WO2023045753A1 - 玻璃组合物 - Google Patents

玻璃组合物 Download PDF

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Publication number
WO2023045753A1
WO2023045753A1 PCT/CN2022/117257 CN2022117257W WO2023045753A1 WO 2023045753 A1 WO2023045753 A1 WO 2023045753A1 CN 2022117257 W CN2022117257 W CN 2022117257W WO 2023045753 A1 WO2023045753 A1 WO 2023045753A1
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WIPO (PCT)
Prior art keywords
glass
glass composition
less
zno
sio
Prior art date
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Ceased
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PCT/CN2022/117257
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English (en)
French (fr)
Inventor
毛露路
匡波
郝良振
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CDGM Glass Co Ltd
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CDGM Glass Co Ltd
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Filing date
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Application filed by CDGM Glass Co Ltd filed Critical CDGM Glass Co Ltd
Priority to EP22871802.9A priority Critical patent/EP4406923A4/en
Priority to JP2024517475A priority patent/JP7778229B2/ja
Publication of WO2023045753A1 publication Critical patent/WO2023045753A1/zh
Anticipated expiration legal-status Critical
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • 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
    • C03C3/097—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
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/11—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen
    • C03C3/112—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine
    • C03C3/115—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine containing boron
    • C03C3/118—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine containing boron containing aluminium
    • G—PHYSICS
    • 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

Definitions

  • the invention relates to a glass composition, in particular to a glass composition with excellent chemical stability and weather resistance.
  • the car light lens can shape the light emitted by the light source, increase the illuminance within the range of 150-400 meters in front of the car, and improve the safety of the car during driving. Therefore, more and more car lights choose to install the car light lens.
  • the car light lens in the prior art is made of soda-lime-silica glass. With the significant increase in the service life requirements of car lights and the development of future car lights to smart car lights, soda-lime-silica glass is becoming less and less suitable for car light lenses. development needs. Soda-lime-silica glass can obtain imaging-grade products, but its chemical stability is poor, especially its water resistance and weather resistance. It will damage safety, and at the same time, it will not be able to meet the imaging requirements of future automotive headlights.
  • the technical problem to be solved by the present invention is to provide a glass composition with excellent chemical stability and weather resistance.
  • Glass composition the components of which are represented by weight percentage, containing: SiO 2 : 52-72%; B 2 O 3 : 3-17%; Al 2 O 3 : 0.5-8%; ZnO: 2-10% %; Rn 2 O: 6-25%, wherein Al 2 O 3 /B 2 O 3 is 0.1-1.0, and the Rn 2 O is the total content of Li 2 O, Na 2 O, and K 2 O.
  • the glass composition according to (1) the components of which are represented by weight percent, and further include: RO: 0-15%; and/or TiO 2 : 0-5%; and/or P 2 O 5 : 0 ⁇ 2%; and/or ZrO 2 : 0 ⁇ 3%; and/or La 2 O 3 : 0 ⁇ 5%; and/or Y 2 O 3 : 0 ⁇ 8%; and/or clarifying agent: 0 ⁇ 1%, the RO is the total content of MgO, CaO, SrO, and BaO, and the clarifying agent is one or more of Sb 2 O 3 , SnO 2 , Na 2 SiF 6 , and K 2 SiF 6 .
  • the glass composition according to (3) the components of which are represented by weight percent, including: SiO 2 : 52-72%; and/or B 2 O 3 : 3-17%; and/or Al 2 O 3 : 0.5-8%; and/or ZnO: 2-10%; and/or TiO 2 : 0-5%; and/or Rn 2 O: 6-25%; and/or RO: 0-15% ; and/or P 2 O 5 : 0-2%; and/or ZrO 2 : 0-3%; and/or La 2 O 3 : 0-5%; and/or Y 2 O 3 : 0-8% and/or clarifying agent: 0-1%, the RO is the total content of MgO, CaO, SrO, BaO, Rn 2 O is the total content of Li 2 O, Na 2 O, K 2 O, and the clarifying agent is Sb One or more of 2 O 3 , SnO 2 , Na 2 SiF 6 , and K 2 SiF 6 .
  • Al 2 O 3 /SiO 2 is 0.01 to 0.1, preferably Al 2 O 3 /SiO 2 0.02 to 0.08, more preferably Al 2 O 3 /SiO 2 is 0.03 to 0.07; and/or Al 2 O 3 /B 2 O 3 is 0.15 to 0.8, preferably Al 2 O 3 /B 2 O 3 is 0.15 to 0.6 and/or ZnO/SiO 2 is 0.03-0.17, preferably ZnO/SiO 2 is 0.04-0.15, more preferably ZnO/SiO 2 is 0.06-0.12; and/or (ZnO+TiO 2 )/B 2 O 3 is 0.2 ⁇ 2.0, preferably (ZnO+TiO 2 )/B 2 O 3 is 0.3 ⁇ 1.5, more preferably (ZnO+TiO 2 )/B 2 O 3 is 0.35 ⁇ 1.0.
  • K 2 O/(Na 2 O+Li 2 O) is 0.8 or less, preferably K 2 O/(Na 2 O+Li 2 O) is 0.05-0.5, more preferably K 2 O/(Na 2 O+Li 2 O) is 0.1-0.3; and/or Li 2 O/Na 2 O is 0.01-0.3 , preferably Li 2 O/Na 2 O is 0.02-0.25, more preferably Li 2 O/Na 2 O is 0.03-0.22; and/or K 2 O/Na 2 O is 0.01-0.8, preferably K 2 O/Na 2 O is 0.05 to 0.5, more preferably K 2 O/Na 2 O is 0.1 to 0.4.
  • the N element content in the glass raw material is lower than 2.0%, preferably lower than 1.5%, more preferably lower than 1.0%, and the N element content is It is the introduction amount of N element for melting 100Kg theoretical glass/100Kg glass weight ⁇ 100%.
  • the refractive index n d of the glass composition according to any one of (1) to (11) is 1.50 to 1.56, preferably 1.505 to 1.55, more preferably 1.51 to 1.54; the Abbe number ⁇ d is 56 to 1.56. 65, preferably 57-63, more preferably 57.5-62.
  • the acid resistance stability D A of the glass composition according to any one of (1) to (12) is 2 or more, preferably 1; and/or the water resistance stability D W is 2 or more, Preferably Class 1; and/or the coefficient of thermal expansion ⁇ 20/300°C is 85 ⁇ 10 -7 /K or less, preferably 82 ⁇ 10 -7 /K or less, more preferably 80 ⁇ 10 -7 /K or less; and/or Or the transition temperature T g is below 580°C, preferably below 570°C, more preferably below 560°C; and/or the density ⁇ is below 2.70g/ cm3 , preferably below 2.65g/ cm3 , more preferably below 2.60g /cm 3 or less; and/or light transmittance ⁇ 400nm is more than 98.0%, preferably more than 98.5%, more preferably more than 99.0%, more preferably more than 99.2%; and/or after 200 hours of weather resistance test, The turbidity is increased by 2.0% or less, preferably
  • the beneficial effect of the present invention is that: through reasonable component design, the glass composition obtained by the present invention has excellent chemical stability and weather resistance, and can be used for manufacturing vehicle lamp lenses.
  • the present invention is not limited to the following embodiments, and can be implemented with appropriate changes within the scope of the purpose of the present invention.
  • the gist of the invention is not limited thereto.
  • the glass composition of the present invention is sometimes simply referred to as glass.
  • each component (ingredient) of the glass composition of the present invention will be described below.
  • the content and total content of each component are all expressed in weight percent (wt%), that is, the content of each component and the total content are relative to the total amount of glass substances converted into oxides.
  • the amount is expressed in weight percent.
  • the “composition in terms of oxides” means that the oxides, composite salts, hydroxides, etc. used as raw materials for the composition of the glass composition of the present invention are decomposed and converted into oxides when melted.
  • the total amount of substances of the oxide is taken as 100%.
  • SiO 2 is the main component of glass. If its content exceeds 72%, the glass will be difficult to melt, and bubbles, inclusions and streaks cannot be excluded, making it difficult to obtain imaging-quality products.
  • the refractive index of the glass will be lower than the design requirements. The refractive index of the glass is too low, which means that under the same diffusion angle requirements of the beam, the lamp lens needs a larger curvature, and a larger curvature requires more difficult heat-pressing. Larger optical errors, as well as more prone to defects in thermocompression molding, accelerate the generation of corrosion spots on the lens surface.
  • the content of SiO 2 is lower than 52%, the chemical stability (especially water resistance) and weather resistance of the glass are difficult to meet the design requirements;
  • the content of SiO 2 is 52-72%, preferably 55-70%, more preferably 56-68%.
  • An appropriate amount of B 2 O 3 can reduce the melting temperature and high-temperature viscosity of the glass.
  • the lower the high-temperature viscosity the easier it is to eliminate glass bubbles, inclusions and streaks. More importantly, an appropriate amount of B 2 O 3 will further tighten the glass network and improve the weather resistance of the glass. If the content is less than 3%, the above effects will not be obvious. If the content of B 2 O 3 is higher than 17%, the water resistance of the glass decreases rapidly. Therefore, its content is limited to 3-17%, preferably 5-15%, more preferably 7-13%.
  • Al 2 O 3 can strengthen the glass network, improve the chemical stability of the glass, and reduce the thermal expansion coefficient of the glass. If the content of Al 2 O 3 is less than 0.5%, the above effects are not obvious; if the content of Al 2 O 3 exceeds 8%, the glass The high-temperature viscosity rises rapidly, and it is difficult to meet the design requirements. Therefore, the content range of Al 2 O 3 is 0.5-8%, preferably 1-6%, more preferably 1-5%.
  • the relative content of Al 2 O 3 and SiO 2 has a significant impact on the weather resistance of the glass.
  • the value of Al 2 O 3 /SiO 2 is less than 0.01, the weather resistance of the glass decreases and it is difficult to meet the design requirements;
  • the value of Al 2 O 3 /SiO 2 is greater than 0.1, the weather resistance of the glass is no longer significantly improved, but the viscosity at high temperature increases rapidly. Therefore, the value of Al 2 O 3 /SiO 2 is preferably 0.01 to 0.1, the value of Al 2 O 3 /SiO 2 is more preferably 0.02 to 0.08, and the value of Al 2 O 3 /SiO 2 is still more preferably 0.03 to 0.07.
  • the relative content of Al 2 O 3 and B 2 O 3 has a significant impact on the water resistance of the glass, and when the value of Al 2 O 3 /B 2 O 3 is less than 0.1, the water resistance of the glass decreases, It is difficult to meet the design requirements; when the value of Al 2 O 3 /B 2 O 3 is greater than 1.0, the water resistance of the glass is no longer significantly improved, but the viscosity at high temperature increases rapidly. Therefore, the value of Al 2 O 3 /B 2 O 3 is preferably 0.1 to 1.0, more preferably 0.15 to 0.8, and even more preferably 0.15 to 0.6.
  • a small amount of P 2 O 5 in glass can significantly improve the chemical strengthening performance of glass, and at the same time, P 2 O 5 in glass can promote the formation of glass crystallites and improve the thermal shock resistance of glass. If the content of P 2 O 5 is higher than 2%, the glass becomes unstable or even devitrified. Therefore, the content of P 2 O 5 is controlled below 2%, preferably below 1%. If the chemical strengthening performance and thermal shock resistance of the glass are sufficient, it is more preferable not to contain P 2 O 5 .
  • an appropriate amount of ZnO can significantly increase the refractive index of the glass and reduce the thermal expansion coefficient and transition temperature of the glass. If the content of ZnO is less than 2%, the above effect is not obvious; if the content of ZnO is higher than 10%, the Abbe number of the glass will decrease. The surface tension of the glass increases during the melting process, the bubbles are not easy to discharge, and the quality of the bubbles is difficult to meet the design requirements. Therefore, the content of ZnO is 2 to 10%, preferably 3 to 9%, more preferably 4 to 8%.
  • the present inventor has found through a large number of experimental studies that, in some embodiments, ZnO in the glass will change the network structure mainly based on SiO 2 , thus causing its relative content to be related to the probability of microcracks on the glass surface, and the microcracks of the glass It will be produced in the stage of hot working or cold working, which can greatly reduce the thermal shock resistance of glass.
  • the existence of microcracks will greatly reduce the ability of glass to resist acid, water and weather erosion. Taking the lens of a car lamp as an example, water vapor will start to erode the glass at the micro-crack defects, and defects will be formed on the glass surface.
  • the ZnO/SiO 2 value is preferably 0.03 to 0.17, the ZnO/SiO 2 value is more preferably 0.04 to 0.15, and the ZnO/SiO 2 value is still more preferably 0.06 to 0.12.
  • BaO, SrO, CaO, and MgO belong to alkaline earth metal oxides.
  • An appropriate amount of alkaline earth metal oxides in the glass can increase the refractive index of the glass and enhance the stability of the glass. If the total content of RO exceeds 15%, the alkaline earth metal oxides are easy to It precipitates under the conditions of water vapor and temperature changes, and forms opaque salts on the glass surface, destroying the imaging effect.
  • more than 15% of the alkaline earth metal oxides in the glass will greatly reduce the acid resistance of the glass, resulting in rapid corrosion spots on the surface of the lamp lens under the corrosion of acid rain, acidic deicing agent, etc. Therefore, the total content RO of BaO, SrO, CaO, and MgO is 15% or less, preferably 12% or less, more preferably 10% or less.
  • TiO 2 can improve the refractive index, water resistance and weather resistance of the glass, but if its content exceeds 5%, the transmittance of the glass, especially the transmittance in the near-ultraviolet-violet band, will drop rapidly. On the one hand, it will make the lens of the car light Decreased illuminance will affect driving safety. On the other hand, the temperature of the lamp lens will rise rapidly during use, the erosion of the lens surface will accelerate, the generation and expansion of micro-cracks will be faster, and the fogging of the lens will be accelerated. Therefore, the content of TiO 2 is 0-5%, preferably 0.05-4%, more preferably 0.2-3%.
  • ZnO and TiO 2 in the glass will lead to changes in the structure of B 2 O 3 , thereby greatly changing the high-temperature viscosity, transition temperature, and water resistance of the glass.
  • the value of (ZnO+TiO 2 )/B 2 O 3 is less than 0.2, the water resistance of the glass decreases rapidly, the transition temperature of the glass increases, but the high temperature viscosity of the glass does not decrease significantly.
  • the value of (ZnO+TiO 2 )/B 2 O 3 is greater than 2.0, the high-temperature viscosity of the glass increases rapidly, but the water resistance of the glass does not improve significantly.
  • the UV and 400nm transmittance of the glass decrease significantly.
  • (ZnO+TiO 2 )/B 2 O 3 is between 0.2 and 2.0, more preferably (ZnO+TiO 2 )/B 2 O 3 is between 0.3 and 1.5, even more preferably (ZnO+TiO 2 )/
  • the B 2 O 3 is between 0.35 and 1.0, the high-temperature viscosity, transition temperature and water resistance of the glass are most balanced.
  • the content of ZrO 2 in the glass can reduce the ability of the molten glass to corrode the furnace body and improve the service life of the melting furnace. If the content of ZrO 2 exceeds 3%, insoluble matter is likely to appear in the glass, resulting in a decrease in the intrinsic quality of the glass. Therefore, the content of ZrO2 is 3% or less, preferably 2% or less, more preferably 1% or less.
  • La 2 O 3 can increase the refractive index of the glass and reduce the high-temperature viscosity of the glass. If its content exceeds 5%, the acid resistance of the glass will decrease rapidly and the cost will increase. Therefore, the content of La 2 O 3 is limited to 5% or less, preferably 3% or less, and more preferably does not contain La 2 O 3 .
  • Y 2 O 3 in glass can improve the refractive index and thermal shock resistance of glass, and if its content exceeds 8%, the chemical stability of glass will drop rapidly. Therefore, the content of Y 2 O 3 is limited to 8% or less, preferably 5% or less, more preferably 3% or less.
  • Alkali metal oxides Li 2 O, Na 2 O, and K 2 O can lower the transition temperature of the glass and improve the melting performance of the glass.
  • the content of Rn 2 O is 6-25%, preferably 7-20%, more preferably 8-18%.
  • Li 2 O has the strongest ability to reduce the glass transition temperature and high temperature viscosity. If its content is less than 0.1%, the above effect is not obvious; if its content exceeds 5%, the glass tends to tend to Due to devitrification, the cost of raw materials rises rapidly. What is more serious is that the glass melts faster, and it is difficult to use efficient cold-top furnaces for production, and the production costs and energy consumption rise rapidly. Therefore, the content of Li 2 O is 0.1-5%, preferably 0.2-3%, more preferably 0.5-2%.
  • An appropriate amount of Na 2 O can improve the melting performance of the glass and reduce the high-temperature viscosity of the glass. If its content is less than 5%, the melting performance and high-temperature viscosity of the glass will hardly meet the design requirements, and the water resistance and weather resistance of the glass will decline rapidly; When the content of Na 2 O is higher than 15%, the thermal expansion coefficient of the glass increases rapidly, and the water resistance and weather resistance of the glass decrease rapidly, making it difficult to meet the design requirements. Therefore, the content of Na 2 O is limited to 5 to 15%, preferably 6 to 14%, more preferably 7 to 13%.
  • the content of K 2 O is higher than 8%, the glass network structure will be severely damaged, and the water resistance and weather resistance of the glass will hardly meet the design requirements. Therefore, the content of K 2 O is limited to 8% or less, preferably 7% or less, more preferably 5% or less.
  • the inventors of the present invention have found that when Li 2 O, Na 2 O, and K 2 O are present in a mixture, the structure of the glass undergoes complex changes compared with those present alone, which leads to a decrease in the water resistance, weather resistance, and water resistance of the glass. Complex changes in thermal shock resistance and high temperature viscosity. Specifically, when the K 2 O/(Na 2 O+Li 2 O) value is greater than 0.8, the chemical stability and weather resistance of the glass decrease rapidly, and the thermal expansion coefficient increases rapidly.
  • the K 2 O/(Na 2 O+Li 2 O) value is preferably 0.8 or less, the K 2 O/(Na 2 O+Li 2 O) value is more preferably 0.05 to 0.5, and the K 2 O/(Na 2 O+Li 2 O) value is more preferably 0.05 to 0.5.
  • the value of (Na 2 O+Li 2 O) is 0.1 to 0.3.
  • the value of Li 2 O/Na 2 O is preferably 0.01 to 0.3, more preferably 0.02 to 0.25, and still more preferably 0.03 to 0.22.
  • K 2 O/Na 2 O when the ratio K 2 O/Na 2 O between the content of K 2 O and the content of Na 2 O exceeds 0.8, the glass structure's ability to limit K + is greatly reduced, and the weather resistance of the glass is reduced; If the value of K 2 O/Na 2 O is lower than 0.01, the "mixed alkali" effect of the glass becomes very weak, K + cannot effectively interfere with the precipitation of Na + , the weather resistance will also decrease, and the precipitation on the surface tends to be serious. Therefore, K 2 O/Na 2 O is preferably 0.01 to 0.8, more preferably 0.05 to 0.5, and even more preferably 0.1 to 0.4.
  • Sb 2 O 3 , SnO 2 , Na 2 SiF 6 , K 2 SiF 6 , etc. can be used as clarifiers, which are beneficial to increase the bubble degree of the glass.
  • they exist alone or in combination they are less than 1%, preferably less than 0.8%, and more Preferably it is 0.5% or less.
  • the inventors have found that when nitrate is introduced in the form of KNO 3 and Ba(NO 3 ) 2, etc., and mixed with the above clarifying agent, the bubble degree of the glass can meet the quality requirements, and the emission of nitrogen oxides can be reduced. to a lower level.
  • the N (nitrogen) element content in the glass raw material is lower than 2.0%, preferably lower than 1.5%, more preferably lower than 1.0% .
  • glass compositions that require transmittance at wavelengths in the visible region are preferably substantially free of it.
  • Oxides of Th, Cd, Tl, Os, Be, and Se have tended to be controlled and used as harmful chemical substances in recent years, not only in the manufacturing process of glass, but also in the process of processing and disposal after production. Measures are required. Therefore, when emphasis is placed on the influence on the environment, it is preferable not to contain them substantially except for unavoidable mixing. Thereby, the glass composition becomes practically free of environmentally polluting substances. Therefore, the glass composition of the present invention can be manufactured, processed, and discarded without taking special environmental measures. Meanwhile, in order to achieve environmental friendliness, the glass composition of the present invention preferably does not contain As 2 O 3 and PbO.
  • does not contain and "0%” described herein mean that the compound, molecule or element etc. are not intentionally added to the glass composition of the present invention as a raw material; but as a raw material and/or equipment for producing the glass composition, there will be Certain impurities or components that are not intentionally added may be contained in a small or trace amount in the final glass composition, and this situation is also within the protection scope of the patent of the present invention.
  • the refractive index (n d ) and Abbe number ( ⁇ d ) of the glass are tested according to the method stipulated in "GB/T 7962.1-2010".
  • the upper limit of the refractive index ( nd ) of the glass composition of the present invention is 1.56, preferably 1.55, more preferably 1.54.
  • the lower limit of the refractive index ( nd ) of the glass composition of the present invention is 1.50, preferably 1.505, more preferably 1.51.
  • the upper limit of the Abbe number ( ⁇ d ) of the glass composition of the present invention is 65, preferably 63, and more preferably 62.
  • the lower limit of the Abbe number ( ⁇ d ) of the glass composition of the present invention is 56, preferably 57, and more preferably 57.5.
  • the acid resistance stability ( DA ) (powder method) of glass is tested according to the method specified in "GB/T 17129".
  • the acid resistance stability ( DA ) of the glass composition of the present invention is Class 2 or higher, preferably Class 1.
  • the water resistance stability (D W ) of the glass composition of the present invention is Class 2 or higher, preferably Class 1.
  • the thermal expansion coefficient of the glass ( ⁇ 20/300°C ) is tested according to the method specified in "GB/T7962.16-2010" for data at 20-300°C.
  • the thermal expansion coefficient ( ⁇ 20/300°C ) of the glass composition of the present invention is not more than 85 ⁇ 10 -7 /K, preferably not more than 82 ⁇ 10 -7 /K, more preferably not more than 80 ⁇ 10 - 7 /K or less.
  • the density ( ⁇ ) of the glass is tested according to the method specified in "GB/T7962.20-2010".
  • the density ( ⁇ ) of the glass composition of the present invention is 2.70 g/cm 3 or less, preferably 2.65 g/cm 3 or less, more preferably 2.60 g/cm 3 or less.
  • the transition temperature (T g ) of the glass is tested according to the method specified in "GB/T7962.16-2010".
  • the transition temperature (T g ) of the glass composition of the present invention is below 580°C, preferably below 570°C, more preferably below 560°C.
  • the light transmittance ( ⁇ 400nm ) of the glass is tested according to the method stipulated in "GB/T 7962.12-2010".
  • the light transmittance ( ⁇ 400nm ) of the glass composition of the present invention is 98.0% or higher, preferably 98.5% or higher, more preferably 99.0% or higher, and even more preferably 99.2% or higher.
  • the bubble degree of the glass is tested according to the method specified in "GB/T7962.8-2010".
  • the glass composition of the present invention has a bubble degree of A grade or higher, preferably A 0 grade or higher, more preferably A 00 grade.
  • the weather resistance of glass is tested by the following method.
  • the turbidity increases by less than 2.0%, preferably by less than 1.0%, more preferably by less than 0.8%, and even more preferably by less than 0.5%.
  • the stripe degree of the glass is compared with the standard sample from the direction where the stripes are most easily seen with a stripe meter composed of a point light source and a lens. It is divided into 4 grades, see Table 1 below for details.
  • the streakiness of the glass composition of the present invention is grade C or higher, preferably grade B or higher.
  • the high-temperature viscosity of glass at 1400°C is tested by the following method: use the THETA Rheotronic II high-temperature viscometer to test it by the rotation method, and the unit of value is dPaS (poise). The smaller the value, the smaller the viscosity.
  • the high temperature viscosity at 1400° C. of the glass composition of the present invention is 220 dPaS or less, preferably 180 dPaS or less, more preferably 150 dPaS or less.
  • glass of the present invention adopts conventional raw material and process production, includes but not limited to using oxide, hydroxide, fluoride, various salts (carbonate, nitrate, sulfate , phosphate, metaphosphate) as raw materials, after batching according to conventional methods, put the prepared charge into a smelting furnace (such as platinum, gold or platinum alloy crucible) at 1400-1550 ° C for melting, and after clarification and After homogenization, a homogeneous molten glass without air bubbles and undissolved substances is obtained, which is cast in a mold and annealed.
  • a smelting furnace such as platinum, gold or platinum alloy crucible
  • a glass preform can be produced from the produced glass composition using compression molding such as direct drop molding, grinding processing, or thermocompression molding. That is, a glass precision preform can be formed by direct precision drop molding of a molten glass composition, or a glass preform can be produced by mechanical processing such as grinding and grinding, or a preform for compression molding can be produced from a glass composition. The preform is reheated and pressed and then ground to produce a glass preform. It should be noted that the means for preparing the glass preform are not limited to the above means.
  • the glass composition of the present invention is useful for various optical elements and optical designs. Among them, it is particularly preferable to form a preform from the glass composition of the present invention, and to use the preform for reheat press molding and precision stamping. Molding, etc., to produce optical elements such as lenses and prisms.
  • Both the glass preform and the optical element of the present invention are formed from the above-mentioned glass composition of the present invention.
  • the glass preform of the present invention has the excellent characteristics of the glass composition;
  • the optical element of the present invention has the excellent characteristics of the glass composition, and can provide various optical elements such as lenses and prisms with high optical value.
  • the lens examples include various lenses such as concave meniscus lenses, convex meniscus lenses, biconvex lenses, biconcave lenses, plano-convex lenses, and plano-concave lenses whose lens surfaces are spherical or aspherical.
  • the lens of the present invention also includes a vehicle lamp lens.
  • Optical components formed from the glass composition of the present invention can be used to make optical instruments, and the optical glass includes but is not limited to photographic equipment, camera equipment, projection equipment, display equipment, vehicle equipment (including car lights), monitoring equipment, and the like.
  • glass compositions having the compositions shown in Tables 2 to 3 were obtained by using the method for producing the above-mentioned glass composition.
  • the properties of each glass were measured by the test method described in the present invention, and the measurement results are shown in Tables 2 to 3.
  • the glass obtained in Examples 1 to 17 of the glass composition is used, for example, by means of grinding processing, or means of compression molding such as reheating molding, precision stamping molding, etc., to produce concave meniscus lenses, convex meniscus lenses, double-lens lenses, etc. Prefabricated parts of various lenses, prisms, etc.
  • These preforms obtained in the above glass preform embodiment are annealed, and fine-tuning is performed while reducing the deformation inside the glass, so that the optical properties such as the refractive index reach the required values.
  • each preform is ground and polished to produce various lenses and prisms such as concave meniscus lens, convex meniscus lens, biconvex lens, biconcave lens, plano-convex lens, and plano-concave lens.
  • An antireflection film may be coated on the surface of the obtained optical element.
  • optical element prepared by the above optical element embodiment can be used for example in imaging equipment, sensor, microscope, medical technology, digital projection, communication, optical communication by using one or more optical elements to form optical components or optical components through optical design.

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Abstract

本发明提供一种玻璃组合物，其组分以重量百分比表示，含有：SiO2：52～72％；B2O3：3～17％；Al2O3：0.5～8％；ZnO：2～10％；Rn2O：6～25％，其中Al2O3/B2O3为0.1～1.0，所述Rn2O为Li2O、Na2O、K2O的合计含量。通过合理的组分设计，本发明获得的玻璃组合物具有优异的化学稳定性和耐候性，能够用于制造车灯透镜。

Description

玻璃组合物 技术领域
本发明涉及一种玻璃组合物，尤其是涉及一种化学稳定性和耐候性优异的玻璃组合物。
背景技术
车灯透镜能够将光源发出的光线进行整形，提升汽车前方150～400米范围内的照度，提高汽车行驶过程的安全性，因此越来越多的汽车车灯选择安装车灯透镜。现有技术中的车灯透镜采用钠钙硅玻璃制造，随着汽车车灯对使用寿命要求的大幅提升，以及未来车灯向智慧车灯发展，钠钙硅玻璃越来越不适应车灯透镜的发展需求。钠钙硅玻璃可以获得成像级产品，但化学稳定性差，尤其是耐水性与耐候性不佳，在高温高湿的条件下透镜表面容易在较短时间内产生腐蚀白斑，不仅降低汽车车灯照度损害安全性，同时也不能满足未来汽车大灯需要成像的要求。
发明内容
本发明所要解决的技术问题是提供一种化学稳定性和耐候性优异的玻璃组合物。
本发明解决技术问题采用的技术方案是：
(1)玻璃组合物，其组分以重量百分比表示，含有：SiO 2：52～72％；B 2O 3：3～17％；Al 2O 3：0.5～8％；ZnO：2～10％；Rn 2O：6～25％，其中Al 2O 3/B 2O 3为0.1～1.0，所述Rn 2O为Li 2O、Na 2O、K 2O的合计含量。
(2)根据(1)所述的玻璃组合物，其组分以重量百分比表示，还含有：RO：0～15％；和/或TiO 2：0～5％；和/或P 2O 5：0～2％；和/或ZrO 2：0～3％；和/或La 2O 3：0～5％；和/或Y 2O 3：0～8％；和/或澄清剂：0～1％，所述RO为MgO、CaO、SrO、BaO的合计含量，澄清剂为Sb 2O 3、SnO 2、Na 2SiF 6、K 2SiF 6中的一种或多种。
(3)玻璃组合物，含有SiO 2、B 2O 3、Al 2O 3、ZnO和碱金属氧化物，其 组分以重量百分比表示，其中Al 2O 3/B 2O 3为0.1～1.0，所述玻璃组合物的耐水作用稳定性D W为2类以上，折射率n d为1.50～1.56，阿贝数ν d为56～65。
(4)根据(3)所述的玻璃组合物，其组分以重量百分比表示，含有：SiO 2：52～72％；和/或B 2O 3：3～17％；和/或Al 2O 3：0.5～8％；和/或ZnO：2～10％；和/或TiO 2：0～5％；和/或Rn 2O：6～25％；和/或RO：0～15％；和/或P 2O 5：0～2％；和/或ZrO 2：0～3％；和/或La 2O 3：0～5％；和/或Y 2O 3：0～8％；和/或澄清剂：0～1％，所述RO为MgO、CaO、SrO、BaO的合计含量，Rn 2O为Li 2O、Na 2O、K 2O的合计含量，澄清剂为Sb 2O 3、SnO 2、Na 2SiF 6、K 2SiF 6中的一种或多种。
(5)根据(1)～(4)任一所述的玻璃组合物，其组分以重量百分比表示，其中：Al 2O 3/SiO 2为0.01～0.1，优选Al 2O 3/SiO 2为0.02～0.08，更优选Al 2O 3/SiO 2为0.03～0.07；和/或Al 2O 3/B 2O 3为0.15～0.8，优选Al 2O 3/B 2O 3为0.15～0.6；和/或ZnO/SiO 2为0.03～0.17，优选ZnO/SiO 2为0.04～0.15，更优选ZnO/SiO 2为0.06～0.12；和/或(ZnO+TiO 2)/B 2O 3为0.2～2.0，优选(ZnO+TiO 2)/B 2O 3为0.3～1.5，更优选(ZnO+TiO 2)/B 2O 3为0.35～1.0。
(6)根据(1)～(5)任一所述的玻璃组合物，其组分以重量百分比表示，其中：SiO 2：55～70％，优选SiO 2：56～68％；和/或B 2O 3：5～15％，优选B 2O 3：7～13％；和/或Al 2O 3：1～6％，优选Al 2O 3：1～5％；和/或ZnO：3～9％，优选ZnO：4～8％；和/或TiO 2：0.05～4％，优选TiO 2：0.2～3％；和/或Rn 2O：7～20％，优选Rn 2O：8～18％；和/或RO：0～12％，优选RO：0～10％；和/或P 2O 5：0～1％；和/或ZrO 2：0～2％，优选ZrO 2：0～1％；和/或La 2O 3：0～3％；和/或Y 2O 3：0～5％，优选Y 2O 3：0～3％；和/或澄清剂：0～0.8％，优选澄清剂：0～0.5％，所述RO为MgO、CaO、SrO、BaO的合计含量，Rn 2O为Li 2O、Na 2O、K 2O的合计含量，澄清剂为Sb 2O 3、SnO 2、Na 2SiF 6、K 2SiF 6中的一种或多种。
(7)根据(1)～(6)任一所述的玻璃组合物，其组分以重量百分比 表示，其中：Li 2O：0.1～5％，优选Li 2O：0.2～3％，更优选Li 2O：0.5～2％；和/或Na 2O：5～15％，优选Na 2O：6～14％，更优选Na 2O：7～13％；和/或K 2O：0～8％，优选K 2O：0～7％，更优选K 2O：0～5％。
(8)根据(1)～(7)任一所述的玻璃组合物，其组分以重量百分比表示，其中：K 2O/(Na 2O+Li 2O)为0.8以下，优选K 2O/(Na 2O+Li 2O)为0.05～0.5，更优选K 2O/(Na 2O+Li 2O)为0.1～0.3；和/或Li 2O/Na 2O为0.01～0.3，优选Li 2O/Na 2O为0.02～0.25，更优选Li 2O/Na 2O为0.03～0.22；和/或K 2O/Na 2O为0.01～0.8，优选K 2O/Na 2O为0.05～0.5，更优选K 2O/Na 2O为0.1～0.4。
(9)根据(1)～(8)任一所述的玻璃组合物，其组分以重量百分比表示，其中：CaO：不超过10％；和/或BaO：不超过10％。
(10)根据(1)～(9)任一所述的玻璃组合物，其组分以重量百分比表示，其中：CaO：不超过5％；和/或BaO：不超过5％。
(11)根据(1)～(10)任一所述的玻璃组合物，玻璃原料中的N元素含量低于2.0％，优选低于1.5％，更优选低于1.0％，所述N元素含量为熔制100Kg理论玻璃的N元素的引入量/100Kg玻璃重量×100％。
(12)根据(1)～(11)任一所述的玻璃组合物的折射率n d为1.50～1.56，优选为1.505～1.55，更优选为1.51～1.54；阿贝数ν d为56～65，优选为57～63，更优选为57.5～62。
(13)根据(1)～(12)任一所述的玻璃组合物的耐酸作用稳定性D A为2类以上，优选为1类；和/或耐水作用稳定性D W为2类以上，优选为1类；和/或热膨胀系数α 20/300℃为85×10 -7/K以下，优选为82×10 -7/K以下，更优选为80×10 -7/K以下；和/或转变温度T g为580℃以下，优选为570℃以下，更优选为560℃以下；和/或密度ρ为2.70g/cm 3以下，优选为2.65g/cm 3以下,更优选为2.60g/cm 3以下；和/或光透过率τ 400nm为98.0％以上，优选为98.5％以上，更优选为99.0％以上，进一步优选为99.2％以上；和/或经200小时耐候性测试后，浊度增加2.0％以下，优选增加1.0％以下， 更优选增加0.8％以下，进一步优选增加0.5％以下；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/或条纹度为C级以上，优选为B级以上；和/或1400℃的高温粘度为220dPaS以下，优选为180dPaS以下，更优选为150dPaS以下。
(14)玻璃预制件，采用(1)～(13)任一所述的玻璃组合物制成。
(15)光学元件，采用(1)～(13)任一所述的玻璃组合物或(14)所述的玻璃预制件制成。
(16)光学仪器，含有(1)～(13)任一所述的玻璃组合物，和/或含有(15)所述的光学元件。
本发明的有益效果是：通过合理的组分设计，本发明获得的玻璃组合物具有优异的化学稳定性和耐候性，能够用于制造车灯透镜。
具体实施方式
下面，对本发明的玻璃组合物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，本发明玻璃组合物有时候简称为玻璃。
[玻璃组合物]
下面对本发明玻璃组合物的各组分(成分)范围进行说明。在本发明中，如果没有特殊说明，各组分的含量、总含量全部采用重量百分比(wt％)表示，即，各组分的含量、总含量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，作为本发明的玻璃组合物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是玻璃的主要组分，若其含量超过72％，玻璃熔化困难，气泡、夹杂物和条纹无法排除，很难获得成像级质量产品。另外玻璃的折射率会低于设计要求，玻璃的折射率过低，意味着光束在相同扩散角的要求下，车灯透镜需要更大的曲率，更大的曲率要求热压型难度更高，光学误差更大，以及热压成型中更容易出现缺陷，加速透镜表面的腐蚀斑点产生。若SiO 2的含量低于52％，玻璃的化学稳定性(尤其是耐水性)和耐候性难以达到设计要求；另一方面，玻璃的阿贝数会低于设计要求，由于一般车灯属于单镜片光学系统，若玻璃的阿贝数过低，色散过大，光束通过玻璃透镜后在照明边缘会发生严重的紫边现象，严重影响照明品质。因此，SiO 2的含量为52～72％，优选为55～70％，更优选为56～68％。
合适量的B 2O 3能够降低玻璃的熔化温度与高温粘度，对于硼硅酸盐玻璃，高温粘度越低，玻璃的气泡、夹杂物和条纹等越容易消除。更重要的是，合适量的B 2O 3会进一步紧固玻璃网络，使玻璃的耐候性提高，若其含量低于3％，上述效果不明显。若B 2O 3的含量高于17％，玻璃的耐水性快速降低。因此，其含量限定为3～17％，优选为5～15％，更优选为7～13％。
合适量的Al 2O 3能够加固玻璃网络，提升玻璃的化学稳定性，降低玻璃的热膨胀系数，若其含量低于0.5％，上述效果不明显；若Al 2O 3的含量超过8％，玻璃的高温粘度快速上升，难以达到设计要求。因此，Al 2O 3的含量范围为0.5～8％，优选1～6％，更优选1～5％。
在一些实施方式中，Al 2O 3与SiO 2的相对含量对于玻璃耐候性有显著的影响，当Al 2O 3/SiO 2的值小于0.01时，玻璃的耐候性降低，难以达到设计要求；当Al 2O 3/SiO 2的值大于0.1时，玻璃的耐候性不再明显提高，但高温粘度快速上升。因此，优选Al 2O 3/SiO 2的值为0.01～0.1，更优选Al 2O 3/SiO 2的值为0.02～0.08，进一步优选Al 2O 3/SiO 2的值为0.03～0.07。
在一些实施方式中，Al 2O 3与B 2O 3的相对含量对玻璃的耐水性有显著的影响，当Al 2O 3/B 2O 3的值小于0.1时，玻璃的耐水性降低，难以达到设计要求；当Al 2O 3/B 2O 3的值大于1.0时，玻璃的耐水性不再明显提高，但高温粘度快速上升。因此，Al 2O 3/B 2O 3的值优选为0.1～1.0，更优选为0.15～0.8，进一步优选为0.15～0.6。
少量的P 2O 5在玻璃中可以显著提升玻璃的化学强化性能，同时P 2O 5在玻璃中能够促进玻璃微晶的形成，提升玻璃的抗热冲击强度。若P 2O 5的含量高于2％，玻璃变得不稳定甚至是失透。因此，P 2O 5的含量控制在2％以下，优选为1％以下，若玻璃的化学强化性能与抗热冲击性能足够，更优选不含有P 2O 5。
合适量的ZnO能够显著提升玻璃的折射率，降低玻璃的热膨胀系数和转变温度，若其含量低于2％，上述效果不明显；若ZnO的含量高于10％，玻璃的阿贝数降低，玻璃在熔化过程中的表面张力增大，气泡不易排出，气泡质量难以达到设计要求。因此，ZnO的含量为2～10％，优选为3～9％，更优选为4～8％。
本发明人大量实验研究发现，在一些实施方式中，ZnO在玻璃中会使以SiO 2为主体的网络结构产生变化，从而导致其相对含量与玻璃表面产生微裂纹的概率有关，玻璃的微裂纹会在热加工或冷加工的阶段产生，能够大幅度降低玻璃的抗热冲击强度。同时，微裂纹的存在还会使玻璃耐酸、耐水和耐气候侵蚀的能力大幅度下降。以车灯透镜为例，水汽会在微裂纹缺陷处开始侵蚀玻璃，在玻璃表面产生缺陷，同时在高低温加水汽的腐蚀下，微裂纹会扩张、风化，玻璃器件表面的缺陷快速增长。若ZnO的含量与SiO 2的含量之间的比值ZnO/SiO 2低于0.03，抑制微裂纹产生的效果不明显；若ZnO/SiO 2的值高于0.17，玻璃液表面张力增加，化料过程中产生大量气泡堆积，降低折射率和阿贝数的一致性，严重时会导致生产停止，造成大量损失。因此，优选ZnO/SiO 2的值为0.03～0.17，更优选ZnO/SiO 2的值为0.04～0.15，进一步优选ZnO/SiO 2的值为0.06～0.12。
BaO、SrO、CaO、MgO属于碱土金属氧化物，合适量的碱土金属氧化物在玻璃中可以提升玻璃的折射率，增强玻璃的稳定性，若其合计含量RO超过15％，碱土金属氧化物容易在水汽以及温度变化条件下析出，在玻璃表面形成不透明的盐类，破坏成像效果。另外，超过15％的碱土金属氧化物在玻璃中会大幅度降低玻璃的耐酸性，导致车灯透镜在酸雨、酸性融雪剂等的腐蚀下表面快速产生腐蚀斑点。因此，BaO、SrO、CaO、MgO的合计含量RO为15％以下，优选为12％以下，更优选为10％以下。
经过发明人大量实验研究发现，从析出能力来看，BaO大于SrO大于CaO大于MgO,因此从析出物控制的角度，优选使用MgO和CaO，其次使用SrO，再次使用BaO。进一步的，少量的CaO与BaO，尤其是BaO能够显著改善玻璃的气泡度，因此从气泡度提升的角度考虑，玻璃中可以含有少量的CaO或BaO。综上所述，若玻璃设计趋向于高温粘度进一步减小，折射率进一步上升，可以考虑含有不超过10％的CaO和/或不超过10％的BaO。若玻璃设计趋向于析出物控制，可以考虑含有不超过5％的CaO和/或不超过5％的BaO。
TiO 2可以提升玻璃的折射率、耐水性和耐候性，但若其含量超过5％，玻璃的透过率，尤其是近紫外-紫色波段透过率快速下降，一方面会使车灯透镜的照度下降，影响行驶安全，另一方面会导致车灯透镜在使用过程中温度快速上升，透镜表面的侵蚀加快，微裂纹产生与扩张更快，透镜起雾加速。因此，TiO 2的含量为0～5％，优选为0.05～4％，更优选为为0.2～3％。
在一些实施方式中，ZnO和TiO 2在玻璃中会导致B 2O 3的结构发生变化，从而使玻璃的高温粘度、转变温度以及耐水性发生较大的变化。当(ZnO+TiO 2)/B 2O 3的值小于0.2时，玻璃的耐水性快速下降，玻璃的转变温度升高，而玻璃的高温粘度下降不明显。当(ZnO+TiO 2)/B 2O 3的值大于2.0时，玻璃的高温粘度快速上升，而玻璃的耐水性提升不明显，另外玻璃紫外以及400nm透过率大幅度下降，应用到车灯中会导致发热急剧上升，从而加剧玻璃表面缺陷的产生。因此，优选(ZnO+TiO 2)/B 2O 3为0.2～2.0 之间，更优选(ZnO+TiO 2)/B 2O 3为0.3～1.5之间，进一步优选(ZnO+TiO 2)/B 2O 3为0.35～1.0之间时，玻璃的高温粘度、转变温度以及耐水性最为平衡。
低于3％的ZrO 2在玻璃中可以降低玻璃液侵蚀炉体的能力，提升熔炼炉寿命。若ZrO 2的含量超过3％，玻璃中容易出现不溶物，导致玻璃内在品质降低。因此，ZrO 2的含量为3％以下，优选为2％以下，更优选为1％以下。
La 2O 3可以提高玻璃的折射率，降低玻璃的高温粘度，若其含量超过5％，玻璃耐酸性快速下降，成本升高。因此，La 2O 3的含量限定为5％以下，优选为3％以下，进一步优选为不含有La 2O 3。
Y 2O 3在玻璃中可以提高玻璃的折射率和抗热冲击性能，若其含量超过8％，玻璃的化学稳定性快速下降。因此，Y 2O 3的含量限定在8％以下，优选为5％以下，更优选为3％以下。
碱金属氧化物Li 2O、Na 2O、K 2O可以降低玻璃的转变温度，改善玻璃的熔化性能，当其合计含量Rn 2O超过25％时，玻璃的化学稳定性降低。因此，Rn 2O的含量为6～25％，优选为7～20％，更优选为8～18％。
从单种碱金属氧化物的作用来看，Li 2O降低玻璃转变温度和高温粘度的能力最强，若其含量低于0.1％，上述效果不明显；若其含量超过5％，玻璃容易趋于失透，原料成本快速上升，更为严重的是，玻璃熔解变快，不易采用高效的冷顶炉方式生产，生产成本与能源消耗快速上升。因此，Li 2O的含量为0.1～5％，优选为0.2～3％，更优选为0.5～2％。
合适量的Na 2O可以改善玻璃的熔化性能，降低玻璃的高温粘度，若其含量低于5％，玻璃的熔化性能和高温粘度难以达到设计要求，玻璃的耐水性与耐候性快速下降；若Na 2O的含量高于15％，玻璃的热膨胀系数快速上升，玻璃的耐水性和耐候性能快速下降，难以达到设计要求。因此，Na 2O的含量限定为5～15％，优选为6～14％，更优选为7～13％。
K 2O的含量若高于8％，玻璃网络结构破坏严重，玻璃耐水性和耐候性难以达到设计要求。因此，K 2O的含量限定为8％以下，优选为7％以下，更 优选为5％以下。
本发明人研究发现，Li 2O、Na 2O、K 2O三种碱金属氧化物混合存在时，与单一存在相比，玻璃的结构出现复杂变化从而导致玻璃的耐水性、耐候性、耐热冲击性与高温粘度出现复杂变化。具体而言，当K 2O/(Na 2O+Li 2O)值大于0.8时，玻璃的化学稳定性和耐候性快速下降，热膨胀系数快速上升。因此，K 2O/(Na 2O+Li 2O)的值优选为0.8以下，更优选K 2O/(Na 2O+Li 2O)的值为0.05～0.5，进一步优选K 2O/(Na 2O+Li 2O)的值为0.1～0.3。
在一些实施方式中，当Li 2O的含量与Na 2O的含量之间的比值Li 2O/Na 2O低于0.01时，玻璃的高温粘度上升，玻璃耐热冲击性能下降；当Li 2O/Na 2O的值高于0.3时，玻璃在生产过程中从液态冷却到固态的时间变长，造成条纹度下降，同时需要成型车灯透镜压型的毛坯体的公差控制变得非常困难，导致材料的利用率下降，良品率降低。因此，Li 2O/Na 2O的值优选为0.01～0.3，更优选为0.02～0.25，进一步优选为0.03～0.22。
在一些实施方式中，K 2O的含量与Na 2O的含量之间的比值K 2O/Na 2O超过0.8以后，玻璃结构对K +的限制能力大幅度下降，玻璃的耐候性下降；若K 2O/Na 2O的值低于0.01，玻璃“混合碱”效应变得非常微弱，K +不能有效的对Na +的析出形成有效的干扰，耐候性也会下降，表面析出趋于严重。因此，K 2O/Na 2O优选为0.01～0.8，更优选为0.05～0.5，进一步优选为0.1～0.4。
Sb 2O 3、SnO 2、Na 2SiF 6、K 2SiF 6等可用于作为澄清剂，有利于提高玻璃的气泡度，其单独或组合存在时为1％以下，优选为0.8％以下，更优选为0.5％以下。
除了组分设计优化玻璃的熔化性能，提升玻璃气泡度以外，类似高粘度的硅酸盐玻璃还通常采用氧化物组分采用硝酸盐引入的方式来优化玻璃的熔化性能与气泡度。硝酸盐在熔化过程中氮元素几乎全部以NO X气体排放到大气中，氮氧化物对人体健康有极大的损害，长期吸入有导致肺癌的风险。因此，本发明人致力于研究在保证玻璃熔化性能的同时，降低氮氧化 物排放问题。本发明人研究发现，硝酸盐以KNO 3和Ba(NO 3) 2等方式引入，并与上述澄清剂混合使用时，玻璃的气泡度能满足质量要求的同时，氮氧化物的排放量可降低至较低水平。通过折算，玻璃原料中的N(氮)元素含量(熔制100Kg理论玻璃的N元素的引入量/100Kg玻璃重量×100％)低于2.0％，优选低于1.5％，更优选低于1.0％。
<不应含有的组分>
本发明玻璃中，V、Cr、Mn、Fe、Co、Ni、Cu、Ag以及Mo等过渡金属的氧化物，即使单独或复合地少量含有的情况下，玻璃也会被着色，在可见光区域的特定的波长产生吸收，从而减弱本发明的提高可见光透过率效果的性质，因此，特别是对于可见光区域波长的透过率有要求的玻璃组合物，优选实际上不含有。
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，玻璃组合物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，本发明的玻璃组合物也能够进行制造、加工以及废弃。同时，为了实现环境友好，本发明的玻璃组合物优选不含有As 2O 3和PbO。
本文所记载的“不含有”“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组合物中；但作为生产玻璃组合物的原材料和/或设备，会存在某些不是故意添加的杂质或组分，会在最终的玻璃组合物中少量或痕量含有，此种情形也在本发明专利的保护范围内。
下面将描述本发明的玻璃组合物的性能：
<折射率与阿贝数>
玻璃的折射率(n d)与阿贝数(ν d)按照《GB/T 7962.1—2010》规定的方法测试。
在一些实施方式中，本发明玻璃组合物的折射率(n d)的上限为1.56， 优选上限为1.55，更优选上限为1.54。
在一些实施方式中，本发明玻璃组合物的折射率(n d)的下限为1.50，优选下限为1.505，更优选下限为1.51。
在一些实施方式中，本发明玻璃组合物的阿贝数(ν d)的上限为65，优选上限为63，更优选上限为62。
在一些实施方式中，本发明玻璃组合物的阿贝数(ν d)的下限为56，优选下限为57，更优选下限为57.5。
<耐酸作用稳定性>
玻璃的耐酸作用稳定性(D A)(粉末法)按照《GB/T 17129》规定的方法测试。
在一些实施方式中，本发明玻璃组合物的耐酸作用稳定性(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。
在一些实施方式中，本发明玻璃组合物的耐水作用稳定性(D W)为2类以上，优选为1类。
<热膨胀系数>
玻璃的热膨胀系数(α 20/300℃)按照《GB/T7962.16-2010》规定的方法进行测试20～300℃的数据。
在一些实施方式中，本发明的玻璃组合物的热膨胀系数(α 20/300℃)为85×10 -7/K以下，优选为82×10 -7/K以下，更优选为80×10 -7/K以下。
<密度>
玻璃的密度(ρ)按《GB/T7962.20-2010》规定的方法进行测试。
在一些实施方式中，本发明玻璃组合物的密度(ρ)为2.70g/cm 3以下，优选为2.65g/cm 3以下,更优选为2.60g/cm 3以下。
<转变温度>
玻璃的转变温度(T g)按照《GB/T7962.16-2010》规定的方法进行测试。
在一些实施方式中，本发明玻璃组合物的转变温度(T g)为580℃以下，优选为570℃以下，更优选为560℃以下。
<光透过率>
玻璃的光透过率(τ 400nm)按《GB/T 7962.12-2010》规定的方法进行测试。
在一些实施方式中，本发明玻璃组合物的光透过率(τ 400nm)为98.0％以上，优选为98.5％以上，更优选为99.0％以上，进一步优选为99.2％以上。
<气泡度>
玻璃的气泡度按《GB/T7962.8-2010》规定的方法测试。
在一些实施方式中，本发明玻璃组合物的气泡度为A级以上，优选为A 0级以上，更优选为A 00级。
<耐候性>
玻璃的耐候性按以下方法进行测试。
将试样放置在相对湿度为90％的饱和水蒸气环境的测试箱内，在40～50℃每隔1小时交替循环，测试其浊度增加量。
在一些实施方式中，本发明玻璃组合物经200小时耐候性测试后，浊度增加2.0％以下，优选增加1.0％以下，更优选增加0.8％以下，进一步优选增加0.5％以下。
<条纹度>
玻璃的条纹度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，与标准试样作比较检查，分为4级，详见下表1。
表1.条纹度等级表
级别 条纹程度
A 在规定检测条件下无肉眼可见的条纹
B 在规定检测条件下有细而分散的条纹
C 在规定检测条件下有轻微的平行条纹
D 在规定检测条件下有粗略的平行条纹
在一些实施方式中，本发明玻璃组合物的条纹度为C级以上，优选为B级以上。
<高温粘度>
玻璃的1400℃的高温粘度按以下方法测试：使用THETA Rheotronic II高温粘度计采用旋转法测试，数值单位为dPaS(泊)，其数值越小，表示粘度越小。
在一些实施方式中，本发明玻璃组合物的1400℃的高温粘度为220dPaS以下，优选为180dPaS以下，更优选为150dPaS以下。
[制造方法]
本发明玻璃组合物的制造方法如下：本发明的玻璃采用常规原料和工艺生产，包括但不限于使用氧化物、氢氧化物、氟化物、各种盐类(碳酸盐、硝酸盐、硫酸盐、磷酸盐、偏磷酸盐)等为原料，按常规方法配料后，将配好的炉料投入到1400～1550℃的熔炼炉(如铂金、黄金或铂合金坩埚)中熔制，并且经澄清和均化后，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。
[玻璃预制件和光学元件]
可以使用例如直接滴料成型、或研磨加工的手段、或热压成型等模压成型的手段，由所制成的玻璃组合物来制作玻璃预制件。即，可以通过对熔融玻璃组合物进行直接精密滴料成型为玻璃精密预制件，或通过磨削和研磨等机械加工来制作玻璃预制件，或通过对由玻璃组合物制作模压成型用的预成型坯，对该预成型坯进行再热压成型后再进行研磨加工来制作玻璃预制件。需要说明的是，制备玻璃预制件的手段不限于上述手段。
如上所述，本发明的玻璃组合物对于各种光学元件和光学设计是有用的，其中特别优选由本发明的玻璃组合物形成预成型坯，使用该预成型坯来进行再热压成型、精密冲压成型等，制作透镜、棱镜等光学元件。
本发明的玻璃预制件与光学元件均由上述本发明的玻璃组合物形成。本发明的玻璃预制件具有玻璃组合物所具有的优异特性；本发明的光学元件具有玻璃组合物所具有的优异特性，能够提供光学价值高的各种透镜、棱镜等光学元件。
作为透镜的例子，可举出透镜面为球面或非球面的凹弯月形透镜、凸弯月形透镜、双凸透镜、双凹透镜、平凸透镜、平凹透镜等各种透镜。本发明所述透镜还包括车灯透镜。
[光学仪器]
本发明玻璃组合物所形成的光学元件可制作光学仪器，所述光学玻璃包括但不限于照相设备、摄像设备、投影设备、显示设备、车载设备(含车灯)和监控设备等。
实施例
<玻璃组合物实施例>
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。
本实施例采用上述玻璃组合物的制造方法得到具有表2～表3所示的组成的玻璃组合物。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2～表3中。
表2.
wt％ 1# 2# 3# 4# 5# 6# 7# 8# 9#
SiO 2 62.0 58.0 68.0 63.3 61.5 63.5 60.5 65.1 63.5
B 2O 3 6.0 6.0 5.0 15.4 15.7 12.7 13.2 10.2 10.0
P 2O 5 0.0 0.0 0.8 0.2 0.0 0.0 0.0 0.1 0.0
Al 2O 3 3.5 3.5 3.0 2.3 1.9 1.3 2.1 2.8 5.0
ZrO 2 0.2 0.1 0.1 0.1 0.1 0.2 0.1 0.1 0.3
TiO 2 1.0 1.0 0.5 1.7 0.2 1.5 1.5 1.5 1.6
Y 2O 3 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
La 2O 3 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
ZnO 8.0 9.0 6.0 5.1 5.1 8.1 7.0 5.8 6.0
BaO 2.0 1.0 1.0 0.0 1.0 0.2 0.5 1.0 0.7
CaO 10.0 9.0 5.2 0.0 2.5 0.4 1.1 0.8 0.5
SrO 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.2
MgO 0.0 1.0 0.0 0.0 0.0 0.0 0.0 0.0 0.5
Li 2O 0.2 0.2 0.2 0.1 0.2 0.2 0.2 0.9 0.7
Na 2O 6.0 9.0 9.0 7.5 7.5 8.6 10.5 9.5 9.4
K 2O 1.0 2.0 1.0 4.1 4.1 3.1 3.1 1.4 1.1
Na 2SiF 6 0.0 0.0 0.0 0.0 0.0 0.1 0.0 0.2 0.2
K 2SiF 6 0.0 0.0 0.0 0.0 0.0 0.0 0.1 0.1 0.0
SnO 2 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.2 0.2
Sb 2O 3 0.1 0.2 0.2 0.2 0.2 0.1 0.1 0.3 0.1
合计 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0
Al 2O 3/B 2O 3 0.58 0.58 0.60 0.15 0.12 0.10 0.16 0.27 0.50
Al 2O 3/SiO 2 0.06 0.06 0.04 0.04 0.03 0.02 0.03 0.04 0.08
ZnO/SiO 2 0.13 0.16 0.09 0.08 0.08 0.13 0.12 0.09 0.09
(ZnO+TiO 2)/B 2O 3 1.50 1.67 1.30 0.44 0.34 0.76 0.64 0.72 0.76
RO 12.0 11.0 6.2 0.0 3.5 0.6 1.6 1.8 1.9
Rn 2O 7.2 11.2 10.2 11.7 11.8 11.9 13.8 11.8 11.2
K 2O/Na 2O 0.17 0.22 0.11 0.55 0.55 0.36 0.30 0.15 0.12
Li 2O/Na 2O 0.03 0.02 0.02 0.01 0.03 0.02 0.02 0.09 0.07
K 2O/(Na 2O+Li 2O) 0.16 0.22 0.11 0.54 0.53 0.35 0.29 0.14 0.11
n d 1.54309 1.55156 1.52747 1.51681 1.51586 1.52423 1.52865 1.52721 1.52523
v d 57.90 57.16 59.20 59.50 62.38 59.57 58.80 58.21 58.34
τ 400nm(％) 99.3 99.4 99.5 99.1 99.3 99.3 99.3 99.3 99.3
耐候性(％) 0.85 0.92 0.60 1.20 1.40 0.85 1.60 0.45 0.35
D A 1类 1类 1类 1类 2类 1类 1类 1类 1类
D W 2类 1类 2类 2类 2类 2类 2类 1类 1类
T g(℃) 580 564 571 542 536 535 540 541 545
α 20/300℃(×10 -7/K) 68.0 83.0 72.0 81.0 82.0 75.0 72.0 73.0 70.0
ρ(g/cm 3) 2.65 2.70 2.57 2.45 2.47 2.53 2.56 2.52 2.54
1400℃高温粘度(dPaS) 118.2 46.1 213.0 180.0 145.3 135.7 88.9 152.0 198.0
气泡度 A 00 A 00 A 0 A 0 A 0 A 0 A 00 A 00 A 0
条纹度 A B C C C C B B C
原料中N元素含量 0.5％ 0.3％ 0.8％ 0.6％ 0.5％ 0.6％ 0.4％ 0.7％ 0.8％
表3.
wt％ 10# 11# 12# 13# 14# 15# 16# 17#
SiO 2 65.5 66.3 60.0 62.4 62.2 68.0 61.0 61.0
B 2O 3 10.4 9.5 15.2 10.0 12.3 9.9 10.4 10.2
P 2O 5 0.0 0.0 0.0 0.0 0.2 0.0 0.0 0.3
Al 2O 3 3.0 4.0 3.0 3.5 2.8 1.0 3.0 2.6
ZrO 2 0.1 0.1 0.1 0.1 0.1 0.2 0.1 0.2
TiO 2 1.7 1.9 1.7 1.7 1.5 2.0 0.1 0.1
Y 2O 3 0.0 0.0 0.0 2.0 0.5 0.0 0.0 0.0
La 2O 3 0.0 0.0 0.0 1.5 0.5 0.0 0.0 0.0
ZnO 5.6 6.1 5.6 5.6 5.6 5.5 5.6 6.0
BaO 1.0 0.0 1.0 1.0 0.5 0.5 1.0 3.0
CaO 0.0 0.0 0.7 0.0 0.4 0.0 6.3 4.0
SrO 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
MgO 0.0 0.0 0.0 0.0 0.1 0.0 0.0 0.0
Li 2O 0.8 0.8 0.8 0.8 0.6 0.5 0.8 0.9
Na 2O 9.7 10.6 9.7 9.2 10.2 11.4 9.7 9.0
K 2O 1.5 0.2 1.5 1.5 1.8 0.5 1.5 2.2
Na 2SiF 6 0.2 0.0 0.0 0.2 0.2 0.0 0.0 0.2
K 2SiF 6 0.0 0.0 0.2 0.0 0.0 0.0 0.0 0.0
SnO 2 0.0 0.2 0.0 0.0 0.2 0.3 0.2 0.1
Sb 2O 3 0.5 0.3 0.5 0.5 0.3 0.2 0.3 0.2
合计 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0
Al 2O 3/B 2O 3 0.29 0.42 0.20 0.35 0.23 0.10 0.29 0.25
Al 2O 3/SiO 2 0.05 0.06 0.05 0.06 0.05 0.01 0.05 0.04
ZnO/SiO 2 0.09 0.09 0.09 0.09 0.09 0.08 0.09 0.10
(ZnO+TiO 2)/B 2O 3 0.70 0.84 0.48 0.73 0.58 0.76 0.55 0.60
RO 1.0 0.0 1.7 1.0 1.0 0.5 7.3 7.0
Rn 2O 12.0 11.6 12.0 11.5 12.6 12.4 12.0 12.1
K 2O/Na 2O 0.15 0.02 0.15 0.16 0.18 0.04 0.15 0.24
Li 2O/Na 2O 0.08 0.08 0.08 0.09 0.06 0.04 0.08 0.10
K 2O/(Na 2O+Li 2O) 0.14 0.02 0.14 0.15 0.17 0.04 0.14 0.22
n d 1.52390 1.52213 1.53832 1.53721 1.52564 1.52466 1.53559 1.53371
v d 58.64 57.95 59.10 57.21 58.47 57.89 60.52 60.65
τ 400nm(％) 99.1 99.2 99.1 99.4 99.3 99.2 99.7 99.7
耐候性(％) 0.40 0.20 0.70 0.50 0.40 0.55 0.40 0.30
D A 1类 1类 1类 1类 1类 1类 1类 1类
D W 1类 1类 2类 1类 1类 2类 1类 1类
T g(℃) 536 536 531 553 542 552 543 541
α 20/300℃(×10 -7/K) 72.0 70.0 74.0 70.0 75.0 73.0 80.0 78.0
ρ(g/cm 3) 2.53 2.51 2.49 2.59 2.54 2.53 2.60 2.62
1400℃高温粘度(dPaS) 167.0 151.1 102.0 121.0 135.0 137.8 73.1 69.7
气泡度 A 00 A 00 A 00 A 00 A 00 A 00 A 00 A 00
条纹度 B B B B B B B B
原料中N元素含量 0.7％ 0.7％ 0.4％ 0.4％ 0.4％ 0.5％ 0.3％ 0.3％
<玻璃预制件实施例>
将玻璃组合物实施例1～17所得到的玻璃使用例如研磨加工的手段、或再热压成型、精密冲压成型等模压成型的手段，来制作凹弯月形透镜、凸弯月形透镜、双凸透镜、双凹透镜、平凸透镜、平凹透镜等各种透镜、棱镜等的预制件。
<光学元件实施例>
将上述玻璃预制件实施例所得到的这些预制件退火，在降低玻璃内部的变形的同时进行微调，使得折射率等光学特性达到所需值。
接着，对各预制件进行磨削、研磨，制作凹弯月形透镜、凸弯月形透镜、双凸透镜、双凹透镜、平凸透镜、平凹透镜等各种透镜、棱镜。所得到的光学元件的表面上还可涂布防反射膜。
<光学仪器实施例>
将上述光学元件实施例制得的光学元件通过光学设计，通过使用一个或多个光学元件形成光学部件或光学组件，可用于例如成像设备、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，或用于车载领域的摄像设备和装置。

Claims (16)

  1. 玻璃组合物，其特征在于，其组分以重量百分比表示，含有：SiO 2：52～72％；B 2O 3：3～17％；Al 2O 3：0.5～8％；ZnO：2～10％；Rn 2O：6～25％，其中Al 2O 3/B 2O 3为0.1～1.0，所述Rn 2O为Li 2O、Na 2O、K 2O的合计含量。
  2. 根据权利要求1所述的玻璃组合物，其特征在于，其组分以重量百分比表示，还含有：RO：0～15％；和/或TiO 2：0～5％；和/或P 2O 5：0～2％；和/或ZrO 2：0～3％；和/或La 2O 3：0～5％；和/或Y 2O 3：0～8％；和/或澄清剂：0～1％，所述RO为MgO、CaO、SrO、BaO的合计含量，澄清剂为Sb 2O 3、SnO 2、Na 2SiF 6、K 2SiF 6中的一种或多种。
  3. 玻璃组合物，其特征在于，含有SiO 2、B 2O 3、Al 2O 3、ZnO和碱金属氧化物，其组分以重量百分比表示，其中Al 2O 3/B 2O 3为0.1～1.0，所述玻璃组合物的耐水作用稳定性D W为2类以上，折射率n d为1.50～1.56，阿贝数ν d为56～65。
  4. 根据权利要求3所述的玻璃组合物，其特征在于，其组分以重量百分比表示，含有：SiO 2：52～72％；和/或B 2O 3：3～17％；和/或Al 2O 3：0.5～8％；和/或ZnO：2～10％；和/或TiO 2：0～5％；和/或Rn 2O：6～25％；和/或RO：0～15％；和/或P 2O 5：0～2％；和/或ZrO 2：0～3％；和/或La 2O 3：0～5％；和/或Y 2O 3：0～8％；和/或澄清剂：0～1％，所述RO为MgO、CaO、SrO、BaO的合计含量，Rn 2O为Li 2O、Na 2O、K 2O的合计含量，澄清剂为Sb 2O 3、SnO 2、Na 2SiF 6、K 2SiF 6中的一种或多种。
  5. 根据权利要求1～4任一所述的玻璃组合物，其特征在于，其组分以重量百分比表示，其中：Al 2O 3/SiO 2为0.01～0.1，优选Al 2O 3/SiO 2为0.02～0.08，更优选Al 2O 3/SiO 2为0.03～0.07；和/或Al 2O 3/B 2O 3为0.15～0.8，优选Al 2O 3/B 2O 3为0.15～0.6；和/或ZnO/SiO 2为0.03～0.17，优选ZnO/SiO 2为0.04～0.15，更优选ZnO/SiO 2为0.06～0.12；和/或(ZnO+TiO 2)/B 2O 3为0.2～2.0，优选(ZnO+TiO 2)/B 2O 3为0.3～1.5，更优选(ZnO+TiO 2)/B 2O 3为0.35～1.0。
  6. 根据权利要求1～4任一所述的玻璃组合物，其特征在于，其组分以重量百分比表示，其中：SiO 2：55～70％，优选SiO 2：56～68％；和/或B 2O 3：5～15％，优选B 2O 3：7～13％；和/或Al 2O 3：1～6％，优选Al 2O 3：1～5％；和/或ZnO：3～9％，优选ZnO：4～8％；和/或TiO 2：0.05～4％，优选TiO 2：0.2～3％；和/或Rn 2O：7～20％，优选Rn 2O：8～18％；和/或RO：0～12％，优选RO：0～10％；和/或P 2O 5：0～1％；和/或ZrO 2：0～2％，优选ZrO 2：0～1％；和/或La 2O 3：0～3％；和/或Y 2O 3：0～5％，优选Y 2O 3：0～3％；和/或澄清剂：0～0.8％，优选澄清剂：0～0.5％，所述RO为MgO、CaO、SrO、BaO的合计含量，Rn 2O为Li 2O、Na 2O、K 2O的合计含量，澄清剂为Sb 2O 3、SnO 2、Na 2SiF 6、K 2SiF 6中的一种或多种。
  7. 根据权利要求1～4任一所述的玻璃组合物，其特征在于，其组分以重量百分比表示，其中：Li 2O：0.1～5％，优选Li 2O：0.2～3％，更优选Li 2O：0.5～2％；和/或Na 2O：5～15％，优选Na 2O：6～14％，更优选Na 2O：7～13％；和/或K 2O：0～8％，优选K 2O：0～7％，更优选K 2O：0～5％。
  8. 根据权利要求1～4任一所述的玻璃组合物，其特征在于，其组分以重量百分比表示，其中：K 2O/(Na 2O+Li 2O)为0.8以下，优选K 2O/(Na 2O+Li 2O)为0.05～0.5，更优选K 2O/(Na 2O+Li 2O)为0.1～0.3；和/或Li 2O/Na 2O为0.01～0.3，优选Li 2O/Na 2O为0.02～0.25，更优选Li 2O/Na 2O为0.03～0.22；和/或K 2O/Na 2O为0.01～0.8，优选K 2O/Na 2O为0.05～0.5，更优选K 2O/Na 2O为0.1～0.4。
  9. 根据权利要求1～4任一所述的玻璃组合物，其特征在于，其组分以重量百分比表示，其中：CaO：不超过10％；和/或BaO：不超过10％。
  10. 根据权利要求1～4任一所述的玻璃组合物，其特征在于，其组分以重量百分比表示，其中：CaO：不超过5％；和/或BaO：不超过5％。
  11. 根据权利要求1～4任一所述的玻璃组合物，其特征在于，玻璃原料中的N元素含量低于2.0％，优选低于1.5％，更优选低于1.0％，所述N元素含量为熔制100Kg理论玻璃的N元素的引入量/100Kg玻璃重量×100％。
  12. 根据权利要求1～4任一所述的玻璃组合物，其特征在于，所述玻璃组合物的折射率n d为1.50～1.56，优选为1.505～1.55，更优选为1.51～1.54；阿贝数ν d为56～65，优选为57～63，更优选为57.5～62。
  13. 根据权利要求1～4任一所述的玻璃组合物，其特征在于，所述玻璃组合物的耐酸作用稳定性D A为2类以上，优选为1类；和/或耐水作用稳定性D W为2类以上，优选为1类；和/或热膨胀系数α 20/300℃为85×10 -7/K以下，优选为82×10 -7/K以下，更优选为80×10 -7/K以下；和/或转变温度T g为580℃以下，优选为570℃以下，更优选为560℃以下；和/或密度ρ为2.70g/cm 3以下，优选为2.65g/cm 3以下,更优选为2.60g/cm 3以下；和/或光透过率τ 400nm为98.0％以上，优选为98.5％以上，更优选为99.0％以上，进一步优选为99.2％以上；和/或经200小时耐候性测试后，浊度增加2.0％以下，优选增加1.0％以下，更优选增加0.8％以下，进一步优选增加0.5％以下；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/或条纹度为C级以上，优选为B级以上；和/或1400℃的高温粘度为220dPaS以下，优选为180dPaS以下，更优选为150dPaS以下。
  14. 玻璃预制件，其特征在于，采用权利要求1～13任一所述的玻璃组合物制成。
  15. 光学元件，其特征在于，采用权利要求1～13任一所述的玻璃组合物或权利要求14所述的玻璃预制件制成。
  16. 光学仪器，其特征在于，含有权利要求1～13任一所述的玻璃组合物，和/或含有权利要求15所述的光学元件。
PCT/CN2022/117257 2021-09-23 2022-09-06 玻璃组合物 Ceased WO2023045753A1 (zh)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117285251A (zh) * 2023-09-25 2023-12-26 成都光明光电股份有限公司 玻璃材料和玻璃元件

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN114956549B (zh) * 2022-06-14 2023-07-04 成都光明光电有限责任公司 封接玻璃
CN115745398B (zh) * 2022-11-30 2024-07-26 成都光明光电股份有限公司 玻璃组合物
CN117185648A (zh) * 2023-08-23 2023-12-08 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
CN117088609B (zh) * 2023-09-05 2025-03-18 成都光明光电股份有限公司 光学玻璃、玻璃预制件、光学元件和光学仪器

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109626814A (zh) * 2019-01-07 2019-04-16 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
CN111423111A (zh) * 2020-05-27 2020-07-17 成都光明光电股份有限公司 玻璃材料
CN111533443A (zh) * 2020-05-27 2020-08-14 成都光明光电股份有限公司 光学玻璃
CN111574049A (zh) * 2020-05-27 2020-08-25 成都光明光电股份有限公司 玻璃组合物
CN112028474A (zh) * 2020-09-11 2020-12-04 成都光明光电股份有限公司 光学玻璃
WO2021070707A1 (ja) * 2019-10-07 2021-04-15 日本電気硝子株式会社 紫外線透過ガラス
CN113045199A (zh) * 2021-03-23 2021-06-29 成都光明光电股份有限公司 透紫外玻璃
CN113735438A (zh) * 2021-09-23 2021-12-03 成都光明光电股份有限公司 玻璃组合物

Family Cites Families (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS496012A (zh) * 1972-05-10 1974-01-19
JPS6177638A (ja) * 1984-09-20 1986-04-21 Asahi Glass Co Ltd 耐水性の改善されたガラス
JPS6265954A (ja) * 1985-09-18 1987-03-25 Nippon Electric Glass Co Ltd アルミナ封着用硼珪酸ガラス
JPS62187141A (ja) * 1986-02-13 1987-08-15 Nippon Electric Glass Co Ltd 太陽電池カバ−用ガラス
JPS6442343A (en) * 1987-08-07 1989-02-14 Nippon Electric Glass Co Borosilicate glass for optical element
JPH0340938A (ja) * 1989-07-07 1991-02-21 Nippon Sheet Glass Co Ltd 紫外線吸収フレーク状ガラス
DE4230607C1 (de) * 1992-09-12 1994-01-05 Schott Glaswerke Chemisch und thermisch hochbelastbares, mit Wolfram verschmelzbares Borosilikatglas und dessen Verwendung
US5843855A (en) * 1997-01-15 1998-12-01 General Electric Company Glass
JP2001076336A (ja) 1999-09-08 2001-03-23 Hoya Corp 情報記録媒体用ガラス基板およびそれを用いた情報記録媒体
JP4697646B2 (ja) * 2001-02-19 2011-06-08 日本電気硝子株式会社 モールドプレス成形用光学ガラス
JP2005037651A (ja) * 2003-07-14 2005-02-10 Hoya Corp プロジェクタ搭載レンズ用光学ガラス、その製造方法、プロジェクタ搭載レンズおよびプロジェクタ
RU2333167C1 (ru) * 2006-11-24 2008-09-10 Юлия Алексеевна Щепочкина Нефриттованная глазурь
JP5729532B2 (ja) * 2008-10-07 2015-06-03 日本電気硝子株式会社 光学ガラス
JP2011168432A (ja) * 2010-02-18 2011-09-01 Nippon Electric Glass Co Ltd 照明用ガラス及び蛍光ランプ用外套管
JP2014108908A (ja) * 2012-12-03 2014-06-12 Nippon Electric Glass Co Ltd 集光型太陽光発電装置用フレネルレンズに用いられるガラス
WO2014192686A1 (ja) * 2013-05-28 2014-12-04 日本電気硝子株式会社 複合粉末、複合粉末ペースト及び着色層付きガラス板
CN104891811A (zh) * 2015-05-29 2015-09-09 成都光明光电股份有限公司 晶质玻璃
CN108975687B (zh) * 2015-06-24 2019-12-24 成都光明光电股份有限公司 光学玻璃
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
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
CN111777327A (zh) * 2020-07-20 2020-10-16 成都光明光电股份有限公司 玻璃组合物、玻璃制品及其制造方法
CN112028475B (zh) * 2020-09-11 2022-04-15 成都光明光电股份有限公司 光学玻璃和光学元件
CN112010561B (zh) * 2020-09-17 2022-04-15 成都光明光电股份有限公司 封装玻璃

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109626814A (zh) * 2019-01-07 2019-04-16 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
WO2021070707A1 (ja) * 2019-10-07 2021-04-15 日本電気硝子株式会社 紫外線透過ガラス
CN111423111A (zh) * 2020-05-27 2020-07-17 成都光明光电股份有限公司 玻璃材料
CN111533443A (zh) * 2020-05-27 2020-08-14 成都光明光电股份有限公司 光学玻璃
CN111574049A (zh) * 2020-05-27 2020-08-25 成都光明光电股份有限公司 玻璃组合物
CN112028474A (zh) * 2020-09-11 2020-12-04 成都光明光电股份有限公司 光学玻璃
CN113045199A (zh) * 2021-03-23 2021-06-29 成都光明光电股份有限公司 透紫外玻璃
CN113735438A (zh) * 2021-09-23 2021-12-03 成都光明光电股份有限公司 玻璃组合物

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP4406923A4 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117285251A (zh) * 2023-09-25 2023-12-26 成都光明光电股份有限公司 玻璃材料和玻璃元件

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