JP2003201568A - Apparatus and method for plasma discharge - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an apparatus having electrodes capable of performing atmospheric plasma discharge even when the treatment temperature is as high as 300°C, the discharge is performed in a high output state, and durable for a long-term continuous operation, and to provide an atmospheric plasma discharge apparatus and an atmospheric plasma discharge method capable of depositing a thin film on a base material at high speed with high performance. <P>SOLUTION: In the plasma discharge apparatus, the reaction gas containing a reactive gas between the electrodes and rare gas is in a plasma state by applying the high frequency voltage under the atmospheric pressure or under the pressure nearby between the electrodes facing each other to perform the discharge, the base material is exposed to the reaction gas in a plasma state to deposit a thin film on the base material. A base metal of the electrodes is a titanium alloy containing ≥70 mass % titanium, or titanium metal. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a plasma discharge treatment apparatus for forming a thin film on a substrate by plasma discharge treatment under atmospheric pressure or a pressure close to the atmospheric pressure, and a plasma discharge for forming a thin film using this apparatus. Regarding processing method.

[0002]

2. Description of the Related Art A high-frequency voltage is applied between electrodes having a counter electrode formed between an applying electrode and a ground electrode to discharge under atmospheric pressure or a pressure close to the ground electrode, thereby causing a reactivity between the counter electrodes. Plasma discharge treatment for forming a thin film on the base material by exposing the base material to the reaction gas in the plasma state by making a reaction gas containing a gas and a rare gas into a plasma state (hereinafter referred to as atmospheric pressure plasma discharge treatment There are many) have been proposed.

Most of the electrodes used in the atmospheric pressure plasma discharge treatment apparatus are composed of a metal base material and a dielectric material coated thereon. As the metal base material of the electrode,
A lot of stainless steel was used, and rubber, ceramics, glass, glass-lined ones, or ceramics sprayed ones were used as the dielectric material coated on the stainless steels. Rubber is often used because of its low cost, elasticity, and good adhesion to the metal base material.
When the temperature exceeds 00 ° C, the rubber softens and cannot be processed, and it must be replaced immediately after aging. Further, a dielectric material such as ceramics or glass is difficult to adhere to a metal base material having a curved surface and is not suitable for a device having a rotating electrode. The dielectric material coated on the metal base material by the ceramic spraying method or the glass lining method can have strong adhesion even if the electrode has a curved surface. Cracks appearing to be caused by the difference in thermal strain in the dielectric, especially when the metal base material is made of stainless steel and coated with the dielectric material by the ceramic spraying method, the surface cracks at about 60 ° C The electrodes had to be changed frequently. In addition, due to the nature of such electrodes, there are limitations on the processing conditions, and plasma discharge processing cannot be performed very efficiently.

[0004]

DISCLOSURE OF THE INVENTION The inventors of the present invention have made earnest studies on an apparatus capable of performing atmospheric pressure plasma discharge treatment with higher efficiency, particularly an electrode and a dielectric. An object of the present invention is to apply a high-frequency voltage between electrodes having a counter electrode formed between an application electrode and a ground electrode under atmospheric pressure or a pressure in the vicinity thereof to cause discharge, thereby causing a reaction between the counter electrodes. When a thin film is formed on the base material by exposing the base material to the reaction gas in the plasma state by exposing the base material to the reaction gas containing the reactive gas and the rare gas, discharge is performed even at a high processing temperature of 300 ° C. Another object of the present invention is to provide a plasma discharge treatment apparatus having a novel electrode capable of withstanding long-term continuous operation even in the high output state. A second object of the present invention is to provide an atmospheric pressure plasma discharge treatment method capable of forming a thin film on a substrate at high speed and with high performance.

[0005]

The present invention has the following constitution.

(1) Under atmospheric pressure or a pressure in the vicinity thereof, a high-frequency voltage is applied between the electrodes in which the counter electrode is formed by the application electrode and the ground electrode to cause discharge, thereby causing a reaction between the counter electrodes. A plasma discharge treatment apparatus for forming a thin film on a base material by exposing a base material to the reaction gas in the plasma state by forming a reaction gas containing a reactive gas and a rare gas into a plasma state. A plasma discharge treatment apparatus, wherein the metal base material is a titanium alloy or titanium metal containing 70% by mass or more of titanium.

(2) Under atmospheric pressure or a pressure in the vicinity thereof, a high-frequency voltage is applied between the electrodes where the counter electrode is formed by the application electrode and the ground electrode to cause discharge, thereby causing a reaction between the counter electrodes. A plasma discharge treatment apparatus for forming a thin film on a base material by exposing a base material to the reaction gas in the plasma state by forming a reaction gas containing a reactive gas and a rare gas into a plasma state. A plasma discharge treatment apparatus, wherein the metal base material is a titanium alloy or titanium metal containing 70% by mass or more of titanium, and the metal base material is covered with a ceramic sprayed dielectric.

(3) Under atmospheric pressure or a pressure in the vicinity thereof, a high-frequency voltage is applied between the electrodes where the counter electrode is formed by the application electrode and the ground electrode to cause discharge, thereby causing a reaction between the counter electrodes. A plasma discharge treatment apparatus for forming a thin film on a base material by exposing a base material to the reaction gas in the plasma state by making a reaction gas containing a reactive gas and a rare gas into a plasma state, wherein the opposing electrodes are A metal base material of a titanium alloy or titanium metal containing 70% by mass or more of titanium, and a metal base material coated with a ceramic sprayed dielectric material, and the metal base material and the dielectric material thereon. Between the thickness of the metal base material surface between 1 ~
A plasma discharge treatment apparatus having a metal base having a lower electric resistance than the metal base material of 1,000 μm.

(4) The underlying metal is Cu, Au,
The plasma discharge treatment apparatus according to (3), which is at least one selected from Ag, Pt, Cr, Ni, and Zn, or an alloy containing an element selected from these.

(5) The plasma discharge treatment apparatus according to claim 3 or 4, wherein the base is applied by a metal spraying method or a plating method.

(6) The plasma discharge treatment apparatus according to any one of (2) to (5), wherein the dielectric has a thickness of 0.1 to 3 mm.

(7) The dielectric is 0.01 to 6% by volume.
The plasma discharge treatment apparatus according to any one of (2) to (6), which has a porosity of

(8) Under atmospheric pressure or a pressure in the vicinity thereof, a high-frequency voltage is applied between the electrodes where the counter electrode is formed by the application electrode and the ground electrode to cause discharge, thereby causing a reaction between the counter electrodes. A plasma discharge treatment apparatus for forming a thin film on a base material by exposing a base material to the reaction gas in the plasma state by forming a reaction gas containing a reactive gas and a rare gas into a plasma state. The metal base material is a titanium alloy or titanium metal containing 70% by mass or more of titanium, and the metal base material is coated with a ceramic sprayed dielectric material, and the temperature of the metal base material is controlled by a heat medium. It is hollow so that the total thickness of the metal base material and the dielectric is 2 to 30 mm.
And a plasma discharge processing apparatus.

(9) Any one of (1) to (8), characterized in that the ground electrode is a rotating electrode and the applying electrode is a cylindrical fixed electrode group arranged along the rotating electrode. The plasma discharge treatment apparatus according to item 1.

(10) The ground electrode is a rotating electrode, and the applying electrode is a concave fixed electrode having a concave surface of a circle of the rotating electrode and a circular arc of a larger concentric circle. The plasma discharge treatment apparatus according to any one of 8).

(11) Any one of (1) to (10)
A plasma discharge treatment method characterized by forming a thin film while maintaining the temperature of the electrode at 100 to 300 ° C. using the plasma discharge treatment apparatus described in the item.

(12) The temperature of the electrode is 120 to 250 ° C.
It is characterized by forming a thin film while maintaining
The plasma discharge treatment method according to 1).

The present invention will be described in detail. The atmospheric pressure plasma discharge treatment apparatus and method of the present invention will be described with reference to the drawings.

In the present invention, the atmospheric pressure or the pressure in the vicinity thereof is in the range of 20 to 110 kPa, preferably 93 to 104 kPa.

FIG. 1 is a diagram showing an example of the atmospheric pressure plasma discharge treatment apparatus of the present invention. FIG. 1 shows the entire atmospheric pressure plasma discharge treatment apparatus, which is composed of a plasma discharge treatment apparatus 30, a voltage applying means 40, a gas filling means 50, and an electrode temperature adjusting means 60. The electrodes of the plasma discharge processing apparatus 30 of FIG. 1 form a counter electrode with an application electrode and a ground electrode, and the counter electrode includes a roll-shaped rotating electrode 25 as a ground electrode and a cylindrical fixed electrode group 36 of the application electrodes. Are formed from. The base film F is unrolled from an unillustrated original roll and conveyed, or is conveyed from the previous step (in the present invention, the base film F is treated in order to process the substrate to be transferred). Is conveyed by the rotating electrode of the ground electrode at a speed synchronized with its rotation), and the nip roll 65 through the guide roll 64 cuts the air and the like entrained in the base film F and contacts the rotating electrode 25. While being wound as it is, it is transferred to the discharge processing section 32 between the cylindrical fixed electrode group 36, and then, after passing through the nip roll 66 and the guide roll 67, it is wound by a winder (not shown) or transferred to the next step. . The reaction gas G generated by the gas generator 51 of the gas filling means 50 is
The flow rate is controlled so that the gas is introduced into the plasma discharge processing container 31 having the discharge processing unit 32 from the air supply port 52, the inside of the plasma discharge processing container 31 is filled with the reaction gas G, and the gas is discharged as the processing exhaust gas G ′ from the exhaust port 53. To Next, the voltage applying means 4
At 0, a voltage is applied to the cylindrical fixed electrode group 36, which is an application electrode, by the high frequency power source 41, and the rotary electrode 2 that is an earth electrode is applied.
A ground is connected to 5 to generate discharge plasma. From the electrode temperature adjusting means 60, a liquid-feeding pump P is supplied from the electrode temperature adjusting means 60 for heating or cooling the medium whose temperature is adjusted by the electrode temperature adjusting means 60.
The rotating electrode 25 and the cylindrical fixed electrode group 3 through the pipe 61 at
6, and the rotary electrode 25 and the cylindrical fixed electrode group 36.
Adjust temperature from inside. During plasma discharge treatment, the physical properties and composition of the resulting thin film may change depending on the temperatures of the base film F and the electrodes, and it is preferable to control this appropriately. As the medium, an oil-based insulating material such as silicone oil is preferably used. During the plasma discharge treatment, the internal temperature of the rotating electrode and the fixed electrode is controlled so that the temperature unevenness of the base film in the width direction or the longitudinal direction is minimized.
It should be noted that reference numerals 68 and 69 denote partition plates that partition the plasma discharge processing container 31 and the outside world.

The discharge processing section 32 is a gap between the opposing electrodes, and the gap between the electrodes (gap distance) is 0.1 to 30 m.
m is preferred. The plasma discharge treatment container 31 may be a metal container insulated by Pyrex (R) glass or plastic. For example, a polyimide resin or the like may be adhered to the inner surface of a frame made of aluminum or stainless steel, and the metal frame may be sprayed with ceramics so as to have an insulating property.

FIG. 2 is a perspective view showing an example of the rotating electrode according to the present invention. In FIG. 2, the rotating electrode 25a has a conductive metal base material 25A covered with a dielectric 25B.

The shape of the cylindrical fixed electrode shown in FIG. 2 is roughly a rectangular cylinder or a cylinder. Here, the prismatic type is referred to as a prismatic fixed electrode, and the cylindrical type is referred to as a cylindrical fixed electrode. The prismatic fixed electrode group is more preferable than the cylindrical fixed electrode group because it has an effect of widening the discharge range and plasma discharge is efficiently performed. The cross-sectional shape of the rectangular tubular fixed electrode is not limited to a quadrangle or a pentagon, but the surface of the rectangular tubular fixed electrode facing the rotating electrode is relative to the line connecting the center of the rectangular tubular rotating electrode and the center of the rotating electrode. It is preferable to install them at right angles. It is more preferable that one surface of the rotary electrode has an arc that is concentric with the circle of the cross section of the rotary electrode.
In the case of the cylindrical fixed electrode group, the cylindrical fixed electrode may be self-rotating on the spot, which is advantageous in that the electrodes are less contaminated.

FIG. 3 is a perspective view showing an example of a square tube fixed electrode of the square tube type fixed electrode group. In FIG. 3, each of the square tube type fixed electrodes 36a of the square tube type fixed electrode group 36 has a conductive metal base material 36A and a dielectric body 36B coated on the metal base material 36A, similar to the rotating electrodes. Has become.

In FIG. 4, the application electrode has a concave fixed electrode,
It is the schematic which shows an example of the atmospheric pressure plasma discharge processing apparatus which has a rotating electrode in the earth electrode. The concave fixed electrode 102 of the application electrode facing the roll-shaped rotary electrode 101 of the ground electrode that rotates in contact with the base film F has a curved surface of a concentric circular arc slightly larger than the circle of the cross section of the rotary electrode 101. Therefore, the counter electrode of this type is also preferably used in the present invention. The length of the arc of the concave surface of the concave fixed electrode 102 is not particularly limited as long as it is equal to or less than the circumference of the cross section of the rotating electrode 101, but the length of the arc of the concave fixed electrode 102 is the circumference of the rotating electrode. Is preferably about 10 to 50%.
The discharge treatment section 103 between the rotary electrode 101 and the concave fixed electrode 102 is set as an atmosphere of the reaction gas G in a plasma state, and although not shown, it is fed from the original film or the base film F fed from the previous process. Base film F
However, when it is guided to the guide roll 104 and passes through the discharge treatment section 103 while being wound around the rotary electrode 101, the base film F is subjected to atmospheric pressure plasma discharge treatment.

In the present invention, it is appropriate that the thickness of the base film F passing through the electric discharge treatment section 103 is about 1 to 200 μm, and the gap of the electric discharge treatment section 103 is the rotating electrode 101.
Not from the surface to the concave fixed electrode surface 102, but from the surface of the base film F having a thickness to the surface of the concave fixed electrode 102, the gap is 5 mm or less, preferably 3 mm or less, more preferably It is 0.5 to 2 mm.

The discharge plasma is generated by being applied to the concave fixed electrode 102 from the high frequency power source 105.
In the present invention, the plasma discharge treatment can be performed without blocking the external environment, but it is preferable to block the external air. To cut off the processing system from the outside world,
It can be carried out by means such as providing a container for shutting off, or shutting off air entrained in the substrate such as a nip roll. A nip roll is effective as a means for blocking the air entrained in the base film F.
The base film F guided to the guide roll 104 can be pressed against the rotating electrode 101 while pressure is applied by the nip roll 106 to shut off the accompanying air. Although the nip roll 106 alone is sufficient as a means for blocking the air entrained in the base film F, as a means for further blocking the entrained air, although not shown in FIG. A preparatory chamber may be provided before the substrate is introduced into. The spare room is JP 2000-0729 A.
The same means as the means described in the publication 03 may be installed. The internal pressure in the electric discharge processing unit 103 is equal to the internal pressure of the electric discharge processing unit 1.
It is necessary to be higher than the internal pressure of the auxiliary chamber adjacent to 03, and preferably higher than 0.3 Pa. By thus providing a pressure difference between the discharge treatment section and the preparatory chamber as well, it is possible to prevent external air from being mixed in, effectively use the reaction gas, and further improve the treatment effect. When two or more auxiliary chambers are provided on the inlet side and two or more auxiliary chambers on the outlet side adjacent to the discharge treatment unit, the differential pressure between the auxiliary chamber and the adjacent auxiliary chambers is
It is preferable that the internal pressure of the auxiliary chamber on the side closer to the electric discharge processing unit be set high, and it is preferable that the internal pressure be set 0.3 Pa or higher. By providing the pressure difference between the plurality of preliminary chambers in this manner, the mixing of the external air can be prevented more efficiently, the reaction gas can be effectively used, and the treatment effect is further improved.

In FIG. 4, the plasma discharge processing container 11 is shown.
The inside of 0 is filled with the reaction gas G introduced from the container gas introduction port 107. Plasma discharge treatment container 1
A processing part container 11 for further performing plasma discharge processing inside 10
1, the reaction gas is introduced into the gap between the rotary electrode 101 and the concave fixed electrode 102 from the processing part gas introduction port 108. The processed gas G ′ is discharged from the processing unit exhaust port 116. The plasma discharge treatment container 110 is a nip roll 10
6 and 112 and partition plates 109 and 115 are isolated from the outside world. The gas with which the plasma discharge processing container 110 is filled through the container gas introduction port 107 preferably has the same composition as the reaction gas introduced into the discharge processing unit 103. It is preferable that the discharge processing section 103 in the processing section container 111 is further surrounded by the side surface of the counter electrode, the side surface of the base material transfer section, and the like so that stable processing can be performed. Further, the reaction gas to be introduced may be divided into layers and introduced into the discharge treatment section 103 as described in Japanese Patent Application No. 2001-286720. In particular, it is also preferable to increase the concentration of the reactive gas on the side of the base film F that is transferred in synchronization with the rotating electrode 101 and the concentration of the rare gas on the side of the fixed electrode 102. The treated gas G ′ is discharged from the container exhaust port 114. The processed base film F ′ exits the plasma discharge treatment container 110 through the nip roll 112, and is wound up by a winder (not shown) or conveyed to the next step through the guide roll 113.

In FIG. 4, 101A and 102A are metal base materials of electrodes, and 101B and 102B are dielectrics.

The shape of the base material is not limited to a film shape, and a shape that can be applied to a base material having various curved surfaces is also used. When a high-frequency voltage is applied by introducing a reaction gas from above between opposing electrodes as shown in FIG. 6 described later, the reaction gas in a plasma state is jetted out downward, and a base material having a curved surface placed below it Also, a thin film can be formed. Further, a thin film can be formed on the base material film by transferring a film-like base material under the counter electrode instead of the base material having a curved surface.

The metal base material of all electrodes (both the application electrode and the ground electrode) in the present invention is a titanium alloy or titanium metal containing titanium in an amount of 70% by mass or more. In the present invention, if the content of titanium in the titanium alloy or titanium metal is 70% by mass or more, it can be used without problems,
It is preferable that the titanium content is 80% by mass or more. As the titanium alloy or titanium metal useful in the present invention, those generally used as industrial pure titanium, corrosion resistant titanium, high strength titanium and the like can be used.
As industrial pure titanium, TIA, TIB, TIC, T
ID, etc. can be mentioned, and all are iron atoms, carbon atoms,
It contains a very small amount of nitrogen atoms, oxygen atoms, hydrogen atoms, etc., and has a titanium content of 99 mass% or more. T15PB can be preferably used as the corrosion-resistant titanium alloy, contains lead in addition to the above-mentioned contained atoms, and has a titanium content of 98% by mass or more. Further, as the titanium alloy, T64, T325, T525, TA3, etc. which contain aluminum in addition to the above-mentioned atoms other than lead and also contain vanadium and tin can be preferably used. The amount is 85% by mass or more. These titanium alloys or titanium metals have a coefficient of thermal expansion of 1 / compared with stainless steel such as AISI316.
It is small by about 2 and can be combined with a titanium alloy or a later-described dielectric material applied on titanium metal as a metal base material, and can withstand use at high temperature for a long time.

In order to further enhance the effect of the present invention, it is selected from Cu, Au, Ag, Pt, Cr, Ni or Zn having excellent conductivity on the metal base material of the titanium alloy or titanium metal according to the present invention. By providing a metal or an alloy selected from these by the metal spraying method or the plating method, the feeding point from the high frequency power source can be directly coupled to the metal underlayer, and as a result, the conductivity of the metal base material can be obtained. It is possible to increase the efficiency and make it easier to pass the current from the high frequency power source, and it is possible to efficiently perform the plasma treatment. It is preferable to apply the metal base to a thickness of 1 to 1000 μm. By applying the metal base to such a metal base material, the electric conductivity can be 10 μΩcm or less, and the metal base material of the electrode can be The conductivity can be remarkably improved. As a result, the amount of self-heating of the electrode is suppressed and the electrode can withstand high output use. The applied metal underlayer thickness depends on the frequency used and is 100 kHz.
Less than z, 100 μm or more, 100 kHz or more, 50
It is preferably 10 μm or more for μm or more and 1 MH or more, and 1 μm or more for 10 MHz or more.

By using the titanium alloy or titanium metal containing titanium of 70% by mass or more according to the present invention as the metal base material, the dielectric material coated thereon is not limited. In particular, good discharge becomes possible for the ceramic sprayed dielectric. On the other hand, when stainless steel is used as a metal base material and an electrode made of a combination of ceramic sprayed dielectrics is used, the coefficient of thermal expansion is large and it is incompatible with respect to durability and workability, especially at about 60 ° C. The dielectric has cracks, high power applied voltage,
It was not an electrode that could withstand high temperature and long time atmospheric pressure plasma discharge treatment. In the present invention, it was found that a titanium alloy or titanium metal containing 70% by mass or more of titanium is used as a metal base material, and thus the combination of the metal base material and a ceramics-sprayed dielectric coating provides durability, It was possible to obtain an electrode excellent in workability, use of a high-power high-frequency power source, treatment at high temperature, and plasma discharge treatability for a long time. It was also found that the coating of the dielectric with a glass lining can provide quite satisfactory performance.

Here, the dielectric will be described. The electrode according to the present invention has a metal base material and a dielectric material as shown in FIGS. 2 and 3, and the dielectric material is obtained by coating the metal base material with an inorganic material. Dielectrics that can be used in the present invention include
It may be constituted by a combination of coating a dielectric material having an inorganic property with a lining, or a combination of coating a dielectric material sealed with a substance having an inorganic property after spraying ceramics on a metal base material. As the dielectric lining material, silicate glass, borate glass, phosphate glass, germanate glass, tellurite glass, aluminate glass, vanadate glass, etc. are used. Among them, borate glass is preferable because it is easily processed. Alumina is preferable as the ceramic used for thermal spraying of the dielectric material, and a sealing material such as silicon oxide is preferable. Further, a material in which an alkoxysilane-based sealing material is subjected to a sol-gel reaction to be mineralized is preferably used (Japanese Patent Application No. 2000-377044). In particular, aluminum oxide and white alumina can be preferably used as a material for ceramics thermal spraying of a dielectric material suitable in the present invention. In addition to aluminum oxide, there are those containing titanium oxide, silicon oxide, or zirconium oxide as a main component, but aluminum oxide is preferable. The particles of the material are preferably finer, and a dense sprayed film can be formed, which is preferable. Thickness of sprayed ceramics dielectric is 0.1-3
mm is preferable, but 0.5-2 mm is more preferable. When the thickness of the ceramics is 0.1 mm or less, not only sufficient insulation may not be obtained, but also the uniformity of discharge tends to deteriorate. On the contrary, when the thickness of the ceramics is 3 mm or more, the efficiency of discharge decreases. The ceramic spraying method is a method in which a ceramic powder material is put into a rare gas heated to about 10,000 ° C. by arc discharge, instantly melted, and sprayed on a metal base material to form a coating film. By using this method, it is possible to obtain an electrode coated with a uniform thin film of ceramics. It is also possible to polish the sprayed coating to obtain a more uniform coating. As another method of thermal spraying, a method of sealing is also a preferable method.
For example, alumina, a silicon nitride compound, or an alkoxysilane-based or alkoxyaluminum-based sealing material is sprayed as an organic solvent solution, and is sol-gel-reacted and cured to be mineralized, or is irradiated with ultraviolet rays to be sol-gel-reacted to accelerate curing and be mineralized. It is preferably used (Japanese Patent Application No. 2000-377).
044). In the present invention, the dielectric constant of the dielectric is 4 to 5
0, and more preferably 10-20.

When the substrate film is placed between the electrodes or conveyed between the electrodes and exposed to plasma, a roll that can convey the substrate film not only on the dielectric surface of the applying electrode but also on the ground electrode. The dielectric surface of the electrode is also polished to a surface roughness Rmax (JIS B 06
By setting 01) to 10 μm or less, the thickness of the dielectric and the gap between the electrodes can be kept constant, the discharge state can be stabilized, and distortion and cracking due to thermal contraction difference and residual stress can be eliminated, and Durability can be greatly improved by coating with a highly accurate inorganic dielectric material that is not porous. Regarding the surface roughness, the maximum value of the surface roughness is more preferably 8 μm or less, and particularly preferably adjusted to 7 μm or less. The center line average roughness (Ra) defined by JIS B 0601 is preferably 0.5 μm or less, more preferably 0.1 μm or less. Furthermore,
As a method of coating the metal base material of the electrode with the dielectric, the ceramics are sprayed densely to a porosity of 10% by volume or less,
Further, it is to carry out a sealing treatment with an inorganic material which is cured by a sol-gel reaction. Here, in order to accelerate the sol-gel reaction, heat curing or ultraviolet curing is good, and further, the sealing liquid is diluted,
By repeating coating and curing several times in succession, the mineralization is further improved, and a dense electrode without deterioration can be obtained.

In FIGS. 2 and 3, the conductive metal base material 2 is used.
Ceramics-coated dielectric 25, which is obtained by spraying ceramics on 5A and 36A and then sealing using an inorganic material.
It is composed of a combination of B and 36B coated respectively. The ceramics-coated dielectric is coated with 1 mm of one-sided wall, and after the roll diameter is coated, it is manufactured to be uniform.

In the present invention, the distance between opposing electrodes is 10 k.
It is preferable to apply a high frequency electric field having a frequency in the range of Hz to 150 MHz. In particular, the higher the frequency, the higher the thin film formation rate, and it is preferable to apply a high frequency electric field exceeding 100 kHz. Further, a high-frequency electric field exceeding 100 kHz is applied between the electrodes facing each other, and 1 W / cm
^It is preferable to supply ^two or more electric powers. By applying such high-power high-frequency electric field,
A highly functional thin film with high film thickness uniformity can be obtained with high production efficiency. In the present invention, the frequency of the high frequency voltage applied between the opposing electrodes is preferably 150 MHz.
It is the following. The frequency of the high frequency voltage is preferably 200 kHz or more, more preferably 800 kHz.
z or more. The power supplied between opposed electrodes is preferably not 1.2 W / cm ² or more, preferably 50 W / cm ² or less, more preferably 20W / cm ²
It is the following. The voltage application area of the opposing electrodes refers to the area in the range where discharge occurs. The high-frequency voltage applied between the electrodes facing each other may be an intermittent pulse wave or a continuous sine wave, but in order to obtain the effect of the present invention high, it is a continuous sine wave. It is preferable. The high frequency electric field has a sine waveform, but it is also possible to apply a pulsed electric field. This pulsing means that the plasma gas temperature can be changed by changing the ON / OFF duty ratio.

The high frequency power source for applying a voltage to the opposing electrodes useful in the present invention is not particularly limited, but is a high frequency power source (50 kHz) manufactured by Shinko Denki Co., Ltd., an impulse high frequency power source (100 kHz in continuous mode) manufactured by Heiden Laboratory, and Pearl. Industrial high frequency power supply (200 kHz), Pearl high frequency power supply (800 kHz), Pearl high frequency power supply (2 MHz), JEOL high frequency power supply (13.56 MH)
z), high frequency power source (27 MHz) manufactured by Pearl Industry, high frequency power source (150 MHz) manufactured by Pearl Industry, and the like can be preferably used.

In the present invention, the difference in the coefficient of linear thermal expansion between the metal base material of the electrode and the dielectric is set to 8 × 10 ^-6 / ° C or less, preferably 4 × 10 ^-6 / ° C or less. As a result, the adhesion between the metal base material and the dielectric can be improved, and the deviation between the dielectric and the metal base material can be eliminated. For example 100 ~
Even at a temperature of 300 ° C., the dielectric does not crack, and a heat resistant and durable electrode that can withstand high temperature and long time treatment can be obtained. In the present invention, the metal base material is 70% by mass.
The difference in the coefficient of thermal expansion can be set as described above by using a titanium alloy or titanium metal containing titanium as described above and using a sprayed ceramic as the dielectric material coated thereon.

In the present invention, it is necessary to employ the above-mentioned electrode capable of maintaining a uniform glow discharge state in a plasma discharge treatment apparatus by applying such a high power voltage. By performing plasma discharge treatment with a high power applied voltage, a uniform thin film can be formed and a dense thin film can be formed. On the other hand, when a low-power voltage is applied and plasma discharge treatment is performed at a relatively low temperature, the electrodes are likely to condense the reaction gas or the reaction gas after the treatment, resulting in uneven or weak plasma generation. And the thin film formation is likely to be non-uniform and less dense. For such a defect, it is preferable to raise the temperature of the electrode and maintain it at a predetermined temperature.

The atmospheric pressure plasma discharge treatment apparatus of the present invention comprises:
The electrode temperature adjusting means is provided, and the medium from the electrode temperature adjusting means is introduced into the electrode having a hollow inside, and the total thickness of the metal base material and the dielectric of the electrode is 2 to 30 mm.
By doing so, the heat exchange efficiency can be improved.
Thereby, the electrode surface can be maintained at a predetermined temperature, and plasma processing at high temperature and high output can be realized. If the total thickness exceeds 30 mm, heat transfer at high temperatures may not work well, resulting in uneven processing or insufficient temperature. For a pipe-shaped electrode such as a cylindrical fixed electrode, the metal base material itself needs to have a thin wall thickness of at least 2 mm, and if it is less than 2 mm, structural strength cannot be maintained.

Next, the reaction gas used in the atmospheric pressure plasma discharge treatment apparatus of the present invention will be described.

The reaction gas used in the present invention is composed of a mixed gas of a rare gas and a reactive gas.

Noble gases useful in the present invention include, for example, H 2.
Noble gases such as e, Ar, Xe, Ne, Kr, and Rn can be mentioned, but He or Ar is preferable, and Ar is particularly preferable.
Is preferred. The mixing ratio of the reactive gas varies depending on the application, the selected gas, or the reactive gas, but the rare gas is preferably 90 to 99.5% by volume.

In the present invention, forming a thin film on a substrate by atmospheric pressure plasma discharge treatment generally means forming a thin film such as an antireflection film, but surface-modifying the film. (Strictly speaking, a thin film is formed) and an action of etching the formed thin film are also included.

Examples of the film surface-treated using the atmospheric pressure plasma discharge treatment apparatus of the present invention include, for example, conventional silver halide photographic light-sensitive materials (hydrophilic surface) and silver salt photothermographic dry imaging materials (surface Are hydrophobized or hydrophilized), but are not limited to these applications.

Examples of the reactive gas useful in the present invention suitable for modifying the surface of the base film include oxygen, water vapor, hydrogen, methanol, ethanol, isopropyl alcohol and isobutyl as those which make the modification hydrophilic. Alcohol, acetone, methyl ethyl ketone, formaldehyde, acetaldehyde, carbon dioxide, carbon monoxide, nitrogen, nitric oxide, nitrogen dioxide, etc., and the modification is made hydrophobic, for example, methane, ethane, propane,
Aromatic hydrocarbons such as butane, hexane, toluene, xylene, benzene, aliphatic hydrocarbons such as propane, butane, pentane, hexane, ethylene, butene, pentene,
Unsaturated aliphatic hydrocarbons such as acetylene, butadiene and styrene, and organic fluorine compounds such as hexafluoroethane, tetrafluoroethylene, hexafluoropropylene, octafluorocyclobutane, difluoromethane, tetrafluoroethane, tetrafluoropropylene, trifluoropropylene , Chlorotrifluoromethane, chlorodifluoromethane, dichlorotetrafluorocyclobutane, tetrafluoromethane, tetrafluoroethylene, hexafluoropropylene, octafluorocyclobutane, difluoromethane, tetrafluoroethane, tetrafluoropropylene, trifluoropropylene, hexafluoroacetone, acrylic Acid, methacrylic acid, maleic anhydride, maleic acid, fumaric acid, 2-hydroxyethyl acryl Over DOO, 2-hydroxyethyl methacrylate, 2,2,2-trifluoroethyl acrylate, 2,2,2-trifluoroethyl methacrylate, perfluoro ethyl acrylate, perfluoro ethyl methacrylate and the like. In addition, by mixing two or more of the above substances, it is possible to exhibit special properties other than hydrophilization or hydrophobization.

In the present invention, a thin film is formed on the surface of a base material to be manufactured, for example, an electrode film, a dielectric protective film, a transparent conductive film, an electrochromic film, a fluorescent film, a magnetic recording film, a reflective film, a selection film. Functional films such as absorptive absorption film, selective transmission film, antireflection film, shadow mask, abrasion resistant film, corrosion resistant film, heat resistant film, lubricating film, and decorative film can be formed. And what formed these functional films on the base film is called a functional film.

Of these, an antireflection film having an antireflection film on a base film will be described as an example.

The antireflection film can be formed, for example, by laminating a high refractive index layer, a medium refractive index layer and a low refractive index layer.

Examples of the reactive gas used for forming the antireflection layer include organic titanium compounds, titanium hydrogen compounds, titanium halides, etc. for the high refractive index layer.
As the organic titanium compound, for example, triethyl titanium, trimethyl titanium, triisopropyl titanium, tributyl titanium, tetraethyl titanium, tetraisopropyl titanium, tetrabutyl titanium, triethoxy titanium,
Trimethoxy titanium, triisopropoxy titanium, tributoxy titanium, tetraethoxy titanium, tetraisopropoxy titanium, methyldimethoxy titanium, ethyl triethoxy titanium, methyl triisopropoxy titanium, tetradimethylamino titanium, dimethyl titanium diacetoacetonate, ethyl Examples of titanium hydrogen compounds include monotitanium hydrogen compounds and dititanium hydrogen compounds, such as titanium triacetoacetonate and tetradimethylaminotitanium, and examples of titanium halides include trichlorotitanium and tetrachlorotitanium.

Examples of the silicon compound used for the low refractive index layer include organic silicon compounds, silicon hydrogen compounds, and silicon halide compounds. Examples of the organic silicon compounds include tetraethylsilane, tetramethylsilane, and tetramethylsilane. Isopropylsilane, tetrabutylsilane,
Tetraethoxysilane, tetraisopropoxysilane,
Tetrabutoxysilane, dimethyldimethoxysilane, diethyldiethoxysilane, diethylsilanediacetacetonate, methyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, etc. Silicon hydrogen compounds include tetrahydrogenated silane and hexahydrogenated Disilane etc. can be mentioned. Further, the above-mentioned fluorine compounds can also be preferably used.

The medium refractive index layer may be a tin compound or a mixture of a fluorinated compound and a silicon compound, the tin compound may be an organic tin compound, a tin hydrogen compound, a tin halide, or the like. For example, tetraethyltin,
Tetramethyltin, di-n-butyltin diacetate, tetrabutyltin, tetraoctyltin, tetraethoxytin, methyltriethoxytin, diethyldiethoxytin, triisopropylethoxytin, diethyltin, dimethyltin, diisopropyltin, dibutyltin , Diethoxytin, dimethoxytin, diisopropoxytin, dibutoxytin, tin dibutyrate, tin diacetoacetonate, ethyltin acetoacetonate, ethoxytin acetoacetonate, dimethyltin diacetoacetonate, etc. Examples of the tin halide such as tin oxide include tin dichloride and tin tetrachloride, and any of them can be preferably used in the present invention. The tin oxide layer thus formed has a surface specific resistance value of 10 ¹² Ω / cm ² or less and is therefore useful as an antistatic layer.

From the viewpoint of handling, the above-mentioned organotin compound, organotitanium compound or organosilicon compound is preferably a metal hydrogen compound or a metal alkoxide, and it is free from corrosiveness, generation of harmful gas, and little stain in the process. From
Metal alkoxides are preferably used. Further, in order to introduce the above-mentioned organotin compound, organotitanium compound or organosilicon compound between the electrodes, which is the discharge space, both may be in a gas, liquid or solid state at normal temperature and pressure. In the case of gas, it can be directly introduced into the discharge space,
In the case of a liquid or solid, it is used after being vaporized by means such as heating, decompression, and ultrasonic irradiation. When an organic tin compound, an organic titanium compound, or an organic silicon compound is vaporized by heating and used, a metal alkoxide, such as metal tetraethoxide or metal tetraisopropoxide, which is liquid at room temperature and has a boiling point of 200 ° C. or lower is an antireflection film. It is preferably used for the formation of The metal alkoxide may be diluted with a solvent before use, and in this case, a rare gas may be bubbled to be used as a reaction gas. As the solvent, methanol, ethanol, isopropanol, butanol, n-
Organic solvents such as hexane and mixed solvents thereof can be used. The vaporization of the reaction gas vapor can be performed by using a vaporizer manufactured by Lintec Co., Ltd., for example. After vaporization, they may be mixed in a rare gas.

Regarding the reactive gas, in order to form a uniform thin film on the substrate by the discharge plasma treatment, the content ratio in the reaction gas is preferably 0.1 to 10% by volume, more preferably. , 0.1 to 5% by volume. Also,
Each of these reactive gases can be used within the target range of 2
You may mix and use 1 or more types simultaneously.

Further, when forming a thin film, as a reactive gas, oxygen, ozone, hydrogen peroxide, carbon dioxide, carbon monoxide,
A component selected from hydrogen and nitrogen may be contained in an amount of 0.01 to 5% by volume, whereby the reaction can be promoted and a dense and high-quality thin film can be formed.

Furthermore, by adding the following organometallic compounds to the reactive gas, it is possible to form various functional thin films for the following advanced technological purposes from the present to the near future. Examples of the metal of the organometallic compound include Li, Be, B, Na, Mg, Al, Si, K,
Ca, Sc, Ti, V, Cr, Mn, Fe, Co, N
i, Cu, Zn, Ga, Ge, Rb, Sr, Y, Zr,
Nb, Mo, Cd, In, Ir, Sn, Sb, Cs, B
a, La, Hf, Ta, W, Tl, Pb, Bi, Ce,
Pr, Nd, Pm, Eu, Gd, Tb, Dy, Ho, E
r, Tm, Yb, Lu and the like can be mentioned, and more preferably, these organometallic compounds are metal alkoxides,
Those selected from alkylated metals and metal complexes are preferable.

Examples of the functional thin film formed of these are shown below, but the present invention is not limited to this.

Electrode film: Au, Al, Ag, Ti, Ti,
Pt, Mo, Mo-Si dielectric protective _{film: SiO 2, SiO, Si 3} N 4, Al
₂ O ₃ , Al ₂ O ₃ , Y ₂ O ₃ transparent conductive film: In ₂ O ₃ , SnO ₂ electrochromic film: WO ₃ , IrO ₂ , MoO ₃ ,
V ₂ O ₅ phosphor layer: ZnS, ZnS + ZnSe, ZnS + CdS Magnetic recording membrane: Fe-Ni, Fe-Si -Al, γ-Fe
₂ O ₃ , Co, Fe ₃ O ₄ , Cr, SiO ₂ , AlO ₃ Superconductive film: Nb, Nb-Ge, NbN Solar cell film: a-Si, Si Reflective film: Ag, Al, Au, Cu Selectivity absorbing film: ZrC-Zr selectively permeable membrane: In ₂ O _3, SnO ₂ antireflective _{film: SiO 2, TiO 2, SnO} 2 shadow mask: Cr wear-resistant film: Cr, Ta, Pt, TiC , TiN corrosion film : Al, Zn, Cd, Ta, Ti, Cr Heat resistant film: W, Ta, Ti Lubricating film: MoS ₂ Decorative film: Cr, Al, Ag, Au, TiC, Cu.

Examples of the substrate include a plastic film, a plastic molded product, a glass molded product, and a glass plate.

For continuous and efficient plasma discharge treatment, a substrate film, that is, a plastic film is preferable as the substrate.

The plastic film used in the present invention is not particularly limited, but examples thereof include cellulose ester films such as cellulose triacetate film, cellulose acetate propionate and cellulose acetate butyrate film, polyester film, polyethylene terephthalate film, polyethylene. Examples thereof include polyester films such as naphthalate films, polycarbonate films, polyether sulfone films, norbornene resin films and the like.

Among the above plastic films, a cellulose ester film is preferably used in the present invention as one having transparency, optical isotropy, strength, suppleness, easiness of production and the like.

[0064]

Example 1 A simple electrode as shown in FIGS. 5 and 6 was prepared for a heat resistance and durability test of an electrode. FIG. 5 is a cross-sectional view of opposing electrodes for heat resistance and durability test. FIG. 6 is a view showing a state in which the counter electrode of FIG. 5 is housed in a container and the equipment necessary for the heat resistance durability test is connected. In FIG. 5, a square with two holes H on the bottom and a side length of 80 mm, a height of 30 mm, and a wall thickness of 5 mm
The side of the hollow box-shaped stainless steel container 203 on the open side has a length of 80 mm and a thickness of 5 to 40 m.
m of metal base materials 201A and 202A of the following materials are used as lids, and each is attached with a heat-resistant adhesive, and the thickness of 1 m is applied to the surface of the square bases of the metal base materials 201A and 202A.
m dielectrics 201B and 202B, respectively,
A solution prepared by diluting tetramethoxysilane with ethyl acetate was applied thereon, dried, and then cured by irradiation with ultraviolet rays to carry out a sealing treatment to prepare two electrodes 201 and 202 having a sprayed alumina white dielectric material having Rmax of 1 μm. . These two electrodes 201 and 202 are connected to the surface of the dielectric 201B and 20
A pair of opposing electrodes 200 were made to face each other such that the 2B planes were spaced by 1 mm. In FIG. 6, two holes H on the bottom surface of the stainless steel container 203 are for the inlet and outlet of the heat exchange medium flow path, and through the holes silicon oil of a constant temperature is pumped into the heat exchanger 210 and the pump outside the container 207. A constant amount can be constantly circulated through the pipes 211 and 212 via. The circulation rate was 12 L / min. The gas introduction port 20 is provided in the container 207 that shields this counter electrode from the outside.
8 was introduced to replace the air with the reaction gas, and the reaction gas was slowly flown and discharged from the exhaust port 209. The reaction gas was directly introduced into the discharge treatment section 204 in the gap between the opposed electrodes through the gas introduction port 205 so as to spread over the entire width of the electrode, and the treated gas was discharged through the exhaust port 206. A high frequency power source and ground were connected to each metal base material or base metal. Silicon oil was set from the heat exchanger 210 to each temperature used for the measurement, and the stainless steel box was filled and circulated. The electrode temperature was measured by a thermal video system TVS3300 manufactured by Nippon Avionics Co., Ltd. and an infrared camera. As a high frequency power source, for 50 ° C and 60 ° C, a high frequency power source (50 kHz) manufactured by Shinko Electric Co., Ltd., 100
High temperature power source made by Heiden Laboratory (continuous mode, 100 kHz) for ℃, high frequency power source made by Pearl Industry (200 kHz) for 150 ° C., high frequency power source made by Pearl Industry (800 kHz) for 250 ° C., Pulse high frequency power supply CF-50 manufactured by Pearl Industrial Co. for 300 ° C
Tests 1 to 8 were carried out using 00-13M (13.56 MHz) while observing the time until cracks were formed in the dielectric. The supplied power was 0.5 to 30 W / cm ² . The pressure was 103 kPa.

<< Combination of Metal Base Material and Dielectric Material >> 1) Metal Base Material: Titanium Alloy (T64) Thickness 5 mm Dielectric: White Alumina Spray 2) Metal Base Material: Industrial Pure Titanium (TIB) Thickness 5 mm Dielectric Body: White alumina sprayed 3) Metal base material: Stainless steel (AISI31)
6) Thickness 5 mm Dielectric: White alumina sprayed 4) Metal base material: Aluminum alloy, thickness 5 mm Dielectric: White alumina sprayed 5) Metal base material: Titanium alloy (T64) Thickness 30 mm Dielectric: Glass lining 6) Metal base material: Titanium alloy (T64) thickness 40 mm Dielectric: White alumina sprayed 7) Metal base material: Titanium alloy (T64) thickness 40 mm Base: Gold plating (10 μm) Dielectric: White alumina sprayed 8) Metal base material: Industrial pure titanium (TIB) thickness 40m
m Base: Gold plating (10 μm) Dielectric: White alumina sprayed.

<< Reaction Gas >> Noble gas: Argon (97% by volume) Reactive gas: Nitrogen (3% by volume) The results of the above electrodes are shown in Table 1.

[0067]

[Table 1]

(Results) The counter electrode, in which the metal base material is titanium alloy or titanium metal and the dielectric is sprayed white alumina, is capable of long-time atmospheric pressure plasma discharge treatment without cracking in the dielectric even at a high temperature of 300 ° C. I found out. Also, even if the dielectric is glass lining,
It was also found that it can be used at a considerably high temperature, although it is inferior to the sprayed white alumina. On the other hand, an electrode coated with stainless steel and aluminum alloy as a metal base material and sprayed with white alumina as a dielectric can be used only at about 50 ° C, and cracks occur in a short time. Atmospheric pressure plasma that can be used for a long time with high power by being damaged and using titanium alloy or titanium metal for the metal base material of the electrode and further coating the sprayed ceramic dielectric on the titanium metal base material A discharge processing device can be provided.

Example 2 As a base material for forming a thin film on the surface of the base material film, 65 μm Konikakak KC4UX (manufactured by Konica Corporation, cellulose triacetate film, abbreviated as TAC) was used.
In the apparatus as shown in FIG. 2, atmospheric pressure plasma discharge treatment was performed while winding the base film around the rotating electrode of the ground electrode. For the rotating electrode of the ground electrode and the cylindrical fixed electrode of the applying electrode, the metal base materials of the following counter electrodes 1 to 5 with a jacket having a heat retaining function with heat retaining water were used. The counter electrodes 1, 2 and 4 were coated with 1 mm of sprayed alumina ceramics (sprayed alumina white), and a solution prepared by diluting tetramethoxysilane with ethyl acetate was applied and dried.
It was cured by irradiation with ultraviolet rays and subjected to a sealing treatment to prepare a rotating electrode and a fixed electrode having a sprayed alumina white dielectric material having an Rmax of 1 μm. For the counter electrodes 3 and 5, a rotating electrode and a fixed electrode were prepared by lining borate glass as a dielectric. For the counter electrode 2, gold was plated on the metal base material. As the cylindrical fixed electrode of the applying electrode, a rectangular fixed electrode group (fixed electrode 1) and the concave fixed electrode (fixed electrode 2) shown in FIG. 4 are used, and the rectangular cylindrical shape faces the rotating electrode. The one in which one surface forms an arc of a slightly larger concentric circle of the cross-sectional circle of the rotating electrode was used. The rotating electrode was grounded (grounded), and the square tubular fixed electrode was connected to each of the following high-frequency power sources. The distance between the dielectrics (electrode gap) in the processing section was 1.0 mm, and the pressure in the processing section was 103 kPa. As shown in Table 2, the following high-frequency power supplies were used under the respective conditions, and the following reaction gas was supplied at a predetermined electrode temperature while adjusting the transfer rate of the base material film and the jacket temperature to obtain the target film thickness. Plasma discharge treatment was carried out using and tests 9 to 22 were carried out.

<< Material and Thickness of Counter Electrode (Rotating Electrode and Square Cylindrical Fixed Electrode Group) >> Counter Electrode 1 Metal Base Material: Titanium Alloy (T64) Thickness 20 mm Dielectric: Sprayed White Alumina Thickness 1 mm Counter Electrode 2 Metal base material: Titanium alloy (T64) Thickness 20 mm Bottom: Gold plating Thickness 10 μm Dielectric: Thermal sprayed white alumina 1 mm thickness Counter electrode 3 Metal base material: Industrial pure titanium (TIB) Thickness 25 mm Dielectric: Glass lining Thickness 1mm Counter electrode 4 Metal base material: Stainless steel (AISI316)
Thickness 20mm Dielectric: Thermal sprayed white alumina Thickness 1mm Counter electrode 5 Metal base material: Stainless steel (AISI316)
Thickness 20mm Dielectric: Glass lining Thickness 1mm << High frequency power source >> High frequency power source 1: High frequency power source manufactured by Shinko Electric Co., Ltd. (50kHz)
z) High frequency power supply 2: High frequency power supply manufactured by Heiden Institute (continuous mode used, 100 kHz) High frequency power supply 3: High frequency power supply manufactured by Pearl Industrial (200 kHz)
z) High frequency power supply 4: High frequency power supply manufactured by Pearl Industry (800 kHz)
z) High frequency power source 5: Pulse high frequency power source CF manufactured by Pearl Industrial Co., Ltd.
-5000-13M (13.56MHz) << Reaction gas (for thin film formation) >> Noble gas: Argon (99% by volume) Reactive gas: Hydrogen (0.7% by volume) Tetraethoxysilane (0.3% by volume) Tetra Ethoxysilane is a high-purity raw material produced by Lintec Co., Ltd.
What was quantitatively vaporized with a vaporizer manufactured was introduced.

[Measurement and Evaluation] <Measurement of Thickness Unevenness of Thin Film> TAC was subjected to atmospheric pressure plasma discharge treatment under the conditions and transfer rates as shown in Table 2, and 1 hour and 24 hours after the start of treatment. A treated sample was taken from each part over a length of 30 m. From the treated sample of 30 m, 10 samples each having a width of 30 cm for film thickness measurement were taken at intervals of 1 m. After roughening the surface (rear surface) opposite to the thin film forming surface of each film thickness measurement sample, light absorption processing was further performed on the surface by using a black spray. Using a spectrophotometer 1U-4000 (manufactured by Hitachi, Ltd.), 20 points in the width direction of 30 cm in total width, a total of 200 points, the reflectance under the condition of 5 degree regular reflection of the thin film forming surface (wavelength of 400 to 700 nm). Was measured to determine the maximum film thickness unevenness ± (nm). The refractive index was also measured at the same time, and the optical film thickness (optical film thickness = film thickness × refractive index) was calculated from them.

<Pencil Hardness Test> According to the pencil hardness test of JIS K5400, pencils of 5H to 3B were prepared and evaluated by drawing so as to scratch the thin film forming surface of the sample.

The above results are shown in Table 2 below.

[0074]

[Table 2]

(Results) In the electrode in which the metal base material of the electrode is titanium alloy or titanium metal, and the dielectric is coated with sprayed white alumina, the pencil hardness is high without unevenness in film thickness, and the discharge treatment is performed at a transfer speed of 10 m / min or more. In addition, the electrode using gold plated electrode is about 20m /
It was found that discharge processing can be performed at a speed of a minute. Further, even glass-lined ones could be discharged at a speed of about 10 m / min, and had a pencil hardness of 3H to 4H, which was a considerable hardness. On the other hand, at a low temperature of 50 ° C. for the coating in which the metal base material is stainless steel and the sprayed white alumina is for the dielectric, or 25 ° C. for the coating in which the glass lining is used, even if the speed is reduced to 5 m / min or less. A thin film with high hardness could not be obtained. Further, when the electrode temperature was raised to 60 ° C., damage to the derivative occurred, and the test could not be performed. As described above, it has been found that an atmospheric pressure plasma discharge treatment apparatus and method can be provided which can be produced at a high speed even at a high temperature and can obtain a thin film of excellent quality.

[0076]

EFFECTS OF THE INVENTION By using a titanium alloy or titanium metal for the electrode, a high-performance thin film can be formed on the surface of the base material by stable plasma discharge treatment at high temperature for a long time, and high quality and excellent atmospheric pressure. A plasma discharge processing apparatus and a discharge processing method can be provided.

[Brief description of drawings]

FIG. 1 is a diagram showing an example of an atmospheric pressure plasma discharge treatment apparatus of the present invention.

FIG. 2 is a perspective view showing an example of a rotating electrode according to the present invention.

FIG. 3 is a perspective view showing an example of a square tube fixed electrode of a square tube type fixed electrode group.

FIG. 4 is a schematic view showing an example of an atmospheric pressure plasma discharge treatment apparatus having a concave fixed electrode as an application electrode and a rotating electrode as a ground electrode.

FIG. 5 is a cross-sectional view of opposing heat resistance and durability test electrodes.

FIG. 6 is a diagram showing a state in which the counter electrode of FIG. 5 is housed in a container and the equipment necessary for the heat resistance durability test is connected.

[Explanation of symbols]

25, 25a, 101 rotating electrodes 25A, 36A, 101A, 102A, 201A, 20
2A metal base materials 25B, 36B, 101B, 102B, 201B, 20
2B Dielectric 30 Plasma discharge treatment device 31, 110 Plasma discharge treatment container 32, 103, 204 Discharge treatment unit 36 Cylindrical fixed electrode group 36a Square tubular fixed electrode 40 Voltage applying means 41, 105, 214 High frequency power supply 50 Gas filling means 51 Gas Generator 52 Air Supply Ports 53, 206, 209 Exhaust Port 60 Electrode Temperature Adjusting Means 61, 211, 212 Pipes 64, 67, 104, 113 Guide Rolls 65, 66, 106, 112 Nip Rolls 68, 69, 109, 115 Partition plate 102 Fixed electrode 107 Container gas introduction port 108 Processing part gas introduction port 111 Processing part container 114 Container exhaust port 116 Processing part exhaust port 200 Counter electrode 201, 202 Electrode 203 Stainless steel container 207 Container 205, 208 Gas introduction port 210 Heat exchanger F Substrate film F'treated Base film G Reaction gas G'H gas after treatment H hole

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Kiyoshi Oishi             Konica Stock Market, 1 Sakura-cho, Hino City, Tokyo             In-house (72) Inventor Akira Nishiwaki             Konica Stock Market, 1 Sakura-cho, Hino City, Tokyo             In-house F-term (reference) 4G075 AA24 AA30 AA63 BC04 CA15                       DA01 EB41 EC21 ED04 ED09                       FB02 FB04 FC15                 4K030 CA07 CA17 FA03 GA14 JA09                       JA10 KA14 KA16 KA22 KA46                       KA47

Claims (12)

[Claims] 1. Reactivity between the opposing electrodes by applying a high-frequency voltage between the electrodes where the opposing electrode is formed by the applying electrode and the ground electrode to discharge under atmospheric pressure or a pressure in the vicinity thereof. A plasma discharge treatment apparatus for forming a thin film on a base material by exposing a base material to the reaction gas in the plasma state by forming a reaction gas containing a gas and a noble gas into a plasma state, and a metal of the opposing electrode. A plasma discharge treatment apparatus, wherein the base material is a titanium alloy or titanium metal containing 70% by mass or more of titanium. 2. The reactivity between the counter electrodes is generated by applying a high-frequency voltage between the electrodes where the counter electrode is formed between the applying electrode and the ground electrode under atmospheric pressure or a pressure in the vicinity thereof to cause discharge. A plasma discharge treatment apparatus for forming a thin film on a base material by exposing a base material to the reaction gas in the plasma state by forming a reaction gas containing a gas and a noble gas into a plasma state, and a metal of the opposing electrode. A plasma discharge treatment apparatus, wherein the base material is a titanium alloy or titanium metal containing 70% by mass or more of titanium, and the metal base material is covered with a ceramic sprayed dielectric. 3. Reactivity between the opposing electrodes by applying a high-frequency voltage between the electrodes where the opposing electrode is formed by the applying electrode and the ground electrode to discharge under atmospheric pressure or a pressure in the vicinity thereof. A plasma discharge treatment apparatus for forming a thin film on a base material by exposing a base material to the reaction gas in the plasma state by forming a reaction gas containing a gas and a rare gas into a plasma state, wherein the opposing electrode is 70 mass%
A metal base material of titanium alloy or titanium metal containing titanium as described above, and a metal base material coated with a ceramics-sprayed dielectric material, and between the metal base material and the dielectric material above the metal base material. 1 to 1,000 μm thick on the surface of the metal base material
A plasma discharge treatment apparatus having a metal base of m having a smaller electric resistance than the metal base material. 4. The base metal is Cu, Au, Ag,
The plasma discharge treatment apparatus according to claim 3, which is at least one selected from Pt, Cr, Ni, and Zn, or an alloy containing an element selected from these. 5. The plasma discharge processing apparatus according to claim 3, wherein the base is applied by a metal spraying method or a plating method. 6. The plasma discharge treatment apparatus according to claim 2, wherein the dielectric has a thickness of 0.1 to 3 mm. 7. The dielectric material according to claim 2, wherein the dielectric material has a porosity of 0.01 to 6% by volume.
The plasma discharge treatment device according to the item. 8. The reactivity between the opposing electrodes is generated by applying a high-frequency voltage between the electrodes in which the opposing electrode is formed between the applying electrode and the ground electrode under atmospheric pressure or a pressure in the vicinity thereof to cause discharge. A plasma discharge treatment apparatus for forming a thin film on a base material by exposing a base material to the reaction gas in the plasma state by forming a reaction gas containing a gas and a noble gas into a plasma state, and a metal of the opposing electrode. The base material is a titanium alloy or titanium metal containing 70% by mass or more of titanium, and the metal base material is coated with a ceramic-sprayed dielectric material, and the temperature of the metal base material can be controlled by a heat medium. As described above, the plasma discharge treatment apparatus is characterized in that the total thickness of the metal base material and the dielectric is 2 to 30 mm. 9. The ground electrode is a rotating electrode, and the applying electrode is a cylindrical fixed electrode group arranged along the rotating electrode, according to any one of claims 1 to 8. The plasma discharge treatment device according to. 10. The ground electrode is a rotating electrode, and the applying electrode is a concave fixed electrode having a concave surface of a circle of the rotating electrode and a circular arc of a larger concentric circle. The plasma discharge treatment apparatus according to any one of claims. 11. A plasma discharge treatment apparatus according to any one of claims 1 to 10, wherein an electrode temperature is set to 100.
A plasma discharge treatment method, which comprises forming a thin film while maintaining the temperature at 300 ° C. 12. The plasma discharge treatment method according to claim 11, wherein the thin film is formed while maintaining the temperature of the electrode at 120 to 250 ° C.