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

Manufacturing method of glass products

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.

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.

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).

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.

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.

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

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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. FIG. 2 is a cross-sectional view taken along the line II-II in FIG. 2 is a diagram illustrating a structure of a first vacuum chamber in Embodiment 1. FIG. 3 is a diagram showing a structure of a second vacuum chamber in Embodiment 1. FIG. 3 is a diagram showing a structure of a third vacuum chamber in Embodiment 1. FIG. 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. It is a figure which shows the relationship between the shutter open time in Example 11, and antifouling film | membrane material temperature. It is a figure which shows the relationship between the shutter open time in Example 12, and antifouling film | membrane material temperature. It is a figure which shows the relationship between the shutter open time in Example 13, and antifouling film | membrane material temperature. It is a figure which shows the relationship between the shutter open time in Example 14, and antifouling film | membrane material temperature. It is a figure which shows the relationship between the shutter open time and antifouling film | membrane material temperature in the comparative example 11. It is a figure which shows the relationship between the shutter open time in Comparative Example 12, and antifouling film | membrane material temperature. It is a figure which shows the relationship between the shutter open time in Comparative Example 13, and antifouling film | membrane material temperature. 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. 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. 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. 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. 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. 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. 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. 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. 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. 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. 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. 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. 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. 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. 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. It is a figure which shows the relationship (vapor deposition conditions) between the open time and temperature in Embodiment 3. 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. 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.

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.

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.

[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.

(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.

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.

[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.

[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.

(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.

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.

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.

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.

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.

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. .

(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.

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).

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.

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.

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.

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).

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.

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.

(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.

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.

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.

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.

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.

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.

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).

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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. .

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. .

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.

(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.

The second vacuum chamber 300 includes an introduction chamber 300A, a base film forming chamber 300B, and an antifouling film forming chamber 300C.

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.

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.

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.

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.

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.

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.

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.

(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.

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).

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.

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.

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.

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.

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.

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.

(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.

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.

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.

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.

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.

(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.

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.

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.

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.

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.

The temperature management may be performed by setting the conditions in advance without always monitoring.

(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.

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.

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.

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.

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.

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.

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.

(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.

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.

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.

(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.

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.

(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.

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.

(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.

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.

(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.

(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.

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.

(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.

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.

(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.

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.

(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.

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.

(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.

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.

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. .

(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.

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.

(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.

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.

(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.

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.

(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.

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.

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.

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.

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.

[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.

(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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

(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.

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).

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.

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.

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.

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.

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.

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.

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.

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.

(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.

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.

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.

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.

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).

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.

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.

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.

(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.

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.

(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.

In the vacuum chamber 200, a Penning vacuum gauge was installed, and the pressure fluctuation in the chamber was measured in real time.

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.

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.

(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.

A Penning vacuum gauge was installed in the chamber, and the pressure fluctuation in the chamber was measured in real time.

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.

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.

(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.

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).

(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.

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).

(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.

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.

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.

(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.

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.

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.

(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.

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).

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.

(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.

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.

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.

(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.

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.

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.

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. .

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.

[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.

(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.

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.

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.

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.

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.

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.

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.

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.

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.

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).

(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.

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.

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.

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.

(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.

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.

(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.

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.

(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.

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.

(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.

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.

(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.

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.

(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.

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.

(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.

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.

(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”.

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.

(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.

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.

(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.

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.

(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.

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.

(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.

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.

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.

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 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

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.
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.
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.
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.
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.
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.
The method for producing a glass product according to any one of claims 1 to 6, wherein the impurities are mainly hydrocarbons.
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.
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.
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.
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.
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.
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.
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.
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.
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.
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.
The method for producing a glass product according to any one of claims 13 to 17, wherein the impurities are mainly hydrocarbons.
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.
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.
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.
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.
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.
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.
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.
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.
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.
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.
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.
The method for producing a glass product according to any one of claims 24 to 29, wherein the impurities are mainly hydrocarbons.
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:
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.
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.
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.
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.