GLASS FOR PHARMACEUTICAL CONTAINER, GLASS TUBE FOR PHARMACEUTICAL CONTAINER, AND PHARMACEUTICAL CONTAINER
20230167007 · 2023-06-01
Assignee
Inventors
Cpc classification
A61J1/1468
HUMAN NECESSITIES
International classification
Abstract
A glass for a pharmaceutical container of the present invention contains, as a glass composition, in terms of mol %, 70% to 85% of SiO.sub.2, 3% to 13% of Al.sub.2O.sub.3, 0% to 5% of B.sub.2O.sub.3, 0.1% to 18% of Li.sub.2O+Na.sub.2O+K.sub.2O, and 0% to 10% of MgO+CaO+SrO+BaO, in which a molar ratio (Li.sub.2O+Na.sub.2O+K.sub.2O)/Al.sub.2O.sub.3 is 1 or more and a molar ratio (Li.sub.2O+Na.sub.2O+K.sub.2O+MgO+CaO+SrO+BaO—Al.sub.2O.sub.3)/(SiO.sub.2+Al.sub.2O.sub.3) is 0.2 or less.
Claims
1. A glass for a pharmaceutical container, comprising, as a glass composition, in terms of mol %, 70% to 85% of SiO.sub.2, 3% to 13% of Al.sub.2O.sub.3, 0% to 5% of B.sub.2O.sub.3, 0.1% to 18% of Li.sub.2O+Na.sub.2O+K.sub.2O, and 0% to 10% of MgO+CaO+SrO+BaO, wherein a molar ratio (Li.sub.2O+Na.sub.2O+K.sub.2O)/Al.sub.2O.sub.3 is 1 or more and a molar ratio (Li.sub.2O+Na.sub.2O+K.sub.2O+MgO+CaO+SrO+BaO—Al.sub.2O.sub.3)/(SiO.sub.2+Al.sub.2O.sub.3) is 0.2 or less.
2. The glass for a pharmaceutical container according to claim 1, wherein a content of Li.sub.2O is 0 mol % to 8.1 mol %, a content of Na.sub.2O is 0.1 mol % to 8 mol %, and a content of K.sub.2O is 0.01 mol % to 5 mol %.
3. The glass for a pharmaceutical container according to claim 1, wherein a content of MgO+CaO+SrO+BaO is 0 mol % to 5 mol %.
4. The glass for a pharmaceutical container according to claim 1, wherein a content of MgO is 0 mol % to 1.5 mol %, a content of CaO is 0 mol % to 4 mol %, a content of SrO is 0 mol % to 0.3 mol %, and a content of BaO is 0 mol % to 0.3 mol %.
5. The glass for a pharmaceutical container according to claim 1, wherein the molar ratio Li.sub.2O/(Li.sub.2O+Na.sub.2O+K.sub.2O) is 0.6 or less.
6. The glass for a pharmaceutical container according to claim 1, wherein a molar ratio (Li.sub.2O+Na.sub.2O+K.sub.2O)/Al.sub.2O.sub.3 is 2 or more.
7. The glass for a pharmaceutical container according to claim 1, wherein a molar ratio CaO/(Li.sub.2O+Na.sub.2O+K.sub.2O+MgO+CaO+SrO+BaO) is less than 0.018.
8. The glass for a pharmaceutical container according to claim 1, wherein CaO is contained, and a molar ratio Li.sub.2O/CaO is 3.1 or less.
9. The glass for a pharmaceutical container according to claim 1, wherein a content of SiO.sub.2+Al.sub.2O.sub.3+Li.sub.2O+Na.sub.2O+K.sub.2O+MgO+CaO+SrO+BaO is 90 mol % or more.
10. The glass for a pharmaceutical container according to claim 1, wherein a content of B.sub.2O.sub.3 is 0.01 mol % to 1 mol %.
11. The glass for a pharmaceutical container according to claim 1, wherein a content of ZrO.sub.2 is 0 mol % to 2 mol %.
12. A glass for a pharmaceutical container, comprising, as a glass composition, in terms of mol %, 70% to 85% of SiO.sub.2, 3% to 10% of Al.sub.2O.sub.3, 0% to 5% of B.sub.2O.sub.3, 0.1% to less than 13.9% of Li.sub.2O+Na.sub.2O+K.sub.2O, and 0% to 10% of MgO+CaO+SrO+BaO, wherein a molar ratio Li.sub.2O/(Li.sub.2O+Na.sub.2O+K.sub.2O) is 0.5 or less, a molar ratio (Li.sub.2O+Na.sub.2O+K.sub.2O)/Al.sub.2O.sub.3 is 2.0 or more, a molar ratio (Li.sub.2O+Na.sub.2O+K.sub.2O+MgO+CaO+SrO+BaO—Al.sub.2O.sub.3)/(SiO.sub.2+Al.sub.2O.sub.3) is 0.156 or less, and a molar ratio CaO/(Li.sub.2O+Na.sub.2O+K.sub.2O+MgO+CaO+SrO+BaO) is less than 0.018.
13. A glass for a pharmaceutical container, comprising, as a glass composition, in terms of mol %, 70% to 85% of SiO.sub.2, 3% to 10% of Al.sub.2O.sub.3, 0% to 5% of B.sub.2O.sub.3, 0.1% to less than 13.9% of Li.sub.2O+Na.sub.2O+K.sub.2O, and CaO, wherein a molar ratio Li.sub.2O/(Li.sub.2O+Na.sub.2O+K.sub.2O) is 0.5 or less, a molar ratio (Li.sub.2O+Na.sub.2O+K.sub.2O)/Al.sub.2O.sub.3 is 2.0 or more, a molar ratio (Li.sub.2O+Na.sub.2O+K.sub.2O+MgO+CaO+SrO+BaO—Al.sub.2O.sub.3)/(SiO.sub.2+Al.sub.2O.sub.3) is 0.156 or less, and a molar ratio Li.sub.2O/CaO is 3.1 or less.
14. The glass for a pharmaceutical container according to claim 1, wherein a molar ratio (MgO+CaO+SrO+BaO)/(Li.sub.2O+Na.sub.2O+K.sub.2O+MgO+CaO+SrO+BaO) is 0.06 or less.
15. A glass for a pharmaceutical container, comprising, as a glass composition, in terms of mol %, 75% to 85% of SiO.sub.2, 3% to 13% of Al.sub.2O.sub.3, 0% to 4% of B.sub.2O.sub.3, 0.11% to 16% of Li.sub.2O+Na.sub.2O+K.sub.2O, 0.1% to 15% of Na.sub.2O, and 0.01% to 5% of K.sub.2O, wherein a molar ratio (Li.sub.2O+Na.sub.2O+K.sub.2O)/Al.sub.2O.sub.3 is 2 or more, a molar ratio (MgO+CaO+SrO+BaO)/(Li.sub.2O+Na.sub.2O+K.sub.2O+MgO+CaO+SrO+BaO) is 0.06 or less, and a molar ratio (Li.sub.2O+Na.sub.2O+K.sub.2O+MgO+CaO+SrO+BaO—Al.sub.2O.sub.3)/(SiO.sub.2+Al.sub.2O.sub.3) is 0.2 or less.
16. The glass for a pharmaceutical container according to claim 1, wherein a molar ratio CaO/(MgO+CaO+SrO+BaO) is 0.5 or more.
17. A glass for a pharmaceutical container, comprising, as a glass composition, in terms of mol %, 70% to 85% of SiO.sub.2, 3% to 13% of Al.sub.2O.sub.3, 0% to 5% of B.sub.2O.sub.3, 0.1% to 16% of Li.sub.2O+Na.sub.2O+K.sub.2O, 0.1% to 15% of Na.sub.2O, and 0.1% to 5% of MgO+CaO+SrO+BaO, wherein a molar ratio (Li.sub.2O+Na.sub.2O+K.sub.2O)/Al.sub.2O.sub.3 is 2 or more, a molar ratio CaO/(MgO+CaO+SrO+BaO) is 0.5 or more, and a molar ratio (Li.sub.2O+Na.sub.2O+K.sub.2O+MgO+CaO+SrO+BaO—Al.sub.2O.sub.3)/(SiO.sub.2+Al.sub.2O.sub.3) is 0.2 or less.
18. The glass for a pharmaceutical container according to claim 1, wherein a molar ratio SiO.sub.2/Al.sub.2O.sub.3 is 10 or more.
19. A glass for a pharmaceutical container, comprising, as a glass composition, in terms of mol %, 70% to 85% of SiO.sub.2, 3% to 13% of Al.sub.2O.sub.3, 0% to 5% of B.sub.2O.sub.3, 0.21% to 16% of Li.sub.2O+Na.sub.2O+K.sub.2O, 0.1% to 10% of Li.sub.2O, 0.1% to 15% of Na.sub.2O, 0.01% to 5% of K.sub.2O, and 0% to 6% of MgO+CaO+SrO+BaO, wherein a molar ratio (Li.sub.2O+Na.sub.2O+K.sub.2O)/Al.sub.2O.sub.3 is 1 or more, a molar ratio SiO.sub.2/Al.sub.2O.sub.3 is more than 13.2, and a molar ratio (Li.sub.2O+Na.sub.2O+K.sub.2O+MgO+CaO+SrO+BaO—Al.sub.2O.sub.3)/(SiO.sub.2+Al.sub.2O.sub.3) is less than 0.155.
20. The glass for a pharmaceutical container according to claim 1, wherein a class in a hydrolytic resistance test (acetone washing) according to ISO 720 is at least HGA1.
21. The glass for a pharmaceutical container according to claim 1, wherein a working point is 1300° C. or less.
22. A glass tube for a pharmaceutical container, comprising the glass for a pharmaceutical container according to claim 1.
23. A pharmaceutical container comprising the glass for a pharmaceutical container according to claim 1.
Description
BRIEF DESCRIPTION OF DRAWINGS
[0041]
[0042]
[0043]
[0044]
DESCRIPTION OF EMBODIMENTS
[0045] The reason why the content range of each ingredient is limited will be described. In the following description, “%” means “mol %” unless otherwise specified.
[0046] SiO.sub.2 is one of ingredients constituting a network structure of glass. As the content of SiO.sub.2 is small, the processability is improved. However, when the content of SiO.sub.2 is too small, the hydrolytic resistance is liable to deteriorate, the vitrification becomes difficult, the thermal expansion coefficient increases, and the thermal impact resistance is liable to decrease. Meanwhile, as the content of SiO.sub.2 is large, the hydrolytic resistance is improved. However, when the content of SiO.sub.2 is too large, the viscosity of the glass increases, the processability is liable to decrease, the liquidus temperature increases, and the glass is liable to devitrify. Therefore, the content of SiO.sub.2 is 70% to 85%, preferably 71% to 84%, 72% to 83%, 73% to 82.5%, 74% to 82%, 75% to 81.5%, particularly preferably 76% to 81%.
[0047] Al.sub.2O.sub.3 is one of ingredients constituting a network structure of glass, and has an effect of improving the hydrolytic resistance. When the content of Al.sub.2O.sub.3 is too small, the hydrolytic resistance is liable to decrease. Meanwhile, when the content of Al.sub.2O.sub.3 is too large, the viscosity of the glass increases. Therefore, the content of Al.sub.2O.sub.3 is 3% to 13%, preferably 3.5% to 12%, 3.6% to 11%, 3.7% to 10%, 3.8% to 9.5%, 3.9% to 9%, 4% to 8.5%, 4.1% to 8%, 4.2% to 7.8%, 4.3% to 7.5%, 4.4% to 7.3%, particularly preferably 4.5% to 7%.
[0048] B.sub.2O.sub.3 has an effect of decreasing the viscosity of the glass to enhance the meltability and processability. However, B.sub.2O.sub.3 is considered to be one of the factors causing delamination. When the content thereof is too large, the delamination resistance deteriorates, and flakes are liable to occur. Therefore, the content of B.sub.2O.sub.3 is 0% to 5%, preferably 0.01% to 4%, 0.02% to 3%, 0.03% to 2%, 0.04% to 1%, 0.04% to 0.8%, particularly preferably 0.05% to 0.5%.
[0049] Li.sub.2O, Na.sub.2O, and K.sub.2O, which are alkali metal oxides (R.sub.2O), are ingredients that break the network structure of the glass, and have an effect of decreasing the viscosity of the glass to enhance the processability and meltability. The lower limit range of the content of Li.sub.2O+Na.sub.2O+K.sub.2O is 0.1% or more, preferably 0.11% or more, 0.21% or more, 0.5% or more, 1% or more, 2% or more, 3% or more, 4% or more, 4.5% or more, 5% or more, 5.5% or more, 6% or more, 6.5% or more, 7% or more, 7.5% or more, particularly preferably 8% or more. When particularly emphasizing the processability, the lower limit range of the content of Li.sub.2O+Na.sub.2O+K.sub.2O is preferably 8.5% or more, 9% or more, 9.5% or more, 10% or more, 10.5% or more, or 11% or more. Meanwhile, when the content of Li.sub.2O+Na.sub.2O+K.sub.2O is too large, the hydrolytic resistance deteriorates, the thermal expansion coefficient increases, and the thermal impact resistance decreases. Therefore, the upper limit range of the content of Li.sub.2O+Na.sub.2O+K.sub.2O is 18% or less, preferably 17% or less, 16.1% or less, 16% or less, 15.9% or less, 15.5% or less, 15% or less, 14.5% or less, 14% or less, 14.0% or less, 13.9% or less, less than 13.9%, 13.8% or less, less than 13.8%, 13.7% or less, 13.5% or less, particularly preferably 13% or less.
[0050] As described above, Li.sub.2O has an effect of decreasing the viscosity of the glass to enhance the processability and the meltability. Among the alkali metal oxides, Li.sub.2O has the highest effect of decreasing the viscosity of the glass, followed by Na.sub.2O and K.sub.2O in that order. However, when the content of Li.sub.2O is too large, the hydrolytic resistance is liable to deteriorate. Therefore, the content of Li.sub.2O is preferably 0% to 9%, 0 to 8.1%, 0% to 8%, 0% to 7%, 0% to 6.8%, 0% to 6.5%, 0% to 6.3%, 0% to 6%, 0% to 5.9%, 0% to 5.8%, 0% to 5.7%, 0% to 5.5%, 0% to 5.0%, 0% to 4.9%, particularly preferably 0% to 4.8%. When the content of Li.sub.2O is 6% or less, devitrification is less likely to occur.
[0051] When emphasizing the processability, the content of Li.sub.2O is preferably 0.1% to 9%, 0.5% to 8%, 1% to 7.5%, 2% to 7.4%, 2.5% to 7.3%, 3% to 7.2%, 3.5% to 7.1%, particularly preferably 4% to 7%.
[0052] When emphasizing both the hydrolytic resistance and the processability, the content of Li.sub.2O is preferably 2% to 8%, 2.5% to 7%, 3% to 6.5%, 3.1% to 6.3%, 3.3% to 6.2%, 3.5% to 6.1%, particularly preferably 4% to 6%.
[0053] Like Li.sub.2O, Na.sub.2O has an effect of decreasing the viscosity of the glass to enhance the processability and meltability. When the content of Na.sub.2O is too small, the devitrification resistance may decrease. Meanwhile, when the content of Na.sub.2O is too large, the hydrolytic resistance is liable to deteriorate. Therefore, the content of Na.sub.2O is preferably 0% to 12%, 0% to 10%, 0% to 9%, 0% to 8.5%, 0% to 8.3%, 0% to 8%, 0% to 7.9%, 0% to 7.5%, 0% to 7%, 0% to 6.5%, 0% to 6%, 0% to 5.5%, particularly preferably 0% to 5%.
[0054] When emphasizing the processability, the content of Na.sub.2O is preferably 0.1% to 12%, 0.5% to 11%, 1% to 10%, 2% to 9%, 2.5% to 8.5%, 3% to 8%, 3.3% to 7.5%, 3.5% to 7%, 3.8% to 6.5%, particularly preferably 4% to 6%.
[0055] K.sub.2O has an effect of decreasing the viscosity of the glass to enhance the processability and meltability, though not as much as the effect of Li.sub.2O and Na.sub.2O. However, when the content of K.sub.2O is too large, the hydrolytic resistance is liable to deteriorate. Meanwhile, when the content of K.sub.2O is too small, the devitrification resistance may decrease. Therefore, the content of K.sub.2O is preferably 0% to 5%, 0% to 4%, 0% to 3.8%, 0% to 3.7%, 0% to 3.6%, 0% to 3.5%, 0% to 3.3%, 0% to 3.1%, 0% to 3%, particularly preferably 0% to less than 3%.
[0056] When emphasizing the processability, the content of K.sub.2O is preferably 0.01% to 11%, 0.05% to 10%, 0.1% to 8%, 0.5% to 6%, 0.8% to 5.5%, 1% to 5%, 1.2% to 4.5%, 1.4% to 4.3%, particularly preferably 1.5% to 4%.
[0057] Among the alkali metal oxides (R.sub.2O), Li.sub.2O has the highest effect of decreasing the viscosity of the glass, followed by Na.sub.2O and K.sub.2O in that order. Therefore, from the viewpoint of decreasing the viscosity of the glass, the relationship of the content of the alkali metal oxides is preferably Li.sub.2O≥Na.sub.2O≥K.sub.2O, Li.sub.2O≥Na.sub.2O>K.sub.2O or Li.sub.2O>Na.sub.2O≥K.sub.2O, and particularly preferably Li.sub.2O>Na.sub.2O>K.sub.2O. When the proportion of K.sub.2O in the alkali metal oxides is too high, it is difficult to achieve both the hydrolytic resistance and processability. Therefore, from the viewpoint of achieving both the hydrolytic resistance and processability, Na.sub.2O>K.sub.2O is preferable.
[0058] When the proportion of Li.sub.2O in the alkali metal oxides is too high, the devitrification resistance is liable to decrease. Therefore, from the viewpoint of devitrification resistance, the relationship of the content of the alkali metal oxides is preferably Na.sub.2O>Li.sub.2O. K.sub.2O has the highest effect of improving the devitrification resistance, followed by Na.sub.2O and Li.sub.2O in that order. From the viewpoint of achieving both the hydrolytic resistance and devitrification resistance, it is preferably Li.sub.2O≥Na.sub.2O≥K.sub.2O, Li.sub.2O≥K.sub.2O>Na.sub.2O or Li.sub.2O>Na.sub.2O≥K.sub.2O, particularly preferably Li.sub.2O>K.sub.2O>Na.sub.2O.
[0059] As described above, when the proportion of Li.sub.2O in the alkali metal oxides is too high, the devitrification resistance is liable to decrease. Therefore, from the viewpoint of the devitrification resistance, the upper limit range of a molar ratio Li.sub.2O/(Li.sub.2O+Na.sub.2O+K.sub.2O) is preferably 0.8 or less, 0.7 or less, 0.6 or less, 0.55 or less, 0.54 or less, 0.53 or less, 0.52 or less, 0.51 or less, 0.5 or less, less than 0.50, 0.49 or less, 0.48 or less, 0.47 or less, 0.46 or less, particularly preferably 0.45 or less.
[0060] When the proportion of K.sub.2O in the alkali metal oxides is too high, the effect of decreasing the viscosity of the glass is reduced. Therefore, the upper limit range of a molar ratio K.sub.2O/(Li.sub.2O+Na.sub.2O+K.sub.2O) is preferably 0.6 or less, 0.5 or less, 0.4 or less, 0.24 or less, 0.22 or less, 0.21 or less, particularly preferably 0.2 or less. Meanwhile, when the molar ratio K.sub.2O/(Li.sub.2O+Na.sub.2O+K.sub.2O) is too small, the devitrification resistance may decrease. Therefore, the lower limit range of the molar ratio K.sub.2O/(Li.sub.2O+Na.sub.2O+K.sub.2O) is preferably more than 0, 0.01 or more, particularly 0.03 or more, 0.05 or more, 0.8 or more, 0.1 or more, particularly preferably 0.13 or more.
[0061] When the content of Al.sub.2O.sub.3 is large, the hydrolytic resistance is improved, but the viscosity of the glass increases. When the content of Li.sub.2O+Na.sub.2O+K.sub.2O is large, the viscosity of the glass decreases, but the hydrolytic resistance deteriorates. Therefore, a molar ratio Al.sub.2O.sub.3/(Li.sub.2O+Na.sub.2O+K.sub.2O) is preferably 50 or less, 40 or less, 30 or less, 20 or less, 10 or less, 5 or less, 3 or less, 2 or less, 1.2 or less, 0 to 1, 0 to 0.85, 0 to 0.8, more than 0 to 0.74, 0.01 to 0.7, 0.1 to 0.67, 0.2 to 0.65, 0.3 to 0.61, 0.35 to 0.60, 0.4 to 0.59, particularly preferably more than 0.4 to 0.55. When the molar ratio Al.sub.2O.sub.3/(Li.sub.2O+Na.sub.2O+K.sub.2O) is out of the above range, it is difficult to achieve both the hydrolytic resistance and the processability. When the molar ratio Al.sub.2O.sub.3/(Li.sub.2O+Na.sub.2O+K.sub.2O) is 0.67 or less, both the hydrolytic resistance and processability are particularly liable to be achieved.
[0062] As described above, the alkali metal oxide is an ingredient that decreases the viscosity of the glass and at the same time deteriorates the chemical durability. This is because the alkali metal oxide cuts the network structure of the glass. However, Al.sub.2O.sub.3 forms a network structure of glass together with the alkali metal oxide in glass. Therefore, when Al.sub.2O.sub.3 is introduced into the glass composition, the role of a part of the alkali metal oxide can be changed from cutting the network structure to forming the network structure. From this, from the viewpoint of emphasizing the hydrolytic resistance, it is preferable that all Al.sub.2O.sub.3 forms a bond together with the alkali metal oxide in a stoichiometric ratio. This state is when the value of the molar ratio (Li.sub.2O+Na.sub.2O+K.sub.2O)/Al.sub.2O.sub.3 is 1 or more. Therefore, as the value of the molar ratio (Li.sub.2O+Na.sub.2O+K.sub.2O)/Al.sub.2O.sub.3 is closer to 1, the network structure increases, and thus the hydrolytic resistance is improved. Meanwhile, in this state, the processability decreases since the amount of the alkali metal oxide is small. Therefore, from the viewpoint of achieving both the hydrolytic resistance and processability, the lower limit range of the molar ratio (Li.sub.2O+Na.sub.2O+K.sub.2O)/Al.sub.2O.sub.3 is 1 or more, preferably 1.5 or more, 1.6 or more, 1.7 or more, 1.8 or more, 1.9 or more, 2 or more, 2.0 or more, 2.1 or more, 2.2 or more, 2.3 or more, 2.4 or more, particularly preferably 2.5 or more. Meanwhile, when the molar ratio (Li.sub.2O+Na.sub.2O+K.sub.2O)/Al.sub.2O.sub.3 is too large, the processability is improved, but the hydrolytic resistance is liable to deteriorate. Therefore, the upper limit range of the molar ratio (Li.sub.2O+Na.sub.2O+K.sub.2O)/Al.sub.2O.sub.3 is preferably 5 or less, 4 or less, 3.5 or less, 3.4 or less, 3.3 or less, 3.2 or less, 3.1 or less, particularly preferably 3 or less.
[0063] When the content of Al.sub.2O.sub.3 is too small with respect to SiO.sub.2, the hydrolytic resistance is liable to deteriorate and the devitrification resistance is also liable to deteriorate. Therefore, the upper limit range of a molar ratio SiO.sub.2/Al.sub.2O.sub.3 is preferably 30 or less, 25 or less, 20 or less, 18 or less, 17 or less, 16 or less, particularly preferably 15 or less. When the content of Al.sub.2O.sub.3 is too large with respect to SiO.sub.2, it becomes difficult to achieve both the hydrolytic resistance and processability. Therefore, the lower limit range of the molar ratio SiO.sub.2/Al.sub.2O.sub.3 is preferably 10 or more, 11 or more, 12 or more, 12.5 or more, 12.8 or more, 12.9 or more, 13 or more, 13.0 or more, 13.1 or more, or 13.2 or more, particularly preferably more than 13.2.
[0064] In order to achieve both the hydrolytic resistance and processability, it is preferable to regulate the ingredient balance between SiO.sub.2 and the alkali metal oxides. A molar ratio SiO.sub.2/(Li.sub.2O+Na.sub.2O+K.sub.2O) is preferably 10 or less, 8 or less, 7.9 or less, 7 or less, 6.9 or less, 6.5 or less, 6.1 or less, 6.0 or less, 5.9 or less, particularly preferably 5.8 or less. In particular, when the molar ratio SiO.sub.2/(Li.sub.2O+Na.sub.2O+K.sub.2O) is 6.9 or less, both the hydrolytic resistance and processability are particularly liable to be achieved.
[0065] The lower limit range of a molar ratio Li.sub.2O/(Na.sub.2O+K.sub.2O) is preferably 0.1 or more, 0.2 or more, 0.3 or more, 0.4 or more, 0.5 or more, 0.6 or more, particularly preferably 0.7 or more. This makes it possible to prevent the adverse effects of Na.sub.2O, which deteriorates the hydrolytic resistance, while accurately enjoying the effects of Li.sub.2O. Meanwhile, when the molar ratio Li.sub.2O/(Na.sub.2O+K.sub.2O) is too large, the raw material cost increases. Therefore, the upper limit range of the molar ratio Li.sub.2O/(Na.sub.2O+K.sub.2O) is preferably 2.0 or less, 1.5 or less, 1.2 or less, 1.1 or less, 1.0 or less, less than 1.0, 0.9 or less, 0.85 or less, 0.83 or less, particularly preferably 0.82 or less.
[0066] MgO, CaO, SrO, and BaO, which are alkaline earth metal oxides (R′O), are ingredients that break the network structure of the glass in the same manner as the alkali metal oxides, and also have the effect of decreasing the viscosity of the glass. In addition, MgO, CaO, SrO, and BaO are ingredients that also affect the hydrolytic resistance. When the content of MgO+CaO+SrO+BaO is too large, not only the hydrolytic resistance is liable to deteriorate, but also the devitrification resistance is liable to decrease, and the alkaline earth metal oxides eluted into the medicament may be precipitated as carbonate or sulfate. Therefore, the content of MgO+CaO+SrO+BaO is 0% to 10%, preferably 0% to 5%, 0% to 4%, 0% to 3.7%, 0% to 3%, 0% to 2%, 0% to 1%, 0% to 0.9%, 0% to 0.8%, 0% to 0.7%, 0% to 0.6%, 0% to 0.5%, 0% to 0.4%, 0% to 0.3%, 0% to 0.2%, 0% to 0.1%, 0% to 0.01%, less than 0.01%, particularly preferably less than 0.001%, from the viewpoint of emphasizing the hydrolytic resistance. From the viewpoint of emphasizing the processability, the content of MgO+CaO+SrO+BaO is preferably 0.01% to 11%, 0.05% to 10%, 0.1% to 9%, 0.5% to 8%, 0.7% to 7%, 0.9% to 6%, 1.0% to 5%, more than 1% to 4.9%, 1.1% to 4.8%, 1.2% to 4.7%, 1.3% to 4.6%, 1.4% to 4.3%, particularly 1.5% to 4%, 1.8% to less than 4%, particularly preferably 1.9% to 3.8%.
[0067] The degree of precipitation of carbonate or sulfate of the alkaline earth metal oxides depends on the solubility of each salt. Specifically, the solubility of MgO is the highest, followed by CaO, SrO, and BaO in that order. That is, MgO is most unlikely to cause the precipitation of the salt, and BaO is most likely to cause the precipitation of the salt. Therefore, when focusing on the solubility, the relationship of the content between alkaline earth metal oxides is preferably MgO≥CaO (particularly MgO>CaO), MgO≥SrO (particularly MgO>SrO), MgO≥BaO (particularly MgO>BaO), CaO≥SrO (particularly CaO>SrO), CaO≥BaO (particularly CaO>BaO), or SrO≥BaO (particularly SrO>BaO), more preferably MgO≥CaO≥SrO≥BaO, and still more preferably MgO>CaO>SrO>BaO.
[0068] Meanwhile, BaO has the highest effect of decreasing the viscosity of glass, followed by SrO, CaO, and MgO in that order. Therefore, when focusing on the processability, the relationship of the content between the alkaline earth metal oxides is preferably MgO≤CaO (particularly MgO<CaO), MgO≤SrO (particularly MgO<SrO), MgO≤BaO (particularly MgO<BaO), CaO≤SrO (particularly CaO<SrO), CaO≤BaO (particularly CaO<BaO), or SrO≤BaO (particularly SrO<BaO), more preferably MgO≤CaO≤SrO≤BaO, and still more preferably MgO<CaO<SrO<BaO.
[0069] As described above, MgO is an ingredient that cause high solubility of carbonate and sulfate and is unlikely to cause salt precipitation. However, since Mg ions are liable to react with hydrated silicic acid, hydrated silicic acid generated on the glass surface and Mg ions may react with each other to form an insoluble magnesium silicate hydrate film when Mg ions in the glass are eluted. This film may be peeled off by vibration or the like to become a flaky insoluble foreign matter. Meanwhile, when the content of MgO is too large, the hydrolytic resistance is liable to deteriorate. Therefore, the content of MgO is preferably 0% to 10%, 0% to 8%, 0% to 5%, 0% to 3%, 0% to 1.5%, 0% to 1%, 0% to 0.9%, 0% to 0.8%, 0% to 0.7%, 0% to 0.6%, 0% to 0.5%, 0% to 0.4%, 0% to 0.3%, 0% to 0.2%, 0% to 0.1%, 0% to 0.05%, 0% to 0.03%, 0% to less than 0.03%, 0% to 0.01%, 0% to less than 0.01%, particularly preferably 0% to less than 0.001%. When emphasizing the processability, MgO may be introduced in an amount of 0.01% or more.
[0070] Among the alkaline earth metal oxides, CaO is an ingredient that can achieve both a decrease in the viscosity of glass and a difficulty in precipitation of salts and insoluble foreign matters. However, when the content of CaO is too large, the hydrolytic resistance may decrease. Therefore, the content of CaO is preferably 0% to 10%, 0% to 8%, 0% to 5%, 0% to 3%, 0% to 1%, 0% to 0.9%, 0% to 0.8%, 0% to 0.7%, 0% to 0.6%, 0% to 0.5%, 0% to 0.4%, 0% to 0.3%, 0% to 0.2%, 0% to 0.1%, 0% to 0.05%, 0% to 0.03%, 0% to less than 0.03%, 0% to 0.01%, 0% to less than 0.01%, particularly preferably 0% to less than 0.001%. From the viewpoint of emphasizing the processability, CaO is preferably contained. The content of CaO is preferably more than 0% to 10%, 1% to 10%, 1.2% to 9%, 1.4% to 8%, 1.6% to 7%, 1.8% to 6%, 2% to 5%, 2.2% to 4.8%, 2.4% to 4.6%, 2.6% to 4.4%, 2.8% to 4.2%, 3% to 4%, particularly 3.2% to 3.8%.
[0071] When emphasizing the hydrolytic resistance, a molar ratio CaO/(Li.sub.2O+Na.sub.2O+K.sub.2O+MgO+CaO+SrO+BaO) is preferably 0.5 or less, 0.4 or less, 0.3 or less, 0.25 or less, 0.24 or less, 0.23 or less, 0.2 or less, 0.1 or less, 0.05 or less, 0.04 or less, 0.03 or less, 0.025 or less, 0.02 or less, 0.019 or less, 0.018 or less, less than 0.018, 0.015 or less, 0.01 or less, particularly preferably 0.001 or less.
[0072] In order to achieve both the hydrolytic resistance and processability, it is preferable to preferentially introduce MgO and CaO that are unlikely to cause precipitation of carbonate or sulfate among the alkaline earth metal oxides. Further, it is preferable to adjust so that the amount of CaO having a high effect of decreasing the viscosity of the glass is relatively large. When emphasizing both the processability and the difficulty in precipitating salts and insoluble foreign matters, it is preferable to increase a value of a molar ratio CaO/(MgO+CaO+SrO+BaO). The lower limit range of the molar ratio CaO/(MgO+CaO+SrO+BaO) is preferably 0.01 or more, 0.03 or more, 0.05 or more, 0.1 or more, 0.2 or more, 0.3 or more, 0.4 or more, 0.5 or more, 0.6 or more, 0.7 or more, 0.8 or more, particularly preferably 0.9 or more.
[0073] The content of SrO is preferably 0% to 1%, 0% to 0.9%, 0% to 0.8%, 0% to 0.7%, 0% to 0.6%, 0% to 0.5%, 0% to 0.4%, 0% to 0.3%, 0% to 0.2%, 0% to 0.1%, 0% to 0.01%, 0% to less than 0.01%, particularly preferably 0% to 0.001%. When the content of SrO is too large, carbonate or sulfate is liable to be precipitated, and the hydrolytic resistance is liable to deteriorate.
[0074] The content of BaO is preferably 0% to 1%, 0% to 0.9%, 0% to 0.8%, 0% to 0.7%, 0% to 0.6%, 0% to 0.5%, 0% to 0.4%, 0% to 0.3%, 0% to 0.2%, 0% to 0.1%, 0% to 0.01%, 0% to less than 0.01%, particularly preferably 0% to 0.001%. When the content of BaO is too large, carbonate or sulfate is liable to be precipitated, and the hydrolytic resistance is liable to deteriorate.
[0075] MgO is an ingredient that cause high solubility of carbonate and sulfate and is unlikely to cause salt precipitation. Meanwhile, Mg ions are liable to react with hydrated silicic acid, which leads to formation of an insoluble magnesium silicate hydrate film. Therefore, a molar ratio MgO/(MgO+CaO+SrO+BaO) is preferably 1 or less, less than 1, 0.9 or less, 0.8 or less, 0.7 or less, 0.6 or less, 0.5 or less, less than 0.5, 0.4 or less, 0.3 or less, 0.2 or less, 0.1 or less, 0.01 or less, particularly preferably 0.001 or less.
[0076] From the viewpoint of preventing the formation of an insoluble magnesium silicate hydrate film, a molar ratio MgO/(Li.sub.2O+Na.sub.2O+K.sub.2O+MgO+CaO+SrO+BaO) is preferably 0.5 or less, 0.4 or less, 0.3 or less, 0.2 or less, 0.1 or less, 0.09 or less, 0.08 or less, 0.07 or less, 0.06 or less, less than 0.06, 0.05 or less, 0.04 or less, 0.03 or less, 0.02 or less, 0.01 or less, particularly preferably 0.001 or less.
[0077] From the viewpoint of emphasizing the hydrolytic resistance, a molar ratio (MgO+CaO+SrO+BaO)/(Li.sub.2O+Na.sub.2O+K.sub.2O+MgO+CaO+SrO+BaO) is preferably 0.5 or less, 0.4 or less, 0.3 or less, 0.2 or less, 0.1 or less, 0.09 or less, 0.08 or less, 0.07 or less, 0.06 or less, less than 0.06, 0.05 or less, 0.04 or less, 0.03 or less, 0.02 or less, 0.01 or less, particularly preferably 0.001 or less.
[0078] The content of MgO+CaO is preferably 0% to 10%, 0% to 5%, 0% to 4%, 0% to 3.7%, 0% to 3%, 0% to 2%, 0% to 1%, 0% to 0.9%, 0% to 0.8%, 0% to 0.7%, 0% to 0.6%, 0% to 0.5%, 0% to 0.4%, 0% to 0.3%, 0% to 0.2%, 0% to 0.1%, 0% to 0.01%, 0% to less than 0.01%, particularly preferably 0% to 0.001%. When the content of MgO+CaO is too large, carbonate or sulfate is liable to be precipitated. “MgO+CaO” refers to the total content of MgO and CaO.
[0079] As described above, MgO leads to formation of an insoluble magnesium silicate hydrate film. CaO is an ingredient that is less likely to react with SiO.sub.2 than MgO, and that is less likely to lead to formation of an insoluble film. Therefore, from the viewpoint of enhancing the safety of the pharmaceutical container, a molar ratio MgO/CaO is preferably less than 9.0, 8.0 or less, 6.0 or less, less than 5.0, less than 3.0, 1.0 or less, less than 1.0, 0.9 or less, less than 0.7, less than 0.5, less than 0.4, less than 0.3, less than 0.2, particularly preferably less than 0.1. When the molar ratio MgO/CaO is too large, the hydrolytic resistance is liable to deteriorate.
[0080] In order to achieve both the hydrolytic resistance and processability, it is preferable to regulate a molar ratio Li.sub.2O/CaO when emphasizing the content of Li.sub.2O in order to balance the ingredients of Li.sub.2O and CaO. The molar ratio Li.sub.2O/CaO is preferably 100 or less, 90 or less, 80 or less, 70 or less, 60 or less, 50 or less, 40 or less, 30 or less, 20 or less, 10 or less, 9 or less, 8 or less, 7 or less, 6 or less, 5 or less, 4 or less, 3.5 or less, 3.4 or less, 3.3 or less, 3.2 or less, 3.1 or less, 3 or less, 2 or less, 1.8 or less, 1.7 or less, 1.6 or less, particularly preferably 1.5 or less.
[0081] In order to achieve both the hydrolytic resistance and processability, it is preferable to regulate the molar ratio CaO/Li.sub.2O when emphasizing the content of CaO in order to balance the ingredients of Li.sub.2O and CaO. The molar ratio CaO/Li.sub.2O is preferably 2.0 or less, 1.5 or less, 1.2 or less, 1.1 or less, 1.0 or less, less than 1.0, 0.9 or less, 0.8 or less, 0.7 or less, 0.6 or less, 0.5 or less, 0.4 or less, 0.3 or less, 0.2 or less, 0.1 or less, particularly preferably 0.001 or less.
[0082] The content of SiO.sub.2+Al.sub.2O.sub.3+Li.sub.2O+Na.sub.2O+K.sub.2O+MgO+CaO+SrO+BaO is preferably 90% or more, 93% or more, 95% or more, 96% or more, 97% or more, 98% or more, 98.5% or more, particularly preferably 99% or more. When the content of SiO.sub.2+Al.sub.2O.sub.3+Li.sub.2O+Na.sub.2O+K.sub.2O+MgO+CaO+SrO+BaO is too small, it is difficult to achieve both the hydrolytic resistance and processability.
[0083] A molar ratio (Li.sub.2O+Na.sub.2O+K.sub.2O+MgO+CaO+SrO+BaO—Al.sub.2O.sub.3)/(SiO.sub.2+Al.sub.2O.sub.3) is a ratio of the ingredient that cuts the network structure in the glass to the ingredient that forms the network structure in the glass. As described above, the alkali metal oxides and the alkaline earth metal oxides have an effect of cutting the network structure in the glass, but the alkali metal oxides in the same amount as the content of Al.sub.2O.sub.3 are not effective in cutting the network since Al.sub.2O.sub.3 forms the network structure in the glass together with the alkali metal oxide. Further, SiO.sub.2 and Al.sub.2O.sub.3 are ingredients that form the network structure in the glass. Accordingly, as the molar ratio (Li.sub.2O+Na.sub.2O+K.sub.2O+MgO+CaO+SrO+BaO—Al.sub.2O.sub.3)/(SiO.sub.2+Al.sub.2O.sub.3) is smaller, the ingredient that cuts the network structure is smaller with respect to the ingredient that forms the network structure, so that the chemical durability, particularly the hydrolytic resistance, is improved. Therefore, the upper limit range of the molar ratio (Li.sub.2O+Na.sub.2O+K.sub.2O+MgO+CaO+SrO+BaO—Al.sub.2O.sub.3)/(SiO.sub.2+Al.sub.2O.sub.3) is 0.2 or less, preferably 0.19 or less, 0.018 or less, 0.17 or less, 0.16 or less, less than 0.159, 0.158 or less, 0.157 or less, 0.156 or less, less than 0.155, 0.15 or less, 0.14 or less, 0.13 or less, 0.12 or less, particularly preferably 0.11 or less. In particular, when the molar ratio (Li.sub.2O+Na.sub.2O+K.sub.2O+MgO+CaO+SrO+BaO—Al.sub.2O.sub.3)/(SiO.sub.2+Al.sub.2O.sub.3) is 0.156 or less, both the hydrolytic resistance and processability are particularly liable to be achieved. Meanwhile, when the molar ratio (Li.sub.2O+Na.sub.2O+K.sub.2O+MgO+CaO+SrO+BaO—Al.sub.2O.sub.3)/(SiO.sub.2+Al.sub.2O.sub.3) is too small, the viscosity of the glass is liable to increase. Therefore, the lower limit range of the molar ratio (Li.sub.2O+Na.sub.2O+K.sub.2O+MgO+CaO+SrO+BaO—Al.sub.2O.sub.3)/(SiO.sub.2+Al.sub.2O.sub.3) is preferably 0 or more, 0.01 or more, 0.02 or more, 0.03 or more, 0.04 or more, 0.05 or more, 0.06 or more, 0.07 or more, 0.08 or more, 0.09 or more, particularly preferably 0.1 or more.
[0084] In addition to the above ingredients, other ingredients may be introduced.
[0085] ZrO.sub.2 is an ingredient that enhances alkali resistance. However, when the content of ZrO.sub.2 is too large, the viscosity of the glass increases, and the devitrification resistance is liable to decrease. Therefore, the content of ZrO.sub.2 is preferably 0% to 3%, 0% to 2.5%, 0% to 2%, 0% to 1.5%, 0.1% to 0.8%, particularly preferably 0.2% to 0.6%.
[0086] ZnO has an effect of decreasing the viscosity of glass. However, when the content of ZnO is too large, the hydrolytic resistance is adversely affected. Therefore, the content of ZnO is preferably 0% to 4%, 0% to 1%, particularly preferably 0% to 0.01%.
[0087] When the glass is desired to be colored, TiO.sub.2 and Fe.sub.2O.sub.3 may be added to the batch raw material. In this case, the total content and individual content of TiO.sub.2 and Fe.sub.2O.sub.3 are preferably 7% or less, 6% or less, more than 0% to 5%, 0.001% to 1%, particularly preferably 0.1% to 0.5%.
[0088] TiO.sub.2 and Fe.sub.2O.sub.3 are also ingredients contained as impurities in the SiO.sub.2 raw material, for example. Therefore, TiO.sub.2 and Fe.sub.2O.sub.3 may be contained in the glass even when the glass is not colored. When the glass is not colored, the content of TiO.sub.2 is preferably 0.1% or less, 0.08% or less, 0.05% or less, 0.03% or less, 0.01% or less, particularly preferably 0.005% or less, and the content of Fe.sub.2O.sub.3 is preferably 0.1% or less, 0.08% or less, 0.05% or less, 0.03% or less, 0.01% or less, particularly preferably 0.005% or less.
[0089] As a fining agent, one or more kinds of F, Cl, Sb.sub.2O.sub.3, SnO.sub.2, SO.sub.3 and the like may be introduced. The total content and individual content of these fining agents are preferably 5% or less, 1% or less, 0.5% or less, particularly preferably 0.3% or less. Note that, even when Cl is not added as a fining agent, Cl may be contained in the glass as impurities contained in the batch raw material. When the content of Cl is too large, white defects are likely to occur when the glass is subjected to heat processing. Therefore, the content of Cl is preferably 0.1% or less, 0.05% or less, 0.01% or less, 0.005% or less, particularly preferably 0.04% or less.
[0090] In order to improve chemical durability, viscosity in high temperature and the like, P.sub.2O.sub.5, Cr.sub.2O.sub.3, PbO, La.sub.2O.sub.3, WO.sub.3, Nb.sub.2O.sub.3, Y.sub.2O.sub.3, and the like may be introduced at 3% or less, 2% or less, 1% or less, less than 1%, or 0.5% or less each.
[0091] As impurities, ingredients such as H.sub.2, CO.sub.2, CO, H.sub.2O, He, Ne, Ar, and N.sub.2 may be introduced up to 0.1% each. The amount of noble metal elements such as Pt, Rh, and Au to be mixed is preferably 500 ppm or less, and more preferably 300 ppm or less.
[0092] In the glass for a pharmaceutical container of the present invention, the class in a hydrolytic resistance test (acetone washing) according to ISO 720 is preferably at least HGA2, and particularly preferably HGA1.
[0093] An elution amount of alkali in terms of Na.sub.2O determined by the hydrolytic resistance test (acetone washing) according to ISO 720 is preferably less than 527 μg/g, 200 μgig or less, 100 μg/g or less, 90 μg/g or less, 80 μg/g or less, 70 μg/g or less, less than 62 μg/g, 60 μg/g or less, 57 μg/g or less, 55 μg/g or less, 53 μg/g or less, particularly preferably 50 μg/g or less. In a case where the elution amount of alkali is too large, the medicament ingredient may be changed in quality due to the alkali component eluted from the glass when the glass is processed into an ampoule or a vial, filled with and stores medicaments.
[0094] Further, the alkali resistance in a test according to ISO 695 is preferably at least class 2. Here, the “alkali resistance test according to ISO 695” refers to the following test.
[0095] (1) A sample is prepared which has a surface area Acm.sup.2 (where A is 10 cm.sup.2 to 15 cm.sup.2) and in which the entire surface is mirror-finished. First, as a pretreatment, hydrofluoric acid (40 mass %) and hydrochloric acid (2 mol/L) are mixed at a volume ratio of 1:9 to prepare a solution. The sample is immersed in the solution, followed by stirring with a magnetic stirrer for 10 minutes. The sample is taken out, ultrasonic washing with purified water for 2 minutes is performed three times, and ultrasonic washing with ethanol for 1 minute is performed twice.
[0096] (2) Thereafter, the sample is dried in an oven at 110° C. for 1 hour, and is allowed to cool in a desiccator for 30 minutes.
[0097] (3) The mass m1 of the sample is measured and recorded to an accuracy of ±0.1 mg.
[0098] (4) An sodium hydroxide aqueous solution (1 mol/L) and a sodium carbonate aqueous solution (0.5 mol/L) are mixed at a volume ratio of 1:1 to prepare 800 mL of a solution. The solution is placed in a stainless steel container and boiled by a mantle heater. Next, after the sample suspended by a platinum wire is put thereto and held for 3 hours, the sample is taken out, ultrasonic washing with purified water for 2 minutes is performed three times, and ultrasonic washing with ethanol for 1 minute is performed twice. Thereafter, the sample is dried in an oven at 110° C. for 1 hour, and is allowed to cool in a desiccator for 30 minutes.
[0099] (5) The mass m2 of the sample is measured and recorded to an accuracy of ±0.1 mg.
[0100] (6) From the masses m1 and m2 (mg) before and after the introduction into the boiling alkaline solution and the surface area A (cm.sup.2) of the sample, a mass loss amount per unit area is calculated by the following calculation formula, and the calculated mass loss amount is used as a measurement value of the alkali resistance test.
(Mass loss amount per unit area)=100×(m1−m2)/A
[0101] The “alkali resistance in the test according to ISO 695 is class 2” means that the mass loss amount per unit area determined as described above is 175 mg/dm.sup.2 or less. When the mass loss amount per unit area determined as described above is 75 mg/dm.sup.2 or less, “alkali resistance in a test according to ISO 695 is class 1”. In the glass for a pharmaceutical container of the present invention, the mass loss amount per unit area is preferably 130 mg/dm.sup.2 or less, particularly preferably 75 mg/dm.sup.2 or less.
[0102] The delamination often occurs when a glass container is filled with and stores medicaments in which a solution (e.g., citric acid, a phosphate buffer solution) is used that exhibits a behavior such as a strong alkaline solution even when the pH is around neutral. When the mass loss amount per unit area determined by the test according to ISO 695 is more than 175 mg/dm.sup.2, the delamination is more likely to occur. Therefore, in the glass for a pharmaceutical container of the present invention, the mass loss amount per unit area is preferably 130 mg/dm.sup.2 or less, particularly preferably 75 mg/dm.sup.2 or less.
[0103] In an acid resistance test according to YBB⋅BR>00342004, the mass loss amount per unit area is preferably 1.5 mg/dm.sup.2 or less, particularly preferably 0.7 mg/dm.sup.2 or less. In a case where the mass loss amount is large, the elution amount of the glass component is significantly increased when a pharmaceutical container such as an ampoule or a vial is prepared, then is filled with and stores aqueous-based medicaments, and the aqueous-based medicament ingredient is caused to be changed in quality.
[0104] The “acid resistance test according to YBB00342004” refers to the following test.
[0105] (1) A sample is prepared which has a surface area Acm.sup.2 (where A is 100±5 cm.sup.2) and in which the entire surface is mirror-finished. First, as a pretreatment, hydrofluoric acid (40 mass %) and hydrochloric acid (2 mol/L) are mixed at a volume ratio of 1:9 to prepare a solution. The sample is immersed in the solution, followed by stirring with a magnetic stirrer for 10 minutes. The sample is taken out, ultrasonic washing with purified water for 2 minutes is performed three times, and ultrasonic washing with ethanol for 1 minute is performed twice.
[0106] (2) Thereafter, the sample is dried in an oven at 110° C. for 1 hour, and is allowed to cool in a desiccator for 30 minutes.
[0107] (3) The mass m1 of the sample is measured and recorded to an accuracy of ±0.1 mg.
[0108] (4) 800 mL of a hydrochloric acid solution (6 mol/L) is prepared. The hydrochloric acid solution is put in a container formed of silica glass and boiled by an electric heater. A sample suspended by a platinum wire is put thereto and held for 6 hours. The sample is taken out, ultrasonic washing with purified water for 2 minutes is performed three times, and ultrasonic washing with ethanol for 1 minute is performed twice. Thereafter, the sample is dried in an oven at 110° C. for 1 hour, and is allowed to cool in a desiccator for 30 minutes.
[0109] (5) The mass m2 of the sample is measured and recorded to an accuracy of ±0.1 mg.
[0110] (6) From the masses m1 and m2 (mg) before and after the introduction into the boiling acid solution and the surface area A (cm.sup.2) of the sample, a half of the mass loss amount per unit area is calculated by the following calculation formula, and is used as a measurement value of the acid resistance test.
(Mass loss amount per unit area=½×100×(m1−m2)/A
[0111] In the glass for a pharmaceutical container of the present invention, the working point is preferably 1350° C. or less, 1300° C. or less, 1260° C. or less, particularly preferably 1250° C. or less. When the working point is high, the processing temperature at the time of processing the glass tube into an ampoule or a vial becomes higher, and the volatilization of the alkali component contained in the glass significantly increases. The volatilized alkali component adheres to the inner wall of the glass tube, and the glass tube in this state is processed into a glass container. Such a glass container becomes a cause of changing the medicaments in quality when the glass container is filled with and stores the medicaments. In addition, in the case of glass containing a large amount of boron, the higher the working point is, the higher the volatilization of boron is, which may cause delamination.
[0112] The glass for a pharmaceutical container of the present invention can be subjected to chemical strengthening (ion exchanging) to form a compression stress layer on the surface thereof. In the glass for a pharmaceutical container of the present invention, a compression stress value of the compression stress layer formed when the glass for a pharmaceutical container is subjected to chemical strengthening by being immersed in a KNO.sub.3 molten salt at 475° C. for 7 hours is preferably 100 MPa or more, more preferably 200 MPa or more, and particularly preferably 300 MPa or more. Further, a stress depth of the compression stress layer formed when the glass for a pharmaceutical container is subjected to chemical strengthening by being immersed in the KNO.sub.3 molten salt at 475° C. for 7 hours is preferably 10 μm or more, more preferably 20 μm or more, and particularly preferably 30 μm or more.
[0113] The compression stress value and the stress depth of the compression stress layer can be measured as follows. First, both surfaces of a sample are mirror-polished, and then the sample is immersed in a KNO.sub.3 molten salt at 475° C. for 7 hours to perform chemical strengthening. Subsequently, the surface of the sample is washed, and the compression stress value and the stress depth are calculated based on the number of interference fringes observed using a surface stress meter (FSM-6000 manufactured by Orihara Seisakusho Co., Ltd.) and an interval between the interference fringes. In the calculation, a refractive index of the sample is 1.50, and a photoelastic constant is 29.5 [(nm/cm)/MPa]. Note that, before and after the chemical strengthening, the glass composition in the glass surface layer is microscopically different, but the glass composition is not substantially different as a whole of the glass.
[0114] Next, a method for manufacturing the glass tube for a pharmaceutical container of the present invention will be described by a Danner process.
[0115] First, a glass raw material is blended so as to have a predetermined glass composition to prepare a batch. Next, this batch is continuously charged into a melting kiln at 1550° C. to 1700° C. to perform melting and fining. Then, while the obtained molten glass is wound around a rotating refractory, air is blown out from a front end portion of the refractory, and the glass is drawn out in a tubular shape from the front end portion of the refractory.
[0116] Subsequently, the drawn tubular glass is cut to a predetermined length to obtain a glass tube. The glass tube thus obtained is used for manufacturing a pharmaceutical container such as a vial or an ampoule.
[0117] The manufacturing of the glass tube for a pharmaceutical container of the present invention is not limited to the Danner process. The glass tube for a pharmaceutical container may be manufactured by another method (for example, a Vello process or a down-draw method).
[0118] Next, a method for manufacturing the pharmaceutical container of the present invention will be described. Hereinafter, a method of manufacturing a pharmaceutical container by processing a glass tube by a vertical processing method will be described, but this method is an example.
[0119] First, after a glass tube is prepared, an end portion on one side of the glass tube is heated by a burner in a state where the glass tube stands vertically, and a shoulder portion and a mouth portion are formed by using a forming tool. Next, a portion of the glass tube above the shoulder portion is heated and fused with a burner. Subsequently, the fused portion is heated and formed with a burner to form a bottom portion, thereby obtaining a pharmaceutical container.
[0120] The fused portion on the glass tube side is opened by heating with a burner, and is used for manufacturing the next pharmaceutical container. By repeating such processing, a plurality of pharmaceutical containers can be obtained from the glass tube.
[0121] If necessary, a chemical strengthened pharmaceutical container can be obtained by immersing a pharmaceutical container such as an ampoule or a vial in a KNO.sub.3 molten salt and performing ion exchange.
[0122] The glass tube for a pharmaceutical container and the pharmaceutical container may have a coating on an inner surface and/or an outer surface thereof. Examples of the coating include inorganic coating such as fluorine, silicon, and a surfactant, and organic coating.
Example
[0123] Hereinafter, the present invention will be described based on examples. The following examples are merely illustrative and do not limit the present invention.
[0124] Tables 1 to 6 show examples (sample Nos. 1 to 69) of the present invention. In the tables, “R.sub.2O” means Li.sub.2O+Na.sub.2O+K.sub.2O, “R′O” means MgO+CaO+SrO+BaO, and “N.A.” means unmeasured.
TABLE-US-00001 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 SiO.sub.2 78.7 79.6 80.1 80.5 79.7 78.7 78.7 77.9 82.8 79.6 80.9 82.2 Al.sub.2O.sub.3 6.8 5.9 5.4 5.0 5.0 5.0 4.5 4.5 3.8 4.9 4.6 4.3 B.sub.2O.sub.3 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.0 0.1 0.1 0.1 Li.sub.2O 6.1 6.1 6.1 6.1 4.8 4.8 4.8 4.8 6.1 6.1 6.1 6.1 Na.sub.2O 4.9 4.9 4.9 4.9 3.6 4.6 4.6 4.6 3.9 5.9 4.9 3.9 K.sub.2O 2.7 2.7 2.7 2.7 2.7 2.7 3.2 4.0 2.7 2.7 2.7 2.7 MgO 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 CaO 0.0 0.0 0.0 0.0 3.4 3.4 3.4 3.4 0.0 0.0 0.0 0.0 SrO 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 BaO 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 ZrO.sub.2 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 SnO.sub.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Fe.sub.2O.sub.3 0.008 0.007 0.008 0.008 0.008 0.007 0.007 0.007 0.008 0.008 0.008 0.010 TiO.sub.2 0.007 0.007 0.007 0.007 0.005 0.007 0.005 0.005 0.007 0.009 0.007 0.005 Cl 0.004 0.004 0.004 0.003 0.004 0.004 0.004 0.004 0.003 0.003 0.003 0.003 SiO.sub.2 + Al.sub.2O.sub.3 + R.sub.2O + 99.2 99.2 99.2 99.2 99.2 99.2 99.2 99.2 99.3 99.2 99.2 99.2 R′O R.sub.2O 13.7 13.7 13.7 13.7 11.1 12.1 12.6 13.4 12.7 14.7 13.7 12.7 R′O 0.0 0.0 0.0 0.0 3.4 3.4 3.4 3.4 0.0 0.0 0.0 0.0 R.sub.2O/Al.sub.2O.sub.3 2.015 2.322 2.537 2.740 2.220 2.420 2.800 2.978 3.342 3.000 2.978 2.953 Li.sub.2O/R.sub.2O 0.445 0.445 0.445 0.445 0.432 0.397 0.381 0.358 0.480 0.415 0.445 0.480 Li.sub.2O/CaO — — — — 1.412 1.412 1.412 1.412 — — — — CaO/R′O — — — — 1.000 1.000 1.000 1.000 — — — — CaO/(R.sub.2O + R′O) 0.000 0.000 0.000 0.000 0.234 0.219 0.213 0.202 0.000 0.000 0.000 0.000 R′O/(R.sub.2O + R′O) 0.000 0.000 0.000 0.000 0.234 0.219 0.213 0.202 0.000 0.000 0.000 0.000 SiO.sub.2/Al.sub.2O.sub.3 11.574 13.492 14.833 16.100 15.940 15.740 17.489 17.311 21.789 16.245 17.587 19.116 (R.sub.2O + R′O − Al.sub.2O.sub.3)/ 0.081 0.091 0.097 0.102 0.112 0.125 0.138 0.149 0.103 0.116 0.106 0.097 (SiO.sub.2 + Al.sub.2O.sub.3) Ps [° C.] N.A. N.A. N.A. N.A. N.A. N.A. N.A. N.A. N.A. N.A. N.A. N.A. Ta [° C.] N.A. N.A. N.A. N.A. N.A. N.A. N.A. N.A. N.A. N.A. N.A. N.A. Ts [° C.] N.A. N.A. N.A. N.A. N.A. N.A. N.A. N.A. N.A. N.A. N.A. N.A. Working point (10.sup.4.0 N.A. N.A. N.A. N.A. N.A. N.A. N.A. N.A. N.A. N.A. N.A. N.A. dPa .Math. s) [° C.] 10.sup.3.0 dPa .Math. s [° C.] N.A. N.A. N.A. N.A. N.A. N.A. N.A. N.A. N.A. N.A. N.A. N.A. Hydrolytic resistance test 33.5 37.5 39.4 45.0 45.3 56.1 71.3 92.7 49.0 61.1 49.6 42.5 [μg/g] Acid resistance test N.A. N.A. N.A. N.A. N.A. N.A. N.A. N.A. N.A. N.A. N.A. N.A. (DIN12116) [mg/dm.sup.2] Alkali resistance test N.A. N.A. N.A. N.A. N.A. N.A. N.A. N.A. N.A. N.A. N.A. N.A. (ISO695) [mg/dm.sup.2] Linear thermal expansion N.A. N.A. N.A. N.A. N.A. N.A. N.A. N.A. N.A. N.A. N.A. N.A. coefficient (20 to 300° C.) Liquidus temperature [° C.] N.A. N.A. N.A. N.A. N.A. N.A. N.A. N.A. N.A. N.A. N.A. N.A. log η at TL [dPa .Math. s] N.A. N.A. N.A. N.A. N.A. N.A. N.A. N.A. N.A. N.A. N.A. N.A.
TABLE-US-00002 TABLE 2 [mol %] No. 13 No. 14 No. 15 No. 16 No. 17 No. 18 No. 19 SiO.sub.2 72.8 74.8 77.3 77.8 77.1 79.4 77.6 Al.sub.2O.sub.3 12.5 11.5 9.0 8.5 6.0 6.0 6.0 B.sub.2O.sub.3 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Li.sub.2O 6.1 6.1 6.1 6.1 6.1 6.1 6.2 Na.sub.2O 5.1 4.1 4.1 4.1 5.9 5.9 5.8 K.sub.2O 2.7 2.7 2.7 2.7 1.9 1.9 1.5 MgO 0.0 0.0 0.0 0.0 0.0 0.0 0.0 CaO 0.0 0.0 0.0 0.0 2.4 0.0 2.3 SrO 0.0 0.0 0.0 0.0 0.0 0.0 0.0 BaO 0.0 0.0 0.0 0.0 0.0 0.0 0.0 ZrO.sub.2 0.5 0.5 0.5 0.5 0.5 0.5 0.5 SnO.sub.2 0.2 0.2 0.2 0.2 0.0 0.1 0.0 Fe.sub.2O.sub.3 0.007 0.007 0.007 0.007 N.A. N.A. 0.005 TiO.sub.2 0.007 0.007 0.007 0.007 N.A. N.A. 0.010 Cl 0.004 0.004 0.004 0.004 N.A. N.A. 0.014 SiO.sub.2 + Al.sub.2O.sub.3 + R.sub.2O + 99.2 99.2 99.2 99.2 99.4 99.3 99.4 R′O R.sub.2O 13.9 12.9 12.9 12.9 13.9 13.9 13.5 R′O 0.0 0.0 0.0 0.0 2.4 0.0 2.3 R.sub.2O/Al.sub.2O.sub.3 1.112 1.122 1.433 1.518 2.317 2.317 2.250 Li.sub.2O/R.sub.2O 0.439 0.473 0.473 0.473 0.439 0.439 0.459 Li.sub.2O/CaO — — — — 2.542 — 2.696 CaO/R′O — — — — 1.000 — 1.000 CaO/(R.sub.2O + R′O) 0.000 0.000 0.000 0.000 0.147 0.000 0.146 R′O/(R.sub.2O + R′O) 0.000 0.000 0.000 0.000 0.147 0.000 0.146 SiO.sub.2/Al.sub.2O.sub.3 5.824 6.504 8.589 9.153 12.850 13.233 12.933 (R.sub.2O + R′O − Al.sub.2O.sub.3)/ 0.016 0.016 0.045 0.051 0.124 0.093 0.117 (SiO.sub.2 + Al.sub.2O.sub.3) Ps [° C.] N.A. N.A. N.A. N.A. N.A. N.A. 479 Ta [° C.] N.A. N.A. N.A. N.A. N.A. N.A. 524 Ts [° C.] N.A. N.A. N.A. N.A. N.A. N.A. 758 Working point (10.sup.4.0 N.A. N.A. N.A. N.A. 1176 1219 1178 dPa .Math. s) [° C.] 10.sup.3.0 dPa .Math. s [° C.] N.A. N.A. N.A. N.A. 1408 1464 1411 Hydrolytic resistance test 40.6 36.0 33.8 31.3 58.9 39.4 55.2 [μg/g] Acid resistance test N.A. N.A. N.A. N.A. N.A. N.A. N.A. (DIN12116) [mg/dm.sup.2] Alkali resistance test N.A. N.A. N.A. N.A. N.A. N.A. N.A. (ISO695)[mg/dm.sup.2] Linear thermal expansion N.A. N.A. N.A. N.A. N.A. N.A. N.A. coefficient (20 to 300° C.) Liquidus temperature [° C.] N.A. N.A. N.A. N.A. N.A. N.A. N.A. log η at TL [dPa .Math. s] N.A. N.A. N.A. N.A. N.A. N.A. N.A. [mol %] No. 20 No. 21 No. 22 No. 23 No. 24 SiO.sub.2 77.6 77.3 77.3 77.8 76.8 Al.sub.2O.sub.3 6.0 6.2 6.1 6.0 6.0 B.sub.2O.sub.3 0.1 0.1 0.1 0.1 0.1 Li.sub.2O 6.1 6.3 6.1 6.1 6.1 Na.sub.2O 5.9 5.8 4.9 5.8 5.9 K.sub.2O 1.5 1.5 1.9 0.0 0.0 MgO 0.0 0.0 0.0 0.0 1.5 CaO 2.3 2.3 3.1 3.6 3.0 SrO 0.0 0.0 0.0 0.0 0.0 BaO 0.0 0.0 0.0 0.0 0.0 ZrO.sub.2 0.5 0.5 0.5 0.5 0.5 SnO.sub.2 0.0 0.0 0.0 0.1 0.1 Fe.sub.2O.sub.3 0.005 0.005 0.005 0.005 0.006 TiO.sub.2 0.010 0.010 0.010 0.010 0.010 Cl 0.016 0.016 0.014 0.014 0.016 SiO.sub.2 + Al.sub.2O.sub.3 + R.sub.2O + 99.4 99.4 99.4 99.3 99.3 R′O R.sub.2O 13.5 13.6 12.9 11.9 12.0 R′O 2.3 2.3 3.1 3.6 4.5 R.sub.2O/Al.sub.2O.sub.3 2.250 2.194 2.115 1.983 2.000 Li.sub.2O/R.sub.2O 0.452 0.463 0.473 0.513 0.508 Li.sub.2O/CaO 2.652 2.739 1.968 1.694 2.033 CaO/R′O 1.000 1.000 1.000 1.000 1.000 CaO/(R.sub.2O + R′O) 0.146 0.145 0.194 0.232 0.182 R′O/(R.sub.2O + R′O) 0.146 0.145 0.194 0.232 0.273 SiO.sub.2/Al.sub.2O.sub.3 12.933 12.468 12.672 12.967 12.800 (R.sub.2O + R′O − Al.sub.2O.sub.3)/ 0.117 0.116 0.119 0.113 0.127 (SiO.sub.2 + Al.sub.2O.sub.3) Ps [° C.] 479 479 487 499 494 Ta [° C.] 523 524 532 544 539 Ts [° C.] 758 758 767 779 777 Working point (10.sup.4.0 1180 1178 1186 1198 1197 dPa .Math. s) [° C.] 10.sup.3.0 dPa .Math. s [° C.] 1411 1410 1418 1428 1422 Hydrolytic resistance test 57.0 54.9 54.7 53.1 55.2 [μg/g] Acid resistance test N.A. N.A. N.A. N.A. N.A. (DIN12116) [mg/dm.sup.2] Alkali resistance test N.A. N.A. N.A. N.A. N.A. (ISO695)[mg/dm.sup.2] Linear thermal expansion N.A. N.A. N.A. N.A. N.A. coefficient (20 to 300° C.) Liquidus temperature [° C.] N.A. N.A. N.A. N.A. N.A. log η at TL [dPa .Math. s] N.A. N.A. N.A. N.A. N.A.
TABLE-US-00003 TABLE 3 [mol %] No. 25 No. 26 No. 27 No. 28 No. 29 No. 30 No. 31 SiO.sub.2 75.8 77.3 78.8 75.3 75.9 76.4 75.0 Al.sub.2O.sub.3 7.0 5.5 4.0 6.5 9.1 8.6 9.1 B.sub.2O.sub.3 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Li.sub.2O 6.1 6.1 6.1 6.1 6.1 6.1 6.1 Na.sub.2O 5.9 5.9 5.9 5.8 5.8 5.8 5.8 K.sub.2O 1.9 1.9 1.9 1.9 2.5 2.5 3.4 MgO 0.0 0.0 0.0 0.0 0.0 0.0 0.0 CaO 2.6 2.6 2.6 3.7 0.0 0.0 0.0 SrO 0.0 0.0 0.0 0.0 0.0 0.0 0.0 BaO 0.0 0.0 0.0 0.0 0.0 0.0 0.0 ZrO.sub.2 0.5 0.5 0.5 0.5 0.5 0.5 0.5 SnO.sub.2 0.1 0.1 0.1 0.1 0.0 0.0 0.0 Fe.sub.2O.sub.3 N.A. N.A. N.A. 0.005 0.004 0.004 0.004 TiO.sub.2 N.A. N.A. N.A. 0.011 0.011 0.011 0.010 Cl N.A. N.A. N.A. 0.012 0.020 0.020 0.018 SiO.sub.2 + Al.sub.2O.sub.3 + R.sub.2O + 99.3 99.3 99.3 99.3 99.4 99.4 99.4 R′O R.sub.2O 13.9 13.9 13.9 13.8 14.4 14.4 15.3 R′O 2.6 2.6 2.6 3.7 0.0 0.0 0.0 R.sub.2O/Al.sub.2O.sub.3 1.986 2.527 3.475 2.123 1.582 1.674 1.681 Li.sub.2O/R.sub.2O 0.439 0.439 0.439 0.442 0.424 0.424 0.399 Li.sub.2O/CaO 2.346 2.346 2.346 1.649 — — — CaO/R′O 1.000 1.000 1.000 1.000 — — — CaO/(R.sub.2O + R′O) 0.158 0.158 0.158 0.211 0.000 0.000 0.000 R′O/(R.sub.2O + R′O) 0.158 0.158 0.158 0.211 0.000 0.000 0.000 SiO.sub.2/Al.sub.2O.sub.3 10.829 14.055 19.700 11.585 8.341 8.884 8.242 (R.sub.2O + R′O − Al.sub.2O.sub.3)/ 0.115 0.133 0.151 0.134 0.062 0.068 0.074 (SiO.sub.2 + Al.sub.2O.sub.3) Ps [° C.] N.A. N.A. N.A. 485 496 490 485 Ta [° C.] N.A. N.A. N.A. 528 545 538 533 Ts [° C.] N.A. N.A. N.A. 753 806 795 784 Working point (10.sup.4.0 N.A. N.A. N.A. 1159 1272 1259 1243 dPa .Math. s) [° C.] 10.sup.3.0 dPa .Math. s [° C.] N.A. N.A. N.A. 1381 1521 1508 1490 Hydrolytic resistance test 57.8 69.8 102.9 63.9 36.9 35.3 37.8 [μg/g] Acid resistance test N.A. N.A. N.A. N.A. N.A. N.A. N.A. (DIN12116) [mg/dm.sup.2] Alkali resistance test N.A. N.A. N.A. 47 N.A. 55 N.A. (ISO695)[mg/dm.sup.2] Linear thermal expansion N.A. N.A. N.A. 72.2 70.6 70.9 75.6 coefficient (20 to 300° C.) Liquidus temperature [° C.] N.A. N.A. N.A. N.A. N.A. N.A. N.A. log η at TL [dPa .Math. s] N.A. N.A. N.A. 5.5 6.8 6.9 N.A. [mol %] No. 32 No. 33 No. 34 No. 35 No. 36 SiO.sub.2 75.6 76.0 75.5 74.8 76.0 Al.sub.2O.sub.3 8.5 8.5 8.5 8.6 8.7 B.sub.2O.sub.3 0.1 0.1 0.1 0.1 0.1 Li.sub.2O 6.1 6.1 6.1 6.1 6.1 Na.sub.2O 5.8 5.8 5.8 5.8 5.8 K.sub.2O 3.4 2.5 2.5 2.5 2.7 MgO 0.0 0.0 0.0 0.0 0.0 CaO 0.0 0.0 0.0 0.0 0.0 SrO 0.0 0.0 0.0 0.0 0.0 BaO 0.0 0.0 0.0 0.0 0.0 ZrO.sub.2 0.5 1.0 1.5 2.0 0.5 SnO.sub.2 0.0 0.0 0.0 0.1 0.1 Fe.sub.2O.sub.3 0.004 0.004 0.004 0.004 0.005 TiO.sub.2 0.011 0.012 0.014 0.015 0.011 Cl 0.020 0.020 0.020 0.020 0.020 SiO.sub.2 + Al.sub.2O.sub.3 + R.sub.2O + 99.4 98.9 98.4 97.8 99.3 R′O R.sub.2O 15.3 14.4 14.4 14.4 14.6 R′O 0.0 0.0 0.0 0.0 0.0 R.sub.2O/Al.sub.2O.sub.3 1.800 1.694 1.694 1.674 1.678 Li.sub.2O/R.sub.2O 0.399 0.424 0.424 0.424 0.418 Li.sub.2O/CaO — — — — — CaO/R′O — — — — — CaO/(R.sub.2O + R′O) 0.000 0.000 0.000 0.000 0.000 R′O/(R.sub.2O + R′O) 0.000 0.000 0.000 0.000 0.000 SiO.sub.2/Al.sub.2O.sub.3 8.894 8.941 8.882 8.698 8.736 (R.sub.2O + R′O − Al.sub.2O.sub.3)/ 0.081 0.070 0.070 0.070 0.070 (SiO.sub.2 + Al.sub.2O.sub.3) Ps [° C.] 481 500 511 522 488 Ta [° C.] 533 549 560 572 536 Ts [° C.] 777 808 822 836 792 Working point (10.sup.4.0 1230 1267 1269 1276 1253 dPa .Math. s) [° C.] 10.sup.3.0 dPa .Math. s [° C.] 1474 1510 1506 1506 1502 Hydrolytic resistance test 39.1 37.8 40.0 41.9 37.5 [μg/g] Acid resistance test N.A. N.A. N.A. N.A. N.A. (DIN12116) [mg/dm.sup.2] Alkali resistance test N.A. 42 37 35 49 (ISO695)[mg/dm.sup.2] Linear thermal expansion 75.4 70.4 70.2 70.0 72.0 coefficient (20 to 300° C.) Liquidus temperature [° C.] N.A. N.A. N.A. N.A. 804 log η at TL [dPa .Math. s] N.A. 7.4 7.1 7.3 7.5
TABLE-US-00004 TABLE 4 [mol %] No. 37 No. 38 No. 39 No. 40 No. 41 No. 42 SiO.sub.2 73.9 73.9 73.9 75.9 75.9 77.9 Al.sub.2O.sub.3 7.2 7.2 7.2 7.2 7.2 7.2 B.sub.2O.sub.3 0.1 0.1 0.1 0.1 0.1 0.1 Li.sub.2O 8.1 6.1 4.1 6.1 4.1 6.1 Na.sub.2O 3.8 5.8 7.8 3.8 5.8 1.8 K.sub.2O 2.7 2.7 2.7 2.7 2.7 2.7 MgO 0.0 0.0 0.0 0.0 0.0 0.0 CaO 3.7 3.7 3.7 3.7 3.7 3.7 SrO 0.0 0.0 0.0 0.0 0.0 0.0 BaO 0.0 0.0 0.0 0.0 0.0 0.0 ZrO.sub.2 0.5 0.5 0.5 0.5 0.5 0.5 SnO.sub.2 0.0 0.0 0.0 0.0 0.0 0.0 Fe.sub.2O.sub.3 0.005 0.005 0.005 0.005 0.006 0.006 TiO.sub.2 0.010 0.010 0.010 0.010 0.011 0.011 Cl 0.014 0.019 0.025 0.014 0.018 0.007 SiO.sub.2 + Al.sub.2O.sub.3 + R.sub.2O + 99.4 99.4 99.4 99.4 99.4 99.4 R′O R.sub.2O 14.6 14.6 14.6 12.6 12.6 10.6 R′O 3.7 3.7 3.7 3.7 3.7 3.7 R.sub.2O/Al.sub.2O.sub.3 2.028 2.028 2.028 1.750 1.750 1.472 Li.sub.2O/R.sub.2O 0.555 0.418 0.281 0.484 0.325 0.575 Li.sub.2O/CaO 2.189 1.649 1.108 1.649 1.108 1.649 CaO/R′O 1.000 1.000 1.000 1.000 1.000 1.000 CaO/(R.sub.2O + R′O) 0.202 0.202 0.202 0.227 0.227 0.259 R′O/(R.sub.2O + R′O) 0.202 0.202 0.202 0.227 0.227 0.259 SiO.sub.2/Al.sub.2O.sub.3 10.264 10.264 10.264 10.542 10.542 10.819 (R.sub.2O + R′O − Al.sub.2O.sub.3)/ 0.137 0.137 0.137 0.110 0.110 0.083 (SiO.sub.2 + Al.sub.2O.sub.3) Ps [° C.] 480 483 489 501 508 528 Ta [° C.] 523 526 533 547 553 576 Ts [° C.] 744 748 757 786 796 833 Working point (10.sup.4.0 1141 1153 1166 1211 1225 1283 dPa .Math. s) [° C.] 10.sup.3.0 dPa .Math. s [° C.] 1361 1374 1390 1442 1458 1522 Hydrolytic resistance test 62.0 63.9 68.8 43.4 47.7 32.6 Acid resistance test N.A. N.A. N.A. N.A. N.A. N.A. (DIN12116) [mg/dm.sup.2] Alkali resistance test N.A. N.A. N.A. N.A. N.A. N.A. (ISO695) [mg/dm.sup.2] Linear thermal expansion 72.4 76.1 79.3 67.7 71.6 58.0 coefficient (20 to 300° C.) Liquidus temperature [° C.] 919 914 925 964 982 982 log η at TL [dPa .Math. s] 5.6 5.7 5.7 5.7 5.6 6.0 [mol %] No. 43 No. 44 No. 45 No. 46 No. 47 No. 48 SiO.sub.2 77.8 77.9 76.9 76.8 76.9 76.8 Al.sub.2O.sub.3 7.2 7.2 7.2 7.2 7.2 7.3 B.sub.2O.sub.3 0.1 0.1 0.1 0.1 0.1 0.1 Li.sub.2O 4.1 2.1 3.1 4.1 4.6 5.1 Na.sub.2O 3.8 5.8 5.7 4.8 4.3 3.8 K.sub.2O 2.7 2.7 2.7 2.7 2.7 2.7 MgO 0.0 0.0 0.0 0.0 0.0 0.0 CaO 3.7 3.6 3.7 3.7 3.7 3.7 SrO 0.0 0.0 0.0 0.0 0.0 0.0 BaO 0.0 0.0 0.0 0.0 0.0 0.0 ZrO.sub.2 0.5 0.5 0.5 0.5 0.5 0.5 SnO.sub.2 0.1 0.1 0.1 0.1 0.0 0.0 Fe.sub.2O.sub.3 0.006 0.006 0.006 0.006 0.006 0.006 TiO.sub.2 0.010 0.011 0.011 0.011 0.011 0.011 Cl 0.013 0.018 0.018 0.016 0.016 0.014 SiO.sub.2 + Al.sub.2O.sub.3 + R.sub.2O + 99.3 99.3 99.3 99.3 99.4 99.4 R′O R.sub.2O 10.6 10.6 11.5 11.6 11.6 11.6 R′O 3.7 3.6 3.7 3.7 3.7 3.7 R.sub.2O/Al.sub.2O.sub.3 1.472 1.472 1.597 1.611 1.611 1.589 Li.sub.2O/R.sub.2O 0.387 0.198 0.270 0.353 0.397 0.440 Li.sub.2O/CaO 1.108 0.583 0.838 1.108 1.243 1.378 CaO/R′O 1.000 1.000 1.000 1.000 1.000 1.000 CaO/(R.sub.2O + R′O) 0.259 0.254 0.243 0.242 0.242 0.242 R′O/(R.sub.2O + R′O) 0.259 0.254 0.243 0.242 0.242 0.242 SiO.sub.2/Al.sub.2O.sub.3 10.806 10.819 10.681 10.667 10.681 10.521 (R.sub.2O + R′O − Al.sub.2O.sub.3)/ 0.084 0.082 0.095 0.096 0.096 0.095 (SiO.sub.2 + Al.sub.2O.sub.3) Ps [° C.] 533 546 524 518 517 515 Ta [° C.] 583 597 572 566 564 562 Ts [° C.] 845 863 828 820 817 814 Working point (10.sup.4.0 1300 1321 1273 1264 1260 1258 dPa .Math. s) [° C.] 10.sup.3.0 dPa .Math. s [° C.] 1541 1563 1511 1504 1498 1494 Hydrolytic resistance test 31.3 35.3 41.2 41.2 41.2 41.5 Acid resistance test N.A. N.A. N.A. N.A. N.A. N.A. (DIN12116) [mg/dm.sup.2] Alkali resistance test N.A. N.A. N.A. N.A. N.A. N.A. (ISO695) [mg/dm.sup.2] Linear thermal expansion 62.6 66.6 68.9 67.0 66.1 65.0 coefficient (20 to 300° C.) Liquidus temperature [° C.] 1025 1046 1020 999 1017 995 log η at TL [dPa .Math. s] 5.8 5.7 5.6 5.7 5.5 5.7
TABLE-US-00005 TABLE 5 [mol %] No. 49 No. 50 No. 51 No. 52 No. 53 No. 54 No. 55 SlO.sub.2 76.8 76.7 75.9 75.7 77.0 78.5 80.0 Al.sub.2O.sub.3 7.2 7.3 7.2 7.3 6.0 5.5 5.0 B.sub.2O.sub.3 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Li.sub.2O 6.1 7.1 5.1 7.1 8.1 7.1 6.1 Na.sub.2O 2.9 1.9 4.8 2.9 1.9 1.9 1.9 K.sub.2O 2.7 2.7 2.7 2.7 2.7 2.7 2.7 MgO 0.0 0.0 0.0 0.0 0.0 0.0 0.0 CaO 3.7 3.7 3.7 3.7 3.6 3.6 3.6 SrO 0.0 0.0 0.0 0.0 0.0 0.0 0.0 BaO 0.0 0.0 0.0 0.0 0.0 0.0 0.0 ZrO.sub.2 0.5 0.5 0.5 0.5 0.5 0.5 0.5 SnO.sub.2 0.0 0.0 0.0 0.0 0.1 0.1 0.1 Fe.sub.2O.sub.3 0.005 0.005 0.005 0.005 N.A. N.A. N.A. TiO.sub.2 0.010 0.010 0.010 0.010 N.A. N.A. N.A. Cl 0.011 0.009 0.016 0.011 N.A. N.A. N.A. SiO.sub.2 + Al.sub.2O.sub.3 + R.sub.2O + 99.4 99.4 99.4 99.4 99.3 99.3 99.3 R′O R.sub.2O 11.7 11.7 12.6 12.7 12.7 11.7 10.7 R′O 3.7 3.7 3.7 3.7 3.6 3.6 3.6 R.sub.2O/Al.sub.2O.sub.3 1.625 1.603 1.750 1.740 2.117 2.127 2.140 Li.sub.2O/R.sub.2O 0.521 0.607 0.405 0.559 0.638 0.607 0.570 Li.sub.2O/CaO 1.649 1.919 1.378 1.919 2.250 1.972 1.694 CaO/R′O 1.000 1.000 1.000 1.000 1.000 1.000 1.000 CaO/(R.sub.2O + R′O) 0.240 0.240 0.227 0.226 0.221 0.235 0.252 R′O/(R.sub.2O + R′O) 0.240 0.240 0.227 0.226 0.221 0.235 0.252 SiO.sub.2/Al.sub.2O.sub.3 10.667 10.507 10.542 10.370 12.833 14.273 16.000 (R.sub.2O + R′O − Al.sub.2O.sub.3)/ 0.098 0.096 0.110 0.110 0.124 0.117 0.109 (SiO.sub.2 + Al.sub.2O.sub.3) Ps [° C.] 513 512 503 500 N.A. N.A. N.A. Ta [° C.] 560 559 549 545 N.A. N.A. N.A. Ts [° C.] 810 807 790 784 N.A. N.A. N.A. Working point (10.sup.4.0 1248 1241 1223 1207 N.A. N.A. 1258 dPa .Math. s) [° C.] 10.sup.3.0 dPa .Math. s [° C.] 1484 1476 1455 1437 N.A. N.A. 1495 Hydrolytic resistance test 40.6 40.7 47.1 45.0 47.1 43.4 38.4 [μg/g] Acid resistance test N.A. N.A. N.A. N.A. N.A. N.A. N.A. (DIN12116) [mg/dm.sup.2] Alkali resistance test N.A. N.A. N.A. N.A. N.A. N.A. N.A. (ISO695) [mg/dm.sup.2] Linear thermal expansion 62.9 60.6 69.4 65.2 N.A. N.A. N.A. coefficient (20 to 300° C.) Liquidus temperature [° C.] 990 960 995 955 N.A. N.A. N.A. log η at TL [dPa .Math. s] 5.7 5.9 5.5 5.7 N.A. N.A. N.A. [mol %] No. 56 No. 57 No. 58 No. 59 No. 60 SlO.sub.2 77.6 78.3 79.1 79.8 78.6 Al.sub.2O.sub.3 7.0 6.8 6.5 6.3 6.0 B.sub.2O.sub.3 0.1 0.1 0.1 0.1 0.1 Li.sub.2O 6.1 6.1 6.1 6.1 6.1 Na.sub.2O 5.9 5.4 4.9 4.4 5.9 K.sub.2O 2.7 2.7 2.7 2.7 2.7 MgO 0.0 0.0 0.0 0.0 0.0 CaO 0.0 0.0 0.0 0.0 0.0 SrO 0.0 0.0 0.0 0.0 0.0 BaO 0.0 0.0 0.0 0.0 0.0 ZrO.sub.2 0.5 0.5 0.5 0.5 0.5 SnO.sub.2 0.1 0.1 0.1 0.1 0.1 Fe.sub.2O.sub.3 0.004 0.004 0.004 0.005 0.005 TiO.sub.2 0.011 0.011 0.011 0.011 0.011 Cl 0.018 0.018 0.016 0.016 0.019 SiO.sub.2 + Al.sub.2O.sub.3 + R.sub.2O + 99.3 99.3 99.3 99.3 99.3 R′O R.sub.2O 14.7 14.2 13.7 13.2 14.7 R′O 0.0 0.0 0.0 0.0 0.0 R.sub.2O/Al.sub.2O.sub.3 2.100 2.088 2.108 2.095 2.450 Li.sub.2O/R.sub.2O 0.415 0.430 0.445 0.462 0.415 Li.sub.2O/CaO — — — — — CaO/R′O — — — — — CaO/(R.sub.2O + R′O) 0.000 0.000 0.000 0.000 0.000 R′O/(R.sub.2O + R′O) 0.000 0.000 0.000 0.000 0.000 SiO.sub.2/Al.sub.2O.sub.3 11.086 11.515 12.169 12.667 13.100 (R.sub.2O + R′O − Al.sub.2O.sub.3)/ 0.091 0.087 0.084 0.080 0.103 (SiO.sub.2 + Al.sub.2O.sub.3) Ps [° C.] 477 478 481 485 469 Ta [° C.] 525 527 530 534 517 Ts [° C.] 775 780 787 797 763 Working point (10.sup.4.0 1223 1230 1246 1257 1206 dPa .Math. s) [° C.] 10.sup.3.0 dPa .Math. s [° C.] 1466 1475 1494 1507 1446 Hydrolytic resistance test 37.8 36.3 34.4 32.9 42.8 [μg/g] Acid resistance test N.A. N.A. 0.46 N.A. N.A. (DIN12116) [mg/dm.sup.2] Alkali resistance test N.A. N.A. 52 N.A. N.A. (ISO695) [mg/dm.sup.2] Linear thermal expansion 70.5 69.2 66.7 64.5 70.6 coefficient (20 to 300° C.) Liquidus temperature [° C.] N.A. N.A. 800 846 N.A. log η at TL [dPa .Math. s] N.A. N.A. 7.4 7.0 N.A.
TABLE-US-00006 TABLE 6 [mol %] No. 61 No. 62 No. 63 No. 64 No. 65 No. 66 No. 67 No. 68 No. 69 SiO.sub.2 79.2 80.1 81.0 81.5 82.3 79.1 79.9 81.9 84.0 Al.sub.2O.sub.3 5.8 5.5 5.3 5.0 4.8 5.3 5.0 4.0 3.5 B.sub.2O.sub.3 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Li.sub.2O 6.1 6.1 6.1 6.1 6.1 4.8 4.8 6.1 6.1 Na.sub.2O 5.5 4.9 4.3 4.1 3.5 2.7 2.7 4.7 3.1 K.sub.2O 2.7 2.7 2.7 2.7 2.7 3.9 3.6 2.7 2.7 MgO 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 CaO 0.0 0.0 0.0 0.0 0.0 3.6 3.4 0.0 0.0 SrO 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 BaO 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 ZrO.sub.2 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 SnO.sub.2 0.1 0.1 0.0 0.0 0.0 0.0 0.0 0.0 0.0 Fe.sub.2O.sub.3 0.005 0.004 0.005 0.005 0.005 0.005 0.005 0.004 0.004 TiO.sub.2 0.011 0.011 0.011 0.012 0.012 0.011 0.011 0.012 0.011 Cl 0.018 0.016 0.014 0.007 0.005 0.005 0.005 0.007 0.005 SiO.sub.2 + Al.sub.2O.sub.3 + R.sub.2O + 99.3 99.3 99.4 99.4 99.4 99.4 99.4 99.4 99.4 R′O R.sub.2O 14.3 13.7 13.1 12.9 12.3 11.4 11.1 13.5 11.9 R′O 0.0 0.0 0.0 0.0 0.0 3.6 3.4 0.0 0.0 R.sub.2O/Al.sub.2O.sub.3 2.466 2.491 2.472 2.580 2.563 2.151 2.220 3.375 3.400 Li.sub.2O/R.sub.2O 0.427 0.445 0.466 0.473 0.496 0.421 0.432 0.452 0.513 Li.sub.2O/CaO — — — — — 1.333 1.412 — — CaO/R′O — — — — — 1.000 1.000 — — CaO/(R.sub.2O + R′O) 0.000 0.000 0.000 0.000 0.000 0.240 0.234 0.000 0.000 R′O/(R.sub.2O + R′O) 0.000 0.000 0.000 0.000 0.000 0.240 0.234 0.000 0.000 SiO.sub.2/Al.sub.2O.sub.3 13.655 14.564 15.283 16.300 17.146 14.925 15.980 20.475 24.000 (R.sub.2O + R′O − Al.sub.2O.sub.3)/ 0.100 0.096 0.090 0.091 0.086 0.115 0.112 0.111 0.096 (SiO.sub.2 + Al.sub.2O.sub.3) Ps [° C.] 470 472 478 477 482 510 509 464 478 Ta [° C.] 518 521 527 527 533 557 557 513 529 Ts [° C.] 767 773 788 788 801 812 814 765 796 Working point (10.sup.4.0 1210 1228 1240 1239 1257 1252 1261 1202 1247 dPa .Math. s) [° C.] 10.sup.3.0 dPa .Math. s [° C.] 1452 1469 1488 1488 1507 1485 1498 1440 1493 Hydrolytic resistance test [μg/g] 42.8 39.1 34.4 36.0 32.2 49.0 46.2 58.9 40.6 Acid resistance test (DIN12116) N.A. 0.59 N.A. N.A. N.A. 0.26 0.36 0.27 N.A. [mg/dm.sup.2] Alkali resistance test (ISO695) N.A. 54 N.A. N.A. N.A. 48 47 52 N.A. [mg/dm.sup.2] Linear thermal expansion 69.6 64.0 66.7 63.0 60.2 64.3 62.6 65.9 58.3 coefficient (20 to 300° C.) Liquidus temperature [° C.] 843 887 977 1002 N.A. 986 977 N.A. N.A. log η at TL [dPa .Math. s] 6.7 6.3 5.7 5.5 N.A. 5.8 5.9 N.A. N.A.
[0125] Each sample was prepared as follows. First, 550 g of a batch was mixed so as to have a glass composition shown in the tables, and the mixture was melted at 1550° C. for 2.5 hours using a platinum crucible. In order to enhance the homogeneity of the sample, stirring was performed twice in the melting process. Further, in order to enhance the homogeneity of the molten glass, the molten glass was water-crushed and dried, and then melted again at 1550° C. for 1 hour using a platinum crucible. After stirring once, the molten glass was melted at 1600° C. for 2 hours in order to reduce bubbles in the glass. Thereafter, the molten glass was poured out to produce an ingot, and the ingot was processed into a shape necessary for measurement and subjected to various evaluations. The results are shown in the tables.
[0126] The strain point Ps was determined by a fiber stretching method in accordance with ASTM C336. The annealing point Ta and the softening point Ts were obtained by a fiber stretching method in accordance with ASTM C388.
[0127] The working point (temperature at which the viscosity of the glass becomes 10.sup.4.0 dPa.Math.s) and the temperature at which the viscosity of the glass becomes 10.sup.3.0 dPa.Math.s were obtained by a platinum sphere pull up method.
[0128] For a hydrolytic resistance test, a hydrolytic resistance test (acetone washing) according to ISO 720 was performed. The detailed test procedure is as described above.
[0129] The acid resistance was evaluated by an acid resistance test according to YBB00342004, and the alkali resistance was evaluated by a test according to ISO 695.
[0130] The linear thermal expansion coefficient was measured in a temperature range of 20° C. to 300° C. by a dilatometer using a glass formed into a rod shape of about 5 mmφ×20 mm as a measurement sample.
[0131] The liquidus temperature was obtained by filling a ground glass into a platinum boat of about 120×20×10 mm, placing the platinum boat in an electric furnace having a linear temperature gradient for 24 hours, then specifying a crystal precipitation site by microscopic observation, and specifying a temperature corresponding to the crystal precipitation site from a temperature gradient graph of the electric furnace.
[0132] The liquidus viscosity log η at TL was obtained by obtaining a viscosity curve of the glass based on the strain point, the annealing point, the softening point, the working temperature, and the viscosity calculation formula of the Fulcher, and calculating the viscosity of the glass at the liquidus temperature from the viscosity curve.
[0133] As is clear from the tables, in Sample Nos. 1 to 69, the content of B.sub.2O.sub.3 in the glass composition was small, the working temperature was 1321° C. or less, and the elution amount of alkali by the hydrolytic resistance test was 102.9 μg/g or less.
[0134]
INDUSTRIAL APPLICABILITY
[0135] The glass for a pharmaceutical container of the present invention is suitable as a glass for a pharmaceutical container for manufacturing a pharmaceutical container such as an ampoule, a vial, a prefilled syringe, and a cartridge, and is also applicable to a pharmaceutical container for an oral agent and bottles for beverages.