WO2019044563A1 - Verre - Google Patents

Verre Download PDF

Info

Publication number
WO2019044563A1
WO2019044563A1 PCT/JP2018/030691 JP2018030691W WO2019044563A1 WO 2019044563 A1 WO2019044563 A1 WO 2019044563A1 JP 2018030691 W JP2018030691 W JP 2018030691W WO 2019044563 A1 WO2019044563 A1 WO 2019044563A1
Authority
WO
WIPO (PCT)
Prior art keywords
glass
content
chemical strengthening
strengthening layer
component
Prior art date
Application number
PCT/JP2018/030691
Other languages
English (en)
Japanese (ja)
Inventor
貴尋 坂上
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.)
Filing date
Publication date
Application filed by Ａｇｃ株式会社 filed Critical Ａｇｃ株式会社
Priority to CN201880055878.1A priority Critical patent/CN111051262B/zh
Priority to JP2019539374A priority patent/JP7092135B2/ja
Publication of WO2019044563A1 publication Critical patent/WO2019044563A1/fr

Links

Images

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
    • C03C21/00—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface
    • 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
    • C03C3/12—Silica-free oxide glass compositions
    • C03C3/16—Silica-free oxide glass compositions containing phosphorus
    • C03C3/17—Silica-free oxide glass compositions containing phosphorus containing aluminium or beryllium
    • 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
    • C03C3/12—Silica-free oxide glass compositions
    • C03C3/23—Silica-free oxide glass compositions containing halogen and at least one oxide, e.g. oxide of boron
    • C03C3/247—Silica-free oxide glass compositions containing halogen and at least one oxide, e.g. oxide of boron containing fluorine and phosphorus
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C4/00—Compositions for glass with special properties
    • C03C4/08—Compositions for glass with special properties for glass selectively absorbing radiation of specified wave lengths
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters

Definitions

  • the present invention relates to a glass in which the variation in mechanical strength is suppressed.
  • a solid-state image sensor module using CCD (Charge Coupled Device) or CMOS (Complementary Metal Oxide Semiconductor) used for digital still cameras etc. uses near-infrared cut filter glass using phosphate glass or fluorophosphate glass It is done.
  • CCD Charge Coupled Device
  • CMOS Complementary Metal Oxide Semiconductor
  • Patent Document 1 a method of chamfering the end face of the glass has been proposed.
  • a bending stress acts on the glass, a flaw on the glass surface becomes a starting point of the crack, and therefore the strength of the glass is enhanced by removing the flaw.
  • Patent Document 2 a method of treating a crack on the end face of a glass plate to a predetermined length or less by etching.
  • Patent Document 3 a method of cutting glass using an internally modified laser has been proposed (see, for example, Patent Document 3).
  • the in-plane strength of the glass can be measured by the breaking load.
  • the breaking load of the glass needs to have a high average value, it is also considered important that the variation of the breaking load is small. That is, when the variation in the breaking load is large, there is a possibility that the glass having a low breaking load may be mixed although the percentage is very small, and there is a risk of the glass breaking when using the device.
  • the minimum value of the breaking load can be estimated to some extent, so that it is possible to prevent the glass having an excessively low breaking load from being used for the device.
  • the present invention has been made under such circumstances, and it is an object of the present invention to provide a glass having a small variation in mechanical strength.
  • the glass of the present invention is a glass in which at least a part of the surface layer is composed of a chemical strengthening layer, and in the glass, the glass interior excluding the chemical strengthening layer is any of P, Al, Li and Na. It is characterized in that it contains an alkali metal consisting of one or both of them.
  • FIG. 1 is a cross-sectional view showing an embodiment of the glass of the present invention.
  • the surface layer including the main surfaces on both sides thereof is constituted by the chemical strengthening layer 2, and the portion excluding the chemical strengthening layer 2 is the inside 1 of the glass.
  • the structure of the chemical strengthening layer in the glass of this invention is not limited to this.
  • at least a part of the surface layer may be constituted of a chemical strengthening layer.
  • the glass interior 1 of the glass 10 contains, as essential components, each component of P (phosphorus), Al (aluminum) and an alkali metal (however, consisting of one or both of Li (lithium) and Na (sodium)). contains.
  • an alkali metal contained in any one or both of Li and Na contained in the glass interior 1 is indicated by “R” as necessary.
  • the surface layer including the main surfaces on both sides of the precursor having the same size as the glass 10 and the entire composition having the same composition as the composition 1 of the glass 10 is converted into the chemical strengthening layer 2 by ion exchange.
  • the configuration is such that a portion maintaining the composition of the precursor that has not been ion-exchanged exists as the glass interior 1 inside the surface layer. That is, in the glass of the present invention, both the chemical strengthening layer and the inside of the crow are made of glass, but the glass compositions of the two are different.
  • the precursor of the glass before ion exchange which has the same composition as the composition inside the glass as a whole, is simply referred to as "glass precursor".
  • Ion exchange specifically refers to the fact that the R component in the glass precursor is ion-exchanged to another monovalent alkali metal ion having a larger ionic radius than this R component.
  • a glass precursor of Li + ionic radius: 60 pm
  • Na + ionic radius: 95pm
  • a glass precursor Na + is K + (ionic radius: 133pm) in ion-exchanged
  • Na + ion-exchanged with Li + in the glass precursor and diffused to the glass may be ion-exchanged to K + .
  • the chemical strengthening layer has a glass composition in which the content of either Na + or K + or both is higher than the glass composition in the glass.
  • the glass of the present invention there is no difference in the composition other than the alkali metal between the glass interior and the chemical strengthening layer.
  • components common to the glass interior and the chemical strengthening layer are described as components of the glass of the present invention.
  • the glass of the present invention contains P and Al.
  • P is a network forming component and a main component necessary for vitrification.
  • Al is a modifying component of glass and is a component that suppresses crystallization and phase separation during glass production.
  • the glass of the present invention contains R inside the glass. That is, in the present invention, the glass precursor which becomes the glass of the present invention by ion exchange of the surface layer contains R for the ion exchange, and the obtained glass of the present invention contains R inside the glass.
  • the present inventor has found that when the chemical strengthening layer 2 is present on at least a part of the surface layer of the glass 10, the variation in mechanical strength of the glass 10 is reduced. The reason is considered to be due to the following mechanism.
  • the factor that the mechanical strength of the glass varies is a flaw present on the glass surface.
  • stress concentration occurs at the tip of the flaw and breakage occurs. Since the flaws on the glass surface are generated by various external factors such as the production process and handling during use, the depth of the flaws is not uniform. In particular, deep flaws are prone to stress concentration, and even with a weak tensile stress, the glass breaks, resulting in variations in the mechanical strength of the glass.
  • the glass of the present invention in the surface layer of the glass precursor, instead of the R component originally present, ions having a larger ion radius are diffused sufficiently deeply to make the surface layer a chemically strengthened layer.
  • the glass structure in the vicinity of the tip of the deep flaw expands, and the stress generated at the tip of the flaw when the tensile stress acts on the glass can be reduced.
  • the mechanical strength does not decrease even if there is a deep scratch, and the variation in mechanical strength is reduced.
  • the chemical strengthening layer 2 may be provided on the entire surface of the glass 10 or may be provided on only a part of the surface. As shown in FIG. 1, when the glass 10 has a plate shape, it is preferable to provide the chemical strengthening layer 2 on the surface layer including the main surface. When a bending stress acts on the plate-shaped glass, the amount of deformation of the main surface is large.
  • the chemical strengthening layer 2 preferably has a thickness of 1 to 100 ⁇ m from the surface of the glass 10 in the depth direction. If the thickness of the chemical strengthening layer 2 is less than 1 ⁇ m, the effect of reducing the variation in mechanical strength of the glass 10 can not be sufficiently obtained. When the thickness of the chemical strengthening layer 2 is more than 100 ⁇ m, the process for forming the chemical strengthening layer 2 takes a long time.
  • the thickness of the chemical strengthening layer 2 is more preferably 2 to 50 ⁇ m, still more preferably 3 to 30 ⁇ m, from the viewpoint of suppressing cracking due to tensile stress generated inside the glass.
  • the chemical strengthening layer 2 of the glass 10 has a content of either Na + or K + or both more than that of the glass interior 1 using an electron probe micro analyzer. It can be measured as a part.
  • the chemical strengthening layer 2 may have a compressive stress. If there is a chemical strengthening layer 2 having a compressive stress on the surface of the glass 10, the glass 10 having high mechanical strength in order to suppress the extension of cracks present on the surface of the glass 10 when a bending stress is applied to the glass 10. You can get Further, as described above, since the dispersion of the mechanical strength of the glass 10 can be reduced by having the chemical strengthening layer 2 on the surface layer of the glass 10, the glass having the same composition without the chemical strengthening layer 2, ie, a glass precursor Compared to the body, it is possible to obtain a glass having a high average breaking load and a small variation in breaking load. Such a glass 10 has a very low probability of occurrence of an excessively low breaking load, so that the risk of breakage of the glass 10 when the glass 10 is used in equipment can be reduced.
  • the compressive stress of the chemical strengthening layer 2 of the glass 10 is preferably 10 to 1000 MPa.
  • the compressive stress of the chemical strengthening layer 2 can be measured using a birefringence measuring device.
  • the glass 10 When the glass 10 is cut into small pieces, for example, according to the size of the product, it is preferable to cut using an internally modified laser.
  • an internally modified laser When the glass is cut by the internally modified laser, a modified region is formed inside the glass by laser focusing, and a crack is extended from there to cut the glass.
  • the glass piece obtained by cutting when an external stress is generated in the glass piece when the modified region reaches the end of the glass piece (the intersection of the main surface and the end face of the glass piece), the end Since the glass pieces are broken from the point of origin, the glass pieces have low mechanical strength.
  • stretching is preferable from the viewpoint of bending stress and the accuracy of the cut surface such as tape expand.
  • the chemical strengthening layer 2 having a compressive stress is present in the surface layer, a tensile stress is present in the glass interior 1 forming the modified region.
  • the output of the laser necessary for forming the modified region can be suppressed, and the modified region becomes smaller. Therefore, there is no modified region at the end of the glass piece obtained by cutting, and as a result, a glass piece with high mechanical strength can be obtained.
  • the glass of the present invention preferably has a glass transition temperature (Tg) of 600 ° C. or less.
  • Tg glass transition temperature
  • the Tg of the chemical strengthening layer and the Tg inside the glass are substantially the same and are treated as the same. That is, the Tg of the glass precursor and the Tg of the glass of the present invention obtained from the glass precursor can be treated as the same.
  • Tg is 600 degrees C or less, it is possible to produce the glass 10 which has the chemical strengthening layer 2 in surface layer from a glass precursor in a short time. Moreover, since the chemical strengthening layer 2 can be formed at a relatively low temperature, the surface of the chemical strengthening layer 2 can be prevented from being roughened, which is preferable for using the glass 10 as an optical element. In addition, when the chemical strengthening layer 2 can be formed at a low temperature for a short time, the effect of suppressing the manufacturing cost (the amount of power) of the glass 10 can also be obtained.
  • the Tg of the glass 10 is preferably 580 ° C. or less, more preferably 570 ° C. or less.
  • the Tg is preferably 300 ° C. or more. That is, the Tg of the glass 10 is preferably 300 to 570 ° C. Tg can be measured, for example, by a thermal expansion method.
  • the glass 10 is preferably a phosphate glass.
  • the phosphate glass is a glass in which P is a main component for forming a network, and in the present invention, phosphate glass, fluorophosphate glass containing fluorine, silicophosphate glass containing silicon, sulfur It is a concept including the sulfated phosphate glass contained.
  • Examples of the phosphoric acid-based glass in the present invention specifically, contain from 35 to 80% of P 2 O 5 in mass% on oxide conversion in the glass inside 1, or 20 to the P 5+ by cationic% 60 It is preferable to contain%.
  • the glass 10 preferably contains F (fluorine) as a glass component. It is known that glasses having P as a network forming component have inferior weather resistance (particularly water resistance). The glass 10 can improve heat resistance significantly by containing F as a glass component.
  • the glass 10 preferably contains Cu (copper) as a glass component.
  • Cu is known as a component that absorbs near-infrared light, for example, light with a wavelength of 700 to 1100 nm.
  • the glass 10 can be used as an optical filter glass excellent in near-infrared absorption characteristics by containing Cu.
  • glass 10 there are, for example, two embodiments of glass having the inside of the glass of the two types of compositions shown below.
  • the glass of the first embodiment is a so-called copper-containing phosphate glass, and in particular, the P component and Cu component (Cu 2+ ) in the glass substantially cut infrared rays by absorbing light in the near infrared wavelength range.
  • the inside of the glass is In mass% display of the following oxide conversion, P 2 O 5 : 35 to 80% Al 2 O 3 : 5 to 20% ⁇ R 2 O: 3 ⁇ 30% ( provided that, R 2 O is any one or more of Li 2 O and Na 2 O, ⁇ R 2 O represents these total amount.) ⁇ R′O: 3 to 35% (wherein R′O is one or more of MgO, CaO, SrO, BaO, and ZnO, and RR′O represents the total amount of these) CuO: 0.5 to 20% It is preferable to contain
  • the reason for limiting the content of each component constituting the inside of the glass as described above will be described below.
  • the content of each component is the mass% display of oxide conversion in glass inside.
  • P 2 O 5 is a main component (glass forming oxide) that forms glass, and is an essential component for enhancing near-infrared cuttability. If the content of P 2 O 5 is less than 35%, the effect is not sufficiently obtained, and if it exceeds 80%, the melting temperature rises and the transmittance in the visible region is reduced, which is not preferable.
  • the content of P 2 O 5 is preferably 38 to 77%, more preferably 40 to 75%.
  • Al 2 O 3 is an essential component for enhancing the weather resistance. If the content of Al 2 O 3 is less than 5%, the effect can not be obtained sufficiently, and if it exceeds 20%, the melting temperature of the glass becomes high, and the near infrared ray cuttability and the visible region transmittance decrease.
  • the content of Al 2 O 3 is preferably 5.5 to 17%, more preferably 6 to 15%.
  • R 2 O is an essential component for lowering the melting temperature of glass to form a chemical strengthening layer.
  • R 2 O is any one or more of Li 2 O and Na 2 O contained in the glass interior.
  • ⁇ R 2 O means the total amount of Li 2 O and Na 2 O, that is, Li 2 O + Na 2 O. If ⁇ R 2 O is less than 3%, the effect is not sufficient, and if it exceeds 30%, the glass becomes unstable.
  • the ⁇ R 2 O is preferably 5 to 28%, more preferably 6 to 25%.
  • Li 2 O is not preferable because when the content of Li 2 O having the effect of forming a chemical strengthening layer and lowering the melting temperature of the glass exceeds 15%, the glass becomes unstable.
  • the content of Li 2 O is preferably 0 to 10%, more preferably 0 to 8%.
  • Na 2 O forms a chemical strengthening layer and has the effect of lowering the melting temperature of the glass.
  • the content of Na 2 O is preferably 0 to 22%, more preferably 0 to 20%.
  • the inside of the glass may contain K 2 O as an alkali metal oxide other than R 2 O.
  • K 2 O has the effect of lowering the melting temperature of glass, which promotes the formation of a chemical strengthening layer.
  • the content of K 2 O is preferably 0 to 25%. When the content of K 2 O exceeds 25%, the glass becomes unstable, which is not preferable.
  • the content of K 2 O is preferably 0 to 20%, more preferably 0 to 15%.
  • R′O is an essential component to enhance the stability of the glass and to lower the melting temperature of the glass.
  • R′O is at least one of MgO, CaO, SrO, BaO and ZnO contained in the glass.
  • ⁇ R′O refers to the total amount of MgO, CaO, SrO, BaO and ZnO, that is, MgO + CaO + SrO + BaO + ZnO. If ⁇ R′O is less than 3%, the effect is not sufficient, and if it exceeds 35%, the glass becomes unstable.
  • the ⁇ R′O is preferably 3.5 to 32%, more preferably 4 to 30%.
  • MgO is not an essential component, it has the effect of enhancing the stability of the glass. If the content of MgO exceeds 5%, the near-infrared cuttability is unfavorably reduced.
  • the content of MgO is preferably 3% or less, more preferably 2% or less.
  • SrO is not an essential component, it has the effect of enhancing the stability of the glass. If the content of SrO exceeds 15%, the near infrared cuttability is unfavorably reduced.
  • the content of SrO is preferably 0 to 12%, more preferably 0 to 10%.
  • BaO is not an essential component, it has the effect of lowering the melting temperature of the glass. If the content of BaO exceeds 30%, the glass becomes unstable.
  • the content of BaO is preferably 0 to 27%, more preferably 0 to 25%.
  • ZnO is not an essential component, it has the effect of lowering the melting temperature of the glass.
  • the content of ZnO is preferably 8% or less, more preferably 5% or less.
  • CuO is a component for enhancing near-infrared cuttability. If the content of CuO is less than 0.5%, the effect is not sufficiently obtained, and if it exceeds 20%, the visible light transmittance is unfavorably reduced.
  • the content of CuO is preferably 0.8 to 19%, more preferably 1.0 to 18%.
  • the glass of the second embodiment is a so-called copper-containing fluorophosphate glass, and in particular, the P component and Cu component (Cu 2+ ) in the glass absorb infrared rays of wavelengths in the near-infrared range to significantly cut infrared rays.
  • the P component and Cu component (Cu 2+ ) in the glass absorb infrared rays of wavelengths in the near-infrared range to significantly cut infrared rays.
  • the inside of the glass is In cation% indication, P 5+ : 20 to 60% Al 3+ : 3 to 20% ⁇ R +: 5 ⁇ 40% (provided that, R + is a Li + and Na + or one or more, .SIGMA.R + represents these total amount.)
  • RR ′ 2+ 5 to 30% (wherein R ′ 2+ is any one or more of Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ , and Zn 2+ , and RR ′ 2+ represents the total amount of these.
  • Total content of Cu 2+ and Cu + 0.5 to 25% While containing In% anion, F -: 10 ⁇ 70% Is preferably contained.
  • cation% and anion% are units as follows. First, constituent components in the composition of glass are divided into a cationic component and an anionic component. And “cation%” is a unit which represented content of each cation component in percentage, when sum total content of all the cation components contained in glass is set to 100 mol%. The “anion%” is a unit in which the content of each anion component is expressed in percentage, when the total content of all the anion components contained in the glass is 100 mol%.
  • the content of each of the cationic components and the value of the total content are the value of the cation% in the glass interior, and the value of each content of the anionic components and the total content are It is a value of the anion% display in glass inside.
  • P 5+ is a main component forming glass, and is an essential component for enhancing the cuttability of the near infrared region. If the content of P 5+ is less than 20%, the effect can not be obtained sufficiently, and if it exceeds 60%, the glass becomes unstable and the weather resistance is lowered, which is not preferable.
  • the content of P 5+ is more preferably 20 to 58%, still more preferably 22 to 56%, still more preferably 24 to 54%, and particularly preferably 25 to 50%.
  • Al 3+ is an essential component for enhancing the weather resistance and the like. If the content of Al 3+ is less than 3%, the effect can not be sufficiently obtained, and if it exceeds 20%, the glass becomes unstable, and problems such as reduction in infrared ray cutability occur, which is not preferable.
  • the content of Al 3+ is more preferably 4 to 18%, still more preferably 4.5 to 15%, still more preferably 5 to 13%.
  • Al 2 O 3 or Al (OH) 3 is used as a raw material for Al 3+ , the glass becomes unstable due to the increase of melting temperature, generation of unmelted substance, and decrease of F ⁇ charge. And the like, which is not preferable because it causes problems such as, and it is preferable to use AlF 3 .
  • R + is an essential component for forming a chemical strengthening layer, lowering the melting temperature of the glass, lowering the liquidus temperature of the glass, stabilizing the glass, and the like.
  • R + refers to any one or more of Li + and Na + contained in the glass interior.
  • RR + refers to the total amount of Li + and Na + , that is, Li + + Na + . If RR + is less than 5%, the effect can not be sufficiently obtained, and if it exceeds 40%, the glass becomes unstable.
  • the ⁇ R + is more preferably 6 to 38%, further preferably 10 to 37%, and still more preferably 15 to 36%.
  • Li + is a component for forming a chemical strengthening layer, lowering the melting temperature of the glass, lowering the liquidus temperature of the glass, stabilizing the glass, and the like.
  • the content of Li + is preferably 5 to 40%. If it is less than 5%, the effect can not be obtained sufficiently, and if it exceeds 40%, the glass becomes unstable.
  • the content of Li + is more preferably 8 to 38%, still more preferably 10 to 35%, and still more preferably 6 to 30%.
  • Na + is a component for forming a chemical strengthening layer, lowering the melting temperature of the glass, lowering the liquidus temperature of the glass, stabilizing the glass, and the like.
  • the content of Na + is preferably 5 to 40%. If it is less than 5%, the effect can not be obtained sufficiently, and if it exceeds 40%, the glass becomes unstable.
  • the content of Na + is more preferably 5 to 35%, still more preferably 6 to 30%.
  • K + is a component that promotes formation of a chemical strengthening layer, lowers the melting temperature of the glass, lowers the liquidus temperature of the glass, and the like.
  • the content of K + is preferably 0.1 to 30%. When K + is contained, if it is less than 0.1%, the effect is not sufficiently obtained, and if it exceeds 30%, the glass becomes unstable, which is not preferable.
  • the content of K + is more preferably 0.5 to 25%, still more preferably 0.5 to 20%.
  • R ′ 2+ is a component for lowering the melting temperature of the glass, lowering the liquidus temperature of the glass, stabilizing the glass, enhancing the strength of the glass, and the like.
  • R ′ 2+ refers to any one or more of Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ and Zn 2+ contained in the glass.
  • RR ′ 2+ refers to the total amount of Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ and Zn 2+ , ie, Mg 2+ + Ca 2+ + Sr 2+ + Ba 2+ + Zn 2+ .
  • ⁇ R ′ 2+ is less than 5%, the effect can not be obtained sufficiently, and if it exceeds 30%, the glass becomes unstable, the infrared ray cutability decreases, and the strength of the glass decreases, which is not preferable.
  • the ⁇ R ′ 2+ is more preferably 5 to 28%, still more preferably 7 to 25%, and still more preferably 9 to 23%.
  • Mg 2+ is not an essential component, it is a component for lowering the melting temperature of the glass, lowering the liquidus temperature of the glass, stabilizing the glass, enhancing the strength of the glass, and the like.
  • the content of Mg 2+ is preferably 1 to 30%. When it contains Mg 2+ , its effect can not be sufficiently obtained if it is less than 1%, and the glass becomes unstable if it exceeds 30%, which is not preferable.
  • the content of Mg 2+ is more preferably 1 to 25%, still more preferably 1 to 20%.
  • Ca 2+ is not an essential component, it is a component for lowering the melting temperature of the glass, lowering the liquidus temperature of the glass, stabilizing the glass, enhancing the strength of the glass, and the like.
  • the content of Ca 2+ is preferably 1 to 30%. When it contains Ca 2+ , its effect can not be sufficiently obtained if it is less than 1%, and the glass becomes unstable if it exceeds 30%, which is not preferable.
  • the content of Ca 2+ is more preferably 1 to 25%, still more preferably 1 to 20%.
  • Sr 2+ is a component for lowering the melting temperature of the glass, lowering the liquidus temperature of the glass, stabilizing the glass, and the like.
  • the content of Sr 2+ is preferably 1 to 30%. When the content of Sr 2+ is less than 1%, the effect is not sufficiently obtained, and when it exceeds 30%, the glass becomes unstable. More preferably, it is 1 to 25%, and still more preferably 1 to 20%.
  • Ba 2+ is not an essential component, it is a component for lowering the melting temperature of the glass, lowering the liquidus temperature of the glass, stabilizing the glass, and the like.
  • the content of Ba 2+ is preferably 1 to 30%. When it contains Ba 2+ , its effect can not be sufficiently obtained if it is less than 1%, and the glass becomes unstable if it exceeds 30%, which is not preferable.
  • the content of Ba 2+ is more preferably 1 to 25%, still more preferably 1 to 20%.
  • Zn 2+ is not an essential component, it has effects such as lowering the melting temperature of the glass and lowering the liquidus temperature of the glass.
  • the content of Zn 2+ is preferably 1 to 30%. When it contains Zn 2+ , its effect can not be sufficiently obtained if it is less than 1%, and the solubility of the glass is deteriorated if it exceeds 30%, which is not preferable.
  • the content of Zn 2+ is more preferably 1 to 25%, still more preferably 1 to 20%.
  • the total content of Cu 2+ and Cu + is an essential component for near infrared cut. If the total content of Cu 2+ and Cu + is less than 0.5%, the effect can not be sufficiently obtained when the thickness of the glass is reduced, and if it exceeds 25%, the visible light transmittance decreases Not desirable for
  • the total content of Cu 2+ and Cu + is more preferably 0.2 to 24%, still more preferably 0.3 to 23%, and still more preferably 0.4 to 22%.
  • Sb 3+ is not an essential component, it has the effect of enhancing the near-infrared cutting performance by enhancing the oxidation of the glass and increasing the concentration of Cu 2+ ions.
  • Sb 3+ is contained, 1% or less is preferable.
  • the content of Sb 3+ exceeds 1%, the stability of the glass is reduced, which is not preferable.
  • the content of Sb 3+ is preferably 0.01 to 8%, more preferably 0.05 to 0.5%, and still more preferably 0.1 to 0.3%.
  • O 2 ⁇ is a component for stabilizing the glass and enhancing mechanical properties such as strength, hardness and elastic modulus.
  • the content of O 2 ⁇ is preferably 30 to 90%. If the content of O 2 ⁇ is less than 30%, the effect can not be sufficiently obtained, and if it exceeds 90%, the glass becomes unstable and the weather resistance is lowered, which is not preferable.
  • the content of O 2 ⁇ is more preferably 30 to 80%, still more preferably 30 to 75%.
  • F ⁇ is a component for improving the weatherability in order to stabilize the glass. If the content of F ⁇ is less than 10%, the effect can not be obtained sufficiently, and if it exceeds 70%, mechanical properties such as strength, hardness and elastic modulus may decrease, which is not preferable.
  • the glass according to the first embodiment preferably contains substantially no PbO, As 2 O 3 , V 2 O 5 , LaY 3 , YF 3 , YbF 3 , or GdF 3 .
  • PbO is a component that lowers the viscosity of glass and improves manufacturing workability.
  • As 2 O 3 is a component that acts as an excellent fining agent capable of generating a fining gas in a wide temperature range.
  • PbO and As 2 O 3 are environmentally hazardous substances, it is desirable not to contain them as much as possible.
  • V 2 O 5 absorbs light in the visible region, the transmittance of ultraviolet light may decrease, and it is desirable that V 2 O 5 be not contained as much as possible.
  • LaY 3 , YF 3 , YbF 3 , and GdF 3 are components for stabilizing the glass, it is desirable not to contain as much as possible because the raw materials are relatively expensive and cost increases.
  • "not substantially contained” means that it is not intended to be used as a raw material, and it is considered that the raw material components and the unavoidable impurities mixed from the manufacturing process are not contained. The amount of such unavoidable impurities is, for example, 0.1% or less with respect to the entire inside of the glass.
  • the glass of the second embodiment it is possible to add a nitrate compound or a sulfate compound having a cation forming the glass in the composition of the glass as an oxidizing agent or a clarifying agent.
  • the oxidizing agent has the effect of adjusting the Cu + / total Cu amount of the Cu component in the glass to a desired range.
  • the addition amount of the nitrate compound and the sulfate compound is preferably 0.5 to 10% by mass in external addition with respect to the total amount of the raw material mixture having the above-described composition inside the glass. If the addition amount is less than 0.5% by mass, there is no effect of improving the transmittance, and if it exceeds 10% by mass, formation of glass becomes difficult.
  • the addition amount is more preferably 1 to 8% by mass, and still more preferably 3 to 6% by mass.
  • the nitrate compounds Al (NO 3) 3, LiNO 3, NaNO 3, KNO 3, Mg (NO 3) 2, Ca (NO 3) 2, Sr (NO 3) 2, Ba (NO 3) 2, Zn (NO 3 ) 2 , Cu (NO 3 ) 2 and the like.
  • As a sulfate compound Al 2 (SO 4 ) 3 .16H 2 O, Li 2 SO 4 , Na 2 SO 4 , Na 2 SO 4 , K 2 SO 4 , MgSO 4 , CaSO 4 , SrSO 4 , BaSO 4 , ZnSO 4 , CuSO 4 Etc.
  • the glass of the second embodiment contains the F (fluorine) component as an essential component, and therefore is excellent in weathering resistance. Specifically, it is possible to suppress the deterioration of the glass surface and the reduction of the transmittance due to the reaction with the moisture in the atmosphere.
  • the evaluation of the weather resistance is, for example, using a high temperature and high humidity tank, and holding the optically polished glass sample in a high temperature and high humidity tank at 65 ° C. and 90% relative humidity for 1000 hours. Then, the burnt state of the glass surface can be visually observed and evaluated.
  • the transmittance of the glass before being introduced into the high temperature and high humidity tank can be evaluated by comparing the transmittance of the glass after being held in the high temperature and high humidity tank for 1000 hours.
  • the glass 10 can be used in any shape such as a plate shape, a lens shape (concave shape, convex shape), a tube shape, and a rod shape.
  • a plate shape a lens shape (concave shape, convex shape), a tube shape, and a rod shape.
  • the glass 10 when using the glass 10 as an optical filter, it is preferable that it is plate shape.
  • the plate thickness is preferably 0.01 to 1 mm. If the thickness of the glass 10 is less than 0.01 mm, the risk of breakage during manufacturing is large. Moreover, when it is more than 1 mm, the mass of the glass 10 is large, which may hinder the weight reduction of the device.
  • the glass 10 can be suitably used for the following applications utilizing the specific optical properties of the phosphate glass.
  • it can be suitably used for near-infrared cut filter glass which is one of optical filters.
  • the glass 10 may be provided with an optical thin film such as an antireflective film, an infrared ray cut film, an ultraviolet ray and an infrared ray cut film on the surface thereof.
  • optical thin films are formed of a single layer film or a multilayer film, and can be formed by a known method such as a vapor deposition method or a sputtering method.
  • a resin layer in which a pigment that absorbs light of a specific wavelength or metal fine particles is dispersed may be provided on the surface of the glass 10.
  • the method for producing the glass 10 is not particularly limited. Typically, a glass precursor having the same shape and size as the glass 10 can be produced, and the surface layer can be manufactured as a chemically strengthened layer by ion exchange treatment.
  • the raw materials are weighed and mixed such that the obtained glass precursor has a predetermined composition range, for example, the above-described composition inside the glass (mixing step).
  • This raw material mixture is placed in a platinum crucible, and heated and melted in an electric furnace at a temperature of 700 ° C. to 1300 ° C. (melting step). After sufficiently stirring and clarifying, it is cast into a mold or the like to form it into a predetermined shape (forming step).
  • the glass precursor is cut and polished to be processed into a predetermined shape (processing step) to obtain a glass precursor.
  • the glass precursor may be formed into a predetermined shape by an appropriate method such as press molding, reheat press molding, reconstructer molding, redraw molding, bellows molding and the like.
  • the surface layer of the obtained glass precursor is subjected to ion exchange treatment to form a chemically strengthened layer 2, and a glass 10 comprising the chemically strengthened layer 2 and the glass interior 1 not ion-exchanged is obtained (chemically reinforced layer forming step).
  • the glass may be cut again, polished, or dipped in a chemical solution (acidic or alkaline solution).
  • the chemical strengthening layer formation step is a step of ion exchange treatment of the surface layer of the glass precursor.
  • the ion exchange treatment can be performed, for example, by immersing the glass precursor in molten salt at 200 ° C. to 450 ° C. for about 1 to 50 hours.
  • the temperature of the molten salt is taken as the ion exchange treatment temperature.
  • the ion exchange treatment temperature is more preferably 215 to 400 ° C.
  • the immersion time is taken as the ion exchange treatment time.
  • the ion exchange treatment time is more preferably 2 to 30 hours.
  • the molten salt used depends on the composition of the alkali metal in the glass precursor. Ion exchange of the Li-containing glass precursor is carried out in the molten salt containing Na + and / or K + . Ion exchange of the Na-containing glass precursor is carried out in the molten salt containing K + .
  • a molten salt of sodium nitrate (NaNO 3 ) or a molten salt in which potassium nitrate (KNO 3 ) and sodium nitrate (NaNO 3 ) are mixed at an appropriate ratio can be used.
  • the glass of the present invention has a chemical strengthening layer on the surface, and the inside of the glass contains P, Al, and an alkali metal composed of either Li or Na, or both, It is a glass with a small variation in mechanical strength.
  • the in-plane strength of the glass is measured by the breaking load, the variation of the breaking load is small.
  • the minimum value of the breaking load can be estimated to some extent, it is possible to prevent the glass having an excessively low breaking load from being used for the device.
  • Examples of the present invention and comparative examples are shown in Table 1. Examples 1 to 4 are examples of the present invention, and Example 5 is a comparative example of the present invention.
  • glass precursors consisting of glass materials all having the same composition were prepared as follows.
  • the composition of the glass material used is as follows, and Tg is 400 ° C.
  • Example 5 is the glass precursor itself in which the chemical strengthening layer is not formed.
  • each glass of the Example of this invention has a small standard deviation of a breaking load with respect to the glass of a comparative example. Therefore, it can be seen that the risk of breakage can be reduced when used in equipment or the like. Therefore, when it uses for an apparatus etc., the risk of breakage is small and it can use with thinner board thickness.
  • the glass of the present invention is a glass in which at least a part of the surface layer is composed of a chemical strengthening layer, and the inside of the glass excluding the chemical strengthening layer is made of P, Al, Li and Na, or both Since it is a structure containing the alkali metal which becomes, it is glass with a small dispersion

Landscapes

  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Glass Compositions (AREA)
  • Surface Treatment Of Glass (AREA)

Abstract

L'invention concerne un verre qui présente une faible variation de résistance mécanique. Un verre est conçu de sorte que : au moins une partie d'une couche de surface est composée d'une couche chimiquement durcie ; et la partie intérieure du verre, à l'exclusion de la couche chimiquement durcie, contient du P, de l'Al et un métal alcalin qui est composé de Li et/ou de Na.
PCT/JP2018/030691 2017-08-31 2018-08-20 Verre WO2019044563A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN201880055878.1A CN111051262B (zh) 2017-08-31 2018-08-20 玻璃
JP2019539374A JP7092135B2 (ja) 2017-08-31 2018-08-20 ガラス

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2017-167161 2017-08-31
JP2017167161 2017-08-31

Publications (1)

Publication Number Publication Date
WO2019044563A1 true WO2019044563A1 (fr) 2019-03-07

Family

ID=65526321

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2018/030691 WO2019044563A1 (fr) 2017-08-31 2018-08-20 Verre

Country Status (3)

Country Link
JP (1) JP7092135B2 (fr)
CN (1) CN111051262B (fr)
WO (1) WO2019044563A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022138299A1 (fr) * 2020-12-25 2022-06-30 Ａｇｃ株式会社 Verre de fluorophosphate et filtre de coupure de rayons infrarouges proches

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114538772B (zh) * 2022-03-24 2022-12-02 成都光明光电股份有限公司 玻璃、玻璃元件及滤光器

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60235740A (ja) * 1984-04-18 1985-11-22 シヨツト　グラスヴエルケ 光学着色フイルター用ガラス
JPH04104918A (ja) * 1990-08-23 1992-04-07 Asahi Glass Co Ltd 近赤外吸収ガラス
JPH0616451A (ja) * 1991-06-18 1994-01-25 Toshiba Glass Co Ltd 近赤外線カットフィルタガラス
JP2005320178A (ja) * 2004-05-06 2005-11-17 Isuzu Seiko Glass Kk 近赤外線カットガラス
JP2006342024A (ja) * 2005-06-09 2006-12-21 Asahi Techno Glass Corp 近赤外線カットフィルタガラス
JP2007099604A (ja) * 2005-09-06 2007-04-19 Hoya Corp 近赤外線吸収ガラス、それを備えた近赤外線吸収素子および撮像装置
JP2012148964A (ja) * 2010-12-23 2012-08-09 Schott Ag フッ化リン酸ガラス
JP2014101255A (ja) * 2012-11-21 2014-06-05 Nippon Electric Glass Co Ltd フツリン酸ガラスの製造方法
JP2015078086A (ja) * 2013-10-16 2015-04-23 日本電気硝子株式会社 光学ガラス
WO2015080043A1 (fr) * 2013-11-26 2015-06-04 旭硝子株式会社 Élément en verre et procédé de production d'élément en verre

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014119780A1 (fr) * 2013-02-04 2014-08-07 旭硝子株式会社 Procédé pour couper un substrat en verre, substrat en verre, verre filtrant coupé par rayons infrarouges proches et procédé de fabrication de substrat en verre
JP6428767B2 (ja) * 2014-04-09 2018-11-28 Ａｇｃ株式会社 近赤外線カットフィルタガラス

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60235740A (ja) * 1984-04-18 1985-11-22 シヨツト　グラスヴエルケ 光学着色フイルター用ガラス
JPH04104918A (ja) * 1990-08-23 1992-04-07 Asahi Glass Co Ltd 近赤外吸収ガラス
JPH0616451A (ja) * 1991-06-18 1994-01-25 Toshiba Glass Co Ltd 近赤外線カットフィルタガラス
JP2005320178A (ja) * 2004-05-06 2005-11-17 Isuzu Seiko Glass Kk 近赤外線カットガラス
JP2006342024A (ja) * 2005-06-09 2006-12-21 Asahi Techno Glass Corp 近赤外線カットフィルタガラス
JP2007099604A (ja) * 2005-09-06 2007-04-19 Hoya Corp 近赤外線吸収ガラス、それを備えた近赤外線吸収素子および撮像装置
JP2012148964A (ja) * 2010-12-23 2012-08-09 Schott Ag フッ化リン酸ガラス
JP2014101255A (ja) * 2012-11-21 2014-06-05 Nippon Electric Glass Co Ltd フツリン酸ガラスの製造方法
JP2015078086A (ja) * 2013-10-16 2015-04-23 日本電気硝子株式会社 光学ガラス
WO2015080043A1 (fr) * 2013-11-26 2015-06-04 旭硝子株式会社 Élément en verre et procédé de production d'élément en verre

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022138299A1 (fr) * 2020-12-25 2022-06-30 Ａｇｃ株式会社 Verre de fluorophosphate et filtre de coupure de rayons infrarouges proches

Also Published As

Publication number Publication date
CN111051262A (zh) 2020-04-21
JP7092135B2 (ja) 2022-06-28
JPWO2019044563A1 (ja) 2020-10-15
CN111051262B (zh) 2022-09-13

Similar Documents

Publication Publication Date Title
JP6879215B2 (ja) 光学ガラス
JP6604337B2 (ja) ガラス基板、積層基板、およびガラス基板の製造方法
KR102564323B1 (ko) 화학 강화용 유리
EP3652124B1 (fr) Articles à base de verre à profil de contrainte améliorés
CN110255886B (zh) 一种玻璃、玻璃制品及其制造方法
JP6922741B2 (ja) 光学ガラス
CN111423111A (zh) 玻璃材料
WO2010119964A1 (fr) Verre filtrant coupant les rayons infrarouges proches
CN110194589B (zh) 近红外光吸收玻璃、玻璃制品、元件及滤光器
JP2022078351A (ja) 無アルカリガラス基板、積層基板、およびガラス基板の製造方法
TW201834991A (zh) 光學玻璃、預成形體以及光學元件
JP2010208906A (ja) 光デバイス用基板ガラス
US20200325063A1 (en) Optical glass and optical member
JP7092135B2 (ja) ガラス
JP6075714B2 (ja) 光学ガラス
JPH0624998B2 (ja) 無アルカリガラス
TW201837005A (zh) 光學玻璃
US20220388893A1 (en) Ultraviolet transmission glass
KR20180041066A (ko) 화학 강화용 유리
JP2004026510A (ja) 多層膜フィルター用基板ガラス及び多層膜フィルター
TWI838347B (zh) 化學強化用玻璃
WO2022085403A1 (fr) Élément optique ayant une couche de contrainte de compression
WO2023219023A1 (fr) Verre, feuille de verre et procédé de fabrication de feuille de verre
TW202319361A (zh) 化學強化光學玻璃
US20230133650A1 (en) Chemically strengthened optical glass

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 18849639

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2019539374

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 18849639

Country of ref document: EP

Kind code of ref document: A1