JPH04270736A - Method for forming cured protective film - Google Patents
Method for forming cured protective filmInfo
- Publication number
- JPH04270736A JPH04270736A JP3030984A JP3098491A JPH04270736A JP H04270736 A JPH04270736 A JP H04270736A JP 3030984 A JP3030984 A JP 3030984A JP 3098491 A JP3098491 A JP 3098491A JP H04270736 A JPH04270736 A JP H04270736A
- Authority
- JP
- Japan
- Prior art keywords
- film
- substrate
- tetraethoxysilane
- plasma
- forming
- 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- Withdrawn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
- 238000000034 method Methods 0.000 title claims abstract description 17
- 230000001681 protective effect Effects 0.000 title claims abstract description 16
- 239000010408 film Substances 0.000 claims abstract description 68
- 239000000758 substrate Substances 0.000 claims abstract description 36
- 239000007789 gas Substances 0.000 claims abstract description 25
- 239000010409 thin film Substances 0.000 claims abstract description 21
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000004033 plastic Substances 0.000 claims abstract description 15
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 claims abstract description 9
- YTEISYFNYGDBRV-UHFFFAOYSA-N [(dimethyl-$l^{3}-silanyl)oxy-dimethylsilyl]oxy-dimethylsilicon Chemical compound C[Si](C)O[Si](C)(C)O[Si](C)C YTEISYFNYGDBRV-UHFFFAOYSA-N 0.000 claims abstract description 4
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 claims abstract description 4
- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 claims abstract description 4
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000012495 reaction gas Substances 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 30
- 229910052681 coesite Inorganic materials 0.000 abstract description 15
- 229910052906 cristobalite Inorganic materials 0.000 abstract description 15
- 239000000377 silicon dioxide Substances 0.000 abstract description 15
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 15
- 229910052682 stishovite Inorganic materials 0.000 abstract description 15
- 229910052905 tridymite Inorganic materials 0.000 abstract description 15
- 150000003961 organosilicon compounds Chemical class 0.000 abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 10
- 239000001301 oxygen Substances 0.000 description 10
- 229910052710 silicon Inorganic materials 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 4
- 239000004417 polycarbonate Substances 0.000 description 4
- 229920000515 polycarbonate Polymers 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- 239000012769 display material Substances 0.000 description 2
- 239000012776 electronic material Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- -1 silicon organic compound Chemical class 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001941 electron spectroscopy Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000003678 scratch resistant effect Effects 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Landscapes
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
- Treatments Of Macromolecular Shaped Articles (AREA)
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は硬化保護膜の製造方法に
関し、特にビルディング・家屋等の窓材、航空機・船舶
・自動車などの窓材、電子材料・光学材料・表示材料等
表面の性質として高硬度，耐摩耗性及び耐擦傷性等が要
求されるプラスチック基板表面の硬化保護膜の形成方法
に関する。[Industrial Application Field] The present invention relates to a method for producing a cured protective film, and in particular, it is used as a surface property for window materials for buildings, houses, etc., window materials for aircraft, ships, automobiles, etc., electronic materials, optical materials, display materials, etc. This invention relates to a method for forming a hardened protective film on the surface of a plastic substrate that requires high hardness, wear resistance, scratch resistance, etc.
【０００２】0002
【従来の技術】従来、プラスチック基板表面を高硬度化
して、耐摩耗性及び耐擦傷性を改良する技術としては、
図４に示す如くプラズマ重合法を用いた成膜装置が知ら
れている。[Prior Art] Conventionally, techniques for improving wear resistance and scratch resistance by increasing the hardness of the surface of plastic substrates include:
As shown in FIG. 4, a film forming apparatus using a plasma polymerization method is known.
【０００３】図中の１は真空容器であり。この真空容器
１には、モノマ−流量調整弁２を介して有機ケイ素化合
物モノマ−３が導入されるようになっている。前記真空
容器１内には高周波電極４とア−ス電極５が平行に配置
され、ア−ス電極５上にプラスチック基板６が配置され
ている。前記高周波電極４には、マッチングボックス７
を介して電源８より電力が供給されるようになっている
。前記真空容器１にはバルブ９を介して真空ポンプ１０
が接続され、この真空ポンプにより真空引きされるよう
になっている。1 in the figure is a vacuum container. An organosilicon compound monomer 3 is introduced into the vacuum container 1 via a monomer flow rate regulating valve 2 . A high frequency electrode 4 and a ground electrode 5 are arranged in parallel in the vacuum container 1, and a plastic substrate 6 is arranged on the ground electrode 5. The high frequency electrode 4 has a matching box 7
Power is supplied from a power source 8 via the power source 8. A vacuum pump 10 is connected to the vacuum container 1 via a valve 9.
is connected and evacuated by this vacuum pump.
【０００４】こうした構成の装置において、前記基板６
に硬化保護膜を形成するには、まず真空容器１を真空ポ
ンプ１０で減圧し、例えば圧力０．０１Ｔｏｒｒ 程度
に設定する。次に、前記調整弁２を開いて、有機ケイ素
化合モノマ−例えばオクタメチルシクロテトラシロキサ
ンを真空容器１内に導入して、その圧力を約５．０×１
０−２ Ｔｏｒｒ にする。つづいて、例えば周波数
１３．５６ＭＨｚの高周波電源８より出力を約１００Ｗ
として、プラズマを発生させ、５．０〜８．０分間、高
硬度膜を前記基板６に堆積する。以上のようにして得ら
れる膜は、ケイ素、酸素、炭素を組成にした高硬度の膜
である。[0004] In an apparatus having such a configuration, the substrate 6
To form a cured protective film on the substrate, first, the pressure of the vacuum container 1 is reduced using the vacuum pump 10, and the pressure is set to, for example, about 0.01 Torr. Next, the regulating valve 2 is opened, an organosilicon compound monomer such as octamethylcyclotetrasiloxane is introduced into the vacuum container 1, and the pressure is adjusted to approximately 5.0×1.
Set it to 0-2 Torr. Next, for example, the output is about 100W from the high frequency power supply 8 with a frequency of 13.56MHz.
A high hardness film is deposited on the substrate 6 for 5.0 to 8.0 minutes by generating plasma. The film obtained as described above is a highly hard film whose composition is silicon, oxygen, and carbon.
【０００５】[0005]
【発明が解決しようとする課題】しかしながら、従来技
術によれば、成膜されたＳｉＯ２ 系、ＳｉＣ系あるい
はＣ系の薄膜は高硬度の膜であるが、以下に述べる欠点
を有し、実用には供せられないという。
（１） ＳｉＯ２ 系，ＳｉＣ系あるいはＣ系の膜は、
Ｓｉ，Ｏ，Ｃを主成分とする高硬度の膜であるが、傷が
付き易く、高度が十分に高くない。
（２） プラスチック基板６と高硬度膜の結合力が十分
に強くないため、高硬度膜がプラスチック基板６から剥
離し易い。[Problems to be Solved by the Invention] However, according to the prior art, the SiO2-based, SiC-based, or C-based thin films formed are highly hard films, but they have the following drawbacks, making them impractical for practical use. It is said that it cannot be offered. (1) SiO2-based, SiC-based, or C-based films are
Although it is a highly hard film mainly composed of Si, O, and C, it is easily scratched and its altitude is not high enough. (2) Since the bond between the plastic substrate 6 and the high-hardness film is not strong enough, the high-hardness film easily peels off from the plastic substrate 6.
【０００６】本発明は上記事情に鑑みてなされたもので
、プラスチック基板との結合力が強力なＳｉ−Ｏ−Ｃ系
薄膜を下地膜として、高硬度膜としてのＳｉＯ２ 膜を
下地膜上に形成して、高硬度膜の損傷を軽減できるとと
もに、高硬度膜が前記基板から剥離するのを回避できる
硬化保護膜の形成方法を提供できる。The present invention has been made in view of the above circumstances, and uses a Si-O-C thin film that has a strong bonding force with a plastic substrate as a base film, and forms a SiO2 film as a high hardness film on the base film. As a result, it is possible to provide a method for forming a cured protective film that can reduce damage to the highly hard film and prevent the highly hard film from peeling off from the substrate.
【０００７】[0007]
【課題を解決するための手段】本発明者らは、上述した
従来法の欠点を解消するため、鋭意研究した結果、プラ
スチック基板表面に予めＳｉ，Ｃ，Ｏを主成分とする有
機系の薄膜を成膜した後、その薄膜の上に高硬度膜とし
て無機系のＳｉＯ２ 膜を成膜する方法、即ちプラスチ
ック基板との結合が強く、かつＳｉＯ２ 膜との結合が
強いＳｉ，Ｃ，Ｏを主成分とするＳｉ−Ｃ−０系の薄膜
を下地膜として用い、その上にＳｉＯ２ 膜を積層させ
ることが著しく効果的であることを究明した。[Means for Solving the Problems] In order to solve the above-mentioned drawbacks of the conventional method, the present inventors have conducted intensive research and have developed an organic thin film containing Si, C, and O as main components on the surface of a plastic substrate. After forming a film, an inorganic SiO2 film is formed as a highly hard film on the thin film. It has been found that it is extremely effective to use a Si-C-0 based thin film as a base film and to stack an SiO2 film thereon.
【０００８】本発明では、まず、原料ガスとして、Ｓｉ
（ＯＣ２ Ｈ５ ）４ （テトラエトキシシラン）ある
いはＳｉＯ２ （ＣＨ３ ）２ （Ｃ２ Ｏ５ ）２（
ジエトキシジメチルシラン）を用いたプラズマＣＶＤに
よりプラスチック基板表面に、Ｓｉ，Ｃ，Ｏを主成分と
するＳｉ−Ｃ−Ｏ系薄膜を下地として活着させ、この後
上記テトラエトキシシラン（又はジエトキシジメチルシ
ラン）とＯ２ の混合ガスを用いたプラズマＣＶＤによ
り、上記Ｓｉ−Ｃ−Ｏ系薄膜の上にＳｉＯ２ 膜を形成
させるようにした。In the present invention, first, Si is used as the raw material gas.
(OC2 H5 )4 (tetraethoxysilane) or SiO2 (CH3 )2 (C2 O5 )2(
A Si-C-O thin film mainly composed of Si, C, and O is adhered to the surface of a plastic substrate by plasma CVD using tetraethoxysilane (or diethoxydimethylsilane), and then the above tetraethoxysilane (or diethoxydimethyl A SiO2 film was formed on the Si--C--O thin film by plasma CVD using a mixed gas of (silane) and O2.
【０００９】即ち、本発明は、反応容器内にプラスチッ
ク基板を配置した状態で、前記反応容器内に反応ガスを
導入するとともに反応容器内でプラズマを発生させて前
記基板上に硬化保護膜を形成する方法において、まずテ
トラエトキシシランまたはジエトキシジメチルシランの
プラズマにより前記基板表面にＳｉ−Ｏ−Ｃ系薄膜を下
地膜として成膜した後、ヘキサメチルジシロキサン，テ
トラエトキシシラン，ヘキサメチルトリシロキサン，ジ
エトキシジメチルシラン，メチルトリエトキシシラン，
オクタメチルシクロテトラシロキサンなどのケイ素有機
化合物ガスとＯ２ の混合ガスのプラズマにより、前記
薄膜上にＳｉＯ２ 膜を形成することを特徴とする硬化
保護膜の形成方法である。That is, in the present invention, with a plastic substrate placed in a reaction container, a reaction gas is introduced into the reaction container and plasma is generated in the reaction container to form a cured protective film on the substrate. In this method, a Si-O-C thin film is first formed as a base film on the surface of the substrate using tetraethoxysilane or diethoxydimethylsilane plasma, and then hexamethyldisiloxane, tetraethoxysilane, hexamethyltrisiloxane, diethoxydimethylsilane, methyltriethoxysilane,
This method of forming a cured protective film is characterized in that a SiO2 film is formed on the thin film using plasma of a mixed gas of a silicon organic compound gas such as octamethylcyclotetrasiloxane and O2.
【００１０】0010
【作用】本発明においては、次のようにして硬化保護膜
を形成する。まず、前記プラスチック基板をア−ス電極
上に設置する。つづいて、真空ポンプを作動させて反応
容器内を排気し、所定の真空度に到達させる。次に、原
料ガスとしてのテトラエトキシシラン（またはジエトキ
シジメチルシラン）を反応容器の中へ所定流量で供給す
る。[Operation] In the present invention, a cured protective film is formed as follows. First, the plastic substrate is placed on the ground electrode. Next, the vacuum pump is operated to evacuate the inside of the reaction vessel to reach a predetermined degree of vacuum. Next, tetraethoxysilane (or diethoxydimethylsilane) as a raw material gas is supplied into the reaction vessel at a predetermined flow rate.
【００１１】次に、高周波電源からマッチングボックス
などを介して高周波電極及びア−ス電極に高周波電力を
供給する。これにより、上記原料ガスは、グロ−放電プ
ラズマ化される。この場合、原料ガスが解離し、Ｓｉ，
Ｃ，Ｏなどから構成されるＳｉ−Ｃ−Ｏ系薄膜が前記基
板上に堆積する。Next, high frequency power is supplied from the high frequency power source to the high frequency electrode and the ground electrode via a matching box or the like. As a result, the raw material gas is turned into glow discharge plasma. In this case, the raw material gas dissociates, and Si,
A Si--C--O based thin film composed of C, O, etc. is deposited on the substrate.
【００１２】次に、酸素供給源より反応容器の中へ酸素
を供給させる。その結果、上記テトラエトキシシランと
上記酸素の混合ガスが、上記高周波電極，ア−ス電極の
間でグロ−放電プラズマ化され、プラズマＣＶＤ現象に
よりＳｉＯ２系の膜が上記Ｓｉ−Ｃ−Ｏ系薄膜の上に堆
積する。Next, oxygen is supplied from the oxygen supply source into the reaction vessel. As a result, the mixed gas of the tetraethoxysilane and the oxygen is turned into glow discharge plasma between the high-frequency electrode and the earth electrode, and the SiO2-based film is transformed into the Si-C-O-based thin film by the plasma CVD phenomenon. deposits on top of.
【００１３】[0013]
【実施例】［実施例１］[Example] [Example 1]
【００１４】図１は本発明の実施例１に係る成膜装置の
全体構成図である。図中の２１は反応容器である。この
反応容器２１内には、高周波電極２２とア−ス電極２３
が平行に配置され、前記ア−ス電極２３上にポリカ−ボ
ネ−ト基板２４が配置されている。前記ア−ス電極２３
は反応容器２１と電気的に導通になっており、上記高周
波電極２２と組合わせて使用することにより反応容器２
１の中のガスをグロ−放電プラズマにする。前記反応容
器２１には、第１の弁２５、第１の流量調整器２６を介
して第１の原料ガスであるテトラエトキシシラン供給源
２７が接続されている。前記反応容器２１には、第２の
弁２８、第２の流量調整器２９を介して第２の原料ガス
である酸素供給源３０が接続されている。FIG. 1 is an overall configuration diagram of a film forming apparatus according to Embodiment 1 of the present invention. 21 in the figure is a reaction container. Inside this reaction vessel 21, there are a high frequency electrode 22 and a ground electrode 23.
are arranged in parallel, and a polycarbonate substrate 24 is arranged on the ground electrode 23. The earth electrode 23
is electrically connected to the reaction vessel 21, and when used in combination with the high frequency electrode 22, the reaction vessel 2
The gas in 1 is turned into glow discharge plasma. A tetraethoxysilane supply source 27, which is a first raw material gas, is connected to the reaction vessel 21 via a first valve 25 and a first flow regulator 26. An oxygen supply source 30, which is a second source gas, is connected to the reaction vessel 21 via a second valve 28 and a second flow rate regulator 29.
【００１５】前記反応容器２１内の高周波電極２２には
電流導入端子３１及びマッチングボックス３２を介して
高周波電源３３が連結され、これにより高周波電極２２
に電力が供給される。前記真空容器２１には第３の弁３
４を介して第１の真空ポンプ３５が連結され、これによ
り真空容器２１内のガスが排出される。前記真空容器２
１には第４の弁３６を介して第２の真空ポンプ３７が連
結され、これにより真空容器２１内のガスが排出される
。前記反応容器２１には真空計３８が連結されている。A high frequency power source 33 is connected to the high frequency electrode 22 in the reaction vessel 21 via a current introduction terminal 31 and a matching box 32, so that the high frequency electrode 22
Power is supplied to the A third valve 3 is provided in the vacuum container 21.
4 is connected to a first vacuum pump 35, thereby discharging the gas in the vacuum container 21. The vacuum container 2
1 is connected to a second vacuum pump 37 via a fourth valve 36, whereby the gas in the vacuum container 21 is exhausted. A vacuum gauge 38 is connected to the reaction vessel 21 .
【００１６】こうした構成の成膜装置において、前記基
板２４に硬化保護膜を形成するには、次のように行う。
（１） まず、前記基板２４をア−ス電極２３上に設置
する。つづいて、第１の真空ポンプ３５，第２の真空ポ
ンプ３７を作動させて反応容器２１内を排気し、約１×
１０−６〜１×１０−７Ｔｏｒｒ の真空度に到達させ
る。次に、第４の弁３６を閉にし、第１の弁２５を開に
して、第１の流量調整器２６を用いて、テトラエトキシ
シランを反応容器２１の中へ、約５０ｃｃ／の流量で供
給する。なお、この場合、反応容器２１の圧力は約０．
０２Ｔｏｒｒ であった。In the film forming apparatus having such a configuration, forming a cured protective film on the substrate 24 is performed as follows. (1) First, the substrate 24 is placed on the ground electrode 23. Next, the first vacuum pump 35 and the second vacuum pump 37 are operated to evacuate the inside of the reaction vessel 21, and about 1×
A vacuum level of 10-6 to 1 x 10-7 Torr is achieved. Next, the fourth valve 36 is closed, the first valve 25 is opened, and the first flow regulator 26 is used to introduce tetraethoxysilane into the reaction vessel 21 at a flow rate of about 50 cc/. supply In this case, the pressure in the reaction vessel 21 is about 0.
It was 0.02 Torr.
【００１７】（２） 次に、高周波電源３３からマッチ
ングボックス３２及び電流導入端子３１などを介して高
周波電極２２及びア−ス電極２３に高周波電力を供給す
る。その結果、上記テトラエトキシシランは、グロ−放
電プラズマ化される。この場合、原料ガスのＳｉ（ＯＣ
２ Ｈ５ ）４ （テトラエトキシシラン）のガスが解
離し、Ｓｉ，Ｃ，Ｏなどから構成されるＳｉ−Ｃ−Ｏ系
薄膜が前記基板２４上に堆積する。なお、図示していな
いが、Ａｒ，Ｈｅ，Ｎｅなどの希ガスを上記原料ガスと
同程度の流量で混入させ、プラズマ化を容易に行わせる
こともできる。(2) Next, high frequency power is supplied from the high frequency power supply 33 to the high frequency electrode 22 and the ground electrode 23 via the matching box 32, the current introduction terminal 31, etc. As a result, the tetraethoxysilane is turned into glow discharge plasma. In this case, the raw material gas Si(OC
2 H5 )4 (tetraethoxysilane) gas is dissociated, and a Si--C--O based thin film composed of Si, C, O, etc. is deposited on the substrate 24. Although not shown, a rare gas such as Ar, He, or Ne may be mixed in at a flow rate comparable to that of the source gas to facilitate plasma formation.
【００１８】（３） 次に、第２の弁２８を開にして、
酸素供給源３０より第２の流量調整器２９及び第２の弁
２８を介して反応容器２１の中へ、約１００ ｃｃ／分
の流量で酸素を供給させる。その結果、上記テトラエト
キシシランと上記酸素の混合ガスが、上記高周波電極２
２，ア−ス電極２３の間でグロ−放電プラズマ化され、
プラズマＣＶＤ現象によりＳｉＯ２ 系の膜が上記Ｓｉ
−Ｃ−Ｏ系薄膜の上に堆積する。なお、上記成膜実験で
は、Ｓｉ−Ｃ−Ｏ系膜の成膜時間は約１０分間，ＳｉＯ
２系膜の成膜は約３０分間であったが、図２に示すよう
に基板２４上に薄膜（有機系下地膜）３９、ＳｉＯ２
膜４０の２種類の膜が積層された。(3) Next, open the second valve 28,
Oxygen is supplied from the oxygen supply source 30 through the second flow regulator 29 and second valve 28 into the reaction vessel 21 at a flow rate of about 100 cc/min. As a result, the mixed gas of the tetraethoxysilane and the oxygen is transferred to the high frequency electrode 2.
2. Glow discharge becomes plasma between the earth electrodes 23,
Due to the plasma CVD phenomenon, the SiO2-based film is
Deposited on the -C-O based thin film. In the above film-forming experiment, the film-forming time of the Si-C-O film was about 10 minutes, and the Si-C-O film was formed for about 10 minutes.
The deposition of the 2-based film took about 30 minutes, and as shown in FIG.
Two types of membrane 40 were laminated.
【００１９】しかして、上記実施例１によれば、テトラ
エトキシシランを用いてポリカ−ボネ−ト基板２４表面
に予めＳｉ，Ｃ，Ｏを主成分とする有機系の薄膜３９を
成膜した後、テトラエトキシシランと酸素の混合ガスを
グロ−放電プラズマ化して前記薄膜３９の上に高硬度膜
としての無機系のＳｉＯ２ 膜４０を成膜するため、十
分に硬く傷が付けにくい高硬度膜が得られると共に、前
記基板２４からの剥離を回避できる。 事実、前記基
板２４上に形成された薄膜３９，ＳｉＯ２ 膜４０の組
成分析をＥＳＣＡ（Ｅｌｅｃｔｒｏｎ Ｓｐｅｃｔｒｏ
ｓｃｏｐｙ ｆｏｒ Ｃｈｅｍｉｃａｌ Ａｎａｌｙｓ
ｉｓ ）で測定したところ、図３に示す結果が得られた
。同図によれば、基板上にＳｉ−Ｃ−Ｏ系薄膜が存在し
、その上にＳｉＯ２ 系膜が堆積していることが判明し
た。得られた膜の付着強度は、接着テ−プ貼付による引
き剥がし方法で調査したところ、非常に強いことが判明
した。According to the first embodiment, after forming an organic thin film 39 containing Si, C, and O as main components on the surface of the polycarbonate substrate 24 using tetraethoxysilane, Since the inorganic SiO2 film 40 as a high hardness film is formed on the thin film 39 by turning a mixed gas of tetraethoxysilane and oxygen into glow discharge plasma, a sufficiently hard and scratch-resistant high hardness film is formed. At the same time, peeling from the substrate 24 can be avoided. In fact, the composition analysis of the thin film 39 and the SiO2 film 40 formed on the substrate 24 was performed using ESCA (Electron Spectrometry).
Scopy for Chemical Analysis
is ), the results shown in FIG. 3 were obtained. According to the figure, it was found that a Si--C--O based thin film was present on the substrate, and an SiO2 based film was deposited thereon. The adhesive strength of the obtained film was investigated by a peeling method using adhesive tape, and it was found to be very strong.
【００２０】なお、上記実施例では、ＳｉＯ２ 系膜を
成膜するのに、テトラエトキシシランとＯ２ の混合ガ
スを用いた場合について説明したが、これに限定されな
い。
例えば、ヘキサメチルジシロキサン、ヘキサメチルトリ
シロキサン，ジエトキシジメチルシラン，メチルトリエ
トキシシランなどのケイ素有機化合物ガスとＯ２ の混
合ガスを用いても、上記実施例と同様に、上記実施例で
得られた膜と同じ高硬度でかつポリカ−ボネ−ト基板と
の結合力の強い膜が得られる。[0020] In the above embodiment, a case was explained in which a mixed gas of tetraethoxysilane and O2 was used to form a SiO2-based film, but the present invention is not limited to this. For example, even if a mixed gas of O2 and a silicon organic compound gas such as hexamethyldisiloxane, hexamethyltrisiloxane, diethoxydimethylsilane, or methyltriethoxysilane is used, the results obtained in the above example can be obtained in the same manner as in the above example. A film can be obtained that has the same high hardness as the other films and has strong bonding strength with the polycarbonate substrate.
【００２１】[0021]
【発明の効果】以上詳述した如く本発明の硬化保護膜の
形成方法によれば、プラスチック基板との結合力が強力
なＳｉ−Ｏ−Ｃ系膜を下地膜として、高硬度膜を下地膜
上に形成して、高硬度膜の損傷を軽減できるとともに、
高硬度膜が前記基板から剥離するのを回避でき、ビルデ
ィング・家屋等の窓材、航空機・船舶・自動車などの窓
材、電子材料・光学材料・表示材料等表面の性質として
高硬度，耐摩耗性及び耐擦傷性等が要求されるプラスチ
ック基板に有用で、産業情著しく価値がある。硬化保護
膜の形成方法を提供できる。Effects of the Invention As detailed above, according to the method for forming a cured protective film of the present invention, a Si-O-C film having strong bonding strength with a plastic substrate is used as a base film, and a high hardness film is used as a base film. It is possible to reduce damage to the high-hardness film by forming it on top of the
The high hardness film can avoid peeling from the substrate, and has high hardness and wear resistance as a surface property for window materials for buildings, houses, etc., window materials for aircraft, ships, automobiles, etc., electronic materials, optical materials, display materials, etc. It is useful for plastic substrates that require high durability and scratch resistance, and is of great value in industry. A method for forming a cured protective film can be provided.
【図１】本発明の一実施例に係る成膜装置の全体構成を
示す説明図。FIG. 1 is an explanatory diagram showing the overall configuration of a film forming apparatus according to an embodiment of the present invention.
【図２】本発明方法により形成された硬化保護膜の説明
図。FIG. 2 is an explanatory diagram of a cured protective film formed by the method of the present invention.
【図３】本発明方法により形成された硬化保護膜の組成
分析をＥＳＣＡで測定した結果を示す説明図。FIG. 3 is an explanatory diagram showing the results of compositional analysis of a cured protective film formed by the method of the present invention measured by ESCA.
【図４】従来の成膜装置の全体構成を示す説明図。FIG. 4 is an explanatory diagram showing the overall configuration of a conventional film forming apparatus.
２１…反応容器、２２…高周波電極、２３…ア−ス電極
、２４…ポリカ−ボネ−ト基板、２５，２８，３４，３
６…弁、２６，２９…流量調整器、２７…テトラエトキ
シ供給源、３０…酸素供給源、３２…マッチングボック
ス、３３…高周波電源、３５，３７…真空ポンプ、３８
…真空計。21... Reaction container, 22... High frequency electrode, 23... Earth electrode, 24... Polycarbonate substrate, 25, 28, 34, 3
6... Valve, 26, 29... Flow rate regulator, 27... Tetraethoxy supply source, 30... Oxygen supply source, 32... Matching box, 33... High frequency power supply, 35, 37... Vacuum pump, 38
…Vacuum gauge.
Claims (1)
した状態で、前記反応容器内に反応ガスを導入するとと
もに反応容器内でプラズマを発生させて前記基板上に硬
化保護膜を形成する方法において、まずテトラエトキシ
シランまたはジエトキシジメチルシランのプラズマによ
り前記基板表面にＳｉ−Ｏ−Ｃ系薄膜を下地膜として成
膜した後、ヘキサメチルジシロキサン，テトラエトキシ
シラン，ヘキサメチルトリシロキサン，ジエトキシジメ
チルシラン，メチルトリエトキシシラン，オクタメチル
シクロテトラシロキサンなどのケイ素有機化合物ガスと
Ｏ２ の混合ガスのプラズマにより、前記薄膜上にＳｉ
Ｏ２ 膜を形成することを特徴とする硬化保護膜の形成
方法。1. A method for forming a cured protective film on the substrate by introducing a reaction gas into the reaction container and generating plasma in the reaction container with a plastic substrate disposed in the reaction container, the method comprising: First, a Si-O-C thin film is formed as a base film on the surface of the substrate using tetraethoxysilane or diethoxydimethylsilane plasma, and then hexamethyldisiloxane, tetraethoxysilane, hexamethyltrisiloxane, diethoxydimethylsilane is used as a base film. , methyltriethoxysilane, octamethylcyclotetrasiloxane, etc., and a mixed gas of O2, Si is deposited on the thin film.
A method for forming a cured protective film, the method comprising forming an O2 film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3030984A JPH04270736A (en) | 1991-02-26 | 1991-02-26 | Method for forming cured protective film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3030984A JPH04270736A (en) | 1991-02-26 | 1991-02-26 | Method for forming cured protective film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04270736A true JPH04270736A (en) | 1992-09-28 |
Family
ID=12318899
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3030984A Withdrawn JPH04270736A (en) | 1991-02-26 | 1991-02-26 | Method for forming cured protective film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04270736A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05345831A (en) * | 1992-06-15 | 1993-12-27 | Toyo Seikan Kaisha Ltd | Production of gas barrier plastic material |
| JPH10500609A (en) * | 1994-03-03 | 1998-01-20 | モンサント カンパニー | High wear resistance and flexible coatings for flexible substrates |
| JP2007238666A (en) * | 2006-03-06 | 2007-09-20 | National Institute Of Advanced Industrial & Technology | Method for producing polymer composite film, polymer composite film and packaging material |
-
1991
- 1991-02-26 JP JP3030984A patent/JPH04270736A/en not_active Withdrawn
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05345831A (en) * | 1992-06-15 | 1993-12-27 | Toyo Seikan Kaisha Ltd | Production of gas barrier plastic material |
| JPH10500609A (en) * | 1994-03-03 | 1998-01-20 | モンサント カンパニー | High wear resistance and flexible coatings for flexible substrates |
| JP2007238666A (en) * | 2006-03-06 | 2007-09-20 | National Institute Of Advanced Industrial & Technology | Method for producing polymer composite film, polymer composite film and packaging material |
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