JPH11236447A - Polyimide evaporated polymerized film - Google Patents
Polyimide evaporated polymerized filmInfo
- Publication number
- JPH11236447A JPH11236447A JP4157798A JP4157798A JPH11236447A JP H11236447 A JPH11236447 A JP H11236447A JP 4157798 A JP4157798 A JP 4157798A JP 4157798 A JP4157798 A JP 4157798A JP H11236447 A JPH11236447 A JP H11236447A
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- Prior art keywords
- polyimide
- vapor deposition
- vapor
- polymer film
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- Prior art date
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- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、酸無水物とジアミ
ンとの蒸着重合にて形成されるポリイミド蒸着重合膜に
関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyimide vapor-deposited polymer film formed by vapor-deposition polymerization of an acid anhydride and a diamine.
【０００２】[0002]
【従来の技術】従来酸無水物とジアミンとの蒸着重合に
て形成されるポリイミド蒸着重合膜としては、ＰＭＤＡ
（無水ピロメリット酸）／ＯＤＡ（４，４’−ジアミノ
ジフェニルエーテル）を蒸着重合して得られるものがあ
った。そしてこのようなポリイミド蒸着重合膜を基材上
に形成することによって、基材に電気絶縁性を付与して
いたものであり、特にリレーの鉄芯等の電磁材料の絶縁
被覆等に用いられていた。2. Description of the Related Art Conventionally, a polyimide vapor deposition polymer film formed by vapor deposition polymerization of an acid anhydride and a diamine is PMDA.
Some were obtained by vapor deposition polymerization of (pyromellitic anhydride) / ODA (4,4'-diaminodiphenyl ether). By forming such a polyimide vapor-deposited polymer film on a base material, the base material is provided with electrical insulation, and is used particularly for insulating coating of an electromagnetic material such as an iron core of a relay. Was.
【０００３】[0003]
【発明が解決しようとする課題】しかし上記のようなポ
リイミド蒸着重合膜は硬く脆いという性質があり、基材
上に蒸着重合膜を形成した後この基材に機械加工等を行
って外力を加えると、蒸着重合膜にひび割れが生じた
り、蒸着重合膜の剥離現象が発生したりして、基材の電
気絶縁性等の特性が低下してしまうという問題があっ
た。However, the above-mentioned polyimide vapor-deposited polymer film has the property of being hard and brittle. After forming the vapor-deposited polymer film on a substrate, the substrate is subjected to mechanical processing or the like to apply an external force. Thus, there is a problem that cracks occur in the vapor-deposited polymer film or a peeling-off phenomenon of the vapor-deposited polymer film occurs, and characteristics such as electric insulation of the base material are deteriorated.
【０００４】本発明は上記の点に鑑みてなされたもので
あり、可撓性が向上され、機械加工等の外力が作用され
た際のひび割れ、剥離等の発生が抑制された、電気絶縁
性の高いポリイミド蒸着重合膜を提供することを目的と
するものである。[0004] The present invention has been made in view of the above points, and has an improved electrical insulation property in which the occurrence of cracks and peeling when an external force such as machining is applied is suppressed. It is an object of the present invention to provide a polyimide vapor-deposited polymer film having a high value.
【０００５】[0005]
【課題を解決するための手段】本発明の請求項１に記載
のポリイミド蒸着重合膜は、上記化学式（Ａ）乃至
（Ｃ）で示される酸無水物のうち少なくとも一つと、上
記化学式（Ｄ）乃至（Ｆ）で示されるジアミンのうち少
なくとも一つとの蒸着重合にて形成されることを特徴と
するものである。The polyimide vapor-deposited polymer film according to claim 1 of the present invention comprises at least one of the acid anhydrides represented by the chemical formulas (A) to (C) and the chemical formula (D) Or (F) by vapor deposition polymerization with at least one of the diamines shown in (F).
【０００６】本発明の請求項２に記載のポリイミド蒸着
重合膜は、請求項１の構成に加えて、酸無水物として上
記化学式（Ｇ）で示される、３，３’，４，４’−ビス
フェニルテトラカルボン酸無水物を用いると共に、ジア
ミンとして上記化学式（Ｈ）で示される２，２−ビス
［４−（４−アミノフェノキシ）フェニル］プロパンを
用いて形成されたことを特徴とするものである。[0006] In addition to the constitution of claim 1, the polyimide vapor-deposited polymer film according to claim 2 of the present invention further comprises, as an acid anhydride, 3,3 ', 4,4'- represented by the above chemical formula (G). It is formed by using bisphenyltetracarboxylic anhydride and using 2,2-bis [4- (4-aminophenoxy) phenyl] propane represented by the chemical formula (H) as a diamine. It is.
【０００７】[0007]
【発明の実施の形態】以下、本発明の実施の形態を説明
する。本発明で用いる酸無水物は、下記の化学式（Ａ）
乃至（Ｃ）に示すものであり、このうち少なくとも一つ
を用いるものである。Embodiments of the present invention will be described below. The acid anhydride used in the present invention has the following chemical formula (A)
To (C), at least one of which is used.
【０００８】[0008]
【化８】 Embedded image
【０００９】[0009]
【化９】 Embedded image
【００１０】[0010]
【化１０】 Embedded image
【００１１】また本発明で用いるジアミンは、下記化学
式（Ｄ）乃至（Ｆ）で示すものであり、このうち少なく
とも一つを用いるものである。The diamine used in the present invention is represented by the following chemical formulas (D) to (F), and at least one of them is used.
【００１２】[0012]
【化１１】 Embedded image
【００１３】[0013]
【化１２】 Embedded image
【００１４】[0014]
【化１３】 Embedded image
【００１５】このような酸無水物及びジアミンの組合せ
としては、例えば下記化学式（Ｇ）で示される、３，
３’，４，４’−ビスフェニルテトラカルボン酸無水物
（ＰＭＤＡ）と、下記化学式（Ｈ）で示される２，２−
ビス［４−（４−アミノフェノキシ）フェニル］プロパ
ン（ＢＡＰＢ）との組合せを挙げることができる。As the combination of such an acid anhydride and diamine, for example, a compound represented by the following chemical formula (G):
3 ′, 4,4′-bisphenyltetracarboxylic anhydride (PMDA) and 2,2- represented by the following chemical formula (H)
Combination with bis [4- (4-aminophenoxy) phenyl] propane (BAPB) can be mentioned.
【００１６】[0016]
【化１４】 Embedded image
【００１７】本発明のポリイミド蒸着重合膜を基材上に
形成する際には、例えば図１に示すような蒸着重合装置
を用いることができる。この蒸着重合装置では、蒸着槽
１の廻りに蒸着槽用ヒーター２を、蒸着槽１を外囲する
ように設けてあり、蒸着槽１内に形成される蒸着空間３
を加熱できるようにしてある。また蒸着槽１には真空ポ
ンプ７が接続してあり、真空ポンプ７にて蒸着空間３内
を減圧できるようにしてある。When the polyimide vapor-deposited polymer film of the present invention is formed on a substrate, for example, a vapor-deposition polymerization apparatus as shown in FIG. 1 can be used. In this vapor deposition polymerization apparatus, a vapor deposition tank heater 2 is provided around a vapor deposition tank 1 so as to surround the vapor deposition tank 1, and a vapor deposition space 3 formed in the vapor deposition tank 1.
Can be heated. A vacuum pump 7 is connected to the vapor deposition tank 1 so that the pressure inside the vapor deposition space 3 can be reduced by the vacuum pump 7.
【００１８】また蒸着槽１には二つのコンダクタンス部
１１ａ、１１ｂが蒸着槽１外から蒸着空間３内に挿通し
て設けてある。このコンダクタンス部１１ａ、１１ｂは
有底円筒状に形成してあり、底部を蒸着空間３内に配置
し、開口部を蒸着槽１外に配置してある。またコンダク
タンス部１１ａ、１１ｂの蒸着空間３内に配置される部
分には複数の通過孔１０ａ、１０ｂが穿設してある。各
コンダクタンス部１１ａ、１１ｂの蒸着槽１外側の開口
にはそれぞれ原料蒸発管８ａ、８ｂを接続するものであ
り、この原料蒸発管８ａ、８ｂの廻りには原料蒸発管用
ヒーター９ａ、９ｂを原料蒸発管８ａ、８ｂを外囲する
ように設けて、原料蒸発管８ａ、８ｂを加熱できるよう
にしてある。The vapor deposition tank 1 is provided with two conductance portions 11a and 11b inserted from outside the vapor deposition tank 1 into the vapor deposition space 3. The conductance portions 11a and 11b are formed in a cylindrical shape with a bottom, and the bottom is disposed in the vapor deposition space 3 and the opening is disposed outside the vapor deposition tank 1. A plurality of passage holes 10a and 10b are formed in portions of the conductance portions 11a and 11b disposed in the vapor deposition space 3. Raw material evaporating tubes 8a and 8b are connected to the openings of the conductance portions 11a and 11b outside the vapor deposition tank 1, respectively, and the raw material evaporating tube heaters 9a and 9b are provided around the raw material evaporating tubes 8a and 8b. The tubes 8a and 8b are provided so as to surround them so that the raw material evaporating tubes 8a and 8b can be heated.
【００１９】また蒸着空間３内には外面を網状に形成す
ると共に両端部が閉じた筒状に形成した回転バレル４が
配置してある。この回転バレル４には蒸着槽１外から蒸
着空間３内に挿通する回転軸５が接続してあり、回転軸
５の蒸着槽１外側の端部にはモーター６を接続して回転
軸５をモーター６にて軸回転させて回転バレル４を回転
できるようにしてある。In the vapor deposition space 3, there is disposed a rotary barrel 4 having an outer surface formed in a net shape and having a cylindrical shape with both ends closed. The rotary barrel 4 is connected to a rotary shaft 5 inserted from outside the vapor deposition tank 1 into the vapor deposition space 3. A motor 6 is connected to an end of the rotary shaft 5 outside the vapor deposition tank 1 to connect the rotary shaft 5. The rotary barrel 4 can be rotated by rotating the shaft by a motor 6.
【００２０】このような蒸着重合装置を用いて基材Ｕに
ポリイミド蒸着重合膜を形成する方法を説明する。まず
あらかじめ一方の原料蒸発管８ａに上記（Ａ）乃至
（Ｃ）で示される酸無水物のうちの少なくとも一つのも
のから成る酸無水物Ｓを投入すると共に、他方の原料蒸
発管８ｂに上記（Ｄ）乃至（Ｆ）で示されるジアミンの
うちの少なくとも一つのものから成るジアミンＴを投入
し、また回転バレル４内に基材Ｕを投入する。そして真
空ポンプ７を作動させて蒸着空間３内を蒸着重合反応に
好適な圧力まで減圧する。ここで蒸着空間３内の圧力は
１×１０-1〜５×１０-5Ｔｏｒｒとし、この圧力条件下
で蒸着重合反応を進行させることが好ましく、更に好ま
しくは、１×１０-2〜１×１０-3Ｔｏｒｒとするもので
ある。またモーター６を作動させて回転バレル４を回転
させると共に蒸着槽用ヒーター２にて蒸着空間３内の基
材Ｕを、蒸着重合反応に好適な反応温度まで加熱する。
ここで基材Ｕは１８０〜２５０℃に加熱し、この温度条
件下で蒸着重合反応を進行させることが好ましい。A method of forming a polyimide vapor-deposited polymer film on the substrate U using such a vapor-deposition polymerization device will be described. First, an acid anhydride S composed of at least one of the acid anhydrides shown in the above (A) to (C) is previously charged into one raw material evaporating tube 8a, and the above-mentioned ( A diamine T composed of at least one of the diamines shown in D) to (F) is charged, and a substrate U is charged in the rotary barrel 4. Then, the vacuum pump 7 is operated to reduce the pressure in the vapor deposition space 3 to a pressure suitable for the vapor deposition polymerization reaction. Here, the pressure in the vapor deposition space 3 is set to 1 × 10 −1 to 5 × 10 −5 Torr, and the vapor deposition polymerization reaction is preferably allowed to proceed under this pressure condition, and more preferably 1 × 10 −2 to 1 ×. 10 −3 Torr. Further, the motor 6 is operated to rotate the rotary barrel 4, and the substrate U in the vapor deposition space 3 is heated by the vapor deposition tank heater 2 to a reaction temperature suitable for the vapor deposition polymerization reaction.
Here, it is preferable that the base material U is heated to 180 to 250 ° C., and the vapor deposition polymerization reaction proceeds under this temperature condition.
【００２１】次に各原料蒸発管８ａ、８ｂを原料蒸発管
用ヒーター９ａ、９ｂにて加熱して各原料蒸発管８ａ、
８ｂ内の酸無水物Ｓ及びジアミンＴを蒸発させる。この
とき酸無水物Ｓを蒸発させるためには酸無水物Ｓを１８
０〜３００℃まで加熱させることが好ましく、更に好ま
しくは２２０〜２６０℃とするものであり、またジアミ
ンＴを蒸発させるためにはジアミンＴを１８０〜２８０
℃まで加熱させることが好ましく、更に好ましくは２０
０〜２４０℃とするものである。このようにして蒸発さ
れた酸無水物Ｓ及びジアミンＴは、各コンダクタンス部
１１ａ、１１ｂを通じて蒸着槽１内に導入され、コンダ
クタンス部１１ａ、１１ｂの通過孔１０ａ、１０ｂを通
じて蒸着空間３内に誘導されて、基材Ｕまで達する。基
材Ｕに達した酸無水物Ｓ及びジアミンＴは基材Ｕ上で蒸
着重合反応により、ポリイミド蒸着重合膜を形成する。Next, the raw material evaporating tubes 8a and 8b are heated by the raw material evaporating tube heaters 9a and 9b, respectively.
The anhydride S and the diamine T in 8b are evaporated. At this time, in order to evaporate the acid anhydride S, 18
It is preferable to heat to 0 to 300 ° C, more preferably to 220 to 260 ° C. In order to evaporate diamine T, diamine T is heated to 180 to 280 ° C.
C., preferably 20 ° C.
0 to 240 ° C. The acid anhydride S and the diamine T thus evaporated are introduced into the vapor deposition tank 1 through the respective conductance portions 11a and 11b, and are guided into the vapor deposition space 3 through the through holes 10a and 10b of the conductance portions 11a and 11b. To the base material U. The acid anhydride S and the diamine T that have reached the substrate U form a polyimide vapor-deposited polymer film on the substrate U by a vapor deposition polymerization reaction.
【００２２】ここで蒸着重合反応によるポリイミド蒸着
重合膜の形成は、下記の反応式（Ｉ）に示すように、ま
ず酸無水物とジアミンが反応してポリアミック酸膜が形
成された後、ポリアミック酸の脱水閉環反応が進行する
ことによって行われるものである。Here, a polyimide vapor-deposited polymer film is formed by a vapor deposition polymerization reaction, as shown in the following reaction formula (I), where an acid anhydride and a diamine react to form a polyamic acid film, and then a polyamic acid film is formed. Is carried out as the dehydration ring closure reaction proceeds.
【００２３】[0023]
【化１５】 Embedded image
【００２４】ここで式中のＲ5 、Ｒ6 で示される部分は
式（Ａ）乃至（Ｆ）で示される酸無水物及びジアミンに
対応するように任意に選択されるものであり、ｎは自然
数である。このようにして形成される本発明のポリイミ
ド蒸着重合膜は膜厚を均一に形成することができるもの
であり、また可撓性が高く、ポリイミド蒸着重合膜が形
成された基材に機械加工等を行って外力を加えてもひび
割れや剥離が生じにくいものであって、電磁材料に使用
する基材に適用する際、その電気絶縁性や表面保護性を
向上することができるものである。Here, the portions represented by R 5 and R 6 in the formula are arbitrarily selected so as to correspond to the acid anhydrides and diamines represented by formulas (A) to (F), and n is It is a natural number. The polyimide vapor-deposited polymer film of the present invention thus formed can be formed to have a uniform thickness, and has high flexibility, and can be machined or the like on a substrate on which the polyimide vapor-deposited polymer film is formed. When applied to a base material used for an electromagnetic material, it is possible to improve the electrical insulation property and the surface protection property of the base material when the external force is applied to apply an external force.
【００２５】[0025]
【実施例】以下、本発明を実施例によって詳述する。 （実施例１乃至９）基材として、電磁軟鉄にプレス加工
を施して図２に示すように、幅ｄ1 ＝１３ｍｍ、奥行き
ｄ4 ＝３ｍｍ、厚みｄ5 ＝１ｍｍの基部１３の両端に、
高さｄ6 ＝３ｍｍ、厚みｄ3 ＝１ｍｍの片部１４、１４
が立設されて片部１４、１４間の寸法がｄ2 ＝１１ｍｍ
となった形状の鉄芯１２を形成し、この表面に銅めっき
及びニッケルめっきを施した。The present invention will be described below in detail with reference to examples. (Examples 1 to 9) As a base material, a magnetic soft iron was subjected to press working, and as shown in FIG. 2, at both ends of a base 13 having a width d 1 = 13 mm, a depth d 4 = 3 mm, and a thickness d 5 = 1 mm,
Pieces 14, 14 having a height d 6 = 3 mm and a thickness d 3 = 1 mm
Is set up, and the dimension between the pieces 14, 14 is d 2 = 11 mm
An iron core 12 having the following shape was formed, and its surface was subjected to copper plating and nickel plating.
【００２６】各実施例について、上記の鉄芯１２に表１
に示す酸無水物及びジアミンを用いてポリイミド蒸着重
合膜を形成した。ポリイミド蒸着重合膜を形成する際
は、酸無水物及びジアミンを各２０ｇ用い、酸無水物を
２８０℃、ジアミンを２６０℃で蒸発させて蒸着槽へ導
入し、蒸着槽内で、反応温度２３０℃、反応圧力２×１
０-2Ｔｏｒｒの条件で鉄芯１２上に表１に示す膜厚のポ
リイミド蒸着重合膜を形成した。For each of the examples, Table 1
A polyimide vapor-deposited polymer film was formed using the acid anhydride and diamine shown in (1). When forming a polyimide vapor-deposited polymer film, an acid anhydride and a diamine were used in an amount of 20 g each, the acid anhydride was evaporated at 280 ° C., and the diamine was evaporated at 260 ° C., and introduced into a vapor deposition tank. , Reaction pressure 2 × 1
A polyimide vapor-deposited polymer film having a film thickness shown in Table 1 was formed on the iron core 12 under the conditions of 0 -2 Torr.
【００２７】ここで表１中の酸無水物（Ｇ）、（Ｂ）、
（Ｃ）は、それぞれ上記化学式（Ｇ）、（Ｂ）、（Ｃ）
で示される酸無水物であり、ジアミン（Ｈ）は上記化学
式（Ｈ）で示されるジアミン、ジアミン（Ｊ）、（Ｋ）
はそれぞれ下記化学式（Ｊ）、（Ｋ）で示されるジアミ
ンである。Here, the acid anhydrides (G), (B), and
(C) is the above chemical formula (G), (B), (C)
Wherein the diamine (H) is a diamine represented by the above formula (H), a diamine (J), or (K)
Is a diamine represented by the following chemical formulas (J) and (K), respectively.
【００２８】[0028]
【化１６】 Embedded image
【００２９】[0029]
【化１７】 Embedded image
【００３０】（比較例１）酸無水物として上記化学式
（Ｇ）で示される酸無水物を用いると共に、ジアミンと
してＯＤＡ（４，４’−ジアミノジフェニルエーテル）
を用いた以外は実施例１と同様に行って、鉄芯１２に膜
厚１０μｍのポリイミド蒸着重合膜を形成した。 （初期耐電圧評価）各実施例及び比較例のポリイミド蒸
着重合膜を形成した鉄芯１２に、ウレタン被覆を施した
φ０．０４２ｍｍのリード線を２０回巻き回した後、リ
ード線の末端の被覆を剥がすと共に、鉄芯１２のポリイ
ミド蒸着重合膜を一部剥がして金属面を露出させた。こ
のような試料を各実施例及び比較例について３０個づつ
用意し、鉄芯１２の金属露出面とリード線の金属露出面
にそれぞれプローブを当て、絶縁破壊試験器（菊水電子
製、品番「ＴＯＳ８６５０」）にて電圧をスローアップ
で印加して、リーク電流が１０ｍＡのときに絶縁破壊が
生じたものとして評価した。 （機械加工後の耐電圧評価）各実施例及び比較例にて形
成したポリイミド蒸着重合膜を形成した鉄芯１２を、図
３（ａ）に示すように両端を固定治具１６に固定し、鉄
芯１２の基部１３の端部付近に成形金型１５を取着する
と共にこの成形金型１５にＬＣＰ樹脂を注入、硬化させ
て図３（ｂ）に示すように基部１２の端部付近にＬＣＰ
樹脂成形物から成るつば部１７を形成した。更に図３
（ｃ）に示すようにこの鉄芯１２の基部１３のつば部１
５に挟まれた部分に、ウレタン被覆を施したφ０．０４
２ｍｍのリード線１９を、このリード線１９に４ｇの張
力をかけながら巻線機にて１５０００ターン巻き回して
コイル１８を形成した。このような試料を各実施例及び
比較例について３０個づつ用意し、このコイル１８につ
いて、初期耐電圧評価の場合と同様にして耐電圧を評価
した。 （耐サージ電圧評価）各実施例及び比較例の鉄芯１２を
用いて、機械加工後の耐電圧評価の際と同様にコイル１
８を形成し、このコイル１８を用いてリレーを組み上げ
た。このような試料を各実施例及び比較例について３０
個づつ用意し、このリレーの接点とコイル端子との間に
サージ電圧を１．２×５０μｓｅｃ．の標準衝撃電圧波
形で、波高値を１５００Ｖから２５０Ｖ毎に上昇させて
繰り返し印加し、絶縁破壊が生じる限界値を測定した。Comparative Example 1 An acid anhydride represented by the above formula (G) was used as an acid anhydride, and ODA (4,4'-diaminodiphenyl ether) was used as a diamine.
A polyimide vapor-deposited polymer film having a film thickness of 10 μm was formed on the iron core 12 in the same manner as in Example 1 except for using. (Evaluation of Initial Withstand Voltage) After winding a urethane-coated lead wire having a diameter of 0.042 mm around the iron core 12 on which the polyimide vapor-deposited polymer film of each example and comparative example was formed 20 times, coating the end of the lead wire. Was peeled off, and a part of the polyimide vapor-deposited polymer film of the iron core 12 was peeled off to expose the metal surface. Thirty such samples were prepared for each Example and Comparative Example, and probes were applied to the exposed metal surface of the iron core 12 and the exposed metal surface of the lead wire, respectively, and a dielectric breakdown tester (manufactured by Kikusui Electronics, product number "TOS8650") )), A voltage was applied in a slow-up manner, and when the leak current was 10 mA, it was evaluated that dielectric breakdown had occurred. (Evaluation of withstand voltage after machining) The iron core 12 on which the polyimide vapor-deposited polymer film formed in each Example and Comparative Example was formed was fixed at both ends to a fixing jig 16 as shown in FIG. A molding die 15 is attached near the end of the base 13 of the iron core 12, and an LCP resin is injected into the molding die 15 and hardened to form a resin near the end of the base 12 as shown in FIG. LCP
A flange portion 17 made of a resin molded product was formed. Further FIG.
As shown in (c), the collar 1 of the base 13 of the iron core 12
Urethane coating is applied to the portion sandwiched between 5 and φ0.04
A 2 mm lead wire 19 was wound 15,000 turns with a winding machine while applying a tension of 4 g to the lead wire 19 to form a coil 18. Thirty such samples were prepared for each Example and Comparative Example, and the withstand voltage of the coil 18 was evaluated in the same manner as in the initial withstand voltage evaluation. (Evaluation of surge withstand voltage) Using the iron cores 12 of the respective examples and comparative examples, the coil 1 was used in the same manner as in the evaluation of the withstand voltage after machining.
8 was formed, and a relay was assembled using the coil 18. Such a sample was prepared for each Example and Comparative Example by 30.
And a surge voltage of 1.2 × 50 μsec. Between the contact of the relay and the coil terminal. In the standard impulse voltage waveform, the peak value was repeatedly increased from 1500 V every 250 V and applied repeatedly, and a limit value at which dielectric breakdown occurred was measured.
【００３１】以上の結果を表１に示す。Table 1 shows the above results.
【００３２】[0032]
【表１】 [Table 1]
【００３３】表１から判るように、比較例１では初期耐
電圧と比較して機械加工後の耐電圧が低下し、また耐サ
ージ電圧も実施例１乃至９のものよりも低く、鉄芯１２
の固定治具１６への固定、成形金型１５の取着、リード
線１９の巻き回し等の機械加工による外力によって、ポ
リイミド蒸着重合膜のひび割れや剥離が生じ、鉄芯１２
の電気的絶縁性が低下したものである。それに対して実
施例１乃至９のものでは、初期耐電圧と機械加工後の耐
電圧との差はほとんどなく、また耐サージ電圧も比較例
１のものよりも高いものであり、本発明のポリイミド蒸
着重合膜の高い可撓性により機械加工により外力がかけ
られた後もポリイミド蒸着重合膜のひび割れや剥離の発
生が抑制され、鉄芯１２の電気的絶縁性を維持すること
ができたことが確認できた。As can be seen from Table 1, in Comparative Example 1, the withstand voltage after machining was lower than the initial withstand voltage, and the surge withstand voltage was also lower than those in Examples 1 to 9;
Is fixed to the fixing jig 16, the molding die 15 is attached, the lead wire 19 is wound, or the like.
The electrical insulation property of the metal was reduced. On the other hand, in Examples 1 to 9, there is almost no difference between the initial withstand voltage and the withstand voltage after machining, and the surge withstand voltage is higher than that of Comparative Example 1. Due to the high flexibility of the vapor-deposited polymer film, the occurrence of cracking and peeling of the polyimide vapor-deposited polymer film was suppressed even after an external force was applied by machining, and the electrical insulation of the iron core 12 could be maintained. It could be confirmed.
【００３４】[0034]
【発明の効果】上記のように本発明のポリイミド蒸着重
合膜は、上記化学式（Ａ）乃至（Ｃ）で示される酸無水
物のうち少なくとも一つと、上記化学式（Ｄ）乃至
（Ｆ）で示されるジアミンのうち少なくとも一つとの蒸
着重合にて形成されるため、可撓製が高く、このポリイ
ミド蒸着重合膜を形成した基材に機械加工等を施して外
力を加えた際のポリイミド蒸着重合膜のひび割れや剥離
の発生を抑制することができ、基材として電磁材料を用
いたときの基材の電気的絶縁性を向上することができる
ものである。As described above, the polyimide vapor-deposited polymer film of the present invention has at least one of the acid anhydrides represented by the chemical formulas (A) to (C) and the chemical formulas (D) to (F). Since it is formed by vapor deposition polymerization with at least one of the diamines, it is highly flexible, and is a polyimide vapor-deposited polymer film obtained by subjecting a substrate on which the polyimide vapor-deposited polymer film is formed to mechanical processing or the like to apply an external force. This can suppress the occurrence of cracks and peeling, and can improve the electrical insulation of the base material when an electromagnetic material is used as the base material.
【図１】本発明のポリイミド蒸着重合膜を形成するため
に用いる蒸着重合装置の一例を示す断面図である。FIG. 1 is a sectional view showing an example of a vapor deposition polymerization apparatus used to form a polyimide vapor deposition polymerization film of the present invention.
【図２】実施例１乃至９及び比較例１にて用いた鉄芯を
示す斜視図である。FIG. 2 is a perspective view showing an iron core used in Examples 1 to 9 and Comparative Example 1.
【図３】（ａ）乃至（ｃ）は、同上の鉄芯からコイルを
形成する各工程を示す正面図である。FIGS. 3 (a) to 3 (c) are front views showing respective steps of forming a coil from the above iron core.
Claims (2)
酸無水物のうち少なくとも一つと、下記化学式（Ｄ）乃
至（Ｆ）で示されるジアミンのうち少なくとも一つとの
蒸着重合にて形成されることを特徴とするポリイミド蒸
着重合膜。 【化１】 【化２】 【化３】 【化４】 【化５】 【化６】 1. A method comprising forming at least one of the acid anhydrides represented by the following chemical formulas (A) to (C) and at least one of the diamines represented by the following chemical formulas (D) to (F) by vapor deposition polymerization. A polyimide-deposited polymer film, characterized in that it is formed. Embedded image Embedded image Embedded image Embedded image Embedded image Embedded image
る、３，３’，４，４’−ビスフェニルテトラカルボン
酸無水物を用いると共に、ジアミンとして下記化学式
（Ｈ）で示される２，２−ビス［４−（４−アミノフェ
ノキシ）フェニル］プロパンを用いて形成されたことを
特徴とする請求項１に記載のポリイミド蒸着重合膜。 【化７】 2. An acid anhydride comprising 3,3 ', 4,4'-bisphenyltetracarboxylic anhydride represented by the following chemical formula (G) and a diamine represented by the following chemical formula (H): 2. The polyimide vapor-deposited polymer film according to claim 1, wherein the film is formed using 2,2-bis [4- (4-aminophenoxy) phenyl] propane. Embedded image
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4157798A JPH11236447A (en) | 1998-02-24 | 1998-02-24 | Polyimide evaporated polymerized film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4157798A JPH11236447A (en) | 1998-02-24 | 1998-02-24 | Polyimide evaporated polymerized film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH11236447A true JPH11236447A (en) | 1999-08-31 |
Family
ID=12612308
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4157798A Pending JPH11236447A (en) | 1998-02-24 | 1998-02-24 | Polyimide evaporated polymerized film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH11236447A (en) |
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|---|---|---|---|---|
| US7279543B2 (en) | 2002-09-06 | 2007-10-09 | Ulvac, Inc. | Anti-bacterial polymer and method for the preparation thereof, anti-bacterial polymer film and method for the preparation thereof, and article having such a film on the surface thereof |
| WO2014199724A1 (en) * | 2013-06-14 | 2014-12-18 | ソマール株式会社 | Solvent soluble polyimide copolymer |
| WO2014199723A1 (en) * | 2013-06-14 | 2014-12-18 | ソマール株式会社 | Polyimide copolymer oligomer, polyimide copolymer, and method for producing each of same |
| JP2015074867A (en) * | 2013-10-11 | 2015-04-20 | ソマール株式会社 | Polyimide fiber and method of producing polyimide fiber |
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1998
- 1998-02-24 JP JP4157798A patent/JPH11236447A/en active Pending
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| US7279543B2 (en) | 2002-09-06 | 2007-10-09 | Ulvac, Inc. | Anti-bacterial polymer and method for the preparation thereof, anti-bacterial polymer film and method for the preparation thereof, and article having such a film on the surface thereof |
| KR20160019554A (en) * | 2013-06-14 | 2016-02-19 | 소마아루 가부시끼가이샤 | Polyimide copolymer oligomer, polyimide copolymer, and method for producing each of same |
| WO2014199723A1 (en) * | 2013-06-14 | 2014-12-18 | ソマール株式会社 | Polyimide copolymer oligomer, polyimide copolymer, and method for producing each of same |
| JP2015000939A (en) * | 2013-06-14 | 2015-01-05 | ソマール株式会社 | Solvent soluble polyimide copolymer |
| JP2015000938A (en) * | 2013-06-14 | 2015-01-05 | ソマール株式会社 | Polyimide copolymer oligomer, polyimide copolymer and method for producing thereof |
| CN105324414A (en) * | 2013-06-14 | 2016-02-10 | 索马龙株式会社 | Solvent soluble polyimide copolymer |
| CN105324415A (en) * | 2013-06-14 | 2016-02-10 | 索马龙株式会社 | Polyimide copolymer oligomer, polyimide copolymer, and method for producing each of same |
| WO2014199724A1 (en) * | 2013-06-14 | 2014-12-18 | ソマール株式会社 | Solvent soluble polyimide copolymer |
| KR20160021237A (en) * | 2013-06-14 | 2016-02-24 | 소마아루 가부시끼가이샤 | Solvent soluble polyimide copolymer |
| TWI636074B (en) * | 2013-06-14 | 2018-09-21 | 日商索瑪爾股份有限公司 | Polyimine copolymer oligomer, polyimine copolymer, and the method of manufacturing the same |
| US10246555B2 (en) | 2013-06-14 | 2019-04-02 | Somar Corporation | Polyimide copolymer oligomer, polyimide copolymer, and method for producing each of same |
| US10308766B2 (en) | 2013-06-14 | 2019-06-04 | Somar Corporation | Solvent soluble polyimide copolymer |
| JP2015074867A (en) * | 2013-10-11 | 2015-04-20 | ソマール株式会社 | Polyimide fiber and method of producing polyimide fiber |
| JP2015074866A (en) * | 2013-10-11 | 2015-04-20 | ソマール株式会社 | Polyimide fiber and aggregate |
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