阅读说明：本技术 低荧光光学玻璃 (Low-fluorescence optical glass ) 是由 蔡冬雪 于 2021-01-12 设计创作，主要内容包括：本发明提供一种低荧光光学玻璃,所述低荧光光学玻璃的组分以重量百分比表示,含有：SiO-2：60～80％、B-2O-3：5～20％、Al-2O-3：1～10％、Rn-2O：5～20％,其中Rn-2O/(SiO-2+B-2O-3)为0.07～0.25,所述Rn-2O为Li-2O、Na-2O、K-2O中的一种以上。本发明光学玻璃在具有期望的折射率和阿贝数的同时荧光度等级较低,同时具备优异的耐水作用稳定性,量产工艺性能好,长期使用透过率不会产生明显下降,特别适于生物观测等领域的使用,尤其适合应用在显微镜的盖玻片、载玻片、接物镜中。(The invention provides low-fluorescence optical glass, which comprises the following components in percentage by weight: SiO 2 2 ：60～80％、B 2 O 3 ：5～20％、Al 2 O 3 ：1～10％、Rn 2 O: 5 to 20%, wherein Rn 2 O/(SiO 2 +B 2 O 3 ) 0.07 to 0.25, the Rn 2 O is Li 2 O、Na 2 O、K 2 And O or more. The optical glass has the advantages of expected refractive index and Abbe number, lower fluorescence level, excellent water-resistant action stability, good mass production process performance, no obvious reduction of transmittance after long-term use, and is particularly suitable for the fields of biological observation and the likeIs particularly suitable for application in microscope cover slips, glass slides and objective lenses.)

1. The low fluorescence optical glass is characterized by comprising the following components in percentage by weight: SiO 2₂：60～80％、B₂O₃：5～20％、Al₂O₃：1～10％、Rn₂O: 5 to 20%, wherein Rn₂O/(SiO₂+B₂O₃) 0.07 to 0.25, the Rn₂O is Li₂O、Na₂O、K₂And O or more.

2. The low fluorescence optical glass according to claim 1, wherein the composition further comprises, in weight percent: and (3) RO: 0 to 10%, and/or Nb₂O₅: 0 to 8%, and/or ZrO₂: 0-3%, and/or a clarifying agent: 0-1%, RO is more than one of BaO, SrO, CaO and MgO, and a clarifying agent is Sb₂O₃、SnO₂、SnO、CeO₂One or more of (a).

3. The low fluorescence optical glass is characterized in that the components of the low fluorescence optical glass contain SiO₂、B₂O₃And Rn₂O, the components of which are expressed in weight percentage, wherein Rn₂O/(SiO₂+B₂O₃) 0.07 to 0.25, the refractive index n of the low fluorescence optical glass_dIs 1.48 to 1.55, and has an Abbe number v_d56-65, fluorescence grade Y above grade 2, water-resistant stability D_wIs more than 2 types, the Rn₂O is Li₂O、Na₂O、K₂And O or more.

4. The low fluorescence optical glass according to claim 3, wherein the composition comprises, in weight percent: SiO 2₂：60～80％、B₂O₃：5～20％、Al₂O₃：1～10％、Rn₂O：5～20％、RO：0～10％、Nb₂O₅：0～8％、ZrO₂: 0-3% of a clarifying agent: 0-1%, RO is more than one of BaO, SrO, CaO and MgO, and a clarifying agent is Sb₂O₃、SnO₂、SnO、CeO₂One or more of (a).

5. The low fluorescence optical glass according to any one of claims 1 to 4, wherein the glass is characterized in thatThe components are expressed by weight percentage, wherein: b is₂O₃/SiO₂0.07 to 0.3, preferably B₂O₃/SiO₂0.08 to 0.25, more preferably B₂O₃/SiO₂0.1 to 0.2, and preferably B₂O₃/SiO₂0.1 to 0.15.

6. The low-fluorescence optical glass according to any one of claims 1 to 4, wherein the composition is represented by weight percentage, wherein: al (Al)₂O₃/B₂O₃0.2 to 1.5, preferably Al₂O₃/B₂O₃0.3 to 1.0, more preferably Al₂O₃/B₂O₃0.4 to 0.9, and more preferably Al₂O₃/B₂O₃0.5 to 0.8.

7. The low-fluorescence optical glass according to any one of claims 1 to 4, wherein the composition is represented by weight percentage, wherein: rn₂O/(SiO₂+B₂O₃) 0.08 to 0.2, preferably Rn₂O/(SiO₂+B₂O₃) 0.1 to 0.18, more preferably Rn₂O/(SiO₂+B₂O₃) 0.11 to 0.16.

8. The low-fluorescence optical glass according to any one of claims 1 to 4, wherein the composition is represented by weight percentage, wherein: RO/Rn₂O is 0.1 to 1.0, preferably RO/Rn₂O is 0.2 to 0.8, and RO/Rn is more preferable₂O is 0.3 to 0.7, and RO/Rn is more preferable₂O is 0.4 to 0.65.

9. The low-fluorescence optical glass according to any one of claims 1 to 4, wherein the composition is represented by weight percentage, wherein: SiO 2₂: 62-78%, preferably SiO₂: 65-75%; and/or B₂O₃: 6 to 18%, preferablyB₂O₃: 7-15%; and/or Al₂O₃: 2 to 9%, preferably Al₂O₃: 3-8%; and/or Rn₂O: 6 to 18%, preferably Rn₂O: 7-15%; and/or RO: 0-9%, preferably RO: 0 to 7 percent; and/or Nb₂O₅: 0 to 6%, preferably Nb₂O₅: 0 to 5 percent; and/or ZrO₂: 0 to 2%, preferably ZrO₂: 0 to 1 percent; and/or a clarifying agent: 0-0.8%, preferably clarifying agent: 0 to 0.5 percent.

10. The low-fluorescence optical glass according to any one of claims 1 to 4, wherein the refractive index n of the low-fluorescence optical glass_d1.48 to 1.55, preferably a refractive index n_d1.49 to 1.54 and/or an Abbe number v_dIs 56-65, and the Abbe number v is preferred_dIs 58 to 64.

11. The low-fluorescence optical glass according to any one of claims 1 to 4, wherein the low-fluorescence optical glass has a fluorescence level Y of at least 2, preferably at least 1, and/or a water-resistant stability D_wIs of 2 or more types, preferably water-resistant stability D_wIs type 1.

12. The glass preform is characterized by being made of the low-fluorescence optical glass according to any one of claims 1 to 11.

13. An optical element produced from the low-fluorescence optical glass according to any one of claims 1 to 11 or the glass preform according to claim 12.

14. An optical instrument comprising the low-fluorescence optical glass according to any one of claims 1 to 11 and/or the optical element according to claim 13.

Technical Field

The invention relates to optical glass, in particular to low-fluorescence optical glass.

Background

Luminescent materials refer to materials that are capable of absorbing other types of energy by some means and then converting this energy into light energy and releasing it as light. The light-emitting mechanism of the light-emitting material is shown in fig. 1, where M denotes a host lattice, in which two foreign ions a and S are doped, and it is assumed that absorption of the host lattice M does not generate radiation. The host lattice M absorbs the excitation energy and transfers it to the dopant ions, causing them to rise to an excited state, which returns to the ground state in 3 ways: 1) the excitation energy is released to the adjacent crystal lattice in the form of heat, becoming "radiationless relaxation", also called fluorescence quenching; 2) release of excitation energy in the form of radiation, known as "luminescence"; 3) s transfers excitation energy to a, i.e. all or part of the excitation energy absorbed by S is released by a producing emission, a phenomenon known as "sensitized luminescence", a being called activator, S being commonly called sensitizer for a.

The lifetime of the excited state after energy absorption by the activator is extremely short, typically only about 10^-8s will automatically return to the ground state and emit photons, a phenomenon known as fluorescence, which stops immediately after the excitation source is removed. If the excited state continues to emit light after the excitation source is turned off, this phenomenon is called phosphorescence. Sometimes phosphorescence can last for tens of minutes or even hours, and such luminescent materials are called long persistence materials.

The luminescence property of a crystal is determined by the composition and crystal structure of the compound constituting it, and often a small change in composition and structure causes a great difference in material properties.

The main local luminescent centers at present are (arrow absorbing to the right and emitting to the left):

1)such as defective luminescent centers (F-centers);

2)such as Ga⁺、In⁺、Tl⁺、Ge²⁺、Sn²⁺、Pb²⁺、As³⁺、Sb³⁺、Bi³⁺Etc.;

3)such as Cu⁺、Ag⁺、Au⁺Etc.;

4)first and second transition metal ions;

5)rare earth ions and actinide ions;

6)low oxidation state rare earth ion Ce³⁺、Sm²⁺、Eu²⁺、Tm²⁺、Yb²⁺；

7) A transfer or charge transfer process between the anion p-electron and the empty cation orbital. Such as VO₄ ^3-，MoO₄ ^2-And WO₄ ^2-Charge transfer within the molecule. Electron of anion p orbital to Eu³⁺Or the transition metal ion transfer occurs only during excitation.

Until now, luminescent materials have been explored and studied for over 100 years. Research on luminescent materials has mainly focused on rare earth ion-doped or transition metal ion-doped inorganic compounds.

Since the development of the technology for tracking and observing the fluorescent target of cancer cells, in order to track and observe the fluorescent target more clearly under a microscope, the observation environment is required not to interfere with the fluorescent target, and therefore, it is important to reduce the fluorescence intensity of the stimulated emission of optical glass used in optical systems such as fluorescent microscopes (particularly, cover slips, glass slides, and objective lenses). Especially low fluorescence biological slide glass, it can effectively improve the efficiency of DNA fixing on glass, so that when making biological chip, it can use less DNA raw material to attain the goal of saving cost. With the progress of biopharmaceuticals and the development of the health industry, the demand of low-fluorescence bioglass is on the rise, so that optical glass for the low-fluorescence biological field is gradually taken attention by people and is becoming the hotspot and the focus of glass material research. In addition to low autofluorescence, the bio-optical glass is also required to have excellent chemical stability in view of resistance to various culture solutions in the test environment.

Refractive index (n) in the prior art_d) 1.48 to 1.55, Abbe number (v)_d) 56-65 optical glass, the fluorescence degree (Y) of which under the excitation of a 486nm wavelength light source is basically lower than 2, and the chemical stability, especially the water-resistant stability (D)_w) Generally, the optical glass is under 3 types (see table 1 below), and if optical glass with a fluorescence level (Y) of 2 types or more and water-resistant stability of 2 types or more can be developed, the problems of fluorescence interference of an observation target, durability of glass of a glass slide and the like can be effectively solved in application.

TABLE 1 stability of water-resistant action of optical glass having partial refractive index of 1.48-1.55 and Abbe number of 56-65

However, if the optical glass with the refractive index and the abbe number is required to achieve a low fluorescence level and have excellent water resistance stability, the component design is different from the conventional component design, and the problems of difficult melting, difficult clarification, poor glass internal quality and the like are generally caused in production. If the high-temperature viscosity of the glass is high, the production difficulty of the glass blank is increased firstly, and then bubbles in the glass liquid are difficult to remove, so that the inherent quality of the glass is poor, and the yield is reduced.

Disclosure of Invention

The invention aims to solve the technical problem of providing the optical glass with the refractive index of 1.48-1.55, the Abbe number of 56-65, lower fluorescence level, excellent water-resistant action stability and good mass production process performance.

The technical scheme adopted by the invention for solving the technical problem is as follows:

(1) the low-fluorescence optical glass comprises the following components in percentage by weight: SiO 2₂：60～80％、B₂O₃：5～20％、Al₂O₃：1～10％、Rn₂O：5～20% of (wherein Rn)₂O/(SiO₂+B₂O₃) 0.07 to 0.25, the Rn₂O is Li₂O、Na₂O、K₂And O or more.

(2) The low-fluorescence optical glass according to (1), which comprises the following components in percentage by weight: and (3) RO: 0 to 10%, and/or Nb₂O₅: 0 to 8%, and/or ZrO₂: 0-3%, and/or a clarifying agent: 0-1%, RO is more than one of BaO, SrO, CaO and MgO, and a clarifying agent is Sb₂O₃、SnO₂、SnO、CeO₂One or more of (a).

(3) The low fluorescence optical glass contains SiO in the components₂、B₂O₃And Rn₂O, the components of which are expressed in weight percentage, wherein Rn₂O/(SiO₂+B₂O₃) 0.07 to 0.25, the refractive index n of the low fluorescence optical glass_dIs 1.48 to 1.55, and has an Abbe number v_d56-65, fluorescence grade Y above grade 2, water-resistant stability D_wIs more than 2 types, the Rn₂O is Li₂O、Na₂O、K₂And O or more.

(4) The low-fluorescence optical glass according to (3), which comprises the following components in percentage by weight: SiO 2₂：60～80％、B₂O₃：5～20％、Al₂O₃：1～10％、Rn₂O：5～20％、RO：0～10％、Nb₂O₅：0～8％、ZrO₂: 0-3% of a clarifying agent: 0-1%, RO is more than one of BaO, SrO, CaO and MgO, and a clarifying agent is Sb₂O₃、SnO₂、SnO、CeO₂One or more of (a).

(5) The low fluorescence optical glass according to any one of (1) to (4), which comprises the following components in percentage by weight: b is₂O₃/SiO₂0.07 to 0.3, preferably B₂O₃/SiO₂0.08 to 0.25, more preferably B₂O₃/SiO₂0.1 to 0.2, and preferably B₂O₃/SiO₂0.1 to 0.15.

(6) The low fluorescence optical glass according to any one of (1) to (4), which comprises the following components in percentage by weight: al (Al)₂O₃/B₂O₃0.2 to 1.5, preferably Al₂O₃/B₂O₃0.3 to 1.0, more preferably Al₂O₃/B₂O₃0.4 to 0.9, and more preferably Al₂O₃/B₂O₃0.5 to 0.8.

(7) The low fluorescence optical glass according to any one of (1) to (4), which comprises the following components in percentage by weight: rn₂O/(SiO₂+B₂O₃) 0.08 to 0.2, preferably Rn₂O/(SiO₂+B₂O₃) 0.1 to 0.18, more preferably Rn₂O/(SiO₂+B₂O₃) 0.11 to 0.16.

(8) The low fluorescence optical glass according to any one of (1) to (4), which comprises the following components in percentage by weight: RO/Rn₂O is 0.1 to 1.0, preferably RO/Rn₂O is 0.2 to 0.8, and RO/Rn is more preferable₂O is 0.3 to 0.7, and RO/Rn is more preferable₂O is 0.4 to 0.65.

(9) The low fluorescence optical glass according to any one of (1) to (4), which comprises the following components in percentage by weight: SiO 2₂: 62-78%, preferably SiO₂: 65-75%; and/or B₂O₃: 6 to 18%, preferably B₂O₃: 7-15%; and/or Al₂O₃: 2 to 9%, preferably Al₂O₃: 3-8%; and/or Rn₂O: 6 to 18%, preferably Rn₂O: 7-15%; and/or RO: 0-9%, preferably RO: 0 to 7 percent; and/or Nb₂O₅: 0 to 6%, preferably Nb₂O₅: 0 to 5 percent; and/or ZrO₂: 0 to 2%, preferably ZrO₂: 0 to 1 percent; and/or a clarifying agent: 0-0.8%, preferably clarifying agent: 0 to 0.5 percent.

(10) The low-fluorescence optical glass according to any one of (1) to (4), wherein the refractive index n of the low-fluorescence optical glass_d1.48 to 1.55, preferably a refractive index n_d1.49 to 1.54 and/or an Abbe number v_dIs 56-65, and the Abbe number v is preferred_dIs 58 to 64.

(11) The low-fluorescence optical glass according to any one of (1) to (4), wherein the low-fluorescence optical glass has a fluorescence level Y of at least 2, preferably at least 1, and/or a water-resistant stability D_wIs of 2 or more types, preferably water-resistant stability D_wIs type 1.

(12) A glass preform made of the low-fluorescence optical glass according to any one of (1) to (11).

(13) An optical element produced from the low-fluorescence optical glass according to any one of (1) to (11) or the glass preform according to (12).

(14) An optical device comprising the low-fluorescence optical glass according to any one of (1) to (11) and/or the optical element according to (13).

The invention has the beneficial effects that: the optical glass has the expected refractive index and Abbe number, has lower fluorescence level, excellent water-resistant action stability, good mass production process performance, no obvious reduction of transmittance after long-term use, is particularly suitable for being used in the fields of biological observation and the like, and is particularly suitable for being applied to cover slips, glass slides and objective lenses of a microscope.

Drawings

Fig. 1 is a schematic diagram of the physical process of solid luminescence.

Detailed Description

The embodiment of the low fluorescence optical glass of the present invention will be described in detail below, but the present invention is not limited to the embodiment described below, and can be implemented by making appropriate changes within the scope of the object of the present invention. Although the description of the overlapping portions may be omitted as appropriate, the invention is not limited thereto, and the low-fluorescence optical glass of the present invention may be simply referred to as an optical glass or a glass in the following description.

[ Low-fluorescence optical glass ]

The ranges of the respective components of the low-fluorescence optical glass of the present invention are explained below. In the present specification, the contents and total contents of the respective components are all expressed in terms of weight percent (wt%) relative to the total amount of glass matter converted into the composition of oxides, if not specifically stated. Here, the "composition converted to oxides" means that when oxides, complex salts, hydroxides, and the like used as raw materials of the optical glass composition component of the present invention are decomposed in the melt and converted to oxides, the total amount of the oxides is 100%.

Unless otherwise indicated herein, the numerical ranges set forth herein include upper and lower values, and the terms "above" and "below" include the endpoints, and all integers and fractions within the range, and are not limited to the specific values listed in the defined range. As used herein, "and/or" is inclusive, e.g., "A and/or B," and means A alone, B alone, or both A and B.

< essential Components and optional Components >

The glass of the invention mainly contains SiO₂、B₂O₃、Al₂O₃RO (RO is more than one of BaO, SrO, CaO and MgO), Rn₂O(Rn₂O is Li₂O、Na₂O、K₂More than one of O) in the glass, and forming the low-fluorescence optical glass according to the invention by reasonable component distribution ratio.

SiO₂And B₂O₃The glass does not fluoresce, is a network former for forming the glass, is the basis for forming the glass, and has content closely related to key indexes of glass forming stability, refractive index, Abbe number, water resistance stability and the like of the glass.

In the present invention, if SiO₂The content exceeds 80 percent, the glass becomes difficult to melt, the glass forming stability is reduced, the devitrification resistance is reduced rapidly, and the refractive index and the Abbe number of the glass cannot meet the design requirements easily, so that the SiO₂The content of (b) is 80% or less, preferably 78% or less, more preferably 75% or less. If SiO₂Less than 60%, the chemical stability, especially the stability against water action, of the glass is reduced, so that SiO₂The content of (b) is 60% or more, preferably 62% or more, and more preferably 65% or more.

In the present invention, B₂O₃If the content of (B) exceeds 20%, the glass is liable to cause phase separation and devitrification, so that B₂O₃The content of (b) is 20% or less, preferably 18% or less, more preferably 15% or less. On the other hand, B₂O₃If the content of (B) is less than 5%, the difficulty of melting the glass increases, so that B₂O₃The content of (b) is 5% or more, preferably 6% or more, and more preferably 7% or more.

The inventor finds that SiO through a large amount of experimental research₂And B₂O₃To a certain extent determines B₂O₃Structural state in glass, and B₂O₃The structural state of (A) has a large influence on indices such as chemical stability, refractive index and Abbe number of the glass. Further, when B₂O₃Content of (D) and SiO₂Ratio B between the contents of₂O₃/SiO₂When the glass phase separation rate is more than 0.3, the glass is easy to phase separate and crystallize; if B is₂O₃/SiO₂Less than 0.07, the water resistance of the glass rapidly decreases. Thus, B₂O₃/SiO₂The value of (b) is preferably 0.07 to 0.3, more preferably 0.08 to 0.25, still more preferably 0.1 to 0.2, and still more preferably 0.1 to 0.15.

Al₂O₃Does not fluoresce, is an important component of the glass of the invention, and can prevent Rn in the glass₂O and B₂O₃The phase separation and the crystallization caused by the aggregation of the glass are improved, and the chemical stability of the glass is improved. When Al is present₂O₃More than 10%, the melting property of the glass is lowered and the refractive index is rapidly lowered, so that Al₂O₃The content of (b) is 10% or less, preferably 9% or less, more preferably 8% or less. If Al is present₂O₃The content of Al is less than 1 percent, the devitrification resistance of the glass is sharply reduced, and the chemical stability does not meet the design requirement, so the Al₂O₃The content of (b) is 1% or more, preferably 2% or more, and more preferably 3% or more.

In some embodiments of the invention, if Al₂O₃Content of (A) and (B)₂O₃Ratio between contents of Al₂O₃/B₂O₃The refractive index of the glass is more than 1.5, and the design requirement is difficult to achieve; if Al is present₂O₃/B₂O₃Less than 0.2, the chemical stability of the glass is reduced. Therefore, Al is preferable₂O₃/B₂O₃The value of (b) is 0.2 to 1.5, more preferably 0.3 to 1.0, still more preferably 0.4 to 0.9, and still more preferably 0.5 to 0.8.

Rn₂O does not fluoresce, B in the bulk system glass₂O₃Is a layered structure of SiO₂Is a frame-shaped structure, and is difficult to form uniform melt due to different structures, and B is difficult to form during the high-temperature cooling process₂O₃And SiO₂The two glasses are mutually insoluble and are enriched into a system, and phase separation is further generated. When Rn is present in the glass₂O, the structure of boron is changed, Rn₂Free oxygen of O makes partial boron oxygen triangle (BO)₃]Conversion to boron-oxygen tetrahedron [ BO₄]The structure of boron is changed from a layer shape to a frame shape and is B₂O₃And SiO₂Forming uniform and consistent glass creating conditions. When the contents of silicon and boron in the glass are constant, Rn₂When the content of O exceeds 20%, the framework structure in the glass is broken and the chemical stability of the glass is drastically lowered, so that Rn₂The content of O is 20% or less, preferably 18% or less, and more preferably 15% or less. If Rn₂The content of O is less than 5%, the melting property of the glass is lowered, and great difficulty is brought to production, so Rn₂The content of O is 5% or more, preferably 6% or more, and more preferably 7% or more.

Through a large amount of experimental research of the inventor, Rn₂O and SiO₂、B₂O₃Total content of (SiO)₂+B₂O₃) The ratio of (a) to (b) determines the structural state of the glass to some extent, and has a large influence on the chemical stability of the glass. Further, when Rn is₂O and (SiO)₂+B₂O₃) Ratio Rn of₂O/(SiO₂+B₂O₃) When the refractive index is more than 0.25, the structure of the glass is loose, and the refractive index is difficult to meet the design requirement; if Rn₂O/(SiO₂+B₂O₃) Less than 0.07, the difficulty of glass melting increases, which is not suitable for mass production. Thus, Rn₂O/(SiO₂+B₂O₃) The value of (b) is preferably 0.07 to 0.25, more preferably 0.08 to 0.2, still more preferably 0.1 to 0.18, and still more preferably 0.11 to 0.16.

RO does not emit fluorescence, can enhance the stability of the glass in the glass and improve the devitrification resistance of the glass, but if the content of RO is higher than 10%, the density and the refractive index of the glass are increased. Therefore, the RO content is 10% or less, preferably 9% or less, and more preferably 7% or less. In some embodiments, MgO does not preferably contain MgO, since MgO deteriorates devitrification resistance of the glass and even causes opalescence of the glass.

In some embodiments of the invention, if the content of RO and Rn are₂The ratio of the contents of O RO and Rn₂O is more than 1.0, and the refractive index of the glass is difficult to meet the design requirement; if RO/Rn₂O is less than 0.1, the devitrification resistance of the glass is poor, and the chemical stability of the glass is difficult to meet the requirements. Therefore, RO/Rn is preferred₂The value of O is 0.1 to 1.0, preferably 0.2 to 0.8, more preferably 0.3 to 0.7, and still more preferably 0.4 to 0.65.

Nb₂O₅The glass does not fluoresce, the refractive index and dispersion of the glass can be adjusted in the glass, the anti-devitrification performance of the glass is improved, and the stability of the glass is improved, but if the content of the glass is higher than 8%, the refractive index of the glass is increased sharply. Thus, Nb₂O₅The content of (b) is 8% or less, preferably 6% or less, more preferably 5% or less.

ZrO₂Does not fluoresce, and can improve the devitrification resistance and the chemical stability of the glass in the glass. More importantly, ZrO₂Can reduce the erosion of molten glass to refractory materials in the production process, can prolong the service life of the furnace body, reduce the maintenance cost of the furnace body and discharge waste materials, and can inhibitImpurities in the prepared refractory material enter the glass, so that the transmittance and the crystallization resistance of the glass are improved. However, ZrO₂The negative anomalous dispersion performance of the glass can be increased, if the content of the negative anomalous dispersion performance exceeds 3%, the negative anomalous dispersion performance of the glass is rapidly improved, meanwhile, the glass is very difficult to melt, and the anti-crystallization performance is rapidly reduced. Thus, ZrO in the invention₂The content is 3% or less, preferably 2% or less, more preferably 1% or less.

In some embodiments of the invention, the Sb content is 0-1%₂O₃、SnO₂SnO and CeO₂One or more components of the glass can be used as a clarifying agent to improve the clarifying effect of the glass. However, the invention has a reasonable formula design and a good clarifying effect, so that the invention preferably contains 0-0.8% of clarifying agent, more preferably contains 0-0.5% of clarifying agent, and further preferably does not contain clarifying agent.

The emission and absorption of light are also related to impurities in the glass, and the observed fluorescence is closely related to the absorbing ions contained in the material, such as most of the luminescent ions of rare earth elements, iron, zinc, vanadium, lead, antimony, arsenic, etc., so that the raw materials are selected to avoid introducing the luminescent impurity components as much as possible.

< component which should not be contained >

In the glass of the present invention, even when a small amount of oxides of transition metals such as V, Cr, Mn, Fe, Co, Ni, Cu, Ag, and Mo is contained singly or in combination, the glass is colored and absorbs at a specific wavelength in the visible light region, thereby impairing the property of the present invention to improve the effect of visible light transmittance.

In recent years, oxides of Th, Cd, Tl, Os, Be, and Se tend to Be used as harmful chemical substances in a controlled manner, and measures for protecting the environment are required not only in the glass production process but also in the processing process and disposal after commercialization. Therefore, when importance is attached to the influence on the environment, it is preferable that these components are not substantially contained except for inevitable mixing. Thereby, the optical glass becomes practically free from substances contaminating the environment. Therefore, the optical glass of the present invention can be manufactured, processed, and discarded without taking special measures for environmental countermeasures.

In order to achieve environmental friendliness, the optical glass of the present invention does not contain As₂O₃And PbO.

"0%" or "0%" is not contained in the present invention, and means that the compound, molecule, element or the like is not intentionally added to the optical glass of the present invention as a raw material; however, it is within the scope of the present invention that certain impurities or components which are not intentionally added may be present as raw materials and/or equipment for producing the optical glass and may be contained in the final optical glass in small or trace amounts.

The performance of the low fluorescence optical glass of the present invention will be described below.

< refractive index and Abbe number >

Refractive index (n) of optical glass_d) And Abbe number (v)_d) The test was carried out according to the method specified in GB/T7962.1-2010.

In some embodiments, the low fluorescence optical glass of the present invention has a refractive index (n)_d) A lower limit of 1.48, preferably a lower limit of 1.49; in some embodiments, the low fluorescence optical glass of the present invention has a refractive index (n)_d) The upper limit of (2) is 1.55, and the preferable upper limit is 1.54.

In some embodiments, the low fluorescence optical glass of the present invention has an Abbe number (. nu.) of_d) A lower limit of 56, preferably a lower limit of 58; in some embodiments, the low fluorescence optical glass of the present invention has an Abbe number (. nu.) of_d) The upper limit of (3) is 65, preferably 64.

< fluorescence level >

The fluorescence grade (Y) of the optical glass was measured according to the method specified in JOGIS 03-1975.

In some embodiments, the low fluorescence optical glass of the present invention has a fluorescence level (Y) of 2 or more, preferably 1 or more.

< stability against Water action >

Stability to Water of optical glass (D)_w) (powder method) the test was carried out according to the method prescribed in GB/T17129.

In some embodiments, the low fluorescence optical glass of the present invention has stability to water effects (D)_w) Is 2 or more, preferably 1.

[ production method ]

The method for manufacturing the low-fluorescence optical glass comprises the following steps: the glass is produced by adopting conventional raw materials and conventional processes, carbonate, nitrate, sulfate, hydroxide, oxide and the like are used as raw materials, the materials are mixed according to a conventional method, the mixed furnace burden is put into a smelting furnace (such as a platinum crucible, a quartz crucible and the like) at 1580-1630 ℃ for smelting, and after clarification, stirring and homogenization, homogeneous molten glass without bubbles and undissolved substances is obtained, and the molten glass is cast in a mold and annealed. Those skilled in the art can appropriately select the raw materials, the process method and the process parameters according to the actual needs.

Glass preform and optical element

The glass preform can be produced from the optical glass produced by, for example, grinding or press molding such as reheat press molding or precision press molding. That is, the glass preform may be produced by machining the optical glass by grinding, polishing, or the like, or by producing a preform for press molding from the optical glass, subjecting the preform to reheat press molding, and then polishing, or by precision press molding the preform obtained by polishing.

It should be noted that the means for producing the glass preform is not limited to the above means. As described above, the optical glass of the present invention is useful for various optical elements and optical designs, and among them, it is particularly preferable to form a preform from the optical glass of the present invention, and use the preform for reheat press forming, precision press forming, or the like to produce optical elements such as lenses, prisms, glass sheets, or the like.

The glass preform of the present invention and the optical element are each formed of the above-described optical glass of the present invention. The glass preform of the present invention has excellent characteristics possessed by optical glass; the optical element of the present invention has excellent characteristics of optical glass, and can provide optical elements such as various lenses and prisms having high optical values.

Examples of the lens include various lenses such as a concave meniscus lens, a convex meniscus lens, a double convex lens, a double concave lens, a plano-convex lens, and a plano-concave lens, each of which has a spherical or aspherical lens surface.

The optical glass of the present invention can also be made into glass sheets of any thickness that is reasonably useful.

[ optical instruments ]

The optical element formed by the optical glass can be used for manufacturing optical instruments such as photographic equipment, image pick-up equipment, display equipment, monitoring equipment, microscopes and the like.

< example of Low fluorescence optical glass >

In order to further clarify the explanation and explanation of the technical solution of the present invention, the following non-limiting examples are provided.

In this example, optical glasses having compositions shown in tables 2 to 3 were obtained by the above-described method for producing a low-fluorescence optical glass. In addition, the characteristics of each glass were measured by the test method described in the present invention, and the measurement results are shown in tables 2 to 3, wherein B₂O₃/SiO₂Is represented by K1, Al₂O₃/B₂O₃Is represented by K2, Rn₂O/(SiO₂+B₂O₃) Is represented by K3, RO/Rn₂The value of O is denoted by K4.

Table 2.

Table 3.

< glass preform example >

Various lenses such as a concave meniscus lens, a convex meniscus lens, a biconvex lens, a biconcave lens, a plano-convex lens and a plano-concave lens, and preforms such as prisms were produced from the glasses obtained in examples 1 to 20 of the low-fluorescence optical glass by means of polishing or press molding such as reheat press molding and precision press molding.

< optical element example >

The preforms obtained from the above glass preform examples were annealed to reduce the internal stress of the glass and to fine-tune the refractive index so that the optical properties such as refractive index reached the desired values.

Next, each preform is ground and polished to produce various lenses such as a concave meniscus lens, a convex meniscus lens, a biconvex lens, a biconcave lens, a plano-convex lens, and a plano-concave lens, and prisms. The surface of the resulting optical element may be coated with an antireflection film.

< optical Instrument example >

The optical element produced by the above-described optical element embodiments can be used, for example, for imaging devices, sensors, microscopes, medical technology, digital projection, communication, optical communication technology/information transmission, optics/illumination in the automotive field, lithography, excimer lasers, wafers, computer chips, and integrated circuits and electronic devices including such circuits and chips, by optical design, by forming an optical component or optical assembly using one or more optical elements.