WO2017188126A1 - 無アルカリガラス - Google Patents
無アルカリガラス Download PDFInfo
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- WO2017188126A1 WO2017188126A1 PCT/JP2017/015923 JP2017015923W WO2017188126A1 WO 2017188126 A1 WO2017188126 A1 WO 2017188126A1 JP 2017015923 W JP2017015923 W JP 2017015923W WO 2017188126 A1 WO2017188126 A1 WO 2017188126A1
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- glass
- less
- alkali
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- sro
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Classifications
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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
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B18/00—Shaping glass in contact with the surface of a liquid
-
- 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
- C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
- C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
- C03C3/087—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal containing calcium oxide, e.g. common sheet or container glass
Definitions
- the present invention relates to an alkali-free glass suitable as a substrate glass for various displays and photomasks.
- glass used for glass plates (glass substrates) for various displays and photomasks have the following characteristics (1) to (4). It is requested. (1) When the glass contains an alkali metal oxide, the alkali metal ions diffuse into the thin film and deteriorate the film properties of the thin film, so that the glass does not substantially contain alkali metal ions. (2) When the glass plate is exposed to a high temperature in the thin film forming step, the strain point is high so that the deformation (thermal shrinkage) accompanying the deformation of the glass plate and the stabilization of the glass structure can be minimized.
- BHF buffered hydrofluoric acid
- ITO various acids used for etching metal electrodes
- resist stripping alkali and the like there are no defects (bubbles, striae, inclusions, pits, scratches, etc.) inside and on the surface.
- a glass having a small average thermal expansion coefficient is required in order to increase productivity by increasing the temperature raising / lowering rate of the heat treatment during the production of the liquid crystal display or to increase the thermal shock resistance.
- the average thermal expansion coefficient of glass is too small, the number of film formation processes such as a gate metal film and a gate insulating film during the production of a liquid crystal display increases, and the warpage of the glass increases. There are problems such as occasional problems such as cracks and scratches, and a large shift in the exposure pattern.
- a glass having a high specific modulus Youngng's modulus / density
- a thin glass plate having a thickness of 1 mm or less, particularly a large size has a problem in that deflection due to its own weight and warpage accompanying various film formations increase. Deflection and warpage can be suppressed by increasing the specific elastic modulus (Young's modulus / density).
- the conventional alkali-free glass having a high specific elastic modulus has problems such as a strain point that is too high, a density that is high, a clarity that is poor, a solubility that is poor, and a thermal expansion coefficient that is too low.
- the present invention is a non-alkali glass that solves the above problems, that is, having a high specific elastic modulus, an appropriate strain point, a low density, a thermal expansion coefficient that is not too low, and a good clarity and solubility. It aims at providing the alkali free glass which has.
- the alkali-free glass of the present invention has a low specific gravity, is difficult to bend even if it is thin, has high production efficiency, and has characteristics suitable for use as a substrate glass in displays, photomasks and the like.
- the alkali-free glass of the present invention will be described.
- the composition range of each component of the glass is expressed in mol% based on the oxide.
- the content of SiO 2 is 62% or more, preferably 63% or more, more preferably 64% or more, particularly preferably 65% or more, and most preferably 65.5% or more.
- the content of SiO 2 exceeds 70%, the solubility of the glass tends to decrease, the Young's modulus decreases, and the devitrification temperature tends to increase. Therefore, the content of SiO 2 is 70% or less, preferably 69% or less, more preferably 68% or less, still more preferably 67% or less, particularly preferably 66.7% or less, and most preferably 66.5%. It is as follows.
- Al 2 O 3 increases the Young's modulus to suppress deflection, suppresses the phase separation of the glass, decreases the average thermal expansion coefficient, increases the strain point, increases the fracture toughness value, and increases the glass strength.
- the content of Al 2 O 3 is less than 11%, these effects are hardly exhibited, and other components that increase the average thermal expansion coefficient are relatively increased. As a result, the average thermal expansion coefficient is There is a tendency to grow. Therefore, the content of Al 2 O 3 is 11% or more, preferably 11.5% or more, more preferably 12% or more. If the content of Al 2 O 3 exceeds 14%, the solubility of the glass is deteriorated, and the devitrification temperature may be increased. Therefore, the content of Al 2 O 3 is 14% or less, preferably 13.5% or less, more preferably 13% or less.
- B 2 O 3 improves the BHF resistance, improves the melting reactivity of the glass, and lowers the devitrification temperature. If the content of B 2 O 3 is less than 3%, this effect is unlikely to appear, the BHF resistance tends to deteriorate, and the strain point may be excessively high. Therefore, the content of B 2 O 3 is 3% or more, preferably 3.5% or more, more preferably 4% or more. If the content of B 2 O 3 exceeds 6%, the surface roughness of the glass plate after the hydrofluoric acid etching treatment (hereinafter also referred to as “thinning treatment”) tends to increase and the strength after the thinning treatment tends to decrease. In addition, the strain point tends to decrease. Therefore, the content of B 2 O 3 is 6% or less, preferably 5.5% or less, more preferably 5.2% or less, and even more preferably 5% or less.
- MgO increases the Young's modulus without increasing the specific gravity, the problem of deflection can be reduced by increasing the specific elastic modulus, and the fracture toughness value is improved to increase the glass strength. MgO also improves solubility. If the content of MgO is less than 7%, these effects are hardly exhibited, and the thermal expansion coefficient may be too low. Therefore, the content of MgO is 7% or more, preferably 7.3% or more, more preferably 7.5% or more. However, when there is too much MgO content, devitrification temperature will rise easily. Therefore, the content of MgO is 10% or less, preferably 9% or less, and more preferably 8.8% or less.
- CaO is characterized in that it has a specific modulus higher than that of MgO in an alkaline earth metal and does not excessively lower the strain point, and improves solubility as well as MgO. Further, it has a feature that it is difficult to increase the devitrification temperature as compared with MgO. If the content of CaO is less than 3%, these effects are difficult to appear. Therefore, the content of CaO is 3% or more, preferably 4% or more, more preferably 4.5% or more. If the content of CaO exceeds 9%, the average thermal expansion coefficient becomes too high, and the devitrification temperature becomes high, and devitrification tends to be a problem during the production of glass. Therefore, the content of CaO is 9% or less, preferably 8% or less, more preferably 7.5% or less.
- SrO does not increase the devitrification temperature of the glass and improves the solubility. However, if the content of SrO is less than 1%, these effects are hardly exhibited. Therefore, the SrO content is 1% or more, preferably 1.2% or more, more preferably 1.5% or more, and further preferably 2% or more. SrO has a lower effect than BaO, and if SrO is increased too much, the effect of increasing the specific gravity is rather superior, and the average thermal expansion coefficient may be too high. Therefore, the SrO content is 5% or less, preferably 4.5% or less, more preferably 4.2% or less, and further preferably 4% or less.
- BaO is not an essential component, but can be contained in order to improve the solubility without increasing the devitrification temperature of the glass.
- the content of BaO is 1% or less, preferably 0.5% or less. More preferably, the alkali-free glass of the present invention is substantially free of BaO.
- substantially does not contain means that it is not contained other than unavoidable impurities mixed from raw materials or the like, that is, it is not intentionally contained.
- substantially not containing BaO is, for example, 0.3% or less, and preferably 0.2% or less.
- the alkali-free glass of the present invention preferably satisfies [MgO] ⁇ [CaO] ⁇ [SrO] ⁇ [BaO]. More preferably, [MgO ⁇ [CaO]> [SrO] ⁇ [BaO], still more preferably [MgO] ⁇ [CaO]> [SrO]> [BaO], and particularly preferably [MgO]> [CaO. ]> [SrO]> [BaO].
- the display of the component enclosed in the square brackets represents the content (mol%) of the component in the alkali-free glass (the same applies to the description of other parts in the present specification).
- RO alkaline earth metal oxide
- MgO / RO is preferably 0.35 or more, more preferably 0.37 or more, and further preferably 0.4 or more.
- the Young's modulus and specific elastic modulus are increased without increasing the devitrification temperature, and the viscosity of the glass is 10 4 dPa ⁇ it is possible to lower the temperature T 4 which is a s.
- the difference between the temperature T 2 at which the glass viscosity becomes 10 2 dPa ⁇ s and the strain point, that is, (T 2 ⁇ strain point) can be reduced.
- MgO / RO is preferably 0.70 or less, more preferably 0.65 or less, and even more preferably 0.60 or less. If MgO / RO is 0.70 or less, (T 2 ⁇ strain point) can be increased.
- the alkali-free glass of the present invention does not substantially contain alkali metal oxides such as Na 2 O and K 2 O.
- substantially not containing an alkali metal oxide is, for example, 0.1% or less, preferably 0.08% or less, more preferably 0.05% or less, most preferably 0.03. % Or less.
- the alkali-free glass of the present invention substantially contains P 2 O 5 so as not to cause deterioration of properties of a thin film such as a metal or oxide provided on the surface of the glass plate. Preferably not.
- substantially not containing P 2 O 5 is, for example, 0.1% or less.
- the alkali-free glass of the present invention does not substantially contain PbO, As 2 O 3 , or Sb 2 O 3 .
- the fact that PbO, As 2 O 3 , Sb 2 O 3 is not substantially contained means that the content of PbO, As 2 O 3 , Sb 2 O 3 is, for example, 0.01% or less, Preferably it is 0.005% or less.
- the alkali-free glass of the present invention includes one of ZrO 2 , ZnO, Fe 2 O 3 , SO 3 , F, Cl, and SnO 2.
- the total amount may be 2% or less, preferably 1% or less, more preferably 0.5% or less.
- the alkali-free glass of the present invention has a value represented by the following formula (I) of 85 or more.
- the value represented by the formula (I) is an index of the density ( ⁇ ) of the alkali-free glass, and when this value is less than 85%, the density increases.
- the value represented by the formula (I) is more preferably 85.4 or more, further preferably 85.8 or more, and particularly preferably 86 or more.
- the value represented by formula (I) is not particularly limited, but is preferably 90 or less, and more preferably 88 or less.
- the alkali-free glass of the present invention has a value represented by the following formula (II) of 72 or more and 75 or less.
- the value represented by the formula (II) is an index of the melting temperature of the alkali-free glass. When this value is less than 72, the temperature T 2 at which the glass viscosity becomes 10 2 dPa ⁇ s is lowered.
- This value represented by the formula (II) is preferably 72.5 or more, more preferably 73 or more. If this value represented by formula (II) is more than 75, T 2 may be high. This value is preferably 74 or less, more preferably 73.5 or less.
- the alkali-free glass of the present invention has a value represented by the following formula (III) of 19 or less.
- the value represented by the formula (III) is an index of the thermal expansion coefficient ⁇ of the alkali-free glass. If this value exceeds 19, the average thermal expansion coefficient becomes too low.
- the value represented by the formula (III) is preferably 18.9 or less, and more preferably 18.7 or less.
- the value represented by the formula (III) is not particularly limited, but is preferably 15.8 or more, and more preferably 16.5 or more.
- the values represented by the above formulas (I) to (III) are expressed in percent (%), but the units are omitted.
- the alkali-free glass of the present invention has a specific modulus (Young's modulus (GPa) / density (g / cm 3 )) of 32 MN ⁇ m / kg or more in order to suppress bending and warping.
- the specific elastic modulus is preferably 33 MN ⁇ m / kg or more, and more preferably 33.5 MN ⁇ m / kg or more.
- the specific elastic modulus is usually 36 MN ⁇ m / kg or less.
- the alkali-free glass of the present invention has a strain point of 690 to 710 ° C.
- the strain point is preferably 695 ° C. or higher.
- the strain point is preferably 705 ° C. or lower, more preferably 700 ° C. or lower.
- the alkali-free glass of the present invention has a density of 2.54 g / cm 3 or less in order to reduce the weight of the product and increase the specific elastic modulus. Density is preferably 2.53 g / cm 3 or less, 2.52 g / cm 3 or less is more preferable. On the other hand, the density is usually 2.40 g / cm 3 or more.
- the alkali-free glass of the present invention has an average coefficient of thermal expansion of 35 ⁇ 10 ⁇ 7 / ° C. or more at 50 to 350 ° C.
- a gate metal film such as copper and a gate insulating film such as silicon nitride may be sequentially laminated on an alkali-free glass, but the average thermal expansion coefficient is 35. If it is less than ⁇ 10 ⁇ 7 / ° C., the difference in expansion coefficient between the gate insulating film and the glass becomes too small. Therefore, the effect of canceling the glass warpage caused by the formation of the gate metal film by the gate insulating film is reduced.
- the average coefficient of thermal expansion is preferably 35.2 ⁇ 10 ⁇ 7 / ° C. or more, and more preferably 35.5 ⁇ 10 ⁇ 7 / ° C. or more.
- the upper limit of the average thermal expansion coefficient is not particularly limited, but is preferably 43 ⁇ 10 ⁇ 7 / ° C. or less, more preferably 40 ⁇ 10 ⁇ 7 / ° C. or less from the viewpoint of productivity and thermal shock resistance in the production of products such as displays. More preferably, it is 38.5 ⁇ 10 ⁇ 7 / ° C. or less.
- the temperature T 2 at which the glass viscosity becomes 10 2 dPa ⁇ s is 1610 to 1680 ° C. If T 2 is less than 1610 ° C., as well as clarity of the glass is deteriorated, erosion and the melting furnace to be described later by melt became low viscosity, the burden of the heater of the forming device can be increased.
- T 2 is preferably 1620 ° C. or higher, more preferably 1630 ° C. or higher.
- T 2 is higher than 1680 ° C., the glass has poor solubility and requires high temperature, increasing the burden on the manufacturing apparatus.
- T 2 is preferably 1670 ° C. or lower, more preferably 1660 ° C. or lower.
- the alkali-free glass of the present invention preferably has a temperature T 4 at which the glass viscosity becomes 10 4 dPa ⁇ s is 1320 ° C. or less, more preferably 1300 ° C. or less, still more preferably 1297 ° C. or less, particularly preferably It is 1295 degrees C or less. Glass having T 4 within the above range is suitable for forming by the float process.
- the alkali-free glass of the present invention the viscosity (devitrification viscosity) at the devitrification temperature, preferably 10 3.6 poise (dPa ⁇ s) or more.
- the devitrification viscosity is more preferably 10 3.8 poise or more, further preferably 10 3.85 poise or more, and particularly preferably 10 3.9 poise or more.
- the devitrification temperature in the present invention can be determined as follows. That is, the crushed glass particles are put in a platinum dish and heat-treated for 17 hours in an electric furnace controlled at a constant temperature. After the heat treatment, the maximum amount of crystals is precipitated on the surface and inside of the glass using an optical microscope. Observe the temperature and the lowest temperature at which crystals do not precipitate, and let the average value be the devitrification temperature.
- the viscosity at the devitrification temperature can be obtained by measuring the viscosity of the glass at the devitrification temperature.
- the devitrification temperature is preferably 1330 ° C. or lower, more preferably 1320 ° C. or lower, and further preferably 1310 ° C. or lower.
- the glass transition point of the alkali-free glass of the present invention is preferably 730 to 770 ° C.
- the glass transition point is preferably 740 ° C. or higher, more preferably 745 ° C. or higher.
- the glass transition point is preferably 760 ° C. or lower, more preferably 755 ° C. or lower.
- the Young's modulus of the alkali-free glass of the present invention is preferably 81 GPa or more.
- a high Young's modulus increases the specific elastic modulus and improves the fracture toughness of the glass. Therefore, it is suitable for various display substrate glasses and photomask substrate glasses that require a larger or thinner glass plate.
- the Young's modulus is more preferably 82 GPa or more, further preferably 83 GPa or more, further preferably 83.5 GPa or more, particularly preferably 84 GPa or more, and most preferably 84.5 GPa or more. Young's modulus can be measured by an ultrasonic method. On the other hand, the Young's modulus is usually 88 GPa or less.
- the difference between the temperature T 2 at which the glass viscosity of the alkali-free glass of the present invention is 10 2 dPa ⁇ s and the strain point, that is, (T 2 ⁇ strain point) is preferably 920 to 1000 ° C.
- (T 2 ⁇ strain point) is less than 920 ° C., it is difficult to make the plate thickness uniform because of a large temperature gradient in glass forming.
- (T 2 ⁇ strain point) is more preferably 930 ° C. or more, and further preferably 935 ° C. or more.
- (T 2 ⁇ strain point) exceeds 1000 ° C., the sensible heat that the glass brings from the melting furnace to the molding apparatus is small, the heater load of the molding apparatus increases, and the burden on the molding apparatus increases.
- (T 2 -strain point) is more preferably 980 ° C. or lower, and further preferably 970 ° C. or lower.
- the thickness of the alkali-free glass of the present invention is not particularly limited, but it is preferably formed into a glass plate of 1.0 mm or less. By reducing the plate thickness, the weight of the display can be easily reduced.
- the thickness of the glass plate obtained by molding is more preferably 0.7 mm or less, further preferably 0.5 mm or less, still more preferably 0.4 mm or less, particularly preferably 0.35 mm or less, and most preferably 0.25 mm. It is as follows.
- the plate thickness can be 0.1 mm or less, or 0.05 mm or less. However, from the viewpoint of preventing deflection due to its own weight, the plate thickness is preferably 0.1 mm or more, and more preferably 0.2 mm or more.
- Manufacture of the alkali free glass of this invention can be implemented in the following procedures, for example.
- the raw materials of the above components are blended so as to have a target content in the glass composition, which is put into a melting furnace, heated to 1500-1800 ° C. and melted to obtain a molten glass.
- the obtained molten glass is formed into a glass ribbon having a predetermined plate thickness with a molding apparatus, and the glass ribbon is gradually cooled and then cut to obtain an alkali-free glass.
- the molten glass is preferably formed into a glass plate by a float method or a fusion method.
- the fusion method By using the fusion method, the average cooling rate near the glass transition point is increased, and when the obtained glass plate is further thinned by hydrofluoric acid (HF) etching treatment, the hydrofluoric acid (HF) etching treatment side
- HF hydrofluoric acid
- the float method from the viewpoint of stably producing a large plate glass (for example, one side of 2 m or more).
- Examples 1 to 20 and 25 to 36 are Examples, and Examples 21 to 24 are Comparative Examples.
- the raw materials of each component were prepared so that the glass composition became the target composition (unit: mol%) shown in Tables 1 to 3, and dissolved at 1600 ° C. for 1 hour using a platinum crucible. After dissolution, the melt was poured onto a carbon plate, held at a temperature of (glass transition point + 30 ° C.) for 60 minutes, and then cooled to room temperature (25 ° C.) at 1 ° C./min to obtain a sheet glass. This was mirror-polished to obtain a glass plate and subjected to various evaluations. The results are shown in Tables 1 to 3. In Tables 1 to 3, the values shown in parentheses are calculated values.
- the measuring method of each physical property is shown below.
- (Average thermal expansion coefficient) According to the method prescribed
- TMA differential thermal dilatometer
- the measurement temperature range was 50 to 350 ° C, and the unit was expressed as 10 -7 / ° C.
- (density) According to the method defined in JIS Z 8807, about 20 g of glass lump containing no foam was measured by Archimedes method.
- T 2 According to the method prescribed in ASTM C 965-96, the viscosity was measured using a rotational viscometer, and the temperature T 2 (° C.) when it reached 10 2 d ⁇ Pa ⁇ s was measured.
- T 4 According to the method prescribed in ASTM C 965-96, the viscosity was measured using a rotational viscometer, and the temperature T 4 (° C.) when it reached 10 4 d ⁇ Pa ⁇ s was measured.
- Devitrification temperature The devitrification temperature was determined by the method described above.
- the glasses of Examples 1 to 20 and 25 to 36 satisfy all the requirements of the present invention, and have good specific modulus, strain point, density, coefficient of thermal expansion, and it has a T 2.
- the glass of Example 21 has an excessively high strain point because B 2 O 3 is less than 3%.
- the glass of Example 21 has a value higher than the range defined by the present invention in terms of the value represented by the formula (I).
- the glass of Example 22 has a low T 2 because the value represented by the formula (II) is lower than the range defined in the present invention. As a result, the melting temperature is lowered, the clarity is deteriorated, and the bubble quality of the glass is poor.
- the glass of Example 22 also has a low strain point.
- the glass of Example 23 has a high T 2 because the value represented by the formula (II) is higher than the range defined in the present invention. As a result, the solubility is poor. Moreover, since the value of the glass of Example 23 is higher than the range defined by the present invention, the coefficient of thermal expansion is too low as a result. In the glass of Example 24, the value represented by the formula (III) is higher than the range defined in the present invention, and the content of MgO is small, so that the thermal expansion coefficient is too low.
- the alkali-free glass of the present invention is suitable for use as a glass plate because of its small deflection, and is particularly suitable as a high-quality glass for substrates such as displays and photomasks.
- substrates such as displays and photomasks.
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Abstract
Description
(1)ガラスがアルカリ金属酸化物を含有している場合、アルカリ金属イオンが上記薄膜中に拡散して薄膜の膜特性を劣化させるため、ガラスが実質的にアルカリ金属イオンを含まないこと。
(2)薄膜形成工程でガラス板が高温にさらされる際に、ガラス板の変形およびガラスの構造安定化に伴う収縮(熱収縮)を最小限に抑えうるように歪点が高いこと。
(4)内部および表面に欠点(泡、脈理、インクルージョン、ピット、キズ等)がないこと。
(5)ディスプレイの軽量化が要求され、ガラス自身も比重の小さいガラスが望まれる。
(6)ディスプレイの軽量化が要求され、ガラス板の薄板化が望まれる。
(7)これまでのアモルファスシリコン(a-Si)タイプの液晶ディスプレイに加え、熱処理温度の高い多結晶シリコン(p-Si)タイプの液晶ディスプレイが作製されるようになってきた(a-Siの耐熱性:約350℃、p-Siの耐熱性:350~550℃)ため、耐熱性が望まれる。
(9)また、近年、ガラス基板の大板化・薄板化に伴い、比弾性率(ヤング率/密度)が高いガラスが求められている。
[1]酸化物基準のモル%表示で、
SiO2:62~70%、Al2O3:11~14%、 B2O3 :3~6%、MgO:7~10%、 CaO:3~9%、 SrO:1~5%、BaO:0~1%を含有し、
[SiO2]+0.7[Al2O3]+1.2[B2O3]+0.5[MgO]+0.4[CaO]-0.25[SrO]-0.88[BaO]が85以上であり、
[SiO2]+0.45[Al2O3]+0.21[B2O3]-0.042[MgO]+0.042[CaO]+0.15[SrO]+0.38[BaO]が72以上かつ75以下であり、
0.4[SiO2]+0.4[Al2O3]+0.25[B2O3]-0.7[MgO]-0.88[CaO]-1.4[SrO]-1.7[BaO]が19以下であり、
比弾性率が32MN・m/kg以上であり、歪点が690~710℃であり、密度が2.54g/cm3以下であり、50~350℃での平均熱膨張係数が35×10-7/℃以上であり、かつ、ガラス粘度が102dPa・sとなる温度T2が1610~1680℃であることを特徴とする無アルカリガラス。
[2][MgO]≧[CaO]≧[SrO]≧[BaO]である、[1]に記載の無アルカリガラス。
[3][MgO]>[CaO]>[SrO]>[BaO]である、[1]1または[2]2に記載の無アルカリガラス。
[4]MgO+CaO+SrO+BaOが15~21%である、[1]~[3]のいずれかに記載の無アルカリガラス。
[5]MgO/(MgO+CaO+SrO+BaO)が0.35~0.70である、[1]~[4]のいずれかに記載の無アルカリガラス。
[6]ガラス粘度が104dPa・sとなる温度T4が1320℃以下である、[1]~[5]のいずれかに記載の無アルカリガラス。
[7]失透粘度が103.6dPa・s以上である、[1]~[6]のいずれかに記載の無アルカリガラス。
[8]ヤング率が81GPa以上である、[1]~[7]のいずれかに記載の無アルカリガラス。
[9](T2-歪点)が920~1000℃である、[1]~[8]のいずれかに記載の無アルカリガラス。
[10]ガラス転位点が730~770℃である、[1]~[9]のいずれかに記載の無アルカリガラス。
[11]厚みが0.1~2.0mmであるガラス板である、[1]~[10]のいずれかに記載の無アルカリガラス。
[12]フロート法又はフージョン法で製造される、[1]~[11]のいずれかに記載の無アルカリガラス。
以下において、ガラスの各成分の組成範囲は、酸化物基準のモル%で表示する。
SiO2の含有量が62モル%(以下、単に、%という)未満では、歪点が充分に上がらず、かつ、平均熱膨張係数が増大し、比重が上昇する傾向がある。そのため、SiO2の含有量は62%以上であり、好ましくは63%以上、より好ましくは64%以上、特に好ましくは65%以上、最も好ましくは65.5%以上である。
SiO2の含有量が70%超では、ガラスの溶解性が低下し、ヤング率が低下し、失透温度が上昇する傾向がある。そのため、SiO2の含有量は70%以下であり、好ましくは69%以下、より好ましくは68%以下、さらに好ましくは67%以下、特に好ましくは66.7%以下、最も好ましくは66.5%以下である。
Al2O3の含有量が14%超ではガラスの溶解性が悪くなる、また、失透温度を上昇させるおそれがある。そのため、Al2O3の含有量は14%以下であり、好ましくは13.5%以下、より好ましくは13%以下である。
B2O3の含有量が6%超ではフッ酸エッチング処理(以下、「薄板化処理」ともいう)後のガラス板の表面粗さが大きくなって薄板化処理後の強度が低くなる傾向があり、さらに歪点も低下する傾向がある。したがってB2O3の含有量は6%以下であり、5.5%以下が好ましく、5.2%以下がより好ましく、5%以下がさらに好ましい。
しかし、MgO含有量が多すぎると、失透温度が上昇しやすくなる。そのため、MgOの含有量は10%以下であり、9%以下が好ましく、8.8%以下がより好ましい。
CaOの含有量が9%超では平均熱膨張係数が高くなりすぎ、また失透温度が高くなってガラスの製造時に失透が問題となりやすくなる。そのため、CaOの含有量は9%以下であり、好ましくは8%以下、より好ましくは7.5%以下である。
SrOは上記効果がBaOよりも低く、SrOを多くしすぎるとむしろ比重を大きくする効果が勝り、平均熱膨張係数も高くなりすぎ得る。そのため、SrOの含有量は5%以下であり、好ましくは4.5%以下であり、より好ましくは4.2%以下であり、さらに好ましくは4%以下である。
ROが多すぎると、平均熱膨張係数を小さくできないおそれがある。そのため、ROは21%以下が好ましく、19%以下がより好ましく、18.5%以下がさらに好ましく、18%以下が特に好ましい。
MgO/ROは0.70以下が好ましく、0.65以下がより好ましく、0.60以下がさらに好ましい。MgO/ROが0.70以下であれば、(T2-歪点)を大きくすることができる。
[SiO2]+0.7[Al2O3]+1.2[B2O3]+0.5[MgO]+0.4[CaO]-0.25[SrO]-0.88[BaO] …(I)
式(I)で表される値は無アルカリガラスの密度(ρ)の指標であり、この値が85%未満であると密度が高くなる。式(I)で表される値は85.4以上がより好ましく、85.8以上がさらに好ましく、86以上が特に好ましい。式(I)で表される値は、特に限定されないが、90以下が好ましく、88以下であるのがより好ましい。
[SiO2]+0.45[Al2O3]+0.21[B2O3]-0.042[MgO]+0.042[CaO]+0.15[SrO]+0.38[BaO] …(II)
式(II)で表される値は無アルカリガラスの溶解温度の指標であり、この値が72未満であると、ガラス粘度が102dPa・sとなる温度T2が低くなる。式(II)で表されるこの値は好ましくは72.5以上であり、より好ましくは73以上である。式(II)で表されるこの値が75超であるとT2が高くなり得る。この値は好ましくは74以下であり、より好ましくは73.5以下である。
0.4[SiO2]+0.4[Al2O3]+0.25[B2O3]-0.7[MgO]-0.88[CaO]-1.4[SrO]-1.7[BaO] …(III)
式(III)で表される値は無アルカリガラスの熱膨張係数αの指標であり、この値が19超であると、平均熱膨張係数が低くなりすぎてしまう。式(III)で表される値は18.9以下が好ましく、18.7以下がより好ましい。式(III)で表される値は、特に限定されないが、15.8以上が好ましく、16.5以上であるのがより好ましい。
なお、上記式(I)~(III)で表される値は、その単位はパーセント(%)であるが、単位を省略して示す。
平均熱膨張係数は35.2×10-7/℃以上が好ましく、35.5×10-7/℃以上がより好ましい。平均熱膨張係数の上限は特に限定されないが、ディスプレイ等の製品製造における生産性や耐熱衝撃性の観点から43×10-7/℃以下が好ましく、40×10-7/℃以下がより好ましく、38.5×10-7/℃以下がさらに好ましい。
上記各成分の原料をガラス組成中で目標含有量となるように調合し、これを溶解炉に投入し、1500~1800℃に加熱して溶解して溶融ガラスを得る。得られた溶融ガラスを成形装置にて、所定の板厚のガラスリボンに成形し、このガラスリボンを徐冷後、切断することによって、無アルカリガラスを得ることができる。
(平均熱膨張係数)
JIS R3102(1995年)に規定されている方法に従い、示差熱膨張計(TMA)を用いて測定した。測定温度範囲は50~350℃で、単位を10-7/℃として表した。
(密度)
JIS Z 8807に規定されている方法に従い、泡を含まない約20gのガラス塊をアルキメデス法によって測定した。
JIS R3103-2(2001年)に規定されている方法に従い測定した。
(ガラス転移点Tg)
JIS R3103-3(2001年)に規定されている方法に従い、示差熱膨張計(TMA)を用いて測定した。
(ヤング率)
JIS Z 2280に規定されている方法に従い、厚さ0.5~10mmのガラスについて、超音波パルス法により測定した。
ASTM C 965-96に規定されている方法に従い、回転粘度計を用いて粘度を測定し、102d・Pa・sとなるときの温度T2(℃)を測定した。
(T4)
ASTM C 965-96に規定されている方法に従い、回転粘度計を用いて粘度を測定し、104d・Pa・sとなるときの温度T4(℃)を測定した。
(失透温度)
前述の方法により、失透温度を求めた。
一方、例21のガラスは、B2O3が3%未満であるため、歪点が過度に高くなっている。また、例21のガラスは、式(I)で表される値が本発明で規定される範囲より低く、密度が高くなっている。例22のガラスは、式(II)で表される値が本発明で規定される範囲より低いため、T2が低くなっている。その結果、溶解温度が低下し、清澄性が悪化して、ガラスの泡品質が悪い。例22のガラスは歪点も低い。例23のガラスは、式(II)で表される値が本発明で規定される範囲より高いため、T2が高くなっている。その結果、溶解性が悪い。また、例23のガラスは式(III)で表される値が本発明で規定される範囲より高いため、結果として熱膨張係数が低くなりすぎている。例24のガラスも、式(III)で表される値が本発明で規定される範囲より高くなっており、MgOの含有量も少ないため、熱膨張係数が低くなりすぎている。
なお、2016年4月27日に出願された日本特許出願2016-088988号の明細書、特許請求の範囲、図面、及び要約書の全内容をここに引用し、本発明の明細書の開示として、取り入れるものである。
Claims (12)
- 酸化物基準のモル%表示で、
SiO2 62~70%、
Al2O3 11~14%、
B2O3 3~6%、
MgO 7~10%、
CaO 3~9%、
SrO 1~5%、
BaO 0~1%、
を含有し、
[SiO2]+0.7[Al2O3]+1.2[B2O3]+0.5[MgO]+0.4[CaO]-0.25[SrO]-0.88[BaO]が85以上であり、
[SiO2]+0.45[Al2O3]+0.21[B2O3]-0.042[MgO]+0.042[CaO]+0.15[SrO]+0.38[BaO]が72~75であり、
0.4[SiO2]+0.4[Al2O3]+0.25[B2O3]-0.7[MgO]-0.88[CaO]-1.4[SrO]-1.7[BaO]が19以下であり、
比弾性率が32MN・m/kg以上であり、歪点が690~710℃であり、密度が2.54g/cm3以下であり、50~350℃での平均熱膨張係数が35×10-7/℃以上であり、かつ、ガラス粘度が102dPa・sとなる温度T2が1610~1680℃であることを特徴とする無アルカリガラス。 - [MgO]≧[CaO]≧[SrO]≧[BaO]である請求項1に記載の無アルカリガラス。
- [MgO]>[CaO]>[SrO]>[BaO]である請求項1または2に記載の無アルカリガラス。
- MgO+CaO+SrO+BaOが15~21%である請求項1~3のいずれかに記載の無アルカリガラス。
- MgO/(MgO+CaO+SrO+BaO)が0.35~0.70である請求項1~4のいずれかに記載の無アルカリガラス。
- ガラス粘度が104dPa・sとなる温度T4が1320℃以下である、請求項1~5のいずれかに記載の無アルカリガラス。
- 失透粘度が103.6dPa・s以上である、請求項1~6のいずれかに記載の無アルカリガラス。
- ヤング率が81GPa以上である、請求項1~7のいずれかに記載の無アルカリガラス。
- (T2-歪点)が920~1000℃である、請求項1~8のいずれかに記載の無アルカリガラス。
- ガラス転位点が730~770℃である請求項1~9のいずれかに記載の無アルカリガラス。
- 厚みが0.1~2.0mmであるガラス板である請求項1~10のいずれかに記載の無アルカリガラス。
- フロート法又はフージョン法で製造される請求項1~11のいずれかに記載の無アルカリガラス。
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