JP6065301B2 - 改良された化学的および機械的耐久性を有するガラス組成物 - Google Patents
改良された化学的および機械的耐久性を有するガラス組成物 Download PDFInfo
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- 239000011521 glass Substances 0.000 title claims description 499
- 239000000203 mixture Substances 0.000 title claims description 325
- 239000000126 substance Substances 0.000 title description 28
- 238000005342 ion exchange Methods 0.000 claims description 77
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims description 62
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 51
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 48
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 claims description 42
- 230000007062 hydrolysis Effects 0.000 claims description 42
- 238000006460 hydrolysis reaction Methods 0.000 claims description 42
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 20
- 229910052796 boron Inorganic materials 0.000 claims description 20
- 239000002253 acid Substances 0.000 claims description 14
- 150000001639 boron compounds Chemical class 0.000 claims description 13
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- 238000005728 strengthening Methods 0.000 description 26
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- 230000000052 comparative effect Effects 0.000 description 14
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- 239000003513 alkali Substances 0.000 description 13
- 150000002500 ions Chemical class 0.000 description 13
- 150000003839 salts Chemical class 0.000 description 12
- 238000000137 annealing Methods 0.000 description 9
- 230000015556 catabolic process Effects 0.000 description 9
- 238000006731 degradation reaction Methods 0.000 description 9
- 239000011574 phosphorus Substances 0.000 description 9
- 229910052698 phosphorus Inorganic materials 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 230000001965 increasing effect Effects 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
- 238000000034 method Methods 0.000 description 7
- 230000004580 weight loss Effects 0.000 description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 6
- 230000008859 change Effects 0.000 description 6
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- 238000003426 chemical strengthening reaction Methods 0.000 description 5
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 229910010413 TiO 2 Inorganic materials 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 239000008213 purified water Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
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- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
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- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 239000003637 basic solution Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
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- 230000000694 effects Effects 0.000 description 2
- 239000005337 ground glass Substances 0.000 description 2
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- 239000000843 powder Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 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 description 1
- 241000047703 Nonion Species 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000005358 alkali aluminosilicate glass Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical group 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
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- 239000000470 constituent Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940126534 drug product Drugs 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000006066 glass batch Substances 0.000 description 1
- 239000000156 glass melt Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 230000036512 infertility Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
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- 238000002156 mixing Methods 0.000 description 1
- 239000006060 molten glass Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000000825 pharmaceutical preparation Substances 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
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- 229910052708 sodium Inorganic materials 0.000 description 1
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- C03C4/20—Compositions for glass with special properties for chemical resistant 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
- C03C3/00—Glass compositions
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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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- C03C21/002—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 to perform ion-exchange between alkali ions
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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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- 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
- 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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- C03—GLASS; MINERAL OR SLAG WOOL
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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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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
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- C03C4/00—Compositions for glass with special properties
- C03C4/18—Compositions for glass with special properties for ion-sensitive glass
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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
- C03C2204/00—Glasses, glazes or enamels with special properties
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y10T428/1317—Multilayer [continuous layer]
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Description
6種の例示的な本発明によるガラス組成物(組成物A〜F)を調製した。各例示的ガラス組成物の具体的組成は以下の表1で報告されている。各例示的ガラス組成物について複数の試料を製作した。各組成の1つの試料セットを少なくとも5時間、450℃の温度で100%KNO3の溶融塩浴中でイオン交換して、試料の表面内に圧縮層を誘発した。圧縮層は、少なくとも500MPaの表面圧縮応力と少なくとも45μmの層深さを有していた。
3種の例示的な本発明によるガラス組成物(組成物G〜I)と3種の比較用ガラス組成物(組成物1〜3)を調製した。各組成物中でアルカリ酸化物対アルミナ(すなわちY:X)の比を変動させて、結果として得たガラス溶融物およびガラスのさまざまな特性に対するこの比の効果を査定した。例示的な本発明によるガラス組成物と比較用ガラス組成物の各々の具体的組成は、表2に報告されている。各ガラス組成物から形成された溶融物の歪点、焼鈍点および軟化点を決定し、表2に報告している。さらに、結果として得たガラスの熱膨張係数(CTE)、密度、および応力光学係数(SOC)も決定し、表2に報告している。各々の例示的な本発明によるガラス組成物と各々の比較用ガラス組成物から形成されたガラス試料の耐加水分解性を、450℃で5時間100%KNO3の溶融塩浴中でイオン交換の前後両方においてISO720規格に準じて決定した。イオン交換されたこれらの試料について、圧縮応力を、基本応力計(FSM)計器を用いて、測定された応力光学係数(SOC)に基づく圧縮応力値で決定した。FSM計器は、複屈折ガラス表面内およびこの表面から外に光を結合させる。その後、測定された複屈折を材料定数、応力光学係数または光弾性係数(SOCまたはPEC)を通して応力に関連づけし、2つのパラメータすなわち最大表面圧縮応力(CS)と交換済み層深さ(DOL)を得る。ガラス中のアルカリイオンの拡散率および時間の平方根あたりの応力変化も決定した。ガラスの拡散率(D)を測定された層深さ(DOL)およびイオン交換時間(t)から以下の関係式にしたがって計算する:DOL=約1.4*sqrt(4*D*t)。拡散率は、アレニウスの関係式にしたがって温度と共に増加し、そのため特定の温度で報告されている。
3種の例示的な本発明によるガラス組成物(組成物J〜L)および3種の比較用ガラス組成物(組成物4〜6)を調製した。ガラス組成物中のMgOおよびCaOの濃度を変動させて、MgO富有組成物(例えば組成物J〜Lと4)およびCaO富有組成物(すなわち組成物5〜6)の両方を生成した。MgOおよびCaOの相対的量も同様に、ガラス組成物が(CaO/(CaO+MgO))について異なる値を有するような形で変動させた。例示的な本発明によるガラス組成物および比較用ガラス組成物各々の具体的組成は、以下で表3中に報告されている。各組成物の特性は、実施例2に関して以上で記述した通りに決定した。
3種の例示的な本発明によるガラス組成物(組成物M〜O)および3種の比較用ガラス組成物(組成物7〜9)を調製した。ガラス組成物中のB2O3の濃度を0モル%〜約4.6モル%まで変動させて、結果として得られるガラスがB2O3/(R2O−Al2O3)比について異なる値を有するようにした。例示的な本発明によるガラス組成物および比較用ガラス組成物の各々の具体的組成は以下で表4中に報告されている。各ガラス組成物の特性は、実施例2および3に関して以上で記述した通りに決定した。
Claims (15)
- 医薬品パッケージ用ガラスであって、
70モル%〜80モル%の濃度のSiO2と、
4モル%〜8モル%の、MgO、CaO、SrOおよびBaOよりなる群から選択されるアルカリ土類酸化物であって、MgOおよびCaOを含有し、CaOの濃度は0.1モル%〜1.0モル%である、アルカリ土類酸化物と、
Xモル%のAl2O3であって、Xは4〜8モル%である、Al2O3と、
Yモル%のアルカリ酸化物であって、Yは9モル%超であり、Na 2 OおよびK 2 Oを含有し、Na 2 Oの濃度は2モル%〜15モル%であり、K2Oの濃度は0.01モル%以上かつ2モル%以下である、アルカリ酸化物と、
を含み、
Y:Xの比が1超であるガラス組成を有する、医薬品パッケージ用ガラス。 - SiO2は74モル%〜78モル%の量で存在する、請求項1記載の医薬品パッケージ用ガラス。
- (CaO(モル%)/(CaO(モル%)+MgO(モル%)))比が0.5以下である、請求項1記載の医薬品パッケージ用ガラス。
- Y:Xの比が2以下である、請求項1記載の医薬品パッケージ用ガラス。
- 前記アルカリ酸化物が、8モル%超の量でNa2Oを含む、請求項4記載の医薬品パッケージ用ガラス。
- 前記ガラス組成が、ホウ素およびホウ素化合物を含まない、請求項1記載の医薬品パッケージ用ガラス。
- 該ガラスは、イオン交換により強化されたものであり、10μm以上の層深さおよび250MPa以上の表面圧縮応力を有する圧縮応力層を有する、請求項1記載の医薬品パッケージ用ガラス。
- ISO719に準じたタイプHGB1の耐加水分解性を有する、請求項1記載の医薬品パッケージ用ガラス。
- ISO720に準じたタイプHGA1の耐加水分解性を有する、請求項7記載の医薬品パッケージ用ガラス。
- DIN12116に準じた少なくともクラスS3の耐酸性を有する、請求項1記載の医薬品パッケージ用ガラス。
- ISO695に準じた少なくともクラスA2の耐塩基性を有する、請求項1記載の医薬品パッケージ用ガラス。
- 70×10−7K−1未満の熱膨張係数を有する、請求項1記載の医薬品パッケージ用ガラス。
- 医薬品パッケージ用ガラスであって、
74モル%〜78モル%のSiO 2 と、
4モル%〜8モル%の、MgO、CaO、SrOおよびBaOよりなる群から選択されるアルカリ土類酸化物であって、MgOおよびCaOを含有し、CaOの濃度は0.1モル%〜1.0モル%であり、(CaO(モル%)/(CaO(モル%)+MgO(モル%)))比が0.5以下である、アルカリ土類酸化物と、
Xモル%のAl 2 O 3 であって、Xは4〜8モル%である、Al 2 O 3 と、
Yモル%のアルカリ酸化物であって、Yは9〜14モル%である、アルカリ酸化物と、
を含み、
Y:Xの比が1超であり、ホウ素およびホウ素化合物を含まない、ガラス組成を有する、医薬品パッケージ用ガラス。 - Y:Xの比が2以下である、請求項13記載の医薬品パッケージ用ガラス。
- 前記アルカリ酸化物が、8モル%超の量でNa 2 Oを含む、請求項14記載の医薬品パッケージ用ガラス。
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