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 + >; 3%-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

Technical Field

[0001] The invention relates to an optical glass, in particular to an optical glass with low refraction and low dispersion, and a glass preform, an optical element and an optical instrument made of the same. Background Art

[0002] Fluorophosphate optical glass is a new type of glass material with a wide range of applications. It has the characteristics of low dispersion and low refractive index. It can eliminate the special dispersion of the secondary spectrum in the optical system, improve the resolution, and significantly improve the imaging quality of the optical system. It also has a low softening temperature and can be directly precision molded into aspheric lenses.

[0003] In the prior art, fluorophosphate optical glass with a refractive index of 1.46 to 1.52 and an Abbe number of 81 to 88 often prioritizes molding stability, but pays less attention to reducing the thermal expansion coefficient and density of the glass. With the development of optical systems in the fields of mobile phones, vehicles, security, etc., optical systems have become more miniaturized and sophisticated, and their application environments have become more complex, placing higher demands on the temperature stability and lightweight of optical systems. On the other hand, if the optical glass has a large thermal expansion coefficient, it will not only affect the imaging stability of the optical system, but also cause the sealing of the optical module to fail, thereby causing damage to the optical components. Summary of the invention

[0004] Based on the above reasons, the technical problem to be solved by the present invention is to provide a low-refractive and low-dispersion optical glass with a lower thermal expansion coefficient and a lower density.

[0005] The technical solution adopted by the present invention to solve the technical problem is:

[0006] Optical glass, the components of which are expressed in mole percentage, contain: 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%.

[0007] Furthermore, the optical glass, expressed in molar percentage, also contains: 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 clarifier: 0-1%, the R+ For Li + 、Na + , K + One or more of the following, the clarifier is Cl - Br - ,I - , Sb 3+ One or more of .

[0008] Optical glass, whose components are expressed in mole percentage, is composed 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%; clarifier: 0~1% composition, the R + For Li + 、Na + , K + One or more of the following, the clarifier is Cl - Br - ,I - , Sb 3+ One or more of .

[0009] Furthermore, the optical glass has its components expressed in molar percentage, wherein: - / (Al 3+ +Mg 2+ +P 5+ +Y 3 + +Gd 3+ ) is 2.0 to 5.0, preferably F - / (Al 3+ +Mg 2+ +P 5+ +Y 3+ +Gd 3+ ) is 2.5 to 4.0, and more preferably F - / (Al 3+ +Mg 2+ +P 5+ +Y 3+ +Gd 3+ ) is 2.7~3.2.

[0010] Furthermore, the optical glass, its components are expressed in molar percentage, wherein: - +O 2- ) / P 5+ 8.0 to 15.0, preferably (F - +O 2- ) / P 5+ 9.0 to 13.0, more preferably (F - +O 2- ) / P 5+ It is 10.0~12.0.

[0011] Furthermore, the components of the optical glass are expressed in molar percentage, wherein:

[0012] (Ba 2+ +Y 3+ +Gd 3+ +La 3+ +O 2- ) / P 5+ 3.0 to 5.5, preferably (Ba 2+ +Y 3+ +Gd 3+ +La 3+ +O 2- ) / P 5+ is 3.5 to 5.0, more preferably (Ba 2+ +Y 3+ +Gd 3+ +La 3+ +O 2- ) / P 5+ It is 3.8 to 4.5.

[0013] Furthermore, the optical glass has its components expressed in molar percentage, wherein: 5+ : 4-8%, preferably P 5 + :4.5~6.5%;and / or Al 3+ : 6-13%, preferably Al 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 to 3%, preferably no Mg 2+ ; and / or Y 3+: 0-2%, preferably 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 to 2%, preferably no R + ; and / or F - : 46-53%, preferably F - : 47-51%; and / or O 2- : 17-23%, preferably O 2- : 19-21%; and / or clarifier: 0-0.5%, preferably clarifier: 0-0.3%, the R + For Li + 、Na + , K + One or more of the following, the clarifier is Cl - Br - ,I - , Sb 3+ One or more of .

[0014] Furthermore, the refractive index n of the optical glass is d The refractive index n is preferably 1.46 to 1.52. d The refractive index n is preferably 1.47 to 1.51. d 1.48~1.50; Abbe number ν d 81 to 88, preferably Abbe number ν d 83 to 88, more preferably Abbe number ν d It is 84 to 87.

[0015] Furthermore, the λ of the optical glass 80 Less than or equal to 340nm, preferably λ 80 Less than or equal to 335nm, more preferably λ 80 Less than or equal to 330nm, more preferably λ 80 Less than or equal to 325nm, more preferably λ 80 less than or equal to 320nm; and / or λ5 is less than or equal to 265nm, preferably λ5 is less than or equal to 260nm, more preferably λ5 is less than or equal to 255nm, further preferably λ5 is less than or equal to 250nm, and further preferably λ5 is less than or equal to 245nm; and / or density ρ is 3.90g / cm 3 Below, the preferred density ρ is 3.82 g / cm 3Below, the more preferred density ρ is 3.78 g / cm 3 Below, the density ρ is further preferably 3.74 g / cm 3 Below; and / or transition temperature T g The preferred transition temperature is 500°C or less. g The transition temperature is preferably 490°C or less. g 480 ° C or less; and / or acid resistance stability RA is 3 or more, preferably acid resistance stability RA is 2 or more; and / or moisture resistance stability RC is 2 or more, preferably moisture resistance stability RC is 1; and / or thermal expansion coefficient α 20～300℃ 165×10 -7 / K or less, preferably with a thermal expansion coefficient of α 20～300℃ 160×10 -7 / K or less, preferably a thermal expansion coefficient of α 20～300℃ 155×10 -7 / K or less.

[0016] The glass preform is made of the above optical glass.

[0017] The optical element is made of the above optical glass, or made of the above glass preform.

[0018] An optical instrument contains the above optical glass and / or contains the above optical element.

[0019] The beneficial effects of the present invention are: through reasonable component design, the optical glass of the present invention has excellent optical properties and molding properties, as well as lower thermal expansion coefficient and density. DETAILED DESCRIPTION

[0020] The following will describe the embodiments of the optical glass of the present invention in detail, 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 invention will not be limited thereby, and in the following content, the optical glass of the present invention is sometimes referred to as glass.

[0021] [Optical glass]

[0022] The following is an explanation of the scope of each component (ingredient) constituting the optical glass of the present invention. In this specification, unless otherwise specified, each component is expressed in mole percentage, that is, the content of each ionic component and the total content are expressed in mole percentage of the total content of the ionic component and all anionic and cationic components.

[0023] Unless otherwise indicated in specific circumstances, the numerical ranges listed herein include upper and lower limits, "above" and "below" include the endpoints, and all integers and fractions included in the range, without being limited to the specific values ​​listed when the range is defined. "And / or" referred to herein is inclusive, for example, "A and / or B" means only A, or only B, or both A and B.

[0024] It should be noted that the ionic valences of the components described below are representative values ​​used for convenience and are not different from other ionic valences. The ionic valences of the components in the optical glass may be other than the representative values. For example, P usually exists in the glass in a state of +5 ionic valence, so in this disclosure, “P 5+ " is used as a representative value, but there is the possibility of existing in other ionic valence states, which is also within the scope of protection of the present disclosure.

[0025] <Essential Components and Optional Components>

[0026] P 5+ It is a component of the optical glass of the present invention, and has the effect of inhibiting the devitrification of the glass and inhibiting the increase of density. 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, resulting in the optical performance being difficult to meet the design requirements. Therefore, P in the present invention 5+ The content of is 3 to 10%, preferably 4 to 8%, and more preferably 4.5 to 6.5%.

[0027] Al 3+ It can improve the stability of the glass of the present invention, and effectively improve the processability and chemical stability of the glass, and at the same time reduce the thermal expansion coefficient of the glass. If its content is less than 3%, it is impossible to form a stable glass skeleton and obtain the above-mentioned effects; if its content is higher than 15%, the transition temperature and liquidus temperature of the glass increase, making it difficult to melt the glass, and at the same time, the temperature increases during molding, resulting in increased volatilization of the glass, making the glass stripe worse; on the other hand, too high a transition temperature makes compression molding difficult. Therefore, Al in the present invention 3+ The content is 3 to 15%, preferably 6 to 13%, and more preferably 8 to 11%.

[0028] Ba 2+ It has the effect of improving the refractive index, thermal stability and weather resistance of glass, but too much Ba 2+ This will lead to an increase in the density and thermal expansion coefficient of the glass, and a worse abrasion resistance. 2+ The content of is 2 to 10%, preferably 3 to 8%, and more preferably 4.5 to 6.5%.

[0029] Sr 2+It can reduce the thermal expansion coefficient of glass and effectively adjust the refractive index and density of glass. However, if its content is too high, the devitrification resistance and chemical stability of glass will be reduced. 2+ The content is 2 to 10%, preferably 3 to 8%, and more preferably 4 to 6%.

[0030] Ca 2+ It has the effect of reducing the thermal expansion coefficient and density of glass, and can improve the chemical stability of glass and improve the grinding performance of glass. However, if its content is too high, the refractive index of glass is difficult to meet the design requirements, and the devitrification resistance may be deteriorated. 2+ The content of is 2 to 10%, preferably 3 to 9%, more preferably 5 to 7%.

[0031] Mg 2+ It can improve the abrasiveness of the glass, but in the glass of the present invention, if Mg 2+ If the content of Mg exceeds 5%, the stability of the glass will be greatly reduced. 2+ The content of Mg is 0-5%, preferably 0-4%, and more preferably 0-3%. In some embodiments, it is further preferred that Mg is not contained. 2+ .

[0032] Y 3+ It can increase the refractive index of glass and reduce the thermal expansion coefficient of glass. If its content is higher than 3%, the liquidus temperature of glass will rise and the resistance to devitrification will decrease. 3+ The content of Y is 0-3%, preferably 0-2%, and more preferably 0-1%. In some embodiments, Y can be introduced by using Y fluoride, oxide, or salt containing Y. 3+ .

[0033] La 3+ It has the effect of increasing the refractive index of glass and improving acid resistance. 3+ When the content of La is too high, the thermal stability and resistance to devitrification of the glass decrease, and the glass is prone to devitrification during the manufacturing process. 3+ The content of La is 0-3%, preferably 0-2%, and more preferably 0-1%. In some embodiments, La can be introduced by using La fluoride, La oxide, La-containing salt, etc. 3+ .

[0034] G 3+ It can improve the chemical stability of glass, maintain low dispersion while appropriately increasing the refractive index, and appropriately increase the mechanical strength and reduce the thermal expansion coefficient. If its content exceeds 3%, the liquidus temperature and stability of the glass will 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 using Gd fluoride, oxide, and salt containing Gd. 3+ .

[0035] R + (R + For Li + 、Na + , K + One or more of these) can reduce the glass transition temperature. + If the content is greater than 5%, the liquidus temperature of the glass will increase. + The content of R is 0 to 5%, preferably 0 to 3%, and more preferably 0 to 2%. + .

[0036] F - It plays a significant role in adjusting the refractive index of glass, reducing the temperature coefficient of refractive index and the transition temperature, and is an important component for increasing the Abbe number and abnormal dispersion. - If the content is too high, it will weaken the stability of the glass, increase the thermal expansion coefficient and abrasion, especially during the melting process. - The volatilization of F will not only pollute the environment, but also make the optical constants of the glass exceed the design range. - When the content of F is less than 45%, the designed Abbe number and abnormal dispersion cannot be obtained; if the content is higher than 55%, the Abbe number of the glass will become too large, and the volatilization will increase sharply when it is melted and used for precision molding. - The content is limited to 45 to 55%, preferably 46 to 53%, and more preferably 47 to 51%.

[0037] The inventors have conducted extensive research and found that in some embodiments, by controlling F - The content of Al 3+ Mg 2+ , P 5+ , Y 3+ , Gd 3+ Total content of Al 3+ +Mg 2+ +P 5+ +Y 3+ +Gd 3+ The ratio F - / (Al 3+ +Mg 2+ +P 5+ +Y 3+ +Gd 3+) is below 5.0, which can effectively reduce the thermal expansion coefficient of the glass. However, when the ratio is lower than 2.0, the transition temperature of the glass increases, the liquidus temperature increases, and the production difficulty increases. Therefore, it is preferred that F - / (Al 3+ +Mg 2+ +P 5+ +Y 3+ +Gd 3+ ) is 2.0 to 5.0, and more preferably F - / (Al 3+ +Mg 2+ +P 5+ +Y 3+ +Gd 3+ ) is 2.5 to 4.0, and more preferably

[0038] F - / (Al 3+ +Mg 2+ +P 5+ +Y 3+ +Gd 3+ ) is 2.7~3.2.

[0039] The optical glass of the present invention contains O 2- , especially by containing more than 15% O 2- , can obtain excellent optical properties and low wear, but when O 2- When the content is greater than 25%, the liquidus temperature of the glass rises rapidly. 2- The content of is 15 to 25%, preferably 17 to 23%, and more preferably 19 to 21%.

[0040] The inventors have found through a large number of experimental studies that in some embodiments, controlling F - and O 2- Total content F - +O 2- With P 5+ The ratio between the contents of - +O 2- ) / P 5+ In the range of 8.0 to 15.0, the glass can have the desired optical constants while reducing the density of the glass and optimizing the thermal stability and coloring of the glass. - +O 2- ) / P 5+ 8.0 to 15.0, more preferably (F - +O 2- ) / P 5+ is 9.0 to 13.0, and more preferably (F - +O 2- ) / P 5+It is 10.0~12.0.

[0041] In some embodiments, Ba 2+ , Y 3+ , Gd 3+ ,La 3+ and O 2- Total content of Ba 2+ +Y 3+ +Gd 3+ +La 3+ +O 2- With P 5+ The ratio between the contents of 2+ +Y 3+ +Gd 3+ +La 3+ +O 2- ) / P 5+ When the value is controlled within the range of 3.0 to 5.5, the glass can obtain a lower density and thermal expansion coefficient while improving the resistance to devitrification of the glass. 2+ +Y 3+ +Gd 3+ +La 3+ +O 2- ) / P 5+ is 3.0 to 5.5, more preferably (Ba 2+ +Y 3+ +Gd 3+ +La 3+ +O 2- ) / P 5+ is 3.5 to 5.0, and more preferably (Ba 2+ +Y 3+ +Gd 3+ +La 3+ +O 2- ) / P 5+ It is 3.8 to 4.5.

[0042] The optical glass of the present invention may contain less than 1% of a clarifier to improve the clarification effect of the glass. The clarifier is Cl - Br - ,I - , Sb 3+ One or more components in the clarifier may corrode platinum utensils when the clarifier content is too high. Therefore, the content of the clarifier in the present invention is 0-1%, preferably 0-0.5%, and more preferably 0-0.3%.

[0043] Without impairing the excellent properties of the glass of the present invention, the optical glass of the present invention may contain Ta, 5+ , W 6+ ,Ge 4+ 、Bi3+ 、Te 4+ And other components.

[0044] <Ingredients that should not be contained>

[0045] Without impairing the excellent properties of the glass of the present invention, other components not mentioned above can be added as needed. However, transition metal components such as Ce, V, Cr, Mn, Fe, Co, Ni, Cu, Ag and Mo, even if contained in small amounts alone or in combination, will color the glass and produce absorption at specific wavelengths in the visible light region, thereby weakening the property of improving the visible light transmittance of the present invention. Therefore, it is preferred that the optical glass, especially for optical glass with required transmittance at wavelengths in the visible light region, substantially does not contain the above components.

[0046] The cations of Pb, 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 not actually contained except for the inevitable mixing. Thus, 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.

[0047] Next, the properties of the optical glass of the present invention will be described.

[0048] <Refractive Index and Abbe Number>

[0049] The refractive index of optical glass (n d ) and the Abbe number (ν d ) Tested according to the method specified in GB / T 7962.1-2010.

[0050] The optical glass of the present invention is a low-refractive-index and low-dispersion optical glass. The lens made of the low-refractive-index and low-dispersion optical glass is often combined with the lens made of the high-refractive-index and high-dispersion optical glass for chromatic aberration correction.

[0051] In some embodiments, the refractive index (n d ) is 1.46 to 1.52, and preferably the refractive index (n d ) is 1.47 to 1.51, and the refractive index (n d ) is 1.48~1.50.

[0052] In some embodiments, the Abbe number (ν d ) is 81 to 88, preferably the Abbe number (ν d) is 83 to 88, and more preferably the Abbe number (ν d ) is 84~87.

[0053] <Color>

[0054] The short-wave transmission spectrum characteristics of the optical glass of the present invention are expressed by the coloring degree (λ 80 / λ5). 80 It refers to the wavelength when the glass transmittance reaches 80%, and λ5 refers to the wavelength when the glass transmittance reaches 5%. 80 The measurement is to use a glass with a thickness of 10±0.1mm and two parallel and optically polished opposite planes, and measure the spectral transmittance in the wavelength range from 280nm to 700nm and the wavelength at which the transmittance is 80%. The so-called spectral transmittance or transmittance refers to the wavelength at which the incident intensity I is perpendicular to the above surface of the glass. in Light of intensity I passes through the glass and is emitted from another plane out In the case of light, through I out / I in λ is a quantity expressed by λ, and also includes the transmittance of the surface reflection loss on the above-mentioned surface of the glass. In the glass of the present invention, λ 80 A small value of means that the glass itself is less colored. The same is true for λ5.

[0055] In some embodiments, the λ of the optical glass of the present invention is 80 Less than or equal to 340nm, preferably λ 80 Less than or equal to 335nm, more preferably λ 80 Less than or equal to 330nm, more preferably λ 80 Less than or equal to 325nm, more preferably λ 80 Less than or equal to 320nm.

[0056] In some embodiments, the λ5 of the optical glass of the present invention 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, further preferably λ5 is less than or equal to 250 nm, and further preferably λ5 is less than or equal to 245 nm.

[0057] <density>

[0058] The density (ρ) of optical glass is measured according to the method specified in GB / T 7962.20-2010 and is the mass per unit volume at 20°C in g / cm 3 express.

[0059] In some embodiments, the density (ρ) of the optical glass of the present invention is 3.90 g / cm 3 Below, preferably 3.82 g / cm3 Below, more preferably 3.78g / cm 3 Below, more preferably 3.74 g / cm 3 the following.

[0060] <Transition Temperature>

[0061] Transition temperature of optical glass (T g ) Tested according to the method specified in GB / T 7962.16-2010.

[0062] In some embodiments, the transition temperature (T g ) is 500°C or lower, preferably 490°C or lower, more preferably 480°C or lower.

[0063] <Acid resistance stability>

[0064] The acid resistance (RA) (surface method) of optical glass is tested according to the method specified in GB / T 7962.14-2010.

[0065] In some embodiments, the acid resistance stability (RA) of the optical glass of the present invention is Class 3 or higher, preferably Class 2 or higher.

[0066] <Moisture resistance stability>

[0067] The moisture resistance stability (RC) (surface method) of optical glass is tested according to the method specified in GB / T 7962.15-2010.

[0068] In some embodiments, the optical glass of the present invention has a moisture resistance stability (RC) of Class 2 or above, preferably Class 1.

[0069] <Coefficient of Thermal Expansion>

[0070] Thermal expansion coefficient of optical glass (α 20～300℃ ) Tested according to the method specified in GB / T7962.16-2010.

[0071] In some embodiments, the thermal expansion coefficient (α 20～300℃ ) is 165×10 -7 / K or less, preferably 160×10 -7 / K or less, more preferably 155×10 -7 / K or less.

[0072] [Method for producing optical glass]

[0073] The manufacturing method of the optical glass of the present invention is as follows: the optical glass of the present invention is produced by conventional raw materials and conventional processes, using carbonates, nitrates, sulfates, phosphates, oxides, fluorides, metaphosphates, etc. as raw materials, and after the materials are prepared according to the conventional method, the prepared furnace materials are put into a melting furnace at 900-1000° C. for melting, and after clarification and sufficient homogenization, the optical glass of the present invention is obtained by pouring or leaking at a temperature below 800° C. Those skilled in the art can appropriately select raw materials, process methods and process parameters according to actual needs.

[0074] [Glass preforms and optical components]

[0075] The glass preform can be made from the produced optical glass by means of grinding, or by means of press molding such as re-hot pressing, precision stamping, etc. That is, the glass preform can be made by mechanical processing such as grinding and polishing the optical glass, or by making a preform for press molding from the optical glass, re-hot pressing the preform and then grinding the preform to make the glass preform, or by precision stamping the preform produced by grinding.

[0076] It should be noted that the means for preparing the glass preform is not limited to the above means. As described above, the optical glass of the present invention is useful for various optical elements and optical designs, and 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 make optical elements such as lenses and prisms.

[0077] The glass preform and the 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, and the optical element of the present invention has 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, which have spherical or aspherical lens surfaces.

[0078] [Optical instruments]

[0079] 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, display equipment and monitoring equipment.

[0080] Example

[0081] <Optical Glass Example>

[0082] In order to further clearly illustrate and describe the technical solution of the present invention, the following non-limiting examples are provided.

[0083] This embodiment adopts the above optical glass manufacturing method to obtain optical glasses having the compositions shown in Tables 1 to 4. In addition, the properties of each glass are measured by the testing method described in the present invention, and the measurement results are shown in Tables 1 to 4.

[0084] Table 1.

[0085] 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+ +Y 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+ +Y 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

[0086] Table 2.

[0087]

[0088]

[0089] Table 3.

[0090]

[0091]

[0092] Table 4.

[0093] 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+ +Y 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+ +Y 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

[0094] <Glass Preform Example>

[0095] The glass obtained from optical glass examples 1 to 30# is 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.

[0096] <Optical Element Embodiment>

[0097] The preforms obtained in the above-mentioned glass preform embodiments are annealed to reduce the internal stress of the glass and fine-tune the refractive index so that the optical properties such as the refractive index reach the desired values.

[0098] 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.

[0099] <Optical Instrument Embodiment>

[0100] 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, and 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.

Claims

1. Optical glass, characterized in that: Its components are expressed in molar percentage and contain: 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%.

2. The optical glass according to claim 1, characterized in that: Its components, expressed in molar percentage, also contain: 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 clarifier: 0-1%, the R + For Li + 、Na + , K + One or more of the following, the clarifier is Cl - Br - ,I - , Sb 3+ One or more of .

3. Optical glass, characterized in that: Its components are expressed in mole percentage, starting with 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%; clarifier: 0~1% composition, the R + For Li + 、Na + , K + One or more of the following, the clarifier is Cl - Br - ,I - , Sb 3+ One or more of .

4. The optical glass according to any one of claims 1 to 3, characterized in that: Its components are expressed in molar percentage, among which: Mg 2+ / Al 3+ 0 to 0.3, preferably Mg 2+ / Al 3+ 0 to 0.2, more preferably Mg 2+ / Al 3+ It is 0 to 0.

1.

5. The optical glass according to any one of claims 1 to 3, characterized in that: Its components are expressed in molar percentage, where: (Al 3+ -Mg 2+ -Li + ) / P 5+ is 1.1 to 2.5, preferably (Al 3+ -Mg 2+ -Li + ) / P 5+ is 1.2 to 2.3, more preferably (Al 3+ -Mg 2 + -Li + ) / P 5+ It is 1.3 to 2.

1.

6. The optical glass according to any one of claims 1 to 3, characterized in that: Its components are expressed in molar percentages, where: (F - -3×Al 3+ ) / P 5+ 2.3 to 5.0, preferably (F - -3×Al 3+ ) / P 5+ is 2.5 to 4.2, more preferably (F - -3×Al 3+ ) / P 5 + It is 2.7 to 3.

4.

7. The optical glass according to any one of claims 1 to 3, characterized in that: Its components are expressed in molar percentage, among which: Mg 2+ +Li + 0-3%, preferably Mg 2+ +Li + 0-2%, more preferably Mg 2+ +Li + 0~1%.

8. The optical glass according to any one of claims 1 to 3, characterized in that: Its components are expressed in molar percentage, where: F - / (Al 3+ +Mg 2+ +P 5+ +Y 3+ +Gd 3+ ) is 2.0 to 5.0, preferably F - / (Al 3+ +Mg 2+ +P 5+ +Y 3+ +Gd 3+ ) is 2.5 to 4.0, and more preferably F - / (Al 3+ +Mg 2+ +P 5+ +Y 3+ +Gd 3+ ) is 2.7~3.

2.

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

0.

10. The optical glass according to any one of claims 1 to 3, characterized in that: Its components are expressed in molar percentage, where: (Ba 2+ +Y 3+ +Gd 3+ +La 3+ +O 2- ) / P 5+ 3.0~5.5, preferably (Ba 2+ +Y 3+ +Gd 3+ +La 3+ +O 2- ) / P 5+ is 3.5 to 5.0, more preferably (Ba 2+ +Y 3+ +Gd 3+ +La 3+ +O 2- ) / P 5+ It is 3.8 to 4.

5.

11. The optical glass according to any one of claims 1 to 3, characterized in that: Its components are expressed in molar percentage, where: P 5+ : 4-8%, preferably P 5+ :4.5~6.5%;and / or Al 3+ : 6-13%, preferably Al 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 to 3%, preferably no Mg 2+ ; and / or Y 3+ : 0-2%, preferably 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 to 2%, preferably no R + ; and / or F - : 46-53%, preferably F - : 47-51%; and / or O 2- : 17-23%, preferably O 2- : 19-21%; and / or clarifier: 0-0.5%, preferably clarifier: 0-0.3%, the R + For Li + 、Na + , K + One or more of the following, the clarifier is Cl - Br - ,I - , Sb 3+ One or more of .

12. 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 refractive index n is preferably 1.46 to 1.

52. d The refractive index n is preferably 1.47 to 1.

51. d 1.48~1.50; Abbe number ν d 81 to 88, preferably Abbe number ν d 83 to 88, more preferably Abbe number ν d It is 84 to 87.

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

14. A glass preform, characterized in that: Made of the optical glass described in any one of claims 1 to 13.

15. An optical element, characterized in that The optical glass is made of any one of claims 1 to 13, or the glass preform is made of claim 14.

16. An optical instrument, characterized in that Contains the optical glass according to any one of claims 1 to 13, and / or contains the optical element according to claim 15.

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