CN109809687A - A kind of base plate glass for high resolution display - Google Patents
A kind of base plate glass for high resolution display Download PDFInfo
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- CN109809687A CN109809687A CN201711164252.8A CN201711164252A CN109809687A CN 109809687 A CN109809687 A CN 109809687A CN 201711164252 A CN201711164252 A CN 201711164252A CN 109809687 A CN109809687 A CN 109809687A
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Abstract
The present invention relates to a kind of base plate glass for high resolution display, glass composition is calculated according to molar percentage, including 66.0%~72.0% SiO2, 11%~16% AL2O3, 4%~8% B2O3, 2.50%~6.5% MgO, 6.0%~10% CaO, 1.2%~4.5% SrO, 0%~3% BaO, and 78.5mol%≤SiO2+AL2O3≤ 82.5mol%, 16≤(SiO2+AL2O3)/B2O3≤ 20,0.7≤(CaO+SrO+BaO)/AL2O3≤ 1.0,0.2≤MgO/ (CaO+SrO+BaO)≤0.5；For this kind of glass at 600 DEG C, heat treatment has the≤thermal contraction of 10ppm, >=30GPa/ (g.cm after ten minutes‑3) than elasticity modulus and >=700 DEG C of strain point temperature, performance it can satisfy the requirement of high resolution display base plate glass.
Description
Technical field
The invention belongs to glass for liquid crystal display technical fields, are related to a kind of substrate glass for high resolution display
Glass.
Background technique
With the continuous development of LCD technology, people pursue high-resolution and high grade picture increasingly.OLED is shown
The development and production of device not only reduce the cost of raw material, and production process also greatly reduces, and due to production of polysilicon technology
Using corresponding liquid crystal display has fast response time, brightness is high, electric quantity consumption is low, high resolution, and display effect is good etc.
A series of advantages become the mainstream of flat-panel monitor production.For monocrystalline silicon (a-Si) manufacturing process, polysilicon (P-
It Si) include more heat treatment steps in LCD display board production technology, it is desirable that temperature reaches 400 DEG C~600 DEG C,
Under the conditions of this temperature, liquid crystal display substrate glass needs to undergo the process tightened, i.e. thermal stability either change in size.This
Kind variation can cause the pixel interval error of TFT, lead to display defect, be on the other hand heat-shrinked and be also possible to lead to pattern errors.
The variation of this size is not allow the problem in panel manufacturing process, it will influences the quality of display, another party
Face, since the increase of display sizes, the increase of glass weight, the transport of glass and dress take and require that glass has smaller scratch
Degree.Above-mentioned a series of problems is all developed one kind there is an urgent need to base plate glass technical field as early as possible and is shown applied to high-resolution liquid crystal
Show the base plate glass of device.
Summary of the invention
The problem to be solved in the present invention is to provide a kind of base plate glass for high resolution display, the base plate glass
With strain point temperature height, the good characteristics such as bigger than elasticity modulus, percent thermal shrinkage is low, and thermal stability, chemical stability are good can
Meet the needs of high-resolution liquid crystal display panel fabrication process processing procedure.
The present invention is achieved by the following technical solutions:
The present invention relates to a kind of base plate glass for high resolution display, composition is calculated according to molar percentage,
Include:
And meet 78.5%≤SiO2+AL2O3≤ 82.5%；
16≤(SiO2+AL2O3)/B2O3≤20；
0.7≤(CaO+SrO+BaO)/AL2O3≤1.0；
0.2≤MgO/(CaO+SrO+BaO)≤0.5；
Impurity (ZrO2+Fe2O3+S+CL+TiO2) content calculated by weight percentage less than 0.2%；
Clarifying agent (SnO2+CeO2+ halide) content is calculated between 0.1%~0.6% by weight percentage；
Alkali metal oxide content is calculated by weight percentage is less than or equal to 0.1%.
Further, the base plate glass, composition are calculated according to molar percentage, comprising:
And meet 78.5%≤SiO2+AL2O3≤ 82.5%；
16≤(SiO2+AL2O3)/B2O3≤20；
0.7≤(CaO+SrO+BaO)/AL2O3≤1.0；
0.2≤MgO/(CaO+SrO+BaO)≤0.5。
Base plate glass of the present invention not only requires SiO2Reach 66%~72%, AL2O3Reach 11%~16% model
Within enclosing；More require SiO2+AL2O3Content control within the scope of 78.5%~82.5%, because of SiO2With AL2O3All it is
Network former, increasing its amount can be improved the strain point temperature of glass, reduce the thermal contraction of glass, improve glass
Elasticity modulus, to reach higher than elastic mould value, on chemical durability, SiO2With AL2O3Even more interdepend,
The total content of the two is higher, and the chemical durability of glass is better.Certainly work as SiO2With AL2O3When content is excessive, glass can also occur
The phenomenon that infusibility, defect increases.B2O3The fusing for being conducive to glass, the strain point temperature of glass can be reduced by increasing its content, thus
By SiO2、AL2O3、B2O3Three kinds of oxide controls are in 16≤(SiO2+AL2O3)/B2O3In the range of≤20, balance very well
State problem.The present invention is even more the ratio by reasonably adjusting alkaline earth oxide, meets the relationship between various oxides
It is claimed below: 0.7≤(CaO+SrO+BaO)/AL2O3The range of≤1.0,0.2≤MgO/ (CaO+SrO+BaO)≤0.5, in this way
Both it ensure that glass was easy to melt, while also having provided broader process margin for overflow down draw forming.
Base plate glass of the present invention is alkali-free glass, alkali metal oxide (weight percent) R2O≤0.1%.This
It is to guarantee that alkali metal ion will not diffuse in film in the process of display, make membrane property be deteriorated.However, by
In present composition large viscosity, glass melting temperature is high, is easy to produce defect, and alkali metal oxide is conducive to the molten of glass
System, improves the refining quality of glass, therefore glass composition of the present invention is introduced micro alkali metal oxide to raw material itself and mentioned
Content requirement is gone out, it is desirable that various alkali metal oxide content (weight percent) Na2O≤0.05%；K2O≤0.02%；
Li2O≤0.02%.
Base plate glass of the present invention is clarified, clarifying agent in melting process using the method for chemical fining agent
Content (weight percent) between 0.1%~0.6%, clarifying agent includes SnO2、CeO2、CL、Fe2O3、SO3One of or
Several mixtures.Since the glass viscosity of glass composition provided by the invention production is big, bubble in glass manufacturing process
Incidence increases, and makes full use of clarifying agent that the spy of redox reaction occurs at a certain temperature in the glass component thus
Point makes in different temperature stages, and bubble parameters are discharged.As different clarifying agents, decomposition temperature in glass is not
With.Sulfate decomposes under 1200 DEG C~1400 DEG C of lower temperature, generates a large amount of SO2Gas (SO3→SO2+1/2O2),
Chloride decomposes at 1400 DEG C~1500 DEG C, generates a large amount of HCL and CL2Gas；SnO2It is reduced at 1450 DEG C or more
SnO generates O2(SnO2→SnO+1/2O2), these gases of generation all play the role of that bubble is made to become larger, and therefore, they are all
Good clarifying agent.However, due to SnO2、CeO2、CL、Fe2O3、SO3Equal oxides are added beyond a certain amount of, it will play
Therefore some negative effects such as color, formation tin calculus in glass composition, there is stringent limitation to their content.By weight
Percentage calculates, SO3Amount≤0.03%, CL amount≤0.05%, SnO2Amount≤0.20%, for Fe2O3With
CeO2Equal metal oxides or metal salt, with SnO2Equally, as the rising of glass solution temperature also generates O2, glass is also risen
It is influenced to certain clarifying effect, but since these oxides suffer from color, every kind of oxide content (weight percent) control
System is below 0.03%.Generally speaking, the various clarifying agents being added in glass are the 0.1% of glass total amount (weight percent)
~0.6%.
The present invention also provides the allotments of glass composition, including preferred cullet to be added in composition, the ratio of cullet
Example is the 20%~30% of batch total amount (weight percent).Because the melted glass of glass composition provided by the invention is glutinous
Degree is big, and Bubbles in Glass is more, takes pure powder as batch, and glass quality can not be guaranteed, and bubble is more in molten sample,
Even being also possible to non-fusant defect, the additions of cullet such as generation quartz particles facilitates the melting of glass, improves glass
Refining quality.
Glass composition allotment provided by the invention, is drawn by boric acid with boric anhydride jointly including the boron oxide in glass composition
Enter.It is a discovery of the invention that only introducing boric acid in batch, due to containing certain moisture in boric acid, become as the temperature rises
At metaboric acid, make batch conglomeration, causes the uneven of mixture.It is collectively incorporated into batch by boric acid and boric anhydride, energy
It is enough to inhibit the phenomenon that batch conglomeration well, so that batch is become more uniform.
SiO2 is the formation skeleton of glass, it can reduce the thermal expansion coefficient of glass, improves the thermal stability of glass, is changed
The performances such as stability, softening point, strain point temperature, heat resistance, hardness, mechanical strength are learned, it provides certain viscosity for glass,
Be conducive to the forming technology of overflow downdraw, but SiO2 content increases, and needs higher fusion temperature, and can make to melt and lack
It falls into and increases.Influence of the granule size and particle size matching of SiO2 to glass production simultaneously is also very big, and particle is too big, and fusing is difficult,
And there may be glass defects such as calculus stripeds, particle is too small, and impurity content is high, is easy to fly upward, and is also unfavorable for the progress of production.
In the present invention, it introduces in 15 μm~200 μ m of quartz sand size requirement of SiO2, and average grain diameter D50 is less than 60 μm, more
Further less than 50 μm, more preferably less than 40 μm.
AL2O3 is also to play the role of glass formers in the present invention, the increase of AL2O3, generally results in density, expansion
The decline of coefficient, it can improve the durability of glass, improve annealing point, strain point and elasticity modulus, while AL2O3 is also glass
Glass provides certain viscosity, compares SiO2, it is higher than SiO2 to the influence degree of viscosity.But if AL2O3 too high levels,
Glass not only melts difficulty, is also easy crystallization.So the present invention requires the additional amount of AL2O3 to be 11.0%~16.0%,
Want relationship between balance aluminium oxide and silica and alkali metal content simultaneously, meet 78.5%≤SiO2+AL2O3≤
82.5%；The requirement of 16≤(SiO2+AL2O3)/B2O3≤20.
B2O3 is also glass former oxide, its effect in glass is more special, can reduce glass at high temperature
The viscosity of glass then can be improved the viscosity of glass in low temperature, reduce liquidus temperature.B2O3 is also played in glass production and is helped
The effect of solvent accelerates the clarification of glass, reduces the crystallizing power of glass, increases the content of boron, can improve fluoride acid
In durability.But when too high levels, the coefficient of expansion of glass can be made to increase, the strain point of glass reduces, and heat resistance reduces, bullet
Property modulus decline, acid resistance is also deteriorated.Therefore, the content of B2O3 is limited in 4%~8% range in glass composition.
The various alkaline earth oxides being added in the present invention are to fully consider the respective characteristic of oxide and want balanced glass
Glass product characteristic and technique require allotment.On the whole, increase alkaline earth element, can reduce melt in the glutinous of fixed temperature
Degree is conducive to the control for melting defects controlling and forming technology.MgO is for reducing high-temperature viscosity and the melting for improving glass
Performance, but if content of MgO is excessively high, liquidus temperature can be increased so that devitrification resistance be deteriorated, be unfavorable for overflow downdraw at
Shape technique, on the other hand, the reaction product of MgO and BHF buffer can be adhered in glass pane surface or equipment, so that glass
Translucency is deteriorated.Therefore MgO is limited within the close limit of total alkaline earth oxide concentration.MgO molar percentage of the present invention
Within the scope of content is 2.5%~6.5%.CaO is also the same with MgO, can reduce the high-temperature viscosity of glass, is conducive to improve
The refining quality of glass, and glass density and strain point will not reduce too much.CaO mole percent level of the present invention between
6.0%~10%.SrO, BaO all advantageously reduce the liquidus temperature of glass, especially BaO for liquidus curve contribution more
Greatly, but increase the content of barium monoxide to replace other alkaline earth oxides, it will increase fusion temperature.BaO is as divalent
Network modifying oxide, it can increase refractive index, density, gloss and the chemical stability of glass, to the erosion of refractory material compared with
Seriously.It must be controlled based on base plate glass environmental protection and lightening development trend, the additional amount of BaO.Compared with BaO, SrO
Also X-ray can be absorbed well, while the influence to density, linear expansion coefficient and strain point is less than BaO.SrO moles of the present invention
Degree controls within the scope of 1.2%~4.5%, and BaO content controls within the scope of 0%~3%.
Although various oxides all play different effects in glass, the additional amount of every kind of oxide has centainly
Limitation, it is best to guarantee that a combination thereof reaches glass properties.In the present invention, 78.5%≤SiO2+AL2O3≤82.5%；16≤
(SiO2+AL2O3)/B2O3≤20, above range limitation both ensure that the strain point temperature of glass was greater than 700 DEG C, and glass exists
600 DEG C, heat treatment has the≤thermal contraction of 10PPm after ten minutes, and the ratio elasticity modulus of glass is greater than 30GPa/g.cm-3, again
The needs that can satisfy glass melting reduce the incidence of defect.By controlling 0.7≤(CaO+SrO+BaO)/AL2O3≤1.0
Guarantee glass so that glass avoids liquidus temperature from increasing under low-viscosity with 0.2≤MgO/ (CaO+SrO+BaO)≤0.5
Melting, while making the liquidus temperature of glass within the scope of reasonable.
It joined in the batch of the present composition and be conducive to remove the gas defects generated in glass melting process
Chemical fining agent.Mixture including one or more of SnO2, CeO2, CL, Fe2O3, SO3.Clarify agent content (SnO2+
CeO2+ halide) it calculates between 0.1%~0.6% by weight percentage, between preferably 0.1~0.3%.
Zirconium oxide and titanium dioxide are considered as the impurity in glass in the present invention, although ZrO2, TiO2 can improve glass
The endurance of glass, especially acid resistance, but ZrO2 can improve liquidus temperature, and generate zirconium calculus；TiO2 content height can make glass
Glass coloring, makes decrease in transmission.So both ingredients all have certain limitations, they are together with other impurity with weight hundred
Score calculates content (TiO2+ZrO2+Fe2O3+SO3+CL)≤0.2%, in which: ZrO2 < 0.08%, TiO2 < 0.01%,
Fe2O3 < 0.05%, SO3 < 0.03%, Cl < 0.03%.
Base plate glass of the present invention follows the steps below allotment preparation under lab:
Step 1:
Be ready to prepare the raw material of composition: the granularity of quartz sand raw material is 15 μm~200 μm, and D50 (average grain diameter) is small
In 60 μm；The raw material for introducing boron oxide is boric acid and boric anhydride；Alkaline-earth metal (MgO, CaO, SrO, BaO) oxide is by different carbon
Hydrochlorate, nitrate introduce；Chemical fining agent is collectively incorporated by compounds such as tin oxide, cerium oxide, sulfate.
Step 2:
According to the proportion of glass composition of the present invention, various raw materials are weighed.Batch is sufficiently mixed in mixing machine
It is even.
Step 3:
The batch mixed is put into high temperature sample-melting stove, sample-melting stove heats up according to the technological temperature of setting, 1650
DEG C~1670 DEG C at a temperature of keep the temperature 4 hours, obtain the glass metal that has melted.
Step 4:
The glass metal melted is directly poured into water, the cullet of batch needs are obtained.
Step 5:
Various raw materials are weighed again, the cullet prepared are added, and additional amount is the 20%~30% of batch, and mixing is equal
It is even, it heats up according to molten sampling technology, and in 1650 DEG C~1670 DEG C of at a temperature of heat preservation 4 hours or more.
Step 6:
The glass metal melted is poured in steel mould rapidly, glass blocks is then removed from the molds, is put into annealing furnace
Middle annealing, preparation process are completed.
In the present invention, role is different in the composition for various oxides, according to inventive technique scheme desired ratio
It weighed, mixed, melted, the glass of formation has the strain point temperature more than or equal to 700 DEG C, at 600 DEG C, is heat-treated 10 points
Have after clock and be less than or equal to 10PPm percent thermal shrinkage, and the ratio elasticity modulus more than or equal to 30GPa/g.cm-3, and reaches glass
The less target of glass internal residual bubble.
Specific embodiment
The embodiment that table 1 is listed further illustrates that the present invention, these embodiments do not constitute and appoint to of the invention for illustrating
What is limited.It is special to high resolution display base plate glass that these embodiments have reacted a variety of different oxides in the present invention
The influence of performance indicator, while these performances also provide foundation for the claims in the present invention.Table 1 lists high-resolution and shows
The content of device base plate glass composition and the glass of test melt the performance of sample.In laboratory, weighing is mixed
Batch pours into platinum crucible, and temperature is controlled at 1650 DEG C~1670 DEG C, and heat preservation poured into ready mold after 4~8 hours
In, product is taken out after being annealed, is tested for the property.Molten sample product is measured using orton ANS-800 annealing strain point instrument
Strain point temperature；The density of molten sample is measured using DH-120M high-precision electronic densimeter；Using MK-6A elasticity modulus instrument
Measure the elasticity modulus of molten sample；The percent thermal shrinkage of molten sample is tested using ortonDIL2010STD dilatometer.
The test of strain point temperature takes loaded fiber elongation method to measure, and is moved back using orton ANS-800
Fiery strain point instrument, reaches the requirement of ASTMC336 standard method.
The test of molten sample rate is carried out according to Archimedes principle.
The test of elasticity modulus is determined according to resonant ultrasonic spectroscopic technique, sample different parts is tapped, according to frequency
With the relationship of modulus, the elastic mould value (GPa) of sample is obtained.The ratio springform of sample is calculated according to elasticity modulus and density
Amount.Bigger than elastic mould value, reaction glass sag deformation extent is smaller, and the present invention is greater than 30GPa cm3/g than elasticity modulus.
Percent thermal shrinkage value reflect base plate glass in use after Overheating Treatment size variation degree.For molten
The thermal contraction of sample, the present invention are measured by ortonDIL2010STD dilatometer.Molten sample is made and meets test request
Rod-like samples, then sample is made annealing treatment, sample is put into dilatometer later, set technological temperature, measure sample
Product keep the temperature 10 minutes thermal contraction situations at 600 DEG C, and dilatometer software can directly calculate the receipts of sample under certain condition
Contracting swell value is to get the shrinking percentage for melting sample to glass.
The glass of preparation of the embodiment of the present invention has the strain point temperature more than or equal to 700 DEG C, at 600 DEG C, heat treatment 10
Have after minute and is less than or equal to 10PPm percent thermal shrinkage, and the ratio elasticity modulus more than or equal to 30GPa/g.cm-3.
The base plate glass produced using glass composition of the present invention and concocting method, it is aobvious that performance can satisfy high-resolution
Show the requirement of device base plate glass.
Table 1:
Claims (11)
1. a kind of base plate glass for high resolution display, composition is calculated according to molar percentage, comprising:
And meet 78.5%≤SiO2+AL2O3≤ 82.5%；
16≤(SiO2+AL2O3)/B2O3≤20；
0.7≤(CaO+SrO+BaO)/AL2O3≤1.0；
0.2≤MgO/(CaO+SrO+BaO)≤0.5；
Impurity (ZrO2+Fe2O3+SO3+CL+TiO2) content calculated by weight percentage less than 0.2%；
Clarifying agent (SnO2+CeO2+ halide) content calculates between 0.1%~0.6% by weight percentage；
Alkali metal oxide content is calculated by weight percentage is less than or equal to 0.1%.
2. base plate glass according to claim 1, which is characterized in that the glass has >=700 DEG C of strain point temperature.
3. base plate glass according to claim 1, which is characterized in that ratio elasticity modulus >=30GPa cm of the glass3/g。
4. base plate glass according to claim 1, which is characterized in that the glass is heat-treated size after ten minutes at 600 DEG C
Shrinking percentage≤10PPm.
5. base plate glass according to claim 1, which is characterized in that it calculates by weight percentage, it should
In glass containing 0.1%~0.6% chemical fining agent, clarifying agent SnO2、CeO2、CL、Fe2O3、SO3In compound
One or more of mixtures.
6. base plate glass according to claim 1, which is characterized in that calculate by weight percentage, impurity ZrO in glass2<
0.08%, TiO2< 0.01%, Fe2O3< 0.05%, SO3< 0.03%, Cl < 0.03%.
7. base plate glass according to claim 1, which is characterized in that when the preparing glass charge produces, cullet are preferably added to,
Additional proportion is the 20%~30% of batch total weight.
8. base plate glass according to claim 1, which is characterized in that when the preparing glass charge produces, the former material work stone that uses
15 μm of 200 μm of ﹤ D ﹤ of sand partial size, average grain diameter is less than 60 μm.
9. base plate glass according to claim 8, which is characterized in that when the preparing glass charge produces, the former material work stone that uses
15 μm of 200 μm of ﹤ D ﹤ of sand partial size, average grain diameter is less than 40 μm.
10. base plate glass according to claim 1, which is characterized in that B2O3 is provided by the mixture of boric acid and boric anhydride.
11. any base plate glass according to claim 1~10, which is characterized in that it is calculated according to molar percentage, including
Consisting of:
And meet 78.5%≤SiO2+AL2O3≤ 82.5%；
16≤(SiO2+AL2O3)/B2O3≤20；
0.7≤(CaO+SrO+BaO)/AL2O3≤1.0；
0.2≤MgO/(CaO+SrO+BaO)≤0.5。
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| CN201711164252.8A CN109809687A (en) | 2017-11-21 | 2017-11-21 | A kind of base plate glass for high resolution display |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201711164252.8A CN109809687A (en) | 2017-11-21 | 2017-11-21 | A kind of base plate glass for high resolution display |
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ID=66599651
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110746111A (en) * | 2019-09-29 | 2020-02-04 | 彩虹显示器件股份有限公司 | Glass substrate and application thereof as glass substrate |
| CN113003931A (en) * | 2021-04-06 | 2021-06-22 | 蚌埠中光电科技有限公司 | Long-material alkaline earth aluminosilicate glass for display |
| CN114644445A (en) * | 2022-05-20 | 2022-06-21 | 武汉荣佳达光电科技有限公司 | Carrier plate glass forming production forming device and method thereof |
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| CN102531386A (en) * | 2010-10-06 | 2012-07-04 | 康宁股份有限公司 | Alkali-free glass compositions having high thermal and chemical stability |
| US20150259241A1 (en) * | 2012-12-21 | 2015-09-17 | Corning Incorporated | Glass with improved total pitch stability |
| CN105705472A (en) * | 2013-03-14 | 2016-06-22 | 康宁股份有限公司 | Dimensionally-stable, damage-resistant, glass sheets |
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| CN101591141A (en) * | 2008-05-30 | 2009-12-02 | 康宁股份有限公司 | Boroalumino silicate glasses |
| CN102531386A (en) * | 2010-10-06 | 2012-07-04 | 康宁股份有限公司 | Alkali-free glass compositions having high thermal and chemical stability |
| US20150259241A1 (en) * | 2012-12-21 | 2015-09-17 | Corning Incorporated | Glass with improved total pitch stability |
| CN105705472A (en) * | 2013-03-14 | 2016-06-22 | 康宁股份有限公司 | Dimensionally-stable, damage-resistant, glass sheets |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110746111A (en) * | 2019-09-29 | 2020-02-04 | 彩虹显示器件股份有限公司 | Glass substrate and application thereof as glass substrate |
| CN113003931A (en) * | 2021-04-06 | 2021-06-22 | 蚌埠中光电科技有限公司 | Long-material alkaline earth aluminosilicate glass for display |
| CN113003931B (en) * | 2021-04-06 | 2022-05-24 | 蚌埠中光电科技有限公司 | Long-material alkaline earth aluminosilicate glass for display |
| CN114644445A (en) * | 2022-05-20 | 2022-06-21 | 武汉荣佳达光电科技有限公司 | Carrier plate glass forming production forming device and method thereof |
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Application publication date: 20190528 |
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