WO2014048362A1 - Environmentally-friendly heavy lanthanum flint optical glass - Google Patents

Environmentally-friendly heavy lanthanum flint optical glass Download PDF

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Publication number
WO2014048362A1
WO2014048362A1 PCT/CN2013/084422 CN2013084422W WO2014048362A1 WO 2014048362 A1 WO2014048362 A1 WO 2014048362A1 CN 2013084422 W CN2013084422 W CN 2013084422W WO 2014048362 A1 WO2014048362 A1 WO 2014048362A1
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Prior art keywords
optical glass
glass
environmentally friendly
sro
friendly heavy
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PCT/CN2013/084422
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French (fr)
Chinese (zh)
Inventor
孙伟
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成都光明光电股份有限公司
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Priority to CN201380048545.3A priority Critical patent/CN104736490A/en
Priority to JP2015533440A priority patent/JP5972469B2/en
Publication of WO2014048362A1 publication Critical patent/WO2014048362A1/en
Priority to HK15106706.5A priority patent/HK1205998A1/en

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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/062—Glass compositions containing silica with less than 40% silica by weight
    • C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
    • C03C3/068—Glass compositions containing silica with less than 40% silica by weight containing boron containing rare earths
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/12—Silica-free oxide glass compositions
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements

Definitions

  • the invention relates to an environmentally friendly optical glass, in particular to an environmentally friendly heavy flint optical glass having a refractive index of 1.85-1.95 and an Abbe number of 25-35.
  • Conventional lanthanide optical glass components generally contain elements such as lead, arsenic, and cadmium. Because lead oxide can increase the refractive index and dispersion of optical glass, arsenic oxide has a clarifying effect, and cadmium oxide can improve the chemical stability of glass. However, as people's environmental awareness increases, such traditional optical glass containing harmful elements is gradually being replaced by environmentally-friendly optical glass.
  • CN1931755A discloses an optical glass having a refractive index greater than 1.80 and an Abbe number less than 30, and the content of Ti0 2 is 22 to 37% (weight percentage, the same below), at such a high Ti0 2 content, the glass It is easy to lose transparency, poor light absorption performance, easy to color glass, high softening temperature and high hardness of glass, which increases the difficulty of secondary pressing and machining.
  • the technical problem to be solved by the present invention is to provide an environmentally-friendly heavy flint optical glass having a relatively low content of Ti0 2 , which has a refractive index of 1.85 to 1.95, an Abbe number of 25 to 35, and a transformation.
  • the temperature is below 67 CTC.
  • the technical solution adopted by the invention to solve the technical problem is: environmentally friendly heavy flint optical glass, the weight percentage composition thereof comprises: La 2 0 3 : 30 ⁇ 50%, Ti0 2 : 3 ⁇ 15%, Nb 2 0 5 : 5 ⁇ 12%, a density of 4.56g/cm 3 or less, a refractive index of 1.85 ⁇ 1. 95, an Abbe number of 25 to 35, and a transition temperature of 67 CTC or less.
  • composition by weight is: Si0 2 : 2 ⁇ 15%, B 2 0 3 : 10 ⁇ 25%, La 2 0 3 : 30 ⁇ 50%, Zr0 2 : 2 ⁇ 15%, Ti0 2 : 3 ⁇ 15%, Nb 2 0 5 : 5 ⁇ 12%, SrO: greater than 5% but Less than 20%, BaO: 4 to 15%.
  • SiO 2 ⁇ 10%
  • Zr0 2 4 ⁇ : 10%
  • Si0 2 , B 2 0 3 , La 2 0 3 , Zr0 2 , Nb 2 0 5 , SrO, BaO is greater than or equal to 90%.
  • the composition of the environmentally friendly heavy flint optical glass is: Si0 2 : 2 ⁇ 15%, B 2 0 3 : 10 ⁇ 25%, La 2 0 3 : 30 ⁇ 50%, Zr0 2 : 2 ⁇ 15%, Ti0 2 : 3 to 15%, Nb 2 0 5 : 5 to 12%, SrO: more than 5% but less than 20%, and BaO: 4 to 15%.
  • a glass preform made of the above-mentioned environmentally friendly heavy flint optical glass made of the above-mentioned environmentally friendly heavy flint optical glass.
  • An optical instrument made of the above-mentioned environmentally friendly heavy flint optical glass has the beneficial effects that: by introducing SrO and BaO components simultaneously, the refractive index of the glass can be increased, the softening point can be lowered, and the chemical resistance can be improved; when the content of B 2 0 3 is high, the volatilization during melting can cause Glass constants and fringe fluctuations, reducing the quality stability of the glass, resulting in a complicated production process.
  • the present invention effectively eliminates various problems caused by B 2 0 3 by introducing a certain amount of SrO, especially when adding 12% or more 03, the optical glass can still be made with sufficient stability; the invention does not contain lead, arsenic, cadmium and other components caused by environmental pollution, it is made into a refractive index of 1. 85 ⁇ 1 95.
  • Optical glass with an Abbe number of 25 to 35 and a transition temperature of 670 ° C or less.
  • Si0 2 is a network-forming body oxide which forms glass.
  • the addition of a certain amount of SiO 2 increases the high-temperature viscosity of the glass and improves the devitrification resistance of the glass.
  • the content of SiO 2 is limited to 2 to 15%, and more preferably 2 to 10%.
  • B 2 0 3 is also an oxide forming glass, and B 2 0 3 is indispensable for a glass having a large content of La 2 0 3 as in the present invention. If the content is less than 10%, the melting property of the glass is poor, and the devitrification tendency of the glass is large; and when the content exceeds 25%, the refractive index of the glass is too low and the chemical stability of the glass is deteriorated, so that it is expected to be obtained.
  • the optical glass having an optical constant range and excellent chemical stability, the content of B 2 O 3 is limited to 10 to 25%, and more preferably 12 to 20%.
  • La 2 0 3 is a main component of high refractive optical glass, which can increase the refractive index of the glass and does not significantly increase the dispersion of the glass.
  • the combination of B 2 0 3 and La 2 0 3 can effectively Improve the devitrification resistance of the glass and improve the chemical stability of the glass.
  • the content of La 2 O 3 is less than 30%, the above effects are not obtained, but when the content exceeds 50%, the devitrification property of the glass is deteriorated, so the content thereof is limited to 30 to 50%, more preferably For 32 ⁇ 40%.
  • Zr0 2 has an effect of improving the resistance to devitrification of the glass and improving the chemical stability, and also functions to increase the refractive index and reduce the dispersion in the bismuth-based glass.
  • the content of Zr0 2 is limited to 2 to 15%, more preferably 4 to 10%.
  • Ti0 2 is effective for increasing the refractive index and dispersion of the glass, and can improve the water resistance of the glass and reduce the specific gravity of the glass.
  • Ti0 2 also functions to increase the high temperature viscosity of the glass and to improve the crystallization property of the glass. However, if the content is too high, the glass is colored. Therefore, the content of Ti0 2 is limited to 3 to 15%, preferably 5 ⁇ : 12%.
  • Nb 2 0 5 is an effective component for increasing the refractive index of glass.
  • the content of Nb 2 0 5 is limited to 5 to 12%, and more preferably 8 to 12%.
  • SrO has a prominent effect on promoting glass defoaming and inhibiting glass crystallization.
  • various problems caused by B 2 0 3 can be effectively eliminated, especially when 12% or more is added.
  • an optical glass having sufficient stability can be produced by introducing a certain amount of SrO.
  • the 5% but less than 15%, and the content of SrO is preferably more than 5% but less than 20%, more preferably more than 5.5% but less than 15%.
  • BaO is an effective component for adjusting the refractive index and Abbe number of glass, improving the chemical stability and thermal stability of glass. Simultaneous introduction of SrO and BaO can increase the refractive index of glass, lower the softening point of glass, and improve chemical resistance. However, when the content exceeds 15%, the Abbe number of the glass increases, and the devitrification tendency of the glass increases, so the content of BaO is preferably 4 to 15%, more preferably 6 to 12%.
  • the optical glass provided by the present invention adopts Si0 2 , B 2 0 3 , La 2 0 3 , Zr0 2 , Nb under the premise that the refractive index is 1.85 ⁇ 1. 95 and the Abbe number is 25 ⁇ 35.
  • the total amount of 2 0 5 , SrO, and BaO is greater than or equal to 85%; preferably, the total amount of Si0 2 , B 2 0 3 , La 2 0 3 , Zr0 2 , Nb 2 0 5 , SrO, and BaO is greater than or equal to 88.
  • the total amount of Si0 2 , B 2 0 3 , La 2 0 3 , Zr0 2 , Nb 2 0 5 , SrO, BaO is greater than or equal to 90%, such glass is not easily devitrified, and the light absorption performance is good.
  • the glass is not easy to be colored.
  • the softening temperature of the glass is low and the hardness is not high, which is very suitable for secondary pressing and machining.
  • the refractive index (nd) value is (_2 ° C / h) ⁇ (_ 6 ° C / h) annealing value, refractive index and Abbe number according to GB/T 7962. 1 1987 colorless optical glass test method Rate and dispersion coefficient test.
  • the transition temperature (Tg) is tested in accordance with the GB/T7962. 16-1987 colorless optical glass test method for linear expansion coefficient, transition temperature and sag temperature.
  • BP The sample to be tested is within a certain temperature range. For every 1 °C increase in temperature, on the expansion curve of the sample to be tested, the linear portion of the low temperature region and the high temperature region are extended to intersect, and the temperature corresponding to the intersection point.
  • the density is tested in accordance with GB/T 7962. 20-1987 Colorless Optical Glass Test Method Density Test Method.
  • the optical glass provided by the present invention has the following properties: density (P) is 4.56g/cm 3 or less; refractive index (nd) is 1. 85 ⁇ : 1. 95; Abbe number (vd) is 25 ⁇ 35; The transition temperature (Tg) is 670 ° C or less.
  • the present invention also provides an optical element formed by the optical glass described in the above technical solution in accordance with a method well known to those skilled in the art. Since the optical glass has a high refractive index, the optical element also has a high refractive index and can be applied to devices such as digital still cameras, digital video cameras, and camera phones.
  • optical glasses (Examples 1 to 30) shown in Tables 1 to 3 were weighed and mixed with ordinary raw materials (such as oxides, hydroxides, and optical glass) according to the ratios of the respective examples shown in Tables 1 to 3. Carbonate, nitrate and fluoride), the mixed raw materials are placed in a platinum crucible, melted at a temperature of 1100 to 130 CTC, and after melting, clarifying, stirring and homogenizing, no bubbles are formed and no undissolved The homogeneous molten glass of the material is formed by casting and annealing the molten glass in a mold.
  • ordinary raw materials such as oxides, hydroxides, and optical glass
  • compositions of Examples 1 to 30 of the present invention are shown in Tables 1 to 3 together with the results of refractive index (nd), Abbe number (vd), density (P), and glass transition temperature (Tg). In these tables, the composition of each component is expressed in % by weight. Table 1
  • the glass of the present invention the density () of 4. 56g / cm 3 or less; a refractive index (nd) of 95 1. 85 ⁇ 1; Abbe number (VD) was 25 ⁇ 35;
  • the transition temperature (Tg) is below 670 °C, and it does not contain environmentally polluting components such as lead, arsenic and cadmium.

Abstract

Environmentally-friendly heavy lanthanum flint optical glass contains the following components by weight percentage: La2O3：30%~50%, TiO2：3%~15%, and Nb2O5：5%~12%, and has a density of below 4.56g/ cm3, a refractive index of 1.85~1.95, an abbe number of 25~35, and a transformation temperature below 670°C. By adding the components SrO and BaO, the refractive index of the optical glass is enhanced, the softening point is reduced, and the chemical properties are improved. The optical glass does not contain components bringing pollution to the environment, such as lead, arsenic, and cadmium.

Description

环保重镧火石光学玻璃 技术领域  Environmental protection heavy flint optical glass
本发明涉及一种环保光学玻璃， 特别是涉及一种折射率为 1. 85-1. 95， 阿贝数为 25-35的环保重镧火石光学玻璃。  The invention relates to an environmentally friendly optical glass, in particular to an environmentally friendly heavy flint optical glass having a refractive index of 1.85-1.95 and an Abbe number of 25-35.
背景技术 Background technique
近年来， 随着光电行业的发展， 对光学元件提出了小型化、 轻量化、 高性能化的要求， 这就使得具有高折射、 中等色散、 低密度的重镧火石光 学玻璃的需求量越来越大。 为使光学玻璃具有上述性能， 玻璃组分中的 La203、 Nb205、 Ti02也应相应增大， 但这些组分会导致生产过程中玻璃液粘 度小、 析晶严重、 光学常数波动大、 对设备腐蚀大等后果， 使玻璃条纹质 量不高， 生产难度大。 传统的镧系光学玻璃组分中一般都含有铅、 砷、 镉 等元素， 因为氧化铅可以提高光学玻璃的折射率和色散， 氧化砷具有澄清 作用， 氧化镉可以改善玻璃的化学稳定性。然而随着人们环保意识的增强， 这类传统的含有有害元素的光学玻璃正逐渐被环保光学玻璃所取代。 CN1931755A公开了一种折射率大于 1. 80、 阿贝数小于 30的光学玻璃， 其 Ti02的含量为 22— 37% (重量百分比含量，以下同）， 在如此高的 Ti02含量 下， 玻璃易失透， 光吸收性能差， 玻璃易着色， 玻璃的软化温度高、 硬度 高， 增加了二次压型和机械加工的难度。 In recent years, with the development of the optoelectronic industry, the requirements for miniaturization, weight reduction, and high performance of optical components have been demanded, which has made the demand for heavy fluorite optical glass with high refraction, medium dispersion, and low density more and more. The bigger. In order to make the optical glass have the above properties, La 2 O 3 , Nb 2 0 5 , Ti0 2 in the glass component should also be correspondingly increased, but these components may cause the viscosity of the molten glass to be small, severe crystallization, and optical constant during the production process. The fluctuations are large, and the corrosion of the equipment is so great that the quality of the glass stripe is not high and the production is difficult. Conventional lanthanide optical glass components generally contain elements such as lead, arsenic, and cadmium. Because lead oxide can increase the refractive index and dispersion of optical glass, arsenic oxide has a clarifying effect, and cadmium oxide can improve the chemical stability of glass. However, as people's environmental awareness increases, such traditional optical glass containing harmful elements is gradually being replaced by environmentally-friendly optical glass. CN1931755A discloses an optical glass having a refractive index greater than 1.80 and an Abbe number less than 30, and the content of Ti0 2 is 22 to 37% (weight percentage, the same below), at such a high Ti0 2 content, the glass It is easy to lose transparency, poor light absorption performance, easy to color glass, high softening temperature and high hardness of glass, which increases the difficulty of secondary pressing and machining.
发明内容 Summary of the invention
本发明所要解决的技术问题是提供一种 Ti02的含量相对较低的环保重 镧火石光学玻璃， 该光学玻璃的折射率为 1. 85〜1. 95， 阿贝数为 25〜35， 转变温度为 67CTC以下。 The technical problem to be solved by the present invention is to provide an environmentally-friendly heavy flint optical glass having a relatively low content of Ti0 2 , which has a refractive index of 1.85 to 1.95, an Abbe number of 25 to 35, and a transformation. The temperature is below 67 CTC.
本发明解决技术问题所采用的技术方案是： 环保重镧火石光学玻璃， 其重量百分比组成含有： La203: 30〜50%、 Ti02 : 3〜15%、 Nb205: 5〜12%， 密度为 4. 56g/cm3以下， 折射率为 1. 85〜1. 95， 阿贝数为 25〜35， 转变温 度为 67CTC以下。 The technical solution adopted by the invention to solve the technical problem is: environmentally friendly heavy flint optical glass, the weight percentage composition thereof comprises: La 2 0 3 : 30~50%, Ti0 2 : 3 ~15%, Nb 2 0 5 : 5 ~ 12%, a density of 4.56g/cm 3 or less, a refractive index of 1.85~1. 95, an Abbe number of 25 to 35, and a transition temperature of 67 CTC or less.
进一歩的，其重量百分比组成为： Si02: 2〜15%、 B203: 10〜25%、 La203： 30〜50%、 Zr02 : 2〜15%、 Ti02 : 3〜15%、 Nb205: 5〜12%、 SrO: 大于 5%但 小于 20%、 BaO: 4〜15%。 Further, the composition by weight is: Si0 2 : 2 ~15%, B 2 0 3 : 10~25%, La 2 0 3 : 30~50%, Zr0 2 : 2 ~15%, Ti0 2 : 3 ~15%, Nb 2 0 5 : 5 ~12%, SrO: greater than 5% but Less than 20%, BaO: 4 to 15%.
进一歩的， 其中： SiO 2〜： 10% 、 Zr02 : 4〜： 10%。 Further, wherein: SiO 2~: 10%, Zr0 2 : 4~: 10%.
进一歩的， 其中 B203 12〜20%、 SrO ： 大于 5. 5%但小于 15%。 Further, wherein B 2 0 3 12~20%, SrO: is greater than 5.5% but less than 15%.
进一歩的， 其中 SrO 大于 5. 5%但小于 15%、 BaO: 6〜12%。  Further, where SrO is greater than 5.5% but less than 15%, BaO: 6 to 12%.
进一歩的， 其中 La203 32〜40<%、 Ti02 ： 5〜12<%、 Nb205 ： 8〜12%。 进一歩的， 其中 Si02、 B203、 La203、 Zr02、 Nb205、 SrO, BaO的合计 i 大于或等于 85%。 Further, wherein La 2 0 3 32~40<%, Ti0 2 : 5~12<%, Nb 2 0 5 : 8~12%. Further, where the total i of Si0 2 , B 2 0 3 , La 2 0 3 , Zr0 2 , Nb 2 0 5 , SrO, BaO is greater than or equal to 85%.
进一歩的， 其中 Si02、 B203、 La203、 Zr02、 Nb205、 SrO, BaO的合计: 大于或等于 88%。 Further, where the total of Si0 2 , B 2 0 3 , La 2 0 3 , Zr0 2 , Nb 2 0 5 , SrO, BaO is greater than or equal to 88%.
进一歩的， 其中 Si02、 B203、 La203、 Zr02、 Nb205、 SrO, BaO的合计: 大于或等于 90%。 Further, where the sum of Si0 2 , B 2 0 3 , La 2 0 3 , Zr0 2 , Nb 2 0 5 , SrO, BaO is greater than or equal to 90%.
环保重镧火石光学玻璃 其重量百分比组成为： Si02: 2〜15%、 B203: 10〜25%、 La203 ： 30〜50%、 Zr02: 2〜15%、 Ti02 : 3〜15%、 Nb205: 5〜12%、 SrO: 大于 5%但小于 20%、 BaO: 4〜15%。 The composition of the environmentally friendly heavy flint optical glass is: Si0 2 : 2 ~15%, B 2 0 3 : 10~25%, La 2 0 3 : 30~50%, Zr0 2 : 2 ~15%, Ti0 2 : 3 to 15%, Nb 2 0 5 : 5 to 12%, SrO: more than 5% but less than 20%, and BaO: 4 to 15%.
进—少 -的， 其中: Si02 2〜： 10% 。 Into-less-of, where: Si0 2 2 ~: 10%.
进—少 -的， 其中: Zr02: 4〜： 10%。 Into-less-of, where: Zr0 2 : 4~: 10%.
进—少 -的， 其中: B203 ： 12〜20%、 SrO ： 大于 5. 5%但小于 15%。 In the case of less than -5%, wherein: B 2 0 3 : 12 to 20%, SrO: greater than 5.5% but less than 15%.
进—少 -的， 其中: SrO ： 大于 5. 5%但小于 15%、 BaO: 6〜12%。  Progressive - less - of which: SrO : greater than 5. 5% but less than 15%, BaO: 6 to 12%.
进—少 -的， 其中: Ti02 ： 5〜12%。 Progressive - less - of which: Ti0 2 : 5 to 12%.
进—少 -的， 其中: La203: 32—40%, Ti02 ： 5〜12%、 Nb205 ： 8〜12%。 进一牛 Progressive - less - of which: La 2 0 3 : 32-40%, Ti0 2 : 5~12%, Nb 2 0 5 : 8~12%. Enter a cow
少的， 其中: Si02、 B203、 La203、 Zr02 Nb205、 SrO, BaO的合计Less, where: Si0 2 , B 2 0 3 , La 2 0 3 , Zr0 2 Nb 2 0 5 , SrO, BaO
：于或等于 85%。 : at or equal to 85%.
进一歩的， 其中： Si02、 B203、 La203、 Zr02、 Nb205、 SrO, BaO的合计： ：于或等于 88%。 Further, wherein: Si0 2 , B 2 0 3 , La 2 0 3 , Zr0 2 , Nb 2 0 5 , SrO, BaO total: : or equal to 88%.
进一歩的， 其中： Si02、 B203、 La203、 Zr02、 Nb205、 SrO, BaO的合计： ：于或等于 90%。 Further, wherein: Si0 2 , B 2 0 3 , La 2 0 3 , Zr0 2 , Nb 2 0 5 , SrO, BaO total: : or equal to 90%.
采用上述环保重镧火石光学玻璃制成的玻璃预制件。  A glass preform made of the above-mentioned environmentally friendly heavy flint optical glass.
采用上述环保重镧火石光学玻璃制成的光学元件。  An optical element made of the above-mentioned environmentally friendly heavy flint optical glass.
采用上述环保重镧火石光学玻璃制成的光学仪器。 本发明的有益效果是： 本发明通过同时引入 SrO和 BaO组分， 可提高 玻璃的折射率， 降低软化点， 改善耐化学性； 当 B203含量高时， 熔化过程 中的挥发会引起玻璃常数和条纹波动， 降低玻璃的质量稳定性， 从而导致 生产工艺复杂化，本发明通过引入一定量的 SrO,有效消除由 B203带来的各 种问题，特别是当加入 12%或更多的 03时，仍能可以制成具有足够稳定性 的光学玻璃； 本发明不含铅、 砷、 镉等对环境造成污染的组分， 仍可制成 折射率为 1. 85〜1. 95， 阿贝数为 25〜35， 转变温度为 670°C以下的光学玻 璃。 An optical instrument made of the above-mentioned environmentally friendly heavy flint optical glass. The invention has the beneficial effects that: by introducing SrO and BaO components simultaneously, the refractive index of the glass can be increased, the softening point can be lowered, and the chemical resistance can be improved; when the content of B 2 0 3 is high, the volatilization during melting can cause Glass constants and fringe fluctuations, reducing the quality stability of the glass, resulting in a complicated production process. The present invention effectively eliminates various problems caused by B 2 0 3 by introducing a certain amount of SrO, especially when adding 12% or more 03, the optical glass can still be made with sufficient stability; the invention does not contain lead, arsenic, cadmium and other components caused by environmental pollution, it is made into a refractive index of 1. 85~1 95. Optical glass with an Abbe number of 25 to 35 and a transition temperature of 670 ° C or less.
具体实施方式 detailed description
下面将描述本发明光学玻璃的各个组分， 除非另有说明， 各个组分的 含量都用重量 %表示。  The respective components of the optical glass of the present invention will be described below, and the contents of the respective components are expressed by weight % unless otherwise stated.
Si02是形成玻璃的网络生成体氧化物， 加入一定量的 Si02可增大玻璃 的高温粘度， 提高玻璃的耐失透性能。 当其含量低于 2%时， 效果不充分； 当其含量高于 15%时， 玻璃的熔融性变差， 气泡难以消除。 因此， Si02的含 量限定为 2〜15%， 更优选含量为 2〜： 10%。 Si0 2 is a network-forming body oxide which forms glass. The addition of a certain amount of SiO 2 increases the high-temperature viscosity of the glass and improves the devitrification resistance of the glass. When the content is less than 2%, the effect is insufficient; when the content is more than 15%, the meltability of the glass is deteriorated, and bubbles are difficult to be eliminated. Therefore, the content of SiO 2 is limited to 2 to 15%, and more preferably 2 to 10%.
B203也是形成玻璃的氧化物， 对本发明这样的 La203含量较多的玻璃来 说， B203是不可缺少的。 若其含量不足 10%时， 玻璃的熔化性能差， 玻璃的 失透倾向大； 而当其含量超过 25%时， 玻璃的折射率过低且玻璃的化学稳 定性变差， 为得到具有所期望的光学常数范围且具有优异的化学稳定性的 光学玻璃， B203的含量限定为 10〜25%， 更优选含量为 12〜20%。 B 2 0 3 is also an oxide forming glass, and B 2 0 3 is indispensable for a glass having a large content of La 2 0 3 as in the present invention. If the content is less than 10%, the melting property of the glass is poor, and the devitrification tendency of the glass is large; and when the content exceeds 25%, the refractive index of the glass is too low and the chemical stability of the glass is deteriorated, so that it is expected to be obtained. The optical glass having an optical constant range and excellent chemical stability, the content of B 2 O 3 is limited to 10 to 25%, and more preferably 12 to 20%.
La203是高折射光学玻璃的主要成分， 可以增加玻璃的折射率且不明显 提高玻璃的色散， 在本发明配方体系中， B203与 La203的组合存在， 可以有 效地提高玻璃的耐失透性能， 提高玻璃的化学稳定性。 当 La203的含量低于 30%时， 不能获得以上的效果， 但当其含量超过 50%时， 玻璃的析晶性能恶 化， 故将其含量限定为 30〜50%， 更优选的含量为 32〜40%。 La 2 0 3 is a main component of high refractive optical glass, which can increase the refractive index of the glass and does not significantly increase the dispersion of the glass. In the formulation system of the present invention, the combination of B 2 0 3 and La 2 0 3 can effectively Improve the devitrification resistance of the glass and improve the chemical stability of the glass. When the content of La 2 O 3 is less than 30%, the above effects are not obtained, but when the content exceeds 50%, the devitrification property of the glass is deteriorated, so the content thereof is limited to 30 to 50%, more preferably For 32~40%.
Zr02具有改善玻璃耐失透性、 提高化学稳定性的效果， 在镧系玻璃中， 还起到提高折射率和降低色散的作用。 当其含量低于 2%时， 起不到上述作 用； 当其含量高于 15%时， 会引起玻璃软化温度上升， 同时玻璃耐失透性 恶化。 因此 Zr02的含量限定为 2〜： 15%, 更优选为 4〜10%。 Ti02对于提高玻璃的折射率和色散很有效， 并能提高玻璃的耐水性， 降低玻璃比重。 在本发明中， Ti02还起到增大玻璃高温粘度以及改善玻璃 析晶性能的作用， 但其含量过高会使玻璃着色， 因此， Ti02 的含量限定为 3〜15%， 优选为 5〜： 12%。 Zr0 2 has an effect of improving the resistance to devitrification of the glass and improving the chemical stability, and also functions to increase the refractive index and reduce the dispersion in the bismuth-based glass. When the content is less than 2%, the above effect is not obtained; when the content is more than 15%, the glass softening temperature is increased, and the glass devitrification resistance is deteriorated. Therefore, the content of Zr0 2 is limited to 2 to 15%, more preferably 4 to 10%. Ti0 2 is effective for increasing the refractive index and dispersion of the glass, and can improve the water resistance of the glass and reduce the specific gravity of the glass. In the present invention, Ti0 2 also functions to increase the high temperature viscosity of the glass and to improve the crystallization property of the glass. However, if the content is too high, the glass is colored. Therefore, the content of Ti0 2 is limited to 3 to 15%, preferably 5 ~: 12%.
Nb205是提高玻璃折射率的有效成分， 当其含量不足 5%时， 玻璃的折射 率达不到设计目标， 而当其含量高于 12%时， 会导致玻璃软化温度升高， 同时使玻璃的透过率大幅下降， 因此 Nb205的含量限定为 5〜12%，更优选为 8〜12%。 Nb 2 0 5 is an effective component for increasing the refractive index of glass. When the content is less than 5%, the refractive index of the glass does not reach the design goal, and when the content is higher than 12%, the glass softening temperature rises, and at the same time, Since the transmittance of the glass is largely lowered, the content of Nb 2 0 5 is limited to 5 to 12%, and more preferably 8 to 12%.
SrO对促进玻璃消泡、抑制玻璃析晶具有突出作用，当 B203的含量高时， 可以有效地消除由 B203带来的各种问题， 特别是当加入 12%或更多的 B203 时， 可以通过引入一定量的 SrO, 仍能制成具有足够稳定性的光学玻璃。 但当 SrO含量高于 20%时， 玻璃熔制困难， 因此 SrO的含量优选为大于 5% 但小于 20%, 更优选为大于 5. 5%但小于 15%。 SrO has a prominent effect on promoting glass defoaming and inhibiting glass crystallization. When the content of B 2 0 3 is high, various problems caused by B 2 0 3 can be effectively eliminated, especially when 12% or more is added. At B 2 0 3 , an optical glass having sufficient stability can be produced by introducing a certain amount of SrO. The 5% but less than 15%, and the content of SrO is preferably more than 5% but less than 20%, more preferably more than 5.5% but less than 15%.
BaO是调整玻璃折射率和阿贝数、提高玻璃化学稳定性和热稳定性的有 效成分， SrO和 BaO 同时引入可提高玻璃折射率、 降低玻璃软化点、 改善 耐化学性。 但当其含量超过 15%时玻璃的阿贝数增加， 玻璃的失透倾向增 大， 因此 BaO的含量优选为 4〜： 15%, 更优选为 6〜12%。  BaO is an effective component for adjusting the refractive index and Abbe number of glass, improving the chemical stability and thermal stability of glass. Simultaneous introduction of SrO and BaO can increase the refractive index of glass, lower the softening point of glass, and improve chemical resistance. However, when the content exceeds 15%, the Abbe number of the glass increases, and the devitrification tendency of the glass increases, so the content of BaO is preferably 4 to 15%, more preferably 6 to 12%.
本发明提供的光学玻璃在保证折射率为 1. 85〜1. 95、阿贝数为 25〜35 的前提下， 本发明采用 Si02、 B203、 La203、 Zr02、 Nb205、 SrO, BaO的合计量 大于或等于 85%； 优选地， Si02、 B203、 La203、 Zr02、 Nb205、 SrO, BaO的合 计量大于或等于 88%； 更优选地， Si02、 B203、 La203、 Zr02、 Nb205、 SrO, BaO 的合计量大于或等于 90%, 这样的玻璃不易失透， 光吸收性能好， 玻璃不 易着色， 玻璃的软化温度低、 硬度不高， 非常适合二次压型和机械加工。 The optical glass provided by the present invention adopts Si0 2 , B 2 0 3 , La 2 0 3 , Zr0 2 , Nb under the premise that the refractive index is 1.85~1. 95 and the Abbe number is 25~35. The total amount of 2 0 5 , SrO, and BaO is greater than or equal to 85%; preferably, the total amount of Si0 2 , B 2 0 3 , La 2 0 3 , Zr0 2 , Nb 2 0 5 , SrO, and BaO is greater than or equal to 88. More preferably, the total amount of Si0 2 , B 2 0 3 , La 2 0 3 , Zr0 2 , Nb 2 0 5 , SrO, BaO is greater than or equal to 90%, such glass is not easily devitrified, and the light absorption performance is good. The glass is not easy to be colored. The softening temperature of the glass is low and the hardness is not high, which is very suitable for secondary pressing and machining.
下面将描述本发明的环保重镧火石光学玻璃的性能。  The performance of the environmentally friendly heavy flint glass of the present invention will be described below.
其中折射率 （nd) 值为 （_2°C/h) 〜 （_6°C/h) 的退火值， 折射率与 阿贝数按照 《GB/T 7962. 1一 1987无色光学玻璃测试方法 折射率和色散系 数》 测试。  The refractive index (nd) value is (_2 ° C / h) ~ (_ 6 ° C / h) annealing value, refractive index and Abbe number according to GB/T 7962. 1 1987 colorless optical glass test method Rate and dispersion coefficient test.
转变温度 （Tg) 按照 《GB/T7962. 16-1987无色光学玻璃测试方法线膨 胀系数、 转变温度和弛垂温度》测试， BP : 被测样品在一定的温度范围内， 温度每升高 1 °C， 在被测样品的膨胀曲线上， 将低温区域和高温区域直线 部分延伸相交， 其交点所对应的温度。 The transition temperature (Tg) is tested in accordance with the GB/T7962. 16-1987 colorless optical glass test method for linear expansion coefficient, transition temperature and sag temperature. BP: The sample to be tested is within a certain temperature range. For every 1 °C increase in temperature, on the expansion curve of the sample to be tested, the linear portion of the low temperature region and the high temperature region are extended to intersect, and the temperature corresponding to the intersection point.
密度按照《GB/T 7962. 20-1987无色光学玻璃测试方法 密度测试方法》 测试。  The density is tested in accordance with GB/T 7962. 20-1987 Colorless Optical Glass Test Method Density Test Method.
经过测试， 本发明提供的光学玻璃具有以下性能： 密度 （ P ) 为 4. 56g/cm3以下； 折射率 （nd) 为 1. 85〜： 1. 95; 阿贝数 （vd) 为 25〜35； 转变温度 （Tg) 为 670°C以下。 After testing, the optical glass provided by the present invention has the following properties: density (P) is 4.56g/cm 3 or less; refractive index (nd) is 1. 85~: 1. 95; Abbe number (vd) is 25~ 35; The transition temperature (Tg) is 670 ° C or less.
本发明还提供一种光学元件， 由上述技术方案所述的光学玻璃按照本 领域技术人员熟知的方法形成。 由于所述的光学玻璃具有高折射率， 所述 光学元件也具有高折射率， 可以应用于数码照相机、 数字摄像机、 照相手 机等设备。  The present invention also provides an optical element formed by the optical glass described in the above technical solution in accordance with a method well known to those skilled in the art. Since the optical glass has a high refractive index, the optical element also has a high refractive index and can be applied to devices such as digital still cameras, digital video cameras, and camera phones.
为了进一歩了解本发明的技术方案， 现在将描述本发明光学玻璃的实 施例。 应该注意到， 这些实施例没有限制本发明的范围。  In order to further understand the technical solution of the present invention, an embodiment of the optical glass of the present invention will now be described. It should be noted that these examples do not limit the scope of the invention.
表 1〜表 3中显示的光学玻璃 （实施例 1〜30) 是通过按照表 1〜表 3 所示各个实施例的比值称重并混合光学玻璃用普通原料 （如氧化物、 氢氧 化物、碳酸盐、硝酸盐和氟化物）， 将混合原料放置在铂金坩埚中， 在 1100 到 130CTC的温度内熔融， 并且在经熔化、 澄清、 搅拌和均化后， 得到没有 气泡及不含未溶解物质的均质熔融玻璃， 将此熔融玻璃在模具内铸型并退 火而成。  The optical glasses (Examples 1 to 30) shown in Tables 1 to 3 were weighed and mixed with ordinary raw materials (such as oxides, hydroxides, and optical glass) according to the ratios of the respective examples shown in Tables 1 to 3. Carbonate, nitrate and fluoride), the mixed raw materials are placed in a platinum crucible, melted at a temperature of 1100 to 130 CTC, and after melting, clarifying, stirring and homogenizing, no bubbles are formed and no undissolved The homogeneous molten glass of the material is formed by casting and annealing the molten glass in a mold.
本发明的实施例 1〜30的组成与折射率（nd)、阿贝数（vd)、密度（ P )、 玻璃转变温度 （Tg) 的结果一起在表 1〜表 3 中表示。 在这些表中， 各个 组分的组成是用重量 %表示的。 表 1  The compositions of Examples 1 to 30 of the present invention are shown in Tables 1 to 3 together with the results of refractive index (nd), Abbe number (vd), density (P), and glass transition temperature (Tg). In these tables, the composition of each component is expressed in % by weight. Table 1
实 施 例  Example
组分 1 2 3 4 5 6 7 8 9 10 Component 1 2 3 4 5 6 7 8 9 10
Si02 2. 12 14. 85 5. 21 3. 12 9. 86 3. 6 4. 2 8. 15 6. 12 7. 25Si0 2 2. 12 14. 85 5. 21 3. 12 9. 86 3. 6 4. 2 8. 15 6. 12 7. 25
B203 24. 96 10. 02 11. 3 10. 26 12. 2 14. 96 19. 87 16. 38 20. 61 13. 2B 2 0 3 24. 96 10. 02 11. 3 10. 26 12. 2 14. 96 19. 87 16. 38 20. 61 13. 2
La203 30. 02 32. 7 34. 48 49. 66 33. 98 39. 79 32. 01 31. 36 38. 15 35. 1La 2 0 3 30. 02 32. 7 34. 48 49. 66 33. 98 39. 79 32. 01 31. 36 38. 15 35. 1
Zr02 14. 68 2. 1 3. 62 3. 12 9. 79 4. 11 5. 3 6. 1 8. 34 7. 12
Figure imgf000007_0001
Zr02 14. 68 2. 1 3. 62 3. 12 9. 79 4. 11 5. 3 6. 1 8. 34 7. 12
Figure imgf000007_0001
Figure imgf000008_0001
通过表 1-3中的实施例可以看出，本发明玻璃的密度（ )为 4. 56g/cm3 以下；折射率（nd)为 1. 85〜1. 95； 阿贝数（vd)为 25〜35；转变温度（Tg) 为 670°C以下， 不含铅、 砷、 镉等对环境造成污染的组分。
Figure imgf000008_0001
Examples can be seen in Table 1-3, the glass of the present invention, the density () of 4. 56g / cm 3 or less; a refractive index (nd) of 95 1. 85~1; Abbe number (VD) was 25~35; The transition temperature (Tg) is below 670 °C, and it does not contain environmentally polluting components such as lead, arsenic and cadmium.

Claims

权利要求书 claims
I、 环保重镧火石光学玻璃， 其特征在于， 其重量百分比组成含有： La203: 30〜50%、 Ti02 : 3〜15%、 Nb205: 5〜12%， 密度为 4. 56g/cm3以下， 折射率为 1. 85〜1. 95， 阿贝数为 25〜35， 转变温度为 670°C以下。 1. Environmentally friendly heavy lanthanum flint optical glass, characterized in that its weight percentage composition contains: La 2 0 3 : 30~50%, Ti0 2: 3~15%, Nb 2 0 5 : 5~12%, and the density is 4 . 56g/ cm3 or less, the refractive index is 1.85~1.95, the Abbe number is 25~35, and the transition temperature is 670°C or less.
2、 如权利要求 1所述的环保重镧火石光学玻璃， 其特征在于， 其重量 百分比组成为： Si02: 2〜15%、 B203: 10〜25%、 La203 ： 30〜50%、 Zr02: 2 — 15%, Ti02: 3〜15%、 Nb205: 5〜12%、 SrO: 大于 5%但小于 20%、 BaO: 4〜 15%。 2. The environmentally friendly heavy lanthanum flint optical glass as claimed in claim 1, characterized in that its weight percentage composition is: Si02 : 2~15%, B203 : 10~25%, La203 : 30 ~50%, Zr0 2 : 2 — 15%, Ti0 2 : 3~15%, Nb 2 0 5 : 5~12%, SrO: more than 5% but less than 20%, BaO: 4~ 15%.
3、 如权利要求 2所述的环保重镧火石光学玻璃， 其特征在于， 其中： Si02 ： 2〜： 10% 、 Zr02 : 4〜： 10%。 3. The environmentally friendly heavy lanthanum flint optical glass as claimed in claim 2, wherein: Si0 2 : 2~: 10%, Zr0 2: 4~: 10%.
4、 如权利要求 2所述的环保重镧火石光学玻璃， 其特征在于， 其中： B203 ： 12〜20%、 SrO ： 大于 5. 5%但小于 15%。 4. The environmentally friendly heavy lanthanum flint optical glass as claimed in claim 2, wherein: B203 : 12~20% , SrO: greater than 5.5% but less than 15%.
5、 如权利要求 2所述的环保重镧火石光学玻璃， 其特征在于， 其中： SrO ： 大于 5. 5%但小于 15%、 BaO: 6〜12%。 5. The environmentally friendly heavy lanthanum flint optical glass as claimed in claim 2, wherein: SrO: greater than 5.5% but less than 15%, BaO: 6~12%.
6、 如权利要求 1或 2所述的环保重镧火石光学玻璃， 其特征在于， 其 中： La203: 32—40%, Ti02 ： 5〜12%、 Nb205 ： 8〜12%。 6. The environmentally friendly heavy lanthanum flint optical glass as claimed in claim 1 or 2, characterized in that: La 2 0 3 : 32-40%, Ti0 2 : 5~12%, Nb 2 0 5 : 8~12 %.
7、 如权利要求 2所述的环保重镧火石光学玻璃， 其特征在于， 其中： Si02、 B203、 La203、 Zr02、 Nb205、 SrO, BaO的合计量大于或等于 85%。 7. The environmentally friendly heavy lanthanum flint optical glass according to claim 2, wherein: the total amount of Si0 2 , B 2 0 3 , La 2 0 3 , Zr0 2 , Nb 2 0 5 , SrO, and BaO is greater than or equal to 85%.
8、 如权利要求 2所述的环保重镧火石光学玻璃， 其特征在于， 其中： Si02、 B203、 La203、 Zr02、 Nb205、 SrO, BaO的合计量大于或等于 88%。 8. The environmentally friendly heavy lanthanum flint optical glass according to claim 2, wherein: the total amount of Si0 2 , B 2 0 3 , La 2 0 3 , Zr0 2 , Nb 2 0 5 , SrO, and BaO is greater than Or equal to 88%.
9、 如权利要求 2所述的环保重镧火石光学玻璃， 其特征在于， 其中： Si02、 B203、 La203、 Zr02、 Nb205、 SrO, BaO的合计量大于或等于 90%。 9. The environmentally friendly heavy lanthanum flint optical glass according to claim 2, wherein: the total amount of Si0 2 , B 2 0 3 , La 2 0 3 , Zr0 2 , Nb 2 0 5 , SrO, and BaO is greater than Or equal to 90%.
10、环保重镧火石光学玻璃，其特征在于，其重量百分比组成为： Si02: 2〜15%、 B203: 10〜25%、 La203 ： 30〜50%、 Zr02: 2〜15%、 Ti02 : 3〜15%、 Nb205: 5〜12%、 SrO: 大于 5%但小于 20%、 BaO: 4〜15%。 10. Environmentally friendly heavy lanthanum flint optical glass, characterized in that its weight percentage composition is: Si0 2 : 2~15%, B 2 0 3 : 10~25%, La 2 0 3 : 30~50%, Zr0 2 : 2~15%, Ti02 : 3~15%, Nb205 : 5 ~12%, SrO: more than 5% but less than 20%, BaO: 4~15%.
I I、如权利要求 10所述的环保重镧火石光学玻璃，其特征在于，其中： Si02 ： 2〜： 10% 。 II. The environmentally friendly heavy lanthanum flint optical glass as claimed in claim 10, wherein: Si0 2 : 2~: 10%.
12、如权利要求 10所述的环保重镧火石光学玻璃，其特征在于，其中： Zr02: 4〜： 10%。 12. The environmentally friendly heavy lanthanum flint optical glass as claimed in claim 10, characterized in that: Zr0 2 : 4~: 10%.
13、如权利要求 10所述的环保重镧火石光学玻璃，其特征在于，其中： B203 ： 12〜20%、 SrO ： 大于 5. 5%但小于 15%。 13. The environmentally friendly heavy lanthanum flint optical glass as claimed in claim 10, wherein: B203 : 12~20% , SrO: greater than 5.5% but less than 15%.
14、如权利要求 10所述的环保重镧火石光学玻璃，其特征在于，其中： SrO ： 大于 5. 5%但小于 15%、 BaO: 6〜12%。 14. The environmentally friendly heavy lanthanum flint optical glass as claimed in claim 10, wherein: SrO: greater than 5.5% but less than 15%, BaO: 6~12%.
15、如权利要求 10所述的环保重镧火石光学玻璃，其特征在于，其中： 15. The environmentally friendly heavy lanthanum flint optical glass as claimed in claim 10, characterized in that:
Ti02 ： 5〜12%。 Ti0 2 : 5~12%.
16、如权利要求 10所述的环保重镧火石光学玻璃，其特征在于，其中： La203: 32〜40%、 Ti02 ： 5〜12%、 Nb205 ： 8〜12%。 16. The environmentally friendly heavy lanthanum flint optical glass according to claim 10, wherein: La 2 0 3 : 32~40%, Ti0 2 : 5~12%, Nb 2 0 5 : 8~12%.
17、如权利要求 10所述的环保重镧火石光学玻璃，其特征在于，其中： Si02、 B203、 La203、 Zr02、 Nb205、 SrO, BaO的合计量大于或等于 85%。 17. The environmentally friendly heavy lanthanum flint optical glass according to claim 10, wherein the total amount of Si0 2 , B 2 0 3 , La 2 0 3 , Zr0 2 , Nb 2 0 5 , SrO, and BaO is greater than or equal to 85%.
18、如权利要求 10所述的环保重镧火石光学玻璃，其特征在于，其中： Si02、 B203、 La203、 Zr02、 Nb205、 SrO, BaO的合计量大于或等于 88%。 18. The environmentally friendly heavy lanthanum flint optical glass according to claim 10, wherein the total amount of Si0 2 , B 2 0 3 , La 2 0 3 , Zr0 2 , Nb 2 0 5 , SrO, and BaO is greater than Or equal to 88%.
19、如权利要求 10所述的环保重镧火石光学玻璃，其特征在于，其中： Si02、 B203、 La203、 Zr02、 Nb205、 SrO, BaO的合计量大于或等于 90%。 19. The environmentally friendly heavy lanthanum flint optical glass according to claim 10, wherein the total amount of Si0 2 , B 2 0 3 , La 2 0 3 , Zr0 2 , Nb 2 0 5 , SrO, and BaO is greater than Or equal to 90%.
20、 采用如权利要求 1〜19中任一权利要求所述的环保重镧火石光学 玻璃制成的玻璃预制件。 20. Glass preforms made of environmentally friendly heavy lanthanum flint optical glass as claimed in any one of claims 1 to 19.
21、 采用如权利要求 1〜19任一权利要求所述的环保重镧火石光学玻 璃制成的光学元件。 21. Optical elements made of environmentally friendly heavy lanthanum flint optical glass as described in any one of claims 1 to 19.
22、 采用如权利要求 1〜19任一权利要求所述的环保重镧火石光学玻 璃制成的光学仪器。 22. Optical instruments made of environmentally friendly heavy lanthanum flint optical glass as described in any one of claims 1 to 19.
PCT/CN2013/084422 2012-09-29 2013-09-27 Environmentally-friendly heavy lanthanum flint optical glass WO2014048362A1 (en)

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CN201380048545.3A CN104736490A (en) 2012-09-29 2013-09-27 Environmentally-friendly heavy lanthanum flint optical glass
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WO2019143645A1 (en) * 2018-01-17 2019-07-25 Corning Incorporated High refractive index optical borate glass
WO2022055709A1 (en) * 2020-09-10 2022-03-17 Corning Incorporated Silicoborate and borosilicate glasses having high refractive index and high transmittance to blue light
WO2022055702A1 (en) * 2020-09-10 2022-03-17 Corning Incorporated Silicoborate and borosilicate glasses having high refractive index and low density

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CN104341100B (en) * 2013-08-05 2018-10-19 成都光明光电股份有限公司 High-refractive and high-dispersive optical glass, optical element and optical instrument
JP6973902B2 (en) * 2016-09-27 2021-12-01 株式会社オハラ Optical glass, preforms and optics
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US20190233323A1 (en) * 2016-10-03 2019-08-01 Ohara Inc. Optical glass, preform, and optical element
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WO2022055709A1 (en) * 2020-09-10 2022-03-17 Corning Incorporated Silicoborate and borosilicate glasses having high refractive index and high transmittance to blue light
WO2022055702A1 (en) * 2020-09-10 2022-03-17 Corning Incorporated Silicoborate and borosilicate glasses having high refractive index and low density
US11802073B2 (en) 2020-09-10 2023-10-31 Corning Incorporated Silicoborate and borosilicate glasses with high refractive index and low density

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JP2015532252A (en) 2015-11-09
CN104736490A (en) 2015-06-24

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