CN115974405A - Filter glass and method for producing same - Google Patents

Abstract

The invention provides a filter glass, the components of the filter glass are expressed by mole percent, and a cation component comprises: si ⁴⁺ ：36～70％；Na ⁺ ：5～25％；Li ⁺ ：0～8％；K ⁺ ：0～10％；Zn ²⁺ ：0～15％；Sb ³⁺ :0 to 6 percent; the anionic component comprises: o is ^2‑ ：90～100％；S ^2‑ :0 to 10 percent. The invention obtains the filter glass with adjustable cut-off wavelength in the range of 480-700 nm and capable of being applied to the high-transmittance requirement of 650-800 nm wave band through reasonable component design and heat treatment process treatment.

Description

Filter glass and method for producing same

Technical Field

The invention relates to glass, in particular to visible-near infrared filter glass with adjustable cut-off wavelength in the range of 480-700 nm.

Background

The filter glass is glass capable of having strong light absorption on light with specific wavelengthA glass material. The application fields of the filter glass comprise stray light elimination of an optical fiber optical system, stray light elimination of a sensor optical system, stray light elimination of an imaging optical system and the like. With the development of laser optical systems, sensing optics and machine vision, materials with high transmittance and high light absorption at specific wavelengths are required. In addition, there is a need for materials that are chemically stable and environmentally friendly. The conventional method for manufacturing colored glass by adopting the combination of transition metal coloring components such as Fe, co, cu, ni, mn and the like is not suitable for manufacturing the glass, and the specific light absorption range is difficult to realize mainly because the transition metal coloring components often have a plurality of absorption peaks and have strong interaction. In the prior art, the glass with high transmittance and high light absorption of specific wavelength is obtained by adopting an optical coating method, and the coating process is complex, and the coating is easy to lose effectiveness due to mechanical scraping and environmental effects, so that the batch supply is not facilitated, and the product stability is improved. Other coating methods, for example, CN109399953A, disclose the use of coating to control the MoS of a glass surface ₂ The microstructure of the coating realizes controllable light absorption, but the chemical stability of the film is poor.

The method of changing the absorption limit of the glass by adjusting the forbidden bandwidth of the glass by using a semiconductor absorption mechanism can realize a specific cut-off limit, but the prior art cannot simultaneously realize the glass with the cut-off limit of 500-625 nm and other necessary properties. For example, some publications report the use of CeO ₂ 、TiO ₂ By the interaction of different CeO ₂ 、TiO ₂ The absorption limit of the glass is adjusted by controlling the content and the proportion. However, the strength of extra absorption generated by Ce-Ti charge transfer is mainly changed due to the content regulation of Ce and Ti, and the absorption cut-off limit of the glass can be adjusted only within the wavelength range of 250-500 nm. The traditional light filtering selenium cadmium glass realizes light filtering by utilizing a semiconductor light absorption mechanism, the cut-off limit of the traditional light filtering selenium cadmium glass can be 300-650 nm, but the cadmium content of the traditional light filtering selenium cadmium glass is high, and the traditional light filtering selenium cadmium glass cannot meet the current environmental protection technical standard. Meanwhile, selenium-cadmium glass also has the defect of poor chemical stability. CN112876066B discloses an environment-friendly material for realizing visible light cutoff by adopting the interaction of components such as S, fe, mo, V and the like. However, the absorption cutoff of the glass is generally 625-700 nm, the high transmittance range of the glass is generally 800-2000 nm, and the high transmittance under the wavelength of less than 800nm cannot be realized.

In summary, the environmental protection glass material limited to 500-625 nm in the prior art is still missing, which is not favorable for meeting the requirement of 650-800 nm band high-transmittance filter glass.

Disclosure of Invention

The invention aims to solve the technical problem of providing visible-near infrared filter glass with adjustable cut-off wavelength in the range of 480-700 nm.

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

(1) Filter glass, the composition of which is expressed in mole percent, the cationic component comprising: si ⁴⁺ ：36～70％；Na ⁺ ：5～25％；Li ⁺ ：0～8％；K ⁺ ：0～10％；Zn ²⁺ ：0～15％；Sb ³⁺ ：0～6％；

The anionic component comprises: o is ^2- ：90～100％；S ^2- ：0～10％。

(2) The filter glass according to (1), whose composition is expressed in mole percent, the cationic component further contains: al (aluminum) ³⁺ :0 to 12 percent; and/or B ³⁺ :0 to 10 percent; and/or P ⁵⁺ :0 to 5 percent; and/or Ag ⁺ :0 to 5 percent; and/or Ba ²⁺ :0 to 10 percent; and/or Mg ²⁺ :0 to 8 percent; and/or Ca ²⁺ :0 to 10 percent; and/or Sr ²⁺ :0 to 5 percent; and/or La ³⁺ :0 to 6 percent; and/or Y ³⁺ :0 to 8 percent; and/or V ⁵⁺ :0 to 5 percent; and/or Ti ⁴⁺ :0 to 5 percent; and/or Ce ⁴⁺ ：0～2％。

(3) Filter glass, the composition of which is expressed in mole percent (Zn) ²⁺ +Mg ²⁺ +Ca ²⁺ +Sr ²⁺ )/(Na ⁺ +Li ⁺ +K ⁺ +Ag ⁺ ) Is 0.2 to 1.0, lambda of the filter glass ₅₀ -λ ₅ λ of 100nm or less _{Work by} -λ ₅₀ Is 80nm or less.

(4) The filter glass according to (3), whose components are expressed in mol percentThe cationic component contains: si ⁴⁺ :36 to 70 percent; and/or Na ⁺ :5 to 25 percent; and/or Li ⁺ :0 to 8 percent; and/or K ⁺ :0 to 10 percent; and/or Zn ²⁺ :0 to 15 percent; and/or Sb ³⁺ :0 to 6 percent; and/or Al ³⁺ :0 to 12 percent; and/or B ³⁺ :0 to 10 percent; and/or P ⁵⁺ :0 to 5 percent; and/or Ag ⁺ :0 to 5 percent; and/or Ba ²⁺ :0 to 10 percent; and/or Mg ²⁺ :0 to 8 percent; and/or Ca ²⁺ :0 to 10 percent; and/or Sr ²⁺ :0 to 5 percent; and/or La ³⁺ :0 to 6 percent; and/or Y ³⁺ :0 to 8 percent; and/or V ⁵⁺ :0 to 5 percent; and/or Ti ⁴⁺ :0 to 5 percent; and/or Ce ⁴⁺ ：0～2％；

The anionic component comprises: o is ^2- :90 to 100 percent; and/or S ^2- ：0～10％。

(5) The filter glass according to any one of (1) to (4), wherein the composition of the filter glass is represented by mole percent, and the cationic component comprises: si ⁴⁺ :44 to 66%, preferably Si ⁴⁺ :50 to 64 percent; and/or Na ⁺ :10 to 23%, preferably Na ⁺ :12 to 20 percent; and/or Li ⁺ :0.2 to 4%, preferably Li ⁺ :0.6 to 3 percent; and/or K ⁺ :0.2 to 8%, preferably K ⁺ :0.5 to 5 percent; and/or Zn ²⁺ :0 to 13%, preferably Zn ²⁺ :3 to 11 percent; and/or Sb ³⁺ :0.1 to 5%, preferably Sb ³⁺ :0.2 to 4 percent; and/or Al ³⁺ :0 to 8%, preferably Al ³⁺ :0 to 4 percent; and/or B ³⁺ :0 to 5%, preferably B ³⁺ :0 to 2 percent; and/or P ⁵⁺ :0.1 to 2.5%, preferably P ⁵⁺ :0.2 to 1.5 percent; and/or Ag ⁺ :0 to 2%, preferably Ag ⁺ :0 to 1 percent; and/or Ba ²⁺ :0 to 5%, preferably Ba ²⁺ :0 to 2 percent; and/or Mg ²⁺ :0 to 4%, preferably Mg ²⁺ :0 to 2 percent; and/or Ca ²⁺ :0 to 4%, preferably Ca ²⁺ :0 to 2 percent; and/or Sr ²⁺ :0 to 2 percent; and/or La ³⁺ :0 to 4%, preferably La ³⁺ :0 to 2 percent; and/or Y ³⁺ ：0～6％，Preferably Y ³⁺ :0 to 3 percent; and/or V ⁵⁺ :0 to 1%, preferably V ⁵⁺ :0 to 0.5 percent; and/or Ti ⁴⁺ :0 to 2 percent; and/or Ce ⁴⁺ ：0～0.5％。

(6) The filter glass according to any one of (1) to (4), wherein the composition of the filter glass is represented by mole percent, and the anionic component comprises: o is ^2- :92 to 100%, preferably O ^2- :95 to 98 percent; and/or S ^2- :0.5 to 7.5%, preferably S ^2- ：1～5％。

(7) The filter glass according to any one of (1) to (4), whose composition is expressed in mol%, wherein: li ⁺ /Na ⁺ 0 to 0.5, preferably Li ⁺ /Na ⁺ 0 to 0.3, more preferably Li ⁺ /Na ⁺ 0.025 to 0.2.

(8) The filter glass according to any one of (1) to (4), whose composition is expressed in mol%, wherein: k ⁺ /(Li ⁺ +Na ⁺ ) Is 0 to 0.4, preferably K ⁺ /(Li ⁺ +Na ⁺ ) Is 0 to 0.25, more preferably K ⁺ /(Li ⁺ +Na ⁺ ) 0.05 to 0.15.

(9) The filter glass according to any one of (1) to (4), whose composition is expressed in mol%, wherein: p ⁵⁺ /Si ⁴⁺ Is 0 to 0.1, preferably P ⁵⁺ /Si ⁴⁺ Is 0 to 0.06, more preferably P ⁵⁺ /Si ⁴⁺ 0.01 to 0.05.

(10) The filter glass according to any one of (1) to (4), whose composition is expressed in mol%, wherein: (Zn) ²⁺ +Mg ²⁺ +Ca ²⁺ +Sr ²⁺ )/(Na ⁺ +Li ⁺ +K ⁺ +Ag ⁺ ) 0.2 to 1.0, preferably (Zn) ²⁺ +Mg ²⁺ +Ca ²⁺ +Sr ²⁺ )/(Na ⁺ +Li ⁺ +K ⁺ +Ag ⁺ ) Is 0.25 to 0.8, more preferably (Zn) ²⁺ +Mg ²⁺ +Ca ²⁺ +Sr ²⁺ )/(Na ⁺ +Li ⁺ +K ⁺ +Ag ⁺ ) 0.3 to 0.6.

(11) The filter glass according to any one of (1) to (4), whose composition is expressed in mol%, wherein: zn ²⁺ +2×La ³⁺ +2×Y ³⁺ 8 to 30%, preferably Zn ²⁺ +2×La ³⁺ +2×Y ³⁺ 9 to 25%, more preferably Zn ²⁺ +2×La ³⁺ +2×Y ³⁺ 10 to 20 percent.

(12) The filter glass according to any one of (1) to (4), wherein the filter glass has a composition comprising, in mole percent, cations further comprising: cu (copper) ⁺ :0 to 0.5%, preferably Cu ⁺ :0 to 0.2%, more preferably Cu ⁺ :0 to 0.1%, and more preferably Cu ⁺ :0 to 0.01 percent; and/or Fe ²⁺ :0 to 0.5%, preferably Fe ²⁺ :0 to 0.2%, more preferably Fe ²⁺ :0 to 0.1%, and more preferably Fe ²⁺ :0 to 0.01 percent; and/or Co ²⁺ :0 to 0.5%, preferably Co ²⁺ :0 to 0.2%, more preferably Co ²⁺ :0 to 0.1%, more preferably Co ²⁺ :0 to 0.01 percent; and/or Mn ²⁺ :0 to 0.5%, preferably Mn ²⁺ :0 to 0.2%, more preferably Mn ²⁺ :0 to 0.1%, more preferably Mn ^{2 +} ：0～0.01％。

(13) The filter glass according to any one of (1) to (4), which comprises, in mole percent: cu (copper) ⁺ +Fe ^{2 +} +Co ²⁺ +Mn ²⁺ +(V ⁵⁺ /100) 0 to 0.5%, preferably Cu ⁺ +Fe ²⁺ +Co ²⁺ +Mn ²⁺ +(V ⁵⁺ /100) is 0 to 0.2%, more preferably Cu ⁺ +Fe ²⁺ +Co ²⁺ +Mn ²⁺ +(V ⁵⁺ /100) is 0 to 0.1%, and Cu is more preferable ⁺ +Fe ²⁺ +Co ²⁺ +Mn ²⁺ +(V ⁵⁺ Per 100) is 0 to 0.01 percent.

(14) The filter glass according to any one of (1) to (4), which contains Cu ⁺ 、Fe ²⁺ 、Co ²⁺ 、Mn ²⁺ 2 or less components, preferably containing Cu ⁺ 、Fe ²⁺ 、Co ²⁺ 、Mn ²⁺ Medium 1 component, or no Cu ⁺ 、Fe ²⁺ 、Co ²⁺ 、Mn ²⁺ 。

(15) The filter glass according to any one of (1) to (4), whose components are expressed in mol%,the anion also contains: f ^- :0 to 5%, preferably F ^- :0 to 1%, more preferably F ^- :0 to 0.5 percent; and/or Se ^2- :0 to 2%, preferably Se ^2- :0 to 1%, more preferably Se ^2- ：0～0.5％。

(16) The filter glass according to any one of (1) to (4), wherein Sr is not contained in the composition ²⁺ (ii) a And/or does not contain Ti ⁴⁺ (ii) a And/or does not contain Ce ⁴⁺ (ii) a And/or does not contain Rb ⁺ (ii) a And/or does not contain Cs ⁺ (ii) a And/or does not contain As ³⁺ (ii) a And/or does not contain Pb ²⁺ (ii) a And/or does not contain Tl ⁺ (ii) a And/or does not contain F ^- (ii) a And/or does not contain Se ^2- 。

(17) The filter glass according to any one of (1) to (4), wherein λ of the filter glass ₅₀ -λ ₅ Is 100nm or less, preferably 80nm or less, more preferably 70nm or less; and/or lambda of the filter glass _{Work in} -λ ₅₀ 80nm or less, preferably 70nm or less, more preferably 60nm or less; and/or microKirschner hardness H _K Is 380X 10 ⁷ Pa or more, preferably 400X 10 ⁷ Pa or more, more preferably 420X 10 ⁷ Pa is above; and/or stability against acid action D _A Is 3 or more, preferably 2 or more, more preferably 1; and/or stability against water action D _W Is 3 or more, preferably 2 or more, and more preferably 1.

(18) A glass preform made of the filter glass according to any one of (1) to (17).

(19) A glass member made of the filter glass according to any one of (1) to (17), or the glass preform according to (18).

(20) An apparatus produced using the filter glass according to any one of (1) to (17), or the glass element according to (19).

(21) The method for producing a filter glass according to any one of (1) to (17), comprising the steps of: a base glass is formed, and then the base glass is subjected to a heat treatment process to form a filter glass.

(22) The manufacturing method of filter glass according to (21), wherein the heat treatment process comprises controlling a heat treatment temperature and controlling a heat treatment time, and the heat treatment temperature is in a range of 450 to 600 ℃, preferably 490 to 570 ℃, and more preferably 510 to 550 ℃; the heat treatment time is 1 to 100 hours, preferably 5 to 60 hours, and more preferably 10 to 40 hours.

The invention has the beneficial effects that: the invention obtains the filter glass with adjustable cut-off wavelength in the range of 480-700 nm and capable of being applied to the high-transmittance requirement of 650-800 nm wave band through reasonable component design and heat treatment process treatment.

Drawings

FIG. 1 is a graph showing the spectral transmittance of a filter glass of example 6 of the present invention.

FIG. 2 is a graph showing the spectral transmittance of a filter glass of example 8 of the present invention.

Detailed Description

The following describes in detail an embodiment of the filter glass of the present invention, 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 gist of the present invention is not limited thereto, and the filter glass of the present invention may be simply referred to as glass in the following description.

[ Filter glass ]

The ranges of the components (ingredients) of the filter glass of the present invention are described below. In the present invention, the contents of the respective components, the total contents are all expressed by ionic mole percentage (mol%), unless otherwise specified. That is, the content of each constituent component (component) of the filter glass is not particularly specified, and the content of the cationic component is expressed in terms of the percentage (mol%) of the cation to the total mole of all the cationic components, and the content of the anionic component is expressed in terms of the percentage (mol%) of the anion to the total mole of all the anionic components.

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.

It should be noted that the ion valences of the components described in the present invention are representative values used for convenience, and are not different from other ion valences. The ion valences of the respective components present in the optical glass are likely to be outside the representative value. For example, the Fe component may be in the form of Fe ²⁺ 、Fe ³⁺ In the present invention, fe ²⁺ It is also within the scope of the present invention to indicate the Fe component, but the possibility exists that it exists in other ionic valence states.

< cationic component >

The glass of the invention is silicate system glass, si ⁴⁺ Is an essential component. Si ⁴⁺ Too low a content will result in a glass of the invention having reduced chemical stability and reduced glass forming properties. Si ⁴⁺ The content is too high, the content of other coloring components in the glass cannot be ensured, and the light filtering effect of the glass is difficult to realize. Thus, si ⁴⁺ The content of (B) is in the range of 36 to 70%, preferably 44 to 66%, more preferably 50 to 64%. In some embodiments, si ⁴⁺ May be in the form of SiO ₂ 、Si ₃ N ₄ SiC, etc.

Al ³⁺ Is an optional component of the glass of the invention, al ³⁺ Has the function of improving the glass forming performance and the chemical stability of the glass. However, al ³⁺ The glass network can be densified resulting in a reduction in the coloring power of the semiconductor. Thus, al ³⁺ The content of (b) is 0 to 12%, preferably 0 to 8%, more preferably 0 to 4%. In some embodiments, al ³⁺ Can be mixed with Al (OH) ₃ 、Al ₂ O ₃ 、Al(PO ₃ ) ₃ And the like. In the glass of the present invention, al (OH) ₃ Since the coloring component is liable to be volatilized to lower the cut-off property of the glass, al (PO) is more preferably introduced ₃ ) ₃ 。

B ³⁺ Is an optional component of the glasses of the invention, B ³⁺ Is beneficial to the conversion of glassThe chemical stability is improved. However, B ³⁺ It is easy to cause volatilization of coloring components and reduces the filtering capability of the glass. Thus, B ³⁺ The content of (b) is in the range of 0 to 10%, preferably 0 to 5%, more preferably 0 to 2%.

Na ⁺ Can reduce the melting temperature of the glass, play a role in reducing the service life loss and energy consumption of the refractory material melted by the glass, and simultaneously Na ⁺ Participate in the semiconductor absorption process of the glass of the present invention. Na (Na) ⁺ The content is too low, the melting difficulty of the glass is higher, and the glass with better internal quality can not be obtained. Na (Na) ⁺ Too high a content results in a decrease in glass forming properties of the glass. Thus, na ⁺ The content of (b) is in the range of 5 to 25%, preferably 10 to 23%. Na is more preferable for the glass to have a more excellent filter effect ⁺ The content range of (A) is 12 to 20%.

Li ⁺ The glass has the functions of reducing the high-temperature viscosity of the glass and greatly reducing the melting temperature of the glass, and in the glass, the function has very important significance for reducing the volatilization of coloring components. In terms of coloring, li ⁺ With Na ⁺ Similarly, it can participate in the semiconductor absorption process of glass, but it is similar to Na ⁺ There is a competing relationship. In one aspect, li ⁺ The forbidden band width of the semiconductor microstructure is less than Na ⁺ 、K ⁺ (ii) a On the other hand, li ⁺ Bonding to glass network vs. Na ⁺ 、K ⁺ And the method is more compact, which is not beneficial to forming a semiconductor absorption microstructure by solid phase diffusion and other modes in the heat treatment process. Thus, li ⁺ The content of (b) is in the range of 0 to 8%, preferably 0.2 to 4%, more preferably 0.6 to 3%.

Li ⁺ In a content of Na ⁺ Ratio between contents of Li ⁺ /Na ⁺ Is a key factor for controlling the filtering capability of the glass. In some embodiments, li ⁺ /Na ⁺ Greater than 0.5, the filter function is difficult to achieve, li ⁺ /Na ⁺ The smaller the glass cutoff wavelength, the more infrared. Therefore, li is preferable ⁺ /Na ⁺ The range of (b) is 0 to 0.5, more preferably 0 to 0.3, and still more preferably 0.025 to 0.2.

K ⁺ Can obviously improve the devitrification resistance of the glass, and is beneficial to the production stability of the glass and the process stability of the subsequent heat treatment process. However, K ⁺ Too high a content results in its reaction with Li ⁺ 、Na ⁺ Contend for points in the semiconductor absorbing microstructure, and K ⁺ The content of (A) is increased, which is not beneficial to realizing short-wave visible light cut-off. Thus, K ⁺ The content of (B) is 0 to 10%, preferably 0.2 to 8%, more preferably 0.5 to 5%.

In some embodiments, K ⁺ /(Li ⁺ +Na ⁺ ) Too large, the light cut-off capability of the glass is insufficient; k is ⁺ /(Li ⁺ +Na ⁺ ) Too small, the devitrification resistance and chemical stability of the glass are poor. Therefore, K is preferred ⁺ /(Li ⁺ +Na ⁺ ) The range of (b) is 0 to 0.4, more preferably 0 to 0.25, and still more preferably 0.05 to 0.15.

Zn ²⁺ Has the function of reducing the volatilization of components forming the semiconductor absorption microstructure. At the same time, zn ²⁺ Belongs to a glass network modifier, and has the function of improving the micro Vickers hardness of glass within a certain content range. However, zn ²⁺ If the content is too high, the tendency of the glass to devitrify increases. Thus, zn ²⁺ The content of (b) is in the range of 0 to 15%, preferably 0 to 13%, more preferably 3 to 11%.

In the glass of the present invention, P ⁵⁺ The chemical stability of the glass is improved, and the semiconductor absorption microstructure is obtained through heat treatment. At P ⁵⁺ The micro Vickers hardness of the glass has no obvious change under the condition of small content; but P is ⁵⁺ Too high a content increases the tendency of the glass to phase separate. Thus, P ⁵⁺ The content of (b) is 0 to 5%, preferably 0.1 to 2.5%, more preferably 0.2 to 1.5%.

In some embodiments, to prevent P ⁵⁺ The presence of resulting opacification of the glass due to severe phase separation, preferably controlled for P ⁵⁺ With Si ⁴⁺ Ratio P between the contents of ⁵⁺ /Si ⁴⁺ Is 0 to 0.1, more preferably 0 to 0.06, and still more preferably 0.01 to 0.05.

Ag ⁺ Are optional components of the glass of the present invention.Ag ⁺ In glass, the glass can be colored by a colloid coloring mechanism, which is beneficial to red shift of an absorption limit, but is not beneficial to improving the transmittance of the glass between 600 and 800 nm. Thus, ag ⁺ The content in the glass is in the range of 0 to 5%, preferably 0 to 2%, more preferably 0 to 1%.

Ba ²⁺ Is an optional component of glass. Ba ²⁺ The existence of the glass can promote micro-area phase separation of the glass, and is beneficial to improving the color development speed of the glass in the heat treatment process; however, if Ba ²⁺ The content of (A) is too high, which causes the crystallization resistance of the glass to be poor, and crystals with the transmittance of 600-1000 nm reduced are easily precipitated in the production process and the heat treatment process. Thus, ba ²⁺ The content of (b) is in the range of 0 to 10%, preferably 0 to 5%, more preferably 0 to 2%.

Mg ²⁺ Are optional components of the glasses of the invention. Mg (Mg) ²⁺ Is favorable for improving the hardness of the glass, and Mg ²⁺ The effect of improving the glass hardness is better than that of Ca ²⁺ 、Sr ²⁺ 、Ba ²⁺ . However, mg ²⁺ Does not have the function of reducing the volatilization of the components forming the semiconductor absorption microstructure. Thus, mg ²⁺ The content of (b) is in the range of 0 to 8%, preferably 0 to 4%, more preferably 0 to 2%.

Ca ²⁺ Are optional components of the glass of the present invention. Ca ²⁺ The melting temperature of the glass can be obviously reduced, the melting temperature of the glass is reduced, and the volatilization of components of a semiconductor absorption microstructure in the glass can be indirectly reduced. However, ca ²⁺ The contribution to the hardness of the glass is relatively low, and the chemical strengthening method is not favorable for improving the strength of the glass. Thus, ca ²⁺ The content of (b) is in the range of 0 to 10%, preferably 0 to 4%, more preferably 0 to 2%.

Sr ²⁺ Are optional components of the glass of the present invention. In silicate glasses, sr ²⁺ Has the function of promoting micro-partition of glass, but the function is not as good as that of Ba ²⁺ 。Sr ²⁺ Also has the function of improving the stability of the water-resistant function of the glass. But Sr ²⁺ Too high content of (b) results in deterioration of the crystallization resistance of the glass. Therefore, sr in the glass of the present invention ²⁺ Is 0 to up5%, preferably 0 to 2%, and more preferably contains no Sr ²⁺ 。

The compactness degree of the glass is too high, which is not beneficial to the heat treatment to separate out the semiconductor absorption microstructure; the degree of compaction of the glass is too low and the hardness of the glass is low. In some embodiments of the invention, (Zn) is ²⁺ +Mg ²⁺ +Ca ²⁺ +Sr ²⁺ )/(Na ⁺ +Li ⁺ +K ⁺ +Ag ⁺ ) The density of the glass is controlled within the range of 0.2-1.0, and the glass has proper density, so that the glass has higher hardness while being easy to separate out a semiconductor absorption microstructure. Therefore, (Zn) is preferred ²⁺ +Mg ²⁺ +Ca ²⁺ +Sr ²⁺ )/(Na ⁺ +Li ⁺ +K ⁺ +Ag ⁺ ) Is 0.2 to 1.0, more preferably 0.25 to 0.8, and still more preferably 0.3 to 0.6.

La ³⁺ Are optional components of the glass of the present invention. At a lower content, la ³⁺ The silicate glass exists in a mixed form of a network former and a network intermediate. At higher contents, la ³⁺ In the form of network intermediates, which tend to lead to the depolymerization of the glass network. La ³⁺ Substitution of Si ⁴⁺ Has the function of reducing the viscosity of the glass. La ³⁺ Has the beneficial effect of reducing the volatilization amount of the composition components of the semiconductor absorption microstructure in the glass, and simultaneously La ³⁺ Is beneficial to improving the hardness of the glass of the invention. However, la ³⁺ The content is too high, which leads to the depolymerization of the glass network, reduces the crystallization resistance of the glass and leads to the reduction of the 800-1200 nm transmittance of the glass after the color development heat treatment. Thus, la ³⁺ The content of (b) is in the range of 0 to 6%, preferably 0 to 4%, more preferably 0 to 2%.

Y ³⁺ Are optional components of the glass of the present invention. Y is ³⁺ And La ³⁺ The effect in the glasses of the invention is essentially the same, but with respect to La ³⁺ Easier access to the glass network. Thus, Y ³⁺ More than La is theoretically present in the glass of the invention ³⁺ 。Y ³⁺ The glass also has the effects of reducing the volatilization amount of the composition components of the semiconductor absorption microstructure and improving the hardness of the glass. Thus, Y ³⁺ The content of (b) is in the range of 0 to 8%, preferably 0 to 6%, more preferably 0 to 3%.

In some embodiments, it is preferred to control Zn in order to achieve reduced volatilization of constituent components of the semiconductor absorbing microstructure in the glasses of the invention ²⁺ +2×La ³⁺ +2×Y ³⁺ 8 to 30%, more preferably 9 to 25%, and still more preferably 10 to 20%.

Cu ⁺ Are optional components in the glasses of the invention. The semiconductor absorption microstructures of the glass are dispersed in the glass, and the problem of insufficient light absorption near the cut-off limit can exist. In the case of the glass melting according to the invention, the Cu component is generally Cu ⁺ In the form of (A), cu ⁺ The light absorption near the glass cutoff can be enhanced. However, cu ⁺ Too high a content may result in a decrease in the transmission of the glass of the invention from 1000 to 1500 nm. Thus, cu ⁺ The content of (b) is in the range of 0 to 0.5%, preferably 0 to 0.2%, more preferably 0 to 0.1%, and still more preferably 0 to 0.01%.

Fe ²⁺ Are optional components in the glasses of the invention. In the case of the melting of the glass according to the invention, the Fe component is generally Fe ²⁺ The form exists. Fe ²⁺ The effect of light absorption near the glass cutoff can be enhanced. Fe in the invention ²⁺ The content of (b) is in the range of 0 to 0.5%, preferably 0 to 0.2%, more preferably 0 to 0.1%, and still more preferably 0 to 0.01%.

Co ²⁺ Are optional components of the glass of the present invention. Co ²⁺ Has strong absorption to 500-700 nm light, and is suitable for existing conditions that the cut-off wavelength is required to be more than 700 nm. Co ²⁺ The content of (b) is in the range of 0 to 0.5%, preferably 0 to 0.2%, more preferably 0 to 0.1%, and still more preferably 0 to 0.01%.

Mn ²⁺ Are optional components of the glass of the present invention. Mn ²⁺ Has absorption effect on light with the wavelength of 420-560 nm, and can improve the light absorption capacity near the cut-off limit of the glass. Mn ²⁺ The content of (b) is in the range of 0 to 0.5%, preferably 0 to 0.2%, more preferably 0 to 0.1%, and still more preferably 0 to 0.01%.

Due to Cu ⁺ 、Fe ²⁺ 、Co ²⁺ 、Mn ²⁺ There is an interaction between them that leads to a decrease in the near infrared transmittance of the glass, so that in Cu ⁺ 、Fe ²⁺ 、Co ²⁺ 、Mn ²⁺ Preferably, the composition contains 2 or less components, more preferably 1 component, or none of the above components.

V ⁵⁺ Are optional components of the glass of the present invention. V ⁵⁺ Has abundant lower valence existing forms, and can enhance the ultraviolet light cut-off function of the glass. However, V ⁵⁺ Too high a content results in a decrease in the near infrared transmittance of the glass. Thus, V ⁵⁺ The content of (b) is in the range of 0 to 5%, preferably 0 to 1%, more preferably 0 to 0.5%.

In some embodiments of the invention, cu is added ⁺ +Fe ²⁺ +Co ²⁺ +Mn ²⁺ +(V ⁵⁺ 100) is controlled below 0.5 percent, which is beneficial to realizing high transmittance in the wavelength range of 800-1200 nm. Therefore, cu is preferable ⁺ +Fe ²⁺ +Co ²⁺ +Mn ²⁺ +(V ⁵⁺ /100) is 0 to 0.5%, more preferably 0 to 0.2%, still more preferably 0 to 0.1%, and still more preferably 0 to 0.01%.

Ti ⁴⁺ Has charge transfer effect with partial valence-variable components, and can improve the light absorption capacity of the glass between 200 and 500 nm. However, the glasses of the present invention generally require a neutral or reducing atmosphere to be melted to provide the Ti component as Ti ³⁺ The forms are present in a large proportion, resulting in additional light absorption of the glass in the wavelength range from 400 to 1500 nm. Thus, the glass of the present invention contains Ti ⁴⁺ The content is 0 to 5%, preferably 0 to 2%, and more preferably Ti is not contained ⁴⁺ 。

Ce ⁴⁺ Is an optional component of glass. Ce ⁴⁺ Has the function of improving the ultraviolet light absorption of the glass and plays a role of clarification in the glass. However, ce ⁴⁺ The constituents are detrimental to the retention of the valence state of the semiconductor absorbing microstructure constituents in the glass of the present invention. Thus, ce ⁴⁺ The content of (B) is in the range of 0 to 2%, preferably 0 to 0.5%, more preferably not containing Ce ⁴⁺ 。

Sb ³⁺ Has the function of improving the ultraviolet light absorption of the glass and plays a role of clarification in the glass. Sb ³⁺ The content of (A) is favorable for promoting phase separation of glass and formation of a semiconductor absorption microstructure. However, sb ³⁺ Too high a content of (b) on the contrary results in glass that is not easily clarified. Thus, sb ³⁺ The content of (b) is in the range of 0 to 6%, preferably 0.1 to 5%, more preferably 0.2 to 4%.

< anionic Components >

O ^2- Is the main anionic component of the glass of the present invention. O is ^2- The content of (b) is in the range of 90 to 100%, preferably 92 to 100%, more preferably 95 to 98%.

S ^2- Semiconductor absorbing microstructures can be formed in the glass. S ^2- The content is too low, and the content of the semiconductor absorption microstructure in the glass is insufficient. S ^2- The content is too high, which is not beneficial to the uniformity of the glass on one hand, and has stronger erosion action on the crucible and refractory materials on the other hand. Thus, S ^2- The content of (b) is in the range of 0 to 10%, preferably 0.5 to 7.5%, more preferably 1 to 5%.

F ^- Is an optional component of the glass of the present invention. F ^- The volatilization of the components of the semiconductor absorption microstructure in the glass can be reduced, and the main principle is to reduce the melting temperature required by the glass by reducing the high-temperature viscosity of the glass. However, F ^- The color uniformity of the heat-treated glass is reduced. Thus, F ^- The content of (b) is in the range of 0 to 5%, preferably 0 to 1%, more preferably 0 to 0.5%, and further preferably F is not contained ^- 。

Se ^2- Are optional components of the glass of the present invention. Se ^2- It is advantageous to shift the cut-off wavelength of the glass in the infrared direction. However, se ^2- The hardness and chemical stability of the glass are reduced. Thus, se is present in the glasses of the invention ^2- The content of (B) is 0 to 2%, preferably 0 to 1%, more preferably 0 to 0.5%, and further preferably not containing Se ^2- 。

< component not contained >

The glasses of the invention preferably do not contain Rb ⁺ 、Cs ⁺ And the like. To achieve environmental friendlinessThe glasses according to the invention preferably do not contain environmentally harmful As ³⁺ 、Pb ²⁺ 、Tl ⁺ And (4) and the like.

The glass of the invention preferably does not contain N ^3- . If N is to be contained in the glass ^3- Precise control of the glass melting atmosphere is required. In glass melting plants suitable for industrial production, it is generally difficult to achieve N ^3- The introduction of (2). The glass of the invention is also preferably SO-free ₄ ^2- 。

"not containing" or "0%" as used herein means that the compound, ion, molecule, element or the like is not intentionally added to the glass of the present invention as a raw material; however, it is also 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 glass, and may be present in small or trace amounts in the final glass.

The presence of the above-mentioned preferred modes of introduction of the starting materials in the context of the present invention, but not excluding the introduction of the above-mentioned components in other forms, is also within the scope of the present invention. The starting materials whose mode of introduction is not specified can be introduced in any usable form.

The semiconductor absorption microstructure is a nano-scale crystal with low forbidden bandwidth, but the semiconductor absorption microstructure is extremely small in size, is surrounded by a glass network, can cause distortion of a crystal structure due to factors such as strain and interface action, and has the characteristics of incapability of generating obvious Bragg diffraction and existence of characteristic vibration. The cut-off limit and the cut-off wavelength described in the present invention both represent wavelengths corresponding to a glass transmittance of 5%.

[ method for producing Filter glass ]

The manufacturing method of the filter glass comprises the following steps: a base glass is formed, and then the base glass is subjected to a heat treatment process to form a filter glass.

The method for producing a matrix glass of the present invention comprises: the raw materials of various glass compositions are uniformly mixed according to the proportioning of the filter glass, and the processes of raw material melting, molten glass homogenization, molten glass clarification and the like of the glass are carried out by utilizing any available glass melting equipment. The matrix glass can be formed by single crucible pouring and leaking forming. The matrix glass of the present invention can have any useful shape and/or size.

The heat treatment process comprises the steps of putting matrix glass into a heat treatment furnace with uniform temperature, preserving heat for a certain time, and then naturally cooling or cooling according to a program control process.

The heat treatment process comprises the steps of controlling the heat treatment temperature and controlling the heat treatment time. The heat treatment temperature of the matrix glass needs to be in a certain range, and the heat treatment temperature is too low to enable a semiconductor absorption microstructure to be formed in the glass; when the heat treatment temperature is too high, other crystals except the semiconductor absorption microstructure can be formed in the glass, so that large Rayleigh scattering exists in the glass, and the transmittance of the filter glass in the light transmission range is reduced. In some embodiments, the heat treatment temperature is preferably in the range of 450 to 600 ℃, more preferably 490 to 570 ℃, and even more preferably 510 to 550 ℃; the heat treatment time is preferably 1 to 100 hours (hours), more preferably 5 to 60 hours (hours), and still more preferably 10 to 40 hours (hours).

The performance of the filter glass of the present invention will be described below.

< spectral Properties >

The test method of the spectral performance comprises the following steps: processing the filter glass sample into a sheet with double-sided polishing and a thickness of 2mm, and testing the spectrum of the glass sample by using an ultraviolet-visible spectrophotometer, wherein the testing wavelength range is 400-2000 nm.

The spectral properties of the filter glass according to the invention are characterized with the parameters defined below.

Definition of lambda ₅ The wavelength corresponding to 5% transmittance; definition of lambda ₅₀ The wavelength corresponding to a transmittance of 50%; definition of lambda _{Work by} The wavelength corresponding to the transmittance of 85%, i.e., the operating wavelength.

Lambda of the glass of the invention ₅ Is adjustable within the range of 480-700 nm.

Lambda of the glass of the invention ₅₀ Is adjustable within the range of 550-750 nm.

Lambda of the glass of the invention _{Work in} Is adjustable within 650-850 nm.

The glass of the invention has a lambda ₅₀ -λ ₅ Small size. If λ ₅₀ -λ ₅ And the cut-off capability of the corresponding glass is weak, so that more light rays with the wavelength lower than the working wavelength of the glass can penetrate through the glass, and the glass is not beneficial to identification and sensing related applications. Lambda [ alpha ] ₅₀ -λ ₅ The material characteristics corresponding to this problem are too low a semiconductor absorption microstructure content in the glass and improper matching of glass heat treatment process and glass components.

In some embodiments, the lambda of the filter glass of the present invention ₅₀ -λ ₅ Is 100nm or less, preferably 80nm or less, and more preferably 70nm or less.

The glass of the invention also has lambda _{Work by} -λ ₅₀ Small size. If λ _{Work in} -λ ₅₀ Large, resulting in more light having a wavelength below the working wavelength of the glass being transmitted through the glass of the present invention, which is not conducive to identification, sensing related applications. Lambda [ alpha ] _{Work in} -λ ₅₀ The large corresponding material problem is that the crystallization with larger grain diameter exists in the glass after heat treatment due to improper component design and improper heat treatment process of the glass, and the scattering effect of the crystallization causes the transmittance of the glass to be poor, particularly at lambda _{Work by} Most significant nearby.

In some embodiments, the λ of the filter glass of the present invention _{Work by} -λ ₅₀ Is 80nm or less, preferably 70nm or less, and more preferably 60nm or less.

< mu.g-apparent hardness >

The microKirschner hardness (H) of the filter glass according to the invention was measured using the microKirschner hardness test method described in Standard GB/T7962.18-2010 _K ). The microgram hardness test is a test method for representing the hardness and scratch resistance of glass. In this context, microkeh hardness is sometimes referred to simply as hardness.

In some embodiments, the filter glasses of the present invention have a microKirschner hardness (H) _K ) Is 380X 10 ⁷ Pa or more, preferably 400X 10 ⁷ Pa or more, more preferably 420X 10 ⁷ Pa or above.

< stability against acid Effect >

Stability of the acid resistance of the glass (D) _A ) (powder method) the test was carried out according to the method specified in the Standard GB/T17129. The more excellent the stability of the glass against acid action, the longer the glass will fail in the natural environment. Acid resistance stability is sometimes referred to herein simply as acid resistance or acid resistance stability.

In some embodiments, the filter glasses of the invention have stability to acid action (D) _A ) Is 3 or more, preferably 2 or more, and more preferably 1.

< stability against Water Effect >

Stability of the glass to Water action (D) _W ) (powder method) the test was carried out according to the method specified in the Standard GB/T17129. The more stable the glass is against water action, the longer it will fail in the natural environment. Stability to hydrolytic action is sometimes referred to herein simply as water resistance or hydrolytic stability.

In some embodiments, the filter glasses of the invention have a stability to water action (D) _W ) Is 3 or more, preferably 2 or more, and more preferably 1.

[ glass preform and glass Member ]

The glass preform can be produced from the produced filter glass by means of, 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 filter glass by grinding or polishing, or by producing a preform for press molding from the filter glass, subjecting the preform to reheat press molding, and then polishing, or by precision press molding the preform obtained by polishing. The glass prefabricated member formed by the glass can also be subjected to a physical toughening or chemical toughening process according to needs.

Note that the means for producing the glass preform is not limited to the above means.

Both the glass preform and the glass element of the invention are formed from the filter glass of the invention described above. The glass preform of the present invention has excellent characteristics possessed by filter glass; the glass element of the present invention has excellent characteristics of filter glass, and can provide glass elements such as various filters, lenses, prisms, and the like, which are valuable.

[ Equipment ]

The filter glass and the glass element formed by the filter glass can be used for manufacturing devices such as optical filters, photographic devices, camera devices, identification and control devices, monitoring devices, sensor devices and the like.

[ examples ]

In order to further clearly illustrate and explain the technical solution of the present invention, the following non-limiting examples 1 to 18 are provided in tables 1 to 3. In this example, filter glasses having compositions shown in tables 1 to 3 were obtained by the above-described method for producing filter glasses. The characteristics of each glass were measured by the test method described in the present invention, and the measurement results are shown in tables 1 to 3.

Table 1.

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Table 2.

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Table 3.

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Claims (22)

1. Filter glass, characterized in that its composition, expressed in mole percentages, is such that the cationic component comprises: si ⁴⁺ ：36～70％；Na ⁺ ：5～25％；Li ⁺ ：0～8％；K ⁺ ：0～10％；Zn ²⁺ ：0～15％；Sb ³⁺ ：0～6％；

The anionic component comprises: o is ^2- ：90～100％；S ^2- ：0～10％。

2. The filter glass according to claim 1, wherein the composition is expressed in mole percent and the cationic component further comprises: al (Al) ³⁺ :0 to 12 percent; and/or B ³⁺ :0 to 10 percent; and/or P ⁵⁺ :0 to 5 percent; and/or Ag ⁺ :0 to 5 percent; and/or Ba ^{2 +} :0 to 10 percent; and/or Mg ²⁺ :0 to 8 percent; and/or Ca ²⁺ :0 to 10 percent; and/or Sr ²⁺ :0 to 5 percent; and/or La ³⁺ :0 to 6 percent; and/or Y ³⁺ :0 to 8 percent; and/or V ⁵⁺ :0 to 5 percent; and/or Ti ⁴⁺ :0 to 5 percent; and/or Ce ⁴⁺ ：0～2％。

3. Filter glass, characterised in that its composition is expressed in mole%, (Zn) ²⁺ +Mg ²⁺ +Ca ²⁺ +Sr ²⁺ )/(Na ⁺ +Li ⁺ +K ⁺ +Ag ⁺ ) Is 0.2 to 1.0, lambda of the filter glass ₅₀ -λ ₅ λ is 100nm or less _{Work by} -λ ₅₀ Is 80nm or less.

4. Filter glass according to claim 3, characterised in that its composition, expressed in mole percentage, contains a cationic component：Si ⁴⁺ :36 to 70 percent; and/or Na ⁺ :5 to 25 percent; and/or Li ⁺ :0 to 8 percent; and/or K ⁺ :0 to 10 percent; and/or Zn ^{2 +} :0 to 15 percent; and/or Sb ³⁺ :0 to 6 percent; and/or Al ³⁺ :0 to 12 percent; and/or B ³⁺ :0 to 10 percent; and/or P ⁵⁺ :0 to 5 percent; and/or Ag ⁺ :0 to 5 percent; and/or Ba ²⁺ :0 to 10 percent; and/or Mg ²⁺ :0 to 8 percent; and/or Ca ²⁺ :0 to 10 percent; and/or Sr ²⁺ :0 to 5 percent; and/or La ³⁺ :0 to 6 percent; and/or Y ³⁺ :0 to 8 percent; and/or V ⁵⁺ :0 to 5 percent; and/or Ti ⁴⁺ :0 to 5 percent; and/or Ce ^{4 +} ：0～2％；

The anionic component comprises: o is ^2- :90 to 100 percent; and/or S ^2- ：0～10％。

5. A filter glass according to any one of claims 1 to 4, characterised in that its composition, expressed in mole percent, comprises a cationic component comprising: si ⁴⁺ :44 to 66%, preferably Si ⁴⁺ :50 to 64 percent; and/or Na ⁺ :10 to 23%, preferably Na ⁺ :12 to 20 percent; and/or Li ⁺ :0.2 to 4%, preferably Li ⁺ :0.6 to 3 percent; and/or K ⁺ :0.2 to 8%, preferably K ⁺ :0.5 to 5 percent; and/or Zn ²⁺ :0 to 13%, preferably Zn ²⁺ :3 to 11 percent; and/or Sb ³⁺ :0.1 to 5%, preferably Sb ³⁺ :0.2 to 4 percent; and/or Al ³⁺ :0 to 8%, preferably Al ³⁺ :0 to 4 percent; and/or B ³⁺ :0 to 5%, preferably B ³⁺ :0 to 2 percent; and/or P ⁵⁺ :0.1 to 2.5%, preferably P ⁵⁺ :0.2 to 1.5 percent; and/or Ag ⁺ :0 to 2%, preferably Ag ⁺ :0 to 1 percent; and/or Ba ²⁺ :0 to 5%, preferably Ba ²⁺ :0 to 2 percent; and/or Mg ²⁺ :0 to 4%, preferably Mg ²⁺ :0 to 2 percent; and/or Ca ²⁺ :0 to 4%, preferably Ca ²⁺ :0 to 2 percent; and/or Sr ²⁺ :0 to 2 percent; and/or La ³⁺ ：0～4％，Preferably La ³⁺ :0 to 2 percent; and/or Y ³⁺ :0 to 6%, preferably Y ³⁺ :0 to 3 percent; and/or V ⁵⁺ :0 to 1%, preferably V ⁵⁺ :0 to 0.5 percent; and/or Ti ⁴⁺ :0 to 2 percent; and/or Ce ⁴⁺ ：0～0.5％。

6. A filter glass according to any one of claims 1 to 4, characterised in that its composition, expressed in mole percent, contains an anionic component comprising: o is ^2- :92 to 100%, preferably O ^2- :95 to 98 percent; and/or S ^2- :0.5 to 7.5%, preferably S ^2- ：1～5％。

7. A filter glass according to any one of claims 1 to 4, having a composition expressed in mole percent, wherein: li ⁺ /Na ⁺ 0 to 0.5, preferably Li ⁺ /Na ⁺ 0 to 0.3, more preferably Li ⁺ /Na ⁺ 0.025 to 0.2.

8. A filter glass according to any one of claims 1 to 4, having a composition expressed in mole percent, wherein: k ⁺ /(Li ⁺ +Na ⁺ ) Is 0 to 0.4, preferably K ⁺ /(Li ⁺ +Na ⁺ ) Is 0 to 0.25, more preferably K ⁺ /(Li ⁺ +Na ⁺ ) 0.05 to 0.15.

9. A filter glass according to any one of claims 1 to 4, having a composition expressed in mole percent, wherein: p ⁵⁺ /Si ⁴⁺ Is 0 to 0.1, preferably P ⁵⁺ /Si ⁴⁺ Is 0 to 0.06, more preferably P ⁵⁺ /Si ⁴⁺ 0.01 to 0.05.

10. A filter glass according to any one of claims 1 to 4, having a composition expressed in mole percent, wherein: (Zn) ²⁺ +Mg ²⁺ +Ca ²⁺ +Sr ²⁺ )/(Na ⁺ +Li ⁺ +K ⁺ +Ag ⁺ ) Is 0.2 &1.0, preferably (Zn) ²⁺ +Mg ²⁺ +Ca ²⁺ +Sr ²⁺ )/(Na ⁺ +Li ⁺ +K ⁺ +Ag ⁺ ) Is 0.25 to 0.8, more preferably (Zn) ²⁺ +Mg ²⁺ +Ca ²⁺ +Sr ²⁺ )/(Na ⁺ +Li ⁺ +K ⁺ +Ag ⁺ ) 0.3 to 0.6.

11. A filter glass according to any one of claims 1 to 4, having a composition expressed in mole percent, wherein: zn ²⁺ +2×La ³⁺ +2×Y ³⁺ 8 to 30%, preferably Zn ²⁺ +2×La ³⁺ +2×Y ³⁺ 9 to 25%, more preferably Zn ²⁺ +2×La ³⁺ +2×Y ³⁺ 10 to 20 percent.

12. A filter glass according to any one of claims 1 to 4, characterised in that its composition, expressed in mole percent, has the cation further comprising: cu (copper) ⁺ :0 to 0.5%, preferably Cu ⁺ :0 to 0.2%, more preferably Cu ⁺ :0 to 0.1%, more preferably Cu ⁺ :0 to 0.01 percent; and/or Fe ²⁺ :0 to 0.5%, preferably Fe ²⁺ :0 to 0.2%, more preferably Fe ²⁺ :0 to 0.1%, more preferably Fe ^{2 +} :0 to 0.01 percent; and/or Co ²⁺ :0 to 0.5%, preferably Co ²⁺ :0 to 0.2%, more preferably Co ²⁺ :0 to 0.1%, more preferably Co ²⁺ :0 to 0.01 percent; and/or Mn ²⁺ :0 to 0.5%, preferably Mn ²⁺ :0 to 0.2%, more preferably Mn ²⁺ :0 to 0.1%, and more preferably Mn ²⁺ ：0～0.01％。

13. A filter glass according to any one of claims 1 to 4, having a composition expressed in mole percent, wherein: cu (copper) ⁺ +Fe ²⁺ +Co ²⁺ +Mn ²⁺ +(V ⁵⁺ /100) 0 to 0.5%, preferably Cu ⁺ +Fe ²⁺ +Co ²⁺ +Mn ²⁺ +(V ⁵⁺ /100) 0 to 0.2%, more preferably Cu ⁺ +Fe ²⁺ +Co ²⁺ +Mn ²⁺ +(V ⁵⁺ /100) is 0 to 0.1%, and Cu is more preferable ⁺ +Fe ²⁺ +Co ²⁺ +Mn ²⁺ +(V ^{5 +} Per 100) is 0 to 0.01 percent.

14. Filter glass according to one of claims 1 to 4, characterised in that it contains Cu ⁺ 、Fe ²⁺ 、Co ²⁺ 、Mn ²⁺ Less than 2 kinds of components, preferably containing Cu ⁺ 、Fe ²⁺ 、Co ²⁺ 、Mn ²⁺ 1 component in, or does not contain Cu ⁺ 、Fe ²⁺ 、Co ²⁺ 、Mn ²⁺ 。

15. A filter glass according to any one of claims 1 to 4, characterised in that its composition, expressed in mole percent, contains anions further comprising: f ^- :0 to 5%, preferably F ^- :0 to 1%, more preferably F ^- :0 to 0.5 percent; and/or Se ^2- :0 to 2%, preferably Se ^2- :0 to 1%, more preferably Se ^2- ：0～0.5％。

16. Filter glass according to one of claims 1 to 4, characterised in that its composition does not contain Sr ²⁺ (ii) a And/or does not contain Ti ⁴⁺ (ii) a And/or does not contain Ce ⁴⁺ (ii) a And/or does not contain Rb ⁺ (ii) a And/or does not contain Cs ⁺ (ii) a And/or does not contain As ³⁺ (ii) a And/or does not contain Pb ²⁺ (ii) a And/or does not contain Tl ⁺ (ii) a And/or does not contain F ^- (ii) a And/or does not contain Se ^2- 。

17. Filter glass according to any one of claims 1 to 4, characterised in that the filter glass has a lambda ₅₀ -λ ₅ Is 100nm or less, preferably 80nm or less, more preferably 70nm or less; and/or lambda of the filter glass _{Work in} -λ ₅₀ 80nm or less, preferably 70nm or less, more preferably 60nm or less; and/or microKirschner hardness H _K Is 380X 10 ⁷ Pa or more, preferably 400X 10 ⁷ Pa is atMore preferably 420X 10 ⁷ Pa is above; and/or stability against acid action D _A Is 3 or more, preferably 2 or more, more preferably 1; and/or stability against water action D _W Is 3 or more, preferably 2 or more, and more preferably 1.

18. A glass preform made of the filter glass according to any one of claims 1 to 17.

19. Glass element, characterized in that it is made of a filter glass according to any one of claims 1 to 17 or of a glass preform according to claim 18.

20. An instrument made of the filter glass according to any one of claims 1 to 17 or made of the glass element according to claim 19.

21. A method for producing a filter glass according to any one of claims 1 to 17, characterized in that the method comprises the steps of: a base glass is formed, and then the base glass is subjected to a heat treatment process to form a filter glass.

22. A method for manufacturing a filter glass according to claim 21, wherein the heat treatment process comprises controlling a heat treatment temperature and controlling a heat treatment time, the heat treatment temperature being in a range of 450 to 600 ℃, preferably 490 to 570 ℃, and more preferably 510 to 550 ℃; the heat treatment time is 1 to 100 hours, preferably 5 to 60 hours, and more preferably 10 to 40 hours.

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