WO2020054762A1 - 電波透過性基板 - Google Patents
電波透過性基板 Download PDFInfo
- Publication number
- WO2020054762A1 WO2020054762A1 PCT/JP2019/035699 JP2019035699W WO2020054762A1 WO 2020054762 A1 WO2020054762 A1 WO 2020054762A1 JP 2019035699 W JP2019035699 W JP 2019035699W WO 2020054762 A1 WO2020054762 A1 WO 2020054762A1
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- WO
- WIPO (PCT)
- Prior art keywords
- radio wave
- heat ray
- opening
- wave transmitting
- reflective film
- Prior art date
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Images
Classifications
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- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/208—Filters for use with infrared or ultraviolet radiation, e.g. for separating visible light from infrared and/or ultraviolet radiation
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
- C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
- C03C17/3644—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer the metal being silver
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
- B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
- B32B17/10009—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets
- B32B17/10036—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets comprising two outer glass sheets
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
- B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
- B32B17/10165—Functional features of the laminated safety glass or glazing
- B32B17/10174—Coatings of a metallic or dielectric material on a constituent layer of glass or polymer
- B32B17/10183—Coatings of a metallic or dielectric material on a constituent layer of glass or polymer being not continuous, e.g. in edge regions
- B32B17/10192—Coatings of a metallic or dielectric material on a constituent layer of glass or polymer being not continuous, e.g. in edge regions patterned in the form of columns or grids
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
- B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
- B32B17/10165—Functional features of the laminated safety glass or glazing
- B32B17/10174—Coatings of a metallic or dielectric material on a constituent layer of glass or polymer
- B32B17/10201—Dielectric coatings
- B32B17/10211—Doped dielectric layer, electrically conductive, e.g. SnO2:F
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
- C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
- C03C17/3652—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer the coating stack containing at least one sacrificial layer to protect the metal from oxidation
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
- C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
- C03C3/087—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal containing calcium oxide, e.g. common sheet or container glass
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/26—Reflecting filters
Definitions
- the present invention relates to a radio wave transmitting substrate.
- a method of giving a window or the like an infrared reflecting function for example, a method of forming a thin film containing a metal having an infrared reflecting function such as silver on a substrate of glass or the like can be mentioned.
- Patent Document 1 discloses a glass laminate including a glass plate and a heat ray reflective film having a metal layer containing silver as a main component on one main surface side of the glass plate.
- a substrate having an infrared reflection function When such a substrate having an infrared reflection function is applied to, for example, a window glass, high transparency to radio waves of a predetermined frequency is also required.
- a substrate having a conventional infrared reflection function has high transparency to radio waves in a relatively low frequency band used in conventional communication, and thus no particular problem of transparency has occurred.
- 4G fourth generation mobile communication systems
- 5G fifth generation mobile communication systems
- the radio wave permeable substrate of the present invention that solves the above-mentioned problems includes a dielectric substrate, a heat reflection film including a conductive film on at least one main surface of the dielectric substrate, and the presence of the conductive film in plan view. And at least a part of the at least one main surface in a plan view is a radio wave permeable area, and the radio wave permeable area is a unit area of all 1 cm squares in the area represented by the following formula ( This is a region that satisfies a).
- L 802.6 ⁇ S-503.7 (a)
- L is the total length (unit: mm / cm 2 ) of the boundary between the heat ray reflective film and the opening in the unit area
- S is the ratio of the area occupied by the heat ray reflective film in the unit area. Is.
- the radio wave transmitting region may satisfy the following expression (b).
- Z is the solar reflectance of the heat reflecting film
- Z ′ is the solar reflectance of the opening
- S ′ is the ratio of the area of the heat reflecting film to the area of the radio wave transmitting region.
- the radio wave transmitting region may satisfy the following expression (c). ⁇ E ⁇ 60.3 ⁇ D ⁇ 0.62 (c) (In equation (c), ⁇ E is the color difference between the heat ray reflective film and the opening, and D is the width (unit: mm) of the opening.)
- the radio wave transmission loss for radio waves having a frequency of 28 GHz in the radio wave transmission region may be 3 dB or less.
- a plurality of parallel or linear lattices of openings may be used.
- At least a part of at least one main surface of the dielectric substrate has a radio wave non-transmissive region, and the radio wave non-transparent region includes all 1 cm square unit regions including the region. May be a region satisfying the following expression (d).
- L 802.6 ⁇ S ⁇ 503.7 (d)
- L is the total length (unit: mm / cm 2 ) of the boundary between the heat ray reflective film and the opening in the unit area
- S is the ratio of the area occupied by the heat ray reflective film in the unit area. Is.
- the conductive film may contain at least one selected from the group consisting of silver and aluminum in a total of 50 atomic% or more.
- the opening may expose the dielectric substrate.
- the dielectric substrate may have a radio wave transmission loss of 4 dB or less for radio waves having a frequency of 28 GHz.
- the conductive film may have a thickness of 1 nm to 100 nm.
- the heat ray reflective film may include at least one of a metal oxide layer and a metal nitride layer different from the conductive film.
- the conductive film may have a structure sandwiched between at least one of a metal oxide layer and a metal nitride layer.
- the dielectric substrate may be formed by stacking a plurality of glass substrates with a resin layer interposed therebetween.
- a radio wave permeable substrate having excellent transparency even for radio waves having a frequency of about several hundred MHz to several tens GHz used in 4G and 5G.
- FIG. 1A and 1B are diagrams illustrating an embodiment of a radio wave transmitting substrate according to the present invention.
- FIG. 1A is a top view
- FIG. 1B is a cross-sectional view taken along line XX of FIG. It is an enlarged view.
- FIG. 2 is a diagram illustrating another embodiment of the radio wave transmitting substrate of the present invention.
- FIG. 3 is a diagram illustrating another embodiment of the radio wave transmitting substrate of the present invention.
- FIG. 1A and 1B are diagrams illustrating an embodiment of a radio wave transmitting substrate according to the present invention.
- FIG. 1A is a top view
- FIG. 1B is a cross-sectional view taken along line XX of FIG. It is an enlarged view.
- the radio wave transmitting substrate 10 of the present embodiment includes a dielectric substrate 11, a heat ray reflective film 13 on at least one main surface of the dielectric substrate 11, and an opening 14 where the heat ray reflective film 13 does not exist in plan view. Is provided. Further, in the radio wave transmitting substrate 10 of the present embodiment, a radio wave transmitting region is formed as a region formed by adjoining a plurality of these in a plan view. In addition, as described later, the opening 14 only needs to have no conductive film included in the heat ray reflective film 13.
- the radio wave permeable region is a region in which all 1 cm square unit regions in the region satisfy the following expression (a).
- L is the total length (unit: mm / cm 2 ) of the boundary between the heat ray reflective film and the opening in the unit area
- S is the ratio of the area occupied by the heat ray reflective film in the unit area. Is.
- the radio wave permeable substrate of the present embodiment having the above-described configuration has excellent transparency even for radio waves having a frequency of about several hundred MHz to several tens GHz.
- features of the radio wave transmitting substrate of the present embodiment will be described in detail.
- the dielectric substrate in the present embodiment is not particularly limited as long as it is a substrate made of a dielectric material.
- a glass substrate such as soda lime glass, non-alkali glass, and quartz glass can be used.
- the glass substrate may be subjected to a physical strengthening process or a chemical strengthening process.
- the glass substrate may be composed of one glass, or may be composed of a plurality of glasses laminated with a resin film (resin film) interposed therebetween.
- the dielectric substrate in the present embodiment is not limited to a glass substrate, and may be, for example, a resin substrate (resin substrate).
- the resin substrate include a substrate made of an acrylic resin such as polymethyl methacrylate, an aromatic polycarbonate resin such as polyphenylene carbonate, and an aromatic polyester resin such as polyethylene terephthalate (PET).
- the shape of the dielectric substrate in the present embodiment is not particularly limited, either, and may be flat or curved. Further, the thickness of the dielectric substrate in the present embodiment is not particularly limited, and can be appropriately adjusted according to desired strength, lightness, and the like.
- the physical properties such as radio wave transmittance and heat ray reflectivity of the dielectric substrate in the present embodiment are not particularly limited as long as the effects of the present invention are exhibited, and may be determined according to the physical properties required for the finally obtained radio wave permeable substrate. , May be adjusted as appropriate.
- the radio wave transmission loss with respect to a 28 GHz radio wave is preferably 4 dB or less, more preferably 3 dB or less, and even more preferably 2 dB or less.
- the radio wave transmission loss can be measured by the method described in the section of Examples.
- each component in the glass substrate is expressed as a mole percentage based on the oxide.
- the expression "substantially does not contain" a certain component of glass means that the component is not actively added unless it is unavoidably mixed as an impurity.
- the specific gravity of the glass substrate is preferably 2.4 or more and 3.0 or less.
- the Young's modulus of the glass substrate is preferably 60 GPa or more and 100 GPa or less.
- the average thermal expansion coefficient of the glass substrate from 50 ° C. to 350 ° C. is preferably from 50 ⁇ 10 ⁇ 7 / ° C. to 120 ⁇ 10 ⁇ 7 / ° C. If the glass substrate satisfies these physical property requirements, it can be suitably used as a window material.
- the glass substrate preferably contains a certain amount or more of SiO 2 in order to secure weather resistance, and as a result, the specific gravity can be 2.4 or more.
- the specific gravity of the glass substrate is more preferably 2.45 or more. Further, when the specific gravity of the glass substrate is 3.0 or less, the glass substrate is less likely to be brittle and lighter.
- the specific gravity of the glass substrate is more preferably 2.6 or less.
- the glass substrate Since the glass substrate has a large Young's modulus, the glass substrate has rigidity, and is more suitable for use in automobile windows and the like.
- the Young's modulus of the glass substrate is preferably 65 GPa or more, more preferably 70 GPa or more, and further preferably 72 GPa or more. If SiO 2 is increased in order to increase the Young's modulus of the glass substrate, the solubility deteriorates. Therefore, an appropriate Young's modulus is 100 GPa or less.
- the Young's modulus of the glass substrate is more preferably 85 GPa or less, and further preferably 78 GPa or less.
- the glass substrate Since the glass substrate has a large average linear expansion coefficient, it can be physically strengthened, and can be preferably used for window applications.
- the average linear expansion coefficient from 50 ° C. to 350 ° C. is more preferably 60 ⁇ 10 ⁇ 7 / ° C. or more, and further preferably 80 ⁇ 10 ⁇ 7 / ° C. or more. If the average linear expansion coefficient is too large, a thermal stress due to the temperature distribution of the glass sheet is likely to be generated in the forming step, the annealing step, or the physical strengthening step, and the sheet may be thermally cracked. In addition, a difference in expansion from a metal sash or the like becomes large, which causes distortion and may lead to cracking.
- the average linear expansion coefficient from 50 ° C. to 350 ° C. is more preferably 110 ⁇ 10 ⁇ 7 / ° C. or less, and further preferably 98 ⁇ 10 ⁇ 7 / ° C. or less.
- T 2 of the glass substrate is preferably 1750 ° C. or lower.
- T 4 of the glass substrate is preferably 1350 ° C. or less.
- T 4 -T L of the glass substrate preferably at least -50 ° C..
- T 2 of the glass substrate is at 1750 ° C. or less, and T 4 is at 1350 ° C. or less, and T 4 -T L is more preferably not less than -50 ° C..
- T 2 represents a temperature at which the glass viscosity becomes 10 2 (dPa ⁇ s)
- T 4 represents a temperature at which the glass viscosity becomes 10 4 (dPa ⁇ s)
- TL represents a temperature of the glass. Represents the liquidus temperature.
- T 2 is more preferably 1600 ° C. or lower, further preferably 1500 ° C. or lower.
- T 4 is more preferably 1350 ° C. or lower, further preferably 1200 ° C. or lower.
- the lower limits of T 2 and T 4 are not particularly limited, but typically T 2 is 1200 ° C. or higher and T 4 is 800 ° C. or higher in order to maintain weather resistance and glass specific gravity.
- T 2 is more preferably 1300 ° C. or higher, further preferably 1400 ° C. or higher.
- T 4 is more preferably 900 ° C. or higher, further preferably 1000 ° C. or higher.
- T 4 -T L of -50 ° C. or higher. If the difference is smaller than ⁇ 50 ° C., devitrification occurs in the glass at the time of molding the glass, and problems such as a decrease in mechanical properties of the glass and a decrease in transparency may occur, and a high quality glass can be obtained. It is not preferable because it may not be available.
- T 4 -T L is more preferably 0 °C or more, still more preferably 20 ° C. or higher.
- T g of the glass substrate 400 ° C. or higher, preferably 750 ° C. or less.
- T g represents the glass transition point of the glass.
- T g is the predetermined temperature range, it is possible to perform bending of the glass within the normal manufacturing conditions range.
- T g is more preferably 450 ° C. or higher, further preferably 480 ° C. or higher, and particularly preferably 520 ° C. or higher.
- T g is too high, a higher temperature during glass bending is required, production becomes more difficult.
- T g is more preferably 600 ° C. or lower, further preferably 550 ° C. or lower.
- the glass substrate can achieve high radio wave transmittance by reducing the dielectric loss by adjusting the glass composition. Similarly, by adjusting the composition, the relative dielectric constant can be adjusted, and a dielectric constant suitable for the intended use can be achieved.
- the glass substrate preferably has a SiO 2 content of 50% or more and 80% or less. Further, the content of Al 2 O 3 is preferably 0% or more and 20% or less. SiO 2 and Al 2 O 3 contribute to the improvement of the Young's modulus, so that it is easy to secure the strength required for architectural applications, automotive window applications, and the like. If the content of Al 2 O 3 and / or SiO 2 is small, it is difficult to secure weather resistance, and the average linear expansion coefficient becomes too large, so that thermal cracking easily occurs. If the amount of Al 2 O 3 and / or SiO 2 is too large, the viscosity at the time of melting the glass increases, which makes glass production unfavorable. If the amount of Al 2 O 3 is too large, the radio wave transmittance may be lowered.
- the content of SiO 2 is more preferably at least 65%, further preferably at least 70%, particularly preferably at least 72%.
- the content of SiO 2 is more preferably 77% or less, further preferably 75% or less.
- the content of Al 2 O 3 is preferably 0.1% or more for improving weather resistance.
- the content of Al 2 O 3 is more preferably 5% or less, still more preferably 1% or less, from the viewpoints of keeping the glass viscosity T 2 low and facilitating the production of glass and improving radio wave transmittance. Particularly preferred is 5% or less.
- the total content of SiO 2 + Al 2 O 3, that is, the content of SiO 2 and the content of Al 2 O 3 is preferably 50% or more and 80% or less.
- the content of SiO 2 + Al 2 O 3 is preferably as small as possible.
- the content of SiO 2 + Al 2 O 3 is more preferably 76% or less, even more preferably 74% or less.
- the content of SiO 2 + Al 2 O 3 is more preferably at least 65%, further preferably at least 72%.
- the glass substrate preferably has a B 2 O 3 content of 0% or more and 15% or less.
- B 2 O 3 can be contained for improving the solubility and the glass strength. Also, there is an effect of increasing the radio wave transmittance. If the content of B 2 O 3 is too large, the alkali element tends to volatilize during melting and molding, which may lead to deterioration of glass quality. On the other hand, when the content of B 2 O 3 is large, the average linear expansion coefficient becomes small, and it becomes difficult to perform physical strengthening.
- the content of B 2 O 3 is more preferably 10% or less, further preferably 3% or less, and particularly preferably substantially no content.
- the glass substrate preferably has a MgO content of 0% or more and 20% or less.
- MgO is a component that promotes melting of the glass raw material and improves weather resistance.
- the content of MgO is preferably 0.1% or more. If the content of MgO is 20% or less, it is difficult to devitrify. MgO may also be effective in increasing the radio wave transmittance.
- the content of MgO is more preferably 4% or less, further preferably 1% or less, and particularly preferably 0.2% or less.
- CaO, SrO, and / or BaO may be included in a certain amount to reduce the dielectric loss of glass.
- the content of CaO is preferably 0% or more and 20% or less.
- the SrO content is preferably 0% or more and 15% or less.
- the BaO content is preferably 0% or more and 15% or less.
- the addition of CaO 3% or more, (decrease in T 2, and decrease in T 4) improve the melting property of the glass may also be effected.
- the content of CaO is more preferably at least 8%, further preferably at least 11%.
- the content of CaO is more preferably 15% or less, and still more preferably 12% or less.
- the content of SrO is more preferably 3% or less, and further preferably substantially no SrO.
- the content of BaO is more preferably 3% or less, and further preferably substantially no content.
- RO indicates the total content of MgO, CaO, SrO, and BaO.
- the glass substrate preferably has an RO of 0% or more and 20% or less. If the RO is at most 20%, the weather resistance will be improved.
- the RO of the glass substrate is more preferably 16% or less, further preferably 13% or less.
- the RO of the glass substrate is preferably more than 0%, more preferably 5% or more, and still more preferably. Is 10% or more.
- the total content of MgO and CaO is preferably 0% or more and 20% or less.
- MgO + CaO is more preferably at most 15%, further preferably at most 13%.
- MgO + CaO is more preferably at least 4%, further preferably at least 10%.
- the glass substrate preferably has a Na 2 O content of 0% or more and 18% or less.
- Na 2 O and K 2 O are components for improving the solubility of the glass, and it is more preferable to contain 0.1% or more of either or both of them. This makes it easier to keep T 2 at 1750 ° C. or less and T 4 at 1350 ° C. or less. Further, by containing Na 2 O, chemical strengthening becomes possible.
- the content of Na 2 O is more preferably 4% or more, and still more preferably 6% or more. If the amount of Na 2 O is too large, the average coefficient of linear expansion becomes too large, so that thermal cracking easily occurs.
- the content of Na 2 O is more preferably 16% or less, further preferably 10% or less, and particularly preferably 8% or less.
- the glass substrate preferably has a K 2 O content of 0% or more and 18% or less.
- K 2 O is a component that improves the solubility of glass, and is more preferably contained at 0.1% or more. This makes it easier to keep T 2 at 1750 ° C. or less and T 4 at 1350 ° C. or less.
- the content of K 2 O is more preferably 2% or more, and still more preferably 5% or more.
- the content of K 2 O is too large, the average coefficient of linear expansion becomes too large, and it is easy to cause thermal cracking. If the content of K 2 O exceeds 18%, the weather resistance is undesirably reduced.
- the content of K 2 O is more preferably at most 12%, further preferably at most 8%.
- the glass substrate preferably has a Li 2 O content of 0% or more and 18% or less.
- Li 2 O is a component that improves the solubility of the glass, and also makes it easy to increase the Young's modulus and contributes to improving the strength of the glass.
- chemical strengthening becomes possible.
- the content may be 0.1% or more, 1% or more, or 3% or more. If the content of Li 2 O is too large, devitrification or phase separation occurs during glass production, which may make production difficult.
- the content of Li 2 O is more preferably 10% or less. Further, since the thermal expansion coefficient may be reduced and physical strengthening may not be performed, it is not preferable to contain too much as glass for automobile windows. Therefore, it is more preferably not more than 7%, further preferably not more than 3%, and particularly preferably substantially not contained.
- R 2 O represents the total amount of the alkali metal oxide. This usually means the sum of the contents of Li 2 O, Na 2 O and K 2 O.
- R 2 O of the glass substrate is preferably 4% or more and 20% or less. When R 2 O is at most 20%, the weather resistance will be improved.
- R 2 O of the glass substrate is more preferably 18% or less, and still more preferably 15% or less.
- R 2 O is preferably at least 4%.
- R 2 O is more preferably at least 9%, further preferably at least 13%, particularly preferably at least 14%.
- the content of ZrO 2 in the glass substrate is preferably 0% or more and 5% or less.
- ZrO 2 has the effect of lowering the viscosity of glass at the time of melting and promoting melting, and can also contribute to the improvement of heat resistance and chemical durability. If the amount of ZrO 2 is large, the liquidus temperature increases, and the average linear expansion coefficient may increase.
- the content of ZrO 2 is more preferably 1.0% or less, and further preferably substantially not contained.
- the content of Fe 2 O 3 in the glass substrate is preferably 0.001% or more and 5% or less. If Fe 2 O 3 is less than 0.001%, it may not be able to be used for applications requiring heat shielding properties, and it is necessary to use expensive raw materials having a low iron content for the production of glass sheets. Is not preferred. Further, by setting the content of Fe 2 O 3 to 0.001% or more, it is possible to suppress the heat radiation from reaching the bottom of the melting furnace more than necessary at the time of melting the glass, and to prevent the load from being applied to the melting furnace. The content of Fe 2 O 3 is more preferably at least 0.01%, further preferably at least 0.05%.
- the content of Fe 2 O 3 is more preferably 1% or less, further preferably 0.3% or less.
- the content of TiO 2 in the glass substrate is preferably 0.001% or more and 5% or less. By setting the content of TiO 2 within this range, it is possible to suppress the formation of a foam layer on the surface of the molten glass during the production of the glass substrate. When the foam layer is formed, the temperature of the molten glass does not rise, making it difficult to clarify, and the productivity tends to deteriorate.
- a titanium compound as an antifoaming agent may be supplied to the foam layer generated on the surface of the molten glass. The titanium compound is taken into the molten glass and exists as TiO 2 .
- the content of TiO 2 is more preferably 0.05% or more.
- the content of TiO 2 may be more preferably 0.1% or more, and further preferably 0.5% or more.
- the content of TiO 2 is preferably limited to 5% or less.
- the content of TiO 2 is more preferably 0.5% or less, further preferably 0.2% or less.
- the glass substrate when moisture is present in the glass substrate, the glass substrate has absorption in the near-infrared light region, so that the light transmittance in the near-infrared light region decreases, which is not suitable for use in infrared irradiation equipment (such as a laser radar).
- Water in the glass generally can be represented by a value of beta-OH value, beta-OH value of the glass substrate is preferably 0.5 mm -1 or less, more preferably 0.3 mm -1 or less, 0.2 mm -1 or less is more preferred.
- ⁇ -OH can be obtained by the following formula from the light transmittance of glass measured using FT-IR (Fourier transform infrared spectrophotometer).
- ⁇ -OH (1 / X) log 10 (T A / T B ) [mm ⁇ 1 ]
- X thickness of sample [mm]
- T A light transmittance [%] at reference wave number 4000 cm ⁇ 1
- T B Minimum light transmittance [%] around 3600 cm ⁇ 1 of hydroxyl group absorption wave number
- beta-OH value of the glass is more preferably 0.05 mm -1 or more preferably 0.10 mm -1, further preferably 0.15 mm -1 or higher .
- the radio wave permeable substrate of the present embodiment has a heat ray reflection film, and the heat ray reflection film has a conductive film, thereby exhibiting a function of reflecting heat rays.
- the heat ray reflective film may include a layer other than the conductive film as long as the effects of the present invention are exerted.
- a layer other than the conductive film in the heat ray reflective film may be referred to as “other layer”.
- the electrical resistivity refers to 10 0 [ ⁇ ⁇ cm] or less of the membrane in 20 ° C.
- the components of the conductive film are not particularly limited, for example, tin oxide (SnO 2 ) doped with at least one of silver, aluminum, indium tin oxide (ITO), fluorine, and antimony having excellent heat ray reflectivity is used.
- F, Sb) a metal such as titanium nitride, niobium nitride, chromium nitride, zirconium nitride, and hafnium nitride (hereinafter also referred to as “conductive film component group A”).
- the term “main component” means that the content of all components is 50 atomic% or more. That is, the conductive film of the present embodiment contains at least one selected from the group consisting of the conductive film component group A, and the content of the conductive film component group A in the conductive film of the present embodiment is a total. Is preferably at least 50 atomic%.
- the conductive film preferably includes at least one of silver and aluminum as a main component, and the conductive film includes silver as a main component (that is, 50%). Is more preferable, and silver is more preferably 95 atom% or more.
- the conductive film containing silver as a main component may contain one or more additional elements such as gold, palladium, copper, bismuth, neodymium, and platinum.
- additional elements such as gold, palladium, copper, bismuth, neodymium, and platinum.
- the thickness of the conductive film of the present embodiment is not particularly limited, and radio wave transmittance of a predetermined frequency required in a finally obtained radio wave permeable substrate, heat ray reflectivity, visible light transmittance, appearance, etc. May be adjusted as appropriate.
- the thickness of the conductive film is usually 1 nm or more, preferably 3 nm or more, more preferably 5 nm or more, and still more preferably 6 nm or more.
- the thickness is preferably 100 nm or less, more preferably 50 nm or less, and even more preferably 20 nm or less.
- the conductive film may be a single layer (single layer) or a multilayer such as two layers or three layers, and when there are multiple layers, they may be adjacent to each other in the thickness direction of the conductive film. Other layers may be interposed between the layers to separate them. In the case where the conductive film is a multilayer, the total thickness may be within the above range.
- the heat ray reflective film of the present embodiment may include a layer (other layer) different from the above-described conductive film as long as the effects of the present invention are exerted.
- the radio wave transmitting substrate of the present embodiment may include, for example, a metal oxide layer or a metal nitride layer, and preferably includes at least one of a metal oxide layer and a metal nitride layer.
- the heat ray reflective film has a layer configuration in which the conductive film is sandwiched between the other layers such as a metal oxide layer and a metal nitride layer.
- the metal oxide layer a layer of a metal oxide containing aluminum oxide, zinc oxide, indium oxide, titanium oxide, niobium oxide, tin oxide, bismuth oxide, tantalum oxide, tungsten oxide, zirconium oxide, silicon oxide, or the like as a main component Is mentioned.
- the metal oxide layer preferably contains zinc oxide as a main component because it has good compatibility with silver, which is a preferable component of the conductive film, and can increase the durability of the conductive film.
- the metal nitride layer include a metal nitride layer containing silicon nitride (Si 3 N 4 ), aluminum nitride (AlN), or the like as a main component.
- the method for forming the heat ray reflective film is not particularly limited.
- a physical vapor deposition method vacuum vapor deposition method, ion plating method, magnetron sputtering method, etc.
- a chemical vapor deposition method thermal CVD method, plasma CVD method, optical CVD method) Etc.
- an ion beam sputtering method or the like can be used.
- the DC magnetron sputtering method, the DC pulse magnetron sputtering method, or the AC dual magnetron sputtering method is preferable because the uniformity of the thickness is easily controlled and the productivity is excellent.
- the heat ray reflective film in this embodiment may be formed directly on the dielectric substrate or may be formed indirectly.
- the method of indirectly forming the heat ray reflective film on the dielectric substrate is not particularly limited, and examples include a method of attaching a resin film having the heat ray reflective film formed thereon to the dielectric substrate.
- the heat ray reflective film 13 (and the opening 14) is formed on one entire main surface of the dielectric substrate 21, but may be formed only on a part thereof.
- FIG. 2 shows an embodiment in which the heat ray reflective film 23 and the opening 24 are provided on a part of one main surface of the dielectric substrate 21 and the dielectric substrate 21 is exposed in a wide range in other parts.
- FIG. 1 shows a top view of a radio wave transmitting substrate 20.
- the opening is a portion where at least the conductive film does not exist in plan view, and is defined by the heat ray reflective film.
- the form of the opening is, for example, when the heat ray reflective film includes a conductive film and a layer other than the conductive film, all the layers other than the conductive film and the conductive film are removed, and the dielectric substrate becomes the outermost surface.
- the form in which a part exists is mentioned. That is, examples of the form of the opening include a form in which the dielectric substrate is exposed.
- the form of the opening is not limited to the form having the portion where the dielectric substrate is the outermost surface.
- the form does not include the conductive film and at least the layer other than the conductive film. It may be a form including one layer. That is, the opening, there is no conductive layer, only a layer of non-conductive film (0 electrical resistivity 10 [ ⁇ ⁇ cm] greater than the film) may be laminated to a dielectric substrate.
- the conductive film may not be present in the opening, and the oxide layer or the nitride layer exemplified in the description of the other layers described above may be stacked on the dielectric substrate.
- the radio wave permeable region includes a plurality of parallel linear openings (hereinafter, also simply referred to as “parallel lines”) in plan view, but the openings are limited to linear.
- the shape may be a circle, an ellipse, a dot, or the like.
- the opening When the opening is linear, the opening may be, for example, a lattice, a curve, a zigzag line, a concentric circle, a spiral, a random line, or the like, in addition to a straight line.
- the linear shape of the opening includes a shape in which the outer edge is a rectangle or a parallelogram when viewed from one opening.
- the method of forming a radio wave permeable region (the method of forming an opening) in the present embodiment is not particularly limited.
- a method of forming a continuous (solid) heat ray reflection film in a predetermined region without providing an opening on a dielectric substrate and then partially removing the heat ray reflection film to form an opening A method of obtaining a radio wave transmitting region by forming a heat ray reflective film only on a predetermined portion on a body substrate is exemplified.
- the heat ray reflective film for example, laser etching, photolithography, or the like can be given.
- the conductive film is removed by photolithography, laser etching, or the like. And the like.
- a portion of the dielectric substrate where the heat ray reflective film is not formed is formed by a sheet or a plate.
- a method of forming a heat ray reflective film by coating (masking) is exemplified.
- the opening is preferably linear, and more preferably straight, from the viewpoint of workability in forming the opening itself.
- the opening is formed by a method of removing a part of the heat ray reflective film by laser etching
- the substrate is transported in the first direction while irradiating the heat ray reflective film with a fixed laser beam.
- a linear opening extending in one direction can be easily formed.
- the substrate is conveyed in a second direction different from the first direction while irradiating a fixed laser to the heat ray reflective film, thereby forming a straight line extending in the first direction and the second direction. Opening can also be easily formed.
- the opening is preferably a linear shape extending in the first direction, or a linear shape extending in the first direction and a linear shape extending in the second direction, from the viewpoint of ease of manufacture as described above.
- the opening is preferably a plurality of parallel lines or lattices, and the heat ray reflective film having a predetermined width and the openings having a predetermined width are alternately arranged in the width direction of the parallel lines or the lattice. It is preferable to have periodicity because the radio wave transmission at a predetermined frequency can be enhanced.
- the openings have a predetermined width and are linear or lattice-shaped extending in one direction, and a plurality of these are arranged in parallel in the width direction, so that the radio wave transmission When the region is formed, the radio wave transmission with respect to the linearly polarized wave orthogonal to the stretching direction becomes high. Therefore, a radio wave transmitting substrate having such a radio wave transmitting region is convenient when a predetermined linearly polarized wave is transmitted with high efficiency.
- such a radio wave permeable substrate as described above is set up vertically with respect to the ground, and when the extending direction of the linear or lattice-shaped opening is set in the horizontal direction with respect to the ground, the vertical polarization is reduced. It is easy to obtain high radio wave permeability for radio waves.
- the radio wave transmitting region is a region in which all 1 cm square unit regions in the region satisfy the following expression (a). Not only radio waves conventionally used but also several hundred MHz to several tens of This is a region having excellent transparency even for radio waves having a frequency of about GHz. In addition, the radio wave transmitting region exhibits more excellent transmission, especially for radio waves of 6 GHz to several tens of GHz, as compared with the related art.
- the radio wave transmitting region in the present embodiment may be formed only on one main surface of the dielectric substrate, or may be formed on both main surfaces. When the radio wave transmitting regions are formed on both main surfaces of the dielectric substrate, the radio wave transmitting regions of both main surfaces may partially or entirely overlap in plan view, or may not overlap at all.
- the present inventors have found that, in the radio wave transmitting region, in addition to the ratio of the area occupied by the heat ray reflecting film in a plan view, that is, the coverage of the heat ray reflecting film, the boundary between the heat ray reflecting film and the opening in the radio wave transmitting region. was also found to be a factor affecting radio wave transmission, and it was found that radio transmission could be improved by increasing the total length of the boundary line.
- a radio wave enters the radio wave permeable area, an electromagnetic field is generated between the conductive films facing each other across the opening, and the radio wave is re-emitted to the opposite side of the incident surface, resulting in high radio wave transparency .
- the portion where the conductive film faces each other across the opening increases, and the efficiency of generation and re-emission of an electromagnetic field increases, thereby improving radio wave transmission.
- the present inventors have found that the radio wave transmission is particularly good in a region satisfying the above formula (a), and that the radio wave has an excellent radio wave transmission at a frequency of about several hundred MHz to several tens of GHz.
- the present inventors have found out that the present invention is effective, and have completed the present invention.
- the values of the total length L of the boundary line between the heat ray reflective film and the opening in the unit area and the value S of the area occupied by the heat ray reflective film in the unit area in plan view are determined by the values in the radio wave permeable area. It depends on whether the unit area is observed.
- the radio wave permeable area L ′ is the average value of the boundary line length per unit area
- a value obtained by dividing the entire area of the heat ray reflective film in the radio wave permeable area by the entire area of the radio wave permeable area (hereinafter, “the radio wave permeable area”) L) and S ′ are different from L ′ and S ′ depending on the unit region to be observed.
- any unit in the radio wave permeable region can be used. Even when the region is observed, L and S substantially match L 'and S'.
- S ′ is preferably at least 65%, more preferably at least 80%, even more preferably at least 90%.
- L' is preferably 100 mm / cm 2 or more, 300 mm / cm 2 or more, and still more preferably 500 mm / cm 2 or more.
- the difference between L and S and L ′ and S ′ is preferably within ⁇ 10%, more preferably within ⁇ 5%.
- the present inventors When the radio wave transmitting region further satisfies the following formula (b), the present inventors have obtained a radio wave transmitting substrate which is particularly excellent in heat ray reflectivity and has both excellent radio wave transmittance and heat ray reflectivity.
- the radio wave transmitting region more preferably satisfies the following expression (b).
- Z is the solar reflectance of the heat ray reflective film
- Z ' is the solar reflectance of the opening
- S' is the coverage of the heat ray reflective film in the radio wave transmitting region.
- the above-mentioned solar reflectance refers to the solar reflectance defined by JIS R3106 (1998), and the standard also applies to the solar reflectance described later.
- Z ′ corresponds to the solar reflectance of the dielectric substrate.
- the radio wave transmitting region more preferably satisfies the following expression (b-1), further preferably satisfies the following expression (b-2), and more preferably satisfies the following expression (b-2). It is particularly preferable to satisfy (b-3).
- Z ( ⁇ Z ′ + Z ′ ⁇ S ′ + 0.35) / S ′ (b-1) Z> ( ⁇ Z ′ + Z ′ ⁇ S ′ + 0.4) / S ′ (b-2) Z> ( ⁇ Z ′ + Z ′ ⁇ S ′ + 0.43) / S ′ (b-3)
- Z is the solar reflectance of the heat ray reflective film
- Z ' is the solar reflectance of the opening
- S' is the radio wave transmission. This is the coverage of the heat ray reflective film in the neutral region.
- the present inventors have found that when the radio wave transmitting region further satisfies the following formula (c), the opening is hardly visually recognized, and a radio wave transmitting region excellent in appearance can be obtained. That is, in the present embodiment, the radio wave transmitting region more preferably satisfies the following expression (c). ⁇ E ⁇ 60.3 ⁇ D ⁇ 0.62 (c) (In equation (c), ⁇ E is the color difference between the heat ray reflective film and the opening, and D is the width (unit: mm) of the opening.) That is, as ⁇ E is smaller and D is smaller, the opening is less visible. When the heat ray reflective film does not exist, the surface of the opening corresponds to a dielectric substrate.
- the radio wave transmitting region more preferably satisfies the following expression (c-1), and further satisfies the following expression (c-2). It is particularly preferable that the following formula (c-3) is satisfied.
- ⁇ E ⁇ 60.3 ⁇ D ⁇ 0.62 ⁇ 50 (c-1) ⁇ E ⁇ 60.3 ⁇ D ⁇ 0.62 ⁇ 150 (c-2) ⁇ E ⁇ 60.3 ⁇ D ⁇ 0.62 ⁇ 350 (c-3) (In Equations (c-1) to (c-3), ⁇ E is the color difference between the heat ray reflective film and the opening, and D is the width (unit: mm) of the opening.)
- ⁇ L * , ⁇ a * , and ⁇ b * are values defined by the following formulas (c-ii) to (c-iv).
- L * (heat ray reflective film), a * (heat ray reflective film), and b * (heat ray reflective film) are each in the L * a * b * color system. This is the color tone of the heat ray reflective film.
- L * (opening), a * (opening), and b * (opening) are respectively the values of the opening in the L * a * b * color system.
- the color tone. ⁇ E can be measured by the method described in the section of Examples.
- the width D of the opening indicates the width (thickness) of the line when the opening is linear.
- the width of the opening D is the shortest length of a line segment passing through the center of gravity of the shape of the opening that can be defined inside the opening when the opening is a dot, a circle, an ellipse, or the like. Point out. That is, the width of the opening D refers to the length of one side of the square when the opening is a square dot, and the width of the rectangle when the opening is a rectangular dot. In the case of a circular shape, the length of the short side refers to the length of the diameter of the circle, and in the case of an elliptical shape, the length of the short axis of the ellipse is referred to.
- the width of the opening having the largest width is defined as the width D of the opening in the above expression (c), and the above expression (c) is used. It is determined whether or not the condition is satisfied.
- the entire area where the radio wave transmitting substrate includes the heat ray reflective film and the opening may be a radio wave transmitting area or a part may be a radio wave transmitting area.
- a region other than the radio wave transmitting region in the region where the radio wave transmitting substrate includes the heat ray reflective film and the opening may be referred to as a radio wave non-transmitting region.
- the whole area on the radio wave permeable substrate is the radio wave permeable area A, but like the radio wave permeable substrate 30 according to another embodiment shown in FIG.
- the upper part may be a radio wave permeable area A, and the other part may be a radio wave opaque area B.
- the radio wave non-transmissive region is a region in which all the 1 cm square unit regions including the region satisfy the following formula (d) among the regions in which the radio wave transmitting substrate includes the heat ray reflective film and the opening.
- L 802.6 ⁇ S ⁇ 503.7 (d)
- L is the total length (unit: [mm / cm 2 ]) of the boundary between the heat ray reflective film and the opening in the unit area
- S is the area occupied by the heat ray reflective film in the unit area. Is the ratio of.
- the radio wave opaque region may or may not have an opening. That is, the radio wave non-transmissive region may be a region in which an opening is formed so as to satisfy the above formula (d), or may be a region in which an opening is not provided and only a heat ray reflective film is provided. .
- the radio wave non-transmissive area is an area formed with only the heat ray reflective film without the opening formed. preferable.
- the radio wave permeable substrate of the present embodiment may or may not include the radio wave opaque region.
- the whole area on the radio wave permeable substrate is a radio wave permeable area, and it is often preferable to not include a radio wave opaque area.
- a radio transmitter / receiver when installed on a part of a radio wave permeable substrate, only a range necessary for transmission / reception of the radio transmitter / receiver is set as a radio wave permeable area, and other parts are radio wave opaque areas. In many cases.
- the radio wave permeable region of the radio wave permeable substrate of the present embodiment exhibits excellent transparency especially for radio waves having a frequency of about several hundred MHz to several tens of GHz, and further has a frequency of about 6 GHz to several tens of GHz. Demonstrates excellent transparency to radio waves. More specifically, the radio wave transmitting substrate of the present embodiment is less likely to hinder the transmission of radio waves of a predetermined frequency in the radio wave transmitting region.
- the radio wave transmission loss with respect to a radio wave having a frequency of 28 GHz in the radio wave transmitting region is preferably 3 dB or less, more preferably 2 dB or less, and further preferably 1 dB or less.
- the radio wave transmission loss with respect to a radio wave having a frequency of 79 GHz is also preferably 3 dB or less, more preferably 2 dB or less, and even more preferably 1 dB or less.
- the radio wave transmission loss for a radio wave having a frequency of 28 GHz (79 GHz) in the radio wave transmission region is calculated from the radio wave transmission loss for a radio wave having a frequency of 28 GHz (79 GHz) for the entire radio wave transmission substrate in the radio wave transmission region.
- (79 GHz) is a value obtained by subtracting a radio wave transmission loss for a radio wave of (79 GHz).
- the radio wave transmission loss for radio waves of frequencies 28 GHz and 79 GHz has been described as an example.
- the radio wave transmission loss similar to the above is not limited to the 28 GHz band and the 79 GHz band, but is also in the frequency band of several hundred MHz to several tens GHz.
- a loss is obtained.
- the radio wave transmitting substrate of the present embodiment preferably has excellent heat ray reflectivity.
- the heat ray reflectivity can be evaluated, for example, by the solar reflectance specified in JIS R3106 (1998).
- the solar reflectance in the radio wave transmitting region of the radio wave transmitting substrate of the present embodiment is preferably 30% or more, more preferably 35% or more, and even more preferably 40% or more.
- a glass plate was manufactured as a dielectric substrate. Specifically, the raw materials were put into a platinum crucible so that the glass composition (unit: mol%) shown in Table 1 was obtained, melted at 1550 ° C. for 2 hours, and then the molten liquid was poured out onto a carbon plate and gradually cooled. After cooling, seven types of glass plates of composition examples 1 to 7 were obtained. Both surfaces of the obtained plate were polished to obtain a glass plate having a size of 100 mm ⁇ 100 mm and a thickness of 2.8 mm. Table 1 shows the specific gravity, average thermal expansion coefficient from 50 ° C.
- the glass plate of Composition Example 1 was washed, introduced into an in-line type sputtering apparatus, and evacuated in the load lock chamber until the degree of vacuum became 2 ⁇ 10 ⁇ 6 Torr or less. Subsequently, the glass plate was introduced into the sputtering chamber, and the total thickness of two layers of tin-doped zinc oxide and aluminum-doped zinc oxide was 43.5 nm on the glass plate surface. A film was formed. Subsequently, the total thickness of the three layers is 87 in the order of 12.5 nm in thickness of silver, 2 nm in titanium, zinc oxide doped with aluminum, zinc oxide doped with tin, and zinc oxide doped with aluminum.
- the laminate was heat-treated at 730 ° C. for 4 minutes in the air to obtain a glass plate on which the heat ray reflective film was formed.
- the entire heat ray reflective film (100 mm ⁇ 100 mm) is parallel to the width direction at equal intervals so that the width of the heat ray reflective film is 0.07 mm and the width of the opening is 0.03 mm.
- a plurality of arranged linear openings were provided, and the radio wave permeable substrate of Example 1 was obtained. Further, the radio wave transmission of Examples 2 to 13 and Comparative Examples 1 to 9 was performed in the same manner as in Example 1 except that the width of the heat ray reflective film and the width of the opening were respectively as shown in Table 2. A functional substrate was obtained.
- Example 14 a glass plate having a composition example 4 and a thickness of 1.8 mm was used.
- a film was formed on the glass plate surface such that the total thickness of two layers of zinc oxide doped with tin and zinc oxide doped with aluminum became 50 nm.
- silver is 17.5 nm in thickness
- titanium is 1 nm
- zinc oxide doped with aluminum zinc oxide doped with tin
- zinc oxide doped with aluminum so that the total thickness of the three layers is 80 nm.
- the laminate was heat-treated at 730 ° C. for 4 minutes in air to obtain a glass plate on which a heat ray reflective film was formed.
- the entire heat ray reflective film (100 mm ⁇ 100 mm) is parallel to the width direction at equal intervals so that the width of the heat ray reflective film becomes 0.2 mm and the width of the opening becomes 0.099 mm.
- a plurality of arranged linear openings were provided to obtain a radio wave permeable substrate of Example 14.
- Example 15 a glass plate having a composition example 5 and a thickness of 1.8 mm was used. After forming the heat ray reflective film in the same manner as in Example 14, the width of the heat ray reflective film was 0.1 mm and the width of the opening was 0.05 mm over the entire heat ray reflective film (100 mm ⁇ 100 mm) by laser decoating. Thus, a plurality of linear openings arranged in a lattice were provided to obtain a radio wave permeable substrate.
- Example 16 a composition example 1 and a glass plate having a thickness of 8.0 mm were used.
- a substrate temperature of 600 ° C. 55 nm of SiOC and 320 nm of fluorine-doped tin oxide (SnO 2 : F) were sequentially formed by a thermal CVD method.
- the heat ray reflective film is parallel to the entire width (100 mm ⁇ 100 mm) and is evenly spaced in parallel with the width direction such that the width of the heat ray reflective film is 0.321 mm and the width of the opening is 0.030 mm.
- a plurality of arranged linear openings were provided to obtain a radio wave permeable substrate of Example 14.
- Example 17 a composition example 1 and a glass plate having a thickness of 6.0 mm were used.
- 30 nm of Al-doped silicon nitride, 30 nm of chromium nitride, and 30 nm of Al-doped silicon nitride were sequentially formed.
- the entire heat ray reflective film (100 mm ⁇ 100 mm) is parallel to the width direction at equal intervals so that the width of the heat ray reflective film is 0.128 mm and the width of the opening is 0.030 mm.
- a plurality of arranged linear openings were provided to obtain a radio wave permeable substrate of Example 17.
- a radio wave transmitting region was formed on the whole (100 mm ⁇ 100 mm) in plan view of the radio wave transmitting substrate.
- the width of the heat ray reflective film, the width D of the opening, the coverage S 'of the heat ray reflective film in the radio wave permeable region, and the average value L' of the boundary line length per unit area in the radio wave permeable region are shown. It is shown in FIG.
- all of the formed film was removed in the opening, that is, the glass plate was exposed in the opening. Therefore, in each of Examples and Comparative Examples, the solar reflectance and chromaticity of the opening coincide with the solar reflectance and chromaticity of the glass plate.
- Table 2 shows the difference (left side-right side) between the left side and the right side of the following equations (a), (b), and (c) for the radio wave permeable substrate of each example.
- L 802.6 ⁇ S-503.7
- the expressions (a) and (b) if the values shown in Table 2 are larger than 0, the expressions (a) and (b) are satisfied.
- the expression (c) if the value shown in Table 2 is smaller than 0, the expression (c) is satisfied.
- the openings are provided at equal intervals, and the widths of the openings and the heat ray reflective film are sufficiently smaller than 1 cm. Therefore, in the calculation of the expression (a), L is used instead of L. 'Was replaced by S' and S 'was used.
- the radio wave transmission loss of the manufactured radio wave permeable substrate was measured by the free space method.
- the radio wave transmission loss is measured by placing the obtained radio wave permeable substrate in the middle of the antenna so that the extension direction of the opening and the polarization direction of the radio wave are orthogonal to each other, and transmitting the radio wave through the opening of 100 mm ⁇ .
- the transmission loss with respect to a radio wave having a frequency of 28 GHz was measured by setting the case where there is no conductive substrate to 0 dB.
- the radio wave transmission loss was measured for only the glass plate before the heat ray reflective film was formed. From these measured values, the radio wave transmission loss with respect to the radio wave having a frequency of 28 GHz in the radio wave transmitting region was calculated for the radio wave transmitting substrate of each example. Table 2 shows the results.
- the radio wave transmitting substrates of Comparative Examples 1 to 9 that do not satisfy the expression (a) have a radio wave transmission loss of more than 3 dB with respect to a radio wave of a frequency of 28 GHz in the radio wave transmitting region, and are inferior in radio wave transmission.
- the radio wave transmission loss with respect to the radio wave transmitting substrates of Examples 1 to 17 satisfying the expression (a) is 3 dB or less. Excellent results were obtained.
- the radio wave transmitting substrates of Examples 1 to 7, 9, 10 and 13 to 17 further satisfying the formula (b) had a relatively high solar reflectance and excellent heat ray reflectivity. Further, all of Examples 1 to 17 satisfied Expression (c), the opening was hardly visually recognized, and the appearance was excellent.
- the radio wave transmitting substrate satisfying the expression (a) has a radio wave transmission loss of 3 dB or less for a radio wave having a frequency of 28 GHz in the radio wave transmitting region. As a result, excellent results in radio wave transmission can be obtained.
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Abstract
Description
L>802.6×S-503.7 ・・・(a)
(式(a)中、Lは単位領域内の熱線反射膜と開口部との境界線の全長(単位はmm/cm2)であり、Sは単位領域内の熱線反射膜の占める面積の割合である。)
Z>(-Z´+Z´×S´+0.3)/S´ ・・・(b)
(式(b)中、Zは熱線反射膜の日射反射率であり、Z´は開口部の日射反射率であり、S´は電波透過性領域の面積に対する熱線反射膜の面積の割合である。)
ΔE<60.3×D-0.62 ・・・(c)
(式(c)中、ΔEは熱線反射膜と開口部との色差であり、Dは開口部の幅(単位はmm)である。)
L≦802.6×S-503.7 ・・・(d)
(式(d)中、Lは単位領域内の熱線反射膜と開口部との境界線の全長(単位はmm/cm2)であり、Sは単位領域内の熱線反射膜の占める面積の割合である。)
L>802.6×S-503.7 ・・・(a)
(式(a)中、Lは単位領域内の熱線反射膜と開口部との境界線の全長(単位はmm/cm2)であり、Sは単位領域内の熱線反射膜の占める面積の割合である。)
本実施形態における誘電体基板は、誘電体からなる基板であれば特に限定されないが、例えば、ソーダライムガラスや無アルカリガラス、石英ガラス等のガラス基板を使用できる。ガラス基板には物理強化処理や化学強化処理が施されていてもよい。またガラス基板は一枚のガラスから構成されてもよく、複数のガラスが樹脂製の膜(樹脂膜)等を挟んで積層されて構成してもよい。
また、本実施形態における誘電体基板はガラス基板に限定されず、例えば樹脂製の基板(樹脂基板)等でもよい。樹脂基板としては例えば、ポリメチルメタクリレート等のアクリル系樹脂やポリフェニレンカーボネート等の芳香族ポリカーボネート系樹脂、ポリエチレンテレフタレート(PET)等の芳香族ポリエステル系樹脂等からなる基板が挙げられる。
例えば、本実施形態における誘電体基板は、28GHzの電波に対する電波透過損失が、4dB以下が好ましく、3dB以下がより好ましく、2dB以下がさらに好ましい。電波透過損失は、実施例の欄に記載の方法により測定できる。
Al2O3の含有量は、耐候性改善のため0.1%以上が好ましい。Al2O3の含有量は、ガラス粘性T2を低く保ちガラスを製造しやすくするために、および電波透過率を良くする観点から5%以下がより好ましく、1%以下がさらに好ましく、0.5%以下が特に好ましい。
また、製造時におけるガラスの粘性T2、T4を下げる観点から、あるいはヤング率を高くする観点から、ガラス基板のROは0%超であることが好ましく、より好ましくは5%以上、さらに好ましくは10%以上である。
Na2Oが多すぎると、平均線膨張係数が大きくなりすぎて熱割れしやすくなる。Na2Oの含有量はより好ましくは16%以下であり、さらに好ましくは10%以下、特に好ましくは8%以下である。
また、K2Oの含有量が多すぎると、平均線膨張係数が大きくなりすぎて熱割れしやすくなる。K2Oの含有量が18%超となると耐候性が低下して好ましくない。K2Oの含有量はより好ましくは12%以下であり、さらに好ましくは8%以下である。
ガラス基板にNa2OとK2Oをともに含有させることで、溶解性を維持しつつ、耐候性を改善することができるためより好ましく、さらに、電波透過率も高くするのにも効果がある場合がある。Na2Oおよび/またはK2Oの含有量が少ないと、平均線膨張係数を大きくすることができず熱強化ができなくなるおそれがある。Na2Oおよび/またはK2Oの含有量を上記所定量にすることで、他の部材との整合性も良い窓用材料として利用できるようになる。電波透過率の観点からは、上記範囲とすることで高い電波透過率を得ることができる。
Li2Oの含有量が多すぎると、ガラス製造時に失透もしくは分相が生じ、製造が困難になるおそれがある。Li2Oの含有量はより好ましくは10%以下である。また、熱膨張係数を低下させ、物理強化ができなくなるおそれがあるため、自動車窓用ガラスとしては含有しすぎても好ましくない。そのため、より好ましくは7%以下、さらに好ましくは3%以下、特に好ましくは実質的に含有しない。
また、製造時におけるガラスの粘性T2、T4を下げる観点から、R2Oは4%以上が好ましい。R2Oはより好ましくは9%以上、さらに好ましくは13%以上、特に好ましくは14%以上である。
Fe2O3の含有量が5%超であると、輻射による伝熱が妨げられて原料が溶融しにくくなるおそれがある。さらに、Fe2O3の含有量が多くなりすぎると、可視域の光透過率の低下がおこるため、自動車窓用途での使用に適さなくなるおそれがある。Fe2O3の含有量はより好ましくは1%以下、さらに好ましくは0.3%以下である。
β-OH=(1/X)log10(TA/TB)[mm-1]
X:サンプルの厚み[mm]
TA:参照波数4000cm-1における光透過率[%]
TB:水酸基吸収波数3600cm-1付近における最小光透過率[%]
本実施形態の電波透過性基板は、熱線反射膜を備え、熱線反射膜は導電性膜を備えることにより、熱線を反射する機能を奏する。また、熱線反射膜は本発明の効果を奏する限りにおいて導電性膜以外の層を備えてもよい。以下、熱線反射膜における導電性膜以外の層を「その他の層」という場合がある。
開口部は、平面視において少なくとも導電性膜が存在しない部分であり、熱線反射膜によって区画される。開口部の形態は、例えば、熱線反射膜が導電性膜と導電性膜以外の層を含む場合、導電性膜と導電性膜以外の層の全てが取り除かれ、誘電体基板が最表面となる部分が存在する形態が挙げられる。すなわち、開口部の形態としては、誘電体基板が露出している形態が挙げられる。
本実施形態において、電波透過性領域は、領域内のすべての1cm四方の単位領域が下記式(a)を満足する領域であり、従来用いられている電波のみならず、数百MHz~数十GHz程度の周波数の電波に対しても優れた透過性を有する領域である。また、電波透過性領域は、とくに6GHz~数十GHzの電波に対して、従来に比べより優れた透過性を発揮する。
L>802.6×S-503.7 ・・・(a)
(式(a)中、Lは単位領域内の熱線反射膜と開口部との境界線の全長(単位はmm/cm2)であり、Sは単位領域内の熱線反射膜の占める面積の割合である。)
なお、本実施形態における電波透過性領域は、誘電体基板の一方の主面のみに形成されてもよく、両方の主面に形成されてもよい。電波透過性領域が誘電体基板の両主面に形成される場合、平面視において両主面の各々の電波透過性領域が一部または全部重なる構成でも、全く重ならない構成でもよい。
L>802.6×S-403.7 ・・・(a-1)
L>802.6×S-103.7 ・・・(a-2)
Z>(-Z´+Z´×S´+0.3)/S´ ・・・(b)
(式(b)中、Zは熱線反射膜の日射反射率であり、Z´は開口部の日射反射率であり、S´は電波透過性領域における熱線反射膜の被覆率である。)
Z>(-Z´+Z´×S´+0.35)/S´ ・・・(b-1)
Z>(-Z´+Z´×S´+0.4)/S´ ・・・(b-2)
Z>(-Z´+Z´×S´+0.43)/S´ ・・・(b-3)
(式(b-1)、(b-2)及び(b-3)中、Zは熱線反射膜の日射反射率であり、Z´は開口部の日射反射率であり、S´は電波透過性領域における熱線反射膜の被覆率である。)
ΔE<60.3×D-0.62 ・・・(c)
(式(c)中、ΔEは熱線反射膜と開口部との色差であり、Dは開口部の幅(単位はmm)である。)
すなわち、ΔEが小さいほど、また、Dが小さいほど、開口部は視認されにくい。また、開口部は、熱線反射膜が存在しない場合、その表面が誘電体基板に相当する。
また、本実施形態において、開口部の視認されにくさの観点からは、電波透過性領域は下記式(c-1)を満たすことがより好ましく、下記式(c-2)を満たすことがさらに好ましく、下記式(c-3)を満たすことが特に好ましい。
ΔE<60.3×D-0.62-50・・・(c-1)
ΔE<60.3×D-0.62-150・・・(c-2)
ΔE<60.3×D-0.62-350・・・(c-3)
(式(c-1)~(c-3)中、ΔEは熱線反射膜と開口部との色差であり、Dは開口部の幅(単位はmm)である。)
ΔE={(ΔL*)2+(Δa*)2+(Δb*)2}1/2 ・・・(c-i)
上記の式(c-i)中、ΔL*、Δa*、及びΔb*は下記式(c-ii)~(c-iv)で定義される値である。
ΔL*=|L*(熱線反射膜)-L*(開口部)| ・・・(c-ii)
Δa*=|a*(熱線反射膜)-a*(開口部)| ・・・(c-iii)
Δb*=|b*(熱線反射膜)-b*(開口部)| ・・・(c-iv)
上記の式(c-ii)~(c-iv)におけるL*(熱線反射膜)、a*(熱線反射膜)、b*(熱線反射膜)はそれぞれL*a*b*表色系における熱線反射膜の色調である。
上記の式(c-ii)~(c-iv)におけるL*(開口部)、a*(開口部)、b*(開口部)はそれぞれL*a*b*表色系における開口部の色調である。
ΔEは、実施例の欄に記載の方法で測定できる。
本実施形態において、電波透過性基板が熱線反射膜と開口部とを備える領域は、その全体が電波透過性領域であってもよく、一部が電波透過性領域であってもよい。なお、以下において電波透過性基板が熱線反射膜と開口部とを備える領域のうち電波透過性領域以外の領域のことを電波非透過性領域と呼ぶことがある。
L≦802.6×S-503.7 ・・・(d)
(式(d)中、Lは単位領域内の熱線反射膜と開口部との境界線の全長(単位は[mm/cm2])であり、Sは単位領域内の熱線反射膜の占める面積の割合である。)
本実施形態の電波透過性基板の電波透過性領域は、特に数百MHz~数十GHz程度の周波数の電波に対しても優れた透過性を発揮し、さらに6GHz~数十GHz程度の周波数の電波に対して優れた透過性を発揮する。より詳細には、本実施形態の電波透過性基板は、電波透過性領域において、所定の周波数の電波の透過を阻害されにくい。
このように、周波数28GHz及び79GHzの電波に対する電波透過損失を例に挙げて説明したが、28GHz帯及び79GHz帯に限らず、数百MHz~数十GHz程度の周波数帯において上記と同様の電波透過損失が得られることが好ましい。
まず、誘電体基板として、ガラス板を作製した。具体的には、表1に示すガラス組成(単位:モル%)となるように、白金坩堝に原料を投入し、1550℃で2時間溶融した後、カーボン板上に溶融液を流し出して徐冷し、組成例1~7の7種類のガラスの板を得た。得られた板の両面を研磨し、100mm×100mm、厚さ2.8mmのガラス板を得た。得られたガラス板の比重、50℃から350℃までの平均熱膨張係数、T2、T4、TL、ガラス転移点Tg、β-OHを表1に示す。なお、表中の「-」は測定しなかったことを示し、組成から計算によって求めた値はカッコを付けて示す。
次いで、レーザーデコートにより、熱線反射膜の全体(100mm×100mm)に、熱線反射膜の幅が0.2mm、開口部の幅が0.099mmとなるように、幅方向に平行で等間隔に配置した複数の線状開口部を設け、実施例14の電波透過性基板を得た。
各例について、熱線反射膜の幅、開口部の幅D、電波透過性領域における熱線反射膜の被覆率S´、電波透過性領域内の単位面積当たりの境界線長の平均値L´を表2に示す。
なお、各実施例及び比較例においては、開口部においては形成された膜が全て除去されており、即ち、開口部においてガラス板が露出している。したがって、各実施例及び比較例においては開口部の日射反射率や色度は、ガラス板の日射反射率や色度と一致する。
各例の電波透過性基板につき、電波透過性領域を設けた面を測定面とし、分光光度計(日立ハイテクノロジーズ社製「U-4100」)を用いて、JIS R3106(1998年)の規定に従って、日射反射率および可視光透過率を測定した。また、開口部を設ける前の全体に導電膜が形成されたガラス板、及び、熱線反射膜を設ける前のガラス板について同様に測定を行い、熱線反射膜の日射反射率Z及び開口部の日射反射率Z´も測定した。結果を表2に示す。
開口部を設ける前の全体に熱線反射膜が形成されたガラス板、及び、熱線反射膜を形成する前のガラス板について、分光光度計(日立ハイテクノロジーズ社製「U-4100」)を用いて波長300nm~800nmの光透過率を測定し、JIS Z8729の規定に従ってC光源を2度入射した場合のL*a*b*表色系の透過光の色度を測定した。得られた色度を用いて、熱線反射膜と開口部との色差ΔEを算出した。結果を表2に示す。
各例の電波透過性基板につき、以下の式(a)、(b)及び(c)の左辺と右辺の差(左辺-右辺)を表2に示す。
L>802.6×S-503.7 ・・・(a)
Z>(-Z´+Z´×S´+0.3)/S´ ・・・(b)
ΔE<60.3×D-0.62 ・・・(c)
即ち、式(a)及び(b)については、表2に示す値が0より大きければ式(a)及び(b)を満足する。式(c)については、表2に示す値が0より小さければ式(c)を満足する。
なお、いずれの例においても開口部は等間隔に設けられており、開口部及び熱線反射膜の幅は1cmに対して十分に小さいので、式(a)の計算においては、Lに替えてL´を、Sに替えてS´を用いた。
自由空間法にて、作製した電波透過性基板の電波透過損失を測定した。電波透過損失は、アンテナを対向させ、それらの中間に、得られた電波透過性基板を開口部の延伸方向と電波の偏波方向が直交するように設置し、100mmΦの開口部にて電波透過性基板がない場合を0dBとして、周波数28GHzの電波に対する電波透過損失を測定した。また、熱線反射膜を形成する前のガラス板のみについても同様に電波透過損失を測定した。これらの測定値より、各例の電波透過性基板について、電波透過性領域における周波数28GHzの電波に対する電波透過損失を算出した。結果を表2に示す。
一方、式(a)を満足する実施例1~17の電波透過性基板に対する電波透過損失の評価では、電波透過性領域における周波数28GHzの電波に対する電波透過損失が3dB以下であり、電波透過性に優れた結果が得られた。
11、21 誘電体基板
13、23、33 熱線反射膜
14、24、34 開口部
A 電波透過性領域
B 電波非透過性領域
Claims (13)
- 誘電体基板と、前記誘電体基板の少なくとも一方の主面上に、導電性膜を含む熱線反射膜と、平面視において前記導電性膜の存在しない開口部とを備え、
前記少なくとも一方の主面上の平面視における少なくとも一部が電波透過性領域であり、
前記電波透過性領域は、該領域内のすべての1cm四方の単位領域が下記式(a)を満足する領域である、電波透過性基板。
L>802.6×S-503.7 ・・・(a)
(式(a)中、Lは前記単位領域内の前記熱線反射膜と前記開口部との境界線の全長(単位はmm/cm2)であり、Sは前記単位領域内の前記熱線反射膜の占める面積の割合である。) - 前記電波透過性領域は、下記式(b)を満足する請求項1に記載の電波透過性基板。
Z>(-Z´+Z´×S´+0.3)/S´ ・・・(b)
(式(b)中、Zは前記熱線反射膜の日射反射率であり、Z´は前記開口部の日射反射率であり、S´は前記電波透過性領域の面積に対する前記熱線反射膜の面積の割合である。) - 前記電波透過性領域は、下記式(c)を満足する請求項1または2に記載の電波透過性基板。
ΔE<60.3×D-0.62 ・・・(c)
(式(c)中、ΔEは前記熱線反射膜と前記開口部との色差であり、Dは前記開口部の幅(単位はmm)である。) - 前記電波透過性領域における周波数28GHzの電波に対する電波透過損失が3dB以下である請求項1~3のいずれか1項に記載の電波透過性基板。
- 前記開口部が平行する複数の線状、又は格子状である請求項1~4のいずれか1項に記載の電波透過性基板。
- 前記誘電体基板の少なくとも一方の主面上の少なくとも一部に、電波非透過性領域を有し、
前記電波非透過性領域は、該領域を含むすべての1cm四方の単位領域が下記式(d)を満足する領域である、請求項1~5のいずれか1項に記載の電波透過性基板。
L≦802.6×S-503.7 ・・・(d)
(式(d)中、Lは前記単位領域内の前記熱線反射膜と前記開口部との境界線の全長(単位はmm/cm2)であり、Sは前記単位領域内の前記熱線反射膜の占める面積の割合である。) - 前記導電性膜は、銀、アルミニウム、インジウムスズ酸化物、フッ素およびアンチモンの少なくとも一つがドープされた酸化スズ、窒化チタン、窒化ニオブ、窒化クロム、窒化ジルコニウム及び窒化ハフニウム、からなる群より選ばれる少なくとも1種を合計で50原子%以上含有する、請求項1~6のいずれか1項に記載の電波透過性基板。
- 前記開口部は、前記誘電体基板が露出している、請求項1~7のいずれか1項に記載の電波透過性基板。
- 前記誘電体基板は、周波数28GHzの電波に対する電波透過損失が4dB以下である請求項1~8のいずれか1項に記載の電波透過性基板。
- 前記導電性膜は、厚さが1nm~100nmである、請求項1~9のいずれか1項に記載の電波透過性基板。
- 前記熱線反射膜は、前記導電性膜とは異なる、金属酸化物層および金属窒化物層のうち少なくとも一方の層を含む、請求項1~10のいずれか1項に記載の電波透過性基板。
- 前記導電性膜は、前記金属酸化物層および前記金属窒化物層のうち少なくとも一方の層で挟まれる構成を有する、請求項11に記載の電波透過性基板。
- 前記誘電体基板は、複数のガラス基板を有し、
前記複数のガラス基板が樹脂膜を挟んで積層される、請求項1~12のいずれか1項に記載の電波透過性基板。
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