CN114685041B - Optical glass, glass preform, optical element, and optical instrument - Google Patents

Optical glass, glass preform, optical element, and optical instrument Download PDF

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CN114685041B
CN114685041B CN202210223336.9A CN202210223336A CN114685041B CN 114685041 B CN114685041 B CN 114685041B CN 202210223336 A CN202210223336 A CN 202210223336A CN 114685041 B CN114685041 B CN 114685041B
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optical glass
glass
bao
cao
percent
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CN114685041A (en
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蔡冬雪
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CDGM Glass Co Ltd
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CDGM Glass Co Ltd
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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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P40/00—Technologies relating to the processing of minerals
    • Y02P40/50—Glass production, e.g. reusing waste heat during processing or shaping
    • Y02P40/57—Improving the yield, e-g- reduction of reject rates

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

Abstract

The invention provides optical glass, which comprises the following components in percentage by weight: p (P) 2 O 5 ：4～30％；BaO：0～20％；Nb 2 O 5 ：10～45％；Li 2 O+K 2 O+Na 2 O: 0-35%; wherein BaO/Nb 2 O 5 0 to 0.5. Through reasonable component design, the optical glass has a lower refractive index temperature coefficient while having a desired refractive index and Abbe number, and brings greater freedom for correcting temperature drift of a fixed focus lens; the glass fiber reinforced plastic composite material has excellent chemical stability and crystallization resistance, can not obviously reduce transmittance after long-term use, is very suitable for vehicle-mounted lenses, and is particularly suitable for imaging applications which need to bear severe working environments, such as sand, mud, abrupt temperature change and the like.

Description

Optical glass, glass preform, optical element, and optical instrument
The present application is a divisional application of the invention patent application with the application number 201911310582.2 and the application date 2019, 12 month and 18 date, named "optical glass, glass preform, optical element and optical instrument".
Technical Field
The present invention relates to an optical glass, and more particularly, to an optical glass having a refractive index of 1.73 to 1.81 and an abbe number of 20 to 30.
Background
In the prior art, glass with a refractive index of 1.73-1.81 and an Abbe number of 20-30 belongs to high-refractive-index high-dispersion optical glass and is widely applied to various lens designs. In recent years, on-vehicle lens devices have been actively developed, and compared with applications such as general photography, the quality of the on-vehicle lens is closely related to safety, so that the design of the on-vehicle lens more emphasizes the reliability of the device, especially the on-vehicle lens device is exposed outside the vehicle body, and needs to bear severe working environments, such as a reversing camera, a front view camera, a rearview mirror auxiliary camera and the like.
The principle of designing the vehicle-mounted lens meeting the severe working environment is that the structure is as simple as possible, and the more complex the structure is, the worse the reliability is. Therefore, in order to meet the design requirement of long service life (more than ten years) of the vehicle-mounted lens which can adapt to severe working environment, a fixed focus lens design is generally adopted in optical design, the number of lenses is smaller than that of a zoom lens, and meanwhile, a zoom driving structure is not arranged, so that the reliability is greatly improved compared with that of the zoom lens.
Although the fixed focus lens has very good reliability, the fixed focus lens is applied to a vehicle, and the fatal weakness is that the temperature drift of the lens is very difficult to correct. The temperature drift of the lens means that when the temperature changes drastically, for example, the day and night temperature difference in the desert area reaches 60 ℃, and the focal length of the lens changes in a scene with very large temperature difference, such as from a tropical zone to a frigid zone, so as to cause imaging blurring. For automobiles, safety is the first, so that the vehicle-mounted camera needs to keep clear imaging under the condition of rapid temperature change.
For optical designs, more different types of lens combinations and zoom systems are often employed to address the temperature drift problem. However, due to the requirement of the vehicle-mounted system on reliability, the problem of temperature drift needs to be solved on a fixed-focus imaging system with a small number of lenses (even 3 lenses), and thus optical glass with a specific refractive index temperature coefficient needs to be developed, which is a new subject for optical design and optical material research in the era.
The optical glass with refractive index of 1.73-1.81 and Abbe number of 20-30 in the prior art has refractive index temperature coefficient value in the range of 40-60 ℃, namely d-line dn/dt relative (10) -6 The temperature/DEG C) is basically 1.0-2.1 (10) -6 Per c), see table 1 below. If glass with refractive index temperature coefficient lower than-2.0, even lower than-3.0 and above optical properties can be developed, the temperature drift problem can be effectively solved in design.
Table 1: refractive index temperature coefficient of glass with partial refractive index of 1.73-1.81 and Abbe number of 20-30
Sequence number n d ν d In the range of 40-60 ℃, d-line dn/dtreltive (10 -6 /℃)
Example 1 1.7373 29.50 1.0
Example 2 1.7400 28.30 2.1
Example 3 1.7847 25.72 1.4
However, if the refractive index and abbe number of the optical glass need to reach a refractive index temperature coefficient lower than-2.0, the composition design is different from that of the conventional optical glass, and the problems of poor crystallization resistance, difficult elimination of stripes and bubbles and the like of the glass are generally caused. If the crystallization resistance of the glass is poor, firstly, the production difficulty of the glass blank is increased, the yield is reduced, and even normal production cannot be carried out when the yield is severe; secondly, crystals are easy to be separated out in the secondary pressing process, so that the yield is reduced, and even the secondary pressing cannot be performed. For glass materials applied to the vehicle-mounted field, if the production yield of glass is low, and the glass cannot be manufactured by adopting a secondary pressing method but by adopting a cold working method, the cost is greatly increased.
Disclosure of Invention
The invention aims to provide optical glass with lower refractive index temperature coefficient and excellent crystallization resistance.
The technical scheme adopted for solving the technical problems is as follows:
(1) The optical glass comprises the following components in percentage by weight: p (P) 2 O 5 ：4～30％；BaO：0～20％；Nb 2 O 5 ：10～45％；Li 2 O+K 2 O+Na 2 O: 0-35%; wherein BaO/Nb 2 O 5 0 to 0.5.
(2) The optical glass according to (1), which comprises the following components in percentage by weight: siO (SiO) 2 ：0～10％；B 2 O 3 ：0～10％；Gd 2 O 3 ：0～8％；Y 2 O 3 ：0～5％；Al 2 O 3 ：0～3％；TiO 2 : 0-15%; mgO: 0-5%; caO: 0-25%; srO: 0-10%; clarifying agent: 0 to 1 percent.
(3) The optical glass comprises the following components in percentage by weight 2 O 5 ：4～30％；Nb 2 O 5 ：10～45％；Li 2 O+K 2 O+Na 2 O：0～35％；SiO 2 ：0～10％；B 2 O 3 ：0～10％；Gd 2 O 3 ：0～8％；Y 2 O 3 ：0～5％；Al 2 O 3 ：0～3％；TiO 2 : 0-15%; mgO: 0-5%; caO: 0-25%; srO: 0-10%; baO: 0-20%; clarifying agent: 0 to 1 percent of BaO/Nb 2 O 5 0 to 0.5.
(4) An optical glass comprising P 2 O 5 、Nb 2 O 5 Alkaline earth metal oxide and alkali metal oxide, the components of which are expressed in weight percent, wherein BaO/Nb 2 O 5 0 to 0.5, li 2 O/(K 2 O+Na 2 O) is 0.5 or less, and the refractive index n of the optical glass d Is 1.73 to 1.81, and Abbe number v d 20 to 30, and the refractive index temperature coefficient dn/dt is-2 multiplied by 10 -6 And/or lower.
(5) The optical glass according to (4), which comprises the following components in percentage by weight: p (P) 2 O 5 : 4-30%; and/or Nb 2 O 5 : 10-45%; and/or Li 2 O+K 2 O+Na 2 O: 0-35%; and/or SiO 2 : 0-10%; and/or B 2 O 3 : 0-10%; and/or Gd 2 O 3 : 0-8%; and/or Y 2 O 3 : 0-5%; and/or Al 2 O 3 :0 to 3 percent; and/or TiO 2 : 0-15%; and/or MgO: 0-5%; and/or CaO: 0-25%; and/or SrO: 0-10%; and/or BaO: 0-20%; and/or clarifying agent: 0 to 1 percent.
(6) The optical glass according to any one of (1) to (5), wherein the components are represented by weight percent: p (P) 2 O 5 : 10-30%; and/or Nb 2 O 5 : 15-45%; and/or Li 2 O+K 2 O+Na 2 O: 5-30%; and/or SiO 2 : 0-8%; and/or B 2 O 3 :1 to 9 percent; and/or Gd 2 O 3 :0 to 6 percent; and/or Y 2 O 3 :0 to 4 percent; and/or Al 2 O 3 :0 to 2 percent; and/or TiO 2 : 0-12%; and/or MgO:0 to 3 percent; and/or CaO: 0-20%; and/or SrO: 0-8%; and/or BaO:0 to 16 percent; and/or clarifying agent: 0 to 0.5 percent.
(7) The optical glass according to any one of (1) to (5), wherein the components are represented by weight percent: p (P) 2 O 5 : 15-25%; and/or Nb 2 O 5 : 20-43%; and/or Li 2 O+K 2 O+Na 2 O: 5-25%; and/or SiO 2 : 0-5%; and/or B 2 O 3 : 2-8%; and/or Gd 2 O 3 :0 to 4 percent; and/or Y 2 O 3 :0 to 3 percent; and/or Al 2 O 3 :0 to 1 percent; and/or TiO 2 : 0-10%; and/or CaO: 0-15%; and/or SrO:0 to 6 percent; and/or BaO:013 percent; and/or clarifying agent: 0 to 0.1 percent.
(8) The optical glass according to any one of (1) to (5), wherein the components are expressed in weight percent, wherein BaO/Nb 2 O 5 From 0 to 0.4, preferably BaO/Nb 2 O 5 0 to 0.3.
(9) The optical glass according to any one of (1) to (5), wherein (SiO) 2 +B 2 O 3 )/P 2 O 5 Is 0.1 to 0.5, preferably (SiO) 2 +B 2 O 3 )/P 2 O 5 Is 0.15 to 0.45, more preferably (SiO) 2 +B 2 O 3 )/P 2 O 5 0.2 to 0.4.
(10) The optical glass according to any one of (1) to (5), wherein the TiO 2 /Nb 2 O 5 Has a value of 1 or less, preferably TiO 2 /Nb 2 O 5 The value of (2) is 0.8 or less, more preferably TiO 2 /Nb 2 O 5 The value of (2) is 0.5 or less.
(11) The optical glass according to any one of (1) to (5), wherein CaO/(BaO+SrO) is 0 to 0.5, preferably CaO/(BaO+SrO) is 0 to 0.4, more preferably CaO/(BaO+SrO) is 0 to 0.3.
(12) The optical glass according to any one of (1) to (5), wherein the components are represented by weight percent, wherein Li 2 O/(K 2 O+Na 2 O) is 0.5 or less, preferably Li 2 O/(K 2 O+Na 2 O) is 0.4 or less, more preferably Li 2 O/(K 2 O+Na 2 O) is 0.3 or less.
(13) The optical glass according to any one of (1) to (5), wherein the components are represented by weight percent, na 2 O/K 2 O is 0.1 to 1.5, preferably Na 2 O/K 2 O is 0.2 to 1.2, more preferably Na 2 O/K 2 O is 0.3-1.0.
(14) The optical glass according to any one of (1) to (5), wherein the components are represented by weight percent (BaO+SrO+CaO)/(Nb) 2 O 5 +Gd 2 O 3 +Y 2 O 3 ) Is preferably (BaO+SrO+CaO)/(Nb) in the range of 0 to 0.5 2 O 5 +Gd 2 O 3 +Y 2 O 3 ) Is 0 to 0.4, more preferably (BaO+SrO+CaO)/(Nb) 2 O 5 +Gd 2 O 3 +Y 2 O 3 ) 0 to 0.3.
(15) The optical glass according to any one of (1) to (5), wherein the components are expressed in weight percent of (CaO+BaO+SrO)/(Al) 2 O 3 +TiO 2 ) Less than 1.0, preferably (CaO+BaO+SrO)/(Al) 2 O 3 +TiO 2 ) Less than 0.8, more preferably (CaO+BaO+SrO)/(Al) 2 O 3 +TiO 2 ) Less than 0.6.
(16) The optical glass according to any one of (1) to (5), wherein the components are represented by weight percent, na 2 O:0 to 15%, preferably Na 2 O:2 to 12%, more preferably Na 2 O: 4-10%; and/or K 2 O:0 to 25%, preferably K 2 O:3 to 20%, more preferably K 2 O: 5-15%; and/or Li 2 O:0 to 5%, preferably Li 2 O:0 to 3%, more preferably no Li is added 2 O。
(17) The optical glass according to any one of (1) to (5), wherein the content of BaO is not less than the content of CaO, preferably the content of SrO is not less than the content of CaO, more preferably the content of BaO is not less than the content of SrO is not less than the content of CaO.
(18) The optical glass according to any one of (1) to (5), which has a refractive index n d 1.73 to 1.81, preferably 1.74 to 1.80, more preferably 1.75 to 1.79; abbe number v d 20 to 30, preferably 21 to 28, more preferably 22 to 26.
(19) The optical glass according to any one of (1) to (5), wherein the optical glass has a refractive index temperature coefficient dn/dt of-2X 10 at 40 to 60 DEG C -6 preferably-2.5X10 or less at a temperature of/DEG C -6 Lower than or equal to-3.0X10 is more preferable -6 Preferably at most-4.0X10. Mu.M -6 And/or lower.
(20) The optical glass according to any one of (1) to (5), which has stability against water action D W More than 3 kinds, preferablyClass 2 or more, more preferably class 1; and/or the streak degree is C or more, preferably B or more, more preferably a.
(21) A glass preform made of the optical glass according to any one of (1) to (20).
(22) An optical element made of the optical glass according to any one of (1) to (20) or made of the glass preform according to (21).
(23) An optical device comprising the optical glass of any one of (1) to (20) or the optical element of (22).
The beneficial effects of the invention are as follows: through reasonable component design, the optical glass has a lower refractive index temperature coefficient while having a desired refractive index and Abbe number, and brings greater freedom for correcting temperature drift of a fixed focus lens; the glass fiber reinforced plastic composite material has excellent chemical stability and crystallization resistance, can not obviously reduce transmittance after long-term use, is very suitable for vehicle-mounted lenses, and is particularly suitable for imaging applications which need to bear severe working environments, such as sand, mud, abrupt temperature change and the like.
Detailed Description
The embodiments of the optical glass of the present invention will be described in detail below, but the present invention is not limited to the following embodiments, and can be implemented with appropriate modifications within the scope of the object of the present invention. In the repeated explanation, explanation is omitted appropriately, but the gist of the invention is not limited thereto. In the following, the optical glass of the present invention may be simply referred to as glass.
[ optical glass ]
The respective component ranges of the optical glass of the present invention are described below. In the present specification, unless otherwise specified, the contents of the respective components are all expressed in terms of weight percentage relative to the total amount of glass substance converted into the composition of oxide. The term "composition converted into oxide" as used herein means that the total amount of oxide used as a raw material of the optical glass composition (component) of the present invention is 100% based on the total amount of oxide when the oxide, composite salt, hydroxide, or the like is decomposed and converted into oxide in the melt.
Unless otherwise indicated in a particular context, numerical ranges set forth herein include upper and lower limits, and "above" and "below" include endpoints, and all integers and fractions within the range, and are not limited to the specific values set forth in the defined range. The term "and/or" as referred to herein is inclusive, e.g. "a; and/or B ", means either a alone, B alone, or both a and B.
< essential Components and optional Components >
The glass of the invention mainly contains P 2 O 5 、Nb 2 O 5 RO (RO is one or more of MgO, caO, srO, baO), R 2 O(R 2 0 is Li 2 O、K 2 O、Na 2 O), through reasonable component proportion, the refractive index temperature coefficient is low, the chemical stability is excellent, the crystallization resistance is strong, the transmittance can not be obviously reduced after long-term use, and the lens is very suitable for vehicle-mounted lenses.
P 2 O 5 The network forming body of the glass is the basis for forming the glass, and the content of the network forming body is closely related to the chemical stability, refractive index, abbe number and other key indexes of the glass. Due to tetrahedra [ PO ] 4 ]One double bond in the four bonds of the glass is used for breaking and deforming one vertex angle of the tetrahedron, so that the glass can obtain a loose network structure with a larger thermal expansion coefficient, and the expected negative refractive index temperature coefficient is obtained. Wherein if P 2 O 5 The content of the (B) is more than 30%, the network structure of the glass is excessively loose, so that the chemical stability, especially the stability of the water-resistant effect is reduced, and the glass is deliquesced when the water-resistant effect is more serious, and the refractive index and the Abbe number of the glass do not reach the design requirements, so that the P in the invention 2 O 5 The upper limit of the content of (2) is 30%, preferably 25%; if P 2 O 5 The content of (2) is lower than 4%, and the refractive index temperature coefficient of the glass does not meet the design requirement, so P 2 O 5 The lower limit of the content of (2) is 4%, preferably 10%, more preferably 15%.
To at P 2 O 5 The inventor researches and discovers that the glass maintains good chemical stability under the condition of higher content, and adds a proper amount of SiO 2 、B 2 O 3 The components can improve the chemical stability and crystallization resistance of the glass.
Specifically, B 2 O 3 As network former, its action is as follows P 2 O 5 Similarly. In the glassy state P 2 O 5 Adding B into 2 O 3 The layered or interlaced chain structure tends to the skeleton structure, and the chemical stability of the glass is improved. But B is 2 O 3 If the content is higher than 10%, the structure of the glass is more compact, so that the thermal expansion coefficient of the glass is reduced, and the temperature coefficient of the refractive index is increased. Thus B 2 O 3 The content of (2) is limited to 0 to 10%, preferably 1 to 9%, more preferably 2 to 8%.
Glass network former SiO 2 Added into glass to replace P 2 O 5 The refractive index and dispersion of the glass are not greatly changed, but if the content exceeds 10%, the temperature coefficient of the refractive index of the glass is rapidly increased, and the crystallization resistance of the glass is reduced. Thus, siO 2 The content of (2) is limited to 0 to 10%, preferably 0 to 8%, more preferably 0 to 5%.
In some embodiments of the invention, siO 2 +B 2 O 3 And P 2 O 5 To a certain extent, determines P 2 O 5 Structural state in glass, P 2 O 5 The structural state of the glass has a great influence on two indexes of refractive index temperature coefficient and chemical stability of the glass. Further, when SiO 2 +B 2 O 3 And P 2 O 5 Ratio (SiO) 2 +B 2 O 3 )/P 2 O 5 When the refractive index of the glass is more than 0.5, the temperature coefficient of the refractive index of the glass is rapidly increased, and the design requirement is not met; if (SiO) 2 +B 2 O 3 )/P 2 O 5 When the water resistance of the glass is less than 0.1, the water resistance of the glass is rapidly lowered, and the use requirement in severe conditions cannot be satisfied. On the other hand, for production, if (SiO 2 +B 2 O 3 )/P 2 O 5 The value of (2) is smaller than 0.1, the volatilization of the glass is increased during forming, so that the refractive index and Abbe number of the glass are greatly changed, and the design requirement cannot be met; the glass has low high-temperature viscosity, and is easy to generate stripes below the C level in the glass, so that the glass cannot be applied to imaging systems with higher requirements. Thus, in the present invention (SiO) 2 +B 2 O 3 )/P 2 O 5 The value of (2) is 0.1 to 0.5, preferably 0.15 to 0.45, more preferably 0.2 to 0.4.
Nb 2 O 5 The glass is an important component of the glass, and the refractive index of the glass can be rapidly improved by adding the glass, so that the glass has the performance of high refractive index and high dispersion. However, if the content exceeds 45%, the devitrification resistance of the glass is drastically reduced, and more seriously, nb 2 O 5 When the content exceeds 45%, the refractive index temperature coefficient of the glass can be rapidly improved, which is contrary to the aim of reducing the refractive index temperature coefficient of the glass; if the content is less than 10%, the refractive index and dispersion of the glass do not meet the design requirements, and the chemical stability, particularly the water resistance, of the glass is lowered. Thus, nb 2 O 5 The content of (2) is limited to 10 to 45%, preferably 15 to 45%, more preferably 20 to 43%.
To at Nb 2 O 5 The inventors have found that the addition of a proper amount of Gd can maintain good crystallization resistance even when the content is relatively high 2 O 3 、Y 2 O 3 、Al 2 O 3 、TiO 2 One or more of the components can improve the crystallization resistance of the glass.
Specifically, gd 2 O 3 Effect on refractive index and dispersion with Nb 2 O 5 Similarly, if the content is higher than 8%, the refractive index temperature coefficient of the glass increases rapidly, the cost increases rapidly, and the crystallization resistance of the glass decreases adversely, so Gd 2 O 3 The content of (2) is limited to 0 to 8%, preferably 0 to 6%, more preferably 0 to 4%.
Y 2 O 3 Added into glass to replace Nb 2 O 5 The refractive index and dispersion of the glass are not greatly changed, but if the content exceeds 5%, the temperature coefficient of the refractive index of the glass is rapidly increased, and the crystallization resistance of the glass is reduced. Thus Y 2 O 3 The content of (2) is limited to 0 to 5%, preferably 0 to 4%, more preferably 0 to 3%.
Al 2 O 3 The glass can be added into the glass to improve the crystallization resistance of the glass, and simultaneously, the capability of molten glass to corrode crucible materials can be reduced. However, if the amount of the additive is more than 3%, the refractive index temperature coefficient of the glass increases, and the melting property of the glass decreases, so that the refractive index also decreases rapidly. Thus, al 2 O 3 The content of (2) is limited to 3% or less, preferably 2% or less, and more preferably 1% or less.
TiO 2 The glass can be added into the glass, so that the sunlight resistance stability of the glass can be improved, and the glass is particularly important for long-term exposure of the vehicle-mounted lens to strong ultraviolet environments such as highland. In addition, small amounts of TiO 2 Can improve the crystallization resistance of glass, but TiO 2 For bulk glass, it is detrimental to the decrease in the temperature coefficient of refractive index. Through a great number of experiments, the inventor finds that if the content exceeds 15%, the refractive index temperature coefficient of the glass does not reach the design requirement. Thus, in the present invention, tiO 2 The content is 0 to 15%, preferably 0 to 12%, more preferably 0 to 10%.
Through a great deal of experimental study by the inventor, nb 2 O 5 And TiO 2 At the same time using TiO than singly using 2 The effect of improving the sunlight resistance stability of the glass is more obvious. However, when TiO 2 With Nb 2 O 5 Ratio of TiO 2 /Nb 2 O 5 Above 1, the solar resistance stability of the glass is not improved but the temperature coefficient of refractive index increases faster, which is contrary to the goal of obtaining a lower temperature coefficient of refractive index. Thus, in some embodiments of the invention, to obtain a glass with a lower refractive index temperature coefficient and strong sunlight resistance stability, tiO 2 /Nb 2 O 5 The value of (2) is 1 or less, preferably 0.8 or less, more preferably 0.5 or lessAnd (3) downwards.
BaO, caO, srO, mgO are alkaline earth metal oxides, and the refractive index and dispersion of the glass can be adjusted by adding the alkaline earth metal oxides into the glass, so that the stability of the glass is enhanced, and the crystallization resistance of the glass is improved. The general technical literature considers the role of the same oxides in such glasses to be essentially the same. However, the inventors found through a large number of experiments that the above alkaline earth oxides are very different in their roles in refractive index temperature coefficient, chemical stability and anti-devitrification properties, which are the most important factors for the glass of the present system.
BaO has the strongest ability to lower the temperature coefficient of the refractive index of the glass, but if the content exceeds 20%, the chemical stability of the glass, particularly the water resistance, is rapidly reduced, and the crystallization resistance of the glass is also rapidly reduced. Therefore, the content of BaO is limited to 0 to 20%, preferably 0 to 16%, more preferably 0 to 13%.
The SrO has a higher refractive index temperature coefficient reducing ability than CaO but lower than BaO, and is added to the glass to deteriorate the chemical stability of the glass, and if the SrO content exceeds 10%, the crystallization resistance of the glass is rather rapidly deteriorated, and the refractive index temperature coefficient of the glass is rapidly increased, so that the SrO content is 10% or less, preferably 0 to 8%, more preferably 0 to 6%.
In the system glass of the present invention, since the ability of CaO to deteriorate the water resistance is the least among three alkaline earth metal oxides of CaO, baO and SrO, caO may be added in an appropriate amount from the viewpoint of improving the water resistance of the glass, and the CaO content in the present invention is limited to 0 to 25%, preferably 0 to 20%, more preferably 0 to 15%. CaO reduces the refractive index temperature coefficient of the glass by a second amount than BaO and SrO, so it is preferred in some embodiments that no CaO is added only from the standpoint of reducing the refractive index temperature coefficient.
For the glass of the system, mgO is unfavorable for reducing the temperature coefficient of the refractive index of the glass, but proper addition can improve the water resistance and the stability of the glass. If the MgO content exceeds 5%, the refractive index temperature coefficient of the glass cannot meet the design requirement, and meanwhile, the crystallization resistance of the glass can be rapidly reduced. Therefore, the content of MgO is limited to 5% or less, preferably 3% or less, and more preferably no MgO is added.
The inventors have found that when BaO, caO, srO alkaline earth oxides are added, the glass undergoes complex synergism, and the properties do not change linearly with the addition of a single substance. In some embodiments of the present invention, when the value of CaO/(bao+sro) exceeds 0.5, although the chemical stability of the glass is improved to some extent, the refractive index temperature coefficient of the glass is rapidly increased and the crystallization resistance of the glass is rapidly lowered, so that the value of CaO/(bao+sro) is 0 to 0.5, preferably 0 to 0.4, and more preferably 0 to 0.3.
In the bulk glass, if a lower refractive index temperature coefficient is desired, it is preferable to satisfy the content of BaO not less than the content of CaO, more preferably the content of SrO not less than the content of CaO, and still more preferably the content of BaO not less than the content of SrO not less than the content of CaO.
Li 2 O、K 2 O、Na 2 O belongs to alkali metal oxide, and proper amount of O can reduce the refractive index temperature coefficient of the glass, but the chemical stability and crystallization resistance of the glass are rapidly reduced. The inventors found through a large number of experimental studies that:
1) In the glass of the system of the invention, the refractive index temperature coefficient of the glass does not linearly decrease along with the growth of the alkali metal oxide, but the refractive index temperature coefficient does not decrease after reaching an extreme value, but the alkali metal oxide is continuously added on the extreme value, so that the crystallization resistance of the glass is rapidly deteriorated. In the present invention, li 2 O、K 2 O and Na 2 Sum of O contents Li 2 O+K 2 O+Na 2 If the value of O exceeds 35%, the refractive index temperature coefficient of the glass is not lowered, and the crystallization resistance and water resistance are drastically lowered.
From the production point of view, it is expected that the lower the high-temperature viscosity at the time of clarification, the more favorable the discharge of bubbles, so if the refractive index temperature coefficient, the water resistance and the crystallization resistance of the glass meet the design requirements, the above-mentioned alkali metal oxide can be added by not more than 35%, the high-temperature viscosity of the glass is improved, and the bubble level of the glass at the time of mass production is improved. Thus Li 2 O+K 2 O+Na 2 Total amount control of OThe content is not more than 35%, preferably 5 to 30%, more preferably 5 to 25%.
2) When the above three alkali metal oxides are all present together, a complex synergistic effect is produced if Li 2 O/(K 2 O+Na 2 When the value of O) is more than 0.5, the crystallization resistance and chemical stability of the glass are drastically reduced, and the refractive index temperature coefficient of the glass is substantially unchanged. Thus Li 2 O/(K 2 O+Na 2 When the value of O) is 0.5 or less, preferably 0.4 or less, more preferably 0.3 or less, the refractive index temperature coefficient of the glass is lowered, and the degradation of the crystallization resistance and chemical stability is small.
From the viewpoint of lowering the temperature coefficient of refractive index, K 2 O and Na 2 O is stronger and Li 2 O times; from the viewpoint of breaking the chemical stability of the glass, K 2 O and Na 2 O is stronger and Li 2 O times; in terms of breaking glass crystallization resistance, li 2 The strongest O, K 2 O and Na 2 O times. Therefore, in order to obtain a refractive index temperature coefficient, chemical stability, and crystallization resistance satisfying design expectations, a great deal of experimental study is required to determine how to select an appropriate kind and an appropriate amount of alkali metal oxide. If Na is 2 Since the O content exceeds 15%, the crystallization resistance and chemical stability of the glass are drastically reduced, and the content thereof is limited to 0 to 15%, preferably 2 to 12%, more preferably 4 to 10%. If K 2 The O content is more than 25%, and the devitrification resistance and chemical stability of the glass are rapidly lowered, so that the content thereof is limited to 0 to 25%, preferably 3 to 20%, more preferably 5 to 15%. Li (Li) 2 If the O content exceeds 5%, the crystallization resistance of the glass is rapidly lowered, and therefore the content is 5% or less, preferably 3% or less, more preferably no Li is added 2 O。
In some embodiments of the invention, na in the glass 2 O and K 2 The ratio of O has a large correlation with the bubble degree and water resistance of the glass. Further, when Na 2 O/K 2 When the value of O is more than 1.5, the water resistance of the glass is drastically reduced; when Na is 2 O/K 2 When the value of O is less than 0.1, the bubble degree of the glass is fastThe speed drops. Thus, na 2 O/K 2 The value of O is 0.1 to 1.5, preferably 0.2 to 1.2, more preferably 0.3 to 1.0.
In some embodiments of the invention, the aggregate content of BaO, srO, caO is equal to Nb 2 O 5 、Gd 2 O 3 、Y 2 O 3 The ratio of the total content of (2) has a large relationship with the refractive index temperature coefficient, crystallization resistance and water resistance of the glass. Further, when (BaO+SrO+CaO)/(Nb) 2 O 5 +Gd 2 O 3 +Y 2 O 3 ) When the value of (2) is larger than 0.5, the refractive index temperature coefficient of the glass is not lowered, and the water resistance and crystallization resistance of the glass are lowered. Therefore, to obtain a glass having a low refractive index and a low temperature coefficient, having water resistance satisfying design requirements and having good crystallization resistance, (BaO+SrO+CaO)/(Nb) 2 O 5 +Gd 2 O 3 +Y 2 O 3 ) The value of (2) is 0 to 0.5, preferably 0 to 0.4, more preferably 0 to 0.3.
In the system glass of the present invention, baO and Nb 2 O 5 The ratio of the content of (2) has a great correlation with the refractive index temperature coefficient of the glass and the water resistance of the glass and the crystallization resistance thereof. Further, when BaO, nb 2 O 5 Ratio BaO/Nb of (B) 2 O 5 When the refractive index is more than 0.5, the refractive index temperature coefficient of the glass is not lowered, but the water resistance and crystallization resistance of the glass are drastically lowered. Thus, baO/Nb 2 O 5 The value of (2) is 0 to 0.5, preferably 0 to 0.4, more preferably 0 to 0.3.
The inventors have found that in some embodiments of the invention, (CaO+BaO+SrO)/(Al) 2 O 3 +TiO 2 ) Has a large correlation with the temperature coefficient of refractive index of the glass. Further, when (CaO+BaO+SrO)/(Al) 2 O 3 +TiO 2 ) When the value of (2) is larger than 1.0, although the chemical stability and the crystallization resistance of the glass are slightly improved, the refractive index temperature coefficient of the glass is rapidly increased, and the design requirement is not met. Thus, (CaO+BaO+SrO)/(Al) 2 O 3 +TiO 2 ) The value of (2) is less than 1.0, preferably less than 0.8, more preferably less than 0.6.
In some embodiments of the invention, the metal is prepared by adding 0 to 1% Sb 2 O 3 、SnO 2 SnO and CeO 2 One or more components of the glass serving as a clarifying agent can improve the clarifying effect of the glass. However, the present invention has a reasonable formulation, and has a good clarifying effect and excellent bubble degree, and therefore, it is preferable to add 0 to 0.5% of the clarifying agent, more preferably 0 to 0.1% of the clarifying agent, and still more preferably, no clarifying agent is added.
< component not to be contained >
In the glass of the present invention, V, cr, mn, fe, co, ni, cu, ag and oxides of transition metals such as Mo are colored even when they are contained in small amounts, either alone or in combination, and absorb at a specific wavelength in the visible light range, so that the property of the present invention of improving the visible light transmittance effect is impaired, and therefore, in particular, an optical glass having a wavelength transmittance in the visible light range is preferably practically not contained.
Th, cd, tl, os, be and Se oxides have a tendency to be used in a controlled manner as harmful chemical substances in recent years, and are required to provide environmental protection not only in the glass manufacturing process but also in the processing steps and disposal after production. Therefore, in the case where the influence on the environment is emphasized, it is preferable that they are not substantially contained except for unavoidable mixing. As a result, the optical glass becomes practically free from environmental pollutants. Therefore, the optical glass of the present invention can be manufactured, processed, and discarded without taking special measures against the environment.
In order to achieve environmental friendliness, the optical glass of the present invention does not contain As 2 O 3 And PbO. Although As 2 O 3 Has the effects of eliminating bubbles and better preventing glass from being colored, but As 2 O 3 The addition of (c) increases the corrosion of the glass to the furnace, and in particular to the platinum of the platinum furnace, resulting in more platinum ions entering the glass, which adversely affects the service life of the platinum furnace. PbO can significantly improve the high refractive index and high dispersion properties of glass, but PbO and As 2 O 3 Substances which cause environmental pollution.
The term "not incorporated" as used herein means that the compound, molecule, element or the like is not intentionally added to the optical glass of the present invention as a raw material; however, it is also within the scope of the present invention that certain impurities or components may be present as raw materials and/or equipment for producing optical glass that are not intentionally added, and that may be present in small or trace amounts in the final optical glass.
The performance of the optical glass of the present invention will be described below.
< refractive index and Abbe number >
Refractive index of optical glass (n) d ) With Abbe number (v) d ) Tested according to the method specified in GB/T7962.1-2010.
Refractive index (n) of the optical glass of the present invention d ) 1.73 to 1.81, preferably 1.74 to 1.80, more preferably 1.75 to 1.79; abbe number (v) d ) 20 to 30, preferably 21 to 28, more preferably 22 to 26.
< stability against Water action >
Stability against water action of optical glass (D) W ) (powder method) the test was carried out according to the method specified in GB/T17129.
Stability against water action of the optical glass of the present invention (D W ) The number is 3 or more, preferably 2 or more, and more preferably 1.
< temperature coefficient of refractive index >
Refractive index temperature coefficient (dn/dt) of optical glass was measured according to the method prescribed in GB/T7962.4-2010, and refractive index temperature coefficient (d-line dn/dt relative (10) -6 /℃))。
The refractive index temperature coefficient (dn/dt) of the optical glass is-2 multiplied by 10 -6 preferably-2.5X10 or less at a temperature of/DEG C -6 Lower than or equal to-3.0X10 is more preferable -6 Preferably at most-4.0X10. Mu.M -6 And/or lower.
< anti-devitrification Property >
Cutting sample glass into 20×20×10mm, and heatingDegree of T g Preserving heat for 30 minutes in a muffle furnace at +230 ℃, taking out, putting into heat-preserving cotton, slowly cooling, and observing whether obvious crystallization exists on the surface. The surface no obvious crystallization means that: the surface has no crystallization spots or has crystallization spots, but the area of the crystallization spots accounts for less than 5 percent of the whole area and the crystallization depth is not more than 0.5mm. If the glass sample has no obvious crystallization, the crystallization resistance of the glass is excellent.
< streak degree >
The streak degree of the glass of the present invention was measured according to the method specified in MLL-G-174B. The method is that a fringe instrument consisting of a point light source and a lens is used for comparing and checking the direction of the easiest visible fringe with a standard sample, and the fringe instrument is divided into 4 grades which are A, B, C, D grades respectively, wherein grade A is that no macroscopic fringe exists under the specified detection condition, grade B is that fine and dispersed fringe exists under the specified detection condition, grade C is that no slight parallel fringe exists under the specified detection condition, and grade D is that rough fringe exists under the specified detection condition.
The degree of streaking of the optical glass of the present invention is C or more, preferably B or more, more preferably A.
[ method of production ]
The manufacturing method of the optical glass comprises the following steps: the glass is produced by adopting conventional raw materials and conventional processes, using carbonate, nitrate, sulfate, hydroxide, oxide and the like as raw materials, proportioning according to a conventional method, putting the prepared furnace burden into a smelting furnace at 1100-1250 ℃ for smelting, clarifying, stirring and homogenizing to obtain homogeneous molten glass without bubbles and undissolved substances, and casting and annealing the molten glass in a mould. Those skilled in the art can appropriately select the raw materials, the process methods, and the process parameters according to actual needs.
[ glass preform and optical element ]
The optical glass thus produced may be used to produce a glass preform by using, for example, polishing, reheat press molding, precision press molding, or other press molding means. That is, the glass preform may be produced by mechanically working the optical glass by grinding or polishing, or by producing a preform for press molding from the optical glass, and then performing the polishing after the hot press molding, or by performing the precision press molding on the preform produced by the polishing.
The means for producing the glass preform is not limited to the above-described means. As described above, the optical glass of the present invention is useful for various optical elements and optical designs, and among them, it is particularly preferable to form a preform from the optical glass of the present invention, and use the preform for performing hot press molding, precision press molding, and the like to produce optical elements such as lenses and prisms.
The glass preform and the optical element of the present invention are each formed of the optical glass of the present invention described above. The glass preform of the present invention has excellent characteristics possessed by an optical glass; the optical element of the present invention has excellent characteristics of optical glass, and can provide various optical elements such as lenses and prisms having high optical value.
Examples of the lens include various lenses such as a concave meniscus lens, a convex meniscus lens, a biconvex lens, a biconcave lens, a plano-convex lens, and a plano-concave lens, each of which has a spherical or aspherical lens surface.
[ optical instrument ]
The optical element formed by the optical glass can be used for manufacturing optical instruments such as photographic equipment, vehicle-mounted equipment, camera equipment, display equipment, monitoring equipment and the like.
The optical glass has excellent chemical stability, lower refractive index temperature coefficient and other performances, and is particularly suitable for being applied to the fields of vehicle-mounted, monitoring, security protection and the like.
Examples
< example of optical glass >
In order to further clearly illustrate and describe the technical solutions of the present invention, the following non-limiting examples are provided.
The optical glass shown in tables 2 to 3 was obtained by the above-described method for producing an optical glass. In addition, the test method of the invention is used for testingThe characteristics of each glass were determined, and the measurement results are shown in tables 2 to 3. In tables 2 to 3, (SiO) 2 +B 2 O 3 )/P 2 O 5 The value of (2) is denoted by K1; tiO (titanium dioxide) 2 /Nb 2 O 5 The value of (2) is represented by K2; li (Li) 2 O+K 2 O+Na 2 The total amount of O is represented by K3; li (Li) 2 O/(K 2 O+Na 2 The value of O) is denoted by K4; na (Na) 2 O/K 2 The value of O is represented by K5; (BaO+SrO+CaO)/(Nb) 2 O 5 +Gd 2 O 3 +Y 2 O 3 ) The value of (2) is denoted by K6; baO/Nb 2 O 3 The value of (2) is denoted by K7; (CaO+BaO+SrO)/(Al) 2 O 3 +TiO 2 ) The value of (2) is denoted by K8. In the anti-crystallization performance test, no obvious crystallization is marked as "A", and no obvious crystallization is marked as "B".
TABLE 2
TABLE 3 Table 3
< example of glass preform >
The glasses obtained in examples 1 to 20 were subjected to polishing, hot press molding, and press molding such as precision press molding to prepare preforms of various lenses such as concave meniscus lenses, convex meniscus lenses, biconvex lenses, biconcave lenses, plano-convex lenses, and plano-concave lenses, prisms, and the like.
< example of optical element >
The glass preforms obtained in the above examples were annealed, and fine-tuning was performed while reducing deformation of the inside of the glass, so that optical characteristics such as refractive index reached a desired value.
Next, each preform was ground and polished to produce various lenses and prisms such as a concave meniscus lens, a convex meniscus lens, a biconvex lens, a biconcave lens, a plano-convex lens, and a plano-concave lens. The surface of the obtained optical element may be coated with an antireflection film.
< example of optical instrument >
The optical element manufactured by the above-described optical element embodiments can be used for, for example, imaging devices, sensors, microscopes, medical technology, digital projection, communication, optical communication technology/information transmission, optics/illumination in the automotive field, lithography technology, excimer lasers, wafers, computer chips, and integrated circuits and electronic devices including such circuits and chips, or for imaging devices and apparatuses in the vehicle field, by forming an optical component or an optical assembly by using one or more optical elements through optical design.

Claims (29)

1. The optical glass is characterized by comprising the following components in percentage by weight: p (P) 2 O 5 ：4～30％；BaO：0～20％；Nb 2 O 5 ：15～45％；TiO 2 ：0～15％；Li 2 O+K 2 O+Na 2 O: 0-35%; wherein BaO/Nb 2 O 5 0 to 0.5, caO/(BaO+SrO) 0 to 0.5, (SiO) 2 +B 2 O 3 )/P 2 O 5 0.15 to 0.5, tiO 2 /Nb 2 O 5 The value of (2) is 0.31 or less.
2. The optical glass according to claim 1, further comprising, in weight percent: siO (SiO) 2 ：0～10％；B 2 O 3 ：0～10％；Gd 2 O 3 ：0～8％；Y 2 O 3 ：0～5％；Al 2 O 3 :0 to 3 percent; mgO: 0-5%; caO: 0-25%; srO: 0-10%; clarifying agent: 0 to 1 percent.
3. The optical glass is characterized by comprising the following components in percentage by weight 2 O 5 ：4～30％；Nb 2 O 5 ：15～45％；Li 2 O+K 2 O+Na 2 O：0～35％；SiO 2 ：0～10％；B 2 O 3 ：0～10％；Gd 2 O 3 ：0～8％；Y 2 O 3 ：0～5％；Al 2 O 3 ：0～3％；TiO 2 : 0-15%; mgO: 0-5%; caO: 0-25%; srO: 0-10%; baO: 0-20%; clarifying agent: 0 to 1 percent of BaO/Nb 2 O 5 0 to 0.5, caO/(BaO+SrO) 0 to 0.5, (SiO) 2 +B 2 O 3 )/P 2 O 5 0.15 to 0.5, tiO 2 /Nb 2 O 5 The value of (2) is 0.31 or less.
4. An optical glass comprising P 2 O 5 、Nb 2 O 5 Alkaline earth metal oxide and alkali metal oxide, the components of which are expressed in weight percent, wherein BaO/Nb 2 O 5 0 to 0.5, li 2 O/(K 2 O+Na 2 O) is 0.5 or less, tiO 2 :0 to 15 percent, caO/(BaO+SrO) is 0 to 0.5, (SiO) 2 +B 2 O 3 )/P 2 O 5 0.15 to 0.5, tiO 2 /Nb 2 O 5 The value of (2) is less than 0.31, and the refractive index n of the optical glass d Is 1.73 to 1.81, and Abbe number v d 20 to 30, and the refractive index temperature coefficient dn/dt is-2 multiplied by 10 -6 And/or lower.
5. The optical glass according to claim 4, wherein the composition comprises, in weight percent: p (P) 2 O 5 : 4-30%; and/or Nb 2 O 5 : 10-45%; and/or Li 2 O+K 2 O+Na 2 O: 0-35%; and/or SiO 2 : 0-10%; and/or B 2 O 3 : 0-10%; and/or Gd 2 O 3 : 0-8%; and/or Y 2 O 3 : 0-5%; and/or Al 2 O 3 :0 to 3 percent; and/or MgO: 0-5%; and/or CaO: 0-25%; and/or SrO: 0-10%; and/or BaO: 0-20%; and/or clarifying agent: 0 to 1 percent.
6. The optical glass according to any one of claims 1 to 5, wherein the components thereof are expressed in weight percent, wherein: p (P) 2 O 5 : 10-30%; and/or Nb 2 O 5 : 20-45%; and/or Li 2 O+K 2 O+Na 2 O: 5-30%; and/or SiO 2 : 0-8%; and/or B 2 O 3 :1 to 9 percent; and/or Gd 2 O 3 :0 to 6 percent; and/or Y 2 O 3 :0 to 4 percent; and/or Al 2 O 3 :0 to 2 percent; and/or TiO 2 : 0-12%; and/or MgO:0 to 3 percent; and/or CaO: 0-20%; and/or SrO: 0-8%; and/or BaO:0 to 16 percent; and/or clarifying agent: 0 to 0.5 percent.
7. The optical glass according to any one of claims 1 to 5, wherein the components thereof are expressed in weight percent, wherein: p (P) 2 O 5 : 15-25%; and/or Nb 2 O 5 : 20-43%; and/or Li 2 O+K 2 O+Na 2 O: 5-25%; and/or SiO 2 : 0-5%; and/or B 2 O 3 : 2-8%; and/or Gd 2 O 3 :0 to 4 percent; and/or Y 2 O 3 :0 to 3 percent; and/or Al 2 O 3 :0 to 1 percent; and/or TiO 2 : 0-10%; and/or CaO: 0-15%; and/or SrO:0 to 6 percent; and/or BaO:0 to 13 percent; and/or clarifying agent: 0 to 0.1 percent.
8. The optical glass according to any one of claims 1 to 5, wherein the components thereof are expressed in weight percent, wherein BaO/Nb 2 O 5 0 to 0.4; and/or (SiO) 2 +B 2 O 3 )/P 2 O 5 0.15 to 0.45; and/or CaO/(BaO+SrO) of 0 to 0.4; and/or Li 2 O/(K 2 O+Na 2 O) is 0.5 or less; and/or Na 2 O/K 2 O is 0.1-1.5; and/or (BaO+SrO+CaO)/(Nb) 2 O 5 +Gd 2 O 3 +Y 2 O 3 ) 0 to 0.5; and/or (CaO+BaO+SrO)/(Al) 2 O 3 +TiO 2 ) Less than 1.0.
9. The optical glass according to any one of claims 1 to 5, wherein the components thereof are expressed in weight percent, wherein BaO/Nb 2 O 5 0 to 0.3; and/or (SiO) 2 +B 2 O 3 )/P 2 O 5 0.2 to 0.4; and/or CaO/(BaO+SrO) of 0 to 0.3; and/or Li 2 O/(K 2 O+Na 2 O) is 0.4 or less; and/or Na 2 O/K 2 O is 0.2-1.2; and/or (BaO+SrO+CaO)/(Nb) 2 O 5 +Gd 2 O 3 +Y 2 O 3 ) 0 to 0.4; and/or (CaO+BaO+SrO)/(Al) 2 O 3 +TiO 2 ) Less than 0.8.
10. The optical glass according to any one of claims 1 to 5, wherein the components thereof are expressed in weight percent, wherein Li 2 O/(K 2 O+Na 2 O) is 0.3 or less; and/or Na 2 O/K 2 O is 0.3-1.0; and/or (BaO+SrO+CaO)/(Nb) 2 O 5 +Gd 2 O 3 +Y 2 O 3 ) 0 to 0.3; and/or (CaO+BaO+SrO)/(CaO+BaO+SrO)
(Al 2 O 3 +TiO 2 ) Less than 0.6.
11. The optical glass according to any one of claims 1 to 5, wherein the components are expressed in weight percent, na 2 O: 0-15%; and/or K 2 O: 0-25%; and/or Li 2 O：0～5％。
12. The optical glass according to any one of claims 1 to 5, wherein the components are expressed in weight percent, na 2 O: 2-12%; and/or K 2 O: 3-20%; and/or Li 2 O：0～3％。
13. The optical glass according to any one of claims 1 to 5, wherein the components are expressed in weight percent, na 2 O: 4-10%; and/or K 2 O: 5-15%; and/or without addition of Li 2 O。
14. The optical glass according to any one of claims 1 to 5, wherein the components thereof are expressed in weight percent, and wherein the content of BaO is not less than the content of CaO.
15. The optical glass according to any one of claims 1 to 5, wherein the composition is expressed in weight percent, and wherein the content of SrO is not less than the content of CaO.
16. The optical glass according to any one of claims 1 to 5, wherein the components thereof are expressed in weight percent, wherein the content of BaO is not less than the content of SrO is not less than the content of CaO.
17. The optical glass according to any one of claims 1 to 5, wherein the optical glass has a refractive index n d 1.73 to 1.81; abbe number v d 20 to 30.
18. The optical glass according to any one of claims 1 to 5, wherein the optical glass has a refractive index n d 1.74 to 1.80; abbe number v d 21 to 28.
19. The optical glass according to any one of claims 1 to 5, wherein the optical glass has a refractive index n d 1.75 to 1.79; abbe number v d 22 to 26.
20. The optical glass according to any one of claims 1 to 5, wherein the optical glass has a refractive index temperature coefficient dn/dt of-2 x 10 at 40 to 60 ℃ -6 And/or lower.
21. According toThe optical glass according to any one of claims 1 to 5, wherein the optical glass has a refractive index temperature coefficient dn/dt of-2.5X10 at 40 to 60 DEG C -6 And/or lower.
22. The optical glass according to any one of claims 1 to 5, wherein the optical glass has a refractive index temperature coefficient dn/dt of-3.0x10 at 40 to 60 ℃ -6 And/or lower.
23. The optical glass according to any one of claims 1 to 5, wherein the optical glass has a refractive index temperature coefficient dn/dt of-4.0X10 at 40 to 60 ℃ -6 And/or lower.
24. The optical glass according to any one of claims 1 to 5, wherein the optical glass has a water-action-resistant stability D W More than 3 types; and/or the streak degree is C level or more.
25. The optical glass according to any one of claims 1 to 5, wherein the optical glass has a water-action-resistant stability D W Is more than 2 types; and/or the streak degree is above B grade.
26. The optical glass according to any one of claims 1 to 5, wherein the optical glass has a water-action-resistant stability D W Class 1; and/or the striping degree is class a.
27. A glass preform made using the optical glass of any one of claims 1 to 26.
28. An optical element made using the optical glass according to any one of claims 1 to 26 or made using the glass preform according to claim 27.
29. An optical device comprising the optical glass according to any one of claims 1 to 26, or the optical element according to claim 28.
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