CN114716143B - Alkali-free boroaluminosilicate glass for liquid crystal glass substrate - Google Patents
Alkali-free boroaluminosilicate glass for liquid crystal glass substrate Download PDFInfo
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- CN114716143B CN114716143B CN202210386232.XA CN202210386232A CN114716143B CN 114716143 B CN114716143 B CN 114716143B CN 202210386232 A CN202210386232 A CN 202210386232A CN 114716143 B CN114716143 B CN 114716143B
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
- C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
- C03C3/093—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium containing zinc or zirconium
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
- C03B5/16—Special features of the melting process; Auxiliary means specially adapted for glass-melting furnaces
- C03B5/18—Stirring devices; Homogenisation
- C03B5/187—Stirring devices; Homogenisation with moving elements
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
- C03C1/004—Refining agents
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/50—Glass production, e.g. reusing waste heat during processing or shaping
- Y02P40/57—Improving the yield, e-g- reduction of reject rates
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Glass Compositions (AREA)
Abstract
The invention disclosesAn alkali-free boroaluminosilicate glass for a liquid crystal glass substrate belongs to the technical field of display glass. The technical scheme is as follows: comprises the following components in percentage by mole on the basis of oxides: siO 2 2 62‑72，Al 2 O 3 8‑12，B 2 O 3 3-6 parts of MgO 2-6 parts, 8-12 parts of CaO, 0-3 parts of SrO, 0-3 parts of BaO and 0-2 parts of ZnO. According to the invention, through reasonable proportioning of the components, the glass has short material property, high liquidus viscosity and low raw material cost.
Description
Technical Field
The invention relates to the technical field of display glass, in particular to alkali-free boroaluminosilicate glass for a liquid crystal glass substrate.
Background
Substrate glass for flat panel displays is roughly classified into alkali glass containing alkali metal oxide and alkali-free glass containing no alkali metal oxide. Alkali glass substrates are used for Plasma Displays (PDPs), inorganic field emission displays, field Emission Displays (FEDs), etc., and alkali-free glass substrates are used for Liquid Crystal Displays (LCDs), organic field emission displays (OLEDs), etc.
Among them, glass substrates for LCDs and the like are required to have the following characteristics because a thin film of a metal or a metal oxide is formed on the surface thereof. No alkali metal ion (in order to prevent deterioration of film characteristics due to diffusion of alkali metal oxide in the glass substrate as an alkali metal ion in the thin film); has a high strain point (for minimizing deformation and shrinkage of a glass substrate caused by exposure of the glass substrate to a high temperature in a process of forming a Thin Film Transistor (TFT)); chemical durability sufficient for various chemical agents used for TFT formation, particularly durability against buffered hydrofluoric acid (hydrofluoric acid + ammonium fluoride, BHF) used for etching SiOx or SiNx, a chemical solution containing hydrochloric acid used for etching ITO (indium oxide doped with tin), various acids (nitric acid, sulfuric acid, etc.) used for etching metal electrodes, or a protective film-removing solution against alkalinity; the defects (bubbles, striae, impurities, undissolved substances, pits, cracks, etc.) that affect the display of the display are not caused to the inside and the surface of the glass substrate.
The production process of the liquid crystal display is very complicated and the properties of the substrate glass are very important. Most importantly, the surface quality and the external dimensions of the glass substrate used for producing the TFT-LCD device must be strictly controlled. The fusion downdraw process is capable of producing glass sheets that can be used as the above-described substrates and does not require costly post-processing operations such as grinding and polishing. However, the glass forming process has quite strict limitation on the viscosity-temperature characteristics of the glass, firstly needs to have shorter material property, is convenient for the glass to be rapidly shaped in forming equipment, and needs higher liquidus viscosity to ensure that the product waste caused by crystallization cannot be caused in the continuous production process of the glass.
Disclosure of Invention
The invention aims to provide the flat glass of the TFT-LCD liquid crystal display, which has short material property, high liquidus viscosity and low raw material cost through the reasonable proportioning of all components.
The technical scheme of the invention is as follows:
alkali-free boroaluminosilicate glass for liquid crystal glass substrates comprising the following components in mole percent on an oxide basis: siO 2 2 62-72，Al 2 O 3 8-12，B 2 O 3 3-6，MgO 2-6，CaO 8-12，SrO 0-3，BaO 0-3，ZnO 0-2。
Preferably, the glass is SiO in mole percent based on oxide 2 、Al 2 O 3 、B 2 O 3 MgO, caO, srO, baO and ZnO have the following relationships: caO is more than MgO + SrO + BaO; b is 2 O 3 +ZnO＞MgO；Al 2 O 3 -CaO＜ZnO；CaO＞B 2 O 3 ×2。
The glass meeting the condition has a smaller material index, namely the glass has short material property so that the glass is easy to form in the production process. Defining the material property index as: the third power of the difference between the softening point and the annealing point divided by the sixth power of ten, the smaller the index of the glass frit is, the shorter the glass frit property is.
Preferably, the glass comprises the following components in mole percentage on the basis of oxides: siO 2 2 63-68，Al 2 O 3 8-10，B 2 O 3 3-6，MgO 4-6，CaO 8-10，SrO 1-2，BaO 1-3，ZnO 0-1。
Preferably, the glass has a strain point greater than 660 ℃.
Preferably, the glass has a 200 poise temperature of less than 1600 ℃.
Preferably, the glass has a temperature of 60000 poise of greater than 1220 ℃.
Preferably, the glass has a liquidus viscosity of greater than 350000 poise.
Preferably, the glass has a Young's modulus of greater than 72 GPa.
The alkali-free glass of the present invention is substantially free of alkali metal oxide and is formed of SiO 2 、Al 2 O 3 、B 2 O 3 The glass with the basic composition of MgO, caO, srO, baO and ZnO has the viscosity of 200 poise, the temperature is below 1600 ℃, if the temperature exceeds 1600 ℃, higher temperature is required for clarification, the defects are that more energy is consumed, the corrosion of refractory materials is accelerated, and the service life of a melting tank furnace is shortened. The temperature when the viscosity reaches 60000 poise is above 1220 ℃, the liquidus viscosity is above 350000 poise, the short material property of the glass is ensured, and meanwhile, the liquidus viscosity is far higher than the viscosity required by a glass forming area of 60000 poise, and the crystallization reaction is not generated in the glass forming process, so that the product defect is caused.
In addition, the strain point of the alkali-free glass is more than 660 ℃, so that the glass can be prevented from generating larger deformation due to repeated heating in the panel manufacturing process, and further the manufacturing yield is influenced.
[SiO 2 ]
SiO as a raw material for the alkali-free glass of the present invention 2 Is a network former and is an essential component. SiO 2 2 The increase of the content can effectively improve the strain point and the Young modulus and reduce the density of the glass. Considering that the viscosity of the glass is too high, the molar percentage is below 72, preferably below 68; on the contrary, the molar percentage is 62 or more, preferably 63 or more, because it causes deterioration of acid resistance, increase of density, decrease of strain point, increase of linear expansion coefficient, and decrease of young's modulus.
[Al 2 O 3 ]
In the alkali-free glass of the present invention, al 2 O 3 Is a component for increasing the strain point, suppressing the phase separation of the glass, and increasing the Young's modulus. The mole percentage is more than 8. However, in order to avoid deterioration of the glass due to high viscosity and devitrification, the molar percentage is 12 or less, preferably 10 or less.
[B 2 O 3 ]
B 2 O 3 Is a good glass fluxing agent, but in order to ensure low production cost, the mol percentage should be controlled to be 3-6 under the conditions of ensuring the glass characteristics and the melting difficulty.
[MgO]
In the alkali-free glass of the present invention, mgO is a component for reducing the viscosity of the glass, and the molar percentage thereof is 2 to 6. The alkaline earth metal oxide preferably contains MgO because it has a reduced density, does not increase the linear expansion coefficient, does not excessively lower the strain point, and improves the meltability. The mole percentage is more than 2, preferably more than 4; however, in order to avoid phase separation of the glass and deterioration of devitrification properties and acid resistance, the molar percentage is 6 or less.
[CaO]
CaO in the glass of the type belongs to a network outer body of a glass network structure, plays a role in gathering the glass network structure, and can effectively reduce the melting temperature of the glass and keep a higher strain point; and more CaO reduces the chemical resistance and bending strength of the glass, so the content of CaO is controlled to be 8-12, and more preferably 8-10.
[SrO]
SrO functions similarly to BaO, the density of the glass with an excessive content becomes large, the shear strain point is greatly lowered, and the price of strontium carbonate as a raw material for providing SrO is high, so that the molar percentage of SrO is 0-3, more preferably 1-2.
[BaO]
BaO has a role of lowering the melting temperature of the glass and reducing the tendency of the glass to devitrify, but too high a content results in too high a density of the glass and thus too heavy a product, so that the molar percentage of BaO is determined to be 0 to 3, more preferably 1 to 3.
[ZnO]
ZnO can reduce the high-temperature viscosity of the glass, increase the chemical resistance of the glass and reduce the thermal expansion coefficient of the glass. However, when the content is too large, the strain point of the glass is remarkably lowered and the tendency of the glass to devitrify is increased, so that the molar percentage of ZnO is 0 to 2, preferably 0 to 1.
Compared with the prior art, the invention has the following beneficial effects:
the glass has short material property, and is convenient for rapid shaping in a forming device; has high liquidus viscosity, and greatly reduces the probability of crystallization in the continuous production process of the glass. The glass containing the component provides a wider process band for production, the fluctuation resistance is higher, and the long-term yield of products is indirectly and greatly improved. While the glass is produced using a higher proportion of lower cost raw materials (e.g., calcium carbonate to provide CaO and barium carbonate to provide BaO) and a lower proportion of higher cost raw materials (e.g., strontium carbonate to provide SrO and barium carbonate to provide B) 2 O 3 The boric anhydride), the raw material purchasing cost is greatly reduced, and the cost benefit is remarkable.
Detailed Description
The present invention is further illustrated by the following examples, which are not intended to limit the practice of the invention.
Examples and comparative examples
The glass compositions of examples 1 to 5 and comparative examples 1 to 3 are shown in Table 1. The glass samples were all produced by the following method: according to the principle that the amount of the obtained glass is 1000g, the required raw materials are calculated according to the glass components, the raw materials are sequentially weighed and placed into a mixer to be uniformly stirred and mixed, then the mixture is poured into a platinum-rhodium crucible, the platinum-rhodium crucible is placed into a high-temperature electric furnace to be melted for 4 hours at 1580 ℃, and then the mixture is heated to 1650 ℃ to be melted for 5 hours. In the melting process, a platinum rod is used for stirring and discharging air bubbles, so that molten glass is homogenized, and then the molten glass is poured into a fully preheated metal mold for cooling and shaping. And fully annealing the shaped glass ingot to eliminate the residual stress. And then carrying out various performance tests on the glass, including testing the annealing strain point of the glass by a wire drawing method, testing the high-temperature viscosity of the glass by a rotary high-temperature viscometer, testing the liquidus temperature of the glass by a gradient temperature furnace, obtaining the corresponding liquidus viscosity according to the tested viscosity-temperature curve, and testing the Young modulus of the glass by an intrinsic mechanics tester. The results of the tests are shown in Table 2.
TABLE 1
TABLE 2
As can be seen from the test results in Table 2, the glass of the present invention has a strain point of greater than 660 ℃, a 200 poise temperature of less than 1600 ℃, a 60000 poise temperature of greater than 1220 ℃, a liquidus viscosity of greater than 350000 poise, and a Young's modulus of greater than 72 GPa.
The glass compositions and the glass composition and the material index of examples 6 to 9 and comparative examples 4 to 7 are shown in Table 3:
TABLE 3
As can be seen from Table 3, in the glass of the present invention, siO is present 2 、Al 2 O 3 、B 2 O 3 MgO, caO, srO, baO and ZnO have the following relationships: caO is more than MgO + SrO + BaO; b 2 O 3 +ZnO＞MgO；Al 2 O 3 -CaO＜ZnO；CaO＞B 2 O 3 X 2, the glass has a shorter glass gob index than the glass of the comparative example not having the above relationship, making it easier to mold during production.
Although the present invention has been described in detail by referring to the preferred embodiments, the present invention is not limited thereto. Various equivalent modifications or substitutions can be made on the embodiments of the present invention by those skilled in the art without departing from the spirit and scope of the present invention, and these modifications or substitutions are within the scope of the present invention/any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (6)
1. Alkali-free boroaluminosilicate glass for liquid crystal glass substrates, characterized by comprising the following components in mole percent on an oxide basis: siO 2 2 63-68，Al 2 O 3 8-10，B 2 O 3 3-6 parts of MgO 4-6 parts, 8-10 parts of CaO, 1-2 parts of SrO, 1-3 parts of BaO and 0-1 part of ZnO; the glass has SiO in mol percent based on oxide 2 、Al 2 O 3 、B 2 O 3 MgO, caO, srO, baO and ZnO have the following relationships: caO is more than MgO + SrO + BaO; b 2 O 3 +ZnO＞MgO；Al 2 O 3 -CaO＜ZnO；CaO＞B 2 O 3 ×2。
2. The alkali-free boroaluminosilicate glass for a liquid crystal glass substrate of claim 1, wherein the glass has a strain point greater than 660 ℃.
3. The alkali-free boroaluminosilicate glass for a liquid crystal glass substrate of claim 1, wherein the glass has a 200 poise temperature of less than 1600 ℃.
4. The alkali-free boroaluminosilicate glass for liquid crystal glass substrates of claim 1, wherein the glass has a temperature of 60000 poise greater than 1220 ℃.
5. The alkali-free boroaluminosilicate glass for a liquid crystal glass substrate according to claim 1, wherein the glass has a liquidus viscosity of greater than 350000 poise.
6. The alkali-free boroaluminosilicate glass for liquid crystal glass substrates of claim 1, wherein the glass has a young's modulus greater than 72 GPa.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202210386232.XA CN114716143B (en) | 2022-04-13 | 2022-04-13 | Alkali-free boroaluminosilicate glass for liquid crystal glass substrate |
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| CN202210386232.XA CN114716143B (en) | 2022-04-13 | 2022-04-13 | Alkali-free boroaluminosilicate glass for liquid crystal glass substrate |
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| CN114716143B true CN114716143B (en) | 2022-12-13 |
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| JP5435394B2 (en) * | 2007-06-08 | 2014-03-05 | 日本電気硝子株式会社 | Tempered glass substrate and manufacturing method thereof |
| CN102584008B (en) * | 2011-12-20 | 2014-10-22 | 东旭集团有限公司 | Formula for light environment-friendly alkali-free boron-alumina silicate glass used in liquid crystal display (LCD) |
| CN104276754A (en) * | 2013-08-27 | 2015-01-14 | 东旭集团有限公司 | Silicate glass substrate for flat-panel display |
| CN107382054A (en) * | 2017-08-10 | 2017-11-24 | 东旭科技集团有限公司 | Alumina silicate glass and its preparation method and application |
| CN107572775A (en) * | 2017-09-27 | 2018-01-12 | 广东星弛光电科技有限公司 | Suitable for the Boroalumino silicate glasses of the not alkali metal containing of flat-panel monitor |
| CN109160727B (en) * | 2018-10-16 | 2020-10-13 | 东旭光电科技股份有限公司 | Aluminosilicate glass composition, aluminosilicate glass, and preparation method and application thereof |
| CN109608039A (en) * | 2019-02-20 | 2019-04-12 | 武汉理工大学 | A kind of Aluminiu, boron silicate glass without alkali and its application |
| CN110255894A (en) * | 2019-04-26 | 2019-09-20 | 武汉理工大学 | High elastic modulus Aluminiu, boron silicate glass without alkali and preparation method thereof suitable for floating process production |
| CN111018345A (en) * | 2019-11-23 | 2020-04-17 | 石家庄旭新光电科技有限公司 | Composition for aluminosilicate glass for OLED panel, aluminosilicate glass and preparation method thereof |
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