Laminate, cover glass, and display device

Abstract

The present invention pertains to the provision of a laminate with which it is possible to achieve both antiviral performance and antifouling performance. The present invention pertains to a laminate comprising: a substrate that has a first main surface and a second main surface; and a CuAlO2 layer and an antifouling layer that are provided on the first main surface side of the substrate. The CuAlO2 layer and the antifouling layer are formed on the outermost surface on the first main surface side so as to contact each other. The thickness of the CuAlO2 layer is 2 nm or greater. The surface resistance value of the outermost surface on the first main surface side is 1.0×1012 Ω / cm2 or greater.

Description

Laminate, cover glass, and display device

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

[0002] With the spread of car sharing and other applications, the cover glass of in-vehicle display devices is required to have antiviral properties on the surface of the cover glass. ２ is known (see, for example, Patent Document 1).

[0003] International Publication No. 2022 / 019244

[0004] However, when a metal oxide layer as disclosed in Patent Document 1 is provided on the surface of the cover glass, there is a risk that both antiviral performance and antifouling performance cannot be achieved at the same time.

[0005] An object of the present invention is to provide a laminate, a cover glass, and a display device that can achieve both antiviral performance and antifouling performance.

[0006] The laminate of the first aspect of the present invention includes a substrate having a first main surface and a second main surface, and a CuAlO ２ a CuAlO ２ The CuAlO ２ The thickness of the layer is 2 nm or more, and the surface resistance of the outermost surface on the first principal surface side is 1.0×10 １２ Ω / cm ２ That's all.

[0007] A laminate according to a second aspect of the present invention includes a substrate having a first main surface and a second main surface, and a CuAlO ２ a CuAlO ２ the antifouling layer and the antifouling layer are formed on the outermost surface of the first principal surface side in a state of contact with each other, and the surface resistivity of the outermost surface of the first principal surface side is 1.0×10 １２ Ω / cm ２or more, and when the antiviral performance evaluation test specified in ISO 21702 is performed on the outermost surface on the first principal surface side for one hour, the antiviral activity value is 2.0 or more.

[0008] The cover glass of the present invention comprises the above-described laminate.

[0009] A display device of the present invention includes the above-described cover glass and a display, wherein the second main surface side of the cover glass is bonded to the display.

[0010] According to the present invention, it is possible to provide a laminate, a cover glass, and a display device that can achieve both antiviral performance and antifouling performance.

[0011] FIG. 1 is a cross-sectional view of a laminate according to an embodiment. FIG. 2 is a schematic diagram showing an application example of a laminate according to an embodiment. FIG. 3A is a cross-sectional view of a laminate according to a first modified example. FIG. 3B is a cross-sectional view of a laminate according to a second modified example. FIG. 4A is a cross-sectional view of a laminate according to a third modified example. FIG. 4B is a cross-sectional view of a laminate according to a fourth modified example. FIG. 5A is a cross-sectional view of a laminate according to a fifth modified example. FIG. 5B is a cross-sectional view of a laminate according to a sixth modified example. FIG. 6A is a cross-sectional view of a laminate according to a seventh modified example. FIG. 6B is a cross-sectional view of a laminate according to an eighth modified example. FIG. 7A is a cross-sectional view of a laminate according to a ninth modified example. FIG. 7B is a cross-sectional view of a laminate according to a tenth modified example. FIG. 7C is a cross-sectional view of a laminate according to an eleventh modified example. FIG. 8A is a cross-sectional view of a laminate according to a twelfth modified example. FIG. 8B is a cross-sectional view of a laminate according to a thirteenth modified example. FIG. 8C is a cross-sectional view of a laminate according to a fourteenth modified example.

[0012] [Embodiments] Hereinafter, embodiments of the present invention will be described. Note that, to facilitate understanding of the present invention, the components in the drawings described below may be exaggerated.

[0013] <Structure of Laminate> First, the structure of the laminate will be described. Fig. 1 is a cross-sectional view of a laminate according to one embodiment of the present invention. In Fig. 1, the laminate 1 includes a glass substrate 2 as a substrate. The glass substrate 2 has a first main surface 21 and a second main surface 22 that face each other, and an end surface 23 that connects the first main surface 21 and the second main surface 22. An anti-reflection layer 3 is laminated on the first main surface 21 of the glass substrate 2. A CuAlO ２ The outermost surface functional layer 10 is formed by the layer 4 and the antifouling layer 5 .

[0014] The glass substrate 2 may be made of alkali-free glass, soda-lime glass, soda-lime silicate glass, aluminosilicate glass, borate glass, lithium aluminosilicate glass, borosilicate glass, or the like. ２ O.K. ２ The term "glass substantially free of alkali metal oxides" refers to glass that is substantially free of alkali metal oxides such as O. Here, "substantially free of alkali metal oxides" means that the total content of alkali metal oxides is 0.1% by mass or less. When the laminate 1 is used as a cover glass for a display device, it is preferable to use glass that contains alkali metal oxides. When glass that contains alkali metal oxides is subjected to a chemical strengthening treatment after molding, a compressive stress layer is formed on the glass surface, thereby increasing the strength. The glass substrate 2 is not limited to a flat plate, and may have curvature on the entire surface or on a part thereof.

[0015] The antireflection layer 3 imparts reflectance reduction performance to the laminate 1, reducing glare caused by reflected light. When the laminate 1 is used in a display device, the antireflection layer 3 can improve the transmittance of light from the display device and improve the visibility of the display device. The configuration of the antireflection layer 3 is not particularly limited as long as it is capable of suppressing light reflection. For example, the antireflection layer 3 can be configured by alternately stacking high-refractive index layers having a refractive index of 1.9 or more at a wavelength of 550 nm and low-refractive index layers having a refractive index of 1.6 or less at a wavelength of 550 nm. The number of low-refractive index layers and high-refractive index layers is not limited, but the low-refractive index layers are preferably 1 to 15 layers, more preferably 10 layers or less, even more preferably 6 layers or less, and most preferably 5 layers or less. The high-refractive index layers preferably have the same number of layers as the low-refractive index layers. Note that FIG. 1 illustrates an example in which the low-refractive index layers and high-refractive index layers each consist of two layers.

[0016] When the antireflection layer 3 is composed of multiple low-refractive-index layers and multiple high-refractive-index layers, the layer farthest from the first main surface 21 of the glass substrate 2 is designated as the outermost layer 31. When counting the layers toward the glass substrate 2, starting with the outermost layer 31 as the first layer, the odd-numbered layers including the outermost layer 31 (i.e., the outermost layer 31 and the third layer 33 in FIG. 1 ) are composed of low-refractive-index layers. When the layer adjacent to the outermost layer 31 on the glass substrate 2 side is designated as the second layer 32, the even-numbered layers including the second layer 32 (i.e., the second layer 32 and the fourth layer 34 in FIG. 1 ) are composed of high-refractive-index layers. The high-refractive-index layer farthest from the outermost layer 31 (i.e., the fourth layer 34 in FIG. 1 ) is in contact with the glass substrate 2. The thickness of the antireflection layer 3 is preferably 100 nm or more and 500 nm or less. A thickness of 100 nm or more for the antireflection layer 3 is preferable because it effectively suppresses reflection of external light.

[0017] In this embodiment, the outermost layer 31 is a low refractive index layer and is made of silicon oxide (SiO ２) as a main component. Here, "main component" means that the layer contains that component at a molar ratio of 50% or more, and implies that impurities may be contained in silicon oxide. Since the main component of the outermost layer 31 is silicon oxide, the antifouling layer 5 adheres firmly to the glass substrate 2 via the antireflection layer 3, as will be described later. The thickness of the outermost layer 31 is preferably 1 nm or more and 120 nm or less, and more preferably 3 nm or more and 100 nm or less.

[0018] The second layer 32 is a high refractive index layer. The material of the second layer 32 is not particularly limited, but the main components thereof are silicon nitride (SiN), titanium oxide (TiO ２ ), niobium oxide (Nb ２ O ５ ), tantalum oxide (Ta ２ O ５ ), zirconium oxide (ZrO ２ ) and mixtures thereof. By using these materials, reflection can be effectively prevented even in a film configuration with one low refractive index layer and one high refractive index layer. Furthermore, among these materials, silicon nitride, niobium oxide, tantalum oxide, and mixtures thereof are more preferred from the viewpoints of productivity and refractive index, and niobium oxide is particularly preferred.

[0019] The third and subsequent odd-numbered layers, for example, the third layer 33 in FIG. 1, are low-refractive-index layers and may be made of the same material as the outermost layer 31 or a different material. Note that any one or all of the odd-numbered layers including the outermost layer 31 may be made of aluminum-doped silicon oxide (Al-SiO ２ ) may be used as the main component.

[0020] The fourth and subsequent even-numbered layers, for example, the fourth layer 34 in FIG. 1, are high refractive index layers and may be made of the same material as the second layer 32, for example, a material whose main component is niobium oxide, or may be made of a material different from that of the second layer 32.

[0021] Examples of methods for forming the antireflection layer 3 include sputtering methods such as pulse sputtering, AC sputtering, and digital sputtering.

[0022] CuAlO constituting the outermost surface functional layer 10 ２ Layer 4 is made of CuAlO, an antiviral material. ２ This compound provides antiviral properties to the laminate 1. ２ It is considered that the layer 4 is provided on the outermost layer 31 of the antireflection layer 3 so as not to cover the entire outermost layer 31 of the antireflection layer 3 but to expose a part of the outermost layer 31. ２ The phrase "layer 4 is provided so as to expose a part of the outermost layer 31" means that CuAlO ２ This means that there are areas where the layer 4 is not provided. ２ Layer 4 is CuAlO ２ It is presumed that the layer 4 is provided with a plurality of holes penetrating it. ２ Although the portions of the layer 4 where the outermost layer 31 is exposed are shown as being regularly arranged, it is estimated that they are actually irregularly arranged. ２ In order to provide the layer 4 so as to expose a part of the outermost layer 31, CuAlO ２ The thickness of the layer 4 is preferably 2 nm or more and 30 nm or less, and more preferably 5 nm or more and 15 nm or less. ２ If the thickness of the layer 4 is less than 2 nm, the antiviral performance may not be sufficiently exhibited. ２ If the thickness of the layer 4 is 30 nm or less, a part of the outermost layer 31 can be appropriately exposed, and CuAlO ２ This is also preferable in that the low reflectivity of the laminate 1 can be maintained even if the layer 4 is a high refractive index layer. ２ The thickness of the layer 4 was measured by scanning electron microscope (SEM) at a magnification of 100,000 times. ２ When the thickness of the layer 4 is measured, it is the average value of the thicknesses at the three thickest points within the field of view.

[0023] CuAlO ２The layer 4 can be formed, for example, by a dry coating method using a vacuum. Examples of the dry coating method include magnetron sputtering, vacuum deposition, ion beam assisted deposition, and ion beam sputtering. In the magnetron sputtering method, CuAlO is deposited by, for example, one of the following methods A to C. ２ Layer 4 can be formed by the following methods: Method A: A method in which a Cu target and an Al target are used and oxygen gas and argon gas are introduced; Method B: A method in which a Cu-Al mixed target is used and oxygen gas and argon gas are introduced; Method C: A method in which a Cu-Al oxide target is used and argon gas is introduced. Methods A to C will be described in detail below.

[0024] (Method A) The glass substrate 2 was placed in the chamber of a magnetron sputtering device in which a Cu target and an Al target were placed, and the pressure was 5.0 × 10 －４ The chamber is evacuated to a vacuum of 5.0×10 Pa or less. Thereafter, the glass substrate 2 is heated in an atmosphere of 200° C. to 500° C., and the heated state may be maintained. After heating, the pressure in the chamber increases, so evacuation is continued until the pressure in the chamber reaches 5.0×10 －４ The chamber is evacuated to a vacuum of not more than Pa. At this time, the Cu target and the Al target may be placed in the same zone, or may be placed in separate zones.

[0025] After heating and evacuation, oxygen gas and argon gas are introduced into the chamber, and a pulsed DC voltage is applied to each target to generate plasma. Then, CuAlO is deposited on the glass substrate 2 by magnetron sputtering while it is being transported through the chamber. ２ The power applied to each target is CuAlO ２ The layer 4 is adjusted to have the desired composition. The voltage applied here may be DC, RF, or AC (bipolar alternating current). The Cu target may be copper oxide. The Al target may be aluminum oxide. When the target material has high electrical resistance, RF is selected as the power source. CuAlO ２The glass substrate 2 on which the layer 4 is formed may be removed from the chamber and heated at atmospheric pressure at a temperature of 200° C. or higher and 500° C. or lower for 5 minutes or longer and 120 minutes or shorter. ２ In order to adjust the crystallinity of the layer 4, the glass substrate 2 may be further heated again under conditions different from those used in the first heating.

[0026] (Method B) CuAlO was deposited on the glass substrate 2 in the same manner as Method A, except that a Cu-Al mixed target was used instead of the Cu target and the Al target. ２ (Method C) A CuAlO layer 4 is formed on a glass substrate 2 in the same manner as in Method A, except that a Cu—Al oxide target is used instead of the Cu target and Al target, and argon gas is used as the type of gas introduced instead of a mixed gas of oxygen gas and argon gas. ２ Layer 4 is formed.

[0027] The antifouling layer 5 constituting the outermost surface functional layer 10 imparts antifouling properties to the laminate 1. The antifouling properties are the ability to inhibit adhesion of organic or inorganic substances, or the ability to easily remove the adhesion by cleaning such as wiping even if an organic or inorganic substance does adhere. The antifouling layer 5 is formed on the outermost surface layer 31 of the antireflection layer 3, and is composed of CuAlO ２ The CuAlO ２ The antifouling layer 5 is formed so as not to cover the entire surface of the layer 4. ２ The antifouling layer 5 is provided so as to be in direct contact with the antifouling layer 4, and is fixed to the glass substrate 2 via the antireflection layer 3. The target thickness of the antifouling layer 5 is preferably 1 to 10 nm, more preferably 2 to 5 nm. The antifouling layer 5 is preferably a layer formed using a compound having an alkoxysilyl group. That is, the antifouling layer 5 is preferably made of a cured product of an organic compound having an alkoxysilyl group. The antifouling layer 5 can be formed by a method of curing a composition containing a compound having an alkoxysilyl group with CuAlO ２A method of applying a compound having an alkoxysilyl group to the layer 4 by spin coating, dip coating, casting, slit coating, spray coating, or the like, followed by heat treatment as required, or a method of applying a compound having an alkoxysilyl group to the layer 4 by spin coating, dip coating, casting, slit coating, spray coating, or the like, followed by heat treatment as required, ２ Examples of methods include vapor-depositing the compound on layer 4 and then heat-treating it as needed. The compound having an alkoxysilyl group may also be a fluorine-containing organosilicon compound. The fluorine-containing organosilicon compound may also be a silane coupling agent having a fluoroalkyl group, such as a perfluoroalkyl group or a fluoroalkyl group containing a perfluoro(polyoxyalkylene) chain. Furthermore, the compound having an alkoxysilyl group may also be an organosilicon compound having an alkyl group.

[0028] When the antifouling layer 5 is formed using a fluorine-containing hydrolyzable silicon compound such as a fluorine-containing organosilicon compound, it is formed by a hydrolysis and condensation reaction as described below, and has water- and oil-repellent properties. A fluorine-containing hydrolyzable silicon compound refers to a compound having a hydrolyzable silyl group in which a hydrolyzable group or atom is bonded to a silicon atom, and a fluorine-containing organic group bonded to the silicon atom. The hydrolyzable group or atom bonded to the silicon atom to form the hydrolyzable silyl group is collectively referred to as the "hydrolyzable group." That is, the hydrolyzable silyl group of the fluorine-containing hydrolyzable silicon compound becomes a silanol group upon hydrolysis, and these further undergo intermolecular dehydration condensation to form a siloxane bond represented by —Si—O—Si—, thereby forming a fluorine-containing organosilicon compound coating. In the fluorine-containing organosilicon compound coating, most of the fluorine-containing organic groups bonded to the silicon atoms of the siloxane bonds are present near the surface of the coating on the antireflection layer 3 side, and the action of these fluorine-containing organic groups enables the development of water- and oil-repellent properties. In this case, the silanol groups chemically bond with hydroxyl groups in the outermost layer 31, which is primarily composed of silicon oxide, through a dehydration condensation reaction, forming adhesion points via siloxane bonds. In this way, in the laminate 1, the anti-fouling layer 5 is firmly fixed to the glass substrate 2 via the anti-reflection layer 3, so the laminate 1 has excellent anti-fouling properties. Similarly, when the anti-fouling layer 5 is formed using an organosilicon compound, the hydrolyzable silyl groups of the organosilicon compound are hydrolyzed to form silanol groups. The silanol groups then chemically bond with hydroxyl groups in the outermost layer 31 through a dehydration condensation reaction, and the anti-fouling layer 5 is firmly fixed to the glass substrate 2 via the anti-reflection layer 3.

[0029] The surface resistance of the outermost surface of the first main surface 21 of the laminate 1, i.e., the outermost surface of the outermost functional layer 10, is 1.0×10 １２ Ω / cm ２ or more, preferably 1.0 × 10 １３ Ω / cm ２ That's all. CuAlO ２ Since CuAlO has electrical conductivity, when the laminate 1 has such a surface resistance value, ２It can be assumed that the layer 4 is provided so as not to cover the entire outermost layer 31 of the antireflection layer 3 but to expose a part of the outermost layer 31. ２ It can be assumed that the antifouling layer 5, which fills the portion where the outermost layer 31 is exposed from the layer 4, is firmly fixed to the outermost layer 31 in a state where it exhibits antifouling performance. The surface resistivity of the outermost surface of the outermost surface functional layer 10 is 1.0 × 10 １５ Ω / cm ２ The laminate 1 having the above-described configuration can achieve both antiviral performance and antifouling performance.

[0030] As mentioned above, CuAlO ２ The thickness of the layer 4 is 2 nm or more. This suggests that the laminate 1 has sufficient antiviral performance. Alternatively, the outermost functional layer 10 of the laminate 1 has an antiviral activity value of 2.0 or more when subjected to an antiviral performance evaluation test defined in ISO 21702 (established in 2019) for one hour. Because the laminate 1 has such properties, the antifouling layer 5 having antifouling performance is made of CuAlO ２ Since the layer 4 is provided so as not to cover the entire surface thereof, it can be assumed that sufficient antiviral performance is imparted to the laminate 1. The laminate 1 having the above-described configuration can achieve both antiviral performance and antifouling performance. ２ It is more preferable that both the thickness characteristic and the antiviral activity value characteristic of the layer 4 be satisfied.

[0031] The water contact angle of the outermost surface functional layer 10 of the laminate 1 is preferably 75° or greater. The water contact angle is the contact angle with water in a state in which, for example, residual uncured components have been removed from the anti-fouling layer of the outermost surface functional layer 10 with alcohol or the like. When the laminate 1 has such a contact angle, it can be assumed that the anti-fouling layer 5 is firmly fixed to the outermost surface layer 31 in a state in which it has sufficient functional groups to exhibit anti-fouling performance, i.e., it can be assumed that it has a sufficient thickness and is in a coarse and dense state. The water contact angle of the outermost surface functional layer 10 of the laminate 1 is more preferably 90° or greater, and even more preferably 100° or greater.

[0032] The luminous reflectance when the laminate 1 is viewed from the outermost functional layer 10 side of the laminate 1 is preferably 3.0% or less. By using such a laminate 1 as a cover glass for a display device, glare due to reflection of light can be reduced, and the visibility of the display device can be improved. The luminous reflectance when the laminate 1 is viewed from the outermost functional layer 10 side of the laminate 1 is more preferably 1.0% or less.

[0033] The visible light transmittance when the laminate 1 is viewed from the outermost functional layer 10 side of the laminate 1 is preferably 85.0% or more. By using such a laminate 1 as a cover glass of a display device, the transmittance of light from the display device can be improved, and the visibility of the display device can be improved. The visible light transmittance when the laminate 1 is viewed from the outermost functional layer 10 side of the laminate 1 is more preferably 90% or more.

[0034] 1, a printed layer 6 may be provided on the peripheral edge of the second main surface 22 of the glass substrate 2. The printed layer 6 is provided so as to conceal wiring circuits arranged near the periphery of the display device or adhesive portions between the housing of the display device and the laminate 1, for the purpose of improving the visibility and aesthetics of the display, for example.

[0035] <Application Example of Laminate> The laminate 1 having the above-described configuration can be applied to a cover glass of a display device. For example, as shown in FIG. 2 , the laminate 1 may be provided so as to cover a display surface 92 of a display 91 of a vehicle 9. In this case, the second main surface 22 of the laminate 1 is bonded to the display surface 92 so that the first main surface 21 faces the driver. The laminate 1 and the display 91 constitute an in-vehicle display device 90. Note that the display device including the laminate 1 as a cover glass may be a display or touch panel of a portable or fixed terminal device, a home appliance, or various devices. The laminate 1 may also be applied as a cover glass of a picture frame. Furthermore, when the laminate 1 is applied to an application that does not require a transparent function, the glass substrate 2 may be opaque.

[0036] [Modifications] Although the embodiments of the present invention have been described above in detail with reference to the drawings, the specific configuration is not limited to this embodiment, and various improvements and design changes that do not deviate from the gist of the present invention are also included in the present invention. Note that in the modifications described below, the same components as those in the above embodiment are given the same names and symbols, and their descriptions will be simplified or omitted.

[0037] <First Modification> As shown in Fig. 3A, a laminate 1A according to a first modification has the same configuration as the laminate 1 of the embodiment, except that a film 2A is provided as a substrate instead of the glass substrate 2. The film 2A is a transparent, deformable or non-deformable substrate made of, for example, an organic resin. Examples of organic resins include polycarbonate, acrylic, polyethylene, polypropylene, and polyethylene terephthalate. The film 2A may be opaque and may have a curvature over the entire surface or a portion thereof, rather than being a flat plate.

[0038] <Second Modification> As shown in FIG. 3B , the laminate 1B according to the second modification has the same configuration as the laminate 1 of the embodiment, except that an antiglare film 2B is provided as a substrate instead of the glass substrate 2. It is preferable that the first main surface 21B of the antiglare film 2B be provided with irregularities. The irregularities on the first main surface 21B of the antiglare film 2B increase the haze value due to external scattering, thereby imparting antiglare properties. The irregularities on the antiglare film 2B are formed, for example, by applying a hard coat layer containing particles to the surface of a transparent, deformable or non-deformable film substrate made of an organic resin. The antiglare film 2B may be formed from a composition containing particles that serve as scattering sources in a transparent resin. In this case, the haze value of the antiglare film 2B increases due to internal scattering, thereby imparting antiglare properties. The antiglare film 2B may be opaque and may be flat, or may have curvature over the entire surface or a portion thereof.

[0039] 4A , a laminate 1C according to a third modification has the same configuration as the laminate 1 of the embodiment, except that an antiglare layer 7 that imparts antiglare performance to the laminate 1C is provided between the glass substrate 2 and the antireflection layer 3. The antiglare layer 7 has an uneven surface on the side of the antireflection layer 3. The uneven shape is formed, for example, by chemically or physically treating the first main surface 21 of the glass substrate 2.

[0040] <Fourth Modification> As shown in FIG. 4B , a laminate 1D according to the fourth modification has the same configuration as the laminate 1A according to the first modification, except that an antiglare layer 7A that imparts antiglare performance to the laminate 1D is provided between the film 2A and the antireflection layer 3. The antiglare layer 7A has an uneven surface on the antireflection layer 3 side. The uneven surface is formed, for example, by chemically or physically treating the first main surface 21A of the film 2A. Such uneven surface increases the haze value through external scattering, thereby imparting antiglare properties. The antiglare layer 7A may be formed by incorporating particles that serve as scattering sources into the first main surface 21A of the film 2A. In this case, the antiglare layer 7A increases the haze value through internal scattering, thereby imparting antiglare properties.

[0041] 5A, the laminate 1E according to the fifth modification has the same configuration as the laminate 1C according to the third modification, except that it does not include the antireflection layer 3. In the laminate 1E, a CuAlO ２ The anti-fouling layer 5 is formed on the anti-glare layer 7. Therefore, the anti-fouling layer 5 is firmly fixed to the anti-glare layer 7.

[0042] <Sixth Modification> As shown in FIG. 5B, a stack 1F according to a sixth modification has the same configuration as the stack 1D of the fourth modification, except that the antireflection layer 3 is not provided.

[0043] 6A , a laminate 1G according to a seventh modification has the same configuration as the laminate 1C according to the third modification, except that an adhesion layer 8 is provided instead of the antireflection layer 3. The outermost layer of the adhesion layer 8, i.e., the layer in contact with the outermost surface functional layer 10, is composed of a silicon oxide layer containing silicon oxide as the main component, similar to the outermost layer 31. Therefore, the antifouling layer 5 is firmly fixed to the adhesion layer 8.

[0044] 6B , a laminate 1H according to an eighth modification has the same configuration as the laminate 1D according to the fourth modification, except that an adhesion layer 8 is provided instead of the antireflection layer 3. In this case, the outermost layer of the adhesion layer 8, i.e., the layer in contact with the outermost surface functional layer 10, may be composed of a silicon oxide layer containing silicon oxide as a main component, similar to the outermost layer 31. Furthermore, the adhesion layer 8 may be a film containing silicon oxide as a main component formed on the film 2A by a dry coating method.

[0045] 7A, a laminate 1J according to a ninth modification has the same configuration as the laminate 1 of the embodiment, except that it does not include an antireflection layer 3. In the laminate 1J, a CuAlO ２ The antifouling layer 5 is formed on the glass substrate 2. Therefore, the antifouling layer 5 is firmly fixed to the glass substrate 2.

[0046] 7B , a laminate 1K according to a tenth modification has the same configuration as the laminate 1A according to the first modification, except that it does not include the antireflection layer 3. In this case, the outermost layer of the film 2A may be plasma-treated in order to firmly fix the antifouling layer 5 and the film 2A together.

[0047] 7C , a laminate 1L according to an eleventh modification has the same configuration as the laminate 1B of the second modification, except that it does not include the antireflection layer 3. In this case, the outermost layer of the antiglare film 2B may be plasma-treated in order to firmly fix the antifouling layer 5 and the antiglare film 2B together.

[0048] <Twelfth Modification> As shown in FIG. 8A, a laminate 1M according to a twelfth modification has the same configuration as the laminate 1 of the embodiment, except that an adhesion layer 8 is provided instead of the antireflection layer 3.

[0049] <Thirteenth Modification> As shown in FIG. 8B , a stack 1N according to a thirteenth modification has the same configuration as the stack 1A according to the first modification, except that an adhesion layer 8 is provided instead of the antireflection layer 3.

[0050] <Fourteenth Modification> As shown in FIG. 8C , a stack 1P according to a fourteenth modification has the same configuration as the stack 1B according to the second modification, except that an adhesion layer 8 is provided instead of the antireflection layer 3.

[0051] <Application Examples of First to Fourteenth Modifications> Laminates 1C, 1E, 1G, 1J, and 1M each including a glass substrate 2 can be used in the same applications as laminate 1 of the embodiment. When film 2A or antiglare film 2B is transparent, laminates 1A, 1D, 1F, 1H, 1K, and 1N each including film 2A and laminates 1B, 1L, and 1P each including antiglare film 2B may be attached to displays or touch panels of portable or fixed terminal devices, home appliances, and various devices, picture frame cover glass, vehicle door trim, and the like. When film 2A or antiglare film 2B is opaque, they may be attached to vehicle door trim and the like for applications in which a transparency function is not required.

[0052] Next, examples of the present invention will be described. Examples 1 and 6 are comparative examples, and Examples 2 to 5 are working examples. However, the present invention is not limited to these examples.

[0053] [Preparation of Laminate] The laminates of Examples 1 to 6 shown below were prepared by the same method as the laminate 1 of the embodiment, using a glass substrate, an anti-reflection layer, and a CuAlO ２The laminates of Examples 1 to 6 each had an outermost functional layer consisting of a low refractive index layer and an antifouling layer. The antireflection layer had a laminated structure in which two low refractive index layers and two high refractive index layers were alternately stacked. As shown in Table 1, the main component of the fourth layer 34, which was a high refractive index layer, and the layer corresponding to the second layer 32 was niobium oxide. The main component of the third layer 33, which was a low refractive index layer, and the layer corresponding to the outermost layer 31 was silicon oxide. When preparing the laminates of Examples 1 to 6, a chemically strengthened glass based on aluminosilicate glass (manufactured by AGC Inc., product name: Dragon Trail (registered trademark)) was prepared as the glass substrate. The size of the glass substrate was 100 mm x 100 mm and the thickness was 1.0 mm. The method for preparing each laminate is described in detail below.

[0054] Example 1 An antireflection layer having the structure A shown in Table 1 was formed on the first main surface of a glass substrate by sputtering. First, a high refractive index layer having a thickness of 11.0 nm was formed on the glass substrate as a layer corresponding to the fourth layer 34. Next, a low refractive index layer having a thickness of 37.6 nm was formed as a layer corresponding to the third layer 33. Next, a high refractive index layer having a thickness of 107.8 nm was formed as a layer corresponding to the second layer 32. Finally, a low refractive index layer having a thickness of 82.5 nm was formed as a layer corresponding to the outermost layer 31. The thickness of each layer constituting the antireflection layer was measured by cross-sectional observation using an SEM. Thereafter, a 1 nm-thick CuAlO 300 was formed on the antireflection layer as shown in Table 2. ２ A CuAlO layer was formed. ２ The layer was formed by Method C described above using a Cu-Al oxide target and argon gas. ２ The thickness of the layer was measured, and the average value of the thickness at the three thickest points within the field of view was calculated as CuAlO ２ Finally, a fluorine-containing organic compound (Afluid (registered trademark) S550, manufactured by AGC) which is a composition for forming an antifouling layer was mixed with CuAlO ２After spray coating onto the layer, it was dried at 120 ° C for 20 minutes to form an antifouling layer. After that, the remaining uncured components on the outermost surface were wiped off with a cloth soaked in ethanol to form an antifouling layer. The target thickness of the antifouling layer was 4 nm.

[0055] Example 2 An antireflection layer having the structure B shown in Table 1 was formed on the first main surface of a glass substrate. Layers having thicknesses of 11.0 nm, 35.6 nm, 106.8 nm, and 71.5 nm corresponding to the fourth layer 34, the third layer 33, the second layer 32, and the outermost layer 31, respectively, were formed by the same method as in Example 1. Thereafter, a CuAlO layer having a thickness of 5 nm was formed on the antireflection layer as shown in Table 2. ２ The layer was formed by the same method as in Example 1. Finally, an anti-fouling layer was formed by the same method as in Example 1. The target thickness of the anti-fouling layer was 4 nm.

[0056] Example 3 An antireflection layer having the structure C shown in Table 1 was formed on the first main surface of a glass substrate. Layers having thicknesses of 12.0 nm, 34.6 nm, 112.8 nm, and 64.5 nm corresponding to the fourth layer 34, the third layer 33, the second layer 32, and the outermost layer 31, respectively, were formed by the same method as in Example 1. Thereafter, a 10-nm-thick CuAlO ２ The layer was formed by the same method as in Example 1. Finally, an anti-fouling layer was formed by the same method as in Example 1. The target thickness of the anti-fouling layer was 4 nm.

[0057] Example 4 An antireflection layer having the structure D shown in Table 1 was formed on the first main surface of a glass substrate. Layers having thicknesses of 18.0 nm, 34.6 nm, 127.8 nm, and 58.5 nm corresponding to the fourth layer 34, the third layer 33, the second layer 32, and the outermost layer 31, respectively, were formed by the same method as in Example 1. Thereafter, a CuAlO layer having a thickness of 15 nm was formed on the antireflection layer as shown in Table 2. ２ The layer was formed by the same method as in Example 1. Finally, an anti-fouling layer was formed by the same method as in Example 1. The target thickness of the anti-fouling layer was 4 nm.

[0058] Example 5 An antireflection layer having the structure A was formed on the first main surface of a glass substrate by the same method as in Example 1. Thereafter, a CuAlO layer having a thickness of 30 nm was formed on the antireflection layer as shown in Table 2. ２ An anti-reflection layer having the structure A was formed on the first main surface of the glass substrate by the same method as in Example 1. Then, a CuAlO layer having a thickness of 50 nm was formed on the anti-reflection layer as shown in Table 2. ２ The layer was formed by the same method as in Example 1. Finally, an anti-fouling layer was formed by the same method as in Example 1. The target thickness of the anti-fouling layer was 4 nm.

[0059] [Evaluation] <Visible Light Transmittance> The visible light transmittance of the laminates of Examples 1 to 6 was measured in accordance with JIS R3106: 1998. The visible light transmittance of the laminates of Examples 1 to 6 was 95.0%, 94.3%, 92.4%, 91.5%, 87.5%, and 83.4%, respectively.

[0060] <Luminous Reflectance> The luminous reflectance of the laminates of Examples 1 to 6 was measured when viewed from the first principal surface side. First, a black PET film (manufactured by Tomoegawa Corporation, product name: Kukkiri Miel) was attached to the second principal surface of the laminate of Example 1, i.e., the principal surface not provided with an anti-reflection layer or the like. Then, using a spectrophotometer (manufactured by Konica Minolta, Inc., model: CM-2600d), the spectral reflectance was measured in SCI mode, and based on the spectral reflectance, the reflection stimulus value Y specified in JIS Z8701 was calculated as the luminous reflectance. The luminous reflectance was 0.16%. The luminous reflectance of the laminates of Examples 2 to 6 was measured using the same method as for the laminate of Example 1. The luminous reflectances of the laminates of Examples 2 to 6 were 0.22%, 0.56%, 0.82%, 2.90%, and 4.90%, respectively.

[0061] <Surface Resistivity> The surface resistance of the first main surface side of the laminates of Examples 1 to 6 was measured in accordance with JIS K6911. First, a flat sample electrode (manufactured by Hioki E.E. Corporation, model: SME-8311) was attached to an ultra-insulation meter (manufactured by Hioki E.E. Corporation, model: SM-8220). Then, a voltage of 1000 V was applied to the laminate of Example 1 in an environment of a temperature of 22±2°C and a humidity of 45±10%, to measure the surface resistance. The surface resistance was 1.0×10 １４ Ω / cm ２ The surface resistance values ​​of the laminates of Examples 2 to 6 were measured in the same manner as for the laminate of Example 1. The surface resistance values ​​of the laminates of Examples 2 to 5 were all greater than 1.0 × 10 １２ Ω / cm ２ On the other hand, the surface resistance of the laminate of Example 6 was greater than 7.3 × 10 １１ Ω / cm ２ It was.

[0062] <Initial Water Contact Angle> The initial water contact angle of the outermost surface functional layer in the laminates of Examples 1 to 6 was measured. First, the laminate of 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 on the outermost surface functional layer, and the contact angle of the water droplet was measured. The contact angle of the water droplet was measured at five locations on the outermost surface functional layer, and the average value of the measurement results was calculated as the initial water contact angle. The initial water contact angle was 116°. The initial water contact angles of the laminates of Examples 2 to 6 were measured using the same method as for the laminate of Example 1. The initial water contact angles of the laminates of Examples 2 to 6 were 116°, 116°, 116°, 95°, and 70°, respectively.

[0063] <Antiviral Activity Value> The antiviral activity values ​​of the laminates of Examples 1 to 6 were measured using the antiviral performance evaluation test specified in ISO 21702 (established in 2019). First, a 50 mm x 50 mm test piece was cut from the laminate of Example 1 as a processed test piece. A 50 mm x 50 mm test piece consisting of only a glass substrate with the same composition as the glass substrate of the laminate of Example 1 was also prepared as an unprocessed test piece. Next, 4 ml of virus solution (bacteriophage Φ6, host Pseudomonas syringae (NBRC14084)) was dripped onto the outermost functional layer of the processed test piece and covered with a 40 mm x 40 mm polypropylene film (manufactured by Kokuyo Co., Ltd., product number: VF-10). Furthermore, 4 ml of virus solution was dripped onto one main surface of the unprocessed test piece and covered with a 40 mm x 40 mm film. The processed and unprocessed test pieces were then left to stand for 1 hour in an environment at 25°C, after which the viruses were washed out. After this, the virus infectivity (PFU / cm) of the processed and unprocessed test pieces was measured. ２ ) was measured, and the antiviral activity value was calculated based on the following formula (1): R = Ut - At (1) R: antiviral activity value Ut: average common logarithm of the viral infectivity titer of unprocessed test pieces after standing for 1 hour At: average common logarithm of the viral infectivity titer of processed test pieces after standing for 1 hour In the antiviral performance evaluation test, an antiviral activity value of 2.0 or more is evaluated as meeting the standard, and the higher the antiviral activity value, the higher the antiviral performance is evaluated. The antiviral activity value of the laminate of Example 1 one hour after the start of the test was 0.7, which is below the standard.

[0064] For the laminate of Example 2, the antiviral activity value was measured 0.25 hours after the start of the test, i.e., 15 minutes after the start of the test, and the antiviral activity value after 1 hour. First, two processed test pieces and two unprocessed test pieces similar to those in Example 1 were prepared. The same treatment as in Example 1 was carried out on each of the processed test pieces and the unprocessed test pieces, except that the standing time was set to 0.25 hours, and the antiviral activity value after 0.25 hours was calculated. The remaining processed test pieces and the unprocessed test pieces were also carried out in the same manner as in Example 1, and the antiviral activity value after 1 hour was calculated. The antiviral activity value of the laminate of Example 2 0.25 hours after the start of the test was 0.5, which is below the standard. On the other hand, the antiviral activity value after 1 hour after the start of the test was 2.7, which is above the standard.

[0065] The laminate of Example 3 was treated in the same manner as in Example 2, 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 of Example 3 0.25 hours after the start of the test was 1.4, which is below the standard. On the other hand, the antiviral activity value of the laminate of Example 3 1 hour after the start of the test was 3.3, which is above the standard. The laminate of Example 4 was treated in the same manner as in Example 1, and the antiviral activity value was measured 1 hour after the start of the test. The antiviral activity value of the laminate of Example 4 1 hour after the start of the test was 4.0, which is above the standard. The laminate of Example 5 was treated in the same manner as in Example 1, and the antiviral activity value was measured 1 hour after the start of the test. The antiviral activity value of the laminate of Example 5 1 hour after the start of the test was 4.0, which is above the standard. The laminate of Example 6 was treated in the same manner as in Example 1, 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 standard.

[0066]

[0067]

[0068] [Discussion] (Discussion 1) The visible light transmittance of the laminates of Examples 1 to 4 was 90% or more, the visible light transmittance of the laminate of Example 5 was 87.5%, while the visible light transmittance of the laminate of Example 6 was 83.4%. In addition, the luminous reflectance of the laminates of Examples 1 to 4 was less than 1%, the luminous reflectance of the laminate of Example 5 was 2.90%, and the luminous reflectance of the laminate of Example 6 was 4.90%. The reason for this is that in the laminate of Example 5, the high refractive index layer, CuAlO ２ The layer thickness is 30 nm, and in the stack of Example 6, CuAlO ２ This is presumably because the layer thickness was 50 nm, which was thicker than the laminates of Examples 1 to 4.

[0069] (Consideration 2) The surface resistance of the laminates of Examples 1 to 4 was 1.0×10 １４ Ω / cm ２ The surface resistance of the laminate of Example 5 exceeded 1.0 × 10 １３ Ω / cm ２ On the other hand, the surface resistance of the laminate of Example 6 was 7.3 × 10 １１ Ω / cm ２ The reason for this is that in the laminates of Examples 1 to 5, CuAlO ２ The layer thickness is 30 nm or less, which is thinner than the stack of Example 6, and CuAlO ２ This is presumably because the portion of the antireflection layer exposed from the laminate was larger than that of the laminate of Example 6, allowing the formation of an antifouling layer with a sufficient area.

[0070] (Discussion 3) The initial water contact angles of the laminates of Examples 1 to 4 were 116°, the initial water contact angle of the laminate of Example 5 was 95°, and the initial water contact angle of the laminate of Example 6 was 70°. In other words, the antifouling performance of the laminates of Examples 1 to 5 was higher than that of the laminate of Example 6. The reason for this is that, as shown in Discussion 2, in the laminates of Examples 1 to 5, CuAlO ２ This is presumably because the portion of the antireflection layer 3 exposed from the layer was larger than in the laminate of Example 6, the adhesion between the outermost layer of the antireflection layer containing silicon oxide as a main component and the antifouling layer was stronger than in the laminate of Example 6, and the amount of fluorine constituting the antifouling layer was greater than in the laminate of Example 6.

[0071] (Discussion 4) The antiviral activity value of the laminate of Example 1 one hour after the start of the test was 0.7, which was lower than the standard, while the antiviral activity values ​​of the laminates of Examples 2 to 6 were 2.7 or higher, which was higher than the standard. Furthermore, the antiviral activity values ​​of the laminates of Examples 2 to 6 were 2.0 or higher one hour after the start of the test, confirming that the standard could be met in an extremely short time after the start of the test. The reason for the above-mentioned difference in antiviral activity value between the laminate of Example 1 and the laminates of Examples 2 to 6 is that the laminate of Example 1 had a high antiviral activity value of 2.0, which was higher than the standard. ２ This is presumably because the layer thickness was 1 nm, which was considerably thinner than the laminates of Examples 2 to 6, and was not thick enough to obtain sufficient antiviral performance. On the other hand, in the laminates of Examples 2 to 6, the antifouling layer was CuAlO ２ It can be assumed that sufficient antiviral performance was obtained because the layer was provided so as not to cover the entire surface. ２ When the layer thickness exceeded 1 nm, the antiviral activity value increased after 1 hour from the start of the test, and CuAlO ２ If the layer thickness is 2 nm or more, it is estimated that the antiviral activity value one hour after the start of the test will be 2.0 or more, which is higher than the standard.

[0072] (Summary of Considerations) From Considerations 2 to 4, it is considered that the substrate is made of CuAlO ２ In the laminate provided with the CuAlO ２ The thickness of the layer is 2 nm or more, and the surface resistance is 1.0 × 10 １２ Ω / cm ２ It was confirmed that the above-mentioned configurations make it possible to achieve both antiviral and antifouling properties. ２ In the laminate having the antifouling layer and the antifouling layer, ２ It was confirmed that by making the layer thickness 30 nm or less, it is possible to achieve sufficient antiviral and antifouling performance, as well as suitable visible light transmittance and reflectance reduction performance.

[0073] Although the present invention has been described in detail and with reference to specific embodiments, 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 present invention. 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.

[0074] 1, 1A, 1B, 1C, 1D, 1E, 1F, 1G, 1H, 1J, 1K, 1L, 1M, 1N, 1P... Laminate, 2... Glass substrate (substrate), 2A... Film (substrate), 2B... Anti-glare film (substrate), 3... Antireflection layer, 4... CuAlO ２ layer, 5... antifouling layer, 7, 7A... antiglare layer, 21, 21A, 21B... first main surface, 22... second main surface, 90... in-vehicle display device (display device).

Claims

1. A substrate having a first main surface and a second main surface; and a CuAlO ２ a CuAlO layer and an antifouling layer, ２ the CuAlO layer and the antifouling layer are formed on the outermost surface of the first principal surface side in contact with each other, ２ the thickness of the layer is 2 nm or more, and the surface resistance of the outermost surface on the first principal surface side is 1.0 × 10 １２ Ω / cm ２ That's it, the laminate.

2. The laminate according to claim 1, wherein the CuAlO ２ The layer thickness is 30 nm or less.

3. A substrate having a first main surface and a second main surface, and a CuAlO ２ a CuAlO layer and an antifouling layer, ２ the antifouling layer and the antifouling layer are formed on the outermost surface of the first principal surface side in a state of contact with each other, and a surface resistance value of the outermost surface of the first principal surface side is 1.0 × 10 １２ Ω / cm ２ or above, wherein the outermost surface on the first principal surface side has an antiviral activity value of 2.0 or more when an antiviral performance evaluation test specified in ISO 21702 is performed for one hour.

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

5. A laminate according to claim 4, wherein at least a portion of the antifouling layer is in direct contact with the surface containing silicon oxide as a main component.

6. The laminate according to any one of claims 1 to 3, wherein the laminate has a water contact angle of 75° or more.

7. A laminate according to any one of claims 1 to 3, having a luminous reflectance of 3.0% or less.

8. The laminate according to any one of claims 1 to 3, having a visible light transmittance of 85.0% or more.

9. The laminate according to any one of claims 1 to 3, wherein the first main surface and the CuAlO ２ an antiglare layer is provided between the antifouling layer and the antiglare layer.

10. The laminate according to any one of claims 1 to 3, wherein the first main surface and the CuAlO ２ an anti-reflection layer is provided between the anti-fouling layer and the anti-reflection layer, the anti-reflection layer has a laminated structure in which low refractive index layers and high refractive index layers are alternately laminated, and is composed of 1 to 15 low refractive index layers and the same number of high refractive index layers as the low refractive index layers.

11. A laminate according to claim 10, wherein the main component of the low refractive index layer is silicon oxide, and 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. A laminate according to any one of claims 1 to 3, wherein the substrate is a glass substrate.

13. A cover glass comprising the laminate according to claim 12.

14. A display device comprising: the cover glass according to claim 13; and a display, wherein the second main surface of the cover glass is bonded to the display.

Images