Optical glass, method for producing the same, and use thereof

Abstract

The present application provides a kind of middle refraction optical glass and its preparation method and use.The optical glass includes the following components in cation mole percentage:Si 4+ :4-16%;B 3+ :40-59%;La 3+ :8-16%;Y 3+ :2-6.5%;Ca 2+ :5-13%;Zn 2+ :3-9%;Zr 4+ :0.01-0.5%;Li + :1.4-4%;Na + :7-12%;K + :0-6%;Al 3+ :0-5%;Mg 2+ :0-5%;Sr 2+ :0-5%;Ba 2+ :0-5%;And Sb 3+ :0-0.05%;The refractive index of the optical glass is 1.65-1.75, and the Abbe number is 50-60.The transition temperature of the optical glass of the present application is low, suitable for molding, and the chemical stability is excellent, which can meet the needs of modern new optoelectronic products.

Description

Technical Field

[0001] This invention relates to a medium-refractive optical glass, its preparation method and uses, and belongs to the field of optical glass. Background Technology

[0002] In recent years, the digitization and high-definition of optical instruments have developed rapidly. In various optical instrument fields such as digital photography equipment, video equipment, projection equipment, projectors, and projection televisions, there is an urgent need to reduce the number of optical components such as lenses and prisms used in optical systems, so as to make the overall optical system lighter and smaller.

[0003] In the manufacture of optical components, the market demand for medium-refractive optical glasses, especially those with a refractive index of 1.65–1.75 and an Abbe number of 50–60, which can correct chromatic aberration and enable miniaturization of optical systems, is increasing. Since optical glasses are widely used in automotive, surveillance, and security fields, they are exposed to complex and even extreme external environments for extended periods. This necessitates excellent weather resistance to extend the lifespan of optical glasses.

[0004] Currently, the mainstream method for manufacturing optical glass into optical components is precision molding (including direct molding and secondary molding). Lenses manufactured using precision molding technology usually do not require further grinding and polishing, thereby reducing raw material consumption, lowering labor and material costs, and reducing environmental pollution. This technology can reduce costs and mass-produce optical components.

[0005] In precision molding, to replicate a high-precision mold surface onto the finished glass product, the glass preform needs to be molded under pressure at high temperatures. Even when the mold is in a protective gas environment, its surface is easily oxidized and corroded under these high temperatures and pressures. To extend the mold's lifespan and suppress damage from the high-temperature environment, the molding temperature must be reduced. Therefore, the transition temperature (Tg) of the glass material used for molding needs to be as low as possible.

[0006] The optical glasses disclosed in patent applications CN107879619A, CN105948483A, CN105906198A all contain F components. During the melting process, the volatilization of F components can lead to environmental pollution, unstable optical constants, and easily cause defects such as streaks in the glass. On the other hand, during the precision molding process, it can also cause the surface of the optical glass to fog up easily.

[0007] The optical glass disclosed in patent applications CN109328182A and CN1950306A contains a high content of Ba. 2+ Ba 2+ Ba has a very high relative molecular mass and a high content.2+ This will result in the glass having an excessively high specific gravity.

[0008] The optical glasses disclosed in patent applications CN100374386C and CN107148404A all contain P. 5+ P 5+ It readily corrodes containers made of precious metals such as platinum, especially phosphate glass containing alkali metals, which is even more corrosive. Furthermore, P... 5+ It is prone to volatilization at high temperatures, which affects the optical stability of the glass.

[0009] The optical glasses disclosed in patent applications CN103214182A and CN1903762A all contain Gd. 3+ The optical glasses disclosed in patent applications CN1099388C and CN114163122A all contain Nb. 5+ Gd 3+ 、Nb 5+ The high price significantly increases costs, which is detrimental to market competition.

[0010] The optical glasses disclosed in patent applications CN109071314A and CN101863617A all contain Ti. 4+ , and Ti 4+ This will cause the color of the glass to deteriorate significantly. Summary of the Invention

[0011] The problem the invention aims to solve

[0012] In view of the technical problems disclosed in the prior art, the present invention first provides a medium-refractive optical glass. The optical glass has a refractive index of 1.65–1.75, a low transition temperature, and excellent resistance to devitrification, chemical stability, and colorability. It is suitable for precision molding and easy to mass-produce.

[0013] The present invention also provides a method for preparing optical glass, which is simple and easy to implement, uses readily available raw materials, and is suitable for mass production.

[0014] The present invention also provides an optical element or optical preform.

[0015] Solution for solving the problem

[0016] This invention provides an optical glass comprising the following components in molar percentage of cations:

[0017] Si 4+ : 4-16%;

[0018] B 3+ 40-59%;

[0019] La3+ 8-16%;

[0020] Y 3+ 2-6.5%;

[0021] Ca 2+ 5-13%;

[0022] Zn 2+ 3-9%;

[0023] Zr 4+ : 0.01~0.5%;

[0024] Li + 1.4%–4%;

[0025] Na + 7-12%;

[0026] K + 0-6%;

[0027] Al 3+ 0-5%;

[0028] Mg 2+ 0-5%;

[0029] Sr 2+ 0-5%;

[0030] Ba 2+ 0-5%; and

[0031] Sb 3+ : 0~0.05%;

[0032] The optical glass has a refractive index of 1.65 to 1.75 and an Abbe number of 50 to 60.

[0033] According to the optical glass of the present invention, the optical glass comprises the following components, in molar percentage of cations:

[0034] Si 4+ 6-14%;

[0035] B 3+ 43-57%;

[0036] La 3+ 9-15%;

[0037] Y 3+ 2.5-6%;

[0038] Ca 2+ 6-12%;

[0039] Zn 2+4-8%;

[0040] Zr 4+ : 0.05~0.45%;

[0041] Li + : 1.7–3.8%;

[0042] Na + 7.5%–11.5%;

[0043] K + 0-3%;

[0044] Al 3+ 0-3%;

[0045] Mg 2+ 0-2%;

[0046] Sr 2+ 0-2%;

[0047] Ba 2+ 0-2%; and

[0048] Sb 3+ : 0~0.03%.

[0049] According to the optical glass of the present invention, the optical glass comprises the following components, in molar percentage of cations:

[0050] Si 4+ 7-13%;

[0051] B 3+ 45-55%;

[0052] La 3+ 10-14%;

[0053] Y 3+ 3-5.5%;

[0054] Ca 2+ 7-11%;

[0055] Zn 2+ 5-7%;

[0056] Zr 4+ : 0.1~0.4%;

[0057] Li + 2-3.5%;

[0058] Na + 8-11%;

[0059] K + 0-1%;

[0060] Al 3+ 0-1%;

[0061] Mg 2+ 0-2%;

[0062] Sr 2+ 0-2%;

[0063] Ba 2+ 0-2%; and

[0064] Sb 3+ : 0~0.01%.

[0065] According to the optical glass of the present invention, the optical glass does not contain F. - P 5+ Ta 5+ Gd 3+ 、Nb 5+ 、Ge 4+ Te 4+ and Ti 4+ One or more combinations of the above.

[0066] The optical glass according to the present invention, wherein Si 4+ mole percentage of B 3+ The ratio of the molar percentage of Si 4+ / B 3+ It ranges from 0.05 to 0.4;

[0067] La 3+ mole percentage and Y 3+ The sum of the mole percentages of La 3+ +Y 3+ It ranges from 12% to 21.5%.

[0068] According to the optical glass of the present invention, wherein B 3+ molar percentage with La 3+ mole percentage and Y 3+ The ratio of the sum of the mole percentages B 3+ / (La 3+ +Y 3+ The value is 2 to 4.5.

[0069] Zn 2+ molar percentage with La 3+ mole percentage and Y 3+ The ratio of the sum of the mole percentages of Zn 2+ / (La 3+ +Y 3 + The value ranges from 0.2 to 0.7.

[0070] According to the optical glass of the present invention, wherein,

[0071] The density ρ of the optical glass is 3.75 g / cm³. 3 the following;

[0072] The tinting degree λ of the optical glass 80 In / λ5, λ 80 The wavelength is below 360nm, and λ5 is below 275nm.

[0073] The hardness HK of the optical glass is 630×10. 7 Pa or above.

[0074] According to the optical glass of the present invention, wherein,

[0075] The optical glass has a water resistance stability of level 1;

[0076] The transition temperature Tg of the optical glass is below 545℃;

[0077] The sag temperature Ts of the optical glass is below 585°C;

[0078] The crystallization temperature Lt of the optical glass is below 1050℃;

[0079] The degree of bubble formation in the optical glass is 0 to 1.

[0080] The present invention also provides a method for preparing optical glass according to the present invention, wherein the method includes weighing and mixing the raw material components of the optical glass in proportion, melting them, and then pouring or casting them into a molding die, or directly pressing them into shape.

[0081] Furthermore, the present invention also provides an optical element or optical preform, wherein the optical glass described in the present invention is included.

[0082] The effects of the invention

[0083] The optical glass of this invention has a refractive index of 1.65 to 1.75, a low transition temperature Tg and sag temperature Ts, and excellent water resistance and tinting strength. Therefore, the optical glass of this invention is a medium-refractive-index optical glass with a low transition temperature suitable for molding and excellent chemical stability, which can meet the needs of modern new optoelectronic products.

[0084] The method for preparing the optical glass of the present invention is simple and easy to implement, the raw materials are readily available, and it is suitable for mass production. Detailed Implementation

[0085] Various exemplary embodiments, features, and aspects of the present invention will be described in detail below. The term "exemplary" as used herein means "serving as an example, embodiment, or illustration." Any embodiment described herein as "exemplary" is not necessarily to be construed as superior to or better than other embodiments.

[0086] Furthermore, to better illustrate the present invention, numerous specific details are set forth in the following detailed embodiments. Those skilled in the art should understand that the present invention can be practiced without certain specific details. In other instances, methods, means, apparatus, and steps well known to those skilled in the art have not been described in detail in order to highlight the spirit of the present invention.

[0087] Unless otherwise stated, all units used in this specification are international standard units, and all numerical values ​​and ranges appearing in this invention should be understood to include systematic errors that are unavoidable in industrial production.

[0088] In this specification, the word "may" has two meanings: to perform a certain process and not to perform a certain process.

[0089] In this specification, references to "some specific / preferred embodiments," "other specific / preferred embodiments," "implementation," etc., refer to specific elements (e.g., features, structures, properties, and / or characteristics) related to that embodiment, which are included in at least one of the embodiments described herein and may or may not be present in other embodiments. Furthermore, it should be understood that these elements may be combined in any suitable manner in various embodiments.

[0090] In this specification, the range of values ​​referred to as "value A to value B" refers to the range including the endpoint values ​​A and B.

[0091] The present invention first provides an optical glass comprising the following components in molar percentage of cations:

[0092] Si 4+ : 4-16%;

[0093] B 3+ 40-59%;

[0094] La 3+ 8-16%;

[0095] Y 3+ 2-6.5%;

[0096] Ca 2+ 5-13%;

[0097] Zn 2+ 3-9%;

[0098] Zr 4+ : 0.01~0.5%;

[0099] Li + 1.4%–4%;

[0100] Na + 7-12%;

[0101] K + 0-6%;

[0102] Al 3+ 0-5%;

[0103] Mg 2+ 0-5%;

[0104] Sr 2+ 0-5%;

[0105] Ba 2+ 0-5%; and

[0106] Sb 3+ : 0~0.05%;

[0107] The refractive index (n) of the optical glass d The value is 1.65–1.75, and the Abbe number (υ) is... d The value is 50-60.

[0108] The composition of the optical glass of the present invention will be described in detail below. Unless otherwise specified, the content of each glass component and the total content are expressed as a cation molar percentage. In addition, in the following description, "below or above a specified value" also includes the specified value.

[0109] B 3+ In this invention, the network-forming component improves the thermal stability and meltability of the glass, thereby enabling the production of glass without any molten residue from the glass raw material. By molar percentage, this invention utilizes a component containing more than 40% B. 3+ To achieve the above effects, B is preferred. 3+ The content is 43% or more, preferably B. 3+ The content is over 45%. But when B 3+ When the content of B is too high, the refractive index of the glass decreases and its chemical stability deteriorates. Therefore, in this invention, B, by molar percentage, 3+ The maximum content of [the substance] is 59%, preferably 57%, and even more preferably 55%.

[0110] Si 4+ It is also a glass-forming material, while Si 4+What forms within the glass is a dense and robust three-dimensional network of silicon-oxygen tetrahedra, which can enhance B. 3+ The resulting loose, chain-like layered network increases the viscosity of molten glass, promotes stable glass formation, and improves mechanical properties. (In molar percentage, by adding Si...) 4+ By controlling the introduction amount of Si below 16%, the partial dispersion ratio of the glass can be reduced, the specific gravity of the glass can be decreased, and the rise in the glass transition temperature can be suppressed; furthermore, when Si 4+ Excessive Si content increases the difficulty of glass melting and is detrimental to lowering the glass transition temperature. 4+ If the Si content is too low, the glass crystallization performance will be poor. Therefore, in this invention, the Si content is low by molar percentage. 4+ The content is 4-16%, preferably 6-14%, and more preferably 7-13%.

[0111] In some specific embodiments of the present invention, by making Si 4+ mole percentage of B 3+ The ratio of the molar percentage of Si 4+ / B 3+ A Si concentration of 0.05–0.4 can give the glass a suitable high-temperature viscosity, which is beneficial for glass homogenization and clarification, while also improving the glass's resistance to crystallization and facilitating glass forming. Furthermore, Si… 4+ / B 3+ Preferably, it is 0.1 to 0.35, more preferably 0.15 to 0.3.

[0112] La 3+ It is a high-refractive-index, low-dispersion component that can increase the refractive index and regulate dispersion in glass, while reducing its high-temperature viscosity. In this invention, La is present in [amount] molar percentage. 3+ The content is above 8%, with La being the preferred choice. 3+ The content is 9% or more, preferably La 3+ The content is above 10%. On the other hand, in molar percentage, by using La 3+ The content of La is limited to below 16%, which can reduce glass devitrification by improving glass stability and suppress the rise of refractive index temperature coefficient and density beyond design requirements; therefore, in molar percentage, La 3+ The content is 16% or less, preferably 15% or less, and more preferably 14% or less.

[0113] Y 3+ This invention improves the refractive index of glass by simultaneously containing Y. 3+ with La 3+In combination, while maintaining high refractive index and low dispersion, the glass's meltability and devitrification resistance are improved, and its density is reduced. By molar percentage, this invention utilizes more than 2% Y... 3+ To achieve the above-mentioned effects, it is preferable to contain more than 2.5% Y. 3+ More preferably, it contains 3% or more Y 3+ In mole percentage, if Y 3+ When the content of Y exceeds 6.5%, the stability and devitrification resistance of the glass decrease, and the transition temperature increases. Therefore, Y 3+ The maximum content is 6.5%, preferably 6%, and more preferably 5.5%.

[0114] La 3+ Y 3+ Rare earth oxides are components that improve the refractive index and chemical stability of glass. In some specific embodiments, the present invention can be achieved by introducing more than 12% La, by molar percentage. 3+ mole percentage and Y 3+ The sum of the mole percentages of La 3+ +Y 3+ To achieve the above effect; however, if La 3+ +Y 3+ Excessive heat reduces the thermal stability and devitrification resistance of the glass. Therefore, in molar percentage terms, La... 3+ +Y 3+ The content is 12-21.5%, preferably 13-20%, and more preferably 14-19%.

[0115] In some specific embodiments of the present invention, the inventors discovered that by controlling B 3+ molar percentage with La 3+ mole percentage and Y 3+ The ratio of the sum of the mole percentages B 3+ / (La 3+ +Y 3+ A viscosity of 2-4.5 can improve the stability and anti-crystallization properties of glass, and give it a suitable viscosity, which is beneficial for glass forming. Furthermore, B... 3+ / (La 3+ +Y 3 + The preferred value is 2.2 to 4.3, and more preferably 2.5 to 4.

[0116] Zr 4+ Zr is a high-refractive-index, low-dispersion component that can increase the refractive index and regulate dispersion in glass, thereby improving its resistance to crystallization. 4+Excessive Zr content increases the difficulty of glass melting, raises the melting temperature, and further leads to the formation of inclusions and a decrease in light transmittance within the glass. Therefore, in molar percentage terms, Zr... 4+ The content is 0.01-0.5%, preferably 0.05-0.45%, and more preferably 0.1-0.4%.

[0117] Zn 2+ In the optical glass of this invention, the refractive index and dispersion of the glass can be adjusted, the transition temperature can be reduced, the anti-crystallization properties of the glass can be improved, and the stability of the glass can be enhanced. Simultaneously, Zn... 2+ It can also reduce the high-temperature viscosity of glass, allowing it to be melted at lower temperatures, thereby improving the light transmittance of the glass. In this invention, by molar percentage, the content of Zn is more than 3%. 2+ To achieve the above effects, Zn is preferred. 2+ The content is 4% or more, preferably Zn. 2+ The content is above 5%. On the other hand, if Zn 2+ Excessive Zn content can easily lead to the formation of platinum particles during melting, resulting in poor colorability, increased forming difficulty, and decreased resistance to crystallization in the glass. Therefore, on a molar percentage basis, Zn... 2+ The content is limited to 9% or less, preferably 8% or less, and more preferably 7% or less.

[0118] In some specific embodiments of the present invention, if Zn 2+ molar percentage with La 3+ mole percentage and Y 3 + The ratio of the sum of the mole percentages of Zn 2+ / (La 3+ +Y 3+ If the Zn content is too low, the glass will have more bubbles and the bubble density will be worse. 2+ / (La 3+ +Y 3+ If the concentration of Zn is too high, the viscosity of the glass decreases, and its formability deteriorates. Therefore, on a molar percentage basis, Zn... 2+ / (La 3+ +Y 3+ The concentration of Zn can be 0.2 to 0.7, preferably 0.25 to 0.65. Furthermore, in some embodiments of the present invention, the molar percentage of Zn is controlled by... 2+ / (La 3+ +Y 3+ The coefficient of thermal expansion of glass is 0.3 to 0.6, and the coefficient of thermal expansion of glass can be further optimized to improve the processing yield and thermal shock resistance of glass components.

[0119] Li + This can lower the glass transition temperature, but if Li+ Excessive Li content is detrimental to the chemical stability and thermal expansion coefficient of the glass. + If the content is too low, it will not be able to play its corresponding role. Therefore, in this invention, the Li content is low, measured in molar percentage. + The content is 1.4-4%, preferably 1.7-3.8%, and more preferably 2-3.5%.

[0120] Na + As a glass network outer body, it is an effective component for lowering the glass transition temperature Tg, relaxation temperature Ts, and improving glass melt properties. If Na... + If the sodium content is too high, the refractive index of the glass will decrease significantly, and its chemical stability and devitrification resistance will deteriorate drastically. + If the content is too low, it will not have the desired effect. Therefore, in molar percentage terms, Na... + The content is 7-12%, preferably 7.5-11.5%, and more preferably 8-11%.

[0121] K + It improves the thermal stability and melt flow properties of glass, but if its content is too high, the glass's devitrification resistance decreases and its chemical stability deteriorates. Therefore, in this invention, K, by molar percentage, + The content is 6% or less, preferably 0-3%, and more preferably 0-1%.

[0122] Ca 2+ It is an essential component for effectively reducing devitrification temperature, conversion temperature, and specific gravity. In this invention, by molar percentage, it contains more than 5% Ca. 2+ To achieve the above effects, Ca is preferred. 2+ The content is 6% or more, preferably Ca 2+ The content of Ca is above 7%; however, if the content is too high, it can easily lead to a deterioration of devitrification resistance. Therefore, in molar percentage, Ca 2+ The content is limited to 13% or less, preferably 12% or less, and more preferably 11% or less.

[0123] Sr 2+ It is an arbitrary component used to lower the devitrification temperature and adjust the refractive index, but if its content is too high, it can easily lead to a deterioration of devitrification resistance. Therefore, in molar percentage, Sr 2+ The content is limited to 0-5%, preferably 0-2%.

[0124] Mg 2+ It is any component that lowers the melting temperature, but if its content is too high, it will worsen the stability relative to devitrification, easily leading to an increased tendency for phase separation, and at the same time, the cost of glass will rise rapidly. Therefore, in molar percentage, Mg 2+The content is limited to 0-5%, preferably 0-2%.

[0125] Ba 2+ Ba is an effective component for reducing devitrification temperature and adjusting optical constants, but excessive amounts can easily lead to deterioration of devitrification resistance. Therefore, in molar percentage, Ba... 2+ The content is limited to 0-5%, preferably 0-2%.

[0126] Al 3+ It can improve the stability and chemical stability of glass formation, but when its content is too high, it tends to worsen glass meltability and reduce devitrification resistance. Therefore, the Al content of this invention... 3+ The content is 5% or less, preferably 3% or less, and more preferably 1% or less.

[0127] On a molar percentage basis, by introducing 0–0.05% Sb 3+ As a clarifying agent, it can improve the clarification effect of glass. It is preferable to introduce 0 to 0.03% of the clarifying agent, and even more preferably 0 to 0.01% of the clarifying agent.

[0128] In the optical 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 in small amounts, either alone or in combination, the glass will be colored and absorb at specific wavelengths in the visible light region, thereby reducing the visible light transmittance of the present invention. Therefore, it is preferable that the optical glass, especially for optical glass where transmittance in the visible light region is required, does not contain these oxides.

[0129] Elements such as Th, Cd, Tl, Os, Be, and Se have been increasingly subject to controlled use in recent years due to their status as hazardous chemical substances. Environmental protection measures are essential not only in the glass manufacturing process but also in its processing and post-product disposal. Therefore, given the importance of environmental impact, it is preferable to exclude them, except where their inclusion is unavoidable. As a result, the optical glass becomes virtually free of pollutants. Therefore, the optical glass of this invention can be manufactured, processed, and disposed of even without special environmental countermeasures.

[0130] To achieve environmental friendliness, the optical glass of this invention does not contain As or Pb. Although As has the effect of eliminating bubbles and preventing glass discoloration, the addition of As will increase the corrosion of platinum in the furnace, especially the platinum furnace, leading to more platinum ions entering the glass and adversely affecting the service life of the platinum furnace. Pb can significantly improve the high refractive index and high dispersion performance of glass, but both Pb and As are substances that cause environmental pollution.

[0131] In some specific embodiments, the optical glass preferably does not contain F.- P 5+ Ta 5+ Gd 3+ 、Nb 5+ 、Ge 4+ Te 4+ and Ti 4+ One or more combinations of F. - During the melting process, the volatilization of sulfur (F) can lead to environmental pollution, unstable optical constants, and defects such as streaks in the glass. Furthermore, during precision molding, it can cause fogging on the surface of the optical glass. Therefore, this invention preferably does not introduce sulfur. - P 5+ It readily corrodes containers made of precious metals such as platinum, especially phosphate glass containing alkali metals, which is even more corrosive; and P 5+ P is easily volatilized at high temperatures, affecting the optical stability of the glass. Therefore, this invention preferably does not introduce P. 5+ Ta 5+ Its price is very high, and from a practical and cost-effective perspective, its usage should be minimized. Therefore, this invention preferably does not introduce Ta. 5+ This reduces the material cost of glass, thereby lowering the manufacturing cost of optical glass. Furthermore, Gd... 3+ 、Nb 5+ 、Ge 4+ And Te 4+ The price is also very high, so it is preferred not to be included in this invention. Furthermore, Ti... 4+ This would lead to a significant deterioration in the colorability of the glass; therefore, it is preferable not to introduce Ti in this invention. 4+ .

[0132] Furthermore, the anion of the optical glass of the present invention is preferably O. 2- .

[0133] The terms "not introduced," "not containing," and "0%" used herein mean that the compound, molecule, or element was not intentionally added to the optical glass of this invention as a raw material; however, as raw materials and / or equipment used in the production of optical glass, there may be certain unintentionally added impurities or components that may be present in small or trace amounts in the final optical glass, and such cases are also within the scope of protection of this patent.

[0134] In this invention, the density ρ of the optical glass is 3.75 g / cm³. 3 The following; shading degree λ 80 In / λ5, λ 80 The wavelength is below 360nm, and λ5 is below 275nm; the hardness HK is 630×10. 7 Pa or higher. The water resistance stability D of the optical glass. WGrade 1, moisture resistance stability R C Grade 1, alkali resistance stability R OH (S) is level 1, and the washability stability RP(S) is level 2 or above; the average linear expansion coefficient α of the optical glass is... -50～80℃ 66×10 -7 / K~82×10 -7 / K, α 100～300℃ 80×10 -7 / K~96×10 -7 / K; the optical glass has a transition temperature Tg below 545℃, a sag temperature Ts below 585℃, and a crystallization temperature Lt below 1050℃; the optical glass has a bubble degree grade of 0 to 1.

[0135] The present invention also provides an optical preform and an optical element, formed from the aforementioned optical glass using methods well known to those skilled in the art. Since the optical glass has a medium refractive index, the optical element also has a medium refractive index and can be applied to devices such as digital cameras, digital video cameras, and camera phones.

[0136] Furthermore, the present invention also provides a method for preparing optical glass, which includes weighing and mixing the raw materials of each component in proportion, melting them, and then pouring or casting them into a molding die, or directly pressing them into shape.

[0137] Specifically, the raw materials of each component of optical glass (such as oxides, hydroxides, carbonates, nitrates, etc.) are mixed and placed in a melting furnace (such as a platinum crucible, alumina crucible, etc.) at 1130-1360°C. After melting, smelting, clarifying, stirring and homogenizing, a homogeneous molten glass without bubbles and undissolved substances is obtained. This molten glass is then cast in a mold and annealed, or directly pressed into shape.

[0138] Example

[0139] The embodiments of the present invention will be described in detail below with reference to examples. However, those skilled in the art will understand that the following examples are for illustrative purposes only and should not be considered as limiting the scope of the invention. Unless otherwise specified in the examples, conventional conditions or conditions recommended by the manufacturer are followed. Reagents or instruments whose manufacturers are not specified are all commercially available conventional products.

[0140] To further understand the technical solution of the present invention, embodiments of the optical glass of the present invention will now be described. It should be noted that these embodiments do not limit the scope of protection of the present invention.

[0141] The optical glasses shown in Tables 1 to 6 (Examples 1 to 32, Comparative Examples A to B) were obtained by weighing and mixing common raw materials (such as lanthanum oxide, yttrium oxide, silicon oxide, calcium carbonate, calcium nitrate, aluminum hydroxide, boric acid, zirconium oxide, zinc oxide, lithium carbonate, sodium carbonate, potassium carbonate, lithium sulfate, magnesium carbonate, barium carbonate, strontium carbonate, and antimony oxide) according to the ratios shown in Tables 1 to 6. The mixed raw materials were placed in a platinum crucible of a melting device and melted at 1250°C. After homogenization, the mixture was clarified at 1360°C to allow the bubbles to rise fully. The temperature of the molten glass was then lowered to about 1130°C, and the glass was poured or poured through a cylindrical pipe into a forming mold. After annealing and cooling, the optical glass of the present invention was obtained.

[0142] Performance testing

[0143] 1. Refractive index n d Abbe number υ d

[0144] The refractive index n of the obtained optical glass was determined according to the test method of GB / T7962.1-2010. d Abbe number υ d The determination of n listed in the table d υ d The data is for annealing at -30℃.

[0145] 2. Knoop Hardness (HK)

[0146] Knoop hardness was measured according to the test method specified in ISO 9385.

[0147] 3. The average linear expansion coefficient α of glass -50～80℃ α 100～300℃

[0148] The measurement shall be performed according to the method specified in GB / T 7962.16.

[0149] 4. Transition temperature Tg and relaxation temperature Ts

[0150] The measurement shall be performed according to the method specified in GB / T 7962.16.

[0151] 5. Density ρ

[0152] The density of the obtained optical glass was determined according to the test method of GB / T7962.20-2010.

[0153] 6. Shading degree λ 80 / λ5

[0154] The short-wavelength transmission spectral characteristics of optical glass are expressed using colorimetric λ. 80 / λ5 represents this. Where λ... 80λ5 refers to the wavelength corresponding to a glass transmittance of 80%, while λ5 refers to the wavelength corresponding to a glass transmittance of 5%.

[0155] 7. Water resistance stability D W

[0156] The chemical stability and water resistance of the obtained optical glass were tested according to the test method of JB / T10576-2006. W Run the test.

[0157] 8. Moisture resistance stability R C

[0158] Under conditions of 50℃ and 85% relative humidity, the stability of optical glass against humid atmospheres is divided into three levels based on the time required for hydrolysis spots to form on the polished glass surface, as shown in Table A.

[0159] Table A

[0160] level 1 2 3 Time (h) >20 5～20 <5

[0161] 9. Alkali resistance R OH (S), Washability stability RP(S)

[0162] A 40mm × 40mm × 5mm sample, polished on all six sides, was immersed in a 0.01mol / L sodium hydroxide aqueous solution at a constant temperature of 50℃ ± 3℃ for 15 hours with thorough stirring. The leaching mass per unit area was calculated as mg / (cm²). 2 •15h), to improve the alkali resistance stability R of optical glass OH (S) is divided into five levels, as shown in Table B.

[0163] Table B

[0164]

[0165] A 35mm × 35mm × 8mm sample, polished on all six sides, was immersed in Na₅P₃O₂ at a constant temperature of 50℃ ± 3℃ and a concentration of 0.01mol / L with thorough stirring. 10 In aqueous solution for 1 hour. Based on the average leaching mass per unit area, the unit is mg / (cm²). 2 The washability stability RP(S) of optical glass is divided into five levels, as shown in Table C.

[0166] Table C

[0167]

[0168] 10. Bubble density

[0169] The bubble content of the obtained optical glass was tested according to GB / T 7962.8-2010 Test Methods for Colorless Optical Glass Part 8: Bubble Content.

[0170] 11. Upper limit temperature for crystallization Lt

[0171] The crystallization properties of glass were determined using the gradient furnace method. The glass was made into a sample of 180×10×10mm, the side was polished, and it was placed in a furnace with a temperature gradient (10℃ / cm) and heated to the highest temperature zone of 1200℃. After holding at this temperature for 4 hours, it was taken out and allowed to cool naturally to room temperature. The crystallization of the glass was observed under a microscope. The highest temperature at which crystals appeared in the glass was the upper limit temperature for crystallization of the glass.

[0172] The refractive index n of the optical glass prepared in Examples 1-32 d Abbe number υ d Hardness HK, average linear expansion coefficient, transformation temperature Tg, sag temperature Ts, density ρ, and chromaticity λ 80 And λ5, water resistance stability D W Moisture resistance and stability R C Alkali resistance stability R OH The washing resistance stability RP(S), crystallization upper limit temperature Lt, and bubble degree are listed in Tables 1-5; the data obtained by measuring comparative example AB are listed in Table 6.

[0173] Table 1: Glass composition and performance parameters of Examples 1-7

[0174]

[0175] Table 2: Glass composition and performance parameters of Examples 8-14

[0176]

[0177] Table 3: Glass composition and performance parameters of Examples 15-21

[0178]

[0179] Table 4: Glass composition and performance parameters of Examples 22-28

[0180]

[0181] Table 5: Glass composition and performance parameters of Examples 29-32

[0182]

[0183] Table 6: Glass composition and performance parameters of comparative examples A and B

[0184]

[0185] As can be seen from the above embodiments, the refractive index (n) of the optical glass of the present invention is... d The value is 1.65–1.75, and the Abbe number (υ) is... d The content of the metal content is 50-60, and the density ρ is 3.75 g / cm³. 3 The following is the hardness (HK) of optical glass: 630 × 10⁻⁶. 7 Above Pa, water resistance stability D W Grade 1, moisture resistance Rc is Grade 1, washing resistance RP(S) is Grade 2, alkali resistance R OH (S) is level 1; the tinting degree λ of the optical glass 80 In / λ5, λ 80 The wavelength is below 360 nm, and λ5 is below 275 nm. Additionally, the linear expansion coefficient α of optical glass... -50～80℃ 66×10 -7 / K~82×10 -7 / K, α 100～300℃ 80×10 -7 / K~96×10 -7 / K; The optical glass has a transition temperature Tg below 545℃, a sag temperature Ts below 585℃, and a crystallization temperature Lt below 1050℃; The optical glass has a bubble degree of 0 to 1, making it suitable for widespread use in digital cameras, digital camcorders, and camera phones.

[0186] As can be seen from Table 6, Comparative Example A contains more than 5% Ti. 4+ While chemical stability has improved, colorimetric properties have deteriorated, failing to meet the high-resolution requirements of advanced optical systems and significantly impacting usability. Comparative Example B contains 10% Ba. 2+ The increased weight does not meet the lightweight requirements of high-end optical systems, and the chemical stability deteriorates.

[0187] It should be noted that although the technical solution of the present invention has been described with specific examples, those skilled in the art will understand that the present invention should not be limited thereto.

[0188] The various embodiments of the present invention have been described above. These descriptions are exemplary and not exhaustive, nor are they limited to the disclosed embodiments. Many modifications and variations will be apparent to those skilled in the art without departing from the scope and spirit of the described embodiments. The terminology used herein is chosen to best explain the principles, practical application, or technical improvements to the embodiments in the market, or to enable others skilled in the art to understand the embodiments disclosed herein.

Claims

1. An optical glass, characterized by comprising: It comprises the following components in terms of cation mole percentage: Si 4+ : 4-16% B 3+ ：40～59％； La 3+ : 8-12.94%; Y 3+ ：2～6.5％； Ca 2+ : 5-13% Zn 2+ : 3-9% Zr 4+ ：0.01～0.5％； Li + : 1.4-4%; Na + : 7-12% K + ：0～6％； Al 3+ ：0～5％； Mg 2+ : 0-5%; Sr 2+ ：0～5％； Ba 2+ : 0-5%; and Sb 3+ : 0-0.05%; The optical glass does not contain F - ; B 3+ molar percentage with La 3+ mole percentage and Y 3+ The ratio of the sum of the mole percentages B 3+ / (La 3+ +Y 3+ The value is 2 to 4.

5. Zn 2+ molar percentage with La 3+ mole percentage and Y 3+ The ratio of the sum of the mole percentages of Zn 2+ / (La 3+ +Y 3+ The value is 0.2 to 0.

7. The optical glass has a coloring degree λ 80 In λ 80 is 360 nm or less, and λ5is 275 nm or less. The transition temperature Tg of the optical glass is 545℃ or less; The sag temperature Ts of the optical glass is 585℃ or less; The refractive index of the optical glass is 1.65-1.75, and the Abbe number is 50-60.

2. The optical glass according to claim 1, characterized by The optical glass comprises the following components in terms of cation mole percentage: Si 4+ : 6-14% B 3+ ：43～57％； La 3+ : 9-12.94%; Y 3+ ：2.5～6％； Ca 2+ : 6-12%; Zn 2+ : 4-8% Zr 4+ ：0.05～0.45％； Li + : 1.7-3.8%; Na + : 7.5-11.5%; K + ：0～3％； Al 3+ ：0～3％； Mg 2+ : 0-2%; Sr 2+ ：0～2％； Ba 2+ : 0-2%; and Sb 3+ : 0 to 0.03%.

3. Optical glass according to claim 2, characterized in that The optical glass comprises the following components in terms of cation mole percentage: Si 4+ : 7-13% B 3+ ：45～55％； La 3+ : 10-12.94%; Y 3+ ：3～5.5％； Ca 2+ : 7-11% Zn 2+ : 5-7% Zr 4+ ：0.1～0.4％； Li + : 2-3.5%; Na + : 8-11% K + ：0～1％； Al 3+ ：0～1％； Mg 2+ : 0-2%; Sr 2+ ：0～2％； Ba 2+ : 0-2%; and Sb 3+ : 0 to 0.01%.

4. Optical glass according to any one of claims 1 to 3, characterized in that The optical glass does not contain P 5+ , Ta 5 + , Gd 3+ , Nb 5+ , Ge 4+ , Te 4+ and Ti 4+ in combination of one or more than two.

5. The optical glass according to any one of claims 1 to 3, characterized by, Si 4+ mole percentage of B 3+ The ratio of the molar percentage of Si 4+ / B 3+ It ranges from 0.05 to 0.4; La 3+ the sum of the molar percentages of La 3+ and Y 3+ + Y 3+ is 12 to 21.5%.

6. The optical glass according to any one of claims 1-3, characterized in that, The optical glass has a density p of 3.75 g / cm 3 The following: The optical glass has a hardness HK of 630 x 10 7 Pa or more.

7. The optical glass according to any one of claims 1-3, characterized in that, The water resistance stability of the optical glass is level 1; The crystallization temperature Lt of the optical glass is 1050℃ or less; The bubble degree of the optical glass is 0-1 level.

8. A method of producing an optical glass according to any one of claims 1 to 7, characterized by, It comprises weighing and mixing the raw material components of the optical glass according to the proportion, melting, and then pouring or pouring in the forming mold, or directly pressing into shape.

9. An optical element or optical preform, characterized in that, It comprises the optical glass according to any one of claims 1-7.

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