CN113666635A

CN113666635A - Optical glass and optical element

Info

Publication number: CN113666635A
Application number: CN202111042942.2A
Authority: CN
Inventors: 匡波
Original assignee: CDGM Glass Co Ltd
Current assignee: CDGM Glass Co Ltd
Priority date: 2021-09-07
Filing date: 2021-09-07
Publication date: 2021-11-19
Also published as: CN117756402A

Abstract

The invention provides optical glass, which comprises the following components in percentage by weight: SiO 2₂+B₂O₃：12～35％；Nb₂O₅+TiO₂+WO₃：20～55％；BaO+SrO+CaO+MgO：16～55％；ZnO：0～10％；Ln₂O₃：0～10％；ZrO₂: 0 to 10% of B, wherein₂O₃/SiO₂Less than 0.4, (SiO)₂+TiO₂)/(Nb₂O₅+ZrO₂The sum of CaO and BaO is 0.5 to 2.2, and the sum of ZnO, SrO and Ln is₂O₃)/SiO₂Is 0.7 or less, the refractive index of the optical glass is 1.88 or more, and the Abbe number is 30 or less. Through reasonable component design, the optical glass obtained by the invention has the expected refractive index and Abbe number, has excellent chemical stability and lower density, and meets the use requirement of high-performance optical instruments.

Description

Optical glass and optical element

Technical Field

The present invention relates to an optical glass, and particularly to an optical glass having a refractive index of 1.88 or more and an abbe number of 30 or less, and an optical element made of the same.

Background

The optical glass with the refractive index of more than 1.88 and the Abbe number of less than 30 belongs to high-refraction high-dispersion optical glass, and the glass can be coupled with low-dispersion optical glass for use, so that chromatic aberration and secondary spectrum are effectively eliminated, the optical total length of a lens can be effectively shortened, and an imaging system is miniaturized, therefore, the glass has wide application prospect in optical design.

In recent years, with the progress of digitalization and high definition of instruments using optical systems, there has been an increasing demand for weight reduction of optical elements such as lenses used in various optical instruments, and optical glasses used for manufacturing optical elements are required to have a low density. On the other hand, the optical glass is inevitably attacked by the environment and various liquids (such as acid, alkali, water, etc.) during processing and use, and therefore the resistance of the optical glass to such attacks, that is, the chemical stability of the optical glass is important for the accuracy of use and the life of the optical instrument.

Disclosure of Invention

For the above reasons, the present invention is to provide an optical glass having excellent chemical stability and low density.

The technical scheme adopted by the invention for solving the technical problem is as follows:

the optical glass comprises the following components in percentage by weight: SiO 2₂+B₂O₃：12～35％；Nb₂O₅+TiO₂+WO₃：20～55％；BaO+SrO+CaO+MgO：16～55％；ZnO：0～10％；Ln₂O₃：0～10％；ZrO₂: 0 to 10% of B, wherein₂O₃/SiO₂Less than 0.4, (SiO)₂+TiO₂)/(Nb₂O₅+ZrO₂The sum of CaO and BaO is 0.5 to 2.2, and the sum of ZnO, SrO and Ln is₂O₃)/SiO₂0.7 or less, the Ln₂O₃Is La₂O₃、Gd₂O₃、Y₂O₃、Yb₂O₃Of the refractive index n of the optical glass_dIs more than 1.88, and has Abbe number v_dIs 30 or less.

Further, the optical glass comprises the following components in percentage by weight: r₂O: 0 to 10 percent; and/or Al₂O₃: 0 to 5 percent; and/or a clarifying agent: 0 to 1%, wherein R₂O is Li₂O、Na₂O、K₂One or more of O and Sb as clarifier₂O₃、SnO₂SnO and CeO₂One or more of (a).

Further, the optical glass comprises the following components in percentage by weight: nb₂O₅The ratio of/BaO is 0.2 to 1.2, and Nb is preferable₂O₅A ratio of/BaO of 0.2 to 1.0, more preferably Nb₂O₅A ratio of/BaO of 0.25 to 0.9, and further preferably Nb₂O₅The ratio of/BaO is 0.3-0.8; and/or TiO₂/(Nb₂O₅+ZrO₂) 0.6 to 5.5, preferably TiO₂/(Nb₂O₅+ZrO₂) 0.7 to 4.0, more preferably TiO₂/(Nb₂O₅+ZrO₂) 0.8 to 3.0, and further preferably TiO₂/(Nb₂O₅+ZrO₂) 1.0 to 2.5; and/or SiO₂/(Nb₂O₅+TiO₂) 0.3 to 1.3, preferably SiO₂/(Nb₂O₅+TiO₂) 0.35 to 1.0, more preferably SiO₂/(Nb₂O₅+TiO₂) 0.4 to 0.8.

Further, the optical glass comprises the following components in percentage by weight: b is₂O₃/SiO₂0.01 to 0.3, preferably B₂O₃/SiO₂0.03 to 0.2; and/or (ZnO + SrO + Ln)₂O₃)/SiO₂Is 0.6 or less, preferably (ZnO + SrO + Ln)₂O₃)/SiO₂Is 0.5 or less, more preferably (ZnO + SrO + Ln)₂O₃)/SiO₂Is 0.3 or less; and/or (SiO)₂+TiO₂)/(Nb₂O₅+ZrO₂+ CaO + BaO) is 0.6 to 2.0, preferably (SiO)₂+TiO₂)/(Nb₂O₅+ZrO₂+ CaO + BaO) is 0.8 to 1.8, more preferably (SiO)₂+TiO₂)/(Nb₂O₅+ZrO₂And + CaO + BaO) is 0.9 to 1.5.

Further, the optical glass comprises the following components in percentage by weight: SiO 2₂+B₂O₃: 15 to 30%, preferably SiO₂+B₂O₃: 18-25%; and/or Nb₂O₅+TiO₂+WO₃: 25 to 50%, preferably Nb₂O₅+TiO₂+WO₃: 30-45%; and/or BaO + SrO + CaO + MgO: 20-50%, preferably BaO + SrO + CaO + MgO: 25-40%; and/or ZnO: 0-5%, preferably ZnO: 0 to 2 percent(ii) a And/or Ln₂O₃: 0 to 9%, preferably Ln₂O₃: 0 to 7 percent; and/or ZrO₂: 1 to 8%, preferably ZrO₂: 2-7%; and/or R₂O: 0 to 6%, preferably R₂O: 0.5-5%; and/or Al₂O₃: 0 to 3%, preferably Al₂O₃: 0-2%; and/or a clarifying agent: 0-0.5%, preferably clarifying agent: 0-0.2%, the Ln₂O₃Is La₂O₃、Gd₂O₃、Y₂O₃、Yb₂O₃One or more of, R₂O is Li₂O、Na₂O、K₂One or more of O and Sb as clarifier₂O₃、SnO₂SnO and CeO₂One or more of (a).

Further, the optical glass comprises the following components in percentage by weight: SiO 2₂: 12-30%, preferably SiO₂: 15 to 25%, more preferably SiO₂: 16-23%; and/or Nb₂O₅: 6 to 20%, preferably Nb₂O₅: 7 to 18%, more preferably Nb₂O₅: 8-17%; and/or TiO₂: 15-35%, preferably TiO₂: 18 to 32%, more preferably TiO₂: 20-30%; and/or BaO: 15-35%, preferably BaO: 18 to 32%, more preferably BaO: 20-30%; and/or CaO: 0-12%, preferably CaO: 1-9%, more preferably CaO: 3-7%; and/or B₂O₃: 0 to 6%, preferably B₂O₃: 0.1 to 5%, more preferably B₂O₃: 0.5-4%; and/or WO₃: 0 to 10%, preferably WO₃: 0 to 5%, more preferably WO₃: 0-2%; and/or SrO: 0 to 8%, preferably SrO: 0 to 4%, more preferably SrO: 0-2%; and/or MgO: 0-8%, preferably MgO: 0 to 4%, more preferably MgO: 0-2%; and/or Li₂O: 0 to 3%, preferably Li₂O: 0 to 2%, more preferably Li₂O: 0 to 1 percent; and/or Na₂O: 0 to 8%, preferably Na₂O: 0 to 6%, more preferably Na₂O: 0.5-5%; and/or K₂O: 0 to 5%, preferably K₂O: 0 to 3%, more preferably K₂O：0～2％。

Further, the optical glass comprises the following components in percentage by weight: na (Na)₂O/CaO is 5.0 or less, preferably Na₂O/CaO is 0.01 to 3.0, and Na is more preferable₂The O/CaO is 0.05-2.5; and/or Li₂O/B₂O₃Is 0.5 or less, preferably Li₂O/B₂O₃Is 0.3 or less, more preferably Li₂O/B₂O₃Is 0.1 or less, and Li is more preferable₂O/B₂O₃Is 0.05 or less; and/or 10 × Li₂O/Nb₂O₅Is 0.7 or less, preferably 10 × Li₂O/Nb₂O₅Is 0.4 or less, more preferably 10 XLi₂O/Nb₂O₅Is 0.2 or less.

Further, the optical glass comprises the following components in percentage by weight: not more than 4% of P₂O₅Preferably not more than 2% of P₂O₅More preferably not more than 1% of P₂O₅(ii) a And/or not more than 4% of Bi₂O₃Preferably not more than 2% of Bi₂O₃More preferably not more than 1% of Bi₂O₃(ii) a And/or not more than 4% of Ta₂O₅Preferably not more than 2% Ta₂O₅More preferably not more than 1% of Ta₂O₅(ii) a And/or not more than 4% of TeO₂Preferably not more than 2% of TeO₂More preferably not more than 1% of TeO₂(ii) a And/or not more than 4% Ga₂O₃Preferably not more than 2% Ga₂O₃More preferably not more than 1% of Ga₂O₃。

Further, the optical glass does not contain ZnO; and/or do not contain Li₂O; and/or does not contain SrO; and/or does not contain MgO; and/or does not contain P₂0₅(ii) a And/or does not contain Bi₂O₃(ii) a And/or does not contain Ta₂O₅(ii) a And/or does not contain TeO₂(ii) a And/or does not contain WO₃(ii) a And/or does not contain Gd₂O₃(ii) a And/or does not contain Y₂O₃。

Further, the refractive index n of the optical glass_d1.89-1.95, preferably 1.90-1.94, more preferably 1.91-1.935; abbe number v_d20 to 27, more preferably 21 to 26, and still more preferably 22 to 25.

Further, λ of the optical glass₇₀Is 460nm or less, preferably λ₇₀Is 450nm or less, more preferably lambda₇₀Is 440nm or less; and/or lambda₅Is 400nm or less, preferably lambda₅Is 390nm or less, more preferably λ₅Is 380nm or less; and/or stability against acid action D_AIs 2 or more, preferably 1; and/or stability against water action D_WIs 2 or more, preferably 1; and/or the upper limit temperature of crystallization is 1180 ℃ or lower, preferably 1160 ℃ or lower, more preferably 1140 ℃ or lower; and/or a Young's modulus E of 9500X 10⁷A pressure of 10000X 10 or more, preferably⁷A value of 10500X 10 or more, more preferably,/Pa⁷More than Pa; and/or coefficient of thermal expansion alpha_100～300℃Is 110 x 10^-7Preferably 105X 10 or less,/K^-7A value of less than or equal to K, more preferably 100X 10^-7below/K; the density rho is 4.30g/cm³Hereinafter, it is preferably 4.20g/cm³Hereinafter, more preferably 4.10g/cm³The following; and/or degree of wear F_A150 or more, preferably 180 or more, more preferably 200 to 300; and/or relative partial dispersion P_g,FIs 0.6000 to 0.6400, preferably 0.6100 to 0.6300, and more preferably 0.6150 to 0.6250.

The glass preform is made of the optical glass.

And the optical element is made of the optical glass or the glass prefabricated member.

An optical device comprising the above optical glass or the above optical element.

The invention has the beneficial effects that: through reasonable component design, the optical glass obtained by the invention has the expected refractive index and Abbe number, has excellent chemical stability and lower density, and meets the use requirement of high-performance optical instruments.

Detailed Description

The optical glass of the present invention is obtained by the following steps, which are not limited to the above-described embodiments, and can be appropriately modified within the scope of the object of the present invention. Note that, although the description of the duplicate description may be appropriately omitted, the gist of the present invention is not limited to this. The optical glass of the present invention may be simply referred to as glass in the following.

[ optical glass ]

The ranges of the respective components of the optical glass of the present invention are explained below. In the present specification, the contents of the respective components are all expressed in terms of weight percent (wt%) relative to the total amount of glass matter converted into the composition of oxides, if not specifically stated. Here, the "composition converted to oxides" means that when oxides, complex salts, hydroxides, and the like used as raw materials of the optical glass composition component of the present invention are decomposed in the melt and converted to oxides, the total amount of the oxides is 100%.

Unless otherwise indicated in a specific context, numerical ranges set forth herein include upper and lower values, and "above" and "below" include end-point values, as well as all integers and fractions within the range, and are not limited to the specific values recited in the defined range. The term "about" as used herein means that the formulations, parameters, and other quantities and characteristics are not, and need not be, exact, and can be approximate and/or larger or smaller, if desired, reflecting tolerances, conversion factors, measurement error and the like. As used herein, "and/or" is inclusive, e.g., "A and/or B," and means A alone, B alone, or both A and B.

< essential Components and optional Components >

SiO₂And B₂O₃Are components constituting the glass skeleton, and can improve the stability of the glass and adjust the melt viscosity of the glass, and when the total content thereof is high, it is difficult to obtain a high refractive index desired in the present invention. Therefore, the temperature of the molten metal is controlled,SiO₂and B₂O₃SiO in total content₂+B₂O₃12 to 35%, preferably SiO₂+B₂O₃15 to 30%, more preferably SiO₂+B₂O₃Is 18 to 25%. In some embodiments, the SiO₂+B₂O₃Is about 12%, 12.5%, 13%, 13.5%, 14%, 14.5%, 15%, 15.5%, 16%, 16.5%, 17%, 17.5%, 18%, 18.5%, 19%, 19.5%, 20%, 20.5%, 21%, 21.5%, 22%, 22.5%, 23%, 23.5%, 24%, 24.5%, 25%, 25.5%, 26%, 26.5%, 27%, 27.5%, 28%, 28.5%, 29%, 29.5%, 30%, 30.5%, 31%, 31.5%, 32%, 32.5%, 33%, 33.5%, 34%, 34.5%, 35%.

SiO₂The network forming body of the glass of the present invention has the effects of maintaining the chemical stability of the glass and the viscosity suitable for the molding of the molten glass, improving the devitrification resistance of the glass, and reducing the erosion of the molten glass to the refractory. If SiO₂The content is less than 12%, and the above-mentioned effects are hardly attained, so that SiO₂The lower limit of the content of (B) is 12%, preferably 15%, more preferably 16%. If SiO₂When the content of (B) is more than 30%, the glass-melting property is lowered and the transition temperature is raised. Thus, SiO₂The upper limit of the content of (B) is 30%, preferably 25%, more preferably 23%. In some embodiments, about 12%, 12.5%, 13%, 13.5%, 14%, 14.5%, 15%, 15.5%, 16%, 16.5%, 17%, 17.5%, 18%, 18.5%, 19%, 19.5%, 20%, 20.5%, 21%, 21.5%, 22%, 22.5%, 23%, 23.5%, 24%, 24.5%, 25%, 25.5%, 26%, 26.5%, 27%, 27.5%, 28%, 28.5%, 29%, 29.5%, 30% SiO may be included₂。

B₂O₃Can improve the thermal stability of glass, improve the meltability of glass, inhibit the rapid escape of gas during the melting of raw materials so as to avoid 'blow out', and properly contain glass which is easy to obtain and has no melting residue of glass raw materials, but when B is used₂O₃Of (1) containsWhen the amount is too large, the refractive index of the glass decreases and the thermal stability deteriorates, so that B in the present invention₂O₃The content of (b) is 6% or less, preferably 0.1 to 5%, more preferably 0.5 to 4%. In some embodiments, about 0%, greater than 0%, 0.01%, 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6% B may be included₂O₃。

In some embodiments of the invention, B is₂O₃Content of (D) and SiO₂Ratio B between contents of₂O₃/SiO₂The content of the glass is controlled to be less than 0.4, which is beneficial to improving the chemical stability of the glass. Therefore, B is preferred₂O₃/SiO₂Is 0.4 or less. Further, by making B₂O₃/SiO₂In the range of 0.01-0.3, the Young modulus and the abrasion degree of the glass are also favorably optimized. Therefore, B is more preferable₂O₃/SiO₂0.01 to 0.3, and preferably B₂O₃/SiO₂0.03 to 0.2. In some embodiments, B₂O₃/SiO₂The value of (b) can be 0, greater than 0, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.11, 0.12, 0.13, 0.14, 0.15, 0.16, 0.17, 0.18, 0.19, 0.2, 0.21, 0.22, 0.23, 0.24, 0.25, 0.26, 0.27, 0.28, 0.29, 0.3, 0.31, 0.32, 0.33, 0.34, 0.35, 0.36, 0.37, 0.38, 0.39, 0.4.

Nb₂O₅、TiO₂、WO₃Belongs to a high-refraction high-dispersion component, when the total content is Nb₂O₅+TiO₂+WO₃When the value of (A) is less than 20%, the refractive index and dispersion of the glass hardly meet the design requirements; when the total content is Nb₂O₅+TiO₂+WO₃When the value of (b) is more than 55%, the resistance to devitrification and chemical stability of the glass are lowered, and the light transmittance is deteriorated.Therefore, Nb in the present invention₂O₅+TiO₂+WO₃20 to 55%, preferably Nb₂O₅+TiO₂+WO₃25 to 50%, more preferably Nb₂O₅+TiO₂+WO₃30 to 45 percent. In some embodiments, Nb₂O₅+TiO₂+WO₃Is about 20%, 20.5%, 21%, 21.5%, 22%, 22.5%, 23%, 23.5%, 24%, 24.5%, 25%, 25.5%, 26%, 26.5%, 27%, 27.5%, 28%, 28.5%, 29%, 29.5%, 30%, 30.5%, 31%, 31.5%, 32%, 32.5%, 33%, 33.5%, 34%, 34.5%, 35%, 35.5%, 36%, 36.5%, 37%, 37.5%, 38%, 38.5%, 39%, 39.5%, 40%, 40.5%, 41%, 41.5%, 42%, 42.5%, 43%, 43.5%, 44%, 44.5%, 45%, 45.5%, 46%, 46.5%, 47%, 47.5%, 48%, 48.5%, 49%, 49.5%, 50%, 50.5%, 51%, 51.5%, 52%, 52.5%, 53%, 53.5%, 54%, 54.5%, 55%.

Nb₂O₅The high-refractive-index high-dispersion component can improve the refractive index and the devitrification resistance of the glass and reduce the thermal expansion coefficient of the glass, and the invention contains more than 6 percent of Nb₂O₅To obtain the above effects, Nb is preferable₂O₅The content of (b) is 7% or more, more preferably 8% or more. If Nb₂O₅More than 20%, the thermal and chemical stability of the glass is lowered and the light transmittance is lowered, so that Nb in the present invention is₂O₅The upper limit of the content of (B) is 20%, preferably 18%, more preferably 17%. In some embodiments, about 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, 10%, 10.5%, 11%, 11.5%, 12%, 12.5%, 13%, 13.5%, 14%, 14.5%, 15%, 15.5%, 16%, 16.5%, 17%, 17.5%, 18%, 18.5%, 19%, 19.5%, 20% Nb may be included₂O₅。

TiO₂Has the effects of improving the refractive index and dispersion of glass, participating in the formation of glass network, and properly containingThe glass can be made more stable and the high temperature viscosity of the glass can be reduced. In the present invention, the content of TiO is 15% or more₂To obtain the above effects, it is preferable to contain 18% or more of TiO₂More preferably, it contains 20% or more of TiO₂. If TiO₂When the content exceeds 35%, the glass tends to be more devitrified, the transition temperature is increased, and the glass tends to be colored during press molding. Thus, TiO in the present invention₂The content of (A) is 35% or less, preferably TiO₂The content of (b) is 32% or less, more preferably 30% or less. In some embodiments of the invention, about 15%, 15.5%, 16%, 16.5%, 17%, 17.5%, 18%, 18.5%, 19%, 19.5%, 20%, 20.5%, 21%, 21.5%, 22%, 22.5%, 23%, 23.5%, 24%, 24.5%, 25%, 25.5%, 26%, 26.5%, 27%, 27.5%, 28%, 28.5%, 29%, 29.5%, 30%, 30.5%, 31%, 31.5%, 32%, 32.5%, 33%, 33.5%, 34%, 34.5%, 35% of TiO may be included₂。

In some embodiments of the invention, the SiO is prepared by reacting SiO₂Content of (2) and Nb₂O₅And TiO₂Total content of (2) Nb₂O₅+TiO₂Ratio of between SiO₂/(Nb₂O₅+TiO₂) The control is within the range of 0.3-1.3, so that the proper abrasion degree and relative partial dispersion of the glass can be obtained while the thermal expansion coefficient and the density of the glass are reduced. Therefore, SiO is preferable₂/(Nb₂O₅+TiO₂) 0.3 to 1.3, more preferably SiO₂/(Nb₂O₅+TiO₂) 0.35 to 1.0, and further preferably SiO₂/(Nb₂O₅+TiO₂) 0.4 to 0.8. In some embodiments of the invention, the SiO₂/(Nb₂O₅+TiO₂) May be 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9, 0.95, 1.0, 1.05, 1.1, 1.15, 1.2, 1.25, 1.3.

WO₃Can improve the refractive index and dispersion of the glass, but the effect is not as good as that of Nb₂O₅And TiO₂And do not haveCost advantage and also a reduction in the light transmittance of the glass. Thus, WO in the present invention₃The content is 0 to 10%, preferably 0 to 5%, more preferably 0 to 2%, and further preferably no WO is contained₃. In some embodiments, about 0%, greater than 0%, 0.01%, 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, 10% of WO may be included₃。

ZnO can adjust the refractive index and dispersion of the glass, reduce the transition temperature of the glass, if the content of ZnO exceeds 10 percent, the devitrification resistance of the glass is reduced, meanwhile, the high-temperature viscosity is small, the forming is difficult, and the thermal expansion coefficient and the refractive index temperature coefficient of the glass are increased. Therefore, the ZnO content in the present invention is 0 to 10%, preferably 0 to 5%, and more preferably 0 to 2%. In some embodiments, it is further preferred that no ZnO is present. In some embodiments, about 0%, greater than 0%, 0.01%, 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, 10% ZnO may be included.

R₂O(R₂O is Li₂O、Na₂O、K₂One or more of O) may lower the transition temperature of the glass, and when the content thereof exceeds 10%, the chemical stability of the glass is lowered. Thus, R₂The content of O is 0 to 10%, preferably 0 to 6%, more preferably 0.5 to 5%. In some embodiments, about 0%, greater than 0%, 0.01%, 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, 10% R may be included₂O。

Li₂O can lower the glass transition temperature, improve the glass meltability,however, when the content is high, it is disadvantageous in chemical stability, devitrification resistance and thermal expansion coefficient of the glass, and therefore, Li in the present invention₂The content of O is 3% or less, preferably 2% or less, and more preferably 1% or less. In some embodiments, it is further preferred not to contain Li₂And O. In some embodiments, about 0%, greater than 0%, 0.01%, 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3% Li may be included₂O。

In some embodiments of the invention, the lithium ion battery is prepared by reacting Li₂Content of O and B₂O₃Ratio between contents of Li₂O/B₂O₃Below 0.5, the chemical stability and the secondary compression surface crystallization resistance of the glass can be improved, and the abrasion degree of the glass is optimized. Therefore, Li is preferable₂O/B₂O₃Is 0.5 or less, more preferably Li₂O/B₂O₃Is 0.3 or less, and Li is more preferable₂O/B₂O₃Is 0.1 or less, and Li is more preferable₂O/B₂O₃Is 0.05 or less. In some embodiments, Li₂O/B₂O₃The value of (a) may be 0, greater than 0, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.11, 0.12, 0.13, 0.14, 0.15, 0.16, 0.17, 0.18, 0.19, 0.2, 0.21, 0.22, 0.23, 0.24, 0.25, 0.26, 0.27, 0.28, 0.29, 0.3, 0.31, 0.32, 0.33, 0.34, 0.35, 0.36, 0.37, 0.38, 0.39, 0.4, 0.41, 0.42, 0.43, 0.44, 0.45, 0.46, 0.47, 0.48, 0.49, 0.5.

In some embodiments of the invention, the composition is prepared by subjecting 10 × Li₂O/Nb₂O₅Below 0.7, it is favorable to raise the chemical stability and secondary compression crystallization resistance of glass and raise the Young's modulus of glass. Therefore, 10 × Li is preferable₂O/Nb₂O₅Is 0.7 or less, more preferably 10 XLi₂O/Nb₂O₅Is 0.4 or less, and more preferably 10 XLi₂O/Nb₂O₅Is 0.2 or less. In some embodiments of the invention, 10 × Li₂O/Nb₂O₅The value of (a) may be 0, greater than 0, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.11, 0.12, 0.13, 0.14, 0.15, 0.16, 0.17, 0.18, 0.19, 0.2, 0.21, 0.22, 0.23, 0.24, 0.25, 0.26, 0.27, 0.28, 0.29, 0.3, 0.31, 0.32, 0.33, 0.34, 0.35, 0.36, 0.37, 0.38, 0.39, 0.4, 0.41, 0.42, 0.43, 0.44, 0.45, 0.46, 0.47, 0.48, 0.49, 0.5, 0.55, 0.6, 0.65, 0.7.

Na₂O has an effect of improving the meltability of glass, can improve the glass melting effect, and can lower the glass transition temperature. If Na₂The content of O exceeds 8%, the chemical stability and weather resistance of the glass are lowered, and therefore Na₂The content of O is 0-8%, preferably Na₂The content of O is 0 to 6%, and Na is more preferable₂The content of O is 0.5-5%. In some embodiments, about 0%, greater than 0%, 0.01%, 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8% Na may be included₂O。

K₂O has an effect of improving the thermal stability and melting property of the glass, but the content thereof exceeds 5%, and the resistance to devitrification and chemical stability of the glass are deteriorated, so that K in the present invention₂The content of O is 5% or less, preferably K₂The content of O is 3% or less, more preferably 2% or less. In some embodiments, K may be included at about 0%, greater than 0%, 0.01%, 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%₂O。

The appropriate amounts of the alkaline earth metal oxides BaO, SrO, CaO and MgO in the glass can adjust the refractive index and dispersion of the glass and at the same time can improve the stability of the glass, and the above effects are obtained by containing 16% or more of the alkaline earth metal oxides in the present invention. On the other hand, if the value of BaO + SrO + CaO + MgO is greater than 55%, the refractive index and dispersion of the glass are difficult to meet the design requirements, and the devitrification resistance of the glass is lowered. Therefore, the content of BaO + SrO + CaO + MgO in the present invention is limited to 16 to 55%, preferably 20 to 50%, more preferably 25 to 40%. In some embodiments, the content of BaO + SrO + CaO + MgO is about 16%, 16.5%, 17%, 17.5%, 18%, 18.5%, 19%, 19.5%, 20%, 20.5%, 21%, 21.5%, 22%, 22.5%, 23%, 23.5%, 24%, 24.5%, 25%, 25.5%, 26%, 26.5%, 27%, 27.5%, 28%, 28.5%, 29%, 29.5%, 30%, 30.5%, 31%, 31.5%, 32%, 32.5%, 33%, 33.5%, 34%, 34.5%, 35%, 35.5%, 36%, 36.5%, 37%, 37.5%, 38%, 38.5%, 39%, 39.5%, 40%, 40.5%, 41%, 41.5%, 42%, 42.5%, 43%, 43.5%, 44%, 44.5%, 45%, 45.5%, 46%, 46.5%, 47%, 47.5%, 48%, 48.5%, 49%, 49.5%, 50%, 50.5%, 51%, 51.5%, 52%, 52.5%, 53%, 53.5%, 54%, 54.5%, 55%.

MgO can reduce the refractive index and melting temperature of the glass, but the refractive index of the glass cannot meet the design requirement when the content of MgO is excessive, the devitrification resistance and stability of the glass are reduced, and the cost of the glass is increased. Therefore, the MgO content is limited to 0 to 8%, preferably 0 to 4%, and more preferably 0 to 2%. In some embodiments, it is further preferred that no MgO be present. In some embodiments, about 0%, greater than 0%, 0.01%, 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8% MgO may be included.

CaO is helpful for adjusting the optical constants of the glass, improving the processability of the glass and reducing the density of the glass, but when the content of CaO is too large, the optical constants of the glass cannot meet the requirements and the devitrification resistance is deteriorated. Therefore, the CaO content is limited to 0 to 12%, preferably 1 to 9%, and more preferably 3 to 7%. In some embodiments, about 0%, greater than 0%, 0.01%, 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, 10%, 10.5%, 11%, 11.5%, 12% CaO may be included.

In some embodiments of the invention, Na is controlled₂Ratio Na between O content and CaO content₂The O/CaO is less than 5.0, and the anti-crystallization performance of the glass can be improved. Therefore, Na is preferred₂The O/CaO ratio is below 5.0. Further, by controlling Na₂The O/CaO is within the range of 0.01-3.0, and is also beneficial to improving the light transmittance and Young modulus of the glass. Therefore, Na is more preferable₂O/CaO is 0.01 to 3.0, and Na is more preferable₂The O/CaO ratio is 0.05 to 2.5. In some embodiments of the invention, Na₂The value of O/CaO may be 0, greater than 0, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4.0, 4.1, 4.2, 4.3, 4.5, 4.6, 4.8, 4.9, 4.0, 4.2, 4.3, 4.5, 4.0.

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 rapidly increased. Therefore, the SrO content is limited to 0 to 8%, preferably 0 to 4%, and more preferably 0 to 2%. In some embodiments, it is further preferred that SrO is absent. In some embodiments, about 0%, greater than 0%, 0.01%, 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8% SrO may be included.

BaO is an essential component for adjusting the refractive index of the glass, improving the transmittance and strength of the glass in the present invention, and the above effect is not significant when the content thereof is less than 15%, and the lower limit of the content of BaO is preferably 18%, and the lower limit of the content of BaO is more preferably 20%. On the other hand, if the content of BaO exceeds 35%, the devitrification resistance and chemical stability of the glass deteriorate, and the density increases significantly. Therefore, the upper limit of the BaO content is 35%, preferably 32%, more preferably 30%. In some embodiments of the invention, about 15%, 15.5%, 16%, 16.5%, 17%, 17.5%, 18%, 18.5%, 19%, 19.5%, 20%, 20.5%, 21%, 21.5%, 22%, 22.5%, 23%, 23.5%, 24%, 24.5%, 25%, 25.5%, 26%, 26.5%, 27%, 27.5%, 28%, 28.5%, 29%, 29.5%, 30%, 30.5%, 31%, 31.5%, 32%, 32.5%, 33%, 33.5%, 34%, 34.5%, 35% BaO may be included.

In some embodiments of the invention, Nb is controlled₂O₅And the content of BaO₂O₅the/BaO is within the range of 0.2-1.2, so that the glass has excellent chemical stability and the thermal expansion coefficient of the glass is reduced. Therefore, Nb is preferable₂O₅A ratio of/BaO of 0.2 to 1.2, more preferably Nb₂O₅The ratio of/BaO is 0.2 to 1.0. Further, by controlling Nb₂O₅the/BaO is within the range of 0.25-0.9, and the Young modulus of the glass can be further improved. Therefore, Nb is more preferable₂O₅The ratio of/BaO is 0.25 to 0.9, and Nb is more preferable₂O₅The ratio of/BaO is 0.3 to 0.8. In some embodiments of the invention, Nb₂O₅The value of/BaO may be 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9, 0.95, 1.0, 1.05, 1.1, 1.15, 1.2.

ZrO₂Can improve the refractive index of glass, adjust the dispersion, and improve the devitrification resistance and strength of glass, if ZrO₂The content of (b) is more than 10%, the difficulty of glass melting is increased, the melting temperature is increased, and even inclusions in the glass are generated and the transmittance is reduced. Thus, ZrO₂The content is 10% or less, preferably 1 to 8%, more preferably 2 to 7%. In some embodiments, about 0%, greater than 0%, 0.01%, 0.05%, 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, 10% ZrO may be included₂。

In some embodiments of the invention, the TiO is controlled₂Content of (2) and Nb₂O₅And ZrO₂Total content of (2) Nb₂O₅+ZrO₂TiO in the ratio of₂/(Nb₂O₅+ZrO₂) In the range of 0.6-5.5, the crystallization resistance and the light transmittance of the glass are improved. Therefore, TiO is preferred₂/(Nb₂O₅+ZrO₂) 0.6 to 5.5, more preferably TiO₂/(Nb₂O₅+ZrO₂) 0.7 to 4.0. Further, by controlling TiO₂/(Nb₂O₅+ZrO₂) In the range of 0.8-3.0, the glass can also obtain proper abrasion degree and relative partial dispersion. Therefore, TiO is more preferable₂/(Nb₂O₅+ZrO₂) 0.8 to 3.0, and further preferably TiO₂/(Nb₂O₅+ZrO₂) 1.0 to 2.5. In some embodiments of the invention, the TiO is₂/(Nb₂O₅+ZrO₂) The value of (a) may be 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9, 0.95, 1.0, 1.05, 1.1, 1.15, 1.2, 1.25, 1.3, 1.35, 1.4, 1.45, 1.5, 1.55, 1.6, 1.65, 1.7, 1.75, 1.8, 1.85, 1.9, 1.95, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4.0, 4.1, 4.2, 4.3, 4.4, 4.5, 5, 5.5, 4.5, 5, 5.5, 4.5, 5, 4.5, 4.

In some embodiments of the invention, the SiO is prepared by reacting SiO₂And TiO₂SiO in total content₂+TiO₂And Nb₂O₅、ZrO₂Total content Nb of CaO and BaO₂O₅+ZrO₂The ratio between + CaO + BaO (SiO)₂+TiO₂)/(Nb₂O₅+ZrO₂And + CaO + BaO) is controlled within the range of 0.5-2.2, so that the glass forming stability and chemical stability of the glass can be improved, and the density of the glass can be reduced. Therefore, (SiO) is preferable₂+TiO₂)/(Nb₂O₅+ZrO₂+ CaO + BaO) is 0.5 to 2.2, more preferably (SiO)₂+TiO₂)/(Nb₂O₅+ZrO₂And + CaO + BaO) is 0.6 to 2.0. Further, by controlling (SiO)₂+TiO₂)/(Nb₂O₅+ZrO₂And the + CaO + BaO) is in the range of 0.8-1.8, so that the secondary compression devitrification resistance and the Young modulus of the glass can be further improved. Therefore, (SiO) is more preferable₂+TiO₂)/(Nb₂O₅+ZrO₂+ CaO + BaO) is 0.8 to 1.8, more preferably (SiO)₂+TiO₂)/(Nb₂O₅+ZrO₂And + CaO + BaO) is 0.9 to 1.5. In some embodiments of the invention, (SiO)₂+TiO₂)/(Nb₂O₅+ZrO₂+ CaO + BaO) may have a value of 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9, 0.95, 1.0, 1.05, 1.1, 1.15, 1.2, 1.25, 1.3, 1.35, 1.4, 1.45, 1.5, 1.55, 1.6, 1.65, 1.7, 1.75, 1.8, 1.85, 1.9, 1.95, 2.0, 2.05, 2.1, 2.15, 2.2.

Ln₂O₃(Ln₂O₃Is La₂O₃、Gd₂O₃、Y₂O₃、Yb₂O₃One or more) is a component for improving the refractive index and chemical stability of the glass by adding Ln₂O₃Is controlled to 10% or less, and is preferably Ln, which prevents the devitrification resistance of the glass from being lowered₂O₃The upper limit of the content range is 9%, and the more preferable upper limit is 7%. In some embodiments, Ln is preferred₂O₃Is La₂O₃. In some embodiments, preferably no Gd is present₂O₃(ii) a And/or does not contain Y₂O₃(ii) a And/or does not contain Yb₂O₃. In some embodiments, about 0%, greater than 0%, 0.01%, 0.05%, 0.1%, 0.2%, 0.3%, or,0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, 10% Ln₂O₃。

In some embodiments of the invention, the ZnO, SrO and Ln are mixed₂O₃ZnO + SrO + Ln in total₂O₃With SiO₂Ratio between contents of (ZnO + SrO + Ln)₂O₃)/SiO₂The control below 0.7 is beneficial to reducing the density and relative partial dispersion of the glass. Therefore, (ZnO + SrO + Ln) is preferable₂O₃)/SiO₂Is 0.7 or less, more preferably (ZnO + SrO + Ln)₂O₃)/SiO₂Is 0.6 or less. Further, by controlling (ZnO + SrO + Ln)₂O₃)/SiO₂When the amount is 0.5 or less, the thermal expansion coefficient of the glass can be reduced. Therefore, (ZnO + SrO + Ln) is more preferable₂O₃)/SiO₂Is 0.5 or less, more preferably (ZnO + SrO + Ln)₂O₃)/SiO₂Is 0.3 or less. In some embodiments of the invention, (ZnO + SrO + Ln)₂O₃)/SiO₂The value of (a) may be 0, greater than 0, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.11, 0.12, 0.13, 0.14, 0.15, 0.16, 0.17, 0.18, 0.19, 0.2, 0.21, 0.22, 0.23, 0.24, 0.25, 0.26, 0.27, 0.28, 0.29, 0.3, 0.31, 0.32, 0.33, 0.34, 0.35, 0.36, 0.37, 0.38, 0.39, 0.4, 0.41, 0.42, 0.43, 0.44, 0.45, 0.46, 0.47, 0.48, 0.49, 0.5, 0.55, 0.6, 0.65, 0.7.

Al₂O₃The chemical stability of the glass can be improved, but when the content is too large, the devitrification resistance and the melting resistance of the glass are lowered, so that the content is 5% or less, preferably 3% or less, and more preferably 2% or less. In some embodiments, about 0%, greater than 0%, 0.01%, 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5% Al may be included₂O₃。

In some embodiments, the glass of the present invention may further comprise 0-1% of a fining agent to improve the defoaming capability of the glass. Such fining agents include, but are not limited to, Sb₂O₃、SnO₂SnO and CeO₂Preferably Sb₂O₃As a clarifying agent. The upper limit of the content of the above-mentioned clarifying agent is preferably 0.5%, more preferably 0.2%, when it is present alone or in combination. In some embodiments, one or more of the above fining agents are present in an amount of about 0%, greater than 0%, 0.01%, 0.05%, 0.1%, 0.15%, 0.2%, 0.25%, 0.3%, 0.35%, 0.4%, 0.45%, 0.5%, 0.55%, 0.6%, 0.65%, 0.7%, 0.75%, 0.8%, 0.85%, 0.9%, 0.95%, 1%.

Other components not mentioned above, such as P, can be added in small amounts as required within the range not impairing the characteristics of the glass of the present invention₂O₅、Bi₂O₃、Ta₂O₅、TeO₂And Ga₂O₃The content of the components, either individually or in total, is preferably not more than 4%, more preferably not more than 2%, still more preferably not more than 1%, and still more preferably not containing P₂O₅(ii) a And/or Bi₂O₃(ii) a And/or Ta₂O₅(ii) a And/or TeO₂(ii) a And/or Ga₂O₃。

< component which should not be contained >

In the glass of the present invention, even when a small amount of oxides of transition metals such as V, Cr, Mn, Fe, Co, Ni, Cu, Ag, and Mo is contained singly or in combination, the glass is colored and absorbs at a specific wavelength in the visible light region, thereby impairing the property of the present invention to improve the effect of visible light transmittance.

In recent years, oxides of Th, Cd, Tl, Os, Be and Se tend to Be used as harmful chemical substances in a controlled manner, not only in glass production steps, but also in processing steps and handling after productionMeasures for environmental protection are necessary. Therefore, when importance is attached to the influence on the environment, it is preferable that these components are not substantially contained except for inevitable mixing. Thereby, the optical glass becomes practically free from substances contaminating the environment. Therefore, the optical glass of the present invention can be manufactured, processed, and discarded without taking special measures for environmental countermeasures. Meanwhile, in order to achieve environmental friendliness, the optical glass of the present invention preferably does not contain As₂O₃And PbO.

"0%" or "0%" is not contained in the present invention, and means that the compound, molecule, element or the like is not intentionally added to the optical glass of the present invention as a raw material; however, it is within the scope of the present invention that certain impurities or components which are not intentionally added may be present as raw materials and/or equipment for producing the optical glass and may be contained in the final optical glass in small or trace amounts.

The properties of the optical glass of the present invention will be described below:

< refractive index and Abbe number >

Refractive index (n) of optical glass_d) And Abbe number (v)_d) The test was carried out according to the method specified in GB/T7962.1-2010.

In some embodiments, the refractive index (n) of the optical glass of the present invention_d) Is 1.88 or more, preferably 1.89 to 1.95, more preferably 1.90 to 1.94, and further preferably 1.91 to 1.935.

In some embodiments, the Abbe number (v) of the optical glass of the present invention_d)30 or less, preferably 28 or less, more preferably 20 to 27, still more preferably 21 to 26, and still more preferably 22 to 25.

< degree of coloration >

Coloring degree (. lamda.) for short-wave transmission spectral characteristics of the glass of the present invention₇₀And λ₅) And (4) showing. Lambda [ alpha ]₇₀Refers to the wavelength corresponding to the glass transmittance of 70%. Lambda [ alpha ]₇₀Is measured by measuring the spectral transmittance in a wavelength region from 280nm to 700nm and exhibiting transmission using a glass having a thickness of 10. + -. 0.1mm with two opposing planes parallel to each other and optically polishedA wavelength with a refractive index of 70%. The spectral transmittance or transmittance is the intensity I of light incident perpendicularly to the surface of the glass_inLight transmitted through the glass and having an intensity I emitted from a plane_outIn the case of light of (1) through (I)_out/I_inThe quantity expressed and also the transmission 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 glasses, λ₇₀A small value of (A) means that the glass itself is rarely colored and has a high light transmittance.

In some embodiments, the λ of the optical glass of the present invention₇₀Is 460nm or less, preferably λ₇₀Is 450nm or less, more preferably lambda₇₀Is 440nm or less.

In some embodiments, the λ of the optical glass of the present invention₅Is 400nm or less, preferably lambda₅Is 390nm or less, more preferably λ₅Is 380nm or less.

< stability against acid Effect >

Stability of acid resistance of optical glasses (D)_A) (powder method) the test was carried out according to the method prescribed in GB/T17129.

In some embodiments, the stability to acid action of the optical glasses of the invention (D)_A) Is 2 or more, preferably 1.

< stability against Water action >

Stability to Water of optical glass (D)_W) (powder method) the test was carried out according to the method prescribed in GB/T17129.

In some embodiments, the optical glass of the present invention has stability to water effects (D)_W) Is 2 or more, preferably 1.

< upper limit temperature of crystallization >

The crystallization performance of the glass is measured by adopting a gradient temperature furnace method, the glass is made into a sample of 180 multiplied by 10mm, the side surface is polished, the sample is put into a furnace with a temperature gradient (10 ℃/cm) and heated to 1300 ℃ (the temperature of the highest temperature zone) for heat preservation for 4 hours, then the sample is taken out and naturally cooled to the room temperature, the crystallization condition of the glass is observed under a microscope, and the highest temperature corresponding to the occurrence of crystals of the glass is the crystallization upper limit temperature of the glass.

In some embodiments, the optical glass of the present invention has an upper crystallization limit temperature of 1180 ℃ or lower, preferably 1160 ℃ or lower, and more preferably 1140 ℃ or lower.

< Young's modulus >

The Young's modulus (E) of the glass is obtained by measuring the longitudinal wave velocity and the transverse wave velocity of the glass by ultrasonic waves and calculating according to the following formula.

G＝V_S ²ρ

In the formula: e is Young's modulus, Pa;

g is shear modulus, Pa;

V_Tis the transverse wave velocity, m/s;

V_Sis the longitudinal wave velocity, m/s;

rho is the density of the glass, g/cm³。

In some embodiments, the optical glass of the present invention has a Young's modulus (E) of 9500X 10⁷A pressure of 10000X 10 or more, preferably⁷A value of 10500X 10 or more, more preferably,/Pa⁷More than Pa.

< coefficient of thermal expansion >

Coefficient of thermal expansion (alpha) of optical glass_100～300℃) The data at 100-300 ℃ are tested according to the method specified in GB/T7962.16-2010.

The coefficient of thermal expansion (. alpha.) of the optical glass of the present invention_100～300℃) Is 110 x 10^-7Preferably 105X 10 or less,/K^-7A value of less than or equal to K, more preferably 100X 10^-7and/K is less than or equal to.

< Density >

The density (. rho.) of the optical glass was measured according to the method specified in GB/T7962.20-2010.

In some embodiments, the optical glass of the present invention has a density (. rho.) of 4.30g/cm³Hereinafter, it is preferably 4.20g/cm³Hereinafter, more preferably 4.10g/cm³The following.

< degree of abrasion >

Degree of abrasion (F) of optical glass_A) The abrasion loss of the sample is multiplied by 100 under the same conditions, and the value is expressed by the following formula:

F_A＝V/V₀×100＝(W/ρ)/(W₀/ρ₀)×100

in the formula: v is the volume abrasion amount of the sample to be measured;

V₀-the amount of wear of the standard sample volume;

w is the abrasion loss of the quality of the sample to be measured;

W₀-abrasion loss of standard sample mass;

rho is the density of the sample to be measured;

ρ₀-standard sample density.

In some embodiments, the optical glass of the present invention has an abrasion degree (F)_A) Is 150 or more, preferably 180 or more, and more preferably 200 to 300.

< relative partial Dispersion >

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)

the following formula (2) holds for most of the so-called "normal glasses" according to the Abbe number formula (hereinafter, H-K6 and F4 are used as "normal glasses")

P_x,y＝m_x,y·v_d+b_x,y (2)

This linear relationship is P_x,yIs ordinate, v_dExpressed on the abscissa, where m_x,yIs a slope, b_x,yIs the intercept.

It is known that the correction of the secondary spectrum, i.e. the achromatization of more than two wavelengths, requires at least one glass which does not conform to the above formula (2) (i.e. its P)_x,yValue deviation from abbe number empirical formula) by Δ P_x,yTo representThen each P_x,y-v_dThe point being shifted by Δ P with respect to a "normal line" corresponding to the above formula (2)_x,yAmount of such a.DELTA.P of each glass_x,yThe 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)

therefore, from the above, relative partial dispersion (P) can be obtained_g,F) The calculation formula of (a) is the following formula (4):

P_g,F＝(n_g-n_F)/(n_F-n_C) (4)

in some embodiments, the relative partial dispersion (P) of the optical glasses of the present invention_g,F) Is 0.6000 to 0.6400, preferably 0.6100 to 0.6300, and more preferably 0.6150 to 0.6250.

< Secondary compression type devitrification resistance >

The test method of the secondary compression type anti-crystallization performance comprises the following steps: cutting the sample glass into a size of 20 × 20 × 10mm, and placing at a temperature T_gAnd (4) preserving the heat in a muffle furnace at 200-250 ℃ for 15-30 minutes, taking out and cooling, and observing whether crystals exist on the surface and the inside of the glass or opacification occurs. If the glass sample has no opacities and/or crystals, the secondary compression crystallization resistance of the glass is excellent.

[ production method ]

The method for manufacturing 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 oxides, hydroxides, fluorides, various salts (carbonates, nitrates, sulfates, phosphates, metaphosphates) and the like as raw materials, the prepared furnace burden is put into a smelting furnace (such as a platinum crucible) with the temperature of 1000-1400 ℃ for smelting after being mixed according to a conventional method, and homogeneous molten glass without bubbles and undissolved substances is obtained after clarification and homogenization, and the molten glass is cast in a mould and annealed. Those skilled in the art can appropriately select the raw materials, the process method and the process parameters according to the actual needs.

Glass preform and optical element

The glass preform can be produced from the optical glass produced by direct gob casting, grinding, or press molding such as hot press molding. That is, a glass preform can be produced by direct precision gob-molding of 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 optical glass, subjecting the preform to reheat press molding, and then performing polishing processing. It should be noted that the means for producing the glass preform is not limited to the above 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 reheat press forming, precision press forming, or the like to produce optical elements such as lenses, prisms, or the like.

The glass preform of the present invention and the optical element are each formed of the above-described optical glass of the present invention. The glass preform of the present invention has excellent characteristics possessed by optical glass; the optical element of the present invention has excellent characteristics of optical glass, and can provide optical elements such as various lenses and prisms having high optical values.

Examples of the lens include various lenses such as a concave meniscus lens, a convex meniscus lens, a double convex lens, a double concave lens, a plano-convex lens, and a plano-concave lens, each of which has a spherical or aspherical lens surface.

[ optical instruments ]

The optical element formed by the optical glass can be used for manufacturing optical instruments such as photographic equipment, camera equipment, projection equipment, display equipment, vehicle-mounted equipment, monitoring equipment and the like.

Examples

< example of optical glass >

In order to further clarify the explanation and explanation of the technical solution of the present invention, the following non-limiting examples are provided.

In this example, optical glasses having compositions shown in tables 1 to 4 were obtained by the above-mentioned method for producing optical glasses. The characteristics of each glass were measured by the test method described in the present invention, and the measurement results are shown in tables 1 to 4. In the secondary press type devitrification resistance tests in tables 1 to 4, according to the above test methods, the glass is not opacified and has no crystal particles on the surface and inside thereof and is denoted by "A", the glass is not opacified and has no crystal particles inside thereof and has crystal particles on the surface thereof and is denoted by "B", the glass is not opacified and has 1 to 10 crystal particles inside thereof and is denoted by "C", the glass is not opacified and has 10 to 20 crystal particles inside thereof and is denoted by "D", and the glass is opacified or has densely devitrified particles inside thereof and is denoted by "X".

Table 1.

Table 2.

Table 3.

Table 4.

< glass preform example >

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, and preforms such as prisms were produced from the glasses obtained in examples 1 to 23 of optical glass by means of polishing or press molding such as reheat press molding and precision press molding.

< optical element example >

The preforms obtained in the above examples of glass preforms were annealed to reduce the deformation in the glass and to fine-tune the optical properties such as refractive index to desired values.

Next, each preform is ground and polished to produce 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, and prisms. The surface of the resulting optical element may be coated with an antireflection film.

< optical Instrument example >

The optical element obtained by the above-described optical element embodiment is used for, for example, imaging devices, sensors, microscopes, medical technologies, digital projection, communications, optical communication technologies/information transmission, optics/lighting in the automobile field, photolithography, excimer lasers, wafers, computer chips, and integrated circuits and electronic devices including such circuits and chips, or for image pickup devices and apparatuses in the vehicle-mounted field, by forming an optical component or an optical assembly by using one or more optical elements through optical design.

Claims

1. Optical glass, characterized in that its components, expressed in weight percent, contain: SiO 2₂+B₂O₃：12～35％；Nb₂O₅+TiO₂+WO₃：20～55％；BaO+SrO+CaO+MgO：16～55％；ZnO：0～10％；Ln₂O₃：0～10％；ZrO₂: 0 to 10% of B, wherein₂O₃/SiO₂Less than 0.4, (SiO)₂+TiO₂)/(Nb₂O₅+ZrO₂The sum of CaO and BaO is 0.5 to 2.2, and the sum of ZnO, SrO and Ln is₂O₃)/SiO₂0.7 or less, the Ln₂O₃Is La₂O₃、Gd₂O₃、Y₂O₃、Yb₂O₃Of the refractive index n of the optical glass_dIs more than 1.88, and has Abbe number v_dIs 30 or less.

2. The optical glass according to claim 1, wherein the composition further comprises, in weight percent: r₂O: 0 to 10 percent; and/or Al₂O₃: 0 to 5 percent; and/or a clarifying agent: 0 to 1%, wherein R₂O is Li₂O、Na₂O、K₂One or more of O and Sb as clarifier₂O₃、SnO₂SnO and CeO₂One or more of (a).

3. An optical glass according to claim 1 or 2, characterised in that its components are expressed in weight percentage, wherein: nb₂O₅The ratio of/BaO is 0.2 to 1.2, and Nb is preferable₂O₅A ratio of/BaO of 0.2 to 1.0, more preferably Nb₂O₅A ratio of/BaO of 0.25 to 0.9, and further preferably Nb₂O₅The ratio of/BaO is 0.3-0.8; and/or TiO₂/(Nb₂O₅+ZrO₂) 0.6 to 5.5, preferably TiO₂/(Nb₂O₅+ZrO₂) 0.7 to 4.0, more preferably TiO₂/(Nb₂O₅+ZrO₂) 0.8 to 3.0, and further preferably TiO₂/(Nb₂O₅+ZrO₂) 1.0 to 2.5; and/or SiO₂/(Nb₂O₅+TiO₂) 0.3 to 1.3, preferably SiO₂/(Nb₂O₅+TiO₂) 0.35 to 1.0, more preferably SiO₂/(Nb₂O₅+TiO₂) 0.4 to 0.8.

4. An optical glass according to claim 1 or 2, characterised in that its components are expressed in weight percentage, wherein: b is₂O₃/SiO₂0.01 to 0.3, preferably B₂O₃/SiO₂0.03 to 0.2; and/or (ZnO + SrO + Ln)₂O₃)/SiO₂Is 0.6 or less, preferably (ZnO + SrO + Ln)₂O₃)/SiO₂Is 0.5 or less, more preferably (ZnO + SrO + Ln)₂O₃)/SiO₂Is 0.3 or less; and/or (SiO)₂+TiO₂)/(Nb₂O₅+ZrO₂+ CaO + BaO) is 0.6 to 2.0, preferably (SiO)₂+TiO₂)/(Nb₂O₅+ZrO₂+ CaO + BaO) is 0.8 to 1.8, more preferably (SiO)₂+TiO₂)/(Nb₂O₅+ZrO₂And + CaO + BaO) is 0.9 to 1.5.

5. An optical glass according to claim 1 or 2, characterised in that its components are expressed in weight percentage, wherein: SiO 2₂+B₂O₃: 15 to 30%, preferably SiO₂+B₂O₃: 18-25%; and/or Nb₂O₅+TiO₂+WO₃: 25 to 50%, preferably Nb₂O₅+TiO₂+WO₃: 30-45%; and/or BaO + SrO + CaO + MgO: 20-50%, preferably BaO + SrO + CaO + MgO: 25-40%; and/or ZnO: 0-5%, preferably ZnO: 0-2%; and/or Ln₂O₃: 0 to 9%, preferably Ln₂O₃: 0 to 7 percent; and/or ZrO₂: 1 to 8%, preferably ZrO₂: 2-7%; and/or R₂O: 0 to 6%, preferably R₂O: 0.5-5%; and/or Al₂O₃: 0 to 3%, preferably Al₂O₃: 0-2%; and/or a clarifying agent: 0 to 0.5 percent of a catalyst,the preferred clarifying agent is: 0-0.2%, the Ln₂O₃Is La₂O₃、Gd₂O₃、Y₂O₃、Yb₂O₃One or more of, R₂O is Li₂O、Na₂O、K₂One or more of O and Sb as clarifier₂O₃、SnO₂SnO and CeO₂One or more of (a).

6. An optical glass according to claim 1 or 2, characterised in that its components are expressed in weight percentage, wherein: SiO 2₂: 12-30%, preferably SiO₂: 15 to 25%, more preferably SiO₂: 16-23%; and/or Nb₂O₅: 6 to 20%, preferably Nb₂O₅: 7 to 18%, more preferably Nb₂O₅: 8-17%; and/or TiO₂: 15-35%, preferably TiO₂: 18 to 32%, more preferably TiO₂: 20-30%; and/or BaO: 15-35%, preferably BaO: 18 to 32%, more preferably BaO: 20-30%; and/or CaO: 0-12%, preferably CaO: 1-9%, more preferably CaO: 3-7%; and/or B₂O₃: 0 to 6%, preferably B₂O₃: 0.1 to 5%, more preferably B₂O₃: 0.5-4%; and/or WO₃: 0 to 10%, preferably WO₃: 0 to 5%, more preferably WO₃: 0-2%; and/or SrO: 0 to 8%, preferably SrO: 0 to 4%, more preferably SrO: 0-2%; and/or MgO: 0-8%, preferably MgO: 0 to 4%, more preferably MgO: 0-2%; and/or Li₂O: 0 to 3%, preferably Li₂O: 0 to 2%, more preferably Li₂O: 0 to 1 percent; and/or Na₂O: 0 to 8%, preferably Na₂O: 0 to 6%, more preferably Na₂O: 0.5-5%; and/or K₂O: 0 to 5%, preferably K₂O: 0 to 3%, more preferably K₂O：0～2％。

7. An optical glass according to claim 1 or 2, characterised in that its components are expressed in weight percentage, wherein:Na₂O/CaO is 5.0 or less, preferably Na₂O/CaO is 0.01 to 3.0, and Na is more preferable₂The O/CaO is 0.05-2.5; and/or Li₂O/B₂O₃Is 0.5 or less, preferably Li₂O/B₂O₃Is 0.3 or less, more preferably Li₂O/B₂O₃Is 0.1 or less, and Li is more preferable₂O/B₂O₃Is 0.05 or less; and/or 10 × Li₂O/Nb₂O₅Is 0.7 or less, preferably 10 × Li₂O/Nb₂O₅Is 0.4 or less, more preferably 10 XLi₂O/Nb₂O₅Is 0.2 or less.

8. An optical glass according to claim 1 or 2, characterised in that it further comprises, in percentages by weight: not more than 4% of P₂O₅Preferably not more than 2% of P₂O₅More preferably not more than 1% of P₂O₅(ii) a And/or not more than 4% of Bi₂O₃Preferably not more than 2% of Bi₂O₃More preferably not more than 1% of Bi₂O₃(ii) a And/or not more than 4% of Ta₂O₅Preferably not more than 2% Ta₂O₅More preferably not more than 1% of Ta₂O₅(ii) a And/or not more than 4% of TeO₂Preferably not more than 2% of TeO₂More preferably not more than 1% of TeO₂(ii) a And/or not more than 4% Ga₂O₃Preferably not more than 2% Ga₂O₃More preferably not more than 1% of Ga₂O₃。

9. The optical glass according to claim 1 or 2, wherein the optical glass does not contain ZnO; and/or do not contain Li₂O; and/or does not contain SrO; and/or does not contain MgO; and/or does not contain P₂0₅(ii) a And/or does not contain Bi₂O₃(ii) a And/or does not contain Ta₂O₅(ii) a And/or does not contain TeO₂(ii) a And/or does not contain WO₃(ii) a And/or does not contain Gd₂O₃(ii) a And/or does not contain Y₂O₃。

10. Optical glass according to claim 1 or 2, characterised in that the refractive index n of the optical glass is_d1.89-1.95, preferably 1.90-1.94, more preferably 1.91-1.935; abbe number v_d20 to 27, more preferably 21 to 26, and still more preferably 22 to 25.

11. An optical glass according to claim 1 or 2, characterized in that λ of the optical glass₇₀Is 460nm or less, preferably λ₇₀Is 450nm or less, more preferably lambda₇₀Is 440nm or less; and/or lambda₅Is 400nm or less, preferably lambda₅Is 390nm or less, more preferably λ₅Is 380nm or less; and/or stability against acid action D_AIs 2 or more, preferably 1; and/or stability against water action D_WIs 2 or more, preferably 1; and/or the upper limit temperature of crystallization is 1180 ℃ or lower, preferably 1160 ℃ or lower, more preferably 1140 ℃ or lower; and/or a Young's modulus E of 9500X 10⁷A pressure of 10000X 10 or more, preferably⁷A value of 10500X 10 or more, more preferably,/Pa⁷More than Pa; and/or coefficient of thermal expansion alpha_100～300℃Is 110 x 10^-7Preferably 105X 10 or less,/K^-7A value of less than or equal to K, more preferably 100X 10^-7below/K; the density rho is 4.30g/cm³Hereinafter, it is preferably 4.20g/cm³Hereinafter, more preferably 4.10g/cm³The following; and/or degree of wear F_A150 or more, preferably 180 or more, more preferably 200 to 300; and/or relative partial dispersion P_g,FIs 0.6000 to 0.6400, preferably 0.6100 to 0.6300, and more preferably 0.6150 to 0.6250.

12. A glass preform characterized by being made of the optical glass according to any one of claims 1 to 11.

13. An optical element produced from the optical glass according to any one of claims 1 to 11 or the glass preform according to claim 12.

14. An optical device comprising the optical glass according to any one of claims 1 to 11 or comprising the optical element according to claim 13.