Microcrystalline glass, microcrystalline glass products, and methods for manufacturing the same

Abstract

This invention provides a microcrystalline glass product, which contains the following components by weight: 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%, where R2O is one or both of Na2O and K2O. Through a rational component design, the matrix glass of this invention can be transformed into microcrystalline glass with blackened and transparent portions by a crystallization process. The microcrystalline glass obtained in this invention is suitable for chemical strengthening, and the microcrystalline glass and microcrystalline glass products manufactured using this microcrystalline glass possess excellent mechanical properties.

Description

[Technical Field]

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

[0002] In recent years, with the continuous rise and development of consumer electronic products, glass has been widely used in electronic devices as a transparent and high-performance material. Because electronic devices use many precision electronic components inside, it is necessary to install covers or enclosures to protect the internal electronic components. As market needs diversify, the usage scenarios for protective cover glass are becoming increasingly complex, and it is necessary to protect internal electronic components while also incorporating other functions. For example, vital sign monitoring by smartwatches requires localized light transmission of the glass material, but light shielding is necessary in other areas to avoid interference from stray light. Therefore, the glass material needs to have both black and transparent parts simultaneously, which can be said to be a new challenge for glass manufacturing technology. Conventional technology can manufacture the above cover material using an inlaid design method with two different materials, transparent and black. However, the strength of the two materials differs, the difference in coefficient of thermal expansion is large, and it is necessary to process through holes. Furthermore, minute cracks exist in the inner wall of the glass, which reduces the strength of the cover material, making it difficult to process small holes and irregular patterns, and resulting in high manufacturing costs.

[0003] Photosensitive microcrystalline glass is a type of microcrystalline glass produced by irradiating a matrix glass with ultraviolet light to induce structural changes within the glass, generating nuclei, and then heat-treating it at a specific temperature to generate a large number of specific crystals in the irradiated area. The exposed areas have a high degree of crystallinity, the glass becomes darker in color, and the light transmittance decreases. The unexposed areas remain transparent because the glass has not crystallized. By performing a mask exposure treatment on these areas, it is possible to make the glass material have both black and transparent areas simultaneously. On the other hand, glass materials used to manufacture protective covers need to have excellent mechanical properties so that they can withstand normal "touch" and other contact during use, as well as accidental bending, scratching, and impact breakage over a long period of time. To increase the ability to withstand breakage due to accidental external forces, the strength of the glass material can be improved by chemical strengthening methods. However, conventional photosensitive microcrystalline glass cannot be chemically strengthened, or the chemical strengthening effect is poor due to the "non-uniformity" of the photosensitive microcrystalline glass itself (differences in the structure of crystalline and uncrystalline parts), making it difficult to meet the requirements for use in high-performance electronic devices, etc. [Overview of the project]

[0004] Based on the reasons stated above, the technical problem that the present invention aims to solve is to provide a matrix glass that can be used in the manufacture of microcrystalline glass having blackened portions and transparent portions.

[0005] The present invention also provides microcrystalline glass suitable for chemical strengthening, and the microcrystalline glass and microcrystalline glass products manufactured using it possess excellent mechanical properties.

[0006] The technical means employed in this invention are as follows: (1) Microcrystalline glass products containing the following components by weight %,: 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 R2O is one or both of Na2O and K2O. (2) The microcrystalline glass product described in (1), further comprising the following components by weight: 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) Microcrystalline glass products containing the following components by weight %, consisting 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 both 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. (4) A microcrystalline glass product containing SiO2, R2O, Li2O, Al2O3, ZrO2, CeO2 and Ag2O, wherein R2O is one or two types of Na2O and K2O, and the steel ball drop test height II of the microcrystalline glass product is 800 mm or more. (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%. (6) A microcrystalline glass product comprising SiO2, R2O, Li2O, Al2O3, ZrO2, CeO2 and Ag2O, wherein 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. (7) Microcrystalline glass products containing SiO2, Li2O, Al2O3 and ZrO2, wherein the components are expressed in weight percent, and the SiO2 / Li2O ratio is 5.5 to 10.0. (8) A microcrystalline glass product containing SiO2, R2O, Li2O, Al2O3 and ZrO2, wherein R2O is one or two of Na2O and K2O, and the components are expressed in weight percent, where (K2O + Na2O) / ZrO2 is 0.5 to 7.1. (9) Microcrystalline glass products containing SiO2, Li2O, Al2O3 and ZrO2, wherein the components are expressed in weight percent, and (SiO2 + Li2O) / ZrO2 is between 8.0 and 55.0. (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 crystalline phase, and the weight % of the lithium metasilicate crystalline phase is higher than that of the other crystalline phases. (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 the microcrystalline glass product having a thickness of 0.2 to 1.5 mm at 870 nm. 870nm The percentage is 15.0% or less. (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 the microcrystalline glass product with a thickness of 0.2 to 1.5 mm is 940 nm. 940nm The percentage is 50.0% or less. (13) Microcrystalline glass products as described in any one of (4) to (12), containing the following components by weight %: 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 S b2O3: 0-1%, and / or SnO2: 0-0.5%, and / or MO: 0-5%, and / or Ln2O3: 0-5%, and / or Fe2O3: 0-1%, where R2O is one or both 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. (14) A microcrystalline glass product according to any one of (1) to (13) containing the following components by weight: 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. (15) A microcrystalline glass product according to any one of (1) to (14) containing the following components by weight %, 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. (16) A microcrystalline glass product according to any one of (1) to (15) containing the following components by weight %: (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. (17) A microcrystalline glass product according to any one of (1) to (16), containing the following components by weight %: 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. (18) A microcrystalline glass product according to any one of (1) to (17), containing the following components by weight %: 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. (19) A microcrystalline glass product according to any one of (1) to (18), containing the following components by weight %: (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. (20) A microcrystalline glass product according to any one of (1) to (19) containing the following components by weight %: 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. (21) A microcrystalline glass product according to any one of (1) to (20) containing the following components by weight %: (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. (22) A microcrystalline glass product according to any one of (1) to (21), containing the following components by weight %: (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. (23) A microcrystalline glass product according to any one of (1) to (22) containing the following components by weight %: 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. (24) A microcrystalline glass product according to any one of (1) to (23), containing the following components by weight %: 15 to 30% R2O + Li2O + Al2O3, preferably 17.5 to 29.5% R2O + Li2O + Al2O3, more preferably 18.5 to 26% R2O + Li2O + Al2O3, and even more preferably 20 to 25% R2O + Li2O + Al2O3, wherein R2O is one or both of Na2O and K2O. (25) A microcrystalline glass product according to any one of (1) to (24) containing the following components by weight %: (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. (26) A microcrystalline glass product according to any one of (1) to (25), containing the following components by weight %: 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 the MO is one or more of MgO, CaO, SrO, BaO, and ZnO. (27) A microcrystalline glass product according to any one of (1) to (26), containing the following components by weight: Sb2O3+SnO2: 0.05 to 1.2%, preferably Sb2O3+SnO2: 0.1 to 1%, more preferably Sb2O3+SnO2: 0.2 to 0.7%. (28) A microcrystalline glass product according to any one of (1) to (27), comprising the following components by weight %,: 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%, 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 no MO, and / or Ln2O3:0~3%, preferably Ln2O3:0~1%, more preferably no Ln2O3, and / or Fe2O3:0~0.5%, preferably Fe2O3:0~0.2%, more preferably no Fe2O3, wherein R2O is one or both 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. (29) The microcrystalline glass product according to any one of (1) to (28), wherein the microcrystalline glass product comprises one or more blackened portions and one or more transparent portions, or the entire microcrystalline glass product is a blackened portion. (30) The microcrystalline glass product according to any one of (1) to (29), wherein the microcrystalline glass product contains a lithium silicate crystalline phase, preferably a lithium metasilicate crystalline phase, more preferably the weight % of the lithium metasilicate crystalline phase in the blackened portion of the microcrystalline glass product is 5 to 50%, even more preferably the weight % of the lithium metasilicate crystalline phase in the blackened portion of the microcrystalline glass product is 5 to 40%, and even more preferably the weight % of the lithium metasilicate crystalline phase in the blackened portion of the microcrystalline glass product is 10 to 30%. (31) Average transmittance T in the 400-800 nm band range of the transparent portion of a microcrystalline glass product with a thickness of 0.2-1.5 mm 400-800nm The average transmittance T in the 400-800 nm band range of the blackened portion of a microcrystalline glass product with a thickness of 0.2-1.5 mm 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 91.5-95.0%. 400-800nm The transmittance T in the 870nm band of the blackened portion of a microcrystalline glass product with a thickness of 0.2 to 1.5 mm is 5.0% or less, preferably 3.0% or less, more preferably 1.5% or less, even more preferably 1.2% or less, and / or even more preferably 0.5% or less. 870nm The transmittance T in the 940nm band of the blackened portion of a microcrystalline glass product with a thickness of 0.2 to 1.5 mm is 15.0% or less, preferably 0.1 to 12.5%, more preferably 0.1 to 10%, even more preferably 0.1 to 8.0%, and / or even more preferably 0.1 to 5.0%. 940nm The microcrystalline glass product according to any one of (1) to (30), wherein 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%. (32) The microcrystalline glass product according to any one of (1) to (31), wherein the thickness of the microcrystalline glass product is 0.5 to 1.5 mm, preferably 0.8 to 1.2 mm, more preferably 0.5 mm, 0.7 mm, 0.8 mm, 0.9 mm, 1.0 mm, 1.1 mm, or 1.2 mm. (33) The microcrystalline glass product according to any one of (1) to (32), wherein the height of the ball drop test 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. (34) Microcrystalline glass containing the following components by weight: 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 R2O is one or both of Na2O and K2O. (35) Microcrystalline glass as described in (34), further comprising the following components by weight: 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. (36) Microcrystalline glass containing the following components by weight %, consisting 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 both 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. (37) A microcrystalline glass comprising one or more blackened portions and one or more transparent portions, wherein the microcrystalline glass contains a lithium metasilicate crystalline phase, and in the blackened portions of the microcrystalline glass, the weight percentage of the lithium metasilicate crystalline phase is 5 to 50%. (38) A microcrystalline glass comprising SiO2, R2O, Li2O, Al2O3, ZrO2, CeO2 and Ag2O, wherein 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. (39) A microcrystalline glass containing SiO2, R2O, Li2O, Al2O3 and ZrO2, wherein R2O is one or two of Na2O and K2O, and the components are expressed in weight percent, where SiO2 / Li2O is 5.5 to 10.0. (40) A microcrystalline glass containing SiO2, R2O, Li2O, Al2O3 and ZrO2, wherein R2O is one or two of Na2O and K2O, and the components are expressed in weight percent, where (K2O + Na2O) / ZrO2 is 0.5 to 7.1. (41) A microcrystalline glass containing SiO2, R2O, Li2O, Al2O3 and ZrO2, wherein R2O is one or two of Na2O and K2O, and the components are expressed in weight percent, where (SiO2 + Li2O) / ZrO2 is 8.0 to 55.0. (42) A microcrystalline glass comprising SiO2, Li2O, Al2O3, CeO2 and Ag2O, wherein R2O is one or both of Na2O and K2O, and the Ag2O / CeO2 ratio is 1.0 to 10.0. (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 crystalline phase, the weight % of the lithium metasilicate crystalline phase is higher than that of the other crystalline phases. (44) 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 silicate crystalline phase. (45) Microcrystalline glass comprising one or more blackened portions and one or more transparent portions, wherein the transmittance T of the blackened portion of the microcrystalline glass with a thickness of 0.2 to 1.5 mm in the 870 nm band. 870nm The percentage is 15.0% or less. (46) Microcrystalline glass comprising one or more blackened portions and one or more transparent portions, wherein the transmittance T of the blackened portion of the microcrystalline glass with a thickness of 0.2 to 1.5 mm in the 940 nm band. 940nm The percentage is 50.0% or less. (47) Microcrystalline glass as described in any one of (37) to (46), containing the following components by weight %: 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 S b2O3: 0-1%, and / or SnO2: 0-0.5%, and / or MO: 0-5%, and / or Ln2O3: 0-5%, and / or Fe2O3: 0-1%, where R2O is one or both 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. (48) Microcrystalline glass according to any one of (34) to (47), containing the following components by weight %: SiO2 / Li2O is 5.5 to 10.0, preferably SiO2 / Li2O is 6.0 to 9.0, more preferably SiO2 / Li2O is 7.0 to 8.5. (49) Microcrystalline glass according to any one of (34) to (48), containing the following components by weight %: (Sb2O3+SnO2) / Ag2O in a ratio of 0.1 to 5.0, preferably (Sb2O3+SnO2) / Ag2O in a ratio of 0.5 to 3.5, and more preferably (Sb2O3+SnO2) / Ag2O in a ratio of 1.0 to 2.6. (50) Microcrystalline glass according to any one of (34) to (49), containing the following components by weight %: (K2O+Na2O) / ZrO2 is 0.5 to 7.1, preferably (K2O+Na2O) / ZrO2 is 0.7 to 4.5, more preferably (K2O+Na2O) / ZrO2 is 0.8 to 2.5. (51) Microcrystalline glass according to any one of (34) to (50), containing the following components by weight %: Ag2O / CeO2 is 1.0 to 10.0, preferably Ag2O / CeO2 is 1.5 to 6.5, more preferably Ag2O / CeO2 is 2.0 to 4.5. (52) Microcrystalline glass according to any one of (34) to (51), containing the following components by weight %: Li2O / ZrO2 in a ratio of 1.0 to 7.5, preferably Li2O / ZrO2 in a ratio of 1.2 to 5.0, more preferably Li2O / ZrO2 in a ratio of 1.4 to 4.3, and even more preferably Li2O / ZrO2 in a ratio of 1.6 to 3.0. (53) Microcrystalline glass according to any one of (34) to (52), containing the following components by weight %: (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. (54) Microcrystalline glass according to any one of (34) to (53), containing the following components by weight %: 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. (55) Microcrystalline glass according to any one of (34) to (54), containing the following components by weight %: (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. (56) Microcrystalline glass according to any one of (34) to (55), containing the following components by weight %: (Sb2O3+SnO2+CeO2) / Ag2O in a concentration of 0.1 to 10.0, preferably (Sb2O3+SnO2+CeO2) / Ag2O in a concentration of 0.4 to 5.0, more preferably (Sb2O3+SnO2+CeO2) / Ag2O in a concentration of 0.7 to 3.7, and even more preferably (Sb2O3+SnO2+CeO2) / Ag2O in a concentration of 1.5 to 3.2. (57) Microcrystalline glass according to any one of (34) to (56), containing the following components by weight %: SnO2 / (CeO2+SnO2) is 0 to 0.9, preferably SnO2 / (CeO2+SnO2) is 0 to 0.6, more preferably SnO2 / (CeO2+SnO2) is 0 to 0.5. (58) Microcrystalline glass according to any one of (34) to (57), comprising the following components by weight %,: 15 to 30% R2O + Li2O + Al2O3, preferably 17.5 to 29.5% R2O + Li2O + Al2O3, more preferably 18.5 to 26% R2O + Li2O + Al2O3, and even more preferably 20 to 25% R2O + Li2O + Al2O3, wherein R2O is one or both of Na2O and K2O. (59) Microcrystalline glass according to any one of (34) to (58), containing the following components by weight %: (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. (60) Microcrystalline glass according to any one of (34) to (59), containing the following components by weight: 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 the MO is one or more of MgO, CaO, SrO, BaO, and ZnO. (61) Microcrystalline glass according to any one of (34) to (60), comprising the following components by weight %: Sb2O3+SnO2: 0.05~1.2%, preferably Sb2O3+SnO2: 0.1~1%, more preferably Sb2O3+SnO2: 0.2~0.7%. (62) Microcrystalline glass according to any one of (34) to (61), comprising the following components by weight %: 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%, 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 no MO, and / or Ln2O3:0~3%, preferably Ln2O3:0~1%, more preferably no Ln2O3, and / or Fe2O3:0~0.5%, preferably Fe2O3:0~0.2%, more preferably no Fe2O3, wherein R2O is one or both 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. (63) The microcrystalline glass according to any one of (34) to (62), wherein the microcrystalline glass includes one or more blackened portions and one or more transparent portions, or the entire microcrystalline glass is a blackened portion. (64) The microcrystalline glass according to any one of (34) to (63), wherein the microcrystalline glass contains a lithium silicate crystalline phase, preferably a lithium metasilicate crystalline phase, more preferably the weight % of the lithium metasilicate crystalline phase in the blackened portion of the microcrystalline glass is 5 to 50%, even more preferably the weight % of the lithium metasilicate crystalline phase in the blackened portion of the microcrystalline glass is 5 to 40%, and even more preferably the weight % of the lithium metasilicate crystalline phase in the blackened portion of the microcrystalline glass is 10 to 30%. (65) Average transmittance T in the 400-800 nm band range of the transparent portion of microcrystalline glass with a thickness of 0.2-1.5 mm400-800nm is 85.0% or more, preferably 88.0% or more, more preferably 90.0% or more, still more preferably 91.0% or more, even more preferably 91.5 - 95.0%, and / or the average transmittance T in the wavelength range of 400 - 800 nm of the blackened portion of the microcrystalline glass with a thickness of 0.2 - 1.5 mm 400-800nm is 5.0% or less, preferably 3.0% or less, more preferably 1.5% or less, still more preferably 1.2% or less, even more preferably 0.5% or less, and / or the transmittance T in the 870 nm wavelength band of the blackened portion of the microcrystalline glass with a thickness of 0.2 - 1.5 mm 870nm is 15.0% or less, preferably 0.1 - 12.5%, more preferably 0.1 - 10%, still more preferably 0.1 - 8.0%, even more preferably 0.1 - 5.0%, and / or the transmittance T in the 940 nm wavelength band of the blackened portion of the microcrystalline glass with a thickness of 0.2 - 1.5 mm 940nm is 50.0% or less, preferably 0.1 - 35.0%, more preferably 0.3 - 20.0%, still more preferably 0.3 - 15.0%, even more preferably 0.3 - 10.0%, the microcrystalline glass according to any one of (34) - (64). (66) The thickness of the microcrystalline glass is 0.5 - 1.5 mm, preferably 0.8 - 1.2 mm, more preferably 0.5 mm, 0.7 mm, 0.8 mm, 0.9 mm, 1.0 mm, 1.1 mm, 1.2 mm, the microcrystalline glass according to any one of (34) - (65). (67) Matrix glass containing the following components by weight%: 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%, where the R2O is one or both of Na2O and K2O. (68) The matrix glass according to (67), further containing the following components by weight%: Sb2O3: 0 - 1%, and / or SnO2: 0 - 0.5%, and / or MO: 0 - 5%, and / or Ln2O3: 0 - 5%, and / or Fe2O3: 0 - 1%, where the MO is one or more of MgO, CaO, SrO, BaO, ZnO, and the Ln2O3 is one or more of La2O3, Gd2O3, Y2O3. (69) A matrix glass comprising the following components by weight %, consisting 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 both 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. (70) A matrix glass containing SiO2, R2O, Li2O, Al2O3 and ZrO2, wherein R2O is one or two of Na2O and K2O, the components are expressed in weight percent, and the SiO2 / Li2O ratio is 5.5 to 10.0. (71) A matrix glass comprising SiO2, R2O, Li2O, Al2O3 and ZrO2, wherein R2O is one or two of Na2O and K2O, the components are expressed in weight percent, and (K2O + Na2O) / ZrO2 is 0.5 to 7.1. (72) A matrix glass comprising SiO2, R2O, Li2O, Al2O3 and ZrO2, wherein R2O is one or two of Na2O and K2O, the components are expressed in weight percent, and (SiO2 + Li2O) / ZrO2 is 8.0 to 55.0. (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. (74) A matrix glass comprising SiO2, R2O, Li2O, Al2O3 and ZrO2, wherein R2O is one or two of Na2O and K2O, and the Young's modulus E of the matrix glass is 7000 × 10 7 Pa~9500×10 7 It is Pa. (75) A matrix glass comprising SiO2, R2O, Li2O, Al2O3 and ZrO2, wherein R2O is one or two of Na2O and K2O, and the relative permittivity of the matrix glass is ε r The range is 5.5 to 8.5. (76) A matrix glass comprising SiO2, R2O, Li2O, Al2O3 and ZrO2, wherein R2O is one or two of Na2O and K2O, and the Knoop hardness Hk of the matrix glass 0.1 It is 450 kgf / mm 2 That's all. (77) A matrix glass comprising SiO2, R2O, Li2O and ZrO2, wherein R2O is one or two types of Na2O and K2O, and the linear expansion coefficient of the matrix glass is α 20℃-300℃ is 100 x 10 -7 It is below / ℃. (78) A matrix glass according to any one of (70) to (77) containing, by weight %, the following components: 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 The composition is as follows: Sb2O3: 0-1%, and / or SnO2: 0-0.5%, and / or MO: 0-5%, and / or Ln2O3: 0-5%, and / or Fe2O3: 0-1%, where R2O is one or both 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. (79) A matrix glass according to any one of (67) to (78) containing the following components by weight: 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. (80) A matrix glass according to any one of (67) to (79) containing the following components by weight: (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. (81) A matrix glass according to any one of (67) to (80) containing the following components by weight: (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. (82) A matrix glass according to any one of (67) to (81) containing the following components by weight: 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. (83) A matrix glass according to any one of (67) to (82) containing the following components by weight: 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. (84) A matrix glass according to any one of (67) to (83) containing the following components by weight: (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. (85) A matrix glass according to any one of (67) to (84) containing the following components by weight %: 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. (86) A matrix glass according to any one of (67) to (85) containing the following components by weight %: (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. (87) A matrix glass according to any one of (67) to (86) containing the following components by weight %: (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. (88) A matrix glass according to any one of (67) to (87) containing the following components by weight: 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. (89) A matrix glass according to any one of (67) to (88), comprising the following components by weight %, wherein R2O+Li2O+Al2O3 is 15-30%, preferably 17.5-29.5%, more preferably 18.5-26%, and even more preferably 20-25%, and the R2O is one or both of Na2O and K2O. (90) A matrix glass according to any one of (67) to (89) containing the following components by weight %: (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. (91) A matrix glass according to any one of (67) to (90) containing the following components by weight: 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 the MO is one or more of MgO, CaO, SrO, BaO, and ZnO. (92) A matrix glass according to any one of (67) to (91) containing the following components by weight: Sb2O3+SnO2: 0.05 to 1.2%, preferably Sb2O3+SnO2: 0.1 to 1%, more preferably Sb2O3+SnO2: 0.2 to 0.7%. (93) A matrix glass according to any one of (67) to (92), comprising the following components by weight %,: 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: 0.0 1-0.7%, 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 no MO, and / or Ln2O3:0-3%, preferably Ln2O3:0-1%, more preferably no Ln2O3, and / or Fe2O3:0-0.5%, preferably Fe2O3:0-0.2%, more preferably no Fe2O3, wherein R2O is one or both 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. (94) The refractive index n of the matrix glass dThe matrix glass according to any of (67) to (93), wherein the Young's modulus E 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, and / or the Young's modulus E is 7000 × 10 7 Pa~9500×10 7 Pa, preferably 7500 × 10 7 Pa~9200×10 7 Pa, uh, 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 is preferably 470-600 kgf / mm². 2 , more preferably 480-582 kgf / mm² 2 More preferably 492-532 kgf / mm² 2 , and / or the height I of the ball drop test 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 -3 The following is preferably 7.0 × 10 -3 ~10.5×10 -3 , more preferably 7.2 × 10 -3 ~9.8×10 -3 More preferably 7.4 × 10 -3 ~9.2×10 -3 , and / or dielectric constant ε r α is 5.5 to 8.5, preferably 6.0 to 8.0, more preferably 6.2 to 7.7, even more preferably 6.3 to 7.0, and / or the coefficient of linear expansion α 20℃-300℃ 100 x 10 -7 / ℃ or lower, preferably 65 × 10 -7 / ℃~100×10 -7 / ℃, more 71×10 -7 / ℃~95×10 -7 / ℃, more preferably 75 × 10 -7 / ℃~90×10 -7 It is / ℃. (95) A glass lid plate comprising a microcrystalline glass product as described in any one of (1) to (33), and / or a microcrystalline glass as described in any one of (34) to (66), and / or a matrix glass as described in any one of (67) to (94). (96) A glass element comprising a microcrystalline glass product as described in any one of (1) to (33), and / or a microcrystalline glass as described in any one of (34) to (66), and / or a matrix glass as described in any one of (67) to (94). (97) An apparatus comprising a microcrystalline glass product as described in any of (1) to (33), and / or a microcrystalline glass as described in any of (34) to (66), and / or a matrix glass as described in any of (67) to (94), and / or a cover glass as described in (95), and / or a glass element as described in (96). (98) A method for manufacturing a microcrystalline glass product according to any one of (1) to (33), the method comprising the following steps: forming a matrix glass; processing the matrix glass into microcrystalline glass by a crystallization process; and processing the microcrystalline glass into a microcrystalline glass product by a chemical strengthening process. (99) The method for producing a microcrystalline glass product according to (98), wherein the crystallization process comprises a mask exposure treatment of the matrix glass and a recrystallization heat treatment, the mask exposure treatment comprising ultraviolet exposure treatment of a specific position or region of the matrix glass, the wavelength of the ultraviolet light is preferably 313 nm, and the exposure time is preferably 5 to 60 minutes. (100) The method for manufacturing a microcrystalline glass product according to (98) or (99), wherein the crystallization heat treatment is carried out in two stages, the two-stage crystallization heat treatment includes a nucleation process treatment at a first temperature and a crystal growth process treatment at a second temperature higher than the temperature of the nucleation process, the first temperature being preferably 490°C to 520°C, the treatment time at the first temperature being preferably 1 to 4 hours, the second temperature being preferably 540°C to 620°C, and the treatment time at the second temperature being preferably 1 to 8 hours. (101) A method for producing a microcrystalline glass product according to any one of (98) to (100), wherein the chemical strengthening process comprises immersing the microcrystalline glass in a salt bath of molten sodium salt and / or potassium salt and / or a mixed salt of sodium and potassium at a temperature of 350°C to 470°C for about 1 to 36 hours, the temperature preferably 380°C to 460°C and the time preferably 2 to 24 hours. A method for producing microcrystalline glass according to any one of (102) (34) to (66), the method comprising the following steps: forming a matrix glass and processing the matrix glass into microcrystalline glass by a crystallization process. (103) The method for producing microcrystalline glass according to (102), wherein the crystallization process comprises a mask exposure treatment of the matrix glass and a recrystallization heat treatment, the mask exposure treatment comprising ultraviolet exposure treatment of a specific position or region of the matrix glass, the wavelength of the ultraviolet light is preferably 313 nm, and the exposure time is preferably 5 to 60 minutes. (104) The method for producing microcrystalline glass according to (102) or (103), wherein the crystallization heat treatment is carried out in two stages, the two-stage crystallization heat treatment includes a nucleation process treatment at a first temperature and a crystal growth process treatment at a second temperature higher than the nucleation process temperature, the first temperature is preferably 490°C to 520°C, the treatment time at the first temperature is preferably 1 to 4 hours, the second temperature is preferably 540°C to 620°C, and the treatment time at the second temperature is preferably 1 to 8 hours.

[0007] The beneficial effects of the present invention are as follows: Through a rational compositional design, the matrix glass of the present invention can be obtained as microcrystalline glass having blackened and transparent portions by crystallization process treatment. The microcrystalline glass obtained in the present invention is suitable for chemical strengthening, and the microcrystalline glass and microcrystalline glass products manufactured using the microcrystalline glass have excellent mechanical properties. In some embodiments, the microcrystalline glass or microcrystalline glass product of the present invention has blackened and transparent portions, the transparent portion has high transmittance in the visible light band, and the blackened portion has low transmittance in the visible light band. [Modes for carrying out the invention]

[0008] The embodiments of the present invention will be described in detail below, but the present invention is not limited to the embodiments described below and can be implemented by modifying them as appropriate within the scope of the object of the present invention. Furthermore, although there may be omissions as appropriate, the gist of the present invention is not limited by repetition of the description.

[0009] The microcrystalline glass and microcrystalline glass products of the present invention are materials having a crystalline phase (sometimes called a crystal) and a glass phase that are different from amorphous solids. The crystalline phase of the microcrystalline glass and microcrystalline glass products can be identified by the peak angle appearing in the X-ray diffraction pattern of X-ray diffraction analysis and / or measured by TEMEDX.

[0010] As a result of repeated experimental research by the inventors, the microcrystalline glass or microcrystalline glass product of the present invention was obtained by precipitating a specific crystalline phase by specifying the content and ratio of specific components constituting microcrystalline glass and microcrystalline glass products to specific values.

[0011] 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 portions are the average transmittance (T) of the microcrystalline glass in the 400-800 nm band range when the microcrystalline glass is processed to a thickness of 0.2 to 1.5 mm. 400-800nm ) refers to the portion where the transmittance is 85.0% or higher, and the blackened portion is the average transmittance (T) of the microcrystalline glass in the 400-800nm ​​band range when the microcrystalline glass is processed to a thickness of 0.2-1.5mm. 400-800nm ) refers to the portion that is 5.0% or less. In some embodiments, the blackened portion of the microcrystalline glass contains a crystalline phase, while the transparent portion of the microcrystalline glass does not. In some embodiments, the crystalline phase in the blackened portion of the microcrystalline glass is uniformly distributed.

[0012] In some embodiments, the microcrystalline glass product of the present invention includes one or more blackened portions and one or more transparent portions, wherein the transparent portions are the average transmittance (T) of the microcrystalline glass product in the 400-800 nm band range when the microcrystalline glass product is processed to a thickness of 0.2 to 1.5 mm. 400-800nm ) refers to the portion where the transmittance is 85.0% or more, and the blackened portion is the average transmittance (T) of the microcrystalline glass product in the 400-800nm ​​band range when the microcrystalline glass product is processed to a thickness of 0.2-1.5mm. 400-800nm ) refers to the portion that is 5.0% or less. In some embodiments, the blackened portion of the microcrystalline glass product contains a crystalline phase, while the transparent portion of the microcrystalline glass product does not. In some embodiments, the crystalline phase in the blackened portion of the microcrystalline glass product is uniformly distributed.

[0013] In some embodiments, the entire microcrystalline glass or microcrystalline glass product of the present invention is a blackened portion, and the blackened portion is the average transmittance (T) of the microcrystalline glass or microcrystalline glass product in the 400-800 nm band range when the microcrystalline glass or microcrystalline glass product is processed to a thickness of 0.2 to 1.5 mm. 400-800nm ) refers to the portion that is 5.0% or less. In some embodiments, the crystalline phase of the blackened portion of the microcrystalline glass or microcrystalline glass product is uniformly distributed.

[0014] In some embodiments, the entire microcrystalline glass or microcrystalline glass product of the present invention is a transparent portion, and the transparent portion is the average transmittance (T) of the microcrystalline glass or microcrystalline glass product in the 400-800 nm band range when the microcrystalline glass or microcrystalline glass product is processed to a thickness of 0.2 to 1.5 mm. 400-800nm ) refers to the portion that is 85.0% or more.

[0015] In some embodiments, the blackened portion of the microcrystalline glass or microcrystalline glass product of the present invention can form a pattern of any shape and / or size.

[0016] The following describes the range of components (components) of the matrix glass, microcrystalline glass, and microcrystalline glass products of the present invention. In this specification, unless otherwise specified, the content of each component shall be expressed as a weight percentage (wt%) of the matrix glass, microcrystalline glass, or microcrystalline glass product converted to an oxide composition. Here, "converted to an oxide composition" means that the total weight of oxide substances when oxides, complex salts, hydroxides, etc. used as raw materials for the composition of the matrix glass, microcrystalline glass, or microcrystalline glass product of the present invention decompose into oxides during melting is taken as 100%. In this specification, "glass" refers to matrix glass before crystallization (i.e., crystallization process treatment), crystallized matrix glass (i.e., crystallization process treatment) is referred to as microcrystalline glass, and microcrystalline glass products refer to products obtained by chemically strengthening microcrystalline glass.

[0017] Specifically, the numerical ranges described herein include upper and lower limits, and “greater than or equal to” and “less than or equal to” include endpoint values, as well as all integers and fractions included in the range, and are not limited to the specific values ​​described where the range is limited. The term “about” as used herein means that recipes, parameters and other quantities, and features are not, and do not need to be, precise and can be approximated and / or greater or less as needed, reflecting tolerances, conversion factors, measurement errors, etc. What is referred to herein as “and / or” is inclusive; for example, “A and / or B” means A only, B only, or both A and B.

[0018] In some embodiments of the present invention, the crystalline phase (crystals) of the microcrystalline glass or microcrystalline glass product includes a lithium silicate crystalline phase, preferably a lithium metasilicate (Li2SiO3) crystalline phase. In some embodiments, the weight percentage of the lithium metasilicate crystalline phase is higher than that of other crystalline phases. In some embodiments, the crystalline phase of the microcrystalline glass or microcrystalline glass product includes only the lithium metasilicate crystalline phase.

[0019] In some embodiments, the weight percentage of the lithium metasilicate crystalline phase in the blackened portion of the microcrystalline glass or microcrystalline glass product is 5 to 50%, preferably 5 to 40%, and more preferably 10 to 30%. In some embodiments, the weight percentage of the lithium metasilicate crystalline phase in the blackened portion of microcrystalline glass or microcrystalline glass products 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%, and 50%.

[0020] SiO2 is a glass-forming oxide that forms the skeleton of glass, has low dielectric constant and dielectric loss, and is a component of lithium metasilicate in microcrystalline glass. If the SiO2 content is less than 65%, the hardness and coefficient of thermal expansion of the glass decrease, and the dielectric constant and dielectric loss of the glass increase. If the SiO2 content exceeds 78%, the transmittance of the blackened parts of microcrystalline glass and microcrystalline glass products increases. Therefore, the SiO2 content is 65-78%, preferably 68-77%, and more preferably 69.5-75.5%. In some embodiments, it can 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%, and 78% SiO2.

[0021] Li2O is the main component that forms the crystals in the microcrystalline glass and microcrystalline glass products of the present invention. When the Li2O content is less than 5%, the crystal content of the microcrystalline glass or microcrystalline glass product decreases, and the transmittance of the blackened portion is relatively high. On the other hand, when the Li2O content exceeds 15%, the Young's modulus of the glass and the height of the steel ball drop test decrease, and the refractive index and dielectric loss of the glass increase. In addition, portions of the matrix glass that are not irradiated with ultraviolet light during the crystallization process tend to crystallize during the heat treatment process, and the transmittance of the transparent portion of the microcrystalline glass and microcrystalline glass product decreases. Therefore, the Li2O content is limited to 5-15%, preferably 7-13%, and more preferably 8.5-12%. In some embodiments, it may contain approximately 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%, and 15% Li2O.

[0022] Through their research, the inventors found that in some embodiments, the hardness of the glass and the height of the steel ball drop test increased with increasing SiO2 / Li2O values, while the refractive index decreased with increasing SiO2 / Li2O values. Furthermore, when SiO2 / Li2O is less than 5.5, the transmittance of the transparent portion of the microcrystalline glass and microcrystalline glass product decreases, while the transmittance of the blackened portion increases. When SiO2 / Li2O is greater than 10.0, the crystal content of the blackened portion of the microcrystalline glass and microcrystalline glass product decreases, and the transmittance of the blackened portion increases. Therefore, in some embodiments, when SiO2 / Li2O is preferably 5.5 to 10.0, more preferably 6.0 to 9.0, and even more preferably 7.0 to 8.5, the transmittance in the visible light band of the transparent portion of the microcrystalline glass and microcrystalline glass product is relatively high, the transmittance of the blackened portion is relatively low, and it is particularly suitable for optical signal channels or light shielding systems in electronic products. In some embodiments, 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.

[0023] Alkali metal oxides R2O (R2O being one or both Na2O and K2O) promote the precipitation of lithium metasilicate crystals and can improve the transmittance of the blackened areas of microcrystalline glass and microcrystalline glass products. If the R2O content is less than 2%, the crystal content of microcrystalline glass and microcrystalline glass products decreases, the transmittance of the blackened areas increases, and the blackening effect may not be achieved. If the R2O content exceeds 12%, the Young's modulus of the glass and the height of the steel ball drop test decrease, and the refractive index, relative permittivity, 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 embodiments, it may contain R2O in amounts of approximately 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%, and 12%.

[0024] Al2O3 can suppress the decrease in transmittance of the transparent portion of microcrystalline glass and microcrystalline glass products after mask exposure and heat treatment, improve the strength and hardness of the glass, and enhance the chemical stability of the glass. If the Al2O3 content is less than 3%, the hardness and Young's modulus of the glass decrease, and the coefficient of linear expansion increases. If the Al2O3 content exceeds 12%, the relative permittivity and dielectric loss of the glass increase, the crystal content of the blackened portion of microcrystalline glass and microcrystalline glass products decreases, the transmittance of the blackened portion increases, and in some cases the blackening effect cannot be achieved. Therefore, the Al2O3 content is 3 to 12%, preferably 4 to 10%, and more preferably 5 to 9%. In some embodiments, the mixture may contain approximately 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.

[0025] 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, and when R2O+Li2O+Al2O3 exceeds 30%, the relative permittivity and dielectric loss of the glass increase. Therefore, preferably, R2O+Li2O+Al2O3 is 15-30%, more preferably 17.5-29.5%, even more preferably 18.5-26%, and even more preferably 20-25%. In some embodiments, the R2O+Li2O+Al2O3 content 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%, and 30%.

[0026] As a result of extensive experimental research conducted by the inventors, they found that in some embodiments, by controlling the ratio (SiO2+Al2O3) / (Li2O+Na2O+K2O) of the total content of SiO2 and Al2O3 to the total content of Li2O, Na2O, and K2O within the range of 3.0 to 7.5, the transmittance of the blackened portion of microcrystalline glass and microcrystalline glass products can be lowered, the refractive index of the glass can be relatively lowered, the reflectance of the optical signal on the glass surface can be reduced, and the incidence rate of the optical signal can be increased. Therefore, preferably (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 embodiments, the value of (SiO2+Al2O3) / (Li2O+Na2O+K2O) may 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.

[0027] ZrO2 adjusts the accuracy of black pattern formation in the blackened areas after mask exposure of glass, clearly defines the boundary between the exposed and unexposed areas, prevents crystallization near the boundary after heat treatment of the unexposed areas, maintains high transmittance in the visible light band after heat treatment of the unexposed areas, and ensures low transmittance in the blackened areas after heat treatment of the exposed areas. If the ZrO2 content is less than 1.5%, the coefficient of thermal expansion of the glass increases, making the unexposed areas more prone to crystallization during heat treatment of the glass, and reducing the transmittance of the transparent areas. If the ZrO2 content exceeds 10%, the crystal content of microcrystalline glass and microcrystalline glass products decreases, increasing the transmittance of the blackened areas, and in some cases the blackening effect cannot be achieved. Therefore, the ZrO2 content is 1.5 to 10%, preferably 2 to 8%, and more preferably 3 to 6.5%. In some embodiments, the mixture may contain approximately 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%, and 10% ZrO2.

[0028] In some embodiments, by controlling the ratio of the total content of K2O and Na2O (K2O+Na2O) to the content of ZrO2 ((K2O+Na2O) / ZrO2) to within the range of 0.5 to 7.1, the transmittance of the transparent portion of the microcrystalline glass and microcrystalline glass products is relatively high, the hardness and Young's modulus of the glass are relatively high, and the relative permittivity of the glass is relatively low. Therefore, (K2O+Na2O) / ZrO2 is preferably 0.5 to 7.1, more preferably 0.7 to 4.5, and even more preferably 0.8 to 2.5. In some embodiments, 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.

[0029] In some embodiments, by controlling the ratio of Li2O content to ZrO2 content, Li2O / ZrO2, within the range of 1.0 to 7.5, the refractive index and dielectric loss of the glass can be reduced, improving the pattern formation accuracy in microcrystalline glass and microcrystalline glass products after mask exposure and heat treatment of the glass. As a result, the transmittance of the transparent parts of the microcrystalline glass and microcrystalline glass products is relatively high, and the transmittance of the blackened parts is relatively low. Therefore, preferably Li2O / ZrO2 is 1.0 to 7.5, more preferably Li2O / ZrO2 is 1.2 to 5.0, even more preferably Li2O / ZrO2 is 1.4 to 4.3, and even more preferably Li2O / ZrO2 is 1.6 to 3.0. In some embodiments, the Li2O / ZrO2 values ​​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, 7.5.

[0030] In some embodiments, by controlling the ratio of the total content of SiO2 and Li2O (SiO2+Li2O) to the content of ZrO2 ((SiO2+Li2O) / ZrO2) to within the range of 8.0 to 55.0, the hardness of the glass and the height of the steel ball drop test can be increased, the coefficient of thermal expansion and relative permittivity of the glass can be decreased, the accuracy of pattern formation in microcrystalline glass and microcrystalline glass products can be improved after mask exposure and heat treatment of the glass, the height of the steel ball drop test of microcrystalline glass and microcrystalline glass products can be increased, and the transmittance of the blackened parts of microcrystalline glass and microcrystalline glass products is relatively low. Therefore, preferably (SiO2+Li2O) / ZrO2 is 8.0 to 55.0, more preferably (SiO2+Li2O) / ZrO2 is 10.0 to 37.0, even more 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 values ​​of (SiO2+Li2O) / ZrO2 are 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, 2 Possible values ​​include 6.0, 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, and 55.0.

[0031] Alkaline earth metal oxides (MO, where MO is 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 microcrystalline glass and microcrystalline glass products. However, if the MO content exceeds 5%, the dielectric constant and dielectric loss of the glass increase, and the Young's modulus and steel ball drop test height of the glass decrease. Therefore, the MO content in this invention is limited to 0-5%, preferably 0-3%, more preferably 0-1%, and even more preferably MO-free. In some embodiments, approximately 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% It can contain MO in the following percentages: 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%.

[0032] In some embodiments, when MO / ZrO2 is greater than 2.5, the dielectric loss of the glass increases, the hardness, Young's modulus, and steel ball drop test height of the glass decrease, and the transmittance of the blackened portion of the microcrystalline glass and microcrystalline glass products increases. Therefore, it is preferable that MO / ZrO2 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 may be 0, greater than 0, 0.01, 0.05, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.1, 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, and 2.5.

[0033] CeO2 is a photosensitizer that provides electrons to components such as Ag, Sb, and Sn. If the CeO2 content is less than 0.01%, it cannot provide enough electrons, the crystal content of the microcrystalline glass is too low, the transmittance of the blackened portion of the microcrystalline glass and microcrystalline glass product decreases, and the Young's modulus of the microcrystalline glass and microcrystalline glass product decreases. If the CeO2 content exceeds 0.6%, the transmittance of the transparent portion of the microcrystalline glass and microcrystalline glass product decreases, the transmission depth in the ultraviolet band of the microcrystalline glass and microcrystalline glass product decreases, the crystal content inside the blackened portion of the microcrystalline glass and microcrystalline glass product decreases, and the transmittance increases. Therefore, the CeO2 content is preferably 0.01 to 0.6%, more preferably 0.07 to 0.4%, and more preferably 0.08 to 0.3%. In some embodiments, 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%, 0.3%, It can contain CeO2 at the following percentages: 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%.

[0034] Ag2O, as a nucleating agent for microcrystalline glass and microcrystalline glass products of the present invention, plays a role in improving the blackening effect in microcrystalline glass and microcrystalline glass products. If the Ag2O content is less than 0.01%, the transmittance of the blackened portion of the microcrystalline glass and microcrystalline glass products increases, blackening may not occur, the height of the steel ball drop test for the microcrystalline glass and microcrystalline glass products decreases, the coefficient of thermal expansion increases, and the pattern accuracy decreases. If the Ag2O content exceeds 0.8%, the transmittance of the transparent portion during glass molding or heat treatment decreases, and because the nucleating agent content is too high, the number of crystals in the microcrystalline glass and microcrystalline glass products increases, the crystal grain size becomes too small, the scattering effect of the crystals in the blackened portion with respect to visible light weakens, the transmittance of the blackened portion tends to increase, and the glass tends to crystallize during molding. Therefore, the Ag2O content is limited to 0.01 to 0.8%, preferably 0.1 to 0.6%, and more preferably 0.2 to 0.5%. In some embodiments, 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%, 0.3%, 0.31%, 0.32%, 0.33%, 0.34%, 0.35%, 0.36%, 0.37%, 0.38%, 0.39%, 0.4%, It can contain Ag2O in the following amounts: 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%, 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%.

[0035] As a result of extensive research by the inventors, they found that in some embodiments, by controlling the ratio of Ag2O content to CeO2 content, Ag2O / CeO2, within the range of 1.0 to 10.0, the crystal grain size in the blackened portion of the microcrystalline glass and microcrystalline glass product is relatively large, the crystal content is higher, the light scattering effect in the visible light band is stronger, the transmittance of the blackened portion is relatively low, and the hardness and steel ball drop test height of the microcrystalline glass and microcrystalline glass product are increased. Therefore, preferably, Ag2O / CeO2 is 1.0 to 10.0, more preferably Ag2O / CeO2 is 1.5 to 6.5, and even more preferably Ag2O / CeO2 is 2.0 to 4.5. In some embodiments, the Ag2O / CeO2 value 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.

[0036] In some embodiments, by controlling the ratio of ZrO2 content to the total content of Ag2O and CeO2, ZrO2 / (Ag2O+CeO2), within the range of 2.3 to 50.0, the thermal expansion coefficient of the glass can be optimized, improving the accuracy of pattern formation in the microcrystalline glass after mask exposure and heat treatment of the glass. Furthermore, the transmittance of the transparent parts of the microcrystalline glass and microcrystalline glass products can be relatively high, the transmittance of the blackened parts can be relatively low, and the hardness and drop height of the glass and microcrystalline glass products can be increased. Therefore, preferably, ZrO2 / (Ag2O+CeO2) is 2.3 to 50.0, more preferably ZrO2 / (Ag2O+CeO2) is 6.5 to 35.0, even more preferably ZrO2 / (Ag2O+CeO2) is 8.5 to 20.0, and even more preferably ZrO2 / (Ag2O+CeO2) is 11.0 to 18.0. In some embodiments, the value of ZrO2 / (Ag2O+CeO2) is 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, 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 are possible.

[0037] Sb2O3 and SnO2 undergo ultraviolet exposure, Ce 3+ It absorbs electrons emitted from the source and stores electrons, and in subsequent heat treatment, it plays a role in the Ag +By providing electrons, Ag colloid particles are formed to nucleate, promoting the blackening of microcrystalline glass. When the Sb2O3+SnO2 content is less than 0.05%, it is difficult to achieve the blackening effect on microcrystalline glass or microcrystalline glass products. When the Sb2O3+SnO2 content exceeds 1.2%, the transmittance of the blackened portion of the microcrystalline glass or microcrystalline glass product tends to increase. Therefore, the Sb2O3+SnO2 content is 0.05 to 1.2%, preferably 0.1 to 1%, and more preferably 0.2 to 0.7%. In some embodiments, the Sb2O3+SnO2 content 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%.

[0038] SnO2 is highly effective in promoting the blackening of microcrystalline glass, but in some embodiments, if the SnO2 content exceeds 0.5%, the transmittance of the transparent portion of the glass may decrease and even devitrify during molding 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 values ​​are 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. It can contain SnO2 in the following proportions: 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 embodiments, 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%, 0.29% It can contain Sb2O3 in the following proportions: 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%.

[0039] As a result of extensive experimental research conducted by the inventors, in some embodiments, it was found that by controlling the ratio of the total content of Sb2O3 and SnO2 (Sb2O3+SnO2) to the content of Ag2O ((Sb2O3+SnO2) / Ag2O) within the range of 0.1 to 5.0, the dielectric loss of the glass can be reduced, the height of the ball drop experiment for the glass and microcrystalline glass products can be increased, and the transmittance of the transparent portion of the microcrystalline glass and microcrystalline glass products is relatively high, while the transmittance of the blackened portion is relatively low. Therefore, preferably (Sb2O3+SnO2) / Ag2O is 0.1 to 5.0, more preferably (Sb2O3+SnO2) / Ag2O is 0.5 to 3.5, and even more preferably (Sb2O3+SnO2) / Ag2O is 1.0 to 2.6. In some embodiments, 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.

[0040] In some embodiments, by controlling the ratio of 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, the transmittance of the blackened portion of microcrystalline glass and microcrystalline glass products can be relatively low, reducing the dielectric constant of the glass while simultaneously increasing its hardness and Young's modulus. Therefore, preferably (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 embodiments, the value of (Ag2O+SnO2+Sb2O3) / CeO2 is 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, Possible values ​​include 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, and 30.0.

[0041] In some embodiments, by controlling the ratio of the total content of Sb2O3, SnO2, and CeO2 (Sb2O3+SnO2+CeO2) to the content of Ag2O ((Sb2O3+SnO2+CeO2) / Ag2O) within the range of 0.1 to 10.0, the dielectric loss and thermal expansion coefficient of the glass can be reduced, resulting in relatively low transmittance in the blackened portions of microcrystalline glass and microcrystalline glass products. Therefore, preferably (Sb2O3+SnO2+CeO2) / Ag2O is 0.1 to 10.0, more preferably (Sb2O3+SnO2+CeO2) / Ag2O is 0.4 to 5.0, even 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. In some embodiments, the values ​​of (Sb2O3+SnO2+CeO2) / Ag2O are 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, Possible values ​​include 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, and 10.0.

[0042] In some embodiments, when the value of SnO2 / (CeO2+SnO2) is greater than 0.9, the transmittance of the transparent portion of the glass may decrease rapidly and even completely devitrify during glass molding 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 embodiments, 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.

[0043] Ln2O3 (Ln2O3 is one or more of La2O3, Gd2O3, and Y2O3) adjusts the relative permittivity and dielectric loss of glass, Ag + It can provide electrons and promote the blackening of microcrystalline glass. When Ln2O3 exceeds 5%, the transmittance of the blackened portion of the microcrystalline glass and microcrystalline glass product increases, and the relative permittivity 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, even more preferably no Ln2O3. In some embodiments, it is about 0%, greater than 0%, 0.01%, 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2%, 2.1%, 2.2%, 2.3%, It can contain Ln2O3 in the following amounts: 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%.

[0044] Fe2O3 absorbs ultraviolet light when glass is exposed to ultraviolet light, Ag + It can provide electrons and promote the blackening of microcrystalline glass. When the Fe2O3 content exceeds 1%, the transmittance in the visible light band range of the transparent portion of the microcrystalline glass and microcrystalline glass product decreases, the transmittance of the blackened portion increases, and the height of the steel ball drop test of the microcrystalline glass and microcrystalline glass product decreases. Therefore, the Fe2O3 content is limited to 0-1%, preferably 0-0.5%, more preferably 0-0.2%, and in some embodiments, even more preferably, it is Fe2O3-free. In some embodiments, 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%, 0.29% It can contain Fe2O3 in the following proportions: 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%.

[0045] The terms “not containing” and “0%” as used herein mean that compounds, molecules, or elements, etc., were not intentionally added as raw materials for the matrix glass, microcrystalline glass, or microcrystalline glass product of the present invention. However, impurities or components that were not intentionally added as raw materials and / or equipment for manufacturing the matrix glass, microcrystalline glass, or microcrystalline glass product may be present in small or trace amounts in the final matrix glass, microcrystalline glass, or microcrystalline glass product, and these are also covered by the patent of the present invention.

[0046] The performance indicators of the microcrystalline glass and / or microcrystalline glass products and / or matrix glass of the present invention are tested according to the following method.

[0047] <Light transmittance> Light transmittance is tested according to the following method: the sample is processed to a certain thickness, the opposing surfaces are polished in parallel, and then tested according to the national standard 'GB / T 7962.12-2010'.

[0048] <Coefficient of linear expansion> Coefficient of linear expansion (α 20℃-300℃ The values ​​shown are from tests conducted at 20°C-300°C in accordance with the national standard 'GB / T 7962.16-2010'. In this invention, the coefficient of linear expansion may be abbreviated as the expansion coefficient.

[0049] <Relative permittivity> Relative permittivity (ε r The data shown is based on tests conducted under 1 GHz conditions in accordance with the national standard GB / T 7265.1-1987.

[0050] <Dielectric Loss> The dielectric loss (tanδ) is data obtained from tests conducted under 1 GHz conditions in accordance with the national standard 'GB / T 7265.1-1987'.

[0051] <Height of ball drop test> A φ20×1mm sample is placed on a stage, and a 32g steel ball is dropped from a predetermined height. The maximum steel ball drop height at which the sample can withstand the impact without breaking is defined as the steel ball drop test height. Specifically, the test is conducted starting from a drop height of 100mm, and if no breakage occurs, the height is changed in the following order: 100mm, 200mm, 300mm, 400mm, 500mm, 600mm, 700mm, 800mm, 900mm, 100mm, 1000mm, 1100mm, and 1200mm or higher. In the specific examples of "Steel Ball Drop Test Height II," a microcrystalline glass product is used as the test subject. In the examples, the test data recorded as 1000mm indicates that the microcrystalline glass product could withstand the impact without breaking even when a steel ball was dropped from a height of 1000mm. In some examples of "Steel Ball Drop Test Height I," matrix glass is used as the test subject. The drop test height of the present invention may be abbreviated as "drop height."

[0052] <Knoop hardness> The load (N) applied when a pyramidal indentation was pressed into a test surface using a diamond square pyramidal indenter with an angle of 172.5° between the relative surfaces was calculated using the length of the indentation and the resulting surface area (mm²). 2 It is expressed as the value obtained by dividing by ). The test is performed with a test load of 100 (N) and a holding time of 15 (seconds). In this invention, Knoop hardness may be abbreviated as hardness.

[0053] Young's modulus Young's modulus (E) is calculated by measuring longitudinal and transverse wave velocities using ultrasound and following the formula below.

number

[0054] <Refractive index> Refractive index (n d) shall be tested according to the method specified in GB / T 7962.1-2010.

[0055] The matrix glass of the present invention has the following properties: 1) In some embodiments, the refractive index (n) of the matrix glass of the present invention d The ratio 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. 2) In some embodiments, the Young's modulus (E) of the matrix glass of the present invention is 7000 × 10 7 Pa~9500×10 7 Pa, preferably 7500 × 10 7 Pa~9200×10 7 Pa, uh, 7836 × 10 7 Pa~9014×10 7 Pa, more preferably 8005 × 10 7 Pa~8488×10 7 It is Pa. 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 is preferably 470-600 kgf / mm². 2 , more preferably 480-582 kgf / mm² 2 More preferably 492-532 kgf / mm² 2 That is the case. 4) In some embodiments, the steel ball drop 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. 5) In some embodiments, the dielectric loss (tanδ) of the matrix glass of the present invention is 11.0 × 10⁻¹⁰ -3 The following is preferably 7.0 × 10 -3 ~10.5×10 -3 , more preferably 7.2 × 10 -3 ~9.8×10 -3 More preferably 7.4 × 10 -3 ~9.2×10 -3 That is the case. 6) In some embodiments, the relative permittivity (ε r ) of the matrix glass of the present invention 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. 7) In some embodiments, the linear expansion coefficient (α 20℃-300℃ ) of the matrix glass of the present invention is 100×10 -7 / °C or less, preferably 65×10 -7 / °C to 100×10 -7 / °C, more preferably 71×10 -7 / °C to 95×10 -7 / °C, and even more preferably 75×10 -7 / °C to 90×10 -7 / °C.

[0056] The microcrystalline glass of the present invention has the following properties: 1) In some embodiments, the average transmittance (T 400-800nm ) in the 400 - 800 nm band range of the transparent part of the microcrystalline glass with a thickness of 0.2 - 1.5 mm 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 - 95.0%. The above 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, 1.2 mm. 2) In some embodiments, the average transmittance (T 400-800nm ) in the 400 - 800 nm band range of the blackened part of the microcrystalline glass with a thickness of 0.2 - 1.5 mm 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 above 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, 1.2 mm. 3) In some embodiments, the transmittance (T 870nmThe content of the material is 15.0% or less, preferably 0.1 to 12.5%, more preferably 0.1 to 10%, even more preferably 0.1 to 8.0%, and even more preferably 0.1 to 5.0%. 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, and 1.2 mm. 4) In some embodiments, the transmittance (T) in the 940nm band of the blackened portion of a microcrystalline glass with a thickness of 0.2 to 1.5 mm is 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%. 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, and 1.2 mm.

[0057] In some embodiments, the transparent portion of the microcrystalline glass of the present invention is not crystallized, and therefore, the Young's modulus (E) and Knoop hardness (Hk 0.1 ), steel ball drop test height, dielectric loss (tanδ), relative permittivity (ε r ), coefficient of linear expansion (α 20℃-300℃ ) and other properties similar to those of the matrix glass described above. Specifically, in some embodiments, the Young's modulus (E) of the transparent portion of the microcrystalline glass of the present invention is 7000 × 10 7 Pa~9500×10 7 Pa, preferably 7500 × 10 7 Pa~9200×10 7 Pa, uh, 7836 × 10 7 Pa~9014×10 7 Pa, more preferably 8005 × 10 7 Pa~8488×10 7 In some embodiments, the Knoop hardness (Hk) of the transparent portion of the microcrystalline glass of the present invention is Pa. 0.1 ) is 450 kgf / mm 2 The above is preferably 470-600 kgf / mm². 2 , more preferably 480-582 kgf / mm²2 More preferably 492-532 kgf / mm² 2 In some embodiments, the height of the steel ball drop test on 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 × 10⁻¹⁰. -3 The following is preferably 7.0 × 10 -3 ~10.5×10 -3 , more preferably 7.2 × 10 -3 ~9.8×10 -3 More preferably 7.4 × 10 -3 ~9.2×10 -3 In some embodiments, the relative permittivity (ε) of the transparent portion of the microcrystalline glass of the present invention is r The coefficient of linear expansion (α) of the transparent portion of the microcrystalline glass of the present invention 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. In some embodiments, the coefficient of linear expansion (α) of the transparent portion of the microcrystalline glass of the present invention 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. 20℃-300℃ ) is 100 x 10 -7 / ℃ or lower, preferably 65 × 10 -7 / ℃~100×10 -7 / ℃, more 71×10 -7 / ℃~95×10 -7 / ℃, more preferably 75 × 10 -7 / ℃~90×10 -7 It is / ℃.

[0058] The microcrystalline glass product of the present invention has the following properties: 1) In some embodiments, the average transmittance (T) in the 400-800 nm band range of the transparent portion of a microcrystalline glass product with a thickness of 0.2-1.5 mm is determined. 400-800nm The content 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, and 1.2 mm. 2) In some embodiments, the average transmittance (T) in the 400-800 nm band range of the transparent portion of a microcrystalline glass product with a thickness of 0.2-1.5 mm is determined. 400-800nm The content of the material 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, and 1.2 mm. 3) In some embodiments, the transmittance (T) in the 870nm band of the blackened portion of a microcrystalline glass product with a thickness of 0.2 to 1.5 mm is measured. 870nm The content of the material is 15.0% or less, preferably 0.1 to 12.5%, more preferably 0.1 to 10%, even more preferably 0.1 to 8.0%, and even more preferably 0.1 to 5.0%. 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, and 1.2 mm. 4) In some embodiments, the transmittance (T) in the 940nm band of the blackened portion of a microcrystalline glass product with a thickness of 0.2 to 1.5 mm is measured. 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%. 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, and 1.2 mm. 5) In some embodiments, the ball drop 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.

[0059] In some embodiments, the relative permittivity and dielectric loss of the matrix glass / microcrystalline glass products of the present invention are relatively low, which can reduce the transmission loss of electrical signals.

[0060] In some embodiments, the Knoop hardness, Young's modulus, and steel ball drop height of the matrix glass / microcrystalline glass / microcrystalline glass product of the present invention are relatively high.

[0061] In some embodiments, the coefficient of thermal expansion of the matrix glass / microcrystalline glass / microcrystalline glass product of the present invention is relatively low, which can improve the accuracy of the optical signal channel and mask pattern.

[0062] In some embodiments, the refractive index of the matrix glass / microcrystalline glass / microcrystalline glass product of the present invention is relatively low, which can reduce the reflectivity of the surface light signal and increase the incidence rate of the light signal.

[0063] Because the microcrystalline glass, microcrystalline glass products, and matrix glass of the present invention possess the above-mentioned excellent performance, they can be used to manufacture cover glass or glass components. Furthermore, the microcrystalline glass, microcrystalline glass products, matrix glass, and cover glass or glass components manufactured using them can be used in the manufacture of various instruments and devices, including but not limited to electronic devices such as mobile phones, watches, computers, and biomedical equipment, medical devices, ornaments, or crafts. In addition, they can be used in local light shielding glass or patterned cover glass for mobile phones, smartphones, tablets, laptops, and televisions, or in optical signal channel glass for smartwatches and biomedical devices, or in patterned ornament or craft glass.

[0064] The matrix glass, microcrystalline glass, and microcrystalline glass products of the present invention can be produced and manufactured by the following methods.

[0065] The method for manufacturing matrix glass includes the following steps: weighing the raw materials according to their component ratios and mixing them uniformly; placing the mixed raw materials in a platinum or quartz crucible; melting them at 1450-1600°C; clarifying and homogenizing them; then lowering the temperature; pouring the molten glass into a mold and shaping it; passing circulating cooling air through the mold to prevent crystallization of the glass; preferably preheating the mold to 200-500°C; placing the shaped glass together with the mold in an annealing furnace and annealing it at a controlled temperature; then turning off the power and cooling the annealing furnace together with the glass to obtain matrix glass.

[0066] The method for manufacturing microcrystalline glass includes the following steps: forming a matrix glass, performing a crystallization process on the matrix glass, or processing the matrix glass into a glass element of a specific shape and then performing a crystallization process to obtain the microcrystalline glass of the present invention. The method for processing the glass into a glass element of a specific shape in the present invention includes methods known to those skilled in the art, such as hot pressing, grinding, or polishing. The crystallization process in the present invention includes the following: performing a mask exposure treatment on the matrix glass, followed by a crystallization heat treatment to uniformly precipitate crystals at the glass exposure location. The mask exposure treatment described in the present invention involves ultraviolet exposure at a specific location or region of the matrix glass, the wavelength of the ultraviolet light is preferably 313 nm, a dedicated photomask pattern can be customized as needed, and the exposure time is preferably 5 to 60 minutes. The crystallization heat treatment in the present invention can be performed in one or two steps, preferably employing two steps. The aforementioned two-stage crystallization heat treatment involves performing a nucleation process at a first temperature, followed by a crystal growth process at a second temperature higher than the nucleation process temperature, wherein the first temperature is preferably 490°C to 520°C, the treatment time at the first temperature is preferably 1 to 4 hours, the second temperature is preferably 540°C to 620°C, and the treatment time at the second temperature is preferably 1 to 8 hours.

[0067] The method for manufacturing a microcrystalline glass product includes the following steps: performing a chemical strengthening process on the microcrystalline glass of the present invention, or processing the microcrystalline glass into a microcrystalline glass element of a specific shape and then performing a chemical strengthening process to obtain the microcrystalline glass product of the present invention. The method for processing the product of the present invention into a specific shape includes methods known to those skilled in the art, such as hot pressing, grinding, or polishing.

[0068] The chemical strengthening described in this invention is, in other words, an ion exchange method. During ion exchange, small metal ions in the microcrystalline glass are replaced or "exchanged" with larger metal ions of the same valence located near the microcrystalline glass. By replacing small ions with larger ions, compressive stress is constructed within the microcrystalline glass, forming a compressive stress layer.

[0069] In some embodiments, the metal ion is a monovalent alkali metal ion (e.g., Na). + , K + , Rb + , Cs + (etc.) Ion exchange is performed by immersing the microcrystalline glass in a salt bath of at least one molten salt containing large metal ions, and these large metal ions are used to replace the small metal ions in the microcrystalline glass. Or, Ag + , Tl + Cu + Monovalent ions can also be exchanged using other monovalent metal ions such as . One or more ion exchange processes used for chemical strengthening microcrystalline glass include, but are not limited to, immersion in a single salt bath or immersion in multiple salt baths having the same or different compositions, with washing and / or tempering steps added between immersions.

[0070] In some embodiments, ion exchange can be performed by immersing the microcrystalline glass in a salt bath of molten sodium salt (such as NaNO3) and / or potassium salt (such as KNO3) and / or a mixed sodium and potassium salt at approximately 350°C to 470°C for 1 to 36 hours. The temperature range is preferably 380°C to 460°C, and the time range is preferably 2 to 24 hours.

[0071] In some embodiments, the matrix glass of the present invention can be used to produce tempered glass by the above chemical strengthening process, and a microcrystalline glass product can be obtained by the above crystallization process. In some embodiments, the matrix glass of the present invention can be processed into a glass element, and the glass element can be used to produce tempered glass by the above chemical strengthening process, and a microcrystalline glass product can be obtained by the above crystallization process.

[0072] Examples To further clarify the technical solutions of the present invention, the following non-limiting embodiments are provided. While every effort has been made to ensure the accuracy of the numerical values ​​(e.g., quantities) in the embodiments of the present invention, it should be noted that there are some errors and deviations. The composition itself is assigned in weight percent based on oxides and standardized to 100%.

[0073] <Examples of matrix glass> In this embodiment, matrix glass having the compositions shown in Tables 1 to 4 is obtained using the above-described method for manufacturing matrix glass. Furthermore, the properties of the matrix glass are measured using the test method described in the present invention, and the measurement results are shown in Tables 1 to 4.

[0074] [Table 1]

[0075] [Table 2]

[0076] [Table 3]

[0077] [Table 4]

[0078] <Examples of microcrystalline glass> In this embodiment, microcrystalline glass having the compositions shown in Tables 5 to 8 is obtained using the above-described method for manufacturing microcrystalline glass. Furthermore, the properties of each microcrystalline glass are measured according to the test method of the present invention, and the measurement results are shown in Tables 5 to 8. The transmittance of the microcrystalline glass in the following embodiments is measured using a sample with a thickness of 1 mm.

[0079] [Table 5]

[0080] [Table 6]

[0081] [Table 7]

[0082] [Table 8]

[0083] <Examples of microcrystalline glass products> In this embodiment, microcrystalline glass products having the compositions shown in Tables 9 to 12 are obtained using the above-described method for manufacturing microcrystalline glass products. Furthermore, the properties of each microcrystalline glass product are measured according to the test method of the present invention, and the measurement results are shown in Tables 9 to 12. The transmittance of the microcrystalline glass products in the following embodiments is measured using a sample with a thickness of 1 mm.

[0084] [Table 9]

[0085] [Table 10]

[0086] Table 11

[0087] Table 12

Claims

1. A microcrystalline glass product containing the following components in weight %: SiO 2 : 65 to 78%; R 2 O: 2 to 12%; Li 2 O: 5 to 15%; Al 2 O 3 : 3 to 12%; ZrO 2 : 1.5 to 10%; CeO 2 : 0.01 to 0.6%; Ag 2 O: 0.01 to 0.8%, wherein the R 2 O is Na 2 O, K 2 O, or one or both of them.

2. The microcrystalline glass product according to claim 1, comprising the following components by weight: Sb 2 O 3 : 0-1%, and / or SnO 2 : 0–0.5%, and / or MO: 0–5%, and / or Ln 2 O 3 : 0-5%, and / or Fe 2 O 3 : 0-1%, the above MO is one or more of MgO, CaO, SrO, BaO, and ZnO, Ln 2 O 3 La 2 O 3 , Gd 2 O 3 , Y 2 O 3 It is one or more species of [something].

3. Microcrystalline glass products containing the following components by weight: SiO 2 : 65-78%; R 2 O: 2-12%; Li 2 O: 5-15%; Al 2 O 3 : 3-12%; ZrO 2 : 1.5–10%; CeO 2 : 0.01–0.6%; Ag 2 O: 0.01–0.8%; Sb 2 O 3 : 0-1%; SnO 2 :0~0.5%;MO:0~5%;Ln 2 O 3 : 0-5%; Fe 2 O 3 : Consists of 0-1%, and the R 2 O is Na 2 OK 2 O is one or both types, MO is one or more types of MgO, CaO, SrO, BaO, ZnO, Ln 2 O 3 La 2 O 3 , Gd 2 O 3 , Y 2 O 3 It is one or more species of [something].

4. A microcrystalline glass product according to any one of claims 1 to 3, wherein the composition is expressed in weight percent and satisfies one or more of the following 14 conditions. 1) SiO 2 / Li 2 O content is 5.5 to 10.0, preferably SiO 2 / Li 2 O content is 6.0 to 9.0, more preferably SiO 2 / Li 2 O is between 7.0 and 8.

5. 2) (Sb 2 O 3 +SnO 2 ) / Ag 2 O is 0.1 to 5.0, preferably (Sb 2 O 3 +SnO 2 ) / Ag 2 O is 0.5 to 3.5, more preferably (Sb 2 O 3 +SnO 2 ) / Ag 2 O is between 1.0 and 2.

6. 3) (K 2 O+Na 2 O) / ZrO 2 is 0.5 to 7.1, preferably (K 2 O+Na 2 O) / ZrO 2 is 0.7 to 4.5, more preferably (K 2 O+Na 2 O) / ZrO 2 The range is 0.8 to 2.

5. 4) Ag 2 O / CeO 2 The value is 1.0 to 10.0, preferably Ag 2 O / CeO 2 1.5 to 6.5, more preferably Ag 2 O / CeO 2 The range is 2.0 to 4.

5. 5) Li 2 O / ZrO 2 is 1.0 to 7.5, preferably Li 2 O / ZrO 2 is 1.2 to 5.0, more preferably Li 2 O / ZrO 2 is 1.4 to 4.3, even more preferably Li 2 O / ZrO 2 is 1.6 to 3.

0. 6) (SiO 2 + Li 2 O) / ZrO 2 is 8.0 to 55.0, preferably (SiO 2 + Li 2 O) / ZrO 2 is 10.0 to 37.0, more preferably (SiO 2 + Li 2 O) / ZrO 2 is 12.0 to 25.0, still more preferably (SiO 2 + Li 2 O) / ZrO 2 is 13.0 to 20.

0. 7) ZrO 2 / (Ag 2 O+CeO 2 ) is 2.3 to 50.0, preferably ZrO 2 / (Ag 2 O+CeO 2 ) is 6.5 to 35.0, more preferably ZrO 2 / (Ag 2 O+CeO 2 ) is 8.5 to 20.0, more preferably ZrO 2 / (Ag 2 O+CeO 2 The range is 11.0 to 18.

0. 8) (Ag 2 O+SnO 2 +Sb 2 O 3 ) / CeO 2 The amount is 1.0 to 30.0, preferably (Ag 2 O+SnO 2 +Sb 2 O 3 ) / CeO 2 is 3.0 to 20.0, more preferably (Ag 2 O+SnO 2 +Sb 2 O 3 ) / CeO 2 is 5.0 to 12.5, more preferably (Ag 2 O+SnO 2 +Sb 2 O 3 ) / CeO 2 The range is 7.5 to 10.

0. 9) (Sb 2 O 3 +SnO 2 +CeO 2 ) / Ag 2 O is 0.1 to 10.0, preferably (Sb 2 O 3 +SnO 2 +CeO 2 ) / Ag 2 O is 0.4 to 5.0, more preferably (Sb 2 O 3 +SnO 2 +CeO 2 ) / Ag 2 O is 0.7 to 3.7, more preferably (Sb 2 O 3 +SnO 2 +CeO 2 ) / Ag 2 O is between 1.5 and 3.

2. 10) SnO 2 / (CeO 2 +SnO 2 ) is 0 to 0.9, preferably SnO 2 / (CeO 2 +SnO 2 ) is 0 to 0.6, more preferably SnO 2 / (CeO 2 +SnO 2 The value is between 0 and 0.

5. 11) R 2 O+Li 2 O+Al 2 O 3 15-30%, preferably R 2 O+Li 2 O+Al 2 O 3 17.5-29.5%, more preferably R 2 O+Li 2 O+Al 2 O 3 18.5-26%, more preferably R 2 O+Li 2 O+Al 2 O 3 The percentage is 20-25%. 12) (SiO 2 +Al 2 O 3 ) / (Li 2 O+Na 2 O+K 2 O) is 3.0 to 7.5, preferably (SiO 2 +Al 2 O 3 ) / (Li 2 O+Na 2 O+K 2 O) is 3.7 to 6.5, more preferably (SiO 2 +Al 2 O 3 ) / (Li 2 O+Na 2 O+K 2 O) is 4.3 to 6.0, more preferably (SiO 2 +Al 2 O 3 ) / (Li 2 O+Na 2 O+K 2 O) is between 4.8 and 5.

8. 13) MO / ZrO 2 The ratio is 2.5 or less, preferably MO / ZrO 2 is 1.5 or less, more preferably MO / ZrO 2 It is 0.5 or less. 14) Sb 2 O 3 +SnO 2 : 0.05 to 1.2%, preferably Sb 2 O 3 +SnO 2 : 0.1–1%, more preferably Sb 2 O 3 +SnO 2 : 0.2-0.7%, the above R 2 O is Na 2 OK 2 O is one or both types, and MO is one or more types of MgO, CaO, SrO, BaO, or ZnO.

5. A microcrystalline glass product according to any one of claims 1 to 3, comprising the following components by weight: SiO 2 : 68-77%, preferably SiO 2 : 69.5–75.5%, and / or R 2 O: 3-10%, preferably R 2 O: 4-8%, and / or Li 2 O: 7-13%, preferably Li 2 O: 8.5–12%, and / or Al 2 O 3 : 4-10%, preferably Al 2 O 3 : 5-9%, and / or ZrO 2 : 2-8%, preferably ZrO 2 : 3–6.5%, and / or CeO 2 : 0.07-0.4%, preferably CeO 2 : 0.08–0.3%, and / or Ag 2 O: 0.1-0.6%, preferably Ag 2 O: 0.2–0.5%, and / or Sb 2 O 3 : 0.01 to 0.7%, preferably Sb 2 O 3 : 0.07–0.5%, and / or SnO 2 : 0-0.3%, preferably SnO 2 : 0-0.2%, and / or MO: 0-3%, preferably MO: 0-1%, more preferably no MO, and / or Ln 2 O 3 : 0-3%, preferably Ln 2 O 3 : 0-1%, more preferably Ln 2 O 3 It does not contain and / or Fe 2 O 3 : 0-0.5%, preferably Fe 2 O 3 : 0-0.2%, more preferably Fe 2 O 3 It does not include the above R 2 O is Na 2 OK 2 O is one or both types, MO is one or more types of MgO, CaO, SrO, BaO, ZnO, Ln 2 O 3 La 2 O 3 , Gd 2 O 3 , Y 2 O 3 It is one or more species of [something].

6. The microcrystalline glass product according to any one of claims 1 to 3, wherein the microcrystalline glass product includes one or more blackened portions and one or more transparent portions, or the entire microcrystalline glass product is a blackened portion.

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

8. Average transmittance T in the 400-800nm ​​band range of the transparent portion of a microcrystalline glass product with a thickness of 0.2-1.5mm 400-800nm The average transmittance T in the 400-800 nm band range of the blackened portion of a microcrystalline glass product with a thickness of 0.2-1.5 mm 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 91.5-95.0%, and / or 85.0% or more, preferably 88.0% or more, more preferably 90.0% or more, even more preferably 91.0% or more, and / or 91.5-95.0% and / or 85.0% or more, and / or 91.5-95.0%. 400-800nm The transmittance T in the 870nm band of the blackened portion of a microcrystalline glass product with a thickness of 0.2 to 1.5 mm is 5.0% or less, preferably 3.0% or less, more preferably 1.5% or less, even more preferably 1.2% or less, and / or even more preferably 0.5% or less. 870nm The transmittance T in the 940nm band of the blackened portion of a microcrystalline glass product with a thickness of 0.2 to 1.5 mm is 15.0% or less, preferably 0.1 to 12.5%, more preferably 0.1 to 10%, even more preferably 0.1 to 8.0%, and / or even more preferably 0.1 to 5.0%. 940nm The microcrystalline glass product according to claim 6, wherein 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 product according to claim 8, wherein the thickness of the microcrystalline glass product is 0.5 to 1.5 mm, preferably 0.8 to 1.2 mm, 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 product according to any one of claims 1 to 3, wherein the height II of the ball drop test 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. Microcrystalline glass containing the following components by weight: SiO 2 : 65-78%; R 2 O: 2-12%; Li 2 O: 5-15%; Al 2 O 3 : 3-12%; ZrO 2 : 1.5–10%; CeO 2 : 0.01–0.6%; Ag 2 O: 0.01-0.8%, the above R 2 O is Na 2 OK 2 It is one or both types of O.

12. The microcrystalline glass according to claim 11, further comprising the following components by weight: Sb 2 O 3 : 0-1%, and / or SnO 2 : 0–0.5%, and / or MO: 0–5%, and / or Ln 2 O 3 : 0-5%, and / or Fe 2 O 3 : 0-1%, the above MO is one or more of MgO, CaO, SrO, BaO, and ZnO, Ln 2 O 3 La 2 O 3 , Gd 2 O 3 , Y 2 O 3 It is one or more species of [something].

13. Microcrystalline glass containing the following components by weight: SiO 2 : 65-78%; R 2 O: 2-12%; Li 2 O: 5-15%; Al 2 O 3 : 3-12%; ZrO 2 : 1.5–10%; CeO 2 : 0.01–0.6%; Ag 2 O: 0.01–0.8%; Sb 2 O 3 : 0-1%; SnO 2 :0~0.5%;MO:0~5%;Ln 2 O 3 : 0-5%; Fe 2 O 3 : Consists of 0-1%, and the R 2 O is Na 2 OK 2 O is one or both types, MO is one or more types of MgO, CaO, SrO, BaO, ZnO, Ln 2 O 3 La 2 O 3 , Gd 2 O 3 , Y 2 O 3 It is one or more species of [something].

14. A microcrystalline glass according to any one of claims 11 to 13, wherein the composition is expressed in weight percent and satisfies one or more of the following 14 conditions. 1) SiO 2 / Li 2 O content is 5.5 to 10.0, preferably SiO 2 / Li 2 O content is 6.0 to 9.0, more preferably SiO 2 / Li 2 O is between 7.0 and 8.

5. 2) (Sb 2 O 3 +SnO 2 ) / Ag 2 O is 0.1 to 5.0, preferably (Sb 2 O 3 +SnO 2 ) / Ag 2 O is 0.5 to 3.5, more preferably (Sb 2 O 3 +SnO 2 ) / Ag 2 O is between 1.0 and 2.

6. 3) (K 2 O+Na 2 O) / ZrO 2 is 0.5 to 7.1, preferably (K 2 O+Na 2 O) / ZrO 2 is 0.7 to 4.5, more preferably (K 2 O+Na 2 O) / ZrO 2 The range is 0.8 to 2.

5. 4) Ag 2 O / CeO 2 The value is 1.0 to 10.0, preferably Ag 2 O / CeO 2 1.5 to 6.5, more preferably Ag 2 O / CeO 2 The range is 2.0 to 4.

5. 5) Li 2 O / ZrO 2 The value is 1.0 to 7.5, preferably Li 2 O / ZrO 2 The range is 1.2 to 5.0, more preferably Li 2 O / ZrO 2 The ratio is 1.4 to 4.3, more preferably Li 2 O / ZrO 2 The range is 1.6 to 3.

0. 6) (SiO 2 +Li 2 O) / ZrO 2 The ratio is 8.0 to 55.0, preferably (SiO₂ 2 +Li 2 O) / ZrO 2 is 10.0 to 37.0, more preferably (SiO 2 +Li 2 O) / ZrO 2 The ratio is 12.0 to 25.0, more preferably (SiO 2 +Li 2 O) / ZrO 2 The range is 13.0 to 20.

0. 7) ZrO 2 / (Ag 2 O+CeO 2 ) is 2.3 to 50.0, preferably ZrO 2 / (Ag 2 O+CeO 2 ) is 6.5 to 35.0, more preferably ZrO 2 / (Ag 2 O+CeO 2 ) is 8.5 to 20.0, more preferably ZrO 2 / (Ag 2 O+CeO 2 The range is 11.0 to 18.

0. 8) (Ag 2 O+SnO 2 +Sb 2 O 3 ) / CeO 2 The amount is 1.0 to 30.0, preferably (Ag 2 O+SnO 2 +Sb 2 O 3 ) / CeO 2 is 3.0 to 20.0, more preferably (Ag 2 O+SnO 2 +Sb 2 O 3 ) / CeO 2 is 5.0 to 12.5, more preferably (Ag 2 O+SnO 2 +Sb 2 O 3 ) / CeO 2 The range is 7.5 to 10.

0. 9) (Sb 2 O 3 +SnO 2 +CeO 2 ) / Ag 2 O is 0.1 to 10.0, preferably (Sb 2 O 3 +SnO 2 +CeO 2 ) / Ag 2 O is 0.4 to 5.0, more preferably (Sb 2 O 3 +SnO 2 +CeO 2 ) / Ag 2 O is 0.7 to 3.7, more preferably (Sb 2 O 3 +SnO 2 +CeO 2 ) / Ag 2 O is between 1.5 and 3.

2. 10) SnO 2 / (CeO 2 +SnO 2 ) is 0 to 0.9, preferably SnO 2 / (CeO 2 +SnO 2 ) is 0 to 0.6, more preferably SnO 2 / (CeO 2 +SnO 2 The value is between 0 and 0.

5. 11) R 2 O+Li 2 O+Al 2 O 3 15-30%, preferably R 2 O+Li 2 O+Al 2 O 3 17.5-29.5%, more preferably R 2 O+Li 2 O+Al 2 O 3 18.5-26%, more preferably R 2 O+Li 2 O+Al 2 O 3 The percentage is 20-25%. 12) (SiO 2 +Al 2 O 3 ) / (Li 2 O+Na 2 O+K 2 O) is 3.0 to 7.5, preferably (SiO 2 +Al 2 O 3 ) / (Li 2 O+Na 2 O+K 2 O) is 3.7 to 6.5, more preferably (SiO 2 +Al 2 O 3 ) / (Li 2 O+Na 2 O+K 2 O) is 4.3 to 6.0, more preferably (SiO 2 +Al 2 O 3 ) / (Li 2 O+Na 2 O+K 2 O) is between 4.8 and 5.

8. 13) MO / ZrO 2 The ratio is 2.5 or less, preferably MO / ZrO 2 is 1.5 or less, more preferably MO / ZrO 2 It is 0.5 or less. 14) Sb 2 O 3 +SnO 2 : 0.05 to 1.2%, preferably Sb 2 O 3 +SnO 2 : 0.1–1%, more preferably Sb 2 O 3 +SnO 2 : 0.2-0.7%, the above R 2 O is Na 2 OK 2 O is one or both types, and MO is one or more types of MgO, CaO, SrO, BaO, or ZnO.

15. Microcrystalline glass according to any one of claims 11 to 13, comprising the following components by weight: SiO 2 : 68-77%, preferably SiO 2 : 69.5–75.5%, and / or R 2 O: 3-10%, preferably R 2 O: 4-8%, and / or Li 2 O: 7-13%, preferably Li 2 O: 8.5–12%, and / or Al 2 O 3 : 4-10%, preferably Al 2 O 3 : 5-9%, and / or ZrO 2 : 2-8%, preferably ZrO 2 : 3–6.5%, and / or CeO 2 : 0.07-0.4%, preferably CeO 2 : 0.08–0.3%, and / or Ag 2 O: 0.1-0.6%, preferably Ag 2 O: 0.2–0.5%, and / or Sb 2 O 3 : 0.01 to 0.7%, preferably Sb 2 O 3 : 0.07–0.5%, and / or SnO 2 : 0-0.3%, preferably SnO 2 : 0-0.2%, and / or MO: 0-3%, preferably MO: 0-1%, more preferably no MO, and / or Ln 2 O 3 : 0-3%, preferably Ln 2 O 3 : 0-1%, more preferably Ln 2 O 3 It does not contain and / or Fe 2 O 3 : 0-0.5%, preferably Fe 2 O 3 : 0-0.2%, more preferably Fe 2 O 3 It does not include the above R 2 O is Na 2 OK 2 O is one or both types, MO is one or more types of MgO, CaO, SrO, BaO, ZnO, Ln 2 O 3 La 2 O 3 , Gd 2 O 3 , Y 2 O 3 It is one or more species of [something].

16. The microcrystalline glass according to any one of claims 11 to 13, wherein the microcrystalline glass includes one or more blackened portions and one or more transparent portions, or the entire microcrystalline glass is a blackened portion.

17. The microcrystalline glass according to claim 16, wherein the microcrystalline glass contains a lithium silicate crystalline phase, preferably a lithium metasilicate crystalline phase, more preferably the weight percentage of the lithium metasilicate crystalline phase in the blackened portion of the microcrystalline glass is 5 to 50%, even more preferably the weight percentage of the lithium metasilicate crystalline phase in the blackened portion of the microcrystalline glass is 5 to 40%, and even more preferably the weight percentage of the lithium metasilicate crystalline phase in the blackened portion of the microcrystalline glass is 10 to 30%.

18. Average transmittance T in the 400-800 nm band range of the transparent portion of microcrystalline glass with a thickness of 0.2-1.5 mm 400-800nm The average transmittance T in the 400-800 nm band range of the blackened portion of a microcrystalline glass with a thickness of 0.2-1.5 mm 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 91.5-95.0%. 400-800nm The transmittance T in the 870nm band of the blackened portion of a microcrystalline glass with a thickness of 0.2 to 1.5 mm is 5.0% or less, preferably 3.0% or less, more preferably 1.5% or less, even more preferably 1.2% or less, and / or even more preferably 0.5% or less. 870nm The transmittance T in the 940nm band of the blackened portion of a microcrystalline glass with a thickness of 0.2 to 1.5 mm is 15.0% or less, preferably 0.1 to 12.5%, more preferably 0.1 to 10%, even more preferably 0.1 to 8.0%, and / or even more preferably 0.1 to 5.0%. 940nm The microcrystalline glass according to claim 16, wherein 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, wherein the thickness of the microcrystalline glass is 0.5 to 1.5 mm, preferably 0.8 to 1.2 mm, 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. Matrix glass containing the following components by weight: SiO 2 : 65-78%; R 2 O: 2-12%; Li 2 O: 5-15%; Al 2 O 3 : 3-12%; ZrO 2 : 1.5–10%; CeO 2 : 0.01–0.6%; Ag 2 O: 0.01-0.8%, the above R 2 O is Na 2 OK 2 It is one or both types of O.

21. The matrix glass according to claim 20, further comprising the following components by weight: Sb 2 O 3 : 0-1%, and / or SnO 2 : 0–0.5%, and / or MO: 0–5%, and / or Ln 2 O 3 : 0-5%, and / or Fe 2 O 3 : 0-1%, the above MO is one or more of MgO, CaO, SrO, BaO, and ZnO, Ln 2 O 3 La 2 O 3 , Gd 2 O 3 , Y 2 O 3 It is one or more species of [something].

22. Matrix glass containing the following components by weight: SiO 2 : 65-78%; R 2 O: 2-12%; Li 2 O: 5-15%; Al 2 O 3 : 3-12%; ZrO 2 : 1.5–10%; CeO 2 : 0.01–0.6%; Ag 2 O: 0.01–0.8%; Sb 2 O 3 : 0-1%; SnO 2 :0~0.5%;MO:0~5%;Ln 2 O 3 : 0-5%; Fe 2 O 3 : Consists of 0-1%, and the R 2 O is Na 2 OK 2 O is one or both types, MO is one or more types of MgO, CaO, SrO, BaO, ZnO, Ln 2 O 3 La 2 O 3 , Gd 2 O 3 , Y 2 O 3 It is one or more species of [something].

23. A matrix glass according to any one of claims 20 to 22, wherein the components are expressed in weight percent and satisfy one or more of the following 14 conditions. 1) SiO 2 / Li 2 O content is 5.5 to 10.0, preferably SiO 2 / Li 2 O content is 6.0 to 9.0, more preferably SiO 2 / Li 2 O is between 7.0 and 8.

5. 2) (Sb 2 O 3 +SnO 2 ) / Ag 2 O is 0.1 to 5.0, preferably (Sb 2 O 3 +SnO 2 ) / Ag 2 O is 0.5 to 3.5, more preferably (Sb 2 O 3 +SnO 2 ) / Ag 2 O is between 1.0 and 2.

6. 3) (K 2 O+Na 2 O) / ZrO 2 is 0.5 to 7.1, preferably (K 2 O+Na 2 O) / ZrO 2 is 0.7 to 4.5, more preferably (K 2 O+Na 2 O) / ZrO 2 The range is 0.8 to 2.

5. 4) Ag 2 O / CeO 2 The value is 1.0 to 10.0, preferably Ag 2 O / CeO 2 1.5 to 6.5, more preferably Ag 2 O / CeO 2 The range is 2.0 to 4.

5. 5) Li 2 O / ZrO 2 The value is 1.0 to 7.5, preferably Li 2 O / ZrO 2 The range is 1.2 to 5.0, more preferably Li 2 O / ZrO 2 The ratio is 1.4 to 4.3, more preferably Li 2 O / ZrO 2 The range is 1.6 to 3.

0. 6) (SiO 2 +Li 2 O) / ZrO 2 The ratio is 8.0 to 55.0, preferably (SiO₂ 2 +Li 2 O) / ZrO 2 is 10.0 to 37.0, more preferably (SiO 2 +Li 2 O) / ZrO 2 The ratio is 12.0 to 25.0, more preferably (SiO 2 +Li 2 O) / ZrO 2 The range is 13.0 to 20.

0. 7) ZrO 2 / (Ag 2 O+CeO 2 ) is 2.3 to 50.0, preferably ZrO 2 / (Ag 2 O+CeO 2 ) is 6.5 to 35.0, more preferably ZrO 2 / (Ag 2 O+CeO 2 ) is 8.5 to 20.0, more preferably ZrO 2 / (Ag 2 O+CeO 2 The range is 11.0 to 18.

0. 8) (Ag 2 O+SnO 2 +Sb 2 O 3 ) / CeO 2 The amount is 1.0 to 30.0, preferably (Ag 2 O+SnO 2 +Sb 2 O 3 ) / CeO 2 is 3.0 to 20.0, more preferably (Ag 2 O+SnO 2 +Sb 2 O 3 ) / CeO 2 is 5.0 to 12.5, more preferably (Ag 2 O+SnO 2 +Sb 2 O 3 ) / CeO 2 The range is 7.5 to 10.

0. 9) (Sb 2 O 3 +SnO 2 +CeO 2 ) / Ag 2 O is 0.1 to 10.0, preferably (Sb 2 O 3 +SnO 2 +CeO 2 ) / Ag 2 O is 0.4 to 5.0, more preferably (Sb 2 O 3 +SnO 2 +CeO 2 ) / Ag 2 O is 0.7 to 3.7, more preferably (Sb 2 O 3 +SnO 2 +CeO 2 ) / Ag 2 O is between 1.5 and 3.

2. 10) SnO 2 / (CeO 2 +SnO 2 ) is 0 to 0.9, preferably SnO 2 / (CeO 2 +SnO 2 ) is 0 to 0.6, more preferably SnO 2 / (CeO 2 +SnO 2 The value is between 0 and 0.

5. 11) R 2 O+Li 2 O+Al 2 O 3 15-30%, preferably R 2 O+Li 2 O+Al 2 O 3 17.5-29.5%, more preferably R 2 O+Li 2 O+Al 2 O 3 18.5-26%, more preferably R 2 O+Li 2 O+Al 2 O 3 The percentage is 20-25%. 12) (SiO 2 +Al 2 O 3 ) / (Li 2 O+Na 2 O+K 2 O) is 3.0 to 7.5, preferably (SiO 2 +Al 2 O 3 ) / (Li 2 O+Na 2 O+K 2 O) is 3.7 to 6.5, more preferably (SiO 2 +Al 2 O 3 ) / (Li 2 O+Na 2 O+K 2 O) is 4.3 to 6.0, more preferably (SiO 2 +Al 2 O 3 ) / (Li 2 O+Na 2 O+K 2 O) is between 4.8 and 5.

8. 13) MO / ZrO 2 The ratio is 2.5 or less, preferably MO / ZrO 2 is 1.5 or less, more preferably MO / ZrO 2 It is 0.5 or less. 14) Sb 2 O 3 +SnO 2 : 0.05 to 1.2%, preferably Sb 2 O 3 +SnO 2 : 0.1–1%, more preferably Sb 2 O 3 +SnO 2 : 0.2-0.7%, the above R 2 O is Na 2 OK 2 O is one or both types, and MO is one or more types of MgO, CaO, SrO, BaO, or ZnO.

24. The matrix glass according to any one of claims 20 to 22, comprising the following components by weight: SiO 2 : 68-77%, preferably SiO 2 : 69.5–75.5%, and / or R 2 O: 3-10%, preferably R 2 O: 4-8%, and / or Li 2 O: 7-13%, preferably Li 2 O: 8.5–12%, and / or Al 2 O 3 : 4-10%, preferably Al 2 O 3 : 5-9%, and / or ZrO 2 : 2-8%, preferably ZrO 2 : 3–6.5%, and / or CeO 2 : 0.07-0.4%, preferably CeO 2 : 0.08–0.3%, and / or Ag 2 O: 0.1-0.6%, preferably Ag 2 O: 0.2–0.5%, and / or Sb 2 O 3 : 0.01 to 0.7%, preferably Sb 2 O 3 : 0.07–0.5%, and / or SnO 2 : 0-0.3%, preferably SnO 2 : 0-0.2%, and / or MO: 0-3%, preferably MO: 0-1%, more preferably no MO, and / or Ln 2 O 3 : 0-3%, preferably Ln 2 O 3 : 0-1%, more preferably Ln 2 O 3 It does not contain and / or Fe 2 O 3 : 0-0.5%, preferably Fe 2 O 3 : 0-0.2%, more preferably Fe 2 O 3 It does not include the above R 2 O is Na 2 OK 2 O is one or both types, MO is one or more types of MgO, CaO, SrO, BaO, ZnO, Ln 2 O 3 La 2 O 3 , Gd 2 O 3 , Y 2 O 3 It is one or more species of [something].

25. The refractive index n of the matrix glass d The ratio is 1.51 to 1.55, preferably 1.52 to 1.54, more preferably 1.53 to 1.535, even more preferably 1.53112 to 1.53284, and / or Young's modulus E is 7000 × 10 7 Pa ~ 9500 x 10 7 Pa, preferably 7500 × 10 7 Pa ~ 9200 x 10 7 Pa, uh, 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 is preferably 470 to 600 kgf / mm². 2 , more preferably 480-582 kgf / mm² 2 More preferably 492-532 kgf / mm 2 , and / or the height I of the ball drop test 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 -3 The following is preferably 7.0 × 10 -3 ~10.5 x 10 -3 , more preferably 7.2 × 10 -3 ~9.8×10 -3 More preferably 7.4 × 10 -3 ~9.2×10 -3 , and / or dielectric constant ε r α is 5.5 to 8.5, preferably 6.0 to 8.0, more preferably 6.2 to 7.7, even more preferably 6.3 to 7.0, and / or the coefficient of linear expansion α 20℃-300℃ 100 x 10 -7 / ℃ or lower, preferably 65 × 10 -7 / ℃~100×10 -7 / ℃, more 71×10 -7 / ℃~95×10 -7 / ℃, more preferably 75 × 10 -7 / ℃~90×10 -7 A matrix glass according to any one of claims 20 to 22, wherein the temperature is / ℃.

26. A microcrystalline glass product 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 cover glass comprising a matrix glass according to any one of claims 20 to 25.

27. A glass element comprising a microcrystalline glass product 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. An apparatus comprising a microcrystalline glass product 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 cover glass according to claim 26, and / or a glass element according to claim 27.

29. A method for manufacturing a microcrystalline glass product according to any one of claims 1 to 10, the method comprising the following steps: forming a matrix glass; processing the matrix glass into microcrystalline glass by a crystallization process; and processing the microcrystalline glass into a microcrystalline glass product by a chemical strengthening process.

30. The method for producing a microcrystalline glass product according to claim 29, wherein the crystallization process comprises a mask exposure treatment of the matrix glass and a recrystallization heat treatment, the mask exposure treatment comprising ultraviolet exposure treatment of a specific position or region of the matrix glass, the wavelength of the ultraviolet light is preferably 313 nm, and the exposure time is preferably 5 to 60 minutes.

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

32. The method for producing a microcrystalline glass product according to claim 29, wherein the chemical strengthening process comprises immersing the microcrystalline glass in a salt bath of molten sodium salt and / or potassium salt and / or a mixed sodium and potassium salt at a temperature of 350°C to 470°C for about 1 to 36 hours, the temperature preferably 380°C to 460°C and the time preferably 2 to 24 hours.

33. A method for manufacturing microcrystalline glass according to any one of claims 11 to 19, the method comprising the following steps: forming a matrix glass and processing the matrix glass into microcrystalline glass by a crystallization process.

34. The method for producing microcrystalline glass according to claim 33, wherein the crystallization process comprises a mask exposure treatment of the matrix glass and a recrystallization heat treatment, the mask exposure treatment comprising ultraviolet exposure treatment of a specific position or region of the matrix glass, the wavelength of the ultraviolet light is preferably 313 nm, and the exposure time is preferably 5 to 60 minutes.

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

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