JP6586142B2 - 高い亀裂発生閾値を有するイオン交換可能なガラス - Google Patents
高い亀裂発生閾値を有するイオン交換可能なガラス Download PDFInfo
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- JP6586142B2 JP6586142B2 JP2017195256A JP2017195256A JP6586142B2 JP 6586142 B2 JP6586142 B2 JP 6586142B2 JP 2017195256 A JP2017195256 A JP 2017195256A JP 2017195256 A JP2017195256 A JP 2017195256A JP 6586142 B2 JP6586142 B2 JP 6586142B2
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- 239000011521 glass Substances 0.000 title claims description 190
- 230000000977 initiatory effect Effects 0.000 title description 21
- 239000005358 alkali aluminosilicate glass Substances 0.000 claims description 140
- 239000011734 sodium Substances 0.000 claims description 63
- 229910052708 sodium Inorganic materials 0.000 claims description 49
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 47
- 229910052760 oxygen Inorganic materials 0.000 claims description 44
- 238000007906 compression Methods 0.000 claims description 38
- 230000006835 compression Effects 0.000 claims description 38
- 238000005342 ion exchange Methods 0.000 claims description 33
- 238000007373 indentation Methods 0.000 claims description 31
- 229910052796 boron Inorganic materials 0.000 claims description 28
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 26
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 25
- 229910052700 potassium Inorganic materials 0.000 claims description 25
- 239000011591 potassium Substances 0.000 claims description 25
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 23
- 150000002500 ions Chemical group 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 17
- 229910052792 caesium Inorganic materials 0.000 claims description 15
- 229910052701 rubidium Inorganic materials 0.000 claims description 15
- 229910001408 cation oxide Inorganic materials 0.000 claims description 10
- 238000005336 cracking Methods 0.000 claims description 5
- 239000005354 aluminosilicate glass Substances 0.000 claims description 4
- 238000005728 strengthening Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 description 70
- 229910001409 divalent cation oxide Inorganic materials 0.000 description 24
- 229910018068 Li 2 O Inorganic materials 0.000 description 14
- 229910021645 metal ion Inorganic materials 0.000 description 10
- 239000000463 material Substances 0.000 description 8
- 239000003513 alkali Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- 229910001423 beryllium ion Inorganic materials 0.000 description 5
- 229910010413 TiO 2 Inorganic materials 0.000 description 4
- 239000000356 contaminant Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 229910017119 AlPO Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910006404 SnO 2 Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 2
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 description 2
- -1 but not limited to Inorganic materials 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 230000001627 detrimental effect Effects 0.000 description 2
- 239000006025 fining agent Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- IBIRZFNPWYRWOG-UHFFFAOYSA-N phosphane;phosphoric acid Chemical compound P.OP(O)(O)=O IBIRZFNPWYRWOG-UHFFFAOYSA-N 0.000 description 2
- 239000005341 toughened glass Substances 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 238000007545 Vickers hardness test Methods 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 229910001491 alkali aluminosilicate Inorganic materials 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- 230000000840 anti-viral effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000003678 scratch resistant effect Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
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- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/097—Glass compositions containing silica with 40% to 90% silica, by weight containing phosphorus, niobium or tantalum
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- C03C14/00—Glass compositions containing a non-glass component, e.g. compositions containing fibres, filaments, whiskers, platelets, or the like, dispersed in a glass matrix
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- C03C21/00—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface
- C03C21/001—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions
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- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
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- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
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- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
- C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
- C03C3/087—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal containing calcium oxide, e.g. common sheet or container glass
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- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
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- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
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- C03C3/062—Glass compositions containing silica with less than 40% silica by weight
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- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
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- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
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- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
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- C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
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Description
i. 0.6<[M2O3(モル%)/RXO(モル%)]<1.4;または
ii. 1.3<[(P2O5+R2O)/M2O3]≦2.3;
であり、式中M2O3=Al2O3+B2O3であり、RXOが、アルカリアルミノケイ酸ガラス中に存在する一価および二価のカチオン酸化物の合計であり、R2Oがアルカリアルミノケイ酸ガラス中に存在する一価カチオン酸化物の合計である、アルカリアルミノケイ酸ガラスを含む。一部の実施形態において、ガラスは0.6<[M2O3(モル%)/RXO(モル%)]<1.4を満たす。一部の実施形態において、ガラスは0.6<[M2O3(モル%)/RXO(モル%)]<1を満たす。一部の実施形態において、ガラスは1.3<[(P2O5+R2O)/M2O3]≦2.3を満たす。一部の実施形態において、ガラスは1.5<[(P2O5+R2O)/M2O3]≦2.0を満たす。一部の実施形態において、アルカリアルミノケイ酸ガラスは1モル%未満のK2Oをさらに含んでいる。一部の実施形態において、アルカリアルミノケイ酸ガラスは、さらに、1モル%未満のB2O3を含む。一部の実施形態において、一価および二価のカチオン酸化物は、Li2O、Na2O、K2O、Rb2O、Cs2O、MgO、CaO、SrO、BaOおよびZnOからなる群から選択される。一部の実施形態において、アルカリアルミノケイ酸ガラスは、410℃で少なくとも約2.4×10−10cm2/sのカリウム/ナトリウム相互拡散係数を有する。一部の実施形態において、カリウム/ナトリウム相互拡散係数は、約2.4×10−10cm2/s〜約1.5×10−9cm2の範囲内にある。一部の実施形態において、ガラスは、その表面から層深さまで延在する圧縮層を有し、ここで圧縮層は少なくとも約300MPaの圧縮応力下にある。一部の実施形態において、ガラスは、少なくとも約7kgfのビッカース圧子圧入亀裂発生荷重を有する。一部の実施形態において、ガラスは少なくとも約12kgfのビッカース圧子圧入亀裂発生荷重を有する。
i. 0.6<[M2O3(モル%)/RXO(モル%)]<1.4;または
ii. 1.3<[(P2O5+R2O)/M2O3]≦2.3;
であり、式中M2O3=Al2O3+B2O3であり、RXOが、アルカリアルミノケイ酸ガラス中に存在する一価および二価のカチオン酸化物の合計であり、R2Oがアルカリアルミノケイ酸ガラス中に存在する一価カチオン酸化物の合計であるアルカリアルミノケイ酸ガラスを提供するステップと;最大約24時間の時限中イオン交換浴中にアルカリアルミノケイ酸ガラスを浸漬して、アルカリアルミノケイ酸ガラスの表面から少なくとも10μmの層深さまで延在する圧縮層を形成するステップとを含む、アルカリアルミノケイ酸ガラスを強化する方法を含んでいる。一部の実施形態において、ガラスは0.6<[M2O3(モル%)/RXO(モル%)]<1.4を満たす。一部の実施形態において、ガラスは0.6<[M2O3(モル%)/RXO(モル%)]<1を満たす。一部の実施形態において、ガラスは1.3<[(P2O5+R2O)/M2O3]≦2.3を満たす。一部の実施形態において、ガラスは1.5<[(P2O5+R2O)/M2O3]≦2.0を満たす。一部の実施形態において、アルカリアルミノケイ酸ガラスは1モル%未満のK2Oを含む。一部の実施形態において、アルカリアルミノケイ酸ガラスは、1モル%未満のB2O3を含む。一部の実施形態において、圧縮層は少なくとも約300MPaの圧縮応力下にある。一部の実施形態において、イオン交換ガラスは、少なくとも約7kgfのビッカース圧子圧入亀裂発生荷重を有する。一部の実施形態において、イオン交換ガラスは少なくとも約12kgfのビッカース圧子圧入亀裂発生荷重を有する。
i. 0.6<[M2O3(モル%)/RXO(モル%)]<1.4;または
ii. 1.3<[(P2O5+R2O)/M2O3]≦2.3;
であり、式中M2O3=Al2O3+B2O3であり、RXOが、アルカリアルミノケイ酸ガラス中に存在する一価および二価のカチオン酸化物の合計であり、R2Oがアルカリアルミノケイ酸ガラス中に存在する一価カチオン酸化物の合計であるアルカリアルミノケイ酸ガラスを提供するステップと;最大約24時間の時限中イオン交換浴中にアルカリアルミノケイ酸ガラスを浸漬して、アルカリアルミノケイ酸ガラスの表面から少なくとも10μmの層深さまで延在する圧縮層を形成するステップとを含む。一部の実施形態において、ガラスは0.6<[M2O3(モル%)/RXO(モル%)]<1.4を満たす。一部の実施形態において、ガラスは0.6<[M2O3(モル%)/RXO(モル%)]<1を満たす。一部の実施形態において、ガラスは1.3<[(P2O5+R2O)/M2O3]≦2.3を満たす。一部の実施形態において、ガラスは1.5<[(P2O5+R2O)/M2O3]≦2.0を満たす。一部の実施形態において、アルカリアルミノケイ酸ガラスは1モル%未満のK2Oを含んでいる。一部の実施形態において、アルカリアルミノケイ酸ガラスは、1モル%未満のB2O3を含む。一部の実施形態において、圧縮層は少なくとも約300MPaの圧縮応力下にある。一部の実施形態において、イオン交換ガラスは、少なくとも約7kgfのビッカース圧子圧入亀裂発生荷重を有する。一部の実施形態において、イオン交換ガラスは少なくとも約12kgfのビッカース圧子圧入亀裂発生荷重を有する。一部の実施形態において、圧縮層は表面から、少なくとも70μmの層深さまで延在する。
0.75≦[(P2O5(モル%)+R2O(モル%))/M2O3(モル%)]≦1.3
(式中、M2O3=Al2O3+B2O3)。
[(Al2O3(モル%)+B2O3(モル%))/(Σ改質酸化物(モル%))]<1.0
一部の実施形態において、ガラスはガラス構造を可能にするのに充分なP2O5を有することができ、ここでP2O5はむしろ構造中に存在するかまたはMPO4に加えて存在する。一部の実施形態において、このような構造は、1.24超の[(P2O5(モル%)+R2O(モル%))/M2O3(モル%)]比により表現されてよく、式中M2O3=Al2O3+B2O3であり、P2O5は4モル%以上であり、R2Oはアルカリアルミノケイ酸ガラス中に存在する二価のカチオン酸化物の合計である。一部の実施形態において、本明細書中に記載のガラスは、4モル%超のP2O5を含み、ここで[(P2O5(モル%)+R2O(モル%))/M2O3(モル%)]の比は1.24超であり、式中M2O3=Al2O3+B2O3であり、ここでR2Oは、アルカリアルミノケイ酸ガラス中に存在する二価のカチオン酸化物の合計である。一部の実施形態において、[(P2O5(モル%)+R2O(モル%))/M2O3(モル%)]の比は1.3超である。一部の実施形態において、この比は1.24≦[(P2O5(モル%)+R2O(モル%))/M2O3(モル%)]≦2.8である。一部の実施形態において、本明細書中に記載のガラスおよびガラス物品は4モル%超のP2O5を含み、
S≦[(P2O5(モル%)+R2O(モル%))/M2O3(モル%)]≦V
の比で表現される。式中、Sは独立して約1.5、1.45、1.4、1.35、1.3、1.25、1.24、1.2または1.15であり、Vは独立して約2.0、2.05、2.1、2.15、2.2、2.25、2.3、2.35、2.4、2.45、2.5、2.55、2.6、2.65、2.7、2.75または2.8である。
Claims (8)
- 40モル%〜70モル%のSiO2;11モル%〜25モル%のAl2O3;4モル%〜15モル%のP2O5;13モル%〜20モル%のNa2O、1モル%未満のB2O3,およびMgOを含み、K2Oを含まないアルカリアルミノケイ酸ガラスであって、
i. Na2O、Rb2O、Cs2Oからなる群より選択される一価のカチオン酸化物R2Oを含有し;かつ
ii. 1.3<[(P2O5(モル%)+R2O(モル%))/M2O3(モル%)]≦2.3;
であり、式中M2O3=Al2O3+B2O3であり、R2Oが前記アルカリアルミノケイ酸ガラス中に存在する一価カチオン酸化物の合計であり、
前記ガラスが少なくとも10μmの層深さまでイオン交換可能なものである、
アルカリアルミノケイ酸ガラス。 - 前記ガラスが、下記式
1.5<[(P2O5(モル%)+R2O(モル%))/M2O3(モル%)]≦2.0
を満たす、請求項1に記載のアルカリアルミノケイ酸ガラス。 - 前記アルカリアルミノケイ酸ガラスが50モル%〜65モル%のSiO2と;14モル%〜20モル%のAl2O3と;4モル%〜10モル%のP2O5と;14モル%〜20モル%のNa2Oを含む、請求項1に記載のアルカリアルミノケイ酸ガラス。
- カリウム/ナトリウム相互拡散係数が、410℃で2.4×10−10cm2/s〜1.5×10−9cm2/sの範囲内にあるか;または、前記ガラスがイオン交換された場合にこのイオン交換されたガラスの表面から前記層深さまで延在する圧縮層を有し、その圧縮層が少なくとも300MPaの圧縮応力下にあるか;または前記ガラスがイオン交換された場合にそのイオン交換されたガラスが少なくとも12kgfのビッカース圧子圧入亀裂発生荷重を有する、請求項1〜3のいずれか1項に記載のアルカリアルミノケイ酸ガラス。
- 請求項1〜4のいずれか1項に記載のアルカリアルミノケイ酸ガラスを含む電子製品。
- アルカリアルミノケイ酸ガラスを強化する方法において、
a.40モル%〜70モル%のSiO2;11モル%〜25モル%のAl2O3;4モル%〜15モル%のP2O5;13モル%〜20モル%のNa2O、1モル%未満のB2O3,およびMgOを含み、K2Oを含まないアルカリアルミノケイ酸ガラスであって、
i. Na2O、Rb2O、Cs2Oからなる群より選択される一価のカチオン酸化物R2Oを含有し;かつ
ii. 1.3<[(P2O5(モル%)+R2O(モル%))/M2O3(モル%)]≦2.3;
であり、式中M2O3=Al2O3+B2O3であり、R2Oが前記アルカリアルミノケイ酸ガラス中に存在する一価カチオン酸化物の合計であるアルカリアルミノケイ酸ガラスを提供するステップと;
b.最大24時間の時限中イオン交換浴中に前記アルカリアルミノケイ酸ガラスを浸漬して、前記アルカリアルミノケイ酸ガラスの表面から少なくとも10μmの層深さまで延在する圧縮層を有するイオン交換されたアルカリアルミノケイ酸ガラスを形成するステップと;
を含む方法。 - 前記ガラスが、下記式
1.5<[(P2O5(モル%)+R2O(モル%))/M2O3(モル%)]≦2.0
を満たす、請求項6に記載の方法。 - 前記ガラスのカリウム/ナトリウム相互拡散係数が410℃で2.4×10−10cm2/s〜1.5×10−9cm2/sの範囲内にあるか;または前記イオン交換されたガラスの圧縮層が少なくとも300MPaの圧縮応力下にあるか;または前記イオン交換されたガラスが少なくとも12kgfのビッカース圧子圧入亀裂発生荷重を有する、請求項6または7に記載の方法。
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