阅读说明：本技术 无碱玻璃 (Alkali-free glass ) 是由 村田哲哉 三和晋吉 于 2014-10-10 设计创作，主要内容包括：本发明提供一种无碱玻璃,其是即使在玻璃组成中的B<Sub>2</Sub>O<Sub>3</Sub>的含量少的情况下,也可以兼具耐开裂性、耐化学药品性的无碱玻璃,其特征在于,以摩尔％计含有SiO<Sub>2</Sub> 66～78％、Al<Sub>2</Sub>O<Sub>3</Sub> 8～15％、B<Sub>2</Sub>O<Sub>3</Sub> 0～1.8％、MgO 0～8％、CaO 1～15％、SrO 0～8％、BaO 1～8％作为玻璃组成,实质上不含有碱金属氧化物,应变点高于725℃。(The invention provides an alkali-free glass, which is B in glass composition 2 O 3 An alkali-free glass having both of cracking resistance and chemical resistance even when the content of (A) is small, characterized by containing SiO in mol% 2 66～78％、Al 2 O 3 8～15％、B 2 O 3 0 to 1.8% of MgO, 1 to 15% of CaO, 0 to 8% of SrO, and 1 to 8% of BaO as a glass composition, and substantially not containing an alkali metal oxide, and having a strain point higher than 725 ℃.)

1. An alkali-free glass characterized by containing SiO in mol%₂66％～78％、Al₂O₃8％～15％、B₂O₃0 to 1.8 percent of glass composition, 0 to 8 percent of MgO, 1 to 15 percent of CaO, 0 to 8 percent of SrO and 1 to 8 percent of BaO, and the glass composition does not substantially contain alkali metal oxides and has a strain point higher than 725 ℃.

2. The alkali-free glass according to claim 1, wherein B is₂O₃Is less than 0.1 mol%.

3. The alkali-free glass according to claim 1, wherein B is₂O₃The content of (b) is 0.1 mol% or more and less than 1 mol%.

4. The alkali-free glass according to any one of claims 1 to 3, further comprising 0.001 to 1 mol% of SnO₂As a glass composition.

5. The alkali-free glass of any one of claims 1 to 4, wherein the Young's modulus is greater than 78 GPa.

6. The alkali-free glass of any one of claims 1 to 5, wherein the Young's modulus/density is greater than 29.5 GPa/g-cm^-3。

7. The alkali-free glass of any one of claims 1 to 6, wherein the liquidus temperature is less than 1260 ℃.

8. The alkali-free glass according to any one of claims 1 to 7, wherein the viscosity is 10^2.5The temperature at the time of mooring is 1720 ℃ or lower.

9. The composition of any one of claims 1 to 8Alkali glass characterized by a viscosity of 10 at liquidus temperature^4.8Poise above.

10. The alkali-free glass according to any one of claims 1 to 9, which is formed by an overflow down-draw method.

11. The alkali-free glass according to any one of claims 1 to 10, which is used for an organic EL device.

Technical Field

The present invention relates to an alkali-free glass, and particularly to an alkali-free glass suitable for an organic EL display.

Background

Electronic devices such as organic EL displays are used for mobile phone displays and the like because they are thin, have excellent moving image display, and consume low power.

As a substrate of an organic EL display, a glass plate is widely used. The glass sheet for this application is mainly required to have the following characteristics. In particular, the following required characteristics (2) are emphasized.

(1) In order to prevent diffusion of alkali ions in the semiconductor material formed in the heat treatment step, the semiconductor material does not substantially contain an alkali metal oxide.

(2) In the process of manufacturing p-Si TFT, the strain point is high to reduce the thermal shrinkage of the glass plate.

(3) The glass sheet is excellent in productivity, particularly in devitrification resistance and meltability, in order to reduce the cost of the glass sheet.

(4) The chemical resistance is high in order to prevent deterioration due to various chemicals such as acids and alkalis used in the photolithography step, particularly hydrofluoric acid-based chemical solutions.

(5) When the glass plate is large and thin, the young's modulus and young's modulus/density (ratio young's modulus) are high in order to reduce the amount of deflection (swing width accompanying deflection) of the glass plate in the manufacturing process of the display.

Disclosure of Invention

Problems to be solved by the invention

In a panel manufacturing plant for organic EL displays, a plurality of individual devices are fabricated on a large glass plate molded by a glass manufacturing plant, and then the glass plate is cut into individual devices to reduce the cost (so-called multi-chamfering). In this multi-chamfering step, since the organic EL display is completed by cutting the glass plate and then bonding 2 glass plates or cutting the glass plate after bonding, the periphery of the glass plate is often subjected to no chamfering process, and the glass plate flows into a post-step or a final product in a state where the cut surface is directly present. In this case, it is important to improve the cracking resistance when chamfering a plurality of corners.

Further, according to the detailed experiments of the present inventors, in order to satisfy the requirement (2) described aboveCharacteristic, reduction of B in glass composition₂O₃The content of (b) is effective. However, if B in the glass composition is reduced₂O₃The content (c) is more likely to decrease the cracking resistance. Further, if B in the glass composition is reduced₂O₃The content (b) is likely to lower chemical resistance and melting property, and it becomes difficult to satisfy the required characteristics of (3) and (4).

Accordingly, the present invention has been made in view of the above circumstances, and an object of the present invention is to provide a glass composition containing B₂O₃When the content of (b) is small, an alkali-free glass having both of cracking resistance and chemical resistance may be used.

Means for solving the problems

The present inventors have repeated various experiments and found that the above technical problems can be solved by strictly limiting the glass composition range of alkali-free glass and limiting the glass properties to a predetermined range, and proposed the present invention. That is, the alkali-free glass of the present invention is characterized by containing SiO in mol%₂66～78％、Al₂O₃8～15％、B₂O₃0 to 1.8% of MgO, 1 to 15% of CaO, 0 to 8% of SrO, and 1 to 8% of BaO, and substantially no alkali metal oxide, and having a strain point higher than 725 ℃. The phrase "substantially not containing an alkali metal oxide" means an alkali metal oxide (Li) in the glass composition₂O、Na₂O、K₂O) is 0.5 mol% or less. "strain point" refers to a value determined based on the method of astm c 336.

Second, the alkali-free glass of the present invention is preferably B₂O₃Is less than 0.1 mol%.

Third, the alkali-free glass of the present invention is preferably B₂O₃The content of (b) is 0.1 mol% or more and less than 1 mol%.

Fourthly, the alkali-free glass of the present invention preferably further contains 0.001 to 1 mol% of SnO₂As a glass composition.

Fifth, the alkali-free glass of the present invention preferably has a Young's modulus of greater than 78 GPa. The "young's modulus" can be measured by a flexural resonance method.

Sixth, the alkali-free glass of the present invention preferably has a specific Young's modulus of more than 29.5GPa/g cm^-3. Among them, the "density" can be measured by the archimedes method.

Seventh, the alkali-free glass of the present invention preferably has a liquidus temperature of less than 1260 ℃. The "liquidus temperature" can be calculated by charging a glass powder having passed through a standard sieve of 30 mesh (500 μm) and remaining on a sieve of 50 mesh (300 μm) into a platinum boat, holding the boat for 24 hours in a temperature gradient furnace, and measuring the temperature at which crystals are precipitated.

Eighth, the alkali-free glass of the present invention preferably has a viscosity of 10^2.5The temperature at the time of mooring is 1720 ℃ or lower. Wherein "viscosity 10^2.5The "temperature under poise" can be determined by the platinum ball Czochralski method.

Ninthly, the alkali-free glass of the present invention preferably has a viscosity (liquidus viscosity) at a liquidus temperature of 10^4.8Poise above. Wherein, the viscosity at the liquidus temperature can be measured by a platinum ball pulling method.

Tenth, the alkali-free glass of the present invention is preferably formed by an overflow down-draw method.

Eleventh, the alkali-free glass of the present invention is preferably used for organic EL devices, particularly organic EL displays.

Detailed Description

The reason why the content of each component is limited in the alkali-free glass of the present invention as described above will be described below. In the description of the content of each component,% represents mol%.

SiO₂Is a component forming the glass skeleton. SiO 2₂The content of (b) is 66-78%, preferably 69-76%, 70-75% or 71-74%, and particularly preferably 72-73%. If SiO₂When the content of (b) is too small, it becomes difficult to increase the strain point, and the density becomes too high. On the other hand, if SiO₂When the content (b) is too large, the high-temperature viscosity increases, the meltability tends to decrease, devitrified crystals such as cristobalite precipitate, and the liquid phase temperature tends to increase.

Al₂O₃Is made of glassThe glass skeleton is a component that increases the strain point and further suppresses phase separation. Al (Al)₂O₃The content of (b) is 8 to 15%, preferably 9 to 14%, 9.5 to 13%, or 10 to 12%, and particularly preferably 10.5 to 11.5%. If Al is present₂O₃When the content of (b) is too small, the strain point is liable to be lowered, and the phase separation of the glass is liable to occur. On the other hand, if Al₂O₃When the content of (A) is too large, crystals such as mullite and anorthite are devitrified and precipitated, and the liquid phase temperature tends to be high.

If B is₂O₃When the content of (b) is too large, the strain point is greatly lowered, and the cracking resistance and the chemical resistance are easily lowered. Thus, B₂O₃The content of (b) is 1.8% or less, preferably 1.5% or less, 1% or less, less than 1% or 0.7% or less, particularly preferably 0.6% or less. On the other hand, if B is introduced in a small amount₂O₃The cracking resistance is improved, and the melting property and the devitrification resistance are improved. Thus, B₂O₃The content of (b) is preferably 0.01% or more, 0.1% or more, 0.2% or more, 0.3% or more, or 0.4% or more, and particularly preferably 0.5% or more.

MgO is a component that reduces the high-temperature viscosity and improves the meltability. The MgO content is 0 to 8%, preferably 0 to 5%, 0 to 4%, 0.01 to 3.5%, 0.1 to 3.2%, or 0.5 to 3%, and particularly preferably 1 to 2.7%. If the content of MgO is too large, the strain point tends to decrease.

From the viewpoint of increasing the strain point, B₂O₃+ MgO content (B)₂O₃The total amount of MgO) is preferably 6% or less, 0.1 to 5% or 1 to 4.5%, particularly preferably 2 to 4%. In addition, if B₂O₃When the content of + MgO is too small, the melting property, the cracking resistance, and the chemical resistance are liable to be lowered.

Molar ratio B₂O₃The amount of/MgO is preferably 0.3 or less, 0.25 or less, 0.22 or less, 0.01 to 0.2 or 0.05 to 0.18, and particularly preferably 0.1 to 0.17. In this way, the devitrification resistance can be easily controlled to an appropriate range.

CaO is a component that lowers the high-temperature viscosity without lowering the strain point and remarkably improves the meltability. Further, CaO is a component that reduces the cost of raw materials because the raw materials are relatively inexpensive to introduce into the alkaline earth metal oxide. The content of CaO is 1 to 15%, preferably 3 to 12%, 4 to 10%, or 4.7 to 8.9%, and particularly preferably 5.8 to 8.5%. If the content of CaO is too small, it becomes difficult to enjoy the above-described effects. On the other hand, if the content of CaO is too large, the thermal expansion coefficient becomes too high, the compositional balance of the glass composition is impaired, and the glass becomes susceptible to devitrification.

SrO is a component that suppresses phase separation and also improves resistance to devitrification. Further, the component is a component that reduces the high-temperature viscosity and improves the meltability without lowering the strain point, and is a component that suppresses an increase in the liquid phase temperature. The SrO content is 0-8%, preferably 0.1-6%, 0.5-5% or 0.8-4%, and particularly preferably 1-3%. If the SrO content is too small, it becomes difficult to obtain the effect of suppressing phase separation and the effect of improving resistance to devitrification. On the other hand, if the SrO content is too large, the compositional balance of the glass composition is impaired, and the strontium silicate-based devitrified crystals are likely to precipitate.

BaO is a component that significantly improves resistance to devitrification in an alkaline earth metal oxide. The content of BaO is 1 to 8%, preferably 2 to 7%, 3 to 6%, or 3.5 to 5.5%, and particularly preferably 4 to 5%. If the content of BaO is too small, the liquidus temperature becomes high, and the devitrification resistance is liable to decrease. On the other hand, if the content of BaO is too large, the compositional balance of the glass composition is impaired, and devitrified crystals containing BaO are likely to precipitate.

RO (the total amount of MgO, CaO, SrO and BaO) is preferably 12 to 18%, 13 to 17.5% or 13.5 to 17%, and particularly preferably 14 to 16.8%. If the RO content is too small, the meltability tends to be low. On the other hand, if the RO content is too large, the compositional balance of the glass composition is impaired, and the devitrification resistance is liable to decrease.

The molar ratio MgO/RO is preferably 0.3 or less, 0.25 or less, 0.22 or less, 0.01 to 0.2 or 0.05 to 0.18, and particularly preferably 0.1 to 0.17. In this way, it becomes easy to suppress the decrease in strain point, cracking resistance, and chemical resistance.

The molar ratio CaO/RO is preferably 0.8 or less, 0.7 or less, 0.1 to 0.7, 0.2 to 0.65, or 0.3 to 0.6, and particularly preferably 0.45 to 0.55. In this way, it becomes easy to optimize the resistance to devitrification and the melting property.

The molar ratio SrO/RO is preferably 0.4 or less, 0.35 or less, 0.3 or less, 0.01 to 0.2 or 0.03 to 0.18, and particularly preferably 0.05 to 0.15. In this way, the precipitation of devitrified crystals of strontium silicate can be easily suppressed.

The molar ratio BaO/RO is preferably 0.5 or less, 0.4 or less, 0.1 to 0.37 or less, 0.2 to 0.35, or 0.24 to 0.32, and particularly preferably 0.27 to 0.3. This makes it easy to improve the meltability and the resistance to devitrification.

In addition to the above components, for example, the following components may be added to the glass composition. In addition, from the viewpoint of ensuring the effects of the present invention, the content of the other components than the above components is preferably 10% or less, particularly 5% or less, in total.

ZnO is a component for improving meltability, but when ZnO is contained in a large amount, the glass is easily devitrified, and the strain point is easily lowered. The content of ZnO is preferably 0 to 5%, 0 to 3%, or 0 to 0.5%, particularly 0 to 0.3%, and it is preferably not substantially contained. Here, "substantially no ZnO" means that the content of ZnO in the glass composition is 0.2% or less.

P₂O₅Is a component for increasing the strain point, but if it contains a large amount of P₂O₅The glass becomes susceptible to phase separation. P₂O₅The content of (B) is preferably 0 to 1.5% or 0 to 1.2%, particularly 0 to 1%.

TiO₂Is a component for lowering high-temperature viscosity and improving meltability and a component for suppressing solarization, but contains TiO in a large amount₂The glass is colored, and the transmittance is liable to decrease. Thus, TiO₂The content of (B) is preferably 0 to 3%, 0 to 1%, or 0 to 0.1%, particularly 0 to 0.02%.

For Y₂O₃、Nb₂O₅、La₂O₃Having increased strainPoint, young's modulus, etc. However, if the content of these components is too large, the density and the raw material cost are likely to increase. Thus, Y₂O₃、Nb₂O₅、La₂O₃The content of (b) is preferably 0 to 3% or 0 to 1%, particularly 0 to 0.1%, respectively.

SnO₂Is a component having a good clarifying action in a high-temperature region, and is a component for increasing the strain point, and is a component for reducing the high-temperature viscosity. SnO₂The content of (B) is preferably 0 to 1%, 0.001 to 1%, or 0.05 to 0.5%, particularly 0.1 to 0.3%. If SnO₂When the content of (A) is too large, SnO₂The devitrified crystals of (2) are liable to precipitate. In addition, if SnO₂When the content of (b) is less than 0.001%, it becomes difficult to obtain the above-mentioned effects.

SnO₂Suitable as fining agents, but other SnO may be used as long as the glass properties are not significantly impaired₂Other clarifying agents. Specifically, As may be added in a total amount of, for example, 1% or less₂O₃、Sb₂O₃、CeO₂、F₂、Cl₂、SO₃For example, 1% or less of metal powder of Al, Si, etc. may be added in total.

As₂O₃、Sb₂O₃Is excellent, but from the viewpoint of environment, it is preferable not to introduce the compound as much as possible. Furthermore, if As₂O₃Since a large amount of glass tends to lower the resistance to solarization, the content thereof is preferably 0.5% or less, particularly 0.1% or less, and is preferably substantially not contained. Wherein "substantially no As is contained₂O₃"means As in the glass composition₂O₃The content of (B) is less than 0.05%. In addition, Sb₂O₃The content of (b) is preferably 1% or less, particularly 0.5% or less, and is preferably substantially not contained. Wherein "substantially no Sb is contained₂O₃"means Sb in the glass composition₂O₃The content of (B) is less than 0.05%.

Cl₂With provision for promoting melting of alkali-free glassEffect if Cl is added₂The melting temperature can be lowered and the action of the refining agent is promoted, so that the melting cost can be reduced and the life of the glass manufacturing furnace can be prolonged. However, if Cl₂If the content of (b) is too large, the strain point is lowered. Thus, Cl₂The content of (b) is preferably 0.5% or less, particularly 0.1% or less. In addition, as Cl₂The raw material for introduction of (b) may be a chloride of an alkaline earth metal oxide such as strontium chloride, or aluminum chloride.

In the alkali-free glass of the present invention, the strain point exceeds 725 ℃, preferably 730 ℃ or higher, more preferably 735 ℃ or higher, and still more preferably 740 ℃ or higher. In this way, the thermal shrinkage of the glass plate can be suppressed in the process of manufacturing the p-Si TFT.

The Young's modulus is preferably more than 78GPa, 78.5GPa or more, 79GPa or more, or 79.5GPa or more, particularly 79.7Pa or more. In this way, since the glass plate can be prevented from being bent, handling of the glass plate is facilitated in a display manufacturing process or the like.

Young's modulus/density is preferably more than 9.5GPa/g cm^-3、29.8GPa/g·cm^-3Above, 30.1GPa/g cm^-3Above or 30.3GPa/g cm^-3Above, especially 30.5GPa/g cm^-3The above. When the value of young's modulus/density is increased, the amount of deflection of the glass sheet can be greatly suppressed.

The temperature of the liquid phase is preferably less than 1260 ℃ or less than 1250 ℃, in particular less than 1240 ℃. In this way, devitrification crystals are easily prevented from occurring during glass production, and productivity is easily prevented from being lowered. Further, since it becomes easy to shape the glass sheet by the overflow down-draw method, the surface quality of the glass sheet can be improved, and the manufacturing cost of the glass sheet can be reduced. The liquidus temperature is an index of resistance to devitrification, and the lower the liquidus temperature, the more excellent the resistance to devitrification.

10^2.5The temperature at the time of mooring is preferably 1720 ℃ or lower, 1700 ℃ or lower, or 1690 ℃ or lower, particularly 1680 ℃ or lower. If 10^2.5When the temperature at the time of mooring is high, it becomes difficult to ensure solubility and clarity,the manufacturing cost of the glass plate is high.

The viscosity at the liquidus temperature is preferably 10^4.8Poo Yuan, 10^5.0Poo above or 10^5.2Poise or higher, especially 10^5.3Poise above. In this way, since devitrification is less likely to occur during the forming, it becomes easier to form the glass sheet by the overflow down-draw method, and as a result, the surface quality of the glass sheet can be improved, and the manufacturing cost of the glass sheet can be reduced. The liquid phase viscosity is an index of moldability, and the higher the liquid phase viscosity, the more excellent the moldability.

In the alkali-free glass of the present invention, the strain point can be increased by decreasing the β -OH value. The beta-OH value is preferably 0.5/mm or less, 0.45/mm or less, 0.4/mm or less, 0.35/mm or less, or 0.3/mm or less, and particularly preferably 0.25/mm or less. If the β -OH value is too large, the strain point tends to be lowered. If the β -OH value is too small, the meltability tends to be low. Therefore, the value of β -OH is preferably 0.01/mm or more, and particularly preferably 0.05/mm or more.

The following methods can be mentioned as a method for reducing the β -OH value. (1) Selecting raw materials with low water content. (2) Adding components (Cl, SO) for reducing beta-OH value into glass₃Etc.). (3) The moisture content in the furnace atmosphere is reduced. (4) N in molten glass₂Bubbling. (5) A small melting furnace is used. (6) The flow rate of the molten glass is increased. (7) An electric melting method is adopted.

The term "β -OH value" refers to the transmittance of the glass measured by FT-IR measurement and is determined by the following equation.

beta-OH value ═ (1/X) log (T)₁/T₂)

In the above formula, X is the glass wall thickness (mm), T₁For reference wavelength 3846cm^-1Transmittance (%) of T₂Has hydroxyl radical absorption wavelength of 3600cm^-1Near minimum transmittance (%).

The alkali-free glass of the present invention is preferably formed by an overflow downdraw method. The overflow down-draw method is a method of producing a glass sheet by causing molten glass to overflow from both sides of a heat-resistant chute-like structure, joining the overflowing molten glass at the lower end of the chute-like structure, and simultaneously drawing and forming the molten glass downward. In the overflow down-draw method, the surface to be the surface of the glass sheet is formed in a free surface state without contacting the trough-like refractory. Therefore, a glass plate having good surface quality and no polishing can be produced at low cost. The structure and material of the chute-like structure used in the overflow downdraw method are not particularly limited as long as the desired dimensional and surface accuracy can be achieved. Further, the method of applying the force during the downward stretch forming is not particularly limited. For example, a method of rotating a heat-resistant roller having a sufficiently large width in contact with glass to perform drawing may be employed, or a method of rotating a plurality of heat-resistant rollers in pairs in contact with only the vicinity of the end faces of glass to perform drawing may be employed.

In addition to the overflow downdraw method, the glass sheet may be formed by, for example, a downdraw method (slit downdraw method or the like), a float method, or the like.

The alkali-free glass of the present invention is preferably used for organic EL devices, particularly organic EL displays. In a panel manufacturing plant for organic EL displays, a plurality of individual devices are fabricated on a large glass plate molded by a glass manufacturing plant, and then the glass plate is divided and cut into individual devices to reduce the cost (so-called, multi-chamfered). In particular, in TV applications, the size of the apparatus itself is increased, and a large glass plate is required for chamfering the apparatus in many cases. The alkali-free glass of the present invention can satisfy such a demand because it is easy to form a large glass sheet because of its low liquidus temperature and high liquidus viscosity.

In the alkali-free glass of the present invention, the thickness (plate thickness) is preferably 0.7mm or less, 0.5mm or less, 0.4mm or less, or 0.3mm or less, particularly 0.05 to 0.1 mm. As the thickness is smaller, it becomes easier to achieve a light weight, a thin thickness, and flexibility of the display.