JP5392764B2 - Method for surface treatment of carbon film - Google Patents
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- JP5392764B2 JP5392764B2 JP2009202235A JP2009202235A JP5392764B2 JP 5392764 B2 JP5392764 B2 JP 5392764B2 JP 2009202235 A JP2009202235 A JP 2009202235A JP 2009202235 A JP2009202235 A JP 2009202235A JP 5392764 B2 JP5392764 B2 JP 5392764B2
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Description
本発明は、カーボン系膜の表面処理方法に関し、特にカーボン系膜の表面上にフッ素官能基を導入する方法に関する。 The present invention relates to a surface treatment method for a carbon-based film, and more particularly to a method for introducing a fluorine functional group onto the surface of a carbon-based film.
ダイヤモンド膜およびダイヤモンド様炭素（以下、「ＤＬＣ」という）膜等のカーボン系膜は、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。このカーボン系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。
Carbon-based films such as diamond films and diamond-like carbon (hereinafter referred to as “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 carbon-based 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。
カーボン系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 a carbon-based surface, utilization as a material that is thermally and chemically stable and can withstand an extreme environment is known.
従来、カーボン系膜表面上にフッ素又はフッ素官能基を導入する方法としては、ウエットプロセスとドライプロセスがある。
前者の方法は、フッ素化表面処理剤で処理する方法（特許文献１）、或いは、フッ素樹脂をコーティングする方法（特許文献２）等があるが、いずれも溶剤を使用しなければならないという問題がある。
Conventionally, there are a wet process and a dry process as a method for introducing fluorine or a fluorine functional group onto the surface of a carbon-based film.
The former method includes a method of treating with a fluorinated surface treatment agent (Patent Document 1), a method of coating a fluororesin (Patent Document 2), and the like, all of which have a problem that a solvent must be used. is there.
また、後者の方法は、カーボン系膜をフッ素ガス等のフッ素含有化合物の雰囲気中でプラズマ処理する方法（特許文献３、４）、或いは、プロセスガスに、炭素原料としての炭化水素ガスと、フッ素源としての炭化フッ素を用いて、プラズマＣＶＤ法によりフッ素を含むカーボン系膜を形成する方法（特許文献５、６）等が知られている。
しかしながら、これらの方法においては大型装置が必要である、或いは、有毒であって、その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等の問題がある。また、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。
Further, the latter method is a method in which a carbon-based film is plasma-treated in an atmosphere of a fluorine-containing compound such as fluorine gas (Patent Documents 3 and 4), or a process gas containing hydrocarbon gas as a carbon raw material and fluorine A method for forming a carbon-based film containing fluorine by plasma CVD using fluorine carbide as a source is known (Patent Documents 5 and 6).
However, in these methods, there is a problem that it is necessary to use a large-sized device, or it is necessary to use fluorine gas which is toxic and difficult to handle. Further, when such a special material gas is used, a special reaction vessel is required, and the operation becomes complicated.
本発明者らは、上記のドライプロセスにおける問題について検討した結果、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、かつ簡便にカーボン系膜表面上にフッ素官能基を導入する方法として、カーボン系膜と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、カーボン系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既に見いだしている（上記特許文献７参照）。しかしながら、上記の方法は、従来のウエット法と同様に、ペルフルオロヘキサンなどの溶液の使用を必須とするものである。 As a result of studying the problems in the dry process, the present inventors introduced a fluorine functional group onto the carbon-based film surface safely and easily without using a toxic gas and without performing complicated operations. As a method for the above, it has already been found that a perfluoroalkyl group can be chemically bonded to the surface of the carbon film by irradiating the film with a carbon film and a perfluoroazoalkane in the solution and irradiating with ultraviolet light. (See Patent Document 7 above). However, like the conventional wet method, the above method requires the use of a solution such as perfluorohexane.
したがって、本発明の目的は、これら従来技術の問題点を解消して、溶液及び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、かつ簡便にカーボン系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。 Therefore, an object of the present invention is to solve these problems of the prior art, and to safely and easily perform fluorine on the carbon-based film surface without using a solution and a toxic gas and without performing complicated operations. It is to provide a method for introducing a functional group.
本発明者らは、上記目的を達成すべく鋭意研究を重ねた結果、カーボン系膜に、ガス状の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、カーボン系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た。 As a result of intensive research aimed at achieving the above object, the present inventors, as a result of irradiating a carbon film with ultraviolet light in the presence of a gaseous perfluoroazoalkane, formed a perfluoroalkyl group on the surface of the carbon film. We found that it can be chemically combined.
本発明はこれらの知見に基づいて完成に至ったものであり、本発明によれば、以下の発明が提供される。
［１］下記一般式（１）で表される気体のペルフルオロアゾアルカンの存在下で、カーボン系膜に紫外光を照射することによりカーボン系膜の表面にペルフルオロアルキル基を化学結合させることを特徴とするカーボン系膜の表面処理方法。
ＲＦＮ＝ＮＲＦ （１）
（式中、ＲＦはペルフルオロアルキル基を示す。）
［２］波長１７０〜３００ｎｍの紫外光を照射することを特徴とする上記［１］に記載のカーボン系膜の表面処理方法。
［３］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］又は［２］のカーボン系膜の表面処理方法。
The present invention has been completed based on these findings, and according to the present invention, the following inventions are provided.
[1] It is characterized in that a perfluoroalkyl group is chemically bonded to the surface of a carbon-based film by irradiating the carbon-based film with ultraviolet light in the presence of a gaseous perfluoroazoalkane represented by the following general formula (1). A carbon-based film surface treatment method.
R F N = NR F (1)
(In the formula, R F represents a perfluoroalkyl group.)
[2] The carbon-based film surface treatment method according to the above [1], wherein ultraviolet light having a wavelength of 170 to 300 nm is irradiated.
[3] The surface treatment method for a carbon-based film according to the above [1] or [2], wherein the light amount is irradiated in a range of 0.1 to 100 mW / cm 2 .
本発明によれば、気体のペルフルオロアゾアルカンに紫外光照射をするだけの簡便な反応操作により、カーボン系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、カーボン系膜の表面に、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。また、従来用いられていたフッ素系溶媒を使用する必要がないため、環境に優しい技術となり、溶媒に弱い材料に対してもフッ素官能基化が可能となり、より大面積基材への応用も可能となる効果がある。 According to the present invention, there is an excellent effect that a fluorine functional group can be introduced onto the surface of a carbon-based film by a simple reaction operation in which a gaseous perfluoroazoalkane is simply irradiated with ultraviolet light. In addition, since no conventionally used toxic gas is used, there is a remarkable effect that the perfluoroalkyl group can be bonded to the surface of the carbon-based film safely and without being complicated. In addition, since it is not necessary to use a fluorine-based solvent that has been used in the past, it is an environmentally friendly technology, and fluorine functionalization is possible even for materials that are weak to the solvent, enabling application to larger area substrates. There is an effect.
本発明の方法で用いられるカーボン系膜は、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カーボン系膜を作製したものでも良く、特にこのカーボン系膜の製造方法には制限はない。 As the carbon-based film used in the method of the present invention, a film produced by using plasma treatment using hydrocarbon as a raw material can be used. However, the carbon-based film may be produced by another manufacturing method, and the method for manufacturing the carbon-based film is not particularly limited.
前記カーボン系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。）
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、１〜８、より好ましくは、５〜８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、ペルフルオロアゾペン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。
The perfluoroazoalkane used for chemically bonding a fluorine functional group to the surface of the carbon-based film is a compound represented by the following general formula (1).
R F N = NR F (1)
(In the formula, R F represents a perfluoroalkyl group.)
The perfluoroalkyl group of the perfluoroazoalkane has 1 to 12, preferably 1 to 8, more preferably 5 to 8 carbon atoms. Specifically, perfluoroazooctane, perfluoroazoheptane, perfluoroazohexane, perfluoroazopentane, 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.
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、気体として反応容器に導入する。
反応に際しては、気体の前記ペルフルオロアゾアルカンおよびカーボン系膜存在下で光照射を行う。本発明の方法は、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１７０ｎｍ〜３００ｎｍとするのが好適である。
In the method of the present invention, the perfluoroazoalkane, which is a raw material, is introduced into a reaction vessel as a gas.
In the reaction, light irradiation is performed in the presence of gaseous perfluoroazoalkane and a carbon-based film. Since the method of the present invention requires generation of perfluoroalkyl radicals by denitrogenation reaction of the perfluoroazoalkane represented by the general formula (1), it is performed under ultraviolet light irradiation for this purpose. The wavelength is preferably 170 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。
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、１０分〜６時間程度とするのが望ましい。これらの条件は、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.
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 10 minutes to 6 hours. For these conditions, conditions outside the above range can be used. The above is a preferable range and is not necessarily limited thereto.
本発明の反応は、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。
このようにして得られるフッ素官能基化カーボン系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などによりフッ素の存在を確認することができ、水に対する接触角測定によっても撥水性を確認することができる。
The reaction of the present invention 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.
Whether the perfluoroalkyl group is chemically bonded to the surface of the fluorine-functionalized carbon film thus obtained is confirmed by an analytical instrument. Various analytical instruments can be used, but the presence of fluorine can be confirmed by XPS or the like, and water repellency can also be confirmed by measuring a contact angle with water.
本発明では、カーボン系膜に、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。 In the present invention, a perfluoroalkyl group can be chemically bonded to the carbon-based film. As a result, a functional group containing a fluorine atom can be bonded to the surface thereof, thereby imparting water repellency, oil repellency, and lubricity. be able to. In that case, it is thermally and chemically stable, and can give the characteristic which can endure an extreme environment.
以下、本発明を実施例に基づいて説明するが、本発明はこの実施例に限定されるものではない。
（実施例１）
合成石英製の反応容器にＤＬＣ膜を入れ、ペルフルオロアゾオクタンを気体として導入した。キセノンエキシマランプを室温で２０分間照射した。紫外光照射の波長は１７２ｎｍである。
その後、ＤＬＣ膜をペルフルオロヘキサンで超音波洗浄し、減圧下で乾燥を行った。反応後のＤＬＣ膜のＸＰＳ測定を行ったところ、図１に示すとおり、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。水に対する接触角が１０８°を示し、高い撥水性が付与された。
EXAMPLES Hereinafter, although this invention is demonstrated based on an Example, this invention is not limited to this Example.
Example 1
A DLC film was placed in a reaction vessel made of synthetic quartz, and perfluoroazooctane was introduced as a gas. A xenon excimer lamp was irradiated at room temperature for 20 minutes. The wavelength of ultraviolet light irradiation is 172 nm.
Thereafter, the DLC film was ultrasonically washed with perfluorohexane and dried under reduced pressure. When XPS measurement was performed on the DLC film after the reaction, as shown in FIG. 1, a peak derived from fluorine was observed, and it was confirmed that a fluorine functional group was introduced on the surface. The contact angle with water was 108 °, and high water repellency was imparted.
（実施例２）
合成石英製の反応容器にダイヤモンド膜を入れ、ペルフルオロアゾオクタンを気体として導入した。キセノンエキシマランプを室温で２０分間照射した。紫外光照射の波長は１７２ｎｍである。
その後、ダイヤモンド膜をペルフルオロヘキサンで超音波洗浄し、減圧下で乾燥を行った。反応後のダイヤモンド膜のＸＰＳ測定を行ったところ、図２に示すとおり、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。水に対する接触角が１１５°を示し、高い撥水性が付与された。
(Example 2)
A diamond film was placed in a reaction vessel made of synthetic quartz, and perfluoroazooctane was introduced as a gas. A xenon excimer lamp was irradiated at room temperature for 20 minutes. The wavelength of ultraviolet light irradiation is 172 nm.
Thereafter, the diamond film was ultrasonically washed with perfluorohexane and dried under reduced pressure. As a result of XPS measurement of the diamond film after the reaction, a peak derived from fluorine was observed as shown in FIG. 2, and it was confirmed that a fluorine functional group was introduced on the surface. The contact angle with water was 115 °, and high water repellency was imparted.
常温の気体中で紫外光照射をするだけの簡便な反応操作により、カーボン系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、溶剤や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、カーボン系膜の表面に、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、カーボン系膜の機能に、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、カーボン系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 carbon-based film by a simple reaction operation in which ultraviolet light irradiation is performed in a gas at room temperature. Since the conventionally used solvent and toxic gas are not used, the perfluoroalkyl group can be bonded to the surface of the carbon-based film safely and without complications.
As a result, the carbon-based film functions can be further possessed with unique properties unique to fluorine atoms and fluorine-containing functional groups, and functions such as physiological activity, water repellency, oil repellency, and lubricity can be expressed. Can do. In other words, the present invention is effective as a material that can be further thermally and chemically stable and can withstand an extreme environment by introducing a fluorine functional group onto the carbon-based surface.
Claims (3)
ＲＦＮ＝ＮＲＦ （１）
（式中、ＲＦはペルフルオロアルキル基を示す。） Carbon characterized by chemically bonding a perfluoroalkyl group to the surface of a carbon-based film by irradiating the carbon-based film with ultraviolet light in the presence of a gaseous perfluoroazoalkane represented by the following general formula (1) Method for surface treatment of system film.
R F N = NR F (1)
(In the formula, R F represents a perfluoroalkyl group.)
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