TWI757490B - Covering member, manufacturing method of covering member, and display device - Google Patents

Abstract

The present invention relates to a covering member comprising a transparent substrate, the transparent substrate having a first main surface facing the member to be covered, and a second main surface opposite to the first main surface, and the transparent substrate has a first main surface opposite to the first main surface. A compound containing F atoms is attached to the main surface, and the contact angle of the first main surface is 50° or less.

Description

Covering member, manufacturing method of covering member, and display device

The present invention relates to a covering member, a method for manufacturing the covering member, and a display device.

Conventionally, in order to protect the display panel of a display device, the cover member which has a transparent base body, such as a glass plate, is used (for example, refer patent document 1). The edge of the main surface on the display panel side of the transparent substrate may be printed in a frame shape with a frame portion for concealing wiring and the like. [Prior Art Literature] [Patent Literature]

[Patent Document 1] International Publication No. 2011/148990

[Problems to be Solved by Invention]

The main surface of the cover member is usually attached to the display surface of the display panel using an adhesive layer such as an optical adhesive film. At this time, gas such as air may enter between the main surface of the cover member (transparent substrate) and the adhesive layer, and bubbles may be generated. In particular, when the cover member having the frame portion on the main surface of the display panel side is attached to the display surface of the display panel, it is easy for the level difference between the frame portion and the transparent substrate to be formed between the cover member and the adhesive layer. bubbles are formed. The air bubbles generated between the cover member and the adhesive layer deteriorate the visibility of the display image when the display surface of the display panel is observed through the cover member. Therefore, when many air bubbles are generated between the covering member and the adhesive layer, it is necessary to perform operations such as eliminating air bubbles using an autoclave, which is complicated.

The present invention has been made in view of the above-mentioned aspects, and an object thereof is to provide a covering member which is disposed on the display surface side of a display panel, a method for manufacturing the covering member, and a display device using the covering member When the display surface of the display panel is attached through the adhesive layer, the generation of air bubbles between the covering member and the adhesive layer can be suppressed. [Technical means to solve problems]

As a result of earnest research, the present inventors found that the above-mentioned object can be achieved by adopting the following configuration, and completed the present invention.

That is, the covering member of one aspect of the present invention includes a transparent substrate having a first main surface facing the covered member, and a second main surface on the opposite side of the first main surface. A compound containing F atoms is attached to the first main surface, and the contact angle of the first main surface is 50° or less. A method of manufacturing a covering member according to an aspect of the present invention is a method of manufacturing a covering member including a transparent substrate, and prepares a first main surface facing the covered member and a second main surface opposite to the first main surface. The transparent substrate on the main surface is prepared as a transfer substrate with a fluorine-containing compound adhered on one side, the first main surface of the transparent substrate is brought into contact with the surface on which the fluorine-containing compound is adhered in the transfer substrate, and the The fluorine-containing compound is transferred to the first main surface of the transparent substrate, the compound containing F atoms is adhered to the first main surface by the transfer, and the contact angle of the first main surface is set to 50° or less . A display device according to an aspect of the present invention is provided with the covering member, the adhesive layer, and the display panel, and the covering member is directed through the adhesive layer in an orientation in which the first main surface of the transparent substrate faces the display panel. And it is attached to the above-mentioned display panel. [Effect of invention]

According to the present invention, it is possible to provide a covering member capable of suppressing the generation of air bubbles between the covering member and the adhesive layer when the covering member and the display surface of the display panel are bonded through the adhesive layer, a method for producing the covering member, and using the covering member Components of the display device.

Embodiments of the present invention will be described based on the drawings.

<Configuration of Display Device of This Embodiment> FIG. 1 is a cross-sectional view showing a display device 100 of the present embodiment. Examples of the display device 100 include display devices such as smartphones and tablet terminals; in-vehicle display devices such as car navigation devices and RSE (Rear Seat Entertainment) devices for rear seat occupants to view images, etc.; Display devices for opening and closing doors of household appliances such as refrigerators, washing machines, and microwave ovens, etc., but not limited to these.

The display device 100 includes a display panel 104 and a cover member 11 , and the display panel 104 and the cover member 11 are bonded together via an adhesive layer 14 . The display device 100 has a frame body 106 for accommodating various parts, and an opening portion is formed in the frame body 106 . In the frame body 106, the above-mentioned display panel 104 and the backlight unit 102 are placed. As shown in FIG. 1 , the backlight unit 102 is placed on the chassis bottom plate 107 , which is the bottom plate of the frame body 106 , and the display panel 104 is placed on the backlight unit 102 . In this embodiment, the display panel 104 is a liquid crystal panel. Inside the frame body 106 and outside the display panel 104 , wirings 141 connected to the display panel 104 are arranged.

The structures of the backlight unit 102 and the display panel 104 are not particularly limited, and well-known structures may be employed. The material and the like of the frame body 106 (including the frame body bottom plate 107 ) are similarly not particularly limited.

The display device 100 is not limited to a display device having a liquid crystal panel as the display panel 104. For example, an organic EL (Electroluminescence) panel, a PDP (Plasma Display Panel), an electronic Display devices such as ink-type panels. Depending on the type of the display panel 104 , the display device 100 may not have the backlight unit 102 . The display device 100 may also have a touch panel or the like. As a touch panel, the touch panel of an electrostatic capacitance type, the touch panel of a resistive film type, etc. are mentioned.

The cover member 11 constituting a part of the display device 100 has a transparent substrate 12 . The transparent substrate 12 is attached to the display panel 104 by the adhesive layer 14 . In this way, the transparent substrate 12 functions as a covering member covering the display panel 104 . In this embodiment, the end of the transparent substrate 12 is bonded to the frame body 106 by the bonding layer 131 .

FIG. 2 is an enlarged cross-sectional view of the cover member 11 , the adhesive layer 14 and the display panel 104 . The transparent base 12 constituting the covering member 11 has a main surface. That is, the transparent substrate 12 has a first main surface 12a facing the display panel 104 as a covered member, and a second main surface 12b opposite to the first main surface 12a and not facing the display panel 104 . In the present embodiment, the display panel 104 is described as the covered member, but the covered member is not limited to the display panel.

In the transparent substrate 12, as described below, a compound containing F atoms is attached to the first main surface 12a, and the contact angle of the first main surface 12a is 50° or less.

In the present embodiment, a frame portion 132 for concealing the wiring 141 (see FIG. 1 ) so as not to be seen from the side of the second main surface 12b is formed in a frame shape on the edge of the first main surface 12a of the transparent substrate 12 . The first main surface 12 a of the transparent base 12 on which the frame portion 132 is formed is attached to the display surface 104 a of the display panel 104 by the adhesive layer 14 .

Preferably, the adhesive layer 14 and the transparent substrate 12 are also transparent, and the difference in refractive index between the transparent substrate 12 and the adhesive layer 14 is small. As the adhesive layer 14, for example, a layer composed of a transparent resin obtained by curing a liquid curable resin composition can be mentioned, and other than that, an optical adhesive film or an optical adhesive tape may be used. The thickness of the adhesive layer 14 is, for example, 5-1000 μm, preferably 50-500 μm.

<Previous Cover Member> FIG. 3 is an enlarged cross-sectional view showing a state in which the previous cover member 511 is attached to the display panel 104 via the adhesive layer 14 . The same reference numerals are assigned to the same parts as those of the present embodiment described with reference to FIGS. 1 and 2 , and descriptions thereof are omitted. The transparent substrate 512 constituting the previous covering member 511 is attached to the display surface 104a of the display panel 104 using the adhesive layer 14 .

At this time, as shown in FIG. 3 , gas such as air may enter between the transparent substrate 512 and the adhesive layer 14 to generate air bubbles 551 . In particular, when the frame portion 132 is printed on the first main surface 512 a of the transparent substrate 512 on the display panel 104 side, the air bubbles 551 are likely to be generated in the step portion 561 formed by the frame portion 132 . The air bubbles 551 deteriorate the visibility of the image (displayed image) displayed on the display surface 104 a when the display panel 104 is viewed through the transparent substrate 512 . Therefore, in the case where many air bubbles 551 are generated, it is necessary to perform an operation of disappearing the air bubbles 551 using an autoclave, which is very complicated.

<Configuration of the covering member of the present embodiment> FIG. 4 is a cross-sectional view showing the covering member 11 of the present embodiment. The cover member 11 has the transparent base body 12 which has the 1st main surface 12a and the 2nd main surface 12b. The cover member 11 has a frame portion 132 on the first main surface 12a of the transparent substrate 12 as needed, and has a functional layer not shown on the first main surface 12a or the second main surface 12b. Hereinafter, each part constituting the covering member 11 will be described in more detail.

<<Transparent Substrate>> The first main surface 12a of the transparent substrate 12 has a compound containing F atoms attached thereto, and the contact angle of the first main surface 12a is 50° or less. Thereby, when the first main surface 12a of the transparent substrate 12 is attached to the display surface 104a of the display panel 104 using the adhesive layer 14, air bubbles can be suppressed from being generated between the transparent substrate 12 and the adhesive layer 14. Furthermore, the compound containing the F atom is preferably an organic compound so that the contact angle of the first main surface 12a can be controlled in a small amount.

Although the reason why the above-mentioned effect can be obtained is not clear, it is presumed as follows. By making the contact angle of the 1st main surface 12a of the transparent base|substrate 12 50 degrees or less, the 1st main surface 12a and the adhesive layer 14 are easily wetted, and adhesiveness can be improved. Furthermore, the compound containing F atoms is attached to the 1st main surface 12a of the transparent base|substrate 12 (for example, the glass plate containing Si). Thereby, the minute water repellent part is formed in the 1st main surface 12a. Furthermore, it is considered that the surface energy of the paths formed by the water repellent portions is reduced, and the gas that becomes the air bubbles is discharged from between the transparent substrate 12 and the adhesive layer 14 through the water repellent portions. Therefore, it is presumed that the generation of air bubbles can be suppressed.

The contact angle of the first main surface 12a of the transparent substrate 12 is preferably 25 to 45°, more preferably 28 to 40°, and still more preferably 30 to 38°, for the reason that the generation of air bubbles can be further suppressed.

The contact angle of the first main surface 12a of the transparent substrate 12 is obtained as follows. First, the first main surface 12a of the transparent base 12 (when the frame portion 132 is printed in a frame shape, the area where the frame portion 132 is not printed) is divided into 4×4 equal parts. Measure the contact angle of water at the intersections (9 points in total) of the lines (3+3) drawn during the equal division. Specifically, at a measurement temperature of 23° C., the contact angle after 5 seconds after the dropwise addition of 5 μL of pure water was measured using a contact angle meter (manufactured by Kyowa Interface Science Co., Ltd., PCA-11). The average value of the contact angles at 9 points in total measured was set as the contact angle of the first main surface 12 a of the transparent substrate 12 . Furthermore, the measurement of the contact angle can be measured by the θ/2 method (A half angle method).

The ratio of the number of F atoms to the number of Si atoms in the first main surface 12a of the transparent substrate 12 (for example, a glass plate containing Si) (F/Si) (hereinafter also referred to as It is "atomic ratio (F/Si)"), Preferably it is 0.005-0.13, More preferably, it is 0.015-0.1, More preferably, it is 0.02-0.08. Furthermore, when the atomic ratio (F/Si) is large, in the first main surface 12a of the transparent substrate 12, the area where the surface energy is lowered becomes larger, and the area where the adhesion with the adhesive layer 14 is lowered becomes larger. . Therefore, when the upper limit value of the atomic ratio (F/Si) is exceeded, air bubbles are likely to remain in the portion where the adhesiveness between the first main surface 1a and the adhesive layer 14 is low.

As long as the atomic ratio (F/Si) of the first main surface 12a of the transparent substrate 12 exceeds 0, it can be considered that the first main surface 12a of the transparent substrate 12 (for example, a glass plate containing Si) adheres to the first main surface 12a containing F atoms. compound.

The atomic ratio (F/Si) of the first main surface 12a of the transparent substrate 12 is obtained as follows. First, an X-ray photoelectron spectroscopy apparatus (manufactured by JEOL Ltd., JPS-9000MC) was used for the first main surface 12a of the transparent substrate 12 (in the case where the frame portion 132 was printed in a frame shape, the area where the frame portion 132 was not printed) ) to obtain the F atomic concentration (unit: atomic %) and the Si atomic concentration (unit: atomic %). The ratio of the obtained concentration of F atoms to the concentration of Si atoms was defined as the atomic ratio (F/Si) of the first main surface 12 a of the transparent substrate 12 . More specifically, the measurement was performed under the conditions that the source of X-rays was MgKα rays, an acceleration voltage of 12 kV, and 25 mA. The measurement was performed with a spot diameter of 6 mmf. There is no tilt of the sample. The measurement was performed with a passing energy of 50 eV, a measurement step of 0.5 eV, a Dwell Time (residence time) of 100 msec, and the number of scans 30 times. For the bonding energy peak obtained after the measurement, after removing the background by the Shirley method, the atomic concentration ratio of F/Si was calculated from the intensity of the F1s peak and the peak intensity of Si2p3/2.

The transparent substrate 12 is not particularly limited as long as it is made of a transparent material, and for example, one made of glass or a combination of glass and resin (composite material, laminate material, etc.) can be preferably used. The shape of the transparent substrate 12 is also not particularly limited, and for example, a rigid plate-like shape can be mentioned. In addition, the transparent base body 12 does not necessarily have to be a flat plate shape, and may be a shape that is curved as a whole or a shape that includes a folded portion in a part.

Examples of the glass plate used as the transparent substrate 12 include ordinary glass mainly composed of silica, such as soda lime silicate glass, aluminosilicate glass, borosilicate glass, alkali-free glass, and quartz glass. A glass plate made of glass.

In the case of using a glass plate as the transparent substrate 12, the composition of the glass is preferably a composition that can be shaped or strengthened by chemical strengthening treatment, and preferably contains sodium.

The composition of glass is not particularly limited, and glass having various compositions can be used. For example, the aluminosilicate glass which has the following composition in terms of molar % on an oxide basis can be mentioned. (i) Contains 50-80% SiO ₂ , 2-25% Al ₂ O ₃ , 0-10% Li ₂ O, 0-18% Na ₂ O, 0-10% K ₂ O, 0 Glass of ~15% MgO, 0~5% CaO and ₀ ~5% ZrO2. (ii) Contains 50-74% SiO ₂ , 1-10% Al ₂ O ₃ , 6-14% Na ₂ O, 3-11% K ₂ O, 2-15% MgO, 0-6% % CaO and 0-5% ZrO ₂ , the total content of SiO ₂ and Al ₂ O ₃ is 75% or less, the total content of Na ₂ O and K ₂ O is 12-25%, and the total content of MgO and CaO For 7 to 15% of the glass. (iii) Contains 68-80% SiO ₂ , 4-10% Al ₂ O ₃ , 5-15% Na ₂ O, 0-1% K ₂ O, 4-15% MgO and 0-1% % of ZrO ₂ in glass. (iv) Contains 67-75% SiO ₂ , 0-4% Al ₂ O ₃ , 7-15% Na ₂ O, 1-9% K ₂ O, 6-14% MgO and 0-1.5% % of ZrO ₂ , the total content of SiO ₂ and Al ₂ O ₃ is 71 to 75%, the total content of Na ₂ O and K ₂ O is 12 to 20%, and the content of CaO is less than 1%. grass. (v) Contains 60-75% SiO ₂ , 0.5-8% Al ₂ O ₃ , 10-18% Na ₂ O, 0-5% K ₂ O, 6-15% MgO, 0-8% % of CaO in glass. (vi) 63-75% SiO ₂ , 3-12% Al ₂ O ₃ , 3-10% MgO, 0.5-10% CaO, 0-3% SrO, 0-3% BaO, 10-18% Na ₂ O, 0-8% K ₂ O, 0-3% ZrO ₂ , 0.005-0.25% Fe ₂ O ₃ , and R ₂ O/Al ₂ O ₃ (wherein R ₂ O is glass whose Na ₂ O+K ₂ O) is 2.0 or more and 4.6 or less. (vii) 66-75% SiO ₂ , 0-3% Al ₂ O ₃ , 1-9% MgO, 1-12% CaO, 10-16% Na ₂ O, 0-5% K ₂ O glass.

As the transparent substrate 12, a glass plate is preferable. The manufacturing method of a glass plate is not specifically limited. It can manufacture by injecting a desired glass raw material into a melting furnace, heating and melting at 1500-1600 degreeC, and clarifying, and supplying it to a shaping|molding apparatus to shape a molten glass into a plate shape, and it can cool slowly. The forming method of the glass plate is not particularly limited, and for example, a down-draw method (for example, an overflow down-draw method, an orifice down-draw method, a redraw method, etc.), a float method, a rolling method, a pressing method, and the like can be used.

In the case of using a glass plate as the transparent substrate 12, in order to increase the strength, it is preferable to perform chemical strengthening treatment or physical strengthening treatment on the glass plate.

The chemical strengthening treatment method is not particularly limited, and the main surface of the glass plate is ion-exchanged to form a surface layer with residual compressive stress. Specifically, at a temperature below the glass transition point, alkali metal ions (for example, Li ions, Na ions) with a smaller ionic radius contained in the glass near the main surface of the glass plate are replaced with alkali metals with a larger ionic radius Ions (eg, Na ions or K ions with respect to Li ions, K ions with respect to Na ions). Thereby, a compressive stress remains on the main surface of a glass plate, and the intensity|strength of a glass plate improves.

The glass plate as the transparent substrate 12 preferably satisfies the following conditions. Such conditions can be satisfied by performing the above-mentioned chemical strengthening treatment. The compressive stress (hereinafter referred to as "CS") of the glass plate is preferably 400 MPa or more and 1200 MPa or less, and more preferably 700 MPa or more and 900 MPa or less. When CS is 400 Pa or more, the practical strength is sufficient. On the other hand, if CS is 1200 MPa or less, it can withstand its own compressive stress, and there is no fear of natural failure. The depth of the stress layer of the glass plate (hereinafter referred to as "DOL") is preferably 15 to 50 μm, more preferably 20 to 40 μm. If the DOL is 15 μm or more, even if a sharp jig such as a glass cutter is used, there is no fear of being easily scratched and damaged. On the other hand, if the DOL is 40 μm or less, it can withstand its own compressive stress without fear of natural failure.

The thickness of the transparent substrate 12 can be appropriately selected according to the application. For example, in the case of a glass plate, the thickness is preferably 0.1 to 5 mm, more preferably 0.2 to 2 mm. When a glass plate is used as the transparent substrate 12 and the above chemical strengthening treatment is performed, in order to make it more effective, the thickness of the glass plate is usually preferably 5 mm or less, more preferably 3 mm or less. The size of the transparent substrate 12 can be appropriately selected according to the application.

<<Frame Portion>> The frame portion 132 is formed by printing colored ink on the transparent base 12 . The frame portion 132 is preferably formed on the peripheral portion of the first main surface 12 a of the transparent substrate 12 . As the printing method, there are, for example, a bar coating method, a reverse coating method, a gravure coating method, a die coating method, a roll coating method, a screen method, an inkjet method, and the like. , The screen printing method is preferable because it can be printed on various transparent base frame parts, and can be printed according to the size of the transparent base frame part.

It does not specifically limit as a coloring ink, For example, the inorganic type ink containing a ceramic calcined body etc.; the organic type ink containing coloring materials, such as a dye and a pigment, and an organic resin, etc. can be used. The coloring ink for forming the frame portion 132 is usually black or white, but the color is not particularly limited. Moreover, the coloring ink which transmits only the wavelength range of infrared rays may be sufficient.

Examples of ceramics contained in inorganic inks include oxides such as chromium oxide and iron oxide; carbides such as chromium carbide and tungsten carbide; carbon black; and mica.

Organic inks are compositions containing dyes or pigments and organic resins. Dyes or pigments can be used without particular limitation. Examples of organic resins include epoxy resins, acrylic resins, polyethylene terephthalate, polyether terephthalate, polyarylate, polycarbonate, transparent ABS (Acrylonitrile Butadiene Styrene, Acrylonitrile Butadiene Styrene, Acrylonitrile Butadiene Styrene, Acrylonitrile Butadiene Styrene) ethylene-styrene) resin, phenolic resin, acrylonitrile-butadiene-styrene resin, polyurethane, polymethyl methacrylate, polyethylene (polyvinyl), polyvinyl butyral, poly Homopolymers of ether ether ketone, polyethylene, polyester, polypropylene, polyamide, polyimide, etc.; copolymers of monomers of these resins and monomers that can be copolymerized with them, etc.

Regarding inorganic inks and organic inks, since the firing temperature is low, it is preferable to use organic inks, and from the viewpoint of chemical resistance, organic inks containing pigments are more preferable.

<<Functional Layer>> The covering member 11 preferably has a functional layer (not shown) on the first main surface 12a or the second main surface 12b of the transparent substrate 12 , and more preferably on the second main surface 12b of the transparent substrate 12 with functional layers. The functional layer is a layer that exhibits properties that the transparent substrate 12 does not possess. As a functional layer, an antiglare layer, an antireflection layer, an antifouling layer, etc. are mentioned, for example.

(Anti-glare layer) The cover member 11 preferably has an anti-glare layer on the first main surface 12 a or the second main surface 12 b of the transparent substrate 12 . By providing the anti-glare layer, the reflection of surrounding light can be reduced, thereby preventing the visibility of the displayed image from being lowered. In particular, it is more preferable to provide an anti-glare layer on the second main surface 12b of the transparent substrate 12 .

The anti-glare layer can be formed by a so-called anti-glare process, which is a process of providing a concavo-convex shape on the first main surface 12 a or the second main surface 12 b of the transparent substrate 12 . As the anti-glare treatment, a known method can be applied. For example, when a glass plate is used as the transparent substrate 12, a desired surface roughness can be formed by chemically or physically applying surface treatment to the main surface of the glass plate. method of concave-convex shape, or wet coating, etc.

As a method of chemically performing anti-glare treatment, specifically, a method of performing frosting treatment can be mentioned. The frosting treatment is carried out, for example, by immersing a glass plate as the object to be treated in a mixed solution of hydrogen fluoride and ammonium fluoride.

As a method of physically performing anti-glare treatment, for example, a so-called sandblasting treatment in which crystalline silica powder, silicon carbide powder, etc. are blown onto the main surface of a glass plate with pressurized air, or a The method of wiping silicon dioxide powder, silicon carbide powder and other brushes wet with water, etc.

Among these, the frosting treatment is preferable as a method of anti-glare treatment for a glass plate because it is difficult to generate microcracks in the surface of the object to be treated, and it is difficult to cause a decrease in mechanical strength.

The main surface of the glass plate after chemically or physically anti-glare treatment in this way is preferably etched to adjust the surface shape. As the etching treatment, for example, a method of chemically etching a glass plate by dipping a glass plate in an etching solution of an aqueous solution of hydrogen fluoride can be used. The etching solution may contain acids such as hydrochloric acid, nitric acid, and citric acid in addition to hydrogen fluoride. By containing these acids, local generation of precipitates due to the reaction of cations such as Na ions and K ions contained in the glass plate and hydrogen fluoride can be suppressed, and etching can be performed uniformly in the processing surface.

In the case of etching treatment, the amount of etching can be adjusted by adjusting the concentration of the etching solution or the immersion time of the glass plate in the etching solution, so that the haze value of the anti-glare treated surface of the glass plate can be adjusted to the desired value. expected value. When physical surface treatment such as sandblasting is performed as an anti-glare treatment, cracks may occur, but such cracks can be removed by etching. The effect of suppressing glare is also obtained by etching. Here, the so-called glare refers to a phenomenon in which, when the transparent substrate 12 is used as a cover member for a display device of a pixel matrix type, a plurality of light particles having a period larger than that of the pixel matrix are observed on the surface of the cover member .

It is preferable that the surface roughness (root mean square roughness, RMS) of the main surface of the glass plate after the anti-glare treatment and the etching treatment is 0.01 to 0.5 μm. The surface roughness (RMS) is more preferably 0.01 to 0.3 μm, still more preferably 0.01 to 0.2 μm. By making the surface roughness (RMS) into the above-mentioned range, the haze value of the glass plate after the anti-glare treatment can be adjusted to 1 to 30%. The haze value is a value specified in JIS K 7136: (2000).

The surface roughness (RMS) can be measured according to the method specified in JIS B 0601:(2001). Specifically, with a laser microscope (trade name: VK-9700, manufactured by KEYENCE Corporation), the glass plate was measured by setting a field of view of 300 μm×200 μm on the measurement surface of the glass plate after the anti-glare treatment as a sample. height information. The measured value is critically corrected and the root mean square of the height obtained is obtained, whereby the surface roughness (RMS) can be calculated. As a critical value, it is preferable to use 0.08 mm.

The surface of the glass plate after the anti-glare treatment and the etching treatment has a concave-convex shape, and when viewed from above the surface of the glass plate, it appears to be a circular hole. The size (diameter) of the circular hole thus observed is preferably 1 μm or more and 10 μm or less. By being in this range, the prevention of glare and the anti-glare properties can be achieved at the same time.

(Anti-reflection layer) If an anti-reflection layer is provided on the main surface of the transparent substrate 12 as a functional layer, the reflection of external light can be reduced, thereby preventing the visibility of the displayed image from being lowered. When an anti-glare layer is provided on the main surface of the transparent substrate 12, it is preferable to provide an anti-reflective layer on the anti-glare layer.

The structure of the antireflection layer is not particularly limited as long as it can suppress the reflection of light within a specific range. For example, a structure obtained by laminating a high refractive index layer and a low refractive index layer can be used. Here, the high refractive index layer refers to, for example, a layer having a refractive index of 1.9 or more for light with a wavelength of 550 nm, and a low refractive index layer refers to a layer with a refractive index of 550 nm wavelength light of 1.6 or less.

The number of layers of the high-refractive-index layer and the low-refractive-index layer in the antireflection layer may be one in each of them, or may be in a configuration in which each of them is two or more layers. When the high-refractive-index layer and the low-refractive-index layer are each composed of one layer, it is preferable that the high-refractive-index layer and the low-refractive-index layer are sequentially laminated on the main surface of the transparent substrate 12 . When the high-refractive-index layer and the low-refractive-index layer are each composed of two or more layers, it is preferable that the high-refractive-index layer and the low-refractive-index layer are alternately laminated in this order.

In order to improve the antireflection performance, the antireflection layer is preferably a laminate formed by laminating a plurality of layers. The layered product is, for example, preferably a layered product of two or more and eight or less layers as a whole, more preferably a layered product of two or more and six or less layers, and still more preferably a layered product of two or more and four or less layers. The layered product here is preferably one obtained by alternately laminating high-refractive-index layers and low-refractive-index layers as described above. The total number of layers of the high-refractive index layer and the low-refractive index layer is preferably within the above-mentioned range. You may add a layer in the range which does not impair optical characteristics. For example, in order to prevent Na diffusion from the glass substrate, a SiO ₂ layer may also be inserted between the glass and the first layer.

The layer thickness of the high refractive index layer and the layer thickness of the low refractive index layer are appropriately adjusted.

The material constituting the high-refractive index layer and the low-refractive index layer is not particularly limited, and can be selected in consideration of the degree of antireflection performance required, productivity, and the like. Examples of materials constituting the high refractive index layer include niobium oxide (Nb ₂ O ₅ ), titanium oxide (TiO ₂ ), zirconium oxide (ZrO ₂ ), tantalum oxide (Ta ₂ O ₅ ), aluminum oxide (Al ₂ O ) ₃ ), silicon nitride (Si ₃ N ₄ ), etc. One or more kinds selected from these materials can be preferably used. Examples of materials constituting the low refractive index layer include silicon oxide (especially silicon dioxide SiO ₂ ), materials containing mixed oxides of Si and Sn, materials containing mixed oxides of Si and Zr, materials containing Si and Al Mixed oxide materials, etc. One or more kinds selected from these materials can be preferably used.

From the viewpoint of productivity or refractive index, it is preferable that the high-refractive index layer is a layer composed of one selected from niobium oxide, tantalum oxide, and silicon nitride, and the low-refractive index layer is A layer composed of silicon oxide.

The method of forming each layer constituting the antireflection layer is not particularly limited, and various methods can be used. For example, a vacuum evaporation method, an ion beam-assisted evaporation method, an ion plating method, a sputtering method, a plasma CVD (Chemical Vapor Deposition, chemical vapor deposition) method, etc. can be used. Among these methods, by using the sputtering method, a dense and highly durable layer can be formed, which is preferable. Sputtering methods such as a pulse sputtering method, an AC (Alternating Current) sputtering method, and a digital sputtering method are particularly preferred.

For example, in the case of the pulse sputtering method, a transparent substrate 12 such as a glass plate is placed in a chamber of a mixed gas atmosphere of an inert gas and oxygen, and a target is selected so as to have a desired composition. At this time, the gas type of the inert gas in the chamber is not particularly limited, and various inert gases such as argon or helium can be used.

The pressure in the chamber generated by the mixed gas of the inert gas and the oxygen gas is not particularly limited, but by setting it in the range of 0.5 Pa or less, the surface roughness of the formed layer can be easily set to a preferable range. The lower limit of the pressure in the chamber generated by the mixed gas of the inert gas and the oxygen is not particularly limited, for example, it is preferably 0.1 Pa or more.

When the high-refractive index layer and the low-refractive index layer are formed by the pulse sputtering method, the adjustment of the layer thickness of each layer can be realized, for example, by adjusting the discharge power or adjusting the time for forming each layer.

(Anti-fouling layer) Preferably, an anti-fouling layer is provided on the main surface of the transparent substrate 12 as a functional layer. If the antifouling layer is provided, the dirt (person's fingerprint, etc.) adhering to the transparent substrate 12 can be easily removed. The antifouling layer is preferably the outermost layer constituting the functional layer so as to fully exert its function. As a method for forming the antifouling layer, dry methods such as vacuum evaporation, ion beam-assisted evaporation, ion plating, sputtering, plasma CVD, spin coating, dip coating, and casting can be used. Any of wet methods such as the slit coating method, the spray method, and the like. From the viewpoint of scratch resistance, the dry method is preferred.

The constituent material of the antifouling layer can be appropriately selected from materials capable of imparting antifouling properties, water repellency, and oil repellency. Specifically, a fluorine-containing organosilicon compound can be mentioned. The fluorine-containing organosilicon compound can be used without any particular limitation as long as it can impart antifouling properties, water repellency, and oil repellency.

As the fluorine-containing organosilicon compound, for example, an organosilicon compound having one or more groups selected from the group consisting of a polyfluoropolyether group, a polyfluoroalkylene group, and a polyfluoroalkyl group can be preferably used. The polyfluoropolyether group refers to a divalent group having a structure in which a polyfluoroalkylene group and an etheric oxygen atom are alternately bonded.

As a commercial product of a fluorine-containing organosilicon compound having one or more groups selected from the group consisting of polyfluoropolyether group, polyfluoroalkylene group, and perfluoroalkyl group, for example, KP can be preferably used -801, KY-178, KY-130, KY-185 (all trade names, manufactured by Shin-Etsu Chemical Co., Ltd.), OPTOOL DSX and OPTOOL AES (all trade names, manufactured by Daikin Corporation), S550 (trade names, manufactured by Asahi Glass Co., Ltd.) )Wait.

The fluorine-containing organosilicon compound is usually mixed with a solvent such as a fluorine-based solvent and stored in order to suppress deterioration due to the reaction with moisture in the atmosphere. The durability of the antifouling layer, etc., has an adverse effect. Therefore, in the case of forming the antifouling layer by the vacuum evaporation method according to the following procedure, it is preferable to use a fluorine-containing organosilicon compound that has been subjected to a solvent removal treatment before being heated in a heating vessel.

Here, as the solvent used for storing the above-mentioned fluorine-containing organosilicon compound, for example, polyfluorohexane, m-xylene hexafluoride (C ₆ H ₄ (CF ₃ ) ₂ ), hydrofluoropolyether, HFE7200/ 7100 (trade name, manufactured by Sumitomo 3M, HFE7200 is represented by the formula: C ₄ F ₉ OC ₂ H ₅ , HFE7100 is represented by the formula: C ₄ F ₉ OCH ₃ ) and the like. For example, the concentration of the solvent contained in the solution of the fluorine-containing organosilicon compound is preferably 1 mol % or less, more preferably 0.2 mol % or less. It is particularly preferable to use a fluorine-containing organosilicon compound that does not contain a solvent.

The treatment of removing the solvent from the solution of the fluorine-containing organosilicon compound containing the above-mentioned fluorine-based solvent can be carried out, for example, by evacuating the container containing the solution of the fluorine-containing organosilicon compound. The vacuum evacuation time varies according to the evacuation capacity of the evacuation line, the vacuum pump, etc., the amount of the solution, etc., so it is not limited. For example, the vacuum evacuation is sufficient for 10 hours or more.

In the case of forming the antifouling layer composed of the above-mentioned fluorine-containing organosilicon compound, it is preferable to use a vacuum evaporation method. In the case of using the vacuum evaporation method, the above-mentioned solvent removal treatment can also be carried out by introducing the solution of the fluorine-containing organosilicon compound into the heating vessel of the film-forming apparatus for forming the antifouling layer, and then raising the temperature. Before, the heating vessel was evacuated at room temperature. The solvent may be removed by an evaporator or the like before the introduction into the heating container.

The above-mentioned fluorine-containing organosilicon compounds containing a small amount of a solvent or containing no solvent are more likely to be degraded by exposure to the atmosphere than those containing a solvent. Therefore, the storage container of the fluorine-containing organosilicon compound with less solvent content (or no solvent) is preferably one obtained by replacing and sealing the container with an inert gas such as nitrogen, so that the exposure time to the atmosphere during handling changes. short.

Specifically, it is preferable to introduce the fluorine-containing organosilicon compound into the heating container of the film forming apparatus immediately after opening the storage container. Furthermore, it is preferable to remove the atmosphere (air) contained in the heating container by evacuating the inside of the heating container or replacing it with an inert gas such as nitrogen or a rare gas after introduction. More preferably, for example, the storage container and the heating container are connected by piping with a valve so that the storage container (storage container) can be introduced into the heating container of the film forming apparatus without contacting with the atmosphere. Furthermore, it is preferable to start heating for film formation immediately after introducing the fluorine-containing organosilicon compound into the heating container and replacing the inside of the container with a vacuum or an inert gas.

Generally speaking, the thickness of the antifouling layer is preferably 2-20 nm, more preferably 2-15 nm, and still more preferably 2-10 nm.

<Manufacturing Method of Covering Member> The manufacturing method of the covering member 11 is not particularly limited, but for example, a method of preparing the transparent substrate 12 having the first main surface 12a and the second main surface 12b, and preparing a transparent substrate 12 having a The transfer substrate (not shown) of the fluorine compound (not shown), the first main surface 12a of the transparent substrate 12 and the surface of the transfer substrate to which the fluorine-containing compound is attached (hereinafter also referred to as the "transfer surface") ”), the fluorine-containing compound is transferred to the first main surface 12a of the transparent substrate 12, and by this transfer, the compound containing F atoms is attached to the first main surface 12a, and the contact angle of the first main surface 12a is changed. Set to 50° or less. As a method of manufacturing the covering member 11, there are also mentioned methods in which the first main surface 12a of the transparent substrate 12 and the surface of the fluorine-containing compound layer on the transfer substrate are separated by a predetermined distance (for example, 1 to 10 mm). ) face each other and let stand for 1 to 48 hours. From the viewpoint of adjustment of the value of the contact angle of the first main surface 12a and easy control of the adhesion amount of the fluorine-containing compound, the method for manufacturing the covering member 11 is preferably the above-described method by transfer.

On at least one surface of the first main surface 12a or the second main surface 12b of the transparent substrate 12, the frame portion 132 or the functional layer is formed as necessary.

When the transparent substrate 12 is a glass plate, it is preferable that the transfer substrate is also a glass plate. The thickness of the transfer substrate is not particularly limited, and the size of the transfer substrate is preferably the same as or larger than the transparent substrate 12 .

The fluorine-containing compound adhering to the transfer surface of the transfer substrate is preferably in the form of a layer having a certain thickness. The layered fluorine-containing compound (hereinafter also referred to as a "transferring fluorine-containing compound layer") is preferably formed on the transfer substrate in an amount sufficiently larger than the thickness of a single molecule. The fluorine-containing compound layer for transfer is formed in the same order as the antifouling layer of the cover member 11 . However, the thickness of the fluorine-containing compound layer for transfer is preferably thicker than that of the antifouling layer of the cover member 11, and specifically, it is, for example, 50 to 180 nm, or preferably 60 to 170 nm. The fluorine-containing compound layer for transfer may not be a continuous layer continuous in the main surface direction of the substrate for transfer, but may be a discontinuous layer (intermittent layer).

Among the fluorine-containing compounds (for example: fluorine-containing organosilicon compounds) constituting the fluorine-containing compound layer for transfer, those which are chemically bonded strongly by the reaction with the transparent substrate 12 such as a glass plate (for example: silane coupling reaction) are usually only chemically bonded. Molecules that are in contact with a transparent substrate 12 such as a glass plate. Therefore, the molecules (fluorine chains) existing on the molecules in contact with the transparent substrate 12 are only physically aggregated, and can be easily released and transferred to other members.

The 1st main surface 12a (the frame part 132 may be formed) of the transparent base body 12 and the transfer surface of the base body for transfer are brought into contact, and after a predetermined time passes, both are peeled off. In this way, the fluorine-containing compound (fluorine-containing compound layer for transfer) adhering to the transfer substrate is transferred to the first main surface 12 a of the transparent substrate 12 .

At this time, the contact time between the transparent substrate 12 and the transfer substrate (also referred to as “transfer time”) is preferably 0.5 minutes or more and less than 60 minutes, more preferably 0.5 minutes or more and 30 minutes or less, and more preferably It is 0.5 minutes or more and 15 minutes or less. [Example]

Hereinafter, embodiments of the present invention will be specifically described with reference to examples and the like. However, the present invention is not limited to the following examples. Examples 1 to 6 are examples, and examples 7 to 8 are comparative examples.

<Example 1> As described below, the covering member of Example 1 was produced.

<<Preparation of a transparent base body (glass plate) >> In each example, a glass plate was used as a transparent base body which becomes a cover member. More specifically, first, Dragontrail (trade name, manufactured by Asahi Glass Co., Ltd., thickness 1.3 mm) as a glass plate for chemical strengthening was prepared. After cutting it into a size of 100 mm × 100 mm, chemical strengthening treatment was carried out. That is, the glass plate for chemical strengthening was immersed in potassium nitrate (molten salt) heated to 450° C. and melted for 2 hours, then pulled from the molten salt, and slowly cooled to room temperature over 1 hour. In this way, a chemically strengthened glass plate having a surface compressive stress (CS) of 730 MPa and a depth of stress layer (DOL) of 30 μm was obtained.

<<Formation of a frame part>> An outer frame-shaped frame part was formed by screen printing on the outer peripheral part of the 1st main surface of the glass plate which becomes a cover member. Specifically, the frame portion was formed by printing in the shape of a black frame having a width of 10 mm on the four sides of the outer peripheral portion of the first main surface of the glass plate in the following procedure. First, after applying black ink to a thickness of 5 μm by a screen printing machine, it was kept at 150° C. for 10 minutes and dried to form a first printed layer. Next, on the first printed layer, black ink was applied to a thickness of 5 μm in the same procedure as above, and then dried at 150° C. for 40 minutes to form a second printed layer. In this way, the frame part in which the 1st printing layer and the 2nd printing layer were laminated|stacked is formed. As the black ink, HFGV3RX01 (trade name, manufactured by Seiko Corporation) was used.

<<Formation of an antifouling layer>> An antifouling layer was formed in the following procedure on the second main surface of the glass plate serving as a covering member. First, a solution of a fluorine-containing organosilicon compound, which is a material of an antifouling layer, is introduced into a heating vessel. 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, and this was used as a composition for forming an antifouling layer. In Example 1, KY185 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) was used as the material of the antifouling layer. Next, the heating container containing the composition for forming an antifouling layer was heated to 270°C, and after reaching 270°C, this state was maintained for 10 minutes until the temperature became stable. Next, after setting the glass plate in the vacuum chamber, the composition for forming the antifouling layer is supplied toward the second main surface of the glass plate from the nozzle connected to the heating container containing the composition for forming the antifouling layer, thereby forming the antifouling layer. . The antifouling layer was formed until the thickness of the antifouling layer was 4 nm while measuring the thickness of the antifouling layer with a crystal oscillator monitor installed in the vacuum chamber. Then, the glass plate taken out from the vacuum chamber was placed on a heating plate so that the antifouling layer was upward, and a heat treatment was performed at 150° C. for 60 minutes in the atmosphere. In this way, the antifouling layer is formed on the entire second main surface of the glass plate.

«Transferring» Using the substrate for transfer, the fluorine-containing compound layer for transfer was transferred to the first main surface (the main surface on the side where the frame portion was formed) of the glass plate serving as the cover member. Specifically, first, another glass plate with the same size (100 mm×100 mm) as the glass plate used as the cover member was prepared, and this was used as the substrate for transfer. On one main surface (transfer surface) of the substrate for transfer, a fluorine-containing compound layer for transfer was formed in the same order as described in the above-mentioned "formation of antifouling layer". The thickness of the fluorine-containing compound layer for transfer was set to 70 nm. Next, the first main surface (the main surface on the side where the frame portion is formed) of the glass plate serving as the cover member and the surface of the fluorine-containing compound layer for transfer formed on the substrate for transfer (the side of the substrate for transfer) face is the face on the opposite side) contacts. The contact time (transfer time) was set to 10 minutes. After transfer, the two are peeled off.

<Example 2> An anti-reflection layer was formed on the second main surface of the glass plate serving as a cover member, an anti-fouling layer was formed on the anti-reflection layer, and the thickness of the fluorine-containing compound layer for transfer was changed from 70 nm to 150 nm In the same procedure as in Example 1, except for that, the covering member of Example 2 was produced.

<<Formation of Antireflection Layer>> An antireflection layer having a structure in which high-refractive-index layers and low-refractive-index layers are alternately laminated is formed on the entire second principal surface of the glass plate. More specifically, in Example 2, a high-refractive-index layer made of niobium oxide and a low-refractive-index layer made of silicon oxide were sequentially formed to form an antireflection layer having two laminated layers. Regarding the thickness of each layer, the high refractive index layer of the first layer was set to 13 nm, and the low refractive index layer of the second layer was set to 120 nm. Hereinafter, the formation methods of the high-refractive-index layer and the low-refractive-index layer will be described, respectively.

(Formation of High Refractive Index Layer) In a vacuum chamber, a mixed gas obtained by mixing oxygen with argon gas in a manner of 10% by volume was introduced into the vacuum chamber, and the pressure was 0.3 Pa, the frequency was 20 kHz, and the power density was 3.8 W/cm ² . 2. Under the condition of inversion pulse width of 5 μsec, use niobium oxide target (trade name: NBO target, manufactured by AGC CERAMICS Co., Ltd.) to perform pulse sputtering, and form the entire surface of the glass plate where the high refractive index layer should be formed. High refractive index layer composed of niobium oxide.

(Formation of low-refractive index layer) In a vacuum chamber, a mixed gas obtained by mixing oxygen with argon gas in a manner of 40% by volume was introduced into a vacuum chamber under a pressure of 0.3 Pa, a frequency of 20 kHz, and a power density of 3.8 W/cm ² 2. Under the condition of inversion pulse width of 5 μsec, pulse sputtering is performed using a silicon target, and a low refractive index layer composed of silicon oxide is formed on the entire surface of the surface where the low refractive index layer should be formed.

<Example 3> An anti-reflection layer was formed on the second main surface of the glass plate serving as a cover member, an anti-fouling layer was formed on the anti-reflection layer, and the materials of the anti-fouling layer and the fluorine-containing compound layer for transfer were changed from KY185 The covering member of Example 3 was produced in the same procedure as in Example 1, except that the transfer time was changed from 10 minutes to 1 minute for OPTOOL DSX (trade name, manufactured by Daikin Corporation). The antireflection layer was formed in the same order as in Example 2.

<Example 4> An anti-reflection layer was formed on the second main surface of the glass plate serving as a cover member, an anti-fouling layer was formed on the anti-reflection layer, and the materials of the anti-fouling layer and the fluorine-containing compound layer for transfer were changed from KY185 The covering member of Example 4 was produced in the same procedure as in Example 1, except that it was S550 (trade name, manufactured by Asahi Glass Co., Ltd.) and the transfer time was changed from 10 minutes to 1 minute. The antireflection layer was formed in the same order as in Example 2.

<Example 5> The cover member of Example 5 was produced in the same procedure as Example 1 except that the fluorine-containing compound layer for transfer was not brought into contact with the first main surface of the glass plate serving as the cover member. Specifically, in Example 5, first, in the same manner as in Example 1, a fluorine-containing compound layer for transfer (thickness: 70 nm) was formed on the transfer surface of the substrate for transfer. Next, the first main surface (the main surface on the side where the frame portion is formed) of the glass plate serving as the cover member and the surface of the fluorine-containing compound layer for transfer formed on the substrate for transfer (the side of the substrate for transfer) The opposite side is the opposite side) facing each other at a distance of 5 mm, and left to stand for 24 hours.

<Example 6> In addition to forming an antireflection layer on the second main surface of the glass plate to be the cover member, forming an antifouling layer on the antireflection layer, and changing the transfer time from 10 minutes to 60 minutes, In the same procedure as in Example 1, the covering member of Example 6 was produced. The antireflection layer was formed in the same order as in Example 2.

<Example 7> Example 7 was prepared in the same procedure as in Example 1, except that the thickness of the fluorine-containing compound layer for transfer was changed from 70 nm to 200 nm, and the transfer time was changed from 10 minutes to 60 minutes. the covering component.

<Example 8> The fluorine-containing compound layer for transcription|transfer was not transcribe|transferred to the 1st main surface of the glass plate used as a cover member. Instead, a polyimide tape (Kapton tape 650S, manufactured by Teraoka Manufacturing Co., Ltd.) coated with a silicone-based adhesive was attached to the first main surface of the glass plate serving as the cover member, and immediately peeled off. Except for this, in the same procedure as in Example 1, the covering member of Example 8 was produced.

<Contact angle> The contact angle of the 1st main surface of a glass plate was calculated|required as follows. First, the area of the unprinted frame-shaped frame portion on the first main surface of the glass plate was divided into 4×4 equal parts. The contact angle of water at the intersection (9 points in total) of the lines (3+3) drawn on the second main surface of the glass plate when divided into equal parts was measured. Specifically, at a measurement temperature of 23° C., the contact angle after 5 seconds after the dropwise addition of 5 μL of pure water was measured using a contact angle meter (manufactured by Kyowa Interface Science Co., Ltd., PCA-11). The average value of the contact angles of the measured 9 points in total was made into the contact angle of the 1st main surface of a glass plate.

<Atomic ratio (F/Si)> The atomic ratio (F/Si) of the 1st main surface of a glass plate was calculated|required as follows. First, the F atomic concentration (unit: atomic %) was obtained using an X-ray photoelectron spectroscopy apparatus (manufactured by JEOL Ltd., JPS-9000MC) in the region of the first main surface of the glass plate in which the frame-shaped frame portion was not printed. and Si atomic concentration (unit: atomic %). The ratio of the obtained concentration of F atoms to the concentration of Si atoms was defined as the ratio (F/Si) of the number of F atoms to the number of Si atoms in the first main surface of the glass plate. More specifically, the measurement was performed under the conditions that the source of X-rays was MgKα rays, an acceleration voltage of 12 kV, and 25 mA. The measurement was performed with a spot diameter of 6 mmf. There is no tilt of the sample. The measurement was performed with a passing energy of 50 eV, a measurement step of 0.5 eV, a Dwell Time of 100 msec, and a number of scans of 30 times. The atomic concentration ratio of F/Si was calculated from the intensity of the F1s peak and the peak intensity of Si2p3/2 after removing the background by the Shirley method for the bonding energy peak obtained from the measurement result.

<Evaluation> The covering member of each example was evaluated as follows.

<<Preparation of test body>> Soda lime glass (plate thickness: 0.7 mm, size: 100 mm×100 mm) was prepared, and this was used as a display panel substitute. The first main surface (including the frame portion) of the glass plate of the cover member in each example was bonded to one of the main surfaces of the display panel substitute using an adhesive layer (manufactured by Kashiwa Paper Co., Ltd., MK64). In this way, a test body was produced. The bonding system used a bonding apparatus (manufactured by CLIMB PRODUCTS). In each example, 300 test bodies were produced.

<<Bubble Foaming Ratio>> It was confirmed whether or not bubbles having a size of 30 μm or more were generated between the glass plate and the adhesive layer in each test body. In each example, the ratio (%) of the number of test objects with bubbles of 30 μm or more generated with respect to the number of all test objects (300 pieces) was obtained. As the ratio is smaller, it can be estimated that the generation of air bubbles between the glass plate and the adhesive layer can be suppressed more, and it is preferably 6% or less.

The above results are summarized in Table 1 below. The "material of the antifouling layer" in the following Table 1 also refers to the "material of the fluorine-containing compound layer for transfer".

[Table 1]

As shown in Table 1 above, Examples 1 to 6 in which a compound containing F atoms (atomic ratio (F/Si) exceeds 0) was attached to the first main surface of the glass plate and the contact angle of the first main surface was 50° or less. Compared with Examples 7-8 which did not satisfy these conditions, the generation of air bubbles between the glass plate and the adhesive layer was suppressed.

In Examples 1 to 4 in which the atomic ratio (F/Si) was within the range of 0.005 to 0.13, the generation of air bubbles between the glass plate and the adhesive layer was suppressed compared with Examples 5 to 6 which were outside the range.

Comparing Examples 1 to 4, the atomic ratio (F/Si) of the first main surface of the glass plate in Example 3 of 0.012 was compared with that of Example 1, in which the atomic ratio (F/Si) was 0.023 to 0.075. 2 and 4 are more capable of suppressing bubble generation. Furthermore, in Example 7, since the atomic ratio (F/Si) is large, there are many regions with low surface energy, so that the generation rate of bubbles is considered to be high on the contrary.

This application is based on Japanese Patent Application No. 2017-102481 filed on May 24, 2017, the contents of which are incorporated herein by reference.

11‧‧‧Covering member 12‧‧‧Transparent substrate 12a‧‧‧First main surface 12b‧‧‧Second main surface 14‧‧‧Adhesive layer 100‧‧‧Display device 102‧‧‧Backlight unit 104‧‧‧ Display panel (covered member) 104a‧‧‧display surface 106‧‧‧frame body 107‧‧‧frame body bottom plate 131‧‧‧adhesive layer 132‧‧‧frame part 141‧‧‧wiring 511‧‧‧covering member 512 ‧‧‧Transparent substrate 512a‧‧‧First main surface 551‧‧‧Bubble 561‧‧‧Step part

FIG. 1 is a cross-sectional view showing a display device of this embodiment. FIG. 2 is an enlarged cross-sectional view showing the cover member, the adhesive layer and the display panel. 3 is an enlarged cross-sectional view showing a state in which the previous cover member is attached to the display panel through the adhesive layer. FIG. 4 is a cross-sectional view showing the covering member of the present embodiment.

11‧‧‧Covering member

12‧‧‧Transparent substrate

12a‧‧‧First main face

12b‧‧‧Second main side

14‧‧‧Adhesive layer

100‧‧‧Display device

102‧‧‧Backlight unit

104‧‧‧Display panel (covered member)

104a‧‧‧Display surface

106‧‧‧Frame

107‧‧‧Frame bottom plate

131‧‧‧Second layer

132‧‧‧Frame

141‧‧‧Wiring

Claims (19)

A covering member comprising a transparent substrate, the transparent substrate having a first main surface facing the covered member, and a second main surface opposite to the first main surface, and attached to the first main surface There is a compound containing an F atom, and the contact angle of water on the first main surface is 50° or less. The covering member according to claim 1, wherein the material of the transparent substrate is glass whose main component is silicon dioxide, and the ratio (F/Si) of the number of F atoms to the number of Si atoms in the first main surface is: 0.005~0.13. The covering member of claim 2, wherein the above ratio (F/Si) is 0.015 to 0.1. The covering member according to any one of claims 1 to 3, wherein the contact angle of water on the first main surface is 25° to 45°. The covering member of claim 4, wherein the contact angle of water on the first main surface is 28° to 40°. The covering member according to any one of claims 1 to 3, wherein the thickness of the transparent substrate is 0.1 mm or more and 5 mm or less. The covering member according to any one of claims 1 to 3, wherein the compound containing the F atom is an organic compound. The covering member according to any one of claims 1 to 3, wherein the transparent substrate is a glass plate. The covering member according to claim 8, wherein the glass plate is a chemically strengthened glass plate. The covering member according to claim 8, wherein the compressive stress (CS) of any main surface of the glass plate is 400 MPa or more and 1200 MPa or less. The covering member according to claim 8, wherein the depth (DOL) of the stress layer on any main surface of the glass plate is 15 μm or more and 50 μm or less. The covering member according to any one of claims 1 to 3, wherein the first main surface has a frame portion. The covering member according to any one of claims 1 to 3, further comprising a functional layer disposed on the second main surface of the transparent substrate. The covering member of claim 13, wherein the above-mentioned functional layer comprises an antifouling layer. The covering member according to claim 14, wherein the thickness of the antifouling layer is 2 nm or more and 20 nm or less. The covering member of claim 13, wherein the above-mentioned functional layer comprises an antireflection layer. A method for manufacturing a covering member, which is a method for manufacturing a covering member including a transparent substrate, and prepares a transparent substrate having a first main surface facing the member to be covered and a second main surface opposite to the first main surface A substrate is prepared on one side of a transfer substrate to which a fluorine-containing compound is adhered, the first main surface of the transparent substrate is brought into contact with the surface of the transfer substrate to which the fluorine-containing compound is adhered, and the fluorine-containing compound is transferred. It is printed on the first main surface of the transparent substrate, the compound containing F atoms is adhered to the first main surface by the transfer, and the contact angle of water on the first main surface is set to 50° or less. The method for manufacturing a covering member according to claim 17, wherein the material of the transparent substrate is glass whose main component is silica, and the contact angle of water on the first main surface is set to 25 to 45 by the transfer transfer. °, the ratio (F/Si) of the number of F atoms with respect to the number of Si atoms in the first main surface is set to 0.005 to 0.13. A display device comprising a covering member, an adhesive layer, and a display panel as claimed in any one of claims 1 to 16, wherein the covering member is formed so that the first main surface of the transparent substrate faces the display panel. oriented, and is bonded to the display panel via the adhesive layer.

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