Conductive-film-equipped glass substrate laminate and method for manufacturing the same, electromagnetic wave control member, and frequency selection plate

Abstract

To prevent breakage of a glass substrate on which a pattern conductive film is formed.SOLUTION: Provided is a conductive-film-equipped glass substrate laminate in which a glass substrate, a thermoplastic resin layer, and a transparent layer are laminated in this order. The glass substrate includes a glass plate and a pattern conductive film formed on at least one of principal surfaces of the glass plate and having a conductive region patterned thereon.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a glass substrate laminate with a conductive film and a manufacturing method thereof.The present invention also relates to an electromagnetic wave control member and a frequency selective plate including the glass substrate laminate with a conductive film. [Background technology]

[0002] In recent years, fifth-generation wireless systems (5G) have become widespread, and many electronic devices are being installed in automobiles and other devices. However, when these devices are used, malfunctions of the electronic devices are likely to occur due to radio wave interference. One method of preventing radio wave interference is to use electromagnetic wave control materials.

[0003] Examples of the electromagnetic wave control member include a wave absorber such as a λ / 4 wave absorber, and a frequency selective surface in which a conductive film patterned on a substrate is provided. For example, Patent Document 1 discloses a glass plate having a low-emissivity (Low-E) coating partially on its surface. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Special Publication No. 2016-534975 Summary of the Invention [Problem to be solved by the invention]

[0005] However, glass substrates with a conductive film partially formed on their main surface are subject to a risk of cracking, and therefore are limited in their applicability. Specifically, because the conductive film is a patterned conductive film rather than covering the entire main surface of the glass substrate, the strength of the glass substrate surface is not uniform. Furthermore, microcracks are likely to occur on the glass surface during patterning of the conductive region, and external impacts increase the probability of the glass substrate cracking due to the microcracks.

[0006] Therefore, an object of the present invention is to prevent cracking of a glass substrate on which a patterned conductive film is formed. [Means for solving the problem]

[0007] As a result of extensive research, the inventors have discovered that the above-mentioned problems can be solved by forming a laminate in which a thermoplastic resin layer and a transparent layer are laminated on a glass substrate on which a patterned conductive film has been formed, and have thus completed the present invention.

[0008] That is, the present invention has the following configuration. [1] A laminate in which a glass substrate, a thermoplastic resin layer, and a transparent layer are laminated in this order, The glass substrate is a glass substrate laminate with a conductive film, the glass substrate including: a glass plate; and a patterned conductive film formed on at least one main surface of the glass plate, the patterned conductive film having a conductive region patterned thereon. [2] The glass plate has the patterned conductive film formed on one main surface thereof, The glass substrate laminate with a conductive film according to [1] above, wherein the thermoplastic resin layer is laminated on the main surface of the glass substrate on which the patterned conductive film is formed. [3] The glass substrate laminate with a conductive film according to [1] or [2] above, wherein the glass plate has a thickness of 2 mm or more. [4] The glass substrate laminate with a conductive film according to any one of [1] to [3], wherein the thermoplastic resin layer contains at least one selected from the group consisting of polyvinyl acetal resin, ethylene-vinyl acetate copolymer resin, cycloolefin polymer resin, urethane-based resin, acrylic-based resin, silicone resin, epoxy resin, vinyl acetate resin, vinyl chloride-based resin, and chloroprene rubber. [5] The glass substrate laminate with a conductive film according to any one of [1] to [4] above, wherein the transparent layer is made of glass or resin. [6] The transparent layer is made of the resin, The glass substrate laminate with a conductive film according to [5] above, wherein the resin comprises at least one selected from the group consisting of polycarbonate-based resins, acrylic-based resins, aromatic polyester-based resins, polystyrene-based resins, vinyl chloride-based resins, polyester-based resins, polypropylene-based resins, ABS resins, olefin-based resins, and silicone resins. [7] The glass substrate laminate with a conductive film according to any one of [1] to [6] above, which has a visible light transmittance of 50% or more. [8] Bending stiffness is 1×10 8 N mm 2 The above-mentioned glass substrate laminate with a conductive film according to any one of [1] to [7]. [9] The glass substrate laminate with a conductive film according to any one of [1] to [8], wherein the conductive region contains silver, and the surface resistance of the patterned conductive film at 20°C is 10 Ω / □ or less.

[10] The glass substrate laminate with a conductive film according to any one of [1] to [9] above, wherein the patterned conductive film is patterned over the entire surface of at least one of the main surfaces of the glass plate.

[11] The glass substrate laminate with a conductive film according to any one of [1] to

[10] above, wherein the pattern of the patterned conductive film is a mesh, a patch, a cross element, or a cross slot.

[12] The glass substrate laminate with a conductive film according to any one of [1] to

[11] above, wherein the patterned conductive film includes a protective layer.

[0009]

[13] A method for producing a glass substrate laminate with a conductive film according to any one of [1] to

[12] , forming a patterned conductive film by patterning a conductive region on at least one main surface of the glass plate; The method for producing a glass substrate laminate with a patterned conductive film, wherein the patterning is performed using at least one method selected from the group consisting of sputtering, vapor deposition, laser processing, etching, photolithography, sandblasting, wet blasting, screen printing, and inkjet printing.

[14] An electromagnetic wave control member comprising the glass substrate laminate with a conductive film according to any one of [1] to

[12] above.

[15] A frequency selective plate comprising the glass substrate laminate with a conductive film according to any one of [1] to

[12] above. [Effects of the Invention]

[0010] According to the present invention, by forming a laminate, it is possible to suppress cracking of a glass substrate on which a patterned conductive film is formed. Therefore, the glass substrate on which the patterned conductive film is formed can be applied to a wide range of locations. Specifically, the laminate including the glass substrate can be applied to any desired location, such as a window of a building, a partition in a space, a ceiling, or a floor, without any particular limitation. [Brief explanation of the drawings]

[0011] [Figure 1] FIG. 1 is a schematic cross-sectional view showing one aspect of a glass substrate laminate with a conductive film according to this embodiment. [Figure 2] FIG. 2 is a schematic cross-sectional view showing one aspect of a glass substrate laminate with a conductive film according to this embodiment. [Figure 3] FIG. 3 is a schematic cross-sectional view showing one aspect of the glass substrate in this embodiment. [Figure 4] FIG. 4 is a schematic diagram for explaining the pattern of the patterned conductive film, where (a) in FIG. 4 is a mesh, (b) in FIG. 4 is a patch, (c) in FIG. 4 is a cross element, and (d) in FIG. 4 is a cross slot. [Figure 5] FIG. 5 is a graph showing the calculation results of the radio wave transmission characteristics of the conductive film-formed glass substrate laminate obtained in Example 1. DETAILED DESCRIPTION OF THE INVENTION

[0012] The present invention will be described in detail below, but the present invention is not limited to the following embodiments and can be implemented in any modified form without departing from the gist of the present invention. Furthermore, the use of "to" to indicate a range of values means that the values before and after it are included as the lower and upper limits. In the following drawings, components and parts having the same function may be denoted by the same reference numerals, and redundant explanations may be omitted or simplified. The embodiments shown in the drawings are schematic in order to clearly explain the present invention, and do not necessarily accurately represent the size or scale of the actual product.

[0013] <<Glass substrate laminate with conductive film>> The conductive film-attached glass substrate laminate according to this embodiment (hereinafter, sometimes simply referred to as "laminate") is a laminate in which a glass substrate, a thermoplastic resin layer, and a transparent layer are laminated in this order. The glass substrate includes a glass plate and a patterned conductive film formed on at least one main surface of the glass plate and having a patterned conductive region.

[0014] One aspect of the laminate according to this embodiment will be described with reference to FIG. The glass substrate laminate 1 with a conductive film according to this embodiment is a laminate in which a glass substrate 10, a thermoplastic resin layer 20, and a transparent layer 30 are laminated in this order. Here, the glass substrate 10 includes a glass plate 11 and a patterned conductive film 12, and the patterned conductive film 12 is formed on a first main surface 11a of the glass plate 11, which is the main surface on the thermoplastic resin layer 20 side. That is, the patterned conductive film 12 and an area of the first main surface 11a of the glass plate 11 on which the patterned conductive film 12 is not formed are in contact with the thermoplastic resin layer 20. In this specification, the term "patterned conductive film" refers to a film in which conductive regions are patterned.

[0015] Another aspect of the laminate according to this embodiment will be described with reference to FIG. The conductive-film-attached glass substrate laminate 1' according to this embodiment is a laminate in which a glass substrate 10', a thermoplastic resin layer 20', and a transparent layer 30' are laminated in this order. Here, the glass substrate 10' includes a glass plate 11' and a patterned conductive film 12', and the patterned conductive film 12' is formed on a second main surface 11'b of the glass plate 11', which is the main surface opposite to the thermoplastic resin layer 20'. In other words, a first main surface 11'a of the glass plate 11' is in contact with the thermoplastic resin layer 20'.

[0016] Each component of the laminate will be described below.

[0017] <Glass substrate> The glass substrate 10 in this embodiment includes a glass plate 11 and a patterned conductive film 12 in which conductive regions are patterned. Here, the patterned conductive film 12 may be formed on at least one of the main surfaces of the glass plate 11, or may be formed on both of the main surfaces.

[0018] In particular, from the viewpoint of further suppressing cracking of the glass substrate and preventing deterioration of the conductive film, it is preferable that a patterned conductive film 12 is formed on a first main surface 11a, which is the main surface of a glass plate 11 on the thermoplastic resin layer 20 side, and that a thermoplastic resin layer 20 is laminated thereon, as shown in FIG.

[0019] Alternatively, a patterned conductive film 12 may be formed on each of the first main surface 11a and the second main surface 11b of the glass plate 11. In this case, a thermoplastic resin layer 20 may be laminated on at least one of the main surfaces, or on both main surfaces (not shown).

[0020] (glass plate) The glass plate 11 in this embodiment is not particularly limited, and may be made of, for example, soda lime glass, alkali-free glass, quartz glass, etc. The glass plate may be subjected to physical or chemical strengthening treatment.

[0021] The glass plate 11 in this embodiment may be transparent. Here, "transparent" means that the visible light transmittance is 70% or more. The visible light transmittance of the glass plate 11 is preferably 80% or more, and more preferably 90% or more. There is no particular upper limit to the visible light transmittance, but it is usually 95% or less. The visible light transmittance in this specification is a value calculated from the transmittance of light with a wavelength of 380 to 780 nm using a standard D65 light source in accordance with JIS R3106 (1998).

[0022] In this embodiment, the shape of the glass plate 11 is preferably flat, from the viewpoint of uniformity of the patterned conductive film 12 and ease of patterning.

[0023] The thickness and size of the glass plate 11 are not particularly limited and can be adjusted appropriately depending on the desired strength, lightness, etc. For example, the thickness of the glass plate 11 is preferably 2 mm or more, more preferably 2 to 20 mm, and even more preferably 3 to 12 mm. From the viewpoint of pattern processability, the thickness is preferably 2 mm or more, more preferably 3 mm or more. The thickness may be 20 mm or less, 12 mm or less, 10 mm or less, 5 mm or less, or 4 mm or less.

[0024] The preferred ranges of various physical properties of the glass plate 11 in this embodiment, such as the specific gravity, Young's modulus, and average thermal expansion coefficient, vary depending on the application of the laminate according to this embodiment. When the laminate according to this embodiment is used as a window material, for example, the specific gravity of the glass plate 11 is preferably 2.4 to 3.0. The Young's modulus of the glass plate 11 is preferably 60 to 100 GPa. The average thermal expansion coefficient of the glass plate 11 at 50 to 350°C is preferably 50×10 -7 ~120×10 -7 / °C is preferred.

[0025] (Patterned conductive film) The patterned conductive film 12 in this embodiment is a film having a patterned conductive region formed on at least one main surface of the glass plate 11. That is, conductive regions and non-conductive regions exist on the main surface, and the patterned conductive film 12 has a patterned conductive region. The conductive region may be any region that has conductivity. For example, if the surface resistance of the patterned region at 20° C. is 100 Ω / □ or less, it can be determined to be a conductive region.

[0026] The thickness of the patterned conductive film 12 in this embodiment is preferably, for example, 5 to 1500 nm. Here, from the viewpoints of durability and conductivity, the thickness is preferably 5 nm or more, more preferably 10 nm or more, even more preferably 15 nm or more, even more preferably 50 nm or more, particularly preferably 80 nm or more, and particularly preferably 100 nm or more. Furthermore, from the viewpoints of stable formation of non-conductive regions where conductive regions are not patterned and productivity, the thickness is preferably 1500 nm or less, more preferably 1200 nm or less, even more preferably 1000 nm or less, even more preferably 500 nm or less, particularly preferably 450 nm or less, and particularly preferably 400 nm or less.

[0027] The components constituting the conductive regions constituting patterned conductive film 12 in this embodiment are not particularly limited as long as they can achieve the desired conductivity. The above components preferably include metals such as silver, aluminum, tin oxide doped with at least one of fluorine and antimony (SnO2:F,Sb), indium tin oxide (ITO), titanium nitride, niobium nitride, chromium nitride, zirconium nitride, and hafnium nitride. From the viewpoints of high conductivity and low emissivity, the conductive region preferably contains silver, more preferably contains silver as the main component, and even more preferably contains 95 atomic % or more of silver. In this specification, the term "main component" refers to a component whose content relative to all constituent components is 50 atomic % or more.

[0028] The conductive region may consist of only silver, but may also contain other components in addition to silver. Examples of the other components include, but are not limited to, gold, palladium, copper, bismuth, neodymium, platinum, etc. One or more of these other components may be included. From the viewpoint of suppressing the diffusion of silver and improving moisture resistance, the conductive region preferably contains the above-mentioned other components in addition to silver, and more preferably contains silver as the main component and further contains the above-mentioned other components.

[0029] From the viewpoint of heat insulation and heat shielding properties, the normal emissivity εn of the conductive region is preferably 0.1 or less. This effectively prevents damage to the substrate in the event of a fire, etc. In this specification, the normal emissivity εn of the conductive region is a value measured in accordance with JIS R3106 (2019).

[0030] The thickness of the conductive region varies depending on whether or not a protective layer (described later) is present, but is preferably 0.1 to 100 nm, more preferably 1 to 50 nm. From the viewpoint of ensuring performance as an electromagnetic wave control member, the thickness is preferably 0.1 nm or more, more preferably 1 nm or more, and even more preferably 5 nm or more. From the viewpoints of productivity and maintaining visible light transmittance, the thickness is preferably 100 nm or less, more preferably 50 nm or less, and even more preferably 20 nm or less. In the present embodiment, when the patterned conductive film 12 is made up of only a conductive region, the thickness of the conductive region is the thickness of the patterned conductive film 12.

[0031] In this embodiment, the sheet resistance of the patterned conductive film 12 is preferably 10 Ω / □ or less, more preferably 3 Ω / □ or less, from the viewpoint of ensuring performance as an electromagnetic wave control member. The lower limit of the sheet resistance is not particularly limited, but may be, for example, 1 Ω / □ or more. The sheet resistance values in this specification are values at 20°C, and are values measured using a four-terminal measuring device. If measurements cannot be made using a four-terminal measuring device, a Hall effect measuring device or an eddy current non-contact resistance measuring device may be used instead.

[0032] In this embodiment, it is more preferable that the conductive region contains silver and that the sheet resistance value of the patterned conductive film 12 at 20° C. is 10 Ω / □ or less.

[0033] In this embodiment, the patterned conductive film 12 may be continuously covered with an oxide film at the edge where it borders the non-conductive region. The oxide film suppresses ion migration, and excellent insulation reliability can be achieved without providing an insulating film. Note that being continuously covered with an oxide film means that the conductive region is not exposed at the end of patterned conductive film 12 located at the boundary with the non-conductive region. This oxide film can be formed by employing laser processing when patterning the conductive region to form patterned conductive film 12.

[0034] The average height of the oxide coating is preferably at least twice the thickness of the patterned conductive film 12, more preferably 2 to 15 times, even more preferably 2.5 to 10 times, and even more preferably 5 to 10 times. From the viewpoint of being able to suppress electrical connection between the patterned conductive films 12 over the long term and maintaining excellent insulation, the average height relative to the thickness is preferably at least twice, more preferably 2.5 times, and even more preferably 5 times. Furthermore, from the viewpoint of ensuring performance as an electromagnetic wave control member, the average height relative to the thickness is preferably 15 times or less, and more preferably 10 times or less.

[0035] In this embodiment, the patterned conductive film 12 preferably further includes a protective layer in addition to the conductive region. By disposing the protective layer adjacent to the conductive region, oxidation of the metal components in the conductive region in a high-temperature environment can be suppressed.

[0036] The arrangement of the protective layer may be determined depending on the purpose. For example, FIG. 3 is a schematic cross-sectional view showing one embodiment of glass substrate 10'', in which patterned conductive film 12'' is formed on one main surface of glass plate 11'', and conductive region 13'' and protective layer 14'' are laminated in patterned conductive film 12''. The region of the main surface of glass plate 11'' where patterned conductive film 12'' is not formed is non-conductive region 15''.

[0037] Here, as shown in FIG. 2, when a patterned conductive film 12′ is formed on one main surface of a glass plate 11′ and a thermoplastic resin layer 20′ is laminated on the opposite main surface, the patterned conductive film 12′ comes into contact with the atmosphere. In this case, as shown in FIG. 3, it is preferable that the patterned conductive film 12″ includes a protective layer 14″ at least on its outermost surface. This prevents contact between the conductive region 13″ and oxygen and moisture in the atmosphere, thereby suppressing deterioration of the conductive region 13″. In addition, exposure of the surface of the conductive region 13″ is also prevented, which is preferable from the viewpoint of insulation reliability.

[0038] On the other hand, it is also preferable to provide the conductive region 13'' via a protective layer 14'' rather than directly forming the conductive region 13'' on the main surface of the glass plate 11''. This can improve the bonding strength of the patterned conductive film 12'' to the glass plate 11''.

[0039] Thus, the patterned conductive film 12'' is preferably a laminate in which a conductive region 13'' and a protective layer 14'' are laminated, and examples thereof include, from the glass plate 11'' side, conductive region 13'' / protective layer 14'', protective layer 14'' / conductive region 13'', or protective layer 14'' / conductive region 13'' / protective layer 14'' (FIG. 3). The patterned conductive film 12'' may be laminated with an increased number of layers. Furthermore, the patterned conductive film 12'' may include layers other than the conductive region 13'' and protective layer 14''.

[0040] In this embodiment, the protective layer 14'' may be made of, for example, a metal oxide or a metal. Examples of the metal oxide include zinc oxide, aluminum oxide, tin oxide, and titanium oxide. Examples of the metal include titanium and Zn alloys. The protective layer 14'' may be made of one material or may contain two or more materials. When the patterned conductive film 12'' contains multiple protective layers 14'', the configuration of each protective layer 14'' may be the same or different.

[0041] When the patterned conductive film 12'' includes a protective layer 14'', the thickness of the protective layer 14'' is not particularly limited, but may be, for example, 0.5 to 100 nm, or 1 to 50 nm. When the patterned conductive film 12'' includes multiple protective layers 14'', each of them preferably has a thickness within the above range.

[0042] In this embodiment, the patterned conductive film 12 may be patterned on at least a portion of at least one of the main surfaces of the glass plate 11, but from the viewpoint of stabilizing the communication environment, it is preferable that it be patterned on the entire main surface.

[0043] The pattern shape of the patterned conductive film 12 in this embodiment may be determined depending on the application. For example, the pattern of the patterned conductive film 12 is preferably a mesh, patch, cross element, or cross slot. The upper diagram in FIG. 4 is a schematic diagram illustrating the pattern of the patterned conductive film, and the lower diagram is a graph showing the frequency response characteristics when a substrate with a conductive film is used as a frequency selective surface. The black parts in the upper diagram in FIG. 4 represent the patterned conductive film 12, and the white parts represent non-conductive regions. That is, FIG. 4(a) represents a mesh, FIG. 4(b) represents a patch, FIG. 4(c) represents a cross element, and FIG. 4(d) represents a cross slot. The pattern shape of the patterned conductive film 12 may be a combination of these four types or another shape.

[0044] The glass plate 11 and the glass plate 11 including the patterned conductive film 12 in this embodiment may further include other layers as long as the effects of the present invention are not impaired. Examples of other layers include a crack diffusion prevention layer and an anti-reflection layer.

[0045] <Thermoplastic resin layer> The thermoplastic resin layer 20 in this embodiment is a layer interposed between the glass substrate 10 and the transparent layer 30. The thermoplastic resin layer 20 makes it possible to bond the glass substrate 10 and the transparent layer 30 together.

[0046] 1, it is preferable that a patterned conductive film 12 is formed on a first main surface 11a, which is one main surface of a glass plate 11, and that a thermoplastic resin layer 20 is laminated on the main surface of the glass substrate 10 on the side on which the patterned conductive film 12 is formed. This is because the thermoplastic resin layer 20 can also serve as an insulating film and further reduces the risk of cracking of the glass substrate 10.

[0047] The thermoplastic resin layer 20 may be made of any known resin, but preferably contains at least one selected from the group consisting of polyvinyl acetal resin, ethylene vinyl acetate copolymer resin (EVA), cycloolefin polymer resin (COP), urethane resin, acrylic resin, silicone resin, epoxy resin, vinyl acetate resin, vinyl chloride resin, and chloroprene rubber. Among these, polyvinyl acetal resin, COP, etc. are preferred from the viewpoint of adhesion to glass.

[0048] A preferred example of the polyvinyl acetal resin is polyvinyl butyral (PVB).

[0049] The thermoplastic resin layer 20 in this embodiment may be a single layer or a laminate of two or more layers. From the viewpoint of cost, a single layer is preferable, and from the viewpoint of suppressing warpage, two or more layers are preferable. When the thermoplastic resin layer 20 is made up of two or more layers, the resins constituting the layers may be the same or different.

[0050] The thickness of the thermoplastic resin layer 20 is not particularly limited, but is preferably 10 to 3000 μm, more preferably 50 to 1500 μm, for example. From the viewpoint of adhesive strength, the thickness is preferably 300 μm or more. When the thermoplastic resin layer 20 is a laminate of two or more layers, it is more preferable that the total thickness of the layers is within the above range.

[0051] <Transparent layer> The transparent layer 30 in this embodiment is a layer that is bonded to the glass substrate 10 via the thermoplastic resin layer 20. By providing the transparent layer 30, it is possible to prevent the glass substrate from cracking. The transparent layer 30 may be transparent, that is, a layer having a visible light transmittance of 70% or more.

[0052] The transparent layer 30 in this embodiment is preferably made of, for example, glass or resin. More specifically, examples of the transparent layer 30 include a glass plate, a glass film, a resin plate, and a resin film.

[0053] Here, the terms "plate" and "film" are concepts that are used differently depending on the thickness and whether or not the plate has self-supporting properties. In the case of glass, for example, a glass plate means one having a thickness of 2 mm or more, and a glass film means one having a thickness of less than 2 mm. In the case of a resin, for example, a resin plate means a thickness of 2 mm or more, and a resin film means a thickness of less than 2 mm.

[0054] When the transparent layer 30 is made of a resin, the resin preferably contains at least one selected from the group consisting of polycarbonate-based resins, acrylic-based resins, aromatic polyester-based resins, polystyrene-based resins, vinyl chloride-based resins, polyester-based resins, polypropylene-based resins, ABS (acrylonitrile-butadiene-styrene) resins, olefin-based resins, and silicone resins. Here, the term "polycarbonate-based resin" encompasses aromatic polycarbonate-based resins. Examples of aromatic polyester-based resins include polyethylene terephthalate resins. Among these, polycarbonate-based resins are preferred from the viewpoint of improving crack resistance.

[0055] When the transparent layer 30 is made of glass, the type of glass is not particularly limited and can be selected according to the desired properties.

[0056] The thickness of the transparent layer 30 is preferably, for example, 0.1 to 10 mm. From the viewpoint of preventing glass cracking, the thickness is preferably 0.1 mm or more, and more preferably 2 mm or more. From the viewpoint of weight reduction, the thickness is preferably 10 mm or less, more preferably 7 mm or less, and even more preferably 4 mm or less.

[0057] <Other configurations> The conductive-film-attached glass substrate laminate 1 according to this embodiment may further include layers other than the glass substrate 10, the thermoplastic resin layer 20, and the transparent layer 30, as long as the effects of the present invention are not impaired. For example, in the glass substrate laminate 1 with a conductive film shown in FIG. 1, another layer may be further laminated on the second main surface 11b of the glass plate 11 in the glass substrate 10, which is located on the opposite side to the thermoplastic resin layer 20.

[0058] <Characteristics> The visible light transmittance of the glass substrate laminate 1 with a conductive film according to this embodiment is preferably 50% or more, more preferably 50 to 90%, and even more preferably 53 to 80%. From the viewpoint of visibility when the glass substrate laminate 1 with a conductive film is used as an electromagnetic wave control member or the like, the visible light transmittance is preferably 50% or more, more preferably 53% or more, and even more preferably 55% or more. The upper limit of the visible light transmittance is not particularly limited, but may be, for example, 90% or less, or may be 80% or less. When the visible light transmittance is 50% or more, it is possible to visually recognize objects through the glass substrate laminate with a conductive film.

[0059] The bending rigidity of the conductive film-formed glass substrate laminate 1 according to this embodiment is 1×10 8 N mm 2 More than 1×10 is preferable. 8 ~1×10 11 N mm 2 is more preferable, and 1×10 8 ~1×10 10 N mm 2 The above bending rigidity can be adjusted appropriately depending on the type and thickness of each layer constituting the conductive film-formed glass substrate laminate 1.

[0060] Electromagnetic wave control materials, frequency selective plates The electromagnetic wave control member or frequency selective plate according to this embodiment includes a glass substrate laminate with a conductive film. As this glass substrate laminate with a conductive film, the glass substrate laminate with a conductive film described above in "Glass substrate laminate with a conductive film" can be adopted, and preferred aspects are also the same.

[0061] For example, the electromagnetic wave control member according to this embodiment is preferable because the conductive film-attached glass substrate laminate has selective radio wave transparency and phase adjustment effects. Examples of the electromagnetic wave control member include a radio wave absorber member such as a λ / 4 type radio wave absorber and a frequency selective surface (FSS). Furthermore, by incorporating a frequency selective surface (FSS) into the conductive layer of a λ / 4 type radio wave absorber, a radio wave absorber thinner than a λ / 4 type can be realized. By forming the non-conductive region in the conductive film-attached glass substrate laminate into an arbitrary shape, radio waves of a desired specific frequency can be controlled.

[0062] The electromagnetic wave control member according to this embodiment can be suitably used in places where human bodies, communication devices, sensors, etc. need to be protected from electromagnetic waves, and where measures against communication failure and malfunction are required. For example, when a box-shaped radio wave absorber is used as a self-checkout or warehouse and automatic product recognition is performed inside the radio wave absorber, unnecessary radio waves are suppressed by the radio wave absorber, preventing mistakes in counting products, etc. In addition, there are cases where the electromagnetic wave control member needs to be highly visible.

[0063] One aspect of the electromagnetic wave control member according to this embodiment is a radio wave absorber member. This radio wave absorber member is a member that absorbs unwanted electromagnetic waves to prevent the influence of electromagnetic waves from electronic devices used in close proximity to each other. Compared to this radio wave absorber member, the glass substrate laminate with a conductive film according to this embodiment is preferable because it has selective radio wave transparency.

[0064] The frequency selective plate according to this embodiment is a plate that selectively passes radar waves in a preset frequency band despite a decrease in radio wave transmittance due to reflection or absorption occurring when radio waves pass through, changes in radio wave transmittance due to differences in angle or thickness, radio wave shielding by a conductive film included in a heat ray reflecting film, etc. Compared to this frequency selective plate, the glass substrate laminate with a conductive film according to this embodiment is preferable because it has selective radio wave transmittance and a phase adjustment effect.

[0065] <<Method for manufacturing a glass substrate laminate with a conductive film>> The method for producing the glass substrate laminate with a conductive film according to this embodiment is not particularly limited as long as it can produce the glass substrate laminate with a conductive film described above.

[0066] The manufacturing method according to this embodiment includes a step of patterning conductive regions on at least one main surface of a glass plate to form a patterned conductive film. The patterning in the above step is preferably carried out using at least one method selected from the group consisting of sputtering, vapor deposition, laser processing, etching, photolithography, sandblasting, wet blasting, screen printing, and inkjet printing.

[0067] As the patterning method, a conventionally known method can be used. For example, when patterning is performed by sputtering, a mask is applied to the areas that are to be non-conductive regions, and the material that will form the conductive regions is sputtered in other areas, thereby patterning the conductive regions and forming a patterned conductive film.

[0068] When patterning is performed by vapor deposition, any of the following vapor deposition methods can be used: physical vapor deposition (vacuum vapor deposition, ion plating, magnetron sputtering, etc.) and chemical vapor deposition (thermal CVD, plasma CVD, photo-CVD, etc.). In this case, as with the case of using sputtering, a mask is applied to the areas to be non-conductive, and the material that will form the conductive areas is vapor-deposited in other areas, thereby patterning the conductive areas and forming a patterned conductive film.

[0069] When patterning is performed by laser processing, a conductive film is formed over the entire main surface of the glass plate, and then the areas to be non-conductive regions are removed by laser processing. In this case, the remaining areas are patterned as conductive regions, thereby forming a patterned conductive film.

[0070] As mentioned above, by using laser processing, the edge of the patterned conductive film, which is the boundary with the non-conductive region, can be continuously covered with an oxide film. This is thought to be formed by applying heat from the laser to the conductive film, oxidizing the material of the conductive layer, and becomes the end of the conductive layer.

[0071] In addition, when the conductive film has a protective layer, the oxide film is formed when the material of the conductive layer combines with the oxidized material of the protective layer and loses its laminated structure. Therefore, the pulse width of the laser used in laser processing is preferably on the order of picoseconds or nanoseconds. Generally, the smaller the pulse width, the less the thermal impact of the laser on the target object, and the larger the pulse width, the greater the thermal impact. When a laser with a large pulse width (e.g., on the order of picoseconds or longer) is used, an oxide film is likely to be formed at the edge that forms the boundary with the non-conductive region while removing the conductive film, and ion migration can be suppressed in the final glass substrate laminate with a conductive film obtained.

[0072] The pulse width of the laser is, for example, preferably 1 ps to 1 μs, more preferably 10 ps to 500 ns, even more preferably 100 ps to 500 ns, even more preferably 1 ns to 100 ns, and particularly preferably 10 ns to 100 ns. Here, the pulse width is preferably 1 ps or more, more preferably 10 ps or more, even more preferably 100 ps or more, even more preferably 1 ns or more, especially preferably 10 ns or more, and particularly preferably 20 ns or more. Furthermore, from the viewpoint of suppressing the influence of laser heat on the glass substrate, the pulse width is preferably 1 μs or less, more preferably 500 ns or less, and even more preferably 100 ns or less.

[0073] The wavelength of the laser is preferably 500 to 1500 nm, more preferably 600 to 1400 nm, and even more preferably 700 to 1300 nm. From the viewpoint of oxide film formation, the wavelength is preferably 500 nm or more, more preferably 600 nm or more, and even more preferably 700 nm or more. From the viewpoint of suppressing the influence of the laser on the glass substrate, the wavelength is preferably 1500 nm or less, more preferably 1400 nm or less, and even more preferably 1300 nm or less.

[0074] The scanning speed of the laser may be, for example, 10 to 1000 mm / sec, or 100 to 500 mm / sec.

[0075] The magnitude of the laser energy can be adjusted by the laser output. Specifically, the laser output is preferably 0.1 to 100 W, more preferably 0.1 W or more but less than 100 W, and even more preferably 1 to 50 W. Here, the laser output is preferably 0.1 W or more, more preferably 1 W or more, and preferably 100 W or less, more preferably less than 100 W, and even more preferably 50 W or less.

[0076] When patterning is performed by etching, a conductive film is formed over the entire main surface of the glass plate, and then the areas to be non-conductive regions are removed by etching. In this case, the remaining areas are patterned as conductive regions, thereby forming a patterned conductive film.

[0077] When patterning is performed by photolithography, a material constituting a conductive layer is applied to the region to be the conductive region, and then patterning is performed by exposure and development.

[0078] When patterning is performed by sandblasting or wet blasting, a conductive film is formed over the entire main surface of the glass substrate, and then a mask is applied to the areas that are to be conductive regions, and other areas are ground away by sandblasting or wet blasting, thereby forming a patterned conductive film with patterned conductive regions.

[0079] When patterning is performed by screen printing or inkjet printing, the material that constitutes the conductive layer is printed in the area that is to be the conductive area, and then patterning is performed.

[0080] In addition to the above, the conductive layer may be formed directly or indirectly on the main surface of the glass substrate. The method for indirectly forming the conductive layer is not particularly limited, but examples thereof include a method in which a conductive layer formed on a resin film is attached to the glass substrate and then the resin film is peeled off. [Example]

[0081] The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto. Examples 1 and 2 are both examples.

[0082] <<Production of Glass Substrate Laminate with Conductive Film>> Example 1 A 3mm thick glass substrate (AGC, FL3, soda lime glass, visible light transmittance 91%) was prepared, and a 200nm thick conductive layer mainly composed of silver (Ag) was deposited on one main surface of the glass substrate by sputtering. The sheet resistance of this conductive layer at 20°C was 1.8Ω / □. Next, a nanosecond laser (Keyence Corporation, model number MD-X1520) is used to irradiate the surface of the conductive film-coated substrate in a linear fashion from the surface on which the conductive film is provided, thereby removing part of the conductive film to form a patterned conductive film and obtain a glass substrate with a patterned conductive film.

[0083] The pattern of the patterned conductive film is a patch as shown in FIG. Each conductive region separated by a non-conductive region is a square with sides of 260 mm when viewed in a plan view, i.e., perpendicular to the main surface of the glass substrate. The width of the non-conductive region separating each conductive region is 140 μm. That is, the distance between each conductive region and its adjacent conductive region is 140 μm.

[0084] Next, a thermoplastic resin layer made of cycloolefin polymer resin (COP) having a thickness of 490 μm is formed on the surface of the glass substrate on which the patterned conductive film has been formed. A 3 mm thick glass plate (visible light transmittance 91%) is placed as a transparent layer on the surface of the thermoplastic resin layer, and pressed together under heat to obtain a glass substrate laminate with a conductive film. The resulting glass substrate laminate with a conductive film has the structure shown in the schematic cross-sectional view of Figure 1. The glass substrate laminate with a conductive film has a visible light transmittance of 76% and a bending rigidity of 1.3 x 10 9 N mm 2 This becomes:

[0085] (Example 2) In the same manner as in Example 1, a glass substrate with a patterned conductive film is obtained. A 490 μm thick layer of cycloolefin polymer resin (COP) is formed on the surface of the glass substrate on which the patterned conductive film is formed, followed by a 400 μm thick layer of acrylic resin and a 490 μm thick layer of cycloolefin polymer resin (COP) in that order, forming a thermoplastic resin layer consisting of three layers: COP layer / acrylic layer / COP layer. A 3 mm thick polycarbonate resin plate (visible light transmittance 90%) is placed on the surface of the thermoplastic resin layer as a transparent layer, and the layers are pressed together under heat to obtain a glass substrate laminate with a conductive film. The resulting glass substrate laminate with a conductive film has the structure shown in the schematic cross-sectional view of Figure 1. The glass substrate laminate with a conductive film has a visible light transmittance of 75% and a bending rigidity of 3.7 x 10 8 N mm 2 This becomes:

[0086] "evaluation" The radio wave transmission characteristics of the conductive film-attached glass substrate laminate obtained in Example 1 were calculated using the following conditions. The results are shown in Figure 5. S21 on the vertical axis represents the electromagnetic wave shielding performance, and the horizontal axis represents the frequency of the electromagnetic waves. (conditions) Configuration: LQ3(FSS) / COP / FL3 FSS pattern dimensions: Conductive area = 260mm square, non-conductive area line width = 0.14mm grid pattern Calculation method: Frequency domain analysis using the finite element method Software: CST Studio Suite (registered trademark, Dassault Systems)

[0087] It has been found that the glass substrate laminate with a conductive film according to this embodiment can suppress cracking of the glass substrate by using a laminate having a thermoplastic resin layer. Furthermore, the glass substrate laminate with a conductive film according to this embodiment can transmit low-frequency waves and block high-frequency waves, as shown in Fig. 5. This suggests that the glass substrate laminate can be suitably used as an electromagnetic wave control member or a frequency selective plate. [Explanation of symbols]

[0088] 1, 1' Conductive film-coated glass substrate laminate 10, 10', 10'' glass substrate 11, 11', 11'' glass plates 11a, 11'a First principal surface 11b, 11'b second principal surface 12, 12', 12'' patterned conductive film 13'' conductive area 14'' protective layer 15'' non-conductive area 20, 20' thermoplastic resin layer 30, 30' transparent layer

Claims

1. A laminate in which a glass substrate, a thermoplastic resin layer, and a transparent layer are laminated in this order, The glass substrate is a glass substrate laminate with a conductive film, the glass substrate including: a glass plate; and a patterned conductive film formed on at least one main surface of the glass plate, the patterned conductive film having a conductive region patterned thereon.

2. the glass plate has the patterned conductive film formed on one main surface thereof, 2 . The glass substrate laminate with a conductive film according to claim 1 , wherein the thermoplastic resin layer is laminated on a main surface of the glass substrate on which the patterned conductive film is formed.

3. 2. The glass substrate laminate with a conductive film according to claim 1, wherein the glass plate has a thickness of 2 mm or more.

4. 2. The glass substrate laminate with a conductive film according to claim 1, wherein the thermoplastic resin layer comprises at least one selected from the group consisting of polyvinyl acetal resin, ethylene-vinyl acetate copolymer resin, cycloolefin polymer resin, urethane-based resin, acrylic-based resin, silicone resin, epoxy resin, vinyl acetate resin, vinyl chloride-based resin, and chloroprene rubber.

5. The conductive-film-attached glass substrate laminate according to claim 1 , wherein the transparent layer is made of glass or resin.

6. the transparent layer is made of the resin, 6. The glass substrate laminate with a conductive film according to claim 5, wherein the resin comprises at least one selected from the group consisting of polycarbonate-based resins, acrylic-based resins, aromatic polyester-based resins, polystyrene-based resins, vinyl chloride-based resins, polyester-based resins, polypropylene-based resins, ABS resins, olefin-based resins, and silicone resins.

7. The conductive film-coated glass substrate laminate according to claim 1 , which has a visible light transmittance of 50% or more.

8. Bending rigidity is 1 x 10 ８ N mm ２ The conductive film-attached glass substrate laminate according to claim 1 .

9. 2. The glass substrate laminate with a conductive film according to claim 1, wherein the conductive region contains silver, and the patterned conductive film has a surface resistance of 10 Ω / □ or less at 20°C.

10. The glass substrate laminate with a conductive film according to claim 1 , wherein the patterned conductive film is patterned over the entire surface of at least one of the main surfaces of the glass plate.

11. The glass substrate laminate with a conductive film according to claim 1 , wherein the pattern of the patterned conductive film is a mesh, a patch, a cross element, or a cross slot.

12. The conductive film-attached glass substrate laminate according to claim 1 , wherein the patterned conductive film includes a protective layer.

13. A method for producing the conductive film-attached glass substrate laminate according to any one of claims 1 to 12, comprising: forming a patterned conductive film by patterning a conductive region on at least one main surface of the glass plate; The method for producing a glass substrate laminate with a patterned conductive film, wherein the patterning is performed using at least one method selected from the group consisting of sputtering, vapor deposition, laser processing, etching, photolithography, sandblasting, wet blasting, screen printing, and inkjet printing.

14. An electromagnetic wave control member comprising the conductive film-attached glass substrate laminate according to any one of claims 1 to 12.

15. A frequency selective plate comprising the conductive film-formed glass substrate laminate according to any one of claims 1 to 12.

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