WO2019172426A1 - Lamelle couvre-objet, et appareil de communication sans fil - Google Patents

Lamelle couvre-objet, et appareil de communication sans fil Download PDF

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Publication number
WO2019172426A1
WO2019172426A1 PCT/JP2019/009367 JP2019009367W WO2019172426A1 WO 2019172426 A1 WO2019172426 A1 WO 2019172426A1 JP 2019009367 W JP2019009367 W JP 2019009367W WO 2019172426 A1 WO2019172426 A1 WO 2019172426A1
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glass
less
crystallized glass
crystallized
cover glass
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PCT/JP2019/009367
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English (en)
Japanese (ja)
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清 李
小池　章夫
一樹 金原
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Ａｇｃ株式会社
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Priority claimed from PCT/JP2018/027578 external-priority patent/WO2019022034A1/fr
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Publication of WO2019172426A1 publication Critical patent/WO2019172426A1/fr

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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
    • C03C21/00—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface

Definitions

  • the present invention relates to a cover glass for a wireless communication device or the like.
  • Chemically tempered glass is used as a cover glass for portable terminals. Chemically tempered glass, for example, by bringing the glass into contact with a molten salt containing alkali metal ions, causing ion exchange between the alkali metal ions in the glass and the alkali metal ions in the molten salt, and compressing stress on the glass surface. A layer is formed.
  • Crystallized glass is obtained by precipitating crystals in glass, and is harder and less damaged than amorphous glass not containing crystals.
  • Patent Document 1 describes an example in which crystallized glass is chemically strengthened by ion exchange treatment. However, crystallized glass is less transparent than amorphous glass.
  • Patent Document 2 describes a transparent crystallized glass.
  • an object of the present invention is to provide a cover glass having high strength and transparency and further having excellent high frequency characteristics.
  • the cover glass of the present invention that solves the above problems is a cover glass including crystallized glass having a visible light transmittance of 85% or more converted to a thickness of 0.8 mm, and the crystallized glass has a thickness of 0.00.
  • the haze value in terms of 8 mm is 1.0% or less, expressed in terms of mass% on the basis of oxide, SiO 2 is 58 to 70%, Al 2 O 3 is 15 to 30%, Li 2 O is 2 to 10%, Na 2 O 0-5%, K 2 O 0-2%, SrO 0-1.8%, BaO 0-2%, SnO 2 0.5-6%, ZrO 2 0.5 -6%, P 2 O 5 0 to 6%, the total content of SrO and BaO is 0.1 to 3%, and the total content of Na 2 O and K 2 O is 1 to 5 It is a crystallized glass having a relative dielectric constant at 10 GHz of 7.0 or less.
  • the crystallized glass may have a dielectric loss tangent at 10 GHz of 0.014 or less. In one embodiment of the cover glass of the present invention, the crystallized glass may contain ⁇ -spodumene. In one embodiment of the cover glass of the present invention, the crystallized glass may have a haze value of 0.6% or less in terms of a thickness of 0.8 mm. In one embodiment of the cover glass of the present invention, the crystallized glass may have an average coefficient of thermal expansion at 50 ° C. to 350 ° C. of 30 ⁇ 10 ⁇ 7 / ° C. or less.
  • the crystallized glass may have a Vickers hardness of 720 or more.
  • the crystallized glass may be a chemically strengthened glass having a surface compressive stress of 600 MPa or more and a compressive stress depth of 80 ⁇ m or more.
  • the chemically strengthened glass may have a maximum depth of 80 ⁇ m or more with a compressive stress value of 50 MPa or more.
  • the wireless communication device of the present invention has the cover glass of the present invention.
  • a cover glass having excellent transparency and strength and excellent high-frequency characteristics can be obtained.
  • FIG. 1 is a diagram showing an example of a stress profile of chemically strengthened glass.
  • FIG. 2 is a diagram showing an example of a powder X-ray diffraction pattern of crystallized glass.
  • FIG. 3 shows an example of an SEM image of the crystallized glass surface.
  • FIG. 4 shows an example of a TEM image of crystallized glass.
  • amorphous glass and “crystallized glass” are collectively referred to as “glass”.
  • amorphous glass refers to glass in which a diffraction peak showing a crystal is not observed by powder X-ray diffraction.
  • Crystalstallized glass is obtained by heat-treating “amorphous glass” to precipitate crystals, and contains crystals.
  • Cu ⁇ radiation is used to measure 2 ⁇ in the range of 10 ° to 80 °, and when a diffraction peak appears, the precipitated crystal is identified by, for example, the three strong line method.
  • chemically tempered glass refers to glass after chemical strengthening treatment
  • chemically strengthened glass refers to glass before chemical strengthening treatment
  • matrix composition of chemically strengthened glass is a glass composition of chemically strengthened glass, and glass in a portion deeper than the compressive stress depth DOL of chemically strengthened glass, except when an extreme ion exchange treatment is performed.
  • the composition is the mother composition of chemically strengthened glass.
  • the glass composition is expressed in terms of mass% based on oxide, and the mass% is simply expressed as “%”. Further, in the present specification, “substantially does not contain” means that it is below the impurity level contained in the raw material or the like, that is, not intentionally added. Specifically, it is less than 0.1%, for example.
  • the “stress profile” refers to a value representing a compressive stress value with the depth from the glass surface as a variable. An example is shown in FIGS. In the stress profile, the tensile stress is expressed as a negative compressive stress.
  • the “compressive stress value (CS)” can be measured by slicing a cross section of the glass and analyzing the sliced sample with a birefringence imaging system.
  • An example of the birefringence imaging system is a birefringence imaging system Abrio-IM manufactured by Tokyo Instruments. It can also be measured using scattered light photoelasticity. In this method, light can be incident from the surface of the glass, and CS can be measured by analyzing the polarization of the scattered light.
  • the “compressive stress layer depth (DOL)” is a depth at which the compressive stress value becomes zero.
  • CT internal tensile stress
  • visible light transmittance refers to an average transmittance of light having a wavelength of 380 nm to 780 nm.
  • haze value refers to a haze value measured according to JIS K3761: 2000 using a C light source.
  • Vickers hardness is Vickers hardness (HV0.1) defined in JIS R1610: 2003.
  • the “fracture toughness value” refers to an indenter press-fitting method (IF method) fracture toughness value defined in JIS R1607: 2010.
  • the cover glass of the present embodiment includes a crystallized glass described later (hereinafter also referred to as “the present crystallized glass”).
  • the entire cover glass may be the present crystallized glass, or there may be a portion made of a material other than the present crystallized glass.
  • This cover glass is, for example, a cover glass for various displays, and specifically, for example, is a cover glass for a display of a wireless communication device. Since the present cover glass includes the present crystallized glass having excellent high-frequency characteristics as will be described later, it is particularly suitable as a cover glass for a display of a radio communication device for high-frequency communication (for example, mobile devices such as mobile phones and smartphones) .
  • this cover glass may be used as a surface member of an electronic device, and may be used as a back surface member or a housing.
  • the cover glass may have holes for speakers, operation buttons, camera lenses, and the like.
  • the crystallized glass is a glass containing crystals obtained by heat-treating an amorphous glass described later to be crystallized.
  • the crystallized glass may or may not be subjected to chemical strengthening treatment, that is, the crystallized glass may or may not include a compressive stress layer.
  • the crystallized glass is preferably subjected to a chemical strengthening treatment. In the following, among the crystallized glasses, those subjected to chemical strengthening treatment may be referred to as “main strengthened glass”.
  • the crystallized glass preferably contains ⁇ -spodumene. That is, the crystallized glass is preferably crystallized glass in which ⁇ -spodumene is precipitated.
  • ⁇ -spodumene is expressed as LiAlSi 2 O 6, and generally has a Bragg angle (2 ⁇ ) of 25.55 ° ⁇ 0.05 °, 22.71 ° ⁇ 0.05 ° in the X-ray diffraction spectrum. 28.20 ° ⁇ 0.05 ° is a crystal showing a diffraction peak.
  • the Rietveld method it is possible to confirm the precipitation of ⁇ -spodumene from the X-ray diffraction spectrum even when the crystal structure is distorted.
  • Crystallized glass containing ⁇ -spodumene is preferable because it has excellent chemical strengthening properties. Since ⁇ -spodumene has a dense crystal structure, a high compressive stress is generated when ions in the deposited crystal are replaced by larger ions by ion exchange treatment for chemical strengthening, and the effect of chemical strengthening is expected to increase. .
  • the crystallized glass containing ⁇ -spodumene is preferable because it has a small coefficient of thermal expansion and can easily obtain a preferable average coefficient of thermal expansion described later.
  • crystallized glass containing ⁇ -spodumene tends to have large crystals, and therefore has low visible light permeability and a large haze value.
  • visible light transmittance can be increased and the haze value can be decreased.
  • the crystal contained in the crystallized glass is not limited to ⁇ -spodumene, but may be other crystals.
  • the crystallized glass preferably has a small thermal expansion coefficient.
  • the average thermal expansion coefficient of the crystallized glass at 50 ° C. to 350 ° C. is preferably 30 ⁇ 10 ⁇ 7 / ° C. or less, more preferably 25 ⁇ 10 ⁇ 7 / ° C. or less, and further preferably 20 ⁇ 10 ⁇ 7 / ° C. Hereinafter, it is particularly preferably 15 ⁇ 10 ⁇ 7 / ° C. or less.
  • the average thermal expansion coefficient at 50 ° C. to 350 ° C. of the crystallized glass is preferably as small as possible, but is usually 10 ⁇ 10 ⁇ 7 / ° C. or more.
  • the crystallization rate of the crystallized glass is preferably 10% or more, more preferably 15% or more, further preferably 20% or more, and particularly preferably 25% or more in order to increase the mechanical strength.
  • the crystallization of the crystallized glass is performed.
  • the rate is preferably 90% or less, more preferably 85% or less, and particularly preferably 80% or less.
  • the crystallization rate can be calculated from the X-ray diffraction intensity by the Rietveld method.
  • the Rietveld method is described in the “Crystal Analysis Handbook” Editorial Committee edited by the Crystallographic Society of Japan, “Crystal Analysis Handbook” (Kyoritsu Publishing 1999, p492-499).
  • the average particle size of the precipitated crystals of the crystallized glass is preferably 300 nm or less, more preferably 200 nm or less, further preferably 150 nm or less, and particularly preferably 100 nm or less.
  • the average particle size of the precipitated crystals can be determined from a transmission electron microscope (TEM) image. It can also be estimated from a scanning electron microscope (SEM) image.
  • FIG. 3 shows an example of an SEM image observed by observing a cross section of the crystallized glass by mirror polishing, etching with hydrofluoric acid. In the SEM image of FIG. 3, the bright portion is a precipitated crystal, and the dark portion is a glass phase.
  • FIG. 4 shows an example of a TEM image obtained by observing the crystallized glass in a thin piece by an ion milling method at an observation magnification of 50000 times.
  • the relative permittivity ⁇ at a frequency of 10 GHz of the crystallized glass is preferably 7.0 or less because the communication efficiency is good when the cover glass is used for a radio communication device for high frequency communication. Accordingly, the relative dielectric constant ⁇ of the crystallized glass at a frequency of 10 GHz is 7.0 or less, preferably 6.7 or less, and more preferably 6.5 or less. Further, ⁇ is usually 3.7 or more.
  • the dielectric tangent tan ⁇ at a frequency of 10 GHz of the crystallized glass is preferable because it is smaller than the non-crystallized glass. This is because tan ⁇ becomes smaller as a whole because crystals having a lower tan ⁇ than glass precipitate in the glass.
  • the dielectric loss tangent tan ⁇ at a frequency of 10 GHz of the crystallized glass is preferably 0.014 or less, more preferably 0.013 or less, and still more preferably 0.012 or less. Further, tan ⁇ is usually 0.0001 or more.
  • the fracture toughness value Kc of the present crystallized glass is preferably 0.8 MPa ⁇ m 1/2 or more, more preferably 1 MPa ⁇ m 1/2 or more, in order to make it difficult for the fragments to scatter when broken.
  • the Vickers hardness of the crystallized glass is preferably 680 or more, more preferably 700 or more, and further preferably 740 or more.
  • the Vickers hardness of the crystallized glass is preferably 1100 or less, more preferably 1050 or less, and even more preferably 1000 or less.
  • the visible light transmittance of the crystallized glass is 85% or more, more preferably 88% or more, when the thickness is 0.8 mm. % Or more is more preferable.
  • the visible light transmittance of the crystallized glass is preferably as high as possible, it is usually 91% or less in terms of a thickness of 0.8 mm.
  • permeability of thickness 0.8mm conversion of normal amorphous glass is about 90%.
  • the haze value of the crystallized glass is 1.0% or less, preferably 0.8% or less, when the thickness is 0.8 mm. 0.6% or less is more preferable, 0.5% or less is more preferable, 0.4% or less is particularly preferable, and 0.3% or less is most preferable.
  • the haze value is preferably as small as possible from the viewpoint of the visibility of the display, mechanical strength and high-frequency characteristics are lowered when the crystallization rate is reduced or the crystal grain size is reduced in order to reduce the haze value.
  • the haze value when the thickness of the crystallized glass is 0.8 mm is preferably 0.05% or more, more preferably 0.07% or more, and 0.09%. The above is more preferable.
  • the thickness (t) of the crystallized glass is preferably 3 mm or less, more preferably 2 mm or less, 1.6 mm or less, stepwise, in order to enable remarkable strength improvement by chemical strengthening. 1 mm or less, 0.9 mm or less, 0.8 mm or less, or 0.7 mm or less. Further, the thickness (t) is preferably 0.3 mm or more, more preferably 0.4 mm or more, and further preferably 0.5 mm or more in order to obtain sufficient strength by the chemical strengthening treatment. . Since the glass composition of the crystallized glass is the same as that of the amorphous glass before crystallization, it will be described in the section of amorphous glass.
  • the surface compressive stress CS 0 of the tempered glass is preferably at least 600 MPa, more 800MPa is more preferable.
  • the compressive stress depth DOL of the tempered glass is preferably 80 ⁇ m or more, and more preferably 100 ⁇ m or more.
  • the maximum depth at which the compressive stress value of the tempered glass is 50 MPa or more (hereinafter sometimes referred to as “50 MPa depth”) is preferably 80 ⁇ m or more, more preferably 100 ⁇ m or more. preferable.
  • the drop strength can be evaluated using, for example, the drop height measured by the following asphalt drop test.
  • a glass plate (120 mm ⁇ 60 mm ⁇ 0.8 mm) to be evaluated is regarded as a cover glass of a smartphone, attached to a housing simulating a smartphone, and dropped on a flat asphalt surface.
  • the total mass of the glass plate and the housing is about 140 g.
  • the test is started from a height of 30 cm, and if the chemically strengthened glass plate is not broken, the test is repeated by dropping the height of the chemically strengthened glass plate by 10 cm, and the height (unit: cm) at the time of breaking is recorded. This test is set as one set, and 10 sets are repeated, and the average value of the height when cracked is defined as “fall height”.
  • the drop height of the tempered glass in the asphalt drop test is preferably 100 cm or more.
  • CT of the tempered glass is 110 MPa or less, it is preferable because scattering of fragments is suppressed when the tempered glass is broken.
  • the CT of the present tempered glass is more preferably 100 MPa or less, and still more preferably 90 MPa or less.
  • CT of this tempered glass is preferably 50 MPa or more, more preferably 55 MPa or more, and further preferably 60 MPa or more.
  • the four-point bending strength of the tempered glass is preferably 900 MPa or more.
  • the 4-point bending strength is measured using a test piece of 40 mm ⁇ 5 mm ⁇ 0.8 mm at a lower span of 30 mm, an upper span of 10 mm, and a crosshead speed of 0.5 mm / min.
  • the average value of 10 test pieces is the 4-point bending strength.
  • the Vickers hardness of the crystallized glass tends to be larger than that before strengthening due to the chemical strengthening treatment. It is thought that this is because compressive stress is generated in the crystal by ion exchange between small ions in the crystal and large ions in the molten salt.
  • the Vickers hardness of the tempered glass is preferably 720 or more, more preferably 740 or more, and further preferably 780 or more. Moreover, the Vickers hardness of this tempered glass is usually 950 or less.
  • FIG. 2 shows an example of an X-ray diffraction pattern of the present tempered glass and crystallized glass (glass for chemical strengthening) before strengthening.
  • the solid line is an X-ray diffraction pattern measured for the crystallized glass plate before strengthening, and a diffraction line of ⁇ -spodumene crystal indicated by a black circle in FIG. 2 is recognized.
  • the dotted line shows the X-ray diffraction pattern measured for the crystallized glass plate after chemical strengthening.
  • the reason why the position of the diffraction peak has shifted to the lower angle side due to chemical strengthening is thought to be that the lattice spacing has increased due to ion exchange between small ions in the crystal and large ions in the molten salt. It is done.
  • the relative dielectric constant ⁇ , the dielectric loss tangent tan ⁇ , the visible light transmittance, and the haze value hardly change before and after the chemical strengthening treatment.
  • the present tempered glass has almost the same composition as the crystallized glass before tempering as a whole, except when an extreme ion exchange treatment is performed.
  • the composition of the deepest part from the glass surface is the same as the composition of the crystallized glass before strengthening, except when an extreme ion exchange treatment is performed.
  • the amorphous glass used for obtaining the crystallized glass will be described.
  • the crystallized glass can be obtained by crystallizing the amorphous glass by heat treatment.
  • This amorphous glass is SiO 2 58 to 70%, Al 2 O 3 15 to 30%, Li 2 O 2 to 10%, Na 2 O 0 to 5% in mass% based on oxide.
  • this glass composition will be described.
  • SiO 2 is a component that forms a network structure of glass.
  • SiO 2 is a component that increases chemical durability and is a constituent component of ⁇ -spodumene, which is a preferred precipitated crystal.
  • the content of SiO 2 in the present amorphous glass is 58% or more, preferably 60% or more, more preferably 64% or more.
  • the SiO 2 content of the present amorphous glass is 70% or less, preferably 68% or less, more preferably 66% or less.
  • Al 2 O 3 is an effective component for increasing the surface compressive stress due to chemical strengthening, and is also a component of ⁇ -spodumene.
  • the content of Al 2 O 3 in the amorphous glass is 15% or more, preferably 20% or more.
  • the content of Al 2 O 3 is 30% or less and preferably 25% or less so that the devitrification temperature of the glass does not become too high.
  • Li 2 O is a component that forms surface compressive stress by ion exchange, and is also a constituent component of ⁇ -spodumene.
  • the content of Li 2 O is 2% or more, preferably 4% or more.
  • the content of Li 2 O is 10% or less, preferably 8% or less, more preferably 6% or less.
  • the content ratio Li 2 O / Al 2 O 3 between Li 2 O and Al 2 O 3 is preferably 0.3 or less in order to increase transparency. If Li 2 O / Al 2 O 3 is too large, crystallization proceeds rapidly during heat treatment, the crystal grain size increases, and the transparency is considered to decrease.
  • Na 2 O is a component that improves the meltability of the glass.
  • Na 2 O is not essential, but the content when it is contained is preferably 0.5% or more, more preferably 1% or more.
  • the content of Na 2 O is preferably 5% or less, preferably 4% or less. More preferred is 3% or less.
  • K 2 O is a component that lowers the melting temperature of the glass and may be contained, though not essential.
  • the content is preferably 0.5% or more, and more preferably 1% or more.
  • the total content Na 2 O + K 2 O of Na 2 O and K 2 O is preferably at least 1%, 2% or more is more preferable.
  • the content of K 2 O is preferably 2% or less.
  • the total content Na 2 O + K 2 O of Na 2 O and K 2 O is preferably 5% or less, more preferably 4% or less, and even more preferably 3% or less in order to increase transparency.
  • ZrO 2 is a component constituting a crystal nucleus in the crystallization process.
  • the content of ZrO 2 is preferably 0.5% or more, more preferably 1% or more.
  • the content of ZrO 2 is preferably 6% or less, more preferably 5% or less, and even more preferably 4% or less.
  • SnO 2 is a component constituting a crystal nucleus in the crystallization treatment, and has a high effect of promoting the precipitation of ⁇ -spodumene crystals. Therefore, SnO 2 is preferably contained in an amount of 0.5% or more.
  • the content of SnO 2 is more preferably 1% or more, and further preferably 1.5% or more.
  • the content of SnO 2 is preferably 6% or less in order to make it difficult to cause defects due to unmelted material in the glass. More preferably, it is 5% or less, More preferably, it is 4% or less.
  • SnO 2 is also a component that increases solarization resistance. In order to suppress solarization, the SnO 2 content is preferably 1% or more, and more preferably 1.5% or more.
  • TiO 2 and ZrO 2 are known as crystal nucleation components of crystallized glass.
  • ZrO 2 is more preferable than TiO 2.
  • the effect of crystal nucleation was higher.
  • SnO 2 the transparency of the crystallized glass was higher.
  • SnO 2 and ZrO 2 of SnO 2 + ZrO 2 of 3% or more are preferable because a large amount of ZrO 2 nuclei are formed and the transmittance is improved.
  • SnO 2 + ZrO 2 is more preferably 4% or more, further preferably 5% or more, particularly preferably 6% or more, and most preferably 7% or more.
  • SnO 2 + ZrO 2 is preferably 12% or less, more preferably 10% or less, still more preferably 9% or less, and particularly preferably 8% or less in order to make it difficult to cause defects due to unmelted material in the glass.
  • the ratio of the amount of SnO 2 with respect to the total amount thereof SnO 2 / (SnO 2 + ZrO 2) is 0.3 or more in order to increase transparency
  • 0.35 or more is more preferable, and 0.45 or more is more preferable.
  • SnO 2 / (SnO 2 + ZrO 2 ) is preferably 0.7 or less, more preferably 0.65 or less, and even more preferably 0.6 or less in order to increase the strength.
  • TiO 2 is a component for forming a crystal nucleus, and is a component that makes it difficult for fragments to scatter when the chemically strengthened glass is broken.
  • the content in the case of containing TiO 2 is preferably 0.1% or more, more preferably 0.15% or more, and further preferably 0.2% or more.
  • the content of TiO 2 in the present amorphous glass is preferably 5% or less, more preferably 3% or less, and still more preferably 1.5% or less.
  • Fe 2 O 3 when Fe 2 O 3 is contained in the glass, if the glass contains TiO 2 , a complex called an ilmenite complex is formed, and yellow or brown coloring is likely to occur. Since Fe 2 O 3 is usually contained as an impurity in the glass, the content of TiO 2 is preferably 1% or less, more preferably 0.5% or less, and still more preferably 0.25 in order to prevent coloring. % Or less, and it is particularly preferred not to contain substantially.
  • P 2 O 5 is not essential, but has an effect of promoting crystallization by promoting phase separation of glass, and may be contained.
  • the content is preferably 0.1% or more, more preferably 0.5% or more, still more preferably 1% or more, and particularly preferably 2% or more.
  • the content of P 2 O 5 is too large, it debris likely to scatter when a chemically tempered glass is broken, also acid resistance is remarkably lowered.
  • the content of P 2 O 5 is preferably 6% or less, more preferably 5% or less, further preferably 4% or less, particularly preferably 3% or less, and most preferably 2% or less.
  • the amorphous glass does not substantially contain P 2 O 5 .
  • B 2 O 3 is a component that improves the chipping resistance of the crystallized glass and improves the meltability, and may be contained.
  • B 2 O 3 is not essential, but the content in the case of containing B 2 O 3 is preferably 0.5% or more, more preferably 1% or more, further preferably, in order to improve the meltability. 2% or more.
  • the content when containing B 2 O 3 is 5% or less. Is preferable, more preferably 4% or less, still more preferably 3% or less, and particularly preferably 1% or less.
  • the amorphous glass does not substantially contain B 2 O 3 .
  • MgO is a component that increases the surface compressive stress of the chemically strengthened glass, and is a component that suppresses the scattering of fragments when the chemically strengthened glass breaks, and may be included.
  • the content is preferably 0.5% or more, more preferably 1% or more.
  • the content of MgO is preferably 5% or less, more preferably 4% or less, and even more preferably 3% or less.
  • CaO is a component that improves the meltability, and may be contained to improve the solubility while preventing devitrification at the time of melting and suppressing an increase in the thermal expansion coefficient.
  • the content is preferably 0.5% or more, more preferably 1% or more.
  • the content when CaO is contained is preferably 4% or less, more preferably 3% or less, and particularly preferably 2% or less.
  • SrO is a component that improves the meltability and is a component that improves the refractive index of the glass.
  • SrO may be contained in order to improve the transmittance of the crystallized glass by bringing the refractive index of the glass phase remaining after crystallization close to the refractive index of the precipitated crystal and to lower the haze value.
  • the content when SrO is contained is preferably 0.1% or more, more preferably 0.2% or more, still more preferably 0.5% or more, and particularly preferably 1% or more. .
  • the SrO content is preferably 2.5% or less, more preferably 1.8% or less, and 1.5% or less. Further preferred is 1% or less, and most preferred is 0.5% or less.
  • BaO is a component that improves the meltability and is a component that improves the refractive index of the glass.
  • BaO may be contained to improve the transmittance of the crystallized glass by reducing the refractive index of the glass phase remaining after crystallization and the refractive index of the ⁇ -spodumene crystal phase, and to reduce the haze value.
  • the content is preferably 0.1% or more, more preferably 0.2% or more, still more preferably 0.5% or more, and particularly preferably 1% or more. .
  • the content when BaO is contained is preferably 2% or less, more preferably 1.5% or less, still more preferably 1% or less, 0 .5% or less is particularly preferable, and 0.3% or less is most preferable.
  • SrO and BaO are contained.
  • the total content of SrO and BaO is 0.1% or more, preferably 0.2% or more, more preferably 0.5% or more, still more preferably 1% or more, and particularly preferably 1.5% or more.
  • the total content of SrO and BaO is 3% or less, preferably 2% or less, more preferably 1.5% or less, further preferably 1% or less, particularly preferably 0.8% or less, and most preferably 0.5% or less.
  • ZnO is a component that lowers the thermal expansion coefficient of the crystallized glass and increases chemical durability, and also improves the transmittance of the crystallized glass and lowers the haze value. Also good.
  • the content when ZnO is contained is preferably 0.5% or more, more preferably 1% or more, and still more preferably 1 .5% or more, particularly preferably 2% or more.
  • the content of ZnO is preferably 4% or less, more preferably 3% or less, and even more preferably 2% or less.
  • Y 2 O 3 , La 2 O 3 , Nb 2 O 5 and Ta 2 O 5 are all components that make it difficult for fragments to scatter when the chemically strengthened glass breaks, and are also components that increase the refractive index. You may make it contain. If the inclusion of these components, Y 2 O 3, La 2 O 3, Nb 2 total Y 2 O content of O 5 3 + La 2 O 3 + Nb 2 O 5 is preferably 0.5% or more, more preferably Is 1% or more, more preferably 1.5% or more, and particularly preferably 2% or more.
  • Y 2 O 3 + La 2 O 3 + Nb 2 O 5 is preferably 4% or less, more preferably 3% or less, and further preferably 2% or less, Particularly preferably, it is 1% or less.
  • the total content of Y 2 O 3 , La 2 O 3 , Nb 2 O 5 and Ta 2 O 5 Y 2 O 3 + La 2 O 3 + Nb 2 O 5 + Ta 2 O 5 is preferably 0.5% or more. More preferably, it is 1% or more, further preferably 1.5% or more, and particularly preferably 2% or more.
  • Y 2 O 3 + La 2 O 3 + Nb 2 O 5 + Ta 2 O 5 is preferably 4% or less, more preferably 3% or less, and further preferably It is 2% or less, and particularly preferably 1% or less.
  • the amorphous glass may contain CeO 2.
  • CeO 2 has an effect of oxidizing glass, and when a large amount of SnO 2 is contained, the reduction of SnO 2 to the coloring component SnO may be suppressed to suppress coloring.
  • the content is preferably 0.03% or more, more preferably 0.05% or more, and further preferably 0.07% or more.
  • the content of CeO 2 is preferably 1.5% or less and more preferably 1% or less in order to increase transparency.
  • the coloring component when coloring this crystallized glass and using it, you may add a coloring component in the range which does not inhibit achievement of a desired characteristic.
  • the coloring component include Co 3 O 4 , MnO 2 , Fe 2 O 3 , NiO, CuO, Cr 2 O 3 , V 2 O 5 , Bi 2 O 3 , SeO 2 , Er 2 O 3 , Nd 2 O. 3 is a preferred example.
  • the total content of the coloring components is preferably 1% or less.
  • the amorphous glass does not substantially contain these components.
  • SO 3 as a refining agent in melting of the glass, SO 3, chlorides, fluorides or the like may be appropriately be contained. It is preferable not to contain As 2 O 3 . In the case of containing Sb 2 O 3 , the content is preferably 0.3% or less, more preferably 0.1% or less, and most preferably not contained.
  • the crystallized glass can be obtained by subjecting the amorphous glass to a crystallization treatment. Further, the present tempered glass can be obtained by subjecting the crystallized glass obtained by subjecting the amorphous glass to crystallization treatment to chemical strengthening treatment.
  • Amorphous glass can be manufactured, for example, by the following method.
  • the manufacturing method described below is an example in the case of manufacturing plate-shaped amorphous glass.
  • glass raw materials are prepared so that amorphous glass having a desired composition is obtained, and heated and melted in a glass melting furnace. Thereafter, the molten glass is homogenized by bubbling, stirring, adding a clarifying agent, etc., formed into a glass plate having a predetermined thickness by a known forming method, and gradually cooled.
  • the molten glass may be formed into a plate shape by a method in which the molten glass is formed into a block shape and slowly cooled and then cut.
  • Examples of the method for forming the sheet glass include a float method, a press method, a fusion method, and a downdraw method.
  • the float method is preferable.
  • continuous molding methods other than the float method for example, a fusion method and a downdraw method are also preferable.
  • Crystallized glass is obtained by heat-treating the amorphous glass obtained by the above procedure.
  • the temperature is raised from room temperature to the first treatment temperature and held for a certain period of time (nucleation treatment), and then kept at a second treatment temperature that is higher than the first treatment temperature for a certain period of time (crystal growth treatment). It is preferable to use two-stage heat treatment.
  • the first treatment temperature is preferably a temperature range in which the crystal nucleation rate is increased in the glass composition
  • the second treatment temperature is a temperature range in which the crystal growth rate is increased in the glass composition.
  • the holding time at the first treatment temperature is preferably long in order to generate a sufficient number of crystal nuclei. By generating a large number of crystal nuclei, the size of each crystal is reduced and crystallized glass with high transparency, that is, crystallized glass with high visible light transmittance and low haze value is obtained.
  • the first treatment temperature is, for example, 550 ° C. to 800 ° C.
  • the second treatment temperature is, for example, 850 ° C. to 1000 ° C. After holding at the first treatment temperature for 2 hours to 10 hours, Hold at processing temperature for 2-10 hours.
  • the crystallized glass obtained by the above procedure is ground and polished as necessary to form a crystallized glass plate.
  • a crystallized glass plate is cut into a predetermined shape and size, or chamfered, if it is cut or chamfered before chemical strengthening, the end face (cut surface) is obtained by subsequent chemical strengthening. Also, a compressive stress layer is formed, which is preferable.
  • the glass is brought into contact with the metal salt by a method such as immersing in a melt of a metal salt (for example, potassium nitrate) containing a metal ion having a large ionic radius (typically, Na ion or K ion).
  • a metal salt for example, potassium nitrate
  • a metal ion having a large ionic radius typically, Na ion or K ion.
  • small ionic radius metal ions typically Na or Li ions
  • Na ions are K ions.
  • Li—Na exchange in which Li ions in the glass are exchanged with Na ions.
  • Na—K exchange In order to form a large compressive stress by ion exchange, it is preferable to use “Na—K exchange” in which Na ions in glass are exchanged with K ions.
  • Examples of molten salts for performing chemical strengthening treatment include nitrates, sulfates, carbonates, and chlorides.
  • examples of the nitrate include lithium nitrate, sodium nitrate, potassium nitrate, cesium nitrate, and silver nitrate.
  • examples of the sulfate include lithium sulfate, sodium sulfate, potassium sulfate, cesium sulfate, and silver sulfate.
  • Examples of the carbonate include lithium carbonate, sodium carbonate, and potassium carbonate.
  • Examples of the chloride include lithium chloride, sodium chloride, potassium chloride, cesium chloride, silver chloride and the like. These molten salts may be used alone or in combination of two or more.
  • the treatment conditions for the chemical strengthening treatment may be selected appropriately in terms of time and temperature in consideration of the glass composition and the type of molten salt.
  • the present tempered glass is preferably obtained by, for example, the following two-stage chemical strengthening treatment.
  • the crystallized glass obtained by the crystallization treatment is immersed in a metal salt (for example, sodium nitrate) containing Na ions at about 350 to 500 ° C. for about 0.1 to 10 hours.
  • a metal salt for example, sodium nitrate
  • This causes ion exchange between Li ions in the crystallized glass and Na ions in the metal salt.
  • a compressive stress layer having a surface compressive stress of 200 MPa or more and a compressive stress depth of 80 ⁇ m or more can be formed.
  • the surface compressive stress is preferably 1000 MPa or less, more preferably 900 MPa or less, and still more preferably 700 MPa or less, particularly preferably 600 MPa or less.
  • the glass after the treatment is immersed in a metal salt (for example, potassium nitrate) containing K ions at about 350 to 500 ° C. for about 0.1 to 10 hours.
  • a metal salt for example, potassium nitrate
  • K ions at about 350 to 500 ° C. for about 0.1 to 10 hours.
  • a large compressive stress is generated in, for example, a portion within a depth of about 10 ⁇ m of the compressive stress layer formed in the previous treatment.
  • a preferable stress profile having a surface compressive stress of 600 MPa or more is easily obtained.
  • the crystallized glass may be kept in the atmosphere at 350 to 500 ° C. for 1 to 5 hours, and then immersed in a metal salt containing K ions.
  • the holding temperature in the atmosphere is preferably 425 ° C. to 475 ° C., more preferably 440 ° C. to 460 ° C.
  • a metal salt containing Na ions and Li ions at 350 to 500 ° C. for example, sodium nitrate and lithium nitrate
  • Immersion in a metal salt containing Na ions and Li ions causes ion exchange between Na ions in the glass and Li ions in the metal salt, and a more favorable stress profile is formed, thereby increasing the drop strength.
  • the total treatment time is preferably 10 hours or less, more preferably 5 hours or less, and even more preferably 3 hours or less from the viewpoint of production efficiency.
  • a total processing time of 0.5 hours or more is required. More preferably, it is 1 hour or more.
  • the wireless communication device includes the cover glass.
  • the wireless communication device may be provided with the cover glass on the front surface portion, as a back member, or as a housing.
  • This wireless communication device is suitable for high-frequency communication of, for example, 5 GHz to 200 GHz.
  • “wireless communication device” refers to an electronic device that uses wireless communication.
  • the wireless communication device includes a mobile phone, a tablet, a personal computer, a clock, glasses, and the like.
  • the obtained glass block was processed into a plate shape having a thickness of 0.5 mm, and a relative permittivity ⁇ and a dielectric loss tangent tan ⁇ at 10 GHz were measured by a slip post dielectric resonance method (SPDR method) using a network analyzer. It measured similarly after the below-mentioned crystallization process. The measurement results after the crystallization treatment are shown in Table 2.
  • Example 1 to Example 4 The obtained glass block was processed into a plate shape of 50 mm ⁇ 50 mm ⁇ 1.5 mm and then heat-treated (crystallization treatment) to obtain crystallized glass (Example 1 to Example 4, Example 8 to Example 10).
  • Table 2 shows the amorphous glass used and the heat treatment conditions.
  • the upper stage is the nucleation treatment condition
  • the lower stage is the crystal growth treatment condition. After holding, it means holding at 920 ° C. for 4 hours.
  • the obtained crystallized glass was processed and mirror-polished to obtain a crystallized glass plate having a thickness t of 0.8 mm. Moreover, the rod-shaped sample for measuring a thermal expansion coefficient was produced. A part of the remaining crystallized glass was pulverized and used for analysis of precipitated crystals. Various physical properties of the crystallized glass were measured by the following methods. The measurement results are shown in Table 2. Blank indicates unrated. (Coefficient of thermal expansion) Based on JIS R1618: 2002, an average thermal expansion coefficient [unit: ⁇ 10 ⁇ 7 / ° C.] at 50 ° C. to 350 ° C. was measured using a thermal dilatometer (manufactured by Bruker AXS Co., Ltd .; TD5000SA). The heating rate was 10 ° C./min.
  • Stress profile The stress value was measured using a surface stress meter FSM-6000 manufactured by Orihara Seisakusho Co., Ltd. and a measuring machine SLP1000 manufactured by Orihara Seisakusho Co., Ltd. using scattered light photoelasticity, and the compression stress value CS 0 [unit: MPa] The depth DOL [unit: ⁇ m] at which the compressive stress value becomes zero was read. The results are shown in Table 2. Moreover, the stress profile of Example 1 is shown in FIG. (Fracture toughness value Kc) Based on JIS R1607: 2010, a fracture toughness value Kc was determined by an indenter press-in method (IF method) using a Vickers hardness tester (Futuretec; FLC-50V).
  • IF method indenter press-in method
  • Indentation was performed with a load of 3 kgf in an atmosphere of a temperature of 22 ° C. and a relative humidity of 40%. Indentation length was measured 20 minutes after indentation in the same atmosphere in consideration of the effect of slow crack growth. Ten samples were measured for each sample, and the average value was calculated as the fracture toughness value Kc [unit: MPa ⁇ m 1/2 ].
  • Example 1 and Example 2 have higher transmittance and smaller haze values than Example 10 using glass 10 containing no SrO or BaO. Comparing Example 1 and Example 9, it can be seen that the crystallized glass containing SrO exceeding 1.8% has a low transmittance and a large haze value.
  • Example 8 uses the same amorphous glass as Example 1, and has a smaller average crystal grain size than Example 1, but a haze value larger than Example 1. This is because in Example 8, the difference in refractive index was increased by the precipitation of crystals having a refractive index different from that of ⁇ -spodumene.
  • Glass 11 produced by simulating a commercially available glass for chemical strengthening has a high transmittance and a low haze value, so that it has excellent transparency and strength, but has a large relative dielectric constant and dielectric loss tangent. On the other hand, it can be seen that the crystallized glass of Example 1 has excellent high frequency characteristics in addition to high strength and transparency.

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  • Engineering & Computer Science (AREA)
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Abstract

L'invention a pour objet de fournir une lamelle couvre-objet dotée d'une haute résistance et d'une haute transparence, et qui comporte d'excellentes propriétés haute fréquence. La lamelle couvre-objet de l'invention présente une transmittance de lumière visible en termes d'épaisseur de 0,8mm supérieure ou égale à 85%, et une valeur de trouble inférieure ou égale à 1,0%. En % en masse en termes de teneur en oxyde, le total des teneurs en ＳｉＯ２、Ａｌ２Ｏ３、Ｌｉ２Ｏ、Ｎａ２Ｏ、Ｋ２Ｏ、ＳｒＯ、ＢａＯ、ＳｎＯ２、ＺｒＯ２、Ｐ２Ｏ５, le total des teneurs en ＳｒＯ et ＢａＯ, et le total des teneurs en Ｎａ２Ｏ et Ｋ２Ｏ, sont compris à l'intérieur de plages prédéfinies. La constante diélectrique relative de cette lamelle couvre-objet à １０ＧＨｚ, est inférieure ou égale à 7,0.
PCT/JP2019/009367 2018-03-09 2019-03-08 Lamelle couvre-objet, et appareil de communication sans fil WO2019172426A1 (fr)

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WO2022044799A1 (fr) * 2020-08-24 2022-03-03 Ａｇｃ株式会社 Verre, verre renforcé chimiquement, et procédé de production d'un verre ayant une forme incurvée
WO2022050105A1 (fr) * 2020-09-04 2022-03-10 株式会社 オハラ Verre cristallisé renforcé

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JPH08151228A (ja) * 1994-11-25 1996-06-11 Asahi Glass Co Ltd 表面結晶化高強度ガラス、その製法及びその用途
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WO2022044799A1 (fr) * 2020-08-24 2022-03-03 Ａｇｃ株式会社 Verre, verre renforcé chimiquement, et procédé de production d'un verre ayant une forme incurvée
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WO2022050105A1 (fr) * 2020-09-04 2022-03-10 株式会社 オハラ Verre cristallisé renforcé

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