Crystallized glass, crystallized glass product and its manufacturing method

Abstract

The present invention provides a crystallized glass product, which contains, by weight percentage, 40-60% SiO2, 20-40% Al2O3, 2-15% Li2O, 3-20% Na2O, and 1-15% P2O5 + ZrO2 as constituents. Due to the rational component design, the crystallized glass product obtained by the present invention has excellent mechanical properties and is suitable for use in fields such as display devices and electronic devices.

Description

[Technical Field]

[0001] The present invention relates to crystallized glass, and more particularly to crystallized glass having excellent mechanical properties, a crystallized glass product, and a method for producing the same. [Background technology]

[0002] In recent years, with the rise and development of consumer electronic products, glass, as a transparent and high-performance material, has been widely applied to such electronic devices. For example, glass used in equipment such as LEDs, LCD displays, and computer monitors, as well as portable electronic products (e.g., mobile phones, tablet computers, and personal media terminals), not only needs to withstand general "touch" contact for a long period of time during application, but also needs to withstand accidental bending, scratches, and impacts that may occur during use, which places high demands on the related performance of glass.

[0003] Glass-ceramics is a material in which crystals are precipitated inside glass by heat-treating the glass. It has superior mechanical properties to conventional glasses, and the crystallites formed in the glass give it clear advantages over conventional glasses in terms of bending resistance, abrasion resistance, and drop resistance. Meanwhile, the mechanical properties of glass-ceramics can also be further improved by chemical strengthening. Based on these advantages, glass-ceramics or glass-ceramics products obtained by processing it are currently used in displays and electronic devices that have high requirements for drop resistance, pressure resistance, scratch resistance, etc., and are particularly used for the front and back covers of portable electronic devices (e.g., mobile phones, watches, PADs, etc.).

[0004] Therefore, developing crystallized glass and crystallized glass products that have excellent mechanical properties and are suitable for display devices or electronic devices has become a goal pursued by scientists. Summary of the Invention [Problem to be solved by the invention]

[0005] The technical problem to be solved by the present invention is to provide a crystallized glass and a crystallized glass product having excellent mechanical properties. [Means for solving the problem]

[0006] The technical means used by the present invention to solve the technical problems are as follows:

[0007] (1) A crystallized glass product containing, by weight percentage, 40-60% SiO2, 20-40% Al2O3, 2-15% Li2O, 3-20% Na2O, and 1-15% P2O5+ZrO2 as constituents.

[0008] (2) The crystallized glass product according to (1), further containing, as constituents, by weight percentage, 0-8% K2O, and / or 0-6% ZnO, and / or 0-6% B2O3, and / or 0-8% RO, and / or 0-5% TiO2, and / or 0-5% Ln2O3, and / or 0-2% fining agent, wherein the RO is one or more of MgO, CaO, SrO, and BaO, and the Ln2O3 is one or more of La2O3, Gd2O3, and Y2O3.

[0009] (3) A crystallized glass product containing, as constituents, by weight percentage, 40-60% SiO2, 20-40% Al2O3, 2-15% Li2O, 3-20% Na2O, 1-15% P2O5 + ZrO2, 0-8% K2O, 0-6% ZnO, 0-6% B2O3, 0-8% RO, 0-5% TiO2, 0-5% Ln2O3, and 0-2% fining agent, wherein the RO is one or more of MgO, CaO, SrO, and BaO, and the Ln2O3 is one or more of La2O3, Gd2O3, and Y2O3.

[0010] (4) A crystallized glass product containing SiO2, Al2O3, Li2O and Na2O as constituent components, containing a nepheline crystalline phase, and having a surface stress of 150 MPa or more.

[0011] (5) Contains nepheline crystal phase as the main crystalline phase, and has a Vickers hardness of 750 kgf / mm 2 That is all for the crystallized glass product.

[0012] (6) A crystallized glass product containing, by weight percentage, 40-60% SiO2, 20-40% Al2O3, 2-15% Li2O, and 3-20% Na2O as constituents, and containing a nepheline crystalline phase.

[0013] (7) A crystallized glass product containing SiO2, Al2O3, Li2O and Na2O as constituent components, and having a thickness of 1 mm or less and a four-point bending strength of 700 MPa or more.

[0014] (8) A crystallized glass product containing SiO2, Al2O3, Li2O and Na2O as constituents, and having a haze of 0.15% or less when the thickness of the crystallized glass product is 1 mm or less.

[0015] (9) A crystallized glass product containing a nepheline crystalline phase and having a thickness of 1 mm or less, the light transmittance at a wavelength of 550 nm being 88% or more.

[0016] (10) A crystallized glass product containing a nepheline crystalline phase and having an ion exchange layer depth of 50 μm or more.

[0017] (11) A crystallized glass product according to any one of (4) to (10), containing, as constituents, by weight percentage, 40 to 60% SiO2, and / or 20 to 40% Al2O3, and / or 2 to 15% Li2O, and / or 3 to 20% Na2O, and / or 1 to 15% P2O5+ZrO2.

[0018] (12) The crystallized glass product according to any one of (4) to (11), further containing, as constituents, by weight percentage, 0 to 8% K2O, and / or 0 to 6% ZnO, and / or 0 to 6% B2O3, and / or 0 to 8% RO, and / or 0 to 5% TiO2, and / or 0 to 5% Ln2O3, and / or 0 to 2% fining agent, wherein the RO is one or more of MgO, CaO, SrO, and BaO, and the Ln2O3 is one or more of La2O3, Gd2O3, and YO3.

[0019] (13) The crystallized glass product according to any one of (1) to (12), wherein, when the weight percentages of the constituent components are calculated, (Al2O3+Na2O) / P2O5 is 3.0 to 30.0, preferably (Al2O3+Na2O) / P2O5 is 4.0 to 20.0, more preferably (Al2O3+Na2O) / P2O5 is 5.0 to 15.0, and even more preferably (Al2O3+Na2O) / P2O5 is 6.0 to 10.0.

[0020] (14) The crystallized glass product according to any one of (1) to (13), wherein the SiO2 / Al2O3 ratio is 1.2 to 2.8, preferably 1.3 to 2.5, more preferably 1.5 to 2.2, and even more preferably 1.6 to 2.0, when calculated as a weight percentage of the constituent components.

[0021] (15) The crystallized glass product according to any one of (1) to (14), wherein, when the components are calculated in weight percentage, SiO2 / (Na2O+B2O3) is 2.0 to 15.0, preferably SiO2 / (Na2O+B2O3) is 3.0 to 10.0, more preferably SiO2 / (Na2O+B2O3) is 4.0 to 8.0, and even more preferably SiO2 / (Na2O+B2O3) is 5.0 to 7.0.

[0022] (16) The crystallized glass product according to any one of (1) to (15), wherein, when the components are calculated in weight percentage, (Na2O+Li2O) / SiO2 is 0.1 to 0.8, preferably (Na2O+Li2O) / SiO2 is 0.15 to 0.7, more preferably (Na2O+Li2O) / SiO2 is 0.2 to 0.6, and even more preferably (Na2O+Li2O) / SiO2 is 0.25 to 0.5.

[0023] (17) The crystallized glass product according to any one of (1) to (16), wherein, when the components are calculated in weight percentage, (ZrO2+ZnO) / Na2O is 2.0 or less, preferably (ZrO2+ZnO) / Na2O is 1.5 or less, more preferably (ZrO2+ZnO) / Na2O is 0.01 to 1.0, and even more preferably (ZrO2+ZnO) / Na2O is 0.1 to 0.5.

[0024] (18) The crystallized glass product according to any one of (1) to (17), wherein, when the components are calculated in weight percentage, (P2O5+Na2O) / Li2O is 0.5 to 8.0, preferably (P2O5+Na2O) / Li2O is 0.8 to 5.0, more preferably (P2O5+Na2O) / Li2O is 1.0 to 3.0, and even more preferably (P2O5+Na2O) / Li2O is 1.5 to 2.5.

[0025] (19) The crystallized glass product according to any one of (1) to (18), wherein, when the components are calculated in weight percentage, K2O / ZrO2 is 0.1 or more, preferably K2O / ZrO2 is 0.2 to 10.0, more preferably K2O / ZrO2 is 0.3 to 5.0, and even more preferably K2O / ZrO2 is 0.4 to 1.5.

[0026] (20) The crystallized glass product according to any one of (1) to (19), wherein, when the components are calculated in weight percentage, (ZnO+RO+B2O3+TiO2) / P2O5 is 1.5 or less, preferably (ZnO+RO+B2O3+TiO2) / P2O5 is 1.0 or less, more preferably (ZnO+RO+B2O3+TiO2) / P2O5 is 0.5 or less, and even more preferably (ZnO+RO+B2O3+TiO2) / P2O5 is 0.2 or less, and the RO is one or more of MgO, CaO, SrO, and BaO.

[0027] (21) Constituents, in weight percentage, are 43 to 55% SiO2, preferably 46 to 53% SiO2, and / or 23 to 36% Al2O3, preferably 25.5 to 32% Al2O3, and / or 3 to 13% Li2O, preferably 5.5 to 11% Li2O, and / or 5 to 15% Na2O, preferably 6.5 to 12% Na2O, and / or 2 to 12% P2O5 + ZrO2, preferably 4 to 10% P2O5 + ZrO2, and / or 0 to 5% K2O, preferably 0.1 to 3% K2O, and / or 0 to 3% ZnO, preferably 0 to 1%. ZnO, and / or 0-3% B2O3, preferably 0-1% B2O3, and / or 0-5% RO, preferably 0-2% RO, and / or 0-3% TiO2, preferably 0-1% TiO2, and / or 0-3% Ln2O3, preferably 0-1% Ln2O3, and / or 0-1% fining agent, preferably 0-0.5% fining agent, wherein the RO is one or more of MgO, CaO, SrO, and BaO, and the Ln2O3 is one or more of La2O3, Gd2O3, and YO3.

[0028] (22) A crystallized glass product according to any one of (1) to (21), containing, as constituents, by weight percentage, 0 to 6% ZrO2, preferably 0 to 5% ZrO2, more preferably 0.1 to 3% ZrO2, and / or 0 to 10% P2O5, preferably 1 to 8% P2O5, more preferably 2 to 6% P2O5.

[0029] (23) The crystallized glass product according to any one of (1), (2), and (4) to (12), further containing, as a constituent, by weight percentage, 0 to 5% of Yb2O3+Nb2O5+WO3+Bi2O3+Ta2O5+TeO2+GeO2, preferably 0 to 2% of Yb2O3+Nb2O5+WO3+Bi2O3+Ta2O5+TeO2+GeO2, more preferably 0 to 1% of Yb2O3+Nb2O5+WO3+Bi2O3+Ta2O5+TeO2+GeO2.

[0030] (24) A crystallized glass product according to any one of (1) to (23), which does not contain, as constituents, SrO, and / or BaO, and / or MgO, and / or CaO, and / or ZnO, and / or PbO, and / or As2O3, and / or TiO2, and / or B2O3, and / or Y2O3, and / or La2O3, and / or Gd2O3.

[0031] (25) The crystallized glass product according to any one of (1) to (24), containing a nepheline crystal phase, and / or a lithium silicate crystal phase, and / or a lithium phosphate crystal phase, and / or a petalite crystal phase, and / or a quartz crystal phase.

[0032] (26) The crystallized glass product according to any one of (1) to (25), wherein the main crystal phase of the crystallized glass product is a nepheline crystal phase, or the crystallized glass product contains only a nepheline crystal phase.

[0033] (27) The crystallized glass product according to any one of (1) to (26), wherein the weight percentage of the neferine crystalline phase in the crystallized glass product is 10 to 80%, preferably, the weight percentage of the neferine crystalline phase in the crystallized glass product is 20 to 70%, and more preferably, the weight percentage of the neferine crystalline phase in the crystallized glass product is 30 to 60%.

[0034] (28) The ion exchange layer depth is 50 μm or more, preferably 60 μm or more, more preferably 80 μm or more, and even more preferably 100 μm or more, and / or the Vickers hardness is 750 kgf / mm 2 or more, and preferably 780 kgf / mm 2 More preferably, it is 800 kgf / mm 2 More preferably, it is 810 kgf / mm 2 and / or the crystal grain size is 80 nm or less, preferably 60 nm or less, more preferably 50 nm or less, and even more preferably 40 nm or less, and / or the surface stress is 150 MPa or more, preferably 170 MPa or more, and more preferably 190 MPa or more, the crystallized glass product according to any one of (1) to (27).

[0035] (29) A crystallized glass product having a thickness of 1 mm or less, according to any one of (1) to (28), wherein the crystallized glass product has a four-point bending strength of 700 MPa or more, preferably 750 MPa or more, and more preferably 800 MPa or more, and / or a ball drop test height of 1100 mm or more, preferably 1300 mm or more, and more preferably 1500 mm or more, and / or a haze of 0.15% or less, preferably 0.12% or less, and more preferably 0.10% or less, and / or a light transmittance at a wavelength of 550 nm of 88% or more, preferably 89% or more, more preferably 90% or more, and even more preferably 91% or more, and / or a |B| value at an average light wavelength of 400 to 800 nm of 1.5 or less, preferably 1.0 or less, and more preferably 0.8 or less.

[0036] (30) The crystallized glass product according to any one of (7) to (9) and (29), having a thickness of 0.2 to 1 mm, preferably 0.3 to 0.9 mm, more preferably 0.5 to 0.8 mm, and even more preferably 0.55 mm, 0.6 mm, 0.68 mm, 0.7 mm, or 0.75 mm.

[0037] (31) The crystallized glass product according to any one of (1), (2), and (4) to (12), further containing, as constituents, by weight percentage, 0 to 4% NiO, and / or 0 to 4% Ni2O3, and / or 0 to 2% CoO, and / or 0 to 2% Co2O3, and / or 0 to 7% Fe2O3, and / or 0 to 4% MnO2, and / or 0 to 8% Er2O3, and / or 0 to 8% Nd2O3, and / or 0 to 4% Cu2O, and / or 0 to 8% Pr2O3, and / or 0 to 4% CeO2.

[0038] (32) is a glass-ceramic containing, by weight percentage, 40-60% SiO2, 20-40% Al2O3, 2-15% Li2O, 3-20% Na2O, and 1-15% P2O5+ZrO2 as its constituents.

[0039] (33) The crystallized glass according to (32), further containing, as constituents, by weight percentage, 0 to 8% K2O, and / or 0 to 6% ZnO, and / or 0 to 6% B2O3, and / or 0 to 8% RO, and / or 0 to 5% TiO2, and / or 0 to 5% Ln2O3, and / or 0 to 2% fining agent, wherein the RO is one or more of MgO, CaO, SrO, and BaO, and the Ln2O3 is one or more of La2O3, Gd2O3, and Y2O3.

[0040] (34) Crystallized glass containing, as constituents, by weight percentage, 40 to 60% SiO2, 20 to 40% Al2O3, 2 to 15% Li2O, 3 to 20% Na2O, 1 to 15% P2O5 + ZrO2, 0 to 8% K2O, 0 to 6% ZnO, 0 to 6% B2O3, 0 to 8% RO, 0 to 5% TiO2, 0 to 5% Ln2O3, and 0 to 2% fining agent, wherein the RO is one or more of MgO, CaO, SrO, and BaO, and the Ln2O3 is one or more of La2O3, Gd2O3, and Y2O3.

[0041] (35) contains SiO2, Al2O3, Li2O, and Na2O as constituents, contains a nepheline crystalline phase, and has a Vickers hardness of 650 kgf / mm 2 That's it, crystallized glass.

[0042] (36) contains nepheline crystal phase as the main crystalline phase and has a Vickers hardness of 650 kgf / mm 2 That's it, crystallized glass.

[0043] (37) is a glass-ceramic containing, by weight percentage, 40-60% SiO2, 20-40% Al2O3, 2-15% Li2O, and 3-20% Na2O, and containing a nepheline crystalline phase.

[0044] (38) Crystallized glass containing SiO2, Al2O3, Li2O and Na2O as constituents, and having a thickness of 1 mm or less and a body falling ball height of 1000 mm or more.

[0045] (39) A crystallized glass containing SiO2, Al2O3, Li2O, and Na2O as constituents, the haze of which is 0.15% or less when the thickness of the crystallized glass is 1 mm or less.

[0046] (40) A crystallized glass containing a nepheline crystalline phase, the crystallized glass having a thickness of 1 mm or less having an optical transmittance of 88% or more at a wavelength of 550 nm.

[0047] (41) Crystallized glass containing SiO2, Al2O3, Li2O, and Na2O as constituent components, wherein the weight percentage of the nepheline crystal phase in the crystallized glass is 10 to 80%.

[0048] (42) The crystallized glass according to any one of (35) to (41), containing, as constituents, by weight percentage, 40 to 60% SiO2, and / or 20 to 40% Al2O3, and / or 2 to 15% Li2O, and / or 3 to 20% Na2O, and / or 1 to 15% P2O5+ZrO2.

[0049] (43) The crystallized glass according to any one of (35) to (42), further containing, as constituents, by weight percentage, 0 to 8% K2O, and / or 0 to 6% ZnO, and / or 0 to 6% B2O3, and / or 0 to 8% RO, and / or 0 to 5% TiO2, and / or 0 to 5% Ln2O3, and / or 0 to 2% of a fining agent, wherein the RO is one or more of MgO, CaO, SrO, and BaO, and the Ln2O3 is one or more of La2O3, Gd2O3, and Y2O3.

[0050] (44) The crystallized glass product according to any one of (32) to (43), wherein, when the components are calculated in weight percentage, (Al2O3+Na2O) / P2O5 is 3.0 to 30.0, preferably (Al2O3+Na2O) / P2O5 is 4.0 to 20.0, more preferably (Al2O3+Na2O) / P2O5 is 5.0 to 15.0, and even more preferably (Al2O3+Na2O) / P2O5 is 6.0 to 10.0.

[0051] (45) The crystallized glass according to any one of (32) to (44), wherein, when the components are calculated in weight percentage, the SiO2 / Al2O3 is 1.2 to 2.8, preferably 1.3 to 2.5, more preferably 1.5 to 2.2, and even more preferably 1.6 to 2.0.

[0052] (46) The crystallized glass according to any one of (32) to (45), wherein, when the components are calculated in weight percentage, SiO2 / (Na2O+B2O3) is 2.0 to 15.0, preferably SiO2 / (Na2O+B2O3) is 3.0 to 10.0, more preferably SiO2 / (Na2O+B2O3) is 4.0 to 8.0, and even more preferably SiO2 / (Na2O+B2O3) is 5.0 to 7.0.

[0053] (47) The crystallized glass according to any one of (32) to (46), wherein, when the components are calculated in weight percentage, (Na2O+Li2O) / SiO2 is 0.1 to 0.8, preferably (Na2O+Li2O) / SiO2 is 0.15 to 0.7, more preferably (Na2O+Li2O) / SiO2 is 0.2 to 0.6, and even more preferably (Na2O+Li2O) / SiO2 is 0.25 to 0.5.

[0054] (48) The crystallized glass according to any one of (32) to (47), wherein, when the components are calculated in weight percentage, (ZrO2+ZnO) / Na2O is 2.0 or less, preferably (ZrO2+ZnO) / Na2O is 1.5 or less, more preferably (ZrO2+ZnO) / Na2O is 0.01 to 1.0, and even more preferably (ZrO2+ZnO) / Na2O is 0.1 to 0.5.

[0055] (49) The crystallized glass according to any one of (32) to (48), wherein, when the components are calculated in weight percentage, (P2O5+Na2O) / Li2O is 0.5 to 8.0, preferably (P2O5+Na2O) / Li2O is 0.8 to 5.0, more preferably (P2O5+Na2O) / Li2O is 1.0 to 3.0, and even more preferably (P2O5+Na2O) / Li2O is 1.5 to 2.5.

[0056] (50) The crystallized glass according to any one of (32) to (49), wherein, when the components are calculated in weight percentage, K2O / ZrO2 is 0.1 or more, preferably K2O / ZrO2 is 0.2 to 10.0, more preferably K2O / ZrO2 is 0.3 to 5.0, and even more preferably K2O / ZrO2 is 0.4 to 1.5.

[0057] (51) The crystallized glass according to any one of (32) to (50), wherein, when the components are calculated in weight percentage, (ZnO+RO+B2O3+TiO2) / P2O5 is 1.5 or less, preferably (ZnO+RO+B2O3+TiO2) / P2O5 is 1.0 or less, more preferably (ZnO+RO+B2O3+TiO2) / P2O5 is 0.5 or less, and even more preferably (ZnO+RO+B2O3+TiO2) / P2O5 is 0.2 or less, and the RO is one or more of MgO, CaO, SrO, and BaO.

[0058] (52) Constituents, in weight percentage, are 43 to 55% SiO2, preferably 46 to 53% SiO2, and / or 23 to 36% Al2O3, preferably 25.5 to 32% Al2O3, and / or 3 to 13% Li2O, preferably 5.5 to 11% Li2O, and / or 5 to 15% Na2O, preferably 6.5 to 12% Na2O, and / or 2 to 12% P2O5 + ZrO2, preferably 4 to 10% P2O5 + ZrO2, and / or 0 to 5% K2O, preferably 0.1 to 3% K2O, and / or 0 to 3% ZnO, preferably 0 to 1%. The crystallized glass according to any one of (32) to (51), containing ZnO and / or 0 to 3% B2O3, preferably 0 to 1% B2O3 and / or 0 to 5% RO, preferably 0 to 2% RO, and / or 0 to 3% TiO2, preferably 0 to 1% TiO2 and / or 0 to 3% Ln2O3, preferably 0 to 1% Ln2O3 and / or 0 to 1% of a fining agent, preferably 0 to 0.5% of a fining agent, wherein the RO is one or more of MgO, CaO, SrO, and BaO, and the Ln2O3 is one or more of La2O3, Gd2O3, and YO3.

[0059] (53) The crystallized glass according to any one of (32) to (52), containing, as constituents, by weight percentage, 0 to 6% ZrO2, preferably 0 to 5% ZrO2, more preferably 0.1 to 3% ZrO2, and / or 0 to 10% P2O5, preferably 1 to 8% P2O5, more preferably 2 to 6% P2O5.

[0060] (54) The crystallized glass according to any one of (32), (33), and (35) to (43), further containing, as a constituent, by weight percentage, 0 to 5% of Yb2O3+Nb2O5+WO3+Bi2O3+Ta2O5+TeO2+GeO2, preferably 0 to 2% of Yb2O3+Nb2O5+WO3+Bi2O3+Ta2O5+TeO2+GeO2, and more preferably 0 to 1% of Yb2O3+Nb2O5+WO3+Bi2O3+Ta2O5+TeO2+GeO2.

[0061] (55) The crystallized glass according to any one of (32) to (54), which does not contain, as constituents, SrO, and / or BaO, and / or MgO, and / or CaO, and / or ZnO, and / or PbO, and / or As2O3, and / or TiO2, and / or B2O3, and / or Y2O3, and / or La2O3, and / or Gd2O3.

[0062] (56) The crystallized glass according to any one of (32) to (55), containing a nepheline crystal phase, and / or a lithium silicate crystal phase, and / or a lithium phosphate crystal phase, and / or a petalite crystal phase, and / or a quartz crystal phase.

[0063] (57) The crystallized glass according to any one of (32) to (56), wherein the main crystal phase of the crystallized glass is a nepheline crystal phase, or the crystallized glass contains only a nepheline crystal phase.

[0064] (58) The crystallized glass according to any one of (32) to (57), wherein the weight percentage of the neferine crystal phase in the crystallized glass is 10 to 80%, preferably 20 to 70%, more preferably 30 to 60%.

[0065] (59), the crystal grain size is 80 nm or less, preferably 60 nm or less, more preferably 50 nm or less, and even more preferably 40 nm or less, and / or the Vickers hardness is 650 kgf / mm 2 or more, and preferably 680 kgf / mm 2 More preferably, it is 700 kgf / mm 2 The crystallized glass according to any one of (32) to (58) above.

[0066] (60) The crystallized glass according to any one of (32) to (59), having a thickness of 1 mm or less, has a body falling ball height of 1000 mm or more, preferably 1200 mm or more, more preferably 1400 mm or more, and / or a haze of 0.15% or less, preferably 0.12% or less, more preferably 0.10% or less, and / or a light transmittance at a wavelength of 550 nm of 88% or more, preferably 89% or more, more preferably 90% or more, even more preferably 91% or more, and / or a |B| value at an average light of 400 to 800 nm of 1.5 or less, preferably 1.0 or less, more preferably 0.8 or less.

[0067] (61) The crystallized glass according to any one of (38) to (40) and (60), having a thickness of 0.2 to 1 mm, preferably 0.3 to 0.9 mm, more preferably 0.5 to 0.8 mm, and even more preferably 0.55 mm, 0.6 mm, 0.68 mm, 0.7 mm, or 0.75 mm.

[0068] (62) The crystallized glass according to any one of (32), (33), and (35) to (43), further containing, as constituents, by weight percentage, 0 to 4% NiO, and / or 0 to 4% Ni2O3, and / or 0 to 2% CoO, and / or 0 to 2% Co2O3, and / or 0 to 7% Fe2O3, and / or 0 to 4% MnO2, and / or 0 to 8% Er2O3, and / or 0 to 8% Nd2O3, and / or 0 to 4% Cu2O, and / or 0 to 8% Pr2O3, and / or 0 to 4% CeO2.

[0069] (63), a matrix glass containing, by weight percentage, 40-60% SiO2, 20-40% Al2O3, 2-15% Li2O, 3-20% Na2O, and 1-15% P2O5+ZrO2.

[0070] (64) The matrix glass according to (63), further containing, as constituents, by weight percentage, 0 to 8% K2O, and / or 0 to 6% ZnO, and / or 0 to 6% B2O3, and / or 0 to 8% RO, and / or 0 to 5% TiO2, and / or 0 to 5% Ln2O3, and / or 0 to 2% fining agent, wherein the RO is one or more of MgO, CaO, SrO, and BaO, and the Ln2O3 is one or more of La2O3, Gd2O3, and Y2O3.

[0071] (65) A matrix glass containing, as components by weight percentage, 40 to 60% SiO2, 20 to 40% Al2O3, 2 to 15% Li2O, 3 to 20% Na2O, 1 to 15% P2O5 + ZrO2, 0 to 8% K2O, 0 to 6% ZnO, 0 to 6% B2O3, 0 to 8% RO, 0 to 5% TiO2, 0 to 5% Ln2O3, and 0 to 2% fining agent, wherein the RO is one or more of MgO, CaO, SrO, and BaO, and the Ln2O3 is one or more of La2O3, Gd2O3, and Y2O3.

[0072] (66) The matrix glass according to any one of (63) to (65), wherein, when the constituent components are calculated in weight percentage, (Al2O3+Na2O) / P2O5 is 3.0 to 30.0, preferably (Al2O3+Na2O) / P2O5 is 4.0 to 20.0, more preferably (Al2O3+Na2O) / P2O5 is 5.0 to 15.0, and even more preferably (Al2O3+Na2O) / P2O5 is 6.0 to 10.0.

[0073] (67) The matrix glass according to any one of (63) to (66), wherein, when calculated as a weight percentage of the constituent components, the SiO2 / Al2O3 ratio is 1.2 to 2.8, preferably 1.3 to 2.5, more preferably 1.5 to 2.2, and even more preferably 1.6 to 2.0.

[0074] (68) The matrix glass according to any one of (63) to (67), wherein, when the components are calculated in weight percentage, SiO2 / (Na2O+B2O3) is 2.0 to 15.0, preferably SiO2 / (Na2O+B2O3) is 3.0 to 10.0, more preferably SiO2 / (Na2O+B2O3) is 4.0 to 8.0, and even more preferably SiO2 / (Na2O+B2O3) is 5.0 to 7.0.

[0075] (69) The matrix glass according to any one of (63) to (68), wherein, when calculated as a weight percentage of the constituent components, (Na2O+Li2O) / SiO2 is 0.1 to 0.8, preferably (Na2O+Li2O) / SiO2 is 0.15 to 0.7, more preferably (Na2O+Li2O) / SiO2 is 0.2 to 0.6, and even more preferably (Na2O+Li2O) / SiO2 is 0.25 to 0.5.

[0076] (70) The matrix glass according to any one of (63) to (69), wherein, when the components are calculated in weight percentage, the ratio (ZrO2+ZnO) / Na2O is 2.0 or less, preferably (ZrO2+ZnO) / Na2O is 1.5 or less, more preferably (ZrO2+ZnO) / Na2O is 0.01 to 1.0, and even more preferably (ZrO2+ZnO) / Na2O is 0.1 to 0.5.

[0077] (71) The matrix glass according to any one of (63) to (70), wherein, when the components are calculated in weight percentage, the ratio (P2O5+Na2O) / Li2O is 0.5 to 8.0, preferably (P2O5+Na2O) / Li2O is 0.8 to 5.0, more preferably (P2O5+Na2O) / Li2O is 1.0 to 3.0, and even more preferably (P2O5+Na2O) / Li2O is 1.5 to 2.5.

[0078] (72) The matrix glass according to any one of (63) to (71), wherein, when the constituent components are calculated in weight percentage, the K2O / ZrO2 ratio is 0.1 or more, preferably 0.2 to 10.0, more preferably 0.3 to 5.0, and even more preferably 0.4 to 1.5.

[0079] (73) The matrix glass according to any one of (63) to (72), wherein, when the constituent components are calculated in weight percentage, (ZnO+RO+B2O3+TiO2) / P2O5 is 1.5 or less, preferably (ZnO+RO+B2O3+TiO2) / P2O5 is 1.0 or less, more preferably (ZnO+RO+B2O3+TiO2) / P2O5 is 0.5 or less, and even more preferably (ZnO+RO+B2O3+TiO2) / P2O5 is 0.2 or less, and the RO is one or more of MgO, CaO, SrO, and BaO.

[0080] (74), as constituents, by weight percentage, 43 to 55% SiO2, preferably 46 to 53% SiO2, and / or 23 to 36% Al2O3, preferably 25.5 to 32% Al2O3, and / or 3 to 13% Li2O, preferably 5.5 to 11% Li2O, and / or 5 to 15% Na2O, preferably 6.5 to 12% Na2O, and / or 2 to 12% P2O5 + ZrO2, preferably 4 to 10% P2O5 + ZrO2, and / or 0 to 5% K2O, preferably 0.1 to 3% K2O, and / or 0 to 3% ZnO, preferably 0 to 1% Z. The matrix glass according to any one of (63) to (73), comprising: MgO, and / or 0 to 3% B2O3, preferably 0 to 1% B2O3, and / or 0 to 5% RO, preferably 0 to 2% RO, and / or 0 to 3% TiO2, preferably 0 to 1% TiO2, and / or 0 to 3% Ln2O3, preferably 0 to 1% Ln2O3, and / or 0 to 1% fining agent, preferably 0 to 0.5% fining agent, wherein the RO is one or more of MgO, CaO, SrO, and BaO, and the Ln2O3 is one or more of La2O3, Gd2O3, and YO3.

[0081] (75) The matrix glass according to any one of (63) to (74), containing, as constituents, by weight percentage, 0 to 6% ZrO2, preferably 0 to 5% ZrO2, more preferably 0.1 to 3% ZrO2, and / or 0 to 10% P2O5, preferably 1 to 8% P2O5, more preferably 2 to 6% P2O5.

[0082] (76) The matrix glass according to (63) or (64), further containing, as components, by weight percentage, 0 to 5% of Yb2O3+Nb2O5+WO3+Bi2O3+Ta2O5+TeO2+GeO2, preferably 0 to 2% of Yb2O3+Nb2O5+WO3+Bi2O3+Ta2O5+TeO2+GeO2, and more preferably 0 to 1% of Yb2O3+Nb2O5+WO3+Bi2O3+Ta2O5+TeO2+GeO2.

[0083] (77) The matrix glass according to any one of (63) to (65), which does not contain, as constituents, SrO, and / or BaO, and / or MgO, and / or CaO, and / or ZnO, and / or PbO, and / or As2O3, and / or TiO2, and / or B2O3, and / or Y2O3, and / or La2O3, and / or Gd2O3.

[0084] (78) A matrix glass according to (63) or (64), further containing, as components, by weight percentage, 0 to 4% NiO, and / or 0 to 4% Ni2O3, and / or 0 to 2% CoO, and / or 0 to 2% Co2O3, and / or 0 to 7% Fe2O3, and / or 0 to 4% MnO2, and / or 0 to 8% Er2O3, and / or 0 to 8% Nd2O3, and / or 0 to 4% Cu2O, and / or 0 to 8% Pr2O3, and / or 0 to 4% CeO2.

[0085] (79) A crystallized glass-molded product containing the crystallized glass according to any one of (32) to (62).

[0086] (80), a glass cover plate comprising the crystallized glass product according to any one of (1) to (31), and / or the crystallized glass according to any one of (32) to (62), and / or the matrix glass according to any one of (63) to (78), and / or the crystallized glass molded body according to (79).

[0087] (81) A glass part comprising the crystallized glass product according to any one of (1) to (31), and / or the crystallized glass according to any one of (32) to (62), and / or the matrix glass according to any one of (63) to (78), and / or the crystallized glass molded body according to (79).

[0088] (82) A display device comprising the crystallized glass product according to any one of (1) to (31), and / or the crystallized glass according to any one of (32) to (62), and / or the matrix glass according to any one of (63) to (78), and / or the crystallized glass molded body according to (79), and / or the glass cover plate according to (80), and / or the glass component according to (81).

[0089] (83) An electronic device comprising the crystallized glass product according to any one of (1) to (31), and / or the crystallized glass according to any one of (32) to (62), and / or the matrix glass according to any one of (63) to (78), and / or the crystallized glass molded body according to (79), and / or the glass cover plate according to (80), and / or the glass part according to (81).

[0090] (84) A method for producing a crystallized glass product according to any one of (1) to (31), comprising the steps of forming a matrix glass, treating the matrix glass by a crystallization process to form a crystallized glass, and then treating the crystallized glass by a chemical strengthening process to form a crystallized glass product.

[0091] (85) The method for producing a crystallized glass product according to (84), wherein the crystallization process includes a step of raising the temperature to a predetermined crystallization temperature, and after reaching the crystallization temperature, maintaining the temperature for a certain period of time, and then lowering the temperature, the crystallization temperature is 580 to 750°C, preferably 600 to 700°C, and the maintaining time at the crystallization temperature is 0 to 8 hours, preferably 1 to 6 hours.

[0092] (86) The method for producing a crystallized glass product according to (84), wherein the crystallization process includes a step of performing a crystal nucleation process at a first temperature and then performing a crystal growth process at a second temperature higher than the temperature of the crystal nucleation process.

[0093] (87) A method for producing a crystallized glass product according to (86), wherein in the crystallization process, the first temperature is 500 to 620°C, the second temperature is 620 to 750°C, the holding time at the first temperature is 0 to 24 hours, preferably 2 to 15 hours, and the holding time at the second temperature is 0 to 10 hours, preferably 0.5 to 6 hours.

[0094] (88) The method for producing a crystallized glass product according to any one of (84) to (87), wherein the chemical strengthening process comprises the steps of: immersing the glass-ceramics in a salt bath of Na molten salt at a temperature of 350 to 470°C, preferably 380 to 460°C, for 1 to 36 hours, preferably 2 to 10 hours; and / or immersing the glass-ceramics in a salt bath of K molten salt at a temperature of 360 to 450°C, for 1 to 36 hours, preferably 1 to 10 hours; and / or immersing the glass-ceramics in a mixed salt bath of K molten salt and Na molten salt at a temperature of 360 to 450°C, for 1 to 36 hours, preferably 2 to 24 hours.

[0095] (89) A method for producing crystallized glass according to any one of (32) to (62), comprising the step of forming a matrix glass, and then treating the matrix glass by a crystallization process to form a crystallized glass.

[0096] (90) The method for producing crystallized glass according to (89), wherein the crystallization process comprises a step of raising the temperature to a predetermined crystallization temperature, and after reaching the crystallization temperature, maintaining the temperature for a certain period of time, and then lowering the temperature, the crystallization temperature is 580 to 750°C, preferably 600 to 700°C, and the maintaining time at the crystallization temperature is 0 to 8 hours, preferably 1 to 6 hours.

[0097] (91) The method for producing crystallized glass according to (89), wherein the crystallization process includes a step of performing a crystal nucleation process at a first temperature and then performing a crystal growth process at a second temperature higher than the temperature of the crystal nucleation process.

[0098] (92) The method for producing crystallized glass according to (91), wherein in the crystallization process, the first temperature is 500 to 620°C, the second temperature is 620 to 750°C, the holding time at the first temperature is 0 to 24 hours, preferably 2 to 15 hours, and the holding time at the second temperature is 0 to 10 hours, preferably 0.5 to 6 hours.

[0099] (93) A method for producing a crystallized glass molded body according to (79), comprising a step of polishing or buffing crystallized glass to produce a crystallized glass molded body, or a step of treating a matrix glass or crystallized glass at a constant temperature by a hot bending process or a press molding process to produce a crystallized glass molded body.

[0100] (94) A method for producing a crystallized glass molded body according to (79), comprising the steps of: subjecting the matrix glass to a primary crystallization heat treatment process including heating, adiabatic nucleation, heating, adiabatic crystallization, and cooling to room temperature to form a pre-crystallized glass; and subjecting the pre-crystallized glass to hot processing and forming to obtain a crystallized glass molded body.

[0101] (95), 1) a temperature-raising preheating step in which the matrix glass, the pre-crystallized glass or the crystallized glass is placed in a mold, the mold is passed through each heating station in order in a hot bending machine, the mold is retained at each station for a certain time to insulate, the temperature of the preheating area is set to 400 to 800°C, the pressure is set to 0.01 to 0.05 MPa, and the time is set to 40 to 200 seconds; 2) a pressure molding step in which the mold is preheated and then transferred to a molding station, and a certain pressure is applied to the mold by the hot bending machine, the pressure range is 0.1 to 0.8 MPa, the temperature range of the molding station is 650 to 850 ° C, and the molding time range is 40 to 200 s; 3) A method for producing a crystallized glass molded body according to (79), comprising: a pressure-holding and temperature-lowering step in which the mold is transferred to a temperature-lowering station and the temperature is lowered at each station, with the temperature range of the temperature-lowering being 750 to 500°C, the pressure being 0.01 to 0.05 MPa, and the time being 40 to 200 seconds. [Effects of the Invention]

[0102] The beneficial effects of the present invention are as follows: Due to the rational component design, the crystallized glass or crystallized glass product obtained by the present invention has excellent mechanical properties and meets the application in fields such as display devices and electronic devices. DETAILED DESCRIPTION OF THE INVENTION

[0103] The crystallized glass and crystallized glass product of the present invention are materials having a crystalline phase (sometimes called a crystal) and a glass phase, and are different from amorphous solids. The crystalline phase of the crystallized glass and crystallized glass product can be identified by the peak angle appearing in the X-ray diffraction pattern of X-ray diffraction analysis, and / or can be measured by TEMEDX.

[0104] As a result of trial and error and research, the inventors of the present invention have set the content and content ratio of specific components constituting the crystallized glass and the crystallized glass product to specific values, and have obtained the crystallized glass or the crystallized glass product of the present invention by precipitating a specific crystalline phase.

[0105] The range of each component (ingredient) of the matrix glass, crystallized glass, and crystallized glass product of the present invention will be explained below. In this specification, unless otherwise specified, the content of each component is expressed as a weight percentage (wt%) of the total material of the matrix glass, crystallized glass, or crystallized glass product, calculated as an oxide. Here, the term "oxide-based composition" refers to the case where oxides, complex salts, hydroxides, etc. used as raw materials for the composition of the matrix glass, crystallized glass, or crystallized glass product of the present invention decompose to oxides upon melting, and the total material weight of the oxide is taken as 100%. In this specification, the term "glass" refers to the matrix glass before crystallization (i.e., crystallization process treatment), while the term "crystallized glass product" refers to the product obtained after crystallization (i.e., crystallization process treatment) of the matrix glass. The term "crystallized glass product" refers to the product obtained after chemically strengthening the crystallized glass.

[0106] Unless otherwise specified, numerical ranges recited herein include upper and lower limits, and "greater than or equal to" and "less than or equal to" include the endpoints, and all integers and fractions within the range, and are not limited to the specific values ​​recited in the limited range. As used herein, the term "about" indicates that formulations, parameters, and other numbers and properties may not be exact and may be approximate and / or larger or smaller, as appropriate, to account for tolerances, conversion factors, measurement errors, and the like. As used herein, "and / or" is inclusive; for example, "A and / or B" refers to A only, or B only, or both A and B.

[0107] In some embodiments, the crystalline phase of the crystallized glass or crystallized glass product of the present invention contains a nepheline crystalline phase (including eucryptite and / or sodium nepheline), specifically, contains eucryptite, or contains sodium nepheline, or contains both eucryptite and sodium nepheline. The crystallized glass of the present invention may further contain other crystalline phases other than the nepheline crystalline phase, such as a lithium silicate crystalline phase (one or two of lithium monosilicate and lithium disilicate), and / or a lithium phosphate crystalline phase, and / or a petalite crystalline phase, and / or a quartz crystalline phase.

[0108] In some embodiments of the present invention, the crystalline phase in the crystallized glass or crystallized glass product contains only nepheline crystalline phases (one or two of eucryptite and sodium nepheline).

[0109] In some embodiments, when the crystallized glass or crystallized glass product contains a nepheline crystalline phase and other crystalline phases, the predominant crystalline phase of the crystallized glass or crystallized glass product is the nepheline crystalline phase, i.e., the nepheline crystalline phase has a higher weight percentage than the other crystalline phases.

[0110] In some embodiments, the weight percentage of the neferine crystalline phase in the crystallized glass or crystallized glass product is 10 to 80%, preferably 20 to 70%, more preferably 30 to 60%. In some embodiments, the weight percentage of the neferine crystalline phase in the crystallized glass or crystallized glass product is about 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%. , 40%, 41%, 42%, 43%, 44%, 45%, 46%, 47%, 48%, 49%, 50%, 51%, 52%, 53%, 54%, 55%, 56%, 57%, 58%, 59%, 60%, 61%, 62%, 63%, 64%, 65%, 66%, 67%, 68%, 69%, 70%, 71%, 72%, 73%, 74%, 75%, 76%, 77%, 78%, 79%, 80%.

[0111] SiO2 is a basic component of the matrix glass, crystallized glass, and crystallized glass products of the present invention. It stabilizes the network structure of the glass and crystallized glass and is one of the components that form a nepheline crystalline phase after crystallization. If the SiO2 content is 40% or less, fewer crystals will form in the crystallized glass, and the crystals will tend to become coarse, affecting the haze of the crystallized glass and the crystallized glass product, as well as the performance of the crystallized glass product in terms of ball drop test height. Therefore, the lower limit of the SiO2 content is 40%, preferably 43%, and more preferably 46%. If the SiO2 content exceeds 60%, the melting temperature of the glass will be high, making it difficult to refine and mold, affecting the glass's uniformity, and affecting the hot bending of the glass and crystallized glass, which is detrimental to the surface stress and ion-exchange layer depth of the crystallized glass product. Therefore, the upper limit of the SiO2 content is 60%, preferably 55%, and more preferably 53%. In some embodiments, the SiO2 content may be about 40%, 40.5%, 41%, 41.5%, 42%, 42.5%, 43%, 43.5%, 44%, 44.5%, 45%, 45.5%, 46%, 46.5%, 47%, 47.5%, 48%, 48.5%, 49%, 49.5%, 50%, 50.5%, 51%, 51.5%, 52%, 52.5%, 53%, 53.5%, 54%, 54.5%, 55%, 55.5%, 56%, 56.5%, 57%, 57.5%, 58%, 58.5%, 59%, 59.5%, or 60%.

[0112] Al2O3 is a component that forms the network structure of glass, helps stabilize glass molding, and is an important component that improves chemical stability. It can also improve the mechanical properties of glass and increase the ion-exchange layer depth and surface stress of crystallized glass products. However, if the Al2O3 content is too high, the meltability and devitrification resistance of the glass will decrease, and crystals will tend to grow during crystallization, reducing the strength of the crystallized glass and crystallized glass products. Therefore, in the present invention, the Al2O3 content is 20 to 40%, preferably 23 to 36%, and more preferably 25.5 to 32%. Some embodiments may contain about 20%, 20.5%, 21%, 21.5%, 22%, 22.5%, 23%, 23.5%, 24%, 24.5%, 25%, 25.5%, 26%, 26.5%, 27%, 27.5%, 28%, 28.5%, 29%, 29.5%, 30%, 30.5%, 31%, 31.5%, 32%, 32.5%, 33%, 33.5%, 34%, 34.5%, 35%, 35.5%, 36%, 36.5%, 37%, 37.5%, 38%, 38.5%, 39%, 39.5%, or 40% Al2O3.

[0113] In some embodiments, by controlling the ratio of SiO2 content to Al2O3 content, SiO2 / Al2O3, within the range of 1.2 to 2.8, the four-point bending strength of the crystallized glass and the crystallized glass product can be improved, and the light transmittance of the crystallized glass and the crystallized glass product can be improved. Therefore, SiO2 / Al2O3 is preferably 1.2 to 2.8, and more preferably 1.3 to 2.5. Furthermore, by controlling SiO2 / Al2O3 within the range of 1.5 to 2.2, the |B| value of the crystallized glass and the crystallized glass product can be further reduced, and the surface stress of the crystallized glass product can be increased. Therefore, SiO2 / Al2O3 is more preferably 1.5 to 2.2, and even more preferably 1.6 to 2.0. In some embodiments, the value of SiO2 / Al2O3 can be 1.2, 1.25, 1.3, 1.35, 1.4, 1.45, 1.5, 1.55, 1.6, 1.65, 1.7, 1.75, 1.8, 1.85, 1.9, 1.95, 2.0, 2.05, 2.1, 2.15, 2.2, 2.25, 2.3, 2.35, 2.4, 2.45, 2.5, 2.55, 2.6, 2.65, 2.7, 2.75, 2.8.

[0114] Li2O promotes glass melting, lowers the glass smelting temperature, and can form a eucryptite crystalline phase after crystallization. It is also a component that primarily replaces sodium and potassium ions during chemical strengthening. It increases the surface stress of crystallized glass products, helps improve the ball drop test height of crystallized glass products, and can increase the dielectric constant of crystallized glass and crystallized glass products. On the other hand, excessive Li2O content tends to reduce the chemical stability of the glass, and reduces the light transmittance of crystallized glass and crystallized glass products. Therefore, in the present invention, the Li2O content is 2 to 15%, preferably 3 to 13%, and more preferably 5.5 to 11%. Some embodiments may contain about 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, 10%, 10.5%, 11%, 11.5%, 12%, 12.5%, 13%, 13.5%, 14%, 14.5%, or 15% LiO.

[0115] After crystallization, Na2O not only participates in crystallization to form a sodium nepheline crystalline phase, but also participates in chemical strengthening, thereby improving the meltability of the glass. On the other hand, if the Na2O content is too high, the crystal grains precipitated during the crystallization process tend to increase in size, or the type of precipitated crystal phase tends to change. Therefore, in the present invention, the Na2O content is 3 to 20%, preferably 5 to 15%, and more preferably 6.5 to 12%. In some embodiments, the NaO may contain about 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, 10%, 10.5%, 11%, 11.5%, 12%, 12.5%, 13%, 13.5%, 14%, 14.5%, 15%, 15.5%, 16%, 16.5%, 17%, 17.5%, 18%, 18.5%, 19%, 19.5%, or 20% NaO.

[0116] In some embodiments, controlling the ratio (Na2O+Li2O) / SiO2 of the total content of Na2O and Li2O (Na2O+Li2O) to the content of SiO2 within a range of 0.1 to 0.8 is advantageous in providing the desired crystalline phase content in the crystallized glass and crystallized glass products, reducing the crystal grain size, and improving the hardness of the crystallized glass and crystallized glass products. Therefore, (Na2O+Li2O) / SiO2 is preferably 0.1 to 0.8, and more preferably 0.15 to 0.7. Furthermore, controlling (Na2O+Li2O) / SiO2 within a range of 0.2 to 0.6 can further improve the light transmittance of the crystallized glass and crystallized glass products and optimize the haze. Therefore, more preferably, (Na2O+Li2O) / SiO2 is 0.2 to 0.6, and even more preferably, (Na2O+Li2O) / SiO2 is 0.25 to 0.5. In some embodiments, the value of (Na2O+Li2O) / SiO2 may be 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8.

[0117] KO is an optional component that helps improve the low-temperature melting property and formability of glass, but excessive KO content can easily reduce the chemical stability of the glass. Therefore, the KO content is 0 to 8%, preferably 0 to 5%, and more preferably 0.1 to 3%. In some embodiments, the KO content may be about 0%, more than 0%, 0.01%, 0.05%, 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, or 8%.

[0118] P2O5 forms crystal nuclei in the glass, promoting uniform crystal growth and improving the low-temperature melting property of the glass. However, excessive P2O5 content can reduce the devitrification resistance of the glass, increase the likelihood of phase separation, and decrease the mechanical properties of the crystallized glass and crystallized glass products. Therefore, in the present invention, the P2O5 content is 0 to 10%, preferably 1 to 8%, and more preferably 2 to 6%. In some embodiments, the P2O5 content may be about 0%, more than 0%, 0.01%, 0.05%, 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, or 10%.

[0119] In some embodiments, controlling the ratio (Al2O3 + Na2O) / P2O5 of the total content of Al2O3 and Na2O (Al2O3 + Na2O) to the content of P2O5 within the range of 3.0 to 30.0 provides the desired crystalline phase content in the crystallized glass and crystallized glass products, and is advantageous in improving the Vickers hardness and ball drop test height of the crystallized glass and crystallized glass products. Therefore, (Al2O3 + Na2O) / P2O5 is preferably 3.0 to 30.0, and more preferably 4.0 to 20.0. Furthermore, controlling (Al2O3 + Na2O) / P2O5 within the range of 5.0 to 15.0 further optimizes the four-point bending strength of the crystallized glass and crystallized glass products, and improves the ion-exchange layer depth of the crystallized glass products. Therefore, more preferably, (Al2O3 + Na2O) / P2O5 is 5.0 to 15.0, and even more preferably, (Al2O3 + Na2O) / P2O5 is 6.0 to 10.0. In some embodiments, the value of (Al2O3 + Na2O) / P2O5 is 3.0, 3.5, 4.0, 4.5, 5.0, 5.5, 6.0, 6.5, 7.0, 7.5, 8.0, 8.5, 9.0, 9.5, 10.0, 10.5, 11.0, 11.5, 12.0, 12.5, 13.0, 13.5, 14.0, 14.5, 15.0, 15.5, 16.0, 16.5, 17.0, 17.5, 18.0, 18.5, 19.0, 19.5, 20.0, 20.5, 21.0, 21.5, 22.0, 22.5, 23.0, 23.5, 24.0, 24.5, 25.0, 25.5, 26.0, 26.5, 27.0, 27.5, 28.0, 28.5, 29.0, 30.0, 30.5, 31.0, 31.5, 32.0, 32.5, 33.0, 33.5, 34.0, 34.5, 35.0, 35.5, 36.0, 36.5, 37.0, 37.5, 38.0, 38.5, 39.0, 40.0, It may be 6.0, 16.5, 17.0, 17.5, 18.0, 18.5, 19.0, 19.5, 20.0, 20.5, 21.0, 21.5, 22.0, 22.5, 23.0, 23.5, 24.0, 24.5, 25.0, 25.5, 26.0, 26.5, 27.0, 27.5, 28.0, 28.5, 29.0, 29.5, or 30.0.

[0120] In some embodiments, controlling the ratio (P2O5+Na2O) / Li2O of the total content of P2O5 and Na2O (P2O5+Na2O) to the content of Li2O within the range of 0.5 to 8.0 is advantageous for improving the ball drop test height of the crystallized glass and crystallized glass products and for improving the ion-exchange layer depth of the crystallized glass products. Therefore, preferably, (P2O5+Na2O) / Li2O is 0.5 to 8.0, and more preferably, (P2O5+Na2O) / Li2O is 0.8 to 5.0. Furthermore, controlling (P2O5+Na2O) / Li2O within the range of 1.0 to 3.0 can further optimize the hardness and |B| value of the crystallized glass and crystallized glass products. Therefore, more preferably, (P2O5+Na2O) / Li2O is 1.0 to 3.0, and even more preferably, (P2O5+Na2O) / Li2O is 1.5 to 2.5. In some embodiments, the value of (P2O5+Na2O) / Li2O can be 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4.0, 4.5, 5.0, 5.5, 6.0, 6.5, 7.0, 7.5, 8.0.

[0121] ZrO2 plays a role in crystal nucleation and improves the chemical stability of glass. Research has shown that ZrO2 also significantly reduces the devitrification resistance of glass during the melting process and improves glass stability by lowering the liquidus temperature. However, excessive ZrO2 content can reduce the devitrification resistance of glass and increase the difficulty of controlling the crystallization process. Therefore, the ZrO2 content is 0 to 6%, preferably 0 to 5%, and more preferably 0.1 to 3%. In some embodiments, ZrO2 may be present at about 0%, more than 0%, 0.01%, 0.05%, 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, or 6%.

[0122] In some embodiments, controlling the ratio of K2O content to ZrO2 content (K2O / ZrO2) to 0.1 or more is advantageous in reducing the crystal grain size and reducing the haze and crystal grain size of the crystallized glass and crystallized glass products. Therefore, K2O / ZrO2 is preferably 0.1 or more, and more preferably 0.2 to 10.0. Furthermore, controlling K2O / ZrO2 within the range of 0.3 to 5.0 can further optimize the light transmittance of the crystallized glass and crystallized glass products and prevent a decrease in the ion-exchange layer depth of the crystallized glass products. Therefore, K2O / ZrO2 is more preferably 0.3 to 5.0, and even more preferably 0.4 to 1.5. In some embodiments, the values ​​of K2O / ZrO2 are 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9, 0.95, 1.0, 1.05, 1.1, 1.15, 1.2, 1.25, 1.3, 1.35, 1.4, 1.45, 1.5, 1.55, 1.6, 1.65, 1.7, 1.75, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 2.10, 2.11, 2.12, 2.13, 2.14, 2.15, 2.16, 2.17, 2.18, 2.19, 2.20, 2.21, 2.22, 2.23, 2.24, 2.25, 2.26, 2.27, 2.28, 2.29, 2.30, 2.31, 2.32, 2.33, 2.34, 2.35, 2.36, 2.37, 2.38, 2.39, 2.40, 2.41, 2.42, 2.43, 2.44, 2.45, 2.46, 2.47, 2.48, 2.49, 2.50, 2 The thickness may be 85, 1.9, 1.95, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4.0, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, 5.0, 5.5, 6.0, 6.5, 7.0, 7.5, 8.0, 8.5, 9.0, 9.5, or 10.0.

[0123] In some embodiments, by controlling the total content of P2O5 and ZrO2 (P2O5+ZrO2) within the range of 1 to 15%, it is advantageous to refine the crystal grains, reduce the crystal grain size of the crystallized glass and the crystallized glass product, reduce the |B| value of the crystallized glass and the crystallized glass product, and improve the light transmittance of the crystallized glass and the crystallized glass product. Therefore, P2O5+ZrO2 is preferably 1 to 15%, more preferably 2 to 12%, and even more preferably 4 to 10%. In some embodiments, P2O5 + ZrO2 can be 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, 10%, 10.5%, 11%, 11.5%, 12%, 12.5%, 13%, 13.5%, 14%, 14.5%, or 15%.

[0124] ZnO improves the melting properties of glass, improves the chemical stability of glass, and refines crystal grains during crystallization. By limiting the ZnO content to 6% or less, deterioration in devitrification resistance can be suppressed. Therefore, the ZnO content is 0 to 6%, preferably 0 to 3%, and more preferably 0 to 1%. In some embodiments, the ZnO content may be about 0%, more than 0%, 0.01%, 0.05%, 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, or 6%.

[0125] In some embodiments, the ratio (ZrO2 + ZnO) / Na2O of the total content of ZrO2 and ZnO (ZrO2 + ZnO) to the content of Na2O is controlled to 2.0 or less, which is advantageous for reducing the haze and grain size of the crystallized glass and crystallized glass products and improving the ball drop test height of the crystallized glass and crystallized glass products. Therefore, preferably, (ZrO2 + ZnO) / Na2O is 2.0 or less, more preferably, (ZrO2 + ZnO) / Na2O is 1.5 or less, even more preferably, (ZrO2 + ZnO) / Na2O is 0.01 to 1.0, and even more preferably, (ZrO2 + ZnO) / Na2O is 0.1 to 0.5. In some embodiments, the value of (ZrO2 + ZnO) / Na2O can be 0, greater than 0, 0.01, 0.05, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9, 0.95, 1.0, 1.05, 1.1, 1.15, 1.2, 1.25, 1.3, 1.35, 1.4, 1.45, 1.5, 1.55, 1.6, 1.65, 1.7, 1.75, 1.8, 1.85, 1.9, 1.95, or 2.0.

[0126] B2O3 improves the glass network structure and adjusts the chemical strengthening performance of crystallized glass. However, excessive B2O3 content is disadvantageous for glass molding, as it tends to crystallize during molding and reduces chemical stability. Therefore, the B2O3 content is 0 to 6%, preferably 0 to 3%, and more preferably 0 to 1%. In some embodiments, the B2O3 content may be about 0%, more than 0%, 0.01%, 0.05%, 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, or 6%.

[0127] In some embodiments, controlling the ratio of SiO2 / (Na2O+B2O3) between the SiO2 content and the total content of Na2O and B2O3 (Na2O+B2O3) within a range of 2.0 to 15.0 is advantageous in improving the ion exchange layer depth of the crystallized glass product and improving the four-point bending strength of the crystallized glass and the crystallized glass product. Therefore, SiO2 / (Na2O+B2O3) is preferably 2.0 to 15.0, and more preferably SiO2 / (Na2O+B2O3) is 3.0 to 10.0. Furthermore, controlling SiO2 / (Na2O+B2O3) within a range of 4.0 to 8.0 further optimizes the surface stress of the crystallized glass product and improves the ball drop test height of the crystallized glass and the crystallized glass product. Therefore, more preferably, SiO2 / (Na2O+B2O3) is 4.0 to 8.0, and even more preferably, SiO2 / (Na2O+B2O3) is 5.0 to 7.0. In some embodiments, the value of SiO2 / (Na2O+B2O3) may be 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, 5.0, 5.5, 6.0, 6.5, 7.0, 7.5, 8.0, 8.5, 9.0, 9.5, 10.0, 10.5, 11.0, 11.5, 12.0, 12.5, 13.0, 13.5, 14.0, 14.5, or 15.0.

[0128] Alkaline earth metal oxides RO (RO is one or more of MgO, CaO, SrO, and BaO) improve the devitrification resistance and strength of glass. However, a high RO content reduces the crystallization ability of the glass, making it difficult to obtain the desired crystal phase type and grain size. Therefore, the RO content is 0 to 8%, preferably 0 to 5%, and more preferably 0 to 2%. In some embodiments, the RO content may be about 0%, more than 0%, 0.01%, 0.05%, 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, or 8%.

[0129] TiO2 is an optional component that helps lower the melting temperature of the glass and improve its chemical stability. In the present invention, the inclusion of 5% or less TiO2 can facilitate control of the crystallization process of the glass, and the TiO2 content is preferably 3% or less, and more preferably 1% or less. In some embodiments, it is even more preferable that TiO2 is not included. In some embodiments, TiO2 may be included at approximately 0%, more than 0%, 0.01%, 0.05%, 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, or 5%.

[0130] In some embodiments, the ratio (ZnO+RO+BO3+TiO2) / PO5 of the total content of ZnO, RO, BO3, and TiO2 (ZnO+RO+BO3+TiO2) to the content of PO5 is controlled to 1.5 or less, which is advantageous for reducing the haze of the crystallized glass and the crystallized glass product, improving the light transmittance, and increasing the surface stress of the crystallized glass product. Therefore, preferably, (ZnO+RO+BO3+TiO2) / PO5 is 1.5 or less, more preferably, (ZnO+RO+BO3+TiO2) / PO5 is 1.0 or less, even more preferably, (ZnO+RO+BO3+TiO2) / PO5 is 0.5 or less, and even more preferably, (ZnO+RO+BO3+TiO2) / PO5 is 0.2 or less. In some embodiments, the value of (ZnO+RO+B2O3+TiO2) / P2O5 can be 0, greater than 0, 0.01, 0.05, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9, 0.95, 1.0, 1.05, 1.1, 1.15, 1.2, 1.25, 1.3, 1.35, 1.4, 1.45, or 1.5.

[0131] Ln2O3 (Ln2O3 is one or more of La2O3, Gd2O3, and YO3) can reduce the smelting difficulty of glass. If its content is too high, crystals are less likely to form during glass crystallization, and the height of the crystallized glass and crystallized glass products in the ball drop test decreases. Therefore, the upper limit of the Ln2O3 content is 5%, preferably 3%, and more preferably 1%. In some embodiments, Ln2O3 may be contained at about 0%, more than 0%, 0.01%, 0.05%, 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, or 5%.

[0132] In some embodiments, the matrix glass, the crystallized glass, or the crystallized glass product may further contain 0-2% of a fining agent to improve the defoaming properties of the matrix glass, the crystallized glass, or the crystallized glass product. Such fining agents include, but are not limited to, one or more of Sb2O3, SnO2, SnO, F (fluorine), Cl (chlorine), and Br (bromine). Preferably, Sb2O3 or SnO2 is the fining agent, and more preferably, Sb2O3 is the fining agent. When the above fining agents are present alone or in combination, the upper limit of their content is preferably 1%, more preferably 0.5%. In some embodiments, the content of one or more of the fining agents is about 0%, greater than 0%, 0.01%, 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, or 2%.

[0133] Other components not mentioned above, such as Yb2O3, Nb2O5, WO3, Bi2O3, Ta2O5, TeO2, and GeO2, may be appropriately contained in the matrix glass, crystallized glass, or crystallized glass product of the present invention, provided that the components do not affect the performance of the matrix glass, crystallized glass, or crystallized glass product of the present invention. However, in order to maintain the excellent performance of the matrix glass, crystallized glass, or crystallized glass product of the present invention, the individual or total content of Yb2O3, Nb2O5, WO3, Bi2O3, Ta2O5, TeO2, and GeO2 is preferably 5% or less, more preferably 2% or less, even more preferably 1% or less, and even more preferably, they are not contained at all.

[0134] PbO and As2O3 are toxic substances, and even small amounts thereof do not meet environmental protection requirements, so in some embodiments, the present invention preferably does not contain PbO and As2O3.

[0135] In some embodiments of the present invention, a colorant can be added to produce a colored matrix glass, crystallized glass, or crystallized glass product, allowing the matrix glass, crystallized glass, or crystallized glass product to exhibit different colors. Preferably, the colorant contains 0-4% NiO, 0-4% Ni2O3, 0-2% CoO, 0-2% Co2O3, 0-7% Fe2O3, 0-4% MnO2, 0-8% Er2O3, 0-8% Nd2O3, 0-4% Cu2O, 0-8% Pr2O5, and / or 0-4% CeO2. The weight percentage, content, and role of the colorant are described in detail below.

[0136] The brown or green matrix glass, crystallized glass, or crystallized glass product produced by the present invention uses NiO, Ni2O3, or Pr2O5 as a colorant. NiO and Ni2O3 are colorants used to produce brown or green matrix glass, crystallized glass, or crystallized glass product. The two components may be used alone or in combination, and their respective contents are generally 4% or less, preferably 3% or less. If the content exceeds 4%, the colorant will not dissolve well in the matrix glass, crystallized glass, or crystallized glass product. The lower limit of each content is 0.1% or more, and if it is less than 0.1%, the color of the matrix glass, crystallized glass, or crystallized glass product will not be noticeable. In some embodiments, the composition may contain about 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2.0%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3.0%, 3.1%, 3.2%, 3.3%, 3.4%, 3.5%, 3.6%, 3.7%, 3.8%, 3.9%, or 4.0% NiO or Ni2O3. When used in combination, the total content of NiO and Ni2O3 is generally 4% or less, and the lower limit of the total content is 0.1% or more. Some embodiments may contain about 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2.0%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3.0%, 3.1%, 3.2%, 3.3%, 3.4%, 3.5%, 3.6%, 3.7%, 3.8%, 3.9%, 4.0% NiO and Ni2O3.Pr2O5 is used as a colorant for green matrix glass, crystallized glass, or crystallized glass products. When used alone, the content is generally 8% or less, preferably 6% or less, and the lower limit of the content is 0.4% or more. When the content is less than 0.4%, the color of the matrix glass, crystallized glass, or crystallized glass product is not noticeable. In some embodiments, Pr2O5 may contain about 0.4%, 0.6%, 0.8%, 1.0%, 1.2%, 1.4%, 1.6%, 1.8%, 2.0%, 2.2%, 2.4%, 2.6%, 2.8%, 3.0%, 3.2%, 3.4%, 3.6%, 3.8%, 4.0%, 4.2%, 4.4%, 4.6%, 4.8%, 5.0%, 5.2%, 5.4%, 5.6%, 5.8%, 6.0%, 6.2%, 6.4%, 6.6%, 6.8%, 7.0%, 7.2%, 7.4%, 7.6%, 7.8%, or 8.0%.

[0137] In the blue matrix glass, crystallized glass or crystallized glass product produced by the present invention, CoO or Co2O3 is used as a colorant, and the two colorant components may be used alone or in combination, and the content of each is generally 2% or less, preferably 1.8% or less. If the content exceeds 2%, the colorant will not dissolve well in the matrix glass, crystallized glass or crystallized glass product. The lower limit of each content is 0.05% or more, and if it is less than 0.05%, the color of the matrix glass, crystallized glass or crystallized glass product will not be noticeable. In some embodiments, it may contain about 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, or 2.0% CoO or Co2O3. When used in combination, the total content of CoO and Co2O3 does not exceed 2%, with the lower limit of the total content being 0.05% or more. Some embodiments may contain about 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, or 2.0% CoO and Co2O3.

[0138] In the yellow matrix glass, crystallized glass or crystallized glass product produced by the present invention, Cu2O or CeO2 is used as a colorant, and the two colorant components are used alone or in combination, and the lower limit of each content is 0.5% or more. If the content is less than 0.5%, the color of the matrix glass, crystallized glass or crystallized glass product is not noticeable. If Cu2O is used alone, it should be 4% or less, preferably 3% or less. If the content exceeds 4%, the matrix glass is prone to crystallization. In some embodiments, the glass may contain about 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2.0%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3.0%, 3.1%, 3.2%, 3.3%, 3.4%, 3.5%, 3.6%, 3.7%, 3.8%, 3.9%, or 4.0% CuO. When CeO is used alone, the content is generally 4% or less, preferably 3% or less. If the content exceeds 4%, the gloss of the matrix glass, the crystallized glass, or the crystallized glass product may be poor. In some embodiments, the colorant may contain about 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2.0%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3.0%, 3.1%, 3.2%, 3.3%, 3.4%, 3.5%, 3.6%, 3.7%, 3.8%, 3.9%, or 4.0% CeO2. When two colorants are used in combination, their total content is generally 4% or less, with the lower limit being 0.5% or more.Some embodiments may contain about 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2.0%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3.0%, 3.1%, 3.2%, 3.3%, 3.4%, 3.5%, 3.6%, 3.7%, 3.8%, 3.9%, or 4.0% CeO2 and Cu2O.

[0139] In the black or smoke gray matrix glass, crystallized glass, or crystallized glass product produced by the present invention, Fe2O3 is used alone as a colorant, or a mixture of Fe2O3 and CoO as a colorant, or a mixture of Fe2O3 and CoO as a colorant, or a mixture of Fe2O3, CoO, and NiO as a colorant, or a mixture of Fe2O3, CoO, and NiO as a colorant. When producing black or smoke gray matrix glass, crystallized glass, or crystallized glass product, Fe2O3 is mainly used for coloring, and the Fe2O3 content is 7% or less, preferably 5% or less, with the lower limit of the content being 0.2% or more. In some embodiments, the FeO may contain about 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2.0%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3.0%, 3.1%, 3.2%, 3.3%, 3.4%, 3.5%, 3.6%, 3.7%, 3.8%, 3.9%, 4.0%, 4.5%, 5.0%, 5.5%, 6.0%, 6.5%, or 7.0% FeO. CoO and Co2O3 absorb visible light, thereby enhancing the color of the matrix glass, crystallized glass, or crystallized glass product. When used in a mixture with Fe2O3, the respective contents are typically 0.6% or less, with a lower limit of 0.2% or more. In some embodiments, the glass may contain approximately 0.2%, 0.3%, 0.4%, 0.5%, or 0.6% CoO and / or Co2O3. NiO absorbs visible light, thereby enhancing the color of the matrix glass, crystallized glass, or crystallized glass product. When used in a mixture, the respective contents are typically 1% or less, with a lower limit of 0.2% or more. In some embodiments, the glass may contain approximately 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, or 1.0% NiO.

[0140] In the purple matrix glass, crystallized glass or crystallized glass product produced by the present invention, MnO2 is used as a colorant, and the content used is generally 4% or less, preferably 3% or less, and the lower limit of the content is 0.1% or more. When the content is less than 0.1%, the color of the matrix glass, crystallized glass or crystallized glass product is not noticeable. In some embodiments, the MnO2 may contain about 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2.0%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3.0%, 3.1%, 3.2%, 3.3%, 3.4%, 3.5%, 3.6%, 3.7%, 3.8%, 3.9%, or 4.0% MnO2.

[0141] The pink matrix glass, crystallized glass or crystallized glass product produced by the present invention uses Er2O3 as a colorant, and the content is generally 8% or less, preferably 6% or less. Because the coloring efficiency of Er2O3 containing rare earth elements is low, even if the content exceeds 8%, the color of the matrix glass, crystallized glass or crystallized glass product cannot be further deepened, and the cost will increase. The lower limit of the content is 0.4% or more. If it is less than 0.4%, the color of the matrix glass, crystallized glass or crystallized glass product will not be noticeable. In some embodiments, Er2O3 may contain about 0.4%, 0.6%, 0.8%, 1.0%, 1.2%, 1.4%, 1.6%, 1.8%, 2.0%, 2.2%, 2.4%, 2.6%, 2.8%, 3.0%, 3.2%, 3.4%, 3.6%, 3.8%, 4.0%, 4.2%, 4.4%, 4.6%, 4.8%, 5.0%, 5.2%, 5.4%, 5.6%, 5.8%, 6.0%, 6.2%, 6.4%, 6.6%, 6.8%, 7.0%, 7.2%, 7.4%, 7.6%, 7.8%, or 8.0%.

[0142] The reddish-purple matrix glass, crystallized glass, or crystallized glass product produced by the present invention uses Nd2O3 as a colorant, and the content is generally 8% or less, preferably 6% or less. Because the coloring efficiency of Nd2O3 containing rare earth elements is low, even if the content exceeds 8%, the color of the matrix glass, crystallized glass, or crystallized glass product cannot be further deepened, and the cost will increase. The lower limit of the content is 0.4% or more. If it is less than 0.4%, the color of the matrix glass, crystallized glass, or crystallized glass product will not be noticeable. In some embodiments, Nd2O3 may contain about 0.4%, 0.6%, 0.8%, 1.0%, 1.2%, 1.4%, 1.6%, 1.8%, 2.0%, 2.2%, 2.4%, 2.6%, 2.8%, 3.0%, 3.2%, 3.4%, 3.6%, 3.8%, 4.0%, 4.2%, 4.4%, 4.6%, 4.8%, 5.0%, 5.2%, 5.4%, 5.6%, 5.8%, 6.0%, 6.2%, 6.4%, 6.6%, 6.8%, 7.0%, 7.2%, 7.4%, 7.6%, 7.8%, or 8.0%.

[0143] The red matrix glass, crystallized glass or crystallized glass product produced by the present invention uses a mixed colorant of Er2O3, Nd2O3 and MnO2, where Er ions in the glass absorb at 400-500nm, Mn ions mainly absorb at 500nm, and Nd ions mainly absorb strongly at 580nm. By mixing these three substances, red matrix glass, crystallized glass or crystallized glass product can be produced. Er2O3 and Nd2O3 are rare earth colorants, so their coloring strength is weak. The amount of Er2O3 used is within 6%, and the amount of Nd2O3 used is within 4%. MnO2 has a strong coloring strength and its amount is within 2%. The lower limit of the total content of the mixed colorants used is 0.9% or more.

[0144] The terms "not contained" and "0%" used in this specification mean that the compound, molecule, element, etc. is not intentionally added as a raw material to the matrix glass, crystallized glass, or crystallized glass product of the present invention. However, impurities or components that are not intentionally added as raw materials and / or equipment for producing the matrix glass, crystallized glass, or crystallized glass product may be contained in small or trace amounts in the final matrix glass, crystallized glass, or crystallized glass product, and such cases also fall within the scope of the claims of the present invention.

[0145] In some embodiments of the present invention, the inclusion of a nepheline crystalline phase as a crystalline phase in the crystallized glass and crystallized glass products provides the crystallized glass and crystallized glass products of the present invention with high strength, resulting in increased ball drop test height and four-point bending strength. In some embodiments, the crystallized glass or crystallized glass product contains a eucryptite crystalline phase, in some embodiments, the crystallized glass or crystallized glass product contains a sodium nepheline crystalline phase, and in some embodiments, the crystallized glass or crystallized glass product contains both a eucryptite crystalline phase and a sodium nepheline crystalline phase. The crystallized glass of the present invention has excellent chemical strengthening performance, and can be processed into a crystallized glass product by a chemical strengthening process to obtain excellent mechanical strength. By rationally designing the components, the crystallized glass and crystallized glass product of the present invention has an appropriate crystal grain size and can have high strength. The crystallized glass and crystallized glass product of the present invention has excellent mechanical properties due to the appropriate content of the crystalline phase.

[0146] The crystal grain size and type of crystalline phase of the crystallized glass or crystallized glass product of the present invention affect the haze and light transmittance of the crystallized glass or crystallized glass product.In some embodiments, the haze of the crystallized glass product or crystallized glass with a thickness of 1 mm or less is 0.15% or less, preferably 0.12% or less, more preferably 0.10% or less.In some embodiments, the crystal grain size of the crystallized glass product or crystallized glass is 80 nm or less, preferably 60 nm or less, more preferably 50 nm or less.

[0147] In some embodiments, the content and refractive index of the crystalline phase in the crystallized glass or crystallized glass product of the present invention affect the |B| value of the crystallized glass or crystallized glass product, and when observed in the visible light range, the crystallized glass or crystallized glass product appears bluish or yellowish, which affects the optical performance of the product, and is expressed as the |B| value in LAB (chromaticity value of the color of material). The crystallized glass or crystallized glass product of the present invention has a low |B| value in the visible light range, and in some embodiments, the |B| value of the crystallized glass product or crystallized glass with a thickness of 1 mm or less under the average light of 400 to 800 nm is 1.5 or less, preferably 1.0 or less, more preferably 0.8 or less.

[0148] In some embodiments, the crystallized glass or crystallized glass product of the present invention has high transparency in the visible light range (i.e., the crystallized glass or crystallized glass product is transparent).The crystallized glass or crystallized glass product has high transmittance in the visible light range, and in some preferred embodiments, the light transmittance at 550 nm of the crystallized glass product or crystallized glass with a thickness of 1 mm or less is preferably 88% or more, more preferably 89% or more, and even more preferably 90% or more.

[0149] In some embodiments, antimicrobial components may be added to the matrix glass, crystallized glass, or crystallized glass product. The crystallized glass or crystallized glass product described herein can be used, for example, in kitchens or food service counters where there is a high risk of exposure to harmful bacteria. Antimicrobial components contained in the matrix glass, crystallized glass, or crystallized glass product include, but are not limited to, Ag, AgO, Cu, CuO, CuO, etc. In some embodiments, the content of the above antimicrobial components alone or in combination is 2% or less, preferably 1% or less.

[0150] The matrix glass, crystallized glass and crystallized glass product of the present invention can be produced and manufactured by the following method.

[0151] To produce matrix glass, raw materials are mixed uniformly according to the component ratio, and the uniform mixture is placed in a platinum or quartz crucible. Depending on the degree of difficulty in melting the glass composition, the mixture is melted in an electric furnace or gas furnace at a temperature range of 1250 to 1650°C for 5 to 24 hours, stirred to make it uniform, and then cooled to an appropriate temperature, poured into a mold, and slowly cooled to produce matrix glass.

[0152] The matrix glass of the present invention can be formed by a known method.

[0153] The matrix glass of the present invention is subjected to a crystallization process after molding or processing to uniformly precipitate crystals within the glass. The crystallization process may be carried out in one stage or two stages, and is preferably carried out in two stages. A crystal nucleation process is carried out at a first temperature, followed by a crystal growth process at a second temperature higher than the temperature of the crystal nucleation process. The crystallization process carried out at the first temperature is called the first crystallization process, and the crystallization process carried out at the second temperature is called the second crystallization process.

[0154] In order for the glass-ceramics to have the desired physical properties, the preferred crystallization process is as follows.

[0155] As described above, by performing the crystallization treatment in one step, the crystal nucleus formation process and the crystal growth process can be carried out continuously. That is, the temperature is raised to a predetermined crystallization treatment temperature, and after reaching the crystallization treatment temperature, that temperature is maintained for a certain period of time and then lowered. The crystallization treatment temperature is preferably 580 to 750°C, and more preferably 600 to 700°C to allow the desired crystalline phase to precipitate. The holding time at the crystallization treatment temperature is preferably 0 to 8 hours, and more preferably 1 to 6 hours.

[0156] When the crystallization treatment is performed in two stages as described above, the first temperature is preferably 500 to 620° C., and the second temperature is preferably 620 to 750° C. The holding time at the first temperature is preferably 0 to 24 hours, more preferably 2 to 15 hours. The holding time at the second temperature is preferably 0 to 10 hours, more preferably 0.5 to 6 hours.

[0157] The holding time of 0 hours means that the temperature is lowered or raised again in less than 1 minute after reaching the temperature.

[0158] In some embodiments, the matrix glass or glass-ceramics described herein can be manufactured into shaped bodies by various processes, including, but not limited to, sheets, including, but not limited to, slit drawing, float, roll pressing, and other sheet forming processes known in the art. Alternatively, the matrix glass or glass-ceramics can be formed by float or roll pressing. Shaped bodies described herein further include lenses, prisms, and the like.

[0159] The matrix glass or crystallized glass of the present invention can be produced into a sheet glass molded body or crystallized glass molded body by methods such as polishing or buffing, but the method for producing the glass molded body or crystallized glass molded body is not limited to these methods.

[0160] The matrix glass or crystallized glass of the present invention can be formed by producing glass molded bodies or crystallized glass molded bodies of various shapes by methods such as a hot bending process or a press molding process at a constant temperature, but is not limited to these methods.

[0161] In some embodiments, a glass molded body or a crystallized glass molded body may be manufactured by a hot bending process. The hot bending process involves placing 2D glass, 2.5D glass, or crystallized glass in a mold, and sequentially carrying out steps such as temperature increase preheating, pressure molding, and pressure hold and temperature decrease in a hot bending machine to manufacture a 3D curved glass molded body or a crystallized glass molded body.

[0162] In some embodiments, the crystallized glass shaped body has a 2.5D structure or a 3D structure, i.e., a non-planar structure. As used herein, the term "non-planar structure" refers to a structure in which, in a 2.5D or 3D shape, at least a portion of the crystallized glass shaped body extends outward or along an included angle with a plane defined by the original layout arrangement of the 2D matrix glass. The 2.5D or 3D crystallized glass shaped body formed by the matrix glass may have one or more protrusions or bends.

[0163] In some embodiments, the method for producing a crystallized glass-shaped body is a hot bending process, in accordance with the characteristics of crystallized glass-shaped bodies, such as the growth and change of crystalline phases. Specifically, the method includes pre-crystallization and hot working molding. The pre-crystallization described in the present invention is to treat a matrix glass with a controlled crystallization process to form a pre-crystallized glass-shaped body, and the crystallinity of the pre-crystallized glass-shaped body does not reach the crystallinity required for the performance index of the target crystallized glass-shaped body. The pre-crystallized glass-shaped body is formed by treating the pre-crystallized glass with a hot working molding process.

[0164] In some embodiments, the method for producing a crystallized glass molded body includes: 1) subjecting a matrix glass to a primary crystallization heat treatment process, including heating, adiabatic nucleation, heating, adiabatic crystallization, and cooling to room temperature, to form a pre-crystallized glass; 2) hot-working and shaping the pre-crystallized glass to obtain a crystallized glass-shaped body.

[0165] The crystallization heat treatment process described in the present invention is performed by heating the matrix glass at a certain temperature T h Nucleation at t h After 2 hours, the temperature reaches a certain T c At c The crystallinity of the pre-crystallized glass-ceramics obtained does not reach the crystallinity required for the performance index of the target crystallized glass-shaped body. Using the XRD measurement data, the total content of the main crystalline phases in the case where the crystallinity of the pre-crystallized glass-ceramics is determined by the Rietveld full pattern fitting refinement method. c1 was calculated. The pre-crystallization of the present invention is a complete process, including a one-stage nucleation process, a one-stage, two-stage, or three or more-stage crystallization process, including heating, adiabatic heating, reheating, re-adiabatic heating, etc., followed by cooling to room temperature according to the process. Unlike the primary crystallization, secondary crystallization, etc. mentioned in some literature or patents, the present invention is actually a continuous process consisting of only the first stage crystallization, the second stage crystallization, etc., in a complete crystallization process, and does not include the process of cooling to room temperature, followed by reheating and crystallization.

[0166] The hot working forming described in the present invention refers to subjecting the pre-crystallized glass to a forming treatment by a hot working process under conditions of certain temperature, time, pressure, etc., and the hot working forming includes one or more hot working processes, and the hot working process includes, but is not limited to, subjecting the pre-crystallized glass to press forming, bending forming, or drawing forming under conditions of certain temperature, time, pressure, etc. In the hot working forming process, a formed body with a complex shape may not be formed in one hot working process, and may need to be hot worked two or more times.

[0167] In some embodiments, the method for producing a crystallized glass molded body is a hot bending process. Specifically, in some embodiments, the method for producing a crystallized glass molded body includes the following steps 1) to 3).

[0168] 1) In the preheating step, matrix glass, pre-crystallized glass, or crystallized glass is placed in a mold, and the mold passes through each heating station in the hot bending machine in sequence, staying at each station for a set time to insulate. The temperature in the preheating zone is 400-800°C, the pressure is 0.01-0.05 MPa, and the time is 40-200 seconds. In some embodiments, for a hot bending machine with five preheating stations, the initial heating is generally set to a stable temperature of approximately 500°C, and the temperature is gradually increased at each subsequent station. The temperature gradient between adjacent two sites gradually decreases from low to high, and the temperature difference between the last preheating station and the first press-forming station can be within a 20°C range.

[0169] 2) In the pressure molding step, the mold is preheated and then transferred to the molding station. A certain pressure is applied to the mold by a hot bending machine. The pressure range is 0.1-0.8 MPa, and the magnitude of the pressure is determined according to factors such as the glass thickness and arc degree. The temperature range of the molding station is 650-850°C, and the molding time range is 40-200 s.

[0170] 3) In the pressure-holding and temperature-reducing step, the mold is transferred to the temperature-reducing station and the temperature is reduced at each station. The temperature range for the temperature reduction is controlled to 750 to 500°C, the pressure is 0.01 to 0.05 MPa, and the time is 40 to 200 seconds.

[0171] When forming a crystallized glass body using a hot bending process, it is necessary to control the appearance quality of common high-aluminum glasses, as well as the effect of crystal growth development during the hot bending process on the performance of the crystallized glass. For example, in the case of 3D curved crystallized glass used for display devices or electronic device cases, close attention must be paid to the light transmittance, haze, |B| value and their uniformity after hot bending.

[0172] The amount of change in crystalline phase before and after hot bending affects the size uniformity, mass production feasibility, and cost control of the crystallized glass molded body. The matrix glass and crystallized glass of the present invention have excellent hot processing performance, and after hot bending, the amount of change in crystalline phase content is 20% or less, preferably 15% or less, and more preferably 10% or less, which ensures the uniformity of the haze and |B| value of the crystallized glass molded body obtained after hot bending.

[0173] The matrix glasses, glass-ceramics and glass-ceramic articles described in this invention may have any reasonable and useful thickness.

[0174] The crystallized glass of the present invention not only improves mechanical properties by precipitating crystals, but also provides better mechanical properties by forming a compressive stress layer, allowing for the production of crystallized glass products.

[0175] In some embodiments, the matrix glass or glass-ceramics can be processed to form a sheet and / or shaped (e.g., punched, hot bent, etc.), shaped, buffed and / or cleaned, and further chemically strengthened by a chemical strengthening process to form a crystallized glass article. In some embodiments, the crystallized glass shaped body can be chemically strengthened by a chemical strengthening process to form a crystallized glass article.

[0176] The chemical strengthening method described in the present invention is an ion exchange method. During the ion exchange process, small metal ions in the matrix glass, crystallized glass, or crystallized glass-shaped body are replaced or "exchanged" with larger metal ions with the same valence that are close to the matrix glass, crystallized glass, or crystallized glass-shaped body. The replacement of the small ions with the larger ions creates compressive stress on the surface of the matrix glass, crystallized glass, or crystallized glass-shaped body, and tensile stress inside.

[0177] In some embodiments, the metal ion is a monovalent alkali metal ion (e.g., Na + , K. + , Rb + , Cs + The ion exchange is carried out by immersing the matrix glass, the crystallized glass, or the crystallized glass shaped body in a salt bath of at least one molten salt containing large metal ions, and the large metal ions are intended to replace the small metal ions in the matrix glass, the crystallized glass, or the crystallized glass shaped body. Alternatively, Ag + , Tl + , Cu + The monovalent ions may be exchanged with other monovalent metal ions, such as ions of a metal such as ammonium ions, ammonium ions, ammonium ions, etc. One or more ion exchange processes for chemically strengthening a matrix glass, a crystallized glass, or a crystallized glass body include, but are not limited to, immersion in a single salt bath or in multiple salt baths of the same or different composition, with washing and / or annealing steps between immersions.

[0178] In some embodiments, the matrix glass, the crystallized glass, or the crystallized glass-shaped body may be immersed in a salt bath of molten Na salt (e.g., NaNO) at a temperature of about 350 to 470°C for about 1 to 36 hours to perform ion exchange, preferably in a temperature range of 380 to 460°C, and for a time range of 2 to 10 hours. In such embodiments, a surface compression layer is formed by substituting some of the Li ions in the matrix glass, the crystallized glass, or the crystallized glass-shaped body with Na ions, resulting in high mechanical properties. In some embodiments, the matrix glass, the crystallized glass, or the crystallized glass-shaped body may be immersed in a salt bath of molten K salt (e.g., KNO) at a temperature of about 360 to 450°C for 1 to 36 hours to perform ion exchange, preferably in a time range of 1 to 10 hours. In some embodiments, the matrix glass, the crystallized glass, or the crystallized glass molded body may be immersed in a mixed salt bath of K molten salt and Na molten salt at a temperature of about 360 to 450°C for 1 to 36 hours to perform ion exchange, preferably for 2 to 24 hours.

[0179] Each performance index of the crystallized glass or crystallized glass product of the present invention is measured by the following method.

[0180] [Hayes] Using a Minolta CM-3600A spectrophotometer, samples of less than 1 mm were prepared and measured according to GB2410-80.

[0181] [Grain size] Measurements are made using an SEM scanning electron microscope. After surface treatment of the crystallized glass in HF acid, the surface of the crystallized glass is coated with metal, and the surface is scanned with an SEM scanning electron microscope to determine the size of the crystal grains.

[0182] [Light transmittance] All light transmittances described in this specification are external transmittances, and may be abbreviated as transmittances.

[0183] The sample is processed to a thickness of 1 mm or less, buffed parallel to the opposing surfaces, and the light transmittance at 550 nm is measured using a Minolta CM-3600A spectrophotometer.

[0184] [Surface stress] and [Ion exchange layer depth] The surface stress is measured using a glass surface stress meter SLP-2000.

[0185] The depth of the ion-exchange layer is measured using a glass surface stress meter SLP-2000.

[0186] The measurement conditions are a refractive index of the sample of 1.56 and an optical elastic constant of 24.5 [(nm / cm) / Mpa].

[0187] [Dropping ball test height] A sample of a crystallized glass product measuring 150 mm x 73 mm in length and width and less than 1 mm thick is placed on a glass mounting jig and a 132 g steel ball is dropped from a predetermined height. The maximum ball drop test height is the height at which the sample can withstand the impact without breaking. Specifically, the test is conducted starting from a 400 mm ball drop test height. If no breakage occurs, the height is increased in 100 mm increments to 400 mm, 500 mm, 600 mm, 700 mm, and higher. For examples with a "ball drop test height," the crystallized glass product is the test subject. In the examples, test data recorded as 1600 mm indicates that the sample did not break when subjected to an impact of 1500 mm, but broke when raised to 1600 mm and measured, indicating that the ball drop test height was 1600 mm. In this specification, the ball drop test height may be abbreviated as "ball drop height."

[0188] [Ball drop height] A crystallized glass sample measuring 150mm x 73mm in length x width and less than 1mm thick is placed on a glass mounting jig, and a 32g steel ball is dropped from a predetermined height. The maximum ball drop test height at which the sample can withstand impact without breaking is defined as the main ball drop height. Specifically, the test is conducted starting from a ball drop test height of 400mm. If no breakage occurs, the height is changed in 100mm increments to 400mm, 500mm, 600mm, 700mm, and above. For examples with a "main ball drop height," the test subject is crystallized glass, i.e., the ball drop test height of crystallized glass. In the examples, the test data recorded as 1300mm indicates that the main ball drop height is 1300mm, because the sample did not break when impacted at 1200mm, but broke when raised to 1300mm and measured.

[0189] [4-point bending strength] The four-point bending strength is measured using a microcomputer-controlled electronic universal testing machine CMT6502, with the sample thickness set to 1 mm or less, according to ASTM C 158-2002. In the present invention, the four-point bending strength may be abbreviated as bending strength.

[0190] [Vickers hardness] The load when a pyramidal indentation is made on the test surface using a diamond pyramidal indenter with a facing angle of 136° is calculated based on the surface area (mm 2 The test is performed with a test load of 200 g and a holding time of 20 seconds. In the present invention, Vickers hardness may be abbreviated to hardness.

[0191] [|B|value] The B value is measured using a Minolta CM-700d. The sample specifications are set so that the thickness is 1mm or less, and the zero point calibration and whiteboard calibration of the equipment are performed using the set of long and short calibration tubes. After calibration, an airborne test is performed using the long tube to determine the stable calibration reliability of the equipment (B≦0.05). After passing the equipment calibration, the product is placed on the zero point long tube and measured.

[0192] The |B| value is the absolute value of the B value.

[0193] The crystallized glass product of the present invention has the following properties.

[0194] 1) In some embodiments, the four-point bending strength of a crystallized glass product having a thickness of 1 mm or less is 700 MPa or more, preferably 750 MPa or more, and more preferably 800 MPa or more. The thickness is preferably 0.2 to 1 mm, more preferably 0.3 to 0.9 mm, even more preferably 0.5 to 0.8 mm, and even more preferably 0.55 mm, 0.6 mm, 0.68 mm, 0.7 mm, or 0.75 mm.

[0195] 2) In some embodiments, the depth of the ion exchange layer of the crystallized glass product is 50 μm or more, preferably 60 μm or more, more preferably 80 μm or more, and even more preferably 100 μm or more.

[0196] 3) In some embodiments, the height of a ball drop test of a crystallized glass product having a thickness of 1 mm or less is 1100 mm or more, preferably 1300 mm or more, and more preferably 1500 mm or more. The thickness is preferably 0.2 to 1 mm, more preferably 0.3 to 0.9 mm, even more preferably 0.5 to 0.8 mm, and even more preferably 0.55 mm, 0.6 mm, 0.68 mm, 0.7 mm, or 0.75 mm.

[0197] 4), in some embodiments, the Vickers hardness (H v ) is 750kgf / mm 2 or more, and preferably 780 kgf / mm 2 More preferably, it is 800 kgf / mm 2 More preferably, it is 810 kgf / mm 2 That's all.

[0198] 5) In some embodiments, the crystal grain size of the crystallized glass product is 80 nm or less, preferably 60 nm or less, more preferably 50 nm or less, and even more preferably 40 nm or less.

[0199] 6) In some embodiments, the surface stress of the crystallized glass article is 150 MPa or more, preferably 170 MPa or more, and more preferably 190 MPa or more.

[0200] 7) In some embodiments, the haze of a crystallized glass product having a thickness of 1 mm or less is 0.15% or less, preferably 0.12% or less, and more preferably 0.10% or less. The thickness is preferably 0.2 to 1 mm, more preferably 0.3 to 0.9 mm, even more preferably 0.5 to 0.8 mm, and even more preferably 0.55 mm, 0.6 mm, 0.68 mm, 0.7 mm, or 0.75 mm.

[0201] 8) In some embodiments, the light transmittance at a wavelength of 550 nm of a crystallized glass product having a thickness of 1 mm or less is 88% or more, preferably 89% or more, more preferably 90% or more, and even more preferably 91% or more. The thickness is preferably 0.2 to 1 mm, more preferably 0.3 to 0.9 mm, even more preferably 0.5 to 0.8 mm, and even more preferably 0.55 mm, 0.6 mm, 0.68 mm, 0.7 mm, or 0.75 mm.

[0202] 9) In some embodiments, the |B| value of a crystallized glass product having a thickness of 1 mm or less under average light of 400 to 800 nm is 1.5 or less, preferably 1.0 or less, and more preferably 0.8 or less. The thickness is preferably 0.2 to 1 mm, more preferably 0.3 to 0.9 mm, even more preferably 0.5 to 0.8 mm, and even more preferably 0.55 mm, 0.6 mm, 0.68 mm, 0.7 mm, or 0.75 mm.

[0203] The crystallized glass of the present invention has the following properties.

[0204] 1) In some embodiments, the crystal grain size of the glass-ceramics is 80 nm or less, preferably 60 nm or less, more preferably 50 nm or less, and even more preferably 40 nm or less.

[0205] 2) In some embodiments, the haze of the crystallized glass having a thickness of 1 mm or less is 0.15% or less, preferably 0.12% or less, and more preferably 0.10% or less. The thickness is preferably 0.2 to 1 mm, more preferably 0.3 to 0.9 mm, even more preferably 0.5 to 0.8 mm, and even more preferably 0.55 mm, 0.6 mm, 0.68 mm, 0.7 mm, or 0.75 mm.

[0206] 3) In some embodiments, the light transmittance at a wavelength of 550 nm of a crystallized glass having a thickness of 1 mm or less is 88% or more, preferably 89% or more, more preferably 90% or more, and even more preferably 91% or more. The thickness is preferably 0.2 to 1 mm, more preferably 0.3 to 0.9 mm, even more preferably 0.5 to 0.8 mm, and even more preferably 0.55 mm, 0.6 mm, 0.68 mm, 0.7 mm, or 0.75 mm.

[0207] 4) In some embodiments, the body falling ball height of a crystallized glass having a thickness of 1 mm or less is 1000 mm or more, preferably 1200 mm or more, and more preferably 1400 mm or more. The thickness is preferably 0.2 to 1 mm, more preferably 0.3 to 0.9 mm, even more preferably 0.5 to 0.8 mm, and even more preferably 0.55 mm, 0.6 mm, 0.68 mm, 0.7 mm, or 0.75 mm.

[0208] 5) In some embodiments, the |B| value of the crystallized glass having a thickness of 1 mm or less under average light of 400 to 800 nm is 1.5 or less, preferably 1.0 or less, and more preferably 0.8 or less. The thickness is preferably 0.2 to 1 mm, more preferably 0.3 to 0.9 mm, even more preferably 0.5 to 0.8 mm, and even more preferably 0.55 mm, 0.6 mm, 0.68 mm, 0.7 mm, or 0.75 mm.

[0209] 6), in some embodiments, the Vickers hardness (H v ) is 650kgf / mm 2 or more, and preferably 680 kgf / mm 2 More preferably, it is 700 kgf / mm 2 That's all.

[0210] Because the crystallized glass, crystallized glass product, matrix glass, glass molded body, and crystallized glass molded body of the present invention have the above-mentioned excellent properties, they can be widely used to manufacture glass cover plates or glass parts, and can be applied to electronic devices or display devices such as mobile phones, watches, computers, and touch displays, and can be used to manufacture protective glass for mobile phones, smartphones, tablet computers, laptops, PDAs, televisions, personal computers, MTA equipment, or industrial displays, or to manufacture touch panels, protective windows, automobile windows, train windows, aircraft windows, and touch panel protective glass, or to manufacture hard disk substrates or solar cell substrates, or to manufacture white home appliances such as refrigerator components or cooking utensils.

[0211] (Example) In order to more clearly understand and explain the technical means of the present invention, the following non-limiting examples are provided. Although great efforts have been made to ensure the accuracy of the numerical values ​​in the examples of the present invention, it is necessary to consider that there are some errors and deviations. The composition of the crystallized glass or crystallized glass product is expressed in weight percent based on oxides and is normalized to 100%.

[0212] <Examples of glass-ceramics> In the present example, crystallized glasses having the compositions shown in Tables 1 to 3 were obtained by the above-mentioned method for producing crystallized glasses. The properties of each crystallized glass were measured by the measuring method described in the present invention, and the measurement results are shown in Tables 1 to 3. In the following examples, the thickness of the measurement sample used for the main body falling ball height, haze, light transmittance, |B| value, etc. was 0.7 mm.

[0213] [Table 1]

[0214] [Table 2]

[0215] [Table 3]

[0216] <Examples of Crystallized Glass Products> In the present examples, crystallized glass products having the compositions shown in Tables 4 to 6 were obtained by the above-mentioned method for producing crystallized glass products. The properties of each crystallized glass product were measured using the measurement method described in the present invention, and the measurement results are shown in Tables 4 to 6. In the following examples, the thickness of the measurement sample used for the four-point bending strength, ball drop test height, haze, light transmittance, |B| value, etc. was 0.7 mm.

[0217] [Table 4]

[0218] [Table 5]

[0219] [Table 6]

Claims

1. As a constituent, 40 to 60% by weight of SiO ２ , 20-40% Al ２ O ３ , 2 to 15% Li ２ O, 3-20% Na ２ O and 1-15% P ２ O ５ + ZrO ２ containing A crystallized glass product characterized by:

2. As a component, 0 to 8% by weight of K ２ O, and / or 0 to 6% ZnO, and / or 0 to 6% B ２ O ３ , and / or 0-8% RO, and / or 0-5% TiO ２ , and / or 0 to 5% Ln ２ O ３ and / or 0 to 2% of a fining agent, wherein the RO is one or more of MgO, CaO, SrO, and BaO, and the Ln ２ O ３ Is, La ２ O ３ , Gd ２ O ３ , Y ２ O ３ one or more of 2. The crystallized glass product according to claim 1.

3. As a constituent, 40 to 60% by weight of SiO ２ , 20-40% Al ２ O ３ , 2 to 15% Li ２ O, 3-20% Na ２ O, 1-15% P ２ O ５ + ZrO ２ 0-8% K ２ O, 0-6% ZnO, 0-6% B ２ O ３ , 0-8% RO, 0-5% TiO ２ , 0-5% Ln ２ O ３ and 0 to 2% of a fining agent, wherein the RO is one or more of MgO, CaO, SrO, and BaO, and the Ln ２ O ３ Is, La ２ O ３ , Gd ２ O ３ , Y ２ O ３ one or more of A crystallized glass product characterized by:

4. When the components are calculated in weight percentage, (Al ２ O ３ +Na ２ O) / P ２ O ５ is 3.0 to 30.0, and preferably (Al ２ O ３ +Na ２ O) / P ２ O ５ is 4.0 to 20.0, and more preferably (Al ２ O ３ +Na ２ O) / P ２ O ５ is 5.0 to 15.0, and more preferably (Al ２ O ３ +Na ２ O) / P ２ O ５ is 6.0 to 10.0, The crystallized glass product according to any one of claims 1 to 3.

5. The components are calculated by weight percentage as follows: SiO ２ / Al ２ O ３ is 1.2 to 2.8, and preferably SiO ２ / Al ２ O ３ is 1.3 to 2.5, and more preferably, SiO ２ / Al ２ O ３ is 1.5 to 2.2, and more preferably SiO ２ / Al ２ O ３ is 1.6 to 2.0, The crystallized glass product according to any one of claims 1 to 3.

6. The components are calculated by weight percentage as follows: SiO ２ / (Na ２ O+B ２ O ３ ) is 2.0 to 15.0, and preferably SiO ２ / (Na ２ O+B ２ O ３ ) is 3.0 to 10.0, and more preferably, SiO ２ / (Na ２ O+B ２ O ３ ) is 4.0 to 8.0, and more preferably, SiO ２ / (Na ２ O+B ２ O ３ ) is 5.0 to 7.0, The crystallized glass product according to any one of claims 1 to 3.

7. When the components are calculated by weight percentage, (Na ２ O + Li ２ O) / SiO ２ is 0.1 to 0.8, and preferably (Na ２ O + Li ２ O) / SiO ２ is 0.15 to 0.7, and more preferably (Na ２ O + Li ２ O) / SiO ２ is 0.2 to 0.6, and more preferably (Na ２ O + Li ２ O) / SiO ２ is 0.25 to 0.5, The crystallized glass product according to any one of claims 1 to 3.

8. The components are calculated in weight percentage as follows: (ZrO ２ +ZnO) / Na ２ O is 2.0 or less, and preferably (ZrO ２ +ZnO) / Na ２ O is 1.5 or less, and more preferably (ZrO ２ +ZnO) / Na ２ O is 0.01 to 1.0, and more preferably (ZrO ２ +ZnO) / Na ２ O is 0.1 to 0.5; The crystallized glass product according to any one of claims 1 to 3.

9. When the components are calculated in weight percentage, (P ２ O ５ +Na ２ O) / Li ２ O is 0.5 to 8.0, and preferably (P ２ O ５ +Na ２ O) / Li ２ O is 0.8 to 5.0, and more preferably, (P ２ O ５ +Na ２ O) / Li ２ O is 1.0 to 3.0, and more preferably, (P ２ O ５ +Na ２ O) / Li ２ O is 1.5 to 2.5; The crystallized glass product according to any one of claims 1 to 3.

10. When the components are calculated by weight percentage, K ２ O / ZrO ２ is 0.1 or more, and preferably, K ２ O / ZrO ２ is 0.2 to 10.0, and more preferably, K ２ O / ZrO ２ is 0.3 to 5.0, and more preferably, K ２ O / ZrO ２ is 0.4 to 1.5, The crystallized glass product according to any one of claims 1 to 3.

11. The weight percentage of the components is calculated as follows: (ZnO + RO + B ２ O ３ + TiO ２ ) / P ２ O ５ is 1.5 or less, and preferably (ZnO + RO + B ２ O ３ + TiO ２ ) / P ２ O ５ is 1.0 or less, and more preferably, (ZnO + RO + B ２ O ３ + TiO ２ ) / P ２ O ５ is 0.5 or less, and more preferably, (ZnO + RO + B ２ O ３ + TiO ２ ) / P ２ O ５ is 0.2 or less, and the RO is one or more of MgO, CaO, SrO, and BaO; The crystallized glass product according to any one of claims 1 to 3.

12. As a constituent, 43 to 55% by weight of SiO ２ , preferably 46-53% SiO ２ and / or 23 to 36% Al ２ O ３ , preferably 25.5 to 32% Al ２ O ３ and / or 3 to 13% Li ２ O, preferably 5.5 to 11% Li ２ O, and / or 5-15% Na ２ O, preferably 6.5 to 12% Na ２ O, and / or 2-12% P ２ O ５ + ZrO ２ , preferably 4 to 10% P ２ O ５ + ZrO ２ , and / or 0 to 5% K ２ O, preferably 0.1 to 3% K ２ O, and / or 0-3% ZnO, preferably 0-1% ZnO, and / or 0-3% B ２ O ３ , preferably 0 to 1% B ２ O ３ and / or 0 to 5% RO, preferably 0 to 2% RO, and / or 0 to 3% TiO ２ , preferably 0 to 1% TiO ２ , and / or 0 to 3% Ln ２ O ３ , preferably 0 to 1% Ln ２ O ３ and / or 0 to 1% of a fining agent, preferably 0 to 0.5%, wherein the RO is one or more of MgO, CaO, SrO, and BaO; and the Ln ２ O ３ Is, La ２ O ３ , Gd ２ O ３ , Y ２ O ３ one or more of The crystallized glass product according to any one of claims 1 to 3.

13. As a component, by weight percentage, 0 to 6% ZrO ２ , preferably 0-5% ZrO ２ , more preferably 0.1 to 3% ZrO ２ , and / or 0-10% P ２ O ５ , preferably 1 to 8% P ２ O ５ , more preferably 2 to 6% P ２ O ５ containing The crystallized glass product according to any one of claims 1 to 3.

14. As a constituent, by weight percentage, 0 to 5% Yb ２ O ３ +Nb ２ O ５ +WO ３ +Bi ２ O ３ +Ta ２ O ５ + TeO ２ +GeO ２ , preferably 0 to 2% Yb ２ O ３ +Nb ２ O ５ +WO ３ +Bi ２ O ３ +Ta ２ O ５ + TeO ２ +GeO ２ , more preferably 0 to 1% Yb ２ O ３ +Nb ２ O ５ +WO ３ +Bi ２ O ３ +Ta ２ O ５ + TeO ２ +GeO ２ Further containing 3. The crystallized glass product according to claim 1 or 2.

15. containing a nepheline crystalline phase, and / or a lithium silicate crystalline phase, and / or a lithium phosphate crystalline phase, and / or a petalite crystalline phase, and / or a quartz crystalline phase; The crystallized glass product according to any one of claims 1 to 3.

16. The crystallized glass product has a nepheline crystal phase as the main crystalline phase, or the crystallized glass product contains only the nepheline crystal phase. The crystallized glass product according to any one of claims 1 to 3.

17. The weight percentage of the neferine crystalline phase in the crystallized glass product is 10 to 80%, preferably 20 to 70%, and more preferably 30 to 60%. The crystallized glass product according to any one of claims 1 to 3.

18. the ion exchange layer depth is 50 μm or more, preferably 60 μm or more, more preferably 80 μm or more, and even more preferably 100 μm or more; and / or the Vickers hardness is 750 kgf / mm or more, preferably 780 kgf / mm or more, more preferably 800 kgf / mm or more, and even more preferably 810 kgf / mm or more; and / or the crystal grain size is 80 nm or less, preferably 60 nm or less, more preferably 50 nm or less, and even more preferably 40 nm or less; and / or the surface stress is 150 MPa or more, preferably 170 MPa or more, and even more preferably 190 MPa or more. The crystallized glass product according to any one of claims 1 to 3.

19. The crystallized glass product having a thickness of 1 mm or less has a four-point bending strength of 700 MPa or more, preferably 750 MPa or more, and more preferably 800 MPa or more, and / or a ball drop test height of 1100 mm or more, preferably 1300 mm or more, and more preferably 1500 mm or more, and / or a haze of 0.15% or less, preferably 0.12% or less, and more preferably 0.10% or less, and / or a light transmittance at a wavelength of 550 nm of 88% or more, preferably 89% or more, more preferably 90% or more, and even more preferably 91% or more, and / or a |B| value for average light of 400 to 800 nm of 1.5 or less, preferably 1.0 or less, and more preferably 0.8 or less. The crystallized glass product according to any one of claims 1 to 3.

20. The thickness is 0.2 to 1 mm, preferably 0.3 to 0.9 mm, more preferably 0.5 to 0.8 mm, and even more preferably 0.55 mm, 0.6 mm, 0.68 mm, 0.7 mm, or 0.75 mm.

20. The crystallized glass product according to claim 19.

21. As components, by weight percentage, 0 to 4% NiO and / or 0 to 4% Ni ２ O ３ , and / or 0-2% CoO, and / or 0-2% Co ２ O ３ and / or 0 to 7% Fe ２ O ３ and / or 0 to 4% MnO ２ , and / or 0 to 8% Er ２ O ３ , and / or 0 to 8% Nd ２ O ３ and / or 0-4% Cu ２ O, and / or 0-8% Pr ２ O ３ and / or 0-4% CeO ２ Further containing 3. The crystallized glass product according to claim 1 or 2.

22. As a constituent, 40 to 60% by weight of SiO ２ , 20-40% Al ２ O ３ , 2 to 15% Li ２ O, 3-20% Na ２ O and 1-15% P ２ O ５ + ZrO ２ containing 1. A crystallized glass characterized by:

23. As a component, 0 to 8% by weight of K ２ O, and / or 0 to 6% ZnO, and / or 0 to 6% B ２ O ３ , and / or 0-8% RO, and / or 0-5% TiO ２ , and / or 0 to 5% Ln ２ O ３ and / or 0 to 2% of a fining agent, wherein the RO is one or more of MgO, CaO, SrO, and BaO, and the Ln ２ O ３ Is, La ２ O ３ , Gd ２ O ３ , Y ２ O ３ one or more of 23. The crystallized glass according to claim 22.

24. As a constituent, 40 to 60% by weight of SiO ２ , 20-40% Al ２ O ３ , 2 to 15% Li ２ O, 3-20% Na ２ O, 1-15% P ２ O ５ + ZrO ２ , 0-8% K ２ O, 0-6% ZnO, 0-6% B ２ O ３ , 0-8% RO, 0-5% TiO ２ , 0-5% Ln ２ O ３ and 0 to 2% of a fining agent, wherein the RO is one or more of MgO, CaO, SrO, and BaO, and the Ln ２ O ３ Is, La ２ O ３ , Gd ２ O ３ , Y ２ O ３ one or more of 1. A crystallized glass characterized by:

25. When the components are calculated in weight percentage, (Al ２ O ３ +Na ２ O) / P ２ O ５ is 3.0 to 30.0, and preferably (Al ２ O ３ +Na ２ O) / P ２ O ５ is 4.0 to 20.0, and more preferably (Al ２ O ３ +Na ２ O) / P ２ O ５ is 5.0 to 15.0, and more preferably (Al ２ O ３ +Na ２ O) / P ２ O ５ is 6.0 to 10.0, The crystallized glass according to any one of claims 22 to 24.

26. The components are calculated by weight percentage as follows: SiO ２ / Al ２ O ３ is 1.2 to 2.8, and preferably SiO ２ / Al ２ O ３ is 1.3 to 2.5, and more preferably, SiO ２ / Al ２ O ３ is 1.5 to 2.2, and more preferably SiO ２ / Al ２ O ３ is 1.6 to 2.0, The crystallized glass according to any one of claims 22 to 24.

27. The components are calculated by weight percentage as follows: SiO ２ / (Na ２ O+B ２ O ３ ) is 2.0 to 15.0, and preferably SiO ２ / (Na ２ O+B ２ O ３ ) is 3.0 to 10.0, and more preferably, SiO ２ / (Na ２ O+B ２ O ３ ) is 4.0 to 8.0, and more preferably, SiO ２ / (Na ２ O+B ２ O ３ ) is 5.0 to 7.0, The crystallized glass according to any one of claims 22 to 24.

28. When the components are calculated by weight percentage, (Na ２ O + Li ２ O) / SiO ２ is 0.1 to 0.8, and preferably (Na ２ O + Li ２ O) / SiO ２ is 0.15 to 0.7, and more preferably (Na ２ O + Li ２ O) / SiO ２ is 0.2 to 0.6, and more preferably (Na ２ O + Li ２ O) / SiO ２ is 0.25 to 0.5, The crystallized glass according to any one of claims 22 to 24.

29. The components are calculated in weight percentage as follows: (ZrO ２ +ZnO) / Na ２ O is 2.0 or less, and preferably (ZrO ２ +ZnO) / Na ２ O is 1.5 or less, and more preferably (ZrO ２ +ZnO) / Na ２ O is 0.01 to 1.0, and more preferably (ZrO ２ +ZnO) / Na ２ O is 0.1 to 0.5; The crystallized glass according to any one of claims 22 to 24.

30. When the components are calculated in weight percentage, (P ２ O ５ +Na ２ O) / Li ２ O is 0.5 to 8.0, and preferably (P ２ O ５ +Na ２ O) / Li ２ O is 0.8 to 5.0, and more preferably, (P ２ O ５ +Na ２ O) / Li ２ O is 1.0 to 3.0, and more preferably, (P ２ O ５ +Na ２ O) / Li ２ O is 1.5 to 2.5; The crystallized glass according to any one of claims 22 to 24.

31. When the components are calculated by weight percentage, K ２ O / ZrO ２ is 0.1 or more, and preferably, K ２ O / ZrO ２ is 0.2 to 10.0, and more preferably, K ２ O / ZrO ２ is 0.3 to 5.0, and more preferably, K ２ O / ZrO ２ is 0.4 to 1.5, The crystallized glass according to any one of claims 22 to 24.

32. The weight percentage of the components is calculated as follows: (ZnO + RO + B ２ O ３ + TiO ２ ) / P ２ O ５ is 1.5 or less, and preferably (ZnO + RO + B ２ O ３ + TiO ２ ) / P ２ O ５ is 1.0 or less, and more preferably, (ZnO + RO + B ２ O ３ + TiO ２ ) / P ２ O ５ is 0.5 or less, and more preferably, (ZnO + RO + B ２ O ３ + TiO ２ ) / P ２ O ５ is 0.2 or less, and the RO is one or more of MgO, CaO, SrO, and BaO; The crystallized glass according to any one of claims 22 to 24.

33. As a constituent, 43 to 55% by weight of SiO ２ , preferably 46-53% SiO ２ and / or 23 to 36% Al ２ O ３ , preferably 25.5 to 32% Al ２ O ３ and / or 3 to 13% Li ２ O, preferably 5.5 to 11% Li ２ O, and / or 5-15% Na ２ O, preferably 6.5 to 12% Na ２ O, and / or 2-12% P ２ O ５ + ZrO ２ , preferably 4 to 10% P ２ O ５ + ZrO ２ , and / or 0 to 5% K ２ O, preferably 0.1 to 3% K ２ O, and / or 0-3% ZnO, preferably 0-1% ZnO, and / or 0-3% B ２ O ３ , preferably 0 to 1% B ２ O ３ and / or 0 to 5% RO, preferably 0 to 2% RO, and / or 0 to 3% TiO ２ , preferably 0 to 1% TiO ２ , and / or 0 to 3% Ln ２ O ３ , preferably 0 to 1% Ln ２ O ３ and / or 0 to 1% of a fining agent, preferably 0 to 0.5%, wherein the RO is one or more of MgO, CaO, SrO, and BaO; and the Ln ２ O ３ Is, La ２ O ３ , Gd ２ O ３ , Y ２ O ３ one or more of The crystallized glass according to any one of claims 22 to 24.

34. As a component, by weight percentage, 0 to 6% ZrO ２ , preferably 0-5% ZrO ２ , more preferably 0.1 to 3% ZrO ２ , and / or 0-10% P ２ O ５ , preferably 1 to 8% P ２ O ５ , more preferably 2 to 6% P ２ O ５ containing The crystallized glass according to any one of claims 22 to 24.

35. As a constituent, by weight percentage, 0 to 5% Yb ２ O ３ +Nb ２ O ５ +WO ３ +Bi ２ O ３ +Ta ２ O ５ + TeO ２ +GeO ２ , preferably 0 to 2% Yb ２ O ３ +Nb ２ O ５ +WO ３ +Bi ２ O ３ +Ta ２ O ５ + TeO ２ +GeO ２ , more preferably 0 to 1% Yb ２ O ３ +Nb ２ O ５ +WO ３ +Bi ２ O ３ +Ta ２ O ５ + TeO ２ +GeO ２ Further containing 24. The crystallized glass according to claim 22 or 23.

36. containing a nepheline crystalline phase, and / or a lithium silicate crystalline phase, and / or a lithium phosphate crystalline phase, and / or a petalite crystalline phase, and / or a quartz crystalline phase; The crystallized glass according to any one of claims 22 to 24.

37. The glass-ceramics has a nepheline crystal phase as a main crystalline phase, or the glass-ceramics contains only a nepheline crystal phase. The crystallized glass according to any one of claims 22 to 24.

38. The weight percentage of the neferine crystalline phase in the glass-ceramics is 10 to 80%, preferably 20 to 70%, and more preferably 30 to 60%. The crystallized glass according to any one of claims 22 to 24.

39. the crystal grain size is 80 nm or less, preferably 60 nm or less, more preferably 50 nm or less, and even more preferably 40 nm or less, and / or the Vickers hardness is 650 kgf / mm or more, preferably 680 kgf / mm or more, and more preferably 700 kgf / mm or more; The crystallized glass according to any one of claims 22 to 24.

40. The crystallized glass having a thickness of 1 mm or less has a body falling ball height of 1000 mm or more, preferably 1200 mm or more, and more preferably 1400 mm or more, and / or a haze of 0.15% or less, preferably 0.12% or less, and more preferably 0.10% or less, and / or a light transmittance at a wavelength of 550 nm of 88% or more, preferably 89% or more, more preferably 90% or more, and even more preferably 91% or more, and / or a |B| value for average light of 400 to 800 nm of 1.5 or less, preferably 1.0 or less, and more preferably 0.8 or less. The crystallized glass according to any one of claims 22 to 24.

41. The thickness is 0.2 to 1 mm, preferably 0.3 to 0.9 mm, more preferably 0.5 to 0.8 mm, and even more preferably 0.55 mm, 0.6 mm, 0.68 mm, 0.7 mm, or 0.75 mm.

41. The crystallized glass according to claim 40.

42. As components, by weight percentage, 0 to 4% NiO and / or 0 to 4% Ni ２ O ３ , and / or 0-2% CoO, and / or 0-2% Co ２ O ３ and / or 0 to 7% Fe ２ O ３ and / or 0 to 4% MnO ２ , and / or 0 to 8% Er ２ O ３ , and / or 0 to 8% Nd ２ O ３ and / or 0-4% Cu ２ O, and / or 0-8% Pr ２ O ３ and / or 0-4% CeO ２ Further containing 24. The crystallized glass according to claim 22 or 23.

43. As a constituent, 40 to 60% by weight of SiO ２ , 20-40% Al ２ O ３ , 2 to 15% Li ２ O, 3-20% Na ２ O and 1-15% P ２ O ５ + ZrO ２ containing A matrix glass characterized by:

44. As a component, 0 to 8% by weight of K ２ O, and / or 0 to 6% ZnO, and / or 0 to 6% B ２ O ３ , and / or 0-8% RO, and / or 0-5% TiO ２ , and / or 0 to 5% Ln ２ O ３ and / or 0 to 2% of a fining agent, wherein the RO is one or more of MgO, CaO, SrO, and BaO, and the Ln ２ O ３ Is, La ２ O ３ , Gd ２ O ３ , Y ２ O ３ one or more of 44. The matrix glass of claim 43.

45. When the components are calculated in weight percentage, (Al ２ O ３ +Na ２ O) / P ２ O ５ is 3.0 to 30.0, and preferably (Al ２ O ３ +Na ２ O) / P ２ O ５ is 4.0 to 20.0, and more preferably (Al ２ O ３ +Na ２ O) / P ２ O ５ is 5.0 to 15.0, and more preferably (Al ２ O ３ +Na ２ O) / P ２ O ５ is 6.0 to 10.0, and / or SiO ２ / Al ２ O ３ is 1.2 to 2.8, and preferably SiO ２ / Al ２ O ３ is 1.3 to 2.5, and more preferably, SiO ２ / Al ２ O ３ is 1.5 to 2.2, and more preferably SiO ２ / Al ２ O ３ is 1.6 to 2.0, and / or SiO ２ / (Na ２ O+B ２ O ３ ) is 2.0 to 15.0, and preferably SiO ２ / (Na ２ O+B ２ O ３ ) is 3.0 to 10.0, and more preferably, SiO ２ / (Na ２ O+B ２ O ３ ) is 4.0 to 8.0, and more preferably, SiO ２ / (Na ２ O+B ２ O ３ ) is 5.0 to 7.0, and / or (Na ２ O + Li ２ O) / SiO ２ is 0.1 to 0.8, and preferably (Na ２ O + Li ２ O) / SiO ２ is 0.15 to 0.7, and more preferably (Na ２ O + Li ２ O) / SiO ２ is 0.2 to 0.6, and more preferably (Na ２ O + Li ２ O) / SiO ２ is 0.25 to 0.5, and / or (ZrO ２ +ZnO) / Na ２ O is 2.0 or less, and preferably (ZrO ２ +ZnO) / Na ２ O is 1.5 or less, and more preferably (ZrO ２ +ZnO) / Na ２ O is 0.01 to 1.0, and more preferably (ZrO ２ +ZnO) / Na ２ O is 0.1 to 0.5, and / or (P ２ O ５ +Na ２ O) / Li ２ O is 0.5 to 8.0, and preferably (P ２ O ５ +Na ２ O) / Li ２ O is 0.8 to 5.0, and more preferably, (P ２ O ５ +Na ２ O) / Li ２ O is 1.0 to 3.0, and more preferably, (P ２ O ５ +Na ２ O) / Li ２ O is 1.5 to 2.5, and / or K ２ O / ZrO ２ is 0.1 or more, and preferably, K ２ O / ZrO ２ is 0.2 to 10.0, and more preferably, K ２ O / ZrO ２ is 0.3 to 5.0, and more preferably, K ２ O / ZrO ２ is 0.4 to 1.5, and / or (ZnO + RO + B ２ O ３ + TiO ２ ) / P ２ O ５ is 1.5 or less, and preferably (ZnO + RO + B ２ O ３ + TiO ２ ) / P ２ O ５ is 1.0 or less, and more preferably, (ZnO + RO + B ２ O ３ + TiO ２ ) / P ２ O ５ is 0.5 or less, and more preferably, (ZnO + RO + B ２ O ３ + TiO ２ ) / P ２ O ５ is 0.2 or less, and the RO is one or more of MgO, CaO, SrO, and BaO; 45. The matrix glass according to claim 43 or 44.

46. As a constituent, 43 to 55% by weight of SiO ２ , preferably 46-53% SiO ２ and / or 23 to 36% Al ２ O ３ , preferably 25.5 to 32% Al ２ O ３ and / or 3 to 13% Li ２ O, preferably 5.5 to 11% Li ２ O, and / or 5-15% Na ２ O, preferably 6.5 to 12% Na ２ O, and / or 2-12% P ２ O ５ + ZrO ２ , preferably 4 to 10% P ２ O ５ + ZrO ２ , and / or 0 to 5% K ２ O, preferably 0.1 to 3% K ２ O, and / or 0-3% ZnO, preferably 0-1% ZnO, and / or 0-3% B ２ O ３ , preferably 0 to 1% B ２ O ３ and / or 0 to 5% RO, preferably 0 to 2% RO, and / or 0 to 3% TiO ２ , preferably 0 to 1% TiO ２ , and / or 0 to 3% Ln ２ O ３ , preferably 0 to 1% Ln ２ O ３ and / or 0 to 1% of a fining agent, preferably 0 to 0.5%, wherein the RO is one or more of MgO, CaO, SrO, and BaO; and the Ln ２ O ３ Is, La ２ O ３ , Gd ２ O ３ , Y ２ O ３ one or more of 45. The matrix glass according to claim 43 or 44.

47. As a component, by weight percentage, 0 to 6% ZrO ２ , preferably 0-5% ZrO ２ , more preferably 0.1 to 3% ZrO ２ , and / or 0-10% P ２ O ５ , preferably 1 to 8% P ２ O ５ , more preferably 2 to 6% P ２ O ５ containing 45. The matrix glass according to claim 43 or 44.

48. As a constituent, by weight percentage, 0 to 5% Yb ２ O ３ +Nb ２ O ５ +WO ３ +Bi ２ O ３ +Ta ２ O ５ + TeO ２ +GeO ２ , preferably 0 to 2% Yb ２ O ３ +Nb ２ O ５ +WO ３ +Bi ２ O ３ +Ta ２ O ５ + TeO ２ +GeO ２ , more preferably 0 to 1% Yb ２ O ３ +Nb ２ O ５ +WO ３ +Bi ２ O ３ +Ta ２ O ５ + TeO ２ +GeO ２ Further containing 45. The matrix glass according to claim 43 or 44.

49. As components, by weight percentage, 0 to 4% NiO and / or 0 to 4% Ni ２ O ３ , and / or 0-2% CoO, and / or 0-2% Co ２ O ３ and / or 0 to 7% Fe ２ O ３ and / or 0 to 4% MnO ２ , and / or 0 to 8% Er ２ O ３ , and / or 0 to 8% Nd ２ O ３ and / or 0-4% Cu ２ O, and / or 0-8% Pr ２ O ３ and / or 0-4% CeO ２ Further containing 45. The matrix glass according to claim 43 or 44.

50. The glass-ceramics according to any one of claims 22 to 42 are included. A crystallized glass molded body characterized by:

51. The crystallized glass product according to any one of claims 1 to 21, and / or the crystallized glass according to any one of claims 22 to 42, and / or the matrix glass according to any one of claims 43 to 49, and / or the crystallized glass molded body according to claim 50. A glass cover plate characterized by:

52. The crystallized glass product according to any one of claims 1 to 21, and / or the crystallized glass according to any one of claims 22 to 42, and / or the matrix glass according to any one of claims 43 to 49, and / or the crystallized glass molded body according to claim 50. A glass part characterized by:

53. The crystallized glass product according to any one of claims 1 to 21, and / or the crystallized glass according to any one of claims 22 to 42, and / or the matrix glass according to any one of claims 43 to 49, and / or the crystallized glass molded body according to claim 50, and / or the glass cover plate according to claim 51, and / or the glass part according to claim 52. A display device characterized by:

54. The crystallized glass product according to any one of claims 1 to 21, and / or the crystallized glass according to any one of claims 22 to 42, and / or the matrix glass according to any one of claims 43 to 49, and / or the crystallized glass molded body according to claim 50, and / or the glass cover plate according to claim 51, and / or the glass part according to claim 52. An electronic device characterized by:

55. forming a matrix glass, treating the matrix glass through a crystallization process to form a crystallized glass, and then treating the crystallized glass through a chemical strengthening process to form a crystallized glass product; The method for producing a crystallized glass product according to any one of claims 1 to 21.

56. The crystallization process includes a step of raising the temperature to a predetermined crystallization temperature, and after reaching the crystallization temperature, maintaining the temperature for a certain period of time and then lowering the temperature, wherein the crystallization temperature is 580 to 750°C, preferably 600 to 700°C, and the maintenance time at the crystallization temperature is 0 to 8 hours, preferably 1 to 6 hours.

56. A method for producing a crystallized glass product according to claim 55.

57. the crystallization process includes a step of performing a crystal nucleation process at a first temperature followed by a crystal growth process at a second temperature higher than the temperature of the crystal nucleation process; 56. A method for producing a crystallized glass product according to claim 55.

58. In the crystallization process, the first temperature is 500 to 620°C, the second temperature is 620 to 750°C, the holding time at the first temperature is 0 to 24 hours, preferably 2 to 15 hours, and the holding time at the second temperature is 0 to 10 hours, preferably 0.5 to 6 hours.

58. A method for producing a crystallized glass product according to claim 57.

59. The chemical strengthening process includes a step of immersing the glass-ceramics in a salt bath of Na molten salt at a temperature of 350 to 470°C, preferably 380 to 460°C, for 1 to 36 hours, preferably 2 to 10 hours, and / or a step of immersing the glass-ceramics in a salt bath of K molten salt at a temperature of 360 to 450°C, for 1 to 36 hours, preferably 1 to 10 hours, and / or a step of immersing the glass-ceramics in a mixed salt bath of K molten salt and Na molten salt at a temperature of 360 to 450°C, for 1 to 36 hours, preferably 2 to 24 hours. A method for producing a crystallized glass product according to any one of claims 55 to 58.

60. forming a matrix glass, and then treating the matrix glass through a crystallization process to form a crystallized glass; The method for producing crystallized glass according to any one of claims 22 to 42.

61. The crystallization process includes a step of raising the temperature to a predetermined crystallization temperature, and after reaching the crystallization temperature, maintaining the temperature for a certain period of time and then lowering the temperature, wherein the crystallization temperature is 580 to 750°C, preferably 600 to 700°C, and the maintenance time at the crystallization temperature is 0 to 8 hours, preferably 1 to 6 hours. A method for producing crystallized glass according to claim 60.

62. the crystallization process includes a step of performing a crystal nucleation process at a first temperature followed by a crystal growth process at a second temperature higher than the temperature of the crystal nucleation process; A method for producing crystallized glass according to claim 60.

63. In the crystallization process, the first temperature is 500 to 620°C, the second temperature is 620 to 750°C, the holding time at the first temperature is 0 to 24 hours, preferably 2 to 15 hours, and the holding time at the second temperature is 0 to 10 hours, preferably 0.5 to 6 hours.

63. The method for producing crystallized glass according to claim 62.

64. The method includes a step of polishing or buffing the crystallized glass to produce a crystallized glass molded body, or a step of treating the matrix glass or the crystallized glass at a certain temperature by a hot bending process or a press molding process to produce a crystallized glass molded body. The method for producing a crystallized glass molded body according to claim 50.

65. The method includes a step of subjecting the matrix glass to a primary crystallization heat treatment process including temperature increase, adiabatic nucleation, temperature increase, adiabatic crystallization, and temperature decrease to room temperature to form a pre-crystallized glass, and a step of subjecting the pre-crystallized glass to hot working and forming to obtain a crystallized glass molded body. The method for producing a crystallized glass molded body according to claim 50.

66. 1) a temperature-raising preheating step in which the matrix glass, the pre-ceramic glass or the crystallized glass is placed in a mold, the mold is passed through each heating station in order in a hot bending machine, the mold is retained at each station for a certain time to insulate, and the temperature of the preheating area is set to 400 to 800°C, the pressure is set to 0.01 to 0.05 MPa, and the time is set to 40 to 200 seconds; 2) a pressure molding step in which the mold is preheated and then transferred to a molding station, and a certain pressure is applied to the mold by the hot bending machine, the pressure range is 0.1 to 0.8 MPa, the temperature range of the molding station is 650 to 850 ° C, and the molding time range is 40 to 200 s; 3) A pressure-holding and temperature-lowering step in which the mold is transferred to a temperature-lowering station and the temperature is lowered at each station, the temperature range of the temperature-lowering is 750 to 500 ° C, the pressure is 0.01 to 0.05 MPa, and the time is 40 to 200 s. The method for producing a crystallized glass molded body according to claim 50.

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