JPH0776767A - Formation of silicon oxide film - Google Patents
Formation of silicon oxide filmInfo
- Publication number
- JPH0776767A JPH0776767A JP22421993A JP22421993A JPH0776767A JP H0776767 A JPH0776767 A JP H0776767A JP 22421993 A JP22421993 A JP 22421993A JP 22421993 A JP22421993 A JP 22421993A JP H0776767 A JPH0776767 A JP H0776767A
- Authority
- JP
- Japan
- Prior art keywords
- siox
- film
- plastic film
- rays
- wavelength
- 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.)
- Withdrawn
Links
Landscapes
- Physical Vapour Deposition (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明はプラスチックフィルム表
面にＳｉＯｘ皮膜を形成する方法に関し、ガスバリヤ性
の優れたＳｉＯｘ蒸着プラスチックフィルムの製造に有
利に適用し得る方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for forming a SiOx film on the surface of a plastic film, and more particularly to a method which can be advantageously applied to the production of a SiOx vapor-deposited plastic film having an excellent gas barrier property.
【０００２】[0002]
【従来の技術】従来、プラスチックフィルムにＳｉＯｘ
（Ｓｉ，ＳｉＯ，ＳｉＯ2 の混合組成）皮膜を蒸着する
に際しては、ＳｉＯ蒸発材料を低コストで生産性のよい
１．３×１０-2Ｐａ以上の圧力の真空槽内でスプラッシ
ュ（蒸発材料の突沸）が発生しないように１５００Ｋ以
下に加熱し、ＳｉＯｘを昇華させプラスチックフィルム
に蒸着している。しかしながら、従来法のような条件で
はガスバリア性の良好なＳｉＯｘ蒸着フィルムを形成す
ることはできなかった。2. Description of the Related Art Conventionally, SiOx is applied to a plastic film.
(Mixed composition of Si, SiO, SiO 2 ) When vapor-depositing a film, the SiO evaporation material is splashed in a vacuum chamber at a pressure of 1.3 × 10 -2 Pa or more with low cost and high productivity. It is heated to 1500 K or less so as not to cause bumping), and SiOx is sublimated and deposited on a plastic film. However, under the conditions as in the conventional method, it was not possible to form a SiOx vapor deposition film having a good gas barrier property.
【０００３】[0003]
【発明が解決しようとする課題】ＳｉＯｘ蒸着フィルム
は食品包装用に用いられるため、酸素透過度が小さい方
が望ましいが、真空槽内の圧力が１．３×１０-2Ｐａ以
上であるとＳｉＯｘ皮膜中のガス巻き込みあるいはＳｉ
Ｏｘのクラスター化により多孔質な皮膜となり、ガスバ
リヤ性の良好な皮膜は得られない。そこで１．３×１０
-2Ｐａ以下で真空蒸着する必要があるが、プラスチック
フィルムからも吸着ガスが放出されるため、真空ポンプ
の排気速度を著しく大きいものにするか、長時間真空引
きする必要があり生産性が悪かった。また、蒸発源温度
を１５００Ｋ以上にすると、スプラッシュという蒸発材
料の塊が飛び跳ね、プラスチックフィルムに穴があく問
題があった。Since the SiOx vapor-deposited film is used for food packaging, it is desirable that the oxygen permeability is small. However, if the pressure in the vacuum chamber is 1.3 × 10 -2 Pa or more, the SiOx vapor-deposited film should be SiOx. Gas entrapment in the coating or Si
Ox clustering results in a porous film, and a film with good gas barrier properties cannot be obtained. So 1.3 × 10
It is necessary to vacuum-deposit at -2 Pa or less, but the adsorbed gas is also released from the plastic film, so it is necessary to either increase the pumping speed of the vacuum pump significantly or to vacuum for a long time, which reduces productivity. It was Further, when the temperature of the evaporation source is 1500 K or higher, there is a problem that a lump of evaporation material called splash splashes and a hole is formed in the plastic film.
【０００４】本発明は上記技術水準に鑑み、真空系がコ
ンパクトで装置で安価で、かつ、真空引時間が短く生産
性の大きな真空槽内圧力が６．６×１０-2Ｐａ程度で、
しかもスプラッシュの発生しない蒸発源温度で酸素透過
度の小さなＳｉＯｘ蒸着プラスチックフィルムを形成で
きる方法を提供しようとするものである。In view of the above-mentioned state of the art, the present invention has a compact vacuum system, an inexpensive apparatus, a short vacuuming time, and a large productivity, and the internal pressure of the vacuum chamber is about 6.6 × 10 -2 Pa.
Moreover, it is an object of the present invention to provide a method capable of forming a SiOx vapor-deposited plastic film having a low oxygen permeability at an evaporation source temperature at which splash does not occur.
【０００５】[0005]
【課題を解決するための手段】本発明はプラスチックフ
ィルム表面にＰＶＤ法によりＳｉＯｘ皮膜を形成する方
法において、ＳｉＯｘ蒸気及び／又はプラスチックフィ
ルム表面に紫外線を照射しつゝ蒸着することを特徴とす
るＳｉＯｘ皮膜の形成方法である。The present invention is a method for forming a SiOx film on a plastic film surface by a PVD method, characterized in that the SiOx vapor and / or the plastic film surface is irradiated with ultraviolet rays and vapor-deposited. It is a method of forming a film.
【０００６】[0006]
【作用】ＳｉＯ分子は紫外線波長域に吸収帯を有し、特
に波長２１０〜２８０ｎｍの紫外領域に強い吸収帯が存
在する。そこでＳｉＯｘ蒸気に３００ｎｍ以下の波長を
カットしていない紫外線を照射すると、ＳｉＯ分子は紫
外線を吸収し励起し、励起したＳｉＯ分子はその励起エ
ネルギによりプラスチックフィルム表面での拡散運動を
促進し、形成したＳｉＯｘ皮膜を緻密化しガスバリア性
を良好にする。The SiO molecule has an absorption band in the ultraviolet wavelength range, and particularly has a strong absorption band in the ultraviolet range of wavelength 210 to 280 nm. Therefore, when the SiOx vapor is irradiated with ultraviolet rays having a wavelength of 300 nm or less which is not cut, the SiO molecules absorb and excite the ultraviolet rays, and the excited SiO molecules are formed by promoting the diffusion motion on the surface of the plastic film by the excitation energy. Improves the gas barrier property by densifying the SiOx film.
【０００７】また、プラスチックフィルム表面に紫外線
を照射すると、以下の（１）〜（３）の作用が働きＳｉ
Ｏｘ皮膜を緻密化し、ガスバリア性を良好にする。 （１）蒸着前に、プラスチックフィルムに紫外線を照射
すると、プラスチックフィルム表面が活性化され、濡れ
性がよくなるため、そこにＳｉＯｘを蒸着するとＳｉＯ
分子の拡散が進み、ＳｉＯｘ皮膜が緻密化する。 （２）プラスチックフィルム表面の吸着気体が除去され
やすくなるため、ＳｉＯｘ皮膜中の気体の巻き込みが少
なくなる。 （３）プラスチックフィルム表面が紫外線で加熱され高
温となるため、プラスチックフィルム表面でのＳｉＯ分
子の拡散運動が促進される。When the surface of the plastic film is irradiated with ultraviolet rays, the following actions (1) to (3) work and Si
Densify the Ox film and improve gas barrier properties. (1) If the plastic film is irradiated with ultraviolet rays before vapor deposition, the surface of the plastic film is activated and the wettability is improved.
The diffusion of molecules proceeds, and the SiOx film becomes dense. (2) Since the adsorbed gas on the surface of the plastic film is easily removed, gas entrapment in the SiOx film is reduced. (3) Since the surface of the plastic film is heated by ultraviolet rays to a high temperature, the diffusion motion of SiO molecules on the surface of the plastic film is promoted.
【０００８】この場合には、プラスチックフィルム表面
に対する紫外線の作用を利用するものであるので、Ｓｉ
Ｏ分子の励起とは無関係であり、３００ｎｍ以下の波長
をカットした紫外線を照射してもその作用は殆んど変わ
らない。In this case, since the action of ultraviolet rays on the surface of the plastic film is utilized, Si is used.
Irrespective of the excitation of the O molecule, the action is almost unchanged even when the ultraviolet rays with a wavelength cut below 300 nm are irradiated.
【０００９】また、ＳｉＯｘ蒸気及びプラスチックフィ
ルム表面の両方に紫外線を照射する場合には上記の両方
の作用が同時に奏され、プラスチックフィルム表面に緻
密なＳｉＯｘ皮膜が蒸着される。この場合もプラスチッ
クフィルム表面が紫外線で照射されるので、３００ｎｍ
以下の波長をカットした紫外線の照射でも、その目的は
達成できる。Further, when both the SiOx vapor and the plastic film surface are irradiated with ultraviolet rays, both of the above-mentioned effects are exhibited at the same time, and a dense SiOx film is deposited on the plastic film surface. In this case also, the surface of the plastic film is irradiated with ultraviolet rays, so 300 nm
The purpose can be achieved even by irradiation with ultraviolet rays with the following wavelengths cut.
【００１０】本発明において使用されるプラスチックフ
ィルムの材質としては、ポリエチレン、ポリプロピレン
などのポリオレフィン系フィルム、セロハン、アセテー
トなどのセルロース系フィルム、ポリエチレンテレフタ
レート、ポリカーボネートなどのポリエステル系フィル
ム、ポリ塩化ビニル、ポリ塩化ビニリデン、ポリビニル
アルコールなどのビニル系フィルム、ポリスチレンフィ
ルム、ナイロン６、ナイロン１２などのポリアミド系フ
ィルム及び塩酸ゴムフィルムなどがあげられる。Examples of the material of the plastic film used in the present invention include polyolefin films such as polyethylene and polypropylene, cellulosic films such as cellophane and acetate, polyester films such as polyethylene terephthalate and polycarbonate, polyvinyl chloride, polyvinyl chloride. Examples thereof include vinyl films such as vinylidene and polyvinyl alcohol, polystyrene films, polyamide films such as nylon 6 and nylon 12, and hydrochloric acid rubber films.
【００１１】蒸発材料はＳｉＯであるが、それを蒸気化
するとき、あるいは被膜化するときには雰囲気中の酸素
と反応したり、酸素を解離したりして、ＳｉＯ2 ，Ｓｉ
も生成し、蒸気または被膜はＳｉ，ＳｉＯ，ＳｉＯ2 の
混合物となる。したがってプラスチックフィルムの表面
に形成される被膜の組成はそれらの平均粗成となるので
ＳｉＯｘと表現する。The evaporating material is SiO, but when it is vaporized or formed into a film, it reacts with oxygen in the atmosphere or dissociates oxygen to form SiO 2 , Si.
Is also produced and the vapor or coating is a mixture of Si, SiO, SiO 2 . Therefore, the composition of the coating film formed on the surface of the plastic film is the average coarseness thereof, and is expressed as SiOx.
【００１２】[0012]
【実施例】 （実施例１）図１に実施例１で使用した装置を示す。真
空容器１を６．６×１０-2Ｐａの圧力に調整し、るつぼ
２を１５００ｋ程度に加熱し、３で示すＳｉＯを蒸発さ
せシャッター８を所定の時間開くことによりポリエステ
ルフィルム４にＳｉＯｘを蒸着する。従来法ではそれだ
けであったが図２に示す分光分布をもつ高圧水銀ランプ
５を点灯し、その紫外線を集光ミラー６で集光してポリ
エステルフィルム４付近でＳｉＯｘ蒸気に照射し、Ｓｉ
Ｏｘを励起させて蒸着した。そのときの出力は点灯する
ランプの個数（１個あるいは２個）で調節した。EXAMPLES Example 1 FIG. 1 shows the apparatus used in Example 1. The vacuum container 1 was adjusted to a pressure of 6.6 × 10 -2 Pa, the crucible 2 was heated to about 1500 k, SiO shown by 3 was evaporated, and the shutter 8 was opened for a predetermined time to deposit SiOx on the polyester film 4. To do. Although it is only that in the conventional method, the high-pressure mercury lamp 5 having the spectral distribution shown in FIG. 2 is turned on, its ultraviolet rays are condensed by the condensing mirror 6, and the SiOx vapor is irradiated in the vicinity of the polyester film 4.
Ox was excited to deposit. The output at that time was adjusted by the number of lamps to be turned on (one or two).
【００１３】また、ＳｉＯｘ分子の励起波長の３００ｎ
ｍ以下の紫外線の照射が効果があることを証明するため
に、逆に３００ｎｍ以上の波長のみでは効果がないこと
を調べた。集光ミラー６の出口に波長が３００ｎｍ以下
の光をカットする紫外シャープカットフィルター７を設
置し波長３００ｎｍ以上のみの紫外線を照射しながらＳ
ｉＯｘ蒸着を実施した。作製したＳｉＯｘ蒸着フィルム
において酸素透過度を測定した結果を表１に示す。Further, the excitation wavelength of the SiOx molecule is 300 n.
In order to prove that the irradiation with ultraviolet rays of m or less is effective, conversely, it was investigated that only the wavelength of 300 nm or more had no effect. An ultraviolet sharp cut filter 7 that cuts light with a wavelength of 300 nm or less is installed at the exit of the condensing mirror 6, and while irradiating ultraviolet rays with a wavelength of 300 nm or more, S
iOx vapor deposition was performed. Table 1 shows the results of measuring the oxygen permeability of the produced SiOx vapor deposition film.
【００１４】その結果、ランプの全波長を照射した実施
例では、酸素透過度が従来法と較べて大きく低減でき
た。しかし波長３００ｎｍ以上のみの紫外線照射では従
来法と大差はなかった。従って全波長を照射した実施例
において、そのうち３００ｎｍ以下の波長の紫外線によ
り酸素透過度が低減したことが証明された。また紫外線
の出力は大きい方が酸素透過度はより低減した。As a result, in the embodiment in which all wavelengths of the lamp were irradiated, the oxygen permeability was significantly reduced as compared with the conventional method. However, irradiation with ultraviolet light having a wavelength of 300 nm or more did not significantly differ from the conventional method. Therefore, it was proved that in the examples irradiated with all wavelengths, the oxygen permeability was reduced by ultraviolet rays having a wavelength of 300 nm or less. Also, the larger the output of ultraviolet light, the lower the oxygen permeability.
【００１５】（実施例２）図３に実施例２で使用した装
置を示す。図３において図２と同一符号は図２と同一の
ものを示すので説明は省略する。実施例１と同様にＳｉ
Ｏｘを蒸着するが、そのとき紫外線をＳｉＯｘ蒸気に照
射するときにポリエステルフィルム４にも照射できるよ
うにした。ＳｉＯｘ蒸気とポリエステルフィルム４の両
方にランプの全波長と３００ｎｍ以上の波長を照射しな
がらＳｉＯｘ蒸着フィルムを作成し、酸素透過度を測定
した。その結果を表１に併せて示す。(Embodiment 2) FIG. 3 shows an apparatus used in Embodiment 2. In FIG. 3, the same symbols as those in FIG. 2 indicate the same components as those in FIG. Si as in Example 1
Ox is vapor-deposited, and when the SiOx vapor is irradiated with ultraviolet rays at that time, the polyester film 4 can also be irradiated. While irradiating both the SiOx vapor and the polyester film 4 with the full wavelength of the lamp and a wavelength of 300 nm or more, a SiOx vapor deposition film was prepared and the oxygen permeability was measured. The results are also shown in Table 1.
【００１６】その結果、３００ｎｍ以上の波長の紫外線
を照射したときでも酸素透過度は従来法と比較し大きく
低減でき、全波長を照射したときには更に酸素透過度が
低減できた。実施例１でＳｉＯｘ蒸気には３００ｎｍ以
下の紫外線が効果があったが、この実施例２ではポリエ
ステルフィルム４にも紫外線を照射したことで３００ｎ
ｍ以上も効果があり、プラスチックフィルムには、いず
れの波長の紫外線の照射も効果があることが判明した。As a result, the oxygen permeability was significantly reduced when irradiated with ultraviolet rays having a wavelength of 300 nm or more, and the oxygen permeability was further reduced when irradiated with all wavelengths. In Example 1, the ultraviolet rays having a wavelength of 300 nm or less were effective for the SiOx vapor, but in this Example 2, the polyester film 4 was also irradiated with the ultraviolet rays, and thus 300 n was obtained.
It was found that the effect of m or more is also effective, and that irradiation of ultraviolet rays of any wavelength is effective for the plastic film.
【００１７】（実施例３）実施例２と同じ図３の装置を
用い、シャッター８を開く前にポリエステルフィルム４
に紫外線を２０秒間照射し、ランプ５を消した直後にシ
ャッター８を開きＳｉＯ蒸着フィルムを作製した。その
ＳｉＯ蒸着フィルムの酸素透過度を測定した結果を表１
に併せて示す。(Embodiment 3) Using the same apparatus as in Embodiment 2 shown in FIG.
Then, the shutter 8 was opened immediately after the lamp 5 was turned off and the SiO vapor deposition film was prepared. The results of measuring the oxygen permeability of the SiO vapor deposition film are shown in Table 1.
Are also shown.
【００１８】その結果、プラスチックフィルムへの紫外
線の照射は、紫外線の波長が３００ｎｍ以上で酸素透過
度が低減でき、全波長ではより低減できた。いずれの波
長も効果があると考えられる。As a result, the irradiation of ultraviolet rays to the plastic film was able to reduce the oxygen permeability when the wavelength of the ultraviolet rays was 300 nm or more, and it was possible to further reduce it at all wavelengths. Both wavelengths are considered to be effective.
【００１９】[0019]
【表１】 [Table 1]
【００２０】[0020]
【発明の効果】本発明によれば、従来の真空槽内の圧力
を緩和な条件（例えば６．６×１０-2Ｐａ）に保つこと
によっても、従来法より緻密なＳｉＯｘが蒸着したプラ
スチックフィルムを得ることができる。According to the present invention, by maintaining the pressure in the conventional vacuum chamber under a mild condition (for example, 6.6 × 10 -2 Pa), a plastic film having a denser SiOx vapor deposition than the conventional method is deposited. Can be obtained.
【図面の簡単な説明】[Brief description of drawings]
【図１】本発明の実施例１を実施する装置の概略図。FIG. 1 is a schematic view of an apparatus for carrying out Example 1 of the present invention.
【図２】本発明の実施例において用いた高圧水銀ランプ
のスペクトル図。FIG. 2 is a spectrum diagram of a high pressure mercury lamp used in Examples of the present invention.
【図３】本発明の実施例２，３を実施する装置の概略
図。FIG. 3 is a schematic view of an apparatus for carrying out Examples 2 and 3 of the present invention.
Claims (1)
よりＳｉＯｘ皮膜を形成する方法において、ＳｉＯｘ蒸
気及び／又はプラスチックフィルム表面に紫外線を照射
しつゝ蒸着することを特徴とするＳｉＯｘ皮膜の形成方
法。1. A method for forming a SiOx film on a surface of a plastic film by a PVD method, which comprises irradiating ultraviolet rays on the SiOx vapor and / or the surface of the plastic film while irradiating with ultraviolet rays to form a SiOx film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22421993A JPH0776767A (en) | 1993-09-09 | 1993-09-09 | Formation of silicon oxide film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22421993A JPH0776767A (en) | 1993-09-09 | 1993-09-09 | Formation of silicon oxide film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0776767A true JPH0776767A (en) | 1995-03-20 |
Family
ID=16810384
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP22421993A Withdrawn JPH0776767A (en) | 1993-09-09 | 1993-09-09 | Formation of silicon oxide film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0776767A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001086707A1 (en) * | 2000-05-08 | 2001-11-15 | Denki Kagaku Kogyo Kabushiki Kaisha | LOW RELATIVE PERMITTIVITY SIOx FILM, PRODUCTION METHOD, SEMICONDUCTOR DEVICE COMPRISING THE FILM |
| WO2019203237A1 (en) * | 2018-04-18 | 2019-10-24 | Ａｇｃ株式会社 | Vapor deposition material, base-layer-comprising substrate, functional-layer-comprising article, and methods for manufacturing same |
-
1993
- 1993-09-09 JP JP22421993A patent/JPH0776767A/en not_active Withdrawn
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001086707A1 (en) * | 2000-05-08 | 2001-11-15 | Denki Kagaku Kogyo Kabushiki Kaisha | LOW RELATIVE PERMITTIVITY SIOx FILM, PRODUCTION METHOD, SEMICONDUCTOR DEVICE COMPRISING THE FILM |
| US7164191B2 (en) | 2000-05-08 | 2007-01-16 | Denki Kagaku Kogyo Kabushiki Kaisha | Low relative permittivity SiOx film including a porous material for use with a semiconductor device |
| WO2019203237A1 (en) * | 2018-04-18 | 2019-10-24 | Ａｇｃ株式会社 | Vapor deposition material, base-layer-comprising substrate, functional-layer-comprising article, and methods for manufacturing same |
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