METHOD OF FABRICATING AN ANTI-GLARE, STRENGTHENED, ANTI-MICROBIAL AND ANTIFINGERPRINT STRENGTHENED GLASS
20180141854 ยท 2018-05-24
Inventors
Cpc classification
C03C17/008
CHEMISTRY; METALLURGY
C03C2217/73
CHEMISTRY; METALLURGY
C03C21/005
CHEMISTRY; METALLURGY
C03C21/002
CHEMISTRY; METALLURGY
C03C17/42
CHEMISTRY; METALLURGY
International classification
C03C15/00
CHEMISTRY; METALLURGY
C03C21/00
CHEMISTRY; METALLURGY
C03C17/00
CHEMISTRY; METALLURGY
Abstract
The present invention provides a method of manufacturing a glass with anti-glare, strengthened, anti-microbial and anti-fingerprint capabilities. A glass substrate is provided with a target surface. Plural treatments are carried out, including: performing an anti-glare treatment upon the target surface by using a mixed acid solution; performing a strengthening treatment by using KNO.sub.3; performing an anti-microbial treatment by using a silver-containing fluid; and performing an anti-fingerprint treatment by forming a fluorocarbon siloxane layer on the target surface.
Claims
1. A method of manufacturing a glass with anti-glare, strengthened, anti-microbial and anti-fingerprint capabilities, comprising: providing a glass substrate with a target surface; performing an anti-glare treatment upon the target surface by using a mixed acid solution; performing a strengthening treatment by using KNO.sub.3; performing an anti-microbial treatment by using a silver-containing fluid; and performing an anti-fingerprint treatment by forming a fluorocarbon siloxane layer on the target surface.
2. The method of manufacturing a glass with anti-glare, strengthened, anti-microbial and anti-fingerprint capabilities according to claim 1, wherein the mixed acid solution in the anti-glare treatment does not comprise hydrofluoric acid (HF) until the use of mixed reaction to produce hydrofluoric acid.
3. The method of manufacturing a glass with anti-glare, strengthened, anti-microbial and anti-fingerprint capabilities according to claim 2, wherein the anti-glare treatment comprises using a fluorine surfactant.
4. The method of manufacturing a glass with anti-glare, strengthened, anti-microbial and anti-fingerprint capabilities according to claim 3, wherein a concentration of the fluorine surfactant is from 50 to 400 parts per million (ppm).
5. The method of manufacturing a glass with anti-glare, strengthened, anti-microbial and anti-fingerprint capabilities according to claim 1, wherein the anti-glare treatment is performed before the strengthening treatment.
6. The method of manufacturing a glass with anti-glare, strengthened, anti-microbial and anti-fingerprint capabilities according to claim 1, wherein the silver-containing fluid in the anti-microbial treatment comprises silver nitrate (AgNO.sub.3)/potassium nitrate (KNO.sub.3) molten salt.
7. The method of manufacturing a glass with anti-glare, strengthened, anti-microbial and anti-fingerprint capabilities according to claim 6, wherein a glass substrate silver ion exchange is performed by using the silver nitrate (AgNO.sub.3)/potassium nitrate (KNO.sub.3) molten salt in the anti-microbial treatment, wherein a concentration of the silver nitrate/potassium nitrate (AgNO.sub.3/KNO.sub.3) molten salt is 0.01% by weight.
8. The method of manufacturing a glass with anti-glare, strengthened, anti-microbial and anti-fingerprint capabilities according to claim 1, wherein the silver-containing fluid in the anti-microbial treatment comprises using a nano-silver-silicon oxide (AgSiO.sub.2) sol to form an anti-microbial coating on the target surface.
9. The method of manufacturing a glass with anti-glare, strengthened, anti-microbial and anti-fingerprint capabilities according to claim 8, wherein the nano-silver-silicon oxide (AgSiO.sub.2) sol comprises silver nitrate (AgNO.sub.3), formaldehyde, amine siloxane chelating agent and silicon dioxide (SiO.sub.2).
10. The method of manufacturing a glass with anti-glare, strengthened, anti-microbial and anti-fingerprint capabilities according to claim 1, wherein the anti-glare treatment is performed, and then the strengthening treatment is performed, followed by the anti-microbial treatment, and then the anti-fingerprint treatment.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
[0012]
[0013]
[0014]
DETAILED DESCRIPTION
[0015] To provide a better understanding of the presented invention to persons having skill in the art, preferred embodiments are described in detail following. The preferred embodiments of the present invention are illustrated in the accompanying drawings with numbered elements and the desired effects are achieved.
[0016] The present invention provides a glass with anti-glare, strengthened, anti-microbial and anti-fingerprint capabilities.
[0017] Step 400: providing a glass substrate with a target surface;
[0018] Step 402: performing an anti-glare treatment upon the target surface;
[0019] Step 404: performing a strengthening treatment upon the target surface;
[0020] Step 406: performing an anti-microbial treatment upon the target surface; the embodiments of this step includes:
[0021] Step 406A: performing an Ag.sup.+ infiltration anti-microbial treatment upon the target surface by using AgNO.sub.3 molten salt;
[0022] Step 406B: performing an anti-microbial treatment upon the target surface by using nano-silver-silicon oxide (AgSiO.sub.2) sol coating;
[0023] Step 408: performing an anti-fingerprint treatment upon the target surface.
[0024] For the purpose of describing in detail the manufacturing steps of the present invention; please refer to
[0025] In one embodiment, the glass substrate 300 is flat glass having a thickness of 0.5 to 6.0 millimeter (mm), and its main content is soda-lime glass or aluminum silicate glass, and may contain silicon oxide (SiO.sub.2), sodium oxide (Na.sub.2O), potassium oxide (K.sub.2O), Lithium oxide (Li.sub.2O), magnesium oxide (MgO), calcium oxide (CaO), boron oxide (B.sub.2O.sub.3), alumina (Al.sub.2O.sub.3), arsenic oxide (As.sub.2O.sub.3), zirconium oxide (ZrO.sub.2), titanium oxide (TiO.sub.2), tin oxide (SnO.sub.2), or cerium oxide (CeO.sub.2); preferable is silicon oxide (SiO.sub.2), sodium oxide (Na.sub.2O), boron oxide (B.sub.2O.sub.3), or alumina (Al.sub.2O.sub.3), but are not limited thereto.
[0026] In one embodiment, the glass substrate 300 contains a silicon oxide (SiO.sub.2) content of 66 mole %, an alumina (Al.sub.2O.sub.3) content of 10 mole %, a sodium oxide (Na.sub.2O) content of 14 mole %, a potassium oxide (K.sub.2O) content of 2.5 mole %, a magnesium oxide (MgO) content of 5.7 mole %, a calcium oxide (CaO) content of 0.6 mole %, a boron oxide (B.sub.2O.sub.3) content of 0.6 mole %.
[0027] Next, as shown in
[0028] Next, as shown in
[0029] Next, as shown in
[0030] In another embodiment, the resulting strengthened anti-glare glass surface 306 is optionally coated with a nano-silver-silicon oxide (AgSiO.sub.2) sol. As shown in
[0031] In another embodiment, an anti-microbial treatment (step 406A) of molten salt silver ion Ag.sup.+ diffusion is performed on the resulting strengthened anti-glare glass surface 306, followed by an anti-microbial treatment (step 406B) of AgSiO.sub.2 sol coating. The above two anti-microbial treatment examples are combined, for example, by performing a treatment with the mixed molten salt of AgNO.sub.3 and KNO.sub.3 to obtain a nano silver permeated anti-microbial surface 308, and then performing a treatment with the nano-silver-silicon oxide (AgSiO.sub.2) sol coating, thereby forming an anti-reflective and anti-microbial coating surface 310.
[0032] Next, as shown in
[0033] The anti-glare treatment, strengthening treatment, anti-microbial treatment and anti-fingerprint treatment may be performed upon the flat glass through the above steps. It should be noted that the aforementioned treatment techniques such as the anti-glare treatment 402, the strengthening treatment 404, the anti-microbial treatment 406A or 406B and anti-fingerprint treatment 408, the resulting multi-functional panel glass has different effects due to performing different anti-microbial treatments 406A or 406B. A glass with anti-reflective capability is obtained by forming an anti-microbial coating surface 310 by using nano-silver-silicon oxide (AgSiO.sub.2) sol, which can enhance the anti-glare effect. Then, the anti-fingerprint treatment is performed to obtain a multi-functional panel glass having the best effect.
[0034] During the anti-microbial treatment, the exchange of silver ions by using the molten salt of AgNO.sub.3 and KNO.sub.3 to obtain an anti-microbial surface 308 can be optionally performed, or an anti-microbial coating surface 310 can be optionally formed by using nano-silver-silicon oxide (AgSiO.sub.2) sol. A glass with a better anti-glare effect is obtained by forming the anti-microbial coating surface 310 by using nano-silver-silicon oxide (AgSiO.sub.2) sol, followed by performing an anti-fingerprint treatment to form an anti-fingerprint coating 312.
[0035] In the embodiments of the present invention, the lower cost processing steps are in the following order: anti-glare treatment 302, strengthening treatment 304, anti-microbial treatment 306, and anti-fingerprint treatment 312.
[0036] Hereinafter, embodiments and experiments of the present invention will be described to confirm the anti-glare, strengthened, anti-microbial and anti-fingerprint capability of glass substrates.
Example 1
[0037] A method of manufacturing a glass with anti-glare capability.
[0038] An anti-glare glass of example 1 is manufactured by performing a glass etched anti-glare roughening process with HF mixed acid. The formulation of HF mixed acid of the present invention has two characteristics: (1) if the concentration of any ingredient used in the formulation is 0, the ingredient may not be used. Therefore, hydrofluoric acid (HF) may not be used in the formulations 1 to 4 to make the process preparation and use safer; (2) a fluorine surfactant in a concentration of 100 ppm is added into the formulation of the HF mixed acid to manufacture an anti-glare rough surface layer having good quality and easy to control by performing a glass etching process. The formulations of HF mixed acid used in the present invention are listed in Table 1.
TABLE-US-00001 TABLE 1 formulation of HF mixed acid formulation ingredient 1 2 3 4 5 6 Hydrofluoric acid (49 wt %)% 0~5 0~5 0~5 3~5 4~6 sulfuric acid (98 wt %)% 15~35 10~20 10~15 0~5 hydrochloric acid (35 wt %)% 0~10 0~10 15~20 acetic acid % 5~20 5~15 5~10 0~5 ammonium fluoride (40%)% 10~35 5~15 0~10 0~5 3-5 3-5 sodium fluoride % 0~5 5~10 0~5 1 potassium fluoride % 0~5 0~5 0~5 ammonium sulfate % 0~5 0~5 0~5 potassium sulfate % 0~5 10~15 potassium bifluoride % 0~5 0~5 20~15 water % 5~70 10~80 15~80 10~55 70~84 68~82 fluorine surfactant ppm 100 100 100 100 100 100 propylene glycol % 0~5 0~5 0~5 0~5 10~20 10~20
[0039] An anti-glare glass having preferable quality is manufactured by performing an anti-glare glass etching process with the formulation 1 of HF mixed acid, wherein the formulation 1 includes sulfuric acid (98 wt %) 15-40%, acetic acid 5-20%, ammonium fluoride (40%) 10-40%, water 5-80% and fluorine surfactant 100400 ppm.
[0040] A method of manufacturing a glass with anti-glare and chemical strengthened capability.
[0041] A chemical strengthening treatment is performed by immersing a glass in the KNO.sub.3 as a raw material at a temperature of 400 to 450 C. for 3 to 6 hours to manufacture a glass with anti-glare, strengthened capabilities.
[0042] First, in order to confirm the effect of the strengthening treatment of the present invention, please refer to Table 2 and Table 3. Table 2 and Table 3 are the measurements of the production temperature, time test and glass strength of, respectively, two kinds of glass substrates: soda-lime glass and aluminum silicate glass, after immersing in the KNO.sub.3. The results are expressed in terms of two parameters: Compressed Strength (CS) and Depth of Layer (DoL). The unit of Compressed Strength (CS) is Mpa and the unit of Depth of Layer (DoL) is microns (m).
[0043] In the case of soda-lime glass, the general untreated soda-lime glass has strength of about 100 MPa. As shown in Table 2, after the chemical strengthening treatment with KNO.sub.3, the soda-lime glass has a Compressed Strength >400 MPa, Depth of Layer >8 m, confirmed that the chemical strengthening treatment of the present invention can effectively strengthen the soda-lime glass. Preferably, performing the chemical strengthening treatment at a temperature 425 C. for 3 hours can get better chemical effect of the soda-lime glass. In the case of aluminum silicate glass, the general untreated aluminum silicate glass has strength of about 100 MPa. As shown in Table 3, after the chemical strengthening treatment with KNO.sub.3, the aluminum silicate glass has a Compressed Strength >800 MPa, Depth of Layer >40 m, confirmed that the chemical strengthening treatment of the present invention can effectively strengthen the aluminum silicate glass. Preferably, performing the chemical strengthening treatment at a temperature 425 C. for 3 hours can get better chemical effect of the aluminum silicate glass.
TABLE-US-00002 TABLE 2 strength of soda-lime glass temperature 400 C. 425 C. 450 C. Compressed Depth of Compressed Depth of Compressed Depth of Strength Layer Strength Layer Strength Layer time (Mpa) (DoL) (Mpa) (DoL) (Mpa) (DoL) 1 Hr 550 50 4 2 700 50 6 2 650 50 8 2 2 Hr 500 50 6 2 700 50 8 2 650 50 12 2 3 Hr 450 50 8 2 600 50 10 2 500 50 14 2 4 Hr 450 50 9 2 650 50 12 2 500 50 17 2
TABLE-US-00003 TABLE 3 strength of aluminum silicate glass temperature 400 C. 425 C. 450 C. Compressed Depth of Compressed Depth of Compressed Depth of Strength Layer Strength Layer Strength Layer time (Mpa) (DoL) (Mpa) (DoL) (Mpa) (DoL) 1 Hr 750 50 14 2 900 50 20 2 900 50 26 2 2 Hr 700 50 20 2 900 50 27 2 850 50 35 2 3 Hr 700 50 25 2 900 50 33 2 850 50 43 2 4 Hr 700 50 28 2 900 50 37 2 850 50 50 2
[0044] A method of manufacturing a glass with anti-glare, strengthened and nano silver anti-microbial capability.
[0045] An anti-glare strengthened glass is immersed in the mixed molten salt of AgNO.sub.3 and KNO.sub.3 for 10-30 minutes to exchange silver ions, thereby forming a nano-silver anti-glare strengthened glass, wherein the AgNO.sub.3/KNO.sub.3 is used in an amount of 0.01-5.0 wt % and the process temperature is 350-425 C. An anti-microbial rate if the resulting glass with nano-silver anti-microbial, anti-glare and strengthened capabilities is 99.9%.
[0046] Optical and surface anti-glare quality measurement results of nano-silver anti-glare strengthened glass productions are shown in Table 4. The sample 1 and the sample 2 refer to two different components of the glass to perform sample manufacture and sample test. In the measured items, GLOSS is measured by BYK-4374 produced by BYK; reflectivity (% R) is measured by spectrophotometer (MCPD-3000) produced by Otsuka; transmittance (% T) and haze are measured by the NDH-5000 haze machine produced by Nippon Denshoku Industries Co. LTD; the image discrimination is measured by IQ-206085 produced by Rhopoint Co; the rough Ra, RPc, Rz and Rmax are measured by the SJ-1 produced by Mitutoyo Co., Ltd.
TABLE-US-00004 TABLE 4 anti-glare measurement of nano-silver anti- microbial anti-glare strengthened glass measured measured instrument items sample 1 sample 2 BYK-4374 GLOSS(GU) 86.2~96.8 107~115 MCPD-3000 % R 6.01% 6.19% NDH-5000 haze % T 91.8% 92.15% machine HAZE(%) 2.79% 2.31% Rhopoint, IQ-206085 DOI(%) 71.9~77.1 94.9~96.4 ROUGHNESS Ra (m) 0.16 0.107 SJ-410 RPc(cm) 327.87 408.16 Roughness meter Rz (m) 1.00 0.51
[0047] A method of manufacturing a glass with anti-glare, strengthened, nano silver anti-microbial and anti-fingerprint capabilities.
[0048] Nano-silver anti-microbial anti-glare strengthened glass coating is performed by using fluorocarbon ether siloxane (RO).sub.3Si(CH.sub.2).sub.3[O(CF.sub.2).sub.2].sub.nF or fluorosilicone (RO).sub.3Si(CH.sub.2).sub.3(C.sub.2F.sub.4).sub.nF as a raw material dissolved in ethanol (EtOH) solvent to obtain fluorosilicone solution in the concentration of 0.01 to 1.0 wt %, thereby manufacturing a glass with anti-glare, strengthened, anti-microbial and anti-fingerprint capabilities. The contact angle and wear resistance of the glass are measured to Measure the anti-microbial changes. The results are list in Table 5. If anti-microbial anti-glare strengthened glass coating is performed by using fluorocarbon ether siloxane (RO).sub.3Si(CH.sub.2).sub.3[O(CF.sub.2).sub.2].sub.nF dissolved in ethanol (EtOH) solvent in the concentration of 0.01 wt %, the water contact angle of the glass may be greater than 100 to make the glass have anti-fingerprint capability. The use of the concentration of 0.05 wt %, water contact angle of the glass may be greater than 110; the use of concentration of 0.5 wt %, water contact angle of the glass is up to 118. The anti-microbial capability of the glass is not reduced by fluorosilicone coating.
TABLE-US-00005 TABLE 5 measurement of water contact angle and anti-microbial capability of anti-glare anti-microbial anti-fingerprint strengthened glass anti-glare anti-microbial anti-fingerprint strengthened glass water contact angle anti-microbial rate Fluorocarbon Before After Before After compounds concentration coating coating coating coating fluorocarbon 0.01 wt % 20 101 99.9% 99.9% ether 0.02 wt % 20 107 99.9% 99.9% siloxane 0.05 wt % 20 110 99.9% 99.9% 0.10 wt % 20 115 99.9% 99.9% 0.20 wt % 20 115 99.9% 99.9% 0.50 wt % 20 118 99.9% 99.9% 1.00 wt % 20 118 99.9% 99.9% fluoro- 0.01 wt % 20 98 99.9% 99.9% silicone 0.02 wt % 20 102 99.9% 99.9% 0.05 wt % 20 105 99.9% 99.9% 0.10 wt % 20 105 99.9% 99.9% 0.20 wt % 20 108 99.9% 99.9% 0.50 wt % 20 108 99.9% 99.9% 1.00 wt % 20 110 99.9% 99.9%
Example 2
[0049] High efficiency anti-glare anti-microbial anti-fingerprint strengthened glass production.
[0050] A glass etched roughening process is performed by using HF mixed acid to manufacture an anti-glare glass. The quality of the anti-glare glass is shown in Table 1 and the anti-glare effects of anti-glare glass are shown in Table 2. The anti-glare glass of the present example is manufactured by using formula 1 of HF mixed acid.
[0051] A chemical strengthening treatment is performed by immersing the glass in the KNO.sub.3 at a temperature of 400 to 450 C. for 3 to 5 hours to manufacture a glass with anti-glare, strengthened capabilities.
[0052] First, nano-silver-silicon oxide (AgSiO.sub.2) sol is prepared. Next, an anti-glare strengthened glass optical coating is performed to manufacture a high efficiency anti-glare anti-microbial glass, wherein the thickness of the coating is , =550 nm. The formulations of the AgSiO.sub.2 sol are listed in Table 6. SiO.sub.2 mixed sol is produced by using nano-silver-silicon oxide sol with different formulations for hydrolysis condensation. A nano-silver anti-microbial coating is performed upon the anti-glare glass. The main components of the formulations are AgNO.sub.3, formaldehyde, amine siloxane chelating agent such as KBM-903 (3-aminopropyltriethoxysilane [(C.sub.2H.sub.5O).sub.3SiC.sub.3H.sub.6NH.sub.2] supplied by Shin-Etsu Co., Ltd., KBM-603 (N-2 aminoethyl-3-aminopropyltrimethoxysilane [(CH.sub.3O).sub.3SiC.sub.3H.sub.6NHC.sub.2H.sub.4NH.sub.2] with a tetraoxysilane. In order to manufacture a high efficiency anti-glare anti-microbial glass, the sol of formulation 2 is used to improve anti-glare effect, wherein the coating refractive index is 1.46.
TABLE-US-00006 TABLE 6 formulations of the AgSiO.sub.2 sol AgSiO.sub.2 sol Formulation 1 Formulation 2 Formulation 3 AgNO.sub.3 (mole) 0.1~1.0 0.1~1.0 0.1~1.0 formaldehyde (mole) 0.2~2.0 0.2~2.0 0.2~2.0 amine siloxane KBM-903(mole) 0.5~5.0 chelating agent KBM-603(mole) 0.5~5.0 0.5~5.0 SiO.sub.2 sol SiO2TiO.sub.2 sol (1:1) 10 mole SiO.sub.2 sol 10 mole 10 mole
[0053] A high efficiency anti-glare anti-microbial glass is manufactured by performing an anti-glare strengthened glass sol coating using the sol with formulation 2. The coating quality of the glass are measured and shown in Table 7. The anti-glare effects of the glass are great, wherein average reflectivity R is <5.0% invisible light, transmittance T is >87%, scattering rate A is >11%. The pencil hardness of the glass is up to 8H grade, CNS 13033 of the glass is A-level and CNS 13033 is B-level.
TABLE-US-00007 TABLE 7 quality measurement of high efficiency anti- glare anti-microbial strengthened glass measured measured measured back- items instruments ranges results ground value % R MCPD-300 380~780 nm 4.82% 550 nm 3.54% % T HITACHI 300~380 nm 46.99% 380~780 nm 87.82% 550 nm 88.27% A % 1-R %-T % 380~780 nm 9.03% 550 nm 9.32% pencil ASTM 765 g 8H hardness D3363-92A Acid and Acid 6Hr After 90% Before 89.74% alkali immersing immersing resistance Acid 24Hr After 89.19% Before 89.21% NDH- immersing immersing 5000 CNS 13033 level A-level alkali 6Hr After 87.42% Before 89.19% immersing immersing alkali 24Hr After 75.60% Before 88.04% immersing immersing CNS 13033 level B-level
[0054] Next, a high efficiency anti-glare anti-microbial anti-fingerprint strengthened glass is manufactured by performing a nano-silver anti-glare strengthened glass coating with fluorosilicone solution. The anti-glare effects of the glass are great and are shown in Table 8, for example, an average reflectance R=5.44% in visible light, transmittance T=92.75%, DOI=89.1%. The microscope shows transmitted image and reflection image.
TABLE-US-00008 TABLE 8 anti-glare effect of high efficiency anti-glare anti- microbial anti-fingerprint strengthened glass measured measured instruments items G/EAG/AB/AF BYK-4374 GLOSS (GU) 96.7~102 MCPD - 3000 % R 5.44% NDH-5000 % T 92.75% RHOPOINT DOI (%) 89.1% IQ-206085 Roughness meter Ra (m) 0.163 SJ-410 RPC/cm 268.46 RZ (m) 1.099 CAM-100 Water droplets angle 110 Digital scale Etching depth (m) 151~166
[0055]
[0056] In view of the above, the present invention provides a method of manufacturing a glass with anti-glare, strengthened, anti-microbial and anti-fingerprint capabilities. The glass of the present invention may be applied to any electronic product, for example on a display device, preferably on a touch display device.
[0057] Those skilled in the art will readily observe that numerous modifications and alterations of the device and method may be made while retaining the teachings of the invention. Accordingly, the above disclosure should be construed as limited only by the metes and bounds of the appended claims.