TWI798501B - Optical glass, glass preforms, optical components and optical instruments - Google Patents

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

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TWI798501B
TWI798501B TW108139276A TW108139276A TWI798501B TW I798501 B TWI798501 B TW I798501B TW 108139276 A TW108139276 A TW 108139276A TW 108139276 A TW108139276 A TW 108139276A TW I798501 B TWI798501 B TW I798501B
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glass
bao
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optical glass
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TW202019846A (en
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毛露路
匡波
吳德林
周佺佺
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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
    • C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
    • C03C1/004—Refining agents
    • 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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Abstract

本發明提供一種中等折射率且折射率溫度係數低的光學玻璃，其組成包含SiO2 、B2 O3 、La2 O3 、RO和Rn2 O的光學玻璃，其中RO為MgO、CaO、SrO和BaO中的一種或一種以上，Rn2 O為Li2 O、K2 O和Na2 O中的一種或一種以上，所述光學玻璃的折射率為1.65～1.73，阿貝數為47～55，同時具有較低的折射率溫度係數、優異的抗析晶性能和化學穩定性。The invention provides an optical glass with a medium refractive index and a low temperature coefficient of refractive index, the optical glass comprising SiO 2 , B 2 O 3 , La 2 O 3 , RO and Rn 2 O, wherein RO is MgO, CaO, SrO and BaO, Rn 2 O is one or more of Li 2 O, K 2 O and Na 2 O, the refractive index of the optical glass is 1.65-1.73, and the Abbe number is 47-55 , while having a low temperature coefficient of refractive index, excellent anti-devitrification performance and chemical stability.

Description

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

本發明涉及一種光學玻璃，尤其是涉及一種折射率為1.65～1.73、阿貝數為47～55的含鑭光學玻璃，以及由該光學玻璃製成的玻璃預製件、光學元件和光學儀器。The invention relates to an optical glass, in particular to a lanthanum-containing optical glass with a refractive index of 1.65-1.73 and an Abbe number of 47-55, as well as glass preforms, optical elements and optical instruments made of the optical glass.

在現有技術中，折射率為1.65～1.73、阿貝數為47～55的玻璃屬於中等折射率玻璃，大量應用在各類鏡頭中；近年來，車載鏡頭設備得到了蓬勃的發展，和一般攝影等應用相比，車載鏡頭的品質跟安全息息相關，因此車載鏡頭更為強調設備的可靠性，尤其是裸露在車體外部，需要承受惡劣工作環境，如倒車攝像頭、前視攝像頭、後視鏡輔助攝像頭等。In the prior art, glass with a refractive index of 1.65-1.73 and an Abbe number of 47-55 is a medium refractive index glass, which is widely used in various lenses; in recent years, vehicle-mounted lens equipment has developed vigorously, and general photography Compared with other applications, the quality of the car lens is closely related to safety, so the car lens puts more emphasis on the reliability of the equipment, especially when it is exposed outside the car body, it needs to withstand the harsh working environment, such as reversing camera, front-view camera, rearview mirror auxiliary camera etc.

設計滿足惡劣工作環境車載鏡頭的原則是結構盡可能的簡單，結構越複雜，可靠性就越差；因此，為了滿足可適應惡劣工作環境的車載鏡頭長壽命（長達十年以上）的設計要求，在光學設計中一般採用定焦鏡頭設計，其鏡片數量比變焦鏡頭少，同時沒有變焦驅動結構，因此可靠性較變焦鏡頭得到大幅度提升。The principle of designing vehicle-mounted lenses to meet harsh working environments is to keep the structure as simple as possible. The more complex the structure, the worse the reliability; therefore, in order to meet the design requirements of long life (more than ten years) for vehicle-mounted lenses that can adapt to harsh working environments , In the optical design, the fixed-focus lens design is generally adopted. The number of lenses is less than that of the zoom lens, and there is no zoom drive structure, so the reliability is greatly improved compared with the zoom lens.

但是，定焦鏡頭雖然可靠性非常好，但應用在車載上，其致命的弱點在於修正鏡頭的溫度漂移是非常困難的；鏡頭的溫度漂移是指當溫度發生劇烈變化時，比如沙漠地區的晝夜溫差達到60℃，汽車從熱帶行駛到寒帶等溫差非常大的場景下，鏡頭的焦距會發生變化，從而導致成像模糊；對於汽車來講，安全是第一位的，因此，車載攝像頭需要在溫度急劇變化的條件下，均能保持清晰的成像。However, although the reliability of the fixed-focus lens is very good, its fatal weakness is that it is very difficult to correct the temperature drift of the lens when it is applied in the car; the temperature drift of the lens refers to when the temperature changes drastically, such as day and night in a desert area The temperature difference reaches 60°C, and the focal length of the lens will change when the temperature difference is very large, such as when the car is driving from the tropics to the frigid zone, resulting in blurred images; for cars, safety is the first priority, therefore, the car camera needs to be in the temperature Under sharply changing conditions, it can maintain clear imaging.

對於光學設計來說，通常可以採用更多的不同類型的鏡片組合和變焦系統來解決溫度漂移問題；但是，由於車載系統對可靠性的要求，需要在鏡片數量很少（甚至是3片）的定焦成像系統上解決溫度漂移問題，這就需要發展具有特異溫度折射率係數的光學玻璃，這也是時代的發展給光學設計和光學材料研究提出的一個新課題。For optical design, usually more different types of lens combinations and zoom systems can be used to solve the temperature drift problem; To solve the problem of temperature drift in fixed-focus imaging systems, it is necessary to develop optical glasses with specific temperature refractive index coefficients. This is also a new topic proposed by the development of the times for optical design and optical material research.

目前現有技術的折射率在1.65～1.73、阿貝數為47～55的光學玻璃，其在20～40℃範圍內，折射率溫度系數值，即d線 dn/dt relative(10-6 /℃)基本在1.0～3.0(10-6 /℃)左右（見下表1）。若能開發出折射率溫度係數低於0，甚至低於-1.0的並處於以上光性的鑭冕玻璃，能夠在設計中有效解決上述溫度漂移問題。 表1：部分折射率為1.65～1.73、阿貝數為47～55範圍內的玻璃的折射率溫度係數

Figure 108139276-A0304-0001
At present, the optical glass with a refractive index of 1.65-1.73 and an Abbe number of 47-55 in the existing technology has a temperature coefficient of refractive index in the range of 20-40°C, that is, the d-line dn/dt relative(10 -6 /°C ) is basically around 1.0~3.0 (10 -6 /℃) (see Table 1 below). If a lanthanum crown glass with a temperature coefficient of refraction index lower than 0, or even lower than -1.0 and in the above optical properties can be developed, the above-mentioned temperature drift problem can be effectively solved in the design. Table 1: Refractive index temperature coefficients of glasses with a partial refractive index of 1.65 to 1.73 and an Abbe number of 47 to 55
Figure 108139276-A0304-0001

但是，上述折射率與阿貝數的鑭冕玻璃若需要達到低於0的折射率溫度係數，在組分設計上需不同於常規，通常會給生產上帶來玻璃抗析晶性能差，條紋氣泡不易消除等問題。However, if the lanthanum crown glass with the above-mentioned refractive index and Abbe number needs to achieve a temperature coefficient of refractive index lower than 0, the component design needs to be different from the conventional ones, which usually leads to poor devitrification resistance and striations in the production. Bubbles are not easy to eliminate and other problems.

如果玻璃的抗析晶能力差，首先會增加玻璃胚料的生產難度，導致良品率下降，嚴重時甚至不能正常生產；其次是在二次壓型過程中容易產生晶體析出，造成良品率下降，甚至不能進行二次壓型，對於應用在車載領域的玻璃材料來說，如果玻璃的生產良品率低，且不能採用二次壓型而是採用冷加工的方法製作，成本上升將會導致難以接受。If the anti-devitrification ability of the glass is poor, it will firstly increase the difficulty of the production of glass blanks, resulting in a decline in the yield rate, and even cannot be produced normally in serious cases; secondly, crystal precipitation is prone to occur during the secondary molding process, resulting in a decline in the yield rate. Even secondary pressing is not possible. For glass materials used in the automotive field, if the yield rate of glass production is low, and secondary pressing cannot be used but cold processing is used, the cost increase will be unacceptable.

本發明所要解決的技術問題是提供一種中等折射率且折射率溫度係數低的光學玻璃。The technical problem to be solved by the present invention is to provide an optical glass with a medium refractive index and a low temperature coefficient of the refractive index.

為了達到上述目的，本發明提供一種光學玻璃，其組成包含SiO2 、B2 O3 、La2 O3 、RO和Rn2 O，其中RO為MgO、CaO、SrO和BaO中的一種或一種以上，Rn2 O為Li2 O、K2 O和Na2 O中的一種或一種以上，玻璃的折射率為1.65～1.73，阿貝數為47～55，折射率溫度係數為≤0。In order to achieve the above purpose, the present invention provides an optical glass whose composition includes SiO 2 , B 2 O 3 , La 2 O 3 , RO and Rn 2 O, wherein RO is one or more of MgO, CaO, SrO and BaO , Rn 2 O is one or more of Li 2 O, K 2 O and Na 2 O, the refractive index of the glass is 1.65-1.73, the Abbe number is 47-55, and the temperature coefficient of refractive index is ≤0.

於其中一項實施例中，光學玻璃組成以重量百分比表示，含有：SiO2 ：4～20%、B2 O3 ：10～30%、La2 O3 ：10～35%、BaO：10～40%、SrO：0～15%、CaO：0～10%、MgO：0～5%、Li2 O：0～5%、K2 O：0～6%、Na2 O：0～8%、Gd2 O3 ：0～8%、Y2 O3 ：0～5%、ZrO2 ：0～3%、Al2 O3 ：0～3%、TiO2 ：0～3%、Nb2 O5 ：0～5%、WO3 ：0～2%、ZnO：0～5%、澄清劑：0～2%。In one of the embodiments, the composition of the optical glass is represented by weight percentage, including: SiO 2 : 4-20%, B 2 O 3 : 10-30%, La 2 O 3 : 10-35%, BaO: 10-30%. 40%, SrO: 0-15%, CaO: 0-10%, MgO: 0-5%, Li 2 O: 0-5%, K 2 O: 0-6%, Na 2 O: 0-8% , Gd 2 O 3 : 0-8%, Y 2 O 3 : 0-5%, ZrO 2 : 0-3%, Al 2 O 3 : 0-3%, TiO 2 : 0-3%, Nb 2 O 5 : 0-5%, WO 3 : 0-2%, ZnO: 0-5%, clarifying agent: 0-2%.

本發明另一項實施例提供一種光學玻璃，其組成以重量百分比表示，含有：SiO2 ：4～20%、B2 O3 ：10～30%、La2 O3 ：10～35%、BaO：10～40%、SrO：0～15%。Another embodiment of the present invention provides an optical glass, the composition of which is represented by weight percentage, containing: SiO 2 : 4-20%, B 2 O 3 : 10-30%, La 2 O 3 : 10-35%, BaO : 10-40%, SrO: 0-15%.

於其中一項實施例中，光學玻璃，更包含有：CaO：0～10%、MgO：0～5%、Li2 O：0～5%、K2 O：0～6%、Na2 O：0～8%、Gd2 O3 ：0～8%、Y2 O3 ：0～5%、ZrO2 ：0～3%、Al2 O3 ：0～3%、TiO2 ：0～3%、Nb2 O5 ：0～5%、WO3 ：0～2%、ZnO：0～5%、澄清劑：0～2%。In one of the embodiments, the optical glass further includes: CaO: 0-10%, MgO: 0-5%, Li 2 O: 0-5%, K 2 O: 0-6%, Na 2 O : 0~8%, Gd 2 O 3 : 0~8%, Y 2 O 3 : 0~5%, ZrO 2 : 0~3%, Al 2 O 3 : 0~3%, TiO 2 : 0~3 %, Nb 2 O 5 : 0-5%, WO 3 : 0-2%, ZnO: 0-5%, clarifying agent: 0-2%.

本發明又一項實施例提供一種光學玻璃，其組成以重量百分比表示由SiO2 ：4～20%、B2 O3 ：10～30%、La2 O3 ：10～35%、BaO：10～40%、SrO：0～15%、CaO：0～10%、MgO：0～5%、Rn2 0：0～8%、Gd2 O3 ：0～8%、Y2 O3 ：0～5%、ZrO2 ：0～3%、Al2 O3 ：0～3%、TiO2 ：0～3%、Nb2 O5 ：0～5%、WO3 ：0～2%、ZnO：0～5%組成，其中Rn2 O為Li2 O、K2 O、Na2 O中的一種或一種以上。Yet another embodiment of the present invention provides an optical glass, the composition of which is represented by weight percent: SiO 2 : 4-20%, B 2 O 3 : 10-30%, La 2 O 3 : 10-35%, BaO: 10% ～40%, SrO: 0～15%, CaO: 0～10%, MgO: 0～5%, Rn 2 0: 0～8%, Gd 2 O 3 : 0～8%, Y 2 O 3 : 0 ～5%, ZrO 2 : 0～3%, Al 2 O 3 : 0～3%, TiO 2 : 0～3%, Nb 2 O 5 : 0～5%, WO 3 : 0～2%, ZnO: 0~5% composition, wherein Rn 2 O is one or more of Li 2 O, K 2 O, Na 2 O.

於其中一項實施例中，SiO2 /B2 O3 為0.4～1.3，優選為0.45～1.2，更優選為0.5～1.1；和/或BaO/La2 O3 為0.6～2，優選為0.65～1.9，更優選為0.7～1.8。In one embodiment, SiO 2 /B 2 O 3 is 0.4-1.3, preferably 0.45-1.2, more preferably 0.5-1.1; and/or BaO/La 2 O 3 is 0.6-2, preferably 0.65 ~1.9, more preferably 0.7~1.8.

於其中一項實施例中，CaO/（BaO+SrO）為0～0.5，優選為0.01～0.4，更優選為0.02～0.3；和/或ZnO/（CaO+SrO+BaO）為0～0.3，優選為0～0.2，更優選為0～0.15；和/或（CaO+SrO+BaO）/（La2 O3 +Gd2 O3 +Y2 O3 ）為0.7～2.5，優選為0.8～2.3，更優選為0.9～2.1；和/或（CaO+SrO+BaO）/（Al2 O3 +ZrO2 +TiO2 ）大於8，優選大於10，更優選大於12；和/或SrO含量≥CaO含量，優選BaO含量≥SrO含量≥CaO含量。In one of the embodiments, CaO/(BaO+SrO) is 0-0.5, preferably 0.01-0.4, more preferably 0.02-0.3; and/or ZnO/(CaO+SrO+BaO) is 0-0.3, Preferably 0-0.2, more preferably 0-0.15; and/or (CaO+SrO+BaO)/(La 2 O 3 +Gd 2 O 3 +Y 2 O 3 ) is 0.7-2.5, preferably 0.8-2.3 , more preferably 0.9 to 2.1; and/or (CaO+SrO+BaO)/(Al 2 O 3 +ZrO 2 +TiO 2 ) greater than 8, preferably greater than 10, more preferably greater than 12; and/or SrO content ≥ CaO content, preferably BaO content≥SrO content≥CaO content.

於其中一項實施例中，Li2 O+Na2 O+K2 O為0～8%，優選為0～6%，更優選為0～5%；和/或Li2 O/（K2 O+Na2 O）為0～0.5，優選為0～0.4，更優選為0～0.3；和/或Na2 O/K2 O為0.2～5.0，優選為0.3～4.0，更優選為0.4～3.0；和/或TiO2 /Nb2 O5 為1以下，優選為0.8以下，更優選為0.5以下。In one of the embodiments, Li 2 O+Na 2 O+K 2 O is 0-8%, preferably 0-6%, more preferably 0-5%; and/or Li 2 O/(K 2 O+Na 2 O) is 0-0.5, preferably 0-0.4, more preferably 0-0.3; and/or Na 2 O/K 2 O is 0.2-5.0, preferably 0.3-4.0, more preferably 0.4- 3.0; and/or TiO 2 /Nb 2 O 5 is 1 or less, preferably 0.8 or less, more preferably 0.5 or less.

於其中一項實施例中，光學玻璃組成以重量百分比表示，包含有：SiO2 ：6～18%、和/或B2 O3 ：12～25%、和/或La2 O3 ：12～30%、和/或BaO：12～35%、和/或SrO：0.5～15%、和/或CaO：0～8%、和/或Gd2 O3 ：1～6%、和/或Y2 O3 ：0～3%、和/或ZrO2 ：0.1～3%、和/或Al2 O3 ：0～2%、和/或TiO2 ：0～2%、和/或Nb2 O5 ：0.1～5%、和/或WO3 ：0～1%、和/或ZnO：0～3%、和/或MgO：0～3%、和/或 Li2 O：0～3%、和/或K2 O：0.3～4%、和/或Na2 O：0.5～6%。In one of the embodiments, the optical glass composition is represented by weight percentage, including: SiO 2 : 6-18%, and/or B 2 O 3 : 12-25%, and/or La 2 O 3 : 12-25% 30%, and/or BaO: 12-35%, and/or SrO: 0.5-15%, and/or CaO: 0-8%, and/or Gd 2 O 3 : 1-6%, and/or Y 2 O 3 : 0-3%, and/or ZrO 2 : 0.1-3%, and/or Al 2 O 3 : 0-2%, and/or TiO 2 : 0-2%, and/or Nb 2 O 5 : 0.1-5%, and/or WO 3 : 0-1%, and/or ZnO: 0-3%, and/or MgO: 0-3%, and/or Li 2 O: 0-3%, And/or K 2 O: 0.3-4%, and/or Na 2 O: 0.5-6%.

於其中一項實施例中，光學玻璃組成以重量百分比表示，包含有：SiO2 ：8～16%、和/或B2 O3 ：15～22%、和/或La2 O3 ：15～28%、和/或BaO：15～32%、和/或SrO：1～12%、和/或CaO：0～6%、和/或Gd2 O3 ：1～4%、和/或Y2 O3 ：1～3%、和/或ZrO2 ：0.1～2%、和/或Al2 O3 ：0.1～1%、和/或TiO2 ：0～1%、和/或Nb2 O5 ：0.5～4%、和/或K2 O：0.5～3%、和/或Na2 O：1～3%。In one of the embodiments, the optical glass composition is represented by weight percentage, including: SiO 2 : 8-16%, and/or B 2 O 3 : 15-22%, and/or La 2 O 3 : 15-22% 28%, and/or BaO: 15-32%, and/or SrO: 1-12%, and/or CaO: 0-6%, and/or Gd 2 O 3 : 1-4%, and/or Y 2 O 3 : 1-3%, and/or ZrO 2 : 0.1-2%, and/or Al 2 O 3 : 0.1-1%, and/or TiO 2 : 0-1%, and/or Nb 2 O 5 : 0.5-4%, and/or K 2 O: 0.5-3%, and/or Na 2 O: 1-3%.

於其中一項實施例中光學玻璃組成以重量百分比表示，含有：ZrO2 ：0.1～1%、和/或Nb2 O5 ：1～3%、和/或SrO：1.5～10%。In one embodiment, the composition of the optical glass is represented by weight percentage, including: ZrO 2 : 0.1-1%, and/or Nb 2 O 5 : 1-3%, and/or SrO: 1.5-10%.

於其中一項實施例中，玻璃的折射率為1.65～1.73，優選為1.67～1.72；阿貝數為47～55，優選為48～52。In one embodiment, the refractive index of the glass is 1.65-1.73, preferably 1.67-1.72; the Abbe number is 47-55, preferably 48-52.

於其中一項實施例中，玻璃的折射率溫度係數為≤0，優選為≤-0.5，更優選為≤-1.0，進一步優選為≤-2.0。In one embodiment, the temperature coefficient of the glass's refractive index is ≤0, preferably ≤-0.5, more preferably ≤-1.0, and even more preferably ≤-2.0.

於其中一項實施例中，玻璃的耐水穩定性為4類及其以上，優選為3類及其以上，更優選為2類及其以上；和/或氣泡度為A級以上，優選為A0 級以上，更優選為A00 級；和/或條紋為C級以上，優選B級以上，更優選為A級；和/或耐日照穩定性為400nm波長處透過率下降不超過10%，優選不超過8%，進一步優選不超過5%。In one of the embodiments, the water resistance stability of the glass is Class 4 or above, preferably Class 3 or above, more preferably Class 2 or above; and/or the bubble degree is above Class A, preferably Class A 0 grade or above, more preferably A 00 grade; and/or the stripes are C grade or above, preferably B grade or above, more preferably A grade; and/or the sunlight resistance stability is such that the transmittance at 400nm wavelength drops by no more than 10%, Preferably not more than 8%, more preferably not more than 5%.

本發明一些實施例提供一種玻璃預製件，使用前述光學玻璃製成。Some embodiments of the present invention provide a glass preform made of the aforementioned optical glass.

本發明一些實施例提供一種光學元件，使用前述光學玻璃或前述玻璃預製件製成。Some embodiments of the present invention provide an optical element made by using the foregoing optical glass or the foregoing glass preform.

本發明一些實施例提供一種光學儀器，使用前述光學玻璃或前述光學元件製成。Some embodiments of the present invention provide an optical instrument made by using the aforementioned optical glass or the aforementioned optical element.

本發明一些實施例提供一種前述光學玻璃或前述光學元件之用途，其光學玻璃或光學元件應用在車載上。Some embodiments of the present invention provide an application of the aforementioned optical glass or the aforementioned optical element, and the optical glass or optical element is applied on a vehicle.

本發明的有益效果是：通過合理的組分設計，使得本發明光學玻璃具有中等折射率和低的折射率溫度係數，量產工藝性能好。The beneficial effect of the invention is that: through reasonable component design, the optical glass of the invention has a medium refractive index and a low temperature coefficient of the refractive index, and the mass production process performance is good.

下面，對本發明光學玻璃的各成分的組成範圍進行說明。在本說明書中，如果沒有特殊說明，各組分的含量全部採用相對于換算成氧化物的組成的玻璃物質總量的重量百分比表示。在這裡，所述「換算成氧化物的組成」是指，作為本發明的光學玻璃組成成分的原料而使用的氧化物、複合鹽及氫氧化物等熔融時分解並轉變為氧化物的情況下，將該氧化物的物質總量作為100%。Next, the composition range of each component of the optical glass of this invention is demonstrated. In this specification, unless otherwise specified, the content of each component is expressed in weight percent relative to the total amount of glass substances converted into oxides. Here, the "composition in terms of oxides" refers to the case where oxides, composite salts, hydroxides, etc. used as raw materials for the optical glass composition of the present invention are decomposed and converted into oxides during melting. , and the total amount of the oxide is taken as 100%.

除非在具體情況下另外指出，本文所列出的數值範圍包括上限和下限值，「以上」和「以下」包括端點值，在該範圍內的所有整數和分數，而不限於所限定範圍時所列的具體值。本文所使用的術語“約”指配方、參數和其他數量以及特徵不是、且無需是精確的，如有需要，可以近似和/或更大或更低，這反映公差、換算因數和測量誤差等。本文所稱“和/或”是包含性的，例如「A和/或B」，是指只有A，或者只有B，或者同時有A和B。Unless otherwise indicated in a specific instance, the numerical ranges set forth herein include the upper and lower values, "above" and "below" include the endpoints, all integers and fractions within the range, and are not intended to be limiting of the defined range. The specific values listed at the time. As used herein, the term "about" means that formulations, parameters and other quantities and characteristics are not, and need not be, exact, but may be approximated and/or greater or lesser if desired, reflecting tolerances, conversion factors and measurement errors, etc. . The term "and/or" in this article is inclusive, for example, "A and/or B" means only A, or only B, or both A and B.

本發明光學玻璃主要由SiO2 、B2 O3 、La2 O3 、RO（RO為MgO、CaO、SrO、BaO中的一種或一種以上，以下同）、Rn2 O（Rn2 O為Li2 O、K2 O、Na2 O中的一種或一種以上，以下同）組成，通過合理的組分配比，形成折射率為1.65～1.73、阿貝數為47～55的光學玻璃，且其在20～40℃溫度範圍內，折射率溫度係數（d線 dn/dt relative(10-6 /℃)）低，抗析晶性能優異，長期使用透過率不會產生明顯下降，非常適合於車載鏡頭使用。The optical glass of the present invention is mainly composed of SiO 2 , B 2 O 3 , La 2 O 3 , RO (RO is one or more of MgO, CaO, SrO, BaO, the same below), Rn 2 O (Rn 2 O is Li 2 O, K 2 O, Na 2 O, or more than one, hereinafter the same), through a reasonable composition ratio, form an optical glass with a refractive index of 1.65-1.73 and an Abbe number of 47-55, and its In the temperature range of 20 ~ 40 ℃, the temperature coefficient of the refractive index (d line dn/dt relative (10 -6 / ℃)) is low, the anti-devitrification performance is excellent, and the transmittance will not decrease significantly after long-term use, which is very suitable for vehicles. lens used.

SiO2 和B2 O3 是構成本發明玻璃的網路形成體，是形成玻璃的基礎，其含量和玻璃的成玻穩定性、抗析晶性能、折射率和阿貝數等關鍵指標息息相關。其中，若SiO2 含量超過20%，玻璃會變得難以融化，同時成玻穩定性會下降，抗析晶性能急劇下降，玻璃的折射率和阿貝數達不到設計要求；若SiO2 的含量低於4%，玻璃的化學穩定性，尤其是耐水作用穩定性會下降，玻璃的抗析晶性能會下降。因此，SiO2 的含量限定在4～20%，優選為6～18%，更優選為8～16%。在一些實施方式中，可包含約4%、5%、6%、7%、8%、9%、10%、11%、12%、13%、14%、15%、16%、17%、18%、19%、20%的SiO2 。SiO 2 and B 2 O 3 are network formers constituting the glass of the present invention, and are the basis for forming glass, and their content is closely related to key indicators such as glass forming stability, devitrification resistance, refractive index and Abbe number of the glass. Among them, if the SiO 2 content exceeds 20%, the glass will become difficult to melt, and at the same time, the stability of glass formation will decrease, the anti-devitrification performance will drop sharply, and the refractive index and Abbe number of the glass will not meet the design requirements; if the SiO 2 If the content is less than 4%, the chemical stability of the glass, especially the stability of water resistance, will decrease, and the anti-devitrification performance of the glass will decrease. Therefore, the content of SiO 2 is limited to 4-20%, preferably 6-18%, more preferably 8-16%. In some embodiments, about 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17% may be included , 18%, 19%, 20% SiO 2 .

B2 O3 的含量若超過30%，玻璃的化學穩定性會下降，阿貝數會高於設計預期；B2 O3 的含量若低於10%，玻璃的抗析晶性能會快速下降，且玻璃的阿貝數達不到設計預期。因此，B2 O3 的含量限定為10～30%，優選為12～25%，更優選為15～22%。在一些實施方式中，可包含約10%、11%、12%、13%、14%、15%、16%、17%、18%、19%、20%、21%、22%、23%、24%、25%、26%、27%、28%、29%、30%的B2 O3 。If the content of B 2 O 3 exceeds 30%, the chemical stability of the glass will decrease, and the Abbe number will be higher than the design expectation; if the content of B 2 O 3 is less than 10%, the anti-devitrification performance of the glass will decrease rapidly, And the Abbe number of the glass does not meet the design expectation. Therefore, the content of B 2 O 3 is limited to 10-30%, preferably 12-25%, more preferably 15-22%. In some embodiments, may comprise about 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23% , 24%, 25%, 26%, 27%, 28%, 29%, 30% of B 2 O 3 .

SiO2 和B2 O3 的相對含量在一定程度上會決定B2 O3 在玻璃中的結構狀態，而B2 O3 的結構狀態會對玻璃的折射率溫度係數與化學穩定性產生較大的影響，當SiO2 與B2 O3 的比值SiO2 /B2 O3 大於1.3時，玻璃的折射率溫度係數會快速升高，達不到設計要求；若SiO2 /B2 O3 小於0.4時，玻璃化學穩定性，尤其是耐水性會快速下降，不能滿足在惡劣條件中使用的要求。因此，本發明中，SiO2 /B2 O3 的值優選限定為0.4～1.3。另外，在一些實施方式中，若SiO2 /B2 O3 的值小於0.45，玻璃在成型時高溫粘度極小，容易在玻璃內部產生C級以下的條紋，造成玻璃不能應用在要求較高的成像系統中，若SiO2 /B2 O3 的值高於1.2，玻璃的氣泡難以消除。因此在一些實施方式中，SiO2 /B2 O3 的值更優選為0.45～1.2，進一步優選為0.5～1.1。在一些實施方式中，SiO2 /B2 O3 的值可為0.4、0.45、0.5、0.55、0.6、0.65、0.7、0.75、0.8、0.85、0.9、0.95、1.0、1.05、1.1、1.15、1.2、1.25、1.3。The relative content of SiO 2 and B 2 O 3 will determine the structural state of B 2 O 3 in the glass to a certain extent, and the structural state of B 2 O 3 will have a greater impact on the temperature coefficient of refractive index and chemical stability of the glass. When the ratio of SiO 2 to B 2 O 3 SiO 2 /B 2 O 3 is greater than 1.3, the temperature coefficient of refractive index of the glass will rise rapidly, which cannot meet the design requirements; if SiO 2 /B 2 O 3 is less than When it is 0.4, the chemical stability of the glass, especially the water resistance will drop rapidly, which cannot meet the requirements for use in harsh conditions. Therefore, in the present invention, the value of SiO 2 /B 2 O 3 is preferably limited to 0.4 to 1.3. In addition, in some embodiments, if the value of SiO 2 /B 2 O 3 is less than 0.45, the high-temperature viscosity of the glass is extremely low during molding, and it is easy to generate streaks below the C level inside the glass, so that the glass cannot be used in high-demand imaging applications. In the system, if the value of SiO 2 /B 2 O 3 is higher than 1.2, it is difficult to eliminate the air bubbles in the glass. Therefore, in some embodiments, the value of SiO 2 /B 2 O 3 is more preferably 0.45-1.2, further preferably 0.5-1.1. In some embodiments, the value of SiO2 / B2O3 can be 0.4, 0.45, 0.5, 0.55 , 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9, 0.95, 1.0, 1.05, 1.1, 1.15, 1.2 , 1.25, 1.3.

La2 O3 是本發明玻璃的重要組成成分，加入玻璃中可以快速提升玻璃的折射率，使玻璃實現高折射率低色散的性能。但是，若其含量超過35%，玻璃的抗析晶性能會急劇下降，更為嚴重的是，發明人研究發現La2 O3 有強烈的集聚效應，含量超過35%時，會快速提升玻璃的折射率溫度係數，這和本發明要降低玻璃的折射率溫度係數的目標相悖；若其含量低於10%，玻璃的折射率和色散達不到設計要求，同時玻璃的化學穩定性，尤其是耐水性會降低。因此，La2 O3 的含量限定為10～35%，優選為12～30%，更優選為15～28%。在一些實施方式中，可包含約10%、11%、12%、13%、14%、15%、16%、17%、18%、19%、20%、21%、22%、23%、24%、25%、26%、27%、28%、29%、30%、31%、32%、33%、34%、35%的La2 O3 。La 2 O 3 is an important component of the glass of the present invention, and adding it to the glass can quickly increase the refractive index of the glass, so that the glass can achieve the performance of high refractive index and low dispersion. However, if its content exceeds 35%, the anti-devitrification performance of the glass will drop sharply. What is more serious is that the inventors have found that La 2 O 3 has a strong agglomeration effect. When the content exceeds 35%, it will rapidly increase the Refractive index temperature coefficient, this and the goal of the present invention will reduce the refractive index temperature coefficient of glass; If its content is lower than 10%, the refractive index of glass and dispersion can not reach design requirement, and the chemical stability of glass, especially Water resistance will be reduced. Therefore, the content of La 2 O 3 is limited to 10-35%, preferably 12-30%, more preferably 15-28%. In some embodiments, may comprise about 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23% , 24%, 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35% La 2 O 3 .

為了在La2 O3 含量比較高的情況下玻璃也能維持較好的抗析晶性能，發明人研究發現，添加一定量的Gd2 O3 、Y2 O3 、ZrO2 、TiO2 、Al2 O3 等可以提升玻璃的抗析晶性能。In order to maintain good anti-devitrification properties of the glass even when the content of La 2 O 3 is relatively high, the inventors found that adding a certain amount of Gd 2 O 3 , Y 2 O 3 , ZrO 2 , TiO 2 , Al 2 O 3 etc. can improve the anti-devitrification performance of the glass.

具體的，Gd2 O3 對於折射率和色散的作用與La2 O3 類似，但含量若高於8%，玻璃的折射率溫度係數會快速上升，成本會快速上升，玻璃的抗析晶性能反而會下降，因此，其含量限定為0～8%，優選為1～6%，更優選為1～4%；在一些實施方式中，可包含約0%、大於0%、1%、1.5%、2%、2.5%、3%、3.5%、4%、4.5%、5%、5.5%、6%、6.5%、7%、7.5%、8%的Gd2 O3 。Specifically, the effect of Gd 2 O 3 on the refractive index and dispersion is similar to that of La 2 O 3 , but if the content is higher than 8%, the temperature coefficient of refractive index of the glass will rise rapidly, and the cost will rise rapidly. On the contrary, it will decrease, therefore, its content is limited to 0-8%, preferably 1-6%, more preferably 1-4%; in some embodiments, it can contain about 0%, greater than 0%, 1%, 1.5% %, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8% of Gd 2 O 3 .

少量的Y2 O3 添加到玻璃中替代La2 O3 不會導致玻璃的折射率和色散有較大改變，但若其含量超過5%，玻璃的折射率溫度係數會快速上升，玻璃的抗析晶性能會下降。因此，其含量限定為0～5%，優選為0～3%，進一步優選為1～3%。在一些實施方式中，可包含約0%、大於0%、1%、1.5%、2%、2.5%、3%、3.5%、4%、4.5%、5%的Y2 O3 。Adding a small amount of Y 2 O 3 to the glass instead of La 2 O 3 will not cause a large change in the refractive index and dispersion of the glass, but if its content exceeds 5%, the temperature coefficient of the glass’s refractive index will rise rapidly, and the resistance of the glass will increase. The crystallization performance will decrease. Therefore, its content is limited to 0-5%, preferably 0-3%, more preferably 1-3%. In some embodiments, about 0%, greater than 0%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5% Y 2 O 3 may be included.

ZrO2 在本發明中是任選組分，少量加入到玻璃中可以提升玻璃的抗析晶性能以及顯著提升玻璃的化學穩定性，同時加入少量ZrO2 可以顯著降低生產過程中玻璃液對耐火材料的侵蝕，一方面可以提升爐體壽命，降低爐體維修的成本和廢料排放，另一方面可以顯著抑制耐火材料中的雜質進入玻璃，提升玻璃的透過率和抗析晶穩定性。但是，ZrO2 在本體系玻璃中對降低玻璃的折射率溫度係數是有害的，若其含量超過3%，玻璃的折射率溫度係數會快速提升，達不到設計要求，同時玻璃變得非常難以融化，抗析晶性能會快速下降，因此，本發明中ZrO2 含量限定為3%以下。若ZrO2 的含量低於0.1%，玻璃對耐火材料的侵蝕明顯上升。因此，本發明中ZrO2 含量優選為0.1～3%，更優選為0.1～2%，進一步優選為0.1～1%。在一些實施方式中，可包含約0%、大於0%、0.1%、0.2%、0.3%、0.4%、0.5%、0.6%、0.7%、0.8%、0.9%、1%、1.1%、1.2%、1.3%、1.4%、1.5%、1.6%、1.7%、1.8%、1.9%、2%、2.1%、2.2%、2.3%、2.4%、2.5%、2.6%、2.7%、2.8%、2.9%、3%的ZrO2 。 ZrO2 is an optional component in the present invention, a small amount added to the glass can improve the anti-devitrification performance of the glass and significantly improve the chemical stability of the glass, while adding a small amount of ZrO2 can significantly reduce the impact of the glass liquid on the refractory material during the production process. On the one hand, it can increase the life of the furnace body, reduce the cost of furnace maintenance and waste emissions, on the other hand, it can significantly inhibit the impurities in the refractory material from entering the glass, and improve the transmittance and anti-devitrification stability of the glass. However, ZrO 2 in this system glass is harmful to reduce the temperature coefficient of refractive index of the glass. If its content exceeds 3%, the temperature coefficient of refractive index of the glass will increase rapidly, failing to meet the design requirements, and the glass becomes very difficult to Melting, the anti-devitrification performance will drop rapidly, therefore, in the present invention, the ZrO2 content is limited to 3% or less. If the content of ZrO 2 is lower than 0.1%, the erosion of glass to refractory materials will increase significantly. Therefore, the ZrO2 content in the present invention is preferably 0.1-3%, more preferably 0.1-2%, and even more preferably 0.1-1%. In some embodiments, about 0%, greater than 0%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2 %, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3% ZrO 2 .

少量的Al2 O3 添加到玻璃中可以提升玻璃的抗析晶性能，同時還可以降低玻璃液腐蝕坩堝材料的能力。但若其添加量高於3%，玻璃的折射率溫度係數會上升，同時玻璃的融化性能會下降，折射率也會快速下降。因此，其含量限定在3%以下，優選為2%以下，更優選為0.1～1%。在一些實施方式中，可包含約0%、大於0%、0.1%、0.2%、0.3%、0.4%、0.5%、0.6%、0.7%、0.8%、0.9%、1%、1.1%、1.2%、1.3%、1.4%、1.5%、1.6%、1.7%、1.8%、1.9%、2%、2.1%、2.2%、2.3%、2.4%、2.5%、2.6%、2.7%、2.8%、2.9%、3%的Al2 O3 。Adding a small amount of Al 2 O 3 to the glass can improve the anti-devitrification performance of the glass, and can also reduce the ability of the glass liquid to corrode the crucible material. However, if the added amount is higher than 3%, the temperature coefficient of the glass's refractive index will increase, and at the same time, the melting performance of the glass will decrease, and the refractive index will also drop rapidly. Therefore, its content is limited to 3% or less, preferably 2% or less, more preferably 0.1-1%. In some embodiments, about 0%, greater than 0%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2 %, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3% Al 2 O 3 .

少量的TiO2 添加到玻璃中，會提升玻璃的耐日照穩定性，尤其是對於車載鏡頭長期暴露在高原等強紫外線環境中特別重要。另外，少量的TiO2 會提升玻璃的抗析晶性能。但TiO2 對於本體系玻璃來說，對折射率溫度係數的降低是有害的；經過發明人大量試驗研究發現，若其含量超過3%，玻璃的折射率溫度係數達不到設計要求，因此，本發明中TiO2 含量為3%以下，優選為0～2%，更優選為0～1%。在一些實施方式中，可包含約0%、大於0%、0.1%、0.2%、0.3%、0.4%、0.5%、0.6%、0.7%、0.8%、0.9%、1%、1.1%、1.2%、1.3%、1.4%、1.5%、1.6%、1.7%、1.8%、1.9%、2%、2.1%、2.2%、2.3%、2.4%、2.5%、2.6%、2.7%、2.8%、2.9%、3%的TiO2 。Adding a small amount of TiO 2 to the glass will improve the sunlight resistance stability of the glass, which is especially important for long-term exposure of vehicle lenses to strong ultraviolet environments such as plateaus. In addition, a small amount of TiO 2 will improve the anti-devitrification performance of the glass. But TiO 2 is harmful to the reduction of the temperature coefficient of refractive index for the glass of this system; through a large number of experiments and researches by the inventor, it is found that if its content exceeds 3%, the temperature coefficient of refractive index of the glass cannot meet the design requirements. Therefore, In the present invention, the TiO2 content is 3% or less, preferably 0-2%, more preferably 0-1%. In some embodiments, about 0%, greater than 0%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2 %, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3% TiO 2 .

Nb2 O5 、WO3 屬於高折射高色散氧化物，添加到玻璃中可以調節玻璃的折射率和色散，同時提升玻璃的化學穩定性。經發明人研究發現，在本體系玻璃中，這兩種氧化物提升玻璃折射率溫度係數的能力比其他高折射高色散氧化物慢，如TiO2 、Bi2 O3 、Ta2 O5 、PbO等；從降低本發明玻璃折射率溫度係數的角度來說，這兩種高色散氧化物是增加玻璃色散的理想氧化物。若Nb2 O5 的含量超過5%，玻璃的阿貝數會快速下降達不到設計要求，玻璃的抗析晶性能也會快速下降，因此，本發明中Nb2 O5 的含量限定為5%以下。若Nb2 O5 的含量低於0.1%，那麼就意味著需要加入更多的WO3 或者上述其他高色散氧化物，這樣會導致玻璃的透過率下降，或者是折射率溫度係數快速上升，因此，Nb2 O5 的含量優選為0.1～5%，更優選為0.5～4%，進一步優選為1～3%。在一些實施方式中，可包含約0%、大於0%、0.1%、0.2%、0.3%、0.4%、0.5%、0.6%、0.7%、0.8%、0.9%、1%、1.1%、1.2%、1.3%、1.4%、1.5%、1.6%、1.7%、1.8%、1.9%、2%、2.1%、2.2%、2.3%、2.4%、2.5%、2.6%、2.7%、2.8%、2.9%、3%的Nb2 O5 。Nb 2 O 5 and WO 3 are high-refractive and high-dispersion oxides, which can be added to the glass to adjust the refractive index and dispersion of the glass, while improving the chemical stability of the glass. The inventors found that in the glass of this system, the ability of these two oxides to increase the temperature coefficient of the glass's refractive index is slower than other high-refractive and high-dispersion oxides, such as TiO 2 , Bi 2 O 3 , Ta 2 O 5 , PbO etc.; from the point of view of reducing the temperature coefficient of refractive index of the glass of the present invention, these two high-dispersion oxides are ideal oxides for increasing the dispersion of the glass. If the content of Nb 2 O 5 exceeds 5%, the Abbe number of the glass will drop rapidly and fail to meet the design requirements, and the anti-devitrification performance of the glass will also drop rapidly. Therefore, the content of Nb 2 O 5 is limited to 5% in the present invention. %the following. If the content of Nb 2 O 5 is lower than 0.1%, it means that more WO 3 or other high-dispersion oxides mentioned above need to be added, which will lead to a decrease in the transmittance of the glass, or a rapid increase in the temperature coefficient of the refractive index, so , the content of Nb 2 O 5 is preferably 0.1 to 5%, more preferably 0.5 to 4%, and even more preferably 1 to 3%. In some embodiments, about 0%, greater than 0%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2 %, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3% Nb 2 O 5 .

WO3 可以少量替代Nb2 O5 使用，但若其含量超過2%，玻璃的透過率會明顯下降；因此，其含量限定為2%以下，優選為1%以下，進一步優選為不引入。在一些實施方式中，可包含約0%、大於0%、0.1%、0.2%、0.3%、0.4%、0.5%、0.6%、0.7%、0.8%、0.9%、1%、1.1%、1.2%、1.3%、1.4%、1.5%、1.6%、1.7%、1.8%、1.9%、2%的WO3 。WO 3 can be used instead of Nb 2 O 5 in a small amount, but if its content exceeds 2%, the transmittance of the glass will decrease significantly; therefore, its content is limited to less than 2%, preferably less than 1%, and more preferably not introduced. In some embodiments, about 0%, greater than 0%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2 %, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2% of WO 3 .

進一步的，本發明涉及的玻璃主要是在露天惡劣環境下使用，比如車載鏡頭，安防鏡頭等，會長期受到陽光暴曬，尤其是在高原地區。傳統的光學玻璃是面向攝影器材設計的，通常沒有考慮到玻璃在長期暴曬後透過率下降的問題；因此，如何提升玻璃的耐日照穩定性，是本發明玻璃關注的一個重點問題。Furthermore, the glass involved in the present invention is mainly used in harsh open-air environments, such as vehicle lenses, security lenses, etc., and will be exposed to sunlight for a long time, especially in plateau areas. Traditional optical glass is designed for photographic equipment, and usually does not consider the problem of glass transmittance decrease after long-term exposure to sunlight; therefore, how to improve the sunlight resistance stability of glass is a key issue of the glass of the present invention.

經發明人多次試驗發現，在一些實施方式中，Nb2 O5 和TiO2 同時使用會比單獨使用TiO2 提升玻璃耐日照穩定性的效果更明顯；但是，當TiO2 與Nb2 O5 的比值TiO2 /Nb2 O5 大於1時，玻璃的耐日照穩定性不再提升，但折射率溫度係數上升較快，這對想獲得更低的折射率溫度係數的目標是相違背的。因此，為了獲得更低折射率溫度係數且耐日照穩定性強的玻璃，TiO2 /Nb2 O5 的值為1以下，優選為0.8以下，進一步優選為0.5以下。在一些實施方式中，TiO2 /Nb2 O5 的值可為0、0.05、0.1、0.15、0.2、0.25、0.3、0.35、0.4、0.45、0.5、0.55、0.6、0.65、0.7、0.75、0.8、0.85、0.9、0.95、1。The inventors have found through many experiments that, in some embodiments, the simultaneous use of Nb 2 O 5 and TiO 2 will be more effective than using TiO 2 alone to improve the sunlight stability of glass; however, when TiO 2 and Nb 2 O 5 When the ratio of TiO 2 /Nb 2 O 5 is greater than 1, the sunlight resistance stability of the glass is no longer improved, but the temperature coefficient of the refractive index rises faster, which is contrary to the goal of obtaining a lower temperature coefficient of the refractive index. Therefore, in order to obtain a glass with a lower temperature coefficient of refraction and strong sunlight resistance stability, the value of TiO 2 /Nb 2 O 5 is 1 or less, preferably 0.8 or less, more preferably 0.5 or less. In some embodiments, the value of TiO2 / Nb2O5 can be 0, 0.05, 0.1, 0.15, 0.2, 0.25, 0.3 , 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8 , 0.85, 0.9, 0.95, 1.

對於本發明體系的玻璃，ZnO添加到玻璃中可以提升玻璃的化學穩定性，降低玻璃的高溫粘度，從而降低玻璃的生產難度。但是，發明人研究發現，若ZnO的含量超過5%，玻璃的折射率溫度係數會快速下降；因此，其含量限定為5%以下，優選為3%以下，進一步優選為不引入。在一些實施方式中，可包含約0%、大於0%、0.1%、0.5%、1%、1.5%、2%、2.5%、3%、3.5%、4%、4.5%、5%的ZnO。For the glass of the system of the present invention, adding ZnO to the glass can improve the chemical stability of the glass, reduce the high-temperature viscosity of the glass, and thus reduce the difficulty of glass production. However, the inventors have found that if the content of ZnO exceeds 5%, the temperature coefficient of refractive index of the glass will drop rapidly; therefore, its content is limited to less than 5%, preferably less than 3%, and more preferably not introduced. In some embodiments, about 0%, greater than 0%, 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5% ZnO can be included .

BaO、CaO、SrO、MgO均為鹼土金屬氧化物，加入到玻璃中可以調節玻璃的折射率和色散，增強玻璃的穩定性，提升玻璃的抗析晶性能，一般的技術文獻認為在此類玻璃中同族氧化物的作用是基本相同的。但是，發明人通過多次試驗發現，對於本系統玻璃最為關注的折射率溫度係數、化學穩定性、抗析晶性能來說，以上幾種鹼土金屬氧化物的作用存在非常大的區別。BaO, CaO, SrO, and MgO are all alkaline earth metal oxides, which can adjust the refractive index and dispersion of the glass when added to the glass, enhance the stability of the glass, and improve the anti-devitrification performance of the glass. The general technical literature believes that in this type of glass The role of the same group of oxides is basically the same. However, the inventors have found through many experiments that, for the temperature coefficient of refractive index, chemical stability, and anti-devitrification performance of the glass of this system, the effects of the above alkaline earth metal oxides are very different.

BaO降低玻璃折射率溫度係數的能力最強，因此其含量需限定在10%以上，才能達到發明期望的折射率溫度係數；但若其含量超過40%，玻璃的化學穩定性，尤其是耐水性會快速下降，玻璃的抗析晶性能也會快速下降。因此其含量限定為10～40%，優選為12～35%，進一步優選為15～32%。在一些實施方式中，可包含約10%、11%、12%、13%、14%、15%、16%、17%、18%、19%、20%、21%、22%、23%、24%、25%、26%、27%、28%、29%、30%、31%、32%、33%、34%、35%、36%、37%、38%、39%、40%的BaO。BaO has the strongest ability to reduce the temperature coefficient of refractive index of glass, so its content must be limited to more than 10% in order to achieve the desired temperature coefficient of refractive index of the invention; but if its content exceeds 40%, the chemical stability of the glass, especially the water resistance will be affected. Rapid decline, the anti-devitrification performance of the glass will also decline rapidly. Therefore, its content is limited to 10-40%, preferably 12-35%, more preferably 15-32%. In some embodiments, may comprise about 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23% , 24%, 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, 40 % BaO.

SrO降低玻璃折射率溫度係數的能力強於CaO但弱於BaO，其加入玻璃中破壞玻璃化學穩定性的能力弱於BaO，若SrO的含量超過15%，玻璃的抗析晶性能反而會快速惡化，同時玻璃的折射率溫度係數會快速上升，因此其含量為15%以下。另一方面，通過大量實驗研究發現，在BaO高於15%時，加入0.5%以上的SrO可以明顯提升玻璃的耐水性和抗析晶穩定性，同時玻璃的折射率溫度係數還不會明顯上升。因此，本發明中優選SrO含量為0.5～15%，更優選為1～12%，進一步優選為1.5～10%。在一些實施方式中，可包含約0%、大於0%、0.1%、0.5%、1%、1.5%、2%、2.5%、3%、3.5%、4%、4.5%、5%、5.5%、6%、6.5%、7%、7.5%、8%、8.5%、9%、9.5%、10%、10.5%、11%、11.5%、12%、12.5%、13%、13.5%、14%、14.5%、15%的SrO。The ability of SrO to reduce the temperature coefficient of refractive index of glass is stronger than that of CaO but weaker than that of BaO. Its ability to destroy the chemical stability of glass is weaker than that of BaO. If the content of SrO exceeds 15%, the anti-devitrification performance of glass will deteriorate rapidly. , At the same time, the temperature coefficient of refractive index of the glass will rise rapidly, so its content is below 15%. On the other hand, a large number of experimental studies have found that when BaO is higher than 15%, adding more than 0.5% SrO can significantly improve the water resistance and anti-devitrification stability of the glass, and at the same time, the temperature coefficient of refractive index of the glass will not increase significantly. . Therefore, in the present invention, the SrO content is preferably 0.5 to 15%, more preferably 1 to 12%, and even more preferably 1.5 to 10%. In some embodiments, about 0%, greater than 0%, 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5% may be included %, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, 10%, 10.5%, 11%, 11.5%, 12%, 12.5%, 13%, 13.5%, 14%, 14.5%, 15% SrO.

通常來講，CaO是鑭冕玻璃中必不可少的組分，其加入玻璃中可以提升玻璃的折射率和色散，顯著降低玻璃的密度，使得鏡片可以輕量化，降低玻璃的高溫粘度和表面張力，降低玻璃的生產難度，但是，對於本發明體系玻璃來講，CaO降低玻璃的折射率溫度係數的能力次於BaO和SrO，因此從降低折射率溫度係數的角度來講，優選是不引入；其中，CaO在以上三種鹼土金屬氧化物中，破壞耐水性的能力最弱，因此從提升玻璃耐水性的角度來講，也是可以適量添加的。因此，CaO含量限定為0～10%，優選為0～8%，進一步優選為0～6%。在一些實施方式中，可包含約0%、大於0%、0.5%、1%、1.5%、2%、2.5%、3%、3.5%、4%、4.5%、5%、5.5%、6%、6.5%、7%、7.5%、8%、8.5%、9%、9.5%、10%的CaO。Generally speaking, CaO is an essential component of lanthanum crown glass. Its addition to glass can increase the refractive index and dispersion of the glass, significantly reduce the density of the glass, make the lens lightweight, and reduce the high-temperature viscosity and surface tension of the glass. , to reduce the production difficulty of glass, but, for the system glass of the present invention, the ability of CaO to reduce the temperature coefficient of refractive index of glass is inferior to that of BaO and SrO, so from the perspective of reducing the temperature coefficient of refractive index, it is preferably not introduced; Among them, CaO has the weakest ability to destroy water resistance among the above three alkaline earth metal oxides, so from the perspective of improving the water resistance of glass, it can also be added in an appropriate amount. Therefore, the CaO content is limited to 0 to 10%, preferably 0 to 8%, and more preferably 0 to 6%. In some embodiments, about 0%, greater than 0%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6 %, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, 10% of CaO.

對於本發明體系玻璃來說，MgO對降低玻璃折射率溫度係數是有害的，但少量加入可以提升玻璃的耐水性和穩定性。若其含量超過5%，玻璃的折射率溫度係數達不到設計要求，同時玻璃的抗析晶能力會快速下降。因此，其含量限定為5%以下，優選為3%以下，進一步優選為不引入；在一些實施方式中，可包含約0%、大於0%、0.1%、0.5%、1%、1.5%、2%、2.5%、3%、3.5%、4%、4.5%、5%的MgO。For the glass of the system of the present invention, MgO is detrimental to lowering the temperature coefficient of refractive index of the glass, but adding a small amount can improve the water resistance and stability of the glass. If its content exceeds 5%, the temperature coefficient of refractive index of the glass will not meet the design requirements, and at the same time, the anti-devitrification ability of the glass will drop rapidly. Therefore, its content is limited to less than 5%, preferably less than 3%, and more preferably not introduced; in some embodiments, it may contain about 0%, greater than 0%, 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5% MgO.

更重要的是，發明人研究發現，在一些實施方式中，當BaO、CaO、SrO三種鹼土金屬氧化物都添加時，玻璃會發生複雜的協同作用，性能並不隨著單一物質的添加發生線性變化，當CaO/(BaO+SrO)的值超過0.5時，雖然玻璃的化學穩定性會有一定提升，但玻璃的折射率溫度係數會快速上升，玻璃的抗析晶性能會快速下降，因此本發明中CaO/(BaO+SrO)的值優選為0～0.5。在一些實施方式中，更優選CaO/(BaO+SrO)的值為0.01～0.4，進一步優選為0.02～0.3時，玻璃的折射率溫度係數、化學穩定性、抗析晶性能均能達到設計預期。在一些實施方式中，CaO/(BaO+SrO)的值可為0，大於0、0.01、0.02、0.05、0.1、0.15、0.2、0.25、0.3、0.35、0.4、0.45、0.5。More importantly, the inventors have found that in some embodiments, when BaO, CaO, and SrO are all added, the glass will have a complex synergistic effect, and the performance will not be linear with the addition of a single substance. When the value of CaO/(BaO+SrO) exceeds 0.5, although the chemical stability of the glass will be improved to a certain extent, the temperature coefficient of the refractive index of the glass will increase rapidly, and the anti-devitrification performance of the glass will decrease rapidly. Therefore, this In the invention, the value of CaO/(BaO+SrO) is preferably 0 to 0.5. In some embodiments, when the value of CaO/(BaO+SrO) is more preferably 0.01-0.4, more preferably 0.02-0.3, the temperature coefficient of refractive index, chemical stability, and devitrification resistance of the glass can all meet the design expectations . In some embodiments, the value of CaO/(BaO+SrO) can be 0, greater than 0, 0.01, 0.02, 0.05, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5.

在一些實施方式中，若想獲得更低溫度折射率係數，優選滿足BaO含量≥CaO含量，進一步滿足SrO含量≥CaO含量，更進一步滿足BaO含量≥SrO含量≥CaO含量。In some embodiments, if one wants to obtain a lower temperature refractive index, it is preferable to satisfy BaO content≥CaO content, further satisfy SrO content≥CaO content, and further satisfy BaO content≥SrO content≥CaO content.

若玻璃體系中添加ZnO來增強玻璃的化學穩定性，就必須考慮到添加ZnO所帶來的折射率溫度係數上升的問題；發明人研究發現，在一些實施方式中，ZnO/（CaO+BaO+SrO）的值會對折射率溫度係數和玻璃的化學穩定性有影響；當ZnO/（CaO+BaO+SrO）的值大於0.3時，玻璃的化學穩定性幾乎不再增長，但玻璃的折射率溫度係數急劇上升。因此，要想獲得化學穩定性較好且折射率溫度係數較低的玻璃，ZnO/（CaO+BaO+SrO）的值應優選為0.3以下，更優選為0.2以下，進一步優選為0.15以下。在一些實施方式中，ZnO/（CaO+BaO+SrO）的值可為0，大於0、0.01、0.02、0.03、0.04、0.05、0.06、0.07、0.08、0.09、0.1、0.11、0.12、0.13、0.14、0.15、0.16、0.17、0.18、0.19、0.2、0.21、0.22、0.23、0.24、0.25、0.26、0.27、0.28、0.29、0.3。If ZnO is added to the glass system to enhance the chemical stability of the glass, the problem that the temperature coefficient of refraction caused by the addition of ZnO must be taken into account; the inventors have found that, in some embodiments, ZnO/(CaO+BaO+ The value of SrO) will affect the temperature coefficient of the refractive index and the chemical stability of the glass; when the value of ZnO/(CaO+BaO+SrO) is greater than 0.3, the chemical stability of the glass will hardly increase, but the refractive index of the glass The temperature coefficient rises sharply. Therefore, in order to obtain a glass with better chemical stability and a lower temperature coefficient of refractive index, the value of ZnO/(CaO+BaO+SrO) should preferably be 0.3 or less, more preferably 0.2 or less, and even more preferably 0.15 or less. In some embodiments, the value of ZnO/(CaO+BaO+SrO) can be 0, greater than 0, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.11, 0.12, 0.13, 0.14, 0.15, 0.16, 0.17, 0.18, 0.19, 0.2, 0.21, 0.22, 0.23, 0.24, 0.25, 0.26, 0.27, 0.28, 0.29, 0.3.

Li2 O、Na2 O、K2 O均屬於鹼金屬氧化物，合適量的加入能降低玻璃的折射率溫度係數，但玻璃的化學穩定性、抗析晶性能會快速降低。發明人通過大量試驗發現：Li 2 O, Na 2 O, and K 2 O are all alkali metal oxides. Adding an appropriate amount can reduce the temperature coefficient of refractive index of the glass, but the chemical stability and devitrification resistance of the glass will decrease rapidly. The inventor finds through a large number of tests:

1）在本發明體系玻璃中，玻璃的折射率溫度係數並不是隨著鹼金屬氧化物增長而線性降低，而是到了一個極值後折射率溫度係數不再下降，但在這個極值上繼續添加鹼金屬氧化物，玻璃的抗析晶性能會急劇惡化；在一些實施方式中，Li2 O、Na2 O與K2 O的含量之和Li2 O+Na2 O+K2 O的值若超過8%，玻璃的折射率溫度係數並不再下降，而抗析晶性能和耐水性急劇下降。1) In the system glass of the present invention, the temperature coefficient of the refractive index of the glass does not decrease linearly with the increase of the alkali metal oxide, but after reaching an extreme value, the temperature coefficient of the refractive index does not decrease any more, but continues at this extreme value. With the addition of alkali metal oxides, the devitrification resistance of the glass will deteriorate sharply; in some embodiments, the value of the sum of the contents of Li 2 O, Na 2 O and K 2 O If it exceeds 8%, the temperature coefficient of refractive index of the glass will not drop any more, but the anti-devitrification performance and water resistance will drop sharply.

從生產的角度來說，期望在澄清時高溫粘度越低，越有利於氣泡的排出，因此，若玻璃的折射率溫度係數、耐水性與抗析晶性能達到設計要求時，可以添加不超過8%的上述鹼金屬氧化物，提升玻璃的高溫粘度，提升量產時玻璃的氣泡度水準。因此，Li2 O+Na2 O+K2 O的合計量控制在8%以下，優選在6%以下，進一步優選在5%以下。在一些實施方式中，Li2 O+Na2 O+K2 O的合計量可為約0%、大於0%、0.5%、1%、1.5%、2%、2.5%、3%、3.5%、4%、4.5%、5%、5.5%、6%、6.5%、7%、7.5%、8%。From the point of view of production, it is expected that the lower the viscosity at high temperature during clarification, the more conducive to the discharge of air bubbles. Therefore, if the temperature coefficient of refractive index, water resistance and anti-devitrification performance of the glass meet the design requirements, no more than 8 % of the above-mentioned alkali metal oxides can increase the high-temperature viscosity of the glass and improve the bubble degree level of the glass during mass production. Therefore, the total amount of Li 2 O+Na 2 O+K 2 O is controlled to be 8% or less, preferably 6% or less, more preferably 5% or less. In some embodiments, the total amount of Li2O + Na2O + K2O can be about 0%, greater than 0%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5% , 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%.

2）當以上三種鹼金屬氧化物都共同存在時，會產生協同效應，在一些實施方式中，若Li2 O/(K2 O+Na2 O)的值大於0.5時，玻璃的折射率溫度係數基本不變，但玻璃的抗析晶性能與化學穩定性急劇下降，因此，Li2 O/(K2 O+Na2 O)的值優選小於0.5，更優選小於0.4，進一步優選小於0.3。在一些實施方式中，Li2 O/(K2 O+Na2 O)的值可為0、大於0、0.01、0.02、0.03、0.04、0.05、0.06、0.07、0.08、0.09、0.1、0.15、0.2、0.25、0.3、0.35、0.4、0.45、0.5。2) When the above three alkali metal oxides coexist, there will be a synergistic effect. In some embodiments, if the value of Li 2 O/(K 2 O+Na 2 O) is greater than 0.5, the refractive index temperature of the glass The coefficient remains basically the same, but the devitrification resistance and chemical stability of the glass drop sharply. Therefore, the value of Li 2 O/(K 2 O+Na 2 O) is preferably less than 0.5, more preferably less than 0.4, and even more preferably less than 0.3. In some embodiments, the value of Li2O /( K2O + Na2O ) can be 0, greater than 0, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5.

發明人研究還發現，從降低折射率溫度係數的角度來說，K2 O和Na2 O較強，而Li2 O次之；從破壞玻璃的化學穩定性的角度來說，K2 O和Na2 O較強，而Li2 O次之；從破壞玻璃的抗析晶性能方面來說，Li2 O最強，K2 O和Na2 O次之。因此，為了獲得滿足設計預期的折射率溫度係數、化學穩定性以及抗析晶性能，如何選用合適種類和合適量的鹼金屬氧化物，需要大量的試驗研究來確定。從單組分的鹼金屬氧化物來說，若Na2 O含量超過8%，玻璃的抗析晶性能和化學穩定性會急劇下降，因此，在一些實施方式中，其含量限定為0～8%，優選為0.5～6%，進一步優選為1～3%。在一些實施方式中，若K2 O含量高於6%，玻璃的抗析晶性能和化學穩定性會快速下降，因此，其含量限定為0～6%,優選為0.3～4%，進一步優選為0.5～3%。在一些實施方式中，Li2 O的含量若超過5%，玻璃的抗析晶性能會快速下降，因此其含量優選為5%以下，更優選3%以下，進一步優選為不引入。在一些實施方式中，Li2 O的含量可為約0%、大於0%、0.5%、1%、1.5%、2%、2.5%、3%、3.5%、4%、4.5%、5%。在一些實施方式中，Na2 O的含量可為約0%、大於0%、0.5%、1%、1.5%、2%、2.5%、3%、3.5%、4%、4.5%、5%、5.5%、6%、6.5%、7%、7.5%、8%。在一些實施方式中，K2 O的含量可為約0%、大於0%、0.3%、0.5%、1%、1.5%、2%、2.5%、3%、3.5%、4%、4.5%、5%、5.5%、6%。The inventors also found that, from the perspective of reducing the temperature coefficient of the refractive index, K 2 O and Na 2 O are stronger, and Li 2 O is second; from the perspective of destroying the chemical stability of the glass, K 2 O and Na 2 O are stronger. Na 2 O is the strongest, followed by Li 2 O; in terms of the anti-devitrification performance of the broken glass, Li 2 O is the strongest, followed by K 2 O and Na 2 O. Therefore, in order to obtain the expected temperature coefficient of refraction index, chemical stability, and anti-devitrification performance, how to select the appropriate type and amount of alkali metal oxides needs a lot of experimental research to determine. For a single-component alkali metal oxide, if the Na 2 O content exceeds 8%, the anti-devitrification performance and chemical stability of the glass will drop sharply. Therefore, in some embodiments, its content is limited to 0-8% %, preferably 0.5 to 6%, more preferably 1 to 3%. In some embodiments, if the K 2 O content is higher than 6%, the devitrification resistance and chemical stability of the glass will decrease rapidly, therefore, its content is limited to 0-6%, preferably 0.3-4%, more preferably 0.5-3%. In some embodiments, if the content of Li 2 O exceeds 5%, the devitrification resistance of the glass will decrease rapidly, so the content is preferably less than 5%, more preferably less than 3%, and even more preferably not introduced. In some embodiments, the content of Li2O can be about 0%, greater than 0%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5% . In some embodiments, the content of Na2O can be about 0%, greater than 0%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5% , 5.5%, 6%, 6.5%, 7%, 7.5%, 8%. In some embodiments, the content of K2O can be about 0%, greater than 0%, 0.3%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5% , 5%, 5.5%, 6%.

發明人大量研究發現，在一些實施方式中，玻璃中Na2 O/K2 O的比例跟玻璃的氣泡度與耐水性有較大的關聯，當Na2 O/K2 O的值大於5.0時，玻璃的耐水性急劇下降；當Na2 O/K2 O的值小於0.2時，玻璃的氣泡度快速下降。因此，Na2 O/K2 O的值處於0.2～5.0之間，優選為0.3～4.0之間，進一步優選為0.4～3.0之間時，玻璃可獲得優異的氣泡度與耐水性。在一些實施方式中，Na2 O/K2 O的值可為0.2、0.3、0.4、0.5、0.6、0.7、0.8、0.9、1.0、1.2、1.4、1.5、1.6、1.8、2.0、2.2、2.4、2.5、2.6、2.8、3.0、3.2、3.4、3.5、3.6、3.8、4.0、4.2、4.4、4.5、4.6、4.8、5.0。The inventors have found through a lot of research that, in some embodiments, the ratio of Na 2 O/K 2 O in the glass has a greater relationship with the bubble degree and water resistance of the glass. When the value of Na 2 O/K 2 O is greater than 5.0 , the water resistance of the glass drops sharply; when the value of Na 2 O/K 2 O is less than 0.2, the bubble degree of the glass drops rapidly. Therefore, when the value of Na 2 O/K 2 O is between 0.2-5.0, preferably between 0.3-4.0, more preferably between 0.4-3.0, the glass can obtain excellent bubble degree and water resistance. In some embodiments, the value of Na2O / K2O can be 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.2, 1.4, 1.5, 1.6, 1.8, 2.0, 2.2, 2.4 , 2.5, 2.6, 2.8, 3.0, 3.2, 3.4, 3.5, 3.6, 3.8, 4.0, 4.2, 4.4, 4.5, 4.6, 4.8, 5.0.

對於本發明體系玻璃來說，BaO、SrO、CaO等鹼土金屬氧化物的合計含量與La2 O3 、Gd2 O3 、Y2 O3 的合計含量的比值與玻璃的折射率溫度係數、抗析晶性能以及耐水性有較大的關係。在一些實施方式中，當（BaO+SrO+CaO）/(La2 O3 +Gd2 O3 +Y2 O3 )的值大於2.5時，玻璃的折射率溫度係數不再下降，而玻璃的耐水性快速下降；當（BaO+SrO+CaO）/(La2 O3 +Gd2 O3 +Y2 O3 )小於0.7時，玻璃的耐水性有所提升，但玻璃的折射率溫度係數快速上升，玻璃的抗析晶性能快速下降。因此，要獲得折射率溫度係數較低，耐水性達到設計要求，並且抗析晶性能較好的玻璃，需要滿足（BaO+SrO+CaO）/(La2 O3 +Gd2 O3 +Y2 O3 )的值為0.7～2.5，優選為0.8～2.3，進一步優選為0.9～2.1。在一些實施方式中，（BaO+SrO+CaO）/( La2 O3 +Gd2 O3 +Y2 O3 )的值可為0.7、0.8、0.9、1.0、1.1、1.2、1.3、1.4、1.5、1.6、1.7、1.8、1.9、2.0、2.1、2.2、2.3、2.4、2.5。For the system glass of the present invention, the ratio of the total content of alkaline earth metal oxides such as BaO, SrO, CaO to the total content of La 2 O 3 , Gd 2 O 3 , Y 2 O 3 is related to the temperature coefficient of refractive index of the glass, the resistance Crystallization performance and water resistance have a great relationship. In some embodiments, when the value of (BaO+SrO+CaO)/(La 2 O 3 +Gd 2 O 3 +Y 2 O 3 ) is greater than 2.5, the temperature coefficient of the glass's refractive index does not decrease any more, and the glass's The water resistance decreases rapidly; when (BaO+SrO+CaO)/(La 2 O 3 +Gd 2 O 3 +Y 2 O 3 ) is less than 0.7, the water resistance of the glass is improved, but the temperature coefficient of refractive index of the glass is rapid As the temperature rises, the anti-devitrification performance of the glass decreases rapidly. Therefore, in order to obtain a glass with a low temperature coefficient of refractive index, water resistance that meets the design requirements, and good devitrification resistance, it is necessary to satisfy (BaO+SrO+CaO)/(La 2 O 3 +Gd 2 O 3 +Y 2 The value of O 3 ) is 0.7 to 2.5, preferably 0.8 to 2.3, more preferably 0.9 to 2.1. In some embodiments, the value of (BaO+SrO+CaO)/(La 2 O 3 +Gd 2 O 3 +Y 2 O 3 ) can be 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5.

在本發明體系玻璃中，BaO和La2 O3 均為主要組分，研究發現，其比值對於玻璃的折射率溫度係數和玻璃的耐水性及其抗析晶性能有較大的關聯。在一些實施方式中，當BaO、La2 O3 含量的比值BaO/La2 O3 大於2時，玻璃的折射率溫度係數不再下降，但玻璃的耐水性急劇下降；當BaO/La2 O3 的值小於0.6時，玻璃的耐水性雖然有較大的提升，但玻璃的折射率溫度係數達不到設計要求，且玻璃的抗析晶性能急劇惡化，甚至在熔煉過程中就發生析晶。因此，BaO/La2 O3 的值限定在0.6～2之間，優選為0.65～1.9，進一步優選為0.7～1.8。在一些實施方式中，BaO/La2 O3 的值可為0.6、0.65、0.7、0.75、0.8、0.85、0.9、0.95、1.0、1.05、1.1、1.15、1.2、1.25、1.3、1.35、1.4、1.45、1.5、1.55、1.6、1.65、1.7、1.75、1.8、1.85、1.9、1.95、2.0。In the system glass of the present invention, both BaO and La 2 O 3 are the main components. It is found that their ratio has a great relationship with the temperature coefficient of refractive index of the glass, the water resistance and the anti-devitrification performance of the glass. In some embodiments, when the content ratio BaO/La 2 O 3 of BaO and La 2 O 3 is greater than 2, the temperature coefficient of refractive index of the glass no longer drops, but the water resistance of the glass drops sharply; when BaO/La 2 O When the value of 3 is less than 0.6, although the water resistance of the glass is greatly improved, the temperature coefficient of the glass’s refractive index does not meet the design requirements, and the anti-devitrification performance of the glass deteriorates sharply, and even devitrification occurs during the melting process . Therefore, the value of BaO/La 2 O 3 is limited to 0.6-2, preferably 0.65-1.9, more preferably 0.7-1.8. In some embodiments, the value of BaO/ La2O3 can be 0.6, 0.65, 0.7, 0.75, 0.8 , 0.85, 0.9, 0.95, 1.0, 1.05, 1.1, 1.15, 1.2, 1.25, 1.3, 1.35, 1.4, 1.45, 1.5, 1.55, 1.6, 1.65, 1.7, 1.75, 1.8, 1.85, 1.9, 1.95, 2.0.

發明人研究發現，在一些實施方式中，（CaO+BaO+SrO） /（Al2 O3 +ZrO2 +TiO2 ）的值和玻璃的折射率溫度係數有較大的關聯。當（CaO+BaO+SrO）/（Al2 O3 +ZrO2 +TiO2 ）的值小於8時，雖然玻璃的化學穩定性和抗析晶性能有微弱的提升，但玻璃的折射率溫度係數急劇上升，達不到設計要求；因此，（CaO+BaO+SrO）/（Al2 O3 +ZrO2 +TiO2 ）的值應大於8，優選大於10，進一步優選大於12。The inventors found that, in some embodiments, the value of (CaO+BaO+SrO)/(Al 2 O 3 +ZrO 2 +TiO 2 ) has a large correlation with the temperature coefficient of refractive index of glass. When the value of (CaO+BaO+SrO)/(Al 2 O 3 +ZrO 2 +TiO 2 ) is less than 8, although the chemical stability and devitrification resistance of the glass are slightly improved, the temperature coefficient of refractive index of the glass Therefore, the value of (CaO+BaO+SrO)/(Al 2 O 3 +ZrO 2 +TiO 2 ) should be greater than 8, preferably greater than 10, more preferably greater than 12.

Sb2 O3 、SnO2 、SnO和CeO2 中的一種或幾種組分可作為澄清劑加入，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2%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形模具的惡化，因此本發明Sb2 O3 的添加量為2%以下，優選為1%以下，更優選為0.5%以下。SnO2 、SnO也可以作為澄清劑來添加，但當其含量超過2%時，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 和SnO的分別含量為2%以下，優選為1%以下，更優選為0.5%以下，進一步優選不引入。CeO2 的作用及添加量比例與SnO2 一致，其含量為2%以下，優選為1%以下，更優選為0.5%以下，進一步優選不引入。在一些實施方式中，以上4種澄清劑中的一種或一種以上的含量約為0%、大於0%、0.1%、0.2%、0.3%、0.4%、0.5%、0.6%、0.7%、0.8%、0.9%、1.0%、1.1%、1.2%、1.3%、1.4%、1.5%、1.6%、1.7%、1.8%、1.9%、2.0%。One or several components of Sb 2 O 3 , SnO 2 , SnO and CeO 2 can be added as clarifiers, and the clarification effect of glass can be improved by adding a small amount of Sb 2 O 3 , SnO 2 , and CeO 2 components, but when When the Sb 2 O 3 content exceeds 2%, the glass has a tendency to reduce the clarification performance, and at the same time, due to its strong oxidation effect, the deterioration of the forming mold is promoted, so the addition of Sb 2 O 3 in the present invention is 2% or less, preferably 1%. or less, more preferably 0.5% or less. SnO 2 and SnO can also be added as clarifiers, but when the content exceeds 2%, the glass will be colored, or when the glass is heated, softened, and molded again, Sn will become the starting point of crystal nucleation, resulting in The tendency of devitrification, so the content of SnO 2 and SnO in the present invention is 2% or less, preferably 1% or less, more preferably 0.5% or less, more preferably not introduced. The role and addition ratio of CeO 2 are consistent with SnO 2 , and its content is 2% or less, preferably 1% or less, more preferably 0.5% or less, and even more preferably not introduced. In some embodiments, the content of one or more of the above four clarifying agents is about 0%, greater than 0%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8% %, 0.9%, 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2.0%.

在一些實施方式中，還可以用As2 O3 、Cl的化合物、Br的化合物等作為澄清劑，其含量分別為2%以下，優選為1%以下，更優選為0.5%以下,但從環保等因素考慮，優選不引入As2 O3 。在一些實施方式中，以上3種澄清劑中的一種或一種以上的含量約為0%、大於0%、0.1%、0.2%、0.3%、0.4%、0.5%、0.6%、0.7%、0.8%、0.9%、1.0%、1.1%、1.2%、1.3%、1.4%、1.5%、1.6%、1.7%、1.8%、1.9%、2.0%。In some embodiments, As 2 O 3 , Cl compounds, Br compounds, etc. can also be used as clarifiers, the contents of which are respectively less than 2%, preferably less than 1%, more preferably less than 0.5%, but from the perspective of environmental protection Considering other factors, it is preferable not to introduce As 2 O 3 . In some embodiments, the content of one or more of the above three clarifying agents is about 0%, greater than 0%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8% %, 0.9%, 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2.0%.

[關於不應含有的成分][About ingredients that should not be contained]

在不損害本發明的玻璃特性的範圍內，根據需要能夠添加上述未曾提及的其他成分。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，從而減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。Other components not mentioned above can be added as needed within the range that does not impair the properties of the glass of the present invention. However, even when transition metal components such as V, Cr, Mn, Fe, Co, Ni, Cu, Ag, and Mo are contained in a small amount alone or in combination, the glass is colored and absorbs at a specific wavelength in the visible light region. Therefore, the properties of the effect of improving the visible light transmittance of the present invention are weakened. Therefore, it is preferable not to actually contain it, especially in optical glass that requires transmittance of wavelengths in the visible light region.

Pb、Th、Cd、Tl、Os、Be以及Se的陽離子，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，藉此，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。Pb, Th, Cd, Tl, Os, Be, and Se cations tend to be controlled as harmful chemical substances in recent years. They are environmentally friendly not only in the glass manufacturing process, but also in the processing process and product disposal. measures are required. Therefore, in the case of emphasizing the impact on the environment, it is preferable not to contain them except that they are inevitably mixed; thus, the optical glass becomes substantially free of substances that pollute the environment, thereby, even if no special measures are taken. As an environmental measure, the optical glass of the present invention can also be manufactured, processed, and discarded.

本文所記載的「不引入」、「不含有」、「0%」是指沒有故意將該化合物、分子或元素等作為原料添加到本發明光學玻璃中；但作為生產光學玻璃的原材料和/或設備，會存在某些不是故意添加的雜質或組分，會在最終的光學玻璃中少量或痕量含有，此種情形也在本發明專利的保護範圍內。"Do not introduce", "do not contain", and "0%" described herein mean that the compound, molecule or element, etc. is not deliberately added as a raw material to the optical glass of the present invention; but as a raw material for the production of optical glass and/or Equipment, there will be some impurities or components that are not intentionally added, and will be contained in a small or trace amount in the final optical glass, which is also within the protection scope of the patent of the present invention.

下面，對本發明的光學玻璃的性能進行說明。Next, the performance of the optical glass of the present invention will be described.

[折射率與阿貝數][Refractive index and Abbe number]

光學玻璃折射率（nd）與阿貝數(νd )按照GB/T 7962.1—2010規定方法測試。The refractive index (nd) and Abbe number (ν d ) of optical glass are tested according to the method specified in GB/T 7962.1-2010.

本發明光學玻璃折射率（nd）的範圍為1.65～1.73，優選的範圍為1.67～1.72；本發明玻璃的阿貝數（νd ）的範圍為47～55，優選範圍為48～52。The refractive index (nd) of the optical glass of the present invention ranges from 1.65 to 1.73, preferably 1.67 to 1.72; the Abbe number (ν d ) of the glass of the present invention ranges from 47 to 55, preferably from 48 to 52.

[折射率溫度係數][Refractive index temperature coefficient]

按照GB/T 7962.4—2010規定方法，測試在20～40℃範圍光學玻璃的折射率溫度係數（d線 dn/dt relative(10-6/℃)）According to the method specified in GB/T 7962.4-2010, test the temperature coefficient of refraction index of optical glass in the range of 20-40 ℃ (d line dn/dt relative(10-6/℃))

本發明光學玻璃折射率溫度係數（dn/dt）為≤0，優選為≤-0.5，更優選為≤-1.0，進一步優選為≤-2.0。The temperature coefficient of refraction index (dn/dt) of the optical glass of the present invention is ≤0, preferably ≤-0.5, more preferably ≤-1.0, even more preferably ≤-2.0.

[耐水作用穩定性][Water resistance stability]

光學玻璃耐水作用穩定性Dw (粉末法)按照GB/T17129規定方法測試。The water resistance stability Dw of optical glass (powder method) is tested according to the method specified in GB/T17129.

本發明光學玻璃耐水作用穩定性Dw 為4類及其以上，優選為3類及其以上，更優選為2類及其以上。The water resistance stability Dw of the optical glass of the present invention is Class 4 or higher, preferably Class 3 or higher, more preferably Class 2 or higher.

[氣泡度][bubble degree]

光學玻璃的氣泡度按GB/T7962.8-2010規定方法測試。The bubble degree of optical glass is tested according to the method specified in GB/T7962.8-2010.

本發明光學玻璃氣泡度為A級以上，優選為A0 級以上，更優選為A00 級。The degree of bubbles of the optical glass of the present invention is grade A or higher, preferably grade A 0 or higher, more preferably grade A 00 .

[條紋度][stripe degree]

本發明玻璃的條紋度按MLL-G-174B規定的方法進行測量；方法為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有輕微的平行條紋，D級為規定檢測條件下有粗略的條紋。The streak degree of the glass of the present invention is measured according to the method specified in MLL-G-174B; the method is to use a streak meter composed of a point light source and a lens, and compare and check with the standard sample from the direction where the streaks are most easily seen, which is divided into 4 Grades are A, B, C, and D respectively. Grade A means no streaks visible to the naked eye under the specified testing conditions, Grade B means fine and scattered streaks under the specified testing conditions, and Grade C means slight streaks under the specified testing conditions. Parallel stripes, grade D means rough stripes under specified detection conditions.

本發明的光學玻璃的條紋為C級以上，優選B級以上，更優選為A級。The striae of the optical glass of the present invention is C class or higher, preferably B class or higher, and more preferably A class.

[耐日照性能][Sunshine resistance performance]

光學玻璃耐日照穩定性能按JOGIS04-1994標準條件下，10mm厚樣品照射4小時，通過比較照射前和照射後的光譜透過率曲線，確定玻璃在400nm波段的衰減情況；玻璃的光譜透過率曲線採用分光光度計測量。The sunlight resistance stability of optical glass is according to JOGIS04-1994 standard conditions, 10mm thick samples are irradiated for 4 hours, and the attenuation of the glass in the 400nm band is determined by comparing the spectral transmittance curves before and after irradiation; the spectral transmittance curve of the glass adopts Spectrophotometer measurement.

本發明光學玻璃耐日照穩定性為400nm波長處透過率下降不超過10%，優選不超過8%，進一步優選不超過5%。The sunlight resistance stability of the optical glass of the present invention is such that the transmittance at a wavelength of 400nm decreases by no more than 10%, preferably no more than 8%, and more preferably no more than 5%.

[抗析晶性能][Anti-devitrification performance]

光學玻璃的抗析晶性能測試方法為：將樣品玻璃切割為20×20×10mm規格，放入溫度為Tg +230℃的馬弗爐中保溫30分鐘，取出後放入保溫棉中徐冷，冷卻後觀察表面析晶情況。The test method for the devitrification resistance of optical glass is as follows: cut the sample glass into 20×20×10mm specifications, put it in a muffle furnace with a temperature of T g +230°C and keep it warm for 30 minutes, take it out and put it in insulation cotton for slow cooling , and observe the surface crystallization after cooling.

本發明光學玻璃的樣品玻璃切割為20×20×10mm規格，放入溫度為Tg +230℃的馬弗爐中保溫30分鐘，取出後放入保溫棉中徐冷，表面無明顯析晶。本發明所述的表面無明顯析晶是指：表面無析晶斑或者表面有析晶斑，但其面積占整體面積的5%以下且析晶深度不超過0.5mm。The sample glass of the optical glass of the present invention is cut into a size of 20×20×10 mm, put into a muffle furnace at T g +230°C for 30 minutes, and then put into the insulation cotton to cool slowly after taking it out, and there is no obvious crystallization on the surface. No obvious crystallization on the surface in the present invention refers to: no crystallization spots on the surface or crystallization spots on the surface, but the area accounts for less than 5% of the overall area and the crystallization depth does not exceed 0.5 mm.

下面，描述本發明的玻璃預製件與光學元件。Next, the glass preform and optical element of the present invention are described.

本發明的玻璃預製件與光學元件均由上述本發明的光學玻璃形成。本發明的玻璃預製件具有中等折射率和較低折射率溫度係數特性；本發明的光學元件具有中等折射率和較低折射率溫度係數特性，能夠提供光學價值高的各種透鏡、棱鏡等光學元件。Both the glass preform and the optical element of the present invention are formed from the above-mentioned optical glass of the present invention. The glass preform of the present invention has medium refractive index and low refractive index temperature coefficient characteristics; the optical element of the present invention has medium refractive index and low refractive index temperature coefficient characteristics, and can provide various optical elements such as lenses and prisms with high optical value .

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。Examples of the lens 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.

另外，對於棱鏡來說，由於折射率相對較高，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。In addition, for prisms, since the refractive index is relatively high, a compact and wide-angle optical system can be realized by combining them in the imaging optical system and bending the optical path to the desired direction.

本發明光學玻璃所形成的光學元件可製作如照相設備、攝像設備、顯示裝置和監控設備等光學儀器。The optical elements formed from the optical glass of the present invention can be used to make optical instruments such as photographic equipment, imaging equipment, display devices, and monitoring equipment.

由於本發明光學玻璃具有優異的化學穩定性和較低折射率溫度係數等性能，特別適合應用於車載、監控安防等領域。Since the optical glass of the present invention has properties such as excellent chemical stability and a relatively low temperature coefficient of refractive index, it is particularly suitable for application in the fields of vehicle, monitoring and security, and the like.

為了進一步瞭解本發明的技術方案，下面將描述本發明光學玻璃的實施例。應該注意到，這些實施例沒有限制本發明的範圍。In order to further understand the technical solutions of the present invention, examples of the optical glass of the present invention will be described below. It should be noted that these examples do not limit the scope of the present invention.

[光學玻璃實施例][Optical glass example]

表2～3中顯示的光學玻璃（實施例1～20）是通過按照表中所示各個實施例的比值稱重並混合玻璃用普通原料（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1300～1350℃中融化2.5～4小時，並且經澄清、攪拌和均化後，得到沒有氣泡及不含未溶解物質的均質熔融玻璃，將此熔融玻璃在模具內鑄型並退火而成。The optical glasses (Examples 1 to 20) shown in Tables 2 to 3 were prepared by weighing and mixing common raw materials for glass (such as oxides, hydroxides, carbonates, nitrates, etc. etc.), put the mixed raw materials in a platinum crucible, melt at 1300-1350°C for 2.5-4 hours, and after clarification, stirring and homogenization, a homogeneous molten glass without bubbles and undissolved substances is obtained. Molten glass is cast in molds and annealed.

實施例1～20顯示光學玻璃組成與折射率（nd）；阿貝數（νd ）；在20～40℃範圍內，折射率溫度係數（d線 dn/dt relative(10-6 /℃)）（dn/dt）；粉末法耐水作用穩定性（Dw ）；將樣品玻璃切割為20×20×10mm規格，放入溫度為Tg +230℃的馬弗爐中保溫30分鐘，取出後放入保溫棉中徐冷，冷卻後觀察表面析晶情況，無明顯析晶記做「A」,有明顯析晶記為「B」；氣泡度，條紋度按標準規定表示；經過耐日照穩定性試驗以後，400nm波長處透過率下降百分率用「ΔT（%）」表示。Examples 1-20 show optical glass composition and refractive index (nd); Abbe number (ν d ); in the range of 20-40 °C, the temperature coefficient of refractive index (d line dn/dt relative(10 -6 / °C) ) (dn/dt); powder method water resistance stability (D w ); cut the sample glass into 20×20×10mm specifications, put it in a muffle furnace with a temperature of T g +230°C for 30 minutes, and take it out Put it into the insulation cotton and let it cool slowly. After cooling, observe the crystallization on the surface. If there is no obvious crystallization, it will be recorded as "A", and if there is obvious crystallization, it will be recorded as "B". After the performance test, the percent decrease of the transmittance at the wavelength of 400nm is represented by "ΔT (%)".

SiO2 /B2 O3 的值以K1表示；TiO2 /Nb2 O5 的值以K2表示；CaO/(BaO+SrO)的值以K3表示；ZnO/(CaO+BaO+SrO)的值以K4表示；Li2 O+Na2 O+K2 O的合計量以K5表示；Li2 O/(K2 O+Na2 O)的值以K6表示；Na2 O/K2 O值以K7表示；（BaO+SrO+CaO）/(La2 O3 +Gd2 O3 +Y2 O3 )的值以K8表示；BaO/La2 O3 的值以K9表示；(CaO+BaO+SrO)/(Al2 O3 +ZrO2 +TiO2 )的值以K10表示。 表2

Figure 108139276-A0304-0002
表3
Figure 108139276-A0304-0003
 The value of SiO 2 /B 2 O 3 is expressed in K1; the value of TiO 2 /Nb 2 O 5 is expressed in K2; the value of CaO/(BaO+SrO) is expressed in K3; the value of ZnO/(CaO+BaO+SrO) It is expressed in K4; the total amount of Li 2 O+Na 2 O+K 2 O is expressed in K5; the value of Li 2 O/(K 2 O+Na 2 O) is expressed in K6; the value of Na 2 O/K 2 O is expressed in K7 represents; (BaO+SrO+CaO)/(La 2 O 3 +Gd 2 O 3 +Y 2 O 3 ) value is represented by K8; BaO/La 2 O 3 value is represented by K9; (CaO+BaO+ The value of SrO)/(Al 2 O 3 +ZrO 2 +TiO 2 ) is represented by K10. Table 2
Figure 108139276-A0304-0002
 table 3
Figure 108139276-A0304-0003

[玻璃預製件實施例][Example of Glass Preform]

將表2中實施例1～10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、棱鏡的預製件。Cut the optical glass obtained in Examples 1 to 10 in Table 2 into a predetermined size, and then apply a release agent evenly on the surface, then heat and soften it, and perform pressure molding to make concave meniscus lenses, convex Prefabricated parts of various lenses and prisms such as meniscus lens, biconvex lens, biconcave lens, plano-convex lens, plano-concave lens, etc.

[光學元件實施例][Example of optical element]

將上述玻璃預製件實施例所得到的這些預製件退火，在降低玻璃內部變形的同時進行微調，使得折射率等光學特性達到所需值。The preforms obtained in the above glass preform embodiment are annealed, and the internal deformation of the glass is reduced while fine-tuning is carried out so that the optical properties such as the refractive index reach the required values.

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、棱鏡。所得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 and prisms such as concave meniscus lens, convex meniscus lens, biconvex lens, biconcave lens, plano-convex lens, and plano-concave lens. An antireflection film may also be coated on the surface of the obtained optical element.

無none

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Claims (30)

一種光學玻璃，其特徵在於，其組成以重量百分比表示，包含SiO2、B2O3、La2O3、RO和Rn2O，其中RO為MgO、CaO、SrO和BaO中的一種以上，Rn2O為Li2O、K2O和Na2O中的一種以上，含有：BaO：10~40%、SrO：1~15%，玻璃的折射率為1.65~1.73，阿貝數為47~55，折射率溫度係數為
Figure 108139276-A0305-02-0030-3
0，BaO/La2O3為0.6~2。 An optical glass, characterized in that its composition is represented by weight percentage, including SiO 2 , B 2 O 3 , La 2 O 3 , RO and Rn 2 O, wherein RO is one or more of MgO, CaO, SrO and BaO, Rn 2 O is more than one of Li 2 O, K 2 O and Na 2 O, containing: BaO: 10~40%, SrO: 1~15%, the refractive index of the glass is 1.65~1.73, and the Abbe number is 47 ~55, the temperature coefficient of refraction is
Figure 108139276-A0305-02-0030-3
0, BaO/La 2 O 3 is 0.6~2. 如請求項1所述的光學玻璃，其中，其組成以重量百分比表示，還含有：SiO2：4~20%、B2O3：10~30%、La2O3：10~35%、CaO：0~10%、MgO：0~5%、Li2O：0~5%、K2O：0~6%、Na2O：0~8%、Gd2O3：0~8%、Y2O3：0~5%、ZrO2：0~3%、Al2O3：0~3%、TiO2：0~3%、Nb2O5：0~5%、WO3：0~2%、ZnO：0~5%、澄清劑：0~2%。 The optical glass according to Claim 1, wherein its composition is expressed in weight percent, and further contains: SiO 2 : 4-20%, B 2 O 3 : 10-30%, La 2 O 3 : 10-35%, CaO: 0~10%, MgO: 0~5%, Li2O : 0~5%, K2O : 0 ~ 6%, Na2O : 0~8%, Gd2O3 : 0~8% , Y 2 O 3 : 0~5%, ZrO 2 : 0~3%, Al 2 O 3 : 0~3%, TiO 2 : 0~3%, Nb 2 O 5 : 0~5%, WO 3 : 0~2%, ZnO: 0~5%, clarifying agent: 0~2%. 一種光學玻璃，其特徵在於，其組成以重量百分比表示，含有：SiO2：4~20%、B2O3：10~30%、La2O3：10~35%、BaO：10~40%、SrO：1~15%，折射率溫度係數為
Figure 108139276-A0305-02-0030-4
0，BaO/La2O3為0.6~2。 An optical glass, characterized in that its composition is represented by weight percentage, containing: SiO 2 : 4-20%, B 2 O 3 : 10-30%, La 2 O 3 : 10-35%, BaO: 10-40% %, SrO: 1~15%, the temperature coefficient of refractive index is
Figure 108139276-A0305-02-0030-4
0, BaO/La 2 O 3 is 0.6~2. 如請求項3所述的光學玻璃，其中，還含有：CaO：0~10%、MgO：0~5%、Li2O：0~5%、K2O：0~6%、Na2O：0~8%、Gd2O3：0~8%、Y2O3：0~5%、ZrO2：0~3%、Al2O3：0~3%、TiO2：0~3%、Nb2O5：0~5%、WO3：0~2%、ZnO：0~5%、澄清劑：0~2%。 The optical glass according to claim 3, further comprising: CaO: 0~10%, MgO: 0~5%, Li 2 O: 0~5%, K 2 O: 0~6%, Na 2 O : 0~8%, Gd 2 O 3 : 0~8%, Y 2 O 3 : 0~5%, ZrO 2 : 0~3%, Al 2 O 3 : 0~3%, TiO 2 : 0~3 %, Nb 2 O 5 : 0~5%, WO 3 : 0~2%, ZnO: 0~5%, clarifying agent: 0~2%. 一種光學玻璃，其特徵在於，其組成以重量百分比表示由SiO2：4~20%、B2O3：10~30%、La2O3：10~35%、BaO：10~40%、SrO：1~15%、CaO：0~10%、MgO：0~5%、Rn2O：0~8%、Gd2O3：0~8%、Y2O3：0~5%、ZrO2：0~3%、Al2O3：0~3%、TiO2：0~3%、Nb2O5：0~5%、WO3：0~2%、ZnO：0~5%組成，其中Rn2O為Li2O、K2O、Na2O中的一種以上，折射率溫度 係數為
Figure 108139276-A0305-02-0031-5
0，BaO/La2O3為0.6~2。 An optical glass, characterized in that its composition is represented by weight percent: SiO 2 : 4-20%, B 2 O 3 : 10-30%, La 2 O 3 : 10-35%, BaO: 10-40%, SrO: 1~15%, CaO: 0~10%, MgO: 0~5%, Rn2O : 0~8%, Gd2O3 : 0~8%, Y2O3 : 0~ 5 %, ZrO 2 : 0~3%, Al 2 O 3 : 0~3%, TiO 2 : 0~3%, Nb 2 O 5 : 0~5%, WO 3 : 0~2%, ZnO: 0~5% composition, wherein Rn 2 O is more than one of Li 2 O, K 2 O, and Na 2 O, and the temperature coefficient of refractive index is
Figure 108139276-A0305-02-0031-5
0, BaO/La 2 O 3 is 0.6~2. 如請求項1~5任一請求項所述的光學玻璃，其中，SiO2/B2O3為0.4~1.3；和/或BaO/La2O3為0.65~1.9。 The optical glass according to any one of claims 1-5, wherein, SiO 2 /B 2 O 3 is 0.4-1.3; and/or BaO/La 2 O 3 is 0.65-1.9. 如請求項1~5任一請求項所述的光學玻璃，其中，SiO2/B2O3為0.45~1.2；和/或BaO/La2O3為0.7~1.8。 The optical glass according to any one of claims 1-5, wherein SiO 2 /B 2 O 3 is 0.45-1.2; and/or BaO/La 2 O 3 is 0.7-1.8. 如請求項1~5任一請求項所述的光學玻璃，其中，SiO2/B2O3為0.5~1.1。 The optical glass according to any one of claims 1 to 5, wherein SiO 2 /B 2 O 3 is 0.5 to 1.1. 如請求項1~5任一請求項所述的光學玻璃，其中，CaO/(BaO+SrO)為0~0.5；和/或ZnO/(CaO+SrO+BaO)為0~0.3；和/或(CaO+SrO+BaO)/(La2O3+Gd2O3+Y2O3)為0.7~2.5；和/或(CaO+SrO+BaO)/(Al2O3+ZrO2+TiO2)大於8；和/或SrO含量
Figure 108139276-A0305-02-0031-6
CaO含量。 The optical glass according to any one of claims 1 to 5, wherein CaO/(BaO+SrO) is 0~0.5; and/or ZnO/(CaO+SrO+BaO) is 0~0.3; and/or (CaO+SrO+BaO)/(La 2 O 3 +Gd 2 O 3 +Y 2 O 3 ) is 0.7~2.5; and/or (CaO+SrO+BaO)/(Al 2 O 3 +ZrO 2 +TiO 2 ) greater than 8; and/or SrO content
Figure 108139276-A0305-02-0031-6
CaO content. 如請求項1~5任一請求項所述的光學玻璃，其中，CaO/(BaO+SrO)為0.01~0.4；和/或ZnO/(CaO+SrO+BaO)為0~0.2；和/或(CaO+SrO+BaO)/(La2O3+Gd2O3+Y2O3)為0.8~2.3；和/或(CaO+SrO+BaO)/(Al2O3+ZrO2+TiO2)大於10；和/或BaO含量
Figure 108139276-A0305-02-0031-7
SrO含量
Figure 108139276-A0305-02-0031-8
CaO含量。 The optical glass according to any one of claims 1 to 5, wherein CaO/(BaO+SrO) is 0.01~0.4; and/or ZnO/(CaO+SrO+BaO) is 0~0.2; and/or (CaO+SrO+BaO)/(La 2 O 3 +Gd 2 O 3 +Y 2 O 3 ) is 0.8~2.3; and/or (CaO+SrO+BaO)/(Al 2 O 3 +ZrO 2 +TiO 2 ) greater than 10; and/or BaO content
Figure 108139276-A0305-02-0031-7
SrO content
Figure 108139276-A0305-02-0031-8
CaO content. 如請求項1~5任一請求項所述的光學玻璃，其中，CaO/(BaO+SrO)為0.02~0.3；和/或ZnO/(CaO+SrO+BaO)為0~0.15；和/或(CaO+SrO+BaO)/(La2O3+Gd2O3+Y2O3)為0.9~2.1；和/或(CaO+SrO+BaO)/(Al2O3+ZrO2+TiO2)大於12。 The optical glass as described in any one of claims 1 to 5, wherein CaO/(BaO+SrO) is 0.02~0.3; and/or ZnO/(CaO+SrO+BaO) is 0~0.15; and/or (CaO+SrO+BaO)/(La 2 O 3 +Gd 2 O 3 +Y 2 O 3 ) is 0.9~2.1; and/or (CaO+SrO+BaO)/(Al 2 O 3 +ZrO 2 +TiO 2 ) Greater than 12. 如請求項1~5任一請求項所述的光學玻璃，其中，Li2O+Na2O+K2O為0~8%；和/或Li2O/(K2O+Na2O)為0~0.5；和/或Na2O/K2O為0.2~5.0；和/或TiO2/Nb2O5為1以下。 The optical glass as described in any one of claims 1-5, wherein Li 2 O+Na 2 O+K 2 O is 0-8%; and/or Li 2 O/(K 2 O+Na 2 O ) is 0~0.5; and/or Na 2 O/K 2 O is 0.2~5.0; and/or TiO 2 /Nb 2 O 5 is 1 or less. 如請求項1~5任一請求項所述的光學玻璃，其中，Li2O+Na2O+K2O 為0~6%；和/或Li2O/(K2O+Na2O)為0~0.4；和/或Na2O/K2O為0.3~4.0；和/或TiO2/Nb2O5為0.8以下。 The optical glass as described in any one of claims 1-5, wherein Li 2 O+Na 2 O+K 2 O is 0-6%; and/or Li 2 O/(K 2 O+Na 2 O ) is 0~0.4; and/or Na 2 O/K 2 O is 0.3~4.0; and/or TiO 2 /Nb 2 O 5 is 0.8 or less. 如請求項1~5任一請求項所述的光學玻璃，其中，Li2O+Na2O+K2O為0~5%；和/或Li2O/(K2O+Na2O)為0~0.3；和/或Na2O/K2O為0.4~3.0；和/或TiO2/Nb2O5為0.5以下。 The optical glass as described in any one of claims 1-5, wherein Li 2 O+Na 2 O+K 2 O is 0-5%; and/or Li 2 O/(K 2 O+Na 2 O ) is 0~0.3; and/or Na 2 O/K 2 O is 0.4~3.0; and/or TiO 2 /Nb 2 O 5 is 0.5 or less. 如請求項1~5任一請求項所述的光學玻璃，其中，其組成以重量百分比表示，含有：SiO2：6~18%、和/或B2O3：12~25%、和/或La2O3：12~30%、和/或BaO：12~35%、和/或SrO：1~15%、和/或CaO：0~8%、和/或Gd2O3：1~6%、和/或Y2O3：0~3%、和/或ZrO2：0.1~3%、和/或Al2O3：0~2%、和/或TiO2：0~2%、和/或Nb2O5：0.1~5%、和/或WO3：0~1%、和/或ZnO：0~3%、和/或MgO：0~3%、和/或Li2O：0~3%、和/或K2O：0.3~4%、和/或Na2O：0.5~6%。 The optical glass as described in any one of claims 1-5, wherein its composition is expressed in weight percentage, including: SiO 2 : 6-18%, and/or B 2 O 3 : 12-25%, and/or Or La 2 O 3 : 12~30%, and/or BaO: 12~35%, and/or SrO: 1~15%, and/or CaO: 0~8%, and/or Gd 2 O 3 : 1 ~6%, and/or Y 2 O 3 : 0~3%, and/or ZrO 2 : 0.1~3%, and/or Al 2 O 3 : 0~2%, and/or TiO 2 : 0~2 %, and/or Nb 2 O 5 : 0.1~5%, and/or WO 3 : 0~1%, and/or ZnO: 0~3%, and/or MgO: 0~3%, and/or Li 2 O: 0~3%, and/or K 2 O: 0.3~4%, and/or Na 2 O: 0.5~6%. 如請求項1~5任一請求項所述的光學玻璃，其中，其組成以重量百分比表示，含有：SiO2：8~16%、和/或B2O3：15~22%、和/或La2O3：15~28%、和/或BaO：15~32%、和/或SrO：1~12%、和/或CaO：0~6%、和/或Gd2O3：1~4%、和/或Y2O3：1~3%、和/或ZrO2：0.1~2%、和/或Al2O3：0.1~1%、和/或TiO2：0~1%、和/或Nb2O5：0.5~4%、和/或K2O：0.5~3%、和/或Na2O：1~3%。 The optical glass as described in any one of claims 1-5, wherein its composition is expressed in weight percent, including: SiO 2 : 8-16%, and/or B 2 O 3 : 15-22%, and/or Or La 2 O 3 : 15~28%, and/or BaO: 15~32%, and/or SrO: 1~12%, and/or CaO: 0~6%, and/or Gd 2 O 3 : 1 ~4%, and/or Y 2 O 3 : 1~3%, and/or ZrO 2 : 0.1~2%, and/or Al 2 O 3 : 0.1~1%, and/or TiO 2 : 0~1 %, and/or Nb 2 O 5 : 0.5~4%, and/or K 2 O: 0.5~3%, and/or Na 2 O: 1~3%. 如請求項1~5任一請求項所述的光學玻璃，其中，其組成以重量百分比表示，含有：ZrO2：0.1~1%、和/或Nb2O5：1~3%、和/或SrO：1.5~10%。 The optical glass as described in any one of claims 1 to 5, wherein its composition is expressed in weight percentage, including: ZrO 2 : 0.1-1%, and/or Nb 2 O 5 : 1-3%, and/or Or SrO: 1.5~10%. 如請求項1~5任一請求項所述的光學玻璃，其中，玻璃的折射率為1.65~1.73；阿貝數為47~55。 The optical glass according to any one of claims 1-5, wherein the glass has a refractive index of 1.65-1.73 and an Abbe number of 47-55. 如請求項1~5任一請求項所述的光學玻璃，其中，玻璃的折射率 為1.67~1.72；阿貝數為48~52。 The optical glass as described in any one of claims 1 to 5, wherein the refractive index of the glass It is 1.67~1.72; the Abbe number is 48~52. 如請求項1~5任一請求項所述的光學玻璃，其中，玻璃的折射率溫度係數為
Figure 108139276-A0305-02-0033-9
0。 The optical glass as described in any one of claims 1 to 5, wherein the temperature coefficient of refractive index of the glass is
Figure 108139276-A0305-02-0033-9
0. 如請求項1~5任一請求項所述的光學玻璃，其中，玻璃的折射率溫度係數為
Figure 108139276-A0305-02-0033-10
-0.5。 The optical glass as described in any one of claims 1 to 5, wherein the temperature coefficient of refractive index of the glass is
Figure 108139276-A0305-02-0033-10
-0.5. 如請求項1~5任一請求項所述的光學玻璃，其中，玻璃的折射率溫度係數為
Figure 108139276-A0305-02-0033-12
-1.0。 The optical glass as described in any one of claims 1 to 5, wherein the temperature coefficient of refractive index of the glass is
Figure 108139276-A0305-02-0033-12
-1.0. 如請求項1~5任一請求項所述的光學玻璃，其中，玻璃的折射率溫度係數為
Figure 108139276-A0305-02-0033-13
-2.0。 The optical glass as described in any one of claims 1 to 5, wherein the temperature coefficient of refractive index of the glass is
Figure 108139276-A0305-02-0033-13
-2.0. 如請求項1~5任一請求項所述的光學玻璃，其中，玻璃的耐水穩定性為4類及其以上；和/或氣泡度為A級以上；和/或條紋為C級以上；和/或耐日照穩定性為400nm波長處透過率下降不超過10%。 The optical glass as described in any one of claims 1 to 5, wherein the water resistance stability of the glass is Class 4 or above; and/or the bubble degree is above grade A; and/or the stripes are above grade C; and / or the stability of sunlight resistance is that the transmittance at the wavelength of 400nm does not decrease by more than 10%. 如請求項1~5任一請求項所述的光學玻璃，其中，玻璃的耐水穩定性為3類及其以上；和/或氣泡度為A0級以上；和/或條紋為B級以上；和/或耐日照穩定性為400nm波長處透過率下降不超過8%。 The optical glass as described in any one of claims 1 to 5, wherein the water resistance stability of the glass is Class 3 or above; and/or the bubble degree is above grade A0 ; and/or the stripes are above grade B; And/or the stability of sunlight resistance is that the transmittance at the wavelength of 400nm does not drop by more than 8%. 如請求項1~5任一請求項所述的光學玻璃，其中，玻璃的耐水穩定性為2類及其以上；和/或氣泡度為A00級；和/或條紋為A級；和/或耐日照穩定性為400nm波長處透過率下降不超過5%。 The optical glass as described in any one of claims 1 to 5, wherein the water resistance stability of the glass is Class 2 or above; and/or the bubble degree is A 00 grade; and/or the stripes are A grade; and/or Or the stability of sunlight resistance is that the transmittance at the wavelength of 400nm does not drop by more than 5%. 一種玻璃預製件，採用請求項1~26任一請求項所述的光學玻璃製成。 A glass prefabricated part made of the optical glass described in any one of claims 1-26. 一種光學元件，採用請求項1~26任一請求項所述的光學玻璃或請求項27所述的玻璃預製件製成。 An optical element made of the optical glass described in any one of claims 1 to 26 or the glass preform described in claim 27. 一種光學儀器，採用請求項1~26任一請求項所述的光學玻璃或 請求項28所述的光學元件製成。 An optical instrument, using the optical glass described in any one of claims 1 to 26 or The optical element described in claim 28 is made. 一種如請求項1~26任一請求項所述的光學玻璃或請求項28所述的光學元件在車載中的應用。 An application of the optical glass described in any one of Claims 1 to 26 or the optical element described in Claim 28 in a vehicle.
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