WO2023171309A1 - 遠赤外線透過部材及び遠赤外線透過部材の製造方法 - Google Patents

遠赤外線透過部材及び遠赤外線透過部材の製造方法 Download PDF

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Publication number
WO2023171309A1
WO2023171309A1 PCT/JP2023/005632 JP2023005632W WO2023171309A1 WO 2023171309 A1 WO2023171309 A1 WO 2023171309A1 JP 2023005632 W JP2023005632 W JP 2023005632W WO 2023171309 A1 WO2023171309 A1 WO 2023171309A1
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WO
WIPO (PCT)
Prior art keywords
far
infrared transmitting
transmitting member
less
layer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2023/005632
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English (en)
French (fr)
Japanese (ja)
Inventor
容二 安井
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
AGC Inc
Original Assignee
Asahi Glass Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Asahi Glass Co Ltd filed Critical Asahi Glass Co Ltd
Priority to CN202380025574.1A priority Critical patent/CN118765267A/zh
Priority to JP2024506008A priority patent/JPWO2023171309A1/ja
Priority to DE112023000747.0T priority patent/DE112023000747T5/de
Publication of WO2023171309A1 publication Critical patent/WO2023171309A1/ja
Priority to US18/824,993 priority patent/US20240427059A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/14—Protective coatings, e.g. hard coatings
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/11—Anti-reflection coatings
    • G02B1/113—Anti-reflection coatings using inorganic layer materials only
    • 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
    • C03C17/3411—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/28—Interference filters
    • G02B5/281—Interference filters designed for the infrared light
    • G02B5/282—Interference filters designed for the infrared light reflecting for infrared and transparent for visible light, e.g. heat reflectors, laser protection
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60R—VEHICLES, VEHICLE FITTINGS, OR VEHICLE PARTS, NOT OTHERWISE PROVIDED FOR
    • B60R11/00—Arrangements for holding or mounting articles, not otherwise provided for
    • B60R11/04—Mounting of cameras operative during drive; Arrangement of controls thereof relative to the vehicle
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60R—VEHICLES, VEHICLE FITTINGS, OR VEHICLE PARTS, NOT OTHERWISE PROVIDED FOR
    • B60R11/00—Arrangements for holding or mounting articles, not otherwise provided for
    • B60R2011/0001—Arrangements for holding or mounting articles, not otherwise provided for characterised by position
    • B60R2011/0003—Arrangements for holding or mounting articles, not otherwise provided for characterised by position inside the vehicle
    • B60R2011/0019—Side or rear panels
    • B60R2011/0022—Pillars
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60R—VEHICLES, VEHICLE FITTINGS, OR VEHICLE PARTS, NOT OTHERWISE PROVIDED FOR
    • B60R11/00—Arrangements for holding or mounting articles, not otherwise provided for
    • B60R2011/0001—Arrangements for holding or mounting articles, not otherwise provided for characterised by position
    • B60R2011/0003—Arrangements for holding or mounting articles, not otherwise provided for characterised by position inside the vehicle
    • B60R2011/0026—Windows, e.g. windscreen
    • H—ELECTRICITY
    • H04—ELECTRIC COMMUNICATION TECHNIQUE
    • H04N—PICTORIAL COMMUNICATION, e.g. TELEVISION
    • H04N23/00—Cameras or camera modules comprising electronic image sensors; Control thereof
    • H04N23/20—Cameras or camera modules comprising electronic image sensors; Control thereof for generating image signals from infrared radiation only
    • H04N23/23—Cameras or camera modules comprising electronic image sensors; Control thereof for generating image signals from infrared radiation only from thermal infrared radiation

Definitions

  • the present invention relates to a far-infrared transmitting member and a method for manufacturing a far-infrared transmitting member.
  • a far-infrared transmitting member when attaching a far-infrared sensor to a vehicle or the like, a far-infrared transmitting member may be provided with a functional film for allowing far-infrared rays to properly enter the far-infrared sensor.
  • Patent Document 1 describes that an infrared transmitting film containing zinc oxide as a main component and a metal oxide is formed on a base material.
  • Such a far-infrared transmitting member is required to appropriately transmit far-infrared rays while improving scratch resistance.
  • An object of the present invention is to provide a far-infrared transmitting member and a method for manufacturing the far-infrared transmitting member that can appropriately transmit far-infrared rays and improve scratch resistance.
  • the far-infrared transmitting member includes a base material that transmits far-infrared rays and a functional film formed on the base material, and has an average transmittance of 50% or more for light with a wavelength of 8 ⁇ m to 12 ⁇ m,
  • the outermost layer of the functional film is a layer containing ZrO 2 as a main component, and the content of ZrO 2 is 50% by mass or more and 100% by mass or less with respect to the entire outermost layer, and it is resistant to light with a wavelength of 550 nm.
  • the refractive index is 2.05 or more.
  • a method for manufacturing a far-infrared transmitting member according to the present disclosure is a method for manufacturing a far-infrared transmitting member in which a functional film is formed on a base material that transmits far infrared rays, the functional film being formed on the base material by sputtering.
  • the far-infrared transmitting member by forming an outermost layer, the far-infrared transmitting member has an average transmittance of 50% or more for light with a wavelength of 8 ⁇ m to 12 ⁇ m, and the outermost layer is made of ZrO 2 , the content of ZrO 2 is 50% by mass or more and 100% by mass or less with respect to the entire outermost layer, and the refractive index for light with a wavelength of 550 nm is 2.05 or more. be.
  • FIG. 1 is a schematic diagram showing a state in which the vehicle glass according to the present embodiment is mounted on a vehicle.
  • FIG. 2 is a schematic plan view of the vehicle glass according to this embodiment.
  • FIG. 3 is a cross-sectional view taken along line AA in FIG.
  • FIG. 4 is a sectional view taken along the BB section in FIG.
  • FIG. 5 is a schematic cross-sectional view of the far-infrared transmitting member according to the present embodiment.
  • FIG. 6 is a schematic diagram illustrating a method of manufacturing a far-infrared transmitting member according to this embodiment.
  • FIG. 1 is a schematic diagram showing a state in which the vehicle glass according to the present embodiment is mounted on a vehicle.
  • a vehicle glass 1 according to this embodiment is mounted on a vehicle V.
  • the vehicle glass 1 is a window member applied to a windshield of a vehicle V. That is, the vehicle glass 1 is used as a front window of the vehicle V, in other words, a windshield.
  • a far-infrared camera CA1 and a visible light camera CA2 are mounted inside the vehicle V (inside the vehicle).
  • the inside of the vehicle V vehicle interior refers to, for example, the interior of the vehicle in which the driver's seat is provided.
  • the vehicle glass 1, the far-infrared camera CA1, and the visible light camera CA2 constitute a camera unit 100 according to the present embodiment.
  • the far-infrared camera CA1 is a camera that detects far-infrared rays, and captures a thermal image of the outside of the vehicle V by detecting far-infrared rays from outside the vehicle V.
  • Visible light camera CA2 is a camera that detects visible light, and captures an image of the outside of vehicle V by detecting visible light from outside of vehicle V.
  • the camera unit 100 may further include, for example, LiDAR or millimeter wave radar in addition to the far-infrared camera CA1 and the visible light camera CA2.
  • the far infrared rays here are, for example, electromagnetic waves with a wavelength range of 8 ⁇ m to 13 ⁇ m
  • the visible light is, for example, electromagnetic waves with a wavelength range of 360 nm to 830 nm.
  • 8 ⁇ m to 13 ⁇ m and 360 nm to 830 nm herein refer to 8 ⁇ m or more and 13 ⁇ m or less, and 360 nm or more and 830 nm or less, and the same applies hereafter.
  • the far infrared rays may be electromagnetic waves having a wavelength range of 8 ⁇ m to 12 ⁇ m.
  • FIG. 2 is a schematic plan view of the vehicle glass according to this embodiment.
  • FIG. 3 is a cross-sectional view taken along line AA in FIG.
  • FIG. 4 is a sectional view taken along the BB section in FIG.
  • the upper edge of the vehicle glass 1 will be referred to as an upper edge portion 1a
  • the lower edge will be referred to as a lower edge portion 1b
  • one side edge will be referred to as a side edge portion 1c
  • the other side edge will be referred to as a lower edge portion 1b.
  • the upper edge portion 1a is an edge portion located on the upper side in the vertical direction when the vehicle glass 1 is mounted on the vehicle V.
  • the lower edge portion 1b is an edge portion located on the lower side in the vertical direction when the vehicle glass 1 is mounted on the vehicle V.
  • the side edge portion 1c is an edge portion located on one side when the vehicle glass 1 is mounted on the vehicle V.
  • the side edge portion 1d is an edge portion located on the other side when the vehicle glass 1 is mounted on the vehicle V.
  • the direction from the upper edge 1a to the lower edge 1b will be referred to as the Y direction
  • the direction from the side edge 1c to the side edge 1d will be referred to as the X direction. do.
  • the X direction and the Y direction are orthogonal.
  • the direction perpendicular to the surface of the vehicle glass 1, that is, the thickness direction of the vehicle glass 1 is defined as the Z direction.
  • the Z direction is, for example, a direction from the outside of the vehicle V toward the inside of the vehicle V when the vehicle glass 1 is mounted on the vehicle V.
  • the X direction and the Y direction are along the surface of the vehicle glass 1, but for example, if the surface of the vehicle glass 1 is a curved surface, the direction is the direction that touches the surface of the vehicle glass 1 at the center point O of the vehicle glass 1. It may be.
  • the center point O is the center position of the vehicle glass 1 when the vehicle glass 1 is viewed from the Z direction.
  • a light-transmitting area A1 and a light-blocking area A2 are formed in the vehicle glass 1.
  • the light-transmitting area A1 is an area occupying the center portion of the vehicle glass 1 when viewed from the Z direction.
  • the light-transmitting area A1 is an area for ensuring the driver's field of view.
  • the light-transmitting area A1 is an area that transmits visible light.
  • the light-blocking area A2 is an area formed around the light-transmitting area A1 when viewed from the Z direction.
  • the light blocking area A2 is an area that blocks visible light.
  • a far-infrared transmitting region B and a visible light transmitting region C are formed in the light-shielding region A2a, which is a portion on the upper edge 1a side of the light-shielding region A2.
  • the far-infrared transmission area B is an area that transmits far-infrared rays, and is an area where the far-infrared camera CA1 is provided. That is, far-infrared camera CA1 is provided at a position overlapping with far-infrared transmission region B when viewed from the optical axis direction of far-infrared camera CA1.
  • the visible light transmission area C is an area that transmits visible light, and is an area where the visible light camera CA2 is provided. That is, the visible light camera CA2 is provided at a position overlapping the visible light transmission area C when viewed from the optical axis direction of the visible light camera CA2.
  • the light shielding area A2 has the far infrared transmitting region B and the visible light transmitting region C, so the light shielding region A2 does not transmit far infrared rays in areas other than the region where the far infrared transmitting region B is formed. Visible light is blocked in areas other than the area where the visible light transmission area C is formed.
  • a light-shielding area A2a is formed around the far-infrared transmission area B and the visible light transmission area C. Providing the light shielding area A2a around the sensor in this manner is preferable because the various sensors are protected from sunlight. This is also preferable from the standpoint of design, since the wiring for the various sensors cannot be seen from outside the vehicle.
  • the vehicle glass 1 includes a glass substrate 12 (first glass substrate), a glass substrate 14 (second glass substrate), an intermediate layer 16, and a light shielding layer 18.
  • a glass substrate 12 first glass substrate
  • a glass substrate 14 second glass substrate
  • an intermediate layer 16 intermediate layer
  • a light shielding layer 18 are laminated in this order in the Z direction.
  • the glass substrate 12 and the glass substrate 14 are fixed (adhered) to each other via an intermediate layer 16.
  • the glass substrates 12 and 14 for example, soda lime glass, borosilicate glass, aluminosilicate glass, etc. can be used.
  • the intermediate layer 16 is an adhesive layer that adheres the glass substrate 12 and the glass substrate 14.
  • the intermediate layer 16 for example, polyvinyl butyral (hereinafter also referred to as PVB) modified material, ethylene-vinyl acetate copolymer (EVA) material, urethane resin material, vinyl chloride resin material, etc. can be used.
  • the glass substrate 12 includes one surface 12A and the other surface 12B, and the other surface 12B is in contact with one surface 16A of the intermediate layer 16 and fixed (adhesive) to the intermediate layer 16. ) has been done.
  • the glass substrate 14 includes one surface 14A and the other surface 14B, and the one surface 14A is fixed (adhered) to the intermediate layer 16 by contacting the other surface 16B of the intermediate layer 16. .
  • the vehicle glass 1 is a laminated glass in which the glass substrate 12 and the glass substrate 14 are laminated.
  • the vehicle glass 1 is not limited to laminated glass, and may include, for example, only one of the glass substrate 12 and the glass substrate 14.
  • the intermediate layer 16 may not be provided either.
  • the glass substrates 12 and 14 are not distinguished, they will be referred to as the glass substrate 10.
  • the light shielding layer 18 includes one surface 18A and the other surface 18B, and the one surface 18A is fixed in contact with the other surface 14B of the glass substrate 14.
  • the light blocking layer 18 is a layer that blocks visible light.
  • a ceramic light-shielding layer or a light-shielding film can be used as the light-shielding layer.
  • a ceramic layer made of a conventionally known material such as a black ceramic layer can be used.
  • the light-shielding film for example, a light-shielding polyethylene terephthalate (PET) film, a light-shielding polyethylene naphthalate (PEN) film, a light-shielding polymethyl methacrylate (PMMA) film, etc. can be used.
  • PET polyethylene terephthalate
  • PEN light-shielding polyethylene naphthalate
  • PMMA light-shielding polymethyl methacrylate
  • the side of the vehicle glass 1 on which the light shielding layer 18 is provided is the inside side of the vehicle V (inside the vehicle), and the side on which the glass base 12 is provided is the outside side of the vehicle V (outside the vehicle).
  • the present invention is not limited thereto, and the light shielding layer 18 may be provided on the outside of the vehicle V.
  • the light shielding layer 18 may be formed between the glass substrate 12 and the glass substrate 14.
  • the light-shielding region A2 is formed by providing the light-shielding layer 18 on the glass substrate 10. That is, the light-shielding region A2 is a region where the glass substrate 10 is provided with the light-shielding layer 18. That is, the light-shielding region A2 is a region in which the glass substrate 12, the intermediate layer 16, the glass substrate 14, and the light-shielding layer 18 are laminated.
  • the light-transmitting region A1 is a region in which the glass substrate 10 does not include the light-shielding layer 18. That is, the light-transmitting area A1 is an area where the glass substrate 12, the intermediate layer 16, and the glass substrate 14 are laminated, but the light-blocking layer 18 is not laminated.
  • the vehicle glass 1 is formed with an opening 19 that penetrates from one surface (here, surface 12A) to the other surface (here, surface 14B) in the Z direction.
  • a far-infrared transmitting member 20 is provided within the opening 19 .
  • the area in which the opening 19 is formed and the far-infrared transmitting member 20 is provided is a far-infrared transmitting region B. That is, the far-infrared transmitting region B is a region in which the opening 19 and the far-infrared transmitting member 20 disposed within the opening 19 are provided.
  • the light shielding layer 18 does not transmit far infrared rays, the light shielding layer 18 is not provided in the far infrared transmitting region B. That is, in the far-infrared transmission region B, the glass substrate 12, the intermediate layer 16, the glass substrate 14, and the light-shielding layer 18 are not provided, and the far-infrared transmission member 20 is provided in the opening 19 formed. .
  • the far-infrared transmitting member 20 will be described later.
  • the visible light transmitting region C is a region in which the glass substrate 10 does not include the light shielding layer 18 in the Z direction, similarly to the light transmitting region A1. That is, the visible light transmitting region C is a region where the glass substrate 12, the intermediate layer 16, and the glass substrate 14 are laminated, but the light shielding layer 18 is not laminated.
  • the visible light transmitting region C is preferably provided near the far infrared transmitting region B.
  • the center of the far-infrared transmission region B viewed from the Z direction is defined as a center point OB
  • the center of the visible light transmission region C viewed from the Z direction is defined as a center point OC.
  • the distance L is preferably greater than 0 mm and less than 100 mm. , more preferably 10 mm or more and 80 mm or less.
  • the visible light transmitting region C By locating the visible light transmitting region C within this range relative to the far infrared transmitting region B, it is possible to capture images at close positions with the far infrared camera CA1 and the visible light camera CA2, while also allowing the visible light transmitting region C to The amount of perspective distortion in the light transmission region C can be suppressed, and images can be appropriately captured by the visible light camera CA2.
  • the load when processing the data obtained from each camera is reduced, and the routing of power and signal cables is also made easier. Become.
  • the visible light transmitting region C and the far infrared transmitting region B are preferably located side by side in the X direction. That is, it is preferable that the visible light transmitting region C is not located on the Y direction side of the far infrared transmitting region B, but is aligned with the far infrared transmitting region B in the X direction.
  • the visible light transmitting region C can be arranged near the upper edge portion 1a. Therefore, it is possible to appropriately secure the driver's field of view in the transparent area A1.
  • FIG. 5 is a schematic cross-sectional view of the far-infrared transmitting member according to the present embodiment.
  • the far-infrared transmitting member 20 includes a base material 30, a first functional film 32 as a functional film formed on the base material 30, and a second functional film formed on the base material 30. 38.
  • the first functional film 32 is formed on one surface 30a of the base material 30.
  • the surface 30a is a surface that faces the outside of the vehicle when mounted on the vehicle glass 1.
  • the second functional film 38 is formed on the other surface 30b of the base material 30.
  • the surface 30b is a surface facing the inside of the vehicle when mounted on the vehicle glass 1.
  • the second functional film 38 is not an essential component, and no layer other than the base material 30 may be provided on the surface 30b.
  • the far-infrared transmitting member 20 is provided in the light-shielding area A2 of the vehicle glass 1, which is a window member of the vehicle V, but is not limited thereto, and is not limited to this, and is provided in a vehicle such as a pillar exterior member of the vehicle V. It may be provided on any exterior member of the V. Further, the far-infrared transmitting member 20 is not limited to being provided in the vehicle V, and may be used for any purpose.
  • the base material 30 is a member that can transmit far infrared rays.
  • the base material 30 preferably has an internal transmittance of 50% or more, more preferably 60% or more, and even more preferably 70% or more for light with a wavelength of 10 ⁇ m (far infrared rays). Further, the average internal transmittance of the base material 30 for light with a wavelength of 8 ⁇ m to 12 ⁇ m (far infrared rays) is preferably 50% or more, more preferably 60% or more, and preferably 70% or more. More preferred.
  • the average internal transmittance is the average value of the internal transmittance for light of each wavelength in the wavelength band (here, from 8 ⁇ m to 12 ⁇ m).
  • the internal transmittance of the base material 30 is the transmittance excluding surface reflection loss on the incident side and the exit side, and is well known in the technical field, and may be measured by a commonly used method. The measurement is performed, for example, as follows.
  • a pair of flat samples (a first sample and a second sample) made of base materials of the same composition and having different thicknesses are prepared. Both surfaces of the flat sample are parallel to each other and optically polished.
  • the external transmittance including the surface reflection loss of the first sample is T1
  • the external transmittance including the surface reflection loss of the second sample is T2
  • the thickness of the first sample is Td1 (mm)
  • the thickness of the second sample is Td2 (mm)
  • Td1 ⁇ Td2 the internal transmittance ⁇ at the thickness Tdx (mm) can be calculated by the following equation (1).
  • the external transmittance of infrared rays can be measured using, for example, a Fourier transform infrared spectrometer (manufactured by Thermo Scientific, trade name: Nicolet iS10).
  • the refractive index of the base material 30 for light with a wavelength of 10 ⁇ m is preferably 1.5 or more and 4.0 or less, more preferably 2.0 or more and 4.0 or less, and 2.2 or more and 3.5 It is more preferable that it is the following. Further, the average refractive index of the base material 30 for light with a wavelength of 8 ⁇ m to 12 ⁇ m is preferably 1.5 or more and 4.0 or less, more preferably 2.0 or more and 4.0 or less, and 2. More preferably, it is 2 or more and 3.5 or less.
  • the average refractive index is the average value of the refractive index for light of each wavelength in the wavelength band (8 ⁇ m to 12 ⁇ m here).
  • the refractive index can be determined using, for example, polarization information obtained by an infrared spectroscopic ellipsometer (manufactured by J.A. Woollam Co., Ltd., IR-VASE-UT) and a spectral transmission spectrum obtained by a Fourier transform infrared spectrometer. This can be determined by fitting the model.
  • the thickness D1 of the base material 30 is preferably 0.5 mm or more and 5 mm or less, more preferably 1 mm or more and 4 mm or less, and even more preferably 1.5 mm or more and 3 mm or less.
  • the thickness D1 can also be said to be the length in the Z direction from the surface 30a to the surface 30b of the base material 30.
  • the material of the base material 30 is not particularly limited, and examples thereof include Si, Ge, ZnS, and chalcogenide glass. It can be said that it is preferable that the base material 30 contains at least one material selected from the group of Si, Ge, ZnS, and chalcogenide glass. By using such a material for the base material 30, far infrared rays can be appropriately transmitted.
  • the preferred composition of chalcogenide glass is: In atomic percent, Ge+Ga; 7% to 25%, Sb; 0% to 35%, Bi; 0% to 20%, Zn; 0% to 20%, Sn: 0% to 20%, Si; 0% to 20%, La: 0% to 20%, S+Se+Te; 55% to 80%, Ti; 0.005% to 0.3%, Li + Na + K + Cs; 0% to 20%, F+Cl+Br+I; composition containing 0% to 20%.
  • This glass preferably has a glass transition point (Tg) of 140°C to 550°C.
  • the material for the base material 30 it is more preferable to use Si or ZnS.
  • the first functional film 32 is formed on the vehicle outer surface 30a of the base material 30.
  • the first functional film 32 includes an intermediate layer 34 and an outermost layer 36.
  • the outermost layer 36 is a layer provided at the part of the first functional film 32 that is farthest from the base material 30, that is, in this embodiment, the outermost layer.
  • the outermost layer 36 is the outermost layer (in this embodiment, the outermost layer of the vehicle) of the far-infrared transmitting member 20, and is exposed to the outside.
  • the intermediate layer 34 is a layer provided in the first functional film 32 closer to the base material 30 than the outermost layer 36 (in this embodiment, closer to the vehicle inner side than the outermost layer 36). That is, the intermediate layer 34 is provided between the base material 30 and the outermost layer 36.
  • the first functional film 32 may not include the intermediate layer 34 and may include only the outermost layer 36.
  • the outermost layer 36 is a layer containing ZrO 2 as a main component.
  • the main component here may refer to the content of the outermost layer 36 as a whole to be 50% by mass or more.
  • the outermost layer 36 has a ZrO 2 content of 50% by mass or more and 100% by mass or less, preferably 70% by mass or more and 100% by mass or less, and 90% by mass or more, based on the entire outermost layer 36. More preferably, it is 100% by mass or less.
  • the outermost layer 36 contains ZrO 2 alone, that is, the content of ZrO 2 excluding inevitable impurities is 100% by mass. When the content of ZrO 2 falls within this range, the outermost layer 36 can appropriately transmit far infrared rays and improve scratch resistance.
  • the outermost layer 36 may contain a subcomponent other than the main component ZrO 2 .
  • the subcomponent is preferably an oxide that transmits far infrared rays, and includes at least one of NiO x , ZnO, Bi 2 O 3 , and CuO x .
  • the thickness D2 of the outermost layer 36 is preferably 20 nm or more, more preferably 50 nm or more and 300 nm or less, even more preferably 100 nm or more and 300 nm or less, and most preferably 150 nm or more and 250 nm or less. Note that the thickness D2 can also be said to be the length in the Z direction from the surface of the outermost layer 36 on the Z direction side to the surface on the opposite side to the Z direction. Further, the ratio of the thickness D2 of the outermost layer 36 to the thickness D1 of the base material 30 is preferably 0.002% or more and 0.030% or less, and preferably 0.005% or more and 0.020% or less. More preferably, it is 0.008% or more and 0.013% or less.
  • the ratio of the thickness D2 of the outermost layer 36 to the thickness D3 of the first functional film 32 is preferably 1% or more and 25% or less, more preferably 3% or more and 25% or less, and 5% or more. It is more preferably 25% or less, and most preferably 7% or more and 21% or less.
  • the thickness D3 of the first functional film 32 can also be said to be the length in the Z direction from the surface of the first functional film 32 on the Z direction side to the surface on the opposite side to the Z direction. When the thickness D2 is within this range, far infrared rays can be transmitted appropriately and scratch resistance can be appropriately improved.
  • the surface of the outermost layer 36 on the side opposite to the base material 30 is referred to as a surface 36a.
  • the surface 36a is the surface exposed to the outside, and can be said to be the surface on the outside of the vehicle in this embodiment.
  • the arithmetic mean roughness Ra (surface roughness) of the surface 36a of the outermost layer 36 is preferably 7.0 nm or less, more preferably 5.0 nm or less, and 4.0 nm or less. is more preferable, and most preferably 3.0 nm or less.
  • the arithmetic mean roughness Ra of the surface 36a falls within this range, the coefficient of dynamic friction and the change in surface roughness before and after scratching can be reduced, and the scratch resistance can be improved more appropriately.
  • the arithmetic mean roughness Ra refers to the arithmetic mean roughness Ra specified in JIS B 0601:2001.
  • the outermost layer 36 can transmit far infrared rays.
  • the outermost layer 36 preferably has an extinction coefficient of 0.10 or less, more preferably 0.05 or less, and even more preferably 0.04 or less for light with a wavelength of 10 ⁇ m.
  • the extinction coefficient is determined using, for example, polarization information obtained by an infrared spectroscopic ellipsometer (manufactured by J.A. Woollam Co., Ltd., IR-VASE-UT) and a spectral transmission spectrum obtained by a Fourier transform infrared spectrometer. This can be determined by fitting an optical model.
  • the outermost layer 36 preferably has a refractive index of 2.05 or more, more preferably 2.05 or more and 2.40 or less, and 2.10 or more and 2.30 or more, with respect to light with a wavelength of 550 nm (visible light). It is more preferably the following, and particularly preferably 2.15 or more and 2.25 or less.
  • the refractive index of light with a wavelength of 550 nm can be determined by fitting an optical model using polarization information obtained by a spectroscopic ellipsometer (manufactured by J.A. Woollam Co., Ltd., M-2000) and spectral transmittance measured based on JIS R3106. You can make a decision by doing this.
  • intermediate layer 34 can transmit far infrared rays.
  • intermediate layer 34 includes an antireflection layer.
  • the intermediate layer 34 is composed of only one antireflection layer, but the intermediate layer 34 is not limited to this, and may be composed of a plurality of laminated layers. .
  • the antireflection layer included in the intermediate layer 34 is a layer containing NiOx as a main component.
  • the main component here may refer to a content of 50% by mass or more with respect to the entire antireflection layer.
  • the content of NiO More preferably, it is 100% by mass or less.
  • the antireflection layer contains NiO x alone, that is, the content of NiO x excluding inevitable impurities is 100% by mass. When the content of NiOx falls within this range, the antireflection layer can suppress reflection of far infrared rays and appropriately transmit far infrared rays.
  • nickel oxide is known to have a plurality of compositions depending on the valence of nickel, and X can take any value from 0.5 to 2. Further, the valence does not have to be single, and two or more valences may be mixed. In this embodiment, it is preferable to use NiO as NiO x .
  • the material of the antireflection layer is not limited thereto, and may be any material, for example, a layer containing at least one of ZnS, Ge, Si, MgO, ZnO, and Bi2O3 .
  • the thickness of the antireflection layer included in the intermediate layer 34 is preferably 1000 nm or more and 2000 nm or less, more preferably 1000 nm or more and 1500 nm or less, and even more preferably 1100 nm or more and 1300 nm or less. Further, the ratio of the thickness of the antireflection layer to the thickness D2 of the outermost layer 36 is preferably 75% or more and 99% or less, more preferably 75% or more and 97% or less, and 75% or more and 95% or less. It is more preferably 79% or more and 93% or less. When the thickness of the antireflection layer falls within this range, reflection of far infrared rays can be suppressed and far infrared rays can be appropriately transmitted. Note that the thickness of the antireflection layer can also be said to be the length in the Z direction from the surface of the antireflection layer on the Z direction side to the surface on the opposite side to the Z direction.
  • the antireflection layer included in the intermediate layer 34 can transmit far infrared rays.
  • the antireflection layer preferably has an extinction coefficient of 0.05 or less, more preferably 0.03 or less, even more preferably 0.02 or less, and 0.05 or less, more preferably 0.02 or less, and even more preferably 0.02 or less. Most preferably, it is 01 or less. When the extinction coefficient falls within this range, far infrared rays can be appropriately transmitted.
  • the antireflection layer included in the intermediate layer 34 preferably has an extinction coefficient of 0.04 or more, more preferably 0.06 or more, and 0.08 or more for light with a wavelength of 550 nm (visible light). It is more preferable that it is, and it is most preferable that it is 0.10 or more. When the extinction coefficient of the antireflection layer for visible light falls within this numerical range, reflectance dispersion of visible light can be appropriately suppressed, and an appearance that maintains designability can be achieved.
  • the intermediate layer 34 may include layers other than the antireflection layer.
  • the intermediate layer 34 may include a hue adjustment layer closer to the outermost layer 36 than the antireflection layer. That is, in this case, it can be said that the base material 30, the antireflection layer, the hue adjustment layer, and the outermost layer 36 may be laminated in this order toward the outside of the vehicle.
  • the hue adjustment layer will be specifically explained below.
  • the hue adjustment layer included in the intermediate layer 34 reduces the difference in reflectance for visible light of different wavelengths (reflectance dispersion) and suppresses interference colors of the far-infrared transmitting member 20 to ensure design. This is the layer of
  • the hue adjustment layer included in the intermediate layer 34 can transmit far infrared rays.
  • the extinction coefficient of the hue adjustment layer for light with a wavelength of 10 ⁇ m is preferably 0.4 or less, more preferably 0.2 or less, and even more preferably 0.1 or less. When the extinction coefficient falls within this range, far infrared rays can be appropriately transmitted.
  • the thickness of the hue adjustment layer included in the intermediate layer 34 is preferably 5 nm or more and 100 nm or less, more preferably 10 nm or more and 60 nm or less, and even more preferably 20 nm or more and 50 nm or less. Further, the ratio of the thickness of the hue adjustment layer to the thickness D2 of the outermost layer 36 is preferably 2.5% or more and 100% or less, more preferably 5% or more and 50% or less, and 10% or more and 30%. It is more preferably at most 10% or more and at most 25%. When the thickness of the hue adjustment layer falls within this range, it is possible to appropriately transmit far infrared rays while suppressing reflection and dispersion of visible light, thereby making the far infrared transmitting member 20 less noticeable. Note that the thickness of the hue adjustment layer can also be said to be the length in the Z direction from the surface of the hue adjustment layer on the Z direction side to the surface on the opposite side to the Z direction.
  • the hue adjustment layer included in the intermediate layer 34 includes a first layer and a second layer provided on the outermost layer 36 side (outside the vehicle) of the first layer.
  • the first layer is a layer of the same material and properties as the outermost layer 36.
  • the thickness of the first layer is preferably 10 nm or more and 40 nm or less, more preferably 15 nm or more and 35 nm or less, and even more preferably 20 nm or more and 30 nm or less.
  • the ratio of the thickness of the first layer to the thickness D2 of the outermost layer 36 is preferably 1.5% or more and 60% or less, more preferably 3% or more and 30% or less, and 6% or more and 20%. It is more preferably at most 6% or more and at most 15%.
  • the second layer is a layer of the same material and properties as the antireflection layer included in the intermediate layer 34.
  • the thickness of the second layer is preferably 5 nm or more and 40 nm or less, more preferably 5 nm or more and 25 nm or less, and even more preferably 10 nm or more and 20 nm or less.
  • the ratio of the thickness of the second layer to the thickness D2 of the outermost layer 36 is preferably 1% or more and 40% or less, more preferably 2% or more and 20% or less, and 4% or more and 12% or less. It is more preferably at least 4% and most preferably at most 10%.
  • the hue adjustment layer is composed of two layers, the first layer and the second layer, but the invention is not limited to this, and the laminate of the first layer and the second layer may be a plurality of stacked layers. Good too.
  • the hue adjustment layer is preferably a layer in which the first layer and the second layer are stacked alternately from the base material 30 side in a number of 2n layers (n is a natural number of 1 or more).
  • the thickness ratio of each layer in the color tone adjustment layer is preferably higher for a layer having a lower refractive index for light with a wavelength of 550 nm (visible light).
  • the configuration of the hue adjustment layer is not limited to including the first layer made of the same material as the outermost layer 36 and the second layer made of the same material as the antireflection layer, and may be any configuration. That is, the hue adjustment layer may be a layer whose refractive index for light with a wavelength of 550 nm (visible light) is different from that of both the outermost layer 36 and the antireflection layer.
  • the hue adjustment layer preferably has a refractive index of 2.2 or more and 2.5 or less, more preferably 2.3 or more and 2.4 or less, with respect to light with a wavelength of 550 nm (visible light).
  • the refractive index of the hue adjustment layer for visible light falls within this numerical range, reflection and dispersion of visible light can be suppressed and the far-infrared transmitting member 20 can be made inconspicuous.
  • the second functional film 38 provided on the vehicle-inside surface 30b of the base material 30 is a layer that transmits far infrared rays.
  • the second functional film 38 may have the same configuration as the intermediate layer 34. That is, for example, the far-infrared transmitting member 20 may be laminated in the order of the base material 30 and the antireflection layer toward the inside of the vehicle. For example, the far-infrared transmitting member 20 may be laminated in the order of the base material 30, the antireflection layer, and the hue adjustment layer (first layer, second layer) toward the inside of the vehicle.
  • an adhesion layer (not shown) may be formed between the intermediate layer 34 and the base material 30.
  • the adhesive film is a film that brings the base material 30 and the intermediate layer 34 into close contact with each other, or in other words, it is a film that improves the adhesive force between the base material 30 and the intermediate layer 34.
  • the refractive index of the adhesive film for light with a wavelength of 10 ⁇ m is preferably 1.0 or more and 4.3 or less, more preferably 1.5 or more and 4.3 or less, and 1.5 or more and 3.8 It is more preferable that it is the following. When the refractive index falls within this range, reflection of far infrared rays can be appropriately suppressed.
  • the thickness of the adhesive film is preferably 0.05 ⁇ m or more and 0.5 ⁇ m or less, more preferably 0.05 ⁇ m or more and 0.3 ⁇ m or less, and even more preferably 0.05 ⁇ m or more and 0.1 ⁇ m or less. preferable.
  • the thickness of the adhesive film can also be said to be the length in the Z direction from the surface of the adhesive film on the Z direction side to the surface on the opposite side to the Z direction.
  • the thickness of the adhesive film is preferably thinner than the thickness of the intermediate layer 34 and the thickness D2 of the outermost layer 36. Since the thickness of the adhesive film is thinner than the thickness of these layers, the influence on optical performance can be reduced.
  • the adhesive film can transmit far infrared rays.
  • the extinction coefficient of the adhesive film for light with a wavelength of 10 ⁇ m is preferably 0.4 or less, more preferably 0.2 or less, and even more preferably 0.1 or less. When the extinction coefficient falls within this range, far infrared rays can be appropriately transmitted.
  • the adhesive film may be made of any material, for example, from the group of Si, Ge, MgO, NiO x , CuO x , ZnS, Al 2 O 3 , ZrO 2 , SiO 2 , TiO 2 , ZnO, and Bi 2 O 3 It is preferable that it contains at least one selected material, and it is more preferable that it contains ZrO 2 . By using such a material, the adhesive film can properly adhere the base material 30 and the intermediate layer 34.
  • the adhesive film may be formed by sputtering, but is not limited thereto, and may be formed, for example, by vapor deposition.
  • the far-infrared transmitting member 20 includes the first functional film 32 having the outermost layer 36 formed on the surface 30a of the base material 30. By forming the outermost layer 36, the far-infrared transmitting member 20 can appropriately transmit far-infrared rays and improve scratch resistance appropriately.
  • the far-infrared transmitting member 20 preferably has a transmittance of 10 ⁇ m light of 50% or more, more preferably 65% or more, and even more preferably 70% or more. Further, the far-infrared transmitting member 20 preferably has an average transmittance of 50% or more, more preferably 65% or more, and even more preferably 70% or more for light having a wavelength of 8 ⁇ m to 12 ⁇ m. When the transmittance and average transmittance are within this range, the function as an infrared transmitting member can be properly exhibited.
  • the far-infrared transmitting member 20 preferably has a reflectance of 10 ⁇ m light of 15% or less, more preferably 10% or less, and even more preferably 5% or less. Further, the far-infrared transmitting member 20 preferably has an average reflectance of 15% or less, more preferably 10% or less, and even more preferably 5% or less for light having a wavelength of 8 ⁇ m to 12 ⁇ m. When the reflectance and average reflectance are within this range, the function as an infrared transmitting member can be properly exhibited.
  • the average reflectance is the average value of the reflectance for light of each wavelength in the wavelength band (here, 8 ⁇ m to 12 ⁇ m). The reflectance can be measured, for example, with a Fourier transform infrared spectrometer (Nicolet iS10, manufactured by Thermo Scientific).
  • the far-infrared transmitting member 20 preferably has an indentation hardness of 9.0 GPa or more, and preferably 10.0 GPa, at the indentation depth of the vehicle outer surface 20A (i.e., the surface 36a of the outermost layer 36) in the range of 90 to 110 nm. It is more preferably at least 11.0 GPa, even more preferably at least 12.0 GPa, most preferably at least 13.0 GPa. When the indentation hardness of the surface 20A falls within this range, the scratch resistance can be appropriately improved.
  • the indentation hardness of the surface 20A is the indentation hardness in the indentation depth range of 90 nm to 110 nm, measured by the nanoindentation method (continuous stiffness measurement method) using a nanoindenter. Point. More specifically, indentation hardness is a value determined from a displacement-load curve from loading to unloading of a measuring indenter, and is defined in ISO 14577. Indentation hardness can be measured as follows. Specifically, using a KLA iMicro type nanoindenter, the indentation depth h (nm) corresponding to the indentation load P (mN) was continuously measured over the entire process from the start of loading to unloading at the measurement location. and create a Ph curve. Then, from the created Ph curve, the indentation hardness H (GPa) is calculated as shown in the following equation (2).
  • the indentation hardness H in the section of indentation depth of 90 nm or more and 110 nm or less is defined as the indentation hardness of the surface 20A. That is, in this embodiment, it is preferable that the indentation hardness H satisfies the above range in the entire range of indentation depth of 90 nm or more and 110 nm or less.
  • ⁇ a * b * is preferably 5 or less, more preferably 4 or less, even more preferably 3 or less, particularly preferably 2 or less, and 1 or less. is most preferred.
  • ⁇ a * b * refers to the distance from the origin coordinates of a * b * in the CIE-Lab color system obtained from the 5-degree incident visible light reflection spectrum. That is, ⁇ a * b * is calculated using the following equation (3). When ⁇ a * b * falls within this range, the visible light reflected from the far-infrared transmitting member 20 has a neutral color, making it possible to provide an appearance that maintains design.
  • a * and b * are the chromaticity coordinates of reflected light in the CIE-Lab color system when standard illuminant D65 is used as the illumination light, and JIS Z 8781 using spectral reflectance measured based on JIS R3106. - It can be calculated based on 4.
  • the far-infrared transmitting member 20 has a NiO x film whose extinction coefficient in the visible range changes depending on the degree of oxidation, a * and Changes in b * can be suppressed.
  • the far-infrared transmitting member 20 has an outer surface 20A formed flush with (continuous with) the outer surface of the light shielding area A2.
  • the surface 20A of the far-infrared transmitting member 20 on the outside of the vehicle is attached so as to be continuous with the surface 12A of the glass base 12. Since the surface 20A of the far-infrared transmitting member 20 is continuous with the surface 12A of the glass base 12 in this way, it is possible to suppress the wiping effect of the wiper from being impaired. Further, it is possible to suppress the possibility that the design of the vehicle V is impaired due to the difference in level, and that dust or the like accumulates on the difference in level.
  • the far-infrared transmitting member 20 is shaped to match the curved shape of the vehicle glass 1 to which it is applied.
  • the method for forming the far-infrared transmitting member 20 is not particularly limited, but polishing or molding is selected depending on the curved shape and the member.
  • the shape of the far-infrared transmitting member 20 is not particularly limited, it is preferably a plate-like shape that matches the shape of the opening 19. That is, for example, when the opening 19 is circular, the far-infrared transmitting member 20 is preferably disk-shaped (cylindrical). Further, from the viewpoint of design, the surface shape of the far-infrared transmitting member 20 on the outside of the vehicle may be processed to match the curvature of the outer surface shape of the glass substrate 12. Further, the far-infrared transmitting member 20 may be shaped like a lens in order to both widen the viewing angle of the far-infrared camera CA1 and improve mechanical properties.
  • the number of lens-shaped far-infrared transmitting members 20 is preferably 1 to 3, and typically 2. Furthermore, it is particularly preferable that the lens-shaped far-infrared transmitting member 20 is aligned in advance and made into a module, and is integrated with a casing or a bracket that adheres the far-infrared camera CA1 to the vehicle glass 1.
  • the area of the opening 19 on the inside surface of the vehicle is smaller than the area of the opening 19 on the outside surface of the vehicle, and the shape of the far-infrared transmitting member 20 is also adjusted accordingly. It is preferable that the area on the inner side of the vehicle is smaller than the area on the outer side of the vehicle. With such a configuration, the strength against impact from outside the vehicle is improved. Furthermore, when the vehicle glass 1 of the present embodiment is a laminated glass including the glass base 12 (outside the vehicle) and the glass base 14 (inside the vehicle), the opening 19 is the opening 12a of the glass base 12. and the opening 14a of the glass substrate 14 are formed so as to overlap with each other.
  • the area of the opening 12 a of the glass base 12 is made larger than the area of the opening 14 a of the glass base 14 , and the far-infrared transmitting member 20 matched to the size of the opening 12 a of the glass base 12 is attached to the glass base 12 . It may be placed within the opening 12a.
  • the length d1 of the longest straight line connecting any two points in the plane on the outside of the vehicle is 80 mm or less.
  • the length d1 is more preferably 70 mm or less, and even more preferably 65 mm or less.
  • the length d1 is 60 mm or more.
  • the opening 19 in the far-infrared transmission region B has a length d2 of the longest straight line connecting any two points on the outside of the vehicle of 80 mm or less.
  • the length d2 is more preferably 70 mm or less, and even more preferably 65 mm or less.
  • the length d2 is 60 mm or more.
  • the length d2 can also be said to be the length of the longest straight line among the straight lines connecting any two points on the outer periphery of the opening 19 on the vehicle outer side surface (surface 12A) of the vehicle glass 1.
  • the lengths d1 and d2 here refer to the lengths when the vehicle glass 1 is mounted on the vehicle V.
  • the lengths d1 and d2 are the lengths after bending. The same applies to dimensions and positions other than the lengths d1 and d2, unless otherwise specified.
  • a method for manufacturing the far-infrared transmitting member 20 will be explained.
  • a base material 30 is prepared, and a first functional film 32 is formed on the surface of the base material 30.
  • the method for forming the first functional film 32 is arbitrary, in this embodiment, the first functional film 32 is formed on the surface of the base material 30 by sputtering. That is, in the example of this embodiment, the intermediate layer 34 is formed on the surface of the base material 30 by sputtering. Then, the outermost layer 36 is formed on the surface of the base material 30, that is, on the surface of the intermediate layer 34 here, by sputtering.
  • the far-infrared transmitting member 20 is manufactured.
  • the adhesion of the film can be improved.
  • the second functional film 38 is formed by sputtering on the surface of the base material 30 on the side opposite to the first functional film 32 side.
  • the sputtering method may be arbitrary, and for example, a reactive sputtering method or a post-oxidation sputtering method may be used, and it is preferable to use a post-oxidation sputtering method.
  • FIG. 6 is a schematic diagram illustrating the method for manufacturing the far-infrared transmitting member according to the present embodiment.
  • the case where the outermost layer 36 is formed directly on the base material 30 will be taken as an example, but when the outermost layer 36 is formed on the intermediate layer 34, the outermost layer 36 is formed on the surface of the base material 30.
  • the same method as described below can be applied except for using the material 30.
  • the base material 30 is placed in the first space SP1 (step S10).
  • a target T is provided in the first space SP1 and is connected to an inert gas supply section M1.
  • the target T is a member that serves as a raw material for the outermost layer 36 that is laminated on the base material 30.
  • the base material 30 is arranged in the first space SP1 so that the surface 30a on the side where the outermost layer 36 is formed faces the target T.
  • the inert gas supply unit M1 is a device that supplies an inert gas G into the first space SP1, and makes the first space SP1 an inert gas G atmosphere.
  • Argon is used as the inert gas G, but the invention is not limited thereto, and for example, a rare gas other than argon may be used.
  • step S12 sputtering is performed by introducing an inert gas G into the first space SP1 where the target T and the base material 30 are placed.
  • the contained Zr is laminated on the surface 30a of the base material 30 (step S12; lamination step).
  • the inert gas G is introduced into the first space SP1 from the inert gas supply section M1 while the first space SP1 is evacuated.
  • the inert gas G is ionized, and the ionized inert gas G is caused to collide with the surface of the base material 30.
  • components (atoms and molecules) contained in the target T are ejected from the target T and stacked on the surface 30a of the base material 30.
  • the laminate containing Zr layered on the surface 30a of the base material 30 will be hereinafter referred to as a laminate 36A.
  • the components ejected from the target T and stacked as the laminate 36A are not limited to only Zr, but other components such as atoms and molecules contained in the target T (for example, ZrO 2 ) are also ejected from the target T. They may be laminated as a laminate 36A. That is, it can be said that the laminate 36A is a layer containing at least Zr.
  • the inert gas G is introduced into the first space SP1 while the first space SP1 is evacuated.
  • the vacuum here may refer to, for example, a pressure of 10 Pa or less, and the same applies hereafter.
  • the inert gas G is introduced so that the pressure in the first space SP1 is preferably less than 0.5 Pa, more preferably less than 0.4 Pa, even more preferably less than 0.3 Pa. It is preferable. That is, in this step, it is preferable to set the atmospheric pressure in the first space SP1 containing the inert gas G to be within the above range. By setting the first space SP to such an atmospheric pressure, it becomes possible to form a highly hard laminate 36A, and the scratch resistance can be improved.
  • the oxygen supply unit M2 is a device that supplies oxygen O.
  • oxygen plasma plasma-like oxygen
  • step S16 oxygen plasma
  • the second space SP2 is in a vacuum
  • oxygen O is supplied from the oxygen supply unit M2 into the second space SP2
  • the oxygen O in the second space SP2 is turned into plasma to generate oxygen plasma.
  • the generated oxygen plasma contacts the laminate 36A stacked on the base material 30, oxidizes the laminate 36A, and forms the outermost layer 36 on the base material 30.
  • Zr contained in the stacked body 36A is oxidized by the oxygen plasma and becomes ZrO 2 . It is thought that the oxidation process causes the film to expand in volume and become denser, resulting in higher hardness. As a result, the laminate 36A becomes the outermost layer 36 containing ZrO 2 as a main component, and the outermost layer 36 is formed on the base material 30. Note that oxidation may be performed by generating not only oxygen plasma but also oxygen radicals and oxygen ions.
  • Target T contains Zr.
  • the Zr content relative to the entire target T is preferably 50 atomic weight % or more and 100 atomic weight % or less, 60 atomic weight % or more and 100 atomic weight % or less, 70 atomic weight % or more and 100 atomic weight % or less, and 80 atomic weight % or more. More preferably, it is 100 atomic weight % or less.
  • the target T may contain ZrO 2 as a component other than Zr.
  • oxygen plasma may be generated by any method, but for example, by providing an electrode in the second space SP2 and applying a voltage to the electrode, oxygen O in the second space SP2 may be turned into plasma. Oxygen plasma may be generated.
  • the power applied to the electrode is preferably 2 kW or more and 4 kW or less, and more preferably 3 kW or more and 4 kW or less.
  • the outermost layer 36 may be formed to gradually become thicker by repeating the processes from step S10 to step S16.
  • the first space SP1 and the second space SP2 are separate spaces (rooms), and the base material 30 is transferred from the first space SP1 to the second space SP2 or the second space SP2.
  • the outermost layer 36 is formed by performing the above-described lamination step and oxidation step while moving from the substrate to the first space SP1. Any method may be used to move the base material 30 between the first space SP1 and the second space SP2, but for example, the base material 30 may be attached to the surface of a rotatable drum and arranged in the rotation direction of the drum. Thus, a first space SP1 and a second space SP2 may be formed.
  • the rotation of the drum moves the base material 30 from the first space SP1 to the second space SP2 (or from the second space SP2 to the first space SP1).
  • the first space SP1 and the second space SP2 may be the same space (room).
  • sputtering is performed by applying a voltage to the target T while introducing an inert gas G after creating a vacuum, and then supplying oxygen plasma into the space.
  • the laminate 36A may be oxidized to form the outermost layer 36.
  • the outermost layer 36 on the surface of the base material 30 by sputtering under conditions of a predetermined pressure and a predetermined temperature.
  • the predetermined pressure here is preferably 0.5 Pa or less, more preferably 0.1 Pa or more and 0.3 Pa or less, and even more preferably 0.15 Pa or more and 0.25 Pa or less.
  • the far-infrared transmitting member 20 includes the base material 30 that transmits far-infrared rays and the first functional film 32 (functional film) formed on the base material 30.
  • the far-infrared transmitting member 20 has an average transmittance of 50% or more for light having a wavelength of 8 ⁇ m to 12 ⁇ m.
  • the outermost layer 36 of the first functional film 32 is a layer containing ZrO 2 as a main component, and the content of ZrO 2 is 50% by mass or more and 100% by mass or less with respect to the entire outermost layer 36, and the wavelength
  • the refractive index for light of 550 nm is 2.05 or more.
  • the far-infrared transmitting member is required to appropriately transmit far-infrared rays and to improve scratch resistance. Since the far-infrared transmitting member 20 according to the present embodiment is provided with the outermost layer 36 mainly composed of ZrO 2 , it can appropriately transmit far-infrared rays and improve scratch resistance. Furthermore, for example, diamond-like carbon (DLC) can also improve scratch resistance, but DLC has a limited film formation process and requires elastic modulus control. load becomes higher. On the other hand, by using the outermost layer 36 mainly composed of ZrO 2 as in this embodiment, it is possible to improve the scratch resistance while reducing the load in the film forming process.
  • DLC diamond-like carbon
  • the outermost layer 36 preferably has an extinction coefficient of 0.10 or less for light with a wavelength of 10 ⁇ m. When the attenuation coefficient of the outermost layer 36 falls within this range, it becomes possible to appropriately transmit far-infrared rays.
  • the thickness D2 of the outermost layer 36 is preferably 20 nm or more. By setting the thickness D2 of the outermost layer 36 within this range, far infrared rays can be transmitted appropriately and scratch resistance can be improved.
  • the arithmetic mean roughness Ra of the surface 36a of the outermost layer 36 is preferably 7.0 nm or less. When the surface roughness falls within this range, it is possible to reduce the dynamic friction coefficient and the change in surface roughness before and after scratching, and to improve the scratch resistance more appropriately.
  • the outermost layer 36 preferably has a refractive index of 2.05 or more for light with a wavelength of 550 nm.
  • the refractive index falls within this range, the film density of the outermost layer 36 can be improved, and the scratch resistance can be improved more appropriately.
  • sputtering in a pressure range of 0.5 Pa or less or target Examples include short-distance sputtering in which the distance between the substrate 30 and the substrate 30 is 100 mm or less, film formation in a high temperature range of 200° C. or higher, and ion beam treatment during film formation.
  • the far-infrared transmitting member 20 has ⁇ a * b * of 5 or less.
  • ⁇ a * b * falls within this range, the visible light reflected from the far-infrared transmitting member 20 has a neutral color, making it possible to provide an appearance that maintains design.
  • the ratio of the thickness D2 of the outermost layer 36 to the thickness D1 of the base material 30 is preferably 0.002% or more and 0.030% or less. When the thickness D2 falls within such a range, it is possible to appropriately transmit far infrared rays and improve scratch resistance.
  • the first functional film 32 further includes an intermediate layer 34 provided between the outermost layer 36 and the base material 30.
  • an intermediate layer 34 By providing the intermediate layer 34, far infrared rays can be appropriately transmitted.
  • intermediate layer 34 includes an antireflection layer.
  • This antireflection layer is a layer containing NiOx as a main component, and the content of NiOx is preferably 50% by mass or more and 100% by mass or less based on the entire antireflection layer.
  • the antireflection layer containing NiOx as a main component, far infrared rays can be appropriately transmitted.
  • the far-infrared transmitting member 20 is preferably mounted on a vehicle.
  • the far-infrared transmitting member 20 is particularly suitable for vehicle use.
  • the far-infrared transmitting member 20 is placed in a window member of a vehicle.
  • the far-infrared transmitting member 20 is particularly suitable for a vehicle window member.
  • the far-infrared transmitting member 20 is disposed in an exterior member for a pillar of a vehicle.
  • the far-infrared transmitting member 20 is particularly suitable for an exterior member for a pillar of a vehicle.
  • the far-infrared transmitting member 20 is disposed within a light-shielding area of the vehicle exterior member.
  • the far-infrared transmitting member 20 is particularly suitable for a vehicle exterior member.
  • the manufacturing method according to the present embodiment is a method for manufacturing a far-infrared transmitting member 20 in which a first functional film 32 (functional film) is formed on a base material 30 that transmits far-infrared rays, and includes sputtering on the base material 30.
  • the method includes a step of manufacturing the far-infrared transmitting member 20 by forming the outermost layer 36 of the first functional film 32.
  • the far-infrared transmitting member 20 has an average transmittance of 50% or more for light with a wavelength of 8 ⁇ m to 12 ⁇ m, and the outermost layer 36 is a layer containing ZrO 2 as a main component, and the content of ZrO 2 is higher than that of the outermost layer 36.
  • the refractive index for light with a wavelength of 550 nm is 2.05 or more. According to this manufacturing method, it is possible to manufacture the far-infrared transmitting member 20 that can appropriately transmit far-infrared rays and improve scratch resistance.
  • the outermost layer 36 In the step of forming the outermost layer 36, it is preferable to perform sputtering under a pressure of 0.30 Pa or less. By performing sputtering under such low pressure, the outermost layer 36 with excellent scratch resistance can be formed.
  • the sputtering is a post-oxidation sputtering method. By performing post-oxidation sputtering, the outermost layer 36 with excellent scratch resistance can be formed.
  • Tables 1 and 2 are tables showing far-infrared transmitting members of each example.
  • Example 1 As shown in Table 1, in Example 1, an intermediate layer was formed on a substrate made of Si (FZ grade) by post-oxidation sputtering using a load-lock sputtering device (RAS-1100BII, manufactured by Synchron). A NiO x film, a ZrO 2 film, and a NiO x film were formed in this order, and the ZrO 2 film as the outermost layer was formed on the surface farthest from the base material. The thicknesses of the base material, NiO x film, and ZrO 2 film were as shown in Table 1. The thickness of the base material was measured with a digital caliper (manufactured by Mitutoyo Co., Ltd., CD-15CX).
  • the thickness of the functional film was evaluated using a stylus profiling system (Dektak XT-S, manufactured by BRUKER).
  • the conditions for forming the NiO x film and ZrO 2 film are as follows. Table 1 lists some of the film forming conditions (sputtering method and film forming pressure).
  • Target Zr target Sputtering gas: Ar gas (flow rate: 150 sccm) Input power: 6kW Reactive gas: O 2 (flow rate: 100 sccm) RF power: 4kW Substrate temperature: Room temperature Deposition pressure: 0.21Pa
  • Example 2 As shown in Table 1, in Example 2, a NiO x film was formed as an intermediate layer and a NiO ZrO 2 films were formed in this order. A far-infrared transmitting member was obtained in the same manner as in Example 1, except that the thicknesses of the base material, NiO x film, and ZrO 2 film were as shown in Table 1.
  • the conditions for forming the NiO x film and ZrO 2 film are as follows. The film forming pressure was adjusted by the opening degree of the APC valve of the turbo molecular pump.
  • Target Zr target Sputtering gas: Ar gas (flow rate: 100 sccm) Reactive gas: O 2 (flow rate: 50 sccm) Input power: 3kW Substrate temperature: Room temperature Deposition pressure: 0.24Pa
  • Example 3-Example 12 far-infrared transmitting members were obtained in the same manner as in Example 2, except that the material and thickness of the film were changed as shown in Tables 1 and 2.
  • the conditions for forming the ZnO film, SiO 2 film, Al 2 O 3 film, and Si film are as follows.
  • Target Zn target Sputtering gas: Ar gas (flow rate: 100 sccm) Reactive gas: O 2 (flow rate: 100 sccm) Input power: 3000W Substrate temperature: Room temperature Deposition pressure: 0.24Pa
  • Target Si target Sputtering gas: Ar gas (flow rate: 100 sccm) Reactive gas: O 2 (flow rate: 100 sccm) Input power: 3000W Substrate temperature: room temperature Deposition pressure: 0.28Pa
  • Target Al target Sputtering gas: Ar gas (flow rate: 100 sccm) Reactive gas: O 2 (flow rate: 100 sccm) Input power: 3000W Substrate temperature: Room temperature Deposition pressure: 0.24Pa
  • Target Si target Sputtering gas: Ar gas (flow rate: 200 sccm) Reactive gas: None Input power: 3000W Substrate temperature: Room temperature Deposition pressure: 0.27Pa
  • Example 13 In Example 13, a far-infrared transmitting member was obtained in the same manner as in Example 2, except that the thickness of the NiO x film and the film forming conditions of the ZrO 2 film were changed as shown in Table 2. .
  • the conditions for forming the ZrO 2 film are as follows.
  • Target Zr target Sputtering gas: Ar gas (flow rate: 100 sccm) Reactive gas: O 2 (flow rate: 50 sccm) Input power: 3000W Substrate temperature: room temperature Deposition pressure: 0.84Pa
  • Example 14 In Example 14, a far-infrared transmitting member was obtained in the same manner as in Example 1 except that the structure of the intermediate layer was changed as shown in Table 2.
  • the physical property values of the far-infrared transmitting member of each example were measured.
  • the refractive index of the film on the farthest side (outermost side) from the base material of the far-infrared transmitting member with respect to light with a wavelength of 550 nm was evaluated.
  • the refractive index is determined by fitting an optical model using polarization information obtained by a spectroscopic ellipsometer (M-2000, manufactured by J.A. Woollam) and spectral transmittance measured based on JIS R3106. did.
  • M-2000 spectroscopic ellipsometer
  • spectral transmittance measured based on JIS R3106. did.
  • the film on the farthest side (outermost) from the base material refers to the outermost layer, for example, refers to the film 4 in Example 1, and refers to the film 2 in Example 2.
  • the arithmetic mean roughness Ra of the farthest side (outermost) surface from the base material of the far-infrared transmitting member was measured based on JIS B0601. Note that the farthest (outermost) surface from the base material refers to the surface of the membrane 4 in Example 1, and the surface of the membrane 2 in Example 2, for example.
  • indentation hardness As a physical property value, the indentation hardness of the first functional film in the film thickness direction (depth direction) was measured by the nanoindentation method using an iMicro type nanoindenter (manufactured by KLA). The measurement conditions are as follows. ⁇ Indenter: Berkovich Actuator: IF50 ⁇ Measurement method: Continuous stiffness measurement method ⁇ Maximum pushing load: 50mN ⁇ Strain rate: 0.2%/s ⁇ Poisson's ratio of sample: 0.25 - Number of measurement points: 15 to 20 points per substrate The average value of indentation hardness at an indentation depth of 108 nm was adopted as the representative value. In order to minimize the influence of the substrate, it is recommended to perform evaluation at a depth of indentation of 1/10 or less of the evaluation film thickness.
  • the average transmittance (FIR-T) of light with a wavelength of 8 ⁇ m to 12 ⁇ m was measured.
  • the measurement method is to measure the transmittance of light at each wavelength of 8 ⁇ m to 12 ⁇ m using a Fourier transform infrared spectrometer (manufactured by Thermo Scientific, trade name: Nicolet iS10), and calculate the average from the measured transmittance. Transmittance was calculated.
  • ⁇ a * b * As a physical property value, ⁇ a * b * was measured. Based on JIS R3106, the reflection spectrum in the visible range was measured using U4100 (manufactured by Hitachi), and based on JIS Z 8781-4, the CIE-Lab color system when using standard illuminant D65 as the illumination light. The chromaticity coordinates L * a * b * of the reflected light were determined, and ⁇ a * b * was calculated based on the above equation (3).
  • the far-infrared transmitting member of each example was evaluated.
  • a wiper test was performed and the number of scratches formed by the wiper test was measured. Specifically, after performing a wiper test on the surface farthest from the base material (outermost) under the following conditions, the sliding area where the wiper was slid was examined using an optical microscope DSX500 (manufactured by OLYMPUS). Dark-field observation was performed using a 350x magnification. In dark field observation, the number of scratches in a 1.8 mm area perpendicular to the sliding direction was measured. In the wiper test, the surface farthest from the base material (outermost) was abraded using a traverse abrasion tester under the test conditions shown below.
  • a wiper rubber (genuine product for Toyota vehicles, model number 85214-47170) was attached to a traverse wear tester, a dust solution was dropped between the wiper and the sample, and reciprocating friction was performed while applying a contact load to the wiper. .
  • the wiper width was 20 mm
  • the stroke width was 40 mm
  • the number of strokes was 2500 reciprocations
  • the load was equivalent to 50 g.
  • a dust solution was prepared by mixing 8 types of JIS test powder 1 and pure water at a mass ratio of 3:100, and 2 ml of the dust solution was dropped onto the sliding area. The substrate was cleaned every 500 reciprocations, and the dust solution was dropped again, so that a total of 2500 reciprocating frictions were performed.
  • Examples 5 to 10 and 13 which correspond to comparative examples, failed the wiper test due to low mechanical strength, and it is presumed that it is not possible to improve the scratch resistance while appropriately transmitting far infrared rays. It can be seen that Examples 5, 7, and 9 corresponding to comparative examples have low wiper abrasion resistance even though the indentation hardness is as high as 8.0 GPa or more. This is presumably because the film type has low resistance to adhesive wear and chemical wear in a mixed system of water and dust. From the above results, it can be said that a ZrO 2 film with high chemical stability and high indentation hardness is suitable as the outermost layer.
  • Example 13 which corresponds to the comparative example, failed the wiper test because the film formation pressure of the ZrO 2 film was high and the ZrO 2 film had a sparse film quality with a refractive index of less than 2.05 for light with a wavelength of 550 nm. Therefore, it is presumed that it is not possible to improve the scratch resistance while appropriately transmitting far infrared rays.
  • color change evaluation and boiling test were performed.
  • color change evaluation and boiling test were performed.
  • the surface farthest from the base material after the wiper test was visually observed to confirm whether the entire worn area had undergone color change. If a color change occurs, it is considered that minute abrasion of the film or a change in surface roughness has occurred, so it is more preferable that no color change occurs.
  • Table 2 by comparing Example 11 with Examples 2, 12, and 14, it can be seen that when the arithmetic mean roughness Ra of the surface is small, color change does not occur and scratch resistance can be improved more suitably. I understand.
  • the boiling test was conducted in accordance with JIS R3212 by holding each sample in pure water at 100°C ⁇ 2°C for 2 hours.
  • the embodiment of the present invention has been described above, the embodiment is not limited by the content of this embodiment. Furthermore, the above-mentioned components include those that can be easily assumed by those skilled in the art, those that are substantially the same, and those that are in a so-called equivalent range. Furthermore, the aforementioned components can be combined as appropriate. Furthermore, various omissions, substitutions, or modifications of the constituent elements can be made without departing from the gist of the embodiments described above.
  • Vehicle glass 10 12
  • Glass substrate 20
  • Far-infrared transmitting member 30
  • Base material 32
  • First functional film (functional film) 34
  • Intermediate layer 36
  • Outermost layer 38

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PCT/JP2023/005632 2022-03-07 2023-02-17 遠赤外線透過部材及び遠赤外線透過部材の製造方法 Ceased WO2023171309A1 (ja)

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WO2025053210A1 (ja) * 2023-09-06 2025-03-13 Ａｇｃ株式会社 透過部材及び透過部材の製造方法
WO2026071060A1 (ja) * 2024-09-26 2026-04-02 Ａｇｃ株式会社 車両用ガラスおよび車両用ガラスの製造方法

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WO2026071060A1 (ja) * 2024-09-26 2026-04-02 Ａｇｃ株式会社 車両用ガラスおよび車両用ガラスの製造方法

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