WO2022193797A1 - 高折射高色散光学玻璃及光学元件 - Google Patents

高折射高色散光学玻璃及光学元件 Download PDF

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WO2022193797A1
WO2022193797A1 PCT/CN2022/070073 CN2022070073W WO2022193797A1 WO 2022193797 A1 WO2022193797 A1 WO 2022193797A1 CN 2022070073 W CN2022070073 W CN 2022070073W WO 2022193797 A1 WO2022193797 A1 WO 2022193797A1
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tio
less
refractive
glass
optical glass
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PCT/CN2022/070073
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English (en)
French (fr)
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匡波
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成都光明光电股份有限公司
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Publication of WO2022193797A1 publication Critical patent/WO2022193797A1/zh

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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
    • 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
    • C03C3/066—Glass compositions containing silica with less than 40% silica by weight containing boron containing zinc
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/12—Silica-free oxide glass compositions
    • C03C3/16—Silica-free oxide glass compositions containing phosphorus
    • C03C3/21—Silica-free oxide glass compositions containing phosphorus containing titanium, zirconium, vanadium, tungsten or molybdenum
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/12—Silica-free oxide glass compositions
    • C03C3/253—Silica-free oxide glass compositions containing germanium

Definitions

  • the present invention relates to an optical glass, in particular to an optical glass with a refractive index of 1.95 or more and an Abbe number of 25 or less.
  • CN1896022A discloses a refractive index of not less than 2.000, Abbe number High-refractive and high-dispersion optical glass not greater than 27, but its transition temperature is high, which is not conducive to precision drop forming or precision molding.
  • the technical problem to be solved by the present invention is to provide a high-refractive and high-dispersion optical glass with a lower transition temperature.
  • High-refractive and high-dispersion optical glass its components are expressed in weight percentage, containing: P 2 O 5 : 8-25%; Bi 2 O 3 : 30-60%; Nb 2 O 5 : 15-35%; WO 3 : 3 to 25%, wherein Bi 2 O 3 /(Nb 2 O 5 +P 2 O 5 ) is 0.6 to 2.3.
  • the high-refractive and high-dispersion optical glass whose components are expressed in weight percentage, further contains: TiO 2 : 0-15%; and/or B 2 O 3 : 0-10%; and/or RO: and/or ZnO: 0-10%; and/or Li 2 O: 0-10%; and/or Na 2 O: 0-10%; and/or K 2 O: 0-10% and/or SiO 2 +Al 2 O 3 +ZrO 2 : 0-10%; and/or Ln 2 O 3 : 0-10%; and/or TeO 2 : 0-5%; and/or GeO 2 : 0-5%; and/or Ga 2 O 3 : 0-5%; and/or Ta 2 O 5 : 0-5%; and/or clarifying agent: 0-2%, the Ln 2 O 3 is La One or more of 2 O 3 , Gd 2 O 3 , Y 2 O 3 , Yb 2 O 3 , Lu 2 O 3 , RO is one or more
  • High-refractive and high-dispersion optical glass containing P 2 O 5 , Nb 2 O 5 , WO 3 and Bi 2 O 3 as essential components, the components are expressed in weight percentage, wherein Bi 2 O 3 /(Nb 2 O 5 + P 2 O 5 ) is 0.6 to 2.3, the high refractive index and high dispersion optical glass has a refractive index nd of 1.95 or more, an Abbe number ⁇ d of 25 or less, and a transition temperature T g of 520° C. or less.
  • the components of the high-refractive and high-dispersion optical glass contain: P 2 O 5 : 8-25%; and/or Bi 2 O 3 : 30-60%; and/or Nb 2O5 : 15-35%; and/or WO3: 3-25 %; and/or TiO2 : 0-15 %; and/or B2O3: 0-10%; and/or RO: 0 and/or ZnO: 0-10%; and/or Li 2 O: 0-10%; and/or Na 2 O: 0-10%; and/or K 2 O: 0-10%; and/or SiO 2 +Al 2 O 3 +ZrO 2 : 0-10%; and/or Ln 2 O 3 : 0-10%; and/or TeO 2 : 0-5%; and/or GeO 2 : 0 and/or Ga 2 O 3 : 0-5%; and/or Ta 2 O 5 : 0-5%; and/or clarifying agent: 0-2%
  • the components of the high-refractive and high-dispersion optical glass satisfy one or more of the following five situations:
  • Bi 2 O 3 /(Nb 2 O 5 +P 2 O 5 ) is 0.7 to 2.0, preferably Bi 2 O 3 /(Nb 2 O 5 +P 2 O 5 ) is 0.8 to 1.5, more preferably Bi 2 O 3 /(Nb 2 O 5 +P 2 O 5 ) is 0.9 to 1.3;
  • Nb 2 O 5 +TiO 2 )/Bi 2 O 3 is 0.3 to 1.3, preferably (Nb 2 O 5 +TiO 2 )/Bi 2 O 3 is 0.4 to 1.0, more preferably (Nb 2 O 5 +TiO 2 )/Bi 2 O 3 is 0.5-0.8, more preferably (Nb 2 O 5 +TiO 2 )/Bi 2 O 3 is 0.55-0.75;
  • Nb 2 O 5 +P 2 O 5 )/WO 3 is 1.0 to 15.0, preferably (Nb 2 O 5 +P 2 O 5 )/WO 3 is 1.5 to 12.0, more preferably (Nb 2 O 5 +P 2 O 5 )/WO 3 is 2.5 to 10.0, more preferably (Nb 2 O 5 +P 2 O 5 )/WO 3 is 3.0 to 7.0;
  • WO 3 /(Li 2 O+Na 2 O+K 2 O) is 0.2 or more, preferably WO 3 /(Li 2 O+Na 2 O+K 2 O) is 0.5 or more, more preferably WO 3 /(Li 2 O+Na 2 O+K 2 O) is 1.0-15.0, more preferably WO 3 /(Li 2 O+Na 2 O+K 2 O) is 1.5-8.0;
  • (Nb 2 O 5 +WO 3 +TiO 2 +P 2 O 5 )/Bi 2 O 3 is 0.5 to 2.5, preferably (Nb 2 O 5 +WO 3 +TiO 2 +P 2 O 5 )/Bi 2 O 3 is 0.7 to 2.0, more preferably (Nb 2 O 5 +WO 3 +TiO 2 +P 2 O 5 )/Bi 2 O 3 is 0.8 to 1.8, still more preferably (Nb 2 O 5 +WO 3 +TiO 2 + P 2 O 5 )/Bi 2 O 3 is 1.0 to 1.5.
  • the components of the high-refractive and high-dispersion optical glass satisfy one or more of the following four situations:
  • (Nb 2 O 5 +P 2 O 5 +TiO 2 +BaO)/(Bi 2 O 3 +WO 3 ) is 0.4 to 2.0, preferably (Nb 2 O 5 +P 2 O 5 +TiO 2 +BaO) /(Bi 2 O 3 +WO 3 ) is 0.5 to 1.5, more preferably (Nb 2 O 5 +P 2 O 5 +TiO 2 +BaO)/(Bi 2 O 3 +WO 3 ) is 0.6 to 1.2, more preferably (Nb 2 O 5 +P 2 O 5 +TiO 2 +BaO)/(Bi 2 O 3 +WO 3 ) is 0.65 to 1.0;
  • TiO 2 /(SiO 2 +Al 2 O 3 +ZrO 2 ) is 0.1 or more, preferably TiO 2 /(SiO 2 +Al 2 O 3 +ZrO 2 ) is 0.3 or more, more preferably TiO 2 /(SiO 2 + Al 2 O 3 +ZrO 2 ) is 0.5-20.0, more preferably TiO 2 /(SiO 2 +Al 2 O 3 +ZrO 2 ) is 0.8-10.0;
  • Na 2 O/(Li 2 O+Na 2 O+K 2 O) is 0.3-1.0, preferably Na 2 O/(Li 2 O+Na 2 O+K 2 O) is 0.4-0.9, more preferably Na 2 O/(Li 2 O+Na 2 O+K 2 O) is 0.5-0.8, more preferably Na 2 O/(Li 2 O+Na 2 O+K 2 O) is 0.5-0.75;
  • ZnO/(TiO 2 +BaO) is 5.0 or less, preferably ZnO/(TiO 2 +BaO) is 3.0 or less, more preferably ZnO/(TiO 2 +BaO) is 1.5 or less, still more preferably ZnO/(TiO 2 +BaO) ) is 0.8 or less.
  • the components of the high-refractive and high-dispersion optical glass contain: P 2 O 5 : 12-22%, preferably P 2 O 5 : 13-19%; and/or Bi 2 O 3 : 35-55%, preferably Bi 2 O 3 : 38-50%; and/or Nb 2 O 5 : 18-30%, preferably Nb 2 O 5 : 20-28%; and/or WO 3 : 4- 20%, preferably WO 3 : 6-15%; and/or TiO 2 : 0.5-8%, preferably TiO 2 : 1-5%; and/or B 2 O 3 : 0-8%, preferably B 2 O 3 : 0-5%; and/or RO: 0-9%, preferably RO: 0-5%; and/or ZnO: 0-6%, preferably ZnO: 0-5%; and/or Li 2 O: 0 ⁇ 5 %, preferably Li2O : 0-3%; and/or Na2O: 0.5-8%, preferably Na2O : 1-
  • RO is one or more of BaO, SrO, CaO, MgO
  • clarifying agent is Sb 2 O 3 , SnO, SnO 2 , CeO one or more of 2 .
  • the components of the high-refractive and high-dispersion optical glass do not contain Ta 2 O 5 ; and/or do not contain GeO 2 ; and/or do not contain Ln 2 O 3 ; and/or do not contain TeO 2 ; and/or without Ga 2 O 3 .
  • the refractive index n d of the high-refractive and high-dispersion optical glass is 1.95 or more, preferably 1.97 or more, more preferably 1.99 or more;
  • Abbe number ⁇ d is 25 or less, preferably 23 or less, more preferably 21 the following.
  • the acid resistance stability D A of the high-refractive and high-dispersion optical glass is 2 or more, preferably 1; and/or the water resistance stability D W is 2 or more, preferably 1; and/ Or the weather resistance CR is 2 or more types, preferably 1 type; and/or the thermal expansion coefficient ⁇ -30/70°C is 110 ⁇ 10 -7 /K or less, preferably 100 ⁇ 10 -7 /K or less, more preferably 90 ⁇ 10 -7 /K or less; and/or transition temperature T g is 520°C or less, preferably 510°C or less, more preferably 500°C or less, further preferably 495°C or less; and/or abrasion degree F A is 390 or less , preferably 380 or less, more preferably 360 or less; and/or Knoop hardness H K of 350 ⁇ 10 7 Pa or more, preferably 360 ⁇ 10 7 Pa or more, more preferably 370 ⁇ 10 7 Pa or more, further preferably 380 ⁇ 10 7 Pa or more; and/or
  • the glass preform is made of the above-mentioned high-refractive and high-dispersion optical glass.
  • the optical element is made of the above-mentioned high-refractive and high-dispersion optical glass or the above-mentioned glass preform.
  • An optical instrument containing the above-mentioned high-refractive and high-dispersion optical glass, and/or containing the above-mentioned optical element.
  • the beneficial effects of the present invention are: through reasonable component design, the optical glass obtained by the present invention has the desired refractive index and Abbe number, and at the same time has a lower transition temperature, and is suitable for precision drop molding or precision molding .
  • the embodiment of the high-refractive-high-dispersion optical glass of the present invention will be described in detail, but the present invention is not limited to the following embodiments, and can be implemented with appropriate modifications within the scope of the object of the present invention.
  • description is abbreviate
  • the high-refractive and high-dispersion optical glass of the present invention is sometimes simply referred to as optical glass or glass.
  • each component (component) of the high-refractive and high-dispersion 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%.
  • P 2 O 5 is a product of the glass of the present invention, and has the functions of lowering the melting temperature of the glass raw material and improving the stability and visible light transmittance of the glass.
  • the above effects are obtained by containing 8% or more of P 2 O 5 , the content of P 2 O 5 is preferably 12% or more, and the content of P 2 O 5 is more preferably 13% or more.
  • the content of P 2 O 5 in the present invention is 25% or less, preferably 22% or less, and more preferably 19% or less.
  • Bi 2 O 3 can increase the refractive index of glass and lower the transition temperature.
  • the above effects are obtained by containing more than 30% of Bi 2 O 3 , preferably the content of Bi 2 O 3 is more than 35%, more preferably Bi 2 O The content of 3 is 38% or more.
  • the upper limit of the content of Bi 2 O 3 is 60%, preferably 55%, and more preferably 50%.
  • Nb 2 O 5 is a high - refractive and high - dispersion component, which can improve the refractive index, light transmittance and devitrification resistance of the glass, and reduce the thermal expansion coefficient of the glass.
  • the lower limit of the content of Nb 2 O 5 is preferably 18%, and the lower limit of the content of Nb 2 O 5 is more preferably 20%. If the content of Nb 2 O 5 exceeds 35%, the thermal stability and chemical stability of the glass will decrease, and the light transmittance will decrease. Therefore, the upper limit of the content of Nb 2 O 5 in the present invention is 35%, preferably the upper limit is 30%, and more The preferred upper limit is 28%.
  • the ratio between the content of Bi 2 O 3 and the total content of Nb 2 O 5 and P 2 O 5 is Bi 2 O 3 /(Nb 2 O 5 +P 2 O 5 ) is controlled in the range of 0.6 to 2.3. While obtaining the desired high refractive index and high dispersion, the optical glass can effectively reduce the transition temperature of the glass and obtain a suitable degree of abrasion .
  • Bi 2 O 3 /(Nb 2 O 5 +P 2 O 5 ) is preferably 0.6 to 2.3, more preferably Bi 2 O 3 /(Nb 2 O 5 +P 2 O 5 ) is 0.7 to 2.0, and even more preferably Bi 2 O 3 /(Nb 2 O 5 +P 2 O 5 ) is 0.8 to 1.5, and more preferably Bi 2 O 3 /(Nb 2 O 5 +P 2 O 5 ) is 0.9 to 1.3.
  • WO 3 can improve the refractive index, central dispersion and mechanical strength of the glass, and reduce the transition temperature of the glass.
  • the above effects are obtained by containing more than 3% of WO 3 , preferably the lower limit of the content of WO 3 is 4%, more preferably WO The lower limit of the content of 3 is 6%.
  • the upper limit of the content of WO 3 is 25%, preferably 20%, and more preferably 15%.
  • (Nb 2 O 5 +P 2 O 5 )/WO 3 is preferably 1.0 to 15.0, and more preferably (Nb 2 O 5 +P 2 O 5 )/WO 3 is 1.5 to 12.0.
  • the ratio of (Nb 2 O 5 +P 2 O 5 )/WO 3 is more preferably 2.5 to 10.0, and the ratio of (Nb 2 O 5 +P 2 O 5 )/WO 3 is more preferably 3.0 to 7.0.
  • TiO 2 has the effect of significantly improving the refractive index and dispersion of glass, and can participate in the formation of glass network, improving the chemical stability of glass, and containing an appropriate amount can make glass more stable and reduce the viscosity of glass.
  • the content of TiO 2 is 15% or less, preferably 0.5 to 8%, and more preferably 1 to 5%.
  • the total content of Nb 2 O 5 , WO 3 , TiO 2 and P 2 O 5 (Nb 2 O 5 +WO 3 +TiO 2 +P 2 O 5 ) is divided by the content of Bi 2 O 3
  • the ratio between (Nb 2 O 5 +WO 3 +TiO 2 +P 2 O 5 )/Bi 2 O 3 is controlled in the range of 0.5-2.5, which can improve the weather resistance and hardness of the glass.
  • (Nb 2 O 5 +WO 3 +TiO 2 +P 2 O 5 )/Bi 2 O 3 is preferably 0.5 to 2.5, more preferably (Nb 2 O 5 +WO 3 +TiO 2 +P 2 O 5 )/ Bi 2 O 3 is 0.7 to 2.0, more preferably (Nb 2 O 5 +WO 3 +TiO 2 +P 2 O 5 )/Bi 2 O 3 is 0.8 to 1.8, still more preferably (Nb 2 O 5 +WO 3 + TiO 2 +P 2 O 5 )/Bi 2 O 3 is 1.0 to 1.5.
  • the control of Bi 2 O 3 in the range of 0.3 to 1.3 can improve the stability and reduce the density of the glass while obtaining the desired optical constant. Therefore, (Nb 2 O 5 +TiO 2 )/Bi 2 O 3 is preferably 0.3 to 1.3, and more preferably (Nb 2 O 5 +TiO 2 )/Bi 2 O 3 is 0.4 to 1.0.
  • the ratio of (Nb 2 O 5 +TiO 2 )/Bi 2 O 3 is more preferably 0.5 to 0.8, and the ratio of (Nb 2 O 5 +TiO 2 )/Bi 2 O 3 is more preferably 0.55 to 0.75.
  • B 2 O 3 acts similarly to P 2 O 5 . Adding an appropriate amount of B 2 O 3 to the glass containing P 2 O 5 can make the layered or interwoven chain structure tend to the skeleton structure, and improve the devitrification resistance and chemical stability of the glass. However, when the content of B 2 O 3 exceeds 10%, the refractive index of the glass decreases, the temperature coefficient of refractive index increases, and the devitrification resistance deteriorates on the contrary. Therefore, the content of B 2 O 3 is limited to 0 to 10%, preferably 0 to 8%, and more preferably 0 to 5%.
  • RO is one or more of BaO, SrO, CaO, and MgO
  • the optical constant of the glass in the present invention can adjust the optical constant of the glass in the present invention and improve the light transmittance of the glass. If its content exceeds 15%, the glass will be resistant to devitrification. Performance and chemical stability deteriorate. Therefore, the content of RO is 0 to 15%, preferably 0 to 9%, and more preferably 0 to 5%.
  • the preferred RO in the present invention is BaO.
  • Nb 2 O 5 , P 2 O 5 , TiO 2 and BaO Nb 2 O 5 +P 2 O 5 +TiO 2 +BaO
  • the ratio between the total content of WO 3 (Bi 2 O 3 +WO 3 ) (Nb 2 O 5 +P 2 O 5 +TiO 2 +BaO)/(Bi 2 O 3 +WO 3 ) is in the range of 0.4 to 2.0 , which can improve the glass-forming stability and devitrification resistance of the glass.
  • (Nb 2 O 5 +P 2 O 5 +TiO 2 +BaO)/(Bi 2 O 3 +WO 3 ) is preferably 0.4 to 2.0, more preferably (Nb 2 O 5 +P 2 O 5 +TiO 2 + BaO)/(Bi 2 O 3 +WO 3 ) is 0.5 to 1.5. Furthermore, by setting (Nb 2 O 5 +P 2 O 5 +TiO 2 +BaO)/(Bi 2 O 3 +WO 3 ) in the range of 0.6 to 1.2, the hardness and chemical stability of the glass can be further improved.
  • (Nb 2 O 5 +P 2 O 5 +TiO 2 +BaO)/(Bi 2 O 3 +WO 3 ) is more preferably 0.6 to 1.2, and more preferably (Nb 2 O 5 +P 2 O 5 +TiO) 2 +BaO)/(Bi 2 O 3 +WO 3 ) is 0.65 to 1.0.
  • ZnO can adjust the refractive index and dispersion of glass and improve the stability of glass. At the same time, ZnO can also reduce the high temperature viscosity and transition temperature of glass, so that glass can be melted at lower temperature, thereby improving the light transmittance of glass. On the other hand, when the content of ZnO is too high, the refractive index of the glass is lowered, and the devitrification resistance is deteriorated. Therefore, the content of ZnO is 0 to 10%, preferably 0 to 6%, and more preferably 0 to 5%.
  • the ratio ZnO/(TiO 2 +BaO) between the content of ZnO and the total content of TiO 2 and BaO (TiO 2 +BaO) is controlled below 5.0, which can prevent the thermal expansion coefficient of the glass from changing. Yamato's anti-devitrification performance deteriorates. Therefore, ZnO/(TiO 2 +BaO) is preferably 5.0 or less, and more preferably ZnO/(TiO 2 +BaO) is 3.0 or less. Further, controlling ZnO/(TiO 2 +BaO) below 1.5 is also beneficial to optimize the high temperature viscosity of the glass and improve the streak degree and bubble degree of the glass. Therefore, ZnO/(TiO 2 +BaO) is more preferably 1.5 or less, and ZnO/(TiO 2 +BaO) is more preferably 0.8 or less.
  • Li 2 O can reduce the transition temperature of glass, but when its content is high, it is unfavorable to the acid resistance and thermal expansion coefficient of glass. Therefore, in the present invention, the content of Li 2 O is 0 to 10%, preferably 0 to 5%, and more preferably 0 to 3%.
  • Na 2 O has the effect of improving the melting property of glass, and at the same time, it can also lower the transition temperature of glass. If the content of Na 2 O exceeds 10%, the chemical stability and weather resistance of glass will be reduced. Therefore, the content of Na 2 O is 0 to 10%, preferably 0.5 to 8%, and more preferably 1 to 6%.
  • K 2 O has the effect of improving the thermal stability and meltability of the glass, but when the content exceeds 10%, the devitrification resistance of the glass decreases and the chemical stability deteriorates. Therefore, the content of K 2 O in the present invention is 0 to 10%, preferably 0 to 6%, and more preferably 0 to 5%.
  • Li 2 O, Na 2 O , and K 2 O all belong to alkali metal oxides . It is beneficial to improve the anti-devitrification performance and light transmittance of glass. Therefore, Na 2 O/(Li 2 O+Na 2 O+K 2 O) is preferably 0.3 to 1.0, and more preferably Na 2 O/(Li 2 O+Na 2 O+K 2 O) is 0.4 to 0.9. Furthermore, by setting Na 2 O/(Li 2 O+Na 2 O+K 2 O) in the range of 0.5 to 0.8, it is also beneficial to improve the weather resistance of the glass. Therefore, Na 2 O/(Li 2 O+Na 2 O+K 2 O) is more preferably 0.5 to 0.8, and more preferably Na 2 O/(Li 2 O+Na 2 O+K 2 O) is 0.5 to 0.75 .
  • WO 3 /(Li 2 O+Na 2 O+K 2 O) can optimize the abrasion degree of glass and reduce the thermal expansion coefficient of glass. Therefore, WO 3 /(Li 2 O + Na 2 O + K 2 O ) is preferably 0.2 or more, and more preferably 0.5 or more. Further, by setting WO 3 /(Li 2 O+Na 2 O+K 2 O) in the range of 1.0 to 15.0, the reduction of the light transmittance of the glass can also be prevented, and the anti-devitrification performance can be optimized. Therefore, WO 3 /(Li 2 O+Na 2 O+K 2 O) is more preferably 1.0 to 15.0, and WO 3 /(Li 2 O+Na 2 O+K 2 O) is more preferably 1.5 to 8.0.
  • SiO 2 , Al 2 O 3 and ZrO 2 can improve the mechanical properties of the glass and improve the stability of the glass, but when the content is high, the transition temperature of the glass increases. Therefore, in the present invention, the total content of SiO 2 , Al 2 O 3 and ZrO 2 is 0 to 10% SiO 2 +Al 2 O 3 +ZrO 2 , preferably SiO 2 +Al 2 O 3 +ZrO 2 is greater than 0 but less than or equal to 8%, more preferably SiO 2 +Al 2 O 3 +ZrO 2 is 0.1 to 5%.
  • TiO 2 /(SiO 2 +Al 2 O 3 +ZrO 2 ) is preferably 0.1 or more, and more preferably TiO 2 /(SiO 2 +Al 2 O 3 +ZrO 2 ) is 0.3 or more. Further, by setting TiO 2 /(SiO 2 +Al 2 O 3 +ZrO 2 ) in the range of 0.5 to 20.0, the glass can obtain a lower thermal expansion coefficient while preventing the glass from being too low in hardness.
  • TiO 2 /(SiO 2 +Al 2 O 3 +ZrO 2 ) is more preferably 0.5 to 20.0, and TiO 2 /(SiO 2 +Al 2 O 3 +ZrO 2 ) is more preferably 0.8 to 10.0.
  • Ln 2 O 3 (Ln 2 O 3 is one or more of La 2 O 3 , Gd 2 O 3 , Y 2 O 3 , Yb 2 O 3 , Lu 2 O 3 ) can improve the refractive index and chemical Stability is an optional component in the optical glass of the present invention. Devitrification resistance of glass can be prevented from falling by controlling the content of Ln 2 O 3 to 10% or less, and the upper limit of the Ln 2 O 3 content is preferably 5%, and more preferably 3%. In some embodiments, it is further preferred not to contain Ln 2 O 3 .
  • TeO 2 is an optional component that increases the refractive index of glass and reduces the transition temperature of glass. When its content is too high, it is easy to react with platinum crucible, which seriously damages the service life of production equipment. Therefore, the TeO 2 content is limited to 5% or less, preferably 3% or less, and more preferably 1% or less. In some embodiments, it is further preferred not to contain TeO 2 .
  • GeO 2 has the effect of increasing the refractive index of the glass and increasing the resistance to devitrification, and is an optional component of the optical glass of the present invention. However, it is expensive, and if it contains too much, it is not conducive to reducing the cost, and the light transmittance of the glass is reduced. Therefore, its content is limited to 5% or less, preferably 3% or less, and more preferably 1% or less. In some embodiments, it is further preferred not to contain GeO 2 .
  • the content of Ga 2 O 3 is 5% or less, preferably 3% or less, and more preferably 1% or less. In some embodiments, it is further preferred not to contain Ga 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 will decrease, and compared with other components, the price of Ta 2 O 5 is very expensive. As well as cost considerations, its usage should be minimized. Therefore, in the present invention, the content of Ta 2 O 5 is limited to 0 to 5%, preferably 0 to 3%, and more preferably 0 to 1%. In some embodiments, it is further preferred not to contain Ta 2 O 5 .
  • one or more components of Sb 2 O 3 , SnO, SnO 2 and CeO 2 are contained in 0-2% as a clarifying agent, so that the clarifying effect of the glass can be improved.
  • the content of the clarifying agent is 0- 1%, more preferably 0 to 0.5%.
  • Sb 2 O 3 is preferably used as a clarifying agent, which has the effect of improving glass coloration.
  • 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, 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 high-refractive and high-dispersion optical glass of the present invention preferably does not contain As 2 O 3 and PbO.
  • Does not contain and "0%” as described herein means that the compound, molecule or element is not intentionally added as a raw material to the high-refractive and high-dispersion optical glass of the present invention; but as a raw material and/or equipment for producing optical glass, There may be some unintentionally added impurities or components, which may 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 1.95 or more, preferably 1.97 or more, and more preferably 1.99 or more.
  • the Abbe number ( ⁇ d ) of the optical glass of the present invention is 25 or less, preferably 23 or less, and more preferably 21 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 520°C or lower, preferably 510°C or lower, more preferably 500°C or lower, and further preferably 495°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 485 nm or less, preferably ⁇ 70 is 480 nm or less, and more preferably ⁇ 70 is 470 nm or less.
  • ⁇ 5 of the optical glass of the present invention is 425 nm or less, preferably ⁇ 5 is 420 nm or less, and more preferably ⁇ 5 is 410 nm or less.
  • the water resistance stability (D W ) of the optical glass of the present invention is 2 or more types, preferably 1 type.
  • 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 this invention is 2 or more types, Preferably it is 1 type.
  • the weather resistance (CR) of the optical glass was tested as follows.
  • the samples were placed in a test box with a relative humidity of 90% saturated water vapor, and alternately cycled at 40-50°C every 1 hour for 15 cycles.
  • the weather resistance category is divided according to the turbidity change before and after the sample is placed. Table 1 shows the weather resistance classification.
  • the weather resistance (CR) of the optical glass of this invention is 2 types or more, Preferably it is 1 type.
  • the thermal expansion coefficient ( ⁇ -30/70°C ) of the optical glass of the present invention is tested according to the method specified in "GB/T7962.16-2010" - 30 ⁇ 70°C data.
  • the thermal expansion coefficient ( ⁇ -30/70°C ) of the optical glass of the present invention is 110 ⁇ 10 -7 /K or less, preferably 100 ⁇ 10 -7 /K or less, and more preferably 90 ⁇ 10 -7 /K or less.
  • the abrasion degree (F A ) of optical glass refers to the value obtained by multiplying the ratio of the abrasion amount of the sample to the abrasion amount (volume) of the standard specimen (H-K9 glass) by 100 under exactly the same conditions.
  • the formula is expressed as follows:
  • V volume wear of the tested sample
  • the abrasion degree (F A ) of the optical glass of the present invention is 390 or less, preferably 380 or less, and more preferably 360 or less.
  • the Knoop hardness (H K ) of the optical glass of the present invention is 350 ⁇ 10 7 Pa or higher, preferably 360 ⁇ 10 7 Pa or higher, more preferably 370 ⁇ 10 7 Pa or higher, further preferably 380 ⁇ 10 7 Pa or more.
  • the manufacturing method of the optical glass of the present invention is as follows: the glass of the present invention can be produced by using conventional raw materials and processes, including but not limited to the use of carbonates, nitrates, phosphates, metaphosphates, pyrophosphates, hydroxides, oxides , fluoride, etc. as raw materials, after batching according to conventional methods, put the prepared charge into a smelting furnace (such as platinum or platinum alloy crucible, gold or gold-containing alloy crucible) at 800 ⁇ 1100 ° C for melting, and after clarification After homogenization, a homogeneous molten glass without bubbles and undissolved substances is obtained, and the molten glass is cast in a mold and annealed.
  • a smelting furnace such as platinum or platinum alloy crucible, gold or gold-containing alloy crucible
  • the glass of the present invention can also be produced by a secondary smelting method, that is, the mixture of the aforementioned raw materials is first put into a quartz, alumina or zirconium crucible for melting, and clinker is prepared after the melting is completed, and then the clinker is put into a platinum or platinum alloy crucible ( Or gold or gold-containing alloy crucibles), so as to obtain the required high-quality glass.
  • a secondary smelting method that is, the mixture of the aforementioned raw materials is first put into a quartz, alumina or zirconium crucible for melting, and clinker is prepared after the melting is completed, and then the clinker is put into a platinum or platinum alloy crucible ( Or gold or gold-containing alloy crucibles), so as to obtain the required high-quality glass.
  • a glass preform can be produced from the produced high-refractive and high-dispersion optical glass using means such as direct drop forming, grinding processing, or press forming means such as thermoforming. That is, it is possible to produce a glass preform by direct precision drop molding of molten optical glass, or to produce a glass preform by mechanical processing such as grinding and grinding, or to produce a preform for press molding from optical glass, This preform is subjected to reheat press molding, followed by grinding to produce a glass preform. It should be noted that the means for preparing the glass preform is not limited to the above-mentioned means.
  • the high-refractive and high-dispersion optical glass of the present invention is useful for various optical elements and optical designs, among which it is particularly preferable to form a preform from the high-refractive and high-dispersion optical glass of the present invention, and to use the preform for reprocessing. Hot pressing molding, precision stamping molding, etc., to produce optical components such as lenses and prisms.
  • Both the glass preform and the optical element of the present invention are formed from the above-mentioned high-refractive and high-dispersion optical glass of the present invention.
  • the glass preform of the present invention has the excellent characteristics of the high-refractive and high-dispersion optical glass;
  • the optical element of the present invention has the excellent characteristics of the high-refractive and high-dispersion optical glass, and can provide various lenses, prisms and other optics with high optical value. element.
  • 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 high-refractive and high-dispersion optical glass of the present invention can be used to manufacture optical instruments such as photographic equipment, imaging equipment, projection equipment, display equipment, vehicle-mounted equipment and monitoring equipment.
  • the high-refractive and high-dispersion optical glass having the compositions shown in Tables 2 to 4 was obtained by the above-mentioned manufacturing method of the optical glass.
  • the properties of each glass were measured by the test method according to the present invention, and the measurement results are shown in Tables 2 to 4.
  • Concave meniscus lenses are produced by using the glass obtained in the examples of high-refractive and high-dispersion optical glass in Tables 2 to 4 above, for example, by means of grinding, or by means of compression molding such as reheat press molding and precision press molding. Preforms for various lenses, prisms, etc., such as convex meniscus lenses, biconvex lenses, biconcave lenses, plano-convex lenses, plano-concave lenses, etc.
  • the preforms obtained in the above glass preform examples are annealed, and the refractive index is fine-tuned while reducing the internal stress of the glass, so that the optical properties such as the refractive index reach desired values.
  • 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.

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Abstract

本发明提供一种高折射高色散光学玻璃，所述高折射高色散光学玻璃的组分以重量百分比表示，含有：P 2O 5：8～25％；Bi 2O 3：30～60％；Nb 2O 5：15～35％；WO 3：3～25％，其中Bi 2O 3/(Nb 2O 5+P 2O 5)为0.6～2.3。通过合理的组分设计，本发明获得的光学玻璃在具有期望的折射率和阿贝数的同时，具有较低的转变温度，适用于精密滴料成型或精密模压成型。

Description

高折射高色散光学玻璃及光学元件 技术领域
本发明涉及一种光学玻璃，尤其是涉及一种折射率为1.95以上，阿贝数为25以下的光学玻璃。
背景技术
随着便携式电子设备(如手机、PAD等)的快速发展，对小尺寸透镜的需求增长迅速，高折射光学玻璃由于可以以较小的体积获得较大的视角，可用于制造小尺寸透镜，因此对便携式电子设备的发展非常重要。
现有技术中制造小尺寸透镜通常采用精密滴料成型或精密模压成型，这就要求光学玻璃需要具有较低的转变温度(T g)，CN1896022A公开了一种折射率不小于2.000，阿贝数不大于27的高折射高色散光学玻璃，但其转变温度较高，不利于精密滴料成型或精密模压成型。
发明内容
本发明所要解决的技术问题是提供一种具有较低转变温度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：
高折射高色散光学玻璃，其组分以重量百分比表示，含有：P 2O 5：8～25％；Bi 2O 3：30～60％；Nb 2O 5：15～35％；WO 3：3～25％，其中Bi 2O 3/(Nb 2O 5+P 2O 5)为0.6～2.3。
进一步的，所述的高折射高色散光学玻璃，其组分以重量百分比表示，还含有：TiO 2：0～15％；和/或B 2O 3：0～10％；和/或RO：0～15％；和/或ZnO：0～10％；和/或Li 2O：0～10％；和/或Na 2O：0～10％；和/或K 2O：0～10％；和/或SiO 2+Al 2O 3+ZrO 2：0～10％；和/或Ln 2O 3：0～10％；和/或TeO 2：0～5％；和/或GeO 2：0～5％；和/或Ga 2O 3：0～5％；和/或Ta 2O 5：0～5％；和/或澄清剂：0～2％，所述Ln 2O 3为La 2O 3、Gd 2O 3、Y 2O 3、Yb 2O 3、Lu 2O 3中的一种或多种,RO为BaO、SrO、CaO、MgO中的一种或多种，澄清剂为Sb 2O 3、SnO、SnO 2、 CeO 2中的一种或多种。
高折射高色散光学玻璃，含有P 2O 5、Nb 2O 5、WO 3和Bi 2O 3作为必要组分，其组分以重量百分比表示，其中Bi 2O 3/(Nb 2O 5+P 2O 5)为0.6～2.3，所述高折射高色散光学玻璃的折射率n d为1.95以上，阿贝数ν d为25以下，转变温度T g为520℃以下。
进一步的，所述的高折射高色散光学玻璃，其组分以重量百分比表示，含有：P 2O 5：8～25％；和/或Bi 2O 3：30～60％；和/或Nb 2O 5：15～35％；和/或WO 3：3～25％；和/或TiO 2：0～15％；和/或B 2O 3：0～10％；和/或RO：0～15％；和/或ZnO：0～10％；和/或Li 2O：0～10％；和/或Na 2O：0～10％；和/或K 2O：0～10％；和/或SiO 2+Al 2O 3+ZrO 2：0～10％；和/或Ln 2O 3：0～10％；和/或TeO 2：0～5％；和/或GeO 2：0～5％；和/或Ga 2O 3：0～5％；和/或Ta 2O 5：0～5％；和/或澄清剂：0～2％，所述Ln 2O 3为La 2O 3、Gd 2O 3、Y 2O 3、Yb 2O 3、Lu 2O 3中的一种或多种,RO为BaO、SrO、CaO、MgO中的一种或多种，澄清剂为Sb 2O 3、SnO、SnO 2、CeO 2中的一种或多种。
进一步的，所述的高折射高色散光学玻璃，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：
1)Bi 2O 3/(Nb 2O 5+P 2O 5)为0.7～2.0，优选Bi 2O 3/(Nb 2O 5+P 2O 5)为0.8～1.5，更优选Bi 2O 3/(Nb 2O 5+P 2O 5)为0.9～1.3；
2)(Nb 2O 5+TiO 2)/Bi 2O 3为0.3～1.3，优选(Nb 2O 5+TiO 2)/Bi 2O 3为0.4～1.0，更优选(Nb 2O 5+TiO 2)/Bi 2O 3为0.5～0.8，进一步优选(Nb 2O 5+TiO 2)/Bi 2O 3为0.55～0.75；
3)(Nb 2O 5+P 2O 5)/WO 3为1.0～15.0，优选(Nb 2O 5+P 2O 5)/WO 3为1.5～12.0，更优选(Nb 2O 5+P 2O 5)/WO 3为2.5～10.0，进一步优选(Nb 2O 5+P 2O 5)/WO 3为3.0～7.0；
4)WO 3/(Li 2O+Na 2O+K 2O)为0.2以上，优选WO 3/(Li 2O+Na 2O+K 2O)为0.5以上，更优选WO 3/(Li 2O+Na 2O+K 2O)为1.0～15.0，进一步优选WO 3/(Li 2O+Na 2O+K 2O)为1.5～8.0；
5)(Nb 2O 5+WO 3+TiO 2+P 2O 5)/Bi 2O 3为0.5～2.5，优选(Nb 2O 5+WO 3+TiO 2+P 2O 5)/Bi 2O 3为0.7～2.0，更优选(Nb 2O 5+WO 3+TiO 2+P 2O 5)/Bi 2O 3为0.8～1.8，进一步优选(Nb 2O 5+WO 3+TiO 2+P 2O 5)/Bi 2O 3为1.0～1.5。
进一步的，所述的高折射高色散光学玻璃，其组分以重量百分比表示，满足以下4种情形中的一种以上：
1)(Nb 2O 5+P 2O 5+TiO 2+BaO)/(Bi 2O 3+WO 3)为0.4～2.0，优选(Nb 2O 5+P 2O 5+TiO 2+BaO)/(Bi 2O 3+WO 3)为0.5～1.5，更优选(Nb 2O 5+P 2O 5+TiO 2+BaO)/(Bi 2O 3+WO 3)为0.6～1.2，进一步优选(Nb 2O 5+P 2O 5+TiO 2+BaO)/(Bi 2O 3+WO 3)为0.65～1.0；
2)TiO 2/(SiO 2+Al 2O 3+ZrO 2)为0.1以上，优选TiO 2/(SiO 2+Al 2O 3+ZrO 2)为0.3以上，更优选TiO 2/(SiO 2+Al 2O 3+ZrO 2)为0.5～20.0，进一步优选TiO 2/(SiO 2+Al 2O 3+ZrO 2)为0.8～10.0；
3)Na 2O/(Li 2O+Na 2O+K 2O)为0.3～1.0，优选Na 2O/(Li 2O+Na 2O+K 2O)为0.4～0.9，更优选Na 2O/(Li 2O+Na 2O+K 2O)为0.5～0.8，进一步优选Na 2O/(Li 2O+Na 2O+K 2O)为0.5～0.75；
4)ZnO/(TiO 2+BaO)为5.0以下，优选ZnO/(TiO 2+BaO)为3.0以下，更优选ZnO/(TiO 2+BaO)为1.5以下，进一步优选ZnO/(TiO 2+BaO)为0.8以下。
进一步的，所述的高折射高色散光学玻璃，其组分以重量百分比表示，含有：P 2O 5：12～22％，优选P 2O 5：13～19％；和/或Bi 2O 3：35～55％，优选Bi 2O 3：38～50％；和/或Nb 2O 5：18～30％，优选Nb 2O 5：20～28％；和/或WO 3：4～20％，优选WO 3：6～15％；和/或TiO 2：0.5～8％，优选TiO 2：1～5％；和/或B 2O 3：0～8％，优选B 2O 3：0～5％；和/或RO：0～9％，优选RO：0～5％；和/或ZnO：0～6％，优选ZnO：0～5％；和/或Li 2O：0～5％，优选Li 2O：0～3％；和/或Na 2O：0.5～8％，优选Na 2O：1～6％；和/或K 2O：0～6％，优选K 2O：0～5％；和/或SiO 2+Al 2O 3+ZrO 2：大于0但小于或等于8％，优选SiO 2+Al 2O 3+ZrO 2：0.1～5％；和/或Ln 2O 3：0～5％，优选Ln 2O 3：0～3％；和/或TeO 2：0～3％，优 选TeO 2：0～1％；和/或GeO 2：0～3％，优选GeO 2：0～1％；和/或Ga 2O 3：0～3％，优选Ga 2O 3：0～1％；和/或Ta 2O 5：0～3％，优选Ta 2O 5：0～1％；和/或澄清剂：0～1％，优选澄清剂：0～0.5％，所述Ln 2O 3为La 2O 3、Gd 2O 3、Y 2O 3、Yb 2O 3、Lu 2O 3中的一种或多种,RO为BaO、SrO、CaO、MgO中的一种或多种，澄清剂为Sb 2O 3、SnO、SnO 2、CeO 2中的一种或多种。
进一步的，所述的高折射高色散光学玻璃，其组分中不含有Ta 2O 5；和/或不含有GeO 2；和/或不含有Ln 2O 3；和/或不含有TeO 2；和/或不含有Ga 2O 3。
进一步的，所述的高折射高色散光学玻璃的折射率n d为1.95以上，优选为1.97以上，更优选为1.99以上；阿贝数ν d为25以下，优选为23以下，更优选为21以下。
进一步的，所述的高折射高色散光学玻璃的耐酸作用稳定性D A为2类以上，优选为1类；和/或耐水作用稳定性D W为2类以上，优选为1类；和/或耐候性CR为2类以上，优选为1类；和/或热膨胀系数α -30/70℃为110×10 -7/K以下，优选为100×10 -7/K以下，更优选为90×10 -7/K以下；和/或转变温度T g为520℃以下，优选为510℃以下，更优选为500℃以下，进一步优选为495℃以下；和/或磨耗度F A为390以下，优选为380以下，更优选为360以下；和/或努氏硬度H K为350×10 7Pa以上，优选为360×10 7Pa以上，更优选为370×10 7Pa以上，进一步优选为380×10 7Pa以上；和/或λ 70为485nm以下，优选为480nm以下，更优选为470nm以下；和/或λ 5为425nm以下，优选为420nm以下，更优选为410nm以下。
玻璃预制件，采用上述的高折射高色散光学玻璃制成。
光学元件，采用上述的高折射高色散光学玻璃或上述的玻璃预制件制成。
光学仪器，含有上述的高折射高色散光学玻璃，和/或含有上述的光学元件。
本发明的有益效果是：通过合理的组分设计，本发明获得的光学玻璃在具有期望的折射率和阿贝数的同时，具有较低的转变温度，适用于精密 滴料成型或精密模压成型。
具体实施方式
下面，对本发明的高折射高色散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，本发明高折射高色散光学玻璃有时候简称为光学玻璃或玻璃。
[高折射高色散光学玻璃]
下面对本发明高折射高色散光学玻璃的各组分(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>
P 2O 5是本发明玻璃的生成体，具有降低玻璃原料的熔融温度，提高玻璃的稳定性和可见光透过率的作用，本发明中通过含有8％以上的P 2O 5以获得上述效果，优选P 2O 5的含量为12％以上，更优选P 2O 5的含量为13％以上。另一方面，若P 2O 5的含量超过25％，玻璃难以获得期望的高折射率，且玻璃的失透倾向增加。因此，本发明中P 2O 5的含量为25％以下，优选为22％以下，更优选为19％以下。
Bi 2O 3可以提高玻璃的折射率，降低转变温度，本发明中通过含有30％ 以上的Bi 2O 3以获得上述效果，优选Bi 2O 3的含量为35％以上，更优选Bi 2O 3的含量为38％以上。若Bi 2O 3的含量超过60％，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，Bi 2O 3的含量上限为60％，优选上限为55％，更优选上限为50％。
Nb 2O 5是高折射高色散组分，可以提高玻璃的折射率、光透过率和耐失透性，降低玻璃的热膨胀系数，本发明中通过含有15％以上的Nb 2O 5以获得上述效果，优选Nb 2O 5的含量下限为18％，更优选Nb 2O 5的含量下限为20％。若Nb 2O 5的含量超过35％，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的含量上限为35％，优选上限为30％，更优选上限为28％。
通过发明人大量实验研究发现，在一些实施方式中，将Bi 2O 3的含量与Nb 2O 5和P 2O 5的合计含量(Nb 2O 5+P 2O 5)之间的比值Bi 2O 3/(Nb 2O 5+P 2O 5)控制在0.6～2.3范围内，光学玻璃在获得期望的高折射高色散的同时，可有效降低玻璃的转变温度，并获得适宜的磨耗度。因此，优选Bi 2O 3/(Nb 2O 5+P 2O 5)为0.6～2.3，更优选Bi 2O 3/(Nb 2O 5+P 2O 5)为0.7～2.0，进一步优选Bi 2O 3/(Nb 2O 5+P 2O 5)为0.8～1.5，更进一步优选Bi 2O 3/(Nb 2O 5+P 2O 5)为0.9～1.3。
WO 3可以提高玻璃的折射率、中部色散和机械强度，降低玻璃的转变温度，本发明中通过含有3％以上的WO 3以获得上述效果，优选WO 3的含量下限为4％，更优选WO 3的含量下限为6％。若WO 3的含量超过25％，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25％，优选上限为20％，更优选上限为15％。
在一些实施方式中，通过将Nb 2O 5和P 2O 5的合计含量(Nb 2O 5+P 2O 5)与WO 3的含量之间的比值(Nb 2O 5+P 2O 5)/WO 3控制在1.0～15.0范围内，可提高玻璃的耐候性。因此，优选(Nb 2O 5+P 2O 5)/WO 3为1.0～15.0，更优选(Nb 2O 5+P 2O 5)/WO 3为1.5～12.0。进一步的，通过使(Nb 2O 5+P 2O 5)/WO 3在2.5～10.0范围内，还可进一步优化玻璃的磨耗度。因此，进一步优选(Nb 2O 5+P 2O 5)/WO 3为2.5～10.0，更进一步优选(Nb 2O 5+P 2O 5)/WO 3为3.0～7.0。
TiO 2具有显著提高玻璃的折射率和色散的作用，并且能参与玻璃网络形成，提升玻璃的化学稳定性，适量含有可使玻璃更稳定并降低玻璃的粘度。但若TiO 2含量超过15％，玻璃的析晶倾向增加，玻璃的转变温度上升，同时玻璃着色度增大。因此，本发明中TiO 2的含量为15％以下，优选为0.5～8％，更优选为1～5％。
在一些实施方式中，将Nb 2O 5、WO 3、TiO 2和P 2O 5的合计含量(Nb 2O 5+WO 3+TiO 2+P 2O 5)与Bi 2O 3的含量之间的比值(Nb 2O 5+WO 3+TiO 2+P 2O 5)/Bi 2O 3控制在0.5～2.5范围内，可以提高玻璃的耐候性和硬度。因此，优选(Nb 2O 5+WO 3+TiO 2+P 2O 5)/Bi 2O 3为0.5～2.5，更优选(Nb 2O 5+WO 3+TiO 2+P 2O 5)/Bi 2O 3为0.7～2.0，进一步优选(Nb 2O 5+WO 3+TiO 2+P 2O 5)/Bi 2O 3为0.8～1.8，更进一步优选(Nb 2O 5+WO 3+TiO 2+P 2O 5)/Bi 2O 3为1.0～1.5。
在本发明的一些实施方式中，将Nb 2O 5和TiO 2的合计含量(Nb 2O 5+TiO 2)与Bi 2O 3的含量之间的比值(Nb 2O 5+TiO 2)/Bi 2O 3控制在0.3～1.3范围内，可使玻璃在获得期望的光学常数的同时，有利于提高稳定性并降低密度。因此，优选(Nb 2O 5+TiO 2)/Bi 2O 3为0.3～1.3，更优选(Nb 2O 5+TiO 2)/Bi 2O 3为0.4～1.0。进一步的，将(Nb 2O 5+TiO 2)/Bi 2O 3控制在0.5～0.8范围内，还可进一步优化玻璃的化学稳定性和磨耗度。因此，进一步优选(Nb 2O 5+TiO 2)/Bi 2O 3为0.5～0.8，更进一步优选(Nb 2O 5+TiO 2)/Bi 2O 3为0.55～0.75。
B 2O 3作为网络形成体，其作用与P 2O 5相似。在含P 2O 5的玻璃中加入适量的B 2O 3，可使层状或交织的链状结构趋向骨架结构，提升玻璃的耐失透性和化学稳定性。但B 2O 3含量若高于10％，玻璃的折射率降低，折射率温度系数增加，耐失透性反而恶化。因此，B 2O 3的含量限定为0～10％，优选为0～8％，更优选为0～5％。
RO(RO为BaO、SrO、CaO、MgO中的一种或多种)在本发明中可以调整玻璃光学常数，改善玻璃的光透过率，若其含量超过15％，则玻璃的抗析晶性能和化学稳定性变差。因此，RO的含量为0～15％，优选含量为0～ 9％，更优选含量为0～5％。为使玻璃较易获得期望的优异性能，本发明优选RO为BaO。
在本发明的一些实施方式中，通过使Nb 2O 5、P 2O 5、TiO 2和BaO的合计含量(Nb 2O 5+P 2O 5+TiO 2+BaO)与Bi 2O 3和WO 3的合计含量(Bi 2O 3+WO 3)之间的比值(Nb 2O 5+P 2O 5+TiO 2+BaO)/(Bi 2O 3+WO 3)在0.4～2.0范围内，可提高玻璃的成玻稳定性和耐失透性。因此，优选(Nb 2O 5+P 2O 5+TiO 2+BaO)/(Bi 2O 3+WO 3)为0.4～2.0，更优选(Nb 2O 5+P 2O 5+TiO 2+BaO)/(Bi 2O 3+WO 3)为0.5～1.5。进一步的，通过使(Nb 2O 5+P 2O 5+TiO 2+BaO)/(Bi 2O 3+WO 3)在0.6～1.2范围内，还可进一步提高玻璃的硬度和化学稳定性。因此，进一步优选(Nb 2O 5+P 2O 5+TiO 2+BaO)/(Bi 2O 3+WO 3)为0.6～1.2，更进一步优选(Nb 2O 5+P 2O 5+TiO 2+BaO)/(Bi 2O 3+WO 3)为0.65～1.0。
ZnO可以调整玻璃的折射率和色散，提高玻璃的稳定性，同时ZnO还可以降低玻璃的高温粘度和转变温度，使得玻璃可以在较低温度下熔制，从而提高玻璃的光透过率。另一方面，若ZnO的含量过高，玻璃的折射率降低，抗析晶性能变差。因此，ZnO的含量为0～10％，优选为0～6％，更优选为0～5％。
在本发明的一些实施方式中，将ZnO的含量与TiO 2和BaO的合计含量(TiO 2+BaO)之间的比值ZnO/(TiO 2+BaO)控制在5.0以下，可防止玻璃热膨胀系数变大和抗析晶性能变差。因此，优选ZnO/(TiO 2+BaO)为5.0以下，更优选ZnO/(TiO 2+BaO)为3.0以下。进一步的，将ZnO/(TiO 2+BaO)控制在1.5以下，还有利于优化玻璃的高温粘度，改善玻璃的条纹度和气泡度。因此，进一步优选ZnO/(TiO 2+BaO)为1.5以下，更进一步优选ZnO/(TiO 2+BaO)为0.8以下。
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性和热膨胀系数不利。因此，本发明中Li 2O的含量为0～10％，优选为0～5％，更优选为0～3％。
Na 2O具有改善玻璃熔融性的作用，同时还可降低玻璃的转变温度，若 Na 2O含量超过10％，玻璃的化学稳定性和耐候性降低。因此，Na 2O的含量为0～10％，优选为0.5～8％，更优选为1～6％。
K 2O具有改善玻璃的热稳定性和熔融性的作用，但若其含量超过10％，玻璃的耐失透性下降，化学稳定性恶化。因此，本发明中K 2O的含量为0～10％，优选为0～6％，更优选为0～5％。
Li 2O、Na 2O、K 2O均属于碱金属氧化物，在一些实施方式中，通过使Na 2O/(Li 2O+Na 2O+K 2O)在0.3～1.0范围内，有利于提高玻璃的抗析晶性能和光透过率。因此，优选Na 2O/(Li 2O+Na 2O+K 2O)为0.3～1.0，更优选Na 2O/(Li 2O+Na 2O+K 2O)为0.4～0.9。进一步的，通过使Na 2O/(Li 2O+Na 2O+K 2O)在0.5～0.8范围内，还有利于提高玻璃的耐候性。因此，进一步优选Na 2O/(Li 2O+Na 2O+K 2O)为0.5～0.8，更进一步优选Na 2O/(Li 2O+Na 2O+K 2O)为0.5～0.75。
在本发明的一些实施方式中，通过使WO 3的含量与碱金属氧化物的合计含量(Li 2O+Na 2O+K 2O)之间的比值WO 3/(Li 2O+Na 2O+K 2O)在0.2以上，可优化玻璃的磨耗度，降低玻璃的热膨胀系数。因此，优选WO 3/(Li 2O+Na 2O+K 2O)为0.2以上，更优选WO 3/(Li 2O+Na 2O+K 2O)为0.5以上。进一步的，通过使WO 3/(Li 2O+Na 2O+K 2O)在1.0～15.0范围内，还可防止玻璃光透过率的降低，优化抗析晶性能。因此，进一步优选WO 3/(Li 2O+Na 2O+K 2O)为1.0～15.0，更进一步优选WO 3/(Li 2O+Na 2O+K 2O)为1.5～8.0。
SiO 2、Al 2O 3和ZrO 2具有提高玻璃的机械性能，改善玻璃稳定性的作用，但含量高时，玻璃的转变温度升高。因此，本发明中SiO 2、Al 2O 3和ZrO 2的合计含量SiO 2+Al 2O 3+ZrO 2为0～10％，优选SiO 2+Al 2O 3+ZrO 2为大于0但小于或等于8％，更优选SiO 2+Al 2O 3+ZrO 2为0.1～5％。
在本发明的一些实施方式中，通过使TiO 2/(SiO 2+Al 2O 3+ZrO 2)在0.1以上，有利于调整玻璃的成型粘度，优化玻璃的条纹度。因此，优选TiO 2/(SiO 2+Al 2O 3+ZrO 2)为0.1以上，更优选TiO 2/(SiO 2+Al 2O 3+ZrO 2)为0.3以上。进一步的，通过使TiO 2/(SiO 2+Al 2O 3+ZrO 2)在0.5～20.0范围内，还 可使玻璃在获得较低热膨胀系数的同时，防止玻璃硬度偏低。因此，进一步优选TiO 2/(SiO 2+Al 2O 3+ZrO 2)为0.5～20.0，更进一步优选TiO 2/(SiO 2+Al 2O 3+ZrO 2)为0.8～10.0。
Ln 2O 3(Ln 2O 3为La 2O 3、Gd 2O 3、Y 2O 3、Yb 2O 3、Lu 2O 3中的一种或多种)可以提高玻璃的折射率和化学稳定性，是本发明光学玻璃中的任选组分。通过将Ln 2O 3的含量控制为10％以下，能够防止玻璃的耐失透性降低，优选Ln 2O 3含量的上限为5％，更优选上限为3％。在一些实施方式中，进一步优选不含有Ln 2O 3。
TeO 2是提高玻璃的折射率并降低玻璃的转变温度的任选组分，当其含量过多时，易与铂金坩埚反应，严重损害生产设备的使用寿命。因此TeO 2含量限定为5％以下，优选为3％以下，更优选为1％以下。在一些实施方式中，进一步优选不含有TeO 2。
GeO 2具有提高玻璃折射率且增加耐失透性的效果，是本发明光学玻璃的任选组分，然而其价格昂贵，过多含有不利于成本的降低，且玻璃的光透过率降低，因此其含量限定为5％以下，优选为3％以下，更优选为1％以下。在一些实施方式中，进一步优选不含有GeO 2。
作为本发明任选组分，通过控制Ga 2O 3的含量在5％以下，可提高玻璃的耐失透性，并优化玻璃的磨耗度。因此，Ga 2O 3的含量为5％以下，优选为3％以下，更优选为1％以下。在一些实施方式中，进一步优选不含有Ga 2O 3。
Ta 2O 5具有提高折射率、提升玻璃耐失透性的作用，但其含量过高，玻璃的化学稳定性下降，且与其他组分相比，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，本发明中Ta 2O 5的含量限定为0～5％，优选为0～3％，更优选为0～1％。在一些实施方式中，进一步优选不含有Ta 2O 5。
本发明中通过含有0～2％的Sb 2O 3、SnO、SnO 2、CeO 2中的一种或多种组分作为澄清剂，可以提高玻璃的澄清效果，优选澄清剂的含量为0～1％，更优选为0～0.5％。优选采用Sb 2O 3作为澄清剂，具有改善玻璃着色的效果。
<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，本发明的高折射高色散光学玻璃优选不含有As 2O 3和PbO。
本文所记载的“不含有”“0％”是指没有故意将该化合物、分子或元素等作为原料添加到本发明高折射高色散光学玻璃中；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，对本发明的高折射高色散光学玻璃的性能进行说明。
<折射率与阿贝数>
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。
在一些实施方式中，本发明光学玻璃的折射率(n d)为1.95以上，优选为1.97以上，更优选为1.99以上。
在一些实施方式中，本发明光学玻璃的阿贝数(ν d)为25以下，优选为23以下，更优选为21以下。
<转变温度>
光学玻璃的转变温度(T g)按照《GB/T7962.16-2010》规定的方法进行 测试。
在一些实施方式中，本发明光学玻璃的转变温度(T g)为520℃以下，优选为510℃以下，更优选为500℃以下，进一步优选为495℃以下。
<着色度>
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。
在一些实施方式中，本发明的光学玻璃的λ 70为485nm以下，优选λ 70为480nm以下，更优选λ 70为470nm以下。
在一些实施方式中，本发明的光学玻璃的λ 5为425nm以下，优选λ 5为420nm以下，更优选λ 5为410nm以下。
<耐水作用稳定性>
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。
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。
<耐酸作用稳定性>
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。
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2类以上，优选为1类。
<耐候性>
光学玻璃的耐候性(CR)按以下方法进行测试。
将试样放置在相对湿度为90％的饱和水蒸气环境的测试箱内，在40～50℃每隔1小时交替循环，循环15个周期。根据试样放置前后的浊度变化量来划分耐候性类别，表1为耐候性分类情况。
表1.耐候性分类情况
Figure PCTCN2022070073-appb-000001
在一些实施方式中，本发明光学玻璃的耐候性(CR)为2类以上，优选为1类。
<热膨胀系数>
本发明光学玻璃的热膨胀系数(α -30/70℃)按照《GB/T7962.16-2010》规定的方法进行测试-30～70℃的数据。
本发明的光学玻璃的热膨胀系数(α -30/70℃)为110×10 -7/K以下，优选为100×10 -7/K以下，更优选为90×10 -7/K以下。
<磨耗度>
光学玻璃的磨耗度(F A)是指在完全相同的条件下，试样的磨损量与标准试样(H-K9玻璃)的磨损量(体积)的比值乘以100后所得的数值，用公式表示如下：
F A＝V/V 0×100＝(W/ρ)/(W 0/ρ 0)×100
式中：V—被测样品体积磨耗量；
V 0—标准样品体积磨耗量；
W—被测样品质量磨耗量；
W 0—标准样品质量磨耗量；
ρ—被测样品密度；
ρ 0—标准样品密度。
本发明光学玻璃的磨耗度(F A)为390以下，优选为380以下，更优选为360以下。
<努氏硬度>
光学玻璃的努氏硬度(H K)按《GB/T7962.18-2010》规定的测试方法进行测试。
在一些实施方式中，本发明的光学玻璃的努氏硬度(H K)为350×10 7Pa以上，优选为360×10 7Pa以上，更优选为370×10 7Pa以上，进一步优选为380×10 7Pa以上。
[光学玻璃的制造方法]
本发明光学玻璃的制造方法如下：本发明的玻璃可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、磷酸盐、偏磷酸盐、焦磷酸盐、氢氧化物、氧化物、氟化物等为原料，按常规方法配料后，将配好的炉料投入到800～1100℃的熔炼炉(如铂或铂合金坩埚、黄金或含黄金的合金坩埚)中熔制，并且经澄清和均化后，得到没有气泡及不含未溶解物质的均质熔融玻璃，将此熔融玻璃在模具内铸型并退火而成。
本发明的玻璃也可采用二次熔炼的方式生产，即将前述原料的混合料先投入石英、氧化铝或锆质坩埚熔炼，熔化完成后制备成熟料，再将熟料投入铂或铂合金坩埚(或者黄金或含黄金的合金坩埚)中熔制，从而得到所需高品质玻璃。
本领域技术人员能够根据实际需要，适当地选择原料、工艺方法和工艺参数。
[玻璃预制件和光学元件]
可以使用例如直接滴料成型、或研磨加工的手段、或热压成型等模压成型的手段，由所制成的高折射高色散光学玻璃来制作玻璃预制件。即，可以通过对熔融光学玻璃进行直接精密滴料成型为玻璃精密预制件，或通过磨削和研磨等机械加工来制作玻璃预制件，或通过对由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。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，本发明的高折射高色散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高折射高色散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高折射高色散光学玻璃形成。本发明的玻璃预制件具有高折射高色散光学玻璃所具有的优异特性；本发明的光学元件具有高折射高色散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。
[光学仪器]
本发明高折射高色散光学玻璃所形成的光学元件可制作如照相设备、摄像设备、投影设备、显示设备、车载设备和监控设备等光学仪器。
实施例
<高折射高色散光学玻璃实施例>
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2～表4所示的组成的高折射高色散光学玻璃。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2～表4中。
表2.
Figure PCTCN2022070073-appb-000002
Figure PCTCN2022070073-appb-000003
Figure PCTCN2022070073-appb-000004
表3.
Figure PCTCN2022070073-appb-000005
Figure PCTCN2022070073-appb-000006
表4.
Figure PCTCN2022070073-appb-000007
Figure PCTCN2022070073-appb-000008
<玻璃预制件实施例>
将上述表2～表4中高折射高色散光学玻璃实施例中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，在降低玻璃内部应力的同时对折射率进行微调，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 (13)

  1. 高折射高色散光学玻璃，其特征在于，其组分以重量百分比表示，含有：P 2O 5：8～25％；Bi 2O 3：30～60％；Nb 2O 5：15～35％；WO 3：3～25％，其中Bi 2O 3/(Nb 2O 5+P 2O 5)为0.6～2.3。
  2. 根据权利要求1所述的高折射高色散光学玻璃，其特征在于，其组分以重量百分比表示，还含有：TiO 2：0～15％；和/或B 2O 3：0～10％；和/或RO：0～15％；和/或ZnO：0～10％；和/或Li 2O：0～10％；和/或Na 2O：0～10％；和/或K 2O：0～10％；和/或SiO 2+Al 2O 3+ZrO 2：0～10％；和/或Ln 2O 3：0～10％；和/或TeO 2：0～5％；和/或GeO 2：0～5％；和/或Ga 2O 3：0～5％；和/或Ta 2O 5：0～5％；和/或澄清剂：0～2％，所述Ln 2O 3为La 2O 3、Gd 2O 3、Y 2O 3、Yb 2O 3、Lu 2O 3中的一种或多种,RO为BaO、SrO、CaO、MgO中的一种或多种，澄清剂为Sb 2O 3、SnO、SnO 2、CeO 2中的一种或多种。
  3. 高折射高色散光学玻璃，其特征在于，含有P 2O 5、Nb 2O 5、WO 3和Bi 2O 3作为必要组分，其组分以重量百分比表示，其中Bi 2O 3/(Nb 2O 5+P 2O 5)为0.6～2.3，所述高折射高色散光学玻璃的折射率n d为1.95以上，阿贝数ν d为25以下，转变温度T g为520℃以下。
  4. 根据权利要求3所述的高折射高色散光学玻璃，其特征在于，其组分以重量百分比表示，含有：P 2O 5：8～25％；和/或Bi 2O 3：30～60％；和/或Nb 2O 5：15～35％；和/或WO 3：3～25％；和/或TiO 2：0～15％；和/或B 2O 3：0～10％；和/或RO：0～15％；和/或ZnO：0～10％；和/或Li 2O：0～10％；和/或Na 2O：0～10％；和/或K 2O：0～10％；和/或SiO 2+Al 2O 3+ZrO 2：0～10％；和/或Ln 2O 3：0～10％；和/或TeO 2：0～5％；和/或GeO 2：0～5％；和/或Ga 2O 3：0～5％；和/或Ta 2O 5：0～5％；和/或澄清剂：0～2％，所述Ln 2O 3为La 2O 3、Gd 2O 3、Y 2O 3、Yb 2O 3、Lu 2O 3中的一种或多种,RO为BaO、SrO、CaO、MgO中的一种或多种，澄清剂为Sb 2O 3、SnO、SnO 2、CeO 2中的一种或多种。
  5. 根据权利要求1～4任一权利要求所述的高折射高色散光学玻璃，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：
    1)Bi 2O 3/(Nb 2O 5+P 2O 5)为0.7～2.0，优选Bi 2O 3/(Nb 2O 5+P 2O 5)为0.8～1.5，更优选Bi 2O 3/(Nb 2O 5+P 2O 5)为0.9～1.3；
    2)(Nb 2O 5+TiO 2)/Bi 2O 3为0.3～1.3，优选(Nb 2O 5+TiO 2)/Bi 2O 3为0.4～1.0，更优选(Nb 2O 5+TiO 2)/Bi 2O 3为0.5～0.8，进一步优选(Nb 2O 5+TiO 2)/Bi 2O 3为0.55～0.75；
    3)(Nb 2O 5+P 2O 5)/WO 3为1.0～15.0，优选(Nb 2O 5+P 2O 5)/WO 3为1.5～12.0，更优选(Nb 2O 5+P 2O 5)/WO 3为2.5～10.0，进一步优选(Nb 2O 5+P 2O 5)/WO 3为3.0～7.0；
    4)WO 3/(Li 2O+Na 2O+K 2O)为0.2以上，优选WO 3/(Li 2O+Na 2O+K 2O)为0.5以上，更优选WO 3/(Li 2O+Na 2O+K 2O)为1.0～15.0，进一步优选WO 3/(Li 2O+Na 2O+K 2O)为1.5～8.0；
    5)(Nb 2O 5+WO 3+TiO 2+P 2O 5)/Bi 2O 3为0.5～2.5，优选(Nb 2O 5+WO 3+TiO 2+P 2O 5)/Bi 2O 3为0.7～2.0，更优选(Nb 2O 5+WO 3+TiO 2+P 2O 5)/Bi 2O 3为0.8～1.8，进一步优选(Nb 2O 5+WO 3+TiO 2+P 2O 5)/Bi 2O 3为1.0～1.5。
  6. 根据权利要求1～4任一权利要求所述的高折射高色散光学玻璃，其特征在于，其组分以重量百分比表示，满足以下4种情形中的一种以上：
    1)(Nb 2O 5+P 2O 5+TiO 2+BaO)/(Bi 2O 3+WO 3)为0.4～2.0，优选(Nb 2O 5+P 2O 5+TiO 2+BaO)/(Bi 2O 3+WO 3)为0.5～1.5，更优选(Nb 2O 5+P 2O 5+TiO 2+BaO)/(Bi 2O 3+WO 3)为0.6～1.2，进一步优选(Nb 2O 5+P 2O 5+TiO 2+BaO)/(Bi 2O 3+WO 3)为0.65～1.0；
    2)TiO 2/(SiO 2+Al 2O 3+ZrO 2)为0.1以上，优选TiO 2/(SiO 2+Al 2O 3+ZrO 2)为0.3以上，更优选TiO 2/(SiO 2+Al 2O 3+ZrO 2)为0.5～20.0，进一步优选TiO 2/(SiO 2+Al 2O 3+ZrO 2)为0.8～10.0；
    3)Na 2O/(Li 2O+Na 2O+K 2O)为0.3～1.0，优选Na 2O/(Li 2O+Na 2O+K 2O)为0.4～0.9，更优选Na 2O/(Li 2O+Na 2O+K 2O)为0.5～0.8，进一步优选Na 2O/(Li 2O+Na 2O+K 2O)为0.5～0.75；
    4)ZnO/(TiO 2+BaO)为5.0以下，优选ZnO/(TiO 2+BaO)为3.0以下， 更优选ZnO/(TiO 2+BaO)为1.5以下，进一步优选ZnO/(TiO 2+BaO)为0.8以下。
  7. 根据权利要求1～4任一权利要求所述的高折射高色散光学玻璃，其特征在于，其组分以重量百分比表示，含有：P 2O 5：12～22％，优选P 2O 5：13～19％；和/或Bi 2O 3：35～55％，优选Bi 2O 3：38～50％；和/或Nb 2O 5：18～30％，优选Nb 2O 5：20～28％；和/或WO 3：4～20％，优选WO 3：6～15％；和/或TiO 2：0.5～8％，优选TiO 2：1～5％；和/或B 2O 3：0～8％，优选B 2O 3：0～5％；和/或RO：0～9％，优选RO：0～5％；和/或ZnO：0～6％，优选ZnO：0～5％；和/或Li 2O：0～5％，优选Li 2O：0～3％；和/或Na 2O：0.5～8％，优选Na 2O：1～6％；和/或K 2O：0～6％，优选K 2O：0～5％；和/或SiO 2+Al 2O 3+ZrO 2：大于0但小于或等于8％，优选SiO 2+Al 2O 3+ZrO 2：0.1～5％；和/或Ln 2O 3：0～5％，优选Ln 2O 3：0～3％；和/或TeO 2：0～3％，优选TeO 2：0～1％；和/或GeO 2：0～3％，优选GeO 2：0～1％；和/或Ga 2O 3：0～3％，优选Ga 2O 3：0～1％；和/或Ta 2O 5：0～3％，优选Ta 2O 5：0～1％；和/或澄清剂：0～1％，优选澄清剂：0～0.5％，所述Ln 2O 3为La 2O 3、Gd 2O 3、Y 2O 3、Yb 2O 3、Lu 2O 3中的一种或多种,RO为BaO、SrO、CaO、MgO中的一种或多种，澄清剂为Sb 2O 3、SnO、SnO 2、CeO 2中的一种或多种。
  8. 根据权利要求1～4任一权利要求所述的高折射高色散光学玻璃，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Ln 2O 3；和/或不含有TeO 2；和/或不含有Ga 2O 3。
  9. 根据权利要求1～4任一权利要求所述的高折射高色散光学玻璃，其特征在于，所述高折射高色散光学玻璃的折射率n d为1.95以上，优选为1.97以上，更优选为1.99以上；阿贝数ν d为25以下，优选为23以下，更优选为21以下。
  10. 根据权利要求1～4任一权利要求所述的高折射高色散光学玻璃，其特征在于，所述高折射高色散光学玻璃的耐酸作用稳定性D A为2类以上，优选为1类；和/或耐水作用稳定性D W为2类以上，优选为1类；和/或耐 候性CR为2类以上，优选为1类；和/或热膨胀系数α -30/70℃为110×10 -7/K以下，优选为100×10 -7/K以下，更优选为90×10 -7/K以下；和/或转变温度T g为520℃以下，优选为510℃以下，更优选为500℃以下，进一步优选为495℃以下；和/或磨耗度F A为390以下，优选为380以下，更优选为360以下；和/或努氏硬度H K为350×10 7Pa以上，优选为360×10 7Pa以上，更优选为370×10 7Pa以上，进一步优选为380×10 7Pa以上；和/或λ 70为485nm以下，优选为480nm以下，更优选为470nm以下；和/或λ 5为425nm以下，优选为420nm以下，更优选为410nm以下。
  11. 玻璃预制件，其特征在于，采用权利要求1～10任一所述的高折射高色散光学玻璃制成。
  12. 光学元件，其特征在于，采用权利要求1～10任一所述的高折射高色散光学玻璃或权利要求11所述的玻璃预制件制成。
  13. 光学仪器，其特征在于，含有权利要求1～10任一所述的高折射高色散光学玻璃，和/或含有权利要求12所述的光学元件。
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