CN115448591B - Optical glass, optical element and optical instrument - Google Patents

Optical glass, optical element and optical instrument Download PDF

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CN115448591B
CN115448591B CN202211273285.7A CN202211273285A CN115448591B CN 115448591 B CN115448591 B CN 115448591B CN 202211273285 A CN202211273285 A CN 202211273285A CN 115448591 B CN115448591 B CN 115448591B
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optical glass
glass according
bao
components
percent
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CN115448591A (en
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孙伟
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CDGM Glass Co Ltd
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CDGM Glass Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/062—Glass compositions containing silica with less than 40% silica by weight
    • 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
    • C03C3/066—Glass compositions containing silica with less than 40% silica by weight containing boron containing zinc
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/062—Glass compositions containing silica with less than 40% silica by weight
    • C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
    • C03C3/068—Glass compositions containing silica with less than 40% silica by weight containing boron containing rare earths
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/097—Glass compositions containing silica with 40% to 90% silica, by weight containing phosphorus, niobium or tantalum
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C4/00—Compositions for glass with special properties
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements

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

Abstract

The invention provides optical glass, which comprises the following components in percentage by weight: siO (SiO) 2 ：26～42％；Nb 2 O 5 ：21～40％；ZrO 2 ：0.5～12％；RO：7～35％；Na 2 O:3 to 18%, wherein the RO is a total content of MgO, caO, srO, baO. Through reasonable component design, the optical glass obtained by the invention has the expected refractive index and Abbe number and also has lower relative partial dispersion P g,F And negative anomalous dispersion, meets the requirement of environmental protection, and meets the application of high-end photoelectric products.

Description

Optical glass, optical element and optical instrument
Technical Field
The present invention relates to an optical glass, and more particularly, to an optical glass having a refractive index of 1.68 to 1.76 and an abbe number of 30 to 39, and an optical element and an optical instrument made thereof.
Background
Optical glass is an important component of photoelectric products, and with the rapid development of photoelectric products such as smart phones, single-lens reflex cameras, monitoring security protection and the like, higher requirements are put on the performance of the optical glass in recent years. For example, optical glasses in optical designs are expected to have properties that are suitable for eliminating or minimizing residual chromatic aberration of the secondary spectrum, which requires that the optical glass have a lower relative partial dispersion (P g,F ) And negative anomalous dispersion.
The optical glass with the refractive index of 1.68-1.76 and the Abbe number of 30-39 can be widely applied to various optical systems. In the prior art, the relative partial dispersion (P g,F ) And the requirements of eliminating the residual chromatic aberration of the secondary spectrum are difficult to meet. For example, CN102442775a discloses an optical glass with refractive index of 1.63-1.72 and abbe number of 29-40, which does not have negative anomalous dispersion, contains 30-60 wt% of PbO component, and does not meet the requirement of environmental protection. For example, CN101549955a discloses an optical glass with refractive index of 1.59-1.71 and abbe number of 30-43, which does not have negative anomalous dispersion, contains 25-60 wt% of PbO component, and does not meet the requirement of environmental protection. Thus, a refractive index of 1.68 to 1.76 and Abbe number of 30 to 39 were developed, relative partial dispersion (P g,F ) Lower anomalous dispersion with negative going and signThe optical glass meeting the environmental protection requirement has important significance for the development of the photoelectric field.
Disclosure of Invention
The invention aims to provide a method for compensating relative partial dispersion (P g,F ) The optical glass has lower negative anomalous dispersion and meets the environmental protection requirement.
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 ：26～42％；Nb 2 O 5 ：21～40％；ZrO 2 ：0.5～12％；RO：7～35％；Na 2 O:3 to 18%, wherein the RO is a total content of MgO, caO, srO, baO.
Further, the optical glass comprises the following components in percentage by weight: b (B) 2 O 3 : 0-10%; and/or Li 2 O: 0-5%; and/or K 2 O: 0-8%; and/or WO 3 : 0-5%; and/or Ta 2 O 5 : 0-5%; and/or TiO 2 : 0-5%; and/or ZnO: 0-8%; and/or Ln 2 O 3 : 0-5%; and/or Al 2 O 3 : 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.
An optical glass, the components of which are represented by weight percentage and are composed of SiO 2 ：26～42％；Nb 2 O 5 ：21～40％；ZrO 2 ：0.5～12％；RO：7～35％；Na 2 O：3～18％；B 2 O 3 ：0～10％；Li 2 O：0～5％；K 2 O：0～8％；WO 3 ：0～5％；Ta 2 O 5 ：0～5％；TiO 2 ：0～5％；ZnO：0～8％；Ln 2 O 3 ：0～5％；Al 2 O 3 : 0-5%; clarifying agent: 0 to 1%, wherein RO is a total content of MgO, caO, srO, baO, 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.
Further, the optical glass comprises the following components in percentage by weight: b (B) 2 O 3 /SiO 2 Is 0.3 or less, preferably B 2 O 3 /SiO 2 Is 0.25 or less, more preferably B 2 O 3 /SiO 2 Is 0.2 or less, more preferably B 2 O 3 /SiO 2 0.01 to 0.15.
Further, the optical glass comprises the following components in percentage by weight: RO/SiO 2 From 0.2 to 1.2, preferably RO/SiO 2 From 0.25 to 1.0, more preferably RO/SiO 2 From 0.3 to 0.8, RO/SiO being more preferred 2 The RO is a total content of MgO, caO, srO, baO and is 0.4 to 0.7.
Further, the optical glass comprises the following components in percentage by weight: RO/Nb 2 O 5 Is 0.2 to 1.5, preferably RO/Nb 2 O 5 Is 0.3 to 1.2, more preferably RO/Nb 2 O 5 From 0.4 to 1.0, RO/Nb is more preferable 2 O 5 The RO is a total content of MgO, caO, srO, baO and is 0.4 to 0.8.
Further, the optical glass comprises the following components in percentage by weight: b (B) 2 O 3 BaO is 1.4 or less, preferably B 2 O 3 BaO is 1.0 or less, more preferably B 2 O 3 BaO is 0.8 or less, and further preferably B 2 O 3 BaO is 0.1 to 0.5.
Further, the optical glass comprises the following components in percentage by weight: (ZrO 2 +ZnO)/BaO of 0.05 to 1.5, preferably (ZrO 2 +ZnO)/BaO of 0.1 to 1.0, more preferablySelecting (ZrO) 2 +ZnO)/BaO is 0.15 to 0.8, more preferably (ZrO 2 +ZnO)/BaO is 0.2 to 0.6.
Further, the optical glass comprises the following components in percentage by weight: (SiO) 2 +Nb 2 O 5 ) BaO is 2.5 to 10.0, preferably (SiO) 2 +Nb 2 O 5 ) BaO is 3.0 to 8.0, more preferably (SiO) 2 +Nb 2 O 5 ) BaO is 3.5 to 7.0, and further preferably (SiO) 2 +Nb 2 O 5 ) BaO is 4.0-6.0.
Further, the optical glass comprises the following components in percentage by weight: (BaO+CaO)/Na 2 O is 0.5 to 5.0, preferably (BaO+CaO)/Na 2 O is 0.8 to 4.0, more preferably (BaO+CaO)/Na 2 O is 1.0 to 3.0, more preferably (BaO+CaO)/Na 2 O is 1.2-2.5.
Further, the optical glass comprises the following components in percentage by weight: (Na) 2 O+Nb 2 O 5 )/SiO 2 Is 0.6 to 2.0, preferably (Na 2 O+Nb 2 O 5 )/SiO 2 Is 0.7 to 1.7, more preferably (Na) 2 O+Nb 2 O 5 )/SiO 2 Is 0.8 to 1.5, more preferably (Na) 2 O+Nb 2 O 5 )/SiO 2 1.0 to 1.5.
Further, the optical glass comprises the following components in percentage by weight: (B) 2 O 3 +Li 2 O+TiO 2 )/(BaO+Nb 2 O 5 ) Is 0.5 or less, preferably (B) 2 O 3 +Li 2 O+TiO 2 )/(BaO+Nb 2 O 5 ) Is 0.3 or less, more preferably (B) 2 O 3 +Li 2 O+TiO 2 )/(BaO+Nb 2 O 5 ) Is 0.2 or less, more preferably (B) 2 O 3 +Li 2 O+TiO 2 )/(BaO+Nb 2 O 5 ) 0.01 to 0.15.
Further, the optical glass comprises the following components in percentage by weight: siO (SiO) 2 :28 to 40%, preferably SiO 2 : 30-37%; andand/or B 2 O 3 :0 to 6%, preferably B 2 O 3 :0.5 to 5 percent; and/or Nb 2 O 5 :25 to 35%, preferably Nb 2 O 5 : 27-33%; and/or ZrO 2 :1 to 10%, preferably ZrO 2 : 2-8%; and/or RO: 11-30%, preferably RO: 13-25%; and/or Na 2 O:5 to 15%, preferably Na 2 O: 7-13%; and/or Li 2 O:0 to 3%, preferably Li 2 O:0 to 2 percent; and/or K 2 O:0 to 5%, preferably K 2 O:0 to 3 percent; and/or WO 3 :0 to 3%, preferably WO 3 :0 to 1 percent; and/or Ta 2 O 5 :0 to 3%, preferably Ta 2 O 5 :0 to 1 percent; and/or TiO 2 :0 to 3%, preferably TiO 2 :0 to 1 percent; and/or ZnO:0 to 4%, preferably ZnO:0 to 1 percent; and/or Ln 2 O 3 :0 to 3%, 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 clarifying agent: 0 to 0.8%, preferably a clarifying agent: 0 to 0.5%, wherein RO is a total content of MgO, caO, srO, baO, 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.
Further, the optical glass comprises the following components in percentage by weight: baO: 6-20%, preferably BaO: 8-18%, more preferably BaO: 10-16%; and/or MgO:0 to 6%, preferably MgO:0 to 3%, more preferably MgO:0 to 1 percent; and/or CaO:0 to 10%, preferably CaO:0.5 to 8%, more preferably CaO:1 to 6 percent; and/or SrO:0 to 6%, preferably SrO:0 to 3%, more preferably SrO:0 to 1 percent.
Further, the optical glass does not contain TiO in the components 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 contain no ZnO; and/orDoes 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 Li 2 O; 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.
Further, the refractive index n of the optical glass d From 1.68 to 1.76, preferably from 1.69 to 1.75, more preferably from 1.70 to 1.74, still more preferably from 1.71 to 1.73, and/or Abbe number v d 30 to 39, preferably 31 to 38, more preferably 32 to 37, and even more preferably 33 to 36.
Further, the relative partial dispersion P of the optical glass g,F 0.7500, preferably 0.7000 or less, more preferably 0.6500 or less, still more preferably 0.6000 or less, and/or a relative partial dispersion deviation Δp g,F It is preferably less than 0, more preferably less than-0.0001, still more preferably less than-0.0005, and still more preferably less than-0.0010.
Further, the optical glass has a density ρ of 3.8g/cm 3 Hereinafter, it is preferably 3.7g/cm 3 Hereinafter, it is more preferably 3.6g/cm 3 The following are set forth; and/or coefficient of thermal expansion alpha -30/70℃ 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 lambda 80 Less than or equal to 400nm, preferably lambda 80 Less than or equal to 390nm, more preferably lambda 80 Less than or equal to 385nm; 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 335nm; and/or weather resistance CR is 2 or more, preferably 1; and/or acid action resistance stability D A More than 2 types, preferably 1 type; and/or stability against water action D W More than 2 types, preferably 1 type; and/or knoop hardness H K 500X 10 7 Pa or more, preferably 510×10 7 Pa or more, more preferably 520×10 7 Pa or more; and/or abrasion degree F A 180 to 220, preferably 185 to 215, more preferably 190 to 210; and/or poplarThe modulus of elasticity E is 8000X 10 7 ～11000×10 7 Pa, preferably 8500×10 7 ～10500×10 7 Pa, more preferably 9000×10 7 ～10000×10 7 Pa。
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: through reasonable component design, the optical glass obtained by the invention has the expected refractive index and Abbe number and also has lower relative partial dispersion (P g,F ) And negative anomalous dispersion, meets the requirement of environmental protection, and meets the application of high-end photoelectric products.
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, the optical glass of the present invention is sometimes referred to simply as glass in the following description, although the explanation is omitted appropriately, and the gist of the present invention is not limited thereto.
[ 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, 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 Is an essential component of the optical glass, is a framework of the optical glass, can improve the acid resistance and the viscosity of the glass and reduce the abrasion degree of the glass, and contains more than 26 percent of SiO 2 To obtain the above effect, it is preferable to contain 28% or more of SiO 2 More preferably, the SiO content is 30% or more 2 . On the other hand, if SiO 2 If the content of (2) is too large, the melting property of the glass becomes poor, the viscosity at high temperature becomes high, and inclusions such as bubbles and stones are likely to occur in the glass. Thus, siO in the present invention 2 The upper limit of the content of (2) is 42%, preferably 40%, more preferably 37%.
B 2 O 3 Has the effect of improving the thermal stability and meltability of the glass, but when the content thereof is more than 10%, the chemical stability, weather resistance and devitrification resistance of the glass are reduced. Thus, in the present invention B 2 O 3 The content of (2) is 0 to 10%, preferably 0 to 6%, more preferably 0.5 to 5%.
In some embodiments, B 2 O 3 Content of (2) and SiO 2 Ratio B between the contents of (2) 2 O 3 /SiO 2 The glass is controlled below 0.3, which is beneficial to improving the weather resistance and Young's modulus of the glass and improving the light transmittance of the glass. Therefore, B is preferred 2 O 3 /SiO 2 Is 0.3 or less, more preferably B 2 O 3 /SiO 2 Is 0.25 or less, more preferably B 2 O 3 /SiO 2 Is 0.2 or less, more preferably B 2 O 3 /SiO 2 0.01 to 0.15.
ZrO 2 Can improve the refractive index of the glass and improve the chemical stability of the glassRegulating short wave special dispersion and reducing delta P of glass g,F If the content is too large, the difficulty of melting the glass increases, the melting temperature increases, and inclusions appear in the glass and the light transmittance decreases. Thus, zrO 2 The content of (2) is 0.5 to 12%, preferably 1 to 10%, more preferably 2 to 8%.
In some embodiments, the alkaline earth oxide RO (RO is the total content of MgO, caO, srO, baO) is controlled to be in the range of 7 to 35%, the glass is easier to obtain a desired optical constant, and the chemical stability and abrasion of the glass are optimized. Therefore, the RO is preferably 7 to 35%, more preferably 11 to 30%, and even more preferably 13 to 25%.
In some embodiments, the RO content is compared to SiO 2 Ratio RO/SiO between the contents of (C) 2 The hardness of the glass can be improved and the chemical stability of the glass can be prevented from deteriorating by controlling the hardness to be in the range of 0.2-1.2. Therefore, RO/SiO is preferred 2 From 0.2 to 1.2, more preferably RO/SiO 2 0.25 to 1.0. Further, control RO/SiO 2 In the range of 0.3 to 0.8, the abrasion degree and Young's modulus of the glass can be further optimized. Therefore, RO/SiO is more preferable 2 From 0.3 to 0.8, more preferably RO/SiO 2 0.4 to 0.7.
MgO can reduce the relative partial dispersion of the glass, but when the MgO content is too high, the refractive index of the glass is difficult to meet the design requirement, and the crystallization resistance and the stability of the glass are reduced. Accordingly, the MgO content is limited to 0 to 6%, preferably 0 to 3%, more preferably 0 to 1%. In some embodiments, it is further preferred that MgO is not contained.
The CaO can adjust the optical constant of the glass, improve the chemical stability of the glass, improve the processing performance of the glass, reduce the high-temperature viscosity and the surface tension of the glass, reduce the production difficulty of the glass, and reduce the devitrification resistance of the glass if the content of the CaO is too high. Therefore, the CaO content is 0 to 10%, preferably 0.5 to 8%, more preferably 1 to 6%.
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 content of SrO is limited to 0 to 6%, preferably 0 to 3%, more preferably 0 to 1%. In some embodiments, it is further preferred that SrO is absent.
BaO can improve the refractive index, the meltability and the thermal stability of the glass, improve the abrasion degree and the light transmittance of the glass, and if the content is too high, the density of the glass is increased and the devitrification resistance is reduced. Therefore, the BaO content is 6 to 20%, preferably 8 to 18%, more preferably 10 to 16%.
In some embodiments, B 2 O 3 Ratio B between the content of BaO and the content of BaO 2 O 3 BaO is controlled to 1.4 or less, which can improve the chemical stability and Young's modulus of the glass and prevent the hardness of the glass from deteriorating. Therefore, B is preferred 2 O 3 BaO is 1.4 or less, more preferably B 2 O 3 BaO is 1.0 or less, and further preferably B 2 O 3 BaO is 0.8 or less, and B is more preferable 2 O 3 BaO is 0.1 to 0.5.
Nb 2 O 5 Is a high-refraction high-dispersion component, can improve the refractive index, dispersion 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 Value of Nb 2 O 5 The content of (2) is too large, the thermal stability and weather resistance of the glass are reduced, and the light transmittance is reduced. Thus, nb 2 O 5 The content of (2) is in the range of 21 to 40%, preferably 25 to 35%, more preferably 27 to 33%.
In some embodiments, the RO content is compared with Nb 2 O 5 Ratio RO/Nb between the contents of (C) 2 O 5 The light transmittance of the glass can be improved while the density of the glass is reduced by controlling the glass within the range of 0.2-1.5. Therefore, RO/Nb is preferable 2 O 5 Is 0.2 to 1.5, more preferably RO/Nb 2 O 5 0.3 to 1.2. Further, control RO/Nb 2 O 5 In the range of 0.4 to 1.0, the abrasion degree and the thermal expansion coefficient of the glass can be further optimized. Therefore, RO/Nb is more preferable 2 O 5 From 0.4 to 1.0, RO/Nb is more preferable 2 O 5 Is 0 to.4～0.8。
In some embodiments, siO 2 And Nb (Nb) 2 O 5 Is the total content of SiO 2 +Nb 2 O 5 Ratio to BaO content (SiO 2 +Nb 2 O 5 ) BaO is controlled within 2.5-10.0, which can make the glass have lower P g,F Value sum delta P g,F While reducing the coefficient of thermal expansion of the glass. Therefore, it is preferable that (SiO 2 +Nb 2 O 5 ) BaO is 2.5 to 10.0, more preferably (SiO) 2 +Nb 2 O 5 ) BaO is 3.0-8.0. Further, control (SiO 2 +Nb 2 O 5 ) BaO is in the range of 3.5 to 7.0, and the abrasion degree and weather resistance of the glass can be further optimized. Therefore, it is more preferable that (SiO 2 +Nb 2 O 5 ) BaO is 3.5 to 7.0, and more preferably (SiO) 2 +Nb 2 O 5 ) BaO is 4.0-6.0.
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. In some embodiments, it is further preferred that Li is not contained 2 O。
Na 2 O has the function of improving the glass melting property, can improve the melting effect of the glass, and simultaneously is helpful for reducing the P of the glass g,F Value sum delta P g,F The value of the composition is that the composition contains more than 3% of Na 2 O to obtain the above-described effects. If Na is 2 O content exceeds 18%, and chemical stability and weather resistance of the glass are lowered, so Na 2 The content of O is 3-18%, preferably Na 2 The content of O is 5 to 15%, more preferably Na 2 The content of O is 7-13%.
In some embodiments, na 2 O and Nb 2 O 5 Is the total content Na of 2 O+Nb 2 O 5 With SiO 2 Ratio between the contents of (Na) 2 O+Nb 2 O 5 )/SiO 2 Control ofIn the range of 0.6 to 2.0, the glass can have lower P g,F Value sum delta P g,F While optimizing the value, the abrasion of the glass. Therefore, it is preferable that (Na 2 O+Nb 2 O 5 )/SiO 2 Is 0.6 to 2.0, more preferably (Na) 2 O+Nb 2 O 5 )/SiO 2 0.7 to 1.7. Further, control (Na 2 O+Nb 2 O 5 )/SiO 2 In the range of 0.8-1.5, the weather resistance of the glass can be further improved, and the density of the glass is prevented from being increased. Therefore, it is more preferable that (Na 2 O+Nb 2 O 5 )/SiO 2 Is 0.8 to 1.5, more preferably (Na) 2 O+Nb 2 O 5 )/SiO 2 1.0 to 1.5.
In some embodiments, the combined content of BaO and CaO, bao+cao, and Na 2 Ratio between O contents (BaO+CaO)/Na 2 O is controlled within the range of 0.5-5.0, so that the glass has lower P g,F Value sum delta P g,F The chemical stability of the glass is improved and the density of the glass is prevented from rising. Therefore, (BaO+CaO)/Na is preferable 2 O is 0.5 to 5.0, more preferably (BaO+CaO)/Na 2 O is 0.8-4.0. Further, control of (BaO+CaO)/Na 2 O is in the range of 1.0-3.0, and the Young's modulus and weather resistance of the glass can be further optimized. Therefore, (BaO+CaO)/Na is more preferable 2 O is 1.0 to 3.0, more preferably (BaO+CaO)/Na 2 O is 1.2-2.5.
K 2 O has an effect of improving the thermal stability and meltability of the glass, but if its content exceeds 8%, the devitrification resistance and chemical stability of the glass are deteriorated. Thus, in the present invention K 2 O content is 0 to 8%, preferably K 2 The content of O is 0 to 5%, more preferably 0 to 3%.
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 The glass has the effects of improving the refractive index and improving the devitrification resistance of the glass, 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 5%, preferably 0 to 3%, more preferably 0 to 1%, and even more preferably not containing Ta 2 O 5 。
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 large. Thus, in the present invention, tiO 2 The content of (2) is 5% or less, preferably 3% or less, more preferably 1% or less, and even more preferably no TiO is contained 2 。
In some embodiments, B 2 O 3 、Li 2 O、TiO 2 Total content B of (2) 2 O 3 +Li 2 O+TiO 2 With BaO and Nb 2 O 5 In total BaO+Nb 2 O 5 Ratio between (B) 2 O 3 +Li 2 O+TiO 2 )/(BaO+Nb 2 O 5 ) The chemical stability of the glass can be improved and the decrease of the light transmittance of the glass can be prevented by controlling the glass content to be less than 0.5. Therefore, (B) is preferable 2 O 3 +Li 2 O+TiO 2 )/(BaO+Nb 2 O 5 ) Is 0.5 or less, more preferably (B) 2 O 3 +Li 2 O+TiO 2 )/(BaO+Nb 2 O 5 ) Is 0.3 or less. Further, control (B 2 O 3 +Li 2 O+TiO 2 )/(BaO+Nb 2 O 5 ) Below 0.2, the hardness and thermal expansion coefficient of the glass may be further optimized. Therefore, (B) is more preferable 2 O 3 +Li 2 O+TiO 2 )/(BaO+Nb 2 O 5 ) Is 0.2 or less, more preferably (B) 2 O 3 +Li 2 O+TiO 2 )/(BaO+Nb 2 O 5 ) 0.01 to 0.15.
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 8%, preferably 0 to 4%, more preferably 0 to 1%. In some embodiments, it is further preferred that ZnO is absent.
In some embodiments, zrO 2 And ZnO in total content of ZrO 2 The ratio between +ZnO and BaO content (ZrO 2 The +ZnO)/BaO is controlled within the range of 0.05 to 1.5, so that the glass has lower P g,F Value sum delta P g,F The Young's modulus of the glass is prevented from deteriorating while the value is obtained. Therefore, (ZrO 2 +ZnO)/BaO of 0.05 to 1.5, more preferably (ZrO 2 +ZnO)/BaO is 0.1 to 1.0. Further, control (ZrO 2 The +ZnO)/BaO is in the range of 0.15 to 0.8, and can further reduce the thermal expansion coefficient of the glass and improve the hardness of the glass. Therefore, it is more preferable that (ZrO 2 +ZnO)/BaO is 0.15 to 0.8, more preferably (ZrO 2 +ZnO)/BaO is 0.2 to 0.6.
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 5% 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 of (2) is 3%, 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 glassAnd the melting property and light transmittance of the polymer are deteriorated. 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 in the glass are used as a clarifying agent, so that the clarifying effect of the glass can be improved, the bubble degree of the glass is improved, the content of the clarifying agent is preferably 0-0.8%, and the content of the clarifying agent is 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 0.8%, still 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 0.8%, still more preferably 0 to 0.5%; the content of SnO is preferably 0 to 1%, more preferably 0 to 0.8%, and still 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 0.8%, even more preferably 0 to 0.5%, and even more preferably no CeO is contained 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 "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 performance 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 ) The lower limit of (2) is 1.68, preferably 1.69, more preferably 1.70, and even more preferably 1.71. In some embodiments, the refractive index (n d ) The upper limit of (2) is 1.76, preferably 1.75, more preferably 1.74, and even more preferably 1.73.
In some embodiments, the Abbe number (. Nu.) of the optical glass of the present invention d ) The lower limit of (2) is preferably 30, more preferably 31, still more preferably 32, and still more preferably 33. In some embodiments, the light of the present invention Abbe number (v) of glass d ) The upper limit of (2) is 39, preferably 38, more preferably 37, and even more preferably 36.
< 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 has a density (ρ) of 3.8g/cm 3 Hereinafter, it is preferably 3.7g/cm 3 Hereinafter, it is more preferably 3.6g/cm 3 The following is given.
< coefficient of thermal expansion >
Coefficient of thermal expansion (. Alpha.) of optical glass -30/70℃ ) Data at-30 to 70℃were tested according to the procedure prescribed in GB/T7962.16-2010.
In some embodiments, the optical glass of the present invention has a coefficient of thermal expansion (α -30/70℃ ) 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.
< 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 glass, lambda 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 80 Less than or equal to 400nm, preferably lambda 80 Less than or equal to 390nm, more preferably lambda 80 Less than or equal to 385nm.
In some embodiments, λ of the optical glass of the present invention 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 335nm.
< 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 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 ) 500X 10 7 Pa or more, preferably 510×10 7 Pa or more, more preferably 520×10 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 ) 0.7500 is preferably 0.7000 or less, more preferably 0.6500 or less, and even more preferably 0.6000 or less.
In some embodiments, the relative partial dispersion deviation value (Δp of the optical glass of the present invention g,F ) It is preferably less than 0, more preferably less than-0.0001, still more preferably less than-0.0005, and still more preferably less than-0.0010.
< abrasion degree >
Abrasion degree (F) of optical glass A ) The abrasion loss of the sample and the abrasion loss (volume) of the standard sample (H-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 abrasiveness (F A ) Lower limit of 180, preferably lower limit of 185, more preferably lower limit of 190, abrasion (F A ) The upper limit of (2) is 220, preferably 215, and more preferably 210.
< 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.
In some embodiments, the water resistance stability (D W ) More than 2 kinds, preferably 1 kind.
< 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.
In some embodiments, the acid action resistance stability (D A ) More than 2 kinds, preferably 1 kind.
< Young's modulus >
Young's modulus (E) is obtained by measuring longitudinal wave velocity and transverse wave velocity by ultrasonic wave and calculating according to the following formula.
G＝V S 2 ρ
Wherein: e is Young's modulus, pa;
g is the shear modulus, pa;
V T is transverse wave speed, m/s;
V S is longitudinal wave speed, m/s;
ρ is the density of the glass, g/cm 3 。
In some embodiments, the Young's modulus (E) of the optical glass of the present invention has a lower limit of 8000X 10 7 Pa, a lower limit of 8500×10 is preferable 7 Pa or more, and more preferably 9000×10 as a lower limit 7 Pa or more.
In some embodiments, the Young's modulus (E) of the optical glass of the present invention has an upper limit of 11000X 10 7 Pa, a preferable upper limit is 10500×10 7 Pa, and more preferably an upper limit of 10000X 10 7 Pa。
[ method for producing optical glass ]
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, compound salt (such as carbonate, nitrate, sulfate 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 >
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 2 to 4 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 2 to 4.
Table 2.
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Table 3.
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Table 4.
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< 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 (53)

1. The optical glass is characterized by comprising the following components in percentage by weight: siO (SiO) 2 ：26～42％；Nb 2 O 5 ：21～40％；ZrO 2 ：0.5～12％；RO：7～35％；Na 2 O:3 to 18 percent, wherein, (SiO) 2 +Nb 2 O 5 ) BaO is 3.5-7.0; (BaO+CaO)/Na 2 O is 1.0 to 3.0, and RO is MgO, caO, srO, baO.
2. The optical glass according to claim 1, wherein the composition, expressed in weight percent, further comprises: b (B) 2 O 3 : 0-10%; and/or Li 2 O: 0-5%; and/or K 2 O: 0-8%; and/or WO 3 : 0-5%; and/or Ta 2 O 5 : 0-5%; and/or TiO 2 : 0-5%; and/or ZnO: 0-8%; and/or Ln 2 O 3 : 0-5%; and/or Al 2 O 3 : 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, characterized in that the components thereof are represented by weight percent and are composed of SiO 2 ：26～42％；Nb 2 O 5 ：21～40％；ZrO 2 ：0.5～12％；RO：7～35％；Na 2 O：3～18％；B 2 O 3 ：0～10％；Li 2 O：0～5％；K 2 O：0～8％；WO 3 ：0～5％；Ta 2 O 5 ：0～5％；TiO 2 ：0～5％；ZnO：0～8％；Ln 2 O 3 ：0～5％；Al 2 O 3 : 0-5%; clarifying agent: 0 to 1 percent of (SiO) 2 +Nb 2 O 5 ) BaO is 3.5-7.0; (BaO+CaO)/Na 2 O is 1.0 to 3.0, RO is the total content of MgO, caO, srO, baO and 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.
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 Is 0.3 or less.
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 Is 0.25 or less.
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 Is 0.2 or less.
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 0.01 to 0.15.
8. An optical glass according to any one of claims 1 to 3, wherein the components thereof are expressed in weight percent, wherein: RO/SiO 2 The RO is a total content of MgO, caO, srO, baO in an amount of 0.2 to 1.2.
9. An optical glass according to any one of claims 1 to 3, wherein the components thereof are expressed in weight percent, wherein: RO/SiO 2 0.25 to 1.0, and the RO is a total content of MgO, caO, srO, baO.
10. An optical glass according to any one of claims 1 to 3, wherein the components thereof are expressed in weight percent, wherein: RO/SiO 2 The RO is a total content of MgO, caO, srO, baO in an amount of 0.3 to 0.8.
11. An optical glass according to any one of claims 1 to 3, wherein the components thereof are expressed in weight percent, wherein: RO/SiO 2 The RO is a total content of MgO, caO, srO, baO and is 0.4 to 0.7.
12. An optical glass according to any one of claims 1 to 3, wherein the components thereof are expressed in weight percent, wherein: RO/Nb 2 O 5 0.2 to 1.5, wherein the RO is a total content of MgO, caO, srO, baO.
13. An optical glass according to any one of claims 1 to 3, wherein the components thereof are expressed in weight percent, wherein: RO/Nb 2 O 5 The RO is a total content of MgO, caO, srO, baO in an amount of 0.3 to 1.2.
14. An optical glass according to any one of claims 1 to 3, wherein the components thereof are expressed in weight percent, wherein: RO/Nb 2 O 5 The RO is a total content of MgO, caO, srO, baO in an amount of 0.4 to 1.0.
15. An optical glass according to any one of claims 1 to 3, wherein the components thereof are expressed in weight percent, wherein: RO/Nb 2 O 5 The RO is a total content of MgO, caO, srO, baO and is 0.4 to 0.8.
16. 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 BaO is 1.4 or less.
17. 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 BaO is 1.0 or less.
18. 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 BaO is 0.8 or less.
19. 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 BaO is 0.1 to 0.5.
20. An optical glass according to any one of claims 1 to 3, wherein the components thereof are expressed in weight percent, wherein: (ZrO 2 +ZnO)/BaO is 0.05 to 1.5.
21. An optical glass according to any one of claims 1 to 3, wherein the components thereof are expressed in weight percent, wherein: (ZrO 2 +ZnO)/BaO is 0.1 to 1.0.
22. An optical glass according to any one of claims 1 to 3, wherein the components thereof are expressed in weight percent, wherein: (ZrO 2 +ZnO)/BaO is 0.15 to 0.8.
23. An optical glass according to any one of claims 1 to 3, wherein the components thereof are expressed in weight percent, wherein: (ZrO 2 +ZnO)/BaO is 0.2 to 0.6.
24. An optical glass according to any one of claims 1 to 3, wherein the components thereof are expressed in weight percent, wherein: (SiO) 2 +Nb 2 O 5 ) BaO is 4.0-6.0.
25. An optical glass according to any one of claims 1 to 3, wherein the components thereof are expressed in weight percent, wherein: (BaO+CaO)/Na 2 O is 1.2-2.5.
26. An optical glass according to any one of claims 1 to 3, wherein the components thereof are expressed in weight percent, wherein: (Na) 2 O+Nb 2 O 5 )/SiO 2 0.6 to 2.0.
27. An optical glass according to any one of claims 1 to 3, wherein the components thereof are expressed in weight percent, wherein: (Na) 2 O+Nb 2 O 5 )/SiO 2 0.7 to 1.7.
28. An optical glass according to any one of claims 1 to 3, wherein the components thereof are expressed in weight percent, wherein: (Na) 2 O+Nb 2 O 5 )/SiO 2 0.8 to 1.5.
29. An optical glass according to any one of claims 1 to 3, wherein the components thereof are as followsExpressed in weight percent, wherein: (Na) 2 O+Nb 2 O 5 )/SiO 2 1.0 to 1.5.
30. An optical glass according to any one of claims 1 to 3, wherein the components thereof are expressed in weight percent, wherein: (B) 2 O 3 +Li 2 O+TiO 2 )/(BaO+Nb 2 O 5 ) Is 0.5 or less.
31. An optical glass according to any one of claims 1 to 3, wherein the components thereof are expressed in weight percent, wherein: (B) 2 O 3 +Li 2 O+TiO 2 )/(BaO+Nb 2 O 5 ) Is 0.3 or less.
32. An optical glass according to any one of claims 1 to 3, wherein the components thereof are expressed in weight percent, wherein: (B) 2 O 3 +Li 2 O+TiO 2 )/(BaO+Nb 2 O 5 ) Is 0.2 or less.
33. An optical glass according to any one of claims 1 to 3, wherein the components thereof are expressed in weight percent, wherein: (B) 2 O 3 +Li 2 O+TiO 2 )/(BaO+Nb 2 O 5 ) 0.01 to 0.15.
34. 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 : 28-40%; and/or B 2 O 3 :0 to 6 percent; and/or Nb 2 O 5 : 25-35%; and/or ZrO 2 :1 to 10 percent; and/or RO: 11-30%; and/or Na 2 O: 5-15%; and/or Li 2 O:0 to 3 percent; and/or K 2 O: 0-5%; and/or WO 3 :0 to 3 percent; and/or Ta 2 O 5 :0 to 3 percent; and/or TiO 2 :0 to 3 percent; and/or ZnO:0 to 4 percent; and/or Ln 2 O 3 :0 to 3 percent; and/or Al 2 O 3 :0 to 3 percent; and/or clarifying agent: 0 to 0.8%, wherein RO is a total content of MgO, caO, srO, baO, 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.
35. 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 : 30-37%; and/or B 2 O 3 :0.5 to 5 percent; and/or Nb 2 O 5 : 27-33%; and/or ZrO 2 : 2-8%; and/or RO: 13-25%; and/or Na 2 O: 7-13%; and/or Li 2 O:0 to 2 percent; and/or K 2 O:0 to 3 percent; and/or WO 3 :0 to 1 percent; and/or Ta 2 O 5 :0 to 1 percent; and/or TiO 2 :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 clarifying agent: 0 to 0.5%, wherein RO is a total content of MgO, caO, srO, baO, 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.
36. An optical glass according to any one of claims 1 to 3, wherein the components thereof are expressed in weight percent, wherein: baO: 6-20%; and/or MgO:0 to 6 percent; and/or CaO: 0-10%; and/or SrO:0 to 6 percent.
37. An optical glass according to any one of claims 1 to 3, wherein the components thereof are expressed in weight percent, wherein: baO: 8-18%; and/or MgO:0 to 3 percent; and/or CaO: 0.5-8%; and/or SrO:0 to 3 percent.
38. An optical glass according to any one of claims 1 to 3, wherein the components thereof are expressed in weight percent, wherein: baO: 10-16%; and/or MgO:0 to 1 percent; and/or CaO:1 to 6 percent; and/or SrO:0 to 1 percent.
39. An optical glass according to any one of claims 1 to 3, wherein the composition 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 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 Li 2 O; 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.
40. An optical glass according to any one of claims 1 to 3, wherein the refractive index n of the optical glass d 1.68 to 1.76; and/or Abbe number v d 30 to 39.
41. An optical glass according to any one of claims 1 to 3, wherein the refractive index n of the optical glass d 1.69 to 1.75; and/or Abbe number v d 31 to 38.
42. An optical glass according to any one of claims 1 to 3, wherein the refractive index n of the optical glass d 1.70 to 1.74; and/or Abbe number v d 32 to 37.
43. An optical glass according to any one of claims 1 to 3, wherein the refractive index n of the optical glass d 1.71 to1.73; and/or Abbe number v d 33 to 36.
44. An optical glass according to any one of claims 1 to 3, wherein the optical glass has a relative partial dispersion P g,F 0.7500 or less; and/or relative partial dispersion deviation value ΔP g,F Is less than 0.
45. An optical glass according to any one of claims 1 to 3, wherein the optical glass has a relative partial dispersion P g,F Is 0.7000 or less; and/or relative partial dispersion deviation value ΔP g,F Is-0.0001 or less.
46. An optical glass according to any one of claims 1 to 3, wherein the optical glass has a relative partial dispersion P g,F 0.6500 or less; and/or relative partial dispersion deviation value ΔP g,F Is-0.0005 or less.
47. An optical glass according to any one of claims 1 to 3, wherein the optical glass has a relative partial dispersion P g,F Is less than 0.6000; and/or relative partial dispersion deviation value ΔP g,F Is-0.0010 or less.
48. An optical glass according to any one of claims 1 to 3, wherein the optical glass has a density ρ of 3.8g/cm 3 The following are set forth; and/or coefficient of thermal expansion alpha -30/70℃ 95X 10 -7 and/K or below; and/or lambda 80 Less than or equal to 400nm; and/or lambda 5 Less than or equal to 350nm; and/or weather resistance CR is more than 2 kinds; and/or stability against water action D W Is more than 2 types; and/or knoop hardness H K 500X 10 7 Pa or more; and/or abrasion degree F A 180-220; and/or Young's modulus E of 8000X 10 7 ～11000×10 7 Pa。
49. An optical glass according to any one of claims 1 to 3Characterized in that the optical glass has a density ρ of 3.7g/cm 3 The following are set forth; and/or coefficient of thermal expansion alpha -30/70℃ 90X 10 -7 and/K or below; and/or lambda 80 Less than or equal to 390nm; and/or lambda 5 Less than or equal to 340nm; and/or weatherability CR is class 1; and/or acid action resistance stability D A Class 1; and/or stability against water action D W Class 1; and/or knoop hardness H K Is 510 multiplied by 10 7 Pa or more; and/or abrasion degree F A 185 to 215; and/or Young's modulus E of 8500×10 7 ～10500×10 7 Pa。
50. An optical glass according to any one of claims 1 to 3, wherein the optical glass has a density ρ of 3.6g/cm 3 The following are set forth; and/or coefficient of thermal expansion alpha -30/70℃ 85X 10 -7 and/K or below; and/or lambda 80 Less than or equal to 385nm; and/or lambda 5 Less than or equal to 335nm; and/or knoop hardness H K Is 520 multiplied by 10 7 Pa or more; and/or abrasion degree F A 190-210; and/or Young's modulus E of 9000×10 7 ～10000×10 7 Pa。
51. A glass preform comprising the optical glass according to any one of claims 1 to 50.
52. An optical element, characterized in that it is made of the optical glass according to any one of claims 1 to 50 or made of the glass preform according to claim 51.
53. An optical instrument comprising the optical glass according to any one of claims 1 to 50 and/or the optical element according to claim 52.
CN202211273285.7A 2022-10-18 2022-10-18 Optical glass, optical element and optical instrument Active CN115448591B (en)

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