Fluorophosphate optical glass

Abstract

The invention provides fluorophosphate optical glass with excellent inherent quality. 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%; the ratio of (P < 5 + > + Ca < 2 + > + R < n + >) / Mg < 2 + > is 1.1-4.0, Ln < 3 + > is one or more of La < 3 + >, Gd < 3 + >, Y < 3 + > and Yb < 3 + >, and R < n + > is one or more of Li < + >, Na < + > and K < + >; and the anion component contains F <-> and O < 2->, wherein the ratio of F <-> to O < 2-> is 1.8-3.8. Through reasonable component design, the fluorophosphate optical glass obtained by the invention has the advantages of fewer bubbles, higher bubble degree grade and excellent internal quality, and can meet the application of high-performance optical instruments.

Description

TECHNICAL FIELD

[0001] The present application relates to a fluorophosphate optical glass, in particular to a fluorophosphate optical glass with excellent intrinsic quality. BACKGROUND

[0002] In recent years, with the popularity of smart phones, monitoring security, vehicle-mounted imaging, etc., optical elements made of optical glass are widely used in these devices. Fluorophosphate optical glass has the characteristics of low refractive index and low dispersion, which can eliminate secondary spectral special dispersion in optical systems, improve resolution, and significantly improve the imaging quality of optical systems. Therefore, it is widely used. For optical glass, refractive index and Abbe number are its core optical properties. Refractive index and Abbe number determine the basic function of the glass. In addition to the expected optical performance, optical glass must also have excellent internal quality (such as bubbles and inclusions, etc.). If the component design of the optical glass is not reasonable, it is easy to cause a large number of bubbles in the glass, thereby causing the quality of the optical glass to decline, and in severe cases, even leading to the scrap of the optical glass. SUMMARY

[0003] The technical problem to be solved by the present application is to provide a fluorophosphate optical glass with excellent intrinsic quality.

[0004] The technical solution adopted by the present application to solve the technical problem is:

[0005] (1) A fluorophosphate optical glass, the components are expressed in mole percentage, the cation components contain: 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 (P 5+ + Ca 2+ + Rn + ) / Mg 2+ is 1.1-4.0, 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 + ;

[0006] The anionic component contains F - and O 2- , where F - / O 2- The value ranges from 1.8 to 3.8.

[0007] (2) The fluorophosphate optical glass according to (1) has components expressed as molar percentages, and the cationic component further 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%;

[0008] The anionic component also contains: Cl - +Br - +I - : 0-2%.

[0009] (3) Fluorophosphate optical glass, whose composition contains 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 (P 5+ +Ca 2+ +Rn + ) / Mg 2+ The value ranges from 1.1 to 4.0, F - / O 2- The value is 1.8 to 3.8, and the Ln is... 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 The value is 78-86, and the bubble degree is Grade A or above.

[0010] (4) The fluorophosphate optical glass according to (3) has components expressed as molar percentages, 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;

[0011] The anionic component contains: Cl - +Br - +I - : 0-2%.

[0012] (5) The fluorophosphate optical glass according to any one of (1) to (4), wherein the composition is expressed in molar percentage, wherein: (P 5+ +Ca 2+ +Rn + ) / Mg 2+ The value is 1.3 to 3.5, preferably (P) 5+ +Ca 2+ +Rn + ) / Mg 2+ The value is 1.5 to 3.0, more preferably (P 5+ +Ca2+ +Rn + ) / Mg 2+ 1.8–2.5; and / or (Mg 2+ -Ln 3+ ) / (Sr 2+ -Ba 2+ -Rn + The content of Mg is 1.0 to 12.0, preferably Mg. 2+ -Ln 3+ ) / (Sr 2+ -Ba 2+ -Rn + The content of (Mg) is 1.5 to 10.0, more preferably (Mg) 2+ -Ln 3+ ) / (Sr 2+ -Ba 2+ -Rn + The content of Mg is 2.0–7.0, with further preference given to (Mg). 2+ -Ln 3+ ) / (Sr 2+ -Ba 2+ -Rn + ) is 2.5–4.5; and / or (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+ ) is 0.6–1.0; and / or (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+1.2–2.0; and / or (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+ It ranges from 1.3 to 2.0.

[0013] (6) The fluorophosphate optical glass according to any one of (1) to (4), wherein the composition is expressed as a molar percentage, wherein: (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+ 0.1–0.7; and / or 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+ Less than 0.1; and / or 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+ Less than 0.5; and / or Rn + / Mg 2+ For values ​​below 0.35, Rn is preferred. + / Mg 2+ For values ​​below 0.3, Rn is preferred. + / Mg2+ For values ​​below 0.2, Rn is further optimized. + / Mg 2+ Less than 0.1; and / or 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+ Below 0.5; and / or 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 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 1.8–3.5, with F being the preferred value. - / O 2- The value is 2.0 to 3.0, with F being more preferred. - / O 2- The value is 2.0 to 2.8, 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.

[0014] (7) The fluorophosphate optical glass according to any one of (1) to (4), wherein the composition is expressed in mole percentage, wherein: 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.

[0015] (8) The fluorophosphate optical glass according to any one of (1) to (4), wherein the composition is expressed as a mole percentage, wherein: F - 61-80%, with F being the preferred option. - 63-75%, preferably F - 65-73%; and / or O 2- 20-39%, preferred O 2- 25-37%, more preferably O 2- 27-35%; and / or Cl - +Br - +I - 0-1%, preferably Cl - +Br - +I - : 0~0.5%.

[0016] (9) The fluorophosphate optical glass according to any one of (1) to (4), wherein the refractive index n of the fluorophosphate optical glass is... 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.

[0017] (10) 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 above, preferably Class 1; and / or the water resistance stability D W For classes 2 or 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 preferred coefficient of thermal expansion α- 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. gThe 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 index is 305-345, with an optimal wear index F. 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.

[0018] (11) Glass preforms are made of any of the fluorophosphate optical glass described in (1) to (10).

[0019] (12) Optical element, made of any of the fluorophosphate optical glass described in (1) to (10) or the glass preform described in (11).

[0020] (13) An optical instrument containing any of the fluorophosphate optical glass described in (1) to (10); and / or containing the optical element described in (12).

[0021] The beneficial effects of this invention are: through reasonable component design, the fluorophosphate optical glass obtained by this invention has fewer bubbles, a higher bubble degree, and excellent intrinsic quality, meeting the application requirements of high-performance optical instruments. Detailed Implementation

[0022] The embodiments of the fluorophosphate optical glass of the present invention will now be described in detail. However, the present invention is not limited to the embodiments described below, and appropriate modifications can be made to implement it within the scope of the purpose of the present invention. Furthermore, regarding repeated descriptions, although there are appropriate omissions, this will not limit the spirit of the invention. In the following text, the fluorophosphate optical glass of the present invention may be simply referred to as optical glass or glass.

[0023] [Fluorophosphate optical glass]

[0024] The following describes the range of each component (ingredient) constituting the optical glass of the present invention. In this specification, unless otherwise specified, the content of a cationic component is expressed as the molar percentage (mol%) of that cationic component relative to all cationic components, and the content of anionic components is expressed as the molar percentage (mol%) of that anionic component relative to all anionic components; the ratio between the contents of cationic components is the ratio of the molar percentage contents of each cationic component; the total content of cationic components is the sum of the molar percentage contents of each cationic component; the difference between the contents of cationic components is the difference in the molar percentage contents of each cationic component; the ratio between the contents of anionic components is the ratio of the molar percentage contents of each anionic component; the total content of cationic and anionic components is the sum of the molar percentage contents of cationic components relative to all cationic components and the molar percentage contents of anionic components relative to all anionic components; the ratio between the contents of cationic and anionic components is the ratio of the molar percentage contents of cationic components relative to all cationic components and the molar percentage contents of anionic components relative to all anionic components.

[0025] Unless otherwise specified in the specific context, the numerical ranges listed herein include upper and lower limits. "Above" and "below" include endpoint values ​​and all integers and fractions included within the range, but are not limited to the specific values ​​listed when the range is defined. The term "and / or" as used herein is inclusive; for example, "A and / or B" means either only A, or only B, or both A and B.

[0026] It should be noted that the ionic valences of the components described below are representative values ​​used for convenience and are not distinguishable from the ionic valences of other components. The ionic valences of the components in optical glass may exist beyond these representative values. For example, phosphorus (P) typically exists in glass with a +5 valence; therefore, in this patent, it is referred to as "P". 5+ "As a representative value, but there is a possibility that it exists in other ionic valence states, which is also within the scope of protection of this patent."

[0027] <About cationic components>

[0028] P 5+ It is a glass network forging component that can improve the stability and devitrification resistance of glass. In this invention, it contains more than 11% P. 5+ To achieve the above effects, it is preferable to contain more than 13% P. 5+ More preferably, it contains more than 15% P 5+ If P 5+ When the content of P exceeds 25%, the weather resistance of the glass tends to decrease, and the coefficient of thermal expansion deteriorates. Therefore, P 5+ The content of P is 25% or less, preferably 23% or less, and more preferably 22% or less. In some embodiments, P 5+ The content can 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%, 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.

[0029] Al 3+ This invention can improve the mechanical properties and weather resistance of glass, and reduce its coefficient of thermal expansion. It utilizes Al content of 16% or more. 3+ To achieve the above-mentioned effects, it is preferable to contain more than 18% Al. 3+ More preferably, it contains more than 20% Al 3+ If Al 3+ When the Al content exceeds 30%, the glass transition temperature and liquidus temperature increase, making glass melting more difficult. Simultaneously, the forming temperature increases, leading to accelerated glass volatilization. Furthermore, excessively high transition temperatures make molding difficult. Therefore, Al... 3+ The content of [agent] is 30% or less, preferably 28% or less, and more preferably 25% or less. In some embodiments, 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.

[0030] 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.

[0031] 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.

[0032] 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.

[0033] 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+ +Ba 2+ ) / (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.

[0034] 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.

[0035] 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.

[0036] 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 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%, 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.

[0037] In some implementations, Zn 2+ The content of Mg 2+ The ratio between the contents of Zn 2+ / Mg 2+ Keeping the concentration below 0.5% can optimize the glass's abrasion resistance while preventing a decrease in acid resistance. Therefore, Zn is preferred. 2+ / Mg 2+ The concentration is 0.5 or less, and Zn is preferred. 2+ / Mg 2+ For Zn content below 0.3, further optimization is needed. 2+ / Mg 2+ For Zn content below 0.2, further optimization is preferred. 2+ / Mg 2+ It is below 0.1. In some implementations, Zn 2+ / Mg 2+ The values ​​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, 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.

[0038] Rn + (Rn + For Li + Na + K + One or more of the following can reduce the glass transition temperature and refractive index, but if their content is too high, the stability and weather resistance of the glass will decrease. Therefore, in this invention, Rn + The content of Rn is 0-8%, preferably 0-4%, and more preferably 0-2%. In some embodiments, it is further preferred that Rn is not present. + In some implementations, Rn + The content 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.

[0039] In some implementations, Rn + / Mg 2+ By controlling Rn below 0.35, the density of the glass can be reduced while preventing a deterioration in its coefficient of thermal expansion. Therefore, Rn is preferred. + / Mg 2+ For values ​​below 0.35, Rn is preferred. + / Mg 2+ For values ​​below 0.3, Rn is further optimized. + / Mg 2+ For values ​​below 0.2, Rn is further preferred. + / Mg 2+ It is below 0.1. In some implementations, Rn + / Mg2+ The values ​​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, 0.11, 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, 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.

[0040] The inventors discovered through extensive experimental research that by making P 5+ Ca 2+ and Rn + Total content P 5+ +Ca 2+ +Rn + With Mg 2 + The ratio between the contents (P) 5+ +Ca 2+ +Rn + ) / Mg 2+ 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.

[0041] 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+ The value is 0.8 to 4.0, more preferably (Al). 3+ +Rn + ) / Mg 2+ The value is 1.0 to 3.0, with further optimization (Al). 3+ +Rn + ) / Mg 2+ The value is 1.2 to 2.5, with a further preferred value (Al). 3+ +Rn + ) / Mg 2+ It is 1.2 to 2.0. In some implementations, (A1) 3+ +Rn + ) / Mg 2+The possible values ​​are 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 0.5, 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, 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.

[0042] The glass of this invention contains an appropriate amount of Ln 3+ (Ln 3+ For La 3+ Gd 3+ Y 3+ Yb 3+ One or more of the following can improve the devitrification resistance and thermal stability of glass, which is beneficial for achieving a higher Abbe number. However, if its content is too high, the refractive index of the glass will be too high, making it difficult to meet design requirements. Therefore, in this invention, Ln 3+ The content 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, 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.

[0043] 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.

[0044] Through extensive experimental research, the inventor discovered that by using (Mg) 2+ -Ln 3+ ) / (Sr 2+ -Ba 2+ -Rn + By controlling the coefficient of thermal shock resistance of the glass within the range of 1.0 to 12.0, the coefficient of thermal expansion of the glass can be improved, and the degradation of the coefficient of thermal expansion can be prevented. Therefore, (Mg) is preferred. 2+ -Ln 3+ ) / (Sr 2+ -Ba 2+ -Rn + The content of (Mg) is 1.0 to 12.0, more preferably (Mg) 2+ -Ln 3+ ) / (Sr 2+ -Ba 2+ -Rn + The content of (Mg) is 1.5–10.0, with further preference given to (Mg). 2+ -Ln 3+ ) / (Sr 2+ -Ba 2+ -Rn + The preferred value is 2.0–7.0, with (Mg) being even more preferred. 2+ -Ln 3+ ) / (Sr2 + -Ba 2+ -Rn + The content of (Mg) is 2.5–4.5. In some embodiments, (Mg) 2+ -Ln 3+ ) / (Sr 2+ -Ba 2+ -Rn + The possible values ​​are 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, 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.

[0045] In some implementations, Rn + / Ln 3+ By keeping Rn below 1.5, the density of the glass can be reduced while preventing a decrease in its thermal shock resistance coefficient. Therefore, Rn is preferred. + / Ln 3+ Rn is preferred to be 1.5 or less. + / Ln 3+ For values ​​below 1.0, Rn is further optimized. + / Ln 3+ For values ​​below 0.8, Rn is further preferred. + / Ln 3+ It is below 0.5. In some implementations, 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.

[0046] 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.

[0047] 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+ The value is 0.01 to 2.0, more preferably (Nb 5+ +W 6+ ) / Ln 3+ The value is 0.05–1.5, with further optimization of (Nb) 5+ +W 6+ ) / Ln 3+ The value is 0.05 to 1.0, and further preferred (Nb) 5+ +W 6+ ) / Ln 3+ It is 0.1 to 0.7. In some implementations, (Nb 5+ +W 6+ ) / Ln 3+ The possible values ​​are 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 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.

[0048] Ti 4+ Ti can increase the refractive index of glass and adjust its Abbe number, but if its content is too high, the tendency of the glass to crystallize increases, the light transmittance decreases, and the glass's meltability decreases. Therefore, in this invention, Ti... 4+ The content of Ti is 0-3%, preferably 0-2%, and more preferably 0-1%. In some embodiments, it is further preferred that Ti is not present. 4+ In some implementations, Ti 4+ The content 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%, 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.

[0049] Ta 5+ It can increase the refractive index of glass, but when its content is high, the glass is prone to devitrification, and the raw material cost of glass increases. Therefore, Ta 5+ The content of Ta is 0-5%, preferably 0-3%, and more preferably 0-1%. In some embodiments, it is further preferred that Ta is not present. 5+ In some implementations, Ta 5+ The content 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%, 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.

[0050] Si 4+ It can improve the devitrification resistance and processability of glass, and adjust the high-temperature viscosity of glass. However, when its content is too high, the melting performance of glass decreases. Therefore, the Si content in the optical glass of this invention... 4+ The content of Si is 0-5%, preferably 0-3%, and more preferably 0-1%. In some embodiments, it is further preferred that Si is not present. 4+ In some implementations, Si 4+ The content 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%, 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.

[0051] B 3+ Fluorine can improve the devitrification resistance of glass, but in fluorine-containing optical glasses, the melting process involves strong volatilization, causing instability in the optical constants and the appearance of streaks. Therefore, B 3+ The content of B is 0-5%, preferably 0-3%, and more preferably 0-1%. In some embodiments, it is further preferred that it does not contain B. 3+ In some implementations, B 3+The content 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%, 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.

[0052] The glass of this invention may contain Sb 3+ Sn 4+ Ce 4+ One or more components in it are used as clarifying agents to improve the defoaming effect of the glass. When Sb 3+ When the content of Sb exceeds 1%, the glass tends to have reduced clarification properties, and its strong oxidizing effect promotes the deterioration of the forming mold. Therefore, in this invention, Sb... 3+ The content of Sb is 0-1%, preferably 0-0.5%, and more preferably 0-0.2%. In some embodiments, Sb 3+ The content 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%, 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. 4+ It can also be used as a clarifying agent, but when its content exceeds 1%, it will cause severe glass coloring, or when the glass is heated, softened, and then molded or re-formed, Sn... 4+ It can become the starting point for crystal nucleation, leading to a tendency for devitrification. Therefore, the Sn of this invention... 4+ The content is 0-1%, preferably 0-0.5%, and more preferably 0-0.2%. In some embodiments, Sn 4+ The content 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%, 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. 4+ Functions and content of Sn 4+Similarly, its content is 0-1%, preferably 0-0.5%, more preferably 0-0.2%. In some embodiments, Ce 4+ The content 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%, 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.

[0053] Without compromising the properties and purpose of the optical glass of this invention, it is permissible to include, as needed, Zr in the optical glass of this invention. 4+ 、Ge 4+ Bi 3+ Te 4+ Other components. In some embodiments, Zr in the optical glass of the present invention 4 + 、Ge 4+ Bi 3+ Te 4+ The individual or total content of Zr is preferably 5% or less, more preferably 3% or less, further preferably 1% or less, and even more preferably 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 + .

[0054] <About Anionic Components>

[0055] F - This invention can reduce the refractive index and transition temperature of glass, and increase the Abbe number of glass. It achieves this by containing more than 61% F... - To achieve the above effects, F is preferred. - The content is 63% or more, preferably F. - The content is over 65%. On the other hand, if F - Excessive F content weakens the stability of glass and increases its coefficient of thermal expansion, especially during the melting process. - The volatilization of F not only easily pollutes the environment, but also easily causes uneven internal composition of the glass. Therefore, in this invention, F - The content of [agent] is 80% or less, preferably 75% or less, and more preferably 73% or less. In some embodiments, 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.

[0056] 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 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.

[0057] The optical glass of this invention contains O 2- In particular, by containing more than 20% O 2- This can improve the stability and weather resistance of glass, and suppress the deterioration of glass abrasion and streaking. On the other hand, by using O... 2- By controlling the content of O to below 39%, it is possible to prevent the glass from experiencing a rise in high-temperature viscosity and melting temperature. Therefore, O 2- The content is 20-39%, preferably 25-37%, and more preferably 27-35%. In some embodiments, O 2- The content can 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%, 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.

[0058] In some implementations, F - / O 2- Maintaining the value within the range of 1.8 to 3.8 is beneficial for improving the glass's resistance to devitrification and bubble formation. Therefore, F is preferred. - / O 2- The value is 1.8 to 3.8, with F being more preferred. - / O 2- The value is 1.8–3.5, with F being the most preferred. - / O 2- The optimal value is 2.0 to 3.0, with F being the most preferred. - / O 2- The value is 2.0 to 2.8. In some implementations, 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.

[0059] 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.

[0060] <Regarding components that should not be present>

[0061] 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.

[0062] Cationic components such as As, Pb, Th, Cd, Tl, Os, Be, and Se have been increasingly subject to controlled use in recent years due to their status as hazardous chemicals. Environmental protection measures are essential not only in glass manufacturing but also in processing and post-product disposal. Therefore, given the importance of environmental impact, it is preferable to eliminate them entirely, except where their contamination is unavoidable. As a result, the optical glass becomes virtually free of pollutants. Therefore, the optical glass of this invention can be manufactured, processed, and disposed of even without special environmental countermeasures.

[0063] The terms "not containing" and "0%" as used herein mean that the component was not intentionally added as a raw material to the fluorophosphate optical glass of this invention; however, as raw materials and / or equipment for producing optical glass, there may be certain impurities or components that are not intentionally added, which may be present in small or trace amounts in the final optical glass, and such situations are also within the scope of protection of this patent.

[0064] The performance of the fluorophosphate optical glass of the present invention will now be described.

[0065] <Refractive Index and Abbe Number>

[0066] The refractive index (n) of optical glass d ) and Abbe number (ν d Tested according to the method specified in the national standard GB / T 7962.1—2010.

[0067] In some embodiments, the refractive index (n) of the fluorophosphate optical glass of the present invention is... d The lower limit of the refractive index (n) is 1.46, preferably 1.47, and more preferably 1.48; in some embodiments, the refractive index (n) of the optical glass of the present invention is... d The upper limit for the refractive index (n) is 1.53, preferably 1.52, and more preferably 1.51. In some embodiments, the refractive index (n) is... dThe possible values ​​are 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, and 1.49. 7, 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, etc., as well as all ranges and subranges between the above values.

[0068] In some embodiments, the Abbe number (ν) of the fluorophosphate optical glass of the present invention is... d The lower limit of the Abbe number (ν) is 78, preferably 79, and more preferably 80; in some embodiments, the Abbe number (ν) of the optical glass of the present invention is... d The upper limit of ) is 86, the preferred upper limit is 84, and the more preferred upper limit is 83.

[0069] In some implementations, the Abbe number (ν) d The range can be 78, 78.1, 78.3, 78.5, 78.7, 78.9, 79, 79.1, 79.3, 79.5, 79.7, 79.9, 80, 80.1, 80.3, 80.5, 80.7, 80.9, 81, 81.1, 81.3, 81.5, 81.7, 81.9, 82, 82.1, 82.3, 82.5, 82.7, 82.9, 83, 83.1, 83.3, 83.5, 83.7, 83.9, 84, 84.1, 84.3, 84.5, 84.7, 84.9, 85, 85.1, 85.3, 85.5, 85.7, 85.9, 86, etc., as well as all ranges and subranges between the above values.

[0070] <Density>

[0071] The density (ρ) of optical glass was tested according to the method specified in the national standard GB / T7962.20—2010.

[0072] In some embodiments, the density (ρ) of the fluorophosphate optical glass of the present invention is 4.20 g / cm³. 3 The preferred value is 4.10 g / cm³. 3 The following is more preferably 4.00 g / cm³ 3 The following is a further preferred value: 3.95 g / cm³ 3Below. In some embodiments, the density (ρ) can be 4.20 g / cm³. 3 4.19 g / cm 3 4.18 g / cm 3 4.17 g / cm 3 4.16 g / cm 3 4.15g / 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 4.05g / cm 3 4.04 g / cm 3 4.03 g / cm 3 4.02 g / cm 3 4.01 g / cm 3 4.00g / cm 3 3.99g / cm 3 3.98g / cm 3 3.97g / cm 3 3.96g / cm 3 3.95g / cm 3 3.94g / cm 3 3.93g / cm 3 3.92g / cm 3 3.91g / cm 3 3.90g / cm 3 3.89 g / cm 3 3.88g / cm 3 3.87 g / cm 3 3.86 g / cm 3 3.85g / cm 3 3.84 g / cm 3 3.83 g / cm 3 3.82g / cm 3 3.81 g / cm 3 3.80g / cm 3 3.79g / cm 3 3.78g / cm 3 3.77 g / cm 3 3.76 g / cm3 3.75g / cm 3 3.74 g / cm 3 3.73 g / cm 3 3.72g / cm 3 3.71 g / cm 3 3.70g / cm 3 And so on, as well as all ranges and subranges between the above values.

[0073] <Weather resistance>

[0074] The weather resistance (CR) of optical glass is tested as follows: the glass sample is placed in a test chamber with a relative humidity of 90% saturated water vapor, and the chamber is alternately cyclical at 40-50°C every hour for 15 cycles. The weather resistance is classified according to the change in turbidity before and after the sample is placed in the chamber. Table 1 shows the weather resistance classification.

[0075] Table 1. Weather Resistance Classification Table

[0076]

[0077] In some embodiments, the fluorophosphate optical glass of the present invention has a weather resistance (CR) of Class 2 or above, preferably Class 1.

[0078] <Stability under water resistance>

[0079] Water resistance stability of optical glass (D) W (Powder method) Tested according to the method specified in the national standard GB / T 17129.

[0080] In some embodiments, the water resistance stability (D) of the fluorophosphate optical glass of the present invention is... W There are two or more categories, with category 1 being preferred.

[0081] <Stability under acid conditions>

[0082] Acid resistance stability of optical glass (D) A (Powder method) Tested according to the method specified in the national standard GB / T 17129.

[0083] In some embodiments, the acid resistance stability (D) of the fluorophosphate optical glass of the present invention is... A It should be of 3 or more categories, preferably 2 or more categories.

[0084] <Coefficient of thermal expansion>

[0085] The coefficient of thermal expansion of optical glass (α) -30～70℃ Data for -30 to 70℃ were tested according to the method specified in the national standard GB / T7962.16—2010.

[0086] In some embodiments, the coefficient of thermal expansion (α) of the fluorophosphate optical glass of the present invention is... -30～70℃ ) is 160×10 -7 / K or less, preferably 150×10 -7 / K or less, preferably 140×10 -7 Below / K, further preferably 120×10 -7 / K~135×10 -7 / K. In some implementations, the coefficient of thermal expansion (α) -30～70℃ It can be 120×10 -7 / K、121×10 -7 / K、123×10 -7 / K、125×10 -7 / K、127×10 -7 / K、129×10 -7 / K、130×10 -7 / K、131×10 -7 / K、133×10 -7 / K、135×10 -7 / K、137×10 -7 / K、139×10 -7 / K、140×10 -7 / K、141×10 -7 / K、143×10 -7 / K、145×10 -7 / K、147×10 -7 / K、149×10 -7 / K、150×10 -7 / K、151×10 -7 / K、153×10 -7 / K、155×10 -7 / K、157×10 -7 / K、159×10 -7 / K、160×10 -7 / K, etc., and all ranges and subranges between the above values.

[0087] <Transition Temperature>

[0088] Transition temperature of optical glass (T) g Test according to the method specified in the national standard GB / T7962.16—2010.

[0089] In some embodiments, the transition temperature (Tf) of the fluorophosphate optical glass of the present invention is... gThe temperature is below 500°C, preferably below 490°C, and more preferably below 485°C.

[0090] In some implementations, the transition temperature (T) g The values ​​can be 460℃, 461℃, 463℃, 465℃, 467℃, 469℃, 470℃, 471℃, 473℃, 475℃, 477℃, 479℃, 480℃, 481℃, 483℃, 485℃, 487℃, 489℃, 490℃, 491℃, 493℃, 495℃, 497℃, 499℃, 500℃, etc., as well as all ranges and subranges between the above values.

[0091] <Coefficient of thermal shock resistance>

[0092] Through extensive and long-term research, the inventors have discovered that the cracking of aspherical lenses manufactured by precision molding of fluorophosphate optical glass mainly occurs during the cooling phase after the glass preform has been hot-pressed, specifically at the molding temperature (usually the sag temperature of the glass). s The transition temperature (T) to glass near the glass transition temperature g In the temperature range of 10–30°C, when using alloy or ceramic molds for precision molding, this temperature range is typically the stage where the mold covers the molded lens for rapid cooling and shaping. To ensure the shaping accuracy of aspherical lenses, the mold often maintains a certain pressure during this process. If the glass's thermal shock resistance is insufficient within this temperature range, the glass element will experience significant thermal stress due to the cooling thermal shock, leading to lens breakage. The thermal shock resistance of optical glass can be represented by its thermal shock resistance coefficient (β). The higher the thermal shock resistance coefficient (β) of optical glass, the less likely the glass element is to break due to the significant thermal stress generated by the cooling thermal shock.

[0093] The formula for calculating the thermal shock resistance coefficient (β) of glass is as follows:

[0094] β=λ(1-ν) / αE

[0095] λ is the thermal conductivity of glass (W / (mK));

[0096] α is the coefficient of thermal expansion of glass (10). -7 / K);

[0097] E is the Young's modulus of the glass (Pa);

[0098] ν is the Poisson's ratio of the glass.

[0099] In some embodiments, the thermal shock resistance coefficient (β) of the fluorophosphate optical glass of the present invention is 10.0 × 10⁻⁶. 3 The preferred value is 13.0 × 10.3 The above is preferred, and more preferably 15.0 × 10 3 The above is further preferred to be 16.0×10 3 That's all. In some embodiments, the thermal shock resistance coefficient (β) can be 10.0 × 10⁻⁶. 3 10.1×10 3 10.3×10 3 10.5×10 3 10.7×10 3 10.9×10 3 11.0×10 3 11.1×10 3 11.3×10 3 11.5×10 3 11.7×10 3 11.9×10 3 12.0×10 3 12.1×10 3 12.3×10 3 12.5×10 3 12.7×10 3 12.9×10 3 13.0×10 3 13.1×10 3 13.3×10 3 13.5×10 3 13.7×10 3 13.9×10 3 14.0×10 3 14.1×10 3 14.3×10 3 14.5×10 3 14.7×10 3 14.9×10 3 15.0×10 3 15.1×10 3 15.3×10 3 15.5×10 3 15.7×10 3 15.9×10 3 16.0×10 3 16.1×10 3 16.3×10 3 16.5×10 3 16.7×10 3 16.9×10 3 17.0×10 317.1×10 3 17.3×10 3 17.5×10 3 17.7×10 3 17.9×10 3 18.0×10 3 And so on, as well as all ranges and subranges between the above values.

[0100] <wear level>

[0101] Abrasion resistance (F) of optical glass A The wear amount (volume) refers to the ratio of the wear amount of the test specimen to the wear amount (volume) of the standard specimen (H-K9 glass) under exactly the same conditions, multiplied by 100. The formula is as follows:

[0102] F A =V / V0×100=(W / ρ) / (W0 / ρ0)×100

[0103] Where: V—volume wear of the tested sample;

[0104] V0—Standard sample volume wear amount;

[0105] W—Mass wear of the tested sample;

[0106] W0—Standard sample mass wear amount;

[0107] ρ—Density of the sample being measured;

[0108] ρ0 — density of the standard sample.

[0109] In some embodiments, the abrasion resistance (F) of the fluorophosphate optical glass of the present invention is... A The lower limit for the abrasion degree (F) is 305, preferably 315, and more preferably 320. In some embodiments, the abrasion degree (F) of the optical glass of the present invention is... A The upper limit of ) is 345, the preferred upper limit is 340, and the more preferred upper limit is 335.

[0110] In some implementations, wear rate (F) A The range 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, etc., as well as all ranges and subranges between the above values.

[0111] <Colorization>

[0112] The short-wavelength transmission spectral characteristics of the glass of this invention are expressed using colorimetric intensity (λ). 80 And λ5) represent. λ 80 This refers to the wavelength corresponding to a glass transmittance of 80%. λ 80 The measurement was performed using a glass with a thickness of 10 ± 0.1 mm and two optically polished, parallel planes. The spectral transmittance was measured in the wavelength range from 280 nm to 700 nm, and wavelengths exhibiting 80% transmittance were recorded. Spectroscopic transmittance, or transmittance, is the value of the light incident perpendicularly to the aforementioned surface of the glass with an intensity I... in Light passes through the glass and exits from a plane with an intensity of I. out In the case of light, through I out / I in The value represents the transmittance, which also includes the surface reflection loss on the aforementioned surfaces of the glass. The higher the refractive index of the glass, the greater the surface reflection loss. Therefore, in optical glass, λ... 80 A small value of λ means that the glass itself has very little coloration, resulting in high light transmittance.

[0113] 5. Similarly.

[0114] In some embodiments, the λ of the fluorophosphate optical glass of the present invention 80 For wavelengths below 350nm, λ is preferred. 80 For wavelengths below 340nm, λ is preferred. 80 The wavelength is below 335 nm. In some embodiments, the λ of the optical glass... 80 It can be 320nm, 321nm, 322nm, 323nm, 324nm, 325nm, 326nm, 327nm, 328nm, 329nm, 330nm, 331nm, 332nm, 333nm, 334nm, 335nm, 336nm, 337nm, 338nm, 339nm, 340nm, 341nm, 342nm, 343nm, 344nm, 345nm, 346nm, 347nm, 348nm, 349nm, 350nm, etc., as well as all ranges and subranges between the above values.

[0115] In some embodiments, the λ5 of the fluorophosphate optical glass of the present invention is 320 nm or less, preferably 310 nm or less, and more preferably 305 nm or less. In some embodiments, the λ5 of the optical glass can be 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., as well as all ranges and sub-ranges between the above values.

[0116] Knoop Hardness

[0117] 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.

[0118] 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.

[0119] <Effervescence>

[0120] The bubble degree of optical glass is tested according to the method specified in the national standard GB / T7962.8—2010.

[0121] 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.

[0122] [Manufacturing Method]

[0123] The manufacturing method of the fluorophosphate optical glass of this invention is as follows: The glass of this invention is produced using conventional raw materials and processes. Carbonates, nitrates, sulfates, hydroxides, oxides, fluorides, phosphates, metaphosphates, etc., are used as raw materials. After being batched according to conventional methods, the batched charge is added to a melting furnace (such as a covered platinum crucible, platinum alloy crucible, etc.) at 850–1200°C for melting. After clarification, stirring, and homogenization, a homogeneous molten glass without bubbles and undissolved substances is obtained. This molten glass is then cast in a mold and annealed. Those skilled in the art can appropriately select raw materials, process methods, and process parameters according to actual needs.

[0124] [Glass preforms and optical components]

[0125] Glass preforms can be manufactured from the produced fluorophosphate optical glass using methods such as grinding, hot pressing, or precision stamping. Specifically, glass preforms can be manufactured by machining the optical glass, such as grinding and polishing; or by hot pressing a preform made from the optical glass for molding and then grinding it; or by precision stamping a preform made from the ground glass.

[0126] It should be noted that the means of preparing the glass preform are not limited to those described above. As mentioned above, the optical glass of the present invention is useful for various optical elements and optical designs, and it is particularly preferred to form a preform from the optical glass of the present invention, using the preform for hot pressing, precision stamping, etc., to manufacture optical elements such as lenses, prisms, and diffraction gratings.

[0127] Both the glass preform and the optical element of the present invention are formed from the fluorophosphate optical glass described above. The glass preform of the present invention possesses the excellent properties of optical glass; the optical element of the present invention possesses the excellent properties of optical glass, and can provide various optical elements such as lenses, prisms, and diffraction gratings with high optical value.

[0128] Examples of lenses include concave meniscus lenses, convex meniscus lenses, biconvex lenses, biconcave lenses, plano-convex lenses, plano-concave lenses, and so on, where the lens surface is spherical or aspherical.

[0129] [Optical Instruments]

[0130] The optical elements formed by the fluorophosphate optical glass of this invention can be used to manufacture optical instruments such as photographic equipment, portable electronic devices (such as mobile phones, watches, etc.), video equipment, display equipment, and monitoring equipment.

[0131] [Example]

[0132] <Examples of Fluorophosphate Optical Glass>

[0133] To further illustrate and explain the technical solution of the present invention, the following non-limiting embodiments are provided.

[0134] In this embodiment, fluorophosphate optical glass with the compositions shown in Tables 2 to 4 was obtained using the optical glass manufacturing method described above. Furthermore, the properties of each glass were measured using the testing method described in this invention, and the measurement results are shown in Tables 2 to 4.

[0135] Table 2.

[0136]

[0137]

[0138] Table 3.

[0139]

[0140]

[0141]

[0142] Table 4.

[0143]

[0144]

[0145] <Example of Glass Prefabricated Components>

[0146] The glass obtained in Tables 2 to 4 of the examples of fluorophosphate optical glass is used, for example, by grinding or by molding such as hot pressing or precision stamping, to produce preforms of various lenses and prisms such as concave meniscus lenses, convex meniscus lenses, biconvex lenses, biconcave lenses, plano-convex lenses, and plano-concave lenses.

[0147] <Optical Component Examples>

[0148] Annealing the preforms obtained from the above glass preform examples reduces the internal stress of the glass while fine-tuning the refractive index, so that the optical properties such as the refractive index reach the desired values.

[0149] Next, the prefabricated parts are ground and polished to produce various lenses and prisms, such as concave meniscus lenses, convex meniscus lenses, biconvex lenses, biconcave lenses, plano-convex lenses, and plano-concave lenses. Anti-reflective coatings can also be applied to the surface of the resulting optical elements.

[0150] <Examples of Optical Instruments>

[0151] The optical elements obtained from the above-described optical element embodiments can be used, through optical design, to form optical components or optical assemblies by using one or more optical elements. These components can be used in, for example, imaging devices, sensors, microscopes, medical technology, digital projection, communications, optical communication technology / information transmission, optics / lighting in the automotive field, lithography technology, excimer lasers, wafers, computer chips, and integrated circuits and electronic devices that include such circuits and chips.

Claims

1. 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 (P 5+ +Ca 2+ +Rn + ) / Mg 2+ The value is 1.1 to 4.0, 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 the following; The anionic component contains F - and O 2- , where F - / O 2- The value ranges from 1.8 to 3.

8.

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 (P 5+ +Ca 2+ +Rn + ) / Mg 2+ The value ranges from 1.1 to 4.0, F - / O 2- The value is 1.8 to 3.8, and the Ln is... 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 The value is 78-86, and the bubble degree is Grade A or 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: 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, of which: (P 5+ +Ca 2+ +Rn + ) / Mg 2+ The value is 1.3 to 3.5, preferably (P) 5+ +Ca 2+ +Rn + ) / Mg 2+ The value is 1.5 to 3.0, more preferably (P 5+ +Ca 2+ +Rn + ) / Mg 2+ 1.8–2.5; and / or (Mg 2+ -Ln 3+ ) / (Sr 2+ -Ba 2+ -Rn + The content of Mg is 1.0 to 12.0, preferably Mg. 2 + -Ln 3+ ) / (Sr 2+ -Ba 2+ -Rn + The content of (Mg) is 1.5 to 10.0, more preferably (Mg) 2+ -Ln 3+ ) / (Sr 2+ -Ba 2+ -Rn + The content of Mg is 2.0–7.0, with further preference given to (Mg). 2+ -Ln 3+ ) / (Sr 2+ -Ba 2+ -Rn + ) is 2.5–4.5; and / or (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+ ) is 0.6–1.0; and / or (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+ 1.2–2.0; and / or (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+ It ranges from 1.3 to 2.

0.

6. The fluorophosphate optical glass according to any one of claims 1 to 4, characterized in that, Its components are expressed as mole percentages, of which: (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+ 0.1–0.7; and / or 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+ Less than 0.1; and / or 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+ Less than 0.5; and / or 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+ Less than 0.1; and / or 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+ Below 0.5; and / or 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 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 1.8–3.5, with F being the preferred value. - / O 2- The value is 2.0 to 3.0, with F being more preferred. - / O 2- The value is 2.0 to 2.8, 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.

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: 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.

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: F - 61-80%, with F being the preferred option. - 63-75%, preferably F - 65-73%; and / or O 2- 20-39%, preferred O 2- 25-37%, more preferably O 2- 27-35%; and / or Cl - +Br - +I - 0-1%, preferably Cl - +Br - +I - : 0~0.5%.

9. 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.

10. 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 or 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 index is 305-345, with an optimal wear index F. 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.

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

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

13. An optical instrument, characterized in that, It contains fluorophosphate optical glass according to any one of claims 1 to 10; and / or contains optical elements according to claim 12.

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