WO2020017495A1 - 光学部材 - Google Patents

光学部材 Download PDF

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Publication number
WO2020017495A1
WO2020017495A1 PCT/JP2019/027906 JP2019027906W WO2020017495A1 WO 2020017495 A1 WO2020017495 A1 WO 2020017495A1 JP 2019027906 W JP2019027906 W JP 2019027906W WO 2020017495 A1 WO2020017495 A1 WO 2020017495A1
Authority
WO
WIPO (PCT)
Prior art keywords
optical member
transparent substrate
refractive index
oxide
glass
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/JP2019/027906
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
山本　宏行
尚洋 眞下
尾山　卓司
田原　慎哉
長嶋　達雄
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 JP2020531312A priority Critical patent/JP7298073B2/ja
Priority to CN201980047241.2A priority patent/CN112424654B/zh
Priority to EP19836948.0A priority patent/EP3825742A4/en
Publication of WO2020017495A1 publication Critical patent/WO2020017495A1/ja
Priority to US17/145,536 priority patent/US11994699B2/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • C03C4/00—Compositions for glass with special properties
    • C03C4/0092—Compositions for glass with special properties for glass with improved high visible transmittance, e.g. extra-clear glass
    • G—PHYSICS
    • G02—OPTICS
    • 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
    • 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
    • B32B17/10082—Properties of the bulk of a glass sheet
    • B32B17/1011—Properties of the bulk of a glass sheet having predetermined tint or excitation purity
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60J—WINDOWS, WINDSCREENS, NON-FIXED ROOFS, DOORS, OR SIMILAR DEVICES FOR VEHICLES; REMOVABLE EXTERNAL PROTECTIVE COVERINGS SPECIALLY ADAPTED FOR VEHICLES
    • B60J1/00—Windows; Windscreens; Accessories therefor
    • B60J1/001—Double glazing for vehicles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60J—WINDOWS, WINDSCREENS, NON-FIXED ROOFS, DOORS, OR SIMILAR DEVICES FOR VEHICLES; REMOVABLE EXTERNAL PROTECTIVE COVERINGS SPECIALLY ADAPTED FOR VEHICLES
    • B60J1/00—Windows; Windscreens; Accessories therefor
    • B60J1/02—Windows; Windscreens; Accessories therefor arranged at the vehicle front, e.g. structure of the glazing, mounting of the glazing
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B27/00—Tempering or quenching glass products
    • C03B27/04—Tempering or quenching glass products using gas
    • C03B27/0413—Stresses, e.g. patterns, values or formulae for flat or bent glass sheets
    • 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
    • C03C17/3417—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 all coatings being oxide coatings
    • 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
    • C03C17/3429—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 at least one of the coatings being a non-oxide coating
    • C03C17/3435—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 at least one of the coatings being a non-oxide coating comprising a nitride, oxynitride, boronitride or carbonitride
    • 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
    • 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
    • C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
    • 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
    • C03C4/00—Compositions for glass with special properties
    • C03C4/10—Compositions for glass with special properties for infrared transmitting glass
    • 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
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/28—Interference filters
    • G02B5/285—Interference filters comprising deposited thin solid films
    • 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
    • C03C17/3429—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 at least one of the coatings being a non-oxide coating
    • C03C17/3482—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 at least one of the coatings being a non-oxide coating comprising silicon, hydrogenated silicon or a silicide
    • 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
    • C03C2217/00—Coatings on glass
    • C03C2217/70—Properties of coatings
    • C03C2217/73—Anti-reflective coatings with specific characteristics
    • C03C2217/734—Anti-reflective coatings with specific characteristics comprising an alternation of high and low refractive indexes
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01S—RADIO DIRECTION-FINDING; RADIO NAVIGATION; DETERMINING DISTANCE OR VELOCITY BY USE OF RADIO WAVES; LOCATING OR PRESENCE-DETECTING BY USE OF THE REFLECTION OR RERADIATION OF RADIO WAVES; ANALOGOUS ARRANGEMENTS USING OTHER WAVES
    • G01S17/00—Systems using the reflection or reradiation of electromagnetic waves other than radio waves, e.g. lidar systems
    • G01S17/88—Lidar systems specially adapted for specific applications
    • G01S17/93—Lidar systems specially adapted for specific applications for anti-collision purposes
    • G01S17/931—Lidar systems specially adapted for specific applications for anti-collision purposes of land vehicles
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01S—RADIO DIRECTION-FINDING; RADIO NAVIGATION; DETERMINING DISTANCE OR VELOCITY BY USE OF RADIO WAVES; LOCATING OR PRESENCE-DETECTING BY USE OF THE REFLECTION OR RERADIATION OF RADIO WAVES; ANALOGOUS ARRANGEMENTS USING OTHER WAVES
    • G01S7/00—Details of systems according to groups G01S13/00, G01S15/00, G01S17/00
    • G01S7/48—Details of systems according to groups G01S13/00, G01S15/00, G01S17/00 of systems according to group G01S17/00
    • G01S7/481—Constructional features, e.g. arrangements of optical elements
    • G01S7/4811—Constructional features, e.g. arrangements of optical elements common to transmitter and receiver
    • G01S7/4813—Housing arrangements

Definitions

  • the present invention relates to an optical member, and more particularly, to an optical member having a high transmittance for infrared light over a wide range of incident angles.
  • Autonomous driving technology requires measuring the distance between a vehicle and surrounding objects.
  • a technique of a LiDAR (Light Detection and Ranging) sensor using light in an infrared region is used.
  • Patent Literature 1 discloses that a glass having a predetermined amount of iron, titania, and ceria is used as a window glass of a vehicle in correspondence with light in a visible region to an infrared region used for a sensor. Discloses a laminated glass having a transmittance of at least 30% in a wavelength range of
  • Patent Literature 1 discusses only the transmittance of the laminated glass with respect to light having an incident angle of 0 degrees, does not consider the transmittance with respect to light having a high incident angle, and has a sufficient transmittance with respect to a high incident angle. Was not a good value. That is, the LiDAR sensor used in the automatic driving technique is required to have high transmittance of infrared light (hereinafter, referred to as “infrared light”) over a wide range of incident angles.
  • infrared light infrared light
  • the laminated glass of Patent Document 1 cannot meet such a demand.
  • An object of the present invention is to provide an optical member having a high transmittance for infrared light over a wide range of incident angles.
  • the optical member of the present invention A transparent substrate including at least one substance selected from glass, glass ceramics, silicon, and sapphire, having a high infrared transmission region having a transmittance of 78% or more in a wavelength region of 700 nm to 1800 nm, and a high infrared transmission region; an optical member comprising a corresponding said transparent substrate optical interference film arranged on the main surface of the, in the infrared high permeability region of the transparent substrate at least one wavelength lambda s of the following wavelength range 700nm or 1800nm
  • the light transmittance of the corresponding region of the optical member has a minimum value of 86.5% or more and a minimum value of 9% or less and a maximum value of 9% or less when the incident angle is in a range of 0 to 60 degrees. It is an optical member having a difference.
  • permeability over a wide range of incident angles with respect to infrared light is obtained.
  • the optical member of the present invention is used, for example, as a cover member of a LiDAR sensor, transmission of infrared light used for sensing by the LiDAR sensor is not prevented over a wide incident angle.
  • the optical member of the present invention is used as a window glass, a reduction in the sensing function via the window glass is suppressed.
  • FIG. 2 is a cross-sectional view schematically illustrating an example of the optical member according to the embodiment. It is a top view showing roughly an example of the optical member (windshield) concerning an embodiment.
  • FIG. 2 is a cross-sectional view of the optical member (front glass) shown in FIG. 1B, taken along line XX.
  • FIG. 1B is a cross-sectional view schematically showing one of the usage examples of the optical member shown in FIG. 1A.
  • 5 is a spectral transmittance curve of the optical member according to Example 1 for incident light at incident angles of 0 ° and 60 °.
  • ⁇ 5 is a spectral transmittance curve near a predetermined wavelength ⁇ s (940 nm) with respect to incident light having an incident angle of 0 ° and 60 ° of the optical member according to Example 1 of the embodiment.
  • 9 is a spectral transmittance curve of the optical member according to Example 2 for incident light at incident angles of 0 ° and 60 °.
  • 9 is a spectral transmittance curve near a predetermined wavelength ⁇ s (940 nm) with respect to incident light having an incident angle of 0 ° and 60 ° of the optical member according to Example 2 of the embodiment.
  • the transmittance for a specific wavelength range, that the transmittance is, for example, 78% or more means that the transmittance does not fall below 78% in the entire wavelength range.
  • a transmittance of, for example, 1% or less means that the transmittance does not exceed 1% in the entire wavelength region.
  • “to” indicating a numerical range includes an upper limit and a lower limit in the numerical range.
  • the optical member according to the embodiment of the present invention includes at least one substance selected from glass, glass ceramics, silicon, and sapphire, and has a transmittance in a wavelength range of 700 nm to 1800 nm.
  • a transparent substrate having a high infrared transmission region (hereinafter, also referred to as a “predetermined region”) having a ratio of 78% or more, and a light interference film disposed on a main surface of the transparent substrate corresponding to the high infrared transmission region.
  • the area of the optical member corresponding to the above-mentioned high infrared transmission area of the transparent substrate satisfies the following requirement (1).
  • the transparent substrate contains at least one substance selected from glass, glass ceramics, silicon and sapphire and has a transmittance of 78% or more in a wavelength range of 700 nm to 1800 nm is hereinafter referred to as requirement (A).
  • the transmittance in the requirement (A) is a transmittance measured with respect to incident light at an incident angle of 0 degree with respect to any one main surface of the transparent substrate, and the irradiation surface is not limited.
  • Light transmittance in at least one wavelength lambda s of 700nm or 1800nm wavelengths below region is in a range of incidence angles of 60 degrees or less than 0 degrees, the minimum value of more than 86.5% (hereinafter, “T ( 1) also referred to as “ min ”) and a difference between the minimum value and the maximum value of 9% or less (hereinafter also referred to as “ ⁇ T (1) ”).
  • T ( 1) also referred to as “ min ”
  • ⁇ T (1) a difference between the minimum value and the maximum value of 9% or less
  • the wavelength ⁇ s may be simply referred to as “ ⁇ s ”.
  • the incident angle is an incident angle with respect to the main surface of the optical member in the predetermined area.
  • the optical characteristics described in this specification are characteristics of light incident from any one main surface of the optical member, and the incident surface is not limited.
  • the transmittance and the reflectance of light having a specific wavelength for example, a wavelength of 700 nm or more and 1800 nm or less, in a transparent substrate and an optical member are determined by a spectrophotometer having a variable incident angle, for example, a V- spectrometer manufactured by Hitachi Spectroscopy. It can be measured at 570 or the like.
  • the optical member has a high transmittance for infrared light having a wavelength of 700 nm or more and 1800 nm or less over a wide range of incident angles.
  • the predetermined wavelength ⁇ s is, for example, the wavelength of laser light used for sensing by the LiDAR sensor used with the present optical member.
  • the present optical member may have at least one predetermined wavelength that satisfies the requirement of (1), and may satisfy the requirement of (1) at two or more predetermined wavelengths.
  • the wavelength lambda s is, 900 nm or less in the range of 750 nm, preferably 875 nm or less in the range of 775 nm, more preferably, it is 800nm or 850nm the range, the.
  • the wavelength ⁇ s is in a range from 830 nm to 980 nm, preferably in a range from 855 nm to 955 nm, and more preferably in a range from 880 nm to 930 nm.
  • the wavelength lambda s is, 1125Nm following range of 975 nm, preferably, 1100 nm or less in the range of 1000 nm, more preferably in the 1075nm following range of 1025Nm.
  • the wavelength ⁇ s is in the range from 1475 nm to 1625 nm, preferably in the range from 1500 nm to 1600 nm, more preferably in the range from 1525 nm to 1575 nm.
  • T (1) min ⁇ 86.5% is also referred to as a requirement of (1-1), and ⁇ T (1) ⁇ 9% is also referred to as a requirement of (1-2).
  • T (1) min is 86.5% or more, for example, when used in combination with a LiDAR sensor, it can be said that the transmittance is sufficient to maintain a wide-angle scan of the LiDAR sensor.
  • T (1) min is preferably at least 87%, more preferably at least 89%, particularly preferably at least 90%.
  • ⁇ T (1) is 9% or less, the fluctuation of the transmittance in the range of the incident angle of 0 ° to 60 ° at the wavelength ⁇ s can be used in combination with the LiDAR sensor, for example. And the possibility that the fluctuation becomes noise is small.
  • ⁇ T (1) is preferably at most 8%, more preferably at most 7%, further preferably at most 5%, particularly preferably at most 3.5%.
  • the present optical member further has at least one of the following requirements (2) to (4) in the predetermined region, and has at least two of the following requirements (2) to (4). It is more preferable that all of the requirements (2) to (4) are satisfied.
  • the light loss of the light of wavelength ⁇ s irradiated at an incident angle of 5 degrees is 3% or less.
  • the light loss can be calculated as a value obtained by subtracting the transmittance and the reflectance from 100%. It is preferable that the present optical member satisfies the requirement (2) when the present optical member is combined with a LiDAR sensor because the sensor can efficiently receive incident light.
  • the light loss is more preferably 2.5% or less, further preferably 1.0% or less, and particularly preferably 0.7% or less.
  • a change in transmittance of light having a wavelength of ⁇ s at an incident angle of 0 ° is 1% or less before and after exposing the optical member to an environment at a temperature of 60 ° C. and a relative humidity of 80% for 48 hours. If the requirement of (3) is satisfied, the present optical member has excellent durability in a high-temperature and high-humidity use environment.
  • the present optical member When the present optical member is used, for example, as a cover member of a LiDAR sensor mounted outside a vehicle, the present optical member is exposed to outside air.
  • the optical member even when the LiDAR sensor is mounted in a vehicle, the optical member may be placed in a high-temperature and high-humidity environment in the vehicle. Even in such a case, long-term stable use is possible if the requirement of (3) is satisfied.
  • the change in transmittance is more preferably 0.8% or less, further preferably 0.6% or less, and particularly preferably 0.4% or less.
  • the Martens hardness at the indentation depth of 50 nm measured on the surface of the optical interference film of the optical member is larger than the Martens hardness at the indentation depth of 50 nm measured on the surface of the transparent substrate.
  • the Martens hardness is measured by a micro hardness tester using a Vickers indenter, a maximum load reaching time of 10 seconds, a creep time of 5 seconds, a pushing load of 0.05 mN to 500 mN, and a load speed of 1 mmN / 10 s.
  • the Martens hardness at an indentation depth of 50 nm measured under the above measurement conditions is simply referred to as “Martens hardness”.
  • an optical member having a higher Martens hardness on the surface of the light interference film than on the surface of the transparent substrate can be obtained. That is, an optical member having high durability can be obtained.
  • the Martens hardness measured on the surface of the optical interference film of the present optical member and the Martens hardness of the transparent substrate used for the present optical member will be specifically described later.
  • FIG. 1 schematically shows an example of a cross-sectional view of the optical member according to the embodiment.
  • the optical member 10A shown in FIG. 1 includes a transparent substrate 1 having a first main surface 1a and a second main surface 1b facing each other, and a light interference film 2.
  • the transparent substrate 1 as a whole satisfies the requirement (A), and the optical interference film 2 is disposed on the entire first main surface 1 a of the transparent substrate 1.
  • the optical member 10A including the transparent substrate 1 and the light interference film 2 satisfies the requirement (1).
  • the light interference film 2 is a multilayer film in which three layers denoted by reference numerals 21, 22, and 23 are sequentially stacked from the transparent substrate 1 side.
  • the number of stacked light interference films satisfying the requirement (1) is not limited in combination with the transparent substrate satisfying the requirement (A).
  • optical member 10A a configuration in which the optical interference film 2 is provided on the second main surface 1b of the transparent substrate 1 or a configuration in which the optical interference film 2 is provided on the first main surface 1a of the transparent substrate 1 and the second On the main surface 1b. Since these examples also satisfy the requirement (1), they are included in the category of the present optical member.
  • the present optical member may have a configuration in which the light interference film 2 is provided only in a predetermined region of the first main surface 1a of the transparent substrate 1.
  • the requirement (1) may be satisfied in the region of the transparent substrate 1 where the light interference film 2 is provided, and the region without the interference film 2 may not satisfy the requirement (1).
  • the transparent substrate 1 does not have to satisfy the requirement (A).
  • the energy transmittance of the region of the optical member corresponding to the region other than the infrared light transmitting region of the transparent substrate 1 measured according to JIS-R3106: 1998 is preferably 60% or less, more preferably 50% or less. It is particularly preferably at most 45%, more preferably at most 40%.
  • the present optical member when the present optical member is applied to a window glass for an automobile and a LiDAR sensor is installed inside the vehicle, only the area of the transparent substrate 1 provided in the size of the window glass through which the laser light from the LiDAR sensor is transmitted.
  • the light interference film 2 may be disposed on the main surface of the transparent substrate 1 that satisfies the requirement (A).
  • the light interference film 2 may be disposed on the vehicle interior surface of the transparent substrate 1, may be disposed on the vehicle exterior surface, or may be disposed on both of them.
  • FIG. 1B is a plan view of an example of the present optical member according to the embodiment, applied to a windshield for an automobile.
  • FIG. 1C is a cross-sectional view obtained by cutting the windshield shown in FIG. 1B along the line XX.
  • the windshield 10B which is the present optical member, includes a transparent substrate 1 and a shielding layer 4 that is provided on the inner surface 1a of the transparent substrate 1 and along the outer periphery of the transparent substrate 1 and that shields visible light. .
  • the shielding layer 4 has a protruding portion formed to protrude from the center of the upper side of the transparent substrate 1 in the in-plane direction (downward).
  • the protruding portion has an opening 3 at the substantially center thereof, through which an infrared laser light signal of the LiDAR sensor is transmitted and received when the signal is transmitted and received.
  • the light interference film 2 is provided on the inner surface 1 a of the opening 3.
  • FIG. 1B is a plan view of the windshield 10B viewed from the inside of the vehicle.
  • FIG. 1B shows a mounting portion A of the LiDAR sensor by a dotted line.
  • the mounting portion A is located around the opening 3 of the shielding layer 4.
  • FIG. 1C schematically shows the configuration of the LiDAR sensor 40 attached to the windshield 10B by a dotted line.
  • the LiDAR sensor 40 has a LiDAR sensor main body 41 and a housing 42 that houses the LiDAR sensor main body 41.
  • the LiDAR sensor 40 is attached, for example, by attaching the housing 42 to the attachment portion A via the adhesive layer 43 to the shielding layer 4.
  • the transparent substrate 1 of the windshield 10B is a laminated glass.
  • the laminated glass that is the transparent substrate 1 has a configuration in which a vehicle interior glass plate 1A and a vehicle exterior glass plate 1B are bonded via an intermediate bonding layer 1C.
  • the laminated glass constituting the transparent substrate 1 is designed to satisfy the requirement (A) in the region inside the opening 3.
  • the windshield 10B has the light interference film 2 on the interior surface 1a of the transparent substrate 1 corresponding to the opening 3.
  • the opening 3 of the windshield 10B satisfies the requirement (1).
  • the decrease in the amount of the infrared laser light of the LiDAR sensor 40 transmitted and received through the opening 3 is suppressed over a wide incident angle, and the sensing function hardly decreases.
  • FIG. 1D shows an example of a LiDAR sensor attached to the inside of a windshield using the optical member 10A shown in FIG. 1A as a cover member of the LiDAR sensor.
  • the front glass 20 has a configuration in which a vehicle interior glass plate 21 and a vehicle exterior glass plate 22 are bonded via an intermediate bonding layer 23.
  • the optical member 10A is installed on the LiDAR sensor main body 41 such that the light interference film 2 is located on the LiDAR sensor main body 41 side.
  • the LiDAR sensor main body 41 with the optical member 10A is attached to the windshield 20 by bonding the transparent substrate 1 of the optical member 10A to the interior surface of the windshield 20 (the laminated glass 20) via the optical adhesive layer 5. Have been.
  • the difference between the maximum value and the minimum value of the plane stress is 10 MPa or less in at least one portion of the region 300 mm inward from the edge of the windshield 20. From the viewpoint of reducing the optical distortion of the sensor mounting portion, more preferably 5 MPa or less, most preferably 1 MPa or less.
  • the infrared laser light is transmitted and received between the inside of the vehicle and the outside of the vehicle via the optical member 10A and the laminated glass 20. Therefore, for example, if the configuration of the laminated glass 20 is designed to satisfy the requirement (A), the effect of the optical member 10A is sufficiently exerted, and the infrared laser light used by the LiDAR sensor main body 41 extends over a wide incident angle. Thus, a decrease in the amount of light is suppressed, and there is almost no decrease in sensing.
  • the transparent substrate 1 has a first main surface 1a and a second main surface 1b facing each other.
  • the transparent substrate 1 includes at least one substance selected from glass, glass ceramics, silicon, and sapphire, and has a minimum transmittance (hereinafter, also referred to as “ TB700-1800 ”) of 78% in a wavelength range of 700 nm to 1800 nm. That is all.
  • TB700-1800 minimum transmittance
  • the transparent substrate 1 may not partially satisfy the requirement (A) as necessary, but the following description will be made on an example in which the transparent substrate 1 as a whole satisfies the requirement (A). I do.
  • the TB700-1800 of the transparent substrate is 78% or more, the present optical member satisfies the requirement of (1).
  • the TB700-1800 of the transparent substrate is preferably at least 80%, more preferably at least 85%, even more preferably at least 88%, particularly preferably at least 88.5%, most preferably at least 89%, and preferably at least 89.5%. Even more preferred.
  • the transparent substrate preferably has a minimum transmittance (hereinafter, also referred to as “ TB800-1600 ”) of 79% or more in a wavelength range of 800 nm to 1600 nm. If the transparent substrate T B800-1600 79% or more, in the optical member (1), in particular, in the case having a wavelength lambda s in a wavelength range 800nm or 1600 nm T (1) min and [Delta] T (1 ) Requirements are more fully satisfied.
  • TB800-1600 of the transparent substrate is preferably at least 81%, more preferably at least 86%, further preferably at least 89%, particularly preferably at least 90.5%, most preferably at least 91%.
  • the transparent substrate 1 may be composed of only one of glass, glass ceramics, silicon, and sapphire, or may be composed of a mixture thereof. Other materials may be included.
  • the transparent substrate 1 may be a single plate or a laminate.
  • the transparent substrate 1 may be a laminated glass having a plurality of glass plates and a resin film disposed therebetween.
  • the transparent substrate 1 is composed of a plurality of layers such as laminated glass, the transmittance of each layer is adjusted so that TB700-1800 becomes 78% or more when the laminated glass is formed.
  • the shape of the transparent substrate 1 may be a flat plate, or may have a curvature on the entire surface or a part thereof.
  • a flat transparent substrate is prepared so as to have the same configuration as the transparent substrate 1, and optical characteristics such as transmittance are measured.
  • an optical member using the transparent substrate 1 having a curvature an optical member using a flat transparent substrate having the same configuration as the optical member is manufactured, and the optical characteristics are measured.
  • the thickness of the transparent substrate 1 can be appropriately adjusted according to the use within a range satisfying the requirement (A).
  • the thickness of the transparent substrate 1 is preferably 0.5 to 5 mm, more preferably 1 to 5 mm, still more preferably 1.5 to 4.5 mm, and more preferably 2 to 4.3 mm from the viewpoint of strength and weight balance by ensuring safety. Particularly preferred.
  • the total of the thickness of the plurality of glass plates and the thickness of the intermediate film is the thickness of the transparent substrate 1. Martens hardness measured at the surface of the transparent substrate 1, 4N / mm 2 or more, more preferably 4.5 N / mm 2 or more, 5N / mm 2 or more is more preferable.
  • the transparent substrate 1 is preferably made of an amorphous material, and more preferably made of glass. From the viewpoint of cost, it is particularly preferable to use an amorphous glass that can be manufactured by the float method.
  • Amorphous glass for example, soda lime glass, borosilicate glass, alkali-free glass, aluminosilicate glass, alkali-free aluminosilicate glass, quartz glass and the like as a basic glass, iron-containing glass containing iron in this preferable.
  • soda lime glass and borosilicate glass are preferable, and soda lime glass is particularly preferable.
  • the amount of iron (Fe) contained in the iron-containing glass is preferably from 1 to 500 ppm by mass, more preferably from 50 to 300 ppm by mass, and more preferably from 80 to 300 ppm by mass in terms of Fe 2 O 3 based on 100% by mass of the basic glass. 180 mass ppm is more preferred.
  • the iron-containing glass contains an Fe amount equal to or less than the above upper limit, TB700-1800 of the transparent substrate is easily adjusted to 78% or more.
  • the iron-containing glass contains the Fe content equal to or more than the above lower limit, it is possible to maintain the temperature by radiant heat during the production and maintain the production characteristics.
  • TB700-1800 is easily maintained at 78% or more.
  • the iron-containing glass is further selected from the group of metal oxides consisting of Cr oxide, Co oxide, Mn oxide, Ce oxide, Cu oxide and Se oxide with respect to 100% by mass of the basic glass. It is preferable to contain 0.0001 to 2.5% by mass of at least one metal oxide.
  • One of the above metal oxides may be used alone, or two or more metal oxides may be used in combination. Among these, preferably one or more metal oxides selected from Cr oxide such as Cr 2 O 3 and CoO, Co 2 O 3, Co 3 O Co oxide such as 4, Cr 2 O 3 and Co oxide It is particularly preferable to use a combination of substances.
  • the iron-containing glass further contains both Cr 2 O 3 and Co oxide, 20 to 500 ppm by mass of Fe and 0.0015 to 1% by mass of Cr 2 O 3 with respect to 100% by mass of the basic glass. , Co oxide in an amount of 0.0001 to 1% by mass.
  • the content of the metal oxide is preferably 1 to 200 ppm by mass, more preferably 2 to 100 ppm by mass, and most preferably 3 to 70 ppm by mass with respect to 100% by mass of the basic glass.
  • Iron-containing glass the said metal oxide contains in the range of the content of the, Redox ([bivalent iron as calculated as Fe 2 O 3 (Fe 2+) ] / [ bivalent in terms of Fe 2 O 3 Of the total of iron (Fe 2+ ) and trivalent iron (Fe 3+ ) (Fe 2+ + Fe 3+ )], thereby improving TB700-1800 while maintaining the manufacturing characteristics.
  • the iron-containing glass has a basic glass of soda lime glass, and preferably contains 0.1 to 30% by mass of Al 2 O 3 , MgO and CaO in total expressed as mass% in terms of oxide.
  • the content is more preferably from 5 to 25% by mass, and still more preferably from 10 to 20% by mass.
  • the composition of the basic glass will be described.
  • “%” represents mass% in terms of oxide, unless otherwise specified.
  • the basic glass used for the iron-containing glass preferably has a ratio represented by B 2 O 3 / (B 2 O 3 + R 2 O) of 0.3 or less in terms of mass% in terms of oxide. It is more preferably at most 2, more preferably at most 0.05.
  • R 2 O represents Na 2 O + K 2 O.
  • composition of the basic glass used for the iron-containing glass the following composition is preferable in terms of mass%. SiO 2 : 55% to 85%, Al 2 O 3 : 0% to 30%, B 2 O 3 : 0% to 20%, CaO: 0% to 20%, MgO: 0% to 15%, BaO: 0% to 20%, Na 2 O: 0% to 25%, K 2 O: 0% to 20%.
  • SiO 2 is a component that forms a glass skeleton.
  • the content of SiO 2 is preferably 60% or more.
  • the content of SiO 2 is preferably at most 78%, more preferably at most 75%.
  • Al 2 O 3 is not an essential component, but when Al 2 O 3 is contained, weather resistance, heat resistance, and chemical durability are improved, and the Young's modulus is increased. When the content of Al 2 O 3 is 30% or less, the viscosity at the time of melting the glass does not become too high, so that the melting property becomes good and the devitrification becomes difficult.
  • the content of Al 2 O 3 is preferably at most 18%, more preferably at most 6%.
  • B 2 O 3 is not an essential component. However, when B 2 O 3 is contained, the viscosity at the time of melting the glass does not become too high, so that the melting property becomes good and the glass is hardly devitrified. When the content of B 2 O 3 is 20% or less, the glass transition temperature can be increased, and the Young's modulus increases. The content of B 2 O 3 is preferably 18% or less, more preferably 4% or less.
  • CaO is not an essential component, but when CaO is contained, the viscosity during melting of the glass does not become too high, so that the melting property is improved and the weather resistance is improved. When the content of CaO is 20% or less, devitrification becomes difficult. The content of CaO is preferably 15% or less.
  • MgO is not an essential component, but when MgO is contained, the viscosity at the time of glass melting does not become too high, so that the melting property is improved, the weather resistance is improved, and the Young's modulus is increased. When the content of MgO is 15% or less, devitrification becomes difficult.
  • the content of MgO is preferably 10% or less.
  • BaO is not an essential component, but when BaO is contained, the viscosity during melting of the glass does not become too high, so that the melting property becomes good and the weather resistance is improved. When the content of BaO is 20% or less, it is difficult to devitrify.
  • the content of BaO is preferably at most 10%, more preferably at most 5%.
  • the content of Na 2 O is preferably from 5% to 20%. Preferably it is 10% or more and 17% or less.
  • K 2 O is not an essential component, but when K 2 O is contained, the dissolution temperature is lowered. When the content of K 2 O is 20% or less, devitrification becomes difficult.
  • the content of K 2 O is preferably at most 10%, more preferably at most 5%.
  • the iron-containing glass may further contain, as a fining agent, for example, a component selected from the group consisting of SnO 2 , SO 3 , and Cl.
  • the iron-containing glass further includes, for example, ZnO, Li 2 O, WO 3 , Nb 2 O 5 , and V 2 in order to further improve weather resistance, melting property, devitrification property, ultraviolet light shielding property, visible light shielding property, and the like.
  • O 5 , Bi 2 O 3 , MoO 3 , P 2 O 5 , Ga 2 O 3 , I 2 O 5 , In 2 O 3 , Ge 2 O 5 and the like may be contained.
  • the visible light transmittance or the like of the optical member can be changed according to the use as described later.
  • the iron-containing glass does not substantially contain As 2 O 3 and Sb 2 O 3 in consideration of the environmental load. Further, for stable float molding, it is preferable that ZnO is not substantially contained.
  • a transparent substrate (hereinafter, referred to as a “glass substrate”) made of glass used for the present optical member is prepared by, for example, mixing various raw materials in appropriate amounts so that the composition is in a desired range, heating and melting, and then defoaming. Homogenize by stirring, etc., and form into a plate or the like by the well-known float method, down draw method, press method or roll-out method, or cast into a block shape, slowly cool, then process into a plate shape Is obtained by
  • the glass substrate for example, it is preferable to use a glass plate formed by a float method. Further, it is preferable that the glass substrate has been strengthened by air cooling (physical strengthening) or chemical strengthening. By the strengthening treatment, a compressive stress layer is formed on the surface of the glass substrate, and the strength against scratches and impact is improved.
  • the linear expansion coefficient of the glass constituting the glass substrate is preferably at least 60 ⁇ 10 -7 / °C, more preferably 71 ⁇ 10 -7 / °C or higher, 75 ⁇ 10 - 7 / ° C. or higher is more preferable, and 85 ⁇ 10 ⁇ 7 / ° C. or higher is particularly preferable.
  • the linear expansion coefficient of the glass is preferably 100 ⁇ 10 ⁇ 6 / ° C. or less, more preferably 95 ⁇ 10 ⁇ 6 / ° C. or less, and 90 ⁇ 10 ⁇ 6 / ° C. in order to improve the dimensional accuracy after physical strengthening. The following are more preferred.
  • the coefficient of linear expansion in the present specification is an average coefficient of linear expansion in the range of 50 ° C. to 350 ° C.
  • the surface compression stress (CS) of the strengthened glass substrate is preferably, for example, 10 MPa or more.
  • the surface compressive stress is more preferably 30 MPa or more, further preferably 50 MPa or more, and particularly preferably 100 MPa or more.
  • the surface compressive stress (CS) is measured according to the following procedure.
  • a disk whose entire surface is a mirror surface is manufactured.
  • a photoelastic constant is determined by a disk compression method.
  • the cut surface is optically polished, and the retardation is measured by a birefringence measuring device. Then, by dividing the measured value of the retardation by the photoelastic constant and the thickness of the glass substrate, the generated stress (compressive stress (CS) on the surface) can be obtained.
  • CS compressive stress
  • the glass substrate used in the present optical member is a tempered glass plate
  • the number of pieces from a 50 mm ⁇ 50 mm square area is 40 or more and 400 or less.
  • the number of pieces from a 50 mm ⁇ 50 mm square area is 40 or more and 400 or less.
  • the glass substrate used in the present optical member is a laminated glass
  • the glass substrate is crushed by a method in accordance with JIS R 3211
  • the total mass of the debris separated from the surface opposite to the impact surface of the glass substrate is 20 g or less.
  • the size of the glass substrate used for the optical member can be appropriately adjusted according to the application.
  • a glass plate obtained by a float method or the like is used after being cut into a predetermined size.
  • the end face connecting the first main face and the second main face of the glass substrate is preferably chamfered for the purpose of preventing cracks at the end portion and the vicinity thereof.
  • the transparent glass is formed by forming the inner glass plate 1A or the outer glass plate 1B from, for example, the iron-containing glass described above. May satisfy the requirement (A).
  • the intermediate adhesive layer 1C mainly contains a thermoplastic resin such as polyvinyl butyral resin (PVB), ethylene-vinyl acetate copolymer resin (EVA), or cycloolefin polymer (COP) used for ordinary laminated glass.
  • PVB polyvinyl butyral resin
  • EVA ethylene-vinyl acetate copolymer resin
  • COP cycloolefin polymer
  • a near-infrared transmitting resin film may be disposed between the intermediate adhesive layer and the glass substrate.
  • the near-infrared transmitting resin film is formed as a coating film on the main surface of the inside glass plate or the outside glass plate on the side of the intermediate adhesive layer.
  • the optical interference film 2 is formed on the first main surface 1a of the transparent substrate 1, and functions so that the obtained optical member 10A satisfies the requirement (1).
  • Light interference film 2 is, for example, in optical members 10A obtained, for light of wavelength lambda s, the range of incident angle of 0 degrees to 60 degrees, the reflectance as compared with the case of using a transparent substrate 1 alone By lowering, the optical member 10A functions so as to satisfy the requirement (1). It is preferable that the optical interference film 2 further functions so that the obtained optical member 10A satisfies one or more requirements selected from requirements (2) to (4).
  • the optical interference film 2 is further made of, for example, visible light as long as the optical member 10A satisfies the requirement (1), and preferably functions so as to further satisfy the requirements (2) to (4).
  • a film having other functions such as enhancing light durability, light shielding property, ultraviolet shielding property, antifouling property, and dustproofing property may be used.
  • the configuration of the light interference film 2 is not particularly limited as long as it has the above function.
  • the optical interference film 2 may be provided only on the first main surface 1a of the transparent substrate 1 like the optical member 10A shown in FIG. 1, or may be provided on the second main surface 1b of the transparent substrate 1. May be provided only on the first main surface 1 a and the second main surface 1 b of the transparent substrate 1.
  • the obtained optical member satisfies the requirement (1) by combining the two optical interference films, and preferably further satisfies the requirements (2) to (4).
  • Each light interference film is designed to satisfy one or more selected requirements.
  • the optical member when each optical interference film is used alone does not have to satisfy the requirement (1).
  • an optical interference film that satisfies requirement (1), and preferably satisfies requirements (2) to (4), is provided on both main surfaces of the transparent substrate.
  • T (1) min and ⁇ T (1) tend to be improved, and the optical loss in (2) tends to increase, as compared with the case where each optical interference film is used alone.
  • the configuration of the light interference film is appropriately selected according to the optical characteristics required of the optical member.
  • the light interference film 2 may be a single-layer film composed of only one layer, or a multilayer film in which two or more layers are stacked, and is preferably a multilayer film.
  • a multilayer film including two or more layers including a low refractive index layer and a high refractive index layer is preferable.
  • the total number of layers of the multilayer film is preferably 10 layers or less, and particularly preferably 4 layers or less, from the viewpoint of manufacturing cost and thinning.
  • the low refractive index layer and the high refractive index layer are preferably stacked adjacent to each other.
  • the low refractive index layer is composed of a material having a low refractive index (low refractive index material)
  • the high refractive index layer is composed of a material having a high refractive index (high refractive index material).
  • the refractive index difference between the low refractive index layer and the high refractive index layer that is, the refractive index difference between the low refractive index material and the high refractive index material may be larger than zero, preferably 0.1 or more.
  • the refractive index of the optical thin film constituting the optical interference films described herein exhibit all refractive index of each material in the light of the predetermined wavelength lambda s.
  • the multilayer film having a low refractive index layer and a high refractive index layer may further have an intermediate refractive index layer.
  • the intermediate refractive index layer is composed of an intermediate refractive index material having a refractive index higher than that of the low refractive index material and lower than that of the high refractive index material.
  • the geometric thickness of each layer is appropriately set according to the material used and the required optical characteristics.
  • the wavelength region in the infrared region is mainly a problem, it is preferable that at least one of the layers constituting the light interference film 2 has a geometric thickness of 50 nm or more.
  • the geometric thickness (thickness per layer) of each layer constituting the light interference film 2 can be set to 5 nm to 500 nm on the assumption that at least one layer is 50 nm or more.
  • the film thickness per layer of the light interference film 2 by setting the upper limit of the film thickness per layer to 500 nm, a decrease in transmittance due to light scattering can be suppressed.
  • the film thickness per layer of the light interference film 2 by setting the film thickness per layer of the light interference film 2 to 5 nm or more, the light interference film 2 actually exists as a continuous film, and its function is sufficiently exhibited.
  • the total geometric thickness of the optical interference film 2 is preferably 300 nm or more, more preferably 400 nm or more, and even more preferably 500 nm or more.
  • the total geometric thickness of the light interference film 2 is preferably 2000 nm or less, more preferably 1500 nm or less, and still more preferably 1200 nm or less, in order to prevent a decrease in transmittance and a warpage of the transparent substrate due to light scattering.
  • each light interference film may have the same configuration as described above.
  • the upper limit of the total geometric thickness of the optical interference films is preferably 4000 nm in total of the two optical interference films.
  • the optical interference film 2 in the optical member 10A shown in FIG. 1 is an example of an optical interference film having a configuration in which an intermediate refractive index layer, a low refractive index layer, and a high refractive index layer are stacked.
  • the light interference film 2 has a configuration in which an intermediate refractive index layer 21, a high refractive index layer 22, and a low refractive index layer 23 are sequentially stacked from the main surface 1 a side of the transparent substrate 1.
  • the refractive index of the low refractive index material constituting the low refractive index layer 23 is preferably 1.35 or more and less than 1.55.
  • the low-refractive-index material include materials mainly containing a low-refractive-index substance such as silicon oxide and magnesium fluoride. Note that “having a substance as a main component” in each refractive index layer means that the substance is contained in an amount of 50 mol% or more.
  • the low-refractive-index material has a low refractive index, and preferably contains at least one kind of low-refractive-index substance as a main component, and further contains an intermediate-refractive-index substance and a high-refractive-index substance, as long as the refractive index is adjusted to the above range.
  • the configuration may be as follows.
  • the low-refractive-index material is preferably composed of only a low-refractive-index substance, more preferably composed of only one kind of low-refractive-index substance. It is preferable to use silicon oxide as the low refractive index material from the viewpoints of reproducibility, stability, economy, and the like in film forming properties.
  • the high refractive index material constituting the high refractive index layer 22 preferably has a refractive index of 1.90 or more and 5.00 or less.
  • the high refractive index material for example, silicon nitride, silicon oxynitride, aluminum nitride, aluminum oxynitride, zirconium oxide, tin oxide, cerium oxide, silicon, copper oxide, germanium, titanium oxide, niobium oxide, tantalum oxide, etc.
  • a material containing a refractive index substance as a main component is used.
  • the high-refractive-index material has a high refractive index, and preferably contains at least one high-refractive-index substance as a main component, and further contains a low-refractive-index substance and an intermediate-refractive-index substance, as long as the refractive index is adjusted to the above range.
  • the configuration may be as follows.
  • the high-refractive-index material is preferably composed only of a high-refractive-index substance.
  • silicon nitride, silicon oxynitride, aluminum nitride, aluminum oxynitride, zirconium oxide, titanium oxide, niobium oxide tin oxide, Cerium oxide, silicon and copper oxide are preferred.
  • silicon nitride, silicon oxynitride, aluminum nitride, aluminum oxynitride, zirconium oxide, tin oxide, and cerium oxide are preferred from the viewpoint of obtaining a desired hardness when formed into a multilayer film, and silicon nitride, zirconium oxide, and aluminum nitride are preferred. Is more preferable, and silicon nitride is particularly preferable.
  • the transparent substrate 1 having a curvature may include the light interference film 2 which is a multilayer film.
  • the optical interference film may be laminated after bending the glass plate into a predetermined shape, or the glass plate may be bent into a predetermined shape after laminating the optical interference film on the glass plate. Good. Bending the glass plate after laminating the optical interference film is preferable because the optical interference film can be laminated on a flat surface. However, in order to bend the glass plate, the glass plate is heated to a temperature close to the softening point, so that an optical interference film that does not deteriorate at high temperatures is required.
  • a light interference film As such a light interference film, as a high refractive material constituting the high refractive layer, zirconium oxide, aluminum oxide, aluminum oxynitride, tantalum oxide, silicon nitride, silicon oxynitride, and a mixture thereof, titanium oxide and zirconium oxide A mixture is preferable, and silicon oxide is preferable as the low refractive material forming the low refractive layer.
  • the refractive index of the intermediate refractive index material constituting the intermediate refractive index layer 21 is preferably 1.55 or more and less than 1.90.
  • the intermediate refractive index material for example, a material mainly containing an intermediate refractive index material such as aluminum oxide, silicon oxynitride, aluminum oxynitride, a mixture of silicon oxide and zirconium oxide, and a mixture of silicon oxide and aluminum nitride can be used. .
  • the intermediate refractive index material has at least one intermediate refractive index material whose refractive index is between the refractive index of the high refractive index material and the refractive index of the low refractive index material, preferably as long as the refractive index is adjusted to the above range.
  • intermediate refractive index materials include a mixture of silicon oxide and aluminum nitride.
  • the intermediate refractive index material is preferably composed of only an intermediate refractive index substance, and more preferably composed of only one kind of intermediate refractive index substance.
  • the intermediate refractive index substance aluminum oxide, silicon oxynitride, and aluminum oxynitride are preferable in terms of obtaining desired optical properties and hardness when formed into a multilayer film, and aluminum oxide, a mixture of zirconium oxide and silicon oxide is particularly preferable. preferable.
  • a metal nitride, oxide, or oxynitride represented by a nitride + metal name, an oxide + metal name, or an oxynitride + metal name is a stoichiometric composition ratio unless otherwise specified.
  • Non-stoichiometric compositions of nitrides, oxides and oxynitrides are shown. If necessary, for example, also be described as SiN x, if silicon nitride.
  • the geometric thicknesses of the intermediate refractive index layer 21, the high refractive index layer 22, and the low refractive index layer 23 in the light interference film 2 are appropriately set according to the material constituting each layer and the required optical characteristics.
  • the thickness of each layer is the following optical thickness. The two combinations (i) and (ii) are preferred.
  • t 21 is the optical thickness of the intermediate refractive index layer 21 made of aluminum oxide
  • t 22 is the optical thickness of the high refractive index layer 22 made of silicon nitride
  • t 23 is made of silicon oxide. The optical thickness of the low refractive index layer 23 is shown.
  • each of the intermediate refractive index layer 21, the high refractive index layer 22, and the low refractive index layer 23 is made of aluminum oxide, silicon nitride, and silicon oxide
  • the thickness of each layer is determined by the optical film thickness.
  • t 21 0.147 ⁇ s
  • t 22 0.663 ⁇ s
  • t 23 0.358 ⁇ s as.
  • the transmittance becomes 85% or more when the incident angle is between 0 degree and 60 degrees, and the maximum value of the transmittance between these incident angles is obtained. Is 8% or less.
  • the light interference film 2 is, for example, an example in which a high-refractive-index layer and a low-refractive-index layer are laminated one by one in total from the main surface 1a side of the transparent substrate 1.
  • the copper oxide high refractive index layer, the thickness of each layer in the case of constituting the low refractive index layer of silicon oxide, as the optical film thickness, respectively is preferably 0.466Ramuda s and 0.155 ⁇ s.
  • silicon and the high refractive index layer, the thickness of each layer in the case of constituting the low refractive index layer of silicon oxide, as the optical film thickness, respectively, is preferably 0.492Ramuda s and 0.148 ⁇ s.
  • the light interference film 2 for example, two high refractive index layers and two low refractive index layers are alternately added in order from the main surface 1a side of the transparent substrate 1 to the high refractive index layer and the low refractive index layer.
  • An example in which four layers are stacked is given.
  • the transmittance of the optical interference film 2 is set such that the incident angle between the light of the sensor wavelength ⁇ s and the optical article is from 0 ° to 60 °.
  • the maximum value is preferably obtained when the incident angle is 25 degrees or more
  • the minimum value is more preferably obtained when the incident angle is 30 degrees or more
  • the maximum value is most preferably obtained when the incident angle is 35 degrees or more.
  • the windshield of the vehicle when being tilted surface of the optical article to the sensor light also ranges preferred in the above, preferably Nari high transmittance in the sensor wavelength lambda s.
  • the light interference film 2 provided on one main surface of the transparent substrate 1 has been described by taking as an example the configuration of two to four layers, but the laminated structure such as the number of layers, the constituent materials of the layers, the order of lamination, the thickness of the layers, etc. Can be appropriately changed according to the required optical characteristics.
  • the optical interference film is provided on both main surfaces of the transparent substrate
  • an optical interference film having two to four layers provided on one main surface of the transparent substrate 1 exemplified above may be used.
  • the configurations of the light interference films provided on both main surfaces may be the same or different.
  • the light interference film 2 can be formed on the transparent substrate 1 by a known film forming method.
  • the film is formed using a film formation method such as a heat evaporation method, a sputtering method, or an ion assisted deposition (IAD: Ion Assisted Deposition) method.
  • IAD Ion Assisted Deposition
  • a film having high scratch resistance is formed as the light interference film 2
  • the optical member 10A including the transparent substrate 1 and the light interference film 2 has been described above with reference to FIGS. 1A to 1D.
  • the design of the transparent substrate 1 and the light interference film 2 can be changed without impairing the effects of the present invention.
  • the optical member 10A may have any component other than the transparent substrate 1 and the light interference film 2 as long as the effects of the present invention are not impaired.
  • Optional components include a coating that imparts a water-repellent function, a hydrophilic function, an anti-fogging function, etc., a low radiation coating, an infrared light shielding coating, a visible light shielding coating, a conductive coating, and the like.
  • the optical member is measured on the surface of the optical interference film in the present optical member.
  • Martens hardness 4N / mm 2 or more, more preferably 4.5 N / mm 2 or more, 5N / mm 2 or more is more preferable.
  • the value of the Martens hardness can be achieved by forming the high refractive index material of the optical interference film from a material which is preferable in terms of hardness in the above.
  • the visible light transmittance in the wavelength region of 380 nm to 780 nm measured at an incident angle of 0 degree is, for example, a design and a safety when the LiDAR sensor or the like in the vehicle is made invisible from the outside of the vehicle. From the viewpoint of, 30% or less is preferable, 20% or less is more preferable, and 10% or less is particularly preferable.
  • the visible light reflectance in the above wavelength range which is measured at an incident angle of 5 degrees on the surface of the optical interference film, is, for example, when the present optical member is mounted on a metallic color vehicle body. Is preferably 60% or more, and more preferably 70% or more, from the viewpoint of maintaining a unified appearance of the vehicle.
  • the visible light reflectance is, for example, preferably 8% or less, more preferably 5% or less, from the viewpoint of not impairing the appearance of the vehicle when it is mounted on a matte vehicle body.
  • the wavefront aberration at the wavelength ⁇ s is preferably not more than 1.0 ⁇ RMS .
  • the wavefront aberration is measured by a surface shape measuring device, for example, a laser interference flatness meter (for example, Verifire, Mark IV; manufactured by Zygo; Fujinon, G310S, manufactured by ToeI; Fiat Master), a laser displacement meter, It can be calculated from the measurement result of the surface shape by an acoustic displacement meter, a contact type displacement meter or the like.
  • the residue obtained by removing the tilt component from the results obtained using various measuring devices is the surface shape, and the difference between the maximum value and the minimum value of the surface shape is the wavefront aberration.
  • the wavefront aberration satisfies predetermined requirements at least in a predetermined region corresponding to a position where the sensor transmits and receives infrared light on the main surface.
  • the optical member may satisfy a predetermined requirement in the entire area of the main surface.
  • wavefront aberration at ⁇ s is preferably not more than 0.9Ramuda RMS, and more preferably not more than 0.6 ⁇ RMS. Even more preferably 0.3 ⁇ RMS or less.
  • the transmittance and reflectance in the visible light region, and the transmission color and reflection color are adjusted so that the appearance thereof is in harmony with the surroundings, depending on the environment and the region in which the optical member is used.
  • a layer of an organic ink, an inorganic ink, or the like may be used in combination.
  • the material of the ink needs to be transparent in the near infrared region.
  • the water contact angle measured on the surface of the light interference film is, for example, the infrared absorption of water when the present optical member is disposed outside the vehicle such as the outer surface of a windshield of a vehicle, a cover member, or the like. Is preferably 90 degrees or more, and more preferably 100 degrees or more from the viewpoint of preventing the transmittance from being lowered. Further, the water contact angle measured on the surface of the light interference film is preferably 20 degrees or less from the viewpoint of ensuring transparency, for example, when the present optical member is disposed on the inner surface of the windshield of the vehicle. Degree or less is more preferable.
  • the present optical member has a high transmittance for infrared light over a wide incident angle.
  • this optical member is used, for example, as a cover member of a LiDAR sensor, it does not prevent transmission of infrared light used for sensing by the LiDAR sensor over a wide range of incident angles.
  • Examples of a method of attaching the present optical member to the LiDAR sensor as a cover member include a method of directly attaching the optical member via an adhesive that transmits infrared light, and a method of attaching the optical member to the housing of the LiDAR sensor.
  • the present optical member has an optical interference film only on one main surface of the transparent substrate, it is preferable that the optical interference film is disposed on the LiDAR sensor side.
  • the LiDAR sensor is used by being mounted on a transport machine, for example, a train, an automobile, a ship, or an aircraft.
  • This optical member is particularly suitable as a cover member of a LiDAR sensor mounted on an automobile.
  • the LiDAR sensor When mounted on an automobile, the LiDAR sensor may be attached to, for example, a bumper, a side mirror, a pillar, or a rear portion of an interior mirror.
  • the present optical member is advantageous in that the strength and design can be adjusted according to the application location.
  • the optical member of the present invention is used as a window glass, it is possible to suppress a decrease in sensing due to the passage of the window glass.
  • the optical member of the present invention is applicable to a windshield, a rear glass, a side glass, a roof glass, and the like in the case of a window glass for an automobile.
  • Examples 1 to 22 Five types of glass substrates having the composition, optical characteristics, and Martens hardness shown in Table 1 were used as the transparent substrates. The optical properties and the Martens hardness of the glass substrate were measured in the same manner as the method used for evaluating optical members described below.
  • the glass substrates GA, GB, GC, and GE are glass substrates satisfying the requirement (A), and the glass substrate GD does not satisfy the requirement (A), and TB700-1800 is less than 78%.
  • “Co” in the composition of the glass substrate GA indicates a component of cobalt (Co) oxide.
  • Table 2 shows the configurations of the eleven types of light interference films IA to IK used in this example, specifically, the number of layers, the order of lamination, the constituent materials of each layer, and the geometric thickness.
  • the optical members according to Examples 1 to 15 and 20 to 29 are obtained by changing one of the 11 types of optical interference films IA to IK shown in Table 2 to a transparent substrate according to the combinations shown in Tables 3 and 4. Was formed by forming a film on only the first main surface or both the first main surface and the second main surface by the following method.
  • Examples 1 and 2 Examples 5-8, Example 13, by setting the wavelength lambda s to 940 nm, were designed optical interference film.
  • Example 15 sets the wavelength lambda s on two wavelengths of 940nm and 1550 nm, were designed optical interference film.
  • the optical members according to Examples 16 to 19 have no light interference film.
  • Table 2 shows the layer structure of the light interference film as the first layer, the second layer, the third layer, and the fourth layer in order from the transparent substrate side.
  • the shaded columns indicate that there are no layers.
  • the formation of the optical interference film was performed using a sputtering apparatus (RAS1100BII, manufactured by SYNCHRON).
  • the first layer is an aluminum oxide layer as an intermediate refractive index layer
  • the second layer is a silicon nitride layer as a high refractive index layer
  • the third layer is a low refractive index layer.
  • Each was composed of a silicon oxide layer as a rate layer.
  • the optical interference films IA to ID and the optical interference films II and IK were formed by the same method except that the geometric thickness of each layer was different.
  • An Al target was used for forming the aluminum oxide layer as the intermediate refractive index layer, argon was used as a discharge gas in the film formation chamber, and oxygen was used as a discharge gas in the reaction chamber.
  • the pressure during film formation was 0.15 Pa.
  • the geometric thickness of the aluminum oxide layer was adjusted in each of the optical interference films IA to ID and the optical interference films II and IK so as to have the thickness [nm] shown in Table 2.
  • the silicon nitride layer which is a high refractive index layer
  • an Si target was used, argon was used as a discharge gas in a film formation chamber, and nitrogen was used as a discharge gas in a reaction chamber.
  • the pressure during film formation was 0.15 Pa.
  • the geometric thickness of the silicon nitride layer was adjusted in the light interference films IA to ID and the light interference films II and IK so as to have the thickness [nm] shown in Table 2, respectively.
  • the silicon oxide layer As a low refractive index layer, an Si target was used, argon was used as a discharge gas in the film formation chamber, and oxygen was used as a gas in the reaction chamber.
  • the pressure during film formation was 0.15 Pa.
  • the geometric thickness of the silicon oxide layer was adjusted in each of the light interference films IA to ID and the light interference films II and IK so as to have the thickness [nm] shown in Table 2.
  • a titanium oxide layer containing zirconium oxide which is a high refractive index material
  • a titanium target containing 50 mol% of zirconium a titanium target for the titanium oxide layer
  • a niobium target for the niobium oxide layer a titanium target for the titanium oxide layer
  • a tantalum target for the tantalum oxide layer argon was used as a discharge gas in the film formation chamber
  • oxygen was used as a discharge gas in the reaction chamber.
  • the pressure during film formation was 0.15 Pa.
  • the geometric thickness of each high refractive index layer was adjusted so that the thickness [nm] shown in Table 2 was obtained in each of the light interference films IL to IP.
  • the copper oxide layer serving as the high refractive index layer and the silicon oxide layer serving as the low refractive index layer are arranged in this order from the glass substrate side. Was formed once or alternately twice each.
  • a Cu target was used for forming the copper oxide layer as the high refractive index layer, argon was used as a discharge gas in the film formation chamber, and oxygen was used as a discharge gas in the reaction chamber.
  • the pressure during film formation was 0.15 Pa.
  • the geometric thickness of the copper oxide layer was adjusted so that each of the optical interference films IE and IG had a thickness [nm] shown in Table 2.
  • the formation of the silicon oxide layer as the low refractive index layer was performed in the same manner as described above. In the light interference film IG, the formation of the copper oxide layer and the formation of the silicon oxide layer were repeatedly performed to obtain a light interference film having a configuration shown in Table 2.
  • a silicon layer which is a high refractive index layer and a silicon oxide layer which is a low refractive index layer are arranged in this order so that the geometric thickness of each layer becomes the value shown in Table 2.
  • the film was formed once or alternately twice.
  • a silicon target which is a high refractive index layer, was deposited using an Si target, and argon was used as a discharge gas in the deposition chamber and the reaction chamber.
  • the pressure during film formation was 0.15 Pa.
  • the geometric thickness of the silicon layer was adjusted so that the thickness [nm] shown in Table 2 was obtained in each of the optical interference films IF and IH.
  • the formation of the silicon oxide layer as the low refractive index layer was performed in the same manner as described above. In the light interference film IH, the formation of the silicon oxide layer and the formation of the silicon layer were repeatedly performed to obtain a light interference film having a configuration shown in Table 2.
  • a silicon oxynitride layer as a high refractive index layer and a silicon oxide layer as a low refractive index layer were sequentially changed in this order from the glass substrate to the values shown in Table 2 below. It formed so that it might become.
  • the silicon oxynitride layer which is a high refractive index layer For the formation of the silicon oxynitride layer which is a high refractive index layer, an Si target was used, argon was used as a discharge gas in a film formation chamber, and a discharge gas in a reaction chamber was 1:10 by volume ratio of oxygen and nitrogen. A mixed gas was used. The pressure during film formation was 0.15 Pa. The geometric thickness of the silicon layer was adjusted so as to have the thickness [nm] shown in Table 2 in the light interference film IJ. The formation of the silicon oxide layer as the low refractive index layer was performed in the same manner as described above.
  • Tables 3 and 4 show the abbreviations of the glass substrates used and the abbreviations of the light interference films formed on one or both main surfaces of the glass substrates, along with the following evaluation results.
  • the light interference film formed on the first main surface 1a of the transparent substrate (glass substrate) 1 is a first light interference film
  • the light interference film formed on the second main surface 1b is a light interference film. This is shown as a second light interference film. "-" Indicates that the light interference film was not formed.
  • T (1) min and ⁇ T (1) In the wavelength range of 200 nm to 1800 nm, 13 transmittances were measured from an incident angle of 0 degree to an incident angle of 60 degrees every 5 degrees. From transmittance curve of this 13, determining the minimum and maximum values of the transmittance at a wavelength lambda s, respectively. In Tables 3 and 4, the minimum value and the maximum value of the transmittance, together with the incident angle ( ⁇ 2 , ⁇ 1 ) at that time, are defined as T (1) min ( ⁇ 2 ) and T (1) max ( ⁇ 1 ). , And their difference as ⁇ T (1) .
  • T (1) min is the transmittance for an incident angle of 60 degrees, i.e., if the theta 2 takes a minimum value when the 60 degrees, wherein the angle bracketed omitted.
  • T (1) max is the transmittance when the degree incidence angle of 0, i.e., if the theta 1 takes a maximum value when the 0 degree, the description of the angle bracketed omitted.
  • T (1) min and T (1) max and ⁇ T (1) are shown in the spectral transmittance curve.
  • T (1) min is the transmittance when the incident angle is 60 degrees
  • T (1) max is the transmittance when the incident angle is 0 degrees, so that the incident angle is 5 degrees.
  • the description of the spectral transmittance curve of up to 55 degrees is omitted.
  • Tables 3 and 4 show optical characteristics corresponding to the wavelength ⁇ s set for designing the optical interference film in Examples 1 to 15 and Examples 20 to 22.
  • the predetermined wavelength lambda s is the assumption that when the 1550nm of 940 nm, was evaluated similar optical properties.
  • Martens hardness was measured on the surface of the first optical interference film of the optical member using PICODENTOR (HM500, manufactured by Fisher Instruments). The measurement was performed 15 times with an indentation depth of 50 ⁇ 10 nm. The average value of 15 times was defined as Martens hardness. For Examples 16 to 19 having no light interference film, no measurement was performed.
  • the optical member was placed in a batch furnace heated to 600 ° and 660 °, held for 10 minutes, taken out, and changed in transmittance at a wavelength of ⁇ s at an incident angle of 0 ° (the transmittance and the transmittance before the test). The difference from the transmittance after the test was evaluated. The change in transmittance is required to be 1% or less.
  • the surface shape is determined based on the residual shape excluding the tilt component from the surface shape measurement result by a laser interference type flatness meter (Verify Mark IV, manufactured by Zygo), and the difference between the maximum value and the minimum value of the surface shape is determined by the wavefront.
  • the measurement was performed in a range of a diameter of 80 mm. Wavefront aberration was measured for the optical members of Examples 23 to 29 before and after the above-mentioned 660 ° heating test.
  • the optical member of the example satisfies the requirements of (1), (2) and (4). Further, the optical member of the embodiment satisfies the requirement of (3) except for Example 10.
  • the optical element of Comparative Example shown in Table 4 the optical member Examples 20 through Example 22, not satisfy the requirement (1) In setting wavelength lambda s of 940 nm, the optical member of Example 16 through Example 19, for example, 940 nm, in the case of setting the 1550nm at a predetermined wavelength lambda s, does not satisfy the requirement (1).
  • the optical member of the comparative example the spectral transmittance curves measured at an incident angle of 0 degrees to 60 degrees, not even meet the requirements (1) when any of the wavelength of 700nm or more 1800nm or less was set to lambda s It was confirmed that.

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JPWO2022149583A1 (https=) * 2021-01-07 2022-07-14
JP7708124B2 (ja) 2021-01-07 2025-07-15 Ａｇｃ株式会社 車両用ガラス
JP2024511455A (ja) * 2021-03-24 2024-03-13 サン－ゴバン グラス フランス 乗り物グレージング及び近赤外線ビジョンシステムを有する関連機器
JP2024540329A (ja) * 2021-11-04 2024-10-31 フーイャォ グラス インダストリー グループ カンパニー リミテッド 車窓アセンブリおよび車両
JP2024547008A (ja) * 2022-01-04 2024-12-26 フーイャォ グラス インダストリー グループ カンパニー リミテッド ウインドシールドおよびウインドシールドアセンブリ
JP7681807B2 (ja) 2022-01-04 2025-05-22 フーイャォ グラス インダストリー グループ カンパニー リミテッド ウインドシールドおよびウインドシールドアセンブリ
WO2024069017A1 (en) 2022-09-30 2024-04-04 Agp Worldwide Operations Gmbh Glazing having high near infrared light transmission capacities
JP2025536261A (ja) * 2022-10-14 2025-11-05 フーイャォ グラス インダストリー グループ カンパニー リミテッド 車窓ガラスとその製造方法、並びに車両

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JP7298073B2 (ja) 2023-06-27
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US11994699B2 (en) 2024-05-28
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