WO2015166890A1 - Non-alkali glass - Google Patents

Non-alkali glass Download PDF

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Publication number
WO2015166890A1
WO2015166890A1 PCT/JP2015/062547 JP2015062547W WO2015166890A1 WO 2015166890 A1 WO2015166890 A1 WO 2015166890A1 JP 2015062547 W JP2015062547 W JP 2015062547W WO 2015166890 A1 WO2015166890 A1 WO 2015166890A1
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mgo
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glass
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PCT/JP2015/062547
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French (fr)
Japanese (ja)
Inventor
博文 ▲徳▼永
和孝 小野
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旭硝子株式会社
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Priority to CN201580023348.5A priority Critical patent/CN106458701B/en
Priority to KR1020167029702A priority patent/KR102291417B1/en
Publication of WO2015166890A1 publication Critical patent/WO2015166890A1/en

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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
    • C03C15/00—Surface treatment of glass, not in the form of fibres or filaments, by etching
    • 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
    • C03C4/00—Compositions for glass with special properties

Definitions

  • the present invention relates to a non-alkali glass which is suitable for various display substrate glasses and photomask substrate glasses and which is substantially free of alkali metal oxides and can be float-molded.
  • the following characteristics have been required for various display substrate glasses, particularly those in which a metal or oxide thin film is formed on the surface.
  • alkali metal oxide When an alkali metal oxide is contained, alkali metal ions diffuse into the thin film and deteriorate the film characteristics, so that the alkali metal ions are not substantially contained.
  • the strain point When exposed to a high temperature in the thin film forming process, the strain point is high so that the deformation (thermal shrinkage) associated with glass deformation and glass structural stabilization can be minimized.
  • BHF buffered hydrofluoric acid
  • ITO various acids used for etching metal electrodes
  • ITO various acids used for etching metal electrodes
  • resistant to alkali of resist stripping solution Resistant to alkali of resist stripping solution.
  • a-Si amorphous silicon
  • p-Si polycrystalline silicon
  • a glass having a small average thermal expansion coefficient is required to increase productivity and thermal shock resistance by increasing the temperature raising / lowering rate of the heat treatment for producing a liquid crystal display.
  • Patent Document 1 discloses SiO 2 —Al 2 O 3 —SrO glass that does not contain B 2 O 3 , but the temperature required for melting is high, which makes manufacturing difficult.
  • Patent Document 2 discloses a glass containing 0 to 5 mol% of B 2 O 3 , but the average coefficient of thermal expansion at 50 to 300 ° C. exceeds 50 ⁇ 10 ⁇ 7 / ° C.
  • an alkali-free glass described in Patent Document 3 has been proposed.
  • the alkali-free glass described in Patent Document 3 has a high strain point, can be molded by a float process, and is suitable for uses such as a display substrate and a photomask substrate.
  • a process of thinning (thinning) the plate thickness by applying an etching process to the glass substrate surface after the array / color filter bonding step is widely employed.
  • the surface of a glass substrate is etched with an etchant containing hydrofluoric acid (HF) (hereinafter referred to as “hydrofluoric acid etching process”) to thin the glass substrate (patent).
  • hydrofluoric acid etching process hydrofluoric acid
  • the object of the present invention is to solve the above drawbacks, have a high strain point, low viscosity, specifically, a temperature T 2 at which the glass viscosity is 10 2 dPa ⁇ s, and a glass viscosity of 10 4 dPa ⁇ s.
  • low temperature T 4 comprising a large etching rate at the time of hydrofluoric acid etching treatment is that the float forming can provide easy alkali-free glass.
  • the strain point is 680 ° C. or higher
  • the average thermal expansion coefficient at 50 to 350 ° C. is 30 ⁇ 10 ⁇ 7 to 43 ⁇ 10 ⁇ 7 / ° C.
  • the glass viscosity is 10 2 dPa ⁇ s.
  • Etching solution 25 ° C., 5%
  • a hydrofluoric acid (HF) having a temperature T 2 of 1670 ° C. or less and a glass viscosity of 10 4 dPa ⁇ s, and a temperature T 4 of 1320 ° C. or less.
  • the mass reduction per unit area when immersed in an HF aqueous solution for 20 minutes is 3.1 mg / cm 2 or more, SiO 2 60 to 70 in terms of mol% based on oxide, Al 2 O 3 11-16, B 2 O 3 more than 0 and 1.5 or less, MgO 7 to 12 or less, CaO More than 0 and less than 7, SrO 4.5 to 10 or less, BaO 0 to 0.5, MgO + CaO + SrO + BaO is 16-22, (SiO 2 + Al 2 O 3 ) / (MgO + CaO + SrO + BaO) is 4.7 or less, MgO / CaO is 1.05 or more, SrO / CaO is 1.05 or more, and (MgO + SrO) / (MgO + CaO + SrO + BaO) is An alkali-free glass that is 0.7 or more is provided.
  • the present invention also relates to SiO 2 63-68 in terms of mol% based on oxide.
  • Al 2 O 3 12-14, B 2 O 3 0.5-1.3, MgO 8-11, CaO 1.5-5, SrO 5-9, BaO 0-0.3, MgO + CaO + SrO + BaO is 17.5-20, (SiO 2 + Al 2 O 3 ) / (MgO + CaO + SrO + BaO) is 4.6 or less, MgO / CaO is 1.3 or more, SrO / CaO is 1.1 or more, and (MgO + SrO) / (MgO + CaO + SrO + BaO) is The alkali-free glass as described above, which is 0.75 or more.
  • the present invention also provides SiO 2 65.5 to 67.5 in terms of mol% based on oxide.
  • the alkali-free glass as described above, which is 8 or more.
  • the alkali-free glass of the present invention is particularly suitable for display substrates for high strain points, photomask substrates, and the like, and is glass that is easy to float.
  • the present invention is not limited to the following embodiments, and can be arbitrarily modified without departing from the gist of the present invention.
  • “wt%” and “mass%” are synonymous.
  • “ ⁇ ” means that the lower limit value and the upper limit value are included, that is, the value is not less than the lower limit value and not more than the upper limit value.
  • the composition range of each component will be described. If the SiO 2 content is less than 60% (mole%, the same unless otherwise specified), the strain point is not sufficiently increased, the thermal expansion coefficient is increased, and the density is increased. It is preferably 63% or more, more preferably 65% or more, and further preferably 65.5% or more. If it exceeds 70%, the solubility is lowered. 69% or less is preferable, 68% or less is more preferable, and 67.5% or less is more preferable.
  • Al 2 O 3 suppresses the phase separation of the glass, lowers the thermal expansion coefficient and raises the strain point. However, if it is less than 11%, this effect does not appear, and other components that increase the expansion increase. As a result, thermal expansion increases. 11.5% or more is preferable, 12% or more is more preferable, and 12.5% or more is more preferable. If it exceeds 16%, the solubility of the glass becomes poor. It is preferably 15% or less, more preferably 14% or less, and further preferably 13.5% or less.
  • B 2 O 3 can be added more than 0% and 1.5% or less in order to improve the melting reactivity of the glass. In order to acquire said effect, 0.2% or more is preferable, 0.5% or more is more preferable, and 0.7% or more is further more preferable. However, if it is too much, the strain point is lowered. Therefore, it is preferably 1.4% or less, more preferably 1.3% or less, and further preferably 1.2% or less.
  • MgO has the characteristics that it does not increase the expansion in alkaline earth and does not excessively lower the strain point, and also improves the solubility. If it is 7% or less, the above-described effect due to the addition of MgO is not sufficiently exhibited. 7.5% or more is preferable, 8% or more is more preferable, and 8.5% or more is more preferable. However, if it exceeds 12%, the devitrification temperature may increase. It is preferably 11% or less, more preferably 10% or less, and even more preferably 9.5% or less.
  • CaO has the characteristics that it does not increase the expansion in alkaline earth next to MgO and does not excessively lower the strain point, and improves the solubility. Therefore, CaO can be added more than 0% and 7% or less. 1% or more is preferable, 1.5% or more is more preferable, and 2% or more is more preferable. However, if it exceeds 7%, a large amount of phosphorus, which is an impurity in limestone (CaCO 3 ), which is a CaO raw material, may be mixed. 6% or less is preferable, 5% or less is more preferable, and 4.5% or less is more preferable.
  • SrO improves the solubility, but this effect does not appear sufficiently at 4.5% or less. 4.7% or more is preferable, 4.9% or more is more preferable, 5.0% or more is more preferable, and 5.3% or more is more preferable. However, if it exceeds 10%, the expansion coefficient may increase. It is preferably 9% or less, more preferably 8.5% or less, and even more preferably 8% or less.
  • BaO is not essential, but can be contained to improve solubility. However, too much increases the expansion and density of the glass excessively, so the content is made 0.5% or less. 0.3% or less is preferable, 0.1% or less is more preferable, and it is still more preferable not to contain substantially. “Substantially not contained” means not containing any inevitable impurities.
  • ZrO 2 may be contained up to 0.5% in order to lower the glass melting temperature or to promote crystal precipitation during firing. If it exceeds 0.5%, the glass becomes unstable or the relative dielectric constant ⁇ of the glass increases. 0.3% or less is preferable, 0.1% or less is more preferable, and it is especially preferable not to contain substantially.
  • MgO, CaO, SrO, and BaO are less than 16% in total, solubility is poor. It is preferably 17% or more, more preferably 17.5% or more, and further preferably 18% or more. If it exceeds 22%, there is a risk that the thermal expansion coefficient cannot be reduced. It is preferably 21% or less, more preferably 20% or less, and further preferably 19.5% or less.
  • the total amount of MgO, CaO, SrO and BaO satisfies the above and satisfies the following conditions, thereby increasing the viscosity of the glass without increasing the thermal expansion coefficient.
  • temperature T 2 which the glass viscosity of 10 2 dPa ⁇ s, and may reduce the temperature T 4 which glass viscosity of 10 4 dPa ⁇ s.
  • SiO 2 + Al 2 O 3 ) / (MgO + CaO + SrO + BaO) is 4.7 or less, preferably 4.6 or less, more preferably 4.5 or less, and even more preferably 4.4 or less.
  • the alkali-free glass of the present invention can lower the glass viscosity, particularly the temperature T 4 at which the glass viscosity is 10 4 dPa ⁇ s, and the etching rate during the hydrofluoric acid etching treatment.
  • MgO / CaO is 1.05 or more, preferably 1.3 or more, more preferably 1.5 or more, and still more preferably 2 or more.
  • SrO / CaO is 1.05 or more, preferably 1.08 or more, more preferably 1.1 or more, and even more preferably 1.15 or more.
  • (MgO + CaO) / (MgO + CaO + SrO + BaO) is 0.7 or more, preferably 0.75 or more, and more preferably 0.8 or more. 0.82 or more is more preferable.
  • the glass of the present invention does not contain an alkali metal oxide in excess of the impurity level (ie substantially) in order not to cause deterioration of the characteristics of the metal or oxide thin film provided on the glass surface during panel production.
  • P 2 O 5 is not substantially contained.
  • PbO, As 2 O 3 , and Sb 2 O 3 are not substantially contained.
  • the alkali-free glass of the present invention contains ZnO, Fe 2 O 3 , SO 3 , F, Cl, SnO 2 and the like in order to improve the solubility, clarity and moldability (float moldability) of the glass in addition to the above components. 1% or less, preferably 0.9% or less, more preferably 0.8% or less, and still more preferably 0.7% or less (preferably contained). It is preferable that ZnO is not substantially contained.
  • the alkali-free glass of the present invention has a strain point of 680 ° C. or higher, thermal shrinkage during panel production can be suppressed. Further, a solid phase crystallization method can be applied as a method for manufacturing a p-Si TFT. Since the alkali-free glass of the present invention has a strain point of 680 ° C. or higher, it is used for a high strain point (for example, a display substrate or lighting substrate for organic EL, or a thin display substrate or lighting plate having a thickness of 100 ⁇ m or less). Suitable for use on a substrate). Preferably it is 690 degreeC or more, More preferably, it is 700 degreeC or more, More preferably, it is 710 degreeC or more.
  • the alkali-free glass of the present invention has a glass transition point of preferably 745 ° C. or higher, more preferably 750 ° C. or higher, and further preferably 755 ° C. or higher for the same reason as the strain point.
  • the alkali-free glass of the present invention has an average coefficient of thermal expansion at 50 to 350 ° C. of 30 ⁇ 10 ⁇ 7 to 43 ⁇ 10 ⁇ 7 / ° C., has high thermal shock resistance, and has high productivity during panel production. it can.
  • the average thermal expansion coefficient at 50 to 350 ° C. is preferably 35 ⁇ 10 ⁇ 7 or more.
  • the average thermal expansion coefficient at 50 to 350 ° C. is preferably 42 ⁇ 10 ⁇ 7 / ° C. or less, more preferably 41 ⁇ 10 ⁇ 7 / ° C. or less, and further preferably 40 ⁇ 10 ⁇ 7 / ° C. or less.
  • the alkali-free glass of the present invention has a specific gravity of preferably 2.7 or less, more preferably 2.67 or less, and even more preferably 2.65 or less.
  • the alkali-free glass of the present invention has a temperature T 2 at which the viscosity ⁇ becomes 10 2 poise (dPa ⁇ s), 1670 ° C. or less, preferably less than 1670 ° C., preferably 1665 ° C. or less, more preferably 1660 ° C. or less, Furthermore, since it is 1655 degrees C or less preferably, melt
  • the alkali-free glass of the present invention has a temperature T 4 at which the viscosity ⁇ becomes 10 4 poise is 1320 ° C. or less, preferably less than 1320 ° C., preferably 1315 ° C. or less, more preferably 1310 ° C. or less, and further preferably 1305 ° C. or less. It is suitable for float forming.
  • the alkali-free glass of the present invention preferably has a devitrification temperature of 1350 ° C. or less because molding by the float method is easy. Preferably it is 1340 degrees C or less, More preferably, it is 1330 degrees C or less.
  • the devitrification temperature is obtained by putting crushed glass particles in a platinum dish and performing heat treatment for 17 hours in an electric furnace controlled at a constant temperature. It is an average value of the maximum temperature at which crystals are deposited inside and the minimum temperature at which crystals are not deposited.
  • the alkali-free glass of the present invention preferably has a Young's modulus of 80 GPa or more, more preferably 82 GPa or more, and further 84 GPa or more.
  • the alkali-free glass of the present invention preferably has a compaction of 120 ppm or less measured by the procedure described in the examples described later. Compaction is the glass heat shrinkage generated by relaxation of the glass structure during the heat treatment.
  • the compaction measured by the procedure described in the examples described later is more preferably 100 ppm or less, further preferably 80 ppm or less, further 60 ppm or less, and particularly preferably 50 ppm or less.
  • the alkali-free glass of the present invention preferably has a photoelastic constant of 31 nm / MPa / cm or less. Due to the birefringence of the glass substrate due to stress generated during the manufacturing process of the liquid crystal display panel and the liquid crystal display device, a phenomenon in which the black display becomes gray and the contrast of the liquid crystal display decreases may be observed. By setting the photoelastic constant to 31 nm / MPa / cm or less, this phenomenon can be suppressed small.
  • the alkali-free glass of the present invention has a photoelastic constant of preferably 23 nm / MPa / cm or more, more preferably 25 nm / MPa / cm or more, considering the ease of securing other physical properties.
  • the photoelastic constant can be measured at a measurement wavelength of 546 nm by a disk compression method.
  • the alkali-free glass of the present invention has a mass reduction per unit area of 3.1 mg / min when immersed in a 5% by mass hydrofluoric acid (HF) aqueous solution at 25 ° C., which is an index of etching rate during hydrofluoric acid etching treatment. cm 2 or more.
  • HF hydrofluoric acid
  • the alkali-free glass of the present invention can be produced, for example, by the following method.
  • the raw materials for each component that are normally used are blended so as to become target components, which are continuously charged into a melting furnace and heated to 1500 to 1800 ° C. for melting.
  • a plate glass can be obtained by forming this molten glass into a predetermined plate thickness by a float method or a fusion method, preferably by a float method, and cutting after slow cooling.
  • the molded plate thickness is preferably 0.7 mm or less, more preferably 0.5 mm or less, 0.3 mm or less, or 0.1 mm or less.
  • Examples 1 to 12, Examples 15 to 20 are examples, and Examples 13 to 14 and Example 21 are comparative examples.
  • the raw materials of each component were prepared so as to have a target composition and melted at a temperature of 1500 to 1650 ° C. using a platinum crucible. In melting, the mixture was stirred using a platinum stirrer to homogenize the glass. Next, the molten glass was poured out, formed into a plate shape, and then slowly cooled.
  • Tables 1 to 3 show the glass composition (unit: mol%), the average thermal expansion coefficient at 50 to 350 ° C. (unit: ⁇ 10 ⁇ 7 / ° C.), the strain point (unit: ° C.), the glass transition point (unit: ° C), specific gravity, Young's modulus (GPa) (measured by ultrasonic method), high-temperature viscosity value, temperature T 2 (temperature at which glass viscosity ⁇ becomes 10 2 poise, unit: ° C) Temperature T 4 (temperature at which the glass viscosity ⁇ becomes 10 4 poise, unit: ° C), devitrification temperature (unit: ° C), photoelastic constant (unit: nm / MPa /) cm) (measured by a disk compression method at a measurement wavelength of 546 nm), mass decrease per unit area when immersed in a 5 mass% hydrofluoric acid (HF) aqueous solution at 25 ° C.
  • GPa Young's modulus
  • a glass plate sample (length 100 mm ⁇ width 10 mm ⁇ thickness 1 mm sample mirror-polished with cerium oxide) is held at a temperature of glass transition point + 100 ° C. for 10 minutes, and then cooled to room temperature at 40 ° C. per minute. Here, the total length (length direction) L1 of the sample is measured. Thereafter, the sample is heated at 100 ° C.
  • all the glasses of the examples have an average coefficient of thermal expansion as low as 30 ⁇ 10 ⁇ 7 to 43 ⁇ 10 ⁇ 7 / ° C. and a strain point of 680 ° C. or higher.
  • Temperature T 2 which is a measure of the solubility is also easy to dissolve low as 1670 ° C. or less
  • a temperature T 4 which is a measure of formability is at 1320 ° C. or less, it is easily molded by a float process.
  • the photoelastic constant is 31 nm / MPa / cm or less, and when used as a glass substrate of a liquid crystal display, a decrease in contrast can be suppressed.
  • the mass loss per unit area when immersed in a 5 mass% hydrofluoric acid (HF) aqueous solution at 25 ° C. for 20 minutes, which is an index of the etching rate during the hydrofluoric acid etching treatment, is 3.1 mg / cm 2 or more.
  • the alkali-free glass of the present invention has a high strain point and can be formed by a float process, and is suitable for uses such as a display substrate and a photomask substrate. It is also suitable for applications such as magnetic disk substrates and solar cell substrates.

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  • Engineering & Computer Science (AREA)
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Abstract

　The purpose of the present invention is to provide non-alkali glass having a high strain point, low viscosity, high etching speed, and high ease of float molding. The present invention pertains to non-alkali glass of a specific oxide composition, the non-alkali glass having a strain point of 680℃ or higher, and an average coefficient of thermal expansion of 30 × 10-7 to 43 × 10-7/℃ at 50-350℃, the temperature (T2) at which the glass viscosity reaches 102dPa・s being 1670℃ or lower, the temperature (T4) at which the glass viscosity reaches 104dPa・s being 1320℃ or lower, and the mass loss being 3.1 mg/cm2 or higher when the non-alkali glass is immersed for 20 minutes in etching solution.

Description

無アルカリガラスAlkali-free glass
　本発明は、各種ディスプレイ用基板ガラスやフォトマスク用基板ガラスとして好適な、アルカリ金属酸化物を実質上含有せず、フロート成形が可能な、無アルカリガラスに関する。 The present invention relates to a non-alkali glass which is suitable for various display substrate glasses and photomask substrate glasses and which is substantially free of alkali metal oxides and can be float-molded.
　従来、各種ディスプレイ用基板ガラス、特に表面に金属ないし酸化物薄膜等を形成するものでは、以下に示す特性が要求されてきた。
（１）アルカリ金属酸化物を含有していると、アルカリ金属イオンが薄膜中に拡散して膜特性を劣化させるため、実質的にアルカリ金属イオンを含まないこと。
（２）薄膜形成工程で高温にさらされる際に、ガラス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。 Conventionally, the following characteristics have been required for various display substrate glasses, particularly those in which a metal or oxide thin film is formed on the surface.
(1) When an alkali metal oxide is contained, alkali metal ions diffuse into the thin film and deteriorate the film characteristics, so that the alkali metal ions are not substantially contained.
(2) When exposed to a high temperature in the thin film forming process, the strain point is high so that the deformation (thermal shrinkage) associated with glass deformation and glass structural stabilization can be minimized.
（３）半導体形成に用いる各種薬品に対して充分な化学耐久性を有すること。特にＳｉＯＸやＳｉＮＸのエッチングのためのバッファードフッ酸（ＢＨＦ：フッ酸とフッ化アンモニウムの混合液）、およびＩＴＯのエッチングに用いる塩酸を含有する薬液、金属電極のエッチングに用いる各種の酸（硝酸、硫酸等）、レジスト剥離液のアルカリに対して耐久性のあること。
（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。 (3) Sufficient chemical durability against various chemicals used for semiconductor formation. In particular, buffered hydrofluoric acid (BHF: liquid mixture of hydrofluoric acid and ammonium fluoride) for etching SiO X and SiN X , and chemicals containing hydrochloric acid used for etching ITO, various acids used for etching metal electrodes (Nitric acid, sulfuric acid, etc.) Resistant to alkali of resist stripping solution.
(4) There are no defects (bubbles, striae, inclusions, pits, scratches, etc.) inside and on the surface.
　上記の要求に加えて、近年では、以下のような状況にある。
（５）ディスプレイの軽量化が要求され、ガラス自身も密度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、基板ガラスの薄板化が望まれる。 In addition to the above requirements, in recent years, there are the following situations.
(5) The weight reduction of the display is required, and the glass itself is desired to have a low density.
(6) A reduction in the weight of the display is required, and a reduction in the thickness of the substrate glass is desired.
（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、若干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：約３５０℃→ｐ－Ｓｉ：３５０～５５０℃）。
（８）液晶ディスプレイ作製熱処理の昇降温速度を速くして、生産性を上げたり耐熱衝撃性を上げるために、ガラスの平均熱膨張係数の小さいガラスが求められる。 (7) In addition to the conventional amorphous silicon (a-Si) type liquid crystal display, a polycrystalline silicon (p-Si) type liquid crystal display having a slightly higher heat treatment temperature has been produced (a-Si). : About 350 ° C. → p-Si: 350 to 550 ° C.).
(8) A glass having a small average thermal expansion coefficient is required to increase productivity and thermal shock resistance by increasing the temperature raising / lowering rate of the heat treatment for producing a liquid crystal display.
　一方、エッチングのドライ化が進み、耐ＢＨＦ性に対する要求が弱くなってきている。これまでのガラスは、耐ＢＨＦ性を良くするために、Ｂ２Ｏ３を６～１０モル％含有するガラスが多く用いられてきた。しかし、Ｂ２Ｏ３は歪点を下げる傾向がある。Ｂ２Ｏ３を含有しないまたは含有量の少ない無アルカリガラスの例としては以下のようなものがある。 On the other hand, dry etching has progressed, and the demand for BHF resistance has become weaker. Conventionally, glass containing 6 to 10 mol% of B 2 O 3 has been often used in order to improve BHF resistance. However, B 2 O 3 tends to lower the strain point. Examples of non-alkali glass that does not contain B 2 O 3 or have a low content are as follows.
　特許文献１にはＢ２Ｏ３を含有しない、ＳｉＯ２－Ａｌ２Ｏ３－ＳｒＯガラスが開示されているが、溶解に必要な温度が高く製造に困難を生ずる。 Patent Document 1 discloses SiO 2 —Al 2 O 3 —SrO glass that does not contain B 2 O 3 , but the temperature required for melting is high, which makes manufacturing difficult.
　特許文献２にはＢ２Ｏ３を０～５モル％含有するガラスが開示されているが、５０～３００℃での平均熱膨張係数が５０×１０－７／℃を超える。 Patent Document 2 discloses a glass containing 0 to 5 mol% of B 2 O 3 , but the average coefficient of thermal expansion at 50 to 300 ° C. exceeds 50 × 10 −7 / ° C.
　特許文献１～２に記載のガラスにおける問題点を解決するため、特許文献３に記載の無アルカリガラスが提案されている。特許文献３に記載の無アルカリガラスは、歪点が高く、フロート法による成形ができ、ディスプレイ用基板、フォトマスク用基板等の用途に好適であるとされている。 In order to solve the problems in the glasses described in Patent Documents 1 and 2, an alkali-free glass described in Patent Document 3 has been proposed. The alkali-free glass described in Patent Document 3 has a high strain point, can be molded by a float process, and is suitable for uses such as a display substrate and a photomask substrate.
日本国特開昭６２－１１３７３５号公報Japanese Unexamined Patent Publication No. Sho 62-1113735 日本国特開平５－２３２４５８号公報Japanese Patent Laid-Open No. 5-232458 日本国特開平１０－４５４２２号公報Japanese Patent Laid-Open No. 10-45422 国際公開第２００９－０６６６２４号International Publication No. 2009-066664
　高品質のｐ－Ｓｉ　ＴＦＴの製造方法として固相結晶化法があるが、これを実施するためには、歪点をより高くすることが求められる。
　一方、ガラス製造プロセス、特に溶解、成形における要請から、ガラスの粘性、具体的には、ガラス粘度が１０２ｄＰａ・ｓとなる温度Ｔ２、および、ガラス粘度が１０４ｄＰａ・ｓとなる温度Ｔ４を低くすることが求められている。
　一方、中小型の液晶ディスプレイ（ＬＣＤ）や有機ＥＬディスプレイ（ＯＥＬＤ）、特にモバイル、デジタルカメラや携帯電話等の携帯型ディスプレイの分野では、ディスプレイの軽量化、薄型化が重要な課題となっている。更なるガラス基板の薄板化を実現するために、アレイ・カラーフィルタ貼合わせ工程後に、ガラス基板表面にエッチング処理を施し、板厚を薄くする（薄板化する）工程が広く採用されている。例えば、ガラス基板の表面を、フッ酸（ＨＦ）を含有するエッチング液でエッチング処理（以下、『フッ酸エッチング処理』という。）して、ガラス基板を薄板化することが行われている（特許文献４参照）。
　フッ酸エッチング処理でガラス基板を薄板化する場合、フッ酸エッチング処理時のエッチング速度が大きいことが求められる。 There is a solid-phase crystallization method as a method for producing a high-quality p-Si TFT. In order to carry out this, it is required to raise the strain point.
On the other hand, the glass viscosity, specifically, the temperature T 2 at which the glass viscosity becomes 10 2 dPa · s, and the temperature at which the glass viscosity becomes 10 4 dPa · s due to demands in the glass production process, particularly melting and molding. to lower of T 4 is required.
On the other hand, in the field of small and medium-sized liquid crystal displays (LCDs) and organic EL displays (OELDs), especially portable displays such as mobiles, digital cameras and mobile phones, weight reduction and thinning of the displays are important issues. . In order to realize further thinning of the glass substrate, a process of thinning (thinning) the plate thickness by applying an etching process to the glass substrate surface after the array / color filter bonding step is widely employed. For example, the surface of a glass substrate is etched with an etchant containing hydrofluoric acid (HF) (hereinafter referred to as “hydrofluoric acid etching process”) to thin the glass substrate (patent). Reference 4).
When the glass substrate is thinned by the hydrofluoric acid etching process, it is required that the etching rate during the hydrofluoric acid etching process be high.
　本発明の目的は、上記欠点を解決し、歪点が高く、低粘性、具体的には、ガラス粘度が１０２ｄＰａ・ｓとなる温度Ｔ２、および、ガラス粘度が１０４ｄＰａ・ｓとなる温度Ｔ４が低く、フッ酸エッチング処理時のエッチング速度が大きく、フロート成形が容易な無アルカリガラスを提供することにある。 The object of the present invention is to solve the above drawbacks, have a high strain point, low viscosity, specifically, a temperature T 2 at which the glass viscosity is 10 2 dPa · s, and a glass viscosity of 10 4 dPa · s. low temperature T 4 comprising a large etching rate at the time of hydrofluoric acid etching treatment is that the float forming can provide easy alkali-free glass.
　本発明は、歪点が６８０℃以上であって、５０～３５０℃での平均熱膨張係数が３０×１０－７～４３×１０－７／℃であって、ガラス粘度が１０２ｄＰａ・ｓとなる温度Ｔ２が１６７０℃以下であって、ガラス粘度が１０４ｄＰａ・ｓとなる温度Ｔ４が１３２０℃以下であって、フッ酸（ＨＦ）を含有するエッチング液（２５℃、５％ＨＦ水溶液）に２０分間浸漬させた際の単位面積当たりの質量減少が３．１ｍｇ／ｃｍ２以上であって、
酸化物基準のモル％表示で
ＳｉＯ２　　　　　　　６０～７０、
Ａｌ２Ｏ３　　　　　　　１１～１６、
Ｂ２Ｏ３　　　　　　　　０超１．５以下、
ＭｇＯ　　　　　　　　　７超１２以下、
ＣａＯ　　　　　　　　　０超７以下、
ＳｒＯ　　　　　　　　　　４．５超１０以下、
ＢａＯ　　　　　　　　　０～０．５を含有し
ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯが１６～２２であり、
（ＳｉＯ２＋Ａｌ２Ｏ３）／（ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯ）が４．７以下であり、ＭｇＯ／ＣａＯが１．０５以上であり、ＳｒＯ／ＣａＯが１．０５以上であり、（ＭｇＯ＋ＳｒＯ）／（ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯ）が０．７以上である無アルカリガラスを提供する。
　また本発明は、酸化物基準のモル％表示で
ＳｉＯ２　　　　　　　　６３～６８、
Ａｌ２Ｏ３　　　　　　　　　１２～１４、
Ｂ２Ｏ３　　　　　　　　　０．５～１．３、
ＭｇＯ　　　　　　　　８～１１、
ＣａＯ　　　　　　　　１．５～５、
ＳｒＯ　　　　　　　　５～９、
ＢａＯ　　　　　　　　０～０．３を含有し
ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯが１７．５～２０であり、
（ＳｉＯ２＋Ａｌ２Ｏ３）／（ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯ）が４．６以下であり、ＭｇＯ／ＣａＯが１．３以上であり、ＳｒＯ／ＣａＯが１．１以上であり、（ＭｇＯ＋ＳｒＯ）／（ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯ）が０．７５以上である上記記載の無アルカリガラスを提供する。
　また本発明は、酸化物基準のモル％表示で
ＳｉＯ２　　　　　　　　６５．５～６７．５、
Ａｌ２Ｏ３　　　　　　　　１２．５～１３．５、
Ｂ２Ｏ３　　　　　　　　　　　０．７～１．２、
ＭｇＯ　　　　　　　　８．５～１０、
ＣａＯ　　　　　　　　２～４．５、
ＳｒＯ　　　　　　　　５．３～８を含有し、
ＢａＯを実質的に含有せず、
ＭｇＯ＋ＣａＯ＋ＳｒＯが１８～１９．５であり、
（ＳｉＯ２＋Ａｌ２Ｏ３）／（ＭｇＯ＋ＣａＯ＋ＳｒＯ）が４．５以下であり、ＭｇＯ／ＣａＯが２以上であり、ＳｒＯ／ＣａＯが１．１５以上であり、（ＭｇＯ＋ＳｒＯ）／（ＭｇＯ＋ＣａＯ＋ＳｒＯ）が０．８以上である上記記載の無アルカリガラスを提供する。 In the present invention, the strain point is 680 ° C. or higher, the average thermal expansion coefficient at 50 to 350 ° C. is 30 × 10 −7 to 43 × 10 −7 / ° C., and the glass viscosity is 10 2 dPa · s. Etching solution (25 ° C., 5%) containing a hydrofluoric acid (HF) having a temperature T 2 of 1670 ° C. or less and a glass viscosity of 10 4 dPa · s, and a temperature T 4 of 1320 ° C. or less. The mass reduction per unit area when immersed in an HF aqueous solution for 20 minutes is 3.1 mg / cm 2 or more,
SiO 2 60 to 70 in terms of mol% based on oxide,
Al 2 O 3 11-16,
B 2 O 3 more than 0 and 1.5 or less,
MgO 　　 7 to 12 or less,
CaO 　　 More than 0 and less than 7,
SrO 　　　　　 4.5 to 10 or less,
BaO 　　 0 to 0.5, MgO + CaO + SrO + BaO is 16-22,
(SiO 2 + Al 2 O 3 ) / (MgO + CaO + SrO + BaO) is 4.7 or less, MgO / CaO is 1.05 or more, SrO / CaO is 1.05 or more, and (MgO + SrO) / (MgO + CaO + SrO + BaO) is An alkali-free glass that is 0.7 or more is provided.
The present invention also relates to SiO 2 63-68 in terms of mol% based on oxide.
Al 2 O 3 12-14,
B 2 O 3 0.5-1.3,
MgO 8-11,
CaO 1.5-5,
SrO 5-9,
BaO 0-0.3, MgO + CaO + SrO + BaO is 17.5-20,
(SiO 2 + Al 2 O 3 ) / (MgO + CaO + SrO + BaO) is 4.6 or less, MgO / CaO is 1.3 or more, SrO / CaO is 1.1 or more, and (MgO + SrO) / (MgO + CaO + SrO + BaO) is The alkali-free glass as described above, which is 0.75 or more.
The present invention also provides SiO 2 65.5 to 67.5 in terms of mol% based on oxide.
Al 2 O 3 12.5 to 13.5,
B 2 O 3 0.7 to 1.2,
MgO 8.5-10,
CaO 2 to 4.5,
Containing SrO 5.3-8,
Substantially free of BaO,
MgO + CaO + SrO is 18 to 19.5,
(SiO 2 + Al 2 O 3 ) / (MgO + CaO + SrO) is 4.5 or less, MgO / CaO is 2 or more, SrO / CaO is 1.15 or more, and (MgO + SrO) / (MgO + CaO + SrO) is 0. The alkali-free glass as described above, which is 8 or more.
　本発明の無アルカリガラスは、特に高歪点用途のディスプレイ用基板、フォトマスク用基板等に好適であり、また、フロート成形が容易なガラスである。 The alkali-free glass of the present invention is particularly suitable for display substrates for high strain points, photomask substrates, and the like, and is glass that is easy to float.
　以下、本発明を詳細に説明するが、本発明は以下の実施形態に限定されるものではなく、本発明の要旨を逸脱しない範囲において、任意に変形して実施することができる。なお、本明細書において、“重量％”と“質量％”とは同義である。また、“～”とは、その下限値と上限値を含み、すなわち、その下限値以上、その上限値以下であることを意味する。
　各成分の組成範囲について説明する。ＳｉＯ２は６０％（モル％、以下特記しないかぎり同じ）未満では、歪点が充分に上がらず、かつ、熱膨張係数が増大し、密度が上昇する。６３％以上が好ましく、６５％以上がより好ましく、６５．５％以上がさらに好ましい。７０％超では、溶解性が低下する。６９％以下が好ましく、６８％以下がより好ましく、６７．５％以下がさらに好ましい。 Hereinafter, the present invention will be described in detail, but the present invention is not limited to the following embodiments, and can be arbitrarily modified without departing from the gist of the present invention. In the present specification, “wt%” and “mass%” are synonymous. Further, “˜” means that the lower limit value and the upper limit value are included, that is, the value is not less than the lower limit value and not more than the upper limit value.
The composition range of each component will be described. If the SiO 2 content is less than 60% (mole%, the same unless otherwise specified), the strain point is not sufficiently increased, the thermal expansion coefficient is increased, and the density is increased. It is preferably 63% or more, more preferably 65% or more, and further preferably 65.5% or more. If it exceeds 70%, the solubility is lowered. 69% or less is preferable, 68% or less is more preferable, and 67.5% or less is more preferable.
　Ａｌ２Ｏ３はガラスの分相性を抑制し、熱膨脹係数を下げ、歪点を上げるが、１１％未満ではこの効果があらわれず、また、ほかの膨張を上げる成分を増加させることになるため、結果的に熱膨張が大きくなる。１１．５％以上が好ましく、１２％以上がより好ましく、１２．５％以上がさらに好ましい。１６％超ではガラスの溶解性が悪くなる。１５％以下が好ましく、１４％以下がより好ましく、１３．５％以下がさらに好ましい。 Al 2 O 3 suppresses the phase separation of the glass, lowers the thermal expansion coefficient and raises the strain point. However, if it is less than 11%, this effect does not appear, and other components that increase the expansion increase. As a result, thermal expansion increases. 11.5% or more is preferable, 12% or more is more preferable, and 12.5% or more is more preferable. If it exceeds 16%, the solubility of the glass becomes poor. It is preferably 15% or less, more preferably 14% or less, and further preferably 13.5% or less.
　Ｂ２Ｏ３は、ガラスの溶解反応性をよくするため０％超１．５％以下添加できる。上記の効果を得るためには、０．２％以上が好ましく、０．５％以上がより好ましく、０．７％以上がさらに好ましい。しかし、多すぎると歪点が低くなる。したがって１．４％以下が好ましく、１．３％以下がより好ましく、１．２％以下がさらに好ましい。 B 2 O 3 can be added more than 0% and 1.5% or less in order to improve the melting reactivity of the glass. In order to acquire said effect, 0.2% or more is preferable, 0.5% or more is more preferable, and 0.7% or more is further more preferable. However, if it is too much, the strain point is lowered. Therefore, it is preferably 1.4% or less, more preferably 1.3% or less, and further preferably 1.2% or less.
　ＭｇＯは、アルカリ土類の中では膨張を高くせず、かつ歪点を過大には低下させないという特徴を有し、溶解性も向上させる。
　７％以下では上述したＭｇＯ添加による効果が十分あらわれない。７．５％以上が好ましく、８％以上がより好ましく、８．５％以上がさらに好ましい。しかし、１２％を超えると、失透温度が上昇するおそれがある。１１％以下が好ましく、１０％以下がより好ましく、９．５％以下がさらに好ましい。 MgO has the characteristics that it does not increase the expansion in alkaline earth and does not excessively lower the strain point, and also improves the solubility.
If it is 7% or less, the above-described effect due to the addition of MgO is not sufficiently exhibited. 7.5% or more is preferable, 8% or more is more preferable, and 8.5% or more is more preferable. However, if it exceeds 12%, the devitrification temperature may increase. It is preferably 11% or less, more preferably 10% or less, and even more preferably 9.5% or less.
　ＣａＯは、ＭｇＯに次いでアルカリ土類中では膨張を高くせず、かつ歪点を過大には低下させないという特徴を有し、溶解性も向上させるため、０％超７％以下添加できる。１％以上が好ましく、１．５％以上がより好ましく、２％以上がさらに好ましい。しかし、７％を超えると、ＣａＯ原料である石灰石（ＣａＣＯ３）中の不純物であるリンが、多く混入するおそれがある。６％以下が好ましく、５％以下がより好ましく、４．５％以下がさらに好ましい。 CaO has the characteristics that it does not increase the expansion in alkaline earth next to MgO and does not excessively lower the strain point, and improves the solubility. Therefore, CaO can be added more than 0% and 7% or less. 1% or more is preferable, 1.5% or more is more preferable, and 2% or more is more preferable. However, if it exceeds 7%, a large amount of phosphorus, which is an impurity in limestone (CaCO 3 ), which is a CaO raw material, may be mixed. 6% or less is preferable, 5% or less is more preferable, and 4.5% or less is more preferable.
　ＳｒＯは、溶解性を向上させるが、４．５％以下ではこの効果が十分あらわれない。４．７％以上が好ましく、４．９％以上がより好ましく、５．０％以上がより好ましく、５．３％以上がさらに好ましい。しかし、１０％を超えると膨脹係数が増大するおそれがある。９％以下が好ましく、８．５％以下がより好ましく、８％以下がさらに好ましい。 SrO improves the solubility, but this effect does not appear sufficiently at 4.5% or less. 4.7% or more is preferable, 4.9% or more is more preferable, 5.0% or more is more preferable, and 5.3% or more is more preferable. However, if it exceeds 10%, the expansion coefficient may increase. It is preferably 9% or less, more preferably 8.5% or less, and even more preferably 8% or less.
　ＢａＯは必須ではないが溶解性向上のために含有できる。しかし、多すぎるとガラスの膨張と密度を過大に増加させるので０．５％以下とする。０．３％以下が好ましく、０．１％以下がより好ましく、実質的に含有しないことがさらに好ましい。実質的に含有しないとは、不可避的不純物を除き含有しない意味である。 BaO is not essential, but can be contained to improve solubility. However, too much increases the expansion and density of the glass excessively, so the content is made 0.5% or less. 0.3% or less is preferable, 0.1% or less is more preferable, and it is still more preferable not to contain substantially. “Substantially not contained” means not containing any inevitable impurities.
　ＺｒＯ２は、ガラス溶融温度を低下させるために、または焼成時の結晶析出を促進するために、０．５％まで含有してもよい。０．５％超ではガラスが不安定になる、またはガラスの比誘電率εが大きくなる。０．３％以下が好ましく、０．１％以下がより好ましく、実質的に含有しないことが特に好ましい。 ZrO 2 may be contained up to 0.5% in order to lower the glass melting temperature or to promote crystal precipitation during firing. If it exceeds 0.5%, the glass becomes unstable or the relative dielectric constant ε of the glass increases. 0.3% or less is preferable, 0.1% or less is more preferable, and it is especially preferable not to contain substantially.
　ＭｇＯ、ＣａＯ、ＳｒＯ、ＢａＯは合量で１６％よりも少ないと、溶解性に乏しい。１７％以上が好ましく、１７．５％以上がより好ましく、１８％以上がさらに好ましい。２２％よりも多いと、熱膨張係数を小さくできないという難点が生じるおそれがある。２１％以下が好ましく、２０％以下がより好ましく、１９．５％以下がさらに好ましい。 When MgO, CaO, SrO, and BaO are less than 16% in total, solubility is poor. It is preferably 17% or more, more preferably 17.5% or more, and further preferably 18% or more. If it exceeds 22%, there is a risk that the thermal expansion coefficient cannot be reduced. It is preferably 21% or less, more preferably 20% or less, and further preferably 19.5% or less.
　本発明の無アルカリガラスは、ＭｇＯ、ＣａＯ、ＳｒＯおよびＢａＯの合量が上記を満たし、かつ、下記条件を満たすことにより、熱膨張係数を増大することなく、ガラスの粘性、具体的には、ガラス粘度が１０２ｄＰａ・ｓとなる温度Ｔ２、および、ガラス粘度が１０４ｄＰａ・ｓとなる温度Ｔ４を下げることができる。
　（ＳｉＯ２＋Ａｌ２Ｏ３）／（ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯ）が４．７以下であり、４．６以下が好ましく、４．５以下がより好ましく、４．４以下がさらに好ましい。 In the alkali-free glass of the present invention, the total amount of MgO, CaO, SrO and BaO satisfies the above and satisfies the following conditions, thereby increasing the viscosity of the glass without increasing the thermal expansion coefficient. temperature T 2 which the glass viscosity of 10 2 dPa · s, and may reduce the temperature T 4 which glass viscosity of 10 4 dPa · s.
(SiO 2 + Al 2 O 3 ) / (MgO + CaO + SrO + BaO) is 4.7 or less, preferably 4.6 or less, more preferably 4.5 or less, and even more preferably 4.4 or less.
　本発明の無アルカリガラスは、下記３条件を満たすことにより、ガラスの粘性、特にガラス粘度が１０４ｄＰａ・ｓとなる温度Ｔ４を下げることができ、かつ、フッ酸エッチング処理時のエッチング速度が大きくなる。
　ＭｇＯ／ＣａＯが１．０５以上であり、１．３以上が好ましく、１．５以上がより好ましく、２以上がさらに好ましい。
　ＳｒＯ／ＣａＯが１．０５以上であり、１．０８以上が好ましく、１．１以上がより好ましく、１．１５以上がさらに好ましい。
　（ＭｇＯ＋ＣａＯ）／（ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯ）が０．７以上であり、０．７５以上が好ましく、０．８以上がより好ましい。０．８２以上がさらに好ましい。 By satisfying the following three conditions, the alkali-free glass of the present invention can lower the glass viscosity, particularly the temperature T 4 at which the glass viscosity is 10 4 dPa · s, and the etching rate during the hydrofluoric acid etching treatment. Becomes larger.
MgO / CaO is 1.05 or more, preferably 1.3 or more, more preferably 1.5 or more, and still more preferably 2 or more.
SrO / CaO is 1.05 or more, preferably 1.08 or more, more preferably 1.1 or more, and even more preferably 1.15 or more.
(MgO + CaO) / (MgO + CaO + SrO + BaO) is 0.7 or more, preferably 0.75 or more, and more preferably 0.8 or more. 0.82 or more is more preferable.
　なお、本発明のガラスは、パネル製造時にガラス表面に設ける金属ないし酸化物薄膜の特性劣化を生じさせないために、アルカリ金属酸化物を不純物レベルを超えて（すなわち実質的に）含有しない。また、同様の理由で、Ｐ２Ｏ５を実質的に含有しないことが好ましい。さらに、ガラスのリサイクルを容易にするため、ＰｂＯ、Ａｓ２Ｏ３、Ｓｂ２Ｏ３は実質的に含有しないことが好ましい。 The glass of the present invention does not contain an alkali metal oxide in excess of the impurity level (ie substantially) in order not to cause deterioration of the characteristics of the metal or oxide thin film provided on the glass surface during panel production. For the same reason, it is preferable that P 2 O 5 is not substantially contained. Furthermore, in order to facilitate recycling of the glass, it is preferable that PbO, As 2 O 3 , and Sb 2 O 3 are not substantially contained.
　本発明の無アルカリガラスは上記成分以外にガラスの溶解性、清澄性、成形性（フロート成形性）を改善するため、ＺｎＯ、Ｆｅ２Ｏ３、ＳＯ３、Ｆ、Ｃｌ、ＳｎＯ２等を総量で１％以下、好ましくは０．９％以下、より好ましくは０．８％以下、さらに好ましくは０．７％以下添加できる（好ましくは含有できる）。ＺｎＯは実質的に含有しないことが好ましい。 The alkali-free glass of the present invention contains ZnO, Fe 2 O 3 , SO 3 , F, Cl, SnO 2 and the like in order to improve the solubility, clarity and moldability (float moldability) of the glass in addition to the above components. 1% or less, preferably 0.9% or less, more preferably 0.8% or less, and still more preferably 0.7% or less (preferably contained). It is preferable that ZnO is not substantially contained.
　本発明の無アルカリガラスは、歪点が６８０℃以上であるため、パネル製造時の熱収縮を抑えられる。また、ｐ－Ｓｉ　ＴＦＴの製造方法として固相結晶化法を適用することができる。
　本発明の無アルカリガラスは、歪点が６８０℃以上であるため、高歪点用途（例えば、有機ＥＬ用のディスプレイ用基板または照明用基板、あるいは板厚１００μｍ以下の薄板のディスプレイ用基板または照明用基板）に適している。
　好ましくは６９０℃以上、より好ましくは７００℃以上、さらに好ましくは７１０℃以上である。 Since the alkali-free glass of the present invention has a strain point of 680 ° C. or higher, thermal shrinkage during panel production can be suppressed. Further, a solid phase crystallization method can be applied as a method for manufacturing a p-Si TFT.
Since the alkali-free glass of the present invention has a strain point of 680 ° C. or higher, it is used for a high strain point (for example, a display substrate or lighting substrate for organic EL, or a thin display substrate or lighting plate having a thickness of 100 μm or less). Suitable for use on a substrate).
Preferably it is 690 degreeC or more, More preferably, it is 700 degreeC or more, More preferably, it is 710 degreeC or more.
　また本発明の無アルカリガラスは、歪点と同様の理由で、ガラス転移点が好ましくは７４５℃以上であり、より好ましくは７５０℃以上であり、さらに好ましくは７５５℃以上である。 The alkali-free glass of the present invention has a glass transition point of preferably 745 ° C. or higher, more preferably 750 ° C. or higher, and further preferably 755 ° C. or higher for the same reason as the strain point.
　また本発明の無アルカリガラスは、５０～３５０℃での平均熱膨張係数が３０×１０－７～４３×１０－７／℃であり、耐熱衝撃性が大きく、パネル製造時の生産性を高くできる。本発明の無アルカリガラスにおいて、５０～３５０℃での平均熱膨張係数は好ましくは３５×１０－７以上である。５０～３５０℃での平均熱膨張係数は好ましくは４２×１０－７／℃以下、より好ましくは４１×１０－７／℃以下、さらに好ましくは４０×１０－７／℃以下である。 The alkali-free glass of the present invention has an average coefficient of thermal expansion at 50 to 350 ° C. of 30 × 10 −7 to 43 × 10 −7 / ° C., has high thermal shock resistance, and has high productivity during panel production. it can. In the alkali-free glass of the present invention, the average thermal expansion coefficient at 50 to 350 ° C. is preferably 35 × 10 −7 or more. The average thermal expansion coefficient at 50 to 350 ° C. is preferably 42 × 10 −7 / ° C. or less, more preferably 41 × 10 −7 / ° C. or less, and further preferably 40 × 10 −7 / ° C. or less.
　さらに、本発明の無アルカリガラスは、比重が好ましくは２．７以下であり、より好ましくは２．６７以下であり、さらに好ましくは２．６５以下である。 Furthermore, the alkali-free glass of the present invention has a specific gravity of preferably 2.7 or less, more preferably 2.67 or less, and even more preferably 2.65 or less.
　また、本発明の無アルカリガラスは、粘度ηが１０２ポイズ（ｄＰａ・ｓ）となる温度Ｔ２が１６７０℃以下、好ましくは１６７０℃未満、好ましくは１６６５℃以下、より好ましくは１６６０℃以下、さらに好ましくは１６５５℃以下であるため、溶解が容易である。 The alkali-free glass of the present invention has a temperature T 2 at which the viscosity η becomes 10 2 poise (dPa · s), 1670 ° C. or less, preferably less than 1670 ° C., preferably 1665 ° C. or less, more preferably 1660 ° C. or less, Furthermore, since it is 1655 degrees C or less preferably, melt | dissolution is easy.
　さらに、本発明の無アルカリガラスは粘度ηが１０４ポイズとなる温度Ｔ４が１３２０℃以下、好ましくは１３２０℃未満、好ましくは１３１５℃以下、より好ましくは１３１０℃以下、さらに好ましくは１３０５℃以下であり、フロート成形に適している。 Further, the alkali-free glass of the present invention has a temperature T 4 at which the viscosity η becomes 10 4 poise is 1320 ° C. or less, preferably less than 1320 ° C., preferably 1315 ° C. or less, more preferably 1310 ° C. or less, and further preferably 1305 ° C. or less. It is suitable for float forming.
　また、本発明の無アルカリガラスは失透温度が、１３５０℃以下であることがフロート法による成形が容易となることから好ましい。好ましくは１３４０℃以下、より好ましくは１３３０℃以下である。
　本明細書における失透温度は、白金製の皿に粉砕されたガラス粒子を入れ、一定温度に制御された電気炉中で１７時間熱処理を行い、熱処理後の光学顕微鏡観察によって、ガラスの表面及び内部に結晶が析出する最高温度と結晶が析出しない最低温度との平均値である。 In addition, the alkali-free glass of the present invention preferably has a devitrification temperature of 1350 ° C. or less because molding by the float method is easy. Preferably it is 1340 degrees C or less, More preferably, it is 1330 degrees C or less.
In this specification, the devitrification temperature is obtained by putting crushed glass particles in a platinum dish and performing heat treatment for 17 hours in an electric furnace controlled at a constant temperature. It is an average value of the maximum temperature at which crystals are deposited inside and the minimum temperature at which crystals are not deposited.
　また、本発明の無アルカリガラスは、ヤング率が８０ＧＰａ以上、さらには８２ＧＰａ以上、さらには８４ＧＰａ以上が好ましい。 Further, the alkali-free glass of the present invention preferably has a Young's modulus of 80 GPa or more, more preferably 82 GPa or more, and further 84 GPa or more.
　本発明の無アルカリガラスは、後述する実施例に記載の手順で測定されるコンパクションが１２０ｐｐｍ以下であることが好ましい。コンパクションとは、加熱処理の際にガラス構造の緩和によって発生するガラス熱収縮率である。
　本発明の無アルカリガラスは、後述する実施例に記載の手順で測定されるコンパクションがより好ましくは１００ｐｐｍ以下、さらに好ましくは８０ｐｐｍ以下、さらには６０ｐｐｍ以下、特に好ましくは５０ｐｐｍ以下である。 The alkali-free glass of the present invention preferably has a compaction of 120 ppm or less measured by the procedure described in the examples described later. Compaction is the glass heat shrinkage generated by relaxation of the glass structure during the heat treatment.
In the alkali-free glass of the present invention, the compaction measured by the procedure described in the examples described later is more preferably 100 ppm or less, further preferably 80 ppm or less, further 60 ppm or less, and particularly preferably 50 ppm or less.
　また、本発明の無アルカリガラスは、光弾性定数が３１ｎｍ／ＭＰａ／ｃｍ以下であることが好ましい。
　液晶ディスプレイパネル製造工程や液晶ディスプレイ装置使用時に発生した応力によってガラス基板が複屈折性を有することにより、黒の表示がグレーになり、液晶ディスプレイのコントラストが低下する現象が認められることがある。光弾性定数を３１ｎｍ／ＭＰａ／ｃｍ以下とすることにより、この現象を小さく抑えることができる。好ましくは３０ｎｍ／ＭＰａ／ｃｍ以下、より好ましくは２９ｎｍ／ＭＰａ／ｃｍ以下、さらに好ましくは２８．５ｎｍ／ＭＰａ／ｃｍ以下、特に好ましくは２８ｎｍ／ＭＰａ／ｃｍ以下である。
　また、本発明の無アルカリガラスは、他の物性確保の容易性を考慮すると、光弾性定数が好ましくは２３ｎｍ／ＭＰａ／ｃｍ以上、より好ましくは２５ｎｍ／ＭＰａ／ｃｍ以上である。
　なお、光弾性定数は円板圧縮法により測定波長５４６ｎｍで測定できる。 The alkali-free glass of the present invention preferably has a photoelastic constant of 31 nm / MPa / cm or less.
Due to the birefringence of the glass substrate due to stress generated during the manufacturing process of the liquid crystal display panel and the liquid crystal display device, a phenomenon in which the black display becomes gray and the contrast of the liquid crystal display decreases may be observed. By setting the photoelastic constant to 31 nm / MPa / cm or less, this phenomenon can be suppressed small. Preferably it is 30 nm / MPa / cm or less, More preferably, it is 29 nm / MPa / cm or less, More preferably, it is 28.5 nm / MPa / cm or less, Most preferably, it is 28 nm / MPa / cm or less.
The alkali-free glass of the present invention has a photoelastic constant of preferably 23 nm / MPa / cm or more, more preferably 25 nm / MPa / cm or more, considering the ease of securing other physical properties.
The photoelastic constant can be measured at a measurement wavelength of 546 nm by a disk compression method.
　本発明無アルカリガラスは、フッ酸エッチング処理時のエッチング速度の指標となる、２５℃の５質量％フッ酸（ＨＦ）水溶液に２０分間浸漬した場合の単位面積当たりの質量減少が３．１ｍｇ／ｃｍ２以上である。 The alkali-free glass of the present invention has a mass reduction per unit area of 3.1 mg / min when immersed in a 5% by mass hydrofluoric acid (HF) aqueous solution at 25 ° C., which is an index of etching rate during hydrofluoric acid etching treatment. cm 2 or more.
　本発明の無アルカリガラスは、例えば次のような方法で製造できる。通常使用される各成分の原料を目標成分になるように調合し、これを溶解炉に連続的に投入し、１５００～１８００℃に加熱して熔融する。この熔融ガラスをフロート法またはフュージョン法、好ましくはフロート法により所定の板厚に成形し、徐冷後切断することによって板ガラスを得ることができる。前記成形された所定の板厚は、０．７ｍｍ以下が好ましく、０．５ｍｍ以下がより好ましく、０．３ｍｍ以下でもよく、０．１ｍｍ以下でもよい。 The alkali-free glass of the present invention can be produced, for example, by the following method. The raw materials for each component that are normally used are blended so as to become target components, which are continuously charged into a melting furnace and heated to 1500 to 1800 ° C. for melting. A plate glass can be obtained by forming this molten glass into a predetermined plate thickness by a float method or a fusion method, preferably by a float method, and cutting after slow cooling. The molded plate thickness is preferably 0.7 mm or less, more preferably 0.5 mm or less, 0.3 mm or less, or 0.1 mm or less.
　以下において例１～１２、例１５～２０は実施例、例１３～１４及び例２１は比較例である。各成分の原料を目標組成になるように調合し、白金坩堝を用いて１５００～１６５０℃の温度で溶解した。溶解にあたっては、白金スターラを用い撹拌しガラスの均質化を行った。次いで溶解ガラスを流し出し、板状に成形後徐冷した。 In the following, Examples 1 to 12, Examples 15 to 20 are examples, and Examples 13 to 14 and Example 21 are comparative examples. The raw materials of each component were prepared so as to have a target composition and melted at a temperature of 1500 to 1650 ° C. using a platinum crucible. In melting, the mixture was stirred using a platinum stirrer to homogenize the glass. Next, the molten glass was poured out, formed into a plate shape, and then slowly cooled.
　表１～３には、ガラス組成（単位：モル％）と５０～３５０℃での平均熱膨脹係数（単位：×１０－７／℃）、歪点（単位：℃）、ガラス転移点（単位：℃）、比重、ヤング率（ＧＰａ）（超音波法により測定）、高温粘性値として、溶解性の目安となる温度Ｔ２（ガラス粘度ηが１０２ポイズとなる温度、単位：℃）、とフロート成形性およびフュージョン成形性の目安となる温度Ｔ４（ガラス粘度ηが１０４ポイズとなる温度、単位：℃）、失透温度（単位：℃）、光弾性定数（単位：ｎｍ／ＭＰａ／ｃｍ）（円板圧縮法により測定波長５４６ｎｍで測定）、２５℃の５質量％フッ酸（ＨＦ）水溶液に２０分間浸漬した場合の単位面積当たりの質量減少（表中、「５％ＨＦ浸漬後質量減少」と記載。単位：ｍｇ／ｃｍ２）（下記手順により測定）、および、コンパクション（単位：ｐｐｍ）を示す。なお、５％ＨＦ浸漬後質量減少の測定方法、および、コンパクションの測定方法は以下に記載した通りである。
［単位面積当たりの質量減少の測定方法］
　各成分の原料を、表１～３に示す目標組成になるように調合し、連続溶融窯にて溶解を行い、フロート法にて板成形を行い、無アルカリガラス基板を得る。鏡面研磨された４０ｍｍ四方に切断した無アルカリガラス基板を洗浄後、質量を測定する。２５℃の５質量％フッ酸（ＨＦ）水溶液に２０分間浸漬し、浸漬後の質量を測定する。サンプル寸法から表面積を算出し、質量減少量を表面積で割ったのち、さらに浸漬時間で割ることで、単位面積および単位時間当たりの質量減少を求める。
［コンパクションの測定方法］
　ガラス板試料（酸化セリウムで鏡面研磨した長さ１００ｍｍ×幅１０ｍｍ×厚さ１ｍｍの試料）をガラス転移点＋１００℃の温度で１０分間保持した後、毎分４０℃で室温まで冷却する。ここで試料の全長（長さ方向）Ｌ１を計測する。その後、毎時１００℃で６００℃まで加熱し、６００℃で８０分間保持し、毎時１００℃で室温まで冷却し、再度試料の全長Ｌ２を計測する。６００℃での熱処理前後での全長の差（Ｌ１－Ｌ２）と、６００℃での熱処理前の試料全長Ｌ１と、の比（Ｌ１－Ｌ２）／Ｌ１をコンパクションとする。
　なお、表１～３中、括弧書で示した値は計算値であり、「ＲＯ」とは（ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯ）である。 Tables 1 to 3 show the glass composition (unit: mol%), the average thermal expansion coefficient at 50 to 350 ° C. (unit: × 10 −7 / ° C.), the strain point (unit: ° C.), the glass transition point (unit: ° C), specific gravity, Young's modulus (GPa) (measured by ultrasonic method), high-temperature viscosity value, temperature T 2 (temperature at which glass viscosity η becomes 10 2 poise, unit: ° C) Temperature T 4 (temperature at which the glass viscosity η becomes 10 4 poise, unit: ° C), devitrification temperature (unit: ° C), photoelastic constant (unit: nm / MPa /) cm) (measured by a disk compression method at a measurement wavelength of 546 nm), mass decrease per unit area when immersed in a 5 mass% hydrofluoric acid (HF) aqueous solution at 25 ° C. for 20 minutes (in the table, “after 5% HF immersion "Decreased mass" Unit: mg / cm 2 ) (following procedure ) And compaction (unit: ppm). In addition, the measuring method of mass reduction after immersion in 5% HF and the measuring method of compaction are as described below.
[Measurement method of mass reduction per unit area]
The raw materials of each component are prepared so as to have the target compositions shown in Tables 1 to 3, dissolved in a continuous melting furnace, and plate-formed by a float method to obtain an alkali-free glass substrate. The alkali-free glass substrate cut into a 40 mm square that has been mirror-polished is washed, and then the mass is measured. It is immersed in a 5% by mass hydrofluoric acid (HF) aqueous solution at 25 ° C. for 20 minutes, and the mass after immersion is measured. The surface area is calculated from the sample dimensions, the mass reduction amount is divided by the surface area, and then the immersion time is further divided to obtain the unit area and the mass reduction per unit time.
[Measurement method of compaction]
A glass plate sample (length 100 mm × width 10 mm × thickness 1 mm sample mirror-polished with cerium oxide) is held at a temperature of glass transition point + 100 ° C. for 10 minutes, and then cooled to room temperature at 40 ° C. per minute. Here, the total length (length direction) L1 of the sample is measured. Thereafter, the sample is heated at 100 ° C. per hour to 600 ° C., held at 600 ° C. for 80 minutes, cooled to room temperature at 100 ° C. per hour, and the total length L2 of the sample is measured again. The ratio (L1−L2) / L1 between the difference in total length before and after the heat treatment at 600 ° C. (L1−L2) and the total length L1 of the sample before the heat treatment at 600 ° C. is defined as compaction.
In Tables 1 to 3, the values shown in parentheses are calculated values, and “RO” is (MgO + CaO + SrO + BaO).
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　表から明らかなように、実施例のガラスはいずれも、平均熱膨脹係数は３０×１０－７～４３×１０－７／℃と低く、歪点が６８０℃以上である。 As is clear from the table, all the glasses of the examples have an average coefficient of thermal expansion as low as 30 × 10 −7 to 43 × 10 −7 / ° C. and a strain point of 680 ° C. or higher.
　溶解性の目安となる温度Ｔ２も１６７０℃以下と低く溶解が容易であり、成形性の目安となる温度Ｔ４が１３２０℃以下であり、フロート法による成形が容易である。 Temperature T 2 which is a measure of the solubility is also easy to dissolve low as 1670 ° C. or less, a temperature T 4 which is a measure of formability is at 1320 ° C. or less, it is easily molded by a float process.
　光弾性定数が３１ｎｍ／ＭＰａ／ｃｍ以下であり、液晶ディスプレイのガラス基板として使用した場合にコントラストの低下を抑制することができる。 The photoelastic constant is 31 nm / MPa / cm or less, and when used as a glass substrate of a liquid crystal display, a decrease in contrast can be suppressed.
　フッ酸エッチング処理時のエッチング速度の指標となる、２５℃の５質量％フッ酸（ＨＦ）水溶液に２０分間浸漬した場合の単位面積当たりの質量減少が３．１ｍｇ／ｃｍ２以上である。 The mass loss per unit area when immersed in a 5 mass% hydrofluoric acid (HF) aqueous solution at 25 ° C. for 20 minutes, which is an index of the etching rate during the hydrofluoric acid etching treatment, is 3.1 mg / cm 2 or more.
　本発明を詳細に、また特定の実施態様を参照して説明したが、本発明の精神と範囲を逸脱することなく様々な変更や修正を加えることができることは当業者にとって明らかである。本出願は２０１４年４月２８日出願の日本特許出願（特願２０１４－０９２６４６）に基づくものであり、その内容はここに参照として取り込まれる。 Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention. This application is based on a Japanese patent application filed on April 28, 2014 (Japanese Patent Application No. 2014-092646), the contents of which are incorporated herein by reference.
　本発明の無アルカリガラスは、歪点が高く、フロート法による成形ができ、ディスプレイ用基板、フォトマスク用基板等の用途に好適である。また、磁気ディスク用基板、太陽電池用基板等の用途にも好適である。 The alkali-free glass of the present invention has a high strain point and can be formed by a float process, and is suitable for uses such as a display substrate and a photomask substrate. It is also suitable for applications such as magnetic disk substrates and solar cell substrates.

Claims (3)

  1. 　歪点が６８０℃以上であって、５０～３５０℃での平均熱膨張係数が３０×１０－７～４３×１０－７／℃であって、ガラス粘度が１０２ｄＰａ・ｓとなる温度Ｔ２が１６７０℃以下であって、ガラス粘度が１０４ｄＰａ・ｓとなる温度Ｔ４が１３２０℃以下であって、フッ酸（ＨＦ）を含有するエッチング液（２５℃、５％ＨＦ水溶液）に２０分間浸漬させた際の単位面積当たりの質量減少が３．１ｍｇ／ｃｍ２以上であって、
    酸化物基準のモル％表示で
    ＳｉＯ２　　　　　　　６０～７０、
    Ａｌ２Ｏ３　　　　　　　１１～１６、
    Ｂ２Ｏ３　　　　　　　　０超１．５以下、
    ＭｇＯ　　　　　　　　　７超１２以下、
    ＣａＯ　　　　　　　　　０超７以下、
    ＳｒＯ　　　　　　　　　　４．５超１０以下、
    ＢａＯ　　　　　　　　　０～０．５を含有し
    ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯが１６～２２であり、
    （ＳｉＯ２＋Ａｌ２Ｏ３）／（ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯ）が４．７以下であり、ＭｇＯ／ＣａＯが１．０５以上であり、ＳｒＯ／ＣａＯが１．０５以上であり、（ＭｇＯ＋ＳｒＯ）／（ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯ）が０．７以上である無アルカリガラス。     The temperature T at which the strain point is 680 ° C. or higher, the average thermal expansion coefficient at 50 to 350 ° C. is 30 × 10 −7 to 43 × 10 −7 / ° C., and the glass viscosity is 10 2 dPa · s. 2 is 1670 ° C. or lower, the temperature T 4 at which the glass viscosity becomes 10 4 dPa · s is 1320 ° C. or lower, and an etching solution (25 ° C., 5% HF aqueous solution) containing hydrofluoric acid (HF) is used. The mass reduction per unit area when immersed for 20 minutes is 3.1 mg / cm 2 or more,
    SiO 2 60 to 70 in terms of mol% based on oxide,
    Al 2 O 3 11-16,
    B 2 O 3 more than 0 and 1.5 or less,
    MgO 　　 7 to 12 or less,
    CaO 　　 More than 0 and less than 7,
    SrO 　　　　　 4.5 to 10 or less,
    BaO 　　 0 to 0.5, MgO + CaO + SrO + BaO is 16-22,
    (SiO 2 + Al 2 O 3 ) / (MgO + CaO + SrO + BaO) is 4.7 or less, MgO / CaO is 1.05 or more, SrO / CaO is 1.05 or more, and (MgO + SrO) / (MgO + CaO + SrO + BaO) is Alkali-free glass that is 0.7 or more.
  2. 　酸化物基準のモル％表示で
    ＳｉＯ２　　　　　　　　６３～６８、
    Ａｌ２Ｏ３　　　　　　　　　１２～１４、
    Ｂ２Ｏ３　　　　　　　　　０．５～１．３、
    ＭｇＯ　　　　　　　　８～１１、
    ＣａＯ　　　　　　　　１．５～５、
    ＳｒＯ　　　　　　　　５～９、
    ＢａＯ　　　　　　　　０～０．３を含有し
    ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯが１７．５～２０であり、
    （ＳｉＯ２＋Ａｌ２Ｏ３）／（ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯ）が４．６以下であり、ＭｇＯ／ＣａＯが１．３以上であり、ＳｒＯ／ＣａＯが１．１以上であり、（ＭｇＯ＋ＳｒＯ）／（ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯ）が０．７５以上である請求項１に記載の無アルカリガラス。     SiO 2 63 to 68 in terms of mol% based on oxide,
    Al 2 O 3 12-14,
    B 2 O 3 0.5-1.3,
    MgO 8-11,
    CaO 1.5-5,
    SrO 5-9,
    BaO 0-0.3, MgO + CaO + SrO + BaO is 17.5-20,
    (SiO 2 + Al 2 O 3 ) / (MgO + CaO + SrO + BaO) is 4.6 or less, MgO / CaO is 1.3 or more, SrO / CaO is 1.1 or more, and (MgO + SrO) / (MgO + CaO + SrO + BaO) is The alkali-free glass according to claim 1, which is 0.75 or more.
  3. 　酸化物基準のモル％表示で
    ＳｉＯ２　　　　　　　　６５．５～６７．５、
    Ａｌ２Ｏ３　　　　　　　　１２．５～１３．５、
    Ｂ２Ｏ３　　　　　　　　　　　０．７～１．２、
    ＭｇＯ　　　　　　　　８．５～１０、
    ＣａＯ　　　　　　　　２～４．５、
    ＳｒＯ　　　　　　　　５．３～８を含有し、
    ＢａＯを実質的に含有せず、
    ＭｇＯ＋ＣａＯ＋ＳｒＯが１８～１９．５であり、
    （ＳｉＯ２＋Ａｌ２Ｏ３）／（ＭｇＯ＋ＣａＯ＋ＳｒＯ）が４．５以下であり、ＭｇＯ／ＣａＯが２以上であり、ＳｒＯ／ＣａＯが１．１５以上であり、（ＭｇＯ＋ＳｒＯ）／（ＭｇＯ＋ＣａＯ＋ＳｒＯ）が０．８以上である請求項１または２に記載の無アルカリガラス。     SiO 2 65.5 to 67.5 in terms of mol% based on oxide,
    Al 2 O 3 12.5 to 13.5,
    B 2 O 3 0.7 to 1.2,
    MgO 8.5-10,
    CaO 2 to 4.5,
    Containing SrO 5.3-8,
    Substantially free of BaO,
    MgO + CaO + SrO is 18 to 19.5,
    (SiO 2 + Al 2 O 3 ) / (MgO + CaO + SrO) is 4.5 or less, MgO / CaO is 2 or more, SrO / CaO is 1.15 or more, and (MgO + SrO) / (MgO + CaO + SrO) is 0. The alkali-free glass according to claim 1 or 2, which is 8 or more.
PCT/JP2015/062547 2014-04-28 2015-04-24 Non-alkali glass WO2015166890A1 (en)

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