CN103313948A - Non-alkali glass - Google Patents
Non-alkali glass Download PDFInfo
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- CN103313948A CN103313948A CN201280005480XA CN201280005480A CN103313948A CN 103313948 A CN103313948 A CN 103313948A CN 201280005480X A CN201280005480X A CN 201280005480XA CN 201280005480 A CN201280005480 A CN 201280005480A CN 103313948 A CN103313948 A CN 103313948A
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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
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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
- C03C3/095—Glass compositions containing silica with 40% to 90% silica, by weight containing rare earths
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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
- C03C3/097—Glass compositions containing silica with 40% to 90% silica, by weight containing phosphorus, niobium or tantalum
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K77/00—Constructional details of devices covered by this subclass and not covered by groups H10K10/80, H10K30/80, H10K50/80 or H10K59/80
- H10K77/10—Substrates, e.g. flexible substrates
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K2102/00—Constructional details relating to the organic devices covered by this subclass
- H10K2102/301—Details of OLEDs
- H10K2102/311—Flexible OLED
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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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
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- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Ceramic Engineering (AREA)
- Glass Compositions (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
The non-alkali glass according to the present invention is characterized by: comprising, as a glass composition, in mass%, 55-80% of SiO2, 10-25% of Al2O3, 2-5.5% of B2O3, 3-8% of MgO, 3-10% of CaO, 0.5-5% of SrO and 0.5-7% of BaO; having a molar ratio MgO/CaO of 0.5-1.5; substantially not containing an alkali metal oxide; and having a Young's modulus of 80 GPa or higher.
Description
Technical field
The present invention relates to a kind of non-alkali glass, particularly relate to the non-alkali glass that is applicable to OLED display.
Background technology
The electronicss such as OLED display are slim, performance excellence aspect animation display, and power consumption is low, therefore is used for the purposes such as indicating meter of mobile telephone.
Substrate as OLED display is widely used sheet glass.With regard to the sheet glass of this purposes, the characteristic that major requirement is following.
(1) situation in order to prevent from spreading in the heat treatment step basic ion semiconductor substance after the film forming, and require not contain in fact alkalimetal oxide.
(2) in order to make cheapization of sheet glass, and require productivity excellent, particularly devitrification resistance, meltbility are excellent.
(3) in LTPS (low temperature poly silicon, low temperature polycrystalline silicon) technique, in order to reduce the thermal contraction of sheet glass, and require strain point high.
In addition, OLED display has become main flow towards mobile product at present, and anticipation can launch to organic EL TV aspect from now on, and intermediate manufacturer has begun the sale of organic EL TV.
Compare with mobile product, the panel size of organic EL TV significantly increases.Therefore, anticipation can be strengthened the maximization to sheet glass, the requirement of slimming from now on.
Patent documentation
Patent documentation 1: No. 4445176 communique of Japanese Patent
Summary of the invention
Invent problem to be solved
Make sheet glass maximization, slimming, then sheet glass becomes and is easy to deflection, and becoming is easy to produce variety of issue.
The sheet glass that is shaped at the glass manufacturer place can via operations such as cut-out, annealing, inspection, cleanings, in these operations, be put into sheet glass in the card casket that is formed with step shelf, and take out of from this card casket that is formed with step shelf.The common following formation of this card casket, that is, and the relative both sides of the shelf of the medial surface about being formed at mounting sheet glass, and can keep in the horizontal direction.But large-scale and thin sheet glass deflection is large, and therefore with the sheet glass directional input cassette time, the part of sheet glass contacts with the card casket and breakage occurs, and perhaps occurs significantly to shake and be easy to become unstable when carrying.Because electronic equipment set manufacturer also is the card casket that uses this form, therefore will produce same problem.
And, make that electronics maximizes, slimming, then be installed in sheet glass on this electronics and become and more be easy to deflection, therefore may see that the image surface of electronics deforms.
In order to address the above problem, studied by the specific Young's modulus (Young's modulus/density) that improves sheet glass or the method that Young's modulus reduces deflection.For example, disclosing specific Young's modulus in the patent documentation 1 is that the above and Young's modulus of 31GPa is the above non-alkali glass of 76GPa.But with regard to the non-alkali glass that patent documentation 1 is put down in writing, SrO and BaO are few, so devitrification resistance is low, are easy to occur devitrification when being shaped.In order to improve devitrification resistance, need to increase B
2O
3Content, B
2O
3It is the composition that reduces simultaneously Young's modulus and strain point.If Young's modulus and strain point reduce, then in LTPS technique, sheet glass will become and be easy to occur thermal contraction, and in the situation that make that sheet glass maximizes, slimming, and the problem that the deflection by sheet glass causes may occur.
Therefore, technical task of the present invention is, by Development and Production rate (particularly devitrification resistance) excellence and strain point and the sufficiently high non-alkali glass of Young's modulus, thereby in cheap for manufacturing costization that makes sheet glass, in LTPS technique, suppress the thermal contraction of sheet glass, even and in the situation that make that sheet glass maximizes, slimming, also can prevent the problem that the deflection by sheet glass causes.
Be used for solving the method for problem
The inventor etc. have carried out various experiments repeatedly, and it found that, by strictly stipulating the glass compositing range of non-alkali glass, and glass performance are defined in the pre-determined range, thereby can solve above-mentioned technical task, and then propose the present invention.That is, non-alkali glass of the present invention is characterized in that, forms as glass, in quality %, contains SiO
255～80%, Al
2O
310～25%, B
2O
32～5.5%, MgO3～8%, CaO3～10%, SrO0.5～5%, BaO0.5～7%, mol ratio MgO/CaO is 0.5～1.5, does not contain in fact alkalimetal oxide, Young's modulus is higher than 80GPa.At this, " not containing in fact alkalimetal oxide " refers to: the alkalimetal oxide (Li during glass forms
2O, Na
2O and K
2O) content is the following situation of 1000ppm (quality)." Young's modulus " refers to measure the value that gets by the bending resonant method.Need to prove, 1GPa is equivalent to approximately 101.9Kgf/mm
2
Non-alkali glass of the present invention is stipulated the glass compositing range in the above described manner.Thus, can improve fully devitrification resistance, strain point, Young's modulus.Particularly, as long as mol ratio MgO/CaO is defined as 0.5～1.5, then can improve significantly devitrification resistance, Young's modulus.
The second, preferably make non-alkali glass of the present invention also contain the SnO of 0.001～1 quality %
2
The 3rd, preferably make the strain point of non-alkali glass of the present invention be higher than 680 ℃.At this, " strain point " refer to based on the method for ASTM C336 measure and value.
The 4th, preferably make the liquidus temperature of non-alkali glass of the present invention be lower than 1210 ℃.At this, " liquidus temperature " can calculate by the following method, namely, will be by standard sieve 30 orders (500 μ m) but the glass powder that remains on 50 orders (300 μ m) is put into the platinum boat, afterwards, in temperature gradient furnace, kept 24 hours, measure the temperature of crystallization.
The 5th, preferably making the mean thermal expansion coefficients of non-alkali glass of the present invention in 30～380 ℃ temperature range is 30～50 * 10
-7/ ℃.At this, " mean thermal expansion coefficients in 30～380 ℃ the temperature range " can enough dilatometer measurements.
The 6th, preferably make non-alkali glass of the present invention 10
2.5Temperature during pool is lower than 1600 ℃.At this, " 10
2.5Temperature during pool " can enough platinum ball lifting the ball methods measure.
The 7th, preferably making the viscosity of non-alkali glass of the present invention under liquidus temperature is 10
4.8More than the pool.Need to prove, " viscosity under the liquidus temperature " can enough platinum ball lifting the ball methods be measured.
The 8th, non-alkali glass of the present invention is shaped with overflow downdraw and gets.
The 9th, preferably make the wall thickness of non-alkali glass of the present invention be thinner than 0.5mm.
The tenth, preferably make non-alkali glass of the present invention be used for organic EL device.
Embodiment
For the related non-alkali glass of embodiments of the present invention, form as glass, in quality %, contain SiO
255～80%, Al
2O
310～25%, B
2O
32～5.5%, MgO3～8%, CaO3～10%, SrO0.5～5%, BaO0.5～7%, mol ratio MgO/CaO is 0.5～1.5, does not contain in fact alkalimetal oxide.Containing shown in the reasons are as follows that scope limits each composition in the above described manner.Need to prove, below, unless otherwise specified, then in the explanation of the content of each composition, mark % refers to % by mole.
SiO
2It is the composition that forms the skeleton of glass.SiO
2Content be 55～80%, be preferably 55～75%, more preferably 55～70%, more preferably 55～65%.If SiO
2Content very few, then be difficult to improve Young's modulus.In addition, acid resistance becomes and is easy to reduce, and density excessively increases.On the other hand, if SiO
2Content too much, then high temperature viscosity increases, meltbility becomes and is easy to reduce, and the devitrification crystallization such as cristobalite becomes and be easy to separate out, liquidus temperature becomes and is easy to rise.
Al
2O
3Be the composition that forms the skeleton of glass, and be the composition that improves Young's modulus, and be the composition that suppresses phase-splitting.Al
2O
3Content be 10～25%, be preferably 12～20%, more preferably 14～20%.If Al
2O
3Content very few, then Young's modulus becomes and is easy to reduce, and glass becomes and is easy to phase-splitting.On the other hand, if Al
2O
3Content too much, then the crystallization of the devitrification such as mullite, lime feldspar becomes and is easy to separate out, liquidus temperature becomes and is easy to rise.
B
2O
3It is the composition that improves meltbility and improve devitrification resistance.B
2O
3Content be 2～5.5%, be preferably 2.5～5.5%, more preferably 3～5.5%, more preferably 3～5%.If B
2O
3Content very few, then meltbility, devitrification resistance become and are easy to reduce, and are that the tolerance of liquid becomes and is easy to reduce to hydrofluoric acid.On the other hand, if B
2O
3Content too much, then Young's modulus, acid resistance become and are easy to reduce.
MgO is the composition that reduces high temperature viscosity and improve meltbility, is the composition that improves significantly Young's modulus in alkaline earth metal oxide.The content of MgO is 3～8%, is preferably 3.5～8%, more preferably 4～8%, more preferably 4.5～8%, be particularly preferably 5～8%.If the content of MgO is very few, then meltbility, Young's modulus become and are easy to reduce.On the other hand, if the content of MgO is too much, then devitrification resistance becomes and is easy to reduce.
CaO does not reduce strain point and reduces high temperature viscosity and improve significantly the composition of meltbility.In addition, in alkaline earth metal oxide, the importing raw material of CaO is less expensive, is the composition that makes cheapization of raw materials cost therefore.The content of CaO is 3～10%, is preferably 3.5～9%, more preferably 4～8.5%, more preferably 4～8%, be particularly preferably 4～7.5%.If the content of CaO is very few, then be difficult to enjoy above-mentioned effect.On the other hand, if the content of CaO is too much, then glass becomes and is easy to devitrification.
SrO is the composition that suppresses phase-splitting and improve devitrification resistance.SrO does not still reduce strain point and reduces high temperature viscosity, improves the composition of meltbility, and is the composition that suppresses the rising of liquidus temperature.The content of SrO is 0.5～5%, is preferably 0.5～4%, more preferably 0.5～3.5%.Be lower than 0.5% if the content of SrO is crossed, then be difficult to enjoy above-mentioned effect.On the other hand, if the content of SrO is too much, then the devitrification crystallization of strontium silicate becomes and is easy to separate out, and devitrification resistance becomes and is easy to reduce.
BaO is the composition that improves devitrification resistance.The content of BaO is 0.5～7%, is preferably 0.5～6%, more preferably 0.5～5%, more preferably 0.5～4.5%.If the content of BaO is very few, then be difficult to enjoy above-mentioned effect.On the other hand, if the content of BaO is too much, then high temperature viscosity becomes too high, and meltbility becomes and is easy to reduce, and the devitrification crystallization that contains BaO becomes and be easy to separate out, and liquidus temperature is easy to rise.
Take into account high Young's modulus and high devitrification resistance and make sheet glass cheap for manufacturing costization aspect, mol ratio CaO/MgO is important component ratio.Mol ratio CaO/MgO is 0.5～1.5, is preferably 0.5～1.3, more preferably 0.5～1.2, more preferably 0.5～1.1, be particularly preferably 0.5～1.0.If mol ratio CaO/MgO is too small, then the devitrification crystallization of cristobalite becomes and is easy to separate out, and devitrification resistance becomes and is easy to reduce, and raw materials cost is easy to surging.On the other hand, if mol ratio CaO/MgO is excessive, then the devitrification crystallization of the alkali earths aluminosilicate such as lime feldspar system becomes and is easy to separate out, and devitrification resistance is easy to reduce, and is difficult to improve Young's modulus.
Except mentioned component, for example can also add following composition as any composition.Need to prove, from enjoying reliably the viewpoint of effect of the present invention, the content of other compositions beyond the mentioned component is preferably below 10% in total amount, is particularly preferably 5%.
ZnO is the composition that improves meltbility.But if contain in large quantities ZnO, then glass becomes and is easy to devitrification, and strain point is easy to reduce.The content of ZnO is 0～5%, more preferably 0～4%, more preferably 0～3%, be particularly preferably 0～2%.
SnO
2Be to have the composition of good clarification at high-temperature area, and be the composition that improves strain point, and be the composition that reduces high temperature viscosity.SnO
2Content be 0～1%, be preferably 0.001～1%, more preferably 0.01～0.5%, be particularly preferably 0.05～0.3%.If SnO
2Content too much, SnO then
2The devitrification crystallization become and be easy to separate out.In addition, if SnO
2Content be less than 0.001%, then be difficult to enjoy above-mentioned effect.
As mentioned above, SnO
2Be suitable as finings, but only otherwise the infringement glass performance, then can add separately F, Cl, SO up to 5%
3, C or the metal-powders such as Al, Si are as finings.In addition, as finings, also can add the CeO up to 5%
2Deng.
As finings, As
2O
3, Sb
2O
3Also be effective.Non-alkali glass of the present invention and incomplete the eliminating are contained these compositions, still from the viewpoint of environment, preferably do one's utmost to avoid using these compositions.And, if contain a large amount of As
2O
3, then have the tendency of anti-being exposed to the sun property reduction.As
2O
3Content be below 1%, be preferably below 0.5%, be particularly preferably below 0.1%, wish not contain in fact As
2O
3At this, " do not contain in fact As
2O
3" refer to: the As during glass forms
2O
3Content be lower than 0.05% situation.In addition, Sb
2O
3Content be below 1%, be particularly preferably below 0.5%, wish not contain in fact Sb
2O
3At this, " do not contain in fact Sb
2O
3" refer to the Sb of glass in forming
2O
3Content be lower than 0.05% situation.
Cl has the effect of the melting that promotes non-alkali glass, if add Cl, then can make melt temperature low temperature, and promotes the effect of finings, consequently, when making with low costization of melting, can realize the long lifetime of glass melter.But if the content of Cl is too much, then strain point becomes and is easy to reduce.Therefore, the content of Cl is below 3%, is preferably below 1%, is particularly preferably below 0.5%.In addition, as the importing raw material of Cl, can use the raw materials such as the muriate of the alkaline earth metal oxides such as strontium chloride or aluminum chloride.
P
2O
5Be the composition that improves strain point, and be the composition that can suppress significantly the devitrification crystallization of the alkali earths aluminosilicate system such as lime feldspar.But, if contain in large quantities P
2O
5, then glass becomes and is easy to phase-splitting.P
2O
5Content be 0～2.5%, be preferably 0～1.5%, more preferably 0～0.5%, more preferably 0～0.3%.
TiO
2Be the composition that reduces high temperature viscosity and improve meltbility, and be the composition that inhibition is exposed to the sun, if but contain in large quantities TiO
2, then the glass generation is painted, and transmissivity becomes and is easy to reduce.TiO
2Content be 0～5%, be preferably 0～3%, more preferably 0～1%, be particularly preferably 0～0.02%.
Y
2O
3, Nb
2O
5, La
2O
3Has the effect that improves strain point, Young's modulus etc.But, if these compositions content separately more than 5%, then density becomes and is easy to increase.
The strain point of non-alkali glass of the present invention preferably surpasses 680 ℃, more preferably more than 685 ℃, more preferably more than 690 ℃, is particularly preferably more than 695 ℃.Thus, in LTPS technique, can suppress the thermal contraction of sheet glass.
The Young's modulus of non-alkali glass of the present invention surpasses 80GPa, is preferably more than the 82GPa, more preferably more than the 83GPa, is particularly preferably more than the 83.5GPa.If Young's modulus is excessively low, then be easy to occur the problem that the deflection by sheet glass causes.
The mean thermal expansion coefficients of the non-alkali glass of present embodiment in 30～380 ℃ temperature range is 30～50 * 10
-7/ ℃, be preferably 32～50 * 10
-7/ ℃, more preferably 33～50 * 10
-7/ ℃, more preferably 34～50 * 10
-7/ ℃, be particularly preferably 35～50 * 10
-7/ ℃.Thus, be easy to matched coefficients of thermal expansion with the employed Si of TFT.
The liquidus temperature of the non-alkali glass of present embodiment is lower than 1210 ℃, is preferably below 1200 ℃, is particularly preferably below 1190 ℃.Thus, be easy to prevent when glass manufacture, produce the devitrification crystallization and situation that productivity is descended.And, be easy to form with overflow downdraw, therefore be easy to improve the surface quality of sheet glass, and can make cheap for manufacturing costization of sheet glass.Need to prove, liquidus temperature is the index of devitrification resistance, and liquidus temperature is lower, and then devitrification resistance is more excellent.
In recent years, be accompanied by the high-precision refinement of indicating meter and have the tendency of circuit pattern miniaturization.Therefore, all the time also unquestioned small foreign matter become just gradually cause open circuit, the reason of short circuit.From preventing the viewpoint of this problem, the meaning that improves devitrification resistance is very large.
The viscosity of the non-alkali glass of present embodiment under liquidus temperature is 10
4.8More than the pool, be preferably 10
5.0More than the pool, more preferably 10
5.2More than the pool, be particularly preferably 10
5.5More than the pool.Thus, be difficult to occur devitrification during shaping, therefore be easy to make glass-pane shaping with overflow downdraw, consequently, can improve the surface quality of sheet glass, and can make cheap for manufacturing costization of sheet glass.Need to prove, the viscosity under the liquidus temperature is the index of plasticity, and the viscosity under the liquidus temperature is higher, and then plasticity more improves.
The non-alkali glass of present embodiment is 10
2.5Temperature during pool is below 1600 ℃, is preferably below 1580 ℃, is particularly preferably below 1570 ℃.If 10
2.5Temperature during pool uprises, and then is difficult to make glass to melt, and the manufacturing cost of sheet glass is surging.Need to prove 10
2.5Temperature during pool is equivalent to melt temperature, and this temperature is lower, and then meltbility more improves.
The non-alkali glass of present embodiment preferably is shaped with overflow downdraw and gets.Overflow downdraw is following method, that is, melten glass is overflowed from the both sides of stable on heating groove shape works, makes the melten glass that overflows when the lower end of groove shape works is converged, extends downwards to be shaped and the manufacturing sheet glass.In the overflow downdraw, the face that will become the surface of sheet glass does not contact with groove shape refractory body, and is shaped with the state of free surface.Therefore, can not make at an easy rate the good sheet glass of surface quality by grinding, and be easy to slimming.Need to prove, as long as structure, the material of the employed groove shape of overflow downdraw works can realize required size, surface accuracy, then do not need to be particularly limited.In addition, when the extension shaping of carrying out downwards, the method that applies power also is not particularly limited.For example, can adopt the method that under the state that makes thermotolerance roller with enough large width and glass contact, makes the rotation of thermotolerance roller and extend, also can adopt a plurality of paired thermotolerance rollers only with near the end face of glass are contacted and the method for extending.
Except overflow downdraw, also can form sheet glass by such as glass tube down-drawing (discharge orifice glass tube down-drawing etc.), float glass process etc.
In the non-alkali glass of present embodiment, wall thickness is not particularly limited, but is preferably less than 0.5mm, more preferably below the 0.4mm, more preferably below the 0.35mm, is particularly preferably below the 0.3mm.Wall thickness is thinner, then more can realize the lightweight of equipment.Flow when wall thickness can be by glass manufacture, plate pull speed etc. are regulated.
The non-alkali glass of present embodiment is preferred for organic EL device, is particularly preferred for OLED display.Particularly in the TV purposes, produce the device of a plurality of parts at sheet glass after, each device separated cuts off, thereby realize cost (so-called jigsaw).The liquidus temperature of non-alkali glass of the present invention is low, and the viscosity under liquidus temperature is high, therefore is easy to the sheet glass of molding large, can satisfy this generic request.
Embodiment
Below, embodiments of the invention are described.Need to prove, following embodiment only is illustration.The present invention is not subjected to any restriction of following examples.
Table 1,2 shows embodiments of the invention (sample No.1～13) and comparative example (sample No.14,15).
[table 1]
[table 2]
At first, form according to the glass in the table, the glass batch that the blending frit is got was put into platinum crucible, 1600～1650 ℃ of lower meltings 24 hours.When the dissolving of glass batch, use the platinum agitator to stir, homogenize.Next, melten glass is cast on the carbon plate, be configured as tabular after, under near the temperature the annealing point annealing 30 minutes.To resulting each sample, mean thermal expansion coefficients CTE, strain point Ps, annealing point Ta, softening temperature Ts, the high temperature viscosity estimated in density, 30～380 ℃ the temperature range are 10
4Temperature during dPas, high temperature viscosity are 10
3Temperature during dPas, high temperature viscosity are 10
2.5Temperature during dPas, liquidus temperature TL, and liquidus temperature TL under viscosity log
10η TL.
Density is for measuring the value that gets according to known Archimedes's method.
The value of mean thermal expansion coefficients CTE in 30～380 ℃ the temperature range for using dilatometer measurement to get.
Strain point Ps, annealing point Ta, softening temperature Ts measure the value that gets for the method based on ASTM C336.
High temperature viscosity is 10
4DPas, 10
3DPas, 10
2.5Temperature during dPas is for measuring the value that gets with platinum ball lifting the ball method.
Liquidus temperature TL is with by standard sieve 30 orders (500 μ m) but the glass powder that remains on 50 orders (300 μ m) is put into the platinum boat, keeps in temperature gradient furnace after 24 hours, measure crystallization temperature and value.
Viscosity log under the liquidus temperature
10η TL is for measuring the value that gets with platinum ball lifting the ball method to the viscosity of the glass under the liquidus temperature TL.
By table 1,2 as can be known, for sample No.1～13, because the glass composition is defined in the pre-determined range, therefore Young's modulus is 80GPa, strain point is higher than 680 ℃, and liquidus temperature is lower than 1210 ℃, can reduce thus the thermal contraction in the LTPS technique, even sheet glass maximizes, slimming, also be difficult to occur the problem that is caused by deflection.Therefore, think that sample No.1～13 are suitable as the substrate of OLED display.
On the other hand, for sample No.14, be not defined in the pre-determined range owing to glass is formed, so liquidus temperature is high, devitrification resistance is low.Therefore, the plasticity of sample No.14 is poor, and may cause because of small foreign matter quality, the reliability decrease of indicating meter.In addition, for sample No.15, be not defined in the pre-determined range owing to glass is formed, therefore 10
2.5The time temperature high, Young's modulus is low.Therefore, the meltbility of sample No.15 is poor, and if make sheet glass maximization, slimming, then may produce the problem that is caused by deflection.
Utilizability on the industry
Non-alkali glass of the present invention be suitable for the flat display substrates such as liquid-crystal display, EL indicating meter, charge coupled cell (CCD), etc. the substrate of the protective glass used of the image sensors such as times contact-type solid-state imager (CIS), used for solar batteries and protective glass, organic EL illuminating with substrate etc., be particularly suitable as the OLED display substrate.
Claims (10)
1. a non-alkali glass is characterized in that, forms as glass, in quality %, contains SiO
255～80%, Al
2O
310～25%, B
2O
32～5.5%, MgO3～8%, CaO3～10%, SrO0.5～5%, BaO0.5～7%, mol ratio MgO/CaO is 0.5～1.5, does not contain in fact alkalimetal oxide, Young's modulus is higher than 80GPa.
2. non-alkali glass according to claim 1 is characterized in that, also contains the SnO of 0.001～1 quality %
2
3. non-alkali glass according to claim 1 and 2 is characterized in that, strain point is higher than 680 ℃.
4. the described non-alkali glass of any one is characterized in that according to claim 1～3, and liquidus temperature is lower than 1210 ℃.
5. the described non-alkali glass of any one is characterized in that according to claim 1～4, and the mean thermal expansion coefficients in 30～380 ℃ the temperature range is 30～50 * 10
-7/ ℃.
6. the described non-alkali glass of any one is characterized in that 10 according to claim 1～5
2.5Temperature during pool is lower than 1600 ℃.
7. the described non-alkali glass of any one is characterized in that according to claim 1～6, and the viscosity under the liquidus temperature is 10
4.8More than the pool.
8. the described non-alkali glass of any one is characterized in that according to claim 1～7, is shaped and gets with overflow downdraw.
9. the described non-alkali glass of any one is characterized in that according to claim 1～8, and wall thickness is thinner than 0.5mm.
10. the described non-alkali glass of any one is characterized in that according to claim 1～9, is used for organic electroluminescence device.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011-049756 | 2011-03-08 | ||
| JP2011049756A JP5831838B2 (en) | 2011-03-08 | 2011-03-08 | Alkali-free glass |
| PCT/JP2012/055802 WO2012121283A1 (en) | 2011-03-08 | 2012-03-07 | Non-alkali glass |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103313948A true CN103313948A (en) | 2013-09-18 |
| CN103313948B CN103313948B (en) | 2016-02-17 |
Family
ID=46798239
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201280005480.XA Active CN103313948B (en) | 2011-03-08 | 2012-03-07 | Non-alkali glass |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP5831838B2 (en) |
| KR (1) | KR101505462B1 (en) |
| CN (1) | CN103313948B (en) |
| TW (1) | TWI555715B (en) |
| WO (1) | WO2012121283A1 (en) |
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Also Published As
| Publication number | Publication date |
|---|---|
| JP2012184146A (en) | 2012-09-27 |
| KR101505462B1 (en) | 2015-03-25 |
| KR20130135903A (en) | 2013-12-11 |
| JP5831838B2 (en) | 2015-12-09 |
| CN103313948B (en) | 2016-02-17 |
| WO2012121283A1 (en) | 2012-09-13 |
| TWI555715B (en) | 2016-11-01 |
| TW201242922A (en) | 2012-11-01 |
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