Near infrared light absorbing glass, element and optical filter

Abstract

Provided in the present invention is a near infrared light absorbing glass having excellent intrinsic quality. Among components, expressed in molar percentage, of the near infrared light absorbing glass, cationic components comprise: 38-52% of P5+, 3-12% of Al3+, 2-16% of Cu2+, 10-40% of Rn+ and 3-30% of R2+, the Rn+ being one or more of Li+, Na+ and K+, and the R2+ being one or more of Mg2+, Ca2+, Sr2+ and Ba2+; and anion components comprise: 82-97% of O2-, and 3-18% of F-. By means of reasonable component design, the near infrared light absorbing glass obtained by the present invention exhibits excellent transmission characteristics in the visible light region and excellent absorption characteristics in the near-infrared region, and also has excellent intrinsic quality, thereby satisfying the use of high-performance devices.

Description

Near-infrared light absorbing glass, components and filters Technical Field

[0001] This invention relates to a glass, and more particularly to a near-infrared light-absorbing glass, as well as near-infrared light-absorbing elements and filters made therefrom. Background Technology

[0002] In recent years, the spectral sensitivity of semiconductor imaging elements such as CCDs and CMOS sensors used in digital cameras, camera phones, and VTR cameras has expanded from the visible field to the near-infrared field. Using filters that absorb light in the near-infrared region can achieve a level of sensitivity similar to human vision. The visible light wavelengths that the human eye can perceive are between 400 and 700 nm. Therefore, by using filters that absorb near-infrared light, images with a brightness factor close to that of the human eye can be obtained. With the miniaturization of optical modules and the increasing demands for reliability, higher requirements are placed on the near-infrared light-absorbing glass used to manufacture these filters. This requires such glass to possess excellent transmittance characteristics in the visible field and excellent absorption characteristics in the near-infrared region.

[0003] Furthermore, spectral characteristics determine the basic functions of near-infrared absorbing glass. Besides possessing the desired spectral characteristics, near-infrared absorbing glass also needs excellent internal quality (such as a high bubble count). If the glass composition is not properly designed, it can easily result in poor internal quality and defects such as poor bubble count (the presence of numerous bubbles and inclusions within the glass). Chinese patent CN102656125A discloses a near-infrared cutoff filter glass containing 16.2%–25% Al in its composition. 3+ This can easily lead to a deterioration in the near-infrared light absorption characteristics of the glass, and it is also prone to internal quality defects such as bubbles, resulting in poor glass bubble degree and making it difficult to meet the requirements of high-performance optical equipment in terms of internal quality. Summary of the Invention

[0004] The technical problem to be solved by the present invention is to provide a near-infrared light absorbing glass with excellent intrinsic quality.

[0005] The technical solution adopted by this invention to solve the technical problem is:

[0006] (1) Near-infrared light absorbing glass, the composition of which is expressed as molar percentage, the cationic component contains: P 5+ 38-52%; Al 3+ 3-12%; Cu 2+ 2-16%; Rn + : 10-40%; R 2+ 3-30%, the Rn + For Li + Na + K+ One or more of them, R 2+ Mg 2+ Ca 2+ 、Sr 2+ Ba 2+ One or more of the following;

[0007] The anionic component contains: O 2- 82-97%; F - 3-18%.

[0008] (2) According to the near-infrared light absorbing glass described in (1), its composition is expressed as a molar percentage, and the cationic component also contains: Ln 3+ : 0–8%; and / or B 3+ : 0-5%; and / or Si 4+ 0–5%; and / or Zn 2+ : 0-10%; and / or Sb 3+ 0-3%, the Ln 3+ For La 3+ Gd 3+ Y 3+ One or more of the following;

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

[0010] (3) Near-infrared light absorbing glass, the composition of which is expressed as mole percentage, the cationic component is composed of P 5+ 38-52%; Al 3+ 3-12%; Cu 2+ 2-16%; Rn + : 10-40%; R 2+ 3-30%; Ln 3+ : 0-8%; B 3+ : 0-5%; Si 4+ 0-5%; Zn 2+ : 0-10%; Sb 3+ Composition: 0-3%, wherein Rn + For Li + Na + K + One or more of them, R 2+ Mg 2+ Ca 2+ 、Sr 2+ Ba 2+ One or more of them, Ln 3+ For La 3+ Gd 3+Y 3+ One or more of the following;

[0011] The anionic component consists of O 2- 82-97%; F - 3-18%; Cl - +Br - +I - Composition: 0-2%

[0012] (4) The near-infrared light absorbing glass according to any one of (1) to (3), wherein the composition is expressed as a mole percentage, and one or more of the following seven conditions are met:

[0013] 1)(P 5+ -38%) / (2×Li + The value is 0.5–30.0, preferably (P). 5+ -38%) / (2×Li + The value is 1.0 to 25.0, more preferably (P) 5+ -38%) / (2×Li + The value ranges from 2.5 to 10.0.

[0014] 2) Cu 2+ / Li + The value is 0.5–30.0, with Cu being preferred. 2+ / Li + The value is 1.0 to 10.0, more preferably Cu. 2+ / Li + The value ranges from 2.0 to 7.0.

[0015] 3) Mg 2+ / Li + The concentration ranges from 0.5 to 15.0, with Mg being the preferred element. 2+ / Li + The value is 1.0 to 10.0, more preferably Mg. 2+ / Li + The value ranges from 1.2 to 8.0.

[0016] 4) Na + / (Mg 2+ +Li + The concentration is 1.0–10.0, with Na being the preferred choice. + / (Mg 2+ +Li + The concentration of Na is 2.0–8.0, with Na being more preferred. + / (Mg 2+ +Li + The value ranges from 4.0 to 7.0.

[0017] 5)(Al 3+ +Y 3+ ) / (3×Li+ The value ranges from 0.4 to 20.0, with (Al) being preferred. 3+ +Y 3+ ) / (3×Li + The value is 0.9 to 15.0, more preferably (Al). 3+ +Y 3+ ) / (3×Li + The value ranges from 1.1 to 6.0.

[0018] 6)(3×Zn 2+ +Li + ) / Ba 2+ The value ranges from 0.2 to 5.0, with (3×Zn) being preferred. 2+ +Li + ) / Ba 2+ The value is 0.4 to 3.0, more preferably (3×Zn). 2+ +Li + ) / Ba 2+ The value is 0.5 to 2.0.

[0019] 7)(P 5+ -38%) / F - Less than 3.0, preferred (P) 5+ -38%) / F - Less than 1.5, more preferably (P) 5+ -38%) / F - Less than 1.0.

[0020] (5) The near-infrared light-absorbing glass according to any one of (1) to (3), wherein its composition is expressed as a molar percentage, wherein: P 5+ 42-51%, P is preferred 5+ 44-50%; and / or Al 3+ 4-10%, preferably Al 3+ 6-9%; and / or Cu 2+ 3-10%, preferably Cu 2+ 4-8%; and / or Rn + 15-35%, preferably Rn + 20-30%; and / or R 2+ 5-20%, preferably R 2+ : 8–18%; and / or Ln 3+ 0-6%, preferably Ln 3+ 0-4%, more preferably free of Ln 3+ ; and / or B 3+ 0-2%, B is preferred 3+ 0-1%, preferably free of B 3+ ; and / or Si 4+ 0-2%, preferably Si 4+0-1%, more preferably free of Si 4+ ; and / or Zn 2+ 1-6%, preferably Zn 2+ : 1-4%; and / or Sb 3+ 0-2%, preferably Sb 3+ 0.01% to 1%, the Rn + For Li + Na + K + One or more of them, R 2+ Mg 2+ Ca 2+ 、Sr 2+ Ba 2+ One or more of them, Ln 3+ For La 3+ Gd 3+ Y 3+ One or more of them.

[0021] (6) The near-infrared light-absorbing glass according to any one of (1) to (3), wherein its composition is expressed in molar percentage, wherein: Li + 0-10%, preferably Li + 0.2-6%, more preferably Li + 0.5–3%; and / or Na + 10-30%, preferably Na + 13-27%, more preferably Na + 15-25%; and / or K + 0-10%, K is preferred + 0-7%, preferably K + 0–5%; and / or Mg 2+ 1-10%, preferably Mg 2+ 1.5-8%, more preferably Mg 2+ 2-5%; and / or Ca 2+ 1-10%, preferably Ca 2+ 1.5-8%, more preferably Ca 2+ 2-6%; and / or Sr 2+ 0-10%, preferably Sr 2+ 0-6%, more preferably Sr 2+ : 1-5%; and / or Ba 2+ 1-10%, Ba is preferred. 2+ 1.5-8%, more preferably Ba 2+ : 2-6%; and / or Y 3+ 0-6%, preferred Y 3+ 0-5%, more preferably Y 3+: 0-2%; and / or La 3+ 0-5%, preferably La 3+ 0-3%, more preferably La 3+ 0–1%; and / or Gd 3+ 0-5%, preferably Gd 3+ 0-3%, more preferably Gd 3+ : 0-1%.

[0022] (7) The near-infrared light-absorbing glass according to any one of (1) to (3), wherein its composition is expressed as a molar percentage, wherein: O 2- 85-95%, preferred: O 2- : 87-93%; and / or F - 5-15%, preferably F - 7–13%; and / or Cl - +Br - +I - 0-1%, preferably Cl - +Br - +I - : 0~0.5%.

[0023] (8) The near-infrared light absorbing glass according to any one of (1) to (3), wherein the weather resistance of the near-infrared light absorbing glass is Class 3 or above, preferably Class 2 or above, more preferably Class 1; and / or the transition temperature is below 430°C, preferably below 420°C, more preferably below 410°C, and even more preferably below 400°C; and / or the Young's modulus is 6000 × 10⁻⁶. 7 ~8000×10 7 Pa, preferably 6200 × 10⁻⁶ 7 ~7500×10 7 Pa, more preferably 6500 × 10 7 ~6900×10 7 Pa; and / or bubble degree of A0 or above, preferably A 00 Grade; and / or viscosity at 800°C is 8.0 poise or less, preferably 5.0 poise or less, more preferably 3.8 poise or less.

[0024] (9) Near-infrared light absorbing glass according to any one of (1) to (3), near-infrared light absorbing glass with a thickness of less than 0.4 mm, and a spectral transmittance τ at a wavelength of 400 nm. 400 The transmittance is 84.0% or more, preferably 86.0% or more, more preferably 88.0% or more; and / or the spectral transmittance τ at a wavelength of 500 nm. 500 The transmittance is 85.0% or more, preferably 87.0% or more, more preferably 89.0% or more; and / or the spectral transmittance τ at a wavelength of 1100 nm. 1100The transmittance is 18.0% or less, preferably 16.0% or less, more preferably 14.0% or less, and even more preferably 12.0% or less; and / or the wavelength λ corresponding to a transmittance of 50% in the spectral transmittance range of 500 to 700 nm. 50 The wavelength is below 640nm, preferably 610-635nm, and more preferably 615-630nm.

[0025] (10) The near-infrared light absorbing glass according to (9) has a thickness of 0.05 to 0.4 mm, preferably 0.1 to 0.3 mm, more preferably 0.15 to 0.25 mm, and even more preferably 0.15 mm, or 0.18 mm, or 0.20 mm, or 0.21 mm, or 0.23 mm, or 0.25 mm.

[0026] (11) Near-infrared light absorbing glass element, made of any of the near-infrared light absorbing glass described in (1) to (10).

[0027] (12) A filter containing any of the near-infrared light absorbing glass described in (1) to (10), or containing the near-infrared light absorbing glass element described in (11).

[0028] (13) An apparatus comprising any of the near-infrared light absorbing glass described in (1) to (10), or comprising the near-infrared light absorbing glass element described in (11), or comprising the filter described in (12).

[0029] The beneficial effects of this invention are: through reasonable component design, the near-infrared light absorbing glass obtained by this invention has excellent transmittance characteristics in the visible light region and excellent absorption characteristics in the near-infrared region, while also having excellent intrinsic quality, meeting the requirements of high-performance equipment. Detailed Implementation

[0030] The embodiments of the near-infrared light-absorbing 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 near-infrared light-absorbing glass of the present invention will sometimes be simply referred to as glass.

[0031] Near-infrared light absorbing glass

[0032] The composition ranges of each component in the near-infrared light absorbing glass of the present invention are described below. In this specification, unless otherwise specified, the content of a cationic component is expressed as the molar percentage (mol%) of that cation among all cationic components; the content of anionic components is expressed as the molar percentage of that anion among all anionic components; the ratio between the contents of cationic components is the ratio of 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 is expressed as an ion molar percentage; the ratio between the contents of cationic and anionic components is the ratio of the molar percentage contents of a cationic component among all cationic components to the molar percentage contents of anionic components among all anionic components.

[0033] 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 or 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.

[0034] 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 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."

[0035] <Catonic Components>

[0036] P 5+ It is an indispensable component of the glass framework in this invention, which can promote glass formation and improve the near-infrared absorption performance of the glass. If P 5+ If the content is less than 38%, the above effects are insufficient, and the near-infrared absorption function of the glass will be difficult to meet the design requirements; if P 5+ When the content of P exceeds 52%, the chemical stability and weather resistance of the glass decrease rapidly. Therefore, in this invention, P... 5+ The content is 38-52%, preferably 42-51%, and more preferably 44-50%.

[0037] Al 3+ Al content is beneficial for increasing glass stability, strength, and weather resistance; however, if its content exceeds 12%, the glass's crystallization tendency increases, its melting properties deteriorate, and its near-infrared light absorption characteristics worsen. Therefore, in this invention, Al... 3+The content is 3-12%, preferably 4-10%, and more preferably 6-9%.

[0038] Cu 2+ Cu is an essential component for the near-infrared light absorption performance of the glass of this invention. If its content is less than 2%, the near-infrared absorption performance of the glass is difficult to meet the design requirements. However, if Cu... 2+ When the Cu content exceeds 16%, the transmittance of the glass in the visible light region decreases, the valence state of Cu in the glass changes, making it difficult to obtain the desired near-infrared light absorption performance, and reducing the glass's devitrification resistance. Therefore, in this invention, Cu... 2+ The content is 2-16%, preferably 3-10%, and more preferably 4-8%.

[0039] Rn + (Rn + For Li + Na + K + One or more of these can lower the melting temperature and viscosity of glass, and promote the melting of more Cu to Cu. 2+ The state exists, but as Rn + As the concentration of Rn increases, the chemical stability of the glass deteriorates, and its resistance to crystallization also deteriorates rapidly. In this invention, a concentration of Rn of 10% or more is used. + To achieve the above effect, but when Rn + When the content of Rn exceeds 40%, the glass's devitrification resistance decreases, its formability deteriorates, and its hardness decreases. Therefore, in this invention, Rn... + The content is 10-40%, preferably 15-35%, and more preferably 20-30%.

[0040] Li + It is a component that improves glass melt properties, but when Li + When the content exceeds 10%, the glass's devitrification resistance, formability, and hardness decrease, while the raw material cost of the glass increases. Therefore, Li + The content is 0-10%, preferably 0.2-6%, and more preferably 0.5-3%.

[0041] In some implementations, by controlling (P) 5+ -38%) / (2×Li + A P value above 0.5 can yield near-infrared absorbing glass with good weather resistance and spectral performance, but when (P) 5+ -38%) / (2×Li + When the value of (P) is greater than 30.0, the high-temperature viscosity of the glass increases, and the degree of bubble formation worsens. Therefore, (P) is preferred. 5+ -38%) / (2×Li + The value is 0.5 to 30.0, more preferably (P 5+-38%) / (2×Li + The value is 1.0 to 25.0, and further optimization is preferred (P). 5+ -38%) / (2×Li + The value ranges from 2.5 to 10.0.

[0042] In some implementations, Cu 2+ The content of Li + The ratio between the contents of Cu 2+ / Li + By controlling the concentration within the range of 0.5 to 30.0, near-infrared absorbing glass that simultaneously possesses excellent spectral properties and weather resistance can be obtained. Therefore, Cu is preferred. 2+ / Li + The value ranges from 0.5 to 30.0, with Cu being more preferred. 2+ / Li + The value is 1.0 to 10.0, with Cu being the more preferred option. 2+ / Li + The value ranges from 2.0 to 7.0.

[0043] Na + It can significantly increase the "alkalinity" of glass, causing the Cu in the glass to be converted into Cu... 2+ The presence of sodium in the form of sodium improves the visible light transmittance of glass, achieving a better filtering effect on near-infrared light. However, excessive sodium... + This can lead to difficulties in glass forming and a decrease in glass hardness. Therefore, in this invention, Na... + The content is 10-30%, preferably 13-27%, and more preferably 15-25%.

[0044] K + It has strong fluxing and holding properties for Cu 2+ While valence states play a role, their content exceeding 10% significantly reduces the chemical stability and devitrification resistance of the glass. Therefore, K... + The content is 0-10%, preferably 0-7%, and more preferably 0-5%.

[0045] R 2+ (R 2+ Mg 2+ Ca 2+ 、Sr 2+ Ba 2+ One or more of these can be used to lower the melting temperature of glass, improve its glass-forming stability and hardness, but if R 2+ When the content of [specific component] exceeds 30%, the devitrification resistance of the glass decreases. Therefore, in this invention, R [specific component]... 2+ The content is 3-30%, preferably 5-20%, and more preferably 8-18%.

[0046] Mg2+ It can enhance the chemical stability of glass and improve its processing performance. However, if its content exceeds 10%, the glass's resistance to crystallization decreases, and its visible light transmittance decreases. Therefore, Mg... 2+ The content is 1-10%, preferably Mg. 2+ The content is 1.5-8%, more preferably Mg. 2+ The content is 2-5%.

[0047] In some implementations, Mg 2+ The content of Li + The ratio between the contents of Mg 2+ / Li + When the Mg content is controlled above 0.5, near-infrared light-absorbing glass with good weather resistance can be obtained, but when Mg... 2+ / Li + When the viscosity exceeds 15.0, the high-temperature viscosity of the glass increases, and the degree of bubble formation deteriorates. Therefore, Mg is preferred. 2+ / Li + The value ranges from 0.5 to 15.0, with Mg being more preferred. 2+ / Li + The value is 1.0 to 10.0, with Mg being more preferred. 2+ / Li + The value ranges from 1.2 to 8.0.

[0048] In some implementations, Na is controlled + / (Mg 2+ +Li + When the value of Na is in the range of 1.0 to 10.0, near-infrared light-absorbing glass with good elastic modulus and excellent spectral performance can be obtained. Therefore, Na is preferred. + / (Mg 2+ +Li + The concentration of Na is 1.0 to 10.0, with Na being more preferred. + / (Mg 2+ +Li + The Na content is 2.0–8.0, with Na being the most preferred. + / (Mg 2+ +Li + The value ranges from 4.0 to 7.0.

[0049] By containing more than 1% Ca 2+ It can enhance the anti-crystallization properties of glass and improve its Young's modulus, but when its content exceeds 10%, the glass's "basicity" is insufficient, leading to poor spectral performance. Therefore, Ca... 2+ The content is 1-10%, preferably 1.5-8%, and more preferably 2-6%.

[0050] Sr 2+It can improve the chemical stability of glass and increase visible light transmittance, but if its content exceeds 10%, the glass's resistance to crystallization decreases. Therefore, Sr... 2+ The content is 0-10%, preferably 0-6%, and more preferably 1-5%.

[0051] Ba 2+ This invention can improve the transmittance of glass in the visible light region, enhance its chemical stability, and increase its strength. It utilizes a Ba content of 1% or more... 2+ To achieve the above effect, but if Ba 2+ When the content of Ba exceeds 10%, the density of the glass increases and its resistance to crystallization deteriorates. Therefore, Ba 2+ The content is 1-10%, preferably Ba. 2+ The content is 1.5-8%, more preferably Ba. 2+ The content is 2-6%.

[0052] Ln 3+ (Ln 3+ For La 3+ Gd 3+ Y 3+ One or more of the following (e.g., Ln) are beneficial for improving the visible light transmittance and near-infrared absorption properties of glass, as well as its chemical stability and hardness. However, if their content exceeds 8%, the glass's resistance to crystallization deteriorates. Therefore, the present invention Ln 3+ The content is 0-8%, preferably 0-6%, and more preferably 0-4%. In some embodiments, it is further preferred that it does not contain Ln. 3+ Y 3+ Compared to La in glass 3+ and Gd 3+ This is more conducive to obtaining the desired spectral characteristics of the present invention; therefore, Y is preferred. 3+ The content is 0-6%, more preferably Y 3+ The content of Y is 0-5%, and Y is further preferred. 3+ The content is 0-2%; La is preferred. 3+ The content is 0-5%, more preferably La 3+ The content of La is 0-3%, and La is further preferred. 3+ The content is 0-1%; preferably Gd 3+ The content is 0-5%, more preferably Gd 3+ The content of Gd is 0-3%, and Gd is further preferred. 3+ The content is 0-1%.

[0053] In some implementations, control (A1) 3+ +Y 3+ ) / (3×Li +A value of α (Al) above 0.4 can yield near-infrared absorbing glass with excellent weather resistance and transition temperature, but if (Al) 3+ +Y 3+ ) / (3×Li + When the value of (Al) exceeds 20.0, the high-temperature viscosity of the glass increases, and the degree of bubble formation worsens. Therefore, (Al) is preferred. 3+ +Y 3+ ) / (3×Li + The value is 0.4 to 20.0, more preferably (Al). 3+ +Y 3+ ) / (3×Li + The value is 0.9–15.0, and further preferred (Al). 3+ +Y 3+ ) / (3×Li + The value ranges from 1.1 to 6.0.

[0054] Zn 2+ In Cu 2+ At higher concentrations, Zn can significantly improve the thermal stability of glass, but when the Zn content is high... 2+ When the content of Zn exceeds 10%, it leads to a decrease in visible light transmittance. Therefore, Zn 2+ The content is 0-10%, preferably 1-6%, and more preferably 1-4%.

[0055] In some implementations, by controlling (3×Zn) 2+ +Li + ) / Ba 2+ A value in the range of 0.2 to 5.0 yields near-infrared absorbing glass with low high-temperature viscosity, excellent bubble density, and superior spectral performance. Therefore, (3×Zn) is preferred. 2+ +Li + ) / Ba 2+ The value is 0.2 to 5.0, more preferably (3×Zn). 2+ +Li + ) / Ba 2+ The value is 0.4–3.0, with further optimization of (3×Zn). 2+ +Li + ) / Ba 2+ The value ranges from 0.5 to 2.0.

[0056] B 3+ It can lower the melting temperature of glass, and when its content exceeds 5%, the near-infrared light absorption characteristics of the glass decrease. Therefore, B 3+ The content is 0-5%, preferably 0-2%, and more preferably 0-1%. In some embodiments, it is further preferred that it does not contain B. 3+ .

[0057] Si 4+Si can promote glass formation and improve the chemical stability of glass. However, if its content exceeds 5%, the meltability of the glass deteriorates, unmelted impurities easily form in the glass, and the near-infrared light absorption characteristics of the glass tend to decrease. Therefore, Si... 4+ The content of Si is 0-5%, preferably 0-2%, and more preferably 0-1%. In some embodiments, it is further preferred that it does not contain Si. 4+ .

[0058] Sb 3+ This is the clarifying agent of the present invention. By containing a small amount of the clarifying agent component, the clarification effect of glass can be improved, internal bubbles in the glass can be eliminated, and an excellent bubble level can be obtained. Therefore, Sb in the present invention 3+ The content is 0-3%, preferably 0-2%, and more preferably 0.01-1%.

[0059] <Anionic components>

[0060] O 2- It is an important anionic component in the glass of this invention, which can stabilize the glass network structure, form a stable glass, and also ensure that Cu in the glass is in the form of Cu. 2+ The presence of this form ensures the glass's ability to absorb near-infrared light. If O 2- If the content of Cu is too low, it is difficult to form a stable glass, and Cu... 2+ It is easily reduced to Cu + It cannot achieve the effect of absorbing light in the near-infrared region; however, O 2- Excessive O content leads to higher glass melting temperatures, resulting in a significant decrease in visible light spectral transmittance. Therefore, O 2- The content is 82-97%, preferably 85-95%, and more preferably 87-93%.

[0061] F - It can lower the melting temperature of glass, increase the transmittance of glass in the visible light region, reduce the viscosity of glass, and contain an appropriate amount of F. - This is beneficial for improving the glass's resistance to crystallization. If F - When the content exceeds 18%, the stability of the glass decreases, it is prone to volatilization during the glass melting process, causing environmental pollution, and the glass is more likely to form streaks. Therefore, F - The content is 3-18%, preferably 5-15%, and more preferably 7-13%.

[0062] In some implementations, by controlling (P) 5+ -38%) / F - A value less than 3.0 allows the glass to achieve both excellent bubble density and excellent weather resistance. Therefore, (P) is preferred. 5+ -38%) / F- Less than 3.0, more preferably (P) 5+ -38%) / F - Less than 1.5, further optimization (P) 5+ -38%) / F - Less than 1.0.

[0063] Cl - ,Br - I - One or more components can be used as clarifying agents to improve the clarification effect of glass and increase its bubble level. - ,Br - I - The total content is 0-2%, preferably 0-1%, and more preferably 0-0.5%.

[0064] <Components not contained>

[0065] Components such as V, Cr, Mn, Fe, Co, Ni, Ag, and Mo, even when present in small amounts individually or in combination, can interfere with the spectral transmittance of the glass, which is not conducive to forming the near-infrared light-absorbing glass of the present invention. Therefore, it is preferable that the glass does not contain the above-mentioned components.

[0066] 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 the glass manufacturing process but also in processing and post-product disposal. Therefore, given the importance of environmental impact, it is preferable to ideally contain virtually none of these components, except where their contamination is unavoidable. This results in glass that is virtually free of pollutants. Consequently, the glass of this invention can be manufactured, processed, and disposed of even without specific environmental countermeasures.

[0067] The terms "not containing" and "0%" as used herein mean that the component was not intentionally added as a raw material to the near-infrared light absorbing glass of this invention; however, as raw materials and / or equipment used in the production of 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 near-infrared light absorbing glass, and such cases are also within the scope of protection of this patent.

[0068] The performance of the near-infrared light absorbing glass of the present invention will now be described.

[0069] <Weather resistance>

[0070] The weather resistance of the glass was tested using the following method: In a constant temperature and humidity chamber, with the temperature set at 85℃ and the humidity at 85%, two large, polished glass samples measuring 30mm × 40mm × 0.21mm were placed in the chamber. Under natural light, the surface condition was visually observed every 50 hours to confirm the degree of surface corrosion. The weather resistance of the glass was judged according to Table 1 below, with Class 1 being the best and Class 5 the worst.

[0071] Table 1. Grading and Judgment Criteria for Glass Weather Resistance

[0072] In some embodiments, the near-infrared light absorbing glass of the present invention has a weather resistance of Class 3 or above, preferably Class 2 or above, and more preferably Class 1.

[0073] <Transition Temperature>

[0074] Glass transition temperature (T) g Test according to the method specified in the national standard GB / T7962.16—2010.

[0075] In some embodiments, the transition temperature (T) of the near-infrared light-absorbing glass of the present invention is... g The temperature is below 430°C, preferably below 420°C, more preferably below 410°C, and even more preferably below 400°C.

[0076] Young's Modulus

[0077] The Young's modulus (E) of glass is obtained by ultrasonic testing of its longitudinal wave velocity and transverse wave velocity, and then calculated according to the following formula.

[0078] Wherein:

[0079] E is Young's modulus, in Pa;

[0080] G is the shear modulus, Pa;

[0081] V T The transverse wave velocity is in m / s;

[0082] ρ is the density of glass, in g / cm³ 3 .

[0083] In some embodiments, the Young's modulus (E) of the glass of the present invention is 6000 × 10⁻⁶. 7 ~8000×10 7 Pa, preferably 6200 × 10⁻⁶ 7 ~7500×10 7 Pa, more preferably 6500 × 10 7 ~6900×10 7 Pa.

[0084] <Effervescence>

[0085] The bubble content of the glass was tested according to the method specified in the national standard GB / T7962.8-2010.

[0086] In some embodiments, the bubble degree of the near-infrared light absorbing glass of the present invention is A0 or higher, preferably A. 00 class.

[0087] <High Temperature Viscosity>

[0088] The high-temperature viscosity of glass is tested using the following method: The high-temperature viscosity of glass is tested using the THETA Rheotronic II high-temperature viscometer with the rotation method. The unit of measurement is dPaS (poise). The smaller the value, the lower the viscosity.

[0089] In some embodiments, the viscosity of the near-infrared light absorbing glass of the present invention at 800°C is 8.0 poise or less, preferably 5.0 poise or less, and more preferably 3.8 poise or less.

[0090] <Spectral transmittance>

[0091] The spectral transmittance of the glass of this invention refers to the value obtained by a spectrophotometer in the manner described above:

[0092] Assuming a glass sample has two parallel and optically polished planes, light is incident perpendicularly from one parallel plane and exits from the other parallel plane. The intensity of the exiting light divided by the intensity of the incident light is the transmittance, also known as the external transmittance.

[0093] When the glass thickness is less than 0.4 mm, the spectral transmittance has the following characteristics:

[0094] In some embodiments, the spectral transmittance (τ) of the glass of the present invention at a wavelength of 400 nm is... 400 The content is 84.0% or more, preferably 86.0% or more, and more preferably 88.0% or more.

[0095] In some embodiments, the spectral transmittance (τ) of the glass of the present invention at a wavelength of 500 nm is... 500 The content is 85.0% or more, preferably 87.0% or more, and more preferably 89.0% or more.

[0096] In some embodiments, the spectral transmittance (τ) of the glass of the present invention at a wavelength of 1100 nm is... 1100 The content of ) is 18.0% or less, preferably 16.0% or less, more preferably 14.0% or less, and even more preferably 12.0% or less.

[0097] In some embodiments, when the thickness of the near-infrared absorbing glass is less than 0.4 mm, the wavelength (λ) corresponding to a transmittance of 50% in the spectral transmittance range of 500–700 nm is... 50 The wavelength is 640nm or less, preferably 610-635nm, and more preferably 615-630nm.

[0098] The thickness of the glass sample is preferably 0.05-0.4 mm, more preferably 0.1-0.3 mm, even more preferably 0.15-0.25 mm, and even more preferably 0.15 mm, 0.18 mm, 0.20 mm, 0.21 mm, 0.23 mm, or 0.25 mm.

[0099] [Manufacturing method of near-infrared light absorbing glass]

[0100] The manufacturing method of the near-infrared light-absorbing glass of the present invention is as follows: The glass of the present invention is produced using conventional raw materials and conventional processes. Carbonates, nitrates, phosphates, metaphosphates, sulfates, hydroxides, oxides, fluorides, etc., are used as raw materials. After being batched according to conventional methods, the batched charge is put into a melting furnace at 700-1000°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.

[0101] The near-infrared light-absorbing glass of the present invention can also be formed by well-known methods. In some embodiments, the near-infrared light-absorbing glass described herein can be manufactured into a shaped body by various processes, including but not limited to sheets, such processes including but not limited to slot drawing, float glass, roll forming, and other sheet forming processes known in the art. Alternatively, the glass can be formed by float glass or roll forming methods known in the art. The glass of the present invention can have any reasonably useful shape or structure, such as 2D, 2.5D, or 3D.

[0102] The near-infrared light absorbing glass of the present invention can be manufactured into a sheet glass body by methods such as grinding or polishing, but the method of manufacturing the glass body is not limited to these methods.

[0103] The near-infrared light-absorbing glass described in this invention can have any reasonably useful thickness.

[0104] [Near-infrared light absorbing glass element]

[0105] The near-infrared light absorbing glass element involved in this invention contains the aforementioned near-infrared light absorbing glass. Examples include thin-plate glass elements or lenses used in near-infrared light absorbing filters. It is suitable for color correction applications in solid-state imaging elements and possesses various excellent properties of the aforementioned glass.

[0106] It should be noted that the thickness of the near-infrared light-absorbing glass element (the distance between the incident and exit surfaces of the transmitted light) is determined by the transmittance characteristics of the element. For convenience, this article uses a thickness of less than 0.4 mm as a representative value, which does not mean that it cannot be used for filter elements with other light absorption properties that can be made by changing the thickness.

[0107] [Filter]

[0108] The filter involved in this invention is a near-infrared filter, which contains the aforementioned near-infrared light absorbing glass or a near-infrared light absorbing glass element. It has a near-infrared light absorbing element composed of near-infrared light absorbing glass with optically ground surfaces on both sides. This element gives the filter a color correction function and also possesses the various excellent properties of the aforementioned glass.

[0109] [equipment]

[0110] The near-infrared light absorbing glass, or near-infrared light absorbing glass element, or filter of the present invention can be manufactured by well-known methods into devices such as portable communication devices (such as mobile phones, PADs, etc.), smart wearable devices (such as smartwatches, etc.), photographic devices (such as SLR cameras, mirrorless cameras, etc.), video recording devices, vehicle-mounted devices, display devices, and monitoring devices.

[0111] Example

[0112] <Example of Near-Infrared Absorbing Glass>

[0113] To further illustrate and explain the technical solution of the present invention, the following non-limiting embodiments are provided.

[0114] In this embodiment, glass with the composition shown in Tables 2 to 4 was obtained using the manufacturing method of the near-infrared light-absorbing glass described above. Furthermore, the characteristics of each near-infrared light-absorbing glass were measured using the testing method described in this invention, and the measurement results are shown in Tables 2 to 4.

[0115] Table 2.

[0116] Table 3.

[0117] Table 4.

[0118] The near-infrared light absorbing glass described in Tables 2 to 4 above was processed into glass sheets with a thickness of 0.21 mm, and the spectral transmittance of the near-infrared light absorbing glass of each embodiment was determined according to the test method described above. The results are shown in Tables 5 to 7 below.

[0119] Table 5.

[0120] Table 6.

[0121] Table 7.

[0122] <Example of Near-Infrared Light Absorbing Glass Element>

[0123] The near-infrared light absorbing glass described in Examples 1 to 24 above can be used to make near-infrared light absorbing glass elements using methods known in the art. Examples of such elements include thin-plate near-infrared light absorbing glass elements or lenses used in near-infrared light absorbing filters. These elements are suitable for color correction applications in solid-state imaging devices and possess the various excellent properties of the aforementioned glass.

[0124] <Filter Examples>

[0125] The near-infrared light absorbing glass and / or near-infrared light absorbing glass elements of the above embodiments 1 to 24# are made into filters by methods known in the art. The filters of the present invention have color correction function and also possess the various excellent properties of the above-mentioned glass.

[0126] <Equipment Example>

[0127] The near-infrared light-absorbing glass and / or near-infrared light-absorbing glass elements and / or filters of this invention can be manufactured using well-known methods into devices such as portable communication devices (e.g., mobile phones), smart wearable devices, photographic equipment, video recording equipment, display devices, and monitoring equipment. They can also be used in, for example, imaging equipment, sensors, microscopes, medical technology, digital projection, optical communication technology / information transmission, or in imaging equipment and devices for the automotive field.

Claims

1. Near-infrared light absorbing glass, characterized in that, The components are expressed in mole percent, the cationic component comprising: P 5+ : 38-52%; Al 3+ : 3-12%; Cu 2+ : 2-16%; Rn + : 10-40%; R 2+ : 3-30%, said Rn + is one or more of Li + , Na + , K + , R 2+ is one or more of Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ ; The anion component contains: O 2- : 82 to 97%; F - : 3 to 18%.

2. The near-infrared light-absorbing glass according to claim 1, characterized in that, its components expressed in mole percent, the cationic component further comprising: Ln 3+ : 0-8%; and / or B 3+ : 0-5%; and / or Si 4+ : 0-5%; and / or Zn 2+ : 0-10%; and / or Sb 3+ : 0-3%, the Ln 3+ is one or more of La 3+ , Gd 3+ , Y 3+ . The anion component also contains: Cl - + Br - + I - : 0-2%.

3. Near-infrared light absorbing glass, characterized in that, Its components are expressed as mole percentages, with the cationic component consisting of P 5+ 38-52%; Al 3+ 3-12%; Cu 2+ 2-16%; Rn + : 10-40%; R 2+ 3-30%; Ln 3+ : 0-8%; B 3+ : 0-5%; Si 4+ 0-5%; Zn 2+ : 0-10%; Sb 3+ Composition: 0-3%, wherein Rn + For Li + Na + K + One or more of them, R 2+ Mg 2+ Ca 2+ 、Sr 2+ Ba 2+ One or more of them, Ln 3+ For La 3+ Gd 3+ Y 3+ One or more of the following; The anion component consists of O 2- : 82 to 97%; F - : 3 to 18%; Cl - + Br - + I - : 0 to 2%.

4. The near-infrared light absorbing glass according to any one of claims 1 to 3, characterized in that, Its components are expressed as mole percentages, wherein one or more of the following seven conditions are met: 1) (P 5+ -38%) / (2 x Li + ) is 0.5 to 30.0, preferably (P 5+ -38%) / (2 x Li + ) is 1.0 to 25.0, more preferably (P 5+ -38%) / (2 x Li + ) is 2.5 to 10.0; 2) Cu 2+ / Li + is 0.5 to 30.0, preferably Cu 2+ / Li + is 1.0 to 10.0, more preferably Cu 2+ / Li + is 2.0 to 7.0; 3) Mg 2+ / Li + is 0.5 to 15.0, preferably Mg 2+ / Li + is 1.0 to 10.0, more preferably Mg 2+ / Li + is 1.2 to 8.0; 4) Na + (Mg 2+ + Li + ) is 1.0 to 10.0, preferably Na + (Mg 2+ + Li + ) is 2.0 to 8.0, more preferably Na + (Mg 2+ + Li + ) is 4.0 to 7.0; 5) (Al 3+ + Y 3+ ) / (3 x Li + ) is 0.4 to 20.0, preferably (Al 3+ + Y 3+ ) / (3 x Li + ) is 0.9 to 15.0, more preferably (Al 3+ + Y 3+ ) / (3 x Li + ) is 1.1 to 6.0; 6) (3 x Zn 2+ + Li + ) / Ba 2+ is 0.2 to 5.0, preferably (3 x Zn 2+ + Li + ) / Ba 2+ is 0.4 to 3.0, more preferably (3 x Zn 2+ + Li + ) / Ba 2+ is 0.5 to 2.0; 7) (P 5+ -38%) / F - less than 3.0, preferably (P 5+ -38%) / F - less than 1.5, more preferably (P 5+ -38%) / F - less than 1.

0.

5. The near-infrared light absorbing glass according to any one of claims 1 to 3, characterized in that, Its components are expressed as mole percentages, where: P 5+ 42-51%, P is preferred 5+ 44-50%; and / or Al 3+ 4-10%, preferably Al 3+ 6-9%; and / or Cu 2+ 3-10%, preferably Cu 2+ 4-8%; and / or Rn + 15-35%, preferably Rn + 20-30%; and / or R 2+ 5-20%, preferably R 2+ : 8–18%; and / or Ln 3+ 0-6%, preferably Ln 3+ 0-4%, more preferably free of Ln 3+ ; and / or B 3+ 0-2%, B is preferred 3+ 0-1%, preferably free of B 3+ ; and / or Si 4+ 0-2%, preferably Si 4+ 0-1%, more preferably free of Si 4+ ; and / or Zn 2+ 1-6%, preferably Zn 2+ : 1-4%; and / or Sb 3+ 0-2%, preferably Sb 3+ : 0.01~1%; and / or O 2- 85-95%, preferred: O 2- : 87-93%; and / or F - 5-15%, preferably F - 7–13%; and / or Cl - +Br - +I - 0-1%, preferably Cl - +Br - +I - : 0~0.5%, the Rn + For Li + Na + K + One or more of them, R 2+ Mg 2+ Ca 2+ 、Sr 2+ Ba 2+ One or more of them, Ln 3+ For La 3+ Gd 3+ Y 3+ One or more of them.

6. The near-infrared light absorbing glass according to any one of claims 1 to 3, characterized in that, Its components are expressed as mole percentages, of which: Li + 0-10%, preferably Li + 0.2-6%, more preferably Li + 0.5–3%; and / or Na + 10-30%, preferably Na + 13-27%, more preferably Na + 15-25%; and / or K + 0-10%, K is preferred + 0-7%, preferably K + 0–5%; and / or Mg 2+ 1-10%, preferably Mg 2+ 1.5-8%, more preferably Mg 2+ 2-5%; and / or Ca 2+ 1-10%, preferably Ca 2+ 1.5-8%, more preferably Ca 2+ 2-6%; and / or Sr 2+ 0-10%, preferably Sr 2+ 0-6%, more preferably Sr 2+ : 1-5%; and / or Ba 2+ 1-10%, Ba is preferred. 2+ 1.5-8%, more preferably Ba 2+ : 2-6%; and / or Y 3+ 0-6%, preferred Y 3+ 0-5%, more preferably Y 3+ : 0-2%; and / or La 3+ 0-5%, preferably La 3+ 0-3%, more preferably La 3+ 0–1%; and / or Gd 3+ 0-5%, preferably Gd 3+ 0-3%, more preferably Gd 3+ : 0-1%.

7. The near-infrared light absorbing glass according to any one of claims 1 to 3, characterized in that, The near-infrared absorbing glass has a weather resistance of Class 3 or higher, preferably Class 2 or higher, more preferably Class 1; and / or a transition temperature of 430°C or lower, preferably 420°C or lower, more preferably 410°C or lower, and even more preferably 400°C or lower; and / or a Young's modulus of 6000 × 10⁻⁶. 7 ~8000×10 7 Pa, preferably 6200 × 10⁻⁶ 7 ~7500×10 7 Pa, more preferably 6500 × 10 7 ~6900×10 7 Pa; and / or bubble degree of A0 or above, preferably A 00 Grade; and / or a viscosity of 8.0 poise or less at 800°C, preferably 5.0 poise or less, more preferably 3.8 poise or less; and / or a near-infrared absorbing glass with a thickness of 0.05 to 0.4 mm and a spectral transmittance τ at a wavelength of 400 nm. 400 The transmittance is 84.0% or more, preferably 86.0% or more, more preferably 88.0% or more; and / or a near-infrared light-absorbing glass with a thickness of 0.05 to 0.4 mm, and a spectral transmittance τ at a wavelength of 500 nm. 500 The transmittance is 85.0% or more, preferably 87.0% or more, more preferably 89.0% or more; and / or a near-infrared light-absorbing glass with a thickness of 0.05 to 0.4 mm, and a spectral transmittance τ at a wavelength of 1100 nm. 1100 The transmittance is 18.0% or less, preferably 16.0% or less, more preferably 14.0% or less, and even more preferably 12.0% or less; and / or a near-infrared light-absorbing glass with a thickness of 0.05 to 0.4 mm, wherein the wavelength λ corresponding to a transmittance of 50% in the spectral transmittance range of 500 to 700 nm is... 50 The wavelength is below 640nm, preferably 610-635nm, and more preferably 615-630nm.

8. A near-infrared light-absorbing glass element, characterized in that, It is made of the near-infrared light absorbing glass described in any one of claims 1 to 7.

9. A filter, characterized in that, It contains the near-infrared light absorbing glass according to any one of claims 1 to 7, or contains the near-infrared light absorbing glass element according to claim 8.

10. A device, characterized in that, It contains the near-infrared light absorbing glass according to any one of claims 1 to 7, or the near-infrared light absorbing glass element according to claim 8, or the filter according to claim 9.

Images