JPH0959777A - Discharge plasma treatment and discharge plasma treating device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To simply conduct desired treatment at the atmospheric pressure with a small amt. of a processing gas by supplying the processing gas to the part to be treated and projecting the discharge plasma produced in an inert gas toward the part to be treated. SOLUTION: An inert gas such as Ar and N2 is circulated through a solid dielectric vessel 4 provided with a discharge plasma projecting port 7 from a gas inlet 6. A pulse voltage is impressed from a power source 1 between one side electrode 2 furnished outside the vessel 4 and the other side electrode 3 coupled with the electrode 2 to produce plasma. Meanwhile, a processing gas is supplied to the part to be treated of a body 5 to be treated by a processing gas supplying machine 8, and the plasma is projected toward the part of the body 5 to be treated from the port 7 while intersecting the supply direction of the processing gas. Further, if necessary, the vessel 4 and the machine 8 are made movable through a movable jig 9 while keeping an almost constant relative position. The body 5 is preferably moved close to the part 7 with a moving device.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a discharge plasma processing method and a discharge plasma processing apparatus.

[0002]

2. Description of the Related Art Surface treatment is performed by forming a functional group layer, a radical layer, etc. on the surface of an object to be treated to control the surface energy,
It imparts hydrophilicity and water repellency. By such a treatment, it becomes possible to modify the wettability, adhesiveness, etc. of the object to be treated, and it is also possible to form a film having a function excellent in electrical characteristics, optical characteristics, etc. on the surface of the object to be treated. It will be possible. As such a surface treatment method, there is known a method of forming a radical layer on the surface of an object to be treated using discharge plasma.

As a method for surface treatment of a solid such as plastic, there is known a method of generating glow discharge plasma at a pressure of 0.01 to 100 Torr. In this method, when the pressure exceeds 100 Torr, the discharge is localized and the arc discharge is generated, which makes it difficult to apply to a plastic substrate having poor heat resistance.
It is necessary to perform processing at a low pressure of 1 to 100 Torr.

Although such a plasma processing method is widely applied industrially, it requires low-pressure processing, so that a vacuum chamber, a vacuum exhaust device, etc. must be installed, so that plasma processing is possible. The apparatus becomes expensive, and when a large area substrate is processed by this method, a large-capacity vacuum container and a large-output vacuum exhaust apparatus are required. Becomes Further, when processing a plastic substrate having high water absorption, it takes a long time to evacuate the vacuum, so that there is a problem that the cost of the processed product becomes high.

Japanese Unexamined Patent Publication No. 1-306569 discloses a thin film forming method using a thin wire type electrode. This thin film forming method is to mix an inert gas such as helium, a fluorine-containing gas, and a monomer gas and supply the mixed gas to a glow discharge plasma region near the substrate from a porous tube having a plurality of apertures, thereby forming a thin film on the substrate. Is formed.

In this thin film manufacturing method, since glow discharge plasma is generated at atmospheric pressure, it is possible to reduce the cost of the apparatus and equipment and to process a large area substrate. But,
In this apparatus, the size and shape of the object to be processed are restricted, and it is difficult to process an arbitrary position of the object to be processed. Further, the device can be further simplified.

In Japanese Unexamined Patent Publication No. 5-275193, discharge gas is generated by holding a mixed gas of a rare gas and a processing gas in a unidirectional flow state between electrodes provided with a solid dielectric. A plasma processing apparatus is disclosed. However, in this apparatus, not only a large amount of processing gas is circulated, but also plasma unnecessary for processing is formed at the same time, and a desired reforming effect cannot be sufficiently obtained.
Further, it is difficult to selectively set the processing section and the non-processing section.

[0008]

SUMMARY OF THE INVENTION In view of the above, the present invention provides a discharge plasma processing apparatus and a discharge plasma processing method capable of performing desired processing with a small amount of processing gas under atmospheric pressure. .

[0009]

According to the discharge plasma processing method of the present invention, a discharge plasma generated in an inert gas is projected toward a target portion while supplying a target gas to the target portion. Is characterized by.

The method of generating the discharge plasma in an inert gas is not particularly limited, but the inert gas is circulated in a solid dielectric container having one electrode and a discharge plasma projecting port. In this state, discharge plasma is generated by applying a voltage between the one electrode and the other electrode that forms a pair, and the processing gas is directed toward the processing target portion from a direction intersecting the discharge plasma protruding direction. Is most advantageous in the apparatus.

The method of supplying the processing gas to the above-mentioned treated portion is not particularly limited, and a known gas feeder can be used. By providing a processing gas supply port near the portion to be processed and supplying the processing gas toward the portion to be processed from the direction intersecting the protruding direction of the discharge plasma, it is possible to perform processing efficiently with a small amount of processing gas. I can.

The discharge plasma treatment method of the present invention will be described below.
Description will be made with reference to the apparatus of FIG. In the apparatus of FIG. 1, one electrode is disposed on the outer surface and a solid dielectric container provided with a discharge plasma projecting port, another electrode paired with the one electrode,
And a discharge plasma processing apparatus comprising a processing gas supply device, wherein discharge plasma is generated by applying a voltage between the pair of electrodes in a state where an inert gas is circulated in the solid dielectric container. In addition, the discharge plasma is arranged so that the protruding direction of the discharge plasma intersects the processing gas protruding direction of the processing gas supplier.

In the figure, 1 indicates a power source. Reference numeral 2 represents one electrode provided on the outer surface of the solid dielectric container. 3 is
It represents another electrode. 4 represents a solid dielectric container. 5 is
Represents an object to be processed. Reference numeral 6 represents an inert gas inlet. 7
Represents a discharge plasma discharge port. Reference numeral 8 represents a processing gas supplier. Reference numeral 9 represents a movable jig.

The power source 1 is preferably one capable of applying a voltage having a frequency on the order of kHz, and more preferably one capable of applying a voltage having a low frequency of 1 to 30 kHz.

In order to generate a stable discharge plasma under atmospheric pressure, it is effective to apply a pulsed voltage. FIG. 2 shows an example of the pulse voltage waveform. The waveforms (a) and (b) are impulse type, the waveform (c) is pulse type, and the waveform (d) is a modulation type. Although FIG. 2 shows the case where the voltage application is repeated positive and negative, a pulse of a type in which a voltage is applied to either the positive or negative polarity side may be used. FIG. 3 shows a block diagram of a power supply when applying such a pulse voltage.

The pulse voltage waveform in the present invention is not limited to the waveforms mentioned here, but the shorter the pulse rise time, the more efficiently the gas is ionized during plasma generation. Preferably, the rise time is 100 μs or less.

Further, the modulation may be performed using pulses having different pulse waveforms, rise times and frequencies. Such modulation is effective in performing a high-speed continuous surface. A higher pulse frequency and a shorter pulse width are more suitable for a high-speed continuous surface.

In the present invention, a voltage is applied between the one electrode 2 and the other electrode 3 to generate discharge plasma. The magnitude of the applied voltage depends on the shape of the one electrode 2,
The electric field strength is preferably 0.1 to 40 kV / cm, although it is appropriately determined depending on the shape of the other electrode 3, the distance between the one electrode 2 and the other electrode 3, and the like. When the electric field strength is less than 0.1 kV / cm, discharge plasma is less likely to be generated, and when it exceeds 40 kV / cm, the solid dielectric container 4 causes a dielectric breakdown, and a behavior of shifting to arc discharge appears. Direct current may be superimposed upon the application of the voltage. The magnitude and polarity of the DC voltage are appropriately determined depending on the pulse voltage and the type of processing gas.

The shapes of the one electrode 2 and the other electrode 3 are not particularly limited, and in addition to the flat plate shape shown in the figure, a curved surface shape such as a cylindrical shape or a spherical pair shape can be used. The one electrode 2 and the other electrode 3 may be made of, for example, a multi-component metal such as stainless steel or brass, or may be made of a pure metal such as copper or aluminum.

The distance between the one electrode 2 and the other electrode 3 is appropriately determined according to the thickness, material, applied voltage, etc. of the solid dielectric container 4, but is preferably 0. ~
30 mm. If it exceeds 30 mm, a high voltage is required, and the discharge plasma easily shifts to arc discharge,
The processing uniformity is impaired.

The one electrode 2 is the solid dielectric container 4 described above.
Is disposed on the outer surface of. The thickness of the surface of the solid dielectric container 4 on which the one electrode 2 is arranged is 0.
03-30 mm is preferable. If the thickness is less than 0.03 mm, dielectric breakdown occurs when a high voltage is applied, and arc discharge occurs.

FIGS. 4 and 5 are views showing an example of the arrangement of the other electrode 3 described above. For example, the other electrode 3 may be arranged to face the one electrode 2, and the other electrode 3 may be
You may arrange | position on the back surface of the to-be-processed object 5.

The solid dielectric container 4 is provided with a projecting port 7 for discharge plasma generated in the solid dielectric container 4. The shape of the discharge plasma protruding port 7 is not particularly limited, and examples thereof include a slit-shaped one, a hole-shaped one, and a tip-shaped one formed by the solid dielectric container.

The shape of the solid dielectric container 4 is not particularly limited, and examples thereof include a square shape and a cylindrical shape. The solid dielectric used in the solid dielectric container 4 is not particularly limited, and examples thereof include plastics such as polyfluoroethylene, polyethylene terephthalate, polymethacrylate, and polyethylene; silicon dioxide, Pyrex glass, aluminum oxide, titanium dioxide, and the like. Glass, ceramics and the like. These may be formed of a sheet, a film, or the like, for example.

The inert gas is introduced into the solid dielectric container 4 through the inert gas inlet 6. A voltage is applied between the one electrode 2 and the other electrode 3 in a state where the inert gas is flown to generate discharge plasma, and the generated discharge plasma is discharged from the discharge plasma protruding port 7. Be projected.

The flow rate of the inert gas introduced can be appropriately determined by the cross-sectional area of the discharge plasma projection port 7, the distance between the object 5 to be processed and the discharge plasma projection port 7, and the like. For example, when the introduction flow rate of the inert gas is increased, the projection flow rate of the discharge plasma increases proportionally and the reaching distance of the discharge plasma increases, so that the target object 5 and the discharge plasma projection port are increased. The distance to 7 can be increased. Although not shown in the drawing, the inert gas is supplied into the solid dielectric container 4 via a general gas flow rate controller.

The processing gas supply device 8 shown in FIG. 1 is provided with processing gas projecting openings so that the discharge plasma projecting direction and the processing gas projecting direction intersect each other. The structure of the processing gas supply device 8 is not particularly limited, and for example,
The same structure as that of the solid dielectric container 4 can be used.

In order to perform the treatment efficiently with a small amount of the processing gas, the region where the discharge plasma projection direction intersects with the processing gas projection direction is located near the processing gas projection port, and the crossing is performed. It is preferable to position the object 5 to be processed in the area. Further, the discharge port 7 for discharge plasma
Also, it is preferable to be near the intersecting region.

The flow rate of the processing gas may be appropriately determined depending on the flow rate of the processing gas, the distance between the processing gas feeder 8 and the object 5 to be processed, and the like. When the distance between the processing gas supply port of the processing gas supply device 8 and the object to be processed 5 is long, it is necessary to increase the flow rate of the processing gas to increase the flow velocity.

In the present invention, the above-mentioned solid dielectric container 4 is used.
And the processing gas supply device 8 are connected to the movable jig 9, and the solid dielectric container 4 and the processing gas supply device 8 are movable while substantially maintaining their relative positions. It is preferable.

In the present invention, it is preferable that a device for moving the object to be processed is provided so that the object to be processed 5 moves near the projecting port of the discharge plasma and is exposed to the discharge plasma.

The distance between the object 5 to be processed and the discharge plasma projecting port 7 is appropriately determined by the flow velocity of the discharge plasma projecting from the discharge plasma projecting port 7. Since it becomes high and a large flow velocity is required, it is preferably 0.01 to 10 cm. More preferably, it is 0.1 to 3 cm.

The solid dielectric container 4 can process, for example, a shaped product or a film-shaped object to be processed continuously or partially. Therefore, the movable jig 9 and the object to be processed 5 are used. It is preferable that the discharge plasma can be continuously moved while keeping a constant distance from the projection port 7.

FIG. 6 is a diagram showing an example of continuously processing shaped articles by the plasma processing apparatus of the present invention. 9
Represents a movable jig. The movable jig 9 is formed by a computer that stores the shape of the object 5 to be processed.
And the discharge port 7 of the discharge plasma are constantly scanned in the XYZ directions while maintaining a constant distance.

FIG. 7 is a diagram showing an example of continuously processing a sheet-shaped or film-shaped object to be processed by the plasma processing apparatus of the present invention. The movable jig 9 scans in the XY directions while keeping a constant distance between the object 5 to be processed and the discharge plasma projection port 7 by a computer that stores the shape of the object 5 to be processed.

FIG. 8 is a diagram showing an example of continuously or partially treating a film-shaped object by the plasma processing apparatus of the present invention. Reference numeral 10 represents a movable jig. The movable jig 9 keeps a constant distance between the object 5 to be processed and the discharge plasma projection 7 and the movable jig 10 keeps the discharge plasma projection 7 and the other electrode 3 constant. Keep a distance. Since the object 5 to be processed is connected to a set of film-shaped material traveling system by a commonly used roll, it can be continuously moved while maintaining a constant distance with respect to the discharge plasma projection port 7.

The above-mentioned FIG. 1 shows a plasma processing apparatus for processing one side of an object to be processed, but when processing both sides of the object to be processed, the same plasma is applied to the other surface of the object to be processed. A processing device may be provided.

Examples of the inert gas used in the present invention include rare gases such as helium, neon, argon and xenon, and nitrogen gas. You may use these individually or in mixture of 2 or more types. Since helium has a long metastable life, it is advantageous for exciting the processing gas.

On the other hand, in the industrial production process, it is preferable to use argon, nitrogen, etc., which are cheaper than helium.
Therefore, as described above, the processing may be performed by the method of applying the pulsed electric field. With the pulsed electric field, it is possible to realize stable treatment at a high level equal to or higher than that when helium is used even in an atmosphere such as argon or nitrogen.

Conventionally, the treatment in the presence of helium has been carried out under a pressure near atmospheric pressure. However, according to the method of applying a pulsed electric field, argon, which is cheaper than helium, Stable treatment in a nitrogen atmosphere is possible, which has a great industrial advantage.

In the surface treatment of the present invention, any treatment can be performed by selecting the treatment gas supplied to the discharge plasma generation space.

By using a fluorine-containing compound gas as the above-mentioned processing gas, a fluorine-containing group can be formed on the surface of the substrate to reduce the surface energy and obtain a water-repellent surface.

Examples of the fluorine element-containing compound include carbon tetrafluoride (CF ₄ ), carbon hexafluoride (C ₂ F ₆ ), propylene hexafluoride (CF ₃ CFCF ₂ ), and cyclobutane octafluoride (C ₄ F ₈ ) Fluorine-carbon compounds such as monochloride
Halogen, such as fluorocarbon (CClF ₃₎ - carbon compound,
6 fluoride such as sulfur hexafluoride (SF ₆₎ - sulfur compounds and the like. From the viewpoint of safety, it is preferable to use carbon tetrafluoride, carbon hexafluoride, propylene hexafluoride, and cyclobutane 8-fluoride which do not generate hydrogen fluoride which is a harmful gas.

Further, the following oxygen element-containing compound, nitrogen element-containing compound and sulfur element-containing compound are used as a processing gas to form hydrophilic functional groups such as carbonyl group, hydroxyl group and amino group on the surface of the substrate. The surface energy can be increased to obtain a hydrophilic surface.

Examples of the oxygen-containing compound include oxygen,
Contains oxygen elements such as ozone, water, carbon monoxide, carbon dioxide, nitric oxide, nitrogen dioxide, alcohols such as methanol and ethanol, ketones such as acetone and methyl ethyl ketone, and aldehydes such as methanal and ethanal. Organic compounds and the like can be mentioned. These alone are 2
Mixtures of more than one species may be used. Further, the oxygen-containing compound and a gas of a hydrocarbon compound such as methane and ethane may be mixed and used. Addition of the fluorine element-containing compound to the oxygen element-containing compound at 50% by volume or less promotes hydrophilicity. As the fluorine element-containing compound, the same compounds as those exemplified above may be used.

As the nitrogen element-containing compound, nitrogen,
Ammonia etc. are mentioned. The nitrogen element-containing compound and hydrogen may be used as a mixture.

Examples of the sulfur-containing compound include sulfur dioxide and sulfur trioxide. Further, sulfuric acid can be vaporized and used. You may use these individually or in mixture of 2 or more types.

A hydrophilic polymer film can be deposited by performing the treatment in an atmosphere of a monomer having a hydrophilic group and a polymerizable unsaturated bond in the molecule. Examples of the hydrophilic group include a hydroxyl group, a sulfonic acid group, a sulfonate group, a primary or secondary or tertiary amino group, an amide group, 4
Examples thereof include hydrophilic groups such as a primary ammonium group, a carboxylic acid group, and a carboxylic acid group. Also, a hydrophilic polymer film can be similarly deposited by using a monomer having a polyethylene glycol chain.

The monomers include acrylic acid, methacrylic acid, acrylamide, methacrylamide, N, N
-Dimethylacrylamide, sodium acrylate, sodium methacrylate, potassium acrylate, potassium methacrylate, sodium styrenesulfonate, allyl alcohol, allylamine, polyethylene glycol dimethacrylate, polyethylene glycol diacrylate, and the like. These monomers are
Used alone or as a mixture.

Since the above-mentioned hydrophilic monomer is generally a solid, it is dissolved in a solvent and vaporized by a means such as reduced pressure before use. Examples of the solvent include organic solvents such as methanol, ethanol, and acetone, water, and mixtures thereof.

Further, by using a processing gas such as a metal-hydrogen compound, a metal-halogen compound, a metal alcoholate of a metal such as Si, Ti, Sn or the like, SiO ₂ , TiO ₂ , Sn or the like is used.
By forming a thin film of a metal oxide such as O ₂ , electrical and optical functions can be given to the substrate surface.

The pressure condition for carrying out the plasma surface treatment method of the present invention is not particularly limited, and the treatment under a pressure near atmospheric pressure is possible. With the pressure near the above atmospheric pressure,
Refers to a pressure of 100 to 800 Torr. The pressure is preferably in the range of 700 to 780 Torr, which facilitates pressure adjustment and makes the apparatus simple.

The time required for the discharge plasma processing method of the present invention is appropriately determined depending on the magnitude of the applied voltage, the material of the object to be processed, the type of processing gas, the flow rate, etc. When the plastic surface is subjected to water repellent treatment using carbon gas, the electric field strength of the applied voltage is 0.
If it is 1 to 40 kV / cm, it can be made water repellent in about 1 second, and even if the treatment is further performed for a long time, the effect cannot be remarkably improved.

The object to which the plasma processing method of the present invention is applied is not particularly limited, and examples thereof include plastic, metal, paper, wood, decorative cloth, glass, ceramics and building materials. These may be in the form of sheets or molded products.

The above-mentioned plastic is not particularly limited, and examples thereof include polyesters such as polyethylene terephthalate and polyethylene naphthalate; polyolefins such as polyethylene and polypropylene; polystyrene, polyamide, polyvinyl chloride, polycarbonate, polyacrylonitrile and the like. When they are in the form of a film, they may be stretched.

The above-mentioned metal is not particularly limited, and examples thereof include general-purpose alloys such as stainless steel, carbon steel, and super steel; metals composed of single components such as aluminum, copper, and nickel.

The thickness and shape of the object to be processed can be appropriately determined according to the application. For example, the above-mentioned one electrode 2
When the other electrode 3 and the other electrode 3 have the electrode arrangement shown in FIG. 3 described above, discharge plasma is likely to be uniformly generated. Therefore, the thickness of the object to be processed is preferably 0.03 to 30 mm. The object to be treated may be subjected to a known treatment for surface cleaning, surface activation and the like.

The object to be treated may be heated or cooled as required. When imparting water repellency, hydrophilicity or the like to the surface of the object to be treated, room temperature conditions are sufficient.

[0059]

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

Example 1 In the discharge plasma processing apparatus shown in FIG.
The solid dielectric container 4 having a tubular shape of (W) × 5 (D) × 50 (H) is made of polymethacrylate having a thickness of 2 mm, is a gas inlet 6, and has a slit-shaped discharge of 100 mm in width × 1 mm in length. A plasma outlet 7 is provided. In addition, a 100 × 30 × 1 mm copper electrode is disposed in the vicinity of the discharge plasma discharge port 7 so as to face it.

The processing gas supplier 8 has the same structure as that of the solid dielectric container 4 (no electrode is provided). The solid dielectric container 4 and the processing gas supply device 8 are arranged in the positional relationship shown in FIG.

A polyethylene terephthalate film (Lumirror T50, manufactured by Toray Industries, Inc.) having a thickness of 50 μm was processed under the following conditions. Inert gas: helium, flow rate 5 SLM Processing gas: propylene hexafluoride, flow rate 10 SCCM Applied voltage: 15 kHz, 4 kV Processing time: 10 seconds

In the case of this embodiment, the discharge plasma of an inert gas is used.
The cross-sectional area of the protruding port 7 of the ma is 100 mm ²And the flow rate is 5S
With the LM gas supply, the flow velocity was about 830 mm / sec.
Was. After the treatment, the static contact angle on the surface of the object to be treated is 2 μL
Semi-automatic contact angle meter (Kyowa Interface Science Co., Ltd. CA-
X150). As a result, the discharge plasma contacts
Contact angle 90 in a rectangular area of 110 mm wide × 5 mm long
~ 105 degrees (contact angle of the object before processing is 72 degrees)
However, it turned out that it was made water repellent.

Example 2 Example 1 was repeated except that a mixed gas of 25% carbon tetrafluoride + 75% oxygen was used as a processing gas at a flow rate of 20 SCCM.
Surface treatment was performed in the same manner as described above. The static contact angle of the surface of the treated object after the treatment was measured. As a result, the contact angle was 3 in the rectangular area of 110 mm in width and 5 mm in length in contact with the discharge plasma.
It was 0 to 55 degrees (the contact angle of the object to be treated before the treatment was 72 degrees), and it was found that it was hydrophilized.

Example 3 In Example 1, which was connected to a movable jig 9 controlled by a computer so as to maintain the relationship among the solid dielectric container 4, the processing gas supplier 8 and the object 5 shown in FIG. The plasma processing apparatus is provided inside the cylindrical container 5 made of vinyl chloride having an inner diameter of φ200 and an outer diameter of φ210 × 100 mm, and the object to be treated 5
Was arranged in the direction along the circumference of the above, and the plasma processing apparatus was rotated to perform the processing under the conditions of Example 2.

When distilled water was applied to the inside and outside of the object to be treated 5, it was visually observed that the spread of water was clearly different between the inside and the outside, and it was clear that the inside front surface was hydrophilized. Example 2 with the same flat plate as the cylindrical container 5
As a result of treating in the same manner as above and evaluating the contact angle, it was found that the object to be treated 5 was hydrophilized at 81 degrees and after treatment at 40 to 50 degrees.

Example 4 A polyethylene terephthalate film (Lumirror T50, manufactured by Toray Industries, Inc.) having a thickness of 50 μm and a film width of 100 mm was used as a roll for unwinding and winding a roll 5 capable of continuously running at a speed of 5 m / min. The set of commonly used film running equipment is arranged in the TD direction with respect to the plasma processing apparatus of Example 1, and the relationship between the solid dielectric container 4, the processing gas supply unit 8 and the object to be processed 5 shown in FIG. 9 is maintained. Meanwhile, the treatment was performed for 10 minutes under the same conditions as in Example 1.

The contact angle was measured at intervals of 1 cm in the width direction for every 10 m of film length. As is clear from the results shown in FIG. 10, it was found that the water repellent treatment was performed uniformly.

Example 5 The surface treatment was carried out in the same manner as in Example 1 except that the treatment conditions were changed as follows and the discharge plasma was generated by applying a pulsed voltage. Inert gas: Argon, flow rate 5 SLM Processing gas: propylene hexafluoride, flow rate 10 SCCM Applied voltage: pulse voltage according to waveform (a) in FIG. 2 Crest value 6.2 kV, frequency 6.3 kHz, pulse width 18
0 μm processing time: 10 seconds

As a result of measuring the static contact angle of the surface of the object to be treated after the treatment, the discharge plasma was in contact with 110 mm in width × 5 in length.
In the rectangular area of mm, the contact angle was 100 to 115 degrees (the contact angle of the object to be treated before the treatment was 72 degrees), and it was found to be water repellent.

Example 6 The surface treatment was carried out in the same manner as in Example 2 except that the treatment conditions were changed as follows and the discharge plasma was generated by applying a pulsed voltage. Inert gas: nitrogen gas, flow rate 5 SLM Processing gas: 25% carbon tetrafluoride + 75% oxygen mixed gas,
Flow rate 20 SCCM Applied voltage: Pulse voltage according to waveform (d) in FIG. 2 Peak value 8.9 kV, frequency 1.2 kHz, pulse width 60
0 μm processing time: 10 seconds

As a result of measuring the static contact angle of the surface of the object to be treated after treatment, the discharge plasma was in contact with 110 mm in width × 5 in length.
In the rectangular area of mm, the contact angle was 15 to 40 degrees (the contact angle of the object to be treated before the treatment was 72 degrees), and it was found that the surface was made hydrophilic.

[0073]

Since the plasma processing method of the present invention has the above-mentioned constitution, a small amount of processing gas is used for continuous processing, partial processing, etc. of a sheet-like material, a molded body, etc. under atmospheric pressure. Can be performed uniformly, and the process can be easily performed in-line, so the adhesiveness and printability of the surface of the sheet or molded product can be easily modified, and antifouling property and conductivity can be achieved. It is also possible to give high functionality by adding.
Further, according to the method of applying the pulsed electric field to generate the discharge plasma, it is possible to perform stable processing at a high level.

[Brief description of drawings]

FIG. 1 is a sectional view of an example of a discharge plasma processing apparatus of the present invention.

FIG. 2 is a voltage waveform diagram showing an example of a pulsed electric field.

FIG. 3 is a block diagram of a power supply that generates a pulsed electric field.

FIG. 4 is a diagram showing an example of arrangement of other electrodes of the discharge plasma processing apparatus of the present invention.

FIG. 5 is a diagram showing an example of arrangement of other electrodes of the discharge plasma processing apparatus of the present invention.

FIG. 6 is a diagram showing an example of continuously processing a shaped product by the discharge plasma processing apparatus of the present invention.

FIG. 7 is a diagram showing an example of continuously processing a sheet-shaped or film-shaped object to be processed by the discharge plasma processing apparatus of the present invention.

FIG. 8 is a diagram showing an example of continuously or partially surface-treating a film-shaped object to be processed by the discharge plasma processing apparatus of the present invention.

FIG. 9 is a diagram showing the arrangement of a solid dielectric container, a processing gas supply unit, and an object to be processed in an example.

FIG. 10 is a diagram showing a contact angle of a surface-treated object in an example, the vertical axis represents the contact angle, and the horizontal axis represents the position in the film width direction.

[Explanation of symbols]

 1 Power Supply 2 One Electrode 3 Other Electrode 4 Solid Dielectric Container 5 Object to be Processed 6 Gas Inlet 7 Discharge Plasma Projecting Port 8 Processing Gas Supply Machine 9 Movable Jig 10 Movable Jig

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location H05H 1/46 C08J 7/00 306 // C08J 7/00 306 H01L 21/302 B

Claims (8)

[Claims] 1. A discharge plasma processing method, characterized in that discharge plasma generated in an inert gas is caused to project toward the treated portion while supplying the treated gas to the treated portion. 2. A state in which an inert gas is circulated in a solid dielectric container provided with one electrode and a discharge plasma projecting port,
A discharge plasma is generated by applying a voltage between the one electrode and the other electrode that forms a pair, and a processing gas is supplied toward the target portion from a direction intersecting with the protruding direction of the discharge plasma. The discharge plasma processing method according to claim 1. 3. The plasma processing method according to claim 1, wherein discharge plasma is generated by applying a pulsed voltage. 4. The plasma processing method according to claim 1, wherein the inert gas is argon and / or nitrogen. 5. A discharge comprising a solid dielectric container having one electrode disposed on an outer surface thereof and having a discharge plasma projecting port, another electrode paired with the one electrode, and a processing gas supplier. A plasma processing apparatus, wherein a discharge plasma is generated by applying a voltage between the pair of electrodes in a state where an inert gas is circulated in the solid dielectric container, and the discharge plasma The plasma processing apparatus is characterized in that it is arranged so that the projecting direction of the process gas and the process gas projecting direction of the process gas supply machine intersect. 6. The solid dielectric container and the processing gas supply device are connected to a movable jig, and the solid dielectric container and the processing gas supply device are movable while maintaining a substantially constant relative position. The plasma processing apparatus according to claim 5, which is made. 7. The plasma processing apparatus according to claim 5, wherein the object-to-be-processed moving device moves the object-to-be-processed in the vicinity of the projecting port of the discharge plasma and is exposed to the discharge plasma. 8. The plasma processing apparatus according to claim 5, wherein the voltage applied between the pair of electrodes is pulsed.