Environmentally friendly glass materials

Abstract

To provide an environment-friendly glass material with a UV and visible light cutoff as well as high near-infrared transmittance.SOLUTION: An environment-friendly glass material includes components like SiO2, ZnO, alkali metal oxide and S, but does not contain Cd. When the thickness of the environment-friendly glass material is 3 mm, the cutoff wavelength is 550 nm or more; the transmittance at 800-850 nm is 75% or more; the transmittance at 850-900 nm is 80% or more; the transmittance at 900-1000 nm is 83% or more; and the transmittance at 1000-2000 nm is 85% or more.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a glass material, and more particularly to an environmentally friendly glass material that blocks ultraviolet and visible light and has high near-infrared transmittance. [Background technology]

[0002] In recent years, with the development of the optoelectronics industry, the use of near-infrared wavelength band detection (800nm ​​to 2000nm) has become increasingly important, especially in smart devices. Near-infrared lasers are urgently needed for real-time sensing of the surrounding environment to determine the operation and movement of smart devices. Their implementation is based on the need for optical systems to filter out ultraviolet and visible light bands that interfere with the near-infrared operating band, necessitating higher transmittance in the near-infrared band.

[0003] Conventional cadmium selenide glass can cut off ultraviolet and visible light and has higher near-infrared transmittance. However, its disadvantage is that it contains a large amount of cadmium (Cd), which does not meet current environmental standards and poses significant harm to the environment and humans during manufacturing, use, and disposal. Furthermore, cadmium selenide glass has poor chemical stability, making it unsuitable for smart devices that must withstand harsh environments. Summary of the Invention [Problem to be solved by the invention]

[0004] The technical problem to be solved by the present invention is to provide an environmentally friendly glass material that blocks ultraviolet and visible light and has high near-infrared transmittance. [Means for solving the problem]

[0005] The technical solutions adopted by the present invention to solve the technical problems are as follows: (1) An environmentally friendly glass material containing components such as SiO2, ZnO, alkali metal oxides, and S, but not containing Cd, which has a cutoff wavelength of 550 nm or more, a transmittance of 75% or more in the 800-850 nm range, a transmittance of 80% or more in the 850-900 nm range, a transmittance of 83% or more in the 900-1000 nm range, and a transmittance of 85% or more in the 1000-2000 nm range when the thickness of the environmentally friendly glass material is 3 mm. (2) The environmentally friendly glass material according to (1), wherein the cutoff wavelength is 600 nm or more, preferably 650 nm or more, more preferably 680 nm or more, and even more preferably 700 nm or more, when the thickness of the environmentally friendly glass material is 3 mm. (3) The environmentally friendly glass material according to (1), wherein when the thickness of the environmentally friendly glass material is 3 mm, the transmittance of light in the range of 800 to 850 nm is 77% or more, preferably 80% or more in the range of 800 to 850 nm. (4) The environmentally friendly glass material according to (1), wherein when the thickness of the environmentally friendly glass material is 3 mm, the transmittance of light from 850 to 900 nm is 82% or more, preferably 83% or more, at 850 to 900 nm. (5) The environmentally friendly glass material according to (1), wherein when the thickness of the environmentally friendly glass material is 3 mm, the transmittance of the glass from 900 to 1000 nm is 84% ​​or more, preferably 85% or more, at 900 to 1000 nm. (6) The environmentally friendly glass material according to (1), wherein when the thickness of the environmentally friendly glass material is 3 mm, the transmittance of the glass from 1000 to 2000 nm is 86% or more, preferably 87% or more, in the range of 1000 to 2000 nm. (7) An environmentally friendly glass material according to (1), the components of which are expressed in weight percent: SiO2 35 to 80%; ZnO 5 to 35%; Na2O 5 to 25%; K2O 1 to 10%; S 0.2 to 8%; and Sb+Ag+Ce+Sn+Te+V+Fe 0.5 to 10%. (8) An environmentally friendly glass material according to (7), the components of which are expressed in weight percent, further comprising: 0 to 5% Li2O; and / or 0 to 10% B2O3; and / or 0 to 5% Al2O3; and / or 0 to 5% MgO; and / or 0 to 5% CaO; and / or 0 to 10% SrO; and / or 0 to 10% BaO; and / or 0 to 5% Se; and / or 0 to 5% F. (9) An environmentally friendly glass material whose components, expressed in weight percent, include: SiO2 35-80%; ZnO 5-35%; Na2O 5-25%; K2O 1-10%; Li2O 0-5%; S 0.2-8%; Sb+Ag+Ce+Sn+Te+V+Fe 0.5-10%; B2O3 0-10%; Al2O3 0%-5%; MgO 0-5%; CaO 0-5%; SrO 0-10%; BaO 0-10%; Se 0-5%; and F 0-5%, but does not contain Cd. (10) An environmentally friendly glass material according to any one of (1) to (9), the components of which are expressed in weight percent: 40 to 75% SiO2; and / or 7 to 30% ZnO; and / or 7 to 22% Na2O; and / or 2 to 8% KO; and / or 0 to 3% Li2O; and / or 0.5 to 7% S; and / or 0.8 to 9% Sb+Ag+Ce+Sn+Te+V+Fe; and / or 0 to 5% B2O3; and / or 0 to 3% Al2O3; and / or 0 to 3% MgO; and / or 0 to 3% CaO; and / or 0 to 5% SrO; and / or 0 to 5% BaO; and / or 0 to 4% Se; and / or 0 to 3% F. (11) An environmentally friendly glass material according to any one of (1) to (9), whose components are expressed in weight percent and contain: 42 to 73% SiO2; and / or 9 to 25% ZnO; and / or 8 to 19% Na2O; and / or 3 to 7% KO; and / or 1 to 6% S; and / or 0.9 to 8% Sb+Ag+Ce+Sn+Te+V+Fe; and / or 0 to 3% Se; and / or 0 to 2% Li2O; and / or 0 to 3% B2O3; and / or 0 to 1% Al2O3; and / or 0 to 2% MgO; and / or 0 to 2% CaO; and / or 0 to 2% SrO; and / or 0 to 2% BaO; and / or 0 to 1% F. (12) An environmentally friendly glass material according to any one of (1) to (9), wherein the components are expressed in weight percent: CuO+TiO2+P2O5 is 0 to 0.5%; preferably CuO+TiO2+P2O5 is 0.0001 to 0.5%; more preferably CuO+TiO2+P2O5 is 0.0001 to 0.4%; and even more preferably CuO+TiO2+P2O5 is 0.0001 to 0.3%. (13) An environmentally friendly glass material according to any one of (1) to (9), wherein the components are expressed in weight percent, and the B2O3 / SiO2 ratio is 0.23 or less, preferably 0.15 or less, and more preferably 0.1 or less. (14) An environmentally friendly glass material according to any one of (1) to (9), wherein the components are expressed in weight percent, and the ZnO / SiO2 ratio is 0.07 to 0.95, preferably 0.10 to 0.75, and more preferably 0.15 to 0.60. (15) An environmentally friendly glass material according to any one of (1) to (9), wherein the components are expressed in weight percent, and the Se / S ratio is 1.5 or less, preferably 1.3 or less, more preferably 1.0 or less, and even more preferably 0.5 or less. (16) The environmentally friendly glass material according to any one of (1) to (9), wherein the components are expressed in weight percent, and (Sb+Ag+Ce+Sn+Te+V+Fe) / (Se+S) is 0.1 to 25.0, preferably (Sb+Ag+Ce+Sn+Te+V+Fe) / (S+Se) is 0.2 to 15.0, more preferably (Sb+Ag+Ce+Sn+Te+V+Fe) / (S+Se) is 0.5 to 8.0, and even more preferably (Sb+Ag+Ce+Sn+Te+V+Fe) / (S+Se) is 1.0 to 5.0. (17) The environmentally friendly glass material according to any one of (1) to (9), wherein the components are expressed in weight percent, and (Ag+Ce+Sn+Te+V+Fe) / Sb is 3.0 or less, preferably (Ag+Ce+Sn+Te+V+Fe) / Sb is 2.0 or less, more preferably (Ag+Ce+Sn+Te+V+Fe) / Sb is 1.0 or less, and even more preferably (Ag+Ce+Sn+Te+V+Fe) / Sb is 0.8 or less. (18) An environmentally friendly glass material according to any one of (1) to (9), wherein the components are expressed in weight percent, and Li2O + Na2O + K2O is 8 to 35%, preferably Li2O + Na2O + K2O is 9 to 30%, and more preferably Li2O + Na2O + K2O is 10 to 22%. (19) An environmentally friendly glass material according to any one of (1) to (9), which is free of B2O3; and / or free of Li2O; and / or free of Sn; and / or free of Te. (20) The environmentally friendly glass material according to (9), wherein the cutoff wavelength is 550 nm or more, preferably 600 nm or more, more preferably 650 nm or more, even more preferably 680 nm or more, and still more preferably 700 nm or more, when the thickness of the environmentally friendly glass material is 3 mm. (21) When the thickness of the environmentally friendly glass material is 3 mm, the transmittance of 800 to 850 nm is 75% or more, preferably 77% or more, and more preferably 80% or more; and / or when the thickness of the environmentally friendly glass material is 3 mm, the transmittance of 850 to 900 nm is 80% or more, preferably 82% or more, and more preferably 83% or more; and / or when the thickness of the environmentally friendly glass material is 3 mm, the transmittance of 850 to 900 nm is 80% or more, preferably 82% or more, and more preferably 83% or more; and / or an environmentally friendly glass material according to (9), wherein when the thickness of the environmentally friendly glass material is 3 mm, the transmittance from 900 to 1000 nm is 83% or more, preferably 84% or more, and more preferably 85% or more from 900 to 1000 nm; and / or when the thickness of the environmentally friendly glass material is 3 mm, the transmittance from 1000 to 2000 nm is 85% or more, preferably 86% or more, and more preferably 87% or more from 1000 to 2000 nm. (22) The environmentally friendly glass material has an acid resistance stability of Class 3 or higher, preferably Class 2 or higher, and more preferably Class 1; and / or a water resistance stability of Class 3 or higher, preferably Class 2 or higher, and more preferably Class 1; and / or a thermal expansion coefficient of 80×10 -7 / K or higher, preferably 85×10 -7 / K or more, preferably 90×10 -7 / K or more, more preferably 95 × 10 -7 The environmentally friendly glass material according to any one of (1) to (9), wherein the glass has a temperature of 100°C or more. (23) A glass preform made from the environmentally friendly glass material according to any one of (1) to (22). (24) A glass member using the environmentally friendly glass material according to any one of (1) to (22) or the glass preform according to (23). (25) A device comprising the environmentally friendly glass material according to any one of (1) to (22) and / or the glass member according to (24). (26) A method for producing an environmentally friendly glass material according to any one of (1) to (22), comprising the following steps: 1) Mix all the raw materials according to the component ratio of the environmentally friendly glass material, put the uniformly mixed raw materials into a melting furnace, and melt them at 1300~1500℃ to form molten glass; 2) Stirring and homogenizing the molten glass; 3) Pouring or leaking the molten glass into a mold to form it; 4) The glass formed in step 3) is maintained at 470 to 600°C for 10 to 60 hours to develop color, or the glass formed in step 3) is further processed into a glass preform or glass member, and then maintained at 470 to 600°C for 10 to 60 hours to develop color. (27) A method for producing an environmentally friendly glass material according to (26), wherein the raw materials for the environmentally friendly glass material are compound salts, and / or hydroxides, and / or oxides, and / or sulfides, and / or selenides, and / or fluorides, and / or simple substances. [Effects of the Invention]

[0006] The beneficial effect of the present invention is that, through rational component design, the glass material of the present invention achieves ultraviolet and visible light blocking and high near-infrared transmittance while being environmentally friendly. [Brief explanation of the drawings]

[0007] [Figure 1] FIG. 1 is a curve graph showing the spectral transmittance of an environmentally friendly glass material according to a second embodiment of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0008] Hereinafter, embodiments of the present invention will be described in detail, but the present invention is not limited to the embodiments described below and can be practiced by appropriately modifying them within the scope of the object of the present invention. Furthermore, repeated explanations will be omitted as appropriate, but this does not limit the gist of the present invention. Hereinafter, the environmentally friendly glass material of the present invention may be referred to as glass.

[0009] [Environmentally friendly glass materials] The ranges of the components (constituent elements) of the environmentally friendly glass material of the present invention will be described below. In this specification, unless otherwise specified, the content of each component and the total content are expressed in weight % (wt%).

[0010] Numerical ranges set forth in this specification include upper and lower limits unless otherwise stated, and the terms "greater than or equal to" and "less than or equal to" include the endpoints, and all integers and fractions within the range, but are not limited to the specific values ​​set forth when a range is limited. References to "and / or" in this specification are inclusive, e.g., "A and / or B" means A only, B only, or both A and B.

[0011] <Required and optional ingredients> SiO2 is one of the main components of glass. In the glass of the present invention, an appropriate amount of SiO2 stabilizes coloration, enabling the glass to achieve the desired cutoff performance. Meanwhile, an appropriate amount of SiO2 enhances the chemical stability of the glass. If the SiO2 content is less than 35%, the cutoff performance of the glass will not meet the design requirements, and the chemical stability of the glass will rapidly decrease. Therefore, in the present invention, the lower limit of the SiO2 content is 35%, preferably 40%, and more preferably 42%. If the SiO2 content exceeds 80%, the melting temperature of the glass will rapidly increase, increasing the volatilization of coloring substances and reducing the cutoff performance of the glass. At the same time, the high-temperature viscosity of the glass will rapidly increase, resulting in a rapid increase in bubbles and inclusions in the product. Therefore, in the present invention, the upper limit of the SiO2 content is 80%, preferably 75%, and more preferably 73%.

[0012] The B2O3 in the glass of the present invention improves the melting performance of the glass and enhances its intrinsic quality and chemical stability. However, the inventors have found through research that B2O3 in the glass causes changes in the glass structure, increases the threshold for colorant binding, and reduces the cut-off ability of the glass. Therefore, if the cut-off ability of the glass meets the requirements, B2O3 can be included in an amount of 10% or less, preferably 5% or less, and more preferably 3% or less to improve the melting performance and chemical stability of the glass. In some implementations, it is even preferable that the glass does not contain B2O3.

[0013] Through extensive experimental research, the present inventors have found that in some implementations, the water resistance stability of glass can be improved while optimizing the cutoff performance of the glass by setting the B2O3 / SiO2 ratio to 0.23 or less, preferably 0.15 or less, and more preferably 0.1 or less.

[0014] ZnO in glass can improve the chemical stability of glass and reduce its high-temperature viscosity. The addition of SiO2 can suppress the volatilization of coloring substances during the melting stage while promoting structural changes in the coloring substances, improving the cut-off performance of the glass. If the ZnO content is less than 5%, the cut-off performance of the glass will not meet the requirements and the chemical stability of the glass will be reduced. Therefore, the lower limit of the ZnO content is 5%, preferably 7%, and more preferably 9%. If the ZnO content exceeds 35%, the glass will be prone to devitrification, especially during the molding and annealing stages, and the near-infrared transmittance of the glass will be significantly reduced. Therefore, the upper limit of the ZnO content is 35%, preferably 30%, and more preferably 25%.

[0015] In some implementations of the present invention, if the ZnO / SiO2 ratio is less than 0.07, the chemical stability of the glass will not meet the design requirements, resulting in a decrease in the cutoff performance of the glass. If the ZnO / SiO2 ratio is 0.95 or greater, non-coloring substances in the glass will be more likely to devitrify, resulting in a rapid decrease in near-infrared transmittance, particularly in the 800-1000 nm range. Therefore, the ZnO / SiO2 ratio is 0.07-0.95, more preferably 0.10-0.75, and even more preferably 0.15-0.60. This lowers the threshold for the formation of coloring substances in the glass, contributing to improved cutoff performance and near-infrared transmittance.

[0016] The alkali metal oxides Li2O, Na2O, and K2O contained in the glass of the present invention can reduce the high-temperature viscosity of the glass and reduce the number of bubbles and inclusions in the glass. While lowering the high-temperature viscosity, they can also increase the solubility of coloring substances, improving the cutoff performance of the glass. Furthermore, alkali metal oxides can supply more free oxygen, achieving better cutoff performance and improving the near-infrared transmittance of the glass. However, if the content is less than 8%, the above effects are not significant, and the expansion coefficient of the glass becomes lower than the design target, making it difficult to match with materials with high hardness and high expansion coefficients. If the content exceeds 35%, the glass is prone to devitrification, resulting in reduced cutoff performance and near-infrared transmittance, and a rapid decline in chemical stability. Therefore, the total content of the alkali metal oxides Li2O+Na2O+K2O is 8 to 35%, preferably 9 to 30%, and more preferably 10 to 22%.

[0017] Li2O has an excellent ability to reduce the high-temperature viscosity of glass and is therefore beneficial for improving the essential quality of glass. However, the inventors have found that Li ions have a strong ability to aggregate in glass, inhibiting structural changes in coloring substances and thereby reducing the cutoff performance of the glass. In particular, if the Li2O content exceeds 5%, the glass will not achieve the desired cutoff performance. Therefore, the Li2O content is preferably 5% or less, more preferably 3% or less, and even more preferably 2% or less. In some implementations, it is even more preferable that the glass does not contain Li2O.

[0018] Na2O in glass can reduce the high-temperature viscosity of the glass and lower the threshold for structural changes of coloring substances. At the same time, it can improve the near-infrared transmittance of the glass and increase the thermal expansion coefficient of the glass, facilitating bonding of the glass of the present invention to high-strength transparent materials. If the Na2O content is less than 5%, the near-infrared transmittance of the glass will not meet the design requirements, the cutoff performance of the glass will be reduced, and the thermal expansion coefficient of the glass will be lower than the design requirements. Therefore, the lower limit of the Na2O content is 5%, preferably 7%, and more preferably 8%. If the Na2O content exceeds 25%, the chemical stability of the glass will be reduced, the glass will be more susceptible to devitrification, the threshold for structural changes of coloring substances will be higher, and the cutoff performance of the glass will be reduced. Therefore, the upper limit of the Na2O content is 25%, preferably 22%, and more preferably 19%.

[0019] In this glass system, K2O plays a similar role to Na2O, but its ability to enhance near-infrared radiation is stronger than that of Na2O; on the other hand, its ability to reduce the chemical stability of the glass and its resistance to devitrification are stronger than those of Na2O. Therefore, from the viewpoint of optimizing the chemical stability, devitrification resistance, and cutoff performance of the glass, the K2O content is limited to 1 to 10%, preferably 2 to 8%, and more preferably 3 to 7%.

[0020] Although Al2O3 in glass can improve the chemical stability of the glass, it also reduces the cutoff performance of the glass. If the content exceeds 5%, the cutoff performance of the glass will not meet the design requirements. The Al2O3 content is 5% or less, preferably 3% or less. If the chemical stability of the glass is insufficient, the Al2O3 content is more preferably 1% or less.

[0021] MgO improves the chemical stability of glass. However, if the content exceeds 5%, the devitrification resistance of the glass decreases, the cutoff ability of the glass decreases, and the near-infrared transmittance also decreases. Therefore, the MgO content is limited to 5% or less, preferably 3% or less, and more preferably 2% or less.

[0022] CaO improves the stability and devitrification resistance of the glass and reduces the high-temperature viscosity. If its content exceeds 5%, it inhibits the formation of the coloring substance structure and reduces the cut-off performance of the glass. Therefore, the CaO content is limited to 5% or less, preferably 3% or less, and more preferably 2% or less.

[0023] Appropriate amounts of BaO and SrO in glass can improve the chemical stability, hardness, and near-infrared transmittance of the glass. However, if their contents exceed 10%, the glass's ability to fix coloring substances may decrease, resulting in a decrease in cutoff ability. Therefore, the contents of BaO and SrO are each limited to 10% or less, preferably 5% or less, and more preferably 2% or less.

[0024] F in glass improves the meltability of the glass, suppresses the volatilization of coloring substances during the supply stage, and improves the cut-off performance of the glass. However, if the F content exceeds 5%, the high-temperature viscosity of the glass drops sharply and coloring substances volatilize excessively. Therefore, from the viewpoint of environmental protection, the F content is 5% or less, preferably 3% or less, more preferably 1% or less, and even more preferably 0%.

[0025] S can form coloring substances with Sb, Ag, Ce, Sn, Te, V, Fe, etc. in the glass of the present invention, causing the glass to exhibit cutoff absorption in the wavelength range before 500 to 720 nm. If the S content exceeds 8%, the glass is prone to devitrification, resulting in a rapid decrease in near-infrared transmittance. If the S content is less than 0.2%, the cutoff performance of the glass will not satisfy the design requirements. Therefore, the S content is limited to 0.2 to 8%, preferably 0.5 to 7%, and more preferably 1 to 6%. The S content in the present invention refers to the content of sulfur that has been completely converted to elemental sulfur among all sulfur-containing substances in the glass. In the present invention, S can be introduced by elemental sulfur and / or a sulfur-containing compound.

[0026] Se can form coloring substances with Sb, Ag, Ce, Sn, Te, V, Fe, etc. in the glass of the present invention, resulting in cutoff absorption in the wavelength range before 650 to 1200 nm, making the glass capable of achieving better cutoff performance than simple S or sulfides. If the Se content exceeds 5%, the glass is prone to devitrification, resulting in a rapid decrease in near-infrared transmittance. Therefore, if the cutoff performance satisfies the design requirements, the Se content in the present glass system is 5% or less, preferably 4% or less, more preferably 3% or less, and even more preferably 0%. The Se content in the present invention refers to the content of selenium that has been completely converted to elemental selenium among all selenium-containing substances in the glass. In the present invention, Se can be introduced by elemental selenium and / or a selenium-containing compound.

[0027] Through extensive experimental research, the present inventors have found that in some implementations, when the Se / S value exceeds 1.5, the transmittance of the glass in the 800-1000 nm range does not meet the design requirements. Therefore, the Se / S value is preferably 1.5 or less, more preferably 1.3 or less, even more preferably 1.0 or less, and even more preferably 0.5 or less.

[0028] One or more of the components in the glass of the present invention, such as Sb, Ag, Ce, Sn, Te, V, and Fe, can form colored compounds with S and / or Se. If the total content of Sb+Ag+Ce+Sn+Te+V+Fe exceeds 10%, the glass is prone to devitrification, resulting in a rapid decrease in near-infrared transmittance. If the total content of Sb+Ag+Ce+Sn+Te+V+Fe is less than 0.5%, colored substances are unlikely to be produced in the glass, and the designed cutoff performance cannot be achieved. Therefore, the content of Sb+Ag+Ce+Sn+Te+V+Fe is 0.5 to 10%, preferably 0.8 to 9%, and more preferably 0.9 to 8%. In the present invention, the content of Sb+Ag+Ce+Sn+Te+V+Fe refers to the total content of Sb in Sb-containing substances, Ag in Ag-containing substances, Ce in Ce-containing substances, Sn in Sn-containing substances, Te in Te-containing substances, V in V-containing substances, and Fe completely converted to elements in Fe-containing substances in the glass. Sb, Ag, Ce, Sn, Te, V, and Fe may be introduced as oxides, sulfides, selenides, fluorides, and / or elemental and / or compound salts and / or hydroxides. In some implementations of the present invention, Sn and / or Te are preferably not included.

[0029] In some implementations of the present invention, when (Sb+Ag+Ce+Sn+Te+V+Fe) / (S+Se) is less than 0.1, the near-infrared transmittance of the glass is significantly reduced.When (Sb+Ag+Ce+Sn+Te+V+Fe) / (S+Se) is greater than 25.0, the cutoff performance of the glass is significantly reduced, and the devitrification resistance of the glass is also rapidly reduced. Therefore, the value of (Sb+Ag+Ce+Sn+Te+V+Fe) / (S+Se) is preferably 0.1 to 25.0, more preferably 0.2 to 15.0, even more preferably 0.5 to 8.0, and even more preferably 1.0 to 5.0.

[0030] In some implementations of the present invention, when Sb, Ag, Ce, Sn, Te, V, and Fe form coloring substances with anions in the glass, they have a synergistic effect; if the value of (Ag+Ce+Sn+Te+V+Fe) / Sb exceeds 3.0, the near-infrared transmittance of the glass is significantly reduced. Therefore, the value of (Ag+Ce+Sn+Te+V+Fe) / Sb is preferably 3.0 or less, more preferably 2.0 or less, even more preferably 1.0 or less, and even more preferably 0.8 or less.

[0031] In some implementations of the present invention, the glass of the present invention can further contain one or more of CuO, TiO2, and P2O5 to promote the formation of coloring substances. However, if the total content of CuO, TiO2, and P2O5 (CuO + TiO2 + P2O5) exceeds 0.5%, the glass is particularly susceptible to devitrification, the structure of the coloring substances changes to a negative polarity, and the near-infrared transmittance is likely to decrease sharply. Therefore, the content of CuO + TiO2 + P2O5 is 0.5% or less. On the other hand, if the content of CuO + TiO2 + P2O5 is less than 0.0001%, the coloring substances can only be formed in impurity defects in the glass, resulting in problems such as poor cutoff performance and poor color uniformity. Therefore, the content of CuO + TiO2 + P2O5 is preferably 0.0001 to 0.5%, more preferably 0.0001 to 0.4%, and even more preferably 0.0001 to 0.3%. The contents of CuO, TiO2 and P2O5 in the present invention are not included in 100 wt% which is the content of all components other than CuO, TiO2 and P2O5 described in the present invention.

[0032] <Unnecessary ingredients> Due to environmental considerations, the glass of the present invention does not contain Cd, As, or Pb. Here, "not containing" and "0%" mean that no compounds, molecules, elements, etc. are intentionally added as raw materials for the glass of the present invention; however, if there are small or trace amounts of specific impurities or components that are not intentionally added as raw materials and / or equipment for producing glass in the final glass, this situation is also included in the scope of protection of the patent of the present invention.

[0033] The properties of the environmentally friendly glass material of the present invention will be described below.

[0034] <Cut-off performance> Using a spectrometer according to the method of GB / T7962.12-2010, the transmittance curve of a 3mm glass sample from 300nm to 2000nm is tested, and the transmittance of 5% is the cutoff wavelength. In the present invention, the higher the cutoff wavelength value of the glass, the better the cutoff performance, and the lower the cutoff wavelength value, the worse the cutoff performance.

[0035] In some implementations of the present invention, the cutoff wavelength of the environmentally friendly glass material is 550 nm or greater, preferably 600 nm or greater, more preferably 650 nm or greater, even more preferably 680 nm or greater, and even more preferably 700 nm or greater.

[0036] <Near infrared transmittance> The transmittance curve of a 3 mm glass sample in the wavelength range of 300 nm to 2000 nm was measured using a spectrometer according to the method of GB / T7962.12-2010, and the near-infrared transmittance in this invention refers to the transmittance value in the wavelength range of 800 nm to 2000 nm. Note that the near-infrared transmittance in this invention refers to the lowest transmittance in the corresponding wavelength range.

[0037] In some implementations of the present invention, the environmentally friendly glass material of the present invention has one or more of the following transmittances:

[0038] 1) The transmittance from 800 to 850 nm is 75% or more, preferably 77% or more, and more preferably 80% or more in the range of 800 to 850 nm.

[0039] 2) The transmittance from 850 to 900 nm is 80% or more, preferably 82% or more, and more preferably 83% or more from 850 to 900 nm.

[0040] 3) The transmittance from 900 to 1000 nm is 83% or more, preferably 84% or more, and more preferably 85% or more from 900 to 1000 nm.

[0041] 4) The transmittance from 1000 to 2000 nm is 85% or more, preferably 86% or more, and more preferably 87% or more from 1000 to 2000 nm.

[0042] <Acid resistance stability> Acid resistance stability of glass materials (D A ) (powder method) is tested in accordance with the method specified in GB / T 17129. Here, acid resistance is sometimes referred to as acid resistance or acid stability.

[0043] In some implementations of the present invention, the acid stability (D A ) is class 3 or higher, preferably class 2 or higher, more preferably class 1.

[0044] <Water resistance stability> Water resistance stability of glass materials (D W ) (powder method) is tested in accordance with the method specified in GB / T 17129. Here, water resistance is sometimes referred to as water resistance or water stability.

[0045] In some implementations of the present invention, the water resistance stability (D W ) is class 3 or higher, preferably class 2 or higher, more preferably class 1.

[0046] <Thermal expansion coefficient> The thermal expansion coefficient in the present invention refers to the average thermal expansion coefficient of glass at 20 to 300°C, and α 20-300℃ and is tested according to the method specified in GB / T7962.16-2010.

[0047] In some implementations of the present invention, the average thermal expansion coefficient (α 20-300℃ ) is 80 x 10-7 / K or higher, preferably 85×10 -7 / K or more, preferably 90×10 -7 / K or more, more preferably 95 × 10 -7 / K or higher.

[0048] [Manufacturing method] The method for producing the environmentally friendly glass material of the present invention includes the following steps: 1) Mix all the raw materials according to the component ratio of the environmentally friendly glass material, put the uniformly mixed raw materials into a melting furnace, and melt them at 1300~1500℃ to form molten glass; 2) Stirring and homogenizing the molten glass; 3) Pouring or leaking the molten glass into a mold to form it; 4) The glass formed in step 3) is maintained at 470 to 600°C for 10 to 60 hours to develop color, or the glass formed in step 3) is further processed into a glass preform or glass member, and then maintained at 470 to 600°C for 10 to 60 hours to develop color.

[0049] Furthermore, the raw materials for the environmentally friendly glass material may be composite salts (carbonates, sulfates, nitrates, etc.), and / or hydroxides, and / or oxides, and / or sulfides, and / or selenides, and / or fluorides, and / or simple substances.

[0050] [Glass preforms and glass components] A glass preform can be produced from the environmentally friendly glass material using compression molding means such as grinding, reheat forming, precision stamping, etc. That is, a glass preform can be produced by polishing and other mechanical processing of the environmentally friendly glass material, by producing a preform for compression molding from the environmentally friendly glass material, and then reheat forming and polishing the preform, or by precision stamping the preform produced by polishing.

[0051] The means for producing the glass preform is not limited to the above means.

[0052] The glass preform and glass member of the present invention are both formed from the above-mentioned environmentally friendly glass material of the present invention. The glass preform of the present invention has the excellent properties of the environmentally friendly glass material, and the glass member of the present invention has the excellent properties of the environmentally friendly glass material, making it possible to provide various valuable glass members such as filters, lenses, and prisms.

[0053] [device] The environmentally friendly glass material of the present invention and glass members formed therefrom can be used to manufacture optical filters, photographic devices, camera equipment, display equipment, monitoring equipment, electronic equipment, intelligent equipment, and the like.

[0054] Embodiment In order to further clearly describe and illustrate the technical solutions of the present invention, the following non-limiting embodiments 1 to 22 are provided.

[0055] In this embodiment, the above-described manufacturing method for an environmentally friendly glass material is used to obtain an environmentally friendly glass material having the components shown in Tables 1 to 3. In addition, the properties of each glass were measured using the test methods described in the present invention, and the results are shown in Tables 1 to 3. [Table 1] [Table 2] [Table 3]

Claims

1. Its components, expressed in weight percent, are: SiO 2 35-80%; ZnO 5-35%; Na 2 O 5-25%; K 2 An environmentally friendly glass material containing 1-10% O; 0.2-8% S; 0.5-10% Sb+Ag+Ce+Sn+Te+V+Fe, ZnO / SiO2 ratio of 0.10-0.95, and no Cd, and having a thickness of 3 mm, has a cutoff wavelength of 550 nm or more, a transmittance of 75% or more in the 800-850 nm range, a transmittance of 80% or more in the 850-900 nm range, a transmittance of 83% or more in the 900-1000 nm range, and a transmittance of 85% or more in the 1000-2000 nm range.

2. Its components expressed in weight percent are: Li 2 O 0-5%; B 2 O 3 0-10%; Al 2 O 3 2. The environmentally friendly glass material according to claim 1, comprising 0 to 5% of: MgO 0 to 5%; CaO 0 to 5%; SrO 0 to 10%; BaO 0 to 10%; Se 0 to 5%; and F 0 to 5%.

3. Its components, expressed in weight percent, are: SiO 2 and / or ZnO 7 to 30%; and / or Na 2 7-22% O; and / or K 2 2-8% O; and / or Li 2 O: 0 to 3%; and / or S: 0.5 to 7%; and / or Sb+Ag+Ce+Sn+Te+V+Fe: 0.8 to 9%; and / or B 2 O 3 0 to 5%; and / or Al 2 O 3 and / or MgO 0 to 3%; and / or CaO 0 to 3%; and / or SrO 0 to 5%; and / or BaO 0 to 5%; and / or Se 0 to 4%; and / or F 0 to 3%.

4. Its components, expressed in weight percent, are: SiO 2 and / or ZnO 9 ​​to 25%; and / or Na 2 8-19% O; and / or K 2 O 3-7%; and / or S 1-6%; and / or Sb+Ag+Ce+Sn+Te+V+Fe 0.9-8%; and / or Se 0-3%; and / or Li 2 O 0-2%; and / or B 2 O 3 0 to 3%; and / or Al 2 O 3 and / or MgO 0 to 2%; and / or CaO 0 to 2%; and / or SrO 0 to 2%; and / or BaO 0 to 2%; and / or F 0 to 1%.

5. Its components are expressed in weight percent as follows: CuO + TiO 2 +P 2 O 5 2. The environmentally friendly glass material according to claim 1, containing 0 to 0.5% of

6. Its components are expressed in weight percent as follows: CuO + TiO 2 +P 2 O 5 2. The environmentally friendly glass material according to claim 1, containing 0.0001 to 0.3% of

7. The components are expressed in weight percent, 1) B 2 O 3 / SiO 2 is 0.23 or less, 2) Se / S is 1.5 or less, 3) (Sb+Ag+Ce+Sn+Te+V+Fe) / (Se+S) is 0.1 to 25.0, 4) (Ag+Ce+Sn+Te+V+Fe) / Sb is 3.0 or less, 5) Li 2 O + Na 2 O+K 2 2. The environmentally friendly glass material according to claim 1, wherein O is 8 to 35%.

8. The components are expressed in weight percent, 1) B 2 O 3 / SiO 2 is 0.15 or less, 2) ZnO / SiO 2 is 0.10 to 0.75, 3) Se / S is 1.0 or less, 4) (Sb+Ag+Ce+Sn+Te+V+Fe) / (Se+S) is 0.5 to 8.0, 5) (Ag+Ce+Sn+Te+V+Fe) / Sb is 2.0 or less, 6) I read 2 O+Na 2 OK 2 Oが9~30%、 2. The environmentally friendly glass material according to claim 1, which satisfies one or more of the following six conditions:

9. The components are expressed in weight percent, 1) B 2 O 3 / SiO 2 is 0.1 or less, 2) ZnO / SiO 2 is 0.15 to 0.60, 3) Se / S is 0.5 or less, 4) (Sb+Ag+Ce+Sn+Te+V+Fe) / (Se+S) is 1.0 to 5.0, 5) (Ag+Ce+Sn+Te+V+Fe) / Sb is 0.8 or less, 6) I read 2 O+Na 2 OK 2 Oが10~22%、 2. The environmentally friendly glass material according to claim 1, which satisfies one or more of the following six conditions:

10. 2. The environmentally friendly glass material according to claim 1, wherein, when the thickness of the environmentally friendly glass material is 3 mm, the cutoff wavelength is 600 nm or more, and / or the transmittance in the range of 800 to 850 nm is 77% or more, and / or the transmittance in the range of 850 to 900 nm is 82% or more, the transmittance in the range of 900 to 1000 nm is 84% ​​or more, and the transmittance in the range of 1000 to 2000 nm is 86% or more.

11. 2. The environmentally friendly glass material according to claim 1, wherein, when the thickness of the environmentally friendly glass material is 3 mm, the cutoff wavelength is 700 nm or more, and / or the transmittance in the range of 800 to 850 nm is 80% or more, and / or the transmittance in the range of 850 to 900 nm is 83% or more, and / or the transmittance in the range of 900 to 1000 nm is 85% or more, and / or the transmittance in the range of 1000 to 2000 nm is 87% or more.

12. The environmentally friendly glass material has an acid resistance stability of Class 1; and / or a water resistance stability of Class 1; and / or a thermal expansion coefficient of 95×10 -7 2. The environmentally friendly glass material according to claim 1, wherein the glass has a temperature of 100°C or higher.

13. A glass preform made from the environmentally friendly glass material according to any one of claims 1 to 12.

14. A glass member using the environmentally friendly glass material according to any one of claims 1 to 12 or the glass preform according to claim 13.

15. A device comprising the environmentally friendly glass material according to any one of claims 1 to 12 and / or the glass member according to claim 14.

16. A method for producing an environmentally friendly glass material according to any one of claims 1 to 12, comprising the steps of: 1) Mix all the raw materials according to the component ratio of the environmentally friendly glass material, put the uniformly mixed raw materials into a melting furnace, and melt them at 1300-1500℃ to form molten glass; 2) Stirring and homogenizing the molten glass; 3) Pouring or leaking the molten glass into a mold to form it; 4) The glass formed in step 3) is maintained at 470 to 600°C for 10 to 60 hours to develop color, or the glass formed in step 3) is further processed into a glass preform or glass member, and then maintained at 470 to 600°C for 10 to 60 hours to develop color. A manufacturing method for environmentally friendly glass materials.

17. 17. The method for producing an environmentally friendly glass material according to claim 16, wherein compound salts, and / or hydroxides, and / or oxides, and / or sulfides, and / or selenides, and / or fluorides, and / or simple substances are used as raw materials for the environmentally friendly glass material.

Images