Optical glass, glass preform, optical element and optical instrument

Abstract

Provided in the present invention is optical glass which has excellent crystallization resistance, a relatively low transition temperature and relative partial dispersion. The optical glass comprises the following components in percentages by weight: SiO2: 30-50%, Nb2O5: 25-38%, ZrO2: 1-10%, BaO: 3-15%, SrO: 3-13%, Li2O: 1-7%, Na2O: 2-9%, and K2O: 1-7%. By means of reasonable component design, the optical glass obtained in the present invention has excellent crystallization resistance and also has a low transition temperature and relative partial dispersion.

Description

Optical glass, glass preforms, optical components and optical instruments Technical Field

[0001] 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. Background Art

[0002] In recent years, with the rapid development of optoelectronic products such as smart phones, SLR cameras and surveillance security, higher requirements have been placed on the performance of optical glass. For example, in optical design, it is expected that optical glass has the performance to eliminate or minimize the residual chromatic aberration of the secondary spectrum, which requires the optical glass to have a low relative partial dispersion (P g,F ).

[0003] 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. Summary of the Invention

[0004] 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.

[0005] The technical solution adopted by the present invention to solve the technical problem is:

[0006] (1) Optical glass, the components of which, expressed in percentage by weight, 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%.

[0007] (2) 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.

[0008] (3) Optical glass, the components of which, expressed in percentage by weight, are composed of 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%, 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.

[0009] (4) Optical glass, the components of which include SiO2, Nb2O5, ZrO2, BaO, SrO, Li2O, Na2O and K2O, and the refractive index of the optical glass is n d is 1.68~1.76, Abbe number v d 31~38, relative partial dispersion P g,F Below 0.6000, the transition temperature T g Below 630°C.

[0010] (5) The optical glass according to (4), wherein the components thereof are expressed in weight percentages as follows: SiO2: 30-50%; and / or Nb2O5: 25-38%; and / or ZrO2: 1-10%; and / or BaO: 3-15%; and / or SrO: 3-13%; and / or Li2O: 1-7%; and / or Na2O: 2-9%; and / or K2O: 1-7%; and / or 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 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.

[0011] (6) The optical glass according to any one of (1) to (5), wherein the composition is expressed in weight percentage, wherein: SiO2 / Nb2O5 is 0.9 to 1.8, preferably SiO2 / Nb2O5 is 1.0 to 1.6, and more preferably SiO2 / Nb2O5 is 1.1 to 1.5.

[0012] (7) The optical glass according to any one of (1) to (5), wherein the components are expressed in weight percentage, wherein: (Na2O+BaO) / (Li2O+SrO) is 0.4 to 5.0, preferably (Na2O+BaO) / (Li2O+SrO) is 0.5 to 3.5, more preferably (Na2O+BaO) / (Li2O+SrO) is 0.7 to 2.5, and further preferably (Na2O+BaO) / (Li2O+SrO) is 0.9 to 2.0.

[0013] (8) The optical glass according to any one of (1) to (5), wherein the components are expressed in weight percentage, wherein: (TiO2 + B2O3 + ZnO) / SrO is less than 1.3, preferably (TiO2 + B2O3 + ZnO) / SrO is less than 1.0, more preferably (TiO2 + B2O3 + ZnO) / SrO is 0.01 to 0.7, and further preferably (TiO2 + B2O3 + ZnO) / SrO is 0.05 to 0.4.

[0014] (9) The optical glass according to any one of (1) to (5), wherein the components are expressed in weight percentage, wherein: (B2O3+Ln2O3) / (MgO+SrO+CaO) is less than 1.5, preferably (B2O3+Ln2O3) / (MgO+SrO+CaO) is less than 1.0, more preferably (B2O3+Ln2O3) / (MgO+SrO+CaO) is less than 0.5, and further preferably (B2O3+Ln2O3) / (MgO+SrO+CaO) is less than 0.3, and the Ln2O3 is one or more of La2O3, Gd2O3, Y2O3, and Yb2O3.

[0015] (10) The optical glass according to any one of (1) to (5), wherein the components are expressed in weight percentage, wherein: (Nb2O5+B2O3+ZnO) / (MgO+SrO+CaO+BaO) is 0.9 to 5.5, preferably (Nb2O5+B2O3+ZnO) / (MgO+SrO+CaO+BaO) is 1.0 to 5.0, more 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.

[0016] (11) The optical glass according to any one of (1) to (5), wherein the components are expressed in weight percentage, wherein: ZnO / ZrO2 is less than 1.0, preferably ZnO / ZrO2 is greater than 0 but less than or equal to 0.8, more preferably ZnO / ZrO2 is 0.01 to 0.6, and further preferably ZnO / ZrO2 is 0.05 to 0.5.

[0017] (12) The optical glass according to any one of (1) to (5), wherein the components are expressed in weight percentage, wherein: (MgO+SrO+CaO+BaO) / (Nb2O5+TiO2) is 0.2 to 1.2, preferably (MgO+SrO+CaO+BaO) / (Nb2O5+TiO2) is 0.25 to 1.0, more preferably (MgO+SrO+CaO+BaO) / (Nb2O5+TiO2) is 0.3 to 0.8, and further preferably (MgO+SrO+CaO+BaO) / (Nb2O5+TiO2) is 0.3 to 0.6.

[0018] (13) The optical glass according to any one of (1) to (5), wherein the components are expressed in weight percentage, wherein: Li2O / (Na2O+K2O) is 0.1 to 2.0, preferably Li2O / (Na2O+K2O) is 0.2 to 1.5, more preferably Li2O / (Na2O+K2O) is 0.2 to 1.0, and further preferably Li2O / (Na2O+K2O) is 0.3 to 0.7.

[0019] (14) The optical glass according to any one of (1) to (5), wherein the components are expressed in weight percentage, wherein: (Li2O+Na2O+K2O) / SrO is 0.5 to 4.5, preferably (Li2O+Na2O+K2O) / SrO is 0.6 to 4.0, more preferably (Li2O+Na2O+K2O) / SrO is 0.8 to 3.0, and further preferably (Li2O+Na2O+K2O) / SrO is 1.0 to 2.5.

[0020] (15) The 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: 0-1%; and / or Al2 O3: 0-2%, preferably Al2O3: 0-1%; and / or TiO2: 0-2%, preferably TiO2: 0-1%; and / or Ln2O3: 0-2%, preferably Ln2O3: 0-1%; and / or ZnO: greater than 0 but less than or equal to 3%, preferably ZnO: 0.1-2%; and / or CaO: 0-3%, preferably CaO: 0-1%; and / or MgO: 0-3%, preferably MgO: 0-1%; and / or P2O5: 0-2%, preferably P2O5: 0-1%; and / or clarifier: 0-0.5%, preferably clarifier: 0-0.1%, 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.

[0021] (16) The optical glass according to any one of (1) to (5), wherein the components do not contain TiO2; and / or do not contain B2O3; and / or do not contain Al2O3; and / or do not contain CaO; and / or do not contain MgO; and / or do not contain P2O5; and / or do not contain La2O3; and / or do not contain Gd2O3; and / or do not contain Y2O3; and / or do not contain Yb2O3.

[0022] (17) The optical glass according to any one of (1) to (5), wherein the refractive index n of the optical glass is d is 1.68 to 1.76, preferably 1.69 to 1.75, more preferably 1.70 to 1.74, and / or the Abbe number v d It is 31-38, preferably 32-37, and more preferably 33-36.

[0023] (18) The optical glass according to any one of (1) to (5), wherein the relative partial dispersion P of the optical glass is g,F is 0.6000 or less, preferably 0.5900 or less, more preferably 0.5860 or less; and / or density ρ is 3.80 g / cm 3 Below, preferably 3.60g / cm 3 Below, more preferably 3.50g / cm 3 Below; and / or transmittance τ within 400nm 400nm 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 further preferably 92.5% or more; and / or anti-crystallization performance is Class B or more, preferably Class A; and / or thermal expansion coefficient α 20 / 120℃ 90×10 -7 / K or less, preferably 85×10 -7 / K or less, more preferably 80×10 -7 / K or less; and / or the bubble degree is A grade or above, preferably A0 grade or above; and / or the viscosity at 1400°C is 50 poise or less, preferably 35 poise or less, more preferably 20 poise or less; and / or the transition temperature T g The temperature is 630°C or lower, preferably 620°C or lower, and more preferably 610°C or lower.

[0024] (19) A glass preform made of the optical glass described in any one of (1) to (18).

[0025] (20) An optical element made of the optical glass described in any one of (1) to (18), or made of the glass preform described in (19).

[0026] (21) An optical instrument comprising the optical glass described in any one of (1) to (18) and / or the optical element described in (20).

[0027] 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. DETAILED DESCRIPTION

[0028] The following describes in detail embodiments of the optical glass of the present invention. However, the present invention is not limited to the embodiments described below and can be implemented with appropriate modifications within the scope of the present invention. Furthermore, although repeated descriptions may be omitted as appropriate, this does not limit the scope of the invention. In the following description, the optical glass of the present invention may be simply referred to as "glass."

[0029] [Optical glass]

[0030] The following describes the ranges of the various components (ingredients) of the optical glass of the present invention. In the present invention, unless otherwise specified, 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. Here, 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%.

[0031] Unless otherwise indicated in specific circumstances, the numerical ranges listed in the present invention include upper and lower limits, and "above" and "below" include the endpoint values, as well as all integers and fractions included in the range, without being limited to the specific values ​​listed when defining the range. The term "and / or" herein is inclusive, for example, "A and / or B" means only A, or only B, or both A and B.

[0032] <Essential Components and Optional Components>

[0033] 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.

[0034] B2O3 improves the meltability of glass, but when its content is too high, the chemical stability of the glass deteriorates, the viscosity of the glass decreases, and its volatility increases, which is not conducive to the stable control of the refractive index and dispersion. In addition, too high a B2O3 content is not conducive to improving the light transmittance of the glass of the present invention. Therefore, 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 is absent.

[0035] Al2O3 can improve the chemical stability of glass, but when its content exceeds 3%, the glass's meltability 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 Al2O3 is not contained.

[0036] ZrO2 increases the refractive index of glass, improves its chemical stability, and regulates its relative partial dispersion. However, excessive ZrO2 content 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%.

[0037] TiO2 increases the refractive index and dispersion of glass. A moderate amount can make the glass more stable and reduce its viscosity. If the TiO2 content exceeds 3%, the glass's tendency to crystallize increases, while the relative partial dispersion of the glass increases, and light transmittance decreases. Therefore, in the present invention, the TiO2 content 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.

[0038] 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%.

[0039] In some embodiments, 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 optimizing the glass's high-temperature viscosity and chemical stability and preventing an increase in the glass's thermal expansion coefficient. Therefore, SiO2 / Nb2O5 is preferably 0.9 to 1.8, more preferably 1.0 to 1.6, and even more preferably 1.1 to 1.5.

[0040] Ln2O3 (Ln2O3 is one or more of La2O3, Gd2O3, Y2O3, and Yb2O3) is a component that increases the refractive index and chemical stability of glass. By controlling the Ln2O3 content to 4% or less, it is possible to prevent a decrease in the glass's devitrification resistance. Therefore, the Ln2O3 content is 4% or less, preferably 2% or less, and more preferably 1% or less. In some embodiments, it is further preferred that the glass contain no La2O3, and / or no Gd2O3, and / or no Y2O3, and / or no Yb2O3.

[0041] 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%.

[0042] In some embodiments, 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 0.01 to 0.6, and even more preferably 0.05 to 0.5.

[0043] BaO can increase the abrasiveness and hardness of glass and reduce its temperature coefficient of refractive index and thermal expansion coefficient. However, 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%.

[0044] SrO can improve the anti-devitrification performance and chemical stability of glass and reduce the density of glass. However, due to its high price, too high a content of SrO will increase the cost of glass. Therefore, the SrO content in the present invention is 3-13%, preferably 4-10%, and more preferably 5-8%.

[0045] In some embodiments, 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 density and anti-devitrification performance of the glass and lower the glass transition temperature. Therefore, preferably, (TiO2 + B2O3 + ZnO) / SrO is 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.

[0046] 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.

[0047] 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.

[0048] In some embodiments, the ratio of the total content of B2O3 and Ln2O3 (B2O3+Ln2O3) to the total content of MgO, CaO, and SrO (MgO+SrO+CaO) (B2O3+Ln2O3) / (MgO+SrO+CaO)) is controlled to be below 1.5, which can prevent relative partial dispersion and density increase of the glass and improve the light transmittance of the glass. Therefore, it is preferred that (B2O3+Ln2O3) / (MgO+SrO+CaO) is below 1.5, more preferably (B2O3+Ln2O3) / (MgO+SrO+CaO) is below 1.0, further preferably (B2O3+Ln2O3) / (MgO+SrO+CaO) is below 0.5, and even more preferably (B2O3+Ln2O3) / (MgO+SrO+CaO) is below 0.3.

[0049] In some embodiments, 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. Therefore, the preferred ratio of (Nb2O5+B2O3+ZnO) / (MgO+SrO+CaO+BaO) is 0.9~5.5, the more preferred ratio of (Nb2O5+B2O3+ZnO) / (MgO+SrO+CaO+BaO) is 1.0~5.0, the further preferred ratio of (Nb2O5+B2O3+ZnO) / (MgO+SrO+CaO+BaO) is 1.2~4.0, and the further preferred ratio of (Nb2O5+B2O3+ZnO) / (MgO+SrO+CaO+BaO) is 1.5~3.0.

[0050] In some embodiments, 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. Therefore, the preferred ratio of (MgO+SrO+CaO+BaO) / (Nb2O5+TiO2) is 0.2~1.2, the more preferred ratio of (MgO+SrO+CaO+BaO) / (Nb2O5+TiO2) is 0.25~1.0, the further preferred ratio of (MgO+SrO+CaO+BaO) / (Nb2O5+TiO2) is 0.3~0.8, and the further preferred ratio of (MgO+SrO+CaO+BaO) / (Nb2O5+TiO2) is 0.3~0.6.

[0051] Li2O can lower the glass transition temperature, adjust the high-temperature viscosity of glass, and improve the glass's meltability. However, high Li2O content is detrimental to the chemical stability of the glass. Therefore, the Li2O content in the present invention is 1-7%, preferably 1-5%, and more preferably 1-4%.

[0052] Na2O improves the meltability of glass, enhancing its melting efficiency and helping to reduce the relative partial dispersion of the glass. However, excessive 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%.

[0053] In some embodiments, controlling the ratio (Na2O+BaO) / (Li2O+SrO) between the total content of Na2O and BaO (Na2O+BaO) and the total content of Li2O and SrO (Li2O+SrO) within the 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, preferably, (Na2O+BaO) / (Li2O+SrO) is 0.4 to 5.0, more preferably, (Na2O+BaO) / (Li2O+SrO) is 0.5 to 3.5, further preferably, (Na2O+BaO) / (Li2O+SrO) is 0.7 to 2.5, and even more preferably, (Na2O+BaO) / (Li2O+SrO) is 0.9 to 2.0.

[0054] 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 will deteriorate. Therefore, the content of K2O in the present invention is 1-7%, preferably 1-5%, and more preferably 1-4%.

[0055] In some embodiments, controlling the ratio of the Li2O content to the combined content of Na2O and K2O (Na2O+K2O), Li2O / (Na2O+K2O), within a range of 0.1 to 2.0 can improve the chemical stability and light transmittance of the glass and prevent a decrease in the anti-devitrification performance of the glass. Therefore, 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.

[0056] In some embodiments, 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 optimize light transmittance while lowering the transition temperature of the glass and prevent an increase in the high-temperature viscosity of the glass. Therefore, (Li2O+Na2O+K2O) / SrO is preferably 0.5 to 4.5, more preferably (Li2O+Na2O+K2O) / SrO is 0.6 to 4.0, further preferably (Li2O+Na2O+K2O) / SrO is 0.8 to 3.0, and even more preferably (Li2O+Na2O+K2O) / SrO is 1.0 to 2.5.

[0057] P2O5 can adjust the Abbe number of 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 less than 3%, preferably less than 2%, and more preferably less than 1%. In some embodiments, it is further preferred that P2O5 be absent.

[0058] The present invention includes 0-1% of one or more of Sb2O3, SnO, SnO2, and CeO2 as clarifiers to enhance the clarification and bubble content of the glass. The preferred clarifier content is 0-0.5%, and more preferably 0-0.1%. When the Sb2O3 content exceeds 1%, the glass tends to have reduced clarity. 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 present invention preferably includes an Sb2O3 content of 0-1%, more preferably 0-0.5%, and even more preferably 0-0.1%. SnO and SnO2 can also serve as clarifiers, but when their content exceeds 1%, the glass tends to color. Furthermore, when the glass is heated, softened, and then re-molded by molding, Sn can serve as a starting point for crystal nucleation, leading to devitrification. Therefore, the content of SnO2 in the present invention is preferably 0-1%, more preferably 0-0.5%, and even more preferably 0-0.1%; the content of SnO is preferably 0-1%, more preferably 0-0.5%, and even more preferably 0-0.1%. The function and content of CeO2 are the same as those of SnO2, and 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.

[0059] <Components that should not be contained>

[0060] In 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.

[0061] 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.

[0062] In order to achieve environmental friendliness, the optical glass of the present invention preferably does not contain As2O3 and PbO.

[0063] 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.

[0064] Next, the properties of the optical glass of the present invention will be described.

[0065] <Refractive Index and Abbe Number>

[0066] The refractive index of optical glass (n d ) and Abbe number (ν d ) Tested in accordance with the method specified in GB / T 7962.1-2010.

[0067] In some embodiments, the refractive index (n d ) is 1.68, preferably 1.69, and more preferably 1.70.

[0068] In some embodiments, the refractive index (n d ) is 1.76, preferably 1.75, and more preferably 1.74.

[0069] In some embodiments, the Abbe number (ν d ) is 31, preferably 32, and more preferably 33.

[0070] In some embodiments, the Abbe number (ν d ) is 38, preferably 37, and more preferably 36.

[0071] <density>

[0072] The density (ρ) of optical glass is tested according to the method specified in GB / T7962.20-2010.

[0073] In some embodiments, the density (ρ) of the optical glass of the present invention is 3.80 g / cm 3 Below, preferably 3.60g / cm 3 Below, more preferably 3.50g / cm 3 the following.

[0074] <Transmittance within 400nm>

[0075] Transmittance of optical glass within 400nm (τ 400nm ) Tested according to the method specified in GB / T7962.12-2010, the thickness of the glass sample is 10mm.

[0076] In some embodiments, the transmittance (τ 400nm ) is 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.

[0077] <Relative Partial Dispersion>

[0078] Relative partial dispersion of optical glass (P g,F )=(n g -n F ) / (n F -n C ).

[0079] In some embodiments, the relative partial dispersion (P g,F ) is 0.6000 or less, preferably 0.5900 or less, and more preferably 0.5860 or less.

[0080] <Strong acid resistance>

[0081] 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.

[0082] In some embodiments, 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.

[0083] <Anti-crystallization performance>

[0084] The anti-crystallization performance of the glass of the present invention is tested in the following manner:

[0085] The experimental glass sample was processed into a size of 20×20×10 mm, polished on both sides, and placed in a g Keep the glass in a crystallization furnace at +200℃ for 30 minutes, take it out and cool it down, then polish the two large surfaces. Judge the crystallization performance of the glass according to Table 1 below, with grade A being the best and grade E being the worst.

[0086] Table 1. Classification and judgment criteria of crystallization

[0087] In some embodiments, the anti-devitrification performance of the optical glass of the present invention is Class B or above, preferably Class A.

[0088] <Coefficient of Thermal Expansion>

[0089] Thermal expansion coefficient of optical glass (α 20 / 120℃ ) Test the optical glass data at 20℃~120℃ according to the method specified in GB / T 7962.16-2010.

[0090] In some embodiments, the thermal expansion coefficient (α 20 / 120℃ ) is 90×10 -7 / K or less, preferably 85×10 -7 / K or less, more preferably 80×10 -7 / K or less.

[0091] <Bubble Degree>

[0092] The bubble degree of optical glass is tested according to the method specified in GB / T7962.8-2010.

[0093] In some embodiments, the bubble degree of the optical glass of the present invention is above grade A, preferably above grade A0.

[0094] <High temperature viscosity>

[0095] The high temperature viscosity of optical glass is tested by the following method: The high temperature viscosity of glass is tested using a THETA Rheotronic II high temperature viscometer using a rotation method. The unit of value is dPaS (poise). The smaller the value, the lower the viscosity.

[0096] In some embodiments, 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.

[0097] <Transition Temperature>

[0098] Transition temperature of optical glass (T g) Test according to the method specified in GB / T7962.16-2010.

[0099] In some embodiments, the transition temperature (T g ) is 630°C or lower, preferably 620°C or lower, more preferably 610°C or lower.

[0100] [Method for manufacturing optical glass]

[0101] 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.

[0102] [Glass preforms and optical components]

[0103] 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.

[0104] As 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.

[0105] 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.

[0106] Examples of the lens 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.

[0107] The optical glass of the present invention can be used to prepare optical elements such as chemically strengthened imaging lenses.

[0108] [Optical Instruments]

[0109] 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.

[0110] Example

[0111] <Optical Glass Example>

[0112] In order to further clearly illustrate and describe the technical solutions of the present invention, the following non-limiting examples are provided.

[0113] This embodiment uses the above-mentioned optical glass manufacturing method to obtain optical glasses having the compositions shown in Tables 2 to 4. In addition, 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.

[0114] Table 2.

[0115] Table 3.

[0116] Table 4.

[0117] <Glass Preform Example>

[0118] The glass obtained from 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.

[0119] <Optical Element Example>

[0120] 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.

[0121] 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.

[0122] <Optical Instrument Example>

[0123] The 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.

Claims

1. Optical glass, characterized in that Its components, expressed in weight percentage, include: SiO2: 30-50%; Nb2O5: 25-38%; ZrO2: 1-10%; BaO: 3-15%; SrO: 3-13%; Li2O: 1-7%; Na2O: 2-9%; and K2O: 1-7%.

2. The optical glass according to claim 1, wherein Its components, expressed in weight percentage, 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 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.

3. Optical glass, characterized in that Its components, expressed in weight percentage, are 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%; clarifier: 0-1%, the Ln2O3 is one or more of La2O3, Gd2O3, Y2O3, Yb2O3, and the clarifier is one or more of Sb2O3, SnO, SnO2, and CeO2.

4. The optical glass according to any one of claims 1 to 3, characterized in that Its components are expressed in weight percentage and meet one or more of the following nine conditions: 1) SiO2 / Nb2O5 is 0.9 to 1.8, preferably SiO2 / Nb2O5 is 1.0 to 1.6, and more preferably SiO2 / Nb2O5 is 1.1 to 1.5; 2) (Na2O+BaO) / (Li2O+SrO) is 0.4 to 5.0, preferably (Na2O+BaO) / (Li2O+SrO) is 0.5 to 3.5, more preferably (Na2O+BaO) / (Li2O+SrO) is 0.7 to 2.5, and further preferably (Na2O+BaO) / (Li2O+SrO) is 0.9 to 2.0; 3) (TiO2+B2O3+ZnO) / SrO is 1.3 or less, preferably (TiO2+B2O3+ZnO) / SrO is 1.0 or less, more preferably (TiO2+B2O3+ZnO) / SrO is 0.01 to 0.7, and further preferably (TiO2+B2O3+ZnO) / SrO is 0.05 to 0.4; 4) (B2O3+Ln2O3) / (MgO+SrO+CaO) is 1.5 or less, preferably (B2O3+Ln2O3) / (MgO+SrO+CaO) is 1.0 or less, more preferably (B2O3+Ln2O3) / (MgO+SrO+CaO) is 0.5 or less, and further preferably (B2O3+Ln2O3) / (MgO+SrO+CaO) is 0.3 or less; 5) (Nb2O5+B2O3+ZnO) / (MgO+SrO+CaO+BaO) is 0.9 to 5.5, preferably (Nb2O5+B2O3+ZnO) / (MgO+SrO+CaO+BaO) is 1.0 to 5.0, more 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; 6) ZnO / ZrO2 is 1.0 or less, preferably ZnO / ZrO2 is greater than 0 but less than or equal to 0.8, more preferably ZnO / ZrO2 is 0.01 to 0.6, and further preferably ZnO / ZrO2 is 0.05 to 0.5; 7) (MgO + SrO + CaO + BaO) / (Nb2O5 + TiO2) is 0.2 to 1.2, preferably (MgO + SrO + CaO + BaO) / (Nb2O5 + TiO2) is 0.25 to 1.0, more preferably (MgO + SrO + CaO + BaO) / (Nb2O5 + TiO2) is 0.3 to 0.8, and further preferably (MgO + SrO + CaO + BaO) / (Nb2O5 + TiO2) is 0.3 to 0.6; 8) Li2O / (Na2O+K2O) is 0.1 to 2.0, preferably Li2O / (Na2O+K2O) is 0.2 to 1.5, more preferably Li2O / (Na2O+K2O) is 0.2 to 1.0, and further preferably Li2O / (Na2O+K2O) is 0.3 to 0.7; 9) (Li2O+Na2O+K2O) / SrO is 0.5~4.5, preferably (Li2O+Na2O+K2O) / SrO is 0.6~4.0, more preferably (Li2O+Na2O+K2O) / SrO is 0.8~3.0, and further preferably (Li2O+Na2O+K2O) / SrO is 1.0~2.5, and the Ln2O3 is one or more of La2O3, Gd2O3, Y2O3, and Yb2O3.

5. The optical glass according to any one of claims 1 to 3, characterized in that: 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: 0-1%; and / or Al2O3: 0-2%, preferably Al2O3 L2O3: 0-1%; and / or TiO2: 0-2%, preferably TiO2: 0-1%; and / or Ln2O3: 0-2%, preferably Ln2O3: 0-1%; and / or ZnO: greater than 0 but less than or equal to 3%, preferably ZnO: 0.1-2%; and / or CaO: 0-3%, preferably CaO: 0-1%; and / or MgO: 0-3%, preferably MgO: 0-1%; and / or P2O5: 0-2%, preferably P2O5: 0-1%; and / or clarifier: 0-0.5%, preferably clarifier: 0-0.1%, 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.

6. The optical glass according to any one of claims 1 to 3, characterized in that: Its components do not contain TiO2; and / or do not contain B2O3; and / or do not contain Al2O3; and / or do not contain CaO; and / or do not contain MgO; and / or do not contain P2O5; and / or do not contain La2O3; and / or do not contain Gd2O3; and / or do not contain Y2O3; and / or do not contain Yb2O3.

7. The optical glass according to any one of claims 1 to 3, characterized in that: The refractive index n of the optical glass d 1.68 to 1.76, preferably 1.69 to 1.75, more preferably 1.70 to 1.74; and / or Abbe number v d 31 to 38, preferably 32 to 37, more preferably 33 to 36; and / or relative partial dispersion P g,F is 0.6000 or less, preferably 0.5900 or less, more preferably 0.5860 or less; and / or density ρ is 3.80 g / cm 3 Below, preferably 3.60g / cm 3 Below, more preferably 3.50g / cm 3 Below; and / or transmittance τ within 400nm 400nm 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 further preferably 92.5% or more; and / or anti-crystallization performance is Class B or more, preferably Class A; and / or thermal expansion coefficient α 20 / 120℃ 90×10 -7 / K or less, preferably 85×10 -7 / K or less, more preferably 80×10 -7 / K or less; and / or the bubble degree is A grade or above, preferably A0 grade or above; and / or the viscosity at 1400°C is 50 poise or less, preferably 35 poise or less, more preferably 20 poise or less; and / or the transition temperature T g The temperature is 630°C or lower, preferably 620°C or lower, and more preferably 610°C or lower.

8. A glass preform, characterized in that Made of the optical glass according to any one of claims 1 to 7.

9. An optical element, characterized in that The optical glass is made of any one of claims 1 to 7, or the glass preform is made of the glass preform of claim 8.

10. An optical instrument, characterized in that Contains the optical glass according to any one of claims 1 to 7, and / or contains the optical element according to claim 9.

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