Microcrystalline glass, microcrystalline glass articles, photosensitive glass, glass elements, and methods of making the same

Abstract

The application provides a kind of glass-ceramics suitable for chemical strengthening, and a glass-ceramics product, a glass element and a manufacturing method thereof. The glass-ceramics, with components expressed in percentage by weight, contains: SiO2+Li2O: 45%~75%; La2O3+Y2O3: 11%~50%; Al2O3: 1%~8%; Ag2O: 0.05%~1%; CeO2: 0.01%~1%, wherein (La2O3+Y2O3) / (Ag2O+CeO2) is 40.0~120.0. Through reasonable component design, the glass-ceramics obtained by the application is suitable for chemical strengthening to make glass-ceramics products; the glass-ceramics has a higher refractive index and visible light transmittance in amorphous part, and the crystalline part of the glass-ceramics has a lower transmittance in visible light and near-infrared band; the glass-ceramics product has a higher refractive index and visible light transmittance in amorphous part, and a lower transmittance in visible light and near-infrared band in the crystalline part of the glass-ceramics product.

Description

Technical Field

[0001] This invention relates to the field of glass technology, and in particular to a microcrystalline glass, as well as microcrystalline glass articles, glass components and manufacturing methods thereof made therefrom. Background Technology

[0002] In recent years, with the continuous development of electronic devices, display devices, and other fields, glass, as a transparent and high-performance material, has been widely used in these areas. For example, in the vital sign monitoring of smartwatches, the glass material needs to be partially transparent while blocking light in other areas to avoid interference from stray light. Therefore, the glass material needs to have both opaque and transparent parts. In optical design, specific light paths can also be achieved by using glass elements that simultaneously have opaque and transparent parts to prevent cross-lighting. Meanwhile, with technological advancements, there are demands for miniaturization, lightweighting, high strength, and high performance in glass elements used in optical systems. High-refractive-index glass has advantages such as shortening the system focal length and reducing the curvature of glass elements, enabling the miniaturization and lightweighting of optical systems. Existing technologies can achieve both opaque and transparent parts in a single glass element using photosensitive microcrystalline glass, but traditional photosensitive microcrystalline glass has a relatively low refractive index (typically less than 1.54) and low strength. To improve its resistance to damage caused by accidental external forces, the strength of the glass can be increased through chemical strengthening. However, traditional photosensitive glass-ceramics cannot be chemically strengthened, or the "inhomogeneity" of the photosensitive glass-ceramic body (the difference in structure between the crystalline and non-crystalline parts) easily leads to poor chemical strengthening effect, making it difficult to meet the application requirements of high-performance electronic devices or display devices. Summary of the Invention

[0003] The technical problem to be solved by the present invention is to provide a microcrystalline glass suitable for chemical strengthening, wherein the amorphous part of the microcrystalline glass has a high refractive index and visible light transmittance, the crystalline part of the microcrystalline glass has low transmittance in the visible and near-infrared bands, and microcrystalline glass articles, glass components and manufacturing methods thereof are made therefrom.

[0004] (1) Microcrystalline glass, whose composition is expressed as a percentage by weight, contains: SiO2+Li2O: 45%~75%; La2O3+Y2O3: 11%~50%; Al2O3: 1%~8%; Ag2O: 0.05%~1%; CeO2: 0.01%~1%, of which (La2O3+Y2O3) / (Ag2O+CeO2) is 40.0~120.0.

[0005] (2) The microcrystalline glass according to (1) further contains, by weight percentage: ZrO2: 0-5%; and / or Sb2O3: 0-1%; and / or K2O: 0-5%; and / or Na2O: 0-5%.

[0006] (3) A microcrystalline glass, comprising SiO2, Li2O, Al2O3, Ag2O, and CeO2, and by weight percentage containing 11%–50% La2O3+Y2O3, wherein (La2O3+Y2O3) / (Ag2O+CeO2) is 40.0–120.0. The microcrystalline glass comprises one or more crystalline portions and one or more amorphous portions. The crystalline portions contain crystalline phases, and the amorphous portions do not contain crystalline phases. The refractive index n of the amorphous portion of the microcrystalline glass is... d The transmittance T of the amorphous portion of a microcrystalline glass with a thickness of 0.3 mm to 1.5 mm and a diameter of 1.55–1.70 nm at a wavelength of 550 nm. 550nm The transmittance T of the crystalline portion of a 0.3mm–1.5mm thick microcrystalline glass at a wavelength of 870nm is above 87.0%. 870nm It is below 10.0%.

[0007] (4) The microcrystalline glass according to (3) contains, by weight percentage: SiO2+Li2O: 45% to 75%; and / or Al2O3: 1% to 8%; and / or Ag2O: 0.05% to 1%; and / or CeO2: 0.01% to 1%; and / or ZrO2: 0% to 5%; and / or Sb2O3: 0% to 1%; and / or K2O: 0% to 5%; and / or Na2O: 0% to 5%.

[0008] (5) The microcrystalline glass according to any one of (1) to (4), wherein the composition is expressed as a weight percentage, wherein: (La2O3+Y2O3) / (Ag2O+CeO2) is 50.0 to 110.0, preferably (La2O3+Y2O3) / (Ag2O+CeO2) is 60.0 to 100.0; and / or (SiO2+Li2O) / (La2O3+Y2O3) is 1.0 to 6.0, preferably (SiO2+Li2O) / (La2O3+Y2O3) is 1.2 to 3.0, more preferably (SiO2+Li2O) / (La2O3+Y2O3) is 1.5 to 2.5; And / or (La2O3+Y2O3) / (Al2O3+ZrO2) is 1.0 to 18.0, preferably (La2O3+Y2O3) / (Al2O3+ZrO2) is 2.0 to 12.0, more preferably (La2O3+Y2O3) / (Al2O3+ZrO2) is 3.5 to 7.0; and / or (La2O3+Y2O3) / (K2O+Na2O) is 2.0 to 20.0, preferably (La2O3+Y2O3) / (K2O+Na2O) is 4.0 to 15.0, more preferably (La2O3+Y2O3) / (K2O+Na2O) is 6.0 to 11.0.

[0009] (6) The microcrystalline glass according to any one of (1) to (4), wherein the components are expressed as weight percentages, wherein: SiO2 / Li2O is 4.0 to 8.0, preferably SiO2 / Li2O is 5.5 to 8.0, more preferably SiO2 / Li2O is 6.0 to 7.5; and / or (SiO2+Li2O) / (K2O+Na2O) is 8.0 to 30.0, preferably (SiO2+Li2O) / (K2O+Na2O) is 10.0 to 25.0, more preferably (SiO2+Li2O) / (K2O+Na2O) is 12.0 to 20.0; and / or Ag2O / CeO2 is 1.0 to 5.0, preferably Ag2O / CeO2 is 1.5 to 4.0, more preferably Ag2O / CeO2 is 2.0 to 3.0.

[0010] (7) The microcrystalline glass according to any one of (1) to (4), wherein the components are expressed as weight percentages, wherein: SiO2+Li2O: 50% to 70%, preferably SiO2+Li2O: 55% to 69%; and / or La2O3+Y2O3: 20% to 45%, preferably La2O3+Y2O3: 25% to 40%; and / or Al2O3: 2% to 6%, preferably Al2O3: 2.5% to 4.8%; and / or Ag2O: 0.05% to 0.8%, preferably Al2O3: 2.5% to 4.8%. g2O: 0.1%–0.5%; and / or CeO2: 0.03%–0.5%, preferably CeO2: 0.05%–0.2%; and / or ZrO2: 0.5%–4%, preferably ZrO2: 1%–3%; and / or Sb2O3: 0.2%–0.8%, preferably Sb2O3: 0.3%–0.6%; and / or K2O: 0.5%–4%, preferably K2O: 1%–3%; and / or Na2O: 0.5%–4%, preferably Na2O: 1%–3%.

[0011] (8) The microcrystalline glass according to any one of (1) to (4), wherein the components are expressed as weight percentages, wherein: SiO2: 35% to 64%, preferably SiO2: 40% to 60%, more preferably SiO2: 45% to 58%; and / or Li2O: 5.5% to 13%, preferably Li2O: 6% to 12%, more preferably Li2O: 7% to 10%; and / or La2O3: 0% to 30%, preferably La2O3: 6% to 28%, more preferably La2O3: 10% to 25%; and / or Y2O3: 0% to 25%, preferably Y2O3: 6% to 22%, more preferably Y2O3: 10% to 20%.

[0012] (9) The glass-ceramic according to any one of (1) to (4), wherein the glass-ceramic comprises one or more crystalline portions and one or more amorphous portions, wherein the crystalline portions contain a crystalline phase and the amorphous portions do not contain a crystalline phase, preferably the crystalline portions contain a lithium metasilicate crystalline phase, more preferably the lithium metasilicate crystalline phase accounts for 5% to 40% of the weight percentage of the crystalline portions of the glass-ceramic, further preferably 10% to 35%, and even more preferably 10% to 30%.

[0013] (10) The glass-ceramic according to (9), wherein the refractive index n of the amorphous portion of the glass-ceramic is... d The dispersion coefficient ν of the amorphous portion of the glass-ceramic is 1.55 to 1.70, preferably 1.57 to 1.68, more preferably 1.58 to 1.65; and / or the dispersion coefficient ν of the amorphous portion of the glass-ceramic. d The transmittance T of the amorphous portion of the 0.3 mm to 1.5 mm thick glass-ceramic at a wavelength of 550 nm is 52.00 to 62.00, preferably 53.00 to 60.00, more preferably 55.00 to 58.00; and / or the transmittance T of the amorphous portion of the glass-ceramic at a wavelength of 550 nm. 550nmThe transmittance T of the crystalline portion of a 0.3 mm to 1.5 mm thick microcrystalline glass at a wavelength of 870 nm is 87.0% or more, preferably 88.0% or more, and more preferably 89.5% or more; and / or the transmittance T of the crystalline portion of the microcrystalline glass at a wavelength of 870 nm. 870nm The transmittance T of the crystalline portion of a 0.3 mm to 1.5 mm thick microcrystalline glass at a wavelength of 1500 nm is 10.0% or less, preferably 5.0% or less, more preferably 3.0% or less, and even more preferably 2.0% or less; and / or the transmittance T of the crystalline portion of the microcrystalline glass at a wavelength of 1500 nm. 1500nm The content is 50.0% or less, preferably 30.0% or less, more preferably 20.0% or less, and even more preferably 10.0% or less; and / or the OD value of the crystalline portion of the microcrystalline glass with a thickness of 0.7 mm at a wavelength of 550 nm. 550nm，0.7mm The OD value is 3.0 to 7.0, preferably 4.0 to 6.0, more preferably 4.5 to 5.5; and / or the OD value of the crystalline portion of the microcrystalline glass with a thickness of 0.3 mm at a wavelength of 550 nm. 550nm，0.3mm The value is 1.0 to 5.0, preferably 2.0 to 4.0, and more preferably 2.5 to 3.5.

[0014] (11) Microcrystalline glass products, whose components are expressed as weight percentages, contain: SiO2+Li2O: 45%~75%; La2O3+Y2O3: 11%~50%; Al2O3: 1%~8%; Ag2O: 0.05%~1%; CeO2: 0.01%~1%, of which (La2O3+Y2O3) / (Ag2O+CeO2) is 40.0~120.0.

[0015] (12) The microcrystalline glass product according to (11) further contains, by weight percentage: ZrO2: 0-5%; and / or Sb2O3: 0-1%; and / or K2O: 0-5%; and / or Na2O: 0-5%.

[0016] (13) A glass-ceramic product containing SiO2, Li2O, Al2O3, Ag2O, and CeO2, and by weight percentage containing 11% to 50% La2O3+Y2O3, wherein (La2O3+Y2O3) / (Ag2O+CeO2) is 40.0 to 120.0, the glass-ceramic product comprising one or more crystalline portions and one or more amorphous portions, the crystalline portions containing crystalline phases, the amorphous portions not containing crystalline phases, and the refractive index n of the amorphous portion of the glass-ceramic product. d The transmittance T of the amorphous portion of a microcrystalline glass product with a thickness of 0.3 mm to 1.5 mm and a diameter of 1.55–1.70 nm at a wavelength of 550 nm. 550nm The transmittance T of the crystalline portion of microcrystalline glass products with a thickness of 0.3 mm to 1.5 mm at a wavelength of 870 nm is above 87.0%. 870nmIt is below 10.0%.

[0017] (14) The microcrystalline glass product according to (13) comprises, by weight percentage: SiO2+Li2O: 45% to 75%; and / or Al2O3: 1% to 8%; and / or Ag2O: 0.05% to 1%; and / or CeO2: 0.01% to 1%; and / or ZrO2: 0% to 5%; and / or Sb2O3: 0% to 1%; and / or K2O: 0% to 5%; and / or Na2O: 0% to 5%.

[0018] (15) The microcrystalline glass article according to any one of (11) to (14) wherein the components are expressed as weight percentages, wherein: (La2O3+Y2O3) / (Ag2O+CeO2) is 50.0 to 110.0, preferably (La2O3+Y2O3) / (Ag2O+CeO2) is 60.0 to 100.0; and / or (SiO2+Li2O) / (La2O3+Y2O3) is 1.0 to 6.0, preferably (SiO2+Li2O) / (La2O3+Y2O3) is 1.2 to 3.0, more preferably (SiO2+Li2O) / (La2O3+Y2O3) is 1.5 to 2. 5; and / or (La2O3+Y2O3) / (Al2O3+ZrO2) is 1.0 to 18.0, preferably (La2O3+Y2O3) / (Al2O3+ZrO2) is 2.0 to 12.0, more preferably (La2O3+Y2O3) / (Al2O3+ZrO2) is 3.5 to 7.0; and / or (La2O3+Y2O3) / (K2O+Na2O) is 2.0 to 20.0, preferably (La2O3+Y2O3) / (K2O+Na2O) is 4.0 to 15.0, more preferably (La2O3+Y2O3) / (K2O+Na2O) is 6.0 to 11.0.

[0019] (16) The microcrystalline glass article according to any one of (11) to (14) has the following components expressed as weight percentages: SiO2 / Li2O is 4.0 to 8.0, preferably SiO2 / Li2O is 5.5 to 8.0, more preferably SiO2 / Li2O is 6.0 to 7.5; and / or (SiO2+Li2O) / (K2O+Na2O) is 8.0 to 30.0, preferably (SiO2+Li2O) / (K2O+Na2O) is 10.0 to 25.0, more preferably (SiO2+Li2O) / (K2O+Na2O) is 12.0 to 20.0; and / or Ag2O / CeO2 is 1.0 to 5.0, preferably Ag2O / CeO2 is 1.5 to 4.0, more preferably Ag2O / CeO2 is 2.0 to 3.0.

[0020] (17) The microcrystalline glass article according to any one of (11) to (14), wherein the components are expressed as weight percentages, wherein: SiO2+Li2O: 50% to 70%, preferably SiO2+Li2O: 55% to 69%; and / or La2O3+Y2O3: 20% to 45%, preferably La2O3+Y2O3: 25% to 40%; and / or Al2O3: 2% to 6%, preferably Al2O3: 2.5% to 4.8%; and / or Ag2O: 0.05% to 0.8%, The preferred concentrations are Ag₂O: 0.1%–0.5%; and / or CeO₂: 0.03%–0.5%, preferably CeO₂: 0.05%–0.2%; and / or ZrO₂: 0.5%–4%, preferably ZrO₂: 1%–3%; and / or Sb₂O₃: 0.2%–0.8%, preferably Sb₂O₃: 0.3%–0.6%; and / or K₂O: 0.5%–4%, preferably K₂O: 1%–3%; and / or Na₂O: 0.5%–4%, preferably Na₂O: 1%–3%.

[0021] (18) The microcrystalline glass article according to any one of (11) to (14) has the following components expressed as weight percentages: SiO2: 35% to 64%, preferably SiO2: 40% to 60%, more preferably SiO2: 45% to 58%; and / or Li2O: 5.5% to 13%, preferably Li2O: 6% to 12%, more preferably Li2O: 7% to 10%; and / or La2O3: 0% to 30%, preferably La2O3: 6% to 28%, more preferably La2O3: 10% to 25%; and / or Y2O3: 0% to 25%, preferably Y2O3: 6% to 22%, more preferably Y2O3: 10% to 20%.

[0022] (19) A glass-ceramic article according to any one of (11) to (14), the glass-ceramic article comprising one or more crystalline portions and one or more amorphous portions, the crystalline portions containing a crystalline phase and the amorphous portions not containing a crystalline phase, preferably the crystalline portions containing a lithium metasilicate crystalline phase, more preferably the lithium metasilicate crystalline phase accounting for 5% to 40% of the weight percentage of the crystalline portion of the glass-ceramic article, further preferably 10% to 35%, and even more preferably 10% to 30%.

[0023] (20) The microcrystalline glass article according to (19), wherein the refractive index n of the amorphous portion of the microcrystalline glass article is... d The dispersion coefficient ν of the amorphous portion of the glass-ceramic article is 1.55 to 1.70, preferably 1.57 to 1.68, more preferably 1.58 to 1.65; and / or the dispersion coefficient ν of the amorphous portion of the glass-ceramic article. dThe transmittance T of the amorphous portion of a 0.3 mm to 1.5 mm thick microcrystalline glass article at a wavelength of 550 nm is 52.00 to 62.00, preferably 53.00 to 60.00, more preferably 55.00 to 58.00; and / or the transmittance T of the amorphous portion of the microcrystalline glass article at a wavelength of 550 nm. 550nm The transmittance is 87.0% or more, preferably 88.0% or more, more preferably 89.5% or more; and / or the drop ball test height I of the amorphous portion of the microcrystalline glass article is 200 mm or more, preferably 300 mm or more, more preferably 400 mm, and even more preferably 450 mm to 600 mm; and / or the transmittance T of the crystalline portion of the microcrystalline glass article with a thickness of 0.3 mm to 1.5 mm at a wavelength of 870 nm. 870nm The transmittance T of the crystalline portion of a 0.3 mm to 1.5 mm thick microcrystalline glass article at a wavelength of 1500 nm is 10.0% or less, preferably 5.0% or less, more preferably 3.0% or less, and even more preferably 2.0% or less; and / or the transmittance T of the crystalline portion of the microcrystalline glass article is 1500 nm or less. 1500nm The content is 50.0% or less, preferably 30.0% or less, more preferably 20.0% or less, and even more preferably 10.0% or less; and / or the OD value of the crystalline portion of the microcrystalline glass article with a thickness of 0.7 mm at a wavelength of 550 nm. 550nm，0.7mm The OD value is 3.0 to 7.0, preferably 4.0 to 6.0, more preferably 4.5 to 5.5; and / or the OD value of the crystalline portion of a microcrystalline glass article with a thickness of 0.3 mm at a wavelength of 550 nm. 550nm，0.3mm The value is 1.0 to 5.0, preferably 2.0 to 4.0, more preferably 2.5 to 3.5; and / or the drop ball test height II of the crystal portion of the microcrystalline glass product is 300 mm or more, preferably 400 mm or more, more preferably 500 mm or more, and even more preferably 600 mm to 800 mm.

[0024] (21) Photosensitive glass, whose composition is expressed as a percentage by weight, contains: SiO2+Li2O: 45%~75%; La2O3+Y2O3: 11%~50%; Al2O3: 1%~8%; Ag2O: 0.05%~1%; CeO2: 0.01%~1%, of which (La2O3+Y2O3) / (Ag2O+CeO2) is 40.0~120.0.

[0025] (22) The photosensitive glass according to (21) further contains, by weight percentage: ZrO2: 0-5%; and / or Sb2O3: 0-1%; and / or K2O: 0-5%; and / or Na2O: 0-5%.

[0026] (23) The photosensitive glass according to (21) or (22) has the following components expressed as weight percentages: (La2O3+Y2O3) / (Ag2O+CeO2) is 50.0 to 110.0, preferably (La2O3+Y2O3) / (Ag2O+CeO2) is 60.0 to 100.0; and / or (SiO2+Li2O) / (La2O3+Y2O3) is 1.0 to 6.0, preferably (SiO2+Li2O) / (La2O3+Y2O3) is 1.2 to 3.0, more preferably (SiO2+Li2O) / (La2O3+Y2O3) is 1.5 to 2.5; And / or (La2O3+Y2O3) / (Al2O3+ZrO2) is 1.0 to 18.0, preferably (La2O3+Y2O3) / (Al2O3+ZrO2) is 2.0 to 12.0, more preferably (La2O3+Y2O3) / (Al2O3+ZrO2) is 3.5 to 7.0; and / or (La2O3+Y2O3) / (K2O+Na2O) is 2.0 to 20.0, preferably (La2O3+Y2O3) / (K2O+Na2O) is 4.0 to 15.0, more preferably (La2O3+Y2O3) / (K2O+Na2O) is 6.0 to 11.0.

[0027] (24) The photosensitive glass according to (21) or (22) has the following components expressed as weight percentages: SiO2 / Li2O is 4.0 to 8.0, preferably SiO2 / Li2O is 5.5 to 8.0, more preferably SiO2 / Li2O is 6.0 to 7.5; and / or (SiO2+Li2O) / (K2O+Na2O) is 8.0 to 30.0, preferably (SiO2+Li2O) / (K2O+Na2O) is 10.0 to 25.0, more preferably (SiO2+Li2O) / (K2O+Na2O) is 12.0 to 20.0; and / or Ag2O / CeO2 is 1.0 to 5.0, preferably Ag2O / CeO2 is 1.5 to 4.0, more preferably Ag2O / CeO2 is 2.0 to 3.0.

[0028] (25) The photosensitive glass according to (21) or (22) comprises, by weight percentage: SiO2+Li2O: 50%–70%, preferably SiO2+Li2O: 55%–69%; and / or La2O3+Y2O3: 20%–45%, preferably La2O3+Y2O3: 25%–40%; and / or Al2O3: 2%–6%, preferably Al2O3: 2.5%–4.8%; and / or Ag2O: 0.05%–0.8%, preferably... Ag2O: 0.1%–0.5%; and / or CeO2: 0.03%–0.5%, preferably CeO2: 0.05%–0.2%; and / or ZrO2: 0.5%–4%, preferably ZrO2: 1%–3%; and / or Sb2O3: 0.2%–0.8%, preferably Sb2O3: 0.3%–0.6%; and / or K2O: 0.5%–4%, preferably K2O: 1%–3%; and / or Na2O: 0.5%–4%, preferably Na2O: 1%–3%.

[0029] (26) The photosensitive glass according to (21) or (22) has the following components expressed in weight percentage: SiO2: 35% to 64%, preferably SiO2: 40% to 60%, more preferably SiO2: 45% to 58%; and / or Li2O: 5.5% to 13%, preferably Li2O: 6% to 12%, more preferably Li2O: 7% to 10%; and / or La2O3: 0% to 30%, preferably La2O3: 6% to 28%, more preferably La2O3: 10% to 25%; and / or Y2O3: 0% to 25%, preferably Y2O3: 6% to 22%, more preferably Y2O3: 10% to 20%.

[0030] (27) The photosensitive glass according to (21) or (22), wherein the refractive index n of the photosensitive glass is d The value is 1.55 to 1.70, preferably 1.57 to 1.68, more preferably 1.58 to 1.65; and / or the dispersion coefficient v d The transmittance T of the photosensitive glass with a thickness of 0.3 mm to 1.5 mm at a wavelength of 550 nm is 52.00 to 62.00, preferably 53.00 to 60.00, more preferably 55.00 to 58.00; and / or the transmittance T of the photosensitive glass with a thickness of 0.3 mm to 1.5 mm at a wavelength of 550 nm. 550nm It is 87.0% or higher, preferably 88.0% or higher, and more preferably 89.5% or higher.

[0031] (28) A glass element made of any of the microcrystalline glass described in (1) to (10), or made of any of the microcrystalline glass products described in (11) to (20), or made of any of the photosensitive glass described in (21) to (27).

[0032] (29) An apparatus comprising any of the microcrystalline glass described in (1) to (10), and / or comprising any of the microcrystalline glass articles described in (11) to (20), and / or comprising any of the photosensitive glass described in (21) to (27), and / or comprising the glass element described in (28).

[0033] The manufacturing method of microcrystalline glass according to any one of (30) (1) to (10) includes the following steps: forming photosensitive glass, processing the photosensitive glass through a crystallization process to obtain microcrystalline glass, or processing the photosensitive glass into a glass mold and then processing it through a crystallization process to obtain microcrystalline glass.

[0034] (31) According to the manufacturing method of the microcrystalline glass described in (30), the crystallization process includes exposure treatment and crystallization heat treatment of the photosensitive glass or glass mold, the exposure treatment includes mask exposure or laser direct writing exposure treatment, the exposure light source is ultraviolet light, preferably with an ultraviolet light wavelength of 300nm to 350nm, more preferably with an ultraviolet light wavelength of 300nm to 330nm, the exposure time is 5 minutes to 60 minutes, and the light power density is 0.5mW / cm². 2 ~20.0mW / cm 2 .

[0035] (32) According to the manufacturing method of microcrystalline glass described in (31), the crystallization heat treatment includes nucleation process at a first temperature and crystal growth process at a second temperature higher than the nucleation process temperature. The first temperature is 490°C to 520°C and the treatment time at the first temperature is 1 hour to 5 hours. The second temperature is 540°C to 650°C and the treatment time at the second temperature is 2 hours to 8 hours.

[0036] The manufacturing method of the microcrystalline glass product according to any one of (33) (11) to (20) includes the following steps: forming photosensitive glass, processing the photosensitive glass through a crystallization process to obtain microcrystalline glass, or processing the photosensitive glass into a glass mold and then processing it through a crystallization process to obtain microcrystalline glass, and then processing the microcrystalline glass through a chemical strengthening process to obtain the microcrystalline glass product.

[0037] (34) According to the manufacturing method of the microcrystalline glass product described in (33), the crystallization process includes exposure treatment and crystallization heat treatment of the photosensitive glass or glass mold, the exposure treatment includes mask exposure or laser direct writing exposure treatment, the exposure light source is ultraviolet light, preferably the ultraviolet light wavelength is 300nm~350nm, more preferably the ultraviolet light wavelength is 300nm~330nm, the exposure time is 5 minutes~60 minutes, and the light power density is 0.5mW / cm². 2 ~20.0mW / cm 2 .

[0038] (35) According to the manufacturing method of the microcrystalline glass product described in (34), the crystallization heat treatment includes a nucleation process at a first temperature and a crystal growth process at a second temperature higher than the nucleation process temperature. The first temperature is 490°C to 520°C and the treatment time at the first temperature is 1 hour to 5 hours. The second temperature is 540°C to 650°C and the treatment time at the second temperature is 2 hours to 8 hours.

[0039] (36) According to the manufacturing method of the microcrystalline glass product described in (33), the chemical strengthening process includes immersing the microcrystalline glass in a salt bath of molten Na salt, and / or K salt, and / or a mixed Na and K salt at a temperature of 350°C to 470°C for 1 hour to 36 hours, preferably at a temperature of 380°C to 460°C, and preferably for a time of 2 hours to 24 hours.

[0040] The beneficial effects of this invention are: through reasonable component design, the microcrystalline glass obtained by this invention is suitable for chemical strengthening to produce microcrystalline glass products; the amorphous portion of the microcrystalline glass of this invention has a high refractive index and visible light transmittance, while the crystalline portion of the microcrystalline glass has a low transmittance in the visible and near-infrared bands; the amorphous portion of the microcrystalline glass product of this invention has a high refractive index and visible light transmittance, while the crystalline portion of the microcrystalline glass product has a low transmittance in the visible and near-infrared bands. Detailed Implementation

[0041] The embodiments of the present invention will now be described in detail. However, the present invention is not limited to the embodiments described below, and appropriate modifications can be made to implement it within the scope of the purpose of the present invention. Furthermore, regarding repeated descriptions, although there are appropriate omissions, this will not limit the spirit of the invention.

[0042] Photosensitive glass, microcrystalline glass, microcrystalline glass products

[0043] The microcrystalline glass and microcrystalline glass articles of the present invention are materials having a crystalline phase (sometimes also called crystal) and a glassy phase, which are different from amorphous solids. The crystalline phase of the microcrystalline glass and microcrystalline glass articles can be identified by the peak angle appearing in the X-ray diffraction pattern of X-ray diffraction analysis and / or measured by TEMEDX.

[0044] In some embodiments, the microcrystalline glass of the present invention comprises one or more crystalline portions and one or more amorphous portions, wherein the crystalline portions contain a crystalline phase and the amorphous portions do not contain a crystalline phase. In some embodiments, the crystalline portions of the microcrystalline glass have low transmittance in the visible and near-infrared bands, while the amorphous portions of the microcrystalline glass have high transmittance in the visible light band. Specifically, in some embodiments, the light transmittance (T0) of the crystalline portion of a 0.3 mm to 1.5 mm thick microcrystalline glass at 870 nm is... 870nmThe transmittance (T) of the crystalline portion of the 0.3 mm to 1.5 mm thick microcrystalline glass at 1500 nm is 10.0% or less, preferably 5.0% or less, more preferably 3.0% or less, and even more preferably 2.0% or less. In some embodiments, the transmittance (T) of the crystalline portion of the microcrystalline glass is... 1500nm The transmittance (T) of the amorphous portion of the 0.3 mm to 1.5 mm thick microcrystalline glass at 550 nm is 50.0% or less, preferably 30.0% or less, more preferably 20.0% or less, and even more preferably 10.0% or less. In some embodiments, the transmittance (T) of the amorphous portion of the microcrystalline glass at 550 nm is... 550nm The content of the crystalline phase is 87.0% or more, preferably 88.0% or more, and more preferably 89.5% or more. Due to the above-mentioned properties, the microcrystalline glass of the present invention is suitable for manufacturing optical signal channels, optical shielding systems, or protective covers for optical systems or electronic products. In some embodiments, the crystalline portions of the microcrystalline glass of the present invention can form patterns of arbitrary shapes and / or sizes. In some embodiments, the microcrystalline glass of the present invention may contain only crystalline portions and no amorphous portions; this occurs when the photosensitive glass is not masked, and the entire photosensitive glass is directly exposed and subjected to crystallization heat treatment to obtain the microcrystalline glass. In some embodiments, the crystalline phase in the crystalline portion of the microcrystalline glass is uniformly distributed. In some embodiments, the crystalline portion of the microcrystalline glass contains a lithium metasilicate crystalline phase (Li2SiO3), and the lithium metasilicate crystalline phase accounts for 5% to 40% of the weight percentage of the crystalline portion of the microcrystalline glass, preferably 10% to 35%, and more preferably 10% to 30%. In some embodiments, the weight percentage of the lithium metasilicate crystalline phase in the crystalline portion of the glass-ceramic can be 5%, 7%, 10%, 13%, 15%, 17%, 20%, 23%, 25%, 27%, 30%, 33%, 35%, 37%, 40%, etc., as well as all ranges and sub-ranges between the above values. It should be understood that, in embodiments, any of the above ranges can be combined with any other range.

[0045] In some embodiments, the microcrystalline glass article of the present invention comprises one or more crystalline portions and one or more amorphous portions, wherein the crystalline portions contain a crystalline phase and the amorphous portions do not contain a crystalline phase. In some embodiments, the crystalline portions of the microcrystalline glass article have low transmittance in the visible and near-infrared bands, while the amorphous portions of the microcrystalline glass article have high transmittance in the visible light band. Specifically, in some embodiments, the light transmittance (T0) of the crystalline portion of a 0.3 mm to 1.5 mm thick microcrystalline glass article at 870 nm is... 870nm The transmittance (T) of the crystalline portion of a 0.3 mm to 1.5 mm thick microcrystalline glass article at 1500 nm is 10.0% or less, preferably 5.0% or less, more preferably 3.0% or less, and even more preferably 2.0% or less. In some embodiments, the transmittance (T) of the crystalline portion of the microcrystalline glass article is... 1500nmThe transmittance (T) of the amorphous portion of the 0.3 mm to 1.5 mm thick microcrystalline glass article at 550 nm is 50.0% or less, preferably 30.0% or less, more preferably 20.0% or less, and even more preferably 10.0% or less. In some embodiments, the transmittance (T) of the amorphous portion of the microcrystalline glass article is 50.0% or less, preferably 30.0% or less, more preferably 20.0% or less, and even more preferably 10.0% or less. 550nm The content of the crystalline phase is 87.0% or more, preferably 88.0% or more, and more preferably 89.5% or more. Due to the above-mentioned properties, the microcrystalline glass product of the present invention is suitable for manufacturing optical signal channels, optical shielding systems, or protective covers for optical systems or electronic products. In some embodiments, the crystalline portion of the microcrystalline glass product of the present invention can form a pattern of arbitrary shape and / or size. In some embodiments, the microcrystalline glass product of the present invention may contain only crystalline portions and not amorphous portions. This is when the photosensitive glass is not masked, and the entire photosensitive glass is directly exposed and subjected to crystallization heat treatment to obtain a microcrystalline glass product, which is then subjected to a strengthening process. In some embodiments, the crystalline phase in the crystalline portion of the microcrystalline glass product is uniformly distributed. In some embodiments, the crystalline portion of the microcrystalline glass product contains a lithium metasilicate crystalline phase (Li2SiO3), and the lithium metasilicate crystalline phase accounts for 5% to 40% of the weight percentage of the crystalline portion of the microcrystalline glass product, preferably 10% to 35%, and more preferably 10% to 30%. In some embodiments, the weight percentage of the lithium metasilicate crystalline phase in the crystalline portion of the glass-ceramic article can be 5%, 7%, 10%, 13%, 15%, 17%, 20%, 23%, 25%, 27%, 30%, 33%, 35%, 37%, 40%, etc., as well as all ranges and sub-ranges between the above values. It should be understood that, in embodiments, any of the above ranges can be combined with any other range.

[0046] The scope of each component (ingredient) of the photosensitive glass, microcrystalline glass, and microcrystalline glass products of the present invention will be described below. In this specification, unless otherwise specified, the content of each component is expressed as a weight percentage (wt%) relative to the total amount of the photosensitive glass, microcrystalline glass, or microcrystalline glass product, converted to oxide composition. Here, "converted to oxide composition" means that when oxides, composite salts, and hydroxides used as raw materials for the photosensitive glass, microcrystalline glass, or microcrystalline glass products of the present invention decompose and transform into oxides upon melting, the total amount of such oxides is taken as 100%. Furthermore, in this specification, when referred to simply as "glass," it refers to photosensitive glass before crystallization processing; photosensitive glass after crystallization processing is referred to as microcrystalline glass; and microcrystalline glass after strengthening processing is referred to as microcrystalline glass products.

[0047] It should be understood that the microcrystalline glass of the present invention is obtained by crystallizing the photosensitive glass of the present invention, without involving changes in the types and contents of glass components. Therefore, the components and contents of the microcrystalline glass are the same as or substantially the same as those of the photosensitive glass. The microcrystalline glass product is obtained by strengthening the microcrystalline glass of the present invention. The weight percentage variation of each component in the overall component content of the microcrystalline glass product is small and almost negligible. Therefore, the components and contents of the microcrystalline glass product are the same as or substantially the same as those of the microcrystalline glass.

[0048] Unless otherwise specified in the specific context, the numerical ranges listed herein include upper and lower limits. "Above" and "below" include endpoint values ​​and all integers and fractions within the range, not limited to the specific values ​​listed when the range is defined. The term "and / or" as used herein is inclusive; for example, "A and / or B" means either only A, or only B, or both A and B.

[0049] SiO2 is a glass-forming component used to form the framework of photosensitive glass, glass-ceramics, and glass-ceramic products. SiO2 is also a major component of the crystalline phase in glass-ceramics and glass-ceramic products. When the SiO2 content is less than 35%, the drop ball test height of photosensitive glass, glass-ceramics, and glass-ceramic products decreases; after crystallization treatment, the content of crystals precipitated inside the glass decreases; and the transmittance of the crystalline portion of glass-ceramics and glass-ceramic products increases in the visible and near-infrared light bands, failing to achieve the effect of shielding stray light. However, if the SiO2 content is higher than 64%, the refractive index of the amorphous portion of photosensitive glass, glass-ceramics, and glass-ceramic products decreases, the dispersion coefficient increases, and the OD value of the crystalline portion of glass-ceramics and glass-ceramic products decreases in the visible light band. Therefore, the SiO2 content is 35%–64%, preferably 40%–60%, and more preferably 45%–58%. In some embodiments, the SiO2 content can be 35%, 35.5%, 36%, 36.5%, 37%, 37.5%, 38%, 38.5%, 39%, 39.5%, 40%, 40.5%, 41%, 41.5%, 42%, 42.5%, 43%, 43.5%, 44%, 44.5%, 45%, 45.5%, 46%, 46.5%, 47%, 47.5%, 48%, 48.5%, 49%, 49%. 5%, 50%, 50.5%, 51%, 51.5%, 52%, 52.5%, 53%, 53.5%, 54%, 54.5%, 55%, 55.5%, 56%, 56.5%, 57%, 57.5%, 58%, 58.5%, 59%, 59.5%, 60%, 60.5%, 61%, 61.5%, 62%, 62.5%, 63%, 63.5%, 64%, etc., as well as all ranges and sub-ranges between the above values. It should be understood that, in the implementation scheme, any of the above ranges can be combined with any other range.

[0050] Li₂O is the main component of the crystalline phase in the microcrystalline glass and microcrystalline glass products of this invention. When the Li₂O content is less than 5.5%, the amount of crystals precipitated inside the photosensitive glass decreases after the crystallization process, and the transmittance of the crystalline portion of the microcrystalline glass and the crystalline portion of the microcrystalline glass products increases in the visible and near-infrared light bands, failing to achieve the effect of shielding stray light. If the Li₂O content is greater than 13%, the refractive index of the amorphous portion of the photosensitive glass, the microcrystalline glass, and the amorphous portion of the microcrystalline glass products decreases, the dispersion coefficient increases, and the drop ball test height of the photosensitive glass, the microcrystalline glass, and the microcrystalline glass products decreases. Therefore, the Li₂O content is 5.5% to 13%, preferably 6% to 12%, and more preferably 7% to 10%. In some embodiments, the Li₂O content can be 5.5%, 5.7%, 6%, 6.3%, 6.5%, 6.7%, 7%, 7.3%, 7.5%, 7.7%, 8%, 8.3%, 8.5%, 8.7%, 9%, 9.3%, 9.5%, 9.7%, 10%, 10.3%, 10.5%, 10.7%, 11%, 11.3%, 11.5%, 11.7%, 12%, 12.3%, 12.5%, 12.7%, 13%, etc., as well as all ranges and sub-ranges between the above values. It should be understood that, in embodiments, any of the above ranges can be combined with any other range.

[0051] In some embodiments, when the SiO2 / Li2O ratio is below 4.0, the visible light transmittance of the amorphous portion of the photosensitive glass, the glass-ceramic, and the amorphous portion of the glass-ceramic product decreases, while the transmittance of the crystalline portion of the glass-ceramic and the crystalline portion of the glass-ceramic product increases in the near-infrared band, and the drop ball test height of the amorphous portion of the glass-ceramic product decreases. However, if the SiO2 / Li2O ratio exceeds 8.0, the transmittance of the crystalline portion of the glass-ceramic and the crystalline portion of the glass-ceramic product increases in the near-infrared band, while the OD value and drop ball test height of the crystalline portion of the glass-ceramic and the crystalline portion of the glass-ceramic product decrease in the visible light band. Therefore, a SiO2 / Li2O ratio of 4.0 to 8.0 is preferred, a SiO2 / Li2O ratio of 5.5 to 8.0 is more preferred, and a SiO2 / Li2O ratio of 6.0 to 7.5 is even more preferred. In some implementations, the SiO2 / Li2O value can be 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, 7.6, 7.7, 7.8, 7.9, 8.0, etc., as well as all ranges and sub-ranges between the above values. It should be understood that, in implementations, any of the above ranges can be combined with any other range.

[0052] In some embodiments, the refractive index of the amorphous portion of the photosensitive glass, the glass-ceramic, and the amorphous portion of the glass-ceramic product decreases with the increase of the total content of SiO2 and Li2O (SiO2+Li2O). If SiO2+Li2O exceeds 75%, it is difficult to achieve the high refractive index objective of the present invention. If SiO2+Li2O is less than 45%, the transmittance of the crystalline portion of the glass-ceramic and the crystalline portion of the glass-ceramic product increases in the near-infrared band, while the OD value and drop ball test height of the crystalline portion of the glass-ceramic and the crystalline portion of the glass-ceramic product decrease in the visible band. Therefore, when SiO2+Li2O is preferably in the range of 45% to 75%, more preferably in the range of 50% to 70%, and even more preferably in the range of 55% to 69%, the amorphous portion of photosensitive glass, glass-ceramic, and glass-ceramic products can more easily obtain higher refractive index and visible light transmittance. The crystalline portion of glass-ceramic and glass-ceramic products have lower transmittance in the near-infrared band, while the crystalline portion of glass-ceramic and glass-ceramic products have higher OD value and drop ball test height in the visible light band, making them particularly suitable for lightweight design and aberration correction of optical systems. In some embodiments, SiO2+Li2O can be 45%, 45.5%, 46%, 46.5%, 47%, 47.5%, 48%, 48.5%, 49%, 49.5%, 50%, 50.5%, 51%, 51.5%, 52%, 52.5%, 53%, 53.5%, 54%, 54.5%, 55%, 55.5%, 56%, 56.5%, 57%, 57.5%, 58%, 58.5%, 59%, 59.5%, 6 0%, 60.5%, 61%, 61.5%, 62%, 62.5%, 63%, 63.5%, 64%, 64.5%, 65%, 65.5%, 66%, 66.5%, 67%, 67.5%, 68%, 68.5%, 69%, 69.5%, 70%, 70.5%, 71%, 71.5%, 72%, 72.5%, 73%, 73.5%, 74%, 74.5%, 75%, etc., as well as all ranges and sub-ranges between the above values. It should be understood that, in the implementation scheme, any of the above ranges can be combined with any other range.

[0053] La₂O₃ and Y₂O₃ can improve the refractive index of photosensitive glass and control the dispersion coefficient. If their combined content (La₂O₃ + Y₂O₃) is less than 11%, the refractive index of the amorphous portion of the photosensitive glass, glass-ceramic, and glass-ceramic products decreases, while the dispersion coefficient increases. If La₂O₃ + Y₂O₃ exceeds 50%, the transmittance of the crystalline portion of the glass-ceramic and glass-ceramic products increases in the near-infrared band, while the OD value of the crystalline portion of the glass-ceramic and glass-ceramic products decreases in the visible light band. Therefore, the content of La₂O₃ + Y₂O₃ is 11%–50%, preferably 20%–45%, and more preferably 25%–40%. In some implementations, La2O3+Y2O3 can be 11%, 11.5%, 12%, 12.5%, 13%, 13.5%, 14%, 14.5%, 15%, 15.5%, 16%, 16.5%, 17%, 17.5%, 18%, 18.5%, 19%, 19.5%, 20%, 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%, 30%, 3 The content of La2O3 is 0.5%, 31%, 31.5%, 32%, 32.5%, 33%, 33.5%, 34%, 34.5%, 35%, 35.5%, 36%, 36.5%, 37%, 37.5%, 38%, 38.5%, 39%, 39.5%, 40%, 40.5%, 41%, 41.5%, 42%, 42.5%, 43%, 43.5%, 44%, 44.5%, 45%, 45.5%, 46%, 46.5%, 47%, 47.5%, 48%, 48.5%, 49%, 49.5%, 50%, etc., as well as all ranges and sub-ranges between the above values. It should be understood that, in embodiments, any of the above ranges can be combined with any other range. Further, in some embodiments, the content of La2O3 is 0-30%, preferably 6%-28%, more preferably 10%-25%.In some embodiments, the La2O3 content can be 0%, greater than 0%, 0.01%, 0.05%, 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, 10%, 10.5%, 11%, 11.5%, 12%, 12.5%, 13%, 13.5%, 14%, 14.5%. 15%, 15.5%, 16%, 16.5%, 17%, 17.5%, 18%, 18.5%, 19%, 19.5%, 20%, 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%, 30%, etc., as well as all ranges and sub-ranges between the above values. It should be understood that, in embodiments, any of the above ranges can be combined with any other range. In some embodiments, the Y₂O₃ content is 0–25%, preferably 6%–22%, more preferably 10%–20%. In some embodiments, the content of Y₂O₃ can be 0%, greater than 0%, 0.01%, 0.05%, 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, 10%, 10.5%, 11%, 11.5%, 12%, 12.5%, 13%, 13.5%, 14%, 14.5%, 15%, 15.5%, 16%, 16.5%, 17%, 17.5%, 18%, 18.5%, 19%, 19.5%, 20%, 20.5%, 21%, 21.5%, 22%, 22.5%, 23%, 23.5%, 24%, 24.5%, 25%, etc., as well as all ranges and sub-ranges between the above values. It should be understood that, in embodiments, any of the above ranges can be combined with any other range.

[0054] In some embodiments, if the ratio of the total content of SiO2 and Li2O (SiO2+Li2O) to the total content of La2O3 and Y2O3 (La2O3+Y2O3) (SiO2+Li2O) / (La2O3+Y2O3) is less than 1.0, the drop ball test height of the photosensitive glass, glass-ceramic, and glass-ceramic products is reduced, and the OD value of the crystalline part of the glass-ceramic and the crystalline part of the glass-ceramic products in the visible light band is reduced; if (SiO2+Li2O) / (La2O3+Y2O3) exceeds 6.0, the refractive index of the amorphous part of the photosensitive glass, glass-ceramic, and the amorphous part of the glass-ceramic products is reduced, and the dispersion coefficient is increased. Therefore, the preferred ratio of (SiO2+Li2O) / (La2O3+Y2O3) is 1.0 to 6.0, more preferably (SiO2+Li2O) / (La2O3+Y2O3) is 1.2 to 3.0, and even more preferably (SiO2+Li2O) / (La2O3+Y2O3) is 1.5 to 2.5. In some implementations, (SiO2+Li2O) / (La2O3+Y2O3) 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, 5.1, 5.2, 5.3, 5.4, 5.5, 5.6, 5.7, 5.8, 5.9, 6.0, etc., as well as all ranges and subranges between the above values. It should be understood that, in the implementation plan, any of the above scopes can be combined with any other scopes.

[0055] Al2O3 can suppress crystallization during the manufacturing process of photosensitive glass, thereby improving the strength and chemical stability of photosensitive glass, glass-ceramics, and glass-ceramic products. When the Al2O3 content is less than 1%, the drop ball test height of photosensitive glass, glass-ceramics, and glass-ceramic products decreases; when the Al2O3 content exceeds 8%, the crystal content of the glass-ceramics formed after the crystallization treatment of photosensitive glass decreases, and the transmittance of the crystalline portion of the glass-ceramics and the crystalline portion of the glass-ceramic products increases in the near-infrared light band. Therefore, in this invention, the Al2O3 content is 1% to 8%, preferably 2% to 6%, and more preferably 2.5% to 4.8%. In some embodiments, the Al2O3 content can be 1%, 1.3%, 1.5%, 1.7%, 2%, 2.3%, 2.5%, 2.7%, 3%, 3.3%, 3.5%, 3.7%, 4%, 4.3%, 4.5%, 4.7%, 4.8%, 5%, 5.3%, 5.5%, 5.7%, 6%, 6.3%, 6.5%, 6.7%, 7%, 7.3%, 7.5%, 7.7%, 8%, etc., as well as all ranges and sub-ranges between the above values. It should be understood that, in embodiments, any of the above ranges can be combined with any other range.

[0056] ZrO2 can adjust the refractive index and dispersion coefficient of photosensitive glass, and simultaneously optimize the boundary accuracy between the crystalline and amorphous parts of the microcrystalline glass obtained after crystallization, thereby ensuring that the amorphous parts of the microcrystalline glass and microcrystalline glass products have high transmittance in the visible light band, while the crystalline parts of the microcrystalline glass and microcrystalline glass products have lower transmittance in the visible and near-infrared bands. When the ZrO2 content is higher than 5%, the refractive index of the amorphous parts of the photosensitive glass, microcrystalline glass, and microcrystalline glass products decreases, the dispersion coefficient increases, and the OD value of the crystalline parts of the microcrystalline glass and microcrystalline glass products decreases in the visible light band. Therefore, the ZrO2 content is 0-5%. In some embodiments, if ZrO2 is not present, the unexposed portion of the photosensitive glass is prone to crystallization during heat treatment, causing the portion of the microcrystalline glass intended to form an amorphous part to precipitate a crystalline phase, thereby reducing the visible light transmittance of that portion. Therefore, the ZrO2 content is preferably 0.5%-4%, more preferably 1%-3%. In some embodiments, the ZrO2 content can be 0%, greater than 0%, 0.01%, 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2%, 2.3%, 2.5%, 2.7%, 3%, 3.3%, 3.5%, 3.7%, 4%, 4.3%, 4.5%, 4.7%, 5%, etc., as well as all ranges and sub-ranges between the above values. It should be understood that, in embodiments, any of the above ranges can be combined with any other range.

[0057] In some embodiments, when the ratio (La2O3+Y2O3) / (Al2O3+ZrO2) between the total content of La2O3 and Y2O3 (La2O3+Y2O3) and the total content of Al2O3 and ZrO2 (Al2O3+ZrO2) is less than 1.0, the refractive index of the amorphous portion of the photosensitive glass, the glass-ceramic, and the amorphous portion of the glass-ceramic product decreases, and the dispersion coefficient increases; when (La2O3+Y2O3) / (Al2O3+ZrO2) is greater than 18.0, the drop ball test height of the amorphous portion of the photosensitive glass, the glass-ceramic, and the amorphous portion of the glass-ceramic product decreases, and the OD value of the crystalline portion of the glass-ceramic and the crystalline portion of the glass-ceramic product decreases in the visible light band. Therefore, the preferred ratio of (La2O3+Y2O3) / (Al2O3+ZrO2) is 1.0 to 18.0, more preferably (La2O3+Y2O3) / (Al2O3+ZrO2) is 2.0 to 12.0, and even more preferably (La2O3+Y2O3) / (Al2O3+ZrO2) is 3.5 to 7.0. In some implementations, the value of (La2O3+Y2O3) / (Al2O3+ZrO2) 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, 5.3, 5.5, 5.7, 6.0, 6.3, 6.5, 6.7. 7.0, 7.3, 7.5, 7.7, 8.0, 8.3, 8.5, 8.7, 9.0, 9.3, 9.5, 9.7, 10.0, 10.3, 10.5, 10.7, 11.0, 11.3, 11.5, 11.7, 12.0, 12.3, 12.5, 12.7, 13.0, 13.3, 13.5, 13.7, 14.0, 14.3, 14.5, 14.7, 15.0, 15.3, 15.5, 15.7, 16.0, 16.3, 16.5, 16.7, 17.0, 17.3, 17.5, 17.7, 18.0, etc., as well as all ranges and subranges between the above values. It should be understood that, in the implementation scheme, any of the above ranges can be combined with any other range.

[0058] K₂O and Na₂O can improve the transmittance of the crystalline portion of glass-ceramics and glass-ceramic products in the visible and near-infrared bands, and promote the formation of crystalline phases in glass-ceramics. However, if their content is too high, the refractive index of the amorphous portion of photosensitive glass, glass-ceramics, and glass-ceramic products decreases, and the dispersion coefficient increases. Therefore, the content of K₂O is 0-5%, preferably 0.5%-4%, and more preferably 1%-3%. The content of Na₂O is 0-5%, preferably 0.5%-4%, and more preferably 1%-3%. In some embodiments, the Na₂O content can be 0%, greater than 0%, 0.01%, 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2%, 2.3%, 2.5%, 2.7%, 3%, 3.3%, 3.5%, 3.7%, 4%, 4.3%, 4.5%, 4.7%, 5%, etc., as well as all ranges and sub-ranges between the above values. It should be understood that, in embodiments, any of the above ranges can be combined with any other range. In some embodiments, the K2O content can be 0%, greater than 0%, 0.01%, 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2%, 2.3%, 2.5%, 2.7%, 3%, 3.3%, 3.5%, 3.7%, 4%, 4.3%, 4.5%, 4.7%, 5%, etc., as well as all ranges and sub-ranges between the above values. It should be understood that, in embodiments, any of the above ranges can be combined with any other range.

[0059] In some embodiments, if the ratio of the total content of SiO2 and Li2O (SiO2+Li2O) to the total content of K2O and Na2O (K2O+Na2O) (SiO2+Li2O) / (K2O+Na2O) is less than 8.0, the drop ball test height of the amorphous portion of the photosensitive glass, the glass-ceramic, and the amorphous portion of the glass-ceramic product decreases. If (SiO2+Li2O) / (K2O+Na2O) is greater than 30.0, the OD value of the crystalline portion of the glass-ceramic and the crystalline portion of the glass-ceramic product decreases in the visible light band, and the light transmittance in the near-infrared band increases. Therefore, it is preferable that (SiO2+Li2O) / (K2O+Na2O) is 8.0 to 30.0, more preferably (SiO2+Li2O) / (K2O+Na2O) is 10.0 to 25.0, and even more preferably (SiO2+Li2O) / (K2O+Na2O) is 12.0 to 20.0. In some implementations, the value of (SiO2+Li2O) / (K2O+Na2O) can be 8.0, 8.5, 9.0, 9.5, 10.0, 10.5, 11.0, 11.5, 12.0, 12.5, 13.0, 13.5, 14.0, 14.5, 15.0, 15.5, 16.0, 16.5, 17.0, 17.5, 18.0, 1 8.5, 19.0, 19.5, 20.0, 20.5, 21.0, 21.5, 22.0, 22.5, 23.0, 23.5, 24.0, 24.5, 25.0, 25.5, 26.0, 26.5, 27.0, 27.5, 28.0, 28.5, 29.0, 29.5, 30.0, etc., as well as all ranges and subranges between the above values. It should be understood that, in the implementation scheme, any of the above ranges can be combined with any other range.

[0060] In some embodiments, when the ratio (La2O3+Y2O3) / (K2O+Na2O) between the total content of La2O3 and Y2O3 (La2O3+Y2O3) and the total content of K2O and Na2O (K2O+Na2O) is less than 2.0, the refractive index of the amorphous portion of the photosensitive glass, the glass-ceramic, and the amorphous portion of the glass-ceramic product decreases, and the dispersion coefficient increases. However, when (La2O3+Y2O3) / (K2O+Na2O) is greater than 20.0, the visible light transmittance and the drop ball test height of the amorphous portion of the photosensitive glass, the glass-ceramic, and the amorphous portion of the glass-ceramic product decrease. Therefore, the preferred ratio of (La2O3+Y2O3) / (K2O+Na2O) is 2.0 to 20.0, more preferably (La2O3+Y2O3) / (K2O+Na2O) is 4.0 to 15.0, and even more preferably (La2O3+Y2O3) / (K2O+Na2O) is 6.0 to 11.0. In some implementations, the value of (La₂O₃+Y₂O₃) / (K₂O+Na₂O) can be 2.0, 2.3, 2.5, 2.7, 3.0, 3.3, 3.5, 3.7, 4.0, 4.3, 4.5, 4.7, 5.0, 5.3, 5.5, 5.7, 6.0, 6.3, 6.5, 6.7, 7.0, 7.3, 7.5, 7.7, 8.0, 8.3, 8.5, 8.7, 9.0, 9.3, 9.5, 9.7, 10.0, 10.3, 10.5, 10.7, 11.0, 11.3 The ranges are: 11.5, 11.7, 12.0, 12.3, 12.5, 12.7, 13.0, 13.3, 13.5, 13.7, 14.0, 14.3, 14.5, 14.7, 15.0, 15.3, 15.5, 15.7, 16.0, 16.3, 16.5, 16.7, 17.0, 17.3, 17.5, 17.7, 18.0, 18.3, 18.5, 18.7, 19.0, 19.3, 19.5, 19.7, 20.0, etc., as well as all ranges and subranges between the above values. It should be understood that, in the implementation scheme, any of the above ranges can be combined with any other range.

[0061] Ag₂O, as a nucleating agent for photosensitive glass, promotes crystal precipitation during the crystallization process. When the Ag₂O content is below 0.05%, the OD value of the crystalline portion of the glass-ceramic and the crystalline portion of the glass-ceramic product decreases in the visible light band, while the light transmittance in the near-infrared band increases. When the Ag₂O content is greater than 1%, the photosensitive glass is prone to crystallization during molding, resulting in impurities inside the glass and a decrease in the visible light transmittance. Therefore, the Ag₂O content is 0.05%–1%, preferably 0.05%–0.8%, and more preferably 0.1%–0.5%. In some embodiments, the Ag₂O content can be 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%, 0.9%, 0.93%, 0.95%, 0.97%, 1%, etc., as well as all ranges and sub-ranges between the above values. It should be understood that, in embodiments, any of the above ranges can be combined with any other range.

[0062] CeO2, as a photosensitizer, can [be used for Ag] +When the CeO2 content is below 0.01%, insufficient electrons are provided, resulting in an excessively low crystalline phase content in the crystalline portions of the glass-ceramic and glass-ceramic products, leading to a decrease in the OD value of the crystalline portions. When the CeO2 content is above 1%, the visible light transmittance of the photosensitive glass, the amorphous portions of the glass-ceramic, and the amorphous portions of the glass-ceramic products decreases, and the penetration depth of the photosensitive glass in the ultraviolet band decreases. Furthermore, uneven crystallization within the glass during the crystallization process during the manufacture of glass-ceramics results in increased light transmittance in the near-infrared band for the crystalline portions of the glass-ceramic and glass-ceramic products. Therefore, the CeO2 content is 0.01%–1%, preferably 0.03%–0.5%, and more preferably 0.05%–0.2%. In some embodiments, the CeO2 content can be 0.01%, 0.02%, 0.03%, 0.04%, 0.05%, 0.06%, 0.07%, 0.08%, 0.09%, 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%, 0.9%, 0.93%, 0.95%, 0.97%, 1%, etc., as well as all ranges and subranges between the above values. It should be understood that, in the implementation plan, any of the above scopes can be combined with any other scopes.

[0063] In some embodiments, when the ratio of Ag₂O content to CeO₂ content (Ag₂O / CeO₂) is controlled within the range of 1.0 to 5.0, the visible light transmittance of the amorphous portion of the photosensitive glass, the glass-ceramic, and the amorphous portion of the glass-ceramic product can be increased, as well as the OD value of the crystalline portion of the glass-ceramic and the crystalline portion of the glass-ceramic product can be increased, while the near-infrared light transmittance of the crystalline portion of the glass-ceramic and the crystalline portion of the glass-ceramic product can be kept at a low value. Therefore, it is preferable that Ag₂O / CeO₂ is 1.0 to 5.0, more preferably 1.5 to 4.0, and even more preferably 2.0 to 3.0. In some implementations, the value of Ag2O / CeO2 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, etc., as well as all ranges and subranges between the above values. It should be understood that, in implementations, any of the above ranges can be combined with any other range.

[0064] In some embodiments, when the ratio (La2O3+Y2O3) / (Ag2O+CeO2) between the total content of La2O3 and Y2O3 (La2O3+Y2O3) and the total content of Ag2O and CeO2 (Ag2O+CeO2) is less than 40.0, the visible light transmittance and refractive index of the amorphous portion of the photosensitive glass, the glass-ceramic, and the amorphous portion of the glass-ceramic product decrease, and the drop ball test height of the crystalline portion of the glass-ceramic and the crystalline portion of the glass-ceramic product deteriorates. If (La2O3+Y2O3) / (Ag2O+CeO2) exceeds 120.0, the OD value of the crystalline portion of the glass-ceramic and the crystalline portion of the glass-ceramic product decreases, and the near-infrared light transmittance of the crystalline portion of the glass-ceramic and the crystalline portion of the glass-ceramic product decreases. Therefore, the preferred value of (La2O3+Y2O3) / (Ag2O+CeO2) is 40.0 to 120.0, more preferably (La2O3+Y2O3) / (Ag2O+CeO2) is 50.0 to 110.0, and even more preferably (La2O3+Y2O3) / (Ag2O+CeO2) is 60.0 to 100.0. In some implementations, the value of (La2O3+Y2O3) / (Ag2O+CeO2) can be 40.0, 43.0, 45.0, 47.0, 50.0, 53.0, 55.0, 57.0, 60.0, 63.0, 65.0, 67.0, 70.0, 73.0, 75.0, 77.0, 80.0, 83.0, 85.0, 87.0, 90.0, 93.0, 95.0, 97.0, 100.0, 103.0, 105.0, 107.0, 110.0, 113.0, 115.0, 117.0, 120.0, etc., as well as all ranges and subranges between the above values. It should be understood that, in implementations, any of the above ranges can be combined with any other range.

[0065] Sb₂O₃ can improve the uniformity of photosensitive glass and promote the crystallization of the crystalline regions in glass-ceramics. If the Sb₂O₃ content exceeds 1%, the molten glass is prone to corroding the platinum crucible, resulting in platinum inclusions in the glass. Therefore, the Sb₂O₃ content is 0–1%. In some embodiments, if the Sb₂O₃ content is less than 0.2%, the OD value of the crystalline regions of the glass-ceramics and the crystalline regions of the glass-ceramics products decreases, and the near-infrared light transmittance of the crystalline regions of the glass-ceramics and the crystalline regions of the glass-ceramics products decreases. Therefore, the Sb₂O₃ content is preferably 0.2%–0.8%, more preferably 0.3%–0.6%. In some embodiments, the Sb₂O₃ content can be 0%, greater than 0%, 0.01%, 0.02%, 0.03%, 0.04%, 0.05%, 0.06%, 0.07%, 0.08%, 0.09%, 0.1%, 0.13%, 0.15%, 0.17%, 0.2%, 0.23%, 0.25%, 0.27%, 0.3%, 0.33%, 0.35%, 0.37%, or 0.4%. The values ​​are 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%, 0.9%, 0.93%, 0.95%, 0.97%, 1%, etc., as well as all ranges and sub-ranges between the above values. It should be understood that, in the implementation scheme, any of the above ranges can be combined with any other range.

[0066] The terms "not containing", "0%", and "0" used herein mean that the compound, molecule, or element was not intentionally added as a raw material to the photosensitive glass, microcrystalline glass, or microcrystalline glass product of this invention. However, as raw materials and / or equipment used in the production of photosensitive glass, microcrystalline glass, or microcrystalline glass products, there may be some other impurities or components that are not intentionally added, which may be present in small or trace amounts (less than 0.01%) in the final photosensitive glass, microcrystalline glass, or microcrystalline glass product. Such cases are also within the scope of protection of this patent.

[0067] The properties of the photosensitive glass and / or glass-ceramic and / or glass-ceramic products of the present invention are tested using the following methods:

[0068] <Refractive index and dispersion coefficient>

[0069] Refractive index (n) d ) and dispersion coefficient (v d Tested according to the method specified in the national standard GB / T7962.1-2010 Colorless Optical Glass Test Methods Part 1: Refractive Index and Dispersion Coefficient.

[0070] <Light transmittance>

[0071] The light transmittance is tested according to the following method: the sample to be tested is processed to a certain thickness and subjected to parallel polishing on opposite surfaces, wherein: 1) the visible light transmittance of the photosensitive glass is tested in accordance with the national standard "GB / T 7962.12-2010 Test Methods for Colourless Optical Glass Part 12: Spectral Internal Transmittance", and the transmittance at the wavelength of 550 nm (T 550nm ) is used for characterization; 2) the visible light transmittance of the amorphous part of the glass-ceramic and the amorphous part of the glass-ceramic product is tested in accordance with the national standard "GB / T 7962.12-2010 Test Methods for Colourless Optical Glass Part 12: Spectral Internal Transmittance", and the transmittance at the wavelength of 550 nm (T 550nm ) is used for characterization; 3) the near-infrared band transmittance of the crystalline part of the glass-ceramic and the crystalline part of the glass-ceramic product is tested in accordance with the national standard "GB / T 15489.1-1995 Test Method for Filter Glass Spectral Characteristics", and the transmittance at the wavelength of 870 nm (T 870nm ) and the transmittance at the wavelength of 1500 nm (T 1500nm ) are used for characterization.

[0072] <OD value>

[0073] The crystalline part of the glass-ceramic or the crystalline part of the glass-ceramic product is respectively made into samples with thicknesses of 0.7 mm ± 0.1 mm and 0.3 mm ± 0.1 mm, the transmittance T of the test samples in the wavelength range of 400 nm to 600 nm is scanned and tested respectively, and the transmittance at 550 nm (T 550nm ) is read. The test method is based on the national standard "GB / T 15489.1-1995 Test Method for Filter Glass Spectral Characteristics". Then the OD value is calculated according to the following formula.

[0074] OD=log 10 (1 / T 550nm )

[0075] <Falling ball test height>

[0076] The photosensitive glass / microcrystalline glass / microcrystalline glass product to be tested is made into a sample with a diameter of φ27.5mm × 0.7mm. This sample is placed on a glass support fixture, and a 64g steel ball is dropped from a specified height. The maximum drop ball test height from which the sample can withstand the impact without breaking is defined as the drop ball test height. Specifically, the test is conducted starting at a height of 50mm, with each subsequent drop at 50mm intervals. Without breaking, the height is increased sequentially to 50mm, 100mm, 150mm, 200mm, 250mm, 300mm, 350mm, 400mm, 450mm, 500mm, 550mm, 600mm, 650mm, 700mm, 750mm, 800mm, and above. In this invention, the drop ball test height is sometimes simply referred to as the drop ball height.

[0077] The photosensitive glass of this invention has the following properties:

[0078] 1) In some embodiments, the transmittance (T0.3mm-1.5mm thick photosensitive glass at a wavelength of 550nm) is... 550nm The transmittance (T) of the photosensitive glass at a wavelength of 550 nm is 87.0% or more, preferably 88.0% or more, and more preferably 89.5% or more. The thickness is preferably 0.5 mm to 1.2 mm, more preferably 0.8 mm to 1.2 mm. In some embodiments, the thickness can be 0.3 mm, 0.4 mm, 0.5 mm, 0.6 mm, 0.7 mm, 0.8 mm, 0.9 mm, 1.0 mm, 1.1 mm, 1.2 mm, 1.3 mm, 1.4 mm, 1.5 mm, etc., and all ranges and sub-ranges between these values. In some embodiments, the transmittance (T) of the photosensitive glass at a wavelength of 550 nm is... 550nm The values ​​can be 87.0%, 87.1%, 87.2%, 87.3%, 87.4%, 87.5%, 87.6%, 87.7%, 87.8%, 87.9%, 88.0%, 88.1%, 88.2%, 88.3%, 88.4%, 88.5%, 88.6%, 88.7%, 88.8%, 88.9%, 89.0%, 89.1%, 89.2%, 89.3%, 89.4%, 89.5%, 89.6%, 89.7%, 89.8%, 89.9%, 90.0%, 90.1%, 90.2%, 90.3%, 90.4%, 90.5%, 90.6%, 90.7%, 90.8%, 90.9%, 91.0%, etc., as well as all ranges and sub-ranges between the above values. It should be understood that, in the implementation scheme, any of the above ranges can be combined with any other range.

[0079] 2) In some embodiments, the refractive index (n) of the photosensitive glass is... dThe refractive index (n) of the photosensitive glass is 1.55–1.70, preferably 1.57–1.68, and more preferably 1.58–1.65. In some embodiments, the refractive index (n) of the photosensitive glass is... d The possible values ​​are 1.550, 1.553, 1.555, 1.557, 1.560, 1.563, 1.565, 1.567, 1.570, 1.753, 1.575, 1.577, 1.580, 1.583, 1.585, 1.587, 1.590, 1.593, 1.595, 1.597, 1.600, 1.603, 1.605, 1.607, 1.610, 1.613, 1.615, 1.617, 1.620, 1.623, 1.625, and 1.62. 7, 1.630, 1.633, 1.635, 1.637, 1.640, 1.643, 1.645, 1.647, 1.650, 1.653, 1.655, 1.657, 1.660, 1.663, 1.665, 1.667, 1.670, 1.673, 1.675, 1.677, 1.680, 1.683, 1.685, 1.687, 1.690, 1.693, 1.695, 1.697, 1.700, etc., as well as all ranges and subranges between the above values. It should be understood that, in the implementation scheme, any of the above ranges can be combined with any other range.

[0080] 3) In some embodiments, the dispersion coefficient (v) of the photosensitive glass d The dispersion coefficient (v) of the glass material is 52.00–62.00, preferably 53.00–60.00, and more preferably 55.00–58.00. In some embodiments, the dispersion coefficient (v) of the glass material is... d The values ​​can be 52.00, 52.30, 52.50, 52.70, 53.00, 53.30, 53.50, 53.70, 54.00, 54.30, 54.50, 54.70, 55.00, 55.30, 55.50, 55.70, 56.00, 56.30, 56.50, 56.70, 57.00, and 57.3. 0, 57.50, 57.70, 58.00, 58.30, 58.50, 58.70, 59.00, 59.30, 59.50, 59.70, 60.00, 60.30, 60.50, 60.70, 61.00, 61.30, 61.50, 61.70, 62.00, etc., as well as all ranges and subranges between the above values. It should be understood that, in the implementation scheme, any of the above ranges can be combined with any other range.

[0081] The microcrystalline glass of this invention has the following properties:

[0082] 1) In some embodiments, the transmittance (T0.3) of the amorphous portion of a 0.3mm to 1.5mm thick microcrystalline glass at a wavelength of 550nm is... 550nm The transmittance is 87.0% or more, preferably 88.0% or more, and more preferably 89.5% or more. The thickness is preferably 0.5 mm to 1.2 mm, more preferably 0.8 mm to 1.2 mm. In some embodiments, the thickness can be 0.3 mm, 0.4 mm, 0.5 mm, 0.6 mm, 0.7 mm, 0.8 mm, 0.9 mm, 1.0 mm, 1.1 mm, 1.2 mm, 1.3 mm, 1.4 mm, 1.5 mm, etc., and all ranges and sub-ranges between these values. In some embodiments, the transmittance (T0) of the amorphous portion of the 0.3 mm to 1.5 mm thick microcrystalline glass at a wavelength of 550 nm is... 550nm The values ​​can be 87.0%, 87.1%, 87.2%, 87.3%, 87.4%, 87.5%, 87.6%, 87.7%, 87.8%, 87.9%, 88.0%, 88.1%, 88.2%, 88.3%, 88.4%, 88.5%, 88.6%, 88.7%, 88.8%, 88.9%, 89.0%, 89.1%, 89.2%, 89.3%, 89.4%, 89.5%, 89.6%, 89.7%, 89.8%, 89.9%, 90.0%, 90.1%, 90.2%, 90.3%, 90.4%, 90.5%, 90.6%, 90.7%, 90.8%, 90.9%, 91.0%, etc., as well as all ranges and sub-ranges between the above values. It should be understood that, in the implementation scheme, any of the above ranges can be combined with any other range.

[0083] 2) In some embodiments, the refractive index (n) of the amorphous portion of the glass-ceramic is... d The refractive index (n) is 1.55 to 1.70, preferably 1.57 to 1.68, and more preferably 1.58 to 1.65. In some embodiments, the refractive index (n) of the amorphous portion of the glass-ceramic is... dThe possible values ​​are 1.550, 1.553, 1.555, 1.557, 1.560, 1.563, 1.565, 1.567, 1.570, 1.753, 1.575, 1.577, 1.580, 1.583, 1.585, 1.587, 1.590, 1.593, 1.595, 1.597, 1.600, 1.603, 1.605, 1.607, 1.610, 1.613, 1.615, 1.617, 1.620, 1.623, 1.625, and 1.62. 7, 1.630, 1.633, 1.635, 1.637, 1.640, 1.643, 1.645, 1.647, 1.650, 1.653, 1.655, 1.657, 1.660, 1.663, 1.665, 1.667, 1.670, 1.673, 1.675, 1.677, 1.680, 1.683, 1.685, 1.687, 1.690, 1.693, 1.695, 1.697, 1.700, etc., as well as all ranges and subranges between the above values. It should be understood that, in the implementation scheme, any of the above ranges can be combined with any other range.

[0084] 3) In some embodiments, the dispersion coefficient (v) of the amorphous portion of the glass-ceramic is... d The dispersion coefficient (v) of the amorphous portion of the glass-ceramic is 52.00 to 62.00, preferably 53.00 to 60.00, and more preferably 55.00 to 58.00. In some embodiments, the dispersion coefficient (v) of the amorphous portion of the glass-ceramic is... d The values ​​can be 52.00, 52.30, 52.50, 52.70, 53.00, 53.30, 53.50, 53.70, 54.00, 54.30, 54.50, 54.70, 55.00, 55.30, 55.50, 55.70, 56.00, 56.30, 56.50, 56.70, 57.00, and 57.3. 0, 57.50, 57.70, 58.00, 58.30, 58.50, 58.70, 59.00, 59.30, 59.50, 59.70, 60.00, 60.30, 60.50, 60.70, 61.00, 61.30, 61.50, 61.70, 62.00, etc., as well as all ranges and subranges between the above values. It should be understood that, in the implementation scheme, any of the above ranges can be combined with any other range.

[0085] 4) In some embodiments, the transmittance (T0.3) of the crystalline portion of a 0.3 mm to 1.5 mm thick microcrystalline glass at a wavelength of 870 nm is... 870nmThe transmittance is 10.0% or less, preferably 5.0% or less, more preferably 3.0% or less, and even more preferably 2.0% or less. The thickness is preferably 0.5 mm to 1.2 mm, more preferably 0.8 mm to 1.2 mm. In some embodiments, the thickness can be 0.3 mm, 0.4 mm, 0.5 mm, 0.6 mm, 0.7 mm, 0.8 mm, 0.9 mm, 1.0 mm, 1.1 mm, 1.2 mm, 1.3 mm, 1.4 mm, 1.5 mm, etc., and all ranges and sub-ranges between the above values. In some embodiments, the transmittance (T0) of the crystalline portion of the microcrystalline glass at a wavelength of 870 nm is... 870nm The values ​​can be 0.01%, 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2.0%, 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%, 5.3%, 5.5%, 5.7%, 6.0%, 6.3%, 6.5%, 6.7%, 7.0%, 7.3%, 7.5%, 7.7%, 8.0%, 8.3%, 8.5%, 8.7%, 9.0%, 9.3%, 9.5%, 9.7%, 10.0%, etc., as well as all ranges and sub-ranges between the above values. It should be understood that, in the implementation scheme, any of the above ranges can be combined with any other range.

[0086] 5) In some embodiments, the transmittance (T0.3) of the crystalline portion of a 0.3 mm to 1.5 mm thick microcrystalline glass at a wavelength of 1500 nm is... 1500nm The transmittance (T) is 50.0% or less, preferably 30.0% or less, more preferably 20.0% or less, and even more preferably 10.0% or less. The thickness is preferably 0.5 mm to 1.2 mm, more preferably 0.8 mm to 1.2 mm. In some embodiments, the thickness can be 0.3 mm, 0.4 mm, 0.5 mm, 0.6 mm, 0.7 mm, 0.8 mm, 0.9 mm, 1.0 mm, 1.1 mm, 1.2 mm, 1.3 mm, 1.4 mm, 1.5 mm, etc., and all ranges and sub-ranges between these values. In some embodiments, the transmittance (T) of the crystalline portion of a 0.3 mm to 1.5 mm thick microcrystalline glass at a wavelength of 1500 nm is... 1500nmThe percentages can be 0.01%, 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2.0%, 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%, 5.3%, 5.5%, 5.7%, 6.0%, 6.3%, 6.5%, 6.7%, 7.0%, 7.3%, 7.5%, 7.7%, 8.0%, 8.3%, 8.5%, 8.7%, 9.0%, 9.3%, 9.5%, 9.7%, 10.0%, 13.0%, 15.0%, 17.0%, 20.0%, 23.0%, 25.0%, 27.0%, 30.0%, 33.0%, 35.0%, 37.0%, 40.0%, 43.0%, 45.0%, 47.0%, 50.0%, etc., as well as all ranges and sub-ranges between the above values. It should be understood that, in the implementation scheme, any of the above ranges can be combined with any other range.

[0087] 6) In some embodiments, the OD value (OD) of the crystalline portion of the 0.7 mm thick microcrystalline glass at a wavelength of 550 nm is... 550nm，0.7mm The OD value (OD) is 3.0 to 7.0, preferably 4.0 to 6.0, and more preferably 4.5 to 5.5. In some embodiments, the OD value (OD) of the crystalline portion of the 0.7 mm thick microcrystalline glass at a wavelength of 550 nm is... 550nm，0.7mm The range can be 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4.0, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, 5.0, 5.1, 5.2, 5.3, 5.4, 5.5, 5.6, 5.7, 5.8, 5.9, 6.0, 6.1, 6.2, 6.3, 6.4, 6.5, 6.6, 6.7, 6.8, 6.9, 7.0, etc., as well as all ranges and subranges between the above values. It should be understood that, in the implementation scheme, any of the above ranges can be combined with any other range.

[0088] 7) In some embodiments, the OD value (OD) of the crystalline portion of the 0.3 mm thick microcrystalline glass at a wavelength of 550 nm is... 550nm，0.3mmThe OD value (OD) is 1.0 to 5.0, preferably 2.0 to 4.0, and more preferably 2.5 to 3.5. In some embodiments, the OD value (OD) of the crystalline portion of the 0.3 mm thick microcrystalline glass at a wavelength of 550 nm is... 550nm，0.3mm The range 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, etc., as well as all ranges and subranges between the above values. It should be understood that, in the implementation scheme, any of the above ranges can be combined with any other range.

[0089] The microcrystalline glass products of this invention have the following properties:

[0090] 1) In some embodiments, the transmittance (T0) of the amorphous portion of a 0.3mm to 1.5mm thick microcrystalline glass article at a wavelength of 550nm is... 550nm The transmittance is 87.0% or more, preferably 88.0% or more, and more preferably 89.5% or more. The thickness is preferably 0.5 mm to 1.2 mm, more preferably 0.8 mm to 1.2 mm. In some embodiments, the thickness can be 0.3 mm, 0.4 mm, 0.5 mm, 0.6 mm, 0.7 mm, 0.8 mm, 0.9 mm, 1.0 mm, 1.1 mm, 1.2 mm, 1.3 mm, 1.4 mm, 1.5 mm, etc., and all ranges and sub-ranges between these values. In some embodiments, the transmittance (T0) of the amorphous portion of the 0.3 mm to 1.5 mm thick microcrystalline glass article at a wavelength of 550 nm is... 550nm The values ​​can be 87.0%, 87.1%, 87.2%, 87.3%, 87.4%, 87.5%, 87.6%, 87.7%, 87.8%, 87.9%, 88.0%, 88.1%, 88.2%, 88.3%, 88.4%, 88.5%, 88.6%, 88.7%, 88.8%, 88.9%, 89.0%, 89.1%, 89.2%, 89.3%, 89.4%, 89.5%, 89.6%, 89.7%, 89.8%, 89.9%, 90.0%, 90.1%, 90.2%, 90.3%, 90.4%, 90.5%, 90.6%, 90.7%, 90.8%, 90.9%, 91.0%, etc., as well as all ranges and sub-ranges between the above values. It should be understood that, in the implementation scheme, any of the above ranges can be combined with any other range.

[0091] 2) In some embodiments, the refractive index (n) of the amorphous portion of the glass-ceramic article is... d The refractive index (n) of the amorphous portion of the glass-ceramic article is 1.55–1.70, preferably 1.57–1.68, and more preferably 1.58–1.65. In some embodiments, the refractive index (n) of the amorphous portion of the glass-ceramic article is... d The possible values ​​are 1.550, 1.553, 1.555, 1.557, 1.560, 1.563, 1.565, 1.567, 1.570, 1.753, 1.575, 1.577, 1.580, 1.583, 1.585, 1.587, 1.590, 1.593, 1.595, 1.597, 1.600, 1.603, 1.605, 1.607, 1.610, 1.613, 1.615, 1.617, 1.620, 1.623, 1.625, and 1.62. 7, 1.630, 1.633, 1.635, 1.637, 1.640, 1.643, 1.645, 1.647, 1.650, 1.653, 1.655, 1.657, 1.660, 1.663, 1.665, 1.667, 1.670, 1.673, 1.675, 1.677, 1.680, 1.683, 1.685, 1.687, 1.690, 1.693, 1.695, 1.697, 1.700, etc., as well as all ranges and subranges between the above values. It should be understood that, in the implementation scheme, any of the above ranges can be combined with any other range.

[0092] 3) In some embodiments, the dispersion coefficient (v) of the amorphous portion of the glass-ceramic article d The dispersion coefficient (v) of the amorphous portion of the glass-ceramic article is 52.00 to 62.00, preferably 53.00 to 60.00, and more preferably 55.00 to 58.00. In some embodiments, the dispersion coefficient (v) of the amorphous portion of the glass-ceramic article is... d The values ​​can be 52.00, 52.30, 52.50, 52.70, 53.00, 53.30, 53.50, 53.70, 54.00, 54.30, 54.50, 54.70, 55.00, 55.30, 55.50, 55.70, 56.00, 56.30, 56.50, 56.70, 57.00, and 57.3. 0, 57.50, 57.70, 58.00, 58.30, 58.50, 58.70, 59.00, 59.30, 59.50, 59.70, 60.00, 60.30, 60.50, 60.70, 61.00, 61.30, 61.50, 61.70, 62.00, etc., as well as all ranges and subranges between the above values. It should be understood that, in the implementation scheme, any of the above ranges can be combined with any other range.

[0093] 4) In some embodiments, the transmittance (T) of the crystalline portion of a 0.3mm to 1.5mm thick microcrystalline glass article at a wavelength of 870nm is... 870nm The transmittance (T) is 10.0% or less, preferably 5.0% or less, more preferably 3.0% or less, and even more preferably 2.0% or less. The thickness is preferably 0.5 mm to 1.2 mm, more preferably 0.8 mm to 1.2 mm. In some embodiments, the thickness can be 0.3 mm, 0.4 mm, 0.5 mm, 0.6 mm, 0.7 mm, 0.8 mm, 0.9 mm, 1.0 mm, 1.1 mm, 1.2 mm, 1.3 mm, 1.4 mm, 1.5 mm, etc., and all ranges and sub-ranges between the above values. In some embodiments, the transmittance (T) of the crystalline portion of a 0.3 mm to 1.5 mm thick microcrystalline glass article at a wavelength of 870 nm is... 870nm The values ​​can be 0.01%, 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2.0%, 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%, 5.3%, 5.5%, 5.7%, 6.0%, 6.3%, 6.5%, 6.7%, 7.0%, 7.3%, 7.5%, 7.7%, 8.0%, 8.3%, 8.5%, 8.7%, 9.0%, 9.3%, 9.5%, 9.7%, 10.0%, etc., as well as all ranges and sub-ranges between the above values. It should be understood that, in the implementation scheme, any of the above ranges can be combined with any other range.

[0094] 5) In some embodiments, the transmittance (T0.3) of the crystalline portion of a 0.3 mm to 1.5 mm thick microcrystalline glass article at a wavelength of 1500 nm is... 1500nmThe transmittance (T) is 50.0% or less, preferably 30.0% or less, more preferably 20.0% or less, and even more preferably 10.0% or less. The thickness is preferably 0.5 mm to 1.2 mm, more preferably 0.8 mm to 1.2 mm. In some embodiments, the thickness can be 0.3 mm, 0.4 mm, 0.5 mm, 0.6 mm, 0.7 mm, 0.8 mm, 0.9 mm, 1.0 mm, 1.1 mm, 1.2 mm, 1.3 mm, 1.4 mm, 1.5 mm, etc., and all ranges and sub-ranges between the above values. In some embodiments, the transmittance (T) of the crystalline portion of a 0.3 mm to 1.5 mm thick microcrystalline glass article at a wavelength of 1500 nm is... 1500nm The percentages can be 0.01%, 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2.0%, 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%, 5.3%, 5.5%, 5.7%, 6.0%, 6.3%, 6.5%, 6.7%, 7.0%, 7.3%, 7.5%, 7.7%, 8.0%, 8.3%, 8.5%, 8.7%, 9.0%, 9.3%, 9.5%, 9.7%, 10.0%, 13.0%, 15.0%, 17.0%, 20.0%, 23.0%, 25.0%, 27.0%, 30.0%, 33.0%, 35.0%, 37.0%, 40.0%, 43.0%, 45.0%, 47.0%, 50.0%, etc., as well as all ranges and sub-ranges between the above values. It should be understood that, in the implementation scheme, any of the above ranges can be combined with any other range.

[0095] 6) In some embodiments, the OD value (OD) of the crystalline portion of a 0.7 mm thick microcrystalline glass article at a wavelength of 550 nm is... 550nm，0.7mm The OD value (OD) of the crystalline portion of a 0.7 mm thick microcrystalline glass article at a wavelength of 550 nm is 3.0 to 7.0, preferably 4.0 to 6.0, and more preferably 4.5 to 5.5. In some embodiments, the OD value (OD) of the crystalline portion of the microcrystalline glass article is... 550nm，0.7mmThe range can be 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4.0, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, 5.0, 5.1, 5.2, 5.3, 5.4, 5.5, 5.6, 5.7, 5.8, 5.9, 6.0, 6.1, 6.2, 6.3, 6.4, 6.5, 6.6, 6.7, 6.8, 6.9, 7.0, etc., as well as all ranges and subranges between the above values. It should be understood that, in the implementation scheme, any of the above ranges can be combined with any other range.

[0096] 7) In some embodiments, the OD value (OD) of the crystalline portion of a 0.3 mm thick microcrystalline glass article at a wavelength of 550 nm is... 550nm，0.3mm The OD value (OD) is 1.0 to 5.0, preferably 2.0 to 4.0, and more preferably 2.5 to 3.5. In some embodiments, the OD value (OD) of the crystalline portion of the microcrystalline glass article with a thickness of 0.3 mm at a wavelength of 550 nm is... 550nm，0.3mm The range 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, etc., as well as all ranges and subranges between the above values. It should be understood that, in the implementation scheme, any of the above ranges can be combined with any other range.

[0097] 8) In some embodiments, the drop ball test height I of the amorphous portion of the glass-ceramic article is 200 mm or more, preferably 300 mm or more, more preferably 400 mm, and even more preferably 450 mm to 600 mm. In some embodiments, the drop ball test height I of the amorphous portion of the glass-ceramic article can be 200 mm, 250 mm, 300 mm, 350 mm, 400 mm, 450 mm, 500 mm, 550 mm, 600 mm, etc., as well as all ranges and sub-ranges between the above values. It should be understood that, in embodiments, any of the above ranges can be combined with any other range.

[0098] 9) In some embodiments, the drop ball test height II of the crystalline portion of the glass-ceramic article is 300 mm or more, preferably 400 mm or more, more preferably 500 mm or more, and even more preferably 600 mm to 800 mm. In some embodiments, the drop ball test height II of the crystalline portion of the glass-ceramic article can be 300 mm, 350 mm, 400 mm, 450 mm, 500 mm, 550 mm, 600 mm, 650 mm, 700 mm, 750 mm, 800 mm, etc., as well as all ranges and sub-ranges between the above values. It should be understood that, in embodiments, any of the above ranges can be combined with any other range.

[0099] [Manufacturing methods for photosensitive glass, glass-ceramic, and glass-ceramic products]

[0100] The photosensitive glass, microcrystalline glass, and microcrystalline glass products of the present invention can be produced and manufactured by the following methods:

[0101] The manufacturing method of photosensitive glass includes the following steps:

[0102] Weigh the raw materials according to the glass component ratio and mix them evenly. The raw materials include, but are not limited to, oxides, hydroxides, and complex salts (such as carbonates, nitrates, sulfates, etc.) of the components. Place the uniformly mixed raw materials into a platinum or quartz crucible and melt, clarify, and homogenize them at 1450-1600℃, then cool them down. Pour the molten glass into a metal mold preheated to about 200-500℃ to form the glass, and circulate cooling air to ensure that the glass does not crystallize. Place the formed glass and the metal mold together in an annealing furnace for heat preservation and annealing, and then turn off the power and cool it with the furnace to obtain photosensitive glass.

[0103] The manufacturing method of glass-ceramic includes the following steps:

[0104] Photosensitive glass is formed according to the above-described manufacturing method. The photosensitive glass is then processed through a crystallization process to obtain the microcrystalline glass of this invention. Alternatively, the photosensitive glass can be processed into a glass mold of a specific shape and then processed through a crystallization process to obtain the microcrystalline glass of this invention. The method for processing the glass mold into a specific shape includes methods known to those skilled in the art, such as hot pressing, grinding, or polishing. The crystallization process of this invention includes exposure treatment and crystallization heat treatment of the photosensitive glass or glass mold. The exposure treatment can be mask exposure or laser direct writing exposure treatment. The exposure light source is ultraviolet light, preferably with a wavelength of 300nm to 350nm, more preferably with a wavelength of 300nm to 330nm. The exposure time is preferably 5 minutes to 60 minutes, and the light power density is preferably 0.5mW / cm². 2 ~20.0mW / cm 2In some embodiments, the ultraviolet light wavelength can be 300nm, 301nm, 302nm, 303nm, 304nm, 305nm, 306nm, 307nm, 308nm, 309nm, 310nm, 311nm, 312nm, 313nm, 314nm, 315nm, 316nm, 317nm, 318nm, 319nm, 320nm, 321nm, 322nm, 323nm, 324nm, or 325nm. The ranges are m, 326nm, 327nm, 328nm, 329nm, 330nm, 331nm, 332nm, 333nm, 334nm, 335nm, 336nm, 337nm, 338nm, 339nm, 340nm, 341nm, 342nm, 343nm, 344nm, 345nm, 346nm, 347nm, 348nm, 349nm, 350nm, etc., as well as all ranges and sub-ranges between the above values. It should be understood that, in the implementation scheme, any of the above ranges can be combined with any other range. In some embodiments, the ultraviolet exposure time can be 5 minutes, 7 minutes, 10 minutes, 13 minutes, 15 minutes, 17 minutes, 20 minutes, 23 minutes, 25 minutes, 27 minutes, 30 minutes, 33 minutes, 35 minutes, 37 minutes, 40 minutes, 43 minutes, 45 minutes, 47 minutes, 50 minutes, 53 minutes, 55 minutes, 57 minutes, 60 minutes, etc., as well as all ranges and sub-ranges between the above values. It should be understood that, in embodiments, any of the above ranges can be combined with any other range. In some embodiments, the optical power density can be 0.5 mW / cm². 2 1.0mW / cm 2 1.5mW / cm 2 2.0mW / cm 2 2.5mW / cm 2 3.0mW / cm 2 3.5mW / cm 2 4.0mW / cm 2 4.5mW / cm 2 5.0mW / cm 2 5.5mW / cm 2 6.0mW / cm 2 6.5mW / cm 2 7.0mW / cm 2 7.5mW / cm 2 8.0mW / cm 2 8.5mW / cm 2 9.0mW / cm 2 9.5mW / cm 2 10.0mW / cm2 、10.5mW / cm 2 、11.0mW / cm 2 、11.5mW / cm 2 、12.0mW / cm 2 、12.5mW / cm 2 、13.0mW / cm 2 、13.5mW / cm 2 、14.0mW / cm 2 、14.5mW / cm 2 、15.0mW / cm 2 、15.5mW / cm 2 、16.0mW / cm 2 、16.5mW / cm 2 、17.0mW / cm 2 、17.5mW / cm 2 、18.0mW / cm 2 、18.5mW / cm 2 、19.0mW / cm 2 、19.5mW / cm 2 、20mW / cm 2And so on, as well as all ranges and subranges between the above values. It should be understood that, in the implementation, any of the above ranges can be combined with any other range. The mask exposure process described in this invention refers to exposure at a specific location or area of ​​the photosensitive glass, and a dedicated photomask pattern can be formulated according to application needs. The exposed glass is then subjected to crystallization heat treatment, which can be performed in one stage or in two stages, preferably in two stages. The two-stage crystallization heat treatment refers to performing a nucleation process at a first temperature, and then performing a crystal growth process at a second temperature higher than the nucleation process temperature. Preferably, the first temperature is 490℃~520℃, and the first temperature treatment time is 1 hour to 5 hours. Preferably, the second temperature is 540℃~650℃, and the second temperature treatment time is 2 hours to 8 hours. In some embodiments, the first temperature can be 490°C, 493°C, 495°C, 497°C, 500°C, 503°C, 505°C, 507°C, 510°C, 513°C, 515°C, 517°C, 520°C, etc., as well as all ranges and sub-ranges between the above values. It should be understood that, in embodiments, any of the above ranges can be combined with any other range. In some embodiments, the first temperature processing time can be 1 hour, 1.5 hours, 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, 4.5 hours, 5 hours, etc., as well as all ranges and sub-ranges between the above values. It should be understood that, in embodiments, any of the above ranges can be combined with any other range. In some embodiments, the second temperature can be 540°C, 545°C, 550°C, 555°C, 560°C, 565°C, 570°C, 575°C, 580°C, 585°C, 590°C, 595°C, 600°C, 605°C, 610°C, 615°C, 620°C, 625°C, 630°C, 635°C, 640°C, 645°C, 650°C, etc., as well as all ranges and sub-ranges between the above values. It should be understood that, in embodiments, any of the above ranges can be combined with any other range. In some embodiments, the second temperature processing time can be 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, 4.5 hours, 5 hours, 5.5 hours, 6 hours, 6.5 hours, 7 hours, 7.5 hours, 8 hours, etc., as well as all ranges and sub-ranges between the above values. It should be understood that, in embodiments, any of the above ranges can be combined with any other range. After the photosensitive glass undergoes the above-mentioned exposure treatment and crystallization heat treatment, it becomes a microcrystalline glass. The exposed part of the microcrystalline glass generates crystals to form a crystalline part, while the unexposed part does not generate crystals and forms an amorphous part. Preferably, the crystals generated in the exposed part of the microcrystalline glass are lithium metasilicate.

[0105] The manufacturing method of microcrystalline glass products includes the following steps:

[0106] Microcrystalline glass is obtained according to the above-described manufacturing method. Then, the microcrystalline glass is treated with a chemical strengthening process, or it is processed into microcrystalline glass components of a specific shape and then treated with a chemical strengthening process to obtain the microcrystalline glass product of this invention. The methods for processing the microcrystalline glass into specific shapes include methods known to those skilled in the art, such as hot pressing, grinding, or polishing.

[0107] The chemical strengthening method described in this invention is ion exchange. During ion exchange, smaller metal ions in the glass-ceramic are replaced or "exchanged" by larger metal ions with the same valence state located nearby. The replacement of smaller ions with larger ions creates compressive stress within the glass-ceramic, forming a compressive stress layer.

[0108] In some embodiments, the metal ion is a monovalent alkali metal ion (e.g., Na+). + K + 、Rb + Cs + Ion exchange is carried out by immersing a glass-ceramic glass in a salt bath containing at least one molten salt containing larger metal ions, which replace smaller metal ions in the glass-ceramic glass. Alternatively, other monovalent metal ions such as Ag can be used. + 、Tl + Cu + It can also be used to exchange monovalent ions. One or more ion exchange processes used for chemical microcrystalline glass products may include, but are not limited to: immersing them in a single salt bath, or immersing them in multiple salt baths having the same or different compositions, with washing and / or annealing steps added between immersions.

[0109] In some embodiments, the microcrystalline glass can be ion-exchanged by immersion in a salt bath of molten Na salt (such as NaNO3) and / or K salt (such as KNO3), and / or a mixed Na and K salt at a temperature of 350°C to 470°C for 1 hour to 36 hours, preferably at a temperature of 380°C to 460°C, and preferably for a time of 2 hours to 24 hours. In some embodiments, the chemical strengthening temperature can be 350°C, 355°C, 360°C, 365°C, 370°C, 375°C, 380°C, 385°C, 390°C, 395°C, 400°C, 405°C, 410°C, 415°C, 420°C, 425°C, 430°C, 435°C, 440°C, 445°C, 450°C, 455°C, 460°C, 465°C, 470°C, etc., as well as all ranges and subranges between the above values. It should be understood that, in the implementation scheme, any of the above ranges can be combined with any other range. In some implementation schemes, the chemical fortification time can be 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours, 12 hours, 13 hours, 14 hours, 15 hours, 16 hours, 17 hours, 18 hours, 19 hours, 20 hours, 21 hours, 22 hours, 23 hours, 24 hours, 25 hours, 26 hours, 27 hours, 28 hours, 29 hours, 30 hours, 31 hours, 32 hours, 33 hours, 34 hours, 35 hours, 36 hours, etc., as well as all ranges and sub-ranges between the above values. It should be understood that, in the implementation scheme, any of the above ranges can be combined with any other range.

[0110] In some embodiments, the photosensitive glass of the present invention can be manufactured into reinforced glass through the above-described chemical strengthening process, and then processed into microcrystalline glass products through the above-described crystallization process. In some embodiments, the photosensitive glass of the present invention can be processed into glass elements, and then the glass elements can be manufactured into reinforced glass through the above-described chemical strengthening process, and then processed into microcrystalline glass products through the above-described crystallization process.

[0111] [Glass components]

[0112] Due to the superior properties described above, the photosensitive glass, microcrystalline glass, and microcrystalline glass products of this invention can be widely used in the manufacture of various glass components. For example, they can be used to manufacture optical lenses (such as spherical or aspherical concave meniscus lenses, convex meniscus lenses, biconvex lenses, biconcave lenses, plano-convex lenses, plano-concave lenses, etc.), prisms, and other glass components; and they can be used to manufacture glass cover plates, glass carrier plates, and other glass components.

[0113] [equipment]

[0114] The photosensitive glass, microcrystalline glass, microcrystalline glass products, and glass components of the present invention can be widely used in various devices, including but not limited to electronic devices, imaging devices, medical devices, decorations or handicrafts, such as mobile phones, smart wearable devices (such as watches), computers, security monitoring, vehicle-mounted devices, biomedical testing equipment, etc.

[0115] Example

[0116] To further clarify and illustrate the technical solution of the present invention, the following non-limiting embodiments are provided. While the embodiments of the present invention have made considerable efforts to ensure numerical accuracy, some errors and deviations must be taken into account.

[0117] <Example of Photosensitive Glass>

[0118] In this embodiment, photosensitive glasses 1# to 20# with the compositions shown in Tables 1 to 3 were obtained using the above-described manufacturing method for photosensitive glass. Furthermore, the characteristics of each photosensitive glass were measured using the testing method described in this invention, and the measurement results are shown in Tables 1 to 3. In the following embodiments, the light transmittance of the photosensitive glass was tested using a sample with a thickness of 1 mm ± 0.1 mm.

[0119] Table 1.

[0120]

[0121] Table 2.

[0122]

[0123] Table 3.

[0124]

[0125] <Examples of Microcrystalline Glass>

[0126] This embodiment uses the photosensitive glass examples 1# to 20# as raw materials, and sequentially obtains microcrystalline glass examples 1#' to 20#' using the aforementioned microcrystalline glass manufacturing method. The characteristics of each microcrystalline glass are measured using the testing method described in this invention, and the measurement results are shown in Tables 4 to 6. Since no component changes are involved in the manufacturing process of microcrystalline glass from photosensitive glass, the components and their contents of the microcrystalline glass are the same as or substantially the same as those of the photosensitive glass; the amorphous portion of the microcrystalline glass... d v d T 550nm Compared to photosensitive glass, the change is much smaller and can be almost ignored. In the following examples, the light transmittance of the microcrystalline glass was tested using a sample with a thickness of 1 mm ± 0.1 mm.

[0127] Table 4.

[0128]

[0129] Table 5.

[0130]

[0131] Table 6.

[0132]

[0133] <Examples of Microcrystalline Glass Products>

[0134] This embodiment uses the aforementioned microcrystalline glass examples 1#' to 20#' as raw materials, and sequentially obtains microcrystalline glass products examples 1#' to 20#' using the aforementioned microcrystalline glass product manufacturing method. The characteristics of each microcrystalline glass product are measured using the aforementioned testing method, and the results are shown in Tables 7 to 9. During the manufacturing process of microcrystalline glass products, the weight percentage variation of each oxide component in the overall composition of the microcrystalline glass product is small and almost negligible. Therefore, the components and their contents of the microcrystalline glass products are the same as or substantially the same as the components and their contents of the microcrystalline glass. The amorphous portion of the microcrystalline glass product... d v d T 550nm OD of the crystallized part of microcrystalline glass products 550nm，0.7mm OD 550nm，0.3mm T 870nm T 1500nm Compared to microcrystalline glass, the variation is small and can be almost ignored.

[0135] Table 7.

[0136]

[0137] Table 8.

[0138]

[0139] Table 9.

[0140]

[0141] The technical features of the above embodiments can be combined in any way. For the sake of brevity, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0142] The embodiments described above are merely illustrative of several implementation methods of this application, intended to facilitate a detailed understanding of the technical solutions of this application, but should not be construed as limiting the scope of protection of the patent application. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of this application, and these all fall within the scope of protection of this application. It should be understood that technical solutions obtained by those skilled in the art based on the technical solutions provided in this application through logical analysis, reasoning, or limited experimentation are all within the scope of protection of the appended claims. Therefore, the scope of protection of this patent application should be determined by the content of the appended claims, and the specification can be used to interpret the content of the claims.

Claims

1. A microcrystalline glass, characterized in that, Its components, expressed as a percentage by weight, contain: SiO2+Li2O: 45%~75%; La2O3+Y2O3: 11%~50%; Al2O3: 1%~8%; Ag2O: 0.05%~1%; CeO2: 0.01%~1%, of which (La2O3+Y2O3) / (Ag2O+CeO2) is 40.0~120.

0.

2. The microcrystalline glass according to claim 1, characterized in that, Its components, expressed as a percentage by weight, also include: ZrO2: 0–5%; and / or Sb2O3: 0–1%; and / or K2O: 0–5%; and / or Na2O: 0–5%.

3. A microcrystalline glass, characterized in that, Its composition includes SiO2, Li2O, Al2O3, Ag2O, and CeO2. By weight percentage, it contains 11%–50% La2O3+Y2O3, where (La2O3+Y2O3) / (Ag2O+CeO2) is 40.0–120.

0. The microcrystalline glass comprises one or more crystalline portions and one or more amorphous portions. The crystalline portions contain crystalline phases, while the amorphous portions do not. The refractive index n of the amorphous portion of the microcrystalline glass is... d The transmittance T of the amorphous portion of a microcrystalline glass with a thickness of 0.3 mm to 1.5 mm and a diameter of 1.55–1.70 nm at a wavelength of 550 nm. 550nm The transmittance T of the crystalline portion of a 0.3mm–1.5mm thick microcrystalline glass at a wavelength of 870nm is above 87.0%. 870nm It is below 10.0%.

4. The microcrystalline glass according to claim 3, characterized in that, Its components, expressed as a percentage by weight, contain: SiO2+Li2O: 45%–75%; and / or Al2O3: 1%–8%; and / or Ag2O: 0.05%–1%; and / or CeO2: 0.01%–1%; and / or ZrO2: 0–5%; and / or Sb2O3: 0–1%; and / or K2O: 0–5%; and / or Na2O: 0–5%.

5. The microcrystalline glass according to any one of claims 1 to 4, characterized in that, Its components are expressed as weight percentages, wherein: (La2O3+Y2O3) / (Ag2O+CeO2) is 50.0-110.0, preferably (La2O3+Y2O3) / (Ag2O+CeO2) is 60.0-100.0; and / or (SiO2+Li2O) / (La2O3+Y2O3) is 1.0-6.0, preferably (SiO2+Li2O) / (La2O3+Y2O3) is 1.2-3.0, more preferably (SiO2+Li2O) / (La2O3+Y2O3) is 1.5-2.5; and / or (La2O3+Y2O3) / (Ag2O3+Y2O3) is 1.5-2.5; and / or (La2O3+Y2O3) / (Ag2O+CeO2 ... The ratio of (La2O3+Y2O3) / (Al2O3+ZrO2) is 1.0 to 18.0, preferably 2.0 to 12.0, more preferably 3.5 to 7.0; and / or (La2O3+Y2O3) / (K2O+Na2O) is 2.0 to 20.0, preferably 4.0 to 15.0, more preferably 6.0 to 11.

0.

6. The microcrystalline glass according to any one of claims 1 to 4, characterized in that, Its components are expressed as a weight percentage, wherein: SiO2 / Li2O is 4.0 to 8.0, preferably 5.5 to 8.0, more preferably 6.0 to 7.5; and / or (SiO2+Li2O) / (K2O+Na2O) is 8.0 to 30.0, preferably 10.0 to 25.0, more preferably 12.0 to 20.0; and / or Ag2O / CeO2 is 1.0 to 5.0, preferably 1.5 to 4.0, more preferably 2.0 to 3.

0.

7. The microcrystalline glass according to any one of claims 1 to 4, characterized in that, Its components are expressed as weight percentages, wherein: SiO2+Li2O: 50%–70%, preferably SiO2+Li2O: 55%–69%; and / or La2O3+Y2O3: 20%–45%, preferably La2O3+Y2O3: 25%–40%; and / or Al2O3: 2%–6%, preferably Al2O3: 2.5%–4.8%; and / or Ag2O: 0.05%–0.8%, preferably Ag2O: 0.1%–0.8%. 5%; and / or CeO2: 0.03%–0.5%, preferably CeO2: 0.05%–0.2%; and / or ZrO2: 0.5%–4%, preferably ZrO2: 1%–3%; and / or Sb2O3: 0.2%–0.8%, preferably Sb2O3: 0.3%–0.6%; and / or K2O: 0.5%–4%, preferably K2O: 1%–3%; and / or Na2O: 0.5%–4%, preferably Na2O: 1%–3%.

8. The microcrystalline glass according to any one of claims 1 to 4, characterized in that, Its components are expressed as weight percentages, wherein: SiO2: 35%–64%, preferably SiO2: 40%–60%, more preferably SiO2: 45%–58%; and / or Li2O: 5.5%–13%, preferably Li2O: 6%–12%, more preferably Li2O: 7%–10%; and / or La2O3: 0%–30%, preferably La2O3: 6%–28%, more preferably La2O3: 10%–25%; and / or Y2O3: 0%–25%, preferably Y2O3: 6%–22%, more preferably Y2O3: 10%–20%.

9. The microcrystalline glass according to any one of claims 1 to 4, characterized in that, The glass-ceramic comprises one or more crystalline portions and one or more amorphous portions. The crystalline portions contain a crystalline phase, and the amorphous portions do not contain a crystalline phase. Preferably, the crystalline portions contain a lithium metasilicate crystalline phase. More preferably, the lithium metasilicate crystalline phase accounts for 5% to 40% of the weight percentage of the crystalline portions of the glass-ceramic, even more preferably 10% to 35%, and still more preferably 10% to 30%.

10. The microcrystalline glass according to claim 9, characterized in that, The refractive index n of the amorphous portion of the microcrystalline glass d The dispersion coefficient ν of the amorphous portion of the glass-ceramic is 1.55 to 1.70, preferably 1.57 to 1.68, more preferably 1.58 to 1.65; and / or the dispersion coefficient ν of the amorphous portion of the glass-ceramic. d The transmittance T of the amorphous portion of the 0.3 mm to 1.5 mm thick glass-ceramic at a wavelength of 550 nm is 52.00 to 62.00, preferably 53.00 to 60.00, more preferably 55.00 to 58.00; and / or the transmittance T of the amorphous portion of the glass-ceramic at a wavelength of 550 nm. 550nm The transmittance T of the crystalline portion of a 0.3 mm to 1.5 mm thick microcrystalline glass at a wavelength of 870 nm is 87.0% or more, preferably 88.0% or more, and more preferably 89.5% or more; and / or the transmittance T of the crystalline portion of the microcrystalline glass at a wavelength of 870 nm. 870nm The transmittance T of the crystalline portion of a 0.3 mm to 1.5 mm thick microcrystalline glass at a wavelength of 1500 nm is 10.0% or less, preferably 5.0% or less, more preferably 3.0% or less, and even more preferably 2.0% or less; and / or the transmittance T of the crystalline portion of the microcrystalline glass at a wavelength of 1500 nm. 1500nm The content is 50.0% or less, preferably 30.0% or less, more preferably 20.0% or less, and even more preferably 10.0% or less; and / or the OD value of the crystalline portion of the microcrystalline glass with a thickness of 0.7 mm at a wavelength of 550 nm. 550nm，0.7mm The OD value is 3.0 to 7.0, preferably 4.0 to 6.0, more preferably 4.5 to 5.5; and / or the OD value of the crystalline portion of the microcrystalline glass with a thickness of 0.3 mm at a wavelength of 550 nm. 550nm，0.3mm The value is 1.0 to 5.0, preferably 2.0 to 4.0, and more preferably 2.5 to 3.

5.

11. A microcrystalline glass product, characterized in that, Its components, expressed as a percentage by weight, contain: SiO2+Li2O: 45%~75%; La2O3+Y2O3: 11%~50%; Al2O3: 1%~8%; Ag2O: 0.05%~1%; CeO2: 0.01%~1%, of which (La2O3+Y2O3) / (Ag2O+CeO2) is 40.0~120.

0.

12. The microcrystalline glass article according to claim 11, characterized in that, Its components, expressed as a percentage by weight, also include: ZrO2: 0–5%; and / or Sb2O3: 0–1%; and / or K2O: 0–5%; and / or Na2O: 0–5%.

13. A microcrystalline glass product, characterized in that, Its composition includes SiO2, Li2O, Al2O3, Ag2O, and CeO2, and by weight percentage contains 11% to 50% La2O3 + Y2O3, wherein the ratio of (La2O3 + Y2O3) to (Ag2O + CeO2) is 40.0 to 120.

0. The microcrystalline glass product comprises one or more crystalline portions and one or more amorphous portions. The crystalline portions contain crystalline phases, and the amorphous portions do not contain crystalline phases. The refractive index n of the amorphous portion of the microcrystalline glass product is... d The transmittance T of the amorphous portion of a microcrystalline glass product with a thickness of 0.3 mm to 1.5 mm and a diameter of 1.55–1.70 nm at a wavelength of 550 nm. 550nm The transmittance T of the crystalline portion of microcrystalline glass products with a thickness of 0.3 mm to 1.5 mm at a wavelength of 870 nm is above 87.0%. 870nm It is below 10.0%.

14. The microcrystalline glass article according to claim 13, characterized in that, Its components, expressed as a percentage by weight, contain: SiO2+Li2O: 45%–75%; and / or Al2O3: 1%–8%; and / or Ag2O: 0.05%–1%; and / or CeO2: 0.01%–1%; and / or ZrO2: 0–5%; and / or Sb2O3: 0–1%; and / or K2O: 0–5%; and / or Na2O: 0–5%.

15. The microcrystalline glass article according to any one of claims 11 to 14, characterized in that, Its components are expressed as weight percentages, wherein: (La2O3+Y2O3) / (Ag2O+CeO2) is 50.0-110.0, preferably (La2O3+Y2O3) / (Ag2O+CeO2) is 60.0-100.0; and / or (SiO2+Li2O) / (La2O3+Y2O3) is 1.0-6.0, preferably (SiO2+Li2O) / (La2O3+Y2O3) is 1.2-3.0, more preferably (SiO2+Li2O) / (La2O3+Y2O3) is 1.5-2.5; and / or (La2O3+Y2O3) / (Ag2O3+Y2O3) is 1.5-2.5; and / or (La2O3+Y2O3) / (Ag2O+CeO2 ... The ratio of (La2O3+Y2O3) / (Al2O3+ZrO2) is 1.0 to 18.0, preferably 2.0 to 12.0, more preferably 3.5 to 7.0; and / or (La2O3+Y2O3) / (K2O+Na2O) is 2.0 to 20.0, preferably 4.0 to 15.0, more preferably 6.0 to 11.

0.

16. The microcrystalline glass article according to any one of claims 11 to 14, characterized in that, Its components are expressed as a weight percentage, wherein: SiO2 / Li2O is 4.0 to 8.0, preferably 5.5 to 8.0, more preferably 6.0 to 7.5; and / or (SiO2+Li2O) / (K2O+Na2O) is 8.0 to 30.0, preferably 10.0 to 25.0, more preferably 12.0 to 20.0; and / or Ag2O / CeO2 is 1.0 to 5.0, preferably 1.5 to 4.0, more preferably 2.0 to 3.

0.

17. The microcrystalline glass article according to any one of claims 11 to 14, characterized in that, Its components are expressed as weight percentages, wherein: SiO2+Li2O: 50%–70%, preferably SiO2+Li2O: 55%–69%; and / or La2O3+Y2O3: 20%–45%, preferably La2O3+Y2O3: 25%–40%; and / or Al2O3: 2%–6%, preferably Al2O3: 2.5%–4.8%; and / or Ag2O: 0.05%–0.8%, preferably Ag2O: 0.1%–0.8%. 5%; and / or CeO2: 0.03%–0.5%, preferably CeO2: 0.05%–0.2%; and / or ZrO2: 0.5%–4%, preferably ZrO2: 1%–3%; and / or Sb2O3: 0.2%–0.8%, preferably Sb2O3: 0.3%–0.6%; and / or K2O: 0.5%–4%, preferably K2O: 1%–3%; and / or Na2O: 0.5%–4%, preferably Na2O: 1%–3%.

18. The microcrystalline glass article according to any one of claims 11 to 14, characterized in that, Its components are expressed as weight percentages, wherein: SiO2: 35%–64%, preferably SiO2: 40%–60%, more preferably SiO2: 45%–58%; and / or Li2O: 5.5%–13%, preferably Li2O: 6%–12%, more preferably Li2O: 7%–10%; and / or La2O3: 0%–30%, preferably La2O3: 6%–28%, more preferably La2O3: 10%–25%; and / or Y2O3: 0%–25%, preferably Y2O3: 6%–22%, more preferably Y2O3: 10%–20%.

19. The microcrystalline glass article according to any one of claims 11 to 14, characterized in that, The microcrystalline glass product comprises one or more crystalline portions and one or more amorphous portions. The crystalline portions contain a crystalline phase, and the amorphous portions do not contain a crystalline phase. Preferably, the crystalline portions contain a lithium metasilicate crystalline phase. More preferably, the lithium metasilicate crystalline phase accounts for 5% to 40% of the weight percentage of the crystalline portion of the microcrystalline glass product. More preferably, it accounts for 10% to 35%, and even more preferably, it accounts for 10% to 30%.

20. The microcrystalline glass article according to claim 19, characterized in that, The refractive index n of the amorphous portion of the microcrystalline glass product d The dispersion coefficient ν of the amorphous portion of the glass-ceramic article is 1.55 to 1.70, preferably 1.57 to 1.68, more preferably 1.58 to 1.65; and / or the dispersion coefficient ν of the amorphous portion of the glass-ceramic article. d The transmittance T of the amorphous portion of a 0.3 mm to 1.5 mm thick microcrystalline glass article at a wavelength of 550 nm is 52.00 to 62.00, preferably 53.00 to 60.00, more preferably 55.00 to 58.00; and / or the transmittance T of the amorphous portion of the microcrystalline glass article at a wavelength of 550 nm. 550nm The transmittance is 87.0% or more, preferably 88.0% or more, more preferably 89.5% or more; and / or the drop ball test height I of the amorphous portion of the microcrystalline glass article is 200 mm or more, preferably 300 mm or more, more preferably 400 mm, and even more preferably 450 mm to 600 mm; and / or the transmittance T of the crystalline portion of the microcrystalline glass article with a thickness of 0.3 mm to 1.5 mm at a wavelength of 870 nm. 870nm The transmittance T of the crystalline portion of a 0.3 mm to 1.5 mm thick microcrystalline glass article at a wavelength of 1500 nm is 10.0% or less, preferably 5.0% or less, more preferably 3.0% or less, and even more preferably 2.0% or less; and / or the transmittance T of the crystalline portion of the microcrystalline glass article is 1500 nm or less. 1500nm The content is 50.0% or less, preferably 30.0% or less, more preferably 20.0% or less, and even more preferably 10.0% or less; and / or the OD value of the crystalline portion of the microcrystalline glass article with a thickness of 0.7 mm at a wavelength of 550 nm. 550nm，0.7mm The OD value is 3.0 to 7.0, preferably 4.0 to 6.0, more preferably 4.5 to 5.5; and / or the OD value of the crystalline portion of a microcrystalline glass article with a thickness of 0.3 mm at a wavelength of 550 nm. 550nm，0.3mm The value is 1.0 to 5.0, preferably 2.0 to 4.0, more preferably 2.5 to 3.5; and / or the drop ball test height II of the crystal portion of the microcrystalline glass product is 300 mm or more, preferably 400 mm or more, more preferably 500 mm or more, and even more preferably 600 mm to 800 mm.

21. Photosensitive glass, characterized in that, Its components, expressed as a percentage by weight, contain: SiO2+Li2O: 45%~75%; La2O3+Y2O3: 11%~50%; Al2O3: 1%~8%; Ag2O: 0.05%~1%; CeO2: 0.01%~1%, of which (La2O3+Y2O3) / (Ag2O+CeO2) is 40.0~120.

0.

22. The photosensitive glass according to claim 21, characterized in that, Its components, expressed as a percentage by weight, also include: ZrO2: 0–5%; and / or Sb2O3: 0–1%; and / or K2O: 0–5%; and / or Na2O: 0–5%.

23. The photosensitive glass according to claim 21 or 22, characterized in that, Its components are expressed as weight percentages, wherein: (La2O3+Y2O3) / (Ag2O+CeO2) is 50.0-110.0, preferably (La2O3+Y2O3) / (Ag2O+CeO2) is 60.0-100.0; and / or (SiO2+Li2O) / (La2O3+Y2O3) is 1.0-6.0, preferably (SiO2+Li2O) / (La2O3+Y2O3) is 1.2-3.0, more preferably (SiO2+Li2O) / (La2O3+Y2O3) is 1.5-2.5; and / or (La2O3+Y2O3) / (Ag2O3+Y2O3) is 1.5-2.5; and / or (La2O3+Y2O3) / (Ag2O+CeO2 ... The ratio of (La2O3+Y2O3) / (Al2O3+ZrO2) is 1.0 to 18.0, preferably 2.0 to 12.0, more preferably 3.5 to 7.0; and / or (La2O3+Y2O3) / (K2O+Na2O) is 2.0 to 20.0, preferably 4.0 to 15.0, more preferably 6.0 to 11.

0.

24. The photosensitive glass according to claim 21 or 22, characterized in that, Its components are expressed as a weight percentage, wherein: SiO2 / Li2O is 4.0 to 8.0, preferably 5.5 to 8.0, more preferably 6.0 to 7.5; and / or (SiO2+Li2O) / (K2O+Na2O) is 8.0 to 30.0, preferably 10.0 to 25.0, more preferably 12.0 to 20.0; and / or Ag2O / CeO2 is 1.0 to 5.0, preferably 1.5 to 4.0, more preferably 2.0 to 3.

0.

25. The photosensitive glass according to claim 21 or 22, characterized in that, Its components are expressed as weight percentages, wherein: SiO2+Li2O: 50%–70%, preferably SiO2+Li2O: 55%–69%; and / or La2O3+Y2O3: 20%–45%, preferably La2O3+Y2O3: 25%–40%; and / or Al2O3: 2%–6%, preferably Al2O3: 2.5%–4.8%; and / or Ag2O: 0.05%–0.8%, preferably Ag2O: 0.1%–0.8%. 5%; and / or CeO2: 0.03%–0.5%, preferably CeO2: 0.05%–0.2%; and / or ZrO2: 0.5%–4%, preferably ZrO2: 1%–3%; and / or Sb2O3: 0.2%–0.8%, preferably Sb2O3: 0.3%–0.6%; and / or K2O: 0.5%–4%, preferably K2O: 1%–3%; and / or Na2O: 0.5%–4%, preferably Na2O: 1%–3%.

26. The photosensitive glass according to claim 21 or 22, characterized in that, Its components are expressed as weight percentages, wherein: SiO2: 35%–64%, preferably SiO2: 40%–60%, more preferably SiO2: 45%–58%; and / or Li2O: 5.5%–13%, preferably Li2O: 6%–12%, more preferably Li2O: 7%–10%; and / or La2O3: 0%–30%, preferably La2O3: 6%–28%, more preferably La2O3: 10%–25%; and / or Y2O3: 0%–25%, preferably Y2O3: 6%–22%, more preferably Y2O3: 10%–20%.

27. The photosensitive glass according to any one of claims 21 to 26, characterized in that, The refractive index n of the photosensitive glass d The value is 1.55 to 1.70, preferably 1.57 to 1.68, more preferably 1.58 to 1.65; and / or the dispersion coefficient v d The transmittance T of the photosensitive glass with a thickness of 0.3 mm to 1.5 mm at a wavelength of 550 nm is 52.00 to 62.00, preferably 53.00 to 60.00, more preferably 55.00 to 58.00; and / or the transmittance T of the photosensitive glass with a thickness of 0.3 mm to 1.5 mm at a wavelength of 550 nm. 550nm It is 87.0% or higher, preferably 88.0% or higher, and more preferably 89.5% or higher.

28. A glass element, characterized in that, It is made of the microcrystalline glass according to any one of claims 1 to 10, or the microcrystalline glass article according to any one of claims 11 to 20, or the photosensitive glass according to any one of claims 21 to 27.

29. A device, characterized in that, The product contains the microcrystalline glass according to any one of claims 1 to 10, and / or contains the microcrystalline glass article according to any one of claims 11 to 20, and / or contains the photosensitive glass according to any one of claims 21 to 27, and / or contains the glass element according to claim 28.

30. A method for manufacturing the microcrystalline glass according to any one of claims 1 to 10, characterized in that, The method includes the following steps: forming photosensitive glass, processing the photosensitive glass through a crystallization process to obtain microcrystalline glass, or processing the photosensitive glass into a glass mold and then processing it through a crystallization process to obtain microcrystalline glass.

31. The method for manufacturing microcrystalline glass according to claim 30, characterized in that, The crystallization process includes exposure treatment and crystallization heat treatment of the photosensitive glass or glass mold. The exposure treatment includes mask exposure or laser direct writing exposure treatment. The exposure light source is ultraviolet light, preferably with a wavelength of 300nm to 350nm, more preferably with a wavelength of 300nm to 330nm. The exposure time is 5 minutes to 60 minutes, and the optical power density is 0.5mW / cm². 2 ~20.0mW / cm 2 .

32. The method for manufacturing microcrystalline glass according to claim 31, characterized in that, The crystallization heat treatment includes a nucleation process at a first temperature and a crystal growth process at a second temperature higher than the nucleation process temperature. The first temperature is 490℃~520℃ and the treatment time at the first temperature is 1 hour~5 hours. The second temperature is 540℃~650℃ and the treatment time at the second temperature is 2 hours~8 hours.

33. The method for manufacturing the microcrystalline glass article according to any one of claims 11 to 20, characterized in that, The method includes the following steps: forming photosensitive glass, processing the photosensitive glass through a crystallization process to obtain microcrystalline glass, or processing the photosensitive glass into a glass mold and then processing it through a crystallization process to obtain microcrystalline glass, and then processing the microcrystalline glass through a chemical strengthening process to obtain microcrystalline glass products.

34. The method for manufacturing a microcrystalline glass article according to claim 33, characterized in that, The crystallization process includes exposure treatment and crystallization heat treatment of the photosensitive glass or glass mold. The exposure treatment includes mask exposure or laser direct writing exposure treatment. The exposure light source is ultraviolet light, preferably with a wavelength of 300nm to 350nm, more preferably with a wavelength of 300nm to 330nm. The exposure time is 5 minutes to 60 minutes, and the optical power density is 0.5mW / cm². 2 ~20.0mW / cm 2 .

35. The method for manufacturing a microcrystalline glass article according to claim 34, characterized in that, The crystallization heat treatment includes a nucleation process at a first temperature and a crystal growth process at a second temperature higher than the nucleation process temperature. The first temperature is 490℃~520℃ and the treatment time at the first temperature is 1 hour~5 hours. The second temperature is 540℃~650℃ and the treatment time at the second temperature is 2 hours~8 hours.

36. The method for manufacturing a microcrystalline glass article according to claim 33, characterized in that, The chemical strengthening process involves immersing the microcrystalline glass in a salt bath of molten Na salt, and / or K salt, and / or a mixture of Na and K salt at a temperature of 350°C to 470°C for 1 hour to 36 hours, preferably at a temperature of 380°C to 460°C, and preferably for a time of 2 hours to 24 hours.

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