WO2021238476A1 - 玻璃材料 - Google Patents

玻璃材料 Download PDF

Info

Publication number
WO2021238476A1
WO2021238476A1 PCT/CN2021/087203 CN2021087203W WO2021238476A1 WO 2021238476 A1 WO2021238476 A1 WO 2021238476A1 CN 2021087203 W CN2021087203 W CN 2021087203W WO 2021238476 A1 WO2021238476 A1 WO 2021238476A1
Authority
WO
WIPO (PCT)
Prior art keywords
glass
zno
glass material
less
sro
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/CN2021/087203
Other languages
English (en)
French (fr)
Inventor
毛露路
郝良振
匡波
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
CDGM Glass Co Ltd
Original Assignee
CDGM Glass Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by CDGM Glass Co Ltd filed Critical CDGM Glass Co Ltd
Priority to US17/923,675 priority Critical patent/US20230174409A1/en
Priority to EP21811829.7A priority patent/EP4159696A4/en
Priority to JP2022572544A priority patent/JP2023528338A/ja
Publication of WO2021238476A1 publication Critical patent/WO2021238476A1/zh
Anticipated expiration legal-status Critical
Priority to JP2025037346A priority patent/JP2025087872A/ja
Ceased legal-status Critical Current

Links

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
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/097—Glass compositions containing silica with 40% to 90% silica, by weight containing phosphorus, niobium or tantalum
    • 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
    • C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
    • C03C1/004—Refining agents
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
    • C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
    • C03C3/093—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium containing zinc or zirconium
    • 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
    • C03C3/095—Glass compositions containing silica with 40% to 90% silica, by weight containing rare earths
    • 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
    • C03C4/20—Compositions for glass with special properties for chemical resistant glass
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy

Definitions

  • the invention relates to a glass material, in particular to a glass material suitable for the field of photosensitive device packaging.
  • COMS, CCD and other photoelectric conversion devices usually use glass materials as window materials, and the window glass plays a role of light transmission and protection of the photoelectric conversion chip.
  • Early photosensitive devices such as COMS and CCD are usually used in cameras and the environment is more comfortable. Therefore, there is no high requirement for the chemical stability (acid resistance, water resistance and alkali resistance, etc.), weather resistance and temperature shock resistance of the protective window of the photosensitive device. .
  • photosensitive devices are required to have high reliability under very harsh conditions.
  • photosensitive devices used in high-temperature fire fields need to withstand extreme temperature environments of 100-200°C or even higher; photosensitive devices observed in marine environments need to be able to withstand long-term alkaline or acid corrosion; used in observation chemical (chemical) experiments
  • the photosensitive device needs to be able to withstand the corrosion of strong acid and alkali; the photosensitive device used in vehicle and security needs to be exposed to the outdoor environment for a long time.
  • the main component of the photosensitive chip is silicon single crystal material, and the package shell is mainly ceramic material. Ceramic materials have very good chemical stability and impact resistance, but their weakness is that they do not transmit light, and brittle glass materials need to be used as light-transmitting windows. Compared with ceramic materials, glass materials have a huge gap in chemical stability and thermal shock resistance. Therefore, improving the chemical stability and temperature shock resistance of window glass materials is the best way to improve the reliability of photosensitive devices in harsh external environments.
  • the glass material is also required to have a higher transmittance in the range of 360nm to 2000nm to meet the needs of different wavelengths of ultraviolet-visible-near infrared light.
  • the transmittance of glass materials gradually increases in the range of 360nm ⁇ 2000nm, so we can use the internal transmittance at 360nm ( ⁇ 360nm ) to characterize the lowest transmittance of glass.
  • ⁇ 360nm is in Above 78%, it means that the encapsulation glass can meet the transmittance requirements of the above-mentioned wavebands.
  • the packaging glass needs to avoid reflection loss as much as possible, if the refractive index exceeds 1.60, the reflection loss of the glass will increase. Although the reflection loss can be reduced by plating anti-reflection coating, it will bring about cost increase and stray light interference problems.
  • the technical problem to be solved by the present invention is to provide a glass material with high light transmittance and excellent chemical stability.
  • Glass material the composition of which is expressed in weight percentage, containing: SiO 2 : 50 ⁇ 70%; B 2 O 3 : 3 ⁇ 15%; TiO 2 : 0.5 ⁇ 10%; ZnO: 1 ⁇ 12%; Al 2 O 3 : 0.5 ⁇ 10%; Na 2 O+K 2 O: 5 ⁇ 22%, of which B 2 O 3 /SiO 2 is 0.06 ⁇ 0.26, (TiO 2 +ZnO)/Al 2 O 3 is 0.5 ⁇ 8.0 .
  • the glass material according to (1) the composition of which is expressed in weight percentage, and further contains: MgO+CaO+SrO+BaO: 0-10%; and/or Li 2 O: 0-5%; and /Or P 2 O 5 : 0-5%; and/or ZrO 2 : 0-5%; and/or La 2 O 3 : 0-5%; and/or Y 2 O 3 : 0-5%; and /Or Gd 2 O 3 : 0 to 5%; and/or Nb 2 O 5 : 0 to 5%; and/or WO 3 : 0 to 5%; and/or clarifying agent: 0 to 1%.
  • (10) The glass material according to any one of (1) to (3), the composition of which is expressed in weight percentage, wherein: (SiO 2 +TiO 2 )/(Na 2 O+ZnO) is 4.0 to 8.0; and / Or ZnO/B 2 O 3 is 0.4 ⁇ 0.8; and/or (Na 2 O+K 2 O)/Al 2 O 3 is 1.5 ⁇ 5.0; and/or (Na 2 O+K 2 O)/(B 2 O 3 +ZnO) is 0.5 to 1.5; and/or (B 2 O 3 +K 2 O)/Al 2 O 3 is 2.0 to 6.0.
  • the total content of 3 is 5% or less, preferably 3% or less, and more preferably 1% or less.
  • the glass material according to any one of (1) to (3), its composition does not contain F; and/or does not contain Ta 2 O 5 ; and/or does not contain Li 2 O; and/or does not contain Contains P 2 O 5 ; and/or does not contain ZrO 2 .
  • the refractive index of the glass material is 1.48 to 1.56, preferably 1.50 to 1.55, more preferably 1.51 to 1.54; and/or Abbe number It is 50-58, preferably 51-57, more preferably 53-56; and/or the coefficient of thermal expansion ⁇ 20-300°C is 60 ⁇ 10 -7 /K to 90 ⁇ 10 -7 /K, preferably 65 ⁇ 10 -7 /K ⁇ 85 ⁇ 10 -7 /K, more preferably 68 ⁇ 10 -7 /K ⁇ 80 ⁇ 10 -7 /K; and/or Young's modulus is 6000 ⁇ 10 7 Pa or more, preferably 6500 ⁇ 10 7 Pa ⁇ 8500 ⁇ 10 7 Pa, more preferably 7000 ⁇ 10 7 Pa ⁇ 8000 ⁇ 10 7 Pa; and/or the transition temperature is 500°C to 610°C, preferably 520°C to 600°C, more preferably 530 °C to 580 °C; and/or the air bubble degree is above grade A, preferably
  • the weight loss of the glass sample is less than 9mg, preferably less than 7mg, more preferably less than 5mg; and/or the light transmittance ⁇ 360nm is 78% or more, preferably 82% or more, more preferably 85% or more.
  • the glass element is made of the glass material described in any one of (1) to (16).
  • the beneficial effects of the present invention are: through reasonable component design, the glass material obtained by the present invention has higher light transmittance and excellent chemical stability, and meets applications in the fields of photosensitive device packaging and the like.
  • the present invention is not limited to the following embodiments, and can be implemented with appropriate changes within the scope of the object of the present invention.
  • the description of overlapping descriptions may be omitted appropriately, this does not limit the gist of the invention.
  • the glass material of the present invention is sometimes simply referred to as glass.
  • each component of the glass material of the present invention will be described below.
  • the content of each component and the total content are all expressed as a percentage by weight relative to the total amount of the glass substance in the composition converted to oxides.
  • the "composition in terms of oxides” means that the oxides, composite salts, hydroxides, etc. used as the raw materials of the glass material of the present invention decompose and transform into oxides when they are melted , The total weight of the oxide is regarded as 100%.
  • SiO 2 is one of the main components of the glass.
  • an appropriate amount of SiO 2 can ensure that the glass has high water resistance and acid resistance, and at the same time can achieve high light transmittance. If the content of SiO 2 is less than 50%, the water resistance, acid resistance and UV transmittance of the glass are lower than the design requirements. If the content of SiO 2 is higher than 70%, the refractive index of the glass cannot meet the design requirements. The melting temperature of the glass will rise sharply, it is not easy to obtain high-quality glass in production, and the thermal expansion coefficient of the glass will become low. Therefore, the content of SiO 2 in the present invention is limited to 50 to 70%, preferably 55 to 68%, and more preferably 60 to 68%.
  • the addition of a proper amount of B 2 O 3 to the glass can transform the structure of the glass to a denser direction, increase the refractive index of the glass, and achieve higher water resistance and acid resistance. If the content is less than 3%, the above effect is not obvious. If the content of B 2 O 3 is higher than 15%, the water resistance and acid resistance of the glass will decrease instead. Therefore, the content of B 2 O 3 is limited to 3 to 15%, preferably more than 5% but less than or equal to 13%, and more preferably 6 to 12%.
  • the value of B 2 O 3 /SiO 2 affects the difficulty of glass production.
  • B 2 O 3 /SiO 2 is less than 0.06, the melting temperature of the glass rises, which intensifies the corrosion of refractory materials, and it is easy to introduce changes into the glass. Too many colored impurities and inclusions cause the transmittance of the glass to not meet the design requirements, and at the same time lead to an increase in the probability of internal defects in the product.
  • B 2 O 3 /SiO 2 is greater than 0.26, the melting temperature will not drop significantly, and the erosion of B 2 O 3 to refractory materials will increase, which will easily introduce more colored impurities and inclusions into the glass, resulting in short-wave penetration of the glass.
  • the value of B 2 O 3 /SiO 2 is 0.06 to 0.26, preferably 0.08 to 0.2, and more preferably 0.1 to 0.18.
  • the addition of a proper amount of Al 2 O 3 to the glass can improve the water resistance and acid resistance of the glass, and at the same time can reduce the thermal expansion coefficient of the glass, especially in the presence of alkali metal oxides. If the content of Al 2 O 3 is higher than 10%, the thermal expansion coefficient of the glass will decrease rapidly, failing to meet the design requirements. Therefore, the content of Al 2 O 3 is limited to 0.5 to 10%, preferably 1 to 8%, and more preferably 2 to 7%.
  • Adding a proper amount of TiO 2 to the glass can increase the refractive index of the glass, increase the water resistance, acid resistance, and alkali resistance of the glass. At the same time, it can reduce the thermal expansion coefficient of the glass and improve the thermal shock resistance of the glass. If the content of TiO 2 is lower than 0.5%, the above effect is not obvious; if the content of TiO 2 exceeds 10%, the Abbe number of the glass is lower than the design expectation, and the short-wave transmittance drops rapidly, especially in an environment where the melting atmosphere is unstable.
  • the high content of TiO 2 leads to a rapid increase in the refractive index of the glass, which increases the reflection loss of short-wavelength wavelengths without antireflection coating, resulting in a further decrease in the short-wave transmittance and a decrease in the thermal expansion coefficient of the glass. , Failing to meet the design requirements. Therefore, the content of TiO 2 in the present invention is limited to 0.5-10%, preferably 1.5-8%. In some embodiments, taking into account the refractive index, Abbe number of the glass, and the difficulty of controlling the atmosphere during the melting process, it is more preferable that the content of TiO 2 is 2 to 7%.
  • ZnO has a higher field strength in divalent metal oxides. When added to glass, it can improve the acid resistance, water resistance and alkali resistance of the glass, increase the refractive index of the glass, and reduce the thermal expansion coefficient of the glass, especially in the glass containing alkali metals. It is more obvious in the system. If the content of ZnO is less than 1%, the above effect is not obvious. If the content of ZnO exceeds 12%, the glass transition temperature drops rapidly, making the glass easy to soften and deform in a high-temperature working environment, which will have a fatal impact on glass devices that need to work at high temperatures. In addition, if its content exceeds 12%, the dispersion of the glass rises rapidly, and the Abbe number cannot meet the design requirements. Therefore, the content of ZnO is limited to 1 to 12%, preferably 2 to 10%, and more preferably 3 to 8%.
  • the value of (TiO 2 +ZnO)/Al 2 O 3 is greater than 8.0, the UV transmittance of the glass decreases and the tendency to crystallize increases. If the value of (TiO 2 +ZnO)/Al 2 O 3 is low Above 0.5, the meltability of the glass decreases, the difficulty of bubble discharge increases, and the internal quality deteriorates. Therefore, the value of (TiO 2 +ZnO)/Al 2 O 3 is 0.5 to 8.0, preferably the value of (TiO 2 +ZnO)/Al 2 O 3 is 0.7 to 7.0, more preferably (TiO 2 +ZnO)/Al 2 The value of O 3 is 1.0 to 5.0.
  • the inventor found that when the glass contains B 2 O 3 , the presence of ZnO further reduces the melting temperature of the glass, making it easier to obtain high-quality products. If the value of ZnO/B 2 O 3 is less than 0.2, the above effect is not Obviously; if the ZnO/B 2 O 3 is higher than 1.8, the glass transition temperature drops rapidly, and the heat resistance cannot meet the design requirements. On the other hand, when the value of ZnO/B 2 O 3 is 0.2 to 1.8, the water resistance, acid resistance and alkali resistance of the glass are more excellent than when B 2 O 3 is added alone. Therefore, in the present invention, the value of ZnO/B 2 O 3 is preferably 0.2 to 1.8, more preferably 0.3 to 1.0, and still more preferably 0.4 to 0.8.
  • MgO, CaO, SrO, and BaO are alkaline earth metal oxides. Adding to the glass can increase the refractive index and transition temperature of the glass, and adjust the stability and thermal expansion coefficient of the glass. However, the addition of alkaline earth metal oxides leads to a rapid increase in the Young's modulus of the glass. When the thermal expansion coefficient of the glass material is the same, the glass with a low Young's modulus has better thermal shock resistance. Therefore, in consideration of the above factors, the total addition amount of alkaline earth metal oxides MgO+CaO+SrO+BaO is preferably 10% or less, more preferably 5% or less. In some embodiments, if the stability, thermal expansion coefficient, and transition temperature of the glass meet the design requirements, it is further preferred that no alkaline earth metal oxide is added.
  • the devitrification resistance and chemical resistance of the glass can be improved.
  • (MgO+CaO+SrO+BaO)/Al 2 O 3 is preferably 0.5 or less
  • (MgO+CaO+SrO+BaO)/Al 2 O 3 is more preferably 0.2 or less.
  • a higher refractive index is required to achieve the matching of the optical system, or a higher transition temperature is required, which requires the addition of a small amount of alkaline earth metal oxide to achieve this.
  • alkaline earth metal oxides in order to avoid the rapid decline of the water resistance, acid resistance and alkali resistance of the glass, it can be considered to add MgO, CaO, SrO, and BaO individually or in combination in the order. If the individual content of alkaline earth metal oxides such as MgO, CaO, SrO, BaO, etc. exceeds 5%, the glass's crystallization resistance will decline rapidly, making it difficult to obtain large-caliber, high-quality products. Therefore, the contents of MgO, CaO, SrO, and BaO are each limited to 5% or less, preferably 3% or less, and more preferably 2% or less.
  • the inventor found that if there is a certain amount of alkaline earth metal oxide in the glass, the ZnO content can be adjusted to reduce the loss of glass chemical stability and thermal shock resistance.
  • the value of (MgO+CaO+SrO+BaO)/ZnO is below 1.0, preferably below 0.5, more preferably below 0.2, it is easier to obtain a higher refractive index and meet the design of the present invention Glass with required chemical stability, thermal expansion coefficient and thermal shock resistance.
  • Li 2 O, Na 2 O, and K 2 O belong to alkali metal oxides.
  • its content is closely related to the thermal expansion coefficient, chemical stability of the glass and the intrinsic quality of the glass.
  • Li 2 O can lower the melting temperature of the glass and increase the degree of bubbles in the glass.
  • the loss of the chemical stability of the glass is minimal.
  • the content of Li 2 O exceeds 5%, the solidification speed of the glass during the molding process, that is, the process of cooling the glass liquid from liquid to solid, will be slower, which is unfavorable for the production of large-scale and high-quality products (such as Products with a width or diameter greater than 340mm and thickness greater than 40mm are prone to unqualified streaks and internal crystallization).
  • the content of Li 2 O is limited to 5% or less, preferably 3% or less, and it is more preferable not to add Li 2 O.
  • the total content of Na 2 O and K 2 O Na 2 O + K 2 O exceeds 22%, the Abbe number of the glass is lower than the design requirement, the thermal expansion coefficient of the glass exceeds the design requirement, and the dielectric of the glass.
  • the rapid rise of the constant leads to a rapid decline in the insulation performance of the glass, which is disadvantageous for certain applications that require insulation.
  • Na 2 O+K 2 O is less than 5%, the thermal expansion coefficient of the glass will not meet the design requirements, and the coloring ability of the variable components in the glass will increase, and the short-wave transmittance of the glass will not meet the design requirements. Therefore, the total content of Na 2 O and K 2 O, Na 2 O+K 2 O, is 5 to 22%, preferably 6 to 20%, and more preferably 8 to 18%.
  • Adding Na 2 O to the glass can significantly increase the thermal expansion coefficient of the glass and reduce the high-temperature viscosity of the glass, making it easier to obtain glass products with a width greater than 330 mm that can be processed into 12-inch packaging wafers.
  • the content of Na 2 O exceeds 12%, the refractive index of the glass decreases, and the chemical stability of the glass decreases rapidly, which cannot meet the design requirements. If the content of Na 2 O is less than 2%, the thermal expansion coefficient of the glass will not meet the design requirements, and the chemical stability will be seriously degraded. Therefore, the content of Na 2 O is limited to 2 to 12%, preferably 3 to 10%, and more preferably 4 to 9%.
  • Adding a proper amount of K 2 O to the glass can increase the thermal expansion coefficient of the glass, reduce the high-temperature viscosity of the glass, and increase the bubble degree of the glass.
  • the appropriate amount of K 2 O is added to the glass and Will not significantly damage the chemical stability of the glass.
  • the content of K 2 O is less than 2%, the effect of increasing the coefficient of thermal expansion and reducing the high-temperature viscosity is not obvious. Therefore, the content of K 2 O is limited to 2 to 12%, preferably 3 to 10%, and more preferably 4 to 9%.
  • the value of (B 2 O 3 +K 2 O)/Al 2 O 3 is greater than 10.0, the alkali resistance of the glass decreases and the thermal expansion coefficient increases; if (B 2 O 3 +K 2 When the value of O)/Al 2 O 3 is less than 1.0, the meltability of the glass decreases and the transition temperature increases. Accordingly, preferably (B 2 O 3 + K 2 O) / Al is 1.0 ⁇ 10.0 2 O 3, more preferably (B 2 O 3 + K 2 O) / Al is 1.5 ⁇ 8.0 2 O 3, and further Preferably, the value of (B 2 O 3 +K 2 O)/Al 2 O 3 is 2.0 to 6.0.
  • the value of (Na 2 O+K 2 O)/(B 2 O 3 +ZnO) is lower than 0.2, the free oxygen in the glass system is insufficient, resulting in the combination of B 2 O 3 and ZnO. The probability of entering the glass network is reduced, resulting in a sharp drop in chemical stability, and at the same time, the expansion coefficient of the glass is reduced, failing to meet the design requirements. If the value of (Na 2 O+K 2 O)/(B 2 O 3 +ZnO) is greater than 2.5, there will be excess free oxygen in the glass system, which will lead to a sharp drop in the chemical stability of the glass, and the expansion coefficient of the glass exceeds the design requirements.
  • alkaline earth metal oxides MgO, CaO, SrO, BaO, etc. to the glass is more conducive to the improvement of chemical stability than the alkali metal oxides Li 2 O, Na 2 O, K 2 O, etc.
  • the present invention in order to obtain a suitable coefficient of thermal expansion, it is necessary to add Na 2 O and K 2 O to the glass, but it will lead to a decrease in the chemical stability of the glass.
  • the inventors have discovered through research that when Al 2 O 3 is present in the glass, the type and relative content of alkali metal oxides will change the microstructure of the glass and have a greater impact on the chemical stability of the glass.
  • the value of (Na 2 O+K 2 O)/Al 2 O 3 is 0.8 to 8.0, preferably 1.0 to 6.0, and more preferably 1.5 to 5.0, the chemical stability of the glass can be improved .
  • the glass becomes difficult to melt and clarify, and it is difficult to remove bubbles and inclusions in the glass. It is difficult to obtain glass with a bubble degree of A 0 or higher, and the internal streaks of the glass are serious. If the value of (SiO 2 +TiO 2 )/(Na 2 O+ZnO) is lower than 3.0, the thermal expansion coefficient of the glass rises rapidly, exceeding the design requirements. Therefore, it is preferable to control the value of (SiO 2 +TiO 2 )/(Na 2 O+ZnO) between 3.0 and 12.0, more preferably between 3.0 and 10.0, and still more preferably between 4.0 and 8.0.
  • Adding a proper amount of ZrO 2 to the glass can improve the chemical stability and thermal shock resistance of the glass, and at the same time increase the refractive index of the glass. But its characteristic is that it will significantly increase the melting temperature of the glass. If its content is higher than 5%, inclusion defects are likely to appear in the glass. Therefore , the content of ZrO 2 is limited to 5% or less, preferably 3% or less. In some embodiments, when the chemical stability and strength of the glass are surplus, it is more preferable not to add ZrO 2 .
  • Adding a proper amount of P 2 O 5 to the glass can increase the strength of the glass, especially when chemical strengthening is required. However, if its content exceeds 5%, differential phases are easily generated inside the glass, which greatly increases the molding temperature of the glass. Therefore, the content of P 2 O 5 is limited to 0 to 5%, preferably 0 to 3%. In some embodiments, when the glass strength design meets usage requirements, it is more preferable not to add P 2 O 5 .
  • an appropriate amount of La 2 O 3 , Y 2 O 3 , Gd 2 O 3 , Nb 2 O 5 , WO 3 and other oxides can be added.
  • its content alone or in combination exceeds 5%, the Young's modulus of the glass rises rapidly.
  • the strength of the glass rises the brittleness of the glass rises faster, and the thermal shock resistance decreases.
  • the devitrification resistance and short-wave transmittance of the glass will deteriorate.
  • the contents of La 2 O 3 , Y 2 O 3 , Gd 2 O 3 , Nb 2 O 5 , and WO 3 are each 5% or less, preferably 3% or less, more preferably 1% or less, and still more preferably not contained. Furthermore, the total content of La 2 O 3 , Y 2 O 3 , Gd 2 O 3 , Nb 2 O 5 , and WO 3 is preferably 5% or less, more preferably 3% or less, and even more preferably 1% or less.
  • Sb 2 O 3 by adding 0 to 1% of one or more of Sb 2 O 3 , SnO 2 , SnO, NaCl, sulfate and CeO 2 as a clarifying agent, it is preferable to use Sb 2 As a clarifying agent, O 3 can improve the clarifying effect of the glass, and it is preferable to add 0 to 0.5% of the clarifying agent.
  • the glass of the present invention preferably does not contain F.
  • Adding Ta 2 O 5 to the glass will greatly increase the refractive index and cost of the glass, and make the melting performance of the glass worse. Therefore, the glass of the present invention preferably does not contain Ta 2 O 5 .
  • the oxides of Th, Cd, Tl, Os, Be, and Se have been used as harmful chemical substances in recent years and have tended to be controlled and used, not only in the glass manufacturing process, but also in the processing process and disposal after productization. Measures are required. Therefore, in the case of attaching importance to the impact on the environment, it is preferable not to actually contain them except for unavoidable mixing. As a result, the glass does not actually contain substances that pollute the environment. Therefore, even if no special environmental countermeasures are taken, the glass of the present invention can be manufactured, processed, and discarded.
  • the glass of the present invention does not contain As 2 O 3 and PbO.
  • As 2 O 3 has the effect of eliminating bubbles and better preventing glass coloration, the addition of As 2 O 3 will increase the corrosion of the glass to the furnace, especially the platinum furnace, and cause more platinum ions to enter the glass. The service life of the platinum furnace is adversely affected.
  • PbO can significantly improve the high refractive index and high dispersion properties of glass, but both PbO and As 2 O 3 cause environmental pollution.
  • does not contain means that the compound, molecule or element is not deliberately added as a raw material to the glass of the present invention; however, it may be used as a raw material and/or equipment for glass production. Certain impurities or components that are not added intentionally will be contained in small or trace amounts in the final glass. This situation is also within the protection scope of the present invention patent.
  • the refractive index (nd) and Abbe number ( ⁇ d ) of glass materials are tested in accordance with the methods specified in GB/T 7962.1-2010.
  • the lower limit of the refractive index (nd) of the glass material of the present invention is 1.48, preferably the lower limit is 1.50, more preferably the lower limit is 1.51, and the upper limit of the refractive index (nd) is 1.56, preferably 1.55, more preferably 1.54;
  • Abbe number ( ⁇ The lower limit of d ) is 50, preferably 51, and more preferably 53, and the upper limit of Abbe number ( ⁇ d ) is 58, preferably 57, and more preferably 56.
  • Acid on stability of the glass material (D A) (Powder Method) The method according to GB / T 17129 specified test. In this article, acid resistance stability is sometimes referred to as acid resistance or acid resistance stability.
  • Acid on stability of the glass material of the present invention (D A) of Class 2 or more, preferably 1 class.
  • the water resistance stability (D W ) (powder method) of the glass material is tested in accordance with the method specified in GB/T 17129. In this article, water resistance stability is sometimes referred to as water resistance or water resistance stability.
  • the water resistance stability (D W ) of the glass material of the present invention is two or more types, preferably one type.
  • the alkali resistance stability of the glass material is measured in accordance with the test conditions and requirements of ISO 10629, expressed as the weight loss of the glass sample.
  • the stability of alkali resistance is sometimes referred to as alkali resistance or alkali resistance stability.
  • the glass into a test sample with a size of 30mm ⁇ 30mm ⁇ 2mm, polish on six sides, and put it into 2000ml of NaOH solution.
  • concentration of the NaOH solution is 0.01mol/L and the pH value is 12.0.
  • the test process is regularly monitored with a pH meter. Change the pH value of the test solution, and replace the reaction test solution in time. After eroding at 50°C for 100 hours, use an electronic balance to measure the weight loss of the sample. The weight loss is expressed in mg.
  • the weight loss of the glass material of the present invention after the above-mentioned test method is less than 9 mg, preferably less than 7 mg, and more preferably less than 5 mg.
  • the thermal expansion coefficient of the present invention refers to the average thermal expansion coefficient of glass at 20-300°C, expressed as ⁇ 20-300°C, and tested according to the method specified in GB/T7962.16-2010.
  • the upper limit of the average thermal expansion coefficient ( ⁇ 20-300°C ) of the glass material of the present invention is 90 ⁇ 10 -7 /K, preferably the upper limit is 85 ⁇ 10 -7 /K, more preferably the upper limit is 80 ⁇ 10 -7 /K, average
  • the lower limit of the coefficient of thermal expansion ( ⁇ 20-300°C ) is 60 ⁇ 10 -7 /K, the preferable lower limit is 65 ⁇ 10 -7 /K, and the more preferable lower limit is 68 ⁇ 10 -7 /K.
  • the light transmittance in the present invention refers to the internal transmittance of a glass sample with a thickness of 10mm at 360nm, expressed as ⁇ 360nm , and tested according to the method specified in GB/T7962.12-2010.
  • the transmittance ( ⁇ 360nm ) at 360 nm of the glass material of the present invention is 78% or more, preferably 82% or more, and more preferably 85% or more.
  • the glass transition temperature (T g ) is tested according to the method specified in GB/T7962.16-2010.
  • the upper limit of the transition temperature (T g ) of the glass of the present invention is 610°C, the preferred upper limit is 600°C, and the more preferred upper limit is 580°C.
  • the lower limit of the transition temperature (T g ) is 500°C, and the preferred lower limit is 520°C, more preferably the lower limit It is 530°C.
  • the Young's modulus (E) of the glass is calculated using the following formula:
  • E Young's modulus, Pa
  • G is the shear modulus, Pa
  • V T is the longitudinal wave velocity, m/s
  • V S is the velocity of transverse wave, m/s
  • ⁇ is the density of the glass, g/cm 3 .
  • the lower limit of the Young's modulus (E) of the glass material of the present invention is 6000 ⁇ 10 7 Pa, preferably the lower limit is 6500 ⁇ 10 7 Pa, more preferably the lower limit is 7000 ⁇ 10 7 Pa, and the upper limit of Young's modulus (E) is 8500 ⁇ 10 7 Pa, preferably the upper limit is 8000 ⁇ 10 7 Pa.
  • the bubble degree of the glass material is tested according to the test method specified in GB/T7962.8-2010.
  • the bubble degree of the glass material of the present invention is A grade or higher, preferably A 0 grade or higher, and more preferably A 00 grade.
  • the fringe degree of the glass material is measured according to the method specified in MLL-G-174B.
  • the method is a fringe meter consisting of a point light source and a lens. From the direction where the fringes are most visible, the inspection is compared with the standard sample. There are 4 levels, namely A, B, C, D, and A is the prescribed test. There are no visible streaks under the conditions, B grade is fine and scattered streaks under the prescribed detection conditions, C grade is slight parallel streaks under the prescribed detection conditions, and D grade is rough streaks under the prescribed detection conditions.
  • the streak of the glass material of the present invention is C-level or higher, preferably B-level or higher.
  • the glass material of the present invention has the above-mentioned excellent properties, and can be widely used in the packaging field of electronic devices and photosensitive devices, and can also be used in the manufacture of glass elements, manufacturing various equipment or instruments, such as imaging equipment, sensors, microscopes, medical technology, and digital projections. , Communications, optical communication technology/information transmission, optics/illumination in the automotive field, lithography technology, excimer lasers, wafers, computer chips, and integrated circuits and electronic devices including such circuits and chips, or used in the automotive field, Camera equipment and devices in the surveillance security field.
  • the manufacturing method of the glass material of the present invention is as follows: the glass of the present invention is produced using conventional raw materials and conventional processes, using carbonates, nitrates, sulfates, hydroxides, oxides, etc. as raw materials, and after compounding according to conventional methods, The good charge is put into a smelting furnace at 1300 ⁇ 1500°C, and after clarification, stirring and homogenization, a homogeneous molten glass without bubbles and no undissolved substances is obtained, and the molten glass is cast in the mold And annealed.
  • a smelting furnace at 1300 ⁇ 1500°C
  • stirring and homogenization a homogeneous molten glass without bubbles and no undissolved substances is obtained, and the molten glass is cast in the mold And annealed.
  • the glass material having the composition shown in Table 1 to Table 2 was obtained by using the above-mentioned manufacturing method of the glass material.
  • the characteristics of each glass were measured by the test method described in the present invention, and the measurement results are shown in Tables 1 to 2.

Landscapes

  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Glass Compositions (AREA)

Abstract

一种玻璃材料，其组分以重量百分比表示，含有：SiO 2：50～70％；B 2O 3：3～15％；TiO 2：0.5～10％；ZnO：1～12％；Al 2O 3：0.5～10％；Na 2O+K 2O：5～22％，其中B 2O 3/SiO 2为0.06～0.26，(TiO 2+ZnO)/Al 2O 3为0.5～8.0。通过合理的组分设计，玻璃材料具有较高的光透过率和优异的化学稳定性，满足感光器件封装等领域的应用。

Description

玻璃材料 技术领域
本发明涉及一种玻璃材料，尤其是涉及一种适用于感光器件封装领域的玻璃材料。
背景技术
COMS、CCD等光电转换器件通常使用玻璃材料作为窗口材料，窗口玻璃起到光透过和保护光电转换芯片的作用。早期的COMS、CCD等感光器件通常在照相机中，使用环境较为舒适，因此对感光器件的保护窗口的化学稳定性(耐酸、耐水和耐碱等)、耐候性和抗温度冲击性无较高要求。近年来随着车载安防、深空海洋探测、机器视觉的发展，需要感光器件在非常恶劣的条件下具备较高的可靠性。比如应用在高温火场的感光器件需要承受100～200℃、甚至更高的极端温度环境；海洋环境下观测的感光器件需要能够承受长期的碱性或酸性侵蚀；应用于观察化学(化工)实验的感光器件需要能够承受强酸、强碱的腐蚀；应用于车载、安防的感光器件需要长期暴露在室外环境中。对于COMS等感光器件来说，感光芯片主要成分是硅单晶材料，封装外壳主要是陶瓷材料。陶瓷材料有非常好的化学稳定性和抗冲击性能，但其弱点在于不透光，需要采用脆性的玻璃材料作为透光窗口。而玻璃材料与陶瓷材料相比，在化学稳定性和抗热冲击能力方面有巨大的差距。因此，提升窗口玻璃材料的化学稳定性，耐温度冲击性是提升感光器件在恶劣外在环境下的可靠性的最佳途径。
作为感光芯片的窗口，还需要玻璃材料在360nm～2000nm范围内有较高的透过率，以满足紫外-可见-近红外不同波段感光的需要。在通常情况下，玻璃材料在360nm～2000nm范围内透过率是逐渐升高的，因此我们可以用360nm处的内透过率(τ 360nm)来表征玻璃的最低透过率，当τ 360nm在78％以上时，代表封装玻璃可满足上述波段的透过率要求。由于封装用玻璃需要尽量避免反射损失，折射率若超过1.60，玻璃反射损失加大。虽然可 以通过镀增透膜的方式来降低反射损失，但会带来成本上升和杂散光干扰问题。
发明内容
本发明所要解决的技术问题是提供一种光透过率高且化学稳定性优异的玻璃材料。
本发明解决技术问题所采用的技术方案是：
(1)玻璃材料，其组分以重量百分比表示，含有：SiO 2：50～70％；B 2O 3：3～15％；TiO 2：0.5～10％；ZnO：1～12％；Al 2O 3：0.5～10％；Na 2O+K 2O：5～22％，其中B 2O 3/SiO 2为0.06～0.26，(TiO 2+ZnO)/Al 2O 3为0.5～8.0。
(2)根据(1)所述的玻璃材料，其组分以重量百分比表示，还含有：MgO+CaO+SrO+BaO：0～10％；和/或Li 2O：0～5％；和/或P 2O 5：0～5％；和/或ZrO 2：0～5％；和/或La 2O 3：0～5％；和/或Y 2O 3：0～5％；和/或Gd 2O 3：0～5％；和/或Nb 2O 5：0～5％；和/或WO 3：0～5％；和/或澄清剂：0～1％。
(3)玻璃材料，其组分以重量百分比表示由SiO 2：50～70％；B 2O 3：3～15％；TiO 2：0.5～10％；ZnO：1～12％；Al 2O 3：0.5～10％；Na 2O+K 2O：5～22％；MgO+CaO+SrO+BaO：0～10％；Li 2O：0～5％；P 2O 5：0～5％；ZrO 2：0～5％；La 2O 3：0～5％；Y 2O 3：0～5％；Gd 2O 3：0～5％；Nb 2O 5：0～5％；WO 3：0～5％；澄清剂：0～1％组成，其中B 2O 3/SiO 2为0.06～0.26，(TiO 2+ZnO)/Al 2O 3为0.5～8.0。
(4)根据(1)～(3)任一所述的玻璃材料，其组分以重量百分比表示，其中：B 2O 3/SiO 2为0.08～0.2；和/或(TiO 2+ZnO)/Al 2O 3为0.7～7.0；和/或(SiO 2+TiO 2)/(Na 2O+ZnO)为3.0～12.0；和/或ZnO/B 2O 3为0.2～1.8；和/或(Na 2O+K 2O)/Al 2O 3为0.8～8.0；和/或(Na 2O+K 2O)/(B 2O 3+ZnO)为0.2～2.5；和/或(B 2O 3+K 2O)/Al 2O 3为1.0～10.0。
(5)根据(1)～(3)任一所述的玻璃材料，其组分以重量百分比表示，其中：(MgO+CaO+SrO+BaO)/ZnO为1.0以下；和/或(MgO+CaO+SrO+BaO)/Al 2O 3为1.0以下；和/或(MgO+CaO+SrO+BaO)/(Na 2O+K 2O)为1.0以下。
(6)根据(1)～(3)任一所述的玻璃材料，其组分以重量百分比表示，其中：SiO 2：55～68％；和/或B 2O 3：大于5％但小于或等于13％；和/或TiO 2：1.5～8％；和/或ZnO：2～10％；和/或Al 2O 3：1～8％；和/或Na 2O+K 2O：6～20％；和/或MgO+CaO+SrO+BaO：0～5％；和/或Li 2O：0～3％；和/或P 2O 5：0～3％；和/或ZrO 2：0～3％；和/或La 2O 3：0～3％；和/或Y 2O 3：0～3％；和/或Gd 2O 3：0～3％；和/或Nb 2O 5：0～3％；和/或WO 3：0～3％；和/或澄清剂：0～0.5％。
(7)根据(1)～(3)任一所述的玻璃材料，其组分以重量百分比表示，其中：B 2O 3/SiO 2为0.1～0.18；和/或(TiO 2+ZnO)/Al 2O 3为1.0～5.0；和/或(SiO 2+TiO 2)/(Na 2O+ZnO)为3.0～10.0；和/或ZnO/B 2O 3为0.3～1.0；和/或(Na 2O+K 2O)/Al 2O 3为1.0～6.0；和/或(Na 2O+K 2O)/(B 2O 3+ZnO)为0.3～2.0；和/或(B 2O 3+K 2O)/Al 2O 3为1.5～8.0。
(8)根据(1)～(3)任一所述的玻璃材料，其组分以重量百分比表示，其中：(MgO+CaO+SrO+BaO)/ZnO为0.5以下；和/或(MgO+CaO+SrO+BaO)/Al 2O 3为0.5以下；和/或(MgO+CaO+SrO+BaO)/(Na 2O+K 2O)为0.5以下。
(9)根据(1)～(3)任一所述的玻璃材料，其组分以重量百分比表示，其中：SiO 2：60～68％；和/或B 2O 3：6～12％；和/或TiO 2：2～7％；和/或ZnO：3～8％；和/或Al 2O 3：2～7％；和/或Na 2O+K 2O：8～18％；和/或La 2O 3：0～1％；和/或Y 2O 3：0～1％；和/或Gd 2O 3：0～1％；和/或Nb 2O 5：0～1％；和/或WO 3：0～1％。
(10)根据(1)～(3)任一所述的玻璃材料，其组分以重量百分比表示，其中：(SiO 2+TiO 2)/(Na 2O+ZnO)为4.0～8.0；和/或ZnO/B 2O 3为0.4～0.8；和/或(Na 2O+K 2O)/Al 2O 3为1.5～5.0；和/或(Na 2O+K 2O)/(B 2O 3+ZnO)为0.5～1.5；和/或(B 2O 3+K 2O)/Al 2O 3为2.0～6.0。
(11)根据(1)～(3)任一所述的玻璃材料，其组分以重量百分比表示，其中：(MgO+CaO+SrO+BaO)/ZnO为0.2以下；和/或 (MgO+CaO+SrO+BaO)/Al 2O 3为0.2以下；和/或(MgO+CaO+SrO+BaO)/(Na 2O+K 2O)为0.2以下。
(12)根据(1)～(3)任一所述的玻璃材料，其组分以重量百分比表示，其中：Na 2O：2～12％，优选Na 2O：3～10％，更优选Na 2O：4～9％；和/或K 2O：2～12％，优选K 2O：3～10％，更优选K 2O：4～9％；和/或MgO：0～5％，优选MgO：0～3％，更优选MgO：0～2％；和/或CaO：0～5％，优选CaO：0～3％，更优选CaO：0～2％；和/或SrO：0～5％，优选SrO：0～3％，更优选SrO：0～2％；和/或BaO：0～5％，优选BaO：0～3％，更优选BaO：0～2％。
(13)根据(1)～(3)任一所述的玻璃材料，其组分以重量百分比表示，其中：La 2O 3、Y 2O 3、Gd 2O 3、Nb 2O 5、WO 3的合计含量为5％以下，优选为3％以下，更优选为1％以下。
(14)根据(1)～(3)任一所述的玻璃材料，其组分中不含有F；和/或不含有Ta 2O 5；和/或不含有Li 2O；和/或不含有P 2O 5；和/或不含有ZrO 2。
(15)根据(1)～(3)任一所述的玻璃材料，所述玻璃材料的折射率为1.48～1.56，优选为1.50～1.55，更优选为1.51～1.54；和/或阿贝数为50～58，优选为51～57，更优选为53～56；和/或热膨胀系数α 20-300℃为60×10 -7/K～90×10 -7/K，优选为65×10 -7/K～85×10 -7/K，更优选为68×10 -7/K～80×10 -7/K；和/或杨氏模量为6000×10 7Pa以上，优选为6500×10 7Pa～8500×10 7Pa，更优选为7000×10 7Pa～8000×10 7Pa；和/或转变温度为500℃～610℃，优选为520℃～600℃，更选为530℃～580℃；和/或气泡度为A级以上，优选为A 0级以上，更优选为A 00级；和/或条纹为C级以上，优选B级以上。
(16)根据(1)～(3)任一所述的玻璃材料，所述玻璃材料的耐酸作用稳定性为2类以上，优选为1类；和/或耐水作用稳定性为2类以上，优选为1类；和/或耐碱作用稳定性按照ISO 10629的测试条件和要求进行测量后的玻璃样品失重小于9mg，优选小于7mg，更优选小于5mg；和/或光透过率τ 360nm为78％以上，优选为82％以上，更优选为85％以上。
(17)(1)～(16)任一所述的玻璃材料在封装领域的应用。
(18)玻璃元件，采用(1)～(16)任一所述的玻璃材料制成。
(19)一种设备，含有(1)～(16)任一所述的玻璃材料，或含有(18)所述的玻璃元件。
本发明的有益效果是：通过合理的组分设计，本发明获得的玻璃材料具有较高的光透过率和优异的化学稳定性，满足感光器件封装等领域的应用。
具体实施方式
下面，对本发明的玻璃材料的实施方式进行详细说明，但本发明不限于下述的实施方式，在本发明目的的范围内可进行适当的变更来加以实施。此外，关于重复说明部分，虽然有适当的省略说明的情况，但不会因此而限制发明的主旨，在以下内容中，本发明玻璃材料有时候简称为玻璃。
[玻璃材料]
下面对本发明玻璃材料的各组分范围进行说明。在本说明书中，如果没有特殊说明，各组分的含量、合计含量全部采用相对于换算成氧化物的组成的玻璃物质总量的重量百分比表示。在这里，所述“换算成氧化物的组成”是指，作为本发明的玻璃材料组成成分的原料而使用的氧化物、复合盐及氢氧化物等熔融时分解并转变为氧化物的情况下，将该氧化物的物质总重量作为100％。
除非在具体情况下另外指出，本文所列出的数值范围包括上限和下限值，“以上”和“以下”包括端点值，以及包括在该范围内的所有整数和分数，而不限于所限定范围时所列的具体值。本文所称“和/或”是包含性的，例如“A；和/或B”，是指只有A，或者只有B，或者同时有A和B。
<必要组分和任选组分>
SiO 2是本玻璃的主要组分之一，在本发明玻璃中，合适量的SiO 2能够保证玻璃具备较高的耐水和耐酸性能，同时能够实现高的光透过率。若SiO 2的含量低于50％，玻璃的耐水性能、耐酸性能以及玻璃的紫外光透过率低 于设计要求。若SiO 2的含量高于70％，玻璃的折射率达不到设计要求。玻璃的熔化温度会急剧升高，在生产中不易获得高品质玻璃，同时玻璃的热膨胀系数变低。因此，本发明中SiO 2的含量限定为50～70％，优选为55～68％，更优选为60～68％。
合适量的B 2O 3添加到玻璃中可以使玻璃的结构向致密方向转化，提升玻璃折射率的同时，实现较高耐水与耐酸性能，若其含量低于3％，上述效果不明显。若B 2O 3的含量高于15％，玻璃耐水、耐酸性能反而下降。因此，B 2O 3的含量限定为3～15％，优选为大于5％但小于或等于13％，更优选为6～12％。
本发明中，B 2O 3/SiO 2的值影响玻璃的生产难度，当B 2O 3/SiO 2小于0.06时，玻璃熔化温度升高，对耐火材料的侵蚀加剧，容易在玻璃中引入更多的着色杂质和夹杂物，导致玻璃的透过率达不到设计要求，同时导致产品内部产生缺陷的几率上升。当B 2O 3/SiO 2大于0.26时，熔炼温度下降不明显，同时B 2O 3对耐火材料的侵蚀上升，也容易在玻璃中引入更多的着色杂质和夹杂物，导致玻璃的短波透过率达不到设计要求，同时导致产品表面产生缺陷的几率上升。因此，本发明中，B 2O 3/SiO 2的值为0.06～0.26，优选为0.08～0.2，更优选为0.1～0.18。
合适量的Al 2O 3添加到玻璃中可以提高玻璃的耐水和耐酸性能，同时能够降低玻璃的热膨胀系数，尤其是在有碱金属氧化物存在的情况下。若Al 2O 3的含量高于10％，玻璃的热膨胀系数快速降低，达不到设计要求。因此，Al 2O 3的含量限定为0.5～10％，优选为1～8％，更优选为2～7％。
合适量的TiO 2加入到玻璃中可以提升玻璃的折射率，提升玻璃的耐水、耐酸和耐碱性，同时能够降低玻璃的热膨胀系数，提升玻璃的抗热冲击性能，若TiO 2的含量低于0.5％，上述效果不明显；若TiO 2的含量超过10％，玻璃的阿贝数低于设计预期，短波透过率快速下降，尤其是在熔炼气氛不稳定的环境下。更为重要的是，高含量的TiO 2导致玻璃的折射率快速上升，在不镀增透膜的情况下增加短波波长的反射损失，造成短波透过率的进一 步降低，同时玻璃的热膨胀系数降低，达不到设计要求。因此，本发明中TiO 2的含量限定为0.5～10％，优选为1.5～8％。在一些实施方式中，综合考虑到玻璃的折射率、阿贝数以及熔化过程中气氛的控制难度，更优选TiO 2的含量为2～7％。
ZnO在二价金属氧化物中场强较大，加入到玻璃中可提升玻璃耐酸、耐水和耐碱性能，提升玻璃的折射率，同时能够降低玻璃的热膨胀系数，尤其是在含有碱金属的玻璃体系中更为明显。若ZnO的含量低于1％，上述效果不明显。若ZnO的含量超过12％，玻璃的转变温度快速降低，使得玻璃在高温工作环境中容易软化变形，对需要工作在高温状态下的玻璃器件产生致命的影响。另外，若其含量超过12％，玻璃的色散快速上升，阿贝数达不到设计要求。因此ZnO的含量限定为1～12％，优选为2～10％，更优选为3～8％。
在本发明中，若(TiO 2+ZnO)/Al 2O 3的值大于8.0，玻璃的紫外透过率降低，析晶倾向增加，若(TiO 2+ZnO)/Al 2O 3的值低于0.5，玻璃的熔融性降低，气泡排出难度增加，内在质量变差。因此，(TiO 2+ZnO)/Al 2O 3的值为0.5～8.0，优选(TiO 2+ZnO)/Al 2O 3的值为0.7～7.0，更优选(TiO 2+ZnO)/Al 2O 3的值为1.0～5.0。
经发明人大量实验研究发现，当玻璃中含有B 2O 3时，ZnO的存在进一步降低玻璃的熔炼温度，更易获得高品质产品，若ZnO/B 2O 3的值低于0.2，上述效果不明显；若ZnO/B 2O 3高于1.8，玻璃的转变温度快速降低，耐热性达不到设计要求。另一方面，当ZnO/B 2O 3的值为0.2～1.8时，玻璃的耐水、耐酸和耐碱性能比单独加入B 2O 3时更为优异。因此，本发明中优选ZnO/B 2O 3的值为0.2～1.8，更优选为0.3～1.0，进一步优选为0.4～0.8。
MgO、CaO、SrO、BaO属于碱土金属氧化物，加入到玻璃中可以提升玻璃的折射率与转变温度，调节玻璃的稳定性和热膨胀系数。但是，碱土金属氧化物的加入导致玻璃杨氏模量的快速上升，玻璃材料在热膨胀系数一致时，杨氏模量低的玻璃抗热冲击性能更好。因此，考虑到上述因素，碱 土金属氧化物的合计添加量MgO+CaO+SrO+BaO优选在10％以下，更优选为5％以下。在一些实施方式中，若玻璃的稳定性、热膨胀系数和转变温度达到设计要求，进一步优选为不添加碱土金属氧化物。
在本发明的一些实施方式中，通过使碱土金属氧化物与Al 2O 3的比例(MgO+CaO+SrO+BaO)/Al 2O 3在1.0以下，可提高玻璃的耐失透性和化学稳定性，优选(MgO+CaO+SrO+BaO)/Al 2O 3为0.5以下，更优选(MgO+CaO+SrO+BaO)/Al 2O 3为0.2以下。
在一些封装应用中，需要更高的折射率来实现光学系统的匹配，或需要更高的转变温度，这就需要添加少量碱土金属氧化物来实现。在加入碱土金属氧化物的同时，为了避免玻璃的耐水、耐酸和耐碱性能的快速下降，可以考虑按MgO、CaO、SrO、BaO的顺序单独或者组合添加。若MgO、CaO、SrO、BaO等碱土金属氧化物单独含量超过5％，玻璃抗析晶性能会快速下降，不易获得大口径高品质的产品。因此，MgO、CaO、SrO、BaO的含量分别限定为5％以下，优选为3％以下，更优选为2％以下。
经发明人大量实验研究发现，若玻璃中存在一定量的碱土金属氧化物时，可以考虑调整ZnO含量来减少玻璃化学稳定性和抗热冲击性的损失。在一些实施方式中，当(MgO+CaO+SrO+BaO)/ZnO的值在1.0以下，优选在0.5以下，更优选在0.2以下时，可较易获得更高折射率，并满足本发明设计要求的化学稳定性、热膨胀系数和抗热冲击性能的玻璃。
Li 2O、Na 2O、K 2O属于碱金属氧化物，在本发明玻璃中，其含量和玻璃的热膨胀系数、化学稳定性和玻璃的内在品质密切相关。
Li 2O加入到玻璃中可以降低玻璃熔炼温度，提升玻璃气泡度，同时较其他两种碱金属氧化物来说，对玻璃的化学稳定性损失最小。但是，若Li 2O的含量超过5％，玻璃在成型过程中，也就是玻璃液从液态冷却到固态的工艺流程中，固化速度较慢，这对大规格高品质产品生产是不利的(如生产宽度或直径大于340mm，厚度大于40mm的产品，容易出现条纹度不合格和内部析晶)。另一方面，还会导致玻璃的转变温度下降，耐热性达不到设计 要求。因此，Li 2O的含量限定为5％以下，优选为3％以下，更优选不添加Li 2O。
在本发明中，Na 2O和K 2O的合计含量Na 2O+K 2O若超过22％，玻璃的阿贝数低于设计要求，玻璃的热膨胀系数超过设计要求，同时玻璃的介电常数快速上升，导致玻璃的绝缘性能快速下降，这对某些需要满足绝缘的应用是不利的。若Na 2O+K 2O低于5％，玻璃的热膨胀系数达不到设计要求，同时导致玻璃中变价组分的着色能力增强，玻璃的短波透过率达不到设计要求。因此，Na 2O和K 2O的合计含量Na 2O+K 2O为5～22％，优选为6～20％，更优选为8～18％。
Na 2O加入到玻璃中可以显著提升玻璃的热膨胀系数，同时可以降低玻璃的高温粘度，使得获得宽度大于330mm、能够加工为12英寸封装晶圆的玻璃产品更为容易。但若Na 2O的含量超过12％，玻璃的折射率下降，玻璃的化学稳定性快速下降，不能满足设计需求。若Na 2O的含量低于2％，玻璃的热膨胀系数达不到设计要求，同时化学稳定性也会劣化严重。因此，Na 2O的含量限定为2～12％，优选为3～10％，更优选为4～9％。
合适量K 2O添加到玻璃中可以提升玻璃的热膨胀系数，降低玻璃的高温粘度，提升玻璃的气泡度，尤其是在与Na 2O共存的情况下，合适量的K 2O加入玻璃中并不会明显损害玻璃的化学稳定性。但若其含量超过12％，玻璃的耐水、耐酸和耐碱性能劣化。若K 2O的含量低于2％，增大热膨胀系数与降低高温粘度的效果不明显。因此，K 2O的含量限定为2～12％，优选为3～10％，更优选为4～9％。
在本发明的一些实施方式中，若(B 2O 3+K 2O)/Al 2O 3的值大于10.0，玻璃的耐碱性降低，热膨胀系数增加；若(B 2O 3+K 2O)/Al 2O 3的值低于1.0，玻璃的熔融性降低，转变温度升高。因此，优选(B 2O 3+K 2O)/Al 2O 3的值为1.0～10.0，更优选(B 2O 3+K 2O)/Al 2O 3的值为1.5～8.0，进一步优选(B 2O 3+K 2O)/Al 2O 3的值为2.0～6.0。
在本发明的一些实施方式中，若(Na 2O+K 2O)/(B 2O 3+ZnO)的值低于0.2， 玻璃体系中游离氧不足，造成B 2O 3和ZnO等组分进入玻璃网络的几率降低，导致化学稳定性急剧下降，同时玻璃的膨胀系数降低，达不到设计要求。若(Na 2O+K 2O)/(B 2O 3+ZnO)的值大于2.5，玻璃体系中游离氧过剩，反而导致玻璃化学稳定性急剧下降，玻璃的膨胀系数超过设计要求。因此，当(Na 2O+K 2O)/(B 2O 3+ZnO)的值处于0.2～2.5之间，优选为0.3～2.0之间，更优选为0.5～1.5之间时，玻璃的化学稳定性和热膨胀系数最为平衡。
现有技术中通常认为，碱土金属氧化物MgO、CaO、SrO、BaO等加入到玻璃中较碱金属氧化物Li 2O、Na 2O、K 2O等更有利于化学稳定性的提升，本发明人通过试验发现，在本体系玻璃中，由于碱土金属氧化物提供游离氧的能力弱于碱金属氧化物，当(MgO+CaO+SrO+BaO)/(Na 2O+K 2O)的值大于1.0时，造成玻璃内部网络断裂严重，进而降低玻璃的化学稳定性，尤其是在强碱性溶液中浸泡时，若(MgO+CaO+SrO+BaO)/(Na 2O+K 2O)的值大于1.0，碱土金属离子更容易被侵蚀析出，这对半导体制程中某些工序是灾难性的。因此，(MgO+CaO+SrO+BaO)/(Na 2O+K 2O)的值为1.0以下，优选为0.5以下，更优选为0.2以下。
本发明中，为了获得合适的热膨胀系数，Na 2O和K 2O加入到玻璃中是必须的，但会导致玻璃化学稳定性的下降。本发明人经过研究发现，当玻璃中有Al 2O 3存在时，碱金属氧化物的种类以及相对含量会改变玻璃的微结构，对玻璃的化学稳定性产生较大的影响。在一些实施方式中，当满足(Na 2O+K 2O)/Al 2O 3的值为0.8～8.0，优选为1.0～6.0，更优选为1.5～5.0时，可提升玻璃的化学稳定性。
在本发明的一些实施方式中，当(SiO 2+TiO 2)/(Na 2O+ZnO)的值大于12.0时，玻璃变得难以熔化和澄清，玻璃内部气泡、夹杂物等排除困难，较难获得气泡度达到A 0级别以上的玻璃，同时玻璃内部条纹严重。若(SiO 2+TiO 2)/(Na 2O+ZnO)的值低于3.0，玻璃的热膨胀系数快速上升，超过设计要求。因此，优选(SiO 2+TiO 2)/(Na 2O+ZnO)的值控制在3.0～12.0之间，更优选为3.0～10.0之间，进一步优选为4.0～8.0之间。
合适量的ZrO 2加入到玻璃中可以提升玻璃的化学稳定性和抗热冲击性能，同时提升玻璃的折射率。但其特点在于会明显升高玻璃的熔化温度，若其含量高于5％，玻璃中容易出现夹杂物缺陷。因此ZrO 2的含量限定为5％以下，优选为3％以下。在一些实施方式中，当玻璃的化学稳定性和强度有富余时，更优选为不添加ZrO 2。
合适量的P 2O 5加入到玻璃中能够增加玻璃的强度，尤其是在需要进行化学强化的情况下。但若其含量超过5％，玻璃内部容易产生微分相，大幅度提升玻璃的成型温度。因此，P 2O 5的含量限定为0～5％，优选为0～3％。在一些实施方式中，当玻璃强度设计满足使用要求时，更优选为不添加P 2O 5。
在本发明的一些实施方式中，当需要提升玻璃折射率和转变温度时，可以添加合适量的La 2O 3、Y 2O 3、Gd 2O 3、Nb 2O 5、WO 3等氧化物，但其单独或组合含量超过5％时，玻璃的杨氏模量快速上升，玻璃的强度虽然上升，但玻璃的脆性上升更快，抗热冲击能力反而下降。另外，玻璃的抗析晶性能和短波透过率会恶化。因此，La 2O 3、Y 2O 3、Gd 2O 3、Nb 2O 5、WO 3的含量分别为5％以下，优选为3％以下，更优选为1％以下，进一步优选不含有。更进一步的，优选La 2O 3、Y 2O 3、Gd 2O 3、Nb 2O 5、WO 3的合计含量为5％以下，更优选为3％以下，进一步优选为1％以下。
在本发明的一些实施方式中，通过加入0～1％的Sb 2O 3、SnO 2、SnO、NaCl、硫酸盐和CeO 2中的一种或多种组分作为澄清剂，优选使用Sb 2O 3作为澄清剂，可以提高玻璃的澄清效果，优选加入0～0.5％的澄清剂。
F加入玻璃中会增加玻璃原料的挥发，易造成环境污染和玻璃条纹度变差，因此本发明玻璃中优选不含有F。Ta 2O 5加入玻璃中会大幅提高玻璃的折射率和成本，并使玻璃的熔化性能变差，因此本发明玻璃中优选不含有Ta 2O 5。
<不应含有的组分>
Th、Cd、Tl、Os、Be以及Se的氧化物，近年来作为有害的化学物质而有控制使用的倾向，不仅在玻璃的制造工序，直至加工工序以及产品化 后的处置上对环境保护的措施是必需的。因此，在重视对环境的影响的情况下，除了不可避免地混入以外，优选实际上不含有它们。由此，玻璃变得实际上不包含污染环境的物质。因此，即使不采取特殊的环境对策上的措施，本发明的玻璃也能够进行制造、加工以及废弃。
为了实现环境友好，本发明的玻璃不含有As 2O 3和PbO。虽然As 2O 3具有消除气泡和较好的防止玻璃着色的效果，但As 2O 3的加入会加大玻璃对熔炉特别是对铂金熔炉的铂金侵蚀，导致更多的铂金离子进入玻璃，对铂金熔炉的使用寿命造成不利影响。PbO可显著提高玻璃的高折射率和高色散性能，但PbO和As 2O 3都造成环境污染的物质。
本文所记载的“不含有”“不添加”“0％”是指没有故意将该化合物、分子或元素等作为原料添加到本发明玻璃中；但作为生产玻璃的原材料和/或设备，会存在某些不是故意添加的杂质或组分，会在最终的玻璃中少量或痕量含有，此种情形也在本发明专利的保护范围内。
下面，对本发明的玻璃材料的性能进行说明。
<折射率与阿贝数>
玻璃材料的折射率(nd)与阿贝数(ν d)按照GB/T 7962.1—2010规定的方法测试。
本发明玻璃材料的折射率(nd)的下限为1.48，优选下限为1.50，更优选下限为1.51，折射率(nd)的上限为1.56，优选为1.55，更优选为1.54；阿贝数(ν d)的下限为50，优选为51，更优选为53，阿贝数(ν d)的上限为58，优选为57，更优选为56。
<耐酸作用稳定性>
玻璃材料的耐酸作用稳定性(D A)(粉末法)按照GB/T 17129规定的方法测试。本文中耐酸作用稳定性有时候简称为耐酸性或耐酸稳定性。
本发明玻璃材料的耐酸作用稳定性(D A)为2类以上，优选为1类。
<耐水作用稳定性>
玻璃材料的耐水作用稳定性(D W)(粉末法)按照GB/T 17129规定的方 法测试。本文中耐水作用稳定性有时候简称为耐水性或耐水稳定性。
本发明玻璃材料的耐水作用稳定性(D W)为2类以上，优选为1类。
<耐碱作用稳定性>
玻璃材料的耐碱作用稳定性按照ISO 10629的测试条件和要求进行测量，以玻璃样品失重量表示。本文中耐碱作用稳定性有时候简称为耐碱性或耐碱稳定性。
将玻璃加工为30mm×30mm×2mm规格的测试样品，六面抛光，放入2000ml的NaOH溶液中，所述NaOH溶液的浓度为0.01mol/L，PH值为12.0，测试过程定时用PH计监控试液PH值变化情况，并及时更换反应试液，在50℃温度下侵蚀100小时后，采用电子天平计量样品失重，失重以mg表示。
本发明玻璃材料按上述测试方法后的失重小于9mg，优选小于7mg，更优选小于5mg。
<热膨胀系数>
本发明所述的热膨胀系数是指玻璃20～300℃平均热膨胀系数,以α 20-300℃表示，按GB/T7962.16-2010规定方法测试。
本发明玻璃材料的平均热膨胀系数(α 20-300℃)的上限为90×10 -7/K，优选上限为85×10 -7/K，更优选上限为80×10 -7/K，平均热膨胀系数(α 20-300℃)的下限为60×10 -7/K，优选下限为65×10 -7/K，更优选下限为68×10 -7/K。
<光透过率>
本发明所述的光透过率是指10mm厚度玻璃样品在360nm处的内透过率，以τ 360nm表示，按GB/T7962.12-2010规定方法测试。
本发明玻璃材料的360nm处内透过率(τ 360nm)为78％以上，优选为82％以上，更优选为85％以上。
<转变温度>
玻璃的转变温度(T g)按GB/T7962.16-2010规定方法测试。
本发明玻璃的转变温度(T g)的上限为610℃，优选上限为600℃，更优选上限为580℃，转变温度(T g)的下限为500℃，优选下限为520℃，更 优选下限为530℃。
<杨氏模量>
玻璃的杨氏模量(E)采用以下公式计算得出：
Figure PCTCN2021087203-appb-000001
其中，G＝V S 2ρ
式中：
E为杨氏模量，Pa；
G为剪切模量，Pa；
V T为纵波速度，m/s；
V S为横波速度，m/s；
ρ为玻璃密度，g/cm 3。
本发明玻璃材料的杨氏模量(E)的下限为6000×10 7Pa，优选下限为6500×10 7Pa，更优选下限为7000×10 7Pa，杨氏模量(E)的上限为8500×10 7Pa，优选上限8000×10 7Pa。
<气泡度>
玻璃材料的气泡度按照GB/T7962.8-2010规定的测试方法进行测试。
本发明玻璃材料的气泡度为A级以上，优选为A 0级以上，更优选为A 00级。
<条纹度>
玻璃材料的条纹度按MLL-G-174B规定的方法进行测量。方法为用点光源和透镜组成的条纹仪，从最容易看见条纹的方向上，与标准试样比较检查，共分为4级，分别为A、B、C、D级，A级为规定检测条件下无肉眼可见的条纹，B级为规定检测条件下有细而分散的条纹，C级为规定检测条件下有轻微的平行条纹，D级为规定检测条件下有粗略的条纹。
本发明的玻璃材料的条纹为C级以上，优选B级以上。
本发明玻璃材料具有上述优异性能，可广泛应用于电子器件、感光器件的封装领域，也可应用于制造玻璃元件，制造各种设备或仪器，例如成 像设备、传感器、显微镜、医药技术、数字投影、通信、光学通信技术/信息传输、汽车领域中的光学/照明、光刻技术、准分子激光器、晶片、计算机芯片以及包括这样的电路及芯片的集成电路和电子器件，或用于车载领域、监控安防领域的摄像设备和装置。
[制造方法]
本发明玻璃材料的制造方法如下：本发明的玻璃采用常规原料和常规工艺生产，使用碳酸盐、硝酸盐、硫酸盐、氢氧化物、氧化物等为原料，按常规方法配料后，将配好的炉料投入到1300～1500℃的熔炼炉中熔制，并且经澄清、搅拌和均化后，得到没有气泡及不含未溶解物质的均质熔融玻璃，将此熔融玻璃在模具内铸型并退火而成。本领域技术人员能够根据实际需要，适当地选择原料、工艺方法和工艺参数。
实施例
为了进一步清楚地阐释和说明本发明的技术方案，提供以下的非限制性实施例1～20。
本实施例采用上述玻璃材料的制造方法得到具有表1～表2所示的组成的玻璃材料。另外，通过本发明所述的测试方法测定各玻璃的特性，并将测定结果表示在表1～表2中。
表1
Figure PCTCN2021087203-appb-000002
Figure PCTCN2021087203-appb-000003
表2
Figure PCTCN2021087203-appb-000004
Figure PCTCN2021087203-appb-000005

Claims (19)

  1. 玻璃材料，其特征在于，其组分以重量百分比表示，含有：SiO 2：50～70％；B 2O 3：3～15％；TiO 2：0.5～10％；ZnO：1～12％；Al 2O 3：0.5～10％；Na 2O+K 2O：5～22％，其中B 2O 3/SiO 2为0.06～0.26，(TiO 2+ZnO)/Al 2O 3为0.5～8.0。
  2. 根据权利要求1所述的玻璃材料，其特征在于，其组分以重量百分比表示，还含有：MgO+CaO+SrO+BaO：0～10％；和/或Li 2O：0～5％；和/或P 2O 5：0～5％；和/或ZrO 2：0～5％；和/或La 2O 3：0～5％；和/或Y 2O 3：0～5％；和/或Gd 2O 3：0～5％；和/或Nb 2O 5：0～5％；和/或WO 3：0～5％；和/或澄清剂：0～1％。
  3. 玻璃材料，其特征在于，其组分以重量百分比表示由SiO 2：50～70％；B 2O 3：3～15％；TiO 2：0.5～10％；ZnO：1～12％；Al 2O 3：0.5～10％；Na 2O+K 2O：5～22％；MgO+CaO+SrO+BaO：0～10％；Li 2O：0～5％；P 2O 5：0～5％；ZrO 2：0～5％；La 2O 3：0～5％；Y 2O 3：0～5％；Gd 2O 3：0～5％；Nb 2O 5：0～5％；WO 3：0～5％；澄清剂：0～1％组成，其中B 2O 3/SiO 2为0.06～0.26，(TiO 2+ZnO)/Al 2O 3为0.5～8.0。
  4. 根据权利要求1～3任一权利要求所述的玻璃材料，其特征在于，其组分以重量百分比表示，其中：B 2O 3/SiO 2为0.08～0.2；和/或(TiO 2+ZnO)/Al 2O 3为0.7～7.0；和/或(SiO 2+TiO 2)/(Na 2O+ZnO)为3.0～12.0；和/或ZnO/B 2O 3为0.2～1.8；和/或(Na 2O+K 2O)/Al 2O 3为0.8～8.0；和/或(Na 2O+K 2O)/(B 2O 3+ZnO)为0.2～2.5；和/或(B 2O 3+K 2O)/Al 2O 3为1.0～10.0。
  5. 根据权利要求1～3任一权利要求所述的玻璃材料，其特征在于，其组分以重量百分比表示，其中：(MgO+CaO+SrO+BaO)/ZnO为1.0以下；和/或(MgO+CaO+SrO+BaO)/Al 2O 3为1.0以下；和/或(MgO+CaO+SrO+BaO)/(Na 2O+K 2O)为1.0以下。
  6. 根据权利要求1～3任一权利要求所述的玻璃材料，其特征在于，其组分以重量百分比表示，其中：SiO 2：55～68％；和/或B 2O 3：大于5％但 小于或等于13％；和/或TiO 2：1.5～8％；和/或ZnO：2～10％；和/或Al 2O 3：1～8％；和/或Na 2O+K 2O：6～20％；和/或MgO+CaO+SrO+BaO：0～5％；和/或Li 2O：0～3％；和/或P 2O 5：0～3％；和/或ZrO 2：0～3％；和/或La 2O 3：0～3％；和/或Y 2O 3：0～3％；和/或Gd 2O 3：0～3％；和/或Nb 2O 5：0～3％；和/或WO 3：0～3％；和/或澄清剂：0～0.5％。
  7. 根据权利要求1～3任一权利要求所述的玻璃材料，其特征在于，其组分以重量百分比表示，其中：B 2O 3/SiO 2为0.1～0.18；和/或(TiO 2+ZnO)/Al 2O 3为1.0～5.0；和/或(SiO 2+TiO 2)/(Na 2O+ZnO)为3.0～10.0；和/或ZnO/B 2O 3为0.3～1.0；和/或(Na 2O+K 2O)/Al 2O 3为1.0～6.0；和/或(Na 2O+K 2O)/(B 2O 3+ZnO)为0.3～2.0；和/或(B 2O 3+K 2O)/Al 2O 3为1.5～8.0。
  8. 根据权利要求1～3任一权利要求所述的玻璃材料，其特征在于，其组分以重量百分比表示，其中：(MgO+CaO+SrO+BaO)/ZnO为0.5以下；和/或(MgO+CaO+SrO+BaO)/Al 2O 3为0.5以下；和/或(MgO+CaO+SrO+BaO)/(Na 2O+K 2O)为0.5以下。
  9. 根据权利要求1～3任一权利要求所述的玻璃材料，其特征在于，其组分以重量百分比表示，其中：SiO 2：60～68％；和/或B 2O 3：6～12％；和/或TiO 2：2～7％；和/或ZnO：3～8％；和/或Al 2O 3：2～7％；和/或Na 2O+K 2O：8～18％；和/或La 2O 3：0～1％；和/或Y 2O 3：0～1％；和/或Gd 2O 3：0～1％；和/或Nb 2O 5：0～1％；和/或WO 3：0～1％。
  10. 根据权利要求1～3任一权利要求所述的玻璃材料，其特征在于，其组分以重量百分比表示，其中：(SiO 2+TiO 2)/(Na 2O+ZnO)为4.0～8.0；和/或ZnO/B 2O 3为0.4～0.8；和/或(Na 2O+K 2O)/Al 2O 3为1.5～5.0；和/或(Na 2O+K 2O)/(B 2O 3+ZnO)为0.5～1.5；和/或(B 2O 3+K 2O)/Al 2O 3为2.0～6.0。
  11. 根据权利要求1～3任一权利要求所述的玻璃材料，其特征在于，其组分以重量百分比表示，其中：(MgO+CaO+SrO+BaO)/ZnO为0.2以下；和/或(MgO+CaO+SrO+BaO)/Al 2O 3为0.2以下；和/或(MgO+CaO+SrO+BaO)/(Na 2O+K 2O)为0.2以下。
  12. 根据权利要求1～3任一权利要求所述的玻璃材料，其特征在于，其组分以重量百分比表示，其中：Na 2O：2～12％，优选Na 2O：3～10％，更优选Na 2O：4～9％；和/或K 2O：2～12％，优选K 2O：3～10％，更优选K 2O：4～9％；和/或MgO：0～5％，优选MgO：0～3％，更优选MgO：0～2％；和/或CaO：0～5％，优选CaO：0～3％，更优选CaO：0～2％；和/或SrO：0～5％，优选SrO：0～3％，更优选SrO：0～2％；和/或BaO：0～5％，优选BaO：0～3％，更优选BaO：0～2％。
  13. 根据权利要求1～3任一权利要求所述的玻璃材料，其特征在于，其组分以重量百分比表示，其中：La 2O 3、Y 2O 3、Gd 2O 3、Nb 2O 5、WO 3的合计含量为5％以下，优选为3％以下，更优选为1％以下。
  14. 根据权利要求1～3任一权利要求所述的玻璃材料，其特征在于，其组分中不含有F；和/或不含有Ta 2O 5；和/或不含有Li 2O；和/或不含有P 2O 5；和/或不含有ZrO 2。
  15. 根据权利要求1～3任一权利要求所述的玻璃材料，其特征在于，所述玻璃材料的折射率为1.48～1.56，优选为1.50～1.55，更优选为1.51～1.54；和/或阿贝数为50～58，优选为51～57，更优选为53～56；和/或热膨胀系数α 20-300℃为60×10 -7/K～90×10 -7/K，优选为65×10 -7/K～85×10 -7/K，更优选为68×10 -7/K～80×10 -7/K；和/或杨氏模量为6000×10 7Pa以上，优选为6500×10 7Pa～8500×10 7Pa，更优选为7000×10 7Pa～8000×10 7Pa；和/或转变温度为500℃～610℃，优选为520℃～600℃，更选为530℃～580℃；和/或气泡度为A级以上，优选为A 0级以上，更优选为A 00级；和/或条纹为C级以上，优选B级以上。
  16. 根据权利要求1～3任一权利要求所述的玻璃材料，其特征在于，所述玻璃材料的耐酸作用稳定性为2类以上，优选为1类；和/或耐水作用稳定性为2类以上，优选为1类；和/或耐碱作用稳定性按照ISO 10629的测试条件和要求进行测量后的玻璃样品失重小于9mg，优选小于7mg，更优选小于5mg；和/或光透过率τ 360nm为78％以上，优选为82％以上，更优选为85％以 上。
  17. 权利要求1～16任一权利要求所述的玻璃材料在封装领域的应用。
  18. 玻璃元件，采用权利要求1～16任一权利要求所述的玻璃材料制成。
  19. 一种设备，含有权利要求1～16任一权利要求所述的玻璃材料，或含有权利要求18所述的玻璃元件。
PCT/CN2021/087203 2020-05-27 2021-04-14 玻璃材料 Ceased WO2021238476A1 (zh)

Priority Applications (4)

Application Number Priority Date Filing Date Title
US17/923,675 US20230174409A1 (en) 2020-05-27 2021-04-14 Glass material
EP21811829.7A EP4159696A4 (en) 2020-05-27 2021-04-14 GLASS MATERIAL
JP2022572544A JP2023528338A (ja) 2020-05-27 2021-04-14 ガラス材料
JP2025037346A JP2025087872A (ja) 2020-05-27 2025-03-10 ガラス材料、ガラス部材および装置

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202010460020.2 2020-05-27
CN202010460020.2A CN111423111B (zh) 2020-05-27 2020-05-27 玻璃材料

Publications (1)

Publication Number Publication Date
WO2021238476A1 true WO2021238476A1 (zh) 2021-12-02

Family

ID=71553125

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2021/087203 Ceased WO2021238476A1 (zh) 2020-05-27 2021-04-14 玻璃材料

Country Status (6)

Country Link
US (1) US20230174409A1 (zh)
EP (1) EP4159696A4 (zh)
JP (2) JP2023528338A (zh)
CN (1) CN111423111B (zh)
TW (1) TWI756113B (zh)
WO (1) WO2021238476A1 (zh)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114873918A (zh) * 2022-06-24 2022-08-09 成都光明光电有限责任公司 光敏玻璃材料

Families Citing this family (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111423111B (zh) * 2020-05-27 2022-04-15 成都光明光电股份有限公司 玻璃材料
CN112010561B (zh) * 2020-09-17 2022-04-15 成都光明光电股份有限公司 封装玻璃
CN112939455B (zh) * 2021-03-23 2022-04-15 成都光明光电股份有限公司 光学玻璃、光学元件和光学仪器
CN113045199B (zh) * 2021-03-23 2022-04-15 成都光明光电股份有限公司 透紫外玻璃
CN113121119B (zh) * 2021-04-25 2022-04-08 中建材玻璃新材料研究院集团有限公司 一种微型射频玻璃绝缘子用低介电封接玻璃粉
CN113213756A (zh) * 2021-06-21 2021-08-06 成都光明光电有限责任公司 玻璃材料
CN113480169A (zh) * 2021-08-03 2021-10-08 四川虹科创新科技有限公司 一种耐酸耐碱锂铝硅玻璃
CN113735438B (zh) * 2021-09-23 2023-06-16 成都光明光电股份有限公司 玻璃组合物
CN113754277B (zh) * 2021-10-29 2023-05-12 成都光明光电股份有限公司 玻璃材料
CN114538775A (zh) * 2022-02-17 2022-05-27 湖北省椿丰光电科技有限公司 一种高均匀性光学玻璃及制备方法
CN114956549B (zh) * 2022-06-14 2023-07-04 成都光明光电有限责任公司 封接玻璃
CN115893833B (zh) * 2022-12-06 2025-01-24 成都光明光电股份有限公司 光学玻璃、玻璃预制件、光学元件及光学仪器
CN116789361A (zh) * 2023-06-28 2023-09-22 咸宁南玻光电玻璃有限公司 含碱玻璃及其制备方法、含玻璃的制品、电子产品和应用
CN117247230A (zh) * 2023-08-01 2023-12-19 咸宁南玻光电玻璃有限公司 玻璃及其通孔加工方法和应用
CN117602828B (zh) * 2023-11-24 2025-06-03 中国建筑材料科学研究总院有限公司 用于中膨胀光纤传像元件的低折射率玻璃及其制备方法
CN119390350A (zh) * 2024-10-18 2025-02-07 清远南玻节能新材料有限公司 玻璃及其制备方法、玻璃纤维和电子器件

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB191517129A (en) 1915-12-06 1916-09-28 Ellen Kent Device for Holding Playing Cards.
US4565791A (en) * 1984-01-13 1986-01-21 Corning Glass Works Glasses for ophthalmic applications
CN1241543A (zh) * 1998-06-29 2000-01-19 肖特玻璃制造厂 无铅光学玻璃
JP2005200296A (ja) * 2003-12-18 2005-07-28 Nippon Electric Glass Co Ltd モールドプレス成形用ガラス
US20070032367A1 (en) * 2004-03-19 2007-02-08 Gerold Sprachmann Lead- and barium-free crystal glass
JP2012051773A (ja) * 2010-09-02 2012-03-15 Nippon Electric Glass Co Ltd 樹脂複合体基板用ガラス
KR20190093512A (ko) * 2018-02-01 2019-08-09 쇼오트 아게 방사선불투과성 유리 및 이의 용도
CN110228945A (zh) * 2019-06-28 2019-09-13 成都光明光电股份有限公司 一种光学玻璃及其玻璃预制件、元件和仪器
CN111423111A (zh) * 2020-05-27 2020-07-17 成都光明光电股份有限公司 玻璃材料

Family Cites Families (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60260443A (ja) * 1984-06-07 1985-12-23 Nippon Sheet Glass Co Ltd アルカリ溶出の少いガラス組成物
JPS62187141A (ja) * 1986-02-13 1987-08-15 Nippon Electric Glass Co Ltd 太陽電池カバ−用ガラス
US6207603B1 (en) * 1999-02-05 2001-03-27 Corning Incorporated Solar cell cover glass
ATE438373T1 (de) * 1999-07-02 2009-08-15 Pentron Ceramics Inc Porzellanmassen für vollkeramischen dentalkernen oder zur verwendung mit kernen aus metallegierungen
EP1227069B1 (en) * 2001-01-29 2004-11-17 Hoya Corporation Optical glass
WO2002072492A1 (fr) * 2001-03-08 2002-09-19 Nippon Electric Glass Co., Ltd. Enveloppe tubulaire pour lampe fluorescente
JP2003342037A (ja) * 2002-05-27 2003-12-03 Central Glass Co Ltd Ｗｄｍ光フィルター用ガラス
US7060640B2 (en) * 2002-07-18 2006-06-13 Kabushiki Kaisha Ohara Optical glass
JP4530618B2 (ja) * 2002-09-27 2010-08-25 コニカミノルタオプト株式会社 ガラス組成物及びガラス基板
DE10245880B4 (de) * 2002-09-30 2004-08-05 Schott Glas Weissgläser/Borosilikatgläser mit spezieller UV-Kante
WO2006003755A1 (ja) * 2004-07-06 2006-01-12 Murata Manufacturing.Co., Ltd. 導電性ペースト及びそれを用いたセラミック電子部品
US20090088309A1 (en) * 2006-02-14 2009-04-02 Nippon Sheet Glass Company, Limited Glass Composition
JP5085049B2 (ja) * 2006-03-31 2012-11-28 Ｈｏｙａ株式会社 モールドプレス用ガラス素材、該ガラス素材の製造方法、及びガラス光学素子の製造方法
US20090286058A1 (en) * 2006-05-19 2009-11-19 Noriaki Shibata Crystal Glass Article
DE102008043317B4 (de) * 2008-10-30 2013-08-08 Schott Ag Verwendung eines solarisationsbeständigen Glases mit einer definierten Steigung der UV-Kante für einen Strahler für Bewitterungsanlagen
WO2011065293A1 (ja) * 2009-11-25 2011-06-03 旭硝子株式会社 ディスプレイカバーガラス用ガラス基板及びその製造方法
DE102011052622B9 (de) * 2011-08-12 2013-03-21 Schott Ag Arsen- und antimonfreies, titanoxidhaltiges Borosilikatglas, Verfahren zu dessen Herstellung, Verwendung des Glases und Verwendung sauerstoffhaltiger Selenverbindungen zur Läuterung
DE102014013550A1 (de) * 2014-09-12 2016-03-31 Schott Ag Beschichtetes chemisch vorgespanntes flexibles dünnes Glas
CN106116143B (zh) * 2016-06-29 2019-12-03 成都光明光电股份有限公司 光学玻璃
WO2018218690A1 (en) * 2017-06-02 2018-12-06 Schott Glass Technologies (Suzhou) Co., Ltd. High contact resistant flexible ultrathin glass
JP7129782B2 (ja) * 2018-01-26 2022-09-02 株式会社松風 耐水性に優れた低融点ガラス組成物
CN109626814B (zh) * 2019-01-07 2021-09-28 成都光明光电股份有限公司 环保光学玻璃、光学预制件、光学元件及光学仪器
CN109809688A (zh) * 2019-04-01 2019-05-28 湖北戈碧迦光电科技股份有限公司 一种光学玻璃、制备方法及其应用
CN110217984A (zh) * 2019-06-28 2019-09-10 成都光明光电股份有限公司 一种光学玻璃及其玻璃预制件、元件和仪器
CN110316960B (zh) * 2019-07-22 2022-02-11 成都光明光电股份有限公司 光学玻璃、玻璃预制件、光学元件及光学仪器

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB191517129A (en) 1915-12-06 1916-09-28 Ellen Kent Device for Holding Playing Cards.
US4565791A (en) * 1984-01-13 1986-01-21 Corning Glass Works Glasses for ophthalmic applications
CN1241543A (zh) * 1998-06-29 2000-01-19 肖特玻璃制造厂 无铅光学玻璃
JP2005200296A (ja) * 2003-12-18 2005-07-28 Nippon Electric Glass Co Ltd モールドプレス成形用ガラス
US20070032367A1 (en) * 2004-03-19 2007-02-08 Gerold Sprachmann Lead- and barium-free crystal glass
JP2012051773A (ja) * 2010-09-02 2012-03-15 Nippon Electric Glass Co Ltd 樹脂複合体基板用ガラス
KR20190093512A (ko) * 2018-02-01 2019-08-09 쇼오트 아게 방사선불투과성 유리 및 이의 용도
CN110228945A (zh) * 2019-06-28 2019-09-13 成都光明光电股份有限公司 一种光学玻璃及其玻璃预制件、元件和仪器
CN111423111A (zh) * 2020-05-27 2020-07-17 成都光明光电股份有限公司 玻璃材料

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114873918A (zh) * 2022-06-24 2022-08-09 成都光明光电有限责任公司 光敏玻璃材料
CN114873918B (zh) * 2022-06-24 2023-08-08 成都光明光电有限责任公司 光敏玻璃材料

Also Published As

Publication number Publication date
TW202144302A (zh) 2021-12-01
CN111423111B (zh) 2022-04-15
JP2023528338A (ja) 2023-07-04
JP2025087872A (ja) 2025-06-10
EP4159696A4 (en) 2024-05-22
US20230174409A1 (en) 2023-06-08
CN111423111A (zh) 2020-07-17
TWI756113B (zh) 2022-02-21
EP4159696A1 (en) 2023-04-05

Similar Documents

Publication Publication Date Title
TWI756113B (zh) 玻璃材料
TWI756114B (zh) 光學玻璃
CN111574049B (zh) 玻璃组合物
WO2022193797A1 (zh) 高折射高色散光学玻璃及光学元件
TW202337853A (zh) 玻璃組合物
CN112142322B (zh) 光学玻璃、玻璃预制件、光学元件和光学仪器
JP2023539916A5 (zh)
CN110342813A (zh) 光学玻璃、光学元件和光学仪器
TW202525740A (zh) 光學玻璃及光學元件
TWI895773B (zh) 光學玻璃、光學元件和光學儀器
TW202400532A (zh) 光學玻璃及光學元件
CN115321814A (zh) 光学玻璃
TWI865119B (zh) 玻璃材料
TWI917192B (zh) 光學玻璃、玻璃預製件、光學元件和光學儀器
CN120794340B (zh) 玻璃组合物
CN111320381A (zh) 光学玻璃、玻璃预制件和光学元件
CN110316962A (zh) 光学玻璃及光学元件
CN115745398A (zh) 玻璃组合物
WO2026061140A1 (zh) 玻璃材料
WO2024041277A1 (zh) 光学玻璃、玻璃预制件、光学元件及光学仪器
CN120794329A (zh) 高模量玻璃
CN120172638A (zh) 光学玻璃、玻璃预制件、光学元件和光学仪器
CN121270089A (zh) 光学玻璃、玻璃预制件、光学元件和光学仪器
JP2026057532A (ja) 光学ガラス、光学素子と光学機器
CN120794344A (zh) 光学玻璃和光学元件

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: 21811829

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2022572544

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 2021811829

Country of ref document: EP

Effective date: 20230102