JPH06116430A - Water-and oil-repellent film and production thereof - Google Patents
Water-and oil-repellent film and production thereofInfo
- Publication number
- JPH06116430A JPH06116430A JP4266169A JP26616992A JPH06116430A JP H06116430 A JPH06116430 A JP H06116430A JP 4266169 A JP4266169 A JP 4266169A JP 26616992 A JP26616992 A JP 26616992A JP H06116430 A JPH06116430 A JP H06116430A
- Authority
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- Japan
- Prior art keywords
- film
- water
- inorganic hard
- oil
- hard film
- Prior art date
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Materials Engineering (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Composite Materials (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Treatments Of Macromolecular Shaped Articles (AREA)
- Laminated Bodies (AREA)
- Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、機能性を高めたプラス
チックフィルムとその製造方法に関するものであり、と
りわけ、透明性を持つ撥水撥油性フィルムとその製造方
法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a plastic film having enhanced functionality and a method for producing the same, and more particularly to a water-repellent and oil-repellent film having transparency and a method for producing the same.
【０００２】[0002]
【従来の技術】撥水撥油性をもつ表面を得るためには、
その表面張力を水(または、油)の表面張力よりも低くす
ることが必要になる。撥水性(または、撥油性)、すなわ
ち物質表面の濡れやすさを示す数字として接触角という
考え方がある。表面に水(または、油)滴を置いた場合、
表面と接触する角度である。一般に、撥水性を持つフィ
ルムとしては、実用的には水に対する接触角で120°〜1
60°程度の撥水状態が必要である。2. Description of the Related Art In order to obtain a surface having water and oil repellency,
It is necessary to make the surface tension lower than that of water (or oil). There is a concept of contact angle as a number indicating water repellency (or oil repellency), that is, the wettability of a material surface. If you put a drop of water (or oil) on the surface,
The angle of contact with the surface. Generally, as a water-repellent film, the contact angle to water is practically 120 ° to 1
Water repellency of about 60 ° is required.
【０００３】従来の撥水撥油性と透明性を併せ持つフィ
ルムとしては、フッ素系の四フッ化エチレン−六フッ化
プロピレン共重合樹脂(ＦＥＰ)などのフィルムなどが代
表的である。また、最近ではポリエステルフィルムなど
の汎用フィルムの表面に撥水性コーティング剤(たとえ
ば、フッ素系コーティング剤)を塗装することにより撥
水性を付与することが一般的に行われている。As a conventional film having both water and oil repellency and transparency, a film such as a fluorine-based tetrafluoroethylene-hexafluoropropylene copolymer resin (FEP) is typical. In addition, recently, it has been generally practiced to impart water repellency by coating a surface of a general-purpose film such as a polyester film with a water repellent coating agent (for example, a fluorine-based coating agent).
【０００４】[0004]
【発明が解決しようとする課題】しかしながら、従来の
フッ素系のフィルムでは透明性が得られるものの、撥水
撥油性については水に対する接触角で100°程度と十分
に満足できるものが得られていない。そればかりかコス
トの面でも実用的でない。この低コスト化に対応するた
め、上述のような汎用フィルム上に撥水性コーティング
剤をコートすることにより、フィルム表面に撥水撥油性
を付与する方法がとられている。However, although the conventional fluorine-based film can provide transparency, the water-repellent and oil-repellent properties have not been sufficiently satisfactory at a contact angle of about 100 ° with respect to water. . Not only that, but also in terms of cost, it is not practical. In order to cope with this cost reduction, there has been adopted a method of imparting water and oil repellency to the film surface by coating a water-repellent coating agent on the above-mentioned general-purpose film.
【０００５】しかし、コスト面では改善されるが、撥水
撥油性についてはフッ素系のフィルムと同程度であるの
に加え、コーティング膜と基体とは単にアンカー効果で
のみ接着されているに過ぎないため、耐環境性，表面強
度の面で劣ってしまう。However, although the cost is improved, the water and oil repellency is about the same as that of the fluorine-based film, and the coating film and the substrate are merely bonded by the anchor effect. Therefore, it is inferior in terms of environmental resistance and surface strength.
【０００６】最近、フィルムに限らず撥水撥油性を向上
させる方法として、フッ素系樹脂，シリコーン系樹脂な
どに無機微粒子を均一に分散した複合塗料をコーティン
グ剤に用いる方法や、ニッケルめっき液中にフッ素樹脂
の微粒子を分散させめっきを行う方法などがある。これ
らの方法を用いると、被覆された表面の形態的効果によ
り水に対する接触角で160°近い超撥水状態が得られて
いるが、フィルム上に応用するためには耐熱性，付着
力，フィルムの持つ透明性維持などの問題が生じてしま
う。Recently, as a method for improving the water and oil repellency not only in the film, a method of using a composite coating in which inorganic fine particles are uniformly dispersed in a fluororesin, a silicone resin or the like as a coating agent, or a nickel plating solution is used. There is a method in which fine particles of fluororesin are dispersed and plating is performed. When these methods are used, a superhydrophobic state with a contact angle to water of nearly 160 ° has been obtained due to the morphological effect of the coated surface, but in order to apply it on the film, heat resistance, adhesion, film There will be problems such as maintaining transparency.
【０００７】また、本発明者等は、超撥水撥油状態を得
る方法として、フィルム表面の形態的撥水撥油効果とコ
ーティング膜が持つ材料的撥水撥油効果とを組み合わせ
た撥水撥油性フィルムも試作したが、透明性を維持しつ
つ水に対する接触角で150°の撥水性を持つものの、フ
ィルム表面が実用的強度を十分に得るまでには至らなか
った。Further, as a method for obtaining a super water-repellent and oil-repellent state, the present inventors have combined the water-repellent effect of the morphological water-repellent and oil-repellent effect of the film surface with the material water- and oil-repellent effect of the coating film. An oil-repellent film was also prototyped, but while maintaining transparency, it had a water repellency of 150 ° at a contact angle with water, but the film surface did not reach sufficient practical strength.
【０００８】したがって、本発明はフィルムの透明性を
維持し超撥水撥油性を持ち、さらに実用強度に耐える表
面強度を併せ持った低コストな撥水撥油性フィルムとそ
の製造方法を提供することを目的とする。Therefore, the present invention provides a low-cost water- and oil-repellent film having super-water- and oil-repellency, maintaining the transparency of the film, and having surface strength capable of withstanding practical strength, and a method for producing the same. To aim.
【０００９】[0009]
【課題を解決するための手段】本発明は、上記の目的を
達成するために、撥水撥油性フィルムはプラスチックフ
ィルムとプラスチックフィルム上の少なくとも片面に微
小な凹凸を形成した無機硬質膜と、前記無機硬質膜上の
微小な凹凸上にシロキサン結合を介して形成させたフッ
素を含む化学吸着単分子膜とから構成されている。In order to achieve the above object, the present invention provides a water-repellent and oil-repellent film which is a plastic film and an inorganic hard film having fine irregularities formed on at least one surface of the plastic film. It is composed of a chemisorption monomolecular film containing fluorine formed on the minute unevenness on the inorganic hard film through a siloxane bond.
【００１０】また、前記構成においては、無機硬質膜が
シリコンを含む酸化膜、または窒化膜であることが好ま
しい。Further, in the above structure, the inorganic hard film is preferably an oxide film containing silicon or a nitride film.
【００１１】また、前記構成においては、無機硬質膜の
膜厚が0.02〜10μmであることが好ましい。Further, in the above constitution, it is preferable that the inorganic hard film has a thickness of 0.02 to 10 μm.
【００１２】また、前記構成においては、無機硬質膜の
凹凸の粗さは、0.01〜0.3μmであることが好ましい。Further, in the above structure, the roughness of the unevenness of the inorganic hard film is preferably 0.01 to 0.3 μm.
【００１３】さらに、前記構成においては、プラスチッ
ク裏面に粘着材が塗布されていることが好ましい。Further, in the above construction, it is preferable that the back surface of the plastic is coated with an adhesive material.
【００１４】本発明の撥水撥油性フィルムの製造方法
は、プラスチックフィルムの少なくとも片面に無機硬質
膜を形成する工程と、前記無機硬質膜の表面を炭素およ
びフッ素を含むガス中でプラズマ放電処理を行い、微小
な凹凸を形成する工程と、前記凹凸に形成した無機硬質
膜表面を少なくとも酸素を含むガスでプラズマ放電処理
を行い、凹凸表面を親水性にする工程と、凹凸に形成さ
れた無機硬質膜を表面上に形成した前記プラスチックフ
ィルムをフッ化炭素基とクロロシリル基を含む化合物
を、非水系の溶媒に溶解した溶液に浸漬し、前記無機硬
質膜の凹凸表面にフッ素を含む化学吸着単分子膜をシロ
キサン結合を介して形成させる工程とからなることを特
徴とする。The method for producing a water / oil repellent film of the present invention comprises a step of forming an inorganic hard film on at least one side of a plastic film, and a plasma discharge treatment of the surface of the inorganic hard film in a gas containing carbon and fluorine. A step of forming minute unevenness, a step of subjecting the surface of the inorganic hard film formed on the unevenness to a plasma discharge treatment with a gas containing at least oxygen to make the uneven surface hydrophilic, and an inorganic hard film formed on the unevenness A compound containing a fluorocarbon group and a chlorosilyl group, the plastic film having a film formed on the surface thereof, is immersed in a solution dissolved in a non-aqueous solvent, and a chemisorption single molecule containing fluorine on the uneven surface of the inorganic hard film. And a step of forming a film through a siloxane bond.
【００１５】[0015]
【作用】本発明によれば、プラスチックフィルム表面上
を直接微小な凹凸に荒らすのではなく、プラスチックフ
ィルム上に無機硬質膜を形成し、その表面を微小に凹凸
に荒らすことにより、無機硬質膜がフィルム表面強度の
弱さを補い、かつ無機硬質膜の微小な凹凸が優れた撥水
撥油性効果を発揮させることができる。According to the present invention, an inorganic hard film is formed by forming an inorganic hard film on the plastic film and then roughening the surface to fine unevenness, instead of directly roughening the surface of the plastic film into fine unevenness. It is possible to make up for the weakness of the film surface strength and to exert an excellent water and oil repellency effect due to the fine irregularities of the inorganic hard film.
【００１６】また、微小な凹凸は0.01〜0.3μmの粗さで
あるために光透過性に優れており、フィルムの透明性を
妨げることもない。さらには、無機硬質膜表面とフッ素
を含む化学吸着単分子膜とがシロキサン結合を介して形
成されているので、優れた撥水撥油性，耐候性，耐磨耗
性，透明性のある撥水撥油性フィルムとすることができ
る。Further, since the fine irregularities have a roughness of 0.01 to 0.3 μm, they are excellent in light transmission and do not interfere with the transparency of the film. Furthermore, since the surface of the inorganic hard film and the chemisorption monomolecular film containing fluorine are formed through the siloxane bond, excellent water / oil repellency, weather resistance, abrasion resistance, and transparent water repellency are provided. It can be an oil repellent film.
【００１７】また、無機硬質膜の膜厚が0.02〜10μmと
いう本発明の好ましい構成によれば、膜の可視光域での
光透過性を妨げることもない。Further, according to the preferable constitution of the present invention in which the thickness of the inorganic hard film is 0.02 to 10 μm, the light transmittance of the film in the visible light region is not hindered.
【００１８】また、無機硬質膜がシリコンを含む酸化
膜、または窒化膜である本発明の好ましい構成によれ
ば、微小な凹凸を比較的簡単に形成することができる。Further, according to the preferred structure of the present invention in which the inorganic hard film is an oxide film containing silicon or a nitride film, minute irregularities can be formed relatively easily.
【００１９】さらに、フィルム裏面に粘着材が塗布され
ているという本発明の好ましい構成によれば、粘着する
べき基材に簡単に張りつけることができる。Further, according to the preferable constitution of the present invention in which the back surface of the film is coated with the adhesive, it can be easily attached to the substrate to be adhered.
【００２０】[0020]
(実施例１)以下、本発明の第１の実施例について図面を
参照しながら説明する。(First Embodiment) A first embodiment of the present invention will be described below with reference to the drawings.
【００２１】図１は本発明の撥水撥油性フィルムの構成
を示す一部断面図であり、図２は図１の一部Ｂを分子レ
ベルまで拡大した断面概念図である。FIG. 1 is a partial sectional view showing the constitution of the water / oil repellent film of the present invention, and FIG. 2 is a sectional conceptual view in which a part B of FIG. 1 is enlarged to a molecular level.
【００２２】図１において、11は100μmの厚みのポリエ
チレンテレフタレートフィルム、12はポリエチレンテレ
フタレートフィルム11上に形成された厚さ２μmの酸化
シリコン膜、13は酸化シリコン膜12上に形成された微小
な凹凸、14はフッ素を含む化学吸着単分子膜である。In FIG. 1, 11 is a polyethylene terephthalate film having a thickness of 100 μm, 12 is a silicon oxide film having a thickness of 2 μm formed on the polyethylene terephthalate film 11, and 13 is a minute unevenness formed on the silicon oxide film 12. , 14 are chemisorption monolayers containing fluorine.
【００２３】最初に、撥水撥油性フィルムの作製手順に
ついて述べる。まず、ポリエチレンテレフタレートフィ
ルム11を真空容器内に入れ、0.4Paに保持したアルゴン
ガス中で、ＲＦ放電電力400ｗでＳiＯ2ターゲットをス
パッタし、ポリエチレンテレフタレートフィルム11上に
２μm厚の酸化シリコン膜12を形成する。First, the procedure for producing the water and oil repellent film will be described. First, the polyethylene terephthalate film 11 was placed in a vacuum container, and a SiO 2 target was sputtered at an RF discharge power of 400 w in an argon gas maintained at 0.4 Pa to form a 2 μm thick silicon oxide film 12 on the polyethylene terephthalate film 11. To do.
【００２４】次に、酸化シリコン膜12の表面を炭素およ
びフッ素を含むガスをポリエチレンテレフタレートフィ
ルム11の表面にシャワー上に供給しながら、放電電力密
度１ｗ／cm2のプラズマ放電を用いて酸化シリコン膜12
上をエッチングし、微小な凹凸13を形成する。このとき
エッチング時間は３分であり、形成された微小な凹凸13
の粗さは0.2μmであり、フィルムの透明性は失われなか
った。Next, while supplying the surface of the silicon oxide film 12 with a gas containing carbon and fluorine onto the surface of the polyethylene terephthalate film 11 on the shower, the silicon oxide film is formed by using plasma discharge having a discharge power density of 1 w / cm 2. 12
The top is etched to form minute irregularities 13. At this time, the etching time is 3 minutes, and the formed minute unevenness 13
The roughness was 0.2 μm, and the transparency of the film was not lost.
【００２５】次に、微小な凹凸13上の表面を活性(親水)
化させるため、５Paに保持した酸素を含むガス中で、Ｒ
Ｆ放電電力100ｗで、５分のプラズマ処理を行う。この
ようにして処理されたフィルムを容器から取り出し、シ
クロヘキサンの溶媒で希釈した１×10~2 Mol/リットル
濃度のフロロカーボン基およびクロロシラン基を含む化
合物(化１)の溶液中に10分浸漬する。Next, the surface on the minute unevenness 13 is activated (hydrophilic).
R in a gas containing oxygen held at 5 Pa
Plasma processing for 5 minutes is performed with 100 W of F discharge power. The film thus treated is taken out of the container and immersed in a solution of a compound (Chemical Formula 1) containing a fluorocarbon group and a chlorosilane group at a concentration of 1 × 10 2 mol / liter diluted with a solvent of cyclohexane for 10 minutes.
【００２６】[0026]
【化１】 [Chemical 1]
【００２７】すると、微小な凹凸13が形成されている酸
化シリコン膜12の表面は酸素を含んだプラズマ処理によ
って親水化されているため、表面で(化２)の結合が形成
され、化合物(化１)による化学吸着単分子膜14が形成さ
れる。(図２)Then, since the surface of the silicon oxide film 12 on which the minute irregularities 13 are formed is made hydrophilic by the plasma treatment containing oxygen, the bond of (Formula 2) is formed on the surface, and The chemisorption monolayer 14 according to 1) is formed. (Fig. 2)
【００２８】[0028]
【化２】 [Chemical 2]
【００２９】このようにしてできた撥水撥油性フィルム
(Ａ)の撥水性，透明性の評価を行うため、水の接触角，
透過率について測定した。比較サンプルとして、ＦＥＰ
フィルム(Ｂ)、フッ素系樹脂をコーティングしたポリエ
チレンテレフタレートフィルム(Ｃ)，シリコーン系樹脂
に無機微粒子(シリカ)を均一に分散した複合塗料をコー
ティングしたポリエチレンテレフタレートフィルム
(Ｄ)、フィルム上に直ちに本発明と同じフロロカーボン
基およびクロロシラン基を含む化合物(化１)を使って化
学吸着単分子膜を形成したポリエチレンテレフタレート
フィルム(Ｅ)、フィルム上を微小な凹凸に加工し、その
上に本発明と同じフロロカーボン基およびクロロシラン
基を含む化合物(化１)を使って化学吸着単分子膜を形成
したポリエチレンテレフタレートフィルム(Ｆ)の５つを
用い、同様に、水の接触角，透過率について測定した。
なお、フィルム厚は、すべて100μmである。これら各フ
ィルム(Ａ)ないし(Ｆ)の測定結果を表１に示す。Water-repellent and oil-repellent film thus formed
In order to evaluate the water repellency and transparency of (A), contact angle of water,
The transmittance was measured. As a comparison sample, FEP
Film (B), polyethylene terephthalate film (C) coated with fluorine resin, polyethylene terephthalate film coated with a composite coating in which inorganic fine particles (silica) are uniformly dispersed in silicone resin
(D), a polyethylene terephthalate film (E) in which a chemisorption monomolecular film is immediately formed on the film by using the same compound (Chemical formula 1) containing a fluorocarbon group and a chlorosilane group as in the present invention, and the film is processed into fine irregularities. Then, five polyethylene terephthalate films (F) each having a chemisorption monomolecular film formed by using the same compound (Chemical Formula 1) containing a fluorocarbon group and a chlorosilane group as in the present invention were used, and contact with water was similarly performed. The angle and the transmittance were measured.
The film thicknesses are all 100 μm. Table 1 shows the measurement results of each of these films (A) to (F).
【００３０】[0030]
【表１】 [Table 1]
【００３１】この表１から明らかなように、本実施例１
により作製した撥水撥油性フィルム(Ａ)は比較サンプル
としてのフィルム(Ｂ)，(Ｃ)，(Ｅ)に比べて、撥水性
(ア)，透明性(イ)，表面強度(ウ)の面で優れた機能性フ
ィルムであることがわかる。As is apparent from Table 1, the first embodiment
The water-repellent and oil-repellent film (A) produced by the method is more water-repellent than the films (B), (C) and (E) as comparative samples.
It can be seen that it is a functional film excellent in terms of (a), transparency (a), and surface strength (c).
【００３２】(実施例２)以下、本発明の第２の実施例に
ついて説明する。(Second Embodiment) A second embodiment of the present invention will be described below.
【００３３】撥水撥油性フィルムの作製手順について図
面を参照しながら説明する。The procedure for producing the water and oil repellent film will be described with reference to the drawings.
【００３４】図３は本発明の撥水撥油性フィルムを作製
するための化学吸着膜形成装置の概略図である。図３に
おいて、21は酸化シリコン膜が形成されたポリエチレン
テレフタレートフィルム、25は真空容器、26は密閉容
器、27は密閉容器26に入っているフロロカーボン基およ
びクロロシラン基を含む化合物の原液(化１)、28は密閉
容器のコックである。FIG. 3 is a schematic view of a chemical adsorption film forming apparatus for producing the water / oil repellent film of the present invention. In FIG. 3, 21 is a polyethylene terephthalate film having a silicon oxide film formed thereon, 25 is a vacuum container, 26 is a closed container, and 27 is a stock solution of a compound containing a fluorocarbon group and a chlorosilane group contained in the closed container 26 (Formula 1). , 28 are cocks of closed containers.
【００３５】実施例１と同様にポリエチレンテレフタレ
ートフィルム21上に２μmの酸化シリコン膜を成膜後、
その酸化シリコン膜表面に0.2μmの粗さの微小な凹凸を
形成し、その表面を酸素ガスを含んだプラズマ放電処理
で活性(親水)化する。次に、真空容器25内を１×10~3Pa
になるまで排気する。密閉容器26のコック28を開き、フ
ロロカーボン基およびクロロシラン基を含む化合物(化
１)の原液27を気化させる。After forming a 2 μm silicon oxide film on the polyethylene terephthalate film 21 in the same manner as in Example 1,
Minute irregularities having a roughness of 0.2 μm are formed on the surface of the silicon oxide film, and the surface is activated (hydrophilic) by a plasma discharge treatment containing oxygen gas. Next, set the inside of the vacuum container 25 to 1 × 10 to 3 Pa
Exhaust until The cock 28 of the closed container 26 is opened, and the stock solution 27 of the compound containing the fluorocarbon group and the chlorosilane group (Formula 1) is vaporized.
【００３６】すると、プラズマ処理を行った酸化シリコ
ン膜表面が親水化されているため、気化した化合物(化
１)と酸化シリコン膜表面とで(化２)の結合が形成さ
れ、化合物(化１)による化学吸着単分子膜が形成され
る。Then, since the surface of the silicon oxide film subjected to the plasma treatment is hydrophilized, a bond of (chemical formula 2) is formed between the vaporized compound (chemical formula 1) and the surface of the silicon oxide film, and the compound (chemical formula 1) is formed. ), A chemisorption monolayer is formed.
【００３７】このようにしてできた撥水撥油性フィルム
を実施例１で作製した撥水撥油性フィルム(Ａ)と比較し
たところ、特性的にはまったく差がなかった。When the water- and oil-repellent film thus produced was compared with the water- and oil-repellent film (A) prepared in Example 1, there was no difference in characteristics.
【００３８】すなわち、実施例１と同様に、表１に示す
撥水性(ア)，透明性(イ)，表面強度(ウ)の面で優れた機
能性フィルムである。また、同時に、同じ真空容器で一
括して膜形成までもできるため、工程時間の短縮，低コ
スト化も実現可能となる。That is, as in Example 1, it is a functional film excellent in terms of water repellency (A), transparency (A) and surface strength (C) shown in Table 1. At the same time, it is possible to form a film in a batch in the same vacuum container, so that it is possible to shorten the process time and reduce the cost.
【００３９】(実施例３)以下、本発明の第３の実施例に
ついて説明する。(Third Embodiment) A third embodiment of the present invention will be described below.
【００４０】撥水撥油性フィルムの作製手順について図
面を参照しながら説明する。The procedure for producing the water and oil repellent film will be described with reference to the drawings.
【００４１】図４は本発明の第３の実施例であるシロキ
サン単分子膜を形成した後の酸化シリコン表面を分子レ
ベルまで拡大した断面概念図である。FIG. 4 is a conceptual cross-sectional view in which the surface of silicon oxide after forming the siloxane monomolecular film according to the third embodiment of the present invention is enlarged to the molecular level.
【００４２】また、図５は本発明の第３の実施例である
フッ素を含んだ化学吸着単分子膜を形成した後の酸化シ
リコン表面を分子レベルまで拡大した断面概念図であ
る。FIG. 5 is a conceptual sectional view in which the surface of silicon oxide after forming the chemisorption monomolecular film containing fluorine which is the third embodiment of the present invention is enlarged to the molecular level.
【００４３】図４において、32はポリエチレンテレフタ
レート上に形成された酸化シリコン膜、39はシロキサン
単分子膜である。また図５において、34はフッ素を含む
化学吸着単分子膜である。In FIG. 4, 32 is a silicon oxide film formed on polyethylene terephthalate, and 39 is a siloxane monomolecular film. Further, in FIG. 5, 34 is a chemisorption monomolecular film containing fluorine.
【００４４】実施例１と同様に、ポリエチレンテレフタ
レートフィルム11上に２μmの酸化シリコン膜32を成膜
後、その酸化シリコン膜32の表面を0.2μmの粗さの微小
な凹凸に加工し、その表面を酸素ガスを含んだプラズマ
放電処理で活性(親水)化する。次に、シクロヘキサンの
溶媒で希釈した２×10~2 Mol/リットル濃度のＳiＣl4の
溶液中に10分浸漬する。As in Example 1, after forming a 2 μm silicon oxide film 32 on the polyethylene terephthalate film 11, the surface of the silicon oxide film 32 was processed into fine irregularities having a roughness of 0.2 μm, and the surface thereof was processed. Is activated (hydrophilic) by plasma discharge treatment containing oxygen gas. Next, it is immersed for 10 minutes in a solution of SiCl 4 having a concentration of 2 × 10 2 mol / liter diluted with a solvent of cyclohexane.
【００４５】すると、酸化シリコン膜32の表面は酸素を
含んだプラズマ処理によって親水化されているため、表
面で脱塩酸反応が生じ、(化３)，(化４)のように分子が
−ＳiＯ−結合を介して表面に固定される。Then, since the surface of the silicon oxide film 32 is made hydrophilic by the plasma treatment containing oxygen, a dehydrochlorination reaction occurs on the surface, and molecules such as (Chemical Formula 3) and (Chemical Formula 4) are converted into --SiO 2. -Fixed to the surface via a bond.
【００４６】[0046]
【化３】 [Chemical 3]
【００４７】[0047]
【化４】 [Chemical 4]
【００４８】その後、非水系の溶媒、例えば、シクロヘ
キサンで洗浄して、さらに水で洗浄するとねフィルムと
反応していないＳiＣl4分子は除去され、図４に示すよ
うに表面に下記(化５)(化６)などのシロキサン単分子膜
39が化学結合した状態で得られる。After that, by washing with a non-aqueous solvent such as cyclohexane and further washing with water, SiCl 4 molecules which have not reacted with the film are removed, and as shown in FIG. Siloxane monomolecular film such as
Obtained in a state in which 39 is chemically bonded.
【００４９】[0049]
【化５】 [Chemical 5]
【００５０】[0050]
【化６】 [Chemical 6]
【００５１】次に、シクロヘキサンの溶媒で希釈した１
×10~2 Mol/リットル濃度のフロロカーボン基およびク
ロロシラン基を含む化合物(化７)の溶液中に10分浸漬す
る。Next, 1 diluted with a solvent of cyclohexane
It immersed 10 minutes in a solution of × compounds containing 10 ~ 2 Mol / l concentration of fluorocarbon groups and chlorosilane groups (of 7).
【００５２】[0052]
【化７】 [Chemical 7]
【００５３】すると、微小な凹凸が形成されている酸化
シリコン膜32の表面は、上述の化学処理で多数の水酸基
を含んでいるので、表面で脱塩酸反応が生じ、(化８)の
結合が生成され、化合物(化７)によるフッ素を含む化学
吸着単分子膜34が形成される。(図５)Then, since the surface of the silicon oxide film 32 on which the minute irregularities are formed contains a large number of hydroxyl groups by the above-mentioned chemical treatment, a dehydrochlorination reaction occurs on the surface, and the bond of Chemical formula 8 is formed. A chemisorption monomolecular film 34 containing fluorine is formed by the compound (Chemical Formula 7). (Fig. 5)
【００５４】[0054]
【化８】 [Chemical 8]
【００５５】また、この膜は、実施例１に比べて高密度
に形成できた。Further, this film could be formed with a higher density than in Example 1.
【００５６】本実施例３と実施例１で作製した撥水撥油
性フィルムを比較したところ、透明性、表面強度はまっ
たく同じで、撥水性、つまり水に対しての接触角は実施
例１で作製したフィルムよりも大きく、150〜160°であ
り、実施例１の撥水撥油性フィルムよりもさらに優れた
ものであった。When the water and oil repellent films produced in Example 3 and Example 1 were compared, the transparency and surface strength were exactly the same, and the water repellency, that is, the contact angle to water in Example 1 was the same. It was larger than the produced film and was 150 to 160 °, which was even better than the water and oil repellent film of Example 1.
【００５７】なお、実施例２において密閉容器から気化
させる溶液を化合物(化１)の原液としたが、非水系の溶
媒、例えば、シクロヘキサン等で希釈した溶液であって
も何ら効果は変わらない。The solution vaporized from the closed container in Example 2 was used as the stock solution of the compound (Chemical formula 1), but the effect does not change even if the solution is diluted with a nonaqueous solvent such as cyclohexane.
【００５８】また、実施例２でクロロシラン系化合物の
分子量が大きくなる、すなわち炭素の数が大きくなると
蒸発しにくくなるが、原液を適度に加熱することで対応
できる。しかし、直鎖状の場合では炭素の数が25程度ま
でが好ましい。Further, in Example 2, when the molecular weight of the chlorosilane compound becomes large, that is, when the number of carbons becomes large, it becomes difficult to evaporate, but it can be dealt with by appropriately heating the stock solution. However, in the case of a straight chain, the number of carbon atoms is preferably up to about 25.
【００５９】なお、実施例１または実施例２において、
吸着させる化合物に化合物(化１)を用いたが、他のフロ
ロカーボン系化合物、例えば、ＣＦ3(ＣＦ2)7(ＣＨ2)2
ＳiＣl3，ＣＦ3(ＣＦ2)5(ＣＨ2)2ＳiＣl3，ＣＦ3ＣＨ2
Ｏ(ＣＨ2)15ＳiＣl3，ＣＦ3(ＣＨ2)2Ｓｉ(ＣＨ3)2(ＣＨ
2)15ＳiＣl3，Ｆ(ＣＦ2)4(ＣＨ2)2Ｓi(ＣＨ3)2(ＣＨ2)9
ＳiＣl3，Ｆ(ＣＦ2)8(ＣＨ2)2Ｓi(ＣＨ3)2(ＣＨ2)9Ｓi
Ｃl3，ＣＦ3ＣＯＯ(ＣＨ2)15ＳiＣl3等、または、それ
らの混合化合物であっても同様の効果を得ることができ
る。さらに、アルキル鎖部分にビニレン基やエチレン基
を付加したり組み込んでおけば、単分子膜形成後、電子
線照射で架橋できるので、さらに硬度を向上させること
もできる。In the first or second embodiment,
The compound (Formula 1) was used as the compound to be adsorbed, but other fluorocarbon compounds such as CF 3 (CF 2 ) 7 (CH 2 ) 2 were used.
SiCl 3 , CF 3 (CF 2 ) 5 (CH 2 ) 2 SiCl 3 , CF 3 CH 2
O (CH 2 ) 15 SiCl 3 , CF 3 (CH 2 ) 2 Si (CH 3 ) 2 (CH
2 ) 15 SiCl 3 , F (CF 2 ) 4 (CH 2 ) 2 Si (CH 3 ) 2 (CH 2 ) 9
SiCl 3, F (CF 2) 8 (CH 2) 2 Si (CH 3) 2 (CH 2) 9 Si
Similar effects can be obtained with Cl 3 , CF 3 COO (CH 2 ) 15 SiCl 3, etc., or a mixed compound thereof. Furthermore, if a vinylene group or an ethylene group is added to or incorporated in the alkyl chain portion, it can be crosslinked by electron beam irradiation after the monomolecular film is formed, so that the hardness can be further improved.
【００６０】また、実施例３において、多数のクロロシ
ラン基を含む化合物に化合物(化７)を用いたが、他のク
ロロシラン基を含む化合物、例えば、ＳiＨＣl3，ＳiＨ
2Ｃl2，Ｃl−(ＳiＣl2Ｏ)n−ＳiＣl3(ｎは整数)等、ま
たは、それらの混合化合物であっても同様の効果を得る
ことができる。In Example 3, the compound (Chemical Formula 7) was used as the compound containing a large number of chlorosilane groups, but other compounds containing a chlorosilane group such as SiHCl 3 , SiH.
2 Cl 2, Cl- (SiCl 2 O) n -SiCl 3 (n is an integer) or the like, or can be a mixture of these compounds to obtain the same effect.
【００６１】また、本実施例で、酸化シリコン膜の厚み
を２μmとしたが、0.02μmより薄くなると十分な微小凹
凸の形成ができなくなり、すなわち、十分な撥水撥油性
が得られなくなり、10μmを越えるとフィルムのもつ柔
軟性が失われるばかりか、膜の付着力が極端に悪くなる
ので、好ましくは、0.02〜10μmである。In the present embodiment, the thickness of the silicon oxide film is set to 2 μm, but if the thickness is less than 0.02 μm, it becomes impossible to form sufficient fine irregularities, that is, sufficient water / oil repellency cannot be obtained and 10 μm If it exceeds, not only the flexibility of the film is lost but also the adhesive force of the film is extremely deteriorated. Therefore, the film thickness is preferably 0.02 to 10 μm.
【００６２】また、無機硬質膜の表面の微小な凹凸の粗
さは、今回は0.2μmとしたが、0.01μm以下になると十
分な撥水性が得られなくなり、また、0.3μmを越えると
無機硬質膜の表面の機械的強度が極力弱くなるばかり
か、透明性も悪くなるため、好ましくは0.01〜0.3μmで
ある。Further, the roughness of the fine irregularities on the surface of the inorganic hard film was 0.2 μm this time, but if it is 0.01 μm or less, sufficient water repellency cannot be obtained, and if it exceeds 0.3 μm, The mechanical strength of the surface of the film is not only weakened as much as possible, but also the transparency is deteriorated, so that it is preferably 0.01 to 0.3 μm.
【００６３】また本実施例では、無機硬質膜として酸化
シリコン膜を使用したが、他の酸化物，窒化物，硫化物
などでも同様の効果が得られる。Further, in this embodiment, the silicon oxide film is used as the inorganic hard film, but other oxides, nitrides, sulfides and the like can also obtain the same effect.
【００６４】さらに、無機硬質膜の作製方法は、スパッ
タに限定されるものではない。Furthermore, the method for producing the inorganic hard film is not limited to sputtering.
【００６５】また、本実施例ではポリエチレンテレフタ
レートフィルムを使用したが、他のプラスチックフィル
ム、例えば、ポリイミド系フィルム，ポリエチレンフィ
ルム，ポリプロピレンフィルム，ポリカーボネートフィ
ルム，３フッ化塩化ポリエチレン等でも同様の結果が得
られることはいうまでもない。Although the polyethylene terephthalate film is used in this embodiment, similar results can be obtained with other plastic films such as polyimide film, polyethylene film, polypropylene film, polycarbonate film and trifluorochloroethylene. Needless to say.
【００６６】さらに、本発明のフィルム裏面に粘着材を
つけておけば、光学特性にも影響せず、粘着するべき基
材に簡単に貼りつけることができる。なお、粘着材の表
面には剥離シートを存在させてもよい。Furthermore, if an adhesive material is attached to the back surface of the film of the present invention, it can be easily attached to the substrate to be adhered without affecting the optical characteristics. A release sheet may be present on the surface of the adhesive material.
【００６７】[0067]
【発明の効果】以上説明したように本発明は、プラスチ
ックフィルムとそのフィルム上に微小な凹凸を形成した
無機硬質膜と、微小な凹凸上にシロキサン結合を介して
形成させたフッ素を含む化学吸着単分子膜とからなるこ
とにより、きわめて撥水撥油効果の高い透明フィルムを
得ることができる。また、表面の化学吸着単分子膜が無
機硬質膜と化学的に結合しているため、剥離したり変質
したりすることがなく、耐久性，耐熱性，耐候性，耐磨
耗性に優れた撥水撥油性フィルムを提供でき、その実用
的価値は多大である。As described above, according to the present invention, a plastic film, an inorganic hard film having minute irregularities formed on the film, and a chemical adsorption containing fluorine formed on the minute irregularities through a siloxane bond. By comprising a monomolecular film, a transparent film having an extremely high water / oil repellency effect can be obtained. Also, since the chemisorption monolayer on the surface is chemically bonded to the inorganic hard film, it does not peel off or deteriorate, and has excellent durability, heat resistance, weather resistance, and abrasion resistance. A water and oil repellent film can be provided, and its practical value is great.
【図１】本発明の第１の実施例における撥水撥油性フィ
ルムの構成を示す一部断面図である。FIG. 1 is a partial cross-sectional view showing the structure of a water / oil repellent film according to a first embodiment of the present invention.
【図２】図１の一部Ｂを分子レベルまで拡大した断面概
念図である。FIG. 2 is a conceptual sectional view in which a part B of FIG. 1 is enlarged to a molecular level.
【図３】本発明の第２の実施例における撥水撥油性フィ
ルムを作製するための化学吸着膜形成装置の概略図であ
る。FIG. 3 is a schematic view of a chemical adsorption film forming apparatus for producing a water / oil repellent film according to a second embodiment of the present invention.
【図４】本発明の第３の実施例におけるシロキサン単分
子膜を形成した後の酸化シリコン表面を分子レベルまで
拡大した断面概念図である。FIG. 4 is a conceptual cross-sectional view in which the surface of silicon oxide after forming a siloxane monomolecular film in the third embodiment of the present invention is enlarged to a molecular level.
【図５】本発明の第３の実施例におけるフッ素を含んだ
化学吸着単分子膜を形成した後の酸化シリコン表面を分
子レベルまで拡大した断面概念図である。FIG. 5 is a conceptual cross-sectional view in which the surface of silicon oxide after forming a chemisorption monomolecular film containing fluorine in the third embodiment of the present invention is enlarged to a molecular level.
11，21…ポリエチレンテレフタレートフィルム、 12…
酸化シリコン膜、 13…酸化シリコン膜上の微小な凹
凸、 14…フッ素を含む化学吸着単分子膜、 25…真空
容器、 26…密閉容器、 27…フロロカーボン基および
クロロシラン基を含む化合物の原液、 28…密閉容器の
コック、 32…酸化シリコン膜、 34…フッ素を含む化
学吸着単分子膜、 39…シロキサン単分子膜。11,21 ... Polyethylene terephthalate film, 12 ...
Silicon oxide film, 13 ... Micro unevenness on silicon oxide film, 14 ... Chemisorption monomolecular film containing fluorine, 25 ... Vacuum container, 26 ... Closed container, 27 ... Stock solution of compound containing fluorocarbon group and chlorosilane group, 28 ... … Cocks in closed containers, 32… Silicon oxide films, 34… Chemisorption monolayers containing fluorine, 39… Siloxane monolayers.
フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ０９Ｋ 3/18 １０４ 8318−4Ｈ (72)発明者 曽我 眞守 大阪府門真市大字門真1006番地 松下電器 産業株式会社内 (72)発明者 中山 一郎 大阪府門真市大字門真1006番地 松下電器 産業株式会社内 (72)発明者 丹野 益男 大阪府門真市大字門真1006番地 松下電器 産業株式会社内Continuation of the front page (51) Int.Cl. 5 Identification number Internal reference number for FI Technical location C09K 3/18 104 8318-4H (72) Inventor Somori Somori 1006 Kadoma, Kadoma-shi, Osaka Matsushita Electric Industrial Co., Ltd. Company (72) Inventor Ichiro Nakayama 1006 Kadoma, Kadoma-shi, Osaka Prefecture Matsushita Electric Industrial Co., Ltd. (72) Inventor, Masuo Tanno 1006 Kadoma, Kadoma-shi, Osaka Prefecture Matsushita Electric Industrial Co., Ltd.
Claims (9)
面に微小な凹凸を形成した無機硬質膜と、前記無機硬質
膜上の微小な凹凸上にシロキサン結合を介して形成させ
たフッ素を含む化学吸着単分子膜とからなることを特徴
とする撥水撥油性フィルム。1. An inorganic hard film having minute irregularities formed on at least one side of a plastic film, and a chemisorption monomolecular film containing fluorine formed on the minute irregularities of the inorganic hard film through a siloxane bond. A water- and oil-repellent film comprising:
たは窒化膜であることを特徴とする請求項１記載の撥水
撥油性フィルム。2. The water / oil repellent film according to claim 1, wherein the inorganic hard film is an oxide film containing silicon or a nitride film.
ことを特徴とする請求項１記載の撥水撥油性フィルム。3. The water- and oil-repellent film according to claim 1, wherein the inorganic hard film has a thickness of 0.02 to 10 μm.
0.01〜0.3μmであることを特徴とする請求項１記載の撥
水撥油性フィルム。4. The roughness of fine irregularities on the surface of the inorganic hard film
The water- and oil-repellent film according to claim 1, having a thickness of 0.01 to 0.3 µm.
布されていることを特徴とする請求項１記載の撥水撥油
性フィルム。5. The water / oil repellent film according to claim 1, wherein an adhesive material is applied to the back surface of the plastic film.
に無機硬質膜を形成する工程と、前記無機硬質膜の表面
を炭素およびフッ素を含むガス中でプラズマ放電処理を
行い、微小な凹凸を形成する工程と、前記凹凸に形成し
た無機硬質膜表面を少なくとも酸素を含むガスでプラズ
マ放電処理を行い、凹凸表面を親水性にする工程と、凹
凸に形成された無機硬質膜を表面上に形成した前記プラ
スチックフィルムをフッ化炭素基とクロロシリル基を含
む化合物を、非水系の溶媒に溶解した溶液に浸漬し、前
記無機硬質膜の凹凸表面にフッ素を含む化学吸着単分子
膜をシロキサン結合を介して形成させる工程とからなる
ことを特徴とする撥水撥油性フィルムの製造方法。6. A step of forming an inorganic hard film on at least one surface of a plastic film, and a step of subjecting the surface of the inorganic hard film to plasma discharge treatment in a gas containing carbon and fluorine to form minute irregularities, The inorganic hard film surface formed in the unevenness is subjected to plasma discharge treatment with a gas containing at least oxygen to make the uneven surface hydrophilic, and the plastic film formed on the surface of the inorganic hard film formed in the unevenness A step of immersing a compound containing a fluorocarbon group and a chlorosilyl group in a solution dissolved in a non-aqueous solvent to form a chemisorption monomolecular film containing fluorine on the uneven surface of the inorganic hard film through a siloxane bond; A method for producing a water- and oil-repellent film comprising:
に無機硬質膜を形成する工程Ｐと、前記無機硬質膜の表
面を炭素およびフッ素を含むガス中でプラズマ放電処理
を行い、微小な凹凸を形成する工程Ｑと、前記凹凸に形
成した無機硬質膜表面を少なくとも酸素を含むガスでプ
ラズマ放電処理を行い、凹凸表面を親水性にする工程Ｒ
と、凹凸に形成された無機硬質膜を表面上に形成した前
記プラスチックフィルムをフッ化炭素基とクロロシリル
基を含む化合物、もしくは、前記化合物を溶剤で希釈し
た溶液をガス状にし、そのガス状雰囲気中で気相により
前記無機硬質膜の凹凸表面にフッ素を含む化学吸着膜を
シロキサン結合を介して形成させる工程Ｓとからなるこ
とを特徴とする撥水撥油性フィルムの製造方法。7. A step P of forming an inorganic hard film on at least one surface of a plastic film, and a step Q of forming a minute unevenness by subjecting the surface of the inorganic hard film to plasma discharge treatment in a gas containing carbon and fluorine. And a step R of subjecting the surface of the inorganic hard film formed in the unevenness to a plasma discharge treatment with a gas containing at least oxygen to make the uneven surface hydrophilic.
And a compound containing a fluorocarbon group and a chlorosilyl group, or a solution obtained by diluting the compound with a solvent, makes the plastic film on the surface of which an inorganic hard film is formed in a concavo-convex gas state, and the gaseous atmosphere And a step S in which a chemical adsorption film containing fluorine is formed on the uneven surface of the inorganic hard film through a siloxane bond in the vapor phase.
合物として、ＣＦ3−(ＣＦ2)n−Ｒ−Ｓi−ＸpＣl3-p
(ただし、ｎは整数、Ｒはアルキル基またはシリコンも
しくは酸素原子を含む置換基を表すがなくてもよい、Ｘ
は水素またはアルキル基、アルコキシ基から選ばれる置
換基、ｐは０または１)を用いることを特徴とする請求
項６、または７記載の撥水撥油性フィルムの製造方法。As 8. A compound containing a fluorocarbon group and a chlorosilyl group, CF 3 - (CF 2) n -R-Si-X p Cl 3-p
(However, n represents an integer, R represents an alkyl group or a substituent containing a silicon or oxygen atom, and may not be present, X
Is a hydrogen atom or a substituent selected from an alkyl group or an alkoxy group, and p is 0 or 1), and the method for producing a water / oil repellent film according to claim 6 or 7.
Ｓが同一真空容器内で一括して行われることを特徴とす
る撥水撥油性フィルムの製造方法。9. Each process P, Q, R, according to claim 7,
A method for producing a water- and oil-repellent film, wherein S is collectively performed in the same vacuum container.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26616992A JP3358131B2 (en) | 1992-10-05 | 1992-10-05 | Water / oil repellent film and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26616992A JP3358131B2 (en) | 1992-10-05 | 1992-10-05 | Water / oil repellent film and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06116430A true JPH06116430A (en) | 1994-04-26 |
| JP3358131B2 JP3358131B2 (en) | 2002-12-16 |
Family
ID=17427231
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP26616992A Expired - Fee Related JP3358131B2 (en) | 1992-10-05 | 1992-10-05 | Water / oil repellent film and method for producing the same |
Country Status (1)
| Country | Link |
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