Glass material, glass member and device

Abstract

To provide a glass material that has high light transmittance and excellent chemical stability and is particularly suitable for use in the field of photosensitive device packaging.SOLUTION: There is provided a glass material, comprising the following components by weight percentage: 50 to 70% of SiO2; 3 to 15% of B2O3; 0.5 to 10% of TiO2; 1 to 12% of ZnO; 0.5 to 10% of Al2O3; 5 to 22% of Na2O+K2O, wherein B2O3 / SiO2 is 0.06 to 0.26, and (TiO2+ZnO) / Al2O3 is 0.5 to 8.0.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a glass material, and particularly to a glass material suitable for use in the package field of a photosensitive device.

Background Art

[0002] Generally, photoelectric conversion devices such as CMOS and CCD use a glass material as a window material, and the window plays a role of light transmission and protection of the photoelectric conversion chip. Conventional photosensitive devices such as CMOS and CCD are usually mounted on cameras in a comfortable use environment, so there are no high requirements for the chemical stability (acid resistance, water resistance, alkali resistance, etc.), weather resistance, and temperature shock resistance of the protection window of the photosensitive device. In recent years, with the development of automotive security, deep space and ocean exploration, machine vision, etc., there is a demand for photosensitive devices with high reliability under extremely harsh conditions. For example, photosensitive devices used during high-temperature fires need to withstand extreme temperature environments of 100 to 200 °C or higher, photosensitive devices used for observing the marine environment need to be able to withstand long-term alkaline or acidic corrosion, photosensitive devices used for observing chemical (chemical) experiments need to be able to withstand strong acid and strong alkali corrosion, and photosensitive devices used for in-vehicle and security purposes are required to be exposed to the outdoor environment for a long time. Photosensitive devices such as CMOS have a silicon single crystal material as the main component of the photosensitive chip, and the package housing is mainly a ceramic material. Although the ceramic material is very excellent in chemical stability and impact resistance, it has the weakness of not transmitting light, and a brittle glass material is required as a window for transmitting light. However, there is a large gap between the glass material and the ceramic material in terms of chemical stability and heat shock resistance. Therefore, improving the chemical stability and temperature shock resistance of the window glass material is the best way to improve the reliability of the photosensitive device under a harsh external environment.

[0003] In addition, the glass material, which is the window of the photosensitive chip, is required to have a high transmittance in the range of 360 nm to 2000 nm in order to meet the photosensitive needs in different wavelength bands of ultraviolet - visible - near infrared. Since the transmittance of the glass material usually increases gradually from 360 nm to 2000 nm, the minimum transmittance of the glass can be characterized by the internal transmittance (τ 360nm ) at 360 nm. If τ 360nm is 78% or more, it indicates that the package glass can meet the requirements of the transmittance in the above wavelength band. Since the package glass needs to avoid reflection loss as much as possible, when the refractive index exceeds 1.60, the reflection loss of the glass increases. Although it is possible to reduce the reflection loss by coating an antireflection film, there may be problems such as cost increase and interference of stray light.

Summary of the Invention

Problems to be Solved by the Invention

[0004] The technical problem to be solved by the present invention is to provide a glass material with high light transmittance and excellent chemical stability.

[0005] The technical solution adopted by the present invention to solve the technical problem is as follows. (1) A glass material containing the following components by weight percentage: SiO 2 : 50 - 70%, B 2 O 3 : 3 - 15%, TiO 2 : 0.5 - 10%, ZnO: 1 - 12%, Al 2 O 3 : 0.5 - 10%, Na 2 O + K 2 O: 5 - 22%, and B 2 O 3 / SiO 2 is 0.06 - 0.26, (TiO 2 + ZnO) / Al 2 O 3 is 0.5 - 8.0.

[0006] (2) The glass material according to (1), further comprising the following components by weight percentage: MgO + CaO + SrO + BaO: 0 to 10%; and / or Li 2 O: 0 to 5%; and / or P 2 O 5 : 0 to 5%; and / or ZrO 2 : 0 to 5%; and / or La 2 O 3 : 0 to 5%; and / or Y 2 O 3 : 0 to 5%, and / or Gd 2 O 3 : 0 to 5%, and / or Nb 2 O 5 : 0 to 5%, and / or WO 3 : 0 to 5%, and / or fining agent: 0 to 1%.

[0007] (3) The glass material consisting of the following components by weight percentage: SiO 2 : 50 to 70%, B 2 O 3 : 3 to 15%, TiO 2 : 0.5 to 10%, ZnO: 1 to 12%, Al 2 O 3 : 0.5 to 10%, Na 2 O + K 2 O: 5 to 22%, MgO + CaO + SrO + BaO: 0 to 10%, Li 2 O: 0 to 5%, P 2 O 5 : 0 to 5%, ZrO 2 : 0 to 5%, La 2 O 3 : 0 to 5%, Y 2 O 3 : 0 to 5%, Gd 2 O 3 : 0 to 5%, Nb 2 O 5 : 0 to 5%, WO 3 : 0 to 5%, fining agent: 0 to 1%, and B 2 O 3 / SiO 2 is 0.06 to 0.26, (TiO 2 + ZnO) / Al 2 O 3 is 0.5 to 8.0.

[0008] (4) A glass material according to any one of (1) to (3), containing the following components by weight%: B 2 O 3 / SiO 2 is 0.08 to 0.2, and / or (TiO 2 +ZnO) / Al 2 O 3 is 0.7 to 7.0, and / or (SiO 2 +TiO 2 ) / (Na 2 O+ZnO) is 3.0 to 12.0; and / or ZnO / B 2 O 3 is 0.2 to 1.8; and / or (Na 2 O+K 2 O) / Al 2 O 3 is 0.8 to 8.0; and / or (Na 2 O+K 2 O) / (B 2 O 3 +ZnO) is 0.2 to 2.5; and / or (B 2 O 3 +K 2 O) / Al 2 O 3 is 1.0 to 10.0.

[0009] (5) A glass material according to any one of (1) to (3), containing the following components by weight%: (MgO+CaO+SrO+BaO) / ZnO is 1.0 or less, and / or (MgO+CaO+SrO+BaO) / Al 2 O 3 is 1.0 or less, and / or (MgO+CaO+SrO+BaO) / (Na 2 O+K 2 O) is 1.0 or less.

[0010] (6) A glass material according to any one of (1) to (3), containing the following components by weight%: SiO 2 : 55 to 68%, and / or B 2 O 3 : more than 5% and 13% or less, and / or TiO2 : 1.5 to 8%, and / or ZnO: 2 to 10%, and / or Al 2 O 3 : 1 to 8%, and / or Na 2 O + K 2 O: 6 to 20%, and / or MgO + CaO + SrO + BaO: 0 to 5%, and / or Li 2 O: 0 to 3%, and / or P 2 O 5 : 0 to 3%, and / or ZrO 2 : 0 to 3%, and / or La 2 O 3 : 0 to 3%, and / or Y 2 O 3 : 0 to 3%, and / or Gd 2 O 3 : 0 to 3%, and / or Nb 2 O 5 : 0 to 3%, and / or WO 3 : 0 to 3%, and / or clarifying agent: 0 to 0.5%.

[0011] (7) A glass material according to any one of (1) to (3), containing the following components by weight%: B 2 O 3 / SiO 2 is 0.1 to 0.18, and / or (TiO 2 + ZnO) / Al 2 O 3 is 1.0 to 5.0, and / or (SiO 2 + TiO 2 ) / (Na 2 O + ZnO) is 3.0 to 10.0, and / or ZnO / B 2 O 3 is 0.3 to 1.0, and / or (Na 2 O + K 2 O) / Al 2 O 3 is 1.0 to 6.0, and / or (Na 2 O + K 2 O) / (B 2 O 3 + ZnO) is 0.3 to 2.0, and / or (B 2 O 3 + K 2 O) / Al 2O 3 is 1.5 to 8.0.

[0012] (8) A glass material according to any one of (1) to (3), containing the following components by weight%: (MgO + CaO + SrO + BaO) / ZnO is 0.5 or less, and / or (MgO + CaO + SrO + BaO) / Al 2 O 3 is 0.5 or less, and / or (MgO + CaO + SrO + BaO) / (Na 2 O + K 2 O) is 0.5 or less.

[0013] (9) A glass material according to any one of (1) to (3), containing the following components by weight%: SiO 2 : 60 to 68%; and / or B 2 O 3 : 6 to 12%; and / or TiO 2 : 2 to 7%; and / or ZnO: 3 to 8%; and / or Al 2 O 3 : 2 to 7%; and / or Na 2 O + K 2 O: 8 to 18%; and / or La 2 O 3 : 0 to 1%; and / or Y 2 O 3 : 0 to 1%; and / or Gd 2 O 3 : 0 to 1%; and / or Nb 2 O 5 : 0 to 1%; and / or WO 3 : 0 to 1%.

[0014] (10) A glass material according to any one of (1) to (3), containing the following components by weight%: (SiO 2 + TiO 2 ) / (Na 2 O + ZnO) is 4.0 to 8.0, and / or ZnO / B 2 O 3 is 0.4 to 0.8, and / or (Na 2 O + K 2 O) / Al2 O 3 is 1.5 to 5.0, and / or (Na 2 O + K 2 O) / (B 2 O 3 + ZnO) is 0.5 to 1.5, and / or (B 2 O 3 + K 2 O) / Al 2 O 3 is 2.0 to 6.0.

[0015] (11) A glass material according to any one of (1) to (3), containing the following components by weight%: (MgO + CaO + SrO + BaO) / ZnO is 0.2 or less, and / or (MgO + CaO + SrO + BaO) / Al 2 O 3 is 0.2 or less, and / or (MgO + CaO + SrO + BaO) / (Na 2 O + K 2 O) is 0.2 or less.

[0016] (12) A glass material according to any one of (1) to (3), containing the following components by weight%: Na 2 O: 2 to 12%, preferably Na 2 O: 3 to 10%, more preferably Na 2 O: 4 to 9%, and / or K 2 O: 2 to 12%, preferably K 2 O: 3 to 10%, more preferably K 2 O: 4 to 9%, and / or MgO: 0 to 5%, preferably MgO: 0 to 3%, more preferably MgO: 0 to 2%; and / or CaO: 0 to 5%, preferably CaO: 0 to 3%, more preferably CaO: 0 to 2%; and / or SrO: 0 to 5%, preferably SrO: 0 to 3%, more preferably SrO: 0 to 2%; and / or BaO: 0 to 5%, preferably BaO: 0 to 3%, more preferably BaO: 0 to 2%.

[0017] (13) A glass material according to any one of (1) to (3), containing the following components by weight%: La 2O 3 、 Y 2 O 3 、 Gd 2 O 3 、 Nb 2 O 5 and WO 3 The total content thereof is 5% or less, preferably 3% or less, more preferably 1% or less.

[0018] (14) The component does not contain F; and / or Ta 2 O 5 and does not contain; and / or Li 2 O and does not contain; and / or P 2 O 5 and does not contain; and / or ZrO 2 and does not contain, the glass material according to any one of (1) to (3).

[0019] (15) The refractive index is 1.48 to 1.56, preferably 1.50 to 1.55, more preferably 1.51 to 1.54; and / or the Abbe number is 50 to 58, preferably 51 to 57, more preferably 53 to 56; and / or the coefficient of thermal expansion α 20-300℃ is 60×10 -7 / K to 90×10 -7 / K, preferably 65×10 -7 / K to 85×10 -7 / K, more preferably 68×10 -7 / K to 80×10 -7 / K; and / or the Young's modulus is 6000×10 7 Pa or more, preferably 6500×10 7 Pa to 8500×10 7 Pa, more preferably 7000×10 7 Pa to 8000×10 7 Pa; and / or the transition temperature is 500°C to 610°C, preferably 520°C to 600°C, more preferably 530°C to 580°C, and / or the bubble degree is Class A or above, preferably Class A 0 Class or above, more preferably Class A 00 Class; and / or the stripe is Class C or above, preferably Class B or above, the glass material according to any one of (1) to (3).

[0020] (16) The acid resistance stability is Class 2 or higher, preferably Class 1; and / or the water resistance stability is Class 2 or higher, preferably Class 1; and / or the weight loss of the glass sample after measuring the alkali resistance according to the test conditions and requirements of ISO10629 is less than 9 mg, preferably less than 7 mg, more preferably less than 5 mg; and / or the light transmittance τ 360nm is 78% or higher, preferably 82% or higher, more preferably 85% or higher, and the glass material according to any one of (1) to (3).

[0021] (17) The glass material according to any one of (1) to (16) used in the field of packaging materials.

[0022] (18) A glass member made of the glass material according to any one of (1) to (16).

[0023] (19) An apparatus comprising the glass material according to any one of (1) to (16), or comprising the glass member according to (18). [Advantages of the Invention]

[0024] The beneficial effects of the present invention are as follows. Through reasonable component design, the glass material obtained by the present invention has high light transmittance and excellent chemical stability, and is suitable for applications in fields such as the packaging of photosensitive devices. [Modes for Carrying Out the Invention]

[0025] Hereinafter, embodiments of the glass material according to the present invention will be described in detail. However, the present invention is not limited to the embodiments described below, and can be appropriately modified and implemented within the scope of the object of the present invention. Furthermore, although there are appropriate omissions, the gist of the present invention is not limited by repeating the description. Hereinafter, the glass material of the present invention may also be simply referred to as glass.

[0026] [Glass Material] The range of the components of the glass material of the present invention will be described below. In this specification, the content and total content of each component are expressed as weight percentages with respect to the total glass material converted into an oxide composition, unless otherwise specified. The term "converted into an oxide composition" as used herein refers to the case where the total weight of the oxide substances when oxides, complex salts, hydroxides, etc. used as raw materials of the composition of the glass material of the present invention are decomposed and converted into oxides during melting is taken as 100%.

[0027] Unless otherwise specified, the numerical ranges described in this specification include upper and lower limit values, and "above" and "below" include the end point values, as well as all integers and fractions included in the range, and are not limited to the specific values described when the range is limited. What is referred to as "and / or" in this specification is inclusive. For example, "A and / or B" means only A, only B, or both A and B.

[0028] <Essential Components and Optional Components> SiO 2 is one of the main components of the glass. In the glass of the present invention, an appropriate amount of SiO 2 can ensure high water resistance, acid resistance, and high light transmittance. If the content of SiO 2 is less than 50%, the water resistance, acid resistance, and ultraviolet transmittance of the glass will be lower than the design requirements. If the content of SiO 2 exceeds 70%, the refractive index of the glass will not meet the design requirements. The melting temperature of the glass will rise rapidly, making it difficult to obtain high-quality glass in terms of manufacturing, and the thermal expansion coefficient of the glass will decrease. Therefore, the content of SiO 2 in the present invention is limited to 50 - 70%, preferably 55 - 68%, more preferably 60 - 68%.

[0029] An appropriate amount of B 2 O 3 changes the glass structure in the direction of densification, improves the refractive index of the glass, and at the same time can achieve higher water resistance and acid resistance. If its content is less than 3%, the above effects are not significant. B2 O 3 When the content of [O] exceeds 15%, the water resistance and acid resistance of the glass decrease. Therefore, [B] 2 O 3 The content of [O] is limited to 3 - 15%, preferably more than 5% and less than or equal to 13%, more preferably 6 - 12%.

[0030] In the present invention, the value of [B] 2 O 3 / SiO 2 affects the difficulty of glass production. When [B] 2 O 3 / SiO 2 is less than 0.06, the glass melting temperature rises, the erosion of refractories becomes severe, it is easy for coloring impurities and inclusions to enter the glass, the glass transmittance cannot meet the design requirements, and at the same time, there is a high possibility of defects occurring inside the product. When [B] 2 O 3 / SiO 2 exceeds 0.26, the melting temperature does not drop much, the erosion of refractories by [B] 2 O 3 progresses, the coloring impurities and inclusions in the glass increase, the short - wavelength transmittance of the glass cannot meet the design requirements, and at the same time, there is a high tendency for defects to occur on the product surface. Therefore, in the present invention, the value of [B] 2 O 3 / SiO 2 is 0.06 - 0.26, preferably 0.08 - 0.2, more preferably 0.1 - 0.18.

[0031] By adding an appropriate amount of Al 2 O 3 to the glass, the water resistance and acid resistance of the glass can be improved, and particularly, the thermal expansion coefficient of the glass can be decreased in the presence of alkali metal oxides. When the content of Al 2 O 3 exceeds 10%, the thermal expansion coefficient of the glass decreases rapidly and cannot meet the design requirements. Therefore, the content of Al 2 O 3 is limited to 0.5 - 10%, preferably 1 - 8%, more preferably 2 - 7%.

[0032] Adding an appropriate amount of TiO 2 to glass can improve the refractive index, water resistance, acid resistance, and alkali resistance of the glass, and is expected to reduce the thermal expansion coefficient and improve the thermal shock resistance. When the content of TiO 2 is less than 0.5%, the above effects are not significant. When it exceeds 10%, the Abbe number of the glass becomes lower than the designed expected value, and particularly under an unstable melting atmosphere, the transmittance at short wavelengths decreases rapidly. More importantly, when the content of TiO 2 is high, the refractive index of the glass increases rapidly. When an antireflection film is not coated, the reflection loss on the short wavelength side increases, the transmittance on the short wavelength side further decreases, and the thermal expansion coefficient of the glass decreases, making it impossible to meet the design requirements. Therefore, the content of TiO 2 in the present invention is limited to 0.5 to 10%, preferably 1.5 to 8%. In some embodiments, considering the refractive index, Abbe number of the glass, and the difficulty of atmosphere control during melting, the content of TiO 2 is more preferably 2 to 7%.

[0033] ZnO has a high electric field strength among divalent metal oxides. Adding ZnO to glass can improve the acid resistance, water resistance, and alkali resistance of the glass, increase the refractive index of the glass, and particularly reduce the thermal expansion coefficient of the glass in a glass system containing alkali metals. These effects will not appear significantly if the content of ZnO is less than 1%. When the content of ZnO exceeds 12%, the transition temperature of the glass drops rapidly, and the glass is likely to soften and deform under a high-temperature operating environment, which becomes a fatal problem for glass devices that require high-temperature operation. Also, when the content exceeds 12%, the dispersion of the glass increases rapidly, and the Abbe number fails to meet the design requirements. Therefore, the content of ZnO is limited to 1 to 12%, preferably 2 to 10%, and more preferably 3 to 8%.

[0034] In the present invention, when the value of (TiO 2 +ZnO) / Al 2 O 3 exceeds 8.0, the ultraviolet transmittance of the glass decreases and it is prone to devitrification. When (TiO 2+ZnO) / Al 2 O 3 If the value is less than 0.5, the fusibility of the glass decreases, making it difficult to expel bubbles, resulting in poor internal quality. Therefore, (TiO 2 +ZnO) / Al 2 O 3 The value of is 0.5 to 8.0, preferably (TiO 2 +ZnO) / Al 2 O 3 The value of is 0.7 to 7.0, and more preferably (TiO 2 +ZnO) / Al 2 O 3 The value is 1.0 to 5.0.

[0035] As a result of intensive experimental research by the inventors, it was found that glass B 2 O 3 It has been found that when ZnO / B is contained, the presence of ZnO further lowers the melting temperature of the glass, making it easier to obtain high-quality products. 2 O 3 When the value is less than 0.2, the above effect is not significant, and the ZnO / B 2 O 3 It was found that if the ratio exceeds 1.8, the glass transition temperature drops rapidly and the heat resistance does not meet the design requirements. 2 O 3 When the value of is between 0.2 and 1.8, B 2 O 3 The glass obtained has better water resistance, acid resistance, and alkali resistance than when ZnO / B is added alone. 2 O 3 The value is preferably 0.2 to 1.8, more preferably 0.3 to 1.0, and further preferably 0.4 to 0.8.

[0036] By adding alkaline earth metal oxides such as MgO, CaO, SrO, and BaO to glass, the refractive index and transition temperature of the glass can be increased, and the stability and thermal expansion coefficient of the glass can be adjusted. However, when adding alkaline earth metal oxides, the Young's modulus of the glass increases rapidly. If the thermal expansion coefficients are the same, a glass material with a lower Young's modulus is superior in thermal shock resistance. Therefore, considering the above factors, the total addition amount of the alkaline earth metal oxides MgO + CaO + SrO + BaO is preferably 10% or less, more preferably 5% or less. In some embodiments, when the stability, thermal expansion coefficient, and transition temperature of the glass meet the design requirements, it is even more preferable not to add alkaline earth metal oxides.

[0037] In some embodiments of the present invention, the ratio of alkaline earth metal oxide to Al 2 O 3 (MgO + CaO + SrO + BaO) / Al 2 O 3 is made 1.0 or less, preferably (MgO + CaO + SrO + BaO) / Al 2 O 3 is made 0.5 or less, and more preferably (MgO + CaO + SrO + BaO / Al 2 O 3 is made 0.2 or less, whereby the devitrification resistance and chemical stability of the glass can be improved.

[0038] Depending on the packaging application, a higher refractive index and a higher transition temperature adapted to the optical system are required, which can be achieved by adding a small amount of alkaline earth metal oxides. When adding alkaline earth metal oxides, it is conceivable to add MgO, CaO, SrO, and BaO alone or in combination so that the water resistance, acid resistance, and alkali resistance of the glass do not decrease rapidly. When the content of an alkaline earth metal oxide alone such as MgO, CaO, SrO, or BaO exceeds 5%, the devitrification resistance of the glass decreases rapidly, and it is not easy to obtain a large-diameter and high-quality product. Therefore, the contents of MgO, CaO, SrO, and BaO are each limited to 5% or less, preferably 3% or less, and more preferably 2% or less.

[0039] As a result of the inventors' intensive experimental research, it has been found that when there is a certain amount of alkaline earth metal oxide in the glass, by adjusting the content of ZnO, it is considered possible to suppress the decrease in the chemical stability and thermal shock resistance of the glass. In some embodiments, when the value of (MgO + CaO + SrO + BaO) / ZnO is 1.0 or less, preferably 0.5 or less, more preferably 0.2 or less, a glass with a higher refractive index and satisfying the chemical stability, thermal expansion coefficient, and thermal shock resistance of the design requirements of the present invention can be more easily obtained.

[0040] Li 2 O, Na 2 O, K 2 O is an alkali metal oxide, and its content in the glass of the present invention is closely related to the thermal expansion coefficient, chemical stability, and internal quality.

[0041] Li 2 By adding LiO, the melting temperature of the glass decreases and the bubble degree of the glass improves. On the other hand, compared with the other two alkali metal oxides, the loss of chemical stability to the glass is minimized. However, when the content of LiO exceeds 5%, the hardening of the glass becomes slow in the forming process, that is, the process of cooling the glass liquid from liquid to solid, which is disadvantageous for the production of large-sized and high-quality products (for example, when producing products with a width or diameter exceeding 340 mm and a thickness exceeding 40 mm, defects such as stripes and internal devitrification are likely to occur). On the other hand, it also causes a decrease in the glass transition temperature and the heat resistance does not meet the design requirements. Therefore, the content of LiO is limited to 5% or less, preferably 3% or less, and more preferably no LiO is added. 2 O's content is 5% or less, preferably 3% or less, and more preferably no LiO is added. 2 O's content is limited to 5% or less, preferably 3% or less, and more preferably no LiO is added. 2 O is added.

[0042] In the present invention, Na 2 O and K 2 O's total content Na 2 O + K 2When O exceeds 22%, the Abbe number of the glass is lower than the design requirements, and at the same time, when the thermal expansion coefficient of the glass exceeds the design requirements, the dielectric constant of the glass rises sharply, the insulation of the glass drops sharply, which is disadvantageous for specific applications where insulation needs to be satisfied. Na 2 O + K 2 When O is less than 5%, while the thermal expansion coefficient of the glass does not meet the design requirements, it causes an increase in the coloring ability of the variable components in the glass, and the short-wavelength transmittance of the glass fails to meet the design requirements. Therefore, Na 2 O and K 2 The total content of Na 2 O + K 2 O is 5 - 22%, preferably 6 - 20%, more preferably 8 - 18%.

[0043] Adding Na 2 O to the glass can significantly increase the thermal expansion coefficient of the glass and lower the high-temperature viscosity of the glass, making it easier to obtain glass products with a width exceeding 330 mm that can be processed into wafers for 12-inch packages. However, Na 2 When the content of O exceeds 12%, the refractive index of the glass decreases, and the chemical stability drops sharply and fails to meet the design requirements. Na 2 When O is less than 2%, the thermal expansion coefficient of the glass does not meet the design requirements, and the chemical stability deteriorates significantly. Therefore, Na 2 The content of O is limited to 2 - 12%, preferably 3 - 10%, more preferably 4 - 9%.

[0044] Adding an appropriate amount of K 2 O to the glass can, especially in the coexistence with Na 2 O, improve the thermal expansion coefficient, reduce the high-temperature viscosity of the glass, and improve the bubble degree of the glass. Adding an appropriate amount of K 2 O to the glass does not significantly impair the chemical stability of the glass. However, when its content exceeds 12%, the water resistance, acid resistance, and alkali resistance of the glass decrease. K 2 When the content of O is less than 2%, the effects of increasing the thermal expansion coefficient and reducing the high-temperature viscosity cannot be expected much. Therefore, K 2The content of O is limited to 2 to 12%, preferably 3 to 10%, more preferably 4 to 9%.

[0045] In some embodiments of the present invention, (B 2 O 3 +K 2 O) / Al 2 O 3 If the value of is more than 10.0, the alkali resistance of the glass decreases, the coefficient of thermal expansion increases, and (B 2 O 3 +K 2 O) / Al 2 O 3 If the value of is less than 1.0, the solubility of the glass decreases and the transition temperature increases. Therefore, (B 2 O 3 +K 2 O) / Al 2 O 3 Preferably, the value of is 1.0 to 10.0, more preferably (B 2 O 3 +K 2 O) / Al 2 O 3 Preferably, the value of is 1.5 to 8.0, still more preferably (B 2 O 3 +K 2 O) / Al 2 O 3 The value of is 2.0 to 6.0.

[0046] In some embodiments of the present invention, if the value of (Na 2 O+K 2 O) / (B 2 O 3 +ZnO) is less than 0.2, there is insufficient free oxygen in the glass system, and the probability of components such as B 2 O 3 and ZnO entering the glass network decreases, resulting in a sharp decrease in chemical stability and a decrease in the expansion coefficient of the glass, making the design requirements unsatisfactory. (Na 2 O+K 2 O) / (B 2 O 3When the value of (Na 2 O + K 2 O) / (B 2 O 3 + ZnO) exceeds 2.5, the free oxygen in the glass system becomes excessive, the chemical stability of the glass rapidly decreases, and the expansion coefficient of the glass exceeds the design requirements. Therefore, when the value of (Na

[0047] In the prior art, it is generally considered that the addition of alkaline earth metal oxides such as MgO, CaO, SrO, BaO to glass is more advantageous for chemical stability than alkali metal oxides such as Li 2 O, Na 2 O, K 2 O, etc. However, the inventors have experimentally found that in the glass of this system, since the free oxygen supply ability of alkaline earth metal oxides is weaker than that of alkali metal oxides, when the value of (MgO + CaO + SrO + BaO) / (Na 2 O + K 2 O) exceeds 1.0, it will cause damage to the deep internal network of the glass. In particular, the chemical stability when immersed in a strong alkali solution becomes low, and when the value of (MgO + CaO + SrO + BaO) / (Na 2 O + K 2 O) exceeds 1.0, it is found that alkaline earth metal ions are more easily precipitated by erosion and are subject to a catastrophic impact depending on the process during semiconductor manufacturing. Therefore, the value of (MgO + CaO + SrO + BaO) / (Na 2 O + K 2 O) can be 1.0 or less, preferably 0.5 or less, more preferably 0.2 or less.

[0048] In the present invention, the addition of Na 2 O or K 2 O is necessary to obtain an appropriate expansion coefficient, but it leads to a decrease in the chemical stability of the glass. As a result of research, the inventors have found that Al 2 O 3When present, it has been found that the fine structure of the glass changes depending on the type of alkali metal oxide and its relative content, significantly affecting the chemical stability of the glass. In some embodiments, when the value of (Na 2 O + K 2 O) / Al 2 O 3 is between 0.8 and 8.0, preferably between 1.0 and 6.0, more preferably between 1.5 and 5.0, the chemical stability of the glass is improved.

[0049] In some embodiments of the present invention, when the value of (SiO 2 + TiO 2 ) / (Na 2 O + ZnO) exceeds 12.0, the glass becomes difficult to melt and clarify, and it becomes difficult to remove bubbles and inclusions inside the glass. As a result, it is difficult to obtain glass of bubble degree A 0 or higher, and the stripes inside the glass become intense. When (SiO 2 + TiO 2 ) / (Na 2 O + ZnO) is less than 3.0, the thermal expansion coefficient of the glass rises rapidly and exceeds the design requirements. Therefore, the value of (SiO 2 + TiO 2 ) / (Na 2 O + ZnO) is preferably controlled to be between 3.0 and 12.0, more preferably between 3.0 and 10.0, and even more preferably between 4.0 and 8.0.

[0050] By adding an appropriate amount of ZrO 2 , the chemical stability and thermal shock resistance of the glass are improved, and the refractive index of the glass is also improved. However, it has the characteristic that the melting temperature of the glass rises significantly. When its content exceeds 5%, inclusion defects are likely to occur in the glass. Therefore, the content of ZrO 2 is limited to 5% or less, preferably 3% or less. In some embodiments, when there is a surplus in the chemical stability and strength of the glass, it is more preferable not to add ZrO 2 .

[0051] Particularly when chemical strengthening is required, an appropriate amount of P2 O 5 Adding it can enhance the strength of the glass. However, if the content exceeds 5%, differential phases are likely to occur in the glass, significantly increasing the glass forming temperature. Therefore, P 2 O 5 The content of is limited to 0 - 5%, preferably 0 - 3%. In some embodiments, when the glass strength design meets the requirements in use, it is more preferable not to add P 2 O 5 .

[0052] In some embodiments of the present invention, when it is necessary to increase the refractive index and transition temperature of the glass, La 2 O 3 , Y 2 O 3 , Gd 2 O 3 , Nb 2 O 5 , WO 3 and other oxides can be added in appropriate amounts. However, if their individual or total content exceeds 5%, the Young's modulus of the glass will increase rapidly. Although the strength of the glass increases, the brittleness of the glass will increase more rapidly, and instead, the resistance to thermal shock will decrease. Also, the devitrification resistance and short - wavelength transmittance of the glass will deteriorate. Therefore, the content of La 2 O 3 , Y 2 O 3 , Gd 2 O 3 , Nb 2 O 5 and WO 3 is 5% or less respectively, preferably 3% or less, more preferably 1% or less, and even more preferably not contained. Furthermore, it is preferable that the total content of La 2 O 3 , Y 2 O 3 , Gd 2 O 3 , Nb 2 O 5 , WO 3 is 5% or less, more preferably 3% or less, and even more preferably 1% or less.

[0053] In some embodiments of the present invention, the fining property of the glass can be improved by adding 0 to 1% of one or more components of Sb 2 O 3 , SnO 2 , SnO, NaCl, sulfate, and CeO 2 . Preferably, Sb 2 O 3 is used as a fining agent, and preferably 0 to 0.5% is added.

[0054] When F is added to the glass, the volatilization amount of the glass raw materials increases, and it tends to cause environmental pollution and deterioration of the stripe pattern of the glass. Therefore, the glass of the present invention preferably does not contain F. In addition, when Ta 2 O 5 is added, the refractive index and cost of the glass increase significantly, and the meltability of the glass deteriorates. Therefore, it is preferable that the glass of the present invention does not contain Ta 2 O 5 .

[0055] <Components that should not be included> Oxides of Th, Cd, Tl, Os, Be, and Se have recently tended to be regulated as harmful chemicals, and measures for environmental protection are required not only in the glass manufacturing process but also in the processing and disposal after productization. Therefore, in situations where importance is attached to the impact on the environment, it is preferable not to contain them except when they are inevitably mixed. As a result, the glass is substantially free of substances that pollute the environment. Therefore, the glass of the present invention can be manufactured, processed, and disposed of without special environmental measures.

[0056] For environmental considerations, the glass of the present invention does not contain As 2 O 3 and PbO. As 2 O 3 has the effect of removing bubbles and further preventing the coloring of the glass. However, As 2 O 3When added, especially in a platinum furnace, the erosion of platinum by the glass progresses, the amount of platinum ions entering the glass increases, and it has an adverse effect on the life of the platinum furnace. It has an adverse effect on the life of the platinum furnace. PbO can significantly improve the high refractive index and high dispersion characteristics of the glass, but PbO is also As 2 O 3 is also an environmental pollutant.

[0057] The terms "not containing", "not adding", and "0%" described in this specification mean that compounds, molecules, elements, etc. were not intentionally added as raw materials for the glass of the present invention. However, as raw materials and / or equipment for manufacturing glass, impurities and components that were not intentionally added may be present in small or trace amounts in the final glass, and these are also the subject of the patent of the present invention.

[0058] Hereinafter, the characteristics of the glass material of the present invention will be described.

[0059] <Refractive Index and Abbe Number> The refractive index (nd) and Abbe number (ν d ) of the glass material have been tested according to the method specified in GB / T 7962.1-2010.

[0060] The lower limit value of the refractive index (nd) of the glass material of the present invention is 1.48, preferably 1.50, more preferably 1.51, and the upper limit value of the refractive index (nd) is 1.56, preferably 1.55, more preferably 1.54. The lower limit value of the Abbe number (ν d ) is 50, preferably 51, more preferably 53, and the upper limit value of the Abbe number (ν d ) is 58, preferably 57, more preferably 56.

[0061] <Acid Resistance Stability> The acid resistance stability (D A )(powder method) of the glass material is tested according to the method specified in GB / T 17129. In this specification, the acid resistance stability may be referred to as acid resistance or acid resistance stability.

[0062] The acid resistance stability (D A ) of the glass material of the present invention is two or more categories, preferably category 1.

[0063] <Water resistance stability> The water resistance stability (D W ) of the glass material (powder method) is tested according to the method specified in GB / T 17129. In this specification, the water resistance stability may be expressed as "water resistance" or "water resistance stability".

[0064] The water resistance stability (D W ) of the glass material of the present invention is two or more categories, preferably category 1.

[0065] <Alkali resistance stability> The alkali resistance stability of the glass material is measured according to the test conditions and requirements of ISO 10629 and is represented by the weight loss of the glass sample. The alkali resistance stability may be referred to as alkali resistance or alkali resistance stability in this specification.

[0066] This glass is processed into a test piece with a size of 30 mm × 30 mm × 2 mm, and after polishing all six sides, it is placed in 2000 ml of NaOH solution. With the concentration of the NaOH solution being 0.01 mol / L and the pH value being 12.0, the change in the pH value during the test is periodically observed with a pH meter, the reaction test solution is appropriately exchanged, and after erosion at 50 °C for 100 hours, the weight loss of the sample represented in mg is measured with an electronic balance.

[0067] The weight loss of the glass material of the present invention by the above test method is less than 9 mg, preferably less than 7 mg, more preferably less than 5 mg.

[0068] <Coefficient of thermal expansion> The coefficient of thermal expansion referred to in the present invention is the average coefficient of thermal expansion of the glass at 20 to 300 °C tested according to the method specified in GB / T7962.16 - 2010, and is represented by α 20-300℃ .

[0069] The average coefficient of thermal expansion (α20-300℃ ) has an upper limit of 90×10 -7 / K, preferably an upper limit of 85×10 -7 / K, more preferably an upper limit of 80×10 -7 / K, and the lower limit of the average coefficient of thermal expansion (α 20-300℃ ) is 60×10 -7 / K, preferably a lower limit of 65×10 -7 / K, more preferably a lower limit of 68×10 -7 / K.

[0070] <Light transmittance> The light transmittance described in the present invention refers to the internal transmittance at 360 nm of a 10-mm-thick glass sample, denoted as τ 360nm and is represented by, and is tested according to the method described in GB / T7962.12-2010.

[0071] The internal transmittance (τ 360nm ) at 360 nm of the glass material of the present invention is 78% or more, preferably 82% or more, more preferably 85% or more.

[0072] <Transition temperature> The transition temperature (T g ) of the glass is tested according to the method specified in GB / T7962.16-2010.

[0073] The upper limit of the transition temperature (T g ) of the glass of the present invention is 610 °C, preferably an upper limit of 600 °C, more preferably an upper limit of 580 °C, and the lower limit of the transition temperature (T g ) is 500 °C, preferably a lower limit of 520 °C, more preferably a lower limit of 530 °C.

[0074] <Young's modulus> The Young's modulus (E) of the glass is calculated by the following formula. TIFF2025087872000001.tif1342 Among them, TIFF2025087872000002.tif516 In the formula: E is the Young's modulus, in Pa. G is the shear modulus, in Pa. V T is the longitudinal wave velocity, in m / s. V S is the velocity of the transverse wave, in m / s. ρ is the density of the glass, g / cm 3 is.

[0075] The lower limit of the Young's modulus (E) of the glass material of the present invention is 6000×10 7 Pa, preferably the lower limit is 6500×10 7 Pa, more preferably the lower limit is 7000×10 7 Pa, and the upper limit of the Young's modulus (E) is 8500×10 7 Pa, preferably the upper limit is 8000×10 7 Pa.

[0076] <Bubble degree> Test the bubble degree of the glass material according to the test method specified in GB / T7962.8 - 2010.

[0077] The bubble degree of the glass material of the present invention is Class A or above, preferably Class A 0 class or above, more preferably Class A 00 class.

[0078] <Stripe> The stripe of the glass material is measured according to the method specified in MLL - G - 174B. Using a stripe meter composed of a point light source and a lens, compare and confirm the standard sample from the direction where the stripes are most visible. The grades are divided into 4 levels: A, B, C, and D. Grade A means no visible stripes under predetermined detection conditions, Grade B means fine and scattered stripes are visible under predetermined detection conditions, Grade C means slightly parallel stripes are visible under predetermined detection conditions, and Grade D means thick stripes are visible under predetermined detection conditions.

[0079] The glass material of the present invention has stripes of Grade C or above, preferably Grade B or above.

[0080] The glass material of the present invention having the excellent characteristics as described above can be widely used in the packaging fields of electronic devices and photosensitive devices, imaging devices, sensors, microscopes, medical technology, digital projection, communication, optical communication technology / information transmission, optical / lighting in the automotive field, the manufacture of glass components for various devices and equipment such as photolithography, excimer lasers, wafers, computer chips and integrated circuits, and electronic devices including them, or camera devices and equipment in the automotive field, surveillance / security field.

[0081] [Manufacturing Method] The glass of the present invention is manufactured by conventional raw materials such as carbonates, nitrates, sulfates, hydroxides, oxides and conventional processes. After doping by a conventional method, the prepared furnace materials are put into a melting furnace at 1300~1500°C and melted. Then, clarification, stirring and homogenization are carried out to obtain a homogeneous molten glass without bubbles and undissolved substances. This molten glass is put into a mold for casting and annealing. Those skilled in the art can appropriately select raw materials, manufacturing methods and process parameters according to the use.

Examples

[0082] To more clearly illustrate and exemplify the technical solutions of the present invention, the following non-limiting embodiments 1 to 20 are provided.

[0083] This embodiment uses the manufacturing method of the glass material described above to obtain a glass material having the compositions shown in Tables 1 to 2. In addition, the properties of each glass were measured by the test methods described in the present invention, and the results are shown in Tables 1 to 2.

[0084]

Table 1

[0085]

Table 2

Claims

1. A glass material comprising the following components in weight percent: SiO 2 : 55-70%, B 2 O 3 : 3-15%, TiO 2 : 0.5~10%, ZnO: 1~12%, Al 2 O 3 : 0.5-10%, Sodium 2 O+K 2 O: 5-22%, B 2 O 3 / SiO 2 is 0.06 to 0.26, (TiO 2 +ZnO) / Al 2 O 3 is 0.5 to 8.

0.

2. 10. The glass material of claim 1 further comprising the following components in weight percent: MgO+CaO+SrO+BaO: 0 to 10%; and / or Li 2 O: 0-5%; and / or P 2 O 5 : 0 to 5%; and / or ZrO 2 : 0 to 5%; and / or La 2 O 3 : 0 to 5%; and / or Y 2 O 3 : 0-5%; and / or Gd 2 O 3 : 0 to 5%, and / or Nb 2 O 5 : 0-5%, and / or WO 3 : 0-5%, and / or fining agents: 0-1%.

3. A glass material consisting of the following components in weight percent: SiO 2 : 55-70%, B 2 O 3 : 3-15%, TiO 2 : 0.5~10%, ZnO: 1~12%, Al 2 O 3 : 0.5-10%, Sodium 2 O+K 2 O: 5-22%, MgO + CaO + SrO + BaO: 0-10%, Li 2 O: 0-5%, P 2 O 5 : 0-5%, ZrO 2 : 0-5%, La 2 O 3 : 0-5%, Y 2 O 3 : 0-5%, Gd 2 O 3 : 0-5%, Nb 2 O 5 : 0-5%, WO 3 : 0-5%, clarifier: 0-1%, B 2 O 3 / SiO 2 is 0.06 to 0.26, (TiO 2 + ZnO) / Al 2 O 3 is 0.5 to 8.

0.

4. The glass material according to any one of claims 1 to 3, comprising the following components in weight percent: B 2 O 3 / SiO 2 is 0.08 to 0.2, and / or (TiO 2 +ZnO) / Al 2 O 3 is 0.7 to 7.0, and / or (SiO 2 +TiO 2 ) / (Na 2 O + ZnO) is 3.0 to 12.0; and / or ZnO / B 2 O 3 is 0.2 to 1.8; and / or (Na 2 O+K 2 O) / Al 2 O 3 is 0.8 to 8.0; and / or (Na 2 O+K 2 O) / (B 2 O 3 +ZnO) is 0.2 to 2.5; and / or (B 2 O 3 +K 2 O) / Al 2 O 3 is 1.0 to 10.0 and / or (MgO+CaO+SrO+BaO) / ZnO is 1.0 or less and / or (MgO+CaO+SrO+BaO) / Al 2 O 3 is 1.0 or less, and / or (MgO+CaO+SrO+BaO) / (Na 2 O+K 2 O) is less than 1.

0.

5. The glass material according to any one of claims 1 to 3, comprising the following components in weight percent: SiO 2 : 55-68%, and / or B 2 O 3 : More than 5% and 13% or less, and / or TiO 2 : 1.5-8%, and / or ZnO: 2-10%, and / or Al 2 O 3 : 1 to 8%, and / or Na 2 O+K 2 O: 6-20%, and / or MgO+CaO+SrO+BaO: 0-5%, and / or Li 2 O: 0-3% and / or P 2 O 5 : 0 to 3%, and / or ZrO 2 : 0 to 3%, and / or La 2 O 3 : 0 to 3%, and / or Y 2 O 3 : 0-3%, and / or Gd 2 O 3 : 0 to 3%, and / or Nb 2 O 5 : 0-3%, and / or WO 3 : 0-3%, and / or fining agents: 0-0.5%.

6. The glass material according to any one of claims 1 to 3, comprising the following components in weight percent: B 2 O 3 / SiO 2 is 0.1 to 0.18, and / or (TiO 2 +ZnO) / Al 2 O 3 is 1.0 to 5.0, and / or (SiO 2 +TiO 2 ) / (Na 2 O+ZnO) is 3.0 to 10.0, and / or ZnO / B 2 O 3 is 0.3 to 1.0, and / or (Na 2 O+K 2 O) / Al 2 O 3 is 1.0 to 6.0, and / or (Na 2 O+K 2 O) / (B 2 O 3 +ZnO) is 0.3 to 2.0, and / or (B 2 O 3 +K 2 O) / Al 2 O 3 is 1.5 to 8.0, and / or (MgO + CaO + SrO + BaO) / ZnO is 0.5 or less, and / or (MgO + CaO + SrO + BaO) / Al 2 O 3 is 0.5 or less, and / or (MgO + CaO + SrO + BaO) / (Na 2 O+K 2 O) is 0.5 or less.

7. The glass material according to any one of claims 1 to 3, comprising the following components in weight percent: SiO 2 : 60-68%; and / or B 2 O 3 : 6 to 12%; and / or TiO 2 : 2-7%; and / or ZnO: 3-8%; and / or Al 2 O 3 : 2-7%; and / or Na 2 O+K 2 O: 8-18%; and / or La 2 O 3 : 0 to 1%; and / or Y 2 O 3 : 0-1%; and / or Gd 2 O 3 : 0 to 1%; and / or Nb 2 O 5 : 0 to 1%; and / or WO 3 : 0-1%.

8. The glass material according to any one of claims 1 to 3, comprising the following components in weight percent: (SiO 2 +TiO 2 ) / (Na 2 O + ZnO) is 4.0 to 8.0; and / or ZnO / B 2 O 3 is 0.4 to 0.8; and / or (Na 2 O+K 2 O) / Al 2 O 3 is 1.5 to 5.0; and / or (Na 2 O+K 2 O) / (B 2 O 3 +ZnO) is 0.5 to 1.5; and / or (B 2 O 3 +K 2 O) / Al 2 O 3 is 2.0 to 6.0; and / or (MgO+CaO+SrO+BaO) / ZnO is 0.2 or less, and / or (MgO+CaO+SrO+BaO) / Al 2 O 3 is 0.2 or less, and / or (MgO+CaO+SrO+BaO) / (Na 2 O+K 2 O) is 0.2 or less.

9. The glass material according to any one of claims 1 to 3, comprising the following components in weight percent: Na 2 O: 2-12% and / or K 2 O: 2-12%, and / or MgO: 0-5%, and / or CaO: 0-5%, and / or SrO: 0-5%, and / or BaO: 0-5%.

10. By weight, Na 2 O: Contains 4-9% and / or K 2 O: containing 4-9%, and / or MgO: containing 0-2%, and / or CaO: containing 0-2%, and / or SrO: containing 0-2%, and / or BaO: containing 0-2%, and / or does not contain F, and / or Ta 2 O 5 does not contain Li; and / or 2 Does not contain O; and / or P 2 O 5 and / or ZrO 2 The glass material according to any one of claims 1 to 3, which does not contain

11. Weight percent La 2 O 3 , Y 2 O 3 , Gd 2 O 3 , Nb 2 O 5 and W.O. 3 The glass material according to any one of claims 1 to 3, wherein the total content of is 3% or less.

12. A refractive index of 1.48 to 1.56, and / or an Abbe number of 50 to 58, and / or a thermal expansion coefficient α 20-300℃ is 60×10 -7 / K~90×10 -7 / K, and / or Young's modulus is 6000×10 7 Pa or higher, and / or a transition temperature between 500°C and 610°C, and / or a bubble level of Class A or higher, and / or stripes of Class C or higher, and / or an acid resistance stability of Class 2 or higher, and / or a water resistance stability of Class 2 or higher, and / or a weight loss of the glass sample after the measurement of the alkali resistance according to the test conditions and requirements of ISO 10629 is less than 9 mg, and / or a light transmittance τ 360nm The glass material according to any one of claims 1 to 3, wherein the glass material has a refractive index of 78% or more.

13. Refractive index is 1.51 to 1.54; and / or Abbe number is 53 to 56; and / or coefficient of thermal expansion α 20-300℃ is 68 x 10 -7 / K~80×10 -7 / K; and / or Young's modulus is 7000×10 7 Pa~8000×10 7 Pa; and / or a transition temperature of 530°C to 580°C; and / or a cellularity of A 00 and / or the stripe is B grade or higher; and / or the acid resistance is Class 1; and / or the water resistance is Class 1; and / or the weight loss of the glass sample after the measurement of the alkali resistance according to the test conditions and requirements of ISO 10629 is less than 5 mg; and / or the light transmittance τ 360nm The glass material according to any one of claims 1 to 3, wherein the glass material is 85% or more.

14. The glass material according to any one of claims 1 to 13, for use in the field of packaging materials.

15. A glass member made of the glass material according to any one of claims 1 to 13.

16. A device comprising the glass material according to any one of claims 1 to 13, or comprising the glass member according to claim 15.

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