WO2022048335A1 - Optical glass and optical element - Google Patents

Optical glass and optical element Download PDF

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Publication number
WO2022048335A1
WO2022048335A1 PCT/CN2021/107560 CN2021107560W WO2022048335A1 WO 2022048335 A1 WO2022048335 A1 WO 2022048335A1 CN 2021107560 W CN2021107560 W CN 2021107560W WO 2022048335 A1 WO2022048335 A1 WO 2022048335A1
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Prior art keywords
glass
less
optical glass
tio
zno
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PCT/CN2021/107560
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French (fr)
Chinese (zh)
Inventor
匡波
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成都光明光电股份有限公司
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Priority to JP2023515188A priority Critical patent/JP2023539916A/en
Publication of WO2022048335A1 publication Critical patent/WO2022048335A1/en

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    • 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
    • C03C3/062—Glass compositions containing silica with less than 40% silica by weight
    • C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
    • C03C3/068—Glass compositions containing silica with less than 40% silica by weight containing boron containing rare earths

Definitions

  • the invention relates to an optical glass, in particular to a high-refractive-index optical glass with low thermal expansion coefficient and suitable for precision molding, as well as glass preforms and optical components made of the same.
  • Optical glass is a glass material used to manufacture lenses, prisms, mirrors and windows in optical instruments or mechanical systems.
  • the mainstream method of manufacturing optical glass into optical components is precision molding (including direct molding and secondary molding).
  • Lenses manufactured by precision molding usually do not need to be ground and polished, thereby reducing the consumption of raw materials.
  • the cost of manpower and material resources is reduced, and environmental pollution is reduced, and the technology can mass-produce optical components at low cost.
  • the so-called precision molding is to use a high-precision mold with a predetermined product shape to mold a glass preform under a certain temperature and pressure, so as to obtain a glass product with the final product shape and optical function.
  • Various optical glass products such as spherical lenses, aspherical lenses, prisms and diffraction gratings, can be manufactured through precision molding technology.
  • the transition temperature (T g ) of the glass material used for molding needs to be as low as possible.
  • optical glass With the advancement of technology and the continuous updating of optoelectronic information products, the demand for optical glass is also increasing, and higher requirements are also placed on the performance of optical glass. For example, because the thermal expansion coefficient of optical glass is too large, it is easy to cause cracks in the thermal processing process, reducing the yield of glass components; at the same time, it also leads to poor thermal shock resistance of optical glass.
  • the glass with higher refractive index can obtain a larger imaging field of view.
  • the demand for glass with high refractive index becomes more and more obvious.
  • the technical problem to be solved by the present invention is to provide a high refractive index optical glass with low thermal expansion coefficient and suitable for precision molding.
  • Optical glass whose components are expressed in weight percentage, and contains: B 2 O 3 : 8-20%; La 2 O 3 : 21-40%; Gd 2 O 3 : 6-20%; ZrO 2 : 1 ⁇ 10%; ZnO: 7 ⁇ 20%; WO 3 : 8 ⁇ 20%; TiO 2 : greater than 0 but less than or equal to 10%, wherein (WO 3 +ZnO)/(La 2 O 3 +TiO 2 +ZrO 2 ) is 0.3 to 1.5.
  • optical glass according to (1) wherein the components are expressed in weight percentage, and further contains: SiO 2 : 0-9%; and/or Y 2 O 3 : 0-10%; and/or Yb 2 O 3 : 0-10%; and/or Nb 2 O 5 : 0-8%; and/or Rn 2 O: 0-10%; and/or RO: 0-10%; and/or Al 2 O 3 : 0-5%; and/or Ta 2 O 5 : 0-5%; and/or clarifying agent: 0-1%, the Rn 2 O is one of Li 2 O, Na 2 O and K 2 O one or more, RO is one or more of MgO, CaO, SrO, BaO, and the clarifying agent is one or more of Sb 2 O 3 , SnO 2 , SnO and CeO 2 .
  • Optical glass containing B 2 O 3 , La 2 O 3 , Gd 2 O 3 , ZrO 2 , ZnO, WO 3 and TiO 2 as essential components, and its components are expressed in weight percent, wherein (WO 3 + ZnO)/(La 2 O 3 +TiO 2 +ZrO 2 ) is 0.3-1.5, the refractive index n d of the optical glass is 1.85-1.91, the Abbe number ⁇ d is 32-38.5, and the thermal expansion coefficient ⁇ is 100/300 °C is 100 ⁇ 10 -7 /K or less.
  • Optical glass its components are expressed in weight percentage, B 2 O 3 : 8-20%; La 2 O 3 : 21-40%; Gd 2 O 3 : 6-20%; ZrO 2 : 1-20% 10%; ZnO: 7-20%; WO 3 : 8-20%; TiO 2 : greater than 0 but less than or equal to 10%; SiO 2 : 0-9%; Y 2 O 3 : 0-10%; Yb 2 O 3 : 0-10%; Nb 2 O 5 : 0-8%; Rn 2 O: 0-10%; RO: 0-10%; Al 2 O 3 : 0-5%; Ta 2 O 5 : 0 ⁇ 5%; clarifier: 0 ⁇ 1% composition, wherein (WO 3 +ZnO)/(La 2 O 3 +TiO 2 +ZrO 2 ) is 0.3 ⁇ 1.5, and the Rn 2 O is Li 2 O, Na 2 One or more of O, K 2 O, RO is one or more of MgO, CaO, S
  • Nb 2 O 5 /Y 2 O 3 is 0.1 to 2.5;
  • Y 2 O 3 /WO 3 is 0.05 to 1.0
  • Y 2 O 3 /TiO 2 is 0.2 to 3.5;
  • 5 ⁇ Nb 2 O 5 /(WO 3 +Gd 2 O 3 ) is 0.05 to 1.5;
  • ZnO/La 2 O 3 is 0.2 ⁇ 0.8;
  • Gd 2 O 3 /(La 2 O 3 +Y 2 O 3 ) is 0.2 to 0.8;
  • Nb 2 O 5 /WO 3 is 0.03 to 0.7.
  • Nb 2 O 5 /Y 2 O 3 is 0.25 to 1.5;
  • Y 2 O 3 /TiO 2 is 0.5 to 2.0;
  • 5 ⁇ Nb 2 O 5 /(WO 3 +Gd 2 O 3 ) is 0.1 to 1.0;
  • ZnO/La 2 O 3 is 0.3 ⁇ 0.7;
  • Gd 2 O 3 /(La 2 O 3 +Y 2 O 3 ) is 0.25 to 0.65;
  • Nb 2 O 5 /WO 3 is 0.05 to 0.5.
  • Nb 2 O 5 /Y 2 O 3 is 0.3 to 0.8;
  • Y 2 O 3 /TiO 2 is 0.8 to 1.3;
  • 5 ⁇ Nb 2 O 5 /(WO 3 +Gd 2 O 3 ) is 0.15 to 0.5;
  • ZnO/La 2 O 3 is 0.35 ⁇ 0.65;
  • Gd 2 O 3 /(La 2 O 3 +Y 2 O 3 ) is 0.35 to 0.55;
  • Nb 2 O 5 /WO 3 is 0.06 to 0.4.
  • Nb 2 O 5 /Y 2 O 3 is 0.4 to 0.7;
  • ZnO/La 2 O 3 is 0.4 ⁇ 0.55;
  • Nb 2 O 5 /WO 3 is 0.08 to 0.3.
  • optical glass according to any one of (1) to (5), wherein the optical glass has a refractive index n d of 1.85 to 1.91, preferably 1.86 to 1.90, more preferably 1.88 to 1.90; Abbe number ⁇ d is 32-38.5, Preferably it is 33-37.5, More preferably, it is 34-37.
  • thermo expansion coefficient ⁇ 100/300°C of the optical glass is 100 ⁇ 10 -7 /K or less, preferably 95 ⁇ 10 -7 /K below, more preferably below 90 ⁇ 10 -7 /K; and/or the transition temperature T g is below 620°C, preferably below 610°C, more preferably below 600°C; and/or the upper limit of crystallization temperature is below 1250°C , preferably 1200°C or lower, more preferably 1180°C or lower, still more preferably 1160°C or lower.
  • optical element is made of the optical glass described in any one of (1) to (16) or the glass preform described in (17).
  • the beneficial effects of the present invention are: through reasonable component design, the optical glass obtained by the present invention has lower transition temperature and thermal expansion coefficient, and is suitable for precision molding.
  • optical glass of this invention is not limited to the following embodiment, It can change suitably within the range of the objective of this invention, and can implement.
  • this does not limit the gist of the invention.
  • the optical glass of the present invention may be simply referred to as glass.
  • each component (component) of the optical glass of the present invention will be described below.
  • the content of each component and the total content are all expressed in weight percent (wt%), that is, the content and total content of each component are relative to the total glass substance of the composition converted into oxides. Amounts are expressed in weight percent.
  • the “composition in terms of oxides” refers to the case where oxides, complex salts, hydroxides, etc. used as raw materials of the optical glass composition of the present invention are decomposed and converted into oxides when melted. , and the total amount of the oxide is taken as 100%.
  • B 2 O 3 is a network forming component, which can improve the thermal stability of the glass and improve the melting property of the glass, so that the glass without the melting residue of the glass raw material can be obtained.
  • the content of B 2 O 3 is preferably 10% or more, and more preferably the content of B 2 O 3 is 11 % or more.
  • the upper limit of the content of B 2 O 3 in the present invention is 20%, preferably 18%, and more preferably 17%. .
  • SiO 2 has the functions of improving the chemical stability of glass, maintaining the viscosity suitable for molten glass molding, and reducing the erosion of refractory materials. If its content is too high, the difficulty of melting the glass will increase, and it will be unfavorable to reduce the transition temperature of the glass. Therefore, in the present invention, the content of SiO 2 is 9% or less, preferably 0.5 to 9%, more preferably 1 to 8%, and further preferably 2 to 6%.
  • La 2 O 3 is a high-refractive and low-dispersion component, which can increase the refractive index of the glass, adjust the dispersion, and reduce the high temperature viscosity of the glass.
  • the content of La 2 O 3 is more than 21%, preferably La 2
  • the content of O 3 is 25% or more, and more preferably the content of La 2 O 3 is 28% or more.
  • the content of La 2 O 3 is 40% or less, preferably 38% or less, and more preferably 35% or less.
  • Gd 2 O 3 is contained in an amount of 6% or more to improve the chemical stability of the optical glass and adjust the thermal expansion coefficient and refractive index of the glass, preferably the content of Gd 2 O 3 is 8% or more, more preferably Gd 2
  • the content of O 3 is 9.5% or more, and more preferably the content of Gd 2 O 3 is 11% or more.
  • the content of Gd 2 O 3 is 20% or less, preferably 18% or less, and more preferably 16% or less.
  • the meltability and devitrification resistance of the glass are improved while maintaining high refractive index and low dispersion. If the content of Y 2 O 3 exceeds 10%, the stability and devitrification resistance of the glass decrease, and the transition temperature increases. Therefore, the content of Y 2 O 3 is 0 to 10%, preferably more than 0 but less than or equal to 6%. In some embodiments, by including 1% or more of Y 2 O 3 , the glass devitrification limit temperature and density can also be lowered. Therefore, the content of Y 2 O 3 in the present invention is more preferably 1 to 5%.
  • Gd 2 O 3 /(La 2 O 3 +Y 2 O 3 ) if Gd 2 O 3 /(La 2 O 3 +Y 2 O 3 ) is lower than 0.2, the stability of the glass is reduced, the temperature coefficient of refractive index is increased, and the glass is affected by temperature changes during use. large; when Gd 2 O 3 /(La 2 O 3 +Y 2 O 3 ) exceeds 0.8, the abrasion degree of the glass deteriorates and the density increases.
  • Gd 2 O 3 /(La 2 O 3 +Y 2 O 3 ) is preferably 0.2 to 0.8, more preferably Gd 2 O 3 /(La 2 O 3 +Y 2 O 3 ) is 0.25 to 0.65, and still more preferably Gd 2 O 3 /(La 2 O 3 +Y 2 O 3 ) is 0.35 to 0.55.
  • Yb 2 O 3 is also a component that imparts high refraction and low dispersion properties to glass, and is an optional component in the present invention.
  • the content of Yb 2 O 3 is limited to 0 to 10%, preferably 0 to 5%, more preferably 0 to 2%, and further preferably not containing Yb 2 O 3 .
  • ZnO can adjust the refractive index and dispersion of the glass, reduce the transition temperature, improve the anti-devitrification performance of the glass, and improve the stability of the glass. Melting at low temperature, which can improve the transmittance of glass.
  • the above effects are obtained by containing 7% or more of ZnO, preferably 8% or more, more preferably 10% or more, and even more preferably 11% or more.
  • the ZnO content is limited to 20% or less, preferably 18% or less, and more preferably 16% or less.
  • ZnO/La 2 O 3 is preferably 0.2 to 0.8, more preferably ZnO/La 2 O 3 is 0.3 to 0.7, still more preferably ZnO/La 2 O 3 is 0.35 to 0.65, and still more preferably ZnO/La 2 O 3 is 0.4 to 0.55.
  • WO 3 can improve the refractive index and mechanical strength of the glass, and reduce the transition temperature of the glass.
  • the above effects are obtained by containing more than 8% of WO 3 , preferably the lower limit of the content of WO 3 is 10%, more preferably the lower limit of the content of WO 3 to 12%.
  • the upper limit of the content of WO 3 is 20%, preferably 18%, and more preferably 17%.
  • Y 2 O 3 /WO 3 is preferably 0.05 to 1.0, more preferably Y 2 O 3 /WO 3 is 0.1 to 0.6, and still more preferably Y 2 O 3 /WO 3 is 0.1 to 0.4.
  • Nb 2 O 5 is a high refractive index and high dispersion component, which can improve the refractive index and devitrification resistance of the glass, and reduce the thermal expansion coefficient of the glass. If the content of Nb 2 O 5 is too high, the thermal stability and chemical stability of the glass will be reduced. , the light transmittance decreases. Therefore, the content of Nb 2 O 5 in the present invention is 0 to 8%, preferably 0.5 to 6%, and more preferably 1 to 5%.
  • Nb 2 O 5 , WO 3 and Gd 2 O 3 can produce a complex synergistic effect in glass, especially to make 5 ⁇ Nb 2 O 5 /( When WO 3 +Gd 2 O 3 ) is in the range of 0.05 to 1.5, the glass can obtain good hot-press stability and at the same time have a suitable degree of abrasion, preferably 5 ⁇ Nb 2 O 5 /(WO 3 +Gd 2 O 3 ) is 0.1 to 1.0.
  • the thermal expansion coefficient of the glass can be further optimized, so 5 ⁇ Nb 2 O 5 /(WO 3 +Gd 2 O 3 ) is 0.15 to 0.5, more preferably 5 ⁇ Nb 2 O 5 /(WO 3 +Gd 2 O 3 ) is 0.2 to 0.4.
  • Nb 2 O 5 /Y 2 O 3 is preferably 0.1 to 2.5, more preferably Nb 2 O 5 /Y 2 O 3 is 0.25 to 1.5, still more preferably Nb 2 O 5 /Y 2 O 3 is 0.3 to 0.8, and more preferably More preferably, Nb 2 O 5 /Y 2 O 3 is 0.4 to 0.7.
  • Nb 2 O 5 /WO 3 in the range of 0.03-0.7, it helps to improve the thermal stability of the glass and optimize the chemical stability of the glass, preferably Nb 2 O 5 /WO 3 It is 0.05-0.5, it is more preferable that Nb2O5 /WO3 is 0.06-0.4 , and it is more preferable that Nb2O5 / WO3 is 0.08-0.3 .
  • TiO 2 has the effect of increasing the refractive index and dispersion of glass, and an appropriate amount can make the glass more stable and reduce the viscosity of the glass.
  • the content of TiO 2 exceeds 10%, the crystallization tendency of the glass increases, the transition temperature of the glass increases, and the glass becomes easy to be colored during press molding. Therefore, in the present invention, the content of TiO 2 is greater than 0 but less than or equal to 10%, preferably the content of TiO 2 is 0.5-7%, more preferably 1-5%.
  • Y 2 O 3 /TiO 2 is preferably 0.2 to 3.5, more preferably Y 2 O 3 /TiO 2 is 0.5 to 2.0, and still more preferably Y 2 O 3 /TiO 2 is 0.8 to 1.3.
  • ZrO 2 is a high-refractive and low-dispersion component, which can increase the refractive index of the glass, adjust the dispersion, and improve the anti-devitrification performance of the glass.
  • the above effects are obtained by containing more than 1% ZrO 2 , preferably The content of ZrO 2 is 2% or more. If the content of ZrO 2 is higher than 10%, the difficulty of melting the glass will increase, the melting temperature will increase, and further, inclusions will appear in the glass and the transmittance will decrease. Therefore, the ZrO 2 content is 10% or less, preferably 8% or less, and more preferably 6% or less.
  • the glass by controlling the ratio between the total content of WO 3 and ZnO WO 3 +ZnO and the total content of La 2 O 3 , TiO 2 and ZrO 2 La 2 O 3 +TiO 2 +ZrO 2 When (WO 3 +ZnO)/(La 2 O 3 +TiO 2 +ZrO 2 ) is in the range of 0.3 to 1.5, the glass can obtain a lower thermal expansion coefficient while having a lower transition temperature.
  • (WO 3 +ZnO)/(La 2 O 3 +TiO 2 +ZrO 2 ) is preferably 0.3 to 1.5, more preferably (WO 3 +ZnO)/(La 2 O 3 +TiO 2 +ZrO 2 ) is 0.5 to 1.0.
  • the bubble degree and abrasion degree of the glass can be further optimized, so (WO 3 + ZnO)/(La 2 O 3 +TiO 2 +ZrO 2 ) is 0.6 to 0.9, and more preferably (WO 3 +ZnO)/(La 2 O 3 +TiO 2 +ZrO 2 ) is 0.7 to 0.85.
  • Rn 2 O is an alkali metal oxide
  • Rn 2 O is one or more of Li 2 O, Na 2 O and K 2 O, which can improve the melting property of glass and lower the transition temperature of glass.
  • the content exceeds 10%, the devitrification resistance of the glass deteriorates, and the refractive index decreases significantly. Therefore, in the present invention, the Rn 2 O content is 0 to 10%, preferably 0 to 5%, and more preferably 0.5 to 3%.
  • Li 2 O can reduce the transition temperature of glass, but when its content is high, it is unfavorable to the acid resistance stability and thermal expansion coefficient of the glass. Therefore, the content of Li 2 O in the present invention is 6% or less, preferably greater than 0 but less than or equal to 4 %, more preferably 0.1 to 3%, still more preferably 0.5 to 2%.
  • the viscosity of the glass can be optimized, and the striae degree and the bubble degree of the glass can be improved, preferably 5 ⁇ Li 2 O/(TiO 2 +SiO 2 ) is 0.1 to 2.0.
  • setting the value of 5 ⁇ Li 2 O/(TiO 2 +SiO 2 ) in the range of 0.2 to 1.0 can significantly improve the moldability of the glass and reduce the probability of fogging of the glass during the molding process. Therefore, 5 ⁇ Li 2 O/(TiO 2 +SiO 2 ) is more preferably 0.2 to 1.0, and still more preferably 5 ⁇ Li 2 O/(TiO 2 +SiO 2 ) is 0.3 to 0.8.
  • Na 2 O has the effect of improving the melting property of glass, which can improve the melting effect of glass and lower the transition temperature of glass. If the content of Na 2 O exceeds 5 %, the chemical stability and weather resistance of glass will be reduced.
  • the content of Na 2 O is 0-5%, preferably the content of Na 2 O is 0-3%, and the content of Na 2 O is more preferably 0-2%.
  • K 2 O has the effect of improving the thermal stability and melting properties of glass, but if its content exceeds 5%, the devitrification resistance of the glass decreases, and the chemical stability of the glass deteriorates. Therefore, the content of K 2 O in the present invention is 5% or less, The content of K 2 O is preferably 0 to 3%, more preferably 0 to 2%.
  • RO is an alkaline earth metal oxide
  • RO is one or more of MgO, CaO, SrO, and BaO. Adding RO into the glass can improve the melting property of the glass and lower the transition temperature of the glass. If the content of RO exceeds 10%, the devitrification resistance of the glass will decrease. Therefore, in the present invention, the RO content is 0 to 10%, preferably 0 to 5%, more preferably 0 to 2%, and further preferably no RO is contained.
  • Al 2 O 3 can improve the chemical stability of glass, but when its content exceeds 5%, the meltability and transmittance of the glass deteriorate. Therefore, the content of Al 2 O 3 in the present invention is 0 to 5%, preferably 0 to 2%, more preferably 0 to 1%, and further preferably not containing Al 2 O 3 .
  • Ta 2 O 5 has the functions of increasing the refractive index and improving the devitrification resistance of the glass, but if its content is too high, the chemical stability of the glass decreases, and the optical constant is difficult to control to the desired range; on the other hand, compared with other components , Ta 2 O 5 is very expensive, from the practical and cost point of view, its usage should be minimized. Therefore, the Ta 2 O 5 content in the present invention is limited to 0 to 5%, preferably 0 to 2%, more preferably 0 to 1%, and further preferably not containing Ta 2 O 5 .
  • the clarifying effect of the glass can be improved, and the content of the clarifying agent is preferably 0- 0.5%, more preferably 0 to 0.1%.
  • the content of Sb 2 O 3 exceeds 1%, the glass tends to reduce the refining performance, and at the same time, due to its strong oxidation effect, it promotes the corrosion of the platinum or platinum alloy utensils in which the glass is melted and the deterioration of the forming mold. Therefore, Sb 2 is preferred in the present invention.
  • the addition amount of O 3 is 0 to 1%, more preferably 0 to 0.5%, still more preferably 0 to 0.1%.
  • SnO and SnO 2 can also be added as fining agents, but when the content exceeds 1%, the tendency to color the glass increases, or when the glass is heated, softened and reshaped by press molding, Sn will become the origin of crystal nucleation , resulting in a tendency to devitrification. Therefore, the content of SnO 2 in the present invention is preferably 0-1%, more preferably 0-0.5, still more preferably 0-0.1%, and even more preferably not contained; the content of SnO is preferably 0-1%, more preferably 0- 0.5%, more preferably 0 to 0.1%, and still more preferably not contained.
  • the function and addition ratio of CeO 2 are the same as those of SnO 2 , and its content is preferably 0 to 1%, more preferably 0 to 0.5%, still more preferably 0 to 0.1%, and still more preferably not contained.
  • F fluorine
  • F can lead to poor glass stability and reduced devitrification resistance, while its volatility can lead to unstable glass optical constants and streaks Since the degree of intensity deteriorates, it is preferable not to contain F.
  • GeO 2 An appropriate amount of GeO 2 can be contained in the glass of the present invention, but in some embodiments, the introduction of GeO 2 will lead to a decrease in the transmittance of the glass, and at the same time, since it is an expensive raw material, it reduces the economy of the glass, so it is preferred Does not contain GeO 2 .
  • P 2 O 5 may be contained in the glass of the present invention, but in some embodiments, the inclusion of P 2 O 5 in the glass makes it difficult to obtain a desired high refractive index, and the devitrification resistance of the glass decreases, so it is preferred Does not contain P 2 O 5 .
  • Bi 2 O 3 An appropriate amount of Bi 2 O 3 may be contained in the glass of the present invention, but in some embodiments, Bi 2 O 3 will reduce the light transmittance of the glass, deteriorate the abrasion degree and chemical stability, and significantly increase the density, Therefore, it is preferable not to contain Bi 2 O 3 .
  • the glass of the present invention even if the oxides of transition metals such as V, Cr, Mn, Fe, Co, Ni, Cu, Ag, and Mo are contained in small amounts alone or in combination, the glass will be colored, and in the visible light region Specified wavelengths are absorbed, thereby weakening the property of the present invention to improve the visible light transmittance effect. Therefore, it is preferable not to actually contain the optical glass, which requires transmittance at wavelengths in the visible light region.
  • Oxides of Th, Cd, Tl, Os, Be, and Se tend to be used in a controlled manner as harmful chemical substances in recent years, and they are environmentally friendly not only in the manufacturing process of glass, but also in the processing process and disposal after productization. Action is required. Therefore, in the case of attaching importance to the influence on the environment, it is preferable not to actually contain them except for unavoidable mixing. Thereby, the optical glass becomes practically free of substances that pollute the environment. Therefore, the optical glass of the present invention can be manufactured, processed, and discarded without taking special measures for environmental measures.
  • the optical glass of the present invention preferably does not contain As 2 O 3 and PbO.
  • As 2 O 3 has the effect of eliminating bubbles and preventing glass coloration, the addition of As 2 O 3 will increase the platinum erosion of the glass to the furnace, especially the platinum furnace, resulting in more platinum ions entering the glass. The service life of the platinum furnace is adversely affected.
  • Does not contain and "0%” described herein means that the compound, molecule or element, etc. is not intentionally added as a raw material to the optical glass of the present invention; however, as a raw material and/or equipment for producing optical glass, there may be some Impurities or components that are not intentionally added will be contained in a small or trace amount in the final optical glass, 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 optical glass are tested according to the methods specified in GB/T 7962.1-2010.
  • the lower limit of the refractive index (n d ) of the optical glass of the present invention is 1.85, preferably the lower limit is 1.86, and more preferably the lower limit is 1.88; the upper limit of the refractive index (n d ) is 1.91, preferably 1.90.
  • the lower limit of the Abbe number ( ⁇ d ) of the optical glass of the present invention is 32, preferably the lower limit is 33, and more preferably the lower limit is 34; the upper limit of the Abbe number ( ⁇ d ) is 38.5, and the preferred upper limit is 37.5 , more preferably the upper limit is 37.
  • the density ( ⁇ ) of optical glass is tested according to the method specified in GB/T7962.20-2010.
  • the density ( ⁇ ) of the optical glass of the present invention is 5.50 g/cm 3 or less, preferably 5.40 g/cm 3 or less, more preferably 5.30 g/cm 3 or less, and even more preferably 5.20 g/cm 3 the following.
  • the thermal expansion coefficient ( ⁇ 100/300°C ) of the optical glass is tested according to the method specified in GB/T7962.16-2010 at 100-300°C.
  • the thermal expansion coefficient ( ⁇ 100/300°C ) of the optical glass of the present invention is 100 ⁇ 10 -7 /K or less, preferably 95 ⁇ 10 -7 /K or less, more preferably 90 ⁇ 10 -7 /K or less.
  • the transition temperature (T g ) of the optical glass is tested according to the method specified in GB/T7962.16-2010.
  • the transition temperature (T g ) of the optical glass of the present invention is 620°C or lower, preferably 610°C or lower, and more preferably 600°C or lower.
  • the short-wave transmission spectral properties of the glasses of the present invention are expressed in terms of tinting degrees ( ⁇ 70 and ⁇ 5 ).
  • ⁇ 70 refers to the wavelength corresponding to the glass transmittance of 70%.
  • ⁇ 70 was measured by measuring the spectral transmittance in the wavelength range from 280 nm to 700 nm using glass with a thickness of 10 ⁇ 0.1 mm having two opposite planes parallel to each other and optically polished and showing a wavelength of 70% transmittance.
  • the so-called spectral transmittance or transmittance is the amount expressed by I out /I in when light of the intensity I in is incident perpendicularly to the above-mentioned surface of the glass, passes through the glass, and emits light of the intensity I out from one plane, and
  • the transmittance of the surface reflection loss on the above-mentioned surface of the glass is also included.
  • ⁇ 70 of the optical glass of the present invention is less than or equal to 410 nm, preferably ⁇ 70 is less than or equal to 405 nm, more preferably ⁇ 70 is less than or equal to 400 nm, further preferably ⁇ 70 is less than or equal to 395 nm.
  • ⁇ 5 of the optical glass of the present invention is less than or equal to 375 nm, preferably ⁇ 5 is less than or equal to 370 nm, more preferably ⁇ 5 is less than or equal to 365 nm, further preferably ⁇ 5 is less than or equal to 360 nm.
  • the acid resistance stability (D A ) (powder method) of optical glass is tested according to the method specified in GB/T 17129.
  • the acid resistance stability (D A ) of the optical glass of the present invention is three or more types, preferably two or more types, and more preferably one type.
  • the water resistance stability (D W ) (powder method) of optical glass is tested according to the method specified in GB/T 17129.
  • the water resistance stability (D W ) of the optical glass of the present invention is 2 or more types, preferably 1 type.
  • the crystallization performance of the glass was measured by the temperature gradient furnace method.
  • the glass was made into a sample of 180 ⁇ 10 ⁇ 10 mm, the sides were polished, and then placed in a furnace with a temperature gradient (10 °C/cm) and heated to 1300 °C for 4 hours. Take it out and cool it to room temperature naturally, and observe the crystallization of the glass under a microscope.
  • the maximum temperature corresponding to the appearance of crystals in the glass is the upper limit temperature of the crystallization of the glass.
  • the crystallization upper limit temperature of the optical glass of this invention is 1250 degrees C or less, Preferably it is 1200 degrees C or less, More preferably, it is 1180 degrees C or less, More preferably, it is 1160 degrees C or less.
  • the manufacturing method of the optical glass of the present invention is as follows: the glass of the present invention is produced by using conventional raw materials and processes, including but not limited to using carbonates, nitrates, sulfates, hydroxides, oxides, etc. , put the prepared charge into a smelting furnace (such as platinum crucible, alumina crucible, etc.) at 1200 ⁇ 1400 ° C for melting, and after clarification, stirring and homogenization, get no bubbles and no undissolved substances. quality molten glass, which is cast in a mold and annealed. Those skilled in the art can appropriately select raw materials, process methods and process parameters according to actual needs.
  • a smelting furnace such as platinum crucible, alumina crucible, etc.
  • a glass preform can be produced from the optical glass produced by using, for example, a means of grinding, or a means of press forming such as reheat press forming and precision press forming. That is, a glass preform can be produced by subjecting optical glass to mechanical processing such as grinding and polishing, or by producing a preform for press-molding from optical glass, reheating the preform, and then grinding the preform. Glass preforms are produced by machining, or by precision stamping of preforms produced by grinding.
  • the means for preparing the glass preform is not limited to the above-mentioned means.
  • the optical glass of the present invention is useful for various optical elements and optical designs, and it is particularly preferable to form a preform from the optical glass of the present invention, and to perform reheat press molding, precision press molding, etc. using the preform , making optical components such as lenses and prisms.
  • Both the glass preform and the optical element of the present invention are formed from the optical glass of the present invention described above.
  • the glass preform of the present invention has the excellent characteristics of optical glass;
  • the optical element of the present invention has the excellent characteristics of optical glass, and can provide various optical elements such as lenses and prisms with high optical value.
  • lenses 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.
  • optical element formed by the optical glass of the present invention can be used to manufacture optical instruments such as photographic equipment, imaging equipment, display equipment and monitoring equipment.
  • the optical glass which has the composition shown in Table 1 - Table 2 was obtained by the manufacturing method of the said optical glass.
  • the properties of each glass were measured by the test method of the present invention, and the measurement results are shown in Tables 1 to 2.
  • a concave meniscus lens, a convex meniscus lens, and a biconvex lens are produced by using the glass obtained in the optical glass Examples 1 to 20, for example, by means of grinding, or by means of press molding such as reheat press molding and precision press molding. , Bi-concave lenses, plano-convex lenses, plano-concave lenses and other lenses, prisms and other prefabricated parts.
  • each preform is ground and polished to produce various lenses and prisms such as a concave meniscus lens, a convex meniscus lens, a biconvex lens, a biconcave lens, a plano-convex lens, and a plano-concave lens.
  • An antireflection film may also be coated on the surface of the obtained optical element.
  • optical elements produced by the above-mentioned optical element embodiments are optically designed and formed by using one or more optical elements to form optical components or optical assemblies, which can be used in, for example, imaging equipment, sensors, microscopes, medical technology, digital projection, communications, optical communications Technology/information transmission, optics/lighting in the automotive field, lithography, excimer lasers, wafers, computer chips and integrated circuits and electronic devices including such circuits and chips, or camera equipment and devices for the automotive field.

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Abstract

The present invention provides an optical glass, comprising the following components in weight percentage: 8-20% of B2O3; 21-40% of La2O3; 6-20% of Gd2O3; 1-10% of ZrO2; 7-20% of ZnO; 8-20% of WO3; and greater than 0 but less than or equal to 10% of TiO2, wherein WO3+ZnO)/(La2O3+TiO2+ZrO2) is 0.3-1.5. By means of a reasonable composition design, the optical glass obtained by the present invention has low transition temperature and thermal expansion coefficient, and is suitable for precision molding.

Description

光学玻璃及光学元件Optical glass and optical components 技术领域technical field
本发明涉及一种光学玻璃，尤其是涉及一种热膨胀系数较低，适用于精密模压的高折射率光学玻璃，以及由其制成的玻璃预制件和光学元件。The invention relates to an optical glass, in particular to a high-refractive-index optical glass with low thermal expansion coefficient and suitable for precision molding, as well as glass preforms and optical components made of the same.
背景技术Background technique
光学玻璃是用于制造光学仪器或机械系统中的透镜、棱镜、反射镜和窗口等的玻璃材料。目前将光学玻璃制造为光学元件的主流方法是精密模压成型(包括直接压型法和二次压型法)，采用精密模压技术制造的透镜通常不用再进行研磨和抛光，从而减少了原材料消耗，降低了人力和物力成本，并且减少了环境污染，该技术可以低成本大批量生产光学元件。所谓精密模压，就是在一定的温度、压力下，用具有预定产品形状的高精密模具模压玻璃预制件，从而获得具有最终产品形状和光学功能的玻璃制品。通过精密模压技术可以制造各种光学玻璃产品，如球面透镜、非球面透镜、棱镜和衍射光栅等。Optical glass is a glass material used to manufacture lenses, prisms, mirrors and windows in optical instruments or mechanical systems. At present, the mainstream method of manufacturing optical glass into optical components is precision molding (including direct molding and secondary molding). Lenses manufactured by precision molding usually do not need to be ground and polished, thereby reducing the consumption of raw materials. The cost of manpower and material resources is reduced, and environmental pollution is reduced, and the technology can mass-produce optical components at low cost. The so-called precision molding is to use a high-precision mold with a predetermined product shape to mold a glass preform under a certain temperature and pressure, so as to obtain a glass product with the final product shape and optical function. Various optical glass products, such as spherical lenses, aspherical lenses, prisms and diffraction gratings, can be manufactured through precision molding technology.
在进行精密模压成型时，为了将高精密的模面复制在玻璃成品上，需要在高温下(通常在玻璃转变温度20～60℃以上)加压成型玻璃预制体，这时成型模在高温和压力下，即使处于保护气体中，模具表面也容易被氧化和侵蚀。为了延长模具的寿命，抑制高温环境对模具的损伤，就必须降低压型温度，因此，用于模压的玻璃材料的转变温度(T g)需要尽可能的低。 When performing precision compression molding, in order to replicate the high-precision mold surface on the glass finished product, it is necessary to press-form the glass preform at a high temperature (usually above the glass transition temperature of 20-60 °C). Under pressure, even in protective gas, the mold surface is susceptible to oxidation and erosion. In order to prolong the life of the mold and suppress damage to the mold in a high temperature environment, it is necessary to reduce the molding temperature. Therefore, the transition temperature (T g ) of the glass material used for molding needs to be as low as possible.
随着科技的进步，光电信息产品的不断更新，对光学玻璃的需求量也越来越大，同时对光学玻璃的性能也提出了更高的要求。如光学玻璃由于热膨胀系数过大，容易在热加工过程中造成破裂，降低玻璃元件的良品率；同时也导致光学玻璃抗热冲击的性能差。With the advancement of technology and the continuous updating of optoelectronic information products, the demand for optical glass is also increasing, and higher requirements are also placed on the performance of optical glass. For example, because the thermal expansion coefficient of optical glass is too large, it is easy to cause cracks in the thermal processing process, reducing the yield of glass components; at the same time, it also leads to poor thermal shock resistance of optical glass.
在相同曲率半径下，折射率越高的玻璃获得的成像视场越大，随着光学器件小型化的发展趋势，高折射率的玻璃需求趋势越来越明显。Under the same curvature radius, the glass with higher refractive index can obtain a larger imaging field of view. With the development trend of miniaturization of optical devices, the demand for glass with high refractive index becomes more and more obvious.
发明内容SUMMARY OF THE INVENTION
本发明所要解决的技术问题是提供一种热膨胀系数较低，适于精密模压的高折射率光学玻璃。The technical problem to be solved by the present invention is to provide a high refractive index optical glass with low thermal expansion coefficient and suitable for precision molding.
本发明解决技术问题采用的技术方案是：The technical scheme adopted by the present invention to solve the technical problem is:
(1)光学玻璃，其组分以重量百分比表示，含有：B 2O 3：8～20％；La 2O 3：21～40％；Gd 2O 3：6～20％；ZrO 2：1～10％；ZnO：7～20％；WO 3：8～20％；TiO 2：大于0但小于或等于10％，其中(WO 3+ZnO)/(La 2O 3+TiO 2+ZrO 2)为0.3～1.5。 (1) Optical glass, whose components are expressed in weight percentage, and contains: B 2 O 3 : 8-20%; La 2 O 3 : 21-40%; Gd 2 O 3 : 6-20%; ZrO 2 : 1 ～10%; ZnO: 7～20%; WO 3 : 8～20%; TiO 2 : greater than 0 but less than or equal to 10%, wherein (WO 3 +ZnO)/(La 2 O 3 +TiO 2 +ZrO 2 ) is 0.3 to 1.5.
(2)根据(1)所述的光学玻璃，其组分以重量百分比表示，还含有：SiO 2：0～9％；和/或Y 2O 3：0～10％；和/或Yb 2O 3：0～10％；和/或Nb 2O 5：0～8％；和/或Rn 2O：0～10％；和/或RO：0～10％；和/或Al 2O 3：0～5％；和/或Ta 2O 5：0～5％；和/或澄清剂：0～1％，所述Rn 2O为Li 2O、Na 2O、K 2O中的一种或多种，RO为MgO、CaO、SrO、BaO中的一种或多种，澄清剂为Sb 2O 3、SnO 2、SnO、CeO 2中的一种或多种。 (2) The optical glass according to (1), wherein the components are expressed in weight percentage, and further contains: SiO 2 : 0-9%; and/or Y 2 O 3 : 0-10%; and/or Yb 2 O 3 : 0-10%; and/or Nb 2 O 5 : 0-8%; and/or Rn 2 O: 0-10%; and/or RO: 0-10%; and/or Al 2 O 3 : 0-5%; and/or Ta 2 O 5 : 0-5%; and/or clarifying agent: 0-1%, the Rn 2 O is one of Li 2 O, Na 2 O and K 2 O one or more, RO is one or more of MgO, CaO, SrO, BaO, and the clarifying agent is one or more of Sb 2 O 3 , SnO 2 , SnO and CeO 2 .
(3)光学玻璃，含有B 2O 3、La 2O 3、Gd 2O 3、ZrO 2、ZnO、WO 3和TiO 2作为必要组分，其组分以重量百分比表示，其中(WO 3+ZnO)/(La 2O 3+TiO 2+ZrO 2)为0.3～1.5，所述光学玻璃的折射率n d为1.85～1.91，阿贝数ν d为32～38.5，热膨胀系数α 100/300℃为100×10 -7/K以下。 (3) Optical glass, containing B 2 O 3 , La 2 O 3 , Gd 2 O 3 , ZrO 2 , ZnO, WO 3 and TiO 2 as essential components, and its components are expressed in weight percent, wherein (WO 3 + ZnO)/(La 2 O 3 +TiO 2 +ZrO 2 ) is 0.3-1.5, the refractive index n d of the optical glass is 1.85-1.91, the Abbe number ν d is 32-38.5, and the thermal expansion coefficient α is 100/300 °C is 100×10 -7 /K or less.
(4)根据(3)所述的光学玻璃，其组分以重量百分比表示，含有：B 2O 3：8～20％；和/或La 2O 3：21～40％；和/或Gd 2O 3：6～20％；和/或ZrO 2：1～10％；和/或ZnO：7～20％；和/或WO 3：8～20％；和/或TiO 2：大于0但小于或等于10％；和/或SiO 2：0～9％；和/或Y 2O 3：0～10％；和/或Yb 2O 3：0～10％；和/或Nb 2O 5：0～8％；和/或Rn 2O：0～10％；和/或RO：0～10％；和/或Al 2O 3：0～5％；和/或Ta 2O 5：0～5％；和/或澄清剂：0～1％，所述Rn 2O为Li 2O、Na 2O、K 2O中的一种或多种，RO为MgO、CaO、SrO、BaO中的一种或多种，澄清剂为Sb 2O 3、SnO 2、SnO、CeO 2中的一种或多种。 (4) The optical glass according to (3), wherein the components are expressed in weight percentage, and contain: B 2 O 3 : 8-20%; and/or La 2 O 3 : 21-40%; and/or Gd 2 O 3 : 6-20%; and/or ZrO 2 : 1-10%; and/or ZnO: 7-20%; and/or WO 3 : 8-20%; and/or TiO 2 : more than 0 but and/or SiO 2 : 0-9%; and/or Y 2 O 3 : 0-10%; and/or Yb 2 O 3 : 0-10%; and/or Nb 2 O 5 : 0-8%; and/or Rn 2 O: 0-10%; and/or RO: 0-10%; and/or Al 2 O 3 : 0-5%; and/or Ta 2 O 5 : 0 ～5%; and/or clarifier: 0～1%, the Rn 2 O is one or more of Li 2 O, Na 2 O, K 2 O, and RO is MgO, CaO, SrO, BaO One or more of the clarifiers are one or more of Sb 2 O 3 , SnO 2 , SnO and CeO 2 .
(5)光学玻璃，其组分以重量百分比表示，由B 2O 3：8～20％；La 2O 3：21～40％；Gd 2O 3：6～20％；ZrO 2：1～10％；ZnO：7～20％；WO 3：8～20％；TiO 2： 大于0但小于或等于10％；SiO 2：0～9％；Y 2O 3：0～10％；Yb 2O 3：0～10％；Nb 2O 5：0～8％；Rn 2O：0～10％；RO：0～10％；Al 2O 3：0～5％；Ta 2O 5：0～5％；澄清剂：0～1％组成，其中(WO 3+ZnO)/(La 2O 3+TiO 2+ZrO 2)为0.3～1.5，所述Rn 2O为Li 2O、Na 2O、K 2O中的一种或多种，RO为MgO、CaO、SrO、BaO中的一种或多种，澄清剂为Sb 2O 3、SnO 2、SnO、CeO 2中的一种或多种。 (5) Optical glass, its components are expressed in weight percentage, B 2 O 3 : 8-20%; La 2 O 3 : 21-40%; Gd 2 O 3 : 6-20%; ZrO 2 : 1-20% 10%; ZnO: 7-20%; WO 3 : 8-20%; TiO 2 : greater than 0 but less than or equal to 10%; SiO 2 : 0-9%; Y 2 O 3 : 0-10%; Yb 2 O 3 : 0-10%; Nb 2 O 5 : 0-8%; Rn 2 O: 0-10%; RO: 0-10%; Al 2 O 3 : 0-5%; Ta 2 O 5 : 0 ～5%; clarifier: 0～1% composition, wherein (WO 3 +ZnO)/(La 2 O 3 +TiO 2 +ZrO 2 ) is 0.3～1.5, and the Rn 2 O is Li 2 O, Na 2 One or more of O, K 2 O, RO is one or more of MgO, CaO, SrO, BaO, clarifier is one or more of Sb 2 O 3 , SnO 2 , SnO, CeO 2 variety.
(6)根据(1)～(5)任一所述的光学玻璃，其组分以重量百分比表示，满足以下9种情形中的一种以上：(6) The optical glass according to any one of (1) to (5), wherein the components are expressed in weight percentage and satisfy one or more of the following nine situations:
1)Nb 2O 5/Y 2O 3为0.1～2.5； 1) Nb 2 O 5 /Y 2 O 3 is 0.1 to 2.5;
2)Y 2O 3/WO 3为0.05～1.0； 2) Y 2 O 3 /WO 3 is 0.05 to 1.0;
3)Y 2O 3/TiO 2为0.2～3.5； 3) Y 2 O 3 /TiO 2 is 0.2 to 3.5;
4)5×Nb 2O 5/(WO 3+Gd 2O 3)为0.05～1.5； 4) 5×Nb 2 O 5 /(WO 3 +Gd 2 O 3 ) is 0.05 to 1.5;
5)ZnO/La 2O 3为0.2～0.8； 5) ZnO/La 2 O 3 is 0.2～0.8;
6)Gd 2O 3/(La 2O 3+Y 2O 3)为0.2～0.8； 6) Gd 2 O 3 /(La 2 O 3 +Y 2 O 3 ) is 0.2 to 0.8;
7)(WO 3+ZnO)/(La 2O 3+TiO 2+ZrO 2)为0.5～1.0； 7) (WO 3 +ZnO)/(La 2 O 3 +TiO 2 +ZrO 2 ) is 0.5 to 1.0;
8)5×Li 2O/(TiO 2+SiO 2)为0.05～5.0； 8) 5×Li 2 O/(TiO 2 +SiO 2 ) is 0.05 to 5.0;
9)Nb 2O 5/WO 3为0.03～0.7。 9) Nb 2 O 5 /WO 3 is 0.03 to 0.7.
(7)根据(1)～(5)任一所述的光学玻璃，其组分以重量百分比表示，其中：B 2O 3：10～18％；和/或La 2O 3：25～38％；和/或Gd 2O 3：8～18％；和/或ZrO 2：1～8％；和/或ZnO：8～18％；和/或WO 3：10～18％；和/或TiO 2：0.5～7％；和/或SiO 2：0.5～9％；和/或Y 2O 3：大于0但小于或等于6％；和/或Yb 2O 3：0～5％；和/或Nb 2O 5：0.5～6％；和/或Rn 2O：0～5％；和/或RO：0～5％；和/或Al 2O 3：0～2％；和/或Ta 2O 5：0～2％；和/或澄清剂：0～0.5％，所述Rn 2O为Li 2O、Na 2O、K 2O中的一种或多种，RO为MgO、CaO、SrO、BaO中的一种或多种，澄清剂为Sb 2O 3、SnO 2、SnO、CeO 2中的一种或多种。 (7) The optical glass according to any one of (1) to (5), whose components are expressed in weight percentage, wherein: B 2 O 3 : 10-18%; and/or La 2 O 3 : 25-38 %; and/or Gd 2 O 3 : 8-18%; and/or ZrO 2 : 1-8%; and/or ZnO: 8-18%; and/or WO 3 : 10-18%; and/or TiO 2 : 0.5-7%; and/or SiO 2 : 0.5-9%; and/or Y 2 O 3 : greater than 0 but less than or equal to 6%; and/or Yb 2 O 3 : 0-5%; and and/or Nb 2 O 5 : 0.5-6%; and/or Rn 2 O: 0-5%; and/or RO: 0-5%; and/or Al 2 O 3 : 0-2%; and/or Ta 2 O 5 : 0-2%; and/or clarifying agent: 0-0.5%, the Rn 2 O is one or more of Li 2 O, Na 2 O and K 2 O, and RO is MgO, One or more of CaO, SrO and BaO, and the clarifying agent is one or more of Sb 2 O 3 , SnO 2 , SnO and CeO 2 .
(8)根据(1)～(5)任一所述的光学玻璃，其组分以重量百分比表示，满足以下9种情形中的一种以上：(8) The optical glass according to any one of (1) to (5), wherein the components are expressed in weight percentage and satisfy one or more of the following nine situations:
1)Nb 2O 5/Y 2O 3为0.25～1.5； 1) Nb 2 O 5 /Y 2 O 3 is 0.25 to 1.5;
2)Y 2O 3/WO 3为0.1～0.6； 2) Y 2 O 3 /WO 3 is 0.1 to 0.6;
3)Y 2O 3/TiO 2为0.5～2.0； 3) Y 2 O 3 /TiO 2 is 0.5 to 2.0;
4)5×Nb 2O 5/(WO 3+Gd 2O 3)为0.1～1.0； 4) 5×Nb 2 O 5 /(WO 3 +Gd 2 O 3 ) is 0.1 to 1.0;
5)ZnO/La 2O 3为0.3～0.7； 5) ZnO/La 2 O 3 is 0.3～0.7;
6)Gd 2O 3/(La 2O 3+Y 2O 3)为0.25～0.65； 6) Gd 2 O 3 /(La 2 O 3 +Y 2 O 3 ) is 0.25 to 0.65;
7)(WO 3+ZnO)/(La 2O 3+TiO 2+ZrO 2)为0.6～0.9； 7) (WO 3 +ZnO)/(La 2 O 3 +TiO 2 +ZrO 2 ) is 0.6 to 0.9;
8)5×Li 2O/(TiO 2+SiO 2)为0.1～2.0； 8) 5×Li 2 O/(TiO 2 +SiO 2 ) is 0.1 to 2.0;
9)Nb 2O 5/WO 3为0.05～0.5。 9) Nb 2 O 5 /WO 3 is 0.05 to 0.5.
(9)根据(1)～(5)任一所述的光学玻璃，其组分以重量百分比表示，其中：B 2O 3：11～17％；和/或La 2O 3：28～35％；和/或Gd 2O 3：9.5～16％，优选Gd 2O 3：11～16％；和/或ZrO 2：2～6％；和/或ZnO：10～16％，优选ZnO：11～16％；和/或WO 3：12～17％；和/或TiO 2：1～5％；和/或SiO 2：1～8％，优选SiO 2：2～6％；和/或Y 2O 3：1～5％；和/或Yb 2O 3：0～2％；和/或Nb 2O 5：1～5％；和/或Rn 2O：0.5～3％；和/或RO：0～2％；和/或Al 2O 3：0～1％；和/或Ta 2O 5：0～1％；和/或澄清剂：0～0.1％，所述Rn 2O为Li 2O、Na 2O、K 2O中的一种或多种，RO为MgO、CaO、SrO、BaO中的一种或多种，澄清剂为Sb 2O 3、SnO 2、SnO、CeO 2中的一种或多种。 (9) The optical glass according to any one of (1) to (5), the components of which are expressed in weight percentage, wherein: B 2 O 3 : 11-17%; and/or La 2 O 3 : 28-35 %; and/or Gd 2 O 3 : 9.5-16%, preferably Gd 2 O 3 : 11-16%; and/or ZrO 2 : 2-6%; and/or ZnO: 10-16%, preferably ZnO: 11-16%; and/or WO 3 : 12-17%; and/or TiO 2 : 1-5%; and/or SiO 2 : 1-8%, preferably SiO 2 : 2-6%; and/or Y 2 O 3 : 1-5%; and/or Yb 2 O 3 : 0-2%; and/or Nb 2 O 5 : 1-5%; and/or Rn 2 O: 0.5-3%; and/or or RO: 0-2%; and/or Al 2 O 3 : 0-1%; and/or Ta 2 O 5 : 0-1%; and/or clarifying agent: 0-0.1%, the Rn 2 O It is one or more of Li 2 O, Na 2 O, K 2 O, RO is one or more of MgO, CaO, SrO, BaO, and the clarifying agent is Sb 2 O 3 , SnO 2 , SnO, One or more of CeO2.
(10)根据(1)～(5)任一所述的光学玻璃，其组分以重量百分比表示，满足以下9种情形中的一种以上：(10) The optical glass according to any one of (1) to (5), wherein the components are expressed in weight percentage and satisfy one or more of the following nine situations:
1)Nb 2O 5/Y 2O 3为0.3～0.8； 1) Nb 2 O 5 /Y 2 O 3 is 0.3 to 0.8;
2)Y 2O 3/WO 3为0.1～0.4； 2) Y 2 O 3 /WO 3 is 0.1 to 0.4;
3)Y 2O 3/TiO 2为0.8～1.3； 3) Y 2 O 3 /TiO 2 is 0.8 to 1.3;
4)5×Nb 2O 5/(WO 3+Gd 2O 3)为0.15～0.5； 4) 5×Nb 2 O 5 /(WO 3 +Gd 2 O 3 ) is 0.15 to 0.5;
5)ZnO/La 2O 3为0.35～0.65； 5) ZnO/La 2 O 3 is 0.35～0.65;
6)Gd 2O 3/(La 2O 3+Y 2O 3)为0.35～0.55； 6) Gd 2 O 3 /(La 2 O 3 +Y 2 O 3 ) is 0.35 to 0.55;
7)(WO 3+ZnO)/(La 2O 3+TiO 2+ZrO 2)为0.7～0.85； 7) (WO 3 +ZnO)/(La 2 O 3 +TiO 2 +ZrO 2 ) is 0.7-0.85;
8)5×Li 2O/(TiO 2+SiO 2)为0.2～1.0； 8) 5×Li 2 O/(TiO 2 +SiO 2 ) is 0.2 to 1.0;
9)Nb 2O 5/WO 3为0.06～0.4。 9) Nb 2 O 5 /WO 3 is 0.06 to 0.4.
(11)根据(1)～(5)任一所述的光学玻璃，其组分以重量百分比表示，满足以下5种情形中的一种以上：(11) The optical glass according to any one of (1) to (5), wherein the components are expressed in weight percentage and satisfy one or more of the following five situations:
1)Nb 2O 5/Y 2O 3为0.4～0.7； 1) Nb 2 O 5 /Y 2 O 3 is 0.4 to 0.7;
2)5×Nb 2O 5/(WO 3+Gd 2O 3)为0.2～0.4； 2) 5×Nb 2 O 5 /(WO 3 +Gd 2 O 3 ) is 0.2 to 0.4;
3)ZnO/La 2O 3为0.4～0.55； 3) ZnO/La 2 O 3 is 0.4～0.55;
4)5×Li 2O/(TiO 2+SiO 2)为0.3～0.8； 4) 5×Li 2 O/(TiO 2 +SiO 2 ) is 0.3-0.8;
5)Nb 2O 5/WO 3为0.08～0.3。 5) Nb 2 O 5 /WO 3 is 0.08 to 0.3.
(12)根据(1)～(5)任一所述的光学玻璃，其组分以重量百分比表示，其中：Li 2O：0～6％，优选Li 2O：大于0但小于或等于4％，更优选Li 2O：0.1～3％，进一步优选Li 2O：0.5～2％；和/或Na 2O：0～5％，优选Na 2O：0～3％，更优选Na 2O：0～2％；和/或K 2O：0～5％，优选K 2O：0～3％，更优选K 2O：0～2％。 (12) The optical glass according to any one of (1) to (5), whose components are expressed in weight percentage, wherein: Li 2 O: 0-6%, preferably Li 2 O: greater than 0 but less than or equal to 4 %, more preferably Li 2 O: 0.1-3%, further preferably Li 2 O: 0.5-2%; and/or Na 2 O: 0-5%, preferably Na 2 O: 0-3%, more preferably Na 2 O: 0 to 2%; and/or K 2 O: 0 to 5%, preferably K 2 O: 0 to 3%, more preferably K 2 O: 0 to 2%.
(13)根据(1)～(5)任一所述的光学玻璃，其组分中不含有Ta 2O 5；和/或不含有GeO 2；和/或不含有F；和/或不含有Al 2O 3；和/或不含有RO；和/或不含有P 2O 5；和/或不含有Bi 2O 3。 (13) The optical glass according to any one of (1) to (5), wherein the components do not contain Ta 2 O 5 ; and/or do not contain GeO 2 ; and/or do not contain F; and/or do not contain and/or no RO ; and/or no P2O5 ; and / or no Bi2O3 .
(14)根据(1)～(5)任一所述的光学玻璃，所述光学玻璃的折射率n d为1.85～1.91，优选为1.86～1.90，更优选为1.88～1.90；阿贝数ν d为32～38.5，优选为33～37.5，更优选为34～37。 (14) The optical glass according to any one of (1) to (5), wherein the optical glass has a refractive index n d of 1.85 to 1.91, preferably 1.86 to 1.90, more preferably 1.88 to 1.90; Abbe number ν d is 32-38.5, Preferably it is 33-37.5, More preferably, it is 34-37.
(15)根据(1)～(5)任一所述的光学玻璃，所述光学玻璃的耐酸作用稳定性D A为3类以上，优选为2类以上，更优选为1类；和/或耐水作用稳定性D W为2类以上，优选为1类；和/或密度ρ为5.50g/cm 3以下，优选为5.40g/cm 3以下，更优选为5.30g/cm 3以下，进一步优选为5.20g/cm 3以下；和/或λ 70小于或等于410nm，优选λ 70小于或等于405nm，更优选λ 70小于或等于400nm，进一步优选λ 70小于或等于395nm；和/或λ 5小于或等于375nm，优选λ 5小于或等于370nm，更优选λ 5小于或等于365nm，进一步优选λ 5为小于或等于360nm。 (15) The optical glass according to any one of (1) to (5), wherein the acid resistance stability D A of the optical glass is three or more types, preferably two or more types, and more preferably one type; and/or Water resistance stability D W is 2 or more types, preferably 1 type; and/or density ρ is 5.50 g/cm 3 or less, preferably 5.40 g/cm 3 or less, more preferably 5.30 g/cm 3 or less, still more preferably and/or λ 70 is less than or equal to 410nm, preferably λ 70 is less than or equal to 405nm, more preferably λ 70 is less than or equal to 400nm, further preferably λ 70 is less than or equal to 395nm; and/or λ 5 is less than or equal to 375 nm, preferably λ 5 is less than or equal to 370 nm, more preferably λ 5 is less than or equal to 365 nm, further preferably λ 5 is less than or equal to 360 nm.
(16)根据(1)～(5)任一所述的光学玻璃，所述光学玻璃的热膨胀系数α 100/300℃为100×10 -7/K以下，优选为95×10 -7/K以下，更优选为90×10 -7/K以下；和/或转变温度T g为620℃以下，优选为610℃以下，更优选为600℃以下；和/或析晶上限温度为1250℃以下，优选为1200℃以下，更优选为1180℃以下，进一步优选为1160℃以下。 (16) The optical glass according to any one of (1) to (5), wherein the thermal expansion coefficient α 100/300°C of the optical glass is 100×10 -7 /K or less, preferably 95×10 -7 /K below, more preferably below 90×10 -7 /K; and/or the transition temperature T g is below 620°C, preferably below 610°C, more preferably below 600°C; and/or the upper limit of crystallization temperature is below 1250°C , preferably 1200°C or lower, more preferably 1180°C or lower, still more preferably 1160°C or lower.
(17)玻璃预制件，采用(1)～(16)任一所述的光学玻璃制成。(17) A glass preform made of the optical glass described in any one of (1) to (16).
(18)光学元件，采用(1)～(16)任一所述的光学玻璃或(17)所述的玻璃预制件制成。(18) The optical element is made of the optical glass described in any one of (1) to (16) or the glass preform described in (17).
(19)光学仪器，含有(1)～(16)任一所述的光学玻璃，和/或含有(18)所述的光学元件。(19) An optical instrument comprising the optical glass described in any one of (1) to (16), and/or the optical element described in (18).
本发明的有益效果是：通过合理的组分设计，本发明获得的光学玻璃具有较低的转变温度和热膨胀系数，适于精密模压。The beneficial effects of the present invention are: through reasonable component design, the optical glass obtained by the present invention has lower transition temperature and thermal expansion coefficient, and is suitable for precision molding.
具体实施方式detailed description
下面，对本发明的光学玻璃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，本发明光学玻璃有时候简称为玻璃。Hereinafter, although embodiment of the optical glass of this invention is demonstrated in detail, this invention is not limited to the following embodiment, It can change suitably within the range of the objective of this invention, and can implement. In addition, although there are cases where descriptions are appropriately omitted regarding overlapping descriptions, this does not limit the gist of the invention. In the following, the optical glass of the present invention may be simply referred to as glass.
[光学玻璃][Optical glass]
下面对本发明光学玻璃的各组分(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，作为本发明的光学玻璃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％。The range of each component (component) of the optical glass of the present invention will be described below. In the present invention, unless otherwise specified, the content of each component and the total content are all expressed in weight percent (wt%), that is, the content and total content of each component are relative to the total glass substance of the composition converted into oxides. Amounts are expressed in weight percent. Here, the "composition in terms of oxides" refers to the case where oxides, complex salts, hydroxides, etc. used as raw materials of the optical glass composition of the present invention are decomposed and converted into oxides when melted. , and the total amount of the oxide is taken as 100%.
除非在具体情况下另外指出，本发明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。Unless otherwise indicated in a specific case, the recitation of numerical ranges herein includes both upper and lower limits, "above" and "below" include the endpoints, and all integers and fractions included within the range, without limitation The specific value listed when limiting the range. References herein to "and/or" are inclusive, such as "A and/or B", meaning only A, or only B, or both.
<必要组分和任选组分><Essential and optional components>
B 2O 3在本发明中是网络形成组分，可以改善玻璃的热稳定性，提高玻璃的熔融性，从而能够得到没有玻璃原料的熔融残留的玻璃，本发明中通过含有8％以上的B 2O 3以获得上述效果，优选B 2O 3的含量为10％以上，更优选B 2O 3的含量为11％以上。但当B 2O 3的含量过多时，玻璃的折射率降低，化学稳定性变差，因此本发明中B 2O 3的含量上限为20％，优选上限为18％，更优选上限为17％。 In the present invention, B 2 O 3 is a network forming component, which can improve the thermal stability of the glass and improve the melting property of the glass, so that the glass without the melting residue of the glass raw material can be obtained. In order to obtain the above effects, the content of B 2 O 3 is preferably 10% or more, and more preferably the content of B 2 O 3 is 11 % or more. However, when the content of B 2 O 3 is too large, the refractive index of the glass decreases and the chemical stability becomes poor. Therefore, the upper limit of the content of B 2 O 3 in the present invention is 20%, preferably 18%, and more preferably 17%. .
SiO 2具有改善玻璃化学稳定性、维持适于熔融玻璃成型的粘度、降低对耐火材料的侵蚀的作用，若其含量过高，玻璃的熔融难度增加，同时对降低玻璃的转变温度不利。因此本发明中SiO 2的含量为9％以下，优选为0.5～9％，更优选为1～8％，进一步优选为2～6％。 SiO 2 has the functions of improving the chemical stability of glass, maintaining the viscosity suitable for molten glass molding, and reducing the erosion of refractory materials. If its content is too high, the difficulty of melting the glass will increase, and it will be unfavorable to reduce the transition temperature of the glass. Therefore, in the present invention, the content of SiO 2 is 9% or less, preferably 0.5 to 9%, more preferably 1 to 8%, and further preferably 2 to 6%.
La 2O 3是一种高折射低色散组分，在玻璃中可以提高玻璃的折射率并调节色散，降低玻璃的高温粘度，本发明中La 2O 3的含量为21％以上，优选La 2O 3的含量为25％以上，更优选La 2O 3的含量为28％以上。另一方面，通过将La 2O 3的含量限定为40％以下，可通过提高玻璃的稳定性来降低玻璃的失透，并抑制折射率温度系数和阿贝数上升超过设计要求。因此，La 2O 3的含量为40％以下，优选为38％以下，更优选为35％以下。 La 2 O 3 is a high-refractive and low-dispersion component, which can increase the refractive index of the glass, adjust the dispersion, and reduce the high temperature viscosity of the glass. In the present invention, the content of La 2 O 3 is more than 21%, preferably La 2 The content of O 3 is 25% or more, and more preferably the content of La 2 O 3 is 28% or more. On the other hand, by limiting the content of La 2 O 3 to 40% or less, the devitrification of the glass can be reduced by improving the stability of the glass, and the temperature coefficient of refractive index and the Abbe number can be suppressed from rising beyond design requirements. Therefore, the content of La 2 O 3 is 40% or less, preferably 38% or less, and more preferably 35% or less.
在本发明中通过含有6％以上的Gd 2O 3，以改善光学玻璃的化学稳定性，并调整玻璃的热膨胀系数和折射率，优选Gd 2O 3的含量为8％以上，更优选Gd 2O 3的含量为9.5％以上，进一步优选Gd 2O 3的含量为11％以上。但当Gd 2O 3含量超过20％时，玻璃的耐失透性变差，玻璃的转变温度升高。因此，本发明中Gd 2O 3的含量20％以下，优选为18％以下，更优选为16％以下。 In the present invention, Gd 2 O 3 is contained in an amount of 6% or more to improve the chemical stability of the optical glass and adjust the thermal expansion coefficient and refractive index of the glass, preferably the content of Gd 2 O 3 is 8% or more, more preferably Gd 2 The content of O 3 is 9.5% or more, and more preferably the content of Gd 2 O 3 is 11% or more. However, when the Gd 2 O 3 content exceeds 20%, the devitrification resistance of the glass deteriorates, and the transition temperature of the glass increases. Therefore, in the present invention, the content of Gd 2 O 3 is 20% or less, preferably 18% or less, and more preferably 16% or less.
本发明中优选还含有10％以下的Y 2O 3，通过同时含有Y 2O 3与La 2O 3相配合，在维持高折射率和低色散的同时，改善玻璃的熔融性和耐失透性，若Y 2O 3的含量超过10％，玻璃的稳定性和耐失透性降低，转变温度升高。因此Y 2O 3的含量为0～10％，优选为大于0但小于或等于6％。在一些实施方式中，通过 含有1％以上的Y 2O 3，还可降低玻璃析晶上限温度和密度。因此，本发明中Y 2O 3的含量更优选为1～5％。 In the present invention, it is preferable to further contain 10% or less of Y 2 O 3 . By simultaneously containing Y 2 O 3 and La 2 O 3 in combination, the meltability and devitrification resistance of the glass are improved while maintaining high refractive index and low dispersion. If the content of Y 2 O 3 exceeds 10%, the stability and devitrification resistance of the glass decrease, and the transition temperature increases. Therefore, the content of Y 2 O 3 is 0 to 10%, preferably more than 0 but less than or equal to 6%. In some embodiments, by including 1% or more of Y 2 O 3 , the glass devitrification limit temperature and density can also be lowered. Therefore, the content of Y 2 O 3 in the present invention is more preferably 1 to 5%.
在一些实施方式中，若Gd 2O 3/(La 2O 3+Y 2O 3)低于0.2，玻璃的稳定性降低，折射率温度系数上升，玻璃在使用过程中受温度变化的影响变大；若Gd 2O 3/(La 2O 3+Y 2O 3)超过0.8，玻璃的磨耗度变差，密度增加。因此，优选Gd 2O 3/(La 2O 3+Y 2O 3)为0.2～0.8，更优选Gd 2O 3/(La 2O 3+Y 2O 3)为0.25～0.65，进一步优选Gd 2O 3/(La 2O 3+Y 2O 3)为0.35～0.55。 In some embodiments, if Gd 2 O 3 /(La 2 O 3 +Y 2 O 3 ) is lower than 0.2, the stability of the glass is reduced, the temperature coefficient of refractive index is increased, and the glass is affected by temperature changes during use. large; when Gd 2 O 3 /(La 2 O 3 +Y 2 O 3 ) exceeds 0.8, the abrasion degree of the glass deteriorates and the density increases. Therefore, Gd 2 O 3 /(La 2 O 3 +Y 2 O 3 ) is preferably 0.2 to 0.8, more preferably Gd 2 O 3 /(La 2 O 3 +Y 2 O 3 ) is 0.25 to 0.65, and still more preferably Gd 2 O 3 /(La 2 O 3 +Y 2 O 3 ) is 0.35 to 0.55.
Yb 2O 3也是一种赋予玻璃高折射低色散性能的组分，在本发明中是一种任选组分，当其含量超过10％时，玻璃的抗析晶性能和化学稳定性下降，因此Yb 2O 3的含量限定为0～10％，优选为0～5％，更优选为0～2％，进一步优选不含有Yb 2O 3。 Yb 2 O 3 is also a component that imparts high refraction and low dispersion properties to glass, and is an optional component in the present invention. When its content exceeds 10%, the anti-devitrification properties and chemical stability of the glass decrease, Therefore, the content of Yb 2 O 3 is limited to 0 to 10%, preferably 0 to 5%, more preferably 0 to 2%, and further preferably not containing Yb 2 O 3 .
ZnO在本发明体系玻璃中，可以调整玻璃的折射率和色散，降低转变温度，改善玻璃的抗析晶性能，提高玻璃的稳定性，同时ZnO还可以降低玻璃的高温粘度，使得玻璃可以在较低温度下熔炼，从而可以提高玻璃的透过率。本发明中通过含有7％以上的ZnO以获得上述效果，优选ZnO的含量为8％以上，更优选ZnO的含量为10％以上，进一步优选ZnO的含量为11％以上。另一方面，若ZnO的含量高于20％，玻璃磨耗度变差，成型难度增加，玻璃的抗析晶性能变差。因此，ZnO含量限定为20％以下，优选为18％以下，更优选为16％以下。In the glass system of the present invention, ZnO can adjust the refractive index and dispersion of the glass, reduce the transition temperature, improve the anti-devitrification performance of the glass, and improve the stability of the glass. Melting at low temperature, which can improve the transmittance of glass. In the present invention, the above effects are obtained by containing 7% or more of ZnO, preferably 8% or more, more preferably 10% or more, and even more preferably 11% or more. On the other hand, when the content of ZnO is higher than 20%, the abrasion degree of the glass is deteriorated, the molding difficulty is increased, and the devitrification resistance of the glass is deteriorated. Therefore, the ZnO content is limited to 20% or less, preferably 18% or less, and more preferably 16% or less.
在本发明的一些实施方式中，通过使ZnO的含量与La 2O 3的含量之间的比例ZnO/La 2O 3在0.2以上，可以改善玻璃的化学稳定性和折射率温度系数，但若ZnO/La 2O 3超过0.8，玻璃的抗析晶性能下降。因此，优选ZnO/La 2O 3为0.2～0.8，更优选ZnO/La 2O 3为0.3～0.7，进一步优选ZnO/La 2O 3为0.35～0.65，更进一步优选ZnO/La 2O 3为0.4～0.55。 In some embodiments of the present invention, by setting the ratio ZnO/La 2 O 3 between the content of ZnO and the content of La 2 O 3 to be 0.2 or more, the chemical stability and the temperature coefficient of refractive index of the glass can be improved, but if When ZnO/La 2 O 3 exceeds 0.8, the devitrification resistance of the glass decreases. Therefore, ZnO/La 2 O 3 is preferably 0.2 to 0.8, more preferably ZnO/La 2 O 3 is 0.3 to 0.7, still more preferably ZnO/La 2 O 3 is 0.35 to 0.65, and still more preferably ZnO/La 2 O 3 is 0.4 to 0.55.
WO 3可提高玻璃折射率和机械强度，降低玻璃的转变温度，本发明中通过含有8％以上的WO 3以获得上述效果，优选WO 3的含量下限为10％，更优选WO 3的含量下限为12％。若WO 3的含量超过20％，玻璃的热稳定性下降，耐失透性 降低。因此，WO 3的含量上限为20％，优选上限为18％，更优选上限为17％。 WO 3 can improve the refractive index and mechanical strength of the glass, and reduce the transition temperature of the glass. In the present invention, the above effects are obtained by containing more than 8% of WO 3 , preferably the lower limit of the content of WO 3 is 10%, more preferably the lower limit of the content of WO 3 to 12%. When the content of WO 3 exceeds 20%, the thermal stability of the glass decreases, and the devitrification resistance decreases. Therefore, the upper limit of the content of WO 3 is 20%, preferably 18%, and more preferably 17%.
在本发明的一些实施方式中，若Y 2O 3/WO 3低于0.05，玻璃的密度上升，不利于实现玻璃的轻量化，若Y 2O 3/WO 3超过1.0，玻璃的热稳定性下降。因此，优选Y 2O 3/WO 3为0.05～1.0，更优选Y 2O 3/WO 3为0.1～0.6，进一步优选Y 2O 3/WO 3为0.1～0.4。 In some embodiments of the present invention, if Y 2 O 3 /WO 3 is less than 0.05, the density of the glass increases, which is not conducive to realizing the lightweight of the glass, and if the Y 2 O 3 /WO 3 exceeds 1.0, the thermal stability of the glass decline. Therefore, Y 2 O 3 /WO 3 is preferably 0.05 to 1.0, more preferably Y 2 O 3 /WO 3 is 0.1 to 0.6, and still more preferably Y 2 O 3 /WO 3 is 0.1 to 0.4.
Nb 2O 5是高折射高色散组分，可以提高玻璃的折射率和耐失透性，降低玻璃的热膨胀系数，若Nb 2O 5的含量过高，玻璃的热稳定性和化学稳定性降低，光透过率下降。因此，本发明中Nb 2O 5的含量为0～8％，优选为0.5～6％，更优选为1～5％。 Nb 2 O 5 is a high refractive index and high dispersion component, which can improve the refractive index and devitrification resistance of the glass, and reduce the thermal expansion coefficient of the glass. If the content of Nb 2 O 5 is too high, the thermal stability and chemical stability of the glass will be reduced. , the light transmittance decreases. Therefore, the content of Nb 2 O 5 in the present invention is 0 to 8%, preferably 0.5 to 6%, and more preferably 1 to 5%.
发明人通过大量实验研究发现，在本发明的一些实施方式中，Nb 2O 5、WO 3和Gd 2O 3在玻璃中会产生复杂的协同作用，尤其是使5×Nb 2O 5/(WO 3+Gd 2O 3)在0.05～1.5范围内，玻璃在获得良好的热压稳定性的同时，还可具有适宜的磨耗度，优选5×Nb 2O 5/(WO 3+Gd 2O 3)为0.1～1.0。进一步的，通过使5×Nb 2O 5/(WO 3+Gd 2O 3)在0.15～0.5范围内，还可进一步优化玻璃的热膨胀系数，因此更优选5×Nb 2O 5/(WO 3+Gd 2O 3)为0.15～0.5，进一步优选5×Nb 2O 5/(WO 3+Gd 2O 3)为0.2～0.4。 The inventor found through extensive experimental research that, in some embodiments of the present invention, Nb 2 O 5 , WO 3 and Gd 2 O 3 can produce a complex synergistic effect in glass, especially to make 5×Nb 2 O 5 /( When WO 3 +Gd 2 O 3 ) is in the range of 0.05 to 1.5, the glass can obtain good hot-press stability and at the same time have a suitable degree of abrasion, preferably 5×Nb 2 O 5 /(WO 3 +Gd 2 O 3 ) is 0.1 to 1.0. Furthermore, by setting 5×Nb 2 O 5 /(WO 3 +Gd 2 O 3 ) in the range of 0.15 to 0.5, the thermal expansion coefficient of the glass can be further optimized, so 5×Nb 2 O 5 /(WO 3 +Gd 2 O 3 ) is 0.15 to 0.5, more preferably 5×Nb 2 O 5 /(WO 3 +Gd 2 O 3 ) is 0.2 to 0.4.
在本发明的一些实施方式中，使Nb 2O 5/Y 2O 3在0.1以上，有助于提高玻璃的抗析晶性能，但若Nb 2O 5/Y 2O 3超过2.5，玻璃的着色倾向增加，光透过率下降。因此，优选Nb 2O 5/Y 2O 3为0.1～2.5，更优选Nb 2O 5/Y 2O 3为0.25～1.5，进一步优选Nb 2O 5/Y 2O 3为0.3～0.8，更进一步优选Nb 2O 5/Y 2O 3为0.4～0.7。 In some embodiments of the present invention, making Nb 2 O 5 /Y 2 O 3 more than 0.1 helps to improve the devitrification resistance of the glass, but if Nb 2 O 5 /Y 2 O 3 exceeds 2.5, the The coloring tendency increases and the light transmittance decreases. Therefore, Nb 2 O 5 /Y 2 O 3 is preferably 0.1 to 2.5, more preferably Nb 2 O 5 /Y 2 O 3 is 0.25 to 1.5, still more preferably Nb 2 O 5 /Y 2 O 3 is 0.3 to 0.8, and more preferably More preferably, Nb 2 O 5 /Y 2 O 3 is 0.4 to 0.7.
在本发明的一些实施方式中，通过使Nb 2O 5/WO 3在0.03～0.7范围内，有助于提高玻璃的热稳定性，优化玻璃的化学稳定性，优选Nb 2O 5/WO 3为0.05～0.5，更优选Nb 2O 5/WO 3为0.06～0.4，进一步优选Nb 2O 5/WO 3为0.08～0.3。 In some embodiments of the present invention, by setting Nb 2 O 5 /WO 3 in the range of 0.03-0.7, it helps to improve the thermal stability of the glass and optimize the chemical stability of the glass, preferably Nb 2 O 5 /WO 3 It is 0.05-0.5, it is more preferable that Nb2O5 /WO3 is 0.06-0.4 , and it is more preferable that Nb2O5 / WO3 is 0.08-0.3 .
TiO 2具有提高玻璃折射率和色散的作用，适量含有可使玻璃更稳定并降低玻璃的粘度。但TiO 2含量超过10％，玻璃的析晶倾向增加，玻璃的转变温度上升，同时玻璃加压成型时变得容易着色。因此，本发明中TiO 2的 含量为大于0但小于或等于10％，优选TiO 2的含量为0.5～7％，更优选为1～5％。 TiO 2 has the effect of increasing the refractive index and dispersion of glass, and an appropriate amount can make the glass more stable and reduce the viscosity of the glass. However, when the content of TiO 2 exceeds 10%, the crystallization tendency of the glass increases, the transition temperature of the glass increases, and the glass becomes easy to be colored during press molding. Therefore, in the present invention, the content of TiO 2 is greater than 0 but less than or equal to 10%, preferably the content of TiO 2 is 0.5-7%, more preferably 1-5%.
在本发明的一些实施方式中，通过控制Y 2O 3的含量与TiO 2的含量之间的比例Y 2O 3/TiO 2在0.2以上，可改善玻璃的耐候性，但若Y 2O 3/TiO 2超过3.5，玻璃的气泡度变差，硬度下降。因此优选Y 2O 3/TiO 2为0.2～3.5，更优选Y 2O 3/TiO 2为0.5～2.0，进一步优选Y 2O 3/TiO 2为0.8～1.3。 In some embodiments of the present invention, by controlling the ratio between the content of Y 2 O 3 and the content of TiO 2 Y 2 O 3 /TiO 2 to be above 0.2, the weather resistance of the glass can be improved, but if Y 2 O 3 When /TiO 2 exceeds 3.5, the degree of bubbles of the glass deteriorates and the hardness decreases. Therefore, Y 2 O 3 /TiO 2 is preferably 0.2 to 3.5, more preferably Y 2 O 3 /TiO 2 is 0.5 to 2.0, and still more preferably Y 2 O 3 /TiO 2 is 0.8 to 1.3.
ZrO 2是一种高折射低色散组分，在玻璃中可以提高玻璃的折射率并调节色散，提高玻璃的抗析晶性能，本发明中通过含有1％以上的ZrO 2以获得上述效果，优选ZrO 2的含量为2％以上。若ZrO 2的含量高于10％，玻璃熔化难度增加，熔炼温度上升，进一步的，还会导致玻璃内部出现夹杂物及透过率下降。因此，ZrO 2含量为10％以下，优选为8％以下，更优选为6％以下。 ZrO 2 is a high-refractive and low-dispersion component, which can increase the refractive index of the glass, adjust the dispersion, and improve the anti-devitrification performance of the glass. In the present invention, the above effects are obtained by containing more than 1% ZrO 2 , preferably The content of ZrO 2 is 2% or more. If the content of ZrO 2 is higher than 10%, the difficulty of melting the glass will increase, the melting temperature will increase, and further, inclusions will appear in the glass and the transmittance will decrease. Therefore, the ZrO 2 content is 10% or less, preferably 8% or less, and more preferably 6% or less.
在本发明的一些实施方式中，通过控制WO 3和ZnO的合计含量WO 3+ZnO与La 2O 3、TiO 2、ZrO 2的合计含量La 2O 3+TiO 2+ZrO 2之间的比例(WO 3+ZnO)/(La 2O 3+TiO 2+ZrO 2)在0.3～1.5范围内，玻璃可以在具有较低转变温度的同时，获得较低的热膨胀系数。因此，本发明中优选(WO 3+ZnO)/(La 2O 3+TiO 2+ZrO 2)为0.3～1.5，更优选(WO 3+ZnO)/(La 2O 3+TiO 2+ZrO 2)为0.5～1.0。进一步的，通过控制(WO 3+ZnO)/(La 2O 3+TiO 2+ZrO 2)在0.6～0.9范围内，还可进一步优化玻璃的气泡度和磨耗度，因此进一步优选(WO 3+ZnO)/(La 2O 3+TiO 2+ZrO 2)为0.6～0.9，更进一步优选(WO 3+ZnO)/(La 2O 3+TiO 2+ZrO 2)为0.7～0.85。 In some embodiments of the present invention, by controlling the ratio between the total content of WO 3 and ZnO WO 3 +ZnO and the total content of La 2 O 3 , TiO 2 and ZrO 2 La 2 O 3 +TiO 2 +ZrO 2 When (WO 3 +ZnO)/(La 2 O 3 +TiO 2 +ZrO 2 ) is in the range of 0.3 to 1.5, the glass can obtain a lower thermal expansion coefficient while having a lower transition temperature. Therefore, in the present invention, (WO 3 +ZnO)/(La 2 O 3 +TiO 2 +ZrO 2 ) is preferably 0.3 to 1.5, more preferably (WO 3 +ZnO)/(La 2 O 3 +TiO 2 +ZrO 2 ) is 0.5 to 1.0. Further, by controlling (WO 3 +ZnO)/(La 2 O 3 +TiO 2 +ZrO 2 ) in the range of 0.6 to 0.9, the bubble degree and abrasion degree of the glass can be further optimized, so (WO 3 + ZnO)/(La 2 O 3 +TiO 2 +ZrO 2 ) is 0.6 to 0.9, and more preferably (WO 3 +ZnO)/(La 2 O 3 +TiO 2 +ZrO 2 ) is 0.7 to 0.85.
Rn 2O是碱金属氧化物，Rn 2O为Li 2O、Na 2O、K 2O中的一种或多种，可以改善玻璃的熔融性，降低玻璃的转变温度，当Rn 2O的含量超过10％时，玻璃耐失透性变差，折射率大幅降低。因此，本发明Rn 2O含量为0～10％，优选为0～5％，更优选为0.5～3％。 Rn 2 O is an alkali metal oxide , and Rn 2 O is one or more of Li 2 O, Na 2 O and K 2 O, which can improve the melting property of glass and lower the transition temperature of glass. When the content exceeds 10%, the devitrification resistance of the glass deteriorates, and the refractive index decreases significantly. Therefore, in the present invention, the Rn 2 O content is 0 to 10%, preferably 0 to 5%, and more preferably 0.5 to 3%.
Li 2O可以降低玻璃的转变温度，但其含量高时对玻璃的耐酸稳定性和热膨胀系数不利，因此，本发明中Li 2O的含量为6％以下，优选为大于0但小于或等于4％，更优选为0.1～3％，进一步优选为0.5～2％。 Li 2 O can reduce the transition temperature of glass, but when its content is high, it is unfavorable to the acid resistance stability and thermal expansion coefficient of the glass. Therefore, the content of Li 2 O in the present invention is 6% or less, preferably greater than 0 but less than or equal to 4 %, more preferably 0.1 to 3%, still more preferably 0.5 to 2%.
在本发明的一些实施方式中，通过使5×Li 2O/(TiO 2+SiO 2)的值在0.05～5.0范围内，可优化玻璃的粘度，改善玻璃的条纹度和气泡度，优选5×Li 2O/(TiO 2+SiO 2)为0.1～2.0。进一步的，使5×Li 2O/(TiO 2+SiO 2)的值在0.2～1.0范围内，还可明显改善玻璃的模压性能，降低压型过程中玻璃起雾的发生概率。因此更优选5×Li 2O/(TiO 2+SiO 2)为0.2～1.0，进一步优选5×Li 2O/(TiO 2+SiO 2)为0.3～0.8。 In some embodiments of the present invention, by setting the value of 5×Li 2 O/(TiO 2 +SiO 2 ) in the range of 0.05 to 5.0, the viscosity of the glass can be optimized, and the striae degree and the bubble degree of the glass can be improved, preferably 5 ×Li 2 O/(TiO 2 +SiO 2 ) is 0.1 to 2.0. Further, setting the value of 5×Li 2 O/(TiO 2 +SiO 2 ) in the range of 0.2 to 1.0 can significantly improve the moldability of the glass and reduce the probability of fogging of the glass during the molding process. Therefore, 5×Li 2 O/(TiO 2 +SiO 2 ) is more preferably 0.2 to 1.0, and still more preferably 5×Li 2 O/(TiO 2 +SiO 2 ) is 0.3 to 0.8.
Na 2O具有改善玻璃熔融性的作用，可以提高玻璃熔制效果，同时还可降低玻璃的转变温度，若Na 2O含量超过5％，玻璃的化学稳定性和耐候性降低，因此Na 2O的含量为0～5％，优选Na 2O的含量为0～3％，更优选Na 2O的含量为0～2％。 Na 2 O has the effect of improving the melting property of glass, which can improve the melting effect of glass and lower the transition temperature of glass. If the content of Na 2 O exceeds 5 %, the chemical stability and weather resistance of glass will be reduced. The content of Na 2 O is 0-5%, preferably the content of Na 2 O is 0-3%, and the content of Na 2 O is more preferably 0-2%.
K 2O具有改善玻璃热稳定性和熔融性的作用，但其含量超过5％，玻璃的耐失透性下降，玻璃化学稳定性恶化，因此本发明中K 2O的含量为5％以下，优选K 2O的含量为0～3％，更优选为0～2％。 K 2 O has the effect of improving the thermal stability and melting properties of glass, but if its content exceeds 5%, the devitrification resistance of the glass decreases, and the chemical stability of the glass deteriorates. Therefore, the content of K 2 O in the present invention is 5% or less, The content of K 2 O is preferably 0 to 3%, more preferably 0 to 2%.
RO是碱土金属氧化物，RO为MgO、CaO、SrO、BaO中的一种或多种。RO加入玻璃中可以改善玻璃的熔融性，降低玻璃的转变温度，若RO的含量超过10％，玻璃的耐失透性降低。因此，本发明RO含量为0～10％，优选为0～5％，更优选为0～2％，进一步优选不含有RO。RO is an alkaline earth metal oxide, and RO is one or more of MgO, CaO, SrO, and BaO. Adding RO into the glass can improve the melting property of the glass and lower the transition temperature of the glass. If the content of RO exceeds 10%, the devitrification resistance of the glass will decrease. Therefore, in the present invention, the RO content is 0 to 10%, preferably 0 to 5%, more preferably 0 to 2%, and further preferably no RO is contained.
Al 2O 3能改善玻璃的化学稳定性，但其含量超过5％时，玻璃的熔融性和透过率变差。因此，本发明Al 2O 3的含量为0～5％，优选为0～2％，更优选为0～1％，进一步优选不含有Al 2O 3。 Al 2 O 3 can improve the chemical stability of glass, but when its content exceeds 5%, the meltability and transmittance of the glass deteriorate. Therefore, the content of Al 2 O 3 in the present invention is 0 to 5%, preferably 0 to 2%, more preferably 0 to 1%, and further preferably not containing Al 2 O 3 .
Ta 2O 5具有提高折射率、提升玻璃耐失透性能的作用，但其含量过高，玻璃的化学稳定性下降，且光学常数难以控制到期望的范围；另一方面，与其他成分相比，Ta 2O 5的价格非常昂贵，从实用以及成本的角度考虑，应尽量减少其使用量。因此，本发明的Ta 2O 5含量限定为0～5％，优选为0～2％，更优选为0～1％，进一步优选不含有Ta 2O 5。 Ta 2 O 5 has the functions of increasing the refractive index and improving the devitrification resistance of the glass, but if its content is too high, the chemical stability of the glass decreases, and the optical constant is difficult to control to the desired range; on the other hand, compared with other components , Ta 2 O 5 is very expensive, from the practical and cost point of view, its usage should be minimized. Therefore, the Ta 2 O 5 content in the present invention is limited to 0 to 5%, preferably 0 to 2%, more preferably 0 to 1%, and further preferably not containing Ta 2 O 5 .
本发明中通过添加0～1％的Sb 2O 3、SnO、SnO 2、CeO 2组分中的一种或多种作为澄清剂，可以提高玻璃的澄清效果，优选澄清剂的含量为0～0.5％， 更优选为0～0.1％。当Sb 2O 3含量超过1％时，玻璃有澄清性能降低的倾向，同时由于其强氧化作用促进了熔制玻璃的铂金或铂合金器皿的腐蚀以及成型模具的恶化，因此本发明优选Sb 2O 3的添加量为0～1％，更优选为0～0.5％，进一步优选0～0.1％。SnO和SnO 2也可以作为澄清剂来添加，但当其含量超过1％时，则玻璃着色倾向增加，或者当加热、软化玻璃并进行模压成形等再次成形时，Sn会成为晶核生成的起点，产生失透的倾向。因此本发明的SnO 2的含量优选为0～1％，更优选为0～0.5，进一步优选0～0.1％，更进一步优选不含有；SnO的含量优选为0～1％，更优选为0～0.5％，进一步优选0～0.1％，更进一步优选不含有。CeO 2的作用及添加量比例与SnO 2一致，其含量优选为0～1％，更优选为0～0.5％，进一步优选0～0.1％，更进一步优选不含有。 In the present invention, by adding 0-1% of one or more of Sb 2 O 3 , SnO, SnO 2 , and CeO 2 components as a clarifying agent, the clarifying effect of the glass can be improved, and the content of the clarifying agent is preferably 0- 0.5%, more preferably 0 to 0.1%. When the content of Sb 2 O 3 exceeds 1%, the glass tends to reduce the refining performance, and at the same time, due to its strong oxidation effect, it promotes the corrosion of the platinum or platinum alloy utensils in which the glass is melted and the deterioration of the forming mold. Therefore, Sb 2 is preferred in the present invention. The addition amount of O 3 is 0 to 1%, more preferably 0 to 0.5%, still more preferably 0 to 0.1%. SnO and SnO 2 can also be added as fining agents, but when the content exceeds 1%, the tendency to color the glass increases, or when the glass is heated, softened and reshaped by press molding, Sn will become the origin of crystal nucleation , resulting in a tendency to devitrification. Therefore, the content of SnO 2 in the present invention is preferably 0-1%, more preferably 0-0.5, still more preferably 0-0.1%, and even more preferably not contained; the content of SnO is preferably 0-1%, more preferably 0- 0.5%, more preferably 0 to 0.1%, and still more preferably not contained. The function and addition ratio of CeO 2 are the same as those of SnO 2 , and its content is preferably 0 to 1%, more preferably 0 to 0.5%, still more preferably 0 to 0.1%, and still more preferably not contained.
在本发明的玻璃中可以含有适量的F(氟)，但在一些实施方式中，F会导致玻璃稳定性变差，耐失透性下降，同时其挥发性会导致玻璃光学常数不稳定和条纹度变差，因此优选不含有F。Appropriate amounts of F (fluorine) can be included in the glasses of the present invention, but in some embodiments, F can lead to poor glass stability and reduced devitrification resistance, while its volatility can lead to unstable glass optical constants and streaks Since the degree of intensity deteriorates, it is preferable not to contain F.
在本发明的玻璃中可以含有适量的GeO 2，但在一些实施方式中，GeO 2的引入会导致玻璃透过率降低，同时由于它是价格昂贵的原料，降低了玻璃的经济性，因此优选不含有GeO 2。 An appropriate amount of GeO 2 can be contained in the glass of the present invention, but in some embodiments, the introduction of GeO 2 will lead to a decrease in the transmittance of the glass, and at the same time, since it is an expensive raw material, it reduces the economy of the glass, so it is preferred Does not contain GeO 2 .
在本发明的玻璃中可以含有适量的P 2O 5，但在一些实施方式中，玻璃中含有P 2O 5导致较难获得期望的高折射率，且玻璃的耐失透性降低，因此优选不含有P 2O 5。 An appropriate amount of P 2 O 5 may be contained in the glass of the present invention, but in some embodiments, the inclusion of P 2 O 5 in the glass makes it difficult to obtain a desired high refractive index, and the devitrification resistance of the glass decreases, so it is preferred Does not contain P 2 O 5 .
在本发明的玻璃中可以含有适量的Bi 2O 3，但在一些实施方式中，Bi 2O 3会导致玻璃的光透过率降低，磨耗度和化学稳定性变差，密度明显增大，因此优选不含有Bi 2O 3。 An appropriate amount of Bi 2 O 3 may be contained in the glass of the present invention, but in some embodiments, Bi 2 O 3 will reduce the light transmittance of the glass, deteriorate the abrasion degree and chemical stability, and significantly increase the density, Therefore, it is preferable not to contain Bi 2 O 3 .
<不应含有的组分><Ingredients that should not be contained>
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光学玻璃，优选实际上不含有。In the glass of the present invention, even if the oxides of transition metals such as V, Cr, Mn, Fe, Co, Ni, Cu, Ag, and Mo are contained in small amounts alone or in combination, the glass will be colored, and in the visible light region Specified wavelengths are absorbed, thereby weakening the property of the present invention to improve the visible light transmittance effect. Therefore, it is preferable not to actually contain the optical glass, which requires transmittance at wavelengths in the visible light region.
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，光学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，本发明的光学玻璃也能够进行制造、加工以及废弃。Oxides of Th, Cd, Tl, Os, Be, and Se tend to be used in a controlled manner as harmful chemical substances in recent years, and they are environmentally friendly not only in the manufacturing process of glass, but also in the processing process and disposal after productization. Action is required. Therefore, in the case of attaching importance to the influence on the environment, it is preferable not to actually contain them except for unavoidable mixing. Thereby, the optical glass becomes practically free of substances that pollute the environment. Therefore, the optical glass of the present invention can be manufactured, processed, and discarded without taking special measures for environmental measures.
为了实现环境友好，本发明的光学玻璃优选不含有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。 In order to achieve environmental friendliness, the optical glass of the present invention preferably does not contain As 2 O 3 and PbO. Although As 2 O 3 has the effect of eliminating bubbles and preventing glass coloration, the addition of As 2 O 3 will increase the platinum erosion of the glass to the furnace, especially the platinum furnace, resulting in more platinum ions entering the glass. The service life of the platinum furnace is adversely affected.
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光学玻璃中；但作为生产光学玻璃的原材料和/或设备，会存在某些不是故意添加的杂质或组分，会在最终的光学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。"Does not contain" and "0%" described herein means that the compound, molecule or element, etc. is not intentionally added as a raw material to the optical glass of the present invention; however, as a raw material and/or equipment for producing optical glass, there may be some Impurities or components that are not intentionally added will be contained in a small or trace amount in the final optical glass, and this situation is also within the protection scope of the patent of the present invention.
下面，对本发明的光学玻璃的性能进行说明。Next, the performance of the optical glass of this invention is demonstrated.
<折射率与阿贝数><Refractive Index and Abbe Number>
光学玻璃的折射率(n d)与阿贝数(ν d)按照GB/T 7962.1—2010规定的方法测试。 The refractive index (n d ) and Abbe number (ν d ) of optical glass are tested according to the methods specified in GB/T 7962.1-2010.
在一些实施方式中，本发明光学玻璃的折射率(n d)的下限为1.85，优选下限为1.86，更优选下限为1.88；折射率(n d)的上限为1.91，优选上限为1.90。 In some embodiments, the lower limit of the refractive index (n d ) of the optical glass of the present invention is 1.85, preferably the lower limit is 1.86, and more preferably the lower limit is 1.88; the upper limit of the refractive index (n d ) is 1.91, preferably 1.90.
在一些实施方式中，本发明光学玻璃的阿贝数(ν d)的下限为32，优选下限为33，更优选下限为34；阿贝数(ν d)的上限为38.5，优选上限为37.5，更优选上限为37。 In some embodiments, the lower limit of the Abbe number (ν d ) of the optical glass of the present invention is 32, preferably the lower limit is 33, and more preferably the lower limit is 34; the upper limit of the Abbe number (ν d ) is 38.5, and the preferred upper limit is 37.5 , more preferably the upper limit is 37.
<密度><density>
光学玻璃的密度(ρ)按GB/T7962.20-2010规定的方法进行测试。The density (ρ) of optical glass is tested according to the method specified in GB/T7962.20-2010.
在一些实施方式中，本发明光学玻璃的密度(ρ)为5.50g/cm 3以下，优选为5.40g/cm 3以下,更优选为5.30g/cm 3以下，进一步优选为5.20g/cm 3以下。 In some embodiments, the density (ρ) of the optical glass of the present invention is 5.50 g/cm 3 or less, preferably 5.40 g/cm 3 or less, more preferably 5.30 g/cm 3 or less, and even more preferably 5.20 g/cm 3 the following.
<热膨胀系数><Coefficient of Thermal Expansion>
光学玻璃的热膨胀系数(α 100/300℃)按照GB/T7962.16-2010规定的方法进行测试100～300℃的数据。 The thermal expansion coefficient (α 100/300°C ) of the optical glass is tested according to the method specified in GB/T7962.16-2010 at 100-300°C.
在一些实施方式中，本发明的光学玻璃的热膨胀系数(α 100/300℃)为100×10 -7/K以下，优选为95×10 -7/K以下，更优选为90×10 -7/K以下。 In some embodiments, the thermal expansion coefficient (α 100/300°C ) of the optical glass of the present invention is 100×10 -7 /K or less, preferably 95×10 -7 /K or less, more preferably 90×10 -7 /K or less.
<转变温度><Transition temperature>
光学玻璃的转变温度(T g)按GB/T7962.16-2010规定的方法进行测试。 The transition temperature (T g ) of the optical glass is tested according to the method specified in GB/T7962.16-2010.
在一些实施方式中，本发明光学玻璃的转变温度(T g)为620℃以下，优选为610℃以下，更优选为600℃以下。 In some embodiments, the transition temperature (T g ) of the optical glass of the present invention is 620°C or lower, preferably 610°C or lower, and more preferably 600°C or lower.
<着色度><coloration degree>
本发明玻璃的短波透射光谱特性用着色度(λ 70和λ 5)表示。λ 70是指玻璃透射比达到70％时对应的波长。λ 70的测定是使用具有彼此平行且光学抛光的两个相对平面的厚度为10±0.1mm的玻璃，测定从280nm到700nm的波长域内的分光透射率并表现出透射率70％的波长。所谓分光透射率或透射率是在向玻璃的上述表面垂直地入射强度I in的光，透过玻璃并从一个平面射出强度I out的光的情况下通过I out/I in表示的量，并且也包含了玻璃的上述表面上的表面反射损失的透射率。玻璃的折射率越高，表面反射损失越大。因此，在高折射率玻璃中，λ 70的值小意味着玻璃自身的着色极少，光透过率高。 The short-wave transmission spectral properties of the glasses of the present invention are expressed in terms of tinting degrees (λ 70 and λ 5 ). λ 70 refers to the wavelength corresponding to the glass transmittance of 70%. λ 70 was measured by measuring the spectral transmittance in the wavelength range from 280 nm to 700 nm using glass with a thickness of 10±0.1 mm having two opposite planes parallel to each other and optically polished and showing a wavelength of 70% transmittance. The so-called spectral transmittance or transmittance is the amount expressed by I out /I in when light of the intensity I in is incident perpendicularly to the above-mentioned surface of the glass, passes through the glass, and emits light of the intensity I out from one plane, and The transmittance of the surface reflection loss on the above-mentioned surface of the glass is also included. The higher the refractive index of the glass, the greater the surface reflection loss. Therefore, in the high refractive index glass, a small value of λ 70 means that the coloring of the glass itself is extremely small and the light transmittance is high.
在一些实施方式中，本发明的光学玻璃的λ 70小于或等于410nm，优选λ 70为小于或等于405nm，更优选λ 70小于或等于400nm，进一步优选λ 70小于或等于395nm。 In some embodiments, λ 70 of the optical glass of the present invention is less than or equal to 410 nm, preferably λ 70 is less than or equal to 405 nm, more preferably λ 70 is less than or equal to 400 nm, further preferably λ 70 is less than or equal to 395 nm.
在一些实施方式中，本发明的光学玻璃的λ 5小于或等于375nm，优选λ 5为小于或等于370nm，更优选λ 5为小于或等于365nm，进一步优选λ 5为小于或等于360nm。 In some embodiments, λ 5 of the optical glass of the present invention is less than or equal to 375 nm, preferably λ 5 is less than or equal to 370 nm, more preferably λ 5 is less than or equal to 365 nm, further preferably λ 5 is less than or equal to 360 nm.
<耐酸作用稳定性><Acid resistance stability>
光学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。 The acid resistance stability (D A ) (powder method) of optical glass is tested according to the method specified in GB/T 17129.
在一些实施方式中，本发明光学玻璃的耐酸作用稳定性(D A)为3类以上，优选为2类以上，更优选为1类。 In some embodiments, the acid resistance stability (D A ) of the optical glass of the present invention is three or more types, preferably two or more types, and more preferably one type.
<耐水作用稳定性><Water resistance stability>
光学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。 The water resistance stability (D W ) (powder method) of optical glass is tested according to the method specified in GB/T 17129.
在一些实施方式中，本发明光学玻璃的耐水作用稳定性(D W)为2类以上，优选为1类。 In some embodiments, the water resistance stability (D W ) of the optical glass of the present invention is 2 or more types, preferably 1 type.
<析晶上限温度><Maximum temperature of crystallization>
采用梯温炉法测定玻璃的析晶性能，将玻璃制成180×10×10mm的样品，侧面抛光，放入带有温度梯度(10℃/cm)的炉内升温至1300℃保温4小时后取出自然冷却到室温，在显微镜下观察玻璃析晶情况，玻璃出现晶体对应的最高温度即为玻璃的析晶上限温度。The crystallization performance of the glass was measured by the temperature gradient furnace method. The glass was made into a sample of 180 × 10 × 10 mm, the sides were polished, and then placed in a furnace with a temperature gradient (10 °C/cm) and heated to 1300 °C for 4 hours. Take it out and cool it to room temperature naturally, and observe the crystallization of the glass under a microscope. The maximum temperature corresponding to the appearance of crystals in the glass is the upper limit temperature of the crystallization of the glass.
在一些实施方式中，本发明的光学玻璃的析晶上限温度为1250℃以下，优选为1200℃以下，更优选为1180℃以下，进一步优选为1160℃以下。In some embodiment, the crystallization upper limit temperature of the optical glass of this invention is 1250 degrees C or less, Preferably it is 1200 degrees C or less, More preferably, it is 1180 degrees C or less, More preferably, it is 1160 degrees C or less.
[光学玻璃的制造方法][Manufacturing method of optical glass]
本发明光学玻璃的制造方法如下：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1200～1400℃的熔炼炉(如铂金坩埚、氧化铝坩埚等)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。The manufacturing method of the optical glass of the present invention is as follows: the glass of the present invention is produced by using conventional raw materials and processes, including but not limited to using carbonates, nitrates, sulfates, hydroxides, oxides, etc. , put the prepared charge into a smelting furnace (such as platinum crucible, alumina crucible, etc.) at 1200 ~ 1400 ° C for melting, and after clarification, stirring and homogenization, get no bubbles and no undissolved substances. quality molten glass, which is cast in a mold and annealed. Those skilled in the art can appropriately select raw materials, process methods and process parameters according to actual needs.
[玻璃预制件和光学元件][Glass Preforms and Optical Components]
可以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，由所制成的光学玻璃来制作玻璃预制件。即，可以通过对光学玻璃进行磨削和研磨等机械加工来制作玻璃预制件，或通过对由光学玻璃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，或通过对进行研磨加工而制成的预成型坯进行精密冲压成型来制作玻璃预制件。A glass preform can be produced from the optical glass produced by using, for example, a means of grinding, or a means of press forming such as reheat press forming and precision press forming. That is, a glass preform can be produced by subjecting optical glass to mechanical processing such as grinding and polishing, or by producing a preform for press-molding from optical glass, reheating the preform, and then grinding the preform. Glass preforms are produced by machining, or by precision stamping of preforms produced by grinding.
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，本发明的光学玻璃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光学玻璃形成预成型坯，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。It should be noted that the means for preparing the glass preform is not limited to the above-mentioned means. As described above, the optical glass of the present invention is useful for various optical elements and optical designs, and it is particularly preferable to form a preform from the optical glass of the present invention, and to perform reheat press molding, precision press molding, etc. using the preform , making optical components such as lenses and prisms.
本发明的玻璃预制件与光学元件均由上述本发明的光学玻璃形成。本发明的玻璃预制件具有光学玻璃所具有的优异特性；本发明的光学元件具有光学玻璃所具有的优异特性，能够提供光学价值高的各种透镜、棱镜等光学元件。Both the glass preform and the optical element of the present invention are formed from the optical glass of the present invention described above. The glass preform of the present invention has the excellent characteristics of optical glass; the optical element of the present invention has the excellent characteristics of optical glass, and can provide various optical elements such as lenses and prisms with high optical value.
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。Examples of lenses 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.
[光学仪器][Optical Instruments]
本发明光学玻璃所形成的光学元件可制作如照相设备、摄像设备、显示设备和监控设备等光学仪器。The optical element formed by the optical glass of the present invention can be used to manufacture optical instruments such as photographic equipment, imaging equipment, display equipment and monitoring equipment.
实施例Example
<光学玻璃实施例><Example of Optical Glass>
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。In order to further clearly illustrate and illustrate the technical solutions of the present invention, the following non-limiting examples are provided.
本实施例采用上述光学玻璃的制造方法得到具有表1～表2所示的组成的光学玻璃。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。In this Example, the optical glass which has the composition shown in Table 1 - Table 2 was obtained by the manufacturing method of the said optical glass. In addition, the properties of each glass were measured by the test method of the present invention, and the measurement results are shown in Tables 1 to 2.
表1.Table 1.
Figure PCTCN2021107560-appb-000001
Figure PCTCN2021107560-appb-000001
Figure PCTCN2021107560-appb-000002
Figure PCTCN2021107560-appb-000002
表2.Table 2.
Figure PCTCN2021107560-appb-000003
Figure PCTCN2021107560-appb-000003
Figure PCTCN2021107560-appb-000004
Figure PCTCN2021107560-appb-000004
<玻璃预制件实施例><Example of glass preform>
将光学玻璃实施例1～20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。A concave meniscus lens, a convex meniscus lens, and a biconvex lens are produced by using the glass obtained in the optical glass Examples 1 to 20, for example, by means of grinding, or by means of press molding such as reheat press molding and precision press molding. , Bi-concave lenses, plano-convex lenses, plano-concave lenses and other lenses, prisms and other prefabricated parts.
<光学元件实施例><Optical element example>
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。These preforms obtained in the above-mentioned glass preform examples are annealed, and the internal deformation of the glass is reduced while fine-tuning is performed, so that the optical properties such as the refractive index can reach desired values.
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。Next, each preform is ground and polished to produce various lenses and prisms such as a concave meniscus lens, a convex meniscus lens, a biconvex lens, a biconcave lens, a plano-convex lens, and a plano-concave lens. An antireflection film may also be coated on the surface of the obtained optical element.
<光学仪器实施例><Optical Instrument Example>
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。The optical elements produced by the above-mentioned optical element embodiments are optically designed and formed by using one or more optical elements to form optical components or optical assemblies, which can be used in, for example, imaging equipment, sensors, microscopes, medical technology, digital projection, communications, optical communications Technology/information transmission, optics/lighting in the automotive field, lithography, excimer lasers, wafers, computer chips and integrated circuits and electronic devices including such circuits and chips, or camera equipment and devices for the automotive field.

Claims (19)

  1. 光学玻璃，其特征在于，其组分以重量百分比表示，含有：B 2O 3：8～20％；La 2O 3：21～40％；Gd 2O 3：6～20％；ZrO 2：1～10％；ZnO：7～20％；WO 3：8～20％；TiO 2：大于0但小于或等于10％，其中(WO 3+ZnO)/(La 2O 3+TiO 2+ZrO 2)为0.3～1.5。 Optical glass, characterized in that its components are expressed in weight percentage, and contain: B 2 O 3 : 8-20%; La 2 O 3 : 21-40%; Gd 2 O 3 : 6-20%; ZrO 2 : 1-10%; ZnO: 7-20%; WO 3 : 8-20%; TiO 2 : greater than 0 but less than or equal to 10%, wherein (WO 3 +ZnO)/(La 2 O 3 +TiO 2 +ZrO 2 ) is 0.3 to 1.5.
  2. 根据权利要求1所述的光学玻璃，其特征在于，其组分以重量百分比表示，还含有：SiO 2：0～9％；和/或Y 2O 3：0～10％；和/或Yb 2O 3：0～10％；和/或Nb 2O 5：0～8％；和/或Rn 2O：0～10％；和/或RO：0～10％；和/或Al 2O 3：0～5％；和/或Ta 2O 5：0～5％；和/或澄清剂：0～1％，所述Rn 2O为Li 2O、Na 2O、K 2O中的一种或多种，RO为MgO、CaO、SrO、BaO中的一种或多种，澄清剂为Sb 2O 3、SnO 2、SnO、CeO 2中的一种或多种。 The optical glass according to claim 1, characterized in that its components are expressed in weight percentage, and further contains: SiO 2 : 0-9%; and/or Y 2 O 3 : 0-10%; and/or Yb 2 O 3 : 0-10%; and/or Nb 2 O 5 : 0-8%; and/or Rn 2 O: 0-10%; and/or RO: 0-10%; and/or Al 2 O 3 : 0-5%; and/or Ta 2 O 5 : 0-5%; and/or clarifying agent: 0-1%, the Rn 2 O is one of Li 2 O, Na 2 O and K 2 O One or more, RO is one or more of MgO, CaO, SrO, BaO, and the clarifying agent is one or more of Sb 2 O 3 , SnO 2 , SnO, CeO 2 .
  3. 光学玻璃，其特征在于，含有B 2O 3、La 2O 3、Gd 2O 3、ZrO 2、ZnO、WO 3和TiO 2作为必要组分，其组分以重量百分比表示，其中(WO 3+ZnO)/(La 2O 3+TiO 2+ZrO 2)为0.3～1.5，所述光学玻璃的折射率n d为1.85～1.91，阿贝数ν d为32～38.5，热膨胀系数α 100/300℃为100×10 -7/K以下。 Optical glass, characterized in that it contains B 2 O 3 , La 2 O 3 , Gd 2 O 3 , ZrO 2 , ZnO, WO 3 and TiO 2 as essential components, the components of which are expressed in weight percentages, wherein (WO 3 +ZnO)/(La 2 O 3 +TiO 2 +ZrO 2 ) is 0.3-1.5, the refractive index n d of the optical glass is 1.85-1.91, the Abbe number ν d is 32-38.5, and the thermal expansion coefficient α 100/ 300°C is 100×10 -7 /K or less.
  4. 根据权利要求3所述的光学玻璃，其特征在于，其组分以重量百分比表示，含有：B 2O 3：8～20％；和/或La 2O 3：21～40％；和/或Gd 2O 3：6～20％；和/或ZrO 2：1～10％；和/或ZnO：7～20％；和/或WO 3：8～20％；和/或TiO 2：大于0但小于或等于10％；和/或SiO 2：0～9％；和/或Y 2O 3：0～10％；和/或Yb 2O 3：0～10％；和/或Nb 2O 5：0～8％；和/或Rn 2O：0～10％；和/或RO：0～10％；和/或Al 2O 3：0～5％；和/或Ta 2O 5：0～5％；和/或澄清剂：0～1％，所述Rn 2O为Li 2O、Na 2O、K 2O中的一种或多种，RO为MgO、CaO、SrO、BaO中的一种或多种，澄清剂为Sb 2O 3、SnO 2、SnO、CeO 2中的一种或多种。 The optical glass according to claim 3, characterized in that, its components are expressed in weight percentage, and contain: B 2 O 3 : 8-20%; and/or La 2 O 3 : 21-40%; and/or Gd 2 O 3 : 6-20%; and/or ZrO 2 : 1-10%; and/or ZnO: 7-20%; and/or WO 3 : 8-20%; and/or TiO 2 : greater than 0 but less than or equal to 10%; and/or SiO 2 : 0-9%; and/or Y 2 O 3 : 0-10%; and/or Yb 2 O 3 : 0-10%; and/or Nb 2 O 5 : 0-8%; and/or Rn 2 O: 0-10%; and/or RO: 0-10%; and/or Al 2 O 3 : 0-5%; and/or Ta 2 O 5 : 0-5%; and/or clarifying agent: 0-1%, the Rn 2 O is one or more of Li 2 O, Na 2 O, K 2 O, and RO is MgO, CaO, SrO, BaO One or more of the clarifying agent is one or more of Sb 2 O 3 , SnO 2 , SnO and CeO 2 .
  5. 光学玻璃，其特征在于，其组分以重量百分比表示，由B 2O 3：8～20％；La 2O 3：21～40％；Gd 2O 3：6～20％；ZrO 2：1～10％；ZnO：7～20％；WO 3：8～20％；TiO 2：大于0但小于或等于10％；SiO 2：0～9％；Y 2O 3：0～10％；Yb 2O 3：0～10％；Nb 2O 5：0～8％；Rn 2O：0～10％；RO：0～10％；Al 2O 3：0～5％；Ta 2O 5： 0～5％；澄清剂：0～1％组成，其中(WO 3+ZnO)/(La 2O 3+TiO 2+ZrO 2)为0.3～1.5，所述Rn 2O为Li 2O、Na 2O、K 2O中的一种或多种，RO为MgO、CaO、SrO、BaO中的一种或多种，澄清剂为Sb 2O 3、SnO 2、SnO、CeO 2中的一种或多种。 Optical glass, characterized in that its components are expressed in weight percentages, B 2 O 3 : 8-20%; La 2 O 3 : 21-40%; Gd 2 O 3 : 6-20%; ZrO 2 : 1 ～10%; ZnO: 7～20%; WO 3 : 8～20%; TiO 2 : more than 0 but less than or equal to 10%; SiO 2 : 0～9%; Y 2 O 3 : 0～10%; Yb 2 O 3 : 0-10%; Nb 2 O 5 : 0-8%; Rn 2 O: 0-10%; RO: 0-10%; Al 2 O 3 : 0-5%; Ta 2 O 5 : 0-5%; clarifier: 0-1% composition, wherein (WO 3 +ZnO)/(La 2 O 3 +TiO 2 +ZrO 2 ) is 0.3-1.5, and the Rn 2 O is Li 2 O, Na One or more of 2 O, K 2 O, RO is one or more of MgO, CaO, SrO, BaO, and the clarifying agent is one of Sb 2 O 3 , SnO 2 , SnO, CeO 2 or more.
  6. 根据权利要求1～5任一权利要求所述的光学玻璃，其特征在于，其组分以重量百分比表示，满足以下9种情形中的一种以上：The optical glass according to any one of claims 1 to 5, characterized in that, its components are expressed in weight percentages and satisfy one or more of the following nine conditions:
    1)Nb 2O 5/Y 2O 3为0.1～2.5； 1) Nb 2 O 5 /Y 2 O 3 is 0.1 to 2.5;
    2)Y 2O 3/WO 3为0.05～1.0； 2) Y 2 O 3 /WO 3 is 0.05 to 1.0;
    3)Y 2O 3/TiO 2为0.2～3.5； 3) Y 2 O 3 /TiO 2 is 0.2 to 3.5;
    4)5×Nb 2O 5/(WO 3+Gd 2O 3)为0.05～1.5； 4) 5×Nb 2 O 5 /(WO 3 +Gd 2 O 3 ) is 0.05 to 1.5;
    5)ZnO/La 2O 3为0.2～0.8； 5) ZnO/La 2 O 3 is 0.2～0.8;
    6)Gd 2O 3/(La 2O 3+Y 2O 3)为0.2～0.8； 6) Gd 2 O 3 /(La 2 O 3 +Y 2 O 3 ) is 0.2 to 0.8;
    7)(WO 3+ZnO)/(La 2O 3+TiO 2+ZrO 2)为0.5～1.0； 7) (WO 3 +ZnO)/(La 2 O 3 +TiO 2 +ZrO 2 ) is 0.5 to 1.0;
    8)5×Li 2O/(TiO 2+SiO 2)为0.05～5.0； 8) 5×Li 2 O/(TiO 2 +SiO 2 ) is 0.05 to 5.0;
    9)Nb 2O 5/WO 3为0.03～0.7。 9) Nb 2 O 5 /WO 3 is 0.03 to 0.7.
  7. 根据权利要求1～5任一权利要求所述的光学玻璃，其特征在于，其组分以重量百分比表示，其中：B 2O 3：10～18％；和/或La 2O 3：25～38％；和/或Gd 2O 3：8～18％；和/或ZrO 2：1～8％；和/或ZnO：8～18％；和/或WO 3：10～18％；和/或TiO 2：0.5～7％；和/或SiO 2：0.5～9％；和/或Y 2O 3：大于0但小于或等于6％；和/或Yb 2O 3：0～5％；和/或Nb 2O 5：0.5～6％；和/或Rn 2O：0～5％；和/或RO：0～5％；和/或Al 2O 3：0～2％；和/或Ta 2O 5：0～2％；和/或澄清剂：0～0.5％，所述Rn 2O为Li 2O、Na 2O、K 2O中的一种或多种，RO为MgO、CaO、SrO、BaO中的一种或多种，澄清剂为Sb 2O 3、SnO 2、SnO、CeO 2中的一种或多种。 The optical glass according to any one of claims 1 to 5, characterized in that its components are expressed in weight percentage, wherein: B 2 O 3 : 10-18%; and/or La 2 O 3 : 25-18% and/or Gd2O3 : 8-18 %; and/or ZrO2: 1-8 %; and/or ZnO: 8-18 %; and/or WO3: 10-18%; and/or or TiO 2 : 0.5-7%; and/or SiO 2 : 0.5-9%; and/or Y 2 O 3 : greater than 0 but less than or equal to 6%; and/or Yb 2 O 3 : 0-5%; and/or Nb 2 O 5 : 0.5-6%; and/or Rn 2 O: 0-5%; and/or RO: 0-5%; and/or Al 2 O 3 : 0-2%; and/or or Ta 2 O 5 : 0-2%; and/or clarifying agent: 0-0.5%, the Rn 2 O is one or more of Li 2 O, Na 2 O and K 2 O, and RO is MgO , one or more of CaO, SrO and BaO, and the clarifying agent is one or more of Sb 2 O 3 , SnO 2 , SnO and CeO 2 .
  8. 根据权利要求1～5任一权利要求所述的光学玻璃，其特征在于，其组分以重量百分比表示，满足以下9种情形中的一种以上：The optical glass according to any one of claims 1 to 5, characterized in that, its components are expressed in weight percentages and satisfy one or more of the following nine conditions:
    1)Nb 2O 5/Y 2O 3为0.25～1.5； 1) Nb 2 O 5 /Y 2 O 3 is 0.25 to 1.5;
    2)Y 2O 3/WO 3为0.1～0.6； 2) Y 2 O 3 /WO 3 is 0.1 to 0.6;
    3)Y 2O 3/TiO 2为0.5～2.0； 3) Y 2 O 3 /TiO 2 is 0.5 to 2.0;
    4)5×Nb 2O 5/(WO 3+Gd 2O 3)为0.1～1.0； 4) 5×Nb 2 O 5 /(WO 3 +Gd 2 O 3 ) is 0.1 to 1.0;
    5)ZnO/La 2O 3为0.3～0.7； 5) ZnO/La 2 O 3 is 0.3～0.7;
    6)Gd 2O 3/(La 2O 3+Y 2O 3)为0.25～0.65； 6) Gd 2 O 3 /(La 2 O 3 +Y 2 O 3 ) is 0.25 to 0.65;
    7)(WO 3+ZnO)/(La 2O 3+TiO 2+ZrO 2)为0.6～0.9； 7) (WO 3 +ZnO)/(La 2 O 3 +TiO 2 +ZrO 2 ) is 0.6 to 0.9;
    8)5×Li 2O/(TiO 2+SiO 2)为0.1～2.0； 8) 5×Li 2 O/(TiO 2 +SiO 2 ) is 0.1 to 2.0;
    9)Nb 2O 5/WO 3为0.05～0.5。 9) Nb 2 O 5 /WO 3 is 0.05 to 0.5.
  9. 根据权利要求1～5任一权利要求所述的光学玻璃，其特征在于，其组分以重量百分比表示，其中：B 2O 3：11～17％；和/或La 2O 3：28～35％；和/或Gd 2O 3：9.5～16％，优选Gd 2O 3：11～16％；和/或ZrO 2：2～6％；和/或ZnO：10～16％，优选ZnO：11～16％；和/或WO 3：12～17％；和/或TiO 2：1～5％；和/或SiO 2：1～8％，优选SiO 2：2～6％；和/或Y 2O 3：1～5％；和/或Yb 2O 3：0～2％；和/或Nb 2O 5：1～5％；和/或Rn 2O：0.5～3％；和/或RO：0～2％；和/或Al 2O 3：0～1％；和/或Ta 2O 5：0～1％；和/或澄清剂：0～0.1％，所述Rn 2O为Li 2O、Na 2O、K 2O中的一种或多种，RO为MgO、CaO、SrO、BaO中的一种或多种，澄清剂为Sb 2O 3、SnO 2、SnO、CeO 2中的一种或多种。 The optical glass according to any one of claims 1 to 5, characterized in that its components are expressed in weight percentage, wherein: B 2 O 3 : 11-17%; and/or La 2 O 3 : 28- 35%; and/or Gd 2 O 3 : 9.5-16%, preferably Gd 2 O 3 : 11-16%; and/or ZrO 2 : 2-6%; and/or ZnO: 10-16%, preferably ZnO : 11-16%; and/or WO 3 : 12-17%; and/or TiO 2 : 1-5%; and/or SiO 2 : 1-8%, preferably SiO 2 : 2-6%; and/or or Y 2 O 3 : 1-5%; and/or Yb 2 O 3 : 0-2%; and/or Nb 2 O 5 : 1-5%; and/or Rn 2 O: 0.5-3%; and and/or RO: 0-2%; and/or Al 2 O 3 : 0-1%; and/or Ta 2 O 5 : 0-1%; and/or clarifying agent: 0-0.1%, the Rn 2 O is one or more of Li 2 O, Na 2 O and K 2 O, RO is one or more of MgO, CaO, SrO and BaO, and the clarifying agent is Sb 2 O 3 , SnO 2 , SnO , one or more of CeO 2 .
  10. 根据权利要求1～5任一权利要求所述的光学玻璃，其特征在于，其组分以重量百分比表示，满足以下9种情形中的一种以上：The optical glass according to any one of claims 1 to 5, characterized in that, its components are expressed in weight percentages and satisfy one or more of the following nine conditions:
    1)Nb 2O 5/Y 2O 3为0.3～0.8； 1) Nb 2 O 5 /Y 2 O 3 is 0.3 to 0.8;
    2)Y 2O 3/WO 3为0.1～0.4； 2) Y 2 O 3 /WO 3 is 0.1 to 0.4;
    3)Y 2O 3/TiO 2为0.8～1.3； 3) Y 2 O 3 /TiO 2 is 0.8 to 1.3;
    4)5×Nb 2O 5/(WO 3+Gd 2O 3)为0.15～0.5； 4) 5×Nb 2 O 5 /(WO 3 +Gd 2 O 3 ) is 0.15 to 0.5;
    5)ZnO/La 2O 3为0.35～0.65； 5) ZnO/La 2 O 3 is 0.35～0.65;
    6)Gd 2O 3/(La 2O 3+Y 2O 3)为0.35～0.55； 6) Gd 2 O 3 /(La 2 O 3 +Y 2 O 3 ) is 0.35 to 0.55;
    7)(WO 3+ZnO)/(La 2O 3+TiO 2+ZrO 2)为0.7～0.85； 7) (WO 3 +ZnO)/(La 2 O 3 +TiO 2 +ZrO 2 ) is 0.7-0.85;
    8)5×Li 2O/(TiO 2+SiO 2)为0.2～1.0； 8) 5×Li 2 O/(TiO 2 +SiO 2 ) is 0.2 to 1.0;
    9)Nb 2O 5/WO 3为0.06～0.4。 9) Nb 2 O 5 /WO 3 is 0.06 to 0.4.
  11. 根据权利要求1～5任一权利要求所述的光学玻璃，其特征在于，其组分以重量百分比表示，满足以下5种情形中的一种以上：The optical glass according to any one of claims 1 to 5, characterized in that, its components are expressed in weight percentages and satisfy one or more of the following five conditions:
    1)Nb 2O 5/Y 2O 3为0.4～0.7； 1) Nb 2 O 5 /Y 2 O 3 is 0.4 to 0.7;
    2)5×Nb 2O 5/(WO 3+Gd 2O 3)为0.2～0.4； 2) 5×Nb 2 O 5 /(WO 3 +Gd 2 O 3 ) is 0.2 to 0.4;
    3)ZnO/La 2O 3为0.4～0.55； 3) ZnO/La 2 O 3 is 0.4～0.55;
    4)5×Li 2O/(TiO 2+SiO 2)为0.3～0.8； 4) 5×Li 2 O/(TiO 2 +SiO 2 ) is 0.3-0.8;
    5)Nb 2O 5/WO 3为0.08～0.3。 5) Nb 2 O 5 /WO 3 is 0.08 to 0.3.
  12. 根据权利要求1～5任一权利要求所述的光学玻璃，其特征在于，其组分以重量百分比表示，其中：Li 2O：0～6％，优选Li 2O：大于0但小于或等于4％，更优选Li 2O：0.1～3％，进一步优选Li 2O：0.5～2％；和/或Na 2O：0～5％，优选Na 2O：0～3％，更优选Na 2O：0～2％；和/或K 2O：0～5％，优选K 2O：0～3％，更优选K 2O：0～2％。 The optical glass according to any one of claims 1 to 5, characterized in that its components are expressed in weight percentage, wherein: Li 2 O: 0-6%, preferably Li 2 O: greater than 0 but less than or equal to 4%, more preferably Li 2 O: 0.1-3%, further preferably Li 2 O: 0.5-2%; and/or Na 2 O: 0-5%, preferably Na 2 O: 0-3%, more preferably Na 2 O: 0 to 2%; and/or K 2 O: 0 to 5%, preferably K 2 O: 0 to 3%, more preferably K 2 O: 0 to 2%.
  13. 根据权利要求1～5任一权利要求所述的光学玻璃，其特征在于，其组分中不含有Ta 2O 5；和/或不含有GeO 2；和/或不含有F；和/或不含有Al 2O 3；和/或不含有RO；和/或不含有P 2O 5；和/或不含有Bi 2O 3。 The optical glass according to any one of claims 1 to 5, characterized in that its components do not contain Ta 2 O 5 ; and/or do not contain GeO 2 ; and/or do not contain F; and/or do not contain and/or no RO ; and/or no P2O5 ; and / or no Bi2O3 .
  14. 根据权利要求1～5任一权利要求所述的光学玻璃，其特征在于，所述光学玻璃的折射率n d为1.85～1.91，优选为1.86～1.90，更优选为1.88～1.90；阿贝数ν d为32～38.5，优选为33～37.5，更优选为34～37。 The optical glass according to any one of claims 1 to 5, wherein the refractive index nd of the optical glass is 1.85-1.91, preferably 1.86-1.90, more preferably 1.88-1.90; Abbe number ν d is 32 to 38.5, preferably 33 to 37.5, and more preferably 34 to 37.
  15. 根据权利要求1～5任一权利要求所述的光学玻璃，其特征在于，所述光学玻璃的耐酸作用稳定性D A为3类以上，优选为2类以上，更优选为1类；和/或耐水作用稳定性D W为2类以上，优选为1类；和/或密度ρ为5.50g/cm 3以下，优选为5.40g/cm 3以下，更优选为5.30g/cm 3以下，进一步优选为5.20g/cm 3以下；和/或λ 70小于或等于410nm，优选λ 70小于或等于405nm，更优选λ 70小于或等于400nm，进一步优选λ 70小于或等于395nm；和/或λ 5小于或等于375nm，优选λ 5小于或等于370nm，更优选λ 5小于或等于365nm，进一步优选λ 5为小于或等于360nm。 The optical glass according to any one of claims 1 to 5, wherein the acid resistance stability D A of the optical glass is 3 or more, preferably 2 or more, and more preferably 1; and/ Or the water resistance stability D W is 2 or more types, preferably 1 type; and/or the density ρ is 5.50 g/cm 3 or less, preferably 5.40 g/cm 3 or less, more preferably 5.30 g/cm 3 or less, further and/or λ 70 is less than or equal to 410 nm, preferably λ 70 is less than or equal to 405 nm, more preferably λ 70 is less than or equal to 400 nm, further preferably λ 70 is less than or equal to 395 nm ; and/or λ 5 It is less than or equal to 375 nm, preferably λ 5 is less than or equal to 370 nm, more preferably λ 5 is less than or equal to 365 nm, further preferably λ 5 is less than or equal to 360 nm.
  16. 根据权利要求1～5任一权利要求所述的光学玻璃，其特征在于， 所述光学玻璃的热膨胀系数α 100/300℃为100×10 -7/K以下，优选为95×10 -7/K以下，更优选为90×10 -7/K以下；和/或转变温度T g为620℃以下，优选为610℃以下，更优选为600℃以下；和/或析晶上限温度为1250℃以下，优选为1200℃以下，更优选为1180℃以下，进一步优选为1160℃以下。 The optical glass according to any one of claims 1 to 5, wherein the thermal expansion coefficient α 100/300°C of the optical glass is 100×10 -7 /K or less, preferably 95×10 -7 / K or less, more preferably 90×10 -7 /K or less; and/or the transition temperature T g is 620°C or less, preferably 610°C or less, more preferably 600°C or less; and/or the crystallization upper limit temperature is 1250°C Below, it is preferably 1200°C or lower, more preferably 1180°C or lower, still more preferably 1160°C or lower.
  17. 玻璃预制件，其特征在于，采用权利要求1～16任一所述的光学玻璃制成。A glass preform is characterized in that it is made of the optical glass according to any one of claims 1-16.
  18. 光学元件，其特征在于，采用权利要求1～16任一所述的光学玻璃或权利要求17所述的玻璃预制件制成。The optical element is characterized in that it is made of the optical glass described in any one of claims 1 to 16 or the glass preform described in claim 17 .
  19. 光学仪器，其特征在于，含有权利要求1～16任一所述的光学玻璃，和/或含有权利要求18所述的光学元件。An optical instrument characterized by comprising the optical glass according to any one of claims 1 to 16 and/or comprising the optical element according to claim 18 .
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