CN104071979A - Composition of environmental glass used for TFT-LCDs - Google Patents
Composition of environmental glass used for TFT-LCDs Download PDFInfo
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- CN104071979A CN104071979A CN201310099901.6A CN201310099901A CN104071979A CN 104071979 A CN104071979 A CN 104071979A CN 201310099901 A CN201310099901 A CN 201310099901A CN 104071979 A CN104071979 A CN 104071979A
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Abstract
A composition of environmental glass used for TFT-LCDs is disclosed. The environmental glass is used in thin film transistor liquid crystal displays (also known as TFT-LCDs). The environmental glass comprises following components by weight: not more than 63% and not less than 59% of SiO2, not more than 17% and not less than 13% of Al2O3, not more than 14% and not less than 7% of B2O3, not more than 3% and not less than 0.1% of BaO, not more than 3.5% and not less than 0.5% of MgO, not more than 11% and not less than 7% of CaO, not more than 6% and not less than 0.2% of SrO, and not more than 0.4% and not less than 0.05% of SnO2, with the total content of the CaO, the BaO, the MgO, the SrO, and the like being 7.8%-23.5% to the best. Accordingly, the components are melt to form the hard and tough environmental glass used for the TFT-LCDs. Chemical resistance and devitrification resistance of the glass are enhanced and the viscosity and the expansion factor decrease, thus overcoming a problem of insufficient strength and hardness of glass at present and a problem that the glass at present comprises PbO, As2O3 or Sb2O3, and other components harmful to the environment.
Description
Technical field
The present invention is the composition of a kind of TFT-LCD environmental protection glass, and the present invention espespecially one can chilled glass structure, promotes its chemical resistant properties and devitrification resistance, and in composition containing PbO, As
2o
3or Sb
2o
3etc. environmentally harmful composition, be conducive to recycling.
Background technology
Mobile electronic equipment is as mobile phone, the indicating meter that panel computer etc. use, the Thin film transistor liquid crystal display that belong to more, TFT-LCD, the main membrane transistor technology that uses is improved image quality, substantially, a slice TFT-LCD panel need use two sheet glass, respectively for making IC and COLOR FILTER sheet, because the processing procedure of TFT comparatively requires thermotolerance, and Jian Cheng branch affects the characteristic of TFT, therefore general TFT-LCD uses alkali-free composition (as lithium with sheet glass, sodium, the alkali metal group elements such as potassium) alkali-free aluminium pyrex, because alkali metal group element is fusing assistant preferably, without fusing assistant in the situation that, melting temperature (Tm) and stickiness relatively also can improve, and make the difficulty of melting, clarification, homogenizing and moulding of glass higher.
Hold, TFT-LCD can utilize the method for forming such as float technology, slot downdraw technology and fusion overflow downdraw technology to make with sheet glass, wherein because pull technology under melt overflow is to use noncontact forming method, therefore the surface of plate glass of making smoothly must not grind, and is applicable to the manufacturing process as TFT-LCD sheet glass.
Generally speaking, while utilizing glass tube down-drawing to manufacture sheet glass, the molten glass liquid of high temperature and tool mobility, sequentially first through devices such as glass calciner, clarifying tank and cooling tubes, flow to the distribution trough with evenly distribute glass flow rate function, then through sheet glass pumping and leading-in device, melten glass is drop-down, low cooling, and make sheet glass.In its processing procedure, in the time that molten glass liquid is flowed through calciner and clarifying tank, high and the tool mobility of its temperature, in the time flowing through cooling tube, its temperature of cooling tube military order reduces, so that while flowing to the distribution trough with evenly distribute glass flow rate function, can be reduced to the required temperature of moulding, make its viscosity scope keep constant.
Generally speaking, when molten glass liquid temp reduces, very easily cause glass and produce crystalline polamer and devitrification (because of glass crystallization devitrification), cause glass surface or the inner impurity that produces, this will change the stress distribution of inside glass, affect glass hard (HRC65Yi Shang) and intensity, caused product yield to decline.
While utilizing the drop-down method of forming to make sheet glass, its temperature is all controlled between approximately 1085～1250 DEG C, therefore, for reducing glass surface or the inner defects such as devitrification or crystallization that occur, the general way that reduces glass liquidus temperature that all adopts, by adjusting glass composition, and then by the liquidus temperature of glass composition, be cut to compared with 1085 DEG C of lower temperature of moulding lower limit temperature, but glass composition is once variation, except glass liquidus temperature by with variation, the physical property that other are important, as: thermal expansivity, strain point and density etc. also can with variation, even part characteristic can be deteriorated to the normal use that hinders glassy product.Therefore, how to adjust composition, make in reducing glass liquidus temperature, the physical property that other are important, also unlikely excessively deteriorated, become the crucial emphasis while adjusting glass composition.
The glass using for production liquid-crystal display, particularly produce the glass that membrane transistor liquid-crystal display uses, requirement in its physical property, strict especially, therefore, the key properties such as thermal expansivity, strain point and the density of glass, should list the emphasis that assessment is considered in the lump in.
Recently, the design and manufacture dealer of base-board of liquid crystal display glass, also for the composition of described each base plate glass, development and Design goes out many new manufacturing technologies, as No. 5811361st, United States Patent (USP), No. 5851939 and No. 6060168, the glass substrate of making according to the disclosed glass composition of described each patent, its glass liquidus temperature is still higher, about more than 1090 DEG C, therefore, described each glass is in the time utilizing glass tube down-drawing moulding, will there is aforementioned all puzzlements, cause glass and produce crystalline polamer, cause strength of glass to decline, and the not good problem of the finished product yield.
Moreover, PbO, As in existing glass composition
2o
3and Sb
2o
3can damage human body and environment, the glass that for example TaiWan, China is announced No. I365861 and I319384 Patent Case discloses, its composition contains a large amount of PbO, can damage human body and environment, do not meet the requirement of environmental protection, in addition, TaiWan, China is announced in the glass composition that I252844 Patent Case discloses and is contained harmful As
2o
3and Sb
2o
3(in making processes as defoamer); But, if substitute As with heterogeneity
2o
3and Sb
2o
3, must change the original optics of glass and physical property, thus must to the composition of glass, weight percent when defoamer research and develop widely and change, can overcome above-mentioned problem.
Through above-mentioned known, improvement direction of the present invention, is TFT-LCD environmental protection glass component how to design a kind of innovation, can replace PbO, As by the mode of interpolation and change group component proportions
2o
3or Sb
2o
3etc. environmentally harmful composition, and then produce the TFT-LCD environmental protection glass with reinforced structure and devitrification resistance, to solve existing TFT-LCD strength of glass and hardness deficiency, and do not meet environmental protection standard, cause reclaiming problem difficult to recycle.
Summary of the invention
In view of the demand, main purpose of the present invention is replacing PbO, As by the mode of interpolation and change group component proportions
2o
3or Sb
2o
3etc. environmentally harmful composition, and then produce the TFT-LCD environmental protection glass with reinforced structure and devitrification resistance.
In order to achieve the above object, the present invention mainly strengthens the structure of TFT-LCD environmental protection glass by the mode of adding and change the weight percent of moiety in glass component, described TFT-LCD is respectively 59.0%≤SiO with the weight percent of the composition of environmental protection glass
2≤ 63.0%, 13.0%≤Al
2o
3≤ 17.0%, 7.0%≤B
2o
3≤ 14%, 0.1%≤BaO≤3%, 0.5%≤MgO≤3.5%, 7%≤CaO≤11%, 0.2%≤SrO≤6% and 0.05%≤SnO
2≤ 0.4%, the wherein total content of the composition such as BaO, MgO, CaO and SrO, taking at 7.8%～23.5% as best, so, the melting of aforementioned component material can be formed to tough and tensile glass, and can borrow SiO
2in glass, form network structure, and borrow Al
2o
3make glass generate tough and tensile surface, and then increase glass thermotolerance and devitrification resistance, reduce glass swelling rate, and borrow B
2o
3, MgO and CaO reduce viscosity and the coefficient of expansion of glass, and increases chemical resistant properties and the devitrification resistance of glass by BaO and SrO, to solve the problem of existing TFT-LCD strength of glass and hardness deficiency, simultaneously by SnO
2replace PbO, As
2o
3or Sb
2o
3deng composition, the finings while melting as glass or defrother, and then solve existing TFT-LCD glass and do not meet environmental protection standard, cause reclaiming difficulty and the problem that cannot recycle.
Embodiment
The present invention mainly provides the composition of a kind of TFT-LCD environmental protection glass, its
combined according to certain weight percent by following material:
(1)59.0%≤SiO
2≤63.0%；
(2)13.0%≤Al
2O
3≤17.0%；
(3)7.0%≤B
2O
3≤14%；
(4)0.1%≤BaO≤3%；
(5)0.5%≤MgO≤3.5%；
(6)7%≤CaO≤11%；
(7) 0.2%≤SrO≤6%; And
(8) total weight percent of the composition such as CaO, BaO, MgO and SrO is wherein 7.8%～23.5%.
In the present invention, the respectively weight percent of this constituent, will be according to its physical property, and the aspects such as characteristic, structure and the making to TFT-LCD use environmental protection glass, cause impact in various degree, therefore respectively this constituent must limit to some extent on weight percent, wherein, SiO
2, Al
2o
3and B
2o
3more Deng the weight percent that three kinds of compositions are shared, and the aspect such as characteristic, structure and making to glass substrate, that causes affects outbalance, therefore the major ingredient that described each composition is glass substrate, wherein SiO
2form the network structure of glass, its preferably weight percent content be 59%～63%, if SiO
2content is less than 59%, and produced glass is easy devitrification, on the other hand, if SiO
2content is more than 63%, and by causing, the melting temperature (Tm) of glass is too high, and made glass is easy devitrification also; Al
2o
3be the intensity that improves glass structure, make glass generate tough and tensile surface, and then increase glass thermotolerance and devitrification resistance, reduce glass swelling rate, its preferably weight percent content at 13%～17%, if Al
2o
3content is less than 13%, and glass, by easy devitrification, is also easily subject to the erosion of extraneous aqueous vapor or chemical reagent, if another Al
2o
3content, more than 17%, also will cause the melting temperature (Tm) of glass too high, and is unfavorable for general calciner manufacture; B
2o
3be used as fusing assistant, the mainly viscosity of glass when reducing fusion cast glass, its preferably weight percent content be 7.0%～14%, if B
2o
3content is less than 7%, and its fusing assistant effect cannot be given full play to, if B
2o
3content, more than 14%, will significantly reduce the strain point of glass, is unfavorable for the application of successive process.
In the present invention, except aforementioned SiO
2, Al
2o
3and B
2o
3outside three kinds of compositions, all the other compositions, as: four kinds of compositions such as CaO, BaO, MgO and SrO, though it is lower to account for the per-cent of overall weight, to molten glass liquid viscosity and melting degree, have very important impact; The effect of CaO is the melting that promotes glass, and its better content is between 7%～11%, if CaO content is less than 7%, cannot effectively reduce the viscosity of glass, if CaO content more than 11%, glass is by easy devitrification, and thermal expansivity can significantly improve, be unfavorable for the application of successive process, the better weight percent content of BaO is 0.1%～3%, if BaO content is less than 0.1%, glass is by easy devitrification, if BaO content is more than 3%, glass density can be too high, and strain point can significantly reduce; The effect of SrO is similar to BaO, and preferably weight percent content is at 0.2%～6% for it, if SrO content is less than 0.2%, glass is easy devitrification, if SrO content more than 6%, glass density can be too high, is unfavorable for the application of product; Viscosity and the coefficient of expansion of MgO glass when reducing fusion cast glass, to reduce bubble wherein or the content of impurity, its preferably content be between 0.5%～3.5%, if but MgO content more than 3.5%, glass is by easy devitrification.
Again, SnO
2for excellent finings, if use SnO
2as the supporting electrode (Auxiliary Boosting) of smelting furnace, along with the consumption gradually of electrode, SnO
2also will incorporate gradually in glass; Moreover, SnO
2also can be by obtaining in formula material, but SnO after melting
2very easily condense in the low temperature place in platinum system (the molten glass liquid delivery system being made up of platinum material is used so that glass metal can successfully be eliminated bubble and stir), causes and produce yield decline; Again, too much SnO
2to affect the transparence of glass, the application of unfavorable display glass, therefore SnO
2content must not exceed 0.4%.
Hold, though the compositions such as aforementioned CaO, BaO, SrO and MgO are in order to promote the melting degree of glass, and adjust the thermal expansivity of glass, but the total content of the compositions such as CaO, BaO, SrO and MgO, taking at 7.8%～23.5% for the best, if the total content of the compositions such as CaO, BaO, SrO and MgO is less than 7.8%, the melting temperature (Tm) of glass will be too high, otherwise, if the total content of the compositions such as CaO, BaO, SrO and MgO is more than 23.5%, glass is easy devitrification, and the thermal expansivity of glass can be too high.
The present invention, in the time implementing, first by aforementioned component thing, after evenly mixing, then imports a glass melting groove by mixing raw material, and mixing raw material melts into after glass metal by the time, its temperature is reduced to the required temperature range of moulding, even its viscosity scope remains on (10
4.6～10
4.8) poise(pool) and temperature range, following pulling shaping method, produces the glass substrate of pre-determined thickness, treats that glass substrate is low cooling, can be cut into the glass substrate finished product that liquid-crystal display is used.
The careful just aforesaid each constituent of the present invention below, with different weight percents, mixed, then gone out different glass samples according to aforementioned program making, and taking described each glass sample as example, tabulate the difference between the characteristic values such as its thermal expansivity, strain point, density and glass liquidus temperature:
Show composition and the characteristic of the made glass sample of the present invention at table one (example 1), i.e. embodiments of the invention.At the glass sample of table one, with following method manufacture; Each composition is got conventional raw material, evenly mix, then with the temperature of (1680 DEG C), melt and stir in platinum heating system, then the glass metal of molten state is drawn to moulding method cooling forming is below sheet according to corresponding weight percent.Now, detect for each glass sample, can obtain respectively the characteristic values such as thermal expansivity, strain point, density and glass liquidus temperature, and be documented on the corresponding field of table one.
The present invention, in the time detecting each characteristic value of each glass sample, is mainly to carry out according to following method:
(1) thermal expansivity (unit: 10
-7/ DEG C) detection: with mechanical push rods formula thermal dilatometer, heat and measure the elongation of glass sample, temperature range is no longer extended to glass from room temperature amount, even because of the temperature (being generally 0～300 DEG C) till softening contraction.
(2) detection of strain point (unit: DEG C): heat and measure the viscosity of glass sample and the relation of temperature, with specific viscosity (10
14.5poise) corresponding temperature is as strain point.
(3) density (unit: g/cm
3) detection: get the not block glass of bubbles of approximately 2 grammes per square metres, the situation of drifting along in specific gravity liquid with glass sample is measured its density.
(4) detection of glass liquidus temperature (unit: DEG C): the cullet that is less than 850 μ m is put into platinum ware, be placed in gradient furnace after 24 hours, measure the crystallization situation of glass with microscope, judge its liquidus temperature and obtain.
Table one
From the each detection data shown in table one, according to the made TFT-LCD of composition of the present invention environmental protection glass, there is the not thermal expansivity higher than 33 (10-7/ DEG C), and its strain point is not less than 660 DEG C, density is not more than the characteristic values such as 2.39g/cm3, the base plate glass of using with general high strength liquid-crystal display is very close, therefore be suitable for the material as liquid crystal display glass substrate.
To sum up, the present invention carrys out reinforced structure by the mode of adding and change the weight percent of moiety in glass component, to form network structure in glass by SiO2, and make glass generate tough and tensile surface by Al2O3, and then increase glass thermotolerance and devitrification resistance, and by B2O3, MgO and CaO reduce viscosity and the coefficient of expansion of glass, while increases chemical resistant properties and the devitrification resistance of glass by BaO and SrO, accordingly, mode by interpolation and change group component proportions is carried out reinforced structure, the present invention is after it implements according to this, really can reach the object that a kind of TFT-LCD environmental protection glass that promotes chemical resistant properties and devitrification resistance and reinforced structure is provided.
Above-described content, it is only preferred embodiment of the present invention, not in order to limit scope of the invention process, anyly have the knack of this skill person, do not departing from the equalization variation and modification under spirit of the present invention and scope, done, all should be covered by impartial variation and modification of the present invention, all should be covered by the scope of the claims of the present invention.
Claims (2)
1. a composition for environmental protection glass for TFT-LCD, is characterized in that, the composition of its each composition and the weight percent of each composition are:
59%≤SiO
2≤63%；
13%≤Al
2O
3≤17%；
7%≤B
2O
3≤14%；
0.1%≤BaO≤3%；
0.5%≤MgO≤3.5%；
7%≤CaO≤11%；
0.2%≤SrO≤6%; And
0.05%≤SnO
2≤0.4%。
2. the composition of environmental protection glass for TFT-LCD as claimed in claim 1, is characterized in that, the total weight percent of the compositions such as CaO, BaO, MgO and SrO is 7.8%～23.5%.
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|---|---|---|---|
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310099901.6A CN104071979A (en) | 2013-03-26 | 2013-03-26 | Composition of environmental glass used for TFT-LCDs |
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| Publication Number | Publication Date |
|---|---|
| CN104071979A true CN104071979A (en) | 2014-10-01 |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102106033A (en) * | 2008-09-19 | 2011-06-22 | 日本电气硝子株式会社 | Substrate for solar cell and oxide semiconductor electrode for dye-sensitized solar cell |
-
2013
- 2013-03-26 CN CN201310099901.6A patent/CN104071979A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102106033A (en) * | 2008-09-19 | 2011-06-22 | 日本电气硝子株式会社 | Substrate for solar cell and oxide semiconductor electrode for dye-sensitized solar cell |
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Application publication date: 20141001 |