Microcrystalline glass, microcrystalline glass product and manufacturing method therefor

Abstract

The present invention provides a microcrystalline glass product. The components of the microcrystalline glass product comprise in percentages by weight: 65-78% of SiO2, 2-12% of R2O, 5-15% of Li2O, 3-12% of Al2O3, 1.5-10% of ZrO2, 0.01-0.6% of CeO2, and 0.01-0.8% of Ag2O, wherein the R2O is one or two of Na2O and K2O. By means of a rational component design, matrix glass in the present invention can be treated by means of a crystallization process to obtain microcrystalline glass having a blackened portion and a transparent portion. The microcrystalline glass obtained by the present invention is suitable for chemical strengthening, and the microcrystalline glass and the microcrystalline glass product prepared therefrom have excellent mechanical properties.

Description

Microcrystalline glass, microcrystalline glass products and their manufacturing methods Technical Field

[0001] This invention relates to a microcrystalline glass, and more particularly to a microcrystalline glass suitable for chemical strengthening. Background Technology

[0002] In recent years, with the rise and development of consumer electronics, glass, as a transparent and high-performance material, has been widely used in electronic devices. Electronic devices contain many delicate electronic components, requiring covers or shells to protect them. With the diversification of market demands, the application scenarios for protective cover glass are becoming increasingly complex, and its role is no longer limited to protecting internal electronic components; sometimes it also needs to perform other functions. For example, in the vital sign monitoring of smartwatches, the glass material needs to be partially transparent, while other areas need to be shaded to avoid interference from stray light. Therefore, the glass material needs to have both black and transparent parts, which poses new challenges to glass manufacturing technology. In existing technologies, the cover material can be manufactured using two different materials, transparent and black, through an embedded design. However, due to the different strengths and large differences in the coefficients of thermal expansion between the two materials, and the need to process through holes, micro-cracks exist on the inner wall of the glass, leading to a reduction in the strength of the cover material. Processing smaller holes or irregular shapes is difficult, resulting in high manufacturing costs.

[0003] Photosensitive microcrystalline glass is a type of glass where the matrix glass undergoes structural changes under ultraviolet light irradiation, generating crystal nuclei. Further heat treatment at a specific temperature results in the formation of numerous specific crystals in the irradiated area. The exposed portions exhibit high crystallinity, a darker glass color, and reduced light transmittance, while the unexposed portions remain transparent, preventing crystallization. Therefore, masking can be used to achieve simultaneous black and transparent portions within the glass material. On the other hand, the glass material used to manufacture protective covers also requires excellent mechanical properties to withstand prolonged exposure to normal touch and potential accidental bending, scratches, and impacts. Chemical strengthening can enhance resistance to accidental damage. However, existing photosensitive microcrystalline glass technologies either cannot be chemically strengthened or suffer from poor chemical strengthening due to the inherent inhomogeneity of the glass body (structural differences between crystalline and non-crystalline portions), making them unsuitable for high-performance electronic devices.

[0004] Summary of the Invention

[0005] Based on the above reasons, the technical problem to be solved by the present invention is to provide a matrix glass that can be used to manufacture microcrystalline glass with blackened and transparent portions.

[0006] The present invention also provides a microcrystalline glass suitable for chemical strengthening, wherein the microcrystalline glass and microcrystalline glass articles made therefrom have excellent mechanical properties.

[0007] The solution adopted by this invention to solve the technical problem is:

[0008] (1) Microcrystalline glass products, the components of which, expressed by weight percentage, contain: SiO2: 65-78%; R2O: 2-12%; Li2O: 5-15%; Al2O3: 3-12%; ZrO2: 1.5-10%; CeO2: 0.01-0.6%; Ag2O: 0.01-0.8%, wherein the R2O is one or both of Na2O and K2O.

[0009] (2) The microcrystalline glass product according to (1) further contains, by weight percentage: Sb2O3: 0-1%; and / or SnO2: 0-0.5%; and / or MO: 0-5%; and / or Ln2O3: 0-5%; and / or Fe2O3: 0-1%, wherein MO is one or more of MgO, CaO, SrO, BaO, and ZnO, and Ln2O3 is one or more of La2O3, Gd2O3, and Y2O3.

[0010] (3) Microcrystalline glass products, the components of which are expressed by weight percentage as follows: SiO2: 65-78%; R2O: 2-12%; Li2O: 5-15%; Al2O3: 3-12%; ZrO2: 1.5-10%; CeO2: 0.01-0.6%; Ag2O: 0.01-0.8%; Sb2O3: 0-1%; SnO2: 0-0.5%; MO: 0-5%; Ln2O3: 0-5%; Fe2O3: 0-1%, wherein R2O is one or two of Na2O and K2O, MO is one or more of MgO, CaO, SrO, BaO and ZnO, and Ln2O3 is one or more of La2O3, Gd2O3 and Y2O3.

[0011] (4) A microcrystalline glass product containing SiO2, R2O, Li2O, Al2O3, ZrO2, CeO2 and Ag2O, wherein R2O is one or two of Na2O and K2O, and the drop ball test height II of the microcrystalline glass product is 800mm or more.

[0012] (5) A microcrystalline glass product comprising one or more blackened portions and one or more transparent portions, wherein the microcrystalline glass product contains a lithium metasilicate crystalline phase, and the weight percentage of the lithium metasilicate crystalline phase in the blackened portion of the microcrystalline glass product is 5 to 50%.

[0013] (6) A microcrystalline glass product, the composition of which contains SiO2, R2O, Li2O, Al2O3, ZrO2, CeO2 and Ag2O, wherein the R2O is one or two of Na2O and K2O, and the microcrystalline glass product comprises one or more blackened portions and one or more transparent portions.

[0014] (7) A microcrystalline glass product containing SiO2, Li2O, Al2O3 and ZrO2, wherein R2O is one or two of Na2O and K2O, and the composition is expressed as a weight percentage, wherein: SiO2 / Li2O is 5.5 to 10.0.

[0015] (8) A microcrystalline glass product containing SiO2, R2O, Li2O, Al2O3 and ZrO2, wherein R2O is one or two of Na2O and K2O, and the composition is expressed as a weight percentage, wherein (K2O+Na2O) / ZrO2 is 0.5 to 7.1.

[0016] (9) Microcrystalline glass products containing SiO2, Li2O, Al2O3 and ZrO2, the composition of which is expressed as a weight percentage, wherein (SiO2+Li2O) / ZrO2 is 8.0 to 55.0.

[0017] (10) A microcrystalline glass product containing SiO2, R2O, Li2O, Al2O3 and ZrO2, wherein R2O is one or two of Na2O and K2O, and the microcrystalline glass product contains a lithium metasilicate crystal phase, wherein the lithium metasilicate crystal phase has a higher weight percentage than other crystal phases.

[0018] (11) A microcrystalline glass product comprising one or more blackened portions and one or more transparent portions, wherein the transmittance T of the blackened portion of a microcrystalline glass product with a thickness of 0.2–1.5 mm at 870 nm is... 870nm It is below 15.0%.

[0019] (12) A microcrystalline glass product comprising one or more blackened portions and one or more transparent portions, wherein the transmittance T of the blackened portion of a microcrystalline glass product with a thickness of 0.2–1.5 mm at 940 nm is... 940nm It is below 50.0%.

[0020] (13) The microcrystalline glass article according to any one of (4) to (12), wherein the components are expressed as weight percentages, wherein: SiO2: 65-78%; and / or R2O: 2-12%; and / or Li2O: 5-15%; and / or Al2O3: 3-12%; and / or ZrO2: 1.5-10%; and / or CeO2: 0.01-0.6%; and / or Ag2O: 0.01-0.8%; and / or Sb2O3: 0-1%; and / or SnO2: 0-0.5%; and / or MO: 0-5%; and / or Ln2O3: 0-5%; and / or Fe2O3: 0-1%, wherein R2O is one or two of Na2O and K2O, MO is one or more of MgO, CaO, SrO, BaO, and ZnO, and Ln2O3 is one or more of La2O3, Gd2O3, and Y2O3.

[0021] (14) The microcrystalline glass article according to any one of (1) to (13) has components expressed as a weight percentage, wherein: SiO2 / Li2O is 5.5 to 10.0, preferably SiO2 / Li2O is 6.0 to 9.0, and more preferably SiO2 / Li2O is 7.0 to 8.5.

[0022] (15) The microcrystalline glass article according to any one of (1) to (14) has its components expressed as a weight percentage, wherein: (Sb2O3+SnO2) / Ag2O is 0.1 to 5.0, preferably (Sb2O3+SnO2) / Ag2O is 0.5 to 3.5, and more preferably (Sb2O3+SnO2) / Ag2O is 1.0 to 2.6.

[0023] (16) The microcrystalline glass article according to any one of (1) to (15) has components expressed as a weight percentage, wherein: (K2O+Na2O) / ZrO2 is 0.5 to 7.1, preferably (K2O+Na2O) / ZrO2 is 0.7 to 4.5, and more preferably (K2O+Na2O) / ZrO2 is 0.8 to 2.5.

[0024] (17) The microcrystalline glass article according to any one of (1) to (16) has components expressed as a weight percentage, wherein: Ag2O / CeO2 is 1.0 to 10.0, preferably Ag2O / CeO2 is 1.5 to 6.5, and more preferably Ag2O / CeO2 is 2.0 to 4.5.

[0025] (18) The microcrystalline glass article according to any one of (1) to (17) has the following components expressed as a weight percentage: Li2O / ZrO2 is 1.0 to 7.5, preferably Li2O / ZrO2 is 1.2 to 5.0, more preferably Li2O / ZrO2 is 1.4 to 4.3, and even more preferably Li2O / ZrO2 is 1.6 to 3.0.

[0026] (19) The microcrystalline glass article according to any one of (1) to (18) has the following composition expressed as a weight percentage: (SiO2+Li2O) / ZrO2 is 8.0 to 55.0, preferably (SiO2+Li2O) / ZrO2 is 10.0 to 37.0, more preferably (SiO2+Li2O) / ZrO2 is 12.0 to 25.0, and even more preferably (SiO2+Li2O) / ZrO2 is 13.0 to 20.0.

[0027] (20) The microcrystalline glass article according to any one of (1) to (19) has the following composition expressed as a weight percentage: ZrO2 / (Ag2O+CeO2) is 2.3 to 50.0, preferably ZrO2 / (Ag2O+CeO2) is 6.5 to 35.0, more preferably ZrO2 / (Ag2O+CeO2) is 8.5 to 20.0, and even more preferably ZrO2 / (Ag2O+CeO2) is 11.0 to 18.0.

[0028] (21) The microcrystalline glass article according to any one of (1) to (20) has the following composition expressed as a weight percentage: (Ag2O+SnO2+Sb2O3) / CeO2 is 1.0 to 30.0, preferably (Ag2O+SnO2+Sb2O3) / CeO2 is 3.0 to 20.0, more preferably (Ag2O+SnO2+Sb2O3) / CeO2 is 5.0 to 12.5, and even more preferably (Ag2O+SnO2+Sb2O3) / CeO2 is 7.5 to 10.0.

[0029] (22) The microcrystalline glass article according to any one of (1) to (21) has components expressed as a weight percentage, wherein: (Sb2O3+SnO2+CeO2) / Ag2O is 0.1 to 10.0, preferably (Sb2O3+SnO2+CeO2) / Ag2O is 0.4 to 5.0, more preferably (Sb2O3+SnO2+CeO2) / Ag2O is 0.7 to 3.7, and even more preferably (Sb2O3+SnO2+CeO2) / Ag2O is 1.5 to 3.2.

[0030] (23) The microcrystalline glass article according to any one of (1) to (22) has components expressed as a weight percentage, wherein: SnO2 / (CeO2+SnO2) is 0 to 0.9, preferably SnO2 / (CeO2+SnO2) is 0 to 0.6, and more preferably SnO2 / (CeO2+SnO2) is 0 to 0.5.

[0031] (24) The microcrystalline glass product according to any one of (1) to (23) has components expressed as weight percentages, wherein: R2O+Li2O+Al2O3 is 15-30%, preferably R2O+Li2O+Al2O3 is 17.5-29.5%, more preferably R2O+Li2O+Al2O3 is 18.5-26%, and even more preferably R2O+Li2O+Al2O3 is 20-25%, wherein R2O is one or two of Na2O and K2O.

[0032] (25) The microcrystalline glass article according to any one of (1) to (24) has the following composition expressed as a weight percentage: (SiO2+Al2O3) / (Li2O+Na2O+K2O) is 3.0 to 7.5, preferably (SiO2+Al2O3) / (Li2O+Na2O+K2O) is 3.7 to 6.5, more preferably (SiO2+Al2O3) / (Li2O+Na2O+K2O) is 4.3 to 6.0, and even more preferably (SiO2+Al2O3) / (Li2O+Na2O+K2O) is 4.8 to 5.8.

[0033] (26) The microcrystalline glass article according to any one of (1) to (25) has components expressed as a weight percentage, wherein: MO / ZrO2 is 2.5 or less, preferably MO / ZrO2 is 1.5 or less, more preferably MO / ZrO2 is 0.5 or less, and MO is one or more of MgO, CaO, SrO, BaO, and ZnO.

[0034] (27) The microcrystalline glass article according to any one of (1) to (26) has the following components expressed as weight percentages: Sb2O3+SnO2: 0.05 to 1.2%, preferably Sb2O3+SnO2: 0.1 to 1%, more preferably Sb2O3+SnO2: 0.2 to 0.7%.

[0035] (28) The microcrystalline glass article according to any one of (1) to (27), wherein the components are expressed as weight percentages, wherein: SiO2: 68-77%, preferably SiO2: 69.5-75.5%; and / or R2O: 3-10%, preferably R2O: 4-8%; and / or Li2O: 7-13%, preferably Li2O: 8.5-12%; and / or Al2O3: 4-10%, preferably Al2O3: 5-9%; and / or ZrO2: 2-8%, preferably ZrO2: 3-6.5%; and / or CeO2: 0.07-0.4%, preferably CeO2: 0.08-0.3%; and / or Ag2O: 0.1-0.6%, preferably Ag2O: 0.2-0.5%; and / or Sb2 O3: 0.01-0.7%, preferably Sb2O3: 0.07-0.5%; and / or SnO2: 0-0.3%, preferably SnO2: 0-0.2%; and / or MO: 0-3%, preferably MO: 0-1%, more preferably without MO; and / or Ln2O3: 0-3%, preferably Ln2O3: 0-1%, more preferably without Ln2O3; and / or Fe2O3: 0-0.5%, preferably Fe2O3: 0-0.2%, more preferably without Fe2O3, wherein R2O is one or two of Na2O and K2O, MO is one or more of MgO, CaO, SrO, BaO, and ZnO, and Ln2O3 is one or more of La2O3, Gd2O3, and Y2O3.

[0036] (29) The microcrystalline glass article according to any one of (1) to (28) comprises one or more blackened portions and one or more transparent portions; or the microcrystalline glass article is entirely composed of blackened portions.

[0037] (30) The glass-ceramic article according to any one of (1) to (29), wherein the glass-ceramic article contains a lithium silicate crystalline phase, preferably a lithium metasilicate crystalline phase, more preferably the lithium metasilicate crystalline phase in the blackened portion of the glass-ceramic article has a weight percentage of 5 to 50%, further preferably the lithium metasilicate crystalline phase in the blackened portion of the glass-ceramic article has a weight percentage of 5 to 40%, and even more preferably the lithium metasilicate crystalline phase in the blackened portion of the glass-ceramic article has a weight percentage of 10 to 30%.

[0038] (31) The microcrystalline glass article according to any one of (1) to (30), the average transmittance T of the transparent portion of the microcrystalline glass article with a thickness of 0.2 to 1.5 mm in the 400 to 800 nm wavelength range. 400-800nmThe transmittance is 85.0% or more, preferably 88.0% or more, more preferably 90.0% or more, further preferably 91.0% or more, and even more preferably 91.5 to 95.0%; and / or the average transmittance T of the blackened portion of a microcrystalline glass article with a thickness of 0.2 to 1.5 mm in the 400 to 800 nm wavelength range. 400-800nm The transmittance T of the blackened portion of a microcrystalline glass article with a thickness of 0.2 to 1.5 mm at 870 nm is 5.0% or less, preferably 3.0% or less, more preferably 1.5% or less, even more preferably 1.2% or less, and still more preferably 0.5% or less; and / or the transmittance T of the blackened portion of the microcrystalline glass article with a thickness of 0.2 to 1.5 mm. 870nm The transmittance T of the blackened portion of a microcrystalline glass article with a thickness of 0.2 to 1.5 mm at 940 nm is 15.0% or less, preferably 0.1 to 12.5%, more preferably 0.1 to 10%, further preferably 0.1 to 8.0%, and even more preferably 0.1 to 5.0%; and / or the transmittance T of the blackened portion of the microcrystalline glass article with a thickness of 0.2 to 1.5 mm. 940nm The content is 50.0% or less, preferably 0.1% to 35.0%, more preferably 0.3% to 20.0%, even more preferably 0.3% to 15.0%, and even more preferably 0.3% to 10.0%.

[0039] (32) The microcrystalline glass article according to any one of (1) to (31) has a thickness of 0.5 to 1.5 mm, preferably 0.8 to 1.2 mm, and more preferably 0.5 mm, 0.7 mm, 0.8 mm, 0.9 mm, 1.0 mm, 1.1 mm, or 1.2 mm.

[0040] (33) The microcrystalline glass article according to any one of (1) to (32) has a drop ball test height II of 800 mm or more, preferably 900 mm or more, more preferably 1000 mm or more, and even more preferably 1100 mm or more.

[0041] (34) Microcrystalline glass, the composition of which, by weight percentage, contains: SiO2: 65-78%; R2O: 2-12%; Li2O: 5-15%; Al2O3: 3-12%; ZrO2: 1.5-10%; CeO2: 0.01-0.6%; Ag2O: 0.01-0.8%, wherein the R2O is one or both of Na2O and K2O.

[0042] (35) The microcrystalline glass according to (34) further comprises, by weight percentage: Sb2O3: 0-1%; and / or SnO2: 0-0.5%; and / or MO: 0-5%; and / or Ln2O3: 0-5%; and / or Fe2O3: 0-1%, wherein MO is one or more of MgO, CaO, SrO, BaO, and ZnO, and Ln2O3 is one or more of La2O3, Gd2O3, and Y2O3.

[0043] (36) Microcrystalline glass, the composition of which, by weight percentage, is composed of SiO2: 65-78%; R2O: 2-12%; Li2O: 5-15%; Al2O3: 3-12%; ZrO2: 1.5-10%; CeO2: 0.01-0.6%; Ag2O: 0.01-0.8%; Sb2O3: 0-1%; SnO2: 0-0.5%; MO: 0-5%; Ln2O3: 0-5%; Fe2O3: 0-1%, wherein R2O is one or two of Na2O and K2O, MO is one or more of MgO, CaO, SrO, BaO, and ZnO, and Ln2O3 is one or more of La2O3, Gd2O3, and Y2O3.

[0044] (37) A glass-ceramic comprising one or more blackened portions and one or more transparent portions, wherein the glass-ceramic contains a lithium metasilicate crystalline phase, wherein the weight percentage of the lithium metasilicate crystalline phase in the blackened portion of the glass-ceramic is 5 to 50%.

[0045] (38) A microcrystalline glass, the composition of which contains SiO2, R2O, Li2O, Al2O3, ZrO2, CeO2 and Ag2O, wherein the R2O is one or two of Na2O and K2O, and the microcrystalline glass comprises one or more blackened portions and one or more transparent portions.

[0046] (39) Microcrystalline glass, the composition of which contains SiO2, R2O, Li2O, Al2O3 and ZrO2, wherein R2O is one or two of Na2O and K2O, and the composition is expressed as a weight percentage, wherein: SiO2 / Li2O is 5.5 to 10.0.

[0047] (40) Microcrystalline glass, the composition of which contains SiO2, R2O, Li2O, Al2O3 and ZrO2, wherein R2O is one or two of Na2O and K2O, and the composition is expressed as a weight percentage, wherein (K2O+Na2O) / ZrO2 is 0.5 to 7.1.

[0048] (41) Microcrystalline glass, the composition of which contains SiO2, R2O, Li2O, Al2O3 and ZrO2, wherein R2O is one or two of Na2O and K2O, and the composition is expressed as a weight percentage, wherein (SiO2+Li2O) / ZrO2 is 8.0 to 55.0.

[0049] (42) Microcrystalline glass, the composition of which contains SiO2, Li2O, Al2O3, CeO2 and Ag2O, wherein R2O is one or two of Na2O and K2O, and the Ag2O / CeO2 ratio is 1.0 to 10.0.

[0050] (43) A microcrystalline glass containing SiO2, R2O, Li2O, Al2O3 and ZrO2, wherein R2O is one or two of Na2O and K2O, and the microcrystalline glass contains a lithium metasilicate crystal phase, wherein the lithium metasilicate crystal phase has a higher weight percentage than other crystal phases.

[0051] (44) A microcrystalline glass, the composition of which contains SiO2, R2O, Li2O, Al2O3 and ZrO2, wherein R2O is one or two of Na2O and K2O, and the microcrystalline glass contains a lithium silicate crystalline phase.

[0052] (45) A microcrystalline glass comprising one or more blackened portions and one or more transparent portions, wherein the transmittance T of the blackened portion of a microcrystalline glass with a thickness of 0.2–1.5 mm at 870 nm is... 870nm It is below 15.0%.

[0053] (46) A microcrystalline glass comprising one or more blackened portions and one or more transparent portions, wherein the transmittance T of the blackened portion of a microcrystalline glass with a thickness of 0.2–1.5 mm at 940 nm is... 940nm It is below 50.0%.

[0054] (47) The microcrystalline glass according to any one of (37) to (46), wherein the components are expressed as weight percentages, wherein: SiO2: 65-78%; and / or R2O: 2-12%; and / or Li2O: 5-15%; and / or Al2O3: 3-12%; and / or ZrO2: 1.5-10%; and / or CeO2: 0.01-0.6%; and / or Ag2O: 0.01-0.8%; and / or Or Sb2O3: 0-1%; and / or SnO2: 0-0.5%; and / or MO: 0-5%; and / or Ln2O3: 0-5%; and / or Fe2O3: 0-1%, wherein R2O is one or two of Na2O and K2O, MO is one or more of MgO, CaO, SrO, BaO, and ZnO, and Ln2O3 is one or more of La2O3, Gd2O3, and Y2O3.

[0055] (48) The microcrystalline glass according to any one of (34) to (47) has the following composition expressed as a weight percentage: SiO2 / Li2O is 5.5 to 10.0, preferably SiO2 / Li2O is 6.0 to 9.0, and more preferably SiO2 / Li2O is 7.0 to 8.5.

[0056] (49) The microcrystalline glass according to any one of (34) to (48) has the following composition expressed as a weight percentage: (Sb2O3+SnO2) / Ag2O is 0.1 to 5.0, preferably (Sb2O3+SnO2) / Ag2O is 0.5 to 3.5, and more preferably (Sb2O3+SnO2) / Ag2O is 1.0 to 2.6.

[0057] (50) The microcrystalline glass according to any one of (34) to (49) has the following composition expressed as a weight percentage: (K2O+Na2O) / ZrO2 is 0.5 to 7.1, preferably (K2O+Na2O) / ZrO2 is 0.7 to 4.5, and more preferably (K2O+Na2O) / ZrO2 is 0.8 to 2.5.

[0058] (51) The microcrystalline glass according to any one of (34) to (50) has the following composition expressed as a weight percentage: Ag2O / CeO2 is 1.0 to 10.0, preferably Ag2O / CeO2 is 1.5 to 6.5, and more preferably Ag2O / CeO2 is 2.0 to 4.5.

[0059] (52) The microcrystalline glass according to any one of (34) to (51) has the following composition expressed in weight percentage: Li2O / ZrO2 is 1.0 to 7.5, preferably Li2O / ZrO2 is 1.2 to 5.0, more preferably Li2O / ZrO2 is 1.4 to 4.3, and even more preferably Li2O / ZrO2 is 1.6 to 3.0.

[0060] (53) The microcrystalline glass according to any one of (34) to (52) has the following composition expressed as a weight percentage: (SiO2+Li2O) / ZrO2 is 8.0 to 55.0, preferably (SiO2+Li2O) / ZrO2 is 10.0 to 37.0, more preferably (SiO2+Li2O) / ZrO2 is 12.0 to 25.0, and even more preferably (SiO2+Li2O) / ZrO2 is 13.0 to 20.0.

[0061] (54) The microcrystalline glass according to any one of (34) to (53) has the following composition expressed as a weight percentage: ZrO2 / (Ag2O+CeO2) is 2.3 to 50.0, preferably ZrO2 / (Ag2O+CeO2) is 6.5 to 35.0, more preferably ZrO2 / (Ag2O+CeO2) is 8.5 to 20.0, and even more preferably ZrO2 / (Ag2O+CeO2) is 11.0 to 18.0.

[0062] (55) The microcrystalline glass according to any one of (34) to (54) has the following composition expressed as a weight percentage: (Ag2O+SnO2+Sb2O3) / CeO2 is 1.0 to 30.0, preferably (Ag2O+SnO2+Sb2O3) / CeO2 is 3.0 to 20.0, more preferably (Ag2O+SnO2+Sb2O3) / CeO2 is 5.0 to 12.5, and even more preferably (Ag2O+SnO2+Sb2O3) / CeO2 is 7.5 to 10.0.

[0063] (56) The microcrystalline glass according to any one of (34) to (55) has the following composition expressed as a weight percentage: (Sb2O3+SnO2+CeO2) / Ag2O is 0.1 to 10.0, preferably (Sb2O3+SnO2+CeO2) / Ag2O is 0.4 to 5.0, more preferably (Sb2O3+SnO2+CeO2) / Ag2O is 0.7 to 3.7, and even more preferably (Sb2O3+SnO2+CeO2) / Ag2O is 1.5 to 3.2.

[0064] (57) The microcrystalline glass according to any one of (34) to (56) has components expressed as a weight percentage, wherein: SnO2 / (CeO2+SnO2) is 0 to 0.9, preferably SnO2 / (CeO2+SnO2) is 0 to 0.6, and more preferably SnO2 / (CeO2+SnO2) is 0 to 0.5.

[0065] (58) The microcrystalline glass according to any one of (34) to (57) has the following composition expressed as a weight percentage: R2O+Li2O+Al2O3 is 15-30%, preferably R2O+Li2O+Al2O3 is 17.5-29.5%, more preferably R2O+Li2O+Al2O3 is 18.5-26%, and even more preferably R2O+Li2O+Al2O3 is 20-25%, wherein R2O is one or both of Na2O and K2O.

[0066] (59) The microcrystalline glass according to any one of (34) to (58) has the following composition expressed as a weight percentage: (SiO2+Al2O3) / (Li2O+Na2O+K2O) is 3.0 to 7.5, preferably (SiO2+Al2O3) / (Li2O+Na2O+K2O) is 3.7 to 6.5, more preferably (SiO2+Al2O3) / (Li2O+Na2O+K2O) is 4.3 to 6.0, and even more preferably (SiO2+Al2O3) / (Li2O+Na2O+K2O) is 4.8 to 5.8.

[0067] (60) The microcrystalline glass according to any one of (34) to (59) has components expressed as a weight percentage, wherein: MO / ZrO2 is 2.5 or less, preferably MO / ZrO2 is 1.5 or less, more preferably MO / ZrO2 is 0.5 or less, and MO is one or more of MgO, CaO, SrO, BaO, and ZnO.

[0068] (61) The microcrystalline glass according to any one of (34) to (60) has the following composition expressed in weight percentage: Sb2O3+SnO2: 0.05 to 1.2%, preferably Sb2O3+SnO2: 0.1 to 1%, more preferably Sb2O3+SnO2: 0.2 to 0.7%.

[0069] (62) The microcrystalline glass according to any one of (34) to (61), wherein the components are expressed in weight percentages, wherein: SiO2: 68-77%, preferably SiO2: 69.5-75.5%; and / or R2O: 3-10%, preferably R2O: 4-8%; and / or Li2O: 7-13%, preferably Li2O: 8.5-12%; and / or Al2O3: 4-10%, preferably Al2O3: 5-9%; and / or ZrO2: 2-8%, preferably ZrO2: 3-6.5%; and / or CeO2: 0.07-0.4%, preferably CeO2: 0.08-0.3%; and / or Ag2O: 0.1-0.6%, preferably Ag2O: 0.2-0.5%; and / or Sb2O 3: 0.01-0.7%, preferably Sb2O3: 0.07-0.5%; and / or SnO2: 0-0.3%, preferably SnO2: 0-0.2%; and / or MO: 0-3%, preferably MO: 0-1%, more preferably without MO; and / or Ln2O3: 0-3%, preferably Ln2O3: 0-1%, more preferably without Ln2O3; and / or Fe2O3: 0-0.5%, preferably Fe2O3: 0-0.2%, more preferably without Fe2O3, wherein R2O is one or two of Na2O and K2O, MO is one or more of MgO, CaO, SrO, BaO, and ZnO, and Ln2O3 is one or more of La2O3, Gd2O3, and Y2O3.

[0070] (63) The glass crystal according to any one of (34) to (62) comprises one or more blackened portions and one or more transparent portions; or the entire glass crystal is blackened.

[0071] (64) The glass-ceramic according to any one of (34) to (63) contains a lithium silicate phase, preferably a lithium metasilicate phase, more preferably the lithium metasilicate phase in the blackened portion of the glass-ceramic contains 5 to 50% by weight, even more preferably the lithium metasilicate phase in the blackened portion of the glass-ceramic contains 5 to 40% by weight, and even more preferably the lithium metasilicate phase in the blackened portion of the glass-ceramic contains 10 to 30% by weight.

[0072] (65) The microcrystalline glass according to any one of (34) to (64), the average transmittance T of the transparent portion of the microcrystalline glass with a thickness of 0.2 to 1.5 mm in the 400 to 800 nm wavelength range. 400-800nm The transmittance is 85.0% or more, preferably 88.0% or more, more preferably 90.0% or more, even more preferably 91.0% or more, and even more preferably 91.5 to 95.0%; and / or the average transmittance T of the blackened portion of the microcrystalline glass with a thickness of 0.2 to 1.5 mm in the 400 to 800 nm wavelength range.400-800nm The transmittance T of the blackened portion of the microcrystalline glass with a thickness of 0.2 to 1.5 mm at 870 nm is 5.0% or less, preferably 3.0% or less, more preferably 1.5% or less, even more preferably 1.2% or less, and still more preferably 0.5% or less; and / or the transmittance T of the blackened portion of the microcrystalline glass with a thickness of 0.2 to 1.5 mm. 870nm The transmittance T of the blackened portion of a microcrystalline glass with a thickness of 0.2 to 1.5 mm at 940 nm is 15.0% or less, preferably 0.1 to 12.5%, more preferably 0.1 to 10%, further preferably 0.1 to 8.0%, and even more preferably 0.1 to 5.0%; and / or the transmittance T of the blackened portion of the microcrystalline glass with a thickness of 0.2 to 1.5 mm. 940nm The content is 50.0% or less, preferably 0.1% to 35.0%, more preferably 0.3% to 20.0%, even more preferably 0.3% to 15.0%, and even more preferably 0.3% to 10.0%.

[0073] (66) The microcrystalline glass according to any one of (34) to (65) has a thickness of 0.5 to 1.5 mm, preferably 0.8 to 1.2 mm, and more preferably 0.5 mm, 0.7 mm, 0.8 mm, 0.9 mm, 1.0 mm, 1.1 mm, or 1.2 mm.

[0074] (67) A matrix glass, the composition of which, by weight percentage, contains: SiO2: 65-78%; R2O: 2-12%; Li2O: 5-15%; Al2O3: 3-12%; ZrO2: 1.5-10%; CeO2: 0.01-0.6%; Ag2O: 0.01-0.8%, wherein the R2O is one or both of Na2O and K2O.

[0075] (68) The matrix glass according to (67) further comprises, by weight percentage: Sb2O3: 0-1%; and / or SnO2: 0-0.5%; and / or MO: 0-5%; and / or Ln2O3: 0-5%; and / or Fe2O3: 0-1%, wherein MO is one or more of MgO, CaO, SrO, BaO, and ZnO, and Ln2O3 is one or more of La2O3, Gd2O3, and Y2O3.

[0076] (69) A matrix glass, the composition of which, by weight percentage, is composed of SiO2: 65-78%; R2O: 2-12%; Li2O: 5-15%; Al2O3: 3-12%; ZrO2: 1.5-10%; CeO2: 0.01-0.6%; Ag2O: 0.01-0.8%; Sb2O3: 0-1%; SnO2: 0-0.5%; MO: 0-5%; Ln2O3: 0-5%; Fe2O3: 0-1%, wherein R2O is one or two of Na2O and K2O, MO is one or more of MgO, CaO, SrO, BaO, and ZnO, and Ln2O3 is one or more of La2O3, Gd2O3, and Y2O3.

[0077] (70) A matrix glass containing SiO2, R2O, Li2O, Al2O3 and ZrO2, wherein R2O is one or two of Na2O and K2O, and the composition is expressed as a weight percentage, wherein SiO2 / Li2O is 5.5 to 10.0.

[0078] (71) A matrix glass containing SiO2, R2O, Li2O, Al2O3 and ZrO2, wherein R2O is one or both of Na2O and K2O, and the composition is expressed as a weight percentage, wherein (K2O+Na2O) / ZrO2 is 0.5 to 7.1.

[0079] (72) A matrix glass containing SiO2, R2O, Li2O, Al2O3 and ZrO2, wherein R2O is one or two of Na2O and K2O, and the composition is expressed as a weight percentage, wherein (SiO2+Li2O) / ZrO2 is 8.0 to 55.0.

[0080] (73) A matrix glass containing SiO2, R2O, Li2O, Al2O3, ZrO2, CeO2 and Ag2O, wherein R2O is one or two of Na2O and K2O, and the Ag2O / CeO2 ratio is 1.0 to 10.0.

[0081] (74) A matrix glass containing SiO2, R2O, Li2O, Al2O3, and ZrO2, wherein R2O is one or both of Na2O and K2O, and the Young's modulus E of the matrix glass is 7000 × 10⁻⁶. 7 Pa ~ 9500 × 10 7 Pa.

[0082] (75) A matrix glass containing SiO2, R2O, Li2O, Al2O3, and ZrO2, wherein the R2O is one or both of Na2O and K2O, and the dielectric constant ε of the matrix glass is... rThe value ranges from 5.5 to 8.5.

[0083] (76) A matrix glass containing SiO2, R2O, Li2O, Al2O3, and ZrO2, wherein the R2O is one or both of Na2O and K2O, and the Knoop hardness of the matrix glass is Hk. 0.1 450 kgf / mm 2 above.

[0084] (77) A matrix glass containing SiO2, R2O, Li2O and ZrO2, wherein the R2O is one or both of Na2O and K2O, and the linear expansion coefficient α of the matrix glass is... 20℃-300℃ 100×10 -7 / ℃ below.

[0085] (78) The matrix glass according to any one of (70) to (77), wherein the components are expressed as weight percentages, wherein: SiO2: 65-78%; and / or R2O: 2-12%; and / or Li2O: 5-15%; and / or Al2O3: 3-12%; and / or ZrO2: 1.5-10%; and / or CeO2: 0.01-0.6%; and / or Ag2O: 0.01-0.8%; and / or Or Sb2O3: 0-1%; and / or SnO2: 0-0.5%; and / or MO: 0-5%; and / or Ln2O3: 0-5%; and / or Fe2O3: 0-1%, wherein R2O is one or two of Na2O and K2O, MO is one or more of MgO, CaO, SrO, BaO, and ZnO, and Ln2O3 is one or more of La2O3, Gd2O3, and Y2O3.

[0086] (79) The matrix glass according to any one of (67) to (78) has the following composition expressed in weight percentage: SiO2 / Li2O is 5.5 to 10.0, preferably SiO2 / Li2O is 6.0 to 9.0, and more preferably SiO2 / Li2O is 7.0 to 8.5.

[0087] (80) The matrix glass according to any one of (67) to (79) has the following composition expressed as a weight percentage: (Sb2O3+SnO2) / Ag2O is 0.1 to 5.0, preferably (Sb2O3+SnO2) / Ag2O is 0.5 to 3.5, and more preferably (Sb2O3+SnO2) / Ag2O is 1.0 to 2.6.

[0088] (81) The matrix glass according to any one of (67) to (80) has the following composition expressed as a weight percentage: (K2O+Na2O) / ZrO2 is 0.5 to 7.1, preferably (K2O+Na2O) / ZrO2 is 0.7 to 4.5, and more preferably (K2O+Na2O) / ZrO2 is 0.8 to 2.5.

[0089] (82) The matrix glass according to any one of (67) to (81) has components expressed as weight percentages, wherein: Ag2O / CeO2 is 1.0 to 10.0, preferably Ag2O / CeO2 is 1.5 to 6.5, and more preferably Ag2O / CeO2 is 2.0 to 4.5.

[0090] (83) The matrix glass according to any one of (67) to (82) has the following composition expressed in weight percentage: Li2O / ZrO2 is 1.0 to 7.5, preferably Li2O / ZrO2 is 1.2 to 5.0, more preferably Li2O / ZrO2 is 1.4 to 4.3, and even more preferably Li2O / ZrO2 is 1.6 to 3.0.

[0091] (84) The matrix glass according to any one of (67) to (83) has the following composition expressed as a weight percentage: (SiO2+Li2O) / ZrO2 is 8.0 to 55.0, preferably (SiO2+Li2O) / ZrO2 is 10.0 to 37.0, more preferably (SiO2+Li2O) / ZrO2 is 12.0 to 25.0, and even more preferably (SiO2+Li2O) / ZrO2 is 13.0 to 20.0.

[0092] (85) The matrix glass according to any one of (67) to (84) has the following composition expressed as a weight percentage: ZrO2 / (Ag2O+CeO2) is 2.3 to 50.0, preferably ZrO2 / (Ag2O+CeO2) is 6.5 to 35.0, more preferably ZrO2 / (Ag2O+CeO2) is 8.5 to 20.0, and even more preferably ZrO2 / (Ag2O+CeO2) is 11.0 to 18.0.

[0093] (86) The matrix glass according to any one of (67) to (85) has the following composition expressed as a weight percentage: (Ag2O+SnO2+Sb2O3) / CeO2 is 1.0 to 30.0, preferably (Ag2O+SnO2+Sb2O3) / CeO2 is 3.0 to 20.0, more preferably (Ag2O+SnO2+Sb2O3) / CeO2 is 5.0 to 12.5, and even more preferably (Ag2O+SnO2+Sb2O3) / CeO2 is 7.5 to 10.0.

[0094] (87) The matrix glass according to any one of (67) to (86) has the following composition expressed as a weight percentage: (Sb2O3+SnO2+CeO2) / Ag2O is 0.1 to 10.0, preferably (Sb2O3+SnO2+CeO2) / Ag2O is 0.4 to 5.0, more preferably (Sb2O3+SnO2+CeO2) / Ag2O is 0.7 to 3.7, and even more preferably (Sb2O3+SnO2+CeO2) / Ag2O is 1.5 to 3.2.

[0095] (88) The matrix glass according to any one of (67) to (87) has components expressed as weight percentages, wherein: SnO2 / (CeO2+SnO2) is 0 to 0.9, preferably SnO2 / (CeO2+SnO2) is 0 to 0.6, and more preferably SnO2 / (CeO2+SnO2) is 0 to 0.5.

[0096] (89) The matrix glass according to any one of (67) to (88) has the following components expressed as weight percentages: R2O+Li2O+Al2O3 is 15-30%, preferably R2O+Li2O+Al2O3 is 17.5-29.5%, more preferably R2O+Li2O+Al2O3 is 18.5-26%, and even more preferably R2O+Li2O+Al2O3 is 20-25%, wherein R2O is one or both of Na2O and K2O.

[0097] (90) The matrix glass according to any one of (67) to (89) has the following composition expressed as a weight percentage: (SiO2+Al2O3) / (Li2O+Na2O+K2O) is 3.0 to 7.5, preferably (SiO2+Al2O3) / (Li2O+Na2O+K2O) is 3.7 to 6.5, more preferably (SiO2+Al2O3) / (Li2O+Na2O+K2O) is 4.3 to 6.0, and even more preferably (SiO2+Al2O3) / (Li2O+Na2O+K2O) is 4.8 to 5.8.

[0098] (91) The matrix glass according to any one of (67) to (90) has components expressed as weight percentages, wherein: MO / ZrO2 is 2.5 or less, preferably MO / ZrO2 is 1.5 or less, more preferably MO / ZrO2 is 0.5 or less, and MO is one or more of MgO, CaO, SrO, BaO, and ZnO.

[0099] (92) The matrix glass according to any one of (67) to (91) has the following components expressed in weight percentage: Sb2O3+SnO2: 0.05 to 1.2%, preferably Sb2O3+SnO2: 0.1 to 1%, more preferably Sb2O3+SnO2: 0.2 to 0.7%.

[0100] (93) The matrix glass according to any one of (67) to (92), wherein its components are expressed as weight percentages, wherein: SiO2: 68-77%, preferably SiO2: 69.5-75.5%; and / or R2O: 3-10%, preferably R2O: 4-8%; and / or Or Li2O: 7-13%, preferably Li2O: 8.5-12%; and / or Al2O3: 4-10%, preferably Al2O3: 5-9%; and / or ZrO2: 2-8%, preferably ZrO2: 3-6.5%; and / or CeO2: 0.07-0.4%, preferably CeO2: 0.08-0.3%; and / or Ag2O: 0.1-0.6%, preferably Ag2O: 0.2-0.5%; and / or Sb2O3: 0.01-0.7%, preferably Sb2O3: 0.07-0.5%; and / or SnO2: 0-0.3%, preferably Sb2O3: 0.07-0.5%; nO2: 0-0.2%; and / or MO: 0-3%, preferably MO: 0-1%, more preferably without MO; and / or Ln2O3: 0-3%, preferably Ln2O3: 0-1%, more preferably without Ln2O3; and / or Fe2O3: 0-0.5%, preferably Fe2O3: 0-0.2%, more preferably without Fe2O3, wherein R2O is one or two of Na2O and K2O, MO is one or more of MgO, CaO, SrO, BaO, and ZnO, and Ln2O3 is one or more of La2O3, Gd2O3, and Y2O3.

[0101] (94) The matrix glass according to any one of (67) to (93), wherein the refractive index n of the matrix glass is... d The value is 1.51–1.55, preferably 1.52–1.54, more preferably 1.53–1.535, and even more preferably 1.53112–1.53284; and / or the Young's modulus E is 7000 × 10⁻⁶. 7 Pa ~ 9500 × 10 7 Pa, preferably 7500 × 10 7 Pa~9200×10 7 Pa, more preferably 7836×10 7 Pa ~ 9014 × 10 7 Pa, more preferably 8005 × 10 7 Pa~8488×10 7 Pa; and / or Knoop hardness Hk 0.1450 kgf / mm 2 The above values ​​are preferably 470–600 kgf / mm². 2 More preferably, it is 480–582 kgf / mm 2 More preferably, it is 492–532 kgf / mm 2 ; and / or the drop ball test height I is 200 mm or more, preferably 300 mm or more, more preferably 400 mm or more; and / or the dielectric loss tanδ is 11.0 × 10⁻⁶. -3 The preferred value is 7.0×10. -3 ~10.5×10 -3 More preferably 7.2×10 -3 ~9.8×10 -3 Further preferred is 7.4×10 -3 ~9.2×10 -3 ; and / or dielectric constant ε r The coefficient of linear expansion is 5.5 to 8.5, preferably 6.0 to 8.0, more preferably 6.2 to 7.7, and even more preferably 6.3 to 7.0; and / or the coefficient of linear expansion α. 20℃-300℃ 100×10 -7 Below / ℃, preferably 65×10 -7 / ℃~100×10 -7 / ℃, more preferably 71×10 -7 / ℃~95×10 -7 / ℃, further preferably 75×10 -7 / ℃~90×10 -7 / ℃.

[0102] (95) A glass cover containing any of the microcrystalline glass articles described in (1) to (33), and / or any of the microcrystalline glass articles described in (34) to (66), and / or any of the matrix glass articles described in (67) to (94).

[0103] (96) Glass components, comprising any of the microcrystalline glass articles described in (1) to (33), and / or any of the microcrystalline glass articles described in (34) to (66), and / or any of the matrix glass articles described in (67) to (94).

[0104] (97) An apparatus comprising the microcrystalline glass article of any one of (1) to (33), and / or the microcrystalline glass of any one of (34) to (66), and / or the matrix glass of any one of (67) to (94), and / or the glass cover plate of (95), and / or the glass component of (96).

[0105] A method for manufacturing a microcrystalline glass article according to any one of (98)(1) to (33), the method comprising the following steps: forming a matrix glass, forming a microcrystalline glass by crystallization process of the matrix glass, and forming a microcrystalline glass article by chemical strengthening process of the microcrystalline glass.

[0106] (99) According to the manufacturing method of the microcrystalline glass product described in (98), the crystallization process includes mask exposure treatment of the substrate glass and then crystallization heat treatment. The mask exposure treatment includes ultraviolet exposure of a specific position or area of ​​the substrate glass. The ultraviolet wavelength is preferably 313 nm and the exposure time is preferably 5 to 60 minutes.

[0107] (100) In the method for manufacturing microcrystalline glass products according to (98) or (99), the crystallization heat treatment is carried out in two stages, the two-stage crystallization heat treatment includes nucleation process treatment at a first temperature and crystal growth process treatment at a second temperature higher than the nucleation process temperature, preferably the first temperature is 490°C to 520°C, preferably the first temperature treatment time is 1 to 4 hours, preferably the second temperature is 540°C to 620°C, preferably the second temperature treatment time is 1 to 8 hours.

[0108] (101) The method for manufacturing a microcrystalline glass article according to any one of (98) to (100), wherein the chemical strengthening process comprises immersing the microcrystalline glass in a salt bath of molten Na salt, and / or K salt, and / or a mixed Na and K salt at a temperature of 350°C to 470°C for about 1 to 36 hours, preferably at a temperature of 380°C to 460°C, and preferably for a time of 2 to 24 hours.

[0109] A method for manufacturing microcrystalline glass according to any one of (102), (34) to (66), the method comprising the following steps: forming a matrix glass, and forming microcrystalline glass from the matrix glass by a crystallization process.

[0110] (103) According to the manufacturing method of microcrystalline glass described in (102), the crystallization process includes mask exposure treatment of the substrate glass and then crystallization heat treatment. The mask exposure treatment includes ultraviolet exposure of a specific position or area of ​​the substrate glass. The ultraviolet wavelength is preferably 313 nm and the exposure time is preferably 5 to 60 minutes.

[0111] (104) According to the method for manufacturing microcrystalline glass according to (102) or (103), the crystallization heat treatment is carried out in two stages, the two-stage crystallization heat treatment includes nucleation process treatment at a first temperature, and then crystal growth process treatment at a second temperature higher than the nucleation process temperature. Preferably, the first temperature is 490°C to 520°C, the first temperature treatment time is 1 to 4 hours, the second temperature is 540°C to 620°C, and the second temperature treatment time is 1 to 8 hours.

[0112] The beneficial effects of this invention are: through reasonable component design, the matrix glass of this invention can be processed by a crystallization process to obtain a microcrystalline glass with blackened and transparent portions. The microcrystalline glass obtained by this invention is suitable for chemical strengthening, and the microcrystalline glass and microcrystalline glass products made therefrom have excellent mechanical properties. In some embodiments, the microcrystalline glass or microcrystalline glass products of this invention have blackened and transparent portions, the transparent portion having high transmittance in the visible light band, and the blackened portion having low transmittance in the visible light band. Detailed Implementation

[0113] The embodiments of the present invention will now be described in detail. However, the present invention is not limited to the embodiments described below, and appropriate modifications can be made to implement it within the scope of the present invention's objectives. Furthermore, regarding repeated descriptions, although there are appropriate omissions, this will not limit the spirit of the invention.

[0114] The microcrystalline glass and microcrystalline glass articles of the present invention are materials having a crystalline phase (sometimes also called crystal) and a glassy phase, which are different from amorphous solids. The crystalline phase of the microcrystalline glass and microcrystalline glass articles can be identified by the peak angle appearing in the X-ray diffraction pattern of X-ray diffraction analysis and / or measured by TEMEDX.

[0115] Through repeated experiments and research, the inventors of this invention have obtained the microcrystalline glass or microcrystalline glass products of this invention by specifying the content and proportion of specific components constituting microcrystalline glass and microcrystalline glass products to specific values ​​and causing them to precipitate specific crystalline phases.

[0116] In some embodiments, the microcrystalline glass of the present invention comprises one or more blackened portions and one or more transparent portions, wherein the transparent portion refers to the average transmittance (T0) of the microcrystalline glass in the 400-800 nm wavelength range when the microcrystalline glass is processed to a thickness of 0.2-1.5 mm. 400-800nm The portion with a transmittance of 85.0% or higher, and the blackened portion refers to the average transmittance (T) of the glass-ceramic in the 400–800 nm wavelength range when the glass-ceramic is processed to a thickness of 0.2–1.5 mm. 400-800nmThe portion containing less than 5.0% of the crystal phase. In some embodiments, the blackened portion of the glass-ceramic contains a crystalline phase, while the transparent portion does not. In some embodiments, the crystalline phase in the blackened portion of the glass-ceramic is uniformly distributed.

[0117] In some embodiments, the microcrystalline glass article of the present invention includes one or more blackened portions and one or more transparent portions, wherein the transparent portion refers to the average transmittance (T0) of the microcrystalline glass article in the 400-800nm ​​wavelength range when the microcrystalline glass article is processed to a thickness of 0.2-1.5mm. 400-800nm The portion with a transmittance of 85.0% or higher, and the blackened portion refers to the average transmittance (T) of the microcrystalline glass product in the 400-800nm ​​wavelength range when the microcrystalline glass product is processed to a thickness of 0.2-1.5mm. 400-800nm The portion containing less than 5.0% of the crystalline phase. In some embodiments, the blackened portion of the glass-ceramic article contains a crystalline phase, while the transparent portion of the glass-ceramic article does not contain a crystalline phase. In some embodiments, the crystalline phase in the blackened portion of the glass-ceramic article is uniformly distributed.

[0118] In some embodiments, the microcrystalline glass or microcrystalline glass product of the present invention is entirely a blackened portion, wherein the blackened portion refers to the average transmittance (T0) of the microcrystalline glass or microcrystalline glass product in the 400-800nm ​​wavelength range when the microcrystalline glass or microcrystalline glass product is processed to a thickness of 0.2-1.5mm. 400-800nm The portion containing less than 5.0% is included. In some embodiments, the crystalline phase of the blackened portion of the glass-ceramic or glass-ceramic article is uniformly distributed.

[0119] In some embodiments, the microcrystalline glass or microcrystalline glass product of the present invention is entirely transparent. The transparent portion refers to the average transmittance (T0) of the microcrystalline glass or microcrystalline glass product in the 400-800nm ​​wavelength range when the microcrystalline glass or microcrystalline glass product is processed to a thickness of 0.2-1.5mm. 400-800nm The percentage is over 85.0%.

[0120] In some embodiments, the blackened portion of the microcrystalline glass or microcrystalline glass product of the present invention can be formed into a pattern of any shape and / or size.

[0121] The scope of each component (ingredient) of the matrix glass, microcrystalline glass, and microcrystalline glass articles of the present invention will be described below. In this specification, unless otherwise specified, the content of each component is expressed as a weight percentage (wt%) relative to the total amount of the matrix glass, microcrystalline glass, or microcrystalline glass article as a component of oxides. Here, "composition converted to oxides" means that when oxides, complex salts, and hydroxides used as raw materials for the matrix glass, microcrystalline glass, or microcrystalline glass articles of the present invention decompose and transform into oxides upon melting, the total amount of such oxides is taken as 100%. Furthermore, in this specification, when referred to simply as "glass," it refers to the matrix glass before crystallization (i.e., crystallization process treatment); after crystallization (i.e., crystallization process treatment), it is referred to as microcrystalline glass; and microcrystalline glass articles refer to products obtained by chemically strengthening microcrystalline glass.

[0122] Unless otherwise specified in the specific context, the numerical ranges listed herein include upper and lower limits. "Above" and "below" include endpoint values ​​and all integers and fractions within the range, not limited to the specific values ​​listed when the range is defined. The term "about" as used herein means that formulations, parameters, and other quantities and characteristics are not, and need not be, exact, and may be approximate and / or larger or lower if necessary, reflecting tolerances, conversion factors, and measurement errors, etc. The term "and / or" as used herein is inclusive; for example, "A and / or B" means only A, or only B, or both A and B.

[0123] In some embodiments of the present invention, the crystalline phase (crystal) in the glass-ceramic or glass-ceramic article contains a lithium silicate crystalline phase, preferably a lithium metasilicate crystalline phase (Li2SiO3). In some embodiments, the lithium metasilicate crystalline phase has a higher weight percentage than other crystalline phases. In some embodiments, the crystalline phase in the glass-ceramic or glass-ceramic article comprises only the lithium metasilicate crystalline phase.

[0124] In some embodiments, the weight percentage of lithium metasilicate crystalline phase in the blackened portion of the glass-ceramic or glass-ceramic article is 5-50%, preferably 5-40%, and more preferably 10-30%. In some embodiments, the weight percentage of lithium metasilicate crystalline phase in the blackened portion of the glass-ceramic or glass-ceramic article is 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, 40%, 41%, 42%, 43%, 44%, 45%, 46%, 47%, 48%, 49%, or 50%.

[0125] SiO2 is a glass-forming oxide, forming the framework of glass. It has a low dielectric constant and dielectric loss. SiO2 is a component of lithium metasilicate in glass-ceramics. When the SiO2 content is less than 65%, the hardness and coefficient of thermal expansion of the glass decrease, while the dielectric constant and dielectric loss increase. When the SiO2 content is higher than 78%, the transmittance of the blackened portion of the glass-ceramic and glass-ceramic products increases. Therefore, the SiO2 content ranges from 65% to 78%, preferably 68% to 77%, and more preferably 69.5% to 75.5%. In some embodiments, it may contain approximately 65%, 65.5%, 66%, 66.5%, 67%, 67.5%, 68%, 68.5%, 69%, 69.5%, 70%, 70.5%, 71%, 71.5%, 72%, 72.5%, 73%, 73.5%, 74%, 74.5%, 75%, 75.5%, 76%, 76.5%, 77%, 77.5%, or 78% SiO2.

[0126] Li₂O is the main component for crystal formation in the microcrystalline glass and microcrystalline glass products of this invention. When the Li₂O content is less than 5%, the crystal content of the microcrystalline glass or microcrystalline glass products decreases, and the transmittance of the blackened portion is higher. When the Li₂O content is greater than 15%, the Young's modulus and falling ball test height of the glass decrease, while the refractive index and dielectric loss of the glass increase. Simultaneously, the portion of the matrix glass not exposed to ultraviolet light during crystallization is prone to crystallization during heat treatment, leading to a decrease in the transmittance of the transparent portion of the microcrystalline glass and microcrystalline glass products. Therefore, the Li₂O content is limited to 5-15%, preferably 7-13%, and more preferably 8.5-12%. In some embodiments, it may contain about 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, 10%, 10.5%, 11%, 11.5%, 12%, 12.5%, 13%, 13.5%, 14%, 14.5%, or 15% Li2O.

[0127] The inventors discovered that in some embodiments, the hardness and drop ball test height of the glass increase with increasing SiO2 / Li2O values, while the refractive index decreases with increasing SiO2 / Li2O values. Simultaneously, when SiO2 / Li2O is below 5.5, the transmittance of the transparent portion of the glass-ceramic and glass-ceramic products decreases, while the transmittance of the blackened portion increases; when SiO2 / Li2O exceeds 10.0, the crystal content of the blackened portion of the glass-ceramic and glass-ceramic products is low, and the transmittance of the blackened portion increases. Therefore, in some embodiments, a SiO2 / Li2O value of 5.5–10.0 is preferred, a SiO2 / Li2O value of 6.0–9.0 is more preferred, and a SiO2 / Li2O value of 7.0–8.5 is even more preferred. This results in higher transmittance of the transparent portion of the glass-ceramic and glass-ceramic products in the visible light band, while the transmittance of the blackened portion is lower, making it particularly suitable for optical signal channels or optical shielding systems in electronic products. In some implementations, the SiO2 / Li2O value can be 5.5, 5.6, 5.7, 5.8, 5.9, 6.0, 6.1, 6.2, 6.3, 6.4, 6.5, 6.6, 6.7, 6.8, 6.9, 7.0, 7.1, 7.2, 7.3, 7.4, 7.5, 7.6, 7.7, 7.8, 7.9, 8.0, 8.1, 8.2, 8.3, 8.4, 8.5, 8.6, 8.7, 8.8, 8.9, 9.0, 9.1, 9.2, 9.3, 9.4, 9.5, 9.6, 9.7, 9.8, 9.9, or 10.0.

[0128] Alkali metal oxides (R₂O, which can be one or both of Na₂O and K₂O) can promote the precipitation of lithium metasilicate crystals and improve the transmittance of the blackened portion of glass-ceramics and glass-ceramic products. When the R₂O content is less than 2%, the crystal content of glass-ceramics and glass-ceramic products decreases, the transmittance of the blackened portion increases, and the blackening effect may not even be achieved. When the R₂O content is greater than 12%, the Young's modulus and falling ball test height of the glass decrease, while the refractive index, dielectric constant, and dielectric loss of the glass increase. Therefore, the R₂O content is limited to 2–12%, preferably 3–10%, and more preferably 4–8%. In some implementations, it may contain about 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, 10%, 10.5%, 11%, 11.5%, or 12% R2O.

[0129] Al2O3 can suppress the decrease in transmittance of the transparent portion of glass-ceramics and glass-ceramic products after mask exposure and heat treatment, and improve the strength and hardness of the glass, as well as enhance its chemical stability. When the Al2O3 content is less than 3%, the hardness and Young's modulus of the glass decrease, while the coefficient of linear expansion increases; when the Al2O3 content is greater than 12%, the dielectric constant and dielectric loss of the glass increase, the crystal content of the blackened portion of the glass-ceramics and glass-ceramic products decreases, the transmittance of the blackened portion increases, and the blackening effect may even be impossible to achieve. Therefore, the Al2O3 content is 3-12%, preferably 4-10%, and more preferably 5-9%. In some embodiments, it may contain about 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, 10%, 10.5%, 11%, 11.5%, and 12% Al2O3.

[0130] In some embodiments, when the total content of R2O, Li2O, and Al2O3 (R2O+Li2O+Al2O3) is less than 15%, the refractive index, hardness, and Young's modulus of the glass decrease; when the content of R2O+Li2O+Al2O3 is greater than 30%, the dielectric constant and dielectric loss of the glass increase. Therefore, it is preferable that the content of R2O+Li2O+Al2O3 is 15-30%, more preferably 17.5-29.5%, even more preferably 18.5-26%, and still more preferably 20-25%. In some embodiments, R2O+Li2O+Al2O3 is approximately 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%, 27.5%, 28%, 28.5%, 29%, 29.5%, or 30%.

[0131] Extensive experimental research by the inventors revealed that, in some embodiments, controlling the ratio of the total content of SiO2 and Al2O3 (SiO2+Al2O3) to the total content of Li2O, Na2O, and K2O (Li2O+Na2O+K2O) within the range of 3.0 to 7.5 results in lower transmittance of the blackened portion of the microcrystalline glass and microcrystalline glass products, as well as a lower refractive index of the glass. This reduces the reflectivity of light signals on the glass surface and increases the incident rate of light signals. Therefore, the preferred ratio of (SiO2+Al2O3) / (Li2O+Na2O+K2O) is 3.0 to 7.5, more preferably (SiO2+Al2O3) / (Li2O+Na2O+K2O) is 3.7 to 6.5, even more preferably (SiO2+Al2O3) / (Li2O+Na2O+K2O) is 4.3 to 6.0, and even more preferably (SiO2+Al2O3) / (Li2O+Na2O+K2O) is 4.8 to 5.8. In some implementations, the value of (SiO2+Al2O3) / (Li2O+Na2O+K2O) can be 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4.0, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, 5.0, 5.1, 5.2, 5.3, 5.4, 5.5, 5.6, 5.7, 5.8, 5.9, 6.0, 6.1, 6.2, 6.3, 6.4, 6.5, 6.6, 6.7, 6.8, 6.9, 7.0, 7.1, 7.2, 7.3, 7.4, 7.5.

[0132] ZrO2 can modulate the precision of the black pattern formation in the blackened areas of glass after mask exposure, improving the interface distinction between the exposed and unexposed areas. This prevents crystallization near the interface in the unexposed areas after heat treatment, thus maintaining high transmittance in the visible light band for the unexposed areas after heat treatment, while ensuring lower transmittance in the blackened areas after heat treatment in the exposed areas. When the ZrO2 content is below 1.5%, the coefficient of thermal expansion of the glass increases, and crystallization is more likely to occur in the unexposed areas during heat treatment, leading to reduced transmittance in the transparent areas. When the ZrO2 content is above 10%, the crystal content of the glass-ceramic and glass-ceramic products decreases, increasing the transmittance of the blackened areas, and may even prevent the blackening effect from being achieved. Therefore, the ZrO2 content is 1.5–10%, preferably 2–8%, and more preferably 3–6.5%. In some embodiments, it may contain about 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, or 10% ZrO2.

[0133] In some embodiments, controlling the total content of K2O and Na2O, specifically the ratio between K2O+Na2O and ZrO2 (K2O+Na2O) / ZrO2, within the range of 0.5 to 7.1, results in higher transmittance of the transparent portion of the glass-ceramic and glass-ceramic products, as well as higher hardness and Young's modulus, and lower dielectric constant. Therefore, a K2O+Na2O) / ZrO2 ratio of 0.5 to 7.1 is preferred, a K2O+Na2O) / ZrO2 ratio of 0.7 to 4.5 is more preferred, and a K2O+Na2O) / ZrO2 ratio of 0.8 to 2.5 is even more preferred. In some implementations, the value of (K2O+Na2O) / ZrO2 can be 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4.0, 4.1, 4.2, 4.3, 4.5, 4.6, 4.7, 4.8, 4.9, 5.0, 5.1, 5.2, 5.3, 5.4, 5.5, 6.0, 6.5, 7.0, 7.1.

[0134] In some embodiments, controlling the ratio of Li2O content to ZrO2 content (Li2O / ZrO2) within the range of 1.0 to 7.5 can result in a glass with a lower refractive index and dielectric loss. This improves the accuracy of the pattern formed within the glass-ceramic and glass-ceramic products after mask exposure and heat treatment, leading to higher transmittance in the transparent portions and lower transmittance in the blackened portions. Therefore, a Li2O / ZrO2 ratio of 1.0 to 7.5 is preferred, more preferably 1.2 to 5.0, further preferably 1.4 to 4.3, and even more preferably 1.6 to 3.0. In some implementations, the Li2O / ZrO2 value can be 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4.0, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, 5.0, 5.5, 6.0, 6.5, 7.0, or 7.5.

[0135] In some embodiments, controlling the total content of SiO2 and Li2O, specifically the ratio between SiO2+Li2O and ZrO2 (SiO2+Li2O) / ZrO2, within the range of 8.0 to 55.0, can improve the hardness and drop ball test height of the glass, reduce the coefficient of thermal expansion and dielectric constant of the glass, improve the accuracy of the pattern formed within the glass-ceramic and glass-ceramic products after mask exposure and heat treatment, and improve the drop ball test height of the glass-ceramic and glass-ceramic products; the transmittance of the blackened portion of the glass-ceramic and glass-ceramic products is relatively low. Therefore, it is preferable that (SiO2+Li2O) / ZrO2 is 8.0 to 55.0, more preferably (SiO2+Li2O) / ZrO2 is 10.0 to 37.0, further preferably (SiO2+Li2O) / ZrO2 is 12.0 to 25.0, and even more preferably (SiO2+Li2O) / ZrO2 is 13.0 to 20.0. In some embodiments, the value of (SiO2+Li2O) / ZrO2 can be 8.0, 8.5, 9.0, 9.5, 10.0, 10.5, 11.0, 11.5, 12.0, 12.5, 13.0, 13.5, 14.0, 14.5, 15.0, 15.5, 16.0, 16.5, 17.0, 17.5, 18.0, 18.5, 19.0, 19.5, 20.0, 20.5, 21.0, 21.5, 22.0, 22.5, 23.0, 23.5, 24.0, 24.5, 25.0, 25.5. 26.0, 26.5, 27.0, 27.5, 28.0, 28.5, 29.0, 29.5, 30.0, 30.5, 31.0, 31.5, 32.0, 32.5, 33.0, 33.5, 34.0, 34.5, 35.0, 35.5, 36.0, 36.5, 37.0, 38.0, 39.0, 40.0, 41.0, 42.0, 43.0, 44.0, 45.0, 46.0, 47.0, 48.0, 49.0, 50.0, 51.0, 52.0, 53.0, 54.0, 55.0.

[0136] Alkaline earth metal oxides (MO, which may be one or more of MgO, CaO, SrO, BaO, and ZnO) can improve the dielectric constant of glass and the transmittance of the blackened portion of glass-ceramics and glass-ceramic products. When the MO content is higher than 5%, the dielectric constant and dielectric loss of the glass increase, while the Young's modulus and drop ball test height decrease. Therefore, the MO content in this invention is limited to 0-5%, preferably 0-3%, more preferably 0-1%, and even more preferably does not contain MO. In some embodiments, it may contain about 0%, greater than 0%, 0.01%, 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, etc. 1.8%, 1.9%, 2%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3%, 3.1%, 3.2%, 3.3%, 3.4% , 3.5%, 3.6%, 3.7%, 3.8%, 3.9%, 4%, 4.1%, 4.2%, 4.3%, 4.4%, 4.5%, 4.6%, 4.7%, 4.8%, 4.9%, 5% MO.

[0137] In some embodiments, when the MO / ZrO2 ratio is greater than 2.5, the dielectric loss of the glass increases, while the hardness, Young's modulus, and drop ball test height of the glass decrease, and the transmittance of the blackened portion of the glass-ceramic and glass-ceramic products increases. Therefore, it is preferable that the MO / ZrO2 ratio is 2.5 or less, more preferably 1.5 or less, and even more preferably 0.5 or less. In some embodiments, the value of MO / ZrO2 can 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, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2, 2.1, 2.2, 2.3, 2.4, or 2.5.

[0138] CeO2 acts as a photosensitizer, providing electrons to components such as Ag, Sb, and Sn. When the CeO2 content is below 0.01%, it cannot provide enough electrons, resulting in an excessively low crystal content in the glass-ceramic, reducing the transmittance of the blackened portion of the glass-ceramic and its products, and also decreasing the Young's modulus. When the CeO2 content is above 0.6%, the transmittance of the transparent portion of the glass-ceramic and its products decreases, as does the penetration depth in the ultraviolet band. The internal crystal content of the blackened portion of the glass-ceramic and its products decreases, leading to increased transmittance. Therefore, the CeO2 content is 0.01–0.6%, preferably 0.07–0.4%, and more preferably 0.08–0.3%. In some embodiments, it may include approximately 0.01%, 0.02%, 0.03%, 0.04%, 0.05%, 0.06%, 0.07%, 0.08%, 0.09%, 0.1%, 0.11%, 0.12%, 0.13%, 0.14%, 0.15%, 0.16%, 0.17%, 0.18%, 0.19%, 0.2%, 0.21%, 0.22%, 0.23%, 0.24%, 0.25%, 0.26%, 0.27%, 0.28%, 0.29%, 0 CeO2 concentrations of 0.3%, 0.31%, 0.32%, 0.33%, 0.34%, 0.35%, 0.36%, 0.37%, 0.38%, 0.39%, 0.4%, 0.41%, 0.42%, 0.43%, 0.44%, 0.45%, 0.46%, 0.47%, 0.48%, 0.49%, 0.5%, 0.51%, 0.52%, 0.53%, 0.54%, 0.55%, 0.56%, 0.57%, 0.58%, 0.59%, and 0.6%.

[0139] Ag₂O, as a nucleating agent in the microcrystalline glass and microcrystalline glass products of this invention, plays a role in improving the blackening effect in the microcrystalline glass and microcrystalline glass products. When the Ag₂O content is less than 0.01%, the transmittance of the blackened portion of the microcrystalline glass and microcrystalline glass products increases, or even fails to blacken, and the drop ball test height of the microcrystalline glass and microcrystalline glass products decreases, the coefficient of thermal expansion increases, and the pattern accuracy decreases. When the Ag₂O content exceeds 0.8%, the transmittance of the transparent portion of the glass decreases during molding or heat treatment, and due to the excessively high nucleating agent content, the number of crystals in the microcrystalline glass and microcrystalline glass products increases, resulting in excessively fine grain size. The scattering effect of the crystals in the blackened portion on visible light weakens, easily leading to an increase in the transmittance of the blackened portion, and the glass is prone to crystallization during molding. Therefore, the Ag₂O content is limited to 0.01-0.8%, preferably 0.1-0.6%, and more preferably 0.2-0.5%. In some embodiments, it may contain approximately 0.01%, 0.02%, 0.03%, 0.04%, 0.05%, 0.06%, 0.07%, 0.08%, 0.09%, 0.1%, 0.11%, 0.12%, 0.13%, 0.14%, 0.15%, 0.16%, 0.17%, 0.18%, 0.19%, 0.2%, 0.21%, 0.22%, 0.23%, 0.24%, etc. 0.25%, 0.26%, 0.27%, 0.28%, 0.29%, 0.3%, 0.31%, 0.32%, 0.33%, 0.34%, 0.35%, 0.36%, 0.37%, 0.38%, 0.39%, 0.4%, 0.41%, 0.42%, 0.43%, 0.44%, 0.45%, 0.46%, 0.47%, 0.48%, 0.49%, 0.5%, 0.51%, 0.52%, 0. Ag2O concentrations of 53%, 0.54%, 0.55%, 0.56%, 0.57%, 0.58%, 0.59%, 0.6%, 0.61%, 0.62%, 0.63%, 0.64%, 0.65%, 0.66%, 0.67%, 0.68%, 0.69%, 0.7%, 0.71%, 0.72%, 0.73%, 0.74%, 0.75%, 0.76%, 0.77%, 0.78%, 0.79%, and 0.8%.

[0140] The inventors discovered that, in some embodiments, controlling the ratio of Ag₂O to CeO₂ (Ag₂O / CeO₂) within the range of 1.0 to 10.0 results in larger grain sizes and higher crystal content in the blackened portion of the glass-ceramic and glass-ceramic products. This leads to stronger light scattering in the visible light band, lower transmittance in the blackened portion, and increased hardness and drop ball test height in the glass-ceramic and glass-ceramic products. Therefore, an Ag₂O / CeO₂ ratio of 1.0 to 10.0 is preferred, 1.5 to 6.5 is more preferred, and 2.0 to 4.5 is even more preferred. In some implementations, the value of Ag2O / CeO2 can be 1.0, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4.0, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, 5.0, 5.5, 6.0, 6.5, 7.0, 7.5, 8.0, 8.5, 9.0, 9.5, or 10.0.

[0141] In some embodiments, controlling the ratio of ZrO2 content to the total content of Ag2O and CeO2 (Ag2O+CeO2), ZrO2 / (Ag2O+CeO2), within the range of 2.3 to 50.0, can optimize the coefficient of thermal expansion of the glass, improve the accuracy of the pattern formed within the glass-ceramic after mask exposure and heat treatment, and simultaneously increase the transmittance of the transparent portion of the glass-ceramic and glass-ceramic products while reducing the transmittance of the blackened portion. It can also improve the hardness and drop height of the glass and glass-ceramic products. Therefore, a ZrO2 / (Ag2O+CeO2) ratio of 2.3 to 50.0 is preferred, more preferably 6.5 to 35.0, further preferably 8.5 to 20.0, and even more preferably 11.0 to 18.0. In some embodiments, the value of ZrO2 / (Ag2O+CeO2) can be 2.3, 2.5, 3.0, 3.5, 4.0, 4.5, 5.0, 5.5, 6.0, 6.5, 7.0, 7.5, 8.0, 8.5, 9.0, 9.5, 10.0, 10.5, 11.0, 11.5, 12.0, 12.5, 13.0, 13.5, 14.0, 14.5, 15.0, 15.5, 16.0, 16.5, 17.0, 17.5, 18.0, 18.5, or 19. 0, 19.5, 20.0, 20.5, 21.0, 21.5, 22.0, 22.5, 23.0, 23.5, 24.0, 24.5, 25.0, 26.0, 27.0, 28.0, 29.0, 30.0, 31.0, 32.0, 33.0, 34.0, 35.0, 36.0, 37.0, 38.0, 39.0, 40.0, 41.0, 42.0, 43.0, 44.0, 45.0, 46.0, 47.0, 48.0, 49.0, 50.0.

[0142] Sb₂O₃ and SnO₂ absorb Ce during ultraviolet exposure. 3+ The released electrons serve to store electrons, providing energy for Ag in subsequent heat treatment processes. +Electrons are provided to form Ag colloid nuclei, promoting the blackening of glass-ceramics. When the content of Sb₂O₃+SnO₂ is below 0.05%, it is difficult for glass-ceramics or glass-ceramic products to achieve a blackening effect. When the content of Sb₂O₃+SnO₂ is above 1.2%, the blackened portion of the glass-ceramics or glass-ceramic products tends to have increased transmittance. Therefore, the content of Sb₂O₃+SnO₂ is 0.05-1.2%, preferably 0.1-1%, and more preferably 0.2-0.7%. In some embodiments, the content of Sb₂O₃ + SnO₂ is approximately 0.05%, 0.1%, 0.15%, 0.2%, 0.25%, 0.3%, 0.35%, 0.4%, 0.45%, 0.5%, 0.55%, 0.6%, 0.65%, 0.7%, 0.75%, 0.8%, 0.85%, 0.9%, 0.95%, 1.0%, 1.05%, 1.1%, 1.15%, and 1.2%.

[0143] SnO2 has a good effect on promoting the blackening of glass-ceramics. However, in some embodiments, when the SnO2 content is higher than 0.5%, the transmittance of the transparent portion of the glass decreases or even becomes devitrified during forming or heat treatment. Therefore, the SnO2 content is limited to 0-0.5%, preferably 0-0.3%, and more preferably 0-0.2%. The Sb2O3 content is limited to 0-1%, preferably 0.01-0.7%, and more preferably 0.07-0.5%. In some embodiments, the content may include approximately 0%, greater than 0%, 0.01%, 0.02%, 0.03%, 0.04%, 0.05%, 0.06%, 0.07%, 0.08%, 0.09%, 0.1%, 0.11%, 0.12%, 0.13%, 0.14%, 0.15%, 0.16%, 0.17%, 0.18%, 0.19%, 0.2%, 0.21%, 0.22%, 0.23%, and 0.2%. SnO2 concentrations of 4%, 0.25%, 0.26%, 0.27%, 0.28%, 0.29%, 0.3%, 0.31%, 0.32%, 0.33%, 0.34%, 0.35%, 0.36%, 0.37%, 0.38%, 0.39%, 0.4%, 0.41%, 0.42%, 0.43%, 0.44%, 0.45%, 0.46%, 0.47%, 0.48%, 0.49%, and 0.5%. In some implementations, the content may include approximately 0%, greater than 0%, 0.01%, 0.02%, 0.03%, 0.04%, 0.05%, 0.06%, 0.07%, 0.08%, 0.09%, 0.1%, 0.11%, 0.12%, 0.13%, 0.14%, 0.15%, 0.16%, 0.17%, 0.18%, 0.19%, 0.2%, 0.21%, 0.22%, 0.23%, 0.24%, 0.25%, 0.26%, 0.27%, 0.28%, etc. 0.29%, 0.3%, 0.31%, 0.32%, 0.33%, 0.34%, 0.35%, 0.36%, 0.37%, 0.38%, 0.39%, 0.4%, 0.41%, 0.42%, 0.43%, 0.44%, 0.45%, 0.46%, 0.47%, 0.48%, 0.49%, 0.5%, 0.55%, 0.6%, 0.65%, 0.7%, 0.75%, 0.8%, 0.85%, 0.9%, 0.95%, and 1% Sb2O3.

[0144] Through extensive experimental research, the inventors discovered that in some embodiments, controlling the total content of Sb₂O₃ and SnO₂, specifically the ratio of Sb₂O₃+SnO₂ to Ag₂O (Sb₂O₃+SnO₂) / Ag₂O, within the range of 0.1 to 5.0, can reduce the dielectric loss of the glass, increase the drop ball test height of the glass and glass-ceramic products, and result in higher transmittance of the transparent portion and lower transmittance of the blackened portion of the glass and glass-ceramic products. Therefore, it is preferable that (Sb₂O₃+SnO₂) / Ag₂O is 0.1 to 5.0, more preferably 0.5 to 3.5, and even more preferably 1.0 to 2.6. In some implementations, the value of (Sb2O3+SnO2) / Ag2O can be 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4.0, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, or 5.0.

[0145] In some embodiments, controlling the total content of Ag2O, SnO2, and Sb2O3 (Ag2O+SnO2+Sb2O3) to the content of CeO2 (Ag2O+SnO2+Sb2O3) / CeO2 within the range of 1.0 to 30.0 can result in lower transmittance of the blackened portion of the glass-ceramic and glass-ceramic products, thereby reducing the dielectric constant of the glass while increasing its hardness and Young's modulus. Therefore, the preferred ratio of (Ag2O+SnO2+Sb2O3) / CeO2 is 1.0 to 30.0, more preferably (Ag2O+SnO2+Sb2O3) / CeO2 is 3.0 to 20.0, even more preferably (Ag2O+SnO2+Sb2O3) / CeO2 is 5.0 to 12.5, and even more preferably (Ag2O+SnO2+Sb2O3) / CeO2 is 7.5 to 10.0. In some implementations, the value of (Ag₂O + SnO₂ + Sb₂O₃) / CeO₂ can be 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, 5.0, 5.5, 6.0, 6.5, 7.0, 7.5, 8.0, 8.5, 9.0, 9.5, 10.0, 10.5, 11.0, 11.5, 12.0, 12.5, 13.0, 13.5, 14.0, 14.5. 15.0, 15.5, 16.0, 16.5, 17.0, 17.5, 18.0, 18.5, 19.0, 19.5, 20.0, 20.5, 21.0, 21.5, 22.0, 22.5, 23.0, 23.5, 24.0, 24.5, 25.0, 25.5, 26.0, 26.5, 27.0, 27.5, 28.0, 28.5, 29.0, 29.5, 30.0.

[0146] In some embodiments, controlling the total content of Sb₂O₃, SnO₂, and CeO₂, and the ratio between the content of Sb₂O₃+SnO₂+CeO₂ and Ag₂O (Sb₂O₃+SnO₂+CeO₂) / Ag₂O, in the range of 0.1 to 10.0, can reduce the dielectric loss and coefficient of expansion of the glass, resulting in lower transmittance of the blackened portion of the glass-ceramic and glass-ceramic products. Therefore, it is preferable that (Sb₂O₃+SnO₂+CeO₂) / Ag₂O is 0.1 to 10.0, more preferably (Sb₂O₃+SnO₂+CeO₂) / Ag₂O is 0.4 to 5.0, further preferably (Sb₂O₃+SnO₂+CeO₂) / Ag₂O is 0.7 to 3.7, and even more preferably (Sb₂O₃+SnO₂+CeO₂) / Ag₂O is 1.5 to 3.2. In some implementations, the value of (Sb₂O₃+SnO₂+CeO₂) / Ag₂O can be 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, or 3.4. 3.5, 3.6, 3.7, 3.8, 3.9, 4.0, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, 5.0, 5.1, 5.2, 5.3, 5.4, 5.5, 5.6, 5.7, 5.8, 5.9, 6.0, 6.1, 6.2, 6.3, 6.4, 6.5, 6.6, 6.7, 6.8, 6.9, 7.0, 7.5, 8.0, 8.5, 9.0, 9.5, 10.0.

[0147] In some embodiments, when the value of SnO2 / (CeO2+SnO2) is greater than 0.9, the transmittance of the transparent portion of the glass decreases sharply or even becomes completely devitrified during glass forming or heat treatment. Therefore, it is preferable that SnO2 / (CeO2+SnO2) is 0 to 0.9, more preferably 0 to 0.6, and even more preferably 0 to 0.5. In some implementations, the value of SnO2 / (CeO2+SnO2) can be 0, greater than 0, 0.01, 0.02, 0.03, 0.04, 0.05, 0.07, 0.1, 0.13, 0.15, 0.17, 0.2, 0.23, 0.25, 0.27, 0.3, 0.33, 0.35, 0.37, 0.4, 0.43, 0.45, 0.47, 0.5, 0.53, 0.55, 0.57, 0.6, 0.63, 0.65, 0.67, 0.7, 0.73, 0.75, 0.77, 0.8, 0.83, 0.85, 0.87, or 0.9.

[0148] Ln₂O₃ (Ln₂O₃ can be one or more of La₂O₃, Gd₂O₃, and Y₂O₃) can adjust the dielectric constant and dielectric loss of glass, and can be used for Ag… + Providing electrons promotes the blackening of glass-ceramics. When Ln2O3 content is higher than 5%, the transmittance of the blackened portion of the glass-ceramic and glass-ceramic articles increases, and the dielectric constant and dielectric loss of the glass increase. Therefore, the Ln2O3 content is limited to 0-5%, preferably 0-3%, more preferably 0-1%, and in some embodiments, it is further preferred to contain no Ln2O3. In some embodiments, it may contain about 0%, greater than 0%, 0.01%, 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2%, 2.1%, 2.2%, etc. 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3%, 3.1%, 3.2%, 3.3%, 3.4%, 3.5%, 3.6%, 3.7%, 3.8%, 3.9%, 4%, 4.1%, 4.2%, 4.3%, 4.4%, 4.5%, 4.6%, 4.7%, 4.8%, 4.9%, and 5% Ln2O3.

[0149] Fe2O3 can absorb ultraviolet light during ultraviolet exposure of glass, which can then act as a catalyst for Ag. +Providing electrons promotes the blackening of the glass-ceramic. When the Fe2O3 content is higher than 1%, the transmittance of the transparent portion of the glass-ceramic and glass-ceramic products decreases in the visible light range, while the transmittance of the blackened portion increases, resulting in a decrease in the drop ball test height of the glass-ceramic and glass-ceramic products. Therefore, the Fe2O3 content is limited to 0-1%, preferably 0-0.5%, more preferably 0-0.2%, and in some embodiments, it is further preferred that it does not contain Fe2O3. In some implementations, the content may include approximately 0%, greater than 0%, 0.01%, 0.02%, 0.03%, 0.04%, 0.05%, 0.06%, 0.07%, 0.08%, 0.09%, 0.1%, 0.11%, 0.12%, 0.13%, 0.14%, 0.15%, 0.16%, 0.17%, 0.18%, 0.19%, 0.2%, 0.21%, 0.22%, 0.23%, 0.24%, 0.25%, 0.26%, 0.27%, 0.28%, etc. 0.29%, 0.3%, 0.31%, 0.32%, 0.33%, 0.34%, 0.35%, 0.36%, 0.37%, 0.38%, 0.39%, 0.4%, 0.41%, 0.42%, 0.43%, 0.44%, 0.45%, 0.46%, 0.47%, 0.48%, 0.49%, 0.5%, 0.55%, 0.6%, 0.65%, 0.7%, 0.75%, 0.8%, 0.85%, 0.9%, 0.95%, and 1% Fe2O3.

[0150] The terms "not containing" and "0%" as used herein mean that the compound, molecule, or element was not intentionally added as a raw material to the matrix glass, glass-ceramic, or glass-ceramic product of this invention. However, as raw materials and / or equipment used in the production of matrix glass, glass-ceramic, or glass-ceramic products, there may be certain impurities or components that are not intentionally added, which may be present in small or trace amounts in the final matrix glass, glass-ceramic, or glass-ceramic product. Such cases are also within the scope of protection of this patent.

[0151] The performance indicators of the microcrystalline glass and / or microcrystalline glass products and / or matrix glass of the present invention are tested using the following methods:

[0152] <Light transmittance>

[0153] Light transmittance is tested according to the following method: the sample to be tested is processed to a certain thickness and the opposite surfaces are polished in parallel, and the test is carried out in accordance with the national standard GB / T 7962.12-2010.

[0154] <Coefficient of linear expansion>

[0155] linear expansion coefficient (α) 20℃-300℃Data were obtained from tests conducted at temperatures ranging from 20℃ to 300℃ according to the national standard GB / T7962.16-2010. In this invention, the linear expansion coefficient is sometimes simply referred to as the expansion coefficient.

[0156] <Dielectric constant>

[0157] Dielectric constant (ε) r The test was conducted according to the national standard GB / T 7265.1-1987, and the data was tested under 1GHz conditions.

[0158] <Dielectric Loss>

[0159] Dielectric loss (tanδ) was tested according to the national standard GB / T 7265.1-1987, with data measured under 1GHz conditions.

[0160] <Drop height test>

[0161] Will The sample is placed on a glass bearing fixture, and a 32g steel ball is dropped from a specified height. The maximum drop ball test height from which the sample can withstand the impact without breaking is defined as the drop ball test height. Specifically, the test begins at a drop ball test height of 100mm, and the height is increased sequentially to 100mm, 200mm, 300mm, 400mm, 500mm, 600mm, 700mm, 800mm, 900mm, 100mm, 1000mm, 1100mm, 1200mm, and above without breakage. For the embodiment with "Drop Ball Test Height II," a microcrystalline glass product is used as the test object. In this embodiment, the test data recorded as 1000mm indicates that the microcrystalline glass product withstood the impact without breaking even when a steel ball is dropped from a height of 1000mm. For the embodiment with "Drop Ball Test Height I," a matrix glass is used as the test object. In this invention, the drop ball test height is sometimes simply referred to as the drop ball height.

[0162] Knoop Hardness

[0163] The load (N) when a diamond pyramid indenter with a relative face angle of 172.5° is used to press a pyramid-shaped indentation into the test surface is calculated by dividing the surface area (mm) calculated by the length of the indentation. 2 The value is represented by ). The test is conducted with a load of 100 (N) and a holding time of 15 (seconds). In this invention, Knoop hardness is sometimes simply referred to as hardness.

[0164] Young's Modulus

[0165] Young's modulus (E) is obtained by ultrasonic testing of its longitudinal and transverse wave velocities, and then calculated using the following formula. G = V S2 ρ

[0166] In the formula: E is Young's modulus, Pa;

[0167] G is the shear modulus, Pa;

[0168] V T The transverse wave velocity is in m / s;

[0169] V S The longitudinal wave velocity is given in m / s.

[0170] ρ is the density of glass, in g / cm³ 3 .

[0171] <Refractive index>

[0172] Refractive index (n) d Test according to the method specified in GB / T7962.1-2010.

[0173] The matrix glass of this invention has the following properties:

[0174] 1) In some embodiments, the refractive index (n) of the matrix glass of the present invention is... d The value is 1.51 to 1.55, preferably 1.52 to 1.54, more preferably 1.53 to 1.535, and even more preferably 1.53112 to 1.53284.

[0175] 2) In some embodiments, the Young's modulus (E) of the matrix glass of the present invention is 7000 × 10⁻⁶. 7 Pa ~ 9500 × 10 7 Pa, preferably 7500 × 10 7 Pa~9200×10 7 Pa, more preferably 7836×10 7 Pa ~ 9014 × 10 7 Pa, more preferably 8005 × 10 7 Pa~8488×10 7 Pa.

[0176] 3) In some embodiments, the Knoop hardness (Hk) of the matrix glass of the present invention 0.1 ) is 450 kgf / mm 2 The above values ​​are preferably 470–600 kgf / mm². 2 More preferably, it is 480–582 kgf / mm 2 More preferably, it is 492–532 kgf / mm 2 .

[0177] 4) In some embodiments, the drop ball test height I of the matrix glass of the present invention is 200 mm or more, preferably 300 mm or more, and more preferably 400 mm or more.

[0178] 5) In some embodiments, the dielectric loss (tanδ) of the matrix glass of the present invention is 11.0 × 10⁻⁶. -3 The preferred value is 7.0×10. -3 ~10.5×10 -3 More preferably 7.2×10 -3 ~9.8×10 -3 Further preferred is 7.4×10 -3 ~9.2×10 -3 .

[0179] 6) In some embodiments, the dielectric constant (ε) of the matrix glass of the present invention r The value is 5.5 to 8.5, preferably 6.0 to 8.0, more preferably 6.2 to 7.7, and even more preferably 6.3 to 7.0.

[0180] 7) In some embodiments, the linear expansion coefficient (α) of the matrix glass of the present invention is... 20℃-300℃ ) is 100×10 -7 Below / ℃, preferably 65×10 -7 / ℃~100×10 -7 / ℃, more preferably 71×10 -7 / ℃~95×10 -7 / ℃, further preferably 75×10 -7 / ℃~90×10 -7 / ℃.

[0181] The microcrystalline glass of this invention has the following properties:

[0182] 1) In some embodiments, the average transmittance (T0.2) of the transparent portion of the 0.2–1.5 mm thick microcrystalline glass in the 400–800 nm wavelength range is... 400-800nm The content of the saturation is 85.0% or more, preferably 88.0% or more, more preferably 90.0% or more, even more preferably 91.0% or more, and even more preferably 91.5 to 95.0%. The thickness is preferably 0.5 to 1.5 mm, more preferably 0.8 to 1.2 mm, and even more preferably 0.5 mm, 0.7 mm, 0.8 mm, 0.9 mm, 1.0 mm, 1.1 mm, or 1.2 mm.

[0183] 2) In some embodiments, the average transmittance (T0.2) of the blackened portion of the 0.2–1.5 mm thick microcrystalline glass in the 400–800 nm wavelength range is... 400-800nmThe content of the component is 5.0% or less, preferably 3.0% or less, more preferably 1.5% or less, even more preferably 1.2% or less, and even more preferably 0.5% or less. The thickness is preferably 0.5 to 1.5 mm, more preferably 0.8 to 1.2 mm, and even more preferably 0.5 mm, 0.7 mm, 0.8 mm, 0.9 mm, 1.0 mm, 1.1 mm, or 1.2 mm.

[0184] 3) In some embodiments, the transmittance (T) of the blackened portion of a 0.2–1.5 mm thick microcrystalline glass at 870 nm is... 870nm The content of the active ingredient is 15.0% or less, preferably 0.1-12.5%, more preferably 0.1-10%, even more preferably 0.1-8.0%, and even more preferably 0.1-5.0%. The thickness is preferably 0.5-1.5 mm, more preferably 0.8-1.2 mm, and even more preferably 0.5 mm, 0.7 mm, 0.8 mm, 0.9 mm, 1.0 mm, 1.1 mm, or 1.2 mm.

[0185] 4) In some embodiments, the transmittance (T) of the blackened portion of the 0.2–1.5 mm thick microcrystalline glass at 940 nm is... 940nm The content of the component is 50.0% or less, preferably 0.1-35.0%, more preferably 0.3-20.0%, even more preferably 0.3-15.0%, and even more preferably 0.3-10.0%. The thickness is preferably 0.5-1.5 mm, more preferably 0.8-1.2 mm, and even more preferably 0.5 mm, 0.7 mm, 0.8 mm, 0.9 mm, 1.0 mm, 1.1 mm, or 1.2 mm.

[0186] In some embodiments, since no crystals are formed in the transparent portion of the microcrystalline glass of the present invention, it possesses the same properties as the aforementioned matrix glass, such as Young's modulus (E) and Knoop hardness (Hk). 0.1 ), drop ball test height, dielectric loss (tanδ), dielectric constant (ε) r ), linear expansion coefficient (α) 20℃-300℃ Specifically, in some embodiments, the Young's modulus (E) of the transparent portion of the microcrystalline glass of the present invention is 7000 × 10⁻⁶. 7 Pa ~ 9500 × 10 7 Pa, preferably 7500 × 10 7 Pa~9200×10 7 Pa, more preferably 7836×10 7 Pa ~ 9014 × 10 7 Pa, more preferably 8005 × 10 7 Pa~8488×10 7Pa. In some embodiments, the Knoop hardness (Hk) of the transparent portion of the microcrystalline glass of the present invention... 0.1 ) is 450 kgf / mm 2 The above values ​​are preferably 470–600 kgf / mm². 2 More preferably, it is 480–582 kgf / mm 2 More preferably, it is 492–532 kgf / mm 2 In some embodiments, the drop ball test height of the transparent portion of the microcrystalline glass of the present invention is 200 mm or more, preferably 300 mm or more, and more preferably 400 mm or more. In some embodiments, the dielectric loss (tanδ) of the transparent portion of the microcrystalline glass of the present invention is 11.0 × 10⁻⁶. -3 The preferred value is 7.0×10. -3 ~10.5×10 -3 More preferably 7.2×10 -3 ~9.8×10 -3 Further preferred is 7.4×10 -3 ~9.2×10 -3 In some embodiments, the dielectric constant (ε) of the transparent portion of the microcrystalline glass of the present invention... r The coefficient of linear expansion (α) of the transparent portion of the microcrystalline glass of the present invention is 5.5–8.5, preferably 6.0–8.0, more preferably 6.2–7.7, and even more preferably 6.3–7.0. In some embodiments, the coefficient of linear expansion (α) of the transparent portion of the microcrystalline glass of the present invention is... 20℃-300℃ ) is 100×10 -7 Below / ℃, preferably 65×10 -7 / ℃~100×10 -7 / ℃, more preferably 71×10 -7 / ℃~95×10 -7 / ℃, further preferably 75×10 -7 / ℃~90×10 -7 / ℃.

[0187] The microcrystalline glass products of this invention have the following properties:

[0188] 1) In some embodiments, the average transmittance (T0.2) of the transparent portion of a microcrystalline glass article with a thickness of 0.2–1.5 mm in the 400–800 nm wavelength range. 400-800nm The content of the saturation is 85.0% or more, preferably 88.0% or more, more preferably 90.0% or more, even more preferably 91.0% or more, and even more preferably 91.5 to 95.0%. The thickness is preferably 0.5 to 1.5 mm, more preferably 0.8 to 1.2 mm, and even more preferably 0.5 mm, 0.7 mm, 0.8 mm, 0.9 mm, 1.0 mm, 1.1 mm, or 1.2 mm.

[0189] 2) In some embodiments, the average transmittance (T0.2) of the blackened portion of a microcrystalline glass article with a thickness of 0.2–1.5 mm in the 400–800 nm wavelength range is... 400-800nm The content of the component is 5.0% or less, preferably 3.0% or less, more preferably 1.5% or less, even more preferably 1.2% or less, and even more preferably 0.5% or less. The thickness is preferably 0.5 to 1.5 mm, more preferably 0.8 to 1.2 mm, and even more preferably 0.5 mm, 0.7 mm, 0.8 mm, 0.9 mm, 1.0 mm, 1.1 mm, or 1.2 mm.

[0190] 3) In some embodiments, the transmittance (T) of the blackened portion of a 0.2–1.5 mm thick microcrystalline glass article at 870 nm is... 870nm The content of the active ingredient is 15.0% or less, preferably 0.1-12.5%, more preferably 0.1-10%, even more preferably 0.1-8.0%, and even more preferably 0.1-5.0%. The thickness is preferably 0.5-1.5 mm, more preferably 0.8-1.2 mm, and even more preferably 0.5 mm, 0.7 mm, 0.8 mm, 0.9 mm, 1.0 mm, 1.1 mm, or 1.2 mm.

[0191] 4) In some embodiments, the transmittance (T) of the blackened portion of a 0.2–1.5 mm thick microcrystalline glass article at 940 nm is... 940nm The content of the component is 50.0% or less, preferably 0.1-35.0%, more preferably 0.3-20.0%, even more preferably 0.3-15.0%, and even more preferably 0.3-10.0%. The thickness is preferably 0.5-1.5 mm, more preferably 0.8-1.2 mm, and even more preferably 0.5 mm, 0.7 mm, 0.8 mm, 0.9 mm, 1.0 mm, 1.1 mm, or 1.2 mm.

[0192] 5) In some embodiments, the drop ball test height II of the microcrystalline glass product of the present invention is 800 mm or more, preferably 900 mm or more, more preferably 1000 mm or more, and even more preferably 1100 mm or more.

[0193] In some embodiments, the matrix glass / microcrystalline glass / microcrystalline glass article of the present invention has a low dielectric constant and dielectric loss, which can reduce the transmission loss of electrical signals.

[0194] In some embodiments, the matrix glass / microcrystalline glass / microcrystalline glass articles of the present invention have high Knoop hardness, Young's modulus, and drop height.

[0195] In some embodiments, the matrix glass / microcrystalline glass / microcrystalline glass article of the present invention has a low coefficient of linear expansion to improve the accuracy of optical signal channels or mask patterns.

[0196] In some embodiments, the matrix glass / microcrystalline glass / microcrystalline glass article of the present invention has a low refractive index, which can reduce the reflectivity of surface light signals and increase the incident rate of light signals.

[0197] Due to the aforementioned superior properties, the microcrystalline glass, microcrystalline glass products, and matrix glass of this invention can be widely used to manufacture glass covers or glass components. Furthermore, the microcrystalline glass, microcrystalline glass products, matrix glass, and glass covers or glass components made therefrom can be applied to the manufacture of various instruments or equipment, including but not limited to electronic devices, medical devices, decorative or handicraft items, such as mobile phones, watches, computers, and biomedical testing equipment. These can be used to manufacture partial light-shielding glass or patterned cover glass for mobile phones, smartphones, tablets, laptops, televisions, etc., or for optical signal channel glass in smartwatches, biomedical devices, etc., or for manufacturing patterned decorative or handicraft glass.

[0198] The matrix glass, glass-ceramic, and glass-ceramic articles of the present invention can be produced and manufactured by the following methods:

[0199] The manufacturing method of matrix glass includes the following steps: weighing raw materials according to the component ratio and mixing them evenly; placing the uniformly mixed raw materials into a platinum or quartz crucible; melting, clarifying, and homogenizing at 1450-1600℃; cooling the mixture; pouring the molten glass into a mold to form the glass; and circulating cooling air to ensure that the glass does not crystallize. Preferably, the mold is preheated to 200-500℃. The formed glass and the mold are placed together in an annealing furnace for heat preservation and annealing. Then, the power is turned off and the glass is cooled with the furnace to obtain matrix glass.

[0200] The manufacturing method of microcrystalline glass includes the following steps: forming a substrate glass, processing the substrate glass through a crystallization process, or processing the substrate glass into a glass element of a specific shape and then processing it through a crystallization process to obtain the microcrystalline glass of the present invention. The method of processing the substrate glass into a glass element of a specific shape includes methods known to those skilled in the art, such as hot pressing, grinding, or polishing. The crystallization process of the present invention includes mask exposure of the substrate glass, followed by crystallization heat treatment, to uniformly precipitate crystals at the exposed locations on the glass. The mask exposure process of the present invention refers to ultraviolet exposure at specific locations or areas of the substrate glass, with the ultraviolet wavelength preferably 313 nm. A dedicated photomask pattern can be customized according to application needs, and the exposure time is preferably 5–60 minutes. The crystallization heat treatment of the present invention can be performed in one stage or in two stages, preferably in two stages. The two-stage crystallization heat treatment refers to performing a nucleation process at a first temperature and then performing a crystal growth process at a second temperature higher than the nucleation process temperature. Preferably, the first temperature is 490℃~520℃ and the first temperature treatment time is 1~4 hours. Preferably, the second temperature is 540℃~620℃ and the second temperature treatment time is 1~8 hours.

[0201] The manufacturing method of the microcrystalline glass product includes the following steps: processing the microcrystalline glass of the present invention through a chemical strengthening process, or processing the microcrystalline glass into a microcrystalline glass element of a specific shape and then processing it through a chemical strengthening process to obtain the microcrystalline glass product of the present invention. The methods for processing the microcrystalline glass into a specific shape include methods known to those skilled in the art, such as hot pressing, grinding, or polishing.

[0202] The chemical strengthening method described in this invention is ion exchange. During ion exchange, smaller metal ions in the glass-ceramic are replaced or "exchanged" by larger metal ions with the same valence state located nearby. The replacement of smaller ions with larger ions creates compressive stress within the glass-ceramic, forming a compressive stress layer.

[0203] In some embodiments, the metal ion is a monovalent alkali metal ion (e.g., Na+). + K + 、Rb + Cs + Ion exchange is carried out by immersing a glass-ceramic glass in a salt bath containing at least one molten salt containing larger metal ions, which replace smaller metal ions in the glass-ceramic glass. Alternatively, other monovalent metal ions such as Ag can be used. + 、Tl + Cu +Ion exchange processes can also be used to exchange monovalent ions. One or more ion exchange processes used to chemically strengthen glass-ceramics may include, but are not limited to, immersing the glass in a single salt bath, or immersing it in multiple salt baths having the same or different compositions, with washing and / or annealing steps added between immersions.

[0204] In some embodiments, the microcrystalline glass can be ion-exchanged by immersing it in a salt bath of molten Na salt (such as NaNO3) and / or K salt (such as KNO3) and / or a mixed Na and K salt at a temperature of about 350°C to 470°C for 1 to 36 hours, preferably at a temperature range of 380°C to 460°C and for a preferred time range of 2 to 24 hours.

[0205] In some embodiments, the matrix glass of the present invention can be manufactured into strengthened glass through the above-described chemical strengthening process, and then processed into microcrystalline glass products through the above-described crystallization process. In some embodiments, the matrix glass of the present invention can be processed into glass elements, and then the glass elements can be manufactured into strengthened glass through the above-described chemical strengthening process, and then processed into microcrystalline glass products through the above-described crystallization process.

[0206] Example

[0207] To further clarify and illustrate the technical solution of the present invention, the following non-limiting embodiments are provided. While the embodiments of the present invention have made considerable efforts to ensure the accuracy of numerical values ​​(e.g., quantities), some errors and deviations must be taken into account. The composition itself is based on oxides and is given in weight percent, and has been normalized to 100%.

[0208] <Matrix Glass Examples>

[0209] In this embodiment, a matrix glass with the composition shown in Tables 1 to 4 was obtained using the above-described matrix glass manufacturing method. Furthermore, the properties of each matrix glass were measured using the testing method described in this invention, and the measurement results are shown in Tables 1 to 4.

[0210] Table 1.

[0211] Table 2.

[0212] Table 3.

[0213] Table 4.

[0214] <Examples of Microcrystalline Glass>

[0215] In this embodiment, the microcrystalline glass with the composition shown in Tables 5 to 8 was obtained using the above-described manufacturing method. Furthermore, the characteristics of each microcrystalline glass were measured using the testing method described in this invention, and the measurement results are shown in Tables 5 to 8. In the following embodiments, the transmittance of the microcrystalline glass was tested using a 1 mm thick sample.

[0216] Table 5.

[0217] Table 6.

[0218] Table 7.

[0219] Table 8.

[0220] <Examples of Microcrystalline Glass Products>

[0221] This embodiment uses the above-described manufacturing method for microcrystalline glass products to obtain microcrystalline glass products with the compositions shown in Tables 9 to 12. Furthermore, the characteristics of each microcrystalline glass product were measured using the testing method described in this invention, and the measurement results are shown in Tables 9 to 12. In the following embodiments, the transmittance of the microcrystalline glass products was tested using a 1 mm thick sample.

[0222] Table 9.

[0223] Table 10.

[0224] Table 11.

[0225] Table 12.

Claims

1. A microcrystalline glass product, characterized in that, Its components, expressed as a percentage by weight, contain: SiO2: 65-78%; R2O: 2-12%; Li2O: 5-15%; Al2O3: 3-12%; ZrO2: 1.5-10%; CeO2: 0.01-0.6%; Ag2O: 0.01-0.8%, wherein the R2O is one or both of Na2O and K2O.

2. The microcrystalline glass product according to claim 1, characterized in that, Its components, expressed as a weight percentage, also contain: Sb2O3: 0-1%; and / or SnO2: 0-0.5%; and / or MO: 0-5%; and / or Ln2O3: 0-5%; and / or Fe2O3: 0-1%, wherein MO is one or more of MgO, CaO, SrO, BaO, and ZnO, and Ln2O3 is one or more of La2O3, Gd2O3, and Y2O3.

3. A microcrystalline glass product, characterized in that, Its components, expressed as a weight percentage, consist of SiO2: 65-78%; R2O: 2-12%; Li2O: 5-15%; Al2O3: 3-12%; ZrO2: 1.5-10%; CeO2: 0.01-0.6%; Ag2O: 0.01-0.8%; Sb2O3: 0-1%; SnO2: 0-0.5%; MO: 0-5%; Ln2O3: 0-5%; Fe2O3: 0-1%. The R2O is one or both of Na2O and K2O, the MO is one or more of MgO, CaO, SrO, BaO, and ZnO, and the Ln2O3 is one or more of La2O3, Gd2O3, and Y2O3.

4. The microcrystalline glass article according to any one of claims 1 to 3, characterized in that, Its components, expressed as a weight percentage, satisfy one or more of the following 14 conditions: 1) The SiO2 / Li2O ratio is 5.5 to 10.0, preferably 6.0 to 9.0, and more preferably 7.0 to 8.5; 2) The ratio of (Sb2O3+SnO2) / Ag2O is 0.1 to 5.0, preferably 0.5 to 3.5, and more preferably 1.0 to 2.6; 3) The ratio of (K2O+Na2O) / ZrO2 is 0.5 to 7.1, preferably 0.7 to 4.5, and more preferably 0.8 to 2.5; 4) The Ag2O / CeO2 ratio is 1.0 to 10.0, preferably 1.5 to 6.5, and more preferably 2.0 to 4.5; 5) The Li2O / ZrO2 ratio is 1.0 to 7.5, preferably 1.2 to 5.0, more preferably 1.4 to 4.3, and even more preferably 1.6 to 3.0; 6) The ratio of (SiO2+Li2O) / ZrO2 is 8.0 to 55.0, preferably 10.0 to 37.0, more preferably 12.0 to 25.0, and even more preferably 13.0 to 20.0; 7) The ZrO2 / (Ag2O+CeO2) ratio is 2.3 to 50.0, preferably 6.5 to 35.0, more preferably 8.5 to 20.0, and even more preferably 11.0 to 18.0; 8) The ratio of (Ag2O+SnO2+Sb2O3) / CeO2 is 1.0 to 30.0, preferably 3.0 to 20.0, more preferably 5.0 to 12.5, and even more preferably 7.5 to 10.

0. 9) The ratio of (Sb2O3+SnO2+CeO2) / Ag2O is 0.1 to 10.0, preferably 0.4 to 5.0, more preferably 0.7 to 3.7, and even more preferably 1.5 to 3.

2. 10) The SnO2 / (CeO2+SnO2) ratio is 0 to 0.9, preferably 0 to 0.6, and more preferably SnO2 / (CeO2+SnO2) is 0~0.5; 11) The content of R2O+Li2O+Al2O3 is 15-30%, preferably 17.5-29.5%, more preferably 18.5-26%, and even more preferably 20-25%. 12)(SiO2+Al2O3) / (Li2O+Na2O+K2O) is 3.0-7.5, preferably 3.7-6.5, more preferably 4.3-6.0, and even more preferably 4.8-5.8; 13) The MO / ZrO2 ratio is 2.5 or less, preferably 1.5 or less, and more preferably 0.5 or less; 14) Sb2O3+SnO2: 0.05-1.2%, preferably Sb2O3+SnO2: 0.1-1%, more preferably Sb2O3+SnO2: 0.2-0.7%, wherein R2O is one or two of Na2O and K2O, and MO is one or more of MgO, CaO, SrO, BaO, and ZnO.

5. The microcrystalline glass article according to any one of claims 1 to 3, characterized in that, Its components are expressed as weight percentages, wherein: SiO2: 68-77%, preferably SiO2: 69.5-75.5%; and / or R2O: 3-10%, preferably R2O: 4-8%; and / or Li2O: 7-13%, preferably Li2O: 8.5-12%; and / or Al2O3: 4-10%, preferably Al2O3: 5-9%; and / or ZrO2: 2-8%, preferably ZrO2: 3-6.5%; and / or CeO2: 0.07-0.4%, preferably CeO2: 0.08-0.3%; and / or Ag2O: 0.1-0.6%, preferably Ag2O: 0.2-0.5%; and / or Sb2O3: 0.01-0.7%. The preferred components are Sb₂O₃: 0.07–0.5%; and / or SnO₂: 0–0.3%, preferably SnO₂: 0–0.2%; and / or MO: 0–3%, preferably MO: 0–1%, more preferably without MO; and / or Ln₂O₃: 0–3%, preferably Ln₂O₃: 0–1%, more preferably without Ln₂O₃; and / or Fe₂O₃: 0–0.5%, preferably Fe₂O₃: 0–0.2%, more preferably without Fe₂O₃, wherein R₂O is one or two of Na₂O and K₂O, MO is one or more of MgO, CaO, SrO, BaO, and ZnO, and Ln₂O₃ is one or more of La₂O₃, Gd₂O₃, and Y₂O₃.

6. The microcrystalline glass article according to any one of claims 1 to 3, characterized in that, The microcrystalline glass product comprises one or more blackened portions and one or more transparent portions; or the entire microcrystalline glass product is blackened.

7. The microcrystalline glass product according to claim 6, characterized in that, The microcrystalline glass product contains a lithium silicate crystalline phase, preferably a lithium metasilicate crystalline phase, more preferably the lithium metasilicate crystalline phase has a weight percentage of 5-50% in the blackened portion of the microcrystalline glass product, even more preferably the lithium metasilicate crystalline phase has a weight percentage of 5-40% in the blackened portion of the microcrystalline glass product, and even more preferably the lithium metasilicate crystalline phase has a weight percentage of 10-30% in the blackened portion of the microcrystalline glass product.

8. The microcrystalline glass article according to claim 6, characterized in that, The average transmittance T of the transparent portion of microcrystalline glass products with a thickness of 0.2–1.5 mm in the 400–800 nm wavelength range. 400-800nm The transmittance is 85.0% or more, preferably 88.0% or more, more preferably 90.0% or more, further preferably 91.0% or more, and even more preferably 91.5 to 95.0%; and / or the average transmittance T of the blackened portion of a microcrystalline glass article with a thickness of 0.2 to 1.5 mm in the 400 to 800 nm wavelength range. 400-800nm The transmittance T of the blackened portion of a microcrystalline glass article with a thickness of 0.2 to 1.5 mm at 870 nm is 5.0% or less, preferably 3.0% or less, more preferably 1.5% or less, even more preferably 1.2% or less, and still more preferably 0.5% or less; and / or the transmittance T of the blackened portion of the microcrystalline glass article with a thickness of 0.2 to 1.5 mm. 870nm The transmittance T of the blackened portion of a microcrystalline glass article with a thickness of 0.2 to 1.5 mm at 940 nm is 15.0% or less, preferably 0.1 to 12.5%, more preferably 0.1 to 10%, further preferably 0.1 to 8.0%, and even more preferably 0.1 to 5.0%; and / or the transmittance T of the blackened portion of the microcrystalline glass article with a thickness of 0.2 to 1.5 mm. 940nm The content is 50.0% or less, preferably 0.1% to 35.0%, more preferably 0.3% to 20.0%, even more preferably 0.3% to 15.0%, and even more preferably 0.3% to 10.0%.

9. The microcrystalline glass article according to claim 8, characterized in that, The thickness of the microcrystalline glass product is 0.5-1.5 mm, preferably 0.8-1.2 mm, and more preferably 0.5 mm, 0.7 mm, 0.8 mm, 0.9 mm, 1.0 mm, 1.1 mm, or 1.2 mm.

10. The microcrystalline glass article according to any one of claims 1 to 3, characterized in that, The drop ball test height II of the microcrystalline glass product is 800 mm or more, preferably 900 mm or more, more preferably 1000 mm or more, and even more preferably 1100 mm or more.

11. A microcrystalline glass, characterized in that, Its components, expressed as a percentage by weight, contain: SiO2: 65-78%; R2O: 2-12%; Li2O: 5-15%; Al2O3: 3-12%; ZrO2: 1.5-10%; CeO2: 0.01-0.6%; Ag2O: 0.01-0.8%, wherein the R2O is one or both of Na2O and K2O.

12. The microcrystalline glass according to claim 11, characterized in that, Its components, expressed as a weight percentage, also contain: Sb2O3: 0-1%; and / or SnO2: 0-0.5%; and / or MO: 0-5%; and / or Ln2O3: 0-5%; and / or Fe2O3: 0-1%, wherein MO is one or more of MgO, CaO, SrO, BaO, and ZnO, and Ln2O3 is one or more of La2O3, Gd2O3, and Y2O3.

13. A microcrystalline glass, characterized in that, Its components, expressed as a weight percentage, consist of SiO2: 65-78%; R2O: 2-12%; Li2O: 5-15%; Al2O3: 3-12%; ZrO2: 1.5-10%; CeO2: 0.01-0.6%; Ag2O: 0.01-0.8%; Sb2O3: 0-1%; SnO2: 0-0.5%; MO: 0-5%; Ln2O3: 0-5%; Fe2O3: 0-1%. The R2O is one or both of Na2O and K2O, the MO is one or more of MgO, CaO, SrO, BaO, and ZnO, and the Ln2O3 is one or more of La2O3, Gd2O3, and Y2O3.

14. The microcrystalline glass according to any one of claims 11 to 13, characterized in that, Its components, expressed as a weight percentage, satisfy one or more of the following 14 conditions: 1) The SiO2 / Li2O ratio is 5.5 to 10.0, preferably 6.0 to 9.0, and more preferably 7.0 to 8.5; 2) The ratio of (Sb2O3+SnO2) / Ag2O is 0.1 to 5.0, preferably 0.5 to 3.5, and more preferably 1.0 to 2.6; 3) The ratio of (K2O+Na2O) / ZrO2 is 0.5 to 7.1, preferably 0.7 to 4.5, and more preferably 0.8 to 2.5; 4) The Ag2O / CeO2 ratio is 1.0 to 10.0, preferably 1.5 to 6.5, and more preferably 2.0 to 4.5; 5) The Li2O / ZrO2 ratio is 1.0 to 7.5, preferably 1.2 to 5.0, more preferably 1.4 to 4.3, and even more preferably 1.6 to 3.0; 6) The ratio of (SiO2+Li2O) / ZrO2 is 8.0 to 55.0, preferably 10.0 to 37.0, more preferably 12.0 to 25.0, and even more preferably 13.0 to 20.0; 7) The ZrO2 / (Ag2O+CeO2) ratio is 2.3 to 50.0, preferably 6.5 to 35.0, more preferably 8.5 to 20.0, and even more preferably 11.0 to 18.0; 8) The ratio of (Ag₂O+SnO₂+Sb₂O₃) / CeO₂ is 1.0–30.0, preferably 3.0– 20.0, more preferably (Ag2O+SnO2+Sb2O3) / CeO2 is 5.0 to 12.5, and even more preferably (Ag2O+SnO2+Sb2O3) / CeO2 is 7.5 to 10.0; 9) The ratio of (Sb2O3+SnO2+CeO2) / Ag2O is 0.1 to 10.0, preferably 0.4 to 5.0, more preferably 0.7 to 3.7, and even more preferably 1.5 to 3.

2. 10) SnO2 / (CeO2+SnO2) is 0 to 0.9, preferably SnO2 / (CeO2+SnO2) is 0 to 0.6, and more preferably SnO2 / (CeO2+SnO2) is 0 to 0.5; 11) The content of R2O+Li2O+Al2O3 is 15-30%, preferably 17.5-29.5%, more preferably 18.5-26%, and even more preferably 20-25%. 12)(SiO2+Al2O3) / (Li2O+Na2O+K2O) is 3.0-7.5, preferably 3.7-6.5, more preferably 4.3-6.0, and even more preferably 4.8-5.8; 13) The MO / ZrO2 ratio is 2.5 or less, preferably 1.5 or less, and more preferably 0.5 or less; 14) Sb2O3+SnO2: 0.05-1.2%, preferably Sb2O3+SnO2: 0.1-1%, more preferably Sb2O3+SnO2: 0.2-0.7%, wherein R2O is one or two of Na2O and K2O, and MO is one or more of MgO, CaO, SrO, BaO, and ZnO.

15. The microcrystalline glass according to any one of claims 11 to 13, characterized in that, Its components are expressed as weight percentages, wherein: SiO2: 68-77%, preferably SiO2: 69.5-75.5%; and / or R2O: 3-10%, preferably R2O: 4-8%; and / or Li2O: 7-13%, preferably Li2O: 8.5-12%; and / or Al2O3: 4-10%, preferably Al2O3: 5-9%; and / or ZrO2: 2-8%, preferably ZrO2: 3-6.5%; and / or CeO2: 0.07-0.4%, preferably CeO2: 0.08-0.3%; and / or Ag2O: 0.1-0.6%, preferably Ag2O: 0.2-0.5%; and / or Sb2O3: 0.01-0.7%. The preferred components are Sb₂O₃: 0.07–0.5%; and / or SnO₂: 0–0.3%, preferably SnO₂: 0–0.2%; and / or MO: 0–3%, preferably MO: 0–1%, more preferably without MO; and / or Ln₂O₃: 0–3%, preferably Ln₂O₃: 0–1%, more preferably without Ln₂O₃; and / or Fe₂O₃: 0–0.5%, preferably Fe₂O₃: 0–0.2%, more preferably without Fe₂O₃, wherein R₂O is one or two of Na₂O and K₂O, MO is one or more of MgO, CaO, SrO, BaO, and ZnO, and Ln₂O₃ is one or more of La₂O₃, Gd₂O₃, and Y₂O₃.

16. The microcrystalline glass according to any one of claims 11 to 13, characterized in that, The microcrystalline glass comprises one or more blackened portions and one or more transparent portions; or the entire microcrystalline glass is composed of blackened portions.

17. The microcrystalline glass according to claim 16, characterized in that, The microcrystalline glass contains a lithium silicate phase, preferably a lithium metasilicate phase, more preferably a lithium metasilicate phase by weight in the blackened portion of the microcrystalline glass, even more preferably a lithium metasilicate phase by weight in the blackened portion of the microcrystalline glass, and even more preferably a lithium metasilicate phase by weight in the blackened portion of the microcrystalline glass ...

18. The microcrystalline glass according to claim 16, characterized in that, The average transmittance T of the transparent portion of microcrystalline glass with a thickness of 0.2–1.5 mm in the 400–800 nm wavelength range. 400-800nm The transmittance is 85.0% or more, preferably 88.0% or more, more preferably 90.0% or more, further preferably 91.0% or more, and even more preferably 91.5 to 95.0%; and / or the average transmittance T of the blackened portion of the microcrystalline glass with a thickness of 0.2 to 1.5 mm in the 400 to 800 nm wavelength range. 400-800nm The transmittance T of the blackened portion of the microcrystalline glass with a thickness of 0.2 to 1.5 mm at 870 nm is 5.0% or less, preferably 3.0% or less, more preferably 1.5% or less, even more preferably 1.2% or less, and still more preferably 0.5% or less; and / or the transmittance T of the blackened portion of the microcrystalline glass with a thickness of 0.2 to 1.5 mm. 870nm The transmittance T of the blackened portion of a microcrystalline glass with a thickness of 0.2 to 1.5 mm at 940 nm is 15.0% or less, preferably 0.1 to 12.5%, more preferably 0.1 to 10%, further preferably 0.1 to 8.0%, and even more preferably 0.1 to 5.0%; and / or the transmittance T of the blackened portion of the microcrystalline glass with a thickness of 0.2 to 1.5 mm. 940nm The content is 50.0% or less, preferably 0.1% to 35.0%, more preferably 0.3% to 20.0%, even more preferably 0.3% to 15.0%, and even more preferably 0.3% to 10.0%.

19. The microcrystalline glass according to claim 18, characterized in that, The thickness of the microcrystalline glass is 0.5-1.5 mm, preferably 0.8-1.2 mm, and more preferably 0.5 mm, 0.7 mm, 0.8 mm, 0.9 mm, 1.0 mm, 1.1 mm, or 1.2 mm.

20. A matrix glass, characterized in that, Its components, expressed as a percentage by weight, contain: SiO2: 65-78%; R2O: 2-12%; Li2O: 5-15%; Al2O3: 3-12%; ZrO2: 1.5-10%; CeO2: 0.01-0.6%; Ag2O: 0.01-0.8%, wherein the R2O is one or both of Na2O and K2O.

21. The matrix glass according to claim 20, characterized in that, Its components, expressed as a weight percentage, also contain: Sb2O3: 0-1%; and / or SnO2: 0-0.5%; and / or MO: 0-5%; and / or Ln2O3: 0-5%; and / or Fe2O3: 0-1%, wherein MO is one or more of MgO, CaO, SrO, BaO, and ZnO, and Ln2O3 is one or more of La2O3, Gd2O3, and Y2O3.

22. A matrix glass, characterized in that, Its components, expressed as a weight percentage, consist of SiO2: 65-78%; R2O: 2-12%; Li2O: 5-15%; Al2O3: 3-12%; ZrO2: 1.5-10%; CeO2: 0.01-0.6%; Ag2O: 0.01-0.8%; Sb2O3: 0-1%; SnO2: 0-0.5%; MO: 0-5%; Ln2O3: 0-5%; Fe2O3: 0-1%. The R2O is one or both of Na2O and K2O, the MO is one or more of MgO, CaO, SrO, BaO, and ZnO, and the Ln2O3 is one or more of La2O3, Gd2O3, and Y2O3.

23. The matrix glass according to any one of claims 20 to 22, characterized in that, Its components, expressed as a weight percentage, satisfy one or more of the following 14 conditions: 1) The SiO2 / Li2O ratio is 5.5 to 10.0, preferably 6.0 to 9.0, and more preferably 7.0 to 8.5; 2) The ratio of (Sb2O3+SnO2) / Ag2O is 0.1 to 5.0, preferably 0.5 to 3.5, and more preferably 1.0 to 2.6; 3) The ratio of (K2O+Na2O) / ZrO2 is 0.5 to 7.1, preferably 0.7 to 4.5, and more preferably 0.8 to 2.5; 4) The Ag2O / CeO2 ratio is 1.0 to 10.0, preferably 1.5 to 6.5, and more preferably 2.0 to 4.5; 5) The Li2O / ZrO2 ratio is 1.0 to 7.5, preferably 1.2 to 5.0, more preferably 1.4 to 4.3, and even more preferably 1.6 to 3.0; 6) The ratio of (SiO2+Li2O) / ZrO2 is 8.0 to 55.0, preferably 10.0 to 37.0, more preferably 12.0 to 25.0, and even more preferably 13.0 to 20.0; 7) The ZrO2 / (Ag2O+CeO2) ratio is 2.3 to 50.0, preferably 6.5 to 35.0, more preferably 8.5 to 20.0, and even more preferably 11.0 to 18.0; 8) The ratio of (Ag2O+SnO2+Sb2O3) / CeO2 is 1.0 to 30.0, preferably 3.0 to 20.0, more preferably 5.0 to 12.5, and even more preferably 7.5 to 10.

0. 9) The ratio of (Sb2O3+SnO2+CeO2) / Ag2O is 0.1 to 10.0, preferably 0.4 to 5.0, more preferably 0.7 to 3.7, and even more preferably 1.5 to 3.

2. 10) SnO2 / (CeO2+SnO2) is 0 to 0.9, preferably SnO2 / (CeO2+SnO2) is 0 to 0.6, and more preferably SnO2 / (CeO2+SnO2) is 0 to 0.5; 11) The content of R2O+Li2O+Al2O3 is 15-30%, preferably 17.5-29.5%, more preferably 18.5-26%, and even more preferably 20-25%. 12)(SiO2+Al2O3) / (Li2O+Na2O+K2O) is 3.0-7.5, preferably 3.7-6.5, more preferably 4.3-6.0, and even more preferably 4.8-5.8; 13) The MO / ZrO2 ratio is 2.5 or less, preferably 1.5 or less, and more preferably 0.5 or less; 14) Sb2O3+SnO2: 0.05-1.2%, preferably Sb2O3+SnO2: 0.1-1%, more preferably Sb2O3+SnO2: 0.2-0.7%, wherein R2O is one or two of Na2O and K2O, and MO is one or more of MgO, CaO, SrO, BaO, and ZnO.

24. The matrix glass according to any one of claims 20 to 22, characterized in that, Its components are expressed as weight percentages, wherein: SiO2: 68-77%, preferably SiO2: 69.5-75.5%; and / or R2O: 3-10%, preferably R2O: 4-8%; and / or Li2O: 7-13%, preferably Li2O: 8.5-12%; and / or Al2O3: 4-10%, preferably Al2O3: 5-9%; and / or ZrO2: 2-8%, preferably ZrO2: 3-6.5%; and / or CeO2: 0.07-0.4%, preferably CeO2: 0.08-0.3%; and / or Ag2O: 0.1-0.6%, preferably Ag2O: 0.2-0.5%; and / or Sb2O3: 0.01-0.7%. The preferred components are Sb₂O₃: 0.07–0.5%; and / or SnO₂: 0–0.3%, preferably SnO₂: 0–0.2%; and / or MO: 0–3%, preferably MO: 0–1%, more preferably without MO; and / or Ln₂O₃: 0–3%, preferably Ln₂O₃: 0–1%, more preferably without Ln₂O₃; and / or Fe₂O₃: 0–0.5%, preferably Fe₂O₃: 0–0.2%, more preferably without Fe₂O₃, wherein R₂O is one or two of Na₂O and K₂O, MO is one or more of MgO, CaO, SrO, BaO, and ZnO, and Ln₂O₃ is one or more of La₂O₃, Gd₂O₃, and Y₂O₃.

25. The matrix glass according to any one of claims 20 to 22, characterized in that, The refractive index n of the matrix glass d The value is 1.51–1.55, preferably 1.52–1.54, more preferably 1.53–1.535, and even more preferably 1.53112–1.53284; and / or the Young's modulus E is 7000 × 10⁻⁶. 7 Pa ~ 9500 × 10 7 Pa, preferably 7500 × 10 7 Pa~9200×10 7 Pa, more preferably 7836×10 7 Pa ~ 9014 × 10 7 Pa, more preferably 8005 × 10 7 Pa~8488×10 7 Pa; and / or Knoop hardness Hk 0.1 450 kgf / mm 2 The above values ​​are preferably 470–600 kgf / mm². 2 More preferably, it is 480–582 kgf / mm 2 More preferably, it is 492–532 kgf / mm 2 ; and / or the drop ball test height I is 200 mm or more, preferably 300 mm or more, more preferably 400 mm or more; and / or the dielectric loss tanδ is 11.0 × 10⁻⁶. -3 The preferred value is 7.0×10. -3 ~10.5×10 -3 More preferably 7.2×10 -3 ~9.8×10 -3 Further preferred is 7.4×10 -3 ~9.2×10 -3 ; and / or dielectric constant ε r The coefficient of linear expansion is 5.5 to 8.5, preferably 6.0 to 8.0, more preferably 6.2 to 7.7, and even more preferably 6.3 to 7.0; and / or the coefficient of linear expansion α. 20℃-300℃ 100×10 -7 Below / ℃, preferably 65×10 -7 / ℃~100×10 -7 / ℃, more preferably 71×10 -7 / ℃~95×10 -7 / ℃, further preferably 75×10 -7 / ℃~90×10 -7 / ℃.

26. A glass cover plate, characterized in that, The product comprises a microcrystalline glass article according to any one of claims 1 to 10, and / or a microcrystalline glass according to any one of claims 11 to 19, and / or a matrix glass according to any one of claims 20 to 25.

27. A glass component, characterized in that, The product comprises a microcrystalline glass article according to any one of claims 1 to 10, and / or a microcrystalline glass according to any one of claims 11 to 19, and / or a matrix glass according to any one of claims 20 to 25.

28. A device, characterized in that, The product comprises a microcrystalline glass article according to any one of claims 1 to 10, and / or a microcrystalline glass according to any one of claims 11 to 19, and / or a matrix glass according to any one of claims 20 to 25, and / or a glass cover according to claim 26, and / or a glass component according to claim 27.

29. A method for manufacturing the microcrystalline glass article according to any one of claims 1 to 10, characterized in that, The method includes the following steps: forming a matrix glass, forming microcrystalline glass from the matrix glass through a crystallization process, and then forming microcrystalline glass products from the microcrystalline glass through a chemical strengthening process.

30. The method for manufacturing a microcrystalline glass article according to claim 29, characterized in that, The crystallization process includes mask exposure of the substrate glass followed by crystallization heat treatment. The mask exposure process includes ultraviolet exposure of a specific location or area of ​​the substrate glass. The ultraviolet wavelength is preferably 313 nm, and the exposure time is preferably 5 to 60 minutes.

31. The method for manufacturing a microcrystalline glass article according to claim 30, characterized in that, The crystallization heat treatment is carried out in two stages. The two-stage crystallization heat treatment includes nucleation process at a first temperature and crystal growth process at a second temperature higher than the nucleation process temperature. Preferably, the first temperature is 490℃~520℃ and the first temperature treatment time is 1~4 hours. Preferably, the second temperature is 540℃~620℃ and the second temperature treatment time is 1~8 hours.

32. The method for manufacturing a microcrystalline glass article according to claim 29, characterized in that, The chemical strengthening process includes immersing the microcrystalline glass in a salt bath of molten Na salt, and / or K salt, and / or a mixed Na and K salt at a temperature of 350°C to 470°C for about 1 to 36 hours, preferably at a temperature of 380°C to 460°C, and preferably for a time of 2 to 24 hours.

33. A method for manufacturing the microcrystalline glass according to any one of claims 11 to 19, characterized in that, The method includes the following steps: forming a matrix glass, and then forming a microcrystalline glass from the matrix glass through a crystallization process.

34. The method for manufacturing microcrystalline glass according to claim 33, characterized in that, The crystallization process includes mask exposure of the substrate glass followed by crystallization heat treatment. The mask exposure process includes ultraviolet exposure of a specific location or area of ​​the substrate glass. The ultraviolet wavelength is preferably 313 nm, and the exposure time is preferably 5 to 60 minutes.

35. The method for manufacturing microcrystalline glass according to claim 34, characterized in that, The crystallization heat treatment is carried out in two stages. The two-stage crystallization heat treatment includes nucleation process at a first temperature and crystal growth process at a second temperature higher than the nucleation process temperature. Preferably, the first temperature is 490℃~520℃ and the first temperature treatment time is 1~4 hours. Preferably, the second temperature is 540℃~620℃ and the second temperature treatment time is 1~8 hours.

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