JPS63297434A - Production of polyether ether ketone film - Google Patents

Production of polyether ether ketone film

Info

Publication number
JPS63297434A
JPS63297434A JP13159587A JP13159587A JPS63297434A JP S63297434 A JPS63297434 A JP S63297434A JP 13159587 A JP13159587 A JP 13159587A JP 13159587 A JP13159587 A JP 13159587A JP S63297434 A JPS63297434 A JP S63297434A
Authority
JP
Japan
Prior art keywords
film
ether ketone
polyether ether
corona discharge
discharge treatment
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.)
Pending
Application number
JP13159587A
Other languages
Japanese (ja)
Inventor
Yoshiki Ochi
越智 与志貴
Mitsuo Kamura
賀村 三男
Hiroyuki Umeda
博之 梅田
Tetsuo Wakino
脇野 哲夫
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Tokuyama Corp
Original Assignee
Tokuyama Corp
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Tokuyama Corp filed Critical Tokuyama Corp
Priority to JP13159587A priority Critical patent/JPS63297434A/en
Publication of JPS63297434A publication Critical patent/JPS63297434A/en
Pending legal-status Critical Current

Links

Classifications

    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00Printed circuits
    • H05K1/02Details
    • H05K1/03Use of materials for the substrate
    • H05K1/0313Organic insulating material
    • H05K1/032Organic insulating material consisting of one material
    • H05K1/0326Organic insulating material consisting of one material containing O
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00Apparatus or processes for manufacturing printed circuits
    • H05K3/38Improvement of the adhesion between the insulating substrate and the metal
    • H05K3/381Improvement of the adhesion between the insulating substrate and the metal by special treatment of the substrate

Landscapes

  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Treatments Of Macromolecular Shaped Articles (AREA)

Abstract

PURPOSE:To obtain a polyether ether ketone film having improved adhesivity to other polymers and metals, by carrying out corona discharge treatment of a polyether ether ketone film at a temperature above the glass transition temperature and below the melting point. CONSTITUTION:The objective film can be produced by corona discharge treatment of a polyether ether ketone film having a crystallinity of preferably >=15% at a temperature above the glass transition temperature (Tg) and below the melting point (Tm) (preferably between Tg+5 deg.C and Tm-10 deg.C). The corona discharge treatment density is preferably 20-80W.min/m<2>.

Description

【発明の詳細な説明】 (産業上の利用分野) 本発明は、接着性を改良したポリエーテルエーテルケト
ンフィルムの製造方法に関する。
DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a method for producing a polyetheretherketone film with improved adhesion.

(従来の技術及び発明が解決しようとする問題点)ポリ
エーテルエーテルケトンフィルム(以下、単K FPE
EKと略す。)は、その優れた耐熱性、耐薬品性、電気
的特性によシ、耐熱絶縁材料として広範囲の利用分野が
期待されている。しかし、ポリエーテルエーテルケトン
(以下、単にPKEKと略す。)は、その化学構造から
推測されるように、他の物質との接着性に乏しく、FP
EEKと他の樹脂もしくは金属箔との接着強度は、接着
剤を用いてもそれほど強くない、このためフレキシブル
プリント基盤などの用途にFPEEKを適用することは
困難でありた。
(Problems to be solved by the prior art and the invention) Polyether ether ketone film (hereinafter referred to as single K FPE)
It is abbreviated as EK. ) is expected to be used in a wide range of fields as a heat-resistant insulating material due to its excellent heat resistance, chemical resistance, and electrical properties. However, as expected from its chemical structure, polyetheretherketone (hereinafter simply referred to as PKEK) has poor adhesion to other substances, and
The adhesive strength between EEK and other resins or metal foils is not so strong even when an adhesive is used, so it has been difficult to apply FPEEK to applications such as flexible printed circuit boards.

そこで、FPEEKの接着性を向上させるために、FP
EEKの表面を二酸化炭素、アルゴン、酸素等のガスの
雰囲気下においてプラズマ処理を行なう方法や、接着剤
との相溶性の良いモノマーをフィルム表面にプラズマ重
合する方法が知られている(特公昭61−26932号
公報)。しかし、プラズマ処理及びプラズマ重合は減圧
下で行なわれるため、操作方法及び装置上の制限が多い
。さらに、処理速度が遅いため、生産性が悪い。ま九、
プラズマ重合では、重合過程を制御することがむつかし
く、得られたフィルムの均一性に問題がある。
Therefore, in order to improve the adhesion of FPEEK,
There are known methods in which the surface of EEK is subjected to plasma treatment in an atmosphere of gases such as carbon dioxide, argon, and oxygen, and a method in which a monomer having good compatibility with the adhesive is plasma-polymerized on the film surface (Japanese Patent Publication No. 61 -26932). However, since plasma treatment and plasma polymerization are performed under reduced pressure, there are many limitations regarding operating methods and equipment. Furthermore, the processing speed is slow, resulting in poor productivity. Maku,
In plasma polymerization, it is difficult to control the polymerization process and there are problems with the uniformity of the resulting film.

一方、常圧下で行なわれるコロナ放電処理によシ、無極
性ポリマーの光面改質を行ない、接着性を向上させるこ
とは広く行なわれている。しかし、FPEEKにコロナ
放電処理を適用しても接着性の改良は十分満足し得るも
のではなかった。
On the other hand, it is widely practiced to modify the optical surface of nonpolar polymers by corona discharge treatment performed under normal pressure to improve adhesive properties. However, even when corona discharge treatment was applied to FPEEK, the improvement in adhesion was not sufficiently satisfactory.

(問題点を解決するための手段) 本発明者等は上記問題について穐々検討し次結果、FP
EEKにPEEKのガラス転位温度(以下、単にTgと
略す。〕以上、融点(以下、単にTmと略す。)の温度
条件下でコロナ放電処理を施すことによシ、上記問題点
を解決できることを見い出し、本発明を提案するに至っ
念。
(Means for solving the problem) The present inventors have thoroughly studied the above problem and found that the FP
We have found that the above-mentioned problems can be solved by subjecting EEK to corona discharge treatment at a temperature above the glass transition temperature (hereinafter simply abbreviated as Tg) of PEEK and the melting point (hereinafter simply abbreviated as Tm). Under the heading, we are inspired to propose the present invention.

すなわち、本発明は、FPEEKにPEEKのTg以上
、Tm以下の温度条件下でコロナ放電処理をすることを
特徴とするFPEEKの製造方法である。
That is, the present invention is a method for manufacturing FPEEK, characterized in that FPEEK is subjected to a corona discharge treatment under a temperature condition of not less than Tg of PEEK and not more than Tm of PEEK.

本発明に用いられるPEEKは、公知のものが何ら制限
・されず用い得る。例えば、一般式なる重合体であって
も良く、またPEEKの結晶化を粗害しない程度に上記
一般式以外の他の単位を含む共重合体でありても良い。
As the PEEK used in the present invention, any known PEEK can be used without any restriction. For example, it may be a polymer having the general formula, or it may be a copolymer containing units other than the above general formula to the extent that it does not impair the crystallization of PEEK.

他の単位としては、特に制限されるものではないが、例
えば、一般式ができる。上記の共重合体の場合には、前
記一般式ルチ以上であることが好ましい、ま次、本発明
で用いられるPEEKは、PEEKの耐熱性、耐薬品性
等の特性を損なわない範囲、例えは、30M量チ未満の
範囲で他の樹脂をブレンドし次ものであっても良い。
Other units include, but are not particularly limited to, a general formula, for example. In the case of the above-mentioned copolymer, it is preferable that the general formula is equal to or higher than that of the above general formula.Next, the PEEK used in the present invention is within a range that does not impair the properties such as heat resistance and chemical resistance of PEEK, for example, , the following may be used by blending other resins in an amount less than 30M.

かかる他の樹脂として は、ポリスルホン、ポリエーテルスルホン、ポリフェニ
レンスルフィド等が挙ケラレル。
Examples of such other resins include polysulfone, polyether sulfone, polyphenylene sulfide, and the like.

本発明に用いられるFPEEKは無延伸フィルム、−軸
延伸フィルム及び二軸延伸フィルムのいずれでも良いが
、機械的特性、耐熱性を考慮すると二軸延伸フィルムが
優れている。上記の無延伸フィルムは、溶融したPEE
Kを120℃以下に保たれ九冷却ドラム上に押し出し、
急冷することによシ製造することができる。得られたフ
ィルムは実質的に無定形フィルムである。上記の無延伸
フィルムの熱処理を行ない、結晶化を向上させることに
よって1寸法安定性を付与することもできる。また、−
軸延伸フィルム又は二軸延伸フィルムは以下のようにし
て製造することができる。上記の実質的に無定形の無延
伸フィルムを140℃〜165℃、好ましくは140℃
〜155℃の温度範囲にて、面積倍率で2倍〜10倍−
軸延伸又は二軸延伸することによシ製造する。得られ九
−軸延伸フィルム又は二軸延伸フィルムの寸法安定性、
耐熱性をよシ向上させる九めKは、緊張下、若しくは、
2oチ以下の制限収縮下において200℃以上融点以下
の温度で1〜600秒間熱処理を行なうことが好ましい
The FPEEK used in the present invention may be an unstretched film, a -axially stretched film, or a biaxially stretched film, but the biaxially stretched film is superior in terms of mechanical properties and heat resistance. The above unstretched film is made of molten PEE
K is extruded onto a nine-cooled drum kept below 120°C,
It can be manufactured by rapid cooling. The resulting film is a substantially amorphous film. One-dimensional stability can also be imparted by heat-treating the above-mentioned unstretched film to improve crystallization. Also, −
An axially stretched film or a biaxially stretched film can be produced as follows. The above substantially amorphous unstretched film is heated at 140°C to 165°C, preferably at 140°C.
In the temperature range of ~155℃, the area magnification is 2 times to 10 times.
Manufactured by axial or biaxial stretching. Dimensional stability of the resulting nine-axially stretched film or biaxially stretched film,
Nine K, which improves heat resistance, is heated under tension or
It is preferable to carry out the heat treatment at a temperature of 200° C. or more and the melting point or less for 1 to 600 seconds under limited shrinkage of 2° C. or less.

本発明に於いて、後述するコロナ放電処理に供するFP
EEKとしては、結晶化度が10チ以上、さらに15%
以上であることが他の樹脂或いは金属との良好外接着性
が得られるために好ましい。
In the present invention, FP subjected to corona discharge treatment described below
As for EEK, the crystallinity is 10 or more, and further 15%.
The above is preferable because good external adhesion with other resins or metals can be obtained.

また、フィルムの表面粗度をコントロールしたシ、機械
的強度をよシ向上させるためK FPEEKに炭カル、
シリカ、ガラス繊維、カーゲン繊維等の無機フィラーを
入れることは本発明を逸脱するものではない。
In addition, in order to control the surface roughness of the film and further improve the mechanical strength, KFPEEK is coated with charcoal,
The inclusion of inorganic fillers such as silica, glass fiber, and Kagen fiber does not depart from the scope of the present invention.

以上に述べ九FPEEKは、特定の温度条件下でコロナ
放電処理される。コロナ放電処理は、Tg以上Tm以下
の温度、好ましくはTg + 5℃からTm −10℃
の範囲で行なわれる。この範囲よシも低い温度でのコロ
ナ放電処理では、得られるFPEEKと他の樹脂又は金
属との接着強度の改善が十分ではなく、ま文、蒸着、ス
パッタリングによシ作成した金属層の蒸着強度も十分で
はない。ま次、この範囲よりも高い温度では、フィルム
が熱のために収縮し、平面性等が失なわれ、フィルムと
しての性状を失なってしまうために適当ではない。
The nine FPEEK mentioned above is subjected to corona discharge treatment under certain temperature conditions. The corona discharge treatment is performed at a temperature of Tg or higher and Tm or lower, preferably Tg + 5°C to Tm -10°C.
It is carried out within the range of Corona discharge treatment at a temperature lower than this range does not sufficiently improve the adhesive strength between the obtained FPEEK and other resins or metals, and the deposition strength of metal layers created by vapor deposition or sputtering is insufficient. is also not enough. Secondly, temperatures higher than this range are not suitable because the film shrinks due to the heat and loses its flatness and properties as a film.

コロナ放電処理密度は、その目的に応じて決定されるが
、一般的には5W’min/m” 〜20QW・min
Δ−1好ましくは、20w−m1nΔ−〜80W’ m
l n/m”の範囲から選択することが好適である。
The corona discharge treatment density is determined depending on the purpose, but is generally 5W'min/m'' to 20QW・min.
Δ-1 Preferably 20w-m1nΔ-~80W'm
It is preferable to select from the range of 1 n/m''.

コロナ放電処理は、大気中だけでなく窒素、アルゴン、
二酸化炭素などの不活性ガス下で行なうこともできるが
、得られるFPEEKの接着性の改善の点からは、窒素
ガス雰囲気下で行なうことが好ましい。
Corona discharge treatment is performed not only in the atmosphere but also in nitrogen, argon,
Although it is possible to carry out the process under an inert gas such as carbon dioxide, it is preferable to carry out the process under a nitrogen gas atmosphere from the viewpoint of improving the adhesiveness of the obtained FPEEK.

(効果) 本発明によって得られたFPEEKは、他の樹脂や金属
との接着性が極めて良好であ夛、t′fi−1金属箔と
の密着性も極めて良好である。従って、本発明によって
得られたFPEEKに銅片を積層されたフジキシグルプ
リント基板及びアルミニウムを蒸着させて得たコンデン
サーは、150℃の高温に於いても銅片及びアルミニウ
ム箔との剥離がほとんど認めら汎ない。
(Effects) FPEEK obtained by the present invention has extremely good adhesion to other resins and metals, and also has extremely good adhesion to t'fi-1 metal foil. Therefore, the Fuji Xiguru printed circuit board in which copper pieces are laminated on FPEEK obtained by the present invention and the capacitor obtained by vapor-depositing aluminum show almost no separation from the copper pieces and aluminum foil even at a high temperature of 150°C. It's not widespread.

この他、本発明によるFPKEKはその優れ次耐熱性、
耐薬品性、機械的特性及び表面物性などを利用して、フ
ィルム着面に金属組成を多く含んだ磁性層を有する磁気
テープとしても有用に使用することができる。
In addition, FPKEK according to the present invention has excellent heat resistance,
Utilizing chemical resistance, mechanical properties, surface properties, etc., it can also be usefully used as a magnetic tape having a magnetic layer containing a large amount of metal composition on the film attachment surface.

(実施例) される単位のみからなるPEEKの無延伸フィルムを横
方向に2.0倍、縦方向に2.5倍延伸し、320℃で
1分間熱処理し念結晶化度30チの二軸延伸フィルムと
、上記の無延伸フィルムを同様に熱処理し九結晶化度1
5チのFPEKKを用い念。接着強度は次のようにして
行なった。FPEEKと電解銅箔(厚み35μ)をエポ
キシ系接着剤(スリーボンド社製:スリーケンド165
0)を用いて貼り合せ、積層フィルムを作成した。該積
層フィルムラ15鱈幅に切り出し、FPEEKと銅箔と
の接着強度をT型はく離性を用いて23℃の温度下でオ
ートグラフにより測定した。蒸着強度は10−4〜1O
−5torrの減圧下において、アルミニウムi FP
EEKに1000又の膜厚に蒸着し、該蒸着面1 cm
”を1−×1−角に100個分割し、セロテープを貼り
つけ、該セロテープをはく離し、セロテープによシはぎ
取らnた個数で蒸着強度を示した。はぎ取られ次個数が
少ない方が蒸着強度が強いことを示す。
(Example) An unstretched film of PEEK consisting only of units of The stretched film and the above-mentioned unstretched film were heat-treated in the same manner to give a degree of crystallinity of 1.
Remember to use 5-inch FPEKK. Adhesive strength was measured as follows. FPEEK and electrolytic copper foil (thickness 35μ) were bonded with epoxy adhesive (manufactured by ThreeBond: ThreeKend 165).
0) to create a laminated film. The laminated film was cut out to a width of 15 mm, and the adhesive strength between FPEEK and copper foil was measured by autograph at a temperature of 23° C. using T-type peelability. Vapor deposition strength is 10-4 to 1O
Under reduced pressure of -5 torr, aluminum i FP
Vapor deposited on EEK to a film thickness of 1000 layers, 1 cm on the vapor deposition surface.
” was divided into 100 1-×1-square pieces, affixed with sellotape, peeled off the sellotape, and the deposition strength was determined by the number of pieces torn off by the sellotape. Indicates strong vapor deposition strength.

尚、二軸延伸し7’j FPEEKの結晶化度は、次の
式により求めた。
The crystallinity of biaxially stretched 7'j FPEEK was determined by the following formula.

Xc:結晶化度(%) do: FPEEKの密度(1/cm” )de:結晶
部の密度(=1.37817cm3)dl:非晶部の密
度(=1.2625,9/c!n” )手続補正書 昭和62年 6月2 日 特許庁長官   黒1)明ta  殿 1、事件の表示 昭和62年5月29日提出の特許願(1)2、発明の名
称 ポリエーテルエーテルケトンフィルムの製造方法 3、補正をする者 事件との関係 特許出願人 郵便番号 745 住  所 山口県徳山市御影町1番1号連絡先  東京
都港区西新橋1−4−5徳山曹達株式会社 東京本部 特許情報部 置 03−597−5111 4、補正の対象 明細書の「発明の詳細な説明」の欄 5、補正の内容 (+)明mW第2頁5行目 「基盤」を「基板」に訂正する。
Xc: Crystallinity (%) do: Density of FPEEK (1/cm") de: Density of crystalline part (=1.37817cm3) dl: Density of amorphous part (=1.2625, 9/c!n") ) Procedural amendment June 2, 1988 Commissioner of the Patent Office Black 1) Akita Tono 1, Indication of the case Patent application filed on May 29, 1988 (1) 2, Name of the invention Polyether ether ketone film Manufacturing method 3, relationship with the case of the person making the amendment Patent applicant postal code: 745 Address: 1-1 Mikage-cho, Tokuyama-shi, Yamaguchi Prefecture Contact: Tokuyama Soda Co., Ltd. Tokyo Headquarters, 1-4-5 Nishi-Shinbashi, Minato-ku, Tokyo Patent Information Department 03-597-5111 4. Column 5, "Detailed Description of the Invention" of the specification subject to amendment, Contents of the amendment (+) Clear mW, page 2, line 5, "base" is corrected to "substrate" do.

(2)明細書第3頁下から3行目 「損害」を「阻害」に訂正する。(2) Third line from the bottom of page 3 of the specification Correct "damage" to "hindrance."

(3)明MA書第8頁12行目 「炭カル」を「炭酸カルシウム」に訂正する。(3) Ming MA, page 8, line 12 Correct "charcoal" to "calcium carbonate".

以  上that's all

Claims (1)

【特許請求の範囲】[Claims] ポリエーテルエーテルケトンフィルムに、ポリエーテル
エーテルケトンのガラス転位温度以上、融点以下の温度
条件下でコロナ放電処理をすることを特徴とするポリエ
ーテルエーテルケトンフィルムの製造方法。
A method for producing a polyether ether ketone film, which comprises subjecting the polyether ether ketone film to a corona discharge treatment under a temperature condition that is above the glass transition temperature and below the melting point of the polyether ether ketone.
JP13159587A 1987-05-29 1987-05-29 Production of polyether ether ketone film Pending JPS63297434A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP13159587A JPS63297434A (en) 1987-05-29 1987-05-29 Production of polyether ether ketone film

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP13159587A JPS63297434A (en) 1987-05-29 1987-05-29 Production of polyether ether ketone film

Publications (1)

Publication Number Publication Date
JPS63297434A true JPS63297434A (en) 1988-12-05

Family

ID=15061731

Family Applications (1)

Application Number Title Priority Date Filing Date
JP13159587A Pending JPS63297434A (en) 1987-05-29 1987-05-29 Production of polyether ether ketone film

Country Status (1)

Country Link
JP (1) JPS63297434A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5757462A (en) * 1996-05-31 1998-05-26 Nidek Company, Ltd. Ophthalmic apparatus for photographing a section of an anterior part of an eye
JP2010070725A (en) * 2008-09-22 2010-04-02 Fujimori Kogyo Co Ltd Adhesive member, method for producing the same and adhesion structure

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5757462A (en) * 1996-05-31 1998-05-26 Nidek Company, Ltd. Ophthalmic apparatus for photographing a section of an anterior part of an eye
JP2010070725A (en) * 2008-09-22 2010-04-02 Fujimori Kogyo Co Ltd Adhesive member, method for producing the same and adhesion structure

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