TWI728429B - Optical glass, glass preforms or optical elements and optical instruments prepared therefrom - Google Patents

Optical glass, glass preforms or optical elements and optical instruments prepared therefrom Download PDF

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TWI728429B
TWI728429B TW108129356A TW108129356A TWI728429B TW I728429 B TWI728429 B TW I728429B TW 108129356 A TW108129356 A TW 108129356A TW 108129356 A TW108129356 A TW 108129356A TW I728429 B TWI728429 B TW I728429B
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optical glass
glass
optical
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TW108129356A
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TW202009226A (en
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孫偉
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大陸商成都光明光電股份有限公司
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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
    • 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

Abstract

本發明揭露一種光學玻璃、由其製備而成的玻璃預製件或光學元件及光學儀器。該光學玻璃相對於以氧化物換算的組成的玻璃總重量，按重量百分含量計，光學玻璃包括：B2 O3 ：5~25%，La2 O3 ：25~45%，Gd2 O3 ：15~35%，Y2 O3 ：0~10%， Yb2 O3 :0~10%，Nb2 O5 ：2~15%，SiO2 ：0.5~15%，ZrO2 ：1~15%，TiO2 ：0.5~10%和WO3 ：0~10%，Nb2 O5 與TiO2 的重量比Nb2 O5 /TiO2 為2.17~8.5，且不含Ta2 O5 。本發明通過嚴格控制光學玻璃的組分、含量及特定組分之間的用量比例，使得光學玻璃在不使用Ta2 O5 的情況下，仍具有優異的性能。The invention discloses an optical glass, a glass preform or an optical element and an optical instrument prepared therefrom. The optical glass relative to the total weight of the glass of the composition converted to oxides, in terms of percentage by weight, the optical glass includes: B 2 O 3 : 5-25%, La 2 O 3 : 25-45%, Gd 2 O 3 : 15~35%, Y 2 O 3 : 0~10%, Yb 2 O 3 :0~10%, Nb 2 O 5 : 2~15%, SiO 2 : 0.5~15%, ZrO 2 :1~ 15%, TiO 2: 0.5 ~ 10% , and WO 3: 0 ~ 10%, Nb 2 O 5 and TiO 2 weight ratio of Nb 2 O 5 / TiO 2 2.17 to 8.5, and does not contain Ta 2 O 5. In the present invention, by strictly controlling the components, content and the dosage ratio between the specific components of the optical glass, the optical glass still has excellent performance without using Ta 2 O 5.

Description

光學玻璃、由其製備而成的玻璃預製件或光學元件及光學儀器Optical glass, glass preforms or optical elements and optical instruments prepared therefrom

本發明關於光學玻璃技術領域，具體而言，關於一種光學玻璃、由其製備而成的玻璃預製件或光學元件及光學儀器。The present invention relates to the technical field of optical glass, in particular, to an optical glass, a glass preform or optical element and optical instrument prepared therefrom.

目前，數位照相設備、攝像設備以及投影設備等的發展，對光學元件的要求要來越高，這就需要更高性能的光學玻璃的研發與生產。其中，高折射率低色散光學玻璃形成的透鏡與由高折射率高色散光學玻璃形成的透鏡進行組合，能夠修正色差，使光學系統小型化，特別是折射率nd大於1.87、阿貝數vd大於38.0的高折射率低色散光學玻璃，市場需求日益增大。At present, the development of digital camera equipment, imaging equipment, and projection equipment has higher requirements for optical components, which requires the development and production of higher-performance optical glass. Among them, the combination of a lens formed of high refractive index and low dispersion optical glass and a lens formed of high refractive index and high dispersion optical glass can correct chromatic aberration and make the optical system compact, especially the refractive index nd is greater than 1.87 and the Abbe number vd is greater than 38.0 high refractive index and low dispersion optical glass, the market demand is increasing.

為了滿足上述光性指標的配方基本體系是B-La-Zr-Ta比較好，易成玻璃利於生產，但Ta貴，不利於生產成本的控制。另外，通常情況下，高折射低色散玻璃配方系統中需要引入較多的稀土氧化物以提高玻璃折射率，但在不同的配方體系裡，越多引入鑭系氧化物會影響成玻璃性，如果含量較多，會使玻璃易析晶，析晶上限溫度較高，給量產工藝製造帶來難度。In order to meet the above light indicators, the basic formula system is B-La-Zr-Ta, which is better. Yicheng glass is good for production, but Ta is expensive, which is not conducive to the control of production costs. In addition, under normal circumstances, it is necessary to introduce more rare earth oxides in the high-refractive low-dispersion glass formulation system to increase the refractive index of the glass. However, in different formulation systems, the more lanthanide oxides introduced will affect the glass formation. A higher content will make the glass easy to crystallize, and the upper limit temperature of crystallization will be higher, which will bring difficulties to the mass production process.

本發明旨在提供一種光學玻璃、由其製備而成的玻璃預製件或光學元件及光學儀器，以解決先前技術中存在的高折射低色散光學玻璃易失透、量產難度高、成本較高的技術問題。The present invention aims to provide an optical glass, a glass preform or an optical element and an optical instrument prepared therefrom, so as to solve the problem of high refraction and low dispersion optical glass in the prior art, which is easy to devitrify, difficult to mass produce, and high in cost. Technical issues.

為了實現上述目的，根據本發明的一個方面，提供了一種光學玻璃。該光學玻璃相對於以氧化物換算的組成的玻璃總重量，按重量百分含量計，光學玻璃包括：B2 O3 ：5~25%，La2 O3 ：25~45%，Gd2 O3 ：15~35%，Y2 O3 ：0~10%， Yb2 O3 :0~10%，Nb2 O5 ：2~15%，SiO2 ：0.5~15%，ZrO2 ：1~15%，TiO2 ：0.5~10%和WO3 ：0~10%，Nb2 O5 與TiO2 的重量比Nb2 O5 /TiO2 為2.17~8.5，且不含Ta2 O5 。In order to achieve the above objective, according to one aspect of the present invention, an optical glass is provided. The optical glass relative to the total weight of the glass of the composition converted to oxides, in terms of percentage by weight, the optical glass includes: B 2 O 3 : 5-25%, La 2 O 3 : 25-45%, Gd 2 O 3 : 15~35%, Y 2 O 3 : 0~10%, Yb 2 O 3 :0~10%, Nb 2 O 5 : 2~15%, SiO 2 : 0.5~15%, ZrO 2 :1~ 15%, TiO 2: 0.5 ~ 10% , and WO 3: 0 ~ 10%, Nb 2 O 5 and TiO 2 weight ratio of Nb 2 O 5 / TiO 2 2.17 to 8.5, and does not contain Ta 2 O 5.

進一步地，La2 O3 、Gd2 O3 、Y2 O3 和Yb2 O3 的合計量為50~75%，TiO2 、Nb2 O5 和WO3 的合計量為1~20%。Furthermore, the total amount of La 2 O 3 , Gd 2 O 3 , Y 2 O 3 and Yb 2 O 3 is 50 to 75%, and the total amount of TiO 2 , Nb 2 O 5 and WO 3 is 1 to 20%.

進一步地，光學玻璃還包括選自由ZnO、BaO、CaO、SrO、MgO、Sb2 O3 、Li2 O、Na2 O和K2 O組成的組中的一種或多種，且含量如下：ZnO：0~15%，BaO：0~10%；CaO：0~10%；SrO：0~10%；MgO：0~10%；Sb2 O3 ：0~1%，Li2 O、Na2 O和K2 O的合計量為0~10%。Further, the optical glass also includes one or more selected from the group consisting of ZnO, BaO, CaO, SrO, MgO, Sb 2 O 3 , Li 2 O, Na 2 O and K 2 O, and the content is as follows: ZnO: 0~15%, BaO: 0~10%; CaO: 0~10%; SrO: 0~10%; MgO: 0~10%; Sb 2 O 3 : 0~1%, Li 2 O, Na 2 O The total amount of K 2 O and K 2 O is 0~10%.

進一步地，相對於以氧化物換算的組成的玻璃總重量，按重量百分含量計，光學玻璃由B2 O3 ：5~25%，SiO2 ：0.5~15%，ZrO2 ：1~15%，ZnO：0~15%，BaO：0~10%，CaO：0~10%，SrO：0~10%，MgO：0~10%，合計量為1~20% 的TiO2 、Nb2 O5 和WO3 ，合計量為0~10%的Li2 O、Na2 O和K2 O，Sb2 O3 ：0~1%，以及合計量為50~75% 的La2 O3 、Gd2 O3 、Y2 O3 和Yb2 O3 組成。Furthermore, with respect to the total weight of the glass composition in terms of oxide conversion, the optical glass consists of B 2 O 3 : 5-25%, SiO 2 : 0.5-15%, ZrO 2 : 1-15 %, ZnO: 0~15%, BaO: 0~10%, CaO: 0~10%, SrO: 0~10%, MgO: 0~10%, the total amount is 1~20% of TiO 2 , Nb 2 O 5 and WO 3 , the total amount of Li 2 O, Na 2 O and K 2 O of 0-10%, Sb 2 O 3 : 0-1%, and the total amount of 50-75% La 2 O 3 , It is composed of Gd 2 O 3 , Y 2 O 3 and Yb 2 O 3.

進一步地，相對於以氧化物換算的組成的玻璃總重量，按重量百分含量計，光學玻璃包括：B2 O3 ：8~22%， SiO2 ：3~10%，ZrO2 ：3~12%，合計量為5~15%的TiO2 、Nb2 O5 和WO3 ，和/或合計量為55~70% 的La2 O3 、Gd2 O3 、Y2 O3 和Yb2 O3 。Further, with respect to the total weight of the glass of the composition in terms of oxide conversion, the optical glass includes: B 2 O 3 : 8-22%, SiO 2 : 3-10%, ZrO 2 : 3~ 12%, 5~15% of TiO 2 , Nb 2 O 5 and WO 3 , and/or 55~70% of La 2 O 3 , Gd 2 O 3 , Y 2 O 3 and Yb 2 O 3 .

進一步地，Nb2 O5 與SiO2 的重量比Nb2 O5 /SiO2 為0.75~2，較佳為1~1.5。Furthermore, Nb 2 O 5 weight ratio of SiO 2 and Nb 2 O 5 / SiO 2 from 0.75 to 2, preferably from 1 to 1.5.

進一步地，La2 O3 與Gd2 O3 的重量比La2 O3 /Gd2 O3 為1.28~1.625，較佳為La2 O3 /Gd2 O3 為1.3~1.6，更佳為1.4~1.5。Further, La 2 O 3 and Gd 2 O 3 weight ratio of La 2 O 3 / Gd 2 O 3 1.28 - 1.625, preferably La 2 O 3 / Gd 2 O 3 1.3 to 1.6, more preferably 1.4 ~1.5.

進一步地，光學玻璃不含Y2 O3 和/或WO3 。Further, the optical glass does not contain Y 2 O 3 and/or WO 3 .

進一步地，ZrO2 與SiO2 的重量比ZrO2 / SiO2 ≥1。Further, ZrO 2 and SiO 2 weight ratio of ZrO 2 / SiO 2 ≥1.

進一步地，光學玻璃的析晶上限溫度低於1350℃，較佳低於1300℃。Further, the upper limit temperature of crystallization of the optical glass is lower than 1350°C, preferably lower than 1300°C.

進一步地，光學玻璃的折射率nd＞1.87，較佳nd＞1.88；阿貝數vd＞38.0，較佳vd＞39.0。Further, the refractive index of the optical glass is nd>1.87, preferably nd>1.88; Abbe number vd>38.0, preferably vd>39.0.

進一步地，光學玻璃的耐水作用穩定性Dw在3級以上，較佳2級以上，更佳1級；耐酸作用穩定性DA 在3級以上，較佳2級以上，更佳1級。Further, the water resistance stability Dw of the optical glass is above level 3, preferably above level 2, and more preferably above level 1, and the acid resistance stability D A is above level 3, preferably above level 2, and more preferably above level 1.

進一步地，光學玻璃的條紋為C級以上，較佳B級以上，更佳A級；氣泡度為A級以上，較佳A0 級以上，更佳A00 級。Further, the fringes of the optical glass are above grade C, preferably above grade B, more preferably above grade A; the bubble degree is above grade A, preferably above grade A 0, more preferably above grade A 00 .

進一步地，光學玻璃的透射比達到70％時對應的波長λ70 小於或等於420nm，較佳小於或等於390nm；玻璃透射比達到5％時對應的波長λ5 小於或等於360nm，較佳小於或等於350nm。Further, when the transmittance of the optical glass reaches 70%, the corresponding wavelength λ 70 is less than or equal to 420 nm, preferably less than or equal to 390 nm; when the transmittance of the glass reaches 5%, the corresponding wavelength λ 5 is less than or equal to 360 nm, preferably less than or Equal to 350nm.

進一步地，光學玻璃的密度小於5.3 g/cm3 ，較佳小於5.23 g/cm3 。Further, the density of the optical glass is less than 5.3 g/cm 3 , preferably less than 5.23 g/cm 3 .

根據本發明的另一方面，提供了一種玻璃預製件或光學元件。該玻璃預製件或光學元件由上述任一種光學玻璃製備而成。According to another aspect of the present invention, a glass preform or optical element is provided. The glass preform or optical element is prepared from any of the above-mentioned optical glasses.

根據本發明的再一方面，提供了一種光學儀器，該光學儀器包括光學元件，光學元件為上述任一種光學元件。According to another aspect of the present invention, an optical instrument is provided, the optical instrument includes an optical element, and the optical element is any of the above-mentioned optical elements.

應用本發明的技術方案，通過嚴格控制光學玻璃的組分、含量及特定組分之間的用量比例，使得本發明的光學玻璃在不使用Ta2 O5 的情況下，能獲得具有耐失透且性能優異的高折射低色散光學玻璃，而且本發明的光學玻璃生產成本低，易於量產。Applying the technical solution of the present invention, by strictly controlling the components, content and the amount ratio between the specific components of the optical glass, the optical glass of the present invention can achieve devitrification resistance without using Ta 2 O 5 Moreover, the high-refraction and low-dispersion optical glass with excellent performance, and the optical glass of the present invention has low production cost and is easy to mass produce.

需要說明的是，在不衝突的情況下，本發明中的實施例及實施例中的特徵可以相互組合。下面將結合實施例來詳細說明本發明。It should be noted that the embodiments of the present invention and the features in the embodiments can be combined with each other if there is no conflict. The present invention will be described in detail below in conjunction with embodiments.

在本說明書中，在沒有特別說明的情況下，各成分的含量全部用相對於以氧化物換算的組成的玻璃總重量的重量%來表示。其中，“以氧化物換算的組成”是指在假設作為本發明的玻璃構成成分的原料在熔融時全部分解轉化為氧化物的情況下，以該生成的氧化物的總重量為100重量%來表示的玻璃中所含有的各成分時的組成。In this specification, unless otherwise specified, the contents of each component are all expressed in% by weight relative to the total weight of the glass of the composition in terms of oxides. Here, "composition in terms of oxides" means that assuming that the raw materials used as the constituent components of the glass of the present invention are all decomposed and converted into oxides during melting, the total weight of the oxides produced is taken as 100% by weight. It shows the composition of each component contained in the glass.

下面將描述各組分在光學玻璃中起到的基本作用，但並不對組分之間由於特定含量的配比帶來的協同作用或意想不到的效果造成不當限定。The basic role played by each component in the optical glass will be described below, but it does not improperly limit the synergy or unexpected effects between the components due to the specific content ratio.

[玻璃成分][Glass composition]

B2 O3 為玻璃的骨架成分，在本發明中具有提高玻璃可熔融性、耐失透性和降低玻璃色散的作用。但當其引入量超過25%時，玻璃穩定性會下降，並且折射率下降，當其引入量不足5%時，玻璃熔融性降低，達不到本發明所需的光學常數。因此，本發明的B2 O3 的含量為5~25% ，較佳B2 O3 含量為8~22%。B 2 O 3 is a skeletal component of glass, and has the functions of improving glass meltability, resistance to devitrification, and reducing glass dispersion in the present invention. However, when the amount of introduction exceeds 25%, the stability of the glass will decrease and the refractive index will decrease. When the amount of introduction is less than 5%, the glass meltability will decrease and the optical constants required by the present invention will not be reached. Therefore, the content of B 2 O 3 in the present invention is 5-25%, and the content of B 2 O 3 is preferably 8-22%.

SiO2 為構成玻璃骨架的成分，其具有提高耐失透性、增大操作溫度範圍的作用，另外，還具有提高玻璃的化學穩定性、改善玻璃的熱穩定性等作用。若其含量超過15%，則玻璃可熔融性能降低，且無法獲得本發明所需要的折射率。在本發明中SiO2 含量為0.5~15% ，較佳SiO2 含量為3~10%。SiO 2 is a component constituting the glass skeleton, and it has the effects of improving the resistance to devitrification and increasing the operating temperature range. In addition, it also has the effects of improving the chemical stability of the glass and improving the thermal stability of the glass. If its content exceeds 15%, the glass meltability is reduced, and the refractive index required by the present invention cannot be obtained. In the present invention, the content of SiO 2 is 0.5-15%, preferably the content of SiO 2 is 3-10%.

ZrO2 為提高折射率和穩定性的成分。由於作為中間氧化物形成玻璃，所以還具有提高耐失透性和化學耐久性的作用。ZrO2 的含量不足1%時，無法達到上述預期效果，當ZrO2 的含量超過15%時，存在失透傾向變強、玻璃化變得困難的傾向。在本發明中ZrO2 含量為1~15%，較佳ZrO2 含量為3~12%。ZrO 2 is a component that improves the refractive index and stability. Since it forms glass as an intermediate oxide, it also has the effect of improving devitrification resistance and chemical durability. When the content of ZrO 2 is less than 1%, the expected effect cannot be achieved, and when the content of ZrO 2 exceeds 15%, the tendency of devitrification becomes stronger and vitrification tends to become difficult. In the present invention, the content of ZrO 2 is 1-15%, preferably the content of ZrO 2 is 3-12%.

本發明人通過研究發現，控制ZrO2 /SiO2 ≥1，還能夠帶來密度輕量化的有益效果。較佳ZrO2 / SiO2 為3以下，較佳0.7~2，更佳1~1.5。The inventor found through research that controlling ZrO 2 /SiO 2 ≥1 can also bring about the beneficial effects of lighter density and weight. Preferably, ZrO 2 / SiO 2 is 3 or less, preferably 0.7 to 2, more preferably 1 to 1.5.

TiO2 也具有提高玻璃折射率的作用，並且能參與玻璃網路形成，適量引入使玻璃更穩定。但若過量含有時，玻璃色散會顯著增加，同時玻璃可見光區域的短波部分的透射率降低，玻璃著色的傾向增加。在本發明中TiO2 含量為0.5~10%，較佳為0.5~7%。TiO 2 also has the effect of increasing the refractive index of the glass, and can participate in the formation of the glass network, and the appropriate amount of introduction makes the glass more stable. However, if it is contained in an excessive amount, the glass dispersion will significantly increase, and at the same time, the transmittance of the short-wave part of the glass in the visible light region will decrease, and the tendency of the glass to be colored increases. In the present invention, the content of TiO 2 is 0.5-10%, preferably 0.5-7%.

Nb2 O5 為提高折射率和色散的成分，也具有提高玻璃的抗析晶性與化學耐久性的作用。TiO2 也具有提高玻璃折射率的作用，並且能參與玻璃網路形成，適量引入使玻璃更穩定。WO3 起到提高折射率的作用，並且發明人經過研究發現，將本發明中TiO2 、Nb2 O5 和WO3 合計含量控制到1~20%的範圍，當TiO2 、Nb2 O5 和WO3 合計含量不足1%時，達不到本發明所需效果；如果其含量超過20%，則玻璃色散會顯著提高，玻璃可見光區域的短波部分的透射率降低，著色傾向增加，無法達到本發明玻璃的光學特性。另外，TiO2 、Nb2 O5 和WO3 與其它組份協同，能有效降低本發明玻璃的密度，較佳合計含量為5~15%，本發明中較佳不含WO3 。Nb 2 O 5 is a component that improves the refractive index and dispersion, and also has the effect of improving the devitrification resistance and chemical durability of the glass. TiO 2 also has the effect of increasing the refractive index of the glass, and can participate in the formation of the glass network, and the appropriate amount of introduction makes the glass more stable. WO 3 plays a role in increasing the refractive index, and the inventors have discovered through research that the total content of TiO 2 , Nb 2 O 5 and WO 3 in the present invention is controlled to the range of 1-20%, when TiO 2 , Nb 2 O 5 When the total content of WO 3 and WO 3 is less than 1%, the desired effect of the present invention will not be achieved; if its content exceeds 20%, the glass dispersion will be significantly increased, the transmittance of the short-wave part of the visible light region of the glass will decrease, and the coloring tendency will increase. Optical properties of the glass of the present invention. In addition, TiO 2 , Nb 2 O 5 and WO 3 are synergistic with other components to effectively reduce the density of the glass of the present invention, and the total content is preferably 5-15%, and WO 3 is preferably not contained in the present invention.

本發明玻璃組分不引入Ta2 O5 ，但可以通過引入Nb2 O5 或TiO2 ，較佳將TiO2 和Nb2 O5 作為玻璃組分共存，更佳控制Nb2 O5 /TiO2 在2.17~8.5，進一步較佳Nb2 O5 /TiO2 在3.8~6.5，更進一步較佳Nb2 O5 /TiO2 在4~5.5，以實現高折射低色散，並在有效抑制玻璃著色度的同時，使玻璃的析晶上限溫度有效降低，並且玻璃穩定性優良。The glass component of the present invention does not introduce Ta 2 O 5 , but Nb 2 O 5 or TiO 2 can be introduced, preferably TiO 2 and Nb 2 O 5 coexist as glass components, and Nb 2 O 5 /TiO 2 is better controlled In the range of 2.17 to 8.5, it is more preferable that Nb 2 O 5 /TiO 2 is in the range of 3.8 to 6.5, and the Nb 2 O 5 /TiO 2 is still more preferably in the range of 4 to 5.5, in order to achieve high refraction and low dispersion, and effectively suppress glass coloration At the same time, the upper limit temperature of crystallization of the glass is effectively reduced, and the stability of the glass is excellent.

La2 O3 、Gd2 O3 、Y2 O3 和Yb2 O3 均是提高玻璃的折射率的主要成分、可以提高折射率但不會明顯增大色散。本發明中加入一定量的上述稀土氧化物可以降低析晶上限溫度，提高玻璃的耐失透性能，改善化學穩定性，在熔製過程不易產生玻璃氣泡，等作用，因此在本發明的高折射低色散玻璃配方體系中La2 O3 、Gd2 O3 、Y2 O3 和Yb2 O3 合計含量不低於50%，不超過75%,以保證實現上述技術效果，達到發明目的；較佳範圍為55-70%，更佳60-67%。La 2 O 3 , Gd 2 O 3 , Y 2 O 3, and Yb 2 O 3 are all main components that increase the refractive index of the glass, and can increase the refractive index without significantly increasing the dispersion. The addition of a certain amount of the above rare earth oxides in the present invention can reduce the upper limit temperature of crystallization, improve the devitrification resistance of the glass, improve the chemical stability, and it is not easy to produce glass bubbles during the melting process. Therefore, the high refractive index of the present invention The total content of La 2 O 3 , Gd 2 O 3 , Y 2 O 3 and Yb 2 O 3 in the low-dispersion glass formula system is not less than 50% and not more than 75%, so as to ensure the realization of the above technical effects and achieve the purpose of the invention; The preferred range is 55-70%, more preferably 60-67%.

但通常情況下，越多引入鑭系氧化物也會影響成玻璃性，如果含量較多，則使玻璃易析晶，析晶上限溫度較高，給量產工藝製造帶來難度；因此一般具有高折射低色散性能的鑭系氧化物含量通常在60%以下才能保證玻璃不易析晶，而本發明的高折射低色散玻璃中通過控制鑭系氧化物La2 O3 與Gd2 O3 的重量比La2 O3 /Gd2 O3 為1.28~1.625的成分及含量，可以使得鑭系氧化物的含量在60%以下及超過60%時，仍然能保證玻璃的析晶上限溫度不升高，析晶上限溫度低於1350℃，較佳低於1300℃，更佳低於1280℃，能確保組分的成玻璃性更好，在熔製過程不易產生玻璃氣泡，並且還保證良好的光學性能和成型性能等，較佳的，La2 O3 /Gd2 O3 為1.3~1.6；更佳的，La2 O3 /Gd2 O3 為1.4~1.5。However, under normal circumstances, the more lanthanide oxides introduced will also affect the glass forming property. If the content is larger, the glass will be easy to crystallize, and the upper limit temperature of crystallization will be higher, which will bring difficulties to the mass production process; therefore, it generally has The content of lanthanide oxides with high refraction and low dispersion properties is usually below 60% to ensure that the glass is not easy to crystallize. In the high refraction and low dispersion glass of the present invention, the weight of lanthanide oxides La 2 O 3 and Gd 2 O 3 is controlled. The ratio La 2 O 3 /Gd 2 O 3 is 1.28~1.625 composition and content, so that when the content of lanthanide oxide is below 60% and exceeds 60%, it can still ensure that the upper crystallization temperature of the glass does not increase. The upper limit of crystallization temperature is lower than 1350°C, preferably lower than 1300°C, more preferably lower than 1280°C, which can ensure better glass-forming properties of the components, less likely to produce glass bubbles during the melting process, and also ensure good optical properties And molding performance, etc., La 2 O 3 /Gd 2 O 3 is preferably 1.3 to 1.6; more preferably, La 2 O 3 /Gd 2 O 3 is 1.4 to 1.5.

ZnO可以調整玻璃的折射率和色散，適量的ZnO可以起到改善玻璃的穩定性或熔融性、改善加壓成型性的作用，但當其含量過高時，折射率降低，達不到本發明的要求，同時玻璃的耐失透性降低，析晶上限溫度上升。因此本發明的ZnO含量為0~15%，較佳0~10%，更佳0~5%。ZnO can adjust the refractive index and dispersion of the glass. A proper amount of ZnO can improve the stability or meltability of the glass and improve the press formability. However, when its content is too high, the refractive index will decrease, which will not reach the present invention. At the same time, the devitrification resistance of the glass decreases, and the upper limit temperature of crystallization increases. Therefore, the ZnO content of the present invention is 0-15%, preferably 0-10%, more preferably 0-5%.

BaO、CaO、SrO和MgO這類的鹼土金屬氧化物，能夠使玻璃的化學穩定性降低和析晶上限溫度上升，但當其各自含量超過10%時，玻璃耐失透性降低，因此本發明的BaO為0~10%；CaO含量為0~10%；SrO含量為0~10%、MgO含量為0~10%。Alkaline earth metal oxides such as BaO, CaO, SrO and MgO can reduce the chemical stability of the glass and increase the upper limit temperature of crystallization, but when their respective content exceeds 10%, the devitrification resistance of the glass is reduced. Therefore, the present invention The content of BaO is 0-10%; the content of CaO is 0-10%; the content of SrO is 0-10% and the content of MgO is 0-10%.

Li2 O、Na2 O和K2 O為用於抑制分相、提高玻璃穩定性的成分。當其含量超過10%時，存在化學穩定性顯著降低或折射率降低的傾向，較佳的，Li2 O、Na2 O和K2 O的合計量為0~10%。Li 2 O, Na 2 O, and K 2 O are components for suppressing phase separation and improving glass stability. When its content exceeds 10%, there is a tendency for the chemical stability to be significantly reduced or the refractive index to decrease. Preferably, the total amount of Li 2 O, Na 2 O, and K 2 O is 0-10%.

根據本發明一種典型的實施方式，提供了一種光學玻璃。該光學玻璃相對於以氧化物換算的組成的玻璃總重量，按重量百分含量計，光學玻璃包括：B2 O3 ：5~25%，La2 O3 ：25~45%，Gd2 O3 ：15~35%，Y2 O3 ：0~10%， Yb2 O3 :0~10%，Nb2 O5 ：2~15%，SiO2 ：0.5~15%，ZrO2 ：1~15%，TiO2 ：0.5~10%和WO3 ：0~10%，Nb2 O5 與TiO2 的重量比Nb2 O5 /TiO2 為2.17~8.5，且不含Ta2 O5 。According to a typical embodiment of the present invention, an optical glass is provided. The optical glass relative to the total weight of the glass of the composition converted to oxides, in terms of percentage by weight, the optical glass includes: B 2 O 3 : 5-25%, La 2 O 3 : 25-45%, Gd 2 O 3 : 15~35%, Y 2 O 3 : 0~10%, Yb 2 O 3 :0~10%, Nb 2 O 5 : 2~15%, SiO 2 : 0.5~15%, ZrO 2 :1~ 15%, TiO 2: 0.5 ~ 10% , and WO 3: 0 ~ 10%, Nb 2 O 5 and TiO 2 weight ratio of Nb 2 O 5 / TiO 2 2.17 to 8.5, and does not contain Ta 2 O 5.

應用本發明的技術方案，通過嚴格控制光學玻璃的組分、含量及特定組分之間的用量比例，使得本發明的光學玻璃在不使用Ta2 O5 的情況下，具有優良的耐失透性和光學性能，易於量產且生產成本低。Applying the technical solution of the present invention, by strictly controlling the components, content and the amount ratio between the specific components of the optical glass, the optical glass of the present invention has excellent devitrification resistance without using Ta 2 O 5 The performance and optical performance are easy to mass produce and the production cost is low.

根據本發明一種典型的實施方式，光學玻璃還包括選自由ZnO、BaO、CaO、SrO、MgO、Sb2 O3 、Li2 O、Na2 O和K2 O組成的組中的一種或多種，且含量如下：ZnO：0~15%，BaO：0~10%；CaO：0~10%；SrO：0~10%；MgO：0~10%；Sb2 O3 ：0~1%，Li2 O、Na2 O和K2 O的合計量為0~10%。According to a typical embodiment of the present invention, the optical glass further includes one or more selected from the group consisting of ZnO, BaO, CaO, SrO, MgO, Sb 2 O 3 , Li 2 O, Na 2 O and K 2 O, And the content is as follows: ZnO: 0~15%, BaO: 0~10%; CaO: 0~10%; SrO: 0~10%; MgO: 0~10%; Sb 2 O 3 : 0~1%, Li The total amount of 2 O, Na 2 O and K 2 O is 0-10%.

根據本發明一種典型的實施方式，相對於以氧化物換算的組成的玻璃總重量，按重量百分含量計，光學玻璃由B2 O3 ：5~25%，SiO2 ：0.5~15%，ZrO2 ：1~15%，ZnO：0~15%，BaO：0~10%，CaO：0~10%，SrO：0~10%，MgO：0~10%，合計量為1~20% 的TiO2 、Nb2 O5 和WO3 ，合計量為0~10%的Li2 O、Na2 O和K2 O，Sb2 O3 ：0~1%，以及合計量為50~75% 的La2 O3 、Gd2 O3 、Y2 O3 和Yb2 O3 組成。其中，La2 O3 與Gd2 O3 的重量比La2 O3 /Gd2 O3 為1.28~1.625。嚴格控制光學玻璃的組分、含量及特定組分之間的用量比例，使得本發明的光學玻璃在不使用Ta2 O5 的情況下，具有較好的耐失透性和優良的光學性能，易於量產且生產成本低。According to a typical implementation of the present invention, relative to the total weight of the glass composition converted by oxides, the optical glass consists of B 2 O 3 : 5-25%, SiO 2 : 0.5-15%, in terms of weight percentage, ZrO 2 : 1~15%, ZnO: 0~15%, BaO: 0~10%, CaO: 0~10%, SrO: 0~10%, MgO: 0~10%, the total amount is 1~20% TiO 2 , Nb 2 O 5 and WO 3 , the total amount is 0~10% Li 2 O, Na 2 O and K 2 O, Sb 2 O 3 : 0~1%, and the total amount is 50~75% The composition of La 2 O 3 , Gd 2 O 3 , Y 2 O 3 and Yb 2 O 3. Wherein, La 2 O 3 and Gd 2 O 3 ratio by weight of La 2 O 3 / Gd 2 O 3 is 1.28 ~ 1.625. Strictly control the components, content and the amount ratio of specific components of the optical glass, so that the optical glass of the present invention has better resistance to devitrification and excellent optical performance without using Ta 2 O 5. Easy to mass produce and low production cost.

較佳的，根據本發明一種典型的實施方式，相對於以氧化物換算的組成的玻璃總重量，按重量百分含量計，所述光學玻璃包括：B2 O3 ：8~22%， SiO2 ：3~10%，ZrO2 ：3~12%，合計量為5~15%的TiO2 、Nb2 O5 和WO3 ，和/或合計量為55~70% 的La2 O3 、Gd2 O3 、Y2 O3 和Yb2 O3 。Preferably, according to a typical embodiment of the present invention, with respect to the total weight of the glass composition in terms of oxide conversion, the optical glass includes: B 2 O 3 : 8-22%, SiO 2 : 3~10%, ZrO 2 : 3~12%, the total amount is 5~15% TiO 2 , Nb 2 O 5 and WO 3 , and/or the total amount is 55~70% La 2 O 3 , Gd 2 O 3 , Y 2 O 3 and Yb 2 O 3 .

本發明中，Y2 O3 可改善玻璃的熔融性、耐失透性，同時還可降低玻璃析晶上限溫度，但若其含量超過一定量，則玻璃的穩定性、耐失透性下降。WO3 起到提高折射率的作用，但當WO3 含量超過10%時，存在失透傾向增強、玻璃化變得困難的傾向，色散提高顯著，並且玻璃可見光區域的短波長側的透射率降低，著色的傾向增加，因此本發明較佳WO3 的含量為0~10%。根據本發明一種典型的實施方式，光學玻璃較佳不含Y2 O3 和/或WO3 。In the present invention, Y 2 O 3 can improve the meltability and devitrification resistance of the glass, and at the same time reduce the upper limit temperature of glass crystallization, but if its content exceeds a certain amount, the stability and devitrification resistance of the glass will decrease. WO 3 plays a role in increasing the refractive index, but when the content of WO 3 exceeds 10%, there is a tendency to increase devitrification and make vitrification difficult, the dispersion increases significantly, and the transmittance on the short-wavelength side of the visible light region of the glass decreases. , The tendency to color increases, so the preferred content of WO 3 in the present invention is 0-10%. According to a typical embodiment of the present invention, the optical glass preferably does not contain Y 2 O 3 and/or WO 3 .

本發明中通過控制Nb2 O5 的含量與SiO2 的含量的比值Nb2 O5 /SiO2 在0.75~2內，不僅可以使玻璃的熔融性增加，有效增加玻璃穩定性，不易產生條紋，玻璃均勻度好，同時具有在不使透過率變差的情況下提高玻璃折射率、抗析晶性和化學耐久性的作用，尤其是當其Nb2 O5 /SiO2 比值為1~1.5時，效果尤其明顯。In the present invention, by controlling the ratio of the content of Nb 2 O 5 to the content of SiO 2 Nb 2 O 5 /SiO 2 within 0.75~2, not only the meltability of the glass can be increased, the stability of the glass is effectively increased, and the streaks are not easily generated. The glass has good uniformity, and at the same time it has the function of improving the refractive index, anti-crystallization and chemical durability of the glass without deteriorating the transmittance, especially when the ratio of Nb 2 O 5 /SiO 2 is 1~1.5 , The effect is particularly obvious.

通過少量添加Sb2 O3 、SnO2 、CeO2 組分可以提高玻璃的澄清效果，但當Sb2 O3 含量超過1%時，玻璃有澄清性能降低的傾向，同時由於其強氧化作用促進了成型模具的惡化，因此本發明較佳Sb2 O3 的添加量為0~1%，更佳為0~0.5%。SnO2 也可以作為澄清劑來添加，但當其含量超過1%時，則玻璃會著色，或者當加熱、軟化玻璃並進行模壓成形等再次成形時，Sn會成為晶核生成的起點，產生失透的傾向。因此本發明的SnO2 的含量較佳為0~1%，更佳為0~0.5%，進一步較佳不添加。CeO2 的作用及添加量比例與SnO2 一致，其含量較佳為0~1%，更佳為0~0.5%，進一步較佳不添加。By adding a small amount of Sb 2 O 3 , SnO 2 , CeO 2 components, the clarification effect of the glass can be improved. However, when the content of Sb 2 O 3 exceeds 1%, the clarification performance of the glass tends to decrease. Due to the deterioration of the molding die, the preferred addition amount of Sb 2 O 3 in the present invention is 0 to 1%, more preferably 0 to 0.5%. SnO 2 can also be added as a fining agent, but when its content exceeds 1%, the glass will be colored, or when the glass is heated, softened and molded again, Sn will become the starting point for crystal nucleation, causing loss Penetrating tendency. Therefore, the content of SnO 2 in the present invention is preferably 0 to 1%, more preferably 0 to 0.5%, and further preferably not added. The effect of CeO 2 and the proportion of addition are the same as SnO 2 , and its content is preferably 0 to 1%, more preferably 0 to 0.5%, and further preferably not added.

在不影響本發明光學玻璃的性能的前提下，可適當引入一定量的P2 O5 、Al2 O3 、Bi2 O3 、GeO2 、Lu2 O3 和F等成分。Under the premise of not affecting the performance of the optical glass of the present invention, a certain amount of P 2 O 5 , Al 2 O 3 , Bi 2 O 3 , GeO 2 , Lu 2 O 3 and F can be appropriately introduced.

本發明的光學玻璃是高折射率低色散玻璃，高折射率低色散玻璃製成的透鏡多與高折射率高色散玻璃製成的透鏡相組合，用於色差校正，且光學玻璃作為透鏡使用的情況下，越提高折射率則透鏡越能夠變薄，對於光學設備的小型化有利，本發明的光學玻璃的折射率nd＞1.87，較佳nd＞1.88，阿貝數vd＞38.0，較佳vd＞39.0。The optical glass of the present invention is a high-refractive index and low-dispersion glass. The lenses made of high-refractive-index and low-dispersion glass are mostly combined with lenses made of high-refractive-index and high-dispersion glass for chromatic aberration correction, and the optical glass is used as a lens In this case, the higher the refractive index, the thinner the lens can be, which is beneficial to the miniaturization of optical devices. The refractive index of the optical glass of the present invention is nd>1.87, preferably nd>1.88, Abbe number vd>38.0, preferably vd >39.0.

光學玻璃元件在製造和使用過程中，其拋光表面抵抗水、酸等各種侵蝕介質作用的能力稱為光學玻璃的化學穩定性，其主要取決於玻璃的化學組分，本發明的光學玻璃的耐水作用穩定性Dw（粉末法）在3級以上，較佳2級以上，更佳1級；耐酸作用穩定性DA （粉末法）在3級以上，較佳2級以上，更佳1級； 採用梯溫爐法測定玻璃的析晶性能，將玻璃製成180*10*10mm的樣品，側面拋光，放入帶有溫度梯度（5℃/cm）的爐內升溫至1400℃保溫4小時後取出自然冷卻到室溫，在顯微鏡下觀察玻璃析晶情況，玻璃出現晶體對應的最高溫度即為玻璃的析晶上限溫度。玻璃的析晶上限溫度越低，則玻璃在高溫時穩定性越強，生產的工藝性能越好。根據本發明一種典型的實施方式，較佳的，光學玻璃的析晶上限溫度低於1350℃，較佳低於1300℃，更佳低於1280℃。During the manufacturing and use of optical glass elements, the ability of the polished surface to resist the action of various corrosive media such as water and acid is called the chemical stability of optical glass, which mainly depends on the chemical composition of the glass. The water resistance of the optical glass of the present invention The action stability Dw (powder method) is above level 3, preferably above level 2, more preferably level 1, and the acid resistance D A (powder method) is above level 3, preferably above level 2, more preferably level 1; The crystallization performance of the glass was measured by the ladder furnace method. The glass was made into a 180*10*10mm sample, polished on the side, and placed in a furnace with a temperature gradient (5°C/cm). The temperature was raised to 1400°C for 4 hours and then taken out. Naturally cool to room temperature, observe the devitrification of the glass under a microscope, the highest temperature corresponding to the appearance of crystals in the glass is the upper limit temperature of glass devitrification. The lower the upper limit temperature of crystallization of the glass, the stronger the stability of the glass at high temperature and the better the process performance of the production. According to a typical embodiment of the present invention, preferably, the upper limit temperature of crystallization of the optical glass is lower than 1350°C, preferably lower than 1300°C, more preferably lower than 1280°C.

本發明玻璃的短波透射光譜特性用著色度（λ70 /λ5 ）表示。λ70 是指玻璃透射比達到70%時對應的波長，λ5 是指玻璃透射比達到5%時對應的波長，其中，λ70 的測定是使用具有彼此平行且光學拋光的兩個相對平面的厚度為10士0.lmm的玻璃，測定從280nm到700nm的波長域內的分光透射率並表現出透射率70%的波長。所謂分光透射率或透射率是在向玻璃的上述表面垂直地入射強度Iin 的光，透過玻璃並從一個平面射出強度Iout 的光的情況下通過。Iout /Iin 表示的量，並且也包含了玻璃的上述表面上的表面反射損失的透射率。玻璃的折射率越高，表面反射損失越大。因此，在高折射率玻璃中，λ70 的值小意味著玻璃自身的著色極少。本發明的光學玻璃透射比達到70％時對應的波長（λ70 ）λ70 小於或等於420nm，較佳小於或等於390nm其玻璃透射比達到5％時對應的波長（λ5 ）小於或等於360nm，較佳小於或等於350nm。The short-wave transmission spectrum characteristics of the glass of the present invention are expressed by the degree of coloration (λ 70 /λ 5 ). λ 70 refers to the wavelength when the glass transmittance reaches 70%, and λ 5 refers to the wavelength when the glass transmittance reaches 5%. Among them, λ 70 is measured using two opposing planes that are parallel to each other and optically polished. For glass with a thickness of 10±0.1mm, the spectral transmittance in the wavelength range from 280nm to 700nm is measured and shows a wavelength at which the transmittance is 70%. The so-called spectral transmittance or transmittance is when light having an intensity I in is perpendicularly incident on the above-mentioned surface of the glass, passing through the glass, and light having an intensity I out is emitted from one plane. I out /I in represents the amount, and also includes the transmittance of the surface reflection loss on the above-mentioned surface of the glass. The higher the refractive index of the glass, the greater the surface reflection loss. Therefore, in high refractive index glass, a small value of λ 70 means that the glass itself has very little coloration. When the optical glass transmittance of the present invention reaches 70%, the corresponding wavelength (λ 70 ) λ 70 is less than or equal to 420 nm, preferably less than or equal to 390 nm, and the corresponding wavelength (λ 5 ) when the glass transmittance reaches 5% is less than or equal to 360 nm , Preferably less than or equal to 350nm.

光學玻璃的密度是溫度為20℃時單位體積的質量，單位以g/cm3 表示，本發明的光學玻璃的密度小於5.3，較佳小於5.23。The density of the optical glass is the mass per unit volume at a temperature of 20°C, and the unit is expressed in g/cm 3. The density of the optical glass of the present invention is less than 5.3, preferably less than 5.23.

條紋度是用點光源和透鏡組成的條紋儀，從最容易看見條紋的方向上，與標準試樣比較檢查，共分為4級，分別為A、B、C、D級，A級為在規定檢測條件下，A級為規定檢測條件下無肉眼可見的條紋，B級為規定檢測條件下有細而分散的條紋，C級為規定檢測條件下無有輕微的平行條紋，D級為規定檢測條件下有粗略的條紋。由於以往技術中該類產品在不使用貴重氧化物如Ta2 O5 的條件下，抗析晶能力較差，生產20mm以上厚度的產品，容易產生析晶條紋。而厚規格產品又是製作大口徑（大於60mm)鏡片的必須規格。而目前由於光學技術的發展，需要大口徑鏡片越來越多，進而要求生產廠商提供20mm厚度以上的毛坯產品。The fringe degree is a fringe meter composed of a point light source and a lens. From the direction where the fringes are most easily seen, compared with the standard sample, it is divided into 4 levels, namely A, B, C, D, and A is in Under the specified detection conditions, Class A means that there are no visible stripes under the specified detection conditions, Class B refers to the thin and scattered stripes under the specified detection conditions, Class C refers to the absence of slight parallel stripes under the specified detection conditions, and Class D is the specification There are rough stripes under the detection conditions. Since this type of product in the past technology does not use expensive oxides such as Ta 2 O 5 , the anti-devitrification ability is poor, and the production of products with a thickness of 20 mm or more is prone to crystallization streaks. The thick specifications are the necessary specifications for the production of large-diameter (greater than 60mm) lenses. At present, due to the development of optical technology, more and more large-diameter lenses are required, and manufacturers are required to provide blank products with a thickness of 20mm or more.

光學玻璃氣泡品質按GB/T 7962.8-2010規定的測試方法進行測量。氣泡度是玻璃中允許氣泡含量的等級，氣泡不僅會影響玻璃製品的外觀品質，更會影響玻璃的光學性能、透明度、機械強度等，對玻璃造成很多不良影響，因此控制玻璃的氣泡度非常重要，本發明通過控制稀土氧化物La2 O3 、Gd2 O3 、Y2 O3 和Yb2 O3 的合計含量還能進一步實現玻璃氣泡度在A級以上，較佳A0 級以上，更佳A00 級。The quality of optical glass bubbles is measured according to the test method specified in GB/T 7962.8-2010. Bubble degree is the level of allowable bubble content in glass. Bubbles will not only affect the appearance quality of glass products, but also affect the optical properties, transparency, and mechanical strength of the glass, and cause many adverse effects on the glass. Therefore, it is very important to control the bubble degree of the glass. In the present invention, by controlling the total content of the rare earth oxides La 2 O 3 , Gd 2 O 3 , Y 2 O 3 and Yb 2 O 3 , the bubble degree of the glass can be further achieved above A level, preferably above A 0 level, and more Good A 00 level.

根據本發明的另一方面，提供了一種玻璃預製件或光學元件。該玻璃預製件或光學元件由上述任一種光學玻璃製備而成。本發明的光學預製件具有高折射率低色散特性；本發明的光學元件具有高折射率低色散特性，能夠以低成本提供光學性能優異的各種透鏡、稜鏡等光學元件。作為透鏡的例子，可舉出透鏡面為球面或非球面的凹彎月形透鏡、凸彎月形透鏡、雙凸透鏡、雙凹透鏡、平凸透鏡、平凹透鏡等各種透鏡。這種透鏡通過與高折射率高色散玻璃製成的透鏡組合，可校正色差，適合作為色差校正用的透鏡。另外，對於光學體系的緊湊化也是有效的透鏡。另外，對於稜鏡來說，由於折射率高，因此通過組合在攝像光學體系中，通過彎曲光路，朝向所需的方向，即可實現緊湊、廣角的光學體系。According to another aspect of the present invention, a glass preform or optical element is provided. The glass preform or optical element is prepared from any of the above-mentioned optical glasses. The optical preform of the present invention has the characteristics of high refractive index and low dispersion; the optical element of the present invention has the characteristics of high refractive index and low dispersion, and can provide various lenses and optical elements with excellent optical performance at low cost. Examples of lenses include various lenses such as concave meniscus lenses, convex meniscus lenses, biconvex lenses, biconcave lenses, plano-convex lenses, and plano-concave lenses whose lens surfaces are spherical or aspherical. This kind of lens can correct chromatic aberration by combining with a lens made of high-refractive-index and high-dispersion glass, and is suitable as a lens for chromatic aberration correction. In addition, it is also an effective lens for making the optical system compact. In addition, because of the high refractive index of the 稜鏡, a compact and wide-angle optical system can be realized by combining it in the imaging optical system by bending the optical path and facing the desired direction.

根據本發明的再一方面，提供了一種光學儀器，該光學儀器包括光學元件，光學元件為上述任一種光學元件。本發明的光學儀器可以是數位照相機、攝像機等。According to another aspect of the present invention, an optical instrument is provided, the optical instrument includes an optical element, and the optical element is any of the above-mentioned optical elements. The optical instrument of the present invention may be a digital camera, a video camera, or the like.

下面將結合實施例進一步說明本發明的有益效果。Hereinafter, the beneficial effects of the present invention will be further described in conjunction with embodiments.

[實施例][Example]

[光學玻璃實施例][Optical Glass Example]

為了得到具有表1至表9所示的組成的玻璃，使用碳酸鹽、硝酸鹽、氫氧化物、氧化物、硼酸等作為原料，將光學玻璃成分所對應的原料按比例稱量各原料，充分混合後成為調合原料，將該調合原料放入到鉑製坩鍋內，加熱至1200~1450℃，經熔化、攪拌、澄清後形成均勻的熔融玻璃，再將該熔融玻璃適度降溫後澆注到預熱的模具中並在650~700℃保持2~4小時之後進行緩冷，得到光學玻璃。另外，通過以下所示的方法測定各玻璃的特性，並將測定結果表示在表1至表9中。In order to obtain the glass with the composition shown in Table 1 to Table 9, use carbonate, nitrate, hydroxide, oxide, boric acid, etc. as raw materials, and weigh the raw materials corresponding to the optical glass components in proportion to fully After mixing, it becomes a blended raw material. The blended raw material is put into a platinum crucible, heated to 1200~1450°C, melted, stirred, and clarified to form a uniform molten glass, and then the molten glass is moderately cooled and poured into the pre-heated glass. In a hot mold, hold at 650-700°C for 2 to 4 hours and then slowly cool to obtain optical glass. In addition, the characteristics of each glass were measured by the method shown below, and the measurement results are shown in Tables 1 to 9.

（1）析晶上限溫度(1) The upper limit temperature of crystallization

採用梯溫爐法測定玻璃的析晶性能，將玻璃製成180*10*10mm的樣品，側面拋光，放入帶有溫度梯度（5℃/cm）的爐內升溫至1400℃保溫4小時後取出自然冷卻到室溫，在顯微鏡下觀察玻璃析晶情況，玻璃出現晶體對應的最高溫度即為玻璃的析晶上限溫度。The crystallization performance of the glass was measured by the ladder furnace method. The glass was made into a 180*10*10mm sample, polished on the side, and placed in a furnace with a temperature gradient (5°C/cm). The temperature was raised to 1400°C for 4 hours and then taken out. Naturally cool to room temperature, observe the devitrification of the glass under a microscope, the highest temperature corresponding to the appearance of crystals in the glass is the upper limit temperature of glass devitrification.

（2）折射率nd和阿貝數vd(2) Refractive index nd and Abbe number vd

折射率與色散係數按照GB/T7962.1-2010規定的方法進行測試。The refractive index and dispersion coefficient are tested according to the method specified in GB/T7962.1-2010.

（3）化學穩定性(3) Chemical stability

按GB/T 17129的測試方法測試耐水作用穩定性Dw和耐酸作用穩定性DA 。Test the water resistance stability Dw and the acid resistance stability D A according to the test method of GB/T 17129.

（4）條紋度(4) Stripe degree

按MLL-G-174B規定的方法進行測量。Measure according to the method specified in MLL-G-174B.

（5）氣泡度(5) Bubble degree

光學玻璃氣泡品質按GB/T7962.8-2010規定的測試方法進行測量。The bubble quality of the optical glass is measured according to the test method specified in GB/T7962.8-2010.

（6）玻璃著色度（λ70 、λ5 ）(6) Glass coloring degree (λ 70 , λ 5 )

使用具有彼此相對的兩個光學拋光平面的厚度為10±0.1mm的玻璃樣品，測定分光透射率，根據其結果而計算得出。A glass sample with a thickness of 10±0.1 mm with two optically polished planes facing each other was used to measure the spectral transmittance, and calculate it based on the result.

（7）密度(7) Density

按GB/T7962.20-2010規定的方法進行測量。Measure according to the method specified in GB/T7962.20-2010.

表1

Figure 108129356-A0304-0001
Table 1
Figure 108129356-A0304-0001

表2

Figure 108129356-A0304-0002
Table 2
Figure 108129356-A0304-0002

表3

Figure 108129356-A0304-0003
table 3
Figure 108129356-A0304-0003

表4

Figure 108129356-A0304-0004
Table 4
Figure 108129356-A0304-0004

表5

Figure 108129356-A0304-0005
table 5
Figure 108129356-A0304-0005

表6

Figure 108129356-A0304-0006
Table 6
Figure 108129356-A0304-0006

表7

Figure 108129356-A0304-0007
Table 7
Figure 108129356-A0304-0007

表8

Figure 108129356-A0304-0008
Table 8
Figure 108129356-A0304-0008

表9

Figure 108129356-A0304-0009
Table 9
Figure 108129356-A0304-0009

光學預製件實施例Examples of optical preforms

將表1中實施例1所得到的光學玻璃切割成預定大小，再在表面上均勻地塗布由氮化硼粉末構成的脫模劑，然後將其加熱、軟化，進行加壓成型，製作凹彎月形透鏡、凸彎月形透鏡、雙凸透鏡、雙凹透鏡、平凸透鏡、平凹透鏡等各種透鏡、稜鏡的預製件。The optical glass obtained in Example 1 in Table 1 was cut into a predetermined size, and then a mold release agent composed of boron nitride powder was uniformly coated on the surface, and then heated, softened, and press-molded to produce a concave curve. Lunar lenses, convex meniscus lenses, bi-convex lenses, bi-concave lenses, plano-convex lenses, plano-concave lenses, and other lenses, prefabricated parts.

[光學元件實施例][Embodiments of Optical Elements]

將上述光學預製件實施例所得到的這些預製件退火，在降低玻璃內部的變形的同時進行微調，使得折射率等光學特性達到所需值。Annealing the preforms obtained in the above-mentioned optical preform embodiment, while reducing the internal deformation of the glass, is fine-tuned to make the optical properties such as refractive index reach the desired value.

接著，對各預製件進行磨削、研磨，製作凹彎月形透鏡、凸彎月形透鏡、雙凸透鏡、雙凹透鏡、平凸透鏡、平凹透鏡等各種透鏡、稜鏡。所得光學元件的表面上還可塗布防反射膜。Next, each preform is ground and polished to produce various lenses, such as concave meniscus lenses, convex meniscus lenses, biconvex lenses, biconcave lenses, plano-convex lenses, and plano-concave lenses. An anti-reflection film may also be coated on the surface of the obtained optical element.

以上所述僅為本發明的較佳實施例而已，並不用於限制本發明，對於本領域的技術人員來說，本發明可以有各種更改和變化。凡在本發明的精神和原則之內，所作的任何修改、等同替換、改進等，均應包含在本發明的保護範圍之內。The above descriptions are only preferred embodiments of the present invention and are not intended to limit the present invention. For those skilled in the art, the present invention can have various modifications and changes. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

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無。no.

Claims (27)

一種光學玻璃，其特徵在於，相對於以氧化物換算的組成的玻璃總重量，按重量百分含量計，所述光學玻璃包括：B2O3：5~25%，La2O3：25~45%，Gd2O3：15~35%，Y2O3：0~10%，Yb2O3：0~10%，Nb2O5：2~15%，SiO2：0.5~15%，ZrO2：1~15%，TiO2：0.5~10%和WO3：0~10%，Nb2O5與TiO2的重量比Nb2O5/TiO2為2.17~8.5，且不含Ta2O5；La2O3與Gd2O3的重量比La2O3/Gd2O3為1.28~1.625；所述光學玻璃的析晶上限溫度低於1350℃。 An optical glass, characterized in that, relative to the total weight of the glass of the composition converted by oxide, the optical glass comprises: B 2 O 3 : 5-25%, La 2 O 3 : 25 ~45%, Gd 2 O 3 : 15~35%, Y 2 O 3 : 0~10%, Yb 2 O 3 : 0~10%, Nb 2 O 5 : 2~15%, SiO 2 : 0.5~15 %, ZrO 2: 1 ~ 15 %, TiO 2: 0.5 ~ 10% , and WO 3: 0 ~ 10%, Nb 2 O 5 and TiO 2 weight ratio of Nb 2 O 5 / TiO 2 2.17 to 8.5, and does not containing Ta 2 O 5; La 2 O 3 and Gd 2 O 3 ratio by weight of La 2 O 3 / Gd 2 O 3 1.625 ~ 1.28; upper devitrification temperature of the optical glass below 1350 ℃. 如請求項1所述之光學玻璃，其中，La2O3、Gd2O3、Y2O3和Yb2O3的合計量為50~75%，TiO2、Nb2O5和WO3的合計量為1~20%。 The optical glass according to claim 1, wherein the total amount of La 2 O 3 , Gd 2 O 3 , Y 2 O 3 and Yb 2 O 3 is 50-75%, and TiO 2 , Nb 2 O 5 and WO 3 The total amount is 1-20%. 如請求項1所述之光學玻璃，其中，所述光學玻璃還包括選自由ZnO、BaO、CaO、SrO、MgO、Sb2O3、Li2O、Na2O和K2O組成的組中的一種或多種，且含量如下：ZnO：0~15%，BaO：0~10%；CaO：0~10%；SrO：0~10%；MgO：0~10%；Sb2O3：0~1%，Li2O、Na2O和K2O的合計量為0~10%。 The optical glass according to claim 1, wherein the optical glass further includes selected from the group consisting of ZnO, BaO, CaO, SrO, MgO, Sb 2 O 3 , Li 2 O, Na 2 O, and K 2 O One or more of ZnO: 0~15%, BaO: 0~10%; CaO: 0~10%; SrO: 0~10%; MgO: 0~10%; Sb 2 O 3 :0 ~1%, the total amount of Li 2 O, Na 2 O and K 2 O is 0~10%. 如請求項2所述之光學玻璃，其中，所述光學玻璃還包括選自由ZnO、BaO、CaO、SrO、MgO、Sb2O3、Li2O、Na2O和K2O組成的組中的一種或多種，且含量如下：ZnO：0~15%，BaO：0~10%；CaO：0~10%；SrO：0~10%；MgO：0~10%；Sb2O3：0~1%，Li2O、Na2O和K2O的合計量為0~10%。 The optical glass according to claim 2, wherein the optical glass further includes selected from the group consisting of ZnO, BaO, CaO, SrO, MgO, Sb 2 O 3 , Li 2 O, Na 2 O and K 2 O One or more of ZnO: 0~15%, BaO: 0~10%; CaO: 0~10%; SrO: 0~10%; MgO: 0~10%; Sb 2 O 3 :0 ~1%, the total amount of Li 2 O, Na 2 O and K 2 O is 0~10%. 如請求項1所述之光學玻璃，其中，相對於以氧化物換算的組成的玻璃總重量，按重量百分含量計，所述光學玻璃由B2O3：5~25%，SiO2：0.5~15%，ZrO2：1~15%，ZnO：0~15%，BaO： 0~10%，CaO：0~10%，SrO：0~10%，MgO：0~10%，合計量為1~20%的TiO2、Nb2O5和WO3，合計量為0~10%的Li2O、Na2O和K2O，Sb2O3：0~1%，以及合計量為50~75%的La2O3、Gd2O3、Y2O3和Yb2O3組成。 The optical glass according to claim 1, wherein, relative to the total weight of the glass of the composition in terms of oxide conversion, the optical glass is composed of B 2 O 3 : 5-25%, SiO 2 : 0.5~15%, ZrO 2 : 1~15%, ZnO: 0~15%, BaO: 0~10%, CaO: 0~10%, SrO: 0~10%, MgO: 0~10%, total amount 1~20% TiO 2 , Nb 2 O 5 and WO 3 , the total amount is 0~10% Li 2 O, Na 2 O and K 2 O, Sb 2 O 3 :0~1%, and the total amount It is composed of 50~75% La 2 O 3 , Gd 2 O 3 , Y 2 O 3 and Yb 2 O 3. 如請求項1所述之光學玻璃，其中，相對於以氧化物換算的組成的玻璃總重量，按重量百分含量計，所述光學玻璃包括：B2O3：8~22%，SiO2：3~10%，ZrO2：3~12%，合計量為5~15%的TiO2、Nb2O5和WO3，和/或合計量為55~70%的La2O3、Gd2O3、Y2O3和Yb2O3。 The optical glass according to claim 1, wherein, relative to the total weight of the glass of the composition in terms of oxide conversion, the optical glass comprises: B 2 O 3 : 8-22%, SiO 2 ：3~10%, ZrO 2 ：3~12%, the total amount is 5~15% TiO 2 , Nb 2 O 5 and WO 3 , and/or the total amount is 55~70% La 2 O 3 , Gd 2 O 3 , Y 2 O 3 and Yb 2 O 3 . 如請求項1至5中任一項所述之光學玻璃，其中，Nb2O5與SiO2的重量比Nb2O5/SiO2為0.75~2。 The requested item 1 to 5 of one of the optical glass, wherein, Nb 2 O 5 weight ratio of SiO 2 and Nb 2 O 5 / SiO 2 from 0.75 to 2. 如請求項7所述之光學玻璃，其中，Nb2O5與SiO2的重量比Nb2O5/SiO2為1~1.5。 The optical glass of the seven requests, wherein, Nb 2 O 5 weight ratio of SiO 2 and Nb 2 O 5 / SiO 2 1 to 1.5. 如請求項1至5中任一項所述之光學玻璃，其中，La2O3與Gd2O3的重量比La2O3/Gd2O3為1.3~1.6。 The requested item 1 to 5, the optical glass of any one, wherein, La 2 O 3 and Gd 2 O 3 weight ratio of La 2 O 3 / Gd 2 O 3 1.3 to 1.6. 如請求項9所述之光學玻璃，其中，La2O3與Gd2O3的重量比La2O3/Gd2O3為1.4~1.5。 The optical glass according to the requested item 9, wherein, La 2 O 3 and Gd 2 O 3 weight ratio of La 2 O 3 / Gd 2 O 3 1.4 to 1.5. 如請求項1至5中任一項所述之光學玻璃，其中，所述光學玻璃不含Y2O3和/或WO3。 The optical glass according to any one of claims 1 to 5, wherein the optical glass does not contain Y 2 O 3 and/or WO 3 . 如請求項1至5中任一項所述之光學玻璃，其中，ZrO2與SiO2的重量比ZrO2/SiO2
Figure 108129356-A0305-02-0025-1
1。 The requested item 1 to 5, the optical glass of any one, wherein, ZrO 2 and SiO 2 weight ratio of ZrO 2 / SiO 2
Figure 108129356-A0305-02-0025-1
1. 如請求項1至4中任一項所述之光學玻璃，其中，所述光學玻璃的析晶上限溫度低於1300℃。 The optical glass according to any one of claims 1 to 4, wherein the upper limit temperature of crystallization of the optical glass is lower than 1300°C. 如請求項1至4中任一項所述之光學玻璃，其中，所述光學玻璃的折射率nd>1.87；阿貝數vd>38.0。 The optical glass according to any one of claims 1 to 4, wherein the refractive index of the optical glass nd>1.87; Abbe number vd>38.0. 如請求項14所述之光學玻璃，其中，所述光學玻璃的折射率nd>1.88；阿貝數vd>39.0。 The optical glass according to claim 14, wherein the refractive index of the optical glass nd>1.88; the Abbe number vd>39.0. 如請求項1至4中任一項所述之光學玻璃，其中，所述光學玻璃的耐水作用穩定性Dw在3級以上；耐酸作用穩定性DA在3級以上。 The optical glass according to any one of claims 1 to 4, wherein the water resistance stability Dw of the optical glass is above level 3; the acid resistance stability D A is above level 3. 如請求項16所述之光學玻璃，其中，所述光學玻璃的耐水作用穩定性Dw在2級以上；耐酸作用穩定性DA在2級以上。 The optical glass according to claim 16, wherein the water resistance stability Dw of the optical glass is above level 2; the acid resistance stability D A is above level 2. 如請求項17所述之光學玻璃，其中，所述光學玻璃的耐水作用穩定性Dw為1級；耐酸作用穩定性DA為1級。 The optical glass according to claim 17, wherein the water resistance stability Dw of the optical glass is level 1, and the acid resistance stability D A is level 1. 如請求項1至4中任一項所述之光學玻璃，其中，所述光學玻璃的條紋為C級以上；氣泡度為A級以上。 The optical glass according to any one of claims 1 to 4, wherein the stripes of the optical glass are C level or higher; and the bubble degree is A level or higher. 如請求項1至4中任一項所述之光學玻璃，其中，所述光學玻璃的條紋為B級以上；氣泡度為A0級以上。 The optical glass according to any one of claims 1 to 4, wherein the streaks of the optical glass are grade B or higher; and the degree of air bubbles is grade A 0 or higher. 如請求項1至4中任一項所述之光學玻璃，其中，所述光學玻璃的條紋為A級；氣泡度為A00級。 The optical glass according to any one of claims 1 to 4, wherein the stripes of the optical glass are A grade; the bubble degree is A 00 grade. 如請求項1至4中任一項所述之光學玻璃，其中，所述光學玻璃的透射比達到70%時對應的波長λ70小於或等於420nm；玻璃透射比達到5%時對應的波長λ5小於或等於360nm。 The optical glass according to any one of claims 1 to 4, wherein the corresponding wavelength λ 70 when the transmittance of the optical glass reaches 70% is less than or equal to 420 nm; the corresponding wavelength λ when the glass transmittance reaches 5% 5 is less than or equal to 360nm. 如請求項1至4中任一項所述之光學玻璃，其中，所述光學玻璃的透射比達到70%時對應的波長λ70小於或等於390nm；玻璃透射比達到5%時對應的波長λ5小於或等於350nm。 The optical glass according to any one of claims 1 to 4, wherein the corresponding wavelength λ 70 when the transmittance of the optical glass reaches 70% is less than or equal to 390 nm; the corresponding wavelength λ when the glass transmittance reaches 5% 5 is less than or equal to 350nm. 如請求項1至4中任一項所述之光學玻璃，其中，所述光學玻璃的密度小於5.3g/cm3。 The optical glass according to any one of claims 1 to 4, wherein the density of the optical glass is less than 5.3 g/cm 3 . 如請求項24所述之光學玻璃，其中，所述光學玻璃的密度小於5.23g/cm3。 The optical glass according to claim 24, wherein the density of the optical glass is less than 5.23 g/cm 3 . 一種玻璃預製件或光學元件，其特徵在於，由請求項1至25中任一項所述之光學玻璃製備而成。 A glass preform or optical element, characterized in that it is prepared from the optical glass described in any one of claims 1-25. 一種光學儀器，包括光學元件，其特徵在於，所述光學元件為如請求項26所述之光學元件。 An optical instrument, comprising an optical element, characterized in that the optical element is an optical element as described in claim 26.
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