CN101838105A - TFT-LCD glass substrate and compound composition thereof - Google Patents
TFT-LCD glass substrate and compound composition thereof Download PDFInfo
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- CN101838105A CN101838105A CN200910074313A CN200910074313A CN101838105A CN 101838105 A CN101838105 A CN 101838105A CN 200910074313 A CN200910074313 A CN 200910074313A CN 200910074313 A CN200910074313 A CN 200910074313A CN 101838105 A CN101838105 A CN 101838105A
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Abstract
The invention relates to a TFT-LCD glass substrate and the compound composition thereof; the glass substrate comprises the following components by the mass percentage of oxide: 56 to 64 percent of SiO2, 7 to 11 percent of B2O3, 14 to 18 percent of Al2O3, 0.01 to 10 percent of BaO, 3 to 8 percent of CaO, 0.5 to 8 percent of SrO, 0 to 0.5 percent of ZnO, 0 to 4 percent of MgO, and 0 to 0.5 percent of ZrO2. The content of SiO2+B2O3 in the components of the glass substrate is 63 to 75 percent, the content of B2O3+ Al2O3 is 21 to 29 percent and the content of CaO+ MgO+other RO is 3 to 13 percent; and R refers any one oxide or the mixture of any two or more than two oxides of Be, Sr and Ba.
Description
Technical field
The present invention relates to a kind of alkaline earth boron lead glass design of components, it can be widely used in making the glass substrate of liquid-crystal display, is referred to as the TFT-LCD glass substrate in the industry.
Background technology
Lcd technology has become the gordian technique of modern most important picture transmission and reproduction.The video picture principle of liquid-crystal display is fairly simple.Material has three-state: solid-state, liquid state and gaseous state, three-state only is classification roughly in fact.The solid-state of some material can be segmented out morphological structure of different nature again.Equally, liquid can have different " attitude " too, wherein molecular arrangement have directivity liquid we just be referred to as " liquid crystal ", be called for short in " liquid crystal ".
With the assembly that liquid crystal is made, be that liquid crystal is wrapped in two parallel plate glass.The material that one deck is called the orientation agent is plated on surface at glass, its characteristic decision liquid crystal form and arranging situation.
The video picture principle of liquid-crystal display, be that liquid crystal is placed between two conductive glass, driving by electric field between two electrodes, cause the electrical effect of liquid crystal molecule twisted-nematic, with control light source transmission or shielding function, close at power supply and to produce light and shade between opening and image is shown, if add colored filter, but display color image then.On two sheet glass substrates, alignment film is housed, so liquid crystal can be along the groove orientation, because glass substrate alignment film groove departs from 90 degree, so liquid crystal molecule becomes twist mode, when glass substrate does not add electric field, light is followed liquid crystal to do 90 degree through Polarizer and is reversed, by the below Polarizer, and the liquid crystal panel display white; When glass substrate added electric field, liquid crystal molecule produces assortment to be changed, and light is kept former direction by the liquid crystal molecule space, is covered by the below Polarizer, and light is absorbed and can't appears, and liquid crystal panel shows black.Liquid-crystal display is to have or not according to this voltage, makes panel reach display effect.
Each pixel of TFT-LCD all is to be controlled by the TFT that is integrated in from one's body, and they are active pixel points.Therefore, not only the reaction times can accelerate greatly; Contrast gradient and brightness have also improved greatly; Resolving power has also obtained unprecedented lifting simultaneously.Because it has higher contrast gradient and abundant colors more, the fluorescent screen renewal frequency is also faster, so we are referred to as " very color ".
TFT liquid-crystal display mode has than old-fashioned LCD and shields fast 600 times pixel response speed.Advanced silicon electrode adds, and has accelerated the pixel response speed of LCD screen greatly, reduces the phenomenon that delays of picture appearance.Glass substrate has been proposed higher technical requirements, the geometrical dimension of the substrate after the processing is the influence of heating condition not, the thermal expansivity that is this class glass substrate is little, and the stress resultant of the production in making according to glass substrate considers that the optimal heat coefficient of expansion is 28 * 10
-7/ ℃ about.
Like this to the having higher requirement of the composition of glass substrate, to guarantee to adapt to the requirement of modern liquid crystal displays.Glass substrate must have following characteristic: contain alkalimetal oxide and be less than 1000ppm; The tool chemical resistant properties; Thermal expansivity must be close with the silicon of thin film transistor; Improve strain point of glass, to reduce the thermal contraction trial of strength.
The glass substrate that TFT-LCD uses must possess following basic physical property according to the technological standard of liquid-crystal display:
1, the thermal expansivity of glass substrate must be enough low, is not higher than 40 * 10
-7/ ℃;
2, the strain point temperature of glass substrate should be higher than 640 ℃;
3, density is lower than 2.6g/cm
3, and light more good more.
The improvement of the glass substrate that TFT-LCD is used is just carried out according to above principle at present.
Summary of the invention
The object of the present invention is to provide the design of components of the more perfect LCD glass substrate of a kind of performance, so that have breakthrough on the technical indicator that the glass substrate that the TFT-LCD that makes uses is little in density, coefficient of expansion variation is little, strain point is high, transmittance is high.
To achieve these goals, the present invention is by the following technical solutions:
A kind of chemical association composition of TFT-LCD glass substrate represents that with oxide compound key is: contain mass percent 56～64%SiO in the TFT-LCD glass substrate
2, 7～11%B
2O
3, 14～18%Al
2O
3, 0.01～10%BaO, 3～8%CaO, 0.5～8%SrO, 0～0.5%ZnO, 0～4%MgO, 0～0.5%ZrO
2
SiO in the above TFT-LCD glass substrate component
2+ B
2O
3Content be 63～75%, B
2O
3+ Al
2O
3Content be 21～29%, the content of other RO of CaO+MgO+ is 3～13%, above-mentioned R represents any one oxide compound or the mixing of two or more oxide compound arbitrarily among Be, Sr, the Ba.
The liquid crystal glass base of producing by means of TFT-LCD glass substrate component principle provided by the invention can reach following technical indicator after testing:
At 10 ℃～300 ℃ thermal expansivity is 31～39 * 10
-7/ ℃; Strain point is more than 640 ℃, and density is less than 2.6g/cm
3, visible light transmissivity can reach more than 91% in 377nm～1000nm wavelength.
Its this physical property of above liquid crystal glass base can be stable reach:
Thermal expansivity is lower than 40 * 10
-7/ ℃ (10～300 ℃), strain point temperature is higher than 640 ℃, and density is lower than 2.6g/cm
3, liquidus temperature is lower than 1150 ℃, and liquidus viscosity is greater than 250,000 pools, and young's modulus is greater than 7100kg/mm
2, the bubbles number of bubble diameter in＞0.1mm is invisible etc. in the per kilogram glass substrate.Requirement strain point height helps to prevent in hot-work subsequently owing to shrink the glass substrate distortion that causes.
Embodiment
The present invention is when implementing, be after the raw material that will include the corresponding oxide mass per-cent of above-mentioned each glass substrate component earlier evenly mixes, again with the mixing raw material melt-processed, stir the discharge bubble and make the glass metal homogenizing with the platinum rod, then its temperature is reduced to the needed glass substrate forming temperature range of moulding, pass through annealing theory, produce the thickness of the glass substrate of liquid-crystal display needs, glass substrate to moulding carries out simple cold work again, and the basic physical property of liquid crystal glass base is tested becomes qualified product at last.
Chemical resistant properties is meant the various etchant solutions erosive stability to using in the processing procedure process.The dry etching condition erosive stability that adopts during particularly to etch silicon layer.A benchmark of dry etching condition is that substrate sample is contacted with etchant solutions.This test is that glass sample is placed in the solution 5 minutes, and mg/cm is pressed in the gravimetry loss
2Calculate, determine chemical resistant properties.
Below in conjunction with specific embodiment the present invention is described in further detail.
The present invention is a kind of component design of TFT-LCD glass substrate, represents that with oxide compound it is characterized in that: containing mass percent in the TFT-LCD glass substrate is 56～64%SiO
2, 7～11%B
2O
3, 14～18%Al
2O
3, 0.01～10%BaO, 3～8%CaO, 0.5～8%SrO, 0～0.5%ZnO, 0～4%MgO, 0～0.5%ZrO
2
SiO in the above-mentioned TFT-LCD glass substrate component
2+ B
2O
3Content be 63～75%, B
2O
3+ Al
2O
3Content be 21～29%, the content of other RO of CaO+MgO+ is 3～13%, above R represents any one oxide compound or the mixing of two or more oxide compound arbitrarily among Be, Sr, the Ba.
In the above TFT-LCD glass substrate component, increase total mass and be not more than 1% beryllium oxide.
Can also in the above TFT-LCD glass substrate component, increase total mass and be not more than 1% stannic oxide.
Contain following at least a compound in the TFT-LCD glass substrate component noted earlier: BeO, SnO
2And Cl, and in described TFT-LCD glass substrate component BeO+SnO
2The shared mass percent of+Cl is 0.1～1%.
Light transmission rate by means of the prepared glass of the present invention is 91%; At 10 ℃～300 ℃ thermal expansivity is 31～39x10
-7℃; Strain point is more than 640 ℃, and density is less than 2.6g/cm
3, liquidus temperature is lower than 1150 ℃.
In the present invention, SiO
2Content be 56～64%.Improve SiO
2Content helps the glass lightweight, and thermal expansivity reduces, and chemical resistant properties increases, but the high temperature viscosity rising is unfavorable for fusion like this, and general kiln is difficult to satisfy, so determine SiO
2Content be 56～64%.
B
2O
3Content be 7～11%, B
2O
3Effect more special, also be a kind of good fusing assistant, it can generate glass, B under the high temperature melting condition separately
2O
3Be difficult to form [BO
4], can reduce high temperature viscosity, B has the free oxygen of capturing to form [BO during low temperature
4] trend, be that structure is tending towards closely, improve the low temperature viscosity of glass, prevent the generation of crystallization phenomenon.But too much B
2O
3Strain point of glass is reduced, so B
2O
3Content be defined as 7～11%.
Al
2O
3Content be 14～18%, in order to improve the intensity of glass structure, high-load Al
2O
3Help increasing of strain point of glass, bending strength, but the crystallization phenomenon appears in too high glass easily, so Al
2O
3Content be defined as 14～18%.
Silicon oxide and aluminum oxide constitute the main body of glass network structure jointly, make glass substrate more stable, are not easy to be subjected to extraneous erosion.So determine that summation content is 70%～82%.
The effect of aluminum oxide and boron oxide is to affect glass viscosity and melting temperature (Tm).
The content of CaO is 3～8%, fusion and the adjustment glass ware forming of calcium oxide in order to promote glass.If calcium oxide content is less than 3%, can't reduce the viscosity of glass, content is too much, and crystallization can appear in glass easily, and also amplitude variation is big greatly for thermal expansivity, and is unfavorable to successive process.So the content of CaO is defined as 3～8%.
The content of BaO is 0.01～10%, and barium oxide is as fusing assistant and prevent that crystallization from appearring in glass, if content is too much, glass density can be too high, causes the quality of product overweight.So the content of BaO is defined as 0.01～10%.
The content of SrO is 0.5～8%, and strontium oxide is similar to barytic effect, and content is too much, and the density of glass can become greatly, and strain point can reduce significantly.So the content of SrO is defined as 0.5～8%.
The content of ZnO is 0～0.5%, and zinc oxide can reduce glass viscosity, increases the chemical resistant properties of glass, reduces the thermal expansivity of glass.Content too much can make the strain point of glass reduce significantly.So the content of ZnO is defined as 0～0.5%.
The content of MgO is 0～4%, and the viscosity of magnesium oxide glass metal when reducing molten glass is used to reduce the bubble or the content of impurity wherein and adjusts glass ware forming, but the content of magnesia height, the crystallization phenomenon appears in glass easily.Therefore the content of MgO is defined as 0～4%.ZrO
2Content be 0～0.5%, the combination of zirconium white and zinc oxide also helps the performance of the acid resistance, elasticity, bending strength and the thermal expansion aspect that improve glass.So ZrO
2Content be defined as 0～0.5%.
Among the present invention, also can one in the glass composition be added with 0.1～1% finings, wherein finings is BeO, SnO
2With wherein one or more of Cl, to improve the fusion quality of glass.If content is few, the effect of its clarification or de-bubble is bad, and glass substrate printing opacity rate variance can produce numerous air-bubble in addition; If content is too much, can cause glass substrate flavescence or blackout etc., also influence transmittance.
Below further specify the present invention with embodiment, but the purpose of data is explanation and example, also uses the physical property of some glass substrates.
In the composition and the physical property of table one, the made glass substrate sample of table two (example 1 is to example 16) data based the present invention, implementation data promptly of the present invention.
At the glass substrate sample of table one, table two, all be in order to the below manufactured; Each composition is to get raw material commonly used, according to the weight percent of correspondence uniform mixing in addition, pass through 1650～1700 ℃ temperature again, high-temperature digestion is 14～20 hours in platinum crucible, in the fusion processes, stir with the platinum stirring rod, to promote the homogeneity of each composition in the glass, then its temperature is reduced to the needed glass substrate forming temperature range of moulding, pass through annealing theory, produce the thickness of the glass substrate of liquid-crystal display needs, the glass substrate to moulding carries out simple cold work again, at last its this physical property of liquid crystal glass base is tested.Can obtain characteristic datas such as thermal expansivity, strain point, density, liquidus temperature, number of bubbles respectively, be presented at respectively below the example 1～example 16 of table one, table two.
Concrete data in following examples are component measured datas in the actual TFT-LED product when adding finings.As not adopting under the situation that increases finings, in following examples short constituent mass ratio, evenly B is gone at the stand respectively
2O
3, Al
2O
3, among the CaO in one or both the component.
Table one
| Oxide compound is formed | Test example 1 | Test example 2 | Test example 3 | Test example 4 | Test example 5 | Test example 6 | Test example 7 | Test example 8 |
| ??SiO 2 | ??56 | ??56.4 | ??56.8 | ??57 | ??57.4 | ??57.6 | ??58.9 | ??59.1 |
| ??B 2O 3 | ??10 | ??11 | ??10 | ??10.8 | ??10 | ??9.5 | ??7 | ??9.5 |
| ??Al 2O 3 | ??14 | ??15 | ??16.8 | ??17.6 | ??14.8 | ??15 | ??17.34 | ??15.1 |
| ??BaO | ??7 | ??5 | ??6 | ??1.5 | ??6 | ??3.2 | ??4.8 | ??4.2 |
| ??CaO | ??8 | ??7.3 | ??5 | ??7.6 | ??7.8 | ??7 | ??6.7 | ??7.2 |
| ??SrO | ??3.9 | ??4.8 | ??2.7 | ??1.5 | ??1.2 | ??4.6 | ??0.6 | ??0.5 |
| ??ZnO | ??0 | ??0 | ??0.3 | ??0.5 | ??0.5 | ??0.07 | ??0.3 | ??0.4 |
| ??MgO | ??0.6 | ??0 | ??1.3 | ??2.44 | ??1.45 | ??2.33 | ??3.66 | ??3 |
| ??ZrO | ??0 | ??0 | ??0.1 | ??0.06 | ??0.15 | ??0.4 | ??0.5 | ??0.5 |
| ??SiO 2+B 2O 3 | ??66 | ??67.4 | ??66.8 | ??67.8 | ??67.4 | ??67.1 | ??65.9 | ??68.6 |
| ??B 2O 3+Al 2O 3 | ??24 | ??26 | ??26.8 | ??28.4 | ??24.8 | ??24.5 | ??24.34 | ??24.6 |
| ??CaO+MgO+RO | ??9.1 | ??7.8 | ??7.3 | ??11.04 | ??9.95 | ??9.63 | ??10.56 | ??10.7 |
| ??BeO+SnO 2+Cl | ??0.5 | ??0.5 | ??1 | ??1 | ??0.7 | ??0.3 | ??0.2 | ??0.5 |
| Thermal expansivity (x10 -7/℃) | ??39 | ??39 | ??35.3 | ??37.6 | ??36.2 | ??34.6 | ??35 | ??34.7 |
| The glass liquidus temperature (℃) | ??1160 | ??1200 | ??1190 | ??1210 | ??1215 | ??1190 | ??1235 | ??1145 |
| Strain point (℃) | ??665 | ??670 | ??672 | ??678 | ??663 | ??660 | ||
| Density (2.6g/cm 3) | ??2.55 | ??2.53 | ??2.5 | ??2.45 | ??2.38 | ??2.37 | ??2.45 | ??2.43 |
| Oxide compound is formed | Test example 1 | Test example 2 | Test example 3 | Test example 4 | Test example 5 | Test example 6 | Test example 7 | Test example 8 |
| Light transmission rate (%) | ??91.5 | ??92.2 | ??93 | ??92.7 | ??92.8 | ??92.4 | ||
| Young's modulus (kg/mm 2) | ??7150 | ??7140 | ??7160 | ??7180 | ??7190 | ??7178 | ??7200 | ??7280 |
| Number of bubbles (individual) | ??0 | ??0 | ??0 | ??0 | ??0 | ??0 | ??0 | ??0 |
Table two
| Oxide compound is formed | Test example 9 | Test example 10 | Test example 11 | Test example 12 | Test example 13 | Test example 14 | Test example 15 | Test example 16 |
| ??SiO 2 | ??59.6 | ??59.9 | ??60.4 | ??60.8 | ??61.6 | ??62.4 | ??63.2 | ??63.8 |
| ??B 2O 3 | ??11 | ??10.8 | ??10.6 | ??10 | ??9.7 | ??10.2 | ??9.7 | ??9.6 |
| ??Al 2O 3 | ??16.6 | ??14.2 | ??14.6 | ??15.2 | ??14.8 | ??15.8 | ??16.4 | ??17.56 |
| ??BaO | ??2.5 | ??1.5 | ??1.4 | ??4.2 | ??3.4 | ??2.3 | ??2.2 | ??0.3 |
| ??CaO | ??7.9 | ??7.5 | ??8 | ??6.5 | ??7.4 | ??7.6 | ??7.04 | ??7.2 |
| ??SrO | ??2.1 | ??5.6 | ??3.6 | ??1.3 | ??1.5 | ??0.8 | ??0.6 | ??0.3 |
| ??ZnO | ??0 | ??0 | ??0 | ??0 | ??0.4 | ??0 | ??0 | ??0.5 |
| ??MgO | ??0 | ??0 | ??0.8 | ??0.8 | ??0 | ??0 | ??0 | ??0 |
| ??ZrO | ??0 | ??0 | ??0.1 | ??0.2 | ??0.5 | ??0.3 | ??0.16 | ??0.24 |
| ??SiO 2+B 2O 3 | ??70.6 | ??70.7 | ??71 | ??70.8 | ??71.3 | ??72.6 | ??72.9 | ??73.4 |
| ??B 2O 3+Al 2O 3 | ??27.6 | ??25 | ??25.2 | ??25.2 | ??24.5 | ??26 | ??26.1 | ??27.16 |
| ??CaO+MgO+RO | ??8.2 | ??8 | ??9.3 | ??8.3 | ??8.1 | ??8.2 | ??7.74 | ??7.7 |
| ??BeO+SnO 2+Cl | ??0.3 | ??0.5 | ??0.5 | ??1 | ??0.7 | ??0.6 | ??0.7 | ??0.5 |
| Thermal expansivity (x10 -7/℃) | ??33 | ??34 | ??33 | ??32 | ??31 | ??32 | ??35 | ??33 |
| Oxide compound is formed | Test example 9 | Test example 10 | Test example 11 | Test example 12 | Test example 13 | Test example 14 | Test example 15 | Test example 16 |
| The glass liquidus temperature (℃) | ??1125 | ??1100 | ??1128 | ??1148 | ??1057 | ??1060 | ??1102 | ??1091 |
| Strain point (℃) | ??667 | ??668 | ??669 | ??678 | ??666 | ??661 | ??671 | ??671 |
| Density (2.6g/cm 3) | ??2.384 | ??2.39 | ??2.38 | ??2.386 | ??2.394 | ??2.358 | ??2.388 | ??2.391 |
| Light transmission rate (%) | ??96 | ??96 | ??96 | ??96 | ??96.8 | ??95.8 | ??96.2 | ??97 |
| Young's modulus (kg/mm 2) | ??7450 | ??7350 | ??7440 | ??7410 | ??7600 | ??7550 | ??7500 | ??7580 |
| Number of bubbles (individual) | ??0 | ??0 | ??0 | ??0 | ??0 | ??0 | ??0 | ??0 |
Claims (7)
1. the chemical association composition of a TFT-LCD glass substrate is represented with oxide compound, it is characterized in that: contain mass percent 56～64%SiO in the TFT-LCD glass substrate
2, 7～11%B
2O
3, 14～18%Al
2O
3, 0.01～10%BaO, 3～8%CaO, 0.5～8%SrO, 0～0.5%ZnO, 0～4%MgO, 0～0.5%ZrO
2
2. according to the chemical association composition of the described TFT-LCD glass substrate of claim 1, it is characterized in that: the SiO in the described TFT-LCD glass substrate component
2+ B
2O
3Content be 63～75%, B
2O
3+ Al
2O
3Content be 21～29%, the content of other RO of CaO+MgO+ is 3～13%, above R represents any one oxide compound or the mixing of two or more oxide compound arbitrarily among Be, Sr, the Ba.
3. according to the chemical association composition of claim 1 or 2 described TFT-LCD glass substrates, it is characterized in that: in the described TFT-LCD glass substrate component, increase total mass and be not more than 1% beryllium oxide.
4. according to the chemical association composition of claim 1 or 2 described TFT-LCD glass substrates, it is characterized in that: in the described TFT-LCD glass substrate component, increase total mass and be not more than 1% stannic oxide.
5. according to the chemical association composition of claim 1 or 2 described TFT-LCD glass substrates, it is characterized in that: contain following at least a compound in the described TFT-LCD glass substrate component: BeO, SnO
2And Cl, and in described TFT-LCD glass substrate component BeO+SnO
2The shared mass percent of+Cl is 0.1～1%.
6. according to the prescription of the described glass substrate of claim 1～5, it is characterized in that: this glass substrate, the light transmission rate of glass are 91%; At 10 ℃～300 ℃ thermal expansivity is 31～39x10
-7℃; Strain point is more than 640 ℃, and density is less than 2.6g/cm
3, liquidus temperature is lower than 1150 ℃.
7. a TFT-LCD glass substrate is characterized in that having the described chemical composition of claim 1-6, and the mass percent that is limited.
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|---|---|---|---|
| CN200910074313A CN101838105A (en) | 2009-05-08 | 2009-05-08 | TFT-LCD glass substrate and compound composition thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910074313A CN101838105A (en) | 2009-05-08 | 2009-05-08 | TFT-LCD glass substrate and compound composition thereof |
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| Publication Number | Publication Date |
|---|---|
| CN101838105A true CN101838105A (en) | 2010-09-22 |
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ID=42741814
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|---|---|---|---|
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109650723A (en) * | 2019-03-01 | 2019-04-19 | 陕西科技大学 | A kind of the alkali-free high alumina Pyrex and preparation method of high rigidity |
| CN109704582A (en) * | 2019-02-25 | 2019-05-03 | 深圳市辉翰科技发展有限公司 | A kind of preparation method of plural gel enhancing modification of microcrystalline glass |
-
2009
- 2009-05-08 CN CN200910074313A patent/CN101838105A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109704582A (en) * | 2019-02-25 | 2019-05-03 | 深圳市辉翰科技发展有限公司 | A kind of preparation method of plural gel enhancing modification of microcrystalline glass |
| CN109650723A (en) * | 2019-03-01 | 2019-04-19 | 陕西科技大学 | A kind of the alkali-free high alumina Pyrex and preparation method of high rigidity |
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Application publication date: 20100922 |