CN117597320A - Glass plate for strengthening and glass plate for strengthening - Google Patents
Glass plate for strengthening and glass plate for strengthening Download PDFInfo
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- CN117597320A CN117597320A CN202280047397.2A CN202280047397A CN117597320A CN 117597320 A CN117597320 A CN 117597320A CN 202280047397 A CN202280047397 A CN 202280047397A CN 117597320 A CN117597320 A CN 117597320A
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- 239000011521 glass Substances 0.000 title claims abstract description 142
- 238000005728 strengthening Methods 0.000 title claims abstract description 43
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 55
- 238000005452 bending Methods 0.000 claims abstract description 48
- 229910018068 Li 2 O Inorganic materials 0.000 claims abstract description 41
- 239000000203 mixture Substances 0.000 claims abstract description 36
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 17
- 230000002787 reinforcement Effects 0.000 claims abstract description 12
- 239000005341 toughened glass Substances 0.000 claims description 53
- 238000005342 ion exchange Methods 0.000 claims description 42
- 238000011282 treatment Methods 0.000 claims description 27
- 239000006058 strengthened glass Substances 0.000 claims 2
- 238000005259 measurement Methods 0.000 description 14
- 238000004031 devitrification Methods 0.000 description 13
- 229910004298 SiO 2 Inorganic materials 0.000 description 12
- 229910006404 SnO 2 Inorganic materials 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- 239000010410 layer Substances 0.000 description 10
- 238000007500 overflow downdraw method Methods 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 8
- 239000006060 molten glass Substances 0.000 description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 7
- 238000001816 cooling Methods 0.000 description 6
- 238000000465 moulding Methods 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000002585 base Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000003280 down draw process Methods 0.000 description 3
- 239000003365 glass fiber Substances 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 239000002344 surface layer Substances 0.000 description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003929 acidic solution Substances 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- 238000009774 resonance method Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229910052596 spinel Inorganic materials 0.000 description 2
- 239000011029 spinel Substances 0.000 description 2
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 1
- 229910017493 Nd 2 O 3 Inorganic materials 0.000 description 1
- 238000006124 Pilkington process Methods 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000008395 clarifying agent Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000007372 rollout process Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000005496 tempering Methods 0.000 description 1
- 238000004017 vitrification Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- Glass Compositions (AREA)
Abstract
The invention provides a bending part with less visibilityA glass plate for reinforcement and a glass plate for reinforcement which are hardly broken when being lowered and bent. The glass plate for strengthening of the present invention is a glass plate for strengthening having a plate thickness of 0.2mm or less, and is characterized by comprising, in mol% as a glass composition: siO (SiO) 2 50～80％、Al 2 O 3 2～25％、Na 2 O2-25%, and mole ratio Al 2 O 3 /Na 2 O is 0.5-2.5, mole ratio Na 2 O/(Li 2 O+Na 2 O+K 2 O) is 0.70 or more.
Description
Technical Field
The present invention relates to a glass sheet for reinforcement and a glass sheet for reinforcement, and more particularly, to a glass sheet for reinforcement suitable for flexible cover members for foldable displays and the like.
Background
In recent years, products such as foldable displays and scroll screen displays that can be folded have been marketed. In such products, a flexible cover member formed by laminating a resin and a reinforced glass plate is used.
In addition, as the tempered glass sheet, a tempered glass sheet subjected to ion exchange treatment is generally used (see patent documents 1 and 2 and non-patent document 1).
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open No. 2006-83045
Patent document 2: international publication No. 2015/031188
Non-patent literature
Non-patent document 1: new glasses and their physical properties such as spring Gu Chelang, national institute of operation, first edition, society, 8 months and 20 days in 1984, p.451-498
The flexible cover member is used in a bent state, but if the flexible cover member is held in a bent state for a certain period of time, visibility of the bent portion of the tempered glass sheet may be deteriorated after the holding state is released. In addition, in the glass composition of the conventional tempered glass sheet, since the young's modulus is large, stress generated at the time of bending is large, and breakage may be caused.
The present invention has been made in view of the above circumstances, and an object thereof is to provide a glass sheet for reinforcement and a glass sheet for reinforcement, which are less likely to deteriorate visibility of a bent portion and are less likely to break during bending.
Disclosure of Invention
Means for solving the problems
As a result of intensive studies, the present inventors have found that the cause of the deterioration in visibility of the bent portion is bending strain, and have found that, in the glass composition, the glass composition is produced by mixing a molar ratio of Al 2 O 3 /Na 2 O and molar ratio Na 2 O/(Li 2 O+Na 2 O+K 2 O) is limited to a proper range, so that the bending deformation becomes small, the young's modulus becomes low, and is proposed as the present invention. That is, the glass plate for strengthening of the present invention is a glass plate for strengthening having a plate thickness of 0.2mm or less, and is characterized by comprising, in mol%, as a glass composition: siO (SiO) 2 50～80％、Al 2 O 3 2～25％、Na 2 O2-25%, mole ratio Al 2 O 3 /Na 2 O is 0.5-2.5, mole ratio Na 2 O/(Li 2 O+Na 2 O+K 2 O) is 0.70 or more. Here, the "molar ratio Al 2 O 3 /Na 2 O "means to make Al 2 O 3 Divided by Na 2 The molar% content of O. "molar ratio Na 2 O/(Li 2 O+Na 2 O+K 2 O) "means Na 2 The mole% content of O divided by Li 2 O、Na 2 O and K 2 A value obtained by adding up the mol% of O.
In addition, the glass plate for strengthening of the present invention is preferably a glass plate for strengthening having a plate thickness of 0.2mm or less, and comprises, in mol%, as a glass composition: siO (SiO) 2 50～80％、Al 2 O 3 2～20％、Na 2 O 2～20％And molar ratio Al 2 O 3 /Na 2 O is more than 0.62 and less than 2, and the mole ratio of Na 2 O/(Li 2 O+Na 2 O+K 2 O) is 0.90 or more.
In addition, the glass plate for strengthening of the present invention is preferably a glass plate for strengthening having a plate thickness of 0.15mm or less, and comprises, in mol%, as a glass composition: siO (SiO) 2 50～80％、Al 2 O 3 2～20％、MgO 0～8％、Na 2 O2-20%, and mole ratio Al 2 O 3 /Na 2 O is 0.68-2, mole ratio Na 2 O/(Li 2 O+Na 2 O+K 2 O) is 0.90 or more.
In addition, the glass plate for strengthening of the present invention preferably has a plate thickness of 0.10mm or less.
In addition, the glass sheet for strengthening of the present invention preferably contains 10.5 to 20 mol% of Al in the glass composition 2 O 3 。
In addition, the glass sheet for strengthening of the present invention preferably contains 1 to 15 mol% of B in the glass composition 2 O 3 。
Further, the glass sheet for strengthening of the present invention preferably has a bending strain of 40.0X10 -5 The following is given. Here, the "bending strain" means that a fibrous glass (evaluation sample) having a length of 150mm and Φ0.13mm was set between two support plates having a distance of 26mm so as to maintain a U-shape, and the glass was held at room temperature for 24 hours, and then the evaluation sample was taken out from between the support plates to release the held state, and further left at room temperature for 5 minutes, and after that, the bending strain generated in the bending portion of the evaluation sample was calculated by the following formula 1 according to JIS K7116 (see fig. 1).
Bending strain= (6×st×d)/(L) 2 ) 1 (1)
St:2 distance between the points of intersection of the midpoint between the base points and the tangent at each base point
d: fiber diameter of evaluation sample (0.13 mm)
L:2 distance between base points
Preferably, the tempered glass sheet of the present invention is a tempered glass sheet obtained by subjecting a tempered glass sheet to an ion exchange treatment, and the tempered glass sheet has a compressive stress layer on a surface thereof.
In the tempered glass sheet of the present invention, the compressive stress value of the outermost surface of the compressive stress layer is preferably 100 to 800MPa. Here, the "compressive stress value of the outermost surface of the compressive stress layer" and the "stress depth" can be calculated from, for example, the number of interference fringes observed by using a surface stress meter (FSM-6000 manufactured by the manufacturing company of folding origin) and the interval thereof.
The tempered glass plate of the present invention is a tempered glass plate having a plate thickness of 0.2mm or less, and is characterized by having a compressive stress layer on the surface, and comprising, as a glass composition in mol%: siO (SiO) 2 50～80％、Al 2 O 3 2～25％、Na 2 O2-25%, and mole ratio Al 2 O 3 /Na 2 O is 0.5-2.5, mole ratio Na 2 O/(Li 2 O+Na 2 O+K 2 O) is 0.70 or more.
In addition, the tempered glass sheet of the present invention is preferably a tempered glass sheet having a sheet thickness of 0.2mm or less, and has a compressive stress layer on a surface thereof, and comprises, as a glass composition, in mol%: siO (SiO) 2 50～80％、Al 2 O 3 2～20％、Na 2 O2-20%, and mole ratio Al 2 O 3 /Na 2 O is more than 0.62 and less than 2, and the mole ratio of Na 2 O/(Li 2 O+Na 2 O+K 2 O) is 0.90 or more.
In addition, the tempered glass sheet of the present invention is preferably a tempered glass sheet having a sheet thickness of 0.15mm or less, and has a compressive stress layer on a surface thereof, and comprises, as a glass composition, in mol%: siO (SiO) 2 50～80％、Al 2 O 3 2～20％、MgO 0～8％、Na 2 O2-20%, and mole ratio Al 2 O 3 /Na 2 O is 0.68-2, mole ratio Na 2 O/(Li 2 O+Na 2 O+K 2 O) is 0.90 or more.
In addition, the thickness of the tempered glass plate of the present invention is preferably 0.10mm or less.
In addition, the bending strain (JIS: K7116) of the tempered glass plate of the present invention is preferably 40.0X10 -5 The following is given.
Drawings
Fig. 1 is an explanatory diagram for explaining an evaluation method of bending strain.
Fig. 2 is an image of the visibility of a glass sample in which a curved portion is formed, and in which the visibility is not easily degraded.
Fig. 3 is an image in which visibility of a glass sample in which a bent portion is formed is easily degraded.
Detailed Description
The glass plate for strengthening and the glass plate for strengthening of the present invention are characterized by comprising, as glass composition, in mol%: siO (SiO) 2 50～80％、Al 2 O 3 2～25％、Na 2 O2-25%, and mole ratio Al 2 O 3 /Na 2 O is 0.5-2.5, mole ratio Na 2 O/(Li 2 O+Na 2 O+K 2 O) is 0.70 or more. The reason why the content ranges of the respective components are defined in the glass sheet for reinforcement and the glass sheet for reinforcement are as follows. In the description of the content ranges of the respective components, unless otherwise specified,% expression means mol%. In the present specification, the numerical range indicated by the term "to" means a range including numerical values described before and after the term "to" as a minimum value and a maximum value, respectively.
SiO 2 Is a component forming a glass network. If SiO is 2 If the content of (C) is too small, vitrification becomes difficult. Thus, siO 2 The lower limit of (2) is preferably 50% or more, 52% or more, 54% or more, 55% or more, 57% or more, 59% or more, 60% or more, 61% or more, 62% or more, 63% or more, particularly preferably 64% or more. On the other hand, if SiO 2 If the content of (b) is too large, the meltability and moldability tend to be lowered, and the coefficient of thermal expansion tends to be too low, making it difficult to match the coefficient of thermal expansion of the peripheral material. Thus, siO 2 The upper limit of (2) is preferably 80% or less, 75% or less, 73% or lessLower, 71% or less, 70% or less, 69% or less, 68% or less, 67% or less, 66% or less, 65% or less, and particularly preferably 64% or less.
Al 2 O 3 Is a component for improving ion exchange performance. If Al is 2 O 3 If the content of (b) is too small, the ion exchange performance tends to be lowered, and the bending strain tends to be increased. Thus, al 2 O 3 The lower limit of (2) is preferably 2% or more, 3% or more, 4% or more, 5% or more, 6% or more, 7% or more, 8% or more, 9% or more, 10% or more, 10.5% or more, 11% or more, 12% or more, particularly preferably 13% or more. On the other hand, if Al 2 O 3 If the content of (b) is too large, devitrification crystals tend to be deposited on the glass, and it is difficult to perform plate-like molding by the overflow downdraw method or the like. In particular, when an alumina refractory is used as a molded body refractory and plate-like molding is performed by the overflow downdraw method, devitrified crystals of spinel are likely to precipitate at the interface with the alumina refractory. Thus, al 2 O 3 The upper limit of (2) is preferably 25% or less, 20% or less, 19% or less, 18% or less, 17% or less, 16% or less, 15% or less, 14% or less, particularly preferably 13% or less.
The alkali metal oxide is an ion exchange component, and is a component that reduces the high-temperature viscosity and improves the meltability and moldability. However, if the content of the alkali metal oxide is too large, bending strain becomes large. In addition, the coefficient of thermal expansion may become high. Thus, alkali metal oxide (Li 2 O+Na 2 O+K 2 The preferable lower limit range of O) is 1% or more, 2% or more, 3% or more, 4% or more, 5% or more, 6% or more, 7% or more, 8% or more, 9% or more, 10% or more, 11% or more, 12% or more, particularly preferably 13% or more, and the preferable upper limit range is 25% or less, 24% or less, 23% or less, 22% or less, 21% or less, 20% or less, 19% or less, 18% or less, 17% or less, 16% or less, 15% or less, 14% or less, particularly preferably 13% or less.
Li 2 O is an effective component for obtaining ion exchange components, particularly deep stress depthIn addition, the composition is a component which reduces the high-temperature viscosity to improve the meltability and moldability. On the other hand, if Li 2 O and Na 2 When O is present, bending strain tends to increase, and the component dissolves out during ion exchange treatment to deteriorate the ion exchange solution. Therefore, the upper limit is preferably 3% or less, 2% or less, 1% or less, 0.1% or less, and particularly preferably less than 0.1%.
Na 2 O is an ion exchange component, and is a component that reduces the high-temperature viscosity to improve the meltability and moldability. In addition, na 2 O is also a component that improves devitrification resistance and reaction devitrification with a shaped refractory, particularly an alumina refractory. Further, if Na is preferentially introduced into the alkali metal oxide 2 O, the bending strain can be reduced. Thus, na 2 The lower limit of O is preferably 2% or more, 5% or more, 6% or more, 7% or more, 8% or more, 9% or more, 10% or more, 11% or more, 12% or more, and particularly preferably 13% or more. On the other hand, if Na 2 When the content of O is too large, bending strain becomes large, and the balance of the glass composition may be lost, and the devitrification resistance may be lowered. Thus, na 2 The preferable upper limit range of O is 25% or less, 22% or less, 20% or less, 19.5% or less, 19% or less, 18% or less, 17% or less, 16.5% or less, 16% or less, 15.5% or less, 15% or less, 14.5% or less, 14% or less, 13.5% or less, and particularly preferably 13% or less.
K 2 O is a component that reduces the high-temperature viscosity and improves the meltability and moldability. In addition, the composition is also a component for improving devitrification resistance. However, if K 2 O and Na 2 When O is present, bending strain tends to be large. In addition, if K is added excessively 2 O, the balance of the glass composition tends to be lowered, and the devitrification resistance tends to be lowered. Therefore, the upper limit is preferably 3% or less, 2% or less, 1% or less, 0.1% or less, and particularly preferably less than 0.1%.
Molar ratio Al 2 O 3 /Na 2 O is a component ratio useful for lowering bending strain, and its value is too large or too small, and bending strain becomes large. In addition, in the case of the optical fiber,if the value is too large or too small, the Young's modulus becomes high. Al (Al) 2 O 3 /Na 2 The preferable lower limit of O is in the range of 0.5 or more, 0.6 or more, more than 0.62, 0.65 or more, 0.68 or more, 0.7 or more, 0.75 or more, 0.8 or more, 0.85 or more, 0.9 or more, 0.92 or more, 0.94 or more, 0.95 or more, 0.96 or more, 0.97 or more, 0.98 or more, particularly preferably 0.99 or more, and the preferable upper limit is in the range of 2.5 or less, 2 or less, 1.9 or less, 1.8 or less, 1.7 or less, 1.6 or less, 1.5 or less, 1.4 or less, 1.3 or less, 1.2 or less, 1.15 or less, 1.1 or less, 1.08 or less, 1.06 or less, 1.04 or less, 1.02 or less, particularly preferably 1.01 or less.
Molar ratio Na 2 O/(Li 2 O+Na 2 O+K 2 O) is a component ratio useful for lowering bending strain, and if the value is too small, bending strain becomes large. In addition, if the value is too large or too small, the Young's modulus becomes high. Na (Na) 2 O/(Li 2 O+Na 2 O+K 2 The preferable lower limit of O) is 0.70 or more, 0.75 or more, 0.80 or more, 0.85 or more, 0.90 or more, 0.92 or more, 0.94 or more, 0.95 or more, 0.96 or more, 0.97 or more, particularly preferably 0.98 or more, and the further preferable upper limit is 1 or less, particularly preferably 0.99 or less.
In addition to the above components, the following components may be added, for example.
B 2 O 3 Is a component which reduces the high-temperature viscosity, density and Young's modulus and improves the devitrification resistance. However, if B 2 O 3 If the content of (a) is too large, the ion exchange rate (particularly the stress depth) tends to be low. Further, the surface of the glass, which is called scorching, is colored by ion exchange, and bending strain is liable to become large, and acid resistance and water resistance are liable to be lowered. Thus B 2 O 3 The lower limit of (2) is preferably 0% or more, 0.1% or more, 0.5% or more, 1% or more, 2% or more, 3% or more, 4% or more, 5% or more, 5.5% or more, 6% or more, 6.5% or more, 7% or more, 7.5% or more, 8% or more, 8.5% or more, and particularly preferably 9% or more. In addition, B 2 O 3 The preferable upper limit of (2) is in the range of 15%Lower, 13% or lower, 12% or lower, 11% or lower, 10.5% or lower, 10% or lower, and particularly preferably 9.5% or lower.
MgO is a component that reduces the high-temperature viscosity and improves the meltability and moldability. However, if the MgO content is too large, the ion exchange performance tends to be lowered, or the glass tends to devitrify. In particular, when an alumina refractory is used as a molded body refractory and plate-like molding is performed by the overflow downdraw method, devitrified crystals of spinel are likely to precipitate at the interface with the alumina refractory. Therefore, the preferable content of MgO is 0 to 8%, 0 to 6%, 0 to 5%, 0 to 4%, 0 to 3.5%, 0 to 3%, 0 to 2%, particularly preferably 0 to 1%.
CaO is a component that reduces the high-temperature viscosity and improves the meltability and moldability without reducing the devitrification resistance as compared with other components. However, if the CaO content is too large, the ion exchange performance tends to be lowered and the ion exchange solution tends to be deteriorated. Therefore, the preferable content of CaO is 0 to 6%, 0 to 5%, 0 to 4%, 0 to 3.5%, 0 to 3%, 0 to 2%, 0 to 1%, particularly preferably 0 to 0.5%.
SrO and BaO are components that lower the high-temperature viscosity and improve the meltability and the formability, but if the content of these components is too large, the ion exchange performance is lowered, the density and the thermal expansion coefficient are increased, and the glass is liable to devitrify. Therefore, the preferable content of SrO and BaO is 0 to 2%, 0 to 1.5%, 0 to 1%, 0 to 0.5%, 0 to 0.1%, and particularly preferably 0 to less than 0.1%, respectively.
The total amount of CaO, srO and BaO is preferably 0 to 5%, 0 to 2.5%, 0 to 2%, 0 to 1.5%, particularly preferably 0 to 1%. If the total amount of CaO, srO and BaO is too large, the ion exchange performance tends to be lowered.
ZnO is a component that improves ion exchange performance, and particularly has an excellent effect of improving the compressive stress value. In addition, the composition is a component which reduces the high-temperature viscosity without reducing the temperature viscosity. However, if the ZnO content is too large, glass phase separation tends to occur, devitrification resistance tends to decrease, density tends to increase, and stress depth tends to decrease. Therefore, the content of ZnO is preferably 0 to 10%, 0 to 6%, 0 to 3%, and particularly preferably 0 to 1%.
P 2 O 5 Is a component for improving ion exchange performance while maintaining a compressive stress value. In addition, the composition is a component for reducing bending strain and Young's modulus. Also, the composition can reduce the high-temperature viscosity, and improve the meltability and moldability. However, if P 2 O 5 If the content is too large, the glass tends to be clouded due to phase separation and the acid resistance tends to be lowered. Thus, P 2 O 5 The upper limit of (2) is preferably 15% or less, 12% or less, 10% or less, 8% or less, 6% or less, 5% or less, 4% or less, 3% or less, 2% or less, 1% or less, 0.5% or less, and particularly preferably 0.1% or less. In addition, at the time of adding P 2 O 5 P in the case of (1) 2 O 5 The lower limit of (2) is preferably 0% or more, 0.1% or more, 0.5% or more, 1% or more, 2% or more, and particularly preferably 3% or more.
TiO 2 The component that improves ion exchange performance and reduces high-temperature viscosity is also a component, but if the content is too large, coloring and devitrification of the glass are likely to occur. Thus, tiO 2 The content of (2) is preferably 0 to 4.5%, 0 to less than 1%, 0 to 0.5%, particularly preferably 0 to 0.3%.
ZrO 2 The component significantly improves ion exchange performance and increases viscosity and strain point near the viscosity of the liquid phase, but if the content is too large, the devitrification resistance may be significantly reduced, and the density may be too high. Thus, zrO 2 The content is preferably 0 to 5%, 0 to 4%, 0 to 3%, 0 to 2%, 0 to 1%, 0 to 0.6%, particularly preferably 0 to 0.4%.
Fe 2 O 3 Is an impurity component derived from a raw material, and is a component that absorbs ultraviolet light adversely affecting human eyes. However, if Fe 2 O 3 If the content of (2) is too large, the coloring of the glass is enhanced. Thus Fe 2 O 3 Preferably less than 1000ppm (i.e. 0.1%), less than 800ppm, less than 600ppm, less than 400ppm, less than 300ppm, less than 250ppm, less than 200ppm, less than 150ppm, particularly preferably less than 100ppm.
Nd 2 O 3 、La 2 O 3 The rare earth oxide is a component for improving Young's modulus. However, the cost of the raw material itself is high, and when the raw material is added in a large amount, the devitrification resistance tends to be lowered. Therefore, the rare earth oxide content is preferably 3% or less, 2% or less, 1% or less, 0.5% or less, and particularly preferably 0.1% or less.
SnO 2 Is a component which acts as a clarifying agent. SnO (SnO) 2 The content is preferably 0 to 3%, 0.001 to 3%, 0.05 to 1%, 0.1 to 0.5%, particularly preferably 0.1 to 0.3%.
From the environmental point of view, it is preferable that the glass composition contains substantially no As 2 O 3 、Sb 2 O 3 、PbO、F、Bi 2 O 3 . "substantially free" means that the content of the indicated component is less than 0.05% in the case where the impurity level is allowed to be mixed in, although the indicated component is not positively added as a glass component.
The glass sheet for strengthening of the present invention preferably has the following characteristics, for example. The tempered glass sheet of the present invention also preferably has the following characteristics, for example.
The bending strain is preferably 40.0X10 -5 Hereinafter, 30.0X10 -5 Hereinafter, 20.0X10 -5 Hereinafter, 10.0X10 -5 The following is 9.0X10 -5 The following are 8.0X10 -5 The following is 7.0X10 -5 Hereinafter, 6.0X10 -5 The following are 5.0X10 -5 Hereinafter, 4.0X10 -5 The following is 3.5X10 -5 The following is 3.0X10 -5 The following is 2.5X10 -5 The following is particularly preferred to be 2.0X10 -5 The following is given. If the bending strain is too large, visibility of the foldable display is lowered.
The strain point is preferably 480℃or higher, 500℃or higher, 520℃or higher, and particularly preferably 530 to 700 ℃. The higher the strain point, the lower the bending strain.
The softening point is preferably 950 ℃ or lower, 900 ℃ or lower, 880 ℃ or lower, 860 ℃ or lower, and particularly preferably 700 to 850 ℃. The lower the softening point, the higher the hot workability, and the less the burden on glass manufacturing equipment such as hot working equipment. Therefore, the lower the softening point, the more easily the manufacturing cost of the tempered glass sheet and the tempered glass sheet can be reduced.
The Young's modulus is preferably 75GPa or less, 73GPa or less, 71GPa or less, 69GPa or less, 67GPa or less, 66GPa or less, 65GPa or less, 64GPa or less, 63GPa or less, 62GPa or less, 61GPa or less, particularly 40 to 60GPa. The lower the Young's modulus, the lower the stress generated when bending the glass, and the less likely the glass will break when bending.
High temperature viscosity 10 2.5 The temperature at dPa.s is preferably less than 1650 ℃, 1630 ℃ or less, 1620 ℃ or less, particularly preferably 1610 ℃ or less. High temperature viscosity 10 2.5 The lower the temperature at dPa.s, the lower the melting temperature, the less burden is imposed on glass manufacturing equipment such as a melting furnace, and the foam quality is easily improved. Thus, high temperature viscosity 10 2.5 The lower the temperature at dPa.s, the more easily the manufacturing cost of the tempered glass plate and the glass plate for tempering can be reduced.
The liquid phase viscosity is preferably 4.0 dPa.s or more, 4.3 dPa.s or more, 4.5 dPa.s or more, 4.8 dPa.s or more, 5.1 dPa.s or more, 5.3 dPa.s or more, and particularly preferably 5.5 dPa.s or more in terms of Log ρ. If the liquid phase viscosity is too low, devitrification resistance is lowered, and it is difficult to produce a glass sheet for strengthening, particularly a glass sheet for strengthening having a small plate thickness, by overflow downdraw method or the like.
The tempered glass sheet of the present invention has a compressive stress layer on the surface. The compressive stress value of the outermost surface is preferably 100MPa or more, 200MPa or more, 400MPa or more, 500MPa or more, 600MPa or more, particularly preferably 700MPa or more. The larger the compressive stress value of the outermost surface, the easier it is to prevent breakage due to tensile stress generated at the bent portion of the tempered glass sheet when bending the foldable display. On the other hand, when a great compressive stress is formed on the surface, there is a possibility that the tensile stress existing in the tempered glass sheet becomes extremely high, and the dimensional change before and after the ion exchange treatment becomes large. Therefore, the compressive stress value of the outermost surface is preferably 1300MPa or less, 1100MPa or less, 900MPa or less, and particularly preferably 800MPa or less.
The stress depth is preferably 1 μm or more, 3 μm or more, 5 μm or more, 7 μm or more, 8 μm or more, 9 μm or more, particularly preferably 10 μm or more, and further 5 to 30%, 6 to 25%, 7 to 20%, 8 to 17%, 10 to 15%, 11 to 14%, particularly 12 to 13% of the plate thickness. The greater the stress depth, the less likely the tempered glass sheet will break and the less the deviation in mechanical strength will be even with deep flaws in the tempered glass sheet. On the other hand, the larger the stress depth, the more easily the dimensional change before and after the ion exchange treatment becomes. Therefore, the stress depth is preferably 20 μm or less and 15 μm or less, and particularly preferably 10 μm or less.
The internal tensile stress value is preferably 400MPa or less, 350MPa or less, 300MPa or less, 250MPa or less, 220MPa or less, 200MPa or less, 180MPa or less, and particularly preferably 170PMa or less. If the internal tensile stress value is too high, the tempered glass sheet is likely to break itself due to physical impact or the like. On the other hand, if the internal tensile stress value is too low, it is difficult to ensure the mechanical strength of the tempered glass sheet. The internal tensile stress value is preferably 60MPa or more, 80MPa or more, 100MPa or more, 125MPa or more, 140MPa or more, particularly preferably 150MPa or more. The internal tensile stress value can be calculated by the following equation 2.
Internal tensile stress value= (compressive stress value of outermost surface x stress depth)/(plate thickness-2 x stress depth) 2
In the glass sheet for strengthening and the glass sheet for strengthening of the present invention, the sheet thickness is preferably 200 μm or less, 150 μm or less, 100 μm or less, less than 100 μm, 80 μm or less, 60 μm or less, 1 to 50 μm, 5 to 40 μm, and particularly preferably 10 to 30 μm. The smaller the plate thickness, the more flexible the tempered glass plate is, and is easily applicable to a foldable display. In addition, the smaller the plate thickness, the smaller the allowable radius of curvature when bending the tempered glass plate, and the easier the tempered glass plate is wound into a roll shape.
The dimensions are preferably ≡50mm or more, ≡60deg.m or more, ≡70mm or more, ≡80mm or more, ≡90mm or more, ≡100deg.m, ≡120mm or more, ≡150mm or more, particularly preferably ≡200-2000 mm. When the size becomes large, the display device can be easily applied to a large flexible display.
The glass sheet for reinforcement of the present invention can be produced as follows. First, a glass raw material prepared to a desired glass composition is preferably charged into a continuous melting furnace, heated and melted at 1500 to 1700 ℃, clarified, and then the molten glass is supplied to a molding apparatus, molded into a plate shape, and cooled. The method of cutting into a predetermined size after forming into a plate shape may be a known method, but it is preferable to cut by laser fusing in order to smooth the end face.
In the molding of the molten glass, the cooling is preferably performed at a cooling rate of 2 ℃/min or more and less than 2500 ℃/min in a temperature region between the annealing point and the strain point of the molten glass, and the cooling rate is preferably 5 ℃/min or more, 10 ℃/min or more, 40 ℃/min or more, 60 ℃/min or more, particularly preferably 100 ℃/min or more, preferably less than 2500 ℃/min, less than 2000 ℃/min, less than 1800 ℃/min, less than 1500 ℃/min, less than 1300 ℃/min, less than 1000 ℃/min, less than 800 ℃/min, particularly preferably less than 500 ℃/min. If the cooling rate is too low, it is difficult to reduce the plate thickness. On the other hand, if the cooling rate is too high, the glass structure becomes rough, and the hardness of the reinforcing glass sheet tends to decrease.
As a method for forming the molten glass, an overflow downdraw method is preferably employed. The overflow downdraw method is a method that enables mass production of high-quality glass sheets and also enables easy production of thin glass sheets. Further, in the overflow downdraw method, alumina or zirconia is used as a refractory for the molded article, but the glass sheet for strengthening of the present invention is particularly suitable for alumina, and thus bubbles, pits, and the like are not easily generated during molding.
In addition to the overflow downdraw process, various shaping methods may be employed. For example, a float method, a downdraw method (a slot downdraw method, a redraw method, etc.), a roll-out method, a press method, etc. may be used.
The tempered glass plate of the present invention is produced by subjecting a tempered glass plate to ion exchange treatment. The conditions of the ion exchange treatment are not particularly limited, and the optimum conditions are selected in consideration of viscosity characteristics, application, sheet thickness, internal tensile stress, dimensional change, and the like of the glassAnd (3) obtaining the product. In particular, if KNO is to be used 3 The K ions in the molten salt are ion-exchanged with Na in the glass, so that a compressive stress layer on the surface can be efficiently formed.
The number of ion exchange treatments is not particularly limited, and may be performed only 1 time or may be performed a plurality of times. If the number of ion exchange treatments is 1, the cost of the tempered glass sheet can be reduced. In the case of performing the ion exchange treatment a plurality of times, the number of times of the ion exchange treatment is preferably 2 times. In this way, the stress depth can be increased, and the total amount of tensile stress accumulated in the glass can be reduced.
The glass sheet for strengthening of the present invention may be etched with an acidic solution such as hydrofluoric acid or an alkaline solution, and in particular, may be etched with an end face. The tempered glass plate of the present invention may be etched with an acidic solution such as hydrofluoric acid or an alkaline solution, and in particular, may be etched with an end face. If the etching treatment is performed before the ion exchange treatment, the plate thickness can be reduced, or the strength degradation due to damage can be suppressed. When the etching treatment is performed after the ion exchange treatment, the influence of scratches, surface roughness, and the like generated during the ion exchange treatment can be reduced.
Example 1
The present invention will be described below based on examples. The following examples are given by way of illustration only. The present invention is not limited in any way by the following examples.
Tables 1 to 10 show examples (sample nos. 1 to 147) and comparative examples (sample No. 148) of the present invention.
Each sample in the table was prepared as follows. First, glass raw materials were prepared so as to have glass compositions shown in tables 1 to 10, and the glass raw materials were melted at 1600 ℃ for 8 hours using a platinum pot. Then, the obtained molten glass was poured onto a carbon plate, formed into a flat plate shape, and cooled slowly. Various properties of the obtained glass sheet for strengthening were evaluated. The results are shown in tables 1 to 10.
TABLE 1
| (mol％) | No.1 | No.2 | No.3 | No.4 | No.5 | No.6 | No.7 | No.8 | No.9 | No.10 | No.11 | No.12 | No.13 | No.14 | No.15 | N0.16 |
| SiO 2 | 65.90 | 65.90 | 68.40 | 70.90 | 63.40 | 68.40 | 70.90 | 65.90 | 65.90 | 68.40 | 65.90 | 68.40 | 65.90 | 67.90 | 68.40 | 68.40 |
| Al 2 O 3 | 12.00 | 12.00 | 12.00 | 12.00 | 12.00 | 12.00 | 12.00 | 12.00 | 12.00 | 12.00 | 12.00 | 12.00 | 12.00 | 12.00 | 12.00 | 12.00 |
| B 2 O 3 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 4.00 | 8.00 | 0.00 | 0.00 | 0.00 | 0.00 | 4.00 | 0.00 | 0.00 |
| Li 2 O | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 |
| Na 2 O | 17.00 | 14.50 | 14.50 | 12.00 | 17.00 | 17.00 | 17.00 | 13.00 | 9.00 | 17.00 | 17.00 | 17.00 | 17.00 | 16.00 | 17.00 | 17.00 |
| K 2 O | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 |
| MgO | 5.00 | 7.50 | 5.00 | 5.00 | 7.50 | 2.50 | 0.00 | 5.00 | 5.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 |
| Ca0 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 2.50 | 5.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 |
| SrO | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 2.50 | 5.00 | 0.00 | 0.00 | 0.00 |
| BaO | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 |
| P 2 O 5 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 2.50 | 0.00 |
| ZrO 2 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 2.50 |
| SnO 2 | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 |
| Al 2 O 3 /Na 2 O | 0.71 | 0.83 | 0.83 | 1.00 | 0.71 | 0.71 | 0.71 | 0.92 | 1.33 | 0.71 | 0.71 | 0.71 | 0.71 | 0.75 | 0.71 | 0.71 |
| Na 2 O/Li 2 O+Na 2 O+K 2 O) | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 |
| Bending strain (. Times.10- 5 ) | 3.6 | 3.4 | 2.6 | 1.7 | 3.7 | 4.2 | 4.7 | 2.6 | 2.9 | 4.4 | 4.6 | 5.0 | 5.0 | 3.6 | Not measured | 3.3 |
| Ps(℃) | 597 | 628 | 633 | 667 | 602 | 587 | 561 | 578 | 580 | 566 | 570 | 552 | 553 | 551 | 583 | 635 |
| Ta(℃) | 648 | 679 | 688 | 726 | 651 | 637 | 610 | 628 | 634 | 612 | 614 | 597 | 595 | 593 | 635 | 690 |
| Ts(℃) | 886 | 917 | 943 | 997 | 875 | 883 | 855 | 877 | 895 | 838 | 823 | 822 | 804 | 801 | 889 | 946 |
| Young's modulus (GPa) | 70 | Not measured | Not measured | Not measured | Not measured | Not measured | 68 | Not measured | Not measured | 71 | 72 | 71 | 72 | 70 | 65 | 71 |
| 10 2.5 dPa·s(℃) | 1575 | 1594 | 1654 | 1721 | 1525 | 1646 | 1681 | 1598 | 1594 | 1592 | 1528 | 1599 | 1522 | 1626 | 1679 | 1659 |
| CS(MPa) | 1108 | Not measured | Not measured | Not measured | Not measured | Not measured | 710 | Not measured | Not measured | 901 | 965 | 814 | 881 | 901 | 714 | 1133 |
| DOL(μm) | 38 | Not measured | Not measured | Not measured | Unmeasured testFixing device | Not measured | 43 | Not measured | Not measured | 31 | 24 | 29 | 21 | 29 | 72 | 40 |
TABLE 2
| (mol％) | No.17 | No.18 | N0.19 | No.20 | No.21 | No.22 | No.23 | No.24 | No.25 | No.26 | No.27 | No.28 | No.29 | No.30 | No.31 | No.32 |
| SiO 2 | 64.62 | 61.60 | 69.90 | 69.90 | 69.90 | 69.90 | 69.90 | 69.90 | 69.90 | 69.90 | 65.90 | 65.90 | 65.90 | 65.90 | 65.90 | 65.90 |
| Al 2 O 3 | 12.50 | 12.50 | 10.00 | 12.00 | 14.00 | 12.00 | 14.00 | 16.00 | 13.00 | 11.00 | 10.00 | 12.00 | 14.00 | 12.00 | 14.00 | 16.00 |
| B 2 O 3 | 4.68 | 7.70 | 6.00 | 6.00 | 6.00 | 2.00 | 2.00 | 2.00 | 4.00 | 4.00 | 6.00 | 6.00 | 6.00 | 2.00 | 2.00 | 2.00 |
| Li 2 O | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 |
| Na 2 O | 12.60 | 12.60 | 14.00 | 12.00 | 10.00 | 16.00 | 14.00 | 12.00 | 13.00 | 15.00 | 14.00 | 12.00 | 10.00 | 16.00 | 14.00 | 12.00 |
| K 2 O | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 |
| MgO | 2.50 | 1.50 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 4.00 | 4.00 | 4.00 | 4.00 | 4.00 | 4.00 |
| CaO | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 |
| SrO | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 |
| BaO | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 |
| P 2 O 5 | 3.00 | 3.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 |
| ZrO 2 | 0.00 | 1.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 |
| SnO 2 | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 |
| Al 2 O 3 /Na 2 O | 0.99 | 0.99 | 0.71 | 1.00 | 1.40 | 0.75 | 1.00 | 1.33 | 1.00 | 0.73 | 0.71 | 1.00 | 1.40 | 0.75 | 1.00 | 1.33 |
| Na 2 O/(Li 2 O+Na 2 O+K 2 O | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 |
| Bending strain (. Times.10) -5 ) | 3.6 | 4.6 | 2.4 | 5.0 | 1.1 | 3.7 | 3.9 | 1.9 | 4.4 | 4.0 | 2.5 | 1.9 | 1.1 | 3.1 | 1.3 | 1.5 |
| Ps(℃) | 560 | 541 | 548 | 566 | 601 | 559 | 634 | 675 | 597 | 554 | 544 | 566 | 603 | 572 | 612 | 652 |
| Ta(℃) | 617 | 593 | 590 | 625 | 666 | 604 | 700 | 744 | 659 | 597 | 586 | 616 | 660 | 621 | 668 | 710 |
| Ts(℃) | 911 | 859 | 791 | 924 | 975 | 836 | 1016 | 1053 | 970 | 809 | 797 | 870 | 924 | 861 | 935 | 974 |
| Young's modulus (GPa) | 63 | 62 | 70 | 63 | 66 | 70 | 65 | 68 | 64 | 70 | 69 | 67 | 60 | 70 | 70 | 73 |
| 10 2.5 dPa·s(℃) | 1653 | 1617 | 1598 | 1718 | 1714 | 1666 | 1768 | 1762 | 1744 | 1646 | 1539 | 1616 | 1615 | 1597 | 1646 | 1648 |
| CS(MPa) | 809 | 774 | 845 | 904 | 7S1 | 834 | 1132 | 986 | 1032 | 842 | 895 | 920 | 809 | 1039 | 1142 | 1011 |
| DOL(μm) | 45 | 33 | 25 | 39 | 25 | 34 | 54 | 34 | 47 | 29 | 22 | 26 | 17 | 31 | 32 | 23 |
TABLE 3
| (mol ％) | No.33 | No.34 | No.35 | No.36 | No.37 | No.38 | No.39 | No.40 | No.41 | No.42 | No.43 | No.44 | No.45 | No.46 | No.47 | No.48 |
| SiO 2 | 65.90 | 65.90 | 65.90 | 65.90 | 65.90 | 65.90 | 65.90 | 65.90 | 65.90 | 65.90 | 65.90 | 65.90 | 65.90 | 65.90 | 65.90 | 65.90 |
| Al 2 O 3 | 12.00 | 14.00 | 16.00 | 14.00 | 16.00 | 18.00 | 10.00 | 12.00 | 14.00 | 12.00 | 14.00 | 16.00 | 15.00 | 17.00 | 19.00 | 10.00 |
| B 2 O 3 | 6.00 | 6.00 | 6.00 | 2.00 | 2.00 | 2.00 | 6.00 | 6.00 | 6.00 | 2.00 | 2.00 | 2.00 | 0.00 | 0.00 | 0.00 | 6.00 |
| Li 2 O | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 |
| Na 2 O | 16.00 | 14.00 | 12.00 | 18.00 | 16.00 | 14.00 | 14.00 | 12.00 | 10.00 | 16.00 | 14.00 | 12.00 | 19.00 | 17.00 | 15.00 | 14.00 |
| K 2 O | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 |
| MgO | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 |
| CaO | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 |
| SrO | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 |
| BaO | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 4.00 |
| P 2 O 5 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 4.00 | 4.00 | 4.00 | 4.00 | 4.00 | 4.00 | 0.00 | 0.00 | 0.00 | 0.00 |
| ZrO 2 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 |
| SnO 2 | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 |
| Al 2 O 3 / Na 2 O | 0.75 | 1.00 | 1.33 | 0.78 | 1.00 | 1.29 | 0.71 | 1.00 | 1.40 | 0.75 | 1.00 | 1.33 | 0.79 | 1.00 | 1.27 | 0.71 |
| Na 2 O/ (Li 2 O+ Na 2 O+ K 2 O) | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 |
| Bending Strain of (×10 -6 ) | Unmeasured test Fixing device | Final measurement Fixing device | Unmeasured test Fixing device | Unmeasured test Fixing device | Unmeasured test Fixing device | Unmeasured test Fixing device | Unmeasured test Fixing device | Not measured | Not measured | Not measured | Not measured | Not measured | 4.4 | 2.4 | 1.2 | Not measured |
| Ps (℃) | 548 | 569 | 603 | 561 | 635 | 674 | 514 | 528 | 565 | 558 | 591 | 639 | 592 | 720 | 739 | 541 |
| Ta (℃) | 588 | 625 | 665 | 607 | 699 | 740 | 559 | 583 | 632 | 610 | 654 | 710 | 643 | 786 | 805 | 579 |
| Ts (℃) | 789 | 911 | 957 | 839 | 1001 | 1032 | 793 | 877 | 962 | 868 | 962 | 1033 | 894 | 1067 | 1083 | 761 |
| Young's disease Modulus of (GPa) | 70 | 63 | 67 | 70 | 66 | 70 | 62 | 60 | 60 | 63 | 63 | 64 | 69 | 68 | 71 | 73 |
| 10 2.5 d Pa·s (℃) | 1569 | 1675 | 1659 | 1652 | 1718 | 1707 | 1611 | 1681 | 1703 | 1663 | 1716 | 1740 | 1673 | 1747 | 1730 | 1506 |
| CS (MPa) | 895 | 1016 | 922 | 880 | Unmeasured test Fixing device | 1124 | 557 | 586 | 629 | 679 | 772 | 811 | Not measured | Not measured | Not measured | 847 |
| DOL(μ m) | 26 | 39 | 26 | 37 | Unmeasured test Fixing device | 35 | 46 | 43 | 42 | 69 | 65 | 56 | Not measured | Not measured | Not measured | 11 |
TABLE 4
| (mol％+B110：R127) | No.49 | No.50 | No.51 | No.52 | No.53 | No.5 4 | No.5 5 | No.5 6 | No.5 7 | No.5 8 | No.5 9 | No.6 0 | No.6 1 | No.6 2 | No.63 | No.64 |
| SiO 2 | 65.90 | 65.90 | 65.90 | 65.90 | 65.90 | 63.9 0 | 63.9 0 | 63.9 0 | 65.9 0 | 65.9 0 | 63.9 0 | 65.9 0 | 65.9 0 | 65.9 0 | 65.90 | 59.90 |
| Al 2 O 3 | 12.00 | 14.00 | 12.00 | 14.00 | 16.00 | 13.0 0 | 14.0 0 | 15.0 0 | 13.0 0 | 14.0 0 | 14.0 0 | 12.0 0 | 13.0 0 | 14.0 0 | 16.00 | 15.00 |
| B 2 O 3 | 6.00 | 6.00 | 2.00 | 2.00 | 2.00 | 8.00 | 8.00 | 8.00 | 8.00 | 8.00 | 6.00 | 6.00 | 6.00 | 6.00 | 6.00 | 0.00 |
| Li 2 O | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 |
| Na 2 O | 12.00 | 10.00 | 16.00 | 14.00 | 12.00 | 15.0 0 | 14.0 0 | 13.0 0 | 13.0 0 | 12.0 0 | 14.0 0 | 14.0 0 | 13.0 0 | 12.0 0 | 8.00 | 23.00 |
| K 2 O | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 |
| MgO | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 |
| CaO | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 |
| SrO | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 |
| BaO | 4.00 | 4.00 | 4.00 | 4.00 | 4.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 |
| P 2 O 5 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 2.00 | 2.00 | 2.00 | 2.00 | 4.00 | 2.00 |
| ZrO 2 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 |
| SnO 2 | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 |
| Al 2 O 3 /Na 2 O | 1.00 | 1.40 | 0.75 | 1.00 | 1.33 | 0.87 | 1.00 | 1.15 | 1.00 | 1.17 | 1.00 | 0.86 | 1.00 | 1.17 | 2.00 | 0.65 |
| Na 2 O/(Li 2 O+Na 2 O+ K 2 O) | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 |
| Bending strain (. Times.10) -5 ) | Final measurement Fixing device | Unmeasured test Fixing device | Unmeasured test Fixing device | Unmeasured test Fixing device | Final measurement Fixing device | 2.1 | 3.8 | 1.7 | 3.0 | 2.5 | 2.6 | 2.1 | 2.1 | 1.3 | Unmeasured test Fixing device | Unmeasured test Fixing device |
| Ps(℃) | 552 | 587 | 535 | 573 | 646 | 540 | 553 | 567 | 547 | 563 | 553 | 537 | 549 | 567 | 602 | 570 |
| Ta(℃) | 595 | 645 | 577 | 620 | 708 | 584 | 609 | 626 | 603 | 623 | 609 | 585 | 606 | 630 | 670 | 617 |
| Ts(℃) | 800 | 921 | 779 | 860 | 1002 | 804 | 888 | 917 | 886 | 924 | 898 | 832 | 901 | 946 | 986 | 849 |
| Young's modulus (GPa) | 71 | 66 | 72 | 72 | 70 | 65 | 62 | 63 | 62 | 63 | 62 | 63 | 62 | 61 | 64 | 66 |
| 10 2.5 dPa·s(℃) | 1587 | 1655 | 1539 | 1657 | 1697 | 1598 | 1637 | 1642 | 1663 | 1668 | 1671 | 1652 | 1687 | 1689 | 1685 | 1551 |
| CS(MPa) | 888 | 845 | 812 | 983 | 1053 | 898 | 925 | 907 | 866 | 837 | 832 | 736 | 770 | 808 | 552 | 656 |
| DOL(μm | 12 | 14 | 16 | 17 | 21 | 28 | 34 | 28 | 34 | 27 | 42 | 39 | 41 | 41 | 25 | 77 |
TABLE 5
| (mol％) | No.65 | No.66 | No.67 | No.68 | No.69 | No.70 | No.71 | No.72 | No.73 | No.74 | No.75 | No.76 | No.77 | No.78 | No.79 | No.80 |
| SiO 2 | 59.90 | 59.90 | 59.90 | 59.90 | 63.90 | 63.90 | 63.90 | 63.90 | 63.90 | 63.90 | 64.90 | 64.90 | 64.90 | 65.90 | 64.90 | 63.90 |
| Al 2 O 3 | 17.00 | 19.00 | 21.00 | 23.00 | 12.00 | 14.00 | 16.00 | 14.00 | 16.00 | 18.00 | 12.00 | 14.00 | 16.00 | 11.50 | 12.00 | 12.50 |
| B 2 O 3 | 0.00 | 0.00 | 0.00 | 0.00 | 6.00 | 6.00 | 6.00 | 2.00 | 2.00 | 2.00 | 6.00 | 6.00 | 6.00 | 11.00 | 11.00 | 11.00 |
| Li 2 O | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 |
| Na 2 O | 21.00 | 19.00 | 17.00 | 15.00 | 16.00 | 14.00 | 12.00 | 18.00 | 16.00 | 14.00 | 16.00 | 14.00 | 12.00 | 11.50 | 12.00 | 12.50 |
| K 2 O | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 |
| MgO | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 |
| CaO | 0.00 | 0.00 | 0.00 | 0.00 | 2.00 | 2.00 | 2.00 | 2.00 | 2.00 | 2.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 |
| SrO | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 |
| BaO | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 |
| P 2 O 5 | 2.00 | 2.00 | 2.00 | 2.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 |
| ZrO 2 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 1.00 | 1.00 | 1.00 | 0.00 | 0.00 | 0.00 |
| SnO 2 | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 |
| Al 2 O 3 /Na 2 O | 0.81 | 1.00 | 1.24 | 1.53 | 0.75 | 1.00 | 1.33 | 0.78 | 1.00 | 1.29 | 0.75 | 1.00 | 1.33 | 1.00 | 1.00 | 1.00 |
| Na 2 O/(Li 2 O+Na 2 O+ K 2 O) | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 |
| Bending strain (. Times.10) -5 ) | Unmeasured test Fixing device | Unmeasured test Fixing device | Final measurement Fixing device | Unmeasured test Fixing device | Unmeasured test Fixing device | Unmeasured test Fixing device | Unmeasured test Fixing device | Unmeasured test Fixing device | Unmeasured test Fixing device | Unmeasured test Fixing device | Unmeasured test Fixing device | Unmeasured test Fixing device | Final measurement Fixing device | Unmeasured test Fixing device | Unmeasured test Fixing device | Unmeasured test Fixing device |
| Ps(℃) | 624 | 701 | 719 | 721 | 542 | 556 | 604 | 558 | 600 | 669 | 552 | 583 | 605 | 519 | 520 | 524 |
| Ta(℃) | 676 | 763 | 782 | 782 | 581 | 603 | 663 | 602 | 653 | 730 | 594 | 642 | 666 | 573 | 574 | 577 |
| Ts(℃) | 924 | 1029 | 1045 | 1031 | 771 | 841 | 936 | 823 | 918 | 1001 | 804 | 928 | 947 | 855 | 851 | 853 |
| Young's modulus (GPa) | 66 | 66 | 69 | 73 | 71 | 68 | 68 | 71 | 70 | 71 | 69 | 64 | 68 | 59 | 59 | 59 |
| 10 2.5 dPa·s(℃) | 1632 | 1676 | 1662 | 1630 | 1524 | 1598 | 1619 | 1588 | 1652 | 1666 | 1571 | 1654 | 1643 | 1680 | 1655 | 1644 |
| CS(MPa) | 953 | Unmeasured test Fixing device | 1231 | 1118 | 930 | 985 | 950 | 950 | 1142 | 1142 | 975 | 1033 | 936 | 669 | 697 | 727 |
| DOL(μm) | 65 | Unmeasured test Fixing device | 46 | 31 | 20 | 24 | 22 | 29 | 34 | 30 | 26 | 37 | 23 | 26 | 26 | 26 |
TABLE 6
| (mol％) | No.81 | No.82 | No.83 | No.84 | No.85 | No.86 | No.87 | No.88 | No.89 | No.90 | No.91 | No.92 | No.93 | No.94 | No.95 | No.96 |
| SiO 2 | 62.90 | 64.90 | 64.90 | 64.90 | 64.83 | 64.83 | 64.83 | 64.83 | 64.83 | 62.33 | 62.33 | 62.33 | 61.83 | 63.33 | 63.33 | 62.33 |
| Al 2 O 3 | 13.00 | 12.00 | 12.50 | 13.00 | 12.00 | 12.50 | 13.00 | 13.50 | 14.00 | 13.50 | 13.50 | 13.50 | 13.50 | 13.50 | 14.00 | 14.00 |
| B 2 O 3 | 11.00 | 10.00 | 10.00 | 10.00 | 9.05 | 9.05 | 9.05 | 9.05 | 9.05 | 9.05 | 9.05 | 9.05 | 9.05 | 9.05 | 9.05 | 9.05 |
| L 2 O | 0.00 | 0.00 | 0.00 | 0.00 | 0.02 | 0.02 | 0.02 | 0.02 | 0.02 | 0.02 | 0.02 | 0.02 | 0.02 | 0.02 | 0.02 | 0.02 |
| Na 2 O | 13.00 | 13.00 | 12.50 | 12.00 | 14.00 | 13.50 | 13.00 | 12.50 | 12.00 | 12.50 | 12.50 | 12.50 | 12.50 | 12.50 | 12.00 | 12.00 |
| K 2 O | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 |
| MgO | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 1.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 1.00 |
| CaO | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 1.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 |
| SrO | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 |
| BaO | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 1.00 | 1.00 | 0.00 | 0.00 | 0.00 |
| P 2 O 5 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 1.50 | 1.50 | 1.50 | 1>50 | 1.50 | 1.50 | 1.50 |
| ZrO 2 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.50 | 0.00 | 0.00 | 0.00 |
| SnO 2 | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 |
| Al 2 O 3 /Na 2 O | 1.00 | 0.92 | 1.00 | 1.08 | 0.86 | 0.93 | 1.00 | 1.08 | 1.17 | 1.08 | 1.08 | 1.08 | 1.08 | 1.08 | 1.17 | 1.17 |
| Na 2 O/(Li 2 O+Na 2 O+ K 2 O) | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 |
| Bending strain (. Times.10) -5 ) | Unmeasured test Fixing device | Unmeasured test Fixing device | Unmeasured test Fixing device | Unmeasured test Fixing device | Unmeasured test Fixing device | Unmeasured test Fixing device | Unmeasured test Fixing device | Unmeasured test Fixing device | Unmeasured test Fixing device | Unmeasured test Fixing device | Unmeasured test Fixing device | Unmeasured test Fixing device | Unmeasured test Fixing device | Unmeasured test Fixing device | Unmeasured test Fixing device | Unmeasured test Fixing device |
| Ps(℃) | 526 | 523 | 528 | 535 | 533 | 532 | 537 | 546 | 555 | 534 | 533 | 531 | 538 | 535 | 543 | 547 |
| Ta(℃) | 579 | 571 | 581 | 592 | 577 | 580 | 591 | 604 | 614 | 587 | 585 | 584 | 591 | 591 | 601 | 603 |
| Ts(℃) | 854 | 811 | 855 | 883 | 792 | 823 | 868 | 899 | 906 | 861 | 852 | 853 | 862 | 881 | 895 | 884 |
| Young's modulus (GPa) | 59 | 61 | 60 | 60 | 64 | 63 | 61 | 61 | 62 | 61 | 61 | 61 | 61 | 59 | 60 | 61 |
| 10 2.5 dPa·s(℃) | 1626 | 1625 | 1650 | 1648 | 1599 | 1641 | 1660 | 1652 | 1647 | 1631 | 1630 | 1647 | 1613 | 1650 | 1646 | 1618 |
| CS(MPa) | 758 | 776 | 767 | 756 | 841 | 837 | 834 | 824 | 816 | 767 | 769 | 765 | 799 | 750 | 755 | 781 |
| DOL(μm) | 26 | 28 | 29 | 28 | 27 | 29 | 32 | 30 | 27 | 28 | 28 | 27 | 26 | 33 | 31 | 28 |
TABLE 7
| (mol％) | No.97 | No.98 | No.99 | No.10 0 | No.10 1 | No.10 2 | No.10 3 | No.10 4 | No.10 5 | No.10 6 | No.10 7 | No.10 8 | No.10 9 | No.11 0 | No.11 1 | No.11 2 |
| SiO 2 | 62.33 | 62.33 | 63.33 | 62.33 | 62.33 | 62.33 | 62.83 | 62.90 | 62.90 | 62.90 | 62.40 | 62.40 | 62.40 | 63.23 | 63.03 | 62.83 |
| Al 2 O 3 | 14.00 | 14.00 | 13.00 | 13.00 | 13.00 | 13.00 | 13.00 | 12.75 | 13.25 | 13.75 | 12.75 | 13.25 | 13.75 | 14.00 | 14.00 | 14.00 |
| B 2 O 3 | 9.05 | 9.05 | 9.05 | 9.05 | 9.05 | 9.05 | 9.05 | 10.50 | 10.50 | 10.50 | 10.50 | 10.50 | 10.50 | 9.05 | 9.05 | 9.05 |
| Li 2 O | 0.02 | 0.02 | 0.02 | 0.02 | 0.02 | 0.02 | 0.02 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.02 | 0.02 | 0.02 |
| Na 2 O | 12.00 | 12.00 | 13.00 | 13.00 | 13.00 | 13.00 | 13.00 | 13.75 | 13.25 | 12.75 | 13.75 | 13.25 | 12.75 | 13.00 | 13.00 | 13.00 |
| K 2 O | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 |
| MgO | 0.00 | 0.00 | 0.00 | 1.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 |
| CaO | 1.00 | 0.00 | 0.00 | 0.00 | 1.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.39 | 0.39 | 0.39 |
| SrO | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 |
| BaO | 0.00 | 1.00 | 0.00 | 0.00 | 0.00 | 1.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.01 | 0.01 | 0.01 |
| P 2 O 5 | 1.50 | 1.50 | 1.50 | 1.50 | 1.50 | 1.50 | 2.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 |
| ZrO 2 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.50 | 0.50 | 0.50 | 0.20 | 0.40 | 0.60 |
| SnO 2 | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 |
| Al 2 O 3 /Na 2 O | 1.17 | 1.17 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 0.93 | 1.00 | 1.08 | 0.93 | 1.00 | 1.08 | 1.08 | 1.08 | 1.08 |
| Na 2 O/(Li 2 O+Na 2 O+ K 2 O) | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 |
| Bending strain (. Times.10) -5 ) | Unmeasured test Fixing device | Unmeasured test Fixing device | Unmeasured test Fixing device | Unmeasured test Fixing device | Unmeasured test Fixing device | Unmeasured test Fixing device | Unmeasured test Fixing device | Unmeasured test Fixing device | Unmeasured test Fixing device | Unmeasured test Fixing device | Unmeasured test Fixing device | Unmeasured test Fixing device | Unmeasured test Fixing device | 3.3 | 4.7 | Unmeasured test Fixing device |
| Ps(℃) | 544 | 540 | 526 | 530 | 633 | 528 | 622 | 524 | 529 | 535 | 627 | 534 | 541 | 550 | 550 | 552 |
| Ta(℃) | 599 | 596 | 578 | 580 | 583 | 576 | 574 | 674 | 581 | 591 | 576 | 587 | 696 | 605 | 606 | 608 |
| Ts(℃) | 877 | 878 | 850 | 843 | Unmeasured test Fixing device | 623 | 837 | 811 | 849 | 874 | 825 | 856 | 873 | 882 | 883 | 883 |
| Young's modulus (GPa) | 61 | 61 | 60 | 61 | 61 | 61 | 60 | 61 | 60 | 60 | 61 | 60 | 61 | 61 | 62 | 62 |
| 10 2.5 dPa·s(℃) | 1617 | 1626 | 1660 | 1636 | 1624 | 1631 | 1641 | 1605 | 1606 | 1617 | 1610 | 1608 | 1599 | 1616 | 1612 | 1601 |
| CS(MPa) | 785 | 775 | 720 | 754 | 756 | 758 | 683 | 800 | 796 | 792 | 827 | 819 | 814 | 891 | 898 | 908 |
| DOL(μm) | 27 | 26 | 32 | 30 | 28 | 26 | 33 | 28 | 28 | 26 | 27 | 27 | 25 | 27 | 27 | 27 |
TABLE 8
| (mol％) | No.11 3 | No.11 4 | No.11 5 | No.11 6 | No.11 7 | No.11 8 | No.11 9 | No.12 0 | No.12 1 | No.12 2 | No.12 3 | No.12 4 | No.12 5 | No.12 6 | No.12 7 | No.12 8 |
| SiO 2 | 63.23 | 62.83 | 64.43 | 64.23 | 63.83 | 64.43 | 64.03 | 63.83 | 64.03 | 65.45 | 62.88 | 63.68 | 64.14 | 63.94 | 63.74 | 63.78 |
| Al 2 O 3 | 14.00 | 14.00 | 13.00 | 13.00 | 13 .0 | 13.00 | 13.00 | 13.00 | 13.00 | 12.95 | 13.02 | 13.00 | 13.00 | 13.00 | 13.00 | 13.00 |
| B 2 O 3 | 9.05 | 9.05 | 9.05 | 9.05 | 9.05 | 9.05 | 9.05 | 9.05 | 9.05 | 8.62 | 9.63 | 9.40 | 9.10 | 9.30 | 9.50 | 9.30 |
| Li 2 O | 0.02 | 0.02 | 0.02 | 0.02 | 0.02 | 0.02 | 0.02 | 0.02 | 0.02 | 0.02 | 0.02 | 0.02 | 0.02 | 0.02 | 0.02 | 0.02 |
| Na 2 O | 13.00 | 13.00 | 12.50 | 12.50 | 12.50 | 12.50 | 12.50 | 12.50 | 12.50 | 12.48 | 12.55 | 12.50 | 12.50 | 12.50 | 12.50 | 12.50 |
| K 2 O | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 |
| MgO | 0.39 | 0.39 | 0.00 | 0.00 | 0.00 | 0.89 | 0.89 | 0.89 | 0.00 | 0.02 | 0.05 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 |
| CaO | 0.00 | 0.00 | 0.89 | 0.89 | 0.89 | 0.00 | 0.00 | 0.00 | 0.89 | 0.24 | 1.20 | 0.89 | 0.89 | 0.89 | 0.89 | 0.89 |
| SrO | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 |
| BaO | 0.01 | 0.01 | 0.01 | 0.01 | 0.01 | 0.01 | 0.01 | 0.01 | 0.01 | 0.01 | 0.01 | 0.01 | 0.01 | 0.01 | 0.01 | 0.01 |
| P 2 O 5 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 |
| ZrO 2 | 0.20 | 0.60 | 0.00 | 0.20 | 0.60 | 0.00 | 0.40 | 0.60 | 0.40 | 0.11 | 0.54 | 0.40 | 0.20 | 0.20 | 0.20 | 0.20 |
| SnO 2 | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 | 0.14 | 0.14 | 0.14 | 0.30 |
| Al 2 O 3 /Na 2 O | 1.08 | 1.08 | 1.04 | 1.04 | 1.04 | 1.04 | 1.04 | 1.04 | 1.04 | 1.04 | 1.04 | 1.04 | 1.04 | 1.04 | 1.04 | 1.04 |
| Na 2 O/(Li 2 O+Na 2 O+ K 2 O) | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 |
| Bending strain (. Times.10) -5 ) | 4.8 | Unmeasured test Fixing device | Unmeasured test Fixing device | 4.3 | Unmeasured test Fixing device | Unmeasured test Fixing device | 5.0 | Unmeasured test Fixing device | Unmeasured test Fixing device | Unmeasured test Fixing device | Unmeasured test Fixing device | Unmeasured test Fixing device | Unmeasured test Fixing device | Unmeasured test Fixing device | Unmeasured test Fixing device | Unmeasured test Fixing device |
| Ps(℃) | 551 | 554 | 540 | 544 | 548 | 541 | 546 | 547 | Unmeasured test Fixing device | Unmeasured test Fixing device | Unmeasured test Fixing device | Unmeasured test Fixing device | 543 | 542 | 540 | 542 |
| Ta(C) | 607 | 609 | 592 | 596 | 601 | 594 | 600 | 601 | Unmeasured test Fixing device | Unmeasured test Fixing device | Unmeasured test Fixing device | Unmeasured test Fixing device | 595 | 594 | 592 | 594 |
| Ts(℃) | 888 | 888 | 853 | 861 | 866 | 868 | 872 | 872 | Unmeasured test Fixing device | Unmeasured test Fixing device | Unmeasured test Fixing device | Unmeasured test Fixing device | 859 | 857 | 855 | 857 |
| Young's modulus (GPa) | 62 | 62 | 62 | 62 | 63 | 62 | 62 | 63 | Unmeasured test Fixing device | Unmeasured test Fixing device | Final measurement Fixing device | Unmeasured test Fixing device | 62 | 62 | 62 | 62 |
| 10 2.5 dPa·s(℃) | 1612 | 1596 | 1632 | 1630 | 1610 | 1640 | 1622 | 1610 | Unmeasured test Fixing device | Unmeasured test Fixing device | Final measurement Fixing device | Unmeasured test Fixing device | 1628 | 1624 | 1621 | 1624 |
| CS(MPa)) | 893 | 907 | 859 | 872 | 886 | 849 | 863 | 872 | Unmeasured test Fixing device | Unmeasured test Fixing device | Unmeasured test Fixing device | Unmeasured test Fixing device | 741 | 741 | 736 | 748 |
| DOL(μm) | 29 | 27 | 26 | 27 | 25 | 27 | 27 | 26 | Unmeasured test Fixing device | Unmeasured test Fixing device | Unmeasured test Fixing device | Unmeasured test Fixing device | 25 | 26 | 25 | 25 |
TABLE 9
| (mol％) | No.12 9 | No.13 0 | No.13 1 | No.13 2 | No.13 3 | No.13 4 | No.13 5 | No.13 6 | No.13 7 | No.13 8 | No.13 9 | No.14 0 | No.14 1 | No.14 2 | No.14 3 | No.14 4 |
| SiO 2 | 64.14 | 64.69 | 65.24 | 65.77 | 65.90 | 60.90 | 63.40 | 65.90 | 65.90 | 65.90 | 65.90 | 65.90 | 65.90 | 65.90 | 65.90 | 65.90 |
| Al 2 O 3 | 13.00 | 12.62 | 12.23 | 11.85 | 12.00 | 12.00 | 12.00 | 12.00 | 12.00 | 12.00 | 12.00 | 12.00 | 12.00 | 12.00 | 15.00 | 17.00 |
| B 2 O 3 | 9.30 | 7.09 | 4.88 | 2.68 | 0.00 | 0.00 | 0.00 | 12.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 |
| Li 2 O | 0.02 | 0.02 | 0.02 | 0.02 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 2.00 | 0.00 | 4.00 | 5.50 | 0.00 | 2.00 | 2.00 |
| Na 2 O | 12.50 | 13.18 | 13.87 | 14.55 | 22.00 | 22.00 | 19.50 | 5.00 | 20.00 | 20.00 | 18.00 | 18.00 | 16.50 | 16.50 | 17.00 | 15.00 |
| K 2 O | 0.00 | 0.35 | 0.70 | 1.05 | 0.00 | 0.00 | 0.00 | 0.00 | 2.00 | 0.00 | 4.00 | 0.00 | 0.00 | 5.50 | 0.00 | 0.00 |
| MgO | 0.00 | 1.21 | 2.42 | 3.63 | 0.00 | 5.00 | 5.00 | 5.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 |
| CaO | 0.89 | 0.69 | 0.49 | 0.30 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 |
| SrO | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 |
| BaO | 0.01 | 0.01 | 0.01 | 0.01 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 |
| P 2 O 5 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 |
| ZrO 2 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 |
| SnO 2 | 0.14 | 0.14 | 0.14 | 0.14 | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 |
| Al 2 O 3 /Na 2 O | 1.04 | 0.96 | 0.88 | 0.81 | 0.55 | 0.55 | 0.62 | 2.40 | 0.60 | 0.60 | 0.67 | 0.67 | 0.73 | 0.73 | 0.88 | 1.13 |
| Na 2 O/(Li 2 O+Na 2 O+ K 2 O) | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 0.91 | 0.91 | 0.82 | 0.82 | 0.75 | 0.75 | 0.89 | 0.88 |
| Bending strain (. Times.10) -5 ) | Final measurement Fixing device | Final measurement Fixing device | Unmeasured test Fixing device | Unmeasured test Fixing device | 5.9 | 5.6 | 6.2 | 6.7 | 21.7 | 29.8 | 28.8 | 32.8 | 31.1 | 32.0 | 22.4 | 11.0 |
| Ps(℃) | 543 | 547 | 552 | 561 | 526 | 548 | 571 | 587 | 512 | 490 | 504 | 476 | 466 | 494 | 548 | 666 |
| Ta(℃) | 596 | 594 | 598 | 609 | 567 | 591 | 617 | 642 | 554 | 532 | 547 | 517 | 507 | 537 | 597 | 727 |
| Ts(℃) | 861 | 835 | 833 | 849 | 774 | 797 | 837 | 892 | 767 | 739 | 764 | 719 | 708 | 759 | 851 | 1009 |
| Young's modulus (GPa) | 62 | Final measurement Fixing device | Unmeasured test Fixing device | Unmeasured test Fixing device | 67 | Unmeasured test Fixing device | Final measurement Fixing device | Unmeasured test Fixing device | 69 | 72 | 69 | 74 | Unmeasured test Fixing device | Unmeasured test Fixing device | Unmeasured test Fixing device | Unmeasured test Fixing device |
| 10 2.5 dPa·s(℃) | 1632 | 1602 | 1592 | 1605 | 1507 | 1444 | 1512 | 1555 | 1520 | 1479 | 1538 | 1462 | 1432 | 1534 | 1654 | 1704 |
| CS(MPa) | 743 | Unmeasured test Fixing device | Unmeasured test Fixing device | Final measurement Fixing device | 495 | Unmeasured test Fixing device | Unmeasured test Fixing device | Unmeasured test Fixing device | 497 | 499 | 525 | 442 | Unmeasured test Fixing device | Unmeasured test Fixing device | Unmeasured test Fixing device | Unmeasured test Fixing device |
| DOL(μm)) | 27 | Unmeasured test Fixing device | Unmeasured test Fixing device | Unmeasured test Fixing device | 57 | Unmeasured test Fixing device | Unmeasured test Fixing device | Unmeasured test Fixing device | 63 | 38 | 67 | 30 | Unmeasured test Fixing device | Unmeasured test Fixing device | Unmeasured test Fixing device | Unmeasured test Fixing device |
TABLE 10
| (mol％) | No.145 | No.146 | No.147 | No.148 |
| SiO 2 | 63.98 | 63.98 | 64.18 | 65.90 |
| Al 2 O 3 | 13.00 | 13.00 | 13.00 | 12.00 |
| B 2 O 3 | 9.30 | 9.30 | 9.30 | 0.00 |
| Li 2 O | 0.02 | 0.02 | 0.02 | 0.00 |
| Na 2 O | 12.50 | 12.50 | 12.50 | 11.00 |
| K 2 O | 0.00 | 0.00 | 0.00 | 11.00 |
| MgO | 0.00 | 0.00 | 0.00 | 0.00 |
| CaO | 0.89 | 0.89 | 0.89 | 0.00 |
| SrO | 0.00 | 0.00 | 0.00 | 0.00 |
| BaO | 0.01 | 0.01 | 0.01 | 0.00 |
| P 2 O 5 | 0.00 | 0.00 | 0.00 | 0.00 |
| ZrO 2 | 0.00 | 0.20 | 0.00 | 0.00 |
| SnO 2 | 0.30 | 0.10 | 0.10 | 0.10 |
| Al 2 O 3 /Na 2 O | 1.04 | 1.04 | 1.04 | 1.09 |
| Na 2 O/(Li 2 O+Na 2 O+K 2 O) | 1.00 | 1.00 | 1.00 | 0.50 |
| Bending strain (. Times.10) -5 ) | Not measured | Final measurement | Not measured | 40.6 |
| Ps(℃) | 543 | 545 | 542 | 499 |
| Ta(℃) | 596 | 598 | 595 | 545 |
| Ts(℃) | 860 | 864 | 861 | 779 |
| Young's modulus (GPa) | 62 | 62 | 62 | Not measured |
| 10 2.5 dPa·s(℃) | 1616 | 1624 | 1629 | 1586 |
| CS(MPa) | 744 | 748 | 737 | Not measured |
| DOL(μm) | 25 | 27 | 27 | Final measurement |
Next, from the obtained reinforcing glass plate, cylindrical glass having a diameter of 6mm was obtained by grinding, and then, a fibrous glass having a length of 150mm and a diameter of 0.13mm was produced by redrawing, to obtain a sample for evaluation. Using this sample for evaluation, bending strain (JIS K7116) was evaluated by the method described above. Further, it was confirmed that the value of bending strain measured on the fibrous glass was the same as that of a glass plate formed by the overflow downdraw method and having a thickness t of 0.2mm or less. Although the glass composition in the surface layer of the glass is microscopically different before and after the ion exchange treatment, the glass composition is not substantially different when viewed as a whole, and thus the bending strain is not changed.
The strain point Ps and the annealing point Ta are values measured by a known fiber elongation method. The softening point Ts refers to a value measured by the method of ASTM C338.
Young's modulus is a value obtained by measuring a glass plate for strengthening by a known resonance method. Although the young's modulus in the surface layer of the glass is microscopically different before and after the ion exchange treatment, the young's modulus is not substantially different when the glass is observed as a whole, since the young's modulus is measured as an average value by a resonance method.
High temperature viscosity 10 2.5 The temperature at dPa.s is a value measured by a platinum ball pulling method.
Further, the obtained glass plate for strengthening was subjected to optical polishing on both surfaces thereof, and after the plate thickness was set to 0.7mm, KNO at 430 ℃ 3 The ion exchange treatment was performed by immersing in the molten salt for 4 hours. The surface of each sample was cleaned after the ion exchange treatment. Then, the compressive stress value CS and the stress depth DOL of the outermost surface were calculated from the number of interference fringes and the intervals thereof observed by using a surface stress meter (FSM-6000 manufactured by the society of manufacturing of folding origin). In the calculation, the refractive index of each sample was 1.50 and the optical elastic constant was 29.5[ (nm/cm)/MPa ]]. Although the glass composition in the surface layer of the glass is microscopically different before and after the ion exchange treatment, the glass composition is not substantially different when the entire glass is observed.
As is clear from the table, since the bending of sample Nos. 1 to 147 should be small, the visibility of the bending portion is not easily degraded. On the other hand, since the sample No.148 should be bent largely, visibility of the bent portion is liable to be deteriorated.
Example 2
Glass batches having glass compositions of sample Nos. 1 to 147 shown in tables 1 to 10 were melted in a test melting furnace to obtain molten glass, which was then formed and cut by the overflow downdraw method to form glass plates for strengthening each having a plate thickness of 50. Mu.m. In addition, the speed of the drawing rolls, the speed of the cooling rolls, the temperature distribution of the heating device, the temperature of the molten glass, the flow rate of the molten glass, and the drawing speed are appropriately adjusted in forming the glass sheet.
The obtained tempered glass plates nos. 1 to 147 were subjected to ion exchange treatment, thereby producing tempered glass plates having compressive stress layers. Then, by appropriately changing the conditions of the ion exchange treatment, the compressive stress value of the outermost surface of the compressive stress layer is adjusted to 600 to 700MPa, and the stress depth is adjusted to 8 to 12. Mu.m.
Sample nos. 1 to 147 before ion exchange treatment were held in a bent state for a predetermined period of time, and when the held state was released, the visibility of the bent portion of the glass plate was hardly degraded (visibility was good). Further, sample nos. 1 to 147 after the ion exchange treatment were held in a bent state for a predetermined period of time, and when the held state was released, the visibility of the bent portion of the glass plate was not easily degraded (visibility was good). On the other hand, sample No.148 of the comparative example was held in a bent state for a certain period of time before and after the ion exchange treatment, and when the held state was released, the visibility of the bent portion of the glass plate was liable to be degraded (visibility was poor).
Specifically, visibility was evaluated in the following manner. First, the glass sample was held for 24 hours in a state where the glass sample was bent so that the radius of curvature of the bent portion was 13mm, and then the held state was released. Next, the glass sample was placed on a horizontal stage so as to face down outward when bent. Further, the surface of the glass sample on the stage was irradiated with light of a fluorescent lamp in a straight tube shape from directly above the glass sample, and the reflection of the light of the fluorescent lamp at the glass surface having the curved portion was visually observed from a position separated by 30cm in the 45±5° direction with respect to the stage. Specifically, when the line of the light of the fluorescent lamp reflected on the surface of the glass sample is not bent at the bent portion but is straight, the glass sample is evaluated as "hardly decreasing in visibility" (fig. 2), and when the line of the light of the fluorescent lamp reflected on the surface of the glass sample is bent at the bent portion into a folded line, the glass sample is evaluated as "easily decreasing in visibility" (fig. 3).
Industrial applicability
The tempered glass plate of the present invention is suitable for a flexible cover member for a foldable display or the like.
Claims (14)
1. A glass plate for reinforcement, characterized in that,
the glass plate for strengthening has a plate thickness of 0.2mm or less,
the glass plate for strengthening contains, as a glass composition, in mol%: siO (SiO) 2 50～80％、Al 2 O 3 2～25％、Na 2 O2-25%, mole ratio Al 2 O 3 /Na 2 O is 0.5-2.5, mole ratio Na 2 O/(Li 2 O+Na 2 O+K 2 O) is 0.70 or more.
2. A glass sheet for strengthening according to claim 1, wherein,
the glass plate for strengthening has a plate thickness of 0.2mm or less,
the glass plate for strengthening contains, as a glass composition, in mol%: siO (SiO) 2 50～80％、Al 2 O 3 2～20％、Na 2 O2-20%, and mole ratio Al 2 O 3 /Na 2 O is more than 0.62 and less than 2, and the mole ratio of Na 2 O/(Li 2 O+Na 2 O+K 2 O) is 0.90 or more.
3. A glass sheet for strengthening according to claim 1, wherein,
the glass plate for strengthening has a plate thickness of 0.15mm or less,
the glass plate for strengthening contains, as a glass composition, in mol%: siO (SiO) 2 50～80％、Al 2 O 3 2～20％、MgO 0～8％、Na 2 O2-20%, and mole ratio Al 2 O 3 /Na 2 O is 0.68-2, mole ratio Na 2 O/(Li 2 O+Na 2 O+K 2 O) is 0.90 or more.
4. A glass sheet for strengthening according to any one of claim 1 to 3,
the glass plate for reinforcement has a plate thickness of 0.10mm or less.
5. A glass sheet for strengthening according to any one of claims 1 to 4,
the glass composition contains 10.5 to 20 mol% of Al 2 O 3 。
6. A glass sheet for strengthening according to any one of claims 1 to 5,
the glass composition contains 1 to 15 mol% of B 2 O 3 。
7. A glass sheet for strengthening according to any one of claims 1 to 6,
the bending strain of the glass sheet for strengthening calculated according to JIS K7116 was 40.0X10 -5 The following is given.
8. A strengthened glass plate is characterized in that,
the tempered glass plate is formed by subjecting a tempered glass plate to ion exchange treatment,
a compressive stress layer is provided on the surface of the tempered glass sheet,
the glass sheet for strengthening according to any one of claims 1 to 7.
9. A tempered glass sheet as claimed in claim 8 wherein,
the compressive stress value of the outermost surface of the compressive stress layer is 100 MPa-800 MPa.
10. A strengthened glass plate is characterized in that,
the plate thickness of the reinforced glass plate is below 0.2mm,
a compressive stress layer is provided on the surface of the tempered glass sheet,
the tempered glass sheet contains, as a glass composition, in mol%: siO (SiO) 2 50～80％、Al 2 O 3 2～25％、Na 2 O2-25%, and mole ratio Al 2 O 3 /Na 2 O is 0.5-2.5, mole ratio Na 2 O/(Li 2 O+Na 2 O+K 2 O) is 0.70 or more.
11. A tempered glass sheet as claimed in claim 10 wherein,
the plate thickness of the reinforced glass plate is below 0.2mm,
a compressive stress layer is provided on the surface of the tempered glass sheet,
the tempered glass sheet contains, as a glass composition, in mol%: siO (SiO) 2 50～80％、Al 2 O 3 2～20％、Na 2 O2-20%, and mole ratio Al 2 O 3 /Na 2 O is more than 0.62 and less than 2, and the mole ratio of Na 2 O/(Li 2 O+Na 2 O+K 2 O) is 0.90 or more.
12. A tempered glass sheet as claimed in claim 10 wherein,
the plate thickness of the reinforced glass plate is below 0.15mm,
a compressive stress layer is provided on the surface of the tempered glass sheet,
the tempered glass sheet contains, as a glass composition, in mol%: siO (SiO) 2 50～80％、Al 2 O 3 2～20％、MgO 0～8％、Na 2 O2-20%, and mole ratio Al 2 O 3 /Na 2 O is 0.68-2 molMolar ratio Na 2 O/(Li 2 O+Na 2 O+K 2 O) is 0.90 or more.
13. Tempered glass sheet according to any of claims 10 to 12, characterized in that,
the plate thickness of the reinforced glass plate is below 0.10 mm.
14. Tempered glass sheet according to any of claims 10 to 13, characterized in that,
the bending strain of the tempered glass plate calculated according to JIS K7116 was 40.0X10 -5 The following is given.
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| JP2021-115466 | 2021-07-13 | ||
| JP2021176509 | 2021-10-28 | ||
| JP2021-176509 | 2021-10-28 | ||
| PCT/JP2022/026815 WO2023286668A1 (en) | 2021-07-13 | 2022-07-06 | Glass plate for tempering, and tempered glass plate |
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| CN117597320A true CN117597320A (en) | 2024-02-23 |
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