Near-infrared light absorbing glass, element and light filter

Abstract

The invention provides near-infrared light absorbing glass with excellent inherent quality. The near-infrared light absorbing glass comprises the following components in percentage by mole: 38-52% of positive ion component P < 5 + >; 3-12% of Al < 3 + >; cu < 2 + >: 2-16%; 10%-40% of Rn < + >; r < n + > is one or more of Li < + >, Na < + > and K < + >, and R < 2 + > is one or more of Mg < 2 + >, Ca < 2 + >, Sr < 2 + > and Ba < 2 + >; the anion component contains 82 to 97 percent of O2 <->; and F: 3-18%. Through reasonable component design, the obtained near-infrared light absorption glass has excellent transmission characteristics in a visible light region, has excellent absorption characteristics in a near-infrared region, has excellent inherent quality and meets the use requirements of high-performance equipment.

Description

Technical Field

[0001] The present invention relates to glass, in particular to near-infrared light absorbing glass, and a near-infrared light absorbing element and an optical filter made of the same. Background Art

[0002] In recent years, the spectral sensitivity of semiconductor imaging devices such as CCDs and CMOS sensors used in digital cameras, camera phones, and VTR cameras has expanded from the visible range to the near-infrared. Using filters that absorb light in the near-infrared region allows for near-human visual acuity. The average human eye can perceive visible light wavelengths between 400 and 700 nm. Therefore, using filters that absorb near-infrared light can produce images with brightness factors similar to those seen by the human eye. With the miniaturization of optical modules and the increasing demand for reliability, higher requirements have been placed on the near-infrared light-absorbing glass used to manufacture these filters. Such glass must possess excellent transmission properties in the visible range and excellent absorption properties in the near-infrared region.

[0003] In addition, the spectral characteristics determine the basic function of near-infrared absorbing glass. In addition to having the desired spectral characteristics, near-infrared absorbing glass also needs to have excellent internal quality (such as a high bubble level). If the glass component design is unreasonable, it is easy to cause the glass to have poor internal quality and defects such as poor bubble level (the presence of many bubbles and stones in the glass). Chinese patent CN102656125A discloses a near-infrared cutoff filter glass, which contains 16.2-25% Al 3+ , which can easily lead to the deterioration of the glass's near-infrared light absorption characteristics and the occurrence of internal quality defects such as stones, resulting in a poor glass bubble degree grade and the internal quality being difficult to meet the requirements of high-performance optical equipment. 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 the present invention to solve the technical problem is:

[0006] (1) Near-infrared light absorbing glass, the components of which are expressed in molar percentages, the cationic component contains: P 5+ :38~52%;Al 3+ :3~12%;Cu 2+ :2~16%;Rn + :10~40%;R 2+ : 3-30%, said Rn + For Li + 、Na + , K + One or more of R2+ Mg 2+ , Ca 2+ 、Sr 2+ 、Ba 2+ One or more of;

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

[0008] (2) The near-infrared light absorbing glass according to (1), wherein the components are expressed in molar percentages, and the cationic component further comprises: 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;

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

[0010] (3) Near-infrared light absorbing glass, whose components are expressed in molar percentages, the cationic component is 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+ : 0 to 3% composition, the Rn + For Li + 、Na + , K + One or more of R 2+ Mg 2+ , Ca 2+ 、Sr 2+ 、Ba 2+ One or more of Ln 3+ For La 3+ 、Gd 3+ 、Y 3+One or more of;

[0011] The anion component is O 2- :82~97%;F - :3~18%;Cl - +Br - +I - : 0~2% composition.

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

[0013] 1)(P 5+ -38%) / (2×Li + ) is 0.5 to 30.0, preferably (P 5+ -38%) / (2×Li + ) is 1.0 to 25.0, more preferably (P 5+ -38%) / (2×Li + ) is 2.5~10.0;

[0014] 2)Cu 2+ / Li + 0.5~30.0, preferably Cu 2+ / Li + 1.0 to 10.0, more preferably Cu 2+ / Li + 2.0~7.0;

[0015] 3)Mg 2+ / Li + 0.5~15.0, preferably Mg 2+ / Li + 1.0 to 10.0, more preferably Mg 2+ / Li + 1.2~8.0;

[0016] 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 4.0~7.0;

[0017] 5)(Al 3+ +Y 3+ ) / (3×Li +) is 0.4 to 20.0, preferably (Al 3+ +Y 3+ ) / (3×Li + ) is 0.9 to 15.0, more preferably (Al 3+ +Y 3+ ) / (3×Li + ) is 1.1 to 6.0;

[0018] 6)(3×Zn 2+ +Li + ) / Ba 2+ 0.2 to 5.0, preferably (3×Zn 2+ +Li + ) / Ba 2+ 0.4 to 3.0, more preferably (3×Zn 2+ +Li + ) / Ba 2+ 0.5~2.0;

[0019] 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.

[0020] (5) The near-infrared light absorbing glass according to any one of (1) to (3), wherein the components are expressed in molar percentages, wherein: 5+ : 42~51%, preferably P 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 no Ln 3+ and / or B 3+ : 0-2%, preferably B 3+ : 0 to 1%, more preferably no B 3+ ; and / or Si 4+ : 0-2%, preferably Si4+ : 0-1%, more preferably no 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%, the Rn + For Li + 、Na + , K + One or more of R 2+ Mg 2+ , Ca 2+ 、Sr 2+ 、Ba 2+ One or more of Ln 3+ For La 3+ 、Gd 3+ 、Y 3+ One or more of .

[0021] (6) The near-infrared light absorbing glass according to any one of (1) to (3), wherein the components are expressed in molar percentages, wherein: Li + : 0-10%, preferably Li + : 0.2 to 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%, preferably K + : 0-7%, more 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%, preferably Ba 2+ : 1.5 to 8%, more preferably Ba 2+ : 2-6%; and / or Y 3+ : 0-6%, preferably Y 3+ : 0-5%, more preferably Y3+ : 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 the components are expressed in molar percentages, wherein: 2- : 85~95%, preferably: 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 higher, preferably Class 2 or higher, and more preferably Class 1; and / or the transition temperature is 430°C or lower, preferably 420°C or lower, more preferably 410°C or lower, and further preferably 400°C or lower; and / or the Young's modulus is 6000×10 7 ~8000×10 7 Pa, preferably 6200×10 7 ~7500×10 7 Pa, more preferably 6500×10 7 ~6900×10 7 Pa; and / or the bubble degree is A0 or above, preferably A 00 and / or a viscosity at 800°C of 8.0 poise or less, preferably 5.0 poise or less, more preferably 3.8 poise or less.

[0024] (9) The near-infrared light absorbing glass according to any one of (1) to (3), wherein the thickness of the near-infrared light absorbing glass is 0.4 mm or less, and the spectral transmittance τ at a wavelength of 400 nm is 400 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 50085.0% 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 1100 18.0% or less, preferably 16.0% or less, more preferably 14.0% or less, and further preferably 12.0% or less; and / or the wavelength λ corresponding to the transmittance of 50% in the spectral transmittance within the wavelength range of 500 to 700 nm is 50 The wavelength is 640 nm or less, preferably 610 to 635 nm, and more preferably 615 to 630 nm.

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

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

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

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

[0029] The beneficial effects of the present invention are as follows: through reasonable component design, the near-infrared light absorbing glass obtained by the present invention has excellent transmission characteristics in the visible light region and excellent absorption characteristics in the near-infrared region, and at the same time has excellent intrinsic quality, meeting the use of high-performance equipment. DETAILED DESCRIPTION

[0030] The following describes in detail embodiments of the near-infrared light-absorbing glass of the present invention. However, the present invention is not limited to the embodiments described below and can be implemented with appropriate modifications within the scope of the present invention. Furthermore, while overlapping descriptions may be omitted as appropriate, this does not limit the scope of the invention. In the following description, the near-infrared light-absorbing glass of the present invention may be simply referred to as "glass."

[0031] [Near-infrared light absorbing glass]

[0032] The following describes the ranges of the various components (ingredients) of the near-infrared light absorbing glass of the present invention. In this specification, unless otherwise specified, the content of a cationic component is expressed as the molar percentage (mol%) of the cation in the total cationic component; the content of an anionic component is expressed as the molar percentage of the anion in the total anionic component; the ratio of the cation component content is the ratio of the molar percentage content of the cation component content; the ratio of the anionic component content is the ratio of the molar percentage content of the anionic component content; the total content is expressed in molar percentage of ions; and the ratio of the cation and anionic component content is the ratio of the molar percentage content of the cation component in the total cationic component content to the molar percentage content of the anionic component in the total anionic component content.

[0033] Unless otherwise indicated in specific circumstances, the numerical ranges listed herein include upper and lower limits, and "above" and "below" include the endpoints, as well as all integers or fractions within the range, without being limited to the specific values listed when defining the range. The term "and / or" herein is inclusive, for example, "A and / or B" means 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 different from other ionic valences. The ionic valences of the components in the glass may be other than the representative values. For example, P usually exists in the glass with an ionic valence of +5, so in this patent, "P 5+ " is used as a representative value, but there is the possibility of existing in other ionic valence states, which is also within the scope of protection of this patent.

[0035] <Cationic Component>

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

[0037] Al 3+ It is beneficial to increase the stability of glass, improve the strength of glass and improve the weather resistance of glass. However, if its content exceeds 12%, the tendency of glass crystallization increases, the melting performance of glass deteriorates, and the near-infrared light absorption characteristics deteriorate. Therefore, Al in the present invention 3+The content of is 3 to 12%, preferably 4 to 10%, more preferably 6 to 9%.

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

[0039] Rn + (Rn + For Li + 、Na + , K + One or more of these) can reduce the melting temperature and viscosity of the glass and promote the 2+ The state exists, but with Rn + Increase, the chemical stability of the glass deteriorates, the anti-crystallization performance also deteriorates rapidly. + To obtain the above effect, but when Rn + When the content of Rn exceeds 40%, the devitrification resistance of the glass decreases, the forming performance of the glass deteriorates, and the hardness decreases. + The content of is 10 to 40%, preferably 15 to 35%, more preferably 20 to 30%.

[0040] Li + It is a component that improves the melting property of glass, but when Li + When the content exceeds 10%, the devitrification resistance, forming performance and hardness of the glass decrease, and the raw material cost of the glass increases. + The content of is 0 to 10%, preferably 0.2 to 6%, more preferably 0.5 to 3%.

[0041] In some embodiments, by controlling (P 5+ -38%) / (2×Li + ) is above 0.5, a near-infrared light absorbing glass with good weather resistance and spectral properties can be obtained. However, when (P 5+ -38%) / (2×Li + ) is greater than 30.0, the high temperature viscosity of the glass increases and the bubble degree deteriorates. 5+ -38%) / (2×Li + ) is 0.5 to 30.0, more preferably (P 5+-38%) / (2×Li + ) is 1.0 to 25.0, and more preferably (P 5+ -38%) / (2×Li + ) is 2.5~10.0.

[0042] In some embodiments, Cu 2+ The content of Li + The ratio between the content of Cu 2+ / Li + When Cu is controlled within the range of 0.5 to 30.0, a near-infrared light absorbing glass with excellent spectral properties and weather resistance can be obtained. 2+ / Li + 0.5 to 30.0, more preferably Cu 2+ / Li + is 1.0 to 10.0, more preferably Cu 2+ / Li + It is 2.0 to 7.0.

[0043] Na + It can significantly increase the "alkalinity" of the glass, making the Cu in the glass 2+ It exists in the form of, improving the visible light transmittance of the glass and achieving a better effect of filtering near-infrared light, but too much Na + It will make the glass difficult to shape and reduce the hardness of the glass. + The content of is 10 to 30%, preferably 13 to 27%, more preferably 15 to 25%.

[0044] K + Has strong fluxing and maintenance of Cu 2+ However, when its content exceeds 10%, the chemical stability and devitrification resistance of the glass will be greatly reduced. + The content of is 0 to 10%, preferably 0 to 7%, more preferably 0 to 5%.

[0045] R 2+ (R 2+ Mg 2+ , Ca 2+ 、Sr 2+ 、Ba 2+ One or more of the above) can be used to reduce the melting temperature of the glass and improve the glass forming stability and hardness of the glass. However, if R 2+ If the content of R exceeds 30%, the devitrification resistance of the glass decreases. 2+ The content of is 3 to 30%, preferably 5 to 20%, more preferably 8 to 18%.

[0046] Mg2+ It can enhance the chemical stability of glass and improve the processing performance of glass. If its content exceeds 10%, the anti-crystallization performance of glass will decrease and the visible light transmittance will decrease. 2+ The content of Mg is 1-10%, preferably Mg 2+ The content of Mg is 1.5-8%, more preferably Mg 2+ The content is 2-5%.

[0047] In some embodiments, Mg 2+ The content of Li + The ratio between the content of Mg 2+ / Li + When the Mg content is controlled above 0.5, a near-infrared light absorbing glass with good weather resistance can be obtained. 2+ / Li + When it is greater than 15.0, the high temperature viscosity of the glass increases and the bubble degree deteriorates. 2+ / Li + 0.5 to 15.0, more preferably Mg 2+ / Li + 1.0 to 10.0, more preferably Mg 2+ / Li + It is 1.2 to 8.0.

[0048] In some embodiments, controlling Na + / (Mg 2+ +Li + ) value is in the range of 1.0 to 10.0, a near-infrared light absorbing glass with a good elastic modulus and excellent spectral properties can be obtained. Therefore, Na + / (Mg 2+ +Li + ) is 1.0 to 10.0, more preferably Na + / (Mg 2+ +Li + ) is 2.0 to 8.0, and Na is more preferably + / (Mg 2+ +Li + ) is 4.0~7.0.

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

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

[0051] Ba 2+ It can improve the transmittance of glass in the visible light region, improve the chemical stability of glass, and enhance the strength of glass. In the present invention, by containing more than 1% of Ba 2+ To obtain the above effect, but if Ba 2+ If the content of Ba exceeds 10%, the density of the glass increases and the anti-crystallization performance deteriorates. 2+ The content of Ba is 1-10%, preferably Ba 2+ The content of Ba 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 above) is beneficial to improving the visible light transmittance and near infrared absorption performance of the glass, improving the chemical stability and hardness of the glass. If its content exceeds 8%, the anti-crystallization performance of the glass will deteriorate. 3+ The content of Ln is 0-8%, preferably 0-6%, more preferably 0-4%. In some embodiments, it is further preferred that Ln is not contained. 3+ .Y 3+ Compared with La in glass 3+ and Gd 3+ , is more conducive to obtaining the desired spectral characteristics of the present invention, therefore, it is preferred that Y 3+ The content of Y is 0-6%, more preferably 3+ The content of Y is 0-5%, and more preferably Y 3+ The content is 0-2%; preferably La 3+ The content of La is 0-5%, more preferably 3+ The content of La is 0-3%, and more preferably 3+ The content is 0-1%; preferably Gd 3+ The content of Gd is 0-5%, more preferably 3+ The content of Gd is 0-3%, more preferably 3+ The content is 0-1%.

[0053] In some embodiments, control (Al 3+ +Y 3+ ) / (3×Li +) is above 0.4, a near-infrared light absorbing glass with excellent weather resistance and transition temperature can be obtained. However, if (Al 3+ +Y 3+ ) / (3×Li + ) value exceeds 20.0, the high temperature viscosity of the glass increases and the bubble degree deteriorates. Therefore, it is preferred that (Al 3+ +Y 3+ ) / (3×Li + ) is 0.4 to 20.0, more preferably (Al 3+ +Y 3 + ) / (3×Li + ) is 0.9 to 15.0, and more preferably (Al 3+ +Y 3+ ) / (3×Li + ) is 1.1~6.0.

[0054] Zn 2+ In Cu 2+ When the content is high, the thermal stability of the glass can be greatly improved. 2+ When the content of Zn exceeds 10%, the visible light transmittance decreases. 2+ The content of is 0 to 10%, preferably 1 to 6%, more preferably 1 to 4%.

[0055] In some embodiments, by controlling (3×Zn 2+ +Li + ) / Ba 2+ When the value of is within the range of 0.2 to 5.0, a near-infrared light absorbing glass with low high-temperature viscosity, excellent bubble density, and excellent spectral properties can be obtained. Therefore, it is preferred that (3×Zn 2+ +Li + ) / Ba 2+ 0.2 to 5.0, more preferably (3×Zn 2+ +Li + ) / Ba 2+ is 0.4 to 3.0, more preferably (3×Zn 2+ +Li + ) / Ba 2+ It is 0.5 to 2.0.

[0056] B 3+ It can reduce the melting temperature of glass. When its content exceeds 5%, the near-infrared light absorption characteristics of glass are reduced. 3+ The content is 0-5%, preferably 0-2%, more preferably 0-1%. In some embodiments, it is further preferred that B is not contained. 3+ .

[0057] Si4+ It can promote the formation of glass and improve the chemical stability of glass. If its content exceeds 5%, the melting property of glass will be deteriorated, unmelted impurities will be easily formed in the glass, and the near-infrared light absorption characteristics of glass will be easily reduced. 4+ The content of Si is 0-5%, preferably 0-2%, more preferably 0-1%. In some embodiments, it is further preferred that Si is not contained. 4+ .

[0058] Sb 3+ It is the clarifier of the present invention. By containing a small amount of clarifier components, the clarification effect of the glass can be improved, bubbles inside the glass can be eliminated, and an excellent bubble degree grade can be obtained. Therefore, Sb in the present invention 3+ The content of is 0 to 3%, preferably 0 to 2%, more preferably 0.01 to 1%.

[0059] <Anion Component>

[0060] O 2- It is an important anion component in the glass of the present invention, which can stabilize the glass network structure, form stable glass, and also ensure that the Cu in the glass is Cu 2+ The glass exists in the form of , thus ensuring the property of absorbing light in the near infrared region. 2- If the content of Cu is too low, it will be difficult to form stable glass. 2+ Easily reduced to Cu + , can not achieve the effect of absorbing light in the near infrared region; but O 2- When the content of O is too high, the melting temperature of the glass will be higher, resulting in a significant decrease in the spectral transmittance in the visible light domain. 2- The content of is 82 to 97%, preferably 85 to 95%, more preferably 87 to 93%.

[0061] F - It can reduce 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 - It is beneficial to improve the anti-crystallization performance of the glass. - If the content exceeds 18%, the stability of the glass will be reduced, the glass will be easily volatile during melting, causing pollution to the environment, and the glass will easily form streaks. - The content of is 3 to 18%, preferably 5 to 15%, more preferably 7 to 13%.

[0062] In some embodiments, by controlling (P 5+ -38%) / F - Less than 3.0, the glass can obtain excellent bubble degree and excellent weather resistance. 5+-38%) / F - Less than 3.0, more preferably (P 5+ -38%) / F - Less than 1.5, more preferably (P 5+ -38%) / F - Less than 1.0.

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

[0064] <Ingredients not contained>

[0065] Components such as V, Cr, Mn, Fe, Co, Ni, Ag, and Mo, even if contained in small amounts alone or in combination, will interfere with the spectral transmittance of the glass, which is not conducive to the formation of the near-infrared light absorbing glass of the present invention. Therefore, it is preferred that the above components are not contained.

[0066] Components such as As, Pb, Th, Cd, Tl, Os, Be, and Se have been increasingly regulated as hazardous chemicals in recent years, necessitating environmental protection measures not only during glass manufacturing but also during processing and post-product disposal. Therefore, given the importance of environmental impact, it is preferable to virtually eliminate these elements, except where they are unavoidably introduced. This ensures that the glass contains virtually no environmentally polluting substances. Therefore, the glass of the present invention can be manufactured, processed, and disposed of even without implementing specific environmental measures.

[0067] The terms "does not contain" and "0%" described herein mean that the component is not intentionally added as a raw material to the near-infrared light absorbing glass of the present invention. However, as raw materials and / or equipment for producing glass, certain impurities or components that are not intentionally added may be present and may be present in small amounts or trace amounts in the final near-infrared light absorbing glass. Such situations are also within the scope of protection of the patent of the present invention.

[0068] Next, the properties of the near-infrared light absorbing glass of the present invention will be described.

[0069] Weather resistance

[0070] Glass weather resistance is tested using the following method: Glass samples, measuring 30 mm x 40 mm x 0.21 mm, with two polished surfaces, are processed into a constant temperature and humidity chamber at 85°C and 85% humidity. The samples are then placed in the chamber. Surface corrosion is visually inspected every 50 hours under natural light. Weather resistance is determined according to Table 1 below, with Category 1 being the best and Category 5 being the worst.

[0071] Table 1. Grading and judgment criteria of glass weather resistance

[0072] level Judgment criteria Category 1 After 200h of constant humidity and heat test, there is no obvious corrosion on the glass surface. Category 2 After 200h constant humidity and heat test, the corrosion area of the glass surface is less than 20%. Category 3 After 100h constant humidity and heat test, the corrosion area of the glass surface is less than 20%. Category 4 After 50 hours of constant humidity and heat testing, the corrosion area on the glass surface is less than 20%. 5 categories After 50 hours of constant humidity and heat testing, the corrosion area of the glass surface exceeded 50%.

[0073] In some embodiments, the weather resistance of the near-infrared light absorbing glass of the present invention is Class 3 or higher, preferably Class 2 or higher, and more preferably Class 1.

[0074] <Transition Temperature>

[0075] The glass transition temperature (T g ) Tested according to the method specified in the national standard "GB / T7962.16-2010".

[0076] In some embodiments, the transition temperature (T g ) is 430°C or lower, preferably 420°C or lower, more preferably 410°C or lower, and further preferably 400°C or lower.

[0077] <Young's modulus>

[0078] The Young's modulus (E) of glass is calculated using the following formula by ultrasonically measuring its longitudinal and transverse wave velocities.

[0079]

[0080] Among them, where:

[0081] E is Young's modulus, Pa;

[0082] G is the shear modulus, Pa;

[0083] V T is the shear wave velocity, m / s;

[0084] ρ is the density of glass, g / cm 3 .

[0085] In some embodiments, the Young's modulus (E) of the glass of the present invention is 6000×10 7 ~8000×10 7 Pa, preferably 6200×10 7 ~7500×10 7Pa, more preferably 6500×10 7 ~6900×10 7 Pa.

[0086] <Bubble Degree>

[0087] The bubble degree of glass is tested according to the method specified in the national standard "GB / T7962.8-2010".

[0088] In some embodiments, the bubble degree of the near-infrared light absorbing glass of the present invention is A0 or above, preferably A 00 class.

[0089] <High Temperature Viscosity>

[0090] The high temperature viscosity of the glass is tested by the following method: The high temperature viscosity of the glass is tested using a THETA Rheotronic II high temperature viscometer using a rotation method. The unit of value is dPaS (poise). The smaller the value, the lower the viscosity.

[0091] 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.

[0092] <Spectral transmittance>

[0093] The spectral transmittance of the glass of the present invention refers to the value obtained by a spectrophotometer in the following manner:

[0094] Assuming that the glass sample has two parallel and optically polished planes, light is incident vertically on one parallel plane and emitted from the other parallel plane. The intensity of the emitted light divided by the intensity of the incident light is the transmittance, which is also called external transmittance.

[0095] When the glass thickness is less than 0.4mm, the spectral transmittance has the characteristics described below:

[0096] In some embodiments, the spectral transmittance (τ 400 ) is 84.0% or more, preferably 86.0% or more, more preferably 88.0% or more.

[0097] In some embodiments, the spectral transmittance (τ 500 ) is 85.0% or more, preferably 87.0% or more, more preferably 89.0% or more.

[0098] In some embodiments, the spectral transmittance (τ 1100) is 18.0% or less, preferably 16.0% or less, more preferably 14.0% or less, and further preferably 12.0% or less.

[0099] In some embodiments, when the thickness of the near-infrared light absorbing glass is less than 0.4 mm, the wavelength (λ) corresponding to the spectral transmittance of 50% in the wavelength range of 500 to 700 nm is 50 ) is 640 nm or less, preferably 610 to 635 nm, and more preferably 615 to 630 nm.

[0100] The thickness of the glass sample is preferably 0.05 to 0.4 mm, more preferably 0.1 to 0.3 mm, further preferably 0.15 to 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.

[0101] [Method for producing near-infrared light absorbing glass]

[0102] 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, using carbonates, nitrates, phosphates, metaphosphates, sulfates, hydroxides, oxides, fluorides, etc. as raw materials. After the ingredients are prepared according to conventional methods, the prepared furnace charge is placed in a melting furnace at 700-1000°C for melting. After clarification, stirring, and homogenization, a homogeneous molten glass free of bubbles and undissolved matter is obtained. The molten glass is then cast in a mold and annealed. Those skilled in the art can appropriately select the raw materials, process methods, and process parameters according to actual needs.

[0103] The near-infrared light-absorbing glass of the present invention can also be formed using well-known methods. In some embodiments, the near-infrared light-absorbing glass described herein can be formed into a formed article, including but not limited to a sheet, using various processes, including but not limited to slot drawing, float glass, roller pressing, and other sheet-forming processes known in the art. Alternatively, the glass can be formed using float or roller pressing methods known in the art. The glass of the present invention can have any reasonably useful shape or structure, including 2D, 2.5D, or 3D.

[0104] The near-infrared light-absorbing glass of the present invention can be manufactured into a glass molded body in the form of a sheet by methods such as grinding and polishing. However, the method for manufacturing the glass molded body is not limited to these methods.

[0105] The near-infrared light absorbing glass of the present invention can have any reasonably useful thickness.

[0106] [Near-infrared light absorbing glass element]

[0107] The near-infrared light absorbing glass element of the present invention contains the above-mentioned near-infrared light absorbing glass, and can be used as a thin plate-shaped glass element or lens in a near-infrared light absorbing filter, etc., and is suitable for color correction applications in solid-state imaging devices, and has various excellent properties of the above-mentioned glass.

[0108] 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, a thickness of 0.4 mm or less is used as a representative value in this article. This does not mean that it cannot be used to produce filter elements with other light-absorbing properties by varying the thickness.

[0109] [Filter]

[0110] The optical filter involved in the present invention is a near-infrared filter, which contains the above-mentioned near-infrared light absorbing glass or contains the above-mentioned near-infrared light absorbing glass element. It has a near-infrared light absorbing element composed of near-infrared light absorbing glass with both sides optically polished. This element gives the filter a color correction function while also possessing the various excellent properties of the above-mentioned glass.

[0111] [equipment]

[0112] 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 for devices such as portable communication devices (such as mobile phones, PADs, etc.), smart wearable devices (such as smart watches, etc.), photographic devices (such as SLR cameras, single-lens reflex cameras, etc.), video equipment, vehicle-mounted equipment, display equipment, and monitoring equipment.

[0113] Example

[0114] <Near-infrared light absorbing glass example>

[0115] In order to further clearly illustrate and describe the technical solutions of the present invention, the following non-limiting examples are provided.

[0116] This example uses the above-described method for producing near-infrared absorbing glass to obtain glasses having the compositions shown in Tables 2 to 4. Furthermore, the properties of each near-infrared absorbing glass were measured using the testing method described herein, and the results are shown in Tables 2 to 4.

[0117] Table 2.

[0118]

[0119]

[0120] Table 3.

[0121]

[0122]

[0123] Table 4.

[0124]

[0125]

[0126] The near-infrared light absorbing glasses described in Tables 2 to 4 were processed into 0.21 mm thick glass sheets, and the spectral transmittance of the near-infrared light absorbing glasses of various examples was measured according to the test method described above. The results are shown in Tables 5 to 7 below.

[0127] Table 5.

[0128] Example 1# 2# 3# 4# 5# 6# 7# 8# <![CDATA[τ 400 (%)]]> 89.9 89.8 89.7 89.5 89.5 89.9 89.8 89.9 <![CDATA[τ 500 (%)]]> 90.7 90.7 90.6 90.5 90.5 90.7 90.7 90.7 <![CDATA[τ 1100 (%)]]> 11.9 11.3 10.7 8.9 8.9 11.2 11.1 11.3 <![CDATA[λ 50 (nm)]]> 629.2 627.7 628.8 624.0 624.2 628.3 628.3 628.1

[0129] Table 6.

[0130]

[0131]

[0132] Table 7.

[0133] Example 17# 18# 19# 20# 21# 22# 23# 24# <![CDATA[τ 400 (%)]]> 89.6 89.7 89.6 90.1 89.6 89.5 89.7 89.8 <![CDATA[τ 500 (%)]]> 90.8 90.9 90.6 91.1 90.8 90.7 90.9 91.0 <![CDATA[τ 1100 (%)]]> 10.5 10.3 11.1 10.9 11.3 11.6 10.4 10.1 <![CDATA[λ 50 (nm)]]> 630.1 630.9 626.8 625.5 627.8 625.7 631.1 632.2

[0134] <Near-infrared light absorbing glass element example>

[0135] The near-infrared light-absorbing glass of Examples 1 to 24 described above can be made into near-infrared light-absorbing glass elements by methods known in the art. Examples of these elements include thin plate-shaped near-infrared light-absorbing glass elements or lenses used in near-infrared light-absorbing filters, and are suitable for color correction applications in solid-state imaging devices, possessing the various excellent properties of the aforementioned glasses.

[0136] <Optical Filter Example>

[0137] The near-infrared light absorbing glass and / or near-infrared light absorbing glass element of Examples 1 to 24 described above are made into optical filters by methods known in the art. The optical filters of the present invention have color correction functions and also possess the various excellent properties of the above-mentioned glasses.

[0138] <Equipment Example>

[0139] The near-infrared light-absorbing glass and / or near-infrared light-absorbing glass element and / or filter of the present invention can be manufactured using well-known methods for use in devices such as portable communication devices (e.g., mobile phones), smart wearable devices, photographic devices, video cameras, display devices, and monitoring devices. They can also be used in imaging devices, sensors, microscopes, medical technology, digital projection, optical communication technology / information transmission, and in automotive video cameras and devices.

Claims

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

2. The near-infrared light absorbing glass according to claim 1, wherein Its components are expressed in molar percentages, 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 anion component also contains: Cl - +Br - +I - :0~2%.

3. Near-infrared light absorbing glass, characterized in that: Its components are expressed in molar percentages, with the cationic component represented by 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+ : 0 to 3% composition, the Rn + For Li + 、Na + , K + One or more of R 2+ Mg 2+ , Ca 2+ 、Sr 2+ 、Ba 2+ One or more of Ln 3+ For La 3+ 、Gd 3+ 、Y 3+ One or more of; The anion component is O 2- :82~97%;F - :3~18%;Cl - +Br - +I - : 0~2% composition.

4. The near-infrared light absorbing glass according to any one of claims 1 to 3, characterized in that: Its components are expressed in mole percentages, and one or more of the following seven conditions are met: 1)(P 5+ -38%) / (2×Li + ) is 0.5 to 30.0, preferably (P 5+ -38%) / (2×Li + ) is 1.0 to 25.0, more preferably (P 5+ -38%) / (2×Li + ) is 2.5~10.0; 2)Cu 2+ / Li + 0.5~30.0, preferably Cu 2+ / Li + 1.0 to 10.0, more preferably Cu 2+ / Li + 2.0~7.0; 3)Mg 2+ / Li + 0.5~15.0, preferably Mg 2+ / Li + 1.0 to 10.0, more preferably Mg 2+ / Li + 1.2~8.0; 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 4.0~7.0; 5)(Al 3+ +Y 3+ ) / (3×Li + ) is 0.4 to 20.0, preferably (Al 3+ +Y 3+ ) / (3×Li + ) is 0.9 to 15.0, more preferably (Al 3+ +Y 3+ ) / (3×Li + ) is 1.1 to 6.0; 6)(3×Zn 2+ +Li + ) / Ba 2+ 0.2 to 5.0, preferably (3×Zn 2+ +Li + ) / Ba 2+ 0.4 to 3.0, more preferably (3×Zn 2 + +Li + ) / Ba 2+ 0.5~2.0; 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 in mole percentages, where: P 5+ : 42~51%, preferably P 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 no Ln 3+ and / or B 3+ : 0-2%, preferably B 3+ : 0 to 1%, more preferably no B 3+ ; and / or Si 4+ : 0-2%, preferably Si 4+ : 0-1%, more preferably no 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%, the Rn + For Li + 、Na + , K + One or more of R 2+ Mg 2+ , Ca 2+ 、Sr 2+ 、Ba 2+ One or more of Ln 3+ For La 3+ 、Gd 3+ 、Y 3+ One or more of .

6. The near-infrared light absorbing glass according to any one of claims 1 to 3, characterized in that: Its components are expressed in molar percentages, where: Li + : 0-10%, preferably Li + : 0.2 to 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%, preferably K + : 0-7%, more 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%, preferably Ba 2+ : 1.5 to 8%, more preferably Ba 2+ : 2-6%; and / or Y 3+ : 0-6%, preferably 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: Its components are expressed in molar percentages, where: 2- : 85~95%, preferably: 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%.

8. The near-infrared light absorbing glass according to any one of claims 1 to 3, characterized in that: The weather resistance of the near-infrared light absorbing glass is Class 3 or higher, preferably Class 2 or higher, more preferably Class 1; and / or the transition temperature is 430°C or lower, preferably 420°C or lower, more preferably 410°C or lower, and further preferably 400°C or lower; and / or the Young's modulus is 6000×10 7 ~8000×10 7 Pa, preferably 6200×10 7 ~7500×10 7 Pa, more preferably 6500×10 7 ~6900×10 7 Pa; and / or the bubble degree is A0 or above, preferably A 00 and / or a viscosity at 800°C of 8.0 poise or less, preferably 5.0 poise or less, more preferably 3.8 poise or less.

9. The near-infrared light absorbing glass according to any one of claims 1 to 3, characterized in that: Spectral transmittance τ at 400nm for near-infrared light absorbing glass with a thickness of less than 0.4mm 400 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 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 1100 18.0% or less, preferably 16.0% or less, more preferably 14.0% or less, and further preferably 12.0% or less; and / or the wavelength λ corresponding to the transmittance of 50% in the spectral transmittance within the wavelength range of 500 to 700 nm is 50 The wavelength is 640 nm or less, preferably 610 to 635 nm, and more preferably 615 to 630 nm.

10. The near-infrared light absorbing glass according to claim 9, characterized in that: The thickness of the near-infrared light absorbing glass is 0.05 to 0.4 mm, preferably 0.1 to 0.3 mm, more preferably 0.15 to 0.25 mm, and further preferably 0.15 mm, 0.18 mm, 0.20 mm, 0.21 mm, 0.23 mm, or 0.25 mm.

11. A near-infrared light absorbing glass element, characterized in that: The near-infrared light absorbing glass is made of any one of claims 1 to 10.

12. An optical filter, characterized in that A device comprising the near-infrared light absorbing glass according to any one of claims 1 to 10, or comprising the near-infrared light absorbing glass according to claim 11.

13. A device, characterized in that A device comprising the near-infrared light absorbing glass according to any one of claims 1 to 10, or a near-infrared light absorbing glass element according to claim 11, or an optical filter according to claim 12.

Images