CN103313948B - Non-alkali glass - Google Patents

Non-alkali glass Download PDF

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Publication number
CN103313948B
CN103313948B CN201280005480.XA CN201280005480A CN103313948B CN 103313948 B CN103313948 B CN 103313948B CN 201280005480 A CN201280005480 A CN 201280005480A CN 103313948 B CN103313948 B CN 103313948B
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glass
alkali glass
easy
temperature
glass according
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CN103313948A (en
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川口贵弘
三和晋吉
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Nippon Electric Glass Co Ltd
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Nippon Electric Glass Co Ltd
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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
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • 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

Non-alkali glass of the present invention, is characterized in that, as glass composition, in mass %, containing 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, and in fact not containing alkalimetal oxide, Young's modulus is higher than 80GPa.

Description

Non-alkali glass
Technical field
The present invention relates to a kind of non-alkali glass, particularly relate to the non-alkali glass being applicable to OLED display.
Background technology
The electronicss such as OLED display are slim, and in animation display, performance is excellent, and power consumption is low, therefore for the purposes such as indicating meter of mobile telephone.
As the substrate of OLED display, widely use sheet glass.With regard to the sheet glass of this purposes, the characteristic below major requirement.
(1) in order to prevent the situation that basic ion spreads in the semiconductor substance after film forming in heat treatment step, and require in fact not containing alkalimetal oxide.
(2) in order to make sheet glass cheapization, and require that productivity is excellent, particularly devitrification resistance, meltbility excellence.
(3) in LTPS (lowtemperaturepolysilicon, low temperature polycrystalline silicon) technique, in order to reduce the thermal contraction of sheet glass, and require that strain point is high.
In addition, OLED display becomes main flow towards mobile product at present, and anticipation can launch to organic EL TV aspect from now on, and intermediate manufacturer has started the sale of organic EL TV.
Compared with mobile product, the panel size of organic EL TV significantly increases.Therefore, anticipation can strengthen the requirement of maximization to sheet glass, slimming from now on.
Patent documentation
Patent documentation 1: Japanese Patent No. 4445176 publication
Summary of the invention
Invent problem to be solved
Make sheet glass maximization, slimming, then sheet glass becomes and is easy to flexure, becomes and is easy to produce various problem.
Sheet glass via operations such as cut-out, annealing, inspection, cleanings, in these operations, can be put into and is formed in the card casket of step shelf, and take out of from this card casket being formed with step shelf by the sheet glass be shaped at glass manufacturer place.This card casket is formed usually as follows, that is, the shelf of medial surface being formed at left and right loads the relative both sides of sheet glass, and can keep in the horizontal direction.But large-scale and thin sheet glass deflection is large, and therefore when by sheet glass directional input cassette, a part for sheet glass contacts with card casket and breakage occurs, or occur when carrying significantly shake and be easy to become unstable.Because electronic equipment set manufacturer is also the card casket using this form, therefore same problem will be produced.
And make electronics maximization, slimming, then the sheet glass installed on the electronic equipment becomes and is more easy to flexure, therefore may see that the image surface of electronics deforms.
In order to solve the problem, have studied the method reducing deflection by improving the specific Young's modulus (Young's modulus/density) of sheet glass or Young's modulus.For example, Patent Document 1 discloses specific Young's modulus is more than 31GPa and Young's modulus is the non-alkali glass of more than 76GPa.But with regard to the non-alkali glass described in patent documentation 1, SrO and BaO is few, and therefore devitrification resistance is low, be easy to when being shaped devitrification occurs.In order to improve devitrification resistance, need to increase B 2o 3content, B 2o 3it is the composition simultaneously reducing 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 thermal contraction occurs, and when making sheet glass maximization, slimming, the problem caused by the flexure of sheet glass may occur.
Therefore, technical task of the present invention is, excellent and strain point and the sufficiently high non-alkali glass of Young's modulus by Development and Production rate (particularly devitrification resistance), thus while cheap for manufacturing costization making sheet glass, the thermal contraction of sheet glass is suppressed in LTPS technique, even and if when making sheet glass maximization, slimming, the problem caused by the flexure of sheet glass also can be prevented.
For solving the method for problem
The present inventor etc. have carried out various experiment repeatedly, and it found that, by strictly specifying the glass compositing range of non-alkali glass, and are defined in pre-determined range by glass performance, thus 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, as glass composition, in mass %, containing 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, and in fact not containing alkalimetal oxide, Young's modulus is higher than 80GPa.At this, " in fact not containing alkalimetal oxide " refers to: the alkalimetal oxide (Li in glass composition 2o, Na 2o and K 2o) content is 1000ppm (quality) situation below." Young's modulus " refers to the value obtained by bending resonant method mensuration.It should be noted that, 1GPa is equivalent to about 101.9Kgf/mm 2.
Non-alkali glass of the present invention specifies glass compositing range in the above described manner.Thereby, it is possible to improve devitrification resistance, strain point, Young's modulus fully.Particularly, as long as mol ratio MgO/CaO is defined as 0.5 ~ 1.5, then can improve devitrification resistance, Young's modulus significantly.
The second, preferably make the SnO of non-alkali glass of the present invention also containing 0.001 ~ 1 quality % 2.
3rd, preferably make the strain point of non-alkali glass of the present invention higher than 680 DEG C.At this, " strain point " refers to that the method based on ASTMC336 measures and the value that obtains.
4th, preferably make the liquidus temperature of non-alkali glass of the present invention lower than 1210 DEG C.At this, " liquidus temperature " calculates by following method, namely, by by standard sieve 30 order (500 μm) but the glass powder remained on 50 orders (300 μm) puts into platinum boat, afterwards, keep 24 hours in temperature gradient furnace, measure the temperature of crystallization.
5th, preferably make the mean thermal expansion coefficients of non-alkali glass of the present invention in the temperature range of 30 ~ 380 DEG C be 30 ~ 50 × 10 -7/ DEG C.At this, " mean thermal expansion coefficients in the temperature range of 30 ~ 380 DEG C " can use dilatometer measurement.
6th, preferably make non-alkali glass of the present invention 10 2.5temperature during pool is lower than 1600 DEG C.At this, " 10 2.5temperature during pool " can measure by platinum ball lifting the ball method.
7th, preferably make the viscosity of non-alkali glass of the present invention under liquidus temperature be 10 4.8more than pool.It should be noted that, " viscosity under liquidus temperature " can measure by platinum ball lifting the ball method.
8th, preferably make non-alkali glass overflow downdraw of the present invention be shaped and obtain.
9th, preferably make the wall thickness of non-alkali glass of the present invention be thinner than 0.5mm.
Tenth, preferably make non-alkali glass of the present invention for organic EL device.
Embodiment
For the non-alkali glass involved by embodiments of the present invention, as glass composition, in mass %, containing 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, in fact not containing alkalimetal oxide.As follows to the reason limited containing scope of each composition in the above described manner.It should be noted that, below, unless otherwise specified, then in the explanation of the content of each composition, mark % refers to % by mole.
SiO 2it is the composition of the skeleton forming glass.SiO 2content be 55 ~ 80%, be preferably 55 ~ 75%, be more preferably 55 ~ 70%, more preferably 55 ~ 65%.If SiO 2content very few, be then 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, and meltbility becomes and is easy to reduce, and the devitrification crystallization such as cristobalite becomes and is easy to separate out, and liquidus temperature becomes and is easy to rise.
Al 2o 3be the composition of the skeleton forming glass, and be the composition improving Young's modulus, and be the composition suppressing phase-splitting.Al 2o 3content be 10 ~ 25%, be preferably 12 ~ 20%, be 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, and liquidus temperature becomes and is easy to rise.
B 2o 3it is the composition improving meltbility and improve devitrification resistance.B 2o 3content be 2 ~ 5.5%, be preferably 2.5 ~ 5.5%, be 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 become the tolerance of hydrofluoric acid system liquid and be easy to reduce.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 reducing high temperature viscometrics and improve meltbility, is the composition improving Young's modulus in alkaline earth metal oxide significantly.The content of MgO is 3 ~ 8%, is preferably 3.5 ~ 8%, is 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 viscometrics and improve the composition of meltbility significantly.In addition, in alkaline earth metal oxide, the importing raw material of CaO is less expensive, is therefore the composition making low raw-material cost.The content of CaO is 3 ~ 10%, is preferably 3.5 ~ 9%, is more preferably 4 ~ 8.5%, more preferably 4 ~ 8%, be particularly preferably 4 ~ 7.5%.If the content of CaO is very few, be then 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 suppressing phase-splitting and improve devitrification resistance.SrO does not still reduce strain point and reduces the composition of high temperature viscometrics, raising meltbility, and is the composition of the rising suppressing liquidus temperature.The content of SrO is 0.5 ~ 5%, is preferably 0.5 ~ 4%, is more preferably 0.5 ~ 3.5%.If the content of SrO is crossed lower than 0.5%, be then 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 improving devitrification resistance.The content of BaO is 0.5 ~ 7%, is preferably 0.5 ~ 6%, is more preferably 0.5 ~ 5%, more preferably 0.5 ~ 4.5%.If the content of BaO is very few, be then 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 containing BaO becomes and is easy to separate out, and liquidus temperature is easy to rise.
Take into account high Young's modulus and high devitrification resistance and make cheap for manufacturing costization of sheet glass in, mol ratio CaO/MgO is important component ratio.Mol ratio CaO/MgO is 0.5 ~ 1.5, is preferably 0.5 ~ 1.3, is 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 system such as lime feldspar 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, such as, can also add following composition as any composition.It should be noted that, from the view point of reliably enjoying effect of the present invention, the content of other compositions beyond mentioned component is preferably less than 10% with total amount, is particularly preferably 5%.
ZnO is the composition improving meltbility.But if in large quantities containing ZnO, then glass becomes and is easy to devitrification, and strain point is easy to reduce.The content of ZnO is 0 ~ 5%, is more preferably 0 ~ 4%, more preferably 0 ~ 3%, be particularly preferably 0 ~ 2%.
SnO 2be the composition at high-temperature area with good clarification, and be the composition improving strain point, and be the composition reducing high temperature viscometrics.SnO 2content be 0 ~ 1%, be preferably 0.001 ~ 1%, be more preferably 0.01 ~ 0.5%, be particularly preferably 0.05 ~ 0.3%.If SnO 2content too much, then SnO 2devitrification crystallization become be easy to separate out.In addition, if SnO 2content be less than 0.001%, be then difficult to enjoy above-mentioned effect.
As mentioned above, SnO 2be suitable as finings, but only otherwise infringement glass performance, then can add separately up to 5% F, Cl, SO 3, the metal-powder such as C or Al, Si is as finings.In addition, as finings, the CeO up to 5% also can be added 2deng.
As finings, As 2o 3, Sb 2o 3also be effective.Non-alkali glass of the present invention is also not exclusively got rid of containing these compositions, but from the view point of environment, preferably does one's utmost to avoid using these compositions.And, if containing a large amount of As 2o 3, then there is the tendency that resistance to being exposed to the sun property reduces.As 2o 3content be less than 1%, be preferably less than 0.5%, be particularly preferably less than 0.1%, wishes in fact not contain As 2o 3.At this, " in fact not containing As 2o 3" refer to: the As in glass composition 2o 3content lower than 0.05% situation.In addition, Sb 2o 3content be less than 1%, be particularly preferably less than 0.5%, wish in fact not containing Sb 2o 3.At this, " in fact not containing Sb 2o 3" refer to glass composition in Sb 2o 3content lower than 0.05% situation.
Cl has the effect of the melting promoting non-alkali glass, if add Cl, then can make melt temperature low temperature, and promote the effect of finings, consequently, while making melting with low costization, 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 less than 3%, is preferably less than 1%, is particularly preferably less than 0.5%.In addition, as the importing raw material of Cl, the raw material such as muriate or aluminum chloride of the alkaline earth metal oxides such as strontium chloride can be used.
P 2o 5be the composition improving strain point, and be the composition that can suppress the devitrification crystallization of the alkali earths aluminosilicate systems such as lime feldspar significantly.But, if in large quantities containing P 2o 5, then glass becomes and is easy to phase-splitting.P 2o 5content be 0 ~ 2.5%, be preferably 0 ~ 1.5%, be more preferably 0 ~ 0.5%, more preferably 0 ~ 0.3%.
TiO 2be the composition reducing high temperature viscometrics and improve meltbility, and be the composition suppressing to be exposed to the sun, but if in large quantities containing TiO 2, then glass occurs painted, and transmissivity becomes and is easy to reduce.TiO 2content be 0 ~ 5%, be preferably 0 ~ 3%, be more preferably 0 ~ 1%, be particularly preferably 0 ~ 0.02%.
Y 2o 3, Nb 2o 5, La 2o 3there is the effect improving strain point, Young's modulus etc.But if these compositions content is separately more than 5%, then density becomes and is easy to increase.
The strain point of non-alkali glass of the present invention, preferably greater than 680 DEG C, is more preferably more than 685 DEG C, more preferably more than 690 DEG C, is particularly preferably more than 695 DEG C.Thus, the thermal contraction of sheet glass can be suppressed in LTPS technique.
The Young's modulus of non-alkali glass of the present invention, more than 80GPa, is preferably more than 82GPa, is more preferably more than 83GPa, is particularly preferably more than 83.5GPa.If Young's modulus is too low, be then easy to the problem occurring to be caused by the flexure of sheet glass.
The mean thermal expansion coefficients of non-alkali glass in the temperature range of 30 ~ 380 DEG C of present embodiment is 30 ~ 50 × 10 -7/ DEG C, be preferably 32 ~ 50 × 10 -7/ DEG C, be more preferably 33 ~ 50 × 10 -7/ DEG C, more preferably 34 ~ 50 × 10 -7/ DEG C, be particularly preferably 35 ~ 50 × 10 -7/ DEG C.Thus, the matched coefficients of thermal expansion of the Si used with TFT is easy to.
The liquidus temperature of the non-alkali glass of present embodiment, lower than 1210 DEG C, is preferably less than 1200 DEG C, is particularly preferably less than 1190 DEG C.Thus, be easy to prevent produce devitrification crystallization when glass manufacture and situation that productivity is declined.And, be easy to form by overflow downdraw, be therefore easy to the surface quality improving sheet glass, and cheap for manufacturing costization of sheet glass can be made.It should be noted that, liquidus temperature is the index of devitrification resistance, and liquidus temperature is lower, then devitrification resistance is more excellent.
In recent years, the tendency of circuit pattern miniaturization is there is along with the high-precision refinement of indicating meter.Therefore, all the time and unquestioned small foreign matter becomes the reason causing open circuit, short circuit just gradually.From the view point of preventing this problem, the meaning improving devitrification resistance is very large.
The viscosity of non-alkali glass under liquidus temperature of present embodiment is 10 4.8more than pool, be preferably 10 5.0more than pool, be more preferably 10 5.2more than pool, be particularly preferably 10 5.5more than pool.Thus, be difficult to during shaping devitrification occurs, be therefore easy to make glass-pane shaping by overflow downdraw, consequently, the surface quality of sheet glass can be improved, and cheap for manufacturing costization of sheet glass can be made.It should be noted that, the viscosity under liquidus temperature is the index of plasticity, and the viscosity under liquidus temperature is higher, then plasticity more improves.
The non-alkali glass of present embodiment is 10 2.5temperature during pool is less than 1600 DEG C, is preferably less than 1580 DEG C, is particularly preferably less than 1570 DEG C.If 10 2.5temperature during pool uprises, be then difficult to glass is melted, and the manufacturing cost of sheet glass is surging.It should be noted that, 10 2.5temperature during pool is equivalent to melt temperature, and this temperature is lower, then meltbility more improves.
The non-alkali glass of present embodiment is preferably shaped by overflow downdraw and obtains.Overflow downdraw is following method, that is, make melten glass overflow from the both sides of the channel-shaped works of thermotolerance, while the lower end making the melten glass of spilling at channel-shaped works is converged, extends downwards and is shaped and manufactures sheet glass.In overflow downdraw, the face becoming the surface of sheet glass is not contacted with channel-shaped refractory body, and is shaped with the state of free surface.Therefore, the good sheet glass of surface quality can not be manufactured at an easy rate by grinding, and be easy to slimming.It should be noted that, as long as the structure of the channel-shaped works that uses of overflow downdraw, material can realize required size, surface accuracy, then do not need to be particularly limited to.In addition, when carrying out extension downwards and being shaped, the method applying power is also not particularly limited.Such as, can adopt and under the state of the thermotolerance roller and glass contact that make to have enough large width, thermotolerance roller rotated and carry out the method that extends, also can adopt make multiple paired thermotolerance roller only with contact near the end face of glass and carry out the method that extends.
Except overflow downdraw, also by such as glass tube down-drawing (discharge orifice glass tube down-drawing etc.), float glass process etc., sheet glass is formed.
In the non-alkali glass of present embodiment, wall thickness is not particularly limited, but is preferably less than 0.5mm, is more preferably below 0.4mm, more preferably below 0.35mm, is particularly preferably below 0.3mm.Wall thickness is thinner, then more can realize the lightweight of equipment.Wall thickness regulates by flow during glass manufacture, plate pull speed etc.
The non-alkali glass of present embodiment is preferred for organic EL device, is particularly preferred for OLED display.Particularly in TV purposes, after producing the device of multiple part on a glass, each Device singulation is driven into row and cut off, thus realize cost reduction (so-called jigsaw).The liquidus temperature of non-alkali glass of the present invention is low, and viscosity under liquidus temperature is high, is therefore easy to the sheet glass of molding large, can meets this generic request.
Embodiment
Below, embodiments of the invention are described.It should be noted that, following embodiment is only illustration.The present invention is not by 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]
First, according to the glass composition in table, the glass batch obtained by blending frit puts into platinum crucible, melting 24 hours at 1600 ~ 1650 DEG C.When the dissolving of glass batch, use platinum agitator to stir, homogenize.Next, make melten glass be cast on carbon plate, after being configured as tabular, anneal 30 minutes at the temperature near annealing point.To obtained each sample, have rated mean thermal expansion coefficients CTE, strain point Ps in density, the temperature range of 30 ~ 380 DEG C, annealing point Ta, softening temperature Ts, high temperature viscosity be 10 4temperature during dPas, high temperature viscosity are 10 3temperature during dPas, high temperature viscosity are 10 2.5viscosity log under temperature during dPas, liquidus temperature TL and liquidus temperature TL 10η TL.
Density is measure according to known Archimedes method the value obtained.
Mean thermal expansion coefficients CTE in the temperature range of 30 ~ 380 DEG C is the value using dilatometer measurement to obtain.
Strain point Ps, annealing point Ta, softening temperature Ts measure based on the method for ASTMC336 the value obtained.
High temperature viscosity is 10 4dPas, 10 3dPas, 10 2.5temperature during dPas is measure by platinum ball lifting the ball method the value obtained.
Liquidus temperature TL is by by standard sieve 30 order (500 μm) but the glass powder remained on 50 orders (300 μm) puts into platinum boat, keeps after 24 hours in temperature gradient furnace, measures the temperature of crystallization and the value that obtains.
Viscosity log under liquidus temperature 10η TL measures by the viscosity of platinum ball lifting the ball method to the glass under liquidus temperature TL the value obtained.
From table 1,2, for sample No.1 ~ 13, due to glass composition is defined in pre-determined range, therefore Young's modulus is 80GPa, strain point is higher than 680 DEG C, and liquidus temperature, lower than 1210 DEG C, can reduce the thermal contraction in LTPS technique thus, even if sheet glass maximizes, slimming, be also difficult to occur by bending the problem caused.Therefore, think that sample No.1 ~ 13 are suitable as the substrate of OLED display.
On the other hand, for sample No.14, owing to not being defined in pre-determined range by glass composition, therefore liquidus temperature is high, and devitrification resistance is low.Therefore, the plasticity of sample No.14 is poor, and may cause quality, the reliability decrease of indicating meter because of small foreign matter.In addition, for sample No.15, owing to glass composition not being defined in pre-determined range, therefore 10 2.5time temperature high, Young's modulus is low.Therefore, the meltbility of sample No.15 is poor, and if make, sheet glass maximizes, slimming, then may produce by bending the problem caused.
Utilizability in industry
Non-alkali glass of the present invention is suitable for the protective glass of the image sensors such as the flat display substrate such as liquid-crystal display, EL indicating meter, charge coupled cell (CCD), equimultiple contact-type solid-state imager (CIS), substrate used for solar batteries and protective glass, organic EL illuminating substrate etc., is particularly suitable as OLED display substrate.

Claims (10)

1. a non-alkali glass, is characterized in that, as glass composition, in mass %, containing SiO 255 ~ 80%, Al 2o 310 ~ 25%, B 2o 32 ~ 5.5%, MgO3.5 ~ 8%, CaO3 ~ 7.5%, SrO0.5 ~ 5%, BaO0.5 ~ 7%, mol ratio MgO/CaO is 0.5 ~ 1.3, and in fact not containing alkalimetal oxide, Young's modulus is more than 83GPa, and liquidus temperature is less than 1210 DEG C.
2. non-alkali glass according to claim 1, is characterized in that, the SnO also containing 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 DEG C.
4. non-alkali glass according to claim 1 and 2, is characterized in that, liquidus temperature is lower than 1210 DEG C.
5. non-alkali glass according to claim 1 and 2, is characterized in that, the mean thermal expansion coefficients in the temperature range of 30 ~ 380 DEG C is 30 ~ 50 × 10 -7/ DEG C.
6. non-alkali glass according to claim 1 and 2, is characterized in that, 10 2.5temperature during pool is lower than 1600 DEG C.
7. non-alkali glass according to claim 1 and 2, is characterized in that, the viscosity under liquidus temperature is 10 4.8more than pool.
8. non-alkali glass according to claim 1 and 2, is characterized in that, is shaped and obtains by overflow downdraw.
9. non-alkali glass according to claim 1 and 2, is characterized in that, wall thickness is thinner than 0.5mm.
10. non-alkali glass according to claim 1 and 2, is characterized in that, for organic electroluminescence device.
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