JPH093221A - Highly adhesive polyimide film - Google Patents
Highly adhesive polyimide filmInfo
- Publication number
- JPH093221A JPH093221A JP7152836A JP15283695A JPH093221A JP H093221 A JPH093221 A JP H093221A JP 7152836 A JP7152836 A JP 7152836A JP 15283695 A JP15283695 A JP 15283695A JP H093221 A JPH093221 A JP H093221A
- Authority
- JP
- Japan
- Prior art keywords
- polyimide film
- treatment
- coupling agent
- film
- highly adhesive
- 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
Links
Landscapes
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
- Treatments Of Macromolecular Shaped Articles (AREA)
- Manufacturing Of Printed Wiring (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は高接着性ポリイミドフィ
ルム、特にはポリイミドフィルムと接着剤との間に優れ
た接着性を有する高接着性ポリイミドフィルムに関する
ものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a highly adhesive polyimide film, and more particularly to a highly adhesive polyimide film having excellent adhesiveness between the polyimide film and the adhesive.
【０００２】[0002]
【従来の技術】フレキシブル印刷配線板のベースフィル
ムは高い耐熱性と優れた電気・機械特性を備えているこ
とが好ましいことから、これには一般にポリイミドフィ
ルムが用いられており、このものはこれらの基材フィル
ムと銅箔とを接着剤を介して積層一体化したものをベー
スとしたものとされている。そして、このフレキシブル
印刷配線板には接着性、耐熱性、耐薬品性、電気特性が
要求されているが、エレクトロニクスの高性能化に伴な
うフレキシブル印刷配線板のファインパターン化、高密
度化の進行に伴なって、これには接着性がより重要なも
のになってきている。2. Description of the Related Art Since it is preferable that the base film of a flexible printed wiring board has high heat resistance and excellent electrical and mechanical properties, a polyimide film is generally used for the base film. It is based on a base film and a copper foil which are laminated and integrated via an adhesive. Adhesiveness, heat resistance, chemical resistance, and electrical characteristics are required for this flexible printed wiring board. As it progresses, adhesion is becoming more important for this.
【０００３】[0003]
【発明が解決しようとする課題】しかし、このポリイミ
ドフィルムは一般的には接着性の乏しいものであり、こ
れをフレキシブル印刷配線用基板のベースフィルムとし
て用いると、ポリイミドと接着剤の界面に剥離が起こっ
て、引き剥し強度が低くなってしまうという欠点があ
り、これを改善するためにアルカリエッチング、シラン
カップリング剤による処理を行なって、この剥離を接着
剤の凝集破壊に移行させるという試みもなされており
（特開平 6-32926号、特開平 6-33653号各公報参照）、
これらの方法によれば接着性の改善は見られるけれど
も、これにはポリイミドフィルム表面に活性基が乏し
く、化学的な結合が不十分であるために接着性において
未だ十分な値が得られていないという問題点がある。However, this polyimide film generally has poor adhesiveness, and when it is used as a base film of a substrate for flexible printed wiring, peeling occurs at the interface between the polyimide and the adhesive. However, there is a drawback that the peel strength becomes low, and in order to improve this, alkali etching and treatment with a silane coupling agent are carried out, and an attempt is made to transfer this peeling to cohesive failure of the adhesive. (See JP-A-6-32926 and JP-A-6-33653).
Although the adhesiveness is improved by these methods, the adhesiveness has not yet been sufficiently obtained due to insufficient active groups on the polyimide film surface and insufficient chemical bonding. There is a problem.
【０００４】[0004]
【課題を解決するための手段】本発明はこのような不
利、問題点を解決した高接着性ポリイミドフィルムに関
するものであり、これはポリイミドフィルムの表面に表
面活性化処理を施した後、この表面活性処理面にカップ
リング剤を塗布してなることを特徴とするものである。The present invention relates to a highly adhesive polyimide film which solves the above disadvantages and problems, which is obtained by subjecting the surface of a polyimide film to a surface activation treatment and then the surface treatment. It is characterized in that a coupling agent is applied to the active treatment surface.
【０００５】すなわち、本発明者らはポリイミドフィル
ムと接着剤との間に優れた接着性を有する高接着ポリイ
ミドフィルムを開発すべく種々検討した結果、これにつ
いてはまずポリイミドフィルムの表面を低温プラズマ処
理、コロナ放電処理、紫外線処理などによって表面活性
化処理したのち、ついでこの表面活性化処理面にカップ
リング剤を塗布したところ、ポリイミドフィルムと接着
剤との間の剥離強度が大きくなり、半田耐熱性も向上す
ることを見出して本発明を完成させた。以下にこれをさ
らに詳述する。That is, as a result of various investigations by the present inventors to develop a highly adhesive polyimide film having excellent adhesiveness between the polyimide film and the adhesive, firstly, the surface of the polyimide film was treated with a low temperature plasma. After surface activation treatment such as corona discharge treatment, ultraviolet treatment, etc., and then applying a coupling agent to this surface activation treated surface, the peel strength between the polyimide film and the adhesive increases and the solder heat resistance The present invention has been completed by finding that it also improves. This will be described in more detail below.
【０００６】[0006]
【作用】本発明は高接着性ポリイミドフィルムに関する
ものであり、これは前記したようにポリイミドフィルム
の表面に表面活性化処理を施したのち、この表面活性化
処理面にカップリング剤を塗布してなるものである。本
発明に使用されるポリイミドフィルムは従来公知のもの
でよく、したがってテトラカルボン酸二無水物と芳香族
ジアミンとの反応から得られる。これには例えばピロメ
リット酸二無水物と４，４’−ジアミノジフェニルエー
テル、３，３’，４，４’−ビフェニルテトラカルボン
酸二無水物とｐ−フェニレンジアミンを主成分とするポ
リイミドフィルム等が例示される。The present invention relates to a highly adhesive polyimide film, which comprises subjecting the surface of a polyimide film to a surface activation treatment as described above and then applying a coupling agent to the surface activation treated surface. It will be. The polyimide film used in the present invention may be any known in the art and is therefore obtained from the reaction of a tetracarboxylic dianhydride and an aromatic diamine. For example, a polyimide film containing pyromellitic dianhydride and 4,4′-diaminodiphenyl ether, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride and p-phenylenediamine as main components, and the like. It is illustrated.
【０００７】また、このポリイミドフィルム表面の表面
活性化処理は低温プラズマ処理、コロナ放電処理、紫外
線処理で活性化した無機ガスでポリイミドフィルムの片
面または両面を処理すればよく、これによればポリイミ
ドフィルムの表面を容易に活性化処理することができ
る。The surface activation treatment of the polyimide film may be performed by treating one or both sides of the polyimide film with an inorganic gas activated by low temperature plasma treatment, corona discharge treatment, or ultraviolet treatment. The surface can be easily activated.
【０００８】この低温プラズマ処理の方法は、減圧可能
な低温プラズマ処理装置内にポリイミドフィルムを入
れ、装置内を無機ガスの雰囲気として圧力を 0.001〜10
Torr、好ましくは0.01〜１Torrに保持した状態で電極間
に 0.1〜10kVの直流あるいは交流を印加してグロー放電
させることにより無機ガスの低温プラズマを発生させ、
このフィルムを順次移動させながらその表面を連続的に
プラズマ処理すればよいが、この処理時間は概ね 0.1〜
100秒とすればよい。なお、この無機ガスとしてはヘリ
ウム、ネオン、アルゴンなどの不活性ガス、または酸
素、一酸化炭素、二酸化炭素、アンモニア、空気を使用
すればよいが、これらは１種に限らず、二種以上を混合
して使用してもよい。This low-temperature plasma treatment method is such that a polyimide film is placed in a low-temperature plasma treatment apparatus capable of reducing the pressure, and the inside of the apparatus is set to an atmosphere of inorganic gas at a pressure of 0.001-10.
A low temperature plasma of an inorganic gas is generated by applying a direct current or an alternating current of 0.1 to 10 kV between the electrodes while maintaining it at Torr, preferably 0.01 to 1 Torr, to perform glow discharge,
The surface of the film may be continuously plasma-treated while sequentially moving the film.
It should be 100 seconds. As the inorganic gas, an inert gas such as helium, neon, or argon, or oxygen, carbon monoxide, carbon dioxide, ammonia, or air may be used, but these are not limited to one type, and two or more types may be used. You may mix and use.
【０００９】また、このコロナ放電処理の方法は、ポリ
イミドフィルムを支えるローラーとこれに対抗して設置
した電極との間に高電圧を加えてコロナ放電を起こさ
せ、この間に表面処理するフィルム面を上にして順次表
面処理を行えばよく、このときの処理条件は周波数１〜
150kHz、出力 0.5〜40kW、処理時間 0.001〜１秒とすれ
ばよいが、この無機ガスとしてはヘリウム、ネオン、ア
ルゴンなどの不活性ガス、または酸素、一酸化炭素、二
酸化炭素、アンモニア、空気を使用すればよく、これら
は１種に限らず、２種以上を混合して使用してもよい。Further, in this corona discharge treatment method, a high voltage is applied between a roller supporting a polyimide film and an electrode installed opposite thereto to cause corona discharge, and during this period, the surface of the film to be surface treated is treated. The surface treatment may be performed sequentially with the upper side set, and the treatment conditions at this time are frequency 1 to
150kHz, output 0.5 to 40kW, processing time 0.001 to 1 second may be used, but as this inorganic gas, inert gas such as helium, neon, or argon, or oxygen, carbon monoxide, carbon dioxide, ammonia, or air is used. It suffices to do so, and these are not limited to one type, and two or more types may be mixed and used.
【００１０】さらに、この紫外線処理の方法は、波長 1
80〜280nm の低圧水銀灯を用いてこの紫外光を連続的に
ポリイミドフィルムに照射すればよいが、この際の処理
条件は処理温度２〜 150℃、処理時間１〜 100秒とすれ
ばよい。このとき無機ガスの雰囲気下で行うことが好ま
しく、無機ガスはヘリウム、ネオン、アルゴンなどの不
活性ガス、または酸素、一酸化炭素、二酸化炭素、アン
モニア、空気が使用できるが、これらは１種に限らず、
二種以上を混合して使用してもよい。その中では低温プ
ラズマ処理による活性化処理が好ましい。Further, the method of this ultraviolet treatment has a wavelength of 1
The polyimide film may be continuously irradiated with this ultraviolet light by using a low-pressure mercury lamp of 80 to 280 nm, and the treatment conditions at this time may be a treatment temperature of 2 to 150 ° C. and a treatment time of 1 to 100 seconds. At this time, it is preferable to carry out in an atmosphere of an inorganic gas, and as the inorganic gas, an inert gas such as helium, neon, or argon, or oxygen, carbon monoxide, carbon dioxide, ammonia, or air can be used. Not limited to
You may use it in mixture of 2 or more types. Among them, activation treatment by low temperature plasma treatment is preferable.
【００１１】このようにしてその表面が活性化処理され
たポリイミドフィルムについては、ついでこの活性化処
理面にカップリング剤が塗布される。活性処理面にカッ
プリング剤を塗布することにより、フィルム表面に存在
する基とカップリング剤との間に架橋反応が起こる。こ
こに使用されるカップリング剤としてはシラン系カップ
リング剤、チタネート系カップリング剤が挙げられる
が、このシラン系カップリング剤としてはγ−グリシド
キシプロピルトリメトキシシラン、γ−グリシドキシプ
ロピルジエトキシシラン、β−（３，４−エポキシシク
ロヘキシル）エチルトリメトキシシラン等のエポキシシ
ラン系、ビニルトリクロルシラン、ビニルトリス（β−
メトキシエトキシ）シラン、ビニルトリエトキシシラ
ン、ビニルトリメトキシシラン等のビニルシラン系、γ
−メタクリロキシプロピルトリメトキシシラン等のアク
リルシラン系、Ｎ−β（アミノエチル）−γ−アミノプ
ロピルトリメトキシシラン、Ｎ−β−（アミノエチル）
−γ−アミノプロピルメチルジメトキシシラン、γ−ア
ミノプロピルトリエトキシシラン、Ｎ−フェニル−γ−
アミノプロピルトリメトキシシラン等のアミノシラン
系、γ−メルカプトプロピルトリメトキシシラン、γ−
クロロプロピルトリメトキシシラン等が例示される。ま
た、チタネート系カップリング剤としてはイソプロピル
トリイソステアロイルチタネート、イソプロピルトリデ
シルベンゼンスルホニルチタネート、イソプロピルトリ
ス（ジオクチルパイロホスフェート）チタネート、テト
ライソプロピルビス（ジオクチルホスファイト）チタネ
ート、テトラ（２，２−ジアリルオキシメチル−１−ブ
チル）ビス（ジ−トリデシル）ホスファイトチタネー
ト、ビス（ジオクチルパイロホスフェート）オキシアセ
テートチタネート、ビス（ジオクチルパイロホスフェー
ト）エチレンチタネート、イソプロピルトリオクタノイ
ルチタネート、イソプロピルトリクミルフェニルチタネ
ート等が例示される。With respect to the polyimide film whose surface has been activated in this way, a coupling agent is then applied to this activated surface. By applying the coupling agent to the active treatment surface, a crosslinking reaction occurs between the groups present on the film surface and the coupling agent. Examples of the coupling agent used here include a silane coupling agent and a titanate coupling agent. Examples of the silane coupling agent include γ-glycidoxypropyltrimethoxysilane and γ-glycidoxypropyl. Epoxysilanes such as diethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, vinyltrichlorosilane, vinyltris (β-
(Methoxyethoxy) silane, vinyltriethoxysilane, vinyltrimethoxysilane and other vinylsilanes, γ
-Acrylic silanes such as methacryloxypropyltrimethoxysilane, N-β (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β- (aminoethyl)
-Γ-aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-
Aminosilanes such as aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-
Examples include chloropropyltrimethoxysilane and the like. Further, as titanate coupling agents, isopropyltriisostearoyl titanate, isopropyltridecylbenzenesulfonyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, tetraisopropyl bis (dioctyl phosphite) titanate, tetra (2,2-diallyloxymethyl) Examples include -1-butyl) bis (di-tridecyl) phosphite titanate, bis (dioctyl pyrophosphate) oxyacetate titanate, bis (dioctyl pyrophosphate) ethylene titanate, isopropyl trioctanoyl titanate, and isopropyl tricumylphenyl titanate. .
【００１２】これらの中ではシラン系カップリング剤に
ついてはエポキシシラン系、アミノシラン系のカップリ
ング剤が好ましく、チタネート系カップリング剤につい
てはアルコキシチタネート系、オキシアセテートチタネ
ート系のカップリング剤が好ましいものとされ、これら
はその１種を使用してもよいし、２種以上を併用しても
よい。Among these, epoxysilane-based and aminosilane-based coupling agents are preferred as the silane-based coupling agent, and alkoxy titanate-based and oxyacetate titanate-based coupling agents are preferred as the titanate-based coupling agent. These may be used alone or in combination of two or more.
【００１３】このカップリング剤のフィルム上の塗布は
これをそのまま塗布する乾式法でもよいが、これはカッ
プリング剤の所定量を水系または水−アルコール系溶媒
で0.05〜５wt％に希釈して塗布する湿式法としてもよ
く、このアルコール系溶媒としてはメタノール、エタノ
ール、イソプロピルアルコールなどの低級アルコールが
あげられる。この場合、水／アルコールの比率は 0/100
〜20/80 とするとよい。この乾式法、湿式法はいずれも
バーコーター、スプレーなどで塗布すればよく、湿式法
ではついで溶剤を乾燥すればよい。The coating of the coupling agent on the film may be carried out by a dry method in which it is applied as it is, but this is carried out by diluting a predetermined amount of the coupling agent with an aqueous or water-alcohol solvent to 0.05 to 5 wt%. The wet method may be used, and examples of the alcohol solvent include lower alcohols such as methanol, ethanol and isopropyl alcohol. In this case, the water / alcohol ratio is 0/100
~ 20/80 is recommended. Both the dry method and the wet method may be applied by a bar coater, a spray, or the like, and the wet method may be followed by drying the solvent.
【００１４】なお、このカップリング剤の処理量は処理
面の表面積に対して 0.1g/m2未満では処理が不十分とな
り、本発明の目的である接着剤の向上が顕著にみられ
ず、５g/m2を超えるとカップリング剤層が厚くなってし
まって、フィルムの耐熱性、接着性が低下するので、こ
れは 0.1〜５g/m2とすることがよいが、これは好ましく
は 0.3〜３g/m2とすることがよく、これによれば接着剤
の組成に関係なく高接着性を有するポリイミドフィルム
を得ることができる。この様にカップリング剤の塗布さ
れたポリイミドフィルムは、フレキシブル銅張積層板、
カバーレイフィルム等の電子部品に利用される。If the amount of the coupling agent to be treated is less than 0.1 g / m 2 with respect to the surface area of the treated surface, the treatment will be insufficient, and the improvement of the adhesive, which is the object of the present invention, will not be noticeable. it exceeds 5 g / m 2 and got coupling agent layer is thicker, the heat resistance of the film, because the adhesion decreases, this is a good be 0.1-5 g / m 2, which is preferably 0.3 It is preferable that the amount is ˜3 g / m 2, which makes it possible to obtain a polyimide film having high adhesiveness regardless of the composition of the adhesive. In this way, the polyimide film coated with the coupling agent is a flexible copper clad laminate,
Used for electronic parts such as coverlay film.
【００１５】[0015]
【実施例】つぎに本発明の実施例、比較例をあげるが、
例中における物性値はつぎの測定方法による測定値を示
したものである。 （剥離強度測定法）JIS C6481 に準拠して、サンプルを
10mm幅に切断し、90°方向に50mm／分の速度でフィルム
側に引き剥がしたときの力を測定する。 （半田耐熱性測定法）JIS C6481 に準拠して、サンプル
を25mm角に切断し、フロー半田上に30秒間浮かべ、膨
れ、剥がれなどが生じない最高温度を測定する。EXAMPLES Examples of the present invention and comparative examples will now be described.
The physical property values in the examples are the values measured by the following measuring methods. (Peeling strength measurement method) The sample is compliant with JIS C6481.
Measure the force when the film is cut into a width of 10 mm and peeled to the film side at a speed of 50 mm / min in the 90 ° direction. (Solder heat resistance measurement method) In accordance with JIS C6481, the sample is cut into 25 mm squares and the maximum temperature at which flow solder does not float, swell, or peel for 30 seconds is measured.
【００１６】実施例１ 厚さが25μｍのポリイミドフィルム・カプトン 100Ｈ
（米国デュポン社製商品名）を、真空度 0.1Torr以下、
酸素流量 1.0Ｌ／分、印加電圧２kV、周波数110kHz、出
力30kW、ラインスピード50ｍ／分で電極４本を円筒状に
配置したプラズマ発生装置の電極の外側40mmのところに
配置し、このポリイミドフィルムを低温プラズマ処理し
てその表面に表面活性化処理を施した。Example 1 Polyimide film Kapton 100H having a thickness of 25 μm
(Product name manufactured by DuPont, USA), vacuum degree 0.1 Torr or less,
Oxygen flow rate of 1.0 L / min, applied voltage of 2 kV, frequency of 110 kHz, output of 30 kW, line speed of 50 m / min. 4 electrodes were placed 40 mm outside the electrode of a plasma generator in a cylindrical shape, and this polyimide film was placed. The surface was subjected to a low temperature plasma treatment and a surface activation treatment.
【００１７】ついで、このポリイミドフィルムのプラズ
マ処理を施した面の上に、メタノール／水（重量比90／
10）の混合溶液で５wt％溶液に希釈したγ−グリシドキ
シプロピルトリメトキシシランをアプリケーターによ
り、フィルム面に対しカップリング剤の量として 0.5g/
m2塗布し、80℃で５分間乾燥し、このようにして得た処
理済みのポリイミドフィルム２枚の間にボンデングシー
トＥ33［信越化学工業（株）製商品名、エポキシ−ＮＢ
Ｒ系接着剤シート］をはさみ、プレスにより50kg/cm2×
160℃×30分で圧着して３層フィルムを作製し、このフ
ィルムについての剥離強度、半田耐熱性をしらべ、剥離
状態を観察したところ、後記する表１に示したとおりの
結果が得られた。Then, methanol / water (weight ratio 90 /
Γ-glycidoxypropyltrimethoxysilane diluted to a 5 wt% solution with the mixed solution of 10) was applied to the film surface by an applicator as an amount of the coupling agent of 0.5 g /
m 2 is applied and dried at 80 ° C. for 5 minutes, and a bonding sheet E 33 [trade name, Epoxy-NB manufactured by Shin-Etsu Chemical Co., Ltd.] is provided between two treated polyimide films thus obtained.
R type adhesive sheet] and press it to 50kg / cm 2 ×
A three-layer film was produced by pressure bonding at 160 ° C. for 30 minutes, and the peeling strength and solder heat resistance of this film were examined and the peeling state was observed. The results shown in Table 1 below were obtained. .
【００１８】実施例２〜４ カップリング剤をイソプロピルトリイソステアロイルチ
タネート（メタノールのみで５wt％溶液に希釈）、Ｎ−
β（アミノエチル）−γ−アミノプロピルトリメトキシ
シラン（水／メタノール混合溶媒で希釈）、イソプロピ
ルトリクミルフェニルチタネート（水／メタノール混合
溶媒で希釈）に代えたほかは、実施例１と同様に処理し
て３層フィルムを作製し、これらについての剥離強度、
半田耐熱性をしらべ、剥離状態を観察したところ、後記
する表１に示したとおりの結果が得られた。Examples 2 to 4 Coupling agent was isopropyltriisostearoyl titanate (diluted with methanol alone to a 5 wt% solution), N-
Same as Example 1 except that β (aminoethyl) -γ-aminopropyltrimethoxysilane (diluted with water / methanol mixed solvent) and isopropyl tricumylphenyl titanate (diluted with water / methanol mixed solvent) were used. To produce a three-layer film, and the peel strength of these films,
When the peeling state was observed by examining the solder heat resistance, the results shown in Table 1 below were obtained.
【００１９】比較例１ 実施例１で使用したポリイミドフィルムを未処理の状態
で、またカップリング剤を塗布せずにこれから実施例１
と同じ方法で３層フィルムを作製し、このものの剥離強
度、半田耐熱性をしらべ、剥離状態を観察したところ、
後記する表１に示したような結果が得られた。COMPARATIVE EXAMPLE 1 The polyimide film used in Example 1 was untreated and was not coated with a coupling agent.
A three-layer film was prepared by the same method as in Example 1, and the peel strength and solder heat resistance of this film were examined and the peeled state was observed.
The results shown in Table 1 described later were obtained.
【００２０】比較例２ 実施例１で使用したポリイミドフィルムに低温プラズマ
処理を行わず、これに実施例１と同じカップリング剤を
実施例１と同様の方法で塗布し、これから実施例１と同
じ方法で３層フィルムを作製し、このものの剥離強度、
半田耐熱性をしらべ、剥離状態を観察したところ、後記
する表１に示したような結果が得られた。Comparative Example 2 The polyimide film used in Example 1 was not subjected to low-temperature plasma treatment, but the same coupling agent as in Example 1 was applied thereto in the same manner as in Example 1, and the same as in Example 1 from now on. A three-layer film is produced by the method, and the peel strength
When the peeling state was observed by examining the solder heat resistance, the results shown in Table 1 below were obtained.
【００２１】比較例３ 実施例１で使用したポリイミドフィルムに実施例１と同
様の方法で低温プラズマ処理をし、この処理面にγ−グ
リシドキシプロピルトリメトキシシランの塗布量を10.0
g/m2に増量したほかは実施例１と同じ方法で塗布したの
ち、実施例１と同じ方法で３層フィルムを作製し、この
ものの剥離強度、半田耐熱性をしらべ、剥離状態を観察
したところ、つぎの表１に示したような結果が得られ
た。Comparative Example 3 The polyimide film used in Example 1 was subjected to low temperature plasma treatment in the same manner as in Example 1, and the treated surface was coated with γ-glycidoxypropyltrimethoxysilane at a coating amount of 10.0.
After coating in the same manner as in Example 1 except that the amount was increased to g / m 2 , a three-layer film was prepared in the same manner as in Example 1, and the peel strength and solder heat resistance of this film were examined and the peeled state was observed. However, the results shown in Table 1 below were obtained.
【００２２】[0022]
【表１】 [Table 1]
【００２３】実施例５ 実施例１で使用したポリイミドフィルムに実施例１と同
じ方法で低温プラズマ処理を施し、このプラズマ処理を
施した面の上に、エタノール／水（重量比90／10）の混
合溶液で５wt％溶液に希釈したγ−アミノプロピルトリ
エトキシシランを、アプリケーターによりフィルム面に
対し 0.8g/m2塗布し、80℃で５分間乾燥した。このよう
にして得た処理済みのポリイミドフィルムの処理面にエ
ポキシ−ナイロン系接着剤を塗布したのち、これと厚さ
が35μｍの電解銅箔・ＪＩＣマット（ジャパンエナジー
社製商品名）とをロールラミネートロール（ロール温度
120℃、線圧 20kg/cm、ラインスピード３ｍ／分）で処
理し、さらに 150℃で３時間加熱処理して接着剤を硬化
させて、フレキシブル印刷配線用基板用の積層フィルム
を作成し、このフィルムの剥離強度、半田耐熱性をしら
べ、この剥離状態を観察したところ、後記する表２に示
したとおりの結果が得られた。Example 5 The polyimide film used in Example 1 was subjected to low-temperature plasma treatment in the same manner as in Example 1, and ethanol / water (weight ratio 90/10) was placed on the plasma-treated surface. Γ-Aminopropyltriethoxysilane diluted to a 5 wt% solution with the mixed solution was applied to the film surface by an applicator at 0.8 g / m 2 and dried at 80 ° C. for 5 minutes. After the epoxy-nylon adhesive is applied to the treated surface of the treated polyimide film thus obtained, this and 35 μm-thick electrolytic copper foil / JIC mat (product name of Japan Energy Co., Ltd.) is rolled. Laminating roll (roll temperature
120 ° C, linear pressure 20kg / cm, line speed 3m / min), and heat treatment at 150 ° C for 3 hours to cure the adhesive to make a laminated film for flexible printed wiring board. When the peeling strength and solder heat resistance of the film were examined and the peeled state was observed, the results shown in Table 2 below were obtained.
【００２４】実施例６、７ カップリング剤の塗布量を変更した以外は実施例１と同
様に３層フィルムを作製し、このものの剥離強度、半田
耐熱性をしらべ、剥離状態を観察したところ、後記する
表２に示した通りの結果が得られた。Examples 6 and 7 A three-layer film was prepared in the same manner as in Example 1 except that the coating amount of the coupling agent was changed, and the peeling strength and solder heat resistance of this film were examined and the peeled state was observed. The results shown in Table 2 below were obtained.
【００２５】実施例８、９ 厚さ25μｍのポリイミドフィルムアピカル（鐘淵化学工
業社製）を使用し、低温プラズマ処理をコロナ放電、紫
外線照射に変更した以外は、実施例１と同様に３層フィ
ルムを作製した。 コロナ放電処理：周波数 100kHz 、出力５kW、Ａｉｒ雰囲気 ラインスピード10ｍ／分 紫外線照射 ：出力 200ｗ、温度80℃、Ａｉｒ雰囲気 ラインスピード５ｍ／分、波長 254nmExamples 8 and 9 Three layers were prepared in the same manner as in Example 1 except that a 25 μm thick polyimide film apical (manufactured by Kanegafuchi Chemical Industry Co., Ltd.) was used and the low temperature plasma treatment was changed to corona discharge and UV irradiation. A film was made. Corona discharge treatment: Frequency 100kHz, output 5kW, Air atmosphere line speed 10m / min Ultraviolet irradiation: Output 200w, temperature 80 ° C, Air atmosphere line speed 5m / min, wavelength 254nm
【００２６】比較例４ 実施例４における低温プラズマ処理を行なわなかったほ
かは実施例４と同様に処理してフレキシブル配線基板用
の積層フィルムを作製し、このフィルムの剥離強度、半
田耐熱性をしらべ、剥離状態を観察したところ、つぎの
表２に示したとおりの結果が得られた。Comparative Example 4 A laminated film for a flexible wiring substrate was prepared in the same manner as in Example 4 except that the low temperature plasma treatment was not performed, and the peel strength and solder heat resistance of this film were examined. When the peeled state was observed, the results shown in Table 2 below were obtained.
【００２７】[0027]
【表２】 [Table 2]
【００２８】[0028]
【発明の効果】本発明は高接着性ポリイミドフィルムに
関するものであり、これによれば接着剤の組成に関係な
くポリイミドフィルムの接着性を向上させることができ
るので、フレキシブル印刷配線用基板、カバーレイなど
を製造するに当り有用なフィルムを容易に供給すること
ができるという有利性が与えられる。Industrial Applicability The present invention relates to a highly adhesive polyimide film, which can improve the adhesiveness of the polyimide film regardless of the composition of the adhesive. This provides an advantage that a film useful for manufacturing such as can be easily supplied.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 栄口 吉次 茨城県鹿島郡神栖町大字東和田１番地 信 越化学工業株式会社高分子機能性材料研究 所 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yoshitsugu Sakae No. 1 Towada, Kamisu-cho, Kashima-gun, Ibaraki Prefecture Shin-Etsu Chemical Co., Ltd.
Claims (3)
処理を施した後、表面活性化処理面にカップリング剤を
塗布してなることを特徴とする高接着性ポリイミドフィ
ルム。1. A highly-adhesive polyimide film which is obtained by subjecting the surface of a polyimide film to a surface activation treatment and then applying a coupling agent to the surface activation treated surface.
ロナ放電処理、紫外線処理から選択される一種の方法で
活性化処理された無機ガスで処理される請求項１に記載
した高接着性ポリイミドフィルム。2. The highly adhesive polyimide film according to claim 1, wherein the surface activation treatment is performed with an inorganic gas activated by a method selected from low temperature plasma treatment, corona discharge treatment, and ultraviolet treatment. .
対して 0.1〜５g/m2の範囲である請求項１に記載した高
接着性ポリイミドフィルム。3. The highly adhesive polyimide film according to claim 1, wherein the treating amount of the coupling agent is in the range of 0.1 to 5 g / m 2 with respect to the film area.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7152836A JPH093221A (en) | 1995-06-20 | 1995-06-20 | Highly adhesive polyimide film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7152836A JPH093221A (en) | 1995-06-20 | 1995-06-20 | Highly adhesive polyimide film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH093221A true JPH093221A (en) | 1997-01-07 |
Family
ID=15549199
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7152836A Pending JPH093221A (en) | 1995-06-20 | 1995-06-20 | Highly adhesive polyimide film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH093221A (en) |
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1995
- 1995-06-20 JP JP7152836A patent/JPH093221A/en active Pending
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