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 present invention relates to optical glass, in particular to low-refractive and low-dispersion optical glass, and glass preforms, optical elements and optical instruments 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 existing technology, 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 fields such as mobile phones, vehicles, and security, optical systems have become more miniaturized and sophisticated, and their application environments have become more complex, placing higher demands on the temperature stability and lightweightness 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, its components expressed in 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%.

[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%, 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, its components are expressed in molar percentage, wherein: Mg 2+ / Al 3+ 0~0.3, preferably Mg 2+ / Al 3+ 0 to 0.2, more preferably Mg 2+ / Al 3+ It is 0 to 0.1.

[0010] Furthermore, the components of the optical glass are expressed in molar percentages, wherein:

[0011] (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.

[0012] Furthermore, the components of the optical glass are expressed in molar percentages, wherein: - -3×Al 3+ ) / P 5+ is 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.

[0013] Furthermore, the optical glass, its components are expressed in molar percentage, wherein: Mg 2+ +Li + 0-3%, preferably Mg 2+ +Li + 0-2%, more preferably Mg 2+ +Li + 0 to 1%.

[0014] Furthermore, the components of the optical glass are expressed in molar percentages, 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, more preferably F - / (Al 3+ +Mg 2+ +P 5+ +Y 3+ +Gd 3+ ) is 2.7~3.2.

[0015] Furthermore, the components of the optical glass are expressed in molar percentages, 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.

[0016] Furthermore, the components of the optical glass are expressed in molar percentages, wherein:

[0017] (Ba 2+ +Y 3+ +Gd 3+ +La 3+ +O 2- ) / P 5+ is 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.

[0018] Furthermore, the components of the optical glass are expressed in molar percentages, 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+ : 0-3%, more 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 Gd3+ : 0-2%, preferably Gd 3+ :0~1%;and / or R + : 0~3%, preferably R + : 0-2%, more preferably no R + ; and / or F - : 46~53%, preferably F - : 47-51%; and / or O 2- : 17~23%, preferably O 2- : 19 to 21%; and / or clarifier: 0 to 0.5%, preferably clarifier: 0 to 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 .

[0019] 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 1.47 to 1.51, and more preferably 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.

[0020] 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 3 Below, the more preferred density ρ is 3.78 g / cm 3 Hereinafter, the density ρ is further preferably 3.74 g / cm 3 Below; and / or transition temperature T gThe transition temperature T is preferably below 500°C. g The transition temperature is 490°C or lower, and more preferably the transition temperature T g 480 ° C or less; and / or acid stability RA 3 or more, preferably acid stability RA 2 or more; and / or moisture stability RC 2 or more, preferably moisture stability RC 1; and / or thermal expansion coefficient α 20～300℃ 165×10 -7 / K or less, preferably the thermal expansion coefficient α 20～300℃ 160×10 -7 / K or less, more preferably the thermal expansion coefficient 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.

[0021] The glass preform is made of the above-mentioned optical glass.

[0022] The optical element is made of the above optical glass, or made of the above glass preform.

[0023] An optical instrument contains the above-mentioned optical glass and / or contains the above-mentioned optical element.

[0024] The beneficial effects of the present invention are: through reasonable component design, the optical glass of the present invention has excellent optical properties and moldability, as well as low thermal expansion coefficient and density. DETAILED DESCRIPTION

[0025] The following describes in detail embodiments of the optical glass of the present invention. However, the present invention is not limited to the embodiments described below and can be implemented with appropriate modifications within the scope of the present invention. Furthermore, although repeated descriptions may be omitted as appropriate, this does not limit the scope of the invention. In the following description, the optical glass of the present invention may be simply referred to as "glass."

[0026] [Optical glass]

[0027] The following describes the ranges of the components (ingredients) that make up the optical glass of the present invention. In this specification, unless otherwise specified, each component is expressed in mole percentage, i.e., 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.

[0028] Unless otherwise indicated in specific circumstances, the numerical ranges listed herein include upper and lower limits, and "above" and "below" include the endpoints, as well as all integers and fractions included in the range, without limitation to the specific values listed when defining the range. The term "and / or" herein is inclusive, for example, "A and / or B" means only A, or only B, or both A and B.

[0029] 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 optical glass may be other than the representative values. For example, P usually exists in the glass with an ionic valence of +5, 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.

[0030] <Essential Components and Optional Components>

[0031] P 5+ It is a component of the optical glass of the present invention, which 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 optical performance that is difficult to meet the design requirements. Therefore, P in the present invention 5+ The content of is 3 to 10%, preferably 4 to 8%, more preferably 4.5 to 6.5%.

[0032] Al 3+ It can improve the stability of the glass of the present invention, 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 achieve the above-mentioned effects; if its content is higher than 15%, the transition temperature and liquidus temperature of the glass increase, making glass melting difficult. At the same time, the temperature during molding increases, resulting in increased volatilization of the glass and worsening the glass striations; on the other hand, too high a transition temperature makes compression molding difficult. Therefore, the Al in the present invention is 3+ The content of is 3 to 15%, preferably 6 to 13%, more preferably 8 to 11%.

[0033] Ba 2+ It has the effect of improving the refractive index, thermal stability and weather resistance of glass, but too much Ba 2+ It will lead to an increase in the density and thermal expansion coefficient of the glass, and a worsening of the abrasiveness. 2+ The content of is 2 to 10%, preferably 3 to 8%, more preferably 4.5 to 6.5%.

[0034] 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 of is 2 to 10%, preferably 3 to 8%, more preferably 4 to 6%.

[0035] 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 much, the refractive index of glass will be 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%.

[0036] Mg 2+ Can improve the abrasiveness of 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%, more preferably 0-3%. In some embodiments, it is further preferred that Mg is not contained. 2+ .

[0037] In some embodiments, by controlling Mg 2+ Content and Al 3+ The ratio between the content of Mg 2+ / Al 3+ When the glass is below 0.3, the thermal expansion coefficient of the glass can be reduced while the glass can obtain excellent anti-devitrification performance. 2+ / Al 3+ 0 to 0.3, more preferably Mg 2+ / Al 3+ 0 to 0.2, more preferably Mg 2+ / Al 3+ It is 0 to 0.1.

[0038] In some embodiments, by controlling Al 3+ The content of Mg 2+ 、Li + The difference in Al content 3+ -Mg 2+ -Li + With P 5+ The ratio between the contents of 3+ -Mg 2+ -Li + ) / P 5+In the range of 1.1 to 2.5, the glass can easily obtain the desired optical constants while reducing the thermal expansion coefficient and liquidus temperature of the glass, thereby reducing the difficulty of glass production. 3+ -Mg 2 + -Li + ) / P 5+ is 1.1 to 2.5, more 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.

[0039] 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%, more preferably 0-1%. In some embodiments, Y can be introduced by using Y fluoride, oxide and Y-containing salts. 3+ .

[0040] 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 easily devitrified 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 fluorides, oxides, and La-containing salts. 3+ .

[0041] Gd 3+ It can improve the chemical stability of glass, maintain low dispersion while properly increasing the refractive index, and properly 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, or salt containing Gd. 3+ .

[0042] R + (R + For Li + 、Na + , K +One or more of these) can reduce the glass transition temperature. If R + If the content is greater than 5%, the liquidus temperature of the glass will increase. + The content of R is 0-5%, preferably 0-3%, more preferably 0-2%. In some embodiments, it is further preferred that R + .

[0043] In some embodiments, by containing a certain amount of Mg 2+ He Li + , can increase the refractive index of glass, but when the total content of Mg 2+ +Li + When it exceeds 3%, the thermal stability of the glass is greatly reduced, the production difficulty increases and the density increases. Therefore, Mg is preferably 2+ +Li + 0-3%, more preferably Mg 2+ +Li + 0-2%, more preferably Mg 2+ +Li + 0 to 1%.

[0044] F - It plays a significant role in adjusting the refractive index of glass, reducing the temperature coefficient of refractive index and 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%.

[0045] 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, more 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.

[0046] In some embodiments, by controlling (F - -3×Al 3+ ) / P 5+ In the range of 2.3 to 5.0, the glass can have a lower thermal expansion coefficient while having the desired optical constants. - -3×Al 3+ ) / P 5+ is 2.3 to 5.0, more 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.

[0047] 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%, more preferably 19 to 21%.

[0048] The inventors have found through a large number of experimental studies that in some embodiments, controlling F - and O2- 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.

[0049] In some embodiments, Ba 2+ 、Y 3+ 、Gd 3+ 、La 3+ and O 2- The 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, more preferably (Ba 2+ +Y 3+ +Gd 3+ +La 3+ +O 2-) / P 5+ It is 3.8 to 4.5.

[0050] 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%.

[0051] 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+ 、Bi 3+ 、Te 4+ and other components.

[0052] <Ingredients that should not be contained>

[0053] Other components not mentioned above may be added as needed without impairing 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 present alone or in combination in small amounts, can color the glass and absorb specific wavelengths in the visible light region, thereby reducing the visible light transmittance-enhancing effect of the present invention. Therefore, for optical glasses requiring transmittance in the visible light region, it is preferred that these components be substantially absent.

[0054] In recent years, the use of cations of Pb, Th, Cd, Tl, Os, Be, and Se has been regulated as hazardous chemicals. Environmental protection measures are essential not only in the glass manufacturing process, but also in processing and post-product disposal. Therefore, given the importance of environmental impact, it is preferable to practically exclude these cations, except where they are unavoidably incorporated. This results in an optical glass that is virtually free of environmentally polluting substances. Therefore, even without taking specific environmental countermeasures, the optical glass of the present invention can be manufactured, processed, and disposed of.

[0055] Next, the properties of the optical glass of the present invention will be described.

[0056] <Refractive Index and Abbe Number>

[0057] The refractive index of optical glass (n d ) and Abbe number (ν d) Tested in accordance with the method specified in GB / T 7962.1-2010.

[0058] The optical glass of the present invention is a low-refractive-index and low-dispersion optical glass. Lenses made of the low-refractive-index and low-dispersion optical glass are often combined with lenses made of high-refractive-index and high-dispersion optical glass to correct chromatic aberration.

[0059] In some embodiments, the refractive index (n d ) is 1.46 to 1.52, and the preferred refractive index (n d ) is 1.47 to 1.51, and the refractive index (n d ) is 1.48~1.50.

[0060] 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 to 87.

[0061] <Color>

[0062] The short-wave transmission spectrum characteristics of the optical glass of the present invention are expressed by the coloration (λ 80 / λ5) indicates. 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 surfaces to 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 The amount expressed by λ 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 applies to λ5.

[0063] 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 80Less than or equal to 320nm.

[0064] 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 even further preferably λ5 is less than or equal to 245 nm.

[0065] <density>

[0066] 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 a temperature of 20°C, in g / cm 3 express.

[0067] 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 / cm 3 Below, more preferably 3.78g / cm 3 Below, more preferably 3.74 g / cm 3 the following.

[0068] <Transition Temperature>

[0069] Transition temperature of optical glass (T g ) Tested in accordance with the method specified in GB / T 7962.16-2010.

[0070] In some embodiments, the transition temperature (T g ) is 500°C or lower, preferably 490°C or lower, more preferably 480°C or lower.

[0071] <Acid resistance stability>

[0072] The acid resistance (RA) (surface method) of optical glass is tested in accordance with the method specified in GB / T 7962.14-2010.

[0073] 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.

[0074] <Moisture resistance stability>

[0075] The moisture resistance (RC) (surface method) of optical glass is tested in accordance with the method specified in GB / T 7962.15-2010.

[0076] In some embodiments, the optical glass of the present invention has a humidity resistance (RC) of Class 2 or higher, preferably Class 1.

[0077] <Coefficient of Thermal Expansion>

[0078] Thermal expansion coefficient of optical glass (α 20～300℃ ) Tested in accordance with the method specified in GB / T7962.16-2010.

[0079] 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.

[0080] <Anti-crystallization performance>

[0081] The test method for the anti-crystallization performance of the optical glass of the present invention is as follows: a glass sample of 10 mm × 20 mm × 20 mm is placed in a semicircular porcelain box with a radius of 15 mm and a depth of 15 mm, and the glass sample and the porcelain box are placed in a T g The first heating is carried out in a test furnace of 140-160℃ for 15 minutes, and then the temperature is lowered to 200℃ in a tunnel annealing furnace; then the holding temperature is stabilized at T g + (140 ~ 160 ℃) test furnace for a second heating, the heating time is 15 minutes, then taken out and cooled again to 200 ℃ in the tunnel annealing furnace. After the second heating, place the glass sample and the porcelain box in the tunnel annealing furnace and reduce the temperature to 200 ℃. After taking out the glass sample, it is naturally cooled to room temperature in the atmosphere. After the glass sample is ground and polished, the overall softening degree and devitrification of the glass are observed with the naked eye, and the inside of the glass is observed under a microscope to confirm the presence of crystallization particles. The anti-crystallization performance of the glass is judged according to Table 1 below, with grade A being the best and grade E being the worst.

[0082] Table 1. Classification and judgment criteria of anti-crystallization performance

[0083]

[0084] In some embodiments, the optical glass of the present invention has an anti-crystallization performance of Class B or above, preferably Class A, and has excellent thermal stability.

[0085] [Method for manufacturing optical glass]

[0086] The optical glass of the present invention is produced using conventional raw materials and processes. Raw materials such as carbonates, nitrates, sulfates, phosphates, oxides, fluorides, and metaphosphates are prepared according to conventional methods. The prepared materials are then melted in a furnace at 900-1000°C. After clarification and thorough homogenization, the glass is cast or funneled at a temperature below 800°C to obtain the optical glass of the present invention. Those skilled in the art will be able to appropriately select the raw materials, process methods, and process parameters based on actual needs.

[0087] [Glass preforms and optical components]

[0088] A glass preform can be produced from the produced optical glass using, for example, grinding, or press molding such as re-hot pressing or precision stamping. Specifically, the glass preform can be produced by mechanical processing such as grinding or lapping the optical glass, or by producing a preform for press molding from the optical glass, re-hot pressing the preform, and then grinding the preform, or by precision stamping the preform produced by grinding.

[0089] It should be noted that the means for preparing glass preforms are not limited to the above-mentioned means. As described above, the optical glass of the present invention is useful for various optical elements and optical designs. It is particularly preferred to form a preform from the optical glass of the present invention and use this preform to perform re-hot pressing, precision stamping, etc. to produce optical elements such as lenses and prisms.

[0090] The glass preform and optical element of the present invention are both formed from the optical glass of the present invention. 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, each having a spherical or aspherical lens surface.

[0091] [Optical Instruments]

[0092] The optical elements formed by the optical glass of the present invention can be used to make optical instruments such as photographic equipment, video equipment, display equipment and monitoring equipment.

[0093] Example

[0094] <Optical Glass Example>

[0095] In order to further clearly illustrate and describe the technical solutions of the present invention, the following non-limiting examples are provided.

[0096] This embodiment uses the above-mentioned optical glass manufacturing method to obtain optical glasses having the compositions shown in Tables 2 to 5. In addition, the properties of each glass were measured using the testing method described in the present invention, and the measurement results are shown in Tables 2 to 5.

[0097] Table 2.

[0098]

[0099]

[0100] Table 3.

[0101]

[0102]

[0103] Table 4.

[0104]

[0105]

[0106] Table 5.

[0107]

[0108]

[0109] <Glass Preform Example>

[0110] The glass obtained from optical glass examples 1 to 30# is used to make preforms of various lenses, prisms, etc., such as concave meniscus lenses, convex meniscus lenses, double convex lenses, double concave lenses, plano-convex lenses, and plano-concave lenses, using methods such as grinding processing, or molding methods such as re-hot pressing, precision stamping, etc.

[0111] <Optical Element Example>

[0112] The preforms obtained from 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.

[0113] Each preform is then ground and polished to produce various lenses and prisms, including concave meniscus lenses, convex meniscus lenses, biconvex lenses, biconcave lenses, plano-convex lenses, and plano-concave lenses. The surfaces of the resulting optical elements can also be coated with an anti-reflection film.

[0114] <Optical Instrument Example>

[0115] The optical elements made from the above-mentioned optical element embodiments are optically designed and formed into optical components or optical assemblies using one or more optical elements, which 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, photolithography 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 percentages 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, wherein 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 percentages, 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%, 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 percentages, where: Mg 2+ / Al 3+ 0~0.3, 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 percentages, 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+ is 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 percentages, where: Mg 2+ +Li + 0-3%, preferably Mg 2+ +Li + 0-2%, more preferably Mg 2+ +Li + 0 to 1%.

8. The optical glass according to any one of claims 1 to 3, characterized in that: Its components are expressed in mole percentages, 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, 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 percentages, 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 mole percentages, 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+ : 0-3%, more 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 + : 0-2%, more preferably no R + ; and / or F - : 46~53%, preferably F - : 47-51%; and / or O 2- : 17~23%, preferably O 2- : 19 to 21%; and / or clarifier: 0 to 0.5%, preferably clarifier: 0 to 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 1.47 to 1.51, and more preferably 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 Hereinafter, 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 490°C or lower, and more preferably the transition temperature T g 480 ° C or less; and / or acid stability RA 3 or more, preferably acid stability RA 2 or more; and / or moisture stability RC 2 or more, preferably moisture stability RC 1; and / or thermal expansion coefficient α 20～300℃ 165×10 -7 / K or less, preferably the thermal expansion coefficient α 20～300℃ 160×10 -7 / K or less, more preferably the thermal expansion coefficient 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 according to 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 Containing the optical glass according to any one of claims 1 to 13, and / or containing the optical element according to claim 15.

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