JPH0629147A - Laminate for laminated film capacitor - Google Patents
Laminate for laminated film capacitorInfo
- Publication number
- JPH0629147A JPH0629147A JP4181974A JP18197492A JPH0629147A JP H0629147 A JPH0629147 A JP H0629147A JP 4181974 A JP4181974 A JP 4181974A JP 18197492 A JP18197492 A JP 18197492A JP H0629147 A JPH0629147 A JP H0629147A
- Authority
- JP
- Japan
- Prior art keywords
- hydrocarbon group
- less
- group
- laminated film
- film capacitor
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、高耐湿性が要求される
電子機器および電気機器に使用される小形の積層フィル
ムコンデンサに用いられる積層フィルムコンデンサ用積
層体に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminated body for laminated film capacitors used in small-sized laminated film capacitors used in electronic equipment and electric equipment requiring high humidity resistance.
【０００２】[0002]
【従来の技術】近年、屋外で使用される電子機器及び電
気機器が急速な伸びを示し、需要は極めて高い。そのた
め、使用される電子部品にも従来以上に大幅な小形・軽
量化や特性上とりわけ耐湿性に関して特に厳しい要求が
増えている。2. Description of the Related Art In recent years, the demand for electronic equipment and electric equipment used outdoors has grown rapidly, and the demand for them is extremely high. For this reason, demands for electronic components to be used are much smaller and lighter than ever before, and particularly strict requirements for moisture resistance are increasing due to their characteristics.
【０００３】以下に、従来の積層フィルムコンデンサ用
の積層体の製造方法について説明する。A conventional method for manufacturing a laminated body for a laminated film capacitor will be described below.
【０００４】図２は従来の積層フィルムコンデンサ用の
積層体の断面図である。図２において、１１はポリエチ
レンテレフタレートフィルム、１２，１３は蒸着電極、
１４，１５はパラフィンオイル薄膜、１６，１７はコー
ティング薄膜である。従来、積層フィルムコンデンサ用
の積層体は以下のようにして製造されてきた。即ち、厚
さ１．５μｍ以上のポリエチレンテレフタレートフィル
ム１１の片面に、まず厚さ７０ｎｍで幅が０．３〜１ｍ
ｍで所定のピッチで連続した多数の帯状のパラフィンオ
イル薄膜１４を形成した直後にアルミニウムを真空蒸着
することにより帯状に分離された蒸着電極１２が形成さ
れる。この後ポリエチレンテレフタレートフィルム１１
を反転して所定の寸法だけずらして所定のピッチで連続
した多数の帯状のパラフィンオイル薄膜１５を形成し、
同様にして蒸着電極１３が形成され一度に数千〜数万メ
ートルの両面金属化フィルムが製造される。続いて、こ
の両面金属化フィルムの片面に、ポリカーボネートと接
着剤と染料を塩素系溶剤で塗料化したものをリバースコ
ート方式で多数の帯状に厚さ約１μｍに全面に塗布し乾
燥してコーティング薄膜１６が形成されロールに巻取ら
れる。その後反体側の面に同様にしてコーティング薄膜
１７が形成され両面コーティング両面金属化フィルムが
製造される。この後、両面コーティング両面金属化フィ
ルムを所定の枚数積層し、分散された接着剤が軟化する
温度で、低い圧力でホットプレスされ、積層フィルムコ
ンデンサ用積層体が製造されてきた。FIG. 2 is a cross-sectional view of a conventional laminated body for a laminated film capacitor. In FIG. 2, 11 is a polyethylene terephthalate film, 12 and 13 are vapor deposition electrodes,
Reference numerals 14 and 15 are paraffin oil thin films, and 16 and 17 are coating thin films. Conventionally, a laminated body for a laminated film capacitor has been manufactured as follows. That is, on one surface of the polyethylene terephthalate film 11 having a thickness of 1.5 μm or more, first, the thickness is 70 nm and the width is 0.3 to 1 m.
Immediately after forming a large number of strip-shaped paraffin oil thin films 14 at a predetermined pitch of m, aluminum is vacuum-deposited to form strip-shaped vapor deposition electrodes 12. After this, polyethylene terephthalate film 11
And a large number of strip-shaped paraffin oil thin films 15 continuous at a predetermined pitch by reversing by
Similarly, the vapor deposition electrode 13 is formed, and a double-sided metallized film having a thickness of several thousand to several tens of thousands meters at a time is manufactured. Subsequently, one side of this double-sided metallized film was coated with polycarbonate, an adhesive and a dye with a chlorine-based solvent in a reverse coating method to form a number of strips with a thickness of about 1 μm, which was then dried to form a coating thin film. 16 is formed and wound on a roll. After that, the coating thin film 17 is similarly formed on the surface on the opposite side, and a double-sided coated double-sided metallized film is manufactured. Thereafter, a predetermined number of double-sided coated double-sided metallized films are laminated and hot pressed at a low pressure at a temperature at which the dispersed adhesive is softened to manufacture a laminated body for a laminated film capacitor.
【０００５】[0005]
【発明が解決しようとする課題】従来の積層フィルムコ
ンデンサを小形化するためには、素子を構成する両面コ
ーティング両面金属化フィルムを薄くする必要があっ
た。そのため、ポリエチレンテレフタレートを１．５μ
ｍ以下にすると、伸びやすく、切れやすく、滑りにくく
なり、両面コーティング両面金属化フィルムを製造する
ための真空蒸着装置やリバースコーターを通すだけで皺
だらけのフィルムとなった。In order to miniaturize the conventional laminated film capacitor, it is necessary to thin the double-sided coated double-sided metallized film that constitutes the device. Therefore, polyethylene terephthalate is 1.5μ
When the thickness was less than m, the film was easily stretched, easily cut, and was less likely to slip, and a wrinkled film was obtained only by passing through a vacuum vapor deposition device or a reverse coater for producing a double-sided coated double-sided metallized film.
【０００６】また、コーティング薄膜の厚さは定格電圧
が５０Ｖの場合、１μｍ前後が従来の実用の限界であっ
た。薄くした場合、ポリエチレンテレフタレートフィル
ムの滑り性を得るために加工している０．２〜０．５μ
ｍの微小な無数の突起と同程度になるため、突起が両面
コーティング両面金属化フィルム同志の接着を妨害した
り、相手のコーティング薄膜を押し潰すために耐圧低下
を招く等の問題があった。以上の問題点から、積層フィ
ルムコンデンサの小形化には限界があり、素子体積で１
割の小形化も困難な状況であった。Further, the thickness of the coating thin film is about 1 μm when the rated voltage is 50 V, which is the limit of practical use in the past. When thinned, 0.2-0.5μ is processed to obtain the slipperiness of the polyethylene terephthalate film.
Since the number of projections is about the same as the countless minute projections of m, there are problems that the projections interfere with the adhesion of the double-sided coated double-sided metallized films, or the coating thin film of the other side is crushed, resulting in a decrease in pressure resistance. From the above problems, there is a limit to miniaturization of the laminated film capacitor, and the device volume is 1
It was a difficult situation to make it smaller.
【０００７】本発明は上記従来の問題点を解決するもの
で、小形で高耐湿性の積層フィルムコンデンサ用の積層
体を提供することを目的とする。The present invention solves the above-mentioned conventional problems, and an object of the present invention is to provide a small-sized laminated body for a high humidity resistance laminated film capacitor.
【０００８】[0008]
【課題を解決するための手段】この目的を達成するため
に本発明の積層フィルムコンデンサ用の積層体は連続し
て接続した基板上に表面部の酸化処理された、一般式がIn order to achieve this object, a laminate for a laminated film capacitor of the present invention has a general formula in which the surface portion is subjected to an oxidation treatment on continuously connected substrates.
【０００９】[0009]
【化３】 [Chemical 3]
【００１０】で示される化合物（ただし、式中のＸは水
素またはメチル基を示し、Ｒはメチレン基数７以上１３
以下の鎖式炭化水素基、炭素数４以上１２以下の環式炭
化水素基、少なくとも一方にメチレン基数６以下の鎖式
炭化水素基を有する炭素数４以上１２以下の環式炭化水
素基であるか、あるいはそれらの水素原子の一部もしく
は全てがハロゲン原子またはアルキル基に置換されたも
の）を単独あるいは併用したものの含有ビニル基の６０
〜９５％を反応させてなる三次元網目構造の誘電体層
と、その上に表面が酸化処理されたアルミニウムの真空
蒸着層を交互に積層したことを特徴としている。A compound represented by the formula (wherein X represents hydrogen or a methyl group, and R represents a number of methylene groups of 7 or more 13
The following are chain hydrocarbon groups, cyclic hydrocarbon groups having 4 to 12 carbon atoms, and cyclic hydrocarbon groups having 4 to 12 carbon atoms and having at least one chain hydrocarbon group having 6 or less methylene groups. Or a vinyl group containing 60 or more of those hydrogen atoms partially or wholly substituted by halogen atoms or alkyl groups, alone or in combination.
It is characterized in that a dielectric layer having a three-dimensional network structure formed by reacting .about.95% of it and a vacuum-deposited layer of aluminum whose surface is oxidized are alternately laminated thereon.
【００１１】[0011]
【作用】一般に、積層フィルムコンデンサを小形化する
ためには、ポリエチレンテレフタレートフィルムを省略
することが最も良い方法である。そのため、従来から、
コーティング薄膜として、テトラフルオロエチレンのプ
ラズマ重合膜や炭化水素基に二個の（メタ）アクリロイ
ルオキシ基を付加した化合物（以下ジ（メタ）アクリレ
ートあるいはジアクリレートまたはジメタクリレートと
略す）を電子線照射して重合させた電子線重合膜（特開
昭６０−１５３１１３号公報、特開昭６０−１５７０６
号公報）等の無溶剤で形成する方法が開発されてきた。In general, it is the best method to omit the polyethylene terephthalate film in order to miniaturize the laminated film capacitor. Therefore, from the past,
As a coating thin film, a plasma polymerized film of tetrafluoroethylene or a compound in which two (meth) acryloyloxy groups are added to a hydrocarbon group (hereinafter abbreviated as di (meth) acrylate or diacrylate or dimethacrylate) is irradiated with an electron beam. Electron-polymerized film polymerized by polymerization (JP-A-60-153113, JP-A-60-15706).
A method of forming without solvent has been developed.
【００１２】しかし、それらの方法では、１μＦの静電
容量のコンデンサを作るのに前者ではコーティング薄膜
の形成に時間がかかりすぎたり、後者では固く脆いため
生産性に欠けたり、屋外での使用に必要な６０℃の温度
で９５％の相対湿度の中での連続通電に堪えない等の問
題が解決できていなかった。[0012] However, in those methods, it takes too much time to form a coating thin film in the former to make a capacitor having a capacitance of 1 µF, and in the latter, it is hard and brittle and lacks in productivity. Problems such as the inability to withstand continuous energization at the required temperature of 60 ° C. and relative humidity of 95% have not been solved.
【００１３】また、定格電圧直流５０Ｖで１μＦの静電
容量の積層フィルムコンデンサを製造するためには、
０．８μｍのコート厚さで約１８００層を積層する必要
があり、さらに１０μＦの静電容量の積層フィルムコン
デンサを製造するためには、約１８０００層を積層する
必要がある。この時、積層フィルムコンデンサの完成寸
法はタンタル電解コンデンサやセラミックコンデンサと
ほぼ同等となる。Further, in order to manufacture a laminated film capacitor having a capacitance of 1 μF at a rated voltage of DC 50 V,
About 1800 layers need to be laminated with a coating thickness of 0.8 μm, and further about 18000 layers need to be laminated to manufacture a laminated film capacitor having a capacitance of 10 μF. At this time, the completed dimensions of the laminated film capacitor are almost the same as those of the tantalum electrolytic capacitor and the ceramic capacitor.
【００１４】以上の点に鑑み、本発明では、小形・高耐
湿性のフィルムコンデンサとしての魅力に富む新ジ（メ
タ）アクリレートを開発し、新加工技術により小形高耐
湿性の積層フィルムコンデンサ用積層体が提供できるよ
うになったものである。In view of the above points, the present invention has developed a new di (meth) acrylate, which is attractive as a small-sized and highly moisture-resistant film capacitor, and uses a new processing technology to laminate a small and highly moisture-resistant laminated film capacitor. It is something that the body can provide.
【００１５】まず、欠点である脆く割れやすい性質に対
し、メチレン基数が７以上１３以下の鎖式炭化水素基の
両末端にアクリロイルオキシ基を付加したジアクリレー
トは炭素数の増加と供に柔軟性が増す事が分かり、さら
に重合度のコントロールが可能な紫外線を照射して、そ
の含有ビニル基の６０〜９５％を重合することで、何千
層にも積層した場合でも、積層体に僅かながら柔軟性を
持たせる事が可能となった。その結果１０ｍｍ以上の厚
さの積層体のコンデンサ加工時において、剥離や欠けに
よる静電容量低下や耐電圧低下の致命的な損傷が防止出
来るようになったものである。First of all, the diacrylate obtained by adding an acryloyloxy group to both ends of a chain hydrocarbon group having a methylene group number of 7 or more and 13 or less is flexible as the number of carbon atoms increases with respect to the drawback of being brittle and easily cracked. It can be seen that the amount of the vinyl group increases, and by irradiating with ultraviolet rays capable of controlling the degree of polymerization to polymerize 60 to 95% of the vinyl group contained, even if it is laminated in thousands, even if it is laminated in thousands, It became possible to have flexibility. As a result, when a laminated body having a thickness of 10 mm or more is processed into a capacitor, it is possible to prevent a fatal damage such as a decrease in electrostatic capacitance or a decrease in withstand voltage due to peeling or chipping.
【００１６】さらに前記ジアクリレートでは硬化収縮率
を２％以下にすることが困難であったが、環式炭化水素
基や、少なくとも一方にメチレン基数が６以下の鎖式炭
化水素基を付加した環式炭化水素基の両末端にアクリロ
イルオキシ基を付加してなるジアクリレートを単独かま
たは二種以上を併用して用い、含有ビニル基の６０〜９
５％を重合することと相まって硬化収縮率を極めて低く
抑えることが可能となり、製造時の収縮による亀裂発生
や金属基板の変形が防止でき製造が容易となった。Further, although it was difficult to reduce the curing shrinkage ratio to 2% or less with the above diacrylate, a cyclic hydrocarbon group or a ring in which a chain hydrocarbon group having a methylene group number of 6 or less is added to at least one of the rings. A diacrylate obtained by adding an acryloyloxy group to both ends of a formula hydrocarbon group is used alone or in combination of two or more types, and the content of the vinyl group is 60 to 9
Coupled with the polymerization of 5%, it is possible to suppress the curing shrinkage rate to an extremely low level, and it is possible to prevent cracking and deformation of the metal substrate due to shrinkage during manufacturing, which facilitates manufacturing.
【００１７】また、一般にジアクリレートの重合物とア
ルミニウムの真空蒸着膜との付着力・接着力は弱い。コ
ンデンサとするために、積層体を加工し、加熱により完
全に重合させた場合に硬化収縮を生じ強い内部応力が残
存する。そのため僅かな外部からの機械応力や湿気の結
露により容易にコーティング薄膜と真空蒸着膜の層間が
剥離し、その部分でさらに湿気が毛細管凝縮を起こした
り層間剥離させますますコンデンサ内に水分が蓄積され
る。その結果、アルミニウムの真空蒸着膜を腐食させ耐
湿性が悪いという問題を招く。この点に対して本発明で
は、ビニル基の残存量の多い三次元網目構造となったコ
ーティング薄膜である誘電体層の表面を、電極形成のた
めのアルミニウム原子が付着する直前に、イオン化され
た酸素原子を衝突させ、酸素原子との化学反応により表
面部だけに酸化を伴うラジカル反応を起こし、水分に対
して剥離しにくい強く付着したアルミニウムの真空蒸着
膜が得られることを見出だしたものである。その結果、
アルミニウムの真空蒸着膜を形成する最後に酸素ガスを
僅かにリークさせることによりその真空蒸着膜の表面と
裏面に厚さが２〜６ｎｍの酸化アルミニウム層が形成さ
れることと相まって耐湿性が著しく改善されたと推定さ
れる。In general, the adhesive force and the adhesive force between the diacrylate polymer and the aluminum vacuum-deposited film are weak. When the laminate is processed to be a capacitor and completely polymerized by heating, curing shrinkage occurs and strong internal stress remains. Therefore, a slight mechanical stress from the outside or dew condensation of moisture easily peels off the layer between the coating thin film and the vacuum-deposited film, causing moisture to cause capillary condensation or delamination in that part. Water accumulates in the capacitor. It As a result, the vacuum-deposited aluminum film is corroded, resulting in poor moisture resistance. On the other hand, in the present invention, the surface of the dielectric layer, which is a coating thin film having a three-dimensional network structure with a large amount of vinyl groups remaining, is ionized immediately before the attachment of aluminum atoms for electrode formation. It was discovered that oxygen atoms collide with each other, and a chemical reaction with oxygen atoms causes a radical reaction accompanied by oxidation only on the surface portion to obtain a vacuum-deposited film of aluminum that is strongly adhered and is hard to peel off against moisture. is there. as a result,
By slightly leaking oxygen gas at the end of forming a vacuum deposited film of aluminum, moisture resistance is remarkably improved in combination with the formation of an aluminum oxide layer having a thickness of 2 to 6 nm on the front and back surfaces of the vacuum deposited film. It is estimated that it was done.
【００１８】そして、不揮発性の液体を塗布して安定な
任意の厚みを得るために、一般的には増粘剤が用いられ
る。しかし、本発明では粘度が３５０センチポイズ以下
のジアクリレートを調合して、厚さに対応して用いるこ
とにより、増粘剤を用いずに静電噴霧法あるいは超音波
噴霧法により０．２〜４μｍの厚みが安定した液体薄膜
が得られる。A thickener is generally used to apply a non-volatile liquid to obtain a stable arbitrary thickness. However, in the present invention, a diacrylate having a viscosity of 350 centipoise or less is blended and used in accordance with the thickness, so that the electrostatic spraying method or the ultrasonic spraying method can be used in an amount of 0.2 to 4 μm without using a thickener. A liquid thin film having a stable thickness can be obtained.
【００１９】さらに、一般にジアクリレートの誘電体損
失角は０．０１０〜０．０２５とポリエチレンテレフタ
レートフィルムを用いたフィルムコンデンサの誘電体損
失角の０．００４に比べると高く、フィルムコンデンサ
としての魅力に欠ける。そのため、電気特性の良い材料
としてエポキシアクリレートを主成分として使用する方
法もあるが粘度が高く、低粘度のジアクリレートを加え
て調整する必要があった。その結果、電気特性が変化
し、フィルムコンデンサに不向きな特性となったり、脆
い重合物となったため耐電圧の低下を招いた。しかし、
本発明では環式炭化水素基や、少なくとも一方にメチレ
ン基数が６以下の鎖式炭化水素基を付加した環式炭化水
素基の両末端にアクリロイルオキシ基を付加してなるジ
アクリレートを単独かまたは併用して用いることにより
誘電体損失角を０．００５〜０．００８に抑えられるこ
とを見出だしたものである。さらに鎖式炭化水素基およ
び環式炭化水素基の一部の水素基をフツ素に置き換えた
とき一部の例外を除いて誘電体損失角を下げる効果を得
た。また、その一部の水素基をメチル基に置き換えたと
き強靱さを増やせそうな効果を得た。Further, the dielectric loss angle of diacrylate is generally higher than 0.010 to 0.025, which is higher than the dielectric loss angle of 0.004 of a film capacitor using a polyethylene terephthalate film, which makes it attractive as a film capacitor. Lack. Therefore, there is a method of using epoxy acrylate as a main component as a material having good electric characteristics, but it has a high viscosity, and it is necessary to adjust it by adding a low-viscosity diacrylate. As a result, the electrical characteristics changed, and the characteristics became unsuitable for film capacitors, and the resulting polymer became brittle, resulting in a decrease in withstand voltage. But,
In the present invention, a cyclic hydrocarbon group or a diacrylate obtained by adding an acryloyloxy group to both ends of a cyclic hydrocarbon group obtained by adding a chain hydrocarbon group having a methylene group number of 6 or less to at least one of It has been found that the dielectric loss angle can be suppressed to 0.005 to 0.008 by using them together. Furthermore, when some hydrogen groups of the chain hydrocarbon group and cyclic hydrocarbon group were replaced with fluorine, the dielectric loss angle was reduced with some exceptions. Moreover, when some of the hydrogen groups were replaced with methyl groups, the effect of increasing toughness was obtained.
【００２０】また、環式炭化水素基に付加する鎖式炭化
水素基のメチレン基数は増やした時、柔軟性が増加する
反面、誘電体損失角と粘度は増加し、その数を６以上に
することは意味がない。そして、鎖式炭化水素基の両端
にアクリロイルオキシ基を付加したジアクリレートにお
いても、メチレン基数を７以上に増やした場合には誘電
体損失角は徐々に良くなり柔軟性が増す傾向を示すが、
反面粘度が増加するため、メチレン基数は１３が使用す
る限界と考えられる。Further, when the number of methylene groups of the chain hydrocarbon group added to the cyclic hydrocarbon group is increased, the flexibility is increased, but the dielectric loss angle and the viscosity are increased, and the number is 6 or more. That doesn't make sense. Then, even in the case of a diacrylate in which an acryloyloxy group is added to both ends of a chain hydrocarbon group, when the number of methylene groups is increased to 7 or more, the dielectric loss angle tends to gradually improve and the flexibility tends to increase.
On the other hand, since the viscosity increases, the number of methylene groups is considered to be the limit of 13 being used.
【００２１】そして、電子線重合法を用いる場合、重合
物の安定した柔軟性を得るためには、炭化水素基の両末
端にメタクリロイルオキシ基を付加したジメタクリレー
トを少なくとも添加した方が良いことが分かった。When the electron beam polymerization method is used, in order to obtain stable flexibility of the polymer, it is preferable to add at least dimethacrylate having a methacryloyloxy group added to both ends of a hydrocarbon group. Do you get it.
【００２２】以上の発明により、小形で、高耐湿性の積
層フィルムコンデンサに用いられる積層フィルムコンデ
ンサ用積層体の提供が可能となったものである。According to the above invention, it is possible to provide a small-sized laminated body for laminated film capacitors which is used in a laminated film capacitor having high humidity resistance.
【００２３】[0023]
【実施例】（実施例１）以下本発明の一実施例について
図面を参照しながら説明する。(Embodiment 1) An embodiment of the present invention will be described below with reference to the drawings.
【００２４】図１において、１，８は保護層、２，３は
蒸着電極、４，５はパラフィンオイル薄膜、６，７はコ
ーティング薄膜である。In FIG. 1, 1 and 8 are protective layers, 2 and 3 are vapor deposition electrodes, 4 and 5 are paraffin oil thin films, and 6 and 7 are coating thin films.
【００２５】以上のように構成された積層フィルム積層
体の製造方法について説明する。まずエンドレスの金属
基板上にノナン−１，９−ジオールジアクリレートを１
００部に対し、２−イソプロポキシ−２−フェニルアセ
フェノンを５部と染料を０．５部からなる塗料を厚さ
０．２５μｍとなるように塗布し紫外線を照射し含有ビ
ニル基を６０％反応させた保護層１を５０回繰り返し形
成した。その後、厚さ７０ｎｍで幅が０．５ｍｍで４．
６ｍｍのピッチで連続した多数の帯状のパラフィンオイ
ル薄膜４を形成した後、高周波でプラズマ化した酸素原
子を全面にむら無く照射し、直ちにアルミニウムを真空
蒸着することにより帯状に分離された蒸着電極２が形成
される。その後再び全面に前述の塗料を厚さ０．２５μ
ｍとなるように塗布し紫外線を照射し含有ビニル基を１
０％反応させたコーティング薄膜６を形成させ誘電体層
となす。次に厚さ７０ｎｍで幅が０．５ｍｍで４．６ｍ
ｍのピッチで連続した多数の帯状のパラフィンオイル薄
膜５をパラフィンオイル薄膜４に対して１ｍｍずらして
形成した後、高周波でプラズマ化した酸素原子を全面に
むら無く照射し、直ちにアルミニウムを真空蒸着するこ
とにより帯状に分離された蒸着電極３が形成されコンデ
ンサの対向電極と成す。以下同様にして、コーティング
と真空蒸着を一つの真空槽の中で連続し、４３００回繰
り返し、所定の積層数に成った時、真空蒸着を停止し、
数十層コーティングのみ繰り返し、保護層８と成し、積
層フィルムコンデンサ用積層体を得た。この積層体を用
い、個別分離、リード線引き出し加工や外装等を行い、
静電容量が１０μＦで定格電圧１６Ｖの積層フィルムコ
ンデンサを製造した。A method of manufacturing the laminated film laminate having the above structure will be described. First, 1 part of nonane-1,9-diol diacrylate is coated on an endless metal substrate.
To 00 parts, a coating consisting of 5 parts of 2-isopropoxy-2-phenylacephenone and 0.5 part of a dye was applied so as to have a thickness of 0.25 μm, and ultraviolet rays were irradiated to 60% of vinyl groups contained. The reacted protective layer 1 was repeatedly formed 50 times. Then, with a thickness of 70 nm and a width of 0.5 mm, 4.
After forming a large number of strip-shaped paraffin oil thin films 4 continuous at a pitch of 6 mm, the entire surface is uniformly irradiated with oxygen atoms converted into plasma at a high frequency, and immediately aluminum is vacuum-deposited to form strip-shaped vapor deposition electrodes 2. Is formed. After that, the above-mentioned paint is applied to the entire surface again to a thickness of 0.25μ.
It is coated so that it becomes m, and ultraviolet rays are radiated to make the contained vinyl group 1
A coating thin film 6 reacted with 0% is formed to form a dielectric layer. Next, thickness 70nm and width 0.5mm 4.6m
After forming a large number of strip-shaped paraffin oil thin films 5 continuous with a pitch of m by 1 mm with respect to the paraffin oil thin films 4, the whole surface is uniformly irradiated with oxygen atoms that are turned into plasma by high frequency, and aluminum is immediately vacuum-deposited by vacuum evaporation. As a result, the vapor-deposited electrodes 3 separated into strips are formed and serve as counter electrodes of the capacitor. In the same manner, coating and vacuum deposition are continuously performed in one vacuum chamber, repeated 4300 times, and when the predetermined number of layers is reached, the vacuum deposition is stopped,
Only several tens layers of coating were repeated to form a protective layer 8 to obtain a laminated body for laminated film capacitor. Using this laminated body, individual separation, lead wire drawing process, exterior, etc.,
A laminated film capacitor having a capacitance of 10 μF and a rated voltage of 16 V was manufactured.
【００２６】（実施例２）以下本発明の第２の実施例に
ついて説明する。(Embodiment 2) A second embodiment of the present invention will be described below.
【００２７】エンドレスの金属基板上にノナン−１，９
−ジオールジメタクリレートを１００部に対し、染料を
０．５部混ぜてなる塗料を厚さ０．２５μｍとなるよう
に塗布し電子線を弱く照射し、硬化反応のむらを含み含
有ビニル基の６０〜９５％を反応させた保護層を数十回
繰り返し形成した。以下実施例１と同様にして積層フィ
ルムコンデンサ用積層体を得た。この積層体を用い、静
電容量が１０μＦで定格電圧１６Ｖの積層フィルムコン
デンサを製造した。Nonane-1,9 on an endless metal substrate
-A coating material prepared by mixing 0.5 part of a dye with 100 parts of diol dimethacrylate so as to have a thickness of 0.25 µm, and weakly irradiating with an electron beam, and containing 60 to 60% of vinyl group containing uneven curing reaction. A protective layer in which 95% was reacted was repeatedly formed several dozen times. Thereafter, a laminate for a laminated film capacitor was obtained in the same manner as in Example 1. Using this laminated body, a laminated film capacitor having a capacitance of 10 μF and a rated voltage of 16 V was manufactured.
【００２８】（実施例３）以下本発明の第３の実施例に
ついて説明する。(Embodiment 3) A third embodiment of the present invention will be described below.
【００２９】エンドレスの金属基板上にビス（アクリロ
イルオキシメチレン）−トリシクロ［５，２，１，０2,
6］デカン（化３）を１００部に対し、２−イソプ ロポ
キシ素基を付加した環式炭化水素基の両末端にアクリロ
イルオキシ基を付加してなる−２−フェニルアセトフェ
ノンを５部と染料を０．５部からなる塗料を厚さ０．８
μｍとなるように塗布し、紫外線を照射し含有ビニル基
の７０％を反応させた保護層を５０層繰り返し形成し
た。以下実施例１と同様にして真空蒸着層を１８０００
層繰り返し形成し積層フィルムコンデンサ用積層体を得
た。この積層体を用い、静電容量が１０μＦで定格電圧
５０Ｖの積層フィルムコンデンサを製造した。On an endless metal substrate, bis (acryloyloxymethylene) -tricyclo [5,2,1,0 2 ,
6 ] To 100 parts of decane (Chemical Formula 3), 5 parts of 2-phenylacetophenone obtained by adding an acryloyloxy group to both ends of a cyclic hydrocarbon group to which a 2-isopropoxyl group is added, and a dye 0.5 parts of paint with a thickness of 0.8
The protective layer was applied so as to have a thickness of μm and irradiated with ultraviolet rays to react 70% of the contained vinyl groups to repeatedly form 50 protective layers. Thereafter, in the same manner as in Example 1, a vacuum deposition layer was formed at 18000
The layers were repeatedly formed to obtain a laminate for a laminated film capacitor. Using this laminate, a laminated film capacitor having a capacitance of 10 μF and a rated voltage of 50 V was manufactured.
【００３０】[0030]
【化４】 [Chemical 4]
【００３１】（実施例４）以下本発明の第４の実施例に
ついて説明する。(Embodiment 4) A fourth embodiment of the present invention will be described below.
【００３２】エンドレスの金属基板上にノナン−１，９
−ジオールジアクリレートを５０部、ビス（アクリロイ
ルオキシメチレン）−トリシクロ［５，２，１，０2，6
デカン（化４）を５０部に対し、２−イソプロポキシ−
２−フェニルアセトフェノンを５部と染料を０．５部か
らなる塗料を厚さ０．４μｍとなるように塗布し、紫外
線を照射し含有ビニル基の９５％を反応させた保護層を
５０層繰り返し形成した。以下実施例１と同様にして真
空蒸着層を７６００層繰り返し形成し積層フィルムコン
デンサ用積層体を得た。この積層体を用い、静電容量が
１０μＦで定格電圧２５Ｖの積層フィルムコンデンサを
製造した。Nonane-1,9 on an endless metal substrate
- 50 parts of a diacrylate, bis (acryloyloxy methylene) - tricyclo [5,2,1,0 2, 6
50 parts of decane (formula 4) was added to 2-isopropoxy-
A coating consisting of 5 parts of 2-phenylacetophenone and 0.5 part of a dye was applied to a thickness of 0.4 μm and irradiated with ultraviolet rays to react 95% of the vinyl groups contained, repeating 50 layers of protective layers. Formed. Thereafter, 7600 vacuum vapor deposition layers were repeatedly formed in the same manner as in Example 1 to obtain a laminate for a laminated film capacitor. Using this laminate, a laminated film capacitor having a capacitance of 10 μF and a rated voltage of 25 V was manufactured.
【００３３】（従来例）以下従来例について説明する。(Conventional Example) A conventional example will be described below.
【００３４】厚さ１．５μｍのポリエチレンテレフタレ
ートフィルムの一方の面に、まず厚さ７０ｎｍで幅が
０．５ｍｍで４．６ｍｍピッチで連続した多数の帯状の
パラフィンオイル薄膜を形成し直ちにアルミニウムを真
空蒸着することにより帯状に分離された蒸着電極が形成
される。この後ポリエチレンテレフタレートフィルムを
反転して１．５ｍｍずらして同様に多数の帯状のパラフ
ィンオイル薄膜を形成した上にアルミニウムの真空蒸着
を行い、多数の帯状蒸着電極を有した２００００ｍの両
面金属化フィルムが製造される。続いて、この両面金属
化フィルムの片面に、ポリカーボネートと接着剤と染料
を塩素系有機溶剤で塗料化したものをリバース方式で厚
さ１μｍに全面に塗布し乾燥してコーティング薄膜が形
成されロールに巻取られる。その後反対側の面に同様に
してコーティング薄膜が形成され両面コーティング両面
金属化フィルムが製造される。この後、両面コーティン
グ両面金属化フィルムを２６０００層積層し積層フィル
ムコンデンサ用積層体を得た。この積層体を用い、静電
容量が１０μＦで定格電圧５０Ｖの積層フィルムコンデ
ンサを製造した。On one surface of a polyethylene terephthalate film having a thickness of 1.5 μm, a number of strip-shaped paraffin oil thin films having a thickness of 70 nm, a width of 0.5 mm and a pitch of 4.6 mm were first formed, and aluminum was immediately vacuumed. By vapor deposition, strip-shaped vapor deposition electrodes are formed. After this, the polyethylene terephthalate film was inverted and displaced by 1.5 mm to form a large number of strip-shaped paraffin oil thin films in the same manner, and then vacuum evaporation of aluminum was performed to obtain a 20000 m double-sided metallized film having a large number of strip-shaped vapor deposition electrodes. Manufactured. Subsequently, one side of this double-sided metallized film was coated with polycarbonate, an adhesive and a dye with a chlorine-based organic solvent to a thickness of 1 μm by the reverse method and dried to form a coating thin film on a roll. It is wound up. Thereafter, a coating thin film is similarly formed on the opposite surface to produce a double-sided coated double-sided metallized film. Then, 26000 layers of double-sided coated double-sided metallized films were laminated to obtain a laminated body for laminated film capacitors. Using this laminate, a laminated film capacitor having a capacitance of 10 μF and a rated voltage of 50 V was manufactured.
【００３５】以上実施例１，２，３，４と従来例の積層
フィルムコンデンサ各２０個の平均寸法と温度６０℃、
相対湿度９５％の雰囲気で直流定格電圧を５００時間と
１０００時間印加した後の平均静電容量変化率を（表
１）に示した。The average dimensions and the temperature of 60 ° C. for each of the laminated film capacitors of Examples 1, 2, 3, 4 and the conventional example as described above are set to 20.
The average capacitance change rate after applying the DC rated voltage for 500 hours and 1000 hours in the atmosphere of 95% relative humidity is shown in (Table 1).
【００３６】[0036]
【表１】 [Table 1]
【００３７】この（表１）から明らかなように、本方法
によると同じ５０Ｖの定格電圧で比較すると、約１／６
に小形化することが出来、さらに一層の積層に約１秒か
かるため積層時間がコスト上に大きな影響を及ぼすが、
従来例と比べると積層時間が約半分で済むため魅力は大
きい。次に、６０℃耐湿負荷試験の結果も良好であり、
優れた耐湿性を示すことが分かった。また、鎖式炭化水
素基として他のメチレン基数が７から１３までのもの、
さらに環式炭化水素基として、シクロブタン，シクロヘ
キサン，シクロヘキセン，クアドリシクロヘプタン，ス
ピロヘプタジェン，アダマンタン，ノルボルネン，トリ
シクロデカンや、それらとベンゼンやナフタレンの少な
くとも一方にメチレン基数が６以下の鎖式炭化水素基を
付加したものや、さらにそれらの水素基の一部もしくは
全てをフッ素基，メチル基，エチル基，プロピル基，イ
ソプロピル基を置き換えたものに以上について２個のア
クリロイルオキシ基やメタクリロイルオキシ基を付加し
てなるジアクリレートやジメタクリレートを単独で用い
るかまたは二種類以上を併用し粘度を３５０センチポイ
ズ以下に調整し紫外線増感剤や染料を加えたものについ
ても同様に特性の優れた積層フィルムコンデンサ用積層
体を製造できた。As is clear from this (Table 1), when compared with the same rated voltage of 50 V according to this method, about 1/6.
It is possible to reduce the size, and it takes about 1 second to stack more layers, so the stacking time has a great impact on the cost.
Compared to the conventional example, the stacking time is about half, which is attractive. Next, the results of the 60 ° C humidity resistance load test were also good,
It was found to show excellent moisture resistance. Further, other chain methylene groups having 7 to 13 methylene groups,
Further, as cyclic hydrocarbon groups, cyclobutane, cyclohexane, cyclohexene, quadricycloheptane, spiroheptagene, adamantane, norbornene, tricyclodecane, and chain hydrocarbons having methylene groups of 6 or less in at least one of them and benzene or naphthalene. Two or more acryloyloxy groups or methacryloyloxy groups are added to those with a group added, or those in which some or all of their hydrogen groups have been replaced with fluorine, methyl, ethyl, propyl, and isopropyl groups. A laminated film capacitor with excellent properties is also used in the case where the added diacrylate or dimethacrylate is used alone or in combination of two or more kinds, and the viscosity is adjusted to 350 centipoise or less and an ultraviolet sensitizer or a dye is added. The laminate for use could be manufactured.
【００３８】[0038]
【発明の効果】以上のように本発明は、表面部の酸化処
理された、（化３）で示される化合物（ただし、式中の
Ｘは水素基またはメチル基を示し、Ｒはメチレン基数７
以上１３以下の鎖式炭化水素基、炭素数４以上１２以下
の鑑識炭化水素基、少なくとも一方にメチレン基数６以
下の鎖式炭化水素基を有する炭素数４以上１２以下の環
式炭化水素基であるか、あるいはそれらの水素原子の一
部もしくは全てがハロゲン原子又はアルキル基に置換さ
れたもの）を単独あるいは２種類以上を併用したものの
含有ビニル基の６０〜９５％を反応させてなる三次元網
目構造の誘電体層と、その上に表面が酸化処理されたア
ルミニウムの真空蒸着層を交互に積層したことにより、
小形化と優れた耐湿性を実現できるようになったもので
ある。INDUSTRIAL APPLICABILITY As described above, according to the present invention, the compound represented by the chemical formula (3) whose surface is oxidized (wherein X represents a hydrogen group or a methyl group, and R represents 7 methylene groups)
A chain hydrocarbon group having 4 or more and 12 or less, a discriminative hydrocarbon group having 4 or more and 12 or less carbon atoms, or a cyclic hydrocarbon group having 4 or more and 12 or less carbon atoms having at least one chain hydrocarbon group having 6 or less methylene groups Or a combination of two or more kinds of hydrogen atoms or those in which some or all of the hydrogen atoms have been substituted with halogen atoms or alkyl groups) By alternately laminating a dielectric layer having a mesh structure and a vacuum-deposited layer of aluminum whose surface is oxidized,
It has become possible to realize miniaturization and excellent moisture resistance.
【００３９】また、本発明によると、誘電体の形成に有
機溶剤とりわけ、環境に対する悪影響が懸念されるジク
ロルメタン、トリクロルエチレン等の塩素系有機溶剤を
含めて完全に廃止できるようになる。さらに、有機溶剤
の高引火性が改善されて防爆対策が容易になり、溶剤回
収装置並びに溶剤再生装置が不要となりコストへの効果
は大である。また、本発明のジ（メタ）アクリレートを
使用した場合には、電気特性がポリエチレンテレフタレ
ートと同等以上に比誘電率の温度依存性が小さく、そし
て誘電体損失角がほぼ同じであり、フィルムコンデンサ
特有の優れた特性を示すと同時に、半田付け温度には全
く影響されない三次元架橋構造のため優れた耐熱性を示
し、リード部品や表面実装部品への切り替えが自由に出
来ることは価値がある。Further, according to the present invention, it becomes possible to completely discontinue the formation of the dielectric material including the organic solvent, especially the chlorine-based organic solvent such as dichloromethane, trichloroethylene or the like, which may adversely affect the environment. Further, the high flammability of the organic solvent is improved, the explosion-proof measure is facilitated, and the solvent recovery device and the solvent regeneration device are not required, which has a great effect on the cost. Further, when the di (meth) acrylate of the present invention is used, the electrical characteristics have a temperature dependence of the relative dielectric constant smaller than that of polyethylene terephthalate, and the dielectric loss angle is almost the same, which is characteristic of film capacitors. In addition to exhibiting excellent characteristics, the three-dimensional cross-linking structure, which is completely unaffected by the soldering temperature, exhibits excellent heat resistance, and it is valuable to be able to freely switch to lead parts and surface mount parts.
【図１】本発明の第１の実施例における積層フィルムコ
ンデンサ用積層体の断面図FIG. 1 is a cross-sectional view of a laminated body for laminated film capacitors according to a first embodiment of the present invention.
【図２】従来の積層フィルムコンデンサ用積層体の断面
図FIG. 2 is a sectional view of a conventional laminated body for laminated film capacitors.
１ 保護層 ２ 蒸着電極 ３ 蒸着電極 ４ パラフィンオイル薄膜 ５ パラフィンオイル薄膜 ６ コーティング薄膜 ７ コーティング薄膜 ８ 保護層 1 protective layer 2 vapor deposition electrode 3 vapor deposition electrode 4 paraffin oil thin film 5 paraffin oil thin film 6 coating thin film 7 coating thin film 8 protective layer
Claims (4)
の６０〜９５％を反応させてなる三次元網目構造の誘電
体層と、その上に表面が酸化処理されたアルミニウムの
真空蒸着層を交互に積層したことを特徴とした積層フィ
ルムコンデンサ用積層体。1. A dielectric layer having a three-dimensional network structure, which is obtained by reacting 60 to 95% of a vinyl group contained in the surface, whose surface is oxidized, and a vacuum-deposited aluminum layer on which the surface is oxidized. A laminated body for a laminated film capacitor, which is characterized by being alternately laminated.
だし、式中のＲはメチレン基数が７以上１３以下の鎖式
炭化水素基、炭素数４以上１２以下の環式炭化水素基、
少なくとも一方にメチレン基数６以下の鎖式炭化水素基
を有する炭素数４以上１２以下の環式炭化水素基である
か、あるいはそれらの水素原子の一部もしくは全てがハ
ロゲン原子またはアルキル基に置換されたもの）で示さ
れるアクリロイル基を二個有する化合物を単独で使用す
るか、もしくは二種類以上を併用したものと染料と紫外
線増感剤を混合してなる粘度が３５０センチポイズ以下
の液体薄膜に紫外線を照射してなるものである請求項１
記載の積層フィルムコンデンサ用積層体。 【化１】 2. The dielectric layer has the following general formula (Formula 1) (wherein R is a chain hydrocarbon group having a methylene group number of 7 or more and 13 or less, or a cyclic carbonization group having a carbon number of 4 or more and 12 or less). Hydrogen radical,
A cyclic hydrocarbon group having 4 to 12 carbon atoms having a chain hydrocarbon group having 6 or less methylene groups in at least one of them, or a part or all of the hydrogen atoms thereof are substituted with a halogen atom or an alkyl group. A compound having two acryloyl groups represented by the formula (1) or a mixture of two or more kinds of acryloyl group and a dye and a UV sensitizer and having a viscosity of 350 centipoise or less with UV light. It is obtained by irradiating with
A laminate for a laminated film capacitor as described above. [Chemical 1]
だし、式中のＸは水素またはメチル基を示し、Ｒはメチ
レン基数が７以上１３以下の鎖式炭化水素基、炭素数４
以上１２以下の環式炭化水素基、少なくとも一方にメチ
レン基数６以下の鎖式炭化水素基を有する炭素数４以上
１２以下の環式炭化水素基であるか、あるいはそれらの
水素原子の一部もしくは全てがハロゲン原子またはアル
キル基に置換されたもの）で示される（メタ）アクリロ
イル基を二個有する化合物を単独で使用するか、もしく
は二種類以上を併用したものと染料を混合してなる粘度
が３５０センチポイズ以下の液体薄膜に電子線を照射し
てなるものである請求項１記載の積層フィルムコンデン
サ用積層体。 【化２】 3. The dielectric layer has the following general formula (Formula 2) (wherein X represents hydrogen or a methyl group, and R represents a chain hydrocarbon group having 7 or more and 13 or less methylene groups, carbon). Number 4
A cyclic hydrocarbon group of 12 or more and 12 or less, a cyclic hydrocarbon group of 4 or more and 12 or less carbon atoms having a chain hydrocarbon group of 6 or less methylene groups on at least one side, or a part of hydrogen atoms thereof or A compound having two (meth) acryloyl groups represented by (all substituted with halogen atoms or alkyl groups) is used alone, or a mixture of two or more kinds and a dye has a viscosity The laminate for a laminated film capacitor according to claim 1, which is formed by irradiating a liquid thin film having a thickness of 350 centipoise or less with an electron beam. [Chemical 2]
アルミニウムの蒸発原子が付着する直前に行ったもので
ある請求項１記載の積層フィルムコンデンサ用積層体。4. The laminate for a laminated film capacitor according to claim 1, wherein the surface of the dielectric layer is subjected to an oxidation treatment under vacuum immediately before vaporized aluminum atoms are attached.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18197492A JP3173143B2 (en) | 1992-07-09 | 1992-07-09 | Laminated body for laminated film capacitor and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18197492A JP3173143B2 (en) | 1992-07-09 | 1992-07-09 | Laminated body for laminated film capacitor and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0629147A true JPH0629147A (en) | 1994-02-04 |
| JP3173143B2 JP3173143B2 (en) | 2001-06-04 |
Family
ID=16110127
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18197492A Expired - Fee Related JP3173143B2 (en) | 1992-07-09 | 1992-07-09 | Laminated body for laminated film capacitor and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3173143B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008263107A (en) * | 2007-04-13 | 2008-10-30 | Matsushita Electric Ind Co Ltd | Metallized film capacitor |
| JP2010093306A (en) * | 2002-07-01 | 2010-04-22 | Rolf Eisenring | Novel method of storing electric energy in quantum battery |
| JP2017033966A (en) * | 2015-07-28 | 2017-02-09 | ルビコン株式会社 | Manufacturing method of thin film polymer multilayer capacitor and thin film polymer multilayer capacitor |
| US9947477B2 (en) | 2014-02-10 | 2018-04-17 | Rubycon Corporation | Method of manufacturing thin-film polymer multi-layer capacitor and thin-film polymer multi-layer capacitor |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110212276B (en) * | 2014-12-01 | 2022-05-10 | 株式会社村田制作所 | Electronic device and electric element |
-
1992
- 1992-07-09 JP JP18197492A patent/JP3173143B2/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010093306A (en) * | 2002-07-01 | 2010-04-22 | Rolf Eisenring | Novel method of storing electric energy in quantum battery |
| JP2008263107A (en) * | 2007-04-13 | 2008-10-30 | Matsushita Electric Ind Co Ltd | Metallized film capacitor |
| US9947477B2 (en) | 2014-02-10 | 2018-04-17 | Rubycon Corporation | Method of manufacturing thin-film polymer multi-layer capacitor and thin-film polymer multi-layer capacitor |
| JP2017033966A (en) * | 2015-07-28 | 2017-02-09 | ルビコン株式会社 | Manufacturing method of thin film polymer multilayer capacitor and thin film polymer multilayer capacitor |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3173143B2 (en) | 2001-06-04 |
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