CN117088605A - Optical glass, glass preform, optical element, and optical instrument - Google Patents

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

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Publication number
CN117088605A
CN117088605A CN202311066494.9A CN202311066494A CN117088605A CN 117088605 A CN117088605 A CN 117088605A CN 202311066494 A CN202311066494 A CN 202311066494A CN 117088605 A CN117088605 A CN 117088605A
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sio
optical glass
percent
tio
glass
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匡波
毛露路
郝良振
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CDGM Glass Co Ltd
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CDGM Glass Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/062—Glass compositions containing silica with less than 40% silica by weight
    • C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
    • 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
    • C03C4/00—Compositions for glass with special properties
    • 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
    • C03C4/20—Compositions for glass with special properties for chemical resistant glass

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

Abstract

The invention provides optical glass, which comprises the following components in percentage by weight: siO (SiO) 2 +B 2 O 3 ：3～18％；La 2 O 3 +Y 2 O 3 +Gd 2 O 3 ：45～65％；ZrO 2 ：3～13％；Nb 2 O 5 ：3～15％；TiO 2 :8 to 22 percent, wherein (La) 2 O 3 +Gd 2 O 3 )/Nb 2 O 5 3.5 to 15.0. Through reasonable component design, the optical glass has the expected refractive index and Abbe number, and also has lower thermal expansion coefficient and excellent light transmittance.

Description

Optical glass, glass preform, optical element, and optical instrument
Technical Field
The present invention relates to an optical glass, and more particularly, to an optical glass having a refractive index of 1.98 or more and an abbe number of 22 to 31, and a glass preform, an optical element, and an optical instrument each made of the same.
Background
The high refractive index optical glass is a key material for manufacturing the diffraction optical waveguide device of the augmented reality/mixed reality (AR/MR) device, the refractive index of the high refractive index optical glass determines the field angle of the AR/MR device, for example, the optical glass with the refractive index of 1.9 can realize the field angle of 65 degrees, but in practical application, the optical glass with the higher refractive index is required to improve the field angle of the AR/MR device, so that the near-reality use experience is brought to a user. In addition, the lens formed of the high refractive index optical glass can miniaturize the optical system, and particularly, the ultra-high refractive index optical glass having a refractive index of 1.98 or more has been increasingly demanded in the market.
CN102050574A discloses an extra-high refractive index optical glass with a refractive index of 2.0-2.3 and an Abbe number of 17-25, which is B 2 O 3 -Bi 2 O 3 -Ga 2 O 3 The system glass, although having a higher refractive index, is known from its embodiment, λ in its embodiment 70 Most preferably 490nm lambda 5 And most preferably 428nm, the light transmittance of the glass is low, and the brightness of the AR/MR device can be greatly reduced. On the other hand, when an optical element mounted in an in-vehicle optical device or an optical element mounted in an optical device that generates heat such as a projector, a copier, a laser printer, or the like is used in an environment where a temperature change is large, if the thermal expansion coefficient of an optical glass is too large, thermal expansion of the optical element occurs due to a change in the environmental temperature, stress occurs in the optical element and birefringence occurs due to a difference in the expansion coefficient from an optical element fixing jig, and imaging characteristics change. Accordingly, it is desirable for the optical glass to have a low thermal expansion coefficient.
Disclosure of Invention
The technical problem to be solved by the invention is to provide an optical glass with a refractive index of more than 1.98, an Abbe number of 22-31, a low thermal expansion coefficient and excellent light transmittance.
The technical scheme adopted for solving the technical problems is as follows:
(1) The optical glass comprises the following components in percentage by weight: siO (SiO) 2 +B 2 O 3 ：3～18％；La 2 O 3 +Y 2 O 3 +Gd 2 O 3 ：45～65％；ZrO 2 ：3～13％；Nb 2 O 5 ：3～15％；TiO 2 :8 to 22 percent, wherein (La) 2 O 3 +Gd 2 O 3 )/Nb 2 O 5 3.5 to 15.0.
(2) The optical glass according to (1), which comprises the following components in percentage by weight:ZnO: 0-5%; and/or RO:0 to 6 percent; and/or Rn 2 O: 0-5%; and/or WO 3 : 0-5%; and/or Ta 2 O 5 : 0-5%; and/or Al 2 O 3 : 0-5%; and/or Yb 2 O 3 : 0-8%; and/or GeO 2 :0 to 3 percent; and/or P 2 O 5 :0 to 4 percent; and/or clarifying agent: 0 to 1 percent of RO is one or more of MgO, caO, srO, baO, rn 2 O is Li 2 O、Na 2 O、K 2 One or more of O and a clarifying agent of Sb 2 O 3 、SnO 2 、CeO 2 One or more of the following.
(3) Optical glass containing ZrO 2 、Nb 2 O 5 、TiO 2 As an essential component, the composition contains 3 to 18 weight percent of SiO 2 +B 2 O 3 And 45 to 65 percent of La 2 O 3 +Y 2 O 3 +Gd 2 O 3 Wherein (La) 2 O 3 +Gd 2 O 3 )/Nb 2 O 5 3.5 to 15.0, and the refractive index n of the optical glass d An Abbe number v of 1.98 or more d Is 22 to 31, the thermal expansion coefficient alpha -30/70℃ 90X 10 -7 and/K or below.
(4) The optical glass according to (3), which comprises the following components in percentage by weight: zrO (ZrO) 2 :3 to 13 percent; and/or Nb 2 O 5 : 3-15%; and/or TiO 2 : 8-22%; and/or ZnO: 0-5%; and/or RO:0 to 6 percent; and/or Rn 2 O: 0-5%; and/or WO 3 : 0-5%; and/or Ta 2 O 5 : 0-5%; and/or Al 2 O 3 : 0-5%; and/or Yb 2 O 3 : 0-8%; and/or GeO 2 :0 to 3 percent; and/or P 2 O 5 :0 to 4 percent; and/or clarifying agent: 0 to 1 percent of RO is one or more of MgO, caO, srO, baO, rn 2 O is Li 2 O、Na 2 O、K 2 One or more of O and a clarifying agent of Sb 2 O 3 、SnO 2 、CeO 2 One or more of the following.
(5) The optical glass according to any one of (1) to (4), wherein the components are represented by weight percent: (La) 2 O 3 +Gd 2 O 3 )/Nb 2 O 5 Is 4.0 to 10.0, preferably (La) 2 O 3 +Gd 2 O 3 )/Nb 2 O 5 Is 5.0 to 8.0, more preferably (La) 2 O 3 +Gd 2 O 3 )/Nb 2 O 5 5.5 to 6.5.
(6) The optical glass according to any one of (1) to (4), wherein the components are represented by weight percent: siO (SiO) 2 /B 2 O 3 From 0.4 to 4.0, preferably SiO 2 /B 2 O 3 From 0.5 to 3.0, more preferably SiO 2 /B 2 O 3 From 0.6 to 2.0, siO is more preferable 2 /B 2 O 3 0.7 to 1.2.
(7) The optical glass according to any one of (1) to (4), wherein the components are represented by weight percent: (ZnO+Y) 2 O 3 )/Gd 2 O 3 Is 0.8 or less, preferably (ZnO+Y) 2 O 3 )/Gd 2 O 3 Is 0.6 or less, more preferably (ZnO+Y) 2 O 3 )/Gd 2 O 3 In the range of 0.01 to 0.5, more preferably (ZnO+Y) 2 O 3 )/Gd 2 O 3 0.05 to 0.3.
(8) The optical glass according to any one of (1) to (4), wherein the components are represented by weight percent: (SiO) 2 +B 2 O 3 )/Gd 2 O 3 Is 0.3 to 2.5, preferably (SiO) 2 +B 2 O 3 )/Gd 2 O 3 Is 0.4 to 2.0, more preferably (SiO) 2 +B 2 O 3 )/Gd 2 O 3 Is 0.5 to 1.5, more preferably (SiO) 2 +B 2 O 3 )/Gd 2 O 3 0.7 to 1.2.
(9) The optical glass according to any one of (1) to (4), wherein the components are represented by weight percent: znO/(SiO) 2 +B 2 O 3 ) Is 0.8 or less, preferably ZnO/(SiO) 2 +B 2 O 3 ) Is 0.6 or less, more preferably ZnO/(SiO) 2 +B 2 O 3 ) In the range of 0.01 to 0.5, znO/(SiO) is more preferable 2 +B 2 O 3 ) 0.02 to 0.3.
(10) The optical glass according to any one of (1) to (4), wherein the components are represented by weight percent: (SiO) 2 +B 2 O 3 +La 2 O 3 )/ZrO 2 Is 4.0 to 15.0, preferably (SiO) 2 +B 2 O 3 +La 2 O 3 )/ZrO 2 Is 5.0 to 12.0, more preferably (SiO) 2 +B 2 O 3 +La 2 O 3 )/ZrO 2 Is 6.5 to 10.0, more preferably (SiO) 2 +B 2 O 3 +La 2 O 3 )/ZrO 2 7.5 to 9.0.
(11) The optical glass according to any one of (1) to (4), wherein the components are represented by weight percent: b (B) 2 O 3 /TiO 2 From 0.1 to 1.0, preferably B 2 O 3 /TiO 2 From 0.2 to 0.8, more preferably B 2 O 3 /TiO 2 From 0.2 to 0.7, further preferably B 2 O 3 /TiO 2 0.3 to 0.5.
(12) The optical glass according to any one of (1) to (4), wherein the components are represented by weight percent: (Gd) 2 O 3 +Nb 2 O 5 +TiO 2 )/(SiO 2 +B 2 O 3 ) Is 1.0 to 8.0, preferably (Gd) 2 O 3 +Nb 2 O 5 +TiO 2 )/(SiO 2 +B 2 O 3 ) Is 1.5 to 6.0, more preferably (Gd) 2 O 3 +Nb 2 O 5 +TiO 2 )/(SiO 2 +B 2 O 3 ) Is 2.0 to 5.0, and more preferably (Gd) 2 O 3 +Nb 2 O 5 +TiO 2 )/(SiO 2 +B 2 O 3 ) 2.5 to 4.0.
(13) The optical glass according to any one of (1) to (4), wherein the components are represented by weight percent: (Gd) 2 O 3 +TiO 2 )/(La 2 O 3 +Nb 2 O 5 ) Is 0.3 to 0.9, preferably (Gd) 2 O 3 +TiO 2 )/(La 2 O 3 +Nb 2 O 5 ) Is 0.35 to 0.8, more preferably (Gd) 2 O 3 +TiO 2 )/(La 2 O 3 +Nb 2 O 5 ) Is 0.4 to 0.7, and more preferably (Gd) 2 O 3 +TiO 2 )/(La 2 O 3 +Nb 2 O 5 ) 0.45 to 0.6.
(14) The optical glass according to any one of (1) to (4), wherein the components are represented by weight percent: (B) 2 O 3 +La 2 O 3 )/(Gd 2 O 3 +Nb 2 O 5 +TiO 2 ) Is 0.7 to 2.5, preferably (B) 2 O 3 +La 2 O 3 )/(Gd 2 O 3 +Nb 2 O 5 +TiO 2 ) Is 0.8 to 2.0, more preferably (B) 2 O 3 +La 2 O 3 )/(Gd 2 O 3 +Nb 2 O 5 +TiO 2 ) Is 0.9 to 1.7, more preferably (B) 2 O 3 +La 2 O 3 )/(Gd 2 O 3 +Nb 2 O 5 +TiO 2 ) 1.0 to 1.5.
(15) The optical glass according to any one of (1) to (4), wherein the components are represented by weight percent: (B) 2 O 3 +La 2 O 3 )/(Gd 2 O 3 +SiO 2 ) Is 1.5 to 5.5, preferably (B) 2 O 3 +La 2 O 3 )/(Gd 2 O 3 +SiO 2 ) Is 2.0 to 4.0, more preferably (B) 2 O 3 +La 2 O 3 )/(Gd 2 O 3 +SiO 2 ) Is 2.3 to 3.3, more preferably (B) 2 O 3 +La 2 O 3 )/(Gd 2 O 3 +SiO 2 ) 2.5 to 3.2.
(16) The optical glass according to any one of (1) to (4), wherein the components are represented by weight percent: b (B) 2 O 3 /(ZrO 2 +Y 2 O 3 ) From 0.2 to 2.5, preferably B 2 O 3 /(ZrO 2 +Y 2 O 3 ) From 0.4 to 2.0, more preferably B 2 O 3 /(ZrO 2 +Y 2 O 3 ) From 0.5 to 1.5, further preferably B 2 O 3 /(ZrO 2 +Y 2 O 3 ) 0.6 to 1.0.
(17) The optical glass according to any one of (1) to (4), wherein the components are represented by weight percent: RO/Nb 2 O 5 Is 0.8 or less, preferably RO/Nb 2 O 5 Is 0.5 or less, more preferably RO/Nb 2 O 5 Is 0.3 or less, and further preferably RO/Nb 2 O 5 Is less than 0.1, and the RO is one or more of MgO, caO, srO, baO.
(18) The optical glass according to any one of (1) to (4), wherein the components are represented by weight percent: (B) 2 O 3 +La 2 O 3 +Y 2 O 3 +RO)/Gd 2 O 3 Is 2.0 to 7.0, preferably (B) 2 O 3 +La 2 O 3 +Y 2 O 3 +RO)/Gd 2 O 3 Is 2.5 to 6.0, more preferably (B) 2 O 3 +La 2 O 3 +Y 2 O 3 +RO)/Gd 2 O 3 Is 3.0 to 4.6, more preferably (B) 2 O 3 +La 2 O 3 +Y 2 O 3 +RO)/Gd 2 O 3 3.5 to 4.5, wherein the RO is one or more of MgO, caO, srO, baO.
(19) The optical glass according to any one of (1) to (4), wherein the components are represented by weight percent: (RO+GeO) 2 +Y 2 O 3 +Ta 2 O 5 )/La 2 O 3 Is 0.3 or less, preferably (RO+GeO) 2 +Y 2 O 3 +Ta 2 O 5 )/La 2 O 3 Is 0.2 or less, more preferably (RO+GeO) 2 +Y 2 O 3 +Ta 2 O 5 )/La 2 O 3 Is 0.15 or less, more preferably (RO+GeO) 2 +Y 2 O 3 +Ta 2 O 5 )/La 2 O 3 Is 0.1 or less, and RO is MgOOne or more of CaO, srO, baO.
(20) The optical glass according to any one of (1) to (4), wherein the components are represented by weight percent: siO (SiO) 2 +B 2 O 3 :5 to 15%, preferably SiO 2 +B 2 O 3 : 7-13%; and/or La 2 O 3 +Y 2 O 3 +Gd 2 O 3 :50 to 63%, preferably La 2 O 3 +Y 2 O 3 +Gd 2 O 3 : 52-60%; and/or ZrO 2 :4 to 11%, preferably ZrO 2 : 6-10%; and/or Nb 2 O 5 :5 to 13%, preferably Nb 2 O 5 : 7-12%; and/or TiO 2 :10 to 20%, preferably TiO 2 : 13-18%; and/or ZnO:0 to 4%, preferably ZnO:0.1 to 3 percent; and/or RO:0 to 4%, preferably RO:0 to 2 percent; and/or Rn 2 O:0 to 3%, preferably Rn 2 O:0 to 1 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 Al 2 O 3 :0 to 3%, preferably Al 2 O 3 :0 to 1 percent; and/or Yb 2 O 3 :0 to 5%, preferably Yb 2 O 3 :0 to 1 percent; and/or GeO 2 :0 to 2%, preferably GeO 2 :0 to 1 percent; and/or P 2 O 5 :0 to 2%, preferably P 2 O 5 :0 to 1 percent; and/or clarifying agent: 0 to 0.5%, preferably a clarifying agent: 0 to 0.2 percent, the RO is one or more of MgO, caO, srO, baO and Rn 2 O is Li 2 O、Na 2 O、K 2 One or more of O and a clarifying agent of Sb 2 O 3 、SnO 2 、CeO 2 One or more of the following.
(21) The optical glass according to any one of (1) to (4), wherein the components are represented by weight percent: siO (SiO) 2 :1 to 10%, preferably SiO 2 :2 to 8%, more preferably SiO 2 : 3-7%; and/or B 2 O 3 :1 to 10%, preferably B 2 O 3 :2 to 9%, more preferably B 2 O 3 : 4-8%; and/or La 2 O 3 :35 to 50%, preferably La 2 O 3 :37 to 47%, more preferably La 2 O 3 : 41-46%; and/or Y 2 O 3 :0 to 6%, preferably Y 2 O 3 :0 to 4%, more preferably Y 2 O 3 :0.1 to 3 percent; and/or Gd 2 O 3 :6 to 20%, preferably Gd 2 O 3 :8 to 18%, more preferably Gd 2 O 3 ：11～15％。
(22) The optical glass according to any one of (1) to (4), wherein the component 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 RO; and/or does not contain Rn 2 O; and/or does not contain P 2 O 5 The method comprises the steps of carrying out a first treatment on the surface of the And/or does not contain Al 2 O 3 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 not containing Yb 2 O 3 The RO is one or more of MgO, caO, srO, baO, rn 2 O is Li 2 O、Na 2 O、K 2 One or more of O.
(23) The refractive index n of the optical glass according to any one of (1) to (4) d An Abbe number v of 1.98 or more, preferably 1.99 or more, more preferably 2.00 to 2.15, still more preferably 2.01 to 2.10, still more preferably 2.03 to 2.07 d 22 to 31, preferably 23 to 30, more preferably 24 to 29, and even more preferably 25 to 28.
(24) The optical glass according to any one of (1) to (4), which has a coefficient of thermal expansion α -30/70℃ 90X 10 -7 Preferably 80X 10, and K is less than or equal to -7 Preferably 75X 10 or less per K -7 and/K or below; and/or acid action resistance stability D A More than 2 types, preferably 1 type; and/or lambda 70 Is 480nm or less, preferably lambda 70 470nm or less, more preferably lambda 70 465nm or less; and/or lambda 5 Is 390nm or less, preferably lambda 5 Is 380nm or less, more preferably lambda 5 Is 375nm or less; and/or weather resistance CR is 2 or more, preferably 1; and/or knoop hardness H K 630X 10 7 Pa or morePreferably 650X 10 7 Pa or more, more preferably 660×10 7 Pa or more; and/or Young's modulus E of 11000X 10 7 Pa or more, preferably 12000×10 7 Pa or more, more preferably 13000×10 7 Pa or more; and/or the degree of air bubbles is a class A or more, preferably A 0 Above the stage, more preferably A 00 A stage; and/or density ρ of 5.50g/cm 3 Hereinafter, it is preferably 5.40g/cm 3 Hereinafter, more preferably 5.30g/cm 3 The following are set forth; and/or abrasion degree F A From 90 to 140, preferably from 100 to 130, more preferably from 110 to 123.
(25) A glass preform made of the optical glass according to any one of (1) to (24).
(26) An optical element made of the optical glass according to any one of (1) to (24), or made of the glass preform according to (25).
(27) An optical instrument comprising the optical glass according to any one of (1) to (24), and/or the optical element according to (26).
The beneficial effects of the invention are as follows: through reasonable component design, the optical glass has the expected refractive index and Abbe number, and also has lower thermal expansion coefficient and excellent light transmittance.
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 The viscosity of the molten glass can be increased, the coloring of the glass can be reduced, the chemical stability of the glass can be improved, and the devitrification resistance can be improved, in the invention, the glass comprises more than 1% of SiO 2 To obtain the above effect, siO is preferred 2 The content of (2) is more than 2%, more preferably SiO 2 The content of (2) is 3% or more. If SiO is 2 The content of (2) is too high, the melting difficulty of the glass is increased, the transition temperature is increased, and the refractive index is reduced. Thus, siO in the present invention 2 The upper limit of the content of (2) is 10%, preferably 8%, more preferably 7%.
B 2 O 3 The glass has improved meltability and devitrification resistance, and is favorable for lowering the glass transition temperature, and the glass comprises more than 1 percent of B 2 O 3 To obtain the above effect, it preferably contains 2% or more of B 2 O 3 More preferably, the content of B is 4% or more 2 O 3 . If B 2 O 3 If the content of (b) is too high, the chemical stability of the glass becomes poor, and the refractive index becomes low, which is disadvantageous in obtaining the high refractive index of the present invention. Thus B 2 O 3 The content of (2) is 10% or less, preferably 9% or less, and more preferably 8% or less.
In some embodiments, siO 2 And B 2 O 3 Is the total content of SiO 2 +B 2 O 3 Controlling the content within the range of 3-18%In addition, the chemical stability of the glass is improved, and the abrasion degree of the glass is optimized. Therefore, siO is preferred 2 +B 2 O 3 3 to 18%, more preferably SiO 2 +B 2 O 3 5 to 15%, further preferably SiO 2 +B 2 O 3 7 to 13 percent.
In some embodiments, siO 2 Content of (B) and B 2 O 3 Ratio between the contents of SiO 2 /B 2 O 3 The glass is controlled within the range of 0.4-4.0, which is beneficial to improving the crystallization resistance of the glass and optimizing the weather resistance and Young modulus of the glass. Therefore, siO is preferred 2 /B 2 O 3 From 0.4 to 4.0, more preferably SiO 2 /B 2 O 3 From 0.5 to 3.0, siO is more preferable 2 /B 2 O 3 From 0.6 to 2.0, siO is more preferable 2 /B 2 O 3 0.7 to 1.2.
La 2 O 3 Is an effective component for improving the refractive index of glass, has obvious effect on improving the chemical stability and the devitrification resistance of the glass, and is difficult to reach the required optical constant if the content is less than 35 percent; if the content is more than 50%, the devitrification tendency of the glass increases, and the thermal stability becomes poor. Therefore La 2 O 3 The content of (2) is limited to 35 to 50%, preferably 37 to 47%, more preferably 41 to 46%.
Gd 2 O 3 The refractive index and chemical stability of the glass can be improved, and the thermal stability of the glass can be improved, but if the content is too high, the devitrification resistance of the glass becomes poor, and the raw material cost increases. Thus Gd 2 O 3 The content of (2) is 6 to 20%, preferably 8 to 18%, more preferably 11 to 15%.
In some embodiments, siO 2 And B 2 O 3 Is the total content of SiO 2 +B 2 O 3 With Gd 2 O 3 Ratio between the contents of (SiO) 2 +B 2 O 3 )/Gd 2 O 3 The abrasion and bubble degree of the glass can be optimized and the Young's modulus of the glass can be improved by controlling the abrasion and bubble degree within the range of 0.3-2.5. Therefore, it is preferable that (SiO 2 +B 2 O 3 )/Gd 2 O 3 Is 0.3 to 2.5, more preferably (SiO) 2 +B 2 O 3 )/Gd 2 O 3 Is 0.4 to 2.0, more preferably (SiO) 2 +B 2 O 3 )/Gd 2 O 3 Is 0.5 to 1.5, more preferably (SiO) 2 +B 2 O 3 )/Gd 2 O 3 0.7 to 1.2.
In some embodiments, B 2 O 3 And La (La) 2 O 3 Total content B of (2) 2 O 3 +La 2 O 3 With Gd 2 O 3 And SiO 2 Is the total content Gd of 2 O 3 +SiO 2 Ratio between (B) 2 O 3 +La 2 O 3 )/(Gd 2 O 3 +SiO 2 ) The control is in the range of 1.5-5.5, which is beneficial to reducing the density of the glass and improving the chemical stability of the glass. Therefore, (B) is preferable 2 O 3 +La 2 O 3 )/(Gd 2 O 3 +SiO 2 ) Is 1.5 to 5.5, more preferably (B) 2 O 3 +La 2 O 3 )/(Gd 2 O 3 +SiO 2 ) 2.0 to 4.0. Further, control (B 2 O 3 +La 2 O 3 )/(Gd 2 O 3 +SiO 2 ) In the range of 2.3 to 3.3, the bubble degree and Young's modulus of the glass can be further optimized. Therefore, (B) is more preferable 2 O 3 +La 2 O 3 )/(Gd 2 O 3 +SiO 2 ) Is 2.3 to 3.3, more preferably (B) 2 O 3 +La 2 O 3 )/(Gd 2 O 3 +SiO 2 ) 2.5 to 3.2.
Y 2 O 3 The refractive index and devitrification resistance of the glass can be improved, and if the content is too high, the chemical stability and weather resistance of the glass become poor. Thus, Y in the present invention 2 O 3 The content of (2) is 0 to 6%, preferably 0 to 4%, more preferably 0.1 to 3%.
In some embodiments, la 2 O 3 、Y 2 O 3 And Gd 2 O 3 Sum of (1) La 2 O 3 +Y 2 O 3 +Gd 2 O 3 The glass is controlled in the range of 45-65%, the desired refractive index and Abbe number are more easily obtained, and the devitrification resistance and weather resistance of the glass are optimized. Therefore, la is preferred 2 O 3 +Y 2 O 3 +Gd 2 O 3 45 to 65%, more preferably La 2 O 3 +Y 2 O 3 +Gd 2 O 3 50 to 63%, more preferably La 2 O 3 +Y 2 O 3 +Gd 2 O 3 52-60%.
Yb 2 O 3 Is a component for imparting high refractive and low dispersion properties to glass, and if the content exceeds 8%, the crystallization resistance of the glass is lowered. Thus Yb 2 O 3 The content of (C) is 0 to 8%, preferably 0 to 5%, more preferably 0 to 1%, and even more preferably no Yb is contained 2 O 3 。
ZrO 2 Can improve the devitrification resistance of the glass, improve the chemical stability and the mechanical property of the glass, and if the content is too high, the melting difficulty of the glass is increased, the melting temperature is increased, and impurities appear in the glass and the light transmittance is reduced. Thus, zrO in the present invention 2 The content of (2) is 3 to 13%, preferably 4 to 11%, more preferably 6 to 10%.
In some embodiments, siO 2 、B 2 O 3 And La (La) 2 O 3 Is the total content of SiO 2 +B 2 O 3 +La 2 O 3 With ZrO 2 Ratio between the contents of (SiO) 2 +B 2 O 3 +La 2 O 3 )/ZrO 2 The Young's modulus and hardness of the glass can be improved and the weather resistance of the glass can be optimized by controlling the Young's modulus and hardness within the range of 4.0-15.0. Therefore, it is preferable that (SiO 2 +B 2 O 3 +La 2 O 3 )/ZrO 2 Is 4.0 to 15.0, more preferably (SiO) 2 +B 2 O 3 +La 2 O 3 )/ZrO 2 Is 5.0 to 12.0, more preferably (SiO) 2 +B 2 O 3 +La 2 O 3 )/ZrO 2 Is 6.5 to 10.0, more preferably (SiO) 2 +B 2 O 3 +La 2 O 3 )/ZrO 2 7.5 to 9.0.
In some embodiments, B 2 O 3 Content of (3) and ZrO 2 And Y 2 O 3 Is based on the sum of ZrO 2 +Y 2 O 3 Ratio B between 2 O 3 /(ZrO 2 +Y 2 O 3 ) The chemical stability and the thermal expansion coefficient of the glass can be improved and the hardness of the glass is prevented from being reduced by controlling the glass within the range of 0.2-2.5. Therefore, B is preferred 2 O 3 /(ZrO 2 +Y 2 O 3 ) From 0.2 to 2.5, more preferably B 2 O 3 /(ZrO 2 +Y 2 O 3 ) From 0.4 to 2.0, further preferably B 2 O 3 /(ZrO 2 +Y 2 O 3 ) From 0.5 to 1.5, more preferably B 2 O 3 /(ZrO 2 +Y 2 O 3 ) 0.6 to 1.0.
Nb 2 O 5 The glass has improved refractive index and devitrification resistance, and reduced thermal expansion coefficient, and the glass contains Nb in an amount of 3% or more 2 O 5 To obtain the above effect, nb is preferable 2 O 5 The lower limit of the content of (2) is 5%, and more preferably the lower limit is 7%. If Nb is 2 O 5 The content of Nb exceeds 15%, 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 15%, preferably 13%, more preferably 12%.
In some embodiments, la 2 O 3 And Gd 2 O 3 Sum of (1) La 2 O 3 +Gd 2 O 3 With Nb 2 O 5 Ratio between the contents of (La) 2 O 3 +Gd 2 O 3 )/Nb 2 O 5 The glass is controlled within the range of 3.5-15.0, which is beneficial to the reduction of the thermal expansion coefficient of the glass and the optimization of the light transmittance and the Young modulus while the glass obtains the expected refractive index and Abbe number. Therefore, (La 2 O 3 +Gd 2 O 3 )/Nb 2 O 5 Is 3.5 to 15.0, more preferably (La) 2 O 3 +Gd 2 O 3 )/Nb 2 O 5 Is 4.0 to 10.0, more preferably (La) 2 O 3 +Gd 2 O 3 )/Nb 2 O 5 Is 5.0 to 8.0, more preferably (La) 2 O 3 +Gd 2 O 3 )/Nb 2 O 5 5.5 to 6.5.
TiO 2 The refractive index of the glass can be increased, the stability of the glass is improved, the density of the glass is reduced, if the content of the glass is too high, the Abbe number of the glass is difficult to reach the design requirement, and the light transmittance of the glass is reduced. Thus, tiO 2 The content of (2) is 8 to 22%, preferably 10 to 20%, more preferably 13 to 18%.
In some embodiments, B 2 O 3 Content of (2) and TiO 2 Ratio B between the contents of (2) 2 O 3 /TiO 2 The bubble degree and chemical stability of the glass can be improved and the light transmittance of the glass can be prevented from being reduced by controlling the bubble degree and chemical stability within the range of 0.1-1.0. Therefore, B is preferred 2 O 3 /TiO 2 From 0.1 to 1.0, more preferably B 2 O 3 /TiO 2 From 0.2 to 0.8, further preferably B 2 O 3 /TiO 2 From 0.2 to 0.7, more preferably B 2 O 3 /TiO 2 0.3 to 0.5.
In some embodiments, gd 2 O 3 、Nb 2 O 5 And TiO 2 Is the total content Gd of 2 O 3 +Nb 2 O 5 +TiO 2 With SiO 2 And B 2 O 3 Is the total content of SiO 2 +B 2 O 3 Ratio between (Gd) 2 O 3 +Nb 2 O 5 +TiO 2 )/(SiO 2 +B 2 O 3 ) The glass is controlled within the range of 1.0-8.0, which is beneficial to reducing the density and the thermal expansion coefficient of the glass and improving the chemical stability and the light transmittance of the glass. Therefore, (Gd 2 O 3 +Nb 2 O 5 +TiO 2 )/(SiO 2 +B 2 O 3 ) Is 1.0 to 8.0, more preferably (Gd) 2 O 3 +Nb 2 O 5 +TiO 2 )/(SiO 2 +B 2 O 3 ) Is 1.5 to 6.0, and more preferably (Gd) 2 O 3 +Nb 2 O 5 +TiO 2 )/(SiO 2 +B 2 O 3 ) Is 2.0 to 5.0, and more preferably (Gd) 2 O 3 +Nb 2 O 5 +TiO 2 )/(SiO 2 +B 2 O 3 ) 2.5 to 4.0.
In some embodiments, gd 2 O 3 And TiO 2 Is the total content Gd of 2 O 3 +TiO 2 With La 2 O 3 And Nb (Nb) 2 O 5 Sum of (1) La 2 O 3 +Nb 2 O 5 Ratio between (Gd) 2 O 3 +TiO 2 )/(La 2 O 3 +Nb 2 O 5 ) The density and the abrasion degree of the glass can be optimized by controlling the glass within the range of 0.3-0.9, and the crystallization resistance and the weather resistance of the glass are improved. Therefore, (Gd 2 O 3 +TiO 2 )/(La 2 O 3 +Nb 2 O 5 ) Is 0.3 to 0.9, more preferably (Gd) 2 O 3 +TiO 2 )/(La 2 O 3 +Nb 2 O 5 ) Is 0.35 to 0.8, more preferably (Gd) 2 O 3 +TiO 2 )/(La 2 O 3 +Nb 2 O 5 ) Is 0.4 to 0.7, and more preferably (Gd) 2 O 3 +TiO 2 )/(La 2 O 3 +Nb 2 O 5 ) 0.45 to 0.6.
In some embodiments, B 2 O 3 And La (La) 2 O 3 Total content B of (2) 2 O 3 +La 2 O 3 With Gd 2 O 3 、Nb 2 O 5 、TiO 2 Is the total content Gd of 2 O 3 +Nb 2 O 5 +TiO 2 Ratio between (B) 2 O 3 +La 2 O 3 )/(Gd 2 O 3 +Nb 2 O 5 +TiO 2 ) The bubble degree of the glass can be improved and the Young's modulus and hardness of the glass are prevented from being deteriorated by controlling the bubble degree to be in the range of 0.7-2.5. Therefore, (B) is preferable 2 O 3 +La 2 O 3 )/(Gd 2 O 3 +Nb 2 O 5 +TiO 2 ) Is 0.7 to 2.5, more preferably (B) 2 O 3 +La 2 O 3 )/(Gd 2 O 3 +Nb 2 O 5 +TiO 2 ) Is 0.8 to 2.0, and more preferably (B) 2 O 3 +La 2 O 3 )/(Gd 2 O 3 +Nb 2 O 5 +TiO 2 ) Is 0.9 to 1.7, more preferably (B) 2 O 3 +La 2 O 3 )/(Gd 2 O 3 +Nb 2 O 5 +TiO 2 ) 1.0 to 1.5.
ZnO can improve devitrification resistance of glass, improve meltability of glass raw materials, and reduce high-temperature viscosity and transition temperature of glass. If the ZnO content is too high, the difficulty in molding glass increases, and the thermal stability becomes poor. Accordingly, the content of ZnO is 0 to 5%, preferably 0 to 4%, more preferably 0.1 to 3%.
In some embodiments, znO and Y 2 O 3 ZnO+Y in the total content of (2) 2 O 3 With Gd 2 O 3 Ratio between the contents of (ZnO+Y) 2 O 3 )/Gd 2 O 3 The Young's modulus and crystallization resistance of the glass are improved by controlling the Young's modulus to be below 0.8. Therefore, (ZnO+Y) is preferable 2 O 3 )/Gd 2 O 3 Is 0.8 or less, more preferably (ZnO+Y) 2 O 3 )/Gd 2 O 3 Is 0.6 or less. Further, control (ZnO+Y 2 O 3 )/Gd 2 O 3 In the range of 0.01 to 0.5, the bubble degree of the glass can be further optimized. Therefore, (ZnO+Y) is more preferable 2 O 3 )/Gd 2 O 3 In the range of 0.01 to 0.5, more preferably (ZnO+Y) 2 O 3 )/Gd 2 O 3 0.05 to 0.3.
In some embodiments, the ZnO content is compared with SiO 2 And B 2 O 3 Is the sum of (1)Quantity of SiO 2 +B 2 O 3 Ratio between ZnO/(SiO) 2 +B 2 O 3 ) The control of the temperature below 0.8 is beneficial to improving the chemical stability and the bubble degree of the glass. Therefore, znO/(SiO) is preferable 2 +B 2 O 3 ) Is 0.8 or less, more preferably ZnO/(SiO) 2 +B 2 O 3 ) Is 0.6 or less. Further, znO/(SiO) is controlled 2 +B 2 O 3 ) In the range of 0.01 to 0.5, the thermal expansion coefficient of the glass can be further optimized. Therefore, znO/(SiO) is more preferable 2 +B 2 O 3 ) In the range of 0.01 to 0.5, znO/(SiO) is more preferable 2 +B 2 O 3 ) 0.02 to 0.3.
Alkaline earth oxide RO (RO is one or more of MgO, caO, srO, baO) can adjust the optical constants of the glass to optimize the chemical stability of the glass, but when its content is high, the devitrification resistance of the glass decreases. Therefore, the RO content is limited to 0 to 6%, preferably 0 to 4%, more preferably 0 to 2%. In some embodiments, it is further preferred that RO is not present.
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 temperature is controlled below 0.8, which is favorable for reducing the thermal expansion coefficient of the glass and preventing the weather resistance and crystallization resistance of the glass from being reduced. Therefore, RO/Nb is preferable 2 O 5 Is 0.8 or less, more preferably RO/Nb 2 O 5 Is 0.5 or less, and further preferably RO/Nb 2 O 5 Is 0.3 or less, and further preferably RO/Nb 2 O 5 Is 0.1 or less.
In some embodiments, B 2 O 3 、La 2 O 3 、Y 2 O 3 And the sum of RO B 2 O 3 +La 2 O 3 +Y 2 O 3 +RO and Gd 2 O 3 Ratio between the contents of (B) 2 O 3 +La 2 O 3 +Y 2 O 3 +RO)/Gd 2 O 3 The glass can be controlled within the range of 2.0 to 7.0, the weather resistance of the glass can be improved, and the abrasion degree and the thermal expansion system of the glass can be optimizedA number. Therefore, (B) is preferable 2 O 3 +La 2 O 3 +Y 2 O 3 +RO)/Gd 2 O 3 Is 2.0 to 7.0, more preferably (B) 2 O 3 +La 2 O 3 +Y 2 O 3 +RO)/Gd 2 O 3 Is 2.5 to 6.0, more preferably (B) 2 O 3 +La 2 O 3 +Y 2 O 3 +RO)/Gd 2 O 3 Is 3.0 to 4.6, more preferably (B) 2 O 3 +La 2 O 3 +Y 2 O 3 +RO)/Gd 2 O 3 3.5 to 4.5.
Alkali metal oxide Rn 2 O(Rn 2 O is Li 2 O、Na 2 O、K 2 One or more of O) can lower the glass transition temperature, adjust the optical constant and high-temperature viscosity of the glass, improve the meltability of the glass, but when the content thereof is high, the devitrification resistance and chemical stability of the glass are reduced. Thus, rn in the present invention 2 The content of O is 0 to 5%, preferably 0 to 3%, more preferably 0 to 1%. In some embodiments, it is further preferred that Rn is absent 2 O。
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 functions of improving the refractive index and improving the devitrification resistance of the glass, but if 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%. In some embodiments, it is further preferred that Ta is not present 2 O 5 。
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 。
P 2 O 5 The devitrification resistance of the glass can be improved, but if the content is too high, the chemical stability is lowered. Thus, P 2 O 5 The content of (C) is 0 to 4%, preferably 0 to 2%, more preferably 0 to 1%, and even more preferably P is not contained 2 O 5 。
GeO 2 Has the effect of improving the refractive index and the devitrification resistance, but if the content is too high, the chemical stability of the glass is reduced; 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 3%, preferably 0 to 2%, more preferably 0 to 1%, and even more preferably no GeO is contained 2 。
In some embodiments, RO, geO 2 、Y 2 O 3 And Ta 2 O 5 Is the sum of RO+GeO 2 +Y 2 O 3 +Ta 2 O 5 With La 2 O 3 Ratio between the contents of (RO+GeO) 2 +Y 2 O 3 +Ta 2 O 5 )/La 2 O 3 The bubble degree and abrasion degree of the glass can be optimized by controlling the glass content below 0.3, and the Young's modulus of the glass can be prevented from deteriorating. Therefore, (RO+GeO) is preferable 2 +Y 2 O 3 +Ta 2 O 5 )/La 2 O 3 Is 0.3 or less, more preferably (RO+GeO) 2 +Y 2 O 3 +Ta 2 O 5 )/La 2 O 3 Is 0.2 or less, more preferably (RO+GeO) 2 +Y 2 O 3 +Ta 2 O 5 )/La 2 O 3 Is 0.15 or less, more preferably (RO+GeO) 2 +Y 2 O 3 +Ta 2 O 5 )/La 2 O 3 Is 0.1 or less.
In the invention, 0 to 1 percent of Sb is contained 2 O 3 、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 0-0.5%, and the content of the clarifying agent is more preferably 0-0.2%. Since the optical glass of the present invention has a reasonable design of the types and contents of components and is excellent in bubble degree, it is further preferable that a clarifier is not contained in some embodiments. 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 (C) is 0 to 1%, more preferably 0 to 0.5%, still more preferably 0 to 0.2%, and still more preferably no Sb is contained 2 O 3 。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%, even more preferably 0 to 0.2%, and still more preferably no SnO is contained 2 。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 0 to 0.2%, and still 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 1.98, preferably 1.99, more preferably 2.00, even more preferably 2.01, and even more preferably 2.03.
In some embodiments, the refractive index (n d ) The upper limit of (2) is 2.15, preferably 2.10, more preferably 2.07.
In some embodiments, the Abbe number (. Nu.) of the optical glass of the present invention d ) The lower limit of (2) is preferably lower limit of 23, more preferably lower limit of 24, and still more preferablyThe lower limit is 25.
In some embodiments, the Abbe number (. Nu.) of the optical glass of the present invention d ) The upper limit of (2) is 31, preferably 30, more preferably 29, and even more preferably 28.
< 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℃ ) 90X 10 -7 Preferably 80X 10, and K is less than or equal to -7 Preferably 75X 10 or less per K -7 and/K or below.
< 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.
< coloring degree >
The glass of the present invention has a coloring degree (lambda) for short-wave transmission spectrum characteristics 70 And lambda (lambda) 5 ) And (3) representing. Lambda (lambda) 70 Refers to the wavelength corresponding to when the glass transmittance reaches 70%. Lambda (lambda) 70 Is to measure spectral transmittance in a wavelength range from 280nm to 700nm and to exhibit a wavelength of 70% 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 70 The small value of (2) means that the glass itself is extremely little colored and the light transmittance is high.
In some embodiments Lambda of the optical glass of the present invention 70 Is 480nm or less, preferably lambda 70 470nm or less, more preferably lambda 70 Is 465nm or less.
In some embodiments, λ of the optical glass of the present invention 5 Is 390nm or less, preferably lambda 5 Is 380nm or less, more preferably lambda 5 Is 375nm or less.
< 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 optical glass of the present invention has a knoop hardness (H K ) 630X 10 7 Pa or more, preferably 650×10 7 Pa or more, more preferably 660×10 7 Pa or more.
< 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 is 11000X 10 7 Pa or more, preferably 12000×10 7 Pa or more, more preferably 13000×10 7 Pa or more.
< bubble degree >
The bubble degree of the optical glass was measured according to the method prescribed in GB/T7962.8-2010.
In some embodiments, the optical glass of the present invention has a bubble degree of class A or more, preferably class A 0 Above the stage, more preferably A 00 A stage.
< 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 5.50g/cm 3 Hereinafter, it is preferably 5.40g/cm 3 Hereinafter, more preferably 5.30g/cm 3 The following is given.
< 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 ) The lower limit of (2) is 90, preferably 100, and more preferably 110.
In some embodiments, the abrasiveness (F A ) The upper limit of (2) is 140, preferably 130, more preferably 123.
[ 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 1200-1450 ℃ 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.
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 (27)

1. The optical glass is characterized by comprising the following components in percentage by weight: siO (SiO) 2 +B 2 O 3 ：3～18％；La 2 O 3 +Y 2 O 3 +Gd 2 O 3 ：45～65％；ZrO 2 ：3～13％；Nb 2 O 5 ：3～15％；TiO 2 :8 to 22 percent, wherein (La) 2 O 3 +Gd 2 O 3 )/Nb 2 O 5 3.5 to 15.0.
2. The optical glass according to claim 1, wherein the composition, expressed in weight percent, further comprises: znO: 0-5%; and/or RO:0 to 6 percent; and/or Rn 2 O: 0-5%; and/or WO 3 : 0-5%; and/or Ta 2 O 5 : 0-5%; and/or Al 2 O 3 : 0-5%; and/or Yb 2 O 3 : 0-8%; and/or GeO 2 :0 to 3 percent; and/or P 2 O 5 :0 to 4 percent; and/or clarifying agent: 0 to 1 percent of RO is one or more of MgO, caO, srO, baO, rn 2 O is Li 2 O、Na 2 O、K 2 One or more of O and a clarifying agent of Sb 2 O 3 、SnO 2 、CeO 2 One or more of the following.
3. An optical glass comprising ZrO 2 、Nb 2 O 5 、TiO 2 As an essential component, the composition contains 3 to 18 weight percent of SiO 2 +B 2 O 3 And 45 to 65 percent of La 2 O 3 +Y 2 O 3 +Gd 2 O 3 Wherein (La) 2 O 3 +Gd 2 O 3 )/Nb 2 O 5 3.5 to 15.0, and the refractive index n of the optical glass d An Abbe number v of 1.98 or more d Is 22 to 31, the thermal expansion coefficient alpha -30/70℃ 90X 10 -7 and/K or below.
4. An optical glass according to claim 3, characterized in that it comprises the following components in weight percent: zrO (ZrO) 2 :3 to 13 percent; and/or Nb 2 O 5 : 3-15%; and/or TiO 2 : 8-22%; and/or ZnO: 0-5%; and/or RO:0 to 6 percent; and/or Rn 2 O: 0-5%; and/or WO 3 : 0-5%; and/or Ta 2 O 5 : 0-5%; and/or Al 2 O 3 : 0-5%; and/or Yb 2 O 3 : 0-8%; and/or GeO 2 :0 to 3 percent; and/or P 2 O 5 :0 to 4 percent; and/or clarifying agent: 0 to 1 percent of RO is one or more of MgO, caO, srO, baO, rn 2 O is Li 2 O、Na 2 O、K 2 One or more of O and a clarifying agent of Sb 2 O 3 、SnO 2 、CeO 2 One or more of the following.
5. The optical glass according to any one of claims 1 to 4, wherein the components thereof are represented by weight percent, wherein: (La) 2 O 3 +Gd 2 O 3 )/Nb 2 O 5 Is 4.0 to 10.0, preferably (La) 2 O 3 +Gd 2 O 3 )/Nb 2 O 5 Is 5.0 to 8.0, more preferably (La) 2 O 3 +Gd 2 O 3 )/Nb 2 O 5 5.5 to 6.5.
6. The optical glass according to any one of claims 1 to 4, wherein the components thereof are represented by weight percent, wherein: siO (SiO) 2 /B 2 O 3 From 0.4 to 4.0, preferably SiO 2 /B 2 O 3 From 0.5 to 3.0, more preferably SiO 2 /B 2 O 3 From 0.6 to 2.0, siO is more preferable 2 /B 2 O 3 0.7 to 1.2.
7. The optical glass according to any one of claims 1 to 4, wherein the components thereof are represented by weight percent, wherein: (ZnO+Y) 2 O 3 )/Gd 2 O 3 Is 0.8 or less, preferably (ZnO+Y) 2 O 3 )/Gd 2 O 3 Is 0.6 or less, more preferably (ZnO+Y) 2 O 3 )/Gd 2 O 3 In the range of 0.01 to 0.5, more preferably (ZnO+Y) 2 O 3 )/Gd 2 O 3 0.05 to 0.3.
8. The optical glass according to any one of claims 1 to 4, wherein the components thereof are represented by weight percent, wherein: (SiO) 2 +B 2 O 3 )/Gd 2 O 3 Is 0.3 to 2.5, preferably (SiO) 2 +B 2 O 3 )/Gd 2 O 3 Is 0.4 to 2.0, more preferably (SiO) 2 +B 2 O 3 )/Gd 2 O 3 Is 0.5 to 1.5, more preferably (SiO) 2 +B 2 O 3 )/Gd 2 O 3 0.7 to 1.2.
9. The optical glass according to any one of claims 1 to 4, wherein the components thereof are represented by weight percent, wherein: znO/(SiO) 2 +B 2 O 3 ) Is 0.8 or less, preferably ZnO/(SiO) 2 +B 2 O 3 ) Is 0.6 or less, more preferably ZnO/(SiO) 2 +B 2 O 3 ) In the range of 0.01 to 0.5, znO/(SiO) is more preferable 2 +B 2 O 3 ) 0.02 to 0.3.
10. The optical glass according to any one of claims 1 to 4, wherein the components thereof are represented by weight percent, wherein: (SiO) 2 +B 2 O 3 +La 2 O 3 )/ZrO 2 Is 4.0 to 15.0, preferably (SiO) 2 +B 2 O 3 +La 2 O 3 )/ZrO 2 Is 5.0 to 12.0, more preferably (SiO) 2 +B 2 O 3 +La 2 O 3 )/ZrO 2 Is 6.5 to 10.0, more preferably (SiO) 2 +B 2 O 3 +La 2 O 3 )/ZrO 2 7.5 to 9.0.
11. The optical glass according to any one of claims 1 to 4, wherein the components thereof are represented by weight percent, wherein: b (B) 2 O 3 /TiO 2 From 0.1 to 1.0, preferably B 2 O 3 /TiO 2 From 0.2 to 0.8, more preferably B 2 O 3 /TiO 2 From 0.2 to 0.7, further preferably B 2 O 3 /TiO 2 0.3 to 0.5.
12. The optical glass according to any one of claims 1 to 4, wherein the components thereof are represented by weight percent, wherein: (Gd) 2 O 3 +Nb 2 O 5 +TiO 2 )/(SiO 2 +B 2 O 3 ) Is 1.0 to 8.0, preferably (Gd) 2 O 3 +Nb 2 O 5 +TiO 2 )/(SiO 2 +B 2 O 3 ) Is 1.5 to 6.0, more preferably (Gd) 2 O 3 +Nb 2 O 5 +TiO 2 )/(SiO 2 +B 2 O 3 ) Is 2.0 to 5.0, and more preferably (Gd) 2 O 3 +Nb 2 O 5 +TiO 2 )/(SiO 2 +B 2 O 3 ) 2.5 to 4.0.
13. The optical glass according to any one of claims 1 to 4, wherein the components thereof are represented by weight percent, wherein: (Gd) 2 O 3 +TiO 2 )/(La 2 O 3 +Nb 2 O 5 ) Is 0.3 to 0.9, preferably (Gd) 2 O 3 +TiO 2 )/(La 2 O 3 +Nb 2 O 5 ) Is thatFrom 0.35 to 0.8, more preferably (Gd) 2 O 3 +TiO 2 )/(La 2 O 3 +Nb 2 O 5 ) Is 0.4 to 0.7, and more preferably (Gd) 2 O 3 +TiO 2 )/(La 2 O 3 +Nb 2 O 5 ) 0.45 to 0.6.
14. The optical glass according to any one of claims 1 to 4, wherein the components thereof are represented by weight percent, wherein: (B) 2 O 3 +La 2 O 3 )/(Gd 2 O 3 +Nb 2 O 5 +TiO 2 ) Is 0.7 to 2.5, preferably (B) 2 O 3 +La 2 O 3 )/(Gd 2 O 3 +Nb 2 O 5 +TiO 2 ) Is 0.8 to 2.0, more preferably (B) 2 O 3 +La 2 O 3 )/(Gd 2 O 3 +Nb 2 O 5 +TiO 2 ) Is 0.9 to 1.7, more preferably (B) 2 O 3 +La 2 O 3 )/(Gd 2 O 3 +Nb 2 O 5 +TiO 2 ) 1.0 to 1.5.
15. The optical glass according to any one of claims 1 to 4, wherein the components thereof are represented by weight percent, wherein: (B) 2 O 3 +La 2 O 3 )/(Gd 2 O 3 +SiO 2 ) Is 1.5 to 5.5, preferably (B) 2 O 3 +La 2 O 3 )/(Gd 2 O 3 +SiO 2 ) Is 2.0 to 4.0, more preferably (B) 2 O 3 +La 2 O 3 )/(Gd 2 O 3 +SiO 2 ) Is 2.3 to 3.3, more preferably (B) 2 O 3 +La 2 O 3 )/(Gd 2 O 3 +SiO 2 ) 2.5 to 3.2.
16. The optical glass according to any one of claims 1 to 4, wherein the components thereof are represented by weight percent, wherein: b (B) 2 O 3 /(ZrO 2 +Y 2 O 3 ) From 0.2 to 2.5, preferably B 2 O 3 /(ZrO 2 +Y 2 O 3 ) From 0.4 to 2.0, more preferably B 2 O 3 /(ZrO 2 +Y 2 O 3 ) From 0.5 to 1.5, further preferably B 2 O 3 /(ZrO 2 +Y 2 O 3 ) 0.6 to 1.0.
17. The optical glass according to any one of claims 1 to 4, wherein the components thereof are represented by weight percent, wherein: RO/Nb 2 O 5 Is 0.8 or less, preferably RO/Nb 2 O 5 Is 0.5 or less, more preferably RO/Nb 2 O 5 Is 0.3 or less, and further preferably RO/Nb 2 O 5 Is less than 0.1, and the RO is one or more of MgO, caO, srO, baO.
18. The optical glass according to any one of claims 1 to 4, wherein the components thereof are represented by weight percent, wherein: (B) 2 O 3 +La 2 O 3 +Y 2 O 3 +RO)/Gd 2 O 3 Is 2.0 to 7.0, preferably (B) 2 O 3 +La 2 O 3 +Y 2 O 3 +RO)/Gd 2 O 3 Is 2.5 to 6.0, more preferably (B) 2 O 3 +La 2 O 3 +Y 2 O 3 +RO)/Gd 2 O 3 Is 3.0 to 4.6, more preferably (B) 2 O 3 +La 2 O 3 +Y 2 O 3 +RO)/Gd 2 O 3 3.5 to 4.5, wherein the RO is one or more of MgO, caO, srO, baO.
19. The optical glass according to any one of claims 1 to 4, wherein the components thereof are represented by weight percent, wherein: (RO+GeO) 2 +Y 2 O 3 +Ta 2 O 5 )/La 2 O 3 Is 0.3 or less, preferably (RO+GeO) 2 +Y 2 O 3 +Ta 2 O 5 )/La 2 O 3 Is not more than 0.2 of the total weight of the composition,more preferably (RO+GeO) 2 +Y 2 O 3 +Ta 2 O 5 )/La 2 O 3 Is 0.15 or less, more preferably (RO+GeO) 2 +Y 2 O 3 +Ta 2 O 5 )/La 2 O 3 Is less than 0.1, and the RO is one or more of MgO, caO, srO, baO.
20. The optical glass according to any one of claims 1 to 4, wherein the components thereof are represented by weight percent, wherein: siO (SiO) 2 +B 2 O 3 :5 to 15%, preferably SiO 2 +B 2 O 3 : 7-13%; and/or La 2 O 3 +Y 2 O 3 +Gd 2 O 3 :50 to 63%, preferably La 2 O 3 +Y 2 O 3 +Gd 2 O 3 : 52-60%; and/or ZrO 2 :4 to 11%, preferably ZrO 2 : 6-10%; and/or Nb 2 O 5 :5 to 13%, preferably Nb 2 O 5 : 7-12%; and/or TiO 2 :10 to 20%, preferably TiO 2 : 13-18%; and/or ZnO:0 to 4%, preferably ZnO:0.1 to 3 percent; and/or RO:0 to 4%, preferably RO:0 to 2 percent; and/or Rn 2 O:0 to 3%, preferably Rn 2 O:0 to 1 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 Al 2 O 3 :0 to 3%, preferably Al 2 O 3 :0 to 1 percent; and/or Yb 2 O 3 :0 to 5%, preferably Yb 2 O 3 :0 to 1 percent; and/or GeO 2 :0 to 2%, preferably GeO 2 :0 to 1 percent; and/or P 2 O 5 :0 to 2%, preferably P 2 O 5 :0 to 1 percent; and/or clarifying agent: 0 to 0.5%, preferably a clarifying agent: 0 to 0.2 percent, the RO is one or more of MgO, caO, srO, baO and Rn 2 O is Li 2 O、Na 2 O、K 2 One or more of O and a clarifying agent of Sb 2 O 3 、SnO 2 、CeO 2 One or more of the following.
21. The optical glass according to any one of claims 1 to 4, wherein the components thereof are represented by weight percent, wherein: siO (SiO) 2 :1 to 10%, preferably SiO 2 :2 to 8%, more preferably SiO 2 : 3-7%; and/or B 2 O 3 :1 to 10%, preferably B 2 O 3 :2 to 9%, more preferably B 2 O 3 : 4-8%; and/or La 2 O 3 :35 to 50%, preferably La 2 O 3 :37 to 47%, more preferably La 2 O 3 : 41-46%; and/or Y 2 O 3 :0 to 6%, preferably Y 2 O 3 :0 to 4%, more preferably Y 2 O 3 :0.1 to 3 percent; and/or Gd 2 O 3 :6 to 20%, preferably Gd 2 O 3 :8 to 18%, more preferably Gd 2 O 3 ：11～15％。
22. The optical glass according to any one of claims 1 to 4, wherein the component 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 RO; and/or does not contain Rn 2 O; and/or does not contain P 2 O 5 The method comprises the steps of carrying out a first treatment on the surface of the And/or does not contain Al 2 O 3 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 not containing Yb 2 O 3 The RO is one or more of MgO, caO, srO, baO, rn 2 O is Li 2 O、Na 2 O、K 2 One or more of O.
23. The optical glass according to any one of claims 1 to 4, wherein the optical glass has a refractive index n d An Abbe number v of 1.98 or more, preferably 1.99 or more, more preferably 2.00 to 2.15, still more preferably 2.01 to 2.10, still more preferably 2.03 to 2.07 d 22 to 31, preferably 23 to 30, more preferably 24 to 29, and even more preferably 25 to 28.
24. The optical glass according to any one of claims 1 to 4, wherein the optical glass has a coefficient of thermal expansion α -30/70℃ 90X 10 -7 Preferably 80X 10, and K is less than or equal to -7 Preferably 75X 10 or less per K -7 and/K or below; and/or acid action resistance stability D A More than 2 types, preferably 1 type; and/or lambda 70 Is 480nm or less, preferably lambda 70 470nm or less, more preferably lambda 70 465nm or less; and/or lambda 5 Is 390nm or less, preferably lambda 5 Is 380nm or less, more preferably lambda 5 Is 375nm or less; and/or weather resistance CR is 2 or more, preferably 1; and/or knoop hardness H K 630X 10 7 Pa or more, preferably 650×10 7 Pa or more, more preferably 660×10 7 Pa or more; and/or Young's modulus E of 11000X 10 7 Pa or more, preferably 12000×10 7 Pa or more, more preferably 13000×10 7 Pa or more; and/or the degree of air bubbles is a class A or more, preferably A 0 Above the stage, more preferably A 00 A stage; and/or density ρ of 5.50g/cm 3 Hereinafter, it is preferably 5.40g/cm 3 Hereinafter, more preferably 5.30g/cm 3 The following are set forth; and/or abrasion degree F A From 90 to 140, preferably from 100 to 130, more preferably from 110 to 123.
25. A glass preform produced by using the optical glass according to any one of claims 1 to 24.
26. An optical element, characterized in that it is made of the optical glass according to any one of claims 1 to 24 or made of the glass preform according to claim 25.
27. An optical instrument comprising the optical glass according to any one of claims 1 to 24 and/or the optical element according to claim 26.
CN202311066494.9A 2023-08-23 2023-08-23 Optical glass, glass preform, optical element, and optical instrument Pending CN117088605A (en)

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CN202311066494.9A CN117088605A (en) 2023-08-23 2023-08-23 Optical glass, glass preform, optical element, and optical instrument

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CN202311066494.9A CN117088605A (en) 2023-08-23 2023-08-23 Optical glass, glass preform, optical element, and optical instrument

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CN117088605A true CN117088605A (en) 2023-11-21

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