WO2022062637A1 - 光学玻璃 - Google Patents

光学玻璃 Download PDF

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Publication number
WO2022062637A1
WO2022062637A1 PCT/CN2021/108874 CN2021108874W WO2022062637A1 WO 2022062637 A1 WO2022062637 A1 WO 2022062637A1 CN 2021108874 W CN2021108874 W CN 2021108874W WO 2022062637 A1 WO2022062637 A1 WO 2022062637A1
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WO
WIPO (PCT)
Prior art keywords
glass
zro
optical glass
optical
sio
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PCT/CN2021/108874
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English (en)
French (fr)
Inventor
郝良振
毛露路
匡波
李赛
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成都光明光电股份有限公司
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Priority to JP2023519502A priority Critical patent/JP2023542723A/ja
Publication of WO2022062637A1 publication Critical patent/WO2022062637A1/zh

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/062—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
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B19/00—Other methods of shaping glass
    • C03B19/02—Other methods of shaping glass by casting molten glass, e.g. injection moulding
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements

Definitions

  • the invention relates to an optical glass, in particular to a high-refractive and high-dispersion optical glass with excellent anti-devitrification properties.
  • the secondary spectrum is the main factor affecting the imaging quality. Correcting the secondary spectrum is a prominent problem in the design of a long focal length optical system, and it is also a difficult problem to solve.
  • the correction of the secondary spectrum in the optical system depends to a large extent on the choice of glass material. Glass with high refraction, high dispersion, and low relative partial dispersion (P g,F ) is beneficial to eliminate the secondary spectrum when applied to the coupling lens. , simplify and optimize the optical system and improve the image quality.
  • Secondary pressing has the advantages of low production cost, low production difficulty, and easy mass production, and is widely used in the production of glass components.
  • Secondary pressing is a production method in which the glass material is placed in a mold and heated to above the softening point, and then the glass material is pressed into a predetermined shape by pressing. This production method often needs to heat the glass to 100-200°C above the transition temperature. At this time, the glass already has a certain fluidity. If the anti-devitrification performance of the glass is not good, the glass will have some problems during the secondary pressing process. Risk of crystallization scrapping.
  • CN104583142A discloses an optical glass with relatively low relative partial dispersion, the composition of which contains more than 5.0% and less than 55.0% of B 2 O 3 and more than 15% and less than 60% of rare earth oxides in mass %.
  • the anti-devitrification performance of optical glass is poor, and the glass has a greater risk of devitrification during secondary pressing.
  • the technical problem to be solved by the present invention is to provide a high-refractive and high-dispersion optical glass with excellent anti-devitrification properties and low relative partial dispersion.
  • Optical glass whose components are expressed in weight percentage, containing: SiO 2 : 25-45%; ZrO 2 : 2-15%; Nb 2 O 5 : 35-60%; Li 2 O: 1-10%; Na 2 O: 2 to 15%; K 2 O: 0 to 10%.
  • the optical glass whose components are expressed in weight percentage, further contains: B 2 O 3 : 0-10%; and/or Al 2 O 3 : 0-5%; and/or La 2 O 3 : 0-10%; and/or Gd 2 O 3 : 0-10%; and/or Y 2 O 3 : 0-10%; and/or Yb 2 O 3 : 0-10%; and/or BaO: and/or SrO: 0-10%; and/or CaO: 0-10%; and/or MgO: 0-5%; and/or ZnO: 0-10%; and/or TiO 2 : 0-10%; and/or WO 3 : 0-10%; and/or Bi 2 O 3 : 0-5%; and/or Ta 2 O 5 : 0-5%; and/or Sb 2 O 3 : 0 to 1%.
  • Optical glass whose components are expressed by weight percentage, including SiO 2 : 25-45%; ZrO 2 : 2-15%; Nb 2 O 5 : 35-60%; Li 2 O: 1-10%; Na 2 O : 2 to 15%; K 2 O : 0 to 10%; B 2 O 3 : 0 to 10%; Al 2 O 3 : 0 to 5%; La 2 O 3 : 0 to 10%; Gd 2 O 3 : 0-10%; Y 2 O 3 : 0-10%; Yb 2 O 3 : 0-10%; BaO: 0-10%; SrO: 0-10%; CaO: 0-10%; MgO: 0- 5%; ZnO: 0-10%; TiO 2 : 0-10%; WO 3 : 0-10%; Bi 2 O 3 : 0-5%; Ta 2 O 5 : 0-5%; Sb 2 O 3 : 0 to 1% composition.
  • optical glass whose components are expressed in weight percentage, satisfies one or more of the following 9 situations:
  • B 2 O 3 +Al 2 O 3 is 0 ⁇ 12%
  • Re 2 O 3 is 0 ⁇ 15%
  • RO is 0 ⁇ 10%
  • SiO 2 +ZrO 2 is 30-55%
  • Nb 2 O 5 +ZrO 2 is 40 ⁇ 70%
  • TiO 2 +WO 3 +Bi 2 O 3 is 0-10%
  • Rn 2 O is 6 ⁇ 20%
  • ZrO 2 /Rn 2 O is 0.1 to 2.3
  • the Re 2 O 3 is the total content of La 2 O 3 , Gd 2 O 3 and Y 2 O 3 , RO is the total content of BaO, SrO, CaO, and MgO, and Rn 2 O is Li 2 O, Na 2 O, Total content of K 2 O.
  • the components of the optical glass are expressed in weight percentage, wherein: SiO 2 : 28-42%; and/or ZrO 2 : 3-12%; and/or Nb 2 O 5 : 38-57% and/or Li 2 O: 2-8%; and/or Na 2 O: 4-13%; and/or K 2 O: 0.5-8%; and/or B 2 O 3 : 0-5%; and/or Al 2 O 3 : 0-2%; and/or La 2 O 3 : 0-5%; and/or Gd 2 O 3 : 0-5%; and/or Y 2 O 3 : 0-5 %; and/or Yb 2 O 3 : 0-5%; and/or BaO: 0-5%; and/or SrO: 0-5%; and/or CaO: 0-8%; and/or MgO: and/or ZnO: 0-5%; and/or TiO 2 : 0-7%; and/or WO 3 : 0-5%; and/or Ta 2 O 5 : 0-2%; and/
  • optical glass whose components are expressed in weight percentage, satisfies one or more of the following 9 situations:
  • B 2 O 3 +Al 2 O 3 is 0 ⁇ 6%
  • SiO 2 +ZrO 2 is 33-52%
  • Nb 2 O 5 +ZrO 2 is 45-65%;
  • TiO 2 +WO 3 +Bi 2 O 3 is 0-7%
  • ZrO 2 /Rn 2 O is 0.2 to 1.8
  • the Re 2 O 3 is the total content of La 2 O 3 , Gd 2 O 3 and Y 2 O 3 , RO is the total content of BaO, SrO, CaO, and MgO, and Rn 2 O is Li 2 O, Na 2 O, Total content of K 2 O.
  • the components of the optical glass are expressed in weight percentage, wherein: SiO 2 : 30-40%; and/or ZrO 2 : 4-10%; and/or Nb 2 O 5 : 41-54% and/or B 2 O 3 : 0-3%; and/or Li 2 O: 3-6%; and/or Na 2 O: 5-12%; and/or K 2 O: 1-6%; and/or BaO: 0-2%; and/or CaO: 0-5%; and/or ZnO: 0-2%; and/or TiO 2 : 0-4%; and/or Sb 2 O 3 : 0 ⁇ 0.1%.
  • optical glass whose components are expressed in weight percentage, satisfies one or more of the following 7 situations:
  • RO is 0 ⁇ 5%
  • SiO 2 +ZrO 2 is 36-49%
  • Nb 2 O 5 +ZrO 2 is 50-60%
  • TiO 2 +WO 3 +Bi 2 O 3 is 0-4%;
  • Rn 2 O is 12 ⁇ 16%
  • ZrO 2 /Rn 2 O is 0.3 to 1.3
  • the RO is the total content of BaO, SrO, CaO, and MgO
  • the Rn 2 O is the total content of Li 2 O, Na 2 O, and K 2 O.
  • the components of the optical glass do not contain B 2 O 3 ; and/or do not contain Al 2 O 3 ; and/or do not contain La 2 O 3 ; and/or do not contain Gd 2 O 3 ; and/or no Y2O3 ; and/or no Yb2O3 ; and/or no MgO; and/or no SrO ; and/or no WO3 ; and/or no Bi2O 3 ; and/or does not contain Ta 2 O 5 ; and/or does not contain Re 2 O 3 , where Re 2 O 3 is the total content of La 2 O 3 , Gd 2 O 3 , and Y 2 O 3 .
  • the refractive index nd of the optical glass is 1.74-1.82, preferably the refractive index nd is 1.76-1.80;
  • the Abbe number ⁇ d is 25-32, preferably the Abbe number ⁇ d is 27-30 .
  • the relative partial dispersion of the optical glass is P g,F ⁇ 0.6497-0.001703 ⁇ d , preferably P g,F ⁇ 0.6477-0.001703 ⁇ d ; and/or the ⁇ 5 of the optical glass is below 360 nm, Preferably, ⁇ 5 is 350 nm or less.
  • the glass preform is made of the above-mentioned optical glass.
  • the optical element is made of the above-mentioned optical glass or the above-mentioned glass preform.
  • An optical instrument containing the above-mentioned optical glass, and/or containing the above-mentioned optical element.
  • the beneficial effects of the present invention are: by containing components such as SiO 2 and alkali metal oxides in an appropriate amount, the optical glass has excellent anti-devitrification properties; by containing Nb 2 O 5 , ZrO 2 and other oxides with high refractive index components, to obtain optical glass with high refractive index and high dispersion; through reasonable component design, the glass has lower relative partial dispersion.
  • 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.
  • description of the repeated description part may be appropriately omitted, this does not limit the gist of the invention.
  • the optical glass of the present invention is sometimes 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 the 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%.
  • SiO 2 is a glass network generator, which can improve the chemical stability and weather resistance of glass and maintain the anti-devitrification performance of glass. If the content of SiO 2 is less than 25%, it is difficult to achieve the above effects. Therefore, the lower limit of the SiO 2 content is 25 %, preferably 28 %, and more preferably 30%. If the content of SiO 2 is higher than 45%, the glass becomes difficult to melt, and it becomes difficult to obtain the refractive index desired in the present invention. Therefore, the upper limit of the content of SiO 2 is 45%, preferably 42%, and more preferably 40%.
  • B 2 O 3 can reduce the difficulty of glass compounding, and at the same time reduce the high temperature viscosity and transition temperature of glass.
  • the relative partial dispersion of the glass is increased.
  • the content of B 2 O 3 in the present invention is 10% or less, preferably 5% or less, more preferably 3% or less, and further preferably does not contain B 2 O 3 .
  • Al 2 O 3 can improve the weather resistance of glass, but it will increase the melting temperature and high temperature viscosity of glass, and increase the difficulty of production.
  • the content of Al 2 O 3 in the present invention is 0 to 5%, preferably 0 to 2%, and more preferably no Al 2 O 3 is contained.
  • B 2 O 3 +Al 2 O 3 is less than 12%, which is beneficial to maintain the relative partial dispersion of the glass within the design range.
  • B 2 O 3 +Al 2 O 3 is 0-6%.
  • La 2 O 3 is a component with high refraction and low dispersion, which can greatly reduce the relative partial dispersion of glass in glass, but when its content is too high, the dispersion of glass will be reduced, and it is difficult to achieve the desired high refraction and high dispersion of the present invention.
  • the content of La 2 O 3 in the present invention is 10% or less, preferably 5% or less, and more preferably no La 2 O 3 is contained.
  • Gd 2 O 3 is a component with high refractive index and low dispersion, which can reduce the relative partial dispersion of glass in glass, but the expensive raw material price limits the use of Gd 2 O 3 in glass. Therefore, the content of Gd 2 O 3 is 0 to 10%, preferably 0 to 5%, and more preferably no Gd 2 O 3 is contained.
  • Y 2 O 3 can improve the melting property of the glass and also improve the weather resistance of the glass, but if its content is too high, the dispersion of the glass will be reduced, and the optical properties of high refraction and high dispersion expected in the present invention cannot be achieved. Therefore, the content of Y 2 O 3 is 0 to 10%, preferably 0 to 5%, and more preferably no Y 2 O 3 is contained.
  • the total content of Re 2 O 3 of La 2 O 3 , Gd 2 O 3 and Y 2 O 3 is preferably 0 to 15%, more preferably 0 to 8% of Re 2 O 3 , and still more preferably not containing Re 2 O 3 .
  • Yb 2 O 3 can increase the refractive index of glass in glass, but it has an obvious absorption peak in the near-infrared region. When used as an optical element, it will change the spectral composition of the transmitted light, thereby affecting the image restoration effect. Therefore, the content range of Yb 2 O 3 is limited to 0 to 10%, preferably 0 to 5%, and more preferably no Yb 2 O 3 is contained.
  • the raw material of BaO is cheap and easy to obtain, and it can well increase the refractive index of glass in glass.
  • BaO is unfavorable for reducing the density of glass.
  • the BaO content is limited to 0 to 10%, preferably 0 to 5%, and more preferably 0 to 2%.
  • SrO is expensive and high content leads to an increase in the cost of the glass
  • the content of SrO is limited to 0 to 10%, preferably 0 to 5%, and more preferably does not contain SrO.
  • CaO can improve the hardness, mechanical strength and weather resistance of glass. More importantly, compared with BaO and SrO, CaO is more favorable for reducing the density of glass. In addition, CaO is also conducive to the control and adjustment of optical constants in the production process. However, when the CaO content is too high, it is difficult to melt the glass, and a calcium-rich hard shell is easily formed in the melting pool during the production process. Therefore, the content of CaO is limited to 0 to 10%, preferably 0 to 8%, and more preferably 0 to 5%.
  • MgO helps to improve the weather resistance of glass, but when the content is high, the refractive index of the glass is difficult to meet the design requirements, the anti-devitrification performance and stability of the glass decrease, and the cost of the glass rises rapidly. Therefore, the MgO content is limited to 0 to 5%, preferably 0 to 3%, and more preferably does not contain MgO.
  • the total content RO of alkaline earth metal oxides is preferably controlled within the range of 0-10%, and more It is preferably 0 to 8%, more preferably 0 to 5%.
  • the content of ZnO in the glass of the present invention is 0 to 10%, preferably 0 to 5%, and more preferably 0 to 2%.
  • ZrO 2 has the effect of improving the weather resistance of glass and improving the devitrification resistance of glass.
  • ZrO 2 in glass can greatly reduce the relative partial dispersion of glass.
  • the solubility of ZrO 2 in the glass of this system is not high, and when the content is too large, it is easy to dissociate from the glass system to form crystallization nuclei, which in turn leads to the deterioration of the anti-devitrification performance of the glass. Therefore, the content of ZrO 2 in the present invention is 2 to 15%, preferably 3 to 12%, and more preferably 4 to 10%.
  • SiO 2 and ZrO 2 can improve the weather resistance of the glass, and at the same time, SiO 2 and ZrO 2 are also the two components which are relatively difficult to melt in the present invention.
  • the glass can not only obtain excellent weather resistance, but also can obtain better production performance. Therefore, 30 to 55% of SiO 2 +ZrO 2 is preferable, 33 to 52% of SiO 2 +ZrO 2 is more preferable, and 36 to 49% of SiO 2 +ZrO 2 is more preferable.
  • Nb 2 O 5 is an essential component of the glass of the present invention, and is a key component to ensure that the glass has the characteristics of high refraction, high dispersion and low relative partial dispersion.
  • the inventors have found that the relative partial dispersion of Nb 2 O 5 to the glass is roughly consistent with the contribution to the Abbe number when the Abbe number is in the range of 25 to 32, that is, with the increase of Nb 2 O 5 in the glass. , the relative partial dispersion deviation ( ⁇ P g,F ) of the glass does not change substantially. Therefore, the content of Nb 2 O 5 in the present invention is 35 to 60%, preferably 38 to 57%, and more preferably 41 to 54%.
  • Nb 2 O 5 and ZrO 2 are the key components to maintain the low relative partial dispersion performance of the present invention.
  • Nb 2 O 5 +ZrO 2 is preferably 40 to 70%, more preferably 45 to 65%, and even more preferably 50 to 60%.
  • TiO 2 can increase the refractive index and dispersion of glass, and improve the anti-devitrification properties of glass.
  • the presence of TiO 2 in the glass will lead to a sharp increase in P g,F .
  • the content of TiO 2 in the glass is higher than 10%, the P g,F characteristics of the glass are difficult to meet the design requirements. Therefore, the content of TiO 2 is 0 to 10%, preferably 0 to 7%, and more preferably 0 to 4%.
  • WO 3 can improve the refractive index and dispersion of the glass, but it will lead to a sharp increase in the P g, F of the glass, and also lead to a decrease in the light transmittance of the glass.
  • the content of WO 3 is 0 to 10%, preferably 0 to 5%, and more preferably no WO 3 is contained.
  • Bi 2 O 3 can improve the refractive index and dispersion of glass, but it will lead to a sharp increase in P g,F of glass.
  • Bi 2 O 3 corrodes the platinum utensils seriously during the smelting process, so its content is limited to within 5%, and it is preferable not to contain Bi 2 O 3 .
  • TiO 2 , WO 3 and Bi 2 O 3 all have the effect of increasing the refractive index and dispersion of the glass, but all of them make the P g,F of the glass increase sharply. Therefore, in the present invention, the total content of TiO 2 , WO 3 and Bi 2 O 3 is preferably 0 to 10 %, and more preferably 0 to 0 to TiO 2 + WO 3 +Bi 2 O 3 7%, more preferably TiO 2 +WO 3 +Bi 2 O 3 is 0 to 4%.
  • Ta 2 O 5 is a high-refractive and high-dispersion component, which can reduce the P g, F value of the glass. At the same time, Ta 2 O 5 can improve the anti-devitrification properties of the glass and enhance the stability of the glass. But the expensive raw material cost greatly limits the use of Ta 2 O 5 .
  • the content of Ta 2 O 5 in the present invention is 0 to 5%, preferably 0 to 2%, and more preferably no Ta 2 O 5 is contained.
  • Li 2 O is an alkali metal oxide, and is a key component for reducing the difficulty of glass production in the present invention.
  • Li 2 O can be used as a flux to reduce the difficulty of glass compounding.
  • Li 2 O can reduce the high temperature viscosity and transition temperature of glass, making glass production and processing easier.
  • the inventor found that by including Li 2 O in the glass, the weather resistance of the glass can be improved by utilizing the accumulation effect of Li 2 O.
  • the content of Li 2 O is 1 to 10%, preferably 2 to 8%, and more preferably 3 to 6%.
  • Na 2 O and K 2 O can also reduce the melting temperature and high temperature viscosity of glass, and reduce the difficulty of glass production, but compared with the accumulation effect of Li 2 O, Na 2 O and K 2 O will cause the fracture of the silicon network structure of the glass , and cause the glass P g,F to increase. Therefore, the content of Na 2 O in the glass of the present invention is 2-15%, preferably 4-13%, more preferably 5-12%; the content of K 2 O is 0-10%, preferably 0.5-8%, More preferably, it is 1 to 6%.
  • Li 2 O, Na 2 O and K 2 O are all alkali metal oxides, which can reduce the difficulty of glass production, but too much content will reduce the chemical stability of the glass. Therefore, in the present invention, the total content Rn 2 O of Li 2 O, Na 2 O and K 2 O is preferably controlled within the range of 6 to 20%, more preferably 10 to 18%, and still more preferably 12 to 16%.
  • the alkali metal oxide Rn 2 O can promote the melting of SiO 2 and ZrO 2 and reduce the difficulty of smelting glass. Further, when the ratio between the total content of SiO 2 and ZrO 2 SiO 2 +ZrO 2 and the content of Rn 2 O (SiO 2 +ZrO 2 )/Rn 2 O is between 1.5 and 8.0, the glass can obtain excellent
  • the melting performance and anti-devitrification performance are preferably (SiO 2 +ZrO 2 )/Rn 2 O of 1.8-6.5, more preferably (SiO 2 +ZrO 2 )/Rn 2 O of 2.0-5.0.
  • the silicate glass network structure does not have strong bearing capacity for ZrO 2 , and when the ZrO 2 content is too high, it is easy to precipitate and form stones during the melting process.
  • the alkali metal oxide Rn 2 O can improve the carrying capacity of the silicate glass for ZrO 2 , when the ratio between the content of ZrO 2 and the content of Rn 2 O is ZrO
  • 2 /Rn 2 O is in the range of 0.1-2.3
  • the bearing capacity of the glass system of the present invention for ZrO 2 can be improved, and the chemical stability of the glass can be improved.
  • ZrO 2 /Rn 2 O is preferably 0.2 to 1.8, and more preferably ZrO 2 /Rn 2 O is 0.3 to 1.3.
  • Sb 2 O 3 can be used as a clarifying agent in the present invention to improve the clarifying effect of the glass, and its content ranges from 0 to 1%, preferably from 0 to 0.5%, and more preferably from 0 to 0.1%.
  • 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, not only in the glass manufacturing process, but also in the processing process and disposal after productization. Action is required. Therefore, when considering 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 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.
  • PbO can significantly improve the high refractive index and high dispersion properties of glass, but both PbO and As 2 O 3 are substances that cause environmental pollution.
  • Does not contain and "0%” as described herein means that the compound, molecule or element is not intentionally added to the optical glass of the present invention as a raw material; 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 refractive index (n d ) of the optical glass of the present invention is 1.74-1.82, preferably 1.76-1.80.
  • the Abbe number ( ⁇ d ) of the optical glass of the present invention is 25-32, preferably 27-30.
  • n g , n F and n C are tested according to the method specified in "GB/T 7962.1-2010".
  • the relative partial dispersion (P g,F ) of the optical glass of the present invention is ⁇ 0.6497-0.001703 ⁇ d , preferably P g,F ⁇ 0.6477-0.001703 ⁇ d .
  • the transmittance of glass ( ⁇ 5 ) is used to measure the short-wave transmittance of glass.
  • the specific test method is: place a 10mm thick double-sided polished sample on a spectrophotometer to test the transmittance of glass.
  • ⁇ 5 refers to the transmittance of glass. The corresponding wavelength when reaching 5%.
  • the ⁇ 5 of the optical glass of the present invention is 360 nm or less, preferably 350 nm or less.
  • test method for the anti-devitrification performance of optical glass is as follows: put the sample in a muffle furnace at T g +230 °C for 15 minutes, take it out, cool it at room temperature, and then observe each cubic meter in the sample after double-sided polishing. Number of crystallized particles in centimeters (A).
  • the number of crystallites (A) of the optical glass of the present invention is 5 or less, preferably 2 or less, and more preferably 0.
  • 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 conventional processes, using compound salts (such as carbonates, nitrates, sulfates), hydroxides, oxides, etc. as raw materials, according to conventional methods. After batching, put the prepared charge into a smelting furnace at 1250-1450°C for melting, and after clarification, stirring and homogenization, a homogeneous molten glass without bubbles and no undissolved substances is obtained. 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 glass preform can be produced from the optical glass produced by means of grinding, or by 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 grinding, 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. It should be noted that 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, vehicle-mounted equipment, imaging equipment, display equipment and monitoring equipment.
  • the optical glass of the present invention has the properties of high refraction, high dispersion and low relative partial dispersion, it is especially suitable for telephoto lenses and high-definition interchangeable lenses.
  • the optical glass shown in Table 1 - Table 4 was obtained by the manufacturing method of the said optical glass.
  • the characteristics of each glass were measured by the test method according to the present invention, and the measurement results are shown in Tables 1 to 4.
  • a concave meniscus lens, a convex meniscus lens, and a biconvex lens are produced by using the glasses obtained in optical glass Examples 1 to 40, 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 for example in imaging equipment, sensors, microscopes, medical technology, digital projection, communication, optical communication 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.

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Abstract

本发明提供一种光学玻璃，其组分以重量百分比表示，含有：SiO 2：25～45％；ZrO 2：2～15％；Nb 2O 5：35～60％；Li 2O：1～10％；Na 2O：2～15％；K 2O：0～10％。本发明通过含有合适量的SiO 2和碱金属氧化物等组分，使光学玻璃具有优异的抗析晶性能；通过含有Nb 2O 5、ZrO 2等具有高折射率氧化物组分，得到具有高折射高色散的光学玻璃；通过合理的组分设计使光学玻璃具有较低的相对部分色散。

Description

光学玻璃 技术领域
本发明涉及一种光学玻璃，尤其是涉及一种抗析晶性能优异的高折射高色散光学玻璃。
背景技术
在长焦距、大视场和高精度光学系统中，二级光谱是影响成像质量的主要因素，校正二级光谱是长焦距光学系统设计中的一个突出问题，也是比较难解决的一个问题。光学系统中二级光谱的校正在很大程度上取决于玻璃材料的选择，高折射、高色散、低相对部分色散(P g,F)的玻璃在应用于耦合透镜时有利于消除二级光谱，简化和优化光学系统，提升成像质量。
二次压型具有制作成本低、生产难度小、便于大批量生产等优势，被广泛应用于玻璃元件制作中。二次压型是将玻璃材料放置在模具中加热到软化点以上，再通过加压的方式将玻璃材料压制成预定形状的生产方式。这种生产方式往往需要将玻璃加热至转变温度以上100～200℃，此时的玻璃已经具有一定的流动性，如果玻璃的抗析晶性能不好，在二次压型的过程中玻璃就有析晶报废的风险。CN104583142A公开了一款具有较低相对部分色散的光学玻璃，其组分中以质量％计含有5.0％以上且55.0％以下的B 2O 3和15％以上且60％以下的稀土氧化物，该光学玻璃的抗析晶性能较差，玻璃在二次压型时存在较大的析晶风险。
发明内容
本发明所要解决的技术问题是提供一种抗析晶性能优异，具有较低相对部分色散的高折射高色散光学玻璃。
本发明解决技术问题所采用的技术方案是：
光学玻璃，其组分以重量百分比表示，含有：SiO 2：25～45％；ZrO 2：2～15％；Nb 2O 5：35～60％；Li 2O：1～10％；Na 2O：2～15％；K 2O：0～10％。
进一步的，所述的光学玻璃，其组分以重量百分比表示，还含有：B 2O 3： 0～10％；和/或Al 2O 3：0～5％；和/或La 2O 3：0～10％；和/或Gd 2O 3：0～10％；和/或Y 2O 3：0～10％；和/或Yb 2O 3：0～10％；和/或BaO：0～10％；和/或SrO：0～10％；和/或CaO：0～10％；和/或MgO：0～5％；和/或ZnO：0～10％；和/或TiO 2：0～10％；和/或WO 3：0～10％；和/或Bi 2O 3：0～5％；和/或Ta 2O 5：0～5％；和/或Sb 2O 3：0～1％。
光学玻璃，其组分以重量百分比表示，由SiO 2：25～45％；ZrO 2：2～15％；Nb 2O 5：35～60％；Li 2O：1～10％；Na 2O：2～15％；K 2O：0～10％；B 2O 3：0～10％；Al 2O 3：0～5％；La 2O 3：0～10％；Gd 2O 3：0～10％；Y 2O 3：0～10％；Yb 2O 3：0～10％；BaO：0～10％；SrO：0～10％；CaO：0～10％；MgO：0～5％；ZnO：0～10％；TiO 2：0～10％；WO 3：0～10％；Bi 2O 3：0～5％；Ta 2O 5：0～5％；Sb 2O 3：0～1％组成。
进一步的，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：
1)B 2O 3+Al 2O 3为0～12％；
2)Re 2O 3为0～15％；
3)RO为0～10％；
4)SiO 2+ZrO 2为30～55％；
5)Nb 2O 5+ZrO 2为40～70％；
6)TiO 2+WO 3+Bi 2O 3为0～10％；
7)Rn 2O为6～20％；
8)(SiO 2+ZrO 2)/Rn 2O为1.5～8.0；
9)ZrO 2/Rn 2O为0.1～2.3，
所述Re 2O 3为La 2O 3、Gd 2O 3、Y 2O 3的合计含量，RO为BaO、SrO、CaO、MgO的合计含量，Rn 2O为Li 2O、Na 2O、K 2O的合计含量。
进一步的，所述的光学玻璃，其组分以重量百分比表示，其中：SiO 2：28～42％；和/或ZrO 2：3～12％；和/或Nb 2O 5：38～57％；和/或Li 2O：2～8％；和/或Na 2O：4～13％；和/或K 2O：0.5～8％；和/或B 2O 3：0～5％；和/或Al 2O 3： 0～2％；和/或La 2O 3：0～5％；和/或Gd 2O 3：0～5％；和/或Y 2O 3：0～5％；和/或Yb 2O 3：0～5％；和/或BaO：0～5％；和/或SrO：0～5％；和/或CaO：0～8％；和/或MgO：0～3％；和/或ZnO：0～5％；和/或TiO 2：0～7％；和/或WO 3：0～5％；和/或Ta 2O 5：0～2％；和/或Sb 2O 3：0～0.5％。
进一步的，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：
1)B 2O 3+Al 2O 3为0～6％；
2)Re 2O 3为0～8％；
3)RO为0～8％；
4)SiO 2+ZrO 2为33～52％；
5)Nb 2O 5+ZrO 2为45～65％；
6)TiO 2+WO 3+Bi 2O 3为0～7％；
7)Rn 2O为10～18％；
8)(SiO 2+ZrO 2)/Rn 2O为1.8～6.5；
9)ZrO 2/Rn 2O为0.2～1.8，
所述Re 2O 3为La 2O 3、Gd 2O 3、Y 2O 3的合计含量，RO为BaO、SrO、CaO、MgO的合计含量，Rn 2O为Li 2O、Na 2O、K 2O的合计含量。
进一步的，所述的光学玻璃，其组分以重量百分比表示，其中：SiO 2：30～40％；和/或ZrO 2：4～10％；和/或Nb 2O 5：41～54％；和/或B 2O 3：0～3％；和/或Li 2O：3～6％；和/或Na 2O：5～12％；和/或K 2O：1～6％；和/或BaO：0～2％；和/或CaO：0～5％；和/或ZnO：0～2％；和/或TiO 2：0～4％；和/或Sb 2O 3：0～0.1％。
进一步的，所述的光学玻璃，其组分以重量百分比表示，满足以下7种情形中的一种以上：
1)RO为0～5％；
2)SiO 2+ZrO 2为36～49％；
3)Nb 2O 5+ZrO 2为50～60％；
4)TiO 2+WO 3+Bi 2O 3为0～4％；
5)Rn 2O为12～16％；
6)(SiO 2+ZrO 2)/Rn 2O为2.0～5.0；
7)ZrO 2/Rn 2O为0.3～1.3，
所述RO为BaO、SrO、CaO、MgO的合计含量，Rn 2O为Li 2O、Na 2O、K 2O的合计含量。
进一步的，所述的光学玻璃，其组分中不含有B 2O 3；和/或不含有Al 2O 3；和/或不含有La 2O 3；和/或不含有Gd 2O 3；和/或不含有Y 2O 3；和/或不含有Yb 2O 3；和/或不含有MgO；和/或不含有SrO；和/或不含有WO 3；和/或不含有Bi 2O 3；和/或不含有Ta 2O 5；和/或不含有Re 2O 3，所述Re 2O 3为La 2O 3、Gd 2O 3、Y 2O 3的合计含量。
进一步的，所述光学玻璃的折射率n d为1.74～1.82，优选折射率n d为1.76～1.80；阿贝数ν d为25～32，优选阿贝数ν d为27～30。
进一步的，所述光学玻璃的相对部分色散P g,F≤0.6497-0.001703×ν d，优选P g,F≤0.6477-0.001703×ν d；和/或所述光学玻璃的λ 5为360nm以下，优选λ 5为350nm以下。
玻璃预制件，采用上述的光学玻璃制成。
光学元件，采用上述的光学玻璃或上述的玻璃预制件制成。
光学仪器，含有上述的光学玻璃，和/或含有上述的光学元件。
本发明的有益效果是：通过含有合适量的SiO 2和碱金属氧化物等组分，使光学玻璃具有优异的抗析晶性能；通过含有Nb 2O 5、ZrO 2等具有高折射率氧化物组分，得到具有高折射高色散的光学玻璃；通过合理的组分设计使玻璃具有较低的相对部分色散。
具体实施方式
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。以下内容中有时候将本发明光学玻璃简称为玻璃。
Ⅰ、光学玻璃
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％。
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。
<必要组分和任选组分>
SiO 2是玻璃网络生成体，具有提升玻璃的化学稳定性和耐候性、维持玻璃抗析晶性能的作用，若SiO 2的含量低于25％，难以达到上述效果。因此SiO 2含量的下限为25％，优选SiO 2含量的下限为28％，更优选SiO 2含量的下限为30％。若SiO 2的含量高于45％，则玻璃变得很难熔，且难以获得本发明所期望的折射率。因此，SiO 2的含量上限为45％，优选上限为42％，更优选上限为40％。
B 2O 3可以降低玻璃的化料难度，同时降低玻璃高温粘度和转变温度。但是在本发明中，当B 2O 3处于[BO3]配位状态时，会使玻璃的相对部分色散增大。为保证玻璃具有低的相对部分色散，本发明中B 2O 3的含量为10％以下，优选为5％以下，更优选为3％以下，进一步优选不含有B 2O 3。
Al 2O 3能改善玻璃的耐候性，但会提升玻璃的化料温度和高温粘度，增加生产难度。当Al 2O 3含量超过5％时，玻璃呈现熔融性变差、耐失透性降低的倾向。因此，本发明Al 2O 3的含量为0～5％，优选为0～2％，更优选不含有Al 2O 3。
在本发明的一些实施方式中，通过控制B 2O 3和Al 2O 3的合计含量
B 2O 3+Al 2O 3在12％以下，有利于将玻璃的相对部分色散维持在设计范围内，优选B 2O 3+Al 2O 3为0～6％。
La 2O 3是一种高折射低色散的组分，在玻璃中能极大地降低玻璃的相对部分色散，但其含量过高时导致玻璃色散降低，较难实现本发明所期望的高折射高色散的光学特性。因此，本发明的La 2O 3的含量为10％以下，优选含量为5％以下，更优选为不含有La 2O 3。
Gd 2O 3是一种高折射低色散的组分，在玻璃中能起到降低玻璃的相对部分色散的作用，但是昂贵的原料价格限制了Gd 2O 3在玻璃中的使用。因此，Gd 2O 3的含量为0～10％，优选0～5％，更优选不含有Gd 2O 3。
Y 2O 3可以改善玻璃的熔融性，同时还可以提升玻璃耐候性，但其含量过高时导致玻璃色散降低，无法实现本发明所期望的高折射高色散的光学特性。因此，Y 2O 3的含量为0～10％，优选0～5％，更优选为不含有Y 2O 3。
La 2O 3、Gd 2O 3和Y 2O 3在玻璃中可以起到提高折射率、降低相对部分色散的作用，但含量过多时将难以实现本发明所期望的高折射高色散的光学特性。因此本发明中La 2O 3、Gd 2O 3、Y 2O 3的合计含量Re 2O 3优选为0～15％，更优选Re 2O 3为0～8％，进一步优选不含有Re 2O 3。
Yb 2O 3在玻璃中可以提高玻璃的折射率，但其在近红外区域有明显的吸收峰，作为光学元件使用时会改变透过光线的光谱构成，进而影响到图像的还原效果。因此，Yb 2O 3的含量范围限定为0～10％，优选为0～5％，更优选不含有Yb 2O 3。
BaO的原料成本低廉、易于获取，在玻璃中能够很好地提升玻璃的折射率。但BaO对降低玻璃的密度是不利的，另外BaO含量过多时，玻璃的耐候性快速下降。因此，BaO含量限定为0～10％，优选为0～5％，更优选为0～2％。
适量的SrO可以提升玻璃的耐候性，降低玻璃的密度，但由于SrO价格昂贵，含量高导致玻璃成本上升，因此SrO的含量限定为0～10％，优选为0～5％，更优选不含有SrO。
CaO可以提升玻璃的硬度、机械强度和耐候性，更为重要的是，相比于BaO和SrO，CaO对降低玻璃的密度更有利，此外CaO还有利于生产过程中光学常数的控制与调节。但是CaO含量过多时，导致玻璃熔化困难，生产过程中容易在熔化池形成一层富钙的硬壳。因此，CaO的含量限定为0～10％，优选为0～8％，更优选为0～5％。
MgO有助于提升玻璃的耐候性，但含量高时玻璃的折射率难以达到设计要求，玻璃的抗析晶性能和稳定性下降，同时玻璃的成本快速上升。因此，MgO含量限定为0～5％，优选为0～3％，更优选不含有MgO。
BaO、SrO、CaO、MgO都属于碱土金属氧化物，在本发明中，为获得优异的抗析晶性能和机械强度，碱土金属氧化物的合计含量RO优选控制在0～10％范围内，更优选为0～8％，进一步优选为0～5％。
ZnO可以改善玻璃的耐酸稳定性，提升玻璃耐候性，降低玻璃的转变温度，但当其含量过高时，会增加熔炼过程中对铂金器皿的侵蚀，降低熔炉的使用寿命。因此，本发明玻璃中的ZnO的含量为0～10％，优选为0～5％，更优选为0～2％。
ZrO 2具有改善玻璃的耐候性，提升玻璃的抗析晶性的作用。同时，ZrO 2在玻璃中可以大幅度降低玻璃的相对部分色散。但ZrO 2在本体系玻璃中的溶解度不高，含量过多时反而容易游离于玻璃系统之外，形成析晶核，进而导致玻璃的抗析晶性能变差。因此，本发明中ZrO 2的含量为2～15％，优选为3～12％，更优选为4～10％。
SiO 2和ZrO 2都可以提升玻璃的耐候性，同时SiO 2和ZrO 2也是本发明中较难熔化的两种组分。通过发明人大量实验研究发现，在一些实施方式中，当SiO 2和ZrO 2的合计含量SiO 2+ZrO 2在30～55％时，玻璃既可以获得优异的 耐候性，又可以获得较好的生产性能。因此，优选SiO 2+ZrO 2为30～55％，更优选SiO 2+ZrO 2为33～52％，进一步优选SiO 2+ZrO 2为36～49％。
Nb 2O 5是本发明玻璃的必要组分，是保证玻璃具有高折射高色散和低相对部分色散特性的关键组分。经本发明人潜心研究发现，Nb 2O 5在阿贝数为25～32范围时，对玻璃的相对部分色散与对阿贝数的贡献大致一致，即随着玻璃中Nb 2O 5的增长，玻璃的相对部分色散偏离值(ΔP g,F)基本没有变化。因此，本发明中Nb 2O 5的含量为35～60％，优选为38～57％，更优选为41～54％。
Nb 2O 5和ZrO 2是维持本发明低的相对部分色散性能的关键组分，在本发明的一些实施方式中，当Nb 2O 5和ZrO 2的合计含量Nb 2O 5+ZrO 2控制在40～70％范围内时，玻璃的折射率、色散和相对部分色散能够较好的达到设计要求。因此，优选Nb 2O 5+ZrO 2为40～70％，更优选为45～65％，进一步优选为50～60％。
TiO 2可以提升玻璃的折射率和色散，改善玻璃的抗析晶性能。但TiO 2在玻璃中会导致P g,F急剧上升，当玻璃中的TiO 2含量高于10％时，玻璃的P g,F特性难以满足设计要求。因此，TiO 2的含量为0～10％，优选为0～7％，更优选为0～4％。
WO 3可以提升玻璃的折射率和色散，但会导致玻璃的P g,F急剧上升，同时也会导致玻璃的光透过率降低。本发明中WO 3含量为0～10％，优选为0～5％，更优选不含有WO 3。
Bi 2O 3可以提升玻璃的折射率和色散，但会导致玻璃的P g,F急剧上升。另外，Bi 2O 3在熔炼过程中对铂金器皿的腐蚀较为严重，因此其含量限定为5％以内，优选不含有Bi 2O 3。
TiO 2、WO 3和Bi 2O 3都具有提升玻璃的折射率和色散的作用，但都会使玻璃的P g,F剧烈上升。因此，本发明中优选TiO 2、WO 3和Bi 2O 3的合计含量TiO 2+WO 3+Bi 2O 3为0～10％，更优选TiO 2+WO 3+Bi 2O 3为0～7％，进一步优选TiO 2+WO 3+Bi 2O 3为0～4％。
Ta 2O 5是一种高折射高色散组分，可以降低玻璃的P g,F值，同时Ta 2O 5可以改善玻璃的抗析晶性能，提升玻璃的稳定性。但是昂贵的原料成本极大地限制了Ta 2O 5的使用。本发明中Ta 2O 5的含量为0～5％，优选为0～2％，更优选不含有Ta 2O 5。
Li 2O属于碱金属氧化物，是本发明中降低玻璃生产难度的关键组分。Li 2O可以作为助熔剂使用，降低玻璃的化料难度。同时，Li 2O可以降低玻璃的高温粘度和转变温度，使玻璃生产和加工更为容易。经发明人潜心研究发现，通过使玻璃中含有Li 2O，利用Li 2O的积聚效应，可以提升玻璃的耐候性。但若Li 2O的含量过高，会造成玻璃的耐酸稳定性下降。因此，在本发明玻璃中，Li 2O的含量为1～10％，优选为2～8％，更优选为3～6％。
Na 2O和K 2O也可以降低玻璃的化料温度和高温粘度，降低玻璃生产难度，但是相比于Li 2O的积聚效应，Na 2O和K 2O会导致玻璃的硅网络结构断裂，并导致玻璃P g,F增大。因此，本发明玻璃中Na 2O的含量为2～15％，优选为4～13％，更优选为5～12％；K 2O的含量为0～10％，优选为0.5～8％，更优选为1～6％。
Li 2O、Na 2O和K 2O都属于碱金属氧化物，可以降低玻璃的生产难度，但含量过多会导致玻璃的化学稳定性降低。因此，本发明中优选将Li 2O、Na 2O和K 2O的合计含量Rn 2O控制在6～20％范围内，更优选为10～18％，进一步优选为12～16％。
经发明人大量实验研究发现，碱金属氧化物Rn 2O可以促进SiO 2和ZrO 2熔化，降低玻璃的熔炼难度。进一步的，当SiO 2和ZrO 2的合计含量SiO 2+ZrO 2与Rn 2O的含量之间的比值(SiO 2+ZrO 2)/Rn 2O在1.5～8.0之间时，玻璃能够获得优异的熔化性能和抗析晶性能，优选(SiO 2+ZrO 2)/Rn 2O为1.8～6.5，更优选(SiO 2+ZrO 2)/Rn 2O为2.0～5.0。
硅酸盐玻璃网络结构对ZrO 2的承载能力不强，当ZrO 2含量过高时，在熔制过程中容易析出形成结石。通过发明人大量实验研究发现，在一些实施方式中，碱金属氧化物Rn 2O可以提升硅酸盐玻璃对ZrO 2的承载能力，当 ZrO 2的含量与Rn 2O的含量之间的比值ZrO 2/Rn 2O在0.1～2.3范围内时，可以提高本发明玻璃系统对ZrO 2的承载能力，并提高玻璃的化学稳定性。优选ZrO 2/Rn 2O为0.2～1.8，更优选ZrO 2/Rn 2O为0.3～1.3。
Sb 2O 3可以在本发明中作为澄清剂使用，以提高玻璃的澄清效果，其含量范围为0～1％，优选为0～0.5％，更优选为0～0.1％。
<不应含有的组分>
本发明玻璃中，V、Cr、Mn、Fe、Co、Ni、Cu、Ag以及Mo等过渡金属的氧化物，即使单独或复合地少量含有的情况下，玻璃也会被着色，在可见光区域的特定的波长产生吸收，从而减弱本发明的提高可见光透过率效果的性质，因此，特别是对于可见光区域波长的透过率有要求的光学玻璃，优选实际上不含有。
Th、Cd、Tl、Os、Be以及Se的氧化物，近年来作为有害的化学物质而有控制使用的倾向，不仅在玻璃的制造工序，直至加工工序以及产品化后的处置上对环境保护的措施是必需的。因此，在重视对环境的影响的情况下，除了不可避免地混入以外，优选实际上不含有它们。由此，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。
为了实现环境友好，本发明的光学玻璃不含有As 2O 3和PbO。虽然As 2O 3具有消除气泡和较好的防止玻璃着色的效果，但As 2O 3的加入会加大玻璃对熔炉特别是对铂金熔炉的铂金侵蚀，导致更多的铂金离子进入玻璃，对铂金熔炉的使用寿命造成不利影响。PbO可显著提高玻璃的高折射率和高色散性能，但PbO和As 2O 3都造成环境污染的物质。
本文所记载的“不含有”“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。
下面，对本发明的光学玻璃的性能进行说明。
<折射率与阿贝数>
光学玻璃折射率(n d)与阿贝数(ν d)按照《GB/T 7962.1—2010》规定的方法测试。
在一些实施方式中，本发明光学玻璃的折射率(n d)为1.74～1.82，优选为1.76～1.80。
在一些实施方式中，本发明光学玻璃的阿贝数(ν d)为25～32，优选为27～30。
<相对部分色散>
光学玻璃的相对部分色散(P g,F)计算方式为：P g,F＝(n g-n F)/(n F-n C)。式中n g、n F与n C按照《GB/T 7962.1—2010》规定的方法测试。
在一些实施方式中，本发明光学玻璃的相对部分色散(P g,F)≤0.6497-0.001703×ν d，优选为P g,F≤0.6477-0.001703×ν d。
<透射比>
玻璃的透射比(λ 5)用于衡量玻璃的短波透过情况，具体测试方法为：将10mm厚的双面抛光样品置于分光光度计上测试玻璃透射情况，λ 5指的是玻璃透射比达到5％时对应的波长。
在一些实施方式中，本发明所述光学玻璃的λ 5为360nm以下，优选为350nm以下。
<抗析晶性能>
光学玻璃的抗析晶性能测试方法如下：将试样放入T g+230℃的马弗炉中保温15分钟后取出，再放置在室温下冷却，再经双面抛光后观察样品内每立方厘米内的析晶颗粒数量(A)。
在一些实施方式中，本发明所述光学玻璃析晶数量(A)为5颗以下，优选为2颗以下，更优选为0颗。
[制造方法]
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常规工艺生产，使用复合盐(如碳酸盐、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1250～1450℃的熔炼炉中熔制，并且经澄清、搅拌和均化后，得到没有气泡及不含未溶解物质的均质熔融玻璃，将此熔融玻璃在模具内铸型并退火而成。本领域技术人员能够根据实际需要，适当地选择原料、工艺方法和工艺参数。
Ⅱ、玻璃预制件和光学元件
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。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。
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。
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。
Ⅲ、光学仪器
本发明光学玻璃所形成的光学元件可制作如照相设备、车载设备、摄像设备、显示设备和监控设备等光学仪器。
由于本发明光学玻璃具有高折射高色散和低相对部分色散性能，因此特别适用于长焦镜头和高清交换镜头中。
实施例
<光学玻璃实施例>
为了进一步清楚地阐释和说明本发明的技术方案，提供以下的非限制性实施例。
本实施例采用上述光学玻璃的制造方法得到具有表1～表4所示的光学玻璃。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4中。
表1.
组分(wt％) 1# 2# 3# 4# 5# 6# 7# 8# 9# 10#
SiO 2 35.24 36.54 26.25 38.01 32.14 25.86 44.24 32.45 29.85 28.32
B 2O 3 0.21 0 0 0 1.27 0 0 0 0 0
Al 2O 3 0 0 0 0 0 0 0 0 0 0
La 2O 3 0 0 0 0 2.35 0 0 0 0 0
Gd 2O 3 0 0 0 0 1.24 0 0 0 0 8.21
Y 2O 3 0 0 0 8 1.34 0.69 0 0 0 0
Yb 2O 3 0 0 0 0 0 0 0 0 0 0
BaO 0 0 9.25 0 0 0 0 0 0 0
SrO 0 0 0 0 0.54 0 0 0 0 0
CaO 0.55 0 0 0 0 0 0 9.75 0 4.52
MgO 0 0 0 0 0.47 0 0 0 0 1
ZnO 0 0 0 0 0 0 0 0 0 1.25
ZrO 2 6.35 4.25 4.25 10.24 6.54 7.58 2.24 2.98 3.25 9.35
Nb 2O 5 43.21 37.25 37.42 35.45 36.87 44.25 40.25 46.78 56.25 41.25
TiO 2 0 8.65 4.61 0 0 5.25 0.78 1.24 0 0
WO 3 0 0 0 0 0 0 0 0 0 0
Bi 2O 3 0 0 0 0 4.25 0 0 0 0 0
Ta 2O 5 0 0 0 2.24 0 0 0 0 0 0
Li 2O 5.31 3.25 9.14 1.78 4.54 4.12 3.01 1.24 6.35 3.25
Na 2O 7.11 9.62 2.54 3.74 8.45 12.25 5.24 2.25 4.12 2.22
K 2O 2.02 0 6.54 0.54 0 0 4.24 3.31 0.18 0.63
Sb 2O 3 0 0.44 0 0 0 0 0 0 0 0
合计 100 100 100 100 100 100 100 100 100 100
B 2O 3+Al 2O 3 0.21 0 0 0 1.27 0 0 0 0 0
Re 2O 3 0 0 0 8 4.93 0.69 0 0 0 8.21
RO 0.55 0 9.25 0 1.01 0 0 9.75 0 5.52
SiO 2+ZrO 2 41.59 40.79 30.50 48.25 38.68 33.44 46.48 35.43 33.10 37.67
Rn 2O 14.44 12.87 18.22 6.06 12.99 16.37 12.49 6.80 10.65 6.10
Nb 2O 5+ZrO 2 49.56 41.50 41.67 45.69 43.41 51.83 42.49 49.76 59.50 50.60
TiO 2+WO 3+Bi 2O 3 0 8.65 4.61 0 4.25 5.25 0.78 1.24 0 0
(SiO 2+ZrO 2)/Rn 2O 2.88 3.17 1.67 7.96 2.98 2.04 3.72 5.21 3.11 6.18
ZrO 2/Rn 2O 0.44 0.33 0.23 1.69 0.50 0.46 0.18 0.44 0.31 1.53
n d 1.77234 1.74365 1.74856 1.76352 1.75458 1.78562 1.76541 1.77965 1.81753 1.78214
v d 29.65 25.24 28.14 28.35 26.54 26.32 30.33 28.86 27.95 28.56
P g,F 0.5961 0.6054 0.6004 0.6002 0.6032 0.6025 0.5974 0.5985 0.6 0.5997
λ 5(nm) 349 359 351 338 354 347 344 346 340 342
A(颗) 0 0 5 0 0 3 0 0 1 0
表2.
组分(wt％) 11# 12# 13# 14# 15# 16# 17# 18# 19# 20#
SiO 2 31.78 25.21 32.81 27.63 26.48 40.67 40.25 25.34 42.05 32.82
B 2O 3 0 9.58 0 4.25 0 0 0 0 2.25 0
Al 2O 3 0 2.34 0 0 0 0 4.25 0 0 0
La 2O 3 0 0 0 1.25 4.25 0 9.21 0 0 0
Gd 2O 3 0 0.44 0 0 0 0 0 0 0 4.45
Y 2O 3 0 0 0 0 0 0 0 0 0 0
Yb 2O 3 7.52 0 0 0 0 0 0 0 0 0
BaO 0 0 0 0 0 0 0 0 0 0
SrO 1.25 0 0 0 0 0 0 0 0 0
CaO 0 0 0 0 0 0 0 2.23 0 0
MgO 4.12 0 0 0 0 0 0 0 0 0
ZnO 0 0 0 0 0 8.86 0 0 0 0
ZrO 2 3.21 8.52 5.51 14.23 11.24 3.27 2.84 12.35 7.00 4.42
Nb 2O 5 37.04 36.00 47.25 46.25 45.25 41.00 37.24 35.75 39.25 52.24
TiO 2 0 0 0 0 0 0 0 2.42 0 0
WO 3 0 0 7.86 0 0 0 0 5.57 0 0
Bi 2O 3 2.23 0 0 0 0 0 0 0 0 0
Ta 2O 5 0 0.75 0 0 0 0 0 0 0 0
Li 2O 1.47 8.58 2.32 3.02 6.54 2.50 1.25 1.34 5.00 2.25
Na 2O 2.24 3.21 4.25 2.27 6.24 3.25 3.56 14.25 2.14 2.72
K 2O 9.14 5.25 0 1.10 0 0.45 1.40 0 2.31 1.10
Sb 2O 3 0 0.12 0 0 0 0 0 0.75 0 0
合计 100 100 100 100 100 100 100 100 100 100
B 2O 3+Al 2O 3 0 11.92 0 4.25 0 0 4.25 0 2.25 0
Re 2O 3 0 0.44 0 1.25 4.25 0 9.21 0 0 4.45
RO 5.37 0 0 0 0 0 0 2.23 0 0
SiO 2+ZrO 2 34.99 33.73 38.32 41.86 37.72 43.94 43.09 37.69 49.05 37.24
Rn 2O 12.85 17.04 6.57 6.39 12.78 6.20 6.21 15.59 9.45 6.07
Nb 2O 5+ZrO 2 40.25 44.52 52.76 60.48 56.49 44.27 40.08 48.1 46.25 56.66
TiO 2+WO 3+Bi 2O 3 2.23 0 7.86 0 0 0 0 7.99 0 0
(SiO 2+ZrO 2)/Rn 2O 2.72 1.98 5.83 6.55 2.95 7.09 6.94 2.42 5.19 6.16
ZrO 2/Rn 2O 0.25 0.5 0.84 2.23 0.88 0.53 0.46 0.79 0.74 0.73
n d 1.74562 1.75845 1.79652 1.81879 1.80412 1.75865 1.74124 1.77521 1.76548 1.81457
v d 28.54 30.11 25.89 28.21 28.95 30.45 30.21 26.21 27.75 27.95
P g,F 0.5998 0.5974 0.6042 0.601 0.5995 0.5965 0.5962 0.6015 0.601 0.6014
λ 5(nm) 350 345 358 345 342 341 340 357 342 339
A(颗) 0 1 0 0 0 0 0 2 0 0
表3.
组分(wt％) 21# 22# 23# 24# 25# 26# 27# 28# 29# 30#
SiO 2 28.56 34.14 40.24 33.10 35.15 34.95 36.21 37.97 34.54 37.24
B 2O 3 0 0 0 0 0 0 0 0 0 0
Al 2O 3 0 0 0 0 0 0 0 1.25 3.50 0
La 2O 3 0 0 0 0 0 0 0 0 0 0
Gd 2O 3 0 2.25 0 0 0 0 0 0 0 0
Y 2O 3 0 0 0 4.58 0 0 0 0 0 0
Yb 2O 3 3.24 0 0 0 2.24 0 0 0 0 0
BaO 0 4.57 0 0 0 0 0 0 2.65 1.53
SrO 0 0 0 0 0 0 0 0 0 0
CaO 0 0 0 0 0 0 4.44 0 0 0
MgO 0 0 0 0 0 2.25 0 0 0 0
ZnO 0 0 0 0 0 0 0 0 2.25 0
ZrO 2 6.25 4.42 7.51 3.21 2.33 5.25 2.10 5.98 3.87 5.42
Nb 2O 5 44.25 41.24 39.75 46.12 48.54 42.94 47.35 42.35 42.67 42.24
TiO 2 0 0 0 0 0 3.12 0 0 0 0
WO 3 0 3.54 0 0 0 0 0 0 0 0
Bi 2O 3 0 0 0 0 0 0 0 0 0 0
Ta 2O 5 0 0 0 0 0 0 0 0 4.42 0
Li 2O 3.21 5.45 6.21 7.45 2.14 1.25 1.42 3.21 1.25 6.24
Na 2O 9.24 3.25 4.51 5.54 2.35 10.24 4.24 9.24 3.65 5.21
K 2O 5.25 1.14 1.78 0 7.25 0 4.24 0 1.20 2.12
Sb 2O 3 0 0 0 0 0 0 0 0 0 0
合计 100 100 100 100 100 100 100 100 100 100
B 2O 3+Al 2O 3 0 0 0 0 0 0 0 1.25 3.50 0
Re 2O 3 0 2.25 0 4.58 0 0 0 0 0 0
RO 0 4.57 0 0 0 2.25 4.44 0 2.65 1.53
SiO 2+ZrO 2 34.81 38.56 47.75 36.31 37.48 40.2 38.31 43.95 38.41 42.66
Rn 2O 17.70 9.84 12.50 12.99 11.74 11.49 9.90 12.45 6.10 13.57
Nb 2O 5+ZrO 2 50.50 45.66 47.26 49.33 50.87 48.19 49.45 48.33 46.54 47.66
TiO 2+WO 3+Bi 2O 3 0 3.54 0 0 0 3.12 0 0 0 0
(SiO 2+ZrO 2)/Rn 2O 1.97 3.92 3.82 2.80 3.19 3.450 3.87 3.53 6.297 3.14
ZrO 2/Rn 2O 0.35 0.45 0.60 0.25 0.20 0.46 0.21 0.48 0.63 0.40
n d 1.78521 1.76251 1.77201 1.77856 1.78354 1.77254 1.77965 1.77451 1.76325 1.77214
v d 30.55 27.24 30.24 30.86 29.32 27.54 30.85 29.64 29.21 29.78
P g,F 0.5962 0.6021 0.5971 0.5961 0.5978 0.6014 0.5962 0.5984 0.5988 0.5977
λ 5(nm) 347 353 339 345 341 352 348 347 344 344
A(颗) 0 0 0 0 0 0 0 0 0 0
表4.
组分(wt％) 31# 32# 33# 34# 35# 36# 37# 38# 39# 40#
SiO 2 39.21 33.24 33.25 30.21 29.85 31.24 32.02 32.54 38.24 35.74
B 2O 3 0 0 0 3.25 0 0 0 2.35 0 0
Al 2O 3 0 0 0 0 0 0 0 0 0 0
La 2O 3 0 0 0 2.37 0 0 0 0.24 0 0
Gd 2O 3 0 0 0 0 0 0 0 3.32 0 0
Y 2O 3 0 0 2.80 0 0 0 0 0 0 0
Yb 2O 3 0 0 0 0 0 0 1.24 0 0 0
BaO 0 0 0 0 0 0 0 0 0 0
SrO 5.39 0 0 9.58 0 0 0 2.32 0 0
CaO 0 0 0 0 0 0 0 0 0 0
MgO 0 0 0 0 0 0 0 0 0 0
ZnO 0 3.66 5.12 0 0 0 0 0 0 0.94
ZrO 2 4.21 8.01 3.88 5.35 3.32 9.21 8.65 5.35 3.24 6.87
Nb 2O 5 36.25 37.25 41.98 37.45 54.34 39.98 45.54 41.11 50.14 40.25
TiO 2 0 0 0 0 0.8 0 0 0 0 0
WO 3 0 0 0 0 0 0 0 0 0 0
Bi 2O 3 0 0 0 1.12 0 0 0 0 0 0
Ta 2O 5 0 0 0 0 0 0 0 2.16 0 0
Li 2O 7.24 4.05 4.45 6.25 4.45 3.01 8.01 2.35 1.74 5.12
Na 2O 6.25 9.54 8.52 4.42 7.24 11.24 4.54 5.01 3.32 7.54
K 2O 1.45 4.25 0 0 0 5.32 0 3.25 3.32 3.54
Sb 2O 3 0 0 0 0 0 0 0 0 0 0
合计 100 100 100 100 100 100 100 100 100 100
B 2O 3+Al 2O 3 0 0 0 3.25 0 0 0 2.35 0 0
Re 2O 3 0 0 2.80 2.37 0 0 0 3.56 0 0
RO 5.39 0 0 9.58 0 0 0 2.32 0 0
SiO 2+ZrO 2 43.42 41.25 37.13 35.56 33.17 40.45 40.67 37.89 41.48 42.61
Rn 2O 14.94 17.84 12.97 10.67 11.69 19.57 12.55 10.61 8.38 16.20
Nb 2O 5+ZrO 2 40.46 45.26 45.86 42.80 57.66 49.19 54.19 46.46 53.38 47.12
TiO 2+WO 3+Bi 2O 3 0 0 0 1.12 0.80 0 0 0 0 0
(SiO 2+ZrO 2)/Rn 2O 2.91 2.31 2.86 3.33 2.84 2.07 3.24 3.57 4.95 2.63
ZrO 2/Rn 2O 0.28 0.45 0.30 0.50 0.28 0.47 0.69 0.50 0.39 0.42
n d 1.74321 1.76021 1.76874 1.75024 1.81021 1.77765 1.80241 1.76584 1.79321 1.77024
v d 29.77 31.47 29.96 29.21 29.55 31.54 31.01 31.25 31.24 31.75
P g,F 0.5976 0.5954 0.5967 0.5985 0.5984 0.5945 0.5954 0.5955 0.5955 0.5941
λ 5(nm) 347 341 350 348 340 350 341 346 349 345
A(颗) 0 5 0 0 0 0 0 0 0 4
<玻璃预制件实施例>
将光学玻璃实施例1～40所得到的玻璃使用例如研磨加工的手段、或再热压成型、精密冲压成型等模压成型的手段，来制作凹弯月形透镜、凸弯月形透镜、双凸透镜、双凹透镜、平凸透镜、平凹透镜等各种透镜、棱镜等的预制件。
<光学元件实施例>
将上述玻璃预制件实施例所得到的这些预制件退火，在降低玻璃内部的变形的同时进行微调，使得折射率等光学特性达到所需值。
接着，对各预制件进行磨削、研磨，制作凹弯月形透镜、凸弯月形透镜、双凸透镜、双凹透镜、平凸透镜、平凹透镜等各种透镜、棱镜。所得到的光学元件的表面上还可涂布防反射膜。
<光学仪器实施例>
将上述光学元件实施例制得的光学元件通过光学设计，通过使用一个或多个光学元件形成光学部件或光学组件，可用于例如成像设备、传感器、显微镜、医药技术、数字投影、通信、光学通信技术/信息传输、汽车领域中的光学/照明、光刻技术、准分子激光器、晶片、计算机芯片以及包括这样的电路及芯片的集成电路和电子器件。

Claims (14)

  1. 光学玻璃，其特征在于，其组分以重量百分比表示，含有：SiO 2：25～45％；ZrO 2：2～15％；Nb 2O 5：35～60％；Li 2O：1～10％；Na 2O：2～15％；K 2O：0～10％。
  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：B 2O 3：0～10％；和/或Al 2O 3：0～5％；和/或La 2O 3：0～10％；和/或Gd 2O 3：0～10％；和/或Y 2O 3：0～10％；和/或Yb 2O 3：0～10％；和/或BaO：0～10％；和/或SrO：0～10％；和/或CaO：0～10％；和/或MgO：0～5％；和/或ZnO：0～10％；和/或TiO 2：0～10％；和/或WO 3：0～10％；和/或Bi 2O 3：0～5％；和/或Ta 2O 5：0～5％；和/或Sb 2O 3：0～1％。
  3. 光学玻璃，其特征在于，其组分以重量百分比表示，由SiO 2：25～45％；ZrO 2：2～15％；Nb 2O 5：35～60％；Li 2O：1～10％；Na 2O：2～15％；K 2O：0～10％；B 2O 3：0～10％；Al 2O 3：0～5％；La 2O 3：0～10％；Gd 2O 3：0～10％；Y 2O 3：0～10％；Yb 2O 3：0～10％；BaO：0～10％；SrO：0～10％；CaO：0～10％；MgO：0～5％；ZnO：0～10％；TiO 2：0～10％；WO 3：0～10％；Bi 2O 3：0～5％；Ta 2O 5：0～5％；Sb 2O 3：0～1％组成。
  4. 根据权利要求1～3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：
    1)B 2O 3+Al 2O 3为0～12％；
    2)Re 2O 3为0～15％；
    3)RO为0～10％；
    4)SiO 2+ZrO 2为30～55％；
    5)Nb 2O 5+ZrO 2为40～70％；
    6)TiO 2+WO 3+Bi 2O 3为0～10％；
    7)Rn 2O为6～20％；
    8)(SiO 2+ZrO 2)/Rn 2O为1.5～8.0；
    9)ZrO 2/Rn 2O为0.1～2.3，
    所述Re 2O 3为La 2O 3、Gd 2O 3、Y 2O 3的合计含量，RO为BaO、SrO、CaO、MgO的合计含量，Rn 2O为Li 2O、Na 2O、K 2O的合计含量。
  5. 根据权利要求1～3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：SiO 2：28～42％；和/或ZrO 2：3～12％；和/或Nb 2O 5：38～57％；和/或Li 2O：2～8％；和/或Na 2O：4～13％；和/或K 2O：0.5～8％；和/或B 2O 3：0～5％；和/或Al 2O 3：0～2％；和/或La 2O 3：0～5％；和/或Gd 2O 3：0～5％；和/或Y 2O 3：0～5％；和/或Yb 2O 3：0～5％；和/或BaO：0～5％；和/或SrO：0～5％；和/或CaO：0～8％；和/或MgO：0～3％；和/或ZnO：0～5％；和/或TiO 2：0～7％；和/或WO 3：0～5％；和/或Ta 2O 5：0～2％；和/或Sb 2O 3：0～0.5％。
  6. 根据权利要求1～3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：
    1)B 2O 3+Al 2O 3为0～6％；
    2)Re 2O 3为0～8％；
    3)RO为0～8％；
    4)SiO 2+ZrO 2为33～52％；
    5)Nb 2O 5+ZrO 2为45～65％；
    6)TiO 2+WO 3+Bi 2O 3为0～7％；
    7)Rn 2O为10～18％；
    8)(SiO 2+ZrO 2)/Rn 2O为1.8～6.5；
    9)ZrO 2/Rn 2O为0.2～1.8，
    所述Re 2O 3为La 2O 3、Gd 2O 3、Y 2O 3的合计含量，RO为BaO、SrO、CaO、MgO的合计含量，Rn 2O为Li 2O、Na 2O、K 2O的合计含量。
  7. 根据权利要求1～3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：SiO 2：30～40％；和/或ZrO 2：4～10％；和/或Nb 2O 5：41～54％；和/或B 2O 3：0～3％；和/或Li 2O：3～6％；和/或Na 2O：5～12％；和/或K 2O：1～6％；和/或BaO：0～2％；和/或CaO：0～5％；和/ 或ZnO：0～2％；和/或TiO 2：0～4％；和/或Sb 2O 3：0～0.1％。
  8. 根据权利要求1～3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7种情形中的一种以上：
    1)RO为0～5％；
    2)SiO 2+ZrO 2为36～49％；
    3)Nb 2O 5+ZrO 2为50～60％；
    4)TiO 2+WO 3+Bi 2O 3为0～4％；
    5)Rn 2O为12～16％；
    6)(SiO 2+ZrO 2)/Rn 2O为2.0～5.0；
    7)ZrO 2/Rn 2O为0.3～1.3，
    所述RO为BaO、SrO、CaO、MgO的合计含量，Rn 2O为Li 2O、Na 2O、K 2O的合计含量。
  9. 根据权利要求1～3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B 2O 3；和/或不含有Al 2O 3；和/或不含有La 2O 3；和/或不含有Gd 2O 3；和/或不含有Y 2O 3；和/或不含有Yb 2O 3；和/或不含有MgO；和/或不含有SrO；和/或不含有WO 3；和/或不含有Bi 2O 3；和/或不含有Ta 2O 5；和/或不含有Re 2O 3，所述Re 2O 3为La 2O 3、Gd 2O 3、Y 2O 3的合计含量。
  10. 根据权利要求1～3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1.74～1.82，优选折射率n d为1.76～1.80；阿贝数ν d为25～32，优选阿贝数ν d为27～30。
  11. 根据权利要求1～3任一权利要求所述的光学玻璃，其特征在于，所述光学玻璃的相对部分色散P g,F≤0.6497-0.001703×ν d，优选P g,F≤0.6477-0.001703×ν d；和/或所述光学玻璃的λ 5为360nm以下，优选λ 5为350nm以下。
  12. 玻璃预制件，其特征在于，采用权利要求1～11任一所述的光学玻璃制成。
  13. 光学元件，其特征在于，采用权利要求1～11任一所述的光学玻 璃或权利要求12所述的玻璃预制件制成。
  14. 光学仪器，其特征在于，含有权利要求1～11任一所述的光学玻璃，和/或含有权利要求13所述的光学元件。
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