Stacked body, glass cover sheet, and display device

Abstract

The present application relates to a laminate which can have both antiviral properties and antifouling properties. The present application relates to a laminate which has a base body having a first main surface and a second main surface, and a CuAlO2 layer and an antifouling layer provided on the first main surface side of the base body, the CuAlO2 layer and the antifouling layer being formed on the most surface on the first main surface side in contact with each other, the thickness of the CuAlO2 layer being 2 nm or more, and the surface resistance value of the most surface on the first main surface side being 1.0 x 10 12 Ω / cm 2 or more.

Description

Technical Field

[0001] This invention relates to laminates, glass covers, and display devices. Background Technology

[0002] Due to the widespread use of car-sharing and other similar services, there is a demand for antiviral properties on the surface of glass covers for in-vehicle display devices. CuAlO2 is known as an antiviral material (see, for example, Patent Document 1).

[0003] Existing technical documents

[0004] Patent documents

[0005] Patent Document 1: International Publication No. 2022 / 019244 Summary of the Invention

[0006] However, if a metal oxide layer, as in Patent Document 1, is applied to the surface of the glass cover, there is a risk that both antiviral and antifouling properties cannot be achieved.

[0007] The purpose of this invention is to provide a laminate, glass cover, and display device that can take into account both antiviral and antifouling properties.

[0008] The laminate of the first embodiment of the present invention comprises a substrate having a first main surface and a second main surface, and a CuAlO2 layer and an antifouling layer disposed on the first main surface side of the substrate. The CuAlO2 layer and the antifouling layer are formed in contact with each other on the outermost surface of the first main surface side. The thickness of the CuAlO2 layer is 2 nm or more, and the surface resistivity of the outermost surface of the first main surface side is 1.0 × 10⁻⁶. 12 Ω / cm 2 above.

[0009] The laminate of the second embodiment of the present invention comprises a substrate having a first main surface and a second main surface, and a CuAlO2 layer and an antifouling layer disposed on the first main surface side of the substrate. The CuAlO2 layer and the antifouling layer are formed in contact with each other on the outermost surface of the first main surface side, and the surface resistivity of the outermost surface of the first main surface side is 1.0 × 10⁻⁶. 12 Ω / cm 2 The antiviral activity value of the outermost surface of the first main surface side is 2.0 or higher when subjected to an antiviral performance evaluation test as specified in ISO 21702 for 1 hour.

[0010] The glass cover sheet of the present invention is composed of the above-described laminate.

[0011] The display device of the present invention includes the aforementioned glass cover and a display, wherein the second main surface side of the aforementioned glass cover is attached to the aforementioned display.

[0012] According to the present invention, a laminate, a glass cover, and a display device that can take into account both antiviral and antifouling properties can be provided. Attached Figure Description

[0013] Figure 1 This is a cross-sectional view of the stacked body of the embodiment.

[0014] Figure 2 This is a schematic diagram illustrating an application example of a stacked body in an implementation method.

[0015] Figure 3A This is a cross-sectional view of the stacked body of the first modified example.

[0016] Figure 3B This is a cross-sectional view of the stacked body of the second variation.

[0017] Figure 4A This is a cross-sectional view of the stacked body in the third variation.

[0018] Figure 4B This is a cross-sectional view of the stacked body of the fourth variation.

[0019] Figure 5A This is a cross-sectional view of the laminated body in the fifth variation.

[0020] Figure 5B This is a cross-sectional view of the stacked body of the sixth variation.

[0021] Figure 6A This is a cross-sectional view of the stacked body of the seventh variation.

[0022] Figure 6B This is a cross-sectional view of the stacked body of the eighth variation.

[0023] Figure 7A This is a cross-sectional view of the stacked body of the ninth variation.

[0024] Figure 7B This is a cross-sectional view of the stacked body of the tenth variation.

[0025] Figure 7C This is a cross-sectional view of the eleventh variation of the stacked body.

[0026] Figure 8A This is a cross-sectional view of the stacked body in the twelfth variation example.

[0027] Figure 8B This is a cross-sectional view of the thirteenth variation of the stacked body.

[0028] Figure 8C This is a cross-sectional view of the stacked body in the fourteenth variation. Detailed Implementation

[0029] The embodiments of the present invention will now be described. It should be noted that, for the purpose of understanding the present invention, the various components are sometimes exaggerated in the figures described below.

[0030] <The Composition of Layered Bodies>

[0031] First, the structure of the laminated body will be explained.

[0032] Figure 1 This is a cross-sectional view of a laminated body according to one embodiment of the present invention.

[0033] Figure 1 In the laminate 1, a glass substrate 2 serves as the base. The glass substrate 2 has a first main surface 21 and a second main surface 22 that are opposite to each other, and an end surface 23 that connects the first main surface 21 and the second main surface 22.

[0034] An anti-reflective layer 3 is stacked on the first main surface 21 of the glass substrate 2. An outermost functional layer 10, consisting of a CuAlO2 layer 4 and an anti-fouling layer 5, is disposed on the anti-reflective layer 3.

[0035] Examples of glass substrates 2 include alkali-free glass, soda-lime glass, soda-lime silicate glass, aluminosilicate glass, borosilicate glass, lithium aluminosilicate glass, and borosilicate glass. Alkali-free glass refers to glass that substantially does not contain alkali metal oxides such as Na₂O and K₂O. Here, "substantially does not contain alkali metal oxides" means that the total content of alkali metal oxides is less than 0.1% by mass.

[0036] When the laminate 1 is used as a glass cover for a display device, glass containing alkali metal oxides is preferred. Glass containing alkali metal oxides can have its strength increased by forming a compressive stress layer on the glass surface through a chemical strengthening treatment after molding.

[0037] The glass substrate 2 is not limited to a flat plate; it can have curvature over the entire surface or a portion thereof.

[0038] The anti-reflective layer 3 reduces the reflectivity of the laminate 1, thereby reducing glare caused by light reflection. When the laminate 1 is used in a display device, the anti-reflective layer 3 can increase the transmittance of light from the display device, thus improving the visual resolution of the display device.

[0039] The composition of the antireflective layer 3 is not particularly limited as long as it can suppress light reflection. For example, it can be composed of alternating layers of a high refractive index layer with a refractive index of 1.9 or higher at a wavelength of 550 nm and a low refractive index layer with a refractive index of 1.6 or lower at a wavelength of 550 nm. The number of low and high refractive index layers is not limited, but the low refractive index layer is preferably 1 to 15 layers, more preferably 10 layers or less, further preferably 6 layers or less, and most preferably 5 layers or less. The high refractive index layer preferably consists of the same number of layers as the low refractive index layer. It should be noted that... Figure 1 The example shows the case where the low-refractive-index layer and the high-refractive-index layer each consist of two layers.

[0040] When both the low-refractive-index layer and the high-refractive-index layer are composed of multiple layers, the layer furthest from the first main surface 21 of the glass substrate 2 is designated as the outermost layer 31. When the outermost layer 31 is designated as the first layer facing the glass substrate 2, the odd-numbered layers including the outermost layer 31... Figure 1 The outermost layer 31 and the third layer 33 are composed of low refractive index layers. If the layer adjacent to the glass substrate 2 side of the outermost layer 31 is designated as the second layer 32, then the even-numbered layers including the second layer 32... Figure 1 The second layer 32 and the fourth layer 34 are composed of high-refractive-index layers. The high-refractive-index layer furthest from the outermost layer 31... Figure 1 The fourth layer 34 is connected to the glass substrate 2.

[0041] The thickness of the anti-reflective layer 3 is preferably 100 nm to 500 nm. By making the thickness of the anti-reflective layer 3 100 nm or more, the reflection of external light can be effectively suppressed, and therefore it is preferred.

[0042] In this embodiment, the outermost layer 31 is a low refractive index layer, which is composed of silicon oxide (SiO2) as the main component.

[0043] The principal component mentioned here refers to the component that contains more than 50% of the product in the layer by molar ratio, which means that impurities can be contained in silicon oxide.

[0044] With the outermost layer 31 being primarily composed of silicon dioxide, as described later, the antifouling layer 5 is firmly bonded to the glass substrate 2 via the antireflective layer 3.

[0045] The thickness of the outermost layer 31 is preferably 1 nm to 120 nm, more preferably 3 nm to 100 nm.

[0046] The second layer 32 is a high refractive index layer. The material of the second layer 32 is not particularly limited, but preferably the main component is one or more selected from silicon nitride (SiN), titanium oxide (TiO2), niobium oxide (Nb2O5), tantalum oxide (Ta2O5), zirconium oxide (ZrO2), and mixtures thereof. By using these materials, even a film consisting of one layer of low refractive index and one layer of high refractive index can effectively prevent reflection. Furthermore, from the viewpoint of productivity and refractive index, silicon nitride, niobium oxide, tantalum oxide, and mixtures thereof are more preferred, with niobium oxide being particularly preferred.

[0047] Odd-numbered layers after the third layer, for example Figure 1 The third layer 33 is a low refractive index layer, which can be formed of the same material as the outermost layer 31, or it can be formed of a different material.

[0048] It should be noted that the odd-numbered layers, including the outermost layer 31, may use aluminum-doped silicon oxide (Al-SiO2), in which aluminum is doped in silicon oxide, as the main component in any one or all of the layers.

[0049] Even-numbered layers after the fourth layer, for example Figure 1 The fourth layer 34 is a high refractive index layer, which can be formed of the same material as the second layer 32, such as niobium oxide as the main component, or it can be formed of a different material than the second layer 32.

[0050] Examples of methods for forming the anti-reflective layer 3 include pulse sputtering, AC sputtering, and digital sputtering.

[0051] The CuAlO2 layer 4, which constitutes the outermost functional layer 10, is composed of CuAlO2 compounds as antiviral materials, giving the laminate 1 antiviral properties.

[0052] It is assumed that the CuAlO2 layer 4 is disposed on the outermost layer 31 of the antireflective layer 3, not covering the entire outermost layer 31 of the antireflective layer 3, but exposing a portion of the outermost layer 31. "The CuAlO2 layer 4 is disposed on the outermost layer 31, exposing a portion of the outermost layer 31" means that there are areas on the outermost layer 31 where the CuAlO2 layer 4 is not disposed. That is, it is presumed that the CuAlO2 layer 4 is disposed with multiple holes penetrating the CuAlO2 layer 4. It should be noted that in... Figure 1 Although the diagram shows the portion of the CuAlO2 layer 4 with its exposed outermost layer 31 arranged in a regular manner, it is presumed that the actual arrangement is irregular.

[0053] As described above, in order to expose a portion of the outermost layer 31, the thickness of the CuAlO2 layer 4 is preferably 2 nm to 30 nm, more preferably 5 nm to 15 nm. If the thickness of the CuAlO2 layer 4 is less than 2 nm, there is a risk that the antiviral performance cannot be fully utilized. On the other hand, if the thickness of the CuAlO2 layer 4 is less than 30 nm, a portion of the outermost layer 31 can be appropriately exposed, and even if the CuAlO2 layer 4 is a high-refractive-index layer, the low-reflectivity performance of the laminate 1 can be maintained, which is also preferable.

[0054] The thickness of CuAlO2 layer 4 is the average of the thicknesses at the three points with the greatest thickness in the field of view when the thickness of CuAlO2 layer 4 is measured using SEM (Scanning Electron Microscope) at a magnification of 100,000x.

[0055] As a method for forming the CuAlO2 layer 4, a vacuum dry coating method can be exemplified. Examples of dry coating methods include magnetron sputtering, vacuum evaporation, ion beam assisted evaporation, and ion beam sputtering.

[0056] In magnetron sputtering, for example, a CuAlO2 layer can be formed by any of the following methods A to C.

[0057] Method A: Introducing oxygen and argon using Cu and Al targets

[0058] Method B: Introducing oxygen and argon using a Cu-Al mixed target

[0059] Method C: Introducing argon gas using a Cu-Al oxide target

[0060] The following is a detailed explanation of methods A through C.

[0061] (Method A)

[0062] A glass substrate 2 is placed inside the chamber of a magnetron sputtering apparatus equipped with Cu and Al targets, and vacuum exhaust is performed until the pressure reaches 5.0 × 10⁻⁶. －4 Pa or less. Then, the glass substrate 2 can be heated in an atmosphere of 200°C to 500°C and maintained in this heated state.

[0063] After heating, the pressure inside the chamber rises, so further venting continues until the pressure inside the chamber reaches 5.0 × 10⁻⁶. －4 Below Pa. At this point, the Cu target and Al target can be configured in the same region or separately in different regions.

[0064] After heating and vacuum degassing, oxygen and argon are introduced into the chamber, and a pulsed DC voltage is applied to each target to generate plasma. Then, a CuAlO2 layer 4 is formed on the glass substrate 2 being transported within the chamber by magnetron sputtering. The applied power to each target is adjusted to achieve the desired composition of the CuAlO2 layer 4. The applied voltage can be DC, RF, or AC (bipolar alternating current). The Cu target can be a copper oxide. Alternatively, the Al target can be an Al oxide. RF is selected as the power source when the target material has high resistance.

[0065] The glass substrate 2 with the CuAlO2 layer 4 formed can be removed from the chamber and heated at atmospheric pressure at a temperature of 200℃ to 500℃ for 5 minutes to 120 minutes. To adjust the crystallinity of the CuAlO2 layer 4, the glass substrate 2 can be further heated under different conditions than the first heating.

[0066] (Method B)

[0067] A Cu-Al mixed target is used instead of a Cu target and an Al target. Furthermore, a CuAlO2 layer 4 is formed on the glass substrate 2 using the same method as in Method A. (Method C)

[0068] A Cu-Al oxide target is used instead of a Cu target and an Al target, and the introduced gas is argon instead of a mixture of oxygen and argon. In addition, a CuAlO2 layer 4 is formed on the glass substrate 2 by the same method as in method A.

[0069] The antifouling layer 5, which constitutes the outermost functional layer 10, imparts antifouling properties to the laminate 1. Antifouling properties refer to the ability to inhibit the adhesion of organic or inorganic substances, or the ability to easily remove the adhered substances by wiping or other cleaning methods even when organic or inorganic substances are adhered.

[0070] The antifouling layer 5 is disposed on the outermost layer 31 of the antireflective layer 3 to fill the portion of the outermost layer 31 exposed from the CuAlO2 layer 4, and does not cover the entire surface of the CuAlO2 layer 4. That is, the antifouling layer 5 is disposed in direct contact with the CuAlO2 layer 4 and is fixed to the glass substrate 2 via the antireflective layer 3.

[0071] The target thickness of the antifouling layer 5 is preferably 1 to 10 nm, more preferably 2 to 5 nm.

[0072] The antifouling layer 5 is preferably a layer formed using a compound having an alkoxysilyl group. That is, the antifouling layer 5 is preferably composed of a cured product of an organic compound having an alkoxysilyl group.

[0073] As a method for forming the antifouling layer 5, examples include coating a composition containing a compound having an alkoxysilyl group onto the CuAlO2 layer 4 by spin coating, dip coating, casting, slot coating or spraying, and then performing heat treatment as needed; or vapor-depositing a compound having an alkoxysilyl group onto the CuAlO2 layer 4 and then performing heat treatment as needed.

[0074] Furthermore, compounds containing alkoxysilyl groups can be fluorinated organosilicon compounds. Fluorinated organosilicon compounds can be silane coupling agents containing perfluoroalkyl groups; or fluoroalkyl groups containing perfluoro(polyoxyalkylene) chains. Moreover, compounds containing alkoxysilyl groups can be organosilicon compounds containing alkyl groups.

[0075] When antifouling layer 5 is formed using fluorinated hydrolyzable silicon compounds such as fluorinated organosilicon compounds, it is formed through a hydrolysis-condensation reaction as follows, and possesses water-repellent and oil-repellent properties. Fluorinated hydrolyzable silicon compounds refer to compounds having hydrolyzable silane groups formed by bonds between hydrolyzable groups or atoms and silicon atoms, and further having fluorinated organic groups bonded to the silicon atoms. It should be noted that the hydrolyzable groups or atoms bonded to the aforementioned silicon atoms to form hydrolyzable silane groups are collectively referred to as "hydrolyzable groups."

[0076] That is, the hydrolyzable silane groups of the fluorinated hydrolyzable silicon compound hydrolyze to become silanol groups, which then undergo intermolecular dehydration condensation to form siloxane bonds represented by -Si-O-Si-, forming a fluorinated organosilicon compound coating. In the fluorinated organosilicon compound coating, most of the fluorinated organic groups bonded to the silicon atoms of the siloxane bonds are located near the surface of the coating on the side of the antireflective layer 3. Through the action of these fluorinated organic groups, water-repellent and oil-repellent properties are exhibited. At this time, the silanol groups chemically bond with the hydroxyl groups of the outermost layer 31, which is mainly composed of silicon oxide, through a dehydration condensation reaction, forming points bonded by siloxane bonds. In this way, the antifouling layer 5 is firmly fixed to the glass substrate 2 in the laminate 1 via the antireflective layer 3, thus the laminate 1 has excellent antifouling properties.

[0077] Similarly, when using an organosilicon compound to form the antifouling layer 5, the hydrolyzable silyl group of the organosilicon compound is hydrolyzed to become a silanol group. Then, the silanol group is chemically bonded to the hydroxyl group of the outermost layer 31 through a dehydration condensation reaction, and the antifouling layer 5 is firmly fixed to the glass substrate 2 via the antireflective layer 3.

[0078] The surface resistivity of the outermost surface of the first main surface 21 side of the laminate 1, i.e., the outermost surface of the outermost functional layer 10, is 1.0 × 10⁻⁶. 12 Ω / cm 2 The preferred value is 1.0 × 10⁴. 13Ω / cm 2 The above is true. Since CuAlO2 is conductive, given that the laminate 1 has this surface resistivity, it can be assumed that the CuAlO2 layer 4 is configured to not completely cover the outermost layer 31 of the antireflective layer 3, but rather expose a portion of the outermost layer 31. Furthermore, it can be assumed that the antifouling layer 5, which buries the portion of the outermost layer 31 exposed from the CuAlO2 layer 4, is firmly fixed to the outermost layer 31 while maintaining its antifouling performance. It should be noted that the surface resistivity of the outermost surface of the outermost functional layer 10 is preferably 1.0 × 10⁻⁶. 15 Ω / cm 2 the following.

[0079] The laminate 1 with the above composition can take into account both antiviral and antifouling properties.

[0080] As mentioned above, the thickness of CuAlO2 layer 4 is greater than 2 nm. Therefore, it can be inferred that the laminate 1 possesses sufficient antiviral properties.

[0081] Alternatively, the antiviral activity value of the outermost functional layer 10 of the laminate 1 is greater than 2.0 when subjected to an antiviral performance evaluation test as specified in ISO 21702 (established in 2019) for 1 hour. Because the laminate 1 possesses this characteristic, and the antifouling layer 5 is configured not to cover the entire surface of the CuAlO2 layer 4, it can be presumed that the laminate 1 is endowed with sufficient antiviral properties.

[0082] The laminate 1 with the above-described structure can possess both antiviral and antifouling properties. It should be noted that it is more preferable to satisfy both the characteristics of the thickness of the CuAlO2 layer 4 and the characteristics of the antiviral activity value described above.

[0083] The water contact angle of the outermost functional layer 10 of the laminate 1 is preferably 75° or more. The water contact angle is the angle of contact with water when, for example, residual uncured components have been removed from the antifouling layer of the outermost functional layer 10 using alcohol or the like. Because the laminate 1 has such a contact angle, it can be assumed that the antifouling layer 5 is firmly fixed to the outermost layer 31 in a state where it possesses functional groups sufficient to perform antifouling functions; that is, it can be assumed that it has sufficient thickness and is in a coarse-dense state. The water contact angle of the outermost functional layer 10 of the laminate 1 is more preferably 90° or more, and even more preferably 100° or more.

[0084] The visual reflectance of the laminate 1 when viewed from the outermost functional layer 10 side is preferably 3.0% or less. By using such a laminate 1 as the glass cover of the display device, glare caused by light reflection can be reduced, and the visual resolution of the display device can be improved. The visual reflectance of the laminate 1 when viewed from the outermost functional layer 10 side is more preferably 1.0% or less.

[0085] The visible light transmittance of the laminate 1 when viewed from the outermost functional layer 10 side is preferably 85.0% or more. By using such a laminate 1 as a glass cover for the display device, the transmittance of light from the display device can be improved, thereby enhancing the visual discernibility of the display device. More preferably, the visible light transmittance of the laminate 1 when viewed from the outermost functional layer 10 side is 90% or more.

[0086] It should be explained that, for example Figure 1 As shown by the double-dotted line, a printed layer 6 can be provided at the periphery of the second main surface 22 of the glass substrate 2. For example, in order to improve the visual recognition and aesthetics of the display, the printed layer 6 is provided in a way that covers the wiring circuits disposed near the outer periphery of the display device, or the bonding part between the housing of the display device and the laminate 1.

[0087] <Examples of Applications of Laminated Structures>

[0088] The laminate 1 having the above-described structure can be applied to the glass cover of a display device.

[0089] For example, Figure 2 As shown, the laminate 1 can be configured to cover the display surface 92 of the display 91 of the vehicle 9. In this case, the laminate 1 has its second main surface 22 attached to the display surface 92 with the first main surface 21 facing the driver. The laminate 1 and the display 91 together constitute an in-vehicle display device 90.

[0090] It should be noted that the display device having the laminate 1 as a glass cover can be a portable or device-type terminal device, a display or touch panel of a home appliance, various machines, etc. Furthermore, the laminate 1 can serve as a glass cover for a frame. Additionally, when the laminate 1 is used for applications where transmission functionality is not required, the glass substrate 2 can be opaque.

[0091] [Variation Example]

[0092] The embodiments of the present invention have been described in detail above with reference to the accompanying drawings. However, the specific configuration is not limited to these embodiments, and various modifications and design changes that do not depart from the spirit of the present invention are also included in the present invention.

[0093] It should be noted that in the following variations, the same names and symbols are used for components that are the same as those in the above embodiments, and the descriptions are simplified or omitted.

[0094] <First Variation>

[0095] The first modified example of the laminate 1A is as follows: Figure 3A The membrane 2A shown is used as the substrate instead of the glass substrate 2, but otherwise has the same structure as the laminate 1 in the embodiment.

[0096] Film 2A is, for example, a transparent and deformable or non-deformable substrate made of an organic resin. Examples of organic resins include polycarbonate, acrylic acid, polyethylene, polypropylene, polyethylene terephthalate, etc. It should be noted that film 2A can be opaque, not limited to a flat sheet, and can have curvature over its entire surface or a portion thereof.

[0097] <Second Variation>

[0098] The second variation of the laminate 1B is as follows: Figure 3B The anti-glare film 2B shown is used as the substrate instead of the glass substrate 2, but otherwise has the same structure as the laminate 1 in the embodiment.

[0099] Preferably, the first main surface 21B of the anti-glare film 2B has an uneven surface. Because the first main surface 21B of the anti-glare film 2B has an uneven surface, the haze value increases due to external scattering, thus imparting anti-glare properties. The uneven surface of the anti-glare film 2B can be formed, for example, by coating a hard coating containing particles onto the surface of a transparent and deformable or non-deformable film substrate made of organic resin. The anti-glare film 2B can be formed from a composition containing particles that act as a scattering source in a transparent resin. In this case, the haze value of the anti-glare film 2B increases due to internal scattering, thus imparting anti-glare properties. It should be noted that the anti-glare film 2B can be opaque, not limited to a flat plate, and can have curvature over its entire surface or a portion thereof.

[0100] <Third Variation>

[0101] The third variation of the laminate 1C is as follows: Figure 4A The anti-glare layer 7, which imparts anti-glare properties to the laminate 1C, is disposed between the glass substrate 2 and the anti-reflective layer 3. Apart from this, it has the same structure as the laminate 1 in the embodiment.

[0102] The anti-glare layer 7 has an uneven surface on the side of the anti-reflective layer 3. The uneven shape is formed, for example, by performing a chemical or physical surface treatment on the first main surface 21 of the glass substrate 2.

[0103] <Fourth Variation>

[0104] The fourth variation of the stacked body 1D is as follows Figure 4B The anti-glare layer 7A, which imparts anti-glare properties to the laminate 1D, is disposed between the film 2A and the anti-reflective layer 3. Apart from this, it has the same structure as the laminate 1A in the first modified example.

[0105] The anti-glare layer 7A has irregularities on the surface of the anti-reflective layer 3. The irregularity shape is formed, for example, by chemically or physically surface-treating the first main surface 21A of the film 2A. This irregularity increases the haze value due to external scattering, thus providing anti-glare properties. The anti-glare layer 7A can also be formed by including particles that act as scattering sources on the first main surface 21A of the film 2A. In this case, the haze value of the anti-glare layer 7A increases due to internal scattering, thus providing anti-glare properties.

[0106] <Fifth Variation>

[0107] The fifth variation of the laminate 1E is as follows Figure 5A The laminate shown does not have the anti-reflective layer 3, but otherwise has the same structure as the laminate 1C in the third variation. In the laminate 1E, a CuAlO2 layer 4 and an anti-fouling layer 5 are formed on the anti-glare layer 7, which is mainly composed of silicon oxide, just like the outermost layer 31. Therefore, the anti-fouling layer 5 is firmly fixed to the anti-glare layer 7.

[0108] <Sixth Variation>

[0109] The sixth variation of the laminate 1F is as follows Figure 5B The one shown does not have the anti-reflective layer 3, but otherwise has the same structure as the laminate 1D of the fourth modified example.

[0110] <Seventh Variation>

[0111] The seventh variation of the laminate 1G is as follows Figure 6A The sealing layer 8 is provided instead of the anti-reflective layer 3, and otherwise has the same structure as the laminate 1C of the third modified example.

[0112] The outermost layer of the sealing layer 8, that is, the layer in contact with the outermost functional layer 10, is also composed of a silicon oxide layer with silicon oxide as the main component, just like the outermost layer 31. Therefore, the antifouling layer 5 is firmly fixed to the sealing layer 8.

[0113] <Eighth Variation>

[0114] The eighth variation of the laminate 1H is as follows Figure 6B The adhesive layer 8 is shown as replacing the anti-reflective layer 3, but otherwise has the same structure as the laminate 1D in the fourth modified example. In this case, the outermost layer of the adhesive layer 8, i.e., the layer in contact with the outermost functional layer 10, can be composed of a silicon oxide layer, primarily composed of silicon oxide, just like the outermost layer 31. Alternatively, the adhesive layer 8 can be a silicon oxide-based film formed on the film 2A by a dry coating method.

[0115] <Ninth Variation Example>

[0116] The ninth variation of the laminate 1J is as follows Figure 7AThe laminate shown does not have the anti-reflective layer 3, but otherwise has the same structure as the laminate 1 of the embodiment. In the laminate 1J, a CuAlO2 layer 4 and an anti-fouling layer 5 are formed on a glass substrate 2, which is mainly composed of silicon oxide, just like the outermost layer 31. Therefore, the anti-fouling layer 5 is firmly fixed to the glass substrate 2.

[0117] <Tenth Variation>

[0118] The tenth variation of the laminate 1K is as follows Figure 7B The model shown does not have the anti-reflective layer 3, but otherwise has the same structure as the laminate 1A in the first modified example. In this case, in order to firmly fix the antifouling layer 5 to the membrane 2A, the outermost layer of the membrane 2A can be subjected to plasma treatment.

[0119] <Eleventh Variation>

[0120] The eleventh variation of the laminate 1L is as follows: Figure 7C The model shown does not have the anti-reflective layer 3, but otherwise has the same structure as the laminate 1B in the second modified example. In this case, in order to firmly fix the anti-fouling layer 5 to the anti-glare film 2B, the outermost layer of the anti-glare film 2B can be subjected to plasma treatment.

[0121] <Twelfth Variation Example>

[0122] The twelfth variation, the laminate 1M, is as follows: Figure 8A The sealing layer 8 is provided instead of the anti-reflective layer 3, but otherwise it has the same structure as the laminate 1 in the embodiment.

[0123] <Thirteenth Variation Example>

[0124] The thirteenth variation of the laminate 1N is as follows: Figure 8B The shown example has a sealing layer 8 instead of an anti-reflective layer 3, but otherwise has the same structure as the laminate 1A of the first modified example.

[0125] <Example 14>

[0126] The fourteenth variation, the laminate 1P, is as follows: Figure 8C The sealing layer 8 is provided instead of the anti-reflective layer 3, and otherwise has the same structure as the laminate 1B of the second modified example.

[0127] <Application Examples of the First to Fourteenth Variations>

[0128] Laminates 1C, 1E, 1G, 1J, and 1M having a glass substrate 2 can be used for the same purposes as laminate 1 in the embodiment.

[0129] The laminates 1A, 1D, 1F, 1H, 1K, and 1N containing film 2A and the laminates 1B, 1L, and 1P containing anti-glare film 2B, when film 2A or anti-glare film 2B is transparent, can be bonded to displays or touch panels, glass covers for frames, and door panels of vehicles in portable or installation-type terminal devices, home appliances, and various machines. When film 2A or anti-glare film 2B is opaque, it can be bonded to door panels of vehicles for applications where transmission functionality is not required.

[0130] Example

[0131] Next, embodiments of the present invention will be described. Examples 1 and 6 are comparative examples, and Examples 2 to 5 are exemplary examples. It should be noted that the present invention is not limited to the embodiments.

[0132] [Creating Layered Objects]

[0133] The laminates shown in Examples 1 to 6 below, like the laminate 1 of Embodiment 1, include a glass substrate, an anti-reflective layer, and an outermost functional layer composed of a CuAlO2 layer and an anti-fouling layer. The anti-reflective layer has a laminate structure consisting of two alternating layers of low-refractive-index and high-refractive-index layers. As shown in Table 1, the main component of the high-refractive-index layers, corresponding to the fourth layer 34 and the second layer 32, is niobium oxide. The main component of the low-refractive-index layers, corresponding to the third layer 33 and the outermost layer 31, is silicon oxide.

[0134] In fabricating the laminates of Examples 1 to 6, a chemically strengthened glass (manufactured by AGC Corporation, trade name: Dragontrail (registered trademark)) with an aluminosilicate glass substrate was prepared as the glass substrate. The glass substrate had dimensions of 100mm × 100mm and a thickness of 1.0mm.

[0135] The following details the fabrication methods for each layer.

[0136] <Example 1>

[0137] An antireflective layer, as shown in Table 1, is formed on the first main surface of a glass substrate by sputtering. First, a high refractive index layer with a thickness of 11.0 nm is formed on the glass substrate as layer 34, corresponding to the fourth layer. Next, a low refractive index layer with a thickness of 37.6 nm is formed as layer 33, corresponding to the third layer. Next, a high refractive index layer with a thickness of 107.8 nm is formed as layer 32, corresponding to the second layer. Finally, a low refractive index layer with a thickness of 82.5 nm is formed as layer 31, corresponding to the outermost layer.

[0138] The thickness of each layer constituting the anti-reflective layer was measured by cross-sectional observation using SEM.

[0139] Then, a CuAlO2 layer with a thickness of 1 nm, as shown in Table 2, is formed on the antireflective layer. The CuAlO2 layer is formed using the method described above, C, with a Cu-Al oxide target and argon gas.

[0140] The thickness of the CuAlO2 layer was measured using SEM at a magnification of 100,000x. The average thickness of the CuAlO2 layer was then calculated as the average of the thicknesses at the three points with the greatest thickness within the field of view.

[0141] Finally, a fluorinated organic compound (manufactured by AGC Corporation, Afluid (registered trademark) S550), which serves as the composition for forming the antifouling layer, is sprayed onto the CuAlO2 layer and dried at 120°C for 20 minutes to form the antifouling layer. Then, the residual uncured components on the outermost surface are wiped away with a cloth containing ethanol to complete the antifouling layer. The target thickness of the antifouling layer is 4 nm.

[0142] <Example 2>

[0143] An antireflective layer, constituting B as shown in Table 1, is formed on the first main surface of the glass substrate. Layers with thicknesses of 11.0 nm, 35.6 nm, 106.8 nm, and 71.5 nm are formed using the same method as in Example 1, serving as layers corresponding to the fourth layer 34, the third layer 33, the second layer 32, and the outermost layer 31, respectively.

[0144] Then, a CuAlO2 layer with a thickness of 5 nm, as shown in Table 2, was formed on the antireflective layer using the same method as in Example 1.

[0145] Finally, the antifouling layer is formed using the same method as in Example 1. The target thickness of the antifouling layer is 4 nm.

[0146] <Example 3>

[0147] An antireflective layer, constituting C as shown in Table 1, is formed on the first main surface of the glass substrate. Layers with thicknesses of 12.0 nm, 34.6 nm, 112.8 nm, and 64.5 nm are formed using the same method as in Example 1, serving as layers corresponding to the fourth layer 34, the third layer 33, the second layer 32, and the outermost layer 31, respectively.

[0148] Then, a CuAlO2 layer with a thickness of 10 nm, as shown in Table 2, was formed on the antireflective layer using the same method as in Example 1.

[0149] Finally, the antifouling layer is formed using the same method as in Example 1. The target thickness of the antifouling layer is 4 nm.

[0150] <Example 4>

[0151] An antireflective layer, constituting D as shown in Table 1, is formed on the first main surface of the glass substrate. Layers with thicknesses of 18.0 nm, 34.6 nm, 127.8 nm, and 58.5 nm are formed using the same method as in Example 1, serving as layers corresponding to the fourth layer 34, the third layer 33, the second layer 32, and the outermost layer 31, respectively.

[0152] Then, a CuAlO2 layer with a thickness of 15 nm, as shown in Table 2, was formed on the antireflective layer using the same method as in Example 1.

[0153] Finally, the antifouling layer is formed using the same method as in Example 1. The target thickness of the antifouling layer is 4 nm.

[0154] <Example 5>

[0155] An antireflective layer constituting A is formed on the first main surface of the glass substrate using the same method as in Example 1.

[0156] Then, a CuAlO2 layer with a thickness of 30 nm, as shown in Table 2, was formed on the antireflective layer using the same method as in Example 1.

[0157] Finally, the antifouling layer is formed using the same method as in Example 1. The target thickness of the antifouling layer is 4 nm.

[0158] <Example 6>

[0159] An antireflective layer constituting A is formed on the first main surface of the glass substrate using the same method as in Example 1.

[0160] Then, a CuAlO2 layer with a thickness of 50 nm, as shown in Table 2, was formed on the antireflective layer using the same method as in Example 1.

[0161] Finally, the antifouling layer is formed using the same method as in Example 1. The target thickness of the antifouling layer is 4 nm.

[0162] [Evaluation] <Visible Light Transmittance>

[0163] The visible light transmittance of the laminates in Examples 1 to 6 was measured according to JIS R3106:1998.

[0164] The visible light transmittance of the laminates in Examples 1 to 6 are 95.0%, 94.3%, 92.4%, 91.5%, 87.5%, and 83.4%, respectively.

[0165] <Visual reflectance>

[0166] The visual reflectance of the laminates of Examples 1 to 6 was measured when viewed from the first principal surface side.

[0167] First, a black PET film (TOMOEGAWA CORPORATION, trade name: Kukkiri Mieru) was attached to the second main surface of the laminate in Example 1, i.e., the main surface without an anti-reflective layer. Then, using a spectrophotometer (Konica Minolta, model: CM-2600d), the spectral reflectance was measured in SCI mode. Based on this spectral reflectance, the stimulus value Y of the reflectance specified in JIS Z8701 was calculated as the visual reflectance. The visual reflectance was 0.16%.

[0168] The visual reflectance of the laminates in Examples 2-6 was measured using the same method as that used for the laminate in Example 1. The visual reflectances of the laminates in Examples 2-6 were 0.22%, 0.56%, 0.82%, 2.90%, and 4.90%, respectively.

[0169] <Surface resistivity>

[0170] The surface resistivity of the first main surface of the laminates in Examples 1 to 6 was measured according to JIS K6911.

[0171] First, a flat sample electrode (manufactured by HIOKI Electric Co., Ltd., model: SM-8220) was mounted on a superinsulation tester (manufactured by HIOKI Electric Co., Ltd., model: SME-8311). Then, a voltage of 1000V was applied to the laminate of Example 1 at an environment of 22±2℃ and 45±10% humidity, and the surface resistivity was measured. The surface resistivity exceeded 1.0×10⁻⁶. 14 Ω / cm 2 .

[0172] The surface resistivity of the laminates in Examples 2-6 was measured using the same method as that used for the laminate in Example 1. The surface resistivity of the laminates in Examples 2-5 all exceeded 1.0 × 10⁻⁶. 12 Ω / cm 2 On the other hand, the surface resistivity of the laminate in Example 6 is 7.3 × 10⁻⁶. 11 Ω / cm 2 .

[0173] <Initial water contact angle>

[0174] The initial water contact angle of the outermost functional layer of the laminates in Examples 1 to 6 was measured.

[0175] First, the laminate from Example 1 was placed on a contact angle meter (manufactured by Kyowa Interface Science Co., Ltd., model: CA-X150). Then, a water droplet with a diameter of 1 mm was dropped onto the outermost functional layer, and the contact angle of the water droplet was measured. The contact angle of the water droplet was measured at 5 locations on the outermost functional layer, and the average value of the measured results was calculated as the initial water contact angle. The initial water contact angle was 116°.

[0176] The initial water contact angles of the laminates in Examples 2 to 6 were determined using the same method as that used for the laminate in Example 1. The initial water contact angles of the laminates in Examples 2 to 6 were 116°, 116°, 116°, 95°, and 70°, respectively.

[0177] <Antiviral activity value>

[0178] The antiviral activity values ​​of the laminates in Examples 1 to 6 were determined by the antiviral performance evaluation test specified in ISO 21702 (established in 2019).

[0179] First, a 50mm × 50mm test piece was cut from the laminate of Example 1 as a processed test piece. Additionally, a 50mm × 50mm test piece was prepared as an unprocessed test piece, consisting only of a glass substrate with the same composition as the glass substrate of the laminate of Example 1.

[0180] Next, 4 ml of viral solution (phage Φ6, host Pseudomonas syringae (NBRC14084)) was dropped onto the outermost functional layer of the processed test strip and covered with a 40 mm × 40 mm polypropylene membrane (manufactured by KOKUYO Co., Ltd., trade number: VF-10). Additionally, 4 ml of viral solution was dropped onto one main surface of the unprocessed test strip and covered with a 40 mm × 40 mm membrane.

[0181] Then, the processed and unprocessed test strips were left to stand at 25°C for 1 hour to wash away the virus. The viral infection titers (PFU / cm³) of the processed and unprocessed test strips were then measured. 2 The antiviral activity value is calculated based on the following formula (1).

[0182] R = Ut - At … (1)

[0183] R: Antiviral activity value

[0184] Ut: The common logarithmic mean of the viral infection titer of an unprocessed test strip after standing for 1 hour.

[0185] At: The average of the common logarithm of the viral infection titer after the processed test strip has stood for 1 hour.

[0186] In the antiviral performance evaluation test, if the antiviral activity value is above 2.0, it is evaluated as exceeding the benchmark. The higher the antiviral activity value, the higher the antiviral performance.

[0187] The antiviral activity of the laminate in Example 1 was 0.7 one hour after the start of the experiment, which was lower than the baseline.

[0188] For the laminate in Example 2, the antiviral activity values ​​were measured 0.25 hours after the start of the test, i.e., 15 minutes after the start of the test, and 1 hour after the start of the test.

[0189] First, prepare two processed test pieces and two unprocessed test pieces, the same as in Example 1.

[0190] For each of the processed and unprocessed test tablets (one tablet each), a standing time of 0.25 hours was applied, followed by the same treatment as in Example 1, and the antiviral activity value after 0.25 hours was calculated. Additionally, for the remaining processed and unprocessed test tablets (one tablet each), the same treatment as in Example 1 was applied, and the antiviral activity value after 1 hour was calculated.

[0191] In Example 2, the antiviral activity value of the laminate was 0.5 0.25 hours after the start of the test, which was lower than the baseline. On the other hand, the antiviral activity value was 2.7 1 hour after the start of the test, which was higher than the baseline.

[0192] For the laminate in Example 3, the same treatment as in Example 2 was performed, and the antiviral activity values ​​were measured 0.25 hours and 1 hour after the start of the test. The antiviral activity value of the laminate in Example 3 was 1.4 0.25 hours after the start of the test, which was lower than the baseline. On the other hand, the antiviral activity value was 3.3 1 hour after the start of the test, which was higher than the baseline.

[0193] For the laminate in Example 4, the same treatment as in Example 1 was performed, and the antiviral activity value was measured one hour after the start of the test. The antiviral activity value of the laminate in Example 4 one hour after the start of the test was 4.0, which is above the baseline.

[0194] For the laminate in Example 5, the same treatment as in Example 1 was performed, and the antiviral activity value was measured one hour after the start of the test. The antiviral activity value of the laminate in Example 5 one hour after the start of the test was 4.0, which is above the baseline.

[0195] For the laminate of Example 6, the same treatment as in Example 1 was performed, and the antiviral activity value was measured 1 hour after the start of the test. The antiviral activity value of the laminate of Example 6 1 hour after the start of the test was 4.0, which is above the baseline.

[0196]

[0197]

[0198] [Inspection]

[0199] (Examination 1)

[0200] The visible light transmittance of the laminates in Examples 1 to 4 is over 90%, the visible light transmittance of the laminate in Example 5 is 87.5%, and the visible light transmittance of the laminate in Example 6 is 83.4%.

[0201] In addition, the visual reflectance of the laminates in Examples 1-4 is less than 1%, the visual reflectance of the laminate in Example 5 is 2.90%, and the visual reflectance of the laminate in Example 6 is 4.90%.

[0202] The reason for this inference is that in the laminate of Example 5, the thickness of the CuAlO2 layer, which is the high refractive index layer, is 30 nm, and in the laminate of Example 6, the thickness of the CuAlO2 layer is 50 nm, which is the thickness of the laminates of Examples 1 to 4.

[0203] (Examination 2)

[0204] The surface resistivity of the laminates in Examples 1-4 exceeds 1.0 × 10⁻⁶. 14 Ω / cm 2 The surface resistivity of the laminate in Example 5 is 1.0 × 10⁻⁶. 13 Ω / cm 2 On the other hand, the surface resistivity of the laminate in Example 6 is 7.3 × 10⁻⁶. 11 Ω / cm 2 .

[0205] The reason for this can be inferred is that in the laminates of Examples 1 to 5, the thickness of the CuAlO2 layer is less than 30 nm, the laminate of Example 6 is thinner, and the portion of the anti-reflective layer exposed from the CuAlO2 layer in Example 6 is larger, thus enabling the formation of a sufficiently large anti-fouling layer.

[0206] (Examination 3)

[0207] The initial water contact angle of the laminates in Examples 1-4 is 116°, the initial water contact angle of the laminate in Example 5 is 95°, and the initial water contact angle of the laminate in Example 6 is 70°. That is, the antifouling performance of the laminates in Examples 1-5 is higher than that of the laminate in Example 6.

[0208] The reason for this can be inferred is that, in the laminates of Examples 1 to 5, as shown in Examination 2, the laminate with the portion of the antireflective layer 3 exposed from the CuAlO2 layer being of a large proportion 6, the laminate with the outermost layer of the antireflective layer, which is mainly composed of silicon oxide, being firmly bonded to the antifouling layer in a fixed proportion 6, and the laminate with a large amount of fluorine constituting the antifouling layer being of a large proportion 6.

[0209] (Examination 4)

[0210] The antiviral activity value of the laminate in Example 1 was 0.7 one hour after the start of the test, which was lower than the baseline. On the other hand, the antiviral activity value of the laminates in Examples 2 to 6 was 2.7 or higher, which was higher than the baseline. In addition, in the laminates in Examples 2 to 6, it can be confirmed that the antiviral activity value was 2.0 or higher one hour after the start of the test, and it can exceed the baseline in a very short time from the start of the test.

[0211] The reason why the antiviral activity values ​​of the laminate in Example 1 differ from those in Examples 2-6 as described above is that, in the laminate of Example 1, the thickness of the CuAlO2 layer is 1 nm, while the laminates in Examples 2-6 are significantly thinner, not thick enough to obtain sufficient antiviral performance. On the other hand, in the laminates of Examples 2-6, it can be presumed that sufficient antiviral performance is obtained because the antifouling layer is designed not to cover the entire surface of the CuAlO2 layer.

[0212] It should be noted that, based on the results of Examples 1 to 6, if the thickness of the CuAlO2 layer exceeds 1 nm, the antiviral activity value increases after 1 hour from the start of the test; if the thickness of the CuAlO2 layer is 2 nm or more, the antiviral activity value is 2.0 or more after 1 hour from the start of the test, which is higher than the baseline.

[0213] (Summary of the investigation)

[0214] As confirmed by examinations 2-4, in a laminate containing a CuAlO2 layer and an antifouling layer on the substrate, the thickness of the CuAlO2 layer should be greater than 2 nm, and the surface resistivity should be 1.0 × 10⁻⁶. 12 Ω / cm 2 Therefore, it possesses both antiviral and antifouling properties.

[0215] Furthermore, as confirmed by examinations 1-4, in a laminate containing an anti-reflective layer, a CuAlO2 layer, and an antifouling layer on a substrate, further reducing the thickness of the CuAlO2 layer to below 30 nm not only achieves sufficient antiviral and antifouling properties, but also achieves suitable reductions in visible light transmittance and reflectance.

[0216] The invention has been described in detail with reference to specific embodiments, but it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.

[0217] This application is based on Japanese Patent Application No. 2024-046935, filed on March 22, 2024, the contents of which are incorporated herein by reference.

[0218] Symbol Explanation

[0219] 1, 1A, 1B, 1C, 1D, 1E, 1F, 1G, 1H, 1J, 1K, 1L, 1M, 1N, 1P…Laminated body, 2…Glass substrate (substrate), 2A…Film (substrate), 2B…Anti-glare film (substrate), 3…Anti-reflective layer, 4…CuAlO2 layer, 5…Anti-fouling layer, 7, 7A…Anti-glare layer, 21, 21A, 21B…First main surface, 22…Second main surface, 90…Vehicle display device (display device).

Claims

1. A laminated body, comprising: A substrate having a first principal surface and a second principal surface, and The CuAlO2 layer and the antifouling layer are disposed on the first main surface side of the substrate. The CuAlO2 layer and the antifouling layer are formed on the outermost surface of the first main surface side in a state of mutual contact. The thickness of the CuAlO2 layer is greater than 2 nm. The surface resistivity of the outermost surface on the first main surface side is 1.0 × 10⁻⁶. 12 Ω / cm 2 above.

2. The laminated body according to claim 1, wherein, The thickness of the CuAlO2 layer is less than 30 nm.

3. A layered body, comprising: A substrate having a first principal surface and a second principal surface, and The CuAlO2 layer and the antifouling layer are disposed on the first main surface side of the substrate. The CuAlO2 layer and the antifouling layer are formed on the outermost surface of the first main surface side in a state of mutual contact. The surface resistivity of the outermost surface on the first main surface side is 1.0 × 10⁻⁶. 12 Ω / cm 2 above, The antiviral activity value of the outermost surface of the first main surface side is greater than 2.0 when subjected to an antiviral performance evaluation test as specified in ISO 21702 for 1 hour.

4. The laminate according to any one of claims 1 to 3, wherein, The antifouling layer is composed of a cured product of an organic compound having an alkoxysilyl group.

5. The laminated body according to claim 4, wherein, At least a portion of the antifouling layer is in direct contact with the surface, which is mainly composed of silicon dioxide.

6. The laminate according to any one of claims 1 to 3, wherein, The water contact angle is 75° or higher.

7. The laminate according to any one of claims 1 to 3, wherein, The visual reflectance is below 3.0%.

8. The laminate according to any one of claims 1 to 3, wherein, Visible light transmittance is above 85.0%.

9. The laminate according to any one of claims 1 to 3, wherein, An anti-glare layer is provided between the first main surface and the CuAlO2 layer and the anti-fouling layer.

10. The laminate according to any one of claims 1 to 3, wherein, An anti-reflective layer is provided between the first main surface and the CuAlO2 layer and the anti-fouling layer. The anti-reflective layer has a stacked structure consisting of alternating layers of low refractive index and high refractive index, comprising 1 to 15 layers of low refractive index layers and the same number of high refractive index layers as the low refractive index layers.

11. The laminate according to claim 10, wherein, The main component of the low-refractive-index layer is silicon oxide. The main component of the high refractive index layer is any one of silicon nitride, titanium oxide, niobium oxide, tantalum oxide, and zirconium oxide.

12. The laminate according to any one of claims 1 to 3, wherein, The substrate is a glass substrate.

13. A glass cover sheet comprising the laminate of claim 12.

14. A display device comprising: The glass cover plate as described in claim 13, and monitor, The second main surface side of the glass cover is attached to the display.

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