WO2020204194A1 - Élément optique - Google Patents

Élément optique Download PDF

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Publication number
WO2020204194A1
WO2020204194A1 PCT/JP2020/015426 JP2020015426W WO2020204194A1 WO 2020204194 A1 WO2020204194 A1 WO 2020204194A1 JP 2020015426 W JP2020015426 W JP 2020015426W WO 2020204194 A1 WO2020204194 A1 WO 2020204194A1
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WO
WIPO (PCT)
Prior art keywords
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optical member
glass
glass substrate
refractive index
Prior art date
Application number
PCT/JP2020/015426
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English (en)
Japanese (ja)
Inventor
山本　宏行
尚洋 眞下
尾山　卓司
Original Assignee
Ａｇｃ株式会社
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.)
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Publication date
Application filed by Ａｇｃ株式会社 filed Critical Ａｇｃ株式会社
Priority to JP2021512338A priority Critical patent/JP7484897B2/ja
Priority to CN202080022124.3A priority patent/CN113646276B/zh
Publication of WO2020204194A1 publication Critical patent/WO2020204194A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/023—Optical properties
    • 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
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
    • C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
    • C03C3/087—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal containing calcium oxide, e.g. common sheet or container glass
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/26—Reflecting filters
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/28—Interference filters

Definitions

  • the present invention relates to an optical member.
  • autonomous driving technology it is essential to measure the distance between a vehicle and surrounding objects, and for that purpose, LiDAR (Light Detection and Ringing) sensor technology using infrared light is used.
  • LiDAR Light Detection and Ringing
  • sensors using light such as LiDAR sensors are arranged outside the vehicle such as the vehicle body, A pillars, B pillar pillars, and bumpers.
  • a cover is required to protect the sensor, and glass is superior in terms of scratch resistance. While the cover is required to have high transmittance for the light used for the sensor, from the viewpoint of sensor accuracy, it is desirable to prevent unnecessary light from entering and to prevent the temperature from becoming high, and from the viewpoint of design, the cover is black or It is preferably silver.
  • Patent Document 1 as a material corresponding to a sensor using light in the visible region to the infrared region, glass is provided with iron and chromium contents of a predetermined amount or less and decorated with black ink. Is disclosed. Further, Patent Document 2 discloses black glass utilizing light in the visible region to the infrared region.
  • Patent Document 1 is prone to uneven thickness of ink, false detection of the sensor due to optical distortion occurs due to deterioration during use, and fogging or ice of the glass is required to operate the sensor normally.
  • the resin may be altered or optically distorted by heating with a heater used to remove the ice cubes.
  • the glass of Patent Document 2 is intended for the transmittance of a configuration having no optical interference film, it does not have a sufficient transmittance for the LiDAR sensor. That is, in the LiDAR sensor used in the automatic driving technology, high transparency of light in the infrared region (hereinafter referred to as "infrared light”) is required to have high transmission rate in a configuration having an optical interference film. Therefore, the glass of Patent Document 2 cannot meet such high required characteristics.
  • the present invention has been made in view of the above problems, and the sensor is concealed by lowering the transmittance of visible light, the malfunction of the sensor due to heat is suppressed, and the infrared light used for the LiDAR sensor is used.
  • the main purpose is to provide an optical member that sufficiently transmits light without being distorted.
  • the optical member of the present invention is an optical member for a sensor cover including an amorphous glass substrate and an optical interference film arranged on at least one main surface of the glass substrate, and has the following characteristics.
  • the minimum value of the transmittance of is 86.5% or more
  • the difference in the maximum transmittance of incident light in the incident angle range of 0 ° C. or higher and 5 ° C. or lower at the wavelength ⁇ s before and after heating the optical member at a temperature of 200 ° C. for 24 hours is 3% or less.
  • an optical member that conceals a sensor by lowering the transmittance of visible light, suppresses malfunction of the sensor due to heat, and sufficiently transmits infrared light used for a LiDAR sensor without distorting it. Can be provided.
  • the transmittance of, for example, 78% or more for a specific wavelength range means that the transmittance does not fall below 78% in the entire wavelength range, and similarly, the transmittance is, for example, 1% or less. It means that the transmittance does not exceed 1% in the entire wavelength range.
  • "-" representing a numerical range includes upper and lower limits.
  • the optical member of the embodiment of the present invention (hereinafter, also referred to as “the present optical member”) includes an amorphous glass substrate and an optical interference film arranged on at least one main surface of the glass substrate. It is an optical member for a sensor cover and includes a region that satisfies the following requirements (1) to (3).
  • T max 400-700 The maximum transmittance in the wavelength range of 400 nm or more and 700 nm or less is 10% or less with respect to the light incident in the range of the incident angle of 0 degrees or more and 5 degrees or less. is there.
  • T min (2) The minimum value of the light transmittance at a predetermined wavelength ⁇ s in the wavelength range of 800 nm or more and 1800 nm or less with respect to the light incident in the range of the incident angle of 0 degrees or more and 5 degrees or less (hereinafter, “T min (2)). ”) Is 86.5% or more.
  • Examples of the sensor to which this optical member is applied include a sensor that performs sensing using infrared light such as a LiDAR sensor.
  • the incident angle is the incident angle with respect to the main surface of the optical member.
  • the description of the optical characteristics is the characteristics in the light incident from one of the main surfaces of the optical members, and the incident surface is not limited, unless otherwise specified.
  • the optical member may satisfy the requirements (1) to (3) at least in a predetermined region corresponding to a position where the sensor transmits / receives infrared light on the main surface.
  • the optical member may satisfy the requirements (1) to (3) in the entire area of the main surface.
  • the transmittance and reflectance of light having a specific wavelength of 700 nm or more and 1800 nm or less in a glass substrate and an optical member are measured by a spectrophotometer having a variable incident angle, for example, V-780 manufactured by JASCO Corporation. Can be measured.
  • This optical member has the required visible light shielding property by satisfying the requirement (1), and sufficiently transmits infrared light used for the sensor by satisfying the requirement (2). By satisfying the requirement of 3), it is possible to suppress the occurrence of distortion in the transparency of the infrared light due to heat.
  • the predetermined wavelength ⁇ s is, for example, the wavelength of the laser light used for sensing by a sensor such as a LiDAR sensor used together with this optical member.
  • the optical member may have one or more predetermined wavelengths satisfying the requirement (2), and may satisfy the requirement (2) with two or more predetermined wavelengths.
  • Specific examples of ⁇ s include 800 nm, 905 nm, 950 nm, 1050 nm, 1550 nm, and the like, and one wavelength or more selected from 800 nm, 905 nm, 950 nm, 1050 nm, and 1550 nm is preferable, and two wavelengths or more are more preferable.
  • T max 400-700 is 10% or less. From the viewpoint of further enhancing the visible light shielding property, T max 400-700 is preferably 3% or less, more preferably 1.0% or less.
  • T min (2) is 86.5% or more. From the viewpoint of further enhancing infrared light transmission at the wavelength ⁇ s, T min (2) is preferably 87% or more, more preferably 89% or more, and particularly preferably 90% or more.
  • ⁇ T 200 ° C. ⁇ s is 3% or less. From the viewpoint of further suppressing the influence of heat of infrared light transmission, ⁇ T 200 ° C. ⁇ s is preferably 1.5% or less, more preferably 0.8% or less.
  • the optical member further preferably has at least one of the following characteristics (4) and (5) in the above-mentioned predetermined region, and more preferably has both characteristics.
  • ⁇ E is preferably 7 or less, more preferably 5 or less, and even more preferably 2.5 or less.
  • the wave surface aberration at the wavelength ⁇ s is 1.0 ⁇ RMS or less.
  • Wave surface aberration is measured by a surface shape measuring device, for example, a laser interference type flatness meter (for example, Zygo; Verifire, Mark IV; Fujinon, G310S, ToeI; Fat Master), a laser displacement meter, and an ultrasonic. It can be calculated from the result of measuring the surface shape with a ultrasonic displacement meter, a contact type displacement meter, or the like.
  • the residue obtained by removing the chill component from the results obtained by 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 wave surface aberration.
  • the optical member may satisfy the requirement (5) for wave surface aberration at least in a predetermined region corresponding to a portion where the sensor transmits / receives infrared light on the main surface.
  • the optical member may satisfy the requirement (5) in the entire area of the main surface.
  • the wave surface aberration at ⁇ s is preferably 0.9 ⁇ RMS or less, more preferably 0.6 ⁇ RMS or less. More preferably 0.3 ⁇ RMS or less.
  • This optical member is further applied by the average reflectance of visible light (hereinafter, also referred to as "Rv1 ave ”) defined in ISO 9050: 2003, which is incident from the main surface on the opposite side of the sensor at an incident angle of 5 degrees. It can be used according to.
  • Rv1 ave average reflectance of visible light
  • the Rv1 ave of this optical member is less than 6%. Is preferable. As a result, the appearance of the vehicle is hardly spoiled.
  • the present optical member preferably has an Rv1 ave of 6% or more and less than 35%.
  • this optical member when metallic luster is required when the sensor is viewed from the outside, specifically when it is mounted on the body of a metallic color vehicle, this optical member has an Rv1 ave of 35% or more. It is preferable to have it. As a result, the appearance of the vehicle is hardly spoiled. Further, if necessary, Rv1 ave may be 60% or more, or 70% or more.
  • this optical member has CIE1976L * a * b * L * in chromaticity coordinates 0 to 25 and a * -13 to 13 for transmitted light obtained by irradiating visible light specified in ISO 9050: 2003.
  • B * is preferably -13 to 13.
  • L * is more preferably 5 to 0, and even more preferably 3 to 0.
  • a * -10 to 10 is more preferable, and -5 to 5 is even more preferable.
  • b * is more preferably -10 to 10, and even more preferably -5 to 5.
  • FIG. 1A A cross-sectional view of an example of the embodiment of this optical member is schematically shown in FIG. 1A.
  • the optical member 10A shown in FIG. 1A includes a glass substrate 1 having a first main surface 1a and a second main surface 1b facing each other, and an optical interference film 2.
  • the glass substrate 1 is made of amorphous glass, and the optical interference film 2 is arranged on the entire surface of the first main surface 1a of the glass substrate 1.
  • the main surface 2a of the optical interference film 2 opposite to the glass substrate 1 is the attachment surface to the sensor, and the main surface 1b of the glass substrate 1 opposite to the optical interference film 2 is the sensor. It is a surface that can be seen from the outside when it is attached (hereinafter, also referred to as "outer surface").
  • the main surface 2a of the optical interference film 2 opposite to the glass substrate 1 may be the outer surface.
  • the optical member 10A satisfies the above requirements (1) to (3) by including the glass substrate 1 and the optical interference film 2.
  • the optical interference film 2 is, for example, a multilayer film in which high refractive index layers and low refractive index layers are alternately laminated in order from the glass substrate 1 side.
  • the number of laminated layers and the laminated structure are not limited as long as the optical interference film satisfies the requirements (1) to (3) in combination with a glass substrate made of amorphous glass.
  • FIG. 1B A cross-sectional view of another example of the embodiment of the optical member is schematically shown in FIG. 1B.
  • the optical member 10B shown in FIG. 1B includes a glass substrate 1 having a first main surface 1a and a second main surface 1b facing each other, a first optical interference film 2, and a second optical interference film 3.
  • the glass substrate 1 is made of amorphous glass
  • the first optical interference film 2 covers the entire surface of the first main surface 1a of the glass substrate 1
  • the second optical interference film 3 is the second main surface of the glass substrate 1. They are arranged on the entire surface of the surface 1b.
  • the main surface 3b of the second optical interference film 3 opposite to the glass substrate 1 is the outer surface
  • the main surface 2a of the first optical interference film 2 opposite to the glass substrate 1 Is the mounting surface to the sensor.
  • the optical member 10B satisfies the above requirements (1) to (3) by including the glass substrate 1, the first optical interference film 2, and the second optical interference film 3.
  • the first optical interference film 2 and the second optical interference film 3 are, for example, multilayer films in which high refractive index layers and low refractive index layers are alternately laminated in order from the glass substrate 1 side. It may be the same or different.
  • the first optical interference film 2 is not provided on the first main surface 1a of the glass substrate 1, and the second optical interference film 3 is on the second main surface 1b.
  • a configuration example having the above can be mentioned.
  • the main surface 3b of the second optical interference film 3 opposite to the glass substrate 1 is the outer surface, and the main surface 2a of the first optical interference film 2 opposite to the glass substrate 1 is. This is the mounting surface for the sensor.
  • This example is also included in the category of this optical member as long as the requirements (1) to (3) are satisfied.
  • the glass substrate and the optical interference film constituting the optical member will be described below.
  • the glass substrate 1 has a first main surface 1a and a second main surface 1b facing each other.
  • the glass constituting the glass substrate 1 is amorphous glass.
  • the glass substrate satisfies the following requirements (G-1) to (G-3).
  • the maximum value of the light transmittance (hereinafter, also referred to as “ TGmax400-700 ”) with respect to the light incident in the range of the incident angle of 0 degrees or more and 5 degrees or less. ) Is 60% or less. If the glass substrate satisfies (G-1), the optical member can easily achieve the requirement (1) without significantly increasing the number of layers of the optical interference film to be combined. That is, it is easy to sufficiently shield visible light.
  • the TGmax 400-700 of the glass substrate in this optical member is larger than 55%, the optical for light in the wavelength band of 400 nm to 700 nm is obtained by increasing the number of layers of the optical interference film in order to satisfy the requirement (1).
  • the transmittance of the member is lowered, the reflected color on the outer surface is less likely to be gray or black, and the angle dependence of the reflected color of visible light becomes large, which is not preferable.
  • the TGmax 400-700 of the glass substrate is more preferably 55% or less, further preferably 50% or less, most preferably 45% or less, still more preferably 30% or less.
  • the width of the wavelength range in which the light transmittance is 25% or more with respect to the light incident in the range of the incident angle of 0 degrees or more and 5 degrees or less (hereinafter, "" Wavelength range width (25% or more) ”) is 250 nm or less. If the glass substrate satisfies (G-2), the optical member can easily achieve the requirement (1) without significantly increasing the number of layers of the optical interference film to be combined.
  • the wavelength range width (25% or more) exceeds 250 nm, the wavelength range reflected or absorbed by the optical interference film for shielding light becomes wider, and the number of layers of the optical interference film required for shielding visible light increases. It ends up. As a result, the angle dependence of the incident light of the reflected color on the outer surface becomes large, and the reflected color when viewed from an angle looks other than black, which is not preferable in terms of design.
  • the wavelength range width (25% or more) of the glass substrate of the optical member is preferably 225 nm or less, still more preferably 200 nm or less, even more preferably 150 nm or less, still more preferably 100 nm or less, and most preferably 50 nm or less. ..
  • the width of the wavelength range in which the light transmittance is 3% or more is preferably 10 nm or more. .. If it is attempted to be 10 nm or less, the amount of Cr 2 O 3 and Co 3 O 4 in the glass increases and the manufacturing characteristics of the glass deteriorate. Further, the transmittance of 800 nm or more and 1800 nm or less is lowered.
  • the wavelength range width (3% or more) is more preferably 50 nm or more, and even more preferably 100 nm or more.
  • the width of the wavelength range in which the light transmittance is 30% or more (hereinafter, also referred to as “wavelength range width (30% or more)”) is preferably 200 nm or less. , 90 nm or less is more preferable.
  • the wavelength range width (30% or more) is most preferably 40 nm or less.
  • the transmittance of light at the wavelength ⁇ s (hereinafter, also referred to as “ TG ⁇ s ”) is 78.5% or more. If the glass substrate satisfies (G-3), the optical member can easily achieve the requirement (2) and can easily obtain sufficient sensor accuracy.
  • the T G ⁇ s of the glass substrate is more preferably 80% or more, further preferably 83% or more, still more preferably 84.5% or more, and most preferably 87% or more.
  • ⁇ s is selected from 800 nm, 905 nm, 950 nm, 1050 nm and 1550 nm, and TG ⁇ s is preferably 78.5% or more, more preferably 80% or more, still more preferably 83 at two or more wavelengths of these. % Or more, more preferably 84.5% or more, and most preferably 87% or more.
  • the present optical member can easily obtain sufficient sensor accuracy in a wide range of two wavelengths or more.
  • the shape of the glass substrate 1 may be a flat plate, or may have a curvature on the entire surface or a part thereof.
  • a flat glass substrate is produced so as to have the same configuration as the glass substrate 1, and optical characteristics such as transmittance are measured.
  • an optical member using a glass substrate 1 having a curvature an optical member using a flat glass substrate is manufactured so as to have the same configuration as the optical member, and the optical characteristics are measured.
  • the thickness of the glass substrate 1 can be appropriately adjusted according to the application.
  • the thickness of the glass substrate 1 is preferably 0.5 to 8 mm, more preferably 1 to 6 mm, still more preferably 2 to 5 mm, from the viewpoint of strength (evaluated by a gravure test) and weight balance due to ensuring safety by stepping stones. 5-4 mm is particularly preferable.
  • physical strengthening can be achieved by setting the thickness to 2.5 mm or more, and sufficient resistance to stepping stones can be obtained by inserting a sufficiently deep compressive stress layer of 400 nm or more.
  • a glass containing chromium (Cr) is preferable from the viewpoint of satisfying the optical properties of (G-1) to (G-3).
  • Cr chromium
  • glass containing Cr at a ratio of 10 mass ppm or more and 20000 mass ppm or less in terms of Cr 2 O 3 is preferable. It is preferable that Cr is contained in glass as an oxide.
  • the optical member using the glass can easily satisfy the characteristics of (1) and (2). Further, it is easy to adjust the content of Cr 6+ within the following range.
  • Content of Cr is in terms of Cr 2 O 3, is preferably from 100 to 11,000 ppm by weight, more preferably from 500 to 9500 ppm by weight, still more preferably from 800 to 8000 ppm by weight, most preferably from 1000 to 7500 ppm by weight ..
  • the content of Cr 6+ in the glass is preferably less than 1000 mass ppm. It is more preferably less than 800 mass ppm, still more preferably less than 600 mass ppm, even more preferably less than 400 mass ppm, and most preferably less than 200 mass ppm.
  • the content of Cr 6+ can be adjusted by adding C according to the atmosphere at the time of melting the glass.
  • the Fe component which is inevitably mixed during the production of glass, lowers the infrared light transmittance.
  • a glass capable of obtaining high infrared light transmission even if it contains such an Fe component is required.
  • the glass containing Cr is preferably used in the present embodiment because it can maintain high infrared light transmittance even if it contains a predetermined amount of Fe.
  • Fe is contained in glass as iron oxide, and is preferably 1 mass ppm or more and 500 mass ppm or less in terms of Fe 2 O 3 . If Fe 2 O 3 is less than 1 mass ppm, the temperature stability due to radiant heat at the time of melting the glass becomes insufficient. On the other hand, if the Fe content exceeds 500 mass ppm in terms of Fe 2 O 3 , the transmittance in the near infrared region may decrease.
  • the Fe content is preferably 5 to 200 mass ppm, more preferably 15 to 120 mass ppm, still more preferably 25 to 75 mass ppm, and most preferably 30 to 55 mass ppm in terms of Fe 2 O 3 .
  • glass containing Cr for example, glass containing silicon dioxide as a main component such as soda lime glass, borosilicate glass, non-alkali glass, aluminosilicate glass, non-alkali aluminum nosilicate glass, and quartz glass is preferable.
  • the glass containing Cr is preferably soda lime glass having the following composition in terms of mass% based on oxides, for example. Further, it may be borosilicate glass or aluminosilicate glass.
  • the Cr-containing glass A has, for example, an oxide-based mass percentage display, SiO 2 of 60 to 73.0%, Al 2 O 3 of 0 to 20%, and RO (where R is Mg, Ca, 5 to 30% (one or more selected from Sr and Ba), 0 to 5% Li 2 O, R 2 O (where R is one or more selected from Li, Na, and K) 3 to 25%, Cr is 10 mass ppm or more and 20000 mass ppm or less in terms of Cr 2 O 3 , and Fe is 1 mass ppm or more and 500 mass ppm or less in terms of Fe 2 O 3 .
  • SiO 2 is 70 to 86.0%
  • Al 2 O 3 is 0 to 10%
  • B 2 O 3 is 5 to 20%
  • RO is one or more selected from Mg, Ca, Sr, and Ba
  • R is one or more selected from Mg, Ca, Sr, and Ba
  • Li 2 O is 0 to 5%
  • R 2 O where R is Li, Na, 0.5 to 7.5% (one or more selected from K)
  • Cr is 10 mass ppm or more and 20000 mass ppm or less in terms of Cr 2 O 3
  • Fe is 1 mass ppm or more and 500 in terms of Fe 2 O 3. Contains less than mass ppm.
  • the glass material used here is a material capable of forming a compressive stress layer on the glass surface by a strengthening treatment, and a material capable of forming a compressive stress layer by a physical strengthening treatment is preferable.
  • the composition of the glass is simply determined by semi-quantitative analysis by the fluorescence X-ray method, but more accurately, it can be measured by a wet analysis method such as ICP emission spectrometry.
  • the content of each component is represented by an oxide-based mass percentage (mass%), and is hereinafter represented by "%" unless otherwise specified.
  • the components constituting the glass compositions A and B will be specifically described below.
  • A is a composition having excellent meltability and infrared transmittance of glass
  • B is a composition having excellent wave surface aberration and stepping stone strength.
  • SiO 2 is a component constituting the skeleton of glass and is indispensable. In addition, it is a component that increases chemical durability and reduces the occurrence of cracks when the glass surface is scratched (indented).
  • the content of SiO 2 is 60% or more. In order to effectively exhibit the above characteristics, the content of SiO 2 is preferably 64% or more, more preferably 67% or more. On the other hand, if the content of SiO 2 is more than 73%, the meltability tends to decrease. Therefore, the content of SiO 2 is 73% or less, preferably 71% or less, and more preferably 70% or less.
  • Al 2 O 3 is a component that improves acid resistance, Young's modulus, and hardness, and is a preferable component if it is contained. Further, Al 2 O 3 is a component that raises the glass transition point (Tg) of the glass and may be contained for adjusting the glass transition point.
  • the content of Al 2 O 3 is preferably 0.1% or more. In order to effectively exhibit the above characteristics, the content of Al 2 O 3 is preferably 0.3% or more. On the other hand, if the content of Al 2 O 3 is more than 20%, the acid resistance of the glass tends to decrease or the devitrification temperature tends to increase, so that the content of Al 2 O 3 is 20% or less. In addition, the viscosity of the glass may increase and the meltability may decrease. Therefore, the content of Al 2 O 3 is preferably 15% or less, more preferably 10% or less, further preferably 8% or less, and particularly preferably 5% or less.
  • RO (where R is one or more selected from Mg, Ca, Sr, and Ba) is a component that improves the meltability of glass, is also a component that improves Young's modulus, and adjusts the expansion coefficient. It is also an ingredient and is an essential ingredient.
  • the RO content indicates the total content of MgO, CaO, SrO, and BaO described below.
  • the RO content is 5 to 30%, preferably 15 to 25%, more preferably 17 to 23%, and even more preferably 19 to 22%.
  • MgO is a component that improves the meltability of glass, a component that improves Young's modulus, a component that adjusts the coefficient of expansion, and may be contained.
  • the content is preferably 0.5% or more, more preferably 1% or more, further preferably 2% or more, particularly preferably 2.4% or more, and most preferably 3% or more.
  • the MgO content exceeds 10%, the devitrification characteristics deteriorate, so the MgO content is preferably 10% or less.
  • the content of MgO is more preferably 7.5% or less, further preferably 5% or less, and most preferably 4% or less.
  • CaO is a component that improves the meltability of glass, a component that improves Young's modulus, and a component that adjusts the expansion coefficient, and may be contained.
  • the content is preferably 0.5% or more, more preferably 1% or more, further preferably 2% or more, particularly preferably 3% or more, and most preferably 4% or more.
  • the CaO content is preferably 12% or less.
  • the CaO content is more preferably 10% or less, further preferably 8% or less, particularly preferably 6% or less, and most preferably 4.5% or less.
  • SrO is a component that improves the meltability of glass, a component that improves Young's modulus, and a component that adjusts the expansion coefficient, and may be contained.
  • the content is preferably 0.5% or more, more preferably 1% or more, further preferably 2% or more, particularly preferably 3% or more, and most preferably 5% or more.
  • the SrO content exceeds 15%, the devitrification characteristics deteriorate, so the SrO content is preferably 15% or less.
  • the content of SrO is more preferably 12% or less, further preferably 10% or less, particularly preferably 8% or less, and most preferably 7% or less. In order to reduce brittleness, it is preferably 5% or less, and more preferably not contained.
  • BaO is a component that improves the meltability of glass, a component that improves Young's modulus, and a component that adjusts the expansion coefficient, and may be contained.
  • the content is preferably 0.5% or more, more preferably 2% or more, further preferably 4% or more, particularly preferably 6% or more, and most preferably 7% or more.
  • the BaO content exceeds 20%, the devitrification characteristic deteriorates, so that the BaO content is preferably 20% or less.
  • the content of BaO is more preferably 15% or less, further preferably 12% or less, particularly preferably 10% or less, and most preferably 8% or less. In order to reduce brittleness, it is preferably 5% or less, and preferably not contained.
  • R 2 O (where R is one or more selected from Li, Na, and K) is a component that adjusts the viscosity of glass and improves meltability, and is essential.
  • the content of R 2 O is the total amount of these components (Li 2 O + Na 2 O + K 2 O).
  • the content of R 2 O is 3% or more, preferably at least 4%, more preferably at least 6%, more preferably 8% or more.
  • R 2 O content is preferably 20% or less, more preferably 15% or less, and most preferably 12% or less.
  • Li 2 O is a useful component for increasing Young's modulus while maintaining a low density in order to realize an infrared transmissive glass that is lightweight, has insulating properties, and has sufficient strength.
  • the melt viscosity can be reduced while maintaining the coefficient of expansion. Further, it is preferably contained in order to improve the transmittance in the infrared region.
  • the Li 2 O content is preferably 1% or more, more preferably 2% or more, and 3%.
  • the above is more preferable, and 3.5% or more is particularly preferable.
  • the content of Li 2 O is 5% or less and 4% or less. Is preferable, and 3.5% or less is more preferable.
  • Li 2 O when it is desired to improve the transmittance in the infrared region while containing less than 0.2% of Cr 2 O 3 , it is preferable to contain Li 2 O.
  • the content of Li 2 O is preferably 0.1% or more, more preferably 0.5% or more, further preferably 1% or more, and particularly preferably 1.3% or more.
  • the content of Li 2 O exceeds 5%, the devitrification property of the glass tends to decrease and the acid resistance of the glass tends to decrease. Therefore, the content of Li 2 O is 5% or less and 4% or less. Is preferable, 3% or less is more preferable, and 2% or less is most preferable.
  • Na 2 O is a component that adjusts the expansion coefficient and improves the meltability of the glass, and is preferably contained.
  • the Na 2 O content is preferably 1% or more, more preferably 2% or more. On the other hand, if the Na 2 O content exceeds 20%, the expansion coefficient becomes too large and the acid resistance decreases.
  • the content of Na 2 O is preferably 15% or less, more preferably 12% or less, further preferably 10% or less, particularly preferably 7% or less, and most preferably 4% or less.
  • K 2 O is a component that adjusts the expansion coefficient and improves the meltability of the glass, and may be contained.
  • the content is preferably 0.1% or more, more preferably 1% or more, and even more preferably 3% or more.
  • the K 2 O content is more than 10%, the expansion coefficient becomes large, the devitrification characteristic is lowered, and the Young's modulus is lowered. Therefore, the K 2 O content is preferably 10% or less.
  • the content of K 2 O is more preferably 8% or less, further preferably 7% or less, particularly preferably 6% or less, and most preferably 5% or less.
  • Cr is contained as an oxide, and when it is contained at a ratio of 10 mass ppm or more and 20000 mass ppm or less in terms of Cr 2 O 3 , the above optical properties are imparted to the glass.
  • Content of Cr is in terms of Cr 2 O 3, is preferably from 100 to 11,000 ppm by weight, more preferably from 500 to 9500 ppm by weight, still more preferably from 800 to 8000 ppm by weight, most preferably from 1000 to 7500 ppm by weight ..
  • the Cr 6+ content in the glass is preferably less than 1000 mass ppm. It is more preferably less than 800 mass ppm, still more preferably less than 600 mass ppm, even more preferably less than 400 mass ppm, and most preferably less than 200 mass ppm.
  • Fe is contained as an oxide, and by containing it at a ratio of 1 mass ppm or more and 500 mass ppm or less in terms of Fe 2 O 3 , it is possible to achieve both improvement of solubility while maintaining infrared transmittance in glass.
  • the Fe content is preferably 5 to 200 mass ppm, more preferably 15 to 120 mass ppm, still more preferably 25 to 75 mass ppm, and most preferably 30 to 55 mass ppm in terms of Fe 2 O 3 .
  • the glass composition of the glass A may contain various arbitrary components as long as the effects of the present embodiment are not impaired.
  • examples of the optional component include the following components.
  • Co 3 O 4 is a component that absorbs light in the visible region, transmits light in the near infrared wavelength region of 800 to 1100 nm, and improves clarity, and may be contained in a proportion of 1000 mass ppm or less. If it exceeds 1000 mass ppm, the infrared transmittance decreases. It is preferably 10 mass ppm or more and 700 mass ppm or less, and more preferably 100 mass ppm or more and 600 mass ppm or less.
  • MnO 2 is a component that absorbs light in the visible region and transmits light in the near infrared region, and may be contained in a proportion of 2000 mass ppm or less. If it exceeds 2000 mass ppm, the infrared transmittance decreases. It is preferably 1500 mass ppm or less, more preferably 1000 mass ppm or less, still more preferably 800 mass ppm or less.
  • B 2 O 3 is a component that reduces the brittleness of infrared transmissive glass, improves impact resistance, and improves meltability.
  • B 2 O 3 is not essential, the content when B 2 O 3 is contained is preferably 0.5% or more, more preferably 2% or more, and 5% in order to improve meltability and impact resistance. The above is more preferable.
  • the content of B 2 O 3 exceeds 15%, acid resistance tends to deteriorate, so 12% or less is preferable, 10% or less is more preferable, and 8% or less is further preferable.
  • P 2 O 5 is a component that stabilizes the glass and reduces brittleness.
  • P 2 O 5 may not be contained, but the content of the case of containing a P 2 O 5 is preferably 0.5% or more, more preferably at least 1%, 2% or more is more preferable.
  • the content of P 2 O 5 exceeds 6%, the devitrification property is lowered and the acid resistance is further lowered. Therefore, the content of P 2 O 5 is preferably 6% or less, more preferably 4% or less. It is preferable, and 3% or less is more preferable. Further, it is preferable not to contain the glass in order to prevent the quality of the glass from being deteriorated due to the occurrence of veins during melting.
  • ZnO is a component that improves the meltability of glass and may be contained.
  • the content is preferably 0.5% or more, more preferably 2% or more.
  • the ZnO content exceeds 15%, the weather resistance of the glass is remarkably lowered, so that the ZnO content is preferably 15% or less.
  • the ZnO content is more preferably 10% or less, further preferably 8% or less, particularly preferably 6% or less, and most preferably 5% or less.
  • TiO 2 is a component that improves Young's modulus and may be contained.
  • the content is preferably 0.1% or more, more preferably 0.5% or more, still more preferably 1% or more.
  • the content of TiO 2 is preferably 7% or less.
  • the content of TiO 2 is preferably 5% or less, more preferably 3% or less, further preferably 2% or less, and particularly preferably 1.5% or less.
  • ZrO 2 is also a component that improves Young's modulus and may be contained.
  • the content is preferably 0.5% or more, more preferably 1% or more.
  • the content of ZrO 2 is preferably 8% or less.
  • the content of ZrO 2 is more preferably 6% or less, further preferably 4% or less, particularly preferably 2% or less, and most preferably 1.2% or less.
  • La 2 O 3 and Nb 2 O 5 are components that improve Young's modulus and may be contained. When these components are contained, the content of each is preferably 0.5% or more, more preferably 1% or more, further preferably 2% or more, particularly preferably 2.5% or more, and most preferably 3% or more. preferable. Meanwhile, La 2 O 3, Nb 2 O content of 5 becomes is 15 percent each glass is easily devitrified when melted, since the quality of the chemically tempered glass may be lowered, La 2 O 3, The content of Nb 2 O 5 is preferably 15% or less, respectively. The contents of La 2 O 3 and Nb 2 O 5 are each more preferably 12% or less, further preferably 10% or less, particularly preferably 8% or less, and most preferably 5% or less.
  • Ta 2 O 5 and Gd 2 O 3 may be contained in a small amount in order to improve Young's modulus, but they are contained because they are likely to be devitrified at the time of melting and the quality of glass may be deteriorated.
  • the content of each of them is preferably 3% or less, more preferably 1% or less, and further preferably not contained.
  • a coloring component may be added within a range that does not hinder the achievement of the desired transmittance characteristics.
  • the coloring component for example, NiO, CuO, V 2 O 5, Bi 2 O 3, SeO 2, TiO 2, CeO 2, Er 2 O 3, Nd 2 O 3 and the like as preferred.
  • the total content of these coloring components is preferably in the range of 7% or less. If it exceeds 7%, the glass tends to be devitrified, which is not desirable. This content is preferably 5% or less, more preferably 3% or less, still more preferably 1% or less. When giving priority to the infrared transmittance of glass, it is preferable that these components are not substantially contained.
  • As 2 O 3 is not contained.
  • As 2 O 3 it is preferably 0.3% or less, more preferably 0.1% or less, and most preferably not contained.
  • SO 3 , chloride, fluoride and the like may be appropriately contained as a fining agent when the glass is melted.
  • the amount of each component added to the glass is preferably 0.01 to 0.5%, more preferably 0.07 to 0.2%, respectively.
  • C is arbitrarily added depending on the atmosphere at the time of melting the glass in order to adjust the content of Cr 6+ in the glass containing Cr.
  • the amount of C added is preferably 0.01 to 0.1%, more preferably 0.02 to 0.06% in terms of external division, with the content of Cr 6+ in the above range.
  • SiO 2 is a component constituting the skeleton of glass and is indispensable. In addition, it is a component that increases chemical durability and reduces the occurrence of cracks when the glass surface is scratched (indented).
  • the content of SiO 2 is 70% or more. In order to effectively exhibit the above characteristics, the content of SiO 2 is preferably 74% or more, more preferably 77% or more. On the other hand, if the content of SiO 2 is more than 86%, the meltability tends to decrease. Therefore, the content of SiO 2 is 86% or less, preferably 84% or less, and more preferably 82% or less.
  • Al 2 O 3 is a component that improves acid resistance, Young's modulus, and hardness, and is a preferable component if it is contained. Further, Al 2 O 3 is a component that raises the glass transition point (Tg) of the glass and may be contained for adjusting the glass transition point.
  • the content of Al 2 O 3 is preferably 0.1% or more. In order to effectively exhibit the above characteristics, the content of Al 2 O 3 is preferably 0.3% or more. On the other hand, if the content of Al 2 O 3 is more than 10%, the meltability of the glass is lowered and the devitrification temperature tends to be higher. Therefore, the content of Al 2 O 3 is 10% or less. Therefore, the content of Al 2 O 3 is preferably 7.5% or less, more preferably 6% or less, further preferably 4% or less, and particularly preferably 2.5% or less.
  • B 2 O 3 is an essential component that improves impact resistance by reducing the brittleness of infrared transmissive glass, further reduces the scratch depth during the gravure test, and improves meltability.
  • the content is 5% or more.
  • the content of B 2 O 3 is preferably 7% or more, more preferably 10% or more.
  • the content of B 2 O 3 is 20% or less, preferably 18% or less, and 16% or less. Is more preferable, and 14% or less is further preferable.
  • RO (where R is one or more selected from Mg, Ca, Sr, and Ba) is a component that improves the meltability of glass, is also a component that improves Young's modulus, and adjusts the expansion coefficient. Therefore, it may be contained in the range of 10% or less. It is preferably 7.5% or less, and most preferably 5% or less.
  • the RO content is the total content of MgO, CaO, SrO, and BaO.
  • R 2 O (where R is one or more selected from Li, Na, and K) is a component that adjusts the viscosity of glass and improves meltability, and is essential.
  • the content of R 2 O is the total amount of these components (Li 2 O + Na 2 O + K 2 O).
  • the content of R 2 O is 0.5% or more, preferably at least 1.5%, more preferably at least 2%, more preferably 3% or more.
  • R 2 O content is preferably 6% or less, more preferably 5.5% or less, and most preferably 5% or less.
  • Li 2 O is a component useful for increasing Young's modulus while maintaining a low density in order to realize an infrared transmissive glass that is lightweight, has insulating properties, and has sufficient strength, and is 5% or less. It is preferable to contain it in a range. If it exceeds 5%, the devitrification temperature may increase. In addition, the melt viscosity can be reduced while maintaining the coefficient of expansion. Further, it is preferably contained in order to improve the transmittance in the infrared region.
  • Na 2 O is a component that adjusts the expansion coefficient and improves the meltability of the glass, and is preferably contained.
  • the Na 2 O content is preferably 1% or more, more preferably 2% or more.
  • the content of Na 2 O is preferably 7% or less, more preferably 6% or less, still more preferably 5% or less.
  • K 2 O is a component that adjusts the expansion coefficient and improves the meltability of the glass, and may be contained.
  • the content is preferably 0.1% or more, more preferably 0.5% or more, and even more preferably 2.5% or more.
  • the content of K 2 O is more than 7.5%, the expansion coefficient becomes large, the devitrification characteristic is lowered, and the Young's modulus is lowered, so that the content of K 2 O is 7.5% or less. Is preferable.
  • the content of K 2 O of is more preferably 6% or less, more preferably 5% or less, particularly preferably 4% or less, most preferably 3% or less.
  • Cr is contained as an oxide, and when it is contained at a ratio of 10 mass ppm or more and 20000 mass ppm or less in terms of Cr 2 O 3 , the above optical properties are imparted to the glass.
  • Content of Cr is in terms of Cr 2 O 3, is preferably from 100 to 10,000 ppm by weight, more preferably from 200 to 8500 ppm by weight, still more preferably from 300 to 7000 ppm by weight, most preferably 500-5000 ppm by weight ..
  • the Cr 6+ content in the glass is preferably less than 1000 mass ppm. It is more preferably less than 800 mass ppm, still more preferably less than 600 mass ppm, even more preferably less than 400 mass ppm, and most preferably less than 200 mass ppm.
  • Fe is contained as an oxide, and by containing it at a ratio of 1 mass ppm or more and 500 mass ppm or less in terms of Fe 2 O 3 , it is possible to achieve both improvement of solubility while maintaining infrared transmittance in glass.
  • the Fe content is preferably 5 to 200 mass ppm, more preferably 15 to 120 mass ppm, still more preferably 25 to 75 mass ppm, and most preferably 30 to 55 mass ppm in terms of Fe 2 O 3 .
  • the glass composition of this glass B can contain various arbitrary components as long as the effects of the present embodiment are not impaired.
  • examples of the optional component include the following components.
  • Co 3 O 4 is a component that absorbs light in the visible region, transmits light in the near infrared wavelength region of 800 to 1100 nm, and improves clarity, and may be contained in a proportion of 1500 mass ppm or less. If it exceeds 1500 mass ppm, the infrared transmittance decreases. It is preferably 10 mass ppm or more and 1300 mass ppm or less, and more preferably 500 mass ppm or more and 1000 mass ppm or less.
  • MnO 2 is a component that absorbs light in the visible region and transmits light in the near infrared region, and may be contained in a proportion of 2000 mass ppm or less. If it exceeds 2000 mass ppm, the infrared transmittance decreases. It is preferably 1500 mass ppm or less, more preferably 1000 mass ppm or less, still more preferably 800 mass ppm or less.
  • P 2 O 5 is a component that stabilizes the glass and reduces brittleness.
  • P 2 O 5 may not be contained, but the content of the case of containing a P 2 O 5 is preferably 0.5% or more, more preferably at least 1%, 2% or more is more preferable.
  • the content of P 2 O 5 exceeds 6%, the devitrification property is lowered and the acid resistance is further lowered. Therefore, the content of P 2 O 5 is preferably 6% or less, more preferably 4% or less. It is preferable, and 3% or less is more preferable. Further, it is preferable not to contain the glass in order to prevent the quality of the glass from being deteriorated due to the occurrence of veins during melting.
  • ZnO is a component that improves the meltability of glass and may be contained.
  • the content is preferably 0.5% or more, more preferably 2% or more.
  • the ZnO content exceeds 15%, the weather resistance of the glass is remarkably lowered, so that the ZnO content is preferably 15% or less.
  • the ZnO content is more preferably 10% or less, further preferably 8% or less, particularly preferably 6% or less, and most preferably 5% or less.
  • TiO 2 is a component that improves Young's modulus and may be contained.
  • the content is preferably 0.1% or more, more preferably 0.5% or more, still more preferably 1% or more.
  • the content of TiO 2 is preferably 7% or less.
  • the content of TiO 2 is preferably 5% or less, more preferably 3% or less, further preferably 2% or less, and particularly preferably 1.5% or less.
  • ZrO 2 is also a component that improves Young's modulus and may be contained.
  • the content is preferably 0.5% or more, more preferably 1% or more.
  • the content of ZrO 2 is preferably 8% or less.
  • the content of ZrO 2 is more preferably 6% or less, further preferably 4% or less, particularly preferably 2% or less, and most preferably 1.2% or less.
  • La 2 O 3 and Nb 2 O 5 are components that improve Young's modulus and may be contained. When these components are contained, the content of each is preferably 0.5% or more, more preferably 1% or more, further preferably 2% or more, particularly preferably 2.5% or more, and most preferably 3% or more. preferable. Meanwhile, La 2 O 3, Nb 2 O content of 5 becomes is 15 percent each glass is easily devitrified when melted, since the quality of the chemically tempered glass may be lowered, La 2 O 3, The content of Nb 2 O 5 is preferably 15% or less, respectively. The contents of La 2 O 3 and Nb 2 O 5 are each more preferably 12% or less, further preferably 10% or less, particularly preferably 8% or less, and most preferably 5% or less.
  • Ta 2 O 5 and Gd 2 O 3 may be contained in a small amount in order to improve Young's modulus, but they are contained because they are likely to be devitrified at the time of melting and the quality of glass may be deteriorated.
  • the content of each of them is preferably 3% or less, more preferably 1% or less, and further preferably not contained.
  • a coloring component may be added within a range that does not hinder the achievement of the desired transmittance characteristics.
  • the coloring component for example, NiO, CuO, V 2 O 5, Bi 2 O 3, SeO 2, TiO 2, CeO 2, Er 2 O 3, Nd 2 O 3 and the like as preferred.
  • the total content of these coloring components is preferably in the range of 7% or less. If it exceeds 7%, the glass tends to be devitrified, which is not desirable. This content is preferably 5% or less, more preferably 3% or less, still more preferably 1% or less. When giving priority to the infrared transmittance of glass, it is preferable that these components are not substantially contained.
  • As 2 O 3 is not contained.
  • As 2 O 3 it is preferably 0.3% or less, more preferably 0.1% or less, and most preferably not contained.
  • SO 3 , chloride, fluoride and the like may be appropriately contained as a fining agent when the glass is melted.
  • the amount of each component added to the glass is preferably 0.01 to 1.5%, more preferably 0.5 to 1.2%, respectively.
  • C is arbitrarily added depending on the atmosphere at the time of melting the glass in order to adjust the content of Cr 6+ in the glass containing Cr.
  • the amount of C added is preferably 0.01 to 0.1%, more preferably 0.02 to 0.06% in terms of external division, with the content of Cr 6+ in the above range.
  • Cd cadmium
  • the glass substrate used for this optical member for example, various raw materials are appropriately mixed so that the glass composition is in a desired range, preferably the composition of the glass containing Cr, heated and melted, and then defoamed and stirred. It is homogenized by the above, and is obtained by forming it into a plate shape or the like by a well-known float method, down draw method, press method or roll-out method, or by casting it into a block shape, slowly cooling it, and then processing it into a plate shape. ..
  • the glass substrate for example, it is preferable to use a glass plate formed by the float method. Further, it is preferable that the glass substrate is strengthened by wind cooling strengthening (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 impacts is improved.
  • the coefficient of linear expansion of the glass constituting the glass substrate is preferably 30 ⁇ 10 -7 / ° C or higher, more preferably 35 ⁇ 10 -7 / ° C or higher, and 60 ⁇ 10-7 / ° C. or higher is more preferable.
  • the coefficient of linear expansion of glass is preferably 100 ⁇ 10-6 / ° C. or lower, more preferably 95 ⁇ 10-6 / ° C. or lower, and 90 ⁇ 10-6 / ° C. from the viewpoint of dimensional accuracy after physical strengthening. The following is more preferable.
  • the coefficient of linear expansion in the present specification is an average coefficient of linear expansion at 50 ° C. to 350 ° C.
  • the linear expansion coefficient of the glass constituting the glass substrate is 20 ⁇ . It is preferably 10-7 / ° C. or higher, more preferably 25 ⁇ 10-7 / ° C. or higher, and even more preferably 30 ⁇ 10-7 / ° C. or higher.
  • the coefficient of linear expansion of glass is preferably 50 ⁇ 10 -6 / ° C or lower, more preferably 40 ⁇ 10 -6 / ° C or lower, and 31 ⁇ 10 ⁇ ° C. from the viewpoint of dimensional accuracy after physical strengthening and wave surface aberration. 6 / ° C. or lower is more preferable.
  • the coefficient of linear expansion in the present specification is an average coefficient of linear expansion at 50 ° C. to 350 ° C.
  • the Tg of the glass constituting the glass substrate is preferably 470 to 630 ° C. from the viewpoint of heat resistance and workability during physical strengthening.
  • Tg is more preferably 500 to 600 ° C, still more preferably 535 to 580 ° C. It is possible to perform physical strengthening in a temperature range of 750 ° C. or lower using an existing physical strengthening furnace.
  • the surface compressive stress (CS) of the strengthened glass substrate is preferably 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. If it is desired to control the dimensional accuracy after physical strengthening with high accuracy, it is preferably 70 MPa or less.
  • the surface compressive stress (CS) is preferably 90 MPa or less.
  • the surface compressive stress is more preferably 65 MPa or less, further preferably 50 MPa or less, and particularly preferably 40 MPa or less.
  • the depth of the compressive stress layer to be inserted into the glass substrate is preferably 300 ⁇ m or more.
  • the depth of the compressive stress layer is more preferably 350 ⁇ m or more, further preferably 400 ⁇ m or more, and most preferably 500 ⁇ m or more. If the depth is less than 300 ⁇ m, sufficient flight strength cannot be secured.
  • the surface compressive stress (CS) and the depth of the compressive stress layer (DOL) can be measured as follows. From the glass substrate before forming the compressive stress layer, a disk having a mirror surface on the entire surface is produced. Using the produced disk, the photoelastic constant is obtained by the disk compression method. Next, after cutting the strengthened glass substrate, the cut surface is optically polished and the retardation is measured by a birefringence measuring device. Then, the generated stress (compressive stress (CS) on the surface) can be obtained by dividing the measured retardation value by the photoelastic constant and the thickness of the glass substrate.
  • the distance from the surface until the compressive stress becomes zero can be calculated to obtain the depth (DOL) of the compressive stress layer.
  • DOL depth of the compressive stress layer.
  • it is typically 1/6 of the plate thickness.
  • the glass substrate is not damaged under the gravure test condition A. By not damaging it, it is possible to protect the internal sensor parts and the like.
  • the glass substrate has a small average scratch depth at any three points under the gravure test condition B.
  • the wound depth is preferably 500 ⁇ m or less, more preferably 300 ⁇ m or less, further preferably 150 ⁇ m or less, and most preferably 100 ⁇ m or less.
  • the size of the glass substrate used for this optical member can be adjusted as appropriate according to the application. For example, a glass plate obtained by a float method or the like is cut into a predetermined size and used.
  • the end surface connecting the first main surface and the second main surface of the glass substrate is preferably chamfered for the purpose of preventing cracks at the end portion and its vicinity.
  • the glass substrate it is preferable to use a single glass plate from the viewpoint of shape stability against heat, particularly satisfying the requirement (3).
  • the glass substrate may be laminated glass if necessary.
  • optical interference film The optical interference film is formed on the main surface of the glass substrate, and the obtained optical member functions so as to achieve the requirements (1) to (3).
  • the optical interference film 2 formed on the first main surface 1a of the glass substrate 1 has the above function
  • the glass substrate 10B shown in FIG. 1B the glass substrate It has the above-mentioned function in the combination of the functions of the optical interference film 2 formed on the first main surface 1a and the optical interference film 3 formed on the second main surface 1b. The same applies when the optical member has the optical interference film only on the second main surface.
  • the optical interference film lowers T max 400-700 in the incident angle range of 0 to 5 degrees as compared with the case where the glass substrate is used alone, and at the wavelength ⁇ s , the glass. It functions to achieve the requirements of (1) and (2) by reducing the reflectance as compared with the case where the substrate is used alone.
  • the requirement (3) can be achieved by forming the optical interference film with a heat-resistant material.
  • the optical interference film further preferably functions so that the obtained optical member satisfies one or more of the requirements (4) and (5).
  • the optical interference film is such that the optical member functions so as to satisfy the requirements (1) to (3), preferably one or more of the requirements (4) and (5).
  • a film having other functions such as imparting visible light shielding property, ultraviolet shielding property, antifouling property, dustproof property, and improving durability may be used.
  • both of the glass substrates are provided with an optical interference film in which the optical member satisfies the requirements (1) to (3), and preferably one or more of the requirements (4) and (5) when used alone.
  • T max 400-700 tends to decrease and T min (2) tends to improve as compared with the case where each optical interference film is used alone.
  • the configuration of the optical interference film is appropriately selected according to the optical characteristics required for the optical member.
  • the optical interference film may be a single-layer film composed of only one layer, or may be a multilayer film in which two or more layers are laminated, and a multilayer film is preferable.
  • a multilayer film composed of 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 32 layers or less, and particularly preferably 20 layers or less, from the viewpoint of manufacturing cost and thinning.
  • the low refractive index layer and the high refractive index layer are preferably laminated 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 difference in refractive index between the low refractive index layer and the high refractive index layer that is, the difference in refractive index between the low refractive index material and the high refractive index material may be more than 0, preferably 0.1 or more.
  • the description of the refractive index of the optical thin film constituting the optical interference film in the present specification means the refractive index of each material at the set wavelength ⁇ 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 refractive index of the low refractive index material constituting the low refractive index layer is preferably 1.35 or more and less than 1.55.
  • the low refractive index material include a material containing a low refractive index substance such as silicon oxide and magnesium fluoride as a main component.
  • the main component in each refractive index layer means that the substance is contained in an amount of 90% or more.
  • the low refractive index material has a low refractive index, preferably at least one of the low refractive index substances as a main component as long as the refractive index is adjusted within the above range, and further contains an intermediate refractive index substance and a high refractive index substance. It may be configured to be used.
  • the low refractive index material is preferably composed of only a low refractive index substance, and more preferably composed of only one kind of low refractive index substance. It is preferable to use silicon oxide as the low refractive index substance from the viewpoint of reproducibility, stability, economy and the like in terms of film forming property.
  • the refractive index of the high-refractive index material constituting the high-refractive index layer is preferably 1.90 or more and 5.00 or less.
  • high refractive index materials include silicon hydride, silicon, silicon nitride, silicon nitride, aluminum nitride, aluminum nitride, zirconium oxide, tin oxide, cerium oxide, silicon, copper oxide, germanium, titanium oxide, and niobium oxide.
  • a material whose main component is a high refractive index substance such as tantalum oxide.
  • these high-refractive index substances may be doped with a metal other than the metal constituting the nitride, oxide or oxynitride.
  • high refractive index substances containing a doped metal include zirconium-doped titanium oxide, zirconium-doped silicon oxide, aluminum-doped zirconium oxide, zirconium-doped niobium oxide, hafnium-doped zinc oxide, aluminum-doped zinc oxide, and aluminum-doped silicon nitride. Examples thereof include aluminum-doped silicon nitride.
  • the high refractive index material has a high refractive index, preferably at least one of the high refractive index substances as a main component as long as the refractive index is adjusted within the above range, and further contains a low refractive index substance and an intermediate refractive index substance. It may be configured to be used.
  • the high refractive index material is preferably composed of only the high refractive index substance, and more preferably composed of only one kind of the high refractive index substance.
  • silicon nitride, silicon oxynitride, aluminum nitride, aluminum oxynitride, zirconium oxide, tin oxide, cerium oxide, silicon, copper oxide, and hydrogenation are obtained from the viewpoint that desired optical characteristics can be obtained when a multilayer film is formed.
  • Silicon, niobium oxide, tantalum oxide, zirconium-doped titanium oxide, and zirconium-doped silicon oxide are preferable.
  • silicon nitride, silicon oxynitride, aluminum nitride, aluminum oxynitride, zirconium oxide, tin oxide, cerium oxide, silicon, silicon hydride, niobium oxide, and oxidation can be obtained from the viewpoint that the desired hardness can be obtained when the multilayer film is formed. Tantal, zirconium-doped titanium oxide, zirconium-doped silicon oxide are preferable, and silicon nitride, zirconium oxide, aluminum nitride, tin oxide, silicon, silicon hydride, niobium oxide, tantalum oxide, zirconium-doped titanium oxide, and zirconium-doped silicon oxide are more preferable. From the viewpoint of shape stability with respect to heat, silicon nitride, niobium oxide, silicon hydride, silicon, and zirconium-doped titanium oxide are particularly preferable.
  • the refractive index of the intermediate refractive index material constituting the intermediate refractive index layer is preferably 1.55 or more and less than 1.90.
  • the intermediate refractive index material include materials containing an intermediate refractive index substance as a main component, such as aluminum oxide, silicon nitride, aluminum nitride, a mixture of silicon oxide and zirconium oxide, and a mixture of silicon oxide and aluminum nitride. ..
  • the intermediate refractive index material is at least one of the intermediate refractive index materials as long as the refractive index is between the refractive index of the high refractive index material and the refractive index of the low refractive index material, and preferably the refractive index is adjusted in the above range.
  • the intermediate refractive index material is preferably composed of only the intermediate refractive index substance, and more preferably composed of only one kind of the intermediate refractive index substance.
  • the intermediate refractive index substance aluminum oxide, silicon nitride, and aluminum nitride are preferable, and aluminum oxide is particularly preferable, from the viewpoint that desired optical characteristics and hardness can be obtained when a multilayer film is formed.
  • the nitrides of metals represented by nitride + metal name, oxidation + metal name, oxynitride + metal name, oxides and oxynitrides have a chemical composition ratio or a chemical composition ratio unless otherwise specified. Nitridees, oxides and oxynitrides with non-chemical composition ratios are shown. If necessary, for example, in the case of silicon nitride, it may be described as SiN x .
  • TiZrO x zirconium-doped titanium oxide
  • SiZrO x zirconium-doped silicon oxide (hereinafter referred to as SiZrO x ) layer and SiO 2 layer, Si layer and SiO 2 layer, Ta 2 O 5 layer and SiO 2 layer, TiO 2 layer and SiO 2 layer, Nb 2 O 5 layer and the SiO 2 layer, ZrO 2 layer and the SiO 2 layer, include SnO 2 layer and the SiO 2 layer, TiZrO x layer and the SiO 2 layer, SiN x layer and the Al 2 O 3 layer and the SiO 2 layer, SiZrO x layer And SiO 2 layer, Si layer and SiZrO x layer and SiO 2 layer, Si layer and SnO 2 layer and SiO 2 layer, Si layer and TiZrO x layer and SiO 2 layer, Si layer and SiN x layer and SiO 2 layer, Si A combination of the layer, the Ta 2 O 5 layer and the SiO 2 layer is particularly preferable.
  • the geometric thickness of each layer is appropriately set according to the material used and the required optical characteristics. Since the main target wavelength region of the optical interference film is the infrared region, it is preferable that at least one layer constituting the optical interference film has a geometric thickness of 50 nm or more.
  • the geometric thickness (thickness per layer) of each layer constituting the optical interference film can be set to 1 nm to 500 nm, respectively.
  • the geometric thickness of each layer is more preferably 1 to 400 nm, even more preferably 1 to 400 nm.
  • the decrease in transmittance due to light scattering can be suppressed by setting the upper limit of the film thickness per layer to 500 nm.
  • the reason why the film thickness per layer of the optical interference film is set to 1 nm or more is that the optical interference film actually exists as a continuous film and its function is fully exhibited.
  • the total geometrical film thickness of the optical interference film is preferably 300 nm or more, more preferably 400 nm or more, still more preferably 500 nm or more.
  • the total geometrical film thickness of the optical interference film is preferably 2000 nm or less, more preferably 1500 nm or less, and further preferably 1200 nm or less from the viewpoint of preventing a decrease in transmittance due to light scattering and preventing warpage of the glass substrate.
  • each optical interference film can have the same configuration as described above.
  • the upper limit of the total geometrical film thickness of the optical interference film is preferably 4000 nm in total of the two optical interference films.
  • the laminated structure such as the number of layers, the constituent materials of the layers, the stacking order, and the thickness of the layers in the optical interference film can be appropriately changed according to the required optical characteristics.
  • the optical interference film is composed of a laminated body of an intermediate refractive index layer, a high refractive index layer, and a low refractive index layer
  • the geometric thickness of each layer depends on the material constituting each layer and the required optical characteristics. Is set as appropriate.
  • the optical member 10B shown in FIG. 1B will be described as an example.
  • the first main surface 1a of the glass substrate 1 is located toward the sensor side, and the second main surface 1b is located toward the outside side.
  • the first optical interference film 2 provided on the first main surface 1a of the glass substrate 1 preferably has a configuration in which high refractive index layers and low refractive index layers are alternately laminated from the first main surface 1a side.
  • the second optical interference film 3 provided on the second main surface 1b of the glass substrate 1 has a configuration in which high refractive index layers and low refractive index layers are alternately laminated from the second main surface 1b side. preferable.
  • the first optical interference film 2 is preferably a multilayer film in which TiZrO x layer or Ta 2 O 5 as a high refractive index layer and SiO 2 layer as a low refractive index layer are alternately laminated, for example.
  • a part of TiZrO x layer or Ta 2 O 5 layer as the high refractive index layer is a silicon hydride (hereinafter,. Indicated by SH x) also configurations substituted layer or silicon Si preferred.
  • the second optical interference film 3 for example, TiZrO x layer as a high refractive index layer, and a SiN x layer or a Ta 2 O 5 layer, SiO 2 layer as a low refractive index layer are laminated alternately
  • a multilayer film is preferable from the viewpoint of heat resistance of the multilayer film.
  • the number of layers of the first optical interference film 2 is preferably 6 to 20, and more preferably 6 to 16.
  • the film thickness of each layer is preferably 1 to 300 nm, more preferably 1 to 250 nm.
  • the total film thickness of the first optical interference film 2 is preferably 400 to 1000 nm, more preferably 400 to 600 nm.
  • the number of layers of the second optical interference film 3 is preferably 6 to 16, and more preferably 6 to 112.
  • the film thickness of each layer is preferably 1 to 400 nm, more preferably 1 to 300 nm.
  • the total film thickness of the second optical interference film 3 is preferably 300 to 1200 nm, more preferably 300 to 700 nm.
  • the reflectance of the visible light region of this optical member is adjusted so as to harmonize the appearance with the surroundings according to the environment and the part used, and the first optical interference is adjusted according to Rv1 ave.
  • the film 2 and the second optical interference film 3 may be designed as follows.
  • the optical interference film of either the first optical interference film 2 or the second optical interference film 3, or both optical interference films has a wavelength of 400 to 400 to The maximum visible light reflectance specified in ISO 9050: 2003, in which a glass article having one or more layers that absorb light of 700 nm is incident from the main surface on the opposite side of the sensor at an incident angle of 5 degrees. It is preferable to design the first optical interference film and the glass substrate so that the value is less than 12%.
  • a glass article in which the first optical interference film 2 and the second optical interference film 3 are formed is placed on the opposite side of the sensor.
  • the first optical interference film and the glass substrate can be designed so that the maximum value of the reflectance of visible light specified in ISO 9050: 2003 when the light is incident from the main surface at an incident angle of 5 degrees is less than Rv1 ave + 5%. preferable.
  • the number of layers of the second optical interference film 3 is increased by setting the high refractive index layer to 3 to 10 layers and the low refractive index layer to 3 to 10 layers. It is preferable to use a multilayer film having a thickness of 6 to 20, each layer having a thickness of 10 to 200 nm, and a total thickness of 300 to 1000 nm.
  • the optical interference film can be formed on a glass substrate by a known film forming method. Specifically, it is formed by using a film forming method such as a thermal thin-film deposition method, a sputtering method, or an ion-assisted deposition (IAD: Ion Assisted Deposition) method. In particular, when forming a film having high scratch resistance as the optical interference film, it is preferable to use a sputtering method or an ion-assisted vapor deposition method so that a dense film can be obtained.
  • a film forming method such as a thermal thin-film deposition method, a sputtering method, or an ion-assisted deposition (IAD: Ion Assisted Deposition) method.
  • IAD Ion Assisted Deposition
  • the optical member 10B composed of the glass substrate 1, the first optical interference film 2, and the second optical interference film 3 has been described above with reference to FIG. 1B.
  • the optical member 10B can change the design of the glass substrate 1, the first optical interference film 2, and the second optical interference film 3 as long as the effects of the present invention are not impaired.
  • the optical member 10B may have any constituent elements other than the glass substrate 1, the first optical interference film 2 and the second optical interference film 3 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 antifogging function, an antifouling function, etc., a low radioactive coating, an infrared light shielding coating, a conductive coating, and the like.
  • a coating that imparts a water-repellent function, an antifouling function, or the like is used as the outermost layer of the outer surface of the optical member, and in the optical member 10B, has a thickness of 5 to 20 nm on the main surface 3b of the second optical interference film 3. It is preferable to be provided.
  • the present optical member suppresses the occurrence of distortion in the transmission of infrared light due to heat. Further, when heat resistance at a higher temperature is required, this optical member has an incident angle of 0 ° C. or more and 5 ° C. or less at the wavelength ⁇ s before and after heating the optical member at a temperature of 600 ° C. for 24 hours in the atmosphere.
  • the difference in the maximum transmittance of the incident light (hereinafter, also referred to as “ ⁇ T 600 ° C. ⁇ s ”) is preferably 3% or less. From the viewpoint of further suppressing the influence of heat of infrared light transmission, ⁇ T 600 ° C. ⁇ s is preferably 1.0% or less, and more preferably 0.5% or less.
  • this optical member has an optical member at 300 w / m 2 at 40 ° C. and a xenon lamp at 300 w / m 2 for 24 hours at the above wavelength ⁇ s. It is preferable that the difference in the maximum transmittance of the incident light in the range of the incident angle of 0 degrees or more and 5 degrees or less (hereinafter, also referred to as “ ⁇ T uv ⁇ s ”) is 2% or less. From the viewpoint of further suppressing the influence of infrared light-transmitting ultraviolet rays, ⁇ Tuv ⁇ s is preferably 1% or less, more preferably 0.5% or less.
  • this optical member has an incident angle of 0 degrees or more and 5 degrees or less at the wavelength ⁇ s before and after the optical member is placed in a 1 mol, 20 ° C. HCl solution and left for 6 hours. It is preferable that the difference in the maximum transmittance of the incident light (hereinafter, also referred to as “ ⁇ T HCl ⁇ s ”) is 2% or less. From the viewpoint of further suppressing the influence of infrared light-transmitting acid rain, ⁇ T HCl ⁇ s is preferably 1% or less, more preferably 0.5% or less.
  • the martence hardness of the indentation depth of 50 nm measured on the surface of the optical interference film is larger than the martence hardness of the indentation depth of 50 nm measured on the surface of the glass substrate.
  • the Martens hardness is determined by using a Vickers indenter with a microhardness tester, 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 / 10s. It is the Martens hardness at a pushing depth of 50 nm when a load-unloading test is performed with a unloading speed of 1 mmN / 10s.
  • the Martens hardness with a pressing depth of 50 nm measured under the above measurement conditions is simply referred to as "Martens hardness”.
  • Martens hardness measured at the surface of the glass substrate in the optical member 4N / mm 2 or more, more preferably 4.5 N / mm 2 or more, 5N / mm 2 or more is more preferable.
  • Martens hardness measured at the surface of the optical interference film while satisfying the greater condition than Martens hardness measured at the surface of the glass substrate, 4N / mm 2 or more preferably, 4.5 N / mm 2 or more, more preferably 5, N / mm 2 or more is more preferable.
  • the Martens hardness can be achieved by using a part of the material constituting the optical interference film as a material which is preferable in terms of hardness.
  • Preferred materials include materials containing SiN x , AlN x , Al 2 O 3 , and ZrO 2 .
  • this optical member when the transmittance of light at an incident angle of 60 degrees at a wavelength ⁇ s is 70% or more, it is possible to maintain sensor accuracy at a higher angle (wide range), which is preferable. It is more preferably 75% or more, further preferably 80% or more, even more preferably 85% or more, and most preferably 87% or more.
  • the average reflectance of visible light specified in ISO 9050: 2003 which is incident from at least one surface at an incident angle of 5 degrees, has a mirror effect and unnecessary light is introduced. It is preferable in terms of absence, avoiding high temperatures, and appearance.
  • the average reflectance is more preferably 80% or more, and even more preferably 85% or more.
  • This optical member prevents a decrease in transmittance due to infrared absorption of water when the water contact angle measured on the surface of the optical interference film is applied to the outside of the vehicle as a sensor cover used for the vehicle, for example. From the viewpoint of preventing stains and the like, 90 degrees or more is preferable, and 100 degrees or more is more preferable.
  • the water contact angle of the optical interference film can be increased by coating the outermost surface of the optical interference film with a fluorine-based antifouling agent or diamond-like carbon to a thickness of 1 to 15 nm.
  • Examples of the method of attaching the optical member to a sensor such as a LiDAR sensor as a cover include a method of directly attaching the optical member via an adhesive that transmits infrared light, a method of attaching the optical member to a sensor housing such as a LiDAR sensor, and the like. ..
  • LiDAR sensors are mounted and used on transport aircraft, such as trains, automobiles, ships, and aircraft.
  • This optical member is particularly suitable as a cover for a LiDAR sensor mounted on an automobile.
  • the LiDAR sensor When the LiDAR sensor is mounted on an automobile, it may be mounted on, for example, a bumper, a side mirror, a pillar, a rear portion of an interior mirror, or the like.
  • This optical member is advantageous in that the strength and designability can be adjusted according to the application location.
  • glass substrates As glass substrates, G1 to G24 glass substrates showing the composition and characteristics in Tables 1 to 3 were prepared.
  • the glass substrates G1 to G15 and G17 to G24 were produced by the following methods.
  • the glass substrate G16 is RG780 (trade name) manufactured by Schott AG.
  • Ingredients are prepared so as to have the compositions shown in Tables 1 to 3 in terms of oxide-based mass percentage display, placed in a platinum crucible, placed in a resistance heating electric furnace at 1550 ° C., melted for 2 hours, and removed. Foam, homogenized. Since the compositions shown in Tables 1 to 3 are listed by rounding off significant figures, the total content of each component in the glass composition may not be 100%.
  • the obtained glass was poured into a mold material, held at a temperature of Tg + 50 ° C. for 1 hour, and then cooled to room temperature at a rate of 1 ° C./min to obtain a glass block.
  • the glass block was cut and polished, and both sides were mirror-finished to obtain a glass substrate of each example having the thickness (unit: mm) shown in Tables 1 to 3.
  • the glass substrates G1 to G18 and G20 to G24 are single plates, and the glass substrate G19 is made of two 2.1 mm thick glass plates made of glass having the same composition as the glass substrate G18 (however, one of them is laminated glass). It is a laminated glass in which an infrared transmissive black ink layer is provided on a main surface in contact with an interlayer film (made of polyvinyl butyral, 0.75 mm thick).
  • thermomechanical analyzer TD5000SA manufactured by NETZSCH
  • TMA thermomechanical analyzer
  • the values in parentheses are the measured values of the coefficient of linear expansion measured by the thermomechanical analyzer, each glass whose coefficient of linear expansion was measured by the thermomechanical analyzer, and the glass for which the coefficient of linear expansion is calculated. It is a calculated value obtained by the linear regression method from the difference in glass composition between. Further, the numerical value of " * 1 " in Table 2 is an actually measured value of the coefficient of linear expansion at 200 to 300 ° C.
  • optical characteristics were measured for the following items using a spectrophotometer (V-780 automatic absolute reflectance measurement system, manufactured by JASCO Corporation).
  • Tv, T max400-700 The average transmittance at a wavelength of 400 to 700 nm at an incident angle of 0 degrees was defined as Tv.
  • T max400-700 For light incident at a range of less than an incident angle of 0 degrees 5 degrees, the maximum value of the transmittance at a wavelength of 400 ⁇ 700 nm was T max400-700.
  • Wavelength range width (3% or more), (25% or more), (30% or more) In the wavelength range of 400 to 700 nm, the width of the wavelength range in which the light transmittance is 3% or more, 25% or more, and 30% or more with respect to the light incident in the range of the incident angle of 0 degrees or more and 5 degrees or less. I asked for each.
  • T 365 , T 800 , T 905 , T 1050 , T 1550 The transmittances at wavelengths of 365 nm, 800 nm, 905 nm, 1050 nm, and 1550 nm at an incident angle of 0 ° are shown by T 365 , T 800 , T 905 , T 1050 , and T 1550 , respectively.
  • Transparent L * , Transparent a * , Transparent b * ISO9050: is the for transmitted light obtained by irradiating the visible light defined 2003, the CIE1976L * a * b * chromaticity coordinates, transmitting L *, transmission a *, showed a transmission b *.
  • T 800-60 deg , T 905-60 deg , T 1050-60 deg , T 1550-60 deg Each wavelength 800nm at an incident angle of 60 °, 905nm, 1050nm, the transmittance of 1550nm, T 800-60deg, T 905-60deg, T 1050-60deg, indicated by T 1550-60deg.
  • the compressive stress (generated stress) of the surface strengthened under different cooling conditions was measured as follows.
  • the wave surface aberration was measured by the same method as that of the optical member described later. The results are shown in Table 4.
  • a disk having a mirror surface on the entire surface was produced from a glass substrate before the compressive stress layer was formed.
  • the photoelastic constant was determined by the disk compression method.
  • a glass having a size of 50 ⁇ 50 ⁇ 4 mm having a mirror surface on the entire surface was prepared, and the glass was heated to a desired temperature (physical strengthening temperature) in 140 seconds using a jig made of SUS, and then held for 70 seconds. Then, compressed air was blown at a desired wind pressure to quench the mixture. After cutting the prepared quenching glass, the cut surface was optically polished and the retardation was measured by a birefringence measuring device. Then, the generated stress (compressive stress on the surface (unit: MPa)) was obtained by dividing the measured retardation value by the photoelastic constant and the glass thickness.
  • Stepping stone resistance was evaluated by performing a Grabello test.
  • a glass substrate 50 ⁇ 50 ⁇ 4 mm having a mirror surface on the entire surface was prepared from the glass substrate. This substrate was attached to a SUS jig having a hole of 45 ⁇ 45, and was attached so that only the peripheral edge of the glass substrate was in contact with the jig. Furthermore, protection was performed using double-sided tape so that the edge of the glass was not exposed.
  • the stepping stones were set so as to collide with the glass substrate at an angle of 45 °, and the gravure test was carried out under the following conditions. The gravure test was carried out using a stepping stone tester JA400 manufactured by Suga Test Instruments Co., Ltd.
  • Condition A Injection pressure 0.5MPa Projection material Basalt No. 6 Projection amount 500ml
  • Condition B Injection pressure 0.2MPa Projection material Basalt No. 7 Projection amount 50g When the glass was broken due to this, x was given, and when the glass was not broken, it was given 0.
  • the scratch depths at any three points on the glass surface were measured with a laser microscope, the deepest part was taken as the scratch depth, and the average value was calculated and used as the scratch depth.
  • each layer is formed by the following method, and the optical members shown in Tables 5 and 6 are laminated.
  • Tables 5 and 6 the uppermost layer of the table is a layer located on the sensor side, and the lowermost layer is a layer which is regarded as the outermost layer when viewed from the outside.
  • the laminated body showing the laminated structure above the substrate is the first optical interference film 2, and the laminated body showing the laminated structure below the substrate is the second optical interference film 3.
  • the total film thickness of the first optical interference film 2 is “total film thickness 1" and the total film thickness of the second optical interference film 3 is “total film thickness 2" together with the film thickness of each layer. The total is described as “total film thickness (1 + 2)”.
  • each layer was laminated on the main surface of the glass substrate in the order and thickness shown in Tables 5 and 6.
  • the high refractive index layer TiZrO x layer, Ta 2 O 5 layer, SiN x layer, SH x layer, was used.
  • An Al 2 O 3 layer was used as the intermediate refractive index layer, and a SiO 2 layer was used as the low refractive index layer.
  • the constituent materials of each layer are described as TiZrOx, Ta2O5, SiNx, SHx, Al2O3, and SiO2, respectively.
  • a pure Ta target was used to form the Ta 2 O 5 layer, 250 sccm of argon was introduced as the discharge gas in the film forming chamber, 5 kW of electric power was applied to the target, and 90 sccm of oxygen was introduced as the discharge gas in the reaction chamber. A 3 kW electric power was applied to the radical source to form a film.
  • a B-doped polycrystalline Si target was used to form the SiN x layer, 90 sccm nitrogen was introduced as the discharge gas in the discharge gas chamber of the film forming chamber, and 1 kW of electric power was applied to the radical source to form the film.
  • a B-doped polycrystalline Si target was used to form the SiH x layer, and 350 sccm of hydrogen was added as a discharge gas in the film forming chamber at an atomic ratio of 7% while the temperature of the substrate was raised to 200 ° C and the temperature was maintained.
  • a mixed gas of added argon was introduced, 5 kW of electric power was applied to the target, and a mixed gas of argon to which 150 sccm of hydrogen was added at an atomic ratio of 7% was introduced as a discharge gas in the reaction chamber, and 4 kW was introduced into the radical source.
  • the film was formed by applying the power of.
  • a B-doped polycrystalline Si target was used to form the SiO 2 layer, 250 sccm of argon was introduced as the discharge gas in the film forming chamber, 7 kW of electric power was applied to the target, and 90 sccm of oxygen was used as the discharge gas in the reaction chamber. It was introduced and a power of 3 kW was applied to the radical source to form a film.
  • a pure Al target was used to form the Al 2 O 3 layer, 250 sccm of argon was introduced as the discharge gas in the film forming chamber, 7 kW of electric power was applied to the target, and 80 sccm of oxygen was introduced as the discharge gas in the reaction chamber. A power of 1.5 kW was applied to the radical source to form a film.
  • FIG. 2 shows a spectral transmittance curve (solid line) of the optical member of Example 6 at an incident angle of 0 degrees and a spectral transmittance curve (broken line) of the glass substrate G4 at an incident angle of 0 degrees.
  • Spectrophotometric measurement A spectrophotometer (V-780 automatic absolute reflectance measurement system, manufactured by JASCO Corporation) was used, and the reflectance and transmittance were measured using an angle variable unit in absolute transmission and absolute reflection measurement. When the incident angle exceeds 5 degrees, the transmittance and reflectance are measured with S-polarized light and P-polarized light sources, respectively, and the average value of the measured values using S-polarized light and P-polarized light as the light source is used as the transmittance and reflectance. And said.
  • the transmittance was measured by irradiating the first optical interference film 2 of the optical member with measurement light.
  • the reflectance is measured by irradiating the first optical interference film 2 of the optical member with the measurement light to measure R2, and irradiating the second optical interference film 3 of the optical member to measure the reflectance.
  • R1 A spectrophotometer (V-780 automatic absolute reflectance measurement system, manufactured by JASCO Corporation) was used, and the reflectance and transmittance were measured using an angle
  • Tv, T max400-700 The average transmittance of light having a wavelength of 400 to 700 nm incident in a range of an incident angle of 0 degrees or more and 5 degrees or less was defined as Tv.
  • T min (2) ; T min (2) 800 , T min (2) 905 , T min (2) 1050 , T min (2) 1550 The minimum values of the transmittance of light incident in the range of incident angles of 0 degrees or more and 5 degrees or less when ⁇ s is 800 nm, 905 nm, 1050 nm, and 1550 nm are T min (2) 800 , T min (2) 905 , and T, respectively. It is shown by min (2) 1050 and T min (2) 1550 .
  • the surface shape is determined by the residue excluding the chill component from the result of measuring the surface shape with a laser interference type flatness meter (Verifire Mark IV manufactured by Zygo), and the difference between the maximum value and the minimum value of the surface shape is called wave surface aberration. did.
  • the measurement wavelength was 633 nm, and the measurement location was ⁇ 30 mm.
  • the change in maximum transmittance ⁇ T 600 ° C. ⁇ s was calculated.
  • the present invention is sufficiently used as a sensor cover to conceal the sensor by lowering the transmittance of visible light, suppress malfunction of the sensor due to heat, and do not distort the infrared light used for the LiDAR sensor.
  • An optical member that transmits light can be obtained. Since the optical member of the present invention has the above-mentioned characteristics, it is suitable as a cover for a LiDAR sensor mounted on a vehicle, particularly an automobile.

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Abstract

L'invention concerne un élément optique pour couvercle de capteur qui est équipé d'un substrat de verre non cristallin, et d'un film d'interférence lumineuse qui est placé sur au moins sur une des faces principales dudit substrat de verre. Cet élément optique est équipé d'une région dans laquelle, vis-à-vis d'une lumière incidente dans une plage d'angle d'incidence supérieur ou égal à 0 degré et inférieur ou égal à 5 degrés, la transmittance maximale à l'intérieur d'une région de longueur d'ondes supérieure ou égale à 400nm et inférieure ou égale à 700nm, est inférieure ou égale à 10%, la valeur minimale de transmittance de la lumière à une longueur d'ondes (λｓ) prédéfinie à l'intérieur d'une région de longueur d'ondes supérieure ou égale à 800nm et inférieure ou égale à 180nm, est supérieure ou égale à ８６,５％, et la différence de transmittance d'une lumière incidente dans une plage d'angle d'incidence supérieur ou égal à 0 degré et inférieur ou égal à 5 degrés à ladite longueur d'ondes (λｓ) avant et après chauffage pendant 24 heures à une température de 200°C sous atmosphère dudit élément optique, est inférieure ou égale à 3%.
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EP4155787A1 (fr) * 2021-09-28 2023-03-29 Viavi Solutions Inc. Filtre optique d'interférence
EP4155786A1 (fr) * 2021-09-28 2023-03-29 Viavi Solutions Inc. Filtre optique d'interférence
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EP4191294A1 (fr) * 2021-12-01 2023-06-07 Viavi Solutions Inc. Filtre optique d'interférence
EP4215499A1 (fr) * 2022-01-19 2023-07-26 Schott Ag Composant optique et composition de verre ainsi que son utilisation

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CN115903112A (zh) * 2020-12-25 2023-04-04 Ａｇｃ株式会社 滤光片
CN115903112B (zh) * 2020-12-25 2024-03-19 Ａｇｃ株式会社 滤光片
EP4155787A1 (fr) * 2021-09-28 2023-03-29 Viavi Solutions Inc. Filtre optique d'interférence
EP4155786A1 (fr) * 2021-09-28 2023-03-29 Viavi Solutions Inc. Filtre optique d'interférence
US11867935B2 (en) 2021-09-28 2024-01-09 Viavi Solutions Inc. Optical interference filter
EP4191294A1 (fr) * 2021-12-01 2023-06-07 Viavi Solutions Inc. Filtre optique d'interférence
EP4215499A1 (fr) * 2022-01-19 2023-07-26 Schott Ag Composant optique et composition de verre ainsi que son utilisation
EP4223712A1 (fr) * 2022-01-19 2023-08-09 Schott Ag Composant optique et composition de verre ainsi que leur utilisation

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