TWI729504B - Optical glass, its preforms, optical components and optical instruments - Google Patents

Optical glass, its preforms, optical components and optical instruments Download PDF

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TWI729504B
TWI729504B TW108134387A TW108134387A TWI729504B TW I729504 B TWI729504 B TW I729504B TW 108134387 A TW108134387 A TW 108134387A TW 108134387 A TW108134387 A TW 108134387A TW I729504 B TWI729504 B TW I729504B
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optical glass
glass
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TW202012330A (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
    • 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
    • C03C4/00—Compositions for glass with special properties
    • 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

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  • Life Sciences & Earth Sciences (AREA)
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  • Organic Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Glass Compositions (AREA)

Abstract

本發明提供了一種按重量百分比計，含有SiO2 ：0-10%，B2 O3 ：5-25%，ZrO2 ：0-15%，ZnO：10-25%，TiO2 +Nb2 O5 +WO3 ：2-30%，Ln2 O3 ：30-55%的光學玻璃，所述Ln2 O3 為La2 O3 、Gd2 O3 、Y2 O3 和Yb2 O3 的合計含量，其中B2 O3 / Ln2 O3 為0.3-0.8，Y2 O3 / B2 O3 為0.15-2。該光學玻璃具有1.84-1.87的折射率（nd）和38-41的阿貝數（vd），同時耐失透性和氣泡度優異，化學穩定性好。The present invention provides a method which contains SiO 2 : 0-10%, B 2 O 3 : 5-25%, ZrO 2 : 0-15%, ZnO: 10-25%, TiO 2 +Nb 2 O based on weight percentage. 5 +WO 3 : 2-30%, Ln 2 O 3 : 30-55% of optical glass, the Ln 2 O 3 is La 2 O 3 , Gd 2 O 3 , Y 2 O 3 and Yb 2 O 3 The total content, where B 2 O 3 / Ln 2 O 3 is 0.3-0.8, and Y 2 O 3 / B 2 O 3 is 0.15-2. The optical glass has a refractive index (nd) of 1.84-1.87 and an Abbe number (vd) of 38-41, and at the same time has excellent devitrification resistance and bubble degree, and good chemical stability.

Description

光學玻璃、其預製件、光學元件和光學儀器Optical glass, its preforms, optical components and optical instruments

本發明屬於光學玻璃領域，具體涉及一種光學玻璃及其製作的預製件、光學元件和光學儀器。The invention belongs to the field of optical glass, and in particular relates to an optical glass and a preform, optical element and optical instrument made thereof.

光學玻璃可用於製造光學儀器中的透鏡、稜鏡、反射鏡等，由光學玻璃構成的部件是光學儀器中的關鍵性元件。具有1.84-1.87折射率（nd）、38-41阿貝數（vd）的光學玻璃因透射性能好、折射率高，被廣泛應用於製造照相機、望遠鏡、顯微鏡以及其它精密光學儀器的透鏡中。近年來，使用非球面透鏡減少光學元件的個數進而使光學儀器小型化和輕質化成為一大趨勢，市場需求也日益强烈。Optical glass can be used to manufacture lenses, mirrors, mirrors, etc. in optical instruments. Components made of optical glass are key components in optical instruments. Optical glass with 1.84-1.87 refractive index (nd) and 38-41 Abbe number (vd) is widely used in the manufacture of lenses for cameras, telescopes, microscopes and other precision optical instruments due to its good transmission performance and high refractive index. In recent years, the use of aspheric lenses to reduce the number of optical components has become a major trend in miniaturization and weight reduction of optical instruments, and the market demand has become increasingly strong.

但是，用熱壓成型再磨削和研磨、熔融玻璃再製造等傳統方法製造非球面透鏡成本高，而且作業工序複雜。精密模壓成型是一種操作更簡單、成本更低的用光學玻璃材料製備光學元件的方法。但是用該方法製作非球面透鏡將對玻璃材料的性能提出更高的要求。要求容易進行精密模壓成型，耐失透性高，熔點低，氣泡度優異等。如果光學元件要用在戶外長期使用的數位相機、攝影機等攝影設備中，還要求光學玻璃材料有較好的化學穩定性，以抵抗戶外環境中水、酸等的侵蝕，保證透鏡的使用質量和使用壽命。此外，對於需要在特殊溫度下工作的光學儀器，還要求玻璃材料有良好的熱膨脹係數，以降低溫度變化下玻璃膨脹和收縮的程度。However, traditional methods such as hot press molding, grinding and polishing, and molten glass remanufacturing are expensive to manufacture aspheric lenses, and the operating procedures are complicated. Precision compression molding is a simpler and lower cost method for preparing optical components from optical glass materials. However, the use of this method to make aspheric lenses will place higher requirements on the performance of glass materials. It is required to be easy to perform precision compression molding, high devitrification resistance, low melting point, and excellent air bubbles. If the optical components are to be used in digital cameras, video cameras and other photography equipment that are used outdoors for a long time, the optical glass materials are also required to have good chemical stability to resist the erosion of water and acid in the outdoor environment, and to ensure the quality and quality of the lens. Service life. In addition, for optical instruments that need to work at special temperatures, glass materials are also required to have a good coefficient of thermal expansion to reduce the degree of glass expansion and contraction under temperature changes.

中國專利CN104803600A、CN104098267A、CN105819682A等分別提供了折射率（nd）和阿貝數（vd）與本發明相同或接近的光學玻璃，但是仍然不能滿足上述的其他要求。Chinese patents CN104803600A, CN104098267A, CN105819682A, etc. respectively provide optical glasses whose refractive index (nd) and Abbe number (vd) are the same as or close to those of the present invention, but still cannot meet the above-mentioned other requirements.

鑒於現有技術存在的前述的不足，本發明的目的在於提供一種具有1.84-1.87折射率（nd）、38-41阿貝數（vd）的光學玻璃。所述光學玻璃容易進行精密模壓成型，且耐失透性高、氣泡度優異、化學穩定性好，成本低。In view of the aforementioned shortcomings in the prior art, the purpose of the present invention is to provide an optical glass with a refractive index (nd) of 1.84-1.87 and an Abbe number (vd) of 38-41. The optical glass is easy to perform precision compression molding, has high devitrification resistance, excellent bubble degree, good chemical stability, and low cost.

本發明還提供了由上述光學玻璃製作的預製件、光學元件和光學儀器。The present invention also provides preforms, optical elements and optical instruments made of the above-mentioned optical glass.

本發明為實現上述目的所採用的技術方案如下：The technical solutions adopted by the present invention to achieve the above-mentioned objectives are as follows:

光學玻璃，以重量%計，含有：SiO2 ：0-10%，B2 O3 ：5-25%，ZrO2 ：0-15%，ZnO：10-25%，TiO2 +Nb2 O5 +WO3 ：2-30%，Ln2 O3 ：30-55%，所述Ln2 O3 為La2 O3 、Gd2 O3 、Y2 O3 和Yb2 O3 的合計含量，其中B2 O3 /Ln2 O3 為0.3-0.8，Y2 O3 /B2 O3 為0.15-2。Optical glass, in% by weight, contains: SiO 2 :0-10%, B 2 O 3 : 5-25%, ZrO 2 : 0-15%, ZnO: 10-25%, TiO 2 +Nb 2 O 5 +WO 3 : 2-30%, Ln 2 O 3 : 30-55%, the Ln 2 O 3 is the total content of La 2 O 3 , Gd 2 O 3 , Y 2 O 3 and Yb 2 O 3, wherein B 2 O 3 /Ln 2 O 3 is 0.3-0.8, and Y 2 O 3 /B 2 O 3 is 0.15-2.

進一步地，上述光學玻璃，以重量%計，還含有：0-10%的RO，0-10%的Rn2 O，0-1%的澄清劑，所述RO為MgO、CaO、SrO或BaO中的一種或多種，所述Rn2 O為Li2 O、Na2 O、K2 O中的一種或多種，所述澄清劑為Sb2 O3 、SnO2 、CeO2 中的一種或多種。Further, the above-mentioned optical glass, in terms of weight %, further contains: 0-10% RO, 0-10% Rn 2 O, 0-1% clarifier, and the RO is MgO, CaO, SrO or BaO The Rn 2 O is one or more of Li 2 O, Na 2 O, and K 2 O, and the clarifying agent is one or more of Sb 2 O 3 , SnO 2 , and CeO 2 .

光學玻璃，以重量%計，由0-10%的SiO2 ，5-25%的B2 O3 ，0-15%的ZrO2 ，10-25%的ZnO，2-30%的TiO2 +Nb2 O5 +WO3 ，30-55%的Ln2 O3 ，0-10%的RO，0-10%的Rn2 O，0-1%的澄清劑組成，所述Ln2 O3 為La2 O3 、Gd2 O3 、Y2 O3 和Yb2 O3 的合計含量，所述RO為MgO、CaO、SrO或BaO中的一種或多種，所述Rn2 O為Li2 O、Na2 O、K2 O中的一種或多種，所述澄清劑為Sb2 O3 、SnO2 、CeO2 中的一種或多種，其中B2 O3 /Ln2 O3 為0.3-0.8，Y2 O3 /B2 O3 為0.15-2。Optical glass, based on weight %, consists of 0-10% SiO 2 , 5-25% B 2 O 3 , 0-15% ZrO 2 , 10-25% ZnO, 2-30% TiO 2 + Nb 2 O 5 +WO 3 , 30-55% Ln 2 O 3 , 0-10% RO, 0-10% Rn 2 O, 0-1% clarifying agent, the Ln 2 O 3 is The total content of La 2 O 3 , Gd 2 O 3 , Y 2 O 3 and Yb 2 O 3 , the RO is one or more of MgO, CaO, SrO or BaO, and the Rn 2 O is Li 2 O, One or more of Na 2 O and K 2 O, the clarifying agent is one or more of Sb 2 O 3 , SnO 2 , CeO 2 , wherein B 2 O 3 /Ln 2 O 3 is 0.3-0.8, Y 2 O 3 /B 2 O 3 is 0.15-2.

進一步地，前述的光學玻璃，各組分含量滿足以下4種情形中的一種或一種以上： 1）SiO2 /（SiO2 +B2 O3 ）為0-0.25； 2）Y2 O3 /Ln2 O3 為0.08-0.45； 3）Y2 O3 /Gd2 O3 為0.3-3； 4）Y2 O3 /（SiO2 +B2 O3 ）為0.16-0.8。Furthermore, in the aforementioned optical glass, the content of each component satisfies one or more of the following four situations: 1) SiO 2 /(SiO 2 +B 2 O 3 ) is 0-0.25; 2) Y 2 O 3 / Ln 2 O 3 is 0.08-0.45; 3) Y 2 O 3 /Gd 2 O 3 is 0.3-3; 4) Y 2 O 3 /(SiO 2 +B 2 O 3 ) is 0.16-0.8.

進一步地，前述的光學玻璃，其中：SiO2 ：1-8%，和/或B2 O3 ：10-23%，和/或ZrO2 ：1-10%，和/或ZnO：10-20%，和/或TiO2 +Nb2 O5 +WO3 ：4-22%，和/或Ln2 O3 ：35-52%，和/或RO：0-5%，和/或R2 O：0-5%，和/或澄清劑0-0.5%。Further, the aforementioned optical glass, wherein: SiO 2 : 1-8%, and/or B 2 O 3 : 10-23%, and/or ZrO 2 : 1-10%, and/or ZnO: 10-20 %, and/or TiO 2 +Nb 2 O 5 +WO 3 : 4-22%, and/or Ln 2 O 3 : 35-52%, and/or RO: 0-5%, and/or R 2 O ：0-5%, and/or clarifying agent 0-0.5%.

進一步地，前述的光學玻璃，各組分含量滿足以下6種情形中的一種或一種以上： 1）SiO2 /（SiO2 +B2 O3 ）為0.05-0.23； 2）Y2 O3 /Ln2 O3 為0.1-0.4； 3）Y2 O3 /Gd2 O3 為0.5-2.5； 4）Y2 O3 /（SiO2 +B2 O3 ）為0.2-0.7； 5）B2 O3 /Ln2 O3 為0.3-0.6； 6）Y2 O3 /B2 O3 為0.2-1.5。Further, in the aforementioned optical glass, the content of each component satisfies one or more of the following six situations: 1) SiO 2 /(SiO 2 +B 2 O 3 ) is 0.05-0.23; 2) Y 2 O 3 / Ln 2 O 3 is 0.1-0.4; 3) Y 2 O 3 /Gd 2 O 3 is 0.5-2.5; 4) Y 2 O 3 /(SiO 2 +B 2 O 3 ) is 0.2-0.7; 5) B 2 O 3 /Ln 2 O 3 is 0.3-0.6; 6) Y 2 O 3 /B 2 O 3 is 0.2-1.5.

進一步地，前述的光學玻璃，其中：SiO2 ：1-4%，和/或B2 O3 ：15-20%，和/或ZrO2 ：2-6%，和/或ZnO：13-17%，和/或TiO2 +Nb2 O5 +WO3 ：10-18%，和/或Ln2 O3 ：40-50%。Further, the aforementioned optical glass, wherein: SiO 2 : 1-4%, and/or B 2 O 3 : 15-20%, and/or ZrO 2 : 2-6%, and/or ZnO: 13-17 %, and/or TiO 2 +Nb 2 O 5 +WO 3 : 10-18%, and/or Ln 2 O 3 : 40-50%.

進一步地，前述的光學玻璃，各組分含量滿足以下6種情形中的一種或一種以上： 1）SiO2 /（SiO2 +B2 O3 ）為0.08-0.2； 2）Y2 O3 /Ln2 O3 為0.1-0.3； 3）Y2 O3 /Gd2 O3 為大於1但小於等於2； 4）Y2 O3 /（SiO2 +B2 O3 ）為0.3-0.6； 5）B2 O3 /Ln2 O3 為0.3-0.5； 6）Y2 O3 /B2 O3 為0.3-1。Furthermore, in the aforementioned optical glass, the content of each component satisfies one or more of the following six situations: 1) SiO 2 /(SiO 2 +B 2 O 3 ) is 0.08-0.2; 2) Y 2 O 3 / Ln 2 O 3 is 0.1-0.3; 3) Y 2 O 3 /Gd 2 O 3 is greater than 1 but less than or equal to 2; 4) Y 2 O 3 /(SiO 2 +B 2 O 3 ) is 0.3-0.6; 5 ) B 2 O 3 /Ln 2 O 3 is 0.3-0.5; 6) Y 2 O 3 /B 2 O 3 is 0.3-1.

進一步地，前述的光學玻璃，其中：Nb2 O5 ：1-15%，和/或WO3 ：1-15%，和/或TiO2 ：0-10%，和/或La2 O3 ：20-45%，和/或Gd2 O3 ：0-15%，和/或Y2 O3 ：1-15%，和/或Yb2 O3 ：0-5%。Further, the aforementioned optical glass, wherein: Nb 2 O 5 : 1-15%, and/or WO 3 : 1-15%, and/or TiO 2 : 0-10%, and/or La 2 O 3 : 20-45%, and/or Gd 2 O 3 : 0-15%, and/or Y 2 O 3 : 1-15%, and/or Yb 2 O 3 : 0-5%.

進一步地，前述的光學玻璃，其中：Nb2 O5 ：2-10%，和/或WO3 ：2-12%，和/或TiO2 ：0-5%，和/或La2 O3 ：25-40%，和/或Gd2 O3 ：1-10%，和/或Y2 O3 ：3-15%。Further, the aforementioned optical glass, wherein: Nb 2 O 5 : 2-10%, and/or WO 3 : 2-12%, and/or TiO 2 : 0-5%, and/or La 2 O 3 : 25-40%, and/or Gd 2 O 3 : 1-10%, and/or Y 2 O 3 : 3-15%.

進一步地，前述的光學玻璃，其中：Nb2 O5 ：4-8%，和/或WO3 ：6-10%，和/或La2 O3 ：30-35%，和/或Gd2 O3 ：3-7%，和/或Y2 O3 ：6-10%，和/或不含TiO2 。Further, the aforementioned optical glass, wherein: Nb 2 O 5 : 4-8%, and/or WO 3 : 6-10%, and/or La 2 O 3 : 30-35%, and/or Gd 2 O 3 : 3-7%, and/or Y 2 O 3 : 6-10%, and/or no TiO 2 .

進一步地，前述的光學玻璃，其折射率（nd）為1.84-1.87，優選為1.85-1.86；阿貝數（vd）為38.0-41.0，優選為38.5-40.0。Further, the refractive index (nd) of the aforementioned optical glass is 1.84-1.87, preferably 1.85-1.86; the Abbe number (vd) is 38.0-41.0, preferably 38.5-40.0.

進一步地，前述的光學玻璃，其粉末法耐水穩定性（DW ）為2類以上，優選為1類，粉末法耐酸穩定性（DA ）為3類以上，優選為2類；其氣泡度為A級或A級以上，優選為A0 級或A0 級以上。Furthermore, the aforementioned optical glass has a powder method water resistance (D W ) of class 2 or more, preferably class 1, and a powder method of acid resistance (D A ) of class 3 or more, preferably class 2; its bubble degree It is A grade or higher, preferably A 0 grade or A 0 grade or higher.

進一步地，前述的光學玻璃，其熱膨脹係數（α-30 ℃ -70 ℃ ）≤75×10-7 /K，優選（α-30 ℃ -70 ℃ ）≤70×10-7 /K；其轉變溫度（Tg ）為640℃以下，優選為630℃以下，更優選為625℃以下；所述光學玻璃的析晶上限溫度為1250℃以下，優選為1200℃以下，更優選為1180℃以下。Further, for the aforementioned optical glass, its thermal expansion coefficient (α -30 ℃ -70 ℃ ) ≤75×10 -7 /K, preferably (α -30 ℃ -70 ℃ ) ≤70×10 -7 /K; its transformation The temperature (T g ) is 640°C or lower, preferably 630°C or lower, more preferably 625°C or lower; the upper limit temperature of crystallization of the optical glass is 1250°C or lower, preferably 1200°C or lower, and more preferably 1180°C or lower.

玻璃預製件，採用前述的光學玻璃製成。The glass preform is made of the aforementioned optical glass.

光學元件，採用前述的光學玻璃或玻璃預製件製成。The optical element is made of the aforementioned optical glass or glass preform.

光學儀器，採用前述的光學元件製成。The optical instrument is made of the aforementioned optical components.

本發明的高折射低色散玻璃材料具有優異的耐失透性，又容易進行精密模壓成型，而且控制了稀土氧化物等高價格原料的含量，成本較低，適合推廣應用於精密模壓成型工藝中。同時，本發明通過合理的組分配比使玻璃的化學穩定性和氣泡度得以改善，提高了產品的成品率。一些優選的技術方案還進一步優化組分配比，以降低玻璃的熱膨脹係數，優化玻璃的抗析晶性能，强化化學穩定性。為製造質量更好、壽命更長的光學元件和光學儀器提供了高性價比的玻璃材料。The high-refractive low-dispersion glass material of the present invention has excellent devitrification resistance, is easy to be precision molded, and controls the content of high-priced raw materials such as rare earth oxides, and has low cost, and is suitable for popularization in precision molding processes . At the same time, the present invention improves the chemical stability and bubble degree of the glass through a reasonable composition ratio, and improves the yield of the product. Some preferred technical solutions further optimize the composition ratio to reduce the thermal expansion coefficient of the glass, optimize the anti-crystallization performance of the glass, and strengthen the chemical stability. It provides cost-effective glass materials for manufacturing better quality and longer life optical components and optical instruments.

光學玻璃Optical glass

下面對本發明的光學玻璃的組成進行詳細說明，在沒有特別說明時，各玻璃組分的含量、合計含量均指重量含量，以重量％表示，是某一組分的重量或幾種組分的重量之和佔光學玻璃總重量的百分數；各玻璃組分之比，或者幾種組分加和之比，是將其對應的重量含量作比或重量含量加和後作比。The composition of the optical glass of the present invention is described in detail below. Unless otherwise specified, the content and total content of each glass component refer to the weight content, expressed in weight %, which is the weight of a certain component or several components. The sum of weight accounts for the percentage of the total weight of the optical glass; the ratio of each glass component, or the ratio of the addition of several components, is the ratio of the corresponding weight content or the sum of the weight content.

本發明的光學玻璃具有滿足製作精密儀器的透鏡材料所需的光學性能，其折射率（nd）為1.84-1.87，阿貝數（vd）為38-41，而且容易精密模壓成型，化學穩定性和氣泡度優異。所述光學玻璃，以重量%計，含有：SiO2 ：0-10%，B2 O3 ：5-25%，ZrO2 ：0-15%，ZnO：10-25%，TiO2 +Nb2 O5 +WO3 ：2-30%，Ln2 O3 ：30-55%，所述Ln2 O3 為La2 O3 、Gd2 O3 、Y2 O3 和Yb2 O3 的合計含量，並且，其中B2 O3 /Ln2 O3 為0.3-0.8，Y2 O3 /B2 O3 為0.15-2。The optical glass of the present invention has the optical performance required to make the lens material of the precision instrument, the refractive index (nd) is 1.84-1.87, the Abbe number (vd) is 38-41, and it is easy to be precision molded and has chemical stability. And the bubble degree is excellent. The optical glass, in% by weight, contains: SiO 2 : 0-10%, B 2 O 3 : 5-25%, ZrO 2 : 0-15%, ZnO: 10-25%, TiO 2 +Nb 2 O 5 +WO 3 : 2-30%, Ln 2 O 3 : 30-55%, the Ln 2 O 3 is the total content of La 2 O 3 , Gd 2 O 3 , Y 2 O 3 and Yb 2 O 3 And, where B 2 O 3 /Ln 2 O 3 is 0.3-0.8, and Y 2 O 3 /B 2 O 3 is 0.15-2.

其中，B2 O3 是玻璃網絡形成組分，具有提高玻璃可熔性和耐失透性。為了達到上述效果，本發明引入5％以上或更多的B2 O3 ，優選引入10％以上的 B2 O3 ，更優選引入15％以上的B2 O3 ；但當其引入量超過25％時，則玻璃成玻穩定性下降，並且折射率下降，因此，本發明的B2 O3 的含量將25％設為上限，優選上限為23％，更優選上限為20％。Among them, B 2 O 3 is a glass network forming component, which can improve glass meltability and resistance to devitrification. In order to achieve the above effect, the present invention introduces 5% or more B 2 O 3 , preferably 10% or more B 2 O 3 , and more preferably 15% or more B 2 O 3 ; but when the amount exceeds 25 %, the glass forming stability is lowered and the refractive index is lowered. Therefore, the content of B 2 O 3 in the present invention is 25% as the upper limit, the upper limit is preferably 23%, and the upper limit is more preferably 20%.

SiO2 在本發明中是一種任選的組分，其也構成玻璃形成體。SiO2 在玻璃中形成的是矽氧四面體三維網絡，非常緻密堅固。這樣的網絡加入到玻璃中，對疏鬆的硼氧三角體網絡進行加固，使其變得緻密，從而提升玻璃的高溫黏度。此外，SiO2 含量越高越有利於降低玻璃的熱膨脹係數。本發明的光學玻璃中SiO2 含量的下限為0％，優選為1％；但若SiO2 的含量過大，會使玻璃的轉變溫度升高，並使玻璃的熔融性降低，增加工藝難度，因此其含量上限為10％，優選上限為8％，進一步優選上限為4％。SiO 2 is an optional component in the present invention, which also constitutes a glass former. SiO 2 forms a three-dimensional network of silicon-oxygen tetrahedrons in the glass, which is very dense and strong. Such a network is added to the glass to reinforce the loose boron-oxygen triangle network to make it dense, thereby increasing the high-temperature viscosity of the glass. In addition, the higher the SiO 2 content, the more beneficial it is to reduce the thermal expansion coefficient of the glass. The lower limit of the content of SiO 2 in the optical glass of the present invention is 0%, preferably 1%; however, if the content of SiO 2 is too large, the glass transition temperature will increase, and the melting of the glass will decrease, increasing the difficulty of the process. The upper limit of its content is 10%, the preferred upper limit is 8%, and the more preferred upper limit is 4%.

SiO2 和B2 O3 都是玻璃網絡形成組分，經本發明人研究發現，在本發明的配方下，SiO2 /（SiO2 +B2 O3 ）會影響玻璃的抗析晶性能和熱膨脹係數。SiO2 /（SiO2 +B2 O3 ）的值越大，玻璃的熱膨脹係數越低，越有利於减小玻璃對溫度的敏感性，但同時將導致玻璃的抗析晶性能劣化。經研究發現，在本發明的配方中，當SiO2 /（SiO2 +B2 O3 ）的值在0-0.25範圍時，能使玻璃的熱膨脹係數低於75×10-7 /K ，而且抗析晶性能優良，優選的比值範圍是0.05-0.23，更優選的範圍是0.08-0.2。Both SiO 2 and B 2 O 3 are glass network forming components. The inventor found that under the formula of the present invention, SiO 2 /(SiO 2 +B 2 O 3 ) will affect the devitrification resistance and thermal expansion of the glass. coefficient. The larger the value of SiO 2 /(SiO 2 +B 2 O 3 ), the lower the thermal expansion coefficient of the glass, which is more conducive to reducing the temperature sensitivity of the glass, but at the same time it will lead to the deterioration of the glass's anti-crystallization performance. It is found through research that in the formula of the present invention, when the value of SiO 2 /(SiO 2 +B 2 O 3 ) is in the range of 0-0.25, the thermal expansion coefficient of the glass can be lower than 75×10 -7 /K, and The devitrification resistance is excellent, the preferred ratio range is 0.05-0.23, and the more preferred range is 0.08-0.2.

ZrO2 在本發明中作為任選的成分，是一種高折射低色散氧化物，加入玻璃中可以提升玻璃的折射率並調節色散。同時，合適量的ZrO2 加入玻璃中，可以提升玻璃的抗析晶性能和化學穩定性。但是在本發明的光學玻璃中，若其含量高於15％，玻璃會變得難以融化，熔煉溫度會上升，容易導致玻璃內部出現夾雜物及其透過率下降。因此，其含量設置為0-15％，優選為1-10％，進一步優選為2-6％。As an optional component in the present invention, ZrO 2 is a high-refractive low-dispersion oxide. Adding to the glass can increase the refractive index of the glass and adjust the dispersion. At the same time, adding a proper amount of ZrO 2 to the glass can improve the glass's anti-crystallization performance and chemical stability. However, in the optical glass of the present invention, if its content is higher than 15%, the glass will become difficult to melt, and the melting temperature will increase, which easily causes inclusions in the glass and a decrease in transmittance. Therefore, its content is set to 0-15%, preferably 1-10%, and more preferably 2-6%.

ZnO可以調整玻璃的折射率和色散，改善玻璃的抗析晶性能，降低玻璃的轉變溫度，提升玻璃的化學穩定性。ZnO還可以降低玻璃的高溫黏度，使得玻璃可以在較低溫度下熔煉，從而可以提升玻璃的透過率。但如果ZnO加入量過多，玻璃的抗析晶性能反而會下降，同時高溫黏度較小，給成型帶來困難。因此，在本發明玻璃體系中，ZnO的含量下限設為10％，優選的下限為13%；ZnO的含量上限設為25%，優選的上限為20%，更優選的上限為17%。ZnO can adjust the refractive index and dispersion of the glass, improve the devitrification resistance of the glass, reduce the glass transition temperature, and improve the chemical stability of the glass. ZnO can also reduce the high temperature viscosity of the glass, so that the glass can be smelted at a lower temperature, which can increase the transmittance of the glass. However, if the amount of ZnO is too much, the devitrification resistance of the glass will decrease, and the high temperature viscosity will be small, which will bring difficulties to the molding. Therefore, in the glass system of the present invention, the lower limit of the ZnO content is set to 10%, and the preferred lower limit is 13%; the upper limit of the ZnO content is set to 25%, the preferred upper limit is 20%, and the more preferred upper limit is 17%.

TiO2 作為任選的組分，能提高玻璃的折射率，適量添加TiO2 到本發明玻璃中，可以增加玻璃抗析晶穩定性，而且可以一定的替代Nb2 O5 和WO3 。但含量過高將導致玻璃透過率下降。在本發明的光學玻璃中，TiO2 的含量為0-10%，優選的含量為0-5%，更優選的含量為0%。As an optional component, TiO 2 can increase the refractive index of the glass. Adding TiO 2 in an appropriate amount to the glass of the present invention can increase the anti-crystallization stability of the glass and can replace Nb 2 O 5 and WO 3 to a certain extent. However, too high a content will cause the glass transmittance to decrease. In the optical glass of the present invention, the content of TiO 2 is 0-10%, the preferred content is 0-5%, and the more preferred content is 0%.

Nb2 O5 是能提高玻璃化學穩定性和折射率的組分。當Nb2 O5 的含量小於1％時，光學常數達不到設計要求；而當其含量超過 15％時，玻璃的抗失透性降低，因此，Nb2 O5 的含量限定為1-15％，優選為2-10％，更優選為4-8％。Nb 2 O 5 is a component that can improve the chemical stability and refractive index of the glass. When the content of Nb 2 O 5 is less than 1%, the optical constant cannot meet the design requirements; when its content exceeds 15%, the devitrification resistance of the glass is reduced. Therefore, the content of Nb 2 O 5 is limited to 1-15 %, preferably 2-10%, more preferably 4-8%.

WO3 在玻璃中的主要作用是維持光學常數，改善玻璃析晶性能，但其含量過高，會使玻璃透過率降低，著色度增大，且析晶性能變壞。所以，WO3 的優選含量是1-15％，更優選含量是2-12％，進一步優選含量為6-10％。The main function of WO 3 in glass is to maintain the optical constant and improve the crystallization performance of the glass, but if its content is too high, the glass transmittance will be reduced, the coloring degree will increase, and the crystallization performance will be deteriorated. Therefore, the preferred content of WO 3 is 1-15%, more preferably the content is 2-12%, and still more preferably the content is 6-10%.

由於TiO2 、Nb2 O5 、WO3 都具有提高折射率但也提高色散的作用，因此，從本發明的光學玻璃需要具有高折射、低色散和高透過率的要求出發，將TiO2 +Nb2 O5 +WO3 的上限設為30%，優選的上限為22%，更優選的上限為18%。但是，當TiO2 +Nb2 O5 +WO3 過低，又將導致玻璃的熱穩定和可壓性下降，因此，將其下限設為2%，優選的下限為4%，更優的下限為10%。Since TiO 2, Nb 2 O 5, WO 3 , but increasing the refractive index are also improved dispersion effect, therefore, the optical glass of the present invention is required to have a high refractive requirements, high transmittance and low dispersion viewpoint, the TiO 2 + The upper limit of Nb 2 O 5 +WO 3 is set to 30%, the preferable upper limit is 22%, and the more preferable upper limit is 18%. However, when TiO 2 +Nb 2 O 5 +WO 3 is too low, the thermal stability and compressibility of the glass will decrease. Therefore, the lower limit is set to 2%, the preferred lower limit is 4%, and the better lower limit Is 10%.

加入稀土氧化物Ln2 O3 （La2 O3 、Gd2 O3 、Y2 O3 和Yb2 O3 ）有助於提高玻璃的折射率，當其總含量低於30％時，無法獲得預期的光學常數，但當其總含量超過55％時，玻璃的化學穩定性、耐失透性將降低，而且將提高玻璃的原料成本。因此 La2 O3 、Gd2 O3 、Y2 O3 和Yb2 O3 的合計含量Ln2 O3 設為30-55％，優選為35-52％，進一步優選為40-50％。The addition of rare earth oxide Ln 2 O 3 (La 2 O 3 , Gd 2 O 3 , Y 2 O 3 and Yb 2 O 3 ) helps to increase the refractive index of the glass. When the total content is less than 30%, it cannot be obtained Expected optical constant, but when its total content exceeds 55%, the chemical stability and devitrification resistance of the glass will be reduced, and the raw material cost of the glass will be increased. Therefore, the total content Ln 2 O 3 of La 2 O 3 , Gd 2 O 3 , Y 2 O 3 and Yb 2 O 3 is 30-55%, preferably 35-52%, and more preferably 40-50%.

稀土氧化物Ln2 O3 分散在玻璃網絡中，主要用於提高折射率，但是本申請發明人在研究中發現，玻璃網格組分B2 O3 與Ln2 O3 的比例對玻璃的化學穩定性有重要的影響。當B2 O3 /Ln2 O3 低於0.3時，化學穩定性，特別是耐酸穩定性不能滿足要求，而當B2 O3 /Ln2 O3 高於0.8時，折射率又將降低，因此本發明將其範圍設為0.3-0.8，優選為0.3-0.6，更優選為0.3-0.5。The rare earth oxide Ln 2 O 3 is dispersed in the glass network and is mainly used to increase the refractive index. However, the inventor of the present application found in the research that the ratio of the glass mesh components B 2 O 3 to Ln 2 O 3 has an effect on the chemistry of the glass. Stability has an important impact. When B 2 O 3 /Ln 2 O 3 is lower than 0.3, the chemical stability, especially the acid resistance stability, cannot meet the requirements, and when B 2 O 3 /Ln 2 O 3 is higher than 0.8, the refractive index will decrease again. Therefore, the present invention sets the range to 0.3-0.8, preferably 0.3-0.6, and more preferably 0.3-0.5.

稀土氧化物中的La2 O3 是可以改善玻璃光學特性的組分，但當其含量超過45％時，玻璃耐失透性與熔融性能均惡化。因此，優選本發明的La2 O3 的含量為20-45％，更優選為25-40％，進一步優選為30-35％。 La 2 O 3 in the rare earth oxide is a component that can improve the optical properties of the glass, but when its content exceeds 45%, the devitrification resistance and melting performance of the glass deteriorate. Therefore, the content of La 2 O 3 in the present invention is preferably 20-45%, more preferably 25-40%, and still more preferably 30-35%.

Gd2 O3 作為任選的組分，可以增加玻璃的折射率且不明顯提高玻璃的色散，本發明中通過引入Gd2 O3 ，可以提高形成玻璃的穩定性，並且使玻璃的化學穩定性顯著增强，在維持折射率的同時，控制色散的過度上升；但如果其含量超過15％時，則玻璃耐失透性降低且玻璃的密度呈上升趨勢。因此，本發明的Gd2 O3 的含量為0-15％，優選範圍為1-10％，更優選範圍為3-7％。As an optional component, Gd 2 O 3 can increase the refractive index of the glass without significantly increasing the dispersion of the glass. In the present invention, by introducing Gd 2 O 3 , the stability of glass formation can be improved, and the chemical stability of the glass can be improved. Significantly enhanced, while maintaining the refractive index, the excessive increase in dispersion is controlled; but if its content exceeds 15%, the devitrification resistance of the glass will decrease and the density of the glass will increase. Therefore, the content of Gd 2 O 3 in the present invention is 0-15%, preferably in the range of 1-10%, and more preferably in the range of 3-7%.

Y2 O3 是維持高折射率和高阿貝數，抑制玻璃材料成本上升，並可改善玻璃的熔融性、耐失透性，還可降低玻璃析晶上限溫度和比重的組分，但在本發明的配方中，若其含量超過15％，則玻璃的化學穩定性、耐失透性降低。因此，優選Y2 O3 含量範圍為1-15％，更優選範圍為3-15％，進一步優選為6-10％。Y 2 O 3 is a component that maintains a high refractive index and a high Abbe number, suppresses the increase in the cost of glass materials, can improve the meltability and devitrification resistance of the glass, and can also reduce the upper limit temperature and specific gravity of glass crystallization. In the formulation of the present invention, if its content exceeds 15%, the chemical stability and devitrification resistance of the glass will decrease. Therefore, the content of Y 2 O 3 is preferably in the range of 1-15%, more preferably in the range of 3-15%, and still more preferably in the range of 6-10%.

Y2 O3 與其他稀土氧化物均能提高玻璃折射率，又因成本較Gd2 O3 低，而且能降低玻璃密度，有利於輕質化，因此，較多的現有技術中均有引入該組分。然而，在本發明的配方體系中，Y2 O3 的含量不僅獨立地對玻璃產生前述的影響，還與其他多個組分協同調節玻璃的多個性能。其中包括：Both Y 2 O 3 and other rare earth oxides can increase the refractive index of the glass, and because the cost is lower than that of Gd 2 O 3 , and can reduce the glass density, it is beneficial to light weight. Therefore, many existing technologies have introduced this Components. However, in the formulation system of the present invention, the content of Y 2 O 3 not only independently exerts the aforementioned effects on the glass, but also synergistically adjusts multiple properties of the glass with other components. These include:

當本發明的光學玻璃均含有Y2 O3 與La2 O3 時，可以更有效地提高玻璃的耐失透性能，並且在玻璃材料製作玻璃元件時更容易進行精密模壓成型，降低玻璃元件製造的難度；When the optical glass of the present invention contains Y 2 O 3 and La 2 O 3 , the devitrification resistance of the glass can be more effectively improved, and it is easier to perform precision compression molding when the glass material is used to make glass components, which reduces the production of glass components. The difficulty of

當Y2 O3 / B2 O3 過低時，在熔煉過程中不易排出氣體，導致玻璃氣泡度較差，因此Y2 O3 /B2 O3 的值下限為0.15，優選為0.2，更優選為0.3；但Y2 O3 /B2 O3 過高，玻璃有化學穩定性下降的趨勢，因此，Y2 O3 /B2 O3 的值上限為2，優選為1.8，更優選為1.5，進一步優選為1.3，更進一步優選為1；When Y 2 O 3 / B 2 O 3 is too low, it is difficult to discharge gas during the smelting process, resulting in poor glass bubbles. Therefore, the lower limit of Y 2 O 3 /B 2 O 3 is 0.15, preferably 0.2, more preferably However, if Y 2 O 3 /B 2 O 3 is too high, the chemical stability of the glass tends to decrease. Therefore, the upper limit of the value of Y 2 O 3 /B 2 O 3 is 2, preferably 1.8, and more preferably 1.5 , More preferably 1.3, still more preferably 1;

Gd2 O3 和Y2 O3 在提高折射率方面可以在一定程度上進行替換，Y2 O3 /Gd2 O3 的值越高，越有利於降低原料成本，此外，發明人還發現當Y2 O3 /Gd2 O3 低於0.3或高於3時，都會導致玻璃的抗析晶性能劣化，因此，將Y2 O3 /Gd2 O3 設為0.3-3，優選為0.5-2.5，更優選為大於1但小於等於2；Gd 2 O 3 and Y 2 O 3 can be replaced to a certain extent in improving the refractive index. The higher the value of Y 2 O 3 /Gd 2 O 3 , the more conducive to reducing the cost of raw materials. In addition, the inventor also found that when When Y 2 O 3 /Gd 2 O 3 is lower than 0.3 or higher than 3, the devitrification resistance of the glass will deteriorate. Therefore, Y 2 O 3 /Gd 2 O 3 is set to 0.3-3, preferably 0.5- 2.5, more preferably greater than 1 but less than or equal to 2;

Y2 O3 在所有稀土氧化物中的佔比Y2 O3 /Ln2 O3 對玻璃的抗析晶性能有明顯的調節作用，當Y2 O3 /Ln2 O3 的值為0.08-0.45時，抗析晶性能優異，更優選的值為0.1-0.4，進一步優選為0.1-0.3。The proportion of Y 2 O 3 in all rare earth oxides Y 2 O 3 /Ln 2 O 3 has a significant adjustment effect on the anti-crystallization performance of glass, when the value of Y 2 O 3 /Ln 2 O 3 is 0.08- At 0.45, the devitrification resistance is excellent, and the more preferable value is 0.1-0.4, and the more preferable value is 0.1-0.3.

此外，Y2 O3 /（SiO2 +B2 O3 ）會影響玻璃的化學穩定性，當該值在0.16-0.8時，玻璃的化學穩定性優異，耐腐蝕性能强，可以有效延長光學儀器的使用壽命，更優選Y2 O3 /（SiO2 + B2 O3 ）的值為0.2-0.7，進一步優選為0.3-0.6。In addition, Y 2 O 3 /(SiO 2 +B 2 O 3 ) will affect the chemical stability of the glass. When the value is 0.16-0.8, the glass has excellent chemical stability and strong corrosion resistance, which can effectively extend the optical instrument The service life of Y 2 O 3 /(SiO 2 + B 2 O 3 ) is more preferably 0.2-0.7, more preferably 0.3-0.6.

Yb2 O3 是高折射率低色散組分，其含量超過5％時，玻璃的穩定性、耐失透性降低，因此，Yb2 O3 含量範圍限定為0-5％。同時，由於Yb2 O3 相對於Gd2 O3 、Y2 O3 比較昂貴，對玻璃的熔融性能改善作用小，因此優選不引入。Yb 2 O 3 is a component with high refractive index and low dispersion. When its content exceeds 5%, the stability and devitrification resistance of the glass will decrease. Therefore, the content of Yb 2 O 3 is limited to 0-5%. At the same time, since Yb 2 O 3 is relatively expensive compared to Gd 2 O 3 and Y 2 O 3 , and has little effect on improving the melting performance of the glass, it is preferably not introduced.

RO屬於鹼土金屬氧化物，為CaO、MgO、SrO和BaO中的一種或多種，在本發明中是任選的組分。合適量的鹼土金屬氧化物加入玻璃中可以提升玻璃的楊氏模量，降低玻璃的高溫黏度，同時平衡玻璃組分，改善玻璃的熔化性能。但是，當RO的合計含量高於10％時，過多的鹼土金屬氧化物會降低玻璃的抗析晶性能。因此，本發明將RO的值設定為0-10%，優選為0-5%。RO belongs to alkaline earth metal oxides, which is one or more of CaO, MgO, SrO and BaO, and is an optional component in the present invention. The addition of an appropriate amount of alkaline earth metal oxides to the glass can increase the Young's modulus of the glass, reduce the high-temperature viscosity of the glass, and at the same time balance the glass components and improve the melting performance of the glass. However, when the total content of RO is higher than 10%, excessive alkaline earth metal oxides will reduce the devitrification resistance of the glass. Therefore, the present invention sets the value of RO to 0-10%, preferably 0-5%.

Rn2 O屬於鹼金屬氧化物，為Li2 O、Na2 O、K2 O中的一種或多種，在本發明中是任選的組分。在本發明玻璃體系中，適量的鹼金屬氧化物可以獲得預期的高溫黏度，同時，當適量的鹼金屬氧化物與B2 O3 共存時，還可以提高B2 O3 網絡的緻密度，獲得更好的光透過率。過少的鹼金屬氧化物不能調整玻璃的黏度到合適的範圍，而過多的鹼金屬氧化物又會急劇破壞玻璃的抗析晶性能。在本發明中，將Rn2 O的值設定為0-10%，優選為0-5%。Rn 2 O is an alkali metal oxide, which is one or more of Li 2 O, Na 2 O, and K 2 O, and is an optional component in the present invention. In the glass system of the present invention, an appropriate amount of alkali metal oxide can obtain the expected high-temperature viscosity. At the same time, when an appropriate amount of alkali metal oxide and B 2 O 3 coexist, it can also increase the density of the B 2 O 3 network and obtain Better light transmittance. Too little alkali metal oxide cannot adjust the viscosity of the glass to an appropriate range, and too much alkali metal oxide will drastically destroy the glass's anti-crystallization performance. In the present invention, the value of Rn 2 O is set to 0-10%, preferably 0-5%.

另外，本發明的玻璃中可以引入0-1％、優選為0-0.5％的澄清劑，這些澄清劑可選用Sb2 O3 或/和CeO2 或/和SnO2 。In addition, 0-1%, preferably 0-0.5% of a fining agent can be introduced into the glass of the present invention, and these fining agents can be Sb 2 O 3 or/and CeO 2 or/and SnO 2 .

在不損害本發明的玻璃特性的範圍內，根據需要能夠添加少量上述未曾提及的其他成分，如P2 O5 、Bi2 O3 、TeO2 、Ga2 O3 、GeO2 、Ta2 O5 、Lu2 O3 等。但是 V、Cr、Mn、Fe、Co、Ni、Cu、Ag以及 Mo等過渡金屬成分，即使單獨或複合地少量含有的情況下，玻璃也會被著色，在可見光區域的特定的波長產生吸收，從而减弱本發明的提高可見光透過率效果的性質，因此，特別是對於可見光區域波長的透過率有要求的光學玻璃，優選實際上不包含。Within the scope of not impairing the characteristics of the glass of the present invention, a small amount of other components not mentioned above can be added as needed, such as P 2 O 5 , Bi 2 O 3 , TeO 2 , Ga 2 O 3 , GeO 2 , Ta 2 O 5. Lu 2 O 3 and so on. However, even if the transition metal components such as V, Cr, Mn, Fe, Co, Ni, Cu, Ag, and Mo are contained in small amounts individually or in combination, the glass will be colored and absorb at a specific wavelength in the visible light region. As a result, the property of the present invention to improve the visible light transmittance effect is weakened. Therefore, it is preferable that the optical glass that requires the transmittance of wavelengths in the visible light region is not actually included.

Pb、As、Th、Cd、Tl、Os、Be以及Se的化合物，近年來作為有害的化學物質而有控制使用的傾向，不僅在玻璃的製造工序，直至加工工序以及產品化後的處置上對環境保護的措施是必需的。因此，在重視對環境的影響的情況下，除了不可避免地混入以外，優選實際上不含有它們。由此，光學玻璃變得實際上不包含污染環境的物質。因此，即使不採取特殊的環境對策上的措施，本發明的光學玻璃也能夠進行製造、加工以及廢棄。Compounds of Pb, As, Th, Cd, Tl, Os, Be, and Se, in recent years, have tended to be controlled as harmful chemical substances, not only in the glass manufacturing process, until the processing process and the disposal after commercialization. Environmental protection measures are necessary. Therefore, in the case of attaching importance to the impact on the environment, it is preferable not to actually contain them except for unavoidable mixing. As a result, the optical glass does not actually contain substances that pollute the environment. Therefore, even if no special environmental countermeasures are taken, the optical glass of the present invention can be manufactured, processed, and discarded.

光學玻璃的性能Performance of optical glass

[光學性能][Optical performance]

折射率（nd）按照GB/T7962.1-2010方法測試。The refractive index (nd) is tested according to the GB/T7962.1-2010 method.

色散係數（即阿貝數，vd）按照GB/T7962.1-2010方法測試。The dispersion coefficient (ie Abbe number, vd) is tested in accordance with the GB/T7962.1-2010 method.

[熱學性能][Thermal Performance]

熱膨脹係數（α-30 ℃ -70 ℃ ）按照GB/T7962.16-2010方法測試，單位10-7 /K。The coefficient of thermal expansion (α -30 ℃ -70 ℃ ) is tested according to the method of GB/T7962.16-2010, and the unit is 10 -7 /K.

轉變溫度（Tg ）按GB/T 7962.16-2010規定的方法進行測量，單位：℃。Transition temperature (T g ) is measured according to the method specified in GB/T 7962.16-2010, unit: ℃.

析晶上限溫度測試方法為：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小時後取出自然冷却到室溫，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强，生產的工藝性能越好。The test method for the upper limit of crystallization temperature is: use the ladder furnace method to determine the crystallization performance of the glass, make the glass into a sample of 180*10*10mm, polish the side, and put it in a furnace with a temperature gradient (5°C/cm) to increase the temperature After keeping it at 1400°C for 4 hours, take it out and cool it naturally to room temperature. Observe the crystallization of the glass under a microscope. The highest temperature corresponding to the appearance of crystals in the glass is the upper limit temperature of the glass. 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.

[化學穩定性][Chemical stability]

耐水作用穩定性（DW ）按照GB/T17129方法測試。Water resistance stability (D W ) is tested in accordance with the GB/T17129 method.

耐酸作用穩定性（DA ）按照GB/T17129方法測試。Acid on stability (D A) in accordance with GB / T17129 test method.

[氣泡度][Bubble degree]

氣泡度按照GB/T7962.8-2010方法測試。The degree of air bubbles is tested in accordance with the GB/T7962.8-2010 method.

經過測試，本發明的玻璃具有以下性能：折射率（nd）為1.84-1.87，優選為1.85-1.86；阿貝數（vd）為38-41，優選為38.5-40；熱膨脹係數（α-30 ℃ -70 ℃ ）≤75×10-7 /K，優選≤70×10-7 /K；耐水作用穩定性（DW ）達到2類以上，優選為1類；耐酸作用穩定性(DA )達到3類以上，優選達到2類以上；析晶上限溫度為1250℃以下，優選為1200℃以下，更優選為1180℃以下；氣泡度達到A級以上，優選為A0 級以上，更優選為A00 級；玻璃轉變溫度（Tg ）為640℃以下，優選為630℃以下，更優選為625℃以下。After testing, the glass of the present invention has the following properties: refractive index (nd) is 1.84-1.87, preferably 1.85-1.86; Abbe number (vd) is 38-41, preferably 38.5-40; thermal expansion coefficient (α -30 ℃ -70 ℃ )≤75×10 -7 /K, preferably ≤70×10 -7 /K; water resistance stability (D W ) reaches class 2 or more, preferably class 1; acid resistance stability (D A ) Class 3 or higher, preferably Class 2 or higher; the upper limit temperature of crystallization is 1250°C or lower, preferably 1200°C or lower, more preferably 1180°C or lower; the air bubble degree is A grade or higher, preferably A 0 or higher, more preferably Class A 00 ; the glass transition temperature (T g ) is 640° C. or lower, preferably 630° C. or lower, and more preferably 625° C. or lower.

光學玻璃實施例Optical glass embodiment

為了進一步清楚地闡釋和說明本發明的技術方案，提供以下的非限制性實施例。In order to further clearly illustrate and illustrate the technical solution of the present invention, the following non-limiting examples are provided.

表1-表6的實施例1-48和表7的對比例1-5是通過按照各個實施例或對比例對應的含量稱重並混合光學玻璃用普通原料（如氧化物、氫氧化物、碳酸鹽、硝酸鹽等），將混合原料放置在鉑金坩堝中，在1200-1500℃中熔化2-6 小時，並經澄清、攪拌和均化後，得到均質熔融玻璃，將此熔融玻璃在模具內鑄型並退火而成。Examples 1-48 in Table 1 to Table 6 and Comparative Examples 1-5 in Table 7 are performed by weighing and mixing common raw materials for optical glass (such as oxides, hydroxides, Carbonate, nitrate, etc.), place the mixed raw materials in a platinum crucible and melt them at 1200-1500°C for 2-6 hours. After clarification, stirring and homogenization, a homogeneous molten glass is obtained. The molten glass is placed in the mold Inner mold and annealed.

表1

Figure 108134387-A0304-0001
Table 1
Figure 108134387-A0304-0001

表2

Figure 108134387-A0304-0002
Table 2
Figure 108134387-A0304-0002

表3

Figure 108134387-A0304-0003
table 3
Figure 108134387-A0304-0003

表4

Figure 108134387-A0304-0004
Table 4
Figure 108134387-A0304-0004

表5

Figure 108134387-A0304-0005
table 5
Figure 108134387-A0304-0005

表6

Figure 108134387-A0304-0006
Table 6
Figure 108134387-A0304-0006

表7

Figure 108134387-A0304-0007
Table 7
Figure 108134387-A0304-0007

本發明上述實施例的光學玻璃容易進行精密模壓成型，耐失透性好，Ln2 O3 的含量低於55%，成本較低。耐水穩定性（DW ）為2類以上，在優選的技術方案中，DW 達到1類；耐酸穩定性(DA )為3類以上，在優選的技術方案中，達到2類以上，化學穩定性好。氣泡度在A級以上，在優選的技術方案中，為A0 級以上，在更優的技術方案中，達到A00 級，氣泡度優異。而且熱膨脹係數（α-30 ℃ -70 ℃ ）≤75×10-7 /K，更優的(α-30 ℃ -70 ℃ )≤70×10-7 /K，受溫度影響發生膨脹或收縮的程度低。同時，還具有優異的抗析晶性能。The optical glass of the above-mentioned embodiment of the present invention is easy to be precision molded, has good devitrification resistance, the content of Ln 2 O 3 is less than 55%, and the cost is low. The water resistance stability (D W ) is above class 2. In the preferred technical solution, D W reaches class 1; the acid resistance stability (D A ) is class 3 or above. In the preferred technical solution, it reaches class 2 or above. Good stability. The air bubble degree is above grade A, and in the preferred technical solution, it is above grade A 0. In a more optimal technical solution, it reaches grade A 00 and the bubble degree is excellent. And thermal expansion coefficient (α -30 ℃ -70 ℃ )≤75×10 -7 /K, better (α -30 ℃ -70 ℃ )≤70×10 -7 /K, expansion or contraction due to temperature The degree is low. At the same time, it also has excellent crystallization resistance.

玻璃預製件實施例Examples of glass preforms

將實施例1-48所得到的光學玻璃切割成預定大小，再在表面上均勻地塗佈脫模劑，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。或者使用實施例1-48所得到的光學玻璃，形成精密模壓成型用的預成型品，再精密模壓成型加工成透鏡及稜鏡的形狀，製作預製件。The optical glass obtained in Examples 1-48 was cut into a predetermined size, and then a release agent was uniformly coated on the surface, and then it was heated, softened, and pressure molded to produce concave meniscus lenses and convex meniscus Preforms of various lenses, such as shaped lenses, biconvex lenses, biconcave lenses, plano-convex lenses, plano-concave lenses, etc. Alternatively, the optical glass obtained in Examples 1-48 is used to form a preform for precision compression molding, and then precision compression molding is processed into the shape of a lens and a rim to produce a preform.

光學元件實施例Optical component embodiment

將上述玻璃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 examples of the glass preforms reduces the internal deformation of the glass while fine-tuning the optical properties such as the refractive index to 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。所得到的光學元件的表面上還可塗佈防反射膜。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. The surface of the obtained optical element may also be coated with an anti-reflection film.

光學儀器實施例Optical instrument embodiment

將上述光學元件實施例制得的光學原件通過光學設計，通過使用一個或多個光學元件形成光學部件或光學組件，可用於例如成像設備、傳感器、顯微鏡、醫藥技術、數位投影、通信、光學通信技術/信息傳輸、汽車領域中的光學/照明、光刻技術、準分子雷射器、晶片、電腦晶片以及包括這樣的電路及晶片的集成電路和電子器件，尤其可用於車載領域的攝像設備和裝置。The optical original made by the above-mentioned optical element embodiment is optically designed to form an optical component or optical assembly by using one or more optical elements, which can be used in, for example, imaging equipment, sensors, microscopes, medical technology, digital projection, communications, and optical communications. Technology/information transmission, optics/illumination in the automotive field, lithography technology, excimer lasers, chips, computer chips, and integrated circuits and electronic devices including such circuits and chips, especially for imaging equipment and Device.

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Claims (25)

一種光學玻璃，其特徵在於，以重量%計，含有：SiO2：0-10%，和B2O3：5-25%，和ZrO2：0-15%，和ZnO：10-25%，和TiO2+Nb2O5+WO3：2-30%，和Ln2O3：30-55%，所述Ln2O3為La2O3、Gd2O3、Y2O3和Yb2O3的合計含量，其中B2O3/Ln2O3為0.3-0.8，Y2O3/B2O3為0.15-2；Y2O3/(SiO2+B2O3)為0.16-0.8。 An optical glass, characterized in that it contains SiO 2 : 0-10%, and B 2 O 3 : 5-25%, and ZrO 2 : 0-15%, and ZnO: 10-25% in terms of weight% , And TiO 2 +Nb 2 O 5 +WO 3 : 2-30%, and Ln 2 O 3 : 30-55%, the Ln 2 O 3 is La 2 O 3 , Gd 2 O 3 , Y 2 O 3 And Yb 2 O 3 , where B 2 O 3 /Ln 2 O 3 is 0.3-0.8, Y 2 O 3 /B 2 O 3 is 0.15-2; Y 2 O 3 /(SiO 2 +B 2 O 3 ) is 0.16-0.8. 如申請專利範圍第1項所述的光學玻璃，其特徵在於：還含有0-10%的RO，和/或0-10%的Rn2O，和/或0-1%的澄清劑，所述RO為MgO、CaO、SrO或BaO中的一種或多種，所述Rn2O為Li2O、Na2O、K2O中的一種或多種，所述澄清劑為Sb2O3、SnO2、CeO2中的一種或多種。 The optical glass described in item 1 of the scope of patent application is characterized in that it also contains 0-10% RO, and/or 0-10% Rn 2 O, and/or 0-1% clarifying agent, so The RO is one or more of MgO, CaO, SrO or BaO, the Rn 2 O is one or more of Li 2 O, Na 2 O, and K 2 O, and the clarifying agent is Sb 2 O 3 , SnO 2. One or more of CeO 2. 一種光學玻璃，其特徵在於，以重量%計，由0-10%的SiO2，和5-25%的B2O3，和0-15%的ZrO2，和10-25%的ZnO，和2-30%的TiO2+Nb2O5+WO3，和30-55%的Ln2O3，和0-10%的RO，和0-10%的Rn2O，和0-1%的澄清劑組成，所述Ln2O3為La2O3、Gd2O3、Y2O3和Yb2O3的合計含量，所述RO為MgO、CaO、SrO或BaO中的一種或多種，所述Rn2O為Li2O、Na2O、K2O中的一種或多種，所述澄清劑為Sb2O3、SnO2、CeO2中的一種或多種，其中B2O3/Ln2O3為0.3-0.8，Y2O3/B2O3為0.15-2。 An optical glass, characterized in that, in terms of weight %, 0-10% SiO 2 , 5-25% B 2 O 3 , 0-15% ZrO 2 , and 10-25% ZnO, And 2-30% TiO 2 +Nb 2 O 5 +WO 3 , and 30-55% Ln 2 O 3 , and 0-10% RO, and 0-10% Rn 2 O, and 0-1 % Clarifying agent composition, the Ln 2 O 3 is the total content of La 2 O 3 , Gd 2 O 3 , Y 2 O 3 and Yb 2 O 3 , and the RO is one of MgO, CaO, SrO or BaO Or more, the Rn 2 O is one or more of Li 2 O, Na 2 O, and K 2 O, and the clarifying agent is one or more of Sb 2 O 3 , SnO 2 , and CeO 2 , wherein B 2 O 3 /Ln 2 O 3 is 0.3-0.8, and Y 2 O 3 /B 2 O 3 is 0.15-2. 如申請專利範圍第1、2或3項所述的光學玻璃，其特徵在於：各組分含量滿足以下3種情形中的一種以上：1)SiO2/(SiO2+B2O3)為0-0.25；2)Y2O3/Ln2O3為0.08-0.45；3)Y2O3/Gd2O3為0.3-3。 The optical glass described in item 1, 2 or 3 of the scope of patent application is characterized in that: the content of each component satisfies more than one of the following three situations: 1) SiO 2 /(SiO 2 +B 2 O 3 ) is 0-0.25; 2) Y 2 O 3 /Ln 2 O 3 is 0.08-0.45; 3) Y 2 O 3 /Gd 2 O 3 is 0.3-3. 如申請專利範圍第1、2或3項所述的光學玻璃，其特徵在於：SiO2：1-8%，和/或B2O3：10-23%，和/或ZrO2：1-10%，和/或ZnO：10-20%，和/或TiO2+Nb2O5+WO3：4-22%，和/或Ln2O3：35-52%，和/或RO：0-5%，和/或R2O：0-5%，和/或澄清劑0-0.5%。 The optical glass described in item 1, 2 or 3 of the scope of patent application is characterized in that: SiO 2 : 1-8%, and/or B 2 O 3 : 10-23%, and/or ZrO 2 : 1- 10%, and/or ZnO: 10-20%, and/or TiO 2 +Nb 2 O 5 +WO 3 : 4-22%, and/or Ln 2 O 3 : 35-52%, and/or RO: 0-5%, and/or R 2 O: 0-5%, and/or clarifying agent 0-0.5%. 如申請專利範圍第1、2或3項所述的光學玻璃，其特徵在於：各組分含量滿足以下6種情形中的一種以上：1)SiO2/(SiO2+B2O3)為0.05-0.23；2)Y2O3/Ln2O3為0.1-0.4；3)Y2O3/Gd2O3為0.5-2.5；4)Y2O3/(SiO2+B2O3)為0.2-0.7；5)B2O3/Ln2O3為0.3-0.6；6)Y2O3/B2O3為0.2-1.5。 The optical glass as described in item 1, 2 or 3 of the scope of patent application is characterized in that: the content of each component satisfies more than one of the following 6 situations: 1) SiO 2 /(SiO 2 +B 2 O 3 ) is 0.05-0.23; 2) Y 2 O 3 /Ln 2 O 3 is 0.1-0.4; 3) Y 2 O 3 /Gd 2 O 3 is 0.5-2.5; 4) Y 2 O 3 /(SiO 2 +B 2 O 3 ) is 0.2-0.7; 5) B 2 O 3 /Ln 2 O 3 is 0.3-0.6; 6) Y 2 O 3 /B 2 O 3 is 0.2-1.5. 如申請專利範圍第1、2或3項所述的光學玻璃，其特徵在於：SiO2：1-4%，和/或B2O3：15-20%，和/或ZrO2：2-6%，和/或ZnO：13-17%，和/或TiO2+Nb2O5+WO3：10-18%，和/或Ln2O3：40-50%。 The optical glass described in item 1, 2 or 3 of the scope of the patent application is characterized in that: SiO 2 : 1-4%, and/or B 2 O 3 : 15-20%, and/or ZrO 2 : 2- 6%, and/or ZnO: 13-17%, and/or TiO 2 +Nb 2 O 5 +WO 3 : 10-18%, and/or Ln 2 O 3 : 40-50%. 如申請專利範圍第1、2或3項所述的光學玻璃，其特徵在於：各組分含量滿足以下6種情形中的一種以上：1)SiO2/(SiO2+B2O3)為0.08-0.2；2)Y2O3/Ln2O3為0.1-0.3；3)Y2O3/Gd2O3為大於1但小於等於2；4)Y2O3/(SiO2+B2O3)為0.3-0.6；5)B2O3/Ln2O3為0.3-0.5； 6)Y2O3/B2O3為0.3-1。 The optical glass as described in item 1, 2 or 3 of the scope of patent application is characterized in that: the content of each component satisfies more than one of the following 6 situations: 1) SiO 2 /(SiO 2 +B 2 O 3 ) is 0.08-0.2; 2) Y 2 O 3 /Ln 2 O 3 is 0.1-0.3; 3) Y 2 O 3 /Gd 2 O 3 is greater than 1 but less than or equal to 2; 4) Y 2 O 3 /(SiO 2 + B 2 O 3 ) is 0.3-0.6; 5) B 2 O 3 /Ln 2 O 3 is 0.3-0.5; 6) Y 2 O 3 /B 2 O 3 is 0.3-1. 如申請專利範圍第1、2或3項所述的光學玻璃，其特徵在於：Nb2O5：1-15%，和/或WO3：1-15%，和/或TiO2：0-10%，和/或La2O3：20-45%，和/或Gd2O3：0-15%，和/或Y2O3：1-15%，和/或Yb2O3：0-5%。 The optical glass described in item 1, 2 or 3 of the scope of patent application is characterized in that: Nb 2 O 5 : 1-15%, and/or WO 3 : 1-15%, and/or TiO 2 : 0- 10%, and/or La 2 O 3 : 20-45%, and/or Gd 2 O 3 : 0-15%, and/or Y 2 O 3 : 1-15%, and/or Yb 2 O 3 : 0-5%. 如申請專利範圍第1、2或3項所述的光學玻璃，其特徵在於：Nb2O5：2-10%，和/或WO3：2-12%，和/或TiO2：0-5%，和/或La2O3：25-40%，和/或Gd2O3：1-10%，和/或Y2O3：3-15%。 The optical glass described in item 1, 2 or 3 of the scope of patent application is characterized in that: Nb 2 O 5 : 2-10%, and/or WO 3 : 2-12%, and/or TiO 2 : 0- 5%, and/or La 2 O 3 : 25-40%, and/or Gd 2 O 3 : 1-10%, and/or Y 2 O 3 : 3-15%. 如申請專利範圍第1、2或3項所述的光學玻璃，其特徵在於：Nb2O5：4-8%，和/或WO3：6-10%，和/或La2O3：30-35%，和/或Gd2O3：3-7%，和/或Y2O3：6-10%，和/或不含TiO2。 The optical glass described in item 1, 2 or 3 of the scope of patent application is characterized in that: Nb 2 O 5 : 4-8%, and/or WO 3 : 6-10%, and/or La 2 O 3 : 30-35%, and/or Gd 2 O 3 : 3-7%, and/or Y 2 O 3 : 6-10%, and/or no TiO 2 . 如申請專利範圍第1、2或3項所述的光學玻璃，其特徵在於：所述光學玻璃的折射率nd為1.84-1.87，阿貝數vd為38.0-41.0。 The optical glass described in item 1, 2 or 3 of the scope of patent application is characterized in that: the refractive index nd of the optical glass is 1.84-1.87, and the Abbe number vd is 38.0-41.0. 如申請專利範圍第1、2或3項所述的光學玻璃，其特徵在於：所述光學玻璃的折射率nd為1.85-1.86，阿貝數vd為38.5-40.0。 The optical glass described in item 1, 2 or 3 of the scope of patent application is characterized in that: the refractive index nd of the optical glass is 1.85-1.86, and the Abbe number vd is 38.5-40.0. 如申請專利範圍第1、2或3項所述的光學玻璃，其特徵在於，所述光學玻璃粉末法耐水穩定性DW為2類以上；和/或粉末法耐酸穩定性DA為3類以上。 The optical glass described in item 1, 2 or 3 of the scope of patent application is characterized in that the water resistance D W of the optical glass powder method is class 2 or more; and/or the acid resistance stability D A of the powder method is class 3 the above. 如申請專利範圍第1、2或3項所述的光學玻璃，其特徵在於，所述光學玻璃粉末法耐水穩定性DW為1類；和/或粉末法耐酸穩定性DA為2類。 The optical glass according to item 1, 2 or 3 of the scope of patent application is characterized in that the water resistance D W of the optical glass powder method is Class 1; and/or the acid resistance stability D A of the powder method is Class 2. 如申請專利範圍第1、2或3項所述的光學玻璃，其特徵在於，所述光學玻璃的熱膨脹係數α-30℃-70℃
Figure 108134387-A0305-02-0027-1
75×10-7/K。 The optical glass described in item 1, 2 or 3 of the scope of patent application is characterized in that the thermal expansion coefficient of the optical glass is α -30℃-70℃
Figure 108134387-A0305-02-0027-1
75×10 -7 /K. 如申請專利範圍第1、2或3項所述的光學玻璃，其特徵在於，所述 光學玻璃的熱膨脹係數α-30℃-70℃
Figure 108134387-A0305-02-0028-3
70×10-7/K。 The optical glass described in item 1, 2 or 3 of the scope of patent application is characterized in that the thermal expansion coefficient of the optical glass is α -30℃-70℃
Figure 108134387-A0305-02-0028-3
70×10 -7 /K. 如申請專利範圍第1、2或3項所述的光學玻璃，其特徵在於，所述光學玻璃的氣泡度為A級以上。 The optical glass described in item 1, 2 or 3 of the scope of the patent application is characterized in that the bubble degree of the optical glass is A grade or higher. 如申請專利範圍第1、2或3項所述的光學玻璃，其特徵在於，所述光學玻璃的氣泡度為A0級以上。 The optical glass described in item 1, 2 or 3 of the scope of patent application is characterized in that the bubble degree of the optical glass is A 0 or higher. 如申請專利範圍第1、2或3項所述的光學玻璃，其特徵在於，所述光學玻璃的轉變溫度Tg為640℃以下；和/或所述光學玻璃的析晶上限溫度為1250℃以下。 The optical glass described in item 1, 2 or 3 of the scope of patent application is characterized in that the transition temperature T g of the optical glass is below 640°C; and/or the upper limit temperature of crystallization of the optical glass is 1250°C the following. 如申請專利範圍第1、2或3項所述的光學玻璃，其特徵在於，所述光學玻璃的轉變溫度Tg為630℃以下；和/或所述光學玻璃的析晶上限溫度為1200℃以下。 The optical glass described in item 1, 2 or 3 of the scope of patent application is characterized in that the transition temperature T g of the optical glass is below 630°C; and/or the upper limit temperature of crystallization of the optical glass is 1200°C the following. 如申請專利範圍第1、2或3項所述的光學玻璃，其特徵在於，所述光學玻璃的轉變溫度Tg為625℃以下；和/或所述光學玻璃的析晶上限溫度為1180℃以下。 The optical glass described in item 1, 2 or 3 of the scope of patent application is characterized in that the transition temperature T g of the optical glass is below 625°C; and/or the upper limit temperature of crystallization of the optical glass is 1180°C the following. 一種玻璃預製件，採用申請專利範圍第1-22項任一項所述的光學玻璃製成。 A glass preform is made of the optical glass described in any one of items 1-22 of the scope of patent application. 一種光學元件，採用申請專利範圍第1-22項任一項所述的光學玻璃製成，或者採用申請專利範圍第23項所述的玻璃預製件製成。 An optical element, made of the optical glass described in any one of items 1-22 of the scope of patent application, or made of glass preform described in item 23 of the scope of patent application. 一種光學儀器，採用申請專利範圍第24項所述的光學元件製成。 An optical instrument made of the optical element described in item 24 of the scope of patent application.
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