JPH04136156A - Transparent protective film structure - Google Patents
Transparent protective film structureInfo
- Publication number
- JPH04136156A JPH04136156A JP25622590A JP25622590A JPH04136156A JP H04136156 A JPH04136156 A JP H04136156A JP 25622590 A JP25622590 A JP 25622590A JP 25622590 A JP25622590 A JP 25622590A JP H04136156 A JPH04136156 A JP H04136156A
- Authority
- JP
- Japan
- Prior art keywords
- fluorine
- protective film
- transparent protective
- film structure
- substrate
- 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
- 230000001681 protective effect Effects 0.000 title claims abstract description 16
- 239000000758 substrate Substances 0.000 claims abstract description 16
- -1 Polytetrafluoroethylene Polymers 0.000 claims abstract description 13
- 238000007733 ion plating Methods 0.000 claims abstract description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052596 spinel Inorganic materials 0.000 claims abstract description 6
- 239000011029 spinel Substances 0.000 claims abstract description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 5
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 10
- 229910052731 fluorine Inorganic materials 0.000 claims description 10
- 239000011737 fluorine Substances 0.000 claims description 10
- 229920000620 organic polymer Polymers 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- 239000000049 pigment Substances 0.000 claims description 3
- 229920000728 polyester Polymers 0.000 claims description 3
- 229920001296 polysiloxane Polymers 0.000 claims description 2
- 239000002245 particle Substances 0.000 abstract description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 6
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 229910052681 coesite Inorganic materials 0.000 abstract description 3
- 229910052906 cristobalite Inorganic materials 0.000 abstract description 3
- 239000000377 silicon dioxide Substances 0.000 abstract description 3
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 3
- 229910052682 stishovite Inorganic materials 0.000 abstract description 3
- 229910052905 tridymite Inorganic materials 0.000 abstract description 3
- 238000007740 vapor deposition Methods 0.000 abstract description 3
- 238000001704 evaporation Methods 0.000 abstract description 2
- 230000007935 neutral effect Effects 0.000 abstract description 2
- 230000005284 excitation Effects 0.000 abstract 3
- 239000000853 adhesive Substances 0.000 abstract 2
- 230000001070 adhesive effect Effects 0.000 abstract 2
- 230000008020 evaporation Effects 0.000 abstract 1
- 239000000203 mixture Substances 0.000 abstract 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 abstract 1
- 239000010408 film Substances 0.000 description 31
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 12
- 229910052786 argon Inorganic materials 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000012860 organic pigment Substances 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 229920005597 polymer membrane Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 210000004243 sweat Anatomy 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000001947 vapour-phase growth Methods 0.000 description 1
Landscapes
- Physical Vapour Deposition (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
この発明は、透明保護膜構造に関するものである。さら
に詳しくは、この発明は、時計、装身具等の外装品や装
飾品に有効な密着性、耐候性等の機能性に優れた透明保
護膜構造に関するものである。DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a transparent protective film structure. More specifically, the present invention relates to a transparent protective film structure with excellent functionality such as adhesion and weather resistance, which is effective for exterior products and accessories such as watches and jewelry.
（従来の技術）
従来より、時計、装身具等の外装品や装飾品については
、金属、合金、プラスティック等の基板に鍍金を施した
り、あるいは金属、無機物、有機ポリマーなどの蒸着薄
膜を形成して、色調を改善し美観性を向上させるととも
に、表面に耐食性、耐候性等の機能性を付与してきてい
る。(Prior art) Exterior products and accessories such as watches and jewelry have traditionally been produced by plating metal, alloy, plastic, etc. substrates, or by forming vapor-deposited thin films of metals, inorganic materials, organic polymers, etc. In addition to improving the color tone and aesthetics, the surface has been given functionality such as corrosion resistance and weather resistance.
（発明が解決しようとする課題）
その一方で、近年、表面保護膜に対するニーズが高まっ
ており、各種の色調や色相を有する基体表面を、水分や
空気、外部からの衝撃等による劣化から防護し、それら
の色合いを損なうことなく、あるいはさらにその色合い
を引き立たせるための耐久性、色調に優れた表面保護膜
への要請が強まっている。(Problem to be solved by the invention) On the other hand, in recent years there has been an increasing need for surface protective films, which protect the surfaces of substrates with various tones and hues from deterioration caused by moisture, air, external impact, etc. There is an increasing demand for a surface protective film with excellent durability and color tone that does not impair the color or even enhances the color.
しかしながら、これまでの技術ではこのような要請に充
分に対応することができなかった。たとえば、Ｓ ｉｏ
、 Ｓ ｉｏ＊等の無機質膜や、アクリル重合膜、さ
らには撥水性に優れたテフロン膜等があるが、気相蒸着
によって形成しても、クラックや剥離が生じ、実用的な
ものとなってはいない。However, conventional techniques have not been able to adequately meet such demands. For example, S io
There are inorganic films such as , Sio*, acrylic polymer films, and even Teflon films with excellent water repellency, but even when formed by vapor phase deposition, cracks and peeling occur, making them impractical. Not there.
この発明は、以上の通りの事情に鑑みてなされたもので
あり、時計、装身具等の外装品や装飾品の透明保護膜と
して、密着性、耐候性等の機能性にも優れた新しい透明
保護膜構造を提供することを目的としている。This invention was made in view of the above circumstances, and is a new transparent protective film that has excellent functionality such as adhesion and weather resistance and can be used as a transparent protective film for exterior products and accessories such as watches and jewelry. The purpose is to provide a membrane structure.
（課題を解決するための手段）
この発明は、上記の課題を解決するものとして、Ｓ ｉ
Ｏ＋ Ｓ ｌ Ｏｔ ＋ スピネルおよび／または
アルミナと含弗素有機物との透明混合膜を高周波励起型
イオンプレーティングにより基体表面に気相蒸着させて
なることを特徴とする透明保護膜構造を提供する。(Means for Solving the Problems) The present invention solves the above problems by providing Si
A transparent protective film structure is provided, characterized in that a transparent mixed film of O+ S l Ot + spinel and/or alumina and a fluorine-containing organic substance is vapor-deposited on the surface of a substrate by high-frequency excited ion plating.
この場合の含弗素有機物としてはポリテトラフルオロエ
チレン、ポリジフルオロエチレン、ポリジフルオロクロ
ルエチレン、その他のポリフルオロオレフィン、含弗素
ポリエステル、含弗素ポリシロキサン等の有機ポリマー
、または含弗素炭化水素等の有機上ツマーガスを使用す
ることができる。In this case, the fluorine-containing organic substances include organic polymers such as polytetrafluoroethylene, polydifluoroethylene, polydifluorochloroethylene, other polyfluoroolefins, fluorine-containing polyesters, and fluorine-containing polysiloxanes, or organic polymers such as fluorine-containing hydrocarbons. Zumagas can be used.
透明混合膜を形成するにあたっては、Ｓｉｎ。In forming the transparent mixed film, Sin.
５ｉｎｓ、スピネルおよび／またはアルミナと上記した
有機ポリマーとを同時に蒸発させるか、あるいはＳ ｉ
ｏ、Ｓ ｉｔｓ 、スピネルおよび／またはアルミナを
蒸発させながら有機モノマーガスを導入して、高周波励
起型イオンプレーティングにより蒸発粒子、あるいは蒸
発粒子とガス分子を真空反応装置内のグロー放電によっ
てプラズマ励起し、イオン化粒子、中性粒子またはラジ
カルの状態として基体表面に蒸着する。この時の真空反
応装置内の圧力は、たとえばｌｏ−２〜１０−’Ｔｏｒ
ｒ程度の真空状態とすることができ、また、基体表面の
温度は、室温〜４００℃程度の範囲とすることができる
。なお、５蒸着に際し、反応装置内にアルゴン等の不活
性ガス、さらには有機色素物質等の蒸発物を導入するこ
とも可能である。5ins, co-evaporate spinel and/or alumina and the organic polymer described above, or Si
o, Sits, an organic monomer gas is introduced while evaporating spinel and/or alumina, and evaporated particles, or evaporated particles and gas molecules are plasma-excited by glow discharge in a vacuum reactor by high-frequency excited ion plating. , deposited on the substrate surface as ionized particles, neutral particles or radicals. The pressure inside the vacuum reactor at this time is, for example, lo-2 to 10-'Tor.
It is possible to create a vacuum state of about 300° C., and the temperature of the substrate surface can be in the range of room temperature to about 400° C. Incidentally, during the vapor deposition, it is also possible to introduce an inert gas such as argon into the reaction apparatus, and further an evaporated material such as an organic dye substance.
有機色素としては、有機顔料、染料等の各種のものが使
用できる。As the organic dye, various organic pigments, dyes, etc. can be used.
また、基体としては、Ａｊ！、Ａｕ、Ａｇ、Ｃｒ。In addition, as a base material, Aj! , Au, Ag, Cr.
Ｚｎ、Ｓｎ、Ｔｉ、Ｎｉ、Ｃｕ等の金属やそれらの合金
、Ｔ ｉＯ！ 、Ｔ ａｏｔ ＋ Ｔ ｔ Ｎ＋ Ｔａ
Ｎ。Metals such as Zn, Sn, Ti, Ni, Cu and their alloys, TiO! , T aot + T t N+ Ta
N.
ＴａＣ，ＷＣ等の化合物、あるいは有機ポリマーなど各
種のものが対象となる。Targets include various compounds such as TaC and WC, and organic polymers.
基体表面への蒸着膜の構造としては、たとえば第１図に
示したように、基体（１）表面に含弗素有機物とＳｉＯ
，ＳｉＯ＊等との透明混合膜（２）を蒸着したものや、
第２図に示したように、さらにその上に別種のたとえば
淡いブルーやピンクに着色することのできる色素物質を
も共存させて形成した透明混合膜（３）を蒸着したもの
を例示することができる。あるいはまた、第３図に示し
たように、基体（１）表面に、着色透明混合膜（３）を
蒸着し、この上に通常の有機重合膜（４）を積層して一
体化したり、第４図に示したように、さらにその上に透
明混合膜（５）を蒸着一体化することもできる。For example, as shown in FIG. 1, the structure of the vapor-deposited film on the surface of the substrate includes a fluorine-containing organic substance and SiO2 on the surface of the substrate (1).
, SiO*, etc. transparent mixed film (2) deposited,
As shown in FIG. 2, an example is a transparent mixed film (3) formed by vapor depositing a different type of pigment material that can be colored, for example, pale blue or pink, on top of the transparent mixed film (3). can. Alternatively, as shown in FIG. 3, a colored transparent mixed film (3) is deposited on the surface of the substrate (1), and an ordinary organic polymer film (4) is laminated and integrated thereon. As shown in FIG. 4, a transparent mixed film (5) can also be integrally deposited thereon.
この場合の有機重合膜（４）の原料としては、前述した
透明混合膜（２）、（３）、（５）の原料と同様のもの
や、あるいはポリカーボネート、ポリアクリレート、ポ
リエステル、ポリエチレン等の有機ポリマー、または炭
化水素等の有機モノマーガスを用いることができ、また
、その形成方法としても、高周波励起型イオンプレーテ
ィングによるプラズマ重合とすることができる。In this case, the raw material for the organic polymer film (4) may be the same as the raw material for the transparent mixed film (2), (3), or (5) described above, or an organic material such as polycarbonate, polyacrylate, polyester, or polyethylene. An organic monomer gas such as a polymer or a hydrocarbon can be used, and the formation method thereof can be plasma polymerization using high frequency excited ion plating.
（実施例）
以下、実施例を示し、この発明の銀表面透明保護膜構造
についてさらに詳しく説明する。(Example) Hereinafter, the structure of the silver surface transparent protective film of the present invention will be explained in more detail with reference to Examples.
実施例１
５ Ｘ １０−”Ｔｏｒｒのアルゴンガスを導入して、
銀基板をボンバード処理し、次いで、４ＸＩＯ−”Ｔｏ
ｒｒのアルゴン圧条件下で高周波励起型イオンプレーテ
ィングによりＳｉＯおよび５ｉｆｔ、ポリテトラフルオ
ロエチレンの蒸発粒子をプラズマイオン化して混合膜を
蒸着した。なお、放電電力は３００Ｗとした。Example 1 Introducing argon gas at 5×10-” Torr,
The silver substrate was bombarded and then 4XIO-”To
A mixed film was deposited by plasma ionizing the evaporated particles of SiO, 5ift, and polytetrafluoroethylene by radio frequency excited ion plating under argon pressure conditions of rr. Note that the discharge power was 300W.
この混合膜は、鉛筆硬度１０Ｈ程度と硬く、耐食性、撥
水性、耐クラツク性、耐候性ともに良好であり、表面保
護性に優れていた。また、密着強度も良好であった。This mixed film had a pencil hardness of about 10H, had good corrosion resistance, water repellency, crack resistance, and weather resistance, and was excellent in surface protection. Moreover, the adhesion strength was also good.
実施例２
実施例１で得られた混合膜の表面に、４×１０−”Ｔｏ
ｒｒのアルゴン圧条件下でポリカーボネート重合膜を積
層一体化した。Example 2 On the surface of the mixed film obtained in Example 1, 4×10-”To
Polycarbonate polymer membranes were laminated and integrated under argon pressure conditions of rr.
硬質の透明重合膜が得られ、表面保護性がさらに向上し
た。A hard transparent polymer film was obtained, and the surface protection properties were further improved.
実施例３
５ Ｘ １０ ’Ｔｏｒｒのアルゴンガスを導入して
、亜鉛基板をボンバード処理した後、４ Ｘ １０ ”
Ｔｏｒｒのアルゴン圧条件下で高周波励起型イオンプレ
ーティングによりＳｉＯとポリテトラフルオロエチレン
との蒸発粒子をプラズマイオン化して混合膜を蒸着した
。この後に、同一の圧力条件下でさらに色素物質として
有機顔料キナクリドンバイオレットを同時蒸発させて鮮
紫色の透明混合膜を形成した。Example 3 After bombarding a zinc substrate by introducing argon gas of 5 x 10' Torr,
A mixed film was deposited by plasma ionizing the evaporated particles of SiO and polytetrafluoroethylene by high frequency excited ion plating under Torr argon pressure conditions. Thereafter, under the same pressure conditions, an organic pigment quinacridone violet was further co-evaporated as a pigment substance to form a bright purple transparent mixed film.
この混合積層膜は、耐食性、撥水性、耐クラツク性、耐
候性に優れ、表面保護性も良好であった。This mixed laminated film had excellent corrosion resistance, water repellency, crack resistance, and weather resistance, and also had good surface protection properties.
また、色調、密着強度も良好であった。In addition, the color tone and adhesion strength were also good.
もちろんこの発明は、以上の例によって限定されるもの
ではない。有機物の種類、蒸着条件等の細部については
様々な態様が可能であることはいうまでもない。Of course, the invention is not limited to the above examples. It goes without saying that various embodiments are possible with respect to details such as the type of organic substance and vapor deposition conditions.
（発明の効果）
以上詳しく説明した通り、この発明によって、高硬度で
、密着性と表面保護性の良好な透明混合膜を形成するこ
とができ、空気、汗、湿気等による基体表面の退色や劣
化を効果的に防止することができる。(Effects of the Invention) As explained in detail above, the present invention makes it possible to form a transparent mixed film with high hardness, good adhesion and surface protection, and prevents discoloration of the substrate surface due to air, sweat, moisture, etc. Deterioration can be effectively prevented.
第１図、第２図、第３図および第４図は、各々、この発
明の一例を示した断面図である。
１・・・基 体
２．３．５・・・透明混合膜
４・・・有機重合膜
第 １
図FIG. 1, FIG. 2, FIG. 3, and FIG. 4 are sectional views each showing an example of the present invention. 1...Substrate 2.3.5...Transparent mixed film 4...Organic polymer film Figure 1
Claims (4)
ルミナと含弗素有機物との透明混合膜を高周波励起型イ
オンプレーティングにより基体表面に気相蒸着させてな
ることを特徴とする透明保護膜構造。(1) A transparent protective film structure characterized in that a transparent mixed film of SiO, SiO_2, spinel and/or alumina and a fluorine-containing organic substance is vapor-deposited on the surface of a substrate by high-frequency excited ion plating.
護膜構造。(2) The transparent protective film structure according to claim (1), which has an organic polymer film layer.
リジフルオロエチレン、ポリジフルオロクロルエチレン
、含弗素ポリエステルおよび／または含弗素ポリシロキ
サンである請求項（１）記載の透明保護膜構造。(3) The transparent protective film structure according to claim (1), wherein the fluorine-containing organic substance is polytetrafluoroethylene, polydifluoroethylene, polydifluorochloroethylene, fluorine-containing polyester, and/or fluorine-containing polysiloxane.
記載の透明保護膜構造。(4) Claim (1) in which the mixed film contains a pigment substance.
Transparent protective film structure as described.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25622590A JPH04136156A (en) | 1990-09-26 | 1990-09-26 | Transparent protective film structure |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25622590A JPH04136156A (en) | 1990-09-26 | 1990-09-26 | Transparent protective film structure |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04136156A true JPH04136156A (en) | 1992-05-11 |
Family
ID=17289675
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP25622590A Pending JPH04136156A (en) | 1990-09-26 | 1990-09-26 | Transparent protective film structure |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04136156A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009179866A (en) * | 2008-01-31 | 2009-08-13 | Shimadzu Corp | Method for producing reflection preventing film for ultraviolet wavelength region |
| JP2017181502A (en) * | 2016-03-29 | 2017-10-05 | ザ・スウォッチ・グループ・リサーチ・アンド・ディベロップメント・リミテッド | Colored timepiece component |
-
1990
- 1990-09-26 JP JP25622590A patent/JPH04136156A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009179866A (en) * | 2008-01-31 | 2009-08-13 | Shimadzu Corp | Method for producing reflection preventing film for ultraviolet wavelength region |
| JP2017181502A (en) * | 2016-03-29 | 2017-10-05 | ザ・スウォッチ・グループ・リサーチ・アンド・ディベロップメント・リミテッド | Colored timepiece component |
| CN107239031A (en) * | 2016-03-29 | 2017-10-10 | 斯沃奇集团研究和开发有限公司 | The timepiece being colored |
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