WO2023218938A1 - Uv-transmitting glass - Google Patents

Uv-transmitting glass Download PDF

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Publication number
WO2023218938A1
WO2023218938A1 PCT/JP2023/016202 JP2023016202W WO2023218938A1 WO 2023218938 A1 WO2023218938 A1 WO 2023218938A1 JP 2023016202 W JP2023016202 W JP 2023016202W WO 2023218938 A1 WO2023218938 A1 WO 2023218938A1
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WO
WIPO (PCT)
Prior art keywords
glass
content
transmittance
ultraviolet
mass
Prior art date
Application number
PCT/JP2023/016202
Other languages
French (fr)
Japanese (ja)
Inventor
幸市 橋本
英佑 高尾
俊輔 藤田
修 小谷
Original Assignee
日本電気硝子株式会社
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.)
Filing date
Publication date
Priority claimed from JP2022167700A external-priority patent/JP2023168201A/en
Application filed by 日本電気硝子株式会社 filed Critical 日本電気硝子株式会社
Publication of WO2023218938A1 publication Critical patent/WO2023218938A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C15/00—Surface treatment of glass, not in the form of fibres or filaments, by etching
    • 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
    • C03C3/11—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen
    • C03C3/112—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine
    • C03C3/115—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine containing boron
    • C03C3/118—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine containing boron containing aluminium
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01J—MEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
    • G01J1/00—Photometry, e.g. photographic exposure meter
    • G01J1/02—Details
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01J—MEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
    • G01J1/00—Photometry, e.g. photographic exposure meter
    • G01J1/02—Details
    • G01J1/04—Optical or mechanical part supplementary adjustable parts

Definitions

  • the present invention relates to ultraviolet-transparent glass.
  • a flame sensor that detects ultraviolet light with a wavelength of 185 to 260 nm that is generated by flames has been developed, and a method has been proposed that uses this flame sensor to detect fires and flames from combustion devices.
  • Ultraviolet transmitting glass for example, Patent Document 1
  • Patent Document 1 which has high transmittance in the deep ultraviolet region, is used for containers and window materials that house such flame sensors.
  • ultraviolet-transmissive glass As the outer cylinder of the flame sensor, high detection sensitivity can be achieved continuously.
  • conventional ultraviolet transmitting glasses have a problem in that their transmittance is low, especially in the deep ultraviolet region of wavelengths from 200 to 250 nm.
  • the present invention aims to obtain a glass having higher transmittance than conventional products in the deep ultraviolet region.
  • the F content at a depth of 15 ⁇ m from the glass surface is x (mass%)
  • the F content at a depth of 1 ⁇ m from the glass surface is y (mass%)
  • y /x is 0.8 or more.
  • the "F content” can be measured with a commercially available electron beam microanalyzer (for example, EPMA-1720H manufactured by Shimadzu Corporation).
  • the transmittance (%) at a thickness of 0.5 mm and a wavelength of 200 nm is T200 , it is preferable that T200 ⁇ 69.
  • the "transmittance at a wavelength of 200 nm” can be measured with a commercially available spectrophotometer (for example, UV-3100PC manufactured by Shimadzu Corporation).
  • the ultraviolet transmitting glass of the present invention preferably has a thickness of 0.2 to 2 mm and is tubular.
  • the ultraviolet transmitting glass of the present invention has, as a glass composition, SiO 2 55 to 75%, Al 2 O 3 1 to 10%, B 2 O 3 10 to 30%, CaO 0 to 5%, BaO 0 to 5%, Li 2 O+Na 2 O+K 2 O 1-15%, TiO 2 0-0.001%, Fe 2 O 3 0-0.001%, and F 0.5-7%.
  • A+B+C refers to the total amount of component A, component B, and component C.
  • Li2O + Na2O + K2O refers to the total amount of Li2O , Na2O and K2O .
  • the ultraviolet transmitting glass of the present invention is preferably used for flame sensors.
  • the method for producing ultraviolet transmitting glass of the present invention is characterized by forming glass into a tubular shape and then immersing the tubular glass in an acid solution for etching.
  • y/x is 0.8 or more, preferably 0.85 or more, particularly 0.9 or more. If y/x is too small, Fe 3+ contained near the glass surface will be difficult to reduce, and the transmittance in the deep ultraviolet region will tend to decrease. Note that the upper limit value of y/x is not particularly limited, but is realistically 1.2 or less. Moreover, the specific numerical value of y/x is as follows.
  • x is 0.5 to 7%, 0.6 to 5%, particularly 0.7 to 3%. If x is too small, the content of F inside the glass will decrease, Fe 3+ contained inside the glass will be difficult to reduce, and the transmittance in the deep ultraviolet region will tend to decrease. On the other hand, if x is too large, it becomes difficult to vitrify.
  • y is 0.4 to 8.4%, 0.45 to 6%, 0.5 to 5%, particularly 0.6 to 3%. If y is too small, the content of F near the glass surface will decrease, making it difficult for Fe 3+ contained near the glass surface to be reduced, and the transmittance in the deep ultraviolet region will tend to decrease. On the other hand, if y is too large, it becomes difficult to vitrify.
  • the transmittance (%) at a thickness of 0.5 mm and a wavelength of 200 nm is T 200
  • T 220 is the transmittance (%) at a thickness of 0.5 mm and a wavelength of 220 nm
  • T 220 ⁇ 79, particularly T 220 ⁇ 80 If the transmittance at a thickness of 0.5 mm and a wavelength of 220 nm is too low, it will be difficult for ultraviolet light to pass through, and the performance of the light source or device mounted thereon will likely deteriorate.
  • T 250 is the transmittance (%) at a thickness of 0.5 mm and a wavelength of 250 nm
  • T 250 ⁇ 87, particularly T 250 ⁇ 88 it is preferable that T 250 ⁇ 87, particularly T 250 ⁇ 88. If the transmittance at a thickness of 0.5 mm and a wavelength of 250 nm is too low, it will be difficult for ultraviolet light to pass through, and the performance of the light source or device mounted thereon will likely deteriorate.
  • the strain point of the ultraviolet transmitting glass of the present invention is preferably 400°C or higher, 410°C or higher, particularly 415°C or higher. If the strain point of the ultraviolet-transmitting glass is too low, for example, when forming a functional film on the surface, the glass is likely to undergo unintended deformation during a high-temperature film-forming process. Note that the upper limit of the strain point is not particularly limited, but realistically it is 600° C. or less.
  • the softening point of the ultraviolet transmitting glass of the present invention is preferably 850°C or lower, 800°C or lower, or 750°C or lower, particularly 700°C or lower. If the softening point is too high, it will be difficult to reheat the glass. Note that the lower limit of the softening point is not particularly limited, but realistically it is 600°C or higher.
  • the temperature at which the ultraviolet transmitting glass of the present invention has a viscosity of 10 2.5 dPa ⁇ s is preferably 1540°C or lower, 1520°C or lower, 1500°C or lower, particularly 1480°C or lower. If the temperature at 10 2.5 dPa ⁇ s is too high, the load on the glass melting furnace increases, the meltability decreases, and the manufacturing cost of glass tends to rise.
  • the "temperature at 10 2.5 dPa ⁇ s" can be measured by the platinum ball pulling method. Note that the lower limit of the temperature at 10 2.5 dPa ⁇ s is not particularly limited, but realistically it is 1300° C. or higher.
  • the average linear thermal expansion coefficient of the ultraviolet transmitting glass of the present invention in the temperature range of 30 to 380°C is preferably 30 x 10 -7 /°C or more, particularly 35 x 10 -7 /°C or more, and 95 x 10 -7 /°C or less, particularly preferably 80 ⁇ 10 -7 /°C or less. If the average linear thermal expansion coefficient is too low, it will be difficult to match the thermal expansion coefficients of various members such as sensor terminals. On the other hand, if the average linear thermal expansion coefficient is too high, the glass will be easily damaged by thermal shock.
  • the liquidus temperature of the ultraviolet transmitting glass of the present invention is preferably 1120°C or lower, 1100°C or lower, 1080°C or lower, 1050°C or lower, 1000°C or lower, 950°C or lower, 900°C or lower, particularly 850°C or lower.
  • the viscosity at the liquidus temperature is 10 4.0 dPa ⁇ s or more, 10 4.3 dPa ⁇ s or more, 10 4.5 dPa ⁇ s or more, 10 4.8 dPa ⁇ s or more, 10 5.1 dPa ⁇ s
  • it is preferably 10 5.3 dPa ⁇ s or more, particularly 10 5.5 dPa ⁇ s or more. In this way, the devitrification resistance is improved and it becomes easier to mold by a down-draw method, particularly an overflow down-draw method, so that it becomes easier to produce glass in a desired shape.
  • the Young's modulus of the ultraviolet transmitting glass of the present invention is preferably 40 GPa or more, particularly 45 GPa or more. If the Young's modulus is too low, it will be difficult for the glass to maintain its rigidity on the conveyance line in the device manufacturing process, and the glass will be more likely to deform, warp, or break.
  • the ultraviolet transmitting glass of the present invention has, as a glass composition, SiO 2 55-75%, Al 2 O 3 1-10%, B 2 O 3 10-30%, CaO 0-5%, BaO 0-0. 5%, Li 2 O+Na 2 O+K 2 O 1-15%, TiO 2 0-0.001%, Fe 2 O 3 0-0.001%, and F 0.5-7%.
  • SiO 2 is the main component that forms the skeleton of glass.
  • the content of SiO 2 is preferably 55-75%, 58-70%, particularly 65-69%. If the content of SiO 2 is too low, Young's modulus and acid resistance tend to decrease. On the other hand, if the content of SiO 2 is too high, the high-temperature viscosity becomes high and the meltability tends to decrease, and in addition, devitrification crystals such as cristobalite tend to precipitate, and the liquidus temperature tends to increase. Become.
  • Al 2 O 3 is a component that increases Young's modulus and also suppresses phase separation and devitrification.
  • the content of Al 2 O 3 is preferably 1 to 10%, 2 to 9%, particularly 3 to 8%. If the content of Al 2 O 3 is too small, the Young's modulus tends to decrease, and the glass tends to undergo phase separation and devitrification. On the other hand, if the content of Al 2 O 3 is too large, the high temperature viscosity will increase and the meltability will tend to decrease.
  • B 2 O 3 is a component that improves melting properties and devitrification resistance, and also improves susceptibility to scratches and increases strength.
  • the content of B 2 O 3 is preferably 10 to 30%, 13 to 28%, particularly 15 to 25%. If the content of B 2 O 3 is too small, meltability and devitrification resistance tend to decrease, and resistance to hydrofluoric acid-based chemicals tends to decrease. On the other hand, if the content of B 2 O 3 is too large, Young's modulus and acid resistance tend to decrease.
  • CaO is a component that lowers high temperature viscosity and increases meltability. Moreover, among alkaline earth metal oxides, since the raw material to be introduced is relatively inexpensive, it is a component that reduces raw material costs.
  • the content of CaO is preferably 0 to 5%, 0.01 to 1%, particularly 0.1 to 0.8%. If the content of CaO is too high, the glass tends to devitrify.
  • BaO is a component that increases resistance to devitrification.
  • the content of BaO is preferably 0 to 5%, 0.1 to 3%, particularly 0.5 to 1.5%. If the BaO content is too high, the glass will easily devitrify.
  • Li 2 O, Na 2 O, and K 2 O are alkali metal oxide components that lower high-temperature viscosity, significantly increase meltability, and contribute to initial melting of the glass raw material.
  • the content of Li 2 O+Na 2 O+K 2 O is preferably 1 to 15%, 2 to 10%, particularly 3 to 6%. If the content of Li 2 O + Na 2 O + K 2 O is too small, the meltability tends to decrease. On the other hand, if the content of Li 2 O+Na 2 O+K 2 O is too large, the coefficient of thermal expansion may become unduly high.
  • Li 2 O is a component that lowers high-temperature viscosity, significantly increases meltability, and contributes to initial melting of the glass raw material.
  • the content of Li 2 O is preferably 0 to 5%, 0 to 3%, particularly 0.1 to 1.2%. If the content of Li 2 O is too large, the glass tends to undergo phase separation.
  • Na 2 O is a component that lowers high-temperature viscosity, significantly increases meltability, and contributes to initial melting of the glass raw material. It is also a component for adjusting the coefficient of thermal expansion.
  • the content of Na 2 O is preferably 0 to 10%, 0 to 8%, 1 to 5%, particularly 1 to 3%. If the content of Na 2 O is too large, the coefficient of thermal expansion may become unduly high.
  • K 2 O is a component that lowers high temperature viscosity, significantly increases meltability, and contributes to the initial melting of the glass raw material. It is also a component for adjusting the coefficient of thermal expansion.
  • the content of K 2 O is preferably 0 to 10%, 0.1 to 5%, particularly 0.5 to 3%. If the content of K 2 O is too large, the coefficient of thermal expansion may become unduly high.
  • TiO 2 is a component that reduces transmittance in the deep ultraviolet region.
  • the content of TiO 2 is preferably 0.001% or less, 0.0008% or less, particularly 0.0001 to 0.0006%. If the content of TiO 2 is too large, the glass becomes colored and the transmittance in the deep ultraviolet region tends to decrease.
  • Fe 2 O 3 is a component that reduces transmittance in the deep ultraviolet region.
  • the content of Fe 2 O 3 is preferably 0.001% or less, 0.0001 to 0.0009%, particularly 0.00001 to 0.0008%. If the content of Fe 2 O 3 is too large, the glass becomes colored and the transmittance in the deep ultraviolet region tends to decrease.
  • Fe ions in iron oxide exist in the state of Fe 2+ or Fe 3+ . If the proportion of Fe 2+ is too small, the transmittance in deep ultraviolet rays tends to decrease. Therefore, the mass ratio of Fe 2+ /(Fe 2+ +Fe 3+ ) in the iron oxide contained in the ultraviolet transmitting glass of the present invention is 0.1 or more, 0.2 or more, 0.3 or more, 0.4 or more, especially It is preferable that it is 0.5 or more.
  • F is a component that reduces Fe 3+ contained in the glass and improves the transmittance in the deep ultraviolet region. It is also a component that lowers viscosity and increases meltability.
  • the content of F is preferably 0.5 to 7%, 0.6 to 5%, particularly 0.7 to 3%. If the F content is too low, it will be difficult to obtain the above effects. On the other hand, if the F content is too high, it becomes difficult to vitrify.
  • SrO is a component that increases resistance to devitrification.
  • the content of SrO is preferably 0 to 7%, 0 to 5%, 0 to 3%, particularly 0 to 1%. If the content of SrO is too large, the glass tends to devitrify.
  • ZrO 2 is a component that improves acid resistance, but if it is included in a large amount in the glass composition, the glass tends to devitrify. Therefore, the content of ZrO 2 is preferably 0.1% or less, 0.001 to 0.02%, particularly 0.0001 to 0.01%.
  • MoO 3 is a component that is contained as an impurity from within the furnace during production, but if it is contained in a large amount in the glass composition, there is a risk of reducing the transmittance in the deep ultraviolet region. Therefore, the content of MoO 3 is preferably 0.05% or less, 0.005 to 0.001%, particularly 0.0001 to 0.0005%.
  • the shape of the ultraviolet transmitting glass of the present invention can be set arbitrarily.
  • the shape of the ultraviolet transmitting glass of the present invention can be, for example, a flat plate, a curved plate, a straight tube, a curved tube, a rod, a sphere, a container, or a block.
  • the thickness of the ultraviolet transmitting glass is preferably 0.2 to 2 mm, particularly 0.25 to 1.9 mm, and preferably has a tubular shape such as a straight tube shape or a curved tube shape. preferable.
  • the ultraviolet transmittance decreases as the thickness of the glass increases, but since the ultraviolet transmitting glass of the present invention has high transmittance in the wavelength region of 250 nm or less, even if the thickness is increased compared to conventional products. High transmittance can be maintained in the same wavelength range.
  • the surface roughness Ra of the surface of the ultraviolet transmitting glass of the present invention is preferably 10 nm or less, 9 nm or less, 8 nm or less, 7 nm or less, 6 nm or less, 5 nm or less, 4 nm or less, 3 nm or less, 2 nm or less, particularly 1 nm or less. . If the surface roughness Ra of the surface is too large, the transmittance in deep ultraviolet rays tends to decrease.
  • the ultraviolet transmitting glass of the present invention can be produced, for example, by mixing various glass raw materials to obtain a glass batch, then melting this glass batch, clarifying and homogenizing the obtained molten glass, and molding it into a predetermined shape. It can be made with
  • a reducing agent as part of the glass raw material.
  • Fe 3+ contained in the glass is reduced and the transmittance of deep ultraviolet rays is improved.
  • materials such as wood powder, carbon powder, metal aluminum, metal silicon, and aluminum fluoride can be used, and among these, metal silicon and aluminum fluoride are preferred.
  • metal silicon as a part of the glass raw material, and the amount added is 0.001 to 3% by mass, 0.005% by mass based on the total mass of the glass batch. -2% by weight, preferably 0.01-1% by weight, particularly 0.05-0.75% by weight. If the amount of metal silicon added is too small, Fe 3+ contained in the glass will not be reduced, and the transmittance in deep ultraviolet rays will tend to decrease. On the other hand, if the amount of metal silicon added is too large, the glass tends to be colored brown.
  • AlF 3 aluminum fluoride
  • the amount added is 0.01 to 2% by mass in terms of F, 0.05% by mass based on the total mass of the glass batch. It is preferably from 1.5% by weight, particularly from 0.3 to 1.5% by weight. If the amount of aluminum fluoride added is too small, Fe 3+ contained in the glass will not be reduced, and the transmittance in deep ultraviolet rays will tend to decrease. On the other hand, if the amount of aluminum fluoride added is too large, there is a possibility that F gas will remain in the glass as bubbles.
  • the method for producing ultraviolet-transparent glass of the present invention when forming the ultraviolet-transparent glass into a flat plate shape, it is preferable to use a down-draw method or an overflow down-draw method.
  • molten glass overflows from both sides of a heat-resistant gutter-like structure, and the overflowing molten glass joins at the bottom end of the gutter-like structure, stretching downward to form a glass plate. This is the way to do it.
  • the surface of the glass plate that is to become the surface does not come into contact with the trough-like refractories and is formed as a free surface.
  • the structure and material of the gutter-like structure are not particularly limited as long as desired dimensions and surface accuracy can be achieved.
  • the method of applying force when performing downward stretch molding is not particularly limited. For example, a method may be adopted in which a heat-resistant roll having a sufficiently large width is rotated while in contact with the glass, or a plurality of pairs of heat-resistant rolls are brought into contact only near the end surface of the glass. You may adopt the method of stretching.
  • the method for producing ultraviolet-transparent glass of the present invention when forming the ultraviolet-transparent glass into a tubular shape, it is preferable to use a down-draw method, a bellows method, a Danner method, or the like.
  • the Danner method is a method in which molten glass is rolled down and wound around the upper end of a heat-resistant sleeve-like structure arranged at an angle, and the molten glass that has flowed down to the lower end is stretched and formed to form a glass tube.
  • a slot-down method for example, a slot-down method, a redraw method, a float method, etc. can also be adopted.
  • the content of F in the surface layer of the glass tends to decrease in some cases.
  • it is possible to increase the F content near the glass surface by immersing the glass in an acid solution and etching it to remove the surface layer where the F content has decreased.
  • the acid used for the etching treatment nitric acid, hydrofluoric acid, sulfuric acid, hydrochloric acid with a concentration of 3 to 50% by mass, or a mixed acid consisting of at least two of the above-mentioned acids with an acid concentration of 3 to 50% by mass, etc. can be used.
  • the immersion time is preferably 1 minute or more, 3 minutes or more, particularly 5 minutes or more.
  • the immersion time is too short, etching may be insufficient and the F content near the glass surface may not increase.
  • the upper limit of the immersion time is not particularly limited, but realistically it is 20 minutes or less.
  • the temperature of the acid is preferably 20°C or higher, 25°C or higher, particularly 30°C or higher. If the temperature of the acid is too low, etching may be insufficient and the F content near the glass surface may not increase.
  • the upper limit of the temperature of the acid is not particularly limited, it is realistically 95°C or lower. Note that it is also possible to remove the surface layer portion where the F content has decreased by physical polishing or the like.
  • Table 1 shows Examples (Samples No. 1 to 5) of the present invention and Comparative Examples (Sample No. 6).
  • a glass batch prepared by mixing the glass raw materials shown in the table so as to have the glass composition shown in the table was placed in a platinum crucible and melted at 1600°C for 6 hours.
  • the obtained molten glass was stirred using a platinum stirrer to homogenize it.
  • the molten glass was poured onto a carbon plate, formed into a flat plate shape, and then slowly cooled from a temperature approximately 20°C higher than the annealing point to room temperature at a rate of 3°C/min, and then etched under the conditions shown in the table. I did it.
  • Transmittance was measured for each sample obtained.
  • the transmittance is a value obtained by measuring the spectral transmittance in the thickness direction using a double beam spectrophotometer (UV-3100PC manufactured by Shimadzu Corporation).
  • UV-3100PC manufactured by Shimadzu Corporation
  • samples having the thicknesses listed in Table 1 and polished on both sides to optically polished surfaces (mirror surfaces) were used.
  • the surface roughness Ra of the surfaces of these measurement samples was measured by AFM, it was 0.5 to 1.0 nm in a measurement area of 10 ⁇ m ⁇ 10 ⁇ m.
  • the F content x (mass %) at a depth of 15 ⁇ m from the glass surface, and the F content y (mass %) at a depth of 1 ⁇ m from the glass surface are It was measured by line analysis using a microanalyzer (EPMA-1720H manufactured by Shimadzu Corporation).
  • sample No. with y/x of 0.81 or more had high transmittance for ultraviolet light with a wavelength of 200 to 250 nm.
  • sample No. with a small y/x of 0.71 No. 6 had a low transmittance of ultraviolet light with a wavelength of 200 to 250 nm. It was also found that the larger y/x, the higher the transmittance of ultraviolet light with a wavelength of 200 to 250 nm.
  • the molten glass was poured out and formed into a flat plate shape.
  • it is formed into a flat plate shape using an overflow down-draw method, etc., with both surfaces unpolished. It is preferable to use it.
  • it is preferable to shape

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Abstract

Provided is a UV-transmitting glass having a high transmissivity of UV light in the far UV region, particularly light having a wavelength between 200 nm and 250 nm.　This UV-transmitting glass is characterized by having a y/x of 0.8 or greater where x is the F content (mass%) at a depth of 15 μm from the glass surface and y is the F content (mass%) at a depth of 1 μm from the glass surface.

Description

紫外線透過ガラスUV transparent glass
　本発明は、紫外線透過ガラスに関する。 The present invention relates to ultraviolet-transparent glass.
　炎が発生する１８５～２６０ｎｍの波長の紫外線を検出する炎センサが開発され、その炎センサを用いて、火災や燃焼装置の炎を検知する方法が提案されている。このような炎センサを収容する容器や窓材には、深紫外域の透過率が高い紫外線透過ガラス（例えば、特許文献１）が用いられている。 A flame sensor that detects ultraviolet light with a wavelength of 185 to 260 nm that is generated by flames has been developed, and a method has been proposed that uses this flame sensor to detect fires and flames from combustion devices. Ultraviolet transmitting glass (for example, Patent Document 1), which has high transmittance in the deep ultraviolet region, is used for containers and window materials that house such flame sensors.
国際公開２０１７／０５７３７５号公報International Publication No. 2017/057375
　炎センサでは、紫外線透過ガラスを外筒として用いることによって、高い検出感度が持続して得られる。しかし、従来の紫外線透過ガラスでは、その透過率、特に、波長２００～２５０ｎｍの深紫外域の透過率が低く、課題となっていた。 By using ultraviolet-transmissive glass as the outer cylinder of the flame sensor, high detection sensitivity can be achieved continuously. However, conventional ultraviolet transmitting glasses have a problem in that their transmittance is low, especially in the deep ultraviolet region of wavelengths from 200 to 250 nm.
　以上に鑑み、本発明は、深紫外域において従来品よりも高い透過率を有するガラスを得ることを目的とする。 In view of the above, the present invention aims to obtain a glass having higher transmittance than conventional products in the deep ultraviolet region.
　本発明者等は、Ｆが軽元素である為に製造プロセスで表面付近の含有量が低くなり易く、ガラス表面近傍のＦの含有量が少ないと、ガラス表面近傍に含まれるＦｅ３＋が還元され難く、深紫外域の透過率の低下を来たしていることを見出した。 The present inventors believe that since F is a light element, its content near the surface tends to be low during the manufacturing process, and that when the F content near the glass surface is low, Fe 3+ contained near the glass surface is reduced. It was found that this resulted in a decrease in transmittance in the deep ultraviolet region.
　即ち、本発明の紫外線透過ガラスは、ガラス表面から１５μｍ深さのＦの含有量をｘ（質量％）、ガラス表面から１μｍ深さのＦの含有量をｙ（質量％）とした場合、ｙ／ｘが０．８以上であることを特徴とする。ここで、「Ｆの含有量」は、市販の電子線マイクロアナライザ（例えば、島津製作所製ＥＰＭＡ－１７２０Ｈ）で測定可能である。 That is, in the ultraviolet transmitting glass of the present invention, when the F content at a depth of 15 μm from the glass surface is x (mass%), and the F content at a depth of 1 μm from the glass surface is y (mass%), y /x is 0.8 or more. Here, the "F content" can be measured with a commercially available electron beam microanalyzer (for example, EPMA-1720H manufactured by Shimadzu Corporation).
　本発明の紫外線透過ガラスは、厚み０．５ｍｍ、波長２００ｎｍにおける透過率（％）をＴ２００とした場合、Ｔ２００≧６９であることが好ましい。ここで、「波長２００ｎｍにおける透過率」は、市販の分光光度計（例えば、島津製作所製ＵＶ―３１００ＰＣ）で測定可能である。 In the ultraviolet transmitting glass of the present invention, when the transmittance (%) at a thickness of 0.5 mm and a wavelength of 200 nm is T200 , it is preferable that T200 ≧69. Here, the "transmittance at a wavelength of 200 nm" can be measured with a commercially available spectrophotometer (for example, UV-3100PC manufactured by Shimadzu Corporation).
　本発明の紫外線透過ガラスは、厚みが０．２～２ｍｍであり、管状であることが好ましい。 The ultraviolet transmitting glass of the present invention preferably has a thickness of 0.2 to 2 mm and is tubular.
　本発明の紫外線透過ガラスは、ガラス組成として、質量％で、ＳｉＯ２　５５～７５％、Ａｌ２Ｏ３　１～１０％、Ｂ２Ｏ３　１０～３０％、ＣａＯ　０～５　％、　ＢａＯ　０～５％、Ｌｉ２Ｏ＋Ｎａ２Ｏ＋Ｋ２Ｏ　１～１５％、ＴｉＯ２　０～０．００１％、Ｆｅ２Ｏ３　０～０．００１％、Ｆ　０．５～７％を含有することが好ましい。なお、「Ａ＋Ｂ＋Ｃ」とは、成分Ａ、成分Ｂ及び成分Ｃの合量を指す。例えば、「Ｌｉ２Ｏ＋Ｎａ２Ｏ＋Ｋ２Ｏ」は、Ｌｉ２Ｏ、Ｎａ２Ｏ及びＫ２Ｏの合量を指す。 The ultraviolet transmitting glass of the present invention has, as a glass composition, SiO 2 55 to 75%, Al 2 O 3 1 to 10%, B 2 O 3 10 to 30%, CaO 0 to 5%, BaO 0 to 5%, Li 2 O+Na 2 O+K 2 O 1-15%, TiO 2 0-0.001%, Fe 2 O 3 0-0.001%, and F 0.5-7%. Note that "A+B+C" refers to the total amount of component A, component B, and component C. For example, " Li2O + Na2O + K2O " refers to the total amount of Li2O , Na2O and K2O .
　本発明の紫外線透過ガラスは、炎センサ用であることが好ましい。 The ultraviolet transmitting glass of the present invention is preferably used for flame sensors.
　本発明の紫外線透過ガラスの製造方法は、ガラスを管状に成形した後、酸溶液中に管状ガラスを浸漬してエッチングすることを特徴とする。 The method for producing ultraviolet transmitting glass of the present invention is characterized by forming glass into a tubular shape and then immersing the tubular glass in an acid solution for etching.
　本発明によれば、深紫外域において従来品よりも高い透過率を有するガラスを得ることができる。 According to the present invention, it is possible to obtain a glass that has higher transmittance than conventional products in the deep ultraviolet region.
　本発明の紫外線透過ガラスにおいて、ガラス表面から１５μｍ深さのＦの含有量をｘ（質量％）、ガラス表面から１μｍ深さのＦの含有量をｙ（質量％）とした場合、ｙ／ｘが０．８以上であり、０．８５以上、特に０．９以上であることが好ましい。ｙ／ｘが小さ過ぎると、ガラス表面近傍に含まれるＦｅ３＋が還元され難く、深紫外域の透過率が低下し易くなる。なお、ｙ／ｘの上限値は特に限定されないが、現実的には１．２以下である。また、ｙ／ｘの具体的な数値は下記の通りである。 In the ultraviolet transmitting glass of the present invention, when the F content at a depth of 15 μm from the glass surface is x (mass%) and the F content at a depth of 1 μm from the glass surface is y (mass%), y/x is 0.8 or more, preferably 0.85 or more, particularly 0.9 or more. If y/x is too small, Fe 3+ contained near the glass surface will be difficult to reduce, and the transmittance in the deep ultraviolet region will tend to decrease. Note that the upper limit value of y/x is not particularly limited, but is realistically 1.2 or less. Moreover, the specific numerical value of y/x is as follows.
　ｘは０．５～７％、０．６～５％、特に０．７～３％であることが好ましい。ｘが小さ過ぎると、ガラス内部のＦの含有量が少なくなり、ガラス内部に含まれるＦｅ３＋が還元され難く、深紫外域の透過率が低下し易くなる。一方、ｘが大き過ぎると、ガラス化し難くなる。 Preferably x is 0.5 to 7%, 0.6 to 5%, particularly 0.7 to 3%. If x is too small, the content of F inside the glass will decrease, Fe 3+ contained inside the glass will be difficult to reduce, and the transmittance in the deep ultraviolet region will tend to decrease. On the other hand, if x is too large, it becomes difficult to vitrify.
　ｙは０．４～８．４％、０．４５～６％、０．５～５％、特に０．６～３％であることが好ましい。ｙが小さ過ぎると、ガラス表面近傍のＦの含有量が少なくなり、ガラス表面近傍に含まれるＦｅ３＋が還元され難く、深紫外域の透過率が低下し易くなる。一方、ｙが大き過ぎると、ガラス化し難くなる。 Preferably, y is 0.4 to 8.4%, 0.45 to 6%, 0.5 to 5%, particularly 0.6 to 3%. If y is too small, the content of F near the glass surface will decrease, making it difficult for Fe 3+ contained near the glass surface to be reduced, and the transmittance in the deep ultraviolet region will tend to decrease. On the other hand, if y is too large, it becomes difficult to vitrify.
　本発明の紫外線透過ガラスにおいて、厚み０．５ｍｍ、波長２００ｎｍにおける透過率（％）をＴ２００とした場合、Ｔ２００≧６９、特にＴ２００≧７０であることが好ましい。厚み０．５ｍｍ、波長２００ｎｍにおける透過率が低過ぎると、紫外光が透過し難くなり、搭載される光源やデバイスの性能が低下し易くなる。 In the ultraviolet transmitting glass of the present invention, when the transmittance (%) at a thickness of 0.5 mm and a wavelength of 200 nm is T 200 , it is preferable that T 200 ≧69, particularly T 200 ≧70. If the transmittance at a thickness of 0.5 mm and a wavelength of 200 nm is too low, it will be difficult for ultraviolet light to pass through, and the performance of the light source or device mounted thereon will likely deteriorate.
　本発明の紫外線透過ガラスにおいて、厚み０．５ｍｍ、波長２２０ｎｍにおける透過率（％）をＴ２２０とした場合、Ｔ２２０≧７９、特にＴ２２０≧８０であることが好ましい。厚み０．５ｍｍ、波長２２０ｎｍにおける透過率が低過ぎると、紫外光が透過し難くなり、搭載される光源やデバイスの性能が低下し易くなる。 In the ultraviolet transmitting glass of the present invention, when T 220 is the transmittance (%) at a thickness of 0.5 mm and a wavelength of 220 nm, it is preferable that T 220 ≧79, particularly T 220 ≧80. If the transmittance at a thickness of 0.5 mm and a wavelength of 220 nm is too low, it will be difficult for ultraviolet light to pass through, and the performance of the light source or device mounted thereon will likely deteriorate.
　本発明の紫外線透過ガラスにおいて、厚み０．５ｍｍ、波長２５０ｎｍにおける透過率（％）をＴ２５０とした場合、Ｔ２５０≧８７、特にＴ２５０≧８８であることが好ましい。厚み０．５ｍｍ、波長２５０ｎｍにおける透過率が低過ぎると、紫外光が透過し難くなり、搭載される光源やデバイスの性能が低下し易くなる。 In the ultraviolet transmitting glass of the present invention, when T 250 is the transmittance (%) at a thickness of 0.5 mm and a wavelength of 250 nm, it is preferable that T 250 ≧87, particularly T 250 ≧88. If the transmittance at a thickness of 0.5 mm and a wavelength of 250 nm is too low, it will be difficult for ultraviolet light to pass through, and the performance of the light source or device mounted thereon will likely deteriorate.
　本発明の紫外線透過ガラスの歪点は、４００℃以上、４１０℃以上、特に４１５℃以上であることが好ましい。紫外線透過ガラスの歪点が低過ぎる場合、例えば、表面に機能性膜を成膜する際に、高温の成膜工程においてガラスに意図しない変形が生じ易くなる。なお、歪点の上限は特に限定されないが、現実的には６００℃以下である。 The strain point of the ultraviolet transmitting glass of the present invention is preferably 400°C or higher, 410°C or higher, particularly 415°C or higher. If the strain point of the ultraviolet-transmitting glass is too low, for example, when forming a functional film on the surface, the glass is likely to undergo unintended deformation during a high-temperature film-forming process. Note that the upper limit of the strain point is not particularly limited, but realistically it is 600° C. or less.
　本発明の紫外線透過ガラスの軟化点は、８５０℃以下、８００℃以下、７５０℃以下、特に７００℃以下であることが好ましい。軟化点が高過ぎると、ガラスの再熱加工がし難くなる。なお、軟化点の下限は特に限定されないが、現実的には６００℃以上である。 The softening point of the ultraviolet transmitting glass of the present invention is preferably 850°C or lower, 800°C or lower, or 750°C or lower, particularly 700°C or lower. If the softening point is too high, it will be difficult to reheat the glass. Note that the lower limit of the softening point is not particularly limited, but realistically it is 600°C or higher.
　本発明の紫外線透過ガラスの粘度１０２．５ｄＰａ・ｓにおける温度は、１５４０℃以下、１５２０℃以下、１５００℃以下、特に１４８０℃以下であることが好ましい。１０２．５ｄＰａ・ｓにおける温度が高過ぎると、ガラス溶融窯への負荷が大きくなるとともに、溶融性が低下して、ガラスの製造コストが高騰し易くなる。ここで、「１０２．５ｄＰａ・ｓにおける温度」は、白金球引き上げ法で測定可能である。なお、１０２．５ｄＰａ・ｓにおける温度の下限は特に限定されないが、現実的には１３００℃以上である。 The temperature at which the ultraviolet transmitting glass of the present invention has a viscosity of 10 2.5 dPa·s is preferably 1540°C or lower, 1520°C or lower, 1500°C or lower, particularly 1480°C or lower. If the temperature at 10 2.5 dPa·s is too high, the load on the glass melting furnace increases, the meltability decreases, and the manufacturing cost of glass tends to rise. Here, the "temperature at 10 2.5 dPa·s" can be measured by the platinum ball pulling method. Note that the lower limit of the temperature at 10 2.5 dPa·s is not particularly limited, but realistically it is 1300° C. or higher.
　本発明の紫外線透過ガラスの３０～３８０℃の温度範囲における平均線熱膨張係数は、３０×１０－７／℃以上、特に３５×１０－７／℃以上であることが好ましく、また９５×１０－７／℃以下、特に８０×１０－７／℃以下であることが好ましい。平均線熱膨張係数が低過ぎると、センサ端子等の各種部材の熱膨張係数に整合させ難くなる。一方、平均線熱膨張係数が高過ぎると、熱衝撃により、ガラスが破損し易くなる。 The average linear thermal expansion coefficient of the ultraviolet transmitting glass of the present invention in the temperature range of 30 to 380°C is preferably 30 x 10 -7 /°C or more, particularly 35 x 10 -7 /°C or more, and 95 x 10 -7 /°C or less, particularly preferably 80×10 -7 /°C or less. If the average linear thermal expansion coefficient is too low, it will be difficult to match the thermal expansion coefficients of various members such as sensor terminals. On the other hand, if the average linear thermal expansion coefficient is too high, the glass will be easily damaged by thermal shock.
　本発明の紫外線透過ガラスの液相温度は、１１２０℃以下、１１００℃以下、１０８０℃以下、１０５０℃以下、１０００℃以下、９５０℃以下、９００℃以下、特に８５０℃以下であることが好ましい。液相温度における粘度は、１０４．０ｄＰａ・ｓ以上、１０４．３ｄＰａ・ｓ以上、１０４．５ｄＰａ・ｓ以上、１０４．８ｄＰａ・ｓ以上、１０５．１ｄＰａ・ｓ以上、１０５．３ｄＰａ・ｓ以上、特に１０５．５ｄＰａ・ｓ以上であることが好ましい。このようにすれば、耐失透性が向上し、ダウンドロー法、特にオーバーフローダウンドロー法で成形し易くなるため、所望の形状のガラスを作製し易くなる。 The liquidus temperature of the ultraviolet transmitting glass of the present invention is preferably 1120°C or lower, 1100°C or lower, 1080°C or lower, 1050°C or lower, 1000°C or lower, 950°C or lower, 900°C or lower, particularly 850°C or lower. The viscosity at the liquidus temperature is 10 4.0 dPa・s or more, 10 4.3 dPa・s or more, 10 4.5 dPa・s or more, 10 4.8 dPa・s or more, 10 5.1 dPa・s As mentioned above, it is preferably 10 5.3 dPa·s or more, particularly 10 5.5 dPa·s or more. In this way, the devitrification resistance is improved and it becomes easier to mold by a down-draw method, particularly an overflow down-draw method, so that it becomes easier to produce glass in a desired shape.
　本発明の紫外線透過ガラスのヤング率は、４０ＧＰａ以上、特に４５ＧＰａ以上であることが好ましい。ヤング率が低過ぎると、デバイスの製造工程における搬送ラインでガラスが剛性を維持し難くなり、ガラスの変形、反り、破損が発生し易くなる。 The Young's modulus of the ultraviolet transmitting glass of the present invention is preferably 40 GPa or more, particularly 45 GPa or more. If the Young's modulus is too low, it will be difficult for the glass to maintain its rigidity on the conveyance line in the device manufacturing process, and the glass will be more likely to deform, warp, or break.
　本発明の紫外線透過ガラスは、ガラス組成として、質量％で、ＳｉＯ２　５５～７５％、Ａｌ２Ｏ３　１～１０％、Ｂ２Ｏ３　１０～３０％、ＣａＯ　０～５％、　ＢａＯ　０～５％、Ｌｉ２Ｏ＋Ｎａ２Ｏ＋Ｋ２Ｏ　１～１５％、ＴｉＯ２　０～０．００１％、Ｆｅ２Ｏ３　０～０．００１％、Ｆ　０．５～７％を含有することが好ましい。 The ultraviolet transmitting glass of the present invention has, as a glass composition, SiO 2 55-75%, Al 2 O 3 1-10%, B 2 O 3 10-30%, CaO 0-5%, BaO 0-0. 5%, Li 2 O+Na 2 O+K 2 O 1-15%, TiO 2 0-0.001%, Fe 2 O 3 0-0.001%, and F 0.5-7%.
　上記のように各成分の含有量を限定した理由を以下に示す。なお、各成分の含有量の説明において、％表示は、特に断りがある場合を除き、質量％を表す。 The reason for limiting the content of each component as described above is shown below. In addition, in the description of the content of each component, % represents mass % unless otherwise specified.
　ＳｉＯ２は、ガラスの骨格を形成する主成分である。ＳｉＯ２の含有量は、５５～７５％、５８～７０％、特に６５～６９％であることが好ましい。ＳｉＯ２の含有量が少な過ぎると、ヤング率、耐酸性が低下し易くなる。一方、ＳｉＯ２の含有量が多過ぎると、高温粘度が高くなり、溶融性が低下し易くなることに加えて、クリストバライト等の失透結晶が析出し易くなって、液相温度が上昇し易くなる。 SiO 2 is the main component that forms the skeleton of glass. The content of SiO 2 is preferably 55-75%, 58-70%, particularly 65-69%. If the content of SiO 2 is too low, Young's modulus and acid resistance tend to decrease. On the other hand, if the content of SiO 2 is too high, the high-temperature viscosity becomes high and the meltability tends to decrease, and in addition, devitrification crystals such as cristobalite tend to precipitate, and the liquidus temperature tends to increase. Become.
　Ａｌ２Ｏ３は、ヤング率を高める成分であると共に、分相、失透を抑制する成分である。Ａｌ２Ｏ３の含有量は、１～１０％、２～９％、特に３～８％であることが好ましい。Ａｌ２Ｏ３の含有量が少な過ぎると、ヤング率が低下し易くなり、またガラスが分相、失透し易くなる。一方、Ａｌ２Ｏ３の含有量が多過ぎると、高温粘度が高くなり、溶融性が低下し易くなる。 Al 2 O 3 is a component that increases Young's modulus and also suppresses phase separation and devitrification. The content of Al 2 O 3 is preferably 1 to 10%, 2 to 9%, particularly 3 to 8%. If the content of Al 2 O 3 is too small, the Young's modulus tends to decrease, and the glass tends to undergo phase separation and devitrification. On the other hand, if the content of Al 2 O 3 is too large, the high temperature viscosity will increase and the meltability will tend to decrease.
　Ｂ２Ｏ３は、溶融性、耐失透性を高める成分であり、また傷の付き易さを改善して、強度を高める成分である。Ｂ２Ｏ３の含有量は、１０～３０％、１３～２８％、特に１５～２５％であることが好ましい。Ｂ２Ｏ３の含有量が少な過ぎると、溶融性、耐失透性が低下し易くなり、またフッ酸系の薬液に対する耐性が低下し易くなる。一方、Ｂ２Ｏ３の含有量が多過ぎると、ヤング率、耐酸性が低下し易くなる。 B 2 O 3 is a component that improves melting properties and devitrification resistance, and also improves susceptibility to scratches and increases strength. The content of B 2 O 3 is preferably 10 to 30%, 13 to 28%, particularly 15 to 25%. If the content of B 2 O 3 is too small, meltability and devitrification resistance tend to decrease, and resistance to hydrofluoric acid-based chemicals tends to decrease. On the other hand, if the content of B 2 O 3 is too large, Young's modulus and acid resistance tend to decrease.
　ＣａＯは、高温粘性を下げて、溶融性を高める成分である。またアルカリ土類金属酸化物の中では、導入原料が比較的安価であるため、原料コストを低廉化する成分である。ＣａＯの含有量は、０～５％、０．０１～１％、特に０．１～０．８％であることが好ましい。ＣａＯの含有量が多過ぎると、ガラスが失透し易くなる。 CaO is a component that lowers high temperature viscosity and increases meltability. Moreover, among alkaline earth metal oxides, since the raw material to be introduced is relatively inexpensive, it is a component that reduces raw material costs. The content of CaO is preferably 0 to 5%, 0.01 to 1%, particularly 0.1 to 0.8%. If the content of CaO is too high, the glass tends to devitrify.
　ＢａＯは、耐失透性を高める成分である。ＢａＯの含有量は、０～５％、０．１～３％、特に０．５～１．５％であることが好ましい。ＢａＯの含有量が多過ぎると、ガラスが失透し易くなる。 BaO is a component that increases resistance to devitrification. The content of BaO is preferably 0 to 5%, 0.1 to 3%, particularly 0.5 to 1.5%. If the BaO content is too high, the glass will easily devitrify.
　Ｌｉ２Ｏ、Ｎａ２Ｏ及びＫ２Ｏは、高温粘性を下げて、溶融性を顕著に高めると共に、ガラス原料の初期の溶融に寄与するアルカリ金属酸化物成分である。Ｌｉ２Ｏ＋Ｎａ２Ｏ＋Ｋ２Ｏの含有量は、１～１５％、２～１０％、特に３～６％であることが好ましい。Ｌｉ２Ｏ＋Ｎａ２Ｏ＋Ｋ２Ｏの含有量が少な過ぎると、溶融性が低下し易くなる。一方、Ｌｉ２Ｏ＋Ｎａ２Ｏ＋Ｋ２Ｏの含有量が多過ぎると、熱膨張係数が不当に高くなる虞がある。 Li 2 O, Na 2 O, and K 2 O are alkali metal oxide components that lower high-temperature viscosity, significantly increase meltability, and contribute to initial melting of the glass raw material. The content of Li 2 O+Na 2 O+K 2 O is preferably 1 to 15%, 2 to 10%, particularly 3 to 6%. If the content of Li 2 O + Na 2 O + K 2 O is too small, the meltability tends to decrease. On the other hand, if the content of Li 2 O+Na 2 O+K 2 O is too large, the coefficient of thermal expansion may become unduly high.
　Ｌｉ２Ｏは、高温粘性を下げて、溶融性を顕著に高めると共に、ガラス原料の初期の溶融に寄与する成分である。Ｌｉ２Ｏの含有量は、０～５％、０～３％、特に０．１～１．２％であることが好ましい。Ｌｉ２Ｏの含有量が多過ぎると、ガラスが分相し易くなる。 Li 2 O is a component that lowers high-temperature viscosity, significantly increases meltability, and contributes to initial melting of the glass raw material. The content of Li 2 O is preferably 0 to 5%, 0 to 3%, particularly 0.1 to 1.2%. If the content of Li 2 O is too large, the glass tends to undergo phase separation.
　Ｎａ２Ｏは、高温粘性を下げて、溶融性を顕著に高めると共に、ガラス原料の初期の溶融に寄与する成分である。また熱膨張係数を調整するための成分である。Ｎａ２Ｏの含有量は、０～１０％、０～８％、１～５％、特に１～３％であることが好ましい。Ｎａ２Ｏの含有量が多過ぎると、熱膨張係数が不当に高くなる虞がある。 Na 2 O is a component that lowers high-temperature viscosity, significantly increases meltability, and contributes to initial melting of the glass raw material. It is also a component for adjusting the coefficient of thermal expansion. The content of Na 2 O is preferably 0 to 10%, 0 to 8%, 1 to 5%, particularly 1 to 3%. If the content of Na 2 O is too large, the coefficient of thermal expansion may become unduly high.
　Ｋ２Ｏは、高温粘性を下げて、溶融性を顕著に高めると共に、ガラス原料の初期の溶融に寄与する成分である。また熱膨張係数を調整するための成分である。Ｋ２Ｏの含有量は、０～１０％、０．１～５％、特に０．５～３％であることが好ましい。Ｋ２Ｏの含有量が多過ぎると、熱膨張係数が不当に高くなる虞がある。 K 2 O is a component that lowers high temperature viscosity, significantly increases meltability, and contributes to the initial melting of the glass raw material. It is also a component for adjusting the coefficient of thermal expansion. The content of K 2 O is preferably 0 to 10%, 0.1 to 5%, particularly 0.5 to 3%. If the content of K 2 O is too large, the coefficient of thermal expansion may become unduly high.
　ＴｉＯ２は、深紫外域での透過率を低下させる成分である。ＴｉＯ２の含有量は、０．００１％以下、０．０００８％以下、特に０．０００１～０．０００６％であることが好ましい。ＴｉＯ２の含有量が多過ぎると、ガラスが着色して、深紫外域での透過率が低下し易くなる。 TiO 2 is a component that reduces transmittance in the deep ultraviolet region. The content of TiO 2 is preferably 0.001% or less, 0.0008% or less, particularly 0.0001 to 0.0006%. If the content of TiO 2 is too large, the glass becomes colored and the transmittance in the deep ultraviolet region tends to decrease.
　Ｆｅ２Ｏ３は、深紫外域での透過率を低下させる成分である。Ｆｅ２Ｏ３の含有量は、０．００１％以下、０．０００１～０．０００９％、特に０．００００１～０．０００８％であることが好ましい。Ｆｅ２Ｏ３の含有量が多過ぎると、ガラスが着色して、深紫外域での透過率が低下し易くなる。 Fe 2 O 3 is a component that reduces transmittance in the deep ultraviolet region. The content of Fe 2 O 3 is preferably 0.001% or less, 0.0001 to 0.0009%, particularly 0.00001 to 0.0008%. If the content of Fe 2 O 3 is too large, the glass becomes colored and the transmittance in the deep ultraviolet region tends to decrease.
　酸化鉄中のＦｅイオンは、Ｆｅ２＋又はＦｅ３＋の状態で存在する。Ｆｅ２＋の割合が少な過ぎると、深紫外線での透過率が低下し易くなる。よって、本発明の紫外線透過ガラスに含まれる酸化鉄中のＦｅ２＋／（Ｆｅ２＋＋Ｆｅ３＋）の質量割合は、０．１以上、０．２以上、０．３以上、０．４以上、特に０．５以上であることが好ましい。 Fe ions in iron oxide exist in the state of Fe 2+ or Fe 3+ . If the proportion of Fe 2+ is too small, the transmittance in deep ultraviolet rays tends to decrease. Therefore, the mass ratio of Fe 2+ /(Fe 2+ +Fe 3+ ) in the iron oxide contained in the ultraviolet transmitting glass of the present invention is 0.1 or more, 0.2 or more, 0.3 or more, 0.4 or more, especially It is preferable that it is 0.5 or more.
　Ｆは、ガラスに含まれるＦｅ３＋を還元し、深紫外域の透過率を向上させる成分である。また、粘性を下げて溶融性を高める成分である。Ｆの含有量は、０．５～７％、０．６～５％、特に０．７～３％であることが好ましい。Ｆの含有量が少な過ぎると、上記効果を得難くなる。一方、Ｆの含有量が多過ぎると、逆にガラス化し難くなる。 F is a component that reduces Fe 3+ contained in the glass and improves the transmittance in the deep ultraviolet region. It is also a component that lowers viscosity and increases meltability. The content of F is preferably 0.5 to 7%, 0.6 to 5%, particularly 0.7 to 3%. If the F content is too low, it will be difficult to obtain the above effects. On the other hand, if the F content is too high, it becomes difficult to vitrify.
　上記成分以外にも、以下の成分を導入してもよい。 In addition to the above components, the following components may also be introduced.
　ＳｒＯは、耐失透性を高める成分である。ＳｒＯの含有量は、０～７％、０～５％、０～３％、特に０～１％であることが好ましい。ＳｒＯの含有量が多過ぎると、ガラスが失透し易くなる。 SrO is a component that increases resistance to devitrification. The content of SrO is preferably 0 to 7%, 0 to 5%, 0 to 3%, particularly 0 to 1%. If the content of SrO is too large, the glass tends to devitrify.
　ＺｒＯ２は、耐酸性を高める成分であるが、ガラス組成中に多量に含有させると、ガラスが失透し易くなる。よって、ＺｒＯ２の含有量は、０．１％以下、０．００１～０．０２％、特に０．０００１～０．０１％であることが好ましい。 ZrO 2 is a component that improves acid resistance, but if it is included in a large amount in the glass composition, the glass tends to devitrify. Therefore, the content of ZrO 2 is preferably 0.1% or less, 0.001 to 0.02%, particularly 0.0001 to 0.01%.
　ＭｏＯ３は、生産時に炉内からの不純物として含有する成分であるが、ガラス組成中に多量に含有すると、深紫外域の透過率を低下させる虞がある。よって、ＭｏＯ３の含有量は０．０５％以下、０．００５～０．００１％、特に０．０００１～０．０００５％であることが好ましい。 MoO 3 is a component that is contained as an impurity from within the furnace during production, but if it is contained in a large amount in the glass composition, there is a risk of reducing the transmittance in the deep ultraviolet region. Therefore, the content of MoO 3 is preferably 0.05% or less, 0.005 to 0.001%, particularly 0.0001 to 0.0005%.
　本発明の紫外線透過ガラスの形状は任意に設定可能である。本発明の紫外線透過ガラスの形状は、例えば、平板状、曲板状、直管状、曲管状、棒状、球状、容器状、ブロック状とすることができる。 The shape of the ultraviolet transmitting glass of the present invention can be set arbitrarily. The shape of the ultraviolet transmitting glass of the present invention can be, for example, a flat plate, a curved plate, a straight tube, a curved tube, a rod, a sphere, a container, or a block.
　炎センサ用途に好適に用いるためには、紫外線透過ガラスの厚みは、０．２～２ｍｍ、特に０．２５～１．９ｍｍであることが好ましく、直管状、曲管状等の管状であることが好ましい。なお、一般的に紫外線透過率はガラスの厚みが厚いほど低下するが、本発明の紫外線透過ガラスは２５０ｎｍ以下の波長領域において高い透過率を有するために、従来品に比べ厚みを増加させても同波長域において高い透過率を維持可能である。 In order to suitably use it for flame sensor applications, the thickness of the ultraviolet transmitting glass is preferably 0.2 to 2 mm, particularly 0.25 to 1.9 mm, and preferably has a tubular shape such as a straight tube shape or a curved tube shape. preferable. In general, the ultraviolet transmittance decreases as the thickness of the glass increases, but since the ultraviolet transmitting glass of the present invention has high transmittance in the wavelength region of 250 nm or less, even if the thickness is increased compared to conventional products. High transmittance can be maintained in the same wavelength range.
　本発明の紫外線透過ガラスの表面の表面粗さＲａは、１０ｎｍ以下、９ｎｍ以下、８ｎｍ以下、７ｎｍ以下、６ｎｍ以下、５ｎｍ以下、４ｎｍ以下、３ｎｍ以下、２ｎｍ以下、特に１ｎｍ以下であることが好ましい。表面の表面粗さＲａが大き過ぎると、深紫外線での透過率が減少する傾向がある。 The surface roughness Ra of the surface of the ultraviolet transmitting glass of the present invention is preferably 10 nm or less, 9 nm or less, 8 nm or less, 7 nm or less, 6 nm or less, 5 nm or less, 4 nm or less, 3 nm or less, 2 nm or less, particularly 1 nm or less. . If the surface roughness Ra of the surface is too large, the transmittance in deep ultraviolet rays tends to decrease.
　本発明の紫外線透過ガラスは、例えば、各種ガラス原料を調合して、ガラスバッチを得た上で、このガラスバッチを溶融し、得られた溶融ガラスを清澄、均質化し、所定形状に成形することで作製することができる。 The ultraviolet transmitting glass of the present invention can be produced, for example, by mixing various glass raw materials to obtain a glass batch, then melting this glass batch, clarifying and homogenizing the obtained molten glass, and molding it into a predetermined shape. It can be made with
　本発明の紫外線透過ガラスの製造方法において、ガラス原料の一部として、還元剤を用いることが好ましい。このようにすれば、ガラス中に含まれるＦｅ３＋が還元されて、深紫外線での透過率が向上する。還元剤として、木粉、カーボン粉末、金属アルミニウム、金属シリコン、フッ化アルミニウム等の材料が使用可能であるが、その中でも金属シリコン、フッ化アルミニウムが好ましい。 In the method for producing ultraviolet transmitting glass of the present invention, it is preferable to use a reducing agent as part of the glass raw material. In this way, Fe 3+ contained in the glass is reduced and the transmittance of deep ultraviolet rays is improved. As the reducing agent, materials such as wood powder, carbon powder, metal aluminum, metal silicon, and aluminum fluoride can be used, and among these, metal silicon and aluminum fluoride are preferred.
　本発明の紫外線透過ガラスの製造方法において、ガラス原料の一部として、金属シリコンを用いることが好ましく、その添加量は、ガラスバッチの全質量に対して０．００１～３質量％、０．００５～２質量％、０．０１～１質量％、特に０．０５～０．７５質量％であることが好ましい。金属シリコンの添加量が少な過ぎると、ガラス中に含まれるＦｅ３＋が還元されず、深紫外線での透過率が低下し易くなる。一方、金属シリコンの添加量が多過ぎると、ガラスが茶色に着色する傾向がある。 In the method for producing ultraviolet transmitting glass of the present invention, it is preferable to use metal silicon as a part of the glass raw material, and the amount added is 0.001 to 3% by mass, 0.005% by mass based on the total mass of the glass batch. -2% by weight, preferably 0.01-1% by weight, particularly 0.05-0.75% by weight. If the amount of metal silicon added is too small, Fe 3+ contained in the glass will not be reduced, and the transmittance in deep ultraviolet rays will tend to decrease. On the other hand, if the amount of metal silicon added is too large, the glass tends to be colored brown.
　また、ガラス原料の一部として、フッ化アルミニウム（ＡｌＦ３）を用いることも好ましく、その添加量は、ガラスバッチの全質量に対して、Ｆ換算で０．０１～２質量％、０．０５～１．５質量％、特に０．３～１．５質量％であることが好ましい。フッ化アルミニウムの添加量が少な過ぎると、ガラス中に含まれるＦｅ３＋が還元されず、深紫外線での透過率が低下し易くなる。一方、フッ化アルミニウムの添加量が多過ぎると、Ｆガスがガラス中に泡として残存する虞がある。 It is also preferable to use aluminum fluoride (AlF 3 ) as part of the glass raw material, and the amount added is 0.01 to 2% by mass in terms of F, 0.05% by mass based on the total mass of the glass batch. It is preferably from 1.5% by weight, particularly from 0.3 to 1.5% by weight. If the amount of aluminum fluoride added is too small, Fe 3+ contained in the glass will not be reduced, and the transmittance in deep ultraviolet rays will tend to decrease. On the other hand, if the amount of aluminum fluoride added is too large, there is a possibility that F gas will remain in the glass as bubbles.
　本発明の紫外線透過ガラスの製造方法において、紫外線透過ガラスを平板形状に成形する場合は、ダウンドロー法や、オーバーフローダウンドロー法を用いて成形することが好ましい。オーバーフローダウンドロー法は、耐熱性の樋状構造物の両側から溶融ガラスを溢れさせて、溢れた溶融ガラスを樋状構造物の下頂端で合流させながら、下方に延伸成形してガラス板を成形する方法である。オーバーフローダウンドロー法では、ガラス板の表面となるべき面は樋状耐火物に接触せず、自由表面の状態で成形される。このため、薄型のガラス板を作製し易くなると共に、表面を研磨しなくても、板厚ばらつきを低減することができる。結果として、ガラス板の製造コストを低廉化することができる。なお、樋状構造物の構造や材質は、所望の寸法や表面精度を実現できるものであれば、特に限定されない。また、下方への延伸成形を行う際に、力を印加する方法も特に限定されない。例えば、充分に大きい幅を有する耐熱性ロールをガラスに接触させた状態で回転させて延伸する方法を採用してもよいし、複数の対になった耐熱性ロールをガラスの端面近傍のみに接触させて延伸する方法を採用してもよい。 In the method for producing ultraviolet-transparent glass of the present invention, when forming the ultraviolet-transparent glass into a flat plate shape, it is preferable to use a down-draw method or an overflow down-draw method. In the overflow down-draw method, molten glass overflows from both sides of a heat-resistant gutter-like structure, and the overflowing molten glass joins at the bottom end of the gutter-like structure, stretching downward to form a glass plate. This is the way to do it. In the overflow downdraw method, the surface of the glass plate that is to become the surface does not come into contact with the trough-like refractories and is formed as a free surface. Therefore, it becomes easier to produce a thin glass plate, and variations in plate thickness can be reduced without polishing the surface. As a result, the manufacturing cost of the glass plate can be reduced. Note that the structure and material of the gutter-like structure are not particularly limited as long as desired dimensions and surface accuracy can be achieved. Furthermore, the method of applying force when performing downward stretch molding is not particularly limited. For example, a method may be adopted in which a heat-resistant roll having a sufficiently large width is rotated while in contact with the glass, or a plurality of pairs of heat-resistant rolls are brought into contact only near the end surface of the glass. You may adopt the method of stretching.
　本発明の紫外線透過ガラスの製造方法において、紫外線透過ガラスを管状に成形する場合は、ダウンドロー法や、ベロー法、ダンナー法等を用いて成形することが好ましい。ダンナー法は、傾斜配置された耐熱性のスリーブ状構造物の上方端側に溶融ガラスを流下して巻き付け、下方端側へ流下した溶融ガラスを延伸成形してガラス管を成形する方法である。 In the method for producing ultraviolet-transparent glass of the present invention, when forming the ultraviolet-transparent glass into a tubular shape, it is preferable to use a down-draw method, a bellows method, a Danner method, or the like. The Danner method is a method in which molten glass is rolled down and wound around the upper end of a heat-resistant sleeve-like structure arranged at an angle, and the molten glass that has flowed down to the lower end is stretched and formed to form a glass tube.
　成形方法として、上記以外にも、例えば、スロットダウン法、リドロー法、フロート法等を採用することもできる。 In addition to the above-mentioned molding method, for example, a slot-down method, a redraw method, a float method, etc. can also be adopted.
　紫外線透過ガラスの製造プロセスでは、ガラス表層部のＦの含有量が減少し易くなる場合がある。その際は、ガラスを成形した後に、酸溶液中にガラスを浸漬してエッチングし、Ｆの含有量が減少した表層部を取り除くことにより、ガラス表面近傍のＦの含有量を多くすることが可能である。なお、エッチング処理に用いる酸としては、３～５０質量％の硝酸、弗酸、硫酸、塩酸、あるいは酸濃度が３～５０質量％で少なくとも前述した酸の２種類からなる混酸などが使用可能である。浸漬時間は１分以上、３分以上、特に５分以上であることが好ましい。浸漬時間が短すぎると、エッチングが不十分となり、ガラス表面近傍のＦの含有量が多くならない虞がある。浸漬時間の上限は特に限定されないが、現実的には２０分以下である。酸の温度は２０℃以上、２５℃以上、特に３０℃以上であることが好ましい。酸の温度が低すぎると、エッチングが不十分となり、ガラス表面近傍のＦの含有量が多くならない虞がある。酸の温度の上限は特に限定されないが、現実的には９５℃以下である。なお、物理研磨等により、Ｆの含有量が減少した表層部を取り除くことも可能である。 In the manufacturing process of ultraviolet transmitting glass, the content of F in the surface layer of the glass tends to decrease in some cases. In that case, after forming the glass, it is possible to increase the F content near the glass surface by immersing the glass in an acid solution and etching it to remove the surface layer where the F content has decreased. It is. In addition, as the acid used for the etching treatment, nitric acid, hydrofluoric acid, sulfuric acid, hydrochloric acid with a concentration of 3 to 50% by mass, or a mixed acid consisting of at least two of the above-mentioned acids with an acid concentration of 3 to 50% by mass, etc. can be used. be. The immersion time is preferably 1 minute or more, 3 minutes or more, particularly 5 minutes or more. If the immersion time is too short, etching may be insufficient and the F content near the glass surface may not increase. The upper limit of the immersion time is not particularly limited, but realistically it is 20 minutes or less. The temperature of the acid is preferably 20°C or higher, 25°C or higher, particularly 30°C or higher. If the temperature of the acid is too low, etching may be insufficient and the F content near the glass surface may not increase. Although the upper limit of the temperature of the acid is not particularly limited, it is realistically 95°C or lower. Note that it is also possible to remove the surface layer portion where the F content has decreased by physical polishing or the like.
　以下、本発明を実施例に基づいて説明する。なお、以下の実施例は単なる例示である。本発明は、以下の実施例に何ら限定されない。 Hereinafter, the present invention will be explained based on examples. Note that the following examples are merely illustrative. The present invention is not limited to the following examples.
　表１は、本発明の実施例（試料Ｎｏ．１～５）及び比較例（試料Ｎｏ．６）を示している。 Table 1 shows Examples (Samples No. 1 to 5) of the present invention and Comparative Examples (Sample No. 6).
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　まず、表中のガラス組成となるように、表に示すガラス原料を調合したガラスバッチを白金坩堝に入れ、１６００℃で６時間溶融した。 First, a glass batch prepared by mixing the glass raw materials shown in the table so as to have the glass composition shown in the table was placed in a platinum crucible and melted at 1600°C for 6 hours.
　得られた溶融ガラスについて、白金スターラーを用いて攪拌し、均質化を行った。次いで、溶融ガラスをカーボン板上に流し出し、平板形状に成形した後、徐冷点より２０℃程度高い温度から室温まで３℃／分の速度で徐冷した後、表に示す条件にてエッチングを行った。 The obtained molten glass was stirred using a platinum stirrer to homogenize it. Next, the molten glass was poured onto a carbon plate, formed into a flat plate shape, and then slowly cooled from a temperature approximately 20°C higher than the annealing point to room temperature at a rate of 3°C/min, and then etched under the conditions shown in the table. I did it.
　得られた各試料について透過率を測定した。透過率は、ダブルビーム型分光光度計（島津製作所製ＵＶ―３１００ＰＣ）を用いて、厚み方向の分光透過率を測定した値である。測定試料としては、表１に記載の厚みで両面を光学研磨面（鏡面）に研磨したものを使用した。なお、ＡＦＭにより、これらの測定試料の表面の表面粗さＲａを測定したところ、測定領域１０μｍ×１０μｍで０．５～１．０ｎｍであった。 Transmittance was measured for each sample obtained. The transmittance is a value obtained by measuring the spectral transmittance in the thickness direction using a double beam spectrophotometer (UV-3100PC manufactured by Shimadzu Corporation). As measurement samples, samples having the thicknesses listed in Table 1 and polished on both sides to optically polished surfaces (mirror surfaces) were used. Incidentally, when the surface roughness Ra of the surfaces of these measurement samples was measured by AFM, it was 0.5 to 1.0 nm in a measurement area of 10 μm×10 μm.
　また、得られた各試料について、ガラス表面から１５μｍ深さのＦの含有量x(質量%)、ガラス表面から１μｍ深さのＦの含有量y(質量%)は、試料の断面を電子線マイクロアナライザ（島津製作所製ＥＰＭＡ－１７２０Ｈ）を用いてライン分析を行うことにより測定した。 In addition, for each sample obtained, the F content x (mass %) at a depth of 15 μm from the glass surface, and the F content y (mass %) at a depth of 1 μm from the glass surface are It was measured by line analysis using a microanalyzer (EPMA-1720H manufactured by Shimadzu Corporation).
　表から分かるように、ｙ／ｘが０．８１以上である試料Ｎｏ．１～５は、波長２００～２５０ｎｍの紫外光の透過率が高かった。一方、ｙ／ｘが０．７１と小さい試料Ｎｏ．６は、波長２００～２５０ｎｍの紫外光の透過率が低かった。また、ｙ／ｘが大きい程、波長２００～２５０ｎｍの紫外光の透過率が高くなることが分かった。 As can be seen from the table, sample No. with y/x of 0.81 or more. Samples 1 to 5 had high transmittance for ultraviolet light with a wavelength of 200 to 250 nm. On the other hand, sample No. with a small y/x of 0.71 No. 6 had a low transmittance of ultraviolet light with a wavelength of 200 to 250 nm. It was also found that the larger y/x, the higher the transmittance of ultraviolet light with a wavelength of 200 to 250 nm.
　なお、上記実施例では、溶融ガラスを流し出して平板形状に成形したが、工業的規模で生産する場合には、オーバーフローダウンドロー法等で平板形状に成形し、両表面が未研磨の状態で使用に供することが好ましい。また、管状に形成する場合は、ダウンドロー法やダンナー法等で管状に成形することが好ましい。 In the above example, the molten glass was poured out and formed into a flat plate shape. However, when producing on an industrial scale, it is formed into a flat plate shape using an overflow down-draw method, etc., with both surfaces unpolished. It is preferable to use it. Moreover, when forming into a tubular shape, it is preferable to shape|mold into a tubular shape by a down draw method, a Danner method, etc.

Claims (6)

  1. 　ガラス表面から１５μｍ深さのＦの含有量をｘ（質量％）、ガラス表面から１μｍ深さのＦの含有量をｙ（質量％）とした場合、ｙ／ｘが０．８以上であることを特徴とする紫外線透過ガラス。 When the F content at a depth of 15 μm from the glass surface is x (mass%) and the F content at a depth of 1 μm from the glass surface is y (mass%), y/x must be 0.8 or more. Ultraviolet transmitting glass featuring
  2. 　厚み０．５ｍｍ、波長２００ｎｍにおける透過率（％）をＴ２００とした場合、Ｔ２００≧６９であることを特徴とする請求項１に記載の紫外線透過ガラス。 The ultraviolet transmitting glass according to claim 1, wherein T200 ≧69, where T200 is the transmittance (%) at a thickness of 0.5 mm and a wavelength of 200 nm.
  3. 　厚みが０．２～２．０ｍｍであり、管状であることを特徴とする請求項１又は２に記載の紫外線透過ガラス。 The ultraviolet transmitting glass according to claim 1 or 2, which has a thickness of 0.2 to 2.0 mm and is tubular.
  4. 　ガラス組成として、質量％で、ＳｉＯ２　５５～７５％、Ａｌ２Ｏ３　１～１０％、Ｂ２Ｏ３　１０～３０％、ＣａＯ　０～５　％、　ＢａＯ　０～５％、Ｌｉ２Ｏ＋Ｎａ２Ｏ＋Ｋ２Ｏ　１～１５％、ＴｉＯ２　０～０．００１％、Ｆｅ２Ｏ３　０～０．００１％、Ｆ　０．５～７％を含有することを特徴とする請求項１又は２に記載の紫外線透過ガラス。 As for the glass composition, in mass %, SiO 2 55-75%, Al 2 O 3 1-10%, B 2 O 3 10-30%, CaO 0-5%, BaO 0-5%, Li 2 O + Na 2 O + K 2. The composition according to claim 1 or 2, characterized in that it contains 1 to 15% of 2 O, 0 to 0.001% of TiO 2 , 0 to 0.001% of Fe 2 O 3 , and 0.5 to 7% of F. UV transparent glass.
  5. 　炎センサ用であることを特徴とする請求項１又は２に記載の紫外線透過ガラス。 The ultraviolet transmitting glass according to claim 1 or 2, which is used for a flame sensor.
  6. 　ガラスを管状に成形した後、酸溶液中に管状ガラスを浸漬してエッチングすることを特徴とする紫外線透過ガラスの製造方法。 A method for producing ultraviolet-transparent glass, which is characterized by forming glass into a tubular shape and then immersing the tubular glass in an acid solution for etching.
PCT/JP2023/016202 2022-05-13 2023-04-25 Uv-transmitting glass WO2023218938A1 (en)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07187706A (en) * 1993-10-15 1995-07-25 Jenaer Glaswerk Gmbh Reductively molten borosilicate glass having improved ultraviolet transmittance and hydrolysis stability and its usage
JP2005247598A (en) * 2004-03-01 2005-09-15 Hoya Corp Method for producing precision press molding preform and method for producing optical element
JP2009023898A (en) * 2007-06-20 2009-02-05 Asahi Glass Co Ltd Synthetic quartz glass body, process for producing the same, optical element, and optical apparatus
JP2013095619A (en) * 2011-10-28 2013-05-20 Olympus Corp Glass optical element
JP2019099414A (en) * 2017-12-01 2019-06-24 クアーズテック株式会社 Silica glass member and manufacturing method of silica glass member
JP2019147722A (en) * 2018-02-28 2019-09-05 日本電気硝子株式会社 Ultraviolet transmission glass and manufacturing method therefor
WO2021070707A1 (en) * 2019-10-07 2021-04-15 日本電気硝子株式会社 Ultraviolet transmission glass

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07187706A (en) * 1993-10-15 1995-07-25 Jenaer Glaswerk Gmbh Reductively molten borosilicate glass having improved ultraviolet transmittance and hydrolysis stability and its usage
JP2005247598A (en) * 2004-03-01 2005-09-15 Hoya Corp Method for producing precision press molding preform and method for producing optical element
JP2009023898A (en) * 2007-06-20 2009-02-05 Asahi Glass Co Ltd Synthetic quartz glass body, process for producing the same, optical element, and optical apparatus
JP2013095619A (en) * 2011-10-28 2013-05-20 Olympus Corp Glass optical element
JP2019099414A (en) * 2017-12-01 2019-06-24 クアーズテック株式会社 Silica glass member and manufacturing method of silica glass member
JP2019147722A (en) * 2018-02-28 2019-09-05 日本電気硝子株式会社 Ultraviolet transmission glass and manufacturing method therefor
WO2021070707A1 (en) * 2019-10-07 2021-04-15 日本電気硝子株式会社 Ultraviolet transmission glass

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