Optical glass, glass preforms, optical elements and optical instruments

Abstract

To provide an optical glass with a refractive index of 1.96 or more, an Abbe number of 34 or less, and low density.SOLUTION: An optical glass provided includes, in wt.%, following components: SiO2: 1-15%, B2O3: 2-18%, La2O3: 35-65%, Y2O3: 5-25%, ZrO2: 2-15%, Nb2O5: 1-15%, and TiO2: 5-20%, the optical glass having a refractive index nd of 1.96 or more. The inventive optical glass features a rational component design, allowing for achievement of a desired refractive index and Abbe number, as well as relatively low density, thereby meeting a demand for lighter optical devices.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to optical glass, and more particularly to optical glass having a refractive index of 1.96 or more and an Abbe number of 34 or less, and to a glass preform, optical element and optical instrument made thereof. [Background technology]

[0002] In recent years, the digitalization of optical devices and the increasing resolution of images and videos have been rapidly developing. The trend toward higher resolution images and videos is particularly evident in optical devices such as digital cameras, video cameras, and projectors. At the same time, efforts are being made to reduce the weight and size of these optical devices by reducing the number of optical elements, such as lenses and prisms, in the optical systems contained in these devices.

[0003] For the same radius of curvature, a glass with a higher refractive index can provide a larger imaging field of view, which is advantageous for reducing the number of optical elements in optical instruments. With the trend toward miniaturization of optical instruments, the demand for high refractive index glass is increasing. In order to achieve the goal of reducing the weight of optical instruments, reducing the density of optical glass is also an important measure, in addition to reducing the number of optical elements in optical systems. CN101734855A discloses high refractive index optical glass with a refractive index greater than 1.95 but not greater than 2.20 and a dispersion coefficient of 15 to 25, but its high density is disadvantageous for further reducing the weight of optical instruments. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Chinese Patent Application Publication No. 1734855 Summary of the Invention [Problem to be solved by the invention]

[0005] The technical problem to be solved by the present invention is to provide an optical glass having a refractive index of 1.96 or more, an Abbe number of 34 or less, and a low density. [Means for solving the problem]

[0006] The technical solutions adopted by the present invention to solve the technical problems are as follows:

[0007] An optical glass containing the following components in weight percent: SiO2: 1 to 15%, B2O3: 2 to 18%, La2O3: 35 to 65%, Y2O3: 5 to 25%, ZrO2: 2 to 15%, Nb2O5: 1 to 15%, TiO2: 5 to 20%, and the refractive index n of said optical glass. d is 1.96 or higher.

[0008] The optical glass further contains the following components in weight percent: Gd2O3: 0-10%, and / or Ta2O5: 0-5%, and / or RO: 0-10%, and / or Rn2O: 0-8%, and / or WO3: 0-5%, and / or ZnO: 0-10%, and / or Al2O3: 0-8%, and / or Yb2O3: 0-10%, and / or GeO2: 0-5%, and / or a fining agent: 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 fining agent is one or more of Sb2O3, SnO, SnO2, and CeO2.

[0009] Optical glass containing the following components by weight: SiO2: 1-15%, B2O3: 2-18%, La2O3: 35-65%, Y2O3: 5-25%, ZrO2: 2-15%, Nb2O5: 1-15%, TiO2: 5-20%, Gd2O3: 0-10%, Ta2O5: 0-5%, RO: 0-10%, Rn2O: 0-8%, WO3: 0-5%, ZnO: 0-10%, Al2O3 : 0 to 8%, Yb2O3: 0 to 10%, GeO2: 0 to 5%, fining agent: 0 to 2%, said RO is one or more of MgO, CaO, SrO and BaO, said Rn2O is one or more of Li2O, Na2O and K2O, and the fining agent is one or more of Sb2O3, SnO, SnO2 and CeO2, and the refractive index n of said optical glass d is 1.96 or higher.

[0010] The optical glass further contains the following components in weight percent: 45 to 75% La2O3+Y2O3+Gd2O3, preferably 50 to 75% La2O3+Y2O3+Gd2O3, and more preferably 55 to 70% La2O3+Y2O3+Gd2O3.

[0011] The optical glass further contains the following components in weight percent: SiO2+B2O3 is 5 to 30%, preferably SiO2+B2O3 is 8 to 25%, and more preferably SiO2+B2O3 is 10 to 20%.

[0012] The optical glass further contains the following components in weight percent: (La2O3+TiO2) / Nb2O5 is 3.0 to 30.0, preferably (La2O3+TiO2) / Nb2O5 is 4.0 to 25.0, more preferably (La2O3+TiO2) / Nb2O5 is 5.0 to 20.0, and even more preferably (La2O3+TiO2) / Nb2O5 is 5.5 to 15.0.

[0013] The optical glass further contains the following components in weight percent: Nb2O5 / Y2O3 is 0.1 to 2.0, preferably Nb2O5 / Y2O3 is 0.2 to 1.5, more preferably Nb2O5 / Y2O3 is 0.3 to 1.3, and even more preferably Nb2O5 / Y2O3 is 0.3 to 1.0.

[0014] The optical glass further contains the following components in weight percent: Y2O3 / TiO2 is 0.3 to 3.0, preferably Y2O3 / TiO2 is 0.4 to 2.0, more preferably Y2O3 / TiO2 is 0.5 to 1.5, and even more preferably Y2O3 / TiO2 is 0.7 to 1.3.

[0015] The optical glass further contains the following components in weight percent: (Nb2O5+WO3+Gd2O3) / TiO2 is 0.1 to 3.0, preferably (Nb2O5+WO3+Gd2O3) / TiO2 is 0.2 to 2.5, more preferably (Nb2O5+WO3+Gd2O3) / TiO2 is 0.3 to 2.0, and even more preferably (Nb2O5+WO3+Gd2O3) / TiO2 is 0.4 to 1.5.

[0016] The optical glass further contains the following components in weight percent: (RO+ZnO) / Y2O3 is 1.0 or less, preferably (RO+ZnO) / Y2O3 is 0.8 or less, more preferably (RO+ZnO) / Y2O3 is 0.5 or less, and even more preferably (RO+ZnO) / Y2O3 is 0.2 or less, and the RO is one or more of MgO, CaO, SrO, and BaO.

[0017] The optical glass further contains the following components in weight percent: (RO+Gd2O3) / Y2O3 is 1.0 or less, preferably (RO+Gd2O3) / Y2O3 is 0.8 or less, more preferably (RO+Gd2O3) / Y2O3 is 0.6 or less, and even more preferably (RO+Gd2O3) / Y2O3 is 0.3 or less, and the RO is one or more of MgO, CaO, SrO, and BaO.

[0018] The optical glass further contains the following components in weight percent: (WO3+TiO2) / Y2O3 is 0.3 to 3.0, preferably (WO3+TiO2) / Y2O3 is 0.4 to 2.5, more preferably (WO3+TiO2) / Y2O3 is 0.5 to 2.0, and even more preferably (WO3+TiO2) / Y2O3 is 0.7 to 1.5.

[0019] The optical glass further contains the following components in weight percent: (SiO2+B2O3) / Y2O3 is 0.2 to 3.5, preferably (SiO2+B2O3) / Y2O3 is 0.4 to 3.0, more preferably (SiO2+B2O3) / Y2O3 is 0.5 to 2.5, and even more preferably (SiO2+B2O3) / Y2O3 is 0.7 to 1.8.

[0020] The optical glass further contains the following components in weight percent: SiO2: 2 to 10%, preferably SiO2: 4 to 9%, and / or B2O3: 4 to 12%, preferably B2O3: 5 to 10%, and / or La2O3: 40 to 60%, preferably La2O3: 42 to 55%, and / or Y2O3: 6 to 20%, preferably Y2O3: 8 to 18%, more preferably Y2O3: 8 to 15%, and / or ZrO2: 3 to 12%. , preferably ZrO2: 4 to 10%, and / or Nb2O5: 3 to 12%, preferably Nb2O5: 5 to 10%, and / or Ta2O5: 0 to 3%, preferably Ta2O5: 0 to 1%, and / or Gd2O3: 0 to 6%, preferably Gd2O3: 0 to 4%, and / or TiO2: 6 to 18%, preferably TiO2: 8 to 15%, and / or RO: 0 to 5%, Preferably, RO: 0-2%, and / or Rn2O: 0-3%, preferably Rn2O: 0-2%, and / or WO3: 0-3%, preferably WO3: 0-2%, and / or ZnO: 0-5%, preferably ZnO: 0-2%, and / or Al2O3: 0-4%, preferably Al2O3: 0-2%, and / or Yb2O3: 0-5%, preferably Yb2O3: 0-2%, and / or GeO2: 0-3%, preferably GeO2: 0-1%, and / or fining agent: 0-1%, preferably fining agent: 0-0.5%, wherein RO is one or more of MgO, CaO, SrO, and BaO, Rn2O is one or more of Li2O, Na2O, and K2O, and the fining agent is one or more of Sb2O3, SnO, SnO2, and CeO2.

[0021] The optical glass further contains the following components in weight percent: SiO2, B2O3, La2O3, Y2O3, ZrO2, Nb2O5, and TiO2, with a total content of 90% or more, preferably SiO2, B2O3, La2O3, Y2O3, ZrO2, Nb2O5, and TiO2 of 92% or more, more preferably SiO2, B2O3, La2O3, Y2O3, ZrO2, Nb2O5, and TiO2 of 94% or more, and even more preferably SiO2, B2O3, La2O3, Y2O3, ZrO2, Nb2O5, and TiO2 of 96% or more.

[0022] The optical glass may further comprise any of the components not containing Ta2O5, and / or not containing WO3, and / or not containing Yb2O3, and / or not containing RO, and / or not containing Rn2O, and / or not containing ZnO, and / or not containing Al2O3, and / or not containing GeO2, wherein RO is one or more of MgO, CaO, SrO, and BaO, and Rn2O is one or more of Li2O, Na2O, and K2O.

[0023] Furthermore, the refractive index n of the optical glass d is 1.97 or more, preferably 1.98 or more, more preferably 1.99 or more, and even more preferably 1.99 to 2.02, and Abbe number v d is 23 to 34, preferably 25 to 33, more preferably 26 to 32, and further preferably 27 to 31.

[0024] Furthermore, the density ρ of the optical glass is 5.20 g / cm 3 or less, preferably 5.10 g / cm 3 or less, more preferably 5.00 g / cm 3 and / or the thermal expansion coefficient α -30 / 70℃ is 85 x 10 -7 / K or less, preferably 80×10 -7 / K or less, preferably 75×10 -7 / K or less, and / or water resistance stability D W is Class 2 or more, preferably Class 1, and / or acid resistance stability D A is Class 2 or more, preferably Class 1, and / or weather resistance CR is Class 2 or more, preferably Class 1, and / or Knoop hardness H K is 670 x 10 7 Pa or more, preferably 680 x 10 7 Pa or more, preferably 690×10 7 Pa or more, and / or Young's modulus E is 11500 × 10 7 Pa~15500×10 7 Pa, preferably 12000 x 10 7 Pa~15000×10 7 Pa, more preferably 12500×10 7 Pa~14500×10 7Pa, more preferably 13000×10 7 Pa~14000×10 7 Pa and / or foaming degree is A class or higher, preferably A0 class or higher, more preferably A 00 Grade and / or wear level F A is 80 to 125, preferably 85 to 115, and more preferably 90 to 105.

[0025] A glass preform manufactured from the above optical glass.

[0026] An optical element manufactured from the above optical glass or the above glass preform.

[0027] An optical instrument comprising the optical glass and / or the optical element. [Effects of the Invention]

[0028] The beneficial effects of the present invention are as follows: By rationally designing the components, the optical glass obtained by the present invention has a desired refractive index and Abbe number, and at the same time, has a relatively low density, which can meet the need for lightweight optical instruments. DETAILED DESCRIPTION OF THE INVENTION

[0029] Hereinafter, embodiments of the optical glass according to the present invention will be described in detail, but the present invention is not limited to the embodiments described below, and can be practiced by making appropriate modifications within the scope of the object of the present invention. Furthermore, although some omissions may be made, the gist of the present invention is not limited by repetition of the description, and hereinafter the optical glass of the present invention may also be referred to simply as glass.

[0030] [Optical glass] The range of components of the optical glass of the present invention is explained below. In this specification, the content and total content of each component are expressed in weight percent (wt%) unless otherwise specified. That is, the content and total content of each component are expressed as weight percent relative to the total weight of the glass material converted into an oxide composition. Here, "converted to an oxide composition" refers to the case where the total weight of the oxide material when the oxides, complex salts, hydroxides, etc. used as raw materials for the optical glass composition of the present invention are decomposed and converted into oxides during melting is taken as 100%.

[0031] Specifically, the numerical ranges set forth herein include upper and lower limits, and the terms "greater than or equal to" and "less than or equal to" include the endpoints, and all integers and fractions subsumed within the range, but are not limited to the specific values ​​set forth when the range is limited. References herein to "and / or" are inclusive, e.g., "A and / or B" means A only, B only, or both A and B.

[0032] <Required and optional ingredients> B2O3 is a glass network-forming component that can improve the meltability and devitrification resistance of glass and lower the glass transition temperature and density. To achieve these effects, the present invention adds 2% or more B2O3, preferably 4% or more, and more preferably 5% or more. However, if the B2O3 content exceeds 18%, the stability of the glass decreases and the refractive index decreases, making it difficult to achieve the high refractive index of the present invention. Therefore, in the present invention, the upper limit of the B2O3 content is 18%, preferably 12%, and more preferably 10%.

[0033] SiO2 is also a network-forming component that adjusts the thermal expansion coefficient of glass, enhances the devitrification resistance and chemical stability of glass, and improves the thermal stability and high-temperature viscosity of glass. However, if the SiO2 content exceeds 15%, the melting performance of glass tends to deteriorate and the transition temperature rises. Therefore, in the present invention, the SiO2 content is 1 to 15%, preferably 2 to 10%, and more preferably 4 to 9%.

[0034] In some embodiments, by controlling the total content of SiO2 and B2O3 (SiO2+B2O3) to within a range of 5 to 30%, the glass forming stability of the glass can be maintained, while the abrasion resistance and weather resistance of the glass can be optimized and a decrease in the devitrification resistance of the glass can be prevented. Therefore, SiO2+B2O3 is preferably 5 to 30%, more preferably 8 to 25%, and even more preferably 10 to 20%.

[0035] La2O3 is an effective component for increasing the refractive index of glass and has a significant effect of improving the chemical stability and devitrification resistance of glass, but if its content is less than 35%, it is difficult to achieve the desired optical constants, and if its content exceeds 65%, the tendency of the glass to devitrify increases and thermal stability deteriorates. Therefore, the La2O3 content is 35 to 65%, preferably 40 to 60%, and more preferably 42 to 55%.

[0036] Y2O3 increases the refractive index and devitrification resistance of glass and can adjust the Young's modulus of glass. In order to achieve the above effects, the present invention adds 5% or more of Y2O3. If the content exceeds 25%, the chemical stability and weather resistance of the glass deteriorate. Therefore, in the present invention, the Y2O3 content is 5 to 25%, preferably 6 to 20%, more preferably 8 to 18%, and even more preferably 8 to 15%.

[0037] In some embodiments, controlling the ratio of the total content of SiO2 and B2O3 (SiO2 + B2O3) to the content of Y2O3 ((SiO2 + B2O3) / Y2O3)) to within 0.2 to 3.5 is advantageous in increasing the cellular content of the glass and preventing an increase in the thermal expansion coefficient of the glass. Therefore, (SiO2 + B2O3) / Y2O3 is preferably 0.2 to 3.5, and more preferably 0.4 to 3.0. Furthermore, controlling (SiO2 + B2O3) / Y2O3 to within 0.5 to 2.5 can further improve the hardness and weather resistance of the glass. Therefore, more preferably, (SiO2 + B2O3) / Y2O3 is 0.5 to 2.5, and even more preferably, 0.7 to 1.8.

[0038] Although Gd2O3 can increase the refractive index and chemical stability of glass, if its content exceeds 10%, the devitrification resistance and abrasion resistance of the glass deteriorate. Therefore, the Gd2O3 content is 0 to 10%, preferably 0 to 6%, and more preferably 0 to 4%.

[0039] In some embodiments, by controlling the total content of La2O3, Y2O3, and Gd2O3 (La2O3+Y2O3+Gd2O3) to within 45 to 75%, the glass can easily achieve the desired refractive index and Abbe number, and the devitrification resistance and weather resistance of the glass can be optimized. Therefore, La2O3+Y2O3+Gd2O3 is preferably 45 to 75%, more preferably 50 to 75%, and even more preferably 55 to 70%.

[0040] Yb2O3 is also a component that imparts high refractive index and low dispersion to the glass, and if its content exceeds 8%, the crystallization resistance of the glass decreases. Therefore, the Yb2O3 content should be 0 to 10%, preferably 0 to 5%, more preferably 0 to 2%, and even more preferably no Yb2O3.

[0041] ZrO2 can increase the viscosity, hardness, refractive index, and chemical stability of optical glass and can also reduce the thermal expansion coefficient of glass, but if the ZrO2 content is too high, the devitrification resistance of the glass decreases, the melting difficulty increases, the melting temperature rises, inclusions occur inside the glass, and the light transmittance decreases. Therefore, in the present invention, the ZrO2 content is 2 to 15%, preferably 3 to 12%, and more preferably 4 to 10%.

[0042] TiO2 is a high refractive index, high dispersion component, and its addition to glass can significantly improve the refractive index and dispersion of the glass. According to the inventors' research, adding an appropriate amount of TiO2 can increase the stability of the glass. However, if the TiO2 content is too high, the transmittance of the glass decreases significantly and the chemical stability of the glass also tends to deteriorate. Therefore, in the present invention, the TiO2 content is 5 to 20%, preferably 6 to 18%, and more preferably 8 to 15%.

[0043] In some embodiments, the weather resistance of the glass can be improved and the abrasion resistance can be optimized by controlling the ratio of the Y2O3 content to the TiO2 content, Y2O3 / TiO2, within a range of 0.3 to 3.0. Therefore, Y2O3 / TiO2 is preferably 0.3 to 3.0, and more preferably 0.4 to 2.0. Furthermore, by controlling Y2O3 / TiO2 within a range of 0.5 to 1.5, the chemical stability and bubble content of the glass can be further improved. Therefore, Y2O3 / TiO2 is more preferably 0.5 to 1.5, and even more preferably 0.7 to 1.3.

[0044] Nb2O5 is a high-refractive, high-dispersion component that can increase the refractive index and devitrification resistance of glass and reduce the thermal expansion coefficient of glass. In order to achieve the above effects, the present invention adds 1% or more of Nb2O5, with the lower limit of the Nb2O5 content being preferably 3%, more preferably 5%. If the Nb2O5 content exceeds 15%, the thermal stability and weather resistance of the glass will decrease and the light transmittance will decrease, so the upper limit of the Nb2O5 content in the present invention is 15%, preferably 12%, more preferably 10%.

[0045] In some embodiments, the ratio (La2O3 + TiO2) / Nb2O5 (the ratio of the total content of La2O3 and TiO2 (La2O3 + TiO2) to the content of Nb2O5) can be controlled within a range of 3.0 to 30.0 to enhance the chemical stability of the glass and optimize its abrasion resistance. Therefore, (La2O3 + TiO2) / Nb2O5 is preferably 3.0 to 30.0, and more preferably 4.0 to 25.0. Furthermore, by controlling (La2O3 + TiO2) / Nb2O5 to a range of 5.0 to 20.0, the thermal expansion coefficient of the glass can be further reduced and the hardness of the glass can be increased. Therefore, more preferably, (La2O3 + TiO2) / Nb2O5 is 5.0 to 20.0, and even more preferably, (La2O3 + TiO2) / Nb2O5 is 5.5 to 15.0.

[0046] In some embodiments, by controlling the ratio of the Nb2O5 content to the Y2O3 content, Nb2O5 / Y2O3, to within a range of 0.1 to 2.0, the Young's modulus of the glass can be increased while preventing a decrease in glass hardness. Therefore, Nb2O5 / Y2O3 is preferably 0.1 to 2.0, and more preferably 0.2 to 1.5. Furthermore, by controlling Nb2O5 / Y2O3 to within a range of 0.3 to 1.3, the bubble content and abrasion resistance of the glass can be further optimized. Therefore, Nb2O5 / Y2O3 is more preferably 0.3 to 1.3, and even more preferably 0.3 to 1.0.

[0047] Alkaline earth metal oxides RO (RO is one or more of MgO, CaO, SrO, and BaO) can adjust the optical constants of glass and optimize the chemical stability of the glass, but a high RO content reduces the devitrification resistance of the glass. Therefore, the RO content is limited to 0 to 10%, preferably 0 to 5%, and more preferably 0 to 2%. In some embodiments, it is even more preferable that the glass does not contain RO.

[0048] In some embodiments, controlling the ratio of the total content of RO and GdO to the content of YO (RO + GdO) (RO + GdO) / YO (YO) to 1.0 or less is advantageous for reducing the density of the glass, improving the chemical stability of the glass, and optimizing the Young's modulus and cellularity of the glass. Therefore, (RO + GdO) / YO is preferably 1.0 or less, more preferably 0.8 or less, even more preferably 0.6 or less, and even more preferably 0.3 or less.

[0049] The alkaline metal oxide RnO (RnO is one or more of LiO, NaO, and KO) can lower the glass transition temperature, adjust the optical constants and high-temperature viscosity of the glass, and improve the meltability of the glass. However, if the RnO content is high, the devitrification resistance and chemical stability of the glass decrease. Therefore, in the present invention, the RnO content is 0 to 8%, preferably 0 to 3%, and more preferably 0 to 2%. In some embodiments, it is even more preferable that the glass does not contain RnO.

[0050] Although WO3 can increase the refractive index and mechanical strength of glass, a WO3 content exceeding 5% reduces the thermal stability and devitrification resistance of the glass. Therefore, the upper limit of the WO3 content is 5%, preferably 3%, and more preferably 2%. In some embodiments, it is even more preferable to have no WO3.

[0051] In some embodiments, by controlling the ratio of the total content of Nb2O5, WO3, and Gd2O3 (Nb2O5 + WO3 + Gd2O3) to the content of TiO2 (Nb2O5 + WO3 + Gd2O3) / TiO2 within a range of 0.1 to 3.0, it is possible to improve the light transmittance of the glass while preventing an increase in density. Therefore, it is preferable that (Nb2O5 + WO3 + Gd2O3) / TiO2 is 0.1 to 3.0, and more preferably that (Nb2O5 + WO3 + Gd2O3) / TiO2 is 0.2 to 2.5. Furthermore, by controlling (Nb2O5 + WO3 + Gd2O3) / TiO2 within a range of 0.3 to 2.0, it is possible to further reduce the thermal expansion coefficient of the glass and increase its Young's modulus. Therefore, more preferably, (Nb2O5+WO3+Gd2O3) / TiO2 is 0.3 to 2.0, and even more preferably, (Nb2O5+WO3+Gd2O3) / TiO2 is 0.4 to 1.5.

[0052] In some embodiments, controlling the ratio of the total content of WO3 and TiO2 (WO3 + TiO2) to the content of Y2O3 ((WO3 + TiO2) / Y2O3)) to within a range of 0.3 to 3.0 is advantageous for improving the chemical stability of the glass and optimizing the abrasion resistance and Young's modulus. Therefore, (WO3 + TiO2) / Y2O3 is preferably 0.3 to 3.0, more preferably 0.4 to 2.5, even more preferably 0.5 to 2.0, and even more preferably 0.7 to 1.5.

[0053] ZnO adjusts the refractive index and dispersion of the glass and can lower the high-temperature viscosity and transition temperature of the glass. If the ZnO content is too high, the glass becomes more difficult to mold and its crystallization resistance deteriorates. Therefore, the ZnO content is 0 to 10%, preferably 0 to 5%, and more preferably 0 to 2%. In some embodiments, it is even more preferable that no ZnO is contained.

[0054] In some embodiments, the ratio (RO+ZnO) / Y2O3 of the total content of RO and ZnO (RO+ZnO) to the content of Y2O3 (RO+ZnO) is controlled to 1.0 or less, thereby improving the weather resistance of the glass, optimizing the abrasion resistance, and preventing a decrease in the number of bubbles and the thermal expansion coefficient of the glass. Therefore, (RO+ZnO) / Y2O3 is preferably 1.0 or less, more preferably 0.8 or less, even more preferably 0.5 or less, and even more preferably 0.2 or less.

[0055] Ta2O5 can increase the refractive index and improve the devitrification resistance of the glass, but if its content is too high, the thermal stability of the glass decreases and the density increases. Furthermore, Ta2O5 is very expensive compared to other components, and from the viewpoints of practicality and cost, it is necessary to minimize its use. Therefore, the Ta2O5 content in the present invention is limited to 0 to 5%, preferably 0 to 3%, and more preferably 0 to 1%. In some embodiments, it is even more preferable that Ta2O5 is not included.

[0056] Although Al2O3 can improve the chemical stability of glass, if its content exceeds 8%, the meltability and light transmittance of the glass deteriorate. Therefore, in the present invention, the Al2O3 content is 0 to 8%, preferably 0 to 4%, and more preferably 0 to 2%. In some embodiments, it is even more preferable that Al2O3 is not contained.

[0057] Although GeO2 can increase the refractive index and devitrification resistance, if its content is too high, the chemical stability of the glass decreases. Furthermore, GeO2 is very expensive compared to other components, and from the viewpoint of practicality and cost, its use amount must be reduced as much as possible. Therefore, the GeO2 content in the present invention is limited to 0 to 5%, preferably 0 to 3%, more preferably 0 to 1%, and even more preferably, GeO2 is not included.

[0058] In the present invention, the addition of 0-2% of one or more of Sb2O3, SnO, SnO2, and CeO2 as a fining agent can enhance the fining effect of the glass and improve the glass's cellularity. The fining agent content is preferably 0-1%, and more preferably 0-0.5%. Because the types and contents of the components of the optical glass of the present invention are rationally designed and the glass has an excellent cellularity, in some embodiments, it is preferable to not include a fining agent. If the Sb2O3 content exceeds 2%, the glass's fining tends to decrease, and its strong oxidizing effect accelerates corrosion of platinum or platinum alloy containers for molten glass and deterioration of molding dies. Therefore, the Sb2O3 content in the present invention is preferably 0-2%, more preferably 0-1%, even more preferably 0-0.5%, and even more preferably no Sb2O3. SnO and SnO2 can also be used as fining agents, but if their content exceeds 2%, the glass's tendency to discolor increases, or when the glass is heated, softened, and reshaped by press molding, the Sn acts as a starting point for crystal nucleation, leading to devitrification. Therefore, the SnO2 content in the present invention is preferably 0-2%, more preferably 0-1%, even more preferably 0-0.5%, and even more preferably no SnO2. The SnO content is preferably 0-2%, more preferably 0-1%, even more preferably 0-0.5%, and even more preferably no SnO. The function and content of CeO2 are identical to those of SnO2, and its content is preferably 0-2%, more preferably 0-1%, even more preferably 0-0.5%, and even more preferably no CeO2.

[0059] In some embodiments, in order to obtain a low coefficient of thermal expansion and density, a relatively high light transmittance and porosity, and an appropriate abrasion resistance and Young's modulus for the optical glass of the present invention, the total content of SiO2, B2O3, La2O3, Y2O3, ZrO2, Nb2O5, and TiO2 is preferably 90% or more, more preferably 92% or more, even more preferably 94% or more, and still more preferably 96% or more.

[0060] <Ingredients that should not be included> In the glass of the present invention, even when oxides of transition metals such as V, Cr, Mn, Fe, Co, Ni, Cu, Ag, and Mo are contained alone or in combination, even in small amounts, the glass is colored and specific wavelengths in the visible light region are absorbed, weakening the visible light transmission effect of the present invention. Therefore, it is preferable that optical glasses that require wavelength transmittance in the visible light region in particular do not actually contain these oxides.

[0061] In recent years, there has been a trend toward restricting the use of oxides of Th, Cd, Tl, Os, Be, and Se as hazardous chemicals, necessitating environmental protection efforts not only in the glass manufacturing process but also in the processing and disposal of finished products. Therefore, when environmental impact is a major concern, it is preferable to avoid these elements except for unavoidable contamination. This ensures that the optical glass does not contain substances that actually pollute the environment. Therefore, the optical glass of the present invention can be manufactured, processed, and disposed of without the need for special environmental measures.

[0062] In consideration of the environment, the optical glass of the present invention preferably does not contain As2O3 and PbO.

[0063] The terms "not added," "not containing," and "0%" used herein mean that the component was not intentionally added as a raw material for the glass of the present invention. However, impurities or components not intentionally added as raw materials and / or equipment for producing the glass may exist in small or trace amounts in the final glass, and these are also within the scope of the present invention.

[0064] The properties of the optical glass of the present invention will be described below.

[0065] <Refractive index and Abbe number> The refractive index of optical glass (n d ) and Abbe number (ν d ) has been tested according to the method specified in GB / T 7962.1-2010.

[0066] In some embodiments, the refractive index (n d ) has a lower limit of 1.96, preferably 1.97, more preferably 1.98, and even more preferably 1.99.

[0067] In some embodiments, the refractive index (n d ) has an upper limit of 2.10, preferably 2.05, and more preferably 2.02.

[0068] In some embodiments, the Abbe number (ν d ) has a lower limit of 23, preferably a lower limit of 25, more preferably a lower limit of 26, and even more preferably a lower limit of 27.

[0069] In some embodiments, the Abbe number (ν d ) has an upper limit of 34, preferably 33, more preferably 32, and even more preferably 31.

[0070] <density> The density (ρ) of optical glass is tested according to the method described in GB / T 7962.20-2010.

[0071] In some embodiments, the density (ρ) of the optical glass of the present invention is 5.20 g / cm 3 or less, preferably 5.10 g / cm 3 or less, more preferably 5.00 g / cm 3 The following is the result.

[0072] <Thermal expansion coefficient> The thermal expansion coefficient of optical glass (α -30 / 70℃ ) is measured at -30 to 70°C according to the method described in GB / T 7962.16-2010.

[0073] In some embodiments, the thermal expansion coefficient (α -30 / 70℃ ) is 85 x 10 -7 / K or less, preferably 80×10 -7 / K or less, preferably 75×10 -7 / K or less.

[0074] <Water resistance stability> Water resistance stability of optical glass (D W ) (powder method) is tested according to the method specified in GB / T 17129.

[0075] In some embodiments, the water resistance stability (D W ) is class 2 or more, preferably class 1.

[0076] <Acid resistance stability> Acid resistance stability of optical glass (D A ) (powder method) is tested according to the method specified in GB / T 17129.

[0077] In some embodiments, the acid resistance stability (D A ) is class 2 or more, preferably class 1.

[0078] <Weather resistance> The weather resistance (CR) test method for optical glass is as follows: the sample is placed in a test box in a saturated water vapor environment with a relative humidity of 90%, and the temperature is alternately circulated at 40-50°C every hour for 15 cycles. The weather resistance categories are classified based on the amount of turbidity change before and after leaving the sample, and the weather resistance categories are shown in Table 1. [Table 1]

[0079] In some embodiments, the weather resistance (CR) of the optical glass of the present invention is Class 2 or higher, preferably Class 1.

[0080] <Knoop hardness> Knoop hardness of optical glass (H K ) has been tested in accordance with the test method specified in GB / T 7962.18-2010.

[0081] In some embodiments, the Knoop hardness (H K ) is 670 x 10 7 Pa or more, preferably 680 x 10 7 Pa or more, preferably 690×10 7 Pa or more.

[0082] <Young's modulus> Young's modulus (E) is calculated by measuring the longitudinal and shear wave velocities using ultrasound and using the following formula: TIFF0007762692000002.tif1236G=V S 2 ρ where: E is Young's modulus, Pa; G is the shear modulus, Pa; V T is the shear wave velocity, m / s; V S is the longitudinal wave velocity, m / s; ρ is the glass density, g / cm 3 is.

[0083] In some embodiments, the lower limit of the Young's modulus (E) of the optical glass of the present invention is 11500×10 7 Pa, preferably with a lower limit of 12000×10 7 Pa, and more preferably, the lower limit is 12500×10 7 Pa, and more preferably the lower limit is 13000×10 7 It is Pa.

[0084] In some embodiments, the upper limit of the Young's modulus (E) of the optical glass of the present invention is 15,500×10 7 Pa, preferably with an upper limit of 15000×10 7 Pa, and more preferably, the upper limit is 14500×10 7 Pa, and more preferably, the upper limit is 14000×10 7 It is Pa.

[0085] <Wear Level> Optical glass wear rate (F A ) is the ratio of the wear volume of the sample to the wear volume (volume) of a standard sample (H-K9 glass) under the exact same conditions, multiplied by 100, and the formula is as follows: F A =V / V0×100=(W / ρ) / (W0 / ρ0)×100 where V is the volumetric wear volume of the sample being measured; V0 is the volumetric wear volume of the standard sample; W is the mass wear amount of the sample to be measured; W0 is the quality wear volume of the standard sample; ρ is the density of the sample being measured; ρ0 is the density of the standard sample.

[0086] In some embodiments, the abrasion rate (F A ) has a lower limit of 80, preferably a lower limit of 85, and more preferably a lower limit of 90.

[0087] In some embodiments, the abrasion rate (F A ) The upper limit is 125, preferably 115, and more preferably 105.

[0088] <Bubble content> The bubble content of optical glass is tested according to the method specified in GB / T 7962.8-2010.

[0089] In some embodiments, the bubble content of the optical glass of the present invention is Class A or higher, preferably Class A0 or higher, more preferably Class A 00 It is a grade.

[0090] [Optical glass manufacturing method] The optical glass of the present invention is manufactured as follows: After mixing conventional raw materials, including but not limited to oxides, hydroxides, complex salts (carbonates, nitrates, sulfates, etc.), and boric acid, using conventional processes, the resulting furnace material is placed in a melting furnace (platinum or platinum alloy crucible) at 1200-1450°C and melted. The mixture is then refined and homogenized to obtain a homogeneous molten glass free of bubbles and undissolved materials. This molten glass is then cast into a mold and annealed. Those skilled in the art will be able to select the appropriate raw materials, manufacturing methods, and process parameters according to actual needs.

[0091] [Glass preforms and optical elements] Glass preforms can be manufactured from optical glass prepared using press molding methods such as direct drop molding, polishing, or hot press molding. That is, molten optical glass can be manufactured into a precision glass preform by direct precision drop molding, or a glass preform can be manufactured by mechanical processing such as grinding or polishing, or a preform blank for press molding can be manufactured using optical glass, and this preform blank can be hot pressed and polished to produce a glass preform. It should be noted that the means for manufacturing optical preforms are not limited to the above means.

[0092] As described above, the optical glass of the present invention is useful for various optical elements and optical designs, and it is particularly preferable to form a blank from the optical glass of the present invention and use this blank to carry out hot press molding, precision press molding, or the like to produce optical elements such as lenses and prisms.

[0093] The optical preform and optical element of the present invention are both formed from the optical glass of the present invention. The optical preform of the present invention has the excellent properties of optical glass, and the optical element of the present invention has the excellent properties of optical glass, making it possible to provide optical elements such as various lenses and prisms with high optical value.

[0094] Examples of lenses include various lenses 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, each having a spherical or aspherical lens surface.

[0095] [Optical equipment] Optical elements formed from the optical glass of the present invention can be used to manufacture optical equipment such as photographic devices, imaging devices, projection devices, display devices, in-vehicle devices, and monitoring devices. [Example]

[0096] <Optical Glass Examples> To further clearly illustrate the technical solutions of the present invention, the following non-limiting examples are provided.

[0097] In the present examples, the above-described optical glass manufacturing method was used to obtain optical glasses having the components shown in Tables 2 to 4. The properties of each glass were measured using the test methods described in the present invention, and the results are shown in Tables 2 to 4. [Table 2]

[0098] [Table 3]

[0099] [Table 4]

[0100] <Example of glass preform> The glasses obtained in Examples 1 to 24 of the optical glass are used to produce preforms for various lenses, such as concave meniscus lenses, convex meniscus lenses, biconvex lenses, biconcave lenses, plano-convex lenses, and plano-concave lenses, as well as prisms, using polishing means or press molding means such as reheat press molding and precision press molding.

[0101] <Optical element examples> These preforms obtained in the glass preform examples above are annealed to fine-tune the refractive index while reducing the stress inside the glass so that the optical properties, such as the refractive index, reach the desired values.

[0102] 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.Anti-reflection coatings can also be applied to the surfaces of the resulting optical elements.

[0103] <Optical equipment example> The optical elements manufactured according to the above optical element embodiments can be used in imaging devices, sensors, microscopes, medical technology, digital projection, communications, optical communication technology / information transmission, optics / illumination in the automotive field, photolithography technology, excimer lasers, wafers, computer chips and integrated circuits and electronic devices containing such circuits and chips, by using one or more optical elements according to optical design to form optical parts or components.

Claims

1. An optical glass comprising the following components in weight percent: SiO ２ : 1 to 15%, B ２ O ３ : 2-18%, La ２ O ３ : 35-65%, Y ２ O ３ :5~25%, ZrO ２ : 2-15%, Nb ２ O ５ :1~15%, TiO ２ :5-16.5%, Gd ２ O ３ :0~7.5%, (WO ３ + TiO ２ ) / Y ２ O ３ is 0.3 to 1.968, (Nb ２ O ５ +WO ３ +Gd ２ O ３ ) / TiO ２ is 0.35 to 1.797, Y ２ O ３ / TiO ２ is 0.7 to 3.0, and Nb 2 O 5 / Y 2 O 3 is 0.1 to 0.894, The refractive index n of the optical glass ｄ is 1.96 or more, Optical glass.

2. Gd in wt% ２ O ３ : 0 to 10%, and / or Ta ２ O ５ : 0 to 5%, and / or RO: 0 to 10%, and / or Rn ２ O: 0 to 8%, and / or WO ３ : 0 to 5%, and / or ZnO: 0 to 10%, and / or Al ２ O ３ : 0 to 8%, and / or Yb ２ O ３ : 0 to 10%, and / or GeO ２ : 0-5%, and / or clarifier: 0-2%, The RO is one or more of MgO, CaO, SrO, and BaO, and Rn ２ O is Li ２ O, Na ２ O.K. ２ The fining agent is one or more of Sb ２ O ３ , SnO, SnO ２ , CeO ２ One or more of the following: The optical glass according to claim 1 .

3. An optical glass comprising the following components in weight percent: SiO ２ : 1 to 15%, B ２ O ３ : 2-18%, La ２ O ３ : 35-65%, Y ２ O ３ :5~25%, ZrO ２ : 2-15%, Nb ２ O ５ :1~15%, TiO ２ :5-16.5%, Gd ２ O ３ :0 to 7.5%, Ta ２ O ５ : 0-5%, RO: 0-10%, Rn ２ O: 0-8%, WO ３ : 0~5%; ZnO: 0~10%, Al ２ O ３ : 0 to 8%, Yb ２ O ３ :0~10%, GeO ２ : 0 to 5%, clarifier: 0 to 2%, (WO ３ + TiO ２ ) / Y ２ O ３ is 0.3 to 1.968, (Nb ２ O ５ +WO ３ +Gd ２ O ３ ) / TiO ２ is 0.35 to 1.797, Y ２ O ３ / TiO ２ is 0.7 to 3.0, and Nb 2 O 5 / Y 2 O 3 is 0.1 to 0.894, The RO is one or more of MgO, CaO, SrO, and BaO, and Rn ２ O is Li ２ O, Na ２ O.K. ２ The fining agent is one or more of Sb ２ O ３ , SnO, SnO ２ , CeO ２ and the refractive index n ｄ is 1.96 or more, Optical glass.

4. % by weight of the composition, and satisfying one or more of the following six conditions: 1) The ２ O ３ +Y ２ O ３ +Gd ２ O ３ は45~75%; 2) SiO ２ +B ２ O ３ is 5-30%; 3) (La ２ O ３ + TiO ２ ) / Nb ２ O ５ is 3.0-30.0; 4) (RO+ZnO) / Y ２ O ３ is less than or equal to 1.0; 5) (RO+Gd ２ O ３ ) / Y ２ O ３ is less than or equal to 1.0; 6) (SiOO ２ +B ２ O ３ ) / Y ２ O ３ は0.2~3.5、 The RO is one or more of MgO, CaO, SrO, and BaO; The optical glass according to any one of claims 1 to 3.

5. % by weight of the component, and satisfying one or more of the following nine conditions: 1) The ２ O ３ +Y ２ O ３ +Gd ２ O ３ は50~75%; 2) SiO ２ +B ２ O ３ is 8-25%; 3) (La ２ O ３ + TiO ２ ) / Nb ２ O ５ is 4.0-25.0; 4) Nb ２ O ５ / Y ２ O ３ is 0.2 to 0.894; 5) Y ２ O ３ / TiO ２ is 0.7-2.0; 6) (RO+ZnO) / Y ２ O ３ is 0.8 or less; 7) (RO+Gd ２ O ３ ) / Y ２ O ３ is 0.8 or less; 8) (W.O. ３ + TiO ２ ) / Y ２ O ３ is 0.4 to 1.968; 9) (SiOO ２ +B ２ O ３ ) / Y ２ O ３ は0.4~3.0、 The RO is one or more of MgO, CaO, SrO, and BaO; The optical glass according to any one of claims 1 to 3.

6. % by weight of the component, and satisfying one or more of the following nine conditions: 1) The ２ O ３ +Y ２ O ３ +Gd ２ O ３ は55~70%; 2) SiO ２ +B ２ O ３ is 10-20%; 3) (La ２ O ３ + TiO ２ ) / Nb ２ O ５ is 5.0-20.0; 4) Nb ２ O ５ / Y ２ O ３ is 0.3 to 0.894; 5) Y ２ O ３ / TiO ２ is 0.7-1.5; 6) (RO+ZnO) / Y ２ O ３ is less than or equal to 0.5; 7) (RO+Gd ２ O ３ ) / Y ２ O ３ is 0.6 or less; 8) (W.O. ３ + TiO ２ ) / Y ２ O ３ is 0.5 to 1.968; 9) (SiOO ２ +B ２ O ３ ) / Y ２ O ３ は0.5~2.5、 The RO is one or more of MgO, CaO, SrO, and BaO; The optical glass according to any one of claims 1 to 3.

7. % by weight of the composition, and satisfying one or more of the following seven conditions: 1) (La ２ O ３ + TiO ２ ) / Nb ２ O ５ is 5.5-15.0; 2) Y ２ O ３ / TiO ２ is 0.7-1.3; 3) (Nb ２ O ５ +WO ３ +Gd ２ O ３ ) / TiO ２ is 0.4-1.5; 4) (RO+ZnO) / Y ２ O ３ is less than or equal to 0.2; 5) (RO+Gd ２ O ３ ) / Y ２ O ３ is less than or equal to 0.3; 6) (W.O. ３ + TiO ２ ) / Y ２ O ３ is 0.7-1.5; 7) (SiOO ２ +B ２ O ３ ) / Y ２ O ３ は0.7~1.8、 The RO is one or more of MgO, CaO, SrO, and BaO; The optical glass according to any one of claims 1 to 3.

8. Contains the following components in weight percent: SiO ２ : 2 to 10%, and / or B ２ O ３ : 4 to 12%, and / or La ２ O ３ : 40 to 60%, and / or Y ２ O ３ : 6 to 20%, and / or ZrO ２ : 3 to 12%, and / or Nb ２ O ５ : 3 to 12%, and / or Ta ２ O ５ : 0 to 3%, and / or Gd ２ O ３ : 0 to 6%, and / or TiO ２ : 6 to 16.5%, and / or RO: 0 to 5%, and / or Rn ２ O: 0 to 3%, and / or WO ３ : 0 to 3%, and / or ZnO: 0 to 5%, and / or Al ２ O ３ : 0 to 4%, and / or Yb ２ O ３ : 0 to 5%, and / or GeO ２ : 0 to 3%, and / or clarifier: 0 to 1%, The RO is one or more of MgO, CaO, SrO, and BaO, and Rn ２ O is Li ２ O, Na ２ O.K. ２ The fining agent is one or more of Sb ２ O ３ , SnO, SnO ２ , CeO ２ One or more of the following: The optical glass according to any one of claims 1 to 3.

9. Contains the following components in weight percent: SiO ２ : 4 to 9%, and / or B ２ O ３ : 5 to 10%, and / or La ２ O ３ : 42 to 55%, and / or Y ２ O ３ : 8 to 15%, and / or ZrO ２ : 4 to 10%, and / or Nb ２ O ５ : 5 to 10%, and / or Ta ２ O ５ : 0 to 1%, and / or Gd ２ O ３ : 0 to 4%, and / or TiO ２ : 8 to 15%, and / or RO: 0 to 2%, and / or Rn ２ O: 0 to 2%, and / or WO ３ : 0 to 2%, and / or ZnO: 0 to 2%, and / or Al ２ O ３ : 0 to 2%, and / or Yb ２ O ３ : 0 to 2%, and / or GeO ２ : 0 to 1%, and / or fining agent: 0 to 0.5%, The RO is one or more of MgO, CaO, SrO, and BaO, and Rn ２ O is Li ２ O, Na ２ O.K. ２ The fining agent is one or more of Sb ２ O ３ , SnO, SnO ２ , CeO ２ One or more of the following: The optical glass according to any one of claims 1 to 3.

10. SiO in wt% ２ , B ２ O ３ , La ２ O ３ , Y ２ O ３ , ZrO ２ , Nb ２ O ５ , TiO ２ The total content is 92% or more, The optical glass according to any one of claims 1 to 3.

11. SiO in wt% ２ , B ２ O ３ , La ２ O ３ , Y ２ O ３ , ZrO ２ , Nb ２ O ５ , TiO ２ The total content is 96% or more, The optical glass according to any one of claims 1 to 3.

12. The component is Ta ２ O ５ does not contain and / or WO ３ and / or Yb ２ O ３ does not contain RO and / or does not contain Rn ２ Does not contain O and / or does not contain ZnO and / or Al ２ O ３ and / or GeO ２ Does not include The RO is one or more of MgO, CaO, SrO, and BaO, and Rn ２ O is Li ２ O, Na ２ O.K. ２ One or more of O, The optical glass according to any one of claims 1 to 3.

13. The refractive index n of the optical glass ｄ is 1.98 or more, Abbe number v ｄ is 23 to 34, The optical glass according to any one of claims 1 to 3.

14. The refractive index n of the optical glass ｄ is 1.99 to 2.02, Abbe number ν ｄ is 27 to 31, The optical glass according to any one of claims 1 to 3.

15. The density ρ of the optical glass is 5.20 g / cm ３ and / or the thermal expansion coefficient α －３０／７０℃ is 85 x 10 －７ / K or less, and / or water resistance stability D Ｗ Class 2 or higher, and / or acid resistance stability D Ａ is Class 2 or higher, and / or weather resistance CR is Class 2 or higher, and / or Knoop hardness H Ｋ is 670 x 10 ７ Pa or more, and / or Young's modulus E is 11500 × 10 ７ Pa~15500×10 ７ Pa and / or porosity is Class A or higher, and / or abrasion level is F Ａ is between 80 and 125, The optical glass according to any one of claims 1 to 3.

16. The density ρ of the optical glass is 5.00 g / cm ３ and / or the thermal expansion coefficient α －３０／７０℃ is 75 x 10 －７ / K or less, and / or water resistance stability D Ｗ Class 1 and / or acid resistance stability D Ａ Class 1, and / or weather resistance CR Class 1, and / or Knoop hardness H Ｋ is 690 x 10 ７ Pa or more, and / or Young's modulus E is 13000 × 10 ７ Pa~14000×10 ７ Pa and / or foaming degree is A ００ Grade and / or wear level F Ａ is 90 to 105, The optical glass according to any one of claims 1 to 3.

17. A glass preform manufactured from the optical glass according to any one of claims 1 to 3.

18. An optical element manufactured using the optical glass according to any one of claims 1 to 3.

19. An optical instrument comprising the optical glass according to any one of claims 1 to 3.

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