Glass laminate, cover glass, and display unit

Abstract

To provide a glass laminate improved in abrasion resistance of an antifouling layer while having surface asperity, a cover glass, and a display unit.SOLUTION: A glass laminate 10 includes: a glass substrate 11 having a first principal plane 11A and a second principal plane 11B; an antiglare layer 12 having a rugged shape formed on a side of the first principal plane 11A; an antireflection layer 13 formed on a surface of the antiglare layer 12; and an anti-fouling layer 14 formed on a surface of the antireflection layer 13. The antireflection layer 13 includes an outermost layer 131 formed as a silicon oxide layer on a plane in contact with the anti-fouling layer 14. The outermost layer 131 includes at least one metal selected from Zr, Al, Sn, and Zn.SELECTED DRAWING: Figure 3

Description

Technical Field

[0001] The present invention relates to a glass laminate, a cover glass, and a display device.

Background Art

[0002] In display devices such as car navigation devices and smartphones, cover glass is used as the front panel of a touch panel or a display panel. As this type of cover glass, a glass laminate is known that includes an antiglare layer formed on one main surface side of a glass substrate, and an antireflection layer and an antifouling layer respectively laminated on the surface of the antiglare layer (see, for example, Patent Document 1). In this type of glass laminate, the antifouling layer has a function of suppressing the adhesion of dirt due to the touch operation of the user, and when dirt adheres, the adherent can be easily removed by cleaning such as wiping.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] By the way, the antiglare layer has an uneven structure formed with a predetermined surface roughness to impart antiglare properties, and the antireflection layer and the antifouling layer are formed to be thin. In such a glass laminate in which the antireflection layer and the antifouling layer are provided laminated on the surface of the antiglare layer, an uneven structure equivalent to that of the antiglare layer appears on the surface of the antifouling layer, so the wear resistance of the antifouling layer is likely to decrease, and improvement of the wear resistance is desired.

[0005] The present invention has been made in view of the above problems, and an object thereof is to provide a glass laminate, a cover glass, and a display device that have an uneven layer such as an antiglare layer on the glass surface and improve the wear resistance of the antifouling layer.

Means for Solving the Problems

[0006] In order to solve the above-described problems and achieve the object, the glass laminate according to the present invention includes a glass substrate having a first main surface and a second main surface, a concavo-convex layer formed on the side of the first main surface, a silicon oxide layer formed on the surface of the concavo-convex layer, and an antifouling layer formed on the surface of the silicon oxide layer, and the silicon oxide layer contains at least one metal selected from Zr, Al, Sn, and Zn.

[0007] The cover glass according to the present invention includes the glass laminate having the above-described configuration. The display device according to the present invention includes the above-described cover glass.

Advantages of the Invention

[0008] According to the present invention, it is possible to improve the wear resistance of the antifouling layer while having a concavo-convex layer such as an antiglare layer.

Brief Description of the Drawings

[0009]

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

Mode for Carrying Out the Invention

[0010] Hereinafter, with reference to the accompanying drawings, preferred embodiments of the present invention will be described in detail. Note that the present invention is not limited by this embodiment, and when there are a plurality of embodiments, those configured by combining each embodiment are also included. Also, numerical values include the range of rounding. In this specification, the notation of the numerical range "α to β" means "α or more and β or less".

[0011] (In-vehicle display device) FIG. 1 is a schematic diagram showing an in-vehicle display device including a glass laminate according to this embodiment. As shown in FIG. 1, the in-vehicle display device 2 is a display device provided in a vehicle, and is provided, for example, on the front side of the steering shaft 1 in the vehicle interior. The in-vehicle display device 2 includes a display panel 3 and a glass laminate 10. On the display panel 3, for example, various meters such as a car navigation screen and a speedometer, and images such as a start button are displayed. The glass laminate 10 is used as a cover glass on the surface (front surface) of the display panel 3. However, the configuration of FIG. 1 is an example, and the vehicle display device to which the glass laminate 10 is applied may have any configuration. Also, the glass laminate 10 is not limited to being used as a cover glass on the surface of the in-vehicle display device, and includes cover glasses for display devices such as smartphones and tablet PCs, and may be used for any application.

[0012] (Glass laminate) Figure 2 is a cross-sectional view showing an outline of the glass laminate. As shown in Figure 2, the glass laminate 10 is a transparent plate-like glass member and includes a glass substrate (glass base plate) 11, an antiglare layer 12, an antireflection layer 13, an antifouling layer 14, and a printing layer 15. The glass substrate 11 includes a first main surface 11A and a second main surface 11B that face each other. On the first main surface 11A, the antiglare layer 12, the antireflection layer 13, and the antifouling layer 14 are laminated in that order. Further, a printing layer 15 is laminated on the peripheral portion of the second main surface 11B. When the glass laminate 10 is mounted on, for example, an in-vehicle display device 2 (mounted object), the side of the first main surface 11A is exposed to the outside, and the side of the second main surface 11B faces the mounted object (display panel 3). Here, the term "transparent" means transmitting visible light.

[0013] The glass substrate 11 is formed of a general glass. Specifically, as the glass substrate 11, non-alkali glass, soda-lime glass, soda-lime silicate glass, aluminosilicate glass, borosilicate glass, lithium aluminosilicate glass, borosilicate glass, etc. can be used. Further, when used for the glass laminate 10, as the glass substrate 11, aluminosilicate glass or lithium aluminosilicate glass, which can obtain high-strength glass with large stress easily even with a thin thickness by strengthening treatment, is preferable. The glass substrate 11 is preferably strengthened, for example, by chemical strengthening treatment. This type of chemical strengthening treatment is usually performed by immersing the glass substrate 11 formed into a predetermined shape in a molten salt containing an alkali metal.

[0014] The shape of the glass substrate 11 used for the glass laminate 10 may be not only a flat shape as shown in FIG. 2, but also a shape including a complex three-dimensional curved surface shape having one or more curved portions or bent portions. The curved surface means a surface having a curvature radius of 10,000 mm or less. When the glass substrate 11 has a curved surface, the curvature radius is preferably 50 mm or more, more preferably 100 mm or more, and still more preferably 200 mm or more. Further, the curvature radius is 10,000 mm or less, preferably 5,000 mm or less, and more preferably 3,000 mm or less. When the glass substrate 11 has a curved surface, the antiglare layer 12, the antireflection layer 13, the antifouling layer 14, and the printing layer 15 laminated on the glass substrate 11 each have a shape following the shape of the glass substrate 11.

[0015] The thickness of the glass substrate 11 is preferably 0.2 mm or more and 5.0 mm or less, more preferably 0.8 mm or more and 3.0 mm or less, and still more preferably 1.0 mm or more and 2.5 mm or less. By setting the thickness within this range, it is possible to achieve both weight reduction and strength of the glass substrate 11, and it is possible to configure a cover glass for an in-vehicle display device with improved design. Note that the thickness of the glass substrate 11 refers to the distance in the normal direction between the first main surface 11A and the second main surface 11B.

[0016] (Antiglare layer) The antiglare layer 12, also called an AG (Anti-Glare) layer, is provided on the side of the first main surface 11A of the glass substrate 11 to impart antiglare properties to the glass laminate 10. The antiglare layer 12 is an uneven layer formed in an uneven shape with a predetermined surface roughness on the side of the first main surface 11A of the glass substrate 11. Here, in the present embodiment, since the antireflection layer 13 and the antifouling layer 14 are each formed to be thin, the uneven structure on the surface of the antiglare layer 12 is directly traced and formed on the surface of the antifouling layer 14. It is preferable that this uneven structure satisfies 0.03 μm to 0.25 μm of the surface roughness RMS of the first main surface 11A, that is, the surface roughness RMS of the surface of the antifouling layer 14, and more preferably satisfies 0.08 μm to 0.20 μm. Further, it is preferable that the uneven structure satisfies 10 μm to 40 μm of the average length RSm of the elements of the roughness curve of the first main surface 11A, that is, the average length RSm of the elements of the roughness curve of the surface of the antifouling layer 14, and more preferably satisfies 15 μm to 35 μm. In the present embodiment, since the antiglare layer 12 is formed in an uneven shape that satisfies 0.03 μm to 0.25 μm of the surface roughness RMS of the first main surface 11A and 10 μm to 40 μm of the average length RSm of the elements of the roughness curve, the surface roughness RMS and the average length RSm of the elements of the roughness curve of the antifouling layer 14 can be set within a desired range.

[0017] Here, the surface roughness RMS is the average depth of the unevenness from the reference surface (here, the surface of the substrate before surface treatment). It is also called the root mean square roughness and may be represented by Rq. Further, the average length RSm of the elements of the roughness curve is the length obtained by averaging the length on the reference surface where one cycle of unevenness occurs in the roughness curve included in the reference length taken on the reference surface. The surface roughness RMS and the average length RSm of the elements of the roughness curve can be measured by a method conforming to the method defined in JIS B 0601 (2001). In the measurement of the surface roughness, the measurement is performed at a plurality of points selected without bias within the plane of the antiglare layer, and the average thereof is taken. It is preferable to take 5 or more measurement points.

[0018] In this embodiment, the antiglare layer 12 is realized by an uneven shape directly formed on the first main surface 11A of the glass substrate 11 by performing an antiglare treatment and an etching treatment on the first main surface 11A. As the antiglare treatment, for example, a method of performing a frosting treatment on the first main surface 11A of the glass substrate 11 can be mentioned. The frosting treatment can be performed, for example, by immersing the glass substrate 11, which is the object to be treated, in a mixed solution of hydrogen fluoride and ammonium fluoride and chemically surface-treating the immersion surface.

[0019] In addition to the method by such chemical treatment, for example, a so-called sandblasting treatment in which crystalline silicon dioxide powder, silicon carbide powder, etc. are blown onto the surface of the transparent substrate with pressurized air, or a physical treatment method such as polishing with a brush to which crystalline silicon dioxide powder, silicon carbide powder, etc. are attached and wet with water can also be used. In particular, in the method of performing a frosting treatment in which the surface is chemically treated using a chemical solution such as hydrogen fluoride, microcracks are less likely to occur on the surface of the object to be treated, and a decrease in mechanical strength is less likely to occur. Therefore, it can be preferably used as a method for surface-treating the transparent substrate.

[0020] After creating the unevenness in this way, in order to adjust the surface shape, the first main surface 11A of the glass substrate 11 is chemically etched. Thereby, the haze can be adjusted to a desired value according to the etching amount, cracks generated by sandblasting treatment or the like can be removed, and glare can be suppressed. As the etching treatment, a method of immersing the glass substrate 11, which is the object to be treated, in a solution mainly composed of hydrogen fluoride is preferably used. As components other than hydrogen fluoride, hydrochloric acid, nitric acid, citric acid, etc. may be contained. By containing these, it is possible to suppress the occurrence of a precipitation reaction locally due to the reaction between the alkali component in the glass and hydrogen fluoride, and the etching can proceed uniformly in the plane.

[0021] Further, the concavo-convex structure of the antiglare layer 12 may be formed from a layer having a material composition different from that of the glass substrate 11. For example, a coating film in which particles having an arbitrary refractive index are dispersed may be used on the first main surface 11A of the glass substrate 11, or an uneven shape may be formed on the main surface of the transparent resin film to be laminated.

[0022] (Anti-reflection layer) FIG. 3 is an enlarged view of the anti-reflection layer. The anti-reflection layer 13, also called an AR (Anti-Reflection) layer, provides an effect of reducing reflectance and reduces glare caused by reflected light. Therefore, when the anti-reflection layer 13 is used in a display device, the transmittance of light from the display device can be improved, and the visibility of the display device can be improved.

[0023] As the configuration of the anti-reflection layer 13, if the outermost layer 131 is a silicon oxide layer, it is not particularly limited. As a configuration capable of suppressing light reflection, for example, a configuration in which a high refractive index layer having a refractive index of 2.0 or more at a wavelength of 550 nm and a low refractive index layer having a refractive index of 1.3 to 1.9 at a wavelength of 550 nm are alternately laminated can be adopted. The number of layers of the low refractive index layer and the high refractive index layer is not limited, but the low refractive index layer is preferably 1 or more and 6 or less layers, and the high refractive index layer preferably has the same number of layers as the low refractive index layer. In FIG. 3, a case where the low refractive index layer and the high refractive index layer are each composed of 2 layers is illustrated. In the present embodiment, the low refractive index layer and the high refractive index layer may each be composed of 1 layer.

[0024] When the low refractive index layer and the high refractive index layer are each composed of a plurality of layers, the layer farthest from the glass substrate 11 (the layer in contact with the antifouling layer 14) is defined as the outermost layer 131. When the layers are numbered toward the glass substrate 11 with the outermost layer 131 being the first layer, the odd-numbered layers including the outermost layer 131, in FIG. 3, the outermost layer 131 and the third layer 133 are composed of the low refractive index layer. If the layer adjacent to the glass substrate 11 side of the outermost layer 131 is defined as the second layer 132, the even-numbered layers including the second layer 132, in FIG. 3, the second layer 132 and the fourth layer 134 are composed of the high refractive index layer. The high refractive index layer farthest from the outermost layer 131, in FIG. 3, the fourth layer 134 is in contact with the antiglare layer 12 (glass substrate 11). When the low refractive index layer and the high refractive index layer are each composed of one layer, the low refractive index layer is the outermost layer 131 and the high refractive index layer is the second layer 132.

[0025] The thickness of the antireflection layer 13 is preferably 5 nm or more and 300 nm or less, and this thickness is the total thickness of all layers of the antireflection layer 13 having the low refractive index layer and the high refractive index layer. By setting the thickness of the antireflection layer 13 to 5 nm or more and 300 nm or less, a practical antireflection layer 13 having desired antireflection characteristics can be formed.

[0026] The measurement of the thickness of the antireflection layer 13 includes measurement of the actual film thickness by cross-sectional observation using SEM (Scanning Electron Microscopy) or TEM (Transmission Electron Microscopy), or optical measurement by a polarization analysis method. When the antiglare treatment is performed, it is preferable to measure the actual film thickness using SEM or TEM.

[0027] The outermost layer 131, which is a low refractive index layer, is formed as a silicon oxide layer containing a predetermined metal element (hereinafter simply referred to as metal) in SiO2 (silicon oxide). In the present embodiment, a silicon oxide layer in which at least one metal selected from Zr (zirconium), Al (aluminum), Sn (tin), and Zn (zinc) is added to SiO2 is adopted. In the silicon oxide layer to which at least one metal selected from the above-mentioned metals is added, it has been found that the number of hydroxyl groups (OH groups) on the surface of this silicon oxide layer increases. By making the outermost layer 131 a silicon oxide layer to which the above metal is added, the outermost layer 131 can covalently bond to the antifouling layer 14 via OH groups, so that the adhesion between the outermost layer 131 and the antifouling layer 14 can be enhanced. Therefore, for low-intensity friction, the wear resistance of the antifouling layer 14 provided on the outermost layer 131 can be improved. As will be described later, in the glass laminate 10 provided with the antiglare layer 12 having an uneven shape, it is considered important to improve the wear resistance against low-intensity friction, and the wear resistance can be improved by adding metal. On the other hand, for each covalent bond formed from each OH group, the addition of metal causes the bond strength to decrease compared to the OH groups in the case of pure SiO2 only, so it is considered that the durability decreases against high-intensity friction. Therefore, in a flat glass laminate having no uneven shape, when high-intensity (intensity above a certain level) friction occurs on the entire flat surface, adding metal actually reduces the wear resistance of the antifouling layer. In contrast, in the glass laminate 10 provided with the antiglare layer 12 having an uneven shape, except for the protruding regions such as the convex portions of the uneven shape, the wear resistance of the antifouling layer 14 can be improved by reducing the friction intensity.

[0028] From the viewpoint of the abrasion resistance of the antifouling layer 14, Zr is particularly preferable among the above-described metals. Since Zr is an atom with a small ionization energy, when Zr is added to SiO2, in the silicon oxide layer, oxygen that is likely to become an OH group without forming a covalent bond increases. As a result, many OH groups are generated on the surface of the silicon oxide layer to which Zr is added, and the abrasion resistance of the antifouling layer 14 can be particularly improved. Here, the outermost layer 131 of the antireflection layer 13 in contact with the antifouling layer 14 will be described as being formed of a silicon oxide layer (SiZrO) to which Zr is added to SiO2.

[0029] In the silicon oxide layer (SiZrO) to which Zr is added, the composition ratio Zr / (Zr + Si) of Zr to the total of Zr and Si (silicon) is preferably 0.05 or more and less than 0.25, and more preferably 0.09 or more and less than 0.20. By setting the above-described composition ratio Zr / (Zr + Si) to 0.05 or more, the abrasion resistance of the contact angle of the glass laminate 10 provided with the antifouling layer 14 in contact with the outermost layer 131 can be sufficiently increased, and a desired antifouling performance can be obtained. Further, by setting the above-described composition ratio Zr / (Zr + Si) to less than 0.25, a decrease in the reflectance of the antireflection layer 13 can be suppressed, and a desired antireflection characteristic can be obtained. By setting the above-described composition ratio Zr / (Zr + Si) to 0.05 or more and less than 0.25, both the antireflection characteristic of the antireflection layer 13 and the antifouling performance of the antifouling layer 14 can be achieved. Further, when the above-described composition ratio Zr / (Zr + Si) is less than 0.25, a decrease in the film strength of the outermost layer 131 (silicon oxide layer) can be suppressed, and furthermore, the color range (range of chromaticity (chromaticity coordinates) a*, b*) of the outermost layer 131 can be made within a predetermined range (for example, the product specification range). Therefore, from these viewpoints as well, it is preferable to set the above-described composition ratio Zr / (Zr + Si) to less than 0.25.

[0030] The outermost layer 131 formed by the silicon oxide layer (SiZrO) added with Zr is preferably 5 nm or more and 300 nm or less, and more preferably 60 nm or more and 120 nm or less. By setting the outermost layer 131 to 5 nm or more, the surface of the antireflection layer 13 can be completely coated with the silicon oxide layer (SiZrO), and the wear resistance of the antifouling layer 14 formed on the outermost layer 131 can be exhibited. Further, by setting the outermost layer 131 to 300 nm or less, the antireflection characteristics of light in the visible region (for example, about wavelength 400 to 750 nm) can be exhibited.

[0031] The silicon oxide layer (SiZrO) added with Zr has a higher refractive index than the silicon oxide layer (SiO2) without added metal. Therefore, in this embodiment, it is preferable that the odd-numbered layers after 3, the third layer 133 in FIG. 3, are formed as a silicon oxide layer (SiO2) containing no metal. That is, when the silicon oxide layer (SiZrO) added with Zr is used as the low refractive index layer, although the adhesion with the antifouling layer 14 is improved, the refractive index of the low refractive index layer becomes high, and the reflection characteristics of the antireflection layer 13 tend to deteriorate. Therefore, by using only the silicon oxide layer (SiO2) with a lower refractive index for the odd-numbered layers after 3, a reduction in the reflectance of the antireflection layer 13 can be realized. On the other hand, for the purpose of simplifying the manufacturing process of the antireflection layer 13, the odd-numbered layers after 3, the third layer 133 in FIG. 3, may be formed as a silicon oxide layer (SiZrO) added with Zr, similar to the outermost layer 131.

[0032] The method of adding Zr, Al, Sn, and Zn to the silicon oxide layer is not particularly limited. For example, in the case of the sputtering method described below, it can be added by preparing a sputtering target as a mixture of Si and various metal elements or their oxides. At this time, by adjusting the mixing ratio of the target material elements, the ratio of the metal elements to Si in the silicon oxide layer after film formation can be adjusted. On the other hand, when confirming the addition of Zr, Al, Sn, and Zn in the silicon oxide layer after film formation, measurement methods such as X-ray photoelectron spectroscopy (XPS) and secondary ion mass spectrometry (SIMS) are preferable. These measurement methods can also specify the elemental ratio in the film.

[0033] The second layer 132 is a high refractive index layer. The material thereof is not particularly limited. For example, it is preferable that one or more main components are selected from silicon nitride, titanium oxide, niobium oxide, tantalum oxide, and zirconium oxide. By using these materials, even when the low refractive index layer and the high refractive index layer are each a single-layer film structure, reflection can be effectively prevented. Further, among these materials, from the viewpoints of productivity and refractive index, silicon nitride, niobium oxide, and tantalum oxide are more preferable, and niobium oxide is particularly preferable.

[0034] Also, for even-numbered layers after 4, in FIG. 3, the fourth layer 134 may be formed of niobium oxide as the main component, similar to the second layer 132, or may be formed of a material different from the second layer 132.

[0035] The antireflection layer 13 can be formed, for example, by using a film-forming method such as a vacuum evaporation method, an ion beam assisted evaporation method, an ion plating method, a sputtering method, or a plasma CVD method. Among these film-forming methods, it is preferable to use the sputtering method because a dense and highly durable film (layer) can be formed. In particular, it is preferable to form a film by a sputtering method such as a pulse sputtering method, an AC sputtering method, or a digital sputtering method.

[0036] The antireflection layer 13 is formed so as to have a structure in which the high refractive index layer and the low refractive index layer as described above are laminated. The raw material of the antireflection layer 13 is selected so as to contain the materials described above for each layer. The lamination method is not particularly limited. For example, a glass substrate 11 having an antiglare layer 12 formed thereon is installed on the outer surface of a cylindrical drum, and the raw materials of each layer are installed on the inner surface of a cylindrical side wall installed so as to surround the drum. A method of laminating each layer on the antiglare layer 12 of the glass substrate 11 by forming a film while rotating the drum (hereinafter referred to as a rotation method) can be mentioned.

[0037] Also, when forming the high refractive index layer and the low refractive index layer by the pulse sputtering method, the adjustment of the layer thickness of each layer is possible, for example, by adjusting the discharge power, the film-forming time, etc.

[0038] (Antifouling layer) The antifouling layer 14, also called an AFP (Anti-Finger-Print) layer, has a function of suppressing the adhesion of various stains such as fingerprint marks, sweat, and dust, making the stains less conspicuous, and keeping the display surface clean. The antifouling layer 14 is formed on the outermost surface of the glass laminate 10 from the viewpoint of its characteristics.

[0039] The antifouling layer 14 is preferably made of a fluorine compound capable of imparting antifouling property, water repellency, and oil repellency. As the fluorine compound, it is preferably composed of a fluorine-containing organic compound (a compound containing a fluorine-containing organic group). The fluorine-containing organic compound is, for example, a fluorine-containing organosilicon compound. Examples of such a fluorine-containing organosilicon compound include a fluorine-containing organosilicon compound having one or more groups selected from the group consisting of a polyfluoropolyether group, a polyfluoroalkylene group, and a polyfluoroalkyl group. The polyfluoropolyether group is a divalent group having a structure in which a polyfluoroalkylene group and an etheric oxygen atom are alternately bonded.

[0040] Specific examples of the antifouling layer 14 include, for example, those described in the following documents. The fluorinated modified hydrogen-containing polymer described in Japanese Patent No. 4138936. The fluorine-containing organosilane compound described in International Publication No. 2012 / 064649. The fluoroxyalkylene group-containing polymer described in JP-A-2012-72272. The fluorine-containing ether compound described in International Publication No. 2013 / 042732. The fluorine-containing ether compound described in International Publication No. 2013 / 121984. The fluorine-containing ether compound described in International Publication No. 2013 / 121985. The fluorine-containing ether compound described in International Publication No. 2013 / 121986. The compound described in International Publication No. 2014 / 126064. The fluorine-containing ether compound described in International Publication No. 2014 / 163004. The fluorine-containing ether compound described in JP-A-2014-080473. The perfluoro(poly)ether-containing silane compound described in JP-A-2014-218639. The fluorine-containing ether compound described in WO 2015 / 087902. The fluoropolyether group-containing polymer-modified silane described in JP-A-2015-199906. The fluoropolyether group-containing polymer-modified silane described in JP-A-2016-204656. The fluoropolyether group-containing polymer-modified silane described in JP-A-2016-210854. The fluoropolyether group-containing polymer-modified silane described in JP-A-2016-222859. The fluorine-containing ether compound described in WO 2017 / 038830. The fluorine-containing ether compound described in WO 2017 / 038832. The fluorine-containing ether compound described in WO 2017 / 187775. The fluorine-containing ether compound described in WO 2018 / 143433.

[0041] In addition, as the fluorine-containing organosilicon compound having one or more groups selected from the group consisting of a polyfluoropolyether group, a polyfluoroalkylene group, and a polyfluoroalkyl group, KP-801 (manufactured by Shin-Etsu Chemical Co., Ltd.), KY-100 series (KY-178, KY-185, X-71-195, KY-1900, etc., manufactured by Shin-Etsu Chemical Co., Ltd.), Optool DSX, Optool UD, and Optool AES series (manufactured by Daikin Industries, Ltd.), SURECO AF series (SURECO3320N, etc., manufactured by AGC Inc.) and the like can be preferably used.

[0042] The thickness of the antifouling layer 14 is not particularly limited. However, when the antifouling layer 14 is made of a fluorine-containing organosilicon compound, it is 2 nm to 20 nm, preferably 2 nm to 10 nm, and more preferably 2 nm to 4 nm. If the thickness is 2 nm or more, the first main surface 11A of the glass substrate 11 is uniformly covered by the antifouling layer 14, and it becomes practical from the viewpoint of abrasion resistance. Also, if the thickness is 20 nm or less, the optical properties such as the haze value of the glass laminate 10 in the state where the antifouling layer 14 is formed are good.

[0043] In the present embodiment, since the antireflection layer 13 and the antifouling layer 14 are each formed to be thin, the uneven structure on the surface of the antiglare layer 12 is directly traced and formed on the surface of the antifouling layer 14. For this reason, the surface characteristics of the antifouling layer 14 in the initial state are equivalent to the surface roughness RMS and the average length RSm of the elements of the roughness curve of the antiglare layer 12. That is, the surface roughness RMS of the antifouling layer 14 is 0.05 μm to 0.25 μm, and the average length RSm of the elements of the roughness curve is 10 μm to 40 μm. This initial state means a state where the glass laminate 10 is unused and the antifouling layer 14 is not worn. Also, it is more preferable that the surface roughness RMS of the antifouling layer 14 is 0.08 μm to 0.20 μm, and it is more preferable that the average length RSm of the elements of the roughness curve is 15 μm to 35 μm.

[0044] For the antifouling layer 14, any film-forming method such as dry methods like vacuum evaporation method, ion beam assisted evaporation method, ion plating method, sputtering method, plasma CVD method, and wet methods like spin coating method, dip coating method, casting method, slit coating method, spraying method can be used. Preferably, the vacuum evaporation method is used.

[0045] (Printing layer) The printing layer 15 is not an essential requirement. For example, as shown in FIG. 2, it is provided on the second main surface 11B of the glass substrate 11. By being provided on at least a part of the peripheral portion of the second main surface 11B, the printing layer 15 shields the glass substrate 11 from light. The peripheral portion of the second main surface 11B means a strip-shaped region having a predetermined width extending from the edge portion away from the center of the second main surface 11B toward the central portion of the second main surface 11B. The printing layer 15 may be formed over the entire periphery of this peripheral portion or at least a part of the peripheral portion. Usually, the printing layer 15 is in contact with the outer peripheral end of the glass substrate 11 and is formed in a strip shape having a predetermined width. The printing layer 15 conceals, for example, wiring members disposed at the peripheral portion of the display panel 3 so that the area outside the display region cannot be visually recognized from the observer side. Further, the printing layer 15 is formed to improve the design property of the display device, enhancing the visibility and aesthetics of the display.

[0046] The printing layer 15 is formed, for example, by a method of printing black ink. The printing method is not particularly limited, but preferred methods include the inkjet method, the transfer decoration method, the screen printing method, and the like. The black ink is not particularly limited and can be used. As the black ink, inorganic inks containing ceramic fired bodies and the like, and organic inks containing coloring materials such as dyes or pigments and organic resins can be used. Note that the printing layer 15 is usually formed in black, but is not limited to black as long as it has high light-shielding properties.

[0047] (Water contact angle of the glass laminate) The contact angle is an index for evaluating the difficulty of soiling of a solid surface. The water contact angle is the value of the contact angle with respect to water. For example, a water droplet of about 1 μL is dropped onto the outermost surface (the surface of the antifouling layer 14) on the first main surface 11A side of the glass laminate 10, and can be measured using a contact angle meter (for example, manufactured by Kyowa Interface Science Co., Ltd., device name: DM-501). The initial water contact angle of the glass laminate 10 is preferably 90° or more, more preferably 100° or more, and even more preferably 115° or more. Further, the water contact angle after rubbing 50,000 times is preferably 84° or more, and more preferably 100° or more. When the water contact angle is within the above-described range, the glass laminate 10 (antifouling layer 14) can exhibit excellent antifouling properties.

[0048] (Effect) As described above, the glass laminate 10 according to the present embodiment includes a glass substrate 11 having a first main surface 11A and a second main surface 11B, an antiglare layer 12 formed on the side of the first main surface 11A, an antireflection layer 13 formed on the surface of the antiglare layer 12, and an antifouling layer 14 formed on the surface of the antireflection layer 13. The antireflection layer 13 has an outermost layer 131 formed as a silicon oxide layer on the surface in contact with the antifouling layer 14, and this outermost layer 131 contains at least one metal selected from Zr, Al, Sn, and Zn. According to this configuration, since the wear resistance of the antifouling layer 14 in the glass laminate 10 provided with the antiglare layer 12, the antireflection layer 13, and the antifouling layer 14 is improved, it is possible to improve the wear resistance of the antifouling layer 14 while having antiglare properties.

[0049] Further, in the glass laminate 10 according to the present embodiment, since the outermost layer 131 as a silicon oxide layer contains Zr, the wear resistance of the antifouling layer 14 can be more effectively exhibited.

[0050] Further, in the glass laminate 10 according to the present embodiment, since the composition ratio Zr / (Zr + Si) of Zr in the outermost layer 131 as a silicon oxide layer to the total of Zr and Si is 0.05 or more, the desired antifouling performance of the antifouling layer 14 can be obtained.

[0051] Further, in the glass laminate 10 according to the present embodiment, since the composition ratio Zr / (Zr + Si) of Zr in the outermost layer 131 as a silicon oxide layer to the total of Zr and Si is less than 0.25, the desired antireflection characteristics of the antireflection layer 13 can be obtained.

[0052] Further, in the glass laminate 10 according to the present embodiment, since the antiglare layer 12 is composed of an uneven structure directly formed on the first main surface 11A by, for example, performing an antiglare treatment and an etching treatment, the antiglare layer 12 can be easily formed on the first main surface 11A of the glass substrate 11.

[0053] In addition, in the glass laminate 10 according to the present embodiment, since the uneven structure satisfies the surface roughness RMS of the first main surface 11A being 0.03 μm to 0.25 μm and the average length RSm of the elements of the roughness curve being 10 μm to 40 μm, the wear resistance of the antifouling layer 14 provided on this uneven structure can be effectively enhanced.

[0054] In addition, in the glass laminate 10 according to the present embodiment, since the antireflection layer 13 is formed by alternately laminating a high refractive index layer having a refractive index of 2.0 or more and a low refractive index layer having a refractive index of 1.3 to 1.9, an antireflection layer 13 having desired reflection characteristics can be realized.

[0055] In addition, in the glass laminate 10 according to the present embodiment, the antireflection layer 13 includes the outermost layer 131 and the third layer 133, which are one or more and six or less low refractive index layers, and the second layer 132 and the fourth layer 134, which are high refractive index layers having the same number of layers as the low refractive index layers. Since the second layer 132 and the fourth layer 134, which are high refractive index layers, contain any one of silicon nitride, titanium oxide, niobium oxide, tantalum oxide, and zirconium oxide as a main component, for example, even in a film configuration where the low refractive index layer and the high refractive index layer are each one layer, reflection can be effectively prevented.

[0056] In addition, in the glass laminate 10 according to the present embodiment, since the thickness of the antireflection layer 13 satisfies 5 nm to 300 nm, the surface shape of the antiglare layer 12 is directly traced to become the surface shape of the antireflection layer 13. Therefore, the wear resistance of the antifouling layer 14 provided on the surface of the antireflection layer 13 can be effectively enhanced.

[0057] In addition, in the glass laminate 10 according to the present embodiment, since the antifouling layer 14 contains, for example, a fluorine-containing organic group, antifouling properties, water repellency, and oil repellency can be effectively exhibited.

[0058] (Modification example) Next, a modified example of the present embodiment will be described. In the present embodiment, the outermost layer of the antireflection layer 13, which is a low refractive index layer, is formed as a silicon oxide layer (SiZrO) doped with Zr. However, as described above, when Zr is added, the refractive index of the outermost layer tends to increase. Therefore, in order to reduce the refractive index of the outermost layer 131 of the antireflection layer 13, the outermost layer may have a laminated structure of SiZrO doped with Zr and SiO2. For example, by forming the outermost layer based on SiO2 and then forming SiZrO doped with Zr only on the uppermost skin, such as SiZrO(5nm) / SiO2(90nm), it is possible to reduce the refractive index of the outermost layer 131 of the antireflection layer 13.

[0059] Further, the glass laminate 10 of the present embodiment has a laminated structure of a glass substrate 11, an antiglare layer 12, an antireflection layer 13, and an antifouling layer 14. However, in another embodiment, the antiglare layer 12 can be replaced with an uneven layer, and the antireflection layer 13 can be replaced with at least one silicon oxide layer. The uneven layer is not limited to having antiglare properties, and the silicon oxide layer is not limited to having antireflection properties. In the glass laminate 10 having such a glass substrate 11, an uneven layer, and a silicon oxide layer, the preferred embodiments described in the above (antiglare layer) and the preferred embodiments described in the above (antireflection layer) are applicable.

[0060] The present disclosure describes the following inventions. However, it is not limited thereto.

[0061] (1) A glass laminate having a glass substrate having a first main surface and a second main surface, an uneven layer formed on the side of the first main surface, a silicon oxide layer formed on the surface of the uneven layer, and an antifouling layer formed on the surface of the silicon oxide layer, wherein the silicon oxide layer contains at least one metal selected from Zr, Al, Sn, and Zn.

[0062] (2) The glass laminate according to (1), wherein the silicon oxide layer contains Zr.

[0063] (3) The glass laminate according to (2), wherein the composition ratio Zr / (Zr + Si) of Zr in the silicon oxide layer to the total of Zr and Si is 0.05 or more.

[0064] (4) The glass laminate according to (2) or (3), wherein the composition ratio Zr / (Zr + Si) of Zr in the silicon oxide layer to the total of Zr and Si is less than 0.25.

[0065] (5) The glass laminate according to any one of (1) to (4), wherein the concavo-convex layer has antiglare properties.

[0066] (6) The glass laminate according to any one of (1) to (5), wherein the concavo-convex layer is composed of a concavo-convex structure directly formed on the first main surface.

[0067] (7) The glass laminate according to any one of (1) to (6), wherein the RMS of the surface of the antifouling layer satisfies 0.03 μm to 0.25 μm, and the average length RSm of the elements of the roughness curve satisfies 10 μm to 40 μm.

[0068] (8) The glass laminate according to any one of (1) to (7), wherein an antireflection layer is provided on the surface of the concavo-convex layer, and the antireflection layer is formed by alternately laminating a high refractive index layer having a refractive index of 2.0 or more and a low refractive index layer having a refractive index of 1.3 to 1.9, and the outermost layer of the antireflection layer is a silicon oxide layer.

[0069] (9) The glass laminate according to (8), wherein the antireflection layer includes one or more to six low refractive index layers and the same number of high refractive index layers as the low refractive index layers, and the high refractive index layer is mainly composed of any one of silicon nitride, titanium oxide, niobium oxide, tantalum oxide, and zirconium oxide.

[0070] (10) The glass laminate according to any one of (1) to (9), wherein an antireflection layer containing a silicon oxide layer is provided on the surface of the concavo-convex layer, and the thickness of the antireflection layer satisfies 5 nm to 300 nm.

[0071] (11) The antifouling layer is a glass laminate according to any one of (1) to (10) containing fluorine.

[0072] (12) The glass laminate according to any one of (1) to (11), wherein the glass substrate has a curved surface shape.

[0073] (13) A cover glass for a display, comprising the glass laminate according to any one of (1) to (12) described above.

[0074] (14) A display device, comprising the cover glass according to (13) described above.

[0075] (Examples) Next, examples will be described. Note that the embodiments may be changed as long as the effects of the invention are achieved. In Examples 1 to 9, a plurality of types of glass laminates were evaluated for the durability of the antifouling layer in the initial state and after 50,000 rubs, respectively. In Examples 10 to 15, a plurality of types of glass laminates were evaluated for the reflection characteristics of the antireflection layer, respectively. Examples 1 to 2, 7 to 8, and 10 to 13 are examples of the present invention, and Examples 3 to 6, 9, and 14 to 15 are comparative examples. Examples 1 to 9 are shown in Table 1, and Examples 10 to 15 are shown in Table 2.

[0076] (Durability of the antifouling layer: Examples 1 to 9) The glass laminate of Example 1 used a plate-shaped glass with a thickness of 1.3 mm and a pair of opposing main surfaces being square as the glass substrate, and an antiglare layer, an antireflection layer, and an antifouling layer were formed on the side of the first main surface. The antiglare layer was subjected to an antiglare treatment consisting of a frosting treatment and an etching treatment on the first main surface, and an uneven structure was directly formed on the first main surface. This uneven structure had a surface roughness RMS of 0.07 μm on the first main surface and an average length RSm of the elements of the roughness curve of 23 μm.

[0077] The antireflection layer consists of a single layer of a low refractive index layer. On the antiglare layer, a low refractive index layer (corresponding to the outermost layer 131 in Fig. 3) mainly composed of SiZrO (silicon zirconium oxide) with Zr (zirconium) added to SiO2 was formed. The thickness of the entire antireflection layer was adjusted to 100 nm. Also, in the outermost layer 131 mainly composed of SiZrO, the composition ratio Zr / (Zr + Si) of Zr to the total of Zr and Si was set to 0.15.

[0078] The antifouling layer was formed on the antireflection layer. As the material of the antifouling layer, a fluorine-containing organosilicon compound (X-71-195 (manufactured by Shin-Etsu Chemical Co., Ltd.); referred to as Material A) was used. The thickness of the antifouling layer was adjusted to 8.1 nm.

[0079] In the glass laminate of Example 2, the outermost layer 131 of the antireflection layer was a low refractive index layer mainly composed of SiAlO (silicon aluminum oxide) with Al (aluminum) added to SiO2. In this case, in the outermost layer 131 mainly composed of SiAlO, the composition ratio Al / (Si + Al) of Al to the total of Al and Si was set to 0.12. Otherwise, the glass laminate was formed under the same conditions as in Example 1.

[0080] In the glass laminate of Example 3, the outermost layer 131 of the antireflection layer was a low refractive index layer mainly composed of SiO2 (silicon oxide). Otherwise, the glass laminate was formed under the same conditions as in Example 1.

[0081] The glass laminate of Example 4 had a flat configuration without an antiglare layer on the side of the first main surface of the glass substrate. That is, the antiglare treatment for the first main surface was not performed. Otherwise, the glass laminate was formed under the same conditions as in Example 3.

[0082] The glass laminate of Example 5 also had a flat configuration without an antiglare layer on the side of the first main surface of the glass substrate, similar to Example 4. Otherwise, the glass laminate was formed under the same conditions as in Example 2.

[0083] The glass laminate of Example 6 also had a flat configuration without an antiglare layer on the side of the first main surface of the glass substrate, similar to Example 4. Otherwise, the glass laminate was formed under the same conditions as in Example 1.

[0084] Also, in the glass laminate of Example 7, the material of the antifouling layer is different from that of Example 1. As the material of the antifouling layer, a fluorine-containing organosilicon compound (SURECO3320N (manufactured by AGC Inc.); referred to as Material B) was used. Otherwise, the glass laminate was formed under the same conditions as in Example 1.

[0085] In the glass laminate of Example 8, Material B was used as the material of the antifouling layer in the same manner as in Example 7. Otherwise, the glass laminate was formed under the same conditions as in Example 2.

[0086] In the glass laminate of Example 9, Material B was used as the material of the antifouling layer in the same manner as in Example 7. Otherwise, the glass laminate was formed under the same conditions as in Example 3.

[0087] (Measurement of initial water contact angle) For the glass laminates obtained in Examples 1 to 9, as an evaluation of the durability of the antifouling layer, the water contact angle was measured as follows. On the surface of the antifouling layer of the glass laminate at the initial unused stage, about 2 μL of pure water droplets were dropped, and the water contact angle was measured using a contact angle meter (manufactured by Kyowa Interface Science Co., Ltd., device name; DM-501). The measurement points of the water contact angle on the surface of the antifouling layer were set to 5, and the average value was calculated and used for the evaluation. The results are shown in Table 1.

[0088] (Measurement of water contact angle after 50,000 rubs) First, a friction element was prepared by attaching a plain-weave cotton cloth No. 3 to the surface of a flat metal indenter with a bottom surface of 10 mm × 10 mm to rub the sample. Next, using this friction element, a wear test was performed with a three-unit flat wear tester (manufactured by Daiei Kagaku Seiki Co., Ltd.). Specifically, the bottom surface of the indenter was attached to the wear tester so as to contact the surface of the antifouling layer of the sample, a weight was placed so that the load on the friction element was 600 g, and the sample was reciprocally slid at an average speed of 3600 mm / min and a one-way distance of 40 mm. The test was performed with 2 rubs per reciprocation, and after 50,000 rubs were completed, the water contact angle of the surface of the antifouling layer was measured in the same manner as above. The results are shown in Table 1.

[0089]

Table 1

[0090] (Evaluation Results on Durability of Antifouling Layer) As shown in Table 1, in the glass laminates of Examples 1 to 6 using Material A for the antifouling layer, in the glass laminates of Examples 1 and 2 which are the examples, since the outermost layer of the antireflection layer was a low refractive index layer mainly composed of silicon oxide (SiZrO, SiAlO) with metal (Zr, Al) added to SiO2, the water contact angles at 50,000 rubs were each 84° or more, and good abrasion resistance of the antifouling layer could be obtained. In particular, in the glass laminate of Example 1, by adding Zr as the metal, the water contact angle at 50,000 rubs was 99° or more, and particularly good abrasion resistance could be obtained. On the other hand, in Example 3 which is a comparative example, since the outermost layer of the antireflection layer was a low refractive index layer mainly composed of SiO2 (silicon oxide), the water contact angles at 50,000 rubs were each less than 84°, and good abrasion resistance of the antifouling layer could not be obtained. Here, it can be considered that the abrasion resistance of the antifouling layer was improved by adding metal (Zr, Al) to SiO2 forming the outermost layer of the antireflection layer.

[0091] However, as shown in Comparative Examples 4 to 6, in the glass laminates without an antiglare layer, the water contact angle at 50,000 rubs of the glass laminate of Example 6 with Zr added to SiO2 was significantly lower than that of the glass laminate of Example 4 using SiO2 as it was.

[0092] From these results, it is presumed that by making the outermost layer of the antireflection layer a low refractive index layer mainly composed of silicon oxide (SiZrO, SiAlO) with metal (Zr, Al) added to SiO2 and providing an antiglare layer under the antireflection layer, the good abrasion resistance of the above-described antifouling layer could be obtained.

[0093] That is, when an antireflection layer and an antifouling layer are provided on the antiglare layer, as shown in FIG. 4, the uneven structure on the surface of the antireflection layer 13 (antiglare layer) is directly traced and formed on the surface of the antifouling layer 14. For this reason, as shown in FIG. 5, when the surface of the antifouling layer 14 is rubbed by a pressure head (not shown), the convex portions 14A (FIG. 4) of the antireflection layer 13 are preferentially worn away, and the antifouling layer 14 in the convex portions 14A also wears. As a result, when rubbed over a long period, it is considered that the antifouling layer 14 remaining in the concave portions 14B contributes to the antifouling performance.

[0094] In the case of a glass laminate in which a metal such as Zr or Al is added to SiO2 to form the outermost layer of the antireflection layer, the wear resistance of the antifouling layer rather decreased in a glass laminate without an antiglare layer, but in a glass laminate with an antiglare layer, good wear resistance could be obtained. That is, when a metal such as Zr or Al is added to SiO2 to form the outermost layer of the antireflection layer, the wear resistance against rubbing due to the high strength of the antifouling layer does not improve, while the wear resistance against low-intensity rubbing improves. For this reason, in FIG. 5, in the concave portions 14B where the pressure head hits only with low intensity as compared with the convex portions, the wear of the antifouling layer 14 is suppressed, and after being rubbed over a long period, it is considered that more of the antifouling layer in the concave portions remains than in the case where the outermost layer is only SiO2. As a result, it is presumed that good wear resistance of the antifouling layer could be obtained.

[0095] Also, in the glass laminates of Examples 7 to 9, even when the material of the antifouling layer was changed to Material B, in the glass laminates of Examples 7 to 8 which are examples, since the outermost layer of the antireflection layer was a low refractive index layer mainly composed of silicon oxide (SiZrO, SiAlO) with metal (Zr, Al) added to SiO2, the water contact angle at 50,000 rubs was 84° or more respectively, and good abrasion resistance of the antifouling layer could be obtained. In particular, in the glass laminate of Example 7, by adding Zr as the metal, the water contact angle at 50,000 rubs was 102° or more, and particularly good abrasion resistance could be obtained. On the other hand, in Example 9 which is a comparative example, since the outermost layer of the antireflection layer was a low refractive index layer mainly composed of SiO2 (silicon oxide), the water contact angle at 50,000 rubs was less than 77° respectively, and good abrasion resistance of the antifouling layer could not be obtained. Thus, even when the material of the antifouling layer was changed to Material B, by making the outermost layer of the antireflection layer a low refractive index layer mainly composed of silicon oxide (SiZrO, SiAlO) with metal (Zr, Al) added to SiO2 and providing an antiglare layer under the antireflection layer, good abrasion resistance of the above-described antifouling layer could be obtained.

[0096] (Reflection characteristics of the antireflection layer: Examples 10 to 15) In the glass laminate of Example 10, the antireflection layer consisted of a total of six layers, three high refractive index layers and three low refractive index layers. On the antiglare layer, a high refractive index layer (the sixth, fourth, and second layers) mainly composed of NbO (niobium oxide) and a low refractive index layer (the fifth and third layers) mainly composed of SiO2 (silicon oxide) were alternately laminated. Also, on the second layer (the second layer 132 in FIG. 3) mainly composed of NbO (niobium oxide), a low refractive index layer (the outermost layer 131 in FIG. 3) mainly composed of SiZrO (silicon oxide) with Zr (zirconium) added to SiO2 was formed. The thicknesses of each layer from the sixth layer to the outermost layer were the values shown in Table 2. Also, in the outermost layer 131 mainly composed of SiZrO, the composition ratio Zr / (Zr + Si) of Zr to the total of Zr and Si was 0.10. Otherwise, the glass laminate was formed under the same conditions as in Example 1.

[0097]

Table 2

[0098] As shown in Table 2, for the glass laminate of Example 11, while the thickness of each layer of the antireflection layer was made different from that of Example 10, in the outermost layer 131 mainly composed of SiZrO, the composition ratio Zr / (Zr + Si) of Zr to the total of Zr and Si was set to 0.19. Otherwise, the glass laminate was formed under the same conditions as in Example 1.

[0099] As shown in Table 2, for the glass laminate of Example 12, while the thickness of each layer of the antireflection layer was made different from that of Example 10, in the outermost layer 131 mainly composed of SiZrO, the composition ratio Zr / (Zr + Si) of Zr to the total of Zr and Si was set to 0.20. Otherwise, the glass laminate was formed under the same conditions as in Example 1.

[0100] In the glass laminate of Example 13, the antireflection layer is composed of a total of five layers, two high refractive index layers and three low refractive index layers. On the antiglare layer, a low refractive index layer (the fifth and third layers) mainly composed of SiO2 (silicon oxide) and a high refractive index layer (the fourth and second layers) mainly composed of NbO (niobium oxide) were alternately laminated. Also, on the second layer (the second layer 132 in FIG. 3) mainly composed of NbO (niobium oxide), a low refractive index layer (the outermost layer 131 in FIG. 3) mainly composed of SiZrO (silicon oxide) with Zr (zirconium) added to SiO2 was formed. The thickness of each layer from the fifth layer to the outermost layer was set to the values shown in Table 2. Also, in the outermost layer 131 mainly composed of SiZrO, the composition ratio Zr / (Zr + Si) of Zr to the total of Zr and Si was set to 0.24. Otherwise, the glass laminate was formed under the same conditions as in Example 1.

[0101] As shown in Table 2, for the glass laminate of Example 14, while the thickness of each layer of the antireflection layer was made different from that of Example 13, in the outermost layer 131 mainly composed of SiZrO, the composition ratio Zr / (Zr + Si) of Zr to the total of Zr and Si was set to 0.25. Otherwise, the glass laminate was formed under the same conditions as in Example 1.

[0102] As shown in Table 2, in the glass laminate of Example 15, the thickness of each layer of the antireflection layer was made different from that of Example 13, and in the outermost layer 131 mainly composed of SiZrO, the composition ratio Zr / (Zr + Si) of Zr to the total of Zr and Si was 0.30. Otherwise, the glass laminate was formed under the same conditions as in Example 1.

[0103] (Measurement of reflectance of antireflection layer and chromaticity of outermost layer) Regarding the glass laminates obtained in Examples 10 to 15, as an evaluation of the antireflection characteristics of the antireflection layer, the visible light reflectance Rv of the antireflection layer and the chromaticity (chromaticity coordinates a*, b* in the CIE1976 color space) of the outermost layer were calculated as follows. Let the absolute values of these be |a| and |b|. At this time, the light source was the CIE standard light source D65, and the incident light from the surface on which the antireflection layer was formed was set. Also, the reflected light from the substrate surface on which the antireflection layer was not formed was excluded. The results are shown in Table 2.

[0104] (Evaluation results regarding antireflection characteristics of antireflection layer) As shown in Table 2, in the glass laminates of Examples 10 to 15, in the glass laminates of Examples 10 to 13 which are examples, since the composition ratio Zr / (Zr + Si) of Zr to the total of Zr and Si in the outermost layer of the antireflection layer was less than 0.25, the reflectance Rv was less than 0.3 respectively, and good antireflection characteristics of the antireflection layer could be obtained. In particular, in the glass laminates of Examples 10 to 11, since the above composition ratio Zr / (Zr + Si) was less than 0.20, the reflectance Rv was less than 0.3, and the chromaticity a*, b* of the outermost layer were both less than 10, and particularly good antireflection characteristics could be obtained. On the other hand, in the glass laminates of Examples 14 to 15 which are comparative examples, since the composition ratio Zr / (Zr + Si) of Zr to the total of Zr and Si in the outermost layer of the antireflection layer was 0.25 or more, the reflectance Rv was 0.3 or more respectively, and good antireflection characteristics of the antireflection layer could not be obtained.

[0105] The embodiments of the present invention have been described above. However, the embodiments are not limited by the content of these embodiments. Further, the above-described components include those that can be easily assumed by those skilled in the art, those that are substantially the same, and those within the so-called equivalent range. Furthermore, the above-described components can be combined as appropriate. Still further, various omissions, substitutions, or changes of the components can be made without departing from the gist of the above-described embodiments.

Explanation of Reference Numerals

[0106] 1 Steering Shaft 2 Vehicle-mounted Display Device 3 Display Panel 10 Glass Laminate 11 Glass Substrate (Glass Substrate Board) 11A First Main Surface 11B Second Main Surface 12 Anti-glare Layer 13 Anti-reflection Layer 14 Anti-fouling Layer 14A Protrusion 14B Recess 15 Printing Layer

Claims

1. A glass substrate having a first main surface and a second main surface, An uneven layer formed on the side of the first main surface, A silicon oxide layer formed on the surface of the uneven layer, And an antifouling layer formed on the surface of the silicon oxide layer, The silicon oxide layer contains at least one metal selected from Zr, Al, Sn, and Zn, and is a glass laminate.

2. The silicon oxide layer contains Zr, and is the glass laminate according to Claim 1.

3. In the silicon oxide layer, the composition ratio Zr / (Zr + Si) of Zr to the total of Zr and Si is 0.05 or more, and is the glass laminate according to Claim 2.

4. In the silicon oxide layer, the composition ratio Zr / (Zr + Si) of Zr to the total of Zr and Si is less than 0.25, and is the glass laminate according to Claim 2 or 3.

5. The uneven layer has antiglare properties, and is the glass laminate according to Claim 1 or 2.

6. The uneven layer is composed of an uneven structure directly formed on the first main surface, and is the glass laminate according to Claim 1 or 2.

7. The RMS of the surface of the antifouling layer satisfies 0.03 μm to 0.25 μm, and the average length RS m of the elements of the roughness curve satisfies 10 μm to 40 μm, and is the glass laminate according to Claim 1 or 2.

8. The uneven layer has an antireflection layer on its surface. The antireflection layer has a high refractive index layer with a refractive index of 2.0 or more and a low refractive index layer with a refractive index of 1.3 to 1.9 laminated alternately, and the outermost layer of the antireflection layer is the silicon oxide layer, and is the glass laminate according to Claim 1 or 2.

9. The antireflection layer includes one or more and six or fewer of the low refractive index layers and the high refractive index layers having the same number of layers as the low refractive index layers. The high refractive index layer contains any one of silicon nitride, titanium oxide, niobium oxide, tantalum oxide, and zirconium oxide as a main component. The glass laminate according to claim 8.

10. The glass laminate according to claim 1 or 2, having an antireflection layer containing the silicon oxide layer on the surface of the concavo-convex layer, and the thickness of the antireflection layer satisfying 5 nm to 300 nm.

11. The glass laminate according to claim 1 or 2, wherein the antifouling layer contains fluorine.

12. The glass laminate according to claim 1 or 2, wherein the glass substrate has a curved surface shape.

13. A cover glass for a display, comprising the glass laminate according to claim 1 or 2.

14. A display device, comprising the cover glass according to claim 13.

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