CN117756402A - Optical glass and optical element - Google Patents

Abstract

The invention provides optical glass, which comprises the following components in percentage by weight: siO (SiO) ₂ +B ₂ O ₃ ：12～35％；Nb ₂ O ₅ +TiO ₂ +WO ₃ ：25～55％；BaO+SrO+CaO+MgO：16～50％；ZnO：0～10％；Ln ₂ O ₃ ：0～10％；ZrO ₂ :0 to 10 percent, wherein B ₂ O ₃ /SiO ₂ Is 0.4 or less, (SiO) ₂ +TiO ₂ )/(Nb ₂ O ₅ +ZrO ₂ +CaO+BaO) of 0.5 to 2.2, (ZnO+SrO+Ln) ₂ O ₃ )/SiO ₂ The refractive index of the optical glass is not more than 0.7, and the Abbe number is not more than 30. Through reasonable component design, the optical glass obtained by the invention has the expected refractive index and Abbe number, and simultaneously has excellent chemical stability and lower density, thereby meeting the use of high-performance optical instruments.

Description

Optical glass and optical components

This application is a divisional application for the invention patent application with application number 202111042942.2, application date September 7, 2021, and name “Optical Glass and Optical Elements”.

Technical Field

The present invention relates to an optical glass, in particular to an optical glass with a refractive index of more than 1.88 and an Abbe number of less than 30, and an optical element made of the optical glass.

Background Art

Optical glass with a refractive index of more than 1.88 and an Abbe number of less than 30 is a high-refractive and high-dispersion optical glass. This type of glass can be coupled with low-dispersion optical glass to effectively eliminate chromatic aberration and secondary spectrum. At the same time, it can effectively shorten the total optical length of the lens and miniaturize the imaging system. Therefore, this type of glass has broad application prospects in optical design.

In recent years, as instruments using optical systems have developed towards digitalization and high precision, the requirements for lightweight optical components such as lenses used in various optical instruments have become increasingly higher, which requires that the optical glass used to manufacture optical components have a lower density. On the other hand, optical glass will inevitably be corroded by the environment and various liquids (such as acid, alkali, water, etc.) during processing and use. Therefore, the resistance of optical glass to these corrosions, that is, the chemical stability of optical glass, is crucial to the accuracy and life of optical instruments.

Summary of the invention

Based on the above reasons, the technical problem to be solved by the present invention is to provide an optical glass with excellent chemical stability and low density.

The technical solution adopted by the present invention to solve the technical problem is:

The optical glass comprises, by weight percentage, the following components: _SiO2 + _B2O3 : 12-35%; _Nb2O5 + _TiO2 +WO3 _: 20-55% _; BaO+SrO+CaO+MgO: 16-55%; ZnO: _0-10 %; _Ln2O3 : 0-10%; ZrO2: 0-10%, wherein _B2O3 / _SiO2 is less _than 0.4, ( _SiO2 + _{TiO2 )} /( _Nb2O5 + _ZrO2 +CaO+BaO) is 0.5-2.2, (ZnO+ _SrO + _Ln2O3 )/ _SiO2 is _less than _0.7 , and _{the Ln2O3} is _La2O3 , _{Gd2O3 , Y2O3 , Yb2O3} or _ZrO2 . ₃ , wherein the refractive index _nd of the optical glass is greater than 1.88 and the Abbe number _νd is less than 30.

Furthermore, the optical glass, expressed in weight percentage, further comprises: _R2O : 0-10%; and/or _Al2O3 : 0-5%; and/or clarifier: 0-1%, wherein _R2O is one or more of _Li2O , _Na2O , _K2O , and the clarifier is one _or more of _Sb2O3 , _SnO2 , _SnO and _CeO2 .

Furthermore, the optical glass, wherein the components are expressed in weight percentage, wherein: Nb ₂ O ₅ /BaO is 0.2-1.2, preferably Nb ₂ O ₅ /BaO is 0.2-1.0, more preferably Nb ₂ O ₅ /BaO is 0.25-0.9, and further preferably Nb ₂ O ₅ /BaO is 0.3-0.8; and/or TiO ₂ /(Nb ₂ O ₅ +ZrO ₂ ) is 0.6-5.5, preferably TiO ₂ /(Nb ₂ O ₅ +ZrO ₂ ) is 0.7-4.0, more preferably TiO ₂ /(Nb ₂ O ₅ +ZrO ₂ ) is 0.8-3.0, and further preferably TiO ₂ /(Nb ₂ O ₅ +ZrO ₂ ) is 1.0-2.5; and/or SiO ₂ /(Nb ₂ O ₅ +TiO ₂ ) is 0.3 to 1.3, preferably SiO ₂ /(Nb ₂ O ₅ +TiO ₂ ) is 0.35 to 1.0, and more preferably SiO ₂ /(Nb ₂ O ₅ +TiO ₂ ) is 0.4 to 0.8.

Furthermore, the optical glass, its components are expressed in weight percentage, wherein: B ₂ O ₃ /SiO ₂ is 0.01-0.3, preferably B ₂ O ₃ /SiO ₂ is 0.03-0.2; and/or (ZnO+SrO+Ln ₂ O ₃ )/SiO ₂ is 0.6 or less, preferably (ZnO+SrO+Ln ₂ O ₃ )/SiO ₂ is 0.5 or less, more preferably (ZnO+SrO+Ln ₂ O ₃ )/SiO ₂ is 0.3 or less; and/or (SiO ₂ +TiO ₂ )/(Nb ₂ O ₅ +ZrO 2 +CaO+BaO) is 0.6-2.0, preferably (SiO ₂ +TiO ₂ )/(Nb 2 O 5 +ZrO ₂ +CaO+BaO) is 0.6-2.0.

(Nb ₂ O ₅ + ZrO ₂ + CaO + BaO) is 0.8 to 1.8, and more preferably (SiO ₂ + TiO ₂ )/(Nb ₂ O ₅ + ZrO ₂ + CaO + BaO) is 0.9 to 1.5.

Furthermore, the optical glass, its components are expressed by weight percentage, wherein: SiO ₂ +B ₂ O ₃ : 15-30%, preferably SiO ₂ +B ₂ O ₃ : 18-25%; and/or Nb ₂ O ₅ +TiO ₂ +WO ₃ : 25-50%, preferably Nb ₂ O ₅ +TiO ₂ +WO ₃ : 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 Ln ₂ O ₃ : 0-9%, preferably Ln ₂ O ₃ : 0-7%; and/or ZrO ₂ : 1-8%, preferably ZrO ₂ : 2-7%; and/or R ₂ O: 0-6%, preferably R ₂ O: 0.5-5%; and/or Al ₂ O ₃ : 0-3%, preferably Al ₂ O ₃ : 0-2%; and/or clarifier: 0-0.5%, preferably clarifier: 0-0.2%, the Ln ₂ O ₃ is one or more of La ₂ O ₃ , Gd ₂ O ₃ , Y ₂ O ₃ , and Yb ₂ O ₃ , R ₂ O is one or more of Li ₂ O, Na ₂ O, and K ₂ O, and the clarifier is one or more of Sb ₂ O ₃ , SnO ₂ , SnO, and CeO ₂ .

Further, the optical glass, its components are expressed by weight percentage, wherein: SiO ₂ : 12-30%, preferably SiO ₂ : 15-25%, more preferably SiO ₂ : 16-23%; and/or Nb ₂ O ₅ : 6-20%, preferably Nb ₂ O ₅ : 7-18%, more preferably Nb ₂ O ₅ : 8-17%; and/or TiO ₂ : 15-35%, preferably TiO ₂ : 18-32%, more preferably TiO ₂ : 20-30%; and/or BaO: 15-35%, preferably BaO: 18-32%, more preferably BaO: 20-30%; and/or CaO: 0-12%, preferably CaO: 1-9%, more preferably CaO: 3-7%; and/or B ₂ O ₃ : 0-6%, preferably B ₂ O ₃ : 0.1-5%, more preferably B ₂ O ₃ : 0.5-4%; and/or WO ₃ : 0-10%, preferably WO ₃ : 0-5%, more preferably WO ₃ : 0-2%; and/or SrO: 0-8%, preferably SrO: 0-4%, more preferably SrO: 0-2%; and/or MgO: 0-8%, preferably MgO: 0-4%, more preferably MgO: 0-2%; and/or Li ₂ O: 0-3%, preferably Li ₂ O: 0-2%, more preferably Li ₂ O: 0-1%; and/or Na ₂ O: 0-8%, preferably Na ₂ O: 0-6%, more preferably Na ₂ O: 0.5-5%; and/or K ₂ O: 0-5%, preferably K ₂ O: 0-3%, more preferably K ₂ O: 0-2%.

Furthermore, the optical glass, whose components are expressed in weight percentage, wherein: Na ₂ O/CaO is less than 5.0, preferably Na ₂ O/CaO is 0.01-3.0, more preferably Na ₂ O/CaO is 0.05-2.5; and/or Li ₂ O/B ₂ O ₃ is less than 0.5, preferably Li ₂ O/B ₂ O ₃ is less than 0.3, more preferably Li ₂ O/B ₂ O ₃ is less than 0.1, further preferably Li ₂ O/B ₂ O ₃ is less than 0.05; and/or 10×Li ₂ O/Nb ₂ O ₅ is less than 0.7, preferably 10×Li ₂ O/Nb ₂ O ₅ is less than 0.4, more preferably 10×Li ₂ O/Nb ₂ O ₅ is less than 0.2.

Furthermore, the optical glass, expressed in terms of components by weight, also contains: no more than 4% of P ₂ O ₅ , preferably no more than 2% of P ₂ O ₅ , more preferably no more than 1% of P ₂ O ₅ ; and/or no more than 4% of Bi ₂ O ₃ , preferably no more than 2% of Bi ₂ O ₃ , more preferably no more than 1% of Bi ₂ O ₃ ; and/or no more than 4% of Ta ₂ O ₅ , preferably no more than 2% of Ta ₂ O ₅ , more preferably no more than 1% of Ta ₂ O ₅ ; and/or no more than 4% of TeO ₂ , preferably no more than 2% of TeO ₂ , more preferably no more than 1% of TeO ₂ ; and/or no more than 4% of Ga ₂ O ₃ , preferably no more than 2% of Ga ₂ O ₃ , more preferably no more than 1% of Ga ₂ O ₃ .

Furthermore, the optical glass does not contain ZnO; and/or does not contain Li ₂ O; and/or does not contain SrO; and/or does not contain MgO; and/or does not contain P ₂ O ₅ ; and/or does not contain Bi ₂ O ₃ ; and/or does not contain Ta ₂ O ₅ ; and/or does not contain TeO ₂ ; and/or does not contain WO ₃ ; and/or does not contain Gd ₂ O ₃ ; and/or does not contain Y ₂ O ₃ .

Furthermore, the refractive index _nd of the optical glass is 1.89-1.95, preferably 1.90-1.94, and more preferably 1.91-1.935; the Abbe number _νd is 20-27, more preferably 21-26, and further preferably 22-25.

Further, the optical glass has a λ ₇₀ of 460 nm or less, preferably λ ₇₀ of 450 nm or less, more preferably λ ₇₀ of 440 nm or less; and/or a λ ₅ of 400 nm or less, preferably λ ₅ of 390 nm or less, more preferably λ ₅ of 380 nm or less; and/or an acid resistance stability _DA of Class 2 or more, preferably Class 1; and/or a water resistance stability _DW of Class 2 or more, preferably Class 1; and/or a crystallization upper limit temperature of 1180°C or less, preferably 1160°C or less, more preferably 1140°C or less; and/or a Young's modulus E of 9500×10 ⁷ /Pa or more, preferably 10000×10 ⁷ /Pa or more, more preferably 10500×10 ⁷ /Pa or more; and/or a thermal expansion coefficient α _100-300°C of 110×10 ^-7 /K or less, preferably 105×10 ^-7 /K or less, more preferably 100×10 ^-7 /K or less; density ρ is 4.30 g/cm ³ or less, preferably 4.20 g/cm ³ or less, more preferably 4.10 g/cm ³ or less; and/or abrasion degree _FA is 150 or more, preferably 180 or more, more preferably 200-300; and/or relative partial dispersion P _g,F is 0.6000-0.6400, preferably 0.6100-0.6300, more preferably 0.6150-0.6250.

The glass preform is made of the above optical glass.

The optical element is made of the above optical glass, or made of the above glass preform.

An optical instrument containing the above optical glass or the above optical element.

The beneficial effects of the present invention are as follows: through reasonable component design, the optical glass obtained by the present invention has the desired refractive index and Abbe number, and at the same time has excellent chemical stability and low density, which meets the requirements for use of high-performance optical instruments.

DETAILED DESCRIPTION

The following is a detailed description of the embodiments of the optical glass of the present invention, but the present invention is not limited to the following embodiments and can be implemented by appropriate changes within the scope of the purpose of the present invention. In addition, although there are appropriate omissions of descriptions of the repeated descriptions, the gist of the present invention is not limited thereto. In the following content, the optical glass of the present invention is sometimes referred to as glass.

[Optical glass]

The following is an explanation of the range of each component of the optical glass of the present invention. In this specification, unless otherwise specified, the content of each component is expressed in terms of weight percentage (wt%) relative to the total amount of glass material converted into an oxide composition. Here, the "composition converted into oxides" means that when oxides, complex salts, hydroxides, etc. used as raw materials for the optical glass components of the present invention are decomposed and converted into oxides during melting, the total amount of the oxide material is taken as 100%.

Unless otherwise indicated in specific cases, the numerical ranges listed herein include upper and lower limits, "above" and "below" include endpoint values, and all integers and fractions within the range, without limitation to the specific values listed when the range is defined. The term "about" as used herein means that the formula, parameters and other quantities and features are not and need not be exact, and may be approximate and/or larger or lower if necessary, reflecting tolerances, conversion factors and measurement errors, etc. "And/or" as used herein is inclusive, for example, "A and/or B" means only A, or only B, or both A and B.

<Essential and Non-essential Components>

SiO ₂ and B ₂ O ₃ are components that constitute the glass skeleton, which can improve the stability of the glass and adjust the melt viscosity of the glass. When the total content of SiO 2 and B ₂ O ₃ is high, it is difficult to obtain the desired high refractive index of the present invention. Therefore, the total content of SiO ₂ and B ₂ O ₃ is SiO ₂ + B ₂ O ₃ is 12 to 35%, preferably SiO ₂ + B 2 O 3 is 15 to 30%, and more preferably SiO ₂ + B ₂ O ₃ is 18 to 25%. In some embodiments, SiO ₂ + B ₂ O The content of ₃ is 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%.

_SiO2 is a network generator of the glass of the present invention, which has the effect of maintaining the chemical stability of the glass and the viscosity suitable for molten glass molding, improving the resistance of the glass to devitrification, and reducing the corrosion of the molten glass liquid to the refractory material. If the _SiO2 content is lower than 12%, it is difficult to achieve the above effect, so the lower limit of the content of _SiO2 is 12%, preferably 15%, and more preferably 16%. If the content of _SiO2 is higher than 30%, the glass meltability decreases and the transition temperature rises. Therefore, the upper limit of the content of _SiO2 is 30%, preferably 25%, and more preferably 23%. In some embodiments, the SiO2 may comprise 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% _.

_B2O3 can improve the thermal stability of glass, enhance the solubility of glass, inhibit the _rapid escape of gas when raw materials are melted, and thus avoid "burning". When contained in an appropriate amount, it is easier to obtain glass without molten glass raw material residue. However, when the content of _B2O3 is too much, the refractive index of the _glass decreases and the thermal stability becomes poor. Therefore, the content of _B2O3 in the present invention is less than ₆ %, preferably 0.1-5%, and more preferably 0.5-4%. 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% _B2O3 can be _included .

In some embodiments of the present invention, the ratio of B ₂ O ₃ to SiO ₂ , B ₂ O ₃ /SiO _2, is controlled to be below 0.4, which is beneficial to improving the chemical stability of the glass. Therefore, B ₂ O ₃ /SiO ₂ is preferably below 0.4. Further, by making B ₂ O ₃ /SiO ₂ in the range of 0.01 to 0.3, it is also beneficial to optimize the Young's modulus and abrasion resistance of the glass. Therefore, B ₂ O ₃ /SiO ₂ is more preferably 0.01 to 0.3, and B ₂ O ₃ /SiO ₂ is further preferably 0.03 to 0.2. In some embodiments, the value of _B2O3 / _SiO2 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.

Nb ₂ O ₅ , TiO ₂ , and WO ₃ are high-refractive and high-dispersion components. When the total content of Nb ₂ O ₅ +TiO ₂ +WO ₃ is less than 20%, the refractive index and dispersion of the glass are difficult to meet the design requirements; when the total content of Nb ₂ O ₅ +TiO ₂ +WO ₃ is greater than 55%, the devitrification resistance and chemical stability of the glass decrease, and the light transmittance deteriorates. Therefore, in the present invention, Nb ₂ O ₅ +TiO ₂ +WO ₃ is 20-55%, preferably Nb ₂ O ₅ +TiO 2 +WO ₃ is 25-50%, and more preferably Nb ₂ O ₅ +TiO ₂ +WO 3 is 30-45%. In some embodiments, Nb 2 O 5 +TiO ₂ +WO 3 is 20% to 50%; preferably Nb ₂ O ₅ +TiO ₂ +WO ₃ is 30% to 45%. The content of ₃ is 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%, 4 9.5%, 50%, 50.5%, 51%, 51.5%, 52%, 52.5%, 53%, 53.5%, 54%, 54.5%, 55%.

_Nb2O5 is _a high-refractive and high-dispersion component, which can improve the refractive index and devitrification resistance of glass and reduce the thermal expansion coefficient of _glass . The present invention achieves the above effects by containing 6% or more of _Nb2O5 , preferably ₇ % or more, more preferably 8% or more. If the content of _Nb2O5 exceeds 20%, the thermal stability _{and chemical} stability of the glass will decrease, and the light transmittance _will decrease. Therefore, the upper limit of the content of _Nb2O5 in the present invention is 20%, preferably 18%, and 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% _Nb2O5 may be included _.

_TiO2 has the function of increasing the refractive index and dispersion of glass, and can participate in the formation of glass network. An appropriate amount of _TiO2 can make the glass more stable and reduce the high-temperature viscosity of the glass. In the present invention, the above-mentioned effect is obtained by containing more than 15% _TiO2 , preferably more than 18% _TiO2 , and more preferably more than 20% _TiO2 . If the TiO2 content exceeds 35%, the _{crystallization} tendency of the glass increases, the transition temperature rises, and the glass becomes easy to color when press-formed. Therefore, the _TiO2 content in the present invention is less than 35%, preferably less than 32%, and more preferably less than 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% TiO2 _{may be included} .

In some embodiments of the present invention, by controlling the ratio of SiO ₂ content to the total content of Nb ₂ O ₅ and TiO ₂ Nb ₂ O ₅ +TiO ₂ SiO ₂ /(Nb ₂ O ₅ +TiO ₂ ) within the range of 0.3 to 1.3, the glass can obtain _{appropriate abrasiveness and relative partial dispersion while reducing the thermal expansion coefficient and density of the glass. Therefore, SiO 2 /(Nb 2 O 5 + TiO 2} ) is preferably 0.3 to _{1.3 ,} more preferably _0.35 to _{1.0 ,} and further preferably _0.4 to 0.8. In some embodiments of the present invention, the value of _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} .

WO ₃ can improve the refractive index and dispersion of glass, but the effect is not as good as Nb ₂ O ₅ and TiO ₂ , and it does not have cost advantages, and it will also cause the light transmittance of glass to decrease. Therefore, the content of WO ₃ in the present invention is 0-10%, preferably 0-5%, more preferably 0-2%, and further preferably does not contain WO _3. 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 ₃ may be included.

ZnO can adjust the refractive index and dispersion of glass and reduce the transition temperature of glass. If its content exceeds 10%, the anti-crystallization performance of glass decreases, and the high temperature viscosity is small, which brings difficulties to molding and increases the thermal expansion coefficient and refractive index temperature coefficient of glass. Therefore, the ZnO content in the present invention is 0-10%, preferably 0-5%, and more preferably 0-2%. In some embodiments, it is further preferred that ZnO is not contained. 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 one or more of _Li2O , _Na2O , _K2O ) can reduce the transition temperature of glass. When its content exceeds 10%, the chemical stability of glass decreases. Therefore, the content of _R2O is 0-10%, preferably 0-6%, and more preferably 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%, 8.5%, 9%, 9.5%, 10% of _R2O can be included.

_Li2O can reduce the transition temperature of glass and improve the melting property of glass, but its high content is not good for the chemical stability, anti-crystallization ability and thermal expansion coefficient of glass. Therefore, the content of _Li2O in the present invention is 3% or less, preferably 2% or less, and more preferably 1% or less. In some embodiments, it is further preferred that _Li2O is not contained. 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% _Li2O may be included.

In some embodiments of the present invention, by making the ratio of Li ₂ O content to B ₂ O ₃ content Li ₂ O/B ₂ O ₃ below 0.5, the chemical stability of the glass and the secondary pressing anti-surface crystallization performance can be improved, and the abrasiveness of the glass can be optimized. Therefore, preferably Li ₂ O/B ₂ O ₃ is below 0.5, more preferably Li ₂ O/B ₂ O ₃ is below 0.3, further preferably Li ₂ O/B ₂ O ₃ is below 0.1, and further preferably Li ₂ O/B ₂ O ₃ is below 0.05. In some embodiments, Li ₂ O/B ₂ O The value of ₃ 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, 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 present invention, by making 10×Li ₂ O/Nb ₂ O ₅ below 0.7, it is beneficial to improve the chemical stability and secondary compression molding anti-crystallization performance of the glass, and improve the Young's modulus of the glass. Therefore, it is preferred that 10×Li ₂ O/Nb ₂ O ₅ is below 0.7, more preferably 10×Li ₂ O/Nb ₂ O ₅ is below 0.4, and further preferably 10×Li ₂ O/Nb ₂ O ₅ is below 0.2. In some embodiments of the present invention, 10×Li ₂ O/Nb ₂ O The value of ₅ 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 6. 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 the function of improving the glass solubility, can improve the glass melting effect, and can also reduce the glass transition temperature. In the present invention, an appropriate amount of Na2O can also improve the light transmittance of the glass. If the content of _Na2O exceeds 8%, the chemical stability and weather resistance of the glass will decrease. Therefore, the content of _Na2O is 0-8%, preferably the content of _Na2O is 0-6%, and more preferably the content of _Na2O 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% of _Na2O can be included.

_K2O has the effect of improving the thermal stability and melting property of glass, but when its content exceeds 5 _% , the devitrification resistance and chemical stability of glass deteriorate. Therefore, in the present invention, the content of _K2O is 5% or less, preferably 3% or less, and more preferably 2% or less. In some embodiments, about 0%, more 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% of _K2O may be included.

Appropriate amounts of alkaline earth metal oxides BaO, SrO, CaO and MgO in glass can adjust the refractive index and dispersion of the glass, and at the same time can improve the stability of the glass. In the present invention, the above effects are obtained by containing more than 16% of alkaline earth metal oxides. 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 anti-crystallization performance of the glass is reduced. Therefore, in the present invention, BaO+SrO+CaO+MgO is limited to 16-55%, preferably BaO+SrO+CaO+MgO is 20-50%, and more preferably BaO+SrO+CaO+MgO is 25-40%. 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%, 34.5%, 35.5%, 36.5%, 37.5%, 38.5%, 39.5%, 40.5%, 41.5%, 42.5%, 43.5%, 44.5%, 45.5%, 46.5%, 47.5%, 48.5%, 49.5%, 50. %, 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 glass, but when the MgO content is too much, the refractive index of the glass cannot meet the design requirements, the anti-crystallization performance and stability of the glass decrease, and the cost of the glass increases. Therefore, the MgO content is limited to 0-8%, preferably 0-4%, and more preferably 0-2%. In some embodiments, it is further preferred that MgO is not contained. 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 helps to adjust the optical constants of glass, improve the processing properties of glass, and reduce the density of glass. However, when the CaO content is too much, the optical constants of glass cannot meet the requirements and the anti-crystallization performance deteriorates. Therefore, the CaO content is limited to 0-12%, preferably 1-9%, and more preferably 3-7%. 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 present invention, by controlling the ratio of Na ₂ O to CaO to be below 5.0, the anti-crystallization performance of the glass can be improved. Therefore, it is preferred that Na ₂ O/CaO is below 5.0. Further, by controlling Na ₂ O/CaO to be within the range of 0.01 to 3.0, it is also beneficial to improve the light transmittance and Young's modulus of the glass. Therefore, it is more preferred that Na ₂ O/CaO is 0.01 to 3.0, and it is further _preferred that Na ₂ O/CaO is 0.05 to 2.5. In some embodiments of the present invention, Na ₂ The value of O/CaO 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, 0.2, 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, 4.4, 4.5, 4.6, 4.7, 4.8, 4 .9, 5.0.

SrO can adjust the refractive index and Abbe number of the glass, but if its content is too large, the chemical stability of the glass will be reduced, and the cost of the glass will also rise rapidly. Therefore, the SrO content is limited to 0-8%, preferably 0-4%, and more preferably 0-2%. In some embodiments, it is further preferred that SrO is not contained. 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 glass, improving the transmittance and strength of glass in the present invention. When its content is less than 15%, the above effects are not obvious. Preferably, the lower limit of BaO content is 18%, and more preferably, the lower limit of BaO content is 20%. On the other hand, if the content of BaO exceeds 35%, the anti-crystallization performance and chemical stability of the glass will deteriorate, and the density will increase significantly. Therefore, the upper limit of BaO content is 35%, preferably 32%, and 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 present invention, by controlling the ratio of Nb _{2 O 5} to BaO in the range of 0.2 to 1.2, the glass of the present invention can have excellent chemical stability while reducing the thermal expansion coefficient of the glass. Therefore, Nb ₂ O ₅ /BaO is preferably 0.2 to 1.2, and more preferably Nb ₂ O ₅ /BaO is 0.2 to 1.0. Furthermore, by controlling Nb _{2 O 5 /BaO in the range of 0.25 to 0.9, the Young's modulus of the glass can be further increased. Therefore, Nb 2 O 5 /} BaO is more preferably 0.25 to 0.9, and even more preferably _{Nb 2} O ₅ /BaO is 0.3 to 0.8. In some embodiments of the present invention, the value of _Nb2O5 /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 .

_ZrO2 can increase the refractive index of glass and adjust dispersion, improve the anti-crystallization performance and strength of glass. If the content of _ZrO2 is higher than 10%, the difficulty of glass melting increases, the melting temperature rises, and even inclusions appear inside the glass and the transmittance decreases. Therefore, the content of _ZrO2 is less than 10%, preferably 1-8%, and more preferably 2-7%. 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% ZrO2 may _{be included} .

In some embodiments of the present invention, by controlling the ratio of TiO ₂ content to the total content of Nb ₂ O ₅ and ZrO ₂ Nb ₂ O ₅ +ZrO ₂ TiO ₂ /(Nb ₂ O ₅ +ZrO ₂ ) in the range of 0.6 to 5.5, it is beneficial to improve the anti-crystallization performance and light transmittance of the glass. Therefore, preferably TiO ₂ /(Nb ₂ O ₅ +ZrO ₂ ) is 0.6 to 5.5, and more preferably TiO ₂ /(Nb ₂ O ₅ +ZrO ₂ ) is 0.7 to 4.0. Furthermore, by controlling TiO ₂ /(Nb ₂ O ₅ +ZrO ₂ ) in the range of 0.8 to 3.0, the glass can also obtain appropriate abrasiveness and relative partial dispersion. Therefore, it is further preferred that TiO ₂ /(Nb ₂ O ₅ +ZrO ₂ ) is 0.8 to 3.0, and it is further preferred that TiO ₂ /(Nb ₂ O ₅ +ZrO ₂ ) is 1.0 to 2.5. In some embodiments of the present invention, the value of TiO ₂ /(Nb ₂ O ₅ +ZrO ₂ ) 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, 2.0, 2.5. 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, 4.6, 4.7, 4.8, 4.9, 5.0, 5.1 ,5.2,5.3,5.4,5.5.

In some embodiments of the present invention, by controlling the ratio of the total content of _SiO2 and _TiO2 ( _SiO2 + _{TiO2 )} to the total content of _Nb2O5 , _ZrO2 , CaO and BaO ( _Nb2O5 + _ZrO2 + _CaO + BaO) within the range of _0.5 to 2.2, the glass forming stability and chemical stability of the glass can be improved and the density of the glass can be reduced. Therefore, preferably, ( _{SiO2 + TiO2} ) / ( _Nb2O5 + _ZrO2 + _CaO + _BaO ) is 0.5 to 2.2, and more preferably, ( _SiO2 + _TiO2 ) / ( _Nb2O5 + _ZrO2 + _{CaO +} BaO) is 0.6 to _2.0 . Furthermore, by controlling ( _SiO2 + _TiO2 )/( _Nb2O5 + _ZrO2 + _CaO +BaO) within the range of 0.8 to 1.8, the secondary compression molding anti-vitrification performance and Young's modulus of the glass can be further improved. Therefore, it is further preferred that ( _SiO2 + _TiO2 )/( _Nb2O5 + _ZrO2 + _CaO +BaO) is 0.8 to 1.8, and it is further preferred that ( _SiO2 + _TiO2 )/( _Nb2O5 + _ZrO2 + _CaO +BaO) is 0.9 to 1.5. In some embodiments of the invention, the value of ( _SiO2 + _TiO2 )/( _Nb2O5 + _ZrO2 +CaO+BaO) may be 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.

Ln ₂ O ₃ (Ln ₂ O ₃ is one or more of La ₂ O ₃ , Gd ₂ O ₃ , Y ₂ O ₃ , and Yb ₂ O ₃ ) is a component that increases the refractive index and chemical stability of glass. By controlling the content of Ln ₂ O ₃ to 10% or less, the devitrification resistance of glass can be prevented from decreasing. Preferably, the upper limit of the content of Ln ₂ O ₃ is 9%, and more preferably, the upper limit is 7%. In some embodiments, Ln ₂ O ₃ is preferably La ₂ O _3. In some embodiments, it is preferred that Gd ₂ O ₃ is not contained; and/or Y ₂ O ₃ is not contained; and/or Yb ₂ O ₃ is not contained. 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% _Ln2O3 may be _included .

In some embodiments of the present invention, by controlling the ratio between the total content of ZnO, SrO and Ln ₂ O ₃ ZnO + SrO + Ln ₂ O ₃ and the content of SiO ₂ (ZnO + SrO + Ln ₂ O ₃ ) / SiO ₂ to be below 0.7, it is beneficial to reduce the density and relative partial dispersion of the glass. Therefore, it is preferred that (ZnO + SrO + Ln ₂ O ₃ ) / SiO ₂ is below 0.7, and it is more preferred that (ZnO + SrO + Ln ₂ O ₃ ) / SiO ₂ is below 0.6. Furthermore, by controlling (ZnO + SrO + Ln ₂ O ₃ ) / SiO ₂ to be below 0.5, the thermal expansion coefficient of the glass can also be reduced. Therefore, it is further preferred that (ZnO + SrO + Ln ₂ O ₃ ) / SiO ₂ is 0.5 or less, and it is further preferred that (ZnO + SrO + Ln ₂ O ₃ ) / SiO ₂ is 0.3 or less. In some embodiments of the present invention, the value of (ZnO + SrO + Ln ₂ O ₃ ) / SiO ₂ 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, 0.30, 0.31, 0.32, 0.33, 0.34, 0.35, 0.36, 0.37, 0.38, 0.39, 0.40, 0.41, 0.42, 0.43, 0.44, 0.45, 0.46, 0.47, 0.48, 0.49, 0.50, 0.51, 0.52, 0.5 6. 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.

_Al2O3 can improve the chemical stability of glass, but when its content is too _large , the devitrification resistance and melting property of glass are reduced, so its 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% of _{Al2O3 may be included} .

In some embodiments, the glass of the present invention may also contain 0-1% of a clarifier to improve the defoaming ability of the glass. Such clarifiers include, but are not limited to, one or more of Sb ₂ O ₃ , SnO ₂ , SnO and CeO ₂ , preferably Sb ₂ O ₃ as a clarifier. When the above clarifiers exist alone or in combination, the upper limit of their content is preferably 0.5%, and the upper limit is more preferably 0.2%. In some embodiments, the content of one or more of the above clarifiers is 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%.

Within the range not damaging the glass properties of the present invention, other components not mentioned above, such as _P2O5 , _{Bi2O3 , Ta2O5 , TeO2} and _{Ga2O3 ,} may be added in small amounts as needed _. Preferably, the content of the above components alone or in total does not exceed 4%, more preferably does not exceed 2%, further preferably does not exceed 1 _% , and further preferably does not contain _P2O5 ; and/or _{Bi2O3 ;} and/or _Ta2O5 ; and _/ or _{TeO2 ;} and/or _Ga2O3 .

<Components that should not be contained>

In the glass of the present invention, even if oxides of transition metals such as V, Cr, Mn, Fe, Co, Ni, Cu, Ag and Mo are contained alone or in combination in small amounts, the glass will be colored and absorption will occur at specific wavelengths in the visible light region, thereby weakening the property of the present invention of improving the visible light transmittance. Therefore, it is preferably substantially free of oxides of transition metals such as V, Cr, Mn, Fe, Co, Ni, Cu, Ag and Mo, especially for optical glasses that require transmittance at wavelengths in the visible light region.

The oxides of Th, Cd, Tl, Os, Be and Se have a tendency to be controlled in recent years as harmful chemical substances, and environmental protection measures are necessary not only in the manufacturing process of glass, but also in the processing process and the disposal after productization. Therefore, in the case of paying attention to the impact on the environment, it is preferred that they are actually not contained except for the inevitable mixing. As a result, the optical glass does not actually contain substances that pollute the environment. Therefore, even if no special environmental countermeasures are taken, the optical glass of the present invention can be manufactured, processed and discarded. At the same time, in order to achieve environmental friendliness, the optical glass of the present invention preferably does not contain As ₂ O ₃ and PbO.

The "does not contain" and "0%" recorded in this article mean that the compound, molecule or element is not intentionally added as a raw material to the optical glass of the present invention; however, as raw materials and/or equipment for producing optical glass, there will be certain impurities or components that are not intentionally added, which will be contained in a small amount or trace amount in the final optical glass, and this situation is also within the scope of protection of the patent of this invention.

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

<Refractive Index and Abbe Number>

The refractive index (n _d ) and Abbe number (ν _d ) of optical glass are tested according to the method specified in GB/T 7962.1—2010.

In some embodiments, the refractive index (n _d ) of the optical glass of the present invention is 1.88 or more, preferably 1.89 to 1.95, more preferably 1.90 to 1.94, and even more preferably 1.91 to 1.935.

In some embodiments, the Abbe number (ν _d ) of the optical glass of the present invention is 30 or less, preferably 28 or less, more preferably 20-27, further preferably 21-26, and further preferably 22-25.

<Color>

The short-wave transmission spectrum characteristics of the glass of the present invention are expressed by the coloration (λ ₇₀ and λ ₅ ). λ ₇₀ refers to the wavelength corresponding to when the glass transmittance reaches 70%. The measurement of λ ₇₀ is to use a glass with a thickness of 10±0.1mm having two relative planes parallel to each other and optically polished, measure the spectral transmittance in the wavelength range from 280nm to 700nm, and show the wavelength at which the transmittance is 70%. The so-called spectral transmittance or transmittance is the amount expressed by I _out /I _in when light with intensity I _in is incident vertically on the above-mentioned surface of the glass, passes through the glass and emits light with intensity I _out from one plane, and also includes the transmittance of the surface reflection loss on the above-mentioned surface of the glass. The higher the refractive index of the glass, the greater the surface reflection loss. Therefore, in high-refractive index glass, a small value of λ ₇₀ means that the glass itself is less colored and the light transmittance is high.

In some embodiments, the λ ₇₀ of the optical glass of the present invention is 460 nm or less, preferably λ ₇₀ is 450 nm or less, and more preferably λ ₇₀ is 440 nm or less.

In some embodiments, the λ ₅ of the optical glass of the present invention is less than 400 nm, preferably less than 390 nm, and more preferably _less than 380 _nm .

<Acid resistance stability>

The acid resistance stability ( _DA ) (powder method) of optical glass is tested according to the method specified in GB/T 17129.

In some embodiments, the acid resistance stability (D _A ) of the optical glass of the present invention is Class 2 or above, preferably Class 1.

<Water resistance stability>

The water resistance stability (D _W ) (powder method) of optical glass is tested according to the method specified in GB/T 17129.

In some embodiments, the water resistance stability (D _W ) of the optical glass of the present invention is Class 2 or higher, preferably Class 1.

<Crystallization upper limit temperature>

The crystallization properties of glass were determined by the gradient temperature furnace method. The glass was made into a sample of 180×10×10mm, polished on the side, placed in a furnace with a temperature gradient (10℃/cm), heated to 1300℃ (temperature in the highest temperature zone), kept warm for 4 hours, taken out and naturally cooled to room temperature. The crystallization of the glass was observed under a microscope. The highest temperature corresponding to the appearance of crystals in the glass was the upper limit temperature of crystallization of the glass.

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

<Young's modulus>

The Young's modulus (E) of glass is calculated using the following formula by ultrasonic testing of its longitudinal wave velocity and transverse wave velocity.

G＝V _S ² ρ

Where: E is Young's modulus, Pa;

G is the shear modulus, Pa;

V _T is the shear wave velocity, m/s;

V _S is the longitudinal wave velocity, m/s;

ρ is the density of glass, g/cm ³ .

In some embodiments, the Young's modulus (E) of the optical glass of the present invention is 9500×10 ⁷ /Pa or more, preferably 10000×10 ⁷ /Pa or more, and more preferably 10500×10 ⁷ /Pa or more.

<Coefficient of Thermal Expansion>

The thermal expansion coefficient of optical glass (α _100～300℃ ) is tested at 100～300℃ according to the method specified in GB/T7962.16-2010.

The thermal expansion coefficient (α _{100-300° C.} ) of the optical glass of the present invention is 110×10 ⁻⁷ /K or less, preferably 105×10 ⁻⁷ /K or less, and more preferably 100×10 ⁻⁷ /K or less.

<density>

The density (ρ) of optical glass is tested according to the method specified in GB/T7962.20-2010.

In some embodiments, the density (ρ) of the optical glass of the present invention is 4.30 g/cm ³ or less, preferably 4.20 g/cm ³ or less, and more preferably 4.10 g/cm ³ or less.

<Abrasion>

The abrasion degree ( _FA ) of optical glass refers to the value obtained by multiplying the ratio of the wear amount of the sample to the wear amount (volume) of the standard sample (H-K9 glass) by 100 under exactly the same conditions. It is expressed by the following formula:

F _A =V/V ₀ ×100=(W/ρ)/(W ₀ /ρ ₀ )×100

Where: V—volume wear of the sample being tested;

V ₀ — volume loss of standard sample;

W—mass wear loss of the sample being tested;

W ₀ — standard sample mass wear;

ρ—density of the sample being tested;

ρ ₀ —density of standard sample.

In some embodiments, the abrasion resistance ( _FA ) of the optical glass of the present invention is 150 or more, preferably 180 or more, and more preferably 200-300.

<Relative partial dispersion>

The relative partial dispersion for wavelengths x and y is expressed by the following equation (1):

P _x,y =(n _x -n _y )/(n _F -n _C ) (1)

According to the Abbe number formula, for most so-called "normal glasses" (H-K6 and F4 are selected as "normal glasses" below), the following formula (2) is valid:

P _x,y =m _x,y ·v _d +b _x,y (2)

This linear relationship is expressed with P _x,y as the ordinate and v _d as the abscissa, where m _x,y is the slope and b _x,y is the intercept.

As is known to all, the correction of the secondary spectrum, i.e. the achromatization of more than two wavelengths, requires at least one glass that does not conform to the above formula (2) (i.e. its P _x,y value deviates from the Abbe number empirical formula), and its deviation value is represented by ΔP x, _y . Then each P _x,y -v _d point is shifted by ΔP _x,y relative to the "normal line" that conforms to the above formula (2). Thus, the ΔP _x,y value of each glass can be calculated using the following formula (3):

P _x,y ＝m _x,y ·v _d +b _x,y +ΔP _x,y (3)

Therefore, the calculation formula of relative partial dispersion (P _g,F ) can be obtained as follows (4):

P _g,F =(n _g -n _F )/(n _F -n _C ) (4)

In some embodiments, the relative partial dispersion (P _g,F ) of the optical glass of the present invention is 0.6000 to 0.6400, preferably 0.6100 to 0.6300, and more preferably 0.6150 to 0.6250.

<Secondary Pressing Anti-Crystallization Performance>

The test method of the secondary pressing anti-crystallization performance is: cut the sample glass into 20×20×10mm specifications, put it into a muffle furnace at a temperature of _Tg + (200-250)℃ and keep it warm for 15-30 minutes, take it out and cool it down, and observe whether there are crystals or opacity on the surface and inside of the glass. If the glass sample has no opacity and/or crystals, the secondary pressing anti-crystallization performance of the glass is excellent.

[Manufacturing method]

The manufacturing method of the optical glass of the present invention is as follows: the glass of the present invention is produced using conventional raw materials and processes, including but not limited to using oxides, hydroxides, fluorides, various salts (carbonates, nitrates, sulfates, phosphates, metaphosphates) and the like as raw materials, and after mixing the materials according to conventional methods, the prepared furnace materials are put into a melting furnace (such as a platinum crucible) at 1000-1400° C. for melting, and after clarification and homogenization, a homogeneous molten glass without bubbles and undissolved substances is obtained, and the molten glass is cast in a mold and annealed. Those skilled in the art can appropriately select raw materials, process methods and process parameters according to actual needs.

[Glass preforms and optical components]

The prepared optical glass can be used to make a glass preform by means of direct drop molding, grinding, or compression molding such as hot press molding. That is, the molten optical glass can be directly precision drop molded into a glass precision preform, or the glass preform can be made by mechanical processing such as grinding and grinding, or the preform for compression molding made of the optical glass can be made by hot press molding and then grinding. It should be noted that the means for preparing the glass preform are 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 it is particularly preferred to form a preform from the optical glass of the present invention and use the preform to perform re-hot pressing, precision stamping, etc. to produce optical elements such as lenses and prisms.

The glass preform and optical element of the present invention are both formed of the optical glass of the present invention. The glass preform of the present invention has the excellent properties of optical glass; the optical element of the present invention has the excellent properties of optical glass, and can provide various optical elements such as lenses and prisms with high optical value.

Examples of the lens include various lenses having spherical or aspherical lens surfaces, 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.

[Optical instruments]

The optical element formed by the optical glass of the present invention can be used to manufacture optical instruments such as photographic equipment, video equipment, projection equipment, display equipment, vehicle-mounted equipment and monitoring equipment.

Example

<Optical Glass Example>

In order to further clearly illustrate and describe the technical solutions of the present invention, the following non-limiting examples are provided.

This embodiment adopts the manufacturing method of the above optical glass to obtain an optical glass having the composition shown in Tables 1 to 4. In addition, the characteristics of each glass are measured by the test method described in the present invention, and the measurement results are shown in Tables 1 to 4. In the secondary pressing anti-crystallization performance test of Tables 1 to 4, according to the aforementioned test method, the glass without opacity and without crystal particles on the surface and inside is recorded as "A", without opacity and without crystallization particles inside but with crystallization particles on the surface is recorded as "B", without opacity but with 1 to 10 crystal particles inside is recorded as "C", without opacity but with 10 to 20 crystal particles inside is recorded as "D", and opacity or dense crystallization particles inside are recorded as "×".

Table 1.

Table 2.

Table 3.

Table 4.

<Glass Preform Example>

The glasses obtained from optical glass embodiments 1 to 23 are used, for example, by grinding processing, or by molding methods such as re-hot pressing, precision stamping, etc., to make preforms of various lenses, prisms, etc., such as concave meniscus lenses, convex meniscus lenses, biconvex lenses, biconcave lenses, plano-convex lenses, and plano-concave lenses.

<Optical Element Embodiment>

The preforms obtained in the above-mentioned glass preform embodiments are annealed to reduce the deformation inside the glass and perform fine adjustments so that the optical properties such as the refractive index reach the desired values.

Next, each preform is ground and polished to produce various lenses and prisms such as concave meniscus lenses, convex meniscus lenses, biconvex lenses, biconcave lenses, plano-convex lenses, and plano-concave lenses. The surface of the obtained optical element may be coated with an anti-reflection film.

<Optical Instrument Embodiment>

The optical element obtained by the above-mentioned optical element embodiment is optically designed to form an optical component or optical assembly by using one or more optical elements. It can be used in, for example, imaging equipment, sensors, microscopes, medical technology, digital projection, communications, optical communication technology/information transmission, optics/lighting in the automotive field, lithography technology, excimer lasers, wafers, computer chips, and integrated circuits and electronic devices including such circuits and chips, or in camera equipment and devices in the vehicle field.

Claims (14)

1. Optical glass, characterized in that its components are expressed in weight percentage and contain: SiO ₂ +B ₂ O ₃ : 12 to 35%; Nb ₂ O ₅ +TiO ₂ +WO ₃ : 25～55%; BaO+SrO+CaO+MgO: 16～50%; ZnO: 0～10%; Ln ₂ O ₃ : 0～10%; ZrO ₂ : 0 ~10%, of which B ₂ O ₃ /SiO ₂ is 0.4 or less, (SiO ₂ +TiO ₂ )/(Nb ₂ O ₅ +ZrO ₂ +CaO + BaO) is 0.5 to 2.2, (ZnO+SrO+Ln ₂ O ₃ )/SiO ₂ is 0.7 or less, and the Ln ₂ O ₃ is one or more of La ₂ O ₃ , Gd ₂ O ₃ , Y ₂ O ₃ , and Yb ₂ O ₃ , the refractive index n _d of the optical glass is above 1.88, and the Abbe number v _d is below 30. 2. The optical glass according to claim 1, characterized in that its components, expressed in weight percentage, also contain: R ₂ O: 0 to 10%; and/or Al ₂ O ₃ : 0 to 5%; and /or clarification agent: 0~1%, wherein R ₂ O is one or more of Li ₂ O, Na ₂ O, K ₂ O, and the clarification agent is Sb ₂ O ₃ , SnO ₂ , SnO and CeO ₂ one or more of them. 3. The optical glass according to claim 1 or 2, characterized in that its components are expressed in weight percentage, wherein: Nb ₂ O ₅ /BaO is 0.2 to 1.2, preferably Nb ₂ O ₅ /BaO is 0.2 to 1.0 , more preferably Nb ₂ O ₅ /BaO is 0.25 to 0.9, further preferably Nb ₂ O ₅ /BaO is 0.3 to 0.8; and/or TiO ₂ /(Nb ₂ O ₅ +ZrO ₂ ) is 0.6 to 5.5, preferably TiO ₂ /(Nb ₂ O ₅ +ZrO ₂ ) is 0.7 to 4.0, more preferably TiO ₂ /(Nb ₂ O ₅ +ZrO ₂ ) is 0.8 to 3.0, further preferably TiO ₂ /(Nb ₂ O ₅ +ZrO ₂ ) is 1.0 ~2.5; and/or SiO ₂ /(Nb ₂ O ₅ +TiO ₂ ) is 0.3 ~ 1.3, preferably SiO ₂ /(Nb ₂ O ₅ +TiO ₂ ) is 0.35 ~ 1.0, more preferably SiO ₂ /(Nb ₂ O ₅ +TiO ₂ ) is 0.4 to 0.8. 4. The optical glass according to claim 1 or 2, characterized in that its components are expressed in weight percentage, wherein: B ₂ O ₃ /SiO ₂ is 0.01 to 0.3, preferably B ₂ O ₃ /SiO ₂ is 0.03 ~0.2; and/or (ZnO+SrO+Ln ₂ O ₃ )/SiO ₂ is 0.6 or less, preferably (ZnO+SrO+Ln ₂ O ₃ )/SiO ₂ is 0.5 or less, more preferably (ZnO+SrO+Ln ₂ O ₃ )/SiO ₂ is 0.3 or less; and/or (SiO ₂ +TiO ₂ )/(Nb ₂ O ₅ +ZrO ₂ +CaO + BaO) is 0.6 to 2.0, preferably (SiO ₂ +TiO ₂ )/(Nb ₂ O ₅ +ZrO ₂ +CaO+BaO) is 0.8 to 1.8, and (SiO ₂ +TiO ₂ )/(Nb ₂ O ₅ +ZrO ₂ +CaO+BaO) is more preferably 0.9 to 1.5. 5. The optical glass according to claim 1 or 2, characterized in that its components are expressed in weight percentage, wherein: SiO ₂ +B ₂ O ₃ : 15 to 30%, preferably SiO ₂ +B ₂ O ₃ : 18～25%; and/or Nb ₂ O ₅ +TiO ₂ +WO ₃ : 25～50%, preferably Nb ₂ O ₅ +TiO ₂ +WO ₃ : 30～45%; and/or BaO+SrO+CaO+ MgO: 20 to 50%, preferably BaO+SrO+CaO+MgO: 25 to 40%; and/or ZnO: 0 to 5%, preferably ZnO: 0 to 2%; and/or Ln ₂ O ₃ : 0 to 9 %, preferably Ln ₂ O ₃ : 0 to 7%; and/or ZrO ₂ : 1 to 8%, preferably ZrO ₂ : 2 to 7%; and/or R ₂ O: 0 to 6%, preferably R ₂ O: 0.5 to 5%; and/or Al ₂ O ₃ : 0 to 3%, preferably Al ₂ O ₃ : 0 to 2%; and/or clarifier: 0 to 0.5%, preferably clarifier: 0 to 0.2%, so Ln ₂ O ₃ is one or more of La ₂ O ₃ , Gd ₂ O ₃ , Y ₂ O ₃ , and Yb ₂ O ₃ , and R ₂ O is one or more of Li ₂ O, Na ₂ O, and K ₂ O One or more clarifiers are one or more of Sb ₂ O ₃ , SnO ₂ , SnO and CeO ₂ . 6. The optical glass according to claim 1 or 2, characterized in that its components are expressed in weight percentage, wherein: SiO ₂ : 12 to 30%, preferably SiO ₂ : 15 to 25%, more preferably SiO ₂ : 16 to 23%; and/or Nb ₂ O ₅ : 6 to 20%, preferably Nb ₂ O ₅ : 7 to 18%, more preferably Nb ₂ O ₅ : 8 to 17%; and/or TiO ₂ : 15 to 35 %, preferably TiO ₂ : 18 to 32%, more preferably TiO ₂ : 20 to 30%; and/or BaO: 15 to 35%, preferably BaO: 18 to 32%, more preferably BaO: 20 to 30%; and/or Or CaO: 0 to 12%, preferably CaO: 1 to 9%, more preferably CaO: 3 to 7%; and/or B ₂ O ₃ : 0 to 6%, preferably B ₂ O ₃ : 0.1 to 5%, more preferably Preferably B ₂ O ₃ : 0.5-4%; and/or WO ₃ : 0-10%, preferably WO ₃ : 0-5%, more preferably WO ₃ : 0-2%; and/or SrO: 0-8% , preferably SrO: 0 to 4%, more preferably SrO: 0 to 2%; and/or MgO: 0 to 8%, preferably MgO: 0 to 4%, more preferably MgO: 0 to 2%; and/or Li ₂ O: 0 to 3%, preferably Li ₂ O: 0 to 2%, more preferably Li ₂ O: 0 to 1%; and/or Na ₂ O: 0 to 8%, preferably Na ₂ O: 0 to 6%, More preferably, Na ₂ O: 0.5 to 5%; and/or K ₂ O: 0 to 5%, preferably K ₂ O: 0 to 3%, and more preferably, K ₂ O: 0 to 2%. 7. The optical glass according to claim 1 or 2, characterized in that its components are expressed in weight percentage, wherein: Na ₂ O/CaO is 5.0 or less, preferably Na ₂ O/CaO is 0.01 to 3.0, more preferably Na ₂ O/CaO is 0.05 to 2.5; and/or Li ₂ O/B ₂ O ₃ is 0.5 or less, preferably Li ₂ O/B ₂ O ₃ is 0.3 or less, and more preferably Li ₂ O/B ₂ O ₃ is 0.1 In the following, it is further preferred that Li ₂ O/B ₂ O ₃ is 0.05 or less; and/or 10×Li ₂ O/Nb ₂ O ₅ is 0.7 or less, preferably 10×Li ₂ O/Nb ₂ O ₅ is 0.4 or less, and more preferably 10×Li ₂ O/Nb ₂ O ₅ is 0.2 or less. 8. The optical glass according to claim 1 or 2, characterized in that its components, expressed in weight percentage, also contain: no more than 4% P ₂ O ₅ , preferably no more than 2% P ₂ O ₅ , More preferably no more than 1% _P2O5 ; and/or no more than ₄ % _Bi2O3 , preferably no more than _{2 % Bi2O3} , more preferably no more than 1 _{% Bi2O3} ; and/or or no more than 4% Ta ₂ O ₅ , preferably no more than 2% Ta ₂ O ₅ , more preferably no more than 1% Ta ₂ O ₅ ; and/or no more than 4% TeO ₂ , preferably no more than 2% TeO ₂ , more preferably no more than 1% TeO ₂ ; and/or no more than 4% Ga ₂ O ₃ , preferably no more than 2% Ga ₂ O ₃ , more preferably no more than 1% Ga ₂ O ₃ . 9. The optical glass according to claim 1 or 2, characterized in that the optical glass does not contain ZnO; and/or does not contain Li ₂ O; and/or does not contain SrO; and/or does not contain MgO; and /or does not contain P ₂ 0 ₅ ; and/or does not contain Bi ₂ O ₃ ; and/or does not contain Ta ₂ O ₅ ; and/or does not contain TeO ₂ ; and/or does not contain WO ₃ ; and/or does not contain Gd ₂ O ₃ ; and/or does not contain Y ₂ O ₃ . 10. The optical glass according to claim 1 or 2, characterized in that the refractive index n _d of the optical glass is 1.89 to 1.95, preferably 1.90 to 1.94, more preferably 1.91 to 1.935; the Abbe number v _d It is 20-27, More preferably, it is 21-26, Even more preferably, it is 22-25. 11. The optical glass according to claim 1 or 2, characterized in that, λ ₇₀ of the optical glass is 460 nm or less, preferably λ ₇₀ is 450 nm or less, more preferably λ ₇₀ is 440 nm or less; and/or λ ₅ is 400 nm or less, preferably λ ₅ is 390 nm or less, more preferably λ ₅ is 380 nm or less; and/or the acid resistance stability D _A is category 2 or above, preferably category 1; and/or the water resistance stability D _W is category 2 or above. , preferably Category 1; and/or the upper limit temperature of crystallization is 1180°C or lower, preferably 1160°C or lower, more preferably 1140°C or lower; and/or Young's modulus E is 9500×10 ⁷ /Pa or higher, preferably 10000×10 ⁷ /Pa or more, more preferably 10500×10 ⁷ /Pa or more; and/or the thermal expansion coefficient α _{from 100 to 300°C} is 110×10 ^-7 /K or less, preferably 105×10 ^-7 /K or less, More preferably, it is 100×10 ^-7 /K or less; the density ρ is 4.30g/cm ³ or less, preferably 4.20g/cm ³ or less, more preferably 4.10g/cm ³ or less; and/or the abrasion degree F _A is 150 Above, it is preferably 180 or more, more preferably 200 to 300; and/or the relative partial dispersion P _g,F is 0.6000 to 0.6400, preferably 0.6100 to 0.6300, more preferably 0.6150 to 0.6250. 12. Glass preform, characterized in that it is made of the optical glass according to any one of claims 1 to 11. 13. Optical element, characterized in that it is made of the optical glass according to any one of claims 1 to 11, or made of the glass preform according to claim 12. 14. An optical instrument, characterized in that it contains the optical glass according to any one of claims 1 to 11, or the optical element according to claim 13.