JPH11222666A - Metal evaporated fluororesin film and its production - Google Patents
Metal evaporated fluororesin film and its productionInfo
- Publication number
- JPH11222666A JPH11222666A JP3955998A JP3955998A JPH11222666A JP H11222666 A JPH11222666 A JP H11222666A JP 3955998 A JP3955998 A JP 3955998A JP 3955998 A JP3955998 A JP 3955998A JP H11222666 A JPH11222666 A JP H11222666A
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- Prior art keywords
- metal
- deposited
- fluororesin film
- film
- layer
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- Physical Vapour Deposition (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は金属蒸着フッ素樹脂
フィルムおよびその製造方法に関し、特に金属蒸着層の
密着力を向上させた金属蒸着フッ素樹脂フィルムおよび
その製造方法に関する。The present invention relates to a metal-deposited fluororesin film and a method for producing the same, and more particularly to a metal-deposited fluororesin film having improved adhesion of a metal-deposited layer and a method for producing the same.
【０００２】[0002]
【従来の技術】フッ素樹脂フィルムは、一般的に密着性
に劣るとという欠点を有しており、通常の真空蒸着法に
より金属を蒸着させると金属蒸着層とフッ素樹脂フィル
ムとの密着性は低く、到底実用に供せるものではない。
フッ素樹脂フィルムの接着性を向上させるための方法と
しては、フッ素樹脂フィルム表面へのコロナ放電処理や
アンカーコーティング処理が知られている。しかしこの
ような処理を施したフッ素樹脂フィルムに金属蒸着を行
って得られる金属蒸着フッ素樹脂フィルムは、後工程で
粘着剤や接着剤をコートする時、粘着剤や接着剤に含ま
れる溶剤が樹脂アンカーコート層を溶解して白化した
り、せっかく行ったコロナ放電処理の効果を失うという
欠点があった。2. Description of the Related Art Fluororesin films generally have a drawback of poor adhesion, and when a metal is deposited by a normal vacuum deposition method, the adhesion between the metal deposition layer and the fluororesin film is low. It is not something that can be put to practical use at all.
As a method for improving the adhesiveness of the fluororesin film, a corona discharge treatment or an anchor coating treatment on the surface of the fluororesin film is known. However, when a metal-deposited fluororesin film obtained by performing metal vapor deposition on a fluororesin film subjected to such a treatment is coated with an adhesive or an adhesive in a later step, the solvent contained in the adhesive or the adhesive is a resin. There were drawbacks that the anchor coat layer was dissolved and whitened, or that the effect of the corona discharge treatment that had been performed was lost.
【０００３】[0003]
【発明が解決しようとする課題】したがって、本発明の
課題は、金属蒸着層の密着性に優れた金属蒸着フッ素樹
脂フィルムおよびその製造方法を提供することにある。SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a metal-deposited fluororesin film having excellent adhesion of a metal-deposited layer and a method for producing the same.
【０００４】[0004]
【課題を解決するための手段】本発明者らの鋭意検討の
結果、本発明の目的は、下記の本発明によって工業的に
有利に達成された。As a result of intensive studies by the present inventors, the object of the present invention has been industrially advantageously achieved by the present invention described below.
【０００５】［１］フッ素樹脂フィルム表面に、プラズ
マ放電下による核付金属蒸着層、およびその上に金属蒸
着層をそれぞれ形成せしめてなる金属蒸着フッ素樹脂フ
ィルム。[1] A metal-deposited fluororesin film in which a nucleated metal-deposited layer is formed on a fluororesin film surface by plasma discharge, and a metal-deposited layer is formed thereon.
【０００６】［２］プラズマ放電の処理強度が１〜１２
ｋｗ／ｍ2であることを特徴とする上記［１］記載の金
属蒸着フッ素樹脂フィルム。[2] A plasma discharge treatment intensity of 1 to 12
kw / m 2 , wherein the metal-deposited fluororesin film according to the above [1].
【０００７】［３］プラズマ放電の放電ガスが酸素であ
ることを特徴とする上記［１］または［２］に記載の金
属蒸着フッ素樹脂フィルム。[3] The metal-deposited fluororesin film according to [1] or [2], wherein the discharge gas of the plasma discharge is oxygen.
【０００８】［４］プラズマ放電下による核付金属蒸着
層の金属が銅であることを特徴とする上記［１］〜
［３］のいずれかに記載の金属蒸着フッ素樹脂フィル
ム。[4] The above [1] to [1], wherein the metal of the nucleated metal deposition layer under plasma discharge is copper.
The metal-deposited fluororesin film according to any one of [3].
【０００９】［５］金属蒸着層が金属アルミニウムであ
ることを特徴とする上記［１］〜［４］のいずれかに記
載の金属蒸着フッ素樹脂フィルム。[5] The metal-deposited fluororesin film according to any one of [1] to [4], wherein the metal-deposited layer is metal aluminum.
【００１０】［６］核付金属蒸着層の平均膜厚が０．０
１〜２．０ｎｍであることを特徴とする上記［１］〜
［５］のいずれかに記載の金属蒸着フッ素樹脂フィル
ム。[6] The average thickness of the cored metal deposition layer is 0.0
[1] to 1 to 2.0 nm,
The metal-deposited fluororesin film according to any one of [5].
【００１１】［７］金属蒸着層の平均膜厚が１０〜１０
０ｎｍであることを特徴とする上記［１］〜［６］のい
ずれかに記載の金属蒸着フッ素樹脂フィルム。[7] The average thickness of the metal deposition layer is 10 to 10
The metal-deposited fluororesin film according to any one of the above [1] to [6], wherein the thickness is 0 nm.
【００１２】［８］フッ素樹脂フィルムがポリ四フッ化
エチレンフィルム、ポリ三フッ化エチレンフィルム、六
フッ化プロピレン−四フッ化エチレン共重合体フィル
ム、ポリフッ化ビニルフィルム、またはポリフッ化ビニ
リデンフィルムであり、かつその厚みが１２〜１００μ
ｍであることを特徴とする上記［１］〜［７］のいずれ
かに記載の金属蒸着フッ素樹脂フィルム。[8] The fluororesin film is a polytetrafluoroethylene film, a polytrifluoroethylene film, a propylene hexafluoride-tetrafluoroethylene copolymer film, a polyvinyl fluoride film, or a polyvinylidene fluoride film , And the thickness is 12-100μ
m, wherein the metal-deposited fluororesin film according to any one of the above [1] to [7].
【００１３】［９］フッ素樹脂フィルム表面に、同一真
空系内で、プラズマ放電下による核付金属蒸着層および
その上に金属蒸着層をそれぞれ形成することを特徴とす
る金属蒸着フッ素樹脂フィルムの製造方法。[9] Production of a metal-deposited fluororesin film characterized by forming a metal-deposited layer with a nucleus and a metal-deposited layer thereon by plasma discharge in the same vacuum system on the surface of the fluororesin film, respectively. Method.
【００１４】本発明の最大の特徴は、フッ素樹脂フィル
ム表面に、プラズマ放電下に核付金属蒸着層、好ましく
は銅からなる核付金属蒸着層を形成させ、その上に金属
蒸着層、好ましくは金属アルミニウムからなる金属蒸着
層を形成させることにより、金属蒸着層とフッ素樹脂フ
ィルムとの密着力を著しく向上させた点にある。核付金
属蒸着層を形成させない場合に比較して、例えば２０倍
以上の密着力が得られる。The most important feature of the present invention is that a nucleated metal deposition layer, preferably a nucleation metal deposition layer made of copper, is formed on a fluororesin film surface by plasma discharge, and a metal deposition layer, preferably The point is that by forming a metal vapor deposition layer made of metal aluminum, the adhesion between the metal vapor deposition layer and the fluororesin film is remarkably improved. Compared to the case where the metal deposition layer with a nucleus is not formed, for example, an adhesion of 20 times or more can be obtained.
【００１５】[0015]
【発明の実施の形態】次に本発明を詳しく説明する。Next, the present invention will be described in detail.
【００１６】本発明において、フッ素樹脂フィルムは、
特に制限を受けないが、ポリ四フッ化エチレンフィル
ム、ポリ三フッ化エチレンフィルム、六フッ化プロピレ
ン−四フッ化エチレン共重合体フィルム、ポリフッ化ビ
ニルフィルム、またはポリフッ化ビニリデンフィルムで
あることが好ましい。本発明において使用されるフッ素
樹脂フィルムの厚みは、通常１０〜１９０μｍである。In the present invention, the fluororesin film is
Although not particularly limited, a polytetrafluoroethylene film, a polytrifluoroethylene film, a hexafluoropropylene-tetrafluoroethylene copolymer film, a polyvinyl fluoride film, or a polyvinylidene fluoride film is preferable. . The thickness of the fluororesin film used in the present invention is usually 10 to 190 μm.
【００１７】本発明におけるプラズマ放電下に核付金属
蒸着層の形成は、次のように行なわれる。好ましくは
０．１〜１００Ｐａの酸素ガス雰囲気下で高周波電源よ
り供給された電流をマグネトロン電極のカソード及びア
ノード間で放電させる。その際カソードに核付金属蒸着
層を構成する金属、好ましくは銅を用いる。カソードに
ガス陽イオンが引き寄せられカソード金属をスパッタす
る。このスパッタされた金属がフッ素樹脂フィルムに付
着し核付金属蒸着層を形成する。The formation of the nucleated metal deposition layer under the plasma discharge in the present invention is performed as follows. Preferably, a current supplied from a high frequency power supply is discharged between the cathode and the anode of the magnetron electrode under an oxygen gas atmosphere of 0.1 to 100 Pa. In this case, a metal constituting the metal deposition layer with a nucleus, preferably copper, is used for the cathode. Gas cations are attracted to the cathode and sputter the cathode metal. The sputtered metal adheres to the fluororesin film to form a nucleated metal deposition layer.
【００１８】本発明において、ブラズマ放電の処理強度
は、１〜１２ｋｗ／ｍ2であることが好ましい。ブラズ
マ放電の処理強度が１ｋｗ／ｍ2未満であるとフィルム
に付着するスパッタ金属の厚みがあまりにも薄くなり、
ブラズマ放電処理の効果が少なくなってしまう恐れがあ
る。またブラズマ放電の処理強度が１２ｋｗ／ｍ2を超
えると、フィルムに付着するスパッタ金属の厚みがあま
りにも厚くなり、その金属色が確認できるようになり外
観上好ましくない。In the present invention, the treatment intensity of the plasma discharge is preferably 1 to 12 kw / m 2 . If the processing intensity of the plasma discharge is less than 1 kw / m 2 , the thickness of the sputtered metal attached to the film becomes too thin,
There is a possibility that the effect of the plasma discharge treatment is reduced. On the other hand, if the treatment intensity of the plasma discharge exceeds 12 kw / m 2 , the thickness of the sputtered metal adhered to the film becomes too large, and the metal color can be confirmed, which is not preferable in appearance.
【００１９】核付金属蒸着層の平均膜厚は、０．０１〜
２．０ｎｍであることが、密着強度の向上を得ること及
び外観を損なわないこと等、から好ましい。The average film thickness of the cored metal deposition layer is 0.01 to
The thickness of 2.0 nm is preferable from the viewpoint of improving the adhesion strength and not impairing the appearance.
【００２０】また、核付金属蒸着層上に蒸着する金属と
しては、特に制限は受けないが、アルミニウム、スズ、
およびクロム等が挙げられ、なかでも色調および蒸着適
性からアルミニウムが最も好ましい。その蒸着方法は、
特に制限されないが、真空蒸着法、イオンプレーティン
グ法、スパッタリング法、およびイオンプレーティング
法等が用いられる。本発明における金属蒸着層の厚み
は、通常１０〜１００ｎｍの範囲内である。The metal deposited on the cored metal deposition layer is not particularly limited, but may be aluminum, tin,
And chromium. Among them, aluminum is most preferable from the viewpoint of color tone and vapor deposition suitability. The deposition method is
Although not particularly limited, a vacuum evaporation method, an ion plating method, a sputtering method, an ion plating method, or the like is used. The thickness of the metal deposition layer in the present invention is usually in the range of 10 to 100 nm.
【００２１】本発明において、核付金属蒸着層と金属蒸
着層との形成は、同一真空系内で行うのが、密着性向上
のために好ましい。核付金属蒸着層の形成後大気に暴露
すると、密着性に悪影響を与えるからである。In the present invention, the formation of the metal deposition layer with nucleus and the metal deposition layer is preferably performed in the same vacuum system in order to improve the adhesion. This is because exposure to the atmosphere after the formation of the metal deposition layer with a nucleus adversely affects adhesion.
【００２２】[0022]
【実施例】以下、実施例により、本発明を具体的に説明
するが、本発明は、これらに限定されるものではない。EXAMPLES The present invention will now be described specifically with reference to examples, but the present invention is not limited to these examples.
【００２３】なお、実施例および比較例中の物性（ラミ
ネート強度）は次のように測定した。The physical properties (laminate strength) in Examples and Comparative Examples were measured as follows.
【００２４】ラミネート強度の測定方法：蒸着面にウレ
タン系２液型接着剤をドライで２μｍ相当コートし２５
μｍの厚みのポリエステルフィルムとラミネートし７２
時間４０℃雰囲気でエージングする。その後１５ｍｍ幅
×２００ｍｍ長に切り取り、オリエンテック社製テンシ
ロン万能試験機を用いて引張速度２００ｍｍ／ｍｉｎで
９０゜剥離時の密着強度を測定した。これをドライラミ
ネート強度とした。９０゜剥離時に剥離界面に蒸留水２
〜３滴滴下して、同様に９０゜剥離時の密着強度を測定
した。これをウェットラミネート強度とした。Measurement method of lamination strength: A 2-part urethane-based adhesive was dry-coated on the vapor-deposited surface to a thickness of 2 μm, and the
Laminated with a polyester film having a thickness of μm.
Aging is carried out for 40 hours in an atmosphere. Thereafter, it was cut into 15 mm width × 200 mm length, and the adhesion strength at 90 ° peeling was measured at a tensile speed of 200 mm / min using a Tensilon universal testing machine manufactured by Orientec. This was defined as dry lamination strength. Distilled water 2 at peeling interface at 90 ° peeling
Approximately 3 drops were dropped, and the adhesion strength at 90 ° peeling was measured in the same manner. This was defined as wet lamination strength.
【００２５】［実施例１］〜［実施例４」、［比較例
１］〜［比較例４」 厚さ２５μｍのポリ四フッ化エチレンフィルムを用い、
通常のロール・ツー・ロール型の真空蒸着機を用いて蒸
着を行った。核付金属の蒸着は１×１０-4ｍｍＨｇの真
空下、マグネトロン電極のカソードに純度９９．９％の
銅材を用い、放電ガスとして０．５リットル／ｍｉｎの
酸素ガスを用いた。さらにマグネトロン電極に電圧をか
け放電雰囲気としフッ素樹脂フィルムそれぞれつぎに示
す平均厚みの核付金属蒸着層を形成した。引き続き同じ
真空蒸着機内で１×１０-4ｍｍＨｇの真空下でアルミニ
ウム蒸着層を形成させた。[Example 1] to [Example 4], [Comparative Example 1] to [Comparative Example 4] Using a polytetrafluoroethylene film having a thickness of 25 μm,
Evaporation was performed using a normal roll-to-roll type vacuum evaporator. For the deposition of the cored metal, a copper material having a purity of 99.9% was used for the cathode of the magnetron electrode under a vacuum of 1 × 10 −4 mmHg, and an oxygen gas of 0.5 liter / min was used as a discharge gas. Further, a voltage was applied to the magnetron electrode to form a discharge atmosphere, and a nucleated metal deposition layer having the following average thickness was formed on each of the fluororesin films. Subsequently, an aluminum deposition layer was formed in the same vacuum deposition machine under a vacuum of 1 × 10 −4 mmHg.
【００２６】実施例１：０．０１ｎｍ 実施例２：０．１ｎｍ 実施例３：１．０ｎｍ 実施例４：２．０ｎｍ 一方、比較例１は、核付金属蒸着層を形成することなく
５０ｎｍのアルミニウム蒸着層を実施例と同様に形成さ
せた。比較例２ではコロナ放電処理面に比較例１と同様
のアルミニウム蒸着層を形成させた。比較例３ではアン
カー処理面に比較例１と同様のアルミニウム蒸着層を形
成させた。比較例４では、抵抗加熱方式で銅を１．０ｍ
ｍの厚みで核付金属蒸着層を形成させ、引き続いて比較
例１と同様のアルミニウム蒸着層を形成させた。Example 1: 0.01 nm Example 2: 0.1 nm Example 3: 1.0 nm Example 4: 2.0 nm On the other hand, Comparative Example 1 has a thickness of 50 nm without forming a nucleated metal deposition layer. An aluminum deposition layer was formed in the same manner as in the example. In Comparative Example 2, an aluminum deposited layer similar to that of Comparative Example 1 was formed on the corona discharge treated surface. In Comparative Example 3, the same aluminum deposited layer as in Comparative Example 1 was formed on the anchored surface. In Comparative Example 4, the resistance heating method
A metal deposition layer with a nucleus was formed with a thickness of m, and subsequently, an aluminum deposition layer similar to that of Comparative Example 1 was formed.
【００２７】表１に実施例１〜４と比較例１〜４の特性
の測定結果をまとめた。Table 1 summarizes the measurement results of the characteristics of Examples 1 to 4 and Comparative Examples 1 to 4.
【００２８】[0028]
【表１】 表１から明らかなように、実施例１〜４により得られた
金属蒸着フッ素樹脂フィルムはラミネート強度（ドライ
およびウェットともに）が比較例１〜４で得られる金属
蒸着フッ素樹脂フィルムに比較してレベルアップした結
果が得られた。[Table 1] As is clear from Table 1, the metal-deposited fluororesin films obtained in Examples 1 to 4 have a laminating strength (both dry and wet) which is lower than that of the metal-deposited fluororesin films obtained in Comparative Examples 1 to 4. The result was up.
【００２９】[0029]
【発明の効果】本発明によれば、フッ素樹脂フィルム上
に特定の核付金属蒸着層および金属蒸着層を順次形成す
ることにより、核付金属蒸着層のないものに比べて金属
蒸着層の脱落の極めてしにくい金属蒸着フッ素樹脂フィ
ルムが得られる。したがって、本発明は、ラミネート強
度の必要な金属蒸着フィルム（例えば、装飾用フィル
ム、ラベル、マーキングフィルム、耐熱服・防火服用フ
ィルム等）に特に有効である。According to the present invention, a metal-deposited layer having a specific nucleus and a metal-deposited layer are sequentially formed on a fluororesin film so that the metal-deposited layer is less likely to fall off as compared with the case without the core-deposited metal-deposited layer. A metal-deposited fluororesin film that is extremely difficult to obtain is obtained. Therefore, the present invention is particularly effective for metal-deposited films requiring a laminate strength (for example, decorative films, labels, marking films, films for heat-resistant clothes and fire-resistant clothes, etc.).
Claims (9)
下による核付金属蒸着層、およびその上に金属蒸着層を
それぞれ形成せしめてなる金属蒸着フッ素樹脂フィル
ム。1. A metal-deposited fluororesin film comprising a nucleated metal-deposited layer formed by plasma discharge on a fluororesin film surface and a metal-deposited layer formed thereon.
ｍ2であることを特徴とする請求項１記載の金属蒸着フ
ッ素樹脂フィルム。2. A plasma discharge treatment intensity of 1 to 12 kW /
metallized fluororesin film according to claim 1, characterized in that the m 2.
を特徴とする請求項１または２記載の金属蒸着フッ素樹
脂フィルム。3. The metal-deposited fluororesin film according to claim 1, wherein the discharge gas of the plasma discharge is oxygen.
属が銅であることを特徴とする請求項１〜３のいずれか
に記載の金属蒸着フッ素樹脂フィルム。4. The metal-deposited fluororesin film according to claim 1, wherein the metal of the metal-deposited nucleation layer under plasma discharge is copper.
を特徴とする請求項１〜４のいずれかに記載の金属蒸着
フッ素樹脂フィルム。5. The metal-deposited fluororesin film according to claim 1, wherein the metal-deposited layer is made of metal aluminum.
２．０ｎｍであることを特徴とする請求項１〜５のいず
れかに記載の金属蒸着フッ素樹脂フィルム。6. An average film thickness of the cored metal deposition layer is from 0.01 to 0.01.
The metal-deposited fluororesin film according to any one of claims 1 to 5, wherein the thickness is 2.0 nm.
であることを特徴とする請求項１〜６のいずれかに記載
の金属蒸着フッ素樹脂フィルム。7. The metal deposited layer has an average thickness of 10 to 100 nm.
The metal-deposited fluororesin film according to any one of claims 1 to 6, wherein
ンフィルム、ポリ三フッ化エチレンフィルム、六フッ化
プロピレン−四フッ化エチレン共重合体フィルム、ポリ
フッ化ビニルフィルム、またはポリフッ化ビニリデンフ
ィルムであり、かつその厚みが１２〜１００μｍである
ことを特徴とする請求項１〜７のいずれかに記載の金属
蒸着フッ素樹脂フィルム。8. The fluororesin film is a polytetrafluoroethylene film, a polytrifluoroethylene film, a propylene hexafluoride-ethylene tetrafluoride copolymer film, a polyvinyl fluoride film, or a polyvinylidene fluoride film, The metal-deposited fluororesin film according to any one of claims 1 to 7, wherein the thickness is 12 to 100 µm.
で、プラズマ放電下による核付金属蒸着層およびその上
に金属蒸着層をそれぞれ形成することを特徴とする金属
蒸着フッ素樹脂フィルムの製造方法。9. A method of manufacturing a metal-deposited fluororesin film, comprising forming a metal-deposited layer with a nucleus and a metal-deposited layer thereon by plasma discharge in the same vacuum system on the surface of the fluororesin film. .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3955998A JPH11222666A (en) | 1998-02-05 | 1998-02-05 | Metal evaporated fluororesin film and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3955998A JPH11222666A (en) | 1998-02-05 | 1998-02-05 | Metal evaporated fluororesin film and its production |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH11222666A true JPH11222666A (en) | 1999-08-17 |
Family
ID=12556439
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3955998A Pending JPH11222666A (en) | 1998-02-05 | 1998-02-05 | Metal evaporated fluororesin film and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH11222666A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5019243B1 (en) * | 2012-01-20 | 2012-09-05 | 尾池工業株式会社 | Antireflection film |
| JPWO2020066457A1 (en) * | 2018-09-25 | 2021-08-30 | 東レ株式会社 | Laminated body and manufacturing method of laminated body |
-
1998
- 1998-02-05 JP JP3955998A patent/JPH11222666A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5019243B1 (en) * | 2012-01-20 | 2012-09-05 | 尾池工業株式会社 | Antireflection film |
| JPWO2020066457A1 (en) * | 2018-09-25 | 2021-08-30 | 東レ株式会社 | Laminated body and manufacturing method of laminated body |
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