CN113387586A

CN113387586A - Glass ceramics, glass ceramics product and manufacturing method thereof

Info

Publication number: CN113387586A
Application number: CN202110901872.5A
Authority: CN
Inventors: 原保平; 李赛; 于天来; 蒋焘; 聂小兵
Original assignee: CDGM Glass Co Ltd
Current assignee: CDGM Glass Co Ltd
Priority date: 2021-08-06
Filing date: 2021-08-06
Publication date: 2021-09-14

Abstract

The invention discloses microcrystalline glass, a microcrystalline glass product and a manufacturing method thereof. The microcrystalline glass product comprises the following components in mol percentage: SiO 2₂：65～75％；Al₂O₃：1～8％；Li₂O：14～27％；P₂O₅+ZrO₂: 0.5 to 6 percent. 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.

Description

Glass ceramics, glass ceramics product and manufacturing method thereof

Technical Field

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

Background

In recent years, cover glass has been used for protecting a display or as a rear cover in portable electronic devices such as smart phones and PADs. In addition, in an optical apparatus for an automobile, a monitor security apparatus, or the like, a lens is protected by a protector. These are required to have high visible light transmittance and excellent color balance as materials for cover glass or protective applications, i.e., the relevant cover glass is required to have excellent optical properties. On the other hand, the portable electronic device is inevitably dropped or dropped during use, and it is required that the cover glass has excellent mechanical properties (such as drop resistance) to reduce the possibility of the electronic device being broken due to the drop or drop as much as possible. Conventionally, chemically strengthened glass has been used as a material for the cover glass. However, since cracks are easily generated vertically from the surface of the conventional chemically strengthened glass, the probability of breakage is increased when the portable electronic device is dropped.

The glass ceramics can have physical properties that cannot be obtained in chemically strengthened glass by forming dispersed crystals in the glass, and the glass ceramics have significant advantages over general glass in terms of bending resistance, abrasion resistance, and the like because they are formed in glass. Based on the above advantages, there is a trend that the glass ceramics or the glass ceramics processed by the glass ceramics are applied to display devices or electronic devices with high requirements for falling resistance, pressure resistance and scratch resistance. However, the microcrystalline glass in the prior art has the defects of high haze value, low drop resistance and the like, and is difficult to meet the application of high-requirement display equipment or electronic equipment.

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 glass-ceramic article having a composition, expressed in mole percent, comprising: SiO 2₂：65～75％；Al₂O₃：1～8％；Li₂O：14～27％；P₂O₅+ZrO₂：0.5～6％。

(2) The glass-ceramic article according to (1), whose composition, expressed in mole percent, further comprises: ZnO + MgO: 0 to 4 percent; and/or Na₂O: 0 to 3.5 percent; and/or B₂O₃: 0 to 3 percent; and/or K₂O: 0 to 3 percent; and/or SrO: 0 to 3 percent; and/or BaO: 0 to 3 percent; and/or CaO: 0 to 3 percent; and/or TiO₂: 0 to 3 percent; and/or Y₂O₃: 0 to 3 percent; and/or a clarifying agent: 0 to 1 percent.

(3) Microcrystalline glass product, the composition of which is expressed in mole percent by SiO₂：65～75％；Al₂O₃：1～8％；Li₂O：14～27％；P₂O₅+ZrO₂：0.5～6％；ZnO+MgO：0～4％；Na₂O：0～3.5％；B₂O₃：0～3％；K₂O：0～3％；SrO：0～3％；BaO：0～3％；CaO：0～3％；TiO₂：0～3％；Y₂O₃: 0 to 3 percent; a clarifying agent: 0 to 1 percent.

(4) A microcrystalline glass article having the composition, expressed in weight percent, comprising: SiO 2₂：65～75％，Al₂O₃：1～8％，Li₂O: 14-27%, wherein the crystalline phase of the microcrystalline glass product contains lithium silicate, and/or quartz and quartz solid solution, and/or petalite.

(5) Microcrystalline glass product containing SiO₂、Al₂O₃And Li₂O is used as an essential component, the crystalline phase of the microcrystalline glass product contains lithium silicate, and the falling resistance of the microcrystalline glass product is more than 1700 mm.

(6) The crystallized glass article according to any one of (4) and (5), which has the following components in mol%: SiO 2₂：65～75％；Al₂O₃：1～8％；Li₂O：14～27％；P₂O₅+ZrO₂：0.5～6％；ZnO+MgO：0～4％；Na₂O：0～3.5％；B₂O₃：0～3％；K₂O：0～3％；SrO：0～3％；BaO：0～3％；CaO：0～3％；TiO₂：0～3％；Y₂O₃: 0 to 3 percent; a clarifying agent: 0 to 1 percent.

(7) The crystallized glass product according to any one of (1) to (6), wherein the components are expressed by mole percentage: (Li)₂O+ZrO₂) /(ZnO + MgO) is 10 or more, preferably (Li)₂O+ZrO₂) The value of (ZnO + MgO) is 12 to 45, and (Li) is more preferable₂O+ZrO₂) (ZnO + MgO) is 13 to 40, and more preferably(Li₂O+ZrO₂) And/or (ZnO + MgO) 15 to 35.

(8) The crystallized glass product according to any one of (1) to (6), wherein the components are expressed by mole percentage: (B)₂O₃+Na₂O+ZrO₂)/(Al₂O₃+ MgO) of 0.05 to 1.5, preferably (B)₂O₃+Na₂O+ZrO₂)/(Al₂O₃+ MgO) of 0.1 to 1, more preferably (B)₂O₃+Na₂O+ZrO₂)/(Al₂O₃+ MgO) of 0.15 to 0.8, more preferably (B)₂O₃+Na₂O+ZrO₂)/(Al₂O₃And + MgO) is 0.2 to 0.7.

(9) The crystallized glass product according to any one of (1) to (6), wherein the components are expressed by mole percentage: (SiO)₂+Li₂O)/(Al₂O₃+ ZnO + MgO) is 5 to 40, preferably (SiO)₂+Li₂O)/(Al₂O₃+ ZnO + MgO) is 8 to 30, more preferably (SiO)₂+Li₂O)/(Al₂O₃+ ZnO + MgO) is 10 to 25, more preferably (SiO)₂+Li₂O)/(Al₂O₃+ ZnO + MgO) is 11 to 20.

(10) The crystallized glass product according to any one of (1) to (6), wherein the components are expressed by mole percentage: (SiO)₂+Al₂O₃+Li₂O+Na₂O+ZrO₂)/(P₂O₅+ MgO) of 30 to 90, preferably (SiO)₂+Al₂O₃+Li₂O+Na₂O+ZrO₂)/(P₂O₅+ MgO) 35 to 80, more preferably (SiO)₂+Al₂O₃+Li₂O+Na₂O+ZrO₂)/(P₂O₅+ MgO) is 38 to 75, more preferably (SiO)₂+Al₂O₃+Li₂O+Na₂O+ZrO₂)/(P₂O₅And + MgO) is 40 to 70.

(11) The crystallized glass product according to any one of (1) to (6), wherein the components are expressed by mole percentage: (SiO)₂+Al₂O₃)/(P₂O₅+ZrO₂) 12 to 75, preferably (SiO)₂+Al₂O₃)/(P₂O₅+ZrO₂) 15 to 70, more preferably (SiO)₂+Al₂O₃)/(P₂O₅+ZrO₂) Is 17 to 65, and (SiO) is more preferable₂+Al₂O₃)/(P₂O₅+ZrO₂) Is 20 to 60.

(12) The crystallized glass product according to any one of (1) to (6), wherein the components are expressed by mole percentage: SiO 2₂: 67-73%, preferably SiO₂: 68-72%; and/or Al₂O₃: 2-6.5%, preferably Al₂O₃: 3-6%; and/or Li₂O: 15.5 to 25%, preferably Li₂O: 17-23.5%; and/or ZnO + MgO: 0.1-4%, preferably ZnO + MgO: 0.2 to 3%, more preferably ZnO + MgO: 0.5-2%; and/or P₂O₅+ZrO₂: 1 to 4%, preferably P₂O₅+ZrO₂: 1.2-3%; and/or Na₂O: 0.5 to 3%, preferably Na₂O: 0.5-2.5%; and/or B₂O₃: 0.5 to 2.5%, preferably B₂O₃: 0.5-2%; and/or K₂O: 0 to 2%, preferably K₂O: 0 to 1.5 percent; and/or SrO: 0 to 2%, preferably SrO: 0 to 1 percent; and/or BaO: 0-2%, preferably BaO: 0 to 1 percent; and/or CaO: 0-2%, preferably CaO: 0 to 1 percent; and/or TiO₂: 0 to 2%, preferably TiO₂: 0 to 1 percent; and/or Y₂O₃: 0 to 2%, preferably Y₂O₃: 0 to 1 percent; and/or a clarifying agent: 0-0.5%, preferably clarifying agent: 0 to 0.2 percent.

(13) The crystallized glass product according to any one of (1) to (6), wherein the components are expressed by mole percentage: ZnO: 0-2%, preferably ZnO: 0 to 1.5%, more preferably ZnO: 0 to 1 percent; and/or MgO: 0-4%, preferably MgO: 0 to 3%, more preferably MgO: 0 to 1.5 percent; and/or P₂O₅: 0 to 3%, preferably P₂O₅: 0.2 to 2%, more preferably P₂O₅：0.4～1.5％，Further preferably P₂O₅: 0.5-1%; and/or ZrO₂: 0 to 4%, preferably ZrO₂: 0.2 to 3.5%, more preferably ZrO₂: 0.5 to 3%, and more preferably ZrO₂：0.7～2.5％。

(14) The crystallized glass product according to any one of (1) to (6), wherein the crystallized glass product contains lithium silicate in a crystal phase; and/or quartz and quartz solid solutions; and/or petalite, preferably the crystalline phase in the glass-ceramic product contains lithium disilicate and petalite, the total content of the lithium disilicate and the petalite is higher than that of other crystalline phases by weight percent, more preferably the total content of the lithium disilicate and the petalite crystalline phase accounts for 50-80 percent of the glass-ceramic product by weight percent, further preferably the total content of the lithium disilicate and the petalite crystalline phase accounts for 55-75 percent of the glass-ceramic product by weight percent, and further preferably the total content of the lithium disilicate and the petalite crystalline phase accounts for 55-70 percent of the glass-ceramic product by weight percent.

(15) The microcrystalline glass product according to any one of (1) to (6), wherein the lithium disilicate crystal phase accounts for 15 to 40% by weight of the microcrystalline glass product, preferably the lithium disilicate crystal phase accounts for 20 to 35% by weight of the microcrystalline glass product, and more preferably the lithium disilicate crystal phase accounts for 25 to 35% by weight of the microcrystalline glass product; and/or the petalite crystal phase accounts for 30-55% of the weight of the glass-ceramic product, preferably the petalite crystal phase accounts for 35-55% of the weight of the glass-ceramic product, and more preferably the petalite crystal phase accounts for 35-50% of the weight of the glass-ceramic product; and/or the quartz and quartz solid solution crystal phase accounts for 5-25% of the weight of the microcrystalline glass product, preferably the quartz and quartz solid solution crystal phase accounts for 7-20% of the weight of the microcrystalline glass product; and/or the lithium monosilicate crystal phase accounts for 0-10% of the weight of the microcrystalline glass product, preferably the lithium monosilicate crystal phase accounts for 0-7% of the weight of the microcrystalline glass product, and more preferably the lithium monosilicate crystal phase accounts for 0-5% of the weight of the microcrystalline glass product.

(16) The crystallized glass product according to any one of (1) to (6), wherein the crystallized glass product has four-point bending strength680MPa or more, preferably 700MPa or more, and more preferably 720MPa or more; and/or the ion exchange layer depth of the glass-ceramic product is 85 μm or more, preferably 100 μm or more, more preferably 110 μm or more; and/or the surface stress of the glass-ceramic product is 150MPa or more, preferably 180MPa or more, more preferably 200MPa or more; and/or the height of the microcrystalline glass product in a falling ball test is more than 1500mm, preferably more than 1600mm, and more preferably more than 1700 mm; and/or the fracture toughness of the glass-ceramic product is 1 MPa.m^1/2Above, preferably 1.1MPa · m^1/2More preferably 1.2MPa · m or more^1/2The above; and/or the Vickers hardness of the glass-ceramic article is 750kgf/mm²Above, preferably 780kgf/mm²Above, more preferably 800kgf/mm²The above; and/or the crystallinity of the glass-ceramic product is 55% or more, preferably 65% or more, more preferably 75% or more; and/or the crystallite glass product has a crystal grain size of 35nm or less, preferably 30nm or less, and more preferably 25nm or less.

(17) The crystallized glass product according to any one of (1) to (6), wherein the crystallized glass product having a thickness of 1mm or less has a haze of 0.2% or less, preferably 0.15% or less, and more preferably 0.12% or less; and/or a microcrystalline glass product having a thickness of 1mm or less, and having an average transmittance at a wavelength of 400 to 800nm of 87% or more, preferably 88% or more, more preferably 89% or more; and/or a microcrystalline glass product having a thickness of 1mm or less, and having a transmittance at a wavelength of 550nm of 88% or more, preferably 90% or more, more preferably 91% or more; and/or a microcrystalline glass product having a thickness of 1mm or less, wherein the average light | B | value of 400 to 800nm is 0.8 or less, preferably 0.75 or less, more preferably 0.7 or less; and/or the shatter resistance of the microcrystalline glass product having a thickness of 1mm or less is 1700mm or more, preferably 1800mm or more, and more preferably 2000mm or more.

(18) The microcrystalline glass product according to (17), wherein the thickness of the microcrystalline glass product is 0.2-1 mm, preferably 0.3-0.9 mm, more preferably 0.5-0.8 mm, and further preferably 0.55mm, 0.6mm, 0.68mm, 0.7mm, or 0.75 mm.

(19) Microcrystalline glass, the composition of which, expressed in mole percent, contains: SiO 2₂：65～75％；Al₂O₃：1～8％；Li₂O：14～27％；P₂O₅+ZrO₂：0.5～6％。

(20) The glass-ceramic according to (19), characterized in that it further comprises, in terms of mole percentages of its components: ZnO + MgO: 0 to 4 percent; and/or Na₂O: 0 to 3.5 percent; and/or B₂O₃: 0 to 3 percent; and/or K₂O: 0 to 3 percent; and/or SrO: 0 to 3 percent; and/or BaO: 0 to 3 percent; and/or CaO: 0 to 3 percent; and/or TiO₂: 0 to 3 percent; and/or Y₂O₃: 0 to 3 percent; and/or a clarifying agent: 0 to 1 percent.

(21) Microcrystalline glass, the composition of which is expressed in mole percent by SiO₂：65～75％；Al₂O₃：1～8％；Li₂O：14～27％；P₂O₅+ZrO₂：0.5～6％；ZnO+MgO：0～4％；Na₂O：0～3.5％；B₂O₃：0～3％；K₂O：0～3％；SrO：0～3％；BaO：0～3％；CaO：0～3％；TiO₂：0～3％；Y₂O₃: 0 to 3 percent; a clarifying agent: 0 to 1 percent.

(22) Microcrystalline glass, the composition of which, expressed in mole percent, contains: SiO 2₂：65～75％；Al₂O₃：1～8％；Li₂O: 14-27%, wherein the crystalline phase of the microcrystalline glass contains lithium silicate, and/or quartz and quartz solid solution, and/or petalite.

(23) Microcrystalline glass containing SiO₂、Al₂O₃、Li₂O is an essential component, the crystalline phase in the glass-ceramics contains lithium disilicate and petalite, the total content of the lithium disilicate and the petalite has higher weight percentage than other crystalline phases, and the haze of the glass-ceramics with the thickness of less than 1mm is less than 0.2 percent.

(24) The crystallized glass according to any one of (22) to (23), which contains, in terms of mole percent, the following components: SiO 2₂：65～75％；Al₂O₃：1～8％；Li₂O：14～27％；P₂O₅+ZrO₂：0.5～6％；ZnO+MgO：0～4％；Na₂O：0～3.5％；B₂O₃：0～3％；K₂O：0～3％；SrO：0～3％；BaO：0～3％；CaO：0～3％；TiO₂：0～3％；Y₂O₃: 0 to 3 percent; a clarifying agent: 0 to 1 percent.

(25) The crystallized glass according to any one of (19) to (24), which has the composition, expressed in mol%, wherein: (Li)₂O+ZrO₂) /(ZnO + MgO) is 10 or more, preferably (Li)₂O+ZrO₂) The value of (ZnO + MgO) is 12 to 45, and (Li) is more preferable₂O+ZrO₂) (ZnO + MgO) is 13 to 40, and (Li) is more preferable₂O+ZrO₂) And/or (ZnO + MgO) 15 to 35.

(26) The crystallized glass according to any one of (19) to (24), which has the composition, expressed in mol%, wherein: (B)₂O₃+Na₂O+ZrO₂)/(Al₂O₃+ MgO) of 0.05 to 1.5, preferably (B)₂O₃+Na₂O+ZrO₂)/(Al₂O₃+ MgO) of 0.1 to 1, more preferably (B)₂O₃+Na₂O+ZrO₂)/(Al₂O₃+ MgO) of 0.15 to 0.8, more preferably (B)₂O₃+Na₂O+ZrO₂)/(Al₂O₃And + MgO) is 0.2 to 0.7.

(27) The crystallized glass according to any one of (19) to (24), which has the composition, expressed in mol%, wherein: (SiO)₂+Li₂O)/(Al₂O₃+ ZnO + MgO) is 5 to 40, preferably (SiO)₂+Li₂O)/(Al₂O₃+ ZnO + MgO) is 8 to 30, more preferably (SiO)₂+Li₂O)/(Al₂O₃+ ZnO + MgO) is 10 to 25, more preferably (SiO)₂+Li₂O)/(Al₂O₃+ ZnO + MgO) is 11 to 20.

(28) The crystallized glass according to any one of (19) to (24), which has the composition, expressed in mol%, wherein: (SiO)₂+Al₂O₃+Li₂O+Na₂O+ZrO₂)/(P₂O₅+ MgO) of 30 to 90, preferably (SiO)₂+Al₂O₃+Li₂O+Na₂O+ZrO₂)/(P₂O₅+ MgO) 35 to 80, more preferably (SiO)₂+Al₂O₃+Li₂O+Na₂O+ZrO₂)/(P₂O₅+ MgO) is 38 to 75, more preferably (SiO)₂+Al₂O₃+Li₂O+Na₂O+ZrO₂)/(P₂O₅And + MgO) is 40 to 70.

(29) The crystallized glass according to any one of (19) to (24), which has the composition, expressed in mol%, wherein: (SiO)₂+Al₂O₃)/(P₂O₅+ZrO₂) 12 to 75, preferably (SiO)₂+Al₂O₃)/(P₂O₅+ZrO₂) 15 to 70, more preferably (SiO)₂+Al₂O₃)/(P₂O₅+ZrO₂) Is 17 to 65, and (SiO) is more preferable₂+Al₂O₃)/(P₂O₅+ZrO₂) Is 20 to 60.

(30) The crystallized glass according to any one of (19) to (24), which has the composition, expressed in mol%, wherein: SiO 2₂: 67-73%, preferably SiO₂: 68-72%; and/or Al₂O₃: 2-6.5%, preferably Al₂O₃: 3-6%; and/or Li₂O: 15.5 to 25%, preferably Li₂O: 17-23.5%; and/or ZnO + MgO: 0.1-4%, preferably ZnO + MgO: 0.2 to 3%, more preferably ZnO + MgO: 0.5-2%; and/or P₂O₅+ZrO₂: 1 to 4%, preferably P₂O₅+ZrO₂: 1.2-3%; and/or Na₂O: 0.5 to 3%, preferably Na₂O: 0.5-2.5%; and/or B₂O₃: 0.5 to 2.5%, preferably B₂O₃: 0.5-2%; and/or K₂O: 0 to 2%, preferably K₂O: 0 to 1.5 percent; and/or SrO: 0 to 2%, preferably SrO: 0 to 1 percent; and/or BaO: 0-2%, preferably BaO: 0 to 1 percent; and/or CaO: 0-2%, preferably CaO: 0 to 1 percent; and/or TiO₂: 0 to 2%, preferably TiO₂: 0 to 1 percent; and/or Y₂O₃: 0 to 2%, preferably Y₂O₃: 0 to 1 percent; and/or a clarifying agent: 0-0.5%, preferably clarifying agent: 0 to 0.2 percent.

(31) The crystallized glass according to any one of (19) to (24), which has the composition, expressed in mol%, wherein: ZnO: 0-2%, preferably ZnO: 0 to 1.5%, more preferably ZnO: 0 to 1 percent; and/or MgO: 0-4%, preferably MgO: 0 to 3%, more preferably MgO: 0 to 1.5 percent; and/or P₂O₅: 0 to 3%, preferably P₂O₅: 0.2 to 2%, more preferably P₂O₅: 0.4 to 1.5%, and preferably P₂O₅: 0.5-1%; and/or ZrO₂: 0 to 4%, preferably ZrO₂: 0.2 to 3.5%, more preferably ZrO₂: 0.5 to 3%, and more preferably ZrO₂：0.7～2.5％。

(32) The crystallized glass of any one of (19) to (24), wherein the crystallized glass contains lithium silicate; and/or quartz and quartz solid solutions; and/or petalite, preferably the crystalline phase in the glass ceramics contains lithium disilicate and petalite, the total content of the lithium disilicate and the petalite is higher than that of other crystalline phases by weight percent, more preferably the total content of the lithium disilicate and the petalite crystalline phase accounts for 50-80 percent of the glass ceramics by weight percent, even more preferably the total content of the lithium disilicate and the petalite crystalline phase accounts for 55-75 percent of the glass ceramics by weight percent, and even more preferably the total content of the lithium disilicate and the petalite crystalline phase accounts for 55-70 percent of the glass ceramics by weight percent.

(33) The microcrystalline glass according to any one of (19) to (24), wherein the content of the lithium disilicate crystal phase in the microcrystalline glass is 15 to 40% by weight, preferably the content of the lithium disilicate crystal phase in the microcrystalline glass is 20 to 35% by weight, and more preferably the content of the lithium disilicate crystal phase in the microcrystalline glass is 25 to 35% by weight; and/or the petalite crystal phase accounts for 30-55% of the weight of the glass ceramics, preferably the petalite crystal phase accounts for 35-55% of the weight of the glass ceramics, and more preferably the petalite crystal phase accounts for 35-50% of the weight of the glass ceramics; and/or the quartz and quartz solid solution crystal phase accounts for 5-25% of the weight of the microcrystalline glass, preferably the quartz and quartz solid solution crystal phase accounts for 7-20% of the weight of the microcrystalline glass; and/or the lithium monosilicate crystal phase accounts for 0-10% of the weight of the microcrystalline glass, preferably the lithium monosilicate crystal phase accounts for 0-7% of the weight of the microcrystalline glass, and more preferably the lithium monosilicate crystal phase accounts for 0-5% of the weight of the microcrystalline glass.

(34) The crystallized glass of any one of (19) to (24), wherein the crystallized glass has a crystallinity of 55% or more, preferably 65% or more, and more preferably 75% or more; and/or the crystallite size of the glass ceramics is 35nm or less, preferably 30nm or less, preferably 25nm or less; and/or the ball falling height of the microcrystalline glass body is 1800mm or more, preferably 1900mm or more, and more preferably 2000mm or more; and/or the Vickers hardness of the glass-ceramic is 680kgf/mm²Above, preferably 700kgf/mm²Above, 710kgf/mm is more preferable²The above; and/or the coefficient of thermal expansion of the glass-ceramics is 60 x 10^-7/K～90×10^-7K; and/or the refractive index of the microcrystalline glass is 1.5250-1.5450.

(35) The crystallized glass according to any one of (19) to (24), wherein the crystallized glass having a thickness of 1mm or less has a haze of 0.2% or less, preferably 0.15% or less, more preferably 0.12% or less; and/or microcrystalline glass having a thickness of 1mm or less, and having an average transmittance of 87% or more, preferably 88% or more, more preferably 89% or more at a wavelength of 400 to 800 nm; and/or a microcrystalline glass having a thickness of 1mm or less, and having a transmittance at a wavelength of 550nm of 88% or more, preferably 90% or more, more preferably 91% or more; and/or microcrystalline glass having a thickness of 1mm or less, wherein the average light | B | value of 400 to 800nm is 0.8 or less, preferably 0.75 or less, more preferably 0.7 or less.

(36) The glass ceramic according to (35), 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 further preferably 0.55mm, 0.6mm, 0.68mm, 0.7mm, or 0.75 mm.

(37) A glass composition having the components, expressed in mole percent, comprising: SiO 2₂：65～75％；Al₂O₃：1～8％；Li₂O：14～27％；P₂O₅+ZrO₂：0.5～6％。

(38) The glass composition according to (37), whose components, expressed in mole percent, further comprise: ZnO + MgO: 0 to 4 percent; and/or Na₂O: 0 to 3.5 percent; and/or B₂O₃: 0 to 3 percent; and/or K₂O: 0 to 3 percent; and/or SrO: 0 to 3 percent; and/or BaO: 0 to 3 percent; and/or CaO: 0 to 3 percent; and/or TiO₂: 0 to 3 percent; and/or Y₂O₃: 0 to 3 percent; and/or a clarifying agent: 0 to 1 percent.

(39) Glass composition, the components of which are expressed in mole percent, consisting of SiO₂：65～75％；Al₂O₃：1～8％；Li₂O：14～27％；P₂O₅+ZrO₂：0.5～6％；ZnO+MgO：0～4％；Na₂O：0～3.5％；B₂O₃：0～3％；K₂O：0～3％；SrO：0～3％；BaO：0～3％；CaO：0～3％；TiO₂：0～3％；Y₂O₃: 0 to 3 percent; a clarifying agent: 0 to 1 percent.

(40) The glass composition according to any one of (37) to (39), whose components are expressed in mol%, wherein: (Li)₂O+ZrO₂) /(ZnO + MgO) is 10 or more, preferably (Li)₂O+ZrO₂) The value of (ZnO + MgO) is 12 to 45, and (Li) is more preferable₂O+ZrO₂) (ZnO + MgO) is 13 to 40, and (Li) is more preferable₂O+ZrO₂) And/or (ZnO + MgO) 15 to 35.

(41) The glass composition according to any one of (37) to (39), whose components are expressed in mol%, wherein: (B)₂O₃+Na₂O+ZrO₂)/(Al₂O₃+ MgO) of 0.05 to 1.5, preferably (B)₂O₃+Na₂O+ZrO₂)/(Al₂O₃+ MgO) of 0.1 to 1, more preferably (B)₂O₃+Na₂O+ZrO₂)/(Al₂O₃+ MgO) of 0.15 to 0.8, more preferably (B)₂O₃+Na₂O+ZrO₂)/(Al₂O₃And + MgO) is 0.2 to 0.7.

(42) The glass composition according to any one of (37) to (39), whose components are expressed in mol%, wherein: (SiO)₂+Li₂O)/(Al₂O₃+ ZnO + MgO) is 5 to 40, preferably (SiO)₂+Li₂O)/(Al₂O₃+ ZnO + MgO) is 8 to 30, more preferably (SiO)₂+Li₂O)/(Al₂O₃+ ZnO + MgO) is 10 to 25, more preferably (SiO)₂+Li₂O)/(Al₂O₃+ ZnO + MgO) is 11 to 20.

(43) The glass composition according to any one of (37) to (39), whose components are expressed in mol%, wherein: (SiO)₂+Al₂O₃+Li₂O+Na₂O+ZrO₂)/(P₂O₅+ MgO) of 30 to 90, preferably (SiO)₂+Al₂O₃+Li₂O+Na₂O+ZrO₂)/(P₂O₅+ MgO) 35 to 80, more preferably (SiO)₂+Al₂O₃+Li₂O+Na₂O+ZrO₂)/(P₂O₅+ MgO) is 38 to 75, more preferably (SiO)₂+Al₂O₃+Li₂O+Na₂O+ZrO₂)/(P₂O₅And + MgO) is 40 to 70.

(44) The glass composition according to any one of (37) to (39), whose components are expressed in mol%, wherein: (SiO)₂+Al₂O₃)/(P₂O₅+ZrO₂) 12 to 75, preferably (SiO)₂+Al₂O₃)/(P₂O₅+ZrO₂) 15 to 70, more preferably (SiO)₂+Al₂O₃)/(P₂O₅+ZrO₂) Is 17 to 65, and (SiO) is more preferable₂+Al₂O₃)/(P₂O₅+ZrO₂) Is 20 to 60.

(45) The glass composition according to any one of (37) to (39), whose components are expressed in mol%, wherein: SiO 2₂: 67-73%, preferably SiO₂: 68-72%; and/or Al₂O₃: 2-6.5%, preferably Al₂O₃: 3-6%; and/or Li₂O: 15.5 to 25%, preferably Li₂O: 17-23.5%; and/or ZnO + MgO: 0.1-4%, preferably ZnO + MgO: 0.2 to 3%, more preferably ZnO + MgO: 0.5-2%; and/or P₂O₅+ZrO₂: 1 to 4%, preferably P₂O₅+ZrO₂: 1.2-3%; and/or Na₂O: 0.5 to 3%, preferably Na₂O: 0.5-2.5%; and/or B₂O₃: 0.5 to 2.5%, preferably B₂O₃: 0.5-2%; and/or K₂O: 0 to 2%, preferably K₂O: 0 to 1.5 percent; and/or SrO: 0 to 2%, preferably SrO: 0 to 1 percent; and/or BaO: 0-2%, preferably BaO: 0 to 1 percent; and/or CaO: 0-2%, preferably CaO: 0 to 1 percent; and/or TiO₂: 0 to 2%, preferably TiO₂: 0 to 1 percent; and/or Y₂O₃: 0 to 2%, preferably Y₂O₃: 0 to 1 percent; and/or a clarifying agent: 0-0.5%, preferably clarifying agent: 0 to 0.2 percent.

(46) The glass composition according to any one of (37) to (39), whose components are expressed in mol%, wherein: ZnO: 0-2%, preferably ZnO: 0 to 1.5%, more preferably ZnO: 0 to 1 percent; and/or MgO: 0-4%, preferably MgO: 0 to 3%, more preferably MgO: 0 to 1.5 percent; and/or P₂O₅: 0 to 3%, preferably P₂O₅: 0.2 to 2%, more preferably P₂O₅: 0.4 to 1.5%, and preferably P₂O₅: 0.5-1%; and/or ZrO₂: 0 to 4%, preferably ZrO₂: 0.2 to 3.5%, more preferably ZrO₂: 0.5 to 3%, and more preferably ZrO₂：0.7～2.5％。

(47) The glass composition according to any one of (37) to (39), wherein the glass composition has a thermal expansion coefficient of 55X 10^-7/K～65×10^-7And/or a refractive index of 1.5100-1.5300.

(48) A glass cover plate made of the crystallized glass product according to any one of (1) to (18), and/or made of the crystallized glass according to any one of (19) to (36), and/or made of the glass composition according to any one of (37) to (47).

(49) A glass component produced from the glass-ceramic product according to any one of (1) to (18), and/or the glass-ceramic product according to any one of (19) to (36), and/or the glass composition according to any one of (37) to (47).

(50) A display device comprising the crystallized glass product according to any one of (1) to (18), and/or comprising the crystallized glass according to any one of (19) to (36), and/or comprising the glass composition according to any one of (37) to (47), and/or comprising the glass cover plate according to (48), and/or comprising the glass component according to (49).

(51) An electronic device comprising the glass-ceramic article according to any one of (1) to (18), and/or comprising the glass-ceramic according to any one of (19) to (36), and/or comprising the glass composition according to any one of (37) to (47), and/or comprising the glass cover plate according to (48), and/or comprising the glass component according to (49).

(52) The method for producing a crystallized glass product according to any one of (1) to (18), comprising the steps of: and (2) generating a glass composition, then forming microcrystalline glass by the glass composition through a crystallization process, and then forming a microcrystalline glass product by the microcrystalline glass through a chemical strengthening process.

(53) The method for producing a crystallized glass product according to item (52), wherein the glass composition is formed into a glass shaped body, the glass shaped body is crystallized to form a crystallized glass, and the crystallized glass is chemically strengthened to form the crystallized glass product, or the crystallized glass is formed into a crystallized glass shaped body, and the crystallized glass product is chemically strengthened to form the crystallized glass product.

(54) The method for manufacturing a crystallized glass article according to (52), 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 650-720 ℃, 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 article according to (52), wherein the crystallization process includes the steps of: the method comprises the steps of carrying out nucleation process treatment at the temperature of 1 st, and then carrying out crystal growth process treatment at the temperature of 2 nd, wherein the temperature of 1 st is 470-600 ℃, the holding time at the temperature of 1 st is 0-24 hours, preferably 2-15 hours, the temperature of 2 nd is 600-750 ℃, and the holding time at the temperature of 2 nd is 0-10 hours, preferably 0.5-6 hours.

(56) The method for manufacturing a crystallized glass article according to (52), wherein the crystallization process includes the steps of: the method comprises the steps of carrying out nucleation process treatment at the temperature of 1 st, and then carrying out crystal growth process treatment at the temperature of 2 nd and the temperature of 3 rd, wherein the temperature of 1 st is 470-550 ℃, the holding time at the temperature of 1 st is 0-24 hours, preferably 2-15 hours, the temperature of 2 nd is 570-630 ℃, the holding time at the temperature of 2 nd is 0-10 hours, preferably 0.5-6 hours, the temperature of 3 rd is 650-750 ℃, and the holding time at the temperature of 3 rd is 0-10 hours, preferably 0.5-6 hours.

(57) The method for manufacturing a crystallized glass article according to (52), 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 340-500 ℃ for 1-24 hours, wherein the preferable time range is 2-10 hours.

(58) The method for producing a crystallized glass according to any one of (19) to (36), the method comprising the steps of: a glass composition is formed and then a glass-ceramic is formed by a crystallization process on the glass composition.

(59) According to the method for producing a glass ceramics described in (58), the glass composition is produced into a glass shaped body, and then the glass shaped body is subjected to a crystallization process to form the glass ceramics.

(60) The method for producing a crystallized glass according to (58), 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 650-720 ℃, and the keeping time at the crystallization treatment temperature is 0-8 hours, preferably 1-6 hours.

(61) The method for producing a crystallized glass according to (58), wherein the crystallization process includes the steps of: the method comprises the steps of carrying out nucleation process treatment at the temperature of 1 st, and then carrying out crystal growth process treatment at the temperature of 2 nd, wherein the temperature of 1 st is 470-600 ℃, the holding time at the temperature of 1 st is 0-24 hours, preferably 2-15 hours, the temperature of 2 nd is 600-750 ℃, and the holding time at the temperature of 2 nd is 0-10 hours, preferably 0.5-6 hours.

(62) The method for producing a crystallized glass according to (58), wherein the crystallization process includes the steps of: the method comprises the steps of carrying out nucleation process treatment at the temperature of 1 st, and then carrying out crystal growth process treatment at the temperature of 2 nd and the temperature of 3 rd, wherein the temperature of 1 st is 470-550 ℃, the holding time at the temperature of 1 st is 0-24 hours, preferably 2-15 hours, the temperature of 2 nd is 570-630 ℃, the holding time at the temperature of 2 nd is 0-10 hours, preferably 0.5-6 hours, the temperature of 3 rd is 650-750 ℃, and the holding time at the temperature of 3 rd is 0-10 hours, preferably 0.5-6 hours.

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.

In the crystallized glass or crystallized glass article of the present invention, the crystal phase contains lithium silicate; and/or quartz and quartz solid solutions; and/or petalite. The lithium silicate crystalline phase of the present invention comprises lithium monosilicate and/or lithium disilicate. The crystalline phase is sometimes referred to as crystalline in the present invention.

In some embodiments of the present invention, the crystalline phases in the microcrystalline glass or microcrystalline glass article comprise lithium disilicate, which is present in an amount having a higher weight percent than other crystalline phases, resulting in superior properties of the microcrystalline glass or microcrystalline glass article of the present invention.

In some embodiments of the present invention, the crystalline phase in the glass-ceramic or glass-ceramic article contains petalite, which is present in an amount having a higher weight percentage than other crystalline phases, resulting in excellent properties of the glass-ceramic or glass-ceramic article of the present invention.

In some embodiments of the present invention, the crystalline phases in the microcrystalline glass or microcrystalline glass article comprise lithium monosilicate, with the lithium monosilicate being present in an amount having a higher weight percent than the other crystalline phases, resulting in superior performance of the microcrystalline glass or microcrystalline glass article of the present invention.

In some embodiments of the present invention, the crystalline phases in the glass-ceramic or glass-ceramic article comprise quartz and quartz solid solutions, the quartz and quartz solid solutions being present in an amount having a higher weight percentage than other crystalline phases, resulting in excellent properties of the glass-ceramic or glass-ceramic article of the present invention.

In some embodiments of the present invention, the crystalline phases in the glass-ceramic or glass-ceramic article comprise lithium disilicate and petalite, the combined content of lithium disilicate and petalite having a higher weight percentage than the other crystalline phases, resulting in excellent properties of the glass-ceramic or glass-ceramic article of the present invention.

In some embodiments of the present invention, the crystalline phases in the glass-ceramic or glass-ceramic article comprise lithium monosilicate and petalite, the combined content of lithium monosilicate and petalite having a higher weight percentage than the other crystalline phases, resulting in the glass-ceramic or glass-ceramic article of the present invention having superior properties.

In some embodiments of the present invention, the crystalline phases in the microcrystalline glass or microcrystalline glass article comprise lithium disilicate and quartz solid solutions, and the combined content of lithium disilicate and quartz solid solutions has a higher weight percentage than other crystalline phases, resulting in excellent properties of the microcrystalline glass or microcrystalline glass article of the present invention.

In some embodiments of the present invention, the crystalline phases in the glass-ceramic or glass-ceramic article comprise petalite and quartz solid solutions, and the combined content of petalite and quartz solid solutions has a higher weight percentage than other crystalline phases, resulting in excellent properties of the glass-ceramic or glass-ceramic article of the present invention.

In some embodiments, the lithium disilicate crystalline phase comprises 15 to 40% by weight of the microcrystalline glass or microcrystalline glass article. In some embodiments, the lithium disilicate crystalline phase comprises 20 to 35% by weight of the microcrystalline glass or microcrystalline glass article. In some embodiments, the lithium disilicate crystalline phase comprises 25 to 35% by weight of the microcrystalline glass or microcrystalline glass article.

In some embodiments, the crystalline quartz and quartz solid solution phases comprise 5 to 25 weight percent of the microcrystalline glass or microcrystalline glass article. In some embodiments, the crystalline quartz and quartz solid solution phases constitute 7-20% by weight of the glass-ceramic or glass-ceramic article.

In some embodiments, the petalite crystalline phase comprises 30 to 55% by weight of the glass ceramic or glass ceramic article. In some embodiments, the petalite crystalline phase comprises 35 to 55% by weight of the glass ceramic or glass ceramic article. In some embodiments, the petalite crystalline phase comprises 35 to 50% by weight of the glass ceramic or glass ceramic article.

In some embodiments, the lithium monosilicate crystal phase comprises 0 to 10% by weight of the microcrystalline glass or microcrystalline glass article. In some embodiments, the lithium monosilicate crystal phase comprises 0 to 7% by weight of the microcrystalline glass or microcrystalline glass article. In some embodiments, the lithium monosilicate crystal phase comprises 0 to 5% by weight of the microcrystalline glass or microcrystalline glass article.

In some embodiments, the lithium disilicate and petalite crystalline phases are present in a combined amount of 50 to 80% by weight of the glass ceramic or glass ceramic article. In some embodiments, the combined content of the lithium disilicate and petalite crystalline phases is 55 to 75% by weight of the microcrystalline glass or microcrystalline glass article. In some embodiments, the combined content of the lithium disilicate and petalite crystalline phases is 55 to 70% by weight of the glass ceramic or glass ceramic article.

The ranges of the respective components (components) of the glass composition, the glass ceramics and the glass ceramics product of the present invention will be described below. In the present specification, unless otherwise specified, the contents of the respective components are all expressed in terms of mole percent (mol%) relative to the total amount of the glass composition, or the glass ceramics product substance converted into the composition of oxides. 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 the glass composition, the crystallized glass, or the crystallized glass product composition of the present invention is decomposed in melting and converted into an oxide, the total molar amount of the oxide is 100%. In the present specification, the term "glass" refers to a glass composition before crystallization, a glass composition after crystallization is referred to as "glass ceramics", and a glass ceramic product refers to glass ceramics after chemical strengthening.

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.

SiO₂Is a basic component of the glass composition, the crystallized glass and the crystallized glass product of the present invention, and is one of the main components forming the crystal phase of the crystallized glass and the crystallized glass product if SiO₂The content of (b) is less than 65%, the formation of crystals in the microcrystalline glass and the microcrystalline glass article is reduced and the crystals are easily coarsened, which affects the falling ball test height and haze of the microcrystalline glass and the microcrystalline glass article. Thus, SiO₂The lower limit of the content is 65%, the lower limit is preferably 67%, and the lower limit is more preferably 68%. On the other hand, if SiO₂If the content exceeds 75%, the glass has high melting temperature, difficult melting and difficult molding in the manufacturing process, and the uniformity of the glass is affected. Thus, SiO₂The upper limit of the content is 75%, preferably 73%, more preferably 72%. In some embodiments, about 65%, 65.5%, 66%, 66.5%, 67%, 67.5%, 68%, 68.5%, 69%, 69.5%, 70%, 70.5%, 71%, 71.5%, 72%, 72.5%, 73%, 73.5%, 74%, 74.5%, 75% SiO may be included₂。

Al₂O₃Is a component forming a glass network structure and is one of components forming a petalite crystal phase, which is beneficial to the chemical strengthening of glass and improves the falling ball test height of the glass ceramic product, but if the content of the petalite crystal phase is less than 1 percent, the effect is not good. Thus, Al₂O₃The lower limit of the content is 1%, preferably 2%, more preferably 3%. On the other hand, if Al₂O₃When the content of (b) exceeds 8%, the glass tends to have a low melting property and a low devitrification resistance, and crystals tend to grow during crystallization of the glass, thereby lowering the strength of the glass ceramics and glass ceramics products. Thus, Al₂O₃The upper limit of the content is 8%, preferably 6.5%, more preferably 6%. In some embodiments, about 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8% Al may be included₂O₃。

Li₂O isThe microcrystalline glass and the microcrystalline glass product in the invention form crystal essential components, and are also essential components participating in chemical strengthening and improving the mechanical property of the microcrystalline glass product, if Li is used₂When the content of O is less than 14%, the content of crystals in the microcrystalline glass and the microcrystalline glass product is insufficient, and the strength of the microcrystalline glass and the microcrystalline glass product is reduced. Thus, Li₂The lower limit of the O content is 14%, preferably 15.5%, more preferably 17%. On the other hand, if Li is contained excessively₂O, the haze of the crystallized glass and the crystallized glass article increases. Thus, Li₂The upper limit of the O content is 27%, preferably 25%, more preferably 23.5%. In some embodiments, about 14%, 14.5%, 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%, 25.5%, 26%, 26.5%, 27% Li may be included₂O。

ZnO and MgO promote the formation of quartz and quartz solid solutions in the glass ceramics, and if the total content of ZnO + MgO is too high, the haze of the glass ceramics and glass ceramics products increases. Therefore, ZnO + MgO is limited to 4% or less. If ZnO + MgO is too low, the microcrystalline glass and the microcrystalline glass product can not form quartz or quartz solid solution under the condition of low haze, which is not beneficial to realizing the excellent mechanical properties of the microcrystalline glass and the microcrystalline glass product. Therefore, ZnO + MgO is preferably 0.1 to 4%, ZnO + MgO is more preferably 0.2 to 3%, and ZnO + MgO is still more preferably 0.5 to 2%. In some embodiments, the content of ZnO is preferably 0 to 2%, more preferably 0 to 1.5%, and further preferably 0 to 1%. In some embodiments, the content of MgO is preferably 0 to 4%, more preferably 0 to 3%, and further preferably 0 to 1.5%. In some embodiments, the ZnO + MgO value may be 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%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%. 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%, 1.5%, 2% ZnO may be included. In some embodiments, MgO may be included at 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%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%.

The inventors have found, through extensive experimental studies, that in some embodiments of the invention, Li is incorporated₂O and ZrO₂Total content of (2) Li₂O+ZrO₂Ratio of ZnO to MgO (Li) based on the total content of ZnO and MgO₂O+ZrO₂) Controlling the ZnO + MgO to be more than 10, the haze of the microcrystalline glass and the microcrystalline glass product can be reduced, and the light transmittance is improved. Therefore, (Li) is preferable₂O+ZrO₂) Where (ZnO + MgO) is 10 or more, more preferably (Li)₂O+ZrO₂) And/or (ZnO + MgO) is 12 to 45. Further, by controlling (Li)₂O+ZrO₂) And/or (ZnO + MgO) in the range of 13-40, the chemical strengthening performance of the microcrystalline glass can be further improved, the depth and the surface stress of an ion exchange layer of the microcrystalline glass product are improved, and the four-point bending strength of the microcrystalline glass product is improved. Therefore, (Li) is more preferable₂O+ZrO₂) (ZnO + MgO) is 13 to 40, and (Li) is more preferable₂O+ZrO₂) And/or (ZnO + MgO) 15 to 35. In some embodiments, Li₂The value of O/(ZnO + MgO) may 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.

In some embodiments, by control (SiO)₂+Li₂O)/(Al₂O₃And + ZnO + MgO) is within the range of 5-40, which is beneficial to improving the height and fracture toughness of the ball drop test of the microcrystalline glass and the microcrystalline glass product. Therefore, (SiO) is preferable₂+Li₂O)/(Al₂O₃+ ZnO + MgO) is 5 to 40, more preferably (SiO)₂+Li₂O)/(Al₂O₃+ ZnO + MgO) is 8 to 30. Further, by controlling (SiO)₂+Li₂O)/(Al₂O₃+ ZnO + MgO) in the range of 10-25, and is also favorable for reducing microcrystalline glass and microcrystalline glassHaze of the product and light transmittance are improved. Therefore, (SiO) is more preferable₂+Li₂O)/(Al₂O₃+ ZnO + MgO) is 10 to 25, more preferably (SiO)₂+Li₂O)/(Al₂O₃+ ZnO + MgO) is 11 to 20. In some embodiments, (SiO)₂+Li₂O)/(Al₂O₃+ ZnO + MgO) may have a value of 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40.

P₂O₅And ZrO₂Has a nucleating effect when its total content P is₂O₅+ZrO₂Above 0.5%, formation of crystals desired in the present invention is facilitated to achieve excellent mechanical properties and optical properties of the crystallized glass and crystallized glass article of the present invention. If the total content P thereof is₂O₅+ZrO₂If the content exceeds 6%, the crystallite size in the glass ceramics or the glass ceramics product becomes large, the haze and transmittance of the glass ceramics or the glass ceramics product increase, and the mechanical properties deteriorate. Thus, P₂O₅+ZrO₂0.5 to 6%, preferably P₂O₅+ZrO₂1 to 4%, more preferably P₂O₅+ZrO₂1.2 to 3 percent. In some embodiments, P₂O₅+ZrO₂Values of (a) may be 0.5%, 1%, 1.2%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%.

In some embodiments, the SiO is₂And Al₂O₃SiO in total content₂+Al₂O₃And P₂O₅And ZrO₂Total content P of₂O₅+ZrO₂Ratio (SiO) between₂+Al₂O₃)/(P₂O₅+ZrO₂) The crystallization degree of the microcrystalline glass and the microcrystalline glass product can be improved and the grain size can be reduced by controlling the crystallization degree within the range of 12-75. Therefore, (SiO) is preferable₂+Al₂O₃)/(P₂O₅+ZrO₂) Is 12 ℃75, more preferably (SiO)₂+Al₂O₃)/(P₂O₅+ZrO₂) 15 to 70. Further, control (SiO)₂+Al₂O₃)/(P₂O₅+ZrO₂) Within the range of 17-65, the fracture toughness and the falling resistance of the microcrystalline glass product can be further improved, and the falling ball test height of the microcrystalline glass and the microcrystalline glass product is improved. Therefore, (SiO) is more preferable₂+Al₂O₃)/(P₂O₅+ZrO₂) Is 17 to 65, and (SiO) is more preferable₂+Al₂O₃)/(P₂O₅+ZrO₂) Is 20 to 60. In some embodiments, (SiO)₂+Al₂O₃)/(P₂O₅+ZrO₂) May be 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.

P₂O₅The crystal nucleus can be formed in the glass, the crystal formation is promoted, the strength of the microcrystalline glass and the microcrystalline glass product is improved, and the haze of the microcrystalline glass and the microcrystalline glass product is favorably reduced. On the other hand, if P is contained excessively₂O₅Devitrification easily occurs during the production of the glass composition, increasing the difficulty of forming the glass. Thus, P₂O₅The content range of (b) is preferably 0 to 3%, more preferably 0.2 to 2%, further preferably 0.4 to 1.5%, further preferably 0.5 to 1%. 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%, 1.5%, 2%, 2.5%, 3% P may be included₂O₅。

ZrO₂Has the function of forming crystal nucleus by crystallization precipitation, can refine crystal grains and reduce the haze of the microcrystalline glass and the microcrystalline glass product. On the other hand, if ZrO is contained excessively₂The haze of the crystallized glass and the crystallized glass product is rather increased. Thus, ZrO₂The content of (b) is preferably 0 to 4%, more preferably 0.2 to 3.5%, further preferably 0.5 to 3%, and further preferably 0.7 to 2.5%. 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%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4% ZrO may be included₂。

Na₂O can reduce the haze of the glass ceramics and the glass ceramics products, increase the glass phase in the glass ceramics, and is beneficial to the hot bending forming of the glass ceramics, but if the content of Na is excessive, the content of Na₂O, in turn, causes coarsening of crystals in the crystallized glass and the crystallized glass article, and in turn causes deterioration of haze and transmittance of the crystallized glass and the crystallized glass article. Thus, Na₂The content of O is 0 to 3.5%, preferably 0.5 to 3%, and more preferably 0.5 to 2.5%. 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%, 1.5%, 2%, 2.5%, 3%, 3.5% Na may be included₂O。

In some embodiments, (SiO)₂+Al₂O₃+Li₂O+Na₂O+ZrO₂)/(P₂O₅And + MgO) is controlled within the range of 30-90, and the | B | value and the haze of the microcrystalline glass and the microcrystalline glass product can be reduced. Therefore, (SiO) is preferable₂+Al₂O₃+Li₂O+Na₂O+ZrO₂)/(P₂O₅+ MgO) of 30 to 90, more preferably

(SiO₂+Al₂O₃+Li₂O+Na₂O+ZrO₂)/(P₂O₅And + MgO) is 35 to 80. Further, mixing (SiO)₂+Al₂O₃+Li₂O+Na₂O+ZrO₂)/(P₂O₅+ MgO) is controlled within the range of 38-75, the four-point bending strength and Vickers hardness of the microcrystalline glass and the microcrystalline glass product can be improved, and the ions of the microcrystalline glass product are improvedExchange layer depth and surface stress. Therefore, (SiO) is more preferable₂+Al₂O₃+Li₂O+Na₂O+ZrO₂)/(P₂O₅+ MgO) is 38 to 75, more preferably (SiO)₂+Al₂O₃+Li₂O+Na₂O+ZrO₂)/(P₂O₅And + MgO) is 40 to 70. In some embodiments, (SiO)₂+Al₂O₃+Li₂O+Na₂O+ZrO₂)/(P₂O₅+ MgO) may have a value of 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, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90.

B₂O₃The glass does not participate in the formation of crystals, the glass phase in the glass ceramics can be increased, and the glass ceramics is beneficial to the hot bending forming of the glass ceramics, but if the glass contains B excessively₂O₃Therefore, the crystal grains are promoted to grow rapidly, and the crystallization treatment is not easy to control. Thus B₂O₃The content is in the range of 0 to 3%, preferably 0.5 to 2.5%, more preferably 0.5 to 2%. 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%, 1.5%, 2%, 2.5%, 3% B may be included₂O₃。

In some embodiments, by controlling (B)₂O₃+Na₂O+ZrO₂)/(Al₂O₃And + MgO) is within the range of 0.05-1.5, the Vickers hardness of the microcrystalline glass and the microcrystalline glass product can be improved, and the grain size of the microcrystalline glass and the microcrystalline glass product can be reduced. Therefore, (B) is preferred₂O₃+Na₂O+ZrO₂)/(Al₂O₃+ MgO) of 0.05 to 1.5, more preferably (B)₂O₃+Na₂O+ZrO₂)/(Al₂O₃And + MgO) is 0.1 to 1. Further, by controlling (B)₂O₃+Na₂O+ZrO₂)/(Al₂O₃And + MgO) is 0.15-0.8, and the crystallinity and the falling resistance of the microcrystalline glass and the microcrystalline glass product can be further improved. Therefore, (B) is more preferable₂O₃+Na₂O+ZrO₂)/(Al₂O₃+ MgO) of 0.15 to 0.8, more preferably (B)₂O₃+Na₂O+ZrO₂)/(Al₂O₃And + MgO) is 0.2 to 0.7. In some embodiments, (B)₂O₃+Na₂O+ZrO₂)/(Al₂O₃+ MgO) may have a value of 0.05, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9, 0.95, 1, 1.05, 1.1, 1.15, 1.2, 1.25, 1.3, 1.35, 1.4, 1.45, 1.5.

K₂O lowers the viscosity of the glass, promotes the formation of crystals during heat treatment, but if K is contained excessively₂And O, the glass crystal is easy to coarsen, and the transmittance and the falling ball test height of the microcrystalline glass and the microcrystalline glass product are reduced. Thus, K₂The content of O is 3% or less, preferably 2% or less, and more preferably 1.5% or less. In some embodiments, K may be included at 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%, 1.5%, 2%, 2.5%, 3%₂O。

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 3%, preferably 0 to 2%, 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% 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 3%, preferably 0 to 2%, 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%.

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 3%, preferably 0 to 2%, 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%.

TiO₂Is an optional component which is helpful for reducing the melting temperature of the glass and improving the chemical stability, and contains less than 3 percent of TiO₂The crystallization process of the glass can be easily controlled, and TiO is preferred₂The content of (b) is 2% 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% TiO may be included₂。

Y₂O₃Can reduce the smelting difficulty of the glass, reduce phase separation in the glass, reduce the haze and the | B | value of the microcrystalline glass and the microcrystalline glass product, if Y is Y, the method can also reduce the phase separation in the glass, and if Y is Y, the method can also reduce the haze and the | B | value of the microcrystalline glass product₂O₃When the content is too large, it is difficult to form crystals during crystallization of glass, and the crystallinity of glass ceramics and glass ceramics products is lowered, so that Y is₂O₃The upper limit of the content is 3%, preferably 2%, more preferably 1%, and further preferably no Y is contained₂O₃. In some embodiments, about 0%, greater than 0%, 0.01%, 0.05%, 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3% Y may be included₂O₃。

In some embodiments, the glass, glass-ceramic or glass-ceramic article may further comprise 0-1% of a fining agent to improve the defoaming capability of the glass, glass-ceramic or glass-ceramic article. Such fining agents include, but are not limited to, Sb₂O₃、SnO₂SnO and CeO₂Preferably Sb₂O₃As a clarifying agent. On the upper partThe upper limit of the content of the above-mentioned clarifying agent, when it is present alone or in combination, is preferably 0.5%, more preferably 0.2%. 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%.

In order to obtain the 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 preferable that F is not contained in some embodiments of the present invention. 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, by including a colorant, a colored glass composition, glass ceramic, or glass ceramic article can be produced, which can be made to exhibit different colors. In some embodiments, an antimicrobial component may be added to the glass composition, the microcrystalline glass, or the 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 can be added to the glass composition, the glass-ceramic, or the 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.

"0%" or "not containing" as used herein means that the compound, molecule, element or the like is not intentionally added as a raw material to the glass composition, the glass ceramics or the glass ceramics 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 glass composition, the crystallized glass or the crystallized glass article, and may be present in small or trace amounts in the final glass composition, the crystallized glass or the crystallized glass article.

In some embodiments of the present invention, the crystalline phase in the glass-ceramic and glass-ceramic articles comprises lithium disilicate and petalite, and/or quartz and quartz solid solution, providing high strength to the glass-ceramic and glass-ceramic articles of the present invention, and the glass-ceramic and glass-ceramic articles have high fracture toughness; the height of the ball drop test and the four-point bending strength of the microcrystalline glass and the microcrystalline glass product are increased; the haze is reduced and the light transmittance is increased. The microcrystalline glass has excellent chemical strengthening performance, and can obtain more excellent 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 55% or more, preferably 65% or more, and more preferably 75% or more.

The size and 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 grains, the higher the transmittance, and 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 0.15% or less, and more preferably 0.12% or less. In some embodiments, the crystallite glass article or crystallite glass has a grain size of 35nm or less, preferably 30nm or less, more preferably 25nm or less.

In some embodiments, the microcrystalline glass or the microcrystalline glass product of the present invention exhibits a high transmittance in the visible light range, and in some embodiments, an average light transmittance of 400 to 800nm of a microcrystalline glass product or a microcrystalline glass having a thickness of 1mm or less is preferably 89% or more. 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.

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

forming a glass composition: 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 1400 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 glass composition of the present invention can be shaped by a well-known method.

The glass composition of the present 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, 2 stages, or 3 stages. 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 720 ℃, in order to precipitate a desired crystal phase, the holding time at the crystallization temperature is preferably 0 to 8 hours, and more preferably 1 to 6 hours.

In the case of performing the crystallization process through 2 stages as described above, the process of the nucleation process is performed at the 1 st temperature, and then the process of the crystal growth process is performed at the 2 nd temperature. The 1 st temperature is preferably 470-600 ℃, and the 2 nd temperature is preferably 600-750 ℃. 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.

When the crystallization is performed through 3 stages, the nucleation process is performed at the 1 st temperature, and then the crystal growth process is performed at the 2 nd and 3 rd temperatures, wherein the 1 st temperature is preferably 470-550 ℃, the 2 nd temperature is preferably 570-630 ℃, and the 3 rd temperature is preferably 650-750 ℃. 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 holding time at the 3 rd 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 glass compositions or glass-ceramics 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 glass composition or glass ceramic may be formed by a float or roll process as is well known in the art.

The glass composition or glass ceramics of the present invention can be used for producing a sheet glass shaped article by a method such as grinding or polishing, but the method for producing a glass shaped article is not limited to these methods.

The glass composition or the glass-ceramic molded article of the present invention can be produced and formed 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 glass compositions, devitrified glasses, and devitrified glass articles of the present invention can 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 glass composition or glass ceramic may be formed into a sheet, and/or shaped (e.g., punched, hot bent, etc.), shaped, polished and/or swept, and chemically strengthened by a chemical strengthening process.

The chemical strengthening method is an ion exchange method. During the ion exchange process, the smaller metal ions in the glass composition or glass-ceramic are replaced or "exchanged" by larger metal ions having the same valence state that are adjacent to the glass composition or glass-ceramic. Replacing the smaller ions with larger ions creates a compressive stress in the glass composition or glass ceramic, forming 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 glass composition 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 glass composition. 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 glass composition 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 glass composition or glass-ceramic can 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 glass composition or the glass ceramics, thereby forming a surface compression layer and exhibiting high mechanical properties. In some embodiments, the glass composition 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 some embodiments, the glass composition or glass-ceramic can be formed by immersion at about 340 ℃ to about 500 DEG CMelting K salt (e.g. KNO) at a temperature of₃) 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 the glass composition or the glass ceramics, and a heat strengthening method of heating the glass composition or the glass ceramics and then rapidly cooling the same.

The performance indexes of the microcrystalline glass and/or the microcrystalline glass product and/or the glass composition 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.

[ surface stress ] and [ depth of ion exchange layer ]

Surface stress measurement was carried out using a glass surface stress meter SLP-2000.

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℃-300℃) 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.

[ | B | value ]

B value detection was performed using Mentenda CM-700 d. And (3) performing zero calibration and white board calibration of the instrument by using the matched long correction cylinder and the matched short correction cylinder respectively, performing an empty test by using the long cylinder after calibration, judging the stability and calibration reliability (B is less than or equal to 0.05) of the instrument, and placing a product on the zero long cylinder for testing after the instrument is qualified for calibration.

The | B | value is the absolute value of the B value.

[ shatter resistance ]

The drop resistance test was carried out using a directional drop tester WH-2101. The 2D glass ceramic product is loaded with glass products with the same specification (each glass product is 20g in weight and is loaded with 2 glass sheets), 60-80 meshes of sand paper is laid on a base, the sand paper freely falls from the specified height, a sample is directly hammered on the sand paper, and the height which can bear the impact without breaking is the falling resistance. Specifically, the test was conducted from a height of 600mm, and the height was changed in the order of 700mm, 800mm, 900mm, 1000mm and more without breaking. For the examples having "drop-resistance", a glass ceramic product was used as a test object. The test data recorded as 2000mm in the examples indicates that even a loaded glass-ceramic article withstood impact without breaking from a height of 2000mm, the maximum test height of the drop tester WH-2101 was 2000 mm.

The microcrystalline glass product has the following properties:

1) in some embodiments, the microcrystalline glass article has a four-point flexural strength of 680MPa or greater, preferably 700MPa or greater, and more preferably 720MPa or greater.

2) In some embodiments, the ion exchange layer depth of the crystallized glass product is 85 μm or more, preferably 100 μm or more, and more preferably 110 μm or more.

3) In some embodiments, the surface stress of the microcrystalline glass article is 150MPa or greater, preferably 180MPa or greater, and more preferably 200MPa or greater.

4) In some embodiments, the crystallized glass article has a ball drop test height of 1500mm or more, preferably 1600mm or more, and more preferably 1700mm or more.

5) 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.

6) In some embodiments, the microcrystalline glass article has a Vickers hardness of 750kgf/mm²Above, preferably 780kgf/mm²Above, more preferably 800kgf/mm²The above.

7) In some embodiments, the microcrystalline glass article has a crystallinity of 55% or more, preferably 65% or more, and more preferably 75% or more.

8) In some embodiments, the crystallite glass article has a grain size of 35nm or less, preferably 30nm or less, and more preferably 25nm or less.

9) In some embodiments, the microcrystalline glass article having a thickness of 1mm or less has a haze of 0.2% or less, preferably 0.15% or less, and more preferably 0.12% 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.

10) In some embodiments, the microcrystalline glass product having a thickness of 1mm or less has an average transmittance of 87% or more, preferably 88% or more, and more preferably 89% 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.

11) 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.

12) In some embodiments, the microcrystalline glass article has a thickness of less than 1mm, and the average light | B | value of 400-800 nm is less than or equal to 0.8, preferably less than or equal to 0.75, and more preferably less than or equal to 0.7. 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.

13) In some embodiments, the shatter resistance of the glass-ceramic article having a thickness of 1mm or less is 1700mm or more, preferably 1800mm or more, and more preferably 2000mm 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 55% or more, preferably 65% or more, and more preferably 75% or more.

2) In some embodiments, the crystallite glass has a grain size of 35nm or less, preferably 30nm or less, preferably 25nm 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 0.15% or less, and more preferably 0.12% 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 88% or more, and more preferably 89% 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 microcrystalline glass article has a thickness of less than 1mm, and the average light | B | value of 400-800 nm is less than or equal to 0.8, preferably less than or equal to 0.75, and more preferably less than or equal to 0.7. 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.

7) In some embodiments, the glass-ceramic body has a ball drop height of 1800mm or more, preferably 1900mm or more, and more preferably 2000mm or more.

8) In some embodiments, the microcrystalline glass has a Vickers hardness of 680kgf/mm²Above, preferably 700kgf/mm²Above, 710kgf/mm is more preferable²The above.

9) In some embodiments, the microcrystalline glass has a coefficient of thermal expansion (α)_20℃-120℃) Is 60X 10^-7/K～90×10^-7/K。

10) In some embodiments, the refractive index (n) of the glass-ceramic_d) 1.5250-1.5450.

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

1) in some embodiments, the glass composition has a coefficient of thermal expansion (α)_20℃-120℃) Is 55X 10^-7/K～65×10^-7/K。

2) In some embodiments, the refractive index (n) of the glass composition_d) Is 1.5100 to 1.5300.

The microcrystalline glass, the microcrystalline glass product and the glass composition can be widely made into glass cover plates or glass components due to the excellent performance; meanwhile, the microcrystalline glass product and the glass composition 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%.

< glass composition examples >

In this example, glass compositions having compositions shown in tables 1 to 2 were obtained by the above-described methods for producing glass compositions. The characteristics of each glass composition were measured by the test method described in the present invention, and the measurement results are shown in tables 1 to 2.

Table 1.

Table 2.

< microcrystalline glass example >

In this example, glass ceramics having compositions shown in tables 3 to 4 were obtained by the above-mentioned 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 3 to 4, and the test thickness of the sample of the glass ceramics in the examples was 0.7 mm.

Table 3.

Table 4.

< microcrystalline glass article example >

In this example, glass ceramics having compositions shown in tables 5 to 6 were obtained by the above-mentioned method for producing glass ceramics. The characteristics of each of the microcrystalline glass products were measured by the test method according to the present invention, and the measurement results are shown in tables 5 to 6, and the test thickness of the sample of the microcrystalline glass product in the example was 0.7 mm.

Table 5.

Table 6.

Claims

1. A microcrystalline glass product, characterized in that its composition, expressed in mole percentages, contains: SiO 2₂：65～75％；Al₂O₃：1～8％；Li₂O：14～27％；P₂O₅+ZrO₂：0.5～6％。

2. The glass-ceramic article according to claim 1, characterized in that its composition, expressed in mole percentages, further comprises: ZnO + MgO: 0 to 4 percent; and/or Na₂O: 0 to 3.5 percent; and/or B₂O₃: 0 to 3 percent; and/or K₂O: 0 to 3 percent; and/or SrO: 0 to 3 percent; and/or BaO: 0 to 3 percent; and/or CaO: 0 to 3 percent; and/or TiO₂: 0 to 3 percent; and/or Y₂O₃: 0 to 3 percent; and/or a clarifying agent: 0 to 1 percent.

3. Microcrystalline glass product, characterized in that its composition, expressed in mole percentage, is represented by SiO₂：65～75％；Al₂O₃：1～8％；Li₂O：14～27％；P₂O₅+ZrO₂：0.5～6％；ZnO+MgO：0～4％；Na₂O：0～3.5％；B₂O₃：0～3％；K₂O：0～3％；SrO：0～3％；BaO：0～3％；CaO：0～3％；TiO₂：0～3％；Y₂O₃: 0 to 3 percent; a clarifying agent: 0 to 1 percent.

4. A microcrystalline glass product according to any of claims 1-3, characterised in that its composition is expressed in mole percentage, where: (Li)₂O+ZrO₂) /(ZnO + MgO) is 10 or more, preferably (Li)₂O+ZrO₂) The value of (ZnO + MgO) is 12 to 45, and (Li) is more preferable₂O+ZrO₂) (ZnO + MgO) is 13 to 40, and (Li) is more preferable₂O+ZrO₂) And/or (ZnO + MgO) 15 to 35.

5. A microcrystalline glass product according to any of claims 1-3, characterised in that its composition is expressed in mole percentage, where: (B)₂O₃+Na₂O+ZrO₂)/(Al₂O₃+ MgO) of 0.05 to 1.5, preferably (B)₂O₃+Na₂O+ZrO₂)/(Al₂O₃+ MgO) of 0.1 to 1, more preferably (B)₂O₃+Na₂O+ZrO₂)/(Al₂O₃+ MgO) of 0.15 to 0.8, more preferably (B)₂O₃+Na₂O+ZrO₂)/(Al₂O₃And + MgO) is 0.2 to 0.7.

6. A microcrystalline glass product according to any of claims 1-3, characterised in that its composition is expressed in mole percentage, where: (SiO)₂+Li₂O)/(Al₂O₃+ ZnO + MgO) is 5 to 40, preferably (SiO)₂+Li₂O)/(Al₂O₃+ ZnO + MgO) is 8 to 30, more preferably (SiO)₂+Li₂O)/(Al₂O₃+ ZnO + MgO) is 10 to 25, more preferably (SiO)₂+Li₂O)/(Al₂O₃+ ZnO + MgO) is 11 to 20.

7. A microcrystalline glass product according to any of claims 1-3, characterised in that its composition is expressed in mole percentage, where: (SiO)₂+Al₂O₃+Li₂O+Na₂O+ZrO₂)/(P₂O₅+ MgO) of 30 to 90, preferably (SiO)₂+Al₂O₃+Li₂O+Na₂O+ZrO₂)/(P₂O₅+ MgO) 35 to 80, more preferably (SiO)₂+Al₂O₃+Li₂O+Na₂O+ZrO₂)/(P₂O₅+ MgO) is 38 to 75, more preferably (SiO)₂+Al₂O₃+Li₂O+Na₂O+ZrO₂)/(P₂O₅And + MgO) is 40 to 70.

8. A microcrystalline glass product according to any of claims 1-3, characterised in that its composition is expressed in mole percentage, where: (SiO)₂+Al₂O₃)/(P₂O₅+ZrO₂) 12 to 75, preferably (SiO)₂+Al₂O₃)/(P₂O₅+ZrO₂) 15 to 70, more preferably (SiO)₂+Al₂O₃)/(P₂O₅+ZrO₂) Is 17 to 65, and (SiO) is more preferable₂+Al₂O₃)/(P₂O₅+ZrO₂) Is 20 to 60.

9. A microcrystalline glass product according to any of claims 1-3, characterised in that its composition is expressed in mole percentage, where: SiO 2₂: 67-73%, preferably SiO₂: 68-72%; and/or Al₂O₃: 2-6.5%, preferably Al₂O₃: 3-6%; and/or Li₂O: 15.5 to 25%, preferably Li₂O: 17-23.5%; and/or ZnO + MgO: 0.1-4%, preferably ZnO + MgO: 0.2 to 3%, more preferably ZnO + MgO: 0.5-2%; and/or P₂O₅+ZrO₂: 1 to 4%, preferably P₂O₅+ZrO₂: 1.2-3%; and/or Na₂O: 0.5 to 3%, preferably Na₂O: 0.5-2.5%; and/or B₂O₃: 0.5 to 2.5%, preferably B₂O₃: 0.5-2%; and/or K₂O: 0 to 2%, preferably K₂O: 0 to 1.5 percent; and/or SrO: 0 to 2%, preferably SrO: 0 to 1 percent; and/or BaO: 0-2%, preferably BaO: 0 to 1 percent; and/or CaO: 0-2%, preferably CaO: 0 to 1 percent; and/or TiO₂: 0 to 2%, preferably TiO₂: 0 to 1 percent; and/or Y₂O₃: 0 to 2%, preferably Y₂O₃: 0 to 1 percent; and/or a clarifying agent: 0-0.5%, preferably clarifying agent: 0 to 0.2 percent.

10. A microcrystalline glass product according to any of claims 1-3, characterised in that its composition is expressed in mole percentage, where: ZnO: 0-2%, preferably ZnO: 0 to 1.5%, more preferably ZnO: 0 to 1 percent; and/or MgO: 0-4%, preferably MgO: 0 to 3%, more preferably MgO: 0 to 1.5 percent; and/or P₂O₅: 0 to 3%, preferably P₂O₅: 0.2 to 2%, more preferably P₂O₅: 0.4 to 1.5%, and preferably P₂O₅: 0.5-1%; and/or ZrO₂: 0 to 4%, preferably ZrO₂: 0.2 to 3.5%, more preferably ZrO₂: 0.5 to 3%, and more preferably ZrO₂：0.7～2.5％。

11. A crystallized glass product according to any one of claims 1 to 3, wherein the crystallized glass product contains lithium silicate; and/or quartz and quartz solid solutions; and/or petalite, preferably the crystalline phase in the glass-ceramic product contains lithium disilicate and petalite, the total content of the lithium disilicate and the petalite is higher than that of other crystalline phases by weight percent, more preferably the total content of the lithium disilicate and the petalite crystalline phase accounts for 50-80 percent of the glass-ceramic product by weight percent, further preferably the total content of the lithium disilicate and the petalite crystalline phase accounts for 55-75 percent of the glass-ceramic product by weight percent, and further preferably the total content of the lithium disilicate and the petalite crystalline phase accounts for 55-70 percent of the glass-ceramic product by weight percent.

12. A glass-ceramic article according to any of claims 1 to 3, characterized in that the lithium disilicate crystalline phase represents 15 to 40% by weight of the glass-ceramic article, preferably the lithium disilicate crystalline phase represents 20 to 35% by weight of the glass-ceramic article, more preferably the lithium disilicate crystalline phase represents 25 to 35% by weight of the glass-ceramic article; and/or the petalite crystal phase accounts for 30-55% of the weight of the glass-ceramic product, preferably the petalite crystal phase accounts for 35-55% of the weight of the glass-ceramic product, and more preferably the petalite crystal phase accounts for 35-50% of the weight of the glass-ceramic product; and/or the quartz and quartz solid solution crystal phase accounts for 5-25% of the weight of the microcrystalline glass product, preferably the quartz and quartz solid solution crystal phase accounts for 7-20% of the weight of the microcrystalline glass product; and/or the lithium monosilicate crystal phase accounts for 0-10% of the weight of the microcrystalline glass product, preferably the lithium monosilicate crystal phase accounts for 0-7% of the weight of the microcrystalline glass product, and more preferably the lithium monosilicate crystal phase accounts for 0-5% of the weight of the microcrystalline glass product.

13. A crystallized glass product according to any one of claims 1 to 3, wherein the four-point bending strength of the crystallized glass product is 680MPa or more, preferably 700MPa or more, and more preferably 720MPa or more; and/or the ion exchange layer depth of the glass-ceramic product is 85 μm or more, preferably 100 μm or more, more preferably 110 μm or more; and/or the surface stress of the glass-ceramic product is 150MPa or more, preferably 180MPa or more, more preferably 200MPa or more; and/or the height of the microcrystalline glass product in a falling ball test is more than 1500mm, preferably more than 1600mm, and more preferably more than 1700 mm; and/or the fracture toughness of the glass-ceramic product is 1 MPa.m^1/2Above, preferably 1.1MPa · m^1/2More preferably 1.2MPa · m or more^1/2The above; and/or the Vickers hardness of the glass-ceramic article is 750kgf/mm²Above, preferably 780kgf/mm²Above, more preferably 800kgf/mm²The above; and/or the crystallinity of the glass-ceramic product is 55% or more, preferably 65% or more, more preferably 75% or more; and/or the crystallite size of the glass-ceramic product is35nm or less, preferably 30nm or less, and more preferably 25nm or less.

14. A crystallized glass product according to any one of claims 1 to 3, wherein the crystallized glass product having a thickness of 1mm or less has a haze of 0.2% or less, preferably 0.15% or less, more preferably 0.12% or less; and/or a microcrystalline glass product having a thickness of 1mm or less, and having an average transmittance at a wavelength of 400 to 800nm of 87% or more, preferably 88% or more, more preferably 89% or more; and/or a microcrystalline glass product having a thickness of 1mm or less, and having a transmittance at a wavelength of 550nm of 88% or more, preferably 90% or more, more preferably 91% or more; and/or a microcrystalline glass product having a thickness of 1mm or less, wherein the average light | B | value of 400 to 800nm is 0.8 or less, preferably 0.75 or less, more preferably 0.7 or less; and/or the shatter resistance of the microcrystalline glass product having a thickness of 1mm or less is 1700mm or more, preferably 1800mm or more, and more preferably 2000mm or more.

15. A crystallized glass product according to claim 14, wherein the crystallized glass product has a thickness of 0.2-1 mm, preferably 0.3-0.9 mm, more preferably 0.5-0.8 mm, and even more preferably 0.55mm or 0.6mm or 0.68mm or 0.7mm or 0.75 mm.

16. Glass ceramic, characterized in that its composition, expressed in mole percentages, contains: SiO 2₂：65～75％；Al₂O₃：1～8％；Li₂O：14～27％；P₂O₅+ZrO₂：0.5～6％。

17. A glass-ceramic according to claim 16, characterized in that its composition, expressed in mole percentages, further comprises: ZnO + MgO: 0 to 4 percent; and/or Na₂O: 0 to 3.5 percent; and/or B₂O₃: 0 to 3 percent; and/or K₂O: 0 to 3 percent; and/or SrO: 0 to 3 percent; and/or BaO: 0 to 3 percent; and/or CaO: 0 to 3 percent; and/or TiO₂: 0 to 3 percent; and/or Y₂O₃: 0 to 3 percent; and/or a clarifying agent: 0 to 1 percent。

18. Microcrystalline glass, characterized in that its composition, expressed in mol%, is represented by SiO₂：65～75％；Al₂O₃：1～8％；Li₂O：14～27％；P₂O₅+ZrO₂：0.5～6％；ZnO+MgO：0～4％；Na₂O：0～3.5％；B₂O₃：0～3％；K₂O：0～3％；SrO：0～3％；BaO：0～3％；CaO：0～3％；TiO₂：0～3％；Y₂O₃: 0 to 3 percent; a clarifying agent: 0 to 1 percent.

19. A glass-ceramic according to any one of claims 16 to 18, characterized in that its composition is expressed in mole percentage, in which: (Li)₂O+ZrO₂) /(ZnO + MgO) is 10 or more, preferably (Li)₂O+ZrO₂) The value of (ZnO + MgO) is 12 to 45, and (Li) is more preferable₂O+ZrO₂) (ZnO + MgO) is 13 to 40, and (Li) is more preferable₂O+ZrO₂) And/or (ZnO + MgO) 15 to 35.

20. A glass-ceramic according to any one of claims 16 to 18, characterized in that its composition is expressed in mole percentage, in which: (B)₂O₃+Na₂O+ZrO₂)/(Al₂O₃+ MgO) of 0.05 to 1.5, preferably (B)₂O₃+Na₂O+ZrO₂)/(Al₂O₃+ MgO) of 0.1 to 1, more preferably (B)₂O₃+Na₂O+ZrO₂)/(Al₂O₃+ MgO) of 0.15 to 0.8, more preferably (B)₂O₃+Na₂O+ZrO₂)/(Al₂O₃And + MgO) is 0.2 to 0.7.

21. A glass-ceramic according to any one of claims 16 to 18, characterized in that its composition is expressed in mole percentage, in which: (SiO)₂+Li₂O)/(Al₂O₃+ ZnO + MgO) is 5 to 40, preferably (SiO)₂+Li₂O)/(Al₂O₃+ ZnO + MgO) is 8 to 30, more preferably (SiO)₂+Li₂O)/(Al₂O₃+ ZnO + MgO) is 10 to 25, more preferably (SiO)₂+Li₂O)/(Al₂O₃+ ZnO + MgO) is 11 to 20.

22. A glass-ceramic according to any one of claims 16 to 18, characterized in that its composition is expressed in mole percentage, in which: (SiO)₂+Al₂O₃+Li₂O+Na₂O+ZrO₂)/(P₂O₅+ MgO) of 30 to 90, preferably (SiO)₂+Al₂O₃+Li₂O+Na₂O+ZrO₂)/(P₂O₅+ MgO) 35 to 80, more preferably (SiO)₂+Al₂O₃+Li₂O+Na₂O+ZrO₂)/(P₂O₅+ MgO) is 38 to 75, more preferably (SiO)₂+Al₂O₃+Li₂O+Na₂O+ZrO₂)/(P₂O₅And + MgO) is 40 to 70.

23. A glass-ceramic according to any one of claims 16 to 18, characterized in that its composition is expressed in mole percentage, in which: (SiO)₂+Al₂O₃)/(P₂O₅+ZrO₂) 12 to 75, preferably (SiO)₂+Al₂O₃)/(P₂O₅+ZrO₂) 15 to 70, more preferably (SiO)₂+Al₂O₃)/(P₂O₅+ZrO₂) Is 17 to 65, and (SiO) is more preferable₂+Al₂O₃)/(P₂O₅+ZrO₂) Is 20 to 60.

24. A glass-ceramic according to any one of claims 16 to 18, characterized in that its composition is expressed in mole percentage, in which: SiO 2₂: 67-73%, preferably SiO₂: 68-72%; and/or Al₂O₃: 2-6.5%, preferably Al₂O₃: 3-6%; and/or Li₂O: 15.5 to 25%, preferably Li₂O: 17-23.5%; and/or ZnO + MgO: 0.1-4%, preferably ZnO + MgO: 0.2 to 3%, more preferably ZnO + MgO: 0.5-2%; and/or P₂O₅+ZrO₂: 1 to 4%, preferably P₂O₅+ZrO₂: 1.2-3%; and/or Na₂O: 0.5 to 3%, preferably Na₂O: 0.5-2.5%; and/or B₂O₃: 0.5 to 2.5%, preferably B₂O₃: 0.5-2%; and/or K₂O: 0 to 2%, preferably K₂O: 0 to 1.5 percent; and/or SrO: 0 to 2%, preferably SrO: 0 to 1 percent; and/or BaO: 0-2%, preferably BaO: 0 to 1 percent; and/or CaO: 0-2%, preferably CaO: 0 to 1 percent; and/or TiO₂: 0 to 2%, preferably TiO₂: 0 to 1 percent; and/or Y₂O₃: 0 to 2%, preferably Y₂O₃: 0 to 1 percent; and/or a clarifying agent: 0-0.5%, preferably clarifying agent: 0 to 0.2 percent.

25. A glass-ceramic according to any one of claims 16 to 18, characterized in that its composition is expressed in mole percentage, in which: ZnO: 0-2%, preferably ZnO: 0 to 1.5%, more preferably ZnO: 0 to 1 percent; and/or MgO: 0-4%, preferably MgO: 0 to 3%, more preferably MgO: 0 to 1.5 percent; and/or P₂O₅: 0 to 3%, preferably P₂O₅: 0.2 to 2%, more preferably P₂O₅: 0.4 to 1.5%, and preferably P₂O₅: 0.5-1%; and/or ZrO₂: 0 to 4%, preferably ZrO₂: 0.2 to 3.5%, more preferably ZrO₂: 0.5 to 3%, and more preferably ZrO₂：0.7～2.5％。

26. The glass-ceramic according to any one of claims 16 to 18, wherein the crystalline phase in the glass-ceramic contains lithium silicate; and/or quartz and quartz solid solutions; and/or petalite, preferably the crystalline phase in the glass ceramics contains lithium disilicate and petalite, the total content of the lithium disilicate and the petalite is higher than that of other crystalline phases by weight percent, more preferably the total content of the lithium disilicate and the petalite crystalline phase accounts for 50-80 percent of the glass ceramics by weight percent, even more preferably the total content of the lithium disilicate and the petalite crystalline phase accounts for 55-75 percent of the glass ceramics by weight percent, and even more preferably the total content of the lithium disilicate and the petalite crystalline phase accounts for 55-70 percent of the glass ceramics by weight percent.

27. A glass-ceramic according to any one of claims 16 to 18, wherein the lithium disilicate crystalline phase accounts for 15 to 40% by weight of the glass-ceramic, preferably the lithium disilicate crystalline phase accounts for 20 to 35% by weight of the glass-ceramic, and more preferably the lithium disilicate crystalline phase accounts for 25 to 35% by weight of the glass-ceramic; and/or the petalite crystal phase accounts for 30-55% of the weight of the glass ceramics, preferably the petalite crystal phase accounts for 35-55% of the weight of the glass ceramics, and more preferably the petalite crystal phase accounts for 35-50% of the weight of the glass ceramics; and/or the quartz and quartz solid solution crystal phase accounts for 5-25% of the weight of the microcrystalline glass, preferably the quartz and quartz solid solution crystal phase accounts for 7-20% of the weight of the microcrystalline glass; and/or the lithium monosilicate crystal phase accounts for 0-10% of the weight of the microcrystalline glass, preferably the lithium monosilicate crystal phase accounts for 0-7% of the weight of the microcrystalline glass, and more preferably the lithium monosilicate crystal phase accounts for 0-5% of the weight of the microcrystalline glass.

28. A glass-ceramic according to any one of claims 16 to 18, wherein the glass-ceramic has a crystallinity of 55% or more, preferably 65% or more, and more preferably 75% or more; and/or the crystallite size of the glass ceramics is 35nm or less, preferably 30nm or less, preferably 25nm or less; and/or the ball falling height of the microcrystalline glass body is 1800mm or more, preferably 1900mm or more, and more preferably 2000mm or more; and/or the Vickers hardness of the glass-ceramic is 680kgf/mm²Above, preferably 700kgf/mm²Above, 710kgf/mm is more preferable²The above; and/or the coefficient of thermal expansion of the glass-ceramics is 60 x 10^-7/K～90×10^-7K; and/or microcrystalsThe refractive index of the glass is 1.5250-1.5450.

29. The crystallized glass according to any one of claims 16 to 18, wherein the crystallized glass having a thickness of 1mm or less has a haze of 0.2% or less, preferably 0.15% or less, more preferably 0.12% or less; and/or microcrystalline glass having a thickness of 1mm or less, and having an average transmittance of 87% or more, preferably 88% or more, more preferably 89% or more at a wavelength of 400 to 800 nm; and/or a microcrystalline glass having a thickness of 1mm or less, and having a transmittance at a wavelength of 550nm of 88% or more, preferably 90% or more, more preferably 91% or more; and/or microcrystalline glass having a thickness of 1mm or less, wherein the average light | B | value of 400 to 800nm is 0.8 or less, preferably 0.75 or less, more preferably 0.7 or less.

30. A glass-ceramic according to claim 29, wherein the thickness of the glass-ceramic is 0.2-1 mm, preferably 0.3-0.9 mm, more preferably 0.5-0.8 mm, and even more preferably 0.55mm or 0.6mm or 0.68mm or 0.7mm or 0.75 mm.

31. Glass composition, characterized in that its components, expressed in mole percentages, contain: SiO 2₂：65～75％；Al₂O₃：1～8％；Li₂O：14～27％；P₂O₅+ZrO₂：0.5～6％。

32. The glass composition according to claim 31, further comprising, in mole percent: ZnO + MgO: 0 to 4 percent; and/or Na₂O: 0 to 3.5 percent; and/or B₂O₃: 0 to 3 percent; and/or K₂O: 0 to 3 percent; and/or SrO: 0 to 3 percent; and/or BaO: 0 to 3 percent; and/or CaO: 0 to 3 percent; and/or TiO₂: 0 to 3 percent; and/or Y₂O₃: 0 to 3 percent; and/or a clarifying agent: 0 to 1 percent.

33. Glass composition, characterized in that its constituents, expressed in mol%, are represented by SiO₂：65～75％；Al₂O₃：1～8％；Li₂O：14～27％；P₂O₅+ZrO₂：0.5～6％；ZnO+MgO：0～4％；Na₂O：0～3.5％；B₂O₃：0～3％；K₂O：0～3％；SrO：0～3％；BaO：0～3％；CaO：0～3％；TiO₂：0～3％；Y₂O₃: 0 to 3 percent; a clarifying agent: 0 to 1 percent.

34. The glass composition according to any one of claims 31 to 33, wherein the components are expressed in mole percent, wherein: (Li)₂O+ZrO₂) /(ZnO + MgO) is 10 or more, preferably (Li)₂O+ZrO₂) The value of (ZnO + MgO) is 12 to 45, and (Li) is more preferable₂O+ZrO₂) (ZnO + MgO) is 13 to 40, and (Li) is more preferable₂O+ZrO₂) And/or (ZnO + MgO) 15 to 35.

35. The glass composition according to any one of claims 31 to 33, wherein the components are expressed in mole percent, wherein: (B)₂O₃+Na₂O+ZrO₂)/(Al₂O₃+ MgO) of 0.05 to 1.5, preferably (B)₂O₃+Na₂O+ZrO₂)/(Al₂O₃+ MgO) of 0.1 to 1, more preferably (B)₂O₃+Na₂O+ZrO₂)/(Al₂O₃+ MgO) of 0.15 to 0.8, more preferably (B)₂O₃+Na₂O+ZrO₂)/(Al₂O₃And + MgO) is 0.2 to 0.7.

36. The glass composition according to any one of claims 31 to 33, wherein the components are expressed in mole percent, wherein: (SiO)₂+Li₂O)/(Al₂O₃+ ZnO + MgO) is 5 to 40, preferably (SiO)₂+Li₂O)/(Al₂O₃+ ZnO + MgO) is 8 to 30, more preferably (SiO)₂+Li₂O)/(Al₂O₃+ ZnO + MgO) is 10 to 25, more preferablySelecting (SiO)₂+Li₂O)/(Al₂O₃+ ZnO + MgO) is 11 to 20.

37. The glass composition according to any one of claims 31 to 33, wherein the components are expressed in mole percent, wherein: (SiO)₂+Al₂O₃+Li₂O+Na₂O+ZrO₂)/(P₂O₅+ MgO) of 30 to 90, preferably (SiO)₂+Al₂O₃+Li₂O+Na₂O+ZrO₂)/(P₂O₅+ MgO) 35 to 80, more preferably (SiO)₂+Al₂O₃+Li₂O+Na₂O+ZrO₂)/(P₂O₅+ MgO) is 38 to 75, more preferably (SiO)₂+Al₂O₃+Li₂O+Na₂O+ZrO₂)/(P₂O₅And + MgO) is 40 to 70.

38. The glass composition according to any one of claims 31 to 33, wherein the components are expressed in mole percent, wherein: (SiO)₂+Al₂O₃)/(P₂O₅+ZrO₂) 12 to 75, preferably (SiO)₂+Al₂O₃)/(P₂O₅+ZrO₂) 15 to 70, more preferably (SiO)₂+Al₂O₃)/(P₂O₅+ZrO₂) Is 17 to 65, and (SiO) is more preferable₂+Al₂O₃)/(P₂O₅+ZrO₂) Is 20 to 60.

39. The glass composition according to any one of claims 31 to 33, wherein the components are expressed in mole percent, wherein: SiO 2₂: 67-73%, preferably SiO₂: 68-72%; and/or Al₂O₃: 2-6.5%, preferably Al₂O₃: 3-6%; and/or Li₂O: 15.5 to 25%, preferably Li₂O: 17-23.5%; and/or ZnO + MgO: 0.1-4%, preferably ZnO + MgO: 0.2 to 3 percent of the total weight of the mixture,more preferably ZnO + MgO: 0.5-2%; and/or P₂O₅+ZrO₂: 1 to 4%, preferably P₂O₅+ZrO₂: 1.2-3%; and/or Na₂O: 0.5 to 3%, preferably Na₂O: 0.5-2.5%; and/or B₂O₃: 0.5 to 2.5%, preferably B₂O₃: 0.5-2%; and/or K₂O: 0 to 2%, preferably K₂O: 0 to 1.5 percent; and/or SrO: 0 to 2%, preferably SrO: 0 to 1 percent; and/or BaO: 0-2%, preferably BaO: 0 to 1 percent; and/or CaO: 0-2%, preferably CaO: 0 to 1 percent; and/or TiO₂: 0 to 2%, preferably TiO₂: 0 to 1 percent; and/or Y₂O₃: 0 to 2%, preferably Y₂O₃: 0 to 1 percent; and/or a clarifying agent: 0-0.5%, preferably clarifying agent: 0 to 0.2 percent.

40. The glass composition according to any one of claims 31 to 33, wherein the components are expressed in mole percent, wherein: ZnO: 0-2%, preferably ZnO: 0 to 1.5%, more preferably ZnO: 0 to 1 percent; and/or MgO: 0-4%, preferably MgO: 0 to 3%, more preferably MgO: 0 to 1.5 percent; and/or P₂O₅: 0 to 3%, preferably P₂O₅: 0.2 to 2%, more preferably P₂O₅: 0.4 to 1.5%, and preferably P₂O₅: 0.5-1%; and/or ZrO₂: 0 to 4%, preferably ZrO₂: 0.2 to 3.5%, more preferably ZrO₂: 0.5 to 3%, and more preferably ZrO₂：0.7～2.5％。

41. The glass composition of any of claims 31-33, wherein the glass composition has a coefficient of thermal expansion of 55 x 10^-7/K～65×10^-7And/or a refractive index of 1.5100-1.5300.

42. Glass cover plate, characterized in that it is made of a glass-ceramic product according to any of claims 1 to 15, and/or made of a glass-ceramic according to any of claims 16 to 30, and/or made of a glass composition according to any of claims 31 to 41.

43. A glass component, characterized in that it is made of a glass-ceramic product as defined in any one of claims 1 to 15, and/or a glass-ceramic product as defined in any one of claims 16 to 30, and/or a glass composition as defined in any one of claims 31 to 41.

44. A display device comprising the crystallized glass product according to any one of claims 1 to 15, and/or comprising the crystallized glass according to any one of claims 16 to 30, and/or comprising the glass composition according to any one of claims 31 to 41, and/or comprising the glass cover plate according to claim 42, and/or comprising the glass component according to claim 43.

45. An electronic device comprising the glass-ceramic product according to any one of claims 1 to 15, and/or comprising the glass-ceramic according to any one of claims 16 to 30, and/or comprising the glass composition according to any one of claims 31 to 41, and/or comprising the glass cover plate according to claim 42, and/or comprising the glass component according to claim 43.

46. A method for producing a crystallized glass product according to any one of claims 1 to 15, characterized by comprising the steps of: and (2) generating a glass composition, then forming microcrystalline glass by the glass composition through a crystallization process, and then forming a microcrystalline glass product by the microcrystalline glass through a chemical strengthening process.

47. The method for producing a crystallized glass product according to claim 46, wherein the glass composition is formed into a glass shaped body, the glass shaped body is crystallized to form a crystallized glass, and the crystallized glass is chemically strengthened to form a crystallized glass product, or the crystallized glass is formed into a crystallized glass shaped body, and the crystallized glass product is chemically strengthened to form a crystallized glass product.

48. The method of manufacturing a crystallized glass article according to claim 46, 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 650-720 ℃, and the keeping time at the crystallization treatment temperature is 0-8 hours, preferably 1-6 hours.

49. The method of manufacturing a crystallized glass article according to claim 46, wherein the crystallization process comprises the steps of: the method comprises the steps of carrying out nucleation process treatment at the temperature of 1 st, and then carrying out crystal growth process treatment at the temperature of 2 nd, wherein the temperature of 1 st is 470-600 ℃, the holding time at the temperature of 1 st is 0-24 hours, preferably 2-15 hours, the temperature of 2 nd is 600-750 ℃, and the holding time at the temperature of 2 nd is 0-10 hours, preferably 0.5-6 hours.

50. The method of manufacturing a crystallized glass article according to claim 46, wherein the crystallization process comprises the steps of: the method comprises the steps of carrying out nucleation process treatment at the temperature of 1 st, and then carrying out crystal growth process treatment at the temperature of 2 nd and the temperature of 3 rd, wherein the temperature of 1 st is 470-550 ℃, the holding time at the temperature of 1 st is 0-24 hours, preferably 2-15 hours, the temperature of 2 nd is 570-630 ℃, the holding time at the temperature of 2 nd is 0-10 hours, preferably 0.5-6 hours, the temperature of 3 rd is 650-750 ℃, and the holding time at the temperature of 3 rd is 0-10 hours, preferably 0.5-6 hours.

51. The method for manufacturing a crystallized glass product according to claim 46, 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 340-500 ℃ for 1-24 hours, wherein the preferable time range is 2-10 hours.

52. A method for producing a glass ceramic according to any one of claims 16 to 30, characterized by comprising: a glass composition is formed and then a glass-ceramic is formed by a crystallization process on the glass composition.

53. The method for producing a glass ceramic according to claim 52, wherein the glass composition is formed into a glass molded body, and then the glass molded body is crystallized to form the glass ceramic.

54. The method for manufacturing crystallized glass according to claim 52, 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 650-720 ℃, and the keeping time at the crystallization treatment temperature is 0-8 hours, preferably 1-6 hours.

55. The method for manufacturing crystallized glass according to claim 52, wherein the crystallization process includes the steps of: the method comprises the steps of carrying out nucleation process treatment at the temperature of 1 st, and then carrying out crystal growth process treatment at the temperature of 2 nd, wherein the temperature of 1 st is 470-600 ℃, the holding time at the temperature of 1 st is 0-24 hours, preferably 2-15 hours, the temperature of 2 nd is 600-750 ℃, and the holding time at the temperature of 2 nd is 0-10 hours, preferably 0.5-6 hours.

56. The method for manufacturing crystallized glass according to claim 52, wherein the crystallization process includes the steps of: the method comprises the steps of carrying out nucleation process treatment at the temperature of 1 st, and then carrying out crystal growth process treatment at the temperature of 2 nd and the temperature of 3 rd, wherein the temperature of 1 st is 470-550 ℃, the holding time at the temperature of 1 st is 0-24 hours, preferably 2-15 hours, the temperature of 2 nd is 570-630 ℃, the holding time at the temperature of 2 nd is 0-10 hours, preferably 0.5-6 hours, the temperature of 3 rd is 650-750 ℃, and the holding time at the temperature of 3 rd is 0-10 hours, preferably 0.5-6 hours.