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JP6653816B2 - Water repellent high hardness film, mold and method for producing water repellent high hardness film - Google Patents
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JP6653816B2 - Water repellent high hardness film, mold and method for producing water repellent high hardness film - Google Patents

Water repellent high hardness film, mold and method for producing water repellent high hardness film Download PDF

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JP6653816B2
JP6653816B2 JP2017500268A JP2017500268A JP6653816B2 JP 6653816 B2 JP6653816 B2 JP 6653816B2 JP 2017500268 A JP2017500268 A JP 2017500268A JP 2017500268 A JP2017500268 A JP 2017500268A JP 6653816 B2 JP6653816 B2 JP 6653816B2
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fluorine
dlc film
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mold
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JPWO2016132562A1 (en
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本多　祐二
祐二 本多
浩平 奥平
浩平 奥平
阿部　浩二
浩二 阿部
有希子 遠藤
有希子 遠藤
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ADVANCED MATERIAL TECHNOLOGIES INC.
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/26—Deposition of carbon only
    • C23C16/27—Diamond only
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30

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  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Chemical Vapour Deposition (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Moulds For Moulding Plastics Or The Like (AREA)

Description

本発明は、フッ素含有ＤＬＣ（Ｄｉａｍｏｎｄ Ｌｉｋｅ Ｃａｒｂｏｎ）膜を有する撥水性高硬度膜、金型及び撥水性高硬度膜の製造方法に関する。   The present invention relates to a water-repellent high-hardness film having a fluorine-containing DLC (Diamond Like Carbon) film, a mold, and a method for manufacturing a water-repellent high-hardness film.

従来の射出成型機は、加熱して軟化した樹脂を射出圧を加えて金型に押込み、その金型に充填して成型するものである。このような射出成型機用の金型では、図１０に示すように、その金型１０１の一部１０２に樹脂の焼き付きが生じることがある。このような焼き付きが生じた金型では、焼き付いた樹脂を掃除しなければならず、その掃除が大変な時間と労力を要する上に、金型の寿命が短くなってしまう。
そこで、樹脂の焼き付きを抑制する方法として高硬度のＤＬＣ膜を金型の表面に成膜することが考えられる。
しかし、従来のＤＬＣ膜の水の接触角は６０°〜７２°程度であるため、成型する樹脂として接着性の高い樹脂（例えばアクリル樹脂、ポリ酢酸樹脂、フェノール樹脂等）を用いると、金型の一部１０２における樹脂の焼き付きを十分に抑制することができない。また、従来のＤＬＣ膜には、樹脂の焼き付きを抑制し、且つ金型にキズを付きにくくするために、水の接触角が大きく、且つ高硬度なＤＬＣ膜がなかった。In a conventional injection molding machine, a resin softened by heating is injected into a mold by applying an injection pressure, and the resin is filled into the mold and molded. In such a mold for an injection molding machine, as shown in FIG. 10, resin seizure may occur on a part 102 of the mold 101. In a mold in which such seizure has occurred, the baked resin must be cleaned, which requires a great deal of time and effort, and shortens the life of the mold.
Therefore, as a method for suppressing the seizure of the resin, it is conceivable to form a DLC film having high hardness on the surface of the mold.
However, since the contact angle of water of the conventional DLC film is about 60 ° to 72 °, if a resin having high adhesiveness (for example, an acrylic resin, a polyacetic acid resin, or a phenol resin) is used as a resin to be molded, a mold may be used. Of the resin in the part 102 cannot be sufficiently suppressed. Further, in the conventional DLC film, there is no DLC film having a large water contact angle and a high hardness in order to suppress seizure of the resin and to prevent the mold from being easily scratched.

本発明の一態様は、水の接触角が８０°以上で、且つ高い硬度を有する撥水性高硬度膜またはその撥水性高硬度膜を表面に成膜した金型または撥水性高硬度膜の製造方法を提供することを課題とする。   One embodiment of the present invention is to manufacture a water-repellent high-hardness film having a water contact angle of 80 ° or more and high hardness, or a mold or a water-repellent high-hardness film formed on the surface of the water-repellent high-hardness film. It is an object to provide a method.

以下に、本発明の種々の態様について説明する。
［１］フッ素を３原子％以上含有するフッ素含有ＤＬＣ膜であり、
前記フッ素含有ＤＬＣ膜は、水の接触角が８０°以上で、且つヌープ硬度が１０５０Ｈｋ以上であることを特徴とする撥水性高硬度膜。
上記のフッ素含有ＤＬＣ膜のフッ素の上限含有量は、１７原子％以下が好ましく、１０原子％以下がより好ましい。
［２］炭素と水素と珪素と窒素を含有する非晶質炭素膜と、
前記非晶質炭素膜上に形成されたＤＬＣ膜と、
前記ＤＬＣ膜上に形成されたフッ素を３原子％以上含有するフッ素含有ＤＬＣ膜を有する積層膜であり、
前記フッ素含有ＤＬＣ膜は、水の接触角が８０°以上（好ましくは９０°以上）で、且つヌープ硬度が１０５０Ｈｋ以上であることを特徴とする撥水性高硬度膜。
上記のフッ素含有ＤＬＣ膜のフッ素の上限含有量は、１７原子％以下が好ましく、１０原子％以下がより好ましい。
［３］上記［２］において、
前記非晶質炭素膜と前記ＤＬＣ膜と前記フッ素含有ＤＬＣ膜の膜厚比は下記式１を満たすことを特徴とする撥水性高硬度膜。
（非晶質炭素膜）：（ＤＬＣ膜）：（フッ素含有ＤＬＣ膜）＝（２．５〜７．５）：（１．５〜４．５）：（１〜３） ・・・式２
［４］上記［１］乃至［３］のいずれか一項において、
前記フッ素含有ＤＬＣ膜は、炭化水素系ガス及びフロオロカーボン系ガスを有する原料ガスと、周波数が１０〜５００ｋＨｚの高周波電力を用いたプラズマＣＶＤ法により成膜された膜であることを特徴とする撥水性高硬度膜。
［５］上記［２］または［３］において、
前記ＤＬＣ膜は、炭化水素系ガスを有する原料ガスと、周波数が１０〜５００ｋＨｚの高周波電力を用いたプラズマＣＶＤ法により成膜された膜であることを特徴とする撥水性高硬度膜。
［６］上記［１］において、
前記フッ素含有ＤＬＣ膜は金型の表面に形成されていることを特徴とする撥水性高硬度膜。
［７］上記［２］、［３］及び［５］のいずれか一項において、
前記非晶質炭素膜は金型の表面に形成されていることを特徴とする撥水性高硬度膜。
［８］上記［６］または［７］において、
前記金型はダイス鋼または高速度鋼により形成されていることを特徴とする撥水性高硬度膜。
［９］フッ素を３原子％以上含有するフッ素含有ＤＬＣ膜が表面に形成された金型であり、
前記フッ素含有ＤＬＣ膜は、水の接触角が８０°以上で、且つヌープ硬度が前記金型のヌープ硬度以上であることを特徴とする金型。
上記のフッ素含有ＤＬＣ膜のフッ素の上限含有量は、１７原子％以下が好ましく、１０原子％以下がより好ましい。
［１０］積層膜が表面に形成された金型であり、
前記積層膜は、炭素と水素と珪素と窒素を含有する非晶質炭素膜と、前記非晶質炭素膜上に形成されたＤＬＣ膜と、前記ＤＬＣ膜上に形成されたフッ素を３原子％以上含有するフッ素含有ＤＬＣ膜を有し、
前記フッ素含有ＤＬＣ膜は、水の接触角が８０°以上（好ましくは９０°以上）で、且つヌープ硬度が前記金型のヌープ硬度以上であることを特徴とする金型。
上記のフッ素含有ＤＬＣ膜のフッ素の上限含有量は、１７原子％以下が好ましく、１０原子％以下がより好ましい。
［１１］炭化水素系ガス及びフロオロカーボン系ガスを有する原料ガスと、周波数が１０〜５００ｋＨｚの高周波電力を用いたプラズマＣＶＤ法によりフッ素含有ＤＬＣ膜を形成することを特徴とする撥水性高硬度膜の製造方法。
［１２］炭素と水素と珪素と窒素を含有する原料ガスを用いたプラズマＣＶＤ法により非晶質炭素膜を形成し、
前記非晶質炭素膜上に、炭化水素系ガスを有する原料ガスと、周波数が１０〜５００ｋＨｚの高周波電力を用いたプラズマＣＶＤ法によりＤＬＣ膜を形成し、
前記ＤＬＣ膜上に、炭化水素系ガス及びフロオロカーボン系ガスを有する原料ガスと、周波数が１０〜５００ｋＨｚの高周波電力を用いたプラズマＣＶＤ法によりフッ素含有ＤＬＣ膜を形成することを特徴とする撥水性高硬度膜の製造方法。
［１３］上記［１１］または［１２］において、
前記フルオロカーボン系ガスは、Ｃ９Ｆ２１Ｎガスであることを特徴とする撥水性高硬度膜の製造方法。
［１４］上記［１１］において、
前記フッ素含有ＤＬＣ膜は金型の表面に形成されることを特徴とする撥水性高硬度膜の製造方法。
［１５］上記［１２］において、
前記非晶質炭素膜は金型の表面に形成されることを特徴とする撥水性高硬度膜の製造方法。Hereinafter, various aspects of the present invention will be described.
[1] A fluorine-containing DLC film containing 3 atomic% or more of fluorine,
The water-repellent high hardness film, wherein the fluorine-containing DLC film has a water contact angle of 80 ° or more and a Knoop hardness of 1050 Hk or more.
The upper limit of the fluorine content of the fluorine-containing DLC film is preferably 17 atomic% or less, more preferably 10 atomic% or less.
[2] an amorphous carbon film containing carbon, hydrogen, silicon and nitrogen;
A DLC film formed on the amorphous carbon film,
A laminated film having a fluorine-containing DLC film containing 3 atomic% or more of fluorine formed on the DLC film,
The fluorine-containing DLC film has a water contact angle of 80 ° or more (preferably 90 ° or more) and a Knoop hardness of 1050 Hk or more, wherein the water-repellent high hardness film is provided.
The upper limit of the fluorine content of the fluorine-containing DLC film is preferably 17 atomic% or less, more preferably 10 atomic% or less.
[3] In the above [2],
A film thickness ratio of the amorphous carbon film, the DLC film, and the fluorine-containing DLC film satisfies the following equation 1.
(Amorphous carbon film): (DLC film): (Fluorine-containing DLC film) = (2.5 to 7.5): (1.5 to 4.5): (1 to 3) Formula 2
[4] In any one of the above items [1] to [3],
The fluorine-containing DLC film is a film formed by a plasma CVD method using a source gas having a hydrocarbon-based gas and a fluorocarbon-based gas and a high-frequency power having a frequency of 10 to 500 kHz. Water-repellent high hardness film.
[5] In the above item [2] or [3],
The DLC film is a film formed by a plasma CVD method using a source gas having a hydrocarbon-based gas and high-frequency power having a frequency of 10 to 500 kHz.
[6] In the above item [1],
The water-repellent high hardness film, wherein the fluorine-containing DLC film is formed on a surface of a mold.
[7] In any one of the above-mentioned [2], [3] and [5],
The amorphous carbon film is formed on a surface of a mold, and is a water-repellent high hardness film.
[8] In the above item [6] or [7],
The water repellent high hardness film, wherein the mold is formed of die steel or high speed steel.
[9] A mold having a surface on which a fluorine-containing DLC film containing 3 atomic% or more of fluorine is formed,
A mold wherein the fluorine-containing DLC film has a contact angle of water of 80 ° or more and a Knoop hardness of at least the Knoop hardness of the mold.
The upper limit of the fluorine content of the fluorine-containing DLC film is preferably 17 atomic% or less, more preferably 10 atomic% or less.
[10] A mold having a laminated film formed on the surface,
The laminated film includes an amorphous carbon film containing carbon, hydrogen, silicon, and nitrogen, a DLC film formed on the amorphous carbon film, and 3 atomic% of fluorine formed on the DLC film. Having a fluorine-containing DLC film containing the above,
The mold wherein the fluorine-containing DLC film has a water contact angle of 80 ° or more (preferably 90 ° or more) and a Knoop hardness of at least the Knoop hardness of the mold.
The upper limit of the fluorine content of the fluorine-containing DLC film is preferably 17 atomic% or less, more preferably 10 atomic% or less.
[11] A water-repellent high hardness, wherein a fluorine-containing DLC film is formed by a plasma CVD method using a source gas having a hydrocarbon-based gas and a fluorocarbon-based gas and high-frequency power having a frequency of 10 to 500 kHz. Manufacturing method of membrane.
[12] forming an amorphous carbon film by a plasma CVD method using a source gas containing carbon, hydrogen, silicon and nitrogen;
Forming a DLC film on the amorphous carbon film by a plasma CVD method using a source gas having a hydrocarbon-based gas and a high-frequency power having a frequency of 10 to 500 kHz;
A fluorine-containing DLC film is formed on the DLC film by a plasma CVD method using a source gas having a hydrocarbon-based gas and a fluorocarbon-based gas and a high-frequency power having a frequency of 10 to 500 kHz. A method for producing an aqueous high hardness film.
[13] In the above item [11] or [12],
The method for producing a water-repellent high hardness film, wherein the fluorocarbon-based gas is a C 9 F 21 N gas.
[14] In the above item [11],
The method for producing a water-repellent high-hardness film, wherein the fluorine-containing DLC film is formed on a surface of a mold.
[15] In the above item [12],
The method for producing a water-repellent high hardness film, wherein the amorphous carbon film is formed on a surface of a mold.

本発明の一態様によれば、水の接触角が８０°以上で、且つ高い硬度を有する撥水性高硬度膜またはその撥水性高硬度膜を表面に成膜した金型または撥水性高硬度膜の製造方法を提供することができる。   According to one embodiment of the present invention, a water-repellent high-hardness film having a water contact angle of 80 ° or more and high hardness, or a mold or a water-repellent high-hardness film having the water-repellent high-hardness film formed on its surface Can be provided.

図１は、本発明の一態様に係る撥水性高硬度膜の製造方法を説明するための断面図である。
図２は、本発明の一態様に係る撥水性高硬度膜の製造方法を説明するための断面図である。
図３は、実施例１のサンプル１−１のフッ素含有ＤＬＣ膜の水の接触角と、比較例のサンプル１−２のフッ素含有ＤＬＣ膜の水の接触角及び比較例のサンプルのＤＬＣ膜の水の接触角を測定した結果を示す図である。
図４は、実施例１のサンプル１−１のフッ素含有ＤＬＣ膜のヌープ硬度と、比較例のサンプル１−２のフッ素含有ＤＬＣ膜のヌープ硬度及び比較例のサンプルのＤＬＣ膜のヌープ硬度を測定した結果を示す図である。
図５は、実施例２のサンプル２−１及びサンプル２−２それぞれのフッ素含有ＤＬＣ膜の水の接触角と、比較例のサンプルのＤＬＣ膜の水の接触角を測定した結果を示す図である。
図６は、実施例２のサンプル２−１及びサンプル２−２それぞれのフッ素含有ＤＬＣ膜のヌープ硬度と、比較例のサンプルのＤＬＣ膜のヌープ硬度を測定した結果を示す図である。
図７は、実施例２のサンプル２−１の写真である。
図８は、実施例２のサンプル２−１及びサンプル２−２それぞれのフッ素含有ＤＬＣ膜にＸＰＳ分析を行った結果を示す図である。
図９は、実施例２のサンプル２−１及びサンプル２−２それぞれのフッ素含有ＤＬＣ膜にＸＰＳ分析を行った結果を示す図である。
図１０は、従来の射出成型機用の金型を模式的に示す断面図である。
図１１（Ａ）は実施例２のサンプル２−２のＨＡＡＤＦによる膜厚測定結果を示す図、図１１（Ｂ）は実施例２のサンプル２−１のＨＡＡＤＦによる膜厚測定結果を示す図である。
図１２は、実施例２のサンプル２−１のＸＰＳ分析のＤｅｐｔｈ−Ｐｒｏｆｉｌｅを示す図である。
図１３は、実施例２のサンプル２−２のＸＰＳ分析のＤｅｐｔｈ−Ｐｒｏｆｉｌｅを示す図である。FIG. 1 is a cross-sectional view illustrating a method for manufacturing a water-repellent high-hardness film according to one embodiment of the present invention.
FIG. 2 is a cross-sectional view illustrating a method for manufacturing a water-repellent high-hardness film according to one embodiment of the present invention.
FIG. 3 shows the water contact angle of the fluorine-containing DLC film of Sample 1-1 of Example 1, the water contact angle of the fluorine-containing DLC film of Sample 1-2 of the comparative example, and the DLC film of the comparative sample. It is a figure showing the result of having measured the contact angle of water.
FIG. 4 shows the Knoop hardness of the fluorine-containing DLC film of Sample 1-1 of Example 1, the Knoop hardness of the fluorine-containing DLC film of Sample 1-2 of the comparative example, and the Knoop hardness of the DLC film of the sample of the comparative example. It is a figure which shows the result.
FIG. 5 is a diagram showing the results of measuring the water contact angle of the fluorine-containing DLC film of each of Samples 2-1 and 2-2 of Example 2 and the water contact angle of the DLC film of the sample of Comparative Example. is there.
FIG. 6 is a diagram showing the results of measuring the Knoop hardness of the fluorine-containing DLC film of each of Samples 2-1 and 2-2 of Example 2 and the Knoop hardness of the DLC film of the sample of Comparative Example.
FIG. 7 is a photograph of Sample 2-1 of Example 2.
FIG. 8 is a diagram showing the results of XPS analysis performed on each of the fluorine-containing DLC films of Sample 2-1 and Sample 2-2 in Example 2.
FIG. 9 is a diagram showing the results of XPS analysis performed on each of the fluorine-containing DLC films of Samples 2-1 and 2-2 in Example 2.
FIG. 10 is a cross-sectional view schematically showing a conventional mold for an injection molding machine.
FIG. 11A is a diagram showing the results of measuring the film thickness of Sample 2-2 of Example 2 using HAADF, and FIG. 11B is a diagram showing the results of measuring the film thickness of Sample 2-1 of Example 2 using HAADF. is there.
FIG. 12 is a diagram illustrating a depth-profile of the XPS analysis of the sample 2-1 in Example 2.
FIG. 13 is a diagram illustrating a depth-profile of the XPS analysis of the sample 2-2 in Example 2.

以下では、本発明の実施形態について図面を用いて詳細に説明する。ただし、本発明は以下の説明に限定されず、本発明の趣旨及びその範囲から逸脱することなくその形態及び詳細を様々に変更し得ることは、当業者であれば容易に理解される。従って、本発明は以下に示す実施形態の記載内容に限定して解釈されるものではない。
［第１の実施形態］
図１は、本発明の一態様に係る撥水性高硬度膜の製造方法を説明するための断面図である。
まず、ダイス鋼または高速度鋼により形成された金型１１を準備する。なお、本実施形態では、金型１１を用いているが、金型に限定されるものではなく、金型以外の種々の基材を用いてもよい。
次に、金型１１の表面上に、炭化水素系ガスとフロオロカーボン系ガスを混合した混合ガスを原料ガスとして用い、１．５〜５Ｐａの圧力下で、周波数が１０〜５００ｋＨｚ（好ましくは１００〜４００ｋＨｚ）の高周波電力を金型１１または金型１１と対向する電極（図示せず）に供給する条件のプラズマＣＶＤ法によりフッ素含有ＤＬＣ膜１２を形成する。この際の温度条件は、室温〜１００℃程度が好ましい。このフッ素含有ＤＬＣ膜１２は、フッ素を３原子％以上含有し、水の接触角が８０°以上で、且つヌープ硬度が１０５０Ｈｋ以上である。また、フッ素含有ＤＬＣ膜１２のフッ素の上限含有量は、１７原子％以下が好ましく、１０原子％以下がより好ましい。
なお、フッ素含有ＤＬＣ膜１２には５原子％以下の窒素が含まれていてもよい。また、フッ素含有ＤＬＣ膜１２の成膜に用いるプラズマＣＶＤ装置としては、例えば平行平板型のプラズマＣＶＤ装置を用いることができる。
また、本明細書において「フルオロカーボン系ガス」とは、炭素とフッ素の結合を持つ有機化合物系のガスを意味する。フルオロカーボン系ガスとしては、Ｃ３Ｆ６、Ｃ４Ｆ６、Ｃ６Ｆ６、Ｃ６Ｆ１２、Ｃ６Ｆ１４、Ｃ７Ｆ８、Ｃ７Ｆ１４、Ｃ７Ｆ１６、Ｃ８Ｆ１６、Ｃ８Ｆ１８、Ｃ９Ｆ１８、Ｃ９Ｆ２０、Ｃ１０Ｆ８、Ｃ１０Ｆ１８、Ｃ１１Ｆ２０、Ｃ１２Ｆ１０、Ｃ１３Ｆ２８、Ｃ１５Ｆ３２、Ｃ２０Ｆ４２、Ｃ２４Ｆ５０、Ｃ３Ｆ３Ｎ３、Ｃ３Ｆ９Ｎ、Ｃ５Ｆ５Ｎ、Ｃ６Ｆ４Ｎ２、Ｃ６Ｆ９Ｎ３、Ｃ６Ｆ１２Ｎ２、Ｃ６Ｆ１５Ｎ、Ｃ７Ｆ５Ｎ、Ｃ８Ｆ４Ｎ２、Ｃ９Ｆ２１Ｎ、Ｃ１２Ｆ４Ｎ４、Ｃ１２Ｆ２７Ｎ、Ｃ１４Ｆ８Ｎ２、Ｃ１５Ｆ３３Ｎ、Ｃ２４Ｆ４５Ｎ３、トリヘプタフルオロプロピルアミン、Ｃ３Ｆ６Ｏ、Ｃ４Ｆ６Ｏ３、Ｃ４Ｆ８Ｏ、Ｃ５Ｆ６Ｏ３、Ｃ６Ｆ４Ｏ２、Ｃ６Ｆ１０Ｏ３、Ｃ８Ｆ４Ｏ３、Ｃ８Ｆ８Ｏ、Ｃ８Ｆ８Ｏ２、Ｃ８Ｆ１４Ｏ３、Ｃ１３Ｆ１０Ｏ、Ｃ１３Ｆ１０Ｏ３、Ｃ２Ｆ６Ｏ（Ｃ３Ｆ６Ｏ）ｎ（ＣＦ２Ｏ）ｍ、及びＣ７Ｆ５ＮＯの少なくとも一つを用いることができる。
本実施形態によれば、上記の成膜条件のプラズマＣＶＤ法によりフッ素含有ＤＬＣ膜１２を形成するため、フッ素含有ＤＬＣ膜１２を水の接触角が８０°以上で、且つヌープ硬度が１０５０Ｈｋ以上である撥水性高硬度膜とすることができる。詳細には、フッ素含有ＤＬＣ膜１２にフッ素を３原子％以上含有させるため、フッ素含有ＤＬＣ膜１２の水の接触角を８０°以上とすることができる。フッ素の含有量の下限値を３原子％とする理由は、水の接触角を８０°以上とするにはフッ素の含有量が少なくとも３原子％必要であるからである。また、フッ素の含有量の好ましい上限値を１７原子％とする理由は、１７原子％より多くフッ素を含有させると１０５０Ｈｋのヌープ硬度を保てなくなるからである。
このようなフッ素含有ＤＬＣ膜１２を樹脂成型用の金型に用いた場合、金型１１の表面を水の接触角が８０°以上の撥水性とすることで、金型１１と樹脂との離型性を高めることができ、その結果、金型１１の一部に樹脂の焼き付きが生じることを抑制できる。従って、焼き付いた樹脂を掃除する頻度を抑制でき、その掃除による時間と労力を低減でき、金型の寿命を長くすることができる。また、フッ素含有ＤＬＣ膜１２が高硬度であるため、金型やフッ素含有ＤＬＣ膜１２にキズが付くのを抑制できる。
また、フッ素含有ＤＬＣ膜１２が、高硬度を得られる理由として、ダイヤモンド構造と呼ばれるｓｐ３を多く含んだＤＬＣ膜を主たる構造としていることがあげられる。ＤＬＣを構成する炭素の一部をフッ素で置換することにより、高硬度と撥水性を兼ねるフッ素含有ＤＬＣ膜を得ることができる。対して、単なる炭素膜ではアモルファス構造と呼ばれるｓｐ２が多く、構造的に強度を得ることが不可能である。よって、単純に炭素膜にフッ素を含有しても高硬度且つ甲撥水性を兼ねる膜をえることはできない。
なお、本実施形態では、フッ素含有ＤＬＣ膜１２のヌープ硬度を１０５０Ｈｋ以上としているが、これに限定されるものではなく、フッ素含有ＤＬＣ膜１２が成膜される下地（金型１１または基材）のヌープ硬度以上であればよい。１０５０Ｈｋのヌープ硬度は高速度鋼の硬度である。
［第２の実施形態］
図２は、本発明の一態様に係る撥水性高硬度膜の製造方法を説明するための断面図である。
まず、第１の実施形態と同様の金型１１を準備する。
次に、金型１１の表面上に、炭素と水素と珪素と窒素を含有する原料ガス（例えばＨＭＤＳ−Ｎを有する原科ガス）を用い、１．５〜５Ｐａの圧力下で、周波数が１０〜５００ｋＨｚ（好ましくは１００〜４００ｋＨｚ）の高周波電力を金型１１または金型１１と対向する電極（図示せず）に供給する条件のプラズマＣＶＤ法により非晶質炭素膜１３を形成する。この際の温度条件は、室温〜１００℃程度が好ましい。この非晶質炭素膜１３は、例えばＣａＨｂＳｉｃＮｄ膜である。但し、ａ，ｂ，ｃ，ｄは、自然数である。また、ＨＭＤＳ−Ｎはヘキサメチルジシラザン（Ｃ６Ｈ１９ＮＳｉ２）である。
なお、本実施の形態では、非晶質炭素膜１３を成膜する際の高周波電力の周波数を１０〜５００ｋＨｚとしているが、これに限定されるものではなく、高周波電力の周波数として１３．５６ＭＨｚを用いてもよい。
次に、非晶質炭素膜１３上に、炭化水素系ガスを有する原料ガス（例えばＣ７Ｈ８を有する原料ガス）を用い、１．５〜５Ｐａの圧力下で、周波数が１０〜５００ｋＨｚ（好ましくは１００〜４００ｋＨｚ）の高周波電力を金型１１または金型１１と対向する電極（図示せず）に供給する条件のプラズマＣＶＤ法によりＤＬＣ膜１４を形成する。この際の温度条件は、室温〜１００℃程度が好ましい。
次に、ＤＬＣ膜１４上に、第１の実施形態と同様の成膜条件のプラズマＣＶＤ法によりフッ素含有ＤＬＣ膜１５を形成する。このフッ素含有ＤＬＣ膜１５は、フッ素を３原子％以上含有し、水の接触角が８０°以上（好ましくは９０°以上）で、且つヌープ硬度が１０５０Ｈｋ以上である。また、フッ素含有ＤＬＣ膜１５のフッ素の上限含有量は、１７原子％以下が好ましく、１０原子％以下がより好ましい。
本実施形態においても第１の実施形態と同様の効果を得ることができる。
また、本実施形態によれば、金型１１とフッ素含有ＤＬＣ膜１５との間に非晶質炭素膜１３とＤＬＣ膜１４を形成するため、第１の実施形態のフッ素含有ＤＬＣ膜１２に比べて高い硬度を維持しても水の接触角をより高くすることができる。以下に詳細に説明する。
非晶質炭素膜１３を形成することで、非晶質炭素膜１３を構成する元素の一部がＤＬＣ膜１４に拡散し、拡散層を形成することにより、金型１１とＤＬＣ膜１４の密着性を高めることができる。同様にＤＬＣ膜１４及びフッ素含有ＤＬＣ膜１５との間にもＤＬＣ膜１５を構成する元素による拡散層が形成され、密着性が高まっている。また、ＤＬＣ膜１４を形成することで、フッ素含有ＤＬＣ膜１５の硬度をより高くすることができる。また、非晶質炭素膜１３にＳｉが含有していると、そのＳｉがフッ素含有ＤＬＣ膜１５のフッ素によってエッチングされてしまうことがあるが、そのフッ素によるＳｉのエッチングをＤＬＣ膜１４によって抑制できる。
また、非晶質炭素膜１３とＤＬＣ膜１４とフッ素含有ＤＬＣ膜１５の膜厚比は、下記の式１で表され、式１を中心値として±５０％の範囲内である下記の式２を満たすことが好ましく、より好ましくは±３０％の範囲内であり、さらに好ましくは±２０％の範囲内である。
（非晶質炭素膜）：（ＤＬＣ膜）：（フッ素含有ＤＬＣ膜）＝５：３：２ ・・・式１
（非晶質炭素膜）：（ＤＬＣ膜）：（フッ素含有ＤＬＣ膜）＝（２．５〜７．５）：（１．５〜４．５）：（１〜３） ・・・式２
フッ素含有ＤＬＣ膜１５を樹脂成型用の金型に用いた場合、フッ素含有ＤＬＣ膜１５は前述したように金型１１と樹脂との離型性を高める機能を有する。それに加えて、ＤＬＣ膜１４は、その硬さが例えば１１００〜１４５０Ｈｋと硬いため（図４参照）、高い耐衝撃性を有する。そのため、フッ素含有ＤＬＣ膜１５に衝撃が加えられた時に、ＤＬＣ膜１４によってその衝撃に耐えることができる。さらに、非晶質炭素膜１３はＤＬＣ膜１４の密着性を高める機能を有するため、その非晶質炭素膜１３によってＤＬＣ膜１４の剥離を防ぐことができる。これらの効果は、上記式２を満たす膜厚比とすることで、十分に発揮することが可能となる。
なお、非晶質炭素膜１３の硬さは、９００Ｈｋ程度であり、例えば８００〜１０００Ｈｖの範囲内である。
また、非晶質炭素膜１３とＤＬＣ膜１４とフッ素含有ＤＬＣ膜１５の合計膜厚は、０．３μｍ以上５μｍ以下（好ましくは１μｍ以上３μｍ以下）である。
なお、本実施形態では、フッ素含有ＤＬＣ膜１５のヌープ硬度を１０５０Ｈｋ以上としているが、これに限定されるものではなく、フッ素含有ＤＬＣ膜１５が成膜される下地（金型１１または基材）のヌープ硬度以上であればよい。Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. However, the present invention is not limited to the following description, and it is easily understood by those skilled in the art that the form and details can be variously changed without departing from the spirit and scope of the present invention. Therefore, the present invention is not construed as being limited to the description of the embodiments below.
[First Embodiment]
FIG. 1 is a cross-sectional view illustrating a method for manufacturing a water-repellent high-hardness film according to one embodiment of the present invention.
First, a mold 11 formed of die steel or high-speed steel is prepared. In the present embodiment, the mold 11 is used, but the invention is not limited to the mold, and various substrates other than the mold may be used.
Next, on the surface of the mold 11, using a mixed gas obtained by mixing a hydrocarbon-based gas and a fluorocarbon-based gas as a raw material gas, at a pressure of 1.5 to 5 Pa and a frequency of 10 to 500 kHz (preferably, A fluorine-containing DLC film 12 is formed by a plasma CVD method under a condition in which high-frequency power of 100 to 400 kHz) is supplied to the mold 11 or an electrode (not shown) facing the mold 11. The temperature condition at this time is preferably from room temperature to about 100 ° C. The fluorine-containing DLC film 12 contains 3 atomic% or more of fluorine, has a water contact angle of 80 ° or more, and has a Knoop hardness of 1050 Hk or more. Further, the upper limit content of fluorine in the fluorine-containing DLC film 12 is preferably 17 atomic% or less, more preferably 10 atomic% or less.
Note that the fluorine-containing DLC film 12 may contain 5 atomic% or less of nitrogen. As a plasma CVD apparatus used for forming the fluorine-containing DLC film 12, for example, a parallel plate type plasma CVD apparatus can be used.
Further, in the present specification, “fluorocarbon-based gas” means an organic compound-based gas having a bond between carbon and fluorine. The fluorocarbon-based gas, C 3 F 6, C 4 F 6, C 6 F 6, C 6 F 12, C 6 F 14, C 7 F 8, C 7 F 14, C 7 F 16, C 8 F 16 , C 8 F 18, C 9 F 18, C 9 F 20, C 10 F 8, C 10 F 18, C 11 F 20, C 12 F 10, C 13 F 28, C 15 F 32, C 20 F 42 , C 24 F 50, C 3 F 3 N 3, C 3 F 9 N, C 5 F 5 N, C 6 F 4 N 2, C 6 F 9 N 3, C 6 F 12 N 2, C 6 F 15 N, C 7 F 5 N, C 8 F 4 N 2, C 9 F 21 N, C 12 F 4 N 4, C 12 F 27 N, C 14 F 8 N 2, C 15 F 33 N, C 24 F 45 N 3 , triheptafluoropropylamine, C 3 F 6 O, C 4 F 6 O 3 , C 4 F 8 O, C 5 F 6 O 3 , C 6 F 4 O 2 , C 6 F 10 O 3 , C 8 F 4 O 3 , C 8 F 8 O, C 8 F 8 O 2 , C 8 F At least one of 14 O 3 , C 13 F 10 O, C 13 F 10 O 3 , C 2 F 6 O (C 3 F 6 O) n (CF 2 O) m, and C 7 F 5 NO is used. Can be.
According to this embodiment, since the fluorine-containing DLC film 12 is formed by the plasma CVD method under the above-described film forming conditions, the fluorine-containing DLC film 12 has a water contact angle of 80 ° or more, and a Knoop hardness of 1050 Hk or more. A certain water repellent high hardness film can be obtained. Specifically, since the fluorine-containing DLC film 12 contains 3 atomic% or more of fluorine, the contact angle of water of the fluorine-containing DLC film 12 can be 80 ° or more. The reason why the lower limit value of the fluorine content is set to 3 atomic% is that at least 3 atomic% of the fluorine content is required to make the contact angle of water 80 ° or more. The reason why the preferable upper limit of the fluorine content is 17 atomic% is that if more than 17 atomic% is contained, the Knoop hardness of 1050 Hk cannot be maintained.
When such a fluorine-containing DLC film 12 is used in a mold for resin molding, the surface of the mold 11 is made water-repellent so that the contact angle of water is 80 ° or more, thereby separating the mold 11 from the resin. The moldability can be improved, and as a result, seizure of the resin on a part of the mold 11 can be suppressed. Therefore, the frequency of cleaning the baked resin can be suppressed, the time and labor for the cleaning can be reduced, and the life of the mold can be prolonged. Further, since the fluorine-containing DLC film 12 has a high hardness, it is possible to prevent the mold and the fluorine-containing DLC film 12 from being scratched.
The reason why the fluorine-containing DLC film 12 can obtain high hardness is that a DLC film mainly containing a large amount of sp3 called a diamond structure is used. By substituting a part of the carbon constituting the DLC with fluorine, a fluorine-containing DLC film having both high hardness and water repellency can be obtained. On the other hand, a simple carbon film has many sp2 called an amorphous structure, and it is impossible to obtain structural strength. Therefore, even if fluorine is simply contained in the carbon film, a film having both high hardness and water repellency cannot be obtained.
In the present embodiment, the Knoop hardness of the fluorine-containing DLC film 12 is set to 1050 Hk or more. However, the present invention is not limited to this, and the underlayer (the mold 11 or the base material) on which the fluorine-containing DLC film 12 is formed. Or more than the Knoop hardness. A Knoop hardness of 1050 Hk is the hardness of high speed steel.
[Second embodiment]
FIG. 2 is a cross-sectional view illustrating a method for manufacturing a water-repellent high-hardness film according to one embodiment of the present invention.
First, a mold 11 similar to that of the first embodiment is prepared.
Next, on the surface of the mold 11, using a source gas containing carbon, hydrogen, silicon, and nitrogen (for example, a raw material gas having HMDS-N) and a pressure of 1.5 to 5 Pa and a frequency of 10 The amorphous carbon film 13 is formed by a plasma CVD method under a condition in which high-frequency power of 500 kHz (preferably 100 to 400 kHz) is supplied to the mold 11 or an electrode (not shown) facing the mold 11. The temperature condition at this time is preferably from room temperature to about 100 ° C. The amorphous carbon film 13 is, for example, C a H b Si c N d membrane. Here, a, b, c, and d are natural numbers. HMDS-N is hexamethyldisilazane (C 6 H 19 NSi 2 ).
In the present embodiment, the frequency of the high-frequency power when the amorphous carbon film 13 is formed is set to 10 to 500 kHz. However, the present invention is not limited to this, and 13.56 MHz is used as the frequency of the high-frequency power. May be used.
Next, on the amorphous carbon film 13, a source gas having a hydrocarbon-based gas (for example, a source gas having C 7 H 8 ) is used at a pressure of 1.5 to 5 Pa and a frequency of 10 to 500 kHz ( The DLC film 14 is formed by a plasma CVD method under a condition that high-frequency power (preferably 100 to 400 kHz) is supplied to the mold 11 or an electrode (not shown) facing the mold 11. The temperature condition at this time is preferably from room temperature to about 100 ° C.
Next, a fluorine-containing DLC film 15 is formed on the DLC film 14 by a plasma CVD method under the same film forming conditions as in the first embodiment. The fluorine-containing DLC film 15 contains 3 atomic% or more of fluorine, has a water contact angle of 80 ° or more (preferably 90 ° or more), and has a Knoop hardness of 1050 Hk or more. Further, the upper limit content of fluorine in the fluorine-containing DLC film 15 is preferably 17 atomic% or less, more preferably 10 atomic% or less.
In the present embodiment, the same effect as in the first embodiment can be obtained.
Further, according to the present embodiment, since the amorphous carbon film 13 and the DLC film 14 are formed between the mold 11 and the fluorine-containing DLC film 15, compared with the fluorine-containing DLC film 12 of the first embodiment. Even if the hardness is kept high, the contact angle of water can be further increased. This will be described in detail below.
By forming the amorphous carbon film 13, some of the elements constituting the amorphous carbon film 13 diffuse into the DLC film 14, and by forming a diffusion layer, the mold 11 and the DLC film 14 adhere to each other. Can be enhanced. Similarly, a diffusion layer made of the elements constituting the DLC film 15 is formed between the DLC film 14 and the fluorine-containing DLC film 15 to increase the adhesion. Further, by forming the DLC film 14, the hardness of the fluorine-containing DLC film 15 can be further increased. If the amorphous carbon film 13 contains Si, the Si may be etched by fluorine of the fluorine-containing DLC film 15, but the etching of Si by the fluorine can be suppressed by the DLC film 14. .
The film thickness ratio of the amorphous carbon film 13, the DLC film 14, and the fluorine-containing DLC film 15 is represented by the following equation 1, and the following equation 2 is within ± 50% with respect to equation 1 as a central value. Is preferably satisfied, more preferably within a range of ± 30%, and still more preferably within a range of ± 20%.
(Amorphous carbon film): (DLC film): (Fluorine-containing DLC film) = 5: 3: 2 Formula 1
(Amorphous carbon film): (DLC film): (Fluorine-containing DLC film) = (2.5 to 7.5): (1.5 to 4.5): (1 to 3) Formula 2
When the fluorine-containing DLC film 15 is used for a mold for resin molding, the fluorine-containing DLC film 15 has a function of improving the releasability between the mold 11 and the resin as described above. In addition, the DLC film 14 has a high impact resistance because its hardness is as high as 1100 to 1450 Hk (see FIG. 4). Therefore, when a shock is applied to the fluorine-containing DLC film 15, the DLC film 14 can withstand the shock. Further, since the amorphous carbon film 13 has a function of enhancing the adhesion of the DLC film 14, the detachment of the DLC film 14 can be prevented by the amorphous carbon film 13. These effects can be sufficiently exerted by setting the film thickness ratio to satisfy the above equation (2).
The hardness of the amorphous carbon film 13 is about 900 Hk, for example, in the range of 800 to 1000 Hv.
The total thickness of the amorphous carbon film 13, the DLC film 14, and the fluorine-containing DLC film 15 is 0.3 μm or more and 5 μm or less (preferably 1 μm or more and 3 μm or less).
In the present embodiment, the Knoop hardness of the fluorine-containing DLC film 15 is set to 1050 Hk or more. However, the present invention is not limited to this, and the underlayer (the mold 11 or the base material) on which the fluorine-containing DLC film 15 is formed. Or more than the Knoop hardness.

実施例１のサンプルは第１の実施形態と同様の膜構造である。
図３は、実施例１のサンプル１−１のフッ素含有ＤＬＣ膜の水の接触角と、比較例のサンプル１−２のフッ素含有ＤＬＣ膜の水の接触角及び比較例のサンプルのＤＬＣ膜の水の接触角を測定した結果を示す図である。図３に示す測定結果は、サンプル上の複数の点の接触角を測定し、平均化したものである。
図４は、実施例１のサンプル１−１のフッ素含有ＤＬＣ膜のヌープ硬度と、比較例のサンプル１−２のフッ素含有ＤＬＣ膜のヌープ硬度及び比較例のサンプルのＤＬＣ膜のヌープ硬度を測定した結果を示す図である。図４に示す測定結果は、サンプル上の複数の点のヌープ硬度を測定し、平均化したものである。
≪実施例１のサンプル１−１≫
実施例１のサンプル１−１は、基材上にフッ素含有ＤＬＣ膜を以下の成膜条件で成膜したものである。
＜フッ素含有ＤＬＣ膜の条件＞
基材：ＳＵＳ板
成膜装置：平行平板型のプラズマＣＶＤ装置
原料ガス：流量１５ｓｃｃｍのＣ７Ｈ８と流量１５ｓｃｃｍのＣ９Ｆ２１Ｎの混合ガス
高周波電源の周波数：３８０ＫＨｚ
高周波出力：１０００Ｗ
圧力：１．５Ｐａ
温度：室温
膜厚：１μｍ
≪比較例のサンプル１−２≫
比較例のサンプル１−２は、基材上にフッ素含有ＤＬＣ膜を以下の成膜条件で成膜したものである。
＜フッ素含有ＤＬＣ膜の条件＞
基材：サンプル１−１と同一
成膜装置：サンプル１−１と同一
原料ガス：流量５ｓｃｃｍのＣ７Ｈ８と流量２５ｓｃｃｍのＣ９Ｆ２１Ｎの混合ガス
高周波電源の周波数：サンプル１−１と同一
高周波出力：サンプル１−１と同一
圧力：サンプル１−１と同一
温度：サンプル１−１と同一
膜厚：１μｍ
≪比較例のサンプルＤＬＣ≫
比較例のサンプルは、基材上にＤＬＣ膜を以下の成膜条件で成膜したものである。
＜ＤＬＣ膜の条件＞
基材：サンプル１−１と同一
成膜装置：サンプル１−１と同一
原料ガス：流量３０ｓｃｃｍのＣ７Ｈ８
高周波電源の周波数：サンプル１−１と同一
高周波出力：サンプル１−１と同一
圧力：サンプル１−１と同一
温度：サンプル１−１と同一
膜厚：０．２μｍ
図３及び図４に示すように、実施例１のサンプル１−１では水の接触角が８０°以上でヌープ硬度が１２６５Ｈｋであるのに対し、比較例のサンプル１−２では水の接触角は９０°と高いが、ヌープ硬度が１０５０Ｈｋより大幅に低くなり、比較例のサンプル（ＤＬＣ）ではヌープ硬度は１０５０Ｈｋより高いが、水の接触角が８０°よりかなり低くなった。The sample of Example 1 has a film structure similar to that of the first embodiment.
FIG. 3 shows the water contact angle of the fluorine-containing DLC film of Sample 1-1 of Example 1, the water contact angle of the fluorine-containing DLC film of Sample 1-2 of the comparative example, and the DLC film of the comparative sample. It is a figure showing the result of having measured the contact angle of water. The measurement results shown in FIG. 3 are obtained by measuring and averaging the contact angles of a plurality of points on the sample.
FIG. 4 shows the Knoop hardness of the fluorine-containing DLC film of Sample 1-1 of Example 1, the Knoop hardness of the fluorine-containing DLC film of Sample 1-2 of the comparative example, and the Knoop hardness of the DLC film of the sample of the comparative example. It is a figure which shows the result. The measurement results shown in FIG. 4 are obtained by measuring and averaging the Knoop hardness at a plurality of points on the sample.
<< Sample 1-1 of Example 1 >>
Sample 1-1 of Example 1 was obtained by forming a fluorine-containing DLC film on a substrate under the following film forming conditions.
<Conditions of fluorine-containing DLC film>
Base material: SUS plate Film forming device: parallel plate type plasma CVD device Source gas: mixed gas of C 7 H 8 at a flow rate of 15 sccm and C 9 F 21 N at a flow rate of 15 sccm High frequency power supply frequency: 380 KHz
High frequency output: 1000W
Pressure: 1.5Pa
Temperature: room temperature Film thickness: 1 μm
<< Sample 1-2 of Comparative Example >>
Sample 1-2 of the comparative example was obtained by forming a fluorine-containing DLC film on a substrate under the following film forming conditions.
<Conditions of fluorine-containing DLC film>
Base material: same as sample 1-1 Film forming apparatus: same as sample 1-1 Source gas: mixed gas of C 7 H 8 at a flow rate of 5 sccm and C 9 F 21 N at a flow rate of 25 sccm High-frequency power supply frequency: sample 1-1 High frequency output: same as sample 1-1 Pressure: same as sample 1-1 Temperature: same as sample 1-1 Film thickness: 1 μm
<< Sample DLC of Comparative Example >>
In the sample of the comparative example, a DLC film was formed on a substrate under the following film forming conditions.
<DLC film conditions>
Base material: same as sample 1-1 Film forming apparatus: same as sample 1-1 Source gas: C 7 H 8 at a flow rate of 30 sccm
Frequency of high-frequency power supply: same as sample 1-1 High-frequency output: same as sample 1-1 Pressure: same as sample 1-1 Temperature: same as sample 1-1 Film thickness: 0.2 μm
As shown in FIGS. 3 and 4, Sample 1-1 of Example 1 has a water contact angle of 80 ° or more and Knoop hardness of 1265 Hk, whereas Sample 1-2 of Comparative Example has a water contact angle. Is as high as 90 °, but the Knoop hardness is significantly lower than 1050Hk, and the Knoop hardness is higher than 1050Hk in the comparative sample (DLC), but the contact angle of water is significantly lower than 80 °.

実施例２のサンプルは第２の実施形態と同様の膜構造である。
図５は、実施例２のサンプル２−１及びサンプル２−２それぞれのフッ素含有ＤＬＣ膜の水の接触角と、比較例のサンプルのＤＬＣ膜の水の接触角を測定した結果を示す図である。図５に示す測定結果は、サンプル上の複数の点の接触角を測定し、平均化したものである。
図６は、実施例２のサンプル２−１及びサンプル２−２それぞれのフッ素含有ＤＬＣ膜のヌープ硬度と、比較例のサンプルのＤＬＣ膜のヌープ硬度を測定した結果を示す図である。図６に示す測定結果は、サンプル上の複数の点のヌープ硬度を測定し、平均化したものである。
図７は、実施例２のサンプル２−１の写真である。
図８及び図９は、実施例２のサンプル２−１及びサンプル２−２それぞれのフッ素含有ＤＬＣ膜にＸＰＳ分析を行った結果を示す図である。ＸＰＳ分析は、Ｘ線光電子分光分析法（ＸＰＳ：Ｘ−ｒａｙ Ｐｈｏｔｏｅｌｅｃｔｒｏｎ Ｓｐｅｃｔｒｏｓｃｏｐｙ）である。
表１は、実施例２のサンプル２−１及びサンプル２−２それぞれのフッ素含有ＤＬＣ膜中の炭素Ｃ、フッ素Ｆ及び窒素Ｎそれぞれの含有量をＸＰＳ分析結果から数値化したものである。
図１１（Ａ）は、実施例２のサンプル２−２のＨＡＡＤＦによる膜厚測定結果を示す図であり、図１１（Ｂ）は、実施例２のサンプル２−１のＨＡＡＤＦによる膜厚測定結果を示す図である。なお、ＨＡＡＤＦとは、ＳＴＥＭ暗視野法の一つであり、大きな角度に散乱された透過電子を、円環状の検出器で検出して画像化すると、原子番号の２乗に比例したコントラスト（Ｚコントラスト）を得ることができるものである。
図１２は、実施例２のサンプル２−１のＸＰＳ分析のＤｅｐｔｈ−Ｐｒｏｆｉｌｅを示す図である。図１３は、実施例２のサンプル２−２のＸＰＳ分析のＤｅｐｔｈ−Ｐｒｏｆｉｌｅを示す図である。図１２及び図１３において、横軸は深さ（ｎｍ）、縦軸は含有量（原子％）を示している。
≪実施例２のサンプル２−１≫
実施例２のサンプル２−１は、基材上に炭素と水素と珪素と窒素を含有する非晶質炭素膜を形成し、この非晶質珪素膜上にＤＬＣ膜を形成し、このＤＬＣ膜上にフッ素含有ＤＬＣ膜を成膜したものである。非晶質炭素膜、ＤＬＣ膜及びフッ素含有ＤＬＣ膜それぞれの成膜条件は以下のとおりである。
＜非晶質炭素膜の条件＞
基材：ＳＵＳ板
成膜装置：平行平板型のプラズマＣＶＤ装置
原料ガス：流量３０ｓｃｃｍのＨＭＤＳ−Ｎ
高周波電源の周波数：３８０ＫＨｚ
高周波出力：１０００Ｗ
圧力：１．５Ｐａ
温度：１００℃
膜厚：０．５μｍ
＜ＤＬＣ膜の条件＞
成膜装置：平行平板型のプラズマＣＶＤ装置
原料ガス：流量３０ｓｃｃｍのＣ７Ｈ８
高周波電源の周波数：３８０ＫＨｚ
高周波出力：１０００Ｗ
圧力：１．５Ｐａ
温度：１００℃
膜厚：０．２μｍ
＜フッ素含有ＤＬＣ膜の条件＞
成膜装置：平行平板型のプラズマＣＶＤ装置
原料ガス：流量１５ｓｃｃｍのＣ７Ｈ８と流量１５ｓｃｃｍのＣ９Ｆ２１Ｎの混合ガス
高周波電源の周波数：３８０ＫＨｚ
高周波出力：１０００Ｗ
圧力：１．５Ｐａ
温度：室温
膜厚：０．３μｍ
≪実施例２のサンプル２−２≫
実施例２のサンプル２−２は、基材上に炭素と水素と珪素と窒素を含有する非晶質炭素膜を形成し、この非晶質珪素膜上にＤＬＣ膜を形成し、このＤＬＣ膜上にフッ素含有ＤＬＣ膜を成膜したものである。非晶質炭素膜、ＤＬＣ膜及びフッ素含有ＤＬＣ膜それぞれの成膜条件は以下のとおりである。
＜非晶質炭素膜の条件＞
基材：サンプル２−１の非晶質炭素膜の条件と同一
成膜装置：サンプル２−１の非晶質炭素膜の条件と同一
原料ガス：サンプル２−１の非晶質炭素膜の条件と同一
高周波電源の周波数：サンプル２−１の非晶質炭素膜の条件と同一
高周波出力：サンプル２−１の非晶質炭素膜の条件と同一
圧力：サンプル２−１の非晶質炭素膜の条件と同一
温度：サンプル２−１の非晶質炭素膜の条件と同一
膜厚：サンプル２−１の非晶質炭素膜の条件と同一
＜ＤＬＣ膜の条件＞
成膜装置：サンプル２−１のＤＬＣ膜と同一
原料ガス：サンプル２−１のＤＬＣ膜と同一
高周波電源の周波数：サンプル２−１のＤＬＣ膜と同一
高周波出力：サンプル２−１のＤＬＣ膜と同一
圧力：サンプル２−１のＤＬＣ膜と同一
温度：サンプル２−１のＤＬＣ膜と同一
膜厚：サンプル２−１のＤＬＣ膜と同一
＜フッ素含有ＤＬＣ膜の条件＞
成膜装置：サンプル２−１のフッ素含有ＤＬＣ膜と同一
原料ガス：流量５ｓｃｃｍのＣ７Ｈ８と流量２５ｓｃｃｍのＣ９Ｆ２１Ｎの混合ガス
高周波電源の周波数：サンプル２−１のフッ素含有ＤＬＣ膜と同一
高周波出力：サンプル２−１のフッ素含有ＤＬＣ膜と同一
圧力：サンプル２−１のフッ素含有ＤＬＣ膜と同一
温度：サンプル２−１のフッ素含有ＤＬＣ膜と同一
膜厚：サンプル２−１のフッ素含有ＤＬＣ膜と同一
≪比較例のサンプルＤＬＣ≫
比較例のサンプルは、基材上にＤＬＣ膜を以下の成膜条件で成膜したものである。
＜ＤＬＣ膜の条件＞
成膜装置：サンプル２−１のＤＬＣ膜の条件と同一
原料ガス：サンプル２−１のＤＬＣ膜の条件と同一
高周波電源の周波数：サンプル２−１のＤＬＣ膜の条件と同一
高周波出力：サンプル２−１のＤＬＣ膜の条件と同一
圧力：サンプル２−１のＤＬＣ膜の条件と同一
温度：サンプル２−１のＤＬＣ膜の条件と同一
膜厚：０．２μｍ
図５及び図６に示すように、実施例２のサンプル２−１及び２−２では水の接触角が８０°以上でヌープ硬度が１０５０Ｈｋ以上である。非晶質炭素膜、ＤＬＣ膜、フッ素含有ＤＬＣ膜の積層構造としているため、水の接触角とヌープ硬度がともに高く維持することができた。これに対し、比較例のサンプル（ＤＬＣ）ではヌープ硬度は１０５０Ｈｋより高いが、水の接触角が８０°よりかなり低くなった。
図７、図８及び表１によれば、フッ素含有ＤＬＣ膜にフッ素が３原子％程度含有されていれば、水の接触角が８０°程度を維持でき、且つヌープ硬度を１２５０Ｈｋより高く維持できることが確認された（実施例２のサンプル２−１参照）。また、フッ素含有ＤＬＣ膜にフッ素を１７原子％程度まで含有させると、水の接触角を９０°より大きくできるが、ヌープ硬度は１０５０Ｈｋより高く維持できるものの１２５０Ｈｋより低くなることが確認された（実施例２のサンプル２−２参照）。このようにフッ素含有量を増加させると接触角は大きくできるが、ヌープ硬度が低下する理由は、フッ素含有ＤＬＣ膜中のｓｐ３が減少するからであると考えられる。
図１１（Ａ）によれば、実施例２のサンプル２−２の非晶質炭素膜の膜厚が３８４．６ｎｍ、ＤＬＣ膜の膜厚が２３７．８ｎｍ、フッ素含有ＤＬＣ膜の膜厚が８６．７ｎｍであった。また、図１１（Ｂ）によれば、実施例２のサンプル２−１の非晶質炭素膜の膜厚が４０２．８ｎｍ、ＤＬＣ膜の膜厚が２５１．７ｎｍ、フッ素含有ＤＬＣ膜の膜厚が１６７．８ｎｍであった。
図１２及び図１３それぞれによれば、非晶質炭素膜とＤＬＣ膜の境界にＳｉが拡散している層が確認され、フッ素含有ＤＬＣ膜とＤＬＣ膜の境界に相互の膜の元素が拡散されていることが確認された。これらのことから、非晶質炭素膜によって基板（ＳＵＳ板）とＤＬＣ膜の密着性を高めることができることが分かり、ＤＬＣ膜とフッ素含有ＤＬＣ膜との密着性を高めることができることが分かる。The sample of Example 2 has the same film structure as that of the second embodiment.
FIG. 5 is a diagram showing the results of measuring the water contact angle of the fluorine-containing DLC film of each of Samples 2-1 and 2-2 of Example 2 and the water contact angle of the DLC film of the sample of Comparative Example. is there. The measurement results shown in FIG. 5 are obtained by measuring and averaging the contact angles of a plurality of points on the sample.
FIG. 6 is a diagram showing the results of measuring the Knoop hardness of the fluorine-containing DLC film of each of Samples 2-1 and 2-2 of Example 2 and the Knoop hardness of the DLC film of the sample of Comparative Example. The measurement results shown in FIG. 6 are obtained by measuring and averaging the Knoop hardness at a plurality of points on the sample.
FIG. 7 is a photograph of Sample 2-1 of Example 2.
8 and 9 are diagrams showing the results of XPS analysis performed on the fluorine-containing DLC films of Samples 2-1 and 2-2 of Example 2. The XPS analysis is an X-ray photoelectron spectroscopy (XPS: X-ray Photoelectron Spectroscopy).
Table 1 shows the content of each of carbon C, fluorine F and nitrogen N in the fluorine-containing DLC film of each of Samples 2-1 and 2-2 in Example 2 quantified from the XPS analysis results.
FIG. 11A is a diagram showing the results of measuring the film thickness of Sample 2-2 of Example 2 using HAADF, and FIG. 11B is the results of measuring the film thickness of Sample 2-1 of Example 2 using HAADF. FIG. HAADF is one of the STEM dark-field methods. When transmitted electrons scattered at a large angle are detected and imaged by an annular detector, the contrast (ZZ) is proportional to the square of the atomic number. Contrast).
FIG. 12 is a diagram illustrating a depth-profile of the XPS analysis of the sample 2-1 in Example 2. FIG. 13 is a diagram illustrating a depth-profile of the XPS analysis of the sample 2-2 in Example 2. 12 and 13, the horizontal axis represents the depth (nm), and the vertical axis represents the content (atomic%).
{Sample 2-1 of Example 2}
The sample 2-1 of Example 2 is obtained by forming an amorphous carbon film containing carbon, hydrogen, silicon, and nitrogen on a base material, forming a DLC film on the amorphous silicon film, A fluorine-containing DLC film is formed thereon. The conditions for forming the amorphous carbon film, the DLC film, and the fluorine-containing DLC film are as follows.
<Conditions of amorphous carbon film>
Base material: SUS plate Film forming device: Parallel plate type plasma CVD device Source gas: HMDS-N with flow rate of 30 sccm
Frequency of high frequency power supply: 380KHz
High frequency output: 1000W
Pressure: 1.5Pa
Temperature: 100 ° C
Film thickness: 0.5 μm
<DLC film conditions>
Film forming apparatus: Parallel plate type plasma CVD apparatus Source gas: C 7 H 8 at a flow rate of 30 sccm
Frequency of high frequency power supply: 380KHz
High frequency output: 1000W
Pressure: 1.5Pa
Temperature: 100 ° C
Film thickness: 0.2 μm
<Conditions of fluorine-containing DLC film>
Film forming apparatus: Parallel plate type plasma CVD apparatus Source gas: Mixed gas of C 7 H 8 at a flow rate of 15 sccm and C 9 F 21 N at a flow rate of 15 sccm High-frequency power supply frequency: 380 KHz
High frequency output: 1000W
Pressure: 1.5Pa
Temperature: room temperature Film thickness: 0.3 μm
<< Sample 2-2 of Example 2 >>
The sample 2-2 of Example 2 forms an amorphous carbon film containing carbon, hydrogen, silicon, and nitrogen on a base material, forms a DLC film on the amorphous silicon film, A fluorine-containing DLC film is formed thereon. The conditions for forming the amorphous carbon film, the DLC film, and the fluorine-containing DLC film are as follows.
<Conditions of amorphous carbon film>
Base material: Same as the condition of the amorphous carbon film of Sample 2-1 Film forming apparatus: Same as the condition of the amorphous carbon film of Sample 2-1 Source gas: Conditions of the amorphous carbon film of Sample 2-1 Frequency of high-frequency power source: Same as the condition of amorphous carbon film of sample 2-1 High frequency output: Same as the condition of amorphous carbon film of sample 2-1 Pressure: amorphous carbon film of sample 2-1 Temperature: Same as the condition of the amorphous carbon film of Sample 2-1 Film thickness: Same as the condition of the amorphous carbon film of Sample 2-1 <DLC film condition>
Film forming apparatus: same as DLC film of sample 2-1 Source gas: same as DLC film of sample 2-1 Frequency of high frequency power supply: same as DLC film of sample 2-1 High frequency output: same as DLC film of sample 2-1 Same Pressure: Same as DLC film of Sample 2-1 Temperature: Same as DLC film of Sample 2-1 Thickness: Same as DLC film of Sample 2-1 <Condition of fluorine-containing DLC film>
Film forming apparatus: same as the fluorine-containing DLC film of sample 2-1 Source gas: mixed gas of C 7 H 8 at a flow rate of 5 sccm and C 9 F 21 N at a flow rate of 25 sccm High-frequency power supply frequency: fluorine-containing DLC of sample 2-1 High-frequency output: same as fluorine-containing DLC film of sample 2-1 Pressure: same as fluorine-containing DLC film of sample 2-1 Temperature: same as fluorine-containing DLC film of sample 2-1 Film thickness: sample 2-1 The same as the fluorine-containing DLC film of Example {Sample DLC of Comparative Example}
In the sample of the comparative example, a DLC film was formed on a substrate under the following film forming conditions.
<DLC film conditions>
Film forming apparatus: same as the condition of DLC film of sample 2-1 Source gas: same as the condition of DLC film of sample 2-1 Frequency of high frequency power supply: same as the condition of DLC film of sample 2-1 High frequency output: sample 2 Pressure: Same as the condition of the DLC film of Sample 2-1 Temperature: Same as the condition of the DLC film of Sample 2-1 Film thickness: 0.2 μm
As shown in FIGS. 5 and 6, samples 2-1 and 2-2 of Example 2 have a water contact angle of 80 ° or more and a Knoop hardness of 1050 Hk or more. Because of the laminated structure of the amorphous carbon film, the DLC film, and the fluorine-containing DLC film, both the contact angle of water and the Knoop hardness could be kept high. On the other hand, in the sample of the comparative example (DLC), the Knoop hardness was higher than 1050 Hk, but the contact angle of water was considerably lower than 80 °.
According to FIGS. 7, 8 and Table 1, when the fluorine-containing DLC film contains about 3 atomic% of fluorine, the contact angle of water can be maintained at about 80 °, and the Knoop hardness can be maintained higher than 1250 Hk. Was confirmed (see Sample 2-1 of Example 2). In addition, it was confirmed that when the fluorine-containing DLC film contains fluorine up to about 17 atomic%, the contact angle of water can be larger than 90 °, but the Knoop hardness can be maintained higher than 1050 Hk but lower than 1250 Hk (implementation). (See Sample 2-2 of Example 2). As described above, the contact angle can be increased by increasing the fluorine content, but the Knoop hardness decreases because the sp3 in the fluorine-containing DLC film is considered to decrease.
According to FIG. 11A, the thickness of the amorphous carbon film of Sample 2-2 of Example 2 was 384.6 nm, the thickness of the DLC film was 237.8 nm, and the thickness of the fluorine-containing DLC film was 86. 0.7 nm. According to FIG. 11B, the thickness of the amorphous carbon film of Sample 2-1 of Example 2 was 402.8 nm, the thickness of the DLC film was 251.7 nm, and the thickness of the fluorine-containing DLC film. Was 167.8 nm.
According to each of FIGS. 12 and 13, a layer in which Si is diffused at the boundary between the amorphous carbon film and the DLC film is confirmed, and elements of the mutual film are diffused at the boundary between the fluorine-containing DLC film and the DLC film. It was confirmed that. From these facts, it can be seen that the adhesion between the substrate (SUS plate) and the DLC film can be enhanced by the amorphous carbon film, and that the adhesion between the DLC film and the fluorine-containing DLC film can be enhanced.

１１…金型
１２…フッ素含有ＤＬＣ膜
１３…非晶質炭素膜
１４…ＤＬＣ膜
１５…フッ素含有ＤＬＣ膜
１０１…金型
１０２…金型の一部DESCRIPTION OF SYMBOLS 11 ... Die 12 ... Fluorine containing DLC film 13 ... Amorphous carbon film 14 ... DLC film 15 ... Fluorine containing DLC film 101 ... Die 102 ... Part of a die

Claims (8)

炭素と水素と珪素と窒素を含有する非晶質炭素膜と、
前記非晶質炭素膜上に形成されたＤＬＣ膜と、
前記ＤＬＣ膜上に形成されたフッ素を３原子％以上含有するフッ素含有ＤＬＣ膜を有する積層膜であり、
前記フッ素含有ＤＬＣ膜は、水の接触角が８０°以上で、且つヌープ硬度が１０５０Ｈｋ以上であることを特徴とする撥水性高硬度膜。 An amorphous carbon film containing carbon, hydrogen, silicon and nitrogen,
A DLC film formed on the amorphous carbon film,
A laminated film having a fluorine-containing DLC film containing 3 atomic% or more of fluorine formed on the DLC film,
The water-repellent high hardness film, wherein the fluorine-containing DLC film has a water contact angle of 80 ° or more and a Knoop hardness of 1050 Hk or more. 請求項１において、
前記非晶質炭素膜と前記ＤＬＣ膜と前記フッ素含有ＤＬＣ膜の膜厚比は下記式１を満たすことを特徴とする撥水性高硬度膜。
（非晶質炭素膜）：（ＤＬＣ膜）：（フッ素含有ＤＬＣ膜）＝（２．５〜７．５）：（１．５〜４．５）：（１〜３） ・・・式２ In claim 1,
A film thickness ratio of the amorphous carbon film, the DLC film, and the fluorine-containing DLC film satisfies the following equation 1.
(Amorphous carbon film): (DLC film): (fluorine-containing DLC film) = (2.5 to 7.5): (1.5 to 4.5): (1 to 3) Formula 2 請求項１または２において、
前記非晶質炭素膜は金型の表面に形成されていることを特徴とする撥水性高硬度膜。 In claim 1 or 2,
The amorphous carbon film is formed on a surface of a mold, and is a water-repellent high hardness film. 請求項３において、
前記金型はダイス鋼または高速度鋼により形成されていることを特徴とする撥水性高硬度膜。 In claim 3,
The water repellent high hardness film, wherein the mold is formed of die steel or high speed steel. 積層膜が表面に形成された金型であり、
前記積層膜は、炭素と水素と珪素と窒素を含有する非晶質炭素膜と、前記非晶質炭素膜上に形成されたＤＬＣ膜と、前記ＤＬＣ膜上に形成されたフッ素を３原子％以上含有するフッ素含有ＤＬＣ膜を有し、
前記フッ素含有ＤＬＣ膜は、水の接触角が８０°以上で、且つヌープ硬度が前記金型のヌープ硬度以上であることを特徴とする金型。 A mold with a laminated film formed on the surface,
The laminated film includes an amorphous carbon film containing carbon, hydrogen, silicon, and nitrogen, a DLC film formed on the amorphous carbon film, and 3 atomic% of fluorine formed on the DLC film. Having a fluorine-containing DLC film containing the above,
A mold wherein the fluorine-containing DLC film has a contact angle of water of 80 ° or more and a Knoop hardness of at least the Knoop hardness of the mold. 炭素と水素と珪素と窒素を含有する原料ガスを用いたプラズマＣＶＤ法により非晶質炭素膜を形成し、
前記非晶質炭素膜上に、炭化水素系ガスを有する原料ガスと、周波数が１０〜５００ｋＨｚの高周波電力を用いたプラズマＣＶＤ法によりＤＬＣ膜を形成し、
前記ＤＬＣ膜上に、炭化水素系ガス及びフルオロカーボン系ガスを有する原料ガスと、周波数が１０〜５００ｋＨｚの高周波電力を用いたプラズマＣＶＤ法によりフッ素を３原子％以上含有するフッ素含有ＤＬＣ膜を形成することを備え、
前記フッ素含有ＤＬＣ膜は、水の接触角が８０°以上で、且つヌープ硬度が１０５０Ｈｋ以上であることを特徴とする撥水性高硬度膜の製造方法。 Forming an amorphous carbon film by a plasma CVD method using a source gas containing carbon, hydrogen, silicon and nitrogen,
Forming a DLC film on the amorphous carbon film by a plasma CVD method using a source gas having a hydrocarbon-based gas and a high-frequency power having a frequency of 10 to 500 kHz;
Said on DLC film, a raw material gas having a hydrocarbon-based gas and full Oro carbon-based gas, a fluorine-containing DLC film frequency contains fluorine 3 atomic% or more by the plasma CVD method using a high frequency power of 10 ~ 500 kHz Comprising forming
The method for producing a water-repellent high-hardness film, wherein the fluorine-containing DLC film has a water contact angle of 80 ° or more and a Knoop hardness of 1050 Hk or more. 請求項６において、
前記フルオロカーボン系ガスは、Ｃ９Ｆ２１Ｎガスであることを特徴とする撥水性高硬度膜の製造方法。 In claim 6,
The method for producing a water-repellent high hardness film, wherein the fluorocarbon-based gas is a C 9 F 21 N gas. 請求項６において、
前記非晶質炭素膜は金型の表面に形成されることを特徴とする撥水性高硬度膜の製造方法。 In claim 6,
The method for producing a water-repellent high hardness film, wherein the amorphous carbon film is formed on a surface of a mold.
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