CN114853336B - Optical glass, glass preform, optical element, and optical instrument - Google Patents
Optical glass, glass preform, optical element, and optical instrument Download PDFInfo
- Publication number
- CN114853336B CN114853336B CN202210710690.4A CN202210710690A CN114853336B CN 114853336 B CN114853336 B CN 114853336B CN 202210710690 A CN202210710690 A CN 202210710690A CN 114853336 B CN114853336 B CN 114853336B
- Authority
- CN
- China
- Prior art keywords
- optical glass
- glass according
- percent
- components
- weight percent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/062—Glass compositions containing silica with less than 40% silica by weight
- C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
- C03C3/068—Glass compositions containing silica with less than 40% silica by weight containing boron containing rare earths
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (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)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Glass Compositions (AREA)
Abstract
The invention provides a method for preparing a crystal silicon wafer with low sagging temperature and N d Consistency and T s An optical glass having excellent stability, the optical glass comprising, in weight percent: siO (SiO) 2 ：17～47％；B 2 O 3 ：20～50％；Al 2 O 3 ：0.5～8％；ZnO：0.5～8％；RO：6～45％；La 2 O 3 +Y 2 O 3 +Gd 2 O 3 ：0.5～15％；Li 2 O：1～7％；Na 2 O:0.1 to 7%, wherein the RO is a total content of BaO, srO, caO, mgO. Through reasonable component design, the optical glass obtained by the invention has the expected refractive index and Abbe number, and simultaneously has lower sag temperature and N d Consistency and T s The stability is excellent.
Description
Technical Field
The present invention relates to an optical glass, and more particularly, to an optical glass having a refractive index of 1.57 to 1.61 and an abbe number of 58 to 64, and a glass preform, an optical element, and an optical instrument each made of the same.
Background
With the rapid development of intelligent driving, portrait identification and other technologies, the demand for optical aspheric lenses with refractive indexes of 1.57-1.61 and Abbe numbers of 58-64 is rapidly growing. The technique of precision molding an aspherical surface of an optical glass can obtain an aspherical lens at low cost, but requires a sag temperature (T s ) As low as possible, better profiling quality and lower mould costs are achieved.
The glasses used in the above fields in the prior art use a large amount of Li 2 O to reduce T s A large amount of Li 2 O is used for glass in the production processThe melting tank has higher corrosiveness, more impurities are introduced, and N is N d Consistency and T s The stability control difficulty is high, the service life of the smelting furnace is prolonged, and the subsequent aspheric profiling process is controlled with great difficulty.
Disclosure of Invention
Based on the above reasons, the invention aims to solve the technical problems of providing a crystal oscillator with lower sagging temperature and N d Consistency and T s An optical glass having excellent stability.
The technical scheme adopted for solving the technical problems is as follows:
the optical glass comprises the following components in percentage by weight: siO (SiO) 2 ：17～47％；B 2 O 3 ：20～50％；Al 2 O 3 ：0.5～8％；ZnO：0.5～8％；RO：6～45％；La 2 O 3 +Y 2 O 3 +Gd 2 O 3 ：0.5～15％；Li 2 O：1～7％；Na 2 O:0.1 to 7%, wherein the RO is a total content of BaO, srO, caO, mgO.
Further, the optical glass comprises the following components in percentage by weight: p (P) 2 O 5 :0 to 3 percent; and/or ZrO 2 :0 to 3 percent; and/or K 2 O: 0-5%; and/or clarifying agent: 0 to 1 percent of clarifying agent which is Sb 2 O 3 、SnO 2 、Na 2 SiF 6 、K 2 SiF 6 One or more of the following.
An optical glass, the components of which are represented by weight percentage and are composed of SiO 2 ：17～47％；B 2 O 3 ：20～50％；Al 2 O 3 ：0.5～8％；ZnO：0.5～8％；RO：6～45％；La 2 O 3 +Y 2 O 3 +Gd 2 O 3 ：0.5～15％；Li 2 O：1～7％；Na 2 O：0.1～7％；P 2 O 5 ：0～3％；ZrO 2 ：0～3％；K 2 O: 0-5%; clarifying agent: 0 to 1 percent of the composite material, wherein the RO is BaO, srO, caO, mgO, and the clarifying agent is Sb 2 O 3 、SnO 2 、Na 2 SiF 6 、K 2 SiF 6 One or more of the following.
Further, the optical glass comprises the following components in percentage by weight: b (B) 2 O 3 /SiO 2 From 0.55 to 2.3, preferably B 2 O 3 /SiO 2 From 0.7 to 2.0, more preferably B 2 O 3 /SiO 2 From 0.8 to 1.8, further preferably B 2 O 3 /SiO 2 1.0 to 1.5.
Further, the optical glass comprises the following components in percentage by weight: (ZrO 2 +Al 2 O 3 )/B 2 O 3 Is 0.05 to 0.4, preferably (ZrO 2 +Al 2 O 3 )/B 2 O 3 Is 0.05 to 0.3, more preferably (ZrO 2 +Al 2 O 3 )/B 2 O 3 Is 0.05 to 0.25, more preferably (ZrO 2 +Al 2 O 3 )/B 2 O 3 0.05 to 0.2.
Further, the optical glass comprises the following components in percentage by weight: baO/RO is 0.4 to 0.95, preferably 0.5 to 0.95, more preferably 0.65 to 0.95, still more preferably 0.7 to 0.9, and the sum of RO is BaO, srO, caO, mgO.
Further, the optical glass comprises the following components in percentage by weight: RO/B 2 O 3 From 0.3 to 1.3, preferably RO/B 2 O 3 From 0.4 to 1.2, more preferably RO/B 2 O 3 From 0.5 to 1.0, RO/B is more preferable 2 O 3 The RO is a total content of BaO, srO, caO, mgO in an amount of 0.6 to 0.9.
Further, the optical glass comprises the following components in percentage by weight: (La) 2 O 3 +Y 2 O 3 +Gd 2 O 3 ) RO is 0.05 to 0.9, preferably (La) 2 O 3 +Y 2 O 3 +Gd 2 O 3 ) RO is 0.1 to 0.6, more preferably (La) 2 O 3 +Y 2 O 3 +Gd 2 O 3 ) RO is 0.1 to 0.4, more preferably (La) 2 O 3 +Y 2 O 3 +Gd 2 O 3 ) and/RO is 0.1 to 0.35, and the RO is BaO, srO, caO, mgO in total content.
Further, the optical glass comprises the following components in percentage by weight: znO/(La) 2 O 3 +Y 2 O 3 +Gd 2 O 3 ) 0.2 to 4.0, preferably ZnO/(La) 2 O 3 +Y 2 O 3 +Gd 2 O 3 ) 0.3 to 3.0, more preferably ZnO/(La) 2 O 3 +Y 2 O 3 +Gd 2 O 3 ) In the range of 0.5 to 2.0, znO/(La) is more preferable 2 O 3 +Y 2 O 3 +Gd 2 O 3 ) 0.6 to 1.6.
Further, the optical glass comprises the following components in percentage by weight: li (Li) 2 O+Na 2 O+K 2 O: less than 15%, preferably Li 2 O+Na 2 O+K 2 O: less than 12%, more preferably Li 2 O+Na 2 O+K 2 O: less than 10%, further preferably Li 2 O+Na 2 O+K 2 O: less than 8%.
Further, the optical glass comprises the following components in percentage by weight: (Na) 2 O+K 2 O)/Li 2 O is 0.1 to 1.5, preferably (Na) 2 O+K 2 O)/Li 2 O is 0.1 to 1.0, more preferably (Na) 2 O+K 2 O)/Li 2 O is 0.2 to 0.8, more preferably (Na 2 O+K 2 O)/Li 2 O is 0.25-0.65.
Further, the optical glass comprises the following components in percentage by weight: siO (SiO) 2 :22 to 40 percent, preferably SiO 2 : 25-38%; and/or B 2 O 3 :22 to 38%, preferably B 2 O 3 : 23-35%; and/or Al 2 O 3 :1 to 7%, preferably Al 2 O 3 :1 to 6.5 percent; and/or ZnO:1 to 7%, preferably ZnO:1 to 6 percent; and/or RO: 8-40%, preferably RO: 10-35%; And/or La 2 O 3 +Y 2 O 3 +Gd 2 O 3 :1 to 12%, preferably La 2 O 3 +Y 2 O 3 +Gd 2 O 3 : 2-10%; and/or Li 2 O:2 to 6.5%, preferably Li 2 O:3 to 5.5 percent; and/or Na 2 O:0.1 to 6%, preferably Na 2 O:0.5 to 5 percent; and/or P 2 O 5 :0 to 1.5 percent; and/or ZrO 2 :0 to 2%, preferably ZrO 2 :0 to 1 percent; and/or K 2 O:0 to 2%, preferably K 2 O:0 to 1 percent; and/or clarifying agent: 0 to 0.8%, preferably a clarifying agent: 0 to 0.5 percent, wherein the RO is BaO, srO, caO, mgO, and the clarifying agent is Sb 2 O 3 、SnO 2 、Na 2 SiF 6 、K 2 SiF 6 One or more of the following.
Further, the optical glass comprises the following components in percentage by weight: baO: 5-30%, preferably BaO:6 to 28%, more preferably BaO: 8-25%; and/or SrO:0.5 to 15%, preferably SrO:0.5 to 13%, more preferably SrO: 0.5-12%; and/or CaO:0 to 10%, preferably CaO:0 to 9%, more preferably CaO: 0-8%; and/or MgO: 0-5%, preferably MgO:0 to 3 percent; and/or La 2 O 3 :0.5 to 10%, preferably La 2 O 3 :1 to 9%, more preferably La 2 O 3 :1.5 to 8 percent; and/or Y 2 O 3 :0 to 8%, preferably Y 2 O 3 :0 to 5%, more preferably Y 2 O 3 :0 to 3 percent; and/or Gd 2 O 3 :0 to 5%, preferably Gd 2 O 3 ：0～3％。
Further, the optical glass comprises the following components in percentage by weight: f:0 to 10%, preferably F:0 to 5%, more preferably F:0 to 3 percent.
Further, the optical glass contains no P in the components 2 O 5 The method comprises the steps of carrying out a first treatment on the surface of the And/or does not contain MgO; and/or does not contain Gd 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the And/or does not contain F.
Further, the optical glassRefractive index n of glass d 1.57 to 1.61, preferably 1.575 to 1.605, more preferably 1.575 to 1.60; abbe number v d 58 to 64, preferably 58.5 to 63.5, more preferably 59 to 63.
Further, N of the optical glass d The consistency is + -50 multiplied by 10 -5 Within, preferably N d The consistency is + -30 multiplied by 10 -5 Is within; and/or T s Stability is within + -5deg.C, preferably T s The stability is within + -3 ℃.
Further, the sagging temperature T of the optical glass s 610 ℃ or lower, preferably 600 ℃ or lower, more preferably 595 ℃ or lower; and/or coefficient of thermal expansion alpha 20-300℃ 85X 10 -7 Hereinafter, 83×10 is preferable -7 Hereinafter, more preferably 81×10 -7 The following are set forth; and/or acid action resistance stability D A More than 5 types, preferably more than 4 types; and/or stability against water action D W More than 4 types, preferably more than 3 types; and/or the degree of air bubbles is a class A or more, preferably A 0 Above the stage, more preferably A 00 A stage; and/or the streak degree is C or more, preferably B or more; and/or a high temperature viscosity of 1200 ℃ of 25 dPascals or less, preferably 23 dPascals or less, more preferably 20 dPascals or less; and/or a high temperature viscosity of 35 dPascals or more, preferably 40 dPascals or more, more preferably 50 dPascals or more at 900 ℃; and/or the crystallization upper limit temperature is 1100 ℃ or lower, preferably 1050 ℃ or lower, more preferably 1020 ℃ or lower; and/or thermoplastic crystallization stability is above grade B, preferably grade A; and/or a refractive index temperature coefficient dn/dt of 6.0X10 or less -6 Preferably at a temperature of 5.5X10 or less -6 Preferably at a temperature of 5.0X10 or less -6 /℃。
And a glass preform made of the optical glass.
The optical element is made of the optical glass or the glass prefabricated member.
An optical instrument comprising the optical glass and/or comprising the optical element.
The beneficial effects of the invention are as follows: the optical glass obtained by the invention has lower content through reasonable component designSag temperature of N d Consistency and T s The stability is excellent.
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 is sometimes simply referred to as glass.
[ optical glass ]
The ranges of the respective components (ingredients) of the optical glass of the present invention are described below. In the present invention, unless otherwise specified, the content and the total content of each component are all expressed in weight percent (wt%), that is, the content and the total content of each component are expressed in weight percent with respect to the total amount of the 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 of the present invention is 100% when the oxide, the composite salt, the hydroxide, and the like are melted and decomposed and converted into oxide.
Unless otherwise indicated in a particular context, numerical ranges set forth herein include upper and lower limits, and "above" and "below" include the 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 used herein is inclusive, e.g. "a and/or B", meaning either a alone, B alone, or both a and B.
< essential Components and optional Components >
SiO 2 Is an essential component of the glass, and if the content exceeds 47%, the refractive index and Abbe number of the glass are lower than the design requirement; on the other hand, the melting temperature of the glass is rapidly increased, the melting difficulty is increased, particularly under the condition of containing a large amount of alkali metal oxide components, the erosion capability of the glass to a melting furnace is rapidly increased, and the service life of a furnace body is reduced and simultaneously, the melting difficulty is increasedN d Consistency, T s The difficulty in controlling stability can also bring the risk of rising the content of bubbles and inclusions in the glass, and even the quality requirement can not be met. If SiO is 2 The content of the glass is lower than 17%, the chemical stability of the glass is rapidly reduced, the water resistance is difficult to meet the design requirement, and fog defects are easy to generate on the surface when the aspheric prefabricated member is prepared and ground, so that the yield of the aspheric prefabricated member is reduced. Thus, siO 2 The content of (2) is 17 to 47%, preferably 22 to 40%, more preferably 25 to 38%.
B 2 O 3 Can raise refractive index and Abbe number of glass and reduce T of glass s . A suitable amount of B 2 O 3 At the same time with SiO 2 Meanwhile, when the glass network is formed, the strength of the glass network can be further improved, so that the chemical stability of the glass, especially the acid resistance of the glass, is further improved. If B 2 O 3 The content of (B) exceeds 50 percent 2 O 3 The glass network is loosened, resulting in a rapid decrease in water resistance. In the production process, B 2 O 3 The boric acid is usually introduced in the form of boric acid, and the inventor has found that the high content of boric acid accelerates the corrosion of a smelting furnace in the melting process; on the other hand, during the melting process, excessive boric acid can cause volatilization to be intensified, the glass component can be greatly changed, and N is caused d Consistency and T s The stability is rapidly reduced; in yet another aspect, boric acid is decomposed to H during melting 2 O，H 2 O is typically present in the form of bubbles in the high temperature glass, and excess boric acid can present a significant challenge to the subsequent fining process. If B 2 O 3 The content of (C) is less than 20%, the Abbe number and T of the glass s It is difficult to meet the design requirements. Thus B 2 O 3 The content of (2) is 20 to 50%, preferably 22 to 38%, more preferably 23 to 35%.
The inventors have found that, in the system glass of the present invention, B 2 O 3 /SiO 2 When the value of (2) is larger than 2.3, the time for cooling the glass liquid from the liquid state to the solid state at the forming temperature is greatly increased, and the surface is cooled and hardened in the forming process, but the temperature of the middle part is still higherThe surface and middle curing history are extremely different, stripes are easy to form in the glass, and the curing history is particularly serious for thick products. The glass of the system of the invention is usually molded at 900-1000 ℃, and if the viscosity is lower than 35dPas in the temperature range, the glass is easy to cause the problems, so that the streak degree can not meet the requirement. Thus B 2 O 3 /SiO 2 The value of (2) is preferably 2.3 or less, more preferably 2.0 or less, further preferably 1.8 or less, and still further preferably 1.5 or less. If B 2 O 3 /SiO 2 Has a value of less than 0.55, T of glass s The glass rises rapidly, the design target is difficult to achieve, and the high-temperature viscosity of the glass at 1200 ℃ is difficult to achieve. In some embodiments, the high temperature viscosity of the glass at 1200 ℃ is too high, the internal bubbles are difficult to remove from the glass, the temperature must be increased to effectively remove the bubbles, but the erosion capacity of the glass liquid above 1200 ℃ on the furnace body is rapidly increased. Thus B 2 O 3 /SiO 2 The value of (2) is preferably 0.55 or more, more preferably 0.7 or more, still more preferably 0.8 or more, and still more preferably 1.0 or more.
Proper amount of Al 2 O 3 Can strengthen the glass network, improve the chemical stability of the glass and improve the high-temperature viscosity of the glass. However, in the glass of the present invention, more than 8% of Al 2 O 3 Can lead to rapid loosening of network structure in glass, especially in B 2 O 3 Under the condition of higher content, corrosion points are easy to generate on the surface of the element in the grinding and polishing process of manufacturing the aspherical prefabricated part, so that the yield is rapidly reduced. In addition, due to Al 2 O 3 Larger dispersion of (c) and excessive inclusion may result in abbe numbers below design requirements. If the content is less than 0.5%, the corrosiveness of the glass raw material to the furnace body during the melting process is sharply increased, and the chemical stability, particularly the water resistance, is rapidly reduced. Thus, al 2 O 3 The content is limited to 0.5 to 8%, preferably 1 to 7%, more preferably 1 to 6.5%.
ZrO 2 The glass can reduce the capability of glass liquid to erode the furnace body, prolong the service life of the smelting furnace and improve the crystallization resistance of the glass. If ZrO 2 Is more than the content ofAnd 3, infusions easily appear in the glass, so that the internal quality of the glass is reduced, and the crystallization resistance of the glass is rapidly reduced. Thus, zrO 2 The content of (2) is 3% or less, preferably 2% or less, and more preferably 1% or less.
In some embodiments, zrO 2 With Al 2 O 3 When mixed, for B 2 O 3 The structural state has a great influence, especially in the case of high alkaline earth metal oxide content, so that the crystallization stability of the thermoplastic glass is influenced. When (ZrO 2 +Al 2 O 3 )/B 2 O 3 When the value of (C) is less than 0.05, the improvement of the crystallization stability of the thermoplastic is not remarkable, and if (ZrO 2 +Al 2 O 3 )/B 2 O 3 The value of (2) is greater than 0.4, and the thermoplastic crystallization resistance of the glass is rather rapidly lowered. Thus, (ZrO 2 +Al 2 O 3 )/B 2 O 3 The value of (2) is preferably 0.05 to 0.4, more preferably 0.05 to 0.3, still more preferably 0.05 to 0.25, and still more preferably 0.05 to 0.2.
The proper amount of ZnO can obviously improve the refractive index and chemical stability of the glass and reduce the thermal expansion coefficient and T of the glass s If the content is less than 0.5%, the above effects are not obvious; if the ZnO content is higher than 8%, the Abbe number of the glass is less likely to meet the design requirements, and the ability of the glass to eliminate bubbles is reduced, especially in B 2 O 3 In the case of higher content. Accordingly, the content of ZnO is limited to 0.5 to 8%, preferably 1 to 7%, more preferably 1 to 6%.
BaO, srO, caO, mgO is an alkaline earth metal oxide, and a proper amount of alkaline earth metal oxide can improve the refractive index in the glass and enhance the crystallization resistance of the glass, but if the total RO content exceeds 45%, the crystallization resistance of the glass is rapidly reduced, and even the glass is emulsified. Therefore, the total RO content of BaO, srO, caO, mgO is 6 to 45%, preferably 8 to 40%, more preferably 10 to 35%.
Through a great deal of experimental researches of the inventor, the BaO is larger than SrO and CaO is larger than MgO from the aspect of improving the crystallization resistance and stability of the glass. Thus, the glass of the present inventionBaO is preferably selected to improve the refractive index and crystallization resistance of the glass, but if the content exceeds 30%, the water resistance of the glass is rapidly reduced, bubbles are easily accumulated in the glass in the melting process, the bubbles are difficult to eliminate, the stability of the production process is seriously influenced, and the N of the glass is influenced d Consistency and T s Stability. If the BaO content is lower than 5%, the refractive index of the glass is hard to reach the design requirement, and the crystallization resistance of the glass is rapidly reduced. Therefore, the BaO content is 5 to 30%, preferably 6 to 28%, more preferably 8 to 25%.
SrO can form a synergistic effect with BaO in the glass, so that the crystallization resistance stability of the glass is more effectively improved, the refractive index of the glass is also improved, if the content of SrO is lower than 0.5%, the effect is not obvious, and if the content of SrO exceeds 15%, the crystallization resistance synergistic effect is weakened, and the cost of the glass is rapidly increased. Therefore, the SrO content is 0.5 to 15%, preferably 0.5 to 13%, and more preferably 0.5 to 12%.
The CaO can improve the crystallization resistance and the refractive index of the glass, and rapidly reduce the high-temperature viscosity of the glass, so that the bubble removal is relatively easier, and the effect is more obvious especially under the condition of lower relative BaO content. If the CaO content is higher than 10%, the crystallization resistance of the glass is rapidly reduced, and the Abbe number is lower than the design requirement. Therefore, the CaO content is 0 to 10%, preferably 0 to 9%, more preferably 0 to 8%.
MgO can improve the stability of the glass, and if the content of MgO is higher than 5%, the crystallization resistance of the glass is reduced rapidly, and the Abbe number is lower than the design requirement. Therefore, the MgO content is limited to 5% or less, preferably 3% or less, and more preferably no MgO is contained.
In some embodiments, the alkaline earth metal oxides of the glasses of the present invention are primarily BaO, and when the value of BaO/RO is preferably from 0.4 to 0.95, more preferably from 0.5 to 0.95, still more preferably from 0.65 to 0.95, still more preferably from 0.7 to 0.9, the synergy between the alkaline earth metal oxides is most pronounced for reducing the upper crystallization limit temperature of the glass.
In some embodiments, the free oxygen provided by the alkaline earth oxide willReinforcement B 2 O 3 Network, strengthen its compactness, thus promote the water resistance and weather resistance of glass, if RO/B 2 O 3 The above effect is not remarkable and the thermal expansion coefficient is increased, the value of (a) is lower than 0.3; if RO/B 2 O 3 The value of (2) is higher than 1.3, and the excessive alkaline earth metal component may adversely affect the glass network, and the water resistance and weather resistance of the glass rapidly deteriorate. Thus, RO/B 2 O 3 The value of (2) is preferably 0.3 to 1.3, more preferably 0.4 to 1.2, still more preferably 0.5 to 1.0, and still more preferably 0.6 to 0.9.
La 2 O 3 The refractive index of the glass can be improved, the high-temperature viscosity of the glass can be reduced, and if the content of the glass is lower than 0.5%, the effect is not obvious. If La is 2 O 3 The content exceeds 10 percent, the acid resistance of the glass is rapidly reduced, the thermoplastic crystallization resistance of the glass is rapidly reduced, and the T of the glass s Raised. Therefore La 2 O 3 The content of (2) is limited to 0.5 to 10%, preferably 1 to 9%, more preferably 1.5 to 8%.
Y 2 O 3 The refractive index and thermal shock resistance can be improved in glass, and if the content exceeds 8%, the chemical stability of the glass is rapidly reduced. Thus Y 2 O 3 The content of (2) is limited to 8% or less, preferably 5% or less, and more preferably 3% or less.
Gd 2 O 3 The refractive index, water resistance and weather resistance of the glass can be improved, but if the content exceeds 5%, the cost of the glass is rapidly increased, and the crystallization resistance is rapidly reduced. Thus Gd 2 O 3 The content of (2) is limited to 5% or less, preferably 3% or less, more preferably Gd-free 2 O 3 。
The time for cooling the glass from the high-temperature solution to the solid state is longer than that of the common optical glass, and the glass is required to be subjected to two high-temperature forming processes and excessive La 2 O 3 、Y 2 O 3 、Gd 2 O 3 The thermoplastic crystallization resistance of the glass is rapidly deteriorated, crystallization and even emulsification are generated in the thermoplastic process, and rapid decrease of acid resistance is caused. Therefore La 2 O 3 、Y 2 O 3 、Gd 2 O 3 Total content La 2 O 3 +Y 2 O 3 +Gd 2 O 3 Preferably 0.5 to 15%, more preferably 1 to 12%, and even more preferably 2 to 10%.
In some embodiments, a suitable amount of La 2 O 3 、Y 2 O 3 、Gd 2 O 3 The refractive index and Abbe number of the glass can be improved by being cooperated with RO, more importantly, the problem of water resistance reduction caused by the large amount of RO contained in the glass can be reduced, and meanwhile, the acid resistance is controlled within a design range, the high-temperature viscosity of the glass is reduced, and further, the melting temperature of the glass is reduced, when (La 2 O 3 +Y 2 O 3 +Gd 2 O 3 ) When the value of/RO is less than 0.05, the above effect is not remarkable. When (La) 2 O 3 +Y 2 O 3 +Gd 2 O 3 ) When the value of/RO is higher than 0.9, the corrosiveness of the molten glass to the furnace body is increased, the stability of the glass is rapidly deteriorated, T s Rising, being difficult to meet the design requirements. Thus, (La) 2 O 3 +Y 2 O 3 +Gd 2 O 3 ) The value of/RO is preferably 0.05 to 0.9, more preferably 0.1 to 0.6, still more preferably 0.1 to 0.4, still more preferably 0.1 to 0.35.
In some embodiments, when La is present in the glass 2 O 3 、Y 2 O 3 、Gd 2 O 3 When the components are equal, the stability of the glass is reduced, and tiny bubbles are easy to appear in the cooling process, so that the product is scrapped. The inventors have found from a great deal of experimental study that when ZnO and La 2 O 3 、Y 2 O 3 、Gd 2 O 3 Coexisting and satisfying ZnO/(La) 2 O 3 +Y 2 O 3 +Gd 2 O 3 ) When the value of (2) is in the range of 0.2 to 4.0, the stability and the bubble degree of the glass can be prevented from being lowered. Therefore, znO/(La) is preferable 2 O 3 +Y 2 O 3 +Gd 2 O 3 ) The value of (2) is 0.2 to 4.0, more preferably 0.3 to 3.0, still more preferably 0.5 to 2.0, still more preferably 0.6 to 1.6.
Alkali metal oxides (e.g. Li 2 O、Na 2 O、K 2 O) is one of the main components of the glass according to the invention, the content and the relative content being relative to the T of the glass s The key indexes such as refractive index, abbe number, thermal expansion coefficient, chemical stability and crystallization resistance are greatly influenced.
From the action of a single alkali metal oxide, li 2 O reduces glass T s If the content is less than 1%, T of the glass s The chemical stability of the glass is rapidly reduced and the high-temperature viscosity of the glass is rapidly increased when the glass is higher than the design requirement. If Li 2 The content of O exceeds 7 percent, the glass liquid not only rapidly enhances the corrosiveness of the furnace body, but also can erode platinum products in the melting process, so that platinum inclusions appear in the glass, and simultaneously the N of the glass d Consistency and T s The stability control difficulty is high. Thus Li 2 The content of O is 1 to 7%, preferably 2 to 6.5%, more preferably 3 to 5.5%.
Proper amount of Na 2 O can improve the melting property of the glass and reduce the T of the glass s The high-temperature viscosity of the glass is lowered, and if the content thereof is less than 0.1%, the above effect is not obvious. If Na is 2 The content of O is higher than 7%, the corrosiveness of the glass to the furnace body is increased, the chemical stability of the glass is reduced, and the thermal expansion coefficient is rapidly increased. Thus, na 2 The O content is 0.1 to 7%, preferably 0.1 to 6%, more preferably 0.5 to 5%.
K 2 If the content of O is higher than 5%, the damage of the network structure of the glass is serious, and the water resistance and weather resistance of the glass are difficult to meet the design requirements. Thus, K is 2 The content of O is limited to 5% or less, preferably 2% or less, and more preferably 1% or less.
The inventors have found that Li 2 O、Na 2 O、K 2 When three alkali metal oxides are mixed, a complex synergistic effect can occur, and the corrosiveness to a furnace body, the high-temperature viscosity and the refractive index temperature coefficient are further influenced. The use of aspherical lenses can greatly reduce the number of lenses used and realize high-definition imaging. But is relatively required toIf the refractive index temperature coefficient of the glass is too large and the number of lenses is small, the temperature drift of the lens is extremely difficult to control, and serious problems of different imaging quality at different temperatures can be brought. The inventors have found that in some embodiments, when Li 2 O+Na 2 O+K 2 The value of O is preferably less than 15%, more preferably less than 12%, even more preferably less than 10%, even more preferably less than 8%, and the aggressiveness of the molten glass to the furnace body is reduced, T s The stability meets the design requirement, and the refractive index temperature coefficient of the glass does not exceed the design requirement.
In some embodiments, when (Na 2 O+K 2 O)/Li 2 The value of O is preferably 0.1 to 1.5, more preferably 0.1 to 1.0, still more preferably 0.2 to 0.8, still more preferably 0.25 to 0.65, and the corrosiveness of the molten glass to the furnace body is reduced, T s The stability meets the design requirement, and the refractive index temperature coefficient of the glass does not exceed the design requirement. More importantly, if the three alkali metal oxides are in the range, a lower thermal expansion coefficient can be realized, which is very important for reducing the burst of the lens in the aspherical profiling process, and greatly improves the degree of freedom and the stability of the aspherical profiling process.
P 2 O 5 The refractive index and dispersion of the glass can be adjusted, but in the system glass of the present invention, if the content exceeds 3%, the crystallization resistance of the glass is rapidly deteriorated, and the critical processes such as continuous melting production of the glass, blank secondary press molding, and aspherical precision press molding are adversely affected, so that the content is limited to 3% or less, preferably 1.5% or less, more preferably, P is not contained 2 O 5 。
The proper amount of F (fluorine) can obviously reduce the T of the glass s The Abbe number of the glass is raised, and the use of alkali metal oxide in the glass can be reduced. If the content exceeds 10%, F is extremely volatile in the high-temperature melting process, and the unit content has a particularly large influence factor on refractive index and Abbe number, so that N is caused in the melting process d Consistency, T s Stability becomes extremely impossibleAnd the control can bring disastrous effects to the subsequent aspheric profiling. Accordingly, the content of F is controlled to 10% or less, preferably 5% or less, and more preferably 3% or less. If the component design can meet the requirement of T s Further preferably, F is not contained.
Sb 2 O 3 、SnO 2 、Na 2 SiF 6 、K 2 SiF 6 And the like, which are useful as a fining agent, are advantageous in improving the bubble degree of glass, and are present in an amount of 1% or less, preferably 0.8% or less, more preferably 0.5% or less, alone or in combination.
In addition to optimizing the melting performance of the glass and improving the bubble degree of the glass by component design, silicate glass with similar high viscosity also generally adopts an oxide component to optimize the melting performance and bubble degree of the glass in a nitrate introduction mode. The nitrate is almost completely dissolved in NO in the process of melting nitrogen element X The gas is discharged into the atmosphere, the nitrogen oxides have great harm to the health of human bodies, and long-term inhalation has the risk of lung cancer. Accordingly, the inventors have made an effort to investigate the problem of reducing emission of nitrogen oxides while securing glass melting properties. The inventor finds that the nitrate is in KNO through a plurality of experimental researches 3 And Ba (NO) 3 ) 2 Introduced in the same manner as the above-mentioned refining agent (such as Sb 2 O 3 、SnO 2 、Na 2 SiF 6 、K 2 SiF 6 Etc.), the emission of nitrogen oxides can be reduced to a lower level while the bubble degree of the glass can meet the quality requirement. By conversion, the N (nitrogen) element content in the glass raw material (the amount of N element introduced in melting 100Kg of theoretical glass per 100Kg of glass weight X100%) is less than 2.0%, preferably less than 1.5%, more preferably less than 1.0%.
< 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. Meanwhile, in order to achieve environmental friendliness, the optical glass of the present invention preferably does not contain As 2 O 3 And PbO.
The term "not containing" or "0%" as used herein means that the compound, molecule, element or the like is not intentionally added as a raw material to the optical glass of the present invention; 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 properties of the optical glass of the present invention will be described below:
< refractive index and Abbe number >
Refractive index (n) d ) With Abbe number (v) d ) Tested according to the method specified in GB/T7962.1-2010.
In some embodiments, the refractive index (n d ) Is 1.57 to 1.61, preferably a refractive index (n d ) Is 1.575 to 1.605, more preferably the refractive index (n d ) 1.575 to 1.60.
In some embodiments, the Abbe number (. Nu.) of the optical glass of the present invention d ) Is from 58 to 64, preferably Abbe number (. Nu.) of d ) From 58.5 to 63.5, more preferably Abbe number (. Nu. d ) 59 to 63.
<N d Consistency of>
In the production processIn the process, 5 glass samples are selected every 24 hours, and after annealing, the refractive index (N) is tested according to the method specified in GB/T7962.1-2010 d ) Calculating the difference between the standard value and the standard value to be N d Consistency.
In some embodiments, the optical glass of the present invention has N d The consistency is + -50 multiplied by 10 -5 Within, preferably N d The consistency is + -30 multiplied by 10 -5 Within the inner part.
< sagging temperature >
Sag temperature (T) of optical glass s ) The test was carried out according to the method prescribed in GB/T7962.16-2010.
In some embodiments, the sag temperature (T s ) Is below 610 ℃, preferably sagging temperature (T s ) At 600 ℃ or lower, more preferably sagging temperature (T s ) Is below 595 ℃.
<T s Stability of>
In the production process, 5 glass samples are selected every 24 hours, and T is regulated according to GB/T7962.16-2010 after annealing s The difference from the standard value represents T s Stability.
In some embodiments, the optical glass of the present invention has a T s Stability is within + -5deg.C, preferably T s The stability is within + -3 ℃.
< coefficient of thermal expansion >
Coefficient of thermal expansion (. Alpha.) of optical glass 20-300℃ ) The data of 20-300 ℃ are tested according to the method specified in GB/T7962.16-2010.
In some embodiments, the optical glass of the present invention has a coefficient of thermal expansion (α 20-300℃ ) 85X 10 -7 Hereinafter, the thermal expansion coefficient (. Alpha.) is preferable 20-300℃ ) 83X 10 -7 Hereinafter, the thermal expansion coefficient (. Alpha.) is more preferable 20-300℃ ) 81X 10 -7 The following is given.
< stability against acid action >
Acid action resistance stability of optical glass (D A ) (powder method) the test was carried out according to the method prescribed in GB/T17129. Herein, a method of manufacturing a semiconductor deviceAcid resistance stability is sometimes referred to simply as acid resistance.
In some embodiments, the acid action resistance stability (D A ) Above 5 kinds, acid resistance stability (D A ) More than 4 kinds.
< stability against Water action >
Stability against Water action of optical glass (D W ) (powder method) the test was carried out according to the method prescribed in GB/T17129. The stability to water action is sometimes referred to herein simply as water resistance.
In some embodiments, the water resistance stability (D W ) Above 4 kinds, preferably stability against water action (D W ) Is more than 3 kinds.
< bubble degree >
The bubble degree of the optical glass was measured according to the method prescribed in GB/T7962.8-2010.
In some embodiments, the optical glass of the present invention has a bubble degree of class A or more, preferably class A 0 Above the stage, more preferably A 00 A stage.
< streak degree >
The degree of streaking of the optical glass was examined by comparing it with a standard sample in the direction in which streaking was most easily seen with a streaking instrument comprising a point light source and a lens, and the results were classified into 4 classes, and are shown in Table 1 below.
TABLE 1 fringe level table
| Level of | Degree of streaking |
| A | No macroscopic streaks under defined detection conditions |
| B | Has fine and dispersed stripes under the specified detection conditions |
| C | With slight parallel streaks under defined detection conditions |
| D | Having coarse parallel stripes under defined detection conditions |
In some embodiments, the optical glass of the present invention has a degree of striae of C or more, preferably B or more.
< high temperature viscosity >
The high temperature viscosity of the optical glass was measured as follows: the measurement was carried out using a THETA Rheotronic II high temperature viscometer using a spin method, the numerical unit being dPaS (poise), the smaller the number, the lower the viscosity.
In some embodiments, the optical glass of the present invention has a high temperature viscosity of 25 dPascals or less at 1200 ℃, preferably 23 dPascals or less at 1200 ℃, and more preferably 20 dPascals or less at 1200 ℃.
In some embodiments, the optical glass of the present invention has a high temperature viscosity of 35 dPascals or more at 900 ℃, preferably 40 dPascals or more at 900 ℃, and more preferably 50 dPascals or more at 900 ℃.
< anti-devitrification Property >
For the glass applied to the aspheric precision press molding, the glass needs to undergo a high-temperature process of 3 stages such as high-temperature molding, high-temperature secondary press molding, high-temperature precision press molding and the like, so that the crystallization resistance stability of the glass is very important. The crystallization resistance is divided into two types, namely, the crystallization resistance of the glass liquid in the process of cooling from a liquid state to a solid state is represented by the crystallization upper limit temperature; the crystallization resistance of the high-temperature secondary compression and high-temperature precise compression can be characterized by a thermoplastic crystallization resistance test. References herein to devitrification resistance (or glass stability) are generally intended to refer to both types of devitrification resistance.
The crystallization resistance stability is divided into two types, namely, the crystallization resistance in the process of cooling glass liquid from a high-temperature (1000-1200 ℃) liquid state to a solid state is characterized by the crystallization upper limit temperature; the crystallization resistance of the high-temperature secondary compression and high-temperature precise compression can be characterized by a thermoplastic crystallization resistance test.
The crystallization upper limit temperature test method comprises the following steps: the crystallization performance of the glass is measured by adopting a gradient temperature furnace method, the glass is manufactured into a sample with the thickness of 180 multiplied by 10mm, the side surface is polished, the glass is put into a furnace with a temperature gradient (10 ℃/cm) and heated to the temperature of 1400 ℃ in the highest temperature zone, the glass is taken out to be naturally cooled to the room temperature after the temperature is kept for 4 hours, the crystallization condition of the glass is observed under a microscope, and the highest temperature corresponding to the occurrence of the crystallization of the glass is the crystallization upper limit temperature of the glass.
In some embodiments, the optical glass of the present invention has an upper crystallization limit temperature of 1100 ℃ or less, preferably 1050 ℃ or less, and more preferably 1020 ℃ or less.
The thermoplastic crystallization stability test method comprises the following steps: processing the test sample into 20×20×10mm specification, polishing both sides, and placing the sample at temperature T s The inside of the crystallization furnace at +200 ℃ was kept for 30 minutes, and after cooling, the two large surfaces were polished, and the crystallization performance of the glass was judged according to the following Table 2, with A being the best and E being the worst.
TABLE 2 grading and judgment criteria for devitrification
In some embodiments, the optical glass of the present invention has a thermoplastic crystallization-resistant stability of class B or more, preferably class a, and excellent crystallization-resistant properties.
< temperature coefficient of refractive index >
The refractive index temperature coefficient (dn/dt) of glass was measured according to the method prescribed in GB/T7962.4-2010The refractive index temperature coefficient of the optical glass was measured at 40 to 60℃and measured (d-line dn/dt relative (10) -6 /℃))
In some embodiments, the optical glass of the present invention has a refractive index temperature coefficient (dn/dt) of 6.0X10 -6 Preferably at a temperature of 5.5X10 or less -6 Preferably at a temperature of 5.0X10 or less -6 /℃。
[ method of production ]
The manufacturing method of the optical glass comprises the following steps: the glass of the invention is produced by adopting conventional raw materials and processes, including but not limited to oxide, hydroxide, fluoride, various salts (carbonate, nitrate, sulfate, phosphate, metaphosphate), boric acid and the like as raw materials, after being proportioned according to a conventional method, the proportioned furnace burden is put into a smelting furnace (such as a platinum, gold or platinum alloy crucible) with the temperature of 1400-1550 ℃ to be smelted, and after clarification and homogenization, homogeneous molten glass without bubbles and undissolved substances is obtained, and the molten glass is cast and annealed 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 direct drop molding, grinding, or compression molding such as hot press molding. That is, the glass preform may be produced by directly precision drop molding a molten optical glass into a glass precision preform, or by mechanical processing such as grinding and polishing, or by producing a preform for press molding from an optical glass, and then performing hot press molding and polishing on the preform. 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. The lens of the invention also comprises a car lamp lens.
[ optical instrument ]
The optical element formed by the optical glass of the invention can be used for manufacturing optical instruments, and the optical glass comprises but is not limited to photographic equipment, image pickup equipment, projection equipment, display equipment, vehicle-mounted equipment (including car lights), monitoring equipment 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.
In this example, optical glasses having compositions shown in tables 3 to 5 were obtained by using the above-described optical glass manufacturing method. The characteristics of each glass were measured by the test method of the present invention, and the measurement results are shown in tables 3 to 5.
Table 3.
/>
Table 4.
/>
Table 5.
/>
< example of glass preform >
The glasses obtained in examples 1 to 20 were subjected to polishing, re-hot press molding, and press molding such as precision press molding to prepare various kinds of lenses such as concave meniscus lenses, convex meniscus lenses, biconvex lenses, biconcave lenses, plano-convex lenses, and plano-concave lenses, and preforms such as prisms.
< 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 (48)
1. The optical glass is characterized by comprising the following components in percentage by weight: siO (SiO) 2 ：17～47％；B 2 O 3 ：20～50％；Al 2 O 3 ：0.5～8％；ZnO：0.5～8％；RO：6～45％；La 2 O 3 +Y 2 O 3 +Gd 2 O 3 ：0.5～15％；Li 2 O：1～7％；Na 2 O：0.1～7％，(Na 2 O+K 2 O)/Li 2 O is 0.25 to 0.65, (ZrO) 2 +Al 2 O 3 )/B 2 O 3 0.08 to 0.3, (La) 2 O 3 +Y 2 O 3 +Gd 2 O 3 ) and/RO is 0.05 to 0.49, wherein RO is BaO, srO, caO, mgO.
2. The optical glass according to claim 1, wherein the composition, expressed in weight percent, further comprises: p (P) 2 O 5 :0 to 3 percent; and/or ZrO 2 :0 to 3 percent; and/or K 2 O: 0-5%; and/or clarifying agent: 0 to 1 percent of clarifying agent which is Sb 2 O 3 、SnO 2 、Na 2 SiF 6 、K 2 SiF 6 One or more of the following.
3. An optical glass, characterized in that the components thereof are represented by weight percent and are composed of SiO 2 ：17～47％；B 2 O 3 ：20～50％；Al 2 O 3 ：0.5～8％；ZnO：0.5～8％；RO：6～45％；La 2 O 3 +Y 2 O 3 +Gd 2 O 3 ：0.5～15％；Li 2 O：1～7％；Na 2 O：0.1～7％；P 2 O 5 ：0～3％；ZrO 2 ：0～3％；K 2 O: 0-5%; clarifying agent: 0 to 1 percent of (Na) 2 O+K 2 O)/Li 2 O is 0.25 to 0.65, (ZrO) 2 +Al 2 O 3 )/B 2 O 3 0.08 to 0.3, (La) 2 O 3 +Y 2 O 3 +Gd 2 O 3 ) RO is 0.05-0.49, the RO is BaO, srO, caO, mgO, and the clarifying agent is Sb 2 O 3 、SnO 2 、Na 2 SiF 6 、K 2 SiF 6 One or more of the following.
4. An optical glass according to any one of claims 1 to 3, wherein the components thereof are expressed in weight percent, wherein: b (B) 2 O 3 /SiO 2 0.55 to 2.3.
5. An optical glass according to any one of claims 1 to 3, wherein the components thereof are expressed in weight percent, wherein: b (B) 2 O 3 /SiO 2 0.7 to 2.0.
6. An optical glass according to any one of claims 1 to 3, wherein the components thereof are expressed in weight percent, wherein: b (B) 2 O 3 /SiO 2 0.8 to 1.8.
7. An optical glass according to any one of claims 1 to 3, wherein the components thereof are expressed in weight percent, wherein: b (B) 2 O 3 /SiO 2 1.0 to 1.5.
8. An optical glass according to any one of claims 1 to 3, wherein the components thereof are expressed in weight percent, wherein: (ZrO 2 +Al 2 O 3 )/B 2 O 3 0.08 to 0.25.
9. An optical glass according to any one of claims 1 to 3, wherein the components thereof are expressed in weight percent, wherein: (ZrO 2 +Al 2 O 3 )/B 2 O 3 0.08 to 0.2.
10. An optical glass according to any one of claims 1 to 3, wherein the components thereof are expressed in weight percent, wherein: baO/RO is 0.4 to 0.95, and RO is BaO, srO, caO, mgO in total content.
11. An optical glass according to any one of claims 1 to 3, wherein the components thereof are expressed in weight percent, wherein: baO/RO is 0.5 to 0.95, and RO is BaO, srO, caO, mgO in total content.
12. An optical glass according to any one of claims 1 to 3, wherein the components thereof are expressed in weight percent, wherein: baO/RO is 0.65 to 0.95, and RO is BaO, srO, caO, mgO in total content.
13. An optical glass according to any one of claims 1 to 3, wherein the components thereof are expressed in weight percent, wherein: baO/RO is 0.7 to 0.9, and RO is BaO, srO, caO, mgO in total content.
14. An optical glass according to any one of claims 1 to 3, wherein the components thereof are expressed in weight percent, wherein: RO/B 2 O 3 The RO is a total content of BaO, srO, caO, mgO in an amount of 0.3 to 1.3.
15. An optical glass according to any one of claims 1 to 3, wherein the components thereof are expressed in weight percent, wherein: RO/B 2 O 3 The RO is a total content of BaO, srO, caO, mgO in an amount of 0.4 to 1.2.
16. An optical glass according to any one of claims 1 to 3, wherein the components thereof are expressed in weight percent, wherein: RO/B 2 O 3 The RO is a total content of BaO, srO, caO, mgO in an amount of 0.5 to 1.0.
17. According toAn optical glass according to any one of claims 1 to 3, characterized in that the components thereof are expressed in weight percent, wherein: RO/B 2 O 3 The RO is a total content of BaO, srO, caO, mgO in an amount of 0.6 to 0.9.
18. An optical glass according to any one of claims 1 to 3, wherein the components thereof are expressed in weight percent, wherein: (La) 2 O 3 +Y 2 O 3 +Gd 2 O 3 ) and/RO is 0.1 to 0.49, and the RO is BaO, srO, caO, mgO in total content.
19. An optical glass according to any one of claims 1 to 3, wherein the components thereof are expressed in weight percent, wherein: (La) 2 O 3 +Y 2 O 3 +Gd 2 O 3 ) and/RO is 0.1 to 0.4, wherein RO is BaO, srO, caO, mgO.
20. An optical glass according to any one of claims 1 to 3, wherein the components thereof are expressed in weight percent, wherein: (La) 2 O 3 +Y 2 O 3 +Gd 2 O 3 ) and/RO is 0.1 to 0.35, and the RO is BaO, srO, caO, mgO in total content.
21. An optical glass according to any one of claims 1 to 3, wherein the components thereof are expressed in weight percent, wherein: znO/(La) 2 O 3 +Y 2 O 3 +Gd 2 O 3 ) 0.2 to 4.0.
22. An optical glass according to any one of claims 1 to 3, wherein the components thereof are expressed in weight percent, wherein: znO/(La) 2 O 3 +Y 2 O 3 +Gd 2 O 3 ) 0.3 to 3.0.
23. An optical glass according to any one of claims 1 to 3, whereinThe components are expressed in weight percent, wherein: znO/(La) 2 O 3 +Y 2 O 3 +Gd 2 O 3 ) 0.5 to 2.0.
24. An optical glass according to any one of claims 1 to 3, wherein the components thereof are expressed in weight percent, wherein: znO/(La) 2 O 3 +Y 2 O 3 +Gd 2 O 3 ) 0.6 to 1.6.
25. An optical glass according to any one of claims 1 to 3, wherein the components thereof are expressed in weight percent, wherein: li (Li) 2 O+Na 2 O+K 2 O: less than 15%.
26. An optical glass according to any one of claims 1 to 3, wherein the components thereof are expressed in weight percent, wherein: li (Li) 2 O+Na 2 O+K 2 O: less than 12%.
27. An optical glass according to any one of claims 1 to 3, wherein the components thereof are expressed in weight percent, wherein: li (Li) 2 O+Na 2 O+K 2 O: less than 10%.
28. An optical glass according to any one of claims 1 to 3, wherein the components thereof are expressed in weight percent, wherein: li (Li) 2 O+Na 2 O+K 2 O: less than 8%.
29. An optical glass according to any one of claims 1 to 3, wherein the components thereof are expressed in weight percent, wherein: siO (SiO) 2 : 22-40%; and/or B 2 O 3 : 22-38%; and/or Al 2 O 3 :1 to 7 percent; and/or ZnO:1 to 7 percent; and/or RO: 8-40%; and/or La 2 O 3 +Y 2 O 3 +Gd 2 O 3 :1 to 12 percent; and/or Li 2 O：2～6.5％The method comprises the steps of carrying out a first treatment on the surface of the And/or Na 2 O:0.1 to 6 percent; and/or P 2 O 5 :0 to 1.5 percent; and/or ZrO 2 :0 to 2 percent; and/or K 2 O:0 to 2 percent; and/or clarifying agent: 0 to 0.8 percent, wherein the RO is BaO, srO, caO, mgO, and the clarifying agent is Sb 2 O 3 、SnO 2 、Na 2 SiF 6 、K 2 SiF 6 One or more of the following.
30. An optical glass according to any one of claims 1 to 3, wherein the components thereof are expressed in weight percent, wherein: siO (SiO) 2 : 25-38%; and/or B 2 O 3 : 23-35%; and/or Al 2 O 3 :1 to 6.5 percent; and/or ZnO:1 to 6 percent; and/or RO: 10-35%; and/or La 2 O 3 +Y 2 O 3 +Gd 2 O 3 : 2-10%; and/or Li 2 O:3 to 5.5 percent; and/or Na 2 O:0.5 to 5 percent; and/or ZrO 2 :0 to 1 percent; and/or K 2 O:0 to 1 percent; and/or clarifying agent: 0 to 0.5 percent, wherein the RO is BaO, srO, caO, mgO, and the clarifying agent is Sb 2 O 3 、SnO 2 、Na 2 SiF 6 、K 2 SiF 6 One or more of the following.
31. An optical glass according to any one of claims 1 to 3, wherein the components thereof are expressed in weight percent, wherein: baO: 5-30%; and/or SrO: 0.5-15%; and/or CaO: 0-10%; and/or MgO: 0-5%; and/or La 2 O 3 : 0.5-10%; and/or Y 2 O 3 : 0-8%; and/or Gd 2 O 3 ：0～5％。
32. An optical glass according to any one of claims 1 to 3, wherein the components thereof are expressed in weight percent, wherein: baO: 6-28%; and/or SrO:0.5 to 13 percent; and/or CaO: 0-9%; and/or MgO:0 to 3 percent; and/or La 2 O 3 :1 to 9 percent; and/or Y 2 O 3 : 0-5%; and/or Gd 2 O 3 ：0～3％。
33. An optical glass according to any one of claims 1 to 3, wherein the components thereof are expressed in weight percent, wherein: baO: 8-25%; and/or SrO: 0.5-12%; and/or CaO: 0-8%; and/or La 2 O 3 :1.5 to 8 percent; and/or Y 2 O 3 ：0～3％。
34. The optical glass according to claim 1 or 2, characterized in that it further comprises, in weight percent: f: 0-10%.
35. The optical glass according to claim 1 or 2, characterized in that it further comprises, in weight percent: f:0 to 5 percent.
36. The optical glass according to claim 1 or 2, characterized in that it further comprises, in weight percent: f:0 to 3 percent.
37. An optical glass according to any one of claims 1 to 3, wherein the composition does not contain P 2 O 5 The method comprises the steps of carrying out a first treatment on the surface of the And/or does not contain MgO; and/or does not contain Gd 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the And/or does not contain F.
38. An optical glass according to any one of claims 1 to 3, wherein the refractive index n of the optical glass d 1.57 to 1.61; abbe number v d 58 to 64.
39. An optical glass according to any one of claims 1 to 3, wherein the refractive index n of the optical glass d 1.575 to 1.605; abbe number v d 58.5 to 63.5.
40. A method according to any one of claims 1 to 3The optical glass of (2) is characterized in that the refractive index n of the optical glass d 1.575 to 1.60; abbe number v d 59 to 63.
41. An optical glass according to any one of claims 1 to 3, wherein the optical glass has N d The consistency is + -50 multiplied by 10 -5 Is within; and/or T s The stability is within + -5 ℃.
42. An optical glass according to any one of claims 1 to 3, wherein the optical glass has N d The consistency is + -30 multiplied by 10 -5 Is within; and/or T s The stability is within + -3 ℃.
43. An optical glass according to any one of claims 1 to 3, wherein the sagging temperature T of the optical glass s Is below 610 ℃; and/or coefficient of thermal expansion alpha 20-300℃ 85X 10 -7 The following are set forth; and/or acid action resistance stability D A More than 5 types; and/or stability against water action D W More than 4 types; and/or the bubble degree is above grade A; and/or the streak degree is above grade C; and/or a high temperature viscosity of below 25dPaS at 1200 ℃; and/or a high temperature viscosity of 35dPaS or more at 900 ℃; and/or the crystallization upper limit temperature is below 1100 ℃; and/or the thermoplastic crystallization resistance is above grade B; and/or a refractive index temperature coefficient dn/dt of 6.0X10 or less -6 /℃。
44. An optical glass according to any one of claims 1 to 3, wherein the sagging temperature T of the optical glass s Is below 600 ℃; and/or coefficient of thermal expansion alpha 20-300℃ 83X 10 -7 The following are set forth; and/or acid action resistance stability D A More than 4 types; and/or stability against water action D W More than 3 types; and/or the bubble degree is A 0 Above the stage; and/or the streak degree is above B grade; and/or a high temperature viscosity of less than 23dPaS at 1200 ℃; and/or a high temperature viscosity of 40dPaS or more at 900 ℃; and/or crystallization upper limit temperature is 1050 ℃ or lower The method comprises the steps of carrying out a first treatment on the surface of the And/or thermoplastic crystallization stability is class a; and/or a refractive index temperature coefficient dn/dt of 5.5X10 or less -6 /℃。
45. An optical glass according to any one of claims 1 to 3, wherein the sagging temperature T of the optical glass s Is below 595 ℃; and/or coefficient of thermal expansion alpha 20-300℃ 81X 10 -7 The following are set forth; and/or the bubble degree is A 00 A stage; and/or a high temperature viscosity of 20dPaS or less at 1200 ℃; and/or a high temperature viscosity of 50dPaS or more at 900 ℃; and/or crystallization upper limit temperature is below 1020 ℃; and/or a refractive index temperature coefficient dn/dt of 5.0X10 or less -6 /℃。
46. A glass preform produced by using the optical glass according to any one of claims 1 to 45.
47. An optical element, characterized in that it is produced by using the optical glass according to any one of claims 1 to 45 or the glass preform according to claim 46.
48. An optical instrument comprising the optical glass according to any one of claims 1 to 45 and/or the optical element according to claim 47.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210710690.4A CN114853336B (en) | 2022-06-22 | 2022-06-22 | Optical glass, glass preform, optical element, and optical instrument |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210710690.4A CN114853336B (en) | 2022-06-22 | 2022-06-22 | Optical glass, glass preform, optical element, and optical instrument |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114853336A CN114853336A (en) | 2022-08-05 |
| CN114853336B true CN114853336B (en) | 2023-09-05 |
Family
ID=82626149
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210710690.4A Active CN114853336B (en) | 2022-06-22 | 2022-06-22 | Optical glass, glass preform, optical element, and optical instrument |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114853336B (en) |
Citations (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS52124012A (en) * | 1976-04-12 | 1977-10-18 | Minolta Camera Kk | Optical glass |
| DE2952705B1 (en) * | 1979-12-29 | 1981-01-29 | Jenaer Glaswerk Schott & Gen | Optical glass with the optical position n? is 1.63 + - (1.5 times 10-2), v? is 59.5 + -1.0, with high chemical resistance and low tendency to crystallize, based on the known SiO2-B2O3-La2O3-SrO- system |
| JPH035341A (en) * | 1989-05-31 | 1991-01-11 | Hoya Corp | Optical glass |
| JPH0492834A (en) * | 1990-08-02 | 1992-03-25 | Sumita Kogaku Glass:Kk | Optical glass for precise press |
| JPH0812368A (en) * | 1994-06-30 | 1996-01-16 | Hoya Corp | Optical glass |
| JP2003089543A (en) * | 2001-09-13 | 2003-03-28 | Nippon Electric Glass Co Ltd | Optical glass for mold press forming |
| JP2003137589A (en) * | 2001-10-29 | 2003-05-14 | Nippon Electric Glass Co Ltd | Glass for mold press molding |
| JP2003176151A (en) * | 2001-12-13 | 2003-06-24 | Nippon Electric Glass Co Ltd | Optical glass for mold pressing |
| JP2005206425A (en) * | 2004-01-23 | 2005-08-04 | Omg Co Ltd | Borate glass for light irradiation, and lens |
| CN1692085A (en) * | 2002-11-08 | 2005-11-02 | Hoya株式会社 | Optical glass, preform for press molding and optical element |
| JP2007063071A (en) * | 2005-08-31 | 2007-03-15 | Hoya Corp | Optical glass, preform for precision press forming and method of manufacturing the same, optical device and method of manufacturing the same |
| JP2007169086A (en) * | 2005-12-20 | 2007-07-05 | Nippon Electric Glass Co Ltd | Optical glass for mold press forming |
| JP2007261877A (en) * | 2006-03-28 | 2007-10-11 | Hoya Corp | Optical glass, preform for precision press molding, optical element, and methods for producing them |
| CN101445322A (en) * | 2008-12-30 | 2009-06-03 | 成都光明光电股份有限公司 | Dense crown optical glass |
| CN101516793A (en) * | 2006-09-13 | 2009-08-26 | 旭硝子株式会社 | Optical glass |
| CN102476915A (en) * | 2010-11-23 | 2012-05-30 | 湖北新华光信息材料有限公司 | Environment-friendly low-melting-point optical glass |
| CN109250901A (en) * | 2018-11-19 | 2019-01-22 | 成都光明光电股份有限公司 | Optical glass, gas preform, optical element and optical instrument |
| CN110267923A (en) * | 2017-02-21 | 2019-09-20 | 株式会社小原 | Optical glass, preform material and optical element |
| CN111204970A (en) * | 2020-03-06 | 2020-05-29 | 成都光明光电股份有限公司 | Optical glass, glass preform and optical element |
| CN113415991A (en) * | 2021-07-28 | 2021-09-21 | 成都光明光电股份有限公司 | Optical glass and optical element |
| CN114590996A (en) * | 2016-12-07 | 2022-06-07 | 株式会社小原 | Optical glass, preform, and optical element |
-
2022
- 2022-06-22 CN CN202210710690.4A patent/CN114853336B/en active Active
Patent Citations (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS52124012A (en) * | 1976-04-12 | 1977-10-18 | Minolta Camera Kk | Optical glass |
| DE2952705B1 (en) * | 1979-12-29 | 1981-01-29 | Jenaer Glaswerk Schott & Gen | Optical glass with the optical position n? is 1.63 + - (1.5 times 10-2), v? is 59.5 + -1.0, with high chemical resistance and low tendency to crystallize, based on the known SiO2-B2O3-La2O3-SrO- system |
| JPH035341A (en) * | 1989-05-31 | 1991-01-11 | Hoya Corp | Optical glass |
| JPH0492834A (en) * | 1990-08-02 | 1992-03-25 | Sumita Kogaku Glass:Kk | Optical glass for precise press |
| JPH0812368A (en) * | 1994-06-30 | 1996-01-16 | Hoya Corp | Optical glass |
| US5744409A (en) * | 1994-06-30 | 1998-04-28 | Hoya Corporation | Optical glass |
| JP2003089543A (en) * | 2001-09-13 | 2003-03-28 | Nippon Electric Glass Co Ltd | Optical glass for mold press forming |
| JP2003137589A (en) * | 2001-10-29 | 2003-05-14 | Nippon Electric Glass Co Ltd | Glass for mold press molding |
| JP2003176151A (en) * | 2001-12-13 | 2003-06-24 | Nippon Electric Glass Co Ltd | Optical glass for mold pressing |
| CN1692085A (en) * | 2002-11-08 | 2005-11-02 | Hoya株式会社 | Optical glass, preform for press molding and optical element |
| JP2005206425A (en) * | 2004-01-23 | 2005-08-04 | Omg Co Ltd | Borate glass for light irradiation, and lens |
| JP2007063071A (en) * | 2005-08-31 | 2007-03-15 | Hoya Corp | Optical glass, preform for precision press forming and method of manufacturing the same, optical device and method of manufacturing the same |
| JP2007169086A (en) * | 2005-12-20 | 2007-07-05 | Nippon Electric Glass Co Ltd | Optical glass for mold press forming |
| JP2007261877A (en) * | 2006-03-28 | 2007-10-11 | Hoya Corp | Optical glass, preform for precision press molding, optical element, and methods for producing them |
| CN101516793A (en) * | 2006-09-13 | 2009-08-26 | 旭硝子株式会社 | Optical glass |
| CN101445322A (en) * | 2008-12-30 | 2009-06-03 | 成都光明光电股份有限公司 | Dense crown optical glass |
| CN102476915A (en) * | 2010-11-23 | 2012-05-30 | 湖北新华光信息材料有限公司 | Environment-friendly low-melting-point optical glass |
| CN114590996A (en) * | 2016-12-07 | 2022-06-07 | 株式会社小原 | Optical glass, preform, and optical element |
| CN110267923A (en) * | 2017-02-21 | 2019-09-20 | 株式会社小原 | Optical glass, preform material and optical element |
| CN109250901A (en) * | 2018-11-19 | 2019-01-22 | 成都光明光电股份有限公司 | Optical glass, gas preform, optical element and optical instrument |
| CN111204970A (en) * | 2020-03-06 | 2020-05-29 | 成都光明光电股份有限公司 | Optical glass, glass preform and optical element |
| CN113415991A (en) * | 2021-07-28 | 2021-09-21 | 成都光明光电股份有限公司 | Optical glass and optical element |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114853336A (en) | 2022-08-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112028475B (en) | Optical glass and optical element | |
| CN112028474B (en) | Optical glass | |
| CN112125511B (en) | Optical glass | |
| CN109626814B (en) | Environment-friendly optical glass, optical prefabricated member, optical element and optical instrument | |
| CN111533443A (en) | Optical glass | |
| CN112142321B (en) | Optical glass, optical element and optical instrument | |
| CN112939455B (en) | Optical glass, optical element and optical instrument | |
| CN113735438A (en) | Glass composition | |
| CN117756406A (en) | Optical glass, glass preform, optical element, and optical instrument | |
| CN110255887B (en) | Optical glass, optical element and optical instrument | |
| CN110372202B (en) | Optical glass, glass preform, optical element and optical instrument | |
| CN114853336B (en) | Optical glass, glass preform, optical element, and optical instrument | |
| CN115028354B (en) | Optical glass and optical element | |
| CN112125513B (en) | Optical glass and optical element | |
| CN112028472B (en) | Optical glass, optical element and optical instrument | |
| CN111333316B (en) | Optical glass, glass preform, optical element and optical instrument | |
| CN111320381B (en) | Optical glass, glass preform and optical element | |
| CN110240399B (en) | Optical glass | |
| CN111320382A (en) | Optical glass | |
| CN111204969A (en) | Optical glass, glass preform, optical element and optical instrument | |
| CN115745398B (en) | Glass composition | |
| CN115231818B (en) | Optical glass, glass preform and optical element | |
| CN111533446B (en) | Optical glass, glass preform, optical element and optical instrument | |
| CN115246707B (en) | Optical glass, optical element and optical instrument | |
| CN114907010B (en) | Optical glass |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |