WO2022193797A1 - Verre optique à haute réfraction et à haute dispersion et élément optique - Google Patents

Verre optique à haute réfraction et à haute dispersion et élément optique 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)
Chinese (zh)
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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/fr

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

Abstract

La présente invention concerne un verre optique à indice de réfraction élevé et à haute dispersion. Le verre optique à indice de réfraction élevé et à haute dispersion comprend des constituants tels que représentés en pourcentage en poids : 8 à 25 % de P2O5 ; 30 à 60 % de Bi2O3 ; 15 à 35 % de Nb2O5 ; et 3 à 25 % de WO3, le rapport Bi2O3/(Nb2O5+P2O5) étant compris entre 0,6 et 2,3. Au moyen d'une conception de constituants raisonnable, le verre optique obtenu dans la présente invention a une température de transition relativement faible tout en ayant un indice de réfraction et un nombre d'Abbe attendus, et est approprié pour un moulage par chute précis ou un moulage par compression précis.
PCT/CN2022/070073 2021-03-18 2022-01-04 Verre optique à haute réfraction et à haute dispersion et élément optique WO2022193797A1 (fr)

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