Devitrified glass, devitrified glass product, and method for producing the same

Abstract

The present invention provides a devitrified glass and a devitrified glass product having excellent mechanical properties and low haze. The devitrified glass product contains, as components, by weight percentage, 60 to 80% of SiO2, 3 to 15% of Al2O3, 5% or more and less than 10% of Li2O, 4 to 8% of Na2O, 0.5 to 5% of P2O5, and more than 5% and 15% or less of ZrO2, and (SiO2 + Li2O) / (ZrO2 + P2O5) is 4.0 to 15.5. Through reasonable component design, the devitrified glass or devitrified glass product according to the present invention has excellent mechanical properties and low haze, and is applicable to display devices or electronic devices with high optical performance requirements.

Description

Technical Field

[0001] The present invention relates to crystallized glass, and particularly to crystallized glass, crystallized glass products having excellent mechanical properties and low haze, and a method for manufacturing the same.

Background Art

[0002] In recent years, crystallized glass has generally been used in various displays and display devices of many electronic products such as mobile phones, music players, e-book readers, notebooks, tablets, notebook computers, cash dispensers, and other similar devices. The materials constituting the cases of display devices and electronic devices are usually selected to meet the mechanical requirements related to the end uses of the electronic devices. On the other hand, electronic devices or display devices have higher requirements for the optical performance of the crystallized glass used therein. The optical performance refers to the performance exhibited when light rays are absorbed, reflected, and refracted by a substance, such as haze, B value, and refractive index. However, currently commercially available crystallized glass has a problem of high haze, so it is difficult to apply it to display devices or electronic devices with high optical performance requirements.

[0003] Therefore, the development of crystallized glass and crystallized glass products having excellent mechanical properties and low haze and suitable for display devices or electronic devices has become the goal pursued by scientists.

Summary of the Invention

Problems to be Solved by the Invention

[0004] The technical problem to be solved by the present invention is to provide crystallized glass and crystallized glass products having excellent mechanical properties and low haze.

Means for Solving the Problems

[0005] The technical means used by the present invention to solve the technical problems are as follows.

[0006] (1) A crystallized glass product containing, by weight percentage, 60 to 80% of SiO2, 3 to 15% of Al2O3, 5% or more and less than 10% of Li2O, 4 to 8% of Na2O, 0.5 to 5% of P2O5, and more than 5% and 15% or less of ZrO2, and (SiO2 + Li2O) / (ZrO2 + P2O5) is 4.0 to 15.5.

[0007] (2) A crystallized glass product containing, by weight percentage, 60 to 80% of SiO2, 3 to 15% of Al2O3, 5% or more and less than 10% of Li2O, 4 to 8% of Na2O, 0.5 to 5% of P2O5, and more than 5% and 15% or less of ZrO2.

[0008] (3) The crystallized glass product according to (1) or (2), further containing, by weight percentage, 0 to 2% of ZnO and / or 0 to 2% of MgO and / or 0 to 4% of B2O3 and / or 0 to 3% of K2O and / or 0 to 2% of Ln2O3 and / or 0 to 2% of a fining agent, and the Ln2O3 is one or more of La2O3, Gd2O3, Y2O3, Yb2O3.

[0009] (4) A crystallized glass product containing SiO2, Al2O3, Li2O, Na2O, P2O5, ZrO2, and (SiO2 + Li2O) / (ZrO2 + P2O5) is 4.0 to 15.5 by weight percentage, and the haze of the crystallized glass product having a thickness of 1 mm or less is 0.2% or less.

[0010] (5) A crystallized glass product containing SiO2, Al2O3, Li2O, Na2O, ZrO2, and containing a lithium silicate crystal phase, and the lithium silicate crystal phase has a higher weight percentage than other crystal phases.

[0011] (6) A crystallized glass product containing SiO2, Al2O3, Li2O, Na2O, ZrO2, and containing a lithium monosilicate crystal phase.

[0012] As a component, by weight percentage, it contains 60 to 80% of SiO2, and / or 3 to 15% of Al2O3, and / or 5% or more and less than 10% of Li2O, and / or 4 to 8% of Na2O, and / or 0.5 to 5% of P2O5, and / or more than 5% and 15% or less of ZrO2, and / or 0 to 2% of ZnO, and / or 0 to 2% of MgO, and / or 0 to 4% of B2O3, and / or 0 to 3% of K2O, and / or 0 to 2% of Ln2O3, and / or 0 to 2% of a clarifying agent, and the Ln2O3 is one or more of La2O3, Gd2O3, Y2O3, Yb2O3, and the crystallized glass product according to any one of (4) to (6).

[0013] As a component, by weight percentage, it contains 60 to 80% of SiO2, 3 to 15% of Al2O3, 5% or more and less than 10% of Li2O, 4 to 8% of Na2O, 0.5 to 5% of P2O5, more than 5% and 15% or less of ZrO2, 0 to 2% of ZnO, 0 to 2% of MgO, 0 to 4% of B2O3, 0 to 3% of K2O, 0 to 2% of Ln2O3, and 0 to 2% of a clarifying agent, and the Ln2O3 is one or more of La2O3, Gd2O3, Y2O3, Yb2O3, and the crystallized glass product.

[0014] (9) The component is, by weight percentage, 1) SiO2 / ZrO2 is 5.0 to 15.0, preferably, SiO2 / ZrO2 is 6.0 to 13.0, more preferably, SiO2 / ZrO2 is 6.5 to 12.0, and even more preferably, SiO2 / ZrO2 is 7.0 to 11.0, and 2) (SiO2 + Li2O) / (ZrO2 + P2O5) is 5.0 to 13.5, preferably, (SiO2 + Li2O) / (ZrO2 + P2O5) is 6.0 to 11.5, more preferably, (SiO2 + Li2O) / (ZrO2 + P2O5) is 6.0 to 10.5, and 3) (SiO2 + Al2O3 + Na2O) / Li2O is from 7.0 to 18.0, preferably, (SiO2 + Al2O3 + Na2O) / Li2O is from 7.5 to 15.0, more preferably, (SiO2 + Al2O3 + Na2O) / Li2O is from 8.5 to 13.0, still more preferably, (SiO2 + Al2O3 + Na2O) / Li2O is from 8.5 to 11.0, and 4) (ZrO2 + Al2O3) / Li2O is from 0.85 to 5.0, preferably, (ZrO2 + Al2O3) / Li2O is from 0.9 to 4.0, more preferably, (ZrO2 + Al2O3) / Li2O is from 1.0 to 3.5, still more preferably, (ZrO2 + Al2O3) / Li2O is from 1.0 to 3.0, and 5) (Li2O + Na2O) / (SiO2 + ZrO2) is from 0.10 to 0.27, preferably, (Li2O + Na2O) / (SiO2 + ZrO2) is from 0.12 to 0.25, more preferably, (Li2O + Na2O) / (SiO2 + ZrO2) is from 0.14 to 0.25, still more preferably, (Li2O + Na2O) / (SiO2 + ZrO2) is from 0.15 to 0.23, and a devitrified glass product according to any one of (1) to (8) that satisfies one or more of the five conditions.

[0015] (10) As components, by weight percentage, 62 to 78% of SiO2, preferably 64 to 75% of SiO2, and / or 5 to 12% of Al2O3, preferably 5 to 10% of Al2O3, and / or 6% or more and less than 10% of Li2O, and / or 4 to 7.5% of Na2O, preferably 4.5 to 7% of Na2O, and / or 1 to 4.5% of P2O5, preferably 1.5 to 4% of P2O5, and / or 5.5 to 13% of ZrO2, preferably 6 to 12% of ZrO2, and / or 0 to 1.5% of ZnO, preferably 0 to 1% of ZnO, and / or 0 to 1.5% of MgO, preferably 0 to 1% of MgO, and / or 0 to 3% of B2O3, preferably 0 to 2% of B2O3, and / or 0 to 2% of K2O, preferably 0 to 1% of K2O, and / or 0 to 1% of Ln2O3, preferably 0 to 0.5% of Ln2O3, and / or 0 to 1% of fining agent, preferably 0 to 0.5% of fining agent, wherein the Ln2O3 is one or more of La2O3, Gd2O3, Y2O3, Yb2O3, the devitrified glass product according to any one of (1) to (8).

[0016] (11) Containing a lithium silicate crystal phase, the lithium silicate crystal phase has a higher weight percentage than other crystal phases. Preferably, the weight percentage of the lithium silicate crystal phase in the devitrified glass product is 5 to 50%. More preferably, the weight percentage of the lithium silicate crystal phase in the devitrified glass product is 5 to 40%. Even more preferably, the weight percentage of the lithium silicate crystal phase in the devitrified glass product is 10 to 30%. The devitrified glass product according to any one of (1) to (8).

[0017] (12) It contains a lithium metasilicate crystal phase, and the lithium metasilicate crystal phase has a higher weight percentage than other crystal phases. Preferably, the weight percentage occupied by the lithium metasilicate crystal phase in the devitrified glass product is 5 to 50%. More preferably, the weight percentage occupied by the lithium metasilicate crystal phase in the devitrified glass product is 5 to 40%. Even more preferably, the weight percentage occupied by the lithium metasilicate crystal phase in the devitrified glass product is 10 to 30%. The devitrified glass product according to any one of (1) to (8).

[0018] (13) It contains a lithium disilicate crystal phase, and the weight percentage occupied by the lithium disilicate crystal phase in the devitrified glass product is 20% or less. Preferably, the weight percentage occupied by the lithium disilicate crystal phase in the devitrified glass product is 10% or less. More preferably, the weight percentage occupied by the lithium disilicate crystal phase in the devitrified glass product is 5% or less. Even more preferably, the said devitrified glass product does not contain a lithium disilicate crystal phase. The devitrified glass product according to any one of (1) to (8).

[0019] (14) It contains a petalite crystal phase, and the weight percentage occupied by the petalite crystal phase in the devitrified glass product is 15% or less. Preferably, the weight percentage occupied by the petalite crystal phase in the devitrified glass product is 10% or less. More preferably, the weight percentage occupied by the petalite crystal phase in the devitrified glass product is 5% or less. Even more preferably, the said devitrified glass product does not contain a petalite crystal phase. The devitrified glass product according to any one of (1) to (8).

[0020] (15) The falling ball test height is 1400 mm or more. Preferably, it is 1500 mm or more. More preferably, it is 1600 mm or more, and / or the fracture toughness is 1 MPa·m 1 / 2 or more. Preferably, it is 1.1 MPa·m 1 / 2 or more. More preferably, it is 1.2 MPa·m 1 / 2is as above, and / or the four-point bending strength is 600 MPa or more, preferably 650 MPa or more, more preferably 700 MPa or more, and / or the Vickers hardness is 670 kgf / mm 2 is as above, preferably 680 kgf / mm 2 is as above, more preferably 700 kgf / mm 2 is as above, and / or the ion exchange layer depth is 80 μm or more, preferably 90 μm or more, more preferably 100 μm or more, and / or the surface stress is 100 MPa or more, preferably 150 MPa or more, more preferably 200 MPa or more, and / or the crystallinity is 10% or more, preferably 15% or more, more preferably 20% or more, and / or the crystal grain size is 50 nm or less, preferably 40 nm or less, more preferably 30 nm or less, and / or the drop resistance is 1500 mm or more, preferably 1600 mm or more, more preferably 1800 mm or more, a crystallized glass product according to any one of (1) to (8).

[0021] (16) The haze of a crystallized glass product having a thickness of 1 mm or less is 0.2% or less, preferably 0.17% or less, more preferably 0.15% or less, and / or the average light transmittance at a wavelength of 400 to 800 nm is 88.0% or more, preferably 89.0% or more, more preferably 90.0% or more, still more preferably 90.5% or more, and / or the light transmittance at a wavelength of 550 nm is 89.0% or more, preferably 90.0% or more, more preferably 91.0% or more, still more preferably 91.5% or more, and / or the average light |B| value at 400 to 800 nm is 1.0 or less, preferably 0.9 or less, more preferably 0.8 or less, a crystallized glass product according to any one of (1) to (8).

[0022] (17) 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, the crystallized glass product according to (16).

[0023] (18) The crystallized glass product according to any one of (1) to (7), containing a colorant.

[0024] (19) The colorant contains, by weight percentage, 0 to 4% of NiO, and / or 0 to 4% of Ni2O3, and / or 0 to 2% of CoO, and / or 0 to 2% of Co2O3, and / or 0 to 7% of Fe2O3, and / or 0 to 4% of MnO2, and / or 0 to 8% of Er2O3, and / or 0 to 8% of Nd2O3, and / or 0 to 4% of Cu2O, and / or 0 to 8% of Pr2O3, and / or 0 to 4% of CeO2, the crystallized glass product according to (18).

[0025] (20) As components, by weight percentage, it contains 60 to 80% of SiO2, 3 to 15% of Al2O3, 5% or more and less than 10% of Li2O, 4 to 8% of Na2O, 0.5 to 5% of P2O5, and more than 5% and 15% or less of ZrO2, and (SiO2 + Li2O) / (ZrO2 + P2O5) is 4.0 to 15.5, the crystallized glass.

[0026] (21) As components, by weight percentage, it contains 60 to 80% of SiO2, 3 to 15% of Al2O3, 5% or more and less than 10% of Li2O, 4 to 8% of Na2O, 0.5 to 5% of P2O5, and more than 5% and 15% or less of ZrO2, the crystallized glass.

[0027] (22) As components, by weight percentage, it further contains 0 to 2% of ZnO, and / or 0 to 2% of MgO, and / or 0 to 4% of B2O3, and / or 0 to 3% of K2O, and / or 0 to 2% of Ln2O3, and / or 0 to 2% of a fining agent, and the Ln2O3 is one or more of La2O3, Gd2O3, Y2O3, Yb2O3, the crystallized glass according to (20) or (21).

[0028] (23) A devitrified glass containing SiO2, Al2O3, Li2O, Na2O, P2O5, and ZrO2 as components, where (SiO2 + Li2O) / (ZrO2 + P2O5) is 4.0 to 15.5 in weight percentage and the haze of the devitrified glass having a thickness of 1 mm or less is 0.2% or less.

[0029] (24) A devitrified glass containing SiO2, Al2O3, Li2O, Na2O, and ZrO2 and containing a lithium silicate crystal phase, where the lithium silicate crystal phase has a higher weight percentage than other crystal phases.

[0030] (25) A devitrified glass containing SiO2, Al2O3, Li2O, Na2O, and ZrO2 and containing a lithium monosilicate crystal phase.

[0031] (26) A devitrified glass according to any one of (23) to (25), containing, as components, in weight percentage, 60 to 80% of SiO2, and / or 3 to 15% of Al2O3, and / or 5% or more and less than 10% of Li2O, and / or 4 to 8% of Na2O, and / or 0.5 to 5% of P2O5, and / or more than 5% and 15% or less of ZrO2, and / or 0 to 2% of ZnO, and / or 0 to 2% of MgO, and / or 0 to 4% of B2O3, and / or 0 to 3% of K2O, and / or 0 to 2% of Ln2O3, and / or 0 to 2% of a fining agent, where the Ln2O3 is one or more of La2O3, Gd2O3, Y2O3, and Yb2O3.

[0032] (27) A devitrified glass containing, as components, in weight percentage, 60 to 80% of SiO2, 3 to 15% of Al2O3, 5% or more and less than 10% of Li2O, 4 to 8% of Na2O, 0.5 to 5% of P2O5, more than 5% and 15% or less of ZrO2, 0 to 2% of ZnO, 0 to 2% of MgO, 0 to 4% of B2O3, 0 to 3% of K2O, 0 to 2% of Ln2O3, and 0 to 2% of a fining agent, where the Ln2O3 is one or more of La2O3, Gd2O3, Y2O3, and Yb2O3.

[0033] (28) The components are, in weight percentage, 1) The value of SiO2 / ZrO2 is from 5.0 to 15.0, preferably from 6.0 to 13.0, more preferably from 6.5 to 12.0, and even more preferably from 7.0 to 11.0, and 2) The value of (SiO2 + Li2O) / (ZrO2 + P2O5) is from 5.0 to 13.5, preferably from 6.0 to 11.5, more preferably from 6.0 to 10.5, and 3) The value of (SiO2 + Al2O3 + Na2O) / Li2O is from 7.0 to 18.0, preferably from 7.5 to 15.0, more preferably from 8.5 to 13.0, and even more preferably from 8.5 to 11.0, and 4) The value of (ZrO2 + Al2O3) / Li2O is from 0.85 to 5.0, preferably from 0.9 to 4.0, more preferably from 1.0 to 3.5, and even more preferably from 1.0 to 3.0, and 5) The value of (Li2O + Na2O) / (SiO2 + ZrO2) is from 0.10 to 0.27, preferably from 0.12 to 0.25, more preferably from 0.14 to 0.25, and even more preferably from 0.15 to 0.23, and the devitrified glass according to any one of (20) to (27) that satisfies one or more of the five conditions.

[0034] (29) As components, by weight percentage, 62 to 78% of SiO2, preferably 64 to 75% of SiO2, and / or 5 to 12% of Al2O3, preferably 5 to 10% of Al2O3, and / or 6% or more and less than 10% of Li2O, and / or 4 to 7.5% of Na2O, preferably 4.5 to 7% of Na2O, and / or 1 to 4.5% of P2O5, preferably 1.5 to 4% of P2O5, and / or 5.5 to 13% of ZrO2, preferably 6 to 12% of ZrO2, and / or 0 to 1.5% of ZnO, preferably 0 to 1% of ZnO, and / or 0 to 1.5% of MgO, preferably 0 to 1% of MgO, and / or 0 to 3% of B2O3, preferably 0 to 2% of B2O3, and / or 0 to 2% of K2O, preferably 0 to 1% of K2O, and / or 0 to 1% of Ln2O3, preferably 0 to 0.5% of Ln2O3, and / or 0 to 1% of fining agent, preferably 0 to 0.5% of fining agent, wherein the Ln2O3 is one or more of La2O3, Gd2O3, Y2O3, Yb2O3, the devitrified glass according to any one of (20) to (27).

[0035] (30) Containing a lithium silicate crystal phase, the lithium silicate crystal phase has a higher weight percentage than other crystal phases. Preferably, the weight percentage of the lithium silicate crystal phase in the devitrified glass is 5 to 50%. More preferably, the weight percentage of the lithium silicate crystal phase in the devitrified glass is 5 to 40%. Even more preferably, the weight percentage of the lithium silicate crystal phase in the devitrified glass is 10 to 30%. The devitrified glass according to any one of (20) to (27).

[0036] (31) Containing a lithium monosilicate crystal phase, the lithium monosilicate crystal phase has a higher weight percentage than other crystal phases. Preferably, the weight percentage of the lithium monosilicate crystal phase in the devitrified glass is 5 to 50%. More preferably, the weight percentage of the lithium monosilicate crystal phase in the devitrified glass is 5 to 40%. Even more preferably, the weight percentage of the lithium monosilicate crystal phase in the devitrified glass is 10 to 30%. The devitrified glass according to any one of (20) to (27).

[0037] (32) It contains a lithium disilicate crystal phase, and the weight percentage occupied by the lithium disilicate crystal phase in the crystallized glass is 20% or less. Preferably, the weight percentage occupied by the lithium disilicate crystal phase in the crystallized glass is 10% or less. More preferably, the weight percentage occupied by the lithium disilicate crystal phase in the crystallized glass is 5% or less. Even more preferably, the crystallized glass does not contain a lithium disilicate crystal phase. The crystallized glass according to any one of (20) to (27).

[0038] (33) It contains a petalite crystal phase, and the weight percentage occupied by the petalite crystal phase in the crystallized glass is 15% or less. Preferably, the weight percentage occupied by the petalite crystal phase in the crystallized glass is 10% or less. More preferably, the weight percentage occupied by the petalite crystal phase in the crystallized glass is 5% or less. Even more preferably, the crystallized glass does not contain a petalite crystal phase. The crystallized glass according to any one of (20) to (27).

[0039] (34) The degree of crystallization is 10% or more, preferably 15% or more, more preferably 20% or more, and / or the crystal grain size is 50 nm or less, preferably 40 nm or less, more preferably 30 nm or less, and / or the body drop ball height is 1700 mm or more, preferably 1900 mm or more, more preferably 2000 mm or more, and / or the Vickers hardness is 600 kgf / mm 2 or more, preferably 620 kgf / mm 2 or more, more preferably 630 kgf / mm 2 or more, and / or the refractive index is 1.520 to 1.545, and / or the Young's modulus is 80 to 100 GPa. The crystallized glass according to any one of (20) to (27).

[0040] (35) The haze of the devitrified glass having a thickness of 1 mm or less is 0.2% or less, preferably 0.17% or less, more preferably 0.15% or less, and / or the average light transmittance at a wavelength of 400 to 800 nm is 88.0% or more, preferably 89.0% or more, more preferably 90.0% or more, still more preferably 90.5% or more, and / or the light transmittance at a wavelength of 550 nm is 89.0% or more, preferably 90.0% or more, more preferably 91.0% or more, still more preferably 91.5% or more, and / or the average light |B| value at 400 to 800 nm is 1.0 or less, preferably 0.9 or less, more preferably 0.8 or less, the devitrified glass according to any one of (20) to (27).

[0041] (36) The thickness is 0.2 to 1 mm, preferably 0.3 to 0.9 mm, more preferably 0.5 to 0.8 mm, still more preferably 0.55 mm, 0.6 mm, 0.68 mm, 0.7 mm or 0.75 mm, the devitrified glass according to (35).

[0042] (37) The devitrified glass according to any one of (20) to (26), containing a colorant.

[0043] (38) The colorant contains, by weight percentage, 0 to 4% of NiO, and / or 0 to 4% of Ni2O3, and / or 0 to 2% of CoO, and / or 0 to 2% of Co2O3, and / or 0 to 7% of Fe2O3, and / or 0 to 4% of MnO2, and / or 0 to 8% of Er2O3, and / or 0 to 8% of Nd2O3, and / or 0 to 4% of Cu2O, and / or 0 to 8% of Pr2O3, and / or 0 to 4% of CeO2, the devitrified glass according to (37).

[0044] (39) As a component, by weight percentage, it contains 60 to 80% of SiO2, 3 to 15% of Al2O3, 5% or more and less than 10% of Li2O, 4 to 8% of Na2O, 0.5 to 5% of P2O5, and more than 5% and 15% or less of ZrO2, and (SiO2 + Li2O) / (ZrO2 + P2O5) is 4.0 to 15.5, a matrix glass.

[0045] (40) As a component, by weight percentage, it contains 60 to 80% of SiO2, 3 to 15% of Al2O3, 5% or more and less than 10% of Li2O, 4 to 8% of Na2O, 0.5 to 5% of P2O5, and more than 5% and 15% or less of ZrO2, a matrix glass.

[0046] (41) As a component, by weight percentage, it further contains 0 to 2% of ZnO, and / or 0 to 2% of MgO, and / or 0 to 4% of B2O3, and / or 0 to 3% of K2O, and / or 0 to 2% of Ln2O3, and / or 0 to 2% of a clarifying agent, and the Ln2O3 is one or more of La2O3, Gd2O3, Y2O3, Yb2O3, the matrix glass according to (39) or (40).

[0047] (42) As a component, by weight percentage, it contains 60 to 80% of SiO2, 3 to 15% of Al2O3, 5% or more and less than 10% of Li2O, 4 to 8% of Na2O, 0.5 to 5% of P2O5, more than 5% and 15% or less of ZrO2, 0 to 2% of ZnO, 0 to 2% of MgO, 0 to 4% of B2O3, 0 to 3% of K2O, 0 to 2% of Ln2O3, and 0 to 2% of a clarifying agent, and the Ln2O3 is one or more of La2O3, Gd2O3, Y2O3, Yb2O3, a matrix glass.

[0048] (43) The component is, by weight percentage, 1) SiO2 / ZrO2 is 5.0 to 15.0, preferably, SiO2 / ZrO2 is 6.0 to 13.0, more preferably, SiO2 / ZrO2 is 6.5 to 12.0, still more preferably, SiO2 / ZrO2 is 7.0 to 11.0, and 2) (SiO2 + Li2O) / (ZrO2 + P2O5) is 5.0 to 13.5, preferably (SiO2 + Li2O) / (ZrO2 + P2O5) is 6.0 to 11.5, more preferably (SiO2 + Li2O) / (ZrO2 + P2O5) is 6.0 to 10.5, and 3) (SiO2 + Al2O3 + Na2O) / Li2O is 7.0 to 18.0, preferably (SiO2 + Al2O3 + Na2O) / Li2O is 7.5 to 15.0, more preferably (SiO2 + Al2O3 + Na2O) / Li2O is 8.5 to 13.0, still more preferably (SiO2 + Al2O3 + Na2O) / Li2O is 8.5 to 11.0, and 4) (ZrO2 + Al2O3) / Li2O is 0.85 to 5.0, preferably (ZrO2 + Al2O3) / Li2O is 0.9 to 4.0, more preferably (ZrO2 + Al2O3) / Li2O is 1.0 to 3.5, still more preferably (ZrO2 + Al2O3) / Li2O is 1.0 to 3.0, and 5) (Li2O + Na2O) / (SiO2 + ZrO2) is 0.10 to 0.27, preferably (Li2O + Na2O) / (SiO2 + ZrO2) is 0.12 to 0.25, more preferably (Li2O + Na2O) / (SiO2 + ZrO2) is 0.14 to 0.25, still more preferably (Li2O + Na2O) / (SiO2 + ZrO2) is 0.15 to 0.23, and satisfying one or more of the following five conditions, the matrix glass according to any one of (39) to (42).

[0049] (44) As components, by weight percentage, 62 to 78% of SiO2, preferably 64 to 75% of SiO2, and / or 5 to 12% of Al2O3, preferably 5 to 10% of Al2O3, and / or 6% or more and less than 10% of Li2O, and / or 4 to 7.5% of Na2O, preferably 4.5 to 7% of Na2O, and / or 1 to 4.5% of P2O5, preferably 1.5 to 4% of P2O5, and / or 5.5 to 13% of ZrO2, preferably 6 to 12% of ZrO2, and / or 0 to 1.5% of ZnO, preferably 0 to 1% of ZnO, and / or 0 to 1.5% of MgO, preferably 0 to 1% of MgO, and / or 0 to 3% of B2O3, preferably 0 to 2% of B2O3, and / or 0 to 2% of K2O, preferably 0 to 1% of K2O, and / or 0 to 1% of Ln2O3, preferably 0 to 0.5% of Ln2O3, and / or 0 to 1% of fining agent, preferably 0 to 0.5% of fining agent, and the Ln2O3 is one or more of La2O3, Gd2O3, Y2O3, Yb2O3, the matrix glass according to any one of (39) to (42).

[0050] (45) The refractive index is 1.510 to 1.530, the matrix glass according to any one of (39) to (42).

[0051] (46) The matrix glass according to any one of (39) to (41), containing a colorant.

[0052] (47) The colorant contains, by weight percentage, 0 to 4% of NiO, and / or 0 to 4% of Ni2O3, and / or 0 to 2% of CoO, and / or 0 to 2% of Co2O3, and / or 0 to 7% of Fe2O3, and / or 0 to 4% of MnO2, and / or 0 to 8% of Er2O3, and / or 0 to 8% of Nd2O3, and / or 0 to 4% of Cu2O, and / or 0 to 8% of Pr2O3, and / or 0 to 4% of CeO2, the matrix glass according to (46).

[0053] (48) A devitrified glass formed body containing the devitrified glass according to any one of (20) to (38).

[0054] (49) A glass cover plate comprising a devitrified glass product according to any one of (1) to (19), and / or a devitrified glass according to any one of (20) to (38), and / or a matrix glass according to any one of (39) to (47), and / or a devitrified glass molded body according to (48).

[0055] (50) A glass component comprising a devitrified glass product according to any one of (1) to (19), and / or a devitrified glass according to any one of (20) to (38), and / or a matrix glass according to any one of (39) to (47), and / or a devitrified glass molded body according to (48).

[0056] (51) A display device comprising a devitrified glass product according to any one of (1) to (19), and / or a devitrified glass according to any one of (20) to (38), and / or a matrix glass according to any one of (39) to (47), and / or a devitrified glass molded body according to (48), and / or a glass cover plate according to (49), and / or a glass component according to (50).

[0057] (52) An electronic device comprising a devitrified glass product according to any one of (1) to (19), and / or a devitrified glass according to any one of (20) to (38), and / or a matrix glass according to any one of (39) to (47), and / or a devitrified glass molded body according to (48), and / or a glass cover plate according to (49), and / or a glass component according to (50).

[0058] (53) A method for manufacturing a devitrified glass product according to any one of (1) to (19), comprising the steps of forming a matrix glass, treating the matrix glass in a crystallization process to form a devitrified glass, and treating the devitrified glass in a chemical strengthening process to form a devitrified glass product.

[0059] (54) The crystallization process includes the steps of heating up to a predetermined crystallization treatment temperature, maintaining that temperature for a certain period of time after reaching the crystallization treatment temperature, and then cooling down. The crystallization treatment temperature is 550 - 700 °C, preferably 580 - 650 °C. The holding time at the crystallization treatment temperature is 0 - 8 hours, preferably 1 - 6 hours. This is the method for manufacturing the crystallized glass product described in (53).

[0060] (55) The crystallization process includes the step of performing the crystal nucleation process treatment at a first temperature and then performing the crystal growth process treatment at a second temperature higher than the temperature of the crystal nucleation process. This is the method for manufacturing the crystallized glass product described in (53).

[0061] (56) In the crystallization process, the first temperature is 450 - 550 °C, the second temperature is 550 - 700 °C. The holding time at the first temperature is 0 - 24 hours, preferably 2 - 15 hours. The holding time at the second temperature is 0 - 10 hours, preferably 0.5 - 6 hours. This is the method for manufacturing the crystallized glass product described in (55).

[0062] (57) The chemical strengthening process includes the step of immersing the crystallized glass in a molten Na salt bath at a temperature of 350 °C - 470 °C, preferably 380 °C - 460 °C, for 1 - 36 hours, preferably 2 - 24 hours, and / or immersing the crystallized glass in a molten K salt bath at a temperature of 360 °C - 450 °C for 1 - 36 hours, preferably 2 - 24 hours, and / or immersing the crystallized glass in a mixed salt bath of molten K salt and Na salt at a temperature of 360 °C - 450 °C for 1 - 36 hours, preferably 2 - 24 hours. This is the method for manufacturing the crystallized glass product described in any one of (53) - (56).

[0063] (58) After forming the matrix glass, the method for manufacturing the crystallized glass described in any one of (20) - (38) includes the step of treating the matrix glass by a crystallization process to form the crystallized glass.

[0064] (59) The crystallization process includes the steps of heating up to a predetermined crystallization treatment temperature, maintaining that temperature for a certain period of time after reaching the crystallization treatment temperature, and then cooling down. The crystallization treatment temperature is 550 to 700 °C, preferably 580 to 650 °C. The holding time at the crystallization treatment temperature is 0 to 8 hours, preferably 1 to 6 hours. The method for manufacturing the crystallized glass according to (58).

[0065] (60) The crystallization process includes the steps of performing a crystal nucleation process treatment at a first temperature and then performing a crystal growth process treatment at a second temperature higher than the temperature of the crystal nucleation process. The method for manufacturing the crystallized glass according to (59).

[0066] (61) In the crystallization process, the first temperature is 450 to 550 °C, the second temperature is 550 to 700 °C. The holding time at the first temperature is 0 to 24 hours, preferably 2 to 15 hours. The holding time at the second temperature is 0 to 10 hours, preferably 0.5 to 6 hours. The method for manufacturing the crystallized glass according to (60).

[0067] (62) The method for manufacturing the crystallized glass compact according to (48) includes the step of polishing or buffing the crystallized glass to manufacture a crystallized glass compact, or the step of processing the matrix glass or the crystallized glass at a certain temperature by a hot bending process or a press forming process to manufacture a crystallized glass compact.

[0068] (63) The method for manufacturing the crystallized glass compact according to (62) includes the step of performing a single crystallization heat treatment process on the matrix glass, including heating up, heat preservation and nucleation, heating up, heat preservation and crystallization, and cooling down to room temperature, to form a preliminary crystallized glass, and the step of performing hot processing and forming on the preliminary crystallized glass to obtain a crystallized glass compact.

[0069] (64) 1) Place the matrix glass, pre-crystallized glass or crystallized glass in a mold, pass the mold through each heating site in sequence in a hot bending machine, let the mold stay at each site for a certain period of time for heat preservation, set the temperature in the preheating area to 400 - 800 °C, the pressure to 0.01 - 0.05 MPa, and the time to 40 - 200 s for the heating and preheating process; 2) After preheating the mold, transfer it to the forming site, apply a certain pressure to the mold by a hot bending machine, set the pressure range to 0.1 - 0.8 Mpa, the temperature range in the forming site to 600 - 850 °C, and the forming time range to 40 - 200 s for the pressure forming process; 3) Transfer the mold to the cooling site and cool it site by site, set the cooling temperature range to 750 - 500 °C, the pressure to 0.01 - 0.05 Mpa, and the time to 40 - 200 s for the pressure maintaining and cooling process, which includes the manufacturing method of the crystallized glass formed body according to (62).

Advantages of the Invention

[0070] The beneficial effects of the present invention are as follows. Through reasonable component design, the crystallized glass or crystallized glass products according to the present invention have excellent mechanical properties and low haze, and are applicable to display devices or electronic devices with high requirements for optical performance.

Embodiments for Carrying out the Invention

[0071] The crystallized glass and crystallized glass products of the present invention are materials having a crystal phase (sometimes called crystals) and a glass phase, which are different from amorphous solids. The crystal phase of the crystallized glass and crystallized glass products can be identified by the peak angles appearing in the X-ray diffraction pattern of X-ray diffraction analysis, and / or measured by TEMEDX.

[0072] As a result of repeated tests and research, the inventors of the present invention have set the content and the ratio of the content of specific components constituting the crystallized glass and crystallized glass products to specific values to precipitate specific crystal phases, thereby obtaining the crystallized glass or crystallized glass products of the present invention at a relatively low cost.

[0073] The ranges of the respective components (elements) of the matrix glass, the devitrified glass, and the devitrified glass product of the present invention will be described below. In this specification, unless otherwise specified, the content of each component is all expressed as a weight percentage (wt%) with respect to the total amount of the matrix glass, the devitrified glass, or the devitrified glass product in terms of the oxide conversion composition. Here, the "oxide conversion composition" means that when oxides, composite salts, hydroxides, etc. used as raw materials for the composition components of the matrix glass, the devitrified glass, or the devitrified glass product of the present invention decompose into oxides during melting, the total amount of the oxides is taken as 100%. In this specification, when simply referred to as "glass", it refers to the matrix glass before crystallization (i.e., the crystallization process treatment), and after the matrix glass is crystallized (i.e., the crystallization process treatment), it is called devitrified glass, and the devitrified glass product refers to the product obtained after chemically strengthening the devitrified glass.

[0074] Unless otherwise indicated in specific cases, the numerical ranges described in this specification include the upper limit value and the lower limit value, and "above" and "below" include the end point values, as well as all integers and fractions within the range, and are not limited to the specific values described within the limited range. The term "about" as used in this specification means that recipes, parameters, and other numbers and characteristics are not exact and do not need to be exact, and may be approximate and / or larger or smaller as needed, reflecting tolerances, conversion factors, measurement errors, etc. In this specification, "and / or" is inclusive. For example, "A, and / or B" means only A, only B, or both A and B.

[0075] In some embodiments of the present invention, the crystal phase in the devitrified glass or the devitrified glass product contains a lithium silicate crystal phase (one or both of lithium metasilicate and lithium disilicate). In some embodiments, the lithium silicate crystal phase has a higher weight percentage than other crystal phases. In some embodiments, the weight percentage occupied by the lithium silicate crystal phase in the devitrified glass or the devitrified glass product is 5 to 50%, preferably, the weight percentage occupied by the lithium silicate crystal phase in the devitrified glass or the devitrified glass product is 5 to 40%, more preferably, the weight percentage occupied by the lithium silicate crystal phase in the devitrified glass or the devitrified glass product is 10 to 30%. In some embodiments, the weight percentage occupied by the lithium silicate crystal phase in the devitrified glass or the devitrified glass product is 5%, 6%, 7%, 8%, 9%, 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%.

[0076] In some embodiments of the present invention, the crystalline phase in the devitrified glass or the devitrified glass product contains a lithium metasilicate crystalline phase. In some embodiments, the lithium metasilicate crystalline phase has a higher weight percentage than other crystalline phases. In some embodiments, the weight percentage of the lithium metasilicate crystalline phase in the devitrified glass or the devitrified glass product is 5 to 50%, preferably, the weight percentage of the lithium metasilicate crystalline phase in the devitrified glass or the devitrified glass product is 5 to 40%, more preferably, the weight percentage of the lithium metasilicate crystalline phase in the devitrified glass or the devitrified glass product is 10 to 30%. In some embodiments, the weight percentage of the lithium metasilicate crystalline phase in the devitrified glass or the devitrified glass product is 5%, 6%, 7%, 8%, 9%, 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%.

[0077] In some embodiments of the present invention, the crystal phase in the devitrified glass or the devitrified glass product contains a lithium disilicate crystal phase. In some embodiments, the weight percentage occupied by the lithium disilicate crystal phase in the devitrified glass or the devitrified glass product is 20% or less. Preferably, the weight percentage occupied by the lithium disilicate crystal phase in the devitrified glass or the devitrified glass product is 10% or less. More preferably, the weight percentage occupied by the lithium disilicate crystal phase in the devitrified glass or the devitrified glass product is 5% or less. Even more preferably, the devitrified glass or the devitrified glass product does not contain a lithium disilicate crystal phase. In some embodiments, the weight percentage occupied by the lithium disilicate crystal phase in the devitrified glass or the devitrified glass product is 0%, greater than 0%, 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%, 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%, 20%.

[0078] In some embodiments of the present invention, the crystalline phase in the devitrified glass or the devitrified glass product contains a petalite crystalline phase, and the weight percentage occupied by the petalite crystalline phase in the devitrified glass or the devitrified glass product is 15% or less. Preferably, the weight percentage occupied by the petalite crystalline phase in the devitrified glass or the devitrified glass product is 10% or less. More preferably, the weight percentage occupied by the petalite crystalline phase in the devitrified glass or the devitrified glass product is 5% or less. Even more preferably, the devitrified glass or the devitrified glass product does not contain a petalite crystalline phase. In some embodiments, the weight percentage occupied by the petalite crystalline phase in the devitrified glass or the devitrified glass product is 0%, more than 0%, 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%, 10%, 10.5%, 11%, 11.5%, 12%, 12.5%, 13%, 13.5%, 14%, 14.5%, 15%.

[0079] SiO₂ is a basic component of the glass, devitrified glass, and devitrified glass products of the present invention, and is one of the components that form the lithium silicate crystal phase. When the content of SiO₂ is 60% or less, the crystals in the devitrified glass tend to be coarse, which affects the light transmittance of the devitrified glass and devitrified glass products. Therefore, the lower limit of the content of SiO₂ is 60%, preferably 62%, and more preferably 64%. When the content of SiO₂ is 80% or more, the melting temperature of the glass is high, making it difficult to melt the material, and the haze of the devitrified glass and devitrified glass products increases. Therefore, the upper limit of the content of SiO₂ is 80%, preferably 78%, and more preferably 75%. In some embodiments, it may contain about 60%, 60.5%, 61%, 61.5%, 62%, 62.5%, 63%, 63.5%, 64%, 64.5%, 65%, 65.5%, 66%, 66.5%, 67%, 67.5%, 68%, 68.5%, 69%, 69.5%, 70%, 70.5%, 71%, 71.5%, 72%, 72.5%, 73%, 73.5%, 74%, 74.5%, 75%, 75.5%, 76%, 76.5%, 77%, 77.5%, 78%, 78.5%, 79%, 79.5%, 80% of SiO₂.

[0080] Al₂O₃ is a component that forms the glass network structure, is advantageous for chemically strengthening the devitrified glass and improving the drop resistance of the devitrified glass products. When its content is less than 3%, the above effects are not preferable. Therefore, the lower limit of the content of Al₂O₃ is 3%, preferably 5%. On the other hand, when the content of Al₂O₃ exceeds 15%, the fragments obtained by pulverizing the devitrified glass products obtained by chemically strengthening the devitrified glass are small (generally in a particulate state), which is disadvantageous for continuous use. Therefore, the upper limit of the content of Al₂O₃ is 15%, preferably 12%, and more preferably 10%. In some embodiments, it 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% of Al₂O₃.

[0081] Li2O is an essential component for the crystallized glass of the present invention to form a crystal phase and is also an essential component for chemical strengthening. However, when its content is less than 5%, the types of crystals formed change, affecting the strength of the crystallized glass and crystallized glass products. Therefore, the lower limit of the Li2O content is 5%, preferably 6%. On the other hand, when Li2O is contained in excess, the haze of the crystallized glass and crystallized glass products increases, and the raw material cost increases. Therefore, the upper limit of the Li2O content is less than 10%. In some embodiments, it may contain about 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, 9.8%, and less than 10% of Li2O.

[0082] Na2O is advantageous for the formation of the lithium monosilicate crystal phase in the crystallized glass and can improve the stability of the crystallized glass after chemical strengthening. However, in the present invention, the above effects are achieved by containing 4% or more of Na2O, preferably 4.5% or more of Na2O. However, when Na2O is contained in excess, it becomes difficult to form the lithium monosilicate crystal phase in the crystallized glass, affecting the light transmittance of the crystallized glass and crystallized glass products. Therefore, the upper limit of the Na2O content is 8%, preferably 7.5%, more preferably 7%. In some embodiments, it may contain about 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8% of Na2O.

[0083] In some embodiments, by controlling the ratio (SiO2+Al2O3+Na2O) / Li2O of the total content of SiO2, Al2O3 and Na2O, i.e., SiO2+Al2O3+Na2O, to the content of Li2O within the range of 7.0 to 18.0, the crystal grains can be refined, the fracture toughness of the crystallized glass and the crystallized glass product can be improved, and it is advantageous to improve the ion exchange layer depth and surface stress of the crystallized glass product. Therefore, preferably, (SiO2+Al2O3+Na2O) / Li2O is 7.0 to 18.0, more preferably, (SiO2+Al2O3+Na2O) / Li2O is 7.5 to 15.0, still more preferably, (SiO2+Al2O3+Na2O) / Li2O is 8.5 to 13.0, and even more preferably, (SiO2+Al2O3+Na2O) / Li2O is 8.5 to 11.0. In some embodiments, the value of (SiO2+Al2O3+Na2O) / Li2O may be 7.0, 7.3, 7.5, 7.7, 8.0, 8.3, 8.5, 8.7, 9.0, 9.3, 9.5, 9.7, 10.0, 10.3, 10.5, 10.7, 11.0, 11.3, 11.5, 11.7, 12.0, 12.3, 12.5, 12.7, 13.0, 13.3, 13.5, 13.7, 14.0, 14.3, 14.5, 14.7, 15.0, 15.3, 15.5, 15.7, 16.0, 16.3, 16.5, 16.7, 17.0, 17.3, 17.5, 17.7, 18.0.

[0084] ZrO₂ can prevent crystallization during glass forming, refine crystal grains during crystallization heat treatment, and reduce the haze of the crystallized glass and crystallized glass products. In the present invention, the lower limit of the ZrO₂ content is more than 5%, preferably 5.5% or more, and more preferably 6% or more. However, when ZrO₂ is contained in excess, ZrO₂ is difficult to melt in the glass, is likely to form stones, and weakens the heat treatment crystallization ability of the glass. Therefore, the upper limit of the ZrO₂ content is 15%, preferably 13%, and more preferably 12%. In some embodiments, it may contain about more than 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% of ZrO₂.

[0085] In some embodiments, by controlling the ratio of the SiO₂ content to the ZrO₂ content, SiO₂ / ZrO₂, within the range of 5.0 to 15.0, the light transmittance and four-point bending strength of the crystallized glass and crystallized glass products can be improved, the drop ball test height of the crystallized glass products and the body drop ball height of the crystallized glass can be increased, and it is advantageous to prevent the increase in haze and |B| value. Therefore, preferably, SiO₂ / ZrO₂ is 5.0 to 15.0, more preferably, SiO₂ / ZrO₂ is 6.0 to 13.0, still more preferably, SiO₂ / ZrO₂ is 6.5 to 12.0, and even more preferably, SiO₂ / ZrO₂ is 7.0 to 11.0. In some embodiments, the value of SiO₂ / ZrO₂ may be 5.0, 5.3, 5.5, 5.7, 6.0, 6.3, 6.5, 6.7, 7.0, 7.3, 7.5, 7.7, 8.0, 8.3, 8.5, 8.7, 9.0, 9.3, 9.5, 9.7, 10.0, 10.3, 10.5, 10.7, 11.0, 11.3, 11.5, 11.7, 12.0, 12.3, 12.5, 12.7, 13.0, 13.3, 13.5, 13.7, 14.0, 14.3, 14.5, 14.7, 15.0.

[0086] In some embodiments, by controlling the ratio (ZrO2 + Al2O3) / Li2O of the total content of ZrO2 and Al2O3, i.e., ZrO2 + Al2O3, to the content of Li2O within the range of 0.85 to 5.0, the bulk ball-drop height of the crystallized glass can be increased, the ball-drop test height and the ion-exchange layer depth of the crystallized glass product can be increased, and a decrease in the light transmittance and crystallinity of the crystallized glass and the crystallized glass product can be prevented. Therefore, preferably, (ZrO2 + Al2O3) / Li2O is 0.85 to 5.0, more preferably, (ZrO2 + Al2O3) / Li2O is 0.9 to 4.0, still more preferably, (ZrO2 + Al2O3) / Li2O is 1.0 to 3.5, and even more preferably, (ZrO2 + Al2O3) / Li2O is 1.0 to 3.0. In some embodiments, the value of (ZrO2 + Al2O3) / Li2O may be 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, 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, 2.85, 2.9, 2.95, 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.

[0087] In some embodiments, by controlling the ratio (Li2O + Na2O) / (SiO2 + ZrO2) of the total content of Li2O and Na2O, Li2O + Na2O, to the total content of SiO2 and ZrO2, SiO2 + ZrO2, within the range of 0.10 to 0.27, the surface stress and the ion-exchange layer depth of the crystallized glass product can be improved, the four-point bending strength and hardness of the crystallized glass and the crystallized glass product can be improved, and it is advantageous to prevent a decrease in the fracture toughness and the drop resistance of the crystallized glass and the crystallized glass product. Therefore, preferably, (Li2O + Na2O) / (SiO2 + ZrO2) is from 0.10 to 0.27, more preferably, (Li2O + Na2O) / (SiO2 + ZrO2) is from 0.12 to 0.25, still more preferably, (Li2O + Na2O) / (SiO2 + ZrO2) is from 0.14 to 0.25, and even more preferably, (Li2O + Na2O) / (SiO2 + ZrO2) is from 0.15 to 0.23. In some embodiments, the value of (Li2O + Na2O) / (SiO2 + ZrO2) may be 0.10, 0.11, 0.12, 0.13, 0.14, 0.15, 0.16, 0.17, 0.18, 0.19, 0.20, 0.21, 0.22, 0.23, 0.24, 0.25, 0.26, 0.27.

[0088] P2O5 can perform non-uniform crystal nucleation in the glass, promote crystal formation, and improve the light transmittance of the crystallized glass and the crystallized glass product. In the present invention, the lower limit of the content of P2O5 is 0.5%, preferably 1%, and more preferably 1.5%. However, when P2O5 is contained in excess, it is likely to directly crystallize during glass forming, and it is difficult to control the heat treatment process. Therefore, the upper limit of the content of P2O5 is 5%, preferably 4.5%, and more preferably 4%. In some embodiments, it may contain about 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5% of P2O5.

[0089] In some embodiments, by controlling the ratio (SiO2+Li2O) / (ZrO2+P2O5) of the total content of SiO2 and Li2O, i.e., SiO2+Li2O, to the total content of ZrO2 and P2O5, i.e., ZrO2+P2O5, within the range of 4.0 to 15.5, the haze and |B| value of the crystallized glass and the crystallized glass product can be reduced, the drop resistance and hardness of the crystallized glass and the crystallized glass product can be improved, and the crystallinity of the crystallized glass and the crystallized glass product can be optimized. Therefore, preferably, (SiO2+Li2O) / (ZrO2+P2O5) is 4.0 to 15.5, more preferably, (SiO2+Li2O) / (ZrO2+P2O5) is 5.0 to 13.5, still more preferably, (SiO2+Li2O) / (ZrO2+P2O5) is 6.0 to 11.5, and even more preferably, (SiO2+Li2O) / (ZrO2+P2O5) is 6.0 to 10.5. In some embodiments, the value of (SiO2+Li2O) / (ZrO2+P2O5) may be 4.0, 4.3, 4.5, 4.7, 5.0, 5.3, 5.5, 5.7, 6.0, 6.3, 6.5, 6.7, 7.0, 7.3, 7.5, 7.7, 8.0, 8.3, 8.5, 8.7, 9.0, 9.3, 9.5, 9.7, 10.0, 10.3, 10.5, 10.7, 11.0, 11.3, 11.5, 11.7, 12.0, 12.3, 12.5, 12.7, 13.0, 13.3, 13.5, 13.7, 14.0, 14.3, 14.5, 14.7, 15.0, 15.3, 15.5.

[0090] ZnO can lower the melting temperature of the glass, but if its content is too high, the haze of the crystallized glass and the crystallized glass product will increase. Therefore, the content of ZnO is limited to 2% or less, preferably limited to 1.5% or less, and more preferably limited to 1% or less. In some embodiments, it may contain about 0%, more 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%, 2% of ZnO.

[0091] MgO can lower the melting temperature of the glass, but if its content is too high, the haze of the crystallized glass and the crystallized glass product will increase. Therefore, the content of MgO is limited to 2% or less, preferably limited to 1.5% or less, and more preferably limited to 1% or less. In some embodiments, it may contain 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%, 2% of MgO.

[0092] B2O3 can lower the melting temperature of the glass, increase the content of the glass phase in the crystallized glass, and is advantageous for hot bending of the crystallized glass and the crystallized glass product. However, when the glass contains an excessive amount of B2O3, it is likely to phase-separate during the crystallization heat treatment, and the light transmittance of the crystallized glass and the crystallized glass product will decrease. Therefore, the content of B2O3 is 0 to 4%, preferably 0 to 3%, and more preferably 0 to 2%. In some embodiments, it may contain 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%, 2%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3%, 3.1%, 3.2%, 3.3%, 3.4%, 3.5%, 3.6%, 3.7%, 3.8%, 3.9%, 4% of B2O3.

[0093] K2O can lower the viscosity of the glass and promote the growth of crystals during the crystallization heat treatment. However, when K2O is contained in excess, the crystals in the glass grow rapidly, and it becomes easy to reduce the light transmittance of the crystallized glass and the crystallized glass product. Therefore, the content of K2O is 3% or less, preferably 2%, more preferably 1% or less. In some embodiments, it may contain 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%, 2%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3% of K2O.

[0094] Ln2O3 (Ln2O3 is one or more of La2O3, Gd2O3, Y2O3, Yb2O3) can reduce the difficulty of melting the glass. If the content is too high, crystallization becomes difficult when the glass crystallizes, the crystallinity of the crystallized glass and the crystallized glass product decreases, and the body ball drop height of the crystallized glass and the ball drop test height of the crystallized glass product decrease. Therefore, the upper limit of the content of Ln2O3 is 2%, preferably 1%, more preferably 0.5%, and even more preferably, it does not contain Ln2O3. In some embodiments, it may contain 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%, 2% of Ln2O3.

[0095] In some embodiments, the glass, glass-ceramic or glass-ceramic product may further contain 0 to 2% of a fining agent in order to improve the defoaming ability of the glass, glass-ceramic or glass-ceramic product. Such fining agents include, but are not limited to, one or more of Sb2O3, SnO2, SnO, CeO2, F (fluorine), Cl (chlorine) and Br (bromine). Preferably, Sb2O3 is used as the fining agent. When the above fining agent is present alone or in combination, the upper limit of its content is preferably 1%, more preferably 0.5%. In some embodiments, the content of one or more of the above 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%, 2%.

[0096] PbO and As2O3 are toxic substances, and even a small amount of them does not meet the requirements of environmental protection. Therefore, in some embodiments, the present invention preferably does not contain PbO and As2O3.

[0097] In some embodiments of the present invention, by containing a colorant, a matrix glass, glass-ceramic or glass-ceramic product having a color can be manufactured, and the matrix glass, glass-ceramic or glass-ceramic product can exhibit different colors. The colorant contains 0 to 4% of NiO, and / or 0 to 4% of Ni2O3, and / or 0 to 2% of CoO, and / or 0 to 2% of Co2O3, and / or 0 to 7% of Fe2O3, and / or 0 to 4% of MnO2, and / or 0 to 8% of Er2O3, and / or 0 to 8% of Nd2O3, and / or 0 to 4% of Cu2O, and / or 0 to 8% of Pr2O5, and / or 0 to 4% of CeO2. The colorant is in weight percentage, and the content and function are as follows.

[0098] In the brown or green matrix glass, devitrified glass or devitrified glass products manufactured by the present invention, NiO, Ni2O3 or Pr2O5 is used as a colorant. NiO and Ni2O3 are colorants and are used in the manufacture of brown or green matrix glass, devitrified glass or devitrified glass products. The two components may be used alone or in combination, and their respective contents are generally 4% or less, preferably 3% or less. When the content exceeds 4%, the colorant cannot be well dissolved in the matrix glass, devitrified glass or devitrified glass products. The lower limit of each content is 0.1% or more. When it is less than 0.1%, the color of the matrix glass, devitrified glass or devitrified glass products is not noticeable. In some embodiments, it 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% of NiO or Ni2O3. When used in combination, the total amount of NiO and Ni2O3 is generally 4% or less, and the lower limit of the total amount is 0.1% or more. In some embodiments, it 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% of NiO and Ni2O3. Pr2O5 is used as a colorant for green matrix glass, devitrified glass or devitrified glass products. When used alone, generally, the content is 8% or less, preferably 6% or less. The lower limit of its content is 0.4% or more. When it is less than 0.4%, the color of the matrix glass, devitrified glass or devitrified glass products is not noticeable.In some embodiments, it may contain Pr2O5 of 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%, 8.0%.

[0099] In the blue matrix glass, devitrified glass or devitrified glass product manufactured by the present invention, CoO or Co2O3 is used as a colorant, and the two colorant components may be used alone or in combination. The content of each is generally 2% or less, preferably 1.8% or less. When the content exceeds 2%, the colorant cannot be well dissolved in the matrix glass, devitrified glass or devitrified glass product. The lower limit of the content of each is 0.05% or more. When it is less than 0.05%, the color of the matrix glass, devitrified glass or devitrified glass product is not noticeable. In some embodiments, it may contain CoO or Co2O3 of 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%, 2.0%. When used in combination, the total amount of CoO and Co2O3 does not exceed 2%, and the lower limit of the total amount is 0.05% or more. In some embodiments, it may contain CoO and Co2O3 of 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%, 2.0%.

[0100] In the yellow matrix glass, devitrified glass or devitrified glass products manufactured by the present invention, Cu2O or CeO2 is used as a colorant, and the two colorant components are used alone or in combination. The lower limit of the content of each is 0.5% or more. When it is less than 0.5%, the color of the matrix glass, devitrified glass or devitrified glass product is not prominent. When used alone, the content of Cu2O is 4% or less, preferably 3% or less. When the content exceeds 4%, the matrix glass is likely to crystallize. In some embodiments, it 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%, 4.0% of Cu2O. When used alone, the content of CeO2 is generally 4% or less, preferably 3% or less. When the content exceeds 4%, the gloss of the matrix glass, devitrified glass or devitrified glass product is not good. In some embodiments, it 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%, 4.0% of CeO2. In addition, when a small amount of CeO2 is added to the glass, it has a defoaming effect, and CeO2 may be used as a fining agent in the glass. When used as a fining agent, its content is 2% or less, preferably 1% or less, and more preferably 0.5% or less. When the two colorants are used in combination, the total amount is generally 4% or less, and the lower limit of the total amount is 0.5% or more.In some embodiments, it may contain CeO2 and Cu2O of 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%, 4.0%.

[0101] In the black or smoky gray matrix glass, devitrified glass or devitrified glass products produced by the present invention, Fe2O3 is used alone as a colorant, or two of Fe2O3 and CoO are mixed and used as a colorant, or two of Fe2O3 and Co2O3 are mixed and used as a colorant, or three of Fe2O3, CoO and NiO are mixed and used as a colorant, or three of Fe2O3, Co2O3 and NiO are mixed and used as a colorant. To produce black and smoky gray matrix glass, devitrified glass or devitrified glass products, mainly Fe2O3 is used as a colorant for coloring, and the content of Fe2O3 is 7% or less, preferably 5% or less, and the lower limit of its content is 0.2% or more. In some embodiments, it 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%, 7.0% of Fe2O3. Since CoO and Co2O3 absorb visible light, the coloring degree of the matrix glass, devitrified glass or devitrified glass products can be increased. Generally, when mixed with Fe2O3, their respective contents are 0.6% or less, and the lower limit is 0.2% or more. In some embodiments, it may contain about 0.2%, 0.3%, 0.4%, 0.5%, 0.6% of CoO and / or Co2O3. Since NiO absorbs visible light, the coloring degree of the matrix glass, devitrified glass or devitrified glass products can be increased. Generally, when used in combination, its content is 1% or less, and the lower limit of the total amount is 0.2% or more. In some embodiments, it may contain about 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0% of NiO.

[0102] In the purple matrix glass, devitrified glass or devitrified glass product manufactured by the present invention, MnO2 is used as a colorant, and the usage content is generally 4% or less, preferably 3% or less. The lower limit of its content is 0.1% or more. When it is less than 0.1%, the color of the matrix glass, devitrified glass or devitrified glass product is not prominent. In some embodiments, it 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% of MnO2.

[0103] In the pink matrix glass, devitrified glass or devitrified glass product manufactured by the present invention, Er2O3 is used as a colorant, and the usage content is generally 8% or less, preferably 6% or less. Since Er2O3 containing rare earth elements has low coloring efficiency, even if the usage content exceeds 8%, the color of the matrix glass, devitrified glass or devitrified glass product cannot be further deepened. On the contrary, it increases the cost. The lower limit of its content is 0.4% or more. When it is less than 0.4%, the color of the matrix glass, devitrified glass or devitrified glass product is not prominent. In some embodiments, it 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%, 8.0% of Er2O3.

[0104] In the red-violet matrix glass, devitrified glass or devitrified glass product manufactured by the present invention, Nd2O3 is used as a colorant, and the usage content is generally 8% or less, preferably 6% or less. Since Nd2O3 containing rare earth elements has low coloring efficiency, even if the usage content exceeds 8%, the color of the matrix glass, devitrified glass or devitrified glass product cannot be further deepened. On the contrary, the cost is increased. The lower limit of its content is 0.4% or more. When it is less than 0.4%, the color of the matrix glass, devitrified glass or devitrified glass product is not prominent. In some embodiments, it 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%, 8.0% of Nd2O3.

[0105] In the red matrix glass, devitrified glass or devitrified glass product manufactured by the present invention, three mixed colorants of Er2O3, Nd2O3 and MnO2 are used. Er ions in the glass are absorbed at 400-500 nm, Mn ions are mainly absorbed at 500 nm, and Nd ions are mainly strongly absorbed at 580 nm. By mixing the three substances, a red matrix glass, devitrified glass or devitrified glass product can be manufactured. Since Er2O3 and Nd2O3 are rare earth colorings, their coloring ability is relatively weak. The usage amount of Er2O3 is within 6%, the usage amount of Nd2O3 is within 4%, MnO2 has strong coloring, and the usage amount is within the range of 2%. The lower limit of the total amount of the mixed colorants used is 0.9% or more.

[0106] As used herein, "not containing" and "0%" mean that the compound, molecule, element, etc. is not intentionally added as a raw material to the matrix glass, devitrified glass or devitrified glass product of the present invention. However, as raw materials and / or equipment for manufacturing matrix glass, devitrified glass or devitrified glass products, there may be some impurities or components that are not intentionally added and are contained in trace or small amounts in the final matrix glass, devitrified glass or devitrified glass product. Such situations are also within the scope of the claims of the present invention.

[0107] In some embodiments of the present invention, the crystal phase in the devitrified glass and the devitrified glass product contains lithium metasilicate, which provides high strength to the devitrified glass and the devitrified glass product of the present invention, increases the fracture toughness of the devitrified glass and the devitrified glass product, and increases the body ball-drop height of the devitrified glass, the ball-drop test height of the devitrified glass product and the four-point bending strength. The devitrified glass of the present invention has excellent chemical strengthening performance and can also obtain excellent mechanical strength by being treated by a chemical strengthening process. Through reasonable component design, the devitrified glass and the devitrified glass product of the present invention can obtain an appropriate crystal grain size and have high strength. The devitrified glass and the devitrified glass product of the present invention have excellent mechanical properties due to their high degree of crystallinity. The degree of crystallinity mentioned here refers to the perfection of the crystal, that is, the arrangement of the mass points inside the complete crystal of the crystal is regular, the diffraction line is strong, sharp and symmetric, and the half-value width of the diffraction peak is close to the width measured by the instrument. In crystals with a low degree of crystallinity, defects such as dislocations cause the peak shape of the diffraction line to be widely dispersed. The lower the degree of crystallinity, the weaker the diffraction ability, and the wider the diffraction peak becomes until it disappears into the background. In some embodiments, the degree of crystallinity of the devitrified glass product or the devitrified glass is 10% or more, preferably 15% or more, and more preferably 20% or more.

[0108] The crystal grain size and the type of crystal phase in the devitrified glass or devitrified glass product of the present invention affect the haze and light transmittance of the devitrified glass or devitrified glass product. The smaller the crystal grains, the higher the light transmittance, and the smaller the haze, the higher the light transmittance. In some embodiments, the haze of the devitrified glass product or devitrified glass having a thickness of 1 mm or less is 0.2% or less, preferably 0.17% or less, and more preferably 0.15% or less. In some embodiments, the crystal grain size of the devitrified glass product or devitrified glass is 50 nm or less, preferably 40 nm or less, and more preferably 30 nm or less.

[0109] In some embodiments, the content and refractive index of the crystal phase in the devitrified glass or devitrified glass product of the present invention affect the |B| value of the devitrified glass or devitrified glass product. Observe that the devitrified glass or devitrified glass product appears bluish or yellowish within the visible light range, which affects the optical performance of the product and is marked with the |B| value in LAB (chromaticity value of the color of a substance). The devitrified glass or devitrified glass product of the present invention exhibits a low |B| value within the visible light range. In some embodiments, the average light |B| value of the devitrified glass product or devitrified glass having a thickness of 1 mm or less at 400 - 800 nm is 1.0 or less, preferably 0.9 or less, and more preferably 0.8 or less.

[0110] In some embodiments, the devitrified glass or devitrified glass product of the present invention exhibits high transparency within the visible light range (i.e., the devitrified glass or devitrified glass product is transparent). The devitrified glass or devitrified glass product exhibits a high transmittance within the visible light range. In some embodiments, the average light transmittance of the devitrified glass product or devitrified glass having a thickness of 1 mm or less at 400 - 800 nm is preferably 90.5% or more. In some preferred embodiments, the light transmittance of the devitrified glass product or devitrified glass having a thickness of 1 mm or less at 550 nm is preferably 91.5% or more.

[0111] In some embodiments, an antimicrobial component may be added to matrix glass, devitrified glass, or a devitrified glass product. The devitrified glass or devitrified glass product described herein can be used, for example, in applications such as kitchen or food preparation countertops that are likely to be exposed to harmful bacteria. The antibacterial components contained in matrix glass, devitrified glass, or a devitrified glass product include, but are not limited to, Ag, AgO, Cu, CuO, Cu2O, etc. In some embodiments, the content of the above antimicrobial component, alone or in combination, is 2% or less, preferably 1% or less.

[0112] The matrix glass, devitrified glass, and devitrified glass products of the present invention can be produced and manufactured by the following methods.

[0113] Regarding the production of matrix glass, the raw materials are uniformly mixed according to the component ratio, and the uniformly mixed raw materials are placed in a platinum or quartz crucible. Depending on the melting difficulty of the glass composition, they are melted in an electric furnace or a gas furnace within a temperature range of 1250 to 1650 °C for 5 to 24 hours. After stirring to make it uniform, the temperature is lowered to an appropriate temperature and then cast into a mold and slowly cooled to form.

[0114] The matrix glass of the present invention can be formed by known methods.

[0115] For the matrix glass of the present invention, after forming or forming processing, a crystallization process is performed for crystallization treatment, and crystals are uniformly precipitated inside the glass. The crystallization treatment may be performed in one step or in two steps, preferably in two steps. The treatment of the crystal nucleation process is performed at a first temperature, and then the treatment of the crystal growth process is performed at a second temperature higher than the temperature of the crystal nucleation process. The crystallization treatment performed at the first temperature is called the first crystallization treatment, and the crystallization treatment performed at the second temperature is called the second crystallization treatment.

[0116] In order for the devitrified glass to obtain the desired physicochemical properties, the preferred crystallization process is as follows.

[0117] By performing the crystallization process in the above-mentioned one-step manner, the crystal nucleation process and the crystal growth process can be carried out continuously. That is, the temperature is raised to a predetermined crystallization temperature, and after reaching the crystallization temperature, the temperature is maintained for a certain period of time, and then the temperature is lowered. The crystallization temperature is preferably 550 to 700 °C, and more preferably 580 to 650 °C in order to precipitate a desired crystal phase. The holding time at the crystallization temperature is preferably 0 to 8 hours, and more preferably 1 to 6 hours.

[0118] When performing the crystallization process in the above-mentioned two-step manner, the first temperature is preferably 450 to 550 °C, and the second temperature is preferably 550 to 700 °C. The holding time at the first temperature is preferably 0 to 24 hours, and more preferably 2 to 15 hours. The holding time at the second temperature is preferably 0 to 10 hours, and more preferably 0.5 to 6 hours.

[0119] The above-mentioned holding time of 0 hours means that the temperature is lowered or raised again within less than 1 minute after reaching the temperature.

[0120] In some embodiments, the matrix glass or crystallized glass described herein can be manufactured into a molded body by various processes. The molded body includes, but is not limited to, a sheet. The processes include, but are not limited to, slit drawing, the float method, roll pressing, and other sheet forming processes known in the art. Alternatively, the matrix glass or crystallized glass can be formed by the float method or roll pressing method known in the art. The molded body described in the present invention further includes lenses, prisms, and the like.

[0121] Regarding the matrix glass or crystallized glass of the present invention, a glass molded body or a crystallized glass molded body of a sheet can be manufactured by methods such as polishing or buff polishing, but the method for manufacturing the glass molded body or the crystallized glass molded body is not limited to these methods.

[0122] Regarding the matrix glass or devitrified glass of the present invention, glass molded articles or devitrified glass molded articles of various shapes can be manufactured and formed by methods such as a hot bending process or a press molding process at a certain temperature, but it is not limited to these methods.

[0123] In some embodiments, a glass molded article or a devitrified glass molded article may be manufactured by a hot bending process. The hot bending process is a process of placing 2D or 2.5D glass or devitrified glass in a mold and sequentially performing steps such as preheating by heating, pressure molding, and pressure holding and cooling in a hot bending machine to manufacture a 3D curved surface glass molded article or devitrified glass molded article.

[0124] In some embodiments, the devitrified glass molded article has a 2.5D or 3D structure, that is, a non-planar structure. The "non-planar structure" described in this specification means that in a 2.5D or 3D shape, at least a part of the devitrified glass molded article extends outward or extends along an included angle with a plane limited by the original layout arrangement of the 2D matrix glass. The 2.5D or 3D devitrified glass molded article formed of matrix glass may have one or more convex portions or bent portions.

[0125] In some embodiments, according to the characteristics such as the growth of the crystal phase and the phase transition of the crystal phase in the devitrified glass, the manufacturing method of the devitrified glass molded article is a hot bending process method. Specifically, the method includes preliminary crystallization and hot processing and molding. The preliminary crystallization described in the present invention is to form preliminary crystallized glass by treating matrix glass by a controlled crystallization process, and the crystallinity of the preliminary crystallized glass does not reach the crystallinity required for the performance index of the target devitrified glass molded article. The preliminary crystallized glass is treated by a hot processing and molding process to form a devitrified glass molded article.

[0126] In some embodiments, the manufacturing method of the devitrified glass molded article is 1) Perform a single crystallization heat treatment process on the matrix glass, including heating, heat preservation, nucleation, heating, heat preservation, and crystallization, and cooling to room temperature to form a preliminary crystallized glass; 2) Perform hot processing and forming on the preliminary crystallized glass to obtain a crystallized glass formed body.

[0127] The crystallization heat treatment process described in the present invention performs nucleation on the matrix glass at a certain temperature T h and time t h and further crystallizes at a certain temperature T c and time t c The crystallinity of the obtained preliminary crystallized glass does not reach the crystallinity required for the performance index of the target crystallized glass formed body. Using XRD measurement data, the total content of the main crystal phase in the crystallinity of the preliminary crystallized glass is calculated as I c1 The preliminary crystallization of the present invention is a complete process in terms of the process of the process, including a one-step nucleation process, a one-step, two-step, or three-step or more crystallization process, etc., and is a complete process including heating, heat preservation, reheating, reheating... and then cooling to room temperature according to the process. Different from the primary crystallization, secondary crystallization... mentioned in some literatures or patents, the present invention is only the first-stage crystallization, the second-stage crystallization... in the actual complete crystallization process, and the intermediate process is continuous, and there is no process of reheating and crystallizing after cooling to room temperature.

[0128] The hot processing and forming described in the present invention refers to performing a forming process on the preliminary crystallized glass by a hot processing process under conditions such as a certain temperature, time, pressure, etc. The hot processing and forming includes one or more hot processing processes, and the hot processing process includes, but is not limited to, performing press forming, bending forming, or drawing forming on the preliminary crystallized glass under conditions such as a certain temperature, time, pressure, etc. In the hot processing and forming process, it may not be possible to complete a formed body with a complex shape in a single hot processing, and it may be realized by performing multiple hot processing processes more than twice.

[0129] In some embodiments, the method for manufacturing a devitrified glass formed body is a hot bending process method. Specifically, in some embodiments, the method for manufacturing a devitrified glass formed body includes the following steps 1) to 3).

[0130] 1) In the heating preheating step, matrix glass, preliminary devitrified glass or devitrified glass is placed in a mold, and the mold is sequentially passed through each heating site in a hot bending machine, and the mold is retained at each site for a certain period of time for heat preservation. The temperature of the preheating region 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 s. In some embodiments, for a hot bending machine with five preheating sites, generally, it is stably set to about 500 °C during the initial heating, and the temperature is gradually increased at subsequent sites. The temperature gradient between two adjacent sites gradually decreases from low to high, and the temperature difference between the last preheating site and the first site for press forming only needs to be within the range of 20 °C.

[0131] 2) In the pressure forming step, after preheating the mold, it is transferred to the forming site, and a certain pressure is applied to the mold by a hot bending machine. The pressure range (the magnitude of the pressure is determined according to factors such as the thickness and radian of the glass) is set to 0.1 to 0.8 Mpa, the temperature range of the forming site is set to 600 to 850 °C, and the forming time range is set to 40 to 200 s.

[0132] 3) In the pressure holding and cooling step, the mold is transferred to the cooling site and cooled site by site. The cooling temperature range is controlled to 750 to 500 °C, the pressure is controlled to 0.01 to 0.05 Mpa, and the time is controlled to 40 to 200 s.

[0133] When forming a devitrified glass formed body by a hot bending process, for example, it is necessary to control the appearance quality of general high-aluminum glass, and it is also necessary to control the influence of crystal growth in the hot bending process on the performance of the devitrified glass. For example, for 3D curved surface devitrified glass used in the case of a display device or an electronic device, it is necessary to closely pay attention to the light transmittance, haze, |B| value and its uniformity after hot bending.

[0134] The matrix glass, devitrified glass, and devitrified glass products described in the present invention may have any reasonable and useful thickness.

[0135] Regarding the devitrified glass of the present invention, in addition to precipitating crystals to improve mechanical properties, by forming a compressive stress layer, more excellent mechanical properties can be obtained, and devitrified glass products can be manufactured.

[0136] In some embodiments, the matrix glass or devitrified glass may be processed into a sheet and / or shaped (e.g., perforated, hot bent, etc.), and after being shaped, it may be buffed and / or polished, and further chemically strengthened by a chemical strengthening process.

[0137] The chemical strengthening described in the present invention is an ion exchange method. During the ion exchange process, small metal ions in the matrix glass or devitrified glass are substituted or "exchanged" by large metal ions having the same valence that are close to the matrix glass or devitrified glass. Substituting small ions with large ions constructs compressive stress in the matrix glass or devitrified glass and forms a compressive stress layer.

[0138] In some embodiments, the metal ions are monovalent alkali metal ions (e.g., Na + , K + , Rb + , Cs + , etc.), and the ion exchange is performed by immersing the matrix glass or devitrified glass in a salt bath of at least one molten salt containing large metal ions for substituting small metal ions in the matrix glass. Alternatively, other monovalent metal ions such as Ag + , Tl + , Cu + , etc. may also be used for the exchange of monovalent ions. One or more ion exchange processes for chemically strengthening the matrix glass or devitrified glass include, but are not limited to, immersing in a single salt bath or in a plurality of salt baths having the same or different compositions, and having a washing and / or annealing step during the immersion.

[0139] In some embodiments, the matrix glass or the crystallized glass can be ion-exchanged by immersing it in a salt bath of molten Na salt (e.g., NaNO3) at a temperature of about 350°C to 470°C for about 1 to 36 hours. Preferably, the temperature range is 380°C to 460°C, and preferably, the time range is 2 to 24 hours. In such embodiments, Na ions replace some of the Li ions in the matrix glass or the crystallized glass to form a surface compression layer, showing high mechanical properties. In some embodiments, the matrix glass or the crystallized glass can be ion-exchanged by immersing it in a salt bath of molten K salt (e.g., KNO3) at a temperature of about 360°C to 450°C for 1 to 36 hours. Preferably, the time range is 2 to 24 hours. In some embodiments, the matrix glass or the crystallized glass can be ion-exchanged by immersing it in a mixed salt bath of molten K salt and Na salt at a temperature of about 360°C to 450°C for 1 to 36 hours. Preferably, the time range is 2 hours to 24 hours.

[0140] Each performance index of the crystallized glass and / or the crystallized glass product and / or the matrix glass of the present invention is measured by the following method.

[0141] [Haze] Measured using a haze meter Minolta CM3600A, manufactured with a sample of 1 mm or less, and measured based on GB2410-80.

[0142] [Crystal grain size] Measured using a SEM scanning electron microscope. The crystallized glass was surface-treated in HF acid, and then metal was sprayed on the surface of the crystallized glass. The surface was scanned with a SEM scanning electron microscope to determine the size of the crystal grains.

[0143] [Light transmittance] All the light transmittances described in this specification are external transmittances and may be abbreviated as transmittance.

[0144] The sample was processed to a size of 1 mm or less, and parallel buff polishing was performed on the opposing surfaces of the sample. The average light transmittance at 400 - 800 nm was measured using a Hitachi U-41000 spectrophotometer.

[0145] The sample was processed to a size of 1 mm or less, and parallel buff polishing was performed on the opposing surfaces of the sample. The light transmittance at 550 nm was measured using a Hitachi U-41000 spectrophotometer.

[0146] [Degree of crystallinity] The degree of crystallinity was obtained by comparing the XRD diffraction peaks with the database patterns and calculating the ratio of the diffraction intensity of the crystal phase to the total pattern intensity. Internal calibration was performed using pure quartz crystals.

[0147] [Ion exchange layer depth] The ion exchange layer depth was measured using a glass surface stress meter SLP-2000.

[0148] As measurement conditions, the refractive index of the sample was set to 1.56, and the photoelastic constant was calculated as 29 [(nm / cm) / Mpa].

[0149] [Surface stress] The surface stress was measured using a glass surface stress meter SLP-2000.

[0150] As measurement conditions, the refractive index of the sample was set to 1.52, and the photoelastic constant was calculated as 29 [(nm / cm) / Mpa].

[0151] [Drop resistance] The drop resistance was measured using the directivity drop tester WH-2101. Glass products of the same standard were loaded onto the 2D crystallized glass products (the weight per sheet was 20 g and two sheets were loaded). Sandpaper with a mesh size of 60 to 80 was laid on the pedestal, and the products were freely dropped from a predetermined height, directly hitting the sandpaper. The height of the impact that the sample could withstand without breaking was defined as the drop resistance. Specifically, the test was carried out from a height of 600 mm. If it did not break, the height was changed in the order of 700 mm, 800 mm, 900 mm, 1000 mm or more. For the examples with "drop resistance", the crystallized glass products were used as the test objects. In the examples, the test data recorded as 2000 mm indicated that the crystallized glass products with the load could withstand the impact without breaking even when dropped from a height of 2000 mm. The maximum test height of the drop tester WH-2101 was 2000 mm.

[0152] [Falling ball test height] A 145 mm × 67 mm × 0.7 mm crystallized glass product sample was placed on a glass placement jig, and a 132 g steel ball was dropped from a predetermined height. The maximum falling ball test height of the impact that the sample could withstand without breaking was defined as the falling ball test height. Specifically, the test was carried out from a falling ball test height of 800 mm. If it did not break, the height was changed in the order of 850 mm, 900 mm, 950 mm, 1000 mm or more. For the examples with "falling ball test height", the crystallized glass products were used as the test objects. In the examples, the test data recorded as 1000 mm indicated that the crystallized glass products could withstand the impact without breaking even when the steel ball was dropped from a height of 1000 mm. In the present invention, the falling ball test height may be abbreviated as the falling ball height.

[0153] [Body falling ball height] A 145 mm × 67 mm × 0.7 mm crystallized glass sample was placed on a glass mounting jig, and a 32 g steel ball was dropped from a predetermined height. The maximum drop ball test height of the impact that the sample could withstand without breaking was defined as the main body drop ball height. Specifically, the test was carried out starting from a drop ball test height of 500 mm. If it did not break, the height was changed in the order of 550 mm, 600 mm, 650 mm, 700 mm, and above. For the examples with the "main body drop ball height", the crystallized glass was the test object, that is, the drop ball test height of the crystallized glass. In the examples, the test data recorded as 1000 mm indicated that the crystallized glass withstood the impact without breaking even when the steel ball was dropped from a height of 1000 mm.

[0154] [Fracture toughness] Using the method of directly measuring the size of the indentation-induced crack, with the sample size of 2 mm × 4 mm × 20 mm, after chamfering, polishing, and buffing to complete the preparation of the sample, a 49 N force was applied to the sample with a Vickers hardness indenter and maintained for 30 s to make an indentation, and then its fracture strength was measured by the three-point bending method.

[0155] [Four-point bending strength] Using a microcomputer-controlled electronic universal testing machine CMT6502, with the sample thickness of 1 mm or less, the measurement was carried out according to the standard of 'ASTM C 158 - 2002'. In the present invention, the four-point bending strength may be abbreviated as the bending strength.

[0156] [Vickers hardness] The value obtained by dividing the load (N) when a diamond square pyramid indenter with a face angle of 136° was pressed into the measurement surface to form a pyramid-shaped indentation by the surface area (mm 2 ) was used to represent it. The test load was 100 (N) and the holding time was 15 (seconds). In the present invention, the Vickers hardness may be abbreviated as the hardness.

[0157] [|B| value] B value detection was performed using a Minolta CM-700d. The standard of the sample was set to a thickness of 1 mm or less. Zero position calibration and white board calibration of the device were performed using the calibrated long tube and short tube, respectively, which were to be set. After calibration, an air test was performed using the long tube to determine the stability calibration reliability of the device (B ≤ 0.05). After passing the device calibration, the product was placed in the zero position long tube for measurement.

[0158] The |B| value is the absolute value of the B value.

[0159] [Young's modulus] Young's modulus (E) was calculated by measuring the longitudinal wave velocity and transverse wave velocity thereof by ultrasonic waves according to the following formula.

[0160]

Equation

[0161] [Refractive index] The refractive index (n d ) was measured according to the method specified in 'GB / T 7962.1-2010'.

[0162] The crystallized glass product of the present invention has the following performance.

[0163] 1) In some embodiments, the four-point bending strength of the crystallized glass product is 600 MPa or more, preferably 650 MPa or more, more preferably 700 MPa or more.

[0164] 2) In some embodiments, the ion-exchange layer depth of the crystallized glass product is 80 μm or more, preferably 90 μm or more, and more preferably 100 μm or more.

[0165] 3) In some embodiments, the surface stress of the crystallized glass product is 100 MPa or more, preferably 150 MPa or more, and more preferably 200 MPa or more.

[0166] 4) In some embodiments, the ball-drop test height of the crystallized glass product is 1400 mm or more, preferably 1500 mm or more, and more preferably 1600 mm or more.

[0167] 5) In some embodiments, the fracture toughness of the crystallized glass product is 1 MPa·m 1 / 2 or more, preferably 1.1 MPa·m 1 / 2 or more, and more preferably 1.2 MPa·m 1 / 2 or more.

[0168] 6) In some embodiments, the Vickers hardness (H v ) of the crystallized glass product is 670 kgf / mm 2 or more, preferably 680 kgf / mm 2 or more, and more preferably 700 kgf / mm 2 or more.

[0169] 7) In some embodiments, the crystallinity of the crystallized glass product is 10% or more, preferably 15% or more, and more preferably 20% or more.

[0170] 8) In some embodiments, the crystal grain size of the crystallized glass product is 50 nm or less, preferably 40 nm or less, and more preferably 30 nm or less.

[0171] 9) In some embodiments, the drop resistance of the devitrified glass product is 1500 mm or more, preferably 1600 mm or more, more preferably 1800 mm or more.

[0172] 10) In some embodiments, the haze of the devitrified glass product having a thickness of 1 mm or less is 0.2% or less, preferably 0.17% or less, more preferably 0.15% or less. The thickness is preferably 0.2 to 1 mm, more preferably 0.3 to 0.9 mm, still 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.

[0173] 11) In some embodiments, the average light transmittance of the devitrified glass product having a thickness of 1 mm or less at a wavelength of 400 to 800 nm is 88.0% or more, preferably 89.0% or more, more preferably 90.0% or more, and still more preferably 90.5% or more. The thickness is preferably 0.2 to 1 mm, more preferably 0.3 to 0.9 mm, still 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.

[0174] 12) In some embodiments, the light transmittance of the devitrified glass product having a thickness of 1 mm or less at a wavelength of 550 nm is 89.0% or more, preferably 90.0% or more, more preferably 91.0% or more, and still more preferably 91.5% or more. The thickness is preferably 0.2 to 1 mm, more preferably 0.3 to 0.9 mm, still 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.

[0175] 13) In some embodiments, the average light |B| value of the devitrified glass product having a thickness of 1 mm or less at 400 to 800 nm is 1.0 or less, preferably 0.9 or less, more preferably 0.8 or less. The thickness is preferably 0.2 to 1 mm, more preferably 0.3 to 0.9 mm, still 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.

[0176] The devitrified glass of the present invention has the following performance.

[0177] 1) In some embodiments, the crystallinity of the devitrified glass is 10% or more, preferably 15% or more, more preferably 20% or more.

[0178] 2) In some embodiments, the crystal grain size of the devitrified glass is 50 nm or less, preferably 40 nm or less, more preferably 30 nm or less.

[0179] 3) In some embodiments, the haze of the devitrified glass having a thickness of 1 mm or less is 0.2% or less, preferably 0.17% or less, more preferably 0.15% or less. The thickness is preferably 0.2 to 1 mm, more preferably 0.3 to 0.9 mm, still 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.

[0180] 4) In some embodiments, the average light transmittance of the devitrified glass having a thickness of 1 mm or less at a wavelength of 400 to 800 nm is 87.0% or more, preferably 88.0% or more, more preferably 88.5% or more. The thickness is preferably 0.2 to 1 mm, more preferably 0.3 to 0.9 mm, still 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.

[0181] 5) In some embodiments, the light transmittance of the devitrified glass having a thickness of 1 mm or less at a wavelength of 550 nm is 89.0% or more, preferably 90.0% or more, more preferably 90.5% or more. The thickness is preferably 0.2 to 1 mm, more preferably 0.3 to 0.9 mm, still 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.

[0182] 6) In some embodiments, the body ball drop height of the devitrified glass is 1700 mm or more, preferably 1900 mm or more, more preferably 2000 mm or more.

[0183] 7) In some embodiments, the average light |B| value of the devitrified glass having a thickness of 1 mm or less in the range of 400 to 800 nm is 1.0 or less, preferably 0.9 or less, more preferably 0.8 or less. The thickness is preferably 0.2 to 1 mm, more preferably 0.3 to 0.9 mm, still 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.

[0184] 8) In some embodiments, the Vickers hardness (H v ) of the devitrified glass is 600 kgf / mm 2 or more, preferably 620 kgf / mm 2 or more, more preferably 630 kgf / mm 2 or more.

[0185] 9) In some embodiments, the refractive index (n d ) of the devitrified glass is 1.520 to 1.545.

[0186] 10) In some embodiments, the Young's modulus (E) of the devitrified glass product is 80 to 100 GPa.

[0187] The matrix glass of the present invention has the following properties.

[0188] 1) In some embodiments, the refractive index (n d ) of the matrix glass is 1.510 to 1.530.

[0189] Since the devitrified glass, devitrified glass product, matrix glass, glass molded body, and devitrified glass molded body of the present invention have the above excellent properties, they can be widely manufactured as 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. They can be used in the manufacture of protective glass for mobile phones, smartphones, tablet computers, notebook computers, PDAs, TVs, computers, MTA devices, or industrial displays, or in the manufacture of touch panels, protective windows, automobile windows, train windows, aircraft windows, touch panel protective glass, or in the manufacture of hard disk substrates or solar cell substrates, or in the manufacture of white goods such as refrigerator components or cooking utensils.

[0190] (Example) In order to more clearly interpret 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 numerical values (for example, quantity, temperature, etc.) in the examples of the present invention, it is necessary to consider that there are some errors and deviations. The composition itself is expressed in weight% based on oxides and normalized to 100%.

[0191] <Examples of Matrix Glass> In this example, matrix glasses having the compositions shown in Tables 1 and 2 were obtained by the method for manufacturing the above matrix glass. Also, the properties of each matrix glass were measured by the measurement method described in the present invention, and the measurement results are shown in Tables 1 and 2.

[0192]

Table 1

[0193]

Table 2

[0194] <Examples of the Crystallized Glass> In this example, crystallized glass having the compositions shown in Tables 3 and 4 was obtained by the above-described method for producing crystallized glass. Further, the properties of each crystallized glass were measured by the measurement method described in the present invention, and the measurement results are shown in Tables 3 and 4. For the haze in the following examples, the average light transmittance at wavelengths of 400 to 800 nm, the light transmittance at a wavelength of 550 nm, and the average light |B| in the case of the value at 400 to 800 nm, the thickness of the measurement sample is 0.7 mm.

[0195]

Table 3

[0196]

Table 4

[0197] <Examples of the Crystallized Glass Products> In this example, crystallized glass products having the compositions shown in Tables 5 and 6 were obtained by the above-described method for producing crystallized glass products. Further, the properties of each crystallized glass product were measured by the measurement method described in the present invention, and the measurement results are shown in Tables 5 and 6. For the haze in the following examples, the average light transmittance at wavelengths of 400 to 800 nm, the light transmittance at a wavelength of 550 nm, and the average light |B| in the case of the value at 400 to 800 nm, the thickness of the measurement sample is 0.7 mm.

[0198]

Table 5

[0199]

Table 6

Claims

1. As components, by weight percentage, 60 to 80% of SiO ２ , 3 to 15% of Al ２ O ３ , 5% or more and less than 10% of Li ２ O, 4 to 8% of Na ２ O, 0.5 to 5% of P ２ O ５ , and more than 5% and 15% or less of ZrO ２ are contained, and (SiO ２ +Li ２ O) / (ZrO ２ +P ２ O ５ ) is 4.0 to 15.

5. A crystallized glass product, characterized in that...

2. As components, ZnO at 0 to 2% by weight, and / or MgO at 0 to 2% by weight, and / or B ２ O ３ , and / or K at 0 to 3% ２ O, and / or Ln at 0 to 2% ２ O ３ , and further contains a clarifying agent at 0 to 2%, wherein the Ln ２ O ３ is one or more of La ２ O ３ , Gd ２ O ３ , Y ２ O ３ , Yb ２ O ３ ​ The crystallized glass product according to Claim 1, characterized in that...

3. As components, SiO ２ , Al ２ O ３ , Li ２ O, Na ２ O, P ２ O ５ , ZrO ２ are contained, and in terms of weight percentage, (SiO ２ + Li ２ O) / (ZrO ２ + P ２ O ５ ) is 4.0 to 15.5, and the haze of the crystallized glass product having a thickness of 1 mm or less is 0.2% or less. A crystallized glass product, characterized in that...

4. As components, in weight percentage, 60 to 80% of SiO ２ and / or 3 to 15% of Al ２ O ３ and / or 5% or more and less than 10% of Li ２ O, and / or 4 to 8% of Na ２ O, and / or 0.5 to 5% of P ２ O ５ and / or more than 5% and 15% or less of ZrO ２ and / or 0 to 2% of ZnO, and / or 0 to 2% of MgO, and / or 0 to 4% of B ２ O ３ and / or 0 to 3% of K ２ O, and / or 0 to 2% of Ln ２ O ３ and / or contains 0 to 2% of a clarifying agent, wherein the Ln ２ O ３ is one or more of La ２ O ３ , Gd ２ O ３ , Y ２ O ３ , Yb ２ O ３ and the like, The crystallized glass product according to Claim 3, characterized in that...

5. The components are in weight percentages, 1) SiO ２ / ZrO ２ is 5.0 to 15.0, preferably, SiO ２ / ZrO ２ is 6.0 to 13.0, more preferably, SiO ２ / ZrO ２ is 6.5 to 12.0, even more preferably, SiO ２ / ZrO ２ is 7.0 to 11.0, and 2) (SiO ２ + Li ２ O) / (ZrO ２ + P ２ O ５ ) is 5.0 to 13.5, preferably, (SiO ２ + Li ２ O) / (ZrO ２ + P ２ O ５ ) is 6.0 to 11.5, more preferably, (SiO ２ + Li ２ O) / (ZrO ２ + P ２ O ５ ) is 6.0 to 10.5, and 3) (SiO ２ + Al ２ O ３ + Na ２ O) / Li ２ O is 7.0 to 18.0, preferably, (SiO ２ + Al ２ O ３ + Na ２ O) / Li ２ O is 7.5 to 15.0, more preferably, (SiO ２ + Al ２ O ３ + Na ２ O) / Li ２ O is 8.5 to 13.0, still more preferably, (SiO ２ + Al ２ O ３ + Na ２ O) / Li ２ O is 8.5 to 11.0, and 4) (ZrO ２ + Al ２ O ３ ) / Li ２ O is 0.85 to 5.0, preferably, (ZrO ２ + Al ２ O ３ ) / Li ２ O is 0.9 to 4.0, more preferably, (ZrO ２ + Al ２ O ３ ) / Li ２ O is 1.0 to 3.5, still more preferably, (ZrO ２ + Al ２ O ３ ) / Li ２ O is 1.0 to 3.0, and 5) (Li ２ O + Na ２ O) / (SiO ２ + ZrO ２ ) is 0.10 to 0.27, preferably, (Li ２ O + Na ２ O) / (SiO ２ + ZrO ２ ) is 0.12 to 0.25, more preferably, (Li ２ O + Na ２ O) / (SiO ２ + ZrO ２ ) is 0.14 to 0.25, still more preferably, (Li ２ O + Na ２ O) / (SiO ２ + ZrO ２ ) is 0.15 to 0.23, and satisfies one or more of the five conditions The crystallized glass product according to any one of Claims 1 to 4, characterized in that...

6. As components, by weight percentage, 62 to 78% of SiO ２ , preferably 64 to 75% of SiO ２ , and / or 5 to 12% of Al ２ O ３ , preferably 5 to 10% of Al ２ O ３ , and / or 6% or more and less than 10% of Li ２ O, and / or 4 to 7.5% of Na ２ O, preferably 4.5 to 7% of Na ２ O, and / or 1 to 4.5% of P ２ O ５ , preferably 1.5 to 4% of P ２ O ５ , and / or 5.5 to 13% of ZrO ２ , preferably 6 to 12% of ZrO ２ , and / or 0 to 1.5% of ZnO, preferably 0 to 1% of ZnO, and / or 0 to 1.5% of MgO, preferably 0 to 1% of MgO, and / or 0 to 3% of B ２ O ３ , preferably 0 to 2% of B ２ O ３ , and / or 0 to 2% of K ２ O, preferably 0 to 1% of K ２ , and / or 0 to 1% of Ln ２ O ３ , preferably 0 to 0.5% of Ln ２ O ３ , and / or 0 to 1% of a clarifying agent, preferably 0 to 0.5% of a clarifying agent, and the Ln ２ O ３ is one or more of La ２ O ３ , Gd ２ O ３ , Y ２ O ３ , Yb ２ O ３ among them, The crystallized glass product according to any one of Claims 1 to 4, characterized in that...

7. containing a lithium silicate crystal phase, the lithium silicate crystal phase having a higher weight percentage than other crystal phases, preferably, the weight percentage of the lithium silicate crystal phase in the crystallized glass product is 5 - 50%, more preferably, the weight percentage of the lithium silicate crystal phase in the crystallized glass product is 5 - 40%, still more preferably, the weight percentage of the lithium silicate crystal phase in the crystallized glass product is 10 - 30%, The crystallized glass product according to any one of Claims 1 to 4, characterized in that...

8. containing a lithium monosilicate crystal phase, the lithium monosilicate crystal phase having a higher weight percentage than other crystal phases, preferably, the weight percentage of the lithium monosilicate crystal phase in the crystallized glass product is 5 - 50%, more preferably, the weight percentage of the lithium monosilicate crystal phase in the crystallized glass product is 5 - 40%, still more preferably, the weight percentage of the lithium monosilicate crystal phase in the crystallized glass product is 10 - 30%, The crystallized glass product according to any one of Claims 1 to 4, characterized in that...

9. containing a lithium disilicate crystal phase, the weight percentage of the lithium disilicate crystal phase in the crystallized glass product being 20% or less, preferably, the weight percentage of the lithium disilicate crystal phase in the crystallized glass product is 10% or less, more preferably, the weight percentage of the lithium disilicate crystal phase in the crystallized glass product is 5% or less, still more preferably, the said crystallized glass product does not contain a lithium disilicate crystal phase, The crystallized glass product according to any one of Claims 1 to 4, characterized in that...

10. It contains a petalite crystal phase, and the weight percentage occupied by the petalite crystal phase in the devitrified glass product is 15% or less. Preferably, the weight percentage occupied by the petalite crystal phase in the devitrified glass product is 10% or less. More preferably, the weight percentage occupied by the petalite crystal phase in the devitrified glass product is 5% or less. Even more preferably, the devitrified glass product does not contain a petalite crystal phase. The devitrified glass product according to any one of claims 1 to 4, characterized in that.

11. The height of the ball drop test is 1400 mm or more, preferably 1500 mm or more, more preferably 1600 mm or more, and / or the fracture toughness is 1 MPa·m １／２ or more, preferably 1.1 MPa·m １／２ or more, more preferably 1.2 MPa·m １／２ or more, and / or the four-point bending strength is 600 MPa or more, preferably 650 MPa or more, more preferably 700 MPa or more, and / or the Vickers hardness is 670 kgf / mm ２ or more, preferably 680 kgf / mm ２ or more, more preferably 700 kgf / mm ２ or more, and / or the ion exchange layer depth is 80 μm or more, preferably 90 μm or more, more preferably 100 μm or more, and / or the surface stress is 100 MPa or more, preferably 150 MPa or more, more preferably 200 MPa or more, and / or the crystallinity is 10% or more, preferably 15% or more, more preferably 20% or more, and / or the crystal grain size is 50 nm or less, preferably 40 nm or less, more preferably 30 nm or less, and / or the drop resistance is 1500 mm or more, preferably 1600 mm or more, more preferably 1800 mm or more. The devitrified glass product according to any one of claims 1 to 4, characterized in that.

12. The haze of the devitrified glass product having a thickness of 1 mm or less is 0.2% or less. Preferably, it is 0.17% or less. More preferably, it is 0.15% or less. And / or the average light transmittance at a wavelength of 400 to 800 nm is 88.0% or more. Preferably, it is 89.0% or more. More preferably, it is 90.0% or more. Even more preferably, it is 90.5% or more. And / or the light transmittance at a wavelength of 550 nm is 89.0% or more. Preferably, it is 90.0% or more. More preferably, it is 91.0% or more. Even more preferably, it is 91.5% or more. And / or the average light |B| value at 400 to 800 nm is 1.0 or less. Preferably, it is 0.9 or less. More preferably, it is 0.8 or less. The devitrified glass product according to any one of claims 1 to 4, characterized in that.

13. The thickness is 0.2 to 1 mm. Preferably, it is 0.3 to 0.9 mm. More preferably, it is 0.5 to 0.8 mm. Even more preferably, it is 0.55 mm, 0.6 mm, 0.68 mm, 0.7 mm or 0.75 mm. The devitrified glass product according to claim 12, characterized in that.

14. Containing a colorant. The devitrified glass product according to any one of claims 1 to 4, characterized in that.

15. The coloring agent contains, by weight percentage, 0 to 4% of NiO and / or 0 to 4% of Ni ２ O ３ , and / or 0 to 2% of CoO and / or 0 to 2% of Co ２ O ３ , and / or 0 to 7% of Fe ２ O ３ , and / or 0 to 4% of MnO ２ , and / or 0 to 8% of Er ２ O ３ , and / or 0 to 8% of Nd ２ O ３ , and / or 0 to 4% of Cu ２ O, and / or 0 to 8% of Pr ２ O ３ , and / or 0 to 4% of CeO ２ and contains The devitrified glass product according to claim 14, characterized in that.

16. As components, by weight percentage, 60 to 80% of SiO ２ , 3 to 15% of Al ２ O ３ , 5% or more and less than 10% of Li ２ O, 4 to 8% of Na ２ O, 0.5 to 5% of P ２ O ５ , and more than 5% and 15% or less of ZrO ２ are contained, and (SiO ２ + Li ２ O) / (ZrO ２ + P ２ O ５ ) is 4.0 to 15.

5. The devitrified glass, characterized in that.

17. As components, ZnO of 0 to 2% by weight, and / or MgO of 0 to 2% by weight, and / or B ２ O ３ , and / or K of 0 to 3% ２ O, and / or Ln of 0 to 2% ２ O ３ , and / or contains 0 to 2% of a clarifying agent, and the Ln ２ O ３ is one or more of La ２ O ３ , Gd ２ O ３ , Y ２ O ３ , Yb ２ O ３ ​ The devitrified glass according to claim 16, characterized in that.

18. As components, SiO ２ , Al ２ O ３ , Li ２ O, Na ２ O, P ２ O ５ , ZrO ２ are contained, and in terms of weight percentage, (SiO ２ + Li ２ O) / (ZrO ２ + P ２ O ５ ) is 4.0 to 15.5, and the haze of the crystallized glass having a thickness of 1 mm or less is 0.2% or less. The devitrified glass, characterized in that.

19. As components, in weight percentage, 60 to 80% of SiO ２ , and / or 3 to 15% of Al ２ O ３ , and / or 5% or more and less than 10% of Li ２ O, and / or 4 to 8% of Na ２ O, and / or 0.5 to 5% of P ２ O ５ , and / or more than 5% and 15% or less of ZrO ２ , and / or 0 to 2% of ZnO, and / or 0 to 2% of MgO, and / or 0 to 4% of B ２ O ３ , and / or 0 to 3% of K ２ , and / or 0 to 2% of Ln ２ O ３ , and / or contains 0 to 2% of a clarifying agent, and the Ln ２ O ３ is one or more of La ２ O ３ , Gd ２ O ３ , Y ２ O ３ , Yb ２ O ３ among them, The devitrified glass according to claim 18, characterized in that.

20. The components are in weight percentages. 1) SiO ２ / ZrO ２ is 5.0 to 15.0, preferably, SiO ２ / ZrO ２ is 6.0 to 13.0, more preferably, SiO ２ / ZrO ２ is 6.5 to 12.0, still more preferably, SiO ２ / ZrO ２ is 7.0 to 11.0, and 2) (SiO ２ + Li ２ O) / (ZrO ２ + P ２ O ５ is 5.0 to 13.5, preferably, (SiO ２ + Li ２ O) / (ZrO ２ + P ２ O ５ is 6.0 to 11.5, more preferably, (SiO ２ + Li ２ O) / (ZrO ２ + P ２ O ５ is 6.0 to 10.5, and 3) (SiO ２ + Al ２ O ３ + Na ２ O) / Li ２ O is 7.0 to 18.0, preferably, (SiO ２ + Al ２ O ３ + Na ２ O) / Li ２ O is 7.5 to 15.0, more preferably, (SiO ２ + Al ２ O ３ + Na ２ O) / Li ２ O is 8.5 to 13.0, still more preferably, (SiO ２ + Al ２ O ３ + Na ２ O) / Li ２ O is 8.5 to 11.0, and 4) (ZrO ２ + Al ２ O ３ ) / Li ２ O is 0.85 to 5.0, preferably, (ZrO ２ + Al ２ O ３ ) / Li ２ O is 0.9 to 4.0, more preferably, (ZrO ２ + Al ２ O ３ ) / Li ２ O is 1.0 to 3.5, still more preferably, (ZrO ２ + Al ２ O ３ ) / Li ２ O is 1.0 to 3.0, and 5) (Li ２ O + Na ２ O) / (SiO ２ + ZrO ２ ) is 0.10 to 0.27, preferably, (Li ２ O + Na ２ O) / (SiO ２ + ZrO ２ ) is 0.12 to 0.25, more preferably, (Li ２ O + Na ２ O) / (SiO ２ + ZrO ２ ) is 0.14 to 0.25, still more preferably, (Li ２ O + Na ２ O) / (SiO ２ + ZrO ２ ) is 0.15 to 0.23, satisfying one or more of the five conditions of The devitrified glass according to any one of claims 16 to 19, characterized in that.

21. As components, by weight percentage, 62 to 78% of SiO ２ , preferably 64 to 75% of SiO ２ , and / or 5 to 12% of Al ２ O ３ , preferably 5 to 10% of Al ２ O ３ , and / or 6% or more and less than 10% of Li ２ O, and / or 4 to 7.5% of Na ２ O, preferably 4.5 to 7% of Na ２ O, and / or 1 to 4.5% of P ２ O ５ , preferably 1.5 to 4% of P ２ O ５ , and / or 5.5 to 13% of ZrO ２ , preferably 6 to 12% of ZrO ２ , and / or 0 to 1.5% of ZnO, preferably 0 to 1% of ZnO, and / or 0 to 1.5% of MgO, preferably 0 to 1% of MgO, and / or 0 to 3% of B ２ O ３ , preferably 0 to 2% of B ２ O ３ , and / or 0 to 2% of K ２ O, preferably 0 to 1% of K ２ , and / or 0 to 1% of Ln ２ O ３ , preferably 0 to 0.5% of Ln ２ O ３ , and / or 0 to 1% of a clarifying agent, preferably 0 to 0.5% of a clarifying agent, and the Ln ２ O ３ is one or more of La ２ O ３ , Gd ２ O ３ , Y ２ O ３ , Yb ２ O ３ among them., The devitrified glass according to any one of claims 16 to 19, characterized in that...

22. containing a lithium silicate crystal phase, the lithium silicate crystal phase having a higher weight percentage than other crystal phases, preferably, the weight percentage of the lithium silicate crystal phase in the devitrified glass is 5 to 50%, more preferably, the weight percentage of the lithium silicate crystal phase in the devitrified glass is 5 to 40%, and even more preferably, the weight percentage of the lithium silicate crystal phase in the devitrified glass is 10 to 30%. The devitrified glass according to any one of claims 16 to 19, characterized in that...

23. containing a lithium monosilicate crystal phase, the lithium monosilicate crystal phase having a higher weight percentage than other crystal phases, preferably, the weight percentage of the lithium monosilicate crystal phase in the devitrified glass is 5 to 50%, more preferably, the weight percentage of the lithium monosilicate crystal phase in the devitrified glass is 5 to 40%, and even more preferably, the weight percentage of the lithium monosilicate crystal phase in the devitrified glass is 10 to 30%. The devitrified glass according to any one of claims 16 to 19, characterized in that...

24. containing a lithium disilicate crystal phase, the weight percentage of the lithium disilicate crystal phase in the devitrified glass being 20% or less, preferably, the weight percentage of the lithium disilicate crystal phase in the devitrified glass is 10% or less, more preferably, the weight percentage of the lithium disilicate crystal phase in the devitrified glass is 5% or less, and even more preferably, the devitrified glass does not contain a lithium disilicate crystal phase. The devitrified glass according to any one of claims 16 to 19, characterized in that...

25. containing a petalite crystal phase, the weight percentage of the petalite crystal phase in the devitrified glass being 15% or less, preferably, the weight percentage of the petalite crystal phase in the devitrified glass is 10% or less, more preferably, the weight percentage of the petalite crystal phase in the devitrified glass is 5% or less, and even more preferably, the devitrified glass does not contain a petalite crystal phase. The devitrified glass according to any one of claims 16 to 19, characterized in that...

26. The degree of crystallinity is 10% or more, preferably 15% or more, more preferably 20% or more, and / or the crystal grain size is 50 nm or less, preferably 40 nm or less, more preferably 30 nm or less, and / or the body impact height is 1700 mm or more, preferably 1900 mm or more, more preferably 2000 mm or more, and / or the Vickers hardness is 600 kgf / mm ２ or more, preferably 620 kgf / mm ２ or more, more preferably 630 kgf / mm ２ or more, and / or the refractive index is 1.520 to 1.545, and / or the Young's modulus is 80 to 100 GPa The devitrified glass according to any one of claims 16 to 19, characterized in that...

27. The haze of the devitrified glass having a thickness of 1 mm or less is 0.2% or less, preferably 0.17% or less, more preferably 0.15% or less, and / or the average light transmittance at a wavelength of 400 to 800 nm is 88.0% or more, preferably 89.0% or more, more preferably 90.0% or more, still more preferably 90.5% or more, and / or the light transmittance at a wavelength of 550 nm is 89.0% or more, preferably 90.0% or more, more preferably 91.0% or more, still more preferably 91.5% or more, and / or the average light |B| value at 400 to 800 nm is 1.0 or less, preferably 0.9 or less, more preferably 0.8 or less. The devitrified glass according to any one of claims 16 to 19, characterized in that.

28. The thickness is 0.2 to 1 mm, preferably 0.3 to 0.9 mm, more preferably 0.5 to 0.8 mm, still more preferably 0.55 mm, 0.6 mm, 0.68 mm, 0.7 mm or 0.75 mm. The devitrified glass according to claim 27, characterized in that.

29. Containing a colorant. The devitrified glass according to any one of claims 16 to 19, characterized in that.

30. The colorant contains, by weight percentage, 0 to 4% of NiO and / or 0 to 4% of Ni ２ O ３ , and / or 0 to 2% of CoO and / or 0 to 2% of Co ２ O ３ , and / or 0 to 7% of Fe ２ O ３ , and / or 0 to 4% of MnO ２ , and / or 0 to 8% of Er ２ O ３ , and / or 0 to 8% of Nd ２ O ３ , and / or 0 to 4% of Cu ２ O, and / or 0 to 8% of Pr ２ O ３ , and / or 0 to 4% of CeO ２ and contains The devitrified glass according to claim 29, characterized in that.

31. As components, by weight percentage, 60 to 80% of SiO ２ , 3 to 15% of Al ２ O ３ , 5% or more and less than 10% of Li ２ O, 4 to 8% of Na ２ O, 0.5 to 5% of P ２ O ５ , and more than 5% and 15% or less of ZrO ２ are contained, and (SiO ２ + Li ２ O) / (ZrO ２ + P ２ O ５ ) is 4.0 to 15.

5. The matrix glass characterized in that.

32. As components, ZnO of 0 to 2% by weight, and / or MgO of 0 to 2% by weight, and / or B ２ O ３ , and / or K of 0 to 3% ２ O, and / or Ln ２ O ３ , and / or a clarifying agent of 0 to 2% is contained, and the Ln ２ O ３ is one or more of La ２ O ３ , Gd ２ O ３ , Y ２ O ３ , Yb ２ O ３ ​ The matrix glass according to claim 37, characterized in that.

33. The components are in weight percentages. 1) SiO ２ / ZrO ２ is 5.0 to 15.0, preferably, SiO ２ / ZrO ２ is 6.0 to 13.0, more preferably, SiO ２ / ZrO ２ is 6.5 to 12.0, even more preferably, SiO ２ / ZrO ２ is 7.0 to 11.0, and 2) (SiO ２ + Li ２ O) / (ZrO ２ + P ２ O ５ ) is 5.0 to 13.5, preferably, (SiO ２ + Li ２ O) / (ZrO ２ + P ２ O ５ ) is 6.0 to 11.5, more preferably, (SiO ２ + Li ２ O) / (ZrO ２ + P ２ O ５ ) is 6.0 to 10.5, and 3) (SiO ２ + Al ２ O ３ + Na ２ O) / Li ２ O is 7.0 to 18.0, preferably, (SiO ２ + Al ２ O ３ + Na ２ O) / Li ２ O is 7.5 to 15.0, more preferably, (SiO ２ + Al ２ O ３ + Na ２ O) / Li ２ O is 8.5 to 13.0, still more preferably, (SiO ２ + Al ２ O ３ + Na ２ O) / Li ２ O is 8.5 to 11.0, and 4) (ZrO ２ + Al ２ O ３ ) / Li ２ O is 0.85 to 5.0, preferably, (ZrO ２ + Al ２ O ３ ) / Li ２ O is 0.9 to 4.0, more preferably, (ZrO ２ + Al ２ O ３ ) / Li ２ O is 1.0 to 3.5, still more preferably, (ZrO ２ + Al ２ O ３ ) / Li ２ O is 1.0 to 3.0, and 5) (Li ２ O + Na ２ O) / (SiO ２ + ZrO ２ ) is 0.10 to 0.27, preferably, (Li ２ O + Na ２ O) / (SiO ２ + ZrO ２ ) is 0.12 to 0.25, more preferably, (Li ２ O + Na ２ O) / (SiO ２ + ZrO ２ ) is 0.14 to 0.25, still more preferably, (Li ２ O + Na ２ O) / (SiO ２ + ZrO ２ ) is 0.15 to 0.23, and satisfies one or more of the five conditions The matrix glass according to claim 31 or 32, characterized in that.

34. As components, by weight percentage, 62 to 78% of SiO ２ , preferably 64 to 75% of SiO ２ , and / or 5 to 12% of Al ２ O ３ , preferably 5 to 10% of Al ２ O ３ , and / or 6% or more and less than 10% of Li ２ O, and / or 4 to 7.5% of Na ２ O, preferably 4.5 to 7% of Na ２ O, and / or 1 to 4.5% of P ２ O ５ , preferably 1.5 to 4% of P ２ O ５ , and / or 5.5 to 13% of ZrO ２ , preferably 6 to 12% of ZrO ２ , and / or 0 to 1.5% of ZnO, preferably 0 to 1% of ZnO, and / or 0 to 1.5% of MgO, preferably 0 to 1% of MgO, and / or 0 to 3% of B ２ O ３ , preferably 0 to 2% of B ２ O ３ , and / or 0 to 2% of K ２ O, preferably 0 to 1% of K ２ , and / or 0 to 1% of Ln ２ O ３ , preferably 0 to 0.5% of Ln ２ O ３ , and / or 0 to 1% of a clarifying agent, preferably 0 to 0.5% of a clarifying agent, and the Ln ２ O ３ is one or more of La ２ O ３ , Gd ２ O ３ , Y ２ O ３ , Yb ２ O ３ among them, The matrix glass according to claim 31 or 32, characterized in that.

35. The refractive index is 1.510 to 1.

530. The matrix glass according to claim 31 or 32, characterized in that.

36. Containing a colorant. The matrix glass according to claim 31 or 32, characterized in that.

37. The colorant contains, by weight percentage, 0 to 4% of NiO and / or 0 to 4% of Ni ２ O ３ , and / or 0 to 2% of CoO and / or 0 to 2% of Co ２ O ３ , and / or 0 to 7% of Fe ２ O ３ , and / or 0 to 4% of MnO ２ , and / or 0 to 8% of Er ２ O ３ , and / or 0 to 8% of Nd ２ O ３ , and / or 0 to 4% of Cu ２ O, and / or 0 to 8% of Pr ２ O ３ , and / or 0 to 4% of CeO ２ and contains The matrix glass according to claim 36, characterized in that.

38. Containing the devitrified glass according to any one of claims 16 to 30. The devitrified glass molded body characterized in that.

39. The crystallization glass product according to any one of claims 1 to 15, and / or the crystallization glass according to any one of claims 16 to 30, and / or the matrix glass according to any one of claims 31 to 37, and / or the crystallization glass compact according to claim 38, characterized in that it is a glass cover plate.

40. The crystallization glass product according to any one of claims 1 to 15, and / or the crystallization glass according to any one of claims 16 to 30, and / or the matrix glass according to any one of claims 31 to 37, and / or the crystallization glass compact according to claim 38, characterized in that it is a glass component.

41. The crystallization glass product according to any one of claims 1 to 15, and / or the crystallization glass according to any one of claims 16 to 30, and / or the matrix glass according to any one of claims 31 to 37, and / or the crystallization glass compact according to claim 38, and / or the glass cover plate according to claim 39, and / or the glass component according to claim 40, characterized in that it is a display device.

42. The crystallization glass product according to any one of claims 1 to 15, and / or the crystallization glass according to any one of claims 16 to 30, and / or the matrix glass according to any one of claims 31 to 37, and / or the crystallization glass compact according to claim 38, and / or the glass cover plate according to claim 39, and / or the glass component according to claim 40, characterized in that it is an electronic device.

43. A process for forming a matrix glass, treating the matrix glass in a crystallization process to form a crystallization glass, and treating the crystallization glass in a chemical strengthening process to form a crystallization glass product, characterized in that it is a method for manufacturing the crystallization glass product according to any one of claims 1 to 15.

44. The crystallization process includes a step of raising the temperature to a predetermined crystallization treatment temperature, maintaining the temperature for a certain period of time after reaching the crystallization treatment temperature, and then lowering the temperature. The crystallization treatment temperature is 550 to 700 °C, preferably 580 to 650 °C, and the holding time at the crystallization treatment temperature is 0 to 8 hours, preferably 1 to 6 hours. characterized in that it is a method for manufacturing the crystallization glass product according to claim 43.

45. The crystallization process includes a step of performing a crystal nucleation process treatment at a first temperature and then performing a crystal growth process treatment at a second temperature higher than the temperature of the crystal nucleation process. The method for manufacturing a crystallized glass product according to claim 43, characterized in that.

46. In the crystallization process, the first temperature is 450 to 550 °C, the second temperature is 550 to 700 °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. The method for manufacturing a crystallized glass product according to claim 45, characterized in that.

47. The chemical strengthening process includes a step of immersing the crystallized glass in a salt bath of molten Na salt at a temperature of 350 °C to 470 °C, preferably 380 °C to 460 °C, for 1 to 36 hours, preferably 2 to 24 hours, and / or immersing the crystallized glass in a salt bath of molten K salt at a temperature of 360 °C to 450 °C for 1 to 36 hours, preferably 2 to 24 hours, and / or immersing the crystallized glass in a mixed salt bath of molten K salt and Na salt at a temperature of 360 °C to 450 °C for 1 to 36 hours, preferably 2 to 24 hours. The method for manufacturing a crystallized glass product according to any one of claims 43 to 46, characterized in that.

48. After forming the matrix glass, it includes a step of treating the matrix glass by a crystallization process to form a crystallized glass. The method for manufacturing a crystallized glass according to any one of claims 16 to 30, characterized in that.

49. The crystallization process includes a step of heating up to a predetermined crystallization treatment temperature, maintaining the temperature for a certain period of time after reaching the crystallization treatment temperature, and then cooling down. The crystallization treatment temperature is 550 to 700 °C, preferably 580 to 650 °C, and the holding time at the crystallization treatment temperature is 0 to 8 hours, preferably 1 to 6 hours. The method for manufacturing a crystallized glass according to claim 48, characterized in that.

50. The crystallization process includes a step of performing a crystal nucleation process treatment at a first temperature and then performing a crystal growth process treatment at a second temperature higher than the temperature of the crystal nucleation process. The method for manufacturing a crystallized glass according to claim 48, characterized in that.

51. In the crystallization process, the first temperature is 450 to 550 °C, the second temperature is 550 to 700 °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. The method for manufacturing the crystallized glass according to claim 50, characterized in that.

52. A step of manufacturing a crystallized glass molded body by polishing or buffing the crystallized glass, or a step of manufacturing a crystallized glass molded body by treating the matrix glass or the crystallized glass at a certain temperature by a hot bending process or a press molding process. The method for manufacturing the crystallized glass molded body according to claim 38, characterized in that.

53. A step of performing a single crystallization heat treatment process including heating, heat preservation, and nucleation, heating, heat preservation, and crystallization, and cooling to room temperature on the matrix glass to form a pre-crystallized glass, and a step of performing hot processing and molding on the pre-crystallized glass to obtain a crystallized glass molded body. The method for manufacturing the crystallized glass molded body according to claim 52, characterized in that.

54. 1) Placing the matrix glass, pre-crystallized glass, or crystallized glass in a mold, passing the mold through each heating site in a hot bending machine in sequence, retaining the mold at each site for a certain time for heat preservation, setting the temperature in the preheating region to 400 to 800 °C, the pressure to 0.01 to 0.05 MPa, and the time to 40 to 200 s, which is a heating and preheating step. 2) After preheating the mold, transferring it to the molding site, applying a certain pressure to the mold by a hot bending machine, setting the pressure range to 0.1 to 0.8 MPa, the temperature range in the molding site to 600 to 850 °C, and the molding time range to 40 to 200 s, which is a pressure molding step. 3) Transferring the mold to the cooling site and cooling it site by site, setting the cooling temperature range to 750 to 500 °C, the pressure to 0.01 to 0.05 MPa, and the time to 40 to 200 s, which is a pressure maintaining and cooling step. The method for manufacturing the crystallized glass molded body according to claim 52, characterized in that.

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