CN106458701B - Alkali-free glass - Google Patents
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- CN106458701B CN106458701B CN201580023348.5A CN201580023348A CN106458701B CN 106458701 B CN106458701 B CN 106458701B CN 201580023348 A CN201580023348 A CN 201580023348A CN 106458701 B CN106458701 B CN 106458701B
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
- C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C15/00—Surface treatment of glass, not in the form of fibres or filaments, by etching
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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
- C03C4/00—Compositions for glass with special properties
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Abstract
The invention aims to provide alkali-free glass which has high strain point, low viscosity, high etching speed and easy float forming. The invention relates to an alkali-free glass, the strain point of which is more than 680 ℃, and the average thermal expansion coefficient of which is 30 multiplied by 10 at the temperature of 50-350 DEG C‑7～43×10‑7At/° C, the glass viscosity reaches 102Temperature T at dPa · s2Below 1670 deg.C, the glass viscosity reaches 104Temperature T at dPa · s4At a temperature of 1320 deg.C or lower, and a mass loss of 3.1mg/cm when immersed in an etching solution for 20 minutes2Above, and the composition of the oxide is specific.
Description
Technical Field
The present invention relates to an alkali-free glass which is suitable as various kinds of display substrate glass or photomask substrate glass, which contains substantially no alkali metal oxide and which can be formed by a float process.
Background
Conventionally, various kinds of substrate glasses for displays, particularly substrate glasses for displays having a metal, oxide thin film or the like formed on the surface thereof, have been required to have the following characteristics.
(1) When an alkali metal oxide is contained, alkali metal ions diffuse into the thin film to deteriorate the film characteristics, and therefore, it is required that the alkali metal oxide is not substantially contained.
(2) When exposed to high temperatures in the film forming process, the strain point is required to be high in order to minimize shrinkage (thermal shrinkage) associated with deformation of the glass and structural stabilization of the glass.
(3) Has sufficient chemical durability against various chemicals used in semiconductor formation. Especially for SiOx、SiNxBuffered hydrofluoric acid (BHF) for etching and a hydrochloric acid-containing chemical solution and metal electrode used for etching ITOVarious acids (nitric acid, sulfuric acid, etc.) used for the extreme etching and bases of the resist stripping liquid have durability.
(4) The interior and the surface are free of defects (bubbles, striae, inclusions, dents, scratches, etc.).
In addition to the above-described requirements, in recent years, the following situation has been developed.
(5) The display is required to be lightweight, and glass itself is desired to be low-density glass.
(6) The display is required to be lightweight, and thinning of the substrate glass is desired.
(7) In addition to the conventional amorphous silicon (a-Si) type liquid crystal display, a polysilicon (p-Si) type liquid crystal display (a-Si: about 350 ℃→ p-Si: 350 ℃ to 550 ℃) having a slightly higher heat treatment temperature was produced.
(8) Glass having a small average thermal expansion coefficient is required for increasing the rate of temperature rise and temperature fall in heat treatment for producing liquid crystal displays, thereby improving productivity or improving thermal shock resistance.
On the other hand, drying of etching progresses, and the requirement for BHF resistance is reduced. In order to improve the BHF resistance, the glass containing 6 to 10 mol% of B has been used in many cases2O3The glass of (2). However, B2O3The strain point tends to be lowered. As containing no B2O3Or B2O3Examples of the alkali-free glass having a small content include the following glasses.
Patent document 1 discloses that B is not contained2O3SiO of (2)2-Al2O3SrO glasses, but the temperatures required for melting are high, creating difficulties in manufacturing.
Patent document 2 discloses that B is contained in an amount of 0 to 5 mol%2O3But an average thermal expansion coefficient of more than 50X 10 at 50 ℃ to 300 ℃-7/℃。
In order to solve the problems of the glasses described in patent documents 1 to 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 formed by a float process, and is suitable for applications such as a display substrate and a photomask substrate.
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. 62-113735
Patent document 2: japanese laid-open patent publication No. 5-232458
Patent document 3: japanese laid-open patent publication No. 10-45422
Patent document 4: international publication No. 2009-066624
Disclosure of Invention
Problems to be solved by the invention
As a method for producing a high-quality p-Si TFT, there is a solid-phase crystallization method, but in order to implement this method, it is required to further increase the strain point.
On the other hand, from the viewpoint of the requirements for glass production processes, particularly for melting and forming, it is required to reduce the viscosity of glass, specifically, to 102Temperature T at dPa · s2And a glass viscosity of up to 104Temperature T at dPa · s4。
On the other hand, in the field of small and medium-sized Liquid Crystal Displays (LCDs) or organic EL displays (OELDs), particularly in the field of portable displays such as mobile devices, digital cameras, and cellular phones, weight reduction and thickness reduction of displays are important issues. In order to further reduce the thickness of the glass substrate, a process of etching the surface of the glass substrate to reduce the thickness (thickness reduction) after the array-color filter bonding process is widely used. For example, the surface of a glass substrate is subjected to etching treatment (hereinafter referred to as "hydrofluoric acid etching treatment") using an etching solution containing hydrofluoric acid (HF), thereby thinning the glass substrate (see patent document 4).
When the glass substrate is thinned by hydrofluoric acid etching treatment, the etching rate in hydrofluoric acid etching treatment is required to be high.
The object of the present invention is to solve the above-mentioned drawbacks by providing a glass with a high strain point and a low viscosity, in particular a glass viscosity of up to 102Temperature T at dPa · s2And a glass viscosity of up to 104Temperature T at dPa · s4Low alkali-free glass which has a high etching rate in hydrofluoric acid etching treatment and is easily formed by the float process.
Means for solving the problems
The invention provides an alkali-free glass, which has a strain point of more than 680 ℃ and an average thermal expansion coefficient of 30 multiplied by 10 at 50-350 DEG C-7～43×10-7At/° C, the glass viscosity reaches 102Temperature T at dPa · s2Below 1670 deg.C, the glass viscosity reaches 104Temperature T at dPa · s4The mass loss per unit area of the steel sheet is 3.1mg/cm when the steel sheet is immersed in an etching solution containing hydrofluoric acid (HF) (25 ℃, 5% HF aqueous solution) for 20 minutes at a temperature of 1320 ℃ or lower2Above, and
the alkali-free glass contains, in mol% on an oxide basis:
16 to 22 parts of MgO + CaO + SrO + BaO,
(SiO2+Al2O3) (MgO + CaO + SrO + BaO) is 4.7 or less,
the ratio MgO/CaO is 1.05 or more,
the SrO/CaO ratio is more than 1.05,
(MgO + SrO)/(MgO + CaO + SrO + BaO) is 0.7 or more.
Further, the present invention provides the alkali-free glass described above, wherein the alkali-free glass contains, in mol% based on oxides:
17.5 to 20 parts of MgO + CaO + SrO + BaO,
(SiO2+Al2O3) (MgO + CaO + SrO + BaO) is 4.6 or less,
the ratio MgO/CaO is 1.3 or more,
the SrO/CaO ratio is more than 1.1,
(MgO + SrO)/(MgO + CaO + SrO + BaO) is 0.75 or more.
Further, the present invention provides the alkali-free glass described above, wherein the alkali-free glass contains, in mol% based on oxides:
the alkali-free glass is substantially free of BaO,
MgO + CaO + SrO is 18 to 19.5,
(SiO2+Al2O3) (MgO + CaO + SrO) is 4.5 or less,
the ratio of MgO/CaO is 2 or more,
the SrO/CaO ratio is more than 1.15,
(MgO + SrO)/(MgO + CaO + SrO) is 0.8 or more.
Effects of the invention
The alkali-free glass of the present invention is particularly suitable for a display substrate, a photomask substrate, and the like for high strain point applications, and is a glass which is easily formed by a float process.
Detailed Description
The present invention will be described in detail below, but the present invention is not limited to the following embodiments, and can be implemented by being arbitrarily modified within a range not departing from the gist of the present invention. In the present specification, "wt%" and "mass%" have the same meaning. The term "to" includes the lower limit and the upper limit, i.e., it is not less than the lower limit and not more than the upper limit.
The composition ranges of the respective components will be described. SiO 22When the content is less than 60% (mol%, the same applies unless otherwise specified), the strain point cannot be sufficiently increased, the thermal expansion coefficient increases, and the density increases. Preferably 63% or more, more preferably 65% or more, and still more preferably 65.5% or more. If it exceeds 70%, the meltability is lowered. Preferably 69% or less, more preferably 68% or less, and still more preferably 67.5% or less.
Al2O3The phase separation of the glass is suppressed, the thermal expansion coefficient is decreased, and the strain point is increased, but when the strain point is less than 11%, the strain point is not exhibitedThis effect is shown, and the thermal expansion increases as a result of increasing other expansion components. Preferably 11.5% or more, more preferably 12% or more, and still more preferably 12.5% or more. When the content exceeds 16%, the glass has poor melting property. Preferably 15% or less, more preferably 14% or less, and still more preferably 13.5% or less.
B2O3The glass is improved in melting reactivity, so that more than 0% and 1.5% or less of B may be added2O3. In order to obtain the above effects, the content is preferably 0.2% or more, more preferably 0.5% or more, and still more preferably 0.7% or more. However, when too much, the strain point is lowered. Therefore, it is preferably 1.4% or less, more preferably 1.3% or less, and still more preferably 1.2% or less.
MgO has characteristics of not increasing expansion and not excessively lowering strain point among alkaline earth groups, and also improves meltability.
When the content is 7% or less, the above-mentioned effects of MgO addition cannot be sufficiently exhibited. Preferably 7.5% or more, more preferably 8% or more, and further preferably 8.5% or more. However, if the amount exceeds 12%, the devitrification temperature may be increased. Preferably 11% or less, more preferably 10% or less, and still more preferably 9.5% or less.
After CaO resides in MgO, it has characteristics of not increasing expansion and not excessively lowering the strain point in alkaline earth, and also improves meltability. Therefore, more than 0% and 7% or less of CaO may be added. Preferably 1% or more, more preferably 1.5% or more, and further preferably 2% or more. However, if the content exceeds 7%, limestone (CaCO) as a CaO raw material may be used3) Phosphorus as an impurity is mixed in a large amount. Preferably 6% or less, more preferably 5% or less, and still more preferably 4.5% or less.
SrO improves the meltability, but when it is 4.5% or less, the effect is not sufficiently exhibited. Preferably 4.7% or more, more preferably 4.9% or more, more preferably 5.0% or more, and further preferably 5.3% or more. However, if the amount exceeds 10%, the expansion coefficient may increase. Preferably 9% or less, more preferably 8.5% or less, and still more preferably 8% or less.
BaO is not essential, but may be contained for improving the meltability. However, if too much, the glass expands and the density increases excessively, so that the content is set to 0.5% or less. Preferably 0.3% or less, more preferably 0.1% or less, and further preferably substantially none. Substantially free means free of other than unavoidable impurities.
ZrO may be contained in an amount of 0.5% or less for lowering the glass melting temperature or for promoting crystal precipitation during firing2. When the content exceeds 0.5%, the glass becomes unstable or the relative dielectric constant ε of the glass increases. Preferably 0.3% or less, more preferably 0.1% or less, and particularly preferably substantially none.
When the total amount of MgO, CaO, SrO and BaO is less than 16%, the meltability is insufficient. Preferably 17% or more, more preferably 17.5% or more, and further preferably 18% or more. When the amount is more than 22%, there is a possibility that the thermal expansion coefficient cannot be reduced. Preferably 21% or less, more preferably 20% or less, and still more preferably 19.5% or less.
In the alkali-free glass of the present invention, the viscosity of the glass can be reduced without increasing the thermal expansion coefficient, specifically, the viscosity of the glass can be reduced to 10 by making the total amount of MgO, CaO, SrO and BaO satisfy the above-mentioned conditions and satisfying the following conditions2Temperature T at dPa · s2And a glass viscosity of up to 104Temperature T at dPa · s4。
(SiO2+Al2O3) /(MgO + CaO + SrO + BaO) is 4.7 or less, preferably 4.6 or less, more preferably 4.5 or less, and still more preferably 4.4 or less.
With the alkali-free glass of the present invention, the viscosity of the glass can be reduced, particularly, the viscosity of the glass can be reduced to 10 by satisfying the following three conditions4Temperature T at dPa · s4And the etching rate at the time of the hydrofluoric acid etching treatment is increased.
The MgO/CaO ratio is 1.05 or more, preferably 1.3 or more, more preferably 1.5 or more, and further preferably 2 or more.
The SrO/CaO ratio is 1.05 or more, preferably 1.08 or more, more preferably 1.1 or more, and still more preferably 1.15 or more.
The ratio of (MgO + SrO)/(MgO + CaO + SrO + BaO) is 0.7 or more, preferably 0.75 or more, more preferably 0.8 or more, and still more preferably 0.82 or more.
The glass of the present invention does not contain an alkali metal oxide exceeding the impurity level (i.e., does not substantially contain) so as not to cause deterioration in the characteristics of the metal or oxide thin film provided on the glass surface when the panel is produced. For the same reason, it is preferable that substantially no P is contained2O5. Further, in order to make the glass easily reusable, it is preferable that PbO and As are not substantially contained2O3、Sb2O3。
In addition to the above components, ZnO and Fe may be added (preferably contained) in an amount of 1% or less in total to the alkali-free glass of the present invention in order to improve the melting property, the clarifying property, and the formability (float formability) of the glass2O3、SO3、F、Cl、SnO2Etc., preferably 0.9% or less, more preferably 0.8% or less, and further preferably 0.7% or less. Preferably substantially no ZnO.
The alkali-free glass of the present invention has a strain point of 680 ℃ or higher, and therefore can suppress thermal shrinkage during panel production. In addition, a solid-phase crystallization method can be applied as a method for manufacturing a p-Si TFT.
The alkali-free glass of the present invention has a strain point of 680 ℃ or higher, and is therefore suitable for high strain point applications (for example, substrates for displays or illumination for organic EL, or substrates for displays or illumination for thin plates having a thickness of 100 μm or less).
Preferably 690 ℃ or higher, more preferably 700 ℃ or higher, and still more preferably 710 ℃ or higher.
The glass transition temperature of the alkali-free glass of the present invention is preferably 745 ℃ or higher, more preferably 750 ℃ or higher, and still more preferably 755 ℃ or higher for the same reason as the strain point.
In addition, the alkali-free glass of the present invention has an average thermal expansion coefficient of 30X 10 at 50 to 350 ℃-7～43×10-7The temperature per DEG C is high in thermal shock resistance, and the productivity in manufacturing the panel can be improved. In the alkali-free glass of the present invention, the average thermal expansion coefficient at 50 ℃ to 350 ℃ is preferably 35X 10-7Above/° c. The average thermal expansion coefficient at 50-350 ℃ is preferably 42X 10-7/° C or less, more preferably 41X 10-7Preferably 40X 10 or less/° C-7Below/° c.
The specific gravity of the alkali-free glass of the present invention is preferably 2.7 or less, more preferably 2.67 or less, and still more preferably 2.65 or less.
In addition, the viscosity η of the alkali-free glass of the present invention reaches 102Temperature T in poise (dPa · s)2The melting point is 1670 ℃ or lower, preferably lower than 1670 ℃, preferably 1665 ℃ or lower, more preferably 1660 ℃ or lower, and further preferably 1655 ℃ or lower, and therefore the melting point is easy.
In addition, the viscosity η of the alkali-free glass of the invention reaches 104Temperature T in poise (dPa · s)4Is 1320 ℃ or lower, preferably lower than 1320 ℃, preferably 1315 ℃ or lower, more preferably 1310 ℃ or lower, and further preferably 1305 ℃ or lower, and is suitable for float forming.
In addition, from the viewpoint of ease of forming by the float process, the devitrification temperature of the alkali-free glass of the present invention is preferably 1350 ℃ or lower. Preferably 1340 ℃ or lower, more preferably 1330 ℃ or lower.
The devitrification temperature in the present specification is the following value: the crushed glass particles were placed in a platinum dish, heat-treated in an electric furnace controlled at a constant temperature for 17 hours, and observed by an optical microscope after the heat treatment to obtain an average value of the highest temperature at which crystals precipitated on the surface and in the interior of the glass and the lowest temperature at which crystals did not precipitate.
The alkali-free glass of the present invention has a Young's modulus of preferably 80GPa or more, more preferably 82GPa or more, and still more preferably 84GPa or more.
The alkali-free glass of the present invention preferably has a shrinkage ratio of 120ppm or less, as measured by the procedure described in the following examples. The shrinkage rate is a thermal shrinkage rate of glass caused by relaxation of a glass structure during heat treatment.
The shrinkage rate of the alkali-free glass of the present invention measured by the procedure described in the following examples is more preferably 100ppm or less, still more preferably 80ppm or less, still more preferably 60ppm or less, and particularly preferably 50ppm or less.
The alkali-free glass of the present invention preferably has a photoelastic constant of 31nm/MPa/cm or less.
In some cases, the glass substrate has birefringence due to stress generated in the process of manufacturing the liquid crystal display panel or in the use of the liquid crystal display device, and thus, a phenomenon that black display becomes gray and the contrast of the liquid crystal display is lowered is observed. This phenomenon can be suppressed to a small extent by setting the photoelastic constant to 31nm/MPa/cm or less. Preferably 30nm/MPa/cm or less, more preferably 29nm/MPa/cm or less, still more preferably 28.5nm/MPa/cm or less, and particularly preferably 28nm/MPa/cm or less.
In addition, in view of easiness of securing other physical properties, the photoelastic constant of the alkali-free glass of the present invention is preferably 23nm/MPa/cm or more, more preferably 25nm/MPa/cm or more.
The photoelastic constant can be measured by a disc compression method at a measurement wavelength of 546 nm.
The alkali-free glass of the present invention has a mass loss per unit area of 3.1mg/cm when immersed in a 5 mass% hydrofluoric acid (HF) aqueous solution at 25 ℃ for 20 minutes as an index of an etching rate in a hydrofluoric acid etching treatment2The above.
The alkali-free glass of the present invention can be produced, for example, by the following method. The raw materials of the respective components generally used are blended to become the target components, and continuously charged into a melting furnace, heated to 1500 to 1800 ℃ and melted. The molten glass is formed into a predetermined plate thickness by a float process or a melting process, preferably a float process, and is slowly cooled and then cut to obtain a flat glass. The predetermined thickness of the above-mentioned molding is preferably 0.7mm or less, more preferably 0.5mm or less, and may be 0.3mm or less, and may be 0.1mm or less.
Examples
Examples 1 to 12 and 15 to 20 are examples, and examples 13 to 14 and 21 are comparative examples. The raw materials of each component were mixed to have a target composition, and melted at 1500 to 1650 ℃ using a platinum crucible. During melting, the glass was homogenized by stirring with a platinum stirrer. Then, the molten glass was poured out, formed into a plate shape, and slowly cooled.
Tables 1 to 3 show the glass composition (unit: mol%) and the average thermal expansion coefficient at 50 ℃ to 350 ℃ (unit:. times.10)-7/° c), strain point (unit: c), glass transition temperature (unit: c), specific gravity, young's modulus (GPa) (measured by the ultrasonic method), and temperature T, which is a value of high-temperature viscosity and is a rough standard of meltability2(glass viscosity η reached 102Temperature at poise, unit: DEG C) and a temperature T which is substantially standard for float formability and melt formability4(glass viscosity η reached 104Temperature at poise, unit: c), devitrification temperature (unit: c), photoelastic constant (unit: nm/MPa/cm) (measured by the disc compression method at a measurement wavelength of 546 nm), and a mass decrease per unit area when immersed in a 5 mass% hydrofluoric acid (HF) aqueous solution at 25 ℃ for 20 minutes (in the table, referred to as "mass decrease after 5% HF immersion"). Unit: mg/cm2) (measured by the following procedure), and the shrinkage ratio (unit: ppm). The method for measuring the mass reduction and the method for measuring the shrinkage after the 5% HF dipping are as follows.
[ method of measuring decrease in mass per unit area ]
The raw materials of each component were blended so as to have the target compositions shown in tables 1 to 3, melted in a continuous melting furnace, and subjected to flat plate forming by a float method, thereby obtaining alkali-free glass substrates. The mirror-polished alkali-free glass substrate cut into a 40mm square was cleaned, and then the mass thereof was measured. The sample was immersed in a 5 mass% hydrofluoric acid (HF) aqueous solution at 25 ℃ for 20 minutes, and the mass after immersion was measured. The surface area was calculated from the sample size, and the mass reduction per unit area and per unit time was determined by dividing the mass reduction by the surface area and then by the immersion time.
[ measurement method of shrinkage ]
A glass plate sample (a sample of 100mm in length. times.10 mm in width. times.1 mm in thickness mirror-polished with cerium oxide) was held at a temperature of glass transition temperature +100 ℃ for 10 minutes and then cooled to room temperature at 40 ℃ per minute. Here, the total length (longitudinal direction) L1 of the sample was measured. Then, the sample was heated to 600 ℃ at 100 ℃ per hour, held at 600 ℃ for 80 minutes, cooled to room temperature at 100 ℃ per hour, and the full length L2 of the sample was measured again. The shrinkage ratio was determined as the ratio (L1-L2)/L1 between the difference (L1-L2) in total length before and after heat treatment at 600 ℃ and the total length L1 of the sample before heat treatment at 600 ℃.
In tables 1 to 3, the value shown in parentheses is a calculation value, and "RO" means (MgO + CaO + SrO + BaO).
TABLE 1
TABLE 2
TABLE 3
As is apparent from the results, the glasses of examples all had an average coefficient of thermal expansion as low as 30X 10-7～43×10-7The strain point is above 680 ℃.
Temperature T as a rough criterion of meltability2Also, the temperature T is as low as 1670 ℃ or lower, easily melted, and approximately standard for moldability4The temperature is 1320 ℃ or lower, and the forming by the float method is easy.
The photoelastic constant is 31nm/MPa/cm or less, and when used as a glass substrate for a liquid crystal display, the decrease in contrast can be suppressed.
When immersed in a 5 mass% aqueous hydrofluoric acid (HF) solution at 25 ℃ for 20 minutes as an index of the etching rate in hydrofluoric acid etching treatmentThe mass reduction per unit area was 3.1mg/cm2The above.
It will be apparent to those skilled in the art that the present invention has been described in detail with reference to specific embodiments, and that various changes and modifications can be made without departing from the scope and spirit of the invention. The present application is based on japanese patent application (japanese patent application 2014-092646) proposed on 28/4/2014, the contents of which are incorporated in the present specification by reference.
Industrial applicability
The alkali-free glass of the present invention has a high strain point, can be formed by a float process, and is suitable for applications such as a display substrate and a photomask substrate. Further, the present invention is also suitable for applications such as a substrate for a magnetic disk and a substrate for a solar cell.
Claims (6)
1. An alkali-free glass having a strain point of 680 ℃ or higher and an average thermal expansion coefficient of 30 x 10 at 50 to 350 DEG C-7～43×10-7At/° C, the glass viscosity reaches 102Temperature T in dPa.s2Below 1670 deg.C, the glass viscosity reaches 104Temperature T in dPa.s4The mass loss per unit area when immersed in a 5% HF aqueous solution at 25 ℃ for 20 minutes, which is an etching solution containing hydrofluoric acid (HF) at 1315 ℃ or lower, is 3.1mg/cm2Above, a photoelastic constant of 28.5nm/MPa/cm or less, and
the alkali-free glass contains, in mol% on an oxide basis:
SiO260～70、
Al2O311～16、
B2O3more than 0 and less than or equal to 1.5,
MgO 8.5～10、
CaO 2～3.9、
SrO 5.3～8、
BaO0 to 0.5, and
16 to 22 parts of MgO + CaO + SrO + BaO,
（SiO2+Al2O3) /(MgO + CaO + SrO + BaO) isThe content of the organic acid is less than 4.7,
the ratio of MgO/CaO is 2 or more,
the SrO/CaO ratio is more than 1.53,
(MgO + SrO)/(MgO + CaO + SrO + BaO) is 0.8 or more.
2. The alkali-free glass according to claim 1, wherein MgO/CaO is 2.33 or more.
3. The alkali-free glass according to claim 1, wherein the alkali-free glass contains, in mol% on an oxide basis:
SiO263～68、
Al2O312～14、
B2O30.5～1.3、
MgO 8.5～10、
CaO 2～3.9、
SrO 5.3～8、
BaO0 to 0.3, and
17.5 to 20 parts of MgO + CaO + SrO + BaO,
（SiO2+Al2O3) (MgO + CaO + SrO + BaO) is 4.6 or less,
the ratio of MgO/CaO is 2 or more,
the SrO/CaO ratio is more than 1.53,
(MgO + SrO)/(MgO + CaO + SrO + BaO) is 0.8 or more.
4. The alkali-free glass according to claim 2, wherein the alkali-free glass contains, in mol% on an oxide basis:
SiO263～68、
Al2O312～14、
B2O30.5～1.3、
MgO 8.5～10、
CaO 2～3.9、
SrO 5.3～8、
BaO0 to 0.3, and
17.5 to 20 parts of MgO + CaO + SrO + BaO,
（SiO2+Al2O3) (MgO + CaO + SrO + BaO) is 4.6 or less,
the ratio MgO/CaO is 2.33 or more,
the SrO/CaO ratio is more than 1.53,
(MgO + SrO)/(MgO + CaO + SrO + BaO) is 0.8 or more.
5. The alkali-free glass according to claim 3, wherein the alkali-free glass contains, in mol% on an oxide basis:
SiO265.5～67.5、
Al2O312.5～13.5、
B2O30.7～1.2、
MgO 8.5～10、
CaO 2～3.9、
SrO 5.3 to 8, and
the alkali-free glass is substantially free of BaO,
MgO + CaO + SrO is 18 to 19.5,
（SiO2+Al2O3) (MgO + CaO + SrO) is 4.5 or less,
the ratio of MgO/CaO is 2 or more,
the SrO/CaO ratio is more than 1.53,
(MgO + SrO)/(MgO + CaO + SrO) is 0.8 or more.
6. The alkali-free glass according to claim 4, wherein the alkali-free glass contains, in mol% on an oxide basis:
SiO265.5～67.5、
Al2O312.5～13.5、
B2O30.7～1.2、
MgO 8.5～10、
CaO 2～3.9、
SrO 5.3 to 8, and
the alkali-free glass is substantially free of BaO,
MgO + CaO + SrO is 18 to 19.5,
（SiO2+Al2O3) (MgO + CaO + SrO) is 4.5 or less,
the ratio MgO/CaO is 2.33 or more,
the SrO/CaO ratio is more than 1.53,
(MgO + SrO)/(MgO + CaO + SrO) is 0.8 or more.
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| JP2014-092646 | 2014-04-28 | ||
| JP2014092646A JP2017114685A (en) | 2014-04-28 | 2014-04-28 | Alkali-free glass |
| PCT/JP2015/062547 WO2015166890A1 (en) | 2014-04-28 | 2015-04-24 | Non-alkali glass |
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| US4634684A (en) | 1985-10-23 | 1987-01-06 | Corning Glass Works | Strontium aluminosilicate glass substrates for flat panel display devices |
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