JP4512744B2 - DLC film surface treatment method - Google Patents
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Description
本発明はＤＬＣ膜（ダイヤモンド様（状）炭素膜）の表面処理方法に関する。 The present invention relates to a surface treatment method for a DLC film (diamond-like (like) carbon film).
ＤＬＣ膜は、工具や各種デバイスの保護膜をはじめとし、種々な分野で用いられている。このＤＬＣ膜の表面に各種の処理を施すことにより、物理的、化学的、機械的に優れた高機能特性を付加することができることが知られている。このようなことから、より広範囲の分野での利用が期待されている材料である。
その一例として表面に化学修飾を施すことにより、より高付加価値を有する材料となることが期待される。化学修飾を施す場合に、従来から特異な特性を有する官能基を導入することにより付加価値を高めることができる。
DLC films are used in various fields including protective films for tools and various devices. It is known that high functional properties excellent in physical, chemical and mechanical properties can be added by performing various treatments on the surface of the DLC film. For these reasons, the material is expected to be used in a wider range of fields.
As an example, it is expected that a material having higher added value can be obtained by chemically modifying the surface. When chemical modification is performed, the added value can be increased by introducing a functional group having unique characteristics.
一般に、フッ素官能基を有する材料は、フッ素原子やフッ素原子含有官能基特有の特異な性質を有し、生理活性、撥水性、撥油性、潤滑性等の機能を発現することができることから、医薬、農薬、機能性材料として有用であるとして注目を浴びてきた材料である。
ＤＬＣ表面上へフッ素官能基を導入することによって、熱的、化学的に安定となり、極限環境に耐えうる材料としての利用が知られている。
In general, a material having a fluorine functional group has a unique property peculiar to a fluorine atom or a fluorine atom-containing functional group, and can exhibit functions such as physiological activity, water repellency, oil repellency, and lubricity. It is a material that has attracted attention as being useful as an agrochemical and a functional material.
By introducing a fluorine functional group onto the DLC surface, it is known to be used as a material that is thermally and chemically stable and can withstand an extreme environment.
従来、ＤＬＣ膜表面上にフッ素を導入する方法としては、（イ）ＤＬＣ膜にCF4プラズマを作用させる方法（特許文献１）、及び（ロ）ＤＬＣ膜にフッ素を作用させる方法（特許文献２）が、知られている。
しかしながら、（イ）、（ロ）の方法においては大型装置が必要であったり、有毒ガスであり、取り扱いが困難であるフッ素ガスを使用する必要がある。このような特殊材料ガスを使用する場合、特別な反応容器が必要となり操作も煩雑となる。
However, in the methods (a) and (b), it is necessary to use a large apparatus or to use a fluorine gas which is a toxic gas and is difficult to handle. When such a special material gas is used, a special reaction vessel is required and the operation becomes complicated.
本発明が解決しようとする課題は、従来この種の方法に用いられてきた有毒ガスを使用することなく、また煩雑な操作を施すことなく、安全、かつ簡便にＤＬＣ膜表面上にフッ素官能基を導入する方法を提供することである。 The problem to be solved by the present invention is to use a fluorine functional group on the surface of the DLC film safely and easily without using a toxic gas conventionally used in this type of method and without performing complicated operations. Is to provide a way to introduce.
本発明者らは、ＤＬＣ膜に、ペルフルオロアゾアルカンの存在下に紫外光を照射すると、ＤＬＣ膜表面上にペルフルオロアルキル基を化学的に結合させることができることを見いだし、本発明を完成させた。
すなわち、本発明は、以下の技術を提供するものである。
１）ＤＬＣ膜と下記一般式（１）で表されるペルフルオロアゾアルカンを、溶液中に存在させて、紫外光を照射することによりＤＬＣ膜の表面に前記ペルフルオロアルキル基を結合させることを特徴とするＤＬＣ膜の表面処理方法。
ＲＦＮ＝ＮＲＦ （１）
（式中、ＲＦはペルフルオロアルキル基を示す。）
２）ペルフルオロ炭化水素中に存在させて紫外光を照射することを特徴とする上記１）記載のＤＬＣ膜の表面処理方法。
３）ペルフルオロアゾアルカン１ｍｇに対して、０．５ｍｌ〜３ｍｌのペルフルオロ炭化水素を使用することを特徴とする２）記載のＤＬＣ膜の表面処理方法。
４）波長１８０〜３００ｎｍの紫外光を照射することを特徴とする１）〜３）のいずれかに記載のＤＬＣ膜の表面処理方法。
５）光量を０．１〜１００ｍＷ／ｃｍ２の範囲で照射することを特徴とする上記１）〜４）のいずれかに記載のＤＬＣ膜の表面処理方法。
６）不活性ガス雰囲気中で光照射を行うことを特徴とする１）〜５）のいずれかに記載のＤＬＣ膜の表面処理方法。
The inventors have found that when a DLC film is irradiated with ultraviolet light in the presence of a perfluoroazoalkane, a perfluoroalkyl group can be chemically bonded to the surface of the DLC film, and the present invention has been completed.
That is, the present invention provides the following techniques.
1) A DLC film and a perfluoroazoalkane represented by the following general formula (1) are present in a solution, and the perfluoroalkyl group is bonded to the surface of the DLC film by irradiation with ultraviolet light. A method for surface treatment of a DLC film.
R F N = NR F (1)
(In the formula, R F represents a perfluoroalkyl group.)
2) The surface treatment method for a DLC film according to 1) above, wherein the ultraviolet light is irradiated in the presence of perfluorohydrocarbon.
3) The DLC film surface treatment method according to 2), wherein 0.5 ml to 3 ml of perfluorohydrocarbon is used per 1 mg of perfluoroazoalkane.
4) The DLC film surface treatment method according to any one of 1) to 3), wherein ultraviolet light having a wavelength of 180 to 300 nm is irradiated.
5) The DLC film surface treatment method according to any one of 1) to 4) above, wherein the light intensity is irradiated in a range of 0.1 to 100 mW / cm 2 .
6) The DLC film surface treatment method according to any one of 1) to 5), wherein light irradiation is performed in an inert gas atmosphere.
本発明は、常温の溶液中で紫外光照射をするだけの簡便な反応操作により、ＤＬＣ膜表面上にフッ素官能基を導入することができるという優れた効果を有する。また、従来用いられてきた有毒ガスを使用することがないので、安全に、煩雑さを伴うことなく、ＤＬＣ膜の表面に、前記ペルフルオロアルキル基を結合させることができるという著しい効果がある。 The present invention has an excellent effect that a fluorine functional group can be introduced onto the surface of a DLC film by a simple reaction operation in which ultraviolet light irradiation is performed in a normal temperature solution. In addition, since a conventionally used toxic gas is not used, there is a remarkable effect that the perfluoroalkyl group can be bonded to the surface of the DLC film safely and without being complicated.
本発明の方法で用いられるＤＬＣ膜は、通常炭化水素を原料としたプラズマ処理を用いて作製されたものが使用することができる。しかし、他の製造方法によってＤＬＣ膜を作製したものでも良く、特にこのＤＬＣ膜の製造方法には制限はない。
前記ＤＬＣ膜表面にフッ素官能基を化学結合させるために用いるペルフルオロアゾアルカンは、下記一般式（１）で表される化合物である。
ＲＦＮ＝ＮＲＦ （１）
（式中、ＲＦは、ペルフルオロアルキル基を示す）。
As the DLC film used in the method of the present invention, a DLC film produced by plasma treatment using hydrocarbon as a raw material can be used. However, the DLC film may be manufactured by other manufacturing methods, and the manufacturing method of the DLC film is not particularly limited.
The perfluoroazoalkane used for chemically bonding a fluorine functional group to the surface of the DLC film is a compound represented by the following general formula (1).
R F N = NR F (1)
(Wherein R F represents a perfluoroalkyl group).
前記ペルフルオロアゾアルカンのペルフルオロアルキル基の炭素数は、１〜１２、好ましくは、６〜１０、より好ましくは、７〜９である。具体的には、ペルフルオロアゾオクタン、ペルフルオロアゾヘプタン、ペルフルオロアゾヘキサン、ペルフルオロアゾプロパン、ペルフルオロアゾエタン、ペルフルオロアゾメタン等を用いることができる。
本発明方法の反応においては、これらのペルフルオロアルカンの鎖長による反応性の差はない。上記のペルフルオロアゾアルカンは例示であり、他のペルフルオロアゾアルカンを使用することもできる。また、一般式（１）で示されるペルフルオロアゾアルカンを主成分とし、他の被膜を同時に被覆することも可能である
本発明においては、ＤＬＣ膜の表面に前記ペルフルオロアルキル基を結合させることを達成することができれば問題はなく、本発明はＤＬＣ膜の表面処理方法は、付加的又は付随的な処理は全て本発明に含まれるものである。
The perfluoroalkyl group of the perfluoroazoalkane has 1 to 12, preferably 6 to 10, more preferably 7 to 9 carbon atoms. Specifically, perfluoroazooctane, perfluoroazoheptane, perfluoroazohexane, perfluoroazopropane, perfluoroazoethane, perfluoroazomethane, or the like can be used.
In the reaction of the method of the present invention, there is no difference in reactivity due to the chain length of these perfluoroalkanes. The above perfluoroazoalkanes are exemplary, and other perfluoroazoalkanes can be used. In the present invention, which is mainly composed of the perfluoroazoalkane represented by the general formula (1) and can be coated with other coatings simultaneously, the perfluoroalkyl group is bonded to the surface of the DLC film. There is no problem if it can be performed, and the present invention includes a DLC film surface treatment method, and any additional or incidental treatment is included in the present invention.
本発明の方法に際しては、原料物質である前記ペルフルオロアゾアルカンを、溶媒中に添加する。溶媒には、ペルフルオロ炭化水素が用いることができる。このペルフオロ炭化水素の具体例としては、ペルフルオロヘキサン、ペルフルオロヘプタン、ペルフルオロオクタンなどをあげることができる。しかし、本発明の条件で、ＤＬＣ膜の表面に前記ペルフルオロアルキル基を結合させることができれば、他の溶媒でも良い。 In the method of the present invention, the perfluoroazoalkane as a raw material is added to a solvent. As the solvent, perfluorohydrocarbon can be used. Specific examples of the perfluorohydrocarbon include perfluorohexane, perfluoroheptane, perfluorooctane and the like. However, other solvents may be used as long as the perfluoroalkyl group can be bonded to the surface of the DLC film under the conditions of the present invention.
溶媒量は、ペルフルオロアゾアルカンの使用量に応じて決定する。この反応原料を溶媒中に保存することができる量であれば差し支えないが、十分に溶媒中に混和することができ、かつ反応に際して光照射を十分に行うことができる量を必要とする。
このようなことを考慮して、ペルフルオロアゾアルカン１ｍｇに対して、０．５ｍｌ以上、３ｍｌ以下のペルフルオロ炭化水素が使用するのが望ましい。しかし、製造コスト、生産速度、歩留り等を考慮し、条件によっては前記範囲外の量を使用することも可能である。前記は好ましい範囲であり、必ずしもこれに特に制限されるものではない。
The amount of solvent is determined according to the amount of perfluoroazoalkane used. Any amount can be used as long as the reaction raw material can be stored in the solvent, but an amount that can be sufficiently mixed in the solvent and sufficiently irradiated with light during the reaction is required.
Considering this, it is desirable to use 0.5 to 3 ml of perfluorohydrocarbon per 1 mg of perfluoroazoalkane. However, considering the manufacturing cost, production speed, yield, etc., it is possible to use an amount outside the above range depending on the conditions. The above is a preferable range and is not necessarily limited thereto.
反応に際しては、溶媒中の前記ペルフルオロアゾアルカンおよびＤＬＣ膜存在下で行う。本発明の方法では、ＤＬＣ膜存在下において、溶媒中の前記ペルフルオロアゾアルカン溶液に、光照射を行う。本発明の方法では、前記一般式（１）で表されるペルフルオロアゾアルカンの脱窒素反応によるペルフルオロアルキルラジカルの発生が必要であることから、このために紫外光照射下に行う。波長は１８０ｎｍ〜３００ｎｍとするのが好適である。 The reaction is performed in the presence of the perfluoroazoalkane and DLC film in a solvent. In the method of the present invention, the perfluoroazoalkane solution in a solvent is irradiated with light in the presence of a DLC film. In the method of the present invention, it is necessary to generate a perfluoroalkyl radical by denitrogenation of the perfluoroazoalkane represented by the general formula (1). The wavelength is preferably 180 nm to 300 nm.
光源としては公知のものが用いることができる。その例を挙げると、低圧水銀灯、高圧水銀灯、ＡｒＦまたはＸｅＣｌエキシマレーザー、エキシマランプ等である。このように、本発明は、広範囲の波長の光を利用できる。
反応の高効率化のためには、２００ｎｍ以下の波長を有する紫外光照射下に反応を行うことが好ましい。しかし、これは製造コスト、生産速度、歩留り等を考慮し、条件によっては前記範囲外の波長を使用することも可能である。前記は好ましい範囲であり、必ずしもこれに特に制限されるものではない。
照射される光量の好ましい範囲は、０．１〜１００ｍＷ／ｃｍ２の範囲である。また、照射時間は、１〜６時間程度とするのが望ましい。これらの条件も、前記範囲外の条件を使用することも可能である。前記は好ましい範囲であり、必ずしもこれに特に制限されるものではない。
A well-known thing can be used as a light source. Examples thereof include a low-pressure mercury lamp, a high-pressure mercury lamp, an ArF or XeCl excimer laser, an excimer lamp, and the like. As described above, the present invention can use light having a wide range of wavelengths.
In order to increase the efficiency of the reaction, the reaction is preferably performed under irradiation with ultraviolet light having a wavelength of 200 nm or less. However, in consideration of manufacturing cost, production speed, yield, etc., it is possible to use a wavelength outside the above range depending on conditions. The above is a preferable range and is not necessarily limited thereto.
A preferable range of the amount of light to be irradiated is in a range of 0.1 to 100 mW / cm 2 . The irradiation time is preferably about 1 to 6 hours. It is also possible to use conditions outside these ranges. The above is a preferable range and is not necessarily limited thereto.
本発明の反応は、加熱する必要がなく、室温下で容易に進行する。これは、本発明の大きな特徴の一つでもある。しかし、加熱を否定するものではない。必要に応じて加熱することも可能である。
本発明の反応を行うにあたっては、アルゴン又は窒素雰囲気等の不活性雰囲気を介して光照射を行うことが望ましい。反応終了後、溶媒を除去する。ＤＬＣ膜を溶剤により洗浄し付着物を除去する。溶剤には前記ペルフルオロアルカン及びアルカンを用いることができる。
The reaction of the present invention does not require heating and proceeds easily at room temperature. This is one of the major features of the present invention. However, heating is not denied. It is also possible to heat as needed.
In carrying out the reaction of the present invention, it is desirable to carry out light irradiation through an inert atmosphere such as an argon or nitrogen atmosphere. After completion of the reaction, the solvent is removed. The DLC film is washed with a solvent to remove deposits. The perfluoroalkane and alkane can be used as the solvent.
このようにして得られるフッ素化ＤＬＣ膜を分析機器により、表面に前記ペルフルオロアルキル基が化学化学結合しているかどうかを確認する。各種の分析機器を用いることができるが、ＸＰＳなどにより確認することができる。
本発明では、ＤＬＣ膜に、ペルフルオロアルキル基を化学結合させることができる結果、フッ素原子を含んだ官能基をその表面に結合させることができるので、撥水性、撥油性、潤滑性を付与することができる。その際に熱的、化学的に安定であり、極限環境に耐える特性を付与することができる。
Whether the perfluoroalkyl group is chemically bonded to the surface of the fluorinated DLC film thus obtained is confirmed by an analytical instrument. Various analytical instruments can be used, but it can be confirmed by XPS or the like.
In the present invention, a perfluoroalkyl group can be chemically bonded to the DLC film, and as a result, a functional group containing a fluorine atom can be bonded to the surface, thereby imparting water repellency, oil repellency, and lubricity. Can do. In that case, it is thermally and chemically stable, and can give the characteristic which can endure an extreme environment.
以下、実施例により、本発明を更に詳細に説明する。
（実施例１）
合成石英製の反応容器に、ペルフルオロアゾオクタン（４ｍｇ）をペルフルオロヘキサン（４ｍｌ）に溶解させ、ＤＬＣ膜を入れた。アルゴン雰囲気下で攪拌しつつ、低圧水銀灯を室温で６時間照射した。紫外光照射の波長は１８５ｎｍであり、照射された光量は５０ｍＷ／ｃｍ２とした。
その後、ペルフルオロヘキサン溶液を除去し、ＤＬＣ膜をペルフルオロヘキサンおよびヘキサンで洗浄し、減圧下で乾燥を行った。反応後のＤＬＣ膜のＸＰＳ測定を行った。図１および図２に示すように、フッ素に由来するピークが観測され、表面上にフッ素官能基が導入されたことが確認された。
Hereinafter, the present invention will be described in more detail by way of examples.
Example 1
In a reaction vessel made of synthetic quartz, perfluoroazooctane (4 mg) was dissolved in perfluorohexane (4 ml), and a DLC film was placed. While stirring in an argon atmosphere, a low-pressure mercury lamp was irradiated at room temperature for 6 hours. The wavelength of ultraviolet light irradiation was 185 nm, and the amount of irradiated light was 50 mW / cm 2 .
Thereafter, the perfluorohexane solution was removed, the DLC film was washed with perfluorohexane and hexane, and dried under reduced pressure. XPS measurement of the DLC film after the reaction was performed. As shown in FIGS. 1 and 2, a peak derived from fluorine was observed, and it was confirmed that a fluorine functional group was introduced on the surface.
（実施例２）
合成石英製の反応容器に、ペルフルオロアゾヘプタン（４ｍｇ）をペルフルオロヘキサン（４ｍｌ）に溶解させ、ＤＬＣ膜を入れた。アルゴン雰囲気下で攪拌しつつ、低圧水銀灯を室温で６時間照射した。紫外光照射の波長は１８５ｎｍであり、照射された光量は４０ｍＷ／ｃｍ２とした。その後、ペルフルオロヘキサン溶液を除去し、ＤＬＣ膜をペルフルオロヘキサンおよびヘキサンで洗浄し、減圧下で乾燥を行った。
実施例１と同様に、反応後のＤＬＣ膜のＸＰＳ測定を行ったが、フッ素に由来するピークが観測され、表面上にフッ素官能基が導入されたことが確認された（同様の結果のため、図示せず）。
(Example 2)
In a reaction vessel made of synthetic quartz, perfluoroazoheptane (4 mg) was dissolved in perfluorohexane (4 ml), and a DLC film was placed. While stirring in an argon atmosphere, a low-pressure mercury lamp was irradiated at room temperature for 6 hours. The wavelength of ultraviolet light irradiation was 185 nm, and the amount of light irradiated was 40 mW / cm 2 . Thereafter, the perfluorohexane solution was removed, the DLC film was washed with perfluorohexane and hexane, and dried under reduced pressure.
As in Example 1, XPS measurement of the DLC film after the reaction was performed, but a peak derived from fluorine was observed, and it was confirmed that a fluorine functional group was introduced on the surface (for the same result). , Not shown).
（実施例３）
合成石英製の反応容器に、ペルフルオロアゾヘキサン（４ｍｇ）をペルフルオロヘキサン（４ｍｌ）に溶解させ、ＤＬＣ膜を入れた。アルゴン雰囲気下で攪拌しつつ、低圧水銀灯を室温で６時間照射した。紫外光照射の波長は１８５ｎｍであり、照射された光量は５０ｍＷ／ｃｍ２とした。その後、ペルフルオロヘキサン溶液を除去し、ＤＬＣ膜をペルフルオロヘキサンおよびヘキサンで洗浄し、減圧下で乾燥を行った。
実施例１と同様に、反応後のＤＬＣ膜のＸＰＳ測定を行ったが、フッ素に由来するピークが観測され、表面上にフッ素官能基が導入されたことが確認された（同様の結果のため、図示せず）。
(Example 3)
In a reaction vessel made of synthetic quartz, perfluoroazohexane (4 mg) was dissolved in perfluorohexane (4 ml), and a DLC film was placed. While stirring in an argon atmosphere, a low-pressure mercury lamp was irradiated at room temperature for 6 hours. The wavelength of ultraviolet light irradiation was 185 nm, and the amount of irradiated light was 50 mW / cm 2 . Thereafter, the perfluorohexane solution was removed, the DLC film was washed with perfluorohexane and hexane, and dried under reduced pressure.
As in Example 1, XPS measurement of the DLC film after the reaction was performed, but a peak derived from fluorine was observed, and it was confirmed that a fluorine functional group was introduced on the surface (for the same result). , Not shown).
（実施例４）
合成石英製の反応容器に、ペルフルオロアゾプロパン（４ｍｇ）をペルフルオロヘキサン（４ｍｌ）に溶解させ、ＤＬＣ膜を入れた。アルゴン雰囲気下で攪拌しつつ、低圧水銀灯を室温で６時間照射した。紫外光照射の波長は１８５ｎｍであり、照射された光量は３０ｍＷ／ｃｍ２とした。その後、ペルフルオロヘキサン溶液を除去し、ＤＬＣ膜をペルフルオロヘキサンおよびヘキサンで洗浄し、減圧下で乾燥を行った。
実施例１と同様に、反応後のＤＬＣ膜のＸＰＳ測定を行ったが、フッ素に由来するピークが観測され、表面上にフッ素官能基が導入されたことが確認された（同様の結果のため、図示せず）。
Example 4
In a reaction vessel made of synthetic quartz, perfluoroazopropane (4 mg) was dissolved in perfluorohexane (4 ml), and a DLC film was placed. While stirring in an argon atmosphere, a low-pressure mercury lamp was irradiated at room temperature for 6 hours. The wavelength of ultraviolet light irradiation was 185 nm, and the amount of light irradiated was 30 mW / cm 2 . Thereafter, the perfluorohexane solution was removed, the DLC film was washed with perfluorohexane and hexane, and dried under reduced pressure.
As in Example 1, XPS measurement of the DLC film after the reaction was performed, but a peak derived from fluorine was observed, and it was confirmed that a fluorine functional group was introduced on the surface (for the same result). , Not shown).
（実施例５）
合成石英製の反応容器に、ペルフルオロアゾエタン（４ｍｇ）をペルフルオロヘキサン（４ｍｌ）に溶解させ、ＤＬＣ膜を入れた。アルゴン雰囲気下で攪拌しつつ、低圧水銀灯を室温で６時間照射した。紫外光照射の波長は１８５ｎｍであり、照射された光量は５０ｍＷ／ｃｍ２とした。その後、ペルフルオロヘキサン溶液を除去し、ＤＬＣ膜をペルフルオロヘキサンおよびヘキサンで洗浄し、減圧下で乾燥を行った。
実施例１と同様に、反応後のＤＬＣ膜のＸＰＳ測定を行ったが、フッ素に由来するピークが観測され、表面上にフッ素官能基が導入されたことが確認された（同様の結果のため、図示せず）。
(Example 5)
In a reaction vessel made of synthetic quartz, perfluoroazoethane (4 mg) was dissolved in perfluorohexane (4 ml), and a DLC film was placed. While stirring in an argon atmosphere, a low-pressure mercury lamp was irradiated at room temperature for 6 hours. The wavelength of ultraviolet light irradiation was 185 nm, and the amount of irradiated light was 50 mW / cm 2 . Thereafter, the perfluorohexane solution was removed, the DLC film was washed with perfluorohexane and hexane, and dried under reduced pressure.
As in Example 1, XPS measurement of the DLC film after the reaction was performed, but a peak derived from fluorine was observed, and it was confirmed that a fluorine functional group was introduced on the surface (for the same result). , Not shown).
（実施例６）
合成石英製の反応容器に、ペルフルオロアゾメタン（４ｍｇ）をペルフルオロヘキサン（４ｍｌ）に溶解させ、ＤＬＣ膜を入れた。アルゴン雰囲気下で攪拌しつつ、低圧水銀灯を室温で６時間照射した。紫外光照射の波長は１８５ｎｍであり、照射された光量は６０ｍＷ／ｃｍ２とした。その後、ペルフルオロヘキサン溶液を除去し、ＤＬＣ膜をペルフルオロヘキサンおよびヘキサンで洗浄し、減圧下で乾燥を行った。
実施例１と同様に、反応後のＤＬＣ膜のＸＰＳ測定を行ったが、フッ素に由来するピークが観測され、表面上にフッ素官能基が導入されたことが確認された（同様の結果のため、図示せず）。
(Example 6)
In a reaction vessel made of synthetic quartz, perfluoroazomethane (4 mg) was dissolved in perfluorohexane (4 ml), and a DLC film was placed. While stirring in an argon atmosphere, a low-pressure mercury lamp was irradiated at room temperature for 6 hours. The wavelength of ultraviolet light irradiation was 185 nm, and the amount of light irradiated was 60 mW / cm 2 . Thereafter, the perfluorohexane solution was removed, the DLC film was washed with perfluorohexane and hexane, and dried under reduced pressure.
As in Example 1, XPS measurement of the DLC film after the reaction was performed, but a peak derived from fluorine was observed, and it was confirmed that a fluorine functional group was introduced on the surface (for the same result). , Not shown).
常温の溶液中で紫外光照射をするだけの簡便な反応操作により、ＤＬＣ膜表面上にフッ素官能基を導入することができる。従来用いられてきた有毒ガスを使用することがないので、安全に、煩雑さを伴うことなく、ＤＬＣ膜の表面に、前記ペルフルオロアルキル基を結合させることができる。
これによって、ＤＬＣ膜の機能に、さらにフッ素原子及びフッ素原子含有官能基特有の特異な性質を保有させることが可能となり、生理活性、撥水性、撥油性、潤滑性等の機能を発現させることができる。すなわち、本発明は、ＤＬＣ表面上へフッ素官能基を導入することによって、さらに熱的、化学的に安定となり、極限環境に耐え得る材料として有効である。
A fluorine functional group can be introduced onto the surface of the DLC film by a simple reaction operation in which ultraviolet light irradiation is performed in a solution at room temperature. Since the conventionally used toxic gas is not used, the perfluoroalkyl group can be bonded to the surface of the DLC film safely and without complications.
As a result, the functions of the DLC film can be further provided with unique properties peculiar to fluorine atoms and fluorine atom-containing functional groups, and functions such as physiological activity, water repellency, oil repellency, and lubricity can be expressed. it can. That is, the present invention is effective as a material that can be further thermally and chemically stable by introducing a fluorine functional group onto the DLC surface and can withstand an extreme environment.
Claims (6)
ＲＦＮ＝ＮＲＦ （１）
（式中、ＲＦはペルフルオロアルキル基を示す。） A DLC film and a perfluoroazoalkane represented by the following general formula (1) are present in a solution and irradiated with ultraviolet light to bond the perfluoroalkyl group to the surface of the DLC film. Membrane surface treatment method.
R F N = NR F (1)
(In the formula, R F represents a perfluoroalkyl group.)
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