JPH10130851A - Continuous treatment of sheet-like substrate and its apparatus - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a continuous treatment method of a sheet-like substrate under a pressure near an atm. pressure. SOLUTION: A pair of counter electrodes 3, 4, are disposed in a treating vessel 2 having a sheet introducing port 7 and sheet discharge port 8 sealed to a non-hermetic state to the extent of permitting the leakage of gas. The opposite surface of one or both of these counter electrodes are coated with solid dielectric substances 9. The sheet-like substrate 6 is made to travel continuously between the counter electrodes and simultaneously gases for treatment are continuously brought into contact with the sheet-like base material 6 from the direction reverse from the traveling direction of the substrate. In addition, pulsed electric fields are impressed between the counter electrodes, by which discharge plasma is generated.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method and an apparatus for continuously treating a sheet-like substrate.

[0002]

2. Description of the Related Art Sheet-like base materials made of plastic, metal, paper, fiber, etc. are widely used as home electric parts, automobile parts and the like. The surface treatment is often performed after the material is formed. As such a surface treatment, for example, a functional group layer is formed on the surface of the sheet-like base material, or a radical layer is formed by discharge plasma to control the surface energy of the sheet-like base material. Examples of the method include imparting water and the like to improve wettability, adhesiveness, and the like, and further forming a film having a function excellent in electric characteristics, optical characteristics, and the like.

Conventionally, as a method of modifying the surface of a sheet-like base material to form a film having excellent functions on the surface, a method by corona discharge treatment under atmospheric pressure, a plasma by glow discharge under reduced pressure, A processing method, a plasma polymerization method, a plasma CVD method and the like are known.

[0004] A method using corona discharge treatment under atmospheric pressure has been put to practical use as a dry process for surface treatment of a sheet-like substrate, but this method oxidizes the surface of the sheet-like substrate to make it hydrophilic. For example, it was difficult to improve water repellency or coat a thin film.

[0005] The plasma processing method using glow discharge under reduced pressure is widely applied industrially as a processing method capable of meeting various purposes of surface treatment. However, since this processing method uses glow discharge plasma in a low pressure range of 0.01 to 10 Torr, a closed tank, a pump, and the like are required, and the apparatus has a drawback that the apparatus becomes large-sized.

As a method for continuously treating the surface of a sheet-like base material, a roll of a long sheet-like base material is put into a vacuum chamber, and the sheet-like base material is rolled from the roll in the chamber. There are known a batch method in which a material is drawn out as needed and the surface of the sheet-like substrate is treated as needed, and a differential treatment method in which the material is gradually evacuated from atmospheric pressure to reduced pressure. However, these continuous processing methods also have a drawback that a very large pump having a large capacity is required for exhausting the inside of the processing chamber, so that an increase in the size of the processing apparatus is inevitable.

For example, continuous treatment of the surface of a sheet-like substrate is performed by
When performing by glow discharge under reduced pressure so that it can correspond to various purposes, the above-described batch method is used,
In this treatment method, for example, when the sheet-like substrate to be subjected to the surface treatment is a highly water-absorbent plastic sheet-like substrate or the like, a long time is required for evacuation or a traveling system such as a roll becomes expensive. Therefore, there is a disadvantage that the cost of the processed product is high.

Japanese Patent Application Laid-Open No. 3-143930 discloses that after the inside of a processing vessel is replaced with a processing gas such as helium gas in order to continuously surface-treat a sheet-like substrate under atmospheric pressure,
There is disclosed a technique for continuously performing a plasma discharge process by introducing a sheet-shaped substrate under an atmospheric pressure from a non-hermetically sealed inlet while continuously introducing a processing gas. However, this method has a drawback that when the traveling speed of the sheet-shaped substrate exceeds about 3 m / min, air is mixed into the discharge plasma due to entrainment of external air, and it is difficult to achieve the object. I was

[0009]

SUMMARY OF THE INVENTION In view of the above, the present invention provides a method for continuously treating the surface of a sheet-like substrate even at a pressure near the atmospheric pressure and at a high traveling speed of the sheet-like substrate. It is an object of the present invention to provide a method and an apparatus for continuous treatment of a sheet-like substrate which are possible.

[0010]

According to the present invention, there is provided a method for continuously treating a sheet-like substrate, comprising a sheet inlet and a sheet outlet which are sealed in a non-hermetic state to such an extent that gas leakage can be tolerated. Inside, a pair of opposing electrodes is provided, one or both opposing surfaces of the opposing electrodes are covered with a solid dielectric, and a sheet-like base material is continuously run between the opposing electrodes, and at the same time, the sheet A discharge plasma is generated by continuously contacting a processing gas from a direction opposite to the running direction of the substrate and applying a pulsed electric field between the opposed electrodes.

In the present invention, the plasma processing can be performed in the processing container under a pressure near the atmospheric pressure. The above-mentioned pressure near the atmospheric pressure refers to a pressure of 100 to 800 Torr. Easy pressure adjustment and simple equipment 700
The range of -780 Torr is preferable.

Examples of the counter electrode include those made of a single metal such as copper and aluminum, alloys such as stainless steel and brass, and intermetallic compounds. The solid dielectric is disposed on one or both of the opposing surfaces of the electrode in close contact with the opposing surface. At this time, if there is a portion where the electrodes directly face each other without being covered by the solid dielectric, an arc discharge occurs therefrom. Therefore, the electrodes are disposed so as to completely cover the facing surface. The shape of the solid dielectric may be a sheet-like substrate or a film, but if it is too thick, a high voltage is required to generate discharge plasma, and if it is too thin, dielectric breakdown occurs when a voltage is applied and an arc discharge occurs. Therefore, the thickness is preferably set to 0.05 to 4 mm.

Examples of the solid dielectric include plastics such as polytetrafluoroethylene and polyethylene terephthalate, glass, metal oxides such as silicon dioxide, aluminum oxide, zirconium dioxide and titanium dioxide, and double oxides such as barium titanate. No.

In particular, the relative dielectric constant under an environment of 25 ° C. is 1
The use of a solid dielectric having a value of 0 or more can generate a high-density discharge plasma at a low voltage, and is suitable for high-speed continuous processing and high-speed front and back processing. The upper limit of the relative permittivity is not particularly limited, but is 18,5 in actual materials.
A solid dielectric having a relative dielectric constant of about 10 to 100 which can be used in the present invention is available on the order of about 00. Specific examples of the solid dielectric having a relative dielectric constant of 10 or more include metal oxides such as zirconium dioxide and titanium dioxide, and double oxides such as barium titanate.

A titanate compound is known as a ferroelectric substance. In the case of TiO ₂ alone, the relative permittivity differs depending on the crystal structure, and the relative permittivity is about 80 in the rutile type crystal structure.
In the case of a compound of a metal oxide such as Ba, Sr, Pb, Ca, Mg, and Zr and TiO ₂ , the relative dielectric constant is about 2,
000-18,500, and its relative permittivity can be changed by purity or crystallinity.

On the other hand, the TiO_TwoWhen used alone, heating ring
Use environment was restricted due to drastic composition change in the environment
Therefore, the film obtained by the normal film forming method has a specific resistance
10^FourIt is easy to shift to arc discharge because it is about Ωcm
Be careful. For this reason TiO_TwoThan alone
Al_TwoO_ThreeIt is better to use it by incorporating it. TiO_TwoAnd A
l_TwoO_ThreeThe mixture is thermally stable because it is thermally stable.
It is suitable. Preferably, 5 to 50% by weight of titanium oxide,
Metallic acid mixed with 50-95% by weight of aluminum oxide
Oxide film. 50% by weight of aluminum oxide
If it is less than 95%, arc discharge is likely to occur.
If it exceeds, a high applied voltage is required for discharge plasma generation.
You. Such a film has a relative dielectric constant of about 10 to 14,
Resistance is 10 ^TenAnd the solid dielectric used in the present invention
It is suitable.

When zirconium oxide alone is used, it has a relative dielectric constant of about 12, which is advantageous for generating discharge plasma at a low voltage. Normally, zirconium oxide is composed of 30 parts of yttrium oxide (Y ₂ O ₃ ), calcium carbonate (CaCO ₃ ), magnesium oxide (MgO) or the like.
It is added within the range of weight% to prevent expansion and shrinkage due to crystal transformation and is stabilized, but such an additive may be added. The relative dielectric constant is determined by the type of the additive and the crystallinity of the metal oxide, and it is preferable that at least 70% by weight be zirconium oxide. For example, a zirconium oxide film containing 4 to 20% by weight of yttrium oxide has a relative dielectric constant of about 8 to 16, and is suitable as the solid dielectric of the present invention.

The solid dielectric may be in the form of a sheet or a film, but preferably has a thickness of 0.01 to 4 mm. If the thickness is too large, a high voltage is required to generate the induced discharge plasma. If the thickness is too small, dielectric breakdown occurs when a voltage is applied, and arc discharge occurs. The solid dielectric may be used in the form of a film on a conductor such as carbon steel or directly on an electrode. In this case, the thickness of the coating is
If the thickness is too thin, discharge plasma is easily generated, but if it is too thin, arc discharge occurs, and if it is too thick, dielectric loss increases, discharge plasma hardly occurs, and it becomes high temperature or cracks occur in the coating, It is preferably between 10 and 1,000 μm, more preferably between 50 and 700 μm. It is preferable that the metal oxide film has a uniform thickness because the obtained discharge plasma becomes uniform.

The present invention has one feature in that discharge plasma is generated by applying a pulsed electric field between the opposed electrodes. FIG. 1 shows an example of a pulse voltage waveform. The waveforms (a) and (b) are impulse waveforms, the waveform (c) is a pulse waveform, and the waveform (d) is a modulation waveform.
Although FIG. 1 shows a case where the voltage application is repeated positive and negative, a pulse of a type that applies a voltage to either the positive or negative polarity side may be used.

The pulse voltage waveform in the present invention is not limited to the above-mentioned waveforms, but the shorter the rise time and the fall time of the pulse, the more efficient the ionization of the gas during plasma generation. In particular, the rise time and fall time of the pulse are preferably 40 ns to 100 μs. Less than 40 ns is not realistic and 10
If it exceeds 0 μs, the discharge state easily shifts to an arc and becomes unstable. More preferably, it is 50 ns to 5 μs. Here, the rise time refers to the time during which the voltage change is continuously positive, and the fall time refers to the time during which the voltage change is continuously negative. Further, the modulation may be performed using pulses having different pulse waveforms, rise times, and frequencies. Such modulation is suitable for performing high-speed continuous surface treatment.

The frequency of the pulse electric field is 1 kHz to 100
Preferably, it is kHz. If it is less than 1 kHz, it takes too much time for the treatment, and if it exceeds 100 kHz, arc discharge is likely to occur. Further, the time during which one pulse electric field is applied is preferably 1 μs to 1000 μs. If it is less than 1 μs, the discharge becomes unstable, and if it exceeds 1000 μs, it tends to shift to arc discharge. More preferably, it is 3 μs to 200 μs. The time during which the one pulse electric field is applied is shown in FIG. 1 as an example, but refers to a continuous ON time of one pulse in a pulse electric field composed of repetition of ON and OFF.

The magnitude of the voltage applied to the above-mentioned counter electrode can be appropriately determined.
It is preferable to set the range to be 00 kV / cm. 1k
If it is less than V / cm, processing takes too long,
If it exceeds kV / cm, arc discharge is likely to occur.
Further, a pulse electric field on which a direct current is superimposed may be applied.

In the present invention, the sheet-like base material to be subjected to the surface treatment is introduced into the processing vessel so as to continuously travel in the space between the opposed electrodes, and is discharged. The introduction and discharge of the sheet-like substrate can be performed by a known method. In the present invention, since the inside of the processing container is under a pressure close to the atmospheric pressure, the sheet introduction port and the sheet discharge port of the processing container may be sealed in a non-hermetic state enough to allow gas leakage. It is not necessary to prevent gas in the container from leaking out.

In the continuous treatment of the sheet-like base material of the present invention, any treatment can be performed by selecting a gas (hereinafter, referred to as a processing gas) existing in a space between the opposed electrodes for generating discharge plasma.

As the processing gas, a fluorine-containing compound gas is used.
To form a fluorine-containing group on the substrate surface.
To reduce the surface energy and obtain a water-repellent surface.
Can be. As the fluorine element-containing compound, 4
Carbon (CF)_Four), Carbon hexafluoride (C_TwoF₆), 6F
Propylene nitride (CF_ThreeCFCF_Two), Octafluorocyclo
Butane (C_FourF₈) And other fluorine-carbon compounds, monochloride 3
Fluorocarbon (CCIF) _ThreeHalogen-carbon compounds such as
Sulfur hexafluoride (SF₆) And other fluorine-sulfur compounds
I can do it. Fluorinated water, a harmful gas, from a safety perspective
Fluorocarbon, Hexafluorocarbon, Hexafluoride that does not generate element
It is preferable to use propylene and octafluorocyclobutane.
New

Further, a hydrophilic functional group such as a carbonyl group, a hydroxyl group or an amino group is formed on the surface of a substrate by using the following oxygen element-containing compound, nitrogen element-containing compound and sulfur element-containing compound as a processing gas. As a result, the surface energy can be increased, and a hydrophilic surface can be obtained.

As the oxygen element-containing compound, 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. Examples of the nitrogen element-containing compound include nitrogen and ammonia. The nitrogen element-containing compound and hydrogen may be used as a mixture. Examples of the sulfur element-containing compound include sulfur dioxide and sulfur trioxide. Further, sulfuric acid can be vaporized and used. These may be used alone or in combination of two or more.

Further, by performing the treatment in an atmosphere of a monomer having a hydrophilic group and a polymerizable unsaturated bond in the molecule, a hydrophilic polymer film can be deposited. Examples of the hydrophilic group include a hydroxyl group, a sulfonic group, a sulfonic group, a primary or secondary or tertiary amino group, an amide group,
And hydrophilic groups such as quaternary ammonium bases, carboxylic acid groups and carboxylic acid groups. In addition, a hydrophilic polymer film can be similarly deposited by using a monomer having a polyethylene glycol chain. Examples of the monomer include (meth) acrylic acid, (meth) acrylamide, N, N-dimethylacrylamide, sodium (meth) acrylate, potassium (meth) acrylate, sodium styrenesulfonate, allyl alcohol, allylamine, and polyethylene glycol diamine. (Meth) acrylic acid esters and the like. These monomers are used alone or as a mixture.

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

From the viewpoint of economy and safety, it is preferable to perform the treatment in an atmosphere in which the treatment gas is diluted with an inert gas. Helium, as an inert gas,
Rare gases such as neon, argon, and xenon, and nitrogen gas are exemplified. These may be used alone or in combination of two or more. Conventionally, treatment has been performed in the presence of helium under a pressure near atmospheric pressure. However, according to the method of applying a pulsed electric field of the present invention, argon and nitrogen are inexpensive compared to helium. Stable processing in gas is possible.

In the present invention, the above-mentioned processing gas is supplied into the processing vessel at the same time as the sheet-like substrate is continuously run between the counter electrodes. At this time, one feature of the present invention resides in that the processing gas is continuously brought into contact with the sheet-like substrate in a direction opposite to the running direction. By supplying the processing gas so as to continuously contact from the direction opposite to the running direction of the sheet-like substrate, it is possible to reduce the entrapment of air into the space where discharge plasma is generated, As a result, a reduction in processing capacity can be prevented. The opposite direction will be described later in detail with examples.

The continuous processing apparatus for a sheet-like substrate according to the second aspect of the present invention includes a pair of a processing container having a sheet inlet and a sheet outlet sealed in a non-hermetic state capable of permitting gas leakage. An opposing electrode is provided, one or both opposing surfaces of the opposing electrode are covered with a solid dielectric, and a sheet-shaped substrate is continuously run between the opposing electrodes, It has a gas flow generating mechanism arranged to continuously contact the processing gas from the direction opposite to the running direction of the sheet-like substrate, and discharges by applying a pulsed electric field between the counter electrodes. It is characterized in that plasma is generated.

Examples of the continuous processing apparatus for the sheet-like base material include the following. FIG. 2 is a cross-sectional view of an example of the continuous sheet-like substrate processing apparatus. The apparatus shown in FIG. 2 includes a power supply unit 1, a processing vessel 2, an upper electrode 3, a lower electrode 4, a gas flow generating mechanism 5 using a turbo blower, a sheet-like substrate 6, a sheet inlet 7, a sheet outlet 8, a solid dielectric. 9, a gas inlet tube 10, a gas outlet 11, a solid dielectric side wall 12, a gas flow path 13, and a set of sheet-like substrate traveling systems. The solid dielectric side wall 12 is provided along the running direction of the sheet-shaped base material so as to surround a space where discharge plasma is generated between the opposed electrodes, and prevents the processing gas from diffusing to the surroundings. .

Although only one set of electrodes is shown in FIG. 2, a large number of sets of electrodes may be provided as necessary to increase the distance at which the sheet-shaped substrate 6 comes into contact with the discharge plasma, thereby increasing the speed. The sheet-like substrate may be run. FIG. 3 is an example of a processing apparatus having many sets of electrodes. By introducing different types of processing gases between the electrodes, the processing layers can be formed in multiple stages.

The power supply unit 1 can apply a pulsed electric field in the above-described range. Less than,
The power supply unit 1 will be described in detail. FIG. 4 shows a block diagram of a power supply when such a pulsed electric field is applied. further,
FIG. 5 shows an example of an equivalent circuit diagram of the power supply. In FIG. 5, SW is a semiconductor element functioning as a switch. By using a semiconductor element having a turn-on time and a turn-off time of 500 ns or less as the switch, the electric field strength as described above is 1 to 100 kV / c.
m, and a high-voltage and high-speed pulsed electric field having a pulse rise time and a fall time of 40 ns to 100 μs can be realized.

Hereinafter, the principle of the power supply will be briefly described with reference to the equivalent circuit diagram of FIG. + E is a positive DC voltage supply unit, and -E is a negative DC voltage supply unit. SW1
Reference numerals 4 to 4 denote switch elements composed of the high-speed semiconductor elements as described above. D1 to D4 indicate diodes. I _{1 to} I ₄ indicate the direction of current flow.

[0037] First, SW1 is when ON, the positive load is charged in the flow direction current I _1. Then, the SW1 is turned OFF, by turning ON the SW2 instantaneously, the electric charge charged is charged in the direction of I ₃ through SW2 and D4. Next, when the switch SW3 is turned on after the switch SW2 is turned off, the load having the negative polarity causes the current I ₂
Charge in the direction of flow. Next, the SW3 is turned OFF, by turning ON the SW4 instantaneously, the electric charge charged is charged in the direction of I ₄ through SW4 and D2. By repeating the above series of operations, the output pulse of FIG. 6 can be obtained. Table 1 shows this operation table.

[Table 1] The advantage of this circuit is that even if the impedance of the load is high, the charged charge is transferred to SW2 and D4 or SW4.
4 and D2 can be reliably discharged, and high-speed charge can be performed using SW1 and SW3 which are high-speed turn-on switch elements. So the rise time,
A pulse signal having a very fast fall time can be obtained.

The processing vessel 2 is not particularly limited.
For example, stainless steel (SUS304), other metal, glass, plastic, and the like can be given. The processing container 2 is provided on both side walls thereof with a sheet inlet 7 into which the sheet-shaped substrate 6 is introduced and a sheet outlet 8 through which a surface treatment end portion of the sheet-shaped substrate 6 is discharged. Have been. The above-mentioned sheet substrate 6
Is provided by a roll provided outside the processing container 2.
The sheet is conveyed from the sheet inlet 7 to the sheet outlet 8. The sheet inlet 7 and the sheet outlet 8 are
It is preferable that the processing container 2 be sealed in a non-hermetic state to the extent that leakage of the filling gas inside the processing container 2 can be tolerated.

As the arrangement structure of the upper electrode 3 and the lower electrode 4, in addition to the parallel plate type structure shown in FIG.
A structure such as a coaxial cylindrical type, a cylindrical opposed flat plate type, a spherical opposed flat plate type, and a hyperboloid opposed type may be used. The distance between the upper electrode 3 and the lower electrode 4 varies depending on the thickness of the solid dielectric 9, the thickness of the sheet-like substrate 6, the magnitude of the applied voltage, and the like. No. 3 is preferred, which is within a range where the uniformity of the discharge plasma is not impaired, that is, about 1 to 50 mm.

The solid dielectric 9 is provided so as to completely cover the surface of the lower electrode 4 facing the upper electrode 3. Conversely, it may be arranged on the surface of the upper electrode 3 facing the lower electrode 4. When the sheet-shaped substrate 6 is made of a conductive material such as a metal, it is preferable to dispose the sheet-shaped substrate 6 on both surfaces of the upper electrode 3 and the lower electrode 4.

In the apparatus for continuously treating a sheet-like substrate shown in FIG. 2, a gas flow disposed so that the above-mentioned processing gas is continuously brought into contact with the surface of the above-mentioned sheet-like substrate 6 in a direction opposite to the running direction. It has a generating mechanism. Examples of the gas flow generating mechanism include a gas flow generating mechanism 5 that circulates a processing gas existing in the space between the electrodes by a pump, a blower, or the like from the sheet-shaped base material discharge side to the introduction side shown in FIG. For example, a gas flow generating mechanism that blows out gas by a nozzle-shaped gas supply device shown in FIG. 7, and supplies the processing gas in a desired direction to an electrode facing a processing surface of a sheet-like substrate shown in FIG. A gas flow generating mechanism that blows out a gas by providing holes, a gas flow generating mechanism that pumps in from the vicinity of the sheet-like base material introduction side electrode end shown in FIG. 9, and a sheet-like base material discharge side electrode shown in FIG. A gas flow generating mechanism that blows out gas from the vicinity of the extreme part by a pump, a blower, or the like, a gas flow generating mechanism that blows air by a fan shown in FIG.

Reference numerals 14 in FIG. 7, 15 in FIG. 8, FIG. 9, 16 in FIG. 10, and 17 in FIG. Reference numeral 17 in FIG. 11 denotes a blower.

The gas flow generating mechanism 5 shown in FIG. 2 is a particularly preferable example because the influence of the gas flow reflected on the side wall of the processing vessel is small and the gas can be easily reused. When the gas generating mechanism 5 has a gas inlet on the sheet inlet 7 side and a gas inlet larger in diameter than the gas outlet and a slit-shaped gas outlet on the sheet outlet 8 side, a high speed is used. A gas flow can be easily generated uniformly, and the consumption efficiency of the processing gas can be improved. In order to generate the gas flow efficiently, a side wall made of a solid dielectric may be provided on the side where the gas flow does not pass, as shown in FIG.

In the continuous processing apparatus shown in FIG. 2, a gas flow is generated on one side of the sheet-like substrate 6 where the processing is performed. The gas flow may be generated. In addition, a sensor for detecting the concentration of the processing gas is disposed in the middle of the gas flow path 13 to control the concentration of the processing gas in the gas flow, or to provide a separator for the unnecessary gas to control the purity of the processing gas. You can do it.

The processing gas is flow-controlled, and is introduced into the processing vessel 2 from the gas introduction pipe 10. When a gas diluted with an inert gas or a mixed gas of a plurality of types is used, it is preferable that the gas is sufficiently mixed and then introduced into the processing container 2 in consideration of a difference in flow rate and mass of each gas.
Excessive processing gas in the processing container 2 is supplied to the gas outlet 1
Emitted from 1. After this, it may be released to the atmosphere,
It may be introduced again into the processing container 2.

The flow rate of the processing gas supplied from the gas flow generating mechanism is determined by the running speed of the sheet-like substrate, the airtightness of the inlet required for introducing the sheet-like substrate, and the type of the sheet-like substrate. And so on. It is preferable that the flow rate of the processing gas be equal to or higher than the traveling speed of the sheet-shaped substrate.

The sheet-like substrate to be subjected to the method and apparatus for continuous treatment of the sheet-like substrate of the present invention is not particularly limited, and is applicable to plastic, metal, glass, paper, fiber, nonwoven fabric and the like.

[0048]

According to the method for continuously treating a sheet-like substrate of the present invention, the processing gas is continuously brought into contact with the surface of the sheet-like substrate in a direction opposite to the running direction, so that air entrained in the discharge plasma is reduced. Thus, the continuous processing of the sheet-like base material can be continuously performed at a high speed under a pressure close to the atmospheric pressure. Also,
Since the discharge plasma is generated by applying a pulsed electric field, the range of selection of the processing gas is wider than that of the conventional method, and a voltage condition or the like that can realize a stable discharge state. The range is wide. Furthermore, by applying a pulsed electric field, it is possible to generate a higher density discharge plasma, which corresponds to high-speed continuous processing.

[0049]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. In the following embodiment, a high-voltage pulse power supply (manufactured by Heiden Laboratories, semiconductor element: IXYS, model number IXBH40N160-62) according to the equivalent circuit diagram of FIG.
7G).

Examples 1 to 3 The apparatus shown in FIG. 2 (electrode width 350 × length 150) provided with a mechanism for circulating by a turbo blower as the gas flow generator 5
mm) and a thickness of 50 μm by the operation described below.
A water-repellent treatment was performed on the surface of a polyethylene terephthalate (L, mirror, T50 manufactured by Toray Industries, contact angle 70 °) film having a width of 300 mm and a width of 300 mm under the processing conditions shown in Table 2. The static contact angle of the film surface after the treatment was measured.

The static contact angle was measured by arbitrarily cutting 1 m from the processed film, dropping 2 mm water droplets at 10 cm intervals, and measuring the contact angle with Kyowa Interface Science Co., Ltd.
-X150), the static contact angle was measured, and the maximum value and the minimum value were also shown in Table 2.

<Operation> First, a polyethylene terephthalate film wound body to be processed was set on an unwinding roll, and the film was passed through the inlet 7 → between the electrodes → the outlet 8 in this order, and was fixed to a winding roll. Then, the inlet 7,
The outlet 8 is closed, and the air inside the processing container 2 is exhausted from the gas introduction pipe 1.
A processing gas having a predetermined gas flow rate from 1 was supplied and replaced with the processing gas to atmospheric pressure. Subsequently, a gas flow having a desired flow rate is generated between the electrodes by the gas flow generator 5, and the film is continuously run at a predetermined speed from the inlet 7 to the outlet 8 by rotating the winding roll. By applying a pulsed electric field (voltage waveform: (a) of FIG. 1) under the conditions shown in Table 2, discharge plasma was generated between the electrodes to continuously process.

Examples 4 and 5 For the purpose of hydrophilic treatment, surface treatment was carried out under the conditions shown in Table 2 by using the apparatus and operation used in Examples 1 to 3. The results of the contact angle measurement are also shown in Table 2.

Comparative Example 1 Processing was performed in the same manner as in Example 1 except that a sine waveform voltage was applied instead of a pulsed electric field. However, a voltage of 10 kV or more was applied to generate a discharge. Since it was necessary and the discharge state was arc discharge, the polyethylene terephthalate film as the object to be processed melted, and the surface treatment could not be performed. For reference, Table 2 shows the results of processing using a sine waveform voltage using He gas instead of Ar gas.

Comparative Example 2 In the apparatus shown in FIG. 2, the processing gas was the same as the running direction of the film in the same manner as in Example 1 except that the running direction of the polyethylene terephthalate film as the object to be processed was reversed. The treatment was performed by contacting from the directions. The results of the contact angle measurement were inferior to Example 1 as shown in Table 2.

[0056]

[Table 2]

As is clear from the examples, the present invention enables a high-speed and uniform continuous surface treatment as compared with the prior art.

[0058]

Since the method and apparatus for continuous treatment of a sheet-like substrate of the present invention have the above-mentioned constitution, the surface of the sheet-like substrate can be treated continuously at a relatively high speed, and the surface can be easily treated. Processing steps can be inlined.

[Brief description of the drawings]

FIG. 1 is a voltage waveform diagram showing an example of a pulsed electric field according to the present invention.

FIG. 2 is a schematic cross-sectional view showing an example of a continuous processing apparatus for a sheet-like substrate according to the present invention.

FIG. 3 is a schematic cross-sectional view showing an example of a continuous processing apparatus for a sheet-like substrate according to the present invention.

FIG. 4 is a block diagram of a power supply that generates a pulsed electric field.

FIG. 5 is an equivalent circuit diagram of a power supply that generates a pulsed electric field.

FIG. 6 is a diagram of an output pulse signal corresponding to an operation table of a pulsed electric field.

FIG. 7 is a schematic diagram showing an example of a gas flow generation mechanism.

FIG. 8 is a schematic diagram showing an example of a gas flow generation mechanism.

FIG. 9 is a schematic view showing an example of a gas flow generating mechanism.

FIG. 10 is a schematic view showing an example of a gas flow generating mechanism.

FIG. 11 is a schematic view showing an example of a gas flow generating mechanism.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Power supply part (high voltage pulse power supply) 2 Processing container 3 Upper electrode 4 Lower electrode 5 Gas flow generation mechanism by turbo blower 6 Sheet base material 7 Sheet inlet 8 Sheet outlet 9 Solid dielectric 10 Gas inlet pipe 11 Gas exhaust Outlet 12 Side wall made of solid dielectric 13 Gas flow path 14 Nozzle 15 Electrode provided with many holes 16 Pump 17 Blower

Claims (6)

[Claims] 1. A pair of counter electrodes are provided in a processing container having a sheet inlet and a sheet outlet sealed in a non-hermetic state to a degree that gas leakage can be tolerated, and one of the counter electrodes is provided. Or, both opposing surfaces are covered with a solid dielectric, and at the same time the sheet-shaped base material is continuously run between the counter electrodes, and the processing gas is continuously fed from the direction opposite to the running direction of the sheet-shaped base material. And generating a discharge plasma by applying a pulsed electric field between the opposed electrodes. 2. The voltage rise time and fall time in a pulsed electric field are 40 ns to 100 μm.
2. The method according to claim 1, wherein the electric field strength is 1 to 100 kV / cm. 3. The method according to claim 1, wherein one pulse electric field is applied for 1 μs to 1000 μs in the pulsed electric field.
3. The method according to claim 1, wherein the frequency is 1 kHz to 100 kHz. 4. A pair of counter electrodes is disposed in a processing container having a sheet inlet and a sheet outlet sealed in a non-hermetic state to a degree that gas leakage can be tolerated, and one of the counter electrodes is provided. Or both opposing surfaces are covered with a solid dielectric, so that the sheet-shaped base material is continuously run between the counter electrodes, and from a direction opposite to the running direction of the sheet-shaped base material. It has a gas flow generating mechanism disposed so as to continuously contact the processing gas, and discharge plasma is generated by applying a pulsed electric field between the counter electrodes. Continuous processing equipment for sheet-like substrates. 5. A DC voltage supply unit capable of supplying a high voltage DC, and a turn-on time and a turn-off time of 50 hours.
The high-voltage pulse power supply comprising a pulse control unit for converting the high-voltage direct current into a high-voltage pulse by a semiconductor element of 0 ns or less is connected between the counter electrodes. Continuous processing equipment for sheet-like substrates. 6. The apparatus according to claim 4, wherein the solid dielectric has a relative dielectric constant of 10 or more in a 25 ° C. environment.