WO2015024351A1 - Optical glass of high refractive index and low dispersion and manufacture method therefor - Google Patents

Optical glass of high refractive index and low dispersion and manufacture method therefor Download PDF

Info

Publication number
WO2015024351A1
WO2015024351A1 PCT/CN2013/090316 CN2013090316W WO2015024351A1 WO 2015024351 A1 WO2015024351 A1 WO 2015024351A1 CN 2013090316 W CN2013090316 W CN 2013090316W WO 2015024351 A1 WO2015024351 A1 WO 2015024351A1
Authority
WO
WIPO (PCT)
Prior art keywords
glass
less
optical glass
optical
refractive index
Prior art date
Application number
PCT/CN2013/090316
Other languages
French (fr)
Chinese (zh)
Inventor
王自力
黄�俊
Original Assignee
成都尤利特光电科技有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 成都尤利特光电科技有限公司 filed Critical 成都尤利特光电科技有限公司
Publication of WO2015024351A1 publication Critical patent/WO2015024351A1/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/062—Glass compositions containing silica with less than 40% silica by weight
    • 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
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B2215/00—Press-moulding glass
    • C03B2215/66—Means for providing special atmospheres, e.g. reduced pressure, inert gas, reducing gas, clean room
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P40/00—Technologies relating to the processing of minerals
    • Y02P40/50—Glass production, e.g. reusing waste heat during processing or shaping
    • Y02P40/57—Improving the yield, e-g- reduction of reject rates

Definitions

  • the present invention relates to a high refractive, low dispersion optical glass, and a method of making the same. More specifically, the present invention can provide an optical glass having an optical property of a refractive index of 1.81 or more, an Abbe number (vd) of 46 or more but less than 48, and good stability and high transmission. Background technique
  • Patent Documents CN101041552A, CN1792918A.
  • the Abbe number (vd) it is within the scope of the present invention, as in the patent document: CN101012102A, the Abbe number (vd) is 46 to 48, but the refractive index (nd) is only 1.80 or less. Moreover, in order to maintain glass stability, Ge0 2 and Ga 2 0 3 components which are very expensive are introduced, and mass production and high transmission requirements cannot be achieved.
  • the present invention is made to achieve the above optical characteristics and to eliminate the high devitrification resistance of the glass surface of the high refractive glass at the time of molding, and the object thereof is not only to provide an optical glass having such optical characteristics, but also to introduce no price.
  • the particularly expensive raw material component enables stable mass production while exhibiting good reproducibility and is available for secondary hot press forming.
  • another object of the present invention is to achieve and achieve high transmission of the optical lens by optimizing the design to meet the high definition requirements of the imaging optical system of the high-end SLR camera, digital camera, and camera.
  • the present invention has been found to be able to adjust different ratios of Si0 2 and B 2 0 3 by continuous repeated research and process tests, and simultaneously to La 2 0 3 , Gd 2 0 3 , Y 2 0 3 , optimized ratio of components such as Ta 2 0 5 , Nb 2 0 5 , Zr0 2 , ZnO , Sn0 2 and the introduction of BaO, W0 3 , Li 2 0 components, and adjustment of properties, and not introduced Based on the very expensive Ge0 2 and Ga 2 03 components, not only the optical properties of the above range are achieved, but also the glass surface has good resistance to devitrification, high transmission, and maximum amplitude. Secondary hot pressing. The present invention has been completed for this purpose.
  • optical glass of the present invention comprises the following mole percent components:
  • ZnO is greater than 0 but less than 10%
  • Sn0 2 is greater than 0 but less than 2.5%
  • ZnO is greater than oi" Sn0 2 is greater than 0 but less than 2%
  • ZnO is greater than 0 but less than 8.12%
  • Sn0 2 is greater than 0 but less than 1.85%
  • the molar ratio of Gd 2 0 3 is greater than 6.0%.
  • the optical glass has a refractive index (nd) greater than 1.81 and an Abbe number (vd) greater than 46 and less than
  • the upper limit of the internal transmission ( ⁇ ⁇ 80) of the optical glass is less than 350 nm.
  • the optical glass has a density of 5.10 g/cm 3 or less.
  • the optical glass has a transition temperature (Tg) of 690 ° C or less and a liquidus temperature (LT) of 1150.
  • the present invention also provides an optical element which is prepared from the aforementioned optical glass.
  • the optical glass blank of the present invention can be produced according to a conventional method or can be produced as follows: melted into a uniform glass liquid by heating, flows into a molding die through a platinum leakage device, and is protected by a closed heating cover and an inert gas.
  • the airflow formed on the outer sides of the leaking point area isolates the dust in the atmosphere from falling into the glass forming surface, eliminates surface defects and increases the surface forming viscosity of the glass, and solidifies into a constant thickness and width, and manufactures the blank material formed by the aforementioned optical glass. .
  • it has lower dispersion and large Abbe number characteristics than existing high-refraction, low-dispersion optical glass. It also has good surface devitrification resistance and can achieve stable mass production under the protection of an inert gas.
  • the optical glass of the present invention has a refractive index (nd) of 1.81 or more, an Abbe number (vd) of 46 or more, but less than 48, and also has a high transmittance, and when directly molded into a raw material in a glass liquid state,
  • the surface has good resistance to devitrification, and on the basis of good stability and reproducibility, it is made into various types of rough materials. Further, it has an optical element which is subjected to repeated hot pressing without repeated devitrification during the secondary hot pressing process, and is formed into various specifications.
  • the glass components constituting the glass 1 to 7 included in the optical glass of the present invention, and the percentage of each component introduced and the total content of each group, which are respectively expressed by (mol%), will be described in detail below.
  • the optical glass of the present invention comprises SiO ⁇ PB 2 0 3 as a component forming a glass network, and contains La 2 O 3 , Gd 2 0 3 , Y 2 0 3 , Ta as refractive index. 2 0 5 , Zr0 2 and other components, while limiting the introduction amount of BaO, W0 3 , Li 2 0.
  • 810 2 is an important component for forming a glass network, and is also a component which most effectively expands the range of glass formation and enhances resistance to devitrification.
  • the amount of SiO ⁇ introduced is less than 8%, the above effects are not obtained.
  • the amount of introduction exceeds 20%, not only the refractive index is lowered, but also the solubility of the melt is deteriorated, and it is difficult to form a high quality glass. Therefore, the amount of SiO ⁇ introduced is limited to the range of 8 to 20%, preferably 9 to 19%, more preferably 10 to 18%.
  • B 2 0 3 is an important component which is most effective for forming a glass network component and which can effectively improve the solubility of the glass, lower the melting temperature and enhance the anti-devitrification resistance of the glass.
  • the amount of introduction of B 2 0 3 is limited to the range of 35 to 50%, preferably 36 to 49%, particularly preferably 37 to 48.6%.
  • the ratio of the amount of SiO ⁇ introduced to the amount of introduction of B203 is more than 0.22, in order to further increase the viscosity of the glass, especially the surface viscosity during molding, More preferably, it is more than 0.28, still more preferably more than 0.31.
  • La 2 O 3 is an important component for increasing the refractive index and controlling the dispersion value within a desired range, and is used for improving the stability of the glass and reducing the probability of devitrification of the glass surface.
  • the introduction amount of La 2 0 3 is less than 10%, it will be difficult to achieve the above effects.
  • the introduction amount of 203 La is controlled within the range of 10 to 20%, preferably 11-18%, particularly preferably in the range of 11.5 to 16.5%.
  • Gd 2 0 3 is an oxide having the same action as La 2 O 3 , and is the most important component having an improved refractive index and a significant increase in the anti-devitrification of the glass surface, not only It also has the effect of improving the transmission of the visible light region and the stability of the glass.
  • the amount of introduction is less than 6%, it is difficult to obtain the above effects. If the amount introduced exceeds 18%, the glass will become extremely unstable, and the devitrification will also deteriorate. Therefore, the amount of introduction of Gd 2 0 3 is controlled within the range of 6 to 16%, more preferably 7 to 15%, and particularly preferably, the amount of introduction of Gd 2 0 3 is 7.5 to 14.8%.
  • Y 2 0 3 which is a rare earth oxide of the same group has the same effect of increasing the refractive index and lowering the dispersion, similar to La 2 0 3 .
  • the introduction amount of Y 2 0 3 is controlled in the range of 0 to 8%, preferably 0 to 6% or less.
  • the total amount of oxide introduced compared with the rare earth oxide containing a single component, simultaneously containing a plurality of rare earth oxides Gd 2 0, La 2 0 3 , Y 2 0 3 components, not only can significantly improve the stability of the glass, and can increase the rare earth The total amount of oxide introduced.
  • the glass of the present invention if it contains L3 ⁇ 40 3 , Gd 2 0 3 , Y 2 0 3 and the like having an increased refractive index, the refractive index can be greatly improved and the stability of the glass can be improved. If the total introduction amount exceeds 35%, the glass resistance to devitrification will deteriorate. Therefore, the total amount of introduction of (La 2 0 3 + Gd 2 0 3 + Y 2 0 3 ) is controlled within 35%, preferably 23 to 35%, more preferably 23 to 33%.
  • Ta 2 0 5 is an essential component having greatly improved stability of the glass, decrease the liquidus temperature and increase the refractive index and optical constants to achieve the desired range.
  • the introduction amount of ⁇ 0 5 is less than 1%, it is difficult to achieve the above effect.
  • the introduction amount of Ta 2 0 5 exceeds 6%, the stability of the glass high temperature range is lowered, the specific gravity of the glass is also increased, and the raw material cost is also increased.
  • the introduction amount of ⁇ 0 5 is limited to the range of 1 to 5%, and the lower limit within the above range is preferably 1.5% or more, and the upper limit is preferably 5% or less, more preferably 4% or less, Ta 2 0
  • the amount of introduction of 5 is particularly preferably in the range of 2 to 3.5%.
  • Nb 2 0 5 is a component for increasing the refractive index, improving the stability of the glass, and improving the resistance to devitrification of the glass.
  • the amount of Nb is introduced 205 exceeds 5%, the glass will not only increase the dispersion value, and the glass devitrification resistance deteriorates, through the glass will be reduced. Therefore, the amount of introduction is limited to 0 to 3.0%, preferably 0 to 2.5%, more preferably 0 to 2.0% or less.
  • Zr0 2 is a component that improves glass stability and resistance to devitrification, and increases refractive index and stability. When the amount of introduction exceeds 12%, the solubility of the glass deteriorates and the stability decreases. Therefore, the introduction amount of Zr0 2 is limited to 12%, preferably in the range of 4 to 12%, more preferably 5 to 11%. Inside.
  • ZnO is a component which lowers the transition temperature, increases glass solubility, and is resistant to devitrification of glass.
  • the amount of introduction of ZnO is controlled in the range of 0.5 to 10%, preferably 1.5 to 9.0%, more preferably 1.5 to 8.5%.
  • Sn0 2 and Zr0 2 is the effect of the same action, when the amount is introduced, the glass surface can significantly improve anti-devitrification resistance, and to decrease the liquidus temperature.
  • the introduction amount of Sn0 2 exceeds 3%, the glass fusibility is deteriorated, the intrinsic quality of the glass is deteriorated, the transmission on the short-wavelength side of the glass is also lowered, and the glass transition temperature (Tg) is rapidly increased. Therefore, the upper limit of the amount of introduction of Sn0 2 is limited to 3.0%, preferably 0.5 to 3.0%, more preferably 0.5 to 2.5%, still more preferably 0.5 to 2.0%.
  • W0 3 is a component that enhances resistance to devitrification, increases glass stability, and refractive index.
  • the amount of introduction of W0 3 exceeds 2%, the tendency of the glass to be colored is significantly deepened, the transmittance is lowered, and the glass dispersion value is also increased. Therefore, the amount of introduction is limited to 2%, preferably 0 to 2%, more preferably 0 to 1.5%, still more preferably 0 to 0.5% or less.
  • the proper introduction of BaO can improve the solubility of glass and improve the stability, and has the effect of reducing the coloration of glass.
  • BaO compared with the similarly acting ZnO, BaO has less effect on improving solubility and improving resistance to devitrification. Therefore, the introduction amount of BaO is limited to the range of 0 to 3.0%, preferably 0 to 2.0%, more preferably 0. ⁇ 1.85%.
  • Li 2 0 is a component which lowers the glass transition temperature, increases the solubility of the glass, lowers the melting temperature, and increases the viscosity of the glass at the time of molding.
  • the amount of introduction of Li 2 0 exceeds 3%, the devitrification resistance of the glass and the devitrification resistance of the glass surface at the time of molding are deteriorated, and the refractive index is also lowered. Therefore, the amount of introduction thereof is limited to the range of 0 to 3.0%, preferably 0 to 2.0%, more preferably 0 to 1.5% or less.
  • Sb 2 0 3 is an optional additive used as a clarifying agent, and by a small amount of addition, light absorption due to reduction of Fe impurities can be alleviated, and glass coloring can be alleviated. If added in excess, it will have the opposite effect and will also deteriorate the intrinsic quality of the glass. Therefore, it is preferable to control the amount of introduction thereof to 0 to 0.3%, more preferably 0 to 0.2% or less.
  • the devitrification resistance of the glass surface is improved, and the stability of glass production is improved.
  • the introduction amount of the ZrO 2 , ZnO , and SnO 2 components is 98% or more, and the introduction amount of the W0 3 , BaO, and Li 2 0 components is 2% or less, and the total introduction amount thereof is 100%.
  • the optical glass of the present invention has a refractive index (nd) of 1.81 or more and an Abbe number (vd) of 46 to 48.
  • nd refractive index
  • vd Abbe number
  • the refractive index (nd) of the present invention is preferably at least 1.81, more preferably 1.816 or 1.821. In order to achieve manufacturing stability, it is desirable to limit the refractive index (nd) to 1.83 or less, and more desirably to be 1.82 or less.
  • the optical glass of the present invention preferably has an Abbe number (vd) of 46 to 48, more preferably 46.5 to 47.5.
  • the blank of the optical glass of the present invention is mainly used for softening pressing by secondary heating to obtain an optical element, or by cold working, and processed to form an optical lens.
  • the optical glass according to the present invention by innovation of the composition and molding process, can effectively control the glass surface devitrification at the time of molding, and control the internal permeation (wavelength ⁇ ⁇ 80 ) to be below 350 nm, preferably 348 nm or less.
  • the internal transmission (wavelength ⁇ ⁇ 5 ) is controlled to be 300 nm or less, preferably 290 nm or less. Since the optical glass of the present invention has a transmission of 90% or more and a ( ⁇ ⁇ 5 ) shift in the short-wave direction in the ( ⁇ ⁇ 80) wavelength range, it is suitable as various high-definition optical lenses.
  • the premise of achieving stability in manufacturing is that the glass has a low liquidus temperature, and when the devitrification resistance of the glass is lowered, the liquidus temperature thereof is sharply increased, and the glass stability is deteriorated. Therefore, the liquidus temperature of the optical glass of the present invention is controlled to be 1150 ° C or lower, more preferably 1140 ° C or lower.
  • Tables 1 and 2 show the compositions of Comparative Examples NQA to N 2 C of the glass compositions of Examples NQ 1 to N27 of the optical glass of the present invention and the same high refractive glass as the glass of the present invention.
  • the following is an indication of the optical glass obtained by annealing the -4.0/h annealing rate and cooling, the refractive index (nd), the Abbe number (vd), and the internal transmission ( ⁇ ⁇ 80 ).
  • the results of measurement of ⁇ ( ⁇ ⁇ 5 ), density ( ⁇ ), transition temperature (Tg), and liquidus temperature (LT) are shown in Tables 1 and 2.
  • Raw materials such as various oxides, carbonates and nitrates corresponding to the raw materials of the respective components are calculated and mixed according to the compositions of the respective examples and comparative examples, and the mixture is mixed and prepared into a platinum container. After melting, stirring, clarifying and homogenizing at a temperature of 1250 ° C to 1370 ° C, it is poured into a conventional mold or leaked into a mold with inert gas protection to form samples and blanks of various sizes.
  • the specific manufacturing method of the rough material through the molten glass liquid, through the platinum leakage device, into the preheated mold for diffusion molding, and through the microporous air flow device on both sides of the leakage point, the inert surface is introduced above the molding surface.
  • Gas which separates the dust from the atmosphere and the tiny particles in the exchange of hot and cold airflow, prevents it from falling into the glass forming surface, and at the same time, through the adjustment and transformation of the airflow conversion device, the tiny particles in the hot and cold airflow are under the action of the pressurized gas.
  • the above state is carried out by using a forming heating hood device for sealing the heat generating body in the inner cavity of the silicon carbide, heating the upper and both sides and the connecting portion without using the usual direct surface heating or flame heating.
  • the blank material produced by the invention is made under the protection of an inert gas, and the surface of the molding surface can achieve good cleanliness, so they have high utilization value.
  • the refractive index (nd) and the Abbe number (vd) were measured to obtain a glass sample at an annealing rate of -4.0/h.
  • Glass transition temperature (Tg) Measured using a thermal analyzer unit and measured at a heating rate of 4.0 ° C / min.
  • Liquidus temperature (LT) 500g glass frit was added to a 0.3L platinum container, set in a test furnace with a 10°C interval, and kept at different temperatures for 2h to obtain a sample. When it appears, the lowest temperature without crystal grains is confirmed as the liquidus temperature (LT).
  • Example (mol%) 500g glass frit was added to a 0.3L platinum container, set in a test furnace with a 10°C interval, and kept at different temperatures for 2h to obtain a sample. When it appears, the lowest temperature without crystal grains is confirmed as the liquidus temperature (LT).
  • the optical glass N2 l ⁇ N 2 7 of the embodiment of the present invention has optical characteristics in the above range, that is, the refractive index (nd) is 1.81239 1.82570, Abbe number (vd) 46.23-47.49, the upper limit of the glass inner transmission is 350 nm or less, the lower limit is 293 nm or less, the specific gravity is lower than 5.10, the transition temperature (Tg) is 690 ° C or lower, and the liquidus temperature (LT) is 1150 ° C or lower.
  • the refractive index (nd) is 1.81239 1.82570
  • Abbe number (vd) 46.23-47.49 Abbe number 46.23-47.49
  • the upper limit of the glass inner transmission is 350 nm or less
  • the lower limit is 293 nm or less
  • the specific gravity is lower than 5.10
  • the transition temperature (Tg) is 690 ° C or lower
  • the liquidus temperature (LT) is 1150 ° C or lower.
  • the Abbe number (vd) belongs to the range of the present invention
  • the refractive index (nd) is lower than the range of the present invention, and is only 1.79. Therefore, it does not belong to the optical characteristics of the present invention.
  • the refractive index (nd) is 1.81 or more
  • the Abbe number (vd) is 42.6 or less, which is far below the range of the present invention. Therefore, it does not belong to the optical characteristics of the present invention.
  • the C case also contains a very expensive Ge0 2 component and low transmittance, which is not only difficult to achieve mass production, but also does not have such high refractive, low dispersion optical characteristics, and is not suitable for high-end SLR cameras, digital cameras. And the optical system design of the camera. Industrial applicability
  • optical glass blank can be formed into various optical components such as cold cutting and secondary hot pressing, and is made into an optical lens for use in a high-end SLR camera, digital In the optical system of the camera and camera. Suitable for a wide range of applications in industry.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Glass Compositions (AREA)

Abstract

Disclosed is an optical glass of a high refractive index and a low dispersion containing a Ta2O5 component. The optical glass has a good anti-devitrification property and can realize stable production. The glass has a refractive index (nd) of more than 1.81, an Abbe number (Vd) of above 46 but less than 48; the upper limit of internal transmittance (λƮ80) of the glass is below 350 nm; and the liquidus temperature is below 1150°C.

Description

高折射、 低色散光学玻璃及其制造方法  High refractive, low dispersion optical glass and manufacturing method thereof
技术领域 Technical field
本发明涉及一种高折射、 低色散的光学玻璃， 以及制造该光学玻璃的方 法。 更具体的讲， 本发明可提供一种具有其折射率 1.81以上、 阿贝数 （vd) 为 46以上但不足 48的光学特性， 并具有良好稳定性和高透过的光学玻璃。 背景技术  The present invention relates to a high refractive, low dispersion optical glass, and a method of making the same. More specifically, the present invention can provide an optical glass having an optical property of a refractive index of 1.81 or more, an Abbe number (vd) of 46 or more but less than 48, and good stability and high transmission. Background technique
近年来， 随着单反相机、摄像机的快速普及和在人们生活中的广泛使用， 作为更高端的单反相机、 数码相机及摄像机也逐渐在人们的生活中被使用。 其作为这类相机和摄像机的光学系统所使用的高折射率光学玻璃， 它不仅要 达到和满足折射率的要求， 同时还以多片不同阿贝数的透镜进行组合， 以缩 小光学系统的色差。 不仅如此， 在高端的摄像光学系统中， 为校正像差需采 用多片光学透镜，而多片镜头的组合叠加将使光学系统的光透过降低。因此， 在满足光学指标的同时， 也必须使每一片透镜都具有高的透过。 以不同的高 折射率、 不同的阿贝数， 以及更高透过率的光学玻璃来满足全方位光学系统 的设计要求。  In recent years, with the rapid spread of SLR cameras and cameras and their widespread use in people's lives, as a higher-end SLR camera, digital camera and video camera, they are gradually being used in people's lives. It is a high-refractive-index optical glass used in the optical systems of such cameras and cameras. It not only meets and satisfies the requirements of refractive index, but also combines lenses with different Abbe numbers to reduce the chromatic aberration of the optical system. . Moreover, in high-end imaging optical systems, multiple optical lenses are required to correct aberrations, and the combined superposition of multiple lenses reduces the light transmission of the optical system. Therefore, it is necessary to make each lens have high transmission while satisfying the optical index. Optical glass with different high refractive index, different Abbe number, and higher transmittance meets the design requirements of omnidirectional optical systems.
因此， 开发这种具有高折射率、 或更低色散的光学玻璃对于高端单反相 机光学系统的设计用途是非常广泛的。  Therefore, the development of such an optical glass having a high refractive index or lower dispersion is very broadly designed for use in a high-end SLR optical system.
作为这类高折射率、 低色散的光学玻璃， 目前已知的仅有折射率 （nd) 在 1.81以上的， 而阿贝数 （vd) 则低于 46以下， 不属于本发明的范围。 如 专利文献： CN101041552A、 CN1792918A。  As such a high refractive index, low dispersion optical glass, it is currently known that only the refractive index (nd) is 1.81 or more, and the Abbe number (vd) is less than 46, which is not within the scope of the present invention. For example, Patent Documents: CN101041552A, CN1792918A.
而作为阿贝数 （vd) 属于本发明范围的， 如专利文献： CN101012102A, 阿贝数 （vd) 为 46~48的， 但折射率 （nd)仅为 1.80以下。 且还为了维持玻 璃稳定性而引入价格非常昂贵的 Ge02、 Ga203成分， 无法实现量产和达到高 透过的要求。 As the Abbe number (vd), it is within the scope of the present invention, as in the patent document: CN101012102A, the Abbe number (vd) is 46 to 48, but the refractive index (nd) is only 1.80 or less. Moreover, in order to maintain glass stability, Ge0 2 and Ga 2 0 3 components which are very expensive are introduced, and mass production and high transmission requirements cannot be achieved.
发明内容 Summary of the invention
本发明是为实现上述光学特性和消除这种高折射玻璃在成型时玻璃表面 具有良好的抗失透性而进行的， 其目的不仅是提供具有这种光学特性的光学 玻璃， 而且在不引入价格特别昂贵的原料组分， 能实现稳定量产， 同时显示 出良好的再现性， 并可供二次热压成型之用。  The present invention is made to achieve the above optical characteristics and to eliminate the high devitrification resistance of the glass surface of the high refractive glass at the time of molding, and the object thereof is not only to provide an optical glass having such optical characteristics, but also to introduce no price. The particularly expensive raw material component enables stable mass production while exhibiting good reproducibility and is available for secondary hot press forming.
不仅如此， 本发明的另一目的， 是通过优化设计， 以达到和实现光学透 镜的高透过， 最大满足高端单反相机、 数码相机、 摄像机的成像光学系统高 清晰度要求。 本发明为达到上述要求， 在经过不断的反复研究及工艺试验中发现， 能 够通过对 Si02、 B203含量的不同比例调整， 同时对 La203、 Gd203、 Y203、 Ta205、 Nb205、 Zr02、 ZnO 、 Sn02等组分的优化配比和 BaO、 W03、 Li20 组分的引入、 并对性能的调整， 并在不引入价格非常昂贵的 Ge02、 Ga203 成分的基础上 ，不仅达到了具有上述范围的光学特性，且还实现了玻璃表面 具有良好的抗失透性、 高的透过、 并能最大幅度满足二次热压。 为此完成了 本发明。 Moreover, another object of the present invention is to achieve and achieve high transmission of the optical lens by optimizing the design to meet the high definition requirements of the imaging optical system of the high-end SLR camera, digital camera, and camera. In order to achieve the above requirements, the present invention has been found to be able to adjust different ratios of Si0 2 and B 2 0 3 by continuous repeated research and process tests, and simultaneously to La 2 0 3 , Gd 2 0 3 , Y 2 0 3 , optimized ratio of components such as Ta 2 0 5 , Nb 2 0 5 , Zr0 2 , ZnO , Sn0 2 and the introduction of BaO, W0 3 , Li 2 0 components, and adjustment of properties, and not introduced Based on the very expensive Ge0 2 and Ga 2 03 components, not only the optical properties of the above range are achieved, but also the glass surface has good resistance to devitrification, high transmission, and maximum amplitude. Secondary hot pressing. The present invention has been completed for this purpose.
本发明的结果还发现， 将 Si02、 B203含量之比逐渐增大、 Gd203引入量 大于 6.0%时， 玻璃稳定性和玻璃表面抗失透性得到完美再现， 进一步完成了 本发明。 As a result of the present invention, it has been found that when the ratio of the content of Si0 2 and B 2 0 3 is gradually increased and the amount of introduction of Gd 2 0 3 is more than 6.0%, the glass stability and the glass surface devitrification resistance are perfectly reproduced, and the completion is further completed. this invention.
本发明光学玻璃， 它包含如下摩尔百分比的成分：  The optical glass of the present invention comprises the following mole percent components:
Si02 8-20% Si0 2 8-20%
B203 35-50% 其中， Si02/ B203 > 0.22 B 2 0 3 35-50% where Si0 2 / B 2 0 3 > 0.22
La203 10-20% La 2 0 3 10-20%
Gd203 6-16% Gd 2 0 3 6-16%
Y203 0- 8% 其中， （Gd203+ La203 +Y203)
Figure imgf000003_0001
23~35%Y 2 0 3 0- 8% where (Gd 2 0 3 + La 2 0 3 + Y 2 0 3 )
Figure imgf000003_0001
23~35%
Ta205 1- 5% Ta 2 0 5 1- 5%
Nb205 0-3% Nb 2 0 5 0-3%
Zr02 4-12% Zr0 2 4-12%
ZnO 大于 0但小于 10%  ZnO is greater than 0 but less than 10%
Sn02 大于 0但小于 2.5% Sn0 2 is greater than 0 but less than 2.5%
BaO 0-3%  BaO 0-3%
W03 0-2% W0 3 0-2%
Li20 0-3% Li 2 0 0-3%
Sb20, 0~0.5%。 Sb 2 0, 0~0.5%.
它包含如下摩尔百分比的成分：  It contains the following mole percent components:
Si02 9- -19% Si0 2 9- -19%
B203 36 -49% 其中， Si02/B20: B 2 0 3 36 -49% where Si0 2 /B 2 0:
La203 11- -18% La 2 0 3 11- -18%
Gd203 7~ 15% Gd 2 0 3 7~ 15%
Y203 0- •6% 其中， （Gd203+ La203 +Y203)
Figure imgf000003_0002
23~33% Y 2 0 3 0- •6% where (Gd 2 0 3 + La 2 0 3 + Y 2 0 3 )
Figure imgf000003_0002
23~33%
Ta205 2· -4% Ta 2 0 5 2· -4%
Nb205 0' -2% Nb 2 0 5 0' -2%
Zr02 5' -11% Zr0 2 5' -11%
ZnO 大于 o i」 Sn02 大于 0但小于 2% ZnO is greater than oi" Sn0 2 is greater than 0 but less than 2%
BaO 0-2%  BaO 0-2%
W03 0-1% W0 3 0-1%
Li20 0-2% Li 2 0 0-2%
Sb203 0~0.3%。 Sb 2 0 3 0~0.3%.
优选地， 它包含如下摩尔百分比的成分：  Preferably, it comprises the following mole percent of ingredients:
Si02 10.25-18% Si0 2 10.25-18%
B203 37.23-46.58% 其中， Si02/B203 > 0.25 B 2 0 3 37.23-46.58% where Si0 2 /B 2 0 3 > 0.25
La203 11.39-16.23% La 2 0 3 11.39-16.23%
Gd203 7.77-14.71% Gd 2 0 3 7.77-14.71%
Y203 0-5.54% 其中， （Gd203+ La203 +Y203) 总量为 23~33%Y 2 0 3 0-5.54% wherein (Gd 2 0 3 + La 2 0 3 + Y 2 0 3 ) total amount is 23~33%
Ta205 2.08-3.07% Ta 2 0 5 2.08-3.07%
Nb205 0-1.6% Nb 2 0 5 0-1.6%
Zr02 5.5-10.04% Zr0 2 5.5-10.04%
ZnO 大于 0但小于 8.12%  ZnO is greater than 0 but less than 8.12%
Sn02 大于 0但小于 1.85% Sn0 2 is greater than 0 but less than 1.85%
BaO 0-1.83%  BaO 0-1.83%
W03 0-0.28% W0 3 0-0.28%
Li20 0-1.48% Li 2 0 0-1.48%
Sb203 0.1~0.13%。 Sb 2 0 3 0.1~0.13%.
所述 Gd203的摩尔比大于 6.0%。 The molar ratio of Gd 2 0 3 is greater than 6.0%.
所述光学玻璃的的折射率（nd)大于 1.81， 阿贝数（vd)大于 46且小于 The optical glass has a refractive index (nd) greater than 1.81 and an Abbe number (vd) greater than 46 and less than
48。 48.
所述光学玻璃的内部透过 （λ τ 80) 上限小于 350nm。  The upper limit of the internal transmission (λ τ 80) of the optical glass is less than 350 nm.
所述光学玻璃的密度为 5.10g/cm3以下。 The optical glass has a density of 5.10 g/cm 3 or less.
所述光学玻璃的转变温度（Tg)为 690°C以下，液相线温度（LT)为 1150 The optical glass has a transition temperature (Tg) of 690 ° C or less and a liquidus temperature (LT) of 1150.
°C以下。 Below °C.
本发明还提供了一种光学元件， 所述光学元件由前述的光学玻璃制备而 成。  The present invention also provides an optical element which is prepared from the aforementioned optical glass.
本发明光学玻璃坯料， 可以按照常规方法制造， 也可以按照如下方法制 造： 经加热融化成均匀的玻璃液态， 经铂金漏料装置流入成型模具中， 并在 密闭式加热罩和惰性气体的保护下， 在漏点区外两侧形成的气流隔离大气中 的尘埃落入玻璃成型表面， 消除表面缺陷和增大玻璃表面成型粘度， 固化为 恒定的厚度和宽度， 制造由前述光学玻璃形成的毛坯料。  The optical glass blank of the present invention can be produced according to a conventional method or can be produced as follows: melted into a uniform glass liquid by heating, flows into a molding die through a platinum leakage device, and is protected by a closed heating cover and an inert gas. The airflow formed on the outer sides of the leaking point area isolates the dust in the atmosphere from falling into the glass forming surface, eliminates surface defects and increases the surface forming viscosity of the glass, and solidifies into a constant thickness and width, and manufactures the blank material formed by the aforementioned optical glass. .
根据本发明， 可获得具有折射率（nd) 1.81以上， 阿贝数（vd)为 46~48 范围内的光学特性， 玻璃内透过（λ τ 80)上限 350nm或更低、 下限 300nm 或更低， 密度（P )5.10或更小， 转变温度 （Tg) 为 690°C或更低。 除此之外， 与现有的高折射、 低色散光学玻璃相比， 不仅具有更低的色散和大的阿贝数 特性。 且还具有良好的表面抗失透性， 并能在一种惰性气体的保护下， 实现 稳定的量产。 According to the present invention, it is possible to obtain a refractive index (nd) of 1.81 or more and an Abbe number (vd) of 46 to 48. The optical characteristics in the range, the intra-glass transmission (λ τ 80) upper limit of 350 nm or lower, the lower limit of 300 nm or less, the density (P) of 5.10 or less, and the transition temperature (Tg) of 690 ° C or lower. In addition, it has lower dispersion and large Abbe number characteristics than existing high-refraction, low-dispersion optical glass. It also has good surface devitrification resistance and can achieve stable mass production under the protection of an inert gas.
显然，根据本发明的上述内容，按照本领域的普通技术知识和惯用手段， 在不脱离本发明上述基本技术思想前提下，还可以做出其它多种形式的修改、 替换或变更。  It is apparent that various other modifications, substitutions and changes can be made in the form of the above-described embodiments of the present invention without departing from the spirit and scope of the invention.
以下通过实施例形式的具体实施方式， 对本发明的上述内容再作进一步 的详细说明。 但不应将此理解为本发明上述主题的范围仅限于以下的实例。 凡基于本发明上述内容所实现的技术均属于本发明的范围。  The above content of the present invention will be further described in detail below by way of specific embodiments in the form of embodiments. However, the scope of the above-mentioned subject matter of the present invention should not be construed as being limited to the following examples. Any technique implemented based on the above description of the present invention is within the scope of the present invention.
具体实施方式 detailed description
本发明的光学玻璃折射率 （nd) 为 1.81以上， 阿贝数（vd) 为 46以上、 但不足 48， 且还具有高透过率的特点， 而且当以玻璃液态直接成型为毛坯料 时其表面具有良好的抗失透性， 在具有良好的稳定性和再现性的基础上， 制 成各类规格的毛坯料。 且还具有在二次热压过程中， 经反复地二次热压而不 出现失透， 并制成各种规格的光学元件。  The optical glass of the present invention has a refractive index (nd) of 1.81 or more, an Abbe number (vd) of 46 or more, but less than 48, and also has a high transmittance, and when directly molded into a raw material in a glass liquid state, The surface has good resistance to devitrification, and on the basis of good stability and reproducibility, it is made into various types of rough materials. Further, it has an optical element which is subjected to repeated hot pressing without repeated devitrification during the secondary hot pressing process, and is formed into various specifications.
以下将详细说明构成本发明光学玻璃所包括的玻璃 1~7的玻璃组分及每 一组分引入量和每一组总含量的百分比， 分别以 （摩尔％) 表示。  The glass components constituting the glass 1 to 7 included in the optical glass of the present invention, and the percentage of each component introduced and the total content of each group, which are respectively expressed by (mol%), will be described in detail below.
为实现上述的各项性能， 本发明的光学玻璃包含作为形成玻璃网络组分 的 SiO^P B203， 包含作为提高折射率的 La203、 Gd203、 Y203、 Ta205、 Zr02 等组分， 同时限制 BaO、 W03、 Li20的引入量。 In order to achieve the above various properties, the optical glass of the present invention comprises SiO^PB 2 0 3 as a component forming a glass network, and contains La 2 O 3 , Gd 2 0 3 , Y 2 0 3 , Ta as refractive index. 2 0 5 , Zr0 2 and other components, while limiting the introduction amount of BaO, W0 3 , Li 2 0.
在本发明的高折射、 低色散玻璃中， 8102是作为形成玻璃网络的重要组 分， 也是最有效扩大玻璃生成范围、 增强抗失透性的组分。 当 SiO^ 引入量 低于 8%时， 达不到以上效果。 但当其引入量超过 20%, 不仅会降低折射率， 且还会使熔化的可溶性变差， 难以形成高质量的玻璃。 因此将 SiO^ 引入量 限制在 8~20%的范围内， 优选 9~19%， 进一步优选 10~18%。 In the high-refraction, low-dispersion glass of the present invention, 810 2 is an important component for forming a glass network, and is also a component which most effectively expands the range of glass formation and enhances resistance to devitrification. When the amount of SiO^ introduced is less than 8%, the above effects are not obtained. However, when the amount of introduction exceeds 20%, not only the refractive index is lowered, but also the solubility of the melt is deteriorated, and it is difficult to form a high quality glass. Therefore, the amount of SiO^ introduced is limited to the range of 8 to 20%, preferably 9 to 19%, more preferably 10 to 18%.
B203是最有效用于形成玻璃网络成分， 且能有效提高玻璃的可溶性、 并 降低熔化温度及增强玻璃抗失透性的重要组分。 但是在本发明的玻璃中， 如 B203的引入量超过 50%时， 不仅会使折射率降低， 同时玻璃的稳定性也将变 差。 因此， 将 B203引入量限制在 35~50%的范围内， 优选 36~49%， 特别优 选为 37~48.6%的范围内。 B 2 0 3 is an important component which is most effective for forming a glass network component and which can effectively improve the solubility of the glass, lower the melting temperature and enhance the anti-devitrification resistance of the glass. However, in the glass of the present invention, when the amount of introduction of B 2 0 3 exceeds 50%, not only the refractive index is lowered but also the stability of the glass is deteriorated. Therefore, the amount of introduction of B 2 0 3 is limited to the range of 35 to 50%, preferably 36 to 49%, particularly preferably 37 to 48.6%.
基于对玻璃抗失透性的考虑， 优选 SiO^ 引入量相对于 B203的引入量 比例（Si02/ B203)大于 0.22， 为进一步增大玻璃的粘度， 尤其是成型时的表 面粘度， 更优选大于 0.28， 再进一步优选大于 0.31。 在本发明的光学玻璃中， La203是提高折射率、 并将色散值控制在所期 望范围内的重要组分， 并用于提高玻璃稳定性和降低玻璃表面失透几率。 然 而，当 La203引入量小于 10%时，将难以达到上述效果。但其引入量超过 22% 时， 则玻璃稳定性将会下降， 尤其是成型时玻璃成型面抗失透性下降， 难以 得到稳定的玻璃。 因此， 将 La203的引入量控制在 10~20%的范围内， 优选 11-18%, 特别优选为 11.5~16.5%的范围内。 Based on the consideration of the resistance to devitrification of the glass, it is preferred that the ratio of the amount of SiO^ introduced to the amount of introduction of B203 (Si0 2 / B 2 0 3 ) is more than 0.22, in order to further increase the viscosity of the glass, especially the surface viscosity during molding, More preferably, it is more than 0.28, still more preferably more than 0.31. In the optical glass of the present invention, La 2 O 3 is an important component for increasing the refractive index and controlling the dispersion value within a desired range, and is used for improving the stability of the glass and reducing the probability of devitrification of the glass surface. However, when the introduction amount of La 2 0 3 is less than 10%, it will be difficult to achieve the above effects. However, when the amount of introduction exceeds 22%, the stability of the glass will be lowered, and in particular, the devitrification resistance of the glass molding surface is lowered during molding, and it is difficult to obtain a stable glass. Therefore, the introduction amount of 203 La is controlled within the range of 10 to 20%, preferably 11-18%, particularly preferably in the range of 11.5 to 16.5%.
在本发明的光学玻璃中， Gd203是具有与 La203相同作用的氧化物， 都 是具有提高折射率、 能显著提高玻璃表面的抗失透的最重要的组分， 不仅如 此， 还具有提高可见光区透过和玻璃稳定性的作用。 当引入量不足 6%时， 难以得到上述效果。 如引入量超过 18%, 玻璃将变得极不稳定， 且失透性也 将恶化。 因此， 将 Gd203的引入量控制在 6~16%的范围内， 更优选 7~15%， 特别优选 Gd203的引入量为 7.5~14.8%。 In the optical glass of the present invention, Gd 2 0 3 is an oxide having the same action as La 2 O 3 , and is the most important component having an improved refractive index and a significant increase in the anti-devitrification of the glass surface, not only It also has the effect of improving the transmission of the visible light region and the stability of the glass. When the amount of introduction is less than 6%, it is difficult to obtain the above effects. If the amount introduced exceeds 18%, the glass will become extremely unstable, and the devitrification will also deteriorate. Therefore, the amount of introduction of Gd 2 0 3 is controlled within the range of 6 to 16%, more preferably 7 to 15%, and particularly preferably, the amount of introduction of Gd 2 0 3 is 7.5 to 14.8%.
作为同族稀土氧化物的 Y203与 La203相同， 具有提高折射率、 降低色散 的作用的。 当引入量超过 8%时， 玻璃的表面抗失透性下降， 液相线温度上 升。 因此， Y203引入量控制在 0~8%的范围内， 优选 0~6%或更低。 Y 2 0 3 which is a rare earth oxide of the same group has the same effect of increasing the refractive index and lowering the dispersion, similar to La 2 0 3 . When the amount of introduction exceeds 8%, the surface devitrification resistance of the glass decreases, and the liquidus temperature rises. Therefore, the introduction amount of Y 2 0 3 is controlled in the range of 0 to 8%, preferably 0 to 6% or less.
另外， 与含有单一组分的稀土氧化物相比， 同时含有多种稀土氧化物 Gd20、 La203、 Y203组分， 不仅可显著提高玻璃稳定性， 并可增大稀土氧化 物的总引入量。 特别是在本发明的玻璃中， 如同时含有具有提高折射率的 L¾03、 Gd203、 Y203等组分， 则可大幅度提高折射率， 同时提高玻璃稳定性。 如总引入量超过 35%,玻璃抗失透性将恶化。因此，将（La203+Gd203+ Y203) 总引入量控制在 35%以内， 优选 23~35%， 更优选为 23~33%。 In addition, compared with the rare earth oxide containing a single component, simultaneously containing a plurality of rare earth oxides Gd 2 0, La 2 0 3 , Y 2 0 3 components, not only can significantly improve the stability of the glass, and can increase the rare earth The total amount of oxide introduced. In particular, in the glass of the present invention, if it contains L3⁄40 3 , Gd 2 0 3 , Y 2 0 3 and the like having an increased refractive index, the refractive index can be greatly improved and the stability of the glass can be improved. If the total introduction amount exceeds 35%, the glass resistance to devitrification will deteriorate. Therefore, the total amount of introduction of (La 2 0 3 + Gd 2 0 3 + Y 2 0 3 ) is controlled within 35%, preferably 23 to 35%, more preferably 23 to 33%.
在本发明的玻璃中， Ta205是具有大幅度提高玻璃稳定性、 降低液相线 温度、 且提高折射率、 并使光学常数达到期望范围的重要成分。 当 Τ 05的 引入量小于 1%时， 难以达到上述效果。 但当 Ta205的引入量超过 6%时， 玻 璃高温范围的稳定性下降， 玻璃比重也将增大， 同时原料成本也将上升。 因 此， 将 Τ 05的引入量限制在 1~5%的范围内， 上述范围内的下限优选 1.5% 或更多， 上限优选 5%或更小， 更优选 4%或更小， Ta205的引入量特别优选 2~3.5%的范围内。 In the glass of the present invention, Ta 2 0 5 is an essential component having greatly improved stability of the glass, decrease the liquidus temperature and increase the refractive index and optical constants to achieve the desired range. When the introduction amount of Τ 0 5 is less than 1%, it is difficult to achieve the above effect. However, when the introduction amount of Ta 2 0 5 exceeds 6%, the stability of the glass high temperature range is lowered, the specific gravity of the glass is also increased, and the raw material cost is also increased. Therefore, the introduction amount of Τ 0 5 is limited to the range of 1 to 5%, and the lower limit within the above range is preferably 1.5% or more, and the upper limit is preferably 5% or less, more preferably 4% or less, Ta 2 0 The amount of introduction of 5 is particularly preferably in the range of 2 to 3.5%.
在适量引入的组分中， Nb205是用于增大折射率、 提高玻璃稳定性及改 善玻璃的抗失透性的组分。 但是， 当 Nb205的引入量超过 5%时， 不仅将使 玻璃色散值上升， 同时玻璃抗失透性变差、 玻璃透过也将降低。 因此， 其引 入量限制在 0~3.0%， 优选为 0~2.5%范围内， 更优选为 0~2.0%范围或更低。 Among the components introduced in an appropriate amount, Nb 2 0 5 is a component for increasing the refractive index, improving the stability of the glass, and improving the resistance to devitrification of the glass. However, when the amount of Nb is introduced 205 exceeds 5%, the glass will not only increase the dispersion value, and the glass devitrification resistance deteriorates, through the glass will be reduced. Therefore, the amount of introduction is limited to 0 to 3.0%, preferably 0 to 2.5%, more preferably 0 to 2.0% or less.
Zr02是提高玻璃稳定性和抗失透性、 并提高折射率和化稳性的组分。 当 其引入量超过 12%时， 玻璃的可溶性变差、 稳定性下降。 因此， 将 Zr02的引 入量限制在 12%以内， 优选其引入量 4~12%的范围内， 更优选 5~11%的范围 内。 Zr0 2 is a component that improves glass stability and resistance to devitrification, and increases refractive index and stability. When the amount of introduction exceeds 12%, the solubility of the glass deteriorates and the stability decreases. Therefore, the introduction amount of Zr0 2 is limited to 12%, preferably in the range of 4 to 12%, more preferably 5 to 11%. Inside.
在本发明中， ZnO是降低转变温度、 提高玻璃可溶性和玻璃抗失透性的 组分。 然而， 当其引入量超过 10%时， 玻璃色散值将增大， 同时抗失透性变 差， 透过率也将下降。 因此， 将 ZnO的引入量控制在 0.5~10%的范围内， 优 选 1.5~9.0%， 更优选为 1.5~8.5%的范围内。  In the present invention, ZnO is a component which lowers the transition temperature, increases glass solubility, and is resistant to devitrification of glass. However, when the amount of introduction exceeds 10%, the glass dispersion value will increase, while the devitrification resistance will be deteriorated, and the transmittance will also decrease. Therefore, the amount of introduction of ZnO is controlled in the range of 0.5 to 10%, preferably 1.5 to 9.0%, more preferably 1.5 to 8.5%.
Sn02是与 Zr02相同作用的效果， 当适量引入时， 将可明显提高玻璃表 面的抗失透性， 并降低液相线温度。 但是， 当 Sn02的引入量超过 3%时， 玻 璃可熔性将变差， 玻璃内在质量变差， 玻璃短波长侧的透过也将下降， 同时 玻璃转变温度（Tg)将会快速上升。因此，将 Sn02的引入量上限限制在 3.0%, 优选 0.5~3.0,%， 更优选 0.5~2.5%， 进一步优选 0.5~2.0%。 Sn0 2 and Zr0 2 is the effect of the same action, when the amount is introduced, the glass surface can significantly improve anti-devitrification resistance, and to decrease the liquidus temperature. However, when the introduction amount of Sn0 2 exceeds 3%, the glass fusibility is deteriorated, the intrinsic quality of the glass is deteriorated, the transmission on the short-wavelength side of the glass is also lowered, and the glass transition temperature (Tg) is rapidly increased. Therefore, the upper limit of the amount of introduction of Sn0 2 is limited to 3.0%, preferably 0.5 to 3.0%, more preferably 0.5 to 2.5%, still more preferably 0.5 to 2.0%.
W03是增强抗失透性、 提高玻璃稳定性和折射率的组分。 在本发明的玻 璃中， 当 W03的引入量超过 2%时， 玻璃着色倾向将明显加深、透过率下降， 且玻璃色散值也将增大。 因此， 将其引入量限制在 2%以内， 优选为 0~2%， 更优选 0~1.5%， 进一步优选 0~0.5%或更低。 W0 3 is a component that enhances resistance to devitrification, increases glass stability, and refractive index. In the glass of the present invention, when the amount of introduction of W0 3 exceeds 2%, the tendency of the glass to be colored is significantly deepened, the transmittance is lowered, and the glass dispersion value is also increased. Therefore, the amount of introduction is limited to 2%, preferably 0 to 2%, more preferably 0 to 1.5%, still more preferably 0 to 0.5% or less.
适量引入 BaO可改善玻璃可溶性和提高稳定性的作用，并具有减轻玻璃 着色的效果。但是与作用相似的 ZnO相比， BaO对改善可溶性、 提高抗失透 性的作用较小，因此，将 BaO的引入量限制在 0~3.0%的范围内，优选 0~2.0%， 更优选 0~1.85%。  The proper introduction of BaO can improve the solubility of glass and improve the stability, and has the effect of reducing the coloration of glass. However, compared with the similarly acting ZnO, BaO has less effect on improving solubility and improving resistance to devitrification. Therefore, the introduction amount of BaO is limited to the range of 0 to 3.0%, preferably 0 to 2.0%, more preferably 0. ~1.85%.
Li20是降低玻璃转变温度、 提高玻璃可溶性、 降低熔化温度、 增大成型 时的玻璃粘度的组分。 但是， 当 Li20的引入量超过 3%时， 将会使玻璃抗失 透性及成型时的玻璃表面的抗失透性会变坏， 同时折射率也将下降。 因此， 将其引入量限制在 0~3.0%范围内， 优选 0~2.0%， 更优选 0~1.5%或更低。 Li 2 0 is a component which lowers the glass transition temperature, increases the solubility of the glass, lowers the melting temperature, and increases the viscosity of the glass at the time of molding. However, when the amount of introduction of Li 2 0 exceeds 3%, the devitrification resistance of the glass and the devitrification resistance of the glass surface at the time of molding are deteriorated, and the refractive index is also lowered. Therefore, the amount of introduction thereof is limited to the range of 0 to 3.0%, preferably 0 to 2.0%, more preferably 0 to 1.5% or less.
Sb203是作为澄清剂使用的任意添加剂， 通过微量的加入， 可减轻由于 Fe杂质的还原而导致的光吸收， 并减轻玻璃着色。 如过量添加， 将起到相反 的作用， 还将使玻璃内在质量变差。 因此， 优选将其引入量控制为 0~0.3%， 更优选 0~0.2%或更低。 Sb 2 0 3 is an optional additive used as a clarifying agent, and by a small amount of addition, light absorption due to reduction of Fe impurities can be alleviated, and glass coloring can be alleviated. If added in excess, it will have the opposite effect and will also deteriorate the intrinsic quality of the glass. Therefore, it is preferable to control the amount of introduction thereof to 0 to 0.3%, more preferably 0 to 0.2% or less.
如上所述， 为了不仅是实现高折射、 低色散的特性， 提高玻璃表面的抗 失透性， 并提高玻璃制造的稳定性。优选 Si02、 B203、 La203、 Gd203、 Y203、 Ta205、 Nb205、 As described above, in order to achieve not only the characteristics of high refraction and low dispersion, the devitrification resistance of the glass surface is improved, and the stability of glass production is improved. Preferably, Si0 2 , B 2 0 3 , La 2 0 3 , Gd 2 0 3 , Y 2 0 3 , Ta 2 0 5 , Nb 2 0 5 ,
Zr02、 ZnO 、 Sn02组分的引入量为 98%或更多， W03、 BaO、 Li20组 分的引入量为 2%或更少， 其总引入量为 100%。 The introduction amount of the ZrO 2 , ZnO , and SnO 2 components is 98% or more, and the introduction amount of the W0 3 , BaO, and Li 2 0 components is 2% or less, and the total introduction amount thereof is 100%.
考虑到其经济性和制造的低成本， 而不引入 Ge02、 Ga203等氧化物， 并 可实现稳定的量产。 Considering its economy and low cost of manufacturing, it does not introduce oxides such as Ge0 2 and Ga 2 0 3 , and stable mass production can be achieved.
本发明的光学玻璃折射率 (nd)为 1.81以上， 阿贝数 (vd)为 46~48。 对于 这类高折射、 低色散的玻璃， 当逐步调高折射率时， 玻璃的抗失透性将会变 差， 然而， 本发明的光学玻璃可实现优异的抗失透性和达到高的透过率， 因 而可进一步提高折射率 （nd)。 因此， 本发明的折射率 （nd) 优选至少 1.81， 更优选 1.816或 1.821。 为实现制造的稳定性， 理想的是将折射率 （nd) 限制 在 1.83或更小， 更理想的是限制在 1.82或更小。 The optical glass of the present invention has a refractive index (nd) of 1.81 or more and an Abbe number (vd) of 46 to 48. For such high refractive, low dispersion glass, the anti-devitrification of the glass will change when the refractive index is gradually increased. Poor, however, the optical glass of the present invention can achieve excellent resistance to devitrification and high transmittance, and thus the refractive index (nd) can be further increased. Therefore, the refractive index (nd) of the present invention is preferably at least 1.81, more preferably 1.816 or 1.821. In order to achieve manufacturing stability, it is desirable to limit the refractive index (nd) to 1.83 or less, and more desirably to be 1.82 or less.
再且， 为实现制造的稳定性和良好的抗失透性， 本发明光学玻璃的阿贝 数 (vd) 优选为 46~48， 更优选为 46.5~47.5。  Further, in order to achieve manufacturing stability and good resistance to devitrification, the optical glass of the present invention preferably has an Abbe number (vd) of 46 to 48, more preferably 46.5 to 47.5.
本发明光学玻璃的毛坯料主要是用于通过二次加热软化压制得到光学元 件、 或经冷加工切割， 并经加工制成光学透镜。  The blank of the optical glass of the present invention is mainly used for softening pressing by secondary heating to obtain an optical element, or by cold working, and processed to form an optical lens.
根据本发明的光学玻璃， 通过组分优选和成型工艺创新， 能有效控制成 型时玻璃表面失透性， 并将内透过（波长 λ τ 80 )控制到 350nm以下， 优选 348nm或更小。 将内透过 （波长 λ τ 5 ) 控制在 300nm以下， 优选 290nm或 更小。 由于本发明光学玻璃在 （λ τ 80) 波长范围内具有 90%以上的透过和 ( λ τ 5 ) 更偏移短波方向， 因而适于作为各种高清晰度的光学透镜。  The optical glass according to the present invention, by innovation of the composition and molding process, can effectively control the glass surface devitrification at the time of molding, and control the internal permeation (wavelength λ τ 80 ) to be below 350 nm, preferably 348 nm or less. The internal transmission (wavelength λ τ 5 ) is controlled to be 300 nm or less, preferably 290 nm or less. Since the optical glass of the present invention has a transmission of 90% or more and a (λ τ 5 ) shift in the short-wave direction in the (λ τ 80) wavelength range, it is suitable as various high-definition optical lenses.
实现制造的稳定性的前提是玻璃具有低的液相线温度， 当玻璃的抗失透 性下降时， 其液相线温度会急剧升高， 玻璃稳定性变差。 因而， 本发明的光 学玻璃的液相线温度控制在 1150°C以下， 更优选 1140°C或更低。 实施例 1 本发明光学玻璃的制备方法及其性质  The premise of achieving stability in manufacturing is that the glass has a low liquidus temperature, and when the devitrification resistance of the glass is lowered, the liquidus temperature thereof is sharply increased, and the glass stability is deteriorated. Therefore, the liquidus temperature of the optical glass of the present invention is controlled to be 1150 ° C or lower, more preferably 1140 ° C or lower. Example 1 Preparation method and properties of optical glass of the invention
下面给出本发明的实施例， 给出下面实施例的目的仅在于举例说明， 而 本发明不限于下述实施例。  The following examples of the invention are given, and the following examples are given for the purpose of illustration only, and the invention is not limited to the following examples.
表 1、 2显示了本发明光学玻璃的实施例 NQ 1~N27的玻璃組成和与本发明 玻璃相同的高折射玻璃的比较例 NQA~N2C的组成。 以下测定每个实施例和比 较例中的指标是通过 -4.0/h退火速率并冷却而获得的光学玻璃，折射率（nd)、 阿贝数 (vd)、 内透过 （λ τ 80 ) 禾卩 （λ τ 5 )、 密度 （ Ρ )、 转变温度 （Tg)、 液相线温度 （LT) 的测定结果， 所测定的结果在表 1、 2中给出。 Tables 1 and 2 show the compositions of Comparative Examples NQA to N 2 C of the glass compositions of Examples NQ 1 to N27 of the optical glass of the present invention and the same high refractive glass as the glass of the present invention. The following is an indication of the optical glass obtained by annealing the -4.0/h annealing rate and cooling, the refractive index (nd), the Abbe number (vd), and the internal transmission (λ τ 80 ). The results of measurement of 卩(λ τ 5 ), density ( Ρ ), transition temperature (Tg), and liquidus temperature (LT) are shown in Tables 1 and 2.
将各组分的原料相应的各种氧化物、 碳酸盐和硝酸盐等原料， 按各实施 例和比较例的组成经计算后进行称量混合， 制成配合料， 将其加入铂金容器 中， 在 1250°C ~1370°C的温度下熔化、 搅拌、 澄清及均化后， 浇入常规模具 或漏入带有惰性气体保护的模具中成型为各种规格尺寸的样品和毛坯料。  Raw materials such as various oxides, carbonates and nitrates corresponding to the raw materials of the respective components are calculated and mixed according to the compositions of the respective examples and comparative examples, and the mixture is mixed and prepared into a platinum container. After melting, stirring, clarifying and homogenizing at a temperature of 1250 ° C to 1370 ° C, it is poured into a conventional mold or leaked into a mold with inert gas protection to form samples and blanks of various sizes.
毛坯料的具体制造方法： 经熔融均匀的玻璃液态， 经由铂金漏料装置， 流入经预热的模具中扩散成型， 同时通过漏点两侧外的微孔气流装置向其成 型面上方通入惰性气体， 隔离大气中的尘埃和冷热气流交换中的微小粒子， 防止其落入玻璃成型面， 同时通过气流转换装置的调节与变换， 将冷热气流 中的微小粒子在压力气体的作用下， 引向牵引方向， 起到完全隔离和消除成 型面因落入尘埃而在其成型面的表面形成缺陷及晶斑， 并加速玻璃液表面粘 度的增大和缩小玻璃体内外粘度差。 The specific manufacturing method of the rough material: through the molten glass liquid, through the platinum leakage device, into the preheated mold for diffusion molding, and through the microporous air flow device on both sides of the leakage point, the inert surface is introduced above the molding surface. Gas, which separates the dust from the atmosphere and the tiny particles in the exchange of hot and cold airflow, prevents it from falling into the glass forming surface, and at the same time, through the adjustment and transformation of the airflow conversion device, the tiny particles in the hot and cold airflow are under the action of the pressurized gas. Leading to the direction of traction, completely separating and eliminating the formation of defects and plaques on the surface of the molding surface due to falling into the dust, and accelerating the surface of the molten glass The degree of increase and decrease of the difference in viscosity inside and outside the glass.
以上状态是在采用将发热体密闭于碳化硅内腔中的成型加热罩装置， 加 热成型上方和两侧以及连接段， 而不采用常用的表面直接加热或火焰加热的 方式下进行。  The above state is carried out by using a forming heating hood device for sealing the heat generating body in the inner cavity of the silicon carbide, heating the upper and both sides and the connecting portion without using the usual direct surface heating or flame heating.
本发明制成的毛坯材料， 因是在惰性气体保护下制得的， 其成型面表面 可达到良好的洁净度， 因此它们具有很高的利用价值。  The blank material produced by the invention is made under the protection of an inert gas, and the surface of the molding surface can achieve good cleanliness, so they have high utilization value.
按以下方法测定上述玻璃的各项性能：  The properties of the above glass were measured as follows:
折射率 （nd) 与阿贝数 （vd) 测量以 -4.0/h的退火降温速率得到玻璃试 样。  The refractive index (nd) and the Abbe number (vd) were measured to obtain a glass sample at an annealing rate of -4.0/h.
内透过 （λ τ ) : 分别测量具有三块平行抛光面的 5mm、 10mm, 15mm 样品的内透过， 即 80%处的波长 （nm) 确定为 λ τ 80， 5%处的波长 （nm) 为 λ τ 5。 （内透过不包含试样表面反射损失时的透射比）  Internal transmission (λ τ ): The internal transmission of a 5 mm, 10 mm, 15 mm sample with three parallel polished faces was measured, that is, the wavelength (nm) at 80% was determined as λ τ 80, the wavelength at 5% (nm ) is λ τ 5 . (Internal transmission does not include the transmittance when the surface of the sample is reflected)
确定密度 （Ρ ) : 采用阿基米德法进行测量。  Determine the density (Ρ): Measured using the Archimedes method.
玻璃转变温度（Tg) : 采用热分析仪装置测量， 升温速率为 4.0°C/分钟下 进行测量。  Glass transition temperature (Tg): Measured using a thermal analyzer unit and measured at a heating rate of 4.0 ° C / min.
液相线温度 （LT) : 在 0.3L铂金容器中加入 500g玻璃料， 设定为 10°C 间隔的试验熔炉内、在不同温度下分别保温 2h得到试样，通过显微镜观察是 否有析晶粒子出现， 将确认无晶粒的最低温度作为液相线温度 （LT)。 实施例 （mol% )  Liquidus temperature (LT): 500g glass frit was added to a 0.3L platinum container, set in a test furnace with a 10°C interval, and kept at different temperatures for 2h to obtain a sample. When it appears, the lowest temperature without crystal grains is confirmed as the liquidus temperature (LT). Example (mol%)
组分 实 施 例  Component embodiment
1 2 3 4 5 6 7 1 2 3 4 5 6 7
Si02 10.25 12.63 15.00 11.14 14.97 13.93 18.00Si02 10.25 12.63 15.00 11.14 14.97 13.93 18.00
B203 46.58 44.27 40.74 48.51 41.62 39.92 37.23B203 46.58 44.27 40.74 48.51 41.62 39.92 37.23
La203 16.15 15.69 13.69 11.39 15.04 14.03 16.23La203 16.15 15.69 13.69 11.39 15.04 14.03 16.23
Gd203 8.33 9.35 14.71 11.70 9.26 11.72 7.77Gd203 8.33 9.35 14.71 11.70 9.26 11.72 7.77
Y203 2.83 1.99 2.23 5.43 0.96Y203 2.83 1.99 2.23 5.43 0.96
Ta205 2.08 2.63 2.94 2.73 2.28 2.76 3.07Ta205 2.08 2.63 2.94 2.73 2.28 2.76 3.07
Nb205 0.81 0.82 1.60 0.59 Nb205 0.81 0.82 1.60 0.59
Zr02 6.81 7.79 6.66 10.04 6.31 5.50 6.04 Zr02 6.81 7.79 6.66 10.04 6.31 5.50 6.04
ZnO 4.13 3.61 3.02 1.78 4.87 2.33 8.12 ZnO 4.13 3.61 3.02 1.78 4.87 2.33 8.12
Figure imgf000010_0001
Figure imgf000010_0002
Figure imgf000010_0003
Figure imgf000010_0001
Figure imgf000010_0002
Figure imgf000010_0003
Sn02 Sn02
BaO  BaO
W03 0.93 3.27 4.71  W03 0.93 3.27 4.71
Li20 9.03  Li20 9.03
Sb203 0.03 0.01  Sb203 0.03 0.01
合计 100.00 100.00 100.00  Total 100.00 100.00 100.00
nd 1.79003 1.81791 1.83746  Nd 1.79003 1.81791 1.83746
Vd 46.6 42.57 40.15  Vd 46.6 42.57 40.15
( λ τ 80)nm 361 365 389  ( λ τ 80)nm 361 365 389
( λ τ 5)nm 303 305 316  ( λ τ 5) nm 303 305 316
P ( g/cm3) 4.35 4.77 4.87  P ( g/cm3) 4.35 4.77 4.87
Tg(°C) 550 543 603  Tg(°C) 550 543 603
LT(°C) 1150 1123 1115 如表 1所示， 本发明实施例的光学玻璃 N2 l~N27具有上述范围的光学特 性， 即折射率 (nd) 为 1.81239 1.82570、 阿贝数 (vd) 46.23-47.49, 玻璃内 透过上限 350nm以下，下限为 293nm以下， 比重低于 5.10，其转变温度（Tg) 690°C以下， 液相线温度 （LT) 1150°C以下。 成型中不仅可实现玻璃表面的 良好抗失透性， 且还可实现稳定的量产。 LT (°C) 1150 1123 1115 As shown in Table 1, the optical glass N2 l~N 2 7 of the embodiment of the present invention has optical characteristics in the above range, that is, the refractive index (nd) is 1.81239 1.82570, Abbe number (vd) 46.23-47.49, the upper limit of the glass inner transmission is 350 nm or less, the lower limit is 293 nm or less, the specific gravity is lower than 5.10, the transition temperature (Tg) is 690 ° C or lower, and the liquidus temperature (LT) is 1150 ° C or lower. In the molding, not only good devitrification resistance of the glass surface but also stable mass production can be achieved.
反之， 如表 2中的比较例所示， A例虽然阿贝数 （vd) 属于本发明的范 围， 但折射率 （nd) 低于本发明的范围， 仅为 1.79。 因此， 不属于本发明的 光学特性。  On the contrary, as shown in the comparative example in Table 2, although the Abbe number (vd) belongs to the range of the present invention, the refractive index (nd) is lower than the range of the present invention, and is only 1.79. Therefore, it does not belong to the optical characteristics of the present invention.
同样如此， B、 C例虽然折射率 (nd)达到了 1.81以上， 但阿贝数 (vd) 为 42.6以下， 远低于本发明的范围。 因此， 也不属于本发明的光学特性。  Similarly, in the case of B and C, although the refractive index (nd) is 1.81 or more, the Abbe number (vd) is 42.6 or less, which is far below the range of the present invention. Therefore, it does not belong to the optical characteristics of the present invention.
同时 C例且还含有非常昂贵的 Ge02成分和低的透过率， 不仅难以实现 量产， 也因不具备这种高折射、 低色散的光学特性， 不适用于高端的单反相 机、 数码相机及摄像机的光学系统设计中。 工业应用性 At the same time, the C case also contains a very expensive Ge0 2 component and low transmittance, which is not only difficult to achieve mass production, but also does not have such high refractive, low dispersion optical characteristics, and is not suitable for high-end SLR cameras, digital cameras. And the optical system design of the camera. Industrial applicability
根据本发明， 可提供这种具有高折射率、 低色散特性、 并具有高透过率 和优异制造稳定性和抗失透性的光学玻璃。 由上述光学玻璃毛坯料可形成冷 切、 二次热压等各种光学元件、 并制成光学透镜， 用于高端单反相机、 数码 相机、 摄像机的光学系统中。 适合工业上广泛应用。 According to the present invention, such an optical glass having a high refractive index, low dispersion characteristics, and having high transmittance and excellent manufacturing stability and resistance to devitrification can be provided. The optical glass blank can be formed into various optical components such as cold cutting and secondary hot pressing, and is made into an optical lens for use in a high-end SLR camera, digital In the optical system of the camera and camera. Suitable for a wide range of applications in industry.

Claims

权 利 要 求 书 claims
1、 种光学玻璃， 其特征在于： 它包含如下摩尔百分比的成分: 1. An optical glass, characterized in that: it contains the following mole percentage components:
SiO 8-20% SiO 8-20%
B203 35-50% 其中， Si02/ B203 > 0.22 B 2 0 3 35-50% Among them, Si0 2 / B 2 0 3 > 0.22
La203 10-20% La 2 0 3 10-20%
Gd203 6-16% Gd 2 0 3 6-16%
Y203 0- 8% 其中， （Gd203+ La203 +Y203) 总量为 23~35% Y 2 0 3 0- 8% Among them, the total amount of (Gd 2 0 3 + La 2 0 3 + Y 2 0 3 ) is 23~35%
Ta205 1- 5% Ta 2 0 5 1- 5%
Nb205 0-3% Nb 2 0 5 0-3%
Zr02 4-12% Zr0 2 4-12%
ZnO 大于 0但小于 10% ZnO greater than 0 but less than 10%
Sn02 大于 0但小于 2.5% Sn0 2 is greater than 0 but less than 2.5%
BaO 0-3% BaO 0-3%
W03 0-2% W0 3 0-2%
Li20 0-3% Li 2 0 0-3%
Sb20 0~0.5%。 Sb 2 0 0~0.5%.
2、按权利要求 1 :述的光学玻璃， 其特征在于： 它包含如下摩尔百分比 的成分： 2. The optical glass according to claim 1 , characterized in that: it contains the following molar percentage components:
SiO 9-19% SiO 9-19%
B203 36-49% 其中， Si02/B2〇3 > 0.25 B 2 0 3 36-49% Among them, Si0 2 /B 2 〇3 > 0.25
La203 11-18% La 2 0 3 11-18%
Gd203 7-15% Gd 2 0 3 7-15%
Y203 0-6% 其中， （Gd203+ La203 +Y203) 总量为 23~33% Y 2 0 3 0-6% Among them, the total amount of (Gd 2 0 3 + La 2 0 3 + Y 2 0 3 ) is 23~33%
Ta205 2-4% Ta 2 0 5 2-4%
Nb205 0-2% Nb 2 0 5 0-2%
Zr02 5-11% Zr0 2 5-11%
ZnO 大于 0但小于 9% ZnO greater than 0 but less than 9%
Sn02 大于 0但小于 2% Sn0 2 is greater than 0 but less than 2%
BaO 0-2% BaO 0-2%
W03 0-1% W0 3 0-1%
Li20 0-2% Li 2 0 0-2%
Sb20, 0~0.3%。 Sb 2 0, 0~0.3%.
3、按权利要求 2所述的光学玻璃， 其特征在于： 它包含如下摩尔百分比 的成分： Si02 10.25-18% 3. The optical glass according to claim 2, characterized in that: it contains the following molar percentage components: Si0 2 10.25-18%
B203 37.23-46.58% 其中， Si02/B203 > 0.25 B 2 0 3 37.23-46.58% Among them, Si0 2 /B 2 0 3 > 0.25
La203 11.39-16.23% La 2 0 3 11.39-16.23%
Gd203 7.77-14.71% Gd 2 0 3 7.77-14.71%
Y203 0-5.54% 其中， （Gd203+ La203 +Y203) 总量为 23~33% Y 2 0 3 0-5.54% Among them, the total amount of (Gd 2 0 3 + La 2 0 3 + Y 2 0 3 ) is 23~33%
Ta205 2.08-3.07% Ta 2 0 5 2.08-3.07%
Nb205 0-1.6% Nb 2 0 5 0-1.6%
Zr02 5.5-10.04% Zr0 2 5.5-10.04%
ZnO 大于 0但小于 8.12% ZnO is greater than 0 but less than 8.12%
Sn02 大于 0但小于 1.85% Sn0 2 is greater than 0 but less than 1.85%
BaO 0-1.83% BaO 0-1.83%
W03 0-0.28% W0 3 0-0.28%
Li20 0-1.48% Li 2 0 0-1.48%
Sb203 0.1~0.13%。 Sb 2 0 3 0.1~0.13%.
4、 按权利要求 1~3任意一项所述的光学玻璃， 其特征在于： 所述 Gd203 的摩尔比大于 6.0%。 4. The optical glass according to any one of claims 1 to 3, characterized in that: the molar ratio of Gd 2 0 3 is greater than 6.0%.
5、 根据权利要求 1~4任意一项所述的光学玻璃， 其特征在于： 所述光 学玻璃的折射率 （nd) 大于 1.81， 阿贝数 （vd) 大于 46且小于 48。 5. The optical glass according to any one of claims 1 to 4, characterized in that: the refractive index (nd) of the optical glass is greater than 1.81, and the Abbe number (vd) is greater than 46 and less than 48.
6、 按权利要求 1~4任意一项所述的光学玻璃， 其特征在于： 所述光学 玻璃的内部透过 （λ τ 80) 上限为 350nm以下。 6. The optical glass according to any one of claims 1 to 4, characterized in that: the upper limit of the internal transmission (λ τ 80) of the optical glass is 350 nm or less.
7、 根据权利要求 1~4任意一项所述的光学玻璃， 其特征在于： 所述光 学玻璃的密度为 5.10g/cm3以下。 7. The optical glass according to any one of claims 1 to 4, characterized in that: the density of the optical glass is 5.10 g/cm 3 or less.
8、 根据权利要求 1~4的任意一项所述的光学玻璃， 其特征在于： 所述 光学玻璃的转变温度（Tg)为 690°C以下， 液相线温度（LT)为 1150°C以下。 8. The optical glass according to any one of claims 1 to 4, characterized in that: the transition temperature (Tg) of the optical glass is 690°C or less, and the liquidus temperature (LT) is 1150°C or less. .
9、 一种光学元件， 其特征在于： 所述光学元件由权利要求 1~8任意一 项所述的光学玻璃制备而成。 9. An optical element, characterized in that: the optical element is made of the optical glass described in any one of claims 1 to 8.
10、 一种光学玻璃坯料的制造方法， 其特征在于： 经加热融化成均匀的 玻璃液态， 经铂金漏料装置流入成型模具中， 并在密闭式加热罩和惰性气体 的保护下，在漏点区外两侧形成的气流隔离大气中的尘埃落入玻璃成型表面， 消除表面缺陷和增大玻璃表面成型粘度， 固化为恒定的厚度和宽度， 制造由 权利要求 1~8任意一项所述光学玻璃形成的毛坯料。 10. A method for manufacturing optical glass blanks, characterized by: melting into a uniform glass liquid state after heating, flowing into the molding mold through a platinum leakage device, and under the protection of a closed heating cover and inert gas, at the leakage point The airflow formed on both sides outside the zone isolates the dust in the atmosphere from falling into the glass molding surface, eliminating surface defects and increasing the glass surface molding viscosity, solidifying to a constant thickness and width, and manufacturing the optical fiber according to any one of claims 1 to 8. The blank formed from glass.
PCT/CN2013/090316 2013-08-22 2013-12-24 Optical glass of high refractive index and low dispersion and manufacture method therefor WO2015024351A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201310369788.9A CN103449720B (en) 2013-08-22 2013-08-22 High refraction, low-dispersion optical glass for mold and manufacture method thereof
CN201310369788.9 2013-08-22

Publications (1)

Publication Number Publication Date
WO2015024351A1 true WO2015024351A1 (en) 2015-02-26

Family

ID=49732621

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2013/090316 WO2015024351A1 (en) 2013-08-22 2013-12-24 Optical glass of high refractive index and low dispersion and manufacture method therefor

Country Status (2)

Country Link
CN (1) CN103449720B (en)
WO (1) WO2015024351A1 (en)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103449720B (en) * 2013-08-22 2016-08-17 成都尤利特光电科技股份有限公司 High refraction, low-dispersion optical glass for mold and manufacture method thereof
CN117865468A (en) * 2015-11-06 2024-04-12 株式会社小原 Optical glass, prefabricated member and optical element
CN112939455B (en) * 2021-03-23 2022-04-15 成都光明光电股份有限公司 Optical glass, optical element and optical instrument
CN114907011B (en) * 2022-06-22 2023-08-01 成都光明光电股份有限公司 Optical glass, glass preform, optical element, and optical instrument

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS512717A (en) * 1974-06-28 1976-01-10 Sumita Optical Glass KOKUTSUSETSUTEIBUNSANKOGAKUGARASU
JPS5214607A (en) * 1975-07-24 1977-02-03 Obara Optical Glass Optical glass not containing thorium
JPS534023A (en) * 1976-07-02 1978-01-14 Obara Optical Glass Optical glass
CN103449720A (en) * 2013-08-22 2013-12-18 成都尤利特光电科技有限公司 High-refraction and low-dispersion optical glass and manufacture method thereof

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4093524B2 (en) * 2001-02-20 2008-06-04 Ｈｏｙａ株式会社 Optical glass, press-molding preform and optical parts
JP3912774B2 (en) * 2002-03-18 2007-05-09 Ｈｏｙａ株式会社 Optical glass for precision press molding, preform for precision press molding and manufacturing method thereof
US20050049135A1 (en) * 2003-08-29 2005-03-03 Kazutaka Hayashi Precision press-molding glass preform, optical element and processes for the production thereof
JP2009084059A (en) * 2007-09-27 2009-04-23 Hoya Corp Optical glass, preform for precise press molding and method of manufacturing the same, optical device and method of manufacturing the same

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS512717A (en) * 1974-06-28 1976-01-10 Sumita Optical Glass KOKUTSUSETSUTEIBUNSANKOGAKUGARASU
JPS5214607A (en) * 1975-07-24 1977-02-03 Obara Optical Glass Optical glass not containing thorium
JPS534023A (en) * 1976-07-02 1978-01-14 Obara Optical Glass Optical glass
CN103449720A (en) * 2013-08-22 2013-12-18 成都尤利特光电科技有限公司 High-refraction and low-dispersion optical glass and manufacture method thereof

Also Published As

Publication number Publication date
CN103449720A (en) 2013-12-18
CN103449720B (en) 2016-08-17

Similar Documents

Publication Publication Date Title
JP6719611B2 (en) Optical glass
TWI609848B (en) High refractive high dispersion optical glass, optical components and optical instruments
JP6382256B2 (en) Optical glass and use thereof
US7531474B2 (en) Optical glass, shaped glass material for press-molding, optical element and process for producing optical element
JP4322217B2 (en) Optical glass, glass gob for press molding, optical component, method for manufacturing glass molded body, and method for manufacturing optical component
JP5880439B2 (en) Glass plate and method for producing the same
US9656904B2 (en) Optical glass, optical element blank, glass material for press forming, optical element, and process for producing these
JP2008254953A (en) Optical glass
WO2014187132A1 (en) High-refraction and low-dispersion optical glass and preparation method therefor
CN110510869B (en) Optical glass
TW201800351A (en) Optical glass and optical component
JP2016069254A (en) Glass, glass blank for press-forming, optical element blank, and optical element
TWI714275B (en) Optical glass and glass preforms, optical elements and optical instruments made from it
JP2008273750A (en) Optical glass
WO2015024351A1 (en) Optical glass of high refractive index and low dispersion and manufacture method therefor
TW201713602A (en) Optical glass
JP2008273751A (en) Optical glass
JP6280284B1 (en) Glass, glass material for press molding, optical element blank, and optical element
CN107010826B (en) Environment-friendly lanthanum flint optical glass and preparation method thereof
TW202113397A (en) Optical glass and optical element in which the optical glass has a desired optical constant and excellent stability upon reheating
JP5690505B2 (en) Optical glass, mold press molding preform and optical element
WO2014161358A1 (en) High-refraction optical glass and method of fabricating same
CN105565656B (en) Optical glass
TW202114956A (en) Optical glass and optical element
CN110204198B (en) Phosphate optical glass

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 13891953

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 13891953

Country of ref document: EP

Kind code of ref document: A1