JP6414784B2 - Electrode for atmospheric pressure plasma generation, atmospheric pressure plasma generator, method for producing surface modified substrate, and method for producing reusable electrode - Google Patents

Description

  The present invention relates to an electrode for generating atmospheric pressure plasma, an apparatus for generating atmospheric pressure plasma, a method for manufacturing a surface-modified substrate, and a method for manufacturing a reuse electrode.

  Conventionally, for the improvement of surface properties such as surface wettability improvement of various substrates such as organic materials and inorganic materials, cleaning for oil removal, physical treatment for improving adhesion, etc. An atmospheric pressure plasma treatment is used in which the surface is irradiated with plasma in the air. In such atmospheric pressure plasma processing, a reactive gas introduced between the plasma electrode and the object to be processed is converted to atmospheric pressure by applying a high voltage between two plasma electrodes arranged opposite to each other by a high frequency pulse power source. By generating a plasma underneath, radicals are generated, and the radicals are chemically and physically modified by the radicals (dielectric barrier discharge type atmospheric pressure plasma treatment).

  Advantages of the dielectric barrier discharge type atmospheric pressure plasma treatment include that it can be efficiently treated by direct contact with plasma, and that equipment such as a pressure vessel can be obtained by treatment under atmospheric pressure. The point which is unnecessary, a point with little discharge | emission of waste liquid etc. are mentioned.

  In Patent Document 1, when performing atmospheric pressure plasma treatment, a through hole is provided in the surface of the substrate, and a reactive gas is introduced between the substrate and the electrode, so that they are opposed to each other with a narrow gap of several mm or less. A method has been proposed in which the reaction gas distribution between the two electrodes is made uniform and the substrate is subjected to atmospheric pressure plasma treatment.

  Further, in Patent Document 2, when performing atmospheric pressure plasma processing on a large-area substrate, a plurality of parallelogram electrodes arranged perpendicular to the traveling direction of the substrate to be processed and a plurality of parallelogram electrodes parallel to each other. By using an electrode part comprising a gas inlet formed in the base plate and flanges provided on both sides in the substrate traveling direction, the gas is held on the substrate moving opposite to the electrode part, and has a large area. Has proposed a method of performing atmospheric pressure plasma treatment with a large electrode by stably maintaining atmospheric pressure plasma.

  As described above, in the atmospheric pressure plasma treatment, it is necessary to keep the concentration of the reaction gas introduced into the electrode portion high in order to efficiently perform the treatment on the base material.

  By the way, in such a dielectric barrier discharge type atmospheric pressure plasma treatment, when a distance between two electrodes is increased and treatment is performed on a thick substrate, a high voltage is applied by a high frequency pulse power source. The plasma cannot be generated efficiently in the atmosphere. Therefore, since the atmospheric pressure plasma treatment is generally strongly restricted by the distance between two electrodes, it can be applied only to a substrate having a thickness of less than 1.5 mm, and for a substrate having a thickness larger than that. When the surface treatment is performed, the surface treatment is performed by a method other than atmospheric pressure plasma, such as ultraviolet treatment or chemical immersion.

JP 2014-063874 A Japanese Patent Laying-Open No. 2015-076328

  The present invention has been made in view of such problems, and in atmospheric pressure plasma processing, for example, an atmospheric pressure plasma generating electrode capable of efficiently surface-treating a large material having a thickness, for example. The purpose is to provide.

This inventor repeated earnest examination in order to solve the subject mentioned above. As a result, in the atmospheric pressure plasma treatment, for example, for a large material having a thickness, a metal layer and a dielectric layer having a thermal expansion coefficient of 40 × 400 ⁻⁶ or less at 40 to 400 ° C. It is found that an atmospheric pressure plasma treatment can be efficiently performed on a substrate by using an electrode having a surface or an electrode having a recess having a cross-sectional shape capable of accommodating at least a part of the substrate on the surface of the electrode. It came to complete. Specifically, the present invention provides the following.

1st invention of this application has the structure where the metal layer and the dielectric material layer were laminated | stacked, and the said dielectric material layer has a thermal expansion coefficient in 40-400 degreeC below 6.5 * 10 < ^-6 > / K. It is an electrode for atmospheric pressure plasma generation containing the dielectric material which is.

  A second invention of the present application is the electrode for generating atmospheric pressure plasma according to the first invention, wherein an average thickness of the dielectric layer is 0.9 mm or less.

  According to a third invention of the present application, in the first or second invention, the dielectric layer includes at least one dielectric selected from the group consisting of silicon nitride, aluminum nitride, or a composite nitride of silicon and aluminum. It is an electrode for generating atmospheric pressure plasma.

  A fourth invention of the present application is the atmospheric pressure plasma generating electrode according to any one of the first to third inventions, wherein the metal layer includes a metal having a specific resistance value of 50 μΩcm or less.

  A fifth invention of the present application has a structure in which a first dielectric layer, a metal layer, and a second dielectric layer are laminated, and the metal layer has a first surface and a second surface, The first dielectric layer covers the first surface, and the second dielectric layer is an electrode for generating atmospheric pressure plasma that extends outward from an end of the metal layer.

  6th invention of this application is an electrode for atmospheric pressure plasma generation for processing to a base material, Comprising: The cross section which is located in the surface of the said electrode for atmospheric pressure plasma generation, and can accommodate at least one part of the said base material It is an atmospheric pressure plasma generating electrode having a concave portion.

  7th invention of this application is an atmospheric pressure plasma generator provided with the electrode for atmospheric pressure plasma generation concerning the invention in any one of 1st-6th.

  An eighth invention of the present application includes the atmospheric pressure plasma generating electrode according to any one of the first to fourth aspects, and a counter electrode containing a metal, and the dielectric layer of the atmospheric pressure plasma generating electrode; In the atmospheric pressure plasma generator, the surface of the counter electrode is disposed so as to be opposed to each other, and the minimum distance between the dielectric layer and the surface of the counter electrode is 1.5 mm or more.

  A ninth invention of the present application includes the atmospheric pressure plasma generating electrode according to the fifth invention and a counter electrode containing a metal, the first dielectric layer of the atmospheric pressure plasma generating electrode, and the counter electrode The atmospheric pressure plasma generator is arranged such that the minimum distance between the first dielectric layer and the counter electrode surface is 1.5 mm or more.

  A tenth aspect of the present invention includes an atmospheric pressure plasma generation electrode according to the sixth aspect of the present invention, a counter electrode containing a metal, the surface of the atmospheric pressure plasma generation electrode having the recess, and the counter electrode The atmospheric pressure plasma generator has a minimum distance of 1.5 mm or more between the surface having the recess and the surface having the recess and the counter electrode surface.

  The eleventh invention of the present application is the dielectric layer of the atmospheric pressure plasma generating electrode according to any one of the first to fourth inventions, and the surface having the concave portion of the atmospheric pressure plasma generating electrode according to the sixth invention. Is an atmospheric pressure plasma generator arranged to face each other.

  A twelfth invention of the present application is the atmospheric pressure plasma generator according to the eleventh invention, wherein a minimum distance between the dielectric layer and the surface having the recess is 1.5 mm or more.

  In a thirteenth aspect of the present application, the first dielectric layer of the atmospheric pressure plasma generation electrode according to the fifth aspect and the surface having the concave portion of the atmospheric pressure plasma generation electrode according to the sixth aspect of the invention include: It is an atmospheric pressure plasma generator arranged so as to face each other.

  A fourteenth invention of the present application is the atmospheric pressure plasma generator according to the thirteenth invention, wherein a minimum distance between the first dielectric layer and the surface having the concave portion is 1.5 mm or more.

  A fifteenth aspect of the present invention is an atmospheric pressure plasma generator for processing a substrate, wherein a plurality of atmospheric pressure plasma generation electrodes according to the fifth aspect are arranged, and the metal layer is arranged in the arrangement direction. It is an atmospheric pressure plasma generator arranged to be continuous.

  16th invention of this application is a manufacturing method of the surface modification base material which performs an atmospheric pressure plasma process to a base material using the atmospheric pressure plasma generator concerning any one of 7th-15th invention.

  A seventeenth invention of the present application is a method for performing an atmospheric pressure plasma treatment on a base material using an atmospheric pressure plasma generator, comprising the atmospheric pressure plasma generation electrode according to the sixth aspect of the invention, After the atmospheric pressure plasma treatment is performed on the base material in a state where at least a part is accommodated in the concave portion, the atmospheric pressure plasma treatment is performed on the base material in a state where the portion accommodated in the concave portion of the base material is exposed. Is a method for producing a surface-modified base material.

  18th invention of this application is a manufacturing method of the reuse electrode which performs the acid treatment or the alkali treatment to the electrode for atmospheric pressure plasma generation which concerns on any 1-5 invention.

  According to the present invention, in the atmospheric pressure plasma treatment, for example, a surface treatment can be efficiently performed on a large material having a thickness.

It is sectional drawing for demonstrating the structure of the electrode for atmospheric pressure plasma generation of a 1st aspect. It is a perspective view for demonstrating the structure of the electrode for atmospheric pressure plasma generation of a 1st aspect. It is sectional drawing for demonstrating the structure of the electrode for atmospheric pressure plasma generation of a 2nd aspect. It is a perspective view for demonstrating the structure of the electrode for atmospheric pressure plasma generation of a 2nd aspect. It is a top view for demonstrating an example of the structure which arrange | positions the electrode for atmospheric pressure plasma generation of a 2nd aspect so that a metal layer may continue. It is a top view for demonstrating an example of the structure which arrange | positions the electrode for atmospheric pressure plasma generation of a 2nd aspect so that a metal layer may continue. It is a perspective view for demonstrating the structure of the electrode for atmospheric pressure plasma generation of a 3rd aspect. It is a perspective view for demonstrating the structure of the electrode for atmospheric pressure plasma generation of a 3rd aspect. It is a perspective view for demonstrating the structure of the electrode for atmospheric pressure plasma generation of a 3rd aspect. It is a schematic diagram for demonstrating the structure of the apparatus for atmospheric pressure plasma generation. It is a schematic diagram for demonstrating the manufacturing method of a modified base material.

  Hereinafter, a specific embodiment of the present invention (hereinafter referred to as “the present embodiment”) will be described in detail with reference to the drawings. In addition, this invention is not limited to the following embodiment, It can implement by adding a change suitably within the range of the objective of this invention.

  Hereinafter, the “base material” is an object to be subjected to the atmospheric pressure plasma treatment by the atmospheric pressure plasma generator according to the present embodiment. Although it does not specifically limit as a base material, Various materials, such as organic, inorganic, and a composite material, can be used. Specifically, for example, glass (quartz, etc.), inorganic oxide materials such as alumina, zirconia, metal materials such as stainless steel, iron, titanium, aluminum, polymers such as polyethylene, polyimide, polypropylene, perfluoroethylene, and acrylic. Examples thereof include materials, graphite, carbon sintered bodies, carbon materials such as silicon carbide, plant fibers such as paper and cotton.

<< 1. Electrode for atmospheric pressure plasma generation >>
<1-1. Electrode for atmospheric pressure plasma generation according to first aspect>
Atmospheric pressure plasma generating electrode according to the present embodiment, the metal layer has a structure in which dielectric layers are laminated, the dielectric layer, the thermal expansion coefficient at 40 to 400 ° C. is 6.5 × 10 ^{- It} includes a dielectric that is ⁶ / K or less. FIG. 1 is a cross-sectional view for explaining the configuration of an electrode for generating atmospheric pressure plasma. FIG. 2 is a perspective view for explaining the configuration of the atmospheric pressure plasma generation electrode.

  The shape of the atmospheric pressure plasma generating electrode 1 is not particularly limited, and an appropriate shape can be used according to the shape of the base material to which the atmospheric pressure plasma treatment is applied and the shape of the pair of electrodes. 1 and 2 show a flat-plate-shaped atmospheric pressure plasma generating electrode 1 as an example, but the present invention is not limited to this example, and the generation of atmospheric pressure plasma in other shapes such as a curved surface is shown. An electrode device can be used.

[Metal layer]
The atmospheric pressure plasma generating electrode 1 includes a metal layer 11. The metal layer 11 contains a metal and has conductivity.

  Although it does not specifically limit as a metal which comprises the metal layer 11, For example, what has a specific resistance value of 1000 microhm-cm or less is preferable, what is 500 microohm-cm or less is more preferable, what is 100 microohm-cm or less is further more preferable, and 50 microohm-cm or less Some are particularly preferred. By forming the metal layer 11 with a metal having a specific resistance value of 1000 μΩcm or less, plasma can be generated efficiently.

  Specifically, as a metal constituting the metal layer 11, for example, platinum, gold, silver, copper, aluminum, tungsten, stainless steel, or an alloy such as brass can be used.

  Although it does not specifically limit as average thickness of the metal layer 11, It is preferable that it is 0.05 mm or more, and it is more preferable that it is 0.1 mm or more. By using the metal layer 11 having an average thickness of 0.05 mm or more, the strength of the metal layer 11 can be increased. Moreover, as an upper limit of the average thickness of the metal layer 11, it is preferable that it is 0.5 mm or less, and it is more preferable that it is 0.3 mm or less. By using the metal layer 11 having an average thickness of 0.5 mm or less, the electrode can be thinned.

  The area of the metal layer 11 is not particularly limited, but is preferably smaller than the dielectric layer 12. Here, the “area” means an area when each layer is viewed in plan. Moreover, it is preferable that at least one entire surface of the metal layer 11 is covered with the dielectric layer 12. Thereby, generation | occurrence | production of the arcing from the exposed surface of the metal layer 11 to the electrode which becomes a pair with the atmospheric pressure plasma generation electrode 1 can be suppressed efficiently.

  In the case where the atmospheric pressure plasma generating electrode 1 is configured only from the two-layered structure of the metal layer 11 and the dielectric layer 12, the area of the metal layer 11 is the area of the dielectric layer 12 in plan view of the stacked structure. It is preferable that the end of the metal layer 11 and the end of the dielectric layer 12 are not in contact with each other. The minimum distance between the end of the metal layer 11 and the end of the dielectric layer 12 is preferably 0.5 cm or more, more preferably 0.8 cm or more, and 1.0 cm or more. Further preferred. If it is 0.5 cm or more, the occurrence of arcing from the metal layer 11 to the electrode paired with the atmospheric pressure plasma generating electrode 1 can be efficiently suppressed. On the other hand, the upper limit of the minimum distance between the end of the metal layer 11 and the end of the dielectric layer 12 can be set to 3.0 cm or less, for example. The “minimum distance between the end portion of the metal layer 11 and the end portion of the dielectric layer 12” refers to the end of the metal layer 11 when the atmospheric pressure plasma generating electrode 1 is viewed in plan view from the side having the metal layer 11. This is the smallest of the distances from the portion to the end of the dielectric layer 12. 1 and 2 show examples of the atmospheric pressure plasma generating electrode 1 in which the area of the metal layer 11 is smaller than the area of the dielectric layer 12, the present invention is limited to this. It is not a thing.

[Dielectric layer]
The dielectric material constituting the dielectric layer 12 has a coefficient of thermal expansion at 40 to 400 ° C. of 6.5 × 10 ⁻⁶ / K or less. Moreover, as a thermal expansion coefficient in 40-400 degreeC of a dielectric material, it is preferable that it is 6.0 * 10 < ^-6 > / K or less, for example, and it is more preferable that it is 5.5 * 10 < ^-6 > / K or less. More preferably, it is 5.0 × 10 ⁻⁶ / K or less. Conventionally, alumina is used as the dielectric layer. When the distance between the electrodes is less than 1.5 mm, the temperature of the electrodes rises to a maximum of about 200 ° C. by applying a voltage, and therefore there is little risk of damage even if alumina is used. On the other hand, when the distance between the electrodes is 1.5 mm or more, the temperature of the electrodes may rise to a maximum of 300 to 400 ° C. by applying a voltage (especially, the reaction gas may be dry air, nitrogen gas, etc.). In the case of polyatomic molecules). Therefore, when alumina is used, if the temperature is increased to such a temperature by the plasma treatment, the expansion increases. By repeating such a plasma treatment, alumina repeatedly undergoes large expansion and contraction and may be damaged. Since the thermal expansion coefficient at 40 to 400 ° C. of the dielectric layer 12 is not more than 6.5 × 10 ⁻⁶ / K, even if the temperature of the electrode rises to 400 ° C., the expansion is small and the plasma treatment is repeated. Damage can be suppressed. Further, even if the dielectric layer is thinned, damage to the layer can be suppressed.

  Although it does not specifically limit as a dielectric constant of the dielectric material which comprises the dielectric material layer 12, For example, it is preferable that it is 2 or more, it is more preferable that it is 3 or more, and it is further more preferable that it is 4 or more. By forming the dielectric layer 12 using a dielectric having a relative dielectric constant of 2 or more, sufficient insulation between the electrodes can be ensured. Moreover, as an upper limit of a dielectric constant, it may be 50 or less, 20 or less, 15 or less, for example.

  Although it does not specifically limit as intensity | strength of a dielectric material, It is preferable that it is 200 Mpa or more by a three-point curvature test, and it is more preferable that it is 220 Mpa or more.

  Specific examples of the dielectric constituting the dielectric layer 12 include silicon nitride, aluminum nitride, and a composite nitride of silicon and aluminum.

The average thickness of the dielectric layer 12 is not particularly limited, but is preferably 0.1 mm or more, more preferably 0.2 mm or more, and further preferably 0.3 mm or more. By being 0.1 mm or more, the strength and insulation between the electrodes can be sufficiently ensured. On the other hand, the upper limit of the average thickness of the dielectric layer 12 is not particularly limited, but is preferably 0.9 mm or less, more preferably 0.8 mm or less, and 0.75 mm or less. Is more preferable. When the average thickness of the dielectric layer 12 is 0.9 mm or less, the efficiency of plasma generation is increased, and the substrate can be processed efficiently. In addition, even if an average thickness is made thin because the coefficient of thermal expansion in 40-400 degreeC of the dielectric material which comprises the dielectric material layer 12 is 6.5 * 10 < ^-6 > / K or less, atmospheric pressure plasma processing It is possible to form the dielectric layer 12 that is not easily damaged even if the above is repeated. The average thickness means a value obtained by arithmetically averaging the average values of the thicknesses of the respective cut surfaces and end portions when the plasma electrode is divided into four equal parts in the width direction.

  The atmospheric pressure plasma generating electrode 1 can be provided with other layers as long as the object of the present invention is not adversely affected. For example, another dielectric layer can be provided on the surface of the metal layer 11 that is not in contact with the dielectric layer 12.

<1-2. Electrode for atmospheric pressure plasma generation of second aspect>
The atmospheric pressure plasma generation electrode according to the present embodiment has a structure in which a first dielectric layer, a metal layer, and a second dielectric layer are stacked, and the metal layer includes a first surface and a second surface. The first dielectric layer covers the entire first surface of the metal layer, and the second dielectric layer extends outward from the end of the metal layer. FIG. 3 is a cross-sectional view for explaining the configuration of the atmospheric pressure plasma generation electrode. FIG. 4 is a perspective view for explaining the configuration of the atmospheric pressure plasma generating electrode.

  Although details will be described later, in the atmospheric pressure plasma generation apparatus, the atmospheric pressure plasma generation electrode 2 has, for example, the first dielectric layer 22 and the surface of the electrode paired with the atmospheric pressure plasma generation electrode 2 facing each other. Thus, it can be used as a set of electrodes for generating atmospheric pressure plasma. When the atmospheric pressure plasma is generated using the electrode by extending the second dielectric layer 23 of the electrode 2 for generating the atmospheric pressure plasma from the end of the metal layer 21 to the outside, the atmospheric pressure plasma is generated. An abnormal discharge (arcing) due to a high voltage from the surface (second surface) of the metal layer 21 of the generating electrode 2 not in contact with the first dielectric layer 22 to the paired electrode is suppressed, and the first dielectric layer The discharge efficiency from 22 can be increased.

  As the metal layer 21, the thing similar to the metal layer 11 in the electrode 1 for atmospheric pressure plasma generation of the 1st aspect can be used. The specific resistance value of the metal constituting the metal layer 21 is preferably as small as possible from the viewpoint of electrical efficiency. On the other hand, the arcing described above occurs between the atmospheric pressure plasma generating electrode 2 and the paired electrodes. It becomes easy. For example, arcing is likely to occur when the specific resistance of the metal constituting the metal layer 21 is 50 μΩcm or less, more likely to occur when it is 30 μΩcm or less, and more likely to occur when it is 20 μΩcm or less. However, even when a metal having such a specific resistance value is used, by providing the second dielectric layer 23, the occurrence of arcing can be suppressed, and as a result, the metal layer 21 having a low specific resistance value can be stably formed. Can be used.

Moreover, arcing is easily generated by increasing the area of the atmospheric pressure plasma generating electrode 2. When the electrode has a large area, it is necessary to increase the amount of power supplied to the high-frequency pulse power source. Along with this, the amount of electric power supplied to the atmospheric pressure plasma electrode increases, and at the same time, the calorific value of the electrode itself increases. Due to this increase in electric energy and heat generation, arcing occurs between the electrodes. However, by providing the second dielectric layer 23, the occurrence of arcing can be efficiently suppressed even when the area is increased. In such a case, the dielectric constant of the dielectric contained in the second dielectric layer 23 is preferably smaller than the dielectric constant of the dielectric contained in the first dielectric layer 22. If the relative dielectric constant of the dielectric contained in the second dielectric layer 23 is smaller than the relative dielectric constant of the dielectric contained in the first dielectric layer 22, it is preferentially over the second dielectric layer 23. Plasma can be generated from the first dielectric layer 22 and plasma corresponding to the amount of added electricity is generated, so that loss of electric energy due to arcing can be suppressed. In particular, arcing is more likely to occur when the area of the electrode in plan view is 300 cm ² or more, more likely to occur when it is 350 cm ² or more, and more likely to occur when it is 400 cm ² or more. By using the second dielectric layer 23 in which the relative dielectric constant of the dielectric contained in the second dielectric layer 23 is smaller than the relative dielectric constant of the dielectric contained in the first dielectric layer 22, the area is large. In addition, it is possible to manufacture the atmospheric pressure plasma generating electrode 2 that can suppress the occurrence of arcing.

  The minimum width of the second dielectric layer 23 is not particularly limited, but is preferably 0.5 cm or more, more preferably 0.8 cm or more, and further preferably 1.0 cm or more. If it is 0.5 cm or more, the above-mentioned arcing can be efficiently suppressed. On the other hand, the upper limit value of the minimum width of the second dielectric layer 23 can be set to 3.0 cm or less, for example. The “minimum width” refers to the atmospheric pressure plasma generation electrode from the end of the exposed surface of the metal layer 21 when the atmospheric pressure plasma generation electrode 2 is viewed from the side having the second dielectric layer 23 in plan view. This is the smallest distance to the end of 2.

  As the first dielectric layer 22 and the second dielectric layer 23, the same material as that of the dielectric layer in the atmospheric pressure plasma generating electrode 1 of the first aspect can be used. The first dielectric layer 22 and the second dielectric layer 23 do not necessarily need to be made of the same material.

  The atmospheric pressure plasma generating electrode 2 can be provided with other layers as long as the object of the present invention is not adversely affected.

  By the way, in the processing of a large-area substrate, in addition to the electrode having a large area, an electrode arranged so as to be continuous in the width direction of the electrode is used. When a plurality of atmospheric pressure plasma generation electrodes 2 are arranged and incorporated in an atmospheric pressure plasma generation apparatus, for example, as shown in FIGS. 5 and 6, the arrangement direction (perpendicular to the substrate transport direction X). The metal layers are preferably arranged so as to be continuous. Since plasma is generated only directly below the metal layer, for example, when the atmospheric pressure plasma generation electrodes 2 are arranged in a horizontal row, the metal layer 21 does not exist in the width direction, and the first dielectric layer 22 and the second dielectric layer A portion where only the body layer 23 exists is generated, and leakage of the atmospheric pressure plasma treatment due to a portion where only the second dielectric layer 23 exists can be prevented.

<1-3. Electrode for atmospheric pressure plasma generation according to third aspect>
The atmospheric pressure plasma generation electrode according to the present embodiment is an atmospheric pressure plasma generation electrode for processing a substrate, and is located on the surface of the electrode and has a cross-sectional shape that can accommodate at least a part of the substrate. Has a recess. Thus, by providing a recess in the atmospheric pressure plasma generating electrode and accommodating a part or all of the thick base material in the recess, the minimum distance between the electrode and the pair of electrodes (between the electrodes) The atmospheric pressure plasma treatment can be performed on the surface of the substantially thick substrate while keeping the distance) small.

  7 to 9 are perspective views for explaining the configuration of the atmospheric pressure plasma generating electrode. In FIG. 7, a groove-like semi-cylindrical recess 32a surrounded by a top 31a is provided at the center of one surface of the atmospheric pressure plasma generating electrode 3a. For example, a columnar or semi-columnar base material can be installed in the recess 32a. In FIG. 8, a rectangular parallelepiped groove-like recess 32b surrounded by a top 31b is provided at the center of one surface of the atmospheric pressure plasma generating electrode 3b. Further, in FIG. 9, a rectangular parallelepiped concave portion 32c surrounded by a top portion 31c is provided at the center of one surface of the atmospheric pressure plasma generating electrode 3c. In the recesses 32b and 32c, for example, a rectangular parallelepiped base material can be installed. Note that the shape of the concave portion and the base material are not necessarily the same or approximate, and is not limited as long as at least a part of the base material is accommodated in the concave portion, and thereby the distance between the electrodes can be kept small. For example, a cylindrical base material can be accommodated in the rectangular parallelepiped recess 32b. A plurality of recesses may be provided for one atmospheric pressure plasma generation electrode.

  The atmospheric pressure plasma generating electrodes 3a and 3b have a groove structure in which concave portions (32a and 32b) are continuous between two end portions of the electrode surface. By having such a structure, even if it is a base material larger than a recessed part, an atmospheric pressure plasma process can be continuously performed, conveying a base material to a groove direction.

  The position of the concave portion is not particularly limited. For example, by providing the concave portion at a position where the concentration of the reactive gas can be relatively high, such as the vicinity of the inlet of the reactive gas or the central portion, a large amount of radicals can be generated efficiently. Atmospheric pressure plasma treatment can be performed.

  The shape of the recess is not particularly limited as long as the shape can accommodate the substrate. In addition, it does not need to be substantially the same as the shape of the base material or a part thereof.

  The depth of the recess is not particularly limited as long as the depth can accommodate the base material. For example, a recess having a depth of 1 mm or more can be provided, and a recess having a depth of 2 mm or more can be provided. “Depth” refers to the distance from the deepest part of the recess to the height of the top. Thus, by increasing the depth of the concave portion of the atmospheric pressure plasma generating electrode in accordance with the thickness of the base material, a thick base material can be processed.

  The ratio of the recesses in the electrode surface is not particularly limited, but when the surface having the recesses is viewed in plan, the ratio of the area of the recesses to the total area of the electrode surface is preferably 1% or more, and preferably 2% or more. It is more preferable that it is 5% or more. When the ratio of the area of the recess to the total area of the electrode surface is 1% or more, it is possible to suppress an excessive increase in the area of the electrode. Moreover, as an upper limit of the ratio of the area of the recessed part with respect to the total area of an electrode surface, it is preferable that it is 80% or less, It is more preferable that it is 70% or less, It is further more preferable that it is 60%. When the ratio of the area of the recess to the total area of the electrode surface is 80% or less, atmospheric pressure plasma can be efficiently generated by maintaining the area of the top.

  The material for the electrode is not particularly limited, and various metals, alloys, and the like can be used. Specifically, for example, metal aluminum or stainless steel (SUS) can be used. The top can also be covered with a dielectric. The dielectric is not particularly limited, and examples thereof include ceramic materials such as alumina, minerals such as mullite and mica, and dielectrics used for the dielectric layer 12 of the atmospheric pressure plasma generating electrode 1 of the first aspect. It is done. In the atmospheric pressure plasma generator, for example, two electrodes are arranged to face each other, but a dielectric is provided on either of the two electrodes, and arcing can be suppressed.

  The atmospheric pressure plasma generating electrode 3 can include other layers as long as the object of the present invention is not adversely affected.

≪2. Atmospheric pressure plasma generator >>
The atmospheric pressure plasma generation electrode according to the present embodiment includes the above-described first aspect atmospheric pressure plasma generation electrode 1, the second aspect atmospheric pressure plasma generation electrode 2, and the third aspect atmospheric pressure plasma. One of the generating electrodes 3 is provided as at least one electrode. Of these, two types of electrodes for generating atmospheric pressure plasma can be used, and two types of electrodes for generating atmospheric pressure plasma can be used.

  In addition, when one of the atmospheric pressure plasmas described above is used as one of the atmospheric pressure plasma generation electrodes, a counter electrode is used. The counter electrode is not particularly limited as long as it includes a metal and has conductivity, and various metals, alloys, and the like can be used. Specifically, for example, metal aluminum or stainless steel (SUS) can be used. In addition, a dielectric can be provided on the surface facing the paired electrode (hereinafter referred to as “opposing surface”). The dielectric is not particularly limited, and examples thereof include ceramic materials such as alumina, minerals such as mullite and mica, and dielectrics used for the dielectric layer 12 of the atmospheric pressure plasma generating electrode 1 of the first aspect. It is done.

  The opposing surfaces are the dielectric layer 12 in the atmospheric pressure plasma generating electrode 1 of the first aspect, the first dielectric layer 22 in the atmospheric pressure plasma generating electrode 2 of the second aspect, and the atmospheric pressure plasma of the third aspect. It is a surface which has a recessed part in the electrode 3a-3c for generation | occurrence | production. In the atmospheric pressure plasma generator, the two electrodes are disposed facing each other with their facing surfaces facing each other.

  The minimum distance (distance between the electrodes) of the facing surfaces of the two electrodes is not particularly limited. For example, the minimum distance of the facing surfaces of the two electrodes is preferably 1.5 mm or more, and is 2.5 mm or more. More preferably, it is 3.5 mm or more. When the minimum distance between the facing surfaces of the two electrodes is 1.5 mm or more, a thick substrate can be subjected to atmospheric pressure plasma treatment. For example, when a pair of conventional electrodes in which two SUS flat plates are arranged to face each other and at least one SUS flat plate is covered with a dielectric material such as alumina or mica is used, the minimum of the facing surfaces of the two electrodes When the distance is 1.5 mm or more, the atmospheric pressure plasma treatment cannot be efficiently performed on the substrate.

  FIG. 10 is a schematic diagram of an example of an atmospheric pressure plasma generator. In FIG. 10, an atmospheric pressure plasma generating apparatus 100 includes an atmospheric pressure plasma generating electrode 1 and an atmospheric pressure plasma generating electrode 3a. In the atmospheric pressure plasma generating apparatus 100, the dielectric layer 12 of the atmospheric pressure plasma generating electrode 1 and the surface having the concave portion 32a of the atmospheric pressure plasma generating electrode 3a are disposed to face each other. The metal layer 11 of the atmospheric pressure plasma generating electrode 1 and the atmospheric pressure plasma generating electrode 3 a are connected to the high frequency pulse power supply device 4.

≪3. Method for producing modified base material >>
The method for producing a modified base material according to the present embodiment performs atmospheric pressure plasma treatment on the base material using any one of the above-described atmospheric pressure plasma generators. The obtained modified base material has different surface characteristics as compared with the base material before the atmospheric pressure plasma treatment, and has high wettability with water, for example.

  Examples of the reaction gas include dry air, nitrogen, argon, helium and the like. From the viewpoint of cost and the like, it is preferable to use dry air.

  FIGS. 11A to 11D are schematic views for explaining a method for producing a modified base material. For example, the atmospheric pressure plasma generator 100 is used in the method of manufacturing the modified base material. In FIG. 11, only the atmospheric pressure plasma generating electrode 1 and the atmospheric pressure plasma generating electrode 3a are shown in the configuration of the atmospheric pressure plasma generating apparatus 100 for convenience. Hereinafter, the manufacturing method of the modified substrate will be described in order.

  As an example of the base material 5 to be processed, the base material 5 has a cylindrical shape, and approximately half of the base material 5 is accommodated in the semi-cylindrical concave portion 32a of the atmospheric pressure plasma generating electrode 3a (FIG. 11A). . First, when atmospheric pressure plasma treatment is performed on the base material 5, the surface of substantially half of the base material 5 is modified (FIG. 11 (b)). In FIGS. 11A to 11D, the shaded portion of the base material 5 is a modified portion.

  For example, when the base material 5 has a shape that is long in the height direction of the cylinder, the base material is transported along the transport direction Y, and subsequently, an unprocessed portion is similarly subjected to atmospheric pressure plasma treatment. (FIG. 11 (c)). By such a method, the atmospheric pressure plasma treatment can be continuously performed on a base material having a length in the same direction as the transport direction Y.

  In addition, when the atmospheric pressure plasma treatment is performed on both surfaces (the entire circumferential direction) of the substrate 5, the substrate 5 is treated on the entire surface in the transport direction (the length direction of the substrate) after the treatment. The base material 5 is rotated with an axis parallel to the conveying direction of the material 5 as a rotation axis, an untreated portion is exposed, and an atmospheric pressure plasma treatment is performed on the portion. Furthermore, the substrate can be transported along the transport direction Z while performing atmospheric pressure plasma treatment. By performing the atmospheric pressure plasma treatment in this way, it is possible to obtain a modified base material that is surface-treated over the entire circumferential direction and length direction of the base material 5.

  In addition, for example, when a base material is flat form, after performing atmospheric pressure plasma processing to a base material, the base material can be turned over and atmospheric pressure plasma processing can be performed again. As described above, in a state where at least a part of the base material is accommodated in the concave portion, after the atmospheric pressure plasma treatment is once performed on the base material, the portion accommodated in the concave portion of the base material is exposed to the base material. By performing the atmospheric pressure plasma treatment, a base material in which the whole base material is modified can be obtained.

<< 4. Manufacturing method of reusable electrode >>
The method of manufacturing a reuse electrode according to the present embodiment includes a method for forming an acid on the surface of a dielectric provided in an atmospheric pressure plasma generation electrode and having a thermal expansion coefficient at 40 to 400 ° C. of 6.5 × 10 ⁻⁶ / K or less. This is a method for producing a reusable electrode by performing treatment or alkali treatment. By subjecting the base material to atmospheric pressure plasma treatment, dirt is attached to the surface of the dielectric of the electrode for generating atmospheric pressure plasma due to organic substances attached to the base material, and accumulates over a long period of use. Thus, if dirt accumulates on the surface of the atmospheric pressure plasma generating electrode, it may cause a decrease in plasma generation efficiency. In particular, the use of a dielectric whose thermal expansion coefficient at 40 to 400 ° C. is 6.5 × 10 ⁻⁶ / K or less is greatly reduced in the dielectric layer of the atmospheric pressure plasma generating electrode, thereby greatly reducing damage caused by repeated use. Can be used for a longer period of time, but on the other hand, dirt accumulates due to a longer period of use.

  Although it does not specifically limit as a method of a process, Specifically, the method of immersing an electrode in a solution and the method of exposing an electrode to vapor | steam are mentioned.

  Although it does not specifically limit as an acid, Hydrochloric acid, a sulfuric acid, nitric acid, an acetic acid etc. can be used. Moreover, when using an acid solution, what is 1 or more and 4 or less can be used as pH of the solution.

  Although it does not specifically limit as an alkali, Sodium hydroxide, potassium hydroxide, sodium hydrogencarbonate, ammonia water, etc. can be used. Moreover, when using an alkaline solution, it is although it does not specifically limit as pH of the solution, What is 9 or more and 14 or less can be used.

[Example 1]

(Preparation of electrode A)
An aluminum nitride plate (made by MARUWA) having a thickness of 0.64 mm is cut into 45 mm × 120 mm, and a silver paste (made by Daiken Chemical Co., Ltd.) is 25 mm × 100 mm on one side and located at the center of the aluminum nitride plate surface. After the coating, an alumina plate having a thickness of 1 mm is applied to the silver coating for the purpose of protecting the silver coating, and the temperature is increased to 850 ° C. at a temperature increase rate of 10 ° C./min in the air atmosphere. After firing for 5 minutes, the mixture was naturally cooled to room temperature to obtain a member having a silver coating between an aluminum nitride plate and an alumina plate. In the alumina plate used for silver coating protection, a hole for attaching an electrode for supplying electricity to the silver coating is provided in advance, and by adhering to the silver coating through a brass rod for energization, Electrode A was produced.

(Preparation of electrode B)
An electrode B was prepared in the same manner as the electrode A, except that a 0.3 mm thick silicon nitride plate (made by MARUWA) was used instead of the 0.64 mm thick aluminum nitride plate.

(Preparation of electrode C)
An electrode C was obtained in the same manner as the electrode A except that a copper paste (Daiken Chemical Co., Ltd.) was used instead of the silver paste.

(Preparation of electrode D)
An electrode D was obtained in the same manner as the electrode B except that a copper paste (manufactured by Daiken Chemical) was used instead of the silver paste.

(Preparation of electrode E)
An electrode E was obtained in the same manner as the electrode A, except that an alumina plate (manufactured by Nikkato) having a thickness of 1.0 mm was used instead of the aluminum nitride plate having a thickness of 0.64 mm.

(Preparation of electrode F)
An electrode F was obtained in the same manner as the electrode C, except that an alumina plate (manufactured by Nikkato) having a thickness of 1.0 mm was used instead of the aluminum nitride plate having a thickness of 0.64 mm.

(Preparation of electrode G)
A 3.0 mm thick SUS plate (manufactured by Nisshin Kikai Co., Ltd.) was cut into 45 mm × 120 mm, and a brass rod for supplying electricity to supply electricity to this SUS plate was bonded to obtain an electrode G.

[Example 1-1]
The surface of the electrode A having aluminum nitride and one surface of the SUS plate were arranged to face each other, and the electrode A and the SUS plate were connected to a high-frequency pulse power source (manufactured by Nisshin Kikai, output current 120 mA, output voltage 10 kV). Each of the electrodes A to F was fixed inside a casing surrounded by an insulator. A nozzle for blowing dry air from the vicinity of the housing was installed, and a constant flow of dry air was supplied between the electrode A and the SUS plate in a fixed direction while the substrate was subjected to atmospheric pressure plasma treatment. Further, a household 100V power source was connected between the electrode A and the SUS plate, and an atmospheric pressure plasma was generated by supplying an input voltage of 100V by a slidac.

  The distance between the electrodes A and the SUS plate facing each other (hereinafter also referred to as “distance between electrodes”) was set to 1 mm, 2 mm, 3 mm, and 4 mm, and the generation state of atmospheric pressure plasma was visually evaluated. . In addition, a glass substrate having a thickness of 0.1 mm was passed between the electrode A and the SUS plate at a feeding speed of 5 m / min, and an atmospheric pressure plasma treatment was performed. Thereafter, the contact angle of the surface of the glass substrate after the atmospheric pressure plasma treatment is measured by using DM-500 (evaluated by θ / 2 method, water droplet 1.5 μL) manufactured by Kyowa Interface Science Co., Ltd. The wettability evaluation of the subsequent glass substrate was performed.

[Example 1-2]
Evaluation was performed in the same manner as in Example 1-1 except that the electrode B was used instead of the electrode A.

[Example 1-3]
Evaluation was performed in the same manner as in Example 1-1 except that the electrode C was used instead of the electrode A.

[Example 1-4]
Evaluation was performed in the same manner as in Example 1-1 except that the electrode D was used instead of the electrode A.

[Comparative Example 1-1]
Evaluation was performed in the same manner as in Example 1-1 except that the electrode E was used instead of the electrode A.

[Comparative Example 1-2]
Evaluation was performed in the same manner as in Example 1-1 except that the electrode F was used instead of the electrode A.

[Comparative Example 1-3]
One surface of the electrode G and a 3.0 mm thick SUS plate (manufactured by Nisshin Kikai Co., Ltd.) were cut out to 200 mm × 200 mm, and a mica plate having a thickness of 0.5 mm was placed on one surface as an insulator. Evaluation was carried out in the same manner as in Example 1-1 except that the electrodes were arranged opposite to each other and used as a pair of electrodes. The reason why the area of the electrode on which the mica plate is placed is larger than the area of the surface of the electrode G is to suppress the occurrence of arcing between the electrodes.

Table 1 shows the results of evaluation of the light emission state of atmospheric pressure plasma in Examples 1-1 to 1-4 and Comparative Examples 1-1 to 1-3. In Table 1, the light emission state of atmospheric pressure plasma was evaluated based on the following criteria.
A: Atmospheric pressure plasma emission was uniform and emitted over the entire surface of the electrode.
○: Atmospheric pressure plasma light emission was uniform and light was emitted almost entirely on the electrode.
(Triangle | delta): Atmospheric pressure plasma light emission is non-uniform | heterogenous and has not light-emitted on the electrode whole surface.
X: Atmospheric pressure plasma light emission is sparse and almost no light emission.
−: No atmospheric pressure plasma emission occurs.

Table 2 shows the results of wettability evaluation in Examples 1-1 to 1-4 and Comparative Examples 1-1 to 1-3. In Table 1, the wettability was evaluated based on the following criteria.
◎: Contact angle after atmospheric pressure plasma treatment is 15 ° or less ○: Contact angle after atmospheric pressure plasma treatment is 30 ° or less △: Contact angle after atmospheric pressure plasma treatment is 40 ° or less ×: Atmospheric pressure plasma The contact angle after the treatment is 60 ° or less −: The contact angle after the atmospheric pressure plasma treatment is the same as that of the untreated glass substrate (75.3 °).

From the above results, the distance between the electrodes can be reduced by using an atmospheric pressure plasma electrode having a metal layer and a dielectric layer having a coefficient of thermal expansion at 40 to 400 ° C. of 6.5 × 10 ⁻⁶ / K or less. It was found that the atmospheric pressure plasma treatment can be efficiently performed even when the thickness exceeds 1 mm.

[Example 2]
(Preparation of electrode H)
A groove-shaped recess capable of accommodating a glass substrate as an object of atmospheric pressure plasma treatment is provided on one surface of a SUS plate having a thickness of 10.5 mm (see FIG. 8), and only on the top of the surface on the side having the recess. An electrode H having a total thickness of 11 mm was prepared by placing a mica plate having a thickness of 0.5 mm (that is, the mica plate was not placed in the recess). In addition, although details will be described later, in Example 2, in order to confirm the influence on the atmospheric pressure plasma processing by changing the thickness of the glass substrate, in accordance with the thickness of the glass substrate to be processed, The depth (groove height) was adjusted.

[Example 2-1]
The surface of the electrode A having aluminum nitride and the surface of the electrode H on the side having the recesses are arranged to face each other to form a pair of electrodes. Glass plates with thicknesses of 1 mm, 3 mm, 6 mm, and 10 mm, respectively, are accommodated in the recesses, and arranged so that the height of the mica plate at the top of the electrode H is the same (level) with the glass substrate. did. The distance between the surface of the aluminum nitride of the electrode A and the surface of the glass substrate accommodated in the recess of the electrode H (and the surface of the mica plate disposed on the top so as to be flush with the surface) was set to 1 mm. . Then, the wettability evaluation of the glass substrate after atmospheric pressure plasma processing was performed like Example 1-1.

[Example 2-2]
The wettability evaluation of the glass substrate after the atmospheric pressure plasma treatment was performed in the same manner as in Example 2-1, except that the electrode B was used instead of the electrode A.

[Example 2-3]
The wettability evaluation of the glass substrate after the atmospheric pressure plasma treatment was performed in the same manner as in Example 2-1, except that the electrode E was used instead of the electrode A.

[Example 2-4]
The wettability evaluation of the glass substrate after the atmospheric pressure plasma treatment was performed in the same manner as in Example 2-1, except that the electrode G was used instead of the electrode A.

[Example 2-5]
The surface of the electrode A having aluminum nitride and the surface of the electrode H on the side having the recesses are arranged to face each other to form a pair of electrodes. Glass plates having thicknesses of 1 mm, 3 mm, 6 mm, and 10 mm, respectively, were accommodated in the recesses, and the glass substrate was arranged so that the height of the glass substrate was 1 mm higher than the height of the mica plate at the top of the electrode H and The distance between the surface of the aluminum nitride of the electrode A and the surface of the glass substrate accommodated in the recess of the electrode H was set to 1 mm. Then, the wettability evaluation of the glass substrate after atmospheric pressure plasma processing was performed like Example 1-1. When the thickness of the glass substrate is 1 mm, the glass substrate is placed on the mica plate so that the height of the glass substrate is 1 mm higher than the height of the mica plate at the top of the electrode H. That's fine. Therefore, since the recessed part is not provided in the electrode H, when the thickness of a glass substrate is 1 mm, it is set as the reference example of this application.

[Example 2-6]
Except for using the electrode B instead of the electrode A, the wettability evaluation of the glass substrate after the atmospheric pressure plasma treatment was performed in the same manner as in Example 2-5.

[Example 2-7]
The wettability evaluation of the glass substrate after the atmospheric pressure plasma treatment was performed in the same manner as in Example 2-5 except that the electrode E was used instead of the electrode A.

[Example 2-8]
Except that the electrode G was used instead of the electrode A, the wettability evaluation of the glass substrate after the atmospheric pressure plasma treatment was performed in the same manner as in Example 2-5.

[Comparative Example 2-1]
The surface of the electrode E having alumina and the one surface of the flat SUS plate are arranged to face each other to form a pair of electrodes. Glass plates having thicknesses of 1 mm, 3 mm, 6 mm, and 10 mm, respectively, were placed on the surface of the SUS plate. And the distance between the surface of the alumina of the electrode E and the surface of the glass substrate installed in the surface of the electrode H was set to 1 mm. Then, the wettability evaluation of the glass substrate after atmospheric pressure plasma processing was performed like Example 1-1.

[Comparative Example 2-2]
One surface of the electrode G and a surface of the mica plate side of a 0.5-mm thick mica plate mounted as an insulator on a flat SUS plate were arranged to face each other to form a pair of electrodes. Glass plates having thicknesses of 1 mm, 3 mm, 6 mm, and 10 mm, respectively, were placed on the surface of the mica plate. And the distance between the surface of the electrode G and the surface of the glass substrate installed in the surface of the electrode H was set to 1 mm. Then, the wettability evaluation of the glass substrate after atmospheric pressure plasma processing was performed like Example 1-1.

  From the above results, the atmospheric pressure plasma treatment is performed on the surface of the base material having a thickness larger than the distance between the electrodes by providing a recess in the electrode and accommodating a part of the base material therein. It was found that it can be applied.

1, 2, 3a, 3b, 3c Atmospheric pressure plasma generating electrode 11, 21 Metal layer 12 Dielectric layer 100 Atmospheric pressure plasma generator 22 First dielectric layer 23 Second dielectric layer 31a, 31b, 31c Top 32a, 32b, 32c Concavity 4 High-voltage pulse power supply 5 Base material

Claims (14)

Having a structure in which a first dielectric layer, a metal layer, and a second dielectric layer are laminated;
The first dielectric layer and the second dielectric layer include a dielectric whose thermal expansion coefficient at 40 to 400 ° C. is 6.5 × 10 ⁻⁶ / K or less,
The dielectric constant of the dielectric contained in the second dielectric layer is smaller than the dielectric constant of the dielectric contained in the first dielectric layer,
The metal layer has a first surface and a second surface;
The first dielectric layer covers all of the first surface;
The second dielectric layer extends outward from an end of the metal layer;
An electrode for atmospheric pressure plasma generation. An atmospheric pressure plasma generating electrode having a structure in which a first dielectric layer, a metal layer, and a second dielectric layer are laminated,
The metal layer has a first surface and a second surface;
The first dielectric layer covers all of the first surface;
The second dielectric layer extends outward from an end of the metal layer;
The atmospheric pressure plasma generating electrode, wherein a minimum distance from an end portion of the metal layer to an end portion of the atmospheric pressure plasma generating electrode in a plan view of the atmospheric pressure plasma generating electrode is 0.5 cm or more. An atmospheric pressure plasma generating electrode for processing a substrate,
Located on a surface of said atmospheric plasma generating electrode, at least a part can accommodate, concave cross-sectional shape you continuously along the conveying direction of the substrate between the ends of the two portions of the surface of the substrate Have
An electrode for generating atmospheric pressure plasma, wherein a ratio of the area of the recess to the area of the electrode for generating atmospheric pressure plasma is 5% or more and 80% or less in a plan view of the electrode for generating atmospheric pressure plasma.   An electrode for generating atmospheric pressure plasma for modifying the surface properties of the base material by modifying the surface of the base material without moving it,
  Located on the surface of the atmospheric pressure plasma generating electrode, and having a recess having a cross-sectional shape capable of accommodating at least a part of the base material,
  When the atmospheric pressure plasma generation electrode is viewed in plan, the ratio of the area of the recess to the area of the atmospheric pressure plasma generation electrode is 5% or more and 80% or less.
  An electrode for atmospheric pressure plasma generation.   An atmospheric pressure plasma generating electrode for modifying the surface of the substrate to change the surface properties of the substrate,
  A metal layer and a dielectric layer, wherein the dielectric layer includes aluminum nitride;
  Used with a minimum distance of 2.5 mm or more between the dielectric layer and the counter electrode arranged to face the dielectric layer.
  An electrode for atmospheric pressure plasma generation. An atmospheric pressure plasma generator comprising the atmospheric pressure plasma generation electrode according to any one of claims 1 to 5 . Used to modify the surface properties of the base material by modifying the surface of the base material, and has a structure in which a metal layer and a dielectric layer are laminated, and the dielectric layer contains atmospheric pressure including aluminum nitride. Comprising a plasma generating electrode and a counter electrode containing a metal;
The dielectric layer of the atmospheric pressure plasma generating electrode;
A surface of the counter electrode,
Arranged to face each other,
An atmospheric pressure plasma generator, wherein a minimum distance between the dielectric layer and the counter electrode surface is 2.5 mm or more. The atmospheric pressure plasma generating electrode according to claim 1 or 2, and a counter electrode containing a metal,
The first dielectric layer of the atmospheric pressure plasma generating electrode;
A surface of the counter electrode,
Arranged to face each other,
An atmospheric pressure plasma generator, wherein a minimum distance between the first dielectric layer and the counter electrode surface is 1.5 mm or more. An atmospheric pressure plasma generating electrode for processing a substrate,
Located on a surface of said atmospheric plasma generating electrode, at least a part can accommodate, concave cross-sectional shape you continuously along the conveying direction of the substrate between the ends of the two portions of the surface of the substrate An atmospheric pressure plasma generating electrode having a counter electrode containing a metal,
A surface having the concave portion of the electrode for generating atmospheric pressure plasma;
A surface of the counter electrode,
Arranged to face each other,
An atmospheric pressure plasma generator, wherein a minimum distance between the surface having the recess and the counter electrode surface is 2.5 mm or more.   An atmospheric pressure plasma generating electrode for modifying the surface of the substrate to change the surface properties of the substrate,
  An atmospheric pressure plasma generation electrode located on the surface of the atmospheric pressure plasma generation electrode and having a recess having a cross-sectional shape capable of accommodating at least a part of the substrate; and a counter electrode containing a metal;
  A surface having the concave portion of the electrode for generating atmospheric pressure plasma;
  A surface of the counter electrode,
  Arranged to face each other,
  The minimum distance between the surface having the recess and the counter electrode surface is 2.5 mm or more,
  The atmospheric pressure plasma generation electrode and the counter electrode are not moved.
  Atmospheric pressure plasma generator. An atmospheric pressure plasma generator for processing a substrate,
An atmospheric pressure plasma generating apparatus in which a plurality of electrodes for generating atmospheric pressure plasma according to claim 1 or 2 are arranged and the metal layers are arranged continuously in the arrangement direction. Method for producing a surface modified substrate by using the atmospheric pressure plasma generating apparatus performing atmospheric pressure plasma treatment to a substrate according to any one of claims 6-11. Comprises atmospheric plasma generating electrode according to claim 3 or 4, using the atmospheric pressure plasma generating apparatus, a method for performing atmospheric pressure plasma treatment to the substrate,
In a state where at least a part of the base material is accommodated in the recess, the base material is subjected to atmospheric pressure plasma treatment,
A method for producing a surface-modified base material, wherein the base material is subjected to an atmospheric pressure plasma treatment in a state where a portion accommodated in the concave portion of the base material is exposed. Generation of atmospheric pressure plasma having a structure in which a metal layer and a dielectric layer are laminated, and the dielectric layer includes a dielectric whose coefficient of thermal expansion at 40 to 400 ° C. is 6.5 × 10 ⁻⁶ / K or less. Using an atmospheric pressure plasma generator having an electrode distance between the electrode for generating atmospheric pressure plasma and the counter electrode of 2.5 mm or more. provide Reinforced pressure plasma treatment method for producing a surface modified substrate which modify the surface of the substrate repeatedly altering the surface properties of the substrate.

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