JPH05140750A - Formation of organic polymer film - Google Patents

Formation of organic polymer film

Info

Publication number
JPH05140750A
JPH05140750A JP32966791A JP32966791A JPH05140750A JP H05140750 A JPH05140750 A JP H05140750A JP 32966791 A JP32966791 A JP 32966791A JP 32966791 A JP32966791 A JP 32966791A JP H05140750 A JPH05140750 A JP H05140750A
Authority
JP
Japan
Prior art keywords
film
plasma
parylene
substrate
parylene film
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
JP32966791A
Other languages
Japanese (ja)
Inventor
Nobuyuki Yoshino
吉野  信幸
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.)
Citizen Watch Co Ltd
Original Assignee
Citizen Watch Co Ltd
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 Citizen Watch Co Ltd filed Critical Citizen Watch Co Ltd
Priority to JP32966791A priority Critical patent/JPH05140750A/en
Publication of JPH05140750A publication Critical patent/JPH05140750A/en
Pending legal-status Critical Current

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Abstract

PURPOSE:To form a Parylene film excellent in characteristics on one of various substrates with satisfactory adhesion by subjecting the surface of a plasma polymerized film formed on the surface of the substrate to plasma treatment in gaseous oxygen and synthesizing poly-p-xylylene in a vapor phase. CONSTITUTION:An Mg alloy casting 10 as a substrate is subjected to plasma treatment in an atmosphere based on gaseous hydrocarbon or an organosilicone compd. to form a plasma polymerized film 20 of about 100-200nm thickness on the surface of the substrate. This film 20 is subjected to plasma treatment in an atmosphere contg. gaseous oxygen or argon to etch the surface of the film 20 to about 20nm depth. By this etching, carbonyl and hydroxyl groups on the surface are decomposed and contaminants are removed. A Parylene film 30 is then formed on the film 20 by vapor phase synthesis in about 2nm thickness.

Description

【発明の詳細な説明】Detailed Description of the Invention

【0001】[0001]

【産業上の利用分野】本発明は有機高分子膜の形成方法
に関し、特に気相合成法によるパリレン膜の基材に対す
る密着性を向上させる方法に関する。
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for forming an organic polymer film, and more particularly to a method for improving the adhesion of a parylene film to a substrate by a vapor phase synthesis method.

【0002】[0002]

【従来の技術】パリレン膜とは米国のユニオン・カーバ
イド・ケミカルズ・アンド・プラスチック社が開発した
ポリパラキシリレン樹脂からなる気相合成法によるコー
ティング膜である。このコーティング膜は原料であるジ
パラキシリレン固体ダイマーを気化、熱分解し、この時
発生した安定なジラジカルパラキシリレンモノマーが基
材上において吸着と重合の同時反応を起こすことによっ
て形成される。このコーティング膜は従来の液状コーテ
ィングや粉末コーティングでは不可能な精密コーティン
グが可能であるほか、コーティング時被着物の形状、材
質を選ばない、室温でのコーティングが可能であるな
ど、他に類の無い数々の優れた特質を有する事により、
超精密部品のコーティングをはじめ、汎用品のコーティ
ングに至るまで、最適なコンフォーマル(同型)コーテ
ィング被膜として知られている。具体的にはハイブリッ
ドICの絶縁膜コーティング、ディスクドライブ部品の
ダスト粉の発生防止、ステッピングモーターの潤滑用
膜、生体材料の腐食防止膜にその応用例を見ることがで
きる。
2. Description of the Related Art A parylene film is a coating film made of a polyparaxylylene resin developed by Union Carbide Chemicals & Plastics Company of the United States by a vapor phase synthesis method. This coating film is formed by vaporizing and thermally decomposing the raw material diparaxylylene solid dimer, and the stable diradical paraxylylene monomer generated at this time causes a simultaneous reaction of adsorption and polymerization on the substrate. This coating film is capable of precision coating, which is not possible with conventional liquid coating or powder coating, as well as the shape and material of the adherend during coating, and coating at room temperature. By having many excellent characteristics,
It is known as the most suitable conformal coating film, from coating of ultra-precision parts to coating of general-purpose products. Specifically, its application examples can be seen in the insulation film coating of hybrid ICs, the prevention of dust generation of disk drive parts, the lubrication film of stepping motors, and the corrosion prevention film of biomaterials.

【0003】[0003]

【発明が解決しようとする課題】しかしながら、パリレ
ン膜の基材に対する密着性は、基材の種類によってその
特性が大きく異なる。例えばセラミックス基材に対する
密着性は一般に優れているが、ガラスや金属基材に対す
る密着性は著しく劣る。粘着テープによる引き剥しによ
って容易に剥離してしまう程度である。また密着性が良
いといわれているセラミックス基材においてもその種
類、使用環境条件によっては充分に要求特性を満たすと
は言い難い。その対策として現在一般的に行われている
のはパリレン膜形成前に前処理として脱脂洗浄後、シラ
ン処理を施すことである。これはパリレン膜コーティン
グ前の基材をオルガノシランカップリング剤を溶解した
アルコール溶液に浸漬、乾燥し、基材表面にシラン処理
層を形成し、その後、パリレン膜を形成する方法であ
る。しかし、このようなシラン処理を施してもシラン処
理層は基材及びパリレン膜に対して化学吸着によって結
合しているだけであるため要求特性によっては充分な密
着性を得ることができない。例えばこのような処理を施
したパリレン膜を形成したセラミックス基材を2次加工
として切断する場合、その切断面から徐々に剥離する現
象が観察される。
However, the adhesiveness of the parylene film to the base material varies greatly depending on the type of the base material. For example, the adhesion to ceramic substrates is generally excellent, but the adhesion to glass or metal substrates is extremely poor. It is easily peeled off by peeling off with an adhesive tape. Further, it is difficult to say that even a ceramic base material that is said to have good adhesiveness will sufficiently satisfy the required characteristics depending on its type and use environment conditions. As a countermeasure against this, a generally performed method is to perform degreasing cleaning as a pretreatment before forming a parylene film, and then perform a silane treatment. This is a method in which a base material before coating with a parylene film is immersed in an alcohol solution in which an organosilane coupling agent is dissolved and dried to form a silane-treated layer on the surface of the base material, and then a parylene film is formed. However, even if such a silane treatment is performed, the silane-treated layer is only bonded to the substrate and the parylene film by chemisorption, so that sufficient adhesion cannot be obtained depending on the required characteristics. For example, when a ceramic substrate having a parylene film that has been subjected to such a treatment is cut as a secondary process, a phenomenon of gradually peeling from the cut surface is observed.

【0004】本発明の目的は優れた特性を持つパリレン
膜を種々の基材上に密着性良く形成する方法を提供する
ことである。
An object of the present invention is to provide a method for forming a parylene film having excellent properties on various substrates with good adhesion.

【0005】[0005]

【課題を解決するための手段】上記目的のため本発明に
おいては、炭化水素ガスあるいは有機ケイ素化合物を主
成分とする雰囲気中におけるプラズマ重合によって基材
の表面にプラズマ重合膜を形成し、次に酸素ガスあるい
はアルゴンガスを含む雰囲気中におけるプラズマ処理に
よりプラズマ重合膜表面を処理し表面の汚染物の除去さ
らにはプラズマ重合膜表面に存在するパリレン膜とプラ
ズマ重合膜間の炭素−炭素共有結合形成を阻害するカル
ボニル基や水酸基を分解する。その後上記で述べた気相
合成法によってパリレン膜を形成するようにした。
To achieve the above object, in the present invention, a plasma polymerized film is formed on the surface of a substrate by plasma polymerization in an atmosphere containing a hydrocarbon gas or an organic silicon compound as a main component, and then, The surface of the plasma-polymerized film is treated by plasma treatment in an atmosphere containing oxygen gas or argon gas to remove surface contaminants and to form a carbon-carbon covalent bond between the parylene film present on the surface of the plasma-polymerized film and the plasma-polymerized film. Decomposes carbonyl groups and hydroxyl groups that interfere. After that, the parylene film was formed by the vapor phase synthesis method described above.

【0006】[0006]

【実施例1】以下に本発明の実施例を第1図を用いて説
明する。第1図は本発明によるパリレン膜を被覆したハ
ードディスクドライブ部品を構成するマグネシウム合金
鋳造物の一部を示す断面図である。この材料は非常にダ
スト粉が発生し易いことからその発生防止のためにパリ
レン膜のコーティングがなされているが、その密着性は
優れているわけではなく、しばしば部分的に剥離を生ず
る。そこで本発明によってまず鋳造物10上にプラズマ
重合法によって膜厚約100nmのプラズマ重合エチレ
ン膜20を形成する。一般にプラズマ重合膜はその成膜
機構から種々の基材に対して優れた密着性を示すことが
知られている。その条件を以下に示す。
Embodiment 1 An embodiment of the present invention will be described below with reference to FIG. FIG. 1 is a sectional view showing a part of a magnesium alloy casting constituting a hard disk drive component coated with a parylene film according to the present invention. Since this material is very likely to generate dust powder, a parylene film is coated to prevent the generation of dust powder, but its adhesiveness is not excellent and often peels off partially. Therefore, according to the present invention, a plasma polymerized ethylene film 20 having a film thickness of about 100 nm is first formed on the casting 10 by the plasma polymerization method. It is generally known that a plasma-polymerized film exhibits excellent adhesion to various substrates due to its film formation mechanism. The conditions are shown below.

【0007】原料ガス:エチレン 励起法 :高周波(13.56MHz) 励起出力:100W ガス流量:50cm3 /min. ガス圧 :0.5Torr 成膜速度:2nm/min. 処理温度:≦150℃Source gas: ethylene Excitation method: high frequency (13.56 MHz) Excitation output: 100 W Gas flow rate: 50 cm 3 / min. Gas pressure: 0.5 Torr Film formation rate: 2 nm / min. Processing temperature: ≤150 ° C

【0008】以上の条件で得られたプラズマ重合エチレ
ン膜20の構造は通常のポリエチレンとは異なり、枝分
かれや高密度の架橋構造を有しており、さらに不飽和二
重結合や芳香族化合物の酸化によって生じるカルボニル
基や水酸基が付随している。この事はプラズマ重合膜と
パリレン膜の密着性を阻害する大きな要因となってい
る。また重合反応中にプラズマ空間中で生成した粉末状
重合物が膜表面に付着することもパリレン膜との密着性
を妨げる要因として上げられる。そのためその対策とし
て、同一処理槽内において連続してプラズマ処理を行
う。その代表条件を以下に示す。
The structure of the plasma-polymerized ethylene film 20 obtained under the above conditions has a branched or high-density cross-linked structure unlike ordinary polyethylene, and further, unsaturated double bonds or oxidation of aromatic compounds. A carbonyl group or a hydroxyl group generated by is attached. This is a major factor that hinders the adhesion between the plasma polymerized film and the parylene film. Further, the adhesion of the powdery polymer produced in the plasma space during the polymerization reaction to the film surface is also a factor that impedes the adhesion to the parylene film. Therefore, as a countermeasure, plasma treatment is continuously performed in the same treatment tank. The representative conditions are shown below.

【0009】原料ガス:アルゴン 励起法 :高周波(13.56MHz) 励起出力:20W ガス流量:50cm3 /min. ガス圧 :0.2Torr 処理温度:≦150℃ 処理時間:3min.Source gas: Argon Excitation method: High frequency (13.56 MHz) Excitation output: 20 W Gas flow rate: 50 cm 3 / min. Gas pressure: 0.2 Torr Treatment temperature: ≦ 150 ° C. Treatment time: 3 min.

【0010】この処理によって膜表面が約20nmエッ
チングされ、阻害原因となるプラズマ重合エチレン膜2
0表面上のカルボニル基及び水酸基が破壊され、汚染物
質も除去される。以上の処理を施したプラズマ重合エチ
レン膜20上に上記で述べた気相合成法によってパリレ
ン膜30を約2μm形成する。プラズマ重合エチレン膜
20表面及び膜中には、ESR(電子スピン共鳴)分析
の結果から残存ラジカルが存在することが確認されてお
り、このラジカルとパリレン膜30形成時に生じたジラ
ジカルパラキシリレンモノマーが反応し、強固な共有結
合を形成する。このためプラズマ重合エチレン膜20と
パリレン膜30とは優れた密着性を示す。この工程も同
一反応器中で連続してパリレン膜を形成する事が望まし
い。
By this treatment, the surface of the film is etched by about 20 nm, which becomes a cause of inhibition.
Carbonyl groups and hydroxyl groups on the surface are destroyed, and contaminants are also removed. A parylene film 30 of about 2 μm is formed on the plasma-polymerized ethylene film 20 that has been subjected to the above-mentioned treatment by the vapor phase synthesis method described above. It has been confirmed from the result of ESR (electron spin resonance) analysis that residual radicals exist on the surface and in the plasma-polymerized ethylene film 20, and this radical and the diradical paraxylylene monomer generated during the formation of the parylene film 30 are present. React to form a strong covalent bond. Therefore, the plasma polymerized ethylene film 20 and the parylene film 30 exhibit excellent adhesion. Also in this step, it is desirable to continuously form a parylene film in the same reactor.

【0011】本発明の実施例の効果を確認するため比較
試料として実施例と同じ鋳造物上に通常のシラン処理を
施し、その後気相合成法によってパリレン膜約2μmを
被覆した比較試料と本発明によって得られた試料を碁盤
目テープ剥離試験によって評価した。その結果を表1に
示す。
In order to confirm the effect of the embodiment of the present invention, as a comparative sample, the same casting as that of the embodiment was subjected to the usual silane treatment, and then a parylene film of about 2 μm was coated by a vapor phase synthesis method. The sample obtained by the above was evaluated by a cross-cut tape peeling test. The results are shown in Table 1.

【0012】[0012]

【表1】 [Table 1]

【0013】[0013]

【実施例2】第2図は本発明によるパリレン膜を被覆し
たインクジェットプリンターに用いられるセラミックス
製圧電素子部品の一部分を示す断面図である。この際パ
リレン膜の水性インクに対する親水性を向上させるため
にパリレン膜の表面を親水性モノマーの液相グラフト重
合によって表面改質を行うが、約80度という反応温度
によってパリレン膜が圧電素子上から剥離する現象が頻
繁に観察された。そこで本発明によってテトラメチルシ
ランを原料とするプラズマ重合膜50を圧電素子40上
に約200nm被覆し、その後酸素プラズマによって表
面処理し、パリレン膜60を約2μm形成した。この結
果、グラフト重合による剥離現象は完全になくなった。
[Embodiment 2] FIG. 2 is a sectional view showing a part of a ceramic piezoelectric element component used in an ink jet printer coated with a parylene film according to the present invention. At this time, in order to improve the hydrophilicity of the parylene film with respect to the aqueous ink, the surface of the parylene film is surface-modified by liquid phase graft polymerization of a hydrophilic monomer. The phenomenon of peeling was frequently observed. Therefore, according to the present invention, a plasma polymerized film 50 made of tetramethylsilane as a raw material was coated on the piezoelectric element 40 by about 200 nm and then surface-treated with oxygen plasma to form a parylene film 60 of about 2 μm. As a result, the peeling phenomenon due to graft polymerization was completely eliminated.

【0014】[0014]

【発明の効果】以上の実施例から明らかなように、本発
明によれば種々の基材上にパリレン膜を密着性良く被覆
することが可能となり、パリレン膜の特性を充分に生か
した実用域での多方面への展開が可能となる。
As is clear from the above examples, according to the present invention, it becomes possible to coat a variety of substrates with a parylene film with good adhesion, and a practical range in which the properties of the parylene film are fully utilized. It will be possible to expand in many directions.

【図面の簡単な説明】[Brief description of drawings]

【図1】本発明の実施例1におけるパリレン膜を被覆し
たマグネシウム合金鋳造物の模式断面図である。
FIG. 1 is a schematic cross-sectional view of a magnesium alloy casting coated with a parylene film in Example 1 of the present invention.

【図2】本発明の実施例2におけるパリレン膜を被覆し
た圧電素子部品の模式断面図である。
FIG. 2 is a schematic cross-sectional view of a piezoelectric element part coated with a parylene film in Example 2 of the present invention.

【符号の説明】[Explanation of symbols]

10 マグネシウム合金鋳造物 20 プラズマ重合膜 30 パリレン膜 40 圧電素子部品 50 プラズマ重合膜 60 パリレン膜 10 Cast Magnesium Alloy 20 Plasma Polymerized Film 30 Parylene Film 40 Piezoelectric Element Component 50 Plasma Polymerized Film 60 Parylene Film

Claims (1)

【特許請求の範囲】[Claims] 【請求項1】炭化水素ガスあるいは有機ケイ素化合物を
主成分とする雰囲気中におけるプラズマ重合によって基
材の表面にプラズマ重合膜を形成する工程と、酸素ガス
あるいはアルゴンガスを含む雰囲気中におけるプラズマ
処理によってプラズマ重合膜表面を処理する工程と、気
相合成法によってパリレン膜を形成する工程とからなる
有機高分子膜の形成方法。
1. A step of forming a plasma polymerized film on the surface of a substrate by plasma polymerization in an atmosphere containing a hydrocarbon gas or an organic silicon compound as a main component, and a plasma treatment in an atmosphere containing oxygen gas or argon gas. A method for forming an organic polymer film, comprising a step of treating a surface of a plasma polymerized film and a step of forming a parylene film by a vapor phase synthesis method.
JP32966791A 1991-11-20 1991-11-20 Formation of organic polymer film Pending JPH05140750A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP32966791A JPH05140750A (en) 1991-11-20 1991-11-20 Formation of organic polymer film

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP32966791A JPH05140750A (en) 1991-11-20 1991-11-20 Formation of organic polymer film

Publications (1)

Publication Number Publication Date
JPH05140750A true JPH05140750A (en) 1993-06-08

Family

ID=18223920

Family Applications (1)

Application Number Title Priority Date Filing Date
JP32966791A Pending JPH05140750A (en) 1991-11-20 1991-11-20 Formation of organic polymer film

Country Status (1)

Country Link
JP (1) JPH05140750A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008523627A (en) * 2004-12-07 2008-07-03 マルティ−ファインライン エレクトロニクス インコーポレイテッド Small circuit, induction component, and manufacturing method thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008523627A (en) * 2004-12-07 2008-07-03 マルティ−ファインライン エレクトロニクス インコーポレイテッド Small circuit, induction component, and manufacturing method thereof

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