PHARMACEUTICAL PACKAGING COMPRISING A CHEMICALLY RESISTANT GLASS

Abstract

A pharmaceutical packaging is provided including a glass, comprising at least the following components (given in mol % on oxide basis): SiO.sub.2:59-84, Al.sub.2O.sub.3:7-18.5, CaO:1-25, SrO:0-6.5, BaO:0-5, ZrO.sub.2:0-3, TiO.sub.2:0-5, B.sub.2O.sub.3:0-1, wherein the ratio (CaO+SrO+BaO)/Al.sub.2O.sub.3<2.8, wherein the ratio (CaO+SrO+BaO)/SiO.sub.2≦0.39, wherein the hydrolytic resistance according to DIN ISO 720 is class HGA 1, and wherein the glass, apart from unavoidable contaminations, is free of alkali oxides and magnesium oxides.

Claims

1. A pharmaceutical packaging comprising a glass, said glass comprising at least the following components (given in mol % on oxide basis): TABLE-US-00004 SiO.sub.2 59-84 Al.sub.2O.sub.3   7-18.5 CaO  1-25 SrO   0-6.5 BaO 0-5 ZrO.sub.2 0-3 TiO.sub.2 0-5 B.sub.2O.sub.3  0-1, wherein the ratio (CaO+SrO+BaO)/Al.sub.2O.sub.3<2.8; wherein the ratio (CaO+SrO+BaO)/SiO.sub.2≦0.39; wherein the hydrolytic resistance according to DIN ISO 720 is class HGA 1; and wherein the glass, apart from unavoidable contaminations, is free of alkali oxides and of magnesium oxide.

2. The pharmaceutical packaging of claim 1, wherein the ratio (CaO+SrO+BaO)/Al.sub.2O.sub.3 is smaller than 2.3.

3. The pharmaceutical packaging of claim 1, wherein the ratio (CaO+SrO+BaO)/Al.sub.2O.sub.3 is larger than 1.9.

4. The pharmaceutical packaging of claim 1, wherein the ratio (CaO+SrO+BaO)/SiO.sub.2>0.25.

5. The pharmaceutical packaging of claim 1, wherein the content of BaO≦3.

6. The pharmaceutical packaging of claim 1, wherein the content of Al.sub.2O.sub.3 is smaller than 12 mol %.

7. The pharmaceutical packaging of claim 1, wherein the content of Al.sub.2O.sub.3 is larger than 9 mol %.

8. The pharmaceutical packaging of claim 1, wherein the content of CaO is larger than 15 mol %.

9. The pharmaceutical packaging of claim 1, wherein the content of SrO is smaller than 4 mol %.

10. The pharmaceutical packaging of claim 1, wherein the total content of TiO.sub.2+ZrO.sub.2 is at least 0.5 mol %.

11. The pharmaceutical packaging of claim 1, wherein the total content of TiO.sub.2+ZrO.sub.2 is 6 mol % at most.

12. The pharmaceutical packaging of claim 1, wherein the content of SiO.sub.2 is larger than 60 mol %.

13. The pharmaceutical packaging of claim 1, wherein the content of SiO.sub.2 is smaller than 70 mol %.

14. A pharmaceutical packaging comprising a glass, said glass comprising at least the following components (given in mol % on oxide basis): TABLE-US-00005 SiO.sub.2 59-84 Al.sub.2O.sub.3   7-18.5 CaO  1-25 SrO   0-6.5 BaO 0-5 ZrO.sub.2 0-3 TiO.sub.2 0-5 B.sub.2O.sub.3 0.1-1,  wherein the ratio (CaO+SrO+BaO)/Al.sub.2O.sub.3<2.8; wherein the ratio (CaO+SrO+BaO)/SiO.sub.2≦0.39; wherein the hydrolytic resistance according to DIN ISO 720 is class HGA 1; and wherein the glass, apart from unavoidable contaminations, is free of alkali oxides and of magnesium oxide.

15. The pharmaceutical packaging of claim 1, which comprises a maximum processing temperature T4 of 1350° C.

16. The pharmaceutical packaging of claim 1, wherein a weight loss according to DIN ISO 720 is smaller than 50 μg Na.sub.2O/g.

17. The pharmaceutical packaging of claim 1, wherein the hydrolytic resistance according to DIN ISO 720 is HGA1.

18. The pharmaceutical packaging of claim 1, which further comprises 0.01 to 2 mol % of refining agents.

19. The pharmaceutical packaging of claim 1, wherein a content of As.sub.2O.sub.3, Sb.sub.2O.sub.3, Cl—, F— and SO.sub.4.sup.2− is a maximum of 1.5 mol % each, wherein the content of SnO2 and CeO2 preferably is a maximum of 1 mol % each.

20. The pharmaceutical packaging of claim 1 for receiving at least one selected from a group consisting of an active pharmaceutical agent, a buffering solution within a pH-range 1-11, and water for injection purposes, said pharmaceutical packaging comprising: TABLE-US-00006 SiO.sub.2 59-84 Al.sub.2O.sub.3   7-18.5 CaO  1-25 SrO   0-6.5 BaO 0-5 ZrO.sub.2 0-3 TiO.sub.2 0-5 B.sub.2O.sub.3  0-1, wherein the ratio (CaO+SrO+BaO)/Al.sub.2O.sub.3<2.8; wherein the ratio (CaO+SrO+BaO)/SiO.sub.2≦0.39; wherein the hydrolytic resistance according to DIN ISO 720 is class HGA 1; and wherein the glass, apart from unavoidable contaminations, is free of alkali oxides and of magnesium oxide.

Description

DESCRIPTION OF PREFERRED EMBODIMENTS

EXAMPLES

[0060] In Table 1 glasses for the pharmaceutical packagings according to the invention are summarized together with their most important characteristics.

[0061] The glasses were molten by melting common raw materials within an inductively heated Pt/Rh (Pt20Rh) melting pot at 1650° C. The melting time was three to four hours. Subsequently the melt was homogenized for one hour at 1600° C. by stirring and was thereafter relieved at this temperature without stirring, giving rise to an ascending of bubbles to the surface. The melt was cooled with a defined cooling rate of 30 K/h.

[0062] All these glasses show a good hydrolytic resistance and a processing temperature T4 below 1350° C., partially substantially below that.

[0063] Comparative examples not belonging to the invention are summarized in Table 2.

TABLE-US-00002 TABLE 1 Examples (compositions in mol %) Examples B1 B2 B3 B4 B5 B6 B7 B8 B9 B10 B11 SiO.sub.2 62.6 67.1 68.4 67.1 66.8 66.7 73.3 72.4 67.5 68.7 68.5 Al.sub.2O.sub.3 11.0 10.3 11.3 10.3 10.3 9.7 11.9 11.6 10.4 10.6 10.9 MgO 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 CaO 24.4 19.9 16.0 18.8 19.8 20.7 11.9 12.7 20.0 17.4 16.3 SrO 0.0 1.6 2.2 2.2 1.9 1.9 2.0 1.0 0.0 0.0 0.0 BaO 0.0 0.0 0.0 0.0 0.0 0.0 0.0 1.5 1.1 2.2 3.5 TiO.sub.2 0.0 0.0 0.0 1.6 1.2 0.4 0.4 0.0 0.0 0.0 0.0 ZrO.sub.2 2.0 1.1 2.0 0.0 0.0 0.5 0.5 0.8 1.1 1.1 0.5 B.sub.2O.sub.3 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.3 Sum 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 (CaO + SrO + BaO)/Al.sub.2O.sub.3 2.2 2.1 1.6 2.0 2.1 2.3 1.2 1.2 1.9 1.6 1.8 (CaO + SrO + BaO)/SiO.sub.2 0.39 0.32 0.27 0.31 0.32 0.34 0.19 0.19 0.30 0.25 0.29 CTE [ppm/K] 5.15 4.84 4.49 4.87 4.87 5.03 3.82 4.02 4.82 4.61 4.7 Tg [° C.] 800 803 817 784 783 786 810 824 807 772 790 Density [g/cm.sup.3] 2.67 2.63 2.63 2.61 2.61 2.63 2.52 2.57 2.63 2.64 2.67 T13 [° C.] 802 801 820 784 785 789 844 835 802 776 795 T7,6 [° C.] 965 989 1015 972 968 968 1065 1054 989 984 1005 T4 [° C.] 1222 1274 1311 1257 1254 1250 1401 1386 1276 1290 1305 ISO 720 45.9 36.5 29.1 35.7 39.2 43.3 37.7 21.6 41.8 32.4 30.0 [μg Na.sub.2O/g] Class ISO 720 1 1 1 1 1 1 1 1 1 1 1

[0064] In Table 2 the examples V1-V3 do not fulfill the second boundary condition (CaO+SrO+BaO)/SiO.sub.2≦0.39, whereby also a hydrolytic resistance according to ISO 720 of the class 2 can be reached at most.

[0065] The pharmaceutical packagings according to the invention are in particular suitable for making pharmaceutical containers which in contact with active agents and buffering systems are chemically inert in the pH-range of 1-11 and thus are excellently suitable for storing these materials.

TABLE-US-00003 TABLE 2 Comparative examples (compositions in mol %) Comparative examples V1 V2 V3 V4 SiO.sub.2 59.1 61.0 60.7 56.0 Al.sub.2O.sub.3 9.0 8.5 7.6 16.0 MgO 5.0 5.0 5.1 9.0 CaO 25.9 24.5 25.6 18.0 SrO 0.0 0.0 0.0 0.0 BaO 0.0 0.0 0.0 0.0 TiO.sub.2 0.0 0.0 0.0 0.0 ZrO.sub.2 1.0 1.0 1.0 1.0 Sum 100.0 100.0 100.0 100.0 (CaO + SrO + BaO)/Al.sub.2O.sub.3 2.9 2.9 3.4 1.1 (CaO + SrO + BaO))/SiO.sub.2 0.44 0.40 0.42 0.32 CTE [ppm/K] 5.54 5.5 5.54 4.7 Tg [° C.] 760 764 759 788 Density [g/cm3] 2.64 2.67 2.68 2.66 T13 [° C.] 766 765 762 788 T7.6 [° C.] 931 933 927 953 T4 [° C.] 1174 1184 1175 1203 ISO 720 66.4 63.2 69.6 62.5 [μg Na.sub.2O/g] Class ISO 720 2 2 2 2

[0066] In particular the pharmaceutical containers made of the glass compositions according to the invention are suitable for the storage of active agents and buffering agents within the pH-range of 4-9 (e.g. 1 Mol of sodium dicarbonate solution NaHCO3, or 8.4%, respectively, with a pH-value of about 8).

[0067] In particular pharmaceutical containers which are made of the glasses according to the invention are suitable for the storage of active agents, buffering solutions in the pH-range of 5-7 (e.g. (1) 10 mmol citrate-buffering, pH=6.0 with 150 mmol NaCl and 0.005% Tween 20, or (2) 10 mmol phosphate-buffering, pH=7.0 with 150 mmol NaCl and 0.005% Tween 20), as well as for the storage of water for injection purposes (e.g. Sartorius ultra-pure water, rinsed through 0.2 μm-filter and having a resistance of 18.2 MΩ.Math.cm).