Fluorophosphate optical glass and optical element

Abstract

The invention provides fluorophosphate optical glass with excellent thermal shock resistance. The fluorophosphate optical glass comprises the following cation components in percentage by mole: 11-25% of P < 5 + >; 16%-30% of Al < 3 + >; ba2 +: greater than or equal to 8% but less than 20%; 12-26% of Sr < 2 + >; 7%-20% of Mg < 2 + >; 7%-20% of Ca < 2 + >; ln3 +: greater than 0% but less than or equal to 10%; 0-8% of Rn < + >, (Mg < 2 + >-Ln < 3 + >) / (Sr < 2 + >-Ba < 2 + >-Rn < + >) is 1.0-12.0, Ln < 3 + > is one or more of La < 3 + >, Gd < 3 + >, Y < 3 + > and Yb < 3 + >, and Rn < + > is one or more of Li < + >, Na < + > and K < + >; the anion component contains 61 to 80 percent of F-; and 20-39% of O < 2->. Through reasonable component design, the fluorophosphate optical glass obtained by the invention has excellent thermal shock resistance, and is suitable for manufacturing optical elements by precise mould pressing.

Description

TECHNICAL FIELD

[0001] The present application relates to an optical glass, in particular to a fluorophosphate optical glass, and an optical element made therefrom. BACKGROUND

[0002] As a new type of glass material widely used, fluorophosphate optical glass has the characteristics of low dispersion, which can eliminate the secondary spectrum special dispersion in optical system, improve the resolution, and significantly improve the imaging quality of optical system. The mainstream manufacturing method of optical elements is precision molding (including direct molding method and secondary molding method). The lenses manufactured by using the precision molding technology usually do not need to be ground and polished, thereby reducing the consumption of raw materials, reducing the cost of manpower and material resources, and reducing environmental pollution. The technology can produce non-spherical elements in large quantities at low cost. So-called precision molding is to mold a glass preform under certain temperature and pressure by using a high-precision mold with a predetermined product shape, so as to obtain a glass product with a final product shape and optical function. Various optical elements such as spherical lenses, aspherical lenses, prisms and diffraction gratings can be manufactured by using the precision molding technology. The optical glass suitable for precision molding needs to have a relatively low transition temperature to ensure the feasibility of molding and prolong the service life of the molding mold. In addition, the optical glass also needs to have excellent molding performance. If the molding performance of the glass is poor, the glass is prone to breakage during precision molding, thereby resulting in a low yield of optical elements. SUMMARY

[0003] Based on the above reasons, the present inventors have found through long-term and large-scale research that the breakage of fluorophosphate glass precision molding to manufacture aspherical lenses mainly occurs in the cooling section after the high-temperature molding of the glass preform, that is, in the temperature range of 10-30℃ below the molding temperature (usually the sag temperature (T s ) of the glass) to the transition temperature (T g ) of the glass. When using alloy or ceramic molds for precision molding, this temperature range is usually the stage of rapid cooling and setting of the molded lenses by the mold covering on the lenses. To ensure the setting accuracy of the aspherical lenses, the mold often maintains a certain pressure at this time. If the heat shock resistance of the glass is insufficient in this temperature range, the thermal stress generated by the heat shock during cooling will cause the lenses to break. Through a large number of experiments, the present inventors have carefully studied and analyzed the content relationship of each component of fluorophosphate glass, especially the content ratio relationship of Mg 2+ , Sr 2+ , Ba 2+ , lanthanide components (Ln 3+ ) and alkali metal components (Rn + ), and solved the problem of insufficient heat shock resistance of the glass, thereby completing the present application.

[0004] The present application provides a fluorophosphate optical glass with excellent heat shock resistance.

[0005] The technical scheme adopted by the present application to solve the technical problem is:

[0006] (1) A fluorophosphate optical glass, the components of which are expressed in mole percentage, the cation component comprising: P 5+ : 11-25%; Al 3+ : 16-30%; Ba 2+ : greater than or equal to 8% but less than 20%; Sr 2+ : 12-26%; Mg 2+ : 7-20%; Ca 2+ : 7-20%; Ln 3+ : greater than 0% but less than or equal to 10%; Rn + : 0-8%, wherein (Mg 2+ -Ln 3+ ) / (Sr 2+ -Ba 2+ -Rn + ) is 1.0-12.0, the Ln 3+ is one or more of La 3+ , Gd 3+ , Y 3+ , Yb 3+ , and the Rn + is one or more of Li + , Na + , K + ;

[0007] The anion component comprises: F - : 61-80%; O 2- : 20-39%.

[0008] (2) The fluorophosphate optical glass according to (1), the components of which are expressed in mole percentage, the cation component further comprising: Nb 5+ + W 6+ : 0-8%; and / or Ti 4+ : 0-3%; and / or Zn 2+ : 0-5%; and / or Ta 5+ : 0-5%; and / or B 3+ : 0-5%; and / or Si 4+ : 0-5%; and / or Sb 3+ : 0-1%; and / or Sn 4+ : 0-1%; and / or Ce 4+ : 0-1%;

[0009] anion component also contains: Cl - + Br - + I - : 0-2%.

[0010] (3) Fluorophosphate optical glass, the component of which contains P 5+ , Al 3+ , Ba 2+ , Sr 2+ , Mg 2+ , Ca 2+ , Ln 3+ , F - and O 2- , the component being expressed in mole percent, contains 0-8% of Rn + , wherein (Mg 2+ -Ln 3+ ) / (Sr 2+ -Ba 2+ -Rn + ) is 1.0-12.0, said Ln 3+ is one or more of La 3+ , Gd 3+ , Y 3+ , Yb 3+ , said Rn + is one or more of Li + , Na + , K + , the refractive index n d of said fluorophosphate optical glass is 1.46-1.53, the Abbe number v d is 78-86, and the heat shock resistance coefficient β is 10.0 x 10 3 or more.

[0011] (4) Fluorophosphate optical glass according to (3), the component of which, expressed in mole percent, contains: P 5+ : 11-25%; and / or Al 3+ : 16-30%; and / or Ba 2+ : more than or equal to 8% but less than 20%; and / or Sr 2+ : 12-26%; and / or Mg 2+ : 7-20%; and / or Ca 2+ : 7-20%; and / or Ln 3+ : more than 0% but less than or equal to 10%; and / or Nb 5+ + W 6+ : 0-8%; and / or Ti 4+ : 0-3%; and / or Zn 2+ : 0-5%; and / or Ta5+ 0 to 5%; and / or B 3+ 0 to 5%; and / or Si 4+ 0 to 5%; and / or Sb 3+ 0 to 1%; and / or Sn 4+ 0 to 1%; and / or Ce 4+ 0 to 1%, the Ln 3+ is one or more of La 3+ , Gd 3+ , Y 3+ , Yb 3+ , the Rn + is one or more of Li + , Na + , K + ;

[0012] The anion component contains: F - 61 to 80%; and / or O 2- 20 to 39%; and / or Cl - + Br - + I - 0 to 2%.

[0013] (5) The fluorophosphate optical glass according to any one of (1) to (4), the components of which are expressed in mole percent, satisfies one or more of the following six conditions:

[0014] 1) (Mg 2+ -Ln 3+ ) / (Sr 2+ -Ba 2+ -Rn + ) is 1.5 to 10.0, preferably (Mg 2+ -Ln 3+ ) / (Sr 2+ -Ba 2+ -Rn + ) is 2.0 to 7.0, more preferably (Mg 2+ -Ln 3+ ) / (Sr 2+ -Ba 2+ -Rn + ) is 2.5 to 4.5;

[0015] 2) (P 5+ + Ca 2+ + Rn + ) / Mg 2+ is 1.1 to 4.0, preferably (P 5+ + Ca 2+ + Rn + ) / Mg 2+1.3 to 3.5, more preferably (P 5+ + Ca 2+ + Rn + ) / Mg 2+ 1.5 to 3.0, further preferably (P 5+ + Ca 2+ + Rn + ) / Mg 2+ 1.8 to 2.5;

[0016] 3) (P 5+ + Ba 2+ ) / (Mg 2+ + Al 3+ ) 0.4 to 1.7, preferably (P 5+ + Ba 2+ ) / (Mg 2+ + Al 3+ ) 0.5 to 1.5, more preferably (P 5+ + Ba 2+ ) / (Mg 2+ + Al 3+ ) 0.6 to 1.2, further preferably (P 5+ + Ba 2+ ) / (Mg 2+ + Al 3+ ) 0.6 to 1.0;

[0017] 4) (Al 3+ + Rn + ) / Mg 2+ 0.8 to 4.0, preferably (Al 3+ + Rn + ) / Mg 2+ 1.0 to 3.0, more preferably (Al 3+ + Rn + ) / Mg 2+ 1.2 to 2.5, further preferably (Al 3+ + Rn + ) / Mg 2+ 1.2 to 2.0;

[0018] 5) (Mg 2+ + Ba 2+ ) / P 5+ 1.0 to 3.5, preferably (Mg 2+ + Ba 2+ ) / P 5+ 1.2 to 3.0, more preferably (Mg 2+ + Ba 2 + ) / P 5+ 1.3 to 2.5, further preferably (Mg2+ +Ba 2+ ) / P 5+ is 1.3 to 2.0;

[0019] 6) (Nb 5+ +W 6+ ) / Ln 3+ is 0.01 to 2.0, preferably (Nb 5+ +W 6+ ) / Ln 3+ is 0.05 to 1.5, more preferably (Nb 5+ +W 6 + ) / Ln 3+ is 0.05 to 1.0, further preferably (Nb 5+ +W 6+ ) / Ln 3+ is 0.1 to 0.7, said Ln 3+ is one or more of La 3+ , Gd 3+ , Y 3+ , Yb 3+ , said Rn + is one or more of Li + , Na + , K + .

[0020] (6) The fluorophosphate optical glass according to any one of (1) to (4), which components are expressed in terms of molar percentage, satisfies one or more of the following 4 cases:

[0021] 1) Zn 2+ / Mg 2+ is 0.5 or less, preferably Zn 2+ / Mg 2+ is 0.3 or less, more preferably Zn 2+ / Mg 2+ is 0.2 or less, further preferably Zn 2+ / Mg 2+ is 0.1 or less;

[0022] 2) Zn 2+ / Ln 3+ is 2.0 or less, preferably Zn 2+ / Ln 3+ is 1.0 or less, more preferably Zn 2+ / Ln 3+ is 0.8 or less, further preferably Zn 2+ / Ln 3+ is 0.5 or less;

[0023] 3) Rn + / Mg2+ is 0.35 or less, preferably Rn + / Mg 2+ is 0.3 or less, more preferably Rn + / Mg 2+ is 0.2 or less, further preferably Rn + / Mg 2+ is 0.1 or less;

[0024] 4) Rn + / Ln 3+ is 1.5 or less, preferably Rn + / Ln 3+ is 1.0 or less, more preferably Rn + / Ln 3+ is 0.8 or less, further preferably Rn + / Ln 3+ is 0.5 or less, said Ln 3+ is one or more of La 3+ , Gd 3+ , Y 3+ , Yb 3+ , said Rn + is one or more of Li + , Na + , K + .

[0025] (7) The fluorophosphate optical glass according to any one of (1) to (4), wherein the components are expressed in terms of molar percentage, and wherein: F - / (P 5+ +B 3+ ) is 2.5 to 6.5, preferably F - / (P 5+ +B 3+ ) is 3.0 to 6.0, more preferably F - / (P 5+ +B 3+ ) is 3.5 to 5.5, further preferably F - / (P 5+ +B 3+ ) is 3.5 to 5.0; and / or F - / O 2- is 1.8 to 3.8, preferably F - / O 2- is 1.8 to 3.5, more preferably F - / O 2- is 2.0 to 3.0, further preferably F - / O 2- is 2.0 to 2.8.

[0026] (8) The fluorophosphate optical glass according to any one of (1) to (4), whose components are expressed in terms of molar percentage, wherein: P 5+ : 13 to 23%, preferably P 5+ : 15 to 22%; and / or Al 3+ : 18 to 28%, preferably Al 3+ : 20 to 25%; and / or Ba 2+ : 10 to 18%, preferably Ba 2+ : 11 to 16%; and / or Sr 2+ : 14 to 24%, preferably Sr 2+ : 16 to 22%; and / or Mg 2+ : 8 to 18%, preferably Mg 2+ : 10.5 to 17%; and / or Ca 2+ : 8 to 18%, preferably Ca 2+ : 10.5 to 16.5%; and / or Ln 3+ : 0.1 to 8%, preferably Ln 3+ : 0.5 to 5%; and / or Nb 5+ + W 6+ : more than 0% but less than or equal to 6%, preferably Nb 5+ + W 6+ : 0.1 to 3%; and / or Ti 4+ : 0 to 2%, preferably Ti 4+ : 0 to 1%, more preferably free of Ti 4+ ; and / or Rn + : 0 to 4%, preferably Rn + : 0 to 2%, more preferably free of Rn + ; and / or Zn 2+ : 0 to 3%, preferably Zn 2+ : 0 to 1%, more preferably free of Zn 2+ ; and / or Ta 5 + : 0 to 3%, preferably Ta 5+ : 0 to 1%, more preferably free of Ta 5+ ; and / or B 3+ : 0 to 3%, preferably B 3+ : 0 to 1%, more preferably free of B 3+ ; and / or Si 4+ : 0 to 3%, preferably Si 4+ : 0 to 1%, more preferably free of Si 4+ ; and / or Sb 3+ : 0 to 0.5%, preferably Sb 3+ : 0 to 0.2%; and / or Sn 4+ : 0 to 0.5%, preferably Sn 4+: 0 to 0.2%, and / or Ce 4+ : 0 to 0.5%, preferably Ce 4+ : 0 to 0.2%, said Ln 3+ is La 3+ , Gd 3+ , Y 3+ , Yb 3+ one or more of, said Rn + is Li + , Na + , K + one or more of.

[0027] (9) The fluorophosphate optical glass according to any one of (1) to (4), wherein the components are expressed in terms of molar percentage, and wherein: F - : 63 to 75%, preferably F - : 65 to 73%; and / or O 2- : 25 to 37%, preferably O 2- : 27 to 35%; and / or Cl - + Br - + I - : 0 to 1%, preferably Cl - + Br - + I - : 0 to 0.5%.

[0028] (10) The fluorophosphate optical glass according to any one of (1) to (4), wherein the refractive index n d of the fluorophosphate optical glass is 1.46 to 1.53, preferably the refractive index n d is 1.47 to 1.52, more preferably the refractive index n d is 1.48 to 1.51; and the Abbe number v d of the fluorophosphate optical glass is 78 to 86, preferably the Abbe number v d is 79 to 84, more preferably the Abbe number v d is 80 to 83.

[0029] (11) The fluorophosphate optical glass according to any one of (1) to (4), wherein the weather resistance CR of the fluorophosphate optical glass is Class 2 or more, preferably the weather resistance CR is Class 1; and / or the water resistance stability D W is Class 2 or more, preferably the water resistance stability D W is Class 1; and / or the acid resistance stability D A is Class 3 or more, preferably the acid resistance stability D A is Class 2 or more; and / or the thermal expansion coefficient a -30～70℃ is 160 x 10 -7 / K or less, preferably the thermal expansion coefficient a 30～70℃ is 150 x 10-7 / K or less, more preferably the coefficient of thermal expansion α -30～70℃ is 140 x 10 -7 / K or less, further preferably the coefficient of thermal expansion α -30～70℃ is 120 x 10 -7 / K to 135 x 10 -7 / K; and / or the transition temperature T g is 500°C or less, preferably the transition temperature T g is 490°C or less, more preferably the transition temperature T g is 485°C or less; and / or the heat shock resistance coefficient β is 10.0 x 10 3 or more, preferably the heat shock resistance coefficient β is 13.0 x 10 3 or more, more preferably the heat shock resistance coefficient β is 15.0 x 10 3 or more, further preferably the heat shock resistance coefficient β is 16.0 x 10 3 or more; and / or the abrasion degree F A is 305 to 345, preferably the abrasion degree F A is 315 to 340, more preferably the abrasion degree F A is 320 to 335; and / or the density p is 4.20 g / cm 3 or less, preferably the density p is 4.10 g / cm 3 or less, more preferably the density p is 4.00 g / cm 3 or less, further preferably the density p is 3.95 g / cm 3 or less; and / or the λ 80 is 350 nm or less, preferably the λ 80 is 340 nm or less, more preferably the λ 80 is 335 nm or less; and / or the λ5 is 320 nm or less, preferably the λ5 is 310 nm or less, more preferably the λ5 is 305 nm or less; and / or the Knoop hardness H K is 330 x 10 7 Pa or more, preferably 350 x 10 7 Pa or more, more preferably 360 x 10 7 Pa or more; and / or the bubble degree is A class or more, preferably A0 class or more, more preferably A 00 class.

[0030] (12) A glass preform made of the fluorophosphate optical glass according to any one of (1) to (11).

[0031] (13) An optical element made of the fluorophosphate optical glass according to any one of (1) to (11) or the glass preform according to (12).

[0032] (14) An optical instrument comprising the fluoro phosphate optical glass according to any one of (1) to (11); and / or the optical element according to (13).

[0033] The present application has the following advantageous effects: By reasonable component design, the fluoro phosphate optical glass obtained by the present application has excellent heat shock resistance, and is suitable for precision mold pressing to manufacture optical elements. DETAILED DESCRIPTION

[0034] Hereinafter, the embodiments of the fluoro phosphate optical glass of the present application will be described in detail, but the present application is not limited to the following embodiments, and can be implemented by appropriately changing within the scope of the object of the present application. In addition, regarding the repeatedly described parts, although there are appropriately omitted descriptions, the gist of the present application is not limited thereto, and in the following content, the fluoro phosphate optical glass of the present application can be simply referred to as an optical glass or a glass.

[0035] [Fluoro phosphate optical glass]

[0036] Hereinafter, the range of each component (ingredient) constituting the optical glass of the present application will be described. In the present specification, unless otherwise specified, the content of the cation component is represented by the molar percentage (mol%) of the cation component with respect to the total cation components, the content of the anion component is represented by the molar percentage (mol%) of the anion component with respect to the total anion components; the ratio between the contents of the cation components is the ratio of the molar percentage contents between the contents of the cation components; the total content between the contents of the cation components is the total value of the molar percentage contents between the contents of the cation components; the difference between the contents of the cation components is the difference of the molar percentage contents between the contents of the cation components; the ratio between the contents of the anion components is the ratio of the molar percentage contents between the contents of the anion components; the total content between the contents of the cation and anion components is the total value between the molar percentage content of the cation component with respect to the total cation components and the molar percentage content of the anion component with respect to the total anion components; and the ratio between the contents of the cation and anion components is the ratio between the molar percentage content of the cation component with respect to the total cation components and the molar percentage content of the anion component with respect to the total anion components.

[0037] Unless otherwise indicated in specific cases, the numerical ranges listed herein include the upper and lower limit values, "above" and "below" include the end point values, and all integers and fractions within the range, and are not limited to the specific values listed in the defined range. As referred to herein, "and / or" is inclusive, for example, "A and / or B" means only A, or only B, or both A and B.

[0038] Note that the ion valence of each component described below is a representative value used for convenience and is not distinguished from other ion valences. There is a possibility that the ion valence of each component in the optical glass deviates from the representative value. For example, P is generally present in the glass in a state of an ion valence of +5, and thus "P 5+ " is used as the representative value in this patent, but there is a possibility that it is present in a state of another ion valence, which is also within the scope of protection of this patent.

[0039] <Regarding the Cation Component>

[0040] P 5+ is a glass network former component, and can improve the stability and devitrification resistance of the glass. In the present invention, 11% or more of P 5+ is contained to obtain the above-mentioned effects, and preferably 13% or more of P 5+ is contained, and more preferably 15% or more of P 5+ is contained. If the content of P 5+ exceeds 25%, the weather resistance of the glass tends to decrease, and the coefficient of thermal expansion becomes poor. Therefore, the content of P 5+ is 25% or less, preferably 23% or less, and more preferably 22% or less. In some embodiments, the content of P 5+ may be 11%, 11.5%, 12%, 12.5%, 13%, 13.5%, 14%, 14.5%, 15%, 15.5%, 16%, 16.5%, 17%, 17.5%, 18%, 18.5%, 19%, 19.5%, 20%, 20.5%, 21%, 21.5%, 22%, 22.5%, 23%, 23.5%, 24%, 24.5%, 25%, and the like, as well as all ranges and sub-ranges between the above-mentioned values. It should be understood that in embodiments, any of the above-mentioned ranges can be combined with any other range.

[0041] Al 3+ can improve the mechanical properties and weather resistance of the glass, and reduce the coefficient of thermal expansion of the glass. In the present invention, 16% or more of Al 3+ is contained to obtain the above-mentioned effects, and preferably 18% or more of Al 3+ is contained, and more preferably 20% or more of Al 3+ is contained. If the content of Al 3+ exceeds 30%, the transition temperature and liquidus temperature of the glass increase, the glass melting becomes difficult, the molding temperature increases, which leads to the intensification of volatilization of the glass, and an excessively high transition temperature makes it difficult to perform press molding. Therefore, the content of Al 3+ is 30% or less, preferably 28% or less, and more preferably 25% or less. In some embodiments, the content of Al 3+The content can be 16%, 16.5%, 17%, 17.5%, 18%, 18.5%, 19%, 19.5%, 20%, 20.5%, 21%, 21.5%, 22%, 22.5%, 23%, 23.5%, 24%, 24.5%, 25%, 25.5%, 26%, 26.5%, 27%, 27.5%, 28%, 28.5%, 29%, 29.5%, 30%, etc., as well as all ranges and sub-ranges between the above values. It should be understood that, in the implementation scheme, any of the above ranges can be combined with any other range.

[0042] Ba 2+ It can increase the refractive index of glass and improve its devitrification resistance; an appropriate amount of Ba can help. 2+ It is beneficial to improve the Al content in glass 3+ The content of Al is used to fully obtain Al. 3+ The effects it brings. On the other hand, if Ba 2+ If the content of Ba is too high, the stability of the glass decreases and the transition temperature increases. Therefore, in this invention... 2+ The content is greater than or equal to 8% but less than 20%, preferably 10-18%, more preferably 11-16%. In some embodiments, Ba 2+ The content can be 8%, 8.5%, 9%, 9.5%, 10%, 10.5%, 11%, 11.5%, 12%, 12.5%, 13%, 13.5%, 14%, 14.5%, 15%, 15.5%, 16%, 16.5%, 17%, 17.5%, 18%, 18.5%, 19%, 19.5%, 19.8%, less than 20%, etc., as well as all ranges and sub-ranges between the above values. It should be understood that, in the implementation scheme, any of the above ranges can be combined with any other range.

[0043] Sr 2+ It can reduce the coefficient of thermal expansion of glass and adjust its optical constants, but if its content is too high, the glass's resistance to devitrification and chemical stability will decrease. Therefore, in this invention, Sr... 2+ The content of Sr is 12-26%, preferably 14-24%, and more preferably 16-22%. In some embodiments, Sr 2+The content can be 12%, 12.5%, 13%, 13.5%, 14%, 14.5%, 15%, 15.5%, 16%, 16.5%, 17%, 17.5%, 18%, 18.5%, 19%, 19.5%, 20%, 20.5%, 21%, 21.5%, 22%, 22.5%, 23%, 23.5%, 24%, 24.5%, 25%, 25.5%, 26%, etc., as well as all ranges and sub-ranges between the above values. It should be understood that, in the implementation scheme, any of the above ranges can be combined with any other range.

[0044] Mg 2+ This invention can improve the thermal stability and processability of glass, as well as its molding properties. It utilizes a magnesium content of 7% or more. 2+ To achieve the above effects, it is preferable to have a content of 8% or more Mg. 2+ More preferably, it contains 10.5% or more Mg. 2+ On the other hand, Mg 2+ The content of Mg is controlled below 20% to prevent the glass from deteriorating in its devitrification resistance and becoming too low in its refractive index. Mg is preferred. 2 + The content is less than 18%, preferably Mg 2+ The content is less than 17%. In some embodiments, Mg 2+ The content can be 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, 10%, 10.5%, 11%, 11.5%, 12%, 12.5%, 13%, 13.5%, 14%, 14.5%, 15%, 15.5%, 16%, 16.5%, 17%, 17.5%, 18%, 18.5%, 19%, 19.5%, 20%, etc., as well as all ranges and sub-ranges between the above values. It should be understood that, in the implementation scheme, any of the above ranges can be combined with any other range.

[0045] In some implementations, P 5+ Ba 2+ Total content P 5+ +Ba 2+ With Mg 2+ Al 3+ Total Mg content 2+ +Al 3 + The ratio between (P) 5+ +Ba 2+ ) / (Mg 2+ +Al 3+ By controlling the pH value within the range of 0.4 to 1.7, the hardness of the glass can be increased while simultaneously improving its weather resistance. Therefore, (P) is preferred. 5+ +Ba2+ ) / (Mg 2+ +Al 3+ The value is 0.4 to 1.7, more preferably (P 5+ +Ba 2+ ) / (Mg 2+ +Al 3+ The value is 0.5–1.5, and further optimization is preferred (P). 5+ +Ba 2+ ) / (Mg 2+ +Al 3+ The value is 0.6–1.2, and further preferred (P) 5+ +Ba 2 + ) / (Mg 2+ +Al 3+ The value is 0.6 to 1.0. In some implementations, (P) 5+ +Ba 2+ ) / (Mg 2+ +Al 3+ The values ​​can be 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9, 0.95, 1.0, 1.05, 1.1, 1.15, 1.2, 1.25, 1.3, 1.35, 1.4, 1.45, 1.5, 1.55, 1.6, 1.65, 1.7, etc., as well as all ranges and subranges between the above values. It should be understood that, in the implementation scheme, any of the above ranges can be combined with any other range.

[0046] In some implementations, Mg 2+ Ba 2+ The total content and P 5+ The ratio between the contents of (Mg) 2+ +Ba 2+ ) / P 5 + By controlling the concentration within the range of 1.0 to 3.5, the hardness of the glass can be improved while preventing an increase in the glass transition temperature. Therefore, (Mg) is preferred. 2+ +Ba 2+ ) / P 5+ The value is 1.0 to 3.5, more preferably (Mg 2+ +Ba 2+ ) / P 5+ The value is 1.2–3.0, with further preference given to (Mg). 2+ +Ba 2+ ) / P 5+ The value is 1.3–2.5, with a further preferred value (Mg). 2+ +Ba 2+ ) / P 5+The value is 1.3 to 2.0. In some embodiments, (Mg) 2+ +Ba 2+ ) / P 5+ It can be 1.0, 1.05, 1.1, 1.15, 1.2, 1.25, 1.3, 1.35, 1.4, 1.45, 1.5, 1.55, 1.6, 1.65, 1.7, 1.75, 1.8, 1.85, 1.9, 1.95, 2.0, 2.05, 2.1, 2.15, 2.2, 2.25, 2.3, 2.35, 2.4, 2.45, 2.5, 2.55, 2.6, 2.65, 2.7, 2.75, 2.8, 2.85, 2.9, 2.95, 3.0, 3.05, 3.1, 3.15, 3.2, 3.25, 3.3, 3.35, 3.4, 3.45, 3.5, etc., as well as all ranges and subranges between the above values. It should be understood that, in the implementation plan, any of the above scopes can be combined with any other scopes.

[0047] Ca 2+ It can improve the chemical stability of glass, improve its abrasion resistance, and reduce its thermal expansion coefficient. However, if its content is too high, the glass's devitrification resistance will deteriorate. Therefore, in this invention, Ca... 2+ The content of Ca is 7-20%, preferably 8-18%, and more preferably 10.5-16.5%. In some embodiments, Ca... 2+ The content can be 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, 10%, 10.5%, 11%, 11.5%, 12%, 12.5%, 13%, 13.5%, 14%, 14.5%, 15%, 15.5%, 16%, 16.5%, 17%, 17.5%, 18%, 18.5%, 19%, 19.5%, 20%, etc., as well as all ranges and sub-ranges between the above values. It should be understood that, in the implementation scheme, any of the above ranges can be combined with any other range.

[0048] Zn 2+ It can lower the glass transition temperature and adjust the glass's coefficient of thermal expansion. However, if its content is too high, the glass dispersion increases, making it difficult to obtain the desired optical constants, and the glass's devitrification resistance decreases. Therefore, Zn... 2+ The content of Zn is 0-5%, preferably 0-3%, and more preferably 0-1%. In some embodiments, it is further preferred that it does not contain Zn. 2+ In some implementations, Zn 2+The content of ZnO can be 0%, greater than 0%, 0.01%, 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, and the like, and all ranges and subranges between the aforementioned values. It should be understood that in embodiments, any of the aforementioned ranges can be combined with any of the other ranges.

[0049] In some embodiments, the content of ZnO is controlled to be less than the content of MgO. 2+ 2+ The ratio of the content of ZnO to the content of MgO, ZnO / MgO, is controlled to be 0.5 or less, which prevents deterioration of acid resistance while optimizing the degree of abrasion of the glass. Therefore, it is preferable that ZnO / MgO be 0.5 or less, more preferable that ZnO / MgO be 0.3 or less, further preferable that ZnO / MgO be 0.2 or less, more further preferable that ZnO / MgO be 0.1 or less. 2+ 2+ The ratio of the content of ZnO to the content of MgO, ZnO / MgO, is controlled to be 0.5 or less, which prevents deterioration of acid resistance while optimizing the degree of abrasion of the glass. Therefore, it is preferable that ZnO / MgO be 0.5 or less, more preferable that ZnO / MgO be 0.3 or less, further preferable that ZnO / MgO be 0.2 or less, more further preferable that ZnO / MgO be 0.1 or less. 2+ 2+ The ratio of the content of ZnO to the content of MgO, ZnO / MgO, is controlled to be 0.5 or less, which prevents deterioration of acid resistance while optimizing the degree of abrasion of the glass. Therefore, it is preferable that ZnO / MgO be 0.5 or less, more preferable that ZnO / MgO be 0.3 or less, further preferable that ZnO / MgO be 0.2 or less, more further preferable that ZnO / MgO be 0.1 or less. 2+ 2+ The ratio of the content of ZnO to the content of MgO, ZnO / MgO, is controlled to be 0.5 or less, which prevents deterioration of acid resistance while optimizing the degree of abrasion of the glass. Therefore, it is preferable that ZnO / MgO be 0.5 or less, more preferable that ZnO / MgO be 0.3 or less, further preferable that ZnO / MgO be 0.2 or less, more further preferable that ZnO / MgO be 0.1 or less. 2+ 2+ The ratio of the content of ZnO to the content of MgO, ZnO / MgO, is controlled to be 0.5 or less, which prevents deterioration of acid resistance while optimizing the degree of abrasion of the glass. Therefore, it is preferable that ZnO / MgO be 0.5 or less, more preferable that ZnO / MgO be 0.3 or less, further preferable that ZnO / MgO be 0.2 or less, more further preferable that ZnO / MgO be 0.1 or less. 2+ 2+ The ratio of the content of ZnO to the content of MgO, ZnO / MgO, is controlled to be 0.5 or less, which prevents deterioration of acid resistance while optimizing the degree of abrasion of the glass. Therefore, it is preferable that ZnO / MgO be 0.5 or less, more preferable that ZnO / MgO be 0.3 or less, further preferable that ZnO / MgO be 0.2 or less, more further preferable that ZnO / MgO be 0.1 or less. 2+ 2+ The ratio of the content of ZnO to the content of MgO, ZnO / MgO, is controlled to be 0.5 or less, which prevents deterioration of acid resistance while optimizing the degree of abrasion of the glass. Therefore, it is preferable that ZnO / MgO be 0.5 or less, more preferable that ZnO / MgO be 0.3 or less, further preferable that ZnO / MgO be 0.2 or less, more further preferable that ZnO / MgO be 0.1 or less.

[0050] Rn + (Rn + is one or more of Li + , Na + , K + ) can lower the transition temperature and the refractive index of the glass, but if the content thereof is too much, the stability and weather resistance of the glass are lowered. Therefore, the content of Rn + in the present application is 0 to 8%, preferably 0 to 4%, more preferably 0 to 2%. In some embodiments, it is further preferable that Rn + not be contained. In some embodiments, it is further preferable that Rn + ​​​​​​​The content of Rnmay be 0%, greater than 0%, 0.01%, 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, and the like, as well as all ranges and sub-ranges between the aforementioned values. It should be understood that in embodiments, any of the aforementioned ranges can be combined with any of the other ranges.

[0051] In some embodiments, Rn + / Mg 2+ is controlled to be 0.35 or less, the thermal expansion coefficient of the glass can be prevented from deteriorating while the density of the glass is reduced. Therefore, it is preferable that Rn + / Mg 2+ be 0.35 or less, more preferably Rn + / Mg 2+ be 0.3 or less, further preferably Rn + / Mg 2+ be 0.2 or less, still further preferably Rn + / Mg 2+ be 0.1 or less. In some embodiments, Rn + / Mg 2+ may be 0, greater than 0, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.11, 0.12, 0.13, 0.14, 0.15, 0.16, 0.17, 0.18, 0.19, 0.2, 0.21, 0.22, 0.23, 0.24, 0.25, 0.26, 0.27, 0.28, 0.29, 0.3, 0.31, 0.32, 0.33, 0.34, 0.35, and the like, as well as all ranges and sub-ranges between the aforementioned values. It should be understood that in embodiments, any of the aforementioned ranges can be combined with any of the other ranges.

[0052] The inventors have found through extensive experimental research that by making the content of P 5+ , Ca 2+ , and Rn + P 5+ + Ca 2+ + Rn + and the content of Mg 2 + , the ratio (P 5+ + Ca 2+ + Rn + ) / Mg2+ Within the range of 1.1 to 4.0, the thermal shock resistance coefficient of the glass can be improved while simultaneously increasing the bubble content. Therefore, (P) is preferred. 5+ +Ca 2+ +Rn + ) / Mg 2+ The value is 1.1 to 4.0, more preferably (P 5+ +Ca 2+ +Rn + ) / Mg 2+ The value is 1.3 to 3.5, and further optimization is preferred (P). 5+ +Ca 2+ +Rn + ) / Mg 2+ The value is 1.5 to 3.0, with a further preferred value (P). 5+ +Ca 2+ +Rn + ) / Mg 2+ It is 1.8 to 2.5. In some implementations, (P) 5+ +Ca 2+ +Rn + ) / Mg 2+ The values ​​can be 1.1, 1.15, 1.2, 1.25, 1.3, 1.35, 1.4, 1.45, 1.5, 1.55, 1.6, 1.65, 1.7, 1.75, 1.8, 1.85, 1.9, 1.95, 2.0, 2.05, 2.1, 2.15, 2.2, 2.25, 2.3, 2.35, 2.4, 2.45, 2.5, 2.55, 2.6, 2 The ranges are 0.65, 2.7, 2.75, 2.8, 2.85, 2.9, 2.95, 3.0, 3.05, 3.1, 3.15, 3.2, 3.25, 3.3, 3.35, 3.4, 3.45, 3.5, 3.55, 3.6, 3.65, 3.7, 3.75, 3.8, 3.85, 3.9, 3.95, 4.0, etc., as well as all ranges and subranges between the above values. It should be understood that, in the implementation scheme, any of the above ranges can be combined with any other range.

[0053] In some implementations, Al 3+ 、Rn + Total Al content 3+ +Rn + With Mg 2+ The ratio between the contents of Al 3+ +Rn + ) / Mg 2+ By controlling the alumina within the range of 0.8 to 4.0, the glass density can be reduced while optimizing its abrasion resistance. Therefore, (Al) is preferred. 3+ +Rn +) / Mg 2+ is 0.8 to 4.0, more preferably (Al 3+ +Rn + ) / Mg 2+ is 1.0 to 3.0, further preferably (Al 3+ +Rn + ) / Mg 2+ is 1.2 to 2.5, still further preferably (Al 3+ +Rn + ) / Mg 2+ is 1.2 to 2.0. In some embodiments, (Al 3+ +Rn + ) / Mg 2+ may be 0.8, 0.85, 0.9, 0.95, 1.0, 1.05, 1.1, 1.15, 1.2, 1.25, 1.3, 1.35, 1.4, 1.45, 1.5, 1.55, 1.6, 1.65, 1.7, 1.75, 1.8, 1.85, 1.9, 1.95, 2.0, 2.05, 2.1, 2.15, 2.2, 2.25, 2.3, 2.35, 2.4, 2.45, 2.5, 2.55, 2.6, 2.65, 2.7, 2.75, 2.8, 2.85, 2.9, 2.95, 3.0, 3.05, 3.1, 3.15, 3.2, 3.25, 3.3, 3.35, 3.4, 3.45, 3.5, 3.55, 3.6, 3.65, 3.7, 3.75, 3.8, 3.85, 3.9, 3.95, 4.0, and all ranges and sub-ranges between the foregoing values. It should be understood that in embodiments, any of the foregoing ranges can be combined with any other range.

[0054] The Ln 3+ (Ln 3+ is one or more of La 3+ , Gd 3+ , Y 3+ , Yb 3+ ) in the glass of the present application can improve the devitrification resistance and thermal stability of the glass, and is conducive to the glass obtaining a higher Abbe number, but if its content is too high, the refractive index of the glass is too high, and it is difficult to meet the design requirements. Therefore, the content of Ln 3+ in the present application is greater than 0% but less than or equal to 10%, preferably 0.1 to 8%, more preferably 0.5 to 5%. In some embodiments, the content of Ln 3+The content can be greater than 0%, 0.01%, 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, 10%, etc., as well as all ranges and sub-ranges between the above values. It should be understood that, in the implementation scheme, any of the above ranges can be combined with any other range.

[0055] In some implementations, Zn 2+ / Ln 3+ Controlling the light transmittance to below 2.0 prevents a decrease in the glass's light transmittance and resistance to crystallization. Therefore, Zn is preferred. 2+ / Ln 3+ For values ​​below 2.0, Zn is preferred. 2+ / Ln 3+ For values ​​below 1.0, Zn is further preferred. 2+ / Ln 3+ For Zn content below 0.8, further optimization is preferred. 2+ / Ln 3+ It is below 0.5. In some implementations, Zn 2+ / Ln 3+ The possible values ​​are 0, greater than 0, 0.01, 0.03, 0.05, 0.07, 0.1, 0.13, 0.15, 0.17, 0.2, 0.23, 0.25, 0.27, 0.3, 0.33, 0.35, 0.37, 0.4, 0.43, 0.45, 0.47, 0.5, 0.53, 0.55, 0.57, 0.6, 0.63, 0.65, and 0.6. 7, 0.7, 0.75, 0.8, 0.85, 0.9, 0.95, 1.0, 1.05, 1.1, 1.15, 1.2, 1.25, 1.3, 1.35, 1.4, 1.45, 1.5, 1.55, 1.6, 1.65, 1.7, 1.75, 1.8, 1.85, 1.9, 1.95, 2.0, etc., as well as all ranges and subranges between the above values. It should be understood that, in the implementation scheme, any of the above ranges can be combined with any other range.

[0056] Through extensive experimental research, the inventor discovered that by using (Mg) 2+ -Ln 3+ ) / (Sr 2+ -Ba 2+ -Rn +) is in the range of 1.0 to 12.0, the coefficient of thermal shock resistance of the glass can be increased, and the coefficient of thermal expansion of the glass can be prevented from deteriorating. Therefore, it is preferable that (Mg 2+ -Ln 3+ ) / (Sr 2+ -Ba 2+ -Rn + ) be in the range of 1.0 to 12.0, more preferably (Mg 2+ -Ln 3+ ) / (Sr 2+ -Ba 2+ -Rn + ) be in the range of 1.5 to 10.0, further preferably (Mg 2+ -Ln 3+ ) / (Sr 2+ -Ba 2+ -Rn + ) be in the range of 2.0 to 7.0, and still further preferably (Mg 2+ -Ln 3+ ) / (Sr 2 + -Ba 2+ -Rn + ) be in the range of 2.5 to 4.5. In some embodiments, (Mg 2+ -Ln 3+ ) / (Sr 2+ -Ba 2+ -Rn +) can be 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4.0, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, 5.0, 5.1, 5.2, 5.3, 5.4, 5.5, 5.6, 5.7, 5.8, 5.9, 6.0, 6.1, 6.2, 6.3, 6.4, 6.5, 6.6, 6.7, 6.8, 6.9, 7.0, 7.1, 7.2, 7.3, 7.4, 7.5, 7.6, 7.7, 7.8, 7.9, 8.0, 8.1, 8.2, 8.3, 8.4, 8.5, 8.6, 8.7, 8.8, 8.9, 9.0, 9.1, 9.2, 9.3, 9.4, 9.5, 9.6, 9.7, 9.8, 9.9, 10.0, 10.1, 10.2, 10.3, 10.4, 10.5, 10.6, 10.7, 10.8, 10.9, 11.0, 11.1, 11.2, 11.3, 11.4, 11.5, 11.6, 11.7, 11.8, 11.9, 12.0, and the like, as well as all ranges and subranges therebetween. It should be understood that in embodiments, any of the above ranges can be combined with any other range.

[0057] In some embodiments, Rn + / Ln 3+ Controlled to be 1.5 or less, the density of the glass can be reduced while preventing the coefficient of thermal shock resistance of the glass from deteriorating. Therefore, it is preferable that Rn + / Ln 3+ be 1.5 or less, more preferably Rn + / Ln 3+ be 1.0 or less, further preferably Rn + / Ln 3+ be 0.8 or less, more further preferably Rn + / Ln 3+ be 0.5 or less. In some embodiments, Rn + / Ln 3+It can be 0, greater than 0, 0.01, 0.03, 0.05, 0.07, 0.1, 0.13, 0.15, 0.17, 0.2, 0.23, 0.25, 0.27, 0.3, 0.33, 0.35, 0.37, 0.4, 0.43, 0.45, 0.47, 0.5, 0.53, 0.55, 0.57, 0.6, 0.63, 0.65, 0.67, 0.7, 0.75, 0.8, 0.85, 0.9, 0.95, 1.0, 1.05, 1.1, 1.15, 1.2, 1.25, 1.3, 1.35, 1.4, 1.45, 1.5, etc., as well as all ranges and subranges between the above values. It should be understood that, in the implementation plan, any of the above scopes can be combined with any other scopes.

[0058] Nb 5+ W 6+ It can increase the refractive index and dispersion of glass, and improve the thermal and chemical stability of glass, if its total content Nb 5+ +W 6+ If the light transmittance exceeds 8%, the glass's devitrification resistance decreases, and the light transmittance deteriorates. Therefore, in this invention, Nb... 5+ +W 6+ The content is 0% to 8%, preferably greater than 0% but less than or equal to 6%, and more preferably 0.1% to 3%. In some embodiments, Nb 5+ W 6+ Total Nb content 5+ +W 6+ The percentage can be 0%, greater than 0%, 0.01%, 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, etc., as well as all ranges and sub-ranges between the above values. It should be understood that, in the implementation scheme, any of the above ranges can be combined with any other range.

[0059] In some implementations, Nb 5+ W 6+ Total Nb content 5+ +W 6+ With Ln 3+ The ratio between the contents of Nb 5+ +W 6+ ) / Ln 3+ By controlling the concentration within the range of 0.01 to 2.0, the glass can achieve suitable abrasion resistance while improving its weather resistance. Therefore, (Nb) is preferred.5+ +W 6+ ) / Ln 3+ 0.01-2.0, more preferably (Nb 5+ +W 6+ ) / Ln 3+ 0.05-1.5, further preferably (Nb 5+ +W 6+ ) / Ln 3+ 0.05-1.0, still further preferably (Nb 5+ +W 6+ ) / Ln 3+ 0.1-0.7. In some embodiments, (Nb 5+ +W 6+ ) / Ln 3+ may be 0.01, 0.03, 0.05, 0.07, 0.1, 0.13, 0.15, 0.17, 0.2, 0.23, 0.25, 0.27, 0.3, 0.33, 0.35, 0.37, 0.4, 0.43, 0.45, 0.47, 0.5, 0.53, 0.55, 0.57, 0.6, 0.63, 0.65, 0.67, 0.7, 0.75, 0.8, 0.85, 0.9, 0.95, 1.0, 1.05, 1.1, 1.15, 1.2, 1.25, 1.3, 1.35, 1.4, 1.45, 1.5, 1.55, 1.6, 1.65, 1.7, 1.75, 1.8, 1.85, 1.9, 1.95, 2.0, and all ranges and sub-ranges between the foregoing values. It is to be understood that in embodiments, any of the foregoing ranges can be combined with any of the other ranges.

[0060] Ti 4+ may increase the refractive index of the glass and adjust the Abbe number of the glass, but if its content is too high, the tendency of the glass to crystallize increases, the light transmittance deteriorates, and the melting property of the glass decreases. Therefore, in the present application, the content of Ti 4+ is 0-3%, preferably 0-2%, and more preferably 0-1%. In some embodiments, it is further preferred that the glass be free of Ti 4+ In some embodiments, the content of Ti 4+ may be 0%, greater than 0%, 0.01%, 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2%, 2.5%, 3%, and all ranges and sub-ranges between the foregoing values. It is to be understood that in embodiments, any of the foregoing ranges can be combined with any of the other ranges.

[0061] Ta 5+ The refractive index of the glass can be improved, but when the content is high, the glass is prone to devitrification, and the raw material cost of the glass increases. Therefore, the content of Ta 5+ is 0-5%, preferably 0-3%, and more preferably 0-1%. In some embodiments, it is further preferred to not contain Ta 5+ In some embodiments, the content of Ta 5+ may be 0%, greater than 0%, 0.01%, 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, and all ranges and sub-ranges between the aforementioned values. It should be understood that in embodiments, any of the aforementioned ranges can be combined with any other range.

[0062] Si 4+ The glass can improve the devitrification resistance and processability of the glass, and adjust the high temperature viscosity of the glass. When the content is too high, the melting performance of the glass decreases. Therefore, the content of Si 4+ in the optical glass of the present application is 0-5%, preferably 0-3%, and more preferably 0-1%. In some embodiments, it is further preferred to not contain Si 4+ In some embodiments, the content of Si 4+ may be 0%, greater than 0%, 0.01%, 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, and all ranges and sub-ranges between the aforementioned values. It should be understood that in embodiments, any of the aforementioned ranges can be combined with any other range.

[0063] B 3+ The glass can improve the devitrification resistance of the glass, but in the optical glass containing fluorine, the glass melting will have a strong volatilization, causing the optical constant of the glass to be unstable and stripes to appear. Therefore, the content of B 3+ is 0-5%, preferably 0-3%, and more preferably 0-1%. In some embodiments, it is further preferred to not contain B 3+ In some embodiments, the content of B 3+The content of Sb can be 0%, greater than 0%, 0.01%, 0.02%, 0.03%, 0.04%, 0.05%, 0.06%, 0.07%, 0.08%, 0.09%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, and all ranges and subranges between the aforementioned values. It should be understood that in embodiments, any of the aforementioned ranges can be combined with any other range.

[0064] The glass of the present application can contain one or more components selected from the group consisting of Sb 3+ , Sn 4+ , Ce 4+ as a fining agent to improve the defoaming effect of the glass. When the content of Sb 3+ exceeds 1%, the glass has a tendency to decrease in fining performance, and simultaneously promotes deterioration of the forming mold due to its strong oxidizing effect. Therefore, the content of Sb 3+ in the present application is 0 to 1%, preferably 0 to 0.5%, and more preferably 0 to 0.2%. In some embodiments, the content of Sb 3+ may be 0%, greater than 0%, 0.01%, 0.02%, 0.03%, 0.04%, 0.05%, 0.06%, 0.07%, 0.08%, 0.09%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, and all ranges and subranges between the aforementioned values. It should be understood that in embodiments, any of the aforementioned ranges can be combined with any other range. Sn 4+ may also be used as a fining agent, but when its content exceeds 1%, it causes the glass to be colored severely, or when the glass is heated, softened, and subjected to re-shaping such as press molding, Sn 4+ becomes a starting point for crystal nucleus generation, and has a tendency to produce devitrification. Therefore, the content of Sn 4+ in the present application is 0 to 1%, preferably 0 to 0.5%, and more preferably 0 to 0.2%. In some embodiments, the content of Sn 4+ may be 0%, greater than 0%, 0.01%, 0.02%, 0.03%, 0.04%, 0.05%, 0.06%, 0.07%, 0.08%, 0.09%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, and all ranges and subranges between the aforementioned values. It should be understood that in embodiments, any of the aforementioned ranges can be combined with any other range. Ce 4+ functions and content are the same as those of Sn 4+Ce, in an amount of 0 to 1%, preferably 0 to 0.5%, more preferably 0 to 0.2%. In some embodiments, Ce 4+ may be 0%, greater than 0%, 0.01%, 0.02%, 0.03%, 0.04%, 0.05%, 0.06%, 0.07%, 0.08%, 0.09%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, etc., as well as all ranges and sub-ranges between the aforementioned values. It should be understood that in embodiments, any of the aforementioned ranges can be combined with any other range.

[0065] Other components such as Zr 4+ , Ge 4+ , Bi 3+ , Te 4+ may be contained in the optical glass of the present application as needed without impairing the characteristics of the optical glass of the present application and the object of the present application. In some embodiments, the individual content or total content of Zr 4 + , Ge 4+ , Bi 3+ , Te 4+ in the optical glass of the present application is preferably 5% or less, more preferably 3% or less, further preferably 1% or less, and still further preferably the optical glass of the present application does not contain Zr 4+ , and / or does not contain Ge 4+ , and / or does not contain Bi 3+ , and / or does not contain Te 4 + .

[0066] <Concerning the anion component>

[0067] F - may lower the refractive index and the transition temperature of the glass and increase the Abbe number of the glass. In the present application, the content of F - is 61% or more to obtain the aforementioned effects, and preferably the content of F - is 63% or more, and more preferably the content of F - is 65% or more. On the other hand, if the content of F - is too high, the stability of the glass is impaired and the coefficient of thermal expansion of the glass is increased. In particular, during the melting process, the volatilization of F - easily contaminates the environment and easily makes the internal composition of the glass uneven. Therefore, in the present application, the content of F - is 80% or less, preferably 75% or less, and more preferably 73% or less. In some embodiments, the content of F -The content can be 61%, 61.5%, 62%, 62.5%, 63%, 63.5%, 64%, 64.5%, 65%, 65.5%, 66%, 66.5%, 67%, 67.5%, 68%, 68.5%, 69%, 69.5%, 70%, 70.5%, 71%, 71.5%, 72%, 72.5%, 73%, 73.5%, 74%, 74.5%, 75%, 75.5%, 76%, 76.5%, 77%, 77.5%, 78%, 78.5%, 79%, 79.5%, 80%, etc., as well as all ranges and sub-ranges between the above values. It should be understood that, in the implementation scheme, any of the above ranges can be combined with any other range.

[0068] In some implementations, F - The content of P 5+ B 3+ Total content P 5+ +B 3+ The ratio F between them - / (P 5+ +B 3 + By controlling the pH value within the range of 2.5 to 6.5, the hardness of the glass can be increased while lowering the glass transition temperature. Therefore, F is preferred. - / (P 5+ +B 3+ The value is 2.5 to 6.5, with F being more preferred. - / (P 5+ +B 3+ The value of F is 3.0 to 6.0, and F is further optimized. - / (P 5+ +B 3+ The optimal value is 3.5–5.5, with F being the most preferred. - / (P 5+ +B 3+ The value is 3.5 to 5.0. In some implementations, F... - / (P 5+ +B 3+ The range can be 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4.0, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, 5.0, 5.1, 5.2, 5.3, 5.4, 5.5, 5.6, 5.7, 5.8, 5.9, 6.0, 6.1, 6.2, 6.3, 6.4, 6.5, etc., as well as all ranges and subranges between the above values. It should be understood that, in the implementation scheme, any of the above ranges can be combined with any other range.

[0069] The optical glass of the present application contains O 2- In particular, by containing 20% or more of O 2- The stability and weather resistance of the glass can be improved, and the degree of wear and the degree of striation of the glass can be inhibited from deteriorating. On the other hand, by controlling the content of O 2- to 39% or less, the high-temperature viscosity and the melting temperature of the glass can be prevented from increasing. Therefore, the content of O 2- is 20 to 39%, preferably 25 to 37%, and more preferably 27 to 35%. In some embodiments, the content of O 2- may be 20%, 20.5%, 21%, 21.5%, 22%, 22.5%, 23%, 23.5%, 24%, 24.5%, 25%, 25.5%, 26%, 26.5%, 27%, 27.5%, 28%, 28.5%, 29%, 29.5%, 30%, 30.5%, 31%, 31.5%, 32%, 32.5%, 33%, 33.5%, 34%, 34.5%, 35%, 35.5%, 36%, 36.5%, 37%, 37.5%, 38%, 38.5%, 39%, and the like, as well as all ranges and sub-ranges between the aforementioned values. It should be understood that in embodiments, any of the aforementioned ranges can be combined with any other range.

[0070] In some embodiments, F - / O 2- is controlled to be in the range of 1.8 to 3.8, which is advantageous for improving the devitrification resistance and the degree of bubbles of the glass. Therefore, it is preferable that F - / O 2- be 1.8 to 3.8, more preferably F - / O 2- be 1.8 to 3.5, further preferably F - / O 2- be 2.0 to 3.0, and still further preferably F - / O 2- be 2.0 to 2.8. In some embodiments, F - / O 2-The values ​​can be 1.8, 1.85, 1.9, 1.95, 2.0, 2.05, 2.1, 2.15, 2.2, 2.25, 2.3, 2.35, 2.4, 2.45, 2.5, 2.55, 2.6, 2.65, 2.7, 2.75, 2.8, 2.85, 2.9, 2.95, 3.0, 3.05, 3.1, 3.15, 3.2, 3.25, 3.3, 3.35, 3.4, 3.45, 3.5, 3.55, 3.6, 3.65, 3.7, 3.75, 3.8, etc., as well as all ranges and subranges between the above values. It should be understood that, in the implementation scheme, any of the above ranges can be combined with any other range.

[0071] In this invention, a solution containing less than 2% Cl can be used. - , and / or Br - , and / or I - As a clarifying agent, Cl can improve the defoaming effect of glass. Therefore, in this invention, Cl - ,Br - I - Total content of Cl - +Br - +I - The concentration is 0-2%, preferably 0-1%, and more preferably 0-0.5%. In some embodiments, Cl - ,Br - I - Total content of Cl - +Br - +I - The percentage can be 0%, greater than 0%, 0.01%, 0.02%, 0.03%, 0.04%, 0.05%, 0.06%, 0.07%, 0.08%, 0.09%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2%, etc., as well as all ranges and sub-ranges between the above values. It should be understood that, in the implementation scheme, any of the above ranges can be combined with any other range.

[0072] <Regarding components that should not be present>

[0073] Even when cationic components such as V, Cr, Mn, Fe, Co, Ni, Cu, Ag, and Mo are present in small amounts, either alone or in combination, the glass will be colored and absorb at specific wavelengths in the visible light region, thereby weakening the property of the present invention to improve visible light transmittance. Therefore, it is preferable that optical glass, especially for optical glass where transmittance in the visible light region is required, does not actually contain the above-mentioned components.

[0074] As, Pb, Th, Cd, Tl, Os, Be and Se and the like, which have been controlled to be used as harmful chemical substances in recent years, not only in the manufacturing process of the glass, but also in the processing process and the disposal after the product is manufactured, measures for environmental protection are necessary. Therefore, in the case of paying attention to the influence on the environment, it is preferable that they are not contained practically except for the inevitable mixture. Thus, the optical glass becomes practically free from the substances polluting the environment. Therefore, even if no special measures for environmental countermeasures are taken, the optical glass of the present application can be manufactured, processed and discarded.

[0075] The "not containing" "0%" described herein means that the component is not intentionally added as a raw material to the fluorophosphate optical glass of the present application; but as a raw material and / or equipment for producing the optical glass, there can be some impurities or components which are not intentionally added and which are contained in a small amount or a trace amount in the final optical glass, and such a case is also within the scope of protection of the present patent.

[0076] Next, the properties of the fluorophosphate optical glass of the present application will be described.

[0077] <Refractive index and Abbe number>

[0078] The refractive index (n d ) and the Abbe number (v d ) of the optical glass were measured according to the method prescribed in the national standard "GB / T 7962.1-2010".

[0079] In some embodiments, the lower limit of the refractive index (n d ) of the fluorophosphate optical glass of the present application is 1.46, preferably 1.47, more preferably 1.48; in some embodiments, the upper limit of the refractive index (n d ) of the optical glass of the present application is 1.53, preferably 1.52, more preferably 1.51. In some embodiments, the refractive index (n d) can be 1.46, 1.461, 1.463, 1.465, 1.467, 1.469, 1.47, 1.471, 1.473, 1.475, 1.477, 1.479, 1.48, 1.481, 1.483, 1.485, 1.487, 1.489, 1.49, 1.491, 1.493, 1.495, 1.497, 1.499, 1.50, 1.501, 1.503, 1.505, 1.507, 1.509, 1.51, 1.511, 1.513, 1.515, 1.517, 1.519, 1.52, 1.521, 1.523, 1.525, 1.527, 1.529, 1.53, and the like, and all ranges and subranges therebetween.

[0080] In some embodiments, the Abbe number (νD) of the fluorophosphate optical glass of the present application can be 78 or greater, preferably 79 or greater, more preferably 80 or greater. d In some embodiments, the Abbe number (νD) of the fluorophosphate optical glass of the present application can be 78 or greater, preferably 79 or greater, more preferably 80 or greater. d In some embodiments, the Abbe number (νD) of the fluorophosphate optical glass of the present application can be 78 or greater, preferably 79 or greater, more preferably 80 or greater.

[0081] In some embodiments, the Abbe number (νD) of the fluorophosphate optical glass of the present application can be 78 or greater, preferably 79 or greater, more preferably 80 or greater. d In some embodiments, the Abbe number (νD) of the fluorophosphate optical glass of the present application can be 78 or greater, preferably 79 or greater, more preferably 80 or greater.

[0082] <Density>

[0083] The density (ρ) of the optical glass is tested according to the method specified in the national standard GB / T 7962.20-2010.

[0084] In some embodiments, the density (ρ) of the fluorophosphate optical glass of the present application is 4.20 g / cm3or greater, preferably 4.25 g / cm3or greater, more preferably 4.30 g / cm3or greater. 3 In some embodiments, the density (ρ) of the fluorophosphate optical glass of the present application is 4.20 g / cm3or greater, preferably 4.25 g / cm3or greater, more preferably 4.30 g / cm3or greater. 3 In some embodiments, the density (ρ) of the fluorophosphate optical glass of the present application is 4.20 g / cm3or greater, preferably 4.25 g / cm3or greater, more preferably 4.30 g / cm3or greater. 3 In some embodiments, the density (ρ) of the fluorophosphate optical glass of the present application is 4.20 g / cm3or greater, preferably 4.25 g / cm3or greater, more preferably 4.30 g / cm3or greater. 3below. In some embodiments, the density (p) can be 4.20 g / cm 3 , 4.19 g / cm 3 , 4.18 g / cm 3 , 4.17 g / cm 3 , 4.16 g / cm 3 , 4.15 g / cm 3 , 4.14 g / cm 3 , 4.13 g / cm 3 , 4.12 g / cm 3 , 4.11 g / cm 3 , 4.10 g / cm 3 , 4.09 g / cm 3 , 4.08 g / cm 3 , 4.07 g / cm 3 , 4.06 g / cm 3 , 4.05 g / cm 3 , 4.04 g / cm 3 , 4.03 g / cm 3 , 4.02 g / cm 3 , 4.01 g / cm 3 , 4.00 g / cm 3 , 3.99 g / cm 3 , 3.98 g / cm 3 , 3.97 g / cm 3 , 3.96 g / cm 3 , 3.95 g / cm 3 , 3.94 g / cm 3 , 3.93 g / cm 3 , 3.92 g / cm 3 , 3.91 g / cm 3 , 3.90 g / cm 3 , 3.89 g / cm 3 , 3.88 g / cm 3 , 3.87 g / cm 3 , 3.86 g / cm 3 , 3.85 g / cm 3 , 3.84 g / cm 3 , 3.83 g / cm 3 , 3.82 g / cm 3 , 3.81 g / cm 3 , 3.80 g / cm 3 , 3.79 g / cm 3 , 3.78 g / cm 3 , 3.77 g / cm 3 , 3.76 g / cm3 , 3.75 g / cm 3 , 3.74 g / cm 3 , 3.73 g / cm 3 , 3.72 g / cm 3 , 3.71 g / cm 3 , 3.70 g / cm 3 and all ranges and sub-ranges between the above values.

[0085] <Weather resistance>

[0086] The weather resistance (CR) of the optical glass is tested according to the following method: the glass sample is placed in a test box with a saturated water vapor environment of 90% relative humidity, and is alternately cycled every 1 hour at 40-50℃, for 15 cycles. The weather resistance category is divided according to the turbidity change before and after the sample is placed, and Table 1 is the weather resistance classification table.

[0087] Table 1. Weather resistance classification table

[0088]

[0089] In some embodiments, the weather resistance (CR) of the fluorophosphate optical glass of the present application is Class 2 or above, preferably Class 1.

[0090] <Resistance to water action stability>

[0091] The resistance to water action stability (D W ) of the optical glass (powder method) is tested according to the method specified in the national standard GB / T 17129.

[0092] In some embodiments, the resistance to water action stability (D W ) of the fluorophosphate optical glass of the present application is Class 2 or above, preferably Class 1.

[0093] <Resistance to acid action stability>

[0094] The resistance to acid action stability (D A ) of the optical glass (powder method) is tested according to the method specified in the national standard GB / T 17129.

[0095] In some embodiments, the resistance to acid action stability (D A ) of the fluorophosphate optical glass of the present application is Class 3 or above, preferably Class 2 or above.

[0096] <Thermal expansion coefficient>

[0097] The thermal expansion coefficient (a -30～70℃ ) of the optical glass is tested according to the method specified in the national standard GB / T 7962.16-2010, and the data at -30-70℃.

[0098] In some embodiments, the present fluorophosphate optical glass has a thermal expansion coefficient (a -30～70℃ ) of 160 x 10 -7 / K or less, preferably 150 x 10 -7 / K or less, more preferably 140 x 10 -7 / K or less, further preferably 120 x 10 -7 / K to 135 x 10 -7 / K. In some embodiments, the thermal expansion coefficient (a -30～70℃ ) can be 120 x 10 -7 / K, 121 x 10 -7 / K, 123 x 10 -7 / K, 125 x 10 -7 / K, 127 x 10 -7 / K, 129 x 10 -7 / K, 130 x 10 -7 / K, 131 x 10 -7 / K, 133 x 10 -7 / K, 135 x 10 -7 / K, 137 x 10 -7 / K, 139 x 10 -7 / K, 140 x 10 -7 / K, 141 x 10 -7 / K, 143 x 10 -7 / K, 145 x 10 -7 / K, 147 x 10 -7 / K, 149 x 10 -7 / K, 150 x 10 -7 / K, 151 x 10 -7 / K, 153 x 10 -7 / K, 155 x 10 -7 / K, 157 x 10 -7 / K, 159 x 10 -7 / K, 160 x 10 -7 / K, etc., and all ranges and subranges therebetween.

[0099] <Transition Temperature>

[0100] The transition temperature (T g ) of the optical glass is tested according to the method specified in the national standard GB / T 7962.16-2010.

[0101] In some embodiments, the present fluorophosphate optical glass has a transition temperature (T g) is 500°C or less, preferably 490°C or less, more preferably 485°C or less.

[0102] In some embodiments, the transition temperature (T g ) can be 460°C, 461°C, 463°C, 465°C, 467°C, 469°C, 470°C, 471°C, 473°C, 475°C, 477°C, 479°C, 480°C, 481°C, 483°C, 485°C, 487°C, 489°C, 490°C, 491°C, 493°C, 495°C, 497°C, 499°C, 500°C, etc., and all ranges and sub-ranges between the aforementioned values.

[0103] <Thermal shock resistance coefficient>

[0104] The thermal shock resistance of the optical glass is represented by the thermal shock resistance coefficient (β) of the glass, and the higher the thermal shock resistance coefficient (β) of the optical glass, the less likely the glass element is to break due to thermal stress caused by the thermal shock of temperature reduction.

[0105] The calculation formula of the thermal shock resistance coefficient (β) of the glass is as follows:

[0106] β = λ(1 - v) / αE

[0107] λ is the thermal conductivity coefficient of the glass (W / (m.K));

[0108] α is the thermal expansion coefficient of the glass (10 -7 / K);

[0109] E is the Young's modulus of the glass (Pa);

[0110] v is the Poisson's ratio of the glass.

[0111] In some embodiments, the thermal shock resistance coefficient (β) of the fluorophosphate optical glass of the present application is 10.0 x 10 3 , preferably 13.0 x 10 3 , more preferably 15.0 x 10 3 , further preferably 16.0 x 10 3 , and in some embodiments, the thermal shock resistance coefficient (β) can be 10.0 x 10 3 , 10.1 x 10 3 , 10.3 x 10 3 , 10.5 x 10 3 , 10.7 x 10 3 , 10.9 x 10 3 , 11.0 x 10 3 , 11.1 x 10 3 , 11.3 x 103 , 11.5 x 10 3 , 11.7 x 10 3 , 11.9 x 10 3 , 12.0 x 10 3 , 12.1 x 10 3 , 12.3 x 10 3 , 12.5 x 10 3 , 12.7 x 10 3 , 12.9 x 10 3 , 13.0 x 10 3 , 13.1 x 10 3 , 13.3 x 10 3 , 13.5 x 10 3 , 13.7 x 10 3 , 13.9 x 10 3 , 14.0 x 10 3 , 14.1 x 10 3 , 14.3 x 10 3 , 14.5 x 10 3 , 14.7 x 10 3 , 14.9 x 10 3 , 15.0 x 10 3 , 15.1 x 10 3 , 15.3 x 10 3 , 15.5 x 10 3 , 15.7 x 10 3 , 15.9 x 10 3 , 16.0 x 10 3 , 16.1 x 10 3 , 16.3 x 10 3 , 16.5 x 10 3 , 16.7 x 10 3 , 16.9 x 10 3 , 17.0 x 10 3 , 17.1 x 10 3 , 17.3 x 10 3 , 17.5 x 10 3 , 17.7 x 10 3 , 17.9 x 10 3 , 18.0 x 10 3 , and all ranges and subranges therebetween.

[0112] <degree of abrasion>

[0113] the degree of abrasion (F A) refers to the value obtained after multiplying the ratio of the abrasion amount of the sample to the abrasion amount (volume) of the standard sample (H-K9 glass) by 100 under the same conditions, and is expressed by the following formula:

[0114] F A = V / V0 x 100 = (W / ρ) / (W0 / ρ0) x 100

[0115] In the formula, V is the volume abrasion amount of the sample to be measured;

[0116] V0 is the volume abrasion amount of the standard sample;

[0117] W is the mass abrasion amount of the sample to be measured;

[0118] W0 is the mass abrasion amount of the standard sample;

[0119] ρ is the density of the sample to be measured;

[0120] ρ0 is the density of the standard sample.

[0121] In some embodiments, the abrasion degree (F A ) of the fluorophosphate optical glass of the present application has a lower limit of 305, preferably a lower limit of 315, and more preferably a lower limit of 320. In some embodiments, the abrasion degree (F A ) of the optical glass of the present application has an upper limit of 345, preferably an upper limit of 340, and more preferably an upper limit of 335.

[0122] In some embodiments, the abrasion degree (F A ) can be 305, 306, 307, 308, 309, 310, 311, 312, 313, 314, 315, 316, 317, 318, 319, 320, 321, 322, 323, 324, 325, 326, 327, 328, 329, 330, 331, 332, 333, 334, 335, 336, 337, 338, 339, 340, 341, 342, 343, 344, 345, and the like, as well as all ranges and sub-ranges between the above-mentioned values.

[0123] <Coloring degree>

[0124] The short-wave transmission spectral characteristics of the glass of the present application are represented by the coloring degrees (λ 80 and λ5). λ 80 refers to the wavelength at which the glass transmission ratio reaches 80%. λ 80The measurement is performed using a glass having two opposite flat surfaces of 10 ± 0.1 mm in thickness, which are parallel to each other and optically polished, and the wavelength at which the transmittance is 80% is determined in a wavelength region from 280 nm to 700 nm. The transmittance or the transmittance is an amount represented by I in / I out , which is a case where light of intensity I out is made to pass through the glass and exit from one flat surface as light of intensity I in , and also includes the transmittance of the surface reflection loss on the above-mentioned surface of the glass. The higher the refractive index of the glass, the greater the surface reflection loss. Therefore, in optical glasses, a small value of λ 80 means that the glass itself is less colored and the light transmittance is high. λ

[0125] 5 is the same as the above.

[0126] In some embodiments, the fluorophosphate optical glass of the present application has λ 80 of 350 nm or less, preferably λ 80 of 340 nm or less, more preferably λ 80 of 335 nm or less. In some embodiments, the optical glass can have λ 80 of 320 nm, 321 nm, 322 nm, 323 nm, 324 nm, 325 nm, 326 nm, 327 nm, 328 nm, 329 nm, 330 nm, 331 nm, 332 nm, 333 nm, 334 nm, 335 nm, 336 nm, 337 nm, 338 nm, 339 nm, 340 nm, 341 nm, 342 nm, 343 nm, 344 nm, 345 nm, 346 nm, 347 nm, 348 nm, 349 nm, 350 nm, etc., and all ranges and subranges between the above values.

[0127] In some embodiments, the fluorophosphate optical glass of the present application has λ5of 320 nm or less, preferably λ5of 310 nm or less, more preferably λ5of 305 nm or less. In some embodiments, the optical glass can have λ5of 290 nm, 291 nm, 292 nm, 293 nm, 294 nm, 295 nm, 296 nm, 297 nm, 298 nm, 299 nm, 300 nm, 301 nm, 302 nm, 303 nm, 304 nm, 305 nm, 306 nm, 307 nm, 308 nm, 309 nm, 310 nm, 311 nm, 312 nm, 313 nm, 314 nm, 315 nm, 316 nm, 317 nm, 318 nm, 319 nm, 320 nm, etc., and all ranges and subranges between the above values.

[0128] Knoop Hardness

[0129] Knoop hardness (H) of optical glass K The test was conducted according to the method specified in the national standard GB / T7962.18—2010. In this invention, Knoop hardness can be simply referred to as hardness.

[0130] In some embodiments, the Knoop hardness (H) of the fluorophosphate optical glass of the present invention is... K ) is 330×10 7 Pa or higher, preferably 350 × 10 Pa 7 Pa or higher, more preferably 360 × 10 Pa 7 Pa or higher. In some embodiments, the Knoop hardness (H) is... K ) can be 330×10 7 Pa, 335×10 7 Pa, 340×10 7 Pa, 345×10 7 Pa, 350×10 7 Pa, 355×10 7 Pa, 360×10 7 Pa, 365×10 7 Pa, 370×10 7 Pa, 375×10 7 Pa, 380×10 7 Pa, 385×10 7 Pa, etc., and all ranges and subranges between the above values.

[0131] <Effervescence>

[0132] The bubble degree of optical glass is tested according to the method specified in the national standard GB / T7962.8—2010.

[0133] In some embodiments, the bubble degree of the fluorophosphate optical glass of the present invention is grade A or above, preferably grade A0 or above, and more preferably grade A. 00 class.

[0134] [Manufacturing Method]

[0135] The fluorophosphate optical glass of the present application is produced by using conventional raw materials and processes. The glass of the present application is produced by using carbonates, nitrates, sulfates, hydroxides, oxides, fluorides, phosphates, metaphosphates, and the like as raw materials, and by melting the raw materials in a melting furnace (e.g., a platinum crucible, a platinum alloy crucible, or the like) at a temperature of 850 to 1200°C after mixing the raw materials in a conventional manner, and by homogenizing the molten glass by clarification, stirring, and the like. The homogenized molten glass is cast in a mold and annealed to produce a glass preform. The raw materials, the process, and the process parameters can be appropriately selected by those skilled in the art as needed.

[0136] [Glass preform and optical element]

[0137] A glass preform can be produced from the fluorophosphate optical glass produced by, for example, a grinding process, or a molding process such as reheat press molding or precision press molding. That is, a glass preform can be produced by machining, such as grinding and polishing, an optical glass, or by machining, such as grinding, a preform blank for molding after reheat press molding the preform blank, or by precision press molding a preform blank produced by machining.

[0138] Note that the method of producing a glass preform is not limited to the above. As described above, the optical glass of the present application is useful for various optical elements and optical designs, and it is particularly preferable to form a preform blank from the optical glass of the present application, and to use the preform blank to perform reheat press molding, precision press molding, or the like, to produce optical elements such as lenses, prisms, and diffraction gratings.

[0139] The glass preform of the present application is formed from the fluorophosphate optical glass of the present application described above. The glass preform of the present application has the excellent properties of the optical glass, and the optical element of the present application has the excellent properties of the optical glass, and can provide various optical elements such as lenses, prisms, and diffraction gratings, which have high optical value.

[0140] As examples of lenses, there are various lenses such as concave meniscus lenses, convex meniscus lenses, lenticular lenses, double concave lenses, plano-convex lenses, and plano-concave lenses, in which the lens surface is a spherical surface or an aspherical surface.

[0141] [Optical instrument]

[0142] The optical element formed from the fluorophosphate optical glass of the present application can be used to produce optical instruments such as photographic equipment, portable electronic equipment (e.g., cellular phones, watches, and the like), video recording equipment, display equipment, and monitoring equipment.

[0143] [Examples]

[0144] <Fluorophosphate optical glass examples>

[0145] In order to further clarify and illustrate the technical solutions of the present application, the following non-limiting examples are provided.

[0146] In this example, fluorophosphate optical glasses having the compositions shown in Tables 2 to 4 were obtained using the above-described optical glass manufacturing method. In addition, the properties of each glass were measured by the test methods described in the present application, and the measurement results are shown in Tables 2 to 4.

[0147] Table 2.

[0148]

[0149]

[0150]

[0151] Table 3.

[0152]

[0153]

[0154] Table 4.

[0155]

[0156]

[0157]

[0158] <Glass preform examples>

[0159] The glasses obtained in the fluorophosphate optical glass examples of Tables 2 to 4 were used to make various lenses, prisms, and the like, such as concave meniscus lenses, convex meniscus lenses, double convex lenses, double concave lenses, plano-convex lenses, plano-concave lenses, and the like, using, for example, a grinding process, or a molding process such as reheat press molding, precision press molding, and the like.

[0160] <Optical element examples>

[0161] The preforms obtained in the above-described glass preform examples were annealed to reduce the internal stress of the glass while fine-tuning the refractive index, so that the optical properties such as the refractive index reached the desired values.

[0162] Next, the preforms were ground and polished to make various lenses, prisms, and the like, such as concave meniscus lenses, convex meniscus lenses, double convex lenses, double concave lenses, plano-convex lenses, plano-concave lenses, and the like. The surfaces of the obtained optical elements can also be coated with an anti-reflection film.

[0163] <Optical instrument embodiments>

[0164] The optical elements made according to the above embodiments of optical elements can be used in optical components or optical assemblies formed by using one or more optical elements by optical design, for example, in imaging devices, sensors, microscopes, medical technology, digital projection, communication, optical communication technology / information transmission, optics / illumination in the automotive sector, lithography technology, excimer lasers, wafers, computer chips, and integrated circuits and electronic devices comprising such circuits and chips.

Claims

1. Fluorophosphate optical glass, characterized in that, Its components are expressed as a mole percentage, and the cationic component contains: P 5+ : 11-25%; Al 3+ : 16-30%; Ba 2+ : Greater than or equal to 8% but less than 20%; Sr 2+ 12-26%; Mg 2+ 7-20%; Ca 2 + 7-20%; Ln 3+ : Greater than 0% but less than or equal to 10%; Rn + 0-8%, of which (Mg 2+ -Ln 3+ ) / (Sr 2+ -Ba 2+ -Rn + The value of Ln is 1.0 to 12.

0. 3+ For La 3+ Gd 3+ Y 3+ Yb 3+ One or more of the following, wherein Rn + For Li + Na + K + One or more of the following; The anionic component contains: F - 61-80%; O 2- 20-39%.

2. The fluorophosphate optical glass according to claim 1, characterized in that, Its components are expressed as molar percentages, and the cationic component also contains: Nb 5+ +W 6+ : 0–8%; and / or Ti 4+ 0–3%; and / or Zn 2+ 0–5%; and / or Ta 5+ : 0-5%; and / or B 3+ : 0-5%; and / or Si 4+ 0–5%; and / or Sb 3+ : 0-1%; and / or Sn 4+ : 0-1%; and / or Ce 4 + 0-1%; The anionic component also contains: Cl - +Br - +I - : 0-2%.

3. Fluorophosphate optical glass, characterized in that, Its components contain P 5+ Al 3+ Ba 2+ 、Sr 2+ Mg 2+ Ca 2+ 、Ln 3+ F - and O 2- Its components are expressed as mole percentages, containing 0–8% Rn. + , of which (Mg 2+ -Ln 3+ ) / (Sr 2+ -Ba 2+ -Rn + The value of Ln is 1.0 to 12.

0. 3+ For La 3+ Gd 3+ Y 3+ Yb 3+ One or more of the following, wherein Rn + For Li + Na + K + One or more of the following, wherein the refractive index n of the fluorophosphate optical glass is... d The Abbe number ν ranges from 1.46 to 1.

53. d Its value is 78–86, and its thermal shock resistance coefficient β is 10.0 × 10⁻⁶. 3 above.

4. The fluorophosphate optical glass according to claim 3, characterized in that, Its components are expressed as a mole percentage, and the cationic component contains: P 5+ : 11-25%; and / or Al 3+ : 16-30%; and / or Ba 2+ : Greater than or equal to 8% but less than 20%; and / or Sr 2+ 12–26%; and / or Mg 2+ 7–20%; and / or Ca 2+ 7–20%; and / or Ln 3+ : greater than 0% but less than or equal to 10%; and / or Nb 5+ +W 6+ : 0–8%; and / or Ti 4+ 0–3%; and / or Zn 2+ 0–5%; and / or Ta 5+ : 0-5%; and / or B 3+ : 0-5%; and / or Si 4+ 0–5%; and / or Sb 3+ : 0-1%; and / or Sn 4+ : 0-1%; and / or Ce 4+ :0~1%, the Ln 3+ For La 3+ Gd 3+ Y 3+ Yb 3+ One or more of the following, wherein Rn + For Li + Na + K + One or more of the following; The anionic component contains: F - 61-80%; and / or O 2- 20–39%; and / or Cl - +Br - +I - : 0-2%.

5. The fluorophosphate optical glass according to any one of claims 1 to 4, characterized in that, Its components are expressed as mole percentages and satisfy one or more of the following six conditions: 1)(Mg 2+ -Ln 3+ ) / (Sr 2+ -Ba 2+ -Rn + The content of Mg is 1.5–10.0, preferably Mg. 2+ -Ln 3+ ) / (Sr 2+ -Ba 2+ -Rn + The content of (Mg) is 2.0 to 7.0, more preferably (Mg) 2+ -Ln 3+ ) / (Sr 2+ -Ba 2+ -Rn + The value is 2.5 to 4.

5. 2)(P 5+ +Ca 2+ +Rn + ) / Mg 2+ The value is 1.1 to 4.0, preferably (P) 5+ +Ca 2+ +Rn + ) / Mg 2+ The value is 1.3 to 3.5, more preferably (P 5+ +Ca 2+ +Rn + ) / Mg 2+ The value is 1.5 to 3.0, with further optimization (P). 5+ +Ca 2+ +Rn + ) / Mg 2+ It ranges from 1.8 to 2.5; 3)(P 5+ +Ba 2+ ) / (Mg 2+ +Al 3+ The value is 0.4–1.7, preferably (P) 5+ +Ba 2+ ) / (Mg 2+ +Al 3+ The value is 0.5 to 1.5, more preferably (P) 5+ +Ba 2+ ) / (Mg 2+ +Al 3+ The value is 0.6–1.2, and further optimization is preferred (P). 5+ +Ba 2+ ) / (Mg 2+ +Al 3+ The value is 0.6–1.0; 4)(Al 3+ +Rn + ) / Mg 2+ The value is 0.8–4.0, preferably (Al). 3+ +Rn + ) / Mg 2+ The value is 1.0 to 3.0, more preferably (Al). 3+ +Rn + ) / Mg 2 + The value is 1.2 to 2.5, with further optimization of (Al). 3+ +Rn + ) / Mg 2+ It ranges from 1.2 to 2.0; 5)(Mg 2+ +Ba 2+ ) / P 5+ The value is 1.0–3.5, preferably (Mg). 2+ +Ba 2+ ) / P 5+ The value is 1.2 to 3.0, more preferably (Mg 2+ +Ba 2+ ) / P 5+ The value is 1.3–2.5, with further preference given to (Mg). 2+ +Ba 2+ ) / P 5+ The value is 1.3 to 2.0; 6)(Nb 5+ +W 6+ ) / Ln 3+ The value is 0.01 to 2.0, preferably (Nb). 5+ +W 6+ ) / Ln 3+ The value is 0.05 to 1.5, more preferably (Nb) 5+ +W 6+ ) / Ln 3+ The value is 0.05–1.0, and further optimization is performed on (Nb). 5+ +W 6+ ) / Ln 3+ The value is 0.1 to 0.7, and the Ln 3+ For La 3+ Gd 3+ Y 3+ Yb 3+ One or more of the following, wherein Rn + For Li + Na + K + One or more of them.

6. The fluorophosphate optical glass according to any one of claims 1 to 4, characterized in that, Its components are expressed as mole percentages and satisfy one or more of the following four conditions: 1) Zn 2+ / Mg 2+ For concentrations below 0.5, Zn is preferred. 2+ / Mg 2+ The content is 0.3 or less, and Zn is preferred. 2+ / Mg 2+ For Zn content below 0.2, further optimization is needed. 2+ / Mg 2+ Below 0.1; 2)Zn 2+ / Ln 3+ For values ​​below 2.0, Zn is preferred. 2+ / Ln 3+ For values ​​below 1.0, Zn is preferred. 2+ / Ln 3+ For Zn content below 0.8, further optimization is needed. 2+ / Ln 3+ Below 0.5; 3)Rn + / Mg 2+ For values ​​below 0.35, Rn is preferred. + / Mg 2+ For values ​​below 0.3, Rn is preferred. + / Mg 2+ For values ​​below 0.2, Rn is further optimized. + / Mg 2+ Below 0.1; 4)Rn + / Ln 3+ For values ​​below 1.5, Rn is preferred. + / Ln 3+ For values ​​below 1.0, Rn is preferred. + / Ln 3+ For values ​​below 0.8, Rn is further optimized. + / Ln 3+ When Ln is below 0.5, 3+ For La 3+ Gd 3+ Y 3+ Yb 3+ One or more of the following, wherein Rn + For Li + Na + K + One or more of them.

7. The fluorophosphate optical glass according to any one of claims 1 to 4, characterized in that, Its components are expressed as mole percentages, where: F - / (P 5+ +B 3+ The value is 2.5–6.5, with F being the preferred option. - / (P 5+ +B 3+ The value is 3.0 to 6.0, with F being more preferred. - / (P 5+ +B 3+ The value of F is 3.5–5.5, and F is further optimized. - / (P 5+ +B 3+ ) is 3.5–5.0; and / or F - / O 2- The value is 1.8 to 3.8, with F being the preferred value. - / O 2- The value is 1.8 to 3.5, with F being more preferred. - / O 2- The value is 2.0 to 3.0, and F is further optimized. - / O 2- It ranges from 2.0 to 2.

8.

8. The fluorophosphate optical glass according to any one of claims 1 to 4, characterized in that, Its components are expressed as mole percentages, where: P 5+ 13-23%, P is preferred 5+ 15–22%; and / or Al 3+ 18-28%, with Al preferred 3+ 20-25%; and / or Ba 2+ 10-18%, Ba is preferred. 2+ : 11-16%; and / or Sr 2+ 14-24%, with Sr preferred 2+ 16–22%; and / or Mg 2+ 8-18%, preferably Mg 2+ : 10.5–17%; and / or Ca 2+ 8-18%, preferably Ca 2+ 10.5–16.5%; and / or Ln 3+ 0.1-8%, preferably Ln 3+ 0.5–5%; and / or Nb 5+ +W 6+ : Greater than 0% but less than or equal to 6%, Nb is preferred. 5+ +W 6 + 0.1–3%; and / or Ti 4+ 0-2%, preferably Ti 4+ 0-1%, more preferably without Ti 4+ ; and / or Rn + 0-4%, preferred Rn + 0-2%, more preferably free of Rn + ; and / or Zn 2+ 0-3%, preferably Zn 2+ 0-1%, preferably free of Zn 2+ ; and / or Ta 5+ 0-3%, preferably Ta 5+ 0-1%, preferably free of Ta 5+ ; and / or B 3+ 0-3%, B is preferred. 3+ 0-1%, preferably free of B 3+ ; and / or Si 4+ 0-3%, preferably Si 4+ 0-1%, more preferably free of Si 4+ ; and / or Sb 3+ 0-0.5%, preferably Sb 3+ : 0–0.2%; and / or Sn 4+ 0-0.5%, Sn preferred 4+ : 0–0.2%; and / or Ce 4+ 0-0.5%, preferably Ce 4+ : 0~0.2%, the Ln 3+ For La 3+ Gd 3+ Y 3+ Yb 3+ One or more of the following, wherein Rn + For Li + Na + K + One or more of them.

9. The fluorophosphate optical glass according to any one of claims 1 to 4, characterized in that, Its components are expressed as mole percentages, where: F - 63-75%, with F being the preferred option. - 65-73%; and / or O 2- 25-37%, preferred O 2- 27-35%; and / or Cl - +Br - +I - 0-1%, preferably Cl - +Br - +I - : 0~0.5%.

10. The fluorophosphate optical glass according to any one of claims 1 to 4, characterized in that, The refractive index n of the fluorophosphate optical glass d The preferred refractive index is 1.46–1.

53. d The refractive index n is 1.47 to 1.52, and more preferably 1.47 to 1.

52. d The Abbe number is 1.48–1.

51. d The optimal Abbe number is ν, which should be between 78 and 86. d The value is 79–84, with the Abbe number ν being more preferred. d It is 80-83.

11. The fluorophosphate optical glass according to any one of claims 1 to 4, characterized in that, The fluorophosphate optical glass has a weather resistance CR of Class 2 or higher, preferably Class 1; and / or water resistance stability D. W For classes 2 and above, water resistance stability D is preferred. W Class 1; and / or acid resistance stability D A For classes 3 or more, acid resistance stability D is preferred. A Class 2 or above; and / or coefficient of thermal expansion α -30～70℃ 160×10 -7 Below / K, the coefficient of thermal expansion α is preferred. -30～70℃ 150×10 -7 Below / K, a coefficient of thermal expansion α is preferred. -30～70℃ 140×10 -7 Below / K, the coefficient of thermal expansion α is further preferred. -30～70℃ 120×10 -7 / K~135×10 -7 / K; and / or transition temperature T g The preferred temperature is below 500℃, with a transition temperature T. g The temperature should be below 490°C, and the preferred transition temperature is T. g Temperature below 485℃; and / or thermal shock resistance coefficient β of 10.0 × 10⁻⁶. 3 The preferred thermal shock resistance coefficient β is 13.0 × 10⁻⁶. 3 The preferred thermal shock resistance coefficient β is 15.0 × 10⁻⁶. 3 The above further optimizes the thermal shock resistance coefficient β to be 16.0 × 10⁻⁶. 3 The above; and / or wear degree F A The preferred wear degree is 305-345. A The wear index is 315-340, with a more preferred wear index F. A The concentration is 320–335; and / or the density ρ is 4.20 g / cm³. 3 The preferred density ρ is 4.10 g / cm³. 3 Hereinafter, a density ρ of 4.00 g / cm³ is preferred. 3 Hereinafter, a density ρ of 3.95 g / cm³ is further preferred. 3 The following; and / or λ 80 For wavelengths below 350nm, λ is preferred. 80 For wavelengths below 340nm, λ is preferred. 80 The wavelength is 335 nm or less; and / or λ5 is 320 nm or less, preferably 310 nm or less, more preferably 305 nm or less; and / or Knoop hardness H K 330×10 7 Pa or higher, preferably 350 × 10 Pa 7 Pa or higher, more preferably 360 × 10 Pa 7 Pa or higher; and / or a bubble degree of A grade or higher, preferably A0 grade or higher, more preferably A. 00 class.

12. A glass precast component, characterized in that, It is made of fluorophosphate optical glass as described in any one of claims 1 to 11.

13. An optical element, characterized in that, It is made using the fluorophosphate optical glass according to any one of claims 1 to 11 or the glass preform according to claim 12.

14. An optical instrument, characterized in that, It contains fluorophosphate optical glass according to any one of claims 1 to 11; and / or contains optical elements according to claim 13.

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