CN115028353B - Optical glass with negative anomalous dispersion - Google Patents

Optical glass with negative anomalous dispersion Download PDF

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CN115028353B
CN115028353B CN202210710068.3A CN202210710068A CN115028353B CN 115028353 B CN115028353 B CN 115028353B CN 202210710068 A CN202210710068 A CN 202210710068A CN 115028353 B CN115028353 B CN 115028353B
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optical glass
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glass
anomalous dispersion
sio
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CN115028353A (en
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匡波
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Cdgm LLC
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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
    • 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

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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 an optical glass with negative anomalous dispersion, which comprises the following components in percentage by weight: siO (SiO) 2 ：20～45％；B 2 O 3 ：20～40％；Nb 2 O 5 ：5～25％；ZrO 2 ：2～20％；Na 2 O: 1-15%; baO:0 to 10%, wherein (Nb) 2 O 5 +Na 2 O+BaO)/B 2 O 3 0.5 to 1.5. Through reasonable component design, the optical glass obtained by the invention has negative anomalous dispersion and lower thermal expansion coefficient, and meets the application of high-end photoelectric products.

Description

Optical glass with negative anomalous dispersion
Technical Field
The invention relates to optical glass, in particular to optical glass with negative anomalous dispersion.
Background
In recent years, with the rapid development of photoelectric products such as smart phones, single-lens reflex cameras, monitoring security protection and the like, optical glass with a refractive index of 1.57-1.67 and an Abbe number of 38-48 has been widely used. In order to improve the degree of freedom in designing an optical system, it is expected that an optical glass has various different properties, and therefore an optical glass having properties suitable for eliminating or eliminating as much as possible the residual chromatic aberration of the secondary spectrum, particularly an optical glass having a low relative partial dispersion (P g,F ) And negative anomalous dispersion optical glass.
CN101549955a discloses an optical glass with refractive index of 1.59-1.71 and abbe number of 30-43, which contains 45-60 wt% of PbO, and does not meet the requirement of environmental protection nor have negative anomalous dispersion. CN107663011a discloses an optical glass with a refractive index of 1.60-1.70 and an abbe number of 40-50, which also does not have negative anomalous dispersion. On the other hand, the optical glass is easy to break in the processing process due to the large thermal expansion coefficient, so that the yield of glass processing is reduced. On the other hand, a larger thermal expansion coefficient may lead to deterioration of the thermal shock resistance of the glass, thereby limiting the application of the optical glass.
Therefore, the development of the optical glass with lower thermal expansion coefficient, refractive index of 1.57-1.67, abbe number of 38-48 and negative anomalous dispersion has important significance for the development of the photoelectric field.
Disclosure of Invention
The invention aims to provide optical glass with low expansion coefficient and negative anomalous dispersion.
The technical scheme adopted for solving the technical problems is as follows:
(1) An optical glass having negative anomalous dispersion, comprising, in weight percent: siO (SiO) 2 ：20～45％；B 2 O 3 ：20～40％；Nb 2 O 5 ：5～25％；ZrO 2 ：2～20％；Na 2 O: 1-15%; baO:0 to 10%, wherein (Nb) 2 O 5 +Na 2 O+BaO)/B 2 O 3 0.5 to 1.5.
(2) The optical glass with negative anomalous dispersion according to (1), wherein the components thereof are represented by weight percent, further comprising: mgO: 0-5%; and/or CaO: 0-10%; and/or SrO: 0-5%; and/or Li 2 O: 0-5%; and/or K 2 O: 0-10%; and/or WO 3 : 0-5%; and/or Ta 2 O 5 : 0-12%; and/or TiO 2 : 0-5%; and/or ZnO: 0-5%; and/or Ln 2 O 3 : 0-8%; and/or Al 2 O 3 : 0-5%; and/or GeO 2 : 0-5%; and/or clarifying agent: 0 to 1 percent of Ln, the Ln 2 O 3 Is La (La) 2 O 3 、Gd 2 O 3 、Y 2 O 3 、Yb 2 O 3 、Lu 2 O 3 One or more of the clarifying agents is Sb 2 O 3 、SnO、SnO 2 、CeO 2 One or more of the following.
(3) Optical glass with negative anomalous dispersion, its component contains SiO 2 、B 2 O 3 、Nb 2 O 5 、ZrO 2 And an alkali metal oxide containing 0 to 10% by weight of BaO, wherein (Nb) 2 O 5 +Na 2 O+BaO)/B 2 O 3 0.5 to 1.5, the refractive index n of the optical glass with negative anomalous dispersion d Is 1.57 to 1.67, abbe number v d At a relative partial dispersion P of 38 to 48 g,F A relative partial dispersion deviation value DeltaP of 0.7000 or less g,F Is-0.0050 or less, and the thermal expansion coefficient alpha 100/300℃ 95X 10 -7 and/K or below.
(4) The method according to (3)The optical glass with negative anomalous dispersion comprises the following components in percentage by weight: siO (SiO) 2 : 20-45%; and/or B 2 O 3 : 20-40%; and/or Nb 2 O 5 : 5-25%; and/or ZrO 2 : 2-20%; and/or Na 2 O: 1-15%; and/or MgO: 0-5%; and/or CaO: 0-10%; and/or SrO: 0-5%; and/or Li 2 O: 0-5%; and/or K 2 O: 0-10%; and/or WO 3 : 0-5%; and/or Ta 2 O 5 : 0-12%; and/or TiO 2 : 0-5%; and/or ZnO: 0-5%; and/or Ln 2 O 3 : 0-8%; and/or Al 2 O 3 : 0-5%; and/or GeO 2 : 0-5%; and/or clarifying agent: 0 to 1 percent of Ln, the Ln 2 O 3 Is La (La) 2 O 3 、Gd 2 O 3 、Y 2 O 3 、Yb 2 O 3 、Lu 2 O 3 One or more of the clarifying agents is Sb 2 O 3 、SnO、SnO 2 、CeO 2 One or more of the following.
(5) The optical glass having negative anomalous dispersion according to any of (1) to (4), wherein the components thereof in weight percent satisfy one or more of the following 9 cases:
1)B 2 O 3 /SiO 2 from 0.51 to 1.6, preferably B 2 O 3 /SiO 2 From 0.6 to 1.5, more preferably B 2 O 3 /SiO 2 From 0.7 to 1.2, more preferably B 2 O 3 /SiO 2 0.75 to 1.0;
2)Nb 2 O 5 /B 2 O 3 is 0.15 to 1.0, preferably Nb 2 O 5 /B 2 O 3 Is 0.2 to 0.9, more preferably Nb 2 O 5 /B 2 O 3 From 0.3 to 0.8, nb being more preferred 2 O 5 /B 2 O 3 0.4 to 0.7;
3)B 2 O 3 /(Nb 2 O 5 +ZrO 2 ) From 0.5 to 2.5, preferably B 2 O 3 /(Nb 2 O 5 +ZrO 2 ) From 0.6 to 2.0, more preferably B 2 O 3 /(Nb 2 O 5 +ZrO 2 ) From 0.7 to 1.5, further preferably B 2 O 3 /(Nb 2 O 5 +ZrO 2 ) 0.8 to 1.3;
4)CaO/ZrO 2 at most 2.0, caO/ZrO is preferable 2 From 0.05 to 1.5, more preferably CaO/ZrO 2 From 0.1 to 1.0, caO/ZrO being more preferable 2 0.1 to 0.8;
5)(SiO 2 +BaO)/B 2 O 3 is 0.6 to 2.0, preferably (SiO) 2 +BaO)/B 2 O 3 Is 0.7 to 1.8, more preferably (SiO) 2 +BaO)/B 2 O 3 Is 0.8 to 1.6, more preferably (SiO) 2 +BaO)/B 2 O 3 1.0 to 1.5;
6)(Nb 2 O 5 +Na 2 O+BaO)/B 2 O 3 is 0.65 to 0.95, preferably (Nb) 2 O 5 +Na 2 O+BaO)/B 2 O 3 Is 0.7 to 0.95, more preferably (Nb) 2 O 5 +Na 2 O+BaO)/B 2 O 3 0.7 to 0.9;
7)CaO/K 2 o is 0.1 to 5.0, preferably CaO/K 2 O is 0.3 to 3.0, more preferably CaO/K 2 O is 0.5 to 2.5, and CaO/K is more preferable 2 O is 0.8-2.0;
8)(CaO+K 2 O)/SiO 2 is 0.05 to 0.8, preferably (CaO+K) 2 O)/SiO 2 Is 0.05 to 0.6, more preferably (CaO+K) 2 O)/SiO 2 Is 0.1 to 0.5, more preferably (CaO+K) 2 O)/SiO 2 0.1 to 0.4;
9)(Li 2 O+Na 2 O+K 2 O)/B 2 O 3 is 0.1 to 1.5, preferably (Li) 2 O+Na 2 O+K 2 O)/B 2 O 3 Is 0.15 to 1.0, more preferably (Li) 2 O+Na 2 O+K 2 O)/B 2 O 3 Is 0.2 to 0.9, more preferably (Li) 2 O+Na 2 O+K 2 O)/B 2 O 3 0.25 to 0.7.
(6) The optical glass having negative anomalous dispersion according to any of (1) to (4), wherein the components are represented by weight percent: siO (SiO) 2 :25 to 40%, preferably SiO 2 : 28-38%; and/or B 2 O 3 :21 to 35%, preferably B 2 O 3 : 23-30%; and/or Nb 2 O 5 :8 to 20%, preferably Nb 2 O 5 : 10-18%; and/or ZrO 2 :5 to 18%, preferably ZrO 2 : 7-15%; and/or Na 2 O:3 to 13%, preferably Na 2 O: 5-12%; and/or MgO: 0-2%, preferably MgO:0 to 1 percent; and/or CaO:0.5 to 8%, preferably CaO:1 to 6 percent; and/or SrO: 0-2%, preferably SrO:0 to 1 percent; and/or BaO: 0-5%, preferably BaO:0 to 3 percent; and/or Li 2 O:0 to 3%, preferably Li 2 O:0 to 2 percent; and/or K 2 O:0.5 to 8%, preferably K 2 O:1 to 6 percent; and/or WO 3 :0 to 3%, preferably WO 3 :0 to 1 percent; and/or Ta 2 O 5 :0 to 5%, preferably Ta 2 O 5 :0 to 1 percent; and/or TiO 2 :0 to 1 percent; and/or ZnO:0 to 3%, preferably ZnO:0 to 1 percent; and/or Ln 2 O 3 :0 to 4%, preferably Ln 2 O 3 :0 to 1 percent; and/or Al 2 O 3 :0 to 3%, preferably Al 2 O 3 :0 to 1 percent; and/or GeO 2 :0 to 3%, preferably GeO 2 :0 to 1 percent; and/or clarifying agent: 0 to 0.8%, preferably a clarifying agent: 0 to 0.5 percent of Ln, the Ln 2 O 3 Is La (La) 2 O 3 、Gd 2 O 3 、Y 2 O 3 、Yb 2 O 3 、Lu 2 O 3 One or more of the clarifying agents is Sb 2 O 3 、SnO、SnO 2 、CeO 2 One or more of the following.
(7) The optical glass having negative anomalous dispersion according to any one of (1) to (4), wherein the component does not contain TiO 2 The method comprises the steps of carrying out a first treatment on the surface of the And/or does not contain WO 3 The method comprises the steps of carrying out a first treatment on the surface of the And/or does not contain Ta 2 O 5 The method comprises the steps of carrying out a first treatment on the surface of the And/or does not contain GeO 2 The method comprises the steps of carrying out a first treatment on the surface of the And/or contain no ZnO; and/or does not containLn 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the And/or does not contain Al 2 O 3 The Ln is 2 O 3 Is La (La) 2 O 3 、Gd 2 O 3 、Y 2 O 3 、Yb 2 O 3 、Lu 2 O 3 One or more of the following.
(8) The optical glass having negative anomalous dispersion according to any one of (1) to (4), wherein the refractive index n of the optical glass d From 1.57 to 1.67, preferably from 1.58 to 1.65, more preferably from 1.60 to 1.64, and/or Abbe number v d 38 to 48, preferably 41 to 47, more preferably 42 to 46.
(9) The relative partial dispersion P of an optical glass having negative anomalous dispersion according to any one of (1) to (4) g,F Is 0.7000 or less, preferably 0.6500 or less, more preferably 0.6000 or less, and/or a relative partial dispersion deviation ΔP g,F Is-0.0050 or less, preferably-0.0060 or less, more preferably-0.0065 or less.
(10) The optical glass having negative anomalous dispersion according to any one of (1) to (4), which has a density ρ of 3.0g/cm 3 Hereinafter, it is preferably 2.90g/cm 3 Hereinafter, it is more preferably 2.85g/cm 3 The following are set forth; and/or coefficient of thermal expansion alpha 100/300℃ 95X 10 -7 Preferably 90X 10, and K is less than or equal to -7 Preferably not more than/K, more preferably 85X 10 -7 and/K or below; and/or transition temperature T g 560 ℃ or lower, preferably 550 ℃ or lower, more preferably 540 ℃ or lower; and/or lambda 80 Less than or equal to 390nm, preferably lambda 80 Less than or equal to 380nm, more preferably lambda 80 Less than or equal to 370nm; and/or lambda 5 Less than or equal to 350nm, preferably lambda 5 Less than or equal to 340nm, more preferably lambda 5 Less than or equal to 330nm; and/or weather resistance CR is 2 or more, preferably 1; and/or knoop hardness H K Is 450 multiplied by 10 7 Pa or more, preferably 480×10 7 Pa or more, more preferably 500×10 7 Pa or more; and/or abrasion degree F A From 80 to 130, preferably from 90 to 120, more preferably from 95 to 115.
(11) A glass preform produced by using the optical glass having negative anomalous dispersion according to any one of (1) to (10).
(12) An optical element made of the optical glass having negative anomalous dispersion according to any of claims (1) to (10), or made of the glass preform according to (11).
(13) An optical instrument comprising the optical glass having negative anomalous dispersion according to any one of (1) to (10), and/or the optical element according to (12).
The beneficial effects of the invention are as follows: through reasonable component design, the optical glass obtained by the invention has negative anomalous dispersion and lower thermal expansion coefficient, and meets the application of high-end photoelectric products.
Detailed Description
The embodiments of the optical glass having negative anomalous dispersion according to the present invention will be described in detail below, but the present invention is not limited to the embodiments described below, and can be implemented with appropriate modifications within the scope of the object of the present invention. In the description of the repetitive description, the optical glass having negative anomalous dispersion according to the present invention is sometimes referred to simply as an optical glass or glass, although description thereof is omitted appropriately, but the gist of the present invention is not limited thereto.
[ optical glass having negative anomalous Dispersion ]
The ranges of the respective components (ingredients) of the optical glass having negative anomalous dispersion according to 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, the 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 Has the effects of improving the chemical stability of glass, maintaining the viscosity suitable for melting glass and reducing the erosion of refractory materials, and the glass is prepared by the method of the invention by containing more than 20 percent of SiO 2 To obtain the above effect, siO is preferred 2 The content of (C) is 25% or more, more preferably SiO 2 The content of (2) is 28% or more. If SiO is 2 Is excessively high, the difficulty in melting the glass increases, and ZrO in the composition 2 Is disadvantageous in melting. Thus, siO in the present invention 2 The upper limit of the content of (c) is 45%, preferably 40%, more preferably 38%.
B 2 O 3 Is favorable for reducing the short-wave special dispersion of the glass, so that the glass has better negative anomalous dispersion performance. If B 2 O 3 The content of (2) is lower than 20%, the high-temperature viscosity of the glass is higher, the melting performance is poorer, and the negative anomalous dispersion is difficult to reach the design requirement. If B 2 O 3 The content of (2) is higher than 40%, and the chemical stability of the glass is deteriorated, and the glass is liable to devitrify. Thus B 2 O 3 The content of (2) is 20 to 40%, preferably 21 to 35%, more preferably 23 to 30%.
The inventors have found through extensive experimental investigation that in some embodiments, B will be 2 O 3 Content of (2) and SiO 2 Ratio B between the contents of (2) 2 O 3 /SiO 2 Controlled within the range of 0.51-1.6, and the glass P is reduced g,F Value sum delta P g,F While at the same time a lower transition temperature is advantageously obtained. Therefore, B is preferred 2 O 3 /SiO 2 From 0.51 to 1.6, more preferably B 2 O 3 /SiO 2 0.6 to 1.5. Further, will B 2 O 3 /SiO 2 Controlled within the range of 0.7-1.2, and is also beneficial to the glass to obtain proper glassThe abrasion degree is improved, and meanwhile, the hardness of the glass is improved. Therefore, B is further preferable 2 O 3 /SiO 2 From 0.7 to 1.2, more preferably B 2 O 3 /SiO 2 0.75 to 1.0.
Nb 2 O 5 Is a high-refraction high-dispersion component, can improve the refractive index and devitrification resistance of the glass, reduces the thermal expansion coefficient of the glass and does not obviously improve P g,F Value sum delta P g,F The value of Nb is 5% or more in the present invention 2 O 5 To obtain the above effect, nb is preferable 2 O 5 The lower limit of the content of (2) is 8%, and more preferably the lower limit is 10%. If Nb is 2 O 5 The content of Nb exceeds 25%, the heat stability and weather resistance of the glass are lowered, and the light transmittance is lowered, so Nb in the present invention 2 O 5 The upper limit of the content of (2) is 25%, preferably 20%, more preferably 18%.
In some embodiments, by adding Nb to the alloy 2 O 5 Content of (B) and B 2 O 3 Ratio Nb between the contents of (C) 2 O 5 /B 2 O 3 The control of the glass P is in the range of 0.15 to 1.0, and the glass P can be reduced g,F Value sum delta P g,F The value of the light transmittance of the glass is prevented from being reduced. Therefore, nb is preferable 2 O 5 /B 2 O 3 Is 0.15 to 1.0, more preferably Nb 2 O 5 /B 2 O 3 0.2 to 0.9. Further, when Nb 2 O 5 /B 2 O 3 In the range of 0.3 to 0.8, it is also advantageous to lower the thermal expansion coefficient and the transformation temperature of the glass. Therefore, nb is more preferable 2 O 5 /B 2 O 3 From 0.3 to 0.8, nb being more preferred 2 O 5 /B 2 O 3 0.4 to 0.7.
ZrO 2 Can improve the refractive index of the glass, adjust the shortwave special dispersion and reduce the delta P of the glass g,F The glass has improved crystallization resistance and strength, and the glass contains ZrO 2% or more 2 To obtain the above effects, preferably containing ZrO 5% or more 2 More preferably, zrO is contained in an amount of 7% or more 2 . If ZrO 2 The content of (2) is higher than 20%, the difficulty of glass melting is increased, the melting temperature is increased, and impurities appear in the glass and the light transmittance is reduced. Thus, zrO 2 The content of (2) is 20% or less, preferably 18% or less, and more preferably 15% or less.
In some embodiments, B 2 O 3 Content of (2) and Nb 2 O 5 And ZrO(s) 2 Is the sum of Nb 2 O 5 +ZrO 2 Ratio B between 2 O 3 /(Nb 2 O 5 +ZrO 2 ) The control of the glass within the range of 0.5 to 2.5 can lead the glass to have lower P g,F Value sum delta P g,F While preventing an increase in glass density. Therefore, B is preferred 2 O 3 /(Nb 2 O 5 +ZrO 2 ) From 0.5 to 2.5, more preferably B 2 O 3 /(Nb 2 O 5 +ZrO 2 ) 0.6 to 2.0. Further, let B 2 O 3 /(Nb 2 O 5 +ZrO 2 ) In the range of 0.7 to 1.5, the weather resistance and the air bubble degree of the glass are also improved. Therefore, B is further preferable 2 O 3 /(Nb 2 O 5 +ZrO 2 ) From 0.7 to 1.5, more preferably B 2 O 3 /(Nb 2 O 5 +ZrO 2 ) 0.8 to 1.3.
MgO can lower the refractive index and melting temperature of the glass, but when the MgO content is excessive, the crystallization resistance and stability of the glass are reduced, and the cost of the glass is increased. Therefore, the MgO content is limited to 0 to 5%, preferably 0 to 2%, more preferably 0 to 1%.
CaO contributes to adjusting the optical constants of the glass, improving the processability of the glass, and reducing the density of the glass, but when the CaO content is too large, the crystallization resistance of the glass is deteriorated. Therefore, the CaO content is limited to 0 to 10%, preferably 0.5 to 8%, more preferably 1 to 6%.
In some embodiments, the CaO is added to the ZrO by mixing the CaO content with the ZrO 2 Ratio between the contents of CaO/ZrO 2 The glass has a suitable abrasion degree and is prevented from being separated out while being controlled to be less than 2.0The crystal properties are deteriorated. Therefore, caO/ZrO is preferable 2 Is 2.0 or less. Further, by controlling CaO/ZrO 2 In the range of 0.05 to 1.5, the weather resistance and alkali resistance of the glass are also improved. Therefore, caO/ZrO is more preferable 2 From 0.05 to 1.5, caO/ZrO being more preferable 2 From 0.1 to 1.0, caO/ZrO being more preferable 2 0.1 to 0.8.
SrO can adjust the refractive index and abbe number of the glass, but if the content is too large, the chemical stability of the glass is lowered, and the cost of the glass is also rapidly increased. Therefore, the SrO content is limited to 0 to 5%, preferably 0 to 2%, more preferably 0 to 1%.
BaO can improve devitrification resistance and hardness of the glass and lower the refractive index temperature coefficient and thermal expansion coefficient of the glass, but its high content causes deterioration of weather resistance and chemical stability of the glass, and therefore, the content of BaO is 0 to 10%, preferably 0 to 5%, more preferably 0 to 3%.
In some embodiments, siO 2 And the total content of BaO SiO 2 +BaO and B 2 O 3 Ratio between the contents of (SiO) 2 +BaO)/B 2 O 3 The glass transition temperature can be prevented from rising while optimizing the hardness and abrasion of the glass by controlling the glass transition temperature to be in the range of 0.6 to 2.0. Therefore, it is preferable that (SiO 2 +BaO)/B 2 O 3 Is 0.6 to 2.0, more preferably (SiO) 2 +BaO)/B 2 O 3 Is 0.7 to 1.8, more preferably (SiO) 2 +BaO)/B 2 O 3 Is 0.8 to 1.6, more preferably (SiO) 2 +BaO)/B 2 O 3 1.0 to 1.5.
Li 2 O can lower the glass transition temperature, adjust the high temperature viscosity of the glass, improve the meltability of the glass, but is unfavorable for the glass melting stability and the cost economy when the content is high. Thus, li in the present invention 2 The content of O is 5% or less, preferably 3% or less, and more preferably 2% or less.
Na 2 O has the function of improving glass melting property, can improve glass melting effect, and simultaneously is helpful for reducing P of glass g,F Value sum delta P g,F Value of Na 2 O content exceeding 15%, chemical stability and weather resistance of the glass are reduced, so Na 2 The content of O is 1-15%, preferably Na 2 The content of O is 3 to 13%, more preferably Na 2 The content of O is 5-12%.
In some embodiments, nb is 2 O 5 、Na 2 Total content of O and BaO Nb 2 O 5 +Na 2 O+BaO and B 2 O 3 Ratio between the contents of (Nb) 2 O 5 +Na 2 O+BaO)/B 2 O 3 The control is in the range of 0.5 to 1.5, and the P of the glass can be reduced g,F Value sum delta P g,F While reducing the coefficient of thermal expansion of the glass. Therefore, it is preferable that (Nb 2 O 5 +Na 2 O+BaO)/B 2 O 3 0.5 to 1.5. Further, (Nb) 2 O 5 +Na 2 O+BaO)/B 2 O 3 The control of the glass is within the range of 0.65-0.95, and the hardness and weather resistance of the glass are improved. Therefore, more preferable is (Nb 2 O 5 +Na 2 O+BaO)/B 2 O 3 Is 0.65 to 0.95, more preferably (Nb) 2 O 5 +Na 2 O+BaO)/B 2 O 3 Is 0.7 to 0.95, more preferably (Nb) 2 O 5 +Na 2 O+BaO)/B 2 O 3 0.7 to 0.9.
K 2 O has an effect of improving the thermal stability and meltability of the glass, but if it is contained in an amount exceeding 10%, the devitrification resistance and chemical stability of the glass are deteriorated. Thus, in the present invention K 2 The content of O is less than 10%, preferably K 2 The O content is 0.5 to 8%, more preferably 1 to 6%.
In some embodiments, the CaO content is related to K 2 Ratio between O contents CaO/K 2 O is controlled within the range of 0.1-5.0, so that the crystallization resistance of the glass is improved, and the density of the glass is reduced. Therefore, caO/K is preferable 2 O is 0.1 to 5.0, more preferably CaO/K 2 O is 0.3-3.0. Further, caO/K is added 2 O is controlled within the range of 0.5-2.5, which is favorable for reducing the thermal expansion coefficient of glass and optimizing the glassThe streak degree of the glass. Therefore, caO/K is further preferable 2 O is 0.5 to 2.5, and CaO/K is more preferable 2 O is 0.8-2.0.
In some embodiments, caO and K 2 Total content of O CaO+K 2 O and SiO 2 The ratio between the contents of (CaO+K) 2 O)/SiO 2 The abrasion degree and the streak degree of the glass can be controlled within the range of 0.05 to 0.8. Therefore, (CaO+K) is preferable 2 O)/SiO 2 Is 0.05 to 0.8, more preferably (CaO+K) 2 O)/SiO 2 0.05 to 0.6. Further, (CaO+K) 2 O)/SiO 2 The control is in the range of 0.1-0.5, and is also beneficial to improving the light transmittance and hardness of the glass. Therefore, (CaO+K) is more preferable 2 O)/SiO 2 From 0.1 to 0.5, more preferably (CaO+K) 2 O)/SiO 2 0.1 to 0.4.
In some embodiments, the total content of alkali metal oxides, li 2 O+Na 2 O+K 2 O and B 2 O 3 Ratio between the contents of (Li) 2 O+Na 2 O+K 2 O)/B 2 O 3 The light transmittance of the glass can be improved while the transition temperature and the density of the glass are reduced by controlling the glass within the range of 0.1-1.5. Therefore, it is preferable that (Li 2 O+Na 2 O+K 2 O)/B 2 O 3 Is 0.1 to 1.5, more preferably (Li) 2 O+Na 2 O+K 2 O)/B 2 O 3 Is 0.15 to 1.0, more preferably (Li) 2 O+Na 2 O+K 2 O)/B 2 O 3 Is 0.2 to 0.9, more preferably (Li 2 O+Na 2 O+K 2 O)/B 2 O 3 0.25 to 0.7.
WO 3 Can improve the refractive index and mechanical strength of the glass, if WO 3 The content of (2) exceeds 5%, the thermal stability of the glass decreases, and the devitrification resistance decreases. Thus, WO 3 The upper limit of the content of (2) is 5%, preferably 3%, more preferably 1%. In some embodiments, it is further preferred that WO is not included 3 。
Ta 2 O 5 With lifting meansThe glass has the effects of high refractive index and improving the devitrification resistance, but the content is too high, the thermal stability of the glass is reduced, the density is increased, and the optical constant is difficult to control to a desired range; on the other hand, ta compared with other components 2 O 5 Is very expensive, and the amount of the catalyst to be used should be reduced as much as possible from the practical and cost viewpoints. Thus, ta in the present invention 2 O 5 The content of (2) is limited to 0 to 12%, preferably 0 to 5%, more preferably 0 to 1%, and even more preferably not containing Ta 2 O 5 。
GeO 2 The glass has the effects of improving the refractive index and the devitrification resistance, but the content is too high, the chemical stability of the glass is reduced, and the optical constant is difficult to control to a desired range; on the other hand, geO is superior to other components 2 Is very expensive, and the amount of the catalyst to be used should be reduced as much as possible from the practical and cost viewpoints. Thus, geO in the present invention 2 The content of (2) is limited to 0 to 5%, preferably 0 to 3%, more preferably 0 to 1%, and even more preferably no GeO is contained 2 。
TiO 2 The glass has the functions of improving the refractive index and dispersion of the glass, and the proper amount of the glass can be more stable and reduce the viscosity of the glass. If TiO 2 The content of (2) exceeds 5%, the crystallization tendency of the glass increases, the transition temperature increases, and the P of the glass g,F Value sum delta P g,F The value becomes drastically large. Thus, in the present invention, tiO 2 The content of (2) is 5% or less, preferably 1% or less, more preferably no TiO 2 。
ZnO can adjust the refractive index and dispersion of the glass, reduce the high-temperature viscosity and the transition temperature of the glass, and enable the glass to be smelted at a lower temperature, thereby improving the light transmittance of the glass. If the content of ZnO is too high, the molding difficulty of the glass is increased, the crystallization resistance is poor, and the glass is not favorable for obtaining negative anomalous dispersion. Accordingly, the content of ZnO is 0 to 5%, preferably 0 to 3%, more preferably 0 to 1%. In some embodiments, it is further preferred that ZnO is absent.
Ln 2 O 3 (Ln 2 O 3 Is La (La) 2 O 3 、Gd 2 O 3 、Y 2 O 3 、Yb 2 O 3 、Lu 2 O 3 One or more of (a) is a component for improving refractive index and chemical stability of glass by mixing Ln 2 O 3 The content of (2) is controlled to 8% or less, and the glass can be prevented from decreasing in devitrification resistance, preferably Ln 2 O 3 The upper limit of the content range is 4%, and more preferably the upper limit is 1%. In some embodiments, it is further preferred that Ln is not present 2 O 3 。
Al 2 O 3 The chemical stability of the glass can be improved, but when the content exceeds 5%, the melting property and light transmittance of the glass become poor. Thus, al in the present invention 2 O 3 The content of (2) is 0 to 5%, preferably 0 to 3%, more preferably 0 to 1%. In some embodiments, it is further preferred that Al is absent 2 O 3 。
In the invention, 0 to 1 percent of Sb is contained 2 O 3 、SnO、SnO 2 、CeO 2 The one or more components of the glass serving as a clarifying agent can improve the clarifying effect of the glass, and the content of the clarifying agent is preferably 0-0.8%, and more preferably 0-0.5%. When Sb is 2 O 3 If the content exceeds 1%, the glass tends to be degraded in fining property, and the strong oxidation promotes corrosion of platinum or platinum alloy vessels for melting the glass and deterioration of molding dies, so that Sb is preferable in the present invention 2 O 3 The content of (2) is 0 to 1%, more preferably 0 to 0.5%. SnO and SnO 2 When the content exceeds 1%, the glass tends to be colored, or when the glass is heated, softened, and subjected to press molding or the like to be reformed, sn becomes a starting point of nucleation and devitrification tends to occur. Thus SnO of the present invention 2 The content of (2) is preferably 0 to 1%, more preferably 0 to 0.5%; the SnO content is preferably 0 to 1%, more preferably 0 to 0.5%. CeO (CeO) 2 Action and content ratio of (2) and SnO 2 The content thereof is preferably 0 to 1%, more preferably 0 to 0.5%, even more preferably no CeO 2 。
< 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 preferably does not contain As 2 O 3 And PbO.
The term "free of" 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 having negative anomalous dispersion 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 performance of the negative anomalous dispersion optical glass according to 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 ) The lower limit of (2) is 1.57, preferably 1.58, more preferably 1.60. In some embodiments, the refractive index (n d ) The upper limit of (2) is 1.67, preferably 1.65, more preferably 1.64.
In some embodiments, the Abbe number (. Nu.) of the optical glass with negative anomalous dispersion of the present invention d ) The lower limit of (2) is 38, preferably 41, and more preferably 42. In some embodiments, the Abbe number (. Nu.) of the optical glass with negative anomalous dispersion of the present invention d ) The upper limit of (2) is 48, preferably 47, more preferably 46.
< Density >
The density (. Rho.) of the optical glass was measured according to the method prescribed in GB/T7962.20-2010.
In some embodiments, the optical glass of the present invention having negative anomalous dispersion has a density (ρ) of 3.0g/cm 3 Hereinafter, it is preferably 2.90g/cm 3 Hereinafter, it is more preferably 2.85g/cm 3 The following is given.
< coefficient of thermal expansion >
Coefficient of thermal expansion (. Alpha.) of optical glass 100/300℃ ) Data at 100-300℃were tested according to the procedure prescribed in GB/T7962.16-2010.
In some embodiments, the optical glass of the present invention having negative anomalous dispersion has a coefficient of thermal expansion (α 100/300℃ ) 95X 10 -7 Preferably 90X 10, and K is less than or equal to -7 Preferably not more than/K, more preferably 85X 10 -7 and/K or below.
< transition temperature >
Transition temperature (T) of optical glass g ) The test was carried out according to the method prescribed in GB/T7962.16-2010.
In some embodiments, the present invention provides an optical glass having negative anomalous dispersion with a transition temperature (T g ) The temperature is 560 ℃ or lower, preferably 550 ℃ or lower, and more preferably 540 ℃ or lower.
< coloring degree >
The glass of the present invention has a coloring degree (lambda) for short-wave transmission spectrum characteristics 80 And lambda (lambda) 5 ) And (3) representing. Lambda (lambda) 80 Refers to the wavelength corresponding to the glass transmittance reaching 80%. Lambda (lambda) 80 Is to measure spectral transmittance in a wavelength range from 280nm to 700nm and to exhibit a wavelength of 80% transmittance using glass having a thickness of 10.+ -. 0.1mm having two opposite planes which are parallel to each other and optically polished. The spectral transmittance or transmittance is the intensity I at right angles to the surface of the glass in Transmits through glass and emits intensity I from a plane out In the case of light passing through I out /I in The indicated amounts, and also the transmittance of the surface reflection losses on the above-mentioned surface of the glass. The higher the refractive index of the glass, the greater the surface reflection loss. Thus, in high refractive index glass, λ 80 The small value of (2) means that the glass itself is extremely little colored and the light transmittance is high.
In some embodiments, λ of the optical glass of the present invention with negative anomalous dispersion 80 Less than or equal to 390nm, preferably lambda 80 Less than or equal to 380nm, more preferably lambda 80 Less than or equal to 370nm.
In some embodiments, λ of the optical glass of the present invention with negative anomalous dispersion 5 Less than or equal to 350nm, preferably lambda 5 Less than or equal to 340nm, more preferably lambda 5 Less than or equal to 330nm.
< weather resistance >
The weather resistance (CR) test method of the optical glass is as follows: the sample is placed in a test box in a saturated steam environment with the relative humidity of 90 percent, and the sample is alternately circulated at the temperature of 40-50 ℃ for 15 cycles every 1 hour. Weather resistance categories were classified according to the amount of turbidity change before and after sample placement, and weather resistance classification conditions are shown in table 1:
table 1.
In some embodiments, the optical glass of the present invention having negative anomalous dispersion has a weatherability (CR) of 2 or more, preferably 1.
< Knoop hardness >
Knoop hardness of optical glass (H K ) The test is carried out according to the test method specified in GB/T7962.18-2010.
In some embodiments, the knoop hardness (H) K ) Is 450 multiplied by 10 7 Pa or more, preferably 480×10 7 Pa or more, more preferably 500×10 7 Pa or more.
< relative partial Dispersion and relative partial Dispersion deviation value >
The relative partial dispersion (P) is described by the following formula g,F ) And relative partial dispersion deviation value (DeltaP) g,F ) Is derived from (a).
The relative partial dispersion for wavelengths x and y is represented by the following formula (1):
P x,y ＝(n x -n y )/(n F -n C ) (1)
according to Abbe's number formula, the following formula (2) is true for most of so-called "normal glasses" (hereinafter H-K6 and F4 are selected as "normal glasses")
P x,y ＝m x,y ·v d +b x,y (2)
The linear relationship is represented by P x,y Is in ordinate, v d Represented by the abscissa, where m x,y Is a slope, b x,y Is the intercept.
It is known that correction of the secondary spectrum, i.e. achromatizing to more than two wavelengths, requires at least one glass which does not correspond to formula (2) above (i.e. P x,y Value deviation from Abbe's empirical formula), which is a deviation from the value ΔP x,y Representation, then each P x,y -v d The point is shifted by ΔP with respect to the "normal line" conforming to the above formula (2) x,y The amount of ΔP of each glass x,y The numerical value can be obtained by the following formula (3):
P x,y ＝m x,y ·v d +b x,y +ΔP x,y (3)
thus DeltaP x,y The deviation characteristic of the special dispersion when compared with "normal glass" is quantitatively expressed.
Thus, the relative partial dispersion (P g,F ) And relative partial dispersion deviation value (DeltaP) g,F ) The calculation formulas of (a) are the following formulas (4) and (5):
P g,F ＝(n g -n F )/(n F -n C ) (4)
ΔP g,F ＝P g,F -0.6457+0.001703v d (5)
in some embodiments, the relative partial dispersion (P g,F ) Is 0.7000 or less, preferably 0.6500 or less, and more preferably 0.6000 or less.
In some embodiments, the relative partial dispersion deviation value (ΔP) of the optical glass of the present invention having negative anomalous dispersion g,F ) Is-0.0050 or less, preferably-0.0060 or less, more preferably-0.0065 or less.
< abrasion degree >
Abrasion degree (F) of optical glass A ) The abrasion loss of the sample and the abrasion loss (volume) of the standard sample (K9 glass) are multiplied by 100 under the identical conditions, and the values are expressed as follows:
F A ＝V/V 0 ×100＝(W/ρ)/(W 0 /ρ 0 )×100
wherein: v-the volume abrasion of the sample to be measured;
V 0 -standard sample volume attrition;
w is the mass abrasion quantity of the sample to be measured;
W 0 -standard sample mass abrasion;
ρ -the measured sample density;
ρ 0 standard sample density.
In some embodiments, the abrasion degree (F A ) The lower limit of (2) is 80, preferably 90More preferably, the lower limit is 95, and the abrasion degree (F A ) The upper limit of (2) is 130, preferably 120, more preferably 115.
[ method for producing optical glass ]
The method for manufacturing the optical glass with negative anomalous dispersion 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, compound salt (such as carbonate, nitrate, phosphate, metaphosphate and the like), 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 or platinum alloy crucible) with the temperature of 1200-1500 ℃ to be smelted, and after clarification and homogenization, homogeneous molten glass without bubbles and undissolved substances is obtained, and the molten glass is cast in a mould and annealed. 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.
[ optical instrument ]
The optical element formed by the optical glass can be used for manufacturing optical instruments such as photographic equipment, image pickup equipment, projection equipment, display equipment, vehicle-mounted equipment, monitoring equipment and the like.
Examples
< example of optical glass having negative anomalous dispersion >
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 negative anomalous dispersion and having compositions shown in tables 2 to 4 were obtained by using the above-mentioned 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 2 to 4.
Table 2.
Table 3.
Table 4.
< example of glass preform >
The glasses obtained in examples 1 to 24 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 the refractive index was fine-tuned while reducing the internal stress of the glass so that the optical characteristics such as refractive index reached the desired values.
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 elements produced by the above-described optical element embodiments are useful, for example, in imaging devices, sensors, microscopes, medical technology, digital projection, communications, optical communication technology/information transmission, optics/illumination in the automotive field, lithography, excimer lasers, wafers, computer chips, and integrated circuits and electronic devices including such circuits and chips, by optical design, by forming optical components or optical assemblies using one or more optical elements.

Claims (23)

1. The optical glass with negative anomalous dispersion is characterized by comprising the following components in percentage by weight: siO (SiO) 2 ：20～45％；B 2 O 3 ：20～40％；Nb 2 O 5 ：5～25％；ZrO 2 ：2～20％；Na 2 O: 1-15%; baO:0 to 10%, wherein (Nb) 2 O 5 +Na 2 O+BaO)/B 2 O 3 0.7 to 1.306, caO/ZrO 2 0.05 to 1.0.
2. The optical glass with negative anomalous dispersion according to claim 1, wherein its composition, expressed in weight percentage, further comprises: mgO: 0-5%; and/or CaO: 0-10%; and/or SrO: 0-5%; and/or Li 2 O: 0-5%; and/or K 2 O: 0-10%; and/or WO 3 : 0-5%; and/or Ta 2 O 5 : 0-12%; and/or TiO 2 : 0-5%; and/or ZnO: 0-5%; and/or Ln 2 O 3 : 0-8%; and/or Al 2 O 3 : 0-5%; and/or GeO 2 : 0-5%; and/or clarifying agent: 0 to 1 percent of Ln, the Ln 2 O 3 Is La (La) 2 O 3 、Gd 2 O 3 、Y 2 O 3 、Yb 2 O 3 、Lu 2 O 3 One or more of the clarifying agents is Sb 2 O 3 、SnO、SnO 2 、CeO 2 One or more of the following.
3. An optical glass having negative anomalous dispersion, characterized by comprising SiO in its composition 2 、B 2 O 3 、Nb 2 O 5 、ZrO 2 And an alkali metal oxide containing 0 to 10% by weight of BaO, wherein (Nb) 2 O 5 +Na 2 O+BaO)/B 2 O 3 0.7 to 1.306, caO/ZrO 2 0.05 to 1.0, and the refractive index n of the optical glass with negative anomalous dispersion d Is 1.57 to 1.67, abbe number v d At a relative partial dispersion P of 38 to 48 g,F A relative partial dispersion deviation value DeltaP of 0.7000 or less g,F Is-0.0050 or less, and the thermal expansion coefficient alpha 100/300℃ 95X 10 -7 and/K or below.
4. An optical glass with negative anomalous dispersion according to claim 3, characterized in that its composition, expressed in weight percentage, contains: siO (SiO) 2 : 20-45%; and/or B 2 O 3 : 20-40%; and/or Nb 2 O 5 : 5-25%; and/or ZrO 2 : 2-20%; and/or Na 2 O: 1-15%; and/or MgO: 0-5%; and/or CaO: 0-10%; and/or SrO: 0-5%; and/or Li 2 O: 0-5%; and/or K 2 O: 0-10%; and/or WO 3 : 0-5%; and/or Ta 2 O 5 : 0-12%; and/or TiO 2 : 0-5%; and/or ZnO: 0-5%; and/or Ln 2 O 3 : 0-8%; and/or Al 2 O 3 : 0-5%; and/or GeO 2 : 0-5%; and/or clarifying agent: 0 to 1 percent of Ln, the Ln 2 O 3 Is La (La) 2 O 3 、Gd 2 O 3 、Y 2 O 3 、Yb 2 O 3 、Lu 2 O 3 One or more of the clarifying agents is Sb 2 O 3 、SnO、SnO 2 、CeO 2 One or more of the following.
5. The optical glass with negative anomalous dispersion according to any of claims 1 to 4, wherein its composition, expressed in weight percentage, satisfies one or more of the following 9 cases:
1)B 2 O 3 /SiO 2 0.51 to 1.6;
2)Nb 2 O 5 /B 2 O 3 0.15 to 1.0;
3)B 2 O 3 /(Nb 2 O 5 +ZrO 2 ) 0.5 to 2.5;
4)CaO/ZrO 2 0.1 to 1.0;
5)(SiO 2 +BaO)/B 2 O 3 0.6 to 2.0;
6)(Nb 2 O 5 +Na 2 O+BaO)/B 2 O 3 0.7 to 0.95;
7)CaO/K 2 o is 0.1-5.0;
8)(CaO+K 2 O)/SiO 2 0.05 to 0.8;
9)(Li 2 O+Na 2 O+K 2 O)/B 2 O 3 0.1 to 1.5.
6. The optical glass with negative anomalous dispersion according to any of claims 1 to 4, wherein its composition, expressed in weight percentage, satisfies one or more of the following 9 cases:
1)B 2 O 3 /SiO 2 0.6 to 1.5;
2)Nb 2 O 5 /B 2 O 3 0.2 to 0.9;
3)B 2 O 3 /(Nb 2 O 5 +ZrO 2 ) 0.6 to 2.0;
4)CaO/ZrO 2 0.1 to 0.8;
5)(SiO 2 +BaO)/B 2 O 3 0.7 to 1.8;
6)(Nb 2 O 5 +Na 2 O+BaO)/B 2 O 3 0.7 to 0.9;
7)CaO/K 2 o is 0.3-3.0;
8)(CaO+K 2 O)/SiO 2 0.05 to 0.6;
9)(Li 2 O+Na 2 O+K 2 O)/B 2 O 3 0.15 to 1.0.
7. The optical glass with negative anomalous dispersion according to any of claims 1 to 4, wherein its composition, expressed in weight percentage, satisfies one or more of the following 7 cases:
1)B 2 O 3 /SiO 2 0.7 to 1.2;
2)Nb 2 O 5 /B 2 O 3 0.3 to 0.8;
3)B 2 O 3 /(Nb 2 O 5 +ZrO 2 ) 0.7 to 1.5;
4)(SiO 2 +BaO)/B 2 O 3 0.8 to 1.6;
5)CaO/K 2 o is 0.5-2.5;
6)(CaO+K 2 O)/SiO 2 0.1 to 0.5;
7)(Li 2 O+Na 2 O+K 2 O)/B 2 O 3 0.2 to 0.9.
8. The optical glass with negative anomalous dispersion according to any of claims 1 to 4, wherein its composition, expressed in weight percentage, satisfies one or more of the following 7 cases:
1)B 2 O 3 /SiO 2 0.75 to 1.0;
2)Nb 2 O 5 /B 2 O 3 0.4 to 0.7;
3)B 2 O 3 /(Nb 2 O 5 +ZrO 2 ) 0.8 to 1.3;
4)(SiO 2 +BaO)/B 2 O 3 1.0 to 1.5;
5)CaO/K 2 o is 0.8-2.0;
6)(CaO+K 2 O)/SiO 2 0.1 to 0.4;
7)(Li 2 O+Na 2 O+K 2 O)/B 2 O 3 0.25 to 0.7.
9. The optical glass with negative anomalous dispersion according to any of claims 1 to 4, wherein its composition is expressed in weight percent, wherein: siO (SiO) 2 : 25-40%; and/or B 2 O 3 : 21-35%; and/or Nb 2 O 5 : 8-20%; and/or ZrO 2 : 5-18%; and/or Na 2 O：3～13%; and/or MgO:0 to 2 percent; and/or CaO: 0.5-8%; and/or SrO:0 to 2 percent; and/or BaO: 0-5%; and/or Li 2 O:0 to 3 percent; and/or K 2 O: 0.5-8%; and/or WO 3 :0 to 3 percent; and/or Ta 2 O 5 : 0-5%; and/or TiO 2 :0 to 1 percent; and/or ZnO:0 to 3 percent; and/or Ln 2 O 3 :0 to 4 percent; and/or Al 2 O 3 :0 to 3 percent; and/or GeO 2 :0 to 3 percent; and/or clarifying agent: 0 to 0.8 percent of Ln, the Ln 2 O 3 Is La (La) 2 O 3 、Gd 2 O 3 、Y 2 O 3 、Yb 2 O 3 、Lu 2 O 3 One or more of the clarifying agents is Sb 2 O 3 、SnO、SnO 2 、CeO 2 One or more of the following.
10. The optical glass with negative anomalous dispersion according to any of claims 1 to 4, wherein its composition is expressed in weight percent, wherein: siO (SiO) 2 : 28-38%; and/or B 2 O 3 : 23-30%; and/or Nb 2 O 5 : 10-18%; and/or ZrO 2 : 7-15%; and/or Na 2 O: 5-12%; and/or MgO:0 to 1 percent; and/or CaO:1 to 6 percent; and/or SrO:0 to 1 percent; and/or BaO:0 to 3 percent; and/or Li 2 O:0 to 2 percent; and/or K 2 O:1 to 6 percent; and/or WO 3 :0 to 1 percent; and/or Ta 2 O 5 :0 to 1 percent; and/or ZnO:0 to 1 percent; and/or Ln 2 O 3 :0 to 1 percent; and/or Al 2 O 3 :0 to 1 percent; and/or GeO 2 :0 to 1 percent; and/or clarifying agent: 0 to 0.5 percent of Ln, the Ln 2 O 3 Is La (La) 2 O 3 、Gd 2 O 3 、Y 2 O 3 、Yb 2 O 3 、Lu 2 O 3 One or more of the clarifying agents is Sb 2 O 3 、SnO、SnO 2 、CeO 2 One or more of the following.
11. The optical glass with negative anomalous dispersion according to any of claims 1 to 4, wherein the component does not contain TiO 2 The method comprises the steps of carrying out a first treatment on the surface of the And/or does not contain WO 3 The method comprises the steps of carrying out a first treatment on the surface of the And/or does not contain Ta 2 O 5 The method comprises the steps of carrying out a first treatment on the surface of the And/or does not contain GeO 2 The method comprises the steps of carrying out a first treatment on the surface of the And/or contain no ZnO; and/or does not contain Ln 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the And/or does not contain Al 2 O 3 The Ln is 2 O 3 Is La (La) 2 O 3 、Gd 2 O 3 、Y 2 O 3 、Yb 2 O 3 、Lu 2 O 3 One or more of the following.
12. The optical glass with negative anomalous dispersion according to any of claims 1 to 2, wherein the refractive index n of the optical glass with negative anomalous dispersion d 1.57 to 1.67; and/or Abbe number v d 38 to 48.
13. The optical glass with negative anomalous dispersion according to any of claims 1 to 4, wherein the refractive index n of the optical glass with negative anomalous dispersion d 1.58 to 1.65; and/or Abbe number v d 41 to 47.
14. The optical glass with negative anomalous dispersion according to any of claims 1 to 4, wherein the refractive index n of the optical glass with negative anomalous dispersion d 1.60 to 1.64; and/or Abbe number v d 42 to 46.
15. The optical glass with negative anomalous dispersion according to any of claims 1 to 2, characterized in that the relative partial dispersion P of the optical glass with negative anomalous dispersion g,F Is 0.7000 or less; and/or relative partial dispersion deviation value ΔP g,F Is-0.0050 or less.
16. A method according to any one of claims 1 to 3 having negative anomalous dispersionThe optical glass of (2) is characterized in that the relative partial dispersion P of the optical glass with negative anomalous dispersion g,F 0.6500 or less; and/or relative partial dispersion deviation value ΔP g,F Is-0.0060 or less.
17. The optical glass having negative anomalous dispersion according to any of claims 1 to 3, wherein the optical glass having negative anomalous dispersion has a relative partial dispersion P g,F Is less than 0.6000; and/or relative partial dispersion deviation value ΔP g,F Is-0.0065 or less.
18. The optical glass with negative anomalous dispersion according to any of claims 1 to 3, wherein the density ρ of the optical glass with negative anomalous dispersion is 3.0g/cm 3 The following are set forth; and/or coefficient of thermal expansion alpha 100/300℃ 95X 10 -7 and/K or below; and/or transition temperature T g Is below 560 ℃; and/or lambda 80 Less than or equal to 390nm; and/or lambda 5 Less than or equal to 350nm; and/or weather resistance CR is more than 2 kinds; and/or knoop hardness H K Is 450 multiplied by 10 7 Pa or more; and/or abrasion degree F A 80 to 130.
19. The optical glass with negative anomalous dispersion according to any of claims 1 to 3, wherein the density ρ of the optical glass with negative anomalous dispersion is 2.90g/cm 3 The following are set forth; and/or coefficient of thermal expansion alpha 100/300℃ 90X 10 -7 and/K or below; and/or transition temperature T g Is below 550 ℃; and/or lambda 80 Less than or equal to 380nm; and/or lambda 5 Less than or equal to 340nm; and/or weatherability CR is class 1; and/or knoop hardness H K 480X 10 7 Pa or more; and/or abrasion degree F A 90 to 120.
20. The optical glass with negative anomalous dispersion according to any of claims 1 to 3, wherein the optical glass with negative anomalous dispersionThe density ρ of the glass was 2.85g/cm 3 The following are set forth; and/or coefficient of thermal expansion alpha 100/300℃ 85X 10 -7 and/K or below; and/or transition temperature T g Is below 540 ℃; and/or lambda 80 Less than or equal to 370nm; and/or lambda 5 Less than or equal to 330nm; and/or knoop hardness H K 500X 10 7 Pa or more; and/or abrasion degree F A 95 to 115.
21. A glass preform, characterized in that it is made of the optical glass having negative anomalous dispersion according to any of claims 1 to 20.
22. An optical element, characterized in that it is made of the optical glass with negative anomalous dispersion according to any of claims 1 to 20 or made of the glass preform according to claim 21.
23. An optical instrument comprising the optical glass having negative anomalous dispersion according to any of claims 1 to 20, and/or comprising the optical element according to claim 22.
CN202210710068.3A 2022-06-22 2022-06-22 Optical glass with negative anomalous dispersion Active CN115028353B (en)

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CN115448591B (en) * 2022-10-18 2023-07-25 成都光明光电股份有限公司 Optical glass, optical element and optical instrument

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CN113582537A (en) * 2021-09-07 2021-11-02 成都光明光电股份有限公司 High-refraction high-dispersion optical glass

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US4980318A (en) * 1989-05-10 1990-12-25 Corning Incorporated High refractive index photochromic glasses
US5858898A (en) * 1996-10-23 1999-01-12 Kabushiki Kaisha Ohara Optical glass having a negative anomalous dispersion
CN101746953A (en) * 2008-12-09 2010-06-23 湖北新华光信息材料股份有限公司 High refractive index optical phosphate glass
CN104129918A (en) * 2013-04-30 2014-11-05 株式会社小原 Optical glass, preform, and optical element
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