Optical glass with high refractive index

Abstract

The invention provides optical glass with high refractive index, which comprises the following components in percentage by weight: 1-12% of SiO2; 3 to 18 percent of B2O3; the content of La2O3 is 45 to 60 percent; 1 to 13 percent of Y2O3; 1 to 13 percent of ZrO2; 3 to 18 percent of Nb2O5; 5%-20% of TiO2; and 0 to 8% of Al2O3, wherein the ratio of La2O3 to (Y2O3 + Al2O3) is 4.0 to 30.0. Through reasonable component design, the optical glass obtained in the invention has an expected optical constant, a high Young modulus and an excellent bubble degree.

Description

[0001] This application is a divisional application for the invention patent application with application number 202211037564.3, application date August 26, 2022, and name “High refractive index optical glass”. Technical Field

[0002] The invention relates to an optical glass, in particular to a high-refractive-index optical glass with higher Young's modulus and excellent bubble degree. Background Art

[0003] In recent years, the rapid development of digitalization and high precision of optical instruments has put forward higher requirements for the lightweight and miniaturization of optical components used in various optical instruments such as digital cameras, video cameras and other photographic equipment, projectors, projection televisions and other projection equipment. Under the same radius of curvature, the higher the refractive index of the glass, the larger the imaging field of view, which is conducive to reducing the number of optical components in optical instruments. With the development trend of miniaturization of optical instruments, the demand for high refractive index optical glass is becoming more and more obvious. In order to achieve the miniaturization of optical components, when optical glass is processed into smaller or thinner optical components, if its Young's modulus is small, it is easy to deform during use. Therefore, the development of high refractive index optical glass with a higher Young's modulus plays an important role in the development of high-performance optoelectronic products. For optical glass, refractive index and Abbe number are its core optical characteristics. Refractive index and Abbe number determine the basic function of glass. In addition to the desired optical properties, optical glass must also have excellent internal quality (streaks, bubbles and inclusions, etc.). If the component design of optical glass is unreasonable, it is easy to cause a large number of bubbles in the glass, resulting in the scrapping of glass. Summary of the invention

[0004] The technical problem to be solved by the present invention is to provide a high-refractive-index optical glass with higher Young's modulus and excellent bubble degree.

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

[0006] (1) High refractive index optical glass, the components of which, expressed in weight percentage, contain: SiO2: 1-12%; B2O3: 3-18%; La2O3: 45-65%; Y2O3: 1-13%; ZrO2: 1-13%; Nb2O5: 3-18%; TiO2: 5-20%; Al2O3: 0-8%, wherein La2O3 / (Y2O3+Al2O3) is 4.0-30.0.

[0007] (2) The high refractive index optical glass according to (1), wherein the components, expressed in weight percentage, further contain: Ta2O5: 0-8%; and / or Gd2O3: 0-8%; and / or RO: 0-8%; and / or Rn2O: 0-8%; and / or WO3: 0-6%; and / or ZnO: 0-8%; and / or Yb2O3: 0-10%; and / or GeO2: 0-5%; and / or a clarifier: 0-1%, wherein RO is one or more of MgO, CaO, SrO, and BaO, Rn2O is one or more of Li2O, Na2O, and K2O, and the clarifier is one or more of Sb2O3, SnO, SnO2, and CeO2.

[0008] (3) A high refractive index optical glass comprising SiO2, B2O3, La2O3, Y2O3, ZrO2, Nb2O5, and TiO2, wherein the components are expressed in weight percentage, and further comprising 0 to 8% Al2O3, wherein La2O3 / (Y2O3+Al2O3) is 4.0 to 30.0, and the refractive index of the high refractive index optical glass is n d is above 1.97, the Abbe number v d is 26-33, and Young's modulus E is 11000×10 7 Pa or above, and the bubble degree is above grade A.

[0009] (4) The high refractive index optical glass according to (3), wherein the components, expressed in weight percentage, include: SiO2: 1-12%; and / or B2O3: 3-18%; and / or La2O3: 45-65%; and / or Y2O3: 1-13%; and / or ZrO2: 1-13%; and / or Nb2O5: 3-18%; and / or TiO2: 5-20%; and / or Ta2O5: 0-8%; and / or Gd2O3: 0-8%; and / or RO: 0~8%; and / or Rn2O: 0~8%; and / or WO3: 0~6%; and / or ZnO: 0~8%; and / or Yb2O3: 0~10%; and / or GeO2: 0~5%; and / or clarifier: 0~1%, wherein RO is one or more of MgO, CaO, SrO, and BaO, Rn2O is one or more of Li2O, Na2O, and K2O, and the clarifier is one or more of Sb2O3, SnO, SnO2, and CeO2.

[0010] (5) The high refractive index optical glass according to any one of (1) to (4), wherein the composition is expressed in weight percentage, wherein: La2O3 / (RO+Nb2O5+Gd2O3) is 3.0 to 14.0, preferably La2O3 / (RO+Nb2O5+Gd2O3) is 4.0 to 12.0, more preferably La2O3 / (RO+Nb2O5+Gd2O3) is 5.0 to 9.0, and further preferably La2O3 / (RO+Nb2O5+Gd2O3) is 5.2 to 7.5; and / or La2O3 / (Y2O3+Al2O3) is 5.0 to 20.0, preferably La2O3 / (Y2O3+Al2O3) is 7.0 to 15.0, and more preferably La2O3 / (Y2O3+Al2O3) is 8.0 to 11.0; and / or La2O3 / (Ta2O5+Nb2O5) is 3.0~15.0, preferably La2O3 / (Ta2O5+Nb2O5) is 4.0~10.0, more preferably La2O3 / (Ta2O5+Nb2O5) is 5.0~8.0, and further preferably La2O3 / (Ta2O5+Nb2O5) is 5.5~7.5; and / or (SiO2+B2O3) / Nb2O5 is 0.5~5.0, preferably (SiO2+B2O3) / Nb2O5 is 0.8~3.5, more preferably (SiO2+B2O3) / Nb2O5 is 1.0~2.5, and further preferably (SiO2+B2O3) / Nb2O5 is 1.2~2.0, and the RO is one or more of MgO, CaO, SrO, and BaO.

[0011] (6) The high refractive index optical glass according to any one of (1) to (4), wherein the components are expressed in weight percentage, wherein: (Ta2O5+Gd2O3) / Y2O3 is less than 1.0, preferably (Ta2O5+Gd2O3) / Y2O3 is less than 0.8, more preferably (Ta2O5+Gd2O3) / Y2O3 is less than 0.5, and further preferably (Ta2O5+Gd2O3) / Y2O3 is less than 0.2; and / or (Gd2O3+ZnO) / Y2O3 is less than 1.0, preferably ( Gd2O3+ZnO) / Y2O3 is less than 0.8, more preferably (Gd2O3+ZnO) / Y2O3 is less than 0.5, and further preferably (Gd2O3+ZnO) / Y2O3 is less than 0.2; and / or (WO3+Gd2O3) / TiO2 is less than 2.0, preferably (WO3+Gd2O3) / TiO2 is less than 1.5, more preferably (WO3+Gd2O3) / TiO2 is less than 1.0, and further preferably (WO3+Gd2O3) / TiO2 is less than 0.5.

[0012] (7) The high refractive index optical glass according to any one of (1) to (4), wherein the components are expressed in weight percentage, wherein: SiO2: 2-10%, preferably SiO2: 3-8%; and / or B2O3: 5-15%, preferably B2O3: 6-12%; and / or La2O3: 47-60%, preferably La2O3: 50-56%; and / or Y2O3: 2-12%, preferably Y2O3: 4-10%; and / or ZrO2: 2-10%, preferably ZrO2: 3-9%; and / or Nb2O5: 5-15%, preferably Nb2O5: 6-12%; and / or Ta2O5: 0-5%, preferably Ta2O5: 0-1%; and / or Gd2O3: 0-4%, preferably Gd2O3: 0-2%; and / or TiO2: 8-18%, preferably TiO2: 11-17% %; and / or RO: 0-4%, preferably RO: 0-2%; and / or Rn2O: 0-4%, preferably Rn2O: 0-2%; and / or WO3: 0-4%, preferably WO3: 0-3%; and / or ZnO: 0-5%, preferably ZnO: 0-1%; and / or Al2O3: 0-5%, preferably Al2O3: 0-2%; and / or Yb2O3: 0-5%, preferably Yb2O3: 0-2%; and / or GeO2: 0-3%, preferably GeO2: 0-1%; and / or clarifier: 0-0.5%, preferably clarifier: 0-0.2%, wherein RO is one or more of MgO, CaO, SrO, and BaO, Rn2O is one or more of Li2O, Na2O, and K2O, and the clarifier is one or more of Sb2O3, SnO, SnO2, and CeO2.

[0013] (8) The high refractive index optical glass according to any one of (1) to (4), wherein its components do not contain Ta2O5; and / or do not contain ZnO; and / or do not contain Rn2O; and / or do not contain Gd2O3; and / or do not contain Yb2O3; and / or do not contain GeO2, and the Rn2O is one or more of Li2O, Na2O, and K2O.

[0014] (9) The high refractive index optical glass according to any one of (1) to (4), wherein the refractive index n of the high refractive index optical glass is d is 1.97 or more, preferably 1.98 or more, more preferably 1.99 to 2.10, and the Abbe number v d It is 26-33, preferably 27-32, and more preferably 28-31.

[0015] (10) The high refractive index optical glass according to any one of (1) to (4), wherein the thermal expansion coefficient α of the high refractive index optical glass is 20 / 120℃ 95×10 -7 / K or less, preferably 90×10 -7 / K or less, more preferably 85×10 -7 / K or less, more preferably 80×10 -7 / K or less; and / or water resistance stability D W 2 or more, preferably 1; and / or acid resistance stability D A 2 or more, preferably 1; and / or weather resistance CR is 2 or more, preferably 1; and / or Knoop hardness H K 670×10 7 Pa or more, preferably 680×10 7 Pa or more, more preferably 690×10 7 Pa or more; and / or Young's modulus E is 11000×10 7 Pa or more, preferably 12000×10 7 Pa or more, more preferably 12500×10 7 Pa or more, more preferably 12800×10 7 Pa or above; and / or λ 70 450nm or less, preferably λ 70 445nm or less, preferably λ 70 440nm or less; and / or λ5 is 390nm or less, preferably λ5 is 385nm or less, more preferably λ5 is 380nm or less; and / or wear degree F A The foaming degree is 70 to 120, preferably 80 to 110, and more preferably 85 to 105; and / or the foaming degree is A grade or higher, preferably A0 grade or higher, and more preferably A 00 class.

[0016] (11) A glass preform made of the high refractive index optical glass described in any one of (1) to (10).

[0017] (12) An optical element made of the high refractive index optical glass described in any one of (1) to (10), or made of the glass preform described in (11).

[0018] (13) An optical instrument comprising the high refractive index optical glass described in any one of (1) to (10) and / or the optical element described in (12).

[0019] The beneficial effects of the present invention are: through reasonable component design, the optical glass obtained by the present invention has desired optical constants, as well as higher Young's modulus and excellent bubble degree. DETAILED DESCRIPTION

[0020] Below, the embodiment of the high refractive index optical glass of the present invention is described in detail, but the present invention is not limited to the following embodiment, and can be implemented by appropriate changes within the scope of the purpose of the present invention. In addition, although there are cases where the description of the repeated description is appropriately omitted, the main purpose of the invention is not limited thereto. In the following content, the high refractive index optical glass of the present invention is sometimes referred to as optical glass or glass.

[0021] [High refractive index optical glass]

[0022] The following is an explanation of the range of each component (ingredient) of the high refractive index 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 in weight percentage relative to the total amount of glass material converted into oxide composition. Here, the "composition converted into oxide" means that when the oxides, complex salts and hydroxides used as raw materials for the optical glass components of the present invention decompose and transform into oxides during melting, the total amount of the oxide material is taken as 100%.

[0023] Unless otherwise specified in specific circumstances, the numerical ranges listed in the present invention include upper and lower limits, "above" and "below" include endpoint values, and all integers and fractions included in the range, without being limited to the specific values ​​listed when the range is defined. "And / or" referred to herein is inclusive, for example, "A and / or B" means only A, or only B, or both A and B.

[0024] <Essential Components and Optional Components>

[0025] B2O3 is a glass network forming component, which has the effect of improving the glass solubility and resistance to devitrification, and reducing the glass transition temperature and density. The present invention obtains the above effects by containing more than 3% B2O3, preferably more than 5% B2O3, and more preferably more than 6% B2O3; but if its content exceeds 18%, the stability of the glass decreases, and the refractive index decreases, and it is difficult to achieve the high refractive index of the present invention. Therefore, the upper limit of the content of B2O3 in the present invention is 18%, preferably 15%, and more preferably 12%.

[0026] SiO2 is also a network-forming component, which can adjust the thermal expansion coefficient of glass, improve the resistance to devitrification and chemical stability of glass, and also improve the thermal stability and high-temperature viscosity of glass; if its content exceeds 12%, the melting performance of glass tends to deteriorate and the transition temperature increases. Therefore, the content of SiO2 in the present invention is 1-12%, preferably 2-10%, and more preferably 3-8%.

[0027] La2O3 is an effective component for increasing the refractive index of glass, and has a significant effect on improving the chemical stability and resistance to devitrification of glass. If its content is less than 45%, it is difficult to achieve the required optical constants; if the content is higher than 65%, the devitrification tendency of the glass increases and the thermal stability deteriorates. Therefore, the content of La2O3 is limited to 45-65%, preferably 47-60%, and more preferably 50-56%.

[0028] Y2O3 can improve the refractive index and devitrification resistance of glass and adjust the Young's modulus of glass. The present invention achieves the above effects by containing more than 1% Y2O3. If its content exceeds 13%, the chemical stability and weather resistance of glass will deteriorate. Therefore, the content of Y2O3 in the present invention is 1-13%, preferably 2-12%, and more preferably 4-10%.

[0029] Gd2O3 can improve the refractive index and chemical stability of glass, but if its content is higher than 8%, the devitrification resistance and abrasion resistance of glass will deteriorate. Therefore, the content of Gd2O3 is 0 to 8%, preferably 0 to 4%, and more preferably 0 to 2%. In some embodiments, it is further preferred that Gd2O3 is not contained.

[0030] Yb2O3 is also a component that gives glass high refractive and low dispersion properties. If its content exceeds 8%, the anti-crystallization performance of the glass decreases. Therefore, the content of Yb2O3 is 0-10%, preferably 0-5%, more preferably 0-2%, and more preferably no Yb2O3 is contained.

[0031] ZrO2 can improve the viscosity, hardness, refractive index and chemical stability of optical glass, and can also reduce the thermal expansion coefficient of glass; when the content of ZrO2 is too high, the resistance to devitrification of glass decreases, the difficulty of melting increases, the melting temperature rises, and inclusions appear inside the glass and the light transmittance decreases. Therefore, the content of ZrO2 in the present invention is 1-13%, preferably 2-10%, and more preferably 3-9%.

[0032] TiO2 is a high-refractive and high-dispersion component, which can significantly improve the refractive index and dispersion of glass. The inventors have found that a proper amount of TiO2 can increase the stability of glass; but if too much TiO2 is contained, the transmittance of the glass will be significantly reduced, and the chemical stability of the glass will also tend to deteriorate. Therefore, the content of TiO2 in the present invention is 5-20%, preferably 8-18%, and more preferably 11-17%.

[0033] Nb2O5 is a high-refractive and high-dispersion component that can increase the refractive index and devitrification resistance of glass and reduce the thermal expansion coefficient of glass. In the present invention, the above effect is obtained by containing more than 3% Nb2O5, preferably more than 5% Nb2O5, and more preferably more than 6% Nb2O5. If the content of Nb2O5 exceeds 18%, the thermal stability and weather resistance of the glass will decrease, and the light transmittance will decrease. Therefore, the upper limit of the content of Nb2O5 in the present invention is 18%, preferably 15%, and more preferably 12%.

[0034] In some embodiments, the ratio of the total content of SiO2 and B2O3 SiO2+B2O3 to the content of Nb2O5 (SiO2+B2O3) / Nb2O5) is controlled within the range of 0.5 to 5.0, which is beneficial to improving the hardness and weather resistance of the glass. Therefore, it is preferred that (SiO2+B2O3) / Nb2O5 is 0.5 to 5.0, and it is more preferred that (SiO2+B2O3) / Nb2O5 is 0.8 to 3.5. Furthermore, by controlling (SiO2+B2O3) / Nb2O5 within the range of 1.0 to 2.5, the abrasiveness and bubble degree of the glass can be further optimized. Therefore, it is further preferred that (SiO2+B2O3) / Nb2O5 is 1.0 to 2.5, and it is further preferred that (SiO2+B2O3) / Nb2O5 is 1.2 to 2.0.

[0035] Alkaline earth metal oxide RO (RO is one or more of MgO, CaO, SrO, BaO) can adjust the optical constants of glass and optimize the chemical stability of glass, but when its content is high, the devitrification resistance of glass decreases. Therefore, the RO content is limited to 0-8%, preferably 0-4%, and more preferably 0-2%.

[0036] In some embodiments, the ratio of La2O3 to the total content of RO, Nb2O5, and Gd2O3 (RO+Nb2O5+Gd2O3) (La2O3 / (RO+Nb2O5+Gd2O3)) is controlled within the range of 3.0 to 14.0, which can improve the light transmittance and bubble degree of the glass. Therefore, La2O3 / (RO+Nb2O5+Gd2O3) is preferably 3.0 to 14.0, and La2O3 / (RO+Nb2O5+Gd2O3) is more preferably 4.0 to 12.0. Further, La2O3 / (RO+Nb2O5+Gd2O3) is controlled within the range of 3.0 to 14.0.

[0037] (RO+Nb2O5+Gd2O3) is within the range of 5.0 to 9.0, which can further optimize the abrasiveness of the glass and reduce the thermal expansion coefficient of the glass. Therefore, it is further preferred that La2O3 / (RO+Nb2O5+Gd2O3) is 5.0 to 9.0, and it is further preferred that La2O3 / (RO+Nb2O5+Gd2O3) is 5.2 to 7.5.

[0038] Alkali metal oxide Rn2O (Rn2O is one or more of Li2O, Na2O, K2O) can reduce the transition temperature of glass, adjust the optical constants and high temperature viscosity of glass, and improve the melting property of glass. However, when its content is high, the devitrification resistance and chemical stability of glass are reduced, and the refractive index is reduced. Therefore, the content of Rn2O in the present invention is 0 to 8%, preferably 0 to 4%, and more preferably 0 to 2%. In some embodiments, it is further preferred that Rn2O is not contained.

[0039] WO3 can improve the refractive index and mechanical strength of glass. If the content of WO3 exceeds 6%, the thermal stability of glass decreases and the resistance to devitrification decreases. Therefore, the content of WO3 is 0-6%, preferably 0-4%, and more preferably 0-3%.

[0040] In some embodiments, the ratio (WO3+Gd2O3) / TiO2 between the total content of WO3 and Gd2O3 WO3+Gd2O3 and the content of TiO2 is controlled to be below 2.0, which can improve the weather resistance and chemical stability of the glass and prevent the light transmittance from decreasing. Therefore, it is preferred that (WO3+Gd2O3) / TiO2 is below 2.0, and it is more preferred that (WO3+Gd2O3) / TiO2 is below 1.5. Furthermore, by controlling (WO3+Gd2O3) / TiO2 to be below 1.0, the thermal expansion coefficient of the glass can be further reduced. Therefore, it is further preferred that (WO3+Gd2O3) / TiO2 is below 1.0, and it is further preferred that (WO3+Gd2O3) / TiO2 is below 0.5.

[0041] ZnO can adjust the refractive index and dispersion of glass, and reduce the high temperature viscosity and transition temperature of glass. If the content of ZnO is too high, the difficulty of glass molding increases and the anti-crystallization performance deteriorates. Therefore, the content of ZnO is 0-8%, preferably 0-5%, and more preferably 0-1%. In some embodiments, it is further preferred that ZnO is not contained.

[0042] In some embodiments, by controlling the ratio (Gd2O3+ZnO) / Y2O3 between the total content of Gd2O3 and ZnO Gd2O3+ZnO and the content of Y2O3 to be below 1.0, the thermal expansion coefficient of the glass can be reduced and the abrasiveness of the glass can be optimized. Therefore, it is preferred that (Gd2O3+ZnO) / Y2O3 is below 1.0, and it is more preferred that (Gd2O3+ZnO) / Y2O3 is below 0.8. Furthermore, controlling (Gd2O3+ZnO) / Y2O3 to be below 0.5 can make it easier for the glass to obtain a suitable Young's modulus and prevent the hardness of the glass from decreasing. Therefore, it is further preferred that (Gd2O3+ZnO) / Y2O3 is below 0.5, and it is further preferred that (Gd2O3+ZnO) / Y2O3 is below 0.2.

[0043] Ta2O5 has the effect of increasing the refractive index and improving the devitrification resistance of glass, but if its content is too high, the thermal stability of the glass will decrease and the density will increase. On the other hand, compared with other components, Ta2O5 is very expensive. From the perspective of practicality and cost, its usage should be minimized. Therefore, the content of Ta2O5 in the present invention is limited to 0-8%, preferably 0-5%, and more preferably 0-1%. In some embodiments, it is further preferred that Ta2O5 is not contained.

[0044] In some embodiments, the ratio of the total content of Ta2O5 and Gd2O3 Ta2O5+Gd2O3 to the content of Y2O3 (Ta2O5+Gd2O3) / Y2O3 is controlled to be below 1.0, which is beneficial for the glass to obtain a suitable abrasiveness, optimize the density and Young's modulus of the glass, and prevent the chemical stability of the glass from deteriorating. Therefore, it is preferred that (Ta2O5+Gd2O3) / Y2O3 is below 1.0, more preferably (Ta2O5+Gd2O3) / Y2O3 is below 0.8, further preferably (Ta2O5+Gd2O3) / Y2O3 is below 0.5, and further preferably (Ta2O5+Gd2O3) / Y2O3 is below 0.2.

[0045] In some embodiments, the ratio of La2O3 to the total content of Ta2O5 and Nb2O5 (Ta2O5+Nb2O5) (La2O3 / (Ta2O5+Nb2O5)) is controlled within the range of 3.0 to 15.0, which can improve the bubble degree and hardness of the glass. Therefore, La2O3 / (Ta2O5+Nb2O5) is preferably 3.0 to 15.0, and La2O3 / (Ta2O5+Nb2O5) is more preferably 4.0 to 10.0. Furthermore, La2O3 / (Ta2O5+Nb2O5) is controlled within the range of 5.0 to 8.0, which can further reduce the thermal expansion coefficient of the glass and improve weather resistance. Therefore, La2O3 /

[0046] (Ta2O5+Nb2O5) is 5.0~8.0, and it is more preferred that La2O3 / (Ta2O5+Nb2O5) is 5.5~7.5.

[0047] Al2O3 can improve the chemical stability of glass, but when its content exceeds 8%, the melting property and light transmittance of glass deteriorate. Therefore, the content of Al2O3 in the present invention is 0-8%, preferably 0-5%, and more preferably 0-2%.

[0048] In some embodiments, the ratio La2O3 / (Y2O3+Al2O3) between the content of La2O3 and the total content of Y2O3 and Al2O3 (Y2O3+Al2O3) is controlled within the range of 4.0 to 30.0, which can improve the Young's modulus and the bubble degree of the glass and prevent the reduction of chemical stability. Therefore, La2O3 / (Y2O3+Al2O3) is preferably 4.0 to 30.0, more preferably La2O3 / (Y2O3+Al2O3) is 5.0 to 20.0, further preferably La2O3 / (Y2O3+Al2O3) is 7.0 to 15.0, and further preferably La2O3 / (Y2O3+Al2O3) is 8.0 to 11.0.

[0049] GeO2 has the effect of increasing the refractive index and resistance to devitrification, but if its content is too high, the chemical stability of the glass will decrease; on the other hand, compared with other components, GeO2 is very expensive, and its usage should be minimized from the perspective of practicality and cost. Therefore, the content of GeO2 in the present invention is limited to 0-5%, preferably 0-3%, more preferably 0-1%, and it is further preferred that GeO2 is not contained.

[0050] In the present invention, by containing 0-1% of one or more of Sb2O3, SnO, SnO2, and CeO2 as a clarifier, the clarification effect of the glass can be improved, and the bubble degree of the glass can be improved. The content of the clarifier is preferably 0-0.5%, and the content of the clarifier is more preferably 0-0.2%. Since the component types and contents of the optical glass of the present invention are reasonably designed and its bubble degree is excellent, it is further preferred in some embodiments that no clarifier is contained. When the Sb2O3 content exceeds 1%, the glass tends to have reduced clarification performance. At the same time, due to its strong oxidizing effect, it promotes the corrosion of platinum or platinum alloy vessels for melting glass and the deterioration of the molding mold. Therefore, the present invention preferably has a Sb2O3 content of 0-1%, more preferably 0-0.5%, further preferably 0-0.2%, and further preferably no Sb2O3. SnO and SnO2 can also be used as clarifiers, but when their content exceeds 1%, the glass tends to color more, or when the glass is heated, softened, and molded again, Sn will become the starting point for nucleation, resulting in a tendency to devitrification. Therefore, the content of SnO2 in the present invention is preferably 0-1%, more preferably 0-0.5%, further preferably 0-0.2%, and further preferably does not contain SnO2; the content of SnO is preferably 0-1%, more preferably 0-0.5%, further preferably 0-0.2%, and further preferably does not contain SnO. The role and content ratio of CeO2 are consistent with those of SnO2, and its content is preferably 0-1%, more preferably 0-0.5%, further preferably 0-0.2%, and further preferably does not contain CeO2.

[0051] <Components that should not be contained>

[0052] 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 absorption will occur at specific wavelengths in the visible light region, thereby weakening the property of the present invention of improving the visible light transmittance. Therefore, it is preferably substantially free of oxides of transition metals such as V, Cr, Mn, Fe, Co, Ni, Cu, Ag and Mo, especially for optical glasses that require transmittance at wavelengths in the visible light region.

[0053] The oxides of Th, Cd, Tl, Os, Be and Se have a tendency to be controlled in recent years as harmful chemical substances, and environmental protection measures are necessary not only in the manufacturing process of glass, but also in the processing process and the disposal after productization. Therefore, in the case of paying attention to the impact on the environment, it is preferred that they are not actually contained except for being inevitably mixed in. Thus, the optical glass does not actually contain substances that pollute the environment. Therefore, even if special environmental countermeasures are not taken, the optical glass of the present invention can be manufactured, processed and discarded.

[0054] In order to achieve environmental friendliness, the optical glass of the present invention preferably does not contain As2O3 and PbO.

[0055] The "does not contain" and "0%" recorded in this article mean 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 will be certain impurities or components that are not intentionally added, which will be contained in a small amount or trace amount in the final optical glass, and this situation is also within the scope of protection of the patent of this invention.

[0056] Next, the properties of the high refractive index optical glass of the present invention will be described.

[0057] <Refractive Index and Abbe Number>

[0058] The refractive index of optical glass (n d ) and the Abbe number (ν d ) Tested according to the method specified in GB / T 7962.1-2010.

[0059] In some embodiments, the refractive index (n d ) has a lower limit of 1.97, a preferred lower limit is 1.98, and a more preferred lower limit is 1.99.

[0060] In some embodiments, the refractive index (n d ) is 2.10, preferably 2.05, and more preferably 2.02.

[0061] In some embodiments, the Abbe number (ν d ) has a lower limit of 26, a preferred lower limit of 27, and a more preferred lower limit of 28.

[0062] In some embodiments, the Abbe number (ν d ) has an upper limit of 33, a preferred upper limit of 32, and a more preferred upper limit of 31.

[0063] <Coefficient of Thermal Expansion>

[0064] Thermal expansion coefficient of optical glass (α 20 / 120℃ ) Test the data at 20-120℃ according to the method specified in GB / T7962.16-2010.

[0065] In some embodiments, the thermal expansion coefficient (α 20 / 120℃ ) is 95×10 -7 / K or less, preferably 90×10 -7 / K or less, more preferably 85×10 -7 / K or less, more preferably 80×10 -7 / K or less.

[0066] <Water resistance stability>

[0067] Water resistance stability of optical glass (D W ) (Powder method) Tested in accordance with the method specified in GB / T 17129.

[0068] In some embodiments, the water resistance stability (D W ) is 2 or more types, preferably 1 type.

[0069] <Acid resistance stability>

[0070] Acid resistance stability of optical glass (D A ) (Powder method) Tested in accordance with the method specified in GB / T 17129.

[0071] In some embodiments, the acid resistance stability (D A ) is 2 or more types, preferably 1 type.

[0072] <Weather resistance>

[0073] The test method for weather resistance (CR) of optical glass is as follows: place the sample in a test box with a saturated water vapor environment of 90% relative humidity, alternately cycle every 1 hour at 40-50°C, and cycle for 15 cycles. The weather resistance category is divided according to the change in turbidity before and after the sample is placed. The weather resistance classification is shown in Table 1:

[0074] Table 1.

[0075]

[0076] In some embodiments, the weather resistance (CR) of the high refractive index optical glass of the present invention is Class 2 or higher, preferably Class 1.

[0077] <Knoop hardness>

[0078] Knoop hardness of optical glass (H K ) The test shall be carried out according to the test method specified in GB / T7962.18-2010.

[0079] In some embodiments, the Knoop hardness (H K ) is 670×10 7 Pa or more, preferably 680×10 7 Pa or more, more preferably 690×10 7 Pa or above.

[0080] <Young's modulus>

[0081] Young's modulus (E) is calculated using the following formula by ultrasonic testing of its longitudinal wave velocity and transverse wave velocity.

[0082]

[0083] G=V S 2 ρ

[0084] Where: E is Young's modulus, Pa;

[0085] G is the shear modulus, Pa;

[0086] V T is the shear wave velocity, m / s;

[0087] V S is the longitudinal wave velocity, m / s;

[0088] ρ is the glass density, g / cm 3 .

[0089] In some embodiments, the Young's modulus (E) of the high refractive index optical glass of the present invention is 11000×10 7Pa or more, preferably 12000×10 7 Pa or more, more preferably 12500×10 7 Pa or more, more preferably 12800×10 7 Pa or above.

[0090] <Abrasion>

[0091] Abrasiveness of optical glass (F A ) refers to the value obtained by multiplying the ratio of the wear volume of the sample to the wear volume (volume) of the standard sample (H-K9 glass) under exactly the same conditions by 100, and is expressed by the following formula:

[0092] F A =V / V0×100=(W / ρ) / (W0 / ρ0)×100

[0093] Where: V—volume wear of the sample being tested;

[0094] V0—Volume loss of standard sample;

[0095] W—mass wear loss of the sample being tested;

[0096] W0—standard sample mass wear;

[0097] ρ—density of the sample being tested;

[0098] ρ0—standard sample density.

[0099] In some embodiments, the abrasiveness (F A ) has a lower limit of 70, a preferred lower limit of 80, and a more preferred lower limit of 85.

[0100] In some embodiments, the abrasiveness (F A ) has an upper limit of 120, a preferred upper limit of 110, and a more preferred upper limit of 105.

[0101] <Color>

[0102] The short-wave transmission spectrum characteristics of the glass of the present invention are expressed by the coloration (λ 70 and λ5). 70 Refers to the wavelength when the glass transmittance reaches 70%. 70 The measurement is to use a glass with a thickness of 10±0.1mm and two opposite planes parallel to each other and optically polished, and measure the spectral transmittance in the wavelength range from 280nm to 700nm and the wavelength at which the transmittance is 70%. The so-called spectral transmittance or transmittance is the wavelength at which the incident intensity I is perpendicular to the above surface of the glass. in Light of intensity I passes through the glass and emerges from a planeout The light of the case through I out / I in The amount expressed by λ also includes the transmittance of the surface reflection loss on the above surfaces of the glass. The higher the refractive index of the glass, the greater the surface reflection loss. Therefore, in high refractive index glass, λ 70 A small value of means that the glass itself is less colored and has a high light transmittance.

[0103] In some embodiments, the λ of the high refractive index optical glass of the present invention is 70 450nm or less, preferably λ 70 445nm or less, preferably λ 70 Below 440nm.

[0104] In some embodiments, the λ5 of the high refractive index optical glass of the present invention is 390 nm or less, preferably 385 nm or less, and more preferably 380 nm or less.

[0105] <Bubble Degree>

[0106] The bubble degree of optical glass is tested according to the method specified in GB / T7962.8-2010.

[0107] In some embodiments, the bubble degree of the high refractive index optical glass of the present invention is above grade A, preferably above grade A0, and more preferably above grade A1. 00 class.

[0108] [Method for producing optical glass]

[0109] The manufacturing method of the high refractive index optical glass of the present invention is as follows: the glass of the present invention is produced using conventional raw materials and processes, including but not limited to using oxides, hydroxides, complex salts (such as carbonates, nitrates, sulfates, etc.), boric acid, etc. as raw materials, and after the ingredients are prepared according to the conventional method, the prepared furnace materials are put into a melting furnace (such as platinum or platinum alloy crucible) at 1200-1500°C for melting, and after clarification and homogenization, a homogeneous molten glass without bubbles and undissolved substances is obtained, and the molten glass is cast in a mold and annealed. Those skilled in the art can appropriately select raw materials, process methods and process parameters according to actual needs.

[0110] [Glass preforms and optical components]

[0111] The prepared optical glass can be used to make a glass preform by means of direct drop molding, grinding, or compression molding such as hot press molding. That is, the molten optical glass can be directly precision drop molded into a glass precision preform, or the glass preform can be made by mechanical processing such as grinding and grinding, or the preform for compression molding made of the optical glass can be made by hot press molding and then grinding. It should be noted that the means for preparing the glass preform are not limited to the above means.

[0112] As described above, the optical glass of the present invention is useful for various optical elements and optical designs, and 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.

[0113] The glass preform and optical element of the present invention are both formed of the optical glass of the present invention. The glass preform of the present invention has the excellent properties of optical glass; the optical element of the present invention has the excellent properties of optical glass, and can provide various optical elements such as lenses and prisms with high optical value.

[0114] 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.

[0115] [Optical instruments]

[0116] The optical element formed by the optical glass of the present invention can be used to manufacture optical instruments such as photographic equipment, video equipment, projection equipment, display equipment, vehicle-mounted equipment and monitoring equipment.

[0117] Example

[0118] <Optical Glass Example>

[0119] In order to further clearly illustrate and describe the technical solution of the present invention, the following non-limiting examples are provided.

[0120] This embodiment adopts the above optical glass manufacturing method to obtain optical glasses having the compositions shown in Tables 2 to 4. In addition, the properties of each glass are measured by the testing method described in the present invention, and the measurement results are shown in Tables 2 to 4.

[0121] Table 2.

[0122]

[0123]

[0124] Table 3.

[0125]

[0126]

[0127] Table 4.

[0128]

[0129]

[0130] <Glass Preform Example>

[0131] The glass obtained from optical glass examples 1 to 24# is used, for example, by grinding processing, or by molding methods such as hot pressing, precision stamping, etc., to make preforms of various lenses, prisms, etc., such as concave meniscus lenses, convex meniscus lenses, biconvex lenses, biconcave lenses, plano-convex lenses, and plano-concave lenses.

[0132] <Optical Element Embodiment>

[0133] The preforms obtained in 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.

[0134] Next, each preform is ground and polished to produce various lenses and prisms such as concave meniscus lenses, convex meniscus lenses, biconvex lenses, biconcave lenses, plano-convex lenses, and plano-concave lenses. The surface of the obtained optical element may be coated with an anti-reflection film.

[0135] <Optical Instrument Embodiment>

[0136] The optical element obtained by the above-mentioned optical element embodiment is optically designed to form an optical component or optical assembly by using one or more optical elements, and 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, lithography technology, excimer lasers, wafers, computer chips, and integrated circuits and electronic devices including such circuits and chips.

Claims

1. High refractive index optical glass, characterized in that: Its components, expressed in weight percentage, include: SiO2: 1-12%; B2O3: 3-18%; La2O3: 45-60%; Y2O3: 1-13%; ZrO2: 1-13%; Nb2O5: 3-18%; TiO2: 5-20%; Al2O3: 0-8%, wherein La2O3 / (Y2O3+Al2O3) is 4.0-30.

0.

2. The high refractive index optical glass according to claim 1, characterized in that: Its components are expressed in weight percentage and further contain: Ta2O5: 0-8%; and / or Gd2O3: 0-8%; and / or RO: 0-8%; and / or Rn2O: 0-8%; and / or WO3: 0-6%; and / or ZnO: 0-8%; and / or Yb2O3: 0-10%; and / or GeO2: 0-5%; and / or clarifier: 0-1%, wherein RO is one or more of MgO, CaO, SrO, and BaO, Rn2O is one or more of Li2O, Na2O, and K2O, and the clarifier is one or more of Sb2O3, SnO, SnO2, and CeO2.

3. High refractive index optical glass, characterized in that: Contains SiO2, B2O3, La2O3, Y2O3, ZrO2, Nb2O5, TiO2, and the components are expressed in weight percentage. It also contains 0-8% Al2O3, wherein La2O3 / (Y2O3+Al2O3) is 4.0-30.

0. The refractive index of the high refractive index optical glass is n d is above 1.97, the Abbe number v d is 26-33, and Young's modulus E is 11000×10 7 Pa or above, and the bubble degree is above grade A.

4. The high refractive index optical glass according to claim 3, characterized in that: Its components, expressed in weight percentage, contain: SiO2: 1-12%; and / or B2O3: 3-18%; and / or La2O3: 45-60%; and / or Y2O3: 1-13%; and / or ZrO2: 1-13%; and / or Nb2O5: 3-18%; and / or TiO2: 5-20%; and / or Ta2O5: 0-8%; and / or Gd2O3: 0-8%; and / or RO: 0-8%; and / or Rn 2O: 0-8%; and / or WO3: 0-6%; and / or ZnO: 0-8%; and / or Yb2O3: 0-10%; and / or GeO2: 0-5%; and / or clarifier: 0-1%, wherein RO is one or more of MgO, CaO, SrO, and BaO, Rn2O is one or more of Li2O, Na2O, and K2O, and the clarifier is one or more of Sb2O3, SnO, SnO2, and CeO2.

5. The high refractive index optical glass according to any one of claims 1 to 4, characterized in that: The components are expressed in weight percentage, wherein: La2O3 / (RO+Nb2O5+Gd2O3) is 3.0-14.0, preferably La2O3 / (RO+Nb2O5+Gd2O3) is 4.0-12.0, more preferably La2O3 / (RO+Nb2O5+Gd2O3) is 5.0-9.0, and further preferably La2O3 / (RO+Nb2O5+Gd2O3) is 5.2-7.5; and / or La2O3 / (Y2O3+Al2O3) is 5.0-20.0, preferably La2O3 / (Y2O3+Al2O3) is 7.0-15.0, and more preferably La2O3 / (Y2O3+Al2O3) is 8.0-11.0; and / or La2O3 / (Ta2O 5+Nb2O5) is 3.0~15.0, preferably La2O3 / (Ta2O5+Nb2O5) is 4.0~10.0, more preferably La2O3 / (Ta2O5+Nb2O5) is 5.0~8.0, and further preferably La2O3 / (Ta2O5+Nb2O5) is 5.5~7.5; and / or (SiO2+B2O3) / Nb2O5 is 0.5~5.0, preferably (SiO2+B2O3) / Nb2O5 is 0.8~3.5, more preferably (SiO2+B2O3) / Nb2O5 is 1.0~2.5, and further preferably (SiO2+B2O3) / Nb2O5 is 1.2~2.0, and the RO is one or more of MgO, CaO, SrO, and BaO.

6. The high refractive index optical glass according to any one of claims 1 to 4, characterized in that: Its components are expressed in weight percentage, wherein: (Ta2O5+Gd2O3) / Y2O3 is less than 1.0, preferably (Ta2O5+Gd2O3) / Y2O3 is less than 0.8, more preferably (Ta2O5+Gd2O3) / Y2O3 is less than 0.5, and further preferably (Ta2O5+Gd2O3) / Y2O3 is less than 0.2; and / or (Gd2O3+ZnO) / Y2O3 is less than 1.0, preferably (Gd2O3+ZnO) / Y2 O3 is less than 0.8, more preferably (Gd2O3+ZnO) / Y2O3 is less than 0.5, and further preferably (Gd2O3+ZnO) / Y2O3 is less than 0.2; and / or (WO3+Gd2O3) / TiO2 is less than 2.0, preferably (WO3+Gd2O3) / TiO2 is less than 1.5, more preferably (WO3+Gd2O3) / TiO2 is less than 1.0, and further preferably (WO3+Gd2O3) / TiO2 is less than 0.

5.

7. The high refractive index optical glass according to any one of claims 1 to 4, characterized in that: Its components are expressed in weight percentage, wherein: SiO2: 2-10%, preferably SiO2: 3-8%; and / or B2O3: 5-15%, preferably B2O3: 6-12%; and / or La2O3: 47-60%, preferably La2O3: 50-56%; and / or Y2O3: 2-12%, preferably Y2O3: 4-10%; and / or ZrO2: 2-10%, preferably ZrO2: 3-9%; and / or Nb2O5: 5-15%, preferably Nb2O5: 6-12%; and / or Ta2O5: 0-5%, preferably Ta2O5: 0-1%, more preferably no Ta2O5; and / or Gd2O3: 0-4%, preferably Gd2O3: 0-2%, more preferably no Gd2O3; and / or TiO2: 8-18%, preferably TiO2: 11-17%; and / or RO: 0-4%, preferably RO: 0-2%; and / or Rn2O: 0-4%, preferably Rn2O: 0-2%, more preferably no Rn2O; and / or WO3: 0-4%, preferably WO3: 0-3%; and / or ZnO: 0-5%, preferably ZnO: 0-1%, more preferably no ZnO; and / or Al2O3: 0-5%, preferably Al2O3: 0-2%; and / or Yb2O3: 0-5%, preferably Yb2O3: 0-2%, more preferably no Yb2O3; and / or GeO2: 0-3%, preferably GeO2: 0-1%, more preferably no GeO2; and / or clarifier: 0-0.5%, preferably clarifier: 0-0.2%, wherein RO is one or more of MgO, CaO, SrO, and BaO, Rn2O is one or more of Li2O, Na2O, and K2O, and the clarifier is one or more of Sb2O3, SnO, SnO2, and CeO2.

8. The high refractive index optical glass according to any one of claims 1 to 4, characterized in that: The refractive index n of the high refractive index optical glass d is 1.97 or more, preferably 1.98 or more, more preferably 1.99 to 2.10, and the Abbe number v d It is 26-33, preferably 27-32, and more preferably 28-31.

9. The high refractive index optical glass according to any one of claims 1 to 4, characterized in that: The thermal expansion coefficient α of the high refractive index optical glass 20 / 120℃ 95×10 -7 / K or less, preferably 90×10 -7 / K or less, more preferably 85×10 -7 / K or less, more preferably 80×10 -7 / K or less; and / or water resistance stability D W 2 or more, preferably 1; and / or acid resistance stability D A 2 or more, preferably 1; and / or weather resistance CR is 2 or more, preferably 1; and / or Knoop hardness H K 670×10 7 Pa or more, preferably 680×10 7 Pa or more, more preferably 690×10 7 Pa or more; and / or Young's modulus E is 11000×10 7 Pa or more, preferably 12000×10 7 Pa or more, more preferably 12500×10 7 Pa or more, more preferably 12800×10 7 Pa or above; and / or λ 70 450nm or less, preferably λ 70 445nm or less, preferably λ 70 440nm or less; and / or λ5 is 390nm or less, preferably λ5 is 385nm or less, more preferably λ5 is 380nm or less; and / or wear degree F A The foaming degree is 70 to 120, preferably 80 to 110, and more preferably 85 to 105; and / or the foaming degree is A grade or higher, preferably A0 grade or higher, and more preferably A 00 class.

10. A glass preform, characterized in that: The optical glass is made of the high refractive index described in any one of claims 1 to 9.

11. An optical element, characterized in that It is made of the high refractive index optical glass described in any one of claims 1 to 9, or is made of the glass preform described in claim 10.

12. An optical instrument, characterized in that A method of manufacturing a high refractive index optical glass comprising the high refractive index optical glass according to any one of claims 1 to 9, and / or an optical element according to claim 11.

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