CN112939469A

CN112939469A - Glass ceramics and glass ceramics product

Info

Publication number: CN112939469A
Application number: CN202110306397.7A
Authority: CN
Inventors: 原保平; 李赛; 陈雪梅; 粟勇; 胡邦红; 司合帅; 黄开文
Original assignee: Huawei Technologies Co Ltd; CDGM Glass Co Ltd
Current assignee: Huawei Technologies Co Ltd; CDGM Glass Co Ltd
Priority date: 2021-03-23
Filing date: 2021-03-23
Publication date: 2021-06-11
Anticipated expiration: 2041-03-23
Also published as: CN112939469B

Abstract

The invention provides a microcrystalline glass product comprising a crystalline phase of lithium metasilicate and quartz solid solution, the total content of lithium metasilicate and quartz solid solution being higher in weight percent than the other crystalline phases, the microcrystalline glass product comprising, in weight percent: SiO 2₂+Al₂O₃：60～80％；P₂O₅：2～10％；ZrO₂：0.5～10％；Ln₂O₃: greater than 0 but less than or equal to 10%; li₂O+Na₂O+K₂O: 21.5 to 30% of (SiO)₂+Al₂O₃)/Ln₂O₃7 or more, said Ln₂O₃Is La₂O₃、Gd₂O₃、Y₂O₃、Yb₂O₃One or more of (a). Through reasonable component design, the microcrystalline glass product obtained by the invention has excellent mechanical property and optical property, and is suitable for electronic equipment or display equipment.

Description

Glass ceramics and glass ceramics product

Technical Field

The invention relates to a microcrystalline glass, in particular to a microcrystalline glass and a microcrystalline glass product with excellent mechanical property and optical property.

Background

In recent years, with the rise and development of consumer electronics, glass is widely used in such electronic products as a transparent and good-performance material. Portable devices such as cell phones, watches, PADs, portable media players, personal computers and cameras, which are particularly susceptible to accidental falls onto hard surfaces during use, often incorporate a cover glass that may be damaged after impact from the hard surface, which requires that the cover glass have excellent mechanical properties to reduce the negative impact on the portable device during use and to extend its useful life. The microcrystalline glass is a material which is crystallized in the glass by carrying out heat treatment on the glass, has more excellent mechanical properties than the conventional glass, forms a microcrystalline in the glass, and has obvious advantages in bending resistance, wear resistance, falling resistance and the like compared with the conventional glass.

With the development of technology, electronic devices or display devices have made higher demands on the optical properties of glass materials used therein, which are properties exhibited when a substance absorbs, reflects, and refracts light, including light transmittance, haze, refractive index, and the like. However, the microcrystalline glass on the market at present has the problems of high haze, low light transmittance and the like, and is difficult to apply to display devices or electronic devices with high requirements.

Disclosure of Invention

The invention aims to provide microcrystalline glass and a microcrystalline glass product with excellent mechanical property and optical property.

The technical scheme adopted by the invention for solving the technical problem is as follows:

(1) a microcrystalline glass product comprising a crystalline phase of lithium metasilicate and quartz solid solution, the combined content of lithium metasilicate and quartz solid solution being in a higher percentage by weight than the other crystalline phases, the composition of said microcrystalline glass product, expressed in percentages by weight, comprising: SiO 2₂+Al₂O₃：60～80％；P₂O₅：2～10％；ZrO₂：0.5～10％；Ln₂O₃: greater than 0 but less than or equal to 10%; li₂O+Na₂O+K₂O: 21.5 to 30% of (SiO)₂+Al₂O₃)/Ln₂O₃7 or more, said Ln₂O₃Is La₂O₃、Gd₂O₃、 Y₂O₃、Yb₂O₃One or more of (a).

(2) The microcrystalline glass product as described in (1), which comprises the following components by weight percent: MgO: 0-2%; and/or ZnO: 0-2%; and/or SrO: 0 to 5 percent; and/or BaO: 0 to 5 percent; and/or CaO: 0 to 5 percent; and/or TiO₂: 0 to 5 percent; and/or B₂O₃: 0 to 5 percent; and/or a clarifying agent: 0-2% of a clarifying agent Sb₂O₃、SnO₂、SnO、CeO₂One or more of (a).

(3) Microcrystalline glass product containing lithium metasilicate and quartz solid solution crystal phases, the total content of lithium metasilicate and quartz solid solution crystal phases having a higher weight percentage than other crystal phases, said microcrystalline glass product containing SiO₂、Al₂O₃、Ln₂O₃And an alkali metal oxide as an essential component, the components of which are expressed in weight percent, wherein (SiO)₂+Al₂O₃)/Ln₂O₃7 or more, the height of the microcrystalline glass product in a falling ball test is 1200mm or more, and Ln is₂O₃Is La₂O₃、Gd₂O₃、Y₂O₃、 Yb₂O₃One or more of (a).

(4) The microcrystalline glass product according to (3), which comprises the following components in percentage by weight: SiO 2₂+Al₂O₃: 60-80%; and/or P₂O₅: 2-10%; and/or ZrO₂: 0.5-10%; and/or Ln₂O₃: greater than 0 but less than or equal to 10%; and/or Li₂O+Na₂O+K₂O: 21.5-30%; and/or MgO: 0-2%; and/or ZnO: 0-2%; and/or SrO: 0 to 5 percent; and/or BaO: 0 to 5 percent; and/or CaO: 0 to 5 percent; and/or TiO₂: 0 to 5 percent; and/or B₂O₃: 0 to 5 percent; and/or a clarifying agent: 0-2% of Ln₂O₃Is La₂O₃、Gd₂O₃、Y₂O₃、Yb₂O₃One or more of Sb as clarifying agent₂O₃、SnO₂、SnO、CeO₂One or more of (a).

(5) The microcrystalline glass product comprises the following components in percentage by weight: SiO 2₂+Al₂O₃： 60～80％；P₂O₅：2～10％；ZrO₂：0.5～10％；Ln₂O₃: greater than 0 but less than or equal to 10%; li₂O+Na₂O+K₂O：21.5～30％；MgO：0～2％；ZnO：0～2％；SrO：0～5％；BaO： 0～5％；CaO：0～5％；TiO₂：0～5％；B₂O₃: 0 to 5 percent; a clarifying agent: 0-2% of Ln₂O₃Is La₂O₃、Gd₂O₃、Y₂O₃、Yb₂O₃One or more of Sb as clarifying agent₂O₃、SnO₂、SnO、 CeO₂One or more of (a).

(6) The microcrystalline glass product according to any one of (1) to (5), wherein the microcrystalline glass product comprises the following components in percentage by weight: (SiO)₂+Al₂O₃)/Ln₂O₃10 to 72, preferably (SiO)₂+Al₂O₃)/Ln₂O₃Is 11 to 50, more preferably (SiO)₂+Al₂O₃)/Ln₂O₃12 to 30; and/or (SiO)₂+Al₂O₃)/ZrO₂10 to 80, preferably (SiO)₂+Al₂O₃)/ZrO₂15 to 50, more preferably (SiO)₂+Al₂O₃)/ZrO₂20 to 40; and/or (Li)₂O+Na₂O+K₂O)/P₂O₅2.5 to 13, preferably (Li)₂O+Na₂O+K₂O) /P₂O₅2.8 to 10, more preferably (Li)₂O+Na₂O+K₂O)/P₂O₅Is 3 to 7.

(7) The crystallized glass product according to any one of (1) to (6), which comprises the following components in percentage by weight: SiO 2₂+Al₂O₃: 68-80%, preferably SiO₂+Al₂O₃: 70-78%; and/or P₂O₅: 3.5-9%, preferably P₂O₅: 4-8%; and/or ZrO₂: 1 to 6%, preferably ZrO₂: 1-5%; and/or Ln₂O₃: 0.5-8%, preferably Ln₂O₃: 1-7%; and/or Li₂O+Na₂O+K₂O: 22-28%; and/or MgO: 0 to 1 percent; and/or ZnO: 0 to 1 percent; and/or SrO: 0 to 3%, preferably SrO: 0 to 1 percent; and/or BaO: 0-3%, preferably BaO: 0 to 1 percent; and/or CaO: 0-3%, preferably CaO: 0 to 1 percent; and/or TiO₂: 0 to 3%, preferably TiO₂: 0 to 1 percent; and/or B₂O₃: 0 to 3%, preferably B₂O₃: 0 to 1 percent; and/or a clarifying agent: 0-1%, preferably clarifying agent: 0 to 0.5 percent of Ln₂O₃Is La₂O₃、 Gd₂O₃、Y₂O₃、Yb₂O₃One or more of Sb as clarifying agent₂O₃、SnO₂、SnO、CeO₂One or more of (a).

(8) The crystallized glass product according to any one of (1) to (7), which comprises the following components in percentage by weight: li₂O: 15 to 25%, preferably Li₂O：16～23％。

(9) The microcrystalline glass product according to any one of (1) to (8), wherein the lithium monosilicate crystal phase accounts for 20 to 60% by weight of the microcrystalline glass product, preferably the lithium monosilicate crystal phase accounts for 25 to 55% by weight of the microcrystalline glass product, more preferably the lithium monosilicate crystal phase accounts for 30 to 50% by weight of the microcrystalline glass product, and/or the quartz and quartz solid solution crystal phase accounts for 45% or less by weight of the microcrystalline glass product, preferably the quartz and quartz solid solution crystal phase accounts for 5 to 40% by weight of the microcrystalline glass product.

(10) The crystallized glass product according to any one of (1) to (9), which has a four-point bending strength of 600MPa or more, preferably 650MPa or more, and more preferably 700MPa or more; and/or the depth of the ion exchange layer is 20 μm or more, preferably 30 μm or more, more preferably 40 μm or more; and/or the ball drop test height is 1200mm or more, preferably 1300mm or more, more preferably 1400mm or more; and/or a fracture toughness of 1MPa m^1/2Above, preferably 1.1MPa · m^1/2More preferably 1.2MPa · m or more^1/2The above; and/or a Vickers hardness of 680kgf/mm²Above, preferably 700kgf/mm²Above, 720kgf/mm is more preferable²The above; and/or a crystallinity of 50% or more, preferably 60% or more, more preferably 70% or more; and/or the crystal grain size is 60nm or less, preferably 50nm or less, more preferably 30nm or less.

(11) The crystallized glass product according to any one of (1) to (10), wherein the crystallized glass product having a thickness of 1mm or less has a haze of 0.2% or less, preferably 0.17% or less, more preferably 0.15% or less; and/or an average transmittance at a wavelength of 400 to 800nm of 87% or more, preferably 89% or more, more preferably 90% or more; and/or a 550nm wavelength transmittance of 88% or more, preferably 90% or more, more preferably 91% or more.

(12) The crystallized glass product according to (11), wherein the crystallized glass product has a thickness of 0.2 to 1mm, preferably 0.3 to 0.9mm, more preferably 0.5 to 0.8mm, and further preferably 0.55mm, or 0.6mm, or 0.68mm, or 0.7mm, or 0.75 mm.

(13) The crystallized glass product according to any one of (1) to (5), which contains a colorant.

(14) The crystallized glass article of (13), wherein said colorant comprises, in weight percent: NiO: 0 to 4 percent; and/or Ni₂O₃: 0 to 4 percent; and/or a CoO: 0-2%; and/or Co₂O₃: 0-2%; and/or Fe₂O₃: 0 to 7 percent; and/or MnO₂: 0 to 4 percent; and/or Er₂O₃: 0-8%; and/or Nd₂O₃: 0-8%; and/or Cu₂O: 0 to 4 percent; and/or Pr₂O₃: 0-8%; and/or CeO₂：0～ 4％。

(15) The glass-ceramic article according to any of (13) or (14), wherein the colorant comprises, in weight percent: NiO: 0.1-4%; and/or Ni₂O₃: 0.1-4%; and/or a CoO: 0.05-2%; and/or Co₂O₃: 0.05-2%; and/or Fe₂O₃: 0.2-7%; and/or MnO₂: 0.1 to 4 percent; and/or Er₂O₃: 0.4-8%; and/or Nd₂O₃: 0.4-8%; and/or Cu₂O: 0.5-4%; and/or Pr₂O₃: 0.4-8%; and/or CeO₂：0.5～4％。

(16) The glass-ceramic article according to any of (13) or (14), wherein the colorant comprises, in weight percent: NiO: 0.1-3%; and/or Ni₂O₃: 0.1-3%; and/or a CoO: 0.05-1.8%; and/or Co₂O₃: 0.05-1.8%; and/or Fe₂O₃: 0.2-5%; and/or MnO₂: 0.1-3%; and/or Er₂O₃: 0.4-6%; and/or Nd₂O₃: 0.4-6%; and/or Cu₂O: 0.5 to 3 percent; and/or Pr₂O₃: 0.4-6%; and/or CeO₂：0.5～3％。

(17) The glass-ceramic article according to any of (13) or (14), wherein the colorant comprises, in weight percent: NiO: 0.1-3%; and/or Ni₂O₃：0.1～3％。

(18) The glass-ceramic article according to any of (13) or (14), wherein the colorant comprises, in weight percent: and (3) CoO: 0.05-1.8%; and/or Co₂O₃：0.05～1.8％。

(19) The glass-ceramic article according to any of (13) or (14), wherein the colorant comprises, in weight percent: cu₂O: 0.5-3%; and/or CeO₂：0.5～3％。

(20) The glass-ceramic article according to any of (13) or (14), wherein the colorant comprises, in weight percent: fe₂O₃: 0.2-5%, CoO: 0.05-0.3%; or Fe₂O₃：0.2～ 5％、Co₂O₃: 0.05-0.3%; or Fe₂O₃: 0.2-5%, CoO: 0.05-0.3%, NiO: 0.1-1%; or Fe₂O₃：0.2～5％、Co₂O₃：0.05～0.3％、NiO：0.1～1％。

(21) The glass-ceramic article according to any of (13) or (14), wherein the colorant comprises, in weight percent: pr (Pr) of₂O₃: 0.4-6%; or Fe₂O₃: 0.2-5%; or MnO₂: 0.1-3%; or Er₂O₃: 0.4-6%; or Nd₂O₃：0.4～6％。

(22) The glass-ceramic article according to any of (13) or (14), wherein the colorant comprises, in weight percent: er₂O₃：0.4～6％、Nd₂O₃：0.4～4％、MnO₂：0.1～2％。

(23) Microcrystalline glass comprising a crystalline phase of lithium silicate and quartz solid solution, the combined content of lithium silicate and quartz solid solution being higher in weight percentage than the other crystalline phases, the composition of the microcrystalline glass being such thatThe ratio, expressed, contains: SiO 2₂+Al₂O₃：60～80％；P₂O₅： 2～10％；ZrO₂：0.5～10％；Ln₂O₃: greater than 0 but less than or equal to 10%; li₂O+Na₂O+K₂O: 21.5 to 30% of (SiO)₂+Al₂O₃)/Ln₂O₃7 or more, said Ln₂O₃Is La₂O₃、Gd₂O₃、 Y₂O₃、Yb₂O₃One or more of (a).

(24) The glass-ceramic according to (23), which comprises the following components in percentage by weight: MgO: 0-2%; and/or ZnO: 0-2%; and/or SrO: 0 to 5 percent; and/or BaO: 0 to 5 percent; and/or CaO: 0 to 5 percent; and/or TiO₂: 0 to 5 percent; and/or B₂O₃: 0 to 5 percent; and/or a clarifying agent: 0-2% of a clarifying agent Sb₂O₃、SnO₂、SnO、CeO₂One or more of (a).

(25) Microcrystalline glass comprising lithium metasilicate and quartz solid solution crystal phases, the combined content of lithium metasilicate and quartz solid solution crystal phases having a higher weight percentage than the other crystal phases, said microcrystalline glass comprising SiO₂、Al₂O₃、Ln₂O₃And an alkali metal oxide as an essential component, the components of which are expressed in weight percent, wherein (SiO)₂+Al₂O₃)/Ln₂O₃Is more than 7, the body falling ball test height of the microcrystalline glass is more than 1100mm, and the Ln₂O₃Is La₂O₃、Gd₂O₃、Y₂O₃、Yb₂O₃One or more of (a).

(26) The glass-ceramic according to (25), which comprises, in terms of weight percent: SiO 2₂+Al₂O₃: 60-80%; and/or P₂O₅: 2-10%; and/or ZrO₂: 0.5-10%; and/or Ln₂O₃: greater than 0 but less10% or less; and/or Li₂O+Na₂O+K₂O: 21.5-30%; and/or MgO: 0-2%; and/or ZnO: 0-2%; and/or SrO: 0 to 5 percent; and/or BaO: 0 to 5 percent; and/or CaO: 0 to 5 percent; and/or TiO₂: 0 to 5 percent; and/or B₂O₃: 0 to 5 percent; and/or a clarifying agent: 0-2% of Ln₂O₃Is La₂O₃、Gd₂O₃、Y₂O₃、Yb₂O₃One or more of Sb as clarifying agent₂O₃、SnO₂、SnO、CeO₂One or more of (a).

(27) The microcrystalline glass comprises the following components in percentage by weight: SiO 2₂+Al₂O₃：60～ 80％；P₂O₅：2～10％；ZrO₂：0.5～10％；Ln₂O₃: greater than 0 but less than or equal to 10%; li₂O+Na₂O+K₂O：21.5～30％；MgO：0～2％；ZnO：0～2％；SrO：0～5％；BaO： 0～5％；CaO：0～5％；TiO₂：0～5％；B₂O₃: 0 to 5 percent; a clarifying agent: 0-2% of Ln₂O₃Is La₂O₃、Gd₂O₃、Y₂O₃、Yb₂O₃One or more of Sb as clarifying agent₂O₃、SnO₂、SnO、 CeO₂One or more of (a).

(28) The glass-ceramic according to any one of (23) to (27), which comprises, in weight percent: (SiO)₂+Al₂O₃)/Ln₂O₃10 to 72, preferably (SiO)₂+Al₂O₃)/Ln₂O₃Is 11 to 50, more preferably (SiO)₂+Al₂O₃)/Ln₂O₃12 to 30; and/or (SiO)₂+Al₂O₃)/ZrO₂10 to 80, preferably (SiO)₂+Al₂O₃)/ZrO₂15 to 50, more preferably (SiO)₂+Al₂O₃)/ZrO₂20 to 40; and/or (Li)₂O+Na₂O+K₂O)/P₂O₅2.5 to 13, preferably (Li)₂O+Na₂O+K₂O) /P₂O₅2.8 to 10, more preferably (Li)₂O+Na₂O+K₂O)/P₂O₅Is 3 to 7.

(29) The glass-ceramic according to any one of (23) to (28), which comprises, in terms of weight percent: SiO 2₂+Al₂O₃: 68-80%, preferably SiO₂+Al₂O₃: 70-78%; and/or P₂O₅: 3.5-9%, preferably P₂O₅: 4-8%; and/or ZrO₂: 1 to 6%, preferably ZrO₂: 1-5%; and/or Ln₂O₃: 0.5-8%, preferably Ln₂O₃: 1-7%; and/or Li₂O+Na₂O+K₂O: 22-28%; and/or MgO: 0 to 1 percent; and/or ZnO: 0 to 1 percent; and/or SrO: 0 to 3%, preferably SrO: 0 to 1 percent; and/or BaO: 0-3%, preferably BaO: 0 to 1 percent; and/or CaO: 0-3%, preferably CaO: 0 to 1 percent; and/or TiO₂: 0 to 3%, preferably TiO₂: 0 to 1 percent; and/or B₂O₃: 0 to 3%, preferably B₂O₃: 0 to 1 percent; and/or a clarifying agent: 0-1%, preferably clarifying agent: 0 to 0.5 percent of Ln₂O₃Is La₂O₃、 Gd₂O₃、Y₂O₃、Yb₂O₃One or more of Sb as clarifying agent₂O₃、SnO₂、SnO、CeO₂One or more of (a).

(30) The glass-ceramic according to any one of (23) to (29), which comprises, in terms of weight percent: li₂O: 15 to 25%, preferably Li₂O：16～23％。

(31) The microcrystalline glass according to any one of (23) to (30), wherein the lithium monosilicate crystal phase accounts for 20 to 60% by weight of the microcrystalline glass, preferably the lithium monosilicate crystal phase accounts for 25 to 55% by weight of the microcrystalline glass, more preferably the lithium monosilicate crystal phase accounts for 30 to 50% by weight of the microcrystalline glass, and/or the quartz and quartz solid solution crystal phase accounts for 45% or less by weight of the microcrystalline glass, preferably the quartz and quartz solid solution crystal phase accounts for 5 to 40% by weight of the microcrystalline glass.

(32) The crystallized glass according to any one of (23) to (31), wherein the crystallized glass has a body falling ball test height of 1100mm or more, preferably 1200mm or more, and more preferably 1300mm or more; and/or a Vickers hardness of 650kgf/mm²Above, it is preferably 660kgf/mm²Above, more preferably 670kgf/mm²The above; and/or a crystallinity of 50% or more, preferably 60% or more, more preferably 70% or more; and/or a crystal grain size of 60nm or less, preferably 50nm or less, more preferably 30nm or less; and/or a coefficient of thermal expansion of 90 x 10^-7/K～100×10^-7K; and/or a refractive index of 1.5500-1.5700.

(33) The crystallized glass according to any one of (23) to (32), wherein the crystallized glass having a thickness of 1mm or less has a haze of 0.2% or less, preferably 0.17% or less, more preferably 0.15% or less; and/or an average transmittance at a wavelength of 400 to 800nm of 87% or more, preferably 89% or more, more preferably 90% or more; and/or a 550nm wavelength transmittance of 88% or more, preferably 90% or more, more preferably 91% or more.

(34) The microcrystalline glass according to (33), wherein the microcrystalline glass has a thickness of 0.2 to 1mm, preferably 0.3 to 0.9mm, more preferably 0.5 to 0.8mm, and still more preferably 0.55mm, 0.6mm, 0.68mm, 0.7mm, or 0.75 mm.

(35) The crystallized glass of any one of (23) to (27), which contains a colorant.

(36) The glass ceramic according to (35), wherein the coloring agent comprises, in weight percent: NiO: 0 to 4 percent; and/or Ni₂O₃: 0 to 4 percent; and/or a CoO: 0-2%; and/or Co₂O₃: 0 to 2 percent; and/or Fe₂O₃: 0 to 7 percent; and/or MnO₂: 0 to 4 percent; and/or Er₂O₃: 0-8%; and/or Nd₂O₃: 0-8%; and/or Cu₂O: 0 to 4 percent; andor Pr₂O₃: 0-8%; and/or CeO₂：0～ 4％。

(37) The glass-ceramic according to any of (35) or (36), wherein the colorant comprises, in weight percent: NiO: 0.1-4%; and/or Ni₂O₃: 0.1-4%; and/or a CoO: 0.05 to 2 percent; and/or Co₂O₃: 0.05-2%; and/or Fe₂O₃: 0.2-7%; and/or MnO₂: 0.1-4%; and/or Er₂O₃: 0.4-8%; and/or Nd₂O₃: 0.4-8%; and/or Cu₂O: 0.5-4%; and/or Pr₂O₃: 0.4-8%; and/or CeO₂：0.5～4％。

(38) The glass-ceramic according to any of (35) or (36), wherein the colorant comprises, in weight percent: NiO: 0.1-3%; and/or Ni₂O₃: 0.1-3%; and/or a CoO: 0.05 to 1.8 percent; and/or Co₂O₃: 0.05-1.8%; and/or Fe₂O₃: 0.2-5%; and/or MnO₂: 0.1 to 3 percent; and/or Er₂O₃: 0.4-6%; and/or Nd₂O₃: 0.4-6%; and/or Cu₂O: 0.5-3%; and/or Pr₂O₃: 0.4-6%; and/or CeO₂：0.5～3％。

(39) The glass-ceramic according to any of (35) or (36), wherein the colorant comprises, in weight percent: NiO: 0.1-3%; and/or Ni₂O₃：0.1～3％。

(40) The glass-ceramic according to any of (35) or (36), wherein the colorant comprises, in weight percent: and (3) CoO: 0.05-1.8%; and/or Co₂O₃：0.05～1.8％。

(41) The glass-ceramic according to any of (35) or (36), wherein the colorant comprises, in weight percent: cu₂O: 0.5-3%; and/or CeO₂：0.5～3％。

(42) The glass-ceramic according to any of (35) or (36), wherein the colorant comprises, in weight percent: fe₂O₃: 0.2-5%, CoO: 0.05-0.3%; or Fe₂O₃：0.2～5％、Co₂O₃: 0.05-0.3%; or Fe₂O₃: 0.2-5%, CoO: 0.05-0.3%, NiO: 0.1-1%; or Fe₂O₃：0.2～5％、Co₂O₃：0.05～0.3％、NiO：0.1～1％。

(43) The glass-ceramic according to any of (35) or (36), wherein the colorant comprises, in weight percent: pr (Pr) of₂O₃: 0.4-6%; or Fe₂O₃: 0.2-5%; or MnO₂: 0.1 to 3 percent; or Er₂O₃: 0.4-6%; or Nd₂O₃：0.4～6％。

(44) The glass-ceramic according to any of (35) or (36), wherein the colorant comprises, in weight percent: er₂O₃：0.4～6％、Nd₂O₃：0.4～4％、MnO₂：0.1～2％。

(45) The matrix glass comprises the following components in percentage by weight: SiO 2₂+Al₂O₃：60～ 80％；P₂O₅：2～10％；ZrO₂：0.5～10％；Ln₂O₃: greater than 0 but less than or equal to 10%; li₂O+Na₂O+K₂O: 21.5 to 30% of (SiO)₂+Al₂O₃)/Ln₂O₃7 or more, said Ln₂O₃Is La₂O₃、Gd₂O₃、Y₂O₃、Yb₂O₃One or more of (a).

(46) The base glass as described in (45), which further comprises, in terms of weight percent: MgO: 0-2%; and/or ZnO: 0-2%; and/or SrO: 0 to 5 percent; and/or BaO: 0 to 5 percent; and/or CaO: 0 to 5 percent; and/or TiO₂: 0 to 5 percent; and/or B₂O₃: 0 to 5 percent; and/or a clarifying agent: 0-2% of a clarifying agent Sb₂O₃、SnO₂、SnO、CeO₂One or more of。

(47) The base glass as described in any one of (45) or (46), which has a composition in terms of weight percentage, wherein: (SiO)₂+Al₂O₃)/Ln₂O₃10 to 72, preferably (SiO)₂+Al₂O₃)/Ln₂O₃Is 11 to 50, more preferably (SiO)₂+Al₂O₃)/Ln₂O₃12 to 30; and/or (SiO)₂+Al₂O₃)/ZrO₂10 to 80, preferably (SiO)₂+Al₂O₃)/ZrO₂15 to 50, more preferably (SiO)₂+Al₂O₃)/ZrO₂20 to 40; and/or (Li)₂O+Na₂O+K₂O)/P₂O₅2.5 to 13, preferably (Li)₂O+Na₂O+K₂O) /P₂O₅2.8 to 10, more preferably (Li)₂O+Na₂O+K₂O)/P₂O₅Is 3 to 7.

(48) The matrix glass according to any one of (45) to (47), which comprises, in terms of weight percent: SiO 2₂+Al₂O₃: 68-80%, preferably SiO₂+Al₂O₃: 70-78%; and/or P₂O₅: 3.5-9%, preferably P₂O₅: 4-8%; and/or ZrO₂: 1 to 6%, preferably ZrO₂: 1-5%; and/or Ln₂O₃: 0.5-8%, preferably Ln₂O₃: 1-7%; and/or Li₂O+Na₂O+K₂O: 22-28%; and/or MgO: 0 to 1 percent; and/or ZnO: 0 to 1 percent; and/or SrO: 0 to 3%, preferably SrO: 0 to 1 percent; and/or BaO: 0-3%, preferably BaO: 0 to 1 percent; and/or CaO: 0-3%, preferably CaO: 0 to 1 percent; and/or TiO₂: 0 to 3%, preferably TiO₂: 0 to 1 percent; and/or B₂O₃: 0 to 3%, preferably B₂O₃: 0 to 1 percent; and/or a clarifying agent: 0-1%, preferably clarifying agent: 0 to 0.5 percent of Ln₂O₃Is La₂O₃、 Gd₂O₃、Y₂O₃、Yb₂O₃One or more of Sb as clarifying agent₂O₃、SnO₂、SnO、CeO₂One or more of (a).

(49) The matrix glass according to any one of (45) to (48), which comprises, in terms of weight percent: li₂O: 15 to 25%, preferably Li₂O：16～23％。

(50) The base glass according to any one of (45) to (49), wherein the base glass has a thermal expansion coefficient of 70X 10^-7/K～90×10^-7And/or a refractive index of 1.5300 to 1.5500.

(51) The matrix glass according to any one of (45) to (50), wherein the matrix glass contains a colorant.

(52) The matrix glass according to (51), wherein the colorant comprises, in weight percent: NiO: 0 to 4 percent; and/or Ni₂O₃: 0 to 4 percent; and/or a CoO: 0-2%; and/or Co₂O₃: 0 to 2 percent; and/or Fe₂O₃: 0 to 7 percent; and/or MnO₂: 0 to 4 percent; and/or Er₂O₃: 0-8%; and/or Nd₂O₃: 0-8%; and/or Cu₂O: 0 to 4 percent; and/or Pr₂O₃: 0-8%; and/or CeO₂：0～ 4％。

(53) The matrix glass according to any one of (51) or (52), wherein the colorant comprises, in terms of weight percent: NiO: 0.1-4%; and/or Ni₂O₃: 0.1-4%; and/or a CoO: 0.05 to 2 percent; and/or Co₂O₃: 0.05-2%; and/or Fe₂O₃: 0.2-7%; and/or MnO₂: 0.1-4%; and/or Er₂O₃: 0.4-8%; and/or Nd₂O₃: 0.4-8%; and/or Cu₂O: 0.5-4%; and/or Pr₂O₃: 0.4-8%; and/or CeO₂：0.5～4％。

(54) The matrix glass according to any one of (51) or (52), wherein the colorant comprises, in terms of weight percent: NiO: 0.1-3%; and/or Ni₂O₃: 0.1-3%; and/or a CoO: 0.05 to 1.8 percent; and/or Co₂O₃: 0.05-1.8%; and/or Fe₂O₃: 0.2-5%; and/or MnO₂: 0.1 to 3 percent; and/or Er₂O₃: 0.4-6%; and/or Nd₂O₃: 0.4-6%; and/or Cu₂O: 0.5-3%; and/or Pr₂O₃: 0.4-6%; and/or CeO₂：0.5～3％。

(55) The matrix glass according to any one of (51) or (52), wherein the colorant comprises, in terms of weight percent: NiO: 0.1-3%; and/or Ni₂O₃：0.1～3％。

(56) The matrix glass according to any one of (51) or (52), wherein the colorant comprises, in terms of weight percent: and (3) CoO: 0.05-1.8%; and/or Co₂O₃：0.05～1.8％。

(57) The matrix glass according to any one of (51) or (52), wherein the colorant comprises, in terms of weight percent: cu₂O: 0.5-3%; and/or CeO₂：0.5～3％。

(58) The matrix glass according to any one of (51) or (52), wherein the colorant comprises, in terms of weight percent: fe₂O₃: 0.2-5%, CoO: 0.05-0.3%; or Fe₂O₃：0.2～ 5％、Co₂O₃: 0.05-0.3%; or Fe₂O₃: 0.2-5%, CoO: 0.05-0.3%, NiO: 0.1-1%; or Fe₂O₃：0.2～5％、Co₂O₃：0.05～0.3％、NiO：0.1～1％。

(59) The matrix glass according to any one of (51) or (52), wherein the colorant comprises, in terms of weight percent: pr (Pr) of₂O₃: 0.4-6%; or Fe₂O₃: 0.2-5%; or MnO₂: 0.1 to 3 percent; or Er₂O₃: 0.4-6%; or Nd₂O₃：0.4～6％。

(60) The matrix glass according to any one of (51) or (52), wherein the colorant comprises, in terms of weight percent: er₂O₃：0.4～6％、Nd₂O₃：0.4～4％、MnO₂：0.1～2％。

(61) A glass cover plate comprising the glass-ceramic product according to any one of (1) to (22), the glass-ceramic according to any one of (23) to (44), and/or the matrix glass according to any one of (45) to (60).

(62) A glass component comprising the glass-ceramic product according to any one of (1) to (22), the glass-ceramic according to any one of (23) to (44), and/or the matrix glass according to any one of (45) to (60).

(63) A display device comprising the glass-ceramic product according to any one of (1) to (22), and/or the glass-ceramic according to any one of (23) to (44), and/or the matrix glass according to any one of (45) to (60), and/or the glass cover plate according to (61), and/or the glass component according to (62).

(64) An electronic device comprising the glass-ceramic article according to any one of (1) to (22), and/or the glass-ceramic according to any one of (23) to (44), and/or the matrix glass according to any one of (45) to (60), and/or the glass cover plate according to (61), and/or the glass component according to (62).

(65) A method of making a crystallized glass article, the method comprising the steps of:

forming a matrix glass, forming a microcrystalline glass by a crystallization process on the matrix glass, and forming a microcrystalline glass product by a chemical strengthening process on the microcrystalline glass, wherein the microcrystalline glass product contains lithium metasilicate, quartz and quartz solid solution crystal phases, the total content of the lithium metasilicate, the quartz and the quartz solid solution crystal phases has higher weight percentage than other crystal phases, and the microcrystalline glass product comprises the following components in percentage by weight: SiO 2₂+Al₂O₃：60～80％；P₂O₅：2～10％；ZrO₂：0.5～ 10％；Ln₂O₃: greater than 0 but less than or equal to 10%; li₂O+Na₂O+K₂O: 21.5 to 30% of (SiO)₂+Al₂O₃)/Ln₂O₃7 or more, said Ln₂O₃Is La₂O₃、Gd₂O₃、Y₂O₃、Yb₂O₃One or more of (a).

(66) A method of making a crystallized glass article, the method comprising the steps of:

forming matrix glass, forming microcrystalline glass by using the matrix glass through a crystallization process, and forming a microcrystalline glass product by using the microcrystalline glass through a chemical strengthening process, wherein the microcrystalline glass product comprises the following components in percentage by weight: SiO 2₂+Al₂O₃：60～80％；P₂O₅：2～10％；ZrO₂： 0.5～10％；Ln₂O₃: greater than 0 but less than or equal to 10%; li₂O+Na₂O+K₂O: 21.5 to 30% of (SiO)₂+Al₂O₃)/Ln₂O₃7 or more, said Ln₂O₃Is La₂O₃、Gd₂O₃、Y₂O₃、Yb₂O₃One or more of (a).

(67) The method for manufacturing a crystallized glass article according to any one of (65) and (66), wherein the crystallized glass article further comprises, in terms of weight percent: MgO: 0-2%; and/or ZnO: 0-2%; and/or SrO: 0 to 5 percent; and/or BaO: 0 to 5 percent; and/or CaO: 0 to 5 percent; and/or TiO₂: 0 to 5 percent; and/or B₂O₃: 0 to 5 percent; and/or a clarifying agent: 0-2% of a clarifying agent Sb₂O₃、 SnO₂、SnO、CeO₂One or more of (a).

(68) The method for producing a crystallized glass product according to any one of (65) to (67), the crystallized glass product having the following components in percentage by weight: (SiO)₂+Al₂O₃)/Ln₂O₃From 10 to 72, preferably (SiO)₂+Al₂O₃)/Ln₂O₃Is 11 to 50, more preferably (SiO)₂+Al₂O₃)/Ln₂O₃Is 12 to 30; and/or (SiO)₂+Al₂O₃)/ZrO₂Is in the range of 10 to 80,preferably (SiO)₂+Al₂O₃)/ZrO₂15 to 50, more preferably (SiO)₂+Al₂O₃)/ZrO₂20 to 40; and/or (Li)₂O+Na₂O+K₂O)/P₂O₅From 2.5 to 13, preferably (Li)₂O+Na₂O+K₂O)/P₂O₅2.8 to 10, more preferably (Li)₂O+Na₂O+K₂O)/P₂O₅Is 3 to 7.

(69) The method for producing a crystallized glass product according to any one of (65) to (68), wherein the crystallized glass product comprises, in terms of weight percent: SiO 2₂+Al₂O₃: 68-80%, preferably SiO₂+Al₂O₃: 70-78%; and/or P₂O₅: 3.5-9%, preferably P₂O₅: 4-8%; and/or ZrO₂: 1 to 6%, preferably ZrO₂: 1-5%; and/or Ln₂O₃: 0.5-8%, preferably Ln₂O₃: 1 to 7 percent; and/or Li₂O+Na₂O+K₂O: 22-28%; and/or MgO: 0 to 1 percent; and/or ZnO: 0 to 1 percent; and/or SrO: 0 to 3%, preferably SrO: 0 to 1 percent; and/or BaO: 0-3%, preferably BaO: 0 to 1 percent; and/or CaO: 0-3%, preferably CaO: 0 to 1 percent; and/or TiO₂: 0 to 3%, preferably TiO₂: 0 to 1 percent; and/or B₂O₃: 0 to 3%, preferably B₂O₃: 0 to 1 percent; and/or a clarifying agent: 0-1%, preferably clarifying agent: 0 to 0.5 percent of Ln₂O₃Is La₂O₃、Gd₂O₃、Y₂O₃、Yb₂O₃One or more of Sb as clarifying agent₂O₃、SnO₂、SnO、CeO₂One or more of (a).

(70) The method for producing a crystallized glass product according to any one of (65) to (69), wherein the crystallized glass product comprises the following components in percentage by weight: li₂O: 15 to 25%, preferably Li₂O： 16～23％。

(71) The method for producing a crystallized glass product according to any one of (65) to (70), wherein the crystallization process includes the steps of: raising the temperature to a specified crystallization treatment temperature, keeping the temperature for a certain time after reaching the crystallization treatment temperature, and then reducing the temperature, wherein the crystallization treatment temperature is 600-750 ℃, preferably 650-700 ℃, and the keeping time at the crystallization treatment temperature is 0-8 hours, preferably 1-6 hours.

(72) The method for producing a crystallized glass product according to any one of (65) to (70), wherein the crystallization process includes the steps of: the treatment of the nucleation process is performed at the 1 st temperature, and then the treatment of the crystal growth process is performed at the 2 nd temperature higher than the nucleation process temperature.

(73) The method for manufacturing a crystallized glass article according to (72), wherein the crystallization process includes the steps of: the temperature of the No. 1 is 470-600 ℃, and the temperature of the No. 2 is 600-750 ℃; the holding time at the temperature of 1 st is 0 to 24 hours, preferably 2 to 15 hours; the holding time at the 2 nd temperature is 0 to 10 hours, preferably 0.5 to 6 hours.

(74) The method for producing a crystallized glass product according to any one of (65) to (73), wherein the chemical strengthening process comprises: immersing the microcrystalline glass in a salt bath of molten Na salt at the temperature of 320-470 ℃ for 6-20 hours, wherein the preferred temperature range is 360-460 ℃, and the preferred time range is 8-13 hours; and/or immersing the microcrystalline glass in a salt bath for melting K salt at the temperature of 340-450 ℃ for 1-24 hours, wherein the preferable time range is 2-10 hours; and/or immersing the microcrystalline glass in a salt bath of a molten K salt and a molten Na salt at the temperature of 340-450 ℃ for 1-24 hours, wherein the preferable time range is 2-10 hours.

(75) The method for producing a crystallized glass product according to any one of (65) to (74), wherein the crystallized glass product contains 20 to 60% by weight of a lithium monosilicate crystal phase, preferably 25 to 55% by weight of the crystallized glass product, more preferably 30 to 50% by weight of the crystallized glass product, and/or 45% or less by weight of a quartz and quartz solid solution crystal phase, preferably 5 to 40% by weight of the crystallized glass product.

(76) The method for producing a crystallized glass product according to any one of (65) to (75), wherein the crystallized glass product has a four-point bending strength of 600MPa or more, preferably 650MPa or more, and more preferably 700MPa or more; and/or the depth of the ion exchange layer is 20 μm or more, preferably 30 μm or more, more preferably 40 μm or more; and/or the ball drop test height is 1200mm or more, preferably 1300mm or more, more preferably 1400mm or more; and/or a fracture toughness of 1MPa m^1/2Above, preferably 1.1MPa · m¹ ^/2More preferably 1.2MPa · m or more^1/2The above; and/or a Vickers hardness of 680kgf/mm²Above, preferably 700kgf/mm²Above, 720kgf/mm is more preferable²The above; and/or a crystallinity of 50% or more, preferably 60% or more, more preferably 70% or more; and/or the crystal grain size is 60nm or less, preferably 50nm or less, more preferably 30nm or less.

(77) The method for producing a crystallized glass product according to any one of (65) to (76), wherein the crystallized glass product having a thickness of 1mm or less has a haze of 0.2% or less, preferably 0.17% or less, more preferably 0.15% or less; and/or an average transmittance at a wavelength of 400 to 800nm of 87% or more, preferably 89% or more, more preferably 90% or more; and/or a 550nm wavelength transmittance of 88% or more, preferably 90% or more, more preferably 91% or more.

(78) The method for producing a crystallized glass product according to (77), wherein the crystallized glass product has a thickness of 0.2 to 1mm, preferably 0.3 to 0.9mm, more preferably 0.5 to 0.8mm, and further preferably 0.55mm, 0.6mm, 0.68mm, 0.7mm, or 0.75 mm.

(79) A method for producing a crystallized glass, comprising the steps of:

forming a matrix glass, and crystallizing the matrix glass to form a microcrystalline glass, wherein the microcrystalline glass comprises a lithium silicate and quartz solid solution crystalline phase, the total content of the lithium silicate and quartz solid solution crystalline phase has a higher weight percentage than other crystalline phases, and the microcrystalline glass comprises the following components in percentage by weightThe composition contains the following components in percentage by weight: SiO 2₂+Al₂O₃：60～80％；P₂O₅：2～10％；ZrO₂： 0.5～10％；Ln₂O₃: greater than 0 but less than or equal to 10%; li₂O+Na₂O+K₂O: 21.5 to 30% of (SiO)₂+Al₂O₃)/Ln₂O₃7 or more, said Ln₂O₃Is La₂O₃、Gd₂O₃、Y₂O₃、Yb₂O₃One or more of (a).

(80) A method for producing a crystallized glass, comprising the steps of:

forming matrix glass, and then forming microcrystalline glass from the matrix glass through a crystallization process, wherein the microcrystalline glass comprises the following components in percentage by weight: SiO 2₂+Al₂O₃：60～80％；P₂O₅：2～ 10％；ZrO₂：0.5～10％；Ln₂O₃: greater than 0 but less than or equal to 10%; li₂O+Na₂O+K₂O: 21.5 to 30% of (SiO)₂+Al₂O₃)/Ln₂O₃7 or more, said Ln₂O₃Is La₂O₃、Gd₂O₃、 Y₂O₃、Yb₂O₃One or more of (a).

(81) The method for producing a glass ceramic according to any one of (79) and (80), wherein the glass ceramic further contains, in terms of the components by weight: MgO: 0-2%; and/or ZnO: 0-2%; and/or SrO: 0 to 5 percent; and/or BaO: 0 to 5 percent; and/or CaO: 0 to 5 percent; and/or TiO₂: 0 to 5 percent; and/or B₂O₃: 0 to 5 percent; and/or a clarifying agent: 0-2% of a clarifying agent Sb₂O₃、SnO₂、 SnO、CeO₂One or more of (a).

(82) The process for producing a crystallized glass according to any one of (79) to (81), wherein the crystallized glass comprises the following components in percentage by weight: (SiO)₂+Al₂O₃)/Ln₂O₃10 to 72, preferably (SiO)₂+Al₂O₃)/Ln₂O₃Is 11 to 50, more preferably (SiO)₂+Al₂O₃)/Ln₂O₃12 to 30; and/or (SiO)₂+Al₂O₃)/ZrO₂10 to 80, preferably (SiO)₂+Al₂O₃)/ZrO₂15 to 50, more preferably (SiO)₂+Al₂O₃)/ZrO₂20 to 40; and/or (Li)₂O+Na₂O+K₂O)/P₂O₅2.5 to 13, preferably (Li)₂O+Na₂O+K₂O)/P₂O₅2.8 to 10, more preferably (Li)₂O+Na₂O+K₂O)/P₂O₅Is 3 to 7.

(83) The process for producing a crystallized glass according to any one of (79) to (82), wherein the crystallized glass comprises, in terms of the components by weight: SiO 2₂+Al₂O₃: 68-80%, preferably SiO₂+Al₂O₃: 70-78%; and/or P₂O₅: 3.5-9%, preferably P₂O₅: 4-8%; and/or ZrO₂: 1 to 6%, preferably ZrO₂: 1-5%; and/or Ln₂O₃: 0.5-8%, preferably Ln₂O₃: 1-7%; and/or Li₂O+Na₂O+K₂O: 22-28%; and/or MgO: 0 to 1 percent; and/or ZnO: 0 to 1 percent; and/or SrO: 0 to 3%, preferably SrO: 0 to 1 percent; and/or BaO: 0-3%, preferably BaO: 0 to 1 percent; and/or CaO: 0-3%, preferably CaO: 0 to 1 percent; and/or TiO₂: 0 to 3%, preferably TiO₂: 0 to 1 percent; and/or B₂O₃: 0 to 3%, preferably B₂O₃: 0 to 1 percent; and/or a clarifying agent: 0-1%, preferably clarifying agent: 0 to 0.5 percent of Ln₂O₃Is La₂O₃、Gd₂O₃、Y₂O₃、Yb₂O₃One or more of Sb as clarifying agent₂O₃、SnO₂、 SnO、CeO₂One or more of (a).

(84) The process for producing a crystallized glass according to any one of (79) to (83), wherein the crystallized glass comprises, in terms of the components by weight: li₂O: 15 to 25%, preferably Li₂O：16～23％。

(85) The method for producing crystallized glass according to any one of (79) to (84), wherein the crystallization process includes the steps of: raising the temperature to a specified crystallization treatment temperature, keeping the temperature for a certain time after reaching the crystallization treatment temperature, and then reducing the temperature, wherein the crystallization treatment temperature is 600-750 ℃, preferably 650-700 ℃, and the keeping time at the crystallization treatment temperature is 0-8 hours, preferably 1-6 hours.

(86) The method for producing crystallized glass according to any one of (79) to (84), wherein the crystallization process includes the steps of: the treatment of the nucleation process is performed at the 1 st temperature, and then the treatment of the crystal growth process is performed at the 2 nd temperature higher than the nucleation process temperature.

(87) The method for manufacturing microcrystalline glass according to (86), wherein the crystallization process comprises the following steps: the temperature of the No. 1 is 470-600 ℃, and the temperature of the No. 2 is 600-750 ℃; the holding time at the temperature of 1 st is 0 to 24 hours, preferably 2 to 15 hours; the holding time at the 2 nd temperature is 0 to 10 hours, preferably 0.5 to 6 hours.

(88) The method for producing a crystallized glass according to any one of (79) to (87), wherein the crystallized glass contains 20 to 60% by weight of a lithium monosilicate crystal phase, preferably 25 to 55% by weight of the crystallized glass, more preferably 30 to 50% by weight of the crystallized glass, and/or 45% or less by weight of a quartz and quartz solid solution crystal phase, preferably 5 to 40% by weight of the crystallized glass.

(89) The process for producing a crystallized glass according to any one of (79) to (88), wherein the crystallized glass has a body falling ball test height of 1100mm or more, preferably 1200mm or more, more preferably 1300mm or more; and/or Vickers hardnessIs 650kgf/mm²Above, it is preferably 660kgf/mm²Above, more preferably 670kgf/mm²The above; and/or a crystallinity of 50% or more, preferably 60% or more, more preferably 70% or more; and/or a crystal grain size of 60nm or less, preferably 50nm or less, more preferably 30nm or less; and/or a coefficient of thermal expansion of 90 x 10^-7/K～100×10^-7K; and/or the refractive index is 1.5500-1.5700.

(90) The process for producing a crystallized glass according to any one of (79) to (89), wherein the crystallized glass having a thickness of 1mm or less has a haze of 0.2% or less, preferably 0.17% or less, more preferably 0.15% or less; and/or an average transmittance at a wavelength of 400 to 800nm of 87% or more, preferably 89% or more, more preferably 90% or more; and/or a 550nm wavelength transmittance of 88% or more, preferably 90% or more, more preferably 91% or more.

(91) The method for producing a glass ceramic according to (90), wherein the glass ceramic has a thickness of 0.2 to 1mm, preferably 0.3 to 0.9mm, more preferably 0.5 to 0.8mm, and still more preferably 0.55mm, 0.6mm, 0.68mm, 0.7mm, or 0.75 mm.

The invention has the beneficial effects that: through reasonable component design, the microcrystalline glass and the microcrystalline glass product obtained by the invention have excellent mechanical property and optical property, and are suitable for electronic equipment or display equipment.

Detailed Description

The crystallized glass and the crystallized glass article of the present invention are materials having a crystal phase and a glass phase, which are different from amorphous solids. The crystalline phases of the glass-ceramic and glass-ceramic articles can be identified by the angle of the peak appearing in the X-ray diffraction pattern of the X-ray diffraction analysis and/or measured by TEMEDX.

The inventors of the present invention have made extensive experiments and studies, and have obtained a crystallized glass or a crystallized glass product of the present invention at a low cost by specifying the content and content ratio of specific components constituting a crystallized glass or a crystallized glass product to specific values and precipitating specific crystal phases.

The ranges of the respective components (components) of the matrix glass, the glass ceramics and the glass ceramics product of the present invention will be described below. In the present specification, the contents of the respective components are all expressed in weight percent (wt%) with respect to the total amount of the substance of the matrix glass, or the glass ceramics product converted into the composition of the oxide, if not specifically stated. Here, the "composition in terms of oxide" means that when an oxide, a complex salt, a hydroxide, or the like used as a raw material of a composition component of a matrix glass, a glass-ceramic, or a glass-ceramic product of the present invention is decomposed at melting and converted into an oxide, the total amount of the oxide is 100%. In the present specification, the term "glass" refers to a matrix glass before crystallization, the term "glass matrix" refers to a crystallized glass after crystallization, and the term "glass-ceramic product" refers to a chemically strengthened glass-ceramic.

Unless otherwise indicated in a specific context, numerical ranges set forth herein include upper and lower values, and "above" and "below" include end-point values, as well as all integers and fractions within the range, and are not limited to the specific values recited in the defined range. The term "about" as used herein means that the formulations, parameters, and other quantities and characteristics are not, and need not be, exact, and can be approximate and/or larger or smaller, if desired, reflecting tolerances, conversion factors, measurement error and the like. The term "and/or" as used herein is inclusive, e.g., "a; and/or B "means A alone, B alone, or both A and B.

In the crystallized glass or crystallized glass product of the present invention, the crystal phase contains lithium monosilicate; and/or quartz and quartz solid solutions; and/or lithium disilicate; and/or petalite.

In some embodiments of the present invention, the crystalline phases in the glass-ceramic or glass-ceramic article comprise lithium monosilicate and quartz solid solution, and the combined content of lithium monosilicate and quartz solid solution crystalline phases having a higher weight percentage than other crystalline phases is that the glass-ceramic or glass-ceramic article of the present invention has excellent mechanical properties.

In some embodiments, the lithium monosilicate crystalline phase comprises 20 to 60% by weight of the glass ceramic or glass ceramic article, in some embodiments, 25 to 55% by weight of the glass ceramic or glass ceramic article, and in some embodiments, 30 to 50% by weight of the glass ceramic or glass ceramic article.

In some embodiments, the quartz and quartz solid solution crystalline phase comprises less than 45% by weight of the microcrystalline glass or microcrystalline glass article, and in some embodiments, the quartz and quartz solid solution crystalline phase comprises 5-40% by weight of the microcrystalline glass or microcrystalline glass article.

In some embodiments, the lithium disilicate crystalline phase comprises less than 10% by weight of the glass ceramic or glass ceramic article, in some embodiments, the lithium disilicate crystalline phase comprises less than 8% by weight of the glass ceramic or glass ceramic article, and in some embodiments, the lithium disilicate crystalline phase comprises less than 5% by weight of the glass ceramic or glass ceramic article.

In some embodiments, the petalite crystalline phase comprises less than 10% by weight of the glass ceramic or glass ceramic article, in some embodiments, the petalite crystalline phase comprises less than 8% by weight of the glass ceramic or glass ceramic article, and in some embodiments, the petalite crystalline phase comprises less than 5% by weight of the glass ceramic or glass ceramic article.

SiO₂And Al₂O₃Is an essential component of the glass of the present invention, and can constitute the network structure of the glass of the present invention by incorporating SiO₂And Al₂O₃SiO in total content₂+Al₂O₃Controlling the content to be more than 60 percent, ensuring that the glass has excellent stability, improving the crystallinity and four-point bending strength of the microcrystalline glass and the microcrystalline glass product, and preferably selecting SiO₂+Al₂O₃Is 68% or more, and SiO is more preferable₂+Al₂O₃Is more than 70%. On the other hand, if SiO₂+Al₂O₃When the content exceeds 80%, the light transmittance of the microcrystalline glass and the microcrystalline glass product is reduced, the haze is increased, and the strengthening performance of the microcrystalline glass is deteriorated, so that SiO₂And Al₂O₃SiO in total content₂+Al₂O₃Is 80% or less, preferably 78% or less. In some embodiments, the SiO₂+Al₂O₃May be 60%, 61%, 62%, 63%, 64%, 65%, 66%, 67%, 68%, 69%, 70%, 71%, 72%, 73%, 74%, 75%, 76%, 77%, 78%, 79%, 80%.

P₂O₅Can form crystal nucleus in the process of glass crystallization, promote the formation of crystal, improve the crystallinity of the microcrystalline glass and the microcrystalline glass product, facilitate chemical strengthening, and increase the hardness, the falling ball height and the bending strength of the microcrystalline glass product, P₂O₅The lower limit of the content is 2%, preferably 3.5%, more preferably 4%. But if it contains P excessively₂O₅It easily causes phase separation of the glass and reduces the chemical stability of the glass. Thus, P₂O₅The upper limit of the content is 10%, preferably 9%, more preferably 8%. In some embodiments, about 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, 10% P may be included₂O₅。

ZrO₂And P₂O₅Can be mutually dissolved to reduce P₂O₅Phase separation is carried out during glass forming, the crystallization temperature of the glass can be increased during crystallization, the integrity degree of the crystalline phase in the microcrystalline glass and the microcrystalline glass product is ensured, the haze of the microcrystalline glass and the microcrystalline glass product is reduced, and the falling ball test height of the microcrystalline glass product is improved, so that ZrO₂The lower limit of the content is 0.5%, and the preferable lower limit is 1%. On the other hand, if ZrO is contained excessively₂The glass is difficult to melt, so that ZrO₂The upper limit of the content is 0%, preferably 6%, more preferably 5%. In some embodiments, about 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% ZrO may be included₂。

In some casesIn the embodiment, SiO₂And Al₂O₃SiO in total content₂+Al₂O₃And ZrO₂Ratio between contents of (A), (B), (C₂+Al₂O₃)/ZrO₂The hardness of the microcrystalline glass and the microcrystalline glass product can be effectively improved by controlling the content of the (SiO) in the range of 10-80, so that the (SiO) is preferred₂+Al₂O₃)/ZrO₂Is 10 to 80. Further, control (SiO)₂+Al₂O₃)/ZrO₂In the range of 15-50, the chemical strengthening performance of the microcrystalline glass can be optimized, and the ion exchange layer depth of the microcrystalline glass product is improved, so that (SiO) is more preferable₂+Al₂O₃) /ZrO₂Is 15 to 50, and (SiO) is more preferable₂+Al₂O₃)/ZrO₂Is 20 to 40. In some embodiments, (SiO)₂+Al₂O₃)/ZrO₂May be 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80.

Ln₂O₃(Ln₂O₃Is La₂O₃、Gd₂O₃、Y₂O₃、Yb₂O₃One or more of) can reduce the melting difficulty of glass, reduce phase separation in the glass, reduce the haze of the microcrystalline glass and the microcrystalline glass product, and improve the hardness and the chemical stability of the microcrystalline glass and the microcrystalline glass product, wherein the Ln is more than 0 percent₂O₃To obtain the above effects, it is preferable to contain 0.5% or more of Ln₂O₃More preferably, it contains 1% or more of Ln₂O₃. On the other hand, if too much Ln is contained₂O₃The difficulty of forming crystals during glass crystallization, the decrease of crystallinity of the glass ceramics and the glass ceramics products, and the influence on the chemical strengthening property of the glassCan reduce the strength of the glass-ceramic product, so Ln₂O₃The content of (b) is 10% or less, preferably 8% or less, more preferably 7% or less. In some embodiments, about greater than 0%, 0.01%, 0.05%, 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, 10% Ln may be included₂O₃。

In some embodiments of the invention, the SiO is prepared by reacting SiO₂And Al₂O₃SiO in total content₂+Al₂O₃And Ln₂O₃Ratio between contents of (A), (B), (C₂+Al₂O₃)/Ln₂O₃Control to 7 or more is preferable because the falling ball test height of the glass ceramics and the glass ceramics product can be increased₂+Al₂O₃)/Ln₂O₃Is 7 or more, more preferably (SiO)₂+Al₂O₃)/Ln₂O₃10 to 72. Further, by controlling (SiO)₂+Al₂O₃) /Ln₂O₃In the range of 11 to 50, the haze and the light transmittance of the microcrystalline glass and the microcrystalline glass product can be optimized, and the fracture toughness of the microcrystalline glass product can be improved, so that (SiO) is more preferable₂+Al₂O₃)/Ln₂O₃Is 11 to 50, and (SiO) is more preferable₂+Al₂O₃)/Ln₂O₃Is 12 to 30. In some embodiments, (SiO)₂+Al₂O₃)/Ln₂O₃The value of (a) may be 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, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72.

Alkali metal oxide Li₂O、Na₂O and K₂O can promote glass melting and reduce glass meltingThe temperature is favorable for the adjustment of the chemical strengthening process of the glass or the glass ceramics, and Li is added in the invention₂O、Na₂O and K₂Total content of O Li₂O+Na₂O+K₂O is controlled to 21.5% or more to obtain the above-mentioned effects, and Li is preferable₂O+Na₂O+K₂O is more than 22%. On the other hand, if the alkali metal oxide is contained excessively, phase separation of the glass is promoted, and the transmittance of the crystallized glass or crystallized glass product is lowered. Therefore, Li is preferable₂O+Na₂O+K₂O is 30% or less, and Li is more preferable₂O+Na₂O+K₂O is 28% or less. In some embodiments, Li₂O+Na₂O+K₂O may be 21.5%, 22%, 22.5%, 23%, 23.5%, 24%, 24.5%, 25%, 25.5%, 26%, 26.5%, 27%, 27.5%, 28%, 28.5%, 29%, 29.5%, 30%.

Li₂O is a main component for forming crystals and is also a component mainly substituted with sodium ions and potassium ions in chemical strengthening treatment, so that the depth of an ion exchange layer of the microcrystalline glass product after chemical strengthening can be increased, and the falling ball height of the microcrystalline glass product is improved. In some embodiments, if Li₂When the content of O is less than 15%, the crystal phase of lithium monosilicate is not formed well, and the falling ball height and the size of fragments of the crystallized glass article are affected, and therefore, Li₂The lower limit of the O content is preferably 15%, more preferably 16%. On the other hand, if Li is contained excessively₂O, which is liable to phase separation during crystallization, affects the transmittance of the glass-ceramic and the glass-ceramic product. Thus, Li₂The upper limit of the O content is preferably 25%, and more preferably 23%. In some embodiments, about 15%, 15.5%, 16%, 16.5%, 17%, 17.5%, 18%, 18.5%, 19%, 19.5%, 20%, 20.5%, 21%, 21.5%, 22%, 22.5%, 23%, 23.5%, 24%, 24.5%, 25% Li may be included₂O。

In some embodiments, the total content of alkali metal oxides, Li₂O+Na₂O+K₂O and P₂O₅Ratio between contents of(Li₂O+Na₂O+K₂O)/P₂O₅The content of (Li) is preferably controlled within a range of 2.5 to 13 because the crystal grains can be refined and the crystal grain sizes of the glass ceramics and the glass ceramics products can be reduced₂O+Na₂O+K₂O) /P₂O₅2.5 to 13. Further, reacting (Li)₂O+Na₂O+K₂O)/P₂O₅In the range of 2.8 to 10, the light transmittance of the glass ceramics and the glass ceramics product can be further improved, and the four-point bending strength of the glass ceramics product can be improved, and therefore (Li) is more preferable₂O+Na₂O+K₂O)/P₂O₅Is 2.8 to 10, and (Li) is more preferable₂O+Na₂O+K₂O)/P₂O₅Is 3 to 7. In some embodiments, (Li)₂O+Na₂O+K₂O)/P₂O₅The value of (a) may be 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, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, 5, 5.1, 5.2, 5.3, 5.4, 5.5, 5.6, 5.7, 5.8, 5.9, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, 10, 10.5, 11, 11.5, 12, 12.5, 13.

MgO can reduce the difficulty of glass melting and is beneficial to increasing the falling ball height of the microcrystalline glass and the microcrystalline glass product, but MgO can easily promote the low-temperature crystallization of the glass and reduce the crystallinity and the transmittance of the microcrystalline glass and the microcrystalline glass product, so the upper limit of the content of MgO is 2 percent, and the preferable upper limit is 1 percent. In some embodiments, 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% MgO may be included.

The content of ZnO can reduce the difficulty of glass melting, but when the content is high, the low-temperature crystallization of the glass is promoted, the crystallinity and transmittance of the glass ceramics and the glass ceramics products are reduced, and the haze of the glass ceramics and the glass ceramics products is increased, so the upper limit of the content is 2%, the upper limit is preferably 1%, and the content does not contain ZnO. In some embodiments, 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% ZnO may be included.

SrO is an optional component for improving the low-temperature melting property of the glass and suppressing devitrification at the time of glass forming, but is not favorable for glass forming when the content is too large. Therefore, in the present invention, the SrO content is in the range of 0 to 5%, preferably 0 to 3%, more preferably 0 to 1%, and further preferably no SrO is contained. In some embodiments, about 0%, greater than 0%, 0.01%, 0.05%, 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5% SrO may be included.

BaO is an optional component which contributes to the improvement of glass forming properties of the glass, and when the content is too large, glass forming is not facilitated. Therefore, the content of BaO in the present invention is in the range of 0 to 5%, preferably 0 to 3%, more preferably 0 to 1%, and further preferably contains no BaO. In some embodiments, BaO may be included at about 0%, greater than 0%, 0.01%, 0.05%, 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%.

CaO can increase the hardness of the glass, and when the content is too large, the glass is easy to be milky during forming. Therefore, in the present invention, the content of CaO is in the range of 0 to 5%, preferably 0 to 3%, more preferably 0 to 1%, and further preferably no CaO is contained. In some embodiments, CaO may be included at about 0%, greater than 0%, 0.01%, 0.05%, 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%.

TiO₂Is an optional component which is helpful for reducing the melting temperature of the glass and improving the chemical stability, and the content of TiO is less than 5 percent in the invention₂The crystallization process of the glass can be easily controlled, and TiO is preferred₂The content of (b) is 3% or less, more preferably 1% or less. In some embodiments, it is further preferred that no TiO is present₂. In some embodiments, about 0%, greater than 0%, 0.01%, 0.05%, 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%5% of TiO₂。

B₂O₃Can improve the network structure of the glass, adjust the chemical strengthening performance of the glass ceramics, if the content is too much, the glass shaping is not good, and the glass is easy to crystallize during shaping, therefore, B₂O₃The upper limit of the content is 5%, preferably 3%, more preferably 1%, and further preferably B is not contained₂O₃. In some embodiments, about 0%, greater than 0%, 0.01%, 0.05%, 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5% B may be included₂O₃。

In some embodiments, the glass, microcrystalline glass or microcrystalline glass product can further comprise 0-2% of a fining agent to improve the defoaming capability of the glass, microcrystalline glass or microcrystalline glass product. Such fining agents include, but are not limited to, Sb₂O₃、SnO₂SnO and CeO₂Preferably Sb₂O₃As a clarifying agent. The upper limit of the content of the above-mentioned clarifying agent, when it is present alone or in combination, is preferably 1%, more preferably 0.5%. In some embodiments, one or more of the above fining agents are present in an amount of about 0%, greater than 0%, 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%.

In order to obtain the desired excellent properties of the glass, glass-ceramic or glass-ceramic article of the present invention, such as mechanical properties, optical properties, productivity and chemical strengthening properties, it is preferred in some embodiments of the present invention that F is not included; and/or does not contain Ta₂O₅。

PbO and As₂O₃Are toxic substances and are not environmentally friendly even when added in small amounts, and thus the present invention preferably does not contain PbO and As in some embodiments₂O₃。

In some embodiments of the present invention, a colored matrix glass, glass ceramic or glass ceramic can be prepared by including a colorantAn article capable of imparting a different color to a substrate glass, glass ceramic or glass ceramic article, the colorant comprising: NiO: 0 to 4 percent; and/or Ni₂O₃: 0 to 4 percent; and/or a CoO: 0-2%; and/or Co₂O₃: 0-2%; and/or Fe₂O₃: 0 to 7 percent; and/or MnO₂: 0 to 4 percent; and/or Er₂O₃: 0-8%; and/or Nd₂O₃: 0-8%; and/or Cu₂O: 0 to 4 percent; and/or Pr₂O₅: 0-8%; and/or CeO₂: 0 to 4 percent. The content of the colorant in percentage by weight and the function thereof are detailed as follows:

NiO and Ni are used for preparing the brown or green matrix glass, the microcrystalline glass or the microcrystalline glass product₂O₃Or Pr₂O₅Is a colorant. NiO and Ni₂O₃For the colouring agent, for the preparation of a brown or green matrix glass, glass ceramic or glass ceramic product, the two components can be used individually or in admixture, each in a content of generally less than 4%, preferably less than 3%, and if the content exceeds 4%, the colouring agent is not very soluble in the matrix glass, glass ceramic or glass ceramic product, each in a content below 0.1%, such as below 0.1%, and the matrix glass, glass ceramic or glass ceramic product is not visibly coloured. In some embodiments, about 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2.0%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3.0%, 3.1%, 3.2%, 3.3%, 3.4%, 3.5%, 3.6%, 3.7%, 3.8%, 3.9%, 4.0% NiO or Ni may be included₂O₃. NiO and Ni, if used in admixture₂O₃The total amount is generally 4% or less, and the lower limit of the total amount is 0.1% or more. In some embodiments, 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 may be included.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. Using Pr₂O₅The colorant for green matrix glass, glass ceramics or glass ceramics is used alone, and is generally contained in an amount of 8% or less, preferably 6% or less, and the lower limit of the content is 0.4% or more, for example, less than 0.4%, and the matrix glass, glass ceramics or glass ceramics product is not conspicuous in color. In some embodiments, 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% Pr may be included₂O₅。

The blue matrix glass, the microcrystalline glass or the microcrystalline glass product prepared by the invention uses CoO or Co₂O₃The two colorant components may be used alone or in combination as a colorant, and their respective contents are generally 2% or less, preferably 1.8% or less, and if the content exceeds 2%, the colorant is not well soluble in the matrix glass, the crystallized glass or the crystallized glass product, and its respective lower limit is 0.05% or more, e.g., less than 0.05%, and the matrix glass, the crystallized glass or the crystallized glass product is not conspicuous in color. In some embodiments, 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% of CoO or Co may be included₂O₃. CoO and Co, if used in admixture₂O₃The total amount is not more than 2%, and the lower limit of the total amount is not less than 0.05%. In some embodiments, 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%, 1.2%7%, 1.8%, 1.9%, 2.0% CoO and Co₂O₃。

The yellow matrix glass, the microcrystalline glass or the microcrystalline glass product prepared by the invention uses Cu₂O or CeO₂The two colorant components are used alone or in combination as colorant, and have a lower limit of 0.5% or more, such as less than 0.5%, no apparent color of the matrix glass, microcrystalline glass or microcrystalline glass product, and Cu alone₂O is 4% or less, preferably 3% or less, and if the content exceeds 4%, the matrix glass is easily crystallized. In some embodiments, 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% Cu may be included₂And O. Using CeO alone₂The content is generally 4% or less, preferably 3% or less, and if the content exceeds 4%, the substrate glass, the crystallized glass or the crystallized glass product is poor in gloss. In some embodiments, CeO 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% may be included₂. At the same time, a small amount of CeO₂Added to glass with a defoaming effect, CeO₂Can also be used as a clarifying agent in glass. When two kinds of 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, 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%, 3.0%, 3.1%, 3.2%, 3.3%, 3.4%, 3.5%, 3.6%, 3.7%, 3.8% may be includedCeO in percentages of 3.9% and 4.0%₂And Cu₂O。

The black or smoke gray matrix glass, the microcrystalline glass or the microcrystalline glass product prepared by the invention independently uses Fe₂O₃Is a colorant; or using Fe₂O₃And CoO; or using Fe₂O₃And Co₂O₃Two colorants used in combination; or using Fe₂O₃Three colorants mixed together, CoO and NiO; or using Fe₂O₃、Co₂O₃And NiO. Colorants for the production of black and smoky grey matrix glass, glass ceramics or glass ceramic articles using predominantly Fe₂O₃Coloration, less than 7%, preferably less than 5%, with a lower limit of 0.2% or more, and in some embodiments, 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% or more of Fe can be included₂O₃. CoO and Co₂O₃Can absorb visible light to increase the coloring degree of matrix glass, microcrystalline glass or microcrystalline glass products, and is generally combined with Fe₂O₃The content of each component is 0.6% or less, and the lower limit is 0.2% or more. In some embodiments, about 0.2%, 0.3%, 0.4%, 0.5%, 0.6% CoO and/or Co may be included₂O₃. NiO absorbs visible light and can increase the degree of coloration of the base glass, glass ceramic or glass ceramic product, and is generally used in a mixture in which the content is 1% or less and the lower limit of the total amount is 0.2% or more. In some embodiments, NiO may be included at about 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%.

The purple matrix glass prepared by the invention,Microcrystalline glass or microcrystalline glass articles using MnO₂As a coloring agent, it is used in an amount of generally 4% or less, preferably 3% or less, and the lower limit thereof is 0.1% or more, for example, less than 0.1%, and the color of the matrix glass, the glass ceramics or the glass ceramics article is not conspicuous. In some embodiments, MnO of 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% may be included₂。

Er is used in the pink substrate glass, the microcrystalline glass or the microcrystalline glass product prepared by the invention₂O₃The content of the colorant used is generally 8% or less, preferably 6% or less. Because of rare earth element Er₂O₃The coloring efficiency is low, when the content exceeds 8%, the color of the matrix glass, the microcrystalline glass or the microcrystalline glass product cannot be further deepened, and the cost is increased, and the lower limit of the content is more than 0.4%, such as less than 0.4%, and the color of the matrix glass, the microcrystalline glass or the microcrystalline glass product is not obvious. In some embodiments, 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% Er may be included₂O₃。

The mauve substrate glass, the microcrystalline glass or the microcrystalline glass product prepared by the invention uses Nd₂O₃The content of the colorant used is generally 8% or less, preferably 6% or less. Due to rare earth element Nd₂O₃The coloring efficiency is low, the use content exceeds 8 percent, the color of the matrix glass, the microcrystalline glass or the microcrystalline glass product cannot be further deepened, but the cost is increased, and the coloring agent containsThe lower limit of the amount is more than 0.4%, for example, less than 0.4%, and the color of the matrix glass, the microcrystalline glass or the microcrystalline glass product is not obvious. In some embodiments, 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% Nd may be included₂O₃。

Er is used for the red matrix glass, the microcrystalline glass or the microcrystalline glass product prepared by the invention₂O₃、 Nd₂O₃And MnO₂The mixed colorant, Er ion in the glass has absorption at 400-500nm, Mn ion has absorption mainly at 500nm, Nd ion has strong absorption mainly at 580nm, and the mixture of the three substances can prepare red matrix glass, microcrystalline glass or microcrystalline glass product₂O₃And Nd₂O₃Coloring rare earth, relatively weak coloring ability, Er₂O₃The usage amount is less than 6 percent, Nd₂O₃The usage amount is less than 4 percent, MnO₂The coloring is strong, the usage amount is within 2 percent, and the lower limit of the total amount of the mixed coloring agent is more than 0.9 percent.

"0%" or "0%" is not included in the present invention, and means that the compound, molecule, element or the like is not intentionally added as a raw material to the matrix glass, the glass ceramic or the glass ceramic product of the present invention; it is within the scope of the present invention that certain impurities or components, which are not intentionally added, may be present as raw materials and/or equipment for producing the matrix glass, microcrystalline glass or microcrystalline glass article and may be present in small or trace amounts in the final matrix glass, microcrystalline glass or microcrystalline glass article.

In some embodiments of the present invention, the crystalline phase in the microcrystalline glass and microcrystalline glass articles comprises lithium metasilicate and quartz solid solution, which provides the microcrystalline glass and microcrystalline glass articles of the present invention with high strength and high fracture toughness; the height of the falling ball test and the four-point bending strength of the microcrystalline glass and the microcrystalline glass product become large. The microcrystalline glass has excellent chemical strengthening performance, and can obtain additional mechanical strength through chemical strengthening. Through reasonable component design, the microcrystalline glass and the microcrystalline glass product can obtain proper grain size, and the microcrystalline glass product have high strength. The microcrystalline glass and the microcrystalline glass product have good crystallinity, so that the microcrystalline glass and the microcrystalline glass product have excellent mechanical properties. The crystallinity is the complete degree of crystallization, the arrangement of mass points in the complete crystal is regular, the diffraction line is strong, sharp and symmetrical, and the half-height width of a diffraction peak is close to the width measured by an instrument; the crystals with poor crystallinity have defects such as dislocation and the like, so that diffraction line peaks are wide and diffuse. The poorer the crystallinity, the weaker the diffraction power, the wider the diffraction peak until it disappears in the background. In some embodiments, the microcrystalline glass article or microcrystalline glass has a crystallinity of 50% or more, preferably 60% or more, and more preferably 70% or more.

The size and the type of crystal grains in the microcrystalline glass or the microcrystalline glass product can influence the haze and the transmittance of the microcrystalline glass or the microcrystalline glass product, and the smaller the crystal grain is, the higher the transmittance is; the smaller the haze, the higher the transmittance. In some embodiments, the haze of the microcrystalline glass article or microcrystalline glass having a thickness of 1mm or less is 0.2% or less, preferably 0.17% or less, and more preferably 0.15% or less. In some embodiments, the crystallite glass article or crystallite glass has a grain size of 60nm or less, preferably 50nm or less, more preferably 30nm or less.

In some embodiments, the microcrystalline glass or microcrystalline glass article of the present invention exhibits high transparency in the visible range (i.e., the microcrystalline glass or microcrystalline glass article is transparent). The microcrystalline glass or the microcrystalline glass product has a high transmittance in the visible light range, and in some embodiments, the microcrystalline glass product or the microcrystalline glass having a thickness of 1mm or less preferably has an average light transmittance of 90% or more in the range of 400 to 800 nm. In some preferred embodiments, the microcrystalline glass product or microcrystalline glass having a thickness of 1mm or less preferably has a light transmittance of 91% or more at 550 nm.

In some embodiments, an antimicrobial component may be added to the matrix glass, microcrystalline glass, or microcrystalline glass article. The crystallized glass or crystallized glass article described herein may be used in applications such as kitchens or countertops where exposure to harmful bacteria is likely. Antimicrobial components that may be added to the matrix glass, glass-ceramic, or glass-ceramic article include, but are not limited to, Ag, AgO, Cu, CuO, Cu₂O, and the like. In some embodiments, the antimicrobial components described above are present at 2% or less, preferably 1% or less, alone or in combination.

The matrix glass, the glass-ceramic and the glass-ceramic product of the invention can be produced and manufactured by the following methods:

and (3) generation of matrix glass: the raw materials are uniformly mixed according to the component proportion, the uniform mixture is put into a crucible made of platinum or quartz, and the melting is carried out for 5 to 24 hours in an electric furnace or a gas furnace within the temperature range of 1250 to 1650 ℃ according to the melting difficulty of the glass composition. Melting, stirring to make it uniform, cooling to proper temperature, casting into mould, and slowly cooling.

The matrix glass of the present invention can be shaped by a well-known method.

The matrix glass of the invention is crystallized by a crystallization process after molding or after molding processing, and crystals are uniformly precipitated in the glass. The crystallization may be performed in 1 stage or 2 stages, and preferably 2 stages. The treatment of the nucleation process is performed at the 1 st temperature, and then the treatment of the crystal growth process is performed at the 2 nd temperature higher than the nucleation process temperature. The crystallization process performed at the 1 st temperature is referred to as a 1 st crystallization process, and the crystallization process performed at the 2 nd temperature is referred to as a 2 nd crystallization process.

In order to obtain desired physical properties of the glass-ceramic, the preferred crystallization process is:

the above-mentioned crystallization treatment is performed in 1 stage, and the nucleus formation process and the crystal growth process can be continuously performed. That is, the temperature is raised to a predetermined crystallization temperature, and after reaching the crystallization temperature, the temperature is maintained for a predetermined time, and then the temperature is lowered. The crystallization temperature is preferably 600 to 750 ℃, and more preferably 650 to 700 ℃ in order to precipitate a desired crystal phase, and the holding time at the crystallization temperature is preferably 0 to 8 hours, and more preferably 1 to 6 hours.

When the crystallization is performed in 2 stages, the 1 st temperature is preferably 470 to 600 ℃, and the 2 nd temperature is preferably 600 to 750 ℃. The holding time at the temperature of 1 st is preferably 0 to 24 hours, more preferably 2 to 15 hours. The holding time at the 2 nd temperature is preferably 0 to 10 hours, more preferably 0.5 to 6 hours.

The above-mentioned holding time of 0 hour means that the temperature is lowered or raised less than 1 minute after the temperature is reached.

In some embodiments, the matrix or glass-ceramic described herein can be fabricated into shaped bodies, including but not limited to sheets, by various processes, including but not limited to slot draw, float, roll, and other sheet forming processes known in the art. Alternatively, the matrix glass or glass-ceramic may be formed by a float process or a roll process as is well known in the art.

The substrate glass or the glass ceramics of the present invention can be produced into a sheet glass molded body by a method such as grinding or polishing, but the method for producing the glass molded body is not limited to these methods.

The matrix glass or glass-ceramic shaped article of the present invention can be produced into various shapes at a certain temperature by a method such as hot bending or press molding, and is not limited to these methods.

The matrix glass, microcrystalline glass, and microcrystalline glass articles of the present invention may have any thickness that is reasonably useful.

The crystallized glass of the present invention can be produced into a crystallized glass product by forming a compressive stress layer to obtain higher strength in addition to improving mechanical properties by precipitation crystallization.

In some embodiments, the substrate glass or glass ceramic may be formed into a sheet, and/or shaped (e.g., punched, hot bent, etc.), shaped, polished and/or scanned, and then chemically strengthened by a chemical strengthening process.

The chemical strengthening method is an ion exchange method. The matrix glass and the glass ceramics of the present invention can be ion-exchanged by a method known in the art. During the ion exchange process, the smaller metal ions in the matrix glass or glass-ceramic are replaced or "exchanged" by larger metal ions having the same valence state that are adjacent to the matrix glass or glass-ceramic. And replacing the smaller ions with the larger ions to build a compressive stress in the matrix glass or the microcrystalline glass to form a compressive stress layer.

In some embodiments, the metal ion is a monovalent alkali metal ion (e.g., Na)⁺、K⁺、Rb⁺、Cs⁺Etc.), ion exchange is performed by immersing the matrix glass or glass-ceramic in a salt bath of at least one molten salt containing larger metal ions for replacing the smaller metal ions in the matrix glass. Alternatively, other monovalent metal ions such as Ag⁺、Tl⁺、Cu⁺Etc. may also be used to exchange monovalent ions. One or more ion exchange processes used to chemically strengthen the matrix glass or glass-ceramic may include, but are not limited to: it is immersed in a single salt bath or in a plurality of salt baths of the same or different composition with washing and/or annealing steps between the immersions.

In some embodiments, the matrix glass or glass-ceramic may be formed by melting a Na salt (e.g., NaNO) by immersion at a temperature of about 320 ℃ to 470 ℃₃) The salt bath is subjected to ion exchange for about 6 to 20 hours, the preferred temperature range is 360 to 460 ℃, and the preferred time range is 8 to 13 hours. In this embodiment, Na ions replace part of Li ions in the matrix glass or the glass ceramics, thereby forming a surface compression layer and exhibiting high mechanical properties. In some embodiments, the matrix glass or glass-ceramic may be formed by melting a K salt (e.g., KNO) by immersion at a temperature of about 340 ℃ to 450 ℃₃) The salt bath is subjected to ion exchange for 1 to 24 hours, and the preferable time range is 2 to 10 hours. In thatIn some embodiments, the matrix glass or glass-ceramic may be formed by melting a K salt (e.g., KNO) by immersion at a temperature of about 340 ℃ to 450 ℃₃) And molten Na salts (e.g., NaNO)₃) And carrying out ion exchange in the mixed salt bath for 1-24 hours, wherein the preferable time range is 2-10 hours.

In some embodiments, there are also an ion implantation method of implanting ions into a surface layer of a base glass or a glass ceramics, and a heat strengthening method of heating a base glass or a glass ceramics and then rapidly cooling it.

The performance indexes of the microcrystalline glass and/or the microcrystalline glass product and/or the matrix glass are tested by adopting the following method:

[ haze ]

A haze tester EEL57D was used, and samples of 1mm or less were prepared and tested according to GB 2410-80.

[ grain size ]

And (3) determining by using an SEM (scanning electron microscope), carrying out surface treatment on the microcrystalline glass in HF (hydrofluoric acid), carrying out gold spraying on the surface of the microcrystalline glass, and carrying out surface scanning under the SEM, so as to determine the size of the crystal grains.

[ light transmittance ]

The light transmittances described herein are external transmittances, sometimes simply referred to as transmittances.

The sample is processed to be less than 1mm, the opposite surfaces are polished in parallel, and the average light transmittance of 400-800 nm is measured by a Hitachi U-41000 spectrophotometer.

The sample was processed to 1mm or less and the opposed faces were polished in parallel, and the light transmittance at 550nm was measured by Hitachi U-41000 spectrophotometer.

[ degree of crystallinity ]

The XRD diffraction peaks were compared with the database spectra, and the degree of crystallinity was obtained by calculating the proportion of the diffraction intensity of the crystalline phase in the intensity of the entire spectrum, and was internally calibrated by using pure quartz crystals.

[ depth of ion exchange layer ]

Ion exchange layer depth was measured using a glass surface stress meter SLP-2000.

The refractive index of the sample was 1.54 and the optical elastic constant was 25.3[ (nm/cm)/MPa, which were used as the measurement conditions.

[ falling ball test height ]

A microcrystalline glass product sample of 150mm × 57mm × 0.7mm was placed on a glass carrier jig, and 132g of a steel ball was dropped from a predetermined height to a maximum ball drop test height at which the sample could withstand an impact without breaking. Specifically, the test was conducted from a ball drop test height of 800mm, and the height was changed in the order of 850mm, 900mm, 950mm, 1000mm and more without breaking. For the examples having the "falling ball test height", a crystallized glass article was used as a test object. The test data recorded as 1000mm in the examples shows that the crystallized glass product was not broken and received an impact even when the steel ball was dropped from the height of 1000 mm. The drop test height is sometimes referred to herein as the drop height.

[ height of falling ball of body ]

A microcrystalline glass sample of 150mm multiplied by 57mm multiplied by 0.7mm is placed on a glass bearing clamp, 32g of steel balls are dropped from a specified height, and the maximum ball drop test height of the sample which can bear the impact without breaking is the body ball drop height. Specifically, the test was conducted from a ball drop test height of 500mm, and the height was changed in the order of 550mm, 600mm, 650mm, 700mm and more without breaking. For the examples having the "body ball drop height", glass ceramics were used as the test subjects. The test data recorded as 1000mm in the examples shows that the glass ceramics were not broken and received impact even when the steel ball was dropped from the height of 1000 mm.

[ fracture toughness ]

The method for directly measuring the size of the indentation propagation crack is used, the specification of a sample is 2mm multiplied by 4mm multiplied by 20mm, after the sample is chamfered, ground and polished, a Vickers hardness indenter is used for applying 49N force on the sample and maintaining the force for 30s, after the indentation is made, the fracture strength is measured by a three-point bending method.

[ four-point bending Strength ]

A microcomputer-controlled electronic universal tester CMT6502 is adopted, the sample specification is below 1mm in thickness, and the test is carried out by taking ASTM C158-2002 as a standard.

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

[ Vickers hardness ]

The load (N) when a pyramid-shaped depression was pressed into a test surface by a diamond quadrangular pyramid indenter having an included angle of 136 degrees with respect to the surface was divided by the surface area (mm) calculated from the length of the depression²) The values of (b) indicate (a). The test load was set to 100(N) and the holding time was set to 15 (sec). In the present invention, Vickers hardness is sometimes referred to simply as hardness.

[ coefficient of thermal expansion ]

Coefficient of thermal expansion (alpha)_20℃-120℃) The test was carried out according to the test method GB/T7962.16-2010.

[ refractive index ]

Refractive index (n)_d) The test was carried out according to the method GB/T7962.1-2010.

The microcrystalline glass product has the following properties:

1) in some embodiments, the microcrystalline glass article has a four-point flexural strength of 600MPa or greater, preferably 650MPa or greater, and more preferably 700MPa or greater.

2) In some embodiments, the ion exchange layer depth of the crystallized glass product is 20 μm or more, preferably 30 μm or more, and more preferably 40 μm or more.

3) In some embodiments, the crystallized glass article has a ball drop test height of 1200mm or more, preferably 1300mm or more, and more preferably 1400mm or more.

4) In some embodiments, the microcrystalline glass article has a fracture toughness of 1 MPa-m^1/2Above, preferably 1.1MPa · m^1/2More preferably 1.2MPa · m or more^1/2The above.

5) In some embodiments, the microcrystalline glass article has a Vickers hardness (H)_v) Is 680kgf/mm²Above, preferably 700kgf/mm²Above, 720kgf/mm is more preferable²The above.

6) In some embodiments, the microcrystalline glass article has a crystallinity of 50% or more, preferably 60% or more, and more preferably 70% or more.

7) In some embodiments, the crystallite glass article has a grain size of 60nm or less, preferably 50nm or less, and more preferably 30nm or less.

8) In some embodiments, the microcrystalline glass article having a thickness of 1mm or less has a haze of 0.2% or less, preferably 0.17% or less, and more preferably 0.15% or less. The thickness is preferably 0.2 to 1mm, more preferably 0.3 to 0.9mm, still more preferably 0.5 to 0.8mm, and still more preferably 0.55mm, or 0.6mm, or 0.68mm, or 0.7mm, or 0.75 mm.

9) In some embodiments, the microcrystalline glass product having a thickness of 1mm or less has an average transmittance of 87% or more, preferably 89% or more, and more preferably 90% or more at a wavelength of 400 to 800 nm. The thickness is preferably 0.2 to 1mm, more preferably 0.3 to 0.9mm, still more preferably 0.5 to 0.8mm, and still more preferably 0.55mm, or 0.6mm, or 0.68mm, or 0.7mm, or 0.75 mm.

10) In some embodiments, the microcrystalline glass product having a thickness of 1mm or less has a transmittance at a wavelength of 550nm of 88% or more, preferably 90% or more, and more preferably 91% or more. The thickness is preferably 0.2 to 1mm, more preferably 0.3 to 0.9mm, still more preferably 0.5 to 0.8mm, and still more preferably 0.55mm, or 0.6mm, or 0.68mm, or 0.7mm, or 0.75 mm.

The microcrystalline glass has the following properties:

1) in some embodiments, the microcrystalline glass has a crystallinity of 50% or more, preferably 60% or more, and more preferably 70% or more.

2) In some embodiments, the crystallite glass has a grain size of 60nm or less, preferably 50nm or less, preferably 30nm or less.

3) In some embodiments, the haze of the microcrystalline glass having a thickness of 1mm or less is 0.2% or less, preferably 0.17% or less, and more preferably 0.15% or less. The thickness is preferably 0.2 to 1mm, more preferably 0.3 to 0.9mm, still more preferably 0.5 to 0.8mm, and still more preferably 0.55mm, or 0.6mm, or 0.68mm, or 0.7mm, or 0.75 mm.

4) In some embodiments, the microcrystalline glass having a thickness of 1mm or less has an average transmittance of 87% or more, preferably 89% or more, and more preferably 90% or more at a wavelength of 400 to 800 nm. The thickness is preferably 0.2 to 1mm, more preferably 0.3 to 0.9mm, still more preferably 0.5 to 0.8mm, and still more preferably 0.55mm, or 0.6mm, or 0.68mm, or 0.7mm, or 0.75 mm.

5) In some embodiments, the microcrystalline glass having a thickness of 1mm or less has a transmittance at a wavelength of 550nm of 88% or more, preferably 90% or more, and more preferably 91% or more. The thickness is preferably 0.2 to 1mm, more preferably 0.3 to 0.9mm, still more preferably 0.5 to 0.8mm, and still more preferably 0.55mm, or 0.6mm, or 0.68mm, or 0.7mm, or 0.75 mm.

6) In some embodiments, the glass-ceramic body has a ball drop height of 1100mm or more, preferably 1200mm or more, and more preferably 1300mm or more.

7) In some embodiments, the microcrystalline glass has a Vickers hardness (H)_v) Is 650kgf/mm²Above, it is preferably 660kgf/mm²Above, more preferably 670kgf/mm²The above.

9) In some embodiments, the microcrystalline glass has a coefficient of thermal expansion (α)_20℃-120℃) Is 90X 10^-7/K～100×10^-7/K。

10) In some embodiments, the refractive index (n) of the glass-ceramic_d) 1.5500-1.5700.

The matrix glass of the present invention has the following properties:

1) in some embodiments, the matrix glass has a coefficient of thermal expansion (α)_20℃-120℃) Is 70X 10^-7/K～90×10^-7/K。

2) In some embodiments, the refractive index (n) of the matrix glass_d) Is 1.5300 to 1.5500.

The microcrystalline glass, the microcrystalline glass product and the matrix glass have the excellent performances, so that the microcrystalline glass, the microcrystalline glass product and the matrix glass can be widely made into glass cover plates or glass components; meanwhile, the microcrystalline glass product and the matrix glass of the present invention are applied to electronic devices or display devices, such as mobile phones, watches, computers, touch display screens, etc., for manufacturing protective glass for mobile phones, smart phones, tablet computers, notebook computers, PDAs, televisions, personal computers, MTA machines or industrial displays, or for manufacturing touch screens, protective windows, automobile windows, train windows, aircraft windows, touch screen protective glass, or for manufacturing hard disk substrates or solar cell substrates, or for manufacturing white home appliances, such as for manufacturing refrigerator parts or kitchen ware.

Examples

In order to further clarify the explanation and explanation of the technical solution of the present invention, the following non-limiting examples are provided. Many efforts have been made to ensure accuracy with respect to numbers (e.g., amounts, temperature, etc.) but some errors and deviations should be accounted for. The composition is itself given in weight% on oxide basis and has been standardized to 100%.

< microcrystalline glass example >

In the present example, glass ceramics having compositions shown in tables 1 to 3 were obtained by the above-described method for producing glass ceramics. The characteristics of each glass ceramics were measured by the test method described in the present invention, and the measurement results are shown in tables 1 to 3.

Table 1.

Table 2.

Table 3.

< microcrystalline glass article example >

In this example, glass ceramics having compositions shown in tables 4 to 6 were obtained by the above-mentioned method for producing glass ceramics. The characteristics of each glass ceramic product were measured by the test method described in the present invention, and the measurement results are shown in tables 4 to 6.

Table 4.

Table 5.

Table 6.

Claims

1. A microcrystalline glass product, characterized in that it contains a crystalline phase of lithium metasilicate and quartz solid solution, the total content of lithium metasilicate and quartz solid solution being higher in weight percentage than the other crystalline phases, the composition of said microcrystalline glass product, expressed in weight percentage, containing: SiO 2₂+Al₂O₃：60～80％；P₂O₅：2～10％；ZrO₂：0.5～10％；Ln₂O₃: greater than 0 but less than or equal to 10%; li₂O+Na₂O+K₂O: 21.5 to 30% of (SiO)₂+Al₂O₃)/Ln₂O₃7 or more, said Ln₂O₃Is La₂O₃、Gd₂O₃、Y₂O₃、Yb₂O₃One or more of (a).

2. The glass-ceramic article according to claim 1, further comprising, in weight percent: MgO: 0-2%; and/or ZnO: 0-2%; and/or SrO: 0 to 5 percent; and/or BaO: 0 to 5 percent; and/or CaO: 0 to 5 percent; and/or TiO₂: 0 to 5 percent; and/or B₂O₃: 0 to 5 percent; and/or a clarifying agent: 0-2% of a clarifying agent Sb₂O₃、SnO₂、SnO、CeO₂One or more of (a).

3. Microcrystalline glass product, characterised in that it contains a crystalline phase of lithium monosilicate and quartz solid solution, the total content of lithium monosilicate and quartz solid solution being higher in weight percentage than the other crystalline phases, said microcrystalline glass product containing SiO₂、Al₂O₃、Ln₂O₃And alkali metal oxide as essential componentsThe components are expressed by weight percentage, wherein (SiO)₂+Al₂O₃)/Ln₂O₃7 or more, the height of the microcrystalline glass product in a falling ball test is 1200mm or more, and Ln is₂O₃Is La₂O₃、Gd₂O₃、Y₂O₃、Yb₂O₃One or more of (a).

4. A glass-ceramic article according to claim 3, characterized in that its composition, expressed in weight percentage, comprises: SiO 2₂+Al₂O₃: 60-80%; and/or P₂O₅: 2-10%; and/or ZrO₂: 0.5-10%; and/or Ln₂O₃: greater than 0 but less than or equal to 10%; and/or Li₂O+Na₂O+K₂O: 21.5-30%; and/or MgO: 0-2%; and/or ZnO: 0-2%; and/or SrO: 0 to 5 percent; and/or BaO: 0 to 5 percent; and/or CaO: 0 to 5 percent; and/or TiO₂: 0 to 5 percent; and/or B₂O₃: 0 to 5 percent; and/or a clarifying agent: 0-2% of Ln₂O₃Is La₂O₃、Gd₂O₃、Y₂O₃、Yb₂O₃One or more of Sb as clarifying agent₂O₃、SnO₂、SnO、CeO₂One or more of (a).

5. A microcrystalline glass product according to any of claims 1-4, characterised in that its composition, expressed in weight percentages, is: (SiO)₂+Al₂O₃)/Ln₂O₃10 to 72, preferably (SiO)₂+Al₂O₃)/Ln₂O₃Is 11 to 50, more preferably (SiO)₂+Al₂O₃)/Ln₂O₃12 to 30; and/or (SiO)₂+Al₂O₃)/ZrO₂10 to 80, preferably (SiO)₂+Al₂O₃)/ZrO₂15 to 50, more preferably (SiO)₂+Al₂O₃)/ZrO₂20 to 40; and/or (Li)₂O+Na₂O+K₂O)/P₂O₅2.5 to 13, preferably (Li)₂O+Na₂O+K₂O)/P₂O₅2.8 to 10, more preferably (Li)₂O+Na₂O+K₂O)/P₂O₅Is 3 to 7.

6. A microcrystalline glass product according to any of claims 1-4, characterised in that it comprises, in weight%: SiO 2₂+Al₂O₃: 68-80%, preferably SiO₂+Al₂O₃: 70-78%; and/or P₂O₅: 3.5-9%, preferably P₂O₅: 4-8%; and/or ZrO₂: 1 to 6%, preferably ZrO₂: 1-5%; and/or Ln₂O₃: 0.5-8%, preferably Ln₂O₃: 1-7%; and/or Li₂O+Na₂O+K₂O: 22-28%; and/or MgO: 0 to 1 percent; and/or ZnO: 0 to 1 percent; and/or SrO: 0 to 3%, preferably SrO: 0 to 1 percent; and/or BaO: 0-3%, preferably BaO: 0 to 1 percent; and/or CaO: 0-3%, preferably CaO: 0 to 1 percent; and/or TiO₂: 0 to 3%, preferably TiO₂: 0 to 1 percent; and/or B₂O₃: 0 to 3%, preferably B₂O₃: 0 to 1 percent; and/or a clarifying agent: 0-1%, preferably clarifying agent: 0 to 0.5 percent of Ln₂O₃Is La₂O₃、Gd₂O₃、Y₂O₃、Yb₂O₃One or more of Sb as clarifying agent₂O₃、SnO₂、SnO、CeO₂One or more of (a).

7. A microcrystalline glass product according to any of claims 1-4, characterised in that it comprises, in weight%: li₂O: 15 to 25%, preferably Li₂O：16～23％。

8. A glass-ceramic product according to any of claims 1 to 4, characterized in that the lithium monosilicate crystal phase is 20 to 60% by weight of the glass-ceramic product, preferably the lithium monosilicate crystal phase is 25 to 55% by weight of the glass-ceramic product, more preferably the lithium monosilicate crystal phase is 30 to 50% by weight of the glass-ceramic product, and/or the quartz and quartz solid-solution crystal phase is 45% or less by weight of the glass-ceramic product, preferably the quartz and quartz solid-solution crystal phase is 5 to 40% by weight of the glass-ceramic product.

9. A crystallized glass product according to any one of claims 1 to 4, wherein the four-point bending strength of the crystallized glass product is 600MPa or more, preferably 650MPa or more, more preferably 700MPa or more; and/or the depth of the ion exchange layer is 20 μm or more, preferably 30 μm or more, more preferably 40 μm or more; and/or the ball drop test height is 1200mm or more, preferably 1300mm or more, more preferably 1400mm or more; and/or a fracture toughness of 1MPa m^1/2Above, preferably 1.1MPa · m^1/2More preferably 1.2MPa · m or more^1/2The above; and/or a Vickers hardness of 680kgf/mm²Above, preferably 700kgf/mm²Above, 720kgf/mm is more preferable²The above; and/or a crystallinity of 50% or more, preferably 60% or more, more preferably 70% or more; and/or the crystal grain size is 60nm or less, preferably 50nm or less, more preferably 30nm or less.

10. A crystallized glass product according to any one of claims 1 to 4, wherein the crystallized glass product having a thickness of 1mm or less has a haze of 0.2% or less, preferably 0.17% or less, more preferably 0.15% or less; and/or an average transmittance at a wavelength of 400 to 800nm of 87% or more, preferably 89% or more, more preferably 90% or more; and/or a 550nm wavelength transmittance of 88% or more, preferably 90% or more, more preferably 91% or more.

11. A crystallized glass product according to claim 10, wherein the crystallized glass product has a thickness of 0.2 to 1mm, preferably 0.3 to 0.9mm, more preferably 0.5 to 0.8mm, and even more preferably 0.55mm or 0.6mm or 0.68mm or 0.7mm or 0.75 mm.

12. A microcrystalline glass product according to any of claims 1-4, characterised in that the microcrystalline glass product contains a colouring agent.

13. Microcrystalline glass, characterized in that it contains a crystalline phase of lithium metasilicate and quartz solid solution, the total content of lithium metasilicate and quartz solid solution being higher in weight percentage than the other crystalline phases, the composition of said microcrystalline glass, expressed in weight percentage, containing: SiO 2₂+Al₂O₃：60～80％；P₂O₅：2～10％；ZrO₂：0.5～10％；Ln₂O₃: greater than 0 but less than or equal to 10%; li₂O+Na₂O+K₂O: 21.5 to 30% of (SiO)₂+Al₂O₃)/Ln₂O₃7 or more, said Ln₂O₃Is La₂O₃、Gd₂O₃、Y₂O₃、Yb₂O₃One or more of (a).

14. The glass-ceramic according to claim 13, characterized in that it further comprises, in weight percent: MgO: 0-2%; and/or ZnO: 0-2%; and/or SrO: 0 to 5 percent; and/or BaO: 0 to 5 percent; and/or CaO: 0 to 5 percent; and/or TiO₂: 0 to 5 percent; and/or B₂O₃: 0 to 5 percent; and/or a clarifying agent: 0-2% of a clarifying agent Sb₂O₃、SnO₂、SnO、CeO₂One or more of (a).

15. Microcrystalline glass, characterised in that it contains a crystalline phase of lithium metasilicate and quartz solid solution, the total content of lithium metasilicate and quartz solid solution being higher in weight percentage than the other crystalline phases, said microcrystals being obtainedThe crystal glass contains SiO₂、Al₂O₃、Ln₂O₃And an alkali metal oxide as an essential component, the components of which are expressed in weight percent, wherein (SiO)₂+Al₂O₃)/Ln₂O₃Is more than 7, the body falling ball test height of the microcrystalline glass is more than 1100mm, and the Ln₂O₃Is La₂O₃、Gd₂O₃、Y₂O₃、Yb₂O₃One or more of (a).

16. The glass-ceramic according to claim 15, characterized in that it comprises, expressed in weight percent: SiO 2₂+Al₂O₃: 60-80%; and/or P₂O₅: 2-10%; and/or ZrO₂: 0.5-10%; and/or Ln₂O₃: greater than 0 but less than or equal to 10%; and/or Li₂O+Na₂O+K₂O: 21.5-30%; and/or MgO: 0-2%; and/or ZnO: 0-2%; and/or SrO: 0 to 5 percent; and/or BaO: 0 to 5 percent; and/or CaO: 0 to 5 percent; and/or TiO₂: 0 to 5 percent; and/or B₂O₃: 0 to 5 percent; and/or a clarifying agent: 0-2% of Ln₂O₃Is La₂O₃、Gd₂O₃、Y₂O₃、Yb₂O₃One or more of Sb as clarifying agent₂O₃、SnO₂、SnO、CeO₂One or more of (a).

17. A glass-ceramic according to any one of claims 13 to 16, characterized in that it comprises, in weight percent: (SiO)₂+Al₂O₃)/Ln₂O₃10 to 72, preferably (SiO)₂+Al₂O₃)/Ln₂O₃Is 11 to 50, more preferably (SiO)₂+Al₂O₃)/Ln₂O₃12 to 30; and/or (SiO)₂+Al₂O₃)/ZrO₂Is 10 to 80Preferably (SiO)₂+Al₂O₃)/ZrO₂15 to 50, more preferably (SiO)₂+Al₂O₃)/ZrO₂20 to 40; and/or (Li)₂O+Na₂O+K₂O)/P₂O₅2.5 to 13, preferably (Li)₂O+Na₂O+K₂O)/P₂O₅2.8 to 10, more preferably (Li)₂O+Na₂O+K₂O)/P₂O₅Is 3 to 7.

18. The glass-ceramic according to any one of claims 13 to 16, characterized in that it comprises, in weight percent: SiO 2₂+Al₂O₃: 68-80%, preferably SiO₂+Al₂O₃: 70-78%; and/or P₂O₅: 3.5-9%, preferably P₂O₅: 4-8%; and/or ZrO₂: 1 to 6%, preferably ZrO₂: 1-5%; and/or Ln₂O₃: 0.5-8%, preferably Ln₂O₃: 1-7%; and/or Li₂O+Na₂O+K₂O: 22-28%; and/or MgO: 0 to 1 percent; and/or ZnO: 0 to 1 percent; and/or SrO: 0 to 3%, preferably SrO: 0 to 1 percent; and/or BaO: 0-3%, preferably BaO: 0 to 1 percent; and/or CaO: 0-3%, preferably CaO: 0 to 1 percent; and/or TiO₂: 0 to 3%, preferably TiO₂: 0 to 1 percent; and/or B₂O₃: 0 to 3%, preferably B₂O₃: 0 to 1 percent; and/or a clarifying agent: 0-1%, preferably clarifying agent: 0 to 0.5 percent of Ln₂O₃Is La₂O₃、Gd₂O₃、Y₂O₃、Yb₂O₃One or more of Sb as clarifying agent₂O₃、SnO₂、SnO、CeO₂One or more of (a).

19. The glass-ceramic according to any one of claims 13 to 16, characterized in that it comprises, in weight percent: li₂O: 15 to 25%, preferablyLi₂O：16～23％。

20. A glass-ceramic according to any one of claims 13 to 16, wherein the lithium monosilicate crystal phase is 20 to 60% by weight of the glass-ceramic, preferably the lithium monosilicate crystal phase is 25 to 55% by weight of the glass-ceramic, more preferably the lithium monosilicate crystal phase is 30 to 50% by weight of the glass-ceramic, and/or the quartz and quartz solid solution crystal phase is 45% or less by weight of the glass-ceramic, preferably the quartz and quartz solid solution crystal phase is 5 to 40% by weight of the glass-ceramic.

21. The glass-ceramic according to any one of claims 13 to 16, wherein the glass-ceramic has a body ball drop test height of 1100mm or more, preferably 1200mm or more, more preferably 1300mm or more; and/or a Vickers hardness of 650kgf/mm²Above, it is preferably 660kgf/mm²Above, more preferably 670kgf/mm²The above; and/or a crystallinity of 50% or more, preferably 60% or more, more preferably 70% or more; and/or a crystal grain size of 60nm or less, preferably 50nm or less, more preferably 30nm or less; and/or a coefficient of thermal expansion of 90 x 10^-7/K～100×10^-7K; and/or the refractive index is 1.5500-1.5700.

22. The crystallized glass according to any one of claims 13 to 16, wherein the crystallized glass having a thickness of 1mm or less has a haze of 0.2% or less, preferably 0.17% or less, more preferably 0.15% or less; and/or an average transmittance at a wavelength of 400 to 800nm of 87% or more, preferably 89% or more, more preferably 90% or more; and/or a 550nm wavelength transmittance of 88% or more, preferably 90% or more, more preferably 91% or more.

23. A glass-ceramic according to claim 22, wherein the thickness of the glass-ceramic is 0.2 to 1mm, preferably 0.3 to 0.9mm, more preferably 0.5 to 0.8mm, and even more preferably 0.55mm or 0.6mm or 0.68mm or 0.7mm or 0.75 mm.

24. The glass-ceramic according to any one of claims 13 to 16, wherein the glass-ceramic contains a colorant.

25. Matrix glass, characterized in that its composition, expressed in weight percentage, contains: SiO 2₂+Al₂O₃：60～80％；P₂O₅：2～10％；ZrO₂：0.5～10％；Ln₂O₃: greater than 0 but less than or equal to 10%; li₂O+Na₂O+K₂O: 21.5 to 30% of (SiO)₂+Al₂O₃)/Ln₂O₃7 or more, said Ln₂O₃Is La₂O₃、Gd₂O₃、Y₂O₃、Yb₂O₃One or more of (a).

26. The matrix glass according to claim 25, further comprising, in weight percent: MgO: 0-2%; and/or ZnO: 0-2%; and/or SrO: 0 to 5 percent; and/or BaO: 0 to 5 percent; and/or CaO: 0 to 5 percent; and/or TiO₂: 0 to 5 percent; and/or B₂O₃: 0 to 5 percent; and/or a clarifying agent: 0-2% of a clarifying agent Sb₂O₃、SnO₂、SnO、CeO₂One or more of (a).

27. The matrix glass according to any one of claims 25 or 26, having a composition, expressed in weight percent, wherein: (SiO)₂+Al₂O₃)/Ln₂O₃10 to 72, preferably (SiO)₂+Al₂O₃)/Ln₂O₃Is 11 to 50, more preferably (SiO)₂+Al₂O₃)/Ln₂O₃12 to 30; and/or (SiO)₂+Al₂O₃)/ZrO₂10 to 80, preferably (SiO)₂+Al₂O₃)/ZrO₂15 to 50, more preferably 15 to 50(SiO₂+Al₂O₃)/ZrO₂20 to 40; and/or (Li)₂O+Na₂O+K₂O)/P₂O₅2.5 to 13, preferably (Li)₂O+Na₂O+K₂O)/P₂O₅2.8 to 10, more preferably (Li)₂O+Na₂O+K₂O)/P₂O₅Is 3 to 7.

28. The matrix glass according to any one of claims 25 or 26, comprising, in weight percent: SiO 2₂+Al₂O₃: 68-80%, preferably SiO₂+Al₂O₃: 70-78%; and/or P₂O₅: 3.5-9%, preferably P₂O₅: 4-8%; and/or ZrO₂: 1 to 6%, preferably ZrO₂: 1-5%; and/or Ln₂O₃: 0.5-8%, preferably Ln₂O₃: 1-7%; and/or Li₂O+Na₂O+K₂O: 22-28%; and/or MgO: 0 to 1 percent; and/or ZnO: 0 to 1 percent; and/or SrO: 0 to 3%, preferably SrO: 0 to 1 percent; and/or BaO: 0-3%, preferably BaO: 0 to 1 percent; and/or CaO: 0-3%, preferably CaO: 0 to 1 percent; and/or TiO₂: 0 to 3%, preferably TiO₂: 0 to 1 percent; and/or B₂O₃: 0 to 3%, preferably B₂O₃: 0 to 1 percent; and/or a clarifying agent: 0-1%, preferably clarifying agent: 0 to 0.5 percent of Ln₂O₃Is La₂O₃、Gd₂O₃、Y₂O₃、Yb₂O₃One or more of Sb as clarifying agent₂O₃、SnO₂、SnO、CeO₂One or more of (a).

29. The matrix glass according to any one of claims 25 or 26, comprising, in weight percent: li₂O: 15 to 25%, preferably Li₂O：16～23％。

30. The matrix glass of any one of claims 25 or 26, wherein the matrix glass has a coefficient of thermal expansion of 70 x 10^-7/K～90×10^-7And/or a refractive index of 1.5300 to 1.5500.

31. The matrix glass of any one of claims 25 or 26, wherein the matrix glass comprises a colorant.

32. A glass cover plate comprising the crystallized glass product according to any one of claims 1 to 12, and/or the crystallized glass according to any one of claims 13 to 24, and/or the matrix glass according to any one of claims 25 to 31.

33. A glass component comprising the crystallized glass product according to any one of claims 1 to 12, the crystallized glass according to any one of claims 13 to 24, and the matrix glass according to any one of claims 25 to 31.

34. A display device comprising the crystallized glass product according to any one of claims 1 to 12, and/or the crystallized glass according to any one of claims 13 to 24, and/or the matrix glass according to any one of claims 25 to 31, and/or the glass cover plate according to claim 32, and/or the glass component according to claim 33.

35. An electronic device comprising the crystallized glass product according to any one of claims 1 to 12, and/or the crystallized glass according to any one of claims 13 to 24, and/or the matrix glass according to any one of claims 25 to 31, and/or the glass cover plate according to claim 32, and/or the glass component according to claim 33.

36. A method for producing a crystallized glass product, characterized by comprising the steps of:

forming a matrix glass, and crystallizing the matrix glassThe microcrystalline glass is formed by a process, and then a microcrystalline glass product is formed by a chemical strengthening process, wherein the microcrystalline glass product contains lithium metasilicate and quartz solid solution crystal phases, the total content of the lithium metasilicate, the quartz and the quartz solid solution crystal phases is higher than that of other crystal phases in percentage by weight, and the microcrystalline glass product comprises the following components in percentage by weight: SiO 2₂+Al₂O₃：60～80％；P₂O₅：2～10％；ZrO₂：0.5～10％；Ln₂O₃: greater than 0 but less than or equal to 10%; li₂O+Na₂O+K₂O: 21.5 to 30% of (SiO)₂+Al₂O₃)/Ln₂O₃7 or more, said Ln₂O₃Is La₂O₃、Gd₂O₃、Y₂O₃、Yb₂O₃One or more of (a).

37. The method for manufacturing a crystallized glass article according to claim 36, wherein the crystallized glass article further comprises, in terms of weight percent: MgO: 0-2%; and/or ZnO: 0-2%; and/or SrO: 0 to 5 percent; and/or BaO: 0 to 5 percent; and/or CaO: 0 to 5 percent; and/or TiO₂: 0 to 5 percent; and/or B₂O₃: 0 to 5 percent; and/or a clarifying agent: 0-2% of a clarifying agent Sb₂O₃、SnO₂、SnO、CeO₂One or more of (a).

38. A method of manufacturing a crystallized glass article according to any one of claims 36 or 37, wherein the crystallized glass article has a composition expressed in weight percent, wherein: (SiO)₂+Al₂O₃)/Ln₂O₃10 to 72, preferably (SiO)₂+Al₂O₃)/Ln₂O₃Is 11 to 50, more preferably (SiO)₂+Al₂O₃)/Ln₂O₃12 to 30; and/or (SiO)₂+Al₂O₃)/ZrO₂10 to 80, preferably (SiO)₂+Al₂O₃)/ZrO₂15 to 50, more preferably (SiO)₂+Al₂O₃)/ZrO₂20 to 40; and/or (Li)₂O+Na₂O+K₂O)/P₂O₅2.5 to 13, preferably (Li)₂O+Na₂O+K₂O)/P₂O₅2.8 to 10, more preferably (Li)₂O+Na₂O+K₂O)/P₂O₅Is 3 to 7.

39. A method for manufacturing a glass-ceramic article according to any of claims 36 or 37, wherein the glass-ceramic article comprises, in weight percent: SiO 2₂+Al₂O₃: 68-80%, preferably SiO₂+Al₂O₃: 70-78%; and/or P₂O₅: 3.5-9%, preferably P₂O₅: 4-8%; and/or ZrO₂: 1 to 6%, preferably ZrO₂: 1-5%; and/or Ln₂O₃: 0.5-8%, preferably Ln₂O₃: 1-7%; and/or Li₂O+Na₂O+K₂O: 22-28%; and/or MgO: 0 to 1 percent; and/or ZnO: 0 to 1 percent; and/or SrO: 0 to 3%, preferably SrO: 0 to 1 percent; and/or BaO: 0-3%, preferably BaO: 0 to 1 percent; and/or CaO: 0-3%, preferably CaO: 0 to 1 percent; and/or TiO₂: 0 to 3%, preferably TiO₂: 0 to 1 percent; and/or B₂O₃: 0 to 3%, preferably B₂O₃: 0 to 1 percent; and/or a clarifying agent: 0-1%, preferably clarifying agent: 0 to 0.5 percent of Ln₂O₃Is La₂O₃、Gd₂O₃、Y₂O₃、Yb₂O₃One or more of Sb as clarifying agent₂O₃、SnO₂、SnO、CeO₂One or more of (a).

40. The method of making a crystallized glass article of any one of claims 36 or 37, wherein the method comprisesThe microcrystalline glass product comprises the following components in percentage by weight: li₂O: 15 to 25%, preferably Li₂O：16～23％。

41. The method of manufacturing a crystallized glass article according to any one of claims 36 or 37, wherein the crystallization process comprises the steps of: raising the temperature to a specified crystallization treatment temperature, keeping the temperature for a certain time after reaching the crystallization treatment temperature, and then reducing the temperature, wherein the crystallization treatment temperature is 600-750 ℃, preferably 650-700 ℃, and the keeping time at the crystallization treatment temperature is 0-8 hours, preferably 1-6 hours.

42. The method of manufacturing a crystallized glass article according to any one of claims 36 or 37, wherein the crystallization process comprises the steps of: the treatment of the nucleation process is performed at the 1 st temperature, and then the treatment of the crystal growth process is performed at the 2 nd temperature higher than the nucleation process temperature.

43. The method of manufacturing a crystallized glass article according to claim 42, wherein the crystallization process comprises the steps of: the temperature of the No. 1 is 470-600 ℃, and the temperature of the No. 2 is 600-750 ℃; the holding time at the temperature of 1 st is 0 to 24 hours, preferably 2 to 15 hours; the holding time at the 2 nd temperature is 0 to 10 hours, preferably 0.5 to 6 hours.

44. The method of manufacturing a crystallized glass article according to any one of claims 36 or 37, wherein the chemical strengthening process comprises: immersing the microcrystalline glass in a salt bath of molten Na salt at the temperature of 320-470 ℃ for 6-20 hours, wherein the preferred temperature range is 360-460 ℃, and the preferred time range is 8-13 hours; and/or immersing the microcrystalline glass in a salt bath for melting K salt at the temperature of 340-450 ℃ for 1-24 hours, wherein the preferable time range is 2-10 hours; and/or immersing the microcrystalline glass in a salt bath of a molten K salt and a molten Na salt at the temperature of 340-450 ℃ for 1-24 hours, wherein the preferable time range is 2-10 hours.

45. The method for producing a crystallized glass product according to any one of claims 36 or 37, wherein the crystallized glass product contains 20 to 60% by weight of the crystallized glass product of a lithium monosilicate crystal phase, preferably 25 to 55% by weight of the crystallized glass product of a lithium monosilicate crystal phase, more preferably 30 to 50% by weight of the crystallized glass product of a lithium monosilicate crystal phase, and/or 45% or less by weight of the crystallized glass product of a quartz and quartz solid solution crystal phase, preferably 5 to 40% by weight of the crystallized glass product of a quartz and quartz solid solution crystal phase.

46. The method for producing a crystallized glass product according to any one of claims 36 and 37, wherein the crystallized glass product has a four-point bending strength of 600MPa or more, preferably 650MPa or more, more preferably 700MPa or more; and/or the depth of the ion exchange layer is 20 μm or more, preferably 30 μm or more, more preferably 40 μm or more; and/or the ball drop test height is 1200mm or more, preferably 1300mm or more, more preferably 1400mm or more; and/or a fracture toughness of 1MPa m^1/2Above, preferably 1.1MPa · m^1/2More preferably 1.2MPa · m or more^1/2The above; and/or a Vickers hardness of 680kgf/mm²Above, preferably 700kgf/mm²Above, 720kgf/mm is more preferable²The above; and/or a crystallinity of 50% or more, preferably 60% or more, more preferably 70% or more; and/or the crystal grain size is 60nm or less, preferably 50nm or less, more preferably 30nm or less.

47. The method for producing a crystallized glass article according to any one of claims 36 and 37, wherein the crystallized glass article having a thickness of 1mm or less has a haze of 0.2% or less, preferably 0.17% or less, more preferably 0.15% or less; and/or an average transmittance at a wavelength of 400 to 800nm of 87% or more, preferably 89% or more, more preferably 90% or more; and/or a 550nm wavelength transmittance of 88% or more, preferably 90% or more, more preferably 91% or more.

48. The method for producing a glass-ceramic product according to claim 47, wherein the glass-ceramic product has a thickness of 0.2 to 1mm, preferably 0.3 to 0.9mm, more preferably 0.5 to 0.8mm, and further preferably 0.55mm or 0.6mm or 0.68mm or 0.7mm or 0.75 mm.

49. A method for producing a crystallized glass, characterized by comprising:

forming a matrix glass, and then forming a microcrystalline glass from the matrix glass through a crystallization process, wherein the microcrystalline glass comprises a lithium metasilicate and quartz solid solution crystal phase, the total content of the lithium metasilicate and quartz solid solution crystal phase has a higher weight percentage than other crystal phases, and the microcrystalline glass comprises the following components in percentage by weight: SiO 2₂+Al₂O₃：60～80％；P₂O₅：2～10％；ZrO₂：0.5～10％；Ln₂O₃: greater than 0 but less than or equal to 10%; li₂O+Na₂O+K₂O: 21.5 to 30% of (SiO)₂+Al₂O₃)/Ln₂O₃7 or more, said Ln₂O₃Is La₂O₃、Gd₂O₃、Y₂O₃、Yb₂O₃One or more of (a).

50. The method for producing a glass ceramic according to claim 49, wherein the glass ceramic further contains, in terms of the components by weight: MgO: 0-2%; and/or ZnO: 0-2%; and/or SrO: 0 to 5 percent; and/or BaO: 0 to 5 percent; and/or CaO: 0 to 5 percent; and/or TiO₂: 0 to 5 percent; and/or B₂O₃: 0 to 5 percent; and/or a clarifying agent: 0-2% of a clarifying agent Sb₂O₃、SnO₂、SnO、CeO₂One or more of (a).

51. As claimed in any of claims 49 or 50The method for manufacturing the microcrystalline glass is characterized in that the microcrystalline glass comprises the following components in percentage by weight: (SiO)₂+Al₂O₃)/Ln₂O₃10 to 72, preferably (SiO)₂+Al₂O₃)/Ln₂O₃Is 11 to 50, more preferably (SiO)₂+Al₂O₃)/Ln₂O₃12 to 30; and/or (SiO)₂+Al₂O₃)/ZrO₂10 to 80, preferably (SiO)₂+Al₂O₃)/ZrO₂15 to 50, more preferably (SiO)₂+Al₂O₃)/ZrO₂20 to 40; and/or (Li)₂O+Na₂O+K₂O)/P₂O₅2.5 to 13, preferably (Li)₂O+Na₂O+K₂O)/P₂O₅2.8 to 10, more preferably (Li)₂O+Na₂O+K₂O)/P₂O₅Is 3 to 7.

52. A method for producing a glass-ceramic according to any one of claims 49 or 50, wherein the glass-ceramic comprises, in terms of weight percent: SiO 2₂+Al₂O₃: 68-80%, preferably SiO₂+Al₂O₃: 70-78%; and/or P₂O₅: 3.5-9%, preferably P₂O₅: 4-8%; and/or ZrO₂: 1 to 6%, preferably ZrO₂: 1-5%; and/or Ln₂O₃: 0.5-8%, preferably Ln₂O₃: 1-7%; and/or Li₂O+Na₂O+K₂O: 22-28%; and/or MgO: 0 to 1 percent; and/or ZnO: 0 to 1 percent; and/or SrO: 0 to 3%, preferably SrO: 0 to 1 percent; and/or BaO: 0-3%, preferably BaO: 0 to 1 percent; and/or CaO: 0-3%, preferably CaO: 0 to 1 percent; and/or TiO₂: 0 to 3%, preferably TiO₂: 0 to 1 percent; and/or B₂O₃: 0 to 3%, preferably B₂O₃: 0 to 1 percent; and/or a clarifying agent: 0-1%, preferably clarifying agent: 0 to 0.5 percent of Ln₂O₃Is La₂O₃、Gd₂O₃、Y₂O₃、Yb₂O₃One or more of Sb as clarifying agent₂O₃、SnO₂、SnO、CeO₂One or more of (a).

53. A method for producing a glass-ceramic according to any one of claims 49 or 50, wherein the glass-ceramic comprises, in terms of weight percent: li₂O: 15 to 25%, preferably Li₂O：16～23％。

54. The method for manufacturing a crystallized glass according to any one of claims 49 and 50, wherein the crystallization process comprises the steps of: raising the temperature to a specified crystallization treatment temperature, keeping the temperature for a certain time after reaching the crystallization treatment temperature, and then reducing the temperature, wherein the crystallization treatment temperature is 600-750 ℃, preferably 650-700 ℃, and the keeping time at the crystallization treatment temperature is 0-8 hours, preferably 1-6 hours.

55. The method for manufacturing a crystallized glass according to any one of claims 49 and 50, wherein the crystallization process comprises the steps of: the treatment of the nucleation process is performed at the 1 st temperature, and then the treatment of the crystal growth process is performed at the 2 nd temperature higher than the nucleation process temperature.

56. The method for manufacturing crystallized glass according to claim 55, wherein the crystallization process comprises the steps of: the temperature of the No. 1 is 470-600 ℃, and the temperature of the No. 2 is 600-750 ℃; the holding time at the temperature of 1 st is 0 to 24 hours, preferably 2 to 15 hours; the holding time at the 2 nd temperature is 0 to 10 hours, preferably 0.5 to 6 hours.

57. A method for producing a crystallized glass according to any one of claims 49 or 50, wherein the crystallized glass contains 20 to 60% by weight of a lithium monosilicate crystal phase, preferably 25 to 55% by weight of the crystallized glass, more preferably 30 to 50% by weight of the crystallized glass, and/or 45% or less by weight of a quartz and quartz solid solution crystal phase, preferably 5 to 40% by weight of the crystallized glass.

58. The method for producing a glass ceramic according to any one of claims 49 and 50, wherein a body falling ball test height of the glass ceramic is 1100mm or more, preferably 1200mm or more, more preferably 1300mm or more; and/or a Vickers hardness of 650kgf/mm²Above, it is preferably 660kgf/mm²Above, more preferably 670kgf/mm²The above; and/or a crystallinity of 50% or more, preferably 60% or more, more preferably 70% or more; and/or a crystal grain size of 60nm or less, preferably 50nm or less, more preferably 30nm or less; and/or a coefficient of thermal expansion of 90 x 10^-7/K～100×10^-7K; and/or the refractive index is 1.5500-1.5700.

59. The method for producing a crystallized glass according to any one of claims 49 and 50, wherein the crystallized glass having a thickness of 1mm or less has a haze of 0.2% or less, preferably 0.17% or less, more preferably 0.15% or less; and/or an average transmittance at a wavelength of 400 to 800nm of 87% or more, preferably 89% or more, more preferably 90% or more; and/or a 550nm wavelength transmittance of 88% or more, preferably 90% or more, more preferably 91% or more.

60. A method for producing a glass ceramic according to claim 59, wherein the glass ceramic has a thickness of 0.2 to 1mm, preferably 0.3 to 0.9mm, more preferably 0.5 to 0.8mm, and still more preferably 0.55mm, 0.6mm, 0.68mm, 0.7mm, or 0.75 mm.