WO2018154973A1 - 結晶化ガラス - Google Patents
結晶化ガラス Download PDFInfo
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- WO2018154973A1 WO2018154973A1 PCT/JP2017/047245 JP2017047245W WO2018154973A1 WO 2018154973 A1 WO2018154973 A1 WO 2018154973A1 JP 2017047245 W JP2017047245 W JP 2017047245W WO 2018154973 A1 WO2018154973 A1 WO 2018154973A1
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- crystallized glass
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Classifications
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/078—Glass compositions containing silica with 40% to 90% silica, by weight containing an oxide of a divalent metal, e.g. an oxide of zinc
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
- C03C10/0036—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and a divalent metal oxide as main constituents
- C03C10/0045—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and a divalent metal oxide as main constituents containing SiO2, Al2O3 and MgO as main constituents
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C21/00—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C21/00—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface
- C03C21/001—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions
- C03C21/002—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions to perform ion-exchange between alkali ions
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
- C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
- C03C3/087—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal containing calcium oxide, e.g. common sheet or container glass
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C4/00—Compositions for glass with special properties
- C03C4/0092—Compositions for glass with special properties for glass with improved high visible transmittance, e.g. extra-clear glass
Definitions
- the present invention relates to a crystallized glass having a compressive stress layer on the surface.
- the present invention relates to crystallized glass suitable for protective members such as portable electronic devices and optical devices.
- Cover glass for protecting the display is used for portable electronic devices such as smartphones and tablet PCs.
- a protector for protecting a lens is also used in an in-vehicle optical device.
- These cover glass and protector materials are required to have high visible light transmittance and excellent color balance. In recent years, there is an increasing demand for materials having higher hardness in cover glass and protector applications so that these devices can withstand more severe use.
- Crystallized glass in which crystals are precipitated inside the glass in order to increase the strength of the glass.
- Crystallized glass can have higher mechanical properties than amorphous glass, but conventional crystallized glass is not suitable for use in the protective member because of its poor visible light transmission.
- Patent Document 1 discloses crystallized glass for information recording media. This crystallized glass has poor visible light permeability. When chemical strengthening is performed, a sufficient compressive stress value cannot be obtained, and the stress layer is not formed deeply.
- An object of the present invention is to obtain a crystallized glass having a high visible light transmittance and a high hardness.
- the present inventors specify the components constituting the crystallized glass and the content thereof, and further adjust the crystallization conditions and the chemical strengthening conditions. It has been found that a very hard transparent crystallized glass can be obtained, and the present invention has been completed. Specifically, the present invention provides the following.
- (Configuration 1) With crystallized glass as the base material, it has a compressive stress layer on the surface, A crystallized glass having a light transmittance of 80% including reflection loss at a thickness of 10 mm, a wavelength of 400 to 669 nm, and a Vickers hardness [Hv] of 835 to 1300.
- (Configuration 2) The crystallized glass according to Configuration 1, wherein the compressive stress layer has a thickness of 20 ⁇ m or more.
- the crystallized glass base material is weight% in terms of oxide, 40.0% to 70.0% of SiO 2 component, Al 2 O 3 component from 11.0% to 25.0%, Na 2 O component of 5.0% to 19.0%, K 2 O component from 0% to 9.0%, 1.0% to 18.0% of MgO component, CaO component 0% to 3.0%, TiO 2 component 0.5% to 12.0%, Containing
- the crystallized glass according to Configuration 1 or 2 which contains 90% or more of the SiO 2 component, Al 2 O 3 component, Na 2 O component, K 2 O component, MgO component, and TiO 2 component.
- the crystallized glass base material is weight% in terms of oxide, 4 to 65.0% of SiO 2 component, Al 2 O 3 component of 13.0% to 23.0%, 8.0% -16.0% Na 2 O component, 1.0% to 7.0% K 2 O component, 2.0% to 15.0% MgO component, CaO component 0.1% to 2.0%, 1.0% to 10.0% of TiO 2 component, and 0.1% to 2.0% of one or more selected from the group consisting of Sb 2 O 3 component, SnO 2 component and CeO 2 component, Containing 4.
- Configuration 5 The crystallized glass according to any one of constitutions 1 to 4, wherein the average crystal diameter of the precipitated crystals is 4 to 15 nm.
- crystallized glass having high visible light transmittance and high hardness can be obtained.
- the crystallized glass of the present invention can be used as a material for optical members such as optical lenses. Moreover, it can also be used for the outer frame member of a portable electronic device, and other decoration applications, taking advantage of the appearance peculiar to glass materials.
- the crystallized glass of the present invention uses a crystallized glass as a base material (also referred to as a crystallized glass base material) and has a compressive stress layer on the surface.
- the compressive stress layer can be formed on the crystallized glass base material by ion exchange treatment, and strengthens the crystallized glass base material.
- the wavelength at which the light transmittance including reflection loss at a thickness of 10 mm (also simply referred to as transmittance) is 80% is 400 to 669 nm, preferably 400 to 620 nm, more preferably Is 400 to 600 nm.
- transmittance can be measured by the method described in the examples.
- Such a transmittance is influenced by the crystal particle diameter, the amount of crystals, the nucleating agent, and the like, and can be obtained by adjusting the crystallization temperature and the crystallization time in particular. When the crystallization temperature is increased, the wavelength tends to increase.
- the Vickers hardness [Hv] is 835 to 1300.
- the Vickers hardness is preferably 840 to 1300. If the hardness is high, it is difficult to scratch and crack. Vickers hardness can be measured by the method described in Examples. Such hardness can be obtained especially by adjusting the chemical strengthening time and temperature with respect to the thickness of the substrate.
- the thickness of the compressive stress layer of crystallized glass is preferably 20 ⁇ m or more.
- the compressive stress layer has such a thickness, even if a deep crack occurs in the crystallized glass substrate, it is possible to prevent the crack from extending or the substrate from cracking. More preferably, it is 43 ⁇ m or more, and most preferably 45 ⁇ m or more.
- an upper limit is not limited, Usually, it is 350 micrometers or less.
- the compressive stress value on the surface of the compressive stress layer is preferably 850 MPa or more. By having such a compressive stress value, extension of cracks can be suppressed and mechanical strength can be increased. More preferably, it is 950 MPa or more, more preferably 1000 MPa or more, and most preferably 1050 MPa or more. Although an upper limit is not limited, Usually, it is 1200 MPa or less.
- the central stress CT (MPa) is generally expressed by the following equation when the surface compressive stress is CS (MPa), the substrate thickness is T ( ⁇ m), and the stress depth is t ( ⁇ m).
- the CT [CS ⁇ t] / [T-2t]
- the CT value increases as the CS value increases and the stress depth t increases.
- CS t increases, the surface hardness and Vickers hardness tend to increase, and the CT value also increases.
- the crystallized glass base material constituting the crystallized glass is a material having a crystal phase and a glass phase, and is distinguished from an amorphous solid.
- the crystal phase of crystallized glass is discriminated using the angle of a peak appearing in an X-ray diffraction pattern of X-ray diffraction analysis and, if necessary, TEMDX.
- Crystallized glass is, for example, MgAl 2 O 4 , MgTi 2 O 5 , MgTi 2 O 4 , Mg 2 TiO 4 , Mg 2 SiO 4 , MgAl 2 Si 2 O 8 and Mg 2 Al 4 Si 5 O 18 as crystal phases. 1 type or more chosen from.
- the average crystal diameter in the crystallized glass is, for example, 4 to 15 nm, and can be 5 to 13 nm or 6 to 10 nm.
- the average crystal diameter can be measured by the method described in the examples. When the average crystal diameter is small, the surface roughness Ra after polishing can be smoothly processed to a few tens of levels. Further, the transmittance is increased.
- the average crystal diameter can be adjusted by the composition and crystallization conditions.
- composition range of each component constituting the crystallized glass is described below.
- content of each component is expressed in terms of weight% in terms of oxide unless otherwise specified.
- oxide conversion means that in the crystallized glass when the total weight of the oxide is 100% by weight, assuming that the crystallized glass constituents are all decomposed and changed to oxides.
- the amount of oxide of each component contained is expressed in weight%.
- the crystallized glass as a base material (hereinafter also simply referred to as crystallized glass) is preferably weight% in terms of oxide, 40.0% to 70.0% of SiO 2 component, Al 2 O 3 component from 11.0% to 25.0%, Na 2 O component of 5.0% to 19.0%, K 2 O component from 0% to 9.0%, 1.0% to 18.0% of MgO component, CaO component 0% to 3.0%, TiO 2 component 0.5% to 12.0%, Containing.
- the crystallized glass is more preferably in oxide-based weight%,
- the crystallized glass preferably further contains 0.01% to 3.0% of one or more selected from the group consisting of Sb 2 O 3 component, SnO 2 component and CeO 2 component.
- the SiO 2 component is contained in an amount of 45.0% to 65.0%, more preferably 50.0% to 60.0%. More preferably, the Al 2 O 3 component is contained in an amount of 13.0% to 23.0%.
- the Na 2 O component is more preferably contained in an amount of 8.0% to 18.0%, further preferably 9.0% to 17.0%, and particularly preferably 10.5% to 16.0%.
- the K 2 O component is more preferably contained in an amount of 1.0% to 7.0%, more preferably 1.0% to 5.0%.
- the MgO component is more preferably contained in an amount of 2.0% to 15.0%, further preferably 3.0% to 13.0%, and particularly preferably 5.0% to 11.0%. More preferably, the CaO component is contained in an amount of 0.1% to 2.0%.
- the TiO 2 component is more preferably contained in an amount of 1.0% to 10.0%, more preferably 2.0% to 8.0%.
- the Sb 2 O 3 component, SnO 2 component and CeO 2 component are contained in a total amount of preferably 0.1% to 2.0%, more preferably 0.3% to 1.0%. The above compounding amounts can be appropriately combined.
- the SiO 2 component, Al 2 O 3 component, Na 2 O component, K 2 O component, MgO component, and TiO 2 component together are 90% or more, preferably 95% or more, more preferably 98% or more, and still more preferably 99 % Or more.
- 90% or more in total of SiO 2 component, Al 2 O 3 component, Na 2 O component, K 2 O component, MgO component, CaO component, TiO 2 component, Sb 2 O 3 component, SnO 2 component and CeO 2 component Preferably it is 95% or more, More preferably, it can be 98% or more, More preferably, it can be 99% or more. You may occupy 100% with these components.
- the crystallized glass may or may not contain a ZnO component and a ZrO 2 component as long as the effects of the present invention are not impaired.
- the blending amount can be 0 to 5.0%, 0 to 3.0%, or 0 to 2.0%. When these components are added, the specific gravity increases. Furthermore, crystallized glass, within a range not to impair the effects of the present invention, B 2 O 3 component, P 2 O 5 component, BaO component, FeO component, Li 2 O component, SrO component, La 2 O 3 component, Y 2 O 3 component, Nb 2 O 5 component, Ta 2 O 5 component, WO 3 component, TeO 2 component, Bi 2 O 3 component may or may not be included.
- the blending amounts can be 0% or more and 2.0% or less, 0% or more and less than 2.0%, or 0% or more and 1.0% or less, respectively.
- the crystallized glass of the present invention in addition to Sb 2 O 3 component, SnO 2 component, CeO 2 component, As 2 O 3 component, a kind selected from the group of F, Cl, NOx, SOx Or you may contain 2 or more types.
- the upper limit of the content of the fining agent is preferably 5.0%, more preferably 2.0%, and most preferably 1.0%.
- the crystallized glass as the base material is preferably mol% in terms of oxide, 43.0 mol% to 73.0 mol% of SiO 2 component, 4.0 mol% to 18.0 mol% of Al 2 O 3 component, Na 2 O component in an amount of 5.0 mol% to 19.0 mol%, 0.1 mol% to 9.0 mol% of K 2 O component, 2.0 mol% to 22.0 mol% of MgO component, 0.01 mol% to 3.0 mol% of CaO component, 0.5 mol% to 11.0 mol% of TiO 2 component and 0.01 mol% to 3.0 mol of one or more selected from the group consisting of Sb 2 O 3 component, SnO 2 component and CeO 2 component Mol%, Containing.
- SiO 2 component, Al 2 O 3 component, Na 2 O component, K 2 O component, MgO component, TiO 2 component are combined in 90 mol% or more, preferably 95 mol% or more, more preferably 98 mol% or more, Preferably it can be 99 mol% or more.
- the value of the molar ratio [Al 2 O 3 / MgO] expressed on an oxide basis may be 0.5 or more and 2.0 or less.
- the value of the molar ratio [TiO 2 / Na 2 O] expressed on an oxide basis may be 0 or more and 0.41 or less.
- the value of the molar ratio [MgO / Na 2 O] expressed on an oxide basis may be 0 or more and 1.60 or less.
- transition metal components such as V, Cr, Mn, Co, Ni, Cu, Ag and Mo, excluding Ti, Fe, Zr, Nb, W, La, Gd, Y, Yb and Lu, are colored by glass. Therefore, it is preferable not to include substantially.
- each component of Pb, Th, Cd, Tl, Os, Be and Se tends to be refrained from being used as a harmful chemical material in recent years, it is preferable that these components are not substantially contained.
- the crystallized glass of the present invention can be produced, for example, by the following method. That is, raw materials are uniformly mixed so that the above components are within a predetermined content range, and melt-molded to produce an original glass. Next, this raw glass is crystallized to produce a crystallized glass base material. Furthermore, the crystallized glass base material is chemically strengthened.
- the original glass is heat-treated to uniformly precipitate crystals inside the glass.
- This heat treatment may be performed in one stage or at two stages.
- a nucleation step is performed by heat treatment at a first temperature
- a crystal growth step is performed by heat treatment at a second temperature higher than the nucleation step.
- the nucleation step and the crystal growth step are continuously performed at one step temperature.
- the temperature is raised to a predetermined heat treatment temperature, and after reaching the heat treatment temperature, the temperature is maintained for a certain time, and then the temperature is lowered.
- the first temperature of the two-stage heat treatment is preferably 600 ° C. to 750 ° C.
- the holding time at the first temperature is preferably 30 minutes to 2000 minutes, and most preferably 180 minutes to 1440 minutes.
- the second temperature of the two-stage heat treatment is preferably 650 ° C. to 850 ° C.
- the holding time at the second temperature is preferably 30 minutes to 600 minutes, and most preferably 60 minutes to 300 minutes.
- the heat treatment temperature is preferably 600 ° C. to 800 ° C., more preferably 630 ° C. to 770 ° C.
- the holding time at the heat treatment temperature is preferably 30 minutes to 500 minutes, more preferably 60 minutes to 300 minutes.
- a molded body can be produced from the crystallized glass base material by means of, for example, grinding and polishing. By processing the molded body into a thin plate shape, a thin plate-like crystallized glass base material can be produced.
- a compressive stress layer is formed on the crystallized glass base material.
- the compressive stress layer is a reinforcing layer formed by ion exchange by a chemical strengthening method.
- the crystallized glass base material can be chemically strengthened by contacting or dipping it in a salt containing potassium or sodium, for example, a molten salt such as potassium nitrate (KNO 3 ) or sodium nitrate (NaNO 3 ).
- a molten salt such as potassium nitrate (KNO 3 ) or sodium nitrate (NaNO 3 ).
- the crystallized glass base material is added to a molten salt obtained by heating potassium nitrate (KNO 3 ) to 350 to 600 ° C. (more preferably 400 to 500 ° C.) for 90 minutes or more, for example, 90 minutes to 60 hours, preferably 90 Immerse for 50 minutes.
- KNO 3 potassium nitrate
- the crystallized glass base material is added to a molten salt obtained by heating potassium nitrate (KNO 3 ) to 350 to 600 ° C. (more preferably 400 to 500 ° C.) for 90 minutes or more, for example, 90 minutes to 60 hours, preferably
- Examples 1 to 29, Comparative Example 1 Select raw materials such as oxide, hydroxide, carbonate, nitrate, fluoride, chloride, hydroxide, metaphosphate compound as raw materials for each component of crystallized glass. They were weighed so as to have a composition ratio and mixed uniformly. (Weight% in terms of oxide) 55% SiO 2 component, 18% Al 2 O 3 component, 12% Na 2 O component, 2 % K 2 O component, 8% MgO component, 1% CaO component, 5% TiO 2 component , 0.1% of Sb 2 O 3 component
- the mixed raw materials were put into a platinum crucible and melted. Thereafter, the molten glass was agitated and homogenized, cast into a mold, etc., and slowly cooled to produce an original glass.
- the obtained raw glass was subjected to a one-step heat treatment for nucleation and crystallization to produce a crystallized glass as a base material.
- the heat treatment temperature was 660 to 740 ° C., and the holding time at that temperature was 5 hours.
- the produced crystallized glass base material was cut and ground so as to have a shape of 40 mm square and a thickness of more than 10 mm, and face-to-face parallel polishing was performed so as to obtain a substrate having a thickness of 1 mm and 10 mm.
- the spectral transmittance of 240 to 800 nm is measured with a U-4000 spectrophotometer manufactured by Hitachi High Technology, and the wavelength at which the transmittance including reflection loss is 80% is obtained. It was. The results are shown in Tables 1 and 2.
- the crystal phase of the crystallized glass base material is determined by measuring the angle of the peak appearing in the X-ray diffraction pattern measured by an X-ray diffraction analyzer (X'PERT-PRO-MPD manufactured by Philips), and if necessary, TEMDX (JEOL JEM2100F) was used for determination.
- X'PERT-PRO-MPD manufactured by Philips
- TEMDX JEOL JEM2100F
- the average crystal diameter of the crystal particles precipitated on the crystallized glass base material was measured from a scanning electron microscope (TEM) photograph image (JEM2100F manufactured by JEOL Ltd.) of 3 million times. Specifically, the crystal diameter of the crystal particles within the range of 180 ⁇ 180 nm 2 was obtained and the average value was calculated. The average crystal diameter is shown in Tables 1 and 2.
- Chemical strengthening is performed by immersing the crystallized glass base material (substrate) face-parallel polished to the thickness shown in Tables 1 and 2 in KNO 3 molten salt at the salt bath temperature and immersion time shown in Tables 1 and 2. Thus, crystallized glass was obtained.
- the specific gravity of the crystallized glass of Example 1 was 2.54. The transmittance and average crystal diameter did not change after chemical strengthening.
- the Vickers hardness (Hv) of the crystallized glass was determined and shown in Tables 1 and 2.
- the Vickers hardness is a value obtained by dividing the load when a pyramid-shaped depression is made on the test surface using a diamond quadrangular pyramid indenter with a facing angle of 136 ° divided by the surface area (mm 2 ) calculated from the length of the depression. Indicated. Using a micro hardness tester MVK-E manufactured by Akashi Seisakusho, measurement was performed with a test load of 100 gf and a holding time of 15 seconds.
- the thickness (stress depth) (DOL) of the compressive stress layer of the crystallized glass and the compressive stress value (CS) of the surface thereof were measured using a glass surface stress meter FSM-6000LE manufactured by Orihara Seisakusho.
- the refractive index was 1.54 and the optical elastic constant was 29.658 [(nm / cm) / MPa].
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Abstract
Description
また、ガラスより硬度が高く、透明性を有する材料としてサファイアが注目されているが、サファイアの製造は、ガラスに比べ生産性が悪く、また加工性も悪い。
結晶化ガラスを母材とし、表面に圧縮応力層を有し、
厚さ10mmにおける反射損失を含む光線透過率が80%である波長が400~669nmであり、ビッカース硬度[Hv]が835~1300である結晶化ガラス。
(構成2)
前記圧縮応力層の厚さが20μm以上である構成1に記載の結晶化ガラス。
(構成3)
前記結晶化ガラス母材が、酸化物換算の重量%で、
SiO2成分を40.0%~70.0%、
Al2O3成分を11.0%~25.0%、
Na2O成分を5.0%~19.0%、
K2O成分を0%~9.0%、
MgO成分を1.0%~18.0%、
CaO成分を0%~3.0%、および
TiO2成分を0.5%~12.0%、
を含有し、
SiO2成分、Al2O3成分、Na2O成分、K2O成分、MgO成分、TiO2成分を合わせて90%以上含有する構成1または2に記載の結晶化ガラス。
(構成4)
前記結晶化ガラス母材が、酸化物換算の重量%で、
SiO2成分を45.0%~65.0%、
Al2O3成分を13.0%~23.0%、
Na2O成分を8.0%~16.0%、
K2O成分を1.0%~7.0%、
MgO成分を2.0%~15.0%、
CaO成分を0.1%~2.0%、
TiO2成分を1.0%~10.0%、並びに
Sb2O3成分、SnO2成分およびCeO2成分からなる群より選択される1種以上を0.1%~2.0%、
を含有し、
SiO2成分、Al2O3成分、Na2O成分、K2O成分、MgO成分、TiO2成分を合わせて90%以上含有する構成1から3のいずれかに記載の結晶化ガラス。
(構成5)
析出結晶の平均結晶径が、4~15nmである構成1から4のいずれかに記載の結晶化ガラス。
本発明の結晶化ガラスは、結晶化ガラスを母材(結晶化ガラス母材ともいう)とし、表面に圧縮応力層を有する。圧縮応力層は、結晶化ガラス母材にイオン交換処理により形成することができ、結晶化ガラス母材を強化する。
CT=[CS×t]/[T-2t]
CT値は、CSの値が大きく、そして、応力深さtが大きいほど高い値となる。CS、tが大きいほど表面硬さとビッカース硬度は増大する傾向となり、CT値も上昇する。
結晶化ガラスを構成する結晶化ガラス母材は、結晶相とガラス相を有する材料であり、非晶質固体とは区別される。一般的に、結晶化ガラスの結晶相は、X線回折分析のX線回折図形において現れるピークの角度、および必要に応じてTEMEDXを用いて判別される。
SiO2成分を40.0%~70.0%、
Al2O3成分を11.0%~25.0%、
Na2O成分を5.0%~19.0%、
K2O成分を0%~9.0%、
MgO成分を1.0%~18.0%、
CaO成分を0%~3.0%、および
TiO2成分を0.5%~12.0%、
を含有する。
SiO2成分を40.0%~70.0%、
Al2O3成分を11.0%~25.0%、
Na2O成分を5.0%~19.0%、
K2O成分を0.1%~9.0%、
MgO成分を1.0%~18.0%、
CaO成分を0.01%~3.0%、および
TiO2成分を0.5%~12.0%、
を含有する。
Al2O3成分は、より好ましくは13.0%~23.0%含まれる。
Na2O成分は、より好ましくは8.0%~18.0%、さらに好ましくは9.0%~17.0%、特に好ましくは10.5%~16.0%含まれる。
K2O成分は、より好ましくは1.0%~7.0%、さらに好ましくは1.0%~5.0%含まれる。
MgO成分は、より好ましくは2.0%~15.0%、さらに好ましくは3.0%~13.0%、特に好ましくは5.0%~11.0%含まれる。
CaO成分は、より好ましくは0.1%~2.0%含まれる。
TiO2成分は、より好ましくは1.0%~10.0%、さらに好ましくは2.0%~8.0%含まれる。
Sb2O3成分、SnO2成分およびCeO2成分は、合計で、より好ましくは0.1%~2.0%、さらに好ましくは0.3%~1.0%含まれる。
上記の配合量は適宜組み合わせることができる。
SiO2成分、Al2O3成分、Na2O成分、K2O成分、MgO成分、CaO成分、TiO2成分、Sb2O3成分、SnO2成分およびCeO2成分を合わせて90%以上、好ましくは95%以上、より好ましくは98%以上、さらに好ましくは99%以上とできる。これら成分で100%を占めてもよい。
また、結晶化ガラスは、本発明の効果を損なわない範囲で、B2O3成分、P2O5成分、BaO成分、FeO成分、Li2O成分、SrO成分、La2O3成分、Y2O3成分、Nb2O5成分、Ta2O5成分、WO3成分、TeO2成分、Bi2O3成分をそれぞれ含んでもよいし、含まなくてもよい。配合量は、各々、0%以上2.0%以下、0%以上2.0%未満または0%以上1.0%以下とできる。
SiO2成分を43.0モル%~73.0モル%、
Al2O3成分を4.0モル%~18.0モル%、
Na2O成分を5.0モル%~19.0モル%、
K2O成分を0.1モル%~9.0モル%、
MgO成分を2.0モル%~22.0モル%、
CaO成分を0.01モル%~3.0モル%、
TiO2成分を0.5モル%~11.0モル%、並びに
Sb2O3成分、SnO2成分およびCeO2成分からなる群より選択される1種以上を0.01モル%~3.0モル%、
を含有する。
SiO2成分、Al2O3成分、Na2O成分、K2O成分、MgO成分、TiO2成分を合わせて90モル%以上、好ましくは95モル%以上、より好ましくは98モル%以上、さらに好ましくは99モル%以上とできる。
酸化物基準で表されたモル比[TiO2/Na2O]の値が0以上0.41以下であってよい。
酸化物基準で表されたモル比[MgO/Na2O]の値が0以上1.60以下であってよい。
本発明の結晶化ガラスは、例えば以下の方法で作製できる。すなわち、上記各成分が所定の含有量の範囲内になるように原料を均一に混合し、熔解成形して原ガラスを製造する。次にこの原ガラスを結晶化して結晶化ガラス母材を作製する。さらに結晶化ガラス母材を化学強化する。
2段階熱処理では、まず第1の温度で熱処理することにより核形成工程を行い、この核形成工程の後に、核形成工程より高い第2の温度で熱処理することにより結晶成長工程を行う。
1段階熱処理では、1段階の温度で核形成工程と結晶成長工程を連続的に行う。通常、所定の熱処理温度まで昇温し、当該熱処理温度に達した後に一定時間その温度を保持し、その後、降温する。
2段階熱処理の第1の温度は600℃~750℃が好ましい。第1の温度での保持時間は30分~2000分が好ましく、180分~1440分が最も好ましい。
2段階熱処理の第2の温度は650℃~850℃が好ましい。第2の温度での保持時間は30分~600分が好ましく、60分~300分が最も好ましい。
1段階の温度で熱処理する場合、熱処理の温度は600℃~800℃が好ましく、630℃~770℃がより好ましい。また、熱処理の温度での保持時間は、30分~500分が好ましく、60分~300分がより好ましい。
結晶化ガラスの各成分の原料として各々相当する酸化物、水酸化物、炭酸塩、硝酸塩、弗化物、塩化物、水酸化物、メタ燐酸化合物等の原料を選定し、これらの原料を以下の組成の割合になるように秤量して均一に混合した。
(酸化物換算の重量%)
SiO2成分を55%、Al2O3成分を18%、Na2O成分を12%、K2O成分を2%、MgO成分を8%、CaO成分を1%、TiO2成分を5%、Sb2O3成分を0.1%
1mm厚および10mm厚の結晶化ガラス母材について、日立ハイテクノロジー製U-4000形分光光度計により240~800nmの分光透過率を測定し、反射損失を含む透過率が80%になる波長を求めた。結果を表1,2に示す。
この明細書に記載の文献および本願のパリ優先の基礎となる日本出願明細書の内容を全てここに援用する。
Claims (5)
- 結晶化ガラスを母材とし、表面に圧縮応力層を有し、
厚さ10mmにおける反射損失を含む光線透過率が80%である波長が400~669nmであり、ビッカース硬度[Hv]が835~1300である結晶化ガラス。 - 前記圧縮応力層の厚さが20μm以上である請求項1に記載の結晶化ガラス。
- 前記結晶化ガラス母材が、酸化物換算の重量%で、
SiO2成分を40.0%~70.0%、
Al2O3成分を11.0%~25.0%、
Na2O成分を5.0%~19.0%、
K2O成分を0%~9.0%、
MgO成分を1.0%~18.0%、
CaO成分を0%~3.0%、および
TiO2成分を0.5%~12.0%、
を含有し、
SiO2成分、Al2O3成分、Na2O成分、K2O成分、MgO成分、TiO2成分を合わせて90%以上含有する請求項1または2に記載の結晶化ガラス。 - 前記結晶化ガラス母材が、酸化物換算の重量%で、
SiO2成分を45.0%~65.0%、
Al2O3成分を13.0%~23.0%、
Na2O成分を8.0%~16.0%、
K2O成分を1.0%~7.0%、
MgO成分を2.0%~15.0%、
CaO成分を0.1%~2.0%、
TiO2成分を1.0%~10.0%、並びに
Sb2O3成分、SnO2成分およびCeO2成分からなる群より選択される1種以上を0.1%~2.0%、
を含有し、
SiO2成分、Al2O3成分、Na2O成分、K2O成分、MgO成分、TiO2成分を合わせて90%以上含有する請求項1から3のいずれかに記載の結晶化ガラス。 - 析出結晶の平均結晶径が、4~15nmである請求項1から4のいずれかに記載の結晶化ガラス。
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