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WO2025180152A1 - Verre optique, préforme de verre, élément optique et instrument optique - Google Patents

Verre optique, préforme de verre, élément optique et instrument optique

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Publication number
WO2025180152A1
WO2025180152A1 PCT/CN2025/073578 CN2025073578W WO2025180152A1 WO 2025180152 A1 WO2025180152 A1 WO 2025180152A1 CN 2025073578 W CN2025073578 W CN 2025073578W WO 2025180152 A1 WO2025180152 A1 WO 2025180152A1
Authority
WO
WIPO (PCT)
Prior art keywords
sro
less
cao
mgo
bao
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/CN2025/073578
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English (en)
Chinese (zh)
Inventor
毛露路
伍旭奕
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
CDGM Glass Co Ltd
Original Assignee
CDGM Glass Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by CDGM Glass Co Ltd filed Critical CDGM Glass Co Ltd
Publication of WO2025180152A1 publication Critical patent/WO2025180152A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/062—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
    • C03C3/04—Glass compositions containing silica
    • C03C3/062—Glass compositions containing silica with less than 40% silica by weight
    • C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
    • C03C3/068—Glass compositions containing silica with less than 40% silica by weight containing boron containing rare earths
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/078—Glass compositions containing silica with 40% to 90% silica, by weight containing an oxide of a divalent metal, e.g. an oxide of 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
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
    • C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements

Definitions

  • the present invention relates to optical glass, in particular to optical glass with a refractive index of 1.68-1.76 and an Abbe number of 31-38, and a glass preform, an optical element and an optical instrument made of the same.
  • optical design requires that optical glass have the appropriate performance to eliminate or minimize residual chromatic aberration in the secondary spectrum, which requires optical glass to have low relative partial dispersion (Pg ,F ).
  • Chinese patent CN101857358A discloses an optical glass with a refractive index of 1.69 to 1.82 and an Abbe number of 33 to 46. This glass has low relative partial dispersion, but the glass has a high transition temperature, making it unsuitable for precision molding of optical components.
  • Chinese patent CN101215086A discloses a low-melting-point optical glass with a refractive index of 1.65 to 1.85 and an Abbe number of 20 to 35. Although this glass has a low transition temperature, its anti-devitrification performance is poor, making it unsuitable for secondary hot pressing.
  • the technical problem to be solved by the present invention is to provide an optical glass with excellent anti-crystallization performance, low transition temperature and relative partial dispersion.
  • Optical glass the components of which, expressed in weight percentage, contain: SiO2 : 30-50%; Nb2O5 : 25-38%; ZrO2 : 1-10%; BaO : 3-15%; SrO: 3-13%; Li2O : 1-7%; Na2O : 2-9%; K2O : 1-7%.
  • the optical glass according to (1) wherein the components are expressed in weight percentage and further contain : B2O3 : 0-4%; and/or Al2O3 : 0-3%; and/or TiO2 : 0-3%; and/or Ln2O3 : 0-4%; and/or ZnO : 0-5%; and/or CaO: 0-5%; and/or MgO : 0-5%; and/or P2O5 : 0-3%; and/or a clarifier: 0-1 % , wherein the Ln2O3 is one or more of La2O3 , Gd2O3 , Y2O3 , and Yb2O3 , and the clarifier is one or more of Sb2O3 , SnO , SnO2 , and CeO2 .
  • Optical glass the components of which are expressed in weight percentages as follows : SiO2 : 30-50%; Nb2O5 : 25-38%; ZrO2: 1-10%; BaO : 3-15%; SrO: 3-13%; Li2O: 1-7 %; Na2O: 2-9%; K2O : 1-7%; B2O3 : 0-4%; Al2O3 : 0-3 %; TiO2 : 0-3%; Ln2O3 : 0-4 %; ZnO : 0-5%; CaO: 0-5%; MgO: 0-5%; P2O5 : 0-3%; and a clarifier: 0-1% .
  • the Ln2O3 is selected from La2O3 , Gd2O3 , Y2O3 , Yb2O3 , and ZnO . 3 , wherein the clarifier is one or more of Sb 2 O 3 , SnO, SnO 2 , and CeO 2 .
  • Optical glass comprising SiO2 , Nb2O5 , ZrO2 , BaO , SrO, Li2O , Na2O and K2O , wherein the optical glass has a refractive index nd of 1.68 to 1.76, an Abbe number vd of 31 to 38, a relative partial dispersion Pg ,F of 0.6000 or less, and a transition temperature Tg of 630°C or less.
  • optical glass according to (4) wherein the components thereof are expressed in weight percentages as follows: SiO 2 : 30-50%; and/or Nb 2 O 5 : 25-38%; and/or ZrO 2 : 1-10%; and/or BaO: 3-15%; and/or SrO: 3-13%; and/or Li 2 O: 1-7%; and/or Na 2 O: 2-9%; and/or K 2 O: 1-7%; and/or B 2 O 3 : 0-4%; and/or Al 2 O 3 : 0-3%; and/or TiO 2 : 0-3%; and/or Ln 2 O 3 : 0-4%; and/or ZnO: 0-5%; and/or CaO: 0-5%; and/or MgO: 0-5%; and/or P 2 O 5 : 0-3%; and/or clarifier: 0-1%, wherein the Ln2O3 is one or more of La2O3 , Gd2O3 , Y2O3 , and Yb
  • (9) The optical glass according to any one of (1) to (5), wherein the composition is expressed in weight percentage, wherein: (B 2 O 3 +Ln 2 O 3 )/(MgO + SrO + CaO) is less than 1.5, preferably (B 2 O 3 +Ln 2 O 3 )/(MgO + SrO + CaO) is less than 1.0, more preferably (B 2 O 3 +Ln 2 O 3 )/(MgO + SrO + CaO) is less than 0.5, and further preferably (B 2 O 3 +Ln 2 O 3 )/(MgO + SrO + CaO) is less than 0.3, and the Ln 2 O 3 is one or more of La 2 O 3 , Gd 2 O 3 , Y 2 O 3 , and Yb 2 O 3 .
  • (10) The optical glass according to any one of (1) to (5), wherein the composition is expressed in weight percentage, wherein: (Nb 2 O 5 +B 2 O 3 +ZnO)/(MgO+SrO+CaO+BaO) is 0.9 to 5.5, preferably (Nb 2 O 5 +B 2 O 3 +ZnO)/(MgO+SrO+CaO+BaO) is 1.0 to 5.0, more preferably (Nb 2 O 5 +B 2 O 3 +ZnO)/(MgO+SrO+CaO+BaO) is 1.2 to 4.0, and further preferably (Nb 2 O 5 +B 2 O 3 +ZnO)/(MgO+SrO+CaO+BaO) is 1.5 to 3.0.
  • optical glass according to any one of (1) to (5), wherein the composition is expressed in weight percentage, wherein: ZnO/ZrO 2 is less than 1.0, preferably ZnO/ZrO 2 is greater than 0 but less than or equal to 0.8, more preferably ZnO/ZrO 2 is 0.01 to 0.6, and further preferably ZnO/ZrO 2 is 0.05 to 0.5.
  • optical glass according to any one of (1) to (5), wherein the components are expressed in weight percentage, wherein: SiO2 : 35-45%, preferably SiO2 : 37-43%; and/or Nb2O5 : 26-36%, preferably Nb2O5 : 28-32%; and/or ZrO2 : 3-8%, preferably ZrO2 : 4-7%; and/or BaO: 4-11%, preferably BaO: 5-9%; and/or SrO : 4-10%, preferably SrO: 5-8%; and/or Li2O: 1-5%, preferably Li2O : 1-4%; and/or Na2O : 2-7%, preferably Na2O : 2-6%; and/or K2O : 1-5%, preferably K2O : 1-4%; and/or B2O3 : 0-2 %, preferably B2O3 3 : 0-1%; and/or Al 2 O 3 : 0-2%, preferably Al 2 O 3 : 0-1%; and/or
  • optical glass according to any one of (1) to (5), which does not contain TiO 2 ; and/or does not contain B 2 O 3 ; and/or does not contain Al 2 O 3 ; and/or does not contain CaO; and/or does not contain MgO; and/or does not contain P 2 O 5 ; and/or does not contain La 2 O 3 ; and/or does not contain Gd 2 O 3 ; and/or does not contain Y 2 O 3 ; and/or does not contain Yb 2 O 3 .
  • optical glass according to any one of (1) to (5), wherein the refractive index nd of the optical glass is 1.68 to 1.76, preferably 1.69 to 1.75, more preferably 1.70 to 1.74, and/or the Abbe number vd is 31 to 38, preferably 32 to 37, more preferably 33 to 36.
  • the beneficial effects of the present invention are: through reasonable component design, the optical glass obtained by the present invention has excellent anti-crystallization performance, low transition temperature and relative partial dispersion.
  • optical glass of the present invention may be simply referred to as "glass.”
  • the content and total content of each component are all expressed in weight percentage (wt%), that is, the content and total content of each component are expressed as the weight percentage of the total amount of the glass material converted into an oxide composition.
  • wt% weight percentage
  • the "composition converted into oxides” refers to the case where the oxides, complex salts, hydroxides, etc. used as raw materials for the optical glass of the present invention decompose and convert to oxides during melting, with the total amount of the oxide material being taken as 100%.
  • SiO2 is an essential component of the optical glass of the present invention and serves as its backbone. If its content is less than 30%, it is difficult to obtain stable glass, and the chemical stability and anti-devitrification properties of the glass deteriorate. Therefore, the SiO2 content in the present invention is 30% or more, preferably 35% or more, and more preferably 37% or more. If the SiO2 content exceeds 50%, the meltability of the glass deteriorates, and it is difficult to obtain the desired optical constants. Therefore, the SiO2 content is 50% or less, preferably 45% or less, and more preferably 43% or less.
  • the B2O3 content in the present invention is 0-4%, preferably 0-2%, and more preferably 0-1%. In some embodiments, it is further preferred that B2O3 be absent.
  • Al2O3 can improve the chemical stability of glass, but if its content exceeds 3%, the glass's solubility and light transmittance deteriorate. Therefore, in the present invention, the Al2O3 content is 0-3%, preferably 0-2%, and more preferably 0-1%. In some embodiments, it is further preferred that no Al2O3 be present.
  • ZrO2 increases the refractive index of glass, improves its chemical stability, and regulates its relative partial dispersion. However, excessive ZrO2 increases melting difficulty, increases melting temperatures, and can lead to inclusions and reduced light transmittance. Therefore, the ZrO2 content is 1-10%, preferably 3-8%, and more preferably 4-7%.
  • TiO2 increases the refractive index and dispersion of glass. A moderate amount can stabilize the glass and reduce its viscosity. A TiO2 content exceeding 3% increases the tendency of the glass to crystallize, increases relative partial dispersion, and reduces light transmittance. Therefore, the TiO2 content in the present invention is 3% or less, preferably 2% or less, and more preferably 1% or less. In some embodiments, it is further preferred that TiO2 be absent.
  • Nb2O5 is a component that improves the devitrification resistance, refractive index, and dispersion of glass, achieving anomalous dispersion. However, if its content is too high, the thermal stability and light transmittance of the glass decrease, and the liquidus temperature tends to rise. Therefore, the Nb2O5 content in the present invention is 25-38%, preferably 26-36%, and more preferably 28-32%.
  • controlling the ratio of SiO2 to Nb2O5 ( SiO2 / Nb2O5 ) within a range of 0.9 to 1.8 helps the glass achieve a lower relative partial dispersion, while also optimizing the high - temperature viscosity and chemical stability of the glass and preventing an increase in the thermal expansion coefficient of the glass . Therefore, the SiO2 / Nb2O5 ratio is preferably 0.9 to 1.8, more preferably 1.0 to 1.6, and even more preferably 1.1 to 1.5 .
  • Ln2O3 is one or more of La2O3 , Gd2O3 , Y2O3 , and Yb2O3
  • Ln2O3 content is 4% or less, preferably 2% or less, and more preferably 1 % or less.
  • La2O3 , Gd2O3 , Y2O3 , and Yb2O3 be excluded.
  • the ZnO can adjust the refractive index and dispersion of glass, lowering its high-temperature viscosity and transition temperature, allowing it to be melted at lower temperatures, thereby increasing its light transmittance. Excessive ZnO content increases glass molding difficulty and deteriorates its anti-devitrification properties. Therefore, the ZnO content is 0-5%, preferably greater than 0 but less than or equal to 3%, and more preferably 0.1-2%.
  • controlling the ratio of ZnO to ZrO2 , ZnO/ ZrO2 , to below 1.0 can optimize the thermal expansion coefficient and high-temperature viscosity of the glass and prevent deterioration of the glass's bubble content and relative partial dispersion. Therefore, ZnO/ZrO2 is preferably below 1.0, more preferably greater than 0 but less than or equal to 0.8, further preferably between 0.01 and 0.6, and even more preferably between 0.05 and 0.5.
  • BaO can increase the abrasiveness and hardness of glass and reduce its temperature coefficient of refractive index and thermal expansion coefficient.
  • a high BaO content can reduce the chemical stability of the glass. Therefore, the BaO content is 3-15%, preferably 4-11%, and more preferably 5-9%.
  • the SrO content in the present invention is 3-13%, preferably 4-10%, and more preferably 5-8%.
  • controlling the ratio of the total content of TiO2, B2O3 , and ZnO ( TiO2 + B2O3 + ZnO ) to the content of SrO (( TiO2 + B2O3 + ZnO)/SrO)) to 1.3 or less can improve the bubble content and anti-vitrification performance of the glass and lower the glass transition temperature.
  • ( TiO2 + B2O3 + ZnO)/SrO is preferably 1.3 or less, more preferably ( TiO2 + B2O3 + ZnO)/SrO is 1.0 or less, further preferably ( TiO2 + B2O3 + ZnO)/SrO is 0.01 to 0.7, and even more preferably ( TiO2 + B2O3 + ZnO)/SrO is 0.05 to 0.4 .
  • CaO helps adjust the optical constants of glass, improves its processing properties, and reduces its density. However, excessive CaO content deteriorates the glass's anti-vitrification properties. Therefore, the CaO content is limited to 5% or less, preferably 3% or less, and more preferably 1% or less. In some embodiments, CaO is preferably absent.
  • MgO helps improve the weather resistance of glass, but high MgO content makes it difficult to meet design requirements for the glass's refractive index, reduces the glass's anti-devitrification performance and stability, and rapidly increases the cost of the glass. Therefore, the MgO content is limited to 0-5%, preferably 0-3%, and more preferably 0-1%. In some embodiments, MgO is preferably absent.
  • the ratio of the total content of B2O3 and Ln2O3 ( B2O3 + Ln2O3 ) to the total content of MgO , CaO, and SrO is controlled to be below 1.5, which can prevent relative partial dispersion and increase in density of the glass and improve the light transmittance of the glass. Therefore, ( B2O3 + Ln2O3 )/ ( MgO + SrO+ CaO ) is preferably 1.5 or less , more preferably 1.0 or less, further preferably 0.5 or less , and even more preferably 0.3 or less.
  • the ratio of the total content of Nb2O5 , B2O3 , and ZnO ( Nb2O5 + B2O3 +ZnO) to the total content of MgO, CaO, SrO , and BaO (MgO+SrO+CaO+BaO) ( Nb2O5 + B2O3 +ZnO)/(MgO+ SrO +CaO+BaO) is controlled within the range of 0.9 to 5.5, which is beneficial to reducing the high-temperature viscosity and transition temperature of the glass and improving the chemical stability of the glass.
  • ( Nb2O5 + B2O3 + ZnO )/(MgO+SrO + CaO+BaO) is preferably 0.9 to 5.5, more preferably ( Nb2O5 + B2O3 + ZnO )/(MgO+ SrO +CaO+BaO) is 1.0 to 5.0, further preferably ( Nb2O5 + B2O3 + ZnO )/(MgO+ SrO +CaO+BaO) is 1.2 to 4.0, and further preferably ( Nb2O5 + B2O3 + ZnO )/(MgO+ SrO +CaO+BaO) is 1.5 to 3.0.
  • the ratio of the total content of MgO, CaO, SrO, and BaO ( MgO+SrO+CaO+BaO) to the total content of Nb2O5 and TiO2 ( Nb2O5 +TiO2 ) (MgO+SrO+CaO+BaO)/( Nb2O5 + TiO2 ) is controlled within the range of 0.2 to 1.2, which can optimize the bubble degree and thermal expansion coefficient of the glass and prevent the density and transition temperature of the glass from increasing.
  • (MgO+SrO+CaO+BaO)/( Nb2O5 + TiO2 ) is preferably 0.2-1.2, more preferably (MgO+SrO+CaO+BaO)/( Nb2O5 + TiO2 ) is 0.25-1.0, further preferably (MgO+ SrO +CaO+BaO)/( Nb2O5 + TiO2 ) is 0.3-0.8, and further preferably (MgO+ SrO +CaO+BaO)/( Nb2O5 + TiO2 ) is 0.3-0.6 .
  • Li2O can lower the glass transition temperature, adjust the high temperature viscosity of glass, and improve the meltability of glass, but its high content is detrimental to the chemical stability of glass. Therefore, the content of Li2O in the present invention is 1-7%, preferably 1-5%, and more preferably 1-4%.
  • Na2O improves the meltability of glass, enhancing its melting efficiency and helping to reduce the relative partial dispersion of the glass.
  • excessively high Na2O content reduces the chemical stability and weather resistance of the glass. Therefore, the Na2O content is 2-9%, preferably 2-7%, and more preferably 2-6%.
  • controlling the ratio ( Na2O +BaO)/(Li2O+SrO) between the combined content of Na2O and BaO ( Na2O +BaO) and the combined content of Li2O and SrO ( Li2O +SrO) ( Na2O +BaO)/( Li2O +SrO) within a range of 0.4 to 5.0 can provide the glass with excellent anti-devitrification performance and high-temperature viscosity while preventing a decrease in the light transmittance of the glass. Therefore, the ratio ( Na2O + BaO )/( Li2O +SrO ) is preferably 0.4 to 5.0, more preferably 0.5 to 3.5, further preferably 0.7 to 2.5, and even more preferably 0.9 to 2.0.
  • K2O improves the thermal stability and meltability of glass, but if its content is too high, the devitrification resistance and chemical stability of the glass deteriorate. Therefore, the content of K2O in the present invention is 1-7%, preferably 1-5%, and more preferably 1-4%.
  • Li2O / ( Na2O + K2O ) is preferably 0.1 to 2.0, more preferably 0.2 to 1.5 , further preferably 0.2 to 1.0 , and even more preferably 0.3 to 0.7.
  • controlling the ratio of the total content of Li2O , Na2O , and K2O ( Li2O + Na2O + K2O ) to the content of SrO (( Li2O + Na2O + K2O )/SrO)) within a range of 0.5 to 4.5 can reduce the transition temperature of the glass while optimizing the light transmittance and preventing an increase in the high - temperature viscosity of the glass . Therefore, ( Li2O + Na2O + K2O )/SrO is preferably 0.5 to 4.5, more preferably 0.6 to 4.0, further preferably 0.8 to 3.0 , and even more preferably 1.0 to 2.5 .
  • P2O5 can adjust the Abbe number of the glass. However, for this system of glass, a P2O5 content exceeding 3% will form a large number of crystal nuclei in the glass, rapidly deteriorating the glass's anti-vitrification properties. Therefore, the P2O5 content is limited to 3% or less, preferably 2% or less, and more preferably 1% or less. In some embodiments, it is further preferred that P2O5 be absent.
  • the inclusion of one or more of Sb2O3 , SnO, SnO2 , and CeO2 as fining agents at a level of 0-1% can enhance the clarification and foaming properties of the glass.
  • the preferred clarifier content is 0-0.5%, and more preferably 0-0.1%.
  • the Sb2O3 content exceeds 1 %, the glass tends to suffer from reduced clarification. Furthermore, its strong oxidizing effect promotes corrosion of the platinum or platinum alloy vessel used for melting the glass and deteriorates the forming mold. Therefore, the preferred Sb2O3 content is 0-1%, more preferably 0-0.5%, and even more preferably 0-0.1%.
  • the SnO2 content of the present invention is preferably 0-1%, more preferably 0-0.5%, and even more preferably 0-0.1%.
  • the SnO content is preferably 0-1%, more preferably 0-0.5%, and even more preferably 0-0.1%.
  • the role and content of CeO2 are the same as those of SnO2 . Its content is preferably 0-1%, more preferably 0-0.5%, and even more preferably 0-0.1%. It is even more preferred that CeO2 be absent.
  • the glass of the present invention even if oxides of transition metals such as V, Cr, Mn, Fe, Co, Ni, Cu, Ag, and Mo are contained alone or in combination in small amounts, the glass will be colored and absorb specific wavelengths in the visible light region, thereby weakening the property of the present invention of improving visible light transmittance. Therefore, it is preferably substantially free of such oxides, especially in optical glasses requiring transmittance at wavelengths in the visible light region.
  • Oxides of Th, Cd, Tl, Os, Be, and Se have been increasingly regulated as hazardous chemicals in recent years, necessitating environmental protection measures not only during glass manufacturing but also during processing and post-product disposal. Therefore, given the importance of environmental impact, it is preferable to virtually eliminate these oxides, except where they are unavoidably incorporated. This results in optical glass being virtually free of environmentally polluting substances. Therefore, even without adopting specific environmental countermeasures, the optical glass of the present invention can be manufactured, processed, and disposed of.
  • the optical glass of the present invention preferably does not contain As 2 O 3 and PbO.
  • the "does not contain” and "0%” recorded herein means that the compound, molecule or element is not intentionally added as a raw material to the optical glass of the present invention; however, as raw materials and/or equipment for producing optical glass, there may be certain impurities or components that are not intentionally added, which may be contained in small amounts or trace amounts in the final optical glass. This situation is also within the scope of protection of the patent of this invention.
  • the refractive index (n d ) and Abbe number ( ⁇ d ) of optical glass are tested in accordance with the method specified in GB/T 7962.1—2010.
  • the lower limit of the refractive index (n d ) of the optical glass of the present invention is 1.68, preferably 1.69, and more preferably 1.70.
  • the upper limit of the refractive index ( nd ) of the optical glass of the present invention is 1.76, preferably 1.75, and more preferably 1.74.
  • the lower limit of the Abbe number ( ⁇ d ) of the optical glass of the present invention is 31, preferably 32, and more preferably 33.
  • the upper limit of the Abbe number ( ⁇ d ) of the optical glass of the present invention is 38, preferably 37, and more preferably 36.
  • the density ( ⁇ ) of optical glass is tested according to the method specified in GB/T7962.20-2010.
  • the density ( ⁇ ) of the optical glass of the present invention is 3.80 g/cm 3 or less, preferably 3.60 g/cm 3 or less, and more preferably 3.50 g/cm 3 or less.
  • the transmittance of optical glass within 400nm is tested according to the method specified in GB/T7962.12-2010, and the thickness of the glass sample is 10mm.
  • the optical glass of the present invention has a transmittance within 400 nm ( ⁇ 400nm ) of 88.0% or more, preferably 90.0% or more, more preferably 90.5% or more, further preferably 91.0% or more, further preferably 92.0% or more, and even more preferably 92.5% or more.
  • Relative partial dispersion of optical glass ( ng - nF )/( nF - nC ).
  • the relative partial dispersion (P g,F ) of the optical glass of the present invention is 0.6000 or less, preferably 0.5900 or less, and more preferably 0.5860 or less.
  • the present invention uses strong acid resistance to characterize the acid resistance and chemical stability of glass.
  • the test method is to polish a large surface of a 30 ⁇ 30 ⁇ 10 mm glass sample, immerse it in an acid solution with a pH of 2.0, and take it out every 5 hours to observe whether there are corrosion spots on the surface. The longer the time from immersion to the appearance of corrosion spots, the better the acid resistance of the glass.
  • the time from immersion of the optical glass of the present invention in the acid solution to the appearance of corrosion spots is more than 60 hours, preferably more than 80 hours, and more preferably more than 100 hours.
  • the anti-crystallization performance of the glass of the present invention is tested in the following manner:
  • the experimental glass samples were processed into a size of 20 ⁇ 20 ⁇ 10mm and polished on both sides.
  • the samples were placed in a crystallization furnace at a temperature of Tg +200°C and kept warm for 30 minutes. After being taken out and cooled, the two large surfaces were polished again.
  • the crystallization performance of the glass was judged according to Table 1 below, with grade A being the best and grade E being the worst.
  • the anti-devitrification performance of the optical glass of the present invention is Class B or above, preferably Class A.
  • the thermal expansion coefficient of optical glass ( ⁇ 20/120°C ) is measured at 20°C ⁇ 120°C according to the method specified in GB/T 7962.16-2010.
  • the thermal expansion coefficient ( ⁇ 20/120° C. ) of the optical glass of the present invention is 90 ⁇ 10 ⁇ 7 /K or less, preferably 85 ⁇ 10 ⁇ 7 /K or less, and more preferably 80 ⁇ 10 ⁇ 7 /K or less.
  • the bubble degree of optical glass is tested according to the method specified in GB/T7962.8-2010.
  • the bubble degree of the optical glass of the present invention is above grade A, preferably above grade A0 .
  • the high temperature viscosity of optical glass is tested as follows: The high temperature viscosity of glass is tested using the THETA Rheotronic II high temperature viscometer using the rotation method. The unit of value is dPaS (poise). The smaller the value, the lower the viscosity.
  • the viscosity of the optical glass of the present invention at 1400° C. is 50 poise or less, preferably 35 poise or less, and more preferably 20 poise or less.
  • the transition temperature (T g ) of 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 630° C. or lower, preferably 620° C. or lower, and more preferably 610° C. or lower.
  • the optical glass of the present invention is produced using conventional raw materials and processes, including but not limited to oxides, hydroxides, complex salts (such as carbonates, nitrates, sulfates, phosphates, metaphosphates, etc.), boric acid, etc., and after being prepared according to conventional methods, the prepared charge is placed in a melting furnace (such as a platinum or platinum alloy crucible) at 1200-1500°C for melting. After clarification and homogenization, a homogeneous molten glass free of bubbles and undissolved matter is obtained. The molten glass is then cast in a mold and annealed. Those skilled in the art can appropriately select the raw materials, process methods, and process parameters according to actual needs.
  • a glass preform can be produced from the produced optical glass using methods such as direct drop molding, grinding, or compression molding such as hot pressing. Specifically, the molten optical glass can be directly drop molded into a precision glass preform, or the glass preform can be produced through mechanical processing such as grinding and lapping. Alternatively, the glass preform can be produced by forming a preform for compression molding from the optical glass, hot pressing the preform, and then grinding the preform. It should be noted that the methods for producing the glass preform are not limited to the methods described above.
  • the optical glass of the present invention is useful for various optical elements and optical designs. It is particularly preferred to form a preform from the optical glass of the present invention and use the preform to perform re-hot pressing, precision stamping, etc. to produce optical elements such as lenses and prisms.
  • the glass preform and optical element of the present invention are both formed from the optical glass of the present invention.
  • the glass preform and optical element of the present invention possess the excellent properties of optical glass, and they can provide various optical elements such as lenses and prisms with high optical value.
  • the lens examples include various lenses having spherical or aspherical lens surfaces, 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.
  • the optical glass of the present invention can be used to prepare optical elements such as chemically strengthened imaging lenses.
  • the optical glass or optical components formed from the present invention can be used to manufacture optical instruments such as photographic equipment, video equipment, display equipment, and monitoring equipment.
  • the optical glass or optical components of the present invention are suitable for use in automotive lighting equipment and optical equipment, and are used in automotive and other fields.
  • the optical glass or optical components of the present invention are suitable for use in optical instruments such as micro-projectors, micro-imaging (video/photography), and micro-lighting.
  • This embodiment uses the above-mentioned optical glass manufacturing method to obtain optical glasses having the compositions shown in Tables 2 to 4.
  • the properties of each glass were measured using the testing method described in the present invention, and the measurement results are shown in Tables 2 to 4.
  • optical glass examples 1 to 24# is used to make preforms of various lenses, prisms, etc., such as concave meniscus lenses, convex meniscus lenses, double convex lenses, double concave lenses, plano-convex lenses, and plano-concave lenses, by means of, for example, grinding processing, or molding methods such as re-hot pressing, precision stamping, etc.
  • various lenses, prisms, etc. such as concave meniscus lenses, convex meniscus lenses, double convex lenses, double concave lenses, plano-convex lenses, and plano-concave lenses
  • the preforms obtained from the above-mentioned glass preform embodiments are annealed to reduce the internal stress of the glass and fine-tune the refractive index so that the optical properties such as the refractive index reach the desired values.
  • Each preform is then ground and polished to produce various lenses and prisms, including concave meniscus lenses, convex meniscus lenses, biconvex lenses, biconcave lenses, plano-convex lenses, and plano-concave lenses.
  • the surfaces of the resulting optical elements can also be coated with an anti-reflection film.
  • optical elements made from the above-mentioned optical element embodiments are optically designed and formed into optical components or optical assemblies using one or more optical elements, which can be used in, for example, imaging equipment, sensors, microscopes, medical technology, digital projection, communications, optical communication technology/information transmission, optics/lighting in the automotive field, photolithography technology, 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)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
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  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Glass Compositions (AREA)

Abstract

La présente invention concerne un verre optique qui présente une excellente résistance à la cristallisation, une température de transition relativement faible et une dispersion partielle relative. Le verre optique comprend les composants suivants, en pourcentage en poids : SiO2 : de 30 à 50%, Nb2O5 : de 25 à 38 %, ZrO2: de 1 à 10 % ; BaO : de 3 à 15 %, SrO : de 3 à 13 %, Li2O : de 1 à 7 % ; Na2O : de 2 à 9 % et K2O de 1 à 7 %. Par une conception raisonnable des composants, le verre optique obtenu dans la présente invention présente une excellente résistance à la cristallisation et présente également une faible température de transition et une dispersion partielle relative.
PCT/CN2025/073578 2024-02-26 2025-01-21 Verre optique, préforme de verre, élément optique et instrument optique Pending WO2025180152A1 (fr)

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CN118005278A (zh) * 2024-02-26 2024-05-10 成都光明光电股份有限公司 光学玻璃、玻璃预制件、光学元件和光学仪器

Citations (6)

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GB1539232A (en) * 1975-07-10 1979-01-31 Hoya Glass Works Ltd Glass compositions for ophthalmic lenses
CN108290768A (zh) * 2015-11-24 2018-07-17 旭硝子株式会社 光学玻璃
CN113292242A (zh) * 2021-06-24 2021-08-24 成都光明光电股份有限公司 特殊色散光学玻璃
CN115448591A (zh) * 2022-10-18 2022-12-09 成都光明光电股份有限公司 光学玻璃、光学元件和光学仪器
CN118005278A (zh) * 2024-02-26 2024-05-10 成都光明光电股份有限公司 光学玻璃、玻璃预制件、光学元件和光学仪器
CN118005277A (zh) * 2024-02-26 2024-05-10 成都光明光电股份有限公司 光学玻璃及光学元件

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CN113264675B (zh) * 2021-06-24 2022-04-15 成都光明光电股份有限公司 光学玻璃、光学元件和光学仪器

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1539232A (en) * 1975-07-10 1979-01-31 Hoya Glass Works Ltd Glass compositions for ophthalmic lenses
CN108290768A (zh) * 2015-11-24 2018-07-17 旭硝子株式会社 光学玻璃
CN113292242A (zh) * 2021-06-24 2021-08-24 成都光明光电股份有限公司 特殊色散光学玻璃
CN115448591A (zh) * 2022-10-18 2022-12-09 成都光明光电股份有限公司 光学玻璃、光学元件和光学仪器
CN118005278A (zh) * 2024-02-26 2024-05-10 成都光明光电股份有限公司 光学玻璃、玻璃预制件、光学元件和光学仪器
CN118005277A (zh) * 2024-02-26 2024-05-10 成都光明光电股份有限公司 光学玻璃及光学元件

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