CN109851232B - Method for manufacturing low reflection film on both sides - Google Patents
Method for manufacturing low reflection film on both sides Download PDFInfo
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- CN109851232B CN109851232B CN201910104255.5A CN201910104255A CN109851232B CN 109851232 B CN109851232 B CN 109851232B CN 201910104255 A CN201910104255 A CN 201910104255A CN 109851232 B CN109851232 B CN 109851232B
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- glass substrate
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- reflection film
- refractive index
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
- C03C17/23—Oxides
- C03C17/245—Oxides by deposition from the vapour phase
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/061—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of metal
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
- C03C17/225—Nitrides
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
- C03C17/38—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal at least one coating being a coating of an organic material
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/70—Properties of coatings
- C03C2217/73—Anti-reflective coatings with specific characteristics
- C03C2217/734—Anti-reflective coatings with specific characteristics comprising an alternation of high and low refractive indexes
Abstract
The invention provides a method for manufacturing a laminated body which is suitable for forming low reflection films on both surfaces of a cover glass of a display device and the like and has no chromatic aberration on the outer periphery. A method for manufacturing a laminate having low-reflection films formed on both surfaces of a glass substrate, characterized in that a light-shielding portion is formed on one surface of the glass substrate by printing; after a low reflection film is formed on the entire surface of the glass substrate on which the light shielding portion is formed by a dry film forming method, a low reflection film is formed on the entire surface of the glass substrate on which the light shielding portion is not formed by a dry film forming method, and low reflection films are formed on both surfaces of the glass substrate.
Description
The present application is a divisional application of the chinese patent application entitled "glass substrate with low reflective film on both sides and method for manufacturing the same" having the national application number of 201410147780.2.
Technical Field
The present invention relates to a method for manufacturing a glass substrate having low-reflection films formed on both surfaces thereof. More specifically, the present invention relates to a chemically strengthened glass substrate having low-reflection films formed on both surfaces thereof, and a method for producing the same.
Background
In recent years, there has been an increasing use of cover glass (protective glass) for improving protection and appearance of a display surface of a display, for mobile devices such as tablet PCs (personal computers) and smartphones (hereinafter, also referred to as "smartphones and the like"), or display devices such as liquid crystal televisions and touch panels (hereinafter, these will be collectively referred to as "display devices and the like" in the present specification).
These cover glasses use glass substrates having low reflection films formed on both surfaces. This can suppress light reflection on the display surface of the display device or the like, and can further improve the visual visibility of the display.
Patent documents 1 and 2 disclose methods for simultaneously forming low reflection films on both surfaces of a glass substrate. Fig. 1 and 2 are schematic views showing a process of forming a conventional low reflection film, showing simultaneous film formation on both surfaces, fig. 1 showing a state when film formation is performed, and fig. 2 showing a state after film formation.
In these methods, since the low reflection film cannot be formed on the outer periphery of the glass substrate due to the holding at the time of film formation, a glass substrate having a size larger than that of the product is prepared, the substrate is held at a position outside the product size, the low reflection film is formed on both surfaces, and then the glass substrate is cut into a predetermined size to obtain a glass substrate as a product. Fig. 3 is a schematic view showing an example of a scribe line of a glass substrate having low reflection films on both surfaces thereof, which is manufactured by the above-described simultaneous film formation on both surfaces.
In the methods described in patent documents 1 and 2, a sputtering method is used for forming the low reflection film. Dry film formation methods such as sputtering and vapor deposition have advantages over wet film formation methods such as coating in terms of the following characteristics: by laminating a plurality of films having different physical properties such as refractive index and the like into a multilayer, low reflection can be achieved; high hardness of the film, excellent scratch resistance, and the like. Further, if a dry film formation method is employed, there are advantages in manufacturing methods such as good controllability of film thickness and stable film formation, as compared with a wet film formation method.
In order to reduce the burden of differentiation and movement due to the thin design, the above-described display device and the like are required to be light in weight and thin. Therefore, a cover glass for protecting the display surface is required to be thin. In order to ensure the strength of the cover glass, tempered cover glass in which a compressive stress layer is formed on the surface of the glass by chemical tempering treatment is also used (see patent document 3). In patent document 3, a compressive stress layer is formed on the surface of the glass by chemical strengthening treatment, but a compressive stress layer may be formed on the surface of the glass by physical strengthening treatment.
However, since the strengthened glass substrate is difficult to be cut into a desired size after the formation of the compressive stress layer, the glass substrate is first cut into a desired product size, then subjected to a physical strengthening treatment or a chemical strengthening treatment, and then subjected to the formation of the low reflection film. In the case of performing film formation on the entire surface in the film formation of the low reflection film, the method of simultaneously forming films on both surfaces as described in patent documents 1 and 2 cannot be employed from the viewpoint of holding the substrate, and it is necessary to employ a step of forming the low reflection film on one surface by a dry film formation method, then inverting the glass substrate, and forming the low reflection film on the other surface of the glass substrate.
Fig. 4 is a schematic view showing a conventional process for forming a low reflection film on one surface of each film, and shows a state when the film is formed on one surface. In fig. 4, a light shielding portion 20 is formed by printing on the outer peripheral portion of one surface (left side surface in the drawing) of the glass substrate 10. In a state where the non-display surface side of the glass substrate 10, that is, the surface on which the light shielding portion 20 is formed is held by the holding jig 50, a low reflection film is formed from the display surface side when used as a cover glass of a display device or the like, that is, the surface side on which the light shielding portion is not formed. Fig. 5 shows a state where the low reflection film 30a is formed on the display surface side of the glass substrate 10. Next, as shown in fig. 6, the glass substrate 10 is turned upside down, and a low reflection film is formed on the entire surface of the glass substrate 10 on which the light shielding portion 20 is formed, on the non-display surface side.
Documents of the prior art
Patent document
Patent document 1: japanese patent No. 3768547 Specification
Patent document 2: japanese patent No. 3254782 Specification
Patent document 3: japanese patent laid-open publication No. 2013-006755
Disclosure of Invention
Technical problem to be solved by the invention
In the above-described dry film formation method, in the step of forming the low-reflection films on one surface of the glass substrate, the display surface side of the glass substrate, that is, the display surface when used as a cover glass, is a surface that can be directly seen, and therefore the low-reflection film on the display surface side needs to be a low-reflection film that is free from air holes, foreign substances, and the like as much as possible. Therefore, it is considered effective to eliminate the risk of film formation on the surface of the substrate contaminated by the inside of the film forming apparatus in the film forming step, and it is desirable to prepare a cleaned clean substrate, first form a film on the display surface side, and then form a film on the non-display surface side.
However, when the low reflection films are formed on both surfaces of the substrate by this step, it is obvious that color difference occurs in the outer peripheral portion of the low reflection film on the display surface side.
An object of the present invention is to solve the above-described problems of the prior art and to provide a method for manufacturing a laminate suitable for forming low reflection films on both surfaces of a cover glass of a display device or the like without color difference in the peripheral portion.
Technical scheme for solving technical problems
In order to achieve the above object, the present invention provides a method for manufacturing a laminate having low reflection films formed on both surfaces of a glass substrate, wherein a light shielding portion is formed on an outer peripheral portion of one surface of the glass substrate by printing; after a low reflection film is formed on the entire surface of the glass substrate on which the light shielding portion is formed by a dry film forming method, a low reflection film is formed on the entire surface of the glass substrate on which the light shielding portion is not formed by a dry film forming method, and low reflection films are formed on both surfaces of the glass substrate.
In the method for producing a laminate of the present invention, the glass substrate may be subjected to a chemical strengthening treatment in advance.
In the method for producing a laminate of the present invention, an antifouling film may be formed on the low reflection film on the surface of the glass substrate on which the light-shielding portion is not formed.
In the method for producing a laminate of the present invention, the reflective film is a laminate film obtained by alternately laminating a film made of a high refractive index material and a film made of a low refractive index material.
In the laminated film, the high refractive index material is preferably niobium oxide or tantalum oxide, and the low refractive index material is preferably silicon oxide.
In the laminated film, the high refractive index material is preferably silicon nitride, and the low refractive index material is preferably any one of a mixed oxide containing Si and Sn, a mixed oxide containing Si and Zr, and a mixed oxide containing Si and Al.
The laminated film is preferably formed by alternately laminating 2 or more and 6 or less layers of a film made of the high refractive index material and a film made of the low refractive index material.
In the method for producing a laminate of the present invention, the reflective film is preferably formed by a sputtering method.
In the method for producing a laminate of the present invention, the antifouling film is preferably composed of a fluorine-containing organosilicon compound.
The fluorine-containing organosilicon compound preferably has at least one group selected from the group consisting of a polyfluoropolyether group, a polyfluoroalkylene group and a polyfluoroalkyl group.
In the method for producing a laminate of the present invention, the antifouling film is preferably formed by a vacuum deposition method.
The present invention also provides a laminate produced by the method of the present invention, in which low-reflection films are formed on both surfaces of a glass substrate.
ADVANTAGEOUS EFFECTS OF INVENTION
The glass substrate with the low reflection films on both sides obtained by the present invention has good low reflection characteristics, high strength, and no color difference in the outer periphery of the display surface. Therefore, the glass is suitable for use as a cover glass for a display device or the like.
Drawings
Fig. 1 is a schematic view showing a conventional process for forming a low reflection film (simultaneous film formation on both surfaces), and shows a state when film formation is performed.
Fig. 2 is a schematic view showing a conventional process for forming a low reflection film (simultaneous film formation on both surfaces), and shows a state after film formation.
Fig. 3 is a schematic view showing an example of a scribe line of a glass substrate having low reflection films on both sides thereof manufactured by a conventional method (simultaneous film formation on both sides).
Fig. 4 is a schematic view showing a conventional process for forming a low reflection film (film formation on one side), and shows a state when film formation on one side is performed.
Fig. 5 is a schematic view showing a conventional process for forming a low reflection film (film formation on one side), and shows a state after film formation on one side.
Fig. 6 is a schematic view showing a conventional process for forming a low reflection film (film formation on one side), and shows a state when film formation on the back side is performed.
Fig. 7 is a schematic view showing a glass substrate with low reflection films on both surfaces, which is manufactured by a conventional method (film formation on one surface).
Fig. 8 is a schematic view of the glass substrate with the low reflection film on both surfaces in fig. 7, as viewed from the low reflection film 30a side.
Fig. 9 is a schematic view showing a process of forming a low reflection film by the method of the present invention, and shows a state when one-side film formation is performed.
Fig. 10 is a schematic view showing a process of forming a low reflection film by the method of the present invention, and shows a state after forming a film on one surface.
Fig. 11 is a schematic view showing a process of forming a low reflection film by the method of the present invention, and shows a state when back surface film formation is performed.
Fig. 12 is a schematic view showing a glass substrate with a low reflection film on both surfaces, which is manufactured by the method of the present invention.
Fig. 13 is a schematic view of the glass substrate with the low reflection film on both surfaces of fig. 13 when viewed from the low reflection film 30b side.
Description of the symbols
10 glass substrate
20 light shielding part
30. 30a, 30b Low reflection film
40 particles after winding
50 holding jig
80 color difference
Detailed Description
The invention is described below with reference to the accompanying drawings.
First, a process for implementing the present invention is shown.
The present inventors have conducted extensive studies on the reason why the color difference occurs in the outer periphery of the low reflection film, and as a result, have found that the reason is: when a low reflection film is formed on one surface by a dry film forming method, the film material detours to the back surface side of the glass substrate, and particles having a nanometer size (hereinafter, also referred to as nanometer size) adhere to the outer peripheral portion on the back surface side of the substrate, thereby generating scattered light. The particles that detour to the back side of the substrate are also referred to as "wrapping particles (coating まわり particles" in the future).
Since the display surface side of the glass substrate is an important surface that can be directly seen, the holding means for the glass substrate is generally designed so that the display surface and the substrate holding jig do not contact each other as much as possible, and then, film formation is first performed on the entire surface of the display surface side.
For example, it was confirmed that nanoscale particles 40a were adhered to the outer peripheral portion of the non-display surface of the glass substrate 10 on which the light-shielding portion 20 was formed, after the low-reflection film was formed on the display surface side while holding the non-display surface side of the glass substrate (fig. 5) (fig. 6). The particles 40a were found to be the following: in the step shown in fig. 4, when the low reflection film is formed on the display surface side of the glass substrate 10, a part of the film forming material bypasses the back surface side of the glass substrate 10, that is, the non-display surface side of the glass substrate 10 on which the light shielding portion 20 is formed, and adheres to the particles on the outer peripheral portion of the non-display surface of the glass substrate 10.
However, in fig. 6, the nano-sized particles 40a adhering to the outer peripheral portion of the non-display surface of the glass substrate 10 do not cause a problem because the low reflection film 30b is formed on the particles 40a even when the low reflection film is formed on the non-display surface side as the next step. Fig. 7 is a schematic view showing a glass substrate with low reflection films on both surfaces, which is manufactured by a conventional method (film formation on one surface).
When a low reflection film is formed on the non-display surface side of the glass substrate 10, the film forming material may similarly bypass the back surface side of the glass substrate 10. The nano-scale particles 40b of fig. 7 are the following particles: a part of the film forming material detours to the back surface side of the glass substrate 10, that is, the display surface side of the glass substrate 10, and adheres to the particles previously formed on the outer peripheral portion of the low reflection film 30a on the display surface side of the glass substrate 10.
As a result, the nano-scale particles 40b adhering to the low reflection film 30a formed in the past generate scattered light, and as shown in fig. 8, a color difference 80 is clearly generated in the outer peripheral portion of the display surface of the glass substrate 10. The chromatic aberration 80 is often generated in the outer peripheral portion of the glass substrate 10 in a range of about 10mm from the end surface of the substrate.
In contrast, in the method for producing a laminate of the present invention, as shown in fig. 9, in a state where the display surface side of the glass substrate 10 is held by the holding jig 50, first, a low reflection film is formed on the entire surface of the non-display surface side, that is, the surface side on which the light shielding portion 20 is formed when used as a cover glass of a display device or the like, and then, a low reflection film is formed on the entire surface of the display surface side. Fig. 10 shows a state in which the low reflection film 30a is formed on the non-display surface side of the glass substrate 10.
At this time, it was confirmed that the nano-sized particles 40a were adhered to the back surface side of the glass substrate 10, that is, the outer peripheral portion of the display surface (fig. 11). The particles 40a are the following particles: in the steps shown in fig. 9 and 10, when the low reflection film is formed on the non-display surface side of the glass substrate 10, a part of the film forming material bypasses the back surface side of the glass substrate 10, that is, the display surface side of the glass substrate 10, and particles adhering to the outer peripheral portion of the display surface of the glass substrate 10.
Next, as shown in fig. 11, the glass substrate 10 is turned upside down, and a low reflection film is formed on the entire display surface side of the glass substrate 10. That is, in a state where the non-display surface side of the glass substrate 10 on which the low reflection film 30a was formed in the previous step is held by the holding jig 50, the low reflection film is formed on the display surface side of the glass substrate 10.
As a result, when the low reflection film is formed on the display surface side, the low reflection film 30b is also formed on the particles 40a, and the nano-sized particles 40a that have previously adhered to the outer peripheral portion of the display surface of the glass substrate 10 are captured in the low reflection film, which is not problematic. Fig. 12 is a schematic view showing a glass substrate with a low reflection film on both surfaces, which is manufactured by the method of the present invention.
As shown in fig. 12, when the low reflection film 30b is formed on the display surface of the glass substrate 10, the film forming material also bypasses the back surface side of the glass substrate 10 and the non-display surface side of the glass substrate 10, and the nano-sized particles 40b adhere to the outer peripheral portion of the non-display surface of the glass substrate 10.
In this case, the nano-scale particles 40b are attached to the low reflection film 30a formed previously, but are on the non-display surface side of the glass substrate 10, so that the particles 40b are not visible from the display surface even if stray light is generated, and as shown in fig. 13, no color difference is generated in the outer peripheral portion of the display surface of the glass substrate 10.
The surface of the glass substrate 10 on which the light shielding portion 20 is formed becomes a non-display surface (a back surface facing the display surface) when the glass substrate is used as a cover glass of a mobile device or a display device. By forming the light shielding portion 20 on the non-display surface, wiring portions of a mobile device, a display device, and the like can be made invisible when viewed from the display surface side, and design can be improved by adopting a design having the light shielding portion. In the illustrated embodiment, the light-shielding portion is formed in a frame shape (in a japanese patent laid-open (kokai) section) shape) on the outer peripheral portion of the glass substrate, but the light-shielding portion may be formed only in a part of the non-display surface, and the shape of the light-shielding portion is not necessarily limited to the frame shape. For example, the light shielding portion may be formed only on a part of the side or only on a part of the side depending on the design of the mobile device and the display device.
The light shielding portion can be formed by a printing method. For example, screen printing or inkjet printing is preferably used from the viewpoint of production cost and printing accuracy.
As the holding means for the glass substrate, various jigs can be used as long as they can cope with film formation over the entire surface, but it is preferable to use, for example, a glass substrate holding means described in japanese patent laid-open No. 2012-89837 as a jig.
The glass substrate may be held by other means, for example, by fixing with an adhesive such as an electrostatic chuck or a double-sided adhesive tape, as long as the low-reflection film is not adversely affected on the entire display surface side of the glass substrate 10. In this respect, the same applies to the case where the low reflection film is formed on the entire non-display surface side of the glass substrate.
The method for producing the laminate of the present invention will be further described below.
Glass substrate
In the present invention, in the production of the laminate, a glass substrate subjected to chemical strengthening treatment in advance is preferably used. However, a glass substrate that has not been subjected to chemical strengthening treatment may be used for the production of the laminate.
In a glass sheet substrate subjected to a chemical strengthening treatment, alkali metal ions having a small ionic radius (typically Li ions or Na ions) and alkali metal ions having a larger ionic radius (typically K ions) on the surface of the substrate are exchanged by ion exchange. Thereby, a compressive stress layer is formed on the surface of the substrate.
Therefore, the glass substrate is made of glass containing an alkali metal component, and examples thereof include soda lime glass, aluminosilicate glass, aluminoborosilicate glass, and lithium aluminosilicate glass. Among them, aluminosilicate glass and soda lime glass are preferable from the viewpoint of the price and the strengthening characteristics when the chemical strengthening treatment is performed.
The glass substrate used for producing the laminate preferably satisfies the following conditions.
That is, the surface compressive stress (hereinafter also referred to as CS) of the glass substrate used for producing the laminate is preferably 400MPa to 1200MPa, and more preferably 700MPa to 900 MPa. If CS is 400Pa or more, the strength is sufficient as a practical strength. Further, if CS is 1200MPa or less, the steel can withstand its own compressive stress and there is no fear of natural fracture. When used as cover glass for display devices and the like, CS is particularly preferably 700MPa to 850 MPa.
The depth of the stress layer (hereinafter also referred to as DOL) of the glass substrate used for producing the laminate is preferably 15 to 50 μm, and more preferably 20 to 40 μm. If the DOL is 15 μm or more, there is no fear that the glass cutter or other sharp jigs will be easily damaged or broken. Further, if DOL is 40 μm or less, the compressive stress of the substrate itself can be tolerated, and there is no fear of natural destruction. When used as a cover glass for a display device or the like, DOL is particularly preferably 25 μm or more and 35 μm or less.
In addition, the size of the glass substrate used in the production of the laminate may be appropriately selected depending on the use of the laminate. When the glass is used as cover glass of mobile equipment, the size is 30mm multiplied by 50 mm-300 multiplied by 400mm, and the thickness is 0.1-2.5 mm; when used as a cover glass for a display device, the glass has a size of 50mm × 100mm to 2000 × 1500mm and a thickness of 0.5 to 4mm.
Low reflection film
The material of the low reflection film is not particularly limited, and various materials can be used as long as they can suppress light reflection. For example, as the low reflection film, a film made of a high refractive index material and a film made of a low refractive index material are laminated. The film made of a high refractive index material as referred to herein is a film made of a material having a refractive index of 1.9 or more at a wavelength of 550nm, and the film made of a low refractive index material is a film made of a material having a refractive index of 1.6 or less at a wavelength of 550 nm.
The film made of a high refractive index material and the film made of a low refractive index material may be in the form of 1 layer each, or may have a structure of 2 or more layers each. When the film made of the high refractive index material and the film made of the low refractive index material each have 2 or more layers, a laminated film in which a film made of the high refractive index material and a film made of the low refractive index material are alternately laminated is preferable.
In particular, in order to improve the antireflection performance, the low reflection film is preferably a laminate obtained by laminating a plurality of layers, and for example, the laminate is preferably a laminate in which 2 to 6 layers, and more preferably 2 to 4 layers, are laminated as a whole. The laminate is preferably a laminate obtained by laminating a film made of a high refractive index material and a film made of a low refractive index material as described above, and the number of layers obtained by summing the numbers of layers of the film made of the high refractive index material and the film made of the low refractive index material is preferably within the above range.
The material of the film made of the high refractive index material and the film made of the low refractive index material is not particularly limited, and may be selected in consideration of the desired degree of antireflection and productivity. As a constituent material of the film made of a high refractive index material, for example, one or more metal oxides selected from silicon nitride, indium oxide, tin oxide, niobium oxide, titanium oxide, zirconium oxide, cerium oxide, tantalum oxide, aluminum oxide, zinc oxide, and the like can be preferably used. As a constituent material of the film made of a low refractive index material, a material selected from silicon dioxide (SiO) can be preferably used 2 ) One or more of a material containing a mixed oxide of Si and Sn, a material containing a mixed oxide of Si and Zr, and a material containing a mixed oxide of Si and Al.
The film made of a high refractive index material is preferably made of any one selected from a niobium oxide layer and a tantalum oxide layer in view of productivity and the degree of refractive index. In this case, the film made of a low refractive index material is preferably made of silica.
In addition, from the viewpoint of hardness and surface roughness of the film material, the film composed of a high refractive index material is preferably composed of silicon nitride, and the film composed of a low refractive index material is preferably composed of any one of a material containing a mixed oxide of Si and Sn, a material containing a mixed oxide of Si and Zr, and a material containing a mixed oxide of Si and Al.
In the method for producing a laminate of the present invention, a dry film formation method is used as a method for forming a low reflection film. The dry film forming method is not particularly limited, and various dry film forming methods such as a sputtering method, a vapor deposition method, and an ion plating method can be used. However, the sputtering method is preferably used from the viewpoint of stability of film thickness and productivity. As the sputtering method, various sputtering methods such as a pulse sputtering method, an AC sputtering method, and a digital sputtering method can be used.
When the laminate produced by the method of the present invention is used as a cover glass for a display device or the like, it is preferable to form an antifouling film on the low reflection film on the display surface side of the glass substrate (on the low reflection film 30b of the laminate shown in fig. 12). As a method for forming the antifouling film, any of a dry method such as a vacuum deposition method, an ion beam assisted deposition method, an ion plating method, a sputtering method, and a plasma CVD method, and a wet method such as a spin coating method, a dip coating method, a cast coating method, a slit coating method, and a spray method can be used. However, from the viewpoint of abrasion resistance, a dry film formation method is preferably used.
In addition, when the anti-fouling film is formed on the low reflection film on the display surface side of the glass substrate, as shown in fig. 11, the anti-fouling film is formed on the low reflection film 30b on the display surface side of the glass substrate 10 in a state where the non-display surface side of the glass substrate 10 on which the low reflection film 30a was formed in the previous step is held by the holding jig 50.
The constituent material of the stain-proofing film may be appropriately selected from materials that can impart stain-proofing properties, water repellency, and oil repellency. Specifically, for example, a fluorine-containing organosilicon compound may be mentioned. The fluorine-containing organosilicon compound may be used without limitation as long as it is a fluorine-containing organosilicon compound that imparts stain-proofing, water-repellency, and oil-repellency.
As such a fluorine-containing organosilicon compound, for example, a fluorine-containing organosilicon compound having one or more groups selected from a polyfluoropolyether group, a polyfluoroalkylene group, and a polyfluoroalkyl group is preferably used. The polyfluoropolyether group is a 2-valent group having a structure in which a polyfluoroalkylene group and an etheric oxygen atom are alternately bonded.
Specific examples of the fluorine-containing organosilicon compound having 1 or more groups selected from the group consisting of the polyfluoropolyether group, the polyfluoroalkylene group and the polyfluoroalkyl group include compounds represented by the following general formulae (I) to (V).
[ solution 1]
Wherein Rf is a linear polyfluoroalkyl group having 1 to 16 carbon atoms (for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, etc., as an alkyl group), X is a hydrogen atom or a lower alkyl group having 1 to 5 carbon atoms (for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, etc.), R1 is a hydrolyzable group (for example, amino, alkoxy, etc.) or a halogen atom (for example, fluorine, chlorine, bromine, iodine, etc.), m is an integer of 1 to 50, preferably 1 to 30, n is an integer of 0 to 2, preferably 1 to 2, and p is an integer of 1 to 10, preferably 1 to 8.
C q F 2q+1 CH 2 CH 2 Si(NH 2 ) 3 (II)
Here, q is an integer of 1 or more, preferably 2 to 20.
Examples of the compound represented by the general formula (II) include n-trifluoro (1,1,2,2-tetrahydro) propylsilazane (n-CF) 3 CH 2 CH 2 Si(NH 2 ) 3 ) N-heptafluoro (1,1,2,2-tetrahydro) pentylsilazane (n-C) 3 F 7 CH 2 CH 2 Si(NH 2 ) 3 ) And the like.
C q 'F 2q'+1 CH 2 CH 2 Si(OCH 3 ) 3 (III)
Here, q' is an integer of 1 or more, preferably 1 to 20.
As the compound represented by the general formula (III), 2- (perfluorooctyl) ethyltrimethoxysilane (n-C) can be exemplified 8 F 17 CH 2 CH 2 Si(OCH 3 ) 3 ) And the like.
[ solution 2]
In the formula (IV), R f2 Is- (OC) 3 F 6 ) s -(OC 2 F 4 ) t -(OCF 2 ) u A 2-valent linear polyfluoropolyether group represented by (s, t, and u are each independently an integer of 0 to 200); r 2 、R 3 Each independently is a monovalent hydrocarbon group having 1 to 8 carbon atoms (e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, etc.). X 2 、X 3 Independently a hydrolyzable group (e.g., amino group, alkoxy group, acyloxy group, alkenyloxy group, isocyanate group, etc.) or a halogen atom (e.g., fluorine atom, chlorine atom, bromine atom, iodine atom, etc.); d. e is independently an integer from 1 to 2; c. f is independently an integer of 1 to 5 (preferably 1 to 2); a and b are independently 2 or 3.
R of Compound (IV) f2 In the above formula, s + t + u is preferably from 20 to 300, more preferably from 25 to 100. Further, as R 2 、R 3 More preferred are methyl, ethyl and butyl. As by X 2 、X 3 The hydrolyzable group represented by (a) is more preferably an alkoxy group having 1 to 6 carbon atoms, and particularly preferably a methoxy group or an ethoxy group. Further, a and b are each preferably 3.
[ solution 3]
F-(CF 2 ) v -(OC 3 F 6 ) w -(OC 2 F 4 ) y -(OCF 2 ) z (CH 2 ) h O(CH 2 ) i -Si(x 4 ) 3-k (R 4 ) k (V)
In the formula (V), V is an integer of 1 to 3; w, y and z are each independently an integer of 0 to 200; h is 1 or 2; i is an integer of 2 to 20; x 4 Is a hydrolyzable group; r 4 Is a linear or branched hydrocarbon group having 1 to 22 carbon atoms; k is an integer of 0 to 2. w + y + z is preferably 20 to 300, more preferably 25 to 100. Further, i is more preferably 2 to 10.X 4 The alkoxy group having 1 to 6 carbon atoms is preferable, and methoxy group and ethoxy group are more preferable. As R 4 More preferably an alkyl group having 1 to 10 carbon atoms.
Further, as commercially available fluorine-containing organosilicon compounds having 1 or more groups selected from a polyfluoropolyether group, a polyfluoroalkylene group and a perfluoroalkyl group, KP-801 (trade name, product of shin-Etsu chemical industries, ltd. (shin-Etsu chemical industries, Co., ltd.)), KY178 (trade name, product of shin-Etsu chemical industries, ltd.), KY-130 (trade name, product of shin-Etsu chemical industries, ltd.), KY185 (trade name, product of shin-Etsu chemical industries, ltd.), OPTOOL (オプツ - ル, registered trademark) DSX and OPTOOL (registered trademark) AES (both trade names, product of King industries, ltd. (ダイキン, ltd.: ), etc. are preferably used.
Further, in order to suppress deterioration or the like due to a reaction with moisture in the air, the fluorine-containing organosilicon compound is usually stored in a mixture with a solvent such as a fluorine-based solvent, but if the fluorine-containing organosilicon compound is directly supplied to a film-forming step in a state of including the solvent, the durability or the like of the resulting thin film may be adversely affected.
Therefore, when the antifouling film is formed by a vacuum deposition method according to the steps described later, it is preferable to use a fluorine-containing organosilicon compound which has been subjected to a solvent removal treatment in advance before heating in a heating vessel. Further, it is preferable to use a fluorine-containing organosilicon compound which is not diluted with a solvent (without adding a solvent). For example, the concentration of the solvent contained in the fluorine-containing organosilicon compound solution is preferably 1 mol% or less, and more preferably 0.2 mol% or less. It is particularly preferable to use a solvent-free fluorine-containing organosilicon compound.
Examples of the solvent used for storing the fluorine-containing organosilicon compound include polyfluorohexane and hexafluorom-xylene (C) 6 H 4 (CF 3 ) 2 ) Hydrofluoropolyether, HFE7200/7100 (trade name, manufactured by Sumitomo 3M corporation, sumitomo スリーエム, HFE7200 represents C 4 F 9 C 2 H 5 HFE7100 denotes C 4 F 9 OCH 3 ) And the like.
The treatment of removing the solvent from the fluorine-containing organosilicon compound solution containing the fluorine-based solvent can be performed by, for example, evacuating a container containing the fluorine-containing organosilicon compound solution.
The time for performing the evacuation varies depending on the exhaust capacity of the exhaust line, the vacuum pump, and the like, the amount of the solution, and the like, and therefore, the evacuation can be performed for, for example, about 10 hours or more without limitation.
As described above, in the method for producing a laminate of the present invention, as a film formation method of the antifouling film, any of a dry method such as a vacuum deposition method, an ion beam assisted deposition method, an ion plating method, a sputtering method, and a plasma CVD method, and a wet method such as a spin coating method, a dip coating method, a cast coating method, a slit coating method, and a spray method can be used. However, from the viewpoint of scratch resistance, a dry film formation method is preferably used. When the antifouling film is formed using the above-exemplified fluorine-containing organosilicon compound, a vacuum deposition method is preferably used.
In the case of using the vacuum vapor deposition method, the solvent removal treatment may be performed by introducing a fluorine-containing organosilicon compound solution into a heating vessel of a film forming apparatus for forming an antifouling film, and then evacuating the heating vessel at room temperature before the temperature is raised. Further, the solvent may be removed by an evaporator or the like in advance before being introduced into the heating vessel.
However, as described above, the fluorine-containing organosilicon compound containing a small amount of solvent or no solvent is more likely to deteriorate due to contact with the atmosphere than the fluorine-containing organosilicon compound containing a solvent.
Therefore, a storage container for the fluorine-containing organosilicon compound having a small (or no) solvent content is preferably used in which the container is replaced with an inert gas such as nitrogen gas and sealed, and exposure to the atmosphere and contact time during handling are shortened.
Specifically, it is preferable to introduce the fluorine-containing organosilicon compound into the heating container of the film forming apparatus for forming the antifouling film immediately after the storage container is opened. After introduction, it is preferable to remove the atmosphere (air) contained in the heating container by evacuating the inside of the heating container or by replacing it with an inert gas such as nitrogen or a rare gas. More preferably, the heating container of the present manufacturing apparatus is introduced from the storage container (storage container) without being exposed to the atmosphere, and for example, the storage container and the heating container are connected by a pipe with a pump.
Next, it is preferable that after the fluorine-containing organosilicon compound is introduced into the heating container, the inside of the container is replaced with vacuum or an inert gas, and then heating for film formation is started immediately.
In the present invention, the thickness of the antifouling film formed on the low reflection film on the display surface side of the glass substrate is not particularly limited, but is preferably 2 to 20nm, more preferably 2 to 15nm, and still more preferably 2 to 10nm. When the film thickness is 2nm or more, the anti-fouling film is uniformly coated on the surface of the low-reflection film, and the article is durable in view of abrasion resistance. Further, if the film thickness is 20nm or less, the film can avoid the reaction sites on the substrate surface and the state where unreacted antifouling film molecules are attached to the substrate, and the optical properties such as haze as a laminate are good.
(laminated body)
The laminate produced by the method of the present invention has low reflection films formed on both surfaces of the glass substrate, and therefore can suppress light reflection on the display surface when used as a cover glass for a display device or the like.
Therefore, the visual reflectance (Japanese: the visual reflectance for viewing and listening) measured according to the procedure described in the examples described later is 3% or less, preferably 2% or less, and more preferably 1% or less.
Therefore, the visual transmittance measured by the procedure described in the examples described later is 93% or more, preferably 95% or more, and more preferably 96% or more.
In addition, the above-described visual reflectance and visual transmittance are satisfied even when the antifouling film is formed on the low reflection film on the display surface side of the glass substrate.
Examples
The present invention will be described in more detail below with reference to examples. However, the present invention is not limited to these examples. Examples 1 to 4 are examples, and examples 5 to 6 are comparative examples.
(example 1)
A substrate with low reflection films on both surfaces was produced by the following procedure, in which low reflection films were formed on both surfaces of a glass substrate.
As the glass substrate, a glass substrate subjected to chemical strengthening treatment (dragonttail (registered trademark) manufactured by asahi glass co.
The reinforced substrate had a size of 600mm × 400mm and a thickness of 2mm, and the degree of chemical reinforcement was 730MPa CS and 30 μm DOL.
A light shielding portion is formed in a frame shape on an outer peripheral portion of one surface of a glass substrate by screen printing, and a surface on which the light shielding portion is formed is a non-display surface of the glass substrate. Specifically, printing was performed in a black frame shape in the following procedure at a width of 2cm on the outer peripheral portion of four sides of one surface of the glass substrate, thereby forming a light shielding portion. First, coating was performed with a screen printer to a thickness of 5 μm using an ink (manufactured by imperial ink manufacturing corporation (imperial インキ manufacturing corporation), GLSHF (product name)). Then, the mixture was dried by keeping the temperature at 150 ℃ for 10 minutes in a dryer. Subsequently, the dried first layer was coated with an ink (GLSHF (product name) manufactured by imperial ink corporation) at a thickness of 5 μm by a screen printer. Then, it was dried by keeping it at 150 ℃ for 40 minutes with a dryer. Thereby, a light shielding portion is formed in the outer peripheral portion on the one surface of the glass substrate.
Next, as shown in fig. 9, in a state where the display surface side of the glass substrate 10 is held by the holding jig 50, a low reflection film is formed on the entire surface of the non-display surface of the glass substrate 10 on which the light shielding portion 20 is formed by the following steps.
First, a niobium oxide target (NBO ターゲット) manufactured by AGC ceramics, inc. (AGC セラミックス, inc.) was used at a pressure of 0.3Pa, a frequency of 20kHz, and a power density of 3.8W/cm, while introducing a mixed gas in which 10 vol% of oxygen gas was mixed with argon gas 2 Pulse sputtering was performed under the condition of a reverse pulse width of 5 μ sec, and niobium oxide (Nb) having a thickness of 14nm was formed on one surface as a film made of a high refractive index material 2 O 5 Hereinafter, the film is also referred to as a niobium oxide (niobia)).
Then, while introducing a mixed gas in which 40 vol% of oxygen gas was mixed into argon gas, a silicon target was used at a pressure of 0.3Pa, a frequency of 20kHz, and a power density of 3.8W/cm 2 Pulse sputtering was performed under a condition of a reverse pulse width of 5 μ sec, and silicon dioxide (SiO) having a thickness of 30nm was formed over the entire surface of the niobium oxide (niobia) film as a film made of a low refractive index material 2 Hereinafter, the film is also referred to as a silica (silica)).
Next, a niobium oxide target (product name: NBO target, manufactured by AGC ceramics) was used while introducing a mixed gas of argon gas and 10 vol% oxygen gas, and the pressure was 0.3Pa, the frequency was 20kHz, and the power density was 3.8W/cm 2 Pulse sputtering was performed under the condition of reverse pulse width of 5 μ sec, and a film of niobium oxide (niobia) having a thickness of 110nm was formed on the entire surface of the silicon dioxide (silica)) film as a film made of a high refractive index material.
Next, a mixed gas in which 40 vol% of oxygen was mixed with argon gas was introduced, and a silicon target was used at a pressure of 0.3Pa, a frequency of 20kHz, and a power density of 3.8W/cm 2 Pulse sputtering was performed under a condition of a reverse pulse width of 5 μ sec, and a film of silicon dioxide (silica) having a thickness of 80nm was formed as a film of a low refractive index material on the entire surface of the niobium oxide (niobia) film.
Thus, a low reflection film in which a total of 4 layers of niobium oxide (niobia) film and silicon dioxide (silica) film were alternately laminated was formed on the entire surface.
Next, as shown in fig. 11, the glass substrate 10 was turned over, and a low reflection film in which a total of 4 layers of niobium oxide (niobia) films and silicon dioxide (silica) films were alternately laminated was formed on the entire surface of the non-display surface of the glass substrate 10 on which the outer frame 20 was formed in a state where the display surface side of the glass substrate 10 was held by the holding jig 50.
Thus, a laminate having low reflection films formed on the entire surfaces of the glass substrates was obtained.
(example 2)
In this example, a low reflection film in which a total of 4 layers of niobium oxide (niobia) film and silicon dioxide (silica) film were alternately laminated was formed on the entire surface of both surfaces (display surface and non-display surface) of the glass substrate in the same manner as in example 1, except that the thickness of the silicon dioxide (silica) film of the fourth layer was 85 nm.
Next, an antifouling film is formed on the low reflection film on the display surface side of the glass substrate by the following steps.
First, KY185 (trade name, product of shin-Etsu chemical Co., ltd.) was introduced into a heating vessel as a fluorine-containing organosilicon compound as a vapor deposition material. Then, the inside of the heating vessel was degassed by a vacuum pump for 10 hours or more to remove the solvent in the solution, thereby obtaining a composition for forming a coating film of a fluorine-containing organosilicon compound.
Next, the heating vessel containing the composition for forming a fluorine-containing organosilicon compound film was heated to 270 ℃. After reaching 270 ℃, the state was maintained for 10 minutes until the temperature stabilized.
Then, a low reflection film on the display surface side of the laminate having low reflection films formed on the entire surfaces of both surfaces of the glass substrate, which was placed in the vacuum chamber, was supplied with the composition for forming a fluorine-containing organosilicon compound film from a nozzle connected to a heating container containing the composition for forming a fluorine-containing organosilicon compound film, and film formation was performed.
In the film formation, the film was formed until the film thickness of the fluorine-containing organosilicon compound film formed on the low reflection film on the display surface side reached 7nm while measuring the film thickness using a quartz crystal resonator provided in a vacuum chamber.
The supply of the raw material from the nozzle was stopped at a time when the fluorine-containing organosilicon compound film reached 7nm, and the resulting laminate was taken out from the vacuum chamber.
The taken-out laminate was placed on a hot plate with the film surface facing upward, and heat-treated at 100 ℃ for 60 minutes in the air.
Thus, a laminate in which low reflection films were formed on both surfaces of the glass substrate and an antifouling layer was formed on the display surface side was obtained.
(example 3)
In this example, a low reflection film was formed by alternately laminating 4 total layers of niobium oxide (niobia) film and silicon dioxide (silica) film on both surfaces (display surface and non-display surface) of a glass substrate in the same manner as in example 1, except that the thickness of the first layer of niobium oxide (niobia) film was set to 13nm, the thickness of the second layer of silicon dioxide (silica) film was set to 35nm, the thickness of the third layer of niobium oxide (niobia) film was set to 120nm, and the thickness of the fourth layer of silicon dioxide (silica) film was set to 80 nm.
Next, an antifouling film was formed on the low reflective film on the display surface side by the same procedure as in example 2, except that OPTOOL (registered trademark) DSX (manufactured by seiko chemical industries) was used instead of KY185 (product name, manufactured by shin-Etsu chemical industries).
(example 4)
In this example, a low reflection film was formed by alternately laminating 4 total layers of niobium oxide (niobia) film and silicon dioxide (silica) film on both surfaces (display surface and non-display surface) of a glass substrate in the same manner as in example 1, except that the thickness of the first layer of niobium oxide (niobia) film was set to 13nm, the thickness of the second layer of silicon dioxide (silica) film was set to 35nm, the thickness of the third layer of niobium oxide (niobia) film was set to 120nm, and the thickness of the fourth layer of silicon dioxide (silica) film was set to 80 nm.
Next, an antifouling film was formed on the low reflective film on the display surface side by the same procedure as in example 2, except that KY178 (trade name, manufactured by shin-Etsu chemical Co., ltd.) was used instead of KY185 (trade name, manufactured by shin-Etsu chemical Co., ltd.) as the fluorine-containing organosilicon compound as the vapor deposition material.
(example 5)
A low reflection film in which a total of 4 layers of niobium oxide (niobia) film and silicon dioxide (silica) film were alternately laminated was formed on the entire surface of both surfaces (display surface and non-display surface) of the glass substrate in the same manner as in example 1, except that after the low reflection film was formed on the display surface side of the glass substrate in the state where the non-display surface side of the outer frame 20 of the glass substrate 10 was held by the holding jig 50, the glass substrate 10 was inverted as shown in fig. 6, and the low reflection film was formed on the non-display surface side of the glass substrate 10 in the state where the display surface side of the glass substrate 10 was held by the holding jig 50.
(example 6)
In this example, a low reflection film was formed by alternately laminating 4 total layers of niobium oxide (niobia) film and silicon dioxide (silica) film on both surfaces (display surface and non-display surface) of a glass substrate in the same manner as in example 5, except that the thickness of the first layer of niobium oxide (niobia) film was set to 13nm, the thickness of the second layer of silicon dioxide (silica) film was set to 35nm, the thickness of the third layer of niobium oxide (niobia) film was set to 120nm, and the thickness of the fourth layer of silicon dioxide (silica) film was set to 80 nm.
Next, in the same manner as in example 3, an antifouling film was formed on the low reflection film on the display surface side by using optol (registered trademark) DSX (manufactured by seikagaku corporation) as a fluorine-containing organosilicon compound as a vapor deposition material.
The laminate obtained by the above-described procedure was subjected to the following evaluation.
(visual transmittance)
The spectral transmittance of the laminate was measured using a spectrophotometer (manufactured by shimadzu corporation) with a device name: solidSpec-3700, and the stimulus value Y specified in JIS Z8701 was calculated from the spectral transmittance. Next, the stimulus value Y was defined as the visual transmittance.
(visual reflectance)
The reflectance of the laminate was measured using a spectrophotometer (model: solidSpec-3700, manufactured by Shimadzu corporation), and the visual reflectance (stimulus value Y of reflection defined in JIS Z8701: 1999) was calculated from the reflectance.
(color difference of reflection)
When the laminate was observed from the display surface side under a fluorescent lamp (1500 Lx), the evaluation that discoloration of the substrate at the ends was observed was x, and the evaluation that discoloration of the substrate at the ends was not observed was o.
(Water contact Angle)
The measurement was carried out by using a contact angle measuring instrument (manufactured by Kyowa interface science Co., ltd.; PCA-1). Specifically, 1 μ L of pure water was dropped on the substrate after film formation using a syringe, and the contact angle was calculated by the 3-point method from the image of the droplet.
The results are shown in the following table.
[ Table 1]
As is clear from table 1, the results of the visual reflectance and the visual transmittance were good in all the examples. However, in examples 5 and 6 in which the low reflection film was formed from the display surface side, color difference was observed at the edge of the display surface of the laminate.
In examples 2 to 4 and 6 in which the antifouling film was formed on the low reflection film on the display surface side, the water contact angle was high, and the effect of water repellency was confirmed.
Claims (11)
1. A method for manufacturing a glass substrate with a low reflection film on both surfaces thereof, the glass substrate having a low reflection film on both surfaces thereof, wherein a light shielding portion is formed on an outer peripheral portion of one surface of the glass substrate by printing,
after a low reflection film is formed on the entire surface of the glass substrate on which the light shielding portion is formed by a dry film forming method, a low reflection film is formed on the entire surface of the glass substrate on which the light shielding portion is not formed by a dry film forming method, and low reflection films are formed on both surfaces of the glass substrate.
2. The method for manufacturing a glass substrate with a low reflection film on both sides according to claim 1, wherein the glass substrate is subjected to a chemical strengthening treatment in advance.
3. The method for producing a glass substrate with a low reflection film on both surfaces according to claim 1 or 2, wherein an antifouling film is formed on the low reflection film on the surface of the glass substrate on which the light shielding portion is not formed.
4. The method for manufacturing a glass substrate with a low reflection film on both sides according to claim 1, wherein the low reflection film is a laminated film in which a film made of a high refractive index material and a film made of a low refractive index material are alternately laminated.
5. The method for manufacturing a glass substrate with a low reflection film on both surfaces according to claim 4, wherein in the laminated film, the high refractive index material is niobium oxide or tantalum oxide, and the low refractive index material is silicon oxide.
6. The method for manufacturing a glass substrate with a low reflection film on both sides according to claim 4, wherein in the laminated film, the high refractive index material is silicon nitride, and the low refractive index material contains any one of a mixed oxide of Si and Sn, a mixed oxide of Si and Zr, and a mixed oxide of Si and Al.
7. The method for producing a glass substrate with a low reflection film on both surfaces according to claim 4, wherein the laminated film is obtained by alternately laminating 2 or more and 6 or less layers of the film made of the high refractive index material and the film made of the low refractive index material.
8. The method for manufacturing a glass substrate with a low reflection film on both surfaces according to claim 1, wherein the low reflection film is formed by a sputtering method.
9. The method for producing a glass substrate having a low reflection film on both surfaces according to claim 3, wherein the anti-fouling film is composed of a fluorine-containing organosilicon compound.
10. The method for producing a glass substrate with a low reflection film on both sides according to claim 9, wherein the fluorine-containing organosilicon compound has at least one group selected from the group consisting of a polyfluoropolyether group, a polyfluoroalkylene group and a polyfluoroalkyl group.
11. The method for producing a glass substrate having a low reflection film on both surfaces thereof according to claim 3, wherein the anti-fouling film is formed by a vacuum evaporation method.
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-
2014
- 2014-02-21 JP JP2014032103A patent/JP6361162B2/en active Active
- 2014-03-05 TW TW103107491A patent/TW201442971A/en unknown
- 2014-04-04 KR KR20140040581A patent/KR20140126663A/en not_active Application Discontinuation
- 2014-04-14 CN CN201410147780.2A patent/CN104118994A/en active Pending
- 2014-04-14 CN CN201910104255.5A patent/CN109851232B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| TW201442971A (en) | 2014-11-16 |
| KR20140126663A (en) | 2014-10-31 |
| JP2014224979A (en) | 2014-12-04 |
| JP6361162B2 (en) | 2018-07-25 |
| CN109851232A (en) | 2019-06-07 |
| CN104118994A (en) | 2014-10-29 |
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