Optical glass, glass preform, optical element and optical instrument

Abstract

The invention provides low-refraction and low-dispersion optical glass with lower thermal expansion coefficient and lower density. The optical glass comprises the following components in molar percentage: 3-10% of P < 5 + >; 6-15% of Al < 3 + >; 2 to 10 percent of Ba < 2 + >; 2-10% of Sr < 2 + >; 2 to 10 percent of Ca < 2 + >; 45%-55% of F <->; and 15 to 25 percent of O2 <->. Through reasonable component design, the optical glass has excellent optical performance and mold pressing performance, and also has low thermal expansion coefficient and density.

Description

[0001] This application is a divisional application of the invention patent application with application number 202411083664.9, application date August 8, 2024, entitled "Optical Glass, Glass Preforms, Optical Elements and Optical Instruments". Technical Field

[0002] This invention relates to an optical glass, and more particularly to a low-refractive-index, low-dispersion optical glass, as well as glass preforms, optical elements, and optical instruments made therefrom. Background Technology

[0003] Fluorophosphate optical glass, as a widely used new type of glass material, has the characteristics of low dispersion and low refractive index. In optical systems, it can eliminate special dispersion in the second-order spectrum, improve resolution, and significantly improve the imaging quality of optical systems. At the same time, it also has a low softening temperature, which can be directly and precisely molded into aspherical lenses.

[0004] In existing technologies, fluorophosphate optical glasses with refractive indices ranging from 1.46 to 1.52 and Abbe numbers from 81 to 88 often prioritize molding stability, but give less consideration to reducing the glass's coefficient of thermal expansion and density. With the development of optical systems in mobile phones, automotive, and security fields, these systems are becoming increasingly miniaturized and sophisticated, and their application environments are becoming more complex, placing higher demands on temperature stability and lightweight design. Furthermore, if the optical glass has a large coefficient of thermal expansion, it will not only affect the imaging stability of the optical system but also lead to sealing failure of the optical module, ultimately causing damage to optical components. Summary of the Invention

[0005] Based on the above reasons, the technical problem to be solved by the present invention is to provide a low-refractive-index and low-dispersion optical glass with a low coefficient of thermal expansion and a low density.

[0006] The technical solution adopted by this invention to solve the technical problem is:

[0007] Optical glass, whose composition is expressed as a mole percentage, contains: P 5+ 3-10%; Al 3+ 3-15%; Ba 2+ : 2-10%; Sr 2+ : 2-10%; Ca 2+ : 2-10%; F - 45-55%; O 2- 15-25%.

[0008] Furthermore, the optical glass, whose composition is expressed as a mole percentage, also contains: Mg 2+ : 0-5%; and / or Y3+ : 0–3%; and / or La 3+ 0–3%; and / or Gd 3+ : 0–3%; and / or R + : 0-5%; and / or clarifying agent: 0-1%, wherein R + For Li + Na + K + One or more of the following, with Cl as the clarifying agent. - ,Br - I - Sb 3+ One or more of them.

[0009] Optical glass, whose composition is expressed as a mole percentage, consists of P 5+ 3-10%; Al 3+ 3-15%; Ba 2+ : 2-10%; Sr 2+ : 2-10%; Ca 2+ 2-10%; Mg 2+ : 0-5%; Y 3+ : 0-3%; La 3+ 0-3%; Gd 3+ : 0-3%; R + : 0-5%; F - 45-55%; O 2- : 15-25%; clarifying agent: 0-1% composition, wherein R + For Li + Na + K + One or more of the following, with Cl as the clarifying agent. - ,Br - I - Sb 3+ One or more of them.

[0010] Furthermore, the composition of the optical glass is expressed as a mole percentage, wherein: F - / (Al 3+ +Mg 2+ +P 5+ +Y 3 + +Gd 3+ The value is 2.0 to 5.0, with F being preferred. - / (Al 3+ +Mg 2+ +P 5+ +Y 3+ +Gd 3+ The value is 2.5 to 4.0, with F being more preferred. - / (Al3+ +Mg 2+ +P 5+ +Y 3+ +Gd 3+ The value ranges from 2.7 to 3.2.

[0011] Furthermore, the optical glass, its composition is expressed as a mole percentage, wherein: (F - +O 2- ) / P 5+ The value is 8.0 to 15.0, preferably (F - +O 2- ) / P 5+ The value is 9.0 to 13.0, more preferably (F - +O 2- ) / P 5+ It ranges from 10.0 to 12.0.

[0012] Furthermore, the composition of the optical glass is expressed as a mole percentage, wherein:

[0013] (Ba 2+ +Y 3+ +Gd 3+ +La 3+ +O 2- ) / P 5+ The value is 3.0 to 5.5, preferably (Ba). 2+ +Y 3+ +Gd 3+ +La 3+ +O 2- ) / P 5+ The value is 3.5 to 5.0, more preferably (Ba 2+ +Y 3+ +Gd 3+ +La 3+ +O 2- ) / P 5+ It ranges from 3.8 to 4.5.

[0014] Furthermore, the composition of the optical glass is expressed as a mole percentage, wherein: P 5+ 4-8%, P is preferred 5 + 4.5–6.5%; and / or Al 3+ 6-13%, with Al preferred 3+ : 8-11%; and / or Ba 2+ 3-8%, preferably Ba 2+ 4.5–6.5%; and / or Sr 2+ 3-8%, preferably Sr 2+ : 4-6%; and / or Ca 2+ 3-9%, preferably Ca2+ 5-7%; and / or Mg 2 + 0-4%, preferably Mg 2+ 0-3%, preferably free of Mg 2+ ; and / or Y 3+ 0-2%, preferred Y 3+ : 0-1%; and / or La 3+ 0-2%, preferably La 3+ 0–1%; and / or Gd 3+ 0-2%, preferably Gd 3+ : 0-1%; and / or R + 0-3%, preferably R + 0-2%, more preferably free of R + ; and / or F - 46-53%, with F being the preferred option. - : 47-51%; and / or O 2- 17-23%, preferred O 2- R: 19-21%; and / or clarifying agent: 0-0.5%, preferably 0-0.3%, wherein R + For Li + Na + K + One or more of the following, with Cl as the clarifying agent. - ,Br - I - Sb 3+ One or more of them.

[0015] Furthermore, the refractive index n of the optical glass... d The preferred refractive index is 1.46–1.52. d The refractive index n is 1.47 to 1.51, and more preferably 1.47 to 1.51. d The Abbe number is 1.48–1.50. d The optimal Abbe number is ν, which is between 81 and 88. d The value is 83-88, with the Abbe number ν being more preferred. d It ranges from 84 to 87.

[0016] Furthermore, the λ of the optical glass 80 340 nm or less, preferably λ 80 Less than or equal to 335nm, preferably λ 80 λ is less than or equal to 330 nm, and is further preferred. 80 λ is preferred to be less than or equal to 325nm. 80The wavelength is less than or equal to 320 nm; and / or λ5 is less than or equal to 265 nm, preferably λ5 is less than or equal to 260 nm, more preferably λ5 is less than or equal to 255 nm, even more preferably λ5 is less than or equal to 250 nm, and still more preferably λ5 is less than or equal to 245 nm; and / or the density ρ is 3.90 g / cm³. 3 The preferred density ρ is 3.82 g / cm³. 3 Below, a density ρ of 3.78 g / cm³ is preferred. 3 Hereinafter, a density ρ of 3.74 g / cm³ is further preferred. 3 The following; and / or transition temperature T g The temperature should be below 500℃, with a preferred transition temperature T. g The temperature should be below 490°C, and the preferred transition temperature is T. g Temperature below 480℃; and / or acid resistance stability RA of class 3 or above, preferably class 2 or above; and / or moisture resistance stability RC of class 2 or above, preferably class 1; and / or coefficient of thermal expansion α 20～300℃ 165×10 -7 Below / K, the coefficient of thermal expansion α is preferred. 20～300℃ 160×10 -7 Below / K, a coefficient of thermal expansion α is preferred. 20～300℃ 155×10 -7 / K or below.

[0017] The glass preform is made of the aforementioned optical glass.

[0018] The optical element is made of the optical glass described above, or of the glass preform described above.

[0019] An optical instrument containing the aforementioned optical glass and / or containing the aforementioned optical elements.

[0020] The beneficial effects of the present invention are: through reasonable component design, the optical glass of the present invention has excellent optical performance and molding performance, while also having a low coefficient of thermal expansion and density. Detailed Implementation

[0021] The embodiments of the optical glass of the present invention will now be described in detail. However, the present invention is not limited to the embodiments described below, and appropriate modifications can be made to implement it within the scope of the purpose of the present invention. Furthermore, regarding repeated descriptions, although there are appropriate omissions, this will not limit the spirit of the invention. In the following text, the optical glass of the present invention will sometimes be simply referred to as glass.

[0022] Optical Glass

[0023] The composition range of each component in the optical glass of the present invention is described below. Unless otherwise specified, each component is expressed as a molar percentage in this specification; that is, the content of each ionic component and the total content are expressed as the molar percentage of that ionic component to the total content of all anionic and cation components.

[0024] Unless otherwise specified in the specific context, the numerical ranges listed herein include upper and lower limits. "Above" and "below" include endpoint values ​​and all integers and fractions included within the range, but are not limited to the specific values ​​listed when the range is defined. The term "and / or" as used herein is inclusive; for example, "A and / or B" means either only A, or only B, or both A and B.

[0025] It should be noted that the ionic valences of the components described below are representative values ​​used for convenience and are not distinguishable from the ionic valences of other components. The ionic valences of the components in optical glass may exist beyond these representative values. For example, phosphorus (P) typically exists in glass with a +5 valence, therefore it is referred to as "P" in this disclosure. 5+ "As a representative value, but there is a possibility that it exists in other ionic valence states, which is also within the scope of protection of this disclosure."

[0026] <Essential and Optional Components>

[0027] P 5+ This component is a constituent of the optical glass of this invention, and it has the function of suppressing devitrification and density increase. If its content is less than 3%, the devitrification resistance of the glass decreases and the density increases. If its content exceeds 10%, the dispersion of the glass increases and the Abbe number decreases, making it difficult to meet the design requirements for optical performance. Therefore, P in this invention... 5+ The content is 3-10%, preferably 4-8%, and more preferably 4.5-6.5%.

[0028] Al 3+ This can improve the stability of the glass of the present invention, effectively enhance its processability and chemical stability, and reduce its coefficient of thermal expansion. If its content is less than 3%, a stable glass framework cannot be formed and the above-mentioned effects cannot be obtained; if its content is greater than 15%, the glass transition temperature and liquidus temperature increase, making glass melting difficult, and the increased temperature during molding leads to intensified glass volatilization, resulting in poor glass striations; on the other hand, excessively high transition temperatures make molding difficult. Therefore, in the present invention, Al... 3+ The content is 3-15%, preferably 6-13%, and more preferably 8-11%.

[0029] Ba 2+ Ba can improve the refractive index, thermal stability, and weather resistance of glass, but excessive Ba can lead to problems. 2+This leads to an increase in the density and coefficient of thermal expansion of the glass, resulting in poorer abrasion resistance. Therefore, in this invention, Ba... 2+ The content is 2-10%, preferably 3-8%, and more preferably 4.5-6.5%.

[0030] Sr 2+ It can reduce the coefficient of thermal expansion of glass and effectively adjust its refractive index and density; however, if its content is too high, the glass's devitrification resistance and chemical stability will decrease. Therefore, in this invention, Sr... 2+ The content is 2-10%, preferably 3-8%, and more preferably 4-6%.

[0031] Ca 2+ It has the effect of reducing the coefficient of thermal expansion and density of glass, and can improve the chemical stability and grinding performance of glass. However, if its content is too high, the refractive index of the glass will be difficult to meet the design requirements, and may lead to a deterioration of devitrification resistance. Therefore, in this invention, Ca... 2+ The content is 2-10%, preferably 3-9%, and more preferably 5-7%.

[0032] Mg 2+ It can improve the abrasion resistance of glass, but in the glass of this invention, if Mg 2+ When the Mg content exceeds 5%, the stability of the glass decreases significantly. Therefore, in this invention, Mg... 2+ The content is 0-5%, preferably 0-4%, and more preferably 0-3%. In some embodiments, it is further preferred that it does not contain Mg. 2+ .

[0033] Y 3+ It can increase the refractive index of glass and reduce its coefficient of thermal expansion. However, if its content exceeds 3%, the liquidus temperature of the glass rises, and its devitrification resistance decreases. Therefore, Y... 3+ The content of Y is 0-3%, preferably 0-2%, and more preferably 0-1%. In some embodiments, Y can be introduced by means of Y fluorides, oxides, and Y-containing salts. 3+ .

[0034] La 3+ It has the effect of increasing the refractive index of glass and improving its acid resistance. 3+ When the content of La is too high, the thermal stability and devitrification resistance of the glass decrease, and the glass is prone to devitrification during the manufacturing process. Therefore, in this invention, La... 3+ The content of La is 0-3%, preferably 0-2%, and more preferably 0-1%. In some embodiments, La can be introduced by means of La fluorides, oxides, and La-containing salts. 3+ .

[0035] Gd 3+It can improve the chemical stability of glass, maintain low dispersion while appropriately increasing the refractive index, and can also appropriately improve mechanical strength and reduce the coefficient of thermal expansion. However, if its content exceeds 3%, the liquidus temperature and stability of the glass decrease. Therefore, Gd... 3+ The content of Gd is 0-3%, preferably 0-2%, and more preferably 0-1%. In some embodiments, Gd can be introduced by means of Gd fluorides, oxides, and Gd-containing salts. 3+ .

[0036] R + (R + For Li + Na + K + One or more of the following can lower the glass transition temperature, if R + A content greater than 5% will lead to an increase in the glass liquid phase temperature. Therefore, R + The content of [R] is 0-5%, preferably 0-3%, and more preferably 0-2%. In some embodiments, it is further preferred that it does not contain [R]. + .

[0037] F - It plays a significant role in adjusting the refractive index of glass, reducing the temperature coefficient of refractive index, and the transition temperature; it is an important component for improving the Abbe number and anomalous dispersion. If F - Excessive F content weakens the stability of glass, increases the coefficient of thermal expansion and abrasion, especially during the melting process. - The volatilization of these substances not only pollutes the environment but also causes the optical constants of the glass to exceed their design limits. When F... - When the content is less than 45%, the designed Abbe number and anomalous dispersion cannot be obtained; if the content is higher than 55%, the Abbe number of the glass will become too large, and volatilization will increase sharply during melting and precision molding. Therefore, F - The content is limited to 45-55%, preferably 46-53%, and more preferably 47-51%.

[0038] The inventors, through extensive research, discovered that in some implementation methods, by controlling F - The content of Al 3+ Mg 2+ P 5+ Y 3+ Gd 3+ Total Al content 3+ +Mg 2+ +P 5+ +Y 3+ +Gd 3+ The ratio F between them - / (Al 3+ +Mg 2+ +P5+ +Y 3+ +Gd 3+ Below 5.0, the coefficient of thermal expansion of glass can be effectively reduced. However, when the ratio is below 2.0, the glass transition temperature and liquidus temperature increase, making production more difficult. Therefore, F is preferred. - / (Al 3+ +Mg 2+ +P 5+ +Y 3+ +Gd 3+ The value is 2.0 to 5.0, with F being more preferred. - / (Al 3+ +Mg 2+ +P 5+ +Y 3+ +Gd 3+ The value is 2.5-4.0, and further optimization is needed.

[0039] F - / (Al 3+ +Mg 2+ +P 5+ +Y 3+ +Gd 3+ The value ranges from 2.7 to 3.2.

[0040] The optical glass of this invention contains O 2- Especially through the presence of more than 15% O 2- It can achieve excellent optical performance and low wear, but when O 2- When the content is greater than 25%, the liquidus temperature of the glass rises rapidly. Therefore, O 2- The content is 15-25%, preferably 17-23%, and more preferably 19-21%.

[0041] Through extensive experimental research, the inventors discovered that in some implementation methods, controlling F - and O 2- Total content F - +O 2- With P 5+ The ratio between the contents of (F) - +O 2- ) / P 5+ Within the range of 8.0 to 15.0, the glass density can be reduced while maintaining the desired optical constants, thus optimizing the glass's thermal stability and colorfastness. Therefore, (F) is preferred. - +O 2- ) / P 5+ The value is 8.0 to 15.0, more preferably (F - +O 2- ) / P 5+ The value is 9.0–13.0, and further optimization is needed (F).- +O 2- ) / P 5+ It ranges from 10.0 to 12.0.

[0042] In some implementations, Ba 2+ Y 3+ Gd 3+ La 3+ and O 2- Total Ba content 2+ +Y 3+ +Gd 3+ +La 3+ +O 2- With P 5+ The ratio between the contents of Ba 2+ +Y 3+ +Gd 3+ +La 3+ +O 2- ) / P 5+ By controlling the coefficient of thermal expansion (CTE) within the range of 3.0 to 5.5, the glass can achieve lower density and coefficient of thermal expansion while improving its devitrification resistance. Therefore, (Ba) is preferred. 2+ +Y 3+ +Gd 3+ +La 3+ +O 2- ) / P 5+ The value is 3.0 to 5.5, more preferably (Ba 2+ +Y 3+ +Gd 3+ +La 3+ +O 2- ) / P 5+ The value is 3.5–5.0, with further optimization (Ba). 2+ +Y 3+ +Gd 3+ +La 3+ +O 2- ) / P 5+ It ranges from 3.8 to 4.5.

[0043] In the optical glass of this invention, the clarification effect of the glass can be improved by containing less than 1% of a clarifying agent, wherein the clarifying agent is Cl. - ,Br - I - Sb 3+ One or more components in the clarifier may corrode platinumware if the clarifier content is too high. Therefore, the clarifier content in this invention is 0-1%, preferably 0-0.5%, and more preferably 0-0.3%.

[0044] Without compromising the excellent properties of the glass of the present invention, the optical glass of the present invention may contain, as needed, elements such as Ta.5+ W 6+ 、Ge 4+ Bi 3+ Te 4+ Other components.

[0045] <Ingredients that should not be present>

[0046] Other components not mentioned above can be added as needed without compromising the excellent properties of the glass of the present invention. However, transition metal components such as Ce, V, Cr, Mn, Fe, Co, Ni, Cu, Ag, and Mo, even when contained in small amounts individually or in combination, can color the glass and cause absorption at specific wavelengths in the visible light region, thereby weakening the visible light transmittance improvement effect of the present invention. Therefore, it is preferable that the above-mentioned components are not actually present, especially for optical glass where transmittance in the visible light region is required.

[0047] The cations Pb, Th, Cd, Tl, Os, Be, and Se have been increasingly subject to controlled use in recent years due to their status as hazardous chemicals. Environmental protection measures are essential not only in glass manufacturing but also in processing and post-product disposal. Therefore, given the importance of environmental impact, it is preferable to ideally contain virtually none of these substances, except where their contamination is unavoidable. Consequently, the optical glass becomes virtually free of pollutants. Therefore, the optical glass of this invention can be manufactured, processed, and disposed of even without specific environmental countermeasures.

[0048] The performance of the optical glass of the present invention will now be described.

[0049] <Refractive Index and Abbe Number>

[0050] The refractive index (n) of optical glass d ) and Abbe number (ν d Test according to the method specified in GB / T 7962.1—2010.

[0051] The optical glass of this invention is a low-refractive-index, low-dispersion optical glass. Lenses made of low-refractive-index, low-dispersion optical glass are often combined with lenses made of high-refractive-index, high-dispersion optical glass for chromatic aberration correction.

[0052] In some embodiments, the refractive index (n) of the optical glass of the present invention d The preferred refractive index (n) is 1.46–1.52. d The refractive index (n) is 1.47–1.51, more preferably 1.47–1.51. d The value is 1.48 to 1.50.

[0053] In some embodiments, the Abbe number (ν) of the optical glass of the present inventiond The optimal Abbe number is 81-88. d The Abbe number is 83-88, and more preferably ν. d The value is 84-87.

[0054] <Colorization>

[0055] The short-wavelength transmission spectral characteristics of the optical glass of this invention are expressed using chromaticity (λ). 80 / λ5) represents. λ 80 λ5 refers to the wavelength corresponding to a glass transmittance of 80%, while λ6 refers to the wavelength corresponding to a glass transmittance of 5%. Where λ... 80 The measurement was performed using a glass with a thickness of 10 ± 0.1 mm and two optically polished, parallel planes. The spectral transmittance was measured in the wavelength range from 280 nm to 700 nm, and wavelengths exhibiting 80% transmittance were recorded. Spectroscopic transmittance, or transmittance, refers to the transmittance of light incident perpendicularly to the aforementioned surface of the glass at wavelengths of intensity I. in Light, passing through the glass and emitted from another plane, has an intensity of I. out In the case of light, through I out / I in The quantity represented also includes the transmittance of the glass due to surface reflection loss on the aforementioned surface. In the glass of the present invention, λ 80 A small value means that the glass itself has very little coloration. The same applies to λ5.

[0056] In some embodiments, the λ of the optical glass of the present invention 80 340 nm or less, preferably λ 80 Less than or equal to 335nm, preferably λ 80 λ is less than or equal to 330 nm, and is further preferred. 80 λ is preferred to be less than or equal to 325nm. 80 Less than or equal to 320nm.

[0057] In some embodiments, the λ5 of the optical glass of the present invention is less than or equal to 265 nm, preferably less than or equal to 260 nm, more preferably less than or equal to 255 nm, even more preferably less than or equal to 250 nm, and even more preferably less than or equal to 245 nm.

[0058] <Density>

[0059] The density (ρ) of optical glass is tested according to the method specified in GB / T 7962.20-2010, and is the mass per unit volume at a temperature of 20℃, expressed in g / cm³. 3 express.

[0060] In some embodiments, the density (ρ) of the optical glass of the present invention is 3.90 g / cm³. 3 The preferred value is 3.82 g / cm³. 3 The preferred value is 3.78 g / cm³. 3 The following is a further preferred value: 3.74 g / cm³ 3 the following.

[0061] <Transition Temperature>

[0062] Transition temperature of optical glass (T) g Test according to the method specified in GB / T 7962.16-2010.

[0063] In some embodiments, the transition temperature (T) of the optical glass of the present invention is... g The temperature is below 500°C, preferably below 490°C, and more preferably below 480°C.

[0064] <Acid resistance>

[0065] The acid resistance stability (RA) (surface method) of optical glass was tested according to the method specified in GB / T 7962.14-2010.

[0066] In some embodiments, the acid resistance (RA) of the optical glass of the present invention is Class 3 or above, preferably Class 2 or above.

[0067] Moisture resistance stability

[0068] The moisture resistance stability (RC) (surface method) of optical glass was tested according to the method specified in GB / T 7962.15-2010.

[0069] In some embodiments, the moisture resistance stability (RC) of the optical glass of the present invention is Class 2 or above, preferably Class 1.

[0070] Coefficient of thermal expansion

[0071] The coefficient of thermal expansion of optical glass (α) 20～300℃ Test according to the method specified in GB / T7962.16-2010.

[0072] In some embodiments, the coefficient of thermal expansion (α) of the optical glass of the present invention is... 20～300℃ ) is 165×10 -7 / K or less, preferably 160×10 -7 / K or less, preferably 155×10 -7 / K or below.

[0073] [Manufacturing methods for optical glass]

[0074] The manufacturing method of the optical glass of this invention is as follows: The optical glass of this invention is produced using conventional raw materials and conventional processes. Carbonates, nitrates, sulfates, phosphates, oxides, fluorides, metaphosphates, etc., are used as raw materials. After being batched according to conventional methods, the batched material is melted in a melting furnace at 900–1000°C. After clarification and thorough homogenization, it is cast or punched at a temperature below 800°C to obtain the optical glass of this invention. Those skilled in the art can appropriately select raw materials, process methods, and process parameters according to actual needs.

[0075] [Glass preforms and optical components]

[0076] Glass preforms can be manufactured from the optical glass using methods such as grinding, hot pressing, or precision stamping. Specifically, glass preforms can be manufactured by machining the optical glass, such as grinding and polishing; or by hot pressing a preform made from the optical glass for molding and then grinding it; or by precision stamping a preform made from the ground glass.

[0077] It should be noted that the means of preparing the glass preform are not limited to those described above. As mentioned above, the optical glass of the present invention is useful for various optical components and optical designs, and it is particularly preferred to form a preform from the optical glass of the present invention, using the preform for re-hot pressing, precision stamping, etc., to manufacture optical components such as lenses and prisms.

[0078] Both the glass preform and the optical element of the present invention are formed from the optical glass described above. The glass preform of the present invention possesses the excellent properties of optical glass, and the optical element of the present invention possesses the excellent properties of optical glass. Examples of lenses include various lenses such as concave meniscus lenses, convex meniscus lenses, biconvex lenses, biconcave lenses, plano-convex lenses, and plano-concave lenses, whose lens surfaces are spherical or aspherical.

[0079] [Optical Instruments]

[0080] The optical elements formed by the optical glass of this invention can be used to manufacture optical instruments such as photographic equipment, video equipment, display equipment, and monitoring equipment.

[0081] Example

[0082] <Example of Optical Glass>

[0083] To further illustrate and explain the technical solution of the present invention, the following non-limiting embodiments are provided.

[0084] In this embodiment, optical glass with the composition shown in Tables 1 to 4 was obtained using the optical glass manufacturing method described above. Furthermore, the properties of each glass were measured using the testing method described in this invention, and the measurement results are shown in Tables 1 to 4.

[0085] Table 1.

[0086] Example (mol%) 1# 2# 3# 4# 5# 6# 7# 8# <![CDATA[P 5+ ]]> 5.29 5.36 5.25 5.01 5.62 5.67 5.99 5.97 <![CDATA[Al 3+ ]]> 10.33 10.01 10.31 10.61 10.20 9.22 9.67 8.69 <![CDATA[Ba 2+ ]]> 4.29 4.59 4.62 5.96 4.70 4.79 4.24 4.34 <![CDATA[Sr 2+ ]]> 3.68 3.74 3.95 3.60 4.21 4.33 4.71 4.73 <![CDATA[Ca 2+ ]]> 5.79 5.91 5.58 4.55 5.43 5.57 5.69 5.65 <![CDATA[Mg 2+ ]]> 1.08 0.71 0 0 0.12 0.86 0 0.50 <![CDATA[La 3+ ]]> 0 0.12 0.22 0 0.11 0 0 0 <![CDATA[Gd 3+ ]]> 0 0 0.20 0.51 0.18 0.14 0.31 0.30 <![CDATA[Y 3+ ]]> 0.20 0.22 0.20 0.33 0.17 0.21 0.20 0 <![CDATA[Li + ]]> 0 0 0.30 0 0 0 0 0.51 <![CDATA[Na + ]]> 0 0 0 0 0 0 0 0 <![CDATA[K + ]]> 0 0 0 0 0 0 0 0.10 Clarifying agent 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10 <![CDATA[F - ]]> 50.57 50.51 50.82 51.23 49.64 49.59 48.24 48.33 <![CDATA[O 2- ]]> 18.67 18.73 18.45 18.10 19.52 19.52 20.85 20.78 total 100 100 100 100 100 100 100 100 <![CDATA[F - / (To the 3+ +Mg 2+ +P 5+ +And 3+ +Gd 3+ )]]> 2.99 3.10 3.18 3.11 3.05 3.08 2.98 3.13 <![CDATA[(F - +O 2- ) / P 5+ ]]> 13.09 12.92 13.19 13.84 12.31 12.19 11.53 11.58 <![CDATA[(Ba 2+ +And 3+ +Gd 3+ +The 3+ +O 2- ) / P 5+ ]]> 4.38 4.41 4.51 4.97 4.39 4.35 4.27 4.26 <![CDATA[n d ]]> 1.47955 1.48066 1.48213 1.48396 1.48346 1.48301 1.48681 1.48773 <![CDATA[v d ]]> 86.21 85.94 86.31 85.78 85.85 86.01 85.12 84.88 <![CDATA[λ 80 / λ5]]> 319 / 204 320 / 206 318 / 215 320 / 219 322 / 218 322 / 216 326 / 237 324 / 238 <![CDATA[ρ(g / cm 3 )]]> 3.67 3.76 3.78 3.86 3.79 3.74 3.74 3.77 <![CDATA[T g (℃)]]> 476 477 484 483 479 472 478 466 RC (Class) 1 1 1 1 1 1 1 1 RA (class) 2 3 2 2 2 2 2 2 <![CDATA[α 20～300℃ (×10 -7 / K)]]> 151 155 148 150 151 153 150 156

[0087] Table 2.

[0088]

[0089]

[0090] Table 3.

[0091]

[0092]

[0093] Table 4.

[0094] Example (mol%) 25# 26# 27# 28# 29# 30# <![CDATA[P 5+ ]]> 6.30 6.60 6.20 6.36 6.43 6.21 <![CDATA[Al 3+ ]]> 9.01 9.54 9.81 9.49 9.27 9.40 <![CDATA[Ba 2+ ]]> 3.96 3.78 3.76 3.90 3.87 3.81 <![CDATA[Sr 2+ ]]> 4.81 4.40 4.88 4.67 4.66 4.85 <![CDATA[Ca 2+ ]]> 5.04 5.04 5.19 5.23 5.20 5.55 <![CDATA[Mg 2+ ]]> 0.48 0.71 0.21 0.55 0.55 0.33 <![CDATA[La 3+ ]]> 0.23 0.20 0.20 0.12 0.12 0.11 <![CDATA[Gd 3+ ]]> 0.53 0.11 0.12 0.17 0.17 0.21 <![CDATA[Y 3+ ]]> 0.31 0.23 0.22 0.32 0.32 0.32 <![CDATA[Li + ]]> 0.12 0.12 0 0 0.22 0 <![CDATA[Na + ]]> 0 0 0 0 0 0 <![CDATA[K + ]]> 0 0 0 0 0 0 Clarifying agent 0.10 0.10 0.10 0.10 0.10 0.10 <![CDATA[F - ]]> 48.21 47.87 48.33 47.93 47.89 48.02 <![CDATA[O 2- ]]> 20.90 21.30 20.98 21.16 21.20 21.09 total 100 100 100 100 100 100 <![CDATA[F - / (To the 3+ +Mg 2+ +P 5+ +And 3+ +Gd 3+ )]]> 2.90 2.78 2.92 2.84 2.86 2.92 <![CDATA[(F - +O 2- ) / P 5+ ]]> 10.97 10.48 11.18 10.86 10.74 11.13 <![CDATA[(Ba 2+ +And 3+ +Gd 3+ +The 3+ +O 2- ) / P 5+ ]]> 4.12 3.88 4.08 4.04 3.99 4.11 <![CDATA[n d ]]> 1.48453 1.48718 1.48556 1.48453 1.48667 1.48501 <![CDATA[v d ]]> 85.47 85.11 85.36 84.88 84.94 85.21 <![CDATA[λ 80 / λ5]]> 332 / 246 325 / 235 322 / 231 323 / 228 325 / 234 322 / 233 <![CDATA[ρ(g / cm 3 )]]> 3.70 3.72 3.73 3.69 3.69 3.70 <![CDATA[T g (℃)]]> 469 473 476 471 467 473 RC (Class) 1 1 1 1 1 1 RA (class) 2 2 2 2 2 2 <![CDATA[α 20～300℃ (×10 -7 / K)]]> 152 148 149 149 149 149

[0095] <Example of Glass Prefabricated Components>

[0096] The glass obtained from optical glass Examples 1 to 30# is used to manufacture preforms of various lenses and prisms, such as concave meniscus lenses, convex meniscus lenses, biconvex lenses, biconcave lenses, plano-convex lenses, and plano-concave lenses, by means of grinding, hot pressing, precision stamping, or other molding methods.

[0097] <Optical Component Examples>

[0098] Annealing the preforms obtained from the above glass preform examples reduces the internal stress of the glass while fine-tuning the refractive index, so that the optical properties such as the refractive index reach the desired values.

[0099] Next, the prefabricated parts are 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. Anti-reflective coatings can also be applied to the surface of the resulting optical elements.

[0100] <Examples of Optical Instruments>

[0101] The optical elements obtained from the above-described optical element embodiments can be used, through optical design, to form optical components or optical assemblies by using one or more optical elements. These components can be used in, for example, imaging devices, 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 that include such circuits and chips.

Claims

1. Optical glass, characterized in that, Its components are expressed as a mole percentage and contain: P 5+ 3-10%; Al 3+ 6-15%; Ba 2+ : 2-10%; Sr 2+ : 2-10%; Ca 2+ : 2-10%; F - 45-55%; O 2- 15-25%.

2. The optical glass according to claim 1, characterized in that, Its components, expressed as a mole percentage, also include: Mg 2 + : 0-5%; and / or Y 3+ : 0–3%; and / or La 3+ 0–3%; and / or Gd 3+ : 0–3%; and / or R + : 0-5%; and / or clarifying agent: 0-1%, wherein R + For Li + Na + K + One or more of the following, with Cl as the clarifying agent. - ,Br - I - Sb 3+ One or more of them.

3. Optical glass, characterized in that, Its components are expressed as mole percentages, derived from P 5+ 3-10%; Al 3+ 6-15%; Ba 2 + : 2-10%; Sr 2+ : 2-10%; Ca 2+ 2-10%; Mg 2+ : 0-5%; Y 3+ : 0-3%; La 3+ 0-3%; Gd 3+ : 0-3%; R + : 0-5%; F - 45-55%; O 2- : 15-25%; clarifying agent: 0-1% composition, wherein R + For Li + Na + K + One or more of the following, with Cl as the clarifying agent. - ,Br - I - Sb 3+ One or more of them.

4. The optical glass according to any one of claims 1 to 3, characterized in that, Its components are expressed as mole percentages, where: F - / (Al 3+ +Mg 2+ +P 5+ +Y 3+ +Gd 3+ The value is 2.0 to 5.0, with F being preferred. - / (Al 3+ +Mg 2+ +P 5+ +Y 3+ +Gd 3+ The value is 2.5 to 4.0, with F being more preferred. - / (Al 3+ +Mg 2+ +P 5+ +Y 3+ +Gd 3+ The value ranges from 2.7 to 3.

2.

5. The optical glass according to any one of claims 1 to 3, characterized in that, Its components are expressed as mole percentages, wherein: (F - +O 2- ) / P 5+ The value is 8.0 to 15.0, preferably (F - +O 2- ) / P 5+ The value is 9.0 to 13.0, more preferably (F - +O 2- ) / P 5+ It ranges from 10.0 to 12.

0.

6. The optical glass according to any one of claims 1 to 3, characterized in that, Its components are expressed as mole percentages, of which: (Ba 2+ +Y 3+ +Gd 3+ +La 3+ +O 2- ) / P 5+ The preferred value is 3.0 to 5.

5. (Ba 2+ +Y 3+ +Gd 3+ +La 3+ +O 2- ) / P 5+ The value is 3.5 to 5.0, more preferably (Ba 2+ +Y 3+ +Gd 3+ +La 3+ +O 2- ) / P 5+ It ranges from 3.8 to 4.

5.

7. The optical glass according to any one of claims 1 to 3, characterized in that, Its components are expressed as mole percentages, where: P 5+ 4-8%, P is preferred 5+ 4.5–6.5%; and / or Al 3+ 6-13%, with Al preferred 3+ : 8-11%; and / or Ba 2+ 3-8%, preferably Ba 2+ 4.5–6.5%; and / or Sr 2+ 3-8%, preferably Sr 2+ : 4-6%; and / or Ca 2+ 3-9%, preferably Ca 2+ 5-7%; and / or Mg 2+ 0-4%, preferably Mg 2+ 0-3%, preferably free of Mg 2+ ; and / or Y 3+ 0-2%, preferred Y 3+ : 0-1%; and / or La 3+ 0-2%, preferably La 3+ 0–1%; and / or Gd 3+ 0-2%, preferably Gd 3+ : 0-1%; and / or R + 0-3%, preferably R + 0-2%, more preferably free of R + ; and / or F - 46-53%, with F being the preferred option. - : 47-51%; and / or O 2- 17-23%, preferred O 2- R: 19-21%; and / or clarifying agent: 0-0.5%, preferably 0-0.3%, wherein R + For Li + Na + K + One or more of the following, with Cl as the clarifying agent. - ,Br - I - Sb 3+ One or more of them.

8. The optical glass according to any one of claims 1 to 3, characterized in that, The refractive index n of the optical glass d The preferred refractive index is 1.46–1.

52. d The refractive index n is 1.47 to 1.51, and more preferably 1.47 to 1.

51. d The Abbe number is 1.48–1.

50. d The optimal Abbe number is ν, which is between 81 and 88. d The value is 83-88, with the Abbe number ν being more preferred. d It ranges from 84 to 87.

9. The optical glass according to any one of claims 1 to 3, characterized in that, The λ of the optical glass 80 340 nm or less, preferably λ 80 Less than or equal to 335nm, preferably λ 80 λ is less than or equal to 330 nm, and is further preferred. 80 λ is preferred to be less than or equal to 325nm. 80 The wavelength is less than or equal to 320 nm; and / or λ5 is less than or equal to 265 nm, preferably λ5 is less than or equal to 260 nm, more preferably λ5 is less than or equal to 255 nm, even more preferably λ5 is less than or equal to 250 nm, and still more preferably λ5 is less than or equal to 245 nm; and / or the density ρ is 3.90 g / cm³. 3 The preferred density ρ is 3.82 g / cm³. 3 Below, a density ρ of 3.78 g / cm³ is preferred. 3 Hereinafter, a density ρ of 3.74 g / cm³ is further preferred. 3 The following; and / or transition temperature T g The temperature should be below 500℃, with a preferred transition temperature T. g The temperature should be below 490°C, and the preferred transition temperature is T. g Temperature below 480℃; and / or acid resistance stability RA of class 3 or above, preferably class 2 or above; and / or moisture resistance stability RC of class 2 or above, preferably class 1; and / or coefficient of thermal expansion α 20～300℃ 165×10 -7 Below / K, the coefficient of thermal expansion α is preferred. 20～300℃ 160×10 -7 Below / K, a coefficient of thermal expansion α is preferred. 20～300℃ 155×10 -7 / K or below.

10. A glass preform, characterized in that, It is made of the optical glass described in any one of claims 1 to 9.

11. An optical element, characterized in that, It is made of the optical glass described in any one of claims 1 to 9, or of the glass preform described in claim 10.

12. An optical instrument, characterized in that, It contains the optical glass according to any one of claims 1 to 9, and / or contains the optical element according to claim 11.

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