Cover component

Abstract

The present invention provides a cover member having a functional film that performs multiple functions with a single membrane, and a method for manufacturing the same. [Solution] The cover member according to the present invention comprises a glass plate having a first surface and a second surface, and a functional film formed on the first surface, wherein the functional film is formed as a single film and has anti-glare function and antibacterial function.

Description

[Technical Field]

[0001] The present invention relates to a cover member provided on a protected component such as a display, and a method for manufacturing the same. [Background technology]

[0002] Patent Document 1 discloses a glass in which an antibacterial substance is provided on the surface of the glass plate by ion exchange of antibacterial ion components. [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Application Publication No. 11-228186 [Overview of the Initiative] [Problems that the invention aims to solve]

[0004] In recent years, there has been a demand for films with additional functions, such as anti-glare properties, in addition to antibacterial properties. However, producing films that perform multiple functions requires laminating multiple films for each function, which complicates manufacturing. The present invention was made to solve this problem and aims to provide a cover member and a method for manufacturing the same, which has a functional film that performs multiple functions with a single film. [Means for solving the problem]

[0005] Item 1. A glass plate having a first surface and a second surface, A functional film formed on the first surface, Equipped with, The functional membrane is a cover member formed from a single membrane and has anti-glare and antibacterial properties.

[0006] Section 2. The functional film is, A matrix containing inorganic oxides that constitutes a three-dimensional network connection, Inorganic oxide nanoparticles and an antibacterial metal ion and The cover member according to claim 1, comprising

[0007] Item 3. The functional film a first region in which the inorganic oxide particles are stacked in the thickness direction of the functional film; a valley-shaped second region surrounding the first region or surrounded by the first region; The cover member according to claim 2, wherein there is

[0008] Item 4. The first region is a stepped region. The cover member according to claim 3.

[0009] Item 5. The second region includes a portion where the inorganic oxide particles are not stacked or the inorganic oxide particles do not exist. The cover member according to claim 3 or 4.

[0010] Item 6. The width of the first region is 3 μm or more, The width of the second region is 1 μm or more. The cover member according to any one of claims 3 to 5.

[0011] Item 7. The width of the first region is 5 μm or more, The width of the second region is 2 μm or more. The cover member according to any one of claims 3 to 5.

[0012] [[ID=​​​​​​​​​​​​Item 10. The cover member according to any one of Items 3 to 9, wherein at least one of the second regions is formed by a closed curve.

[0015] Item 11. The cover member according to Item 10, wherein the second region includes a region formed by a plurality of closed curves of different sizes.

[0016] Item 12. The cover member according to any one of Items 3 to 11, wherein in the first region, the vicinity of the boundary with the second region is raised.

[0017] Item 13. A step of forming a coating liquid by adding inorganic oxide fine particles and antibacterial metal ions to silicon alkoxide; A step of applying the coating liquid to a glass plate; A step of heating the glass plate coated with the coating liquid; A manufacturing method of a cover member, comprising:

Effect of the Invention

[0018] According to the present invention, a functional film having a plurality of functions can be provided with a single film.

Brief Description of the Drawings

[0019] [Figure 1] It is a cross-sectional view showing an embodiment of a cover member according to the present invention. [Figure 2] It is an enlarged cross-sectional view of FIG. 1. [Figure 3] It is an enlarged cross-sectional view of FIG. 1. [Figure 4] It is a cross-sectional view schematically showing a cross-section of a convex portion of a functional film. [Figure 5] It is each cross-sectional view of FIG. 1. [Figure 6] It is a SEM photograph showing the surface property of Example 1. [Figure 7] It is a SEM photograph showing the surface property of Example 4. [Figure 8] It is a SEM photograph showing the surface property of a comparative example. [Modes for carrying out the invention]

[0020] Hereinafter, an embodiment of the cover member according to the present invention will be described with reference to the drawings. The cover member according to this embodiment protects a protected component such as a display, keyboard, or electronic whiteboard, and is configured to allow these components to be visible from the outside. The display refers to displays used in various devices, including general desktop displays, mobile PCs, tablet PCs, and in-vehicle devices such as car navigation systems. In addition, this cover member can also be used as the document glass of a copier or scanner. In this case, the protected component is a part of an electronic device such as a copier or scanner that is covered by the cover member.

[0021] Figure 1 is a cross-sectional view of the cover member. As shown in Figure 1, the cover member 100 according to this embodiment comprises a glass plate 10 having a first surface and a second surface, and functional films 50 and 60 laminated on the first surface of the glass plate 10. The cover member 10 is positioned to cover the protected member 200 described above. At this time, the second surface of the glass plate 10 is positioned to face the protected member 200, and the functional films 50 and 60 are positioned to face outwards. A detailed explanation follows below.

[0022] <1. Glass plate> The glass plate 10 can be formed from, for example, general-purpose soda-lime glass, borosilicate glass, aluminosilicate glass, alkali-free glass, or other types of glass. The glass plate 10 can also be formed by the float process. This method yields a glass plate 10 with a smooth surface. However, the glass plate 10 may have irregularities on its main surface, for example, it may be patterned glass. Patterned glass can be formed by a method called the roll-out method. Patterned glass produced by this method typically has periodic irregularities in one direction along the main surface of the glass plate.

[0023] The float process involves continuously supplying molten glass onto a molten metal such as molten tin, allowing the supplied molten glass to flow on the molten metal and form it into a strip. Glass formed in this way is called a glass ribbon.

[0024] As the glass ribbon moves downstream, it cools and solidifies, then is lifted from the molten metal by rollers. It is then transported by rollers to an annealing furnace, where it cools slowly and is cut. In this way, a float glass sheet is obtained.

[0025] The thickness of the glass plate 10 is not particularly limited, but a thinner plate is preferable for weight reduction. For example, it is preferably 0.3 to 5 mm thick, and more preferably 0.6 to 2.5 mm thick. This is because if the glass plate 10 is too thin, its strength will decrease, and if it is too thick, distortion may occur in the protected member 200 that is visible through the glass member 10.

[0026] The glass plate 10 may be a flat plate, but it may also be a curved plate. In particular, if the surface shape of the protected member 200 to be protected is a non-planar surface such as a curved surface, it is preferable that the glass plate 10 has a main surface with a non-planar shape that conforms to it. In this case, the glass plate 10 may be bent so that the entire surface has a constant curvature, or it may be bent locally. The main surface of the glass plate 10 may be composed of, for example, multiple planes connected to each other by curved surfaces. The radius of curvature of the glass plate 10 can be, for example, 5000 mm or less. The lower limit of this radius of curvature can be, for example, 10 mm or more, but it may be even smaller in the locally bent parts, for example, 1 mm or more.

[0027] Glass plates with the following compositions can also be used. In the following, unless otherwise specified, all percentages indicating the components of glass plate 10 mean mol%. Furthermore, in this specification, "substantially constitutes" means that the total content of the listed components is 99.5% by mass or more, preferably 99.9% by mass or more, and more preferably 99.95% by mass or more. "Substantially absent" means that the content of the component is 0.1% by mass or less, preferably 0.05% by mass or less.

[0028] Based on the composition of float glass, which is widely used as a glass composition suitable for the manufacture of glass plates by the float method (hereinafter sometimes referred to as "SL in the narrow sense" or simply "SL"), the inventors investigated a composition that can improve the chemical strengthening properties of SL in the narrow sense while approximating properties such as T2 and T4 to SL in the narrow sense, within the composition range that those skilled in the art consider to be suitable for the float method (hereinafter sometimes referred to as "SL in the broad sense"), specifically within the following mass% range. SiO265~80% Al2O30~16% MgO 0-20% CaO 0-20% Na2O 10-20% K2O 0-5%

[0029] The following describes each component that makes up the glass composition of the glass plate 10. (SiO2) SiO2 is a major component of the glass plate 10, and if its content is too low, the chemical durability, such as water resistance, and heat resistance of the glass will decrease. On the other hand, if the SiO2 content is too high, the viscosity of the glass plate 10 will increase at high temperatures, making it difficult to melt and mold. Therefore, an appropriate SiO2 content is in the range of 66 to 72 mol%, and 67 to 70 mol% is preferred.

[0030] (Al2O3) Al2O3 is a component that improves the chemical durability of the glass plate 10, such as its water resistance, and further increases the surface compressive stress after chemical strengthening by facilitating the movement of alkali metal ions in the glass, as well as increasing the depth of the stress layer. On the other hand, if the Al2O3 content is too high, it increases the viscosity of the glass melt, increases T2 and T4, and deteriorates the clarity of the glass melt, making it difficult to manufacture high-quality glass plates.

[0031] Therefore, an appropriate Al2O3 content is in the range of 1 to 12 mol%. Preferably, the Al2O3 content is 10 mol% or less, and 2 mol% or more.

[0032] (MgO) MgO is an essential component for improving the solubility of glass. From the viewpoint of fully obtaining this effect, it is preferable that MgO is added to this glass plate 10. Furthermore, if the MgO content falls below 8 mol%, the surface compressive stress after chemical strengthening decreases, and the depth of the stress layer tends to become shallower. On the other hand, if the content is increased beyond the appropriate amount, the strengthening performance obtained by chemical strengthening decreases, and in particular, the depth of the surface compressive stress layer becomes rapidly shallower. Among alkaline earth metal oxides, MgO has the least adverse effect, but in this glass plate 1, the MgO content is 15 mol% or less. Also, if the MgO content is high, T2 and T4 increase, and the clarity of the glass melt deteriorates, making it difficult to manufacture high-quality glass plates.

[0033] Therefore, in this glass plate 10, the MgO content is in the range of 1 to 15 mol%, and preferably 8 mol% or more and 12 mol% or less.

[0034] (CaO) CaO has the effect of reducing viscosity at high temperatures, but if the content is too high beyond a moderate range, the glass plate 10 becomes more prone to devitrification, and the movement of sodium ions in the glass plate 10 is inhibited. When CaO is not present, the surface compressive stress after chemical strengthening tends to decrease. On the other hand, when CaO is present in amounts exceeding 8 mol%, the surface compressive stress after chemical strengthening decreases significantly, the depth of the compressive stress layer becomes significantly shallower, and the glass plate 10 becomes more prone to devitrification.

[0035] Therefore, a CaO content in the range of 1 to 8 mol% is appropriate. Preferably, the CaO content is 7 mol% or less, and preferably 3 mol% or more.

[0036] (SrO, BaO) SrO and BaO significantly reduce the viscosity of the glass plate 10, and in small amounts, the liquidus temperature T L The effect of reducing the stress is more pronounced than with CaO. However, even with the addition of very small amounts, SrO and BaO significantly hinder the movement of sodium ions in the glass plate 10, greatly reducing the surface compressive stress and making the depth of the compressive stress layer considerably shallower.

[0037] Therefore, it is preferable that this glass plate 10 substantially does not contain SrO and BaO.

[0038] (Na2O) Na2O is a component that increases surface compressive stress and deepens the surface compressive stress layer by substituting sodium ions with potassium ions. However, if the content is increased beyond the appropriate amount, the stress relaxation during the chemical strengthening treatment will outweigh the generation of surface compressive stress due to ion exchange during the chemical strengthening treatment, resulting in a tendency for the surface compressive stress to decrease.

[0039] Furthermore, while Na2O is a component that improves solubility and lowers T4 and T2, if the Na2O content is too high, the water resistance of the glass will be significantly reduced. In the glass plate 10, if the Na2O content is 10 mol% or more, the effect of lowering T4 and T2 is sufficiently obtained, and if it exceeds 16 mol%, the reduction in surface compressive stress due to stress relaxation becomes significant.

[0040] Therefore, the Na2O content in the glass plate 10 of this embodiment is appropriately in the range of 10 to 16 mol%. The Na2O content is preferably 12 mol% or more, and more preferably 15 mol% or less.

[0041] (K2O) K2O, like Na2O, is a component that improves the solubility of glass. Furthermore, in the range of low K2O content, the ion exchange rate in chemical strengthening increases, and the depth of the surface compressive stress layer increases, while the liquidus temperature T of the glass plate 10 increases. L This reduces the concentration of K2O. Therefore, it is preferable to include K2O at a low concentration.

[0042] On the other hand, K2O has a smaller effect on lowering T4 and T2 compared to Na2O, but a large amount of K2O hinders the clarification of the glass melt. Also, the higher the K2O content, the lower the surface compressive stress after chemical strengthening. Therefore, a K2O content in the range of 0 to 1 mol% is appropriate.

[0043] (Li2O) Even a small amount of Li2O significantly reduces the depth of the compressive stress layer. Furthermore, when a glass component containing Li2O is chemically strengthened with potassium nitrate alone, the rate at which the molten salt deteriorates is significantly faster compared to a glass component without Li2O. Specifically, when the same molten salt is repeatedly used for chemical strengthening, the surface compressive stress formed on the glass surface decreases with fewer repetitions. Therefore, although the glass plate 10 of this embodiment may contain 1 mol% or less of Li2O, it is preferable to substantially omit Li2O.

[0044] (B2O3) B2O3 is a component that reduces the viscosity of the glass plate 10 and improves its solubility. However, if the B2O3 content is too high, the glass plate 10 becomes more prone to phase separation, and its water resistance decreases. In addition, compounds formed by B2O3 and alkali metal oxides may volatilize and damage the refractory material in the glass melting chamber. Furthermore, the presence of B2O3 reduces the depth of the compressive stress layer in chemical strengthening. Therefore, a B2O3 content of 0.5 mol% or less is appropriate. In the present invention, it is more preferable that the glass plate 10 substantially does not contain B2O3.

[0045] (Fe2O3) Normally Fe is Fe 2+ or Fe 3+ In this state, it exists in the glass and acts as a coloring agent. Fe 3+ Fe is an ingredient that enhances the UV absorption performance of glass. 2+ This component enhances heat absorption performance. When the glass plate 10 is used as a cover glass for a display, it is desirable that the coloring is not noticeable, so a low Fe content is preferable. However, Fe is often inevitably mixed in due to industrial raw materials. Therefore, the iron oxide content, converted to Fe2O3, is preferably 0.15% by mass or less, more preferably 0.1% by mass or less, and even more preferably 0.02% by mass or less, with the entire glass plate 10 being expressed as 100% by mass.

[0046] (TiO2) TiO2 is a component that reduces the viscosity of the glass plate 10 and simultaneously increases the surface compressive stress due to chemical strengthening, but it can cause the glass plate 10 to have a yellowish tint. Therefore, an appropriate TiO2 content is 0 to 0.2 mass%. In addition, it is inevitably mixed in with commonly used industrial raw materials, and may be present in the glass plate 10 at a concentration of about 0.05 mass%. At this level of concentration, it does not cause discoloration of the glass, so it may be included in the glass plate 10 of this embodiment.

[0047] (ZrO2) ZrO2 can sometimes be mixed into the glass plate 10 from the refractory bricks that make up the glass melting furnace, especially when manufacturing glass plates using the float process, and its content is known to be around 0.01% by mass. On the other hand, ZrO2 is a component that improves the water resistance of glass and increases the surface compressive stress due to chemical strengthening. However, a high ZrO2 content can lead to an increase in the working temperature T4 and the liquidus temperature T L This can cause a rapid increase in Zr, and in the production of glass plates by the float method, precipitated Zr-containing crystals tend to remain as foreign matter in the manufactured glass. Therefore, a ZrO2 content of 0 to 0.1 mass% is appropriate.

[0048] (SO3) In the float process, sulfates such as sodium hydroxide (Na2SO4) are commonly used as clarifying agents. The sulfates decompose in the molten glass to produce gaseous components, which promote degassing of the molten glass. However, some of the gaseous components dissolve and remain in the glass plate 10 as SO3. In the glass plate 10 of the present invention, the SO3 content is preferably 0 to 0.3% by mass.

[0049] (CeO2) CeO2 is used as a clarifying agent. CeO2 generates O2 gas in the molten glass, thus contributing to degassing. On the other hand, too much CeO2 can cause the glass to turn yellow. Therefore, the CeO2 content is preferably 0 to 0.5% by mass, more preferably 0 to 0.3% by mass, and even more preferably 0 to 0.1% by mass.

[0050] (SnO2) In glass plates formed by the float process, it is known that tin diffuses from the tin bath to the surface that came into contact with the tin bath during molding, and this tin exists as SnO2. Furthermore, SnO2 mixed with the glass raw material contributes to degassing. In the glass plate 10 of the present invention, the SnO2 content is preferably 0 to 0.3% by mass.

[0051] (Other ingredients) The glass plate 10 according to the present embodiment is preferably substantially composed of each of the components listed above. However, the glass plate 10 according to the present embodiment may contain components other than the components listed above, preferably in a range where the content rate of each component is less than 0.1% by mass.

[0052] Examples of components whose inclusion is allowed include As2O5, Sb2O5, Cl, and F, which are added for the purpose of defoaming molten glass in addition to the above-mentioned SO3 and SnO2. However, it is preferable not to add As2O5, Sb2O5, Cl, and F because of their large adverse effects on the environment. Another example of components whose inclusion is allowed is ZnO, P2O5, GeO2, Ga2O3, Y2O3, and La2O3. Components other than the above derived from raw materials used industrially are also allowed as long as they do not exceed 0.1% by mass. Since these components are added as appropriate or inevitably mixed as necessary, the glass plate 10 of the present embodiment may not substantially contain these components.

[0053] (Density (specific gravity): d) From the above composition, in the present embodiment, the density of the glass plate 10 is 2.53 g·cm -3 or less, and further 2.51 g·cm -3 or less, and in some cases 2.50 g·cm -3 or less can be reduced.

[0054] In the float process or the like, if the difference in density between glass varieties is large, when switching the glass variety to be manufactured, the molten glass with a higher density may stay at the bottom of the melting furnace, which may cause problems in switching the variety. Currently, the density of soda-lime glass mass-produced by the float process is about 2.50 g·cm -3 . Therefore, considering mass production by the float process, the density of the glass plate 10 is close to the above value. Specifically, 2.45 to 2.55 g·cm -3 [[ID=​​​​​

[0055] (Modulus of elasticity: E) Chemical strengthening involving ion exchange can cause warping of the glass substrate. To suppress this warping, it is preferable that the elastic modulus of the glass plate 10 be high. According to the present invention, the elastic modulus (Young's modulus: E) of the glass plate 10 can be increased to 70 GPa or higher, and even to 72 GPa or higher.

[0056] The following describes the chemical strengthening of the glass plate 10. (Conditions for chemical strengthening and compressive stress layer) Chemical strengthening of the glass plate 10 according to the present invention can be carried out by bringing a sodium-containing glass plate 10 into contact with a molten salt containing a monovalent cation, preferably a potassium ion, which has a larger ionic radius than sodium ions, and performing an ion exchange treatment in which the sodium ions in the glass plate 10 are replaced by the above-mentioned monovalent cation. As a result, a compressive stress layer is formed on the surface, in which compressive stress is applied.

[0057] A typical example of a molten salt is potassium nitrate. A mixed molten salt of potassium nitrate and sodium nitrate can also be used, but because it is difficult to control the concentration of mixed molten salts, a molten salt of potassium nitrate alone is preferred.

[0058] The surface compressive stress and compressive stress layer depth in a tempered glass component can be controlled not only by the glass composition of the article, but also by the temperature of the molten salt and the processing time in the ion exchange treatment.

[0059] By contacting the glass plate 10 described above with a molten potassium nitrate salt, a tempered glass member with a very high surface compressive stress and a very deep compressive stress layer can be obtained. Specifically, a tempered glass member with a surface compressive stress of 700 MPa or more and a compressive stress layer depth of 20 μm or more can be obtained, and further, a tempered glass member with a compressive stress layer depth of 20 μm or more and a surface compressive stress of 750 MPa or more can also be obtained.

[0060] Furthermore, when using glass plates 10 with a thickness of 3 mm or more, wind strengthening can be used as a general strengthening method instead of chemical strengthening. Strengthening treatment is generally performed on cover members, but it is not essential depending on the application and required properties. In addition, strengthening treatment is often performed prior to the formation of the functional film (described later), but it may also be performed after the formation of the functional film as long as it does not hinder the expression of the functional film.

[0061] <2. Functional membranes> Next, the functional film will be described with reference to Figures 2 and 3. Figure 2 is a partial cross-sectional view of a glass plate on which functional films are laminated, and Figure 3 is another example partial cross-sectional view of a glass plate on which functional films are laminated. As shown in Figures 2 and 3, the cover members 400 and 500 comprise a glass plate 10 and functional films 50 and 60 provided on the glass plate 10. In Figures 2 and 3, the functional films 50 and 60 are directly formed on the first surface 10s of the glass plate 10, but another film may be interposed between the glass plate 10 and the functional films 50 and 60. The functional films 50 and 60 contain inorganic oxide fine particles 5 (hereinafter sometimes simply referred to as "particles"), a matrix 2 that constitutes a three-dimensional network connection, and antibacterial metal ions. The functional films 50 and 60 may contain voids. The voids may exist in the matrix 2 or in contact with the particles 5 and the matrix 2.

[0062] The functional films 50 and 60 have a first region 50p and 60p and a second region 50v and 60v. In the first region 50p and 60p, particles 5 are stacked in the thickness direction of the functional films 50 and 60. When the functional films 50 and 60 are observed from the surface side along the thickness direction, the second region 50v and 60v surround the first region 50p and 60p. However, the second region 50v and 60v may also be surrounded by the first region 50p and 60p. The first region 50p and 60p and the second region 50v and 60v are, for example, interposed between multiple other regions that are spaced apart from each other.

[0063] This structure is sometimes called a sea-island structure. The second regions 50v and 60v are valley-like regions whose surfaces recede from the surrounding first region. Therefore, the island portion of the sea-island structure protrudes from the sea portion when the island portion is the first region 50p and 60p, and is recessed from the sea portion when the island portion is the second region 50v and 60v. In the second regions 50v and 60v, there is less accumulation of particles 5 than in the first regions 50p and 60p. The second regions 50v and 60v may include a portion 50t where particles 5 are accumulated (see Figure 2). Alternatively, the second regions 50v and 60v may include a portion where particles 5 are not accumulated or do not exist (see Figure 3). At least a portion of the second regions 50v and 60v may consist of a portion where particles 5 are not accumulated or do not exist. The first regions 50p and 60p may be plateau-like regions in part, or even 50% or more, or possibly all, of them based on the number of particles. Matrix 2 is present in both the first regions 50p and 60p and the second regions 50v and 60v, but in the second regions 50v and 60v, at least a portion is exposed to the outside. On the other hand, in the first regions 50p and 60p, matrix 2 is arranged on a glass plate 10, and particles 5 are stacked on top of it.

[0064] "Plateau-like" means that when the film is observed using SEM or the like, the upper part of the convex portions of the functional films 50 and 60 appears plateau-like. More precisely, it means that in the cross-section of the film, L2 / L1 ≥ 0.75, and especially L2 / L1 ≥ 0.8, is satisfied. Here, as shown in Figure 4, L1 is the length of the portion corresponding to 50% of the height H of each convex portion, and L2 is the length of the portion corresponding to 70%, preferably 75%, of the height H. As shown in Figure 4, for one L1, L2 may exist in two or more parts. In this case, L2 is determined by the total length of the two or more parts.

[0065] The boundaries 50b and 60b between the first region 50p and 60p and the second region 50v and 60v can be determined by the average thickness T of the functional films 50 and 60 (see Figure 3). The average thickness T can be measured using a laser microscope, as described later. The spacing of the boundaries 50b and 60b determines the width Wp of the first region 50p and 60p and the width Wv of the second region 50v and 60v.

[0066] The width Wp may be 3 μm or more, more preferably 5 μm or more, and more preferably 7 μm or more. The width Wv may be 1 μm or more, 2 μm or more, and more preferably 3 μm or more. For example, it is preferable that the width Wp is greater than the width Wv. When the width Wp is large, visible light is more easily transmitted directly in the functional films 50 and 60, so the haze rate tends to be low. On the other hand, when the width Wv is small, the boundaries between the first regions 50p and 60p and the second regions 50v and 60v are close together. As a result, near the boundary with the second regions 50v and 60v, visibility becomes difficult due to scattering of visible light by the walls of the first regions 50p and 60p, and the gross value becomes low. For example, if the second regions 50v and 60v do not exist, the functional film will consist only of the first regions 50p and 60p, and the visible light transmission performance will be the same as that of the first region. Therefore, if the second regions 50v and 60v are absent, the scattering effect by the walls of the first regions 50p and 60p may be relatively weakened. Accordingly, it is preferable that the width Wv is 1 μm or more as described above. When the widths Wp and Wv simultaneously satisfy the above range, this functional film 50,60 is particularly suitable for achieving both a low haze rate and low gloss.

[0067] The first region 50p and 60p and the second region 50v and 60v are, for example, 0.25 μm in size. 2 Furthermore, 0.5 μm 2 The above, especially regarding 1 μm 2 In some cases, the above may be 5 μm 2 Furthermore, 10 μm 2 It may also encompass a wide range of areas.

[0068] The functional films 50 and 60 have a first region 50p and 60p and a second region 50v and 60v. The ratio of the second region 50v and 60v to the area of ​​the region where the functional film 50 is formed may be, for example, 5 to 90%, more specifically 10 to 70%, and particularly 20 to 50%. The functional films 50 and 60 may also consist only of the first region 50p and 60p and the second region 50v and 60v.

[0069] Furthermore, as shown in Figure 5, at least a portion of the first region 60p is raised near the boundary with the second region 60v. This also causes a moderate scattering of visible light incident on the functional film 60, resulting in a tendency for lower gloss. The same applies to the functional film 50. Moreover, this effect is particularly pronounced when the widths of the second regions 50v and 60v are small, as the raised portions are closer together.

[0070] The shapes of the second regions 50v and 60v are not particularly limited, but various shapes can be cited, such as shapes formed by closed curves (e.g., circular shapes including ellipses), polygonal shapes, and irregular shapes. Furthermore, the sizes of the multiple second regions 50v and 60v may differ. That is, multiple second regions 50v and 60v of different sizes may be dispersed in the functional films 50 and 60.

[0071] <2-1. Particles> The shape of particle 5 is not particularly limited, but it is preferably spherical. Particle 5 may be substantially composed of spherical particles. However, some of the particles 5 may have a shape other than spherical, such as a flat plate shape. Particle 5 may also be composed only of spherical particles. Here, a spherical particle is a particle in which the ratio of the longest diameter to the shortest diameter passing through the center of gravity is 1 or more and 1.8 or less, particularly 1 or more and 1.5 or less, and the surface is composed of a curved surface. The average particle size of the spherical particles may be 5 nm to 200 nm, more specifically 10 nm to 100 nm, and particularly 20 nm to 60 nm. The average particle size of the spherical particles is determined by the average of the individual particle sizes, specifically the average of the shortest diameter and the longest diameter as described above, but it is desirable to measure this based on SEM images and target 30, preferably 50, particles.

[0072] The material constituting particle 5 is not particularly limited, but it is preferable to include inorganic oxides such as metal oxides, and especially silicon oxide. However, the metal oxide may include, for example, an oxide of at least one metal element selected from the group consisting of Al, Ti, Zr, Ta, Nb, Nd, La, Ce, and Sn.

[0073] As described later, particles 5 can be supplied from a dispersion of particles 5 to the functional membranes 50 and 60. In this case, it is preferable to use a dispersion in which particles 5 are individually and independently dispersed. Compared to a dispersion in which particles are linked together in a chain, using a dispersion in which particles are not aggregated is suitable for achieving a desirable aggregate state of particles in the functional membranes 50 and 60. This is because the independent particles 5 are more likely to move as the liquid such as the dispersion medium evaporates, and are more likely to form an aggregate state in the membrane that is suitable for achieving good properties.

[0074] <2-2. Matrix> Matrix 2 contains silicon oxide, which is an oxide of Si, and preferably has silicon oxide as its main component. Matrix 2, which has silicon oxide as its main component, is suitable for lowering the refractive index of the film and suppressing the reflectivity of the film. Matrix 2 may also contain components other than silicon oxide, and may contain components that partially contain silicon oxide.

[0075] Components partially containing silicon oxide include, for example, a portion composed of silicon atoms and oxygen atoms, to which atoms other than these two atoms, functional groups, and others are bonded. Examples of atoms other than silicon atoms and oxygen atoms include nitrogen atoms, carbon atoms, hydrogen atoms, and the metallic elements described in the next paragraph. Examples of functional groups include the organic group described as R in the next paragraph. Such components are not strictly silicon oxide in that they are not composed solely of silicon atoms and oxygen atoms. However, in describing the properties of Matrix 2, it is appropriate to treat the silicon oxide portion composed of silicon atoms and oxygen atoms as "silicon oxide," and this is consistent with the conventions of the field. In this specification, the silicon oxide portion will also be treated as silicon oxide. As is clear from the above explanation, the atomic ratio of silicon atoms to oxygen atoms in silicon oxide does not have to be stoichiometric (1:2).

[0076] Matrix 2 may include metal oxides other than silicon oxide, specifically metal oxide components or metal oxide moieties other than silicon. The metal oxides that Matrix 2 may contain are not particularly limited, but for example, they are oxides of at least one metal element selected from the group consisting of Al, Ti, Zr, Ta, Nb, Nd, La, Ce, and Sn. Matrix 2 may also contain inorganic compound components other than oxides, such as nitrides, carbides, halides, etc., and may also contain organic compound components.

[0077] Metal oxides such as silicon oxide can be formed from hydrolyzable organometallic compounds. Examples of hydrolyzable silicon compounds include the compound shown in formula (1). R n SiY 4-n (1) R is an organic group comprising at least one selected from alkyl groups, vinyl groups, epoxy groups, styryl groups, methacryloyl groups, and acryloyl groups. Y is a hydrolyzable organic group, or a halogen atom, which is at least one selected from alkoxy groups, acetoxy groups, alkenyloxy groups, and amino groups. The halogen atom is preferably Cl. n is an integer from 0 to 3, preferably 0 or 1.

[0078] For R, an alkyl group, such as an alkyl group having 1 to 3 carbon atoms, particularly a methyl group, is preferred. For Y, an alkoxy group, such as an alkoxy group having 1 to 4 carbon atoms, particularly a methoxy group and an ethoxy group, is preferred. Two or more compounds represented by the above formula may be used in combination. For example, such a combination may be a tetraalkoxysilane with n = 0 and a monoalkyltrialkoxysilane with n = 1.

[0079] The compound represented by formula (1) forms a network structure in which silicon atoms are bonded to each other via oxygen atoms after hydrolysis and polycondensation. In this structure, the organic group represented by R is included in a state where it is directly bonded to the silicon atoms.

[0080] <2-3. Metal Ions> The metal ions are antibacterial and can be formed from monovalent or divalent copper ions, silver ions, etc. The metal ion content of the functional membranes 50 and 60 is preferably 2 to 50% by molar ratio, and more preferably 5 to 25%, relative to the main component with the largest weight ratio among the compounds constituting the network bond.

[0081] Metal ions are contained in matrix 2. Therefore, in the second region 50v, 60v where matrix 2 is exposed to the outside, it exhibits antibacterial or antiviral properties against bacteria and viruses that come into contact with the second region 50v, 60v. On the other hand, in the first region 50p, 60p, there are almost no metal ions on the surface, but if attached bacteria or viruses pass between the particles 5 and come into contact with matrix 2 near the glass plate 10, the metal ions contained in it will exhibit antibacterial or antiviral properties.

[0082] <2-4. Physical properties of functional films> The ratio of particles 1 to matrix 2 in the functional films 50 and 60 is, for example, 0.05 to 10, more preferably 0.05 to 7, on a mass basis. The volume ratio of voids in the functional films 50 and 60 is not particularly limited, but may be 10% or more, and more preferably 10 to 20%. However, voids do not need to be present.

[0083] The film thickness of the functional films 50 and 60 is not particularly limited, but from the viewpoint of easily obtaining appropriate anti-glare properties, the film thickness of the first region 50p and 60p is suitable, for example, 50 nm to 1000 nm, more preferably 100 nm to 700 nm, and especially suitable 100 nm to 500 nm. On the other hand, the film thickness of the second region 50v and 60v is suitable, for example, 10 nm to 500 nm, preferably 30 nm to 300 nm. In particular, the difference between the highest and lowest points of the functional films 50 and 60 measured from the first surface of the glass plate 10 may be 3 times or more, and even more preferably 4 times or more, the average particle size of the particles 5.

[0084] Sparkles are bright spots that occur depending on the relationship between the minute irregularities that provide the anti-glare function and the pixel size of the display panel. Sparkles are observed as irregular fluctuations of light that occur with changes in the relative position between the display device and the user's viewpoint. Sparkles have become more apparent with the increasing resolution of display devices. By setting the widths Wp and Wv within the ranges described above, the functional films 50 and 60 are particularly suitable for suppressing sparkles while reducing gloss and haze in a balanced manner.

[0085] <2-5. Method for forming functional membranes> The method for forming the functional films 50 and 60 is not particularly limited, but for example, they can be formed as follows. First, a precursor solution is prepared by dissolving the material constituting the matrix described above, for example, a silicon alkoxide such as tetraethoxysilane, in an alcohol solution under acidic conditions. Then, a dispersion containing inorganic oxide fine particles such as colloidal silica is mixed into the precursor solution. Furthermore, a dispersion containing the antibacterial metal ions described above, for example, an aqueous solution of copper chloride or an aqueous solution of copper nitrate, is mixed into the precursor solution. In addition, various additives can be mixed in as needed. For example, boron can be added as boric acid. For example, if boron remains in the functional films 50 and 60, boron (BO) - Because it has the effect of attracting antibacterial copper ions, it can suppress the aggregation of copper ions and the formation of crystals such as copper oxide. In this way, a coating solution for functional films 50 and 60 is produced.

[0086] The solvent for the dispersion containing inorganic oxide fine particles is not particularly limited, but examples include propylene glycol monomethyl ether (PGME), methyl ethyl ketone, toluene, and methyl isobutyl ketone. Among these, it is preferable to use a nonpolar compound with a high boiling point (e.g., 75°C or higher), such as methyl ethyl ketone, cyclohexane, toluene, or methyl isobutyl ketone, as the solvent, because the first region 50p, 60p and the second region 50v, 60v described above are formed.

[0087] Next, a coating solution is applied to the first surface of the cleaned glass plate 10. The application method is not particularly limited, but for example, a flow coating method, a spray coating method, or a spin coating method can be used. After that, the applied coating solution is dried in an oven or the like at a predetermined temperature (e.g., 80-120°C) to volatilize the alcohol in the solution, and then sintered at a predetermined temperature (e.g., 200-500°C) for hydrolysis and decomposition of organic chains, to obtain functional films 50 and 60.

[0088] <3. Optical properties of the cover material> As described above, the optical properties of the cover member 100 on which the antibacterial film 2 is formed are preferably such that the visible light transmittance is 85% or more, and more preferably 90% or more. The haze rate of the cover member 10 is, for example, 20% or less, more preferably 15% or less, particularly 10% or less, and in some cases may be 1 to 8%, or even 1 to 6%.

[0089] Gloss can be evaluated by specular gloss. The 60° specular gloss of the glass plate 10 is, for example, 60-130%, more specifically 70-120%, particularly 80-110%, and 85-100%. These specular gloss values ​​are measured on the surface 10s on which the functional films 50 and 60 are formed. Generally, glass plates exhibiting a gloss of 120-140% are used as cover members for displays in in-vehicle equipment such as car navigation systems. On the other hand, the haze rate of the glass plate 10 is, for example, 20% or less, more specifically 15% or less, particularly 10% or less, and in some cases may be 1-8%, more specifically 1-6%, and particularly 1-5%.

[0090] Preferably, the relationship between the 60° specular gloss G and the haze rate H (%) is given by equation (a), more preferably by equation (b), and even more preferably by equation (c). G and H may also satisfy the relationship given by equation (d). H ≤ -0.2G + 25 (a) H≦-0.2G+24.5 (b) H ≤ -0.2G + 24 (c) H≦-0.15G+18 (d)

[0091] Furthermore, gloss can be measured according to "Method 3 (60-degree specular gloss)" of "Method for measuring specular gloss" in JIS Z8741-1997, and haze can be measured according to JIS K7136:2000.

[0092] <4. Features> The cover member 100 according to this embodiment can achieve the following effects. (1) In the glass member 100 according to this embodiment, antibacterial metal ions are supported on the matrix 2 in the functional films 50 and 60. Therefore, antibacterial and antiviral functions can be exhibited. In particular, since the metal ions are supported on the matrix 2 which constitutes a three-dimensional network connection, the elution of metal ions can be suppressed. For example, in the first regions 50p and 60p, the matrix 2 supporting the metal ions is covered with particles 5, so the elution of metal ions can be further suppressed.

[0093] (2) In the functional films 50 and 60, since there are first regions 50p and 60p in which particles are stacked, visible light is more easily transmitted directly, and the haze rate can be reduced. On the other hand, if there are second regions 50v and 60v, visibility becomes difficult due to scattering of visible light near the boundary with the first regions 50p and 60p, and the gloss value is reduced. This effect is particularly enhanced when the width of the second regions 50v and 60v is small, as the walls and raised parts of the first regions 50p and 60p are in close proximity. Therefore, the functional film of this embodiment can improve the anti-glare effect.

[0094] (3) As described above, in the present invention, a single functional film 50, 60 can exhibit both anti-glare function and antibacterial / antiviral function. Therefore, the manufacturing of the functional films 50, 60 is simple.

[0095] <5. Variation> Although one embodiment of the present invention has been described above, the present invention is not limited to the above embodiment, and various modifications are possible without departing from the spirit of the invention. The following modifications can be combined as appropriate.

[0096] <5-1> The functional membrane shown in the above embodiment has first regions 50p and 60p and second regions 50v and 60v, but it may also be formed only of the first regions 50p and 60p. In this case, the particle dispersion can be formed with propylene glycol monomethyl ether. Thus, even if the functional membrane is formed only of the first regions 50p and 60p, it can exhibit anti-glare function and antibacterial / antiviral function, as will be described later.

[0097] <5-2> The cover member according to the present invention can be colorless and transparent, or it can be made colored and transparent or semi-transparent by coloring at least one of the glass plate 1 and the functional films 50 and 60. [Examples]

[0098] The following describes embodiments of the present invention. However, the present invention is not limited to the following embodiments. (1) Preparation of Examples and Comparative Examples Cover members according to Examples 1-4 and the Comparative Example were formed by laminating a functional film onto a 50mm x 50mm float glass plate.

[0099] A coating solution having the composition shown in Table 1 was prepared. First, a precursor solution for the matrix was prepared (in grams). Then, these mixed solutions were stirred at 60°C for 7 hours to obtain a precursor solution by hydrolysis of TEOS. To this precursor solution, a dispersion of particles and copper nitrate were mixed while stirring. Then, this mixed solution was stirred at room temperature to obtain a coating solution. The difference between Examples 1-4 and the comparative example is that the coating solution of the comparative example does not contain copper nitrate. Therefore, the comparative example does not have antibacterial or antiviral properties. [Table 1] • KBM-903 (manufactured by Shin-Etsu Silicone) • MEK-ST-L (organosilica sol manufactured by Nissan Chemical Corporation) • PGM-AC-4130Y (Organosilica sol manufactured by Nissan Chemical Corporation) • MIBK-ST-L (Organosilica sol manufactured by Nissan Chemical Corporation)

[0100] Next, this coating liquid was applied to a glass plate by flow coating to a thickness of approximately 200-300 nm. After air drying for 10 minutes, it was heated in an oven set to 300°C for 30 minutes to form a functional film. In this way, the cover members according to Examples 1-4 and the comparative example were completed.

[0101] (2) Evaluation The following tests were performed on the cover members of Examples 1-4 and the Comparative Example. The results are shown in Table 2.

[0102] (2-1) Optical properties The gloss value and haze rate were measured. For the gloss value, the 60° gloss value was measured from the side where the functional film was formed using a gloss checker (Gloss Checker IG-320, Horiba, Ltd.). The haze rate was measured using a haze meter NDH2000, manufactured by Nippon Denshoku Industries, Ltd. In this case, the functional film was used as the incident surface, and the haze rate was measured at three points on the sample, and the average value was taken as the haze rate.

[0103] (2-2) Exterior The second surface of the cover member was placed on an illuminated inspection table, and with the light shining on the cover member, the appearance of the cover member as viewed from the functional membrane side was inspected according to the following criteria. A: No film irregularities are observed visually. B: Slight film irregularities are visible to the naked eye.

[0104] (2-2) Durability Test The cover members according to Examples 2 to 4 were immersed in 25 ml of water for 24 hours. During this time, 1.5 ml was extracted from the water at predetermined intervals, and the amount of copper ions eluted (eluted per unit area of ​​coating) was calculated. The calculation of this eluted amount was performed as follows: First, the water sample, which had been colored using Pack Test Copper (manufactured by Kyoritsu Chemical Laboratory), was measured using Digital Pack Test Copper (same as above) to determine the copper ion concentration contained in the liquid, and then the mass % of the amount eluted relative to the copper before the test was calculated.

[0105] (2-3) Antiviral testing The antibacterial properties were evaluated as follows, based on JIS Z2801:2012 (film contact method) (equivalent to ISO 22916). • Test bacterium: E. coli (NBRC3972) • Sample form: Cover member as described above • Duration of action: 24 hours • Calculation of antibacterial activity value (R): R = (Ut - U0) - (At - U0) = Ut - At U0: The average logarithmic value of the number of viable bacteria on the glass plate immediately after inoculation. Ut: The average logarithmic value of the number of viable bacteria on a glass plate after 24 hours. At: The average logarithmic value of the number of viable bacteria in the cover material after 24 hours. • Operating conditions: Temperature 35°C, humidity 90% or higher (JIS compliant) • Adhesive film: 40mm x 40mm PP film (JIS standard) • Amount of test bacterial solution to be taken: 0.2 ml • Number of viable cells in the test bacterial suspension: 1.1 × 10⁶ 6 • Measurement of viable bacterial count: The number of viable bacteria in the cover material was measured immediately after inoculation of the glass plate with bacterial solution and after 24 hours of incubation.

[0106] (2-4) Discussion The results of the above tests showed that the cover members in Examples 1 to 4 had appropriate gloss values ​​and haze rates, and that sufficient anti-glare function was obtained. In addition, the antiviral activity was 2.5 or higher in all cases. Since an antiviral activity is evaluated as being 2.0 or higher, sufficient antiviral performance was confirmed in the cover members in Examples 1 to 4. Furthermore, although the amount of copper eluted was not measured in Example 1 and the comparative example, in Examples 2 to 4, approximately 30-40% of copper remained in the functional film even after durability testing, so it is considered that they have sufficient durability. Regarding appearance, slight film unevenness was observed in Example 1, but there were no particular problems in Examples 2 to 4.

[0107] [Table 2]

[0108] The functional films of Examples 1 and 4 and the Comparative Example were imaged using a scanning electron microscope (SEM) to observe their surface properties. Example 1, shown in Figure 6, consists only of the first region described above. As mentioned above, the anti-glare and antiviral functions were sufficient, but the surface was very uneven, and slight film irregularities were observed in the appearance. On the other hand, the functional film of Example 4, shown in Figure 7, had a first region and a roughly circular second region, and the anti-glare and antiviral functions were sufficient, and the appearance was also fine. The functional film of the Comparative Example, shown in Figure 8, also had a first and second region, but the second region was irregularly shaped. [Explanation of symbols]

[0109] 10 glass plates 50,60 Functional membrane 100 Cover component 200 Protected member

Claims

1. A glass plate having a first surface and a second surface, The functional film formed on the first surface, Equipped with, The functional membrane is a cover member formed from a single membrane and has anti-glare and antibacterial properties.

2. The aforementioned functional membrane is The matrix that constitutes the three-dimensional network connection, Inorganic oxide nanoparticles and Antibacterial metal ions, The cover member according to claim 1, comprising:

3. The aforementioned functional membrane is A first region in which the inorganic oxide particles are stacked in the thickness direction of the functional film, A valley-shaped second region that surrounds or is surrounded by the first region, The cover member according to claim 2, wherein such a member exists.

4. The cover member according to claim 3, wherein the first region is a plateau-like region.

5. The cover member according to claim 3 or 4, wherein the second region includes a portion where the inorganic oxide particles are not piled up or where the inorganic oxide particles are absent.

6. The width of the first region is 3 μm or more. The cover member according to any one of claims 3 to 5, wherein the width of the second region is 1 μm or more.

7. The width of the first region is 5 μm or more. The cover member according to any one of claims 3 to 5, wherein the width of the second region is 2 μm or more.

8. In the second region, the matrix is ​​exposed. The cover member according to any one of claims 3 to 7, wherein the exposed matrix contains the metal ions.

9. In the first region, the matrix is ​​arranged on the glass plate, and the inorganic oxide particles are stacked on the matrix. The cover member according to any one of claims 3 to 8, wherein the matrix of the first region contains the metal ions.

10. The cover member according to any one of claims 3 to 9, wherein at least one of the second regions is formed by a closed curve.

11. The cover member according to claim 10, wherein the second region includes a region formed by a plurality of closed curves of different sizes.

12. The cover member according to any one of claims 3 to 11, wherein the area near the boundary with the second region in the first region is raised.

13. The steps include forming a coating solution by adding inorganic oxide fine particles and antibacterial metal ions to a silicon alkoxide, The steps include applying the aforementioned coating liquid to a glass plate, The steps include: heating the glass plate to which the coating liquid has been applied, A method for manufacturing a cover member, which includes the following features.

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