JP5503904B2 - Discharge electrode and method of manufacturing the discharge electrode - Google Patents
Discharge electrode and method of manufacturing the discharge electrode Download PDFInfo
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Description
本発明は、放電用電極、及び該放電用電極の製造方法に関するものである。 The present invention relates to a discharge electrode and a method for producing the discharge electrode.
プラズマ放電処理は、医療機器の滅菌処理、シート材（フィルムを含む、以下同じ）の表面処理（例えば、濡れ性向上）、あるいはシート材表面の有機物除去等に広く用いられている。ところで、プラズマ放電処理を大気圧下で行なうと、電子温度、イオン温度、ガス分子温度がほぼ等しい熱平衡プラズマとなるため、シート材等の被処理物の温度が高くなりすぎて、被処理物を損傷してしまう場合がある。そこで、大気圧下でのプラズマ放電処理は、一般的に、一方の電極表面を誘電体で被覆した放電用電極を用いて行なわれている。 Plasma discharge treatment is widely used for sterilization of medical equipment, surface treatment of a sheet material (including a film, the same applies hereinafter) (for example, improvement of wettability), or removal of organic substances on the surface of the sheet material. By the way, if the plasma discharge treatment is performed under atmospheric pressure, it becomes a thermal equilibrium plasma in which the electron temperature, the ion temperature, and the gas molecule temperature are almost equal. It may be damaged. Therefore, plasma discharge treatment under atmospheric pressure is generally performed using a discharge electrode in which one electrode surface is covered with a dielectric.
例えば、特許文献１や特許文献２には、低温プラズマの一種であるコロナ放電に関し、コロナ放電処理ロールのロール基材表面に、アルミナもしくはアルミナとチタニアの混合物の粉末を溶射して、絶縁性皮膜を形成させる方法が開示されている。 For example, Patent Document 1 and Patent Document 2 relate to corona discharge, which is a kind of low-temperature plasma, and spray a powder of alumina or a mixture of alumina and titania on the surface of a roll base of a corona discharge treatment roll to form an insulating film. A method is disclosed for forming.
しかしながら、これまで用いられてきた放電用電極のように、一方の電極（ロール基材）にのみ誘電体層（絶縁性皮膜）を設けた場合には、他方の電極からの電子放出量が多くなり、ストリーマと呼ばれる電子なだれが多く発生する場合がある。そして、このストリーマの位置が固定すると、ストリーマ付近の電界が局所的に強いことから、誘電体層が劣化するという問題がある。また、放電によってオゾンが発生するため、誘電体層で被覆されていない方の電極の表面が部分的に酸化されて、放電が不均一になるという問題もある。さらに、この電極表面の酸化に伴い、被処理物への金属コンタミが生じるという問題もある。なお、従来技術としては一方の電極がロールである場合を述べたが、処理目的や処理対象に対応した電極形状が採用されていることは言うまでもない。 However, when a dielectric layer (insulating film) is provided only on one electrode (roll substrate) as in the case of the discharge electrode that has been used so far, the amount of electron emission from the other electrode is large. In many cases, avalanche called streamer is often generated. When the position of the streamer is fixed, the electric field in the vicinity of the streamer is locally strong, which causes a problem that the dielectric layer is deteriorated. Further, since ozone is generated by the discharge, there is a problem that the surface of the electrode not covered with the dielectric layer is partially oxidized and the discharge becomes non-uniform. Furthermore, there is a problem that metal contamination to the object to be processed occurs with the oxidation of the electrode surface. In addition, although the case where one electrode was a roll was described as a prior art, it cannot be overemphasized that the electrode shape corresponding to the process objective and the process target is employ | adopted.
上記の様な状況の下で、本発明者らは、他方の電極にも誘電体層を設ければ、上記問題を解決できるのではないかと考えた。 Under the circumstances as described above, the present inventors thought that the above problem could be solved by providing a dielectric layer on the other electrode.
しかしながら、双方の電極に誘電体層を設けただけでは、回路全体のインピーダンスが高くなるという新たな問題が生じた。 However, a new problem arises that the impedance of the entire circuit is increased only by providing dielectric layers on both electrodes.
本発明は上記の様な状況の下でなされたものであり、大気圧プラズマ放電処理の際の、電極表面の誘電体層の劣化や不均一放電、及び被処理物への金属コンタミなどを防ぐことのできるのみならず、回路全体のインピーダンスを下げることのできる放電用電極を提供することを課題として掲げた。 The present invention has been made under the circumstances as described above, and prevents deterioration of the dielectric layer on the electrode surface, non-uniform discharge, and metal contamination on the object to be processed during the atmospheric pressure plasma discharge treatment. An object of the present invention is to provide a discharge electrode that can reduce the impedance of the entire circuit.
上記課題を解決することのできた本発明の放電用電極は、対向する二つの電極を備え、これら電極には、対向側表面に誘電体層が形成され、前記各誘電体層の一方が体積抵抗率１０11Ωｃｍ以下であることを特徴とする。 The discharge electrode of the present invention that has solved the above problems includes two opposing electrodes, each of which has a dielectric layer formed on the surface on the opposite side, and one of the dielectric layers has a volume resistance. The rate is 10 11 Ωcm or less.
本発明では、いずれの電極にも誘電体層を設けることにより、電極の一方にのみ誘電体層が形成された放電用電極に比べて、放電の際のストリーマの発生を抑えたり、たとえ発生しても個々のストリーマを細くできる。また、ストリーマを放電空間内で分散させやすい。また、電極表面がオゾンと接触し難くなる。 In the present invention, by providing a dielectric layer on any of the electrodes, it is possible to suppress the occurrence of a streamer during the discharge, even if it occurs compared to a discharge electrode having a dielectric layer formed on only one of the electrodes. Even individual streamers can be made thinner. In addition, the streamer can be easily dispersed in the discharge space. Moreover, it becomes difficult for the electrode surface to come into contact with ozone.
さらに、一方の誘電体層の体積抵抗率を１０11Ωｃｍ以下にすることにより、体積抵抗率の高い誘電体層を双方の電極に設けた場合に比べて、回路全体のインピーダンスを小さくできる。 Furthermore, by setting the volume resistivity of one dielectric layer to 10 11 Ωcm or less, the impedance of the entire circuit can be reduced as compared with the case where a dielectric layer having a high volume resistivity is provided on both electrodes.
本発明では、前記各誘電体層の他方は体積抵抗率１０11Ωｃｍ以上であることが好ましい実施態様である。これにより、アーキングの発生を抑制しやすくなる。 In the present invention, the other dielectric layer preferably has a volume resistivity of 10 11 Ωcm or more. Thereby, it becomes easy to suppress the occurrence of arcing.
また、本発明では、体積抵抗率１０11Ωｃｍ以下の誘電体層の膜厚が０．１〜５．０ｍｍであり、また、体積抵抗率１０11Ωｃｍ以上の誘電体層の膜厚が０．２〜５．０ｍｍであり、さらに、放電ギャップが０．０２〜５．０ｍｍであることも好ましい実施態様である。また、電極間電圧３〜３０ｋＶで使用されるのが好ましい実施態様である。 In the present invention, the thickness of the dielectric layer having a volume resistivity of 10 11 Ωcm or less is 0.1 to 5.0 mm, and the thickness of the dielectric layer having a volume resistivity of 10 11 Ωcm or more is 0.1 mm. The preferred embodiment is 2 to 5.0 mm, and the discharge gap is 0.02 to 5.0 mm. Moreover, it is a preferable embodiment to be used at an interelectrode voltage of 3 to 30 kV.
さらに、本発明には、電極基板に誘電体形成材料を溶射するか、または誘電体に導電金属を蒸着して、上記の放電用電極を製造することを特徴とする放電用電極の製造方法も包含される。 Furthermore, the present invention also provides a method for manufacturing a discharge electrode, characterized in that the discharge electrode is manufactured by spraying a dielectric forming material on an electrode substrate or depositing a conductive metal on the dielectric. Is included.
本発明によれば、いずれの電極にも誘電体層を設けることにより、電極の一方にのみ誘電体層が形成された放電用電極に比べて、放電の際のストリーマの発生が抑えられ、たとえ発生しても個々のストリーマが細くなるため、誘電体層の劣化を防ぐことができた。また、電極表面がオゾンと接触し難いため、電極表面の酸化を抑えることができた。このため、不均一放電を防ぐことが期待できる。さらに、回路全体のインピーダンスが小さくなるため、放電電力を高くすることができた。 According to the present invention, by providing a dielectric layer on any electrode, the generation of streamers during discharge can be suppressed as compared to a discharge electrode in which a dielectric layer is formed only on one of the electrodes. Even if it occurs, the individual streamers become thinner, so that the deterioration of the dielectric layer can be prevented. Moreover, since the electrode surface was difficult to contact with ozone, the oxidation of the electrode surface could be suppressed. For this reason, it can be expected to prevent non-uniform discharge. Furthermore, since the impedance of the entire circuit is reduced, the discharge power can be increased.
本発明の放電用電極は、対向する二つの電極を備え、これら電極には、対向側表面に誘電体層が形成され、前記各誘電体層の一方が体積抵抗率１０11Ωｃｍ以下であることを特徴とする。 The discharge electrode of the present invention includes two electrodes facing each other, each of which has a dielectric layer formed on the surface on the opposite side, and one of the dielectric layers has a volume resistivity of 10 11 Ωcm or less. It is characterized by.
本発明では、いずれの電極表面にも誘電体層を設けることにより、電極からの電子放出量を抑えることができるため、ストリーマの発生を抑えたり、ストリーマを細くできる。また、ストリーマが放電空間内で分散しやすく、電界集中が生じにくい。その結果、電極表面の誘電体層の劣化を防ぐことができる。 In the present invention, by providing a dielectric layer on any electrode surface, the amount of electron emission from the electrode can be suppressed, so that the generation of the streamer can be suppressed or the streamer can be made thin. In addition, the streamer is easily dispersed in the discharge space, and electric field concentration hardly occurs. As a result, deterioration of the dielectric layer on the electrode surface can be prevented.
また、電極表面が誘電体層で被覆されて、オゾンとの接触が抑制されているため、電極表面が酸化されにくい。その結果、放電が不均一になったり、電極由来の金属が被処理物に混入するのを防ぐことができる。 In addition, since the electrode surface is covered with a dielectric layer and contact with ozone is suppressed, the electrode surface is hardly oxidized. As a result, it is possible to prevent the discharge from becoming uneven and preventing the electrode-derived metal from being mixed into the workpiece.
さらに、本発明では、一方の誘電体層の体積抵抗率を１０11Ωｃｍ以下としているため、回路全体のインピーダンスを小さくすることができる。その結果、双方の電極に誘電体層を設けたことによる放電電力低下の問題を解消することができ、被処理物への処理効率を高めることができる。 Furthermore, in the present invention, since the volume resistivity of one dielectric layer is 10 11 Ωcm or less, the impedance of the entire circuit can be reduced. As a result, the problem of reduced discharge power due to the provision of the dielectric layers on both electrodes can be solved, and the processing efficiency of the object to be processed can be increased.
以下、本発明の放電用電極について詳述する。 Hereinafter, the discharge electrode of the present invention will be described in detail.
（電極）
本発明の電極の全体形状は、特に限定されるものではなく、例えば、図１に示すように、放電用電極１の双方の電極５が平板状（図１（ａ））や円筒状（図１（ｃ））であっても、また、一方の電極（例えば電極５）が円筒状で、他方の電極（例えば電極５’）が平板状であってもよい。なお、電極を棒状とすると、電極の対向側面にも誘電体層を設ける必要が生じ手間がかかりやすく、また角部に形成された誘電体層の絶縁破壊電圧は平坦部と比較して低くなりやすく、さらに角部に電界が集中して絶縁破壊を起こしやすい。
(electrode)
The overall shape of the electrode of the present invention is not particularly limited. For example, as shown in FIG. 1, both electrodes 5 of the discharge electrode 1 are flat (FIG. 1A) or cylindrical (FIG. 1 (c)), one electrode (for example, electrode 5) may be cylindrical and the other electrode (for example, electrode 5 ') may be flat. If the electrode is a rod, it is necessary to provide a dielectric layer on the opposite side of the electrode, which is troublesome, and the dielectric breakdown voltage of the dielectric layer formed at the corner is lower than that of the flat part. In addition, the electric field concentrates on the corners, and dielectric breakdown is likely to occur.
電極材料としては、従来から電極として用いられている電導材料が使用可能であり、例えば、鉄、銀、白金、銅、真鍮、アルミニウム等の金属（合金を含む）やカーボン等が挙げられる。 As the electrode material, a conductive material conventionally used as an electrode can be used, and examples thereof include metals (including alloys) such as iron, silver, platinum, copper, brass, and aluminum, and carbon.
（誘電体層）
図２に示すように、本発明の電極５は、互いに対向する対向側表面に、それぞれ誘電体層１５を有しており、いずれか一方の誘電体層は、体積抵抗率を１０11Ωｃｍ以下としている。
(Dielectric layer)
As shown in FIG. 2, the electrode 5 of the present invention has dielectric layers 15 on opposing surfaces facing each other, and either one of the dielectric layers has a volume resistivity of 10 11 Ωcm or less. It is said.
＜体積抵抗率＞
本発明では、二つの電極のそれぞれに誘電体層を形成することにより、一方の電極にのみ誘電体層が形成される放電用電極に比べて、誘電体層の劣化や不均一放電を防ぎやすいが、一方で、回路全体のインピーダンスは大きくなるという問題がある。そこで、本発明では、いずれか一方の誘電体層の体積抵抗率を、１０11Ωｃｍ以下としている。これにより、回路全体のインピーダンスが大きくなって放電電力が低下する問題を解消することができる。
<Volume resistivity>
In the present invention, by forming a dielectric layer on each of the two electrodes, it is easier to prevent deterioration of the dielectric layer and non-uniform discharge compared to a discharge electrode in which the dielectric layer is formed only on one electrode. However, there is a problem that the impedance of the entire circuit becomes large. Therefore, in the present invention, the volume resistivity of one of the dielectric layers is set to 10 11 Ωcm or less. Thereby, the problem that the impedance of the whole circuit becomes large and the discharge power decreases can be solved.
また、本発明では、いずれか一方の誘電体層の体積抵抗率を１０11Ωｃｍ以下とするとともに、他方の誘電体層の体積抵抗率は１０11Ωｃｍ以上とすることが好ましい。両方とも体積抵抗率を低くすると（例えば、１０8Ωｃｍ）、かえってストリーマを放電空間内で分散させることができず、むしろアーキングによる電流集中で誘電体層を劣化させる場合がある。これに対し、他方の誘電体層の体積抵抗率を１０11Ωｃｍ以上にすれば、ストリーマを放電空間内で分散させ易く、また、アーキングによる電流集中を抑制することができる。 In the present invention, either one of the dielectric layer volume resistivity of as well as the 10 11 [Omega] cm or less, the volume resistivity of the other dielectric layer is preferably set to 10 11 [Omega] cm or more. In both cases, when the volume resistivity is lowered (for example, 10 8 Ωcm), the streamer cannot be dispersed in the discharge space, but rather the current concentration due to arcing may deteriorate the dielectric layer. On the other hand, if the volume resistivity of the other dielectric layer is 10 11 Ωcm or more, the streamer can be easily dispersed in the discharge space, and current concentration due to arcing can be suppressed.
本発明では、体積抵抗率が１０11Ωｃｍ以下の誘電体層は、好ましくは１０10Ωｃｍ以下、より好ましくは１０9Ωｃｍ以下、さらに好ましくは１０8Ωｃｍ以下が望まれる。これにより、被処理物への放電処理速度をより一層高めることができる。なお、この誘電体層の体積抵抗率の下限については、誘電体層としての機能を発揮できればよく、実用上１０6Ωｃｍであることが好ましい。１０6Ωｃｍより低い場合には、得られる誘電体層が絶縁破壊し易い。 In the present invention, the dielectric layer having a volume resistivity of 10 11 Ωcm or less is preferably 10 10 Ωcm or less, more preferably 10 9 Ωcm or less, and even more preferably 10 8 Ωcm or less. Thereby, the discharge process speed to a to-be-processed object can be raised further. Note that the lower limit of the volume resistivity of the dielectric layer is not particularly limited as long as it can function as a dielectric layer, and is preferably 10 6 Ωcm in practice. When it is lower than 10 6 Ωcm, the obtained dielectric layer is likely to break down.
また、本発明では、体積抵抗率が１０11Ωｃｍ以上の誘電体層は、好ましくは１０12Ωｃｍ以上、より好ましくは１０13Ωｃｍ以上が望まれる。これにより、電界集中が生じにくくなるため、誘電体層の劣化を防ぐことができる。なお、この誘電体層の体積抵抗率の上限については、実用上１０16Ωｃｍである。一般に体積抵抗率が１０16Ωｃｍより高い誘電体層を作製するのは困難であるからである。 In the present invention, the dielectric layer having a volume resistivity of 10 11 Ωcm or more is preferably 10 12 Ωcm or more, more preferably 10 13 Ωcm or more. As a result, electric field concentration is unlikely to occur, so that deterioration of the dielectric layer can be prevented. The upper limit of the volume resistivity of this dielectric layer is practically 10 16 Ωcm. This is because it is generally difficult to produce a dielectric layer having a volume resistivity higher than 10 16 Ωcm.
なお、誘電体層の体積抵抗率の測定方法については後述する。 A method for measuring the volume resistivity of the dielectric layer will be described later.
＜誘電体層組成＞
電極の対向側表面に形成される誘電体層は、大気圧下での放電処理の際に、被処理物の温度が高くなりすぎることを防ぐとともに、ストリーマの発生を抑えたり分散させたり、電極表面を酸化しにくくすることができればよいが、さらに熱伝導性、強度、機械加工性、耐熱性等に優れていることが好ましい。そこで、本発明の誘電体層はセラミックスで構成されるのが好ましい。
<Dielectric layer composition>
The dielectric layer formed on the opposite surface of the electrode prevents the temperature of the workpiece from becoming too high during discharge treatment under atmospheric pressure, and suppresses or disperses the generation of streamers. Although it is sufficient if the surface can be made difficult to oxidize, it is preferable that the surface is further excellent in thermal conductivity, strength, machinability, heat resistance and the like. Therefore, the dielectric layer of the present invention is preferably composed of ceramics.
特に、体積抵抗率１０11Ωｃｍ以下の誘電体層は、高絶縁性セラミックスを母相として、さらに低絶縁性材料を含んで構成されることが好ましい。 In particular, it is preferable that the dielectric layer having a volume resistivity of 10 11 Ωcm or less includes a high insulating ceramic as a parent phase and further includes a low insulating material.
ここで、高絶縁性セラミックスとしては、絶縁抵抗値が１０13Ωｃｍ以上のセラミックスが好ましく、具体的には、アルミナ、ジルコニア、シリカ等から選ばれる少なくとも１種が挙げられる。 Here, the highly insulating ceramic is preferably a ceramic having an insulation resistance value of 10 13 Ωcm or more, and specifically includes at least one selected from alumina, zirconia, silica and the like.
また、低絶縁性材料としては、誘電体層中の絶縁抵抗を下げることができる材料であればよく、それ自体低絶縁性（絶縁抵抗値が１０11Ωｃｍ以下）を示す材料の他、それ自体低絶縁性を示さなくとも、（例えば溶射によって）形成された誘電体層中で低絶縁性（絶縁抵抗値が１０11Ωｃｍ以下）を示す材料であってもよい。具体的には、それ自体低絶縁性を示す材料としては、炭化ケイ素（ＳｉＣ）等の炭化物、酸化亜鉛（ＺｎＯ）等の酸化物等から選ばれる少なくとも１種が挙げられる。また、形成された誘電体層中で低絶縁性を示す材料としては、チタニア、クロミア等から選ばれる少なくとも１種が挙げられる。 The low-insulating material may be any material that can lower the insulation resistance in the dielectric layer. In addition to a material that itself exhibits low insulation (insulation resistance value of 10 11 Ωcm or less), the material itself Even if it does not exhibit low insulation, it may be a material that exhibits low insulation (insulation resistance value of 10 11 Ωcm or less) in a formed dielectric layer (for example, by thermal spraying). Specifically, examples of the material that exhibits low insulating properties include at least one selected from carbides such as silicon carbide (SiC), oxides such as zinc oxide (ZnO), and the like. In addition, examples of the material exhibiting low insulation in the formed dielectric layer include at least one selected from titania, chromia, and the like.
体積抵抗率１０11Ωｃｍ以下の誘電体層中での低絶縁性材料の含有率は、それ自体低絶縁性を示す材料を用いる場合は、１〜３０質量％であることが好ましく、５〜１５質量％であることがより好ましい。また、形成された誘電体層中で低絶縁性を示す材料を用いる場合には、低絶縁性材料の含有率は２〜５０質量％であることが好ましく、５〜１５質量％であることがより好ましい。 The content of the low-insulating material in the dielectric layer having a volume resistivity of 10 11 Ωcm or less is preferably 1 to 30% by mass in the case of using a material that itself exhibits low insulation, and 5 to 15 More preferably, it is mass%. Moreover, when using the material which shows low insulation in the formed dielectric material layer, it is preferable that the content rate of a low insulation material is 2-50 mass%, and it is 5-15 mass%. More preferred.
なお、体積抵抗率１０11Ωｃｍ以上の誘電体層は、前記高絶縁性セラミックスのみで構成されてもよいし、また必要に応じて前記低絶縁性材料を含んで構成されてもよい。具体的には、低絶縁性材料の含有率は、それ自体低絶縁性を示す材料を用いる場合は、６質量％以下であることが好ましく、３質量％以下であることがより好ましい。また、形成された誘電体層中で低絶縁性を示す材料を用いる場合には、５質量％以下であることが好ましく、３質量％以下であることがより好ましい。 Note that the dielectric layer having a volume resistivity of 10 11 Ωcm or more may be composed of only the high-insulating ceramic, or may include the low-insulating material as necessary. Specifically, the content of the low-insulating material is preferably 6% by mass or less, more preferably 3% by mass or less when using a material that exhibits low insulation itself. Moreover, when using the material which shows low insulation in the formed dielectric material layer, it is preferable that it is 5 mass% or less, and it is more preferable that it is 3 mass% or less.
本発明の誘電体層は、アルミナとチタニアの組み合わせで構成されることが最も好ましい。アルミナ−チタニア系セラミックスは、誘電体層の体積抵抗率を容易に調整できるのみならず、市場において入手容易であるため低コスト化を図ることができるからである。 The dielectric layer of the present invention is most preferably composed of a combination of alumina and titania. This is because alumina-titania ceramics can not only easily adjust the volume resistivity of the dielectric layer, but also can be reduced in cost because it is readily available in the market.
＜膜厚＞
本発明では、体積抵抗率１０11Ωｃｍ以下の誘電体層の膜厚を０．１ｍｍ以上とする。体積抵抗率１０11Ωｃｍ以下の誘電体層の膜厚を０．１ｍｍ以上とすることにより、アーキングの発生、及びストリーマの集中による絶縁破壊を防ぐことができる。かかる膜厚は、好ましくは０．２ｍｍ以上、より好ましくは０．５ｍｍ以上、さらに好ましくは０．７ｍｍ以上である。上限については、５．０ｍｍが好ましく、３．０ｍｍがより好ましく、１．０ｍｍがさらに好ましい。膜厚が５．０ｍｍを超える場合には、誘電体層が電極から剥離し易くなる。また、製造コストが上がる場合がある。
<Film thickness>
In the present invention, the thickness of the dielectric layer having a volume resistivity of 10 11 Ωcm or less is set to 0.1 mm or more. By setting the film thickness of the dielectric layer having a volume resistivity of 10 11 Ωcm or less to 0.1 mm or more, generation of arcing and dielectric breakdown due to streamer concentration can be prevented. Such a film thickness is preferably 0.2 mm or more, more preferably 0.5 mm or more, and further preferably 0.7 mm or more. About an upper limit, 5.0 mm is preferable, 3.0 mm is more preferable, and 1.0 mm is further more preferable. When the film thickness exceeds 5.0 mm, the dielectric layer is easily peeled off from the electrode. In addition, the manufacturing cost may increase.
また、本発明では、体積抵抗率１０11Ωｃｍ以上の誘電体層の膜厚を０．２ｍｍ〜５．０ｍｍとする。体積抵抗率１０11Ωｃｍ以上の誘電体層の膜厚を上記範囲とすることにより、誘電体層が絶縁破壊したり、誘電体層が電極から剥離するのを防ぐことができる。また、製造コストを抑えることができる。かかる膜厚は、０．４ｍｍ〜４．０ｍｍであることが好ましく、０．６ｍｍ〜３．０ｍｍであることがより好ましく、０．８ｍｍ〜２．０ｍｍであることがさらに好ましい。 In the present invention, the film thickness of the dielectric layer having a volume resistivity of 10 11 Ωcm or more is set to 0.2 mm to 5.0 mm. By setting the film thickness of the dielectric layer having a volume resistivity of 10 11 Ωcm or more in the above range, it is possible to prevent the dielectric layer from being broken down or peeling from the electrode. Moreover, manufacturing cost can be suppressed. The film thickness is preferably 0.4 mm to 4.0 mm, more preferably 0.6 mm to 3.0 mm, and still more preferably 0.8 mm to 2.0 mm.
本発明では、体積抵抗率１０11Ωｃｍ以下の誘電体層の膜厚を、体積抵抗率１０11Ωｃｍ以上の誘電体層の膜厚に対して、０．２〜１倍とすることが好ましい。０．２倍未満では、アーキングの発生、及びストリーマの集中による絶縁破壊を抑えることができない場合がある。また、１倍を超えると、低コスト化を図りにくくなる。 In the present invention, the thickness of the volume resistivity of 10 11 [Omega] cm or less of the dielectric layer, for a film thickness of the volume resistivity of 10 11 [Omega] cm or more dielectric layers, it is preferable that the 0.2 to 1-fold. If it is less than 0.2 times, the occurrence of arcing and the dielectric breakdown due to the concentration of streamers may not be suppressed. Moreover, when it exceeds 1 time, it will become difficult to aim at cost reduction.
＜誘電体層を備えた電極の作製方法＞
誘電体層を備えた電極の作製方法としては、誘電体形成材料、例えば、上記高絶縁性セラミックス材料と低絶縁性材料との混合粉末を用いて誘電体を得、これを電極基板に貼着させて行なう方法や、この誘電体に電極材料（導電金属）を蒸着させて行なう方法や、電極基板に上記混合粉末を溶射して行なう方法等が挙げられる。本発明では、電極の大型化とロール形状電極への成膜に対応するため、溶射法を採用するのが好ましい。溶射方法としては、具体的には、水素（Ｈ２）、窒素（Ｎ２）、希ガス等を真空中で電離させて生じる高温、高圧のプラズマジェットに、上記混合粉末を供給し、プラズマジェット中で溶融、加速して電極に衝突させて形成するプラズマ溶射法が挙げられる。
<Method for Producing Electrode with Dielectric Layer>
As a method of manufacturing an electrode provided with a dielectric layer, a dielectric is obtained by using a dielectric forming material, for example, a mixed powder of the above-mentioned high-insulating ceramic material and low-insulating material, and this is adhered to an electrode substrate And a method in which an electrode material (conductive metal) is deposited on the dielectric, a method in which the mixed powder is sprayed onto the electrode substrate, and the like. In the present invention, it is preferable to employ a thermal spraying method in order to cope with the enlargement of the electrode and the film formation on the roll-shaped electrode. Specifically, as the thermal spraying method, the mixed powder is supplied to a high-temperature, high-pressure plasma jet generated by ionizing hydrogen (H 2 ), nitrogen (N 2 ), a rare gas or the like in a vacuum, and the plasma jet Among them, there is a plasma spraying method which is formed by melting and accelerating and colliding with an electrode.
特に、本発明では、レーザー回折式粒度分布測定装置を用いて測定される平均粒径（Ｄ５０）（体積基準）が１００μｍ以下の誘電体形成材料（例えば、高絶縁性セラミックス材料粉末と低絶縁性材料粉末との混合粉末）を用いて作製することが好ましく、より好ましい粒径は３０μｍ以下である。平均粒径（Ｄ５０）が１００μｍ以下の誘電体形成材料を用いることによって、体積抵抗率が均一な誘電体層を形成することができる。 In particular, in the present invention, a dielectric forming material (for example, a high insulating ceramic material powder and a low insulating property) having an average particle diameter (D50) (volume basis) of 100 μm or less measured using a laser diffraction particle size distribution measuring apparatus. (Mixed powder with material powder) is preferable, and a more preferable particle size is 30 μm or less. By using a dielectric forming material having an average particle diameter (D50) of 100 μm or less, a dielectric layer having a uniform volume resistivity can be formed.
本発明では、電極への誘電体層の形成前に、電極表面をブラスト処理により粗面化してもよい。また、ブラスト処理に代えて、あるいはブラスト処理に続いて、電極表面に、Ｎｉ−Ａｌ、Ｎｉ−Ｃｒ、あるいはＣｒ−Ｆｅ等の合金のアンダーコートを、５０〜２００μｍ厚で形成してもよい。これにより、電極と誘電体層の密着性を高めることができる。 In the present invention, the electrode surface may be roughened by blasting before the dielectric layer is formed on the electrode. Further, instead of blasting or following blasting, an undercoat of an alloy such as Ni—Al, Ni—Cr, or Cr—Fe may be formed on the electrode surface in a thickness of 50 to 200 μm. Thereby, the adhesiveness of an electrode and a dielectric material layer can be improved.
電極表面に溶射法によって形成された誘電体層には、通常、２〜２０％程度の気孔がある。そこで、誘電体を溶射法で形成した後、封孔処理を施してもよい。これにより、大気圧中で高い電気絶縁性、気密性、及び密着性を有する誘電体層にすることができる。この封孔処理は、具体的には、溶射法によって誘電体層を形成した後、誘電体層の表面に、Ｂ２Ｏ３、Ｐ２Ｏ５、Ｎａ２ＳｉＯ３等のガラス形成物質の少なくとも１種と、ＳｉＯ２、Ａｌ２Ｏ３、ＭｇＯ、ＡｌＮ等の無機物質微粉末の少なくとも１種と、水やアルコール等の溶媒とを混合した液状物質（充填材）を塗布して、誘電体層中の気孔中に侵入させた後、１５０〜４５０℃で０．５〜５時間加熱する方法が挙げられる。これにより、Ｂ２Ｏ３やＰ２Ｏ５等を主成分とするガラス質物質を気孔中に生成させることができる。 The dielectric layer formed on the electrode surface by spraying usually has about 2 to 20% of pores. Therefore, a sealing process may be performed after the dielectric is formed by a thermal spraying method. Thereby, it can be set as the dielectric layer which has high electrical insulation, airtightness, and adhesiveness in atmospheric pressure. Specifically, this sealing treatment is performed by forming a dielectric layer by a thermal spraying method, and then forming at least a glass-forming substance such as B 2 O 3 , P 2 O 5 , Na 2 SiO 3 on the surface of the dielectric layer. Applying a liquid substance (filler), which is a mixture of at least one kind of inorganic substance fine powder such as SiO 2 , Al 2 O 3 , MgO, and AlN and a solvent such as water or alcohol to form a dielectric A method of intruding into the pores in the layer and then heating at 150 to 450 ° C. for 0.5 to 5 hours can be mentioned. Thus, a glassy material mainly composed of B 2 O 3 and P 2 O 5 or the like can be produced in the pores.
（放電ギャップ）
本発明の放電用電極は、放電ギャップを０．０２〜５．０ｍｍとすることが好ましく、０．０５〜４．０ｍｍとすることがより好ましく、０．１０〜３．０ｍｍとすることがさらに好ましい。放電電力は、放電ギャップの他に、誘電体層の体積抵抗率や膜厚によっても影響を受けるものであり、誘電体層の構成を勘案しつつ上記範囲内とすれば、電圧一定下での放電電力を大きくし易い。また、製造コストの点からも好ましい。特に、対向する二つの電極に設けられる誘電体層の体積抵抗率が、それぞれ１０8Ωｃｍと１０12Ωｃｍの組み合わせの場合であって、膜厚が双方とも０．５ｍｍの場合に、放電ギャップを０．７５〜１．２５ｍｍとすることが、放電電力をより大きくできる点で最も好ましい。
(Discharge gap)
The discharge electrode of the present invention preferably has a discharge gap of 0.02 to 5.0 mm, more preferably 0.05 to 4.0 mm, and further preferably 0.10 to 3.0 mm. preferable. In addition to the discharge gap, the discharge power is also affected by the volume resistivity and film thickness of the dielectric layer. It is easy to increase the discharge power. Moreover, it is preferable also from the point of manufacturing cost. In particular, when the volume resistivity of the dielectric layers provided on the two opposing electrodes is a combination of 10 8 Ωcm and 10 12 Ωcm, respectively, and the film thickness is both 0.5 mm, the discharge gap is increased. The thickness of 0.75 to 1.25 mm is most preferable in that the discharge power can be increased.
（使用方法）
本発明の放電用電極は、電極間電極を３〜３０ｋＶ、より好ましくは８〜２０ｋＶで使用されることが好ましい。この範囲において、被処理物の損傷を防ぎつつ、放電処理をすることができる。なお、電極間電圧はオシロスコープによって測定した。
(how to use)
In the discharge electrode of the present invention, the interelectrode electrode is preferably used at 3 to 30 kV, more preferably 8 to 20 kV. In this range, discharge treatment can be performed while preventing damage to the object to be processed. The interelectrode voltage was measured with an oscilloscope.
本発明の放電用電極を用いて、被処理物を処理する方法としては、例えば、電極間に水素ガス、窒素ガス、希ガス等の放電ガスを導入しながら、電極間に高周波電圧を印加して放電ガスをプラズマ化あるいは活性化した後、これを被処理物の表面に曝して行なう方法が挙げられる。また、電極間に高周波電圧を印加しながら、電極間に被処理物を通過させて行ってもよい。本発明では、電極の双方が誘電体層を有しており、一方の電極にのみ誘電体層を有する放電用電極に比べて、大気圧放電の際にストリーマが発生しにくく、また、発生してもストリーマが細く、さらに分散しやすいため、電極間に被処理物を直接通過させても、放電によって被処理物が損傷をうけにくい。 As a method of processing an object to be processed using the discharge electrode of the present invention, for example, a high frequency voltage is applied between electrodes while introducing a discharge gas such as hydrogen gas, nitrogen gas, or rare gas between the electrodes. For example, the discharge gas may be plasmatized or activated and then exposed to the surface of the object to be processed. Moreover, you may carry out by passing a to-be-processed object between electrodes, applying a high frequency voltage between electrodes. In the present invention, both electrodes have a dielectric layer, and streamers are less likely to occur during atmospheric pressure discharge, as compared to a discharge electrode having a dielectric layer only on one electrode. However, since the streamer is thin and easily dispersed, the object to be processed is not easily damaged by the discharge even if the object to be processed is directly passed between the electrodes.
本発明の放電用電極で処理される被処理物としては、特に限定されるものではなく、例えば、高分子フィルムやシート、紙、アルミ箔等が挙げられる。 The material to be processed with the discharge electrode of the present invention is not particularly limited, and examples thereof include polymer films, sheets, paper, and aluminum foil.
以下、実施例に基づいて本発明を詳細に述べる。ただし、下記実施例は本発明を制限するものではなく、前・後記の趣旨を逸脱しない範囲で変更実施をすることは全て本発明の技術的範囲に包含される。なお、特に断らない限り、「部」は「質量部」を、「％」は「質量％」をそれぞれ意味する。 Hereinafter, the present invention will be described in detail based on examples. However, the following examples are not intended to limit the present invention, and all modifications made without departing from the spirit of the preceding and following descriptions are included in the technical scope of the present invention. Unless otherwise specified, “part” means “part by mass” and “%” means “% by mass”.
本発明で用いた評価方法について、以下説明する。 The evaluation method used in the present invention will be described below.
（体積抵抗率）
基材上に、実験例で用いた誘電体形成材料を溶射して誘電体層を形成し、次いで基材を剥離除去して誘電体（試験片）を作製した。その後、この試験片の体積抵抗率を、ＪＩＳ Ｃ２１３９の規定に準じて測定した。
(Volume resistivity)
On the base material, the dielectric material used in the experimental example was sprayed to form a dielectric layer, and then the base material was peeled and removed to prepare a dielectric (test piece). Thereafter, the volume resistivity of the test piece was measured in accordance with JIS C2139.
（放電電力）
作製した放電用電極対（放電ギャップ：１ｍｍ）を用いて、図３に示すようなＳａｗｙｅｒ−Ｔｏｗｅｒ回路を作製し、オシロスコープ２５で放電中の電極間電圧（ＶＥ）と標準コンデンサー電圧（ＶＳ）を同時に測定してリサージュ図形を描いた。描かれたリサージュ図形の面積を算出し、次式から放電用電極対における放電電力Ｐを求めた。
(Discharge power)
A Sawyer-Tower circuit as shown in FIG. 3 is produced using the produced discharge electrode pair (discharge gap: 1 mm), and the interelectrode voltage (V E ) and the standard capacitor voltage (V S ) during discharge with the oscilloscope 25 are produced. ) Was measured at the same time to draw a Lissajous figure. The area of the drawn Lissajous figure was calculated, and the discharge power P at the discharge electrode pair was determined from the following equation.
（式中、Ｐは放電電力、ＶＥは電極間電圧≒電源電圧、Ｑは電荷量、ＣＳは標準コンデンサー静電容量、ｆは周波数、ｍは高圧プローブ倍率、ΔＶは高圧プローブの低圧側電位、Ｓはリサージュ図形面積をそれぞれ示す。） (Wherein, P is discharge power, V E is the inter-electrode voltage ≒ supply voltage, Q is the charge amount, C S is the standard condenser capacitance, f is the frequency, m is the high pressure probe magnification, [Delta] V is the low pressure side of the high pressure probe The potential and S indicate the Lissajous figure area.)
（被処理物の濡れ性）
放電用電極対を用いて処理された被処理物に水滴を滴下して、被処理物表面での水滴の状態を観察して評価した。水滴が表面をよく濡らした場合を○、表面上で水玉となった場合を×とした。
(Wettability of workpiece)
Water droplets were dropped on the object to be processed using the discharge electrode pair, and the state of the water droplets on the surface of the object to be processed was observed and evaluated. The case where water droplets wet the surface well was marked with ◯, and the case where water drops became polka dots on the surface was marked with ×.
（放電用電極対の作製）
以下の方法により、本発明の放電用電極対で用いる電極を作製した。
(Preparation of discharge electrode pair)
The electrodes used in the discharge electrode pair of the present invention were produced by the following method.
実験例１
炭素鋼ＳＳ４００平板を、５０×５０×５ｍｍにカットし、両面を平面研磨して、電極１とした。
Experimental example 1
A carbon steel SS400 flat plate was cut into 50 × 50 × 5 mm, and both surfaces were polished to obtain an electrode 1.
実験例２
電極１の一方の表面をブラスト処理により粗面化した後、その上に、溶射ガン（Ｓｕｌｚｅｒ Ｍｅｔｃｏ社製、Ｆ４）を用いて、チタニア含有率３質量％のアルミナ−チタニア粉末（平均粒径（Ｄ５０）２０μｍ）をプラズマ溶射し、電極表面に厚さ１．０ｍｍの誘電体層を有する電極２を得た（体積抵抗率１０12Ωｃｍ）。
Experimental example 2
After roughening one surface of the electrode 1 by blasting, an alumina-titania powder (average particle size (average particle size (3%) by weight) with a spray gun (Sulzer Metco, F4) is used. D50) 20 μm) was plasma sprayed to obtain an electrode 2 having a dielectric layer with a thickness of 1.0 mm on the electrode surface (volume resistivity 10 12 Ωcm).
実験例３
チタニア含有率３質量％のアルミナ−チタニア粉末を用い、誘電体層の膜厚を０．５ｍｍとした以外は実験例２と同様にして、電極３を得た（体積抵抗率１０12Ωｃｍ）。
Experimental example 3
An electrode 3 was obtained in the same manner as in Experimental Example 2 except that an alumina-titania powder having a titania content of 3% by mass was used and the thickness of the dielectric layer was changed to 0.5 mm (volume resistivity 10 12 Ωcm).
実験例４
チタニア含有率１３質量％のアルミナ−チタニア粉末（平均粒径（Ｄ５０）２０μｍ）を用い、誘電体層の膜厚を０．５ｍｍとした以外は実験例２と同様にして、電極４を得た（体積抵抗率１０8Ωｃｍ）。
Experimental Example 4
An electrode 4 was obtained in the same manner as in Experimental Example 2 except that alumina-titania powder (average particle diameter (D50) 20 μm) having a titania content of 13% by mass was used and the thickness of the dielectric layer was 0.5 mm. (Volume resistivity 10 8 Ωcm).
（実施例１）
電極３と電極４とを用い、互いの誘電体層が対向するように配置（放電ギャップ：１ｍｍ）して、放電用電極対１を作製した。
Example 1
The electrode 3 and the electrode 4 were used and arranged so that the dielectric layers face each other (discharge gap: 1 mm), and the discharge electrode pair 1 was produced.
（参考例）
電極４を二つ用いた以外は実施例１と同様にして、放電用電極対２を作製した。
( Reference example )
A discharge electrode pair 2 was produced in the same manner as in Example 1 except that two electrodes 4 were used.
（比較例１）
電極１と電極２とを用いた以外は実施例１と同様にして、放電用電極対３を作製した。なお、この場合、一方の電極表面には誘電体層は形成されていない。
(Comparative Example 1)
A discharge electrode pair 3 was produced in the same manner as in Example 1 except that the electrode 1 and the electrode 2 were used. In this case, a dielectric layer is not formed on one electrode surface.
（比較例２）
電極３を二つ用いた以外は実施例１と同様にして、放電用電極対４を作製した。
(Comparative Example 2)
A discharge electrode pair 4 was produced in the same manner as in Example 1 except that two electrodes 3 were used.
（放電電力評価）
上記の方法によって、放電用電極対１〜４の放電電力を求めた。その結果を表１に示す。なお、放電用電極対１、３及び４については電極間電圧ＡＣ６ｋＶ、周波数１０ｋＨｚとし、放電用電極対２については電極間電圧ＡＣ４ｋＶ、周波数１０ｋＨｚとした。
(Discharge power evaluation)
The discharge power of the discharge electrode pairs 1 to 4 was determined by the above method. The results are shown in Table 1. The discharge electrode pair 1, 3 and 4 were set to an interelectrode voltage AC of 6 kV and a frequency of 10 kHz, and the discharge electrode pair 2 was set to an interelectrode voltage AC of 4 kV and a frequency of 10 kHz.
（印加後の外観評価）
放電用電極対１、３及び４について、それぞれ二つの電極に電圧ＡＣ６ｋＶ、周波数１０ｋＨｚを１０分間印加した後の、放電用電極対の外観（錆の発生、及びストリーマ痕の有無）を観察した。また、放電用電極対２については、電圧ＡＣ４ｋＶ、周波数１０ｋＨｚを１０分間印加した後の、放電用電極の外観（錆の発生、及びストリーマ痕の有無）を観察した。その結果を表１に示す。
(Appearance evaluation after application)
With respect to the discharge electrode pairs 1, 3 and 4, the appearance of the discharge electrode pair (the occurrence of rust and the presence of streamer marks) after applying a voltage AC of 6 kV and a frequency of 10 kHz to the two electrodes for 10 minutes was observed. Moreover, about the electrode pair 2 for discharge, the external appearance (generation | occurrence | production of rust and the presence or absence of streamer traces) of the electrode for discharge after applying voltage AC4kV and frequency 10kHz for 10 minutes was observed. The results are shown in Table 1.
なお、放電用電極対２については、電圧ＡＣ４．５ｋＶで誘電体層が絶縁破壊を生じた。 For the discharge electrode pair 2, the dielectric layer caused dielectric breakdown at a voltage of AC 4.5 kV.
（被処理物の濡れ性評価）
放電用電極対１、３及び４を用いて、それぞれ二つの電極に電圧ＡＣ６ｋＶ、周波数１０ｋＨｚを印加しながら、電極間に被処理物（ＰＥＴフィルム）を通過させて放電処理を施した。また、放電用電極対２については、電圧ＡＣ４ｋＶ、周波数１０ｋＨｚを印加しながら、被処理物（ＰＥＴフィルム）に同様の処理を施した。得られた処理後の被処理物の表面の濡れ性を評価した。その結果を表１に示す。
(Evaluation of wettability of workpieces)
Using discharge electrode pairs 1, 3, and 4, an object to be treated (PET film) was passed between the electrodes while applying a voltage of AC 6 kV and a frequency of 10 kHz to the two electrodes, and a discharge treatment was performed. Moreover, about the electrode pair 2 for discharge, the same process was performed to the to-be-processed object (PET film), applying voltage AC4kV and frequency 10kHz. The wettability of the surface of the processed object obtained was evaluated. The results are shown in Table 1.
上記表から、双方の電極に誘電体層を設けることにより、電極表面の錆の発生や誘電体層の劣化（ストリーマ痕の発生）が抑えられることが分かった（実施例１及び参考例）。 From the said table | surface, it turned out that generation | occurrence | production of the rust of an electrode surface and deterioration (distance generation | occurrence | production of a streamer trace) are suppressed by providing a dielectric layer in both electrodes (Example 1 and a reference example ).
これに対し、一方の電極にのみ誘電体層を設けた場合には、誘電体層を設けなかった側の電極（電極Ａ）表面に錆が発生し、また、誘電体層にはストリーマ痕が見られた（比較例１）。 On the other hand, when the dielectric layer is provided only on one electrode, rust is generated on the surface of the electrode (electrode A) on which the dielectric layer is not provided, and streamer marks are formed on the dielectric layer. It was seen (Comparative Example 1).
また、双方の電極に誘電体層を設けただけでは、錆の発生や誘電体層の劣化（ストリーマ痕の発生）は防げるものの放電電力は低下することが分かった（比較例１及び２）。これに対し、誘電体層の少なくとも一方を体積抵抗率１０11Ωｃｍ以下とすることにより、放電電力を高くできることが分かった（実施例１及び参考例と比較例２）。 It was also found that the discharge power was reduced by providing the dielectric layers on both electrodes, although the generation of rust and the deterioration of the dielectric layers (generation of streamer marks) could be prevented (Comparative Examples 1 and 2). On the other hand, it was found that the discharge power can be increased by setting at least one of the dielectric layers to a volume resistivity of 10 11 Ωcm or less (Example 1, Reference Example and Comparative Example 2).
放電用電極対２については、電圧ＡＣ４．５ｋＶで印加すると誘電体層に絶縁破壊が見られたことから、誘電体層の他方を体積抵抗率１０11Ωｃｍ以上とすることにより、誘電体層がより劣化し難くなることが分かった（参考例）。 With respect to the discharge electrode pair 2, since dielectric breakdown was observed in the dielectric layer when applied at a voltage of AC 4.5 kV, the dielectric layer was formed by setting the other dielectric layer to a volume resistivity of 10 11 Ωcm or more. It turned out that it becomes harder to deteriorate ( reference example ).
本発明は、不均一放電や被処理物への金属コンタミを防ぐことのできる放電用電極の製造に有用である。 INDUSTRIAL APPLICATION This invention is useful for manufacture of the electrode for discharge which can prevent nonuniform discharge and the metal contamination to a to-be-processed object.
１：放電用電極、５、５’：電極、１５：誘電体層、２０：標準コンデンサー、２５：オシロスコープ、３０：高圧プローブ 1: discharge electrode, 5, 5 ': electrode, 15: dielectric layer, 20: standard capacitor, 25: oscilloscope, 30: high voltage probe
Claims (6)
これら電極には、対向側表面に誘電体層が形成され、
前記各誘電体層の一方が体積抵抗率１０11Ωｃｍ以下であり、他方が体積抵抗率１０ 11 Ωｃｍ以上であり、且つ前記他方の体積抵抗率は前記一方の体積抵抗率より高いことを特徴とする放電用電極。 With two opposing electrodes,
These electrodes have a dielectric layer formed on the opposite surface,
Wherein Ri der one volume resistivity 10 11 [Omega] cm or less of the dielectric layer, the other is a volume resistivity of 10 11 [Omega] cm or more and volume resistivity of the other being greater than the volume resistivity of the one Discharge electrode.
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