TWI699447B - Water-repellent high-hardness film, casting mold and manufacturing method of water-repellent high-hardness film - Google Patents

Water-repellent high-hardness film, casting mold and manufacturing method of water-repellent high-hardness film Download PDF

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TWI699447B
TWI699447B TW105102705A TW105102705A TWI699447B TW I699447 B TWI699447 B TW I699447B TW 105102705 A TW105102705 A TW 105102705A TW 105102705 A TW105102705 A TW 105102705A TW I699447 B TWI699447 B TW I699447B
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film
fluorine
dlc film
water
aforementioned
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TW201634728A (en
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本多祐二
奧平浩平
阿部浩二
遠藤有希子
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日商前進材料科技股份有限公司
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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

Abstract

本發明提供水之接觸角為80°以上且具有高硬度之撥水性高硬度膜。本發明之一樣態係含有3原子%以上之氟的含氟DLC膜，前述含氟DLC膜係水之接觸角為80°以上且努普硬度(Knoop hardness)為1050Hk以上之撥水性高硬度膜。 The present invention provides a water-repellent, high-hardness film with a water contact angle of 80° or more and high hardness. The same aspect of the present invention is a fluorine-containing DLC film containing more than 3 atomic% of fluorine. The aforementioned fluorine-containing DLC film is a water-repellent high-hardness film with a water contact angle of 80° or more and a Knoop hardness of 1050Hk or more .

Description

撥水性高硬度膜、鑄模及撥水性高硬度膜之製造方法 Water-repellent high-hardness film, casting mold and manufacturing method of water-repellent high-hardness film

本發明係有關具有含氟DLC(Diamond Like Carbon，似金剛石碳)膜之撥水性高硬度膜、鑄模及撥水性高硬度膜之製造方法。 The present invention relates to a method for manufacturing a water-repellent high-hardness film with a fluorine-containing DLC (Diamond Like Carbon) film, a casting mold, and a water-repellent high-hardness film.

以往之射出成型機係對加熱軟化之樹脂施加射出壓擠入鑄模中，填充於該鑄模而成型者。使用如此射出成型機之鑄模如圖10所示，會有於該鑄模101之一部分102產生樹脂烙印之情況。於產生此種烙印之鑄模中，必須掃除烙印之樹脂，其掃除除了需要耗費時間及勞力以外，亦會使鑄模之壽命變短。 In the conventional injection molding machine, the heated and softened resin is injected and pressed into the mold, and the mold is filled to form. The mold using such an injection molding machine is shown in FIG. 10, and resin imprinting may occur on a part 102 of the mold 101. In the mold that produces this kind of branding, the resin of the brand must be removed. In addition to time-consuming and labor-intensive removal, the service life of the mold is shortened.

因此作為抑制樹脂烙印之方法考慮有於鑄模表面成膜高硬度DLC膜。 Therefore, as a method to suppress resin burn-in, a high-hardness DLC film can be formed on the surface of the mold.

然而，以往之DLC膜之水接觸角為60°~72°左右，故作為成型樹脂若使用接著性高的樹脂(例如丙烯酸系樹脂、聚乙酸樹脂、酚樹脂等)時，無法充分抑制鑄模之一部分102中之樹脂烙印。且於以往之DLC膜中，並無為了抑制樹脂之烙印且不易於對鑄模附加傷痕，水之接觸角 大且高硬度之DLC膜。 However, the water contact angle of the conventional DLC film is about 60°~72°. Therefore, if a resin with high adhesiveness (such as acrylic resin, polyacetate resin, phenol resin, etc.) is used as the molding resin, the mold cannot be sufficiently suppressed. Resin imprinting in part 102. And in the previous DLC film, there is no purpose to suppress resin imprinting and it is not easy to add scars to the mold, the contact angle of water Large and high hardness DLC film.

本發明之一樣態之課題在於提供水之接觸角為80°以上且具有高硬度之撥水性高硬度膜或於表面成膜該撥水性高硬度膜之鑄模或撥水性高硬度膜之製造方法。 The subject of the same aspect of the present invention is to provide a water-repellent high-hardness film with a water contact angle of 80° or more and high hardness, or a mold for forming the water-repellent high-hardness film on the surface, or a method for manufacturing a water-repellent high-hardness film.

以下針對本發明之各種樣態加以說明。 The various aspects of the present invention are described below.

[1]一種撥水性高硬度膜，其特徵係含有3原子%以上之氟的含氟DLC膜，且前述含氟DLC膜係水之接觸角為80°以上且努普硬度(Knoop hardness)為1050Hk以上。 [1] A water-repellent high-hardness film characterized by a fluorine-containing DLC film containing 3 atomic% or more of fluorine, and the contact angle of the aforementioned fluorine-containing DLC film water is 80° or more, and the Knoop hardness is Above 1050Hk.

上述之含氟DLC膜之氟上限含量較好為17原子%以下，更好為10原子%以下。 The upper limit of fluorine content of the above-mentioned fluorine-containing DLC film is preferably 17 atomic% or less, more preferably 10 atomic% or less.

[2]一種撥水性高硬度膜，其特徵係具有下述膜之積層膜，含有碳、氫、矽與氮之非晶質碳膜、形成於前述非晶質碳膜上之DLC膜、形成於前述DLC膜上之含有3原子%以上之氟的含氟DLC膜，且前述含氟DLC膜係水接觸角為80°以上(較好90°以上)且努普硬度為1050Hk以上。 [2] A water-repellent, high-hardness film characterized by a laminated film having the following films, an amorphous carbon film containing carbon, hydrogen, silicon and nitrogen, a DLC film formed on the aforementioned amorphous carbon film, and A fluorine-containing DLC film containing 3 atomic% or more of fluorine on the DLC film, and 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.

上述之含氟DLC膜之氟上限含量較好為17原子%以下，更好為10原子%以下。 The upper limit of fluorine content of the above-mentioned fluorine-containing DLC film is preferably 17 atomic% or less, more preferably 10 atomic% or less.

[3]如上述[2]之撥水性高硬度膜，其中前述非晶質碳膜與前述DLC膜與前述含氟DLC膜之膜厚比滿足下述式1：(非晶質碳膜)：(DLC膜)：(含氟DLC膜)=(2.5~7.5)：(1.5~4.5)：(1~3)---式1。 [3] The water-repellent, high-hardness film according to [2] above, wherein the film thickness ratio of the amorphous carbon film to the DLC film to the fluorine-containing DLC film satisfies the following formula 1: (amorphous carbon film): (DLC film): (Fluorine-containing DLC film)=(2.5~7.5): (1.5~4.5): (1~3)---Formula 1.

[4]如上述[1]至[3]中任一項之撥水性高硬度膜，其中前述含氟DLC膜係藉由使用具有烴系氣體及氟碳系氣體之原料氣體及頻率為10~500kHz之高頻電力而為之電漿CVD法所成膜之膜。 [4] The water-repellent, high-hardness film according to any one of [1] to [3] above, wherein the aforementioned fluorine-containing DLC film is formed by using a raw material gas having a hydrocarbon-based gas and a fluorocarbon-based gas and the frequency is 10~ The film is formed by plasma CVD method with high frequency power of 500kHz.

[5]如上述[2]或[3]之撥水性高硬度膜，其中前述DLC膜係藉由使用具有烴系氣體之原料氣體及頻率為10~500kHz之高頻電力而為之電漿CVD法所成膜之膜。 [5] The water-repellent, high-hardness film as described in [2] or [3] above, wherein the aforementioned DLC film is plasma CVD by using a source gas with a hydrocarbon-based gas and high-frequency power with a frequency of 10 to 500 kHz The film formed by the law.

[6]如上述[1]之撥水性高硬度膜，其中前述含氟DLC膜係形成於鑄模表面。 [6] The water-repellent, high-hardness film of [1] above, wherein the fluorine-containing DLC film is formed on the surface of the mold.

[7]如上述[2]、[3]及[5]中任一項之撥水性高硬度膜，其中前述非晶質碳膜係形成於鑄模表面。 [7] The water-repellent high-hardness film according to any one of [2], [3], and [5] above, wherein the aforementioned amorphous carbon film is formed on the surface of the mold.

[8]如上述[6]或[7]之撥水性高硬度膜，其中前述鑄模係藉由模具鋼(die steel)或高速鋼所形成。 [8] The water-repellent high-hardness film of [6] or [7] above, wherein the mold is formed by die steel or high-speed steel.

[9]一種鑄模，其係於表面形成含有3原子%以上之氟的含氟DLC膜之鑄模，且前述含氟DLC膜係水之接觸角為80°以上且努普硬度為前述鑄模之努普硬度以上。 [9] A casting mold in which a fluorine-containing DLC film containing 3 atomic% or more of fluorine is formed on the surface, and the contact angle of the fluorine-containing DLC film with water is 80° or more, and the Knoop hardness is equivalent to that of the mold Above normal hardness.

上述之含氟DLC膜之氟上限含量較好為17原子%以下，更好為10原子%以下。 The upper limit of fluorine content of the above-mentioned fluorine-containing DLC film is preferably 17 atomic% or less, more preferably 10 atomic% or less.

[10]一種鑄模，其係於表面形成積層膜之鑄模，且前述積層膜具有含有碳、氫、矽與氮之非晶質碳膜、形成於前述非晶質碳膜上之DLC膜、與形成於前述DLC膜上之含有3原子%以上之氟的含氟DLC膜，前述含氟DLC膜係水之接觸角為80°以上(較好90°以上)且努普硬度為前述鑄模之努普硬度以上。 [10] A casting mold, which is a casting mold for forming a laminated film on the surface, and the laminated film has an amorphous carbon film containing carbon, hydrogen, silicon and nitrogen, a DLC film formed on the amorphous carbon film, and The fluorine-containing DLC film containing 3 atomic% or more of fluorine formed on the aforementioned DLC film, the contact angle of the aforementioned fluorine-containing DLC film system water is 80° or more (preferably 90° or more), and the Knoop hardness is that of the aforementioned mold Above normal hardness.

上述之含氟DLC膜之氟上限含量較好為17原子%以下，更好為10原子%以下。 The upper limit of fluorine content of the above-mentioned fluorine-containing DLC film is preferably 17 atomic% or less, more preferably 10 atomic% or less.

[11]一種撥水性高硬度膜之製造方法，其特徵係藉由使用具有烴系氣體及氟碳系氣體之原料氣體及頻率為10~500kHz之高頻電力而為之電漿CVD法形成含氟之DLC膜。 [11] A method for producing a water-repellent, high-hardness film, which is characterized by using a plasma CVD method containing hydrocarbon-based gas and fluorocarbon-based gas and high-frequency power with a frequency of 10 to 500 kHz. Fluorine DLC film.

[12]一種撥水性高硬度膜之製造方法，其特徵係藉由使用含有碳、氫、矽及氮之原料氣體而為之電漿CVD法形成非晶質碳膜，於前述非晶質碳膜上，藉由使用具有烴系氣體之原料氣體及頻率為10~500kHz之高頻電力而為之電漿CVD法形成DLC膜，於前述DLC膜上，藉由使用具有烴系氣體及氟碳系氣體之原料氣體及頻率為10~500kHz之高頻電力而為之電漿CVD法形成含氟之DLC膜。 [12] A method for producing a water-repellent, high-hardness film characterized by forming an amorphous carbon film by plasma CVD using raw material gases containing carbon, hydrogen, silicon, and nitrogen. On the film, the DLC film is formed by the plasma CVD method using a source gas with a hydrocarbon-based gas and high-frequency power with a frequency of 10 to 500 kHz. On the aforementioned DLC film, a DLC film is formed by using a hydrocarbon-based gas and a fluorocarbon The fluorine-containing DLC film is formed by the plasma CVD method using the raw material gas of the gas and the high frequency power of 10~500kHz.

[13]如上述[11]或[12]之撥水性高硬度膜之製造方 法，其中前述氟碳系氣體係C9F21N氣體。 [13] The method for producing a water-repellent, high-hardness film as described in [11] or [12], wherein the fluorocarbon-based gas system C 9 F 21 N gas.

[14]如上述[11]之撥水性高硬度膜之製造方法，其中前述含氟DLC膜係形成於鑄模表面。 [14] The method for producing a water-repellent high-hardness film according to [11] above, wherein the fluorine-containing DLC film is formed on the surface of the mold.

[15]如上述[12]之撥水性高硬度膜之製造方法，其中前述非晶質碳膜係形成於鑄模表面。 [15] The method for producing a water-repellent, high-hardness film according to [12], wherein the amorphous carbon film is formed on the surface of the mold.

依據本發明之一樣態，可提供水之接觸角為80°以上且具有高硬度之撥水性高硬度膜或於表面成膜該撥水性高硬度膜之鑄模或撥水性高硬度膜之製造方法。 According to one aspect of the present invention, it is possible to provide a water-repellent high-hardness film with a water contact angle of 80° or more and high hardness, or a mold for forming the water-repellent high-hardness film on the surface, or a method for manufacturing a water-repellent high-hardness film.

11‧‧‧鑄模 11‧‧‧Mould

12‧‧‧含氟DLC膜 12‧‧‧Fluorinated DLC film

13‧‧‧非晶質碳膜 13‧‧‧Amorphous Carbon Film

14‧‧‧DLC膜 14‧‧‧DLC film

15‧‧‧含氟DLC膜 15‧‧‧Fluorinated DLC film

101‧‧‧鑄模 101‧‧‧Mould

102‧‧‧鑄模之一部分 102‧‧‧Part of the mold

圖1係用以說明本發明之一樣態之撥水性高硬度膜之製造方法之剖面圖。 Fig. 1 is a cross-sectional view for explaining the manufacturing method of the water-repellent high-hardness film in the same state of the present invention.

圖2係用以說明本發明之一樣態之撥水性高硬度膜之製造方法之剖面圖。 Fig. 2 is a cross-sectional view for explaining the manufacturing method of the water-repellent high-hardness film in the same state of the present invention.

圖3係顯示測定實施例1之樣品1-1之含氟DLC膜之水接觸角與比較例之樣品1-2之含氟DLC膜之水接觸角及比較例之樣品之DLC膜之水接觸角的結果之圖。 Figure 3 shows the measurement of the water contact angle of the fluorine-containing DLC film of the sample 1-1 of Example 1 and the water contact angle of the fluorine-containing DLC film of the sample 1-2 of the comparative example and the water contact of the DLC film of the sample of the comparative example Diagram of the result of the angle.

圖4係顯示測定實施例1之樣品1-1之含氟DLC膜之努普硬度與比較例之樣品1-2之含氟DLC膜之努普硬度及比較例之樣品之DLC膜之努普硬度的結果之圖。 Figure 4 shows the measurement of the Knoop hardness of the fluorine-containing DLC film of the sample 1-1 of Example 1 and the Knoop hardness of the fluorine-containing DLC film of the sample 1-2 of the comparative example and the Knoop hardness of the DLC film of the sample of the comparative example Graph of the result of hardness.

圖5係顯示測定實施例2之樣品2-1及樣品2-2各者之含氟DLC膜之水接觸角與比較例之樣品之DLC膜之水 接觸角的結果之圖。 Figure 5 shows the measurement of the water contact angle of the fluorine-containing DLC film of each of the sample 2-1 and sample 2-2 of Example 2 and the water of the DLC film of the sample of the comparative example A graph of the result of the contact angle.

圖6係顯示測定實施例2之樣品2-1及樣品2-2各者之含氟DLC膜之努普硬度與比較例之樣品之DLC膜之努普硬度的結果之圖。 6 is a graph showing the results of measuring the Knoop hardness of the fluorine-containing DLC film of each of the sample 2-1 and the sample 2-2 of Example 2 and the Knoop hardness of the DLC film of the sample of the comparative example.

圖7係實施例2之樣品2-1之照片。 Figure 7 is a photograph of sample 2-1 of Example 2.

圖8係顯示對實施例2之樣品2-1及樣品2-2各者之含氟DLC膜進行XPS分析的結果之圖。 8 is a diagram showing the results of XPS analysis of the fluorine-containing DLC film of each of the sample 2-1 and the sample 2-2 of Example 2.

圖9係顯示對實施例2之樣品2-1及樣品2-2各者之含氟DLC膜進行XPS分析的結果之圖。 9 is a graph showing the results of XPS analysis of the fluorine-containing DLC film of each of the sample 2-1 and the sample 2-2 of Example 2.

圖10係示意性顯示以往之射出成型機用之鑄模之剖面圖。 Fig. 10 is a cross-sectional view schematically showing a mold used in a conventional injection molding machine.

圖11(A)係實施例2之樣品2-2之利用HAADF之膜厚測定結果之圖。 Fig. 11(A) is a graph showing the measurement result of the film thickness using HAADF of the sample 2-2 of Example 2.

圖11(B)係實施例2之樣品2-1之利用HAADF之膜厚測定結果之圖。 Fig. 11(B) is a graph showing the measurement result of the film thickness of the sample 2-1 of Example 2 using HAADF.

圖12係顯示對實施例2之樣品2-1之XPS分析之深度-分佈(Depth-Profile)之圖。 FIG. 12 is a graph showing the depth-profile (Depth-Profile) of the XPS analysis of the sample 2-1 of Example 2.

圖13係顯示對實施例2之樣品2-2之XPS分析之深度-分佈之圖。 FIG. 13 is a graph showing the depth-distribution of the XPS analysis of the sample 2-2 of Example 2. FIG.

以下針對本發明之實施形態使用圖式詳細說明。惟，本發明不限於以下之說明，在不脫離本發明之主旨及其範圍之其形態及細節可進行各種變更，此為本技藝者可容易 理解。因此，本發明不應解釋為限定於以下所示之實施形態之記載內容者。 The following is a detailed description of the embodiments of the present invention using drawings. However, the present invention is not limited to the following description, and various changes can be made to the form and details without departing from the spirit and scope of the present invention. This is easy for those skilled in the art. understanding. Therefore, the present invention should not be interpreted as being limited to the description of the embodiments shown below.

[第1實施形態] [First Embodiment]

圖1係用以說明本發明之一樣態之撥水性高硬度膜之製造方法之剖面圖。 Fig. 1 is a cross-sectional view for explaining the manufacturing method of the water-repellent high-hardness film in the same state of the present invention.

首先，準備藉由模具鋼或高速鋼所形成之鑄模11。又，本實施形態中，使用鑄模11，但並非限定於鑄模者，亦可使用鑄模以外之各種基材。 First, prepare a mold 11 formed of mold steel or high-speed steel. In addition, in this embodiment, the mold 11 is used, but it is not limited to the mold, and various base materials other than the mold may be used.

其次，於鑄模11之表面上，使用使烴系氣體與氟碳系氣體混合之混合氣體作為原料氣體，於1.5~5Pa之壓力下，對鑄模11或與鑄模11對向之電極(未圖示)供給頻率為10~500kHz(較好100~400kHz)之高頻電力之條件之電漿CVD法形成含氟DLC膜12。此時之溫度條件較好為室溫~100℃左右。該含氟DLC膜12含有3原子%以上之氟，水接觸角為80°以上且努普硬度為1050Hk以上。又，含氟DLC膜12之氟上限含量較好為17原子%以下，更好為10原子%以下。 Next, on the surface of the mold 11, a mixed gas of a hydrocarbon-based gas and a fluorocarbon-based gas is used as the raw material gas, and the mold 11 or the electrode facing the mold 11 (not shown) is applied under a pressure of 1.5 to 5 Pa. ) The fluorine-containing DLC film 12 is formed by the plasma CVD method under the conditions of supplying high-frequency power at a frequency of 10 to 500 kHz (preferably 100 to 400 kHz). 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 a Knoop hardness of 1050 Hk or more. In addition, the upper limit of the fluorine content of the fluorine-containing DLC film 12 is preferably 17 atomic% or less, more preferably 10 atomic% or less.

又，含氟DLC膜12中亦可含有5原子%以下之氮。且含氟DLC膜12之成膜所用之電漿CVD裝置可使用例如平行平板型之電漿CVD裝置。 In addition, the fluorine-containing DLC film 12 may contain 5 atomic% or less of nitrogen. In addition, the plasma CVD device used for forming the fluorine-containing DLC film 12 can be, for example, a parallel plate type plasma CVD device.

又，本說明書中所謂「氟碳系氣體」意指具有碳與氟之鍵的有機化合物系之氣體。作為氟碳系氣體，可使用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、三-七氟丙基胺、C3F6O、C4F6O3、C4F8O、C5F6O3、C6F4O2、C6F10O3、C8F4O3、C8F8O、C8F8O2、C8F14O3、C13F10O、C13F10O3、C2F6O(C3F6O)n(CF2O)m及C7F5NO之至少一種。 In addition, the term "fluorocarbon-based gas" in this specification means an organic compound-based gas having a bond between carbon and fluorine. As the fluorocarbon 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 can be used 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 , tris-heptafluoropropylamine, 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 14 O 3 , C 13 F 10 O, C 13 F 10 O 3 , C 2 F 6 O( At least one of C 3 F 6 O)n(CF 2 O)m and C 7 F 5 NO.

依據本實施形態，由於藉由上述成膜條件之電漿CVD法形成含氟DLC膜12，故含氟DLC膜12可成為水接觸角為80°以上且努普硬度為1050Hk以上之撥水性高硬度膜。詳細而言，由於含氟DLC膜12中含有3原子%以上之氟，故可使含氟DLC膜12之水接觸角成為80°以上。氟含量之下限值設為3原子%之理由係因為水接觸角設為80°以上時，氟含量必須至少為3原子%。且，氟含量之較佳上限值設為17原子%之理由係氟若含有多於17原子%，則無法保持1050Hk之努普硬度。 According to this embodiment, since the fluorine-containing DLC film 12 is formed by the plasma CVD method under the above-mentioned film forming conditions, the fluorine-containing DLC film 12 can have a water contact angle of 80° or more and a Knoop hardness of 1050Hk or more with high water repellency. Hardness film. Specifically, since the fluorine-containing DLC film 12 contains 3 atomic% or more of fluorine, the water contact angle of the fluorine-containing DLC film 12 can be 80° or more. The reason why the lower limit of the fluorine content is 3 at% is because when the water contact angle is set to 80° or more, the fluorine content must be at least 3 at%. The reason why the preferable upper limit of the fluorine content is 17 at% is that if fluorine contains more than 17 at%, the Knoop hardness of 1050Hk cannot be maintained.

於樹脂成型用之鑄模中使用如此含氟DLC膜12時，藉由將鑄模11表面設為水接觸角為80°以上之撥水性，可提高鑄模11與樹脂之脫模性，其結果，可抑制於鑄模11之一部分產生樹脂烙印。因此，可抑制掃除烙印樹脂之頻度，可減低該掃除之時間及勞力，可延長鑄模之壽命。且，由於含氟DLC膜12為高硬度，故可抑制於鑄模或含氟DLC膜12上賦予傷痕。 When such a fluorine-containing DLC film 12 is used in a mold for resin molding, by setting the surface of the mold 11 to a water repellency with a water contact angle of 80° or more, the mold release between the mold 11 and the resin can be improved. As a result, The resin imprinting is suppressed in a part of the mold 11. Therefore, the frequency of cleaning the imprinted resin can be suppressed, the time and labor of the cleaning can be reduced, and the life of the mold can be prolonged. In addition, since the fluorine-containing DLC film 12 has high hardness, it is possible to suppress the formation of scratches on the mold or the fluorine-containing DLC film 12.

且，含氟DLC膜12獲得高硬度之理由舉例為以稱為金剛石構造之含較多sp3之DLC膜作為主要構造。藉由使構成DLC之碳之一部分以氟取代，可獲得兼具高硬度與撥水性之含氟DLC膜。相對地，僅為碳膜時稱為非晶型構造之sp2較多，無法獲得構造上之強度。因此，即使單純於碳膜中含有氟亦無法獲得兼具高硬度且高撥水性之膜。 In addition, the reason why the fluorine-containing DLC film 12 obtains high hardness is, for example, a DLC film with a large amount of sp3 called a diamond structure as the main structure. By substituting part of the carbon constituting the DLC with fluorine, a fluorine-containing DLC film with both high hardness and water repellency can be obtained. In contrast, there are many sp2 called amorphous structures when only carbon films are used, and structural strength cannot be obtained. Therefore, even if fluorine is simply contained in the carbon film, a film having both high hardness and high water repellency cannot be obtained.

又，本實施形態中，含氟DLC膜12之努普硬度設為1050Hk以上，但並非限定於此者，只要含氟DLC膜12為成膜之基底(鑄模11或基材)之努普硬度以上即可。1050Hk之努普硬度為高速鋼之硬度。 In addition, in this embodiment, the Knoop hardness of the fluorine-containing DLC film 12 is set to 1050Hk or more, but it is not limited to this, as long as the fluorine-containing DLC film 12 is the base (mold 11 or substrate) on which the film is formed. That's all. The Knoop hardness of 1050Hk is the hardness of high-speed steel.

[第2實施形態] [Second Embodiment]

圖2係用以說明本發明之一樣態之撥水性高硬度膜之製造方法之剖面圖。 Fig. 2 is a cross-sectional view for explaining the manufacturing method of the water-repellent high-hardness film in the same state of the present invention.

首先，準備與第1實施形態同樣之鑄模11。 First, the same mold 11 as in the first embodiment is prepared.

其次，於鑄模11之表面上，使用含有碳、氫、矽及氮之原料氣體(例如具有HMDS-N之原料氣體)，於1.5~5Pa之壓力下，對鑄模11或與鑄模11對向之電極(未圖示)供給頻率為10~500kHz(較好100~400kHz)之高頻電力之條件之電漿CVD法形成非晶質碳膜13。此時之溫度條件較好為室溫~100℃左右。該非晶質碳膜13為例如CaHbSicNd膜。但，a、b、c、d為自然數。且HMDS-N為六甲基二矽氮烷(C6H19NSi2)。 Secondly, on the surface of the mold 11, use a raw material gas containing carbon, hydrogen, silicon, and nitrogen (for example, a raw material gas with HMDS-N), under a pressure of 1.5 to 5 Pa, against the mold 11 or opposite to the mold 11 The electrode (not shown) is supplied with high frequency power at a frequency of 10 to 500 kHz (preferably 100 to 400 kHz) by plasma CVD to form the amorphous carbon film 13. The temperature condition at this time is preferably from room temperature to about 100°C. The amorphous carbon film 13 is, for example, a Ca H b Si c N d film. However, a, b, c, and d are natural numbers. And HMDS-N is hexamethyldisilazane (C 6 H 19 NSi 2 ).

又，本實施形態中，成膜非晶質碳膜13時之高頻電力之頻率設為10~500kHz，但並非限定於此，作為高頻電力之頻率亦可使用13.56MHz。 In addition, in this embodiment, the frequency of the high-frequency power when forming the amorphous carbon film 13 is set to 10 to 500 kHz, but it is not limited to this, and 13.56 MHz may be used as the frequency of the high-frequency power.

其次，於非晶質碳膜13上，使用具有烴系氣體之原料氣體(例如具有C7H8之原料氣體)，於1.5~5Pa之壓力下，對鑄模11或與鑄模11對向之電極(未圖示)供給頻率為10~500kHz(較好100~400kHz)之高頻電力之條件之電漿CVD法形成DLC膜14。此時之溫度條件較好為室溫~100℃左右。 Secondly, on the amorphous carbon film 13, a raw material gas with a hydrocarbon gas (for example, a raw material gas with C 7 H 8 ) is used for the mold 11 or the electrode facing the mold 11 under a pressure of 1.5 to 5 Pa (Not shown) The DLC film 14 is formed by the plasma CVD method under the conditions of supplying high frequency power at a frequency of 10 to 500 kHz (preferably 100 to 400 kHz). The temperature condition at this time is preferably from room temperature to about 100°C.

其次，於DLC膜14上，藉由與第1實施形態同樣之成膜條件之電漿CVD法形成含氟DLC膜15。該含氟DLC膜15含有3原子%以上之氟，水之接觸角為80°以上(較好90°以上)且努普硬度為1050Hk以上。又，含氟DLC膜15之氟上限含量較好為17原子%以下，更好10原子%以下。 Next, on the DLC film 14, the fluorine-containing DLC film 15 is formed by the 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, the contact angle of water is 80° or more (preferably 90° or more), and the Knoop hardness is 1050 Hk or more. In addition, the upper limit of the fluorine content of the fluorine-containing DLC film 15 is preferably 17 atomic% or less, more preferably 10 atomic% or less.

本實施形態亦可獲得與第1實施形態同樣之效果。 This embodiment can also obtain the same effect as the first embodiment.

又，依據本實施形態，由於於鑄模11與含氟DLC膜15之間形成非晶質碳膜13與DLC膜14，故亦可維持比第1實施形態之含氟DLC膜12更高之硬度，且可更提高水之接觸角。以下詳細說明。 Furthermore, according to this 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, it is possible to maintain a higher hardness than the fluorine-containing DLC film 12 of the first embodiment. , And can further increase the contact angle of water. The following details.

藉由形成非晶質碳膜13，構成非晶質碳膜13之元素之一部分擴散至DLC膜14，形成擴散層，因而可提高鑄模11與DLC膜14之密著性。同樣地於DLC膜14及含氟DLC膜15之間亦由構成DLC膜15之元素形成擴散 層，而提高密著性。又，藉由形成DLC膜14，可更提高含氟DLC膜15之硬度。且非晶質碳膜13中含有Si時，會有該Si藉由含氟DLC膜15之氟而蝕刻之情況，但因該氟所致之Si之蝕刻可藉由DLC膜14而抑制。 By forming the amorphous carbon film 13, part of the elements constituting the amorphous carbon film 13 diffuses into the DLC film 14 to form a diffusion layer, so that the adhesion between the mold 11 and the DLC film 14 can be improved. Similarly, between the DLC film 14 and the fluorine-containing DLC film 15 are diffused by the elements constituting the DLC film 15 Layer to improve adhesion. In addition, by forming the DLC film 14, the hardness of the fluorine-containing DLC film 15 can be further improved. When Si is contained in the amorphous carbon film 13, the Si may be etched by the fluorine of the fluorine-containing DLC film 15, but the etching of Si due to the fluorine can be suppressed by the DLC film 14.

又，非晶質碳膜13與DLC膜14與含氟DLC膜15之膜厚比，係以下述式1表示，較好滿足以式1作為中心值±50%之範圍內之下述式2，更好為±30%之範圍內，又更好為±20%之範圍內。 In addition, the film thickness ratio of the amorphous carbon film 13 to the DLC film 14 to the fluorine-containing DLC film 15 is expressed by the following formula 1, which preferably satisfies the following formula 2 in the range of ±50% with the formula 1 as the center value , More preferably within the range of ±30%, still more preferably within the range of ±20%.

(非晶質碳膜)：(DLC膜)：(含氟DLC膜)=5：3：2---式1。 (Amorphous Carbon Film): (DLC Film): (Fluorine-containing DLC Film)=5:3:2---Formula 1.

(非晶質碳膜)：(DLC膜)：(含氟DLC膜)=(2.5~7.5)：(1.5~4.5)：(1~3)---式2。 (Amorphous Carbon Film): (DLC Film): (Fluorine-containing DLC Film)=(2.5~7.5): (1.5~4.5): (1~3)---Formula 2.

樹脂成型用之鑄模中使用含氟DLC膜15時，含氟DLC膜15具有如前述提高鑄模11與樹脂之脫模性之機能。除此之外，DCL膜14其硬度例如為1100~1450Hk而較硬(參考圖4)，故具有高的耐衝擊性。因此，對含氟DLC膜15施加衝擊時，利用DLC膜14可耐受該衝擊。進而，非晶質碳膜13由於具有提高DLC膜14之密著性之機能，故藉由該非晶質碳膜13可防止DLC膜14剝離。該等效果藉由成為滿足上述式2之膜厚比，而可充分發揮。 When the fluorine-containing DLC film 15 is used in the mold for resin molding, the fluorine-containing DLC film 15 has the function of improving the mold release between the mold 11 and the resin as described above. In addition, the hardness of the DCL film 14 is, for example, 1100 to 1450 Hk, which is relatively hard (refer to FIG. 4), and therefore has high impact resistance. Therefore, when an impact is applied to the fluorine-containing DLC film 15, the DLC film 14 can withstand the impact. Furthermore, since the amorphous carbon film 13 has a function of improving the adhesion of the DLC film 14, the amorphous carbon film 13 can prevent the DLC film 14 from being peeled off. These effects can be fully exhibited by becoming a film thickness ratio that satisfies Equation 2 above.

又，非晶質碳膜13之硬度為900Hk左右，例如於800~1000Hv之範圍。 In addition, the hardness of the amorphous carbon film 13 is about 900 Hk, for example, in the range of 800 to 1000 Hv.

且非晶質碳膜13與DLC膜14與含氟DLC膜15之 合計膜厚為0.3μm以上5μm以下(較好1μm以上3μm以下)。 And the amorphous carbon film 13 and the DLC film 14 and the fluorine-containing DLC film 15 The total film thickness is 0.3 μm or more and 5 μm or less (preferably 1 μm or more and 3 μm or less).

又，本實施形態中，含氟DLC膜15之努普硬度為1050Hk以上，但並非限定於此，只要含氟DLC膜15為所成膜之基底(鑄模11或基材)之努普硬度以上即可。 In addition, in this embodiment, the fluorine-containing DLC film 15 has a Knoop hardness of 1050Hk or more, but it is not limited to this, as long as the fluorine-containing DLC film 15 is the base (mold 11 or base material) on which the film is formed. OK.

實施例1 Example 1

實施例1之樣品係與第1實施形態同樣之膜構造。 The sample of Example 1 has the same film structure as that of the first embodiment.

圖3係顯示測定實施例1之樣品1-1之含氟DLC膜之水接觸角與比較例之樣品1-2之含氟DLC膜之水接觸角及比較例之樣品之DLC膜之水接觸角的結果之圖。圖3所示之測定結果係測定樣品上之複數點之接觸角並平均化者。 Figure 3 shows the measurement of the water contact angle of the fluorine-containing DLC film of the sample 1-1 of Example 1 and the water contact angle of the fluorine-containing DLC film of the sample 1-2 of the comparative example and the water contact of the DLC film of the sample of the comparative example Diagram of the result of the angle. The measurement results shown in Figure 3 are those obtained by measuring and averaging the contact angles of multiple points on the sample.

圖4係顯示測定實施例1之樣品1-1之含氟DLC膜之努普硬度與比較例之樣品1-2之含氟DLC膜之努普硬度及比較例之樣品之DLC膜之努普硬度的結果之圖。圖4所示之測定結果係測定樣品上之複數點之努普硬度並平均化者。 Figure 4 shows the measurement of the Knoop hardness of the fluorine-containing DLC film of the sample 1-1 of Example 1 and the Knoop hardness of the fluorine-containing DLC film of the sample 1-2 of the comparative example and the Knoop hardness of the DLC film of the sample of the comparative example Graph of the result of hardness. The measurement results shown in Figure 4 are those obtained by measuring and averaging the Knoop hardness of multiple points on the sample.

《實施例1之樣品1-1》 "Sample 1-1 of Example 1"

實施例1之樣品1-1係於基材上藉以下成膜條件成膜含氟DLC膜者。 The sample 1-1 of Example 1 was obtained by forming a fluorine-containing DLC film on a substrate under the following film forming conditions.

〈含氟DLC膜之條件〉 <Conditions of fluorine-containing DLC film>

基板：SUS板 Substrate: SUS board

成膜裝置：平行平板型之電漿CVD裝置 Film forming device: parallel plate type plasma CVD device

原料氣體：流量15sccm之C7H8與流量15sccm之C9F21N之混合氣體 Raw material gas: mixed gas of C 7 H 8 with a flow rate of 15 sccm and C 9 F 21 N with a flow rate of 15 sccm

高頻電源之頻率：380KHz Frequency of high frequency power supply: 380KHz

高頻輸出：1000W High frequency output: 1000W

壓力：1.5Pa Pressure: 1.5Pa

溫度：室溫 Temperature: room temperature

膜厚：1μm Film thickness: 1μm

《比較例之樣品1-2》 "Sample 1-2 of Comparative Example"

比較例之樣品1-2係於基材上藉以下成膜條件成膜含氟DLC膜者。 The sample 1-2 of the comparative example was a fluorine-containing DLC film formed on a substrate under the following film forming conditions.

〈含氟DLC膜之條件〉 <Conditions of fluorine-containing DLC film>

基板：與樣品1-1相同 Substrate: Same as sample 1-1

成膜裝置：與樣品1-1相同 Film forming device: same as sample 1-1

原料氣體：流量5sccm之C7H8與流量25sccm之C9F21N之混合氣體 Raw material gas: mixed gas of C 7 H 8 with a flow rate of 5 sccm and C 9 F 21 N with a flow rate of 25 sccm

高頻電源之頻率：與樣品1-1相同 Frequency of high frequency power supply: same as sample 1-1

高頻輸出：與樣品1-1相同 High frequency output: same as sample 1-1

壓力：與樣品1-1相同 Pressure: same as sample 1-1

溫度：與樣品1-1相同 Temperature: same as sample 1-1

膜厚：1μm Film thickness: 1μm

《比較例之樣品DLC》 "Sample DLC of Comparative Example"

比較例之樣品係於基材上藉以下成膜條件成膜DLC膜者。 The sample of the comparative example is a DLC film formed on a substrate under the following film forming conditions.

〈DLC膜之條件〉 <Conditions of DLC film>

基板：與樣品1-1相同 Substrate: Same as sample 1-1

成膜裝置：與樣品1-1相同 Film forming device: same as sample 1-1

原料氣體：流量30sccm之C7H8 Raw material gas: C 7 H 8 with a flow rate of 30sccm

高頻電源之頻率：與樣品1-1相同 Frequency of high frequency power supply: same as sample 1-1

高頻輸出：與樣品1-1相同 High frequency output: same as sample 1-1

壓力：與樣品1-1相同 Pressure: same as sample 1-1

溫度：與樣品1-1相同 Temperature: same as sample 1-1

膜厚：0.2μm Film thickness: 0.2μm

如圖3及圖4所示，實施例1之樣品1-1係水接觸角為80°以上且努普硬度為1265Hk，相對地，比較例之樣品1-2係水接觸角較高而為90°且努普硬度大幅低於1050Hk，比較例之樣品(DLC)之努普硬度雖高於1050Hk，但水之接觸角遠低於80°。 As shown in Figures 3 and 4, the sample 1-1 of Example 1 has a water contact angle of 80° or more and a Knoop hardness of 1265Hk. On the contrary, the sample 1-2 of the comparative example has a higher water contact angle. 90° and the Knoop hardness is much lower than 1050Hk. Although the Knoop hardness of the sample (DLC) of the comparative example is higher than 1050Hk, the contact angle of water is much lower than 80°.

實施例2 Example 2

實施例2之樣品係與第2實施形態同樣之膜構造。 The sample of Example 2 has the same film structure as that of the second embodiment.

圖5係顯示測定實施例2之樣品2-1及樣品2-2各者之含氟DLC膜之水接觸角與比較例之樣品之DLC膜之水 接觸角的結果之圖。圖5所示之測定結果係測定樣品上之複數點之接觸角並平均化者。 Figure 5 shows the measurement of the water contact angle of the fluorine-containing DLC film of each of the sample 2-1 and sample 2-2 of Example 2 and the water of the DLC film of the sample of the comparative example A graph of the result of the contact angle. The measurement results shown in Figure 5 are those obtained by measuring and averaging the contact angles of multiple points on the sample.

圖6係顯示測定實施例2之樣品2-1及樣品2-2各者之含氟DLC膜之努普硬度與比較例之樣品之DLC膜之努普硬度的結果之圖。圖6所示之測定結果係測定樣品上之複數點之努普硬度並平均化者。 6 is a graph showing the results of measuring the Knoop hardness of the fluorine-containing DLC film of each of the sample 2-1 and the sample 2-2 of Example 2 and the Knoop hardness of the DLC film of the sample of the comparative example. The measurement result shown in Fig. 6 is obtained by measuring and averaging the Knoop hardness of multiple points on the sample.

圖7係實施例2之樣品2-1之照片。 Figure 7 is a photograph of sample 2-1 of Example 2.

圖8及圖9係顯示對實施例2之樣品2-1及樣品2-2各者之含氟DLC膜進行XPS分析的結果之圖。XPS分析係X射線光電子分光分析法(XPS：X-ray Photoelectron Spectroscopy)。 8 and 9 are graphs showing the results of XPS analysis of the fluorine-containing DLC film of each of sample 2-1 and sample 2-2 of Example 2. XPS analysis is X-ray photoelectron spectroscopy (XPS: X-ray Photoelectron Spectroscopy).

表1係實施例2之樣品2-1及樣品2-2各者之含氟DLC膜中之碳C、氟F及氮N分別之含量由XPS分析結果經數值化者。 Table 1 shows the content of carbon C, fluorine F, and nitrogen N in the fluorine-containing DLC film of each of sample 2-1 and sample 2-2 of Example 2 after being quantified by XPS analysis results.

Figure 105102705-A0202-12-0015-1
Figure 105102705-A0202-12-0015-1

圖11(A)係實施例2之樣品2-2之利用HAADF之膜厚測定結果之圖，圖11(B)係實施例2之樣品2-1之利用HAADF之膜厚測定結果之圖。又，所謂HAADF為STEM暗視野法之一，係以圓環狀之檢測器檢測以大角度散射之透過電子並圖像化時，可獲得與原子編號之平方成比例之對比度(Z對比度)者。 FIG. 11(A) is a graph of the measurement result of the film thickness using HAADF of the sample 2-2 of Example 2, and FIG. 11(B) is a graph of the measurement result of the film thickness using HAADF of the sample 2-1 of Example 2. In addition, the so-called HAADF is one of the STEM dark-field methods. When a circular detector detects transmitted electrons scattered at a large angle and imaged, the contrast ratio (Z contrast) proportional to the square of the atomic number can be obtained. .

圖12係顯示對實施例2之樣品2-1之XPS分析之深度-分佈(Depth-Profile)之圖。圖13係顯示對實施例2之樣品2-2之XPS分析之深度-分佈之圖。圖12及圖13中，橫軸表示深度(nm)，縱軸表示含量(原子%)。 FIG. 12 is a graph showing the depth-profile (Depth-Profile) of the XPS analysis of the sample 2-1 of Example 2. FIG. 13 is a graph showing the depth-distribution of the XPS analysis of the sample 2-2 of Example 2. FIG. In FIGS. 12 and 13, the horizontal axis represents depth (nm), and the vertical axis represents content (atom %).

《實施例2之樣品2-1》 "Sample 2-1 of Example 2"

實施例2之樣品2-1係於基材上形成含有碳、氫、矽及氮之非晶質碳膜，於該非晶質碳膜上形成DLC膜，於該DLC膜上成膜含氟DLC膜者。非晶質碳膜、DLC膜及含氟DLC膜分別之成膜條件係如下。 In the sample 2-1 of Example 2, an amorphous carbon film containing carbon, hydrogen, silicon and nitrogen is formed on the substrate, a DLC film is formed on the amorphous carbon film, and a fluorine-containing DLC film is formed on the DLC film Film. The film forming conditions of the amorphous carbon film, the DLC film, and the fluorine-containing DLC film are as follows.

〈非晶質碳膜之條件〉 <Conditions of Amorphous Carbon Film>

基板：SUS板 Substrate: SUS board

成膜裝置：平行平板型之電漿CVD裝置 Film forming device: parallel plate type plasma CVD device

原料氣體：流量30sccm之HMDS-N Raw material gas: HMDS-N with a flow rate of 30sccm

高頻電源之頻率：380KHz Frequency of high frequency power supply: 380KHz

高頻輸出：1000W High frequency output: 1000W

壓力：1.5Pa Pressure: 1.5Pa

溫度：100℃ Temperature: 100℃

膜厚：0.5μm Film thickness: 0.5μm

〈DLC膜之條件〉 <Conditions of DLC film>

成膜裝置：平行平板型之電漿CVD裝置 Film forming device: parallel plate type plasma CVD device

原料氣體：流量30sccm之C7H8 Raw material gas: C 7 H 8 with a flow rate of 30sccm

高頻電源之頻率：380KHz Frequency of high frequency power supply: 380KHz

高頻輸出：1000W High frequency output: 1000W

壓力：1.5Pa Pressure: 1.5Pa

溫度：100℃ Temperature: 100℃

膜厚：0.2μm Film thickness: 0.2μm

〈含氟DLC膜之條件〉 <Conditions of fluorine-containing DLC film>

成膜裝置：平行平板型之電漿CVD裝置 Film forming device: parallel plate type plasma CVD device

原料氣體：流量15sccm之C7H8與流量15sccm之C9F21N之混合氣體 Raw material gas: mixed gas of C 7 H 8 with a flow rate of 15 sccm and C 9 F 21 N with a flow rate of 15 sccm

高頻電源之頻率：380KHz Frequency of high frequency power supply: 380KHz

高頻輸出：1000W High frequency output: 1000W

壓力：1.5Pa Pressure: 1.5Pa

溫度：室溫 Temperature: room temperature

膜厚：0.3μm Film thickness: 0.3μm

《實施例2之樣品2-2》 "Sample 2-2 of Example 2"

實施例2之樣品2-2係於基材上形成含有碳、氫、矽及氮之非晶質碳膜，於該非晶質碳膜上形成DLC膜，於該DLC膜上成膜含氟DLC膜者。非晶質碳膜、DLC膜及含氟DLC膜分別之成膜條件係如下。 Sample 2-2 of Example 2 is to form an amorphous carbon film containing carbon, hydrogen, silicon and nitrogen on a substrate, a DLC film is formed on the amorphous carbon film, and a fluorine-containing DLC film is formed on the DLC film Film. The film forming conditions of the amorphous carbon film, the DLC film, and the fluorine-containing DLC film are as follows.

〈非晶質碳膜之條件〉 <Conditions of Amorphous Carbon Film>

基板：與樣品2-1之非晶質膜之條件相同 Substrate: the same conditions as the amorphous film of sample 2-1

成膜裝置：與樣品2-1之非晶質膜之條件相同 Film forming device: the same conditions as the amorphous film of sample 2-1

原料氣體：與樣品2-1之非晶質膜之條件相同 Raw material gas: the same conditions as the amorphous film of sample 2-1

高頻電源之頻率：與樣品2-1之非晶質膜之條件相同 Frequency of high-frequency power supply: the same conditions as the amorphous film of sample 2-1

高頻輸出：與樣品2-1之非晶質膜之條件相同 High frequency output: the same conditions as the amorphous film of sample 2-1

壓力：與樣品2-1之非晶質膜之條件相同 Pressure: the same conditions as the amorphous film of sample 2-1

溫度：與樣品2-1之非晶質膜之條件相同 Temperature: the same conditions as the amorphous film of sample 2-1

膜厚：與樣品2-1之非晶質膜之條件相同 Film thickness: the same conditions as the amorphous film of sample 2-1

〈DLC膜之條件〉 <Conditions of DLC film>

成膜裝置：與樣品2-1之DLC膜之條件相同 Film forming device: the same conditions as the DLC film of sample 2-1

原料氣體：與樣品2-1之DLC膜之條件相同 Raw material gas: the same conditions as the DLC film of sample 2-1

高頻電源之頻率：與樣品2-1之DLC膜之條件相同 The frequency of the high-frequency power supply: the same conditions as the DLC film of sample 2-1

高頻輸出：與樣品2-1之DLC膜之條件相同 High frequency output: the same conditions as the DLC film of sample 2-1

壓力：與樣品2-1之DLC膜之條件相同 Pressure: the same conditions as the DLC film of sample 2-1

溫度：與樣品2-1之DLC膜之條件相同 Temperature: the same conditions as the DLC film of sample 2-1

膜厚：與樣品2-1之DLC膜之條件相同 Film thickness: the same conditions as the DLC film of sample 2-1

〈含氟DLC膜之條件〉 <Conditions of fluorine-containing DLC film>

成膜裝置：與樣品2-1之含氟DLC膜之條件相同 Film forming device: the same conditions as the fluorine-containing DLC film of sample 2-1

原料氣體：流量5sccm之C7H8與流量25sccm之C9F21N之混合氣體 Raw material gas: mixed gas of C 7 H 8 with a flow rate of 5 sccm and C 9 F 21 N with a flow rate of 25 sccm

高頻電源之頻率：與樣品2-1之含氟DLC膜之條件相同 The frequency of the high-frequency power supply: the same conditions as the fluorine-containing DLC film of sample 2-1

高頻輸出：與樣品2-1之含氟DLC膜之條件相同 High frequency output: the same conditions as the fluorine-containing DLC film of sample 2-1

壓力：與樣品2-1之含氟DLC膜之條件相同 Pressure: the same conditions as the fluorine-containing DLC film of sample 2-1

溫度：與樣品2-1之含氟DLC膜之條件相同 Temperature: the same conditions as the fluorine-containing DLC film of sample 2-1

膜厚：與樣品2-1之含氟DLC膜之條件相同 Film thickness: the same conditions as the fluorine-containing DLC film of sample 2-1

《比較例之樣品DLC》 "Sample DLC of Comparative Example"

比較例之樣品係於基材上藉以下成膜條件成膜DLC膜者。 The sample of the comparative example is a DLC film formed on a substrate under the following film forming conditions.

〈DLC膜之條件〉 <Conditions of DLC film>

成膜裝置：與樣品2-1之DLC膜之條件相同 Film forming device: the same conditions as the DLC film of sample 2-1

原料氣體：與樣品2-1之DLC膜之條件相同 Raw material gas: the same conditions as the DLC film of sample 2-1

高頻電源之頻率：與樣品2-1之DLC膜之條件相同 The frequency of the high-frequency power supply: the same conditions as the DLC film of sample 2-1

高頻輸出：與樣品2-1之DLC膜之條件相同 High frequency output: the same conditions as the DLC film of sample 2-1

壓力：與樣品2-1之DLC膜之條件相同 Pressure: the same conditions as the DLC film of sample 2-1

溫度：與樣品2-1之DLC膜之條件相同 Temperature: the same conditions as the DLC film of sample 2-1

膜厚：0.2μm Film thickness: 0.2μm

如圖5及圖6所示，實施例2之樣品2-1及2-2係水接觸角為80°以上且努普硬度為1050Hk以上。由於設為非晶質碳膜、DLC膜、含氟DLC膜之積層構造，故水之接觸角與努普硬度均可維持較高。相對地，比較例之樣品(DLC)之努普硬度雖高於1050Hk，但水之接觸角遠低於80°。 As shown in Figs. 5 and 6, the samples 2-1 and 2-2 of Example 2 have a water contact angle of 80° or more and a Knoop hardness of 1050Hk or more. Due to the laminated structure of amorphous carbon film, DLC film, and fluorine-containing DLC film, the water contact angle and Knoop hardness can be maintained high. In contrast, although the Knoop hardness of the sample (DLC) of the comparative example is higher than 1050Hk, the contact angle of water is much lower than 80°.

依據圖7、圖8及表1，確認若含氟DLC膜中含有3 原子%左右之氟，則水之接觸角可維持80°左右，且努普硬度可維持高於1250Hk(參考實施例2之樣品2-1)。且確認，含氟DLC膜中含有至多17原子%之氟時，水之接觸角可大於90°，努普硬度雖可維持高於1050Hk，但低於1250Hk(參考實施例2之樣品2-2)。若如此增加含氟量則可增大接觸角，但努普硬度較低之理由認為係因為含氟DLC膜中之sp3減少之故。 According to Figure 7, Figure 8 and Table 1, confirm that if the fluorine-containing DLC film contains 3 With fluorine of about atomic %, the contact angle of water can be maintained at about 80°, and the Knoop hardness can be maintained above 1250Hk (refer to sample 2-1 of Example 2). It is also confirmed that when the fluorine-containing DLC film contains up to 17 atomic% of fluorine, the contact angle of water can be greater than 90°, and the Knoop hardness can be maintained higher than 1050Hk, but lower than 1250Hk (reference example 2 sample 2-2 ). If the fluorine content is increased in this way, the contact angle can be increased, but the reason for the lower Knoop hardness is believed to be due to the decrease of sp3 in the fluorine-containing DLC film.

依據圖11(A)，實施例2之樣品2-2之非晶質碳膜之膜厚為384.6nm，DLC膜之膜厚為237.8nm，含氟DLC膜之膜厚為86.7nm。且，依據圖11(B)，實施例2之樣品2-1之非晶質碳膜之膜厚為402.8nm，DLC膜之膜厚為251.7nm，含氟DLC膜之膜厚為167.8nm。 According to FIG. 11(A), the film thickness of the amorphous carbon film of the sample 2-2 of Example 2 is 384.6 nm, the film thickness of the DLC film is 237.8 nm, and the film thickness of the fluorine-containing DLC film is 86.7 nm. Furthermore, according to FIG. 11(B), the film thickness of the amorphous carbon film of the sample 2-1 of Example 2 is 402.8 nm, the film thickness of the DLC film is 251.7 nm, and the film thickness of the fluorine-containing DLC film is 167.8 nm.

依據圖12及圖13之各者，確認於非晶質碳膜與DLC膜之交界有Si擴散之層，確認於含氟DLC膜與DLC膜之交界相互膜之元素擴散。由此可知藉由非晶質碳膜可提高基板(SUS板)與DLC膜之密著性，可知可提高DLC膜與含氟DLC膜之密著性。 According to each of FIGS. 12 and 13, it is confirmed that there is a Si diffusion layer at the boundary between the amorphous carbon film and the DLC film, and the element diffusion between the fluorine-containing DLC film and the DLC film is confirmed. It can be seen that the amorphous carbon film can improve the adhesion between the substrate (SUS plate) and the DLC film, and it can be seen that the adhesion between the DLC film and the fluorine-containing DLC film can be improved.

11‧‧‧鑄模 11‧‧‧Mould

12‧‧‧含氟DLC膜 12‧‧‧Fluorinated DLC film

Claims (16)

一種撥水性高硬度膜，其特徵係含有3原子%以上之氟的含氟DLC膜，且前述含氟DLC膜係藉由電漿CVD法所成膜之膜，水之接觸角為80°以上且努普硬度(Knoop hardness)為1050Hk以上。 A water-repellent high-hardness film characterized by a fluorine-containing DLC film containing more than 3 atomic% of fluorine, and the aforementioned fluorine-containing DLC film is a film formed by plasma CVD method, and the contact angle of water is 80° or more And the Knoop hardness is 1050Hk or more. 一種撥水性高硬度膜，其特徵係具有下述膜之積層膜，含有碳、氫、矽與氮之非晶質碳膜、形成於前述非晶質碳膜上之DLC膜、形成於前述DLC膜上之含有3原子%以上之氟的含氟DLC膜，且前述含氟DLC膜係藉由電漿CVD法所成膜之膜，水接觸角為80°以上且努普硬度為1050Hk以上。 A water-repellent, high-hardness film characterized by a laminated film having the following films, an amorphous carbon film containing carbon, hydrogen, silicon and nitrogen, a DLC film formed on the aforementioned amorphous carbon film, and a DLC film formed on the aforementioned DLC The fluorine-containing DLC film containing 3 atomic% or more of fluorine on the film, and the aforementioned fluorine-containing DLC film is a film formed by a plasma CVD method, with a water contact angle of 80° or more and a Knoop hardness of 1050Hk or more. 如請求項2之撥水性高硬度膜，其中前述非晶質碳膜與前述DLC膜與前述含氟DLC膜之膜厚比滿足下述式2：(非晶質碳膜)：(DLC膜)：(含氟DLC膜)=(2.5~7.5)：(1.5~4.5)：(1~3)---式2。 Such as the water-repellent high-hardness film of claim 2, wherein the film thickness ratio of the aforementioned amorphous carbon film to the aforementioned DLC film and the aforementioned fluorine-containing DLC film satisfies the following formula 2: (amorphous carbon film): (DLC film) ：(Fluorine-containing DLC film)=(2.5~7.5):(1.5~4.5):(1~3)---Equation 2. 如請求項1至3中任一項之撥水性高硬度膜，其中前述含氟DLC膜係藉由使用具有烴系氣體及氟碳系氣體之原料氣體及頻率為10~500kHz之高頻電力而為之電漿CVD法所成膜之膜。 Such as the water-repellent high-hardness film of any one of claims 1 to 3, wherein the aforementioned fluorine-containing DLC film is produced by using a raw material gas with hydrocarbon-based gas and fluorocarbon-based gas and high-frequency power with a frequency of 10 to 500 kHz It is a film formed by plasma CVD method. 如請求項2或3之撥水性高硬度膜，其中前述 DLC膜係藉由使用具有烴系氣體之原料氣體及頻率為10~500kHz之高頻電力而為之電漿CVD法所成膜之膜。 Such as the water-repellent high-hardness film of claim 2 or 3, where the aforementioned The DLC film is a film formed by a plasma CVD method using a raw material gas with a hydrocarbon gas and a high frequency power with a frequency of 10 to 500 kHz. 如請求項1之撥水性高硬度膜，其中前述含氟DLC膜係形成於鑄模表面。 The water-repellent high-hardness film of claim 1, wherein the aforementioned fluorine-containing DLC film is formed on the surface of the mold. 如請求項2或3之撥水性高硬度膜，其中前述非晶質碳膜係形成於鑄模表面。 The water-repellent high-hardness film of claim 2 or 3, wherein the aforementioned amorphous carbon film is formed on the surface of the mold. 如請求項6之撥水性高硬度膜，其中前述鑄模係藉由模具鋼(die steel)或高速鋼所形成。 The water-repellent high-hardness film of claim 6, wherein the aforementioned mold is formed by die steel or high-speed steel. 一種鑄模，其係於表面形成含有3原子%以上之氟的含氟DLC膜之鑄模，且前述含氟DLC膜係藉由電漿CVD法所成膜之膜，水之接觸角為80°以上且努普硬度為前述鑄模之努普硬度以上。 A casting mold that forms a fluorine-containing DLC film containing 3 atomic% or more of fluorine on the surface, and the aforementioned fluorine-containing DLC film is a film formed by a plasma CVD method, and the contact angle of water is 80° or more In addition, the Knoop hardness is more than the Knoop hardness of the aforementioned mold. 一種鑄模，其係於表面形成積層膜之鑄模，且前述積層膜具有：含有碳、氫、矽與氮之非晶質碳膜、形成於前述非晶質碳膜上之DLC膜、與形成於前述DLC膜上之含有3原子%以上之氟的含氟DLC膜，前述含氟DLC膜係藉由電漿CVD法所成膜之膜，水之接觸角為80°以上且努普硬度為前述鑄模之努普硬度以上。 A casting mold, which is a mold for forming a laminated film on the surface, and the laminated film has: an amorphous carbon film containing carbon, hydrogen, silicon and nitrogen, a DLC film formed on the amorphous carbon film, and The fluorine-containing DLC film containing 3 atomic% or more of fluorine on the aforementioned DLC film. The aforementioned fluorine-containing DLC film is a film formed by plasma CVD. The contact angle of water is 80° or more and the Knoop hardness is the aforementioned The Knoop hardness of the mold is above. 一種撥水性高硬度膜之製造方法，其特徵係藉由使用具有烴系氣體及氟碳系氣體之原料氣體及頻率為10~500kHz之高頻電力而為之電漿CVD法形成含氟之DLC膜。 A method for manufacturing a water-repellent, high-hardness film, which is characterized by forming a fluorine-containing DLC by using a plasma CVD method with hydrocarbon-based gas and fluorocarbon-based gas and high-frequency power with a frequency of 10~500kHz membrane. 一種撥水性高硬度膜之製造方法，其特徵係藉由使用含有碳、氫、矽及氮之原料氣體而為之電漿CVD法形成非晶質碳膜，於前述非晶質碳膜上，藉由使用具有烴系氣體之原料氣體及頻率為10~500kHz之高頻電力而為之電漿CVD法形成DLC膜，於前述DLC膜上，藉由使用具有烴系氣體及氟碳系氣體之原料氣體及頻率為10~500kHz之高頻電力而為之電漿CVD法形成含氟之DLC膜。 A method for manufacturing a water-repellent, high-hardness film, characterized by forming an amorphous carbon film on the aforementioned amorphous carbon film by a plasma CVD method using raw material gases containing carbon, hydrogen, silicon and nitrogen, The DLC film is formed by the plasma CVD method using a source gas with a hydrocarbon-based gas and high-frequency power with a frequency of 10 to 500 kHz. On the aforementioned DLC film, by using a hydrocarbon-based gas and a fluorocarbon-based gas The fluorine-containing DLC film is formed by the plasma CVD method using raw material gas and high-frequency power with a frequency of 10~500kHz. 如請求項11或12之撥水性高硬度膜之製造方法，其中前述氟碳系氣體係C9F21N氣體。 The method for producing a water-repellent high-hardness film of claim 11 or 12, wherein the aforementioned fluorocarbon-based gas system is C 9 F 21 N gas. 如請求項11之撥水性高硬度膜之製造方法，其中前述含氟DLC膜係形成於鑄模表面。 The method for manufacturing a water-repellent high-hardness film of claim 11, wherein the aforementioned fluorine-containing DLC film is formed on the surface of the mold. 如請求項12之撥水性高硬度膜之製造方法，其中前述非晶質碳膜係形成於鑄模表面。 According to claim 12, the method for producing a water-repellent high-hardness film, wherein the aforementioned amorphous carbon film is formed on the surface of the mold. 一種撥水性高硬度膜，其特徵係具有下述膜之積層膜，含有碳、氫、矽與氮之非晶質碳膜、形成於前述非晶質碳膜上之DLC膜、形成於前述DLC膜上之含有3原子%以上之氟的含氟DLC膜，且前述含氟DLC膜係水接觸角為80°以上且努普硬度為1050Hk以上前述非晶質碳膜與前述DLC膜與前述含氟DLC膜之 膜厚比滿足下述式2：(非晶質碳膜)：(DLC膜)：(含氟DLC膜)=(2.5~7.5)：(1.5~4.5)：(1~3)---式2。 A water-repellent, high-hardness film characterized by a laminated film having the following films, an amorphous carbon film containing carbon, hydrogen, silicon and nitrogen, a DLC film formed on the aforementioned amorphous carbon film, and a DLC film formed on the aforementioned DLC The fluorine-containing DLC film containing 3 atomic% or more of fluorine on the film, and the aforementioned fluorine-containing DLC film has a water contact angle of 80° or more and a Knoop hardness of 1050Hk or more. The aforementioned amorphous carbon film and the aforementioned DLC film are combined with the aforementioned Fluorine DLC film The film thickness ratio satisfies the following formula 2: (amorphous carbon film): (DLC film): (fluorine-containing DLC film)=(2.5~7.5): (1.5~4.5): (1~3)--- formula 2.
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW201302323A (en) * 2011-06-06 2013-01-16 Taiyo Chemical Industry Co Ltd Method of fixing water-shedding coating onto amorphous carbon film

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06344495A (en) * 1993-06-10 1994-12-20 Sekisui Chem Co Ltd Gas barrier film
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JP2007213715A (en) * 2006-02-10 2007-08-23 Saitama Prefecture Method for forming fluorinated diamondlike carbon thin film, and fluorinated diamondlike carbon thin film obtained thereby
JP2010189694A (en) * 2009-02-17 2010-09-02 Miyako Roller Industry Co Aluminum roll and carbon roll having dlc film formed thereon at atmospheric temperature
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JP6383910B2 (en) * 2012-11-27 2018-09-05 地方独立行政法人山口県産業技術センター Plasma CVD apparatus and film manufacturing method

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW201302323A (en) * 2011-06-06 2013-01-16 Taiyo Chemical Industry Co Ltd Method of fixing water-shedding coating onto amorphous carbon film

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