WO2014045904A1

WO2014045904A1 - Method for manufacturing glass product

Info

Publication number: WO2014045904A1
Application number: PCT/JP2013/074087
Authority: WO
Inventors: 宗矩川路; 正章能勢; 亮二松田
Original assignee: コニカミノルタ株式会社
Priority date: 2012-09-21
Filing date: 2013-09-06
Publication date: 2014-03-27

Abstract

In this method for manufacturing a glass product, a preheating step is carried out in a state where impurities discharged from an anti-fouling film material (M1) do not reach a film forming surface (11) of a glass substrate (10), and a film forming step is carried out in a state where a material for an anti-fouling film (PC) discharged from the anti-fouling film material (M1) reaches the film forming surface (11) of the glass substrate (10).

Description

ガラス製品の製造方法Manufacturing method of glass products

　本発明は、ガラス基板の被成膜面にフッ素系の防汚膜を成膜する工程を含む、ガラス製品の製造方法に関する。 The present invention relates to a glass product manufacturing method including a step of forming a fluorine-based antifouling film on a film formation surface of a glass substrate.

　近年、スマートフォンに代表されるように、タッチパネル式のディスプレイ面が情報表示装置に広く採用されている。タッチパネルの表面には、付着した指先の汚れの除去を容易にするため、指先の滑りをよくするため、または、細かい擦傷キズの発生を防止するために、防汚膜（防汚膜コート）が施されている。 In recent years, as represented by smartphones, touch panel type display surfaces have been widely adopted for information display devices. An antifouling film (antifouling film coating) is provided on the surface of the touch panel in order to facilitate the removal of dirt on the fingertips, to improve the sliding of the fingertips, or to prevent the generation of fine scratches. It has been subjected.

　被成膜面に薄膜を成膜する方法が、特開２００３－１４９０４号公報（特許文献１）および特開２０１０－１０６３４４号公報（特許文献２）に開示されている。 A method for forming a thin film on a film formation surface is disclosed in Japanese Patent Application Laid-Open No. 2003-14904 (Patent Document 1) and Japanese Patent Application Laid-Open No. 2010-106344 (Patent Document 2).

　特許文献１には、撥水性薄膜を有する光学部材およびレンズの製造方法に関する技術が開示されている。この技術によれば、撥水性薄膜の蒸着条件およびフッ素化合物の蒸発温度域の温度条件を特定の範囲にすることで、反射防止膜の熱クラック等の欠陥を生じることなく、かつムラなく、しかも短時間で成膜することを可能としている。 Patent Document 1 discloses a technique related to a method of manufacturing an optical member having a water-repellent thin film and a lens. According to this technology, by setting the vapor deposition conditions of the water-repellent thin film and the temperature conditions of the evaporation temperature range of the fluorine compound to a specific range, defects such as thermal cracks of the antireflection film do not occur, and there is no unevenness. It is possible to form a film in a short time.

　特許文献２には、透明基材への防護層の蒸着方法およびその装置に関する技術が開示されている。この技術によれば、反射防止膜の形成と連続して、比較的高分子量である沸点の高いフッ素含有有機ケイ素化合物を用いた撥水膜の成膜を可能としている。 Patent Document 2 discloses a technique related to a method for depositing a protective layer on a transparent substrate and an apparatus therefor. According to this technique, it is possible to form a water-repellent film using a fluorine-containing organosilicon compound having a relatively high molecular weight and a high boiling point in succession to the formation of the antireflection film.

特開２００３－１４９０４号公報Japanese Patent Laid-Open No. 2003-14904 特開２０１０－１０６３４４号公報JP 2010-106344 A

　しかしながら、上記特許文献１および特許文献２等に開示される技術を用いて、ガラス基板の被成膜面にフッ素系の防汚膜を成膜した場合であっても、ガラス基板の製造過程において、そのバッチごとで防汚膜の耐久性にバラツキが生じることが知見された。さらに、発明者らによる鋭意研究の結果、薄膜の蒸着時に使用する防汚膜材料に含まれるハイドロカーボン等の不純物が、防汚膜材料の加熱の初期段階で蒸発し、不純物がガラス基板に付着することで、防汚膜の耐久性に悪影響を与えていることを知見した。 However, even when a fluorine-based antifouling film is formed on the film formation surface of the glass substrate using the techniques disclosed in Patent Document 1 and Patent Document 2, etc., in the manufacturing process of the glass substrate It was found that the durability of the antifouling film varies from batch to batch. Furthermore, as a result of earnest research by the inventors, impurities such as hydrocarbons contained in the antifouling film material used during thin film deposition evaporate in the initial stage of heating the antifouling film material, and the impurities adhere to the glass substrate. As a result, it was found that the durability of the antifouling film was adversely affected.

　本発明は上記の課題に鑑みてなされたものであり、その主たる目的は、防汚膜材料に含まれる不純物のガラス基板への付着を抑制することが可能な防汚膜の成膜工程を含むガラス製品の製造方法を提供することである。 The present invention has been made in view of the above problems, and its main purpose includes a film-forming process of an antifouling film capable of suppressing the adhesion of impurities contained in the antifouling film material to the glass substrate. It is to provide a method for producing a glass product.

　本発明に基づいたガラス成形品の製造方法のある局面においては、真空チャンバー内において、フッ素系化合物を含有する防汚膜材料を用いた真空蒸着法により、ガラス基板の被成膜面にフッ素系の防汚膜を成膜する工程を含む、ガラス製品の製造方法であって、以下の工程を備えている。 In one aspect of the method for producing a glass molded product according to the present invention, a fluorine-based film is formed on a film-forming surface of a glass substrate by a vacuum deposition method using an antifouling film material containing a fluorine-based compound in a vacuum chamber. The manufacturing method of glass products including the process of forming an antifouling film | membrane of the following, Comprising: The following processes are provided.

　上記ガラス基板を準備する工程と、上記ガラス基板の上記被成膜面にフッ素系の上記防汚膜を成膜する工程と、を備えている。 The step of preparing the glass substrate and the step of forming the fluorine-based antifouling film on the film-forming surface of the glass substrate are provided.

　上記防汚膜を成膜する工程は、上記防汚膜材料に含有する不純物を放出するため、上記フッ素系化合物を、上記フッ素系化合物の沸点－５０度の温度より高く、かつ、上記沸点より低い温度にまで（一度以上）加熱する予備加熱工程と、上記予備加熱工程の後、上記フッ素系化合物を上記沸点より低い温度から上記沸点より高い温度にまで加熱し、上記ガラス基板の上記被成膜面に上記防汚膜を成膜する成膜工程と、を備える。 The step of depositing the antifouling film releases impurities contained in the antifouling film material, so that the fluorine compound is higher than the boiling point of the fluorine compound −50 ° C. After the preheating step of heating to a low temperature (at least once) and after the preheating step, the fluorine-based compound is heated from a temperature lower than the boiling point to a temperature higher than the boiling point, and the deposition of the glass substrate is performed. A film forming step of forming the antifouling film on the film surface.

　上記予備加熱工程は、上記ガラス基板の上記被成膜面に、上記防汚膜材料から放出される上記不純物が到達しない状態で行なわれ、上記成膜工程は、上記ガラス基板の上記被成膜面に、上記防汚膜材料から放出される上記防汚膜の材料が到達する状態で行なわれる。 The preheating step is performed in a state where the impurities released from the antifouling film material do not reach the film formation surface of the glass substrate, and the film formation step is performed on the glass substrate. The surface of the antifouling film released from the antifouling film material reaches the surface.

　本発明に基づいたガラス成形品の製造方法の他の局面においては、真空チャンバー内において、フッ素系化合物を含有する防汚膜材料を用いた真空蒸着法により、ガラス基板の被成膜面にフッ素系の防汚膜を成膜する工程を含む、ガラス製品の製造方法であって、以下の工程を備える。 In another aspect of the method for producing a glass molded product according to the present invention, fluorine is applied to the film formation surface of the glass substrate by a vacuum deposition method using an antifouling film material containing a fluorine-based compound in a vacuum chamber. The manufacturing method of a glass product including the process of forming a system antifouling film | membrane, Comprising: The following processes are provided.

　上記防汚膜を成膜する工程は、上記防汚材料を沸点未満の温度で加熱し、上記防汚材料に含まれる不純物を放出させる予備加熱工程と、上記予備加熱工程の後、上記防汚材料を沸点以上まで加熱を行ない、上記ガラス基板の上記被成膜面に上記防汚膜を成膜する成膜工程と、を備える。 The step of forming the antifouling film comprises heating the antifouling material at a temperature below the boiling point to release impurities contained in the antifouling material, and after the preheating step, the antifouling material A film forming step of heating the material to the boiling point or higher and forming the antifouling film on the film formation surface of the glass substrate.

　上記予備加熱工程から上記成膜工程への移行は、上記真空チャンバー内の圧力の変化率が上昇から減少に転じた後、変化率が急峻な状態から緩やかな状態に転じた後に行なう。 The transition from the preheating step to the film forming step is performed after the rate of change in pressure in the vacuum chamber has changed from an increase to a decrease and then the rate of change has changed from a steep state to a gentle state.

　この発明に基づいたガラス製品の製造方法のさらに他の局面においては、真空チャンバー内において、フッ素系化合物を含有する防汚膜材料を用いた真空蒸着法により、ガラス基板の被成膜面にフッ素系の防汚膜を成膜する工程を含む、ガラス製品の製造方法であって、以下の工程を備える。 In still another aspect of the glass product manufacturing method according to the present invention, fluorine is deposited on the film-forming surface of the glass substrate by a vacuum deposition method using an antifouling film material containing a fluorine-based compound in a vacuum chamber. The manufacturing method of a glass product including the process of forming a system antifouling film | membrane, Comprising: The following processes are provided.

　上記ガラス基板を準備する工程と、上記ガラス基板の上記被成膜面にフッ素系の上記防汚膜を成膜する工程と、を備える。 A step of preparing the glass substrate, and a step of forming the fluorine-based antifouling film on the film-forming surface of the glass substrate.

　上記防汚膜を成膜する工程は、上記防汚材料を沸点未満の温度で加熱し、上記防汚材料に含まれる不純物を放出させる予備加熱工程と、上記予備加熱工程の後、上記防汚材料を沸点以上の温度まで加熱を行ない、上記ガラス基板の上記被成膜面に上記防汚膜を成膜する成膜工程と、を備える。 The step of forming the antifouling film comprises heating the antifouling material at a temperature below the boiling point to release impurities contained in the antifouling material, and after the preheating step, the antifouling material A film forming step of heating the material to a temperature equal to or higher than the boiling point and forming the antifouling film on the film formation surface of the glass substrate.

　上記予備加熱工程から上記成膜工程への移行は、上記防汚材料中の有効成分量の占める質量％濃度が、９５ｗｔ％以上となった後に行なう。 The transition from the preheating step to the film forming step is performed after the mass% concentration of the active ingredient amount in the antifouling material becomes 95 wt% or more.

　本発明によれば、防汚膜材料に含まれる不純物のガラス基板への付着を抑制することが可能な防汚膜の成膜工程を含むガラス製品の製造方法を提供することを可能とする。 According to the present invention, it is possible to provide a method for producing a glass product including an antifouling film forming step capable of suppressing the adhesion of impurities contained in the antifouling film material to the glass substrate.

実施の形態１におけるディスプレイ用カバーガラスを備えるディスプレイ装置の分解した状態を示す斜視図である。It is a perspective view which shows the state which the display apparatus provided with the cover glass for displays in Embodiment 1 decomposed | disassembled. 図１中のＩＩ－ＩＩ線に沿った矢視断面図である。FIG. 2 is a cross-sectional view taken along the line II-II in FIG. 実施の形態１における第１の真空チャンバーの構造を示す図である。2 is a diagram illustrating a structure of a first vacuum chamber in Embodiment 1. FIG. 実施の形態１における第２の真空チャンバーの構造を示す図である。3 is a diagram showing a structure of a second vacuum chamber in Embodiment 1. FIG. 実施の形態１における第３の真空チャンバーの構造を示す図である。3 is a diagram showing a structure of a third vacuum chamber in Embodiment 1. FIG. 第１の真空チャンバーを用いた場合の、実施例１から実施例４および比較例１から比較例３の各種条件を示す図である。It is a figure which shows the various conditions of Example 1 to Example 4 and Comparative Example 1 to Comparative Example 3 at the time of using a 1st vacuum chamber. 実施例１１におけるシャッター開放時間と防汚膜材料温度との関係を示す図である。It is a figure which shows the relationship between the shutter open time in Example 11, and antifouling film | membrane material temperature. 実施例１２におけるシャッター開放時間と防汚膜材料温度との関係を示す図である。It is a figure which shows the relationship between the shutter open time in Example 12, and antifouling film | membrane material temperature. 実施例１３におけるシャッター開放時間と防汚膜材料温度との関係を示す図である。It is a figure which shows the relationship between the shutter open time in Example 13, and antifouling film | membrane material temperature. 実施例１４におけるシャッター開放時間と防汚膜材料温度との関係を示す図である。It is a figure which shows the relationship between the shutter open time in Example 14, and antifouling film | membrane material temperature. 比較例１１におけるシャッター開放時間と防汚膜材料温度との関係を示す図である。It is a figure which shows the relationship between the shutter open time and antifouling film | membrane material temperature in the comparative example 11. 比較例１２におけるシャッター開放時間と防汚膜材料温度との関係を示す図である。It is a figure which shows the relationship between the shutter open time in Comparative Example 12, and antifouling film | membrane material temperature. 比較例１３におけるシャッター開放時間と防汚膜材料温度との関係を示す図である。It is a figure which shows the relationship between the shutter open time in Comparative Example 13, and antifouling film | membrane material temperature. 第２の真空チャンバーを用いた場合の、実施例１５および実施例１６、並びに比較例１４および比較例１５の各種条件を示す第１図である。It is FIG. 1 which shows the various conditions of Example 15 and Example 16, and the comparative example 14 and the comparative example 15 at the time of using a 2nd vacuum chamber. 第２の真空チャンバーを用いた場合の、実施例１５および実施例１６、並びに比較例１４および比較例１５の各種条件を示す第２図である。It is FIG. 2 which shows the various conditions of Example 15 and Example 16, and the comparative example 14 and the comparative example 15 at the time of using a 2nd vacuum chamber. 第１の真空チャンバーを用いた場合の、実施例１７、実施例１８、比較例１６および比較例１７の各種条件を示す図である。It is a figure which shows the various conditions of Example 17, Example 18, Comparative Example 16, and Comparative Example 17 at the time of using a 1st vacuum chamber. 実施例１７および実施例１８におけるシャッター開放時間と防汚膜材料温度との関係を示す図である。It is a figure which shows the relationship between the shutter open time in Example 17 and Example 18, and antifouling film | membrane material temperature. 比較例１６および比較例１７におけるシャッター開放時間と防汚膜材料温度との関係を示す図である。It is a figure which shows the relationship between the shutter opening time in Comparative Example 16 and Comparative Example 17, and antifouling film | membrane material temperature. 実施の形態２における第１の真空チャンバーを用いた場合の、実施例２１から実施例２２および比較例２１から比較例２３の各種条件を示す図である。It is a figure which shows the various conditions of Example 21 to Example 22 and Comparative Example 21 to Comparative Example 23 at the time of using the 1st vacuum chamber in Embodiment 2. FIG. 実施例２１におけるシャッター開放時間、圧力、真空度、および水晶レートの関係を示す図である。It is a figure which shows the relationship between the shutter open time in Example 21, a pressure, a vacuum degree, and a crystal rate. 実施例２２におけるシャッター開放時間、圧力、真空度、および水晶レートの関係を示す図である。It is a figure which shows the relationship between the shutter open time in Example 22, a pressure, a vacuum degree, and a crystal rate. 実施例２３におけるシャッター開放時間、圧力、真空度、および水晶レートの関係を示す図である。It is a figure which shows the relationship between the shutter open time in Example 23, a pressure, a vacuum degree, and a crystal rate. 実施例２４におけるシャッター開放時間、圧力、真空度、および水晶レートの関係を示す図である。It is a figure which shows the relationship between the shutter open time in Example 24, a pressure, a vacuum degree, and a crystal rate. 比較例２１におけるシャッター開放時間、圧力、真空度、および水晶レートの関係を示す図である。It is a figure which shows the relationship between the shutter open time in a comparative example 21, a pressure, a vacuum degree, and a crystal rate. 比較例２２におけるシャッター開放時間、圧力、真空度、および水晶レートの関係を示す図である。It is a figure which shows the relationship between the shutter open time in a comparative example 22, a pressure, a vacuum degree, and a crystal rate. 比較例２３におけるシャッター開放時間、圧力、真空度、および水晶レートの関係を示す図である。It is a figure which shows the relationship between the shutter open time in a comparative example 23, a pressure, a vacuum degree, and a crystal rate. 比較例２４におけるシャッター開放時間、圧力、真空度、および水晶レートの関係を示す図である。It is a figure which shows the relationship between the shutter opening time in Comparative Example 24, a pressure, a vacuum degree, and a crystal rate. 比較例２５におけるシャッター開放時間、圧力、真空度、および水晶レートの関係を示す図である。It is a figure which shows the relationship of the shutter open time in a comparative example 25, a pressure, a vacuum degree, and a crystal rate. 実施の形態３における開放時間と温度との関係（蒸着条件）を示す図である。It is a figure which shows the relationship (vapor deposition conditions) between the open time and temperature in Embodiment 3. 実施の形態３における第１の真空チャンバーを用いた場合の、実施例３１から実施例３４および比較例３１から比較例３４の各種条件を示す図である。It is a figure which shows the various conditions of Example 31 to Example 34 and Comparative Example 31 to Comparative Example 34 at the time of using the 1st vacuum chamber in Embodiment 3. FIG. 実施の形態３における第１の真空チャンバーを用いた場合の、実施例３５、実施例３６、比較例３５、および比較例３６の各種条件を示す図である。It is a figure which shows the various conditions of Example 35, Example 36, Comparative Example 35, and Comparative Example 36 at the time of using the 1st vacuum chamber in Embodiment 3. FIG.

　本発明に基づいた各実施の形態および各実施例について、以下、図面を参照しながら説明する。各実施の形態および各実施例の説明において、個数、量などに言及する場合、特に記載がある場合を除き、本発明の範囲は必ずしもその個数、量などに限定されない。実施の形態および各実施例の説明において、同一の部品、相当部品に対しては、同一の参照番号を付し、重複する説明は繰り返さない場合がある。 Embodiments and examples based on the present invention will be described below with reference to the drawings. In the description of each embodiment and each example, when referring to the number, amount, and the like, the scope of the present invention is not necessarily limited to the number, amount, and the like unless otherwise specified. In the description of the embodiment and each example, the same parts and corresponding parts are denoted by the same reference numerals, and redundant description may not be repeated.

　以下の実施の形態においては、ガラス製品としてスマートフォンに用いられるディスプレイ用カバーガラスに本発明を適用した場合について説明しているが、ディスプレイ用カバーガラスはスマートフォンに限定されず、タブレット型の携帯型端末装置、携帯電話（フィーチャーフォン）、設置型の情報表示装置、その他のタッチパネル式のディスプレイを採用する情報表示装置に、広く本発明を適用することができる。 In the following embodiment, the case where the present invention is applied to a display cover glass used for a smartphone as a glass product is described. However, the display cover glass is not limited to a smartphone, and is a tablet-type portable terminal. The present invention can be widely applied to information display devices that employ devices, mobile phones (feature phones), stationary information display devices, and other touch panel displays.

　［実施の形態１］
　本発明に基づいた実施の形態１におけるガラス製品の製造方法について、以下、図を参照しながら説明する。 [Embodiment 1]
A method for manufacturing a glass product in Embodiment 1 based on the present invention will be described below with reference to the drawings.

　（ディスプレイ装置１００，ディスプレイ用カバーガラス１０）
　図１は、実施の形態１におけるディスプレイ用カバーガラス１０を備えるディスプレイ装置１００の分解した状態を示す斜視図である。図２は、図１中のＩＩ－ＩＩ線に沿った矢視断面図である。 (Display device 100, cover glass 10 for display)
FIG. 1 is a perspective view showing a disassembled state of a display device 100 including a display cover glass 10 according to the first embodiment. 2 is a cross-sectional view taken along the line II-II in FIG.

　図１に示すように、ディスプレイ装置１００は、ガラス製品としてのディスプレイ用カバーガラス１０、平板状の形状を有する外装プレート２０、外装プレート２０の上に配置される回路基板３０、回路基板３０の上に実装されるディスプレイ４０、および、回路基板３０の上に実装されるスピーカー３１を備える。 As shown in FIG. 1, a display device 100 includes a display cover glass 10 as a glass product, an outer plate 20 having a flat plate shape, a circuit board 30 disposed on the outer plate 20, and an upper surface of the circuit board 30. And a speaker 31 mounted on the circuit board 30.

[規則91に基づく訂正 20.09.2013]　
　ディスプレイ用カバーガラス１０は、外装プレート２０に取り付けられる（矢印ＡＲ参照）。ディスプレイ用カバーガラス１０は、回路基板３０、ディスプレイ４０、およびスピーカー３１を、外装プレート２０上に封止する。[Correction based on Rule 91 20.09.2013]
The display cover glass 10 is attached to the exterior plate 20 (see arrow AR). The display cover glass 10 seals the circuit board 30, the display 40, and the speaker 31 on the exterior plate 20.

[規則91に基づく訂正 20.09.2013]　
　ディスプレイ用カバーガラス１０は、ディスプレイ４０の画像表示部４２を覆うように設けられ、スピーカー３１に対応するように設けられる開口部１０Ｈを含む。開口部１０Ｈは、ディスプレイ用カバーガラス１０の表面１１（図２参照）側から裏面１２（図２参照）側に向かって貫通している。[Correction based on Rule 91 20.09.2013]
The display cover glass 10 is provided so as to cover the image display unit 42 of the display 40, and includes an opening 10 H provided so as to correspond to the speaker 31. The opening 10H penetrates from the front surface 11 (see FIG. 2) side of the display cover glass 10 toward the back surface 12 (see FIG. 2) side.

　（ディスプレイ用カバーガラス１０）
　図１および図２に示すように、ディスプレイ用カバーガラス１０は、主面部１３（図２参照）、接続部１４（図２参照）、および、側面部１５（図２参照）を有する。本実施の形態においては、主面部１３の表面（被成膜面）１１上に、二酸化珪素を主成分とした下地膜ＵＣおよびその下地膜ＵＣの上にフッ素系の防汚膜ＰＣが成膜されている。 (Display cover glass 10)
As shown in FIGS. 1 and 2, the display cover glass 10 includes a main surface portion 13 (see FIG. 2), a connection portion 14 (see FIG. 2), and a side surface portion 15 (see FIG. 2). In the present embodiment, a base film UC mainly composed of silicon dioxide and a fluorine-based antifouling film PC are formed on the base film UC on the surface (deposition surface) 11 of the main surface portion 13. Has been.

　表面１１の上に直接防汚膜ＰＣが成膜される場合、表面１１にフッ素系の防汚膜ＰＣを成膜する前に、表面１１に、光学膜とこの光学膜の上に二酸化珪素を主成分とした無機膜を成膜してもよい。この光学膜は、無機膜を積層した多層膜であるとよい。下地膜ＵＣが設けられず、フッ素系の防汚膜ＰＣのみを成膜してもよい。 When the antifouling film PC is directly formed on the surface 11, before forming the fluorine-based antifouling film PC on the surface 11, the optical film and silicon dioxide on the optical film are formed on the surface 11. An inorganic film having a main component may be formed. This optical film is preferably a multilayer film in which inorganic films are stacked. Only the fluorine-based antifouling film PC may be formed without the base film UC.

　主面部１３は、略平板状の形状を有する。ディスプレイ用カバーガラス１０がディスプレイ４０に取り付けられた状態では、主面部１３の表面１１側が外部に露出する。本実施の形態における主面部１３の外縁は、４つの角部が丸みを帯びた略矩形状の形状を有している。 The main surface portion 13 has a substantially flat plate shape. In the state where the display cover glass 10 is attached to the display 40, the surface 11 side of the main surface portion 13 is exposed to the outside. The outer edge of the main surface portion 13 in the present embodiment has a substantially rectangular shape in which four corners are rounded.

　接続部１４は、主面部１３の外縁に連設される。接続部１４は、主面部１３から外方に向かうにしたがって、表面１１から遠ざかる方向に湾曲する。側面部１５は、接続部１４の外縁に連設される。側面部１５は、全体として環状の形状を有し、接続部１４を挟んで主面部１３の反対側に位置している。ディスプレイ用カバーガラス１０は、主面部１３側から側面部１５側に向かうにつれて、接続部１４において３Ｄ（three　dimension）形状を持って湾曲するように形成されている。 The connecting portion 14 is connected to the outer edge of the main surface portion 13. The connecting portion 14 curves in a direction away from the surface 11 as it goes outward from the main surface portion 13. The side surface portion 15 is connected to the outer edge of the connection portion 14. The side surface portion 15 has an annular shape as a whole, and is located on the opposite side of the main surface portion 13 with the connection portion 14 interposed therebetween. The display cover glass 10 is formed to be curved with a 3D (three dimension) shape at the connection portion 14 as it goes from the main surface portion 13 side to the side surface portion 15 side.

　ディスプレイ用カバーガラス１０の画像表示部４２側に位置する裏面１２側から表面１１側に向かって、所定の画像情報を含む光Ｌ（図２参照）が主面部１３を透過する。画像表示部４２上に表示された各種の画像情報は、使用者により認識される。主面部１３の表面１１がタッチパネル式のディスプレイ面を構成している場合、主面部１３の表面１１は、使用者の手指（図示せず）によって押圧されたり、主面部１３の表面１１はペン（図示せず）などによって押圧されたりする。 The light L (see FIG. 2) including predetermined image information passes through the main surface portion 13 from the back surface 12 side located on the image display portion 42 side of the display cover glass 10 toward the front surface 11 side. Various types of image information displayed on the image display unit 42 are recognized by the user. When the surface 11 of the main surface portion 13 constitutes a touch panel display surface, the surface 11 of the main surface portion 13 is pressed by a user's finger (not shown) or the surface 11 of the main surface portion 13 is a pen ( (Not shown) or the like.

　ディスプレイ用カバーガラス１０の形状は、図１および図２に示すように、４つの角部が丸みを帯びた略矩形状の形状に限定されるものではなく、平板状の形状であってもよい。 As shown in FIGS. 1 and 2, the shape of the display cover glass 10 is not limited to a substantially rectangular shape in which four corners are rounded, and may be a flat plate shape. .

　（第１の真空チャンバー２００）
　次に、図３を参照して、ディスプレイ用カバーガラス１０の表面１１に防汚膜を成膜する際に用いられる第１の真空チャンバー２００の構成について説明する。図３は、実施の形態１における第１の真空チャンバー２００の構造を示す図である。 (First vacuum chamber 200)
Next, with reference to FIG. 3, the structure of the 1st vacuum chamber 200 used when forming an antifouling film | membrane on the surface 11 of the cover glass 10 for a display is demonstrated. FIG. 3 is a diagram showing the structure of the first vacuum chamber 200 in the first embodiment.

　この第１の真空チャンバー２００は、ケーシング２０１で覆われた一つの部屋を構成している。ケーシング２０１の内部下方には、ベース２０３、ベース２０３に設けられたヒーター２０５、ヒーター２０５の上に載置される防汚膜材料収容容器２０７、防汚膜材料収容容器２０７内に蓄えられる防汚膜材料Ｍ１の温度を測定するとともに温度を制御する熱電対２０９とを備えている。防汚膜材料収容容器２０７は上方が開口された鍋状の容器である。ヒーター２０５および熱電対２０９は、図示しない温度制御部によって、所定の温度となるように制御されている。 The first vacuum chamber 200 constitutes one room covered with the casing 201. Below the inside of the casing 201, there are a base 203, a heater 205 provided on the base 203, an antifouling film material container 207 placed on the heater 205, and an antifouling material stored in the antifouling film material container 207. A thermocouple 209 that measures the temperature of the film material M1 and controls the temperature is provided. The antifouling film material container 207 is a pan-like container having an upper opening. The heater 205 and the thermocouple 209 are controlled to have a predetermined temperature by a temperature control unit (not shown).

　防汚膜材料収容容器２０７の内部には、防汚膜材料Ｍ１として、フッ素系シランカップリング剤が蓄積される。具体的には、ダイキン工業株式会社製のオプツール（登録商標）ＤＳＸ、信越化学工業株式会社製のＫＹ－１７８、東レダウコーニング株式会社製のＣｏｒｎｉｎｇ（登録商標）２６３４、メルク株式会社製のＷＲ４、キヤノンオプトロン株式会社製のＯＦＳＲ等が挙げられる。 In the antifouling film material container 207, a fluorine-based silane coupling agent is accumulated as the antifouling film material M1. Specifically, OPTOOL (registered trademark) DSX manufactured by Daikin Industries, Ltd., KY-178 manufactured by Shin-Etsu Chemical Co., Ltd., Corning (registered trademark) 2634 manufactured by Toray Dow Corning Corporation, WR4 manufactured by Merck Corporation, Examples include OFSR manufactured by Canon Optron Co., Ltd.

　ケーシング２０１の内部上方には、複数のディスプレイ用カバーガラス１０を保持する丸型ドーム形状の基板支持部材２１３が設けられている。ディスプレイ用カバーガラス１０の被成膜面である表面１１が、防汚膜材料収容容器２０７に対向するように、複数のディスプレイ用カバーガラス１０は基板支持部材２１３に保持される。 A round dome-shaped substrate support member 213 that holds a plurality of display cover glasses 10 is provided in the upper part of the casing 201. The plurality of display cover glasses 10 are held by the substrate support member 213 such that the surface 11 that is the film formation surface of the display cover glass 10 faces the antifouling film material container 207.

　ケーシング２０１には排気口２０１ｈが設けられ、表面１１に防汚膜ＰＣを成膜する工程においては、常に排気状態が維持されている。 The casing 201 is provided with an exhaust port 201h, and in the process of forming the antifouling film PC on the surface 11, the exhaust state is always maintained.

　ディスプレイ用カバーガラス１０の表面１１と防汚膜材料Ｍ１との間には、シャッター２１１が配設されている。このシャッター２１１は、後述の予備加熱工程においては、ディスプレイ用カバーガラス１０の表面１１に、防汚膜材料Ｍ１から放出される不純物が到達しないように防汚膜材料Ｍ１を覆う位置と（図３中のＰ１）と、後述の成膜工程においては、ディスプレイ用カバーガラス１０の表面１１に、防汚膜材料Ｍ１から放出される防汚膜ＰＣの材料が到達するように、防汚膜材料Ｍ１を開放する位置（図３中のＰ２）との間を移動可能に設けられている。 A shutter 211 is disposed between the surface 11 of the display cover glass 10 and the antifouling film material M1. The shutter 211 is positioned so as to cover the antifouling film material M1 so that impurities released from the antifouling film material M1 do not reach the surface 11 of the display cover glass 10 in the preheating step described later (FIG. 3). In the film forming step described later, the antifouling film material M1 so that the material of the antifouling film PC released from the antifouling film material M1 reaches the surface 11 of the display cover glass 10. It is provided so as to be movable between a position where P is opened (P2 in FIG. 3).

　シャッター２１１と防汚膜材料Ｍ１との間は、約５ｃｍ程度離されている。このようにシャッター２１１を用いることにより、予備加熱工程において、表面１１と防汚膜材料Ｍ１との間が物理的に遮られた状態と、表面１１と防汚膜材料Ｍ１との間が物理的に開放された状態との選択が可能となる。 The distance between the shutter 211 and the antifouling film material M1 is about 5 cm. By using the shutter 211 in this way, in the preheating step, the surface 11 and the antifouling film material M1 are physically blocked and the surface 11 and the antifouling film material M1 are physically separated. It is possible to select an open state.

　シャッター２１１に限らず、予備加熱工程においては、ディスプレイ用カバーガラス１０の表面１１に、防汚膜材料Ｍ１から放出される不純物が到達しない状態で行なわれ、成膜工程においては、ディスプレイ用カバーガラス１０の表面１１に、防汚膜材料Ｍ１から放出される防汚膜ＰＣの材料が到達する状態で行なわれる構成であれば、どのような構成の採用も可能である。 Not only the shutter 211 but also the preheating step is performed in a state where impurities released from the antifouling film material M1 do not reach the surface 11 of the display cover glass 10, and the display cover glass is used in the film forming step. Any configuration may be adopted as long as the configuration is performed in a state where the material of the antifouling film PC released from the antifouling film material M1 reaches the surface 11 of the ten.

　（ガラス製品の製造方法）
　上記構成を備える第１の真空チャンバー２００を用いた場合の、本実施の形態におけるディスプレイ用カバーガラス１０の製造方法に関し、フッ素系化合物を含有する防汚膜材料Ｍ１を用いた真空蒸着法により、ディスプレイ用カバーガラス１０の表面１１にフッ素系の防汚膜ＰＣを成膜する工程について以下する。 (Glass product manufacturing method)
In the case of using the first vacuum chamber 200 having the above-described configuration, the manufacturing method of the display cover glass 10 in the present embodiment, by the vacuum deposition method using the antifouling film material M1 containing a fluorine-based compound, The process of forming the fluorine-based antifouling film PC on the surface 11 of the display cover glass 10 will be described below.

　まず、第１の真空チャンバー２００内に防汚膜が成膜されていないディスプレイ用カバーガラス１０を準備する。具体的には、ディスプレイ用カバーガラス１０の被成膜面である表面１１が、防汚膜材料収容容器２０７に対向するように、複数のディスプレイ用カバーガラス１０を基板支持部材２１３に保持させる。 First, a display cover glass 10 in which an antifouling film is not formed in the first vacuum chamber 200 is prepared. Specifically, the plurality of display cover glasses 10 are held on the substrate support member 213 such that the surface 11 that is the film formation surface of the display cover glass 10 faces the antifouling film material container 207.

　次に、ディスプレイ用カバーガラス１０の温度を室温からフッ素系化合物の沸点未満の範囲で加熱する。フッ素系化合物の性能バラツキの観点から、５０度～８０度の範囲でディスプレイ用カバーガラス１０を加熱する。予めディスプレイ用カバーガラス１０の表面１１に、下地膜ＵＣとしてＳｉＯ_２膜を５ｎｍ～２００ｎｍ、より好ましくは１０ｎｍ～１００ｎｍ堆積させておくとよい。 Next, the temperature of the display cover glass 10 is heated in the range from room temperature to less than the boiling point of the fluorine compound. From the viewpoint of variation in performance of the fluorine compound, the display cover glass 10 is heated in the range of 50 to 80 degrees. An SiO ₂ film as a base film UC may be deposited in advance on the surface 11 of the display cover glass 10 in a range of 5 nm to 200 nm, more preferably 10 nm to 100 nm.

　下地膜ＵＣ（光学膜）の最上層をＳｉＯ_２膜（無機膜）として５ｎｍ～２００ｎｍ、より好ましくは１０ｎｍ～１００ｎｍ堆積させてもよい。下地膜ＵＣ（光学膜）は、無機膜を積層した多層膜であってもよい。 The uppermost layer of the base film UC (optical film) may be deposited as a SiO ₂ film (inorganic film) of 5 nm to 200 nm, more preferably 10 nm to 100 nm. The base film UC (optical film) may be a multilayer film in which inorganic films are stacked.

　ＳｉＯ_２膜の下地膜ＵＣを形成しなくても、ディスプレイ用カバーガラス１０が二酸化珪素が主体であれば、フッ素系の防汚膜ＰＣの性能を十分に発揮することが可能である。しかし、フッ素系の防汚膜ＰＣと母体であるディスプレイ用カバーガラス１０との結合が形成される反応速度の面から、ＳｉＯ_２膜の下地膜ＵＣを成膜してからフッ素系化合物の防汚膜ＰＣを形成したほうが、反応がより早く進みより好ましい。 Even if the base film UC of the SiO ₂ film is not formed, if the display cover glass 10 is mainly made of silicon dioxide, the performance of the fluorine-based antifouling film PC can be sufficiently exhibited. However, from the viewpoint of reaction rate bonds are formed between the antifouling film display cover glass 10 is a PC and maternal fluorine, after formation of the base film UC of the SiO ₂ film of the fluorine compound antifouling It is more preferable to form the film PC because the reaction proceeds faster.

　下地膜ＵＣの成膜においては、ＳｉＯ_２膜の堆積中もしくは堆積前に、ＡｒもしくはＯ_２、または、両者の混合ガスによるイオンビーム照射を行なってもよい。 In the formation of the base film UC, ion beam irradiation with Ar or O ₂ or a mixed gas of both may be performed during or before the deposition of the SiO ₂ film.

　次に、防汚膜ＰＣを成膜する工程として、防汚膜材料Ｍ１に含有する不純物を放出させるための予備加熱工程として、フッ素系化合物である防汚膜材料Ｍ１の温度が、防汚膜材料Ｍ１の沸点（Ｔ３）－５０度の温度（Ｔ１）より高く、かつ、沸点（Ｔ３）より低い温度（Ｔ２）にまで加熱する。 Next, as a process for forming the antifouling film PC, as a preheating process for releasing impurities contained in the antifouling film material M1, the temperature of the antifouling film material M1, which is a fluorine-based compound, is increased. The boiling point (T3) of the material M1 is heated to a temperature (T2) higher than the temperature (T1) of −50 degrees and lower than the boiling point (T3).

　この予備加熱工程においては、シャッター２１１を、防汚膜材料Ｍ１を覆う位置Ｐ１に移動させた状態で、防汚膜材料Ｍ１の加熱を行なう。 In this preliminary heating step, the antifouling film material M1 is heated in a state where the shutter 211 is moved to the position P1 covering the antifouling film material M1.

　一般的に防汚膜材料Ｍ１には、フッ素系化合物の有効成分と、有効成分の機能の失活を防ぐための溶剤とを含み、研究を重ねた結果、溶剤が揮発し、さらにフッ素系化合物の沸点から－５０度より高温で加熱することで、耐久性能が発揮されることが分かった。さらに、防汚膜材料Ｍ１の加熱温度は、フッ素系化合物の沸点を超えることは熱分解による材料の劣化、および有効成分の無駄になるために好ましくなく、沸点（Ｔ３）未満で行なわれることが好ましい。 In general, the antifouling film material M1 contains an active ingredient of a fluorine compound and a solvent for preventing the deactivation of the function of the active ingredient, and as a result of repeated research, the solvent is volatilized. It was found that durability performance is exhibited by heating at a temperature higher than −50 ° C. from the boiling point of. Furthermore, it is not preferable that the heating temperature of the antifouling film material M1 exceeds the boiling point of the fluorine-based compound because the material deteriorates due to thermal decomposition and the active component is wasted, and may be performed below the boiling point (T3). preferable.

　次に、防汚膜材料Ｍ１の温度を、防汚膜材料Ｍ１の沸点（Ｔ３）－５０度の温度（Ｔ１）より高く、かつ、沸点（Ｔ３）より低い温度（Ｔ２）にまで上昇したのちに、シャッター２１１を防汚膜材料Ｍ１が開放される位置Ｐ２にまで移動させる。その後、防汚膜材料Ｍ１の温度を上昇させて、成膜工程を実施する。 Next, after raising the temperature of the antifouling film material M1 to a temperature (T2) higher than the boiling point (T3) -50 ° C. (T1) and lower than the boiling point (T3) of the antifouling film material M1 Then, the shutter 211 is moved to the position P2 where the antifouling film material M1 is opened. Thereafter, the temperature of the antifouling film material M1 is raised and a film forming process is performed.

　防汚膜材料Ｍ１として、ダイキン工業社製オプツール（登録商標）ＤＳＸを用いた場合は、成膜中に水晶振動子で防汚膜の堆積経過のモニタリングを行なうと、１８０度でダイキン工業社製オプツール（登録商標）ＤＳＸの蒸発が確認できるので、１８０度が沸点であると分かった。 When the OPTOOL (registered trademark) DSX manufactured by Daikin Industries, Ltd. is used as the antifouling film material M1, if the antifouling film deposition process is monitored with a crystal unit during film formation, it is manufactured by Daikin Industries, Ltd. at 180 degrees. Since evaporation of OPTOOL (registered trademark) DSX can be confirmed, it was found that the boiling point is 180 degrees.

　この場合、鋭意研究を行った結果、予備加熱工程は、１３０度（沸点（Ｔ３）－５０）より高温で行ない、その間はシャッター２１１をＰ１に移動させ、防汚膜材料Ｍ１に含有する不純物を放出させる。防汚膜材料Ｍ１は、シャッター２１１により覆われているため、防汚膜材料Ｍ１に含まれる不純物がディスプレイ用カバーガラス１０の表面１１に到達することはない。 In this case, as a result of diligent research, the preheating step is performed at a temperature higher than 130 degrees (boiling point (T3) -50), and during that time, the shutter 211 is moved to P1 to remove impurities contained in the antifouling film material M1. Release. Since the antifouling film material M1 is covered by the shutter 211, the impurities contained in the antifouling film material M1 do not reach the surface 11 of the display cover glass 10.

　この時、防汚膜材料Ｍ１の有効成分量のバラつきや、材料の使用量のバラつきによって、防汚膜の性能バラつきが見込まれるため、好ましくは沸点（Ｔ３）により近い１７０度に達するまで、防汚膜材料Ｍ１は、シャッター２１１により覆われているとよい。これにより、より性能の安定した成膜を行なうことが確認できた。 At this time, since the variation in the performance of the antifouling film is expected due to the variation in the amount of the active ingredient of the antifouling film material M1 and the variation in the amount of the material used, the antifouling film is preferably protected until it reaches 170 degrees closer to the boiling point (T3). The dirty film material M1 may be covered with the shutter 211. Thereby, it was confirmed that film formation with more stable performance was performed.

　予備加熱工程後、１７０度の温度でシャッター２１１をＰ１からＰ２に移動して、ディスプレイ用カバーガラス１０の表面１１に、フッ素系の防汚膜ＰＣを所望の膜厚まで成膜する成膜工程を実施する。膜厚さは、ｎｍオーダーで制御され、所望の膜厚とは、成膜後、ディスプレイ用カバーガラス１０が防汚膜ＰＣによって白濁しない程度の膜厚のことを言う。 After the preheating process, the shutter 211 is moved from P1 to P2 at a temperature of 170 degrees to form a fluorine-based antifouling film PC on the surface 11 of the display cover glass 10 to a desired film thickness. To implement. The film thickness is controlled on the order of nm, and the desired film thickness means a film thickness that does not cause the display cover glass 10 to become clouded by the antifouling film PC after film formation.

　急激な温度上昇による突沸での防汚膜ＰＣの膜質のばらつきを防ぐため、成膜時は温度勾配をつけて堆積速度を制御することが、防汚膜ＰＣの膜質を制御する上で好ましい。鋭意実験を重ねた結果、０．１度／ｓｅｃから３００度／ｓｅｃの温度上昇によって、防汚膜材料Ｍ１の温調を制御するとよい。これにより、防汚膜ＰＣの耐久性能の向上を図ることができる。 In order to prevent variation in the film quality of the antifouling film PC due to bumping due to a rapid temperature rise, it is preferable to control the deposition rate with a temperature gradient during film formation in order to control the film quality of the antifouling film PC. As a result of repeated experiments, it is preferable to control the temperature control of the antifouling film material M1 by increasing the temperature from 0.1 degrees / sec to 300 degrees / sec. Thereby, the durability performance of the antifouling film PC can be improved.

　予備加熱工程および成膜工程の真空チャンバー内の圧力は、１０^－９Ｐａ～１Ｐａの範囲であるとよい。 The pressure in the vacuum chamber in the preheating step and the film forming step is preferably in the range of 10 ⁻⁹ Pa to 1 Pa.

　このように、ディスプレイ用カバーガラス１０の表面１１にフッ素系の防汚膜ＰＣを成膜する工程において、予備加熱工程は、ディスプレイ用カバーガラス１０の表面１１に防汚膜材料Ｍ１から放出される不純物が到達しない状態で行なわれ、成膜工程は、ディスプレイ用カバーガラス１０の表面１１に、防汚膜材料Ｍ１から放出される防汚膜ＰＣの材料が到達する状態で行なわれる。 In this way, in the step of forming the fluorine-based antifouling film PC on the surface 11 of the display cover glass 10, the preheating step is released from the antifouling film material M1 on the surface 11 of the display cover glass 10. The film formation process is performed in a state in which the material of the antifouling film PC released from the antifouling film material M1 reaches the surface 11 of the display cover glass 10.

　具体的には、予備加熱工程および膜工程は、同一の第１の真空チャンバー２００の内部で行なわれ、予備加熱工程および前記成膜工程は、第１の真空チャンバー２００の内部が常に排気状態で行なわれ、表面１１と防汚膜材料Ｍ１との間には、シャッター２１１が配設され、シャッター２１１は、予備加熱工程においては、表面１１に、防汚膜材料Ｍ１から放出される不純物が到達しないように防汚膜材料Ｍ１を覆い、成膜工程においては、表面１１に、防汚膜材料Ｍ１から放出される防汚膜ＰＣの材料が到達するように、防汚膜材料Ｍ１を開放する。 Specifically, the preheating process and the film process are performed in the same first vacuum chamber 200, and the preheating process and the film forming process are always performed in an exhausted state in the first vacuum chamber 200. The shutter 211 is disposed between the surface 11 and the antifouling film material M1, and the shutter 211 has an impurity released from the antifouling film material M1 reaching the surface 11 in the preheating step. In the film forming process, the antifouling film material M1 is opened so that the material of the antifouling film PC released from the antifouling film material M1 reaches the surface 11. .

　これにより、防汚膜材料Ｍ１に含まれる不純物のディスプレイ用カバーガラス１０への付着を抑制することが可能な防汚膜ＰＣの成膜工程を含むディスプレイ用カバーガラス１０の製造方法を可能としている。 Thereby, the manufacturing method of the cover glass 10 for a display including the film-forming process of the antifouling film | membrane PC which can suppress the adhesion to the cover glass 10 for a display of the impurity contained in the antifouling film material M1 is enabled. .

　防汚膜材料Ｍ１から放出したガスが第１の真空チャンバー２００内に充満し、第１の真空チャンバー２００内の圧力（真空度）が一時的に悪くなり、防汚膜ＰＣの膜質がばらつく可能性がある場合には、一度圧力（真空度）を落ち着かせるために防汚膜材料Ｍ１の温度が１７０度に達した後、第１の真空チャンバー２００内からガスの放出が落ち着くまで待機することが好ましい。 The gas released from the antifouling film material M1 fills the first vacuum chamber 200, the pressure (degree of vacuum) in the first vacuum chamber 200 temporarily deteriorates, and the film quality of the antifouling film PC can vary. If there is a possibility, after the temperature of the antifouling film material M1 reaches 170 degrees in order to settle the pressure (vacuum degree) once, wait until the gas release from the first vacuum chamber 200 settles. Is preferred.

　（第２の真空チャンバー３００）
　次に、図４を参照して、ディスプレイ用カバーガラス１０の表面１１に防汚膜を成膜する際に用いられる第２の真空チャンバー３００の構成について説明する。図４は、実施の形態１における第２の真空チャンバー３００の構造を示す図である。 (Second vacuum chamber 300)
Next, with reference to FIG. 4, the structure of the 2nd vacuum chamber 300 used when forming an antifouling film | membrane on the surface 11 of the cover glass 10 for a display is demonstrated. FIG. 4 is a diagram showing the structure of the second vacuum chamber 300 in the first embodiment.

　この第２の真空チャンバー３００は、導入チャンバー３００Ａ、下地成膜チャンバー３００Ｂ、および、防汚成膜チャンバー３００Ｃと備えている。 The second vacuum chamber 300 includes an introduction chamber 300A, a base film forming chamber 300B, and an antifouling film forming chamber 300C.

導入チャンバー３００Ａは、第１ケーシング３０１を有し、第１ケーシング３０１の内部上方には、基板支持部材３１３を支持する第１支持部材３１５が設けられている。この導入チャンバー３００Ａにおいては、ディスプレイ用カバーガラス１０の被成膜面である表面１１が、後述の防汚膜材料収容容器３５７に対向するように、複数のディスプレイ用カバーガラス１０を基板支持部材３１３に保持される。 The introduction chamber 300 A includes a first casing 301, and a first support member 315 that supports the substrate support member 313 is provided above the inside of the first casing 301. In this introduction chamber 300A, a plurality of display cover glasses 10 are attached to the substrate support member 313 so that the surface 11 as the film formation surface of the display cover glass 10 faces an antifouling film material container 357 described later. Retained.

下地成膜チャンバー３００Ｂは、第２ケーシング３３１を有し、第２ケーシング３３１の内部上方には、基板支持部材３１３を支持する第２支持部材３４５が設けられている。第２ケーシング３３１の内部下方には、ベース３３３、ベース３３３に設けられたヒーター３３５、および、ヒーター３３５の上に載置される下地膜材料収容容器３３７を備えている。下地成膜チャンバー３００Ｂは、下地膜の膜厚を管理するための水晶モニター（不図示）を備えている。 The base film forming chamber 300 B has a second casing 331, and a second support member 345 that supports the substrate support member 313 is provided above the inside of the second casing 331. Below the second casing 331, a base 333, a heater 335 provided on the base 333, and a base film material storage container 337 placed on the heater 335 are provided. The base film forming chamber 300B includes a crystal monitor (not shown) for managing the film thickness of the base film.

　下地膜材料収容容器３３７は上方が開口された鍋状の容器である。ヒーター３３５は、図示しない温度制御部によって、所定の温度となるように制御されている。第１ケーシング３０１と第２ケーシング３３１との間は、基板支持部材３１３が移動可能設けられている。第１ケーシング３０１と第２ケーシング３３１との間には、第１開閉部材３７０が設けられている。 The base film material storage container 337 is a pan-shaped container having an upper opening. The heater 335 is controlled to have a predetermined temperature by a temperature control unit (not shown). A substrate support member 313 is movably provided between the first casing 301 and the second casing 331. A first opening / closing member 370 is provided between the first casing 301 and the second casing 331.

防汚成膜チャンバー３００Ｃは、第３ケーシング３５１を有し、第３ケーシング３５１の内部上方には、基板支持部材３１３を支持する第３支持部材３６５が設けられている。第３ケーシング３５１の内部下方には、ヒーター３５５、ヒーター３５５の上に載置される防汚膜材料収容容器３５７、防汚膜材料収容容器３５７内に蓄えられる防汚膜材料Ｍ１の温度を測定するとともに温度を制御する熱電対３５９とを備えている。 The antifouling film forming chamber 300 C has a third casing 351, and a third support member 365 that supports the substrate support member 313 is provided above the inside of the third casing 351. Below the third casing 351, the temperature of the antifouling film material M1 stored in the heater 355, the antifouling film material container 357 placed on the heater 355, and the antifouling film material container 357 is measured. And a thermocouple 359 for controlling the temperature.

　防汚膜材料収容容器３５７は上方が開口された鍋状の容器である。ヒーター３５５および熱電対３５９は、図示しない温度制御部によって、所定の温度となるように制御されている。第２ケーシング３３１と第３ケーシング３５１との間は、基板支持部材３１３が移動可能設けられている。第２ケーシング３３１と第３ケーシング３５１との間には、第２開閉部材３８０が設けられている。 The antifouling film material container 357 is a pan-shaped container having an upper opening. The heater 355 and the thermocouple 359 are controlled to have a predetermined temperature by a temperature control unit (not shown). A substrate support member 313 is movably provided between the second casing 331 and the third casing 351. A second opening / closing member 380 is provided between the second casing 331 and the third casing 351.

　この構成により、予備加熱工程において、表面１１と防汚膜材料Ｍ１との間が物理的に遮られた状態と、表面１１と防汚膜材料Ｍ１との間が物理的に開放された状態との選択が可能となる。 With this configuration, in the preheating step, a state where the surface 11 and the antifouling film material M1 are physically blocked and a state where the surface 11 and the antifouling film material M1 are physically opened are Can be selected.

　第１ケーシング３０１、第２ケーシング３３１、および第３ケーシング３５１は、表面１１に防汚膜ＰＣを成膜する工程においては、常に排気状態が維持されている。排気口の図示は省略している。第１ケーシング３０１、第２ケーシング３３１、および第３ケーシング３５１には、ロードロック式のチャンバーを用いるとよい。 The first casing 301, the second casing 331, and the third casing 351 are always kept in an exhaust state in the step of forming the antifouling film PC on the surface 11. The exhaust port is not shown. As the first casing 301, the second casing 331, and the third casing 351, a load-lock chamber may be used.

　（他のガラス製品の製造方法）
　上記構成を備える第２の真空チャンバー３００を用いた場合の、本実施の形態におけるディスプレイ用カバーガラス１０の製造方法に関し、フッ素系化合物を含有する防汚膜材料Ｍ１を用いた真空蒸着法により、ディスプレイ用カバーガラス１０の表面１１にフッ素系の防汚膜ＰＣを成膜する工程について以下する。 (Manufacturing method of other glass products)
In the case of using the second vacuum chamber 300 having the above-described configuration, the manufacturing method of the display cover glass 10 in the present embodiment, by the vacuum deposition method using the antifouling film material M1 containing a fluorine-based compound, The process of forming the fluorine-based antifouling film PC on the surface 11 of the display cover glass 10 will be described below.

導入チャンバー３００Ａ内に、ディスプレイ用カバーガラス１０の被成膜面である表面１１が、防汚膜材料収容容器３５７に対向するように、複数のディスプレイ用カバーガラス１０を基板支持部材３１３に保持させた状態で、第１支持部材３１５に基板支持部材３１３を載置する（ガラス基板の準備）。 In the introduction chamber 300 A, a plurality of display cover glasses 10 are held by the substrate support member 313 so that the surface 11 as a film formation surface of the display cover glass 10 faces the antifouling film material container 357. In this state, the substrate support member 313 is placed on the first support member 315 (preparation of a glass substrate).

　次に、第１開閉部材３７０を開放して、基板支持部材３１３を下地成膜チャンバー３００Ｂに移送する（図４中Ｔ１方向）。次に、ディスプレイ用カバーガラス１０の温度を室温からフッ素系化合物の沸点未満の範囲で加熱する。フッ素系化合物の性能バラツキの観点から、５０度～８０度の範囲でディスプレイ用カバーガラス１０を加熱する。予めディスプレイ用カバーガラス１０の表面１１に、下地膜ＵＣとしてＳｉＯ_２膜を５ｎｍ～２００ｎｍ、より好ましくは１０ｎｍ～１００ｎｍ堆積する。 Next, the first opening / closing member 370 is opened, and the substrate support member 313 is transferred to the base film forming chamber 300B (direction T1 in FIG. 4). Next, the temperature of the display cover glass 10 is heated in the range from room temperature to less than the boiling point of the fluorine compound. From the viewpoint of variation in performance of the fluorine compound, the display cover glass 10 is heated in the range of 50 to 80 degrees. A SiO ₂ film is deposited in advance on the surface 11 of the display cover glass 10 as a base film UC in a range of 5 nm to 200 nm, more preferably 10 nm to 100 nm.

　一方、防汚成膜チャンバー３００Ｃにおいては、防汚膜材料Ｍ１に含有する不純物を放出させるための予備加熱工程として、フッ素系化合物である防汚膜材料Ｍ１の温度が、防汚膜材料Ｍ１の沸点（Ｔ３）－５０度の温度（Ｔ１）より高く、かつ、沸点（Ｔ３）より低い温度（Ｔ２）にまで加熱する。この温度帯域で加熱する理由は、上述と同じである。 On the other hand, in the antifouling film forming chamber 300C, as a preheating step for releasing impurities contained in the antifouling film material M1, the temperature of the antifouling film material M1, which is a fluorine compound, is the same as that of the antifouling film material M1. Boiling point (T3) —heats to a temperature (T2) higher than the temperature (T1) of −50 degrees and lower than the boiling point (T3). The reason for heating in this temperature range is the same as described above.

　次に、防汚膜材料Ｍ１の温度を、防汚膜材料Ｍ１の沸点（Ｔ３）－５０度の温度（Ｔ１）より高く、かつ、沸点（Ｔ３）より低い温度（Ｔ２）にまで上昇したのちに、第２開閉部材３８０を開放して、基板支持部材３１３を防汚成膜チャンバー３００Ｃに移送する（図４中Ｔ２方向）。その後、防汚膜材料Ｍ１の温度を沸点以上に上昇させて、防汚成膜チャンバー３００Ｃ内で成膜工程を実施する。 Next, after raising the temperature of the antifouling film material M1 to a temperature (T2) higher than the boiling point (T3) -50 ° C. (T1) and lower than the boiling point (T3) of the antifouling film material M1 Then, the second opening / closing member 380 is opened, and the substrate support member 313 is transferred to the antifouling film formation chamber 300C (direction T2 in FIG. 4). Thereafter, the temperature of the antifouling film material M1 is raised to the boiling point or higher, and the film forming process is performed in the antifouling film forming chamber 300C.

　基板支持部材３１３の下地成膜チャンバー３００Ｂから防汚成膜チャンバー３００Ｃへの移送は、防汚成膜チャンバー３００Ｃ内の真空状態が維持された状態で、防汚成膜チャンバー３００Ｃ内に基板支持部材３１３が導入されるとよい。予備加熱工程および成膜工程における真空チャンバー内の圧力は、１０^－９Ｐａ～１Ｐａの範囲であるとよい。成膜時における成膜条件および温調制御は、上記と同じである。 The substrate supporting member 313 is transferred from the base film forming chamber 300B to the antifouling film forming chamber 300C in a state where the vacuum state in the antifouling film forming chamber 300C is maintained, and the substrate supporting member is placed in the antifouling film forming chamber 300C. 313 may be introduced. The pressure in the vacuum chamber in the preheating step and the film forming step is preferably in the range of 10 ⁻⁹ Pa to 1 Pa. Film formation conditions and temperature control during film formation are the same as described above.

　具体的には、予備加熱工程および成膜工程は、同一の防汚成膜チャンバー３００Ｃの内部で行なわれ、予備加熱工程および成膜工程は、防汚成膜チャンバー３００Ｃの内部が常に排気状態で実施され、予備加熱工程は、ディスプレイ用カバーガラス１０が導入されていない防汚成膜チャンバー３００Ｃ内で行なわれることにより、防汚膜材料Ｍ１に含有する不純物が放出される工程を含み、成膜工程は、予備加熱工程の後に防汚成膜チャンバー３００Ｃ内の真空状態が維持された状態で、防汚成膜チャンバー３００Ｃ内にディスプレイ用カバーガラス１０が導入される工程を含んでいる。 Specifically, the preheating step and the film forming step are performed inside the same antifouling film forming chamber 300C, and the preheating step and the film forming step are always performed in an exhausted state inside the antifouling film forming chamber 300C. The preheating step is performed, and includes a step of releasing impurities contained in the antifouling film material M1 by being performed in the antifouling film forming chamber 300C in which the display cover glass 10 is not introduced. The process includes a process in which the display cover glass 10 is introduced into the antifouling film forming chamber 300C in a state where the vacuum state in the antifouling film forming chamber 300C is maintained after the preheating process.

　防汚膜材料Ｍ１から放出したガスが防汚成膜チャンバー３００Ｃ内に充満し、防汚成膜チャンバー３００Ｃの圧力（真空度）が一時的に悪くなり、防汚膜ＰＣの膜質がばらつく可能性がある場合には、一度圧力（真空度）を落ち着かせるために防汚膜材料Ｍ１の温度が１７０度に達した後、防汚成膜チャンバー３００Ｃ内からガスの放出が落ち着くまで待機することが好ましい。 The gas released from the antifouling film material M1 is filled in the antifouling film forming chamber 300C, the pressure (vacuum degree) of the antifouling film forming chamber 300C is temporarily deteriorated, and the film quality of the antifouling film PC may vary. If there is, the temperature of the antifouling film material M1 reaches 170 degrees in order to settle the pressure (vacuum degree) once, and then waiting until the release of gas from the antifouling film forming chamber 300C is settled. preferable.

　（第３の真空チャンバー４００）
　次に、図５を参照して、ディスプレイ用カバーガラス１０の表面１１に防汚膜を成膜する際に用いられる第３の真空チャンバー４００の構成について説明する。図５は、実施の形態１における第３の真空チャンバー４００の構造を示す図である。 (Third vacuum chamber 400)
Next, with reference to FIG. 5, the structure of the 3rd vacuum chamber 400 used when forming an antifouling film | membrane on the surface 11 of the cover glass 10 for a display is demonstrated. FIG. 5 is a diagram showing a structure of the third vacuum chamber 400 in the first embodiment.

　上記第２の真空チャンバー３００の構成と比較した場合、予備加熱チャンバー３００Ｄが付加されており、導入チャンバー３００Ａ、下地成膜チャンバー３００Ｂ、および、防汚成膜チャンバー３００Ｃの構成は同じである。 When compared with the configuration of the second vacuum chamber 300, a preheating chamber 300D is added, and the configuration of the introduction chamber 300A, the base film forming chamber 300B, and the antifouling film forming chamber 300C is the same.

予備加熱チャンバー３００Ｄは、第４ケーシング３７１を有し、第４ケーシング３７１の内部下方には、ヒーター３５５、および、ヒーター３５５の上に載置される防汚膜材料収容容器３５７を備えている。 The preheating chamber 300 D has a fourth casing 371, and includes a heater 355 and an antifouling film material container 357 placed on the heater 355 below the fourth casing 371.

　第３ケーシング３５１と第４ケーシング３７１との間は、ヒーター３５５および防汚膜材料収容容器３５７が移動可能設けられている。第３ケーシング３５１と第４ケーシング３７１との間には、第３開閉部材３９０が設けられている。 Between the third casing 351 and the fourth casing 371, a heater 355 and an antifouling film material container 357 are movably provided. A third opening / closing member 390 is provided between the third casing 351 and the fourth casing 371.

　第４ケーシング３７１は、表面１１に防汚膜ＰＣを成膜する工程においては、常に排気状態が維持されている。排気口の図示は省略している。 The exhaust state of the fourth casing 371 is always maintained in the step of forming the antifouling film PC on the surface 11. The exhaust port is not shown.

　（他のガラス製品の製造方法）
　上記構成を備える第３の真空チャンバー４００を用いた場合の、本実施の形態におけるディスプレイ用カバーガラス１０の製造方法に関し、フッ素系化合物を含有する防汚膜材料Ｍ１を用いた真空蒸着法により、ディスプレイ用カバーガラス１０の表面１１にフッ素系の防汚膜ＰＣを成膜する工程について以下する。 (Manufacturing method of other glass products)
In the case of using the third vacuum chamber 400 having the above-described configuration, the manufacturing method of the display cover glass 10 in the present embodiment, by the vacuum deposition method using the antifouling film material M1 containing a fluorine-based compound, The process of forming the fluorine-based antifouling film PC on the surface 11 of the display cover glass 10 will be described below.

　基本的な製造方法は、第２の真空チャンバー３００を用いた場合と同様であるが、予備加熱チャンバー３００Ｄにおいて、防汚膜材料Ｍ１に含有する不純物を放出させるための予備加熱工程として、フッ素系化合物である防汚膜材料Ｍ１の温度が、防汚膜材料Ｍ１の沸点（Ｔ３）－５０度の温度（Ｔ１）より高く、かつ、沸点（Ｔ３）より低い温度（Ｔ２）にまで加熱する。この温度帯域で加熱する理由は、上述と同じである。 The basic manufacturing method is the same as that in the case where the second vacuum chamber 300 is used. In the preheating chamber 300D, as a preheating step for releasing impurities contained in the antifouling film material M1, a fluorine-based process is performed. The temperature of the antifouling film material M1, which is a compound, is heated to a temperature (T2) higher than the boiling point (T3) -50 ° C. (T1) and lower than the boiling point (T3) of the antifouling film material M1. The reason for heating in this temperature range is the same as described above.

　次に、第３開閉部材３９０を開放して、ヒーター３５５、および、防汚膜材料収容容器３５７を、防汚成膜チャンバー３００Ｃに移送して（図５中Ｔ３）、防汚膜材料Ｍ１の温度を、防汚膜材料Ｍ１の沸点（Ｔ３）－５０度の温度（Ｔ１）より高く、かつ、沸点（Ｔ３）より低い温度（Ｔ２）にまで上昇させる。その後、第２開閉部材３８０を開放して、基板支持部材３１３を防汚成膜チャンバー３００Ｃに移送する（図４中Ｔ２方向）。その後、防汚膜材料Ｍ１の温度を上昇させて、防汚成膜チャンバー３００Ｃ内で成膜工程を実施する。 Next, the third opening / closing member 390 is opened, the heater 355 and the antifouling film material container 357 are transferred to the antifouling film forming chamber 300C (T3 in FIG. 5), and the antifouling film material M1 is transferred. The temperature is raised to a temperature (T2) higher than the boiling point (T3) -50 ° C. (T1) of the antifouling film material M1 and lower than the boiling point (T3). Thereafter, the second opening / closing member 380 is opened, and the substrate support member 313 is transferred to the antifouling film forming chamber 300C (T2 direction in FIG. 4). Thereafter, the temperature of the antifouling film material M1 is raised, and the film forming process is performed in the antifouling film forming chamber 300C.

　防汚膜材料収容容器３５７の防汚成膜チャンバー３００Ｃへの移送、および、基板支持部材３１３の下地成膜チャンバー３００Ｂから防汚成膜チャンバー３００Ｃへの移送は、防汚成膜チャンバー３００Ｃ内の真空状態が維持された状態で、防汚成膜チャンバー３００Ｃ内に基板支持部材３１３が導入されるとよい。予備加熱工程および成膜工程の真空チャンバー内の圧力は、１０^－９Ｐａ～１Ｐａの範囲であるとよい。成膜時における成膜条件および温調制御は、上記と同じである。 The transfer of the antifouling film material container 357 to the antifouling film forming chamber 300C and the transfer of the substrate support member 313 from the base film forming chamber 300B to the antifouling film forming chamber 300C are performed in the antifouling film forming chamber 300C. The substrate support member 313 is preferably introduced into the antifouling film forming chamber 300C while the vacuum state is maintained. The pressure in the vacuum chamber in the preheating step and the film forming step is preferably in the range of 10 ⁻⁹ Pa to 1 Pa. Film formation conditions and temperature control during film formation are the same as described above.

　具体的には、予備加熱工程は、予備加熱チャンバー３００Ｄで行なわれ、成膜工程は、防汚成膜チャンバー３００Ｃで行なわれ、予備加熱工程および成膜工程は、予備加熱チャンバー３００Ｄおよび防汚成膜チャンバー３００Ｃの内部が常に排気状態で実施され、予備加熱工程は、ディスプレイ用カバーガラス１０が導入された防汚成膜チャンバー３００Ｃとは異なる予備加熱チャンバー３００Ｄで行なわれることにより、防汚膜材料Ｍ１に含有する不純物が放出され工程を含み、成膜工程は、予備加熱工程の後に防汚成膜チャンバー３００Ｃ内に、予備加熱工程が終了した防汚膜材料Ｍ１が導入される工程を含んでいる。 Specifically, the preheating process is performed in the preheating chamber 300D, the film forming process is performed in the antifouling film forming chamber 300C, and the preheating process and the film forming process are performed in the preheating chamber 300D and the antifouling process. The inside of the film chamber 300C is always evacuated, and the preheating process is performed in a preheating chamber 300D different from the antifouling film forming chamber 300C into which the display cover glass 10 is introduced. Impurities contained in M1 are released, and the film forming process includes a process in which the antifouling film material M1 after the preheating process is introduced into the antifouling film forming chamber 300C after the preheating process. Yes.

　温度管理は、常時モニタリングしなくても、事前に条件を設定して成膜を行なってよい。 The temperature management may be performed by setting the conditions in advance without always monitoring.

　（実施例）
　次に、上記第１の真空チャンバー２００を用いて実施したガラス製品の製造方法の実施例１１から１４、および、第２の真空チャンバー３００を用いて実施したガラス製品の製造方法の実施例１５から１６について以下説明する。 (Example)
Next, Examples 11 to 14 of the glass product manufacturing method performed using the first vacuum chamber 200 and Examples 15 to 14 of the glass product manufacturing method performed using the second vacuum chamber 300 are used. 16 will be described below.

　実施例１５から１６の実施例の結果は、第３の真空チャンバー４００を用いた場合にも同様である。比較例１１から１５を実施した。実施例１１から１６および比較例１１から１５において用いた防汚膜材料Ｍ１は、ダイキン社製の『オプツール（登録商標）ＤＳＸ』である。 The results of Examples 15 to 16 are the same when the third vacuum chamber 400 is used. Comparative examples 11 to 15 were carried out. The antifouling film material M1 used in Examples 11 to 16 and Comparative Examples 11 to 15 is “OPTOOL (registered trademark) DSX” manufactured by Daikin.

　各実施例および比較例における各種成膜条件は、図６から図１５に示すとおりである。
　（実施例１１）
　６０度のチャンバー雰囲気内で、まず下地膜ＵＣとしてガラス基板の表面にＳｉＯ_２を３０ｎｍ堆積させた。ガラス基板として、硬さ９Ｈの白板ガラスＳを用いた。次に防汚膜ＰＣの成膜を行なった。防汚膜ＰＣの成膜条件は、まず予備加熱工程として、防汚膜材料Ｍ１をシャッター２１１で覆い、１６０度まで防汚膜材料Ｍ１を加熱した。その後、シャッター２１１を移動し防汚膜材料Ｍ１を開放して、さらに防汚膜材料Ｍ１を３００度まで加熱した。シャッター開放時間と防汚膜材料温度との関係を図７に示す。 Various film forming conditions in each example and comparative example are as shown in FIGS.
(Example 11)
In a 60 degree chamber atmosphere, first, SiO ₂ was deposited to a thickness of 30 nm on the surface of the glass substrate as the base film UC. A white plate glass S having a hardness of 9H was used as the glass substrate. Next, an antifouling film PC was formed. As the film forming conditions for the antifouling film PC, first, as a preheating step, the antifouling film material M1 was covered with the shutter 211, and the antifouling film material M1 was heated to 160 degrees. Thereafter, the shutter 211 was moved to release the antifouling film material M1, and the antifouling film material M1 was further heated to 300 degrees. FIG. 7 shows the relationship between the shutter opening time and the antifouling film material temperature.

　図６に示すように、防汚膜ＰＣの成膜後のガラス基板表面の摩耗試験のキズ本数は０本であった。摩耗試験後の接触角は１１４．２度であった。よって、良好な耐久性能を備えるガラス基板が得られた。 As shown in FIG. 6, the number of scratches in the abrasion test on the glass substrate surface after the formation of the antifouling film PC was zero. The contact angle after the wear test was 114.2 degrees. Therefore, the glass substrate provided with favorable durability performance was obtained.

　摩耗試験は、摩耗試験機（商品名「トライボギア」（新東科学社製））を用い、スチールウール＃００００番、１ｃｍ^２に対して荷重２ｋｇで摩耗２０００回摩耗し、摩耗後に油性マジックで摩耗面を擦りキズの本数と純水の接触角を測定した。サンプル試作は１条件につき１０バッチ行ない、その平均値をとり評価を行なった。温度の測定は、防汚膜材料Ｍ１を入れる防汚膜材料収容容器に熱電対を接触させて測定した。各ガラス基板は成膜後、２４時間室温放置し、その後測定を行なった。以下の実施例および比較例でも同様である。 The wear test was performed using a wear tester (trade name “Tribogear” (manufactured by Shinto Kagaku Co., Ltd.)), and the steel wool # 0000, 1 cm ² , was worn 2000 times with a load of 2 kg, and was worn with oily magic after wear. The surface was rubbed and the number of scratches and the contact angle of pure water were measured. The sample trial production was performed 10 batches per condition, and the average value was evaluated. The temperature was measured by bringing a thermocouple into contact with the antifouling film material container into which the antifouling film material M1 was placed. Each glass substrate was allowed to stand at room temperature for 24 hours after film formation, and then measured. The same applies to the following examples and comparative examples.

　（実施例１２）
　６０度のチャンバー雰囲気内で、まず下地膜ＵＣとしてガラス基板の表面にＳｉＯ_２を３０ｎｍ堆積させた。ガラス基板として、硬さ９Ｈの白板ガラスＳを用いた。次に防汚膜ＰＣの成膜を行なった。防汚膜ＰＣの成膜条件は、まず予備加熱工程として、防汚膜材料Ｍ１をシャッター２１１で覆い、１７０度まで防汚膜材料Ｍ１を加熱した。その後、シャッター２１１を移動し防汚膜材料Ｍ１を開放して、さらに防汚膜材料Ｍ１を３００度まで加熱した。シャッター開放時間と防汚膜材料温度との関係を図８に示す。 Example 12
In a 60 degree chamber atmosphere, first, SiO ₂ was deposited to a thickness of 30 nm on the surface of the glass substrate as the base film UC. A white plate glass S having a hardness of 9H was used as the glass substrate. Next, an antifouling film PC was formed. As the film forming conditions for the antifouling film PC, first, as a preheating step, the antifouling film material M1 was covered with the shutter 211, and the antifouling film material M1 was heated to 170 degrees. Thereafter, the shutter 211 was moved to release the antifouling film material M1, and the antifouling film material M1 was further heated to 300 degrees. FIG. 8 shows the relationship between the shutter opening time and the antifouling film material temperature.

　図６に示すように、防汚膜ＰＣの成膜後のガラス基板表面の摩耗試験のキズ本数は０本であった。摩耗試験後の接触角は１１３．９度であった。よって、良好な耐久性能を備えるガラス基板が得られた。 As shown in FIG. 6, the number of scratches in the abrasion test on the glass substrate surface after the formation of the antifouling film PC was zero. The contact angle after the abrasion test was 113.9 degrees. Therefore, the glass substrate provided with favorable durability performance was obtained.

　（実施例１３）
　６０度のチャンバー雰囲気内で、まず下地膜ＵＣとしてガラス基板の表面にＳｉＯ_２を３０ｎｍ堆積させた。ガラス基板として、硬さ９Ｈの白板ガラスＳを用いた。次に防汚膜ＰＣの成膜を行なった。防汚膜ＰＣの成膜条件は、まず予備加熱工程として、防汚膜材料Ｍ１をシャッター２１１で覆い、１６０度まで防汚膜材料Ｍ１を加熱した。 (Example 13)
In a 60 degree chamber atmosphere, first, SiO ₂ was deposited to a thickness of 30 nm on the surface of the glass substrate as the base film UC. A white plate glass S having a hardness of 9H was used as the glass substrate. Next, an antifouling film PC was formed. As the film forming conditions for the antifouling film PC, first, as a preheating step, the antifouling film material M1 was covered with the shutter 211, and the antifouling film material M1 was heated to 160 degrees.

　その後、７０度まで防汚膜材料Ｍ１の温度を下げてチャンバー内の圧力（真空度）を落ち着かせた。その後、さらに防汚膜材料Ｍ１を加熱させ、沸点以下の温度でシャッター２１１を移動し防汚膜材料Ｍ１を開放して、さらに防汚膜材料Ｍ１を３００度まで加熱した。シャッター開放時間と防汚膜材料温度との関係を図９に示す。 Thereafter, the temperature of the antifouling film material M1 was lowered to 70 degrees to calm the pressure (vacuum degree) in the chamber. Thereafter, the antifouling film material M1 was further heated, the shutter 211 was moved at a temperature below the boiling point to release the antifouling film material M1, and the antifouling film material M1 was further heated to 300 degrees. FIG. 9 shows the relationship between the shutter opening time and the antifouling film material temperature.

　図６に示すように、防汚膜ＰＣの成膜後のガラス基板表面の摩耗試験のキズ本数は０本であった。摩耗試験後の接触角は１１４．１度であった。よって、良好な耐久性能を備えるガラス基板が得られた。 As shown in FIG. 6, the number of scratches in the abrasion test on the glass substrate surface after the formation of the antifouling film PC was zero. The contact angle after the wear test was 114.1 degrees. Therefore, the glass substrate provided with favorable durability performance was obtained.

　（実施例１４）
　６０度のチャンバー雰囲気内で、まず下地膜ＵＣとしてガラス基板の表面にＳｉＯ_２を３０ｎｍ堆積させた。ガラス基板として、硬さ９Ｈの白板ガラスＳを用いた。次に防汚膜ＰＣの成膜を行なった。防汚膜ＰＣの成膜条件は、まず予備加熱工程として、防汚膜材料Ｍ１をシャッター２１１で覆い、１６０度まで防汚膜材料Ｍ１を加熱した。その直後、シャッター２１１を移動し防汚膜材料Ｍ１を開放して、さらに防汚膜材料Ｍ１を３００度まで加熱した。シャッター開放時間と防汚膜材料温度との関係を図１０に示す。 (Example 14)
In a 60 degree chamber atmosphere, first, SiO ₂ was deposited to a thickness of 30 nm on the surface of the glass substrate as the base film UC. A white plate glass S having a hardness of 9H was used as the glass substrate. Next, an antifouling film PC was formed. As the film forming conditions for the antifouling film PC, first, as a preheating step, the antifouling film material M1 was covered with the shutter 211, and the antifouling film material M1 was heated to 160 degrees. Immediately thereafter, the shutter 211 was moved to release the antifouling film material M1, and the antifouling film material M1 was further heated to 300 degrees. FIG. 10 shows the relationship between the shutter opening time and the antifouling film material temperature.

　図６に示すように、防汚膜ＰＣの成膜後のガラス基板表面の摩耗試験のキズ本数は０本であった。摩耗試験後の接触角は１１３．７度であった。よって、良好な耐久性能を備えるガラス基板が得られた。 As shown in FIG. 6, the number of scratches in the abrasion test on the glass substrate surface after the formation of the antifouling film PC was zero. The contact angle after the wear test was 113.7 degrees. Therefore, the glass substrate provided with favorable durability performance was obtained.

　（比較例１１）
　６０度のチャンバー雰囲気内で、まず下地膜ＵＣとしてガラス基板の表面にＳｉＯ_２を３０ｎｍ堆積させた。ガラス基板として、硬さ９Ｈの白板ガラスＳを用いた。次に防汚膜ＰＣの成膜を行なった。防汚膜ＰＣの成膜条件は、予備加熱工程は実施せずに、３００度まで防汚膜材料Ｍ１を加熱した。シャッター開放時間と防汚膜材料温度との関係を図１１に示す。 (Comparative Example 11)
In a 60 degree chamber atmosphere, first, SiO ₂ was deposited to a thickness of 30 nm on the surface of the glass substrate as the base film UC. A white plate glass S having a hardness of 9H was used as the glass substrate. Next, an antifouling film PC was formed. As for the film formation conditions of the antifouling film PC, the antifouling film material M1 was heated to 300 degrees without performing the preheating step. FIG. 11 shows the relationship between the shutter opening time and the antifouling film material temperature.

　図６に示すように、防汚膜ＰＣの成膜後のガラス基板表面の摩耗試験のキズ本数は５本以上であった。摩耗試験後の接触角は１０３．４度であった。よって、良好な耐久性能を備えるガラス基板を得ることはできなかった。 As shown in FIG. 6, the number of scratches in the abrasion test on the glass substrate surface after the formation of the antifouling film PC was 5 or more. The contact angle after the wear test was 103.4 degrees. Therefore, a glass substrate having good durability could not be obtained.

　（比較例１２）
　６０度のチャンバー雰囲気内で、まず下地膜ＵＣとしてガラス基板の表面にＳｉＯ_２を３０ｎｍ堆積させた。ガラス基板として、硬さ９Ｈの白板ガラスＳを用いた。次に防汚膜ＰＣの成膜を行なった。防汚膜ＰＣの成膜条件は、まず予備加熱工程として、防汚膜材料Ｍ１をシャッター２１１で覆い、１３０度まで防汚膜材料Ｍ１を加熱した。その後、シャッター２１１を移動し防汚膜材料Ｍ１を開放して、さらに防汚膜材料Ｍ１を３００度まで加熱した。シャッター開放時間と防汚膜材料温度との関係を図１２に示す。 (Comparative Example 12)
In a 60 degree chamber atmosphere, first, SiO ₂ was deposited to a thickness of 30 nm on the surface of the glass substrate as the base film UC. A white plate glass S having a hardness of 9H was used as the glass substrate. Next, an antifouling film PC was formed. As the film forming conditions for the antifouling film PC, first, as a preheating step, the antifouling film material M1 was covered with the shutter 211, and the antifouling film material M1 was heated to 130 degrees. Thereafter, the shutter 211 was moved to release the antifouling film material M1, and the antifouling film material M1 was further heated to 300 degrees. FIG. 12 shows the relationship between the shutter opening time and the antifouling film material temperature.

　図６に示すように、防汚膜ＰＣの成膜後のガラス基板表面の摩耗試験のキズ本数は５本以上であった。摩耗試験後の接触角は１０２．３度であった。よって、良好な耐久性能を備えるガラス基板を得ることはできなかった。 As shown in FIG. 6, the number of scratches in the abrasion test on the glass substrate surface after the formation of the antifouling film PC was 5 or more. The contact angle after the wear test was 102.3 degrees. Therefore, a glass substrate having good durability could not be obtained.

　（比較例１３）
　６０度のチャンバー雰囲気内で、まず下地膜ＵＣとしてガラス基板の表面にＳｉＯ_２を３０ｎｍ堆積させた。ガラス基板として、硬さ９Ｈの白板ガラスＳを用いた。次に防汚膜ＰＣの成膜を行なった。防汚膜ＰＣの成膜条件は、まず予備加熱工程として、防汚膜材料Ｍ１をシャッター２１１で覆い、２００度まで防汚膜材料Ｍ１を加熱した。その後、シャッター２１１を移動し防汚膜材料Ｍ１を開放して、さらに防汚膜材料Ｍ１を３００度まで加熱した。シャッター開放時間と防汚膜材料温度との関係を図１３に示す。 (Comparative Example 13)
In a 60 degree chamber atmosphere, first, SiO ₂ was deposited to a thickness of 30 nm on the surface of the glass substrate as the base film UC. A white plate glass S having a hardness of 9H was used as the glass substrate. Next, an antifouling film PC was formed. As the film forming conditions for the antifouling film PC, first, as a preheating step, the antifouling film material M1 was covered with the shutter 211, and the antifouling film material M1 was heated to 200 degrees. Thereafter, the shutter 211 was moved to release the antifouling film material M1, and the antifouling film material M1 was further heated to 300 degrees. FIG. 13 shows the relationship between the shutter opening time and the antifouling film material temperature.

　（実施例１５）
　まず、ガラス基板が導入されていない防汚成膜チャンバー３００Ｃで、予備加熱工程として１７０度まで防汚膜材料Ｍ１を加熱した。並行して、ガラス基板が導入されている下地成膜チャンバー３００ＢでＳｉＯ_２を３０ｎｍ堆積させ、予備加熱と下地膜ＵＣの形成が共に終了した後に、ガラス基板を防汚成膜チャンバー３００Ｃに搬送し、防汚膜材料Ｍ１を３００度まで加熱させて成膜工程とした。 (Example 15)
First, the antifouling film material M1 was heated to 170 degrees as a preheating step in the antifouling film forming chamber 300C into which the glass substrate was not introduced. In parallel, 30 nm of SiO ₂ is deposited in the base film formation chamber 300B into which the glass substrate is introduced, and after both preheating and formation of the base film UC are completed, the glass substrate is transferred to the antifouling film formation chamber 300C. Then, the antifouling film material M1 was heated to 300 degrees to form a film forming process.

　図１４および図１５に示すように、防汚膜ＰＣの成膜後のガラス基板表面の摩耗試験のキズ本数は０本であった。摩耗試験後の接触角は１１３．２度であった。よって、良好な耐久性能を備えるガラス基板を得ることができた。 As shown in FIGS. 14 and 15, the number of scratches in the abrasion test on the glass substrate surface after the formation of the antifouling film PC was zero. The contact angle after the wear test was 113.2 degrees. Therefore, the glass substrate provided with favorable durability performance was able to be obtained.

　（実施例１６）
　まず、ガラス基板が導入されていない防汚成膜チャンバー３００Ｃで、予備加熱工程として１５０度まで防汚膜材料Ｍ１を加熱した。並行して、ガラス基板が導入されている下地成膜チャンバー３００ＢでＳｉＯ_２を３０ｎｍ堆積させ、予備加熱と下地膜ＵＣの形成が共に終了した後に、ガラス基板を防汚成膜チャンバー３００Ｃに搬送し、防汚膜材料Ｍ１を３００度まで加熱させて成膜工程とした。 (Example 16)
First, the antifouling film material M1 was heated to 150 degrees as a preheating step in the antifouling film forming chamber 300C into which the glass substrate was not introduced. In parallel, 30 nm of SiO ₂ is deposited in the base film formation chamber 300B into which the glass substrate is introduced, and after both preheating and formation of the base film UC are completed, the glass substrate is transferred to the antifouling film formation chamber 300C. Then, the antifouling film material M1 was heated to 300 degrees to form a film forming process.

　図１４および図１５に示すように、防汚膜ＰＣの成膜後のガラス基板表面の摩耗試験のキズ本数は０本であった。摩耗試験後の接触角は１１４．６度であった。よって、良好な耐久性能を備えるガラス基板を得ることができた。 As shown in FIGS. 14 and 15, the number of scratches in the abrasion test on the glass substrate surface after the formation of the antifouling film PC was zero. The contact angle after the abrasion test was 114.6 degrees. Therefore, the glass substrate provided with favorable durability performance was able to be obtained.

　（比較例１４）
　まず、ガラス基板が導入されていない防汚成膜チャンバー３００Ｃで、予備加熱工程として１３０度まで防汚膜材料Ｍ１を加熱した。並行して、ガラス基板が導入されている下地成膜チャンバー３００ＢでＳｉＯ_２を３０ｎｍ堆積させ、予備加熱と下地膜ＵＣの形成が共に終了した後に、ガラス基板を防汚成膜チャンバー３００Ｃに搬送し、防汚膜材料Ｍ１を３００度まで加熱させて成膜工程とした。 (Comparative Example 14)
First, the antifouling film material M1 was heated to 130 degrees as a preheating step in the antifouling film forming chamber 300C into which the glass substrate was not introduced. In parallel, 30 nm of SiO ₂ is deposited in the base film formation chamber 300B into which the glass substrate is introduced, and after both preheating and formation of the base film UC are completed, the glass substrate is transferred to the antifouling film formation chamber 300C. Then, the antifouling film material M1 was heated to 300 degrees to form a film forming process.

　図１４および図１５に示すように、防汚膜ＰＣの成膜後のガラス基板表面の摩耗試験のキズ本数は２本であった。摩耗試験後の接触角は１０９．３度であった。よって、良好な耐久性能を備えるガラス基板を得ることができなかった。 As shown in FIGS. 14 and 15, the number of scratches in the abrasion test on the glass substrate surface after the antifouling film PC was formed was two. The contact angle after the wear test was 109.3 degrees. Therefore, a glass substrate with good durability could not be obtained.

　（比較例１５）
　まず、ガラス基板が導入されていない防汚成膜チャンバー３００Ｃで、予備加熱工程として２００度まで防汚膜材料Ｍ１を加熱した。並行して、ガラス基板が導入されている下地成膜チャンバー３００ＢでＳｉＯ_２を３０ｎｍ堆積させ、予備加熱と下地膜ＵＣの形成が共に終了した後に、ガラス基板を防汚成膜チャンバー３００Ｃに搬送し、防汚膜材料Ｍ１を３００度まで加熱させて成膜工程とした。 (Comparative Example 15)
First, the antifouling film material M1 was heated to 200 degrees as a preheating step in the antifouling film forming chamber 300C into which the glass substrate was not introduced. In parallel, 30 nm of SiO ₂ is deposited in the base film formation chamber 300B into which the glass substrate is introduced, and after both preheating and formation of the base film UC are completed, the glass substrate is transferred to the antifouling film formation chamber 300C. Then, the antifouling film material M1 was heated to 300 degrees to form a film forming process.

　図１４および図１５に示すように、防汚膜ＰＣの成膜後のガラス基板表面の摩耗試験のキズ本数は３本であった。摩耗試験後の接触角は１０５．３度であった。よって、良好な耐久性能を備えるガラス基板を得ることができなかった。 As shown in FIGS. 14 and 15, the number of scratches in the abrasion test on the glass substrate surface after the antifouling film PC was formed was 3. The contact angle after the wear test was 105.3 degrees. Therefore, a glass substrate with good durability could not be obtained.

　（実施例１７，１８　比較例１６，１７）
　第１の真空チャンバー２００を用いた場合において、防汚膜材料Ｍ１として、信越化学工業株式会社製の『ＫＹ－１７８』を用いた実施例１７および比較例１６、並びに、東レダウコーニング株式会社製の『Ｃｏｒｎｉｎｇ（登録商標）２６３４』を用いた実施例１８および比較例１７の場合を、図１６から図１８に示した。 (Examples 17 and 18 Comparative Examples 16 and 17)
In the case of using the first vacuum chamber 200, Example 17 and Comparative Example 16 using “KY-178” manufactured by Shin-Etsu Chemical Co., Ltd. as the antifouling film material M1, and manufactured by Toray Dow Corning Co., Ltd. Examples 18 and Comparative Example 17 using “Corning (registered trademark) 2634” are shown in FIGS. 16 to 18.

　図１６は、第１の真空チャンバーを用いた場合の、実施例１７、実施例１８、比較例１６および比較例１７の各種条件を示す図、図１７は、実施例１７および実施例１８におけるシャッター開放時間と防汚膜材料温度との関係を示す図、図１８は、比較例１６および比較例１７におけるシャッター開放時間と防汚膜材料温度との関係を示す図である。 FIG. 16 is a diagram showing various conditions of Example 17, Example 18, Comparative Example 16 and Comparative Example 17 when the first vacuum chamber is used, and FIG. 17 is a shutter in Example 17 and Example 18. FIG. 18 is a diagram showing the relationship between the opening time and the antifouling film material temperature, and FIG. 18 is a diagram showing the relationship between the shutter opening time and the antifouling film material temperature in Comparative Example 16 and Comparative Example 17.

　実施例１７および実施例１８において、シャッター開放時間と防汚膜材料温度との関係は同じであり、比較例１６および比較例１７におけるシャッター開放時間と防汚膜材料温度との関係は同じである。 In Example 17 and Example 18, the relationship between the shutter opening time and the antifouling film material temperature is the same, and the relationship between the shutter opening time and the antifouling film material temperature in Comparative Example 16 and Comparative Example 17 is the same. .

　（実施例１７）
　６０度のチャンバー雰囲気内で、まず下地膜ＵＣとしてガラス基板の表面にＳｉＯ_２を３０ｎｍ堆積させた。ガラス基板として、硬さ９Ｈの白板ガラスＳを用いた。次に防汚膜ＰＣの成膜を行なった。防汚膜ＰＣの成膜条件は、まず予備加熱工程として、防汚膜材料Ｍ１をシャッター２１１で覆い、１３０度まで防汚膜材料Ｍ１を加熱した。その後、シャッター２１１を移動し防汚膜材料Ｍ１を開放して、さらに防汚膜材料Ｍ１を３００度まで加熱した。シャッター開放時間と防汚膜材料温度との関係を図１７に示す。 (Example 17)
In a 60 degree chamber atmosphere, first, SiO ₂ was deposited to a thickness of 30 nm on the surface of the glass substrate as the base film UC. A white plate glass S having a hardness of 9H was used as the glass substrate. Next, an antifouling film PC was formed. As the film forming conditions for the antifouling film PC, first, as a preheating step, the antifouling film material M1 was covered with the shutter 211, and the antifouling film material M1 was heated to 130 degrees. Thereafter, the shutter 211 was moved to release the antifouling film material M1, and the antifouling film material M1 was further heated to 300 degrees. FIG. 17 shows the relationship between the shutter opening time and the antifouling film material temperature.

　図１６に示すように、防汚膜ＰＣの成膜後のガラス基板表面の摩耗試験のキズ本数は０本であった。摩耗試験後の接触角は１１４．３度であった。よって、良好な耐久性能を備えるガラス基板が得られた。 As shown in FIG. 16, the number of scratches in the abrasion test on the glass substrate surface after the antifouling film PC was formed was zero. The contact angle after the wear test was 114.3 degrees. Therefore, the glass substrate provided with favorable durability performance was obtained.

　（実施例１８）
　６０度のチャンバー雰囲気内で、まず下地膜ＵＣとしてガラス基板の表面にＳｉＯ_２を３０ｎｍ堆積させた。ガラス基板として、硬さ９Ｈの白板ガラスＳを用いた。次に防汚膜ＰＣの成膜を行なった。防汚膜ＰＣの成膜条件は、まず予備加熱工程として、防汚膜材料Ｍ１をシャッター２１１で覆い、１３０度まで防汚膜材料Ｍ１を加熱した。その後、シャッター２１１を移動し防汚膜材料Ｍ１を開放して、さらに防汚膜材料Ｍ１を３００度まで加熱した。シャッター開放時間と防汚膜材料温度との関係を図１７に示す。 (Example 18)
In a 60 degree chamber atmosphere, first, SiO ₂ was deposited to a thickness of 30 nm on the surface of the glass substrate as the base film UC. A white plate glass S having a hardness of 9H was used as the glass substrate. Next, an antifouling film PC was formed. As the film forming conditions for the antifouling film PC, first, as a preheating step, the antifouling film material M1 was covered with the shutter 211, and the antifouling film material M1 was heated to 130 degrees. Thereafter, the shutter 211 was moved to release the antifouling film material M1, and the antifouling film material M1 was further heated to 300 degrees. FIG. 17 shows the relationship between the shutter opening time and the antifouling film material temperature.

　図１６に示すように、防汚膜ＰＣの成膜後のガラス基板表面の摩耗試験のキズ本数は０本であった。摩耗試験後の接触角は１１４度であった。よって、良好な耐久性能を備えるガラス基板が得られた。 As shown in FIG. 16, the number of scratches in the abrasion test on the glass substrate surface after the antifouling film PC was formed was zero. The contact angle after the abrasion test was 114 degrees. Therefore, the glass substrate provided with favorable durability performance was obtained.

　（比較例１６）
　６０度のチャンバー雰囲気内で、まず下地膜ＵＣとしてガラス基板の表面にＳｉＯ_２を３０ｎｍ堆積させた。ガラス基板として、硬さ９Ｈの白板ガラスＳを用いた。次に防汚膜ＰＣの成膜を行なった。防汚膜ＰＣの成膜条件は、予備加熱工程は実施せずに、常温から３００度まで防汚膜材料Ｍ１を加熱した。シャッター開放時間と防汚膜材料温度との関係を図１８に示す。 (Comparative Example 16)
In a 60 degree chamber atmosphere, first, SiO ₂ was deposited to a thickness of 30 nm on the surface of the glass substrate as the base film UC. A white plate glass S having a hardness of 9H was used as the glass substrate. Next, an antifouling film PC was formed. As for the film forming conditions of the antifouling film PC, the antifouling film material M1 was heated from room temperature to 300 degrees without performing the preheating step. FIG. 18 shows the relationship between the shutter opening time and the antifouling film material temperature.

　図１６に示すように、防汚膜ＰＣの成膜後のガラス基板表面の摩耗試験のキズ本数は２本であった。摩耗試験後の接触角は１０５．２度であった。よって、良好な耐久性能を備えるガラス基板を得ることはできなかった。 As shown in FIG. 16, the number of scratches in the abrasion test on the glass substrate surface after the formation of the antifouling film PC was two. The contact angle after the abrasion test was 105.2 degrees. Therefore, a glass substrate having good durability could not be obtained.

　（比較例１７）
　ガラス基板として、硬さ９Ｈの白板ガラスＳを用いて防汚膜ＰＣの成膜を行なった。下地膜ＵＣは成膜していない。防汚膜ＰＣの成膜条件は、予備加熱工程は実施せずに、常温から３００度まで防汚膜材料Ｍ１を加熱した。シャッター開放時間と防汚膜材料温度との関係を図１８に示す。 (Comparative Example 17)
The antifouling film PC was formed using a white plate glass S having a hardness of 9H as the glass substrate. The base film UC is not formed. As for the film forming conditions of the antifouling film PC, the antifouling film material M1 was heated from room temperature to 300 degrees without performing the preheating step. FIG. 18 shows the relationship between the shutter opening time and the antifouling film material temperature.

　図１６に示すように、防汚膜ＰＣの成膜後のガラス基板表面の摩耗試験のキズ本数は３本であった。摩耗試験後の接触角は１００．１度であった。よって、良好な耐久性能を備えるガラス基板を得ることはできなかった。 As shown in FIG. 16, the number of scratches in the abrasion test on the glass substrate surface after the formation of the antifouling film PC was 3. The contact angle after the wear test was 100.1 degrees. Therefore, a glass substrate having good durability could not be obtained.

　以上、実施の形態１において、各実施例および各比較例から、予備加熱工程は、ガラス基板の被成膜面に、防汚膜材料Ｍ１から放出される不純物が到達しない状態で行ない、かつ、予備加熱工程は、防汚膜材料Ｍ１に含有する不純物を放出するため、フッ素系化合物を、フッ素系化合物の沸点（Ｔ３）－５０度の温度（Ｔ１）より高く、かつ、沸点（Ｔ３）より低い温度（Ｔ２）にまで加熱するとよい。 As described above, in the first embodiment, from each example and each comparative example, the preheating step is performed in a state where impurities released from the antifouling film material M1 do not reach the film formation surface of the glass substrate, and In the preheating step, impurities contained in the antifouling film material M1 are released, so that the fluorine compound is higher than the boiling point (T3) -50 ° C. of the fluorine compound (T1) and higher than the boiling point (T3). Heating to a low temperature (T2) is good.

　たとえば、防汚膜材料Ｍ１に、ダイキン工業株式会社製のオプツール（登録商標）ＤＳＸ、信越化学工業株式会社製のＫＹ－１７８、東レダウコーニング株式会社製のＣｏｒｎｉｎｇ（登録商標）２６３４等を用いた場合には、１３０度以上に加熱し、さらに成膜工程の際のシャッター２１１の開閉移動のタイミングを、材料の沸点以下で開き、その後成膜を実施することで耐久性が向上することが確認できた。 For example, as the antifouling film material M1, OPTOOL (registered trademark) DSX manufactured by Daikin Industries, Ltd., KY-178 manufactured by Shin-Etsu Chemical Co., Ltd., Corning (registered trademark) 2634 manufactured by Toray Dow Corning Co., Ltd., and the like were used. In this case, it is confirmed that the durability is improved by heating to 130 ° C. or more, opening the opening / closing movement timing of the shutter 211 during the film forming process below the boiling point of the material, and then performing film formation. did it.

　以上、本実施の形態おいては、予備加熱工程を、防汚膜材料Ｍ１に含有する不純物を放出するため、フッ素系化合物を、フッ素系化合物の沸点－５０度の温度より高く、かつ、上記沸点より低い温度にまで加熱するとともに、ガラス基板の被成膜面に、防汚膜材料Ｍ１から放出される不純物が到達しない状態で実施している。これにより、防汚膜材料に含まれる不純物がガラス基板に曝されることを抑制でき、防汚膜材料に含まれる不純物が防汚膜の蒸着成膜工程時には除去されている。その結果、防汚膜材料の有効成分のみがガラス基板に成膜され、膜質が安定し摩耗耐久性を向上させることが可能となる。 As described above, in the present embodiment, in order to release the impurities contained in the antifouling film material M1 in the preheating step, the fluorine compound is higher than the boiling point of the fluorine compound −50 degrees C. The heating is performed to a temperature lower than the boiling point, and the impurity released from the antifouling film material M1 does not reach the film formation surface of the glass substrate. Thereby, it can suppress that the impurity contained in antifouling film material is exposed to a glass substrate, and the impurity contained in antifouling film material is removed at the time of the vapor deposition film-forming process of antifouling film. As a result, only the effective component of the antifouling film material is deposited on the glass substrate, and the film quality is stabilized and the wear durability can be improved.

　［実施の形態２］
　本発明に基づいた実施の形態２におけるガラス製品の製造方法について、以下、図を参照しながら説明する。ディスプレイ装置１００およびディスプレイ用カバーガラス１０の構成は、上記実施の形態１と同じであるため、ここでの説明は省略する。 [Embodiment 2]
A method for manufacturing a glass product in Embodiment 2 based on the present invention will be described below with reference to the drawings. Since the configurations of the display device 100 and the display cover glass 10 are the same as those of the first embodiment, description thereof is omitted here.

　（ガラス製品の製造方法）
　図３に示した第１の真空チャンバー２００を用いた場合の、本実施の形態におけるディスプレイ用カバーガラス１０の製造方法に関し、フッ素系化合物を含有する防汚膜材料Ｍ１を用いた真空蒸着法により、ディスプレイ用カバーガラス１０の表面１１にフッ素系の防汚膜ＰＣを成膜する工程について以下する。 (Glass product manufacturing method)
With respect to the manufacturing method of the display cover glass 10 in the present embodiment when the first vacuum chamber 200 shown in FIG. 3 is used, the vacuum deposition method using the antifouling film material M1 containing a fluorine compound is used. A process for forming a fluorine-based antifouling film PC on the surface 11 of the display cover glass 10 will be described below.

　まず、真空チャンバー２００内に防汚膜が成膜されていないディスプレイ用カバーガラス１０を準備する。具体的には、ディスプレイ用カバーガラス１０の被成膜面である表面１１が、防汚膜材料収容容器２０７に対向するように、複数のディスプレイ用カバーガラス１０を基板支持部材２１３に保持させる。 First, a display cover glass 10 in which an antifouling film is not formed in the vacuum chamber 200 is prepared. Specifically, the plurality of display cover glasses 10 are held on the substrate support member 213 such that the surface 11 that is the film formation surface of the display cover glass 10 faces the antifouling film material container 207.

　防汚材料Ｍ１を沸点未満の温度で加熱し、防汚材料Ｍ１に含まれる不純物を放出させる予備加熱工程と、この予備加熱工程の後、防汚材料Ｍ１を沸点以上まで加熱を行ない、ディスプレイ用カバーガラス１０の表面１１に防汚膜ＰＣを成膜する成膜工程とを行なう。 For the display, the antifouling material M1 is heated at a temperature lower than the boiling point to release impurities contained in the antifouling material M1, and after this preheating step, the antifouling material M1 is heated to the boiling point or more. A film forming step for forming the antifouling film PC on the surface 11 of the cover glass 10 is performed.

　予備加熱工程においては、防汚膜材料Ｍ１に含有する不純物を放出させるため防汚膜材料Ｍ１の加熱を行ない、真空チャンバー２００内の圧力のモニタリングを行なう。 In the preheating process, the antifouling film material M1 is heated to release impurities contained in the antifouling film material M1, and the pressure in the vacuum chamber 200 is monitored.

　防汚膜材料Ｍ１を加熱することによって、含まれる不純物が真空チャンバー２００内に放出され、真空チャンバー２００内の圧力が増加（真空度が悪化）する。しかし、不純物が放出しきれば、沸点に至るまでの温度域で圧力が上昇から減少に転じ、その後、圧力の変化は一定になる。真空チャンバー２００内の圧力の変化率が上昇から減少に転じた後、この変化率が一定になることをモニタリングするには、０．１度／ｓｅｃから３００度／ｓｅｃの温度上昇、好ましくは、０．１度／ｓｅｃから５０度／ｓｅｃの温度上昇で加熱することで、圧力の経時変化が緩やかになるためモニタリングしやすい。 By heating the antifouling film material M1, the contained impurities are released into the vacuum chamber 200, and the pressure in the vacuum chamber 200 increases (the degree of vacuum deteriorates). However, once the impurities are released, the pressure changes from increasing to decreasing in the temperature range up to the boiling point, and thereafter the pressure change becomes constant. In order to monitor that the rate of change of the pressure in the vacuum chamber 200 changes from an increase to a decrease, a temperature increase of 0.1 to 300 degrees / sec, preferably, By heating at a temperature increase of 0.1 degrees / sec to 50 degrees / sec, the change over time of the pressure becomes gentle, so monitoring is easy.

　モニタリングは成膜条件を抽出するときのみに行なわれ、真空チャンバー２００内の圧力の変化率が上昇から減少に転じて一定になっている状態を確実にモニタリングできる場合は、常時モニタリングを実施しなくてもよい。 Monitoring is performed only when film formation conditions are extracted, and monitoring is not always performed when the rate of change in pressure in the vacuum chamber 200 can be reliably monitored when the pressure changes from increasing to decreasing. May be.

　予備加熱工程から成膜工程への移行は、真空チャンバー２００内の圧力の変化率が上昇から減少に転じた後、変化率が急峻な状態から緩やかな状態に転じた後に行なう。 The transition from the preheating process to the film forming process is performed after the rate of change in the pressure in the vacuum chamber 200 has changed from an increase to a decrease and then the rate of change has changed from a steep state to a gentle state.

　変化率が急峻な状態から緩やかな状態に転じた後に行なうことに対して好ましい条件として、予備加熱工程から成膜工程への移行は、防汚成膜チャンバー内の圧力の変化率が予備加熱工程前の圧力の変化率よりも小さい状態で行なうことが好ましい。防汚成膜チャンバー内の圧力の変化率が予備加熱工程前の圧力の変化率よりも小さい状態では、防汚膜材料Ｍ１に含まれる不純物が放出され、不純物が防汚成膜チャンバー内から排気された状態となっている。 As a preferable condition to be performed after the rate of change has changed from a steep state to a gradual state, the transition from the preheating step to the film forming step is such that the rate of change in pressure in the antifouling film forming chamber is the preheating step. It is preferable to carry out in a state smaller than the rate of change of the previous pressure. In a state where the rate of change of pressure in the antifouling film forming chamber is smaller than the rate of change of pressure before the preheating step, impurities contained in the antifouling film material M1 are released, and the impurities are exhausted from the inside of the antifouling film forming chamber. It has become a state.

　さらに好ましい予備加熱工程から成膜工程への移行は、真空チャンバー内の圧力の変化率が上昇に転じる直前の変化率よりも小さい状態で行なわれることがよい。 More preferably, the transition from the preheating step to the film forming step is preferably performed in a state where the rate of change of the pressure in the vacuum chamber is smaller than the rate of change just before the increase.

　予備加熱工程においては、シャッター２１１を、防汚膜材料Ｍ１を覆う位置Ｐ１に移動させた状態で、防汚膜材料Ｍ１の加熱を行なう。成膜工程においては、シャッター２１１を、防汚膜材料Ｍ１を開放する位置Ｐ２に移動させた状態で、防汚膜材料Ｍ１の加熱を行なう。ガラス１０の表面１１に、フッ素系の防汚膜ＰＣを所望の膜厚まで成膜する成膜工程を実施する。膜厚さは、ｎｍオーダーで制御され、所望の膜厚とは、成膜後、ディスプレイ用カバーガラス１０が防汚膜ＰＣによって白濁しない程度の膜厚のことを言う。 In the preheating step, the antifouling film material M1 is heated in a state where the shutter 211 is moved to the position P1 covering the antifouling film material M1. In the film forming process, the antifouling film material M1 is heated in a state where the shutter 211 is moved to the position P2 where the antifouling film material M1 is opened. A film forming step for forming a fluorine-based antifouling film PC to a desired film thickness on the surface 11 of the glass 10 is performed. The film thickness is controlled on the order of nm, and the desired film thickness means a film thickness that does not cause the display cover glass 10 to become clouded by the antifouling film PC after film formation.

　具体的には、表面１１と防汚膜材料Ｍ１との間には、シャッター２１１が配設され、シャッター２１１は、予備加熱工程においては、表面１１に、防汚膜材料Ｍ１から放出される不純物が到達しないように防汚膜材料Ｍ１を覆い、成膜工程においては、表面１１に、防汚膜材料Ｍ１から放出される防汚膜ＰＣの材料が到達するように、汚膜材料Ｍ１を開放する。予備加熱工程から成膜工程への移行は、真空チャンバー２００内の圧力の変化率が上昇から減少に転じた後、変化率が急峻な状態から緩やかな状態に転じた後に行なう。 Specifically, a shutter 211 is disposed between the surface 11 and the antifouling film material M1, and the shutter 211 is an impurity released from the antifouling film material M1 on the surface 11 in the preheating step. The antifouling film material M1 is covered so that the antifouling film material M1 does not reach, and in the film forming process, the antifouling film material M1 is opened so that the surface of the antifouling film material M1 can be reached on the surface 11. To do. The transition from the preheating process to the film forming process is performed after the rate of change of the pressure in the vacuum chamber 200 has changed from an increase to a decrease and then the rate of change has changed from a steep state to a gentle state.

　（他のガラス製品の製造方法）
　図４に示した第２の真空チャンバー３００を用いた場合の、本実施の形態におけるディスプレイ用カバーガラス１０の製造方法に関し、フッ素系化合物を含有する防汚膜材料Ｍ１を用いた真空蒸着法により、ディスプレイ用カバーガラス１０の表面１１にフッ素系の防汚膜ＰＣを成膜する工程について以下する。 (Manufacturing method of other glass products)
With respect to the manufacturing method of the display cover glass 10 in the present embodiment when the second vacuum chamber 300 shown in FIG. 4 is used, the vacuum deposition method using the antifouling film material M1 containing a fluorine compound is used. A process for forming a fluorine-based antifouling film PC on the surface 11 of the display cover glass 10 will be described below.

　まず、導入チャンバー３００Ａ内に、ディスプレイ用カバーガラス１０の被成膜面である表面１１が、防汚膜材料収容容器３５７に対向するように、複数のディスプレイ用カバーガラス１０を基板支持部材３１３に保持させた状態で、第１支持部材３１５に基板支持部材３１３を載置する（ガラス基板の準備）。 First, a plurality of display cover glasses 10 are placed on the substrate support member 313 so that the surface 11 that is the film formation surface of the display cover glass 10 faces the antifouling film material container 357 in the introduction chamber 300A. In a state of being held, the substrate support member 313 is placed on the first support member 315 (preparation of a glass substrate).

　次に、第１開閉部材３７０を開放して、基板支持部材３１３を下地成膜チャンバー３００Ｂに移送する（図４中Ｔ１方向）。次に、ディスプレイ用カバーガラス１０の温度を、５０度～８０度の範囲で加熱する。予めディスプレイ用カバーガラス１０の表面１１に、下地膜ＵＣとしてＳｉＯ_２膜を５ｎｍ～２００ｎｍ、より好ましくは１０ｎｍ～１００ｎｍ堆積する。 Next, the first opening / closing member 370 is opened, and the substrate support member 313 is transferred to the base film forming chamber 300B (direction T1 in FIG. 4). Next, the temperature of the display cover glass 10 is heated in the range of 50 to 80 degrees. A SiO ₂ film is deposited in advance on the surface 11 of the display cover glass 10 as a base film UC in a range of 5 nm to 200 nm, more preferably 10 nm to 100 nm.

　一方、防汚成膜チャンバー３００Ｃにおいては、防汚材料Ｍ１を沸点未満の温度で加熱し、防汚材料Ｍ１に含まれる不純物を放出させる予備加熱工程と、この予備加熱工程の後、防汚材料Ｍ１を沸点以上まで加熱を行ない、ディスプレイ用カバーガラス１０の表面１１に防汚膜ＰＣを成膜する成膜工程とを行なう。 On the other hand, in the antifouling film forming chamber 300C, the antifouling material M1 is heated at a temperature lower than the boiling point to release impurities contained in the antifouling material M1, and after this preheating step, the antifouling material M1 is heated to the boiling point or higher, and a film forming step for forming the antifouling film PC on the surface 11 of the display cover glass 10 is performed.

　予備加熱工程においては、防汚膜材料Ｍ１に含有する不純物を放出させるため防汚膜材料Ｍ１の加熱を行ない、防汚成膜チャンバー３００Ｃ内の圧力（真空度）のモニタリングを行なう。 In the preheating step, the antifouling film material M1 is heated to release impurities contained in the antifouling film material M1, and the pressure (degree of vacuum) in the antifouling film forming chamber 300C is monitored.

　防汚膜材料Ｍ１を加熱することによって、含まれる不純物が真空チャンバー２００内に放出され、防汚成膜チャンバー３００Ｃ内の圧力が上昇する。しかし、不純物が放出しきれば、沸点に至るまでの温度域で圧力が上昇から減少転じ、その後、圧力の変化は一定になる。防汚成膜チャンバー３００Ｃ内の圧力の変化率が上昇から減少に転じた後、この変化率が一定になることをモニタリングするには、０．１度／ｓｅｃから３００度／ｓｅｃの温度上昇、好ましくは、０．１度／ｓｅｃから５０度／ｓｅｃの温度上昇で加熱することで、圧力の経時変化が緩やかになるためモニタリングしやすい。 By heating the antifouling film material M1, the contained impurities are released into the vacuum chamber 200, and the pressure in the antifouling film forming chamber 300C increases. However, if the impurities are completely released, the pressure starts to decrease in the temperature range up to the boiling point, and thereafter the pressure change becomes constant. In order to monitor that the rate of change of the pressure in the antifouling film forming chamber 300C changes from an increase to a decrease, a temperature increase of 0.1 to 300 degrees / sec is monitored. Preferably, heating is performed at a temperature increase of 0.1 ° C./sec to 50 ° C./sec, so that the change over time of the pressure becomes gentle, so that monitoring is easy.

　モニタリングは成膜条件を抽出するときのみに行なわれ、防汚成膜チャンバー３００Ｃ内の圧力の変化率が上昇から減少に転じて一定になっている状態を確実にモニタリングできる場合は、常時モニタリングを実施しなくてもよい。 Monitoring is performed only when the film formation conditions are extracted. When the rate of change in the pressure in the antifouling film formation chamber 300C can be reliably monitored from the increase to the decrease, always monitor it. It is not necessary to carry out.

　予備加熱工程から成膜工程への移行は、防汚成膜チャンバー３００Ｃ内の圧力の変化率が上昇から減少に転じた後、変化率が急峻な状態から緩やかな状態に転じた後に行なう。第２開閉部材３８０を開放して、基板支持部材３１３を防汚成膜チャンバー３００Ｃに移送する（図４中Ｔ２方向）。その後、防汚膜材料Ｍ１の温度を上昇させて、防汚成膜チャンバー３００Ｃ内で成膜工程を実施する。 The transition from the preheating process to the film forming process is performed after the rate of change in the pressure in the antifouling film forming chamber 300C has changed from an increase to a decrease and then the rate of change has changed from a steep state to a gentle state. The second opening / closing member 380 is opened, and the substrate support member 313 is transferred to the antifouling film formation chamber 300C (direction T2 in FIG. 4). Thereafter, the temperature of the antifouling film material M1 is raised, and the film forming process is performed in the antifouling film forming chamber 300C.

　基板支持部材３１３の下地成膜チャンバー３００Ｂから防汚成膜チャンバー３００Ｃへの移送は、防汚成膜チャンバー３００Ｃ内の真空状態が維持された状態で、防汚成膜チャンバー３００Ｃ内に基板支持部材３１３が導入されるとよい。予備加熱工程および成膜工程の防汚成膜チャンバー３００Ｃ内の圧力は、１０^－９Ｐａ～１Ｐａの範囲であるとよい。成膜時における成膜条件および温調制御は、上記と同じである。 The substrate supporting member 313 is transferred from the base film forming chamber 300B to the antifouling film forming chamber 300C in a state where the vacuum state in the antifouling film forming chamber 300C is maintained, and the substrate supporting member is placed in the antifouling film forming chamber 300C. 313 may be introduced. The pressure in the antifouling film forming chamber 300C in the preheating process and the film forming process is preferably in the range of 10 ⁻⁹ Pa to 1 Pa. Film formation conditions and temperature control during film formation are the same as described above.

　具体的には、予備加熱工程および成膜工程は、防汚成膜チャンバー３００Ｃの内部が常に排気状態で実施され、予備加熱工程は、ディスプレイ用カバーガラス１０が導入されていない防汚成膜チャンバー３００Ｃ内で行なわれ、成膜工程は、予備加熱工程の後に防汚成膜チャンバー３００Ｃ内の真空状態が維持された状態で、防汚成膜チャンバー３００Ｃ内にディスプレイ用カバーガラス１０が導入される工程を含む。予備加熱工程から成膜工程への移行は、防汚成膜チャンバー３００Ｃ内の圧力の変化率が上昇から減少に転じた後、変化率が急峻な状態から緩やかな状態に転じた後に行なう。 Specifically, the preheating step and the film forming step are always performed while the inside of the antifouling film forming chamber 300C is exhausted, and the preheating step is performed in the antifouling film forming chamber in which the display cover glass 10 is not introduced. The display cover glass 10 is introduced into the antifouling film forming chamber 300C in a state where the vacuum state in the antifouling film forming chamber 300C is maintained after the preheating step. Process. The transition from the preheating process to the film forming process is performed after the rate of change in the pressure in the antifouling film forming chamber 300C changes from an increase to a decrease and then the change rate changes from a steep state to a gentle state.

　（他のガラス製品の製造方法）
　図５に示した第３の真空チャンバー４００を用いた場合の、本実施の形態におけるディスプレイ用カバーガラス１０の製造方法に関し、フッ素系化合物を含有する防汚膜材料Ｍ１を用いた真空蒸着法により、ディスプレイ用カバーガラス１０の表面１１にフッ素系の防汚膜ＰＣを成膜する工程について以下する。 (Manufacturing method of other glass products)
With respect to the manufacturing method of the display cover glass 10 in the present embodiment when the third vacuum chamber 400 shown in FIG. 5 is used, the vacuum evaporation method using the antifouling film material M1 containing a fluorine-based compound is used. A process for forming a fluorine-based antifouling film PC on the surface 11 of the display cover glass 10 will be described below.

　基本的な製造方法は、第２の真空チャンバー３００を用いた場合と同様であるが、予備加熱チャンバー３００Ｄにおいて、防汚膜材料Ｍ１に含有する不純物を放出させるための予備加熱工程においては、防汚膜材料Ｍ１に含有する不純物を放出させるため防汚膜材料Ｍ１の加熱を行ない、予備加熱チャンバー３００Ｄ内の圧力（真空度）のモニタリングを行なう。 The basic manufacturing method is the same as that in the case where the second vacuum chamber 300 is used, but in the preheating step for releasing impurities contained in the antifouling film material M1 in the preheating chamber 300D, The antifouling film material M1 is heated in order to release impurities contained in the fouling film material M1, and the pressure (degree of vacuum) in the preheating chamber 300D is monitored.

　防汚膜材料Ｍ１を加熱することによって、含まれる不純物が予備加熱チャンバー３００Ｄ内に放出され、予備加熱チャンバー３００Ｄ内の圧力が上昇する。しかし、不純物が放出しきれば、沸点に至るまでの温度域で圧力が上昇から減少転じ、その後、圧力の変化は一定になる。予備加熱チャンバー３００Ｄ内の圧力の変化率が上昇から減少に転じた後、この変化率が一定になることをモニタリングするには、０．１度／ｓｅｃから３００度／ｓｅｃの温度上昇、好ましくは、０．１度／ｓｅｃから５０度／ｓｅｃの温度上昇で加熱することで、圧力（真空度）の経時変化が緩やかになるのでモニタリングしやすい。 By heating the antifouling film material M1, the contained impurities are released into the preheating chamber 300D, and the pressure in the preheating chamber 300D increases. However, if the impurities are completely released, the pressure starts to decrease in the temperature range up to the boiling point, and thereafter the pressure change becomes constant. In order to monitor that the rate of change of the pressure in the preheating chamber 300D changes from an increase to a decrease, a temperature increase of 0.1 to 300 degrees / sec, preferably, By heating at a temperature increase of 0.1 ° / sec to 50 ° / sec, the change over time in the pressure (vacuum degree) becomes gentle, so that monitoring is easy.

　モニタリングは成膜条件を抽出するときのみに行なわれ、予備加熱チャンバー３００Ｄ内の圧力の変化率が上昇から減少に転じて一定になっている状態を確実にモニタリングできる場合は、常時モニタリングを実施しなくてもよい。 Monitoring is performed only when the film formation conditions are extracted. If the rate of change in the pressure in the preheating chamber 300D can be reliably monitored when the pressure changes from increasing to decreasing, the monitoring is always performed. It does not have to be.

　予備加熱工程から成膜工程への移行は、予備加熱チャンバー３００Ｄ内の圧力の変化率が上昇から減少に転じた後、変化率が急峻な状態から緩やかな状態に転じた後に行なう。第２開閉部材３８０を開放して、基板支持部材３１３を防汚成膜チャンバー３００Ｃに移送する（図４中Ｔ２方向）。 The transition from the preheating process to the film forming process is performed after the change rate of the pressure in the preheating chamber 300D has changed from an increase to a decrease and then the change rate has changed from a steep state to a gentle state. The second opening / closing member 380 is opened, and the substrate support member 313 is transferred to the antifouling film formation chamber 300C (direction T2 in FIG. 4).

　次に、第３開閉部材３９０を開放して、ヒーター３５５、および、防汚膜材料収容容器３５７を、防汚成膜チャンバー３００Ｃに移送して（図５中Ｔ３）、防汚膜材料Ｍ１の温度を上昇させて、防汚成膜チャンバー３００Ｃ内で成膜工程を実施する。 Next, the third opening / closing member 390 is opened, the heater 355 and the antifouling film material container 357 are transferred to the antifouling film forming chamber 300C (T3 in FIG. 5), and the antifouling film material M1 is transferred. The film forming step is performed in the antifouling film forming chamber 300C by raising the temperature.

　防汚膜材料収容容器３５７の防汚成膜チャンバー３００Ｃへの移送、および、基板支持部材３１３の下地成膜チャンバー３００Ｂから防汚成膜チャンバー３００Ｃへの移送は、防汚成膜チャンバー３００Ｃ内の真空状態が維持された状態で、防汚成膜チャンバー３００Ｃ内に基板支持部材３１３が導入されるとよい。予備加熱工程および成膜工程の防汚成膜チャンバー３００Ｃ内の圧力は、１０^－９Ｐａ～１Ｐａの範囲であるとよい。成膜時における成膜条件および温調制御は、上記と同じである。 The transfer of the antifouling film material container 357 to the antifouling film forming chamber 300C and the transfer of the substrate support member 313 from the base film forming chamber 300B to the antifouling film forming chamber 300C are performed in the antifouling film forming chamber 300C. The substrate support member 313 is preferably introduced into the antifouling film forming chamber 300C while the vacuum state is maintained. The pressure in the antifouling film forming chamber 300C in the preheating process and the film forming process is preferably in the range of 10 ⁻⁹ Pa to 1 Pa. Film formation conditions and temperature control during film formation are the same as described above.

　具体的には、成膜工程は、防汚成膜チャンバー３００Ｃの内部が常に排気状態で実施され、予備加熱工程は、ディスプレイ用カバーガラス１０が導入された防汚成膜チャンバー３００Ｃとは異なる予備加熱チャンバー３００Ｄで行なわれることにより、防汚膜材料Ｍ１に含有する不純物が放出される工程を含み、成膜工程は、予備加熱工程の後に防汚成膜チャンバー３００Ｃ内に予備加熱工程が終了した防汚膜材料Ｍ１が導入される工程を含む。予備加熱工程から成膜工程への移行は、予備加熱チャンバー３００Ｄ内の圧力の変化率が上昇から減少に転じた後、変化率が急峻な状態から緩やかな状態に転じた後に行なう。 Specifically, the film forming step is always performed while the inside of the antifouling film forming chamber 300C is in an exhausted state, and the preheating step is a spare different from the antifouling film forming chamber 300C into which the display cover glass 10 is introduced. By being performed in the heating chamber 300D, the step of releasing impurities contained in the antifouling film material M1 is included, and the film forming step is completed in the antifouling film forming chamber 300C after the preheating step. A step of introducing the antifouling film material M1 is included. The transition from the preheating step to the film forming step is performed after the rate of change in pressure in the preheating chamber 300D has changed from an increase to a decrease and then the rate of change has changed from a steep state to a gentle state.

　（実施例）
　次に、上記第１の真空チャンバー２００を用いて実施したガラス製品の製造方法の実施例２１から２４、および比較例２１から２５について以下説明する。実施例２１、２２および比較例２１から２３において用いた防汚膜材料Ｍ１は、ダイキン社製の『オプツール（登録商標）ＤＳＸ』である。実施例２３および比較例２４において用いた防汚膜材料Ｍ１は、東レダウコーニング株式会社製の『Ｃｏｒｎｉｎｇ（登録商標）２６３４』である。実施例２４および比較例２５において用いた防汚膜材料Ｍ１は、信越化学工業株式会社製の『ＫＹ－１７８』である。 (Example)
Next, Examples 21 to 24 and Comparative Examples 21 to 25 of the glass product manufacturing method performed using the first vacuum chamber 200 will be described below. The antifouling film material M1 used in Examples 21 and 22 and Comparative Examples 21 to 23 is “OPTOOL (registered trademark) DSX” manufactured by Daikin. The antifouling film material M1 used in Example 23 and Comparative Example 24 is “Corning (registered trademark) 2634” manufactured by Toray Dow Corning Co., Ltd. The antifouling film material M1 used in Example 24 and Comparative Example 25 is “KY-178” manufactured by Shin-Etsu Chemical Co., Ltd.

　各実施例および各比較例における各種成膜条件は、図１９から図２８に示すとおりである。各図中の△印は真空チャンバー内の圧力を示し、×印は、真空チャンバー内に設けられた単位時間当たりの着膜の厚さをモニターする水晶モニターの出力を示している。 The various film forming conditions in each example and each comparative example are as shown in FIGS. In each figure, Δ indicates the pressure in the vacuum chamber, and X indicates the output of a crystal monitor that monitors the thickness of the deposited film per unit time provided in the vacuum chamber.

　（実施例２１）
　６０度のチャンバー雰囲気内で、まず下地膜ＵＣとしてガラス基板の表面にＳｉＯ_２を３０ｎｍ堆積させた。ガラス基板として、硬さ９Ｈの白板ガラスＳを用いた。次に防汚膜ＰＣの成膜を行なった。防汚膜ＰＣの成膜条件は、まず予備加熱工程として、防汚膜材料Ｍ１をシャッター２１１で覆い、防汚膜材料Ｍ１の沸点－５０℃以上、沸点未満の温度で加熱を行なった。予備加熱温度は１６０℃、成膜温度は３００℃まで加熱した。 (Example 21)
In a 60 degree chamber atmosphere, first, SiO ₂ was deposited to a thickness of 30 nm on the surface of the glass substrate as the base film UC. A white plate glass S having a hardness of 9H was used as the glass substrate. Next, an antifouling film PC was formed. As the film forming conditions for the antifouling film PC, first, as a preheating step, the antifouling film material M1 was covered with the shutter 211, and the antifouling film material M1 was heated at a temperature not lower than the boiling point of −50 ° C. and lower than the boiling point. The preheating temperature was 160 ° C., and the film formation temperature was 300 ° C.

　真空チャンバー２００内には、ペニング真空計を配設し、チャンバー内の圧力変動をリアルタイムで測定した。 In the vacuum chamber 200, a Penning vacuum gauge was installed, and the pressure fluctuation in the chamber was measured in real time.

　図２０に示すように、予備加熱工程から成膜工程への移行は、真空チャンバー２００内の圧力の変化率が上昇から減少に転じた後、変化率が急峻な状態から緩やかな状態に転じた後、しばらく時間が経過した位置Ｐ１（約５００秒）で行なった。 As shown in FIG. 20, in the transition from the preheating process to the film forming process, the change rate of the pressure in the vacuum chamber 200 changed from an increase to a decrease, and then the change rate changed from a steep state to a gentle state. Thereafter, the test was performed at a position P1 (about 500 seconds) after a while.

　図１９に示すように、防汚膜ＰＣの成膜後のガラス基板表面の摩耗試験のキズ本数は０本であった。摩耗試験後の接触角は１１４．０度であった。よって、良好な耐久性能を備えるガラス基板が得られた。 As shown in FIG. 19, the number of scratches in the abrasion test on the glass substrate surface after the formation of the antifouling film PC was zero. The contact angle after the abrasion test was 114.0 degrees. Therefore, the glass substrate provided with favorable durability performance was obtained.

　（実施例２２）
　６０度のチャンバー雰囲気内で、まず下地膜ＵＣとしてガラス基板の表面にＳｉＯ_２を３０ｎｍ堆積させた。ガラス基板として、硬さ９Ｈの白板ガラスＳを用いた。次に防汚膜ＰＣの成膜を行なった。防汚膜ＰＣの成膜条件は、まず予備加熱工程として、防汚膜材料Ｍ１をシャッター２１１で覆い、防汚膜材料Ｍ１の沸点－５０℃以上、沸点未満の温度で加熱を行なった。予備加熱温度は１６０℃、成膜温度は３００℃まで加熱した。 (Example 22)
In a 60 degree chamber atmosphere, first, SiO ₂ was deposited to a thickness of 30 nm on the surface of the glass substrate as the base film UC. A white plate glass S having a hardness of 9H was used as the glass substrate. Next, an antifouling film PC was formed. As the film forming conditions for the antifouling film PC, first, as a preheating step, the antifouling film material M1 was covered with the shutter 211, and the antifouling film material M1 was heated at a temperature not lower than the boiling point of −50 ° C. and lower than the boiling point. The preheating temperature was 160 ° C., and the film formation temperature was 300 ° C.

　チャンバー内には、ペニング真空計を配設し、チャンバー内の圧力変動をリアルタイムで測定した。 A Penning vacuum gauge was installed in the chamber, and the pressure fluctuation in the chamber was measured in real time.

　図２１に示すように、予備加熱工程から成膜工程への移行は、上記実施例２１よりも早く、真空チャンバー２００内の圧力の変化率が上昇から減少に転じた後、変化率が急峻な状態から緩やかな状態に転じた後となる位置Ｐ２（約３００秒）で行なった。 As shown in FIG. 21, the transition from the preheating process to the film forming process is faster than in Example 21, and after the rate of change in the pressure in the vacuum chamber 200 changes from increasing to decreasing, the rate of change is steep. The test was performed at the position P2 (about 300 seconds) after the transition from the state to the gentle state.

　図１９に示すように、防汚膜ＰＣの成膜後のガラス基板表面の摩耗試験のキズ本数は０本であった。摩耗試験後の接触角は１１３．９度であった。よって、良好な耐久性能を備えるガラス基板が得られた。 As shown in FIG. 19, the number of scratches in the abrasion test on the glass substrate surface after the formation of the antifouling film PC was zero. The contact angle after the abrasion test was 113.9 degrees. Therefore, the glass substrate provided with favorable durability performance was obtained.

　（実施例２３）
　６０度のチャンバー雰囲気内で、まず下地膜ＵＣとしてガラス基板の表面にＳｉＯ_２を３０ｎｍ堆積させた。ガラス基板として、硬さ９Ｈの白板ガラスＳを用いた。次に防汚膜ＰＣの成膜を行なった。防汚膜ＰＣの成膜条件は、まず予備加熱工程として、防汚膜材料Ｍ１をシャッター２１１で覆い、防汚膜材料Ｍ１の沸点－５０℃以上、沸点未満の温度で加熱を行なった。予備加熱温度は１３０℃、成膜温度は３００℃まで加熱した。 (Example 23)
In a 60 degree chamber atmosphere, first, SiO ₂ was deposited to a thickness of 30 nm on the surface of the glass substrate as the base film UC. A white plate glass S having a hardness of 9H was used as the glass substrate. Next, an antifouling film PC was formed. As the film forming conditions for the antifouling film PC, first, as a preheating step, the antifouling film material M1 was covered with the shutter 211, and the antifouling film material M1 was heated at a temperature not lower than the boiling point of −50 ° C. and lower than the boiling point. The preheating temperature was 130 ° C. and the film formation temperature was 300 ° C.

　図２２に示すように、予備加熱工程から成膜工程への移行は、真空チャンバー２００内の圧力の変化率が上昇から減少に転じた後、変化率が急峻な状態から緩やかな状態に転じた後となる位置Ｐ３（約２００秒）で行なった。 As shown in FIG. 22, in the transition from the preheating process to the film forming process, after the rate of change in the pressure in the vacuum chamber 200 changed from an increase to a decrease, the rate of change changed from a steep state to a gentle state. This was performed at a later position P3 (about 200 seconds).

　（実施例２４）
　６０度のチャンバー雰囲気内で、まず下地膜ＵＣとしてガラス基板の表面にＳｉＯ_２を３０ｎｍ堆積させた。ガラス基板として、硬さ９Ｈの白板ガラスＳを用いた。次に防汚膜ＰＣの成膜を行なった。防汚膜ＰＣの成膜条件は、まず予備加熱工程として、防汚膜材料Ｍ１をシャッター２１１で覆い、防汚膜材料Ｍ１の沸点－５０℃以上、沸点未満の温度で加熱を行なった。予備加熱温度は１３０℃、成膜温度は３００℃まで加熱した。 (Example 24)
In a 60 degree chamber atmosphere, first, SiO ₂ was deposited to a thickness of 30 nm on the surface of the glass substrate as the base film UC. A white plate glass S having a hardness of 9H was used as the glass substrate. Next, an antifouling film PC was formed. As the film forming conditions for the antifouling film PC, first, as a preheating step, the antifouling film material M1 was covered with the shutter 211, and the antifouling film material M1 was heated at a temperature not lower than the boiling point of −50 ° C. and lower than the boiling point. The preheating temperature was 130 ° C. and the film formation temperature was 300 ° C.

　図２３に示すように、予備加熱工程から成膜工程への移行は、真空チャンバー２００内の圧力の変化率が上昇から減少に転じた後、変化率が急峻な状態から緩やかな状態に転じた後となる位置Ｐ４（約１９０秒）で行なった。 As shown in FIG. 23, in the transition from the preheating process to the film forming process, after the rate of change in the pressure in the vacuum chamber 200 changed from an increase to a decrease, the rate of change changed from a steep state to a gentle state. This was performed at a later position P4 (about 190 seconds).

　（比較例２１）
　６０度のチャンバー雰囲気内で、まず下地膜ＵＣとしてガラス基板の表面にＳｉＯ_２を３０ｎｍ堆積させた。ガラス基板として、硬さ９Ｈの白板ガラスＳを用いた。次に防汚膜ＰＣの成膜を行なった。防汚膜ＰＣの成膜条件は、まず予備加熱工程として、防汚膜材料Ｍ１をシャッター２１１で覆い、防汚膜材料Ｍ１の沸点未満の温度で加熱を行なった。予備加熱温度は１６０℃、成膜温度は３００℃まで加熱した。 (Comparative Example 21)
In a 60 degree chamber atmosphere, first, SiO ₂ was deposited to a thickness of 30 nm on the surface of the glass substrate as the base film UC. A white plate glass S having a hardness of 9H was used as the glass substrate. Next, an antifouling film PC was formed. The film forming conditions for the antifouling film PC were as follows. First, as a preheating step, the antifouling film material M1 was covered with the shutter 211 and heated at a temperature lower than the boiling point of the antifouling film material M1. The preheating temperature was 160 ° C., and the film formation temperature was 300 ° C.

　図２４に示すように、予備加熱工程から成膜工程への移行は、真空チャンバー２００内の圧力の変化率が上昇から減少に転じた直後の位置Ｐ５（約２００秒）で行なった。成膜工程においては、防汚膜材料Ｍ１の沸点以上の温度で加熱を行なった。 As shown in FIG. 24, the transition from the preheating process to the film forming process was performed at a position P5 (about 200 seconds) immediately after the rate of change in pressure in the vacuum chamber 200 changed from increasing to decreasing. In the film forming step, heating was performed at a temperature equal to or higher than the boiling point of the antifouling film material M1.

　図１９に示すように、防汚膜ＰＣの成膜後のガラス基板表面の摩耗試験のキズ本数は３本であった。摩耗試験後の接触角は１１３．８度であった。よって、良好な耐久性能を備えるガラス基板を得ることはできなかった。 As shown in FIG. 19, the number of scratches in the abrasion test on the glass substrate surface after the formation of the antifouling film PC was 3. The contact angle after the wear test was 113.8 degrees. Therefore, a glass substrate having good durability could not be obtained.

　（比較例２２）
　６０度のチャンバー雰囲気内で、まず下地膜ＵＣとしてガラス基板の表面にＳｉＯ_２を３０ｎｍ堆積させた。ガラス基板として、硬さ９Ｈの白板ガラスＳを用いた。次に防汚膜ＰＣの成膜を行なった。防汚膜ＰＣの成膜条件は、まず予備加熱工程として、防汚膜材料Ｍ１をシャッター２１１で覆い、防汚膜材料Ｍ１の沸点以上の温度で加熱を行なった。予備加熱温度は１６０℃、成膜温度は３００℃まで加熱した。 (Comparative Example 22)
In a 60 degree chamber atmosphere, first, SiO ₂ was deposited to a thickness of 30 nm on the surface of the glass substrate as the base film UC. A white plate glass S having a hardness of 9H was used as the glass substrate. Next, an antifouling film PC was formed. The film forming conditions for the antifouling film PC were as follows. First, as a preheating step, the antifouling film material M1 was covered with the shutter 211 and heated at a temperature equal to or higher than the boiling point of the antifouling film material M1. The preheating temperature was 160 ° C., and the film formation temperature was 300 ° C.

　図２５に示すように、予備加熱工程から成膜工程への移行は、真空チャンバー２００内の圧力の変化率が上昇に転じた直後の位置Ｐ４（約１００秒）で行なった。成膜工程においては、防汚膜材料Ｍ１の沸点以上の温度で加熱を行なった。 As shown in FIG. 25, the transition from the preheating process to the film forming process was performed at position P4 (about 100 seconds) immediately after the rate of change in pressure in the vacuum chamber 200 started to increase. In the film forming step, heating was performed at a temperature equal to or higher than the boiling point of the antifouling film material M1.

　図１９に示すように、防汚膜ＰＣの成膜後のガラス基板表面の摩耗試験のキズ本数は５本以上であった。摩耗試験後の接触角は１１３．４度であった。よって、良好な耐久性能を備えるガラス基板を得ることはできなかった。 As shown in FIG. 19, the number of scratches in the abrasion test on the glass substrate surface after the formation of the antifouling film PC was 5 or more. The contact angle after the wear test was 113.4 degrees. Therefore, a glass substrate having good durability could not be obtained.

　（比較例２３）
　６０度のチャンバー雰囲気内で、まず下地膜ＵＣとしてガラス基板の表面にＳｉＯ_２を３０ｎｍ堆積させた。ガラス基板として、硬さ９Ｈの白板ガラスＳを用いた。次に防汚膜ＰＣの成膜を行なった。防汚膜ＰＣの成膜条件は、まず予備加熱工程として、防汚膜材料Ｍ１をシャッター２１１で覆い、防汚膜材料Ｍ１の沸点以上の温度で加熱を行なった。予備加熱温度は１６０℃、成膜温度は３００℃まで加熱した。 (Comparative Example 23)
In a 60 degree chamber atmosphere, first, SiO ₂ was deposited to a thickness of 30 nm on the surface of the glass substrate as the base film UC. A white plate glass S having a hardness of 9H was used as the glass substrate. Next, an antifouling film PC was formed. The film forming conditions for the antifouling film PC were as follows. First, as a preheating step, the antifouling film material M1 was covered with the shutter 211 and heated at a temperature equal to or higher than the boiling point of the antifouling film material M1. The preheating temperature was 160 ° C., and the film formation temperature was 300 ° C.

　図２６に示すように、予備加熱工程から成膜工程への移行は、真空チャンバー２００内の圧力の変化率が上昇から減少に転じた後、変化率が急峻な状態から緩やかな状態に転じた後となる位置Ｐ７（約１５０秒）で行なった。 As shown in FIG. 26, in the transition from the preheating process to the film forming process, after the rate of change in the pressure in the vacuum chamber 200 changed from an increase to a decrease, the rate of change changed from a steep state to a gentle state. This was performed at a later position P7 (about 150 seconds).

　図１９に示すように、防汚膜ＰＣの成膜後のガラス基板表面の摩耗試験のキズ本数は５本以上であった。摩耗試験後の接触角は１０８．４度であった。よって、良好な耐久性能を備えるガラス基板を得ることはできなかった。 As shown in FIG. 19, the number of scratches in the abrasion test on the glass substrate surface after the formation of the antifouling film PC was 5 or more. The contact angle after the wear test was 108.4 degrees. Therefore, a glass substrate having good durability could not be obtained.

　（比較例２４）
　６０度のチャンバー雰囲気内で、まず下地膜ＵＣとしてガラス基板の表面にＳｉＯ_２を３０ｎｍ堆積させた。ガラス基板として、硬さ９Ｈの白板ガラスＳを用いた。次に防汚膜ＰＣの成膜を行なった。防汚膜ＰＣの成膜条件は、まず予備加熱工程として、防汚膜材料Ｍ１をシャッター２１１で覆い、防汚膜材料Ｍ１の沸点以上の温度で加熱を行なった。予備加熱温度は１３０℃、成膜温度は３００℃まで加熱した。 (Comparative Example 24)
In a 60 degree chamber atmosphere, first, SiO ₂ was deposited to a thickness of 30 nm on the surface of the glass substrate as the base film UC. A white plate glass S having a hardness of 9H was used as the glass substrate. Next, an antifouling film PC was formed. The film forming conditions for the antifouling film PC were as follows. First, as a preheating step, the antifouling film material M1 was covered with the shutter 211 and heated at a temperature not lower than the boiling point of the antifouling film material M1. The preheating temperature was 130 ° C. and the film formation temperature was 300 ° C.

　図２７に示すように、予備加熱工程から成膜工程への移行は、真空チャンバー２００内の圧力の変化率が上昇から減少に転じる前となる位置Ｐ８（約５０秒）で行なった。 As shown in FIG. 27, the transition from the preheating process to the film forming process was performed at a position P8 (about 50 seconds) before the rate of change of the pressure in the vacuum chamber 200 changed from increasing to decreasing.

　図１９に示すように、防汚膜ＰＣの成膜後のガラス基板表面の摩耗試験のキズ本数は３本であった。摩耗試験後の接触角は１０２．４度であった。よって、良好な耐久性能を備えるガラス基板を得ることはできなかった。 As shown in FIG. 19, the number of scratches in the abrasion test on the glass substrate surface after the formation of the antifouling film PC was 3. The contact angle after the wear test was 102.4 degrees. Therefore, a glass substrate having good durability could not be obtained.

　（比較例２５）
　６０度のチャンバー雰囲気内で、まず下地膜ＵＣとしてガラス基板の表面にＳｉＯ_２を３０ｎｍ堆積させた。ガラス基板として、硬さ９Ｈの白板ガラスＳを用いた。次に防汚膜ＰＣの成膜を行なった。防汚膜ＰＣの成膜条件は、まず予備加熱工程として、防汚膜材料Ｍ１をシャッター２１１で覆い、防汚膜材料Ｍ１の沸点以上の温度で加熱を行なった。予備加熱温度は１３０℃、成膜温度は３００℃まで加熱した。 (Comparative Example 25)
In a 60 degree chamber atmosphere, first, SiO ₂ was deposited to a thickness of 30 nm on the surface of the glass substrate as the base film UC. A white plate glass S having a hardness of 9H was used as the glass substrate. Next, an antifouling film PC was formed. The film forming conditions for the antifouling film PC were as follows. First, as a preheating step, the antifouling film material M1 was covered with the shutter 211 and heated at a temperature equal to or higher than the boiling point of the antifouling film material M1. The preheating temperature was 130 ° C. and the film formation temperature was 300 ° C.

　図２８に示すように、予備加熱工程から成膜工程への移行は、真空チャンバー２００内の圧力の変化率が上昇となる位置Ｐ９（約５０秒）で行なった。 As shown in FIG. 28, the transition from the preheating process to the film forming process was performed at a position P9 (about 50 seconds) at which the rate of change in pressure in the vacuum chamber 200 increased.

　図１９に示すように、防汚膜ＰＣの成膜後のガラス基板表面の摩耗試験のキズ本数は３本であった。摩耗試験後の接触角は１０４．７度であった。よって、良好な耐久性能を備えるガラス基板を得ることはできなかった。 As shown in FIG. 19, the number of scratches in the abrasion test on the glass substrate surface after the formation of the antifouling film PC was 3. The contact angle after the wear test was 104.7 degrees. Therefore, a glass substrate having good durability could not be obtained.

　以上、本実施の形態においては、防汚膜を成膜する工程は、防汚材料を沸点未満の温度で加熱し、防汚材料に含まれる不純物を放出させる予備加熱工程と、予備加熱工程の後、防汚材料を沸点以上まで加熱を行ない、ガラス基板の被成膜面に防汚膜を成膜する成膜工程とを備え、予備加熱工程は、ガラス基板の前記被成膜面に、防汚膜材料から放出される前記不純物が到達しない状態で行なわれ、成膜工程は、ラス基板の被成膜面に、防汚膜材料から放出される前記防汚膜の材料が到達する状態で行なわれ、予備加熱工程から成膜工程への移行は、真空チャンバー内の圧力の変化率が上昇から減少に転じた後、変化率が急峻な状態から緩やかな状態に転じた後に行なっている。 As described above, in the present embodiment, the step of forming the antifouling film includes the preheating step of heating the antifouling material at a temperature lower than the boiling point and releasing impurities contained in the antifouling material, and the preheating step. Thereafter, the antifouling material is heated to a boiling point or more, and a film forming step for forming an antifouling film on the film formation surface of the glass substrate is provided.A preheating step is performed on the film formation surface of the glass substrate. The state where the impurities released from the antifouling film material are not reached, and the film forming step is a state where the material of the antifouling film released from the antifouling film material reaches the film formation surface of the lath substrate The transition from the preheating process to the film forming process is performed after the rate of change in pressure in the vacuum chamber has changed from an increase to a decrease and then the rate of change has changed from a steep state to a gentle state. .

　これにより、防汚膜材料に含まれる不純物がガラス基板に曝されることを抑制でき、防汚膜材料に含まれる不純物が防汚膜の蒸着成膜工程時には除去されている。その結果、防汚膜材料の有効成分のみがガラス基板に成膜され、膜質が安定し摩耗耐久性を向上させることが可能となる。 Thereby, it is possible to suppress the impurities contained in the antifouling film material from being exposed to the glass substrate, and the impurities contained in the antifouling film material are removed during the deposition process of the antifouling film. As a result, only the effective component of the antifouling film material is deposited on the glass substrate, and the film quality is stabilized and the wear durability can be improved.

　［実施の形態３］
　本発明に基づいた実施の形態３におけるガラス製品の製造方法について、以下、図を参照しながら説明する。ディスプレイ装置１００およびディスプレイ用カバーガラス１０の構成は、上記実施の形態１と同じであるため、ここでの説明は省略する。 [Embodiment 3]
A glass product manufacturing method according to Embodiment 3 based on the present invention will be described below with reference to the drawings. Since the configurations of the display device 100 and the display cover glass 10 are the same as those of the first embodiment, description thereof is omitted here.

　（ガラス製品の製造方法）
　図３に示した第１の真空チャンバー２００を用いた場合の、本実施の形態におけるディスプレイ用カバーガラス１０の製造方法に関し、図２９を参照して、フッ素系化合物を含有する防汚膜材料Ｍ１を用いた真空蒸着法により、ディスプレイ用カバーガラス１０の表面１１にフッ素系の防汚膜ＰＣを成膜する工程について以下する。 (Glass product manufacturing method)
With reference to FIG. 29, the antifouling film material M1 containing a fluorine-based compound will be described with reference to FIG. 29 regarding the method for manufacturing the display cover glass 10 in the present embodiment when the first vacuum chamber 200 shown in FIG. 3 is used. A process of forming a fluorine-based antifouling film PC on the surface 11 of the display cover glass 10 by a vacuum deposition method using the following will be described.

　予備加熱工程においては、防汚膜材料Ｍ１に含有する有効成分が、９５ｗｔ％以上になるまで加熱を行なう。ここで、加熱温度が防汚膜材料Ｍ１の沸点以上に達してしまうと、有効成分が熱的要因により失活したり、有効成分が蒸発し無駄に使用したりしてしまうので、沸点－５０°以上沸点未満の温度で実施することが好ましい。 In the preheating step, heating is performed until the active ingredient contained in the antifouling film material M1 is 95 wt% or more. Here, if the heating temperature reaches or exceeds the boiling point of the antifouling film material M1, the active ingredient is deactivated due to a thermal factor, or the active ingredient evaporates and is used wastefully. It is preferable to carry out at a temperature not lower than the boiling point and lower than the boiling point.

　たとえば、有効成分濃度２０％の防汚膜材料Ｍ１を１ｇ使用して成膜を行ないたい場合、９５ｗｔ％となる０．２１ｇ以下になるまで加熱を行なう。より好ましくは、１００ｗｔ％となる０．２ｇまで加熱を行なう。防汚膜材料Ｍ１を加熱することによって、防汚膜材料Ｍ１に含まれる不純物が放出される。 For example, when it is desired to form a film using 1 g of the antifouling film material M1 having an active ingredient concentration of 20%, heating is performed until the film becomes 0.21 g or less, which is 95 wt%. More preferably, the heating is performed up to 0.2 g which is 100 wt%. By heating the antifouling film material M1, impurities contained in the antifouling film material M1 are released.

　防汚膜材料Ｍ１の質量のモニタリングは、真空チャンバー２００内に熱源と重量計とを兼ね備えた蒸発源を用いることが最も好ましい。予め、加熱条件とその加熱による質量の増減量を測定しておき、それに基づき設定された成膜条件を定常的に使っても良い。 For monitoring the mass of the antifouling film material M1, it is most preferable to use an evaporation source having both a heat source and a weight meter in the vacuum chamber 200. The heating conditions and the amount of increase / decrease in mass due to the heating may be measured in advance, and the film-forming conditions set based on them may be used regularly.

　予備加熱工程から成膜工程への移行は、防汚材料Ｍ１中の有効成分量の占める質量％濃度が、９５ｗｔ％以上となった後に行なう。 The transition from the preheating step to the film forming step is performed after the mass% concentration of the active ingredient amount in the antifouling material M1 becomes 95 wt% or more.

　上記したように、予備加熱工程においては、防汚膜材料Ｍ１を加熱することによって、防汚膜材料Ｍ１に含まれる不純物が放出される。この不純物は、後の成膜工程に悪影響を与える。したがって、同一の真空チャンバー２００内で予備加熱工程および成膜工程を行なう場合には、真空チャンバー２００内に以下の構成を備えるとよい。不純物が後の成膜工程に悪影響を与えない場合には、下記の構成を採用する必要はない。 As described above, in the preheating step, the impurities contained in the antifouling film material M1 are released by heating the antifouling film material M1. This impurity adversely affects the subsequent film forming process. Therefore, when the preheating step and the film forming step are performed in the same vacuum chamber 200, the following configuration may be provided in the vacuum chamber 200. In the case where impurities do not adversely affect the subsequent film formation process, it is not necessary to adopt the following configuration.

　真空チャンバー２００内にシャッター２１１を設ける予備加熱工程においては、シャッター２１１を、防汚膜材料Ｍ１を覆う位置Ｐ１に移動させた状態で、防汚膜材料Ｍ１の加熱を行なう。成膜工程においては、シャッター２１１を、防汚膜材料Ｍ１を開放する位置Ｐ２に移動させた状態で、防汚膜材料Ｍ１の加熱を行なう。ガラス１０の表面１１に、フッ素系の防汚膜ＰＣを所望の膜厚まで成膜する成膜工程を実施する。膜厚さは、ｎｍオーダーで制御され、所望の膜厚とは、成膜後、ディスプレイ用カバーガラス１０が防汚膜ＰＣによって白濁しない程度の膜厚のことを言う。 In the preheating step of providing the shutter 211 in the vacuum chamber 200, the antifouling film material M1 is heated in a state where the shutter 211 is moved to the position P1 covering the antifouling film material M1. In the film forming process, the antifouling film material M1 is heated in a state where the shutter 211 is moved to the position P2 where the antifouling film material M1 is opened. A film forming step for forming a fluorine-based antifouling film PC to a desired film thickness on the surface 11 of the glass 10 is performed. The film thickness is controlled on the order of nm, and the desired film thickness means a film thickness that does not cause the display cover glass 10 to become clouded by the antifouling film PC after film formation.

　これにより、防汚材料Ｍ１に含まれる不純物がガラス基板に曝されることを抑制でき、ガラス基板と撥油性を有する有効成分との密着性が向上し摩耗耐久性が向上する効果と、防汚材料Ｍ１に含まれる不純物が成膜工程時には除去されていることで、有効成分のみがガラス基板に成膜され、膜質が安定し摩耗耐久性が向上する効果とを得ることが可能な、ディスプレイ用カバーガラス１０の製造方法を可能としている。 As a result, the impurities contained in the antifouling material M1 can be prevented from being exposed to the glass substrate, the adhesion between the glass substrate and the active ingredient having oil repellency is improved, and the wear durability is improved. For the display, the impurities contained in the material M1 are removed during the film forming process, so that only the active ingredient is formed on the glass substrate, and the film quality is stabilized and the wear durability is improved. The manufacturing method of the cover glass 10 is made possible.

　予備加熱工程から成膜工程への移行は、防汚材料Ｍ１中の有効成分量の占める質量％濃度が、９５ｗｔ％以上となった後に行なう。第２開閉部材３８０を開放して、基板支持部材３１３を防汚成膜チャンバー３００Ｃに移送する（図４中Ｔ２方向）。その後、防汚膜材料Ｍ１の温度を上昇させて、防汚成膜チャンバー３００Ｃ内で成膜工程を実施する。 The transition from the preheating step to the film forming step is performed after the mass% concentration of the active ingredient amount in the antifouling material M1 becomes 95 wt% or more. The second opening / closing member 380 is opened, and the substrate support member 313 is transferred to the antifouling film formation chamber 300C (direction T2 in FIG. 4). Thereafter, the temperature of the antifouling film material M1 is raised, and the film forming process is performed in the antifouling film forming chamber 300C.

　基板支持部材３１３の下地成膜チャンバー３００Ｂから防汚成膜チャンバー３００Ｃへの移送は、防汚成膜チャンバー３００Ｃ内の真空状態が維持された状態で、防汚成膜チャンバー３００Ｃ内に基板支持部材３１３が導入されるとよい。予備加熱工程および成膜工程の真空チャンバー内の圧力は、１０^－９Ｐａ～１Ｐａの範囲であるとよい。成膜時における成膜条件および温調制御は、上記と同じである。 The substrate supporting member 313 is transferred from the base film forming chamber 300B to the antifouling film forming chamber 300C in a state where the vacuum state in the antifouling film forming chamber 300C is maintained, and the substrate supporting member is placed in the antifouling film forming chamber 300C. 313 may be introduced. The pressure in the vacuum chamber in the preheating step and the film forming step is preferably in the range of 10 ⁻⁹ Pa to 1 Pa. Film formation conditions and temperature control during film formation are the same as described above.

　基本的な製造方法は、第２の真空チャンバー３００を用いた場合と同様である。予備加熱工程から成膜工程への移行は、防汚材料Ｍ１中の有効成分量の占める質量％濃度が、９５ｗｔ％以上となった後に行なう。第２開閉部材３８０を開放して、基板支持部材３１３を防汚成膜チャンバー３００Ｃに移送する（図４中Ｔ２方向）。 The basic manufacturing method is the same as that when the second vacuum chamber 300 is used. The transition from the preheating process to the film forming process is performed after the mass% concentration of the active ingredient amount in the antifouling material M1 becomes 95 wt% or more. The second opening / closing member 380 is opened, and the substrate support member 313 is transferred to the antifouling film formation chamber 300C (direction T2 in FIG. 4).

　（実施例）
　次に、上記第１の真空チャンバー２００を用いて実施したガラス製品の製造方法の実施例３１から３４、および比較例３１から３４について以下説明する。実施例３１から３４および比較例３１から３４において用いた防汚膜材料Ｍ１は、ダイキン社製の『オプツール（登録商標）ＤＳＸ』である。 (Example)
Next, Examples 31 to 34 and Comparative Examples 31 to 34 of the glass product manufacturing method performed using the first vacuum chamber 200 will be described below. The antifouling film material M1 used in Examples 31 to 34 and Comparative Examples 31 to 34 is “OPTOOL (registered trademark) DSX” manufactured by Daikin.

　各実施例および各比較例における各種成膜条件は、図７に示すとおりである。
　（実施例３１）
　６０度のチャンバー雰囲気内で、まず下地膜ＵＣとしてガラス基板の表面にＳｉＯ_２を３０ｎｍ堆積させた。ガラス基板として、硬さ９Ｈの白板ガラスＳを用いた。次に防汚膜ＰＣの成膜を行なった。防汚膜ＰＣの成膜条件は、まず予備加熱工程として、防汚膜材料Ｍ１をシャッター２１１で覆い、有効成分濃度２０％が０．５ｇの防汚膜材料Ｍ１を沸点－５０℃以上沸点未満の１６０度で、防汚膜材料Ｍ１が０．１ｇになるまで加熱を行なった。有効成分量の占める質量％濃度は１００ｗｔ％である。その後、シャッター２１１を開放し、防汚膜材料Ｍ１を沸点以上の温度（到達温度３００℃）に加熱して、ガラス基板上に防汚膜ＰＣを成膜した。 Various film forming conditions in each example and each comparative example are as shown in FIG.
(Example 31)
In a 60 degree chamber atmosphere, first, SiO ₂ was deposited to a thickness of 30 nm on the surface of the glass substrate as the base film UC. A white plate glass S having a hardness of 9H was used as the glass substrate. Next, an antifouling film PC was formed. The film forming conditions of the antifouling film PC are as follows. First, as a preheating process, the antifouling film material M1 is covered with the shutter 211, and the antifouling film material M1 having an active ingredient concentration of 20% is 0.5 g. Was heated until the antifouling film material M1 became 0.1 g. The mass% concentration occupied by the amount of the active ingredient is 100 wt%. Thereafter, the shutter 211 was opened, and the antifouling film material M1 was heated to a temperature equal to or higher than the boiling point (attainment temperature 300 ° C.) to form the antifouling film PC on the glass substrate.

　図３０に示すように、防汚膜ＰＣの成膜後のガラス基板表面の摩耗試験のキズ本数は０本であった。摩耗試験後の接触角は１１４．０度であった。よって、最良な耐久性能を備えるガラス基板が得られた。 As shown in FIG. 30, the number of scratches in the abrasion test on the glass substrate surface after the formation of the antifouling film PC was zero. The contact angle after the abrasion test was 114.0 degrees. Therefore, a glass substrate having the best durability performance was obtained.

　摩耗試験は、摩耗試験機（商品名「トライボギア」（新東科学社製））を用い、スチールウール＃００００番、１ｃｍ２に対して荷重２ｋｇで摩耗２０００回摩耗し、摩耗後に油性マジックで摩耗面を擦りキズの本数と純水の接触角を測定した。サンプル試作は１条件につき１０バッチ行ない、その平均値をとり評価を行なった。温度の測定は、防汚膜材料Ｍ１を入れる防汚膜材料収容容器に熱電対を接触させて測定した。各ガラス基板は成膜後、２４時間室温放置し、その後測定を行なった。以下の実施例および比較例でも同様である。 The wear test was performed using a wear tester (trade name “Tribogear” (manufactured by Shinto Kagaku Co., Ltd.)), and the steel wool # 0000, 1 cm 2, was worn 2000 times with a load of 2 kg. The number of scratches and the contact angle of pure water were measured. The sample trial production was performed 10 batches per condition, and the average value was evaluated. The temperature was measured by bringing a thermocouple into contact with the antifouling film material container into which the antifouling film material M1 was placed. Each glass substrate was allowed to stand at room temperature for 24 hours after film formation, and then measured. The same applies to the following examples and comparative examples.

　（実施例３２）
　６０度のチャンバー雰囲気内で、まず下地膜ＵＣとしてガラス基板の表面にＳｉＯ_２を３０ｎｍ堆積させた。ガラス基板として、硬さ９Ｈの白板ガラスＳを用いた。次に防汚膜ＰＣの成膜を行なった。防汚膜ＰＣの成膜条件は、まず予備加熱工程として、防汚膜材料Ｍ１をシャッター２１１で覆い、有効成分濃度２０％が０．５ｇの防汚膜材料Ｍ１を沸点－５０°以上沸点未満の１６０度で、防汚膜材料Ｍ１が０．１０５ｇになるまで加熱を行なった。有効成分量の占める質量％濃度は９５ｗｔ％である。その後、シャッター２１１を開放し、防汚膜材料Ｍ１を沸点以上の温度（到達温度３００℃）に加熱して、ガラス基板上に防汚膜ＰＣを成膜した。 (Example 32)
In a 60 degree chamber atmosphere, first, SiO ₂ was deposited to a thickness of 30 nm on the surface of the glass substrate as the base film UC. A white plate glass S having a hardness of 9H was used as the glass substrate. Next, an antifouling film PC was formed. The film forming conditions of the antifouling film PC are as follows. First, as a preheating process, the antifouling film material M1 is covered with the shutter 211, and the antifouling film material M1 having an active ingredient concentration of 20% is 0.5 g. Was heated until the antifouling film material M1 became 0.105 g. The mass% concentration occupied by the active ingredient amount is 95 wt%. Thereafter, the shutter 211 was opened, and the antifouling film material M1 was heated to a temperature equal to or higher than the boiling point (attainment temperature 300 ° C.) to form the antifouling film PC on the glass substrate.

　図３０に示すように、防汚膜ＰＣの成膜後のガラス基板表面の摩耗試験のキズ本数は０本であった。摩耗試験後の接触角は１１１．２度であった。よって、最良な耐久性能を備えるガラス基板が得られた。 As shown in FIG. 30, the number of scratches in the abrasion test on the glass substrate surface after the formation of the antifouling film PC was zero. The contact angle after the wear test was 111.2 degrees. Therefore, a glass substrate having the best durability performance was obtained.

　（実施例３３）
　６０度のチャンバー雰囲気内で、まず下地膜ＵＣとしてガラス基板の表面にＳｉＯ_２を３０ｎｍ堆積させた。ガラス基板として、硬さ９Ｈの白板ガラスＳを用いた。次に防汚膜ＰＣの成膜を行なった。防汚膜ＰＣの成膜条件は、まず予備加熱工程として、防汚膜材料Ｍ１をシャッター２１１で覆い、有効成分濃度２０％が０．５ｇの防汚膜材料Ｍ１を沸点－５０°以上沸点未満の１６０度で、防汚膜材料Ｍ１が０．１０３ｇになるまで加熱を行なった。有効成分量の占める質量％濃度は９７ｗｔ％である。その後、シャッター２１１を開放し、防汚膜材料Ｍ１を沸点以上の温度（到達温度３００℃）に加熱して、ガラス基板上に防汚膜ＰＣを成膜した。 (Example 33)
In a 60 degree chamber atmosphere, first, SiO ₂ was deposited to a thickness of 30 nm on the surface of the glass substrate as the base film UC. A white plate glass S having a hardness of 9H was used as the glass substrate. Next, an antifouling film PC was formed. The film forming conditions of the antifouling film PC are as follows. First, as a preheating process, the antifouling film material M1 is covered with the shutter 211, and the antifouling film material M1 having an active ingredient concentration of 20% is 0.5 g. Was heated until the antifouling film material M1 reached 0.103 g. The concentration by mass of the active ingredient is 97 wt%. Thereafter, the shutter 211 was opened, and the antifouling film material M1 was heated to a temperature equal to or higher than the boiling point (attainment temperature 300 ° C.) to form the antifouling film PC on the glass substrate.

　図３０に示すように、防汚膜ＰＣの成膜後のガラス基板表面の摩耗試験のキズ本数は０本であった。摩耗試験後の接触角は１１１．９度であった。よって、最良な耐久性能を備えるガラス基板が得られた。 As shown in FIG. 30, the number of scratches in the abrasion test on the glass substrate surface after the formation of the antifouling film PC was zero. The contact angle after the wear test was 111.9 degrees. Therefore, a glass substrate having the best durability performance was obtained.

　（実施例３４）
　６０度のチャンバー雰囲気内で、まず下地膜ＵＣとしてガラス基板の表面にＳｉＯ_２を３０ｎｍ堆積させた。ガラス基板として、硬さ９Ｈの白板ガラスＳを用いた。次に防汚膜ＰＣの成膜を行なった。防汚膜ＰＣの成膜条件は、まず予備加熱工程として、防汚膜材料Ｍ１をシャッター２１１で覆い、有効成分濃度２０％が０．５ｇの防汚膜材料Ｍ１を沸点－５０°以上沸点未満の１６０度で、防汚膜材料Ｍ１が０．１１１ｇになるまで加熱を行なった。有効成分量の占める質量％濃度は９０ｗｔ％である。その後、シャッター２１１を開放し、防汚膜材料Ｍ１を沸点以上の温度（到達温度３００℃）に加熱して、ガラス基板上に防汚膜ＰＣを成膜した。 (Example 34)
In a 60 degree chamber atmosphere, first, SiO ₂ was deposited to a thickness of 30 nm on the surface of the glass substrate as the base film UC. A white plate glass S having a hardness of 9H was used as the glass substrate. Next, an antifouling film PC was formed. The film forming conditions of the antifouling film PC are as follows. First, as a preheating process, the antifouling film material M1 is covered with the shutter 211, and the antifouling film material M1 having an active ingredient concentration of 20% is 0.5 g. The film was heated at 160 degrees until the antifouling film material M1 reached 0.111 g. The mass% concentration occupied by the amount of the active ingredient is 90 wt%. Thereafter, the shutter 211 was opened, and the antifouling film material M1 was heated to a temperature equal to or higher than the boiling point (attainment temperature 300 ° C.) to form the antifouling film PC on the glass substrate.

　図３０に示すように、防汚膜ＰＣの成膜後のガラス基板表面の摩耗試験のキズ本数は１本であった。摩耗試験後の接触角は１０９．４度であった。よって、良好な耐久性能を備えるガラス基板が得られた。 As shown in FIG. 30, the number of scratches in the abrasion test on the surface of the glass substrate after the formation of the antifouling film PC was one. The contact angle after the abrasion test was 109.4 degrees. Therefore, the glass substrate provided with favorable durability performance was obtained.

　（比較例３１）
　６０度のチャンバー雰囲気内で、まず下地膜ＵＣとしてガラス基板の表面にＳｉＯ_２を３０ｎｍ堆積させた。ガラス基板として、硬さ９Ｈの白板ガラスＳを用いた。次に防汚膜ＰＣの成膜を行なった。防汚膜ＰＣの成膜条件は、まず予備加熱工程として、防汚膜材料Ｍ１をシャッター２１１で覆い、有効成分濃度２０％が０．５ｇの防汚膜材料Ｍ１を沸点未満の１６０度で、防汚膜材料Ｍ１が０．１３ｇになるまで加熱を行なった。有効成分量の占める質量％濃度は７７ｗｔ％である。その後、シャッター２１１を開放し、防汚膜材料Ｍ１を沸点以上の温度（到達温度３００℃）に加熱して、ガラス基板上に防汚膜ＰＣを成膜した。 (Comparative Example 31)
In a 60 degree chamber atmosphere, first, SiO ₂ was deposited to a thickness of 30 nm on the surface of the glass substrate as the base film UC. A white plate glass S having a hardness of 9H was used as the glass substrate. Next, an antifouling film PC was formed. The film forming conditions of the antifouling film PC are as follows. First, as a preheating process, the antifouling film material M1 is covered with the shutter 211, and the antifouling film material M1 having an active ingredient concentration of 20% of 0.5 g is 160 degrees below the boiling point. Heating was performed until the antifouling film material M1 was 0.13 g. The concentration by mass of the active ingredient is 77 wt%. Thereafter, the shutter 211 was opened, and the antifouling film material M1 was heated to a temperature equal to or higher than the boiling point (attainment temperature 300 ° C.) to form the antifouling film PC on the glass substrate.

　図３０に示すように、防汚膜ＰＣの成膜後のガラス基板表面の摩耗試験のキズ本数は５本以上であった。摩耗試験後の接触角は１０３．４度であった。よって、良好な耐久性能を備えるガラス基板を得ることはできなかった。 As shown in FIG. 30, the number of scratches in the abrasion test on the surface of the glass substrate after the formation of the antifouling film PC was 5 or more. The contact angle after the wear test was 103.4 degrees. Therefore, a glass substrate having good durability could not be obtained.

　（比較例３２）
　６０度のチャンバー雰囲気内で、まず下地膜ＵＣとしてガラス基板の表面にＳｉＯ_２を３０ｎｍ堆積させた。ガラス基板として、硬さ９Ｈの白板ガラスＳを用いた。次に防汚膜ＰＣの成膜を行なった。防汚膜ＰＣの成膜条件は、まず予備加熱工程として、防汚膜材料Ｍ１をシャッター２１１で覆い、有効成分濃度２０％が０．５ｇの防汚膜材料Ｍ１を沸点未満の１６０度で、防汚膜材料Ｍ１が０．１３ｇになるまで加熱を行なった。有効成分量の占める質量％濃度は８３ｗｔ％である。その後、シャッター２１１を開放し、防汚膜材料Ｍ１を沸点以上の温度（到達温度３００℃）に加熱して、ガラス基板上に防汚膜ＰＣを成膜した。 (Comparative Example 32)
In a 60 degree chamber atmosphere, first, SiO ₂ was deposited to a thickness of 30 nm on the surface of the glass substrate as the base film UC. A white plate glass S having a hardness of 9H was used as the glass substrate. Next, an antifouling film PC was formed. The film forming conditions of the antifouling film PC are as follows. First, as a preheating process, the antifouling film material M1 is covered with the shutter 211, and the antifouling film material M1 having an active ingredient concentration of 20% of 0.5 g is 160 degrees below the boiling point. Heating was performed until the antifouling film material M1 was 0.13 g. The concentration by mass of the active ingredient is 83 wt%. Thereafter, the shutter 211 was opened, and the antifouling film material M1 was heated to a temperature equal to or higher than the boiling point (attainment temperature 300 ° C.) to form the antifouling film PC on the glass substrate.

　図３０に示すように、防汚膜ＰＣの成膜後のガラス基板表面の摩耗試験のキズ本数は５本であった。摩耗試験後の接触角は１０２．８度であった。よって、良好な耐久性能を備えるガラス基板を得ることはできなかった。 As shown in FIG. 30, the number of scratches in the abrasion test on the surface of the glass substrate after the formation of the antifouling film PC was 5. The contact angle after the wear test was 102.8 degrees. Therefore, a glass substrate having good durability could not be obtained.

　（比較例３３）
　６０度のチャンバー雰囲気内で、まず下地膜ＵＣとしてガラス基板の表面にＳｉＯ_２を３０ｎｍ堆積させた。ガラス基板として、硬さ９Ｈの白板ガラスＳを用いた。次に防汚膜ＰＣの成膜を行なった。防汚膜ＰＣの成膜条件は、まず予備加熱工程として、防汚膜材料Ｍ１をシャッター２１１で覆い、有効成分濃度２０％が０．５ｇの防汚膜材料Ｍ１を沸点以上の２００度で、防汚膜材料Ｍ１が０．０８ｇになるまで加熱を行なった。有効成分量の占める質量％濃度は１００ｗｔ％である。その後、シャッター２１１を開放し、防汚膜材料Ｍ１を沸点以上の温度（到達温度３００℃）に加熱して、ガラス基板上に防汚膜ＰＣを成膜した。 (Comparative Example 33)
In a 60 degree chamber atmosphere, first, SiO ₂ was deposited to a thickness of 30 nm on the surface of the glass substrate as the base film UC. A white plate glass S having a hardness of 9H was used as the glass substrate. Next, an antifouling film PC was formed. The film forming conditions of the antifouling film PC are as follows. First, as a preheating process, the antifouling film material M1 is covered with the shutter 211, and the antifouling film material M1 having an active ingredient concentration of 20% of 0.5 g is 200 ° C. above the boiling point. Heating was performed until the antifouling film material M1 was 0.08 g. The mass% concentration occupied by the amount of the active ingredient is 100 wt%. Thereafter, the shutter 211 was opened, and the antifouling film material M1 was heated to a temperature equal to or higher than the boiling point (attainment temperature 300 ° C.) to form the antifouling film PC on the glass substrate.

　図３０に示すように、防汚膜ＰＣの成膜後のガラス基板表面の摩耗試験のキズ本数は５本であった。摩耗試験後の接触角は１００．４度であった。予備加熱工程での加熱温度が防汚膜材料Ｍ１の沸点温度を越えているため、良好な耐久性能を備えるガラス基板を得ることはできなかった。 As shown in FIG. 30, the number of scratches in the abrasion test on the surface of the glass substrate after the formation of the antifouling film PC was 5. The contact angle after the abrasion test was 100.4 degrees. Since the heating temperature in the preheating step exceeds the boiling point temperature of the antifouling film material M1, a glass substrate having good durability could not be obtained.

　（比較例３４）
　６０度のチャンバー雰囲気内で、まず下地膜ＵＣとしてガラス基板の表面にＳｉＯ_２を３０ｎｍ堆積させた。ガラス基板として、硬さ９Ｈの白板ガラスＳを用いた。次に防汚膜ＰＣの成膜を行なった。防汚膜ＰＣの成膜条件は、まず予備加熱工程として、防汚膜材料Ｍ１をシャッター２１１で覆い、有効成分濃度２０％が０．５ｇの防汚膜材料Ｍ１を沸点未満の２００度で、防汚膜材料Ｍ１が０．１ｇになるまで加熱を行なった。有効成分量の占める質量％濃度は１００ｗｔ％である。その後、シャッター２１１を開放し、防汚膜材料Ｍ１を沸点以上の温度（到達温度３００℃）に加熱して、ガラス基板上に防汚膜ＰＣを成膜した。 (Comparative Example 34)
In a 60 degree chamber atmosphere, first, SiO ₂ was deposited to a thickness of 30 nm on the surface of the glass substrate as the base film UC. A white plate glass S having a hardness of 9H was used as the glass substrate. Next, an antifouling film PC was formed. The film forming conditions of the antifouling film PC are as follows. First, as a preheating process, the antifouling film material M1 is covered with the shutter 211, and the antifouling film material M1 having an active ingredient concentration of 20% is 0.5 g at 200 degrees below the boiling point. Heating was performed until the antifouling film material M1 became 0.1 g. The mass% concentration occupied by the amount of the active ingredient is 100 wt%. Thereafter, the shutter 211 was opened, and the antifouling film material M1 was heated to a temperature equal to or higher than the boiling point (attainment temperature 300 ° C.) to form the antifouling film PC on the glass substrate.

　図３０に示すように、防汚膜ＰＣの成膜後のガラス基板表面の摩耗試験のキズ本数は３本であった。摩耗試験後の接触角は１０７．２度であった。シャッター２１１により防汚膜材料Ｍ１を覆わずに防汚膜材料Ｍ１の加熱を行なったため、良好な耐久性能を備えるガラス基板を得ることはできなかった。 As shown in FIG. 30, the number of scratches in the abrasion test on the surface of the glass substrate after the antifouling film PC was formed was 3. The contact angle after the abrasion test was 107.2 degrees. Since the antifouling film material M1 was heated without covering the antifouling film material M1 with the shutter 211, a glass substrate having good durability performance could not be obtained.

　（実施例３５，３６　比較例３５，３６）
　第１の真空チャンバー２００を用いた場合において、防汚膜材料Ｍ１として、信越化学工業株式会社製の『ＫＹ－１７８』を用いた実施例５および比較例５、並びに、東レダウコーニング株式会社製の『Ｃｏｒｎｉｎｇ（登録商標）２６３４』を用いた実施例６および比較例６の場合を、図８に示した。 (Examples 35 and 36 Comparative Examples 35 and 36)
In the case of using the first vacuum chamber 200, Example 5 and Comparative Example 5 using “KY-178” manufactured by Shin-Etsu Chemical Co., Ltd. as the antifouling film material M1, and manufactured by Toray Dow Corning Co., Ltd. FIG. 8 shows the case of Example 6 and Comparative Example 6 using “Corning (registered trademark) 2634”.

　図３１は、第１の真空チャンバーを用いた場合の、実施例３５、実施例３６、比較例３５および比較例３６の各種条件を示す図である。 FIG. 31 is a diagram showing various conditions of Example 35, Example 36, Comparative Example 35, and Comparative Example 36 when the first vacuum chamber is used.

　（実施例３５）
　６０度のチャンバー雰囲気内で、まず下地膜ＵＣとしてガラス基板の表面にＳｉＯ_２を３０ｎｍ堆積させた。ガラス基板として、硬さ９Ｈの白板ガラスＳを用いた。次に防汚膜ＰＣの成膜を行なった。防汚膜ＰＣの成膜条件は、まず予備加熱工程として、防汚膜材料Ｍ１をシャッター２１１で覆い、有効成分濃度２０％が０．５ｇの防汚膜材料Ｍ１を沸点未満の１３０度で、防汚膜材料Ｍ１が０．１ｇになるまで加熱を行なった。有効成分量の占める質量％濃度は１００ｗｔ％である。その後、シャッター２１１を開放し、防汚膜材料Ｍ１を沸点以上の温度（到達温度３００℃）に加熱して、ガラス基板上に防汚膜ＰＣを成膜した。 (Example 35)
In a 60 degree chamber atmosphere, first, SiO ₂ was deposited to a thickness of 30 nm on the surface of the glass substrate as the base film UC. A white plate glass S having a hardness of 9H was used as the glass substrate. Next, an antifouling film PC was formed. The film forming conditions of the antifouling film PC are as follows. First, as a preheating step, the antifouling film material M1 is covered with the shutter 211, and the antifouling film material M1 having an active ingredient concentration of 20% of 0.5 g is 130 degrees below the boiling point. Heating was performed until the antifouling film material M1 became 0.1 g. The mass% concentration occupied by the amount of the active ingredient is 100 wt%. Thereafter, the shutter 211 was opened, and the antifouling film material M1 was heated to a temperature equal to or higher than the boiling point (attainment temperature 300 ° C.) to form the antifouling film PC on the glass substrate.

　図３１に示すように、防汚膜ＰＣの成膜後のガラス基板表面の摩耗試験のキズ本数は０本であった。摩耗試験後の接触角は１１４．１度であった。よって、最良な耐久性能を備えるガラス基板が得られた。 As shown in FIG. 31, the number of scratches in the abrasion test of the glass substrate surface after the antifouling film PC was formed was zero. The contact angle after the wear test was 114.1 degrees. Therefore, a glass substrate having the best durability performance was obtained.

　（実施例３６）
　６０度のチャンバー雰囲気内で、まず下地膜ＵＣとしてガラス基板の表面にＳｉＯ_２を３０ｎｍ堆積させた。ガラス基板として、硬さ９Ｈの白板ガラスＳを用いた。次に防汚膜ＰＣの成膜を行なった。防汚膜ＰＣの成膜条件は、まず予備加熱工程として、防汚膜材料Ｍ１をシャッター２１１で覆い、有効成分濃度２０％が０．５ｇの防汚膜材料Ｍ１を沸点未満の１３０度で、防汚膜材料Ｍ１が０．１ｇになるまで加熱を行なった。有効成分量の占める質量％濃度は１００ｗｔ％である。その後、シャッター２１１を開放し、防汚膜材料Ｍ１を沸点以上の温度（到達温度３００℃）に加熱して、ガラス基板上に防汚膜ＰＣを成膜した。 (Example 36)
In a 60 degree chamber atmosphere, first, SiO ₂ was deposited to a thickness of 30 nm on the surface of the glass substrate as the base film UC. A white plate glass S having a hardness of 9H was used as the glass substrate. Next, an antifouling film PC was formed. The film forming conditions of the antifouling film PC are as follows. First, as a preheating step, the antifouling film material M1 is covered with the shutter 211, and the antifouling film material M1 having an active ingredient concentration of 20% of 0.5 g is 130 degrees below the boiling point. Heating was performed until the antifouling film material M1 became 0.1 g. The mass% concentration occupied by the amount of the active ingredient is 100 wt%. Thereafter, the shutter 211 was opened, and the antifouling film material M1 was heated to a temperature equal to or higher than the boiling point (attainment temperature 300 ° C.) to form the antifouling film PC on the glass substrate.

　図３１に示すように、防汚膜ＰＣの成膜後のガラス基板表面の摩耗試験のキズ本数は０本であった。摩耗試験後の接触角は１１３．９度であった。よって、最良な耐久性能を備えるガラス基板が得られた。 As shown in FIG. 31, the number of scratches in the abrasion test of the glass substrate surface after the antifouling film PC was formed was zero. The contact angle after the abrasion test was 113.9 degrees. Therefore, a glass substrate having the best durability performance was obtained.

　（比較例３５）
　６０度のチャンバー雰囲気内で、まず下地膜ＵＣとしてガラス基板の表面にＳｉＯ_２を３０ｎｍ堆積させた。ガラス基板として、硬さ９Ｈの白板ガラスＳを用いた。次に防汚膜ＰＣの成膜を行なった。防汚膜ＰＣの成膜条件は、まず予備加熱工程として、防汚膜材料Ｍ１をシャッター２１１で覆い、有効成分濃度２０％が０．５ｇの防汚膜材料Ｍ１を沸点未満の１３０度で、防汚膜材料Ｍ１が０．１３ｇになるまで加熱を行なった。有効成分量の占める質量％濃度は８３ｗｔ％である。その後、シャッター２１１を開放し、防汚膜材料Ｍ１を沸点以上の温度（到達温度３００℃）に加熱して、ガラス基板上に防汚膜ＰＣを成膜した。 (Comparative Example 35)
In a 60 degree chamber atmosphere, first, SiO ₂ was deposited to a thickness of 30 nm on the surface of the glass substrate as the base film UC. A white plate glass S having a hardness of 9H was used as the glass substrate. Next, an antifouling film PC was formed. The film forming conditions of the antifouling film PC are as follows. First, as a preheating step, the antifouling film material M1 is covered with the shutter 211, and the antifouling film material M1 having an active ingredient concentration of 20% of 0.5 g is 130 degrees below the boiling point. Heating was performed until the antifouling film material M1 was 0.13 g. The concentration by mass of the active ingredient is 83 wt%. Thereafter, the shutter 211 was opened, and the antifouling film material M1 was heated to a temperature equal to or higher than the boiling point (attainment temperature 300 ° C.) to form the antifouling film PC on the glass substrate.

　図３１に示すように、防汚膜ＰＣの成膜後のガラス基板表面の摩耗試験のキズ本数は５本以上であった。摩耗試験後の接触角は９８．２度であった。よって、良好な耐久性能を備えるガラス基板を得ることはできなかった。 As shown in FIG. 31, the number of scratches in the abrasion test on the glass substrate surface after the formation of the antifouling film PC was 5 or more. The contact angle after the wear test was 98.2 degrees. Therefore, a glass substrate having good durability could not be obtained.

　（比較例３６）
　６０度のチャンバー雰囲気内で、まず下地膜ＵＣとしてガラス基板の表面にＳｉＯ_２を３０ｎｍ堆積させた。ガラス基板として、硬さ９Ｈの白板ガラスＳを用いた。次に防汚膜ＰＣの成膜を行なった。防汚膜ＰＣの成膜条件は、まず予備加熱工程として、防汚膜材料Ｍ１をシャッター２１１で覆い、有効成分濃度２０％が０．５ｇの防汚膜材料Ｍ１を沸点未満の１３０度で、防汚膜材料Ｍ１が０．１３ｇになるまで加熱を行なった。有効成分量の占める質量％濃度は８３ｗｔ％である。その後、シャッター２１１を開放し、防汚膜材料Ｍ１を沸点以上の温度（到達温度３００℃）に加熱して、ガラス基板上に防汚膜ＰＣを成膜した。 (Comparative Example 36)
In a 60 degree chamber atmosphere, first, SiO ₂ was deposited to a thickness of 30 nm on the surface of the glass substrate as the base film UC. A white plate glass S having a hardness of 9H was used as the glass substrate. Next, an antifouling film PC was formed. The film forming conditions of the antifouling film PC are as follows. First, as a preheating step, the antifouling film material M1 is covered with the shutter 211, and the antifouling film material M1 having an active ingredient concentration of 20% of 0.5 g is 130 degrees below the boiling point. Heating was performed until the antifouling film material M1 was 0.13 g. The concentration by mass of the active ingredient is 83 wt%. Thereafter, the shutter 211 was opened, and the antifouling film material M1 was heated to a temperature equal to or higher than the boiling point (attainment temperature 300 ° C.) to form the antifouling film PC on the glass substrate.

　図３１に示すように、防汚膜ＰＣの成膜後のガラス基板表面の摩耗試験のキズ本数は５本以上であった。摩耗試験後の接触角は１００．２度であった。よって、良好な耐久性能を備えるガラス基板を得ることはできなかった。 As shown in FIG. 31, the number of scratches in the abrasion test on the glass substrate surface after the formation of the antifouling film PC was 5 or more. The contact angle after the wear test was 100.2 degrees. Therefore, a glass substrate having good durability could not be obtained.

　以上、本実施の形態においては、上記予備加熱工程から上記成膜工程への移行は、上記防汚材料(M1)中の有効成分量の占める質量％濃度が、９５ｗｔ％以上となった後に行なっている。これにより、防汚材料に含まれる不純物がガラス基板に曝されることを抑制でき、ガラス基板と撥油性を有する有効成分との密着性が向上し摩耗耐久性が向上する効果と、防汚材料に含まれる不純物が成膜工程時には除去されていることで、有効成分のみがガラス基板に成膜され、膜質が安定し摩耗耐久性が向上する効果とを得ることが可能な、ディスプレイ用カバーガラスの製造方法を可能としている。 As described above, in the present embodiment, the transition from the preheating step to the film forming step is performed after the mass% concentration of the active ingredient amount in the antifouling material (M1) becomes 95 wt% or more. ing. This prevents the impurities contained in the antifouling material from being exposed to the glass substrate, improves the adhesion between the glass substrate and the active ingredient having oil repellency and improves the wear durability, and the antifouling material. Is removed during the film formation process, so that only the active ingredient is formed on the glass substrate, and the film quality is stabilized and the wear durability can be improved. The manufacturing method is possible.

　以上、本発明の各実施の形態および実施例について説明したが、今回開示された実施の形態および実施例はすべての点で例示であって制限的なものではないと考えられるべきである。本発明の範囲は請求の範囲によって示され、請求の範囲と均等の意味および範囲内でのすべての変更が含まれることが意図される。 Although the embodiments and examples of the present invention have been described above, the embodiments and examples disclosed this time should be considered as illustrative and not restrictive in all respects. The scope of the present invention is defined by the terms of the claims, and is intended to include any modifications within the scope and meaning equivalent to the terms of the claims.

　１０　ディスプレイ用カバーガラス、１０Ｈ　開口部、１１　表面、１２　裏面、１３　主面部、１４　接続部、１５　側面部、２０　外装プレート、３０　回路基板、３１　スピーカー、４０　ディスプレイ、４２　画像表示部、１００　ディスプレイ装置、２００　第１の真空チャンバー、２０１　ケーシング、２０１ｈ　排気口、２０３，３３３　ベース、２０５，３３５，３５５　ヒーター、２０７，３５７　膜材料収容容器、２０９，３５９　熱電対、２１１　シャッター、２１３，３１３　基板支持部材、３００　第２の真空チャンバー、３００Ａ　導入チャンバー、３００Ｂ　下地成膜チャンバー，３００Ｃ　防汚成膜チャンバー、３００Ｄ　予備加熱チャンバー、３０１　第１ケーシング、３１５　第１支持部材、３３１　第２ケーシング、３３７　下地膜材料収容容器、３４５　第２支持部材、３５１　第３ケーシング、３６５　第３支持部材、３７０　第１開閉部材、３７１　第４ケーシング、３８０　第２開閉部材、３９０　第３開閉部材、４００　第３の真空チャンバー。 10 display cover glass, 10H opening, 11 front surface, 12 back surface, 13 main surface portion, 14 connection portion, 15 side surface portion, 20 exterior plate, 30 circuit board, 31 speaker, 40 display, 42 image display portion, 100 display device , 200 first vacuum chamber, 201 casing, 201h exhaust port, 203,333 base, 205, 335, 355 heater, 207, 357 membrane material container, 209, 359 thermocouple, 211 shutter, 213, 313 substrate support member , 300 Second vacuum chamber, 300A introduction chamber, 300B foundation film forming chamber, 300C antifouling film forming chamber, 300D preheating chamber, 301 first casing, 315, first support member, 331 Second casing, 337, base film material container, 345, second support member, 351, third casing, 365, third support member, 370, first opening / closing member, 371, fourth casing, 380, second opening / closing member, 390, third opening / closing member 400 Third vacuum chamber.

Claims

　真空チャンバー内において、フッ素系化合物を含有する防汚膜材料を用いた真空蒸着法により、ガラス基板の被成膜面にフッ素系の防汚膜を成膜する工程を含む、ガラス製品の製造方法であって、
　前記ガラス基板を準備する工程と、
　前記ガラス基板の前記被成膜面にフッ素系の前記防汚膜を成膜する工程と、を備え、
　前記防汚膜を成膜する工程は、
　前記防汚膜材料に含有する不純物を放出するため、前記フッ素系化合物を、前記フッ素系化合物の沸点－５０度の温度より高く、かつ、前記沸点より低い温度にまで加熱する予備加熱工程と、
　前記予備加熱工程の後、前記フッ素系化合物を前記沸点より低い温度から前記沸点より高い温度にまで加熱し、前記ガラス基板の前記被成膜面に前記防汚膜を成膜する成膜工程と、
を備え、
　前記予備加熱工程は、前記ガラス基板の前記被成膜面に、前記防汚膜材料から放出される前記不純物が到達しない状態で行なわれ、
　前記成膜工程は、前記ガラス基板の前記被成膜面に、前記防汚膜材料から放出される前記防汚膜の材料が到達する状態で行なわれる、ガラス製品の製造方法。 A method for producing a glass product, comprising a step of forming a fluorine-based antifouling film on a film-forming surface of a glass substrate by a vacuum deposition method using an antifouling film material containing a fluorine-based compound in a vacuum chamber Because
Preparing the glass substrate;
Forming the fluorine-based antifouling film on the film-forming surface of the glass substrate,
The step of forming the antifouling film includes
A preheating step of heating the fluorine compound to a temperature higher than the boiling point of the fluorine compound and lower than the boiling point in order to release impurities contained in the antifouling film material;
A film forming step of heating the fluorine-based compound from a temperature lower than the boiling point to a temperature higher than the boiling point after the preliminary heating step, and forming the antifouling film on the film formation surface of the glass substrate; ,
With
The preheating step is performed in a state where the impurities released from the antifouling film material do not reach the film formation surface of the glass substrate,
The method of manufacturing a glass product, wherein the film forming step is performed in a state where the antifouling film material released from the antifouling film material reaches the film formation surface of the glass substrate.
　前記予備加熱工程および前記成膜工程は、同一のチャンバーの内部で行なわれ、
　前記予備加熱工程および前記成膜工程は、前記チャンバーの内部が常に排気状態で行なわれ、
　前記予備加熱工程は、前記被成膜面に、前記防汚膜材料から放出される前記不純物が到達しないように、前記被成膜面と前記防汚膜材料との間が物理的に遮られた状態で行なわれ、
　前記成膜工程は、前記被成膜面に、前記防汚膜材料から放出される前記防汚膜の材料が到達するように、前記被成膜面と前記防汚膜材料との間が物理的に開放された状態で行なわれる、請求項１に記載のガラス製品の製造方法。 The preheating step and the film forming step are performed inside the same chamber,
The preheating step and the film forming step are always performed in an exhausted state inside the chamber,
In the preheating step, the film formation surface and the antifouling film material are physically blocked so that the impurities released from the antifouling film material do not reach the film formation surface. Performed in a state
In the film formation step, a physical gap between the film formation surface and the antifouling film material is obtained so that the material of the antifouling film released from the antifouling film material reaches the film formation surface. The manufacturing method of the glassware of Claim 1 performed in the state open | released automatically.
　前記被成膜面と前記防汚膜材料との間には、シャッターが配設され、
　前記シャッターは、
　前記予備加熱工程においては、前記被成膜面に、前記防汚膜材料から放出される前記不純物が到達しないように前記防汚膜材料を覆い、
　前記成膜工程においては、前記被成膜面に、前記防汚膜材料から放出される前記防汚膜の材料が到達するように、前記防汚膜材料を開放する、請求項２に記載のガラス製品の製造方法。 A shutter is disposed between the film formation surface and the antifouling film material,
The shutter is
In the preliminary heating step, the antifouling film material is covered so that the impurities released from the antifouling film material do not reach the film formation surface,
3. The antifouling film material is opened in the film forming step so that the material of the antifouling film released from the antifouling film material reaches the film formation surface. Manufacturing method of glass products.
　前記予備加熱工程および前記成膜工程は、同一のチャンバーの内部で行なわれ、
　前記予備加熱工程および前記成膜工程は、前記チャンバーの内部が常に排気状態で実施され、
　前記予備加熱工程は、
　前記ガラス基板が導入されていない前記チャンバー内で行なわれることにより、前記防汚膜材料に含有する不純物が放出される工程を含み、
　前記成膜工程は、
　前記予備加熱工程の後に前記チャンバー内の真空状態が維持された状態で、前記チャンバー内に前記ガラス基板が導入される工程を含む、請求項１に記載のガラス製品の製造方法。 The preheating step and the film forming step are performed inside the same chamber,
The preheating step and the film forming step are always performed in an exhausted state inside the chamber,
The preheating step
Including the step of releasing impurities contained in the antifouling film material by being performed in the chamber into which the glass substrate is not introduced,
The film forming step includes
The manufacturing method of the glassware of Claim 1 including the process of introducing the said glass substrate in the said chamber in the state by which the vacuum state in the said chamber was maintained after the said preheating process.
　前記予備加熱工程は、予備加熱チャンバーで行なわれ、
　前記成膜工程は、防汚成膜チャンバーで行なわれ、
　前記予備加熱工程および前記成膜工程は、前記予備加熱チャンバーおよび前記防汚成膜チャンバーの内部が常に排気状態で実施され、
　前記予備加熱工程は、
　前記ガラス基板が導入された前記防汚成膜チャンバーとは異なる前記予備加熱チャンバーで行なわれることにより、前記防汚膜材料に含有する不純物が放出され工程を含み、
　前記成膜工程は、
　前記予備加熱工程の後に前記防汚成膜チャンバー内に、前記予備加熱工程が終了した前記防汚膜材料が導入される工程を含む、請求項１に記載のガラス製品の製造方法。 The preheating step is performed in a preheating chamber,
The film forming step is performed in an antifouling film forming chamber,
The preheating step and the film forming step are always performed in an exhausted state inside the preheating chamber and the antifouling film forming chamber,
The preheating step
Including the step of releasing impurities contained in the antifouling film material by being performed in the preheating chamber different from the antifouling film forming chamber into which the glass substrate is introduced,
The film forming step includes
The manufacturing method of the glassware of Claim 1 including the process of introduce | transducing the said antifouling film | membrane material which the said preheating process completed in the said antifouling film-forming chamber after the said preheating process.
　前記予備加熱工程は、前記防汚膜材料に含有する不純物を放出するため、前記防汚膜材料を、前記フッ素系化合物の沸点未満の温度にまで加熱する工程を含む、請求項１から５のいずれか１項に記載のガラス製品の製造方法。 The preheating step includes a step of heating the antifouling film material to a temperature below the boiling point of the fluorine-based compound in order to release impurities contained in the antifouling film material. The manufacturing method of the glass product of any one.
　前記不純物は、主にハイドロカーボンである、請求項１から６のいずれか１項に記載のガラス製品の製造方法。 The method for producing a glass product according to any one of claims 1 to 6, wherein the impurities are mainly hydrocarbons.
　前記ガラス基板の前記被成膜面にフッ素系の前記防汚膜を成膜する前に、前記ガラス基板の前記被成膜面に、二酸化珪素を主成分とした下地膜を成膜する工程をさらに含む、請求項１から７のいずれか１項に記載のガラス製品の製造方法。 Before forming the fluorine-based antifouling film on the film-forming surface of the glass substrate, forming a base film mainly composed of silicon dioxide on the film-forming surface of the glass substrate; Furthermore, the manufacturing method of the glass product of any one of Claim 1 to 7 included.
　前記ガラス基板の前記被成膜面にフッ素系の前記防汚膜を成膜する前に、前記ガラス基板の前記被成膜面に、光学膜と前記光学膜の上に二酸化珪素を主成分とした無機膜を成膜する工程をさらに含み、
　前記光学膜は、無機膜を積層した多層膜である、請求項１から８のいずれか１項に記載のガラス製品の製造方法。 Before forming the fluorine-based antifouling film on the film formation surface of the glass substrate, an optical film on the film formation surface of the glass substrate and silicon dioxide on the optical film as a main component And further including a step of forming the inorganic film,
The method for producing a glass product according to any one of claims 1 to 8, wherein the optical film is a multilayer film in which inorganic films are laminated.
　前記成膜工程は、０．１度／ｓｅｃから３００度／ｓｅｃの温度上昇によって達成される、請求項１から９のいずれか１項に記載のガラス製品の製造方法。 The method for producing a glass product according to any one of claims 1 to 9, wherein the film forming step is achieved by a temperature increase of 0.1 degrees / sec to 300 degrees / sec.
　前記予備加熱工程および前記成膜工程の前記真空チャンバー内の圧力は、１０^－９Ｐａ～１Ｐａの範囲である請求項１から１０のいずれか１項に記載のガラス製品の製造方法。 The method for producing a glass product according to any one of claims 1 to 10, wherein a pressure in the vacuum chamber in the preheating step and the film forming step is in a range of 10 ^-9 Pa to 1 Pa.
　前記予備加熱工程および前記成膜工程における前記ガラス基板の温度は、室温から前記沸点未満の範囲である、請求項１から１１のいずれか１項に記載のガラス製品の製造方法。 The method for producing a glass product according to any one of claims 1 to 11, wherein a temperature of the glass substrate in the preheating step and the film forming step is in a range from room temperature to less than the boiling point.
　真空チャンバー内において、フッ素系化合物を含有する防汚膜材料を用いた真空蒸着法により、ガラス基板の被成膜面にフッ素系の防汚膜を成膜する工程を含む、ガラス製品の製造方法であって、
　前記ガラス基板を準備する工程と、
　前記ガラス基板の前記被成膜面にフッ素系の前記防汚膜を成膜する工程と、を備え、
　前記防汚膜を成膜する工程は、
　前記防汚材料を沸点未満の温度で加熱し、前記防汚材料に含まれる不純物を放出させる予備加熱工程と、
　前記予備加熱工程の後、前記防汚材料を沸点以上まで加熱を行ない、前記ガラス基板の前記被成膜面に前記防汚膜を成膜する成膜工程と、
を備え、
　前記予備加熱工程は、前記ガラス基板の前記被成膜面に、前記防汚膜材料から放出される前記不純物が到達しない状態で行なわれ、
　前記成膜工程は、前記ガラス基板の前記被成膜面に、前記防汚膜材料から放出される前記防汚膜の材料が到達する状態で行なわれ、
　前記予備加熱工程から前記成膜工程への移行は、前記真空チャンバー内の圧力の変化率が上昇から減少に転じた後、変化率が急峻な状態から緩やかな状態に転じた後に行なう、ガラス製品の製造方法。 A method for producing a glass product, comprising a step of forming a fluorine-based antifouling film on a film-forming surface of a glass substrate by a vacuum deposition method using an antifouling film material containing a fluorine-based compound in a vacuum chamber Because
Preparing the glass substrate;
Forming the fluorine-based antifouling film on the film-forming surface of the glass substrate,
The step of forming the antifouling film includes
A preheating step of heating the antifouling material at a temperature below the boiling point to release impurities contained in the antifouling material;
After the preliminary heating step, the antifouling material is heated to a boiling point or more, and a film forming step of forming the antifouling film on the film formation surface of the glass substrate;
With
The preheating step is performed in a state where the impurities released from the antifouling film material do not reach the film formation surface of the glass substrate,
The film forming step is performed in a state where the antifouling film material released from the antifouling film material reaches the film formation surface of the glass substrate,
The transition from the preheating step to the film forming step is performed after the rate of change in pressure in the vacuum chamber has changed from an increase to a decrease and then the rate of change has changed from a steep state to a gentle state. Manufacturing method.
　前記予備加熱工程および前記成膜工程は、同一の前記真空チャンバーの内部で行なわれ、
　前記予備加熱工程および前記成膜工程は、前記真空チャンバーの内部が常に排気状態で行なわれ、
　前記予備加熱工程は、前記被成膜面に、前記防汚膜材料から放出される前記不純物が到達しないように、前記被成膜面と前記防汚膜材料との間が物理的に遮られた状態で行なわれ、
　前記成膜工程は、前記被成膜面に、前記防汚膜材料から放出される前記防汚膜の材料が到達するように、前記被成膜面と前記防汚膜材料との間が物理的に開放された状態で行なわれる、請求項１３に記載のガラス製品の製造方法。 The preheating step and the film forming step are performed inside the same vacuum chamber,
The preliminary heating step and the film forming step are always performed in an exhausted state inside the vacuum chamber,
In the preheating step, the film formation surface and the antifouling film material are physically blocked so that the impurities released from the antifouling film material do not reach the film formation surface. Performed in a state
In the film formation step, a physical gap between the film formation surface and the antifouling film material is obtained so that the material of the antifouling film released from the antifouling film material reaches the film formation surface. The method for producing a glass product according to claim 13, wherein the method is performed in an open state.
　前記被成膜面と前記防汚膜材料との間には、シャッターが配設され、
　前記シャッターは、
　前記予備加熱工程においては、前記被成膜面に、前記防汚膜材料から放出される前記不純物が到達しないように前記防汚膜材料を覆い、
　前記成膜工程においては、前記被成膜面に、前記防汚膜材料から放出される前記防汚膜の材料が到達するように、前記防汚膜材料を開放する、請求項１４に記載のガラス製品の製造方法。 A shutter is disposed between the film formation surface and the antifouling film material,
The shutter is
In the preliminary heating step, the antifouling film material is covered so that the impurities released from the antifouling film material do not reach the film formation surface,
The antifouling film material is opened in the film forming step so that the antifouling film material released from the antifouling film material reaches the film formation surface. Manufacturing method of glass products.
　前記予備加熱工程および前記成膜工程は、前記真空チャンバーの内部が常に排気状態で実施され、
　前記予備加熱工程は、
　前記ガラス基板が導入されていない前記真空チャンバー内で行なわれ、
　前記成膜工程は、
　前記予備加熱工程の後に前記真空チャンバー内の真空状態が維持された状態で、前記真空チャンバー内に前記ガラス基板が導入される工程を含む、請求項１３に記載のガラス製品の製造方法。 The preliminary heating step and the film forming step are always performed in an exhausted state inside the vacuum chamber,
The preheating step
Performed in the vacuum chamber where the glass substrate is not introduced,
The film forming step includes
The method for producing a glass product according to claim 13, comprising a step of introducing the glass substrate into the vacuum chamber in a state where the vacuum state in the vacuum chamber is maintained after the preheating step.
　前記予備加熱工程および前記成膜工程は、前記真空チャンバーの内部が常に排気状態で実施される、
　前記予備加熱工程は、
　前記ガラス基板が導入された前記真空チャンバーとは異なる予備加熱チャンバーで行なわれることにより、前記防汚膜材料に含有する不純物が放出される工程を含み、
　前記成膜工程は、
　前記予備加熱工程の後に前記真空チャンバー内に前記予備加熱工程が終了した前記防汚膜材料が導入される工程を含む、請求項１３に記載のガラス製品の製造方法。 The preliminary heating step and the film forming step are performed with the inside of the vacuum chamber always exhausted.
The preheating step
Including a step of releasing impurities contained in the antifouling film material by being performed in a preheating chamber different from the vacuum chamber into which the glass substrate is introduced,
The film forming step includes
The manufacturing method of the glassware of Claim 13 including the process of introduce | transducing the said antifouling film | membrane material which the said preheating process completed in the said vacuum chamber after the said preheating process.
　前記不純物は、主にハイドロカーボンである、請求項１３から１７のいずれか１項に記載のガラス製品の製造方法。 The method for producing a glass product according to any one of claims 13 to 17, wherein the impurities are mainly hydrocarbons.
　前記ガラス基板の前記被成膜面にフッ素系の前記防汚膜を成膜する前に、前記ガラス基板の前記被成膜面に、二酸化珪素を主成分とした下地膜を成膜する工程をさらに含む、請求項１３から１８のいずれか１項に記載のガラス製品の製造方法。 Before forming the fluorine-based antifouling film on the film-forming surface of the glass substrate, forming a base film mainly composed of silicon dioxide on the film-forming surface of the glass substrate; Furthermore, the manufacturing method of the glass product of any one of Claim 13 to 18 included.
　前記ガラス基板の前記被成膜面にフッ素系の前記防汚膜を成膜する前に、前記ガラス基板の前記被成膜面に、光学膜と前記光学膜の上に二酸化珪素を主成分とした無機膜を成膜する工程をさらに含み、
　前記光学膜は、無機膜を積層した多層膜である、請求項１３から１９のいずれか１項に記載のガラス製品の製造方法。 Before forming the fluorine-based antifouling film on the film formation surface of the glass substrate, an optical film on the film formation surface of the glass substrate and silicon dioxide on the optical film as a main component And further including a step of forming the inorganic film,
The said optical film is a manufacturing method of the glass product of any one of Claim 13 to 19 which is a multilayer film which laminated | stacked the inorganic film.
　前記成膜工程は、０．１度／ｓｅｃから３００度／ｓｅｃの温度上昇によって達成される、請求項１３から２０のいずれか１項に記載のガラス製品の製造方法。 21. The method for producing a glass product according to claim 13, wherein the film forming step is achieved by a temperature increase of 0.1 degrees / sec to 300 degrees / sec.
　前記予備加熱工程および前記成膜工程の前記真空チャンバー内の圧力は、１０－９Ｐａ～１Ｐａの範囲である、請求項１３から２１のいずれか１項に記載のガラス製品の製造方法。 The glass product manufacturing method according to any one of claims 13 to 21, wherein a pressure in the vacuum chamber in the preheating step and the film forming step is in a range of 10-9 Pa to 1 Pa.
　前記予備加熱工程および前記成膜工程における前記ガラス基板の温度は、室温から前記沸点未満の範囲である、請求項１３から２２のいずれか１項に記載のガラス製品の製造方法。 The method for producing a glass product according to any one of claims 13 to 22, wherein a temperature of the glass substrate in the preheating step and the film forming step is in a range from room temperature to less than the boiling point.
　真空チャンバー内において、フッ素系化合物を含有する防汚膜材料を用いた真空蒸着法により、ガラス基板の被成膜面にフッ素系の防汚膜を成膜する工程を含む、ガラス製品の製造方法であって、
　前記ガラス基板を準備する工程と、
　前記ガラス基板の前記被成膜面にフッ素系の前記防汚膜を成膜する工程と、を備え、
　前記防汚膜を成膜する工程は、
　前記防汚材料を沸点未満の温度で加熱し、前記防汚材料に含まれる不純物を放出させる予備加熱工程と、
　前記予備加熱工程の後、前記防汚材料を沸点以上の温度まで加熱を行ない、前記ガラス基板の前記被成膜面に前記防汚膜を成膜する成膜工程と、
を備え、
　前記予備加熱工程から前記成膜工程への移行は、前記防汚材料中の有効成分量の占める質量％濃度が、９５ｗｔ％以上となった後に行なう、ガラス製品の製造方法。 A method for producing a glass product, comprising a step of forming a fluorine-based antifouling film on a film-forming surface of a glass substrate by a vacuum deposition method using an antifouling film material containing a fluorine-based compound in a vacuum chamber Because
Preparing the glass substrate;
Forming the fluorine-based antifouling film on the film-forming surface of the glass substrate,
The step of forming the antifouling film includes
A preheating step of heating the antifouling material at a temperature below the boiling point to release impurities contained in the antifouling material;
After the preheating step, the antifouling material is heated to a temperature equal to or higher than the boiling point, and a film forming step of forming the antifouling film on the film formation surface of the glass substrate;
With
The method for producing a glass product, wherein the transition from the preheating step to the film forming step is performed after the mass% concentration of the active ingredient in the antifouling material reaches 95 wt% or more.
　前記予備加熱工程および前記成膜工程は、同一の前記真空チャンバーの内部で行なわれ、
　前記予備加熱工程および前記成膜工程は、前記真空チャンバーの内部が常に排気状態で行なわれ、
　前記予備加熱工程は、前記ガラス基板の前記被成膜面に、前記防汚膜材料から放出される前記不純物が到達しない状態で行なわれ、
　前記成膜工程は、前記ガラス基板の前記被成膜面に、前記防汚膜材料から放出される前記防汚膜の材料が到達する状態で行なわれる、請求項２４に記載のガラス製品の製造方法。 The preheating step and the film forming step are performed inside the same vacuum chamber,
The preliminary heating step and the film forming step are always performed in an exhausted state inside the vacuum chamber,
The preheating step is performed in a state where the impurities released from the antifouling film material do not reach the film formation surface of the glass substrate,
The glass film production according to claim 24, wherein the film forming step is performed in a state where the antifouling film material released from the antifouling film material reaches the film formation surface of the glass substrate. Method.
　前記予備加熱工程は、前記被成膜面に、前記防汚膜材料から放出される前記不純物が到達しないように、前記被成膜面と前記防汚膜材料との間が物理的に遮られた状態で行なわれ、
　前記成膜工程は、前記被成膜面に、前記防汚膜材料から放出される前記防汚膜の材料が到達するように、前記被成膜面と前記防汚膜材料との間が物理的に開放された状態で行なわれる、請求項２５に記載のガラス製品の製造方法。 In the preheating step, the film formation surface and the antifouling film material are physically blocked so that the impurities released from the antifouling film material do not reach the film formation surface. Performed in a state
In the film formation step, a physical gap between the film formation surface and the antifouling film material is obtained so that the material of the antifouling film released from the antifouling film material reaches the film formation surface. The method for producing a glass product according to claim 25, wherein the method is performed in an open state.
　前記被成膜面と前記防汚膜材料との間には、シャッターが配設され、
　前記シャッターは、
　前記予備加熱工程においては、前記被成膜面に、前記防汚膜材料から放出される前記不純物が到達しないように前記防汚膜材料を覆い、
　前記成膜工程においては、前記被成膜面に、前記防汚膜材料から放出される前記防汚膜の材料が到達するように、前記防汚膜材料を開放する、請求項２６に記載のガラス製品の製造方法。 A shutter is disposed between the film formation surface and the antifouling film material,
The shutter is
In the preliminary heating step, the antifouling film material is covered so that the impurities released from the antifouling film material do not reach the film formation surface,
27. The antifouling film material is opened in the film formation step so that the antifouling film material released from the antifouling film material reaches the film formation surface. Manufacturing method of glass products.
　前記予備加熱工程および前記成膜工程は、前記真空チャンバーの内部が常に排気状態で実施され、
　前記予備加熱工程は、
　前記ガラス基板が導入されていない前記真空チャンバー内で行なわれ、
　前記成膜工程は、
　前記予備加熱工程の後に前記真空チャンバー内の真空状態が維持された状態で、前記真空チャンバー内に前記ガラス基板が導入される工程を含む、請求項２４に記載のガラス製品の製造方法。 The preliminary heating step and the film forming step are always performed in an exhausted state inside the vacuum chamber,
The preheating step
Performed in the vacuum chamber where the glass substrate is not introduced,
The film forming step includes
The manufacturing method of the glass product of Claim 24 including the process of introducing the said glass substrate in the said vacuum chamber in the state by which the vacuum state in the said vacuum chamber was maintained after the said preheating process.
　前記予備加熱工程および前記成膜工程は、前記真空チャンバーの内部が常に排気状態で実施される、
　前記予備加熱工程は、
　前記ガラス基板が導入された前記真空チャンバーとは異なる予備加熱チャンバーで行なわれることにより、前記防汚膜材料に含有する不純物が放出される工程を含み、
　前記成膜工程は、
　前記予備加熱工程の後に前記真空チャンバー内に前記予備加熱工程が終了した前記防汚膜材料が導入される工程を含む、請求項２４に記載のガラス製品の製造方法。 The preliminary heating step and the film forming step are performed with the inside of the vacuum chamber always exhausted.
The preheating step
Including a step of releasing impurities contained in the antifouling film material by being performed in a preheating chamber different from the vacuum chamber into which the glass substrate is introduced,
The film forming step includes
25. The method for producing a glass product according to claim 24, further comprising a step of introducing the antifouling film material having been subjected to the preheating step into the vacuum chamber after the preheating step.
　前記不純物は、主にハイドロカーボンである、請求項２４から２９のいずれか１項に記載のガラス製品の製造方法。 The method for producing a glass product according to any one of claims 24 to 29, wherein the impurities are mainly hydrocarbons.
　前記ガラス基板の前記被成膜面にフッ素系の前記防汚膜を成膜する前に、前記ガラス基板の前記被成膜面に、二酸化珪素を主成分とした下地膜を成膜する工程をさらに含む、請求項２４から３０のいずれか１項に記載のガラス製品の製造方法。 Before forming the fluorine-based antifouling film on the film-forming surface of the glass substrate, forming a base film mainly composed of silicon dioxide on the film-forming surface of the glass substrate; The method for producing a glass product according to any one of claims 24 to 30, further comprising:
　前記ガラス基板の前記被成膜面にフッ素系の前記防汚膜を成膜する前に、前記ガラス基板の前記被成膜面に、光学膜と前記光学膜の上に二酸化珪素を主成分とした無機膜を成膜する工程をさらに含み、
　前記光学膜は、無機膜を積層した多層膜である、請求項２４から３１のいずれか１項に記載のガラス製品の製造方法。 Before forming the fluorine-based antifouling film on the film formation surface of the glass substrate, an optical film on the film formation surface of the glass substrate and silicon dioxide on the optical film as a main component And further including a step of forming the inorganic film,
32. The method for manufacturing a glass product according to claim 24, wherein the optical film is a multilayer film in which inorganic films are laminated.
　前記成膜工程は、０．１度／ｓｅｃから３００度／ｓｅｃの温度上昇によって達成される、請求項２４から３２のいずれか１項に記載のガラス製品の製造方法。 The method of manufacturing a glass product according to any one of claims 24 to 32, wherein the film forming step is achieved by a temperature increase of 0.1 degrees / sec to 300 degrees / sec.
　前記予備加熱工程および前記成膜工程の前記真空チャンバー内の圧力は、１０^－９Ｐａ～１Ｐａの範囲である、請求項２４から３３のいずれか１項に記載のガラス製品の製造方法。 The method for producing a glass product according to any one of claims 24 to 33, wherein the pressure in the vacuum chamber in the preheating step and the film forming step is in a range of 10 ^-9 Pa to 1 Pa.
　前記予備加熱工程および前記成膜工程における前記ガラス基板の温度は、室温から前記沸点未満の範囲である、請求項２４から３４のいずれか１項に記載のガラス製品の製造方法。 The method for producing a glass product according to any one of claims 24 to 34, wherein a temperature of the glass substrate in the preheating step and the film forming step is in a range from room temperature to less than the boiling point.