TW201228974A - Glass composition for chemical strengthening - Google Patents

Abstract

To provide a glass composition which has excellent heat resistance and excellent ion exchange ability and is capable of providing high strength through a chemical strengthening treatment by means of ion exchange. A glass composition of the present invention contains, in mass%, 53-62% of SiO2, 11-17% of Al2O3, 0-5% of Li2O, 10-15% of Na2O, 3-9% of K2O, 0-4% of MgO, 0-4% of CaO, 0-6% of SrO, 0-5% of BaO, 1-4% of ZrO2 and 2-6% of TiO2.

Description

201228974 VI. TECHNOLOGICAL FIELD OF THE INVENTION The present invention relates to a glass composition having a high heat resistance and capable of imparting a reinforcing layer having a high mechanical strength by chemical strengthening treatment accompanying ion exchange. [Prior Art] Since glass has excellent properties such as high surface smoothness or large surface strength, it is widely used for display substrates such as touch panels and color filters. However, there is a disadvantage that the glass is easily broken. As a countermeasure against this, a so-called strengthening treatment in which a compressive stress is applied to the surface by quenching or ion exchange can be performed. In the strengthening treatment, the chemical strengthening treatment by ion exchange is easier to strengthen than the other strengthening treatments even if the thickness of the glass is thin, so that the display substrate material and the like are preferably strengthened. The chemical strengthening treatment imparts compressive stress to the surface of the glass by exchanging ions (usually Na) in the vicinity of the surface of the glass into ions having a larger ionic radius, and the ease or strength of strengthening is of course affected by the composition of the glass. . For example, there is disclosed a glass for chemical strengthening which is of mass. /❶ indicates that 58~65% of SiO2, 8~15% of Al2〇3, 4~10% of Li2〇, 9~13〇/〇 of Na20, 0.5~2% of Zr02, and 2~5% of ZnO 0.5 to 2% of 卩2〇5 (refer to Patent Document 1). Further, for example, a glass for chemical strengthening is disclosed, which comprises, by mass%, 59 to 68% of SiO 2 , 9.5 to 15% of Al 2 〇 3, 0 to 1% of Li 2 〇, 3 to 18% of Na 20 , and 0 to 3.5. % K20, 〇~15% MgO, 1~15% CaO, 16021I.doc 201228974 0-4.5% SrO, 〇~1% BaO, 1~1〇°/. Zr02, 0 to 2% of Ti02 (see Patent Document 2). CITATION LIST Patent Literature Patent Literature 1: Patent Publication No. 2000-7372 Patent Document 2: Japanese Patent Laid-Open Publication No. Hei No. No. 2005-15328 [Draft of the Invention] [Problems to be Solved by the Invention] Chemically strengthened glass The mechanical strength of the reinforcing layer is resistant to damage to the glass surface, and the greater the mechanical strength of the reinforcing layer, the greater the damage resistance. Further, the strengthening layer is also related to the amount of ion exchange in ion exchange. However, the ease of reinforcement and the mechanical strength of the reinforcement layer are affected by the composition of the glass. For example, it is necessary to include a large amount of U2〇, ΙΟ" Zn〇, so that the glass transition point is low', and bending is likely to occur during reinforcement, for example, as disclosed in Japanese Laid-Open Patent Publication No. Hei. Moreover, since it contains ?2〇5, the chemical stability is poor. Further, although the scope of the patent application is broad in the disclosure of Japanese Laid-Open Patent Publication No. 2005-15328, a large amount of Ca 含有 is contained in the examples. In the potassium nitrate solution which is usually used, it is known that the strengthening ability is remarkably lowered due to dissolution of Ca ’, and it is considered that it is not suitable for chemical strengthening. In view of such prior art, it is an object of the present invention to provide a glass combination which is strong in preventing surface damage even when used as a glass for a touch panel display, and which can be subjected to chemical strengthening treatment to give a large mechanical strength. Things. 160211.doc 201228974 [Technical means for solving the problem] The present invention is characterized by: % by mass: 53 to 62% of SiO 2 , 11 to 17% of Al 2 〇 3 ' 10 to 15% of Na 20 , 3 to 9% K20, 0 to 4% of CaO, 0 to 4% of MgO, 0 to 6% of SrO, 0 to 5% of BaO, 1 to 4% of Zr〇2, and 2 to 5% of 1102. Further, the present invention is the above glass composition, wherein the ion exchange capacity (the ion exchange weight per glass surface area in the chemical strengthening treatment is mg/cm 2 in the chemical strengthening treatment of the potassium nitrate solution at a temperature of 9 times the glass strain point) Further, the present invention is the glass composition of the above, wherein the glass transition point is further. The present invention provides a chemically strengthened article by impregnating a glass article comprising the above glass composition to contain a radius larger than a cerium ion. In the molten salt of the ionic radius-valence cation, the Na ion contained in the glass article is ion-exchanged with the monovalent cation. The present invention is a method for producing the glass composition, which utilizes a glass strain point. The hetero-potassium solution at a temperature of 0.9 times is chemically strengthened. The ion exchange capacity (the ion exchange weight per glass surface area in the chemical strengthening treatment) is 〇.2 mg/cm 2 or more. Further, the present invention Is a method for producing the above glass composition, which has a glass transition point of 58 〇t or more. Further, the present invention is a A method for producing a glass article comprising the above glass composition by impregnating a molten salt containing a monovalent cation having an ionic radius larger than a radius of Na ions, thereby oxidizing ions contained in the glass article with the monovalent cation [Effect of the Invention] The glass composition of the present invention can obtain a chemically strengthened layer having a large mechanical strength by chemical strengthening, and it is difficult to cause deformation due to heat even when the glass is heated to a high temperature. [Embodiment] The glass composition of the present invention is preferably represented by mass%: 53 to 62% of SiO 2 , 11 to 17% of Al 2 〇 3, 10 to 15% of Na 20 , and 3 to 9% of K 20 , 0 . ~4% CaO, 0~4% MgO, 0~6% SrO, 0~5% BaO, 1~4% Zr02, 2~5% Ti02. 160211.doc 201228974 with the preferred glass The glass composition of the composition can be more reliably imparted with a chemical strengthening layer by chemical strengthening treatment. The glass composition of the glass composition preferably has a glass transition point of at least 580 ° C. Even if the glass composition is Salt dissolved by, for example, chemical strengthening In the heat treatment such as heating, the deformation of the glass is not easily generated. According to the chemically strengthened glass article of the present invention, since a large reinforcing layer is formed on the surface of the glass article, the mechanical strength is increased, so that it can be subjected to an external impact. Further, the chemically strengthened glass article of the present invention forms a reinforcing layer having a large mechanical strength on the surface of the glass article, and thus the strength is less reduced due to friction from the outside or damage due to scratches. In the following description, the reason for limiting the composition of the glass composition of the present invention will be described. In the following description, the % of the composition is indicated as all mass%.

Si〇2 is a component which forms glass, and preferably contains ～62% by mass%. If Si〇2 is less than S3%, the chemical stability is poor. If it is more than 62%, the melting temperature of the glass becomes high, and it becomes difficult to obtain a homogeneous glass, which is not preferable.

Al2〇3 is the main component of glass as well as Si〇2, and is a component which increases the ion exchange rate and improves the water resistance of the glass. It is preferable that the effect is not easily exhibited by the mass (4) containing 11% of ruthenium. On the other hand, if it is more than 17%, the viscosity of the glass melt becomes high, and it becomes difficult to obtain a homogeneous glass, which is not preferable. Further, it is expected to be u to i5%. 160211.doc 201228974

LhO is a component which increases the strength of glass by ion exchange of Li ions with other cations such as Na ions and κ ions in the molten salt. However, 'if it has a high content rate, it has the disadvantage of impairing the heat resistance of the glass. Therefore, the content ratio of LhO is desirably 5% or less.

NaaO is a component which increases the strength of glass by ion exchange of Na ions with other cations such as κ ions in the molten salt, and is a component for improving the meltability. At 10. /. In the following cases, the effect is not sufficient and the meltability is also poor. On the other hand, if it exceeds 15 ° / 〇, the chemical durability is deteriorated. Κ2〇 is a component which improves the meltability of glass as well as NazO, and therefore is preferably 3% or more. However, in general, the chemical strengthening system uses potassium nitrate molten salt, so if the content of K2〇 exceeds 9% ', sufficient ion exchange is not caused. Therefore, it is preferably 9% or less.

Mg Ο is a component which lowers the viscosity of the glass and enhances the refining property of the glass. However, since the devitrification temperature of the glass is increased, it is preferable to contain 〇~4〇/0 in mass%.

Similarly to MgO, CaO is an ingredient which lowers the viscosity of the glass and improves the meltability. However, since the devitrification temperature of the glass rises, it is preferably contained in an amount of 0 to 5% by mass.

SrO is also a component which lowers the viscosity of the glass and improves the solubility as in the case of MgO or CaO. However, since SrO hinders the movement of the alkaline component in the glass, it is preferably contained in an amount of 0 to 6% by mass%.

In the same manner as MgO or CaO, BaO is a component which lowers the viscosity of the glass and improves the solubility. However, since BaO hinders the movement of the test component in the glass, it is preferably 5% or less by mass%.

Zr〇2 is used to increase the ion exchange rate and also improve the water resistance of the glass. 1602 II.doc 201228974 When the knife is below 1 /〇, the effect is not sufficient. If it exceeds 4%, the melting temperature becomes high. Contains 1~4〇/0.

Ti〇2 is a component that lowers the viscosity of the glass and improves the meltability, but does not deteriorate the chemical stability more than the alkaline component, so it must be 2% or more. If the content of Ti〇2 exceeds 5%, Since the devitrification temperature rises and the formability is inhibited, it is preferably 2 to 5% by mass%. More preferably 4 to 5 〇 / 0. Also, quality can be used as needed. /. As a purifying agent, As2〇3, Sb203, and Sn〇2 are contained up to a total of 1%. [Examples] Hereinafter, description will be made based on examples. A glass having the glass composition shown in Examples 1 to 11 of the glass composition of the present invention was produced by a melting test, and the obtained glass was melted at a temperature, a working temperature, a coefficient of thermal expansion, and a glass transition point (°c). The measurement results of strain point, devitrification temperature (Art), and ion exchange capacity (mg/cm2) are shown in Table 1. Further, a comparative example is shown in Table 2. "ND" in the devitrification temperature column indicates that no devitrification was found. [Table 1] Glass No. 1 2 3 4 5 6 7 8 9 10 ~ SiO^ 57,1 61.9 57.5 59.5 58.2 59.0 55.7 58.7 53.1 60.2 ai2o3 12.3 12.0 14.9 11.8 11.4 11.7 17.0 11.8 15.0 11.9 Na2〇14.0 14.1 13.8 13.8 13.4 10 , 0 13.6 13.8 14.7 14,0 K2O 5.7 3.0 3.0 3.0 3.0 8.6 3.0 3.0 5.6 3.0 MgO 2.4 4.0 4.0 1.6 1.5 4.0 4.0 4.0 0.0 4.0 CaO 0.0 0.0 0.0 3.5 0.0 0.0 0.0 0.0 3.3 0.0 0.0 SrO 0.0 0.0 0.0 0.0 6.0 0.0 0.0 0.0 0.0 0.0 Zr〇2 3.7 0.0 1.9 1.9 1,7 1.9 1.9 3.8 3.6 1.9 Ti〇2 Mass % 4.8 5.0 4.9 4.9 4.8 4.8 4.8 4.9 4.7 5.0 Count 100.0 100,0 100.0 100.0 100.0 100.0 100.0 ]〇0.0 100.0 100.0 Viscosity (° C) log??=2.〇1590 1620 1628 1554 1565 1625 1643 1616 1543 1615 = 4.0 1143 1149 1182 1106 1107 1169 1201 1169 1106 1155 Thermal expansion αχ HT Vc 93.9 85,6 84.6 85.4 89.3 90.9 85 83.4 96.9 84.5 Transfer point 604 597 620 598 588 608 634 619 601 609 Strain point (°C) Ts 556 544 570 546 538 554 587 568 551 557 Devitrification temperature ND ND 1060 ND ND ND 1160 ND ND ND Ion exchange capacity 0.45 0.35 0.41 0.25 0.21 0.34 0.49 0.36 0.33 0.30 160211. Doc •9· 201228974 [Table 2] Glass No. — — 1 2 3 4 Si〇2 AI2O3 71.91 1.97 62.5 11.5 64.1 9.94 56.3 11.1 Li2〇- Na20 K20 0.0 13.09 0.92 7.64 12.2 0.0 0.6 14.8 0.0 0.0 13.1 2.7 MgU CaO 3.69 8.41 0.0 0.0 3 6.18 1.5 0.0 BaO --- 0.0 0.0 0.0 8.9 Zr〇2 Ti02 ZnO P2O5 Sb203% by mass 4» ~----- 0.0 0.0 0.0 0.0 0.0 1.4 0.0 2.9 1.0 0.8 2.0 0.0 0.0 0.0 0.0 1.8 4.6 0.0 0.0 0.0 100.0 99.9 100.0 100.0 Viscosity (C) l〇g7/=2.0 = 4.0 1461 1037 1371 1010 1559 1123 1570 1100 Thermal expansion αχ1〇·7/° (3 Transfer point 85.5 555 97, 4 450 79.9 594 88.2 583 Strain point 502 408 550 529 Devitrification temperature '1032 860 1050 ND ion exchange capacity 0.06 0.40 0.17 0.17 ------ - The glass of Examples 1 to 10 and Comparative Examples 1 to 4 were prepared and the physical properties of the obtained decomposed were The following sequence is implemented. (Production of Glass) In order to obtain the glass composition shown in Table 1 or Table 2, cerium oxide, aluminum oxide, lithium carbonate, sodium carbonate, potassium carbonate, magnesium oxide, calcium carbonate, cesium carbonate, which is a usual glass raw material, is used. The bismuth carbonate, titanium oxide, and bismuth acid are mismatched to prepare a glass raw material (masterbatch). After the blended masterbatch was mixed, it was put into a platinum crucible and kept in an electric furnace at 16 GG ° C for 3 hours, and then it was mixed twice with an Ming rod. After heating for another 2 hours, it was discharged on a carbon plate at 15001, and immediately placed in a slow cooling furnace at 650 ° C, and cooled for 4 hours until 55 ° C, and then placed in a furnace for cooling to form a glass monument. . (Measurement of physical properties) 1602U.doc 201228974 The sample glass is processed into a cylindrical shape of Φ5 mm and a length of 20 mm, using a differential thermal expansion meter (Thermo plus, Ding] 八8310, manufactured by RIGAKU Co., Ltd.), and according to 15 113102, 30 was measured at 3103. (:~300. (: thermal expansion coefficient and glass transition point. High temperature viscosity log 7? = 2 and 4 are measured using OPTO's pull ball viscometer B VB_ 13LH. Use beam deflection viscometer BBVM-900 (Measurement of bending speed and measurement of strain point (manufactured by OPTO Co., Ltd.). (According to JIS R3 103-2) Using a temperature tilting furnace (manufactured by Incheon) at a specific temperature for 2 hours, use a polarizing microscope ECLIPSE ΕόΟΟ P〇L ( Nikon manufacture) confirms the presence or absence of crystallization and measures the devitrification temperature. The ion exchange capacity is an ion exchange capacity which increases the weight per glass surface area due to the exchange of Na+ to K+. If the amount of increase is large, the ion exchange capacity becomes high. The glass was optically ground to about 40×40×3 mm, and ion exchange treatment was carried out for 4 hours in potassium nitrate at a temperature 9 times the strain point, and the weight (0.1 mg unit) and size before and after the treatment were measured, and the increase per surface area was calculated. As shown in Table 1 and Table 2, the glass transition point of the embodiment (7) in the present invention is 58 (TC or more, heat resistance. Further, if the ion exchange capacity is also 〇2 mg/cm2) On the other hand, it is a glass which is easy to perform ion exchange. If the ion exchange is much straighter, m becomes deeper from the surface of the glass to the inside of the ion exchange layer, and it is considered to be a glass which is more resistant to damage of the surface. 1 is a normal float glass, but its ion exchange 160211.doc 201228974 has a low t* force of 0 06 mg/cm2, which is considered to be a glass that prevents damage to the weaker. Comparative Example 2 is a special patent of 2000. The glass of Example 4 of the publication No. 7372, but the glass transition point is lower than 45 Å, so that the heat resistance is low. Further, Comparative Example 3 is the glass of Example 5 of JP-A-2005-15328, but the ion The exchange capacity is less than 0.17 mg/cm2. The BaO of Comparative Example 4 is 8.9% more, and the ion exchange capacity is less than 0.17 mg/cm2. [Industrial Applicability] The present invention provides, for example, a touch panel. In the display substrate, it is possible to prevent damage to the external surface such as damage, and it is possible to impart a mechanical strength with a large mechanical strength by chemical strengthening treatment. 160211.doc 12-

Claims (1)

201228974 VII. Patent application scope: 1. A glass composition, which is of mass. /〇 indicates: 53~62% of Si〇2, 11~17% of Al2〇3, 10~15% of Na20, 3~9% of Κ·2〇, 0~4% of CaO, 0~4 % of MgO, 0 to 6% of SrO, 0 to 5% of BaO, 1 to 4% of Zr〇2, and 2 to 5% of Ti02. 2. The glass composition of claim 1, wherein in the chemical strengthening treatment of the potassium nitrate solution at a temperature nine times the glass strain point, the ion exchange capacity (the ion exchange weight per glass crucible area in the chemical strengthening zone) is 〇2 m „/__2 , the above. 4. A method for producing a valence of an ionic radius of a Na ion radius of a glass article of any one of the items -1 -* · · · · · · · · · · · It is chemically strengthened by using a potassium nitrate solution having a temperature of 0.9 times the glass strain point of the glass composition 16021J.doc 201228974 of claim 1 to achieve ion exchange capacity (ion per glass surface area in chemical strengthening treatment) The exchange weight) is 〇_2 mg/cm2 or more. 6. A method for producing a glass composition according to claim 2 or 2, which has a glass transition point of 580 ° C or higher. 7. The species includes the request item (1) A method for producing a glass article of a glass composition according to any one of the preceding claims, wherein the glass material is contained by impregnating (4) a valence cation having an ionic radius greater than the ionic radius of the ion. The above-mentioned cation cation is ion exchanged. 〇〇160211.doc 201228974 IV. Designated representative map: (1) The representative representative of the case is: (none) (2) The symbol of the representative figure is simple Description: Fifth, if the case of formula, please reveal most features of the present invention shows the chemical formula: (None) 160211.doc