WO2021246345A1 - 高ケイ酸ガラス基板の製造方法、高ケイ酸ガラス基板及び多孔質ガラス - Google Patents

高ケイ酸ガラス基板の製造方法、高ケイ酸ガラス基板及び多孔質ガラス Download PDF

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WO2021246345A1
WO2021246345A1 PCT/JP2021/020568 JP2021020568W WO2021246345A1 WO 2021246345 A1 WO2021246345 A1 WO 2021246345A1 JP 2021020568 W JP2021020568 W JP 2021020568W WO 2021246345 A1 WO2021246345 A1 WO 2021246345A1
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Prior art keywords
glass
less
high silicate
glass substrate
silicate glass
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PCT/JP2021/020568
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English (en)
French (fr)
Japanese (ja)
Inventor
朝敬 小川
裕 黒岩
公章 赤塚
博之 土屋
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AGC Inc
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Asahi Glass Co Ltd
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Priority to JP2022528812A priority Critical patent/JP7810107B2/ja
Publication of WO2021246345A1 publication Critical patent/WO2021246345A1/ja
Priority to US18/060,058 priority patent/US20230093194A1/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
    • C03C11/00—Multi-cellular glass ; Porous or hollow glass or glass particles
    • C03C11/005—Multi-cellular glass ; Porous or hollow glass or glass particles obtained by leaching after a phase separation step
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B32/00—Thermal after-treatment of glass products not provided for in groups C03B19/00, C03B25/00 - C03B31/00 or C03B37/00, e.g. crystallisation, eliminating gas inclusions or other impurities; Hot-pressing vitrified, non-porous, shaped glass products
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B19/00—Other methods of shaping glass
    • C03B19/06—Other methods of shaping glass by sintering, e.g. by cold isostatic pressing of powders and subsequent sintering, by hot pressing of powders, by sintering slurries or dispersions not undergoing a liquid phase reaction
    • 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
    • C03C23/00—Other surface treatment of glass not in the form of fibres or filaments
    • C03C23/0085—Drying; Dehydroxylation
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
    • C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/097—Glass compositions containing silica with 40% to 90% silica, by weight containing phosphorus, niobium or tantalum
    • 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
    • C03B18/02—Forming sheets

Definitions

  • the present invention relates to a method for manufacturing a high silicate glass substrate, a high silicate glass substrate and porous glass.
  • quartz glass is expensive to manufacture and process. Therefore, by producing a phase-dividing glass of borosilicate glass, elution of components other than silicic acid with an acid to form a porous glass, and using high-silicic acid glass densified by sintering as a high-frequency substrate material. , Cost can be suppressed.
  • Patent Document 1 as a method for producing high silicic acid glass containing silicic acid as a main component, alkaline borosilicate-based glass is heat-treated to form a SiO 2- rich insoluble phase and a B 2 O 3- rich soluble phase.
  • a method of producing a porous glass containing SiO 2 as a main component by eluting a soluble phase with an acid after phase separation, and then firing the porous glass to produce a high silicate glass.
  • an object of the present invention is to provide a method for producing a high-silicic acid glass substrate, which is suitable for a high-frequency substrate material and has a large area and can be sintered without breaking, a high-silicic acid glass substrate, and a porous glass.
  • the present inventors obtain a high silicate glass substrate by drying a porous glass having a specific composition so that the water content is within a specific range before sintering, thereby sintering a large area without breaking. It was found that it could be obtained, and the present invention was completed based on such findings. That is, the present invention is as follows.
  • the present invention relates to a method for producing a high silicate glass substrate, which comprises the following (1) to (5).
  • R 2 O R is at least one selected from Li, Na and K
  • R'O R'is at least one selected from Mg, Ca, Sr and Ba
  • the glass precursor is subjected to the first heat treatment and phase-separated to obtain a phase-separated glass.
  • the present invention is an oxide-based molar percentage display containing 90% to less than 100% SiO 2 , 0% to 1% Al 2 O 3 , 0% to 10% B 2 O 3 , and a bottom area.
  • the present invention relates to a high silicate glass substrate having an area of 300 cm 2 or more and an OH group concentration of 1200 mass ppm or less.
  • the present invention is an oxide-based molar percentage display, containing 90% to less than 100% SiO 2 , 0% to 1% Al 2 O 3 , 0% to 10% B 2 O 3 , and a bottom area.
  • the present invention relates to porous glass having a thickness of 300 cm 2 or more, a thickness of 3 mm or less, and a median pore size distribution of 150 nm or less.
  • a porous glass having a specific composition is dried so as to have a water content within a specific range before sintering, so that the porous glass has a large area and is baked without cracking.
  • a high silicic acid substrate can be manufactured.
  • the high silicate glass substrate of the present invention has a specific composition and can have a large area because the OH group concentration is in a specific range, and is suitable for a high frequency substrate material. Since the median value of the composition, the thickness and the pore diameter distribution of the porous glass of the present invention is within a specific range, a high-frequency substrate material can be produced without breaking even in a large area by sintering.
  • FIG. 1 is a diagram showing a change in dielectric loss tangent depending on the OH group concentration of glass.
  • FIG. 2 is a diagram showing the results of measuring the fluorescence of glass.
  • the glass composition is indicated by an oxide-based molar percentage display, and mol% may be simply described as%. Further, "-" indicating a numerical range is used in the sense that the numerical values described before and after the numerical range are included as the lower limit value and the upper limit value.
  • the method for manufacturing a high silicate glass substrate of the present invention includes the steps (1) to (5) shown below.
  • R 2 O R is at least one selected from Li, Na and K
  • R'O R'is at least one selected from Mg, Ca, Sr and Ba
  • the glass precursor is subjected to the first heat treatment and phase-separated to obtain a phase-separated glass.
  • Step (1) is a step of producing a glass precursor.
  • SiO 2 is 60% to 75%
  • Al 2 O 3 is 0% to 15%
  • B 2 O 3 is 15% to 30%
  • P 2 O. 5 is selected from 0% to 3%
  • R 2 O is one selected from Li, Na and K
  • R'O is one selected from Mg, Ca, Sr and Ba.
  • the glass raw materials are prepared so as to have a glass composition containing a total of 1% to 10% of one or more of these.
  • SiO 2 is a main component forming the skeleton of glass, and is also a main component of glass after being made porous by acid treatment, and is a component that improves dielectric properties.
  • the content of SiO 2 is 60% or more, preferably 62% or more, more preferably 63% or more, and particularly preferably 65% or more. When the content of SiO 2 is 60% or more, the weather resistance can be improved.
  • the content of SiO 2 is 75% or less, preferably 72% or less, more preferably 70% or less, and particularly preferably 69% or less. When the content of SiO 2 is 75% or less, the composition region suitable for phase separation is obtained.
  • Al 2 O 3 is a component that improves the mechanical strength of the glass precursor and suppresses the enlargement of the phase separation structure.
  • the content thereof is preferably 0.5% or more, more preferably 1% or more, still more preferably 1.5% or more, and particularly preferably 2% or more.
  • the content of Al 2 O 3 is 0.5% or more, the effect of suppressing the phase separation structure from becoming too large, suppressing shrinkage during sintering, and making it difficult to crack is exhibited.
  • the content of Al 2 O 3 is 15% or less, preferably 10% or less, more preferably 8% or less, still more preferably 6% or less, and particularly preferably 4% or less. When the content of Al 2 O 3 is 15% or less, the composition region is suitable for phase separation.
  • B 2 O 3 is a component that promotes melting of the glass raw material and lowers the viscosity of the molten glass. In addition, it is a component that improves the mechanical properties and weather resistance of the glass precursor and promotes phase separation. It is also a component that lowers the dielectric loss tangent of glass after porosification.
  • the content of B 2 O 3 is 15% or more, preferably 20% or more, more preferably 22% or more, and particularly preferably 24% or more. When the content of B 2 O 3 is 15% or more, a phase-separated glass can be obtained.
  • the content of B 2 O 3 is 30% or less, preferably 28% or less, more preferably 26% or less, and particularly preferably 25% or less. When the content of B 2 O 3 is 30% or less, volatilization during glass melting can be suppressed.
  • R 2 O (R is at least one selected from Li, Na, and K) is not an essential component, but is useful for promoting melting of glass raw materials, adjusting thermal expansion, viscosity, etc., and is a glass precursor. It is a component that promotes the phase separation of glass.
  • the total content of R 2 O is preferably at least 1%, more preferably 2% or more, more preferably 3% or more, particularly preferably 4% or more.
  • the content of R 2 O is preferably 10% or less, more preferably 9% or less, more preferably 8% or less, particularly preferably not more than 7%. When the content of R 2 O is 10 percent or less, it can be secured weather resistance of the glass precursor.
  • R'O (R'is at least one selected from Mg, Ca, Sr and Ba) is not an essential component, but does not increase the devitrification temperature of glass, improves solubility and promotes phase separation. It is an ingredient that makes you.
  • the total content of R'O is preferably 1% or more, more preferably 2% or more, still more preferably 3% or more, and particularly preferably 4% or more. When the content of R'O is 1% or more, phase separation can be promoted. If there is too much R'O, it will be difficult to separate the phases.
  • the total content of R'O is preferably 10% or less, more preferably 9% or less, still more preferably 8% or less, and particularly preferably 7% or less. When the content of R'O is 10% or less, phase separation is easy.
  • the total content of R 2 O and R'O is more than 10%, preferably not more than 8%, more preferably 7% or less.
  • the total content of R 2 O and R'O is 10% or less, the cracking of the acid treatment can be suppressed components to gel upon acid treatment can be suppressed. Further, in the cleaning step after the acid treatment, alkaline cleaning for removing the gel can be omitted.
  • the total content of R 2 O and R'O is at least 1%, preferably at least 2%, more preferably 3% or more, particularly preferably 4% or more.
  • P 2 O 5 is a component that promotes phase separation.
  • the content thereof is preferably 0.1% or more, more preferably 0.2% or more, still more preferably 0.3% or more, and particularly preferably 0.4% or more. Is.
  • the content of P 2 O 5 is 0.1% or more, the effect of promoting phase separation can be sufficiently obtained, and phase separation can be performed online in a continuous forming process such as float forming. Additional heat treatment for the phase can be omitted.
  • the content of P 2 O 5 is 3% or less, preferably 2% or less, more preferably 1% or less, and particularly preferably 0.9% or less.
  • brick erosion and volatilization during glass melting can be suppressed in a mass production furnace, and excessive increase in the coefficient of thermal expansion can be suppressed to suppress glass breakage during acid treatment. ..
  • Cl is a component that improves the clarity of molten glass.
  • the Cl content is preferably 0.1% or more, more preferably 0.15% or more, still more preferably 0.2% or more, and particularly preferably 0.25% or more.
  • the Cl content is 0.1% or more, sufficient clarity can be obtained, so that the number of bubbles in the glass precursor and the phase-separated glass can be suppressed.
  • the Cl content is preferably 1% or less, more preferably 0.7% or less, still more preferably 0.5% or less, and particularly preferably 0.3% or less.
  • 2 O 3 and the like may be contained in a range of preferably 5% or less, more preferably 3% or less, and particularly preferably 1% or less.
  • the prepared glass batch is melted at 1300 to 1600 ° C. for 4 to 12 hours.
  • the molten glass is formed into a plate shape and then slowly cooled at 400 to 600 ° C. for 10 minutes to 10 hours to obtain a glass precursor.
  • the method for obtaining the glass precursor is not particularly limited, but in the case of small-quantity production, for example, a crucible and a mold may be used, and in the case of mass production, for example, continuous production in a refractory furnace may be performed. good.
  • molten glass having a temperature equal to or higher than the softening point is discharged in a strip shape from the refractory furnace to form a glass ribbon, which is supplied onto the surface of the molten metal and is supplied on the surface of the molten metal.
  • the glass ribbon supplied to the container is transferred, and the glass ribbon transferred thereafter is cooled in the region on the upstream side in the transfer direction so that the temperature of the glass ribbon is lower than the softening point in the entire width direction.
  • the viscosity of the glass melt when supplied to the surface of the molten metal is preferably 0.5 or more, more preferably 1.0 or more, still more preferably 1.5 or more, and particularly preferably 2.0 or more in log ⁇ . be. Further, 5.5 or less is preferable, 5.0 or less is more preferable, 4.5 or less is further preferable, 4.0 or less is particularly preferable, and 3.5 or less is further preferable.
  • the temperature of the molten metal is preferably equal to or higher than the slow cooling point and lower than the softening point of the glass to be manufactured.
  • T 2 which the glass viscosity becomes 10 2 dPa ⁇ s is 1700 ° C. or less.
  • T 2 is 1700 ° C. or lower, the solubility of the glass is excellent and the burden on the manufacturing equipment can be reduced. For example, it is possible to extend the life of equipment such as a kiln that melts glass and improve productivity. In addition, defects derived from the kiln (for example, lump defects, Zr defects, etc.) can be reduced.
  • T 2 is more preferably 1680 ° C or lower, and even more preferably 1670 ° C or lower.
  • T 2 is preferably 1630 ° C. or higher.
  • the temperature T 4 which glass viscosity of 10 4 dPa ⁇ s is 1290 ° C. or less. This makes the glass excellent in moldability. Further, for example, by lowering the temperature during glass molding, it is possible to reduce the amount of volatilized substances in the atmosphere around the glass, thereby reducing the defects of the glass. Since the glass can be molded at a low temperature, the burden on the manufacturing equipment can be reduced. For example, it is possible to extend the life of equipment such as a float bath for forming glass and improve productivity. T 4 is more preferably 1280 ° C. or lower.
  • T 4 in accordance with the method specified in ASTM C 965-96, the viscosity using a rotational viscometer was measured and determined as the temperature at which the 10 4 dPa ⁇ s.
  • NBS710 and NIST717a were used as reference samples for device calibration.
  • the shape of the main surface is not particularly limited, but for example, a rectangle or a circle is preferable.
  • the bottom area of the glass precursor obtained as described above is preferably 300 ⁇ 5000 cm 2, more preferably 700 ⁇ 3600 cm 2, more preferably from 900 ⁇ 2000 cm 2.
  • the thickness of the glass precursor is preferably 0.5 to 3 mm, more preferably 0.7 to 2.5 mm, still more preferably 1 to 2 mm.
  • the term "bottom area" refers to the area of the main surface.
  • the aspect ratio of the glass precursor is preferably 500 to 36000, more preferably 1000 to 20000, and even more preferably 5000 to 10000. If the aspect ratio is too small, there will be a large difference in the speed at which the boron oxide-rich phase is removed between the surface and the inside of the glass precursor in the step (3) of making it porous, which will be described later, so stress is likely to occur and the glass is porous. The glass is fragile. On the other hand, if the aspect ratio is too large, it becomes difficult to handle. As used herein, the term "aspect ratio" refers to the area (cm 2 ) / thickness (cm) of the main surface.
  • the number of bubbles in the glass precursor should be 0.1 / cm 2 or less on the main surface in order to suppress the probability of cracking / cracking during acid treatment or sintering with bubbles as the starting point during mass production. preferable.
  • the number of bubbles in the glass precursor is measured visually or by using an optical microscope using a high-intensity light source or the like.
  • Step (2) Phase separation step>
  • the glass precursor obtained in the step (1) is subjected to the first heat treatment, and the insoluble phase (silicic acid phase) containing SiO 2 as the main component and B 2 O 3 as the main components are used.
  • This is a step of separating the phase into a soluble phase (boric acid phase) to obtain a phase-separated glass. Whether or not the glass is phase-separated can be determined by SEM. When the glass is phase-separated, it can be observed that it is divided into two or more phases when observed by SEM.
  • phase-dividing glass examples include a binodal-type phase-dividing glass in a binodal state and a spinodal-type phase-dividing glass in a spinodal state.
  • the binodal state is a phase separation due to the nucleation-growth mechanism and is generally spherical.
  • the spinodal state is a state in which the phase divisions are entwined with each other and continuously in three dimensions with some regularity.
  • the spinodal type phase-dividing glass described later is particularly preferable.
  • the heat treatment temperature is preferably 50 ° C. or higher, more preferably 100 ° C. or higher than the glass transition point. Further, from the viewpoint of suppressing deformation of the glass, the heat treatment temperature is preferably 400 ° C. higher or lower than the glass transition point, and more preferably 300 ° C. or lower.
  • the heat treatment temperature is, for example, preferably 400 ° C. or higher and 1000 ° C. or lower, more preferably 500 ° C. or higher and 900 ° C. or lower, and further preferably 550 ° C. or higher and 800 ° C. or lower. If the heat treatment temperature is too high, the glass precursor will soften and it will be difficult to obtain the desired shape. On the other hand, if the heat treatment temperature is too low, it becomes difficult to separate the phase of the glass precursor.
  • the heat treatment time is preferably 10 minutes or more, more preferably 1 hour or more, and further preferably 3 hours or more. If the heat treatment time is too short, it becomes difficult to separate the phase of the glass precursor.
  • the upper limit of the heat treatment time is not particularly limited, but from the viewpoint of mass productivity, 36 hours or less is preferable, 24 hours or less is more preferable, and 12 hours or less is further preferable.
  • Examples of the method for separating the phase of glass include a method of heat-treating the glass after molding and a method of holding the glass at a phase separation temperature or higher before molding.
  • Examples of the method of holding the glass at the phase splitting temperature or higher before molding include a method of holding the glass at the phase splitting start temperature or higher and then holding it at the phase splitting start temperature or lower for phase splitting.
  • a method of holding the glass online at a phase separation start temperature or higher and then holding it at a phase split start temperature or lower to split the phase can be mentioned.
  • Step (3) Acid treatment step>
  • the phase-dividing glass obtained in the step (2) is immersed in an acid and treated with an acid to remove the soluble phase (boric acid phase) containing B 2 O 3 as a main component and make it porous.
  • the acid include hydrochloric acid and nitric acid. It should be noted that these acids may be used alone or in combination.
  • the acid concentration is preferably 0.1 to 5 mol / L, more preferably 0.5 to 4 mol / L, and even more preferably 1 to 3 mol / L.
  • the acid treatment temperature is preferably 40 ° C. or higher, more preferably 50 ° C. or higher, still more preferably 60 ° C.
  • the immersion temperature is low, abnormal expansion and contraction will occur at the initial stage, and the cracks will be liable to occur. This is because when the immersion temperature is low, the elution ratio of Na 2 O / B 2 O 3 becomes large, and the swelling of the glass due to the substitution of Na + and H 3 O + is compared with the Si skeleton contraction due to the elution of B. This is because it grows larger. By setting the immersion temperature to 40 ° C. or higher, such initial abnormal expansion and contraction are suppressed, and cracking becomes difficult.
  • the upper limit of the immersion temperature is not particularly limited, but in reality, it is preferably 100 ° C. or lower.
  • the acid immersion time is preferably 1 hour or longer, more preferably 5 hours or longer, still more preferably 10 hours or longer, and particularly preferably 20 hours or longer. If the immersion time is too short, it becomes difficult to obtain porous glass.
  • the upper limit of the immersion time is not particularly limited, but in reality, it is 50 hours or less.
  • the median value of the pore size distribution of the porous glass obtained by acid-treating the phase-separated glass is preferably 150 nm or less, more preferably 100 nm or less, and further preferably 80 nm or less.
  • the median value of the pore size distribution is preferably 10 nm or more, more preferably 20 nm or more, and further preferably 30 nm or less.
  • the step (4) is a step of drying the porous glass obtained in the step (3).
  • the water adhering to the porous glass evaporates to become water vapor, which is removed from the porous glass.
  • a cleaning step may be performed between the step (3) and the step (4) by immersing in water (for example, purified water) or the like.
  • the temperature of water or the like used in the cleaning step preferably has a difference of ⁇ 20 ° C from the acid treatment temperature, more preferably ⁇ 10 ° C, and further preferably ⁇ 5. It is preferably within ° C.
  • ultrasonic waves may be applied at the time of cleaning from the viewpoint of removing the residual component in the porous glass.
  • the mass change rate defined by the following formula 1 is 10% or more, preferably 11% or more, more preferably 12% or more, and further preferably 13% or more.
  • Porous glass is prone to cracking during production due to the moisture remaining in the glass, but it is baked in step (4) after being dried so that the mass change rate is 10% or more in step (3). By tying, it can be made into a plate and sintered without cracking.
  • the upper limit of the mass change rate is not particularly limited, but is usually preferably 20% or less, and more preferably 15% or less.
  • Mass change rate (%) [(mass before drying-mass after drying) / mass before drying] x 100 ... (Equation 1)
  • the mass change rate is measured by allowing the porous glass obtained in step (3) to stand overnight in a normal atmospheric pressure atmosphere (this state is referred to as before drying), measuring the mass before drying, and then measuring the mass. Drying is performed and the mass after heating is measured.
  • the drying method is not particularly limited, but for example, in an atmospheric pressure atmosphere, it is preferably 20 ° C. or higher and 100 ° C. or lower, more preferably 30 ° C. or higher and 90 ° C. or lower, and further preferably 40 ° C. or higher and 80 ° C. or lower.
  • Step (5) is a step of obtaining a high silicate glass substrate by subjecting the porous glass dried in step (4) to a second heat treatment and sintering it.
  • the temperature up to a controlled temperature at a heating rate of preferably 100 ° C./hour or less, more preferably 70 ° C./hour or less, still more preferably 50 ° C./hour or less.
  • a heating rate preferably 100 ° C./hour or less, more preferably 70 ° C./hour or less, still more preferably 50 ° C./hour or less.
  • the lower limit of the temperature rising rate is not particularly limited, but is usually 10 ° C./hour or more.
  • the control temperature in the second heat treatment is preferably 900 ° C. or higher, more preferably 1000 ° C. or higher, still more preferably 1100 ° C. or higher.
  • the control temperature is preferably 1250 ° C. or lower, more preferably 1200 ° C. or lower, still more preferably 1150 ° C. or lower, from the viewpoint of suppressing fusion with the setter.
  • the second heat treatment has a dew point of preferably 60 ° C. or lower, more preferably 56 ° C. or lower, still more preferably 39 ° C. or lower, still more preferably 22 ° C. or lower, still more preferably 20 ° C. or lower, and particularly preferably 10 ° C. or lower. Most preferably, it is carried out in an environment of 0 ° C. or lower. If the dew point during the second heat treatment is too high, moisture is likely to be adsorbed on the porous glass. By setting the dew point to 60 ° C. or lower, it is possible to suppress the adsorption of water on the porous glass, suppress the OH group concentration of the obtained high silicate glass substrate, and improve the dielectric loss tangent.
  • the lower limit of the dew point is not particularly limited, but in reality, it is ⁇ 40 ° C. or higher.
  • the second heat treatment may be performed under atmospheric pressure, but it is preferably performed under nitrogen, dry air, hydrogen, or a mixed atmosphere thereof from the viewpoint of controlling the concentration of OH groups.
  • porous glass can be sandwiched between setters and heated to be sintered, and warpage can be suppressed to flatten the glass.
  • the material of the setter is not particularly limited, and examples thereof include ceramic materials such as alumina, cordierite, and mullite.
  • the surface roughness Ra of the setter is preferably 1 ⁇ m or less, more preferably 0.5 ⁇ m or less, and further preferably 0.1 ⁇ m or less. By setting Ra to 1 ⁇ m or less, the glass surface roughness after sintering can be reduced, and the load in the subsequent processing process can be reduced. On the other hand, Ra is typically 1 nm or more.
  • the weight of the setter can effectively suppress the warp when the load per unit area is preferably 3 g / cm 2 or more.
  • the flatness of the setter defined in JIS0621-1984 is preferably 1 mm or less, more preferably 0.5 mm or less, still more preferably 0.1 mm or less. By setting the flatness to 1 mm or less, the warp of the glass substrate after sintering can be reduced, and the load in the subsequent processing process can be reduced. On the other hand, the flatness is typically 0.001 mm or more.
  • the bottom area of the setter is preferably 1 time or more and 1.5 times or less, more preferably 1.05 times or more and 1.3 times or less, still more preferably 1. It is 1 times or more and 1.2 times or less.
  • the content of SiO 2 after sintering is 90% or more, preferably 92% or more, more preferably 94% or more, and particularly preferably 96% or more.
  • the content of SiO 2 after sintering is less than 100%, preferably 99% or less, more preferably 98% or less, and particularly preferably 97% or less.
  • the content of SiO 2 is less than 100%, the decrease in mechanical strength can be suppressed.
  • Al 2 O 3 is a component that improves mechanical strength. Further, it is a component that controls the expansion and contraction of the glass in the acid treatment when the glass precursor is made porous, and may be contained.
  • the content thereof is preferably 0.05% or more, more preferably 0.1% or more.
  • the content of Al 2 O 3 after sintering is 0.05% or more, the mechanical strength can be improved.
  • the content of Al 2 O 3 after sintering is 1% or less, preferably 0.5% or less, and more preferably 0.3% or less. When the content of Al 2 O 3 is 1% or less, devitrification during sintering can be suppressed.
  • the content of B 2 O 3 after sintering is preferably 0.5% or more, more preferably 1% or more, still more preferably 2% or more, particularly. It is preferably 3% or more.
  • the content of B 2 O 3 after sintering is 0.5% or more, the viscosity can be lowered and the sintering temperature can be lowered.
  • the content of B 2 O 3 after sintering is 10% or less, preferably 8% or less, more preferably 6% or less, and particularly preferably 4% or less. When the content of B 2 O 3 is 10% or less, the decrease in weather resistance can be suppressed.
  • R 2 O (R is at least one selected from Li, Na and K), R'O (R'is at least one selected from Mg, Ca, Sr and Ba), ZrO 2 , TiO 2 , La 2 O 3 , Ta 2 O 5 , TeO 2 , Nb 2 O 5 , Gd 2 O 3 , Y 2 O 3 , Eu 2 O 3 , Sb 2 O 3 , SnO 2 , P 2 O 5 and Bi 2 O 3 and the like may be contained in a range of preferably 3% or less, more preferably 2% or less, particularly preferably 1% or less, still more preferably 0.5% or less, still more preferably 0.1% or less.
  • R 2 O and R'O of the high silicate glass are in the above range, the dielectric adjacency is not deteriorated, and when the glass precursor contains R 2 O and R'O at the time of production, as a large area.
  • R 2 O and R'O is the range of the high silicate glass.
  • a high silicate glass substrate can be formed by the above steps.
  • the high silicate glass substrate of the present invention When the high silicate glass substrate of the present invention is used as a high-frequency substrate material, holes may be formed in the high silicate glass.
  • the method for forming the pores is not particularly limited, but in order to accurately form small pores having a diameter of 200 ⁇ m or less, for example, a method of irradiating a high silicate glass substrate with a laser is preferable.
  • the high silicate glass substrate of the present invention is excellent in processability by laser irradiation.
  • the wavelength of the laser is not particularly limited, but for example, a laser having a wavelength of 10.6 ⁇ m or less, 3000 nm or less, 2050 nm or less, 1090 nm or less, 540 nm, and 400 nm or less is used. In particular, when forming a small hole having a diameter of 50 ⁇ m or less, the following two methods are suitable.
  • the high silicate glass substrate of the present invention has an oxide-based molar percentage display, which contains 90% to less than 100% SiO 2 , 0% to 1% Al 2 O 3 , and B 2 O 3 . Contains 0% to 10%. The reason why the content of each component is specified in the above range will be described below.
  • SiO 2 is a main component forming the skeleton of glass, and is a component that improves weather resistance and lowers the dielectric loss tangent.
  • the content of SiO 2 is 90% or more, preferably 92% or more, more preferably 94% or more, and particularly preferably 96% or more. When the content of SiO 2 is 90% or more, the weather resistance can be improved.
  • the content of SiO 2 is less than 100%, preferably 99% or less, more preferably 98% or less, and particularly preferably 97% or less. When the content of SiO 2 is less than 100%, the decrease in mechanical strength can be suppressed.
  • Al 2 O 3 is a component that improves mechanical strength. It is also a component that controls the expansion and contraction of glass in the acid treatment when making the glass precursor porous.
  • the content of Al 2 O 3 is preferably 0.05% or more, more preferably 0.1% or more.
  • the mechanical strength can be improved.
  • the content of Al 2 O 3 is 1% or less, preferably 0.5% or less, and more preferably 0.3% or less. When the content of Al 2 O 3 is 1% or less, devitrification during sintering can be suppressed.
  • B 2 O 3 is a component that lowers the viscosity and lowers the sintering temperature. It is also a component that lowers the dielectric loss tangent.
  • the content of B 2 O 3 is preferably 0.5% or more, more preferably 1% or more, still more preferably 2% or more, and particularly preferably 3% or more. ..
  • the content of B 2 O 3 is 10% or less, preferably 8% or less, more preferably 6% or less, and particularly preferably 4% or less.
  • the content of B 2 O 3 is 10% or less, the decrease in weather resistance can be suppressed.
  • R 2 O (R is at least one selected from Li, Na and K), R'O (R'is at least one selected from Mg, Ca, Sr and Ba), ZrO 2 , TiO 2 , La 2 O 3 , Ta 2 O 5 , TeO 2 , Nb 2 O 5 , Gd 2 O 3 , Y 2 O 3 , Eu 2 O 3 , Sb 2 O 3 , SnO 2 , P 2 O 5 and Bi 2 O 3 and the like may be contained in a range of preferably 3% or less, more preferably 2% or less, particularly preferably 1% or less, still more preferably 0.5% or less, still more preferably 0.1% or less.
  • R 2 O and R'O of the high silicate glass are in the above range, the dielectric adjacency is not deteriorated, and when the glass precursor contains R 2 O and R'O at the time of production, as a large area.
  • R 2 O and R'O is the range of the high silicate glass.
  • the high silicate glass substrate of the present invention has a bottom area of 300 cm 2 or more, preferably 600 cm 2 or more, more preferably 900 cm 2 or more, and further preferably 1200 cm 2 or more. Since the bottom area is 300 cm 2 or more, it is suitable for high frequency substrate material applications. From the viewpoint of ensuring strength, the bottom area is preferably 5000 cm 2 or less.
  • the high silicate glass substrate of the present invention has an OH group concentration of 1200 mass ppm or less, more preferably 1000 mass ppm or less, and particularly preferably 800 mass ppm or less.
  • the OH group concentration is 1200 mass ppm or less, the dielectric loss tangent (dissipation factor, hereinafter also abbreviated as Df) can be reduced.
  • the lower limit of the OH group concentration is not particularly limited, but is typically 10 mass ppm or more.
  • the OH group concentration is measured by an infrared spectrophotometer according to the literature [Cer. Bull., 55 (5), 524, 1976]. The detection limit of this measurement is 1 mass ppm.
  • the OH group concentration can be adjusted by adjusting the atmosphere, dew point, etc. in the sintering step described later. Specific examples of the means for adjusting the OH group concentration include, for example, setting the atmosphere in the sintering step to nitrogen or dry air, setting the dew point to 60 ° C. or lower, and the like.
  • the high silicate glass substrate of the present invention preferably has a dielectric loss tangent at 60 GHz of 0.001 or less, more preferably 0.009 or less, still more preferably 0.0008 or less, and particularly preferably 0.0007 or less. ..
  • the lower limit of the dielectric loss tangent at 60 GHz is not particularly limited, but is typically 0.0001 or more.
  • the high silicate glass substrate of the present invention preferably has a thickness of 0.05 to 2 mm, more preferably 0.1 to 1 mm, and even more preferably 0.3 to 0.8 mm. By setting the thickness within the above range, it can be suitably used as a high-frequency substrate material.
  • the high silicate glass substrate of the present invention is suitable for high frequency substrate materials, aerospace applications materials, and heat resistant materials. In addition, since it has low fluorescence, it is also suitable as a substrate material for DNA chips and a cell culture container.
  • the high silicate glass substrate of the present invention When used as a high-frequency substrate material, a substrate material for a DNA chip, or a cell culture container, holes may be formed in the high silicate glass, and these holes are used, for example, as an electrode.
  • the high silicate glass substrate of the present invention has excellent workability, and it is easy to form fine holes by a laser or the like.
  • the hole may be a through hole or a non-through hole.
  • the opening diameter of the hole is, for example, 200 ⁇ m or less, 100 ⁇ m or less, and 50 ⁇ m or less.
  • the porous glass of the present invention is an oxide-based molar percentage display, in which SiO 2 is 90% to less than 100%, Al 2 O 3 is 0% to 1%, and B 2 O 3 is 0% to 10. %,
  • the bottom area is 300 cm 2 or more, the thickness is 3 mm or less, and the median value of the pore size distribution is 150 nm or less.
  • the reason why the median value of the composition range, bottom area, thickness, and pore size distribution is set to the above range is as follows. Method for manufacturing high silicate glass substrate> and ⁇ 2. It is the same as the above-mentioned in the high silicate glass substrate>.
  • a high frequency substrate material can be produced without breaking even in a large area.
  • Applications of the porous glass of the present invention include, for example, a window material having both transparency and gas permeability, which are the characteristics thereof, or a base body in which pores are impregnated with various functional materials and supported.
  • the method for producing the porous glass of the present invention is as follows: ⁇ 1.
  • the production method including the above-mentioned steps (1) to (3) in the method for producing a high silicate glass substrate> is preferably mentioned because a porous body having a large bottom area can be obtained.
  • Dissipation factor Dissipation factor is described in the document [Y. Kato and M. Horibe, “Permittivity measurements and associated uncertainties up to 110 GHz in circular-disk resonator method” Proceedings of the 46th European Microwave Conference (2016) 4-6 Oct 2016.] It was measured according to the method of.
  • OH group concentration The OH group concentration was measured by an infrared spectrophotometer according to the literature [Cer. Bull., 55 (5), 524, 1976]. The detection limit of this measurement is 1 mass ppm.
  • the plate-shaped glass After pouring the molten glass onto a carbon plate and forming it into a plate shape, the plate-shaped glass is placed in an electric furnace at a temperature of about Tg + 50 ° C. and held for 1 hour, and then Tg-100 ° C. at a cooling rate of 1 ° C./min. The temperature of the electric furnace was lowered to room temperature, and then the glass was allowed to cool to room temperature.
  • ⁇ Process (2) Phase separation process >> After holding the glass obtained in the step (1) at 600 ° C. for 27 hours, the electric furnace is cooled to Tg-100 ° C. at a cooling rate of 1 ° C./min, and then allowed to cool until the glass reaches room temperature to separate the phases. I let you. After that, a glass substrate having a thickness of 1.0 mm, a shape of 50 ⁇ 50 mm, and an arithmetic average roughness Ra of the main surface of 1.0 nm was prepared by cutting and polishing.
  • step (3) Drying process >> The glass obtained in step (3) is immersed in purified water at 80 ° C., washed for 20 minutes while applying ultrasonic waves at 28 kHz, taken out, left at room temperature for 12 hours, and then under reduced pressure of 20 kPa in a vacuum furnace. The mixture was dried for 3 hours so that the rate of change in mass was 10 to 50%.
  • Examples 1, 2, 4, 5, 10 and 11 of Examples are high silicate glass precursors having a composition within the specified range in the present invention and are acid-treated. Cracks and cracks occurred at the time and during sintering. On the other hand, in Examples 3, 6 to 9, 12 to 18, which are comparative examples, cracks and cracks occurred during the acid treatment and the sintering.
  • Step (1) Preparation step of glass precursor >> Each reagent was weighed and mixed so as to have the glass composition shown in the molar percentage display based on the oxide of Example 20, and a preparation batch of 13 kg was obtained. Then, the raw material was charged at 1550 ° C. using a platinum crucible for 4 hours, then stirred for 1 hour using a platinum stirrer, allowed to stand for 2 hours, then cooled at 1250 ° C., and then cast into a carbon mold to 400 mm. A glass (glass precursor) block of ⁇ 400 mm ⁇ 30 mm was obtained.
  • Phase separation process >> After polishing the glass obtained in the step (1), heat treatment was performed under the conditions shown in Table 1 to separate the phases. Then, the block was sliced and ground to obtain a glass substrate having a size of 375 mm ⁇ 375 mm ⁇ 1.2 mm.
  • Example 23 and 24 are dried so that the water content is within the range specified in the present invention in the drying step before sintering the porous glass in the sintering step. By doing so, a high silicate glass substrate could be manufactured by sintering with a large area and without cracking.
  • Examples 25 and 26 which are comparative examples, the amount of water in the drying step was not within the range specified in the present invention, and cracks occurred during sintering.
  • Example 4 For Example 24 in Experimental Example 3, ⁇ Step (5): Sintering Step >> in Experimental Example 3 was carried out under the sintering conditions shown in Table 4. Table 4 shows the results of measuring the OH group concentration of the obtained glass substrate. Examples 27 to 32 are examples.
  • FIG. 1 shows the results of evaluating the change in Df depending on the OH group concentration of the glass plate obtained in Experimental Example 4. As shown in FIG. 1, it was found that the lower the OH group concentration, the better the dielectric loss tangent.
  • Example 6 The glass plate obtained in Example 24 of Experimental Example 3 was subjected to composition analysis using ICP emission spectroscopic analysis. Table 5 shows the results in terms of oxide-based molar percentage display.
  • the glass plate of Example 24 as an example has a relative fluorescence intensity of 100 or less in the fluorescence spectrum of 550 nm to 850 nm, which is smaller than EN-A1 manufactured by AGC and D263-bio manufactured by Shott. I understand.

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2106744A (en) * 1934-03-19 1938-02-01 Corning Glass Works Treated borosilicate glass
JPS57205337A (en) * 1981-06-11 1982-12-16 Hoya Corp Manufacture of high silicate glass with high ultraviolet-ray transmittance
JPS58140341A (ja) * 1982-02-15 1983-08-20 Agency Of Ind Science & Technol 高ケイ酸多孔質ガラスの製造方法
WO2004083145A1 (ja) * 2003-03-20 2004-09-30 Japan Science And Technology Agency 高ケイ酸ガラスの製造方法および高ケイ酸ガラス
JP2005336047A (ja) * 2004-04-28 2005-12-08 Asahi Glass Co Ltd 合成石英ガラス製光学部材およびその製造方法
JP2020007180A (ja) * 2018-07-05 2020-01-16 日本電気硝子株式会社 多孔質ガラス部材の製造方法

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EP1740512A1 (en) * 2004-04-28 2007-01-10 Asahi Glass Company, Limited Optical member made of synthetic quartz glass, and process for its production
JP2012091996A (ja) * 2010-09-30 2012-05-17 Canon Inc 多孔質ガラスの製造方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2106744A (en) * 1934-03-19 1938-02-01 Corning Glass Works Treated borosilicate glass
JPS57205337A (en) * 1981-06-11 1982-12-16 Hoya Corp Manufacture of high silicate glass with high ultraviolet-ray transmittance
JPS58140341A (ja) * 1982-02-15 1983-08-20 Agency Of Ind Science & Technol 高ケイ酸多孔質ガラスの製造方法
WO2004083145A1 (ja) * 2003-03-20 2004-09-30 Japan Science And Technology Agency 高ケイ酸ガラスの製造方法および高ケイ酸ガラス
JP2005336047A (ja) * 2004-04-28 2005-12-08 Asahi Glass Co Ltd 合成石英ガラス製光学部材およびその製造方法
JP2020007180A (ja) * 2018-07-05 2020-01-16 日本電気硝子株式会社 多孔質ガラス部材の製造方法

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