WO2019117122A1 - Las-based crystallized glass plate production method and las-based crystallized glass plate - Google Patents

Las-based crystallized glass plate production method and las-based crystallized glass plate Download PDF

Info

Publication number
WO2019117122A1
WO2019117122A1 PCT/JP2018/045446 JP2018045446W WO2019117122A1 WO 2019117122 A1 WO2019117122 A1 WO 2019117122A1 JP 2018045446 W JP2018045446 W JP 2018045446W WO 2019117122 A1 WO2019117122 A1 WO 2019117122A1
Authority
WO
WIPO (PCT)
Prior art keywords
las
crystallized glass
glass plate
based crystallized
producing
Prior art date
Application number
PCT/JP2018/045446
Other languages
French (fr)
Japanese (ja)
Inventor
裕基 横田
Original Assignee
日本電気硝子株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 日本電気硝子株式会社 filed Critical 日本電気硝子株式会社
Priority to JP2019559646A priority Critical patent/JPWO2019117122A1/en
Publication of WO2019117122A1 publication Critical patent/WO2019117122A1/en

Links

Classifications

    • 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
    • C03B32/02—Thermal crystallisation, e.g. for crystallising glass bodies into glass-ceramic articles
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B6/00—Heating by electric, magnetic or electromagnetic fields
    • H05B6/02—Induction heating
    • H05B6/10—Induction heating apparatus, other than furnaces, for specific applications
    • H05B6/12—Cooking devices

Definitions

  • the present invention relates to a method for producing a Li 2 O-Al 2 O 3 -SiO 2 -based (hereinafter, LAS-based) crystallized glass plate and a LAS-based crystallized glass plate.
  • LAS-based Li 2 O-Al 2 O 3 -SiO 2 -based
  • the role of the top plate hides the internal structure of the cooking device such as the heating device, wiring etc. It is to raise.
  • Patent Document 1 discloses a low expansion crystallized glass colored in a deep color by a coloring agent
  • Patent Document 2 discloses a low expansion having visible light transmission characteristics ranging from transparent to opaque.
  • a crystallized glass plate is disclosed.
  • the second method is a method of forming a decorative film on the surface of a transparent low expansion crystallized glass plate using a printing method and concealing the internal structure of the cooker by the decorative film.
  • Patent Document 3 describes a crystallized glass plate provided with a decorative film of raster color consisting of a noble metal and a base metal on the back surface (surface opposite to the cooking surface).
  • the crystallized glass plate described in Patent Document 1 has a dark color tone, there is a problem that it is difficult to transmit the light of the indicator for displaying the amount of applied power and the like. That is, when the crystallized glass plate described in Patent Document 1 is used for the top plate of the electromagnetic heating cooker, when the indicator is provided on the back side of the top plate, the light of the red indicator is only barely visible from the cooking surface side Even when the indicator emits a color other than red, such color light can not be displayed on the cooking surface side because the top plate transmits no light other than red (for example, blue or yellow) at all.
  • red for example, blue or yellow
  • the indicator When the indicator emits a color other than red, it is necessary to open a hole at a predetermined location on the top plate in order to display the light of that color on the cooking surface side. As a result, the top plate is chipped or broken Is apt to occur. Furthermore, as one of the factors to enhance the commercial value of the cooker top plate, the appearance design is emphasized, and dark colors have been the mainstream in the past, but recently bright colors are being favored. However, since the crystallized glass plate of Patent Document 1 has a deep color tone, it can not sufficiently respond to the recent tastes of consumers.
  • the crystallized glass plate described in Patent Document 2 contains 2 to 5% by mass of ZnO in order to precipitate zinc spinel in the glass, but when a large amount of ZnO is thus contained, It becomes easy to precipitate foreign crystals during heat treatment. As a result, when it is intended to obtain a semi-transparent color tone, there is a problem that the color tone is likely to change delicately, making stable production difficult.
  • Patent Document 4 discloses a top plate having a new appearance and optical properties, and the top plate is made of LAS-based crystallized glass plate and exhibits a haze of 50% or more. It contains ⁇ -spodumene solid solution with a small crystal grain size. However, since a crystallized glass plate having a small crystal grain diameter hardly scatters visible light and has high transparency, the color tone is very thin and it is difficult to conceal the internal structure of the cooker.
  • Patent Document 5 discloses a semitransparent LAS-based crystallized glass plate on which a ⁇ -spodumene solid solution having an average crystal grain size of 100 to 1000 nm is precipitated. Since this crystallized glass plate has a bright color and is not too noticeable, it is possible to display the light of various indicators. However, since this crystallized glass plate has been subjected to a long crystallization process (heat treatment process for at least 8 hours), there is a problem that the manufacturing cost is increased.
  • the present invention has been made in view of such circumstances, and the technical problem is that the internal structure of the cooker can be concealed with a bright color, and the decorative film is formed even when the decorative film is formed on the back side.
  • the temperature of the crystalline glass sheet is raised to the maximum heat treatment temperature which exceeds 900 ° C. at a temperature rising rate of 300 to 900 ° C./hour. It has the process of depositing a ⁇ -spodumene solid solution of ⁇ 1000 nm to obtain a LAS-based crystallized glass plate. In this way, it is possible to efficiently produce a LAS-based crystallized glass plate which has a bright color and in which the decorative film is not noticeable when the decorative film is formed on the back side. That is, a crystallized glass plate having an opal-like and translucent appearance can be produced in a short time.
  • the holding time at the (maximum heat treatment temperature ⁇ 10 ° C.) is preferably less than 60 minutes. In this way, the productivity of the crystallized glass plate can be enhanced.
  • a ⁇ -spodumene solid solution having an average crystal grain size of 150 to 900 nm.
  • the method of producing a LAS-based crystallized glass plate of the present invention is a LAS-based LAS-based glass plate in which the lightness value L * of the L * a * b * display system according to JIS Z8729 is 30 to 80 in terms of 3.0 mm thickness. It is preferable to obtain a crystallized glass plate. In this way, it is easy to obtain an opal-like appearance that is excellent in aesthetics.
  • a LAS-based crystallized glass plate of the present invention it is preferable to obtain a LAS-based crystallized glass plate having an average transmittance of 10 to 50% at a wavelength of 400 to 800 nm in terms of a plate thickness of 3.0 mm. . In this way, the amount of light transmitted through the top plate can be easily made appropriate.
  • a LAS-based crystallized glass plate of the present invention it is preferable to obtain a LAS-based crystallized glass plate having an average transmittance of 50% or more at a wavelength of 800 to 1500 nm in terms of a plate thickness of 3.0 mm. In this way, it becomes easy to transmit the heat rays at the time of cooking
  • the method for producing a LAS-based crystallized glass plate of the present invention is a LAS-based crystallized glass plate having an average linear thermal expansion coefficient of -10 ⁇ 10 -7 to + 30 ⁇ 10 -7 / ° C. at 30 to 750 ° C. It is preferable to obtain. In this way, even when a large temperature distribution occurs inside the top plate, the crystallized glass plate is less likely to be damaged. As a result, it becomes easy to apply to the cooker top plate.
  • group crystallized glass board is less than 2 mass%. In this way, it becomes difficult to precipitate foreign crystals during heat treatment.
  • the LAS-based crystallized glass plate has a composition of 55 to 75% SiO 2 , 15 to 30% Al 2 O 3 , and Li 2 O 3 by mass. 2 to 6%, MgO 0 to 3%, BaO 0 to 5%, ZnO 0 to less than 2%, TiO 2 1 to 6%, ZrO 2 0 to 4%, P 2 O 5 0 to 5%, Na 2 O It is preferable to contain 0 to 4% and K 2 O 0 to 4%.
  • group crystallized glass board of this invention uses a LAS type
  • the LAS-based crystallized glass plate of the present invention is a LAS-based crystallized glass plate on which a ⁇ -spodumene solid solution having an average crystal grain diameter of 100 to 1000 nm is precipitated, and in accordance with JIS Z8729 in terms of a plate thickness of 3.0 mm.
  • the lightness value L * of the L * a * b * display system is 30 to 80.
  • the LAS-based crystallized glass plate of the present invention preferably has an average transmittance of 10 to 50% at a wavelength of 400 to 800 nm in terms of a plate thickness of 3.0 mm.
  • the LAS-based crystallized glass plate of the present invention preferably has an average transmittance of 50% or more at a wavelength of 800 to 1500 nm in terms of a plate thickness of 3.0 mm.
  • the LAS-based crystallized glass sheet of the present invention preferably has an average linear thermal expansion coefficient at 30 to 750 ° C. of ⁇ 10 ⁇ 10 ⁇ 7 to + 30 ⁇ 10 ⁇ 7 / ° C.
  • the composition is, by mass%, 55 to 75% SiO 2 , 15 to 30% Al 2 O 3, 2 to 6% Li 2 O, and 0 to 3% MgO.
  • the LAS-based crystallized glass plate of the present invention has a composition as SiO 2 60-70%, Al 2 O 3 20 over 30%, Li 2 O 3-5%, MgO 0-1% by mass. , BaO 1 to 2%, ZnO 0 to less than 0.4%, TiO 2 1 to 4%, ZrO 2 2 to 3%, P 2 O 5 0 to 2%, Na 2 O 0 to 4%, K 2 O It is preferable to contain 0 to 4%.
  • the method for producing a LAS-based crystallized glass sheet of the present invention comprises the step of preparing a crystalline glass sheet.
  • the crystalline glass plate can be produced by a known method.
  • a crystalline glass plate can be produced by preparing a glass material so as to have a predetermined composition, melting the obtained glass batch at a temperature of 1550 to 1750 ° C., and then forming it into a plate shape. .
  • a forming method there are a float method, a roll out method, a pressing method and the like, but when it is desired to improve the surface smoothness of a crystalline glass plate, the float method is preferable, and when producing a large crystalline glass plate
  • the roll-out method is preferable, and when it is desired to suppress the devitrification at the time of molding, the press method is preferable.
  • the method for producing a LAS-based crystallized glass sheet of the present invention is characterized in that the temperature of the crystalline glass sheet is raised to the maximum heat treatment temperature which exceeds 900 ° C. (preferably 1000 to 1230 ° C.).
  • the maximum heat treatment temperature is too low, the ⁇ -quartz solid solution is easily precipitated, so that the transparency becomes high, and it becomes difficult to obtain an opal-like translucent appearance.
  • the method for producing a LAS-based crystallized glass sheet of the present invention is characterized in that the temperature of the crystalline glass sheet is raised at a temperature rising rate of 300 to 900 ° C./hour (preferably, a temperature rising rate of 350 to 850 ° C./hour).
  • a temperature rising rate 300 to 900 ° C./hour
  • the crystal grain size is coarsened, so the cloudiness becomes too strong and it tends to be opaque.
  • the temperature rising rate becomes high the crystal grain size becomes finer, the scattering effect of visible light decreases, the transparency becomes high, and it becomes difficult to obtain an opal translucent appearance.
  • the holding time at the (maximum heat treatment temperature ⁇ 10 ° C.) is preferably less than 60 minutes, particularly less than 45 minutes.
  • the holding time near the maximum heat treatment temperature is too long, the manufacturing cost of the crystallized glass plate increases.
  • the crystal grain size is coarsened, the cloudiness becomes too strong and tends to be opaque.
  • a nucleation step may be provided to form crystal nuclei before the temperature is raised to the maximum heat treatment temperature.
  • the heat treatment step crystal growth step
  • the decorative film is formed on the back side, it is possible to stably produce a LAS-based crystallized glass plate in which the decorative film is not noticeable.
  • the heat treatment temperature in the nucleation step is preferably 700 to 950 ° C., 750 to 950 ° C., in particular 750 to 930 ° C.
  • the heat treatment time in the nucleation step is preferably within 7 hours, within 5 hours, particularly within 4 hours. If the heat treatment time is too long, the production cost of the LAS-based crystallized glass sheet tends to increase.
  • the nucleation step although it may be held only once at a predetermined temperature, it is preferable to hold a plurality of times from the viewpoint of appropriately obtaining a ⁇ -spodumene solid solution having an average crystal grain size of 100 to 1000 nm.
  • the nucleation step may be performed while raising the temperature without holding at a specific temperature.
  • the method for producing a LAS crystallized glass sheet of the present invention is characterized in that a ⁇ -spodumene solid solution having an average crystal grain size of 100 to 1000 nm is precipitated to obtain a LAS crystallized glass sheet.
  • a ⁇ -spodumene solid solution having an average crystal grain size of 100 to 1000 nm is precipitated to obtain a LAS crystallized glass sheet.
  • the average particle size of the ⁇ -spodumene solid solution is 100 to 1000 nm, preferably 150 to 900 nm, more preferably 200 to 900 nm.
  • the average particle diameter of the ⁇ -spodumene solid solution is too small, the scattering effect of visible light is reduced, the transparency is increased, and it is difficult to obtain an opal-like translucent appearance.
  • the average particle size of the ⁇ -spodumene solid solution is too large, the cloudiness becomes too strong and tends to be opaque.
  • "opal tone” means an appearance or color tone having a unique visible light scattering characteristically shown in opal in general. Such appearance and color tone can be obtained by scattering light emitted from an object being yellowish and scattering light being bluish by scattering of particles that are scatterers in a short wavelength region of visible light.
  • the lightness value L * of the L * a * b * display system according to JIS Z8729 is preferably 30 to 80, more preferably 30 in terms of a plate thickness of 3.0 mm. To 70, more preferably 30 to 60.
  • the lightness value L * is out of the above range, it becomes difficult to obtain an opal-like appearance excellent in aesthetic appearance.
  • the average transmittance at a wavelength of 400 to 800 nm is preferably 10 to 50%, more preferably 15 to 40%, still more preferably 18 to 50% in terms of 3.0 mm plate thickness. It is preferably 30%, and particularly preferably 20% or more when it is desired to transmit light of a blue or yellow indicator.
  • the average transmittance at a wavelength of 400 to 800 nm is too low, the amount of light passing through the top plate decreases too much, making it difficult to obtain an opal-like appearance. Moreover, it becomes difficult to visually recognize the light of the indicator provided in the back surface side of a top plate.
  • the average transmittance at a wavelength of 400 to 800 nm is too high, the light scattering property is reduced and the color tone becomes very thin, so it becomes difficult to conceal the internal structure of the cooker.
  • the average transmittance at a wavelength of 400 to 800 nm is restricted to the above range in terms of a plate thickness of 3.0 mm, even if a decorative film with high gloss is formed on the back surface of the top plate, the reflected light from this decorative film is Since the light is scattered moderately inside the top plate, the sharp gloss color is alleviated, and it becomes easy to obtain a high-class appearance having a soft tint.
  • the average transmittance at a wavelength of 800 to 1500 nm is preferably 50% or more, more preferably 60% or more, particularly preferably 70 to 90%, in terms of a plate thickness of 3.0 mm. It is.
  • the average transmittance at a wavelength of 800 to 1500 nm is too low, it becomes difficult to transmit heat rays, and it becomes difficult to heat the food to be cooked.
  • the average linear thermal expansion coefficient at 30 to 750 ° C. is preferably ⁇ 10 ⁇ 10 ⁇ 7 to + 30 ⁇ 10 ⁇ 7 / ° C., more preferably ⁇ 10 ⁇ 10 ⁇ 7. To + 20 ⁇ 10 ⁇ 7 / ° C.
  • the average linear thermal expansion coefficient at 30 to 750 ° C. is out of the above range, when a large temperature distribution occurs inside the top plate, there is a possibility that the expansion difference may cause division.
  • the crystallization degree of the LAS crystallized glass plate is preferably 70% or more, more preferably 80% or more, and still more preferably 85% or more. If the degree of crystallinity is too low, the thermal expansion coefficient is increased, and the thermal shock resistance tends to be reduced.
  • the LAS-based crystallized glass sheet according to the present invention has a composition by mass as follows: SiO 2 55-75%, Al 2 O 3 15-30%, Li 2 O 2-6%, MgO 0-3%, BaO 0 to 5%, ZnO 0 to less than 2%, TiO 2 1 to 6%, ZrO 2 0 to 4%, P 2 O 5 0 to 5%, Na 2 O 0 to 4%, K 2 O 0 to 4% It is preferable to contain
  • the reason for limiting the composition of the LAS-based crystallized glass plate is as follows.
  • % display means mass%.
  • SiO 2 is a glass network former and is a component constituting LAS-based crystals. However, when the content of SiO 2 decreases, the glass is likely to be devitrified during molding or slow cooling, and the chemical durability is also likely to be reduced. On the other hand, when the content of SiO 2 increases, the solubility of the glass batch is likely to decrease. Therefore, the content of SiO 2 is preferably 55 to 75%, more preferably 60 to 70%.
  • Al 2 O 3 is a component constituting the LAS-based crystal.
  • the content of Al 2 O 3 decreases, the meltability tends to decrease.
  • the content of Al 2 O 3 increases, the glass is likely to be devitrified during molding or slow cooling, and the chemical durability is also likely to be reduced. Therefore, the content of Al 2 O 3 is preferably 15 to 30%, more preferably 15 to 25%, and still more preferably more than 20 to 25%.
  • Li 2 O is a component constituting the LAS-based crystal. However, when the content of Li 2 O decreases, it becomes difficult to precipitate LAS crystals. On the other hand, when the content of Li 2 O is increased, the chemical durability tends to be reduced. Therefore, the content of Li 2 O is preferably 2 to 6%, more preferably 3 to 5%.
  • MgO is a component that facilitates the precipitation of LAS crystals.
  • the content of MgO is preferably 0 to 3%, more preferably 0 to 2%, still more preferably 0 to 1.5%, particularly preferably 0 to 1%.
  • BaO is a component that improves the meltability and prevents the occurrence of devitrification.
  • the content of BaO increases, it becomes difficult to precipitate LAS crystals.
  • the thermal expansion coefficient is increased, and the thermal characteristics are likely to be degraded. Therefore, the content of BaO is preferably 0 to 5%, more preferably 0 to 4%, still more preferably 0 to 3%, particularly preferably 1 to 2%.
  • ZnO is a component that enhances the meltability and facilitates the precipitation of LAS-based crystals.
  • the content of ZnO is preferably less than 2%, more preferably less than 1.5%, still more preferably less than 1%, particularly preferably less than 0.4%.
  • TiO 2 is a component that acts as a nucleation agent.
  • the content of TiO 2 decreases, the LAS-based crystal becomes coarse, and chemical durability tends to decrease.
  • the content of TiO 2 increases, the color tone becomes brown, and it becomes difficult to secure an opal-like appearance. Therefore, the content of TiO 2 is preferably 1 to 6%, more preferably 1 to 5%, still more preferably 1 to 4%.
  • ZrO 2 is a component that acts as a nucleation agent.
  • the content of ZrO 2 is preferably 0 to 4%, more preferably 0 to 3%, still more preferably 1 to 3%, and particularly preferably 2 to 3%.
  • the total amount of TiO 2 and ZrO 2 is preferably 2 to 6.9%, more preferably 3 to 6.5%, and still more preferably 3.5 to 5.5%.
  • the total amount of TiO 2 and ZrO 2 decreases, the LAS-based crystal becomes coarse, and chemical durability tends to decrease.
  • the solubility of the glass batch tends to be reduced, and the color tone becomes brown, making it difficult to secure an opal-like appearance.
  • P 2 O 5 is a component that significantly improves the low solubility of ZrO 2 .
  • the content of P 2 O 5 is preferably 0 to 5%, more preferably 0 to 3%, still more preferably 0 to 2%.
  • Na 2 O and K 2 O are components that enhance the solubility of the glass batch.
  • the content of Na 2 O and K 2 O is increased, the chemical durability may be significantly reduced.
  • the crystallinity decreases and the thermal expansion coefficient becomes too high. Therefore, the content of each of Na 2 O and K 2 O is preferably 0 to 4%, particularly 0 to 3%.
  • components such as CaO and PbO may be added up to 2% each. When these components are added, solubility, clarity, homogeneity, etc. can be enhanced. In order to further enhance the clarity, one or more of SnO 2 , Cl, SO 3 and Fe 2 O 3 may be added to a total amount of up to 0.5%.
  • the transparency of the LAS-based crystallized glass plate is high, if a decorative film having a high gloss is formed on the back surface (surface on the inner side of the cooker), light such as illumination is likely to be reflected to be dazzled.
  • the LAS-based crystallized glass plate according to the present invention has an opal-like and semi-transparent appearance, even if a highly glossy decorative film (for example, a TiN film) is formed, the reflected light is moderately scattered inside thereof Thus, it is possible to obtain a high-class appearance having a soft tint.
  • the LAS-based crystallized glass plate according to the present invention has an antiglare effect to appropriately suppress regular reflection light, it is possible to apply a decorative film having a high gloss. As a result, the design variation can be greatly expanded, and the appearance design can be improved more than before.
  • the decorative film may be a nitride of one metal selected from the group consisting of Ti, Nb, W and Mo, and a group consisting of Si, Ti, Al, Nb, W, Mo, Sn, Cr, Pt and Au. Containing nitrides of one selected metal, one alloy selected from the group consisting of stainless steel, hastelloy, inconel and nichrome, one alloy selected from the group consisting of stainless steel, hastelloy, inconel and nichrome Membranes are preferred.
  • the light shielding film made of TiN changes the nitrogen content in the film, the appearance changes steplessly from silver to gold, red, black and black in order of decreasing nitrogen, so it is easy to obtain a desired color tone and preferable .
  • the antioxidant film is selected from the group consisting of nitrides of one or more metals selected from the group consisting of Si, Ti, Al, Nb, Mo, Ta and Sn, or the group consisting of Si, Al and Ti.
  • a film containing an oxide of one kind of metal is preferable, and it can be formed on the upper layer of the light shielding film or can be formed between the LAS-based crystallized glass plate and the light shielding film.
  • the LAS-based crystallized glass plate of the present invention is a LAS-based crystallized glass plate on which a ⁇ -spodumene solid solution having an average crystal grain diameter of 100 to 1000 nm is precipitated, and in accordance with JIS Z8729 in terms of a plate thickness of 3.0 mm.
  • the lightness value L * of the L * a * b * display system is 30 to 80.
  • group crystallized glass board of this invention has already been described in the description column of the manufacturing method of the LAS type
  • Table 1 shows Examples (Sample Nos. 1 to 3) of the present invention and Comparative Examples (Sample Nos. 4 and 5).
  • the composition is, in mass%, SiO 2 65.6%, Al 2 O 3 22.2%, Li 2 O 3.7%, MgO 0.7%, BaO 1.2%, TiO 2 2.0 Raw materials of glass so that composition of 2 % ZrO 2 2.2% P 2 O 5 1.4% Na 2 O 0.4% K 2 O 0.3% SnO 2 0.3% Formulated to make a glass batch.
  • the glass batch was melted at 1600 ° C. for 23 hours, further heated to 1650 ° C., and melted for 1 hour. Then, after pouring out on a carbon stand, after forming in 5 mm thickness with a forming roller, furnace cooling was carried out with a 700 ° C slow cooling furnace.
  • the temperature is raised from room temperature to the maximum heat treatment temperature in the table at a temperature rising rate in the table, and then the crystallized glass plate is held by holding time in the table.
  • main crystal phase of each sample average crystal grain size, crystallinity, average linear thermal expansion coefficient, L * a * b * lightness value L * of display system, average transmittance, diffuse reflectance, appearance and antiglare property was evaluated. The results are shown in the table.
  • the main crystal phase and the degree of crystallinity were evaluated by X-ray diffraction according to a powder method using Rigaku RINT-2100.
  • ⁇ -S means ⁇ -spodumene solid solution
  • ⁇ -Q means ⁇ -quartz solid solution.
  • the average grain size is obtained by observing a part of the crystallized glass plate with an electron microscope, and specifically, it is in the range of 1 mm in depth from the outermost surface and 1 mm in depth to 1.5 mm in depth In the range of 1.5 mm in depth to 2 mm in depth, two 1-cm 2 observation points are extracted, and the crystal grain sizes of those are averaged.
  • the average transmittance and the diffuse reflectance are values measured using a spectrophotometer UV-3100 manufactured by Shimadzu Corporation.
  • the lightness value L * of the L * a * b * display system is a value measured by a method in accordance with JIS Z8729.
  • a mirror-polished product with a thickness of 3.0 mm was used as a sample for measuring the average transmittance, the diffuse reflectance, and the lightness value L * of the L * a * b * display system.
  • the incident angle was set to 8 degrees and the total reflectance was measured.
  • the average linear thermal expansion coefficient is a value measured by a differential detection type relative dilatometer in a temperature range of 30 to 750.degree. The appearance was evaluated by visual observation.
  • the antiglare property is obtained by forming a TiN film having a film thickness of 0.5 ⁇ m on one side of each sample by a sputtering method, and illuminating the side on which the TiN film is not formed with a 40 W lamp. The case where the user did not feel the hardness was evaluated as "good”, and the case where he felt the glare was evaluated as "defective".
  • the sample no. 1 to 3 have a heating rate of 400 to 800 ° C./hour, maximum heat treatment temperature of 1130 ° C., holding time of 5 to 30 minutes, main crystal phase is ⁇ -spodumene solid solution, average grain size of 400 to 900 nm Lightness value L * of 30.8 to 51.5, average transmittance at a wavelength of 400 to 800 nm of 12.5 to 26.3%, average transmittance of a wavelength of 800 to 1500 nm at 57.9 to 74.8%, The thermal expansion coefficient was + 11 ⁇ 10 ⁇ 7 / ° C., the appearance was opal, and the antiglare property was good. Therefore, sample no. It is considered that the production cost is low in addition to having a bright gloss but not being too noticeable.
  • sample no. In No. 4 the average crystal grain size was 1200 nm and the appearance was white and opaque because the heating rate was low. Moreover, sample No. In No. 5, because the temperature rise rate and the maximum heat treatment temperature were low, ⁇ -quartz solid solution was precipitated as the main crystal, the average crystal grain size became 70 nm, the transparency was high, and the antiglare property was poor.
  • Table 2 shows Examples of the present invention (Sample Nos. 6 to 16).
  • the composition is, in mass%, SiO 2 65.6%, Al 2 O 3 22.2%, Li 2 O 3.7%, MgO 0.7%, BaO 1.2%, TiO 2 2.0 Raw materials of glass so that composition of 2 % ZrO 2 2.2% P 2 O 5 1.4% Na 2 O 0.4% K 2 O 0.3% SnO 2 0.3% Formulated to make a glass batch.
  • the glass batch was melted at 1600 ° C. for 23 hours, further heated to 1650 ° C., and melted for 1 hour. Then, after pouring out on a carbon stand, after forming in 5 mm thickness with a forming roller, furnace cooling was carried out with a 700 ° C slow cooling furnace.
  • the temperature of the obtained crystalline glass plate is raised from room temperature at a temperature rising rate of 600 ° C./hour, and held at the heat treatment temperature of the first nucleation step in the table for the holding time in the table.
  • the temperature was raised at a temperature rising rate of 600 ° C./hour, and held at the heat treatment temperature in the second nucleation step for the holding time in the table.
  • the temperature is raised from the heat treatment temperature in the second nucleation step to the maximum heat treatment temperature in the table at a temperature rising rate in the table without lowering the temperature, and then held for a holding time in the table to obtain crystallized glass A board was made.
  • the main crystal phase and the degree of crystallinity were evaluated by X-ray diffraction according to a powder method using Rigaku RINT-2100.
  • the average grain size is determined by observing a part of the crystallized glass plate with an electron microscope.
  • the average transmittance and the diffuse reflectance are values measured using a spectrophotometer UV-3100 manufactured by Shimadzu Corporation.
  • the lightness value L * of the L * a * b * display system is a value measured by a method in accordance with JIS Z8729.
  • a mirror-polished product with a thickness of 3.0 mm was used as a sample for measuring the average transmittance, the diffuse reflectance, and the lightness value L * of the L * a * b * display system.
  • the incident angle was set to 8 degrees and the total reflectance was measured.
  • the average linear thermal expansion coefficient is a value measured by a differential detection type relative dilatometer in a temperature range of 30 to 750.degree.
  • the appearance was evaluated by visual observation. Specifically, when each sample was placed on a black background, bluish scattered light was observed, and a case where transmitted light was observed to be yellow was evaluated as opal tone.
  • the antiglare property is obtained by forming a TiN film having a film thickness of 0.5 ⁇ m on one side of each sample by a sputtering method, and illuminating the side on which the TiN film is not formed with a 40 W lamp. The case where the user did not feel the hardness was evaluated as "good", and the case where he felt the glare was evaluated as "defective".
  • sample No. 6 to 16 is a ⁇ -spodumene solid solution
  • the average crystal grain size is 200 to 800 nm
  • the lightness value L * is 36.9 to 72.8
  • the appearance is opal
  • the antiglare property is good. The Therefore, sample no. 6 to 16 are considered to have low production costs in addition to having a bright gloss but not being too noticeable.
  • the LAS-based crystallized glass plate according to the present invention has a bright color, and the decorative film is not noticeable even when the decorative film is formed on the back side, and the production cost is low. It is suitable as a top plate of a vessel, and also suitable as a top plate of a gas cooker. Furthermore, since the LAS-based crystallized glass plate according to the present invention transmits the light of various indicators, it can also be used for sensor components other than the top plate for a cooker.

Abstract

The present invention provides a method for producing a LAS-based crystallized glass plate containing, as a main crystal phase thereof, a β-spodumene solid solution, and is characterized by comprising: a step for preparing a crystalline glass plate; and a step for increasing the temperature of the crystalline glass plate to a maximum thermal treatment temperature of higher than 900°C at a temperature increase rate of 300-900°C/h, and causing a β-spodumene solid solution having an average crystal grain size of 100-1000 nm to be deposited to obtain the LAS-based crystallized glass plate.

Description

ＬＡＳ系結晶化ガラス板の製造方法及びＬＡＳ系結晶化ガラス板Method for producing LAS-based crystallized glass plate and LAS-based crystallized glass plate
　本発明は、Ｌｉ２Ｏ－Ａｌ２Ｏ３－ＳｉＯ２系（以下、ＬＡＳ系）結晶化ガラス板の製造方法及びＬＡＳ系結晶化ガラス板に関する。 The present invention relates to a method for producing a Li 2 O-Al 2 O 3 -SiO 2 -based (hereinafter, LAS-based) crystallized glass plate and a LAS-based crystallized glass plate.
　家庭用や業務用の調理器として、ガスコンロを採用したガス調理器だけでなく、ラジエントヒーターやハロゲンヒーターを採用した赤外線加熱調理器、電磁加熱調理器が使用されている。電磁加熱調理器に用いられるトッププレートには、高熱効率、安全性、熱衝撃性が要求されるため、電磁誘導加熱量が少なく、熱膨張係数が低い結晶化ガラス板が使用されている。 Not only gas cookers that use gas stoves, but also infrared heating cookers that use radiant heaters and halogen heaters, and electromagnetic heating cookers are used as cookers for home and business use. The top plate used in the electromagnetic heating cooker is required to have high thermal efficiency, safety and thermal shock resistance, and therefore, a crystallized glass plate having a small amount of electromagnetic induction heating and a low thermal expansion coefficient is used.
　ところで、トッププレートの役割は、加熱装置に対して、水、調味料、食品等が飛散する事態を防止することに加えて、加熱装置、配線等の調理器の内部構造を隠蔽して美観を高めることである。 By the way, in addition to preventing the situation where water, seasoning, food etc. scatter to the heating device, the role of the top plate hides the internal structure of the cooking device such as the heating device, wiring etc. It is to raise.
　トッププレートとして結晶化ガラス板を用いる場合、調理器の内部構造を隠蔽する方法として、主に２つの方法がある。第１の方法は、低膨張結晶化ガラス板自体を不透明又は半透明にする方法である。例えば、特許文献１には、着色剤によって濃色に着色された低膨張結晶化ガラスが開示されており、また特許文献２には、透明から不透明までの範囲の可視光線透過特性を有する低膨張結晶化ガラス板が開示されている。第２の方法は、透明な低膨張結晶化ガラス板の表面に印刷法を用いて装飾膜を形成し、この装飾膜によって調理器の内部構造を隠蔽する方法である。例えば、特許文献３には、裏面（調理面の反対側の面）に、貴金属と卑金属からなるラスター彩の装飾膜を設けた結晶化ガラス板が記載されている。 When using a crystallized glass plate as the top plate, there are mainly two methods for concealing the internal structure of the cooker. The first method is to make the low expansion crystallized glass plate itself opaque or translucent. For example, Patent Document 1 discloses a low expansion crystallized glass colored in a deep color by a coloring agent, and Patent Document 2 discloses a low expansion having visible light transmission characteristics ranging from transparent to opaque. A crystallized glass plate is disclosed. The second method is a method of forming a decorative film on the surface of a transparent low expansion crystallized glass plate using a printing method and concealing the internal structure of the cooker by the decorative film. For example, Patent Document 3 describes a crystallized glass plate provided with a decorative film of raster color consisting of a noble metal and a base metal on the back surface (surface opposite to the cooking surface).
　しかし、特許文献１に記載の結晶化ガラス板は、色調が濃いため、印加される電力量等を表示するインジケータの光を透過し難いという問題がある。すなわち特許文献１に記載の結晶化ガラス板を電磁加熱調理器のトッププレートに用いる場合、インジケータをトッププレートの裏面側に設けると、調理面側からは赤色のインジケータの光がかろうじて見えるだけになり、インジケータが赤色以外の色を発光しても、トッププレートが赤色以外の光（例えば青色や黄色）を全く透過しないために、そのような色の光を調理面側に表示することができない。そして、インジケータが赤色以外の色を発光する場合、その色の光を調理面側に表示させるためには、トッププレートの所定箇所に孔を開ける必要があり、その結果、トッププレートに欠けや割れが生じ易くなるという問題が生じる。更に、調理器用トッププレートの商品価値を高める要素の一つとして、外観意匠性が重視されつつあり、以前は濃色が主流であったが、最近は明るい色合いのものが好まれつつある。しかし、特許文献１の結晶化ガラス板は、色調が濃いため、消費者の最近の趣向に十分に応えることができない。 However, since the crystallized glass plate described in Patent Document 1 has a dark color tone, there is a problem that it is difficult to transmit the light of the indicator for displaying the amount of applied power and the like. That is, when the crystallized glass plate described in Patent Document 1 is used for the top plate of the electromagnetic heating cooker, when the indicator is provided on the back side of the top plate, the light of the red indicator is only barely visible from the cooking surface side Even when the indicator emits a color other than red, such color light can not be displayed on the cooking surface side because the top plate transmits no light other than red (for example, blue or yellow) at all. When the indicator emits a color other than red, it is necessary to open a hole at a predetermined location on the top plate in order to display the light of that color on the cooking surface side. As a result, the top plate is chipped or broken Is apt to occur. Furthermore, as one of the factors to enhance the commercial value of the cooker top plate, the appearance design is emphasized, and dark colors have been the mainstream in the past, but recently bright colors are being favored. However, since the crystallized glass plate of Patent Document 1 has a deep color tone, it can not sufficiently respond to the recent tastes of consumers.
　また、特許文献２に記載の結晶化ガラス板は、ガラス中に亜鉛尖晶石を析出させるため、ＺｎＯを２～５質量％含有しているが、このようにＺｎＯを多量に含有させると、熱処理時に異種結晶が析出し易くなる。その結果、半透明の色調を得ようとする場合に、色調が微妙に変化し易く、安定生産が困難になるという問題が生じる。 Further, the crystallized glass plate described in Patent Document 2 contains 2 to 5% by mass of ZnO in order to precipitate zinc spinel in the glass, but when a large amount of ZnO is thus contained, It becomes easy to precipitate foreign crystals during heat treatment. As a result, when it is intended to obtain a semi-transparent color tone, there is a problem that the color tone is likely to change delicately, making stable production difficult.
　更に、特許文献３に記載の結晶化ガラス板は、装飾膜の色調や光沢がそのままトッププレートの外観に反映されるため、トッププレートが目立ち過ぎてしまい、キッチン全体と調和せず、美観が損なわれることがある。また装飾膜の光沢が強過ぎると、照明等の光が反射して、調理する人が眩しく調理し難いという問題もある。 Furthermore, in the crystallized glass plate described in Patent Document 3, since the color tone and gloss of the decorative film are directly reflected on the appearance of the top plate, the top plate becomes too noticeable, and it is not in harmony with the entire kitchen and the appearance is impaired May be In addition, when the gloss of the decorative film is too strong, light such as illumination is reflected, and there is also a problem that a person who cooks is dazzling and difficult to cook.
特公平３－９０５６号公報Japanese Examined Patent Publication 3-9056 特開平５－２１３６２９号公報Unexamined-Japanese-Patent No. 5-213629 特公平７－１７４０９号公報Japanese Examined Patent 7-17409 特表２００１－５０１１６８号公報Japanese Patent Application Publication No. 2001-501168 特許第４３１５０７５号公報Patent No. 4315075
　このような事情から、特許文献４には、新しい外観と光学特性を有するトッププレートが開示されており、このトッププレートは、ＬＡＳ系結晶化ガラス板からなり、５０％以上の曇り度を呈し、結晶粒径が小さいβ－スポジュメン固溶体を含んでいる。しかし、結晶粒径が小さい結晶化ガラス板は、可視光が散乱し難く、透明性が高いため、色調が非常に薄く、調理器の内部構造を隠蔽し難い。 Under such circumstances, Patent Document 4 discloses a top plate having a new appearance and optical properties, and the top plate is made of LAS-based crystallized glass plate and exhibits a haze of 50% or more. It contains β-spodumene solid solution with a small crystal grain size. However, since a crystallized glass plate having a small crystal grain diameter hardly scatters visible light and has high transparency, the color tone is very thin and it is difficult to conceal the internal structure of the cooker.
　また、特許文献５には、平均結晶粒径１００～１０００ｎｍのβ－スポジュメン固溶体が析出し、半透明のＬＡＳ系結晶化ガラス板が開示されている。この結晶化ガラス板は、明るい色合いを有しながら、目立ち過ぎないため、各種インジケータの光を表示することが可能である。しかし、この結晶化ガラス板は、長時間の結晶化工程（少なくとも８時間の熱処理工程）を経ているため、製造コストが高騰してしまうという問題がある。 Patent Document 5 discloses a semitransparent LAS-based crystallized glass plate on which a β-spodumene solid solution having an average crystal grain size of 100 to 1000 nm is precipitated. Since this crystallized glass plate has a bright color and is not too noticeable, it is possible to display the light of various indicators. However, since this crystallized glass plate has been subjected to a long crystallization process (heat treatment process for at least 8 hours), there is a problem that the manufacturing cost is increased.
　本発明は、このような事情に鑑みなされたものであり、その技術的課題は、明るい色合いで調理器の内部構造を隠蔽し得ると共に、裏側に装飾膜が形成された場合でも、装飾膜が目立ち過ぎないＬＡＳ系結晶化ガラス板を効率良く生産する方法及びＬＡＳ系結晶化ガラス板を創案することである。 The present invention has been made in view of such circumstances, and the technical problem is that the internal structure of the cooker can be concealed with a bright color, and the decorative film is formed even when the decorative film is formed on the back side. A method of efficiently producing a LAS-based crystallized glass plate which is not remarkable and a method of creating a LAS-based crystallized glass plate.
　本発明者が鋭意検討した結果、結晶性ガラス板の熱処理条件を厳密に規制することにより、上記技術的課題を解決し得ることを見出し、本発明として提案するものである。すなわち、本発明のＬＡＳ系結晶化ガラス板の製造方法は、主結晶相としてβ－スポジュメン固溶体を含むＬＡＳ系結晶化ガラス板の製造方法において、結晶性ガラス板を用意する工程と、３００～９００℃／時間の昇温速度で９００℃超となる最高熱処理温度まで結晶性ガラス板を昇温すると共に、平均結晶粒径が１００～１０００ｎｍとなるβ－スポジュメン固溶体を析出させて、ＬＡＳ系結晶化ガラス板を得る工程と、を有することを特徴とする。 As a result of intensive investigations made by the present inventor, it is found out that the above technical problems can be solved by strictly controlling the heat treatment conditions of a crystalline glass plate, and proposed as the present invention. That is, in the method of producing a LAS-based crystallized glass sheet according to the present invention, a process of preparing a crystalline glass sheet in a method of producing a LAS-based crystallized glass sheet containing β-spodumene solid solution as a main crystalline phase; The temperature of the crystalline glass plate is raised to the maximum heat treatment temperature which exceeds 900 ° C. at a temperature rising rate of 100 ° C./hour, and a β-spodumene solid solution having an average crystal grain size of 100 to 1000 nm is precipitated to obtain LAS system crystallization Obtaining a glass plate.
　本発明のＬＡＳ系結晶化ガラス板の製造方法は、３００～９００℃／時間の昇温速度で９００℃超となる最高熱処理温度まで結晶性ガラス板を昇温すると共に、平均結晶粒径が１００～１０００ｎｍとなるβ－スポジュメン固溶体を析出させて、ＬＡＳ系結晶化ガラス板を得る工程を有する。このようにすれば、明るい色合いを有し、また裏側に装飾膜が形成された場合に、装飾膜が目立ち過ぎないＬＡＳ系結晶化ガラス板を効率良く生産することができる。つまりオパール調で半透明の外観を有する結晶化ガラス板を短時間で作製することができる。 According to the method for producing a LAS-based crystallized glass sheet of the present invention, the temperature of the crystalline glass sheet is raised to the maximum heat treatment temperature which exceeds 900 ° C. at a temperature rising rate of 300 to 900 ° C./hour. It has the process of depositing a β-spodumene solid solution of ̃1000 nm to obtain a LAS-based crystallized glass plate. In this way, it is possible to efficiently produce a LAS-based crystallized glass plate which has a bright color and in which the decorative film is not noticeable when the decorative film is formed on the back side. That is, a crystallized glass plate having an opal-like and translucent appearance can be produced in a short time.
　また、本発明のＬＡＳ系結晶化ガラス板の製造方法は、（最高熱処理温度±１０℃）における保持時間が６０分間未満であることが好ましい。このようにすれば、結晶化ガラス板の生産性を高めることができる。 Further, in the method for producing a LAS-based crystallized glass sheet of the present invention, the holding time at the (maximum heat treatment temperature ± 10 ° C.) is preferably less than 60 minutes. In this way, the productivity of the crystallized glass plate can be enhanced.
　また、本発明のＬＡＳ系結晶化ガラス板の製造方法は、平均結晶粒径が１５０～９００ｎｍとなるβ－スポジュメン固溶体を析出させることが好ましい。 Further, in the method of producing a LAS-based crystallized glass sheet of the present invention, it is preferable to precipitate a β-spodumene solid solution having an average crystal grain size of 150 to 900 nm.
　また、本発明のＬＡＳ系結晶化ガラス板の製造方法は、板厚３．０ｍｍ換算で、ＪＩＳ　Ｚ８７２９に準拠したＬ＊ａ＊ｂ＊表示系の明度値Ｌ＊が３０～８０となるＬＡＳ系結晶化ガラス板を得ることが好ましい。このようにすれば、美観に優れたオパール調の外観を得易くなる。 Further, the method of producing a LAS-based crystallized glass plate of the present invention is a LAS-based LAS-based glass plate in which the lightness value L * of the L * a * b * display system according to JIS Z8729 is 30 to 80 in terms of 3.0 mm thickness. It is preferable to obtain a crystallized glass plate. In this way, it is easy to obtain an opal-like appearance that is excellent in aesthetics.
　また、本発明のＬＡＳ系結晶化ガラス板の製造方法は、板厚３．０ｍｍ換算で、波長４００～８００ｎｍにおける平均透過率が１０～５０％になるＬＡＳ系結晶化ガラス板を得ることが好ましい。このようにすれば、トッププレートを透過する光量を適正化し易くなる。 In the method of producing a LAS-based crystallized glass plate of the present invention, it is preferable to obtain a LAS-based crystallized glass plate having an average transmittance of 10 to 50% at a wavelength of 400 to 800 nm in terms of a plate thickness of 3.0 mm. . In this way, the amount of light transmitted through the top plate can be easily made appropriate.
　また、本発明のＬＡＳ系結晶化ガラス板の製造方法は、板厚３．０ｍｍ換算で、波長８００～１５００ｎｍにおける平均透過率が５０％以上になるＬＡＳ系結晶化ガラス板を得ることが好ましい。このようすれば、調理時に熱線を透過し易くなる Further, in the method for producing a LAS-based crystallized glass plate of the present invention, it is preferable to obtain a LAS-based crystallized glass plate having an average transmittance of 50% or more at a wavelength of 800 to 1500 nm in terms of a plate thickness of 3.0 mm. In this way, it becomes easy to transmit the heat rays at the time of cooking
　また、本発明のＬＡＳ系結晶化ガラス板の製造方法は、３０～７５０℃における平均線熱膨張係数が－１０×１０－７～＋３０×１０－７／℃になるＬＡＳ系結晶化ガラス板を得ることが好ましい。このようすれば、トッププレート内部に大きな温度分布が生じた時でも、結晶化ガラス板が破損し難くなる。結果として、調理器用トッププレートに適用し易くなる。 Further, the method for producing a LAS-based crystallized glass plate of the present invention is a LAS-based crystallized glass plate having an average linear thermal expansion coefficient of -10 × 10 -7 to + 30 × 10 -7 / ° C. at 30 to 750 ° C. It is preferable to obtain. In this way, even when a large temperature distribution occurs inside the top plate, the crystallized glass plate is less likely to be damaged. As a result, it becomes easy to apply to the cooker top plate.
　また、本発明のＬＡＳ系結晶化ガラス板の製造方法は、ＬＡＳ系結晶化ガラス板中のＺｎＯの含有量が２質量％未満であることが好ましい。このようにすれば、熱処理時に異種結晶が析出し難くなる。 Moreover, as for the manufacturing method of the LAS type | system | group crystallized glass board of this invention, it is preferable that content of ZnO in a LAS type | system | group crystallized glass board is less than 2 mass%. In this way, it becomes difficult to precipitate foreign crystals during heat treatment.
　また、本発明のＬＡＳ系結晶化ガラス板の製造方法は、ＬＡＳ系結晶化ガラス板が、組成として、質量％で、ＳｉＯ２　５５～７５％、Ａｌ２Ｏ３　１５～３０％、Ｌｉ２Ｏ　２～６％、ＭｇＯ　０～３％、ＢａＯ　０～５％、ＺｎＯ　０～２％未満、ＴｉＯ２　１～６％、ＺｒＯ２　０～４％、Ｐ２Ｏ５　０～５％、Ｎａ２Ｏ　０～４％、Ｋ２Ｏ　０～４％を含有することが好ましい。 Further, according to the method of producing a LAS-based crystallized glass plate of the present invention, the LAS-based crystallized glass plate has a composition of 55 to 75% SiO 2 , 15 to 30% Al 2 O 3 , and Li 2 O 3 by mass. 2 to 6%, MgO 0 to 3%, BaO 0 to 5%, ZnO 0 to less than 2%, TiO 2 1 to 6%, ZrO 2 0 to 4%, P 2 O 5 0 to 5%, Na 2 O It is preferable to contain 0 to 4% and K 2 O 0 to 4%.
　また、本発明のＬＡＳ系結晶化ガラス板の製造方法は、ＬＡＳ系結晶化ガラス板を調理器用トッププレートに用いることが好ましい。 Moreover, it is preferable that the manufacturing method of the LAS type | system | group crystallized glass board of this invention uses a LAS type | system | group crystallized glass board for the top plate for cookers.
　本発明のＬＡＳ系結晶化ガラス板は、平均結晶粒径が１００～１０００ｎｍとなるβ－スポジュメン固溶体が析出したＬＡＳ系結晶化ガラス板であって、板厚３．０ｍｍ換算で、ＪＩＳ　Ｚ８７２９に準拠したＬ＊ａ＊ｂ＊表示系の明度値Ｌ＊が３０～８０であることを特徴とする。 The LAS-based crystallized glass plate of the present invention is a LAS-based crystallized glass plate on which a β-spodumene solid solution having an average crystal grain diameter of 100 to 1000 nm is precipitated, and in accordance with JIS Z8729 in terms of a plate thickness of 3.0 mm. The lightness value L * of the L * a * b * display system is 30 to 80.
　また、本発明のＬＡＳ系結晶化ガラス板は、板厚３．０ｍｍ換算で、波長４００～８００ｎｍにおける平均透過率が１０～５０％であることが好ましい。 The LAS-based crystallized glass plate of the present invention preferably has an average transmittance of 10 to 50% at a wavelength of 400 to 800 nm in terms of a plate thickness of 3.0 mm.
　また、本発明のＬＡＳ系結晶化ガラス板は、板厚３．０ｍｍ換算で、波長８００～１５００ｎｍにおける平均透過率が５０％以上であることが好ましい。 The LAS-based crystallized glass plate of the present invention preferably has an average transmittance of 50% or more at a wavelength of 800 to 1500 nm in terms of a plate thickness of 3.0 mm.
　また、本発明のＬＡＳ系結晶化ガラス板は、３０～７５０℃における平均線熱膨張係数が－１０×１０－７～＋３０×１０－７／℃であことが好ましい。 The LAS-based crystallized glass sheet of the present invention preferably has an average linear thermal expansion coefficient at 30 to 750 ° C. of −10 × 10 −7 to + 30 × 10 −7 / ° C.
　また、本発明のＬＡＳ系結晶化ガラス板は、組成として、質量％で、ＳｉＯ２　５５～７５％、Ａｌ２Ｏ３　１５～３０％、Ｌｉ２Ｏ　２～６％、ＭｇＯ　０～３％、ＢａＯ　０～５％、ＺｎＯ　０～２％未満、ＴｉＯ２　１～６％、ＺｒＯ２　０～４％、Ｐ２Ｏ５　０～５％、Ｎａ２Ｏ　０～４％、Ｋ２Ｏ　０～４％を含有することが好ましい。 In the LAS-based crystallized glass plate of the present invention, the composition is, by mass%, 55 to 75% SiO 2 , 15 to 30% Al 2 O 3, 2 to 6% Li 2 O, and 0 to 3% MgO. BaO 0 to 5%, ZnO 0 to less than 2%, TiO 2 1 to 6%, ZrO 2 0 to 4%, P 2 O 5 0 to 5%, Na 2 O 0 to 4%, K 2 O 0 to 4 It is preferable to contain%.
　また、本発明のＬＡＳ系結晶化ガラス板は、組成として、質量％で、ＳｉＯ２　６０～７０％、Ａｌ２Ｏ３　２０超～３０％、Ｌｉ２Ｏ　３～５％、ＭｇＯ　０～１％、ＢａＯ　１～２％、ＺｎＯ　０～０．４％未満、ＴｉＯ２　１～４％、ＺｒＯ２　２～３％、Ｐ２Ｏ５　０～２％、Ｎａ２Ｏ　０～４％、Ｋ２Ｏ　０～４％を含有することが好ましい。 Further, the LAS-based crystallized glass plate of the present invention has a composition as SiO 2 60-70%, Al 2 O 3 20 over 30%, Li 2 O 3-5%, MgO 0-1% by mass. , BaO 1 to 2%, ZnO 0 to less than 0.4%, TiO 2 1 to 4%, ZrO 2 2 to 3%, P 2 O 5 0 to 2%, Na 2 O 0 to 4%, K 2 O It is preferable to contain 0 to 4%.
　本発明のＬＡＳ系結晶化ガラス板の製造方法は、結晶性ガラス板を用意する工程を有する。結晶性ガラス板は、公知の方法で作製することが可能である。例えば、所定の組成になるようにガラス原料を調合し、得られたガラスバッチを１５５０～１７５０℃の温度で溶融した後、板状に成形することにより、結晶性ガラス板を作製することができる。なお、成形方法として、フロート法、ロールアウト法、プレス法等があるが、結晶性ガラス板の表面平滑性を高めたい場合は、フロート法が好ましく、大型の結晶性ガラス板を作製したい場合は、ロールアウト法が好ましく、成形時の失透を抑制したい場合は、プレス法が好ましい。 The method for producing a LAS-based crystallized glass sheet of the present invention comprises the step of preparing a crystalline glass sheet. The crystalline glass plate can be produced by a known method. For example, a crystalline glass plate can be produced by preparing a glass material so as to have a predetermined composition, melting the obtained glass batch at a temperature of 1550 to 1750 ° C., and then forming it into a plate shape. . As a forming method, there are a float method, a roll out method, a pressing method and the like, but when it is desired to improve the surface smoothness of a crystalline glass plate, the float method is preferable, and when producing a large crystalline glass plate The roll-out method is preferable, and when it is desired to suppress the devitrification at the time of molding, the press method is preferable.
　本発明のＬＡＳ系結晶化ガラス板の製造方法は、９００℃超（好ましくは１０００～１２３０℃）となる最高熱処理温度まで結晶性ガラス板を昇温することを特徴とする。最高熱処理温度が低過ぎると、β－石英固溶体が析出し易くなるため、透明性が高くなり、オパール調で半透明の外観を得難くなる。 The method for producing a LAS-based crystallized glass sheet of the present invention is characterized in that the temperature of the crystalline glass sheet is raised to the maximum heat treatment temperature which exceeds 900 ° C. (preferably 1000 to 1230 ° C.). When the maximum heat treatment temperature is too low, the β-quartz solid solution is easily precipitated, so that the transparency becomes high, and it becomes difficult to obtain an opal-like translucent appearance.
　本発明のＬＡＳ系結晶化ガラス板の製造方法は、３００～９００℃／時間の昇温速度（好ましくは３５０～８５０℃／時間の昇温速度）で結晶性ガラス板を昇温することを特徴とする。昇温速度が低くなると、結晶粒径が粗大化するため、白濁が強くなり過ぎて、不透明になり易い。一方、昇温速度が高くなると、結晶粒径が微細化するため、可視光の散乱効果が低減して、透明性が高くなり、オパール調で半透明の外観を得難くなる。 The method for producing a LAS-based crystallized glass sheet of the present invention is characterized in that the temperature of the crystalline glass sheet is raised at a temperature rising rate of 300 to 900 ° C./hour (preferably, a temperature rising rate of 350 to 850 ° C./hour). I assume. When the heating rate is low, the crystal grain size is coarsened, so the cloudiness becomes too strong and it tends to be opaque. On the other hand, when the temperature rising rate becomes high, the crystal grain size becomes finer, the scattering effect of visible light decreases, the transparency becomes high, and it becomes difficult to obtain an opal translucent appearance.
　本発明のＬＡＳ系結晶化ガラス板の製造方法は、（最高熱処理温度±１０℃）における保持時間が６０分間未満、特に４５分間未満であることが好ましい。最高熱処理温度付近での保持時間が長過ぎると、結晶化ガラス板の製造コストが上昇する。また結晶粒径が粗大化するため、白濁が強くなり過ぎて、不透明になり易い。 In the method for producing a LAS-based crystallized glass sheet of the present invention, the holding time at the (maximum heat treatment temperature ± 10 ° C.) is preferably less than 60 minutes, particularly less than 45 minutes. When the holding time near the maximum heat treatment temperature is too long, the manufacturing cost of the crystallized glass plate increases. In addition, since the crystal grain size is coarsened, the cloudiness becomes too strong and tends to be opaque.
　本発明のＬＡＳ系結晶化ガラス板の製造方法では、最高熱処理温度に昇温する前に、結晶核を形成させるための核形成工程を設けてもよい。このようにすれば、最高熱処理温度まで昇温する熱処理工程（結晶成長工程）で、平均結晶粒径が１００～１０００ｎｍとなるβ－スポジュメン固溶体を析出させ易くなる。結果として、明るい色合いを有し、また裏側に装飾膜が形成された場合に、装飾膜が目立ち過ぎないＬＡＳ系結晶化ガラス板を安定的に生産することができる。核形成工程における熱処理温度は、好ましくは７００～９５０℃、７５０～９５０℃、特に７５０～９３０℃である。熱処理温度が上記範囲外になると、核形成を適正に行うことが困難になる。また、核形成工程における熱処理時間は、好ましくは７時間以内、５時間以内、特に４時間以内が好ましい。熱処理時間が長過ぎると、ＬＡＳ系結晶化ガラス板の生産コストが上昇し易くなる。なお、核形成工程では、所定の温度で一度だけ保持してもよいが、平均結晶粒径が１００～１０００ｎｍとなるβ－スポジュメン固溶体を適正に得る観点から、複数回保持することが好ましい。また、核形成工程は、特定の温度に保持することなく、昇温しながら行ってもよい。 In the method of producing a LAS-based crystallized glass sheet of the present invention, a nucleation step may be provided to form crystal nuclei before the temperature is raised to the maximum heat treatment temperature. In this way, in the heat treatment step (crystal growth step) of raising the temperature to the maximum heat treatment temperature, it becomes easy to precipitate the β-spodumene solid solution having an average crystal grain size of 100 to 1000 nm. As a result, when the decorative film is formed on the back side, it is possible to stably produce a LAS-based crystallized glass plate in which the decorative film is not noticeable. The heat treatment temperature in the nucleation step is preferably 700 to 950 ° C., 750 to 950 ° C., in particular 750 to 930 ° C. When the heat treatment temperature is out of the above range, it is difficult to properly perform nucleation. The heat treatment time in the nucleation step is preferably within 7 hours, within 5 hours, particularly within 4 hours. If the heat treatment time is too long, the production cost of the LAS-based crystallized glass sheet tends to increase. In the nucleation step, although it may be held only once at a predetermined temperature, it is preferable to hold a plurality of times from the viewpoint of appropriately obtaining a β-spodumene solid solution having an average crystal grain size of 100 to 1000 nm. In addition, the nucleation step may be performed while raising the temperature without holding at a specific temperature.
　本発明のＬＡＳ系結晶化ガラス板の製造方法は、平均結晶粒径が１００～１０００ｎｍとなるβ－スポジュメン固溶体を析出させて、ＬＡＳ系結晶化ガラス板を得ることを特徴とする。平均結晶粒径が１００～１０００ｎｍとなるβ－スポジュメン固溶体を析出させると、明るく柔らかな色合いの上品な外観を得ることができる。更に可視光を適正に散乱させることが可能になり、優れた防眩効果を享受することができる。 The method for producing a LAS crystallized glass sheet of the present invention is characterized in that a β-spodumene solid solution having an average crystal grain size of 100 to 1000 nm is precipitated to obtain a LAS crystallized glass sheet. By depositing a β-spodumene solid solution having an average crystal grain size of 100 to 1000 nm, it is possible to obtain an elegant appearance with a bright and soft color. Furthermore, it becomes possible to properly scatter visible light, and an excellent antiglare effect can be enjoyed.
　β－スポジュメン固溶体の平均粒子径は１００～１０００ｎｍであり、好ましくは１５０～９００ｎｍ、より好ましくは２００～９００ｎｍである。β－スポジュメン固溶体の平均粒子径が小さ過ぎると、可視光の散乱効果が低減して、透明性が高くなり、オパール調で半透明の外観を得難くなる。一方、β－スポジュメン固溶体の平均粒子径が大き過ぎると、白濁が強くなり過ぎて、不透明になり易い。ここで、「オパール調」とは、一般にオパールに特徴的に示される特異な可視光の散乱を有する外観や色調を意味している。このような外観や色調は、散乱体である粒子が可視光の短波長領域を散乱することで、物体の透過光が黄色みを帯び、散乱光が青みを帯びることで得られるものである。 The average particle size of the β-spodumene solid solution is 100 to 1000 nm, preferably 150 to 900 nm, more preferably 200 to 900 nm. When the average particle diameter of the β-spodumene solid solution is too small, the scattering effect of visible light is reduced, the transparency is increased, and it is difficult to obtain an opal-like translucent appearance. On the other hand, when the average particle size of the β-spodumene solid solution is too large, the cloudiness becomes too strong and tends to be opaque. Here, "opal tone" means an appearance or color tone having a unique visible light scattering characteristically shown in opal in general. Such appearance and color tone can be obtained by scattering light emitted from an object being yellowish and scattering light being bluish by scattering of particles that are scatterers in a short wavelength region of visible light.
　本発明に係るＬＡＳ系結晶化ガラス板において、板厚３．０ｍｍ換算で、ＪＩＳ　Ｚ８７２９に準拠したＬ＊ａ＊ｂ＊表示系の明度値Ｌ＊は、好ましくは３０～８０、より好ましくは３０～７０、更に好ましくは３０～６０である。明度値Ｌ＊が上記範囲外になると、美観に優れたオパール調の外観を得難くなる。 In the LAS-based crystallized glass plate according to the present invention, the lightness value L * of the L * a * b * display system according to JIS Z8729 is preferably 30 to 80, more preferably 30 in terms of a plate thickness of 3.0 mm. To 70, more preferably 30 to 60. When the lightness value L * is out of the above range, it becomes difficult to obtain an opal-like appearance excellent in aesthetic appearance.
　本発明に係るＬＡＳ系結晶化ガラス板において、板厚３．０ｍｍ換算で、波長４００～８００ｎｍの平均透過率は、好ましくは１０～５０％、より好ましくは１５～４０％、更に好ましくは１８～３０％であり、特に青色や黄色のインジケータの光を透過させたい場合は２０％以上が好ましい。波長４００～８００ｎｍにおける平均透過率が低過ぎると、トッププレートを透過する光量が減少し過ぎて、オパール調の外観を得難くなる。またトッププレートの裏面側に設けられるインジケータの光を視認し難くなる。一方、波長４００～８００ｎｍにおける平均透過率が高過ぎると、光散乱性が低下して、色調が非常に薄くなるため、調理器の内部構造を隠蔽し難くなる。なお、板厚３．０ｍｍ換算で、波長４００～８００ｎｍにおける平均透過率を上記範囲に規制すると、トッププレートの裏面に光沢の強い装飾膜を形成しても、この装飾膜からの反射光が、トッププレート内部で程良く散乱されるため、鋭い光沢色が緩和されて、柔らかい色合いを有する高級感のある外観を得易くなる。 In the LAS-based crystallized glass plate according to the present invention, the average transmittance at a wavelength of 400 to 800 nm is preferably 10 to 50%, more preferably 15 to 40%, still more preferably 18 to 50% in terms of 3.0 mm plate thickness. It is preferably 30%, and particularly preferably 20% or more when it is desired to transmit light of a blue or yellow indicator. When the average transmittance at a wavelength of 400 to 800 nm is too low, the amount of light passing through the top plate decreases too much, making it difficult to obtain an opal-like appearance. Moreover, it becomes difficult to visually recognize the light of the indicator provided in the back surface side of a top plate. On the other hand, when the average transmittance at a wavelength of 400 to 800 nm is too high, the light scattering property is reduced and the color tone becomes very thin, so it becomes difficult to conceal the internal structure of the cooker. If the average transmittance at a wavelength of 400 to 800 nm is restricted to the above range in terms of a plate thickness of 3.0 mm, even if a decorative film with high gloss is formed on the back surface of the top plate, the reflected light from this decorative film is Since the light is scattered moderately inside the top plate, the sharp gloss color is alleviated, and it becomes easy to obtain a high-class appearance having a soft tint.
　本発明に係るＬＡＳ系結晶化ガラス板において、板厚３．０ｍｍ換算で、波長８００～１５００ｎｍの平均透過率は、好ましくは５０％以上、より好ましくは６０％以上、特に好ましくは７０～９０％である。波長８００～１５００ｎｍの平均透過率が低過ぎると、熱線を透過し難くなるため、被調理物を加熱し難くなる。 In the LAS-based crystallized glass plate according to the present invention, the average transmittance at a wavelength of 800 to 1500 nm is preferably 50% or more, more preferably 60% or more, particularly preferably 70 to 90%, in terms of a plate thickness of 3.0 mm. It is. When the average transmittance at a wavelength of 800 to 1500 nm is too low, it becomes difficult to transmit heat rays, and it becomes difficult to heat the food to be cooked.
　調理器用トッププレートに使用される結晶化ガラス板は、加熱、冷却が繰り返されるため、熱膨張係数が低く、耐熱衝撃性に優れていることが要求される。本発明に係るＬＡＳ系結晶化ガラス板において、３０～７５０℃における平均線熱膨張係数は、好ましくは－１０×１０－７～＋３０×１０－７／℃、より好ましくは－１０×１０－７～＋２０×１０－７／℃である。３０～７５０℃における平均線熱膨張係数が上記範囲外になると、トッププレート内部に大きな温度分布が生じた時に、膨張差で割れる虞がある。 A crystallized glass plate used for a cooker top plate is required to have a low thermal expansion coefficient and excellent thermal shock resistance because heating and cooling are repeated. In the LAS crystallized glass sheet according to the present invention, the average linear thermal expansion coefficient at 30 to 750 ° C. is preferably −10 × 10 −7 to + 30 × 10 −7 / ° C., more preferably −10 × 10 −7. To + 20 × 10 −7 / ° C. When the average linear thermal expansion coefficient at 30 to 750 ° C. is out of the above range, when a large temperature distribution occurs inside the top plate, there is a possibility that the expansion difference may cause division.
　本発明に係るＬＡＳ系結晶化ガラス板において、ＬＡＳ系結晶化ガラス板の結晶化度は、好ましくは７０％以上、より好ましくは８０％以上、更に好ましくは８５％以上である。結晶化度が低過ぎると、熱膨張係数が上昇して、耐熱衝撃性が低下し易くなる。 In the LAS crystallized glass plate according to the present invention, the crystallization degree of the LAS crystallized glass plate is preferably 70% or more, more preferably 80% or more, and still more preferably 85% or more. If the degree of crystallinity is too low, the thermal expansion coefficient is increased, and the thermal shock resistance tends to be reduced.
　本発明に係るＬＡＳ系結晶化ガラス板は、組成として、質量％で、ＳｉＯ２　５５～７５％、Ａｌ２Ｏ３　１５～３０％、Ｌｉ２Ｏ　２～６％、ＭｇＯ　０～３％、ＢａＯ　０～５％、ＺｎＯ　０～２％未満、ＴｉＯ２　１～６％、ＺｒＯ２　０～４％、Ｐ２Ｏ５　０～５％、Ｎａ２Ｏ　０～４％、Ｋ２Ｏ　０～４％を含有することが好ましい。ＬＡＳ系結晶化ガラス板の組成を限定した理由は下記の通りである。なお、各成分の含有範囲の説明において、％表示は、質量％を意味する。 The LAS-based crystallized glass sheet according to the present invention has a composition by mass as follows: SiO 2 55-75%, Al 2 O 3 15-30%, Li 2 O 2-6%, MgO 0-3%, BaO 0 to 5%, ZnO 0 to less than 2%, TiO 2 1 to 6%, ZrO 2 0 to 4%, P 2 O 5 0 to 5%, Na 2 O 0 to 4%, K 2 O 0 to 4% It is preferable to contain The reason for limiting the composition of the LAS-based crystallized glass plate is as follows. In addition, in description of the content range of each component,% display means mass%.
　ＳｉＯ２は、ガラスのネットワークフォーマーであると共に、ＬＡＳ系結晶を構成する成分である。しかし、ＳｉＯ２の含有量が少なくなると、成形や徐冷時にガラスが失透し易くなり、化学的耐久性も低下し易くなる。一方、ＳｉＯ２の含有量が多くなると、ガラスバッチの溶解性が低下し易くなる。よって、ＳｉＯ２の含有量は、好ましくは５５～７５％、より好ましくは６０～７０％である。 SiO 2 is a glass network former and is a component constituting LAS-based crystals. However, when the content of SiO 2 decreases, the glass is likely to be devitrified during molding or slow cooling, and the chemical durability is also likely to be reduced. On the other hand, when the content of SiO 2 increases, the solubility of the glass batch is likely to decrease. Therefore, the content of SiO 2 is preferably 55 to 75%, more preferably 60 to 70%.
　Ａｌ２Ｏ３は、ＬＡＳ系結晶を構成する成分である。しかし、Ａｌ２Ｏ３の含有量が少なくなると、溶融性が低下し易くなる。一方、Ａｌ２Ｏ３の含有量が多くなると、成形や徐冷時にガラスが失透し易くなり、化学的耐久性も低下し易くなる。よって、Ａｌ２Ｏ３の含有量は、好ましくは１５～３０％、より好ましくは１５～２５％、更に好ましくは２０超～２５％である。 Al 2 O 3 is a component constituting the LAS-based crystal. However, when the content of Al 2 O 3 decreases, the meltability tends to decrease. On the other hand, when the content of Al 2 O 3 increases, the glass is likely to be devitrified during molding or slow cooling, and the chemical durability is also likely to be reduced. Therefore, the content of Al 2 O 3 is preferably 15 to 30%, more preferably 15 to 25%, and still more preferably more than 20 to 25%.
　Ｌｉ２Ｏは、ＬＡＳ系結晶を構成する成分である。しかし、Ｌｉ２Ｏの含有量が少なくなると、ＬＡＳ系結晶が析出し難くなる。一方、Ｌｉ２Ｏの含有量が多くなると、化学的耐久性が低下し易くなる。よって、Ｌｉ２Ｏの含有量は、好ましくは２～６％、より好ましくは３～５％である。 Li 2 O is a component constituting the LAS-based crystal. However, when the content of Li 2 O decreases, it becomes difficult to precipitate LAS crystals. On the other hand, when the content of Li 2 O is increased, the chemical durability tends to be reduced. Therefore, the content of Li 2 O is preferably 2 to 6%, more preferably 3 to 5%.
　ＭｇＯは、ＬＡＳ系結晶を析出し易くする成分である。しかし、ＭｇＯの含有量が多くなると、熱膨張係数が高くなり過ぎる。よって、ＭｇＯの含有量は、好ましくは０～３％、より好ましくは０～２％、更に好ましくは０～１．５％、特に好ましくは０～１％である。 MgO is a component that facilitates the precipitation of LAS crystals. However, when the content of MgO is increased, the thermal expansion coefficient becomes too high. Therefore, the content of MgO is preferably 0 to 3%, more preferably 0 to 2%, still more preferably 0 to 1.5%, particularly preferably 0 to 1%.
　ＢａＯは、溶融性を高めると共に、失透ブツの発生を防止する成分である。しかし、ＢａＯの含有量が多くなると、ＬＡＳ系結晶が析出し難くなる。また熱膨張係数が高くなって、熱的特性が低下し易くなる。よって、ＢａＯの含有量は、好ましくは０～５％、より好ましくは０～４％、更に好ましくは０～３％、特に好ましくは１～２％である。 BaO is a component that improves the meltability and prevents the occurrence of devitrification. However, when the content of BaO increases, it becomes difficult to precipitate LAS crystals. In addition, the thermal expansion coefficient is increased, and the thermal characteristics are likely to be degraded. Therefore, the content of BaO is preferably 0 to 5%, more preferably 0 to 4%, still more preferably 0 to 3%, particularly preferably 1 to 2%.
　ＺｎＯは、溶融性を高めると共に、ＬＡＳ系結晶を析出させ易くする成分である。しかし、ＺｎＯの含有量が多くなると、成形時にガラスが失透し易くなり、徐冷時や結晶化時に異種結晶が析出し易くなる。よって、ＺｎＯの含有量は、好ましくは２％未満、より好ましくは１．５％未満、更に好ましくは１％未満、特に好ましくは０．４％未満である。 ZnO is a component that enhances the meltability and facilitates the precipitation of LAS-based crystals. However, when the content of ZnO is increased, the glass is likely to be devitrified at the time of molding, and heterogeneous crystals are easily precipitated at the time of slow cooling or crystallization. Therefore, the content of ZnO is preferably less than 2%, more preferably less than 1.5%, still more preferably less than 1%, particularly preferably less than 0.4%.
　ＴｉＯ２は、核形成剤として作用する成分である。ＴｉＯ２の含有量が少なくなると、ＬＡＳ系結晶が粗大になって、化学的耐久性が低下し易くなる。一方、ＴｉＯ２の含有量が多くなると、色調が褐色になって、オパール調の外観を確保し難くなる。よって、ＴｉＯ２の含有量は、好ましくは１～６％、より好ましくは１～５％、更に好ましくは１～４％である。 TiO 2 is a component that acts as a nucleation agent. When the content of TiO 2 decreases, the LAS-based crystal becomes coarse, and chemical durability tends to decrease. On the other hand, when the content of TiO 2 increases, the color tone becomes brown, and it becomes difficult to secure an opal-like appearance. Therefore, the content of TiO 2 is preferably 1 to 6%, more preferably 1 to 5%, still more preferably 1 to 4%.
　ＺｒＯ２は、核形成剤として作用する成分である。ＺｒＯ２の含有量が多くなると、成形や徐冷時にガラスが失透し易くなる。よって、ＺｒＯ２の含有量は、好ましくは０～４％、より好ましくは０～３％、更に好ましくは１～３％、特に好ましくは２～３％である。 ZrO 2 is a component that acts as a nucleation agent. When the content of ZrO 2 increases, the glass is likely to be devitrified during molding or slow cooling. Therefore, the content of ZrO 2 is preferably 0 to 4%, more preferably 0 to 3%, still more preferably 1 to 3%, and particularly preferably 2 to 3%.
　ＴｉＯ２とＺｒＯ２の合量は、好ましくは２～６．９％、より好ましくは３～６．５％、更に好ましくは３．５～５．５％である。ＴｉＯ２とＺｒＯ２の合量が少なくなると、ＬＡＳ系結晶が粗大になって、化学的耐久性が低下し易くなる。一方、ＴｉＯ２とＺｒＯ２の合量が多くなると、ガラスバッチの溶解性が低下し易くなり、また色調が褐色になって、オパール調の外観を確保し難くなる。 The total amount of TiO 2 and ZrO 2 is preferably 2 to 6.9%, more preferably 3 to 6.5%, and still more preferably 3.5 to 5.5%. When the total amount of TiO 2 and ZrO 2 decreases, the LAS-based crystal becomes coarse, and chemical durability tends to decrease. On the other hand, when the total amount of TiO 2 and ZrO 2 is increased, the solubility of the glass batch tends to be reduced, and the color tone becomes brown, making it difficult to secure an opal-like appearance.
　Ｐ２Ｏ５は、ＺｒＯ２の難溶解性を著しく改善する成分である。Ｐ２Ｏ５の含有量が多くなると、ガラスが分相し易くなる。よって、Ｐ２Ｏ５の含有量は、好ましくは０～５％、より好ましくは０～３％、更に好ましくは０～２％である。 P 2 O 5 is a component that significantly improves the low solubility of ZrO 2 . When the content of P 2 O 5 is increased, the glass is likely to be separated. Therefore, the content of P 2 O 5 is preferably 0 to 5%, more preferably 0 to 3%, still more preferably 0 to 2%.
　Ｎａ２ＯとＫ２Ｏは、ガラスバッチの溶解性を高める成分である。しかし、Ｎａ２ＯとＫ２Ｏの含有量が多くなると、化学的耐久性が大幅に低下する虞がある。また結晶性が低下したり、熱膨張係数が高くなり過ぎる。よって、Ｎａ２ＯとＫ２Ｏの含有量は、それぞれ０～４％、特に０～３％が好ましい。 Na 2 O and K 2 O are components that enhance the solubility of the glass batch. However, when the content of Na 2 O and K 2 O is increased, the chemical durability may be significantly reduced. In addition, the crystallinity decreases and the thermal expansion coefficient becomes too high. Therefore, the content of each of Na 2 O and K 2 O is preferably 0 to 4%, particularly 0 to 3%.
　上記成分以外にも、ＣａＯ、ＰｂＯ等の成分を各々２％まで添加してもよい。これらの成分を添加すると、溶解性、清澄性、均質性等を高めることができる。更に清澄性を高めるために、ＳｎＯ２、Ｃｌ、ＳＯ３、Ｆｅ２Ｏ３の１種又は２種以上を合量で０．５％まで添加してもよい。 In addition to the above components, components such as CaO and PbO may be added up to 2% each. When these components are added, solubility, clarity, homogeneity, etc. can be enhanced. In order to further enhance the clarity, one or more of SnO 2 , Cl, SO 3 and Fe 2 O 3 may be added to a total amount of up to 0.5%.
　ＬＡＳ系結晶化ガラス板の透明性が高い場合、その裏面（調理器の内部側の面）に光沢の強い装飾膜を形成すると、照明等の光が反射して眩しくなり易い。一方、本発明に係るＬＡＳ系結晶化ガラス板は、オパール調で半透明の外観を有するため、光沢の強い装飾膜（例えばＴｉＮ膜）を形成しても、その内部で反射光が程良く散乱して、柔らかい色合いを有する高級感のある外観を得ることができる。つまり本発明に係るＬＡＳ系結晶化ガラス板は、正反射光を適度に抑制する防眩効果を有するため、光沢の強い装飾膜を適用することが可能である。その結果、デザインバリエーションが大幅に拡大されて、従来よりも外観意匠性を高めることができる。 When the transparency of the LAS-based crystallized glass plate is high, if a decorative film having a high gloss is formed on the back surface (surface on the inner side of the cooker), light such as illumination is likely to be reflected to be dazzled. On the other hand, since the LAS-based crystallized glass plate according to the present invention has an opal-like and semi-transparent appearance, even if a highly glossy decorative film (for example, a TiN film) is formed, the reflected light is moderately scattered inside thereof Thus, it is possible to obtain a high-class appearance having a soft tint. That is, since the LAS-based crystallized glass plate according to the present invention has an antiglare effect to appropriately suppress regular reflection light, it is possible to apply a decorative film having a high gloss. As a result, the design variation can be greatly expanded, and the appearance design can be improved more than before.
　装飾膜としては、Ｔｉ、Ｎｂ、Ｗ及びＭｏからなる群より選ばれた１種の金属の窒化物、Ｓｉ、Ｔｉ、Ａｌ、Ｎｂ、Ｗ、Ｍｏ、Ｓｎ、Ｃｒ、Ｐｔ及びＡｕからなる群より選ばれた１種の金属、ステンレス、ハステロイ、インコネル及びニクロムからなる群より選ばれた１種の合金、ステンレス、ハステロイ、インコネル及びニクロムからなる群より選ばれた１種の合金の窒化物を含む膜が好適である。特にＴｉＮからなる遮光膜は、膜中の窒素含有量を変化させると、窒素の少ない順に、銀色、金色、赤黒色、黒色と無段階的に外観が変化するため、所望の色調を得易く好ましい。 The decorative film may be a nitride of one metal selected from the group consisting of Ti, Nb, W and Mo, and a group consisting of Si, Ti, Al, Nb, W, Mo, Sn, Cr, Pt and Au. Containing nitrides of one selected metal, one alloy selected from the group consisting of stainless steel, hastelloy, inconel and nichrome, one alloy selected from the group consisting of stainless steel, hastelloy, inconel and nichrome Membranes are preferred. In particular, when the light shielding film made of TiN changes the nitrogen content in the film, the appearance changes steplessly from silver to gold, red, black and black in order of decreasing nitrogen, so it is easy to obtain a desired color tone and preferable .
　また、遮光膜の酸化や変質を防止するために、遮光膜に加えて、酸化防止膜を形成することも可能である。酸化防止膜は、Ｓｉ、Ｔｉ、Ａｌ、Ｎｂ、Ｗ、Ｍｏ、Ｔａ及びＳｎからなる群より選ばれた１種又は２種以上の金属の窒化物、又はＳｉ、Ａｌ及びＴｉからなる群より選ばれた１種の金属の酸化物を含む膜が好適であり、遮光膜の上層に形成したり、ＬＡＳ系結晶化ガラス板と遮光膜との間に形成したりすることができる。 In addition to the light shielding film, it is also possible to form an antioxidant film in order to prevent the oxidation and deterioration of the light shielding film. The antioxidant film is selected from the group consisting of nitrides of one or more metals selected from the group consisting of Si, Ti, Al, Nb, Mo, Ta and Sn, or the group consisting of Si, Al and Ti. A film containing an oxide of one kind of metal is preferable, and it can be formed on the upper layer of the light shielding film or can be formed between the LAS-based crystallized glass plate and the light shielding film.
　本発明のＬＡＳ系結晶化ガラス板は、平均結晶粒径が１００～１０００ｎｍとなるβ－スポジュメン固溶体が析出したＬＡＳ系結晶化ガラス板であって、板厚３．０ｍｍ換算で、ＪＩＳ　Ｚ８７２９に準拠したＬ＊ａ＊ｂ＊表示系の明度値Ｌ＊が３０～８０であることを特徴とする。なお、本発明のＬＡＳ系結晶化ガラス板の技術的特徴は、本発明のＬＡＳ系結晶化ガラス板の製造方法の説明欄に記載済みであるため、ここでは、その詳細な説明を省略する。 The LAS-based crystallized glass plate of the present invention is a LAS-based crystallized glass plate on which a β-spodumene solid solution having an average crystal grain diameter of 100 to 1000 nm is precipitated, and in accordance with JIS Z8729 in terms of a plate thickness of 3.0 mm. The lightness value L * of the L * a * b * display system is 30 to 80. In addition, since the technical feature of the LAS type | system | group crystallized glass board of this invention has already been described in the description column of the manufacturing method of the LAS type | system | group crystallized glass board of this invention, the detailed description is abbreviate | omitted here.
　以下、本発明を実施例に基づいて説明する。なお、以下の実施例は単なる例示である。本発明は、以下の実施例に何ら限定されない。 Hereinafter, the present invention will be described based on examples. The following embodiments are merely illustrative. The present invention is not limited in any way to the following examples.
　表１は、本発明の実施例（試料Ｎｏ．１～３）と比較例（試料Ｎｏ．４、５）を示している。 Table 1 shows Examples (Sample Nos. 1 to 3) of the present invention and Comparative Examples (Sample Nos. 4 and 5).
Figure JPOXMLDOC01-appb-T000001
  
Figure JPOXMLDOC01-appb-T000001
  
　まず、組成が、質量％で、ＳｉＯ２　６５．６％、Ａｌ２Ｏ３　２２．２％、Ｌｉ２Ｏ　３．７％、ＭｇＯ　０．７％、ＢａＯ　１．２％、ＴｉＯ２　２．０％、ＺｒＯ２　２．２％、Ｐ２Ｏ５　１．４％、Ｎａ２Ｏ　０．４％、Ｋ２Ｏ　０．３％、ＳｎＯ２　０．３％の組成になるように、ガラス原料を調合し、ガラスバッチを作製した。次に、白金ルツボを用いて、ガラスバッチを１６００℃で２３時間溶融し、更に１６５０℃に昇温し１時間溶融した。その後、カーボン台上に流し出した上で、成形ローラーで５ｍｍ厚に成形した後、７００℃の徐冷炉で炉冷した。 First, the composition is, in mass%, SiO 2 65.6%, Al 2 O 3 22.2%, Li 2 O 3.7%, MgO 0.7%, BaO 1.2%, TiO 2 2.0 Raw materials of glass so that composition of 2 % ZrO 2 2.2% P 2 O 5 1.4% Na 2 O 0.4% K 2 O 0.3% SnO 2 0.3% Formulated to make a glass batch. Next, using a platinum crucible, the glass batch was melted at 1600 ° C. for 23 hours, further heated to 1650 ° C., and melted for 1 hour. Then, after pouring out on a carbon stand, after forming in 5 mm thickness with a forming roller, furnace cooling was carried out with a 700 ° C slow cooling furnace.
　続いて、得られた結晶性ガラス板について、表中の昇温速度で、室温から表中の最高熱処理温度まで昇温した後、表中の保持時間で保持することによって、結晶化ガラス板を作製した。また各試料の主結晶相、平均結晶粒径、結晶化度、平均線熱膨張係数、Ｌ＊ａ＊ｂ＊表示系の明度値Ｌ＊、平均透過率、拡散反射率、外観及び防眩性を評価した。その結果を表中に示す。 Subsequently, with respect to the obtained crystalline glass plate, the temperature is raised from room temperature to the maximum heat treatment temperature in the table at a temperature rising rate in the table, and then the crystallized glass plate is held by holding time in the table. Made. In addition, main crystal phase of each sample, average crystal grain size, crystallinity, average linear thermal expansion coefficient, L * a * b * lightness value L * of display system, average transmittance, diffuse reflectance, appearance and antiglare property Was evaluated. The results are shown in the table.
　主結晶相と結晶化度は、リガク製ＲＩＮＴ－２１００を用いて、粉末法によるＸ線回折により評価した。なお、表中の「β－Ｓ」はβ－スポジュメン固溶体、「β－Ｑ」はβ－石英固溶体を意味している。また平均結晶粒径は、結晶化ガラス板の一部を電子顕微鏡で観察して求めたものであり、具体的には最表面から深さ１ｍｍの範囲、深さ１ｍｍから深さ１．５ｍｍの範囲、深さ１．５ｍｍから深さ２ｍｍの範囲について、１ｃｍ２の観察箇所をそれぞれ２か所抽出し、それらの結晶粒径を平均化した値である。平均透過率と拡散反射率は、株式会社島津製作所社製分光光度計ＵＶ－３１００を用いて測定した値である。Ｌ＊ａ＊ｂ＊表示系の明度値Ｌ＊は、ＪＩＳ　Ｚ８７２９に準拠した方法で測定した値である。平均透過率、拡散反射率及びＬ＊ａ＊ｂ＊表示系の明度値Ｌ＊の測定試料として、肉厚３．０ｍｍの鏡面研磨品を用いた。また、拡散反射率については、入射角度を８°に設定し、全反射率を測定した。平均線熱膨張係数は、３０～７５０℃の温度範囲において、差動検出式相対膨張計で測定した値である。外観は、目視観察で評価した。具体的には、各試料を黒い背景上に置いた時、青白い散乱光が観察され、且つ透過光が黄色に観察される場合をオパール調として評価した。防眩性は、各試料の片面に膜厚０．５μｍのＴｉＮ膜をスパッタ法によって成膜し、ＴｉＮ膜を形成していない側の面を４０Ｗランプで照らした時、反射光の直視により眩しさを感じなかった場合を「良好」、眩しさを感じた場合を「不良」として評価したものである。 The main crystal phase and the degree of crystallinity were evaluated by X-ray diffraction according to a powder method using Rigaku RINT-2100. In the table, "β-S" means β-spodumene solid solution, and "β-Q" means β-quartz solid solution. The average grain size is obtained by observing a part of the crystallized glass plate with an electron microscope, and specifically, it is in the range of 1 mm in depth from the outermost surface and 1 mm in depth to 1.5 mm in depth In the range of 1.5 mm in depth to 2 mm in depth, two 1-cm 2 observation points are extracted, and the crystal grain sizes of those are averaged. The average transmittance and the diffuse reflectance are values measured using a spectrophotometer UV-3100 manufactured by Shimadzu Corporation. The lightness value L * of the L * a * b * display system is a value measured by a method in accordance with JIS Z8729. A mirror-polished product with a thickness of 3.0 mm was used as a sample for measuring the average transmittance, the diffuse reflectance, and the lightness value L * of the L * a * b * display system. Moreover, about the diffuse reflectance, the incident angle was set to 8 degrees and the total reflectance was measured. The average linear thermal expansion coefficient is a value measured by a differential detection type relative dilatometer in a temperature range of 30 to 750.degree. The appearance was evaluated by visual observation. Specifically, when each sample was placed on a black background, bluish scattered light was observed, and a case where transmitted light was observed to be yellow was evaluated as opal tone. The antiglare property is obtained by forming a TiN film having a film thickness of 0.5 μm on one side of each sample by a sputtering method, and illuminating the side on which the TiN film is not formed with a 40 W lamp. The case where the user did not feel the hardness was evaluated as "good", and the case where he felt the glare was evaluated as "defective".
　表１から明らかなように、試料Ｎｏ．１～３は、昇温速度が４００～８００℃／時間、最高熱処理温度が１１３０℃、保持時間が５～３０分間、主結晶相がβ－スポジュメン固溶体であり、平均結晶粒径が４００～９００ｎｍ、明度値Ｌ＊が３０．８～５１．５、波長４００～８００ｎｍにおける平均透過率が１２．５～２６．３％、波長８００～１５００ｎｍにおける平均透過率が５７．９～７４．８％、熱膨張係数が＋１１×１０－７／℃、外観がオパール調、防眩性が良好であった。よって、試料Ｎｏ．１～３は、明るい光沢を有しながら、目立ち過ぎないことに加えて、生産コストが低いと考えられる。 As apparent from Table 1, the sample no. 1 to 3 have a heating rate of 400 to 800 ° C./hour, maximum heat treatment temperature of 1130 ° C., holding time of 5 to 30 minutes, main crystal phase is β-spodumene solid solution, average grain size of 400 to 900 nm Lightness value L * of 30.8 to 51.5, average transmittance at a wavelength of 400 to 800 nm of 12.5 to 26.3%, average transmittance of a wavelength of 800 to 1500 nm at 57.9 to 74.8%, The thermal expansion coefficient was + 11 × 10 −7 / ° C., the appearance was opal, and the antiglare property was good. Therefore, sample no. It is considered that the production cost is low in addition to having a bright gloss but not being too noticeable.
　一方、試料Ｎｏ．４は、昇温速度が低いため、平均結晶粒径が１２００ｎｍになり、外観が白色不透明になった。また試料Ｎｏ．５は、昇温速度と最高熱処理温度が低いため、主結晶としてβ-石英固溶体が析出し、平均結晶粒径が７０ｎｍになり、透明性が高く、防眩性が不良であった。 On the other hand, for sample no. In No. 4, the average crystal grain size was 1200 nm and the appearance was white and opaque because the heating rate was low. Moreover, sample No. In No. 5, because the temperature rise rate and the maximum heat treatment temperature were low, β-quartz solid solution was precipitated as the main crystal, the average crystal grain size became 70 nm, the transparency was high, and the antiglare property was poor.
　表２は、本発明の実施例（試料Ｎｏ．６～１６）を示している。 Table 2 shows Examples of the present invention (Sample Nos. 6 to 16).
Figure JPOXMLDOC01-appb-T000002
  
Figure JPOXMLDOC01-appb-T000002
  
　まず、組成が、質量％で、ＳｉＯ２　６５．６％、Ａｌ２Ｏ３　２２．２％、Ｌｉ２Ｏ　３．７％、ＭｇＯ　０．７％、ＢａＯ　１．２％、ＴｉＯ２　２．０％、ＺｒＯ２　２．２％、Ｐ２Ｏ５　１．４％、Ｎａ２Ｏ　０．４％、Ｋ２Ｏ　０．３％、ＳｎＯ２　０．３％の組成になるように、ガラス原料を調合し、ガラスバッチを作製した。次に、白金ルツボを用いて、ガラスバッチを１６００℃で２３時間溶融し、更に１６５０℃に昇温し１時間溶融した。その後、カーボン台上に流し出した上で、成形ローラーで５ｍｍ厚に成形した後、７００℃の徐冷炉で炉冷した。 First, the composition is, in mass%, SiO 2 65.6%, Al 2 O 3 22.2%, Li 2 O 3.7%, MgO 0.7%, BaO 1.2%, TiO 2 2.0 Raw materials of glass so that composition of 2 % ZrO 2 2.2% P 2 O 5 1.4% Na 2 O 0.4% K 2 O 0.3% SnO 2 0.3% Formulated to make a glass batch. Next, using a platinum crucible, the glass batch was melted at 1600 ° C. for 23 hours, further heated to 1650 ° C., and melted for 1 hour. Then, after pouring out on a carbon stand, after forming in 5 mm thickness with a forming roller, furnace cooling was carried out with a 700 ° C slow cooling furnace.
　続いて、得られた結晶性ガラス板について、室温から６００℃／時間の昇温速度で昇温して、表中の第一核形成工程の熱処理温度において表中の保持時間で保持した後、６００℃／時間の昇温速度で昇温して、第二核形成工程の熱処理温度において表中の保持時間で保持した。その後、降温させることなく、表中の昇温速度で、第二核形成工程の熱処理温度から表中の最高熱処理温度まで昇温した後、表中の保持時間で保持することによって、結晶化ガラス板を作製した。また各試料の主結晶相、平均結晶粒径、結晶化度、平均線熱膨張係数、Ｌ＊ａ＊ｂ＊表示系の明度値Ｌ＊、平均透過率、拡散反射率、外観及び防眩性を評価した。その結果を表中に示す。 Subsequently, the temperature of the obtained crystalline glass plate is raised from room temperature at a temperature rising rate of 600 ° C./hour, and held at the heat treatment temperature of the first nucleation step in the table for the holding time in the table. The temperature was raised at a temperature rising rate of 600 ° C./hour, and held at the heat treatment temperature in the second nucleation step for the holding time in the table. Thereafter, the temperature is raised from the heat treatment temperature in the second nucleation step to the maximum heat treatment temperature in the table at a temperature rising rate in the table without lowering the temperature, and then held for a holding time in the table to obtain crystallized glass A board was made. In addition, main crystal phase of each sample, average crystal grain size, crystallinity, average linear thermal expansion coefficient, L * a * b * lightness value L * of display system, average transmittance, diffuse reflectance, appearance and antiglare property Was evaluated. The results are shown in the table.
　主結晶相と結晶化度は、リガク製ＲＩＮＴ－２１００を用いて、粉末法によるＸ線回折により評価した。また平均結晶粒径は、結晶化ガラス板の一部を電子顕微鏡で観察して求めたものである。平均透過率と拡散反射率は、株式会社島津製作所社製分光光度計ＵＶ－３１００を用いて測定した値である。Ｌ＊ａ＊ｂ＊表示系の明度値Ｌ＊は、ＪＩＳ　Ｚ８７２９に準拠した方法で測定した値である。平均透過率、拡散反射率及びＬ＊ａ＊ｂ＊表示系の明度値Ｌ＊の測定試料として、肉厚３．０ｍｍの鏡面研磨品を用いた。また、拡散反射率については、入射角度を８°に設定し、全反射率を測定した。平均線熱膨張係数は、３０～７５０℃の温度範囲において、差動検出式相対膨張計で測定した値である。外観は、目視観察で評価した。具体的には、各試料を黒い背景上に置いた時、青白い散乱光が観察され、且つ透過光が黄色に観察される場合をオパール調として評価した。防眩性は、各試料の片面に膜厚０．５μｍのＴｉＮ膜をスパッタ法によって成膜し、ＴｉＮ膜を形成していない側の面を４０Ｗランプで照らした時、反射光の直視により眩しさを感じなかった場合を「良好」、眩しさを感じた場合を「不良」として評価したものである。 The main crystal phase and the degree of crystallinity were evaluated by X-ray diffraction according to a powder method using Rigaku RINT-2100. The average grain size is determined by observing a part of the crystallized glass plate with an electron microscope. The average transmittance and the diffuse reflectance are values measured using a spectrophotometer UV-3100 manufactured by Shimadzu Corporation. The lightness value L * of the L * a * b * display system is a value measured by a method in accordance with JIS Z8729. A mirror-polished product with a thickness of 3.0 mm was used as a sample for measuring the average transmittance, the diffuse reflectance, and the lightness value L * of the L * a * b * display system. Moreover, about the diffuse reflectance, the incident angle was set to 8 degrees and the total reflectance was measured. The average linear thermal expansion coefficient is a value measured by a differential detection type relative dilatometer in a temperature range of 30 to 750.degree. The appearance was evaluated by visual observation. Specifically, when each sample was placed on a black background, bluish scattered light was observed, and a case where transmitted light was observed to be yellow was evaluated as opal tone. The antiglare property is obtained by forming a TiN film having a film thickness of 0.5 μm on one side of each sample by a sputtering method, and illuminating the side on which the TiN film is not formed with a 40 W lamp. The case where the user did not feel the hardness was evaluated as "good", and the case where he felt the glare was evaluated as "defective".
　表２から明らかなように、試料Ｎｏ．６～１６は、主結晶相がβ－スポジュメン固溶体であり、平均結晶粒径が２００～８００ｎｍ、明度値Ｌ＊が３６．９～７２．８、外観がオパール調、防眩性が良好であった。よって、試料Ｎｏ．６～１６は、明るい光沢を有しながら、目立ち過ぎないことに加えて、生産コストが低いと考えられる。 As apparent from Table 2, the sample No. The main crystal phase of 6 to 16 is a β-spodumene solid solution, the average crystal grain size is 200 to 800 nm, the lightness value L * is 36.9 to 72.8, the appearance is opal, and the antiglare property is good. The Therefore, sample no. 6 to 16 are considered to have low production costs in addition to having a bright gloss but not being too noticeable.
　本発明に係るＬＡＳ系結晶化ガラス板は、明るい色合いを有し、また装飾膜を裏側に形成した場合でも装飾膜が目立ち過ぎず、しかも製造コストが低いため、赤外線加熱調理器や電磁加熱調理器のトッププレートとして好適であり、またガス調理器のトッププレートにも好適である。更に、本発明に係るＬＡＳ系結晶化ガラス板は、各種のインジケータの光を通すため、調理器用トッププレート以外のセンサー部品にも使用することができる。 The LAS-based crystallized glass plate according to the present invention has a bright color, and the decorative film is not noticeable even when the decorative film is formed on the back side, and the production cost is low. It is suitable as a top plate of a vessel, and also suitable as a top plate of a gas cooker. Furthermore, since the LAS-based crystallized glass plate according to the present invention transmits the light of various indicators, it can also be used for sensor components other than the top plate for a cooker.

Claims (16)

  1. 　主結晶相としてβ－スポジュメン固溶体を含むＬＡＳ系結晶化ガラス板の製造方法において、
    　結晶性ガラス板を用意する工程と、
    　３００～９００℃／時間の昇温速度で９００℃超となる最高熱処理温度まで結晶性ガラス板を昇温すると共に、平均結晶粒径が１００～１０００ｎｍとなるβ－スポジュメン固溶体を析出させて、ＬＡＳ系結晶化ガラス板を得る工程と、を有することを特徴とするＬＡＳ系結晶化ガラス板の製造方法。     In a method of producing a LAS-based crystallized glass sheet containing β-spodumene solid solution as a main crystal phase,
    Preparing a crystalline glass plate;
    While raising the temperature of the crystalline glass plate to the maximum heat treatment temperature of over 900 ° C. at a temperature rising rate of 300 to 900 ° C./hour, precipitate a β-spodumene solid solution having an average crystal grain size of 100 to 1000 nm, Obtaining a system crystallized glass plate, and a method of producing a LAS system crystallized glass plate.
  2. 　（最高熱処理温度±１０℃）における保持時間が６０分間未満であることを特徴とする請求項１に記載のＬＡＳ系結晶化ガラス板の製造方法。 The method for producing a LAS-based crystallized glass sheet according to claim 1, wherein the holding time at the (maximum heat treatment temperature ± 10 ° C) is less than 60 minutes.
  3. 　平均結晶粒径が１５０～９００ｎｍとなるβ－スポジュメン固溶体を析出させることを特徴とする請求項１又は２に記載のＬＡＳ系結晶化ガラス板の製造方法。 3. The method for producing a LAS crystallized glass sheet according to claim 1, wherein a β-spodumene solid solution having an average crystal grain size of 150 to 900 nm is precipitated.
  4. 　板厚３．０ｍｍ換算で、ＪＩＳ　Ｚ８７２９に準拠したＬ＊ａ＊ｂ＊表示系の明度値Ｌ＊が３０～８０となるＬＡＳ系結晶化ガラス板を得ることを特徴とする請求項１～３の何れかに記載のＬＡＳ系結晶化ガラス板の製造方法。 Sheet thickness 3.0mm terms claims 1 to 3, wherein the obtaining the LAS-type crystallized glass plate L in compliance with JIS Z8729 * a * b * display system lightness value L * is 30 to 80 The manufacturing method of the LAS type | system | group crystallized glass board in any one of these.
  5. 　板厚３．０ｍｍ換算で、波長４００～８００ｎｍにおける平均透過率が１０～５０％になるＬＡＳ系結晶化ガラス板を得ることを特徴とする請求項１～４の何れかに記載のＬＡＳ系結晶化ガラス板の製造方法。 The LAS-based crystal according to any one of claims 1 to 4, characterized in that a LAS-based crystallized glass plate having an average transmittance of 10 to 50% at a wavelength of 400 to 800 nm in terms of a plate thickness of 3.0 mm is obtained. Method of producing a glass sheet
  6. 　板厚３．０ｍｍ換算で、波長８００～１５００ｎｍにおける平均透過率が５０％以上になるＬＡＳ系結晶化ガラス板を得ることを特徴とする請求項１～５の何れかに記載のＬＡＳ系結晶化ガラス板の製造方法。 The LAS-based crystallization according to any one of claims 1 to 5, characterized in that a LAS-based crystallized glass plate having an average transmittance of 50% or more at a wavelength of 800 to 1500 nm in terms of a plate thickness of 3.0 mm is obtained. Method of manufacturing glass plate.
  7. 　３０～７５０℃における平均線熱膨張係数が－１０×１０－７～＋３０×１０－７／℃になるＬＡＳ系結晶化ガラス板を得ることを特徴とする請求項１～６の何れかに記載のＬＡＳ系結晶化ガラス板の製造方法。 7. A LAS-based crystallized glass plate having an average linear thermal expansion coefficient of −10 × 10 −7 to + 30 × 10 −7 / ° C. at 30 to 750 ° C. is obtained. Of LAS-based crystallized glass sheet.
  8. 　ＬＡＳ系結晶化ガラス板中のＺｎＯの含有量が２質量％未満であることを特徴とする請求項１～７の何れかに記載のＬＡＳ系結晶化ガラス板の製造方法。 8. The method for producing a LAS-based crystallized glass plate according to any one of claims 1 to 7, wherein the content of ZnO in the LAS-based crystallized glass plate is less than 2% by mass.
  9. 　ＬＡＳ系結晶化ガラス板が、組成として、質量％で、ＳｉＯ２　５５～７５％、Ａｌ２Ｏ３　１５～３０％、Ｌｉ２Ｏ　２～６％、ＭｇＯ　０～３％、ＢａＯ　０～５％、ＺｎＯ　０～２％未満、ＴｉＯ２　１～６％、ＺｒＯ２　０～４％、Ｐ２Ｏ５　０～５％、Ｎａ２Ｏ　０～４％、Ｋ２Ｏ　０～４％を含有することを特徴とする請求項１～８の何れかに記載のＬＡＳ系結晶化ガラス板の製造方法。 The LAS-based crystallized glass plate has a composition by mass as follows: SiO 2 55-75%, Al 2 O 3 15-30%, Li 2 O 2-6%, MgO 0-3%, BaO 0-5% , ZnO 0 to 2%, TiO 2 1 to 6%, ZrO 2 0 to 4%, P 2 O 5 0 to 5%, Na 2 O 0 to 4%, K 2 O 0 to 4% The method for producing a LAS crystallized glass sheet according to any one of claims 1 to 8, characterized in that
  10. 　ＬＡＳ系結晶化ガラス板を調理器用トッププレートに用いることを特徴とする請求項１～９の何れかに記載のＬＡＳ系結晶化ガラス板の製造方法。 The method for producing a LAS-based crystallized glass plate according to any one of claims 1 to 9, wherein the LAS-based crystallized glass plate is used as a top plate for a cooker.
  11. 　平均結晶粒径が１００～１０００ｎｍとなるβ－スポジュメン固溶体が析出したＬＡＳ系結晶化ガラス板であって、板厚３．０ｍｍ換算で、ＪＩＳ　Ｚ８７２９に準拠したＬ＊ａ＊ｂ＊表示系の明度値Ｌ＊が３０～８０であることを特徴とするＬＡＳ系結晶化ガラス板。 A LAS-based crystallized glass plate on which a β-spodumene solid solution having an average crystal grain size of 100 to 1000 nm is deposited, and the lightness of L * a * b * display system according to JIS Z8729 in terms of a plate thickness of 3.0 mm. A LAS-based crystallized glass sheet having a value L * of 30 to 80.
  12. 　板厚３．０ｍｍ換算で、波長４００～８００ｎｍにおける平均透過率が１０～５０％であることを特徴とする請求項１１に記載のＬＡＳ系結晶化ガラス板。 The LAS-based crystallized glass sheet according to claim 11, wherein the average transmittance at a wavelength of 400 to 800 nm is 10 to 50% in terms of a plate thickness of 3.0 mm.
  13. 　板厚３．０ｍｍ換算で、波長８００～１５００ｎｍにおける平均透過率が５０％以上であることを特徴とする請求項１１又は１２に記載のＬＡＳ系結晶化ガラス板。 13. The LAS-based crystallized glass sheet according to claim 11, wherein the average transmittance at a wavelength of 800 to 1500 nm is 50% or more in terms of a plate thickness of 3.0 mm.
  14. 　３０～７５０℃における平均線熱膨張係数が－１０×１０－７～＋３０×１０－７／℃であことを特徴とする請求項１１～１３の何れかに記載のＬＡＳ系結晶化ガラス板。 The LAS-based crystallized glass sheet according to any one of claims 11 to 13, characterized in that the average linear thermal expansion coefficient at 30 to 750 ° C is -10 x 10 -7 to +30 x 10 -7 / ° C.
  15. 　組成として、質量％で、ＳｉＯ２　５５～７５％、Ａｌ２Ｏ３　１５～３０％、Ｌｉ２Ｏ　２～６％、ＭｇＯ　０～３％、ＢａＯ　０～５％、ＺｎＯ　０～２％未満、ＴｉＯ２　１～６％、ＺｒＯ２　０～４％、Ｐ２Ｏ５　０～５％、Ｎａ２Ｏ　０～４％、Ｋ２Ｏ　０～４％を含有することを特徴とする請求項１１～１４の何れかに記載のＬＡＳ系結晶化ガラス板。 The composition is, by mass%, SiO 2 55-75%, Al 2 O 3 15-30%, Li 2 O 2-6%, MgO 0-3%, BaO 0-5%, ZnO 0-2%, TiO 2 1 ~ 6%, ZrO 2 0 ~ 4%, P 2 O 5 0 ~ 5%, Na 2 O 0 ~ 4%, claim 11, characterized in that it contains K 2 O 0 ~ 4% ~ The LAS type | system | group crystallized glass board in any one of 14.
  16. 　組成として、質量％で、ＳｉＯ２　６０～７０％、Ａｌ２Ｏ３　２０超～３０％、Ｌｉ２Ｏ　３～５％、ＭｇＯ　０～１％、ＢａＯ　１～２％、ＺｎＯ　０～０．４％未満、ＴｉＯ２　１～４％、ＺｒＯ２　２～３％、Ｐ２Ｏ５　０～２％、Ｎａ２Ｏ　０～４％、Ｋ２Ｏ　０～４％を含有することを特徴とする請求項１１～１５の何れかに記載のＬＡＳ系結晶化ガラス板。 Composition:% by mass of SiO 2 60 to 70%, Al 2 O 3 over 20 to 30%, Li 2 O 3 to 5%, MgO 0 to 1%, BaO 1 to 2%, ZnO 0 to 0.4 %, TiO 2 1 to 4%, ZrO 2 2 to 3%, P 2 O 5 0 to 2%, Na 2 O 0 to 4%, and K 2 O 0 to 4%. Item 21. A LAS-based crystallized glass sheet according to any one of Items 11 to 15.
PCT/JP2018/045446 2017-12-15 2018-12-11 Las-based crystallized glass plate production method and las-based crystallized glass plate WO2019117122A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2019559646A JPWO2019117122A1 (en) 2017-12-15 2018-12-11 Manufacturing method of LAS-based crystallized glass plate and LAS-based crystallized glass plate

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2017240182 2017-12-15
JP2017-240182 2017-12-15

Publications (1)

Publication Number Publication Date
WO2019117122A1 true WO2019117122A1 (en) 2019-06-20

Family

ID=66820839

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2018/045446 WO2019117122A1 (en) 2017-12-15 2018-12-11 Las-based crystallized glass plate production method and las-based crystallized glass plate

Country Status (2)

Country Link
JP (1) JPWO2019117122A1 (en)
WO (1) WO2019117122A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4140964A1 (en) 2021-08-25 2023-03-01 Schott Ag Crystallizable lithium aluminosilicate glass and glass ceramic produced therefrom and method for producing glass ceramic and use of the glass ceramic

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005037906A (en) * 2003-06-25 2005-02-10 Nippon Electric Glass Co Ltd Reflection mirror and its manufacturing method
JP2005063949A (en) * 2003-07-30 2005-03-10 Nippon Electric Glass Co Ltd Top plate for cooking device, and its manufacturing method
JP2005325018A (en) * 2004-05-12 2005-11-24 Schott Ag Translucent or opaque colored glass ceramic product used as cooking surface and its use
JP2009531261A (en) * 2006-03-31 2009-09-03 ユーロケラ β-spodumene glass ceramic material and its manufacturing process
JP2015520097A (en) * 2012-04-13 2015-07-16 コーニング インコーポレイテッド White opaque β-spodumene / rutile glass-ceramic, articles containing the same, and methods for making the same
JP2016536244A (en) * 2013-10-09 2016-11-24 コーニング インコーポレイテッド Crack-resistant glass-ceramic article and method for producing the same
DE102016208300B3 (en) * 2016-05-13 2017-08-03 Schott Ag Crystallizable lithium aluminum silicate glass and transparent glass ceramic produced therefrom, and also methods for producing the glass and the glass ceramic and use of the glass ceramic
JP2018180331A (en) * 2017-04-14 2018-11-15 日本電気硝子株式会社 Transparent screen and graphic display device using the same

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005037906A (en) * 2003-06-25 2005-02-10 Nippon Electric Glass Co Ltd Reflection mirror and its manufacturing method
JP2005063949A (en) * 2003-07-30 2005-03-10 Nippon Electric Glass Co Ltd Top plate for cooking device, and its manufacturing method
JP2005325018A (en) * 2004-05-12 2005-11-24 Schott Ag Translucent or opaque colored glass ceramic product used as cooking surface and its use
JP2009531261A (en) * 2006-03-31 2009-09-03 ユーロケラ β-spodumene glass ceramic material and its manufacturing process
JP2015520097A (en) * 2012-04-13 2015-07-16 コーニング インコーポレイテッド White opaque β-spodumene / rutile glass-ceramic, articles containing the same, and methods for making the same
JP2016536244A (en) * 2013-10-09 2016-11-24 コーニング インコーポレイテッド Crack-resistant glass-ceramic article and method for producing the same
DE102016208300B3 (en) * 2016-05-13 2017-08-03 Schott Ag Crystallizable lithium aluminum silicate glass and transparent glass ceramic produced therefrom, and also methods for producing the glass and the glass ceramic and use of the glass ceramic
JP2018180331A (en) * 2017-04-14 2018-11-15 日本電気硝子株式会社 Transparent screen and graphic display device using the same

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
NINOMIYA, MASAYUKI: "Development of low expansion crystallization glass to new applications", NEW GLASS 78, vol. 20, no. 3, 2005, pages 22 - 28 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4140964A1 (en) 2021-08-25 2023-03-01 Schott Ag Crystallizable lithium aluminosilicate glass and glass ceramic produced therefrom and method for producing glass ceramic and use of the glass ceramic
DE102021122035A1 (en) 2021-08-25 2023-03-02 Schott Ag Crystallizable lithium aluminum silicate glass and glass ceramics produced therefrom, as well as methods for producing the glass ceramics and use of the glass ceramics

Also Published As

Publication number Publication date
JPWO2019117122A1 (en) 2020-10-22

Similar Documents

Publication Publication Date Title
US11267748B2 (en) Transparent coloured lithium aluminium silicate glass ceramic and process for production and use of the glass ceramic
US10160685B2 (en) Non-opaque arsenic-free beta-spodumene glass ceramic exhibiting brown-grey coloration
JP7097783B2 (en) Colored transparent lithium aluminum silicate glass ceramic and its use
CN104411647B (en) The manufacturing method of glass ceramics with predetermined transmissivity
JP5889297B2 (en) Transparent or transparent colored lithium aluminum silicate glass-ceramic material having a suitable coefficient of thermal expansion and use thereof
KR102257715B1 (en) Glass ceramic item and enamel for coating same
JP4315075B2 (en) Top plate for cooker and method for manufacturing the same
KR102661700B1 (en) Fitout articles and articles of equipment for kitchens or laboratories with a display device
JP4120793B2 (en) Cooker top plate
JP2001501168A (en) Glass ceramic plate and method of manufacturing the same
JP2668075B2 (en) Transparent crystallized glass
JP6301965B2 (en) Enamels suitable for glass-ceramic articles and their coatings
CN104619661B (en) Glass ceramics and preparation method thereof
JP5182102B2 (en) Cooker top plate
WO2019117122A1 (en) Las-based crystallized glass plate production method and las-based crystallized glass plate
JPH05193983A (en) Transparent glass and glass goods
KR20200123418A (en) Glass-ceramic articles
JP2021138602A (en) Crystallizable lithium aluminosilicate glass and glass ceramic produced therefrom and method for producing glass and glass ceramic and use of the glass ceramic
KR20200123417A (en) Glass-ceramic articles
JP2005055005A (en) Top plate for cooking device
JP2004211910A (en) Top plate for cooking device
KR101657922B1 (en) - - glass-ceramic of lithium aluminosilicate type containing a solid solution of -spodumene
US20230100027A1 (en) Crystallizable lithium aluminum silicate glass and glass ceramic produced therefrom
JP2008185233A (en) Top plate for cooker
JP2021138604A (en) Crystallizable lithium aluminosilicate glass and glass ceramic produced therefrom and method for producing glass and glass ceramic and use of the glass ceramic

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 18889738

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2019559646

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 18889738

Country of ref document: EP

Kind code of ref document: A1