the capacitance per unit area of the dielectric is 0.13 z FZm ² or less. A plasma processing sheet manufacturing apparatus in the range of ²⁰ FZm2.

2. The counter electrode is composed of one rotating roll electrode supported on a fixed rotating shaft and rotating in the sheet traveling direction of the traveling path, and the surface of the rotating roll electrode is covered with the dielectric. 2. The apparatus for producing a plasma-processed sheet according to claim 1, wherein the discharge electrode comprises at least one fixed electrode having no coating with the dielectric.

3. The plasma processing sheet manufacturing apparatus according to claim 2, wherein the counter electrode is connected to a grounded non-resonant power supply.

4. The plasma processing sheet manufacturing apparatus according to claim 3, wherein the discharge electrodes are provided in a plurality of rows, and discharge powers acting on the discharge electrodes in each row can be controlled independently of each other.

5. The plasma processing sheet manufacturing apparatus according to claim 1, wherein a relative dielectric constant of the dielectric is 10 or more.

6. The plasma processing sheet manufacturing apparatus according to claim 5, wherein the dielectric is a composite dielectric obtained by laminating at least two different types of dielectrics.

7. The plasma processing sheet manufacturing apparatus according to claim 5, wherein the thickness of the dielectric is in a range of 0.5 mm to 5 mm.

8. The plasma processing sheet manufacturing apparatus according to claim 5, wherein the dielectric is at least one dielectric selected from the group consisting of barium titanate, titania, zirconia, magnesium, and yttria.

9. A sheet traveling path having a discharge electrode and a counter electrode facing each other, and having a sheet traveling path through which a sheet continuously traveling through a plasma processing region formed by the discharge between the discharge electrode and the counter electrode passes. In a plasma processing sheet manufacturing apparatus in which at least one of an electrode and a counter electrode is coated with a dielectric, a plasma chamber for substantially shielding the plasma processing area from the outside is provided; A gas supply port for supplying a gas containing a rare gas element into the chamber; and an inlet and an outlet of the sheet traveling path, outside the entrance of the sheet traveling path. Manufacturing of a plasma processing sheet provided with a gas chamber having a pressurized gas supply port for supplying a pressurized gas toward the sheet travel path near an entrance of the travel path Dress

1 0. Surface of at least one of the electrodes of the discharge electrode and the counter electrode is coated with a dielectric, and the capacitance per unit area of the dielectric is from 0. 1 3 ^ F / m 2 2 oF Zm plasma processing sheet manufacturing apparatus according to claim 9 in a range of ^2.

11. The counter electrode is composed of one rotating roll electrode supported on a fixed rotating shaft and rotating in a sheet traveling direction of the traveling path, and the surface of the rotating roll electrode is made of the dielectric material. 10. The apparatus for producing a plasma processing sheet according to claim 10, wherein the discharge electrode is covered with at least one fixed electrode that does not have a coating with the dielectric.

12. The plasma processing sheet manufacturing apparatus according to claim 11, wherein the counter electrode is connected to a grounded non-resonant power supply.

13. The plasma processing sheet manufacturing apparatus according to claim 12, wherein the discharge electrodes are provided in a plurality of rows, and discharge powers acting on the discharge electrodes in each row can be controlled independently of each other.

14. The apparatus for manufacturing a plasma processing sheet according to claim 10, wherein a relative dielectric constant of the dielectric is 10 or more.

15. The plasma processing sheet manufacturing apparatus according to claim 14, wherein the thickness of the dielectric is in a range of 0.5 mm to 5 mm.

16. The production of the plasma processing sheet according to claim 15, wherein the dielectric is at least one dielectric selected from the group consisting of barium titanate, titania, zirconia, magnesium, and yttria. apparatus.

17. A gas suction port for discharging the gas supplied from the pressurized gas supply port is provided in the gas chamber on a side opposite to the inlet side of the traveling path with respect to the pressurized gas supply port. 14. The plasma processing sheet according to claim 9, further comprising a gas circulating means for pressurizing the gas sucked from the gas suction port and supplying the gas to the pressurized gas supply port. manufacturing device.

18. In the traveling direction of the traveling sheet, the discharge electrodes are located on the upstream side of the discharge electrode located at the most upstream side of the plurality of rows of discharge electrodes and on the downstream side of the discharge electrode located at the most downstream side. A plasma confinement electrode having a discharge power smaller than that of the discharge electrode adjacent to the rotating electrode is provided so as to face the surface of the roll of the rotating roll electrode. An apparatus for producing a plasma processing sheet according to any one of the claims.

19. In the traveling direction of the traveling sheet, the discharge electrodes are located on the upstream side of the discharge electrode located on the most upstream side of the plurality of rows of discharge electrodes and on the downstream side of the discharge electrode located on the most downstream side. And a plasma confinement electrode having a discharge power smaller than that of the discharge electrode is provided to face the surface of the roll of the rotating roll electrode, respectively. The manufacturing apparatus of the plasma processing sheet described in the above.

20. A plasma processing sheet produced by causing a sheet to run on a travel path of the apparatus for manufacturing a plasma processing sheet according to any one of claims 1 to 19, and performing the plasma processing on the sheet in a plasma processing area. Manufacturing method.

21. The method according to claim 20, wherein the plasma processing area is substantially at atmospheric pressure.

22. The method according to claim 21, wherein the rare gas element is argon.

23. The method for producing a plasma-treated sheet according to claim 22, wherein the sheet is a sheet made of a resin.

24. The method according to claim 23, wherein the resin is a polyimide.

25. The method for producing a plasma processing sheet according to claim 24, wherein the current density in the plasma processing area is 0.1 μm / m ² or more.