JPH07207449A - Method for manufacturing laminated body - Google Patents

Abstract

(57) [Summary] [Object] To provide a method for producing a laminate having excellent surface performance by subjecting a substrate to plasma surface treatment at a low voltage under a pressure near atmospheric pressure. A solid conductor 6 having a specific conductivity of 10 or more and containing a titanic acid compound is disposed on at least one opposing surface of a pair of opposing metal electrodes 4 and 5 so as to completely cover the electrode surface. A base material 7 to be treated is mounted between the metal electrodes 4 and 5. An inert gas and a reaction gas are introduced into the space between the metal electrodes 4 and 5. A voltage is applied to the metal electrodes 4 and 5 under a pressure near atmospheric pressure to generate discharge plasma, and the excited active species are brought into contact with the surface of the base material for surface treatment.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a laminate having excellent surface performance by subjecting a substrate to plasma surface treatment at a low voltage under a pressure near atmospheric pressure.

[0002]

2. Description of the Related Art Conventionally, as a method of controlling the wettability of a solid surface and modifying the surface, a method of performing surface treatment by glow discharge plasma under a low pressure of 0.1 Torr or more and less than 10 Torr is known, and is industrially used. Has also been applied. In this case, if the surface treatment of the solid surface is carried out at a pressure higher than this, the discharge will be localized and it will shift to arc discharge, so it should be applied to the surface treatment of plastic substrates with poor heat resistance. I can't.

Therefore, the container requires an expensive vacuum chamber and also an evacuation device. Furthermore, since it is processed in a vacuum, when processing a large-area substrate, the capacity of the vacuum chamber must be increased,
In addition, the vacuum exhaust device also needs to have a large output, and the equipment becomes extremely expensive. In addition, when the surface treatment of a plastic substrate having a high water absorption rate is performed, it takes a long time to evacuate, and the cost of the treated product becomes high.

Therefore, in order to deal with such a problem, for example, Japanese Unexamined Patent Publication No. 2-15171 discloses a double-dielectric-coated electrode in which a solid dielectric is provided on the surfaces of an upper electrode and a lower electrode. There has been proposed an atmospheric pressure plasma reaction method in which a rare gas and a monomer gas are mixed and introduced into a reaction container having the above, and plasma is excited under atmospheric pressure to treat the substrate surface.

Further, in Japanese Unexamined Patent Publication No. 2-48626, a monomer gas mixed with an inert gas and introduced into a reaction vessel having an upper electrode composed of a plurality of thin wires is converted into a plasma state under atmospheric pressure, and the surface of the substrate is treated. A thin film forming method for forming a thin film has been proposed.

Further, in Japanese Patent Laid-Open No. 2-73979, a high resistance element of 10 ¹¹ Ωcm or more is arranged on at least one of the facing surfaces of two electrodes facing each other, and an attempt is made to form a film on the surface of the high resistance element. A material consisting of at least one of the constituent elements of the thin film is coated, and the sample substrate is placed on the electrode facing the high resistance or on the high resistance, and a mixed gas consisting of the film forming gas and helium. A thin film forming method has been proposed in which a thin film is formed on a sample substrate by supplying a gas to a discharge space on the sample substrate and causing a glow discharge by a high frequency discharge applied to a counter electrode under a pressure near atmospheric pressure. There is.

[0007]

However, in any of the above methods, glass, ceramics, plastics, etc. are provided on at least one electrode to prevent arc discharge. Since these materials are low-conductivity materials having a specific conductivity of one digit, it was necessary to apply a high voltage in order to cause discharge and perform surface treatment.

The present invention solves the above conventional problems, discharge plasma is generated at a low voltage under a pressure near atmospheric pressure, and surface treatment with plasma can be performed in a short time. The object of the present invention is to provide a method for producing a laminated body that can obtain a laminated body with excellent performance.

[0009]

According to the present invention, a specific conductivity is 10 on at least one opposing surface of a pair of opposing metal electrodes.
The base material to be treated is placed between the metal electrodes arranged so that the solid conductor containing the titanic acid-based compound completely covers the electrode surface, and an inert gas and a reaction gas are provided in the space between the metal electrodes. And a voltage is applied to the metal electrode under a pressure near the atmospheric pressure to generate discharge plasma, and the active species excited by the plasma are brought into contact with the surface of the substrate for surface treatment. Is the way.

In the present invention, the surface treatment means, for example, forming a surface functional group layer on the surface of a substrate, forming a free radical layer, imparting hydrophilicity or water repellency to control the surface energy, Improve the wettability and adhesion of materials,
Forming a thin film having optical, electrical, mechanical, etc. functions on the surface.

For example, by chemically bonding fluorine to the surface of the base material,
For low surface energy and water repellency,
A gas containing nitrogen is supplied. Examples of fluorine-containing gas
For example, carbon tetrafluoride (CF_Four), Carbon hexafluoride (C ₂F
₆) Fluorocarbon gas such as tetrafluorocarbon, 1 chlorine
Carbon trifluoride (CClF₃) Chlorinated fluorocarbon gas
Halogenated hydrocarbon gas such as sulfur, sulfur hexafluoride (S
F₆), Etc., and is a safe and harmful gas such as hydrogen fluoride.
Carbon tetrafluoride (CF)_Four), Carbon hexafluoride
(C₂F₆) And the like are preferable.

On the contrary, in the case of increasing the surface energy and imparting hydrophilicity, a gas of a hydrocarbon compound is used to form a layer having a functional group such as a carbonyl group, a hydroxyl group and an amino group on the surface. Or steam, for example, alkane-based gases such as methane, ethane, propane, butane, pentane, and hexane, alkene-based gases such as ethylene, propylene, butene, and pentene, alkadiene-based gases such as pentadiene and butadiene, acetylene, methyl Alkyne-based gases such as acetylene, aromatic hydrocarbon-based gases such as benzene, toluene, xylene, indene, naphthalene and phenanthrene, cycloalkane-based gases such as cyclopropane and cyclohexane, cycloalkene-based gases such as cyclopentene and cyclohexene Alcohol such as methanol, ethanol, etc. System gases, acetone, ketone-based gas such as methyl ethyl ketone, methanal, include such aldehyde gas such as ethanal, These may be used alone or may be used in combination of two or more.
It is also possible to use oxygen gas, a mixed gas of oxygen and hydrogen, steam, ammonia gas, or the like.

When forming a metal oxide thin film of silicon oxide, titanium oxide, tin oxide or the like, a gas composed of a metal organic compound such as metal hydrogen gas, metal halogenated gas, metal alcoholate or the like can be used. .

In the present invention, the surface-treated portion is formed between a pair of opposing metal electrodes in which a solid dielectric having a relative dielectric constant of 10 or more and containing a titanate compound is disposed on at least one of the opposing surfaces. . The relative dielectric constant in the present invention is 2
It means the value under 5 ° C environment (the same applies below). Relative permittivity is 10
When a solid dielectric material of less than 1 is used, a high voltage is required to perform the surface treatment, and the surface treatment takes time.

Titanium-based compounds are known as ferroelectric materials. When titanium oxide alone is used, the relative dielectric constant differs depending on the crystal structure. Titanium oxide having a rutile crystal structure has a relative dielectric constant of about 80. In addition, barium, strontium, lead,
The relative permittivity is controlled to 10 or more by using a compound of titanium oxide and at least one selected from oxides of metals such as calcium, magnesium and zinc.

For example, barium titanate has a relative dielectric constant of about 2,000 to 18,500, and the relative dielectric constant can be changed depending on the purity and crystallinity. These titanic acid compounds may be used alone, or may be used as a mixture with other metal oxides or organic substances.

In the case of mixing, powders of other materials are added to the above-mentioned titanic acid compound powder, and formed into a lump by a known method such as various press, papermaking method, casting, etc., and further baked if necessary. Examples of the method include binding.

The ferroelectric material is plastic,
It may be laminated as another solid bulk dielectric such as glass or ceramic. When a low relative dielectric constant material is laminated, the thickness of the low dielectric constant material depends on the dielectric constant of the titanic acid-based compound, but if it is too thick, it is difficult to discharge, so a thinner thickness is preferable, and a thickness of 2 mm or less is preferable.

The ferroelectric material may be in powder form. In that case, a container having a conductivity of 10 ⁻⁸ S / m or less is filled with a powder containing a titanic acid compound having a relative dielectric constant of 10 or more, and the container is arranged so as to completely cover the electrode surface. .
When using a container whose conductivity exceeds 10 ^-8 S / m,
Arc discharge will occur.

As a container having an electric conductivity of 10 ^-8 S / m or less,
Plastics such as polytetrafluoroethylene, polyimide, polyethylene terephthalate and polystyrene, quartz glass, borosilicate glass, glass such as soda glass,
Examples include containers made of ceramics such as alumina.
A container having a top surface-bottom surface-side surface into which powder can be filled is used.

The wall thickness of the container is appropriately determined depending on the material of the container, the applied voltage, the relative dielectric constant of the powder filled therein, and the like. The total thickness is preferably 5 mm or less, but the side wall thickness does not contribute to the occurrence of discharge.

The height of the container is also appropriately determined depending on the material of the container, the applied voltage, the relative dielectric constant of the powder filled therein, and the like, but is preferably 0.1 to 20 mm. If the height exceeds 20 mm, it becomes difficult to discharge, and conversely, if the height is less than 0.1 mm, the arc discharge easily occurs.

The shape of the container may be square or cylindrical. Further, these containers have no problem even if the materials of the upper surface, the side surface and the bottom surface are different. The smaller the average particle size of the powder filled in the container is, the denser the powder is packed in the container. Therefore, the average particle size is preferably 5 μm or less.

The thickness of the solid dielectric layer of the titanic acid-based compound depends on the material, but the thinner the layer is, the easier the discharge is. However, if it is too thin, arc discharge easily occurs. Conversely, if it is too thick, the dielectric loss becomes large. Since it is difficult to generate discharge plasma and the temperature becomes high, 0.01 to 4 mm is preferable.

Further, although these lumps do not necessarily require a uniform thickness, a uniform thickness is preferable because a uniform discharge plasma can be obtained. The solid dielectric may be dense or porous as long as the entire surface of the electrode provided with the dielectric is covered. That is, it may be a sheet or film of the dielectric itself, or may be a metal coated with a physical or chemical coating method such as vapor deposition, sputtering, CVD or thermal spraying. If the dielectric layer is thin, it is difficult to obtain a sheet-like material, so that the one coated by the above coating method is used.

The metal electrode arrangement structure is a parallel plate type,
Examples include a circular axis cylindrical type, a cylinder facing flat plate type, a sphere facing flat plate type, a double-sided facing flat plate type, and a plurality of thin wires.
It is appropriately determined according to the application.

In the present invention, the material and shape of the base material are not particularly limited. Examples of the material of the base material include plastic, metal, glass, ceramics, cement, paper and fibers, which may be dense or porous. Examples of 9 plastics include polyesters such as polyethylene terephthalate and polyethylene naphthalate, polyolefins such as polyethylene and polypropylene, polystyrene, polyamide, polyvinyl chloride, polycarbonate, polyacrylonitrile and the like.

The substrate may be in the form of a film or sheet, or may be one that has been subjected to a known treatment and subjected to surface cleaning or surface activation treatment. In the case of a film, it may be stretched or unstretched.

When treating a conductive base material such as metal, it is necessary to dispose a dielectric on both electrodes in order to prevent arc discharge. In addition, you may arrange | position the solid dielectric material containing the said titanic acid type compound to both electrodes. In addition, the above-mentioned solid dielectric is arranged only on one electrode, and on the other, a glass or ceramic derivative such as silicon oxide or aluminum oxide, or a solid dielectric such as a ferroelectric of a titanic acid-based compound having a different composition. You can place it.

As an example of the method for producing a laminate of the present invention, a case of imparting water repellency to a plastic surface will be described below with reference to the drawings. FIG. 1 is a partial cross-sectional view showing an example of an atmospheric pressure plasma surface treatment apparatus used in the present invention.

This apparatus comprises a low-frequency power source unit 1, a processing container 2, an upper metal electrode 4 and a lower metal electrode 5. The low-frequency power source unit 1 can apply a power source with a frequency on the order of kHz, but a low frequency of 10 to 30 kHz is preferable in order to impart water repellency to a substrate having low heat resistance. Plasma formation is performed by applying a voltage, but the electric field strength is 1 to 40 k.
It is preferable to apply the voltage so as to be about V / cm. When the electric field strength is less than 1 kV / cm, the plasma density and the self-bias are small, so that the treatment takes time and is inefficient, and conversely, the electric field strength is 40 kV / c.
When it exceeds m, the dielectric substance becomes hot and exhibits a behavior of transition to arc discharge.

The processing container 2 is made of Pyrex glass, but may be made of metal such as stainless steel or aluminum as long as it is insulated from the electrodes. A surface treatment part 3 by glow discharge plasma is formed in a space between a pair of opposing upper and lower metal electrodes 4 and 5. The upper metal electrode 4 has a porous structure. The lower metal electrode 5 is provided with the solid dielectric 6 so as to cover the entire surface facing the upper metal electrode 4.

The plastic substrate 7 to be surface-treated is mounted on the solid dielectric 6 and surface-treated. That is,
The plastic substrate 7 is mounted on one side (upper surface in the figure)
Only the surface is treated. If treatment of both sides of the base material is required, it is necessary to float between the metal electrodes 4 and 5.

The metal electrodes 4 and 5 may be made of 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 discharges is appropriately determined depending on the gas flow rate of the reaction gas, the magnitude of the applied voltage, and the thickness of the treated substrate, but is preferably 1 to 20 mm. If the distance exceeds 20 mm, the uniformity of the gas in the metal electrode space is likely to be impaired, and conversely, if it is less than 1 mm, the amount of unused reaction gas increases and the efficiency tends to increase.

The flow rate of the reaction gas for treatment is controlled by a gas flow controller (not shown), and is supplied from the upper metal electrode 4 having a porous structure to the surface treatment section 3 through the reaction gas introduction pipe 8. The inert gas and the reaction gas for surface treatment may be mixed and introduced from the upper metal electrode 4, but in order to impart water repellency with good uniformity, only the reaction gas is introduced from the upper metal electrode 4, The inert gas is preferably introduced through the inert gas introduction pipe 9. Unused reaction gas and inert gas are discharged from the gas outlet 10 of the container. Reference numeral 11 denotes an exhaust port for discharging the air remaining in the processing container 2 when the reaction gas and the inert gas are introduced into the container 2.

A fluorine-containing gas is preferably used as the surface-treating reaction gas for imparting water repellency. The surface treatment of the plastic base material 7 is performed at a pressure near the atmospheric pressure in an inert gas atmosphere. The pressure near atmospheric pressure is 100 to 80
It is 0 Torr, and 700 to 770 Torr is more preferable in view of cost reduction of the device and equipment.

As the inert gas, helium, neon,
A rare gas such as argon or xenon, a nitrogen gas, or the like is used alone or as a mixed gas, and it is preferable to use a helium gas which has a long metastable state life and is advantageous in excitating and decomposing the reaction gas. When an inert gas other than helium gas is used, it is necessary to mix an organic vapor such as acetone or methanol within 2% by volume or a hydrocarbon gas such as methane or ethane.

The mixing ratio of the inert gas and the fluorine-containing gas is
It seems that the content of fluorine-containing gas exceeds 10% by volume, and discharge plasma which is good for imparting water repellency does not occur even when a high voltage is applied. 0.3 to 5.0% by volume is particularly preferable.

The atmospheric pressure plasma treatment for water repellency is sufficiently possible at room temperature without the need to heat or cool the substrate. or,
The treatment time is determined by the magnitude of the applied voltage. Within the range of the applied voltage, the treatment is made water repellent in about 5 seconds, and even if the treatment is performed for a longer time, the water repellent effect is not improved, and the treatment is performed for a short period of time. Is sufficient.

[0040]

According to the method for producing a laminate of the present invention, a solid conductor having a specific conductivity of 10 or more and containing a titanic acid-based compound completely covers the electrode surface on at least one opposing surface of a pair of opposing metal electrodes. The substrate to be treated is placed between the metal electrodes arranged as described above, an inert gas and a reaction gas are introduced into the space between the metal electrodes, and a voltage is applied to the metal electrodes under a pressure near atmospheric pressure. A special vacuum is formed compared with the conventional surface treatment method of the substrate by low pressure glow discharge plasma by generating discharge plasma and bringing the active species excited by the plasma into contact with the substrate surface for surface treatment. No need for special equipment for vacuum formation, no special operation for vacuum formation, no need for high power, which was a problem of atmospheric pressure plasma, low applied voltage and short time At the surface of various substrates Performs management, excellent laminate surface properties can be easily and inexpensively manufactured.

[0041]

EXAMPLES The present invention will be described below with reference to examples. Example 1 Using the apparatus shown in FIG. 1 (metal electrode diameter 80 mm), a substrate made of a circular polyester film having a diameter of 80 mm and a thickness of 100 μm (manufactured by Toray Industries, Inc., trade name “Lumirror S10”) was used, having a diameter of 120 mm and a thickness of 120 mm. 2 mm barium titanate (relative permittivity: about 15,000) was mounted on the lower metal electrode, and the distance between the metal electrodes was set to about 15 mm.
The oil rotary pump exhausted to Torr.

Then, a carbon tetrafluoride gas having a gas flow rate of 2 sccm is passed through the reaction gas introducing pipe 8 and the metal electrode 4 having a porous structure.
In addition, helium gas with a gas flow rate of 198 sccm was introduced into the processing container 2 through the inert gas introduction pipe 9, and 760T
After setting the atmospheric pressure to orr, at a frequency of 15 kHz, 2.1
Power of kV and 40.5 mA was applied and left for 10 seconds. Plasma emission was observed with the application of voltage.

The treated surface was measured for contact angle with pure water. As a result, 100 to 10 in the area hit by the plasma.
It was 8 degrees, and it became clear that it was water repellent.
The contact angle of the substrate used was 65 degrees. In addition, as a result of analyzing the processing section by X-ray electron spectroscopy, the average electron ratio was 6
It was found that 4% of fluorine was chemically bonded to the surface.

The contact angle was measured by dropping water with a contact angle measuring device (trade name "CA-D") manufactured by Kyowa Interface Science Co., Ltd.
The static contact angle was measured. The relative permittivity is Polyme
r Laboratories Ltd. Using a dielectric constant thermal analyzer (trade name "PL-DETA") manufactured by a company, a dielectric having a diameter of 33 mm was prepared, and a reference relative dielectric constant was measured at room temperature of 25 ° C in a frequency band of 20 to 100 kHz. For powder, the catalog value of the powder manufacturer was used instead.

Example 2 Instead of barium titanate, diameter 120 mm × thickness 2
The same treatment as in Example 1 was performed, except that a titanium oxide sintered body having a rutile crystal structure of mm (relative permittivity of about 70) was provided and a power of 4.2 kV and 37.5 mA was applied. The contact angle of the treated surface with pure water was measured.

As a result, in the area hit by the plasma, 10
It was 0 to 108 degrees, and it became clear that it was made water repellent. As a result of treating the treated portion by X-ray electron spectroscopy, it was found that 62% of fluorine in average atomic ratio was chemically bonded to the surface.

Example 3 A titanium oxide film having a rutile crystal structure with a porosity of 5% (relative permittivity of about 25) was formed by plasma spraying on an aluminum plate having a diameter of 130 mm and a thickness of 2 mm of 500 μm on one side and all sides.
Formed to a thickness and installed on the lower electrode, voltage 5.4k
Example 1 except that power of V and current of 35.7 mA was applied.
Is the same as.

As a result, in the area hit by the plasma, 10
It was 0 to 108 degrees, and it became clear that it was made water repellent. As a result of analyzing the treated part by X-ray electron spectroscopy, it was found that 62% of fluorine in average atomic ratio was chemically bonded to the surface.

Example 4 The same as Example 1 except that a polyethylene film (polybag NP-70 manufactured by Sekisui Chemical Co., Ltd. was cut and used) was used as the substrate in Example 1 instead of the polyethylene terephthalate film. is there.

The contact angle of the treated surface with pure water was measured. As a result, 118 to 12 in the area hit by the plasma
It was 8 degrees, and it became clear that it was water repellent.
Further, as a result of analyzing the treated part by X-ray electron spectroscopy, it was found that 67% of fluorine in terms of atomic ratio was chemically bonded to the surface.

Example 5 A polymethylmethacrylate sheet having a diameter of 50 mm and a thickness of 3 mm (trade name "Acrylite EX" manufactured by Mitsubishi Rayon Co., Ltd.) was used as a base material, except that a power of 4.9 kV and 36 mA was applied. Similar to Example 1.

The contact angle of the treated surface with pure water was measured. As a result, 100 to 10 in the area hit by the plasma.
It was 8 degrees, and it became clear that it was water repellent.
Further, as a result of analyzing the treated portion by X-ray electron spectroscopy, it was found that 61% of fluorine in terms of atomic ratio was chemically bonded to the surface.

Example 6 Using the apparatus shown in FIG. 1 (metal electrode diameter: about 80 mm),
On a lower electrode provided with a polystyrene petri dish having a diameter of 90 mm and a thickness of 15 mm filled with barium titanate powder (manufactured by Fuji Titanium Co., Ltd., trade name “BT-203”, relative permittivity of about 17,000). 80m diameter installed
A polyester film (trade name: “Lumirror S10”, manufactured by Toray Industries, Inc.) having a size of m × 100 μm was installed, and the distance between the metal electrodes was set to about 15 mm, and then exhausted to 1 Torr with an oil rotary pump.

Then, a carbon tetrafluoride gas having a gas flow rate of 2 sccm is passed through the reaction gas introducing pipe 8 and the metal electrode 4 having a porous structure.
Further, helium gas with a gas flow rate of 198 sccm was introduced into the container 2 through the inert gas introduction pipe 9, and 760 Tor
After setting the atmospheric pressure to r, 3.2k at a frequency of 15kHz
A power of V and 40 mA was applied and left for 10 seconds. Plasma emission was observed as the voltage was applied.

The contact angle of the treated surface with pure water was measured. As a result, 100 to 10 in the area hit by the plasma.
It was 8 degrees, and it became clear that it was water repellent.
The contact angle of the substrate used was 65 degrees. In addition, as a result of analyzing the processing part by X-ray electron spectroscopy, the atomic ratio is 64%.
It was found that the above fluorine was chemically bonded to the surface.

Example 7 Instead of barium titanate, titanium oxide having a rutile structure (manufactured by Fuji Titanium Industry Co., Ltd., trade name "TP-3", having a relative dielectric constant of about 80) was filled, and 5.2 kV, 36. The same treatment as in Example 6 was performed except that a power of 5 mA was applied.

The contact angle of the treated surface with pure water was measured. As a result, 100 to 10 in the area hit by the plasma.
It was 8 degrees, and it became clear that it was water repellent. As a result of analyzing the processing part by X-ray electron spectroscopy, the atomic ratio was 62.
It was found that% fluorine was chemically bonded to the surface.

Example 8 A polyethylene terephthalate film having a diameter of 120 mm and a thickness of 100 μm (trade name “Lumirror S10” manufactured by Toray Industries, Inc.) was used on the top and bottom surfaces, and the side was 1 mm in thickness and 60 m in inner diameter.
In a container made of polytetrafluoroethylene having an outer diameter of 80 mm and a diameter of 80 mm, barium titanate powder (manufactured by Fuji Titanium Industry Co., Ltd., trade name "HBT-1", relative dielectric constant of about 2,000).
And charging power of 3.9 kV and 38.0 mA was applied.

The contact angle of the treated surface with pure water was measured. As a result, 100 to 10 in the area hit by the plasma.
It was 8 degrees, and it became clear that it was water repellent.
Further, as a result of analyzing the treated portion by X-ray electron spectroscopy, it was found that 61% of atomic ratio of fluorine was chemically bonded to the surface.

Example 9 Carbon tetrafluoride gas having a gas flow rate of 1 sccm and a gas flow rate of 2 s
A mixed gas of oxygen gas of ccm is passed through the reaction gas introduction pipe 8 from the upper metal electrode 4 having a porous structure, and the gas flow rate is 197.
2. After introducing sccm of helium gas into the container 2 through the inert gas introducing pipe 9 and setting the atmospheric pressure to 760 Torr, 3.
Example 6 is the same as Example 6 except that a power of 2 kV and 38.5 mA is applied and left for 1 minute.

The contact angle of pure water on the treated surface was measured. As a result, it was revealed that the region exposed to the plasma exhibited a temperature of 25 to 35 degrees and was hydrophilized.

Example 10 Carbon tetrafluoride gas having a gas flow rate of 1 sccm and a gas flow rate of 2 s
A mixed gas of oxygen gas of ccm is passed through the reaction gas introducing pipe 8 from the metal electrode 4 having a porous structure, and the gas flow rate is 197 sc.
After introducing helium gas (cm) into the container 2 through the inert gas introducing pipe 9 and setting the atmospheric pressure to 760 Torr, 3.5 k
Example 6 is the same as Example 6 except that an electric power of 39 mA is applied and V is left for 1 minute.

The contact angle of the treated surface with pure water was measured. As a result, it was revealed that the region exposed to the plasma had a temperature of 28 to 35 degrees and was hydrophilic.

Comparative Example Example 1 except that quartz glass having a diameter of 120 mm and a thickness of 2 mm (relative permittivity of about 4.5) was used as the solid dielectric pair.
Same as. A voltage of 2.1 kV was applied, but no discharge was confirmed. It should be noted that plasma emission was first confirmed by applying a voltage of 7.0 kV. It took a processing time of 1 minute or more to show a contact angle of 100 degrees or more in the region hit by the plasma.

[0065]

EFFECTS OF THE INVENTION The method for producing a laminated body of the present invention, having the above-mentioned constitution, performs the surface treatment of various base materials at a low applied voltage for a short time, and has excellent surface characteristics. Can be manufactured easily and at low cost.

[0066]

[Brief description of drawings]

FIG. 1 is a partial cross-sectional view showing an example of an atmospheric pressure plasma surface treatment apparatus used in the present invention.

[Simple explanation of symbols]

 1 Low Frequency Power Supply Unit 2 Treatment Container 3 Surface Treatment Unit 4 Upper Metal Electrode 5 Lower Metal Electrode 6 Solid Dielectric 7 Plastic Base Material 8 Reactive Gas Introducing Pipe 9 Inert Gas Introducing Pipe 10 Exhaust Port

Claims (1)

[Claims] 1. A metal electrode in which a solid conductor having a specific conductivity of 10 or more and containing a titanic acid-based compound is disposed on at least one opposing surface of a pair of opposing metal electrodes so as to completely cover the electrode surfaces. A base material to be treated is placed between them, an inert gas and a reaction gas are introduced into the space between the metal electrodes, and a voltage is applied to the metal electrodes under a pressure near atmospheric pressure to generate discharge plasma. A method for producing a laminate, which comprises subjecting the surface of a base material to contact with active species excited by the surface treatment.