Delamination resistant glass containers with heat-tolerant coatings
Disclosed herein are delamination resistant glass pharmaceutical containers which may include a glass body having a Class HGA1 hydrolytic resistance when tested according to the ISO 720:1985 testing standard. The glass body may have an interior surface and an exterior surface. The interior surface of the glass body does not comprise a boron-rich layer when the glass body is in an as-formed condition. A heat-tolerant coating may be bonded to at least a portion of the exterior surface of the glass body. The heat-tolerant coating may have a coefficient of friction of less than about 0.7 and is thermally stable at a temperature of at least 250° C. for 30 minutes.
1. A method of making a delamination-resistant glass pharmaceutical container, the method comprising the steps of:
combining constituent elements of a glass composition into a glass melt;
forming the glass melt into a glass tube;
re-forming the glass tube into a glass pharmaceutical container having an interior surface and an exterior surface, wherein an interior surface of the glass pharmaceutical container does not comprise a boron-rich layer when the glass pharmaceutical container is in as-formed condition;
chemically strengthening the glass pharmaceutical container; and
applying a coating having a thickness of less than 100 microns to the exterior surface such that a portion of the glass pharmaceutical container with the coating has a coefficient of friction less than or equal to 0.7.
2. The method of claim 1 , further comprising the step of subjecting the glass pharmaceutical container to a depyrogenation cycle whereby the coefficient of friction does not increase by more than 30% after the depyrogenation cycle.
3. The method of claim 2 , wherein the depyrogenation cycle comprises heating the glass pharmaceutical container with the coating to a temperature of at least 250° C. for at least 30 minutes.
4. The method of claim 2 , wherein the depyrogenation cycle comprises heating the glass pharmaceutical container with the coating to a temperature of at least 250° C. for up to 72 hours.
5. The method of claim 2 , wherein the depyrogenation cycle comprises heating the glass pharmaceutical container with the coating to a temperature of from about 250° C. to about 400° C. for a time period of from about 30 minutes to about 72 hours.
6. The method of claim 1 , wherein the step of applying a coating comprises:
applying a coupling agent layer in direct contact with the exterior surface; and
applying a polymer layer in direct contact with the coupling agent layer.
7. The method of claim 1 , further comprising subjecting the glass container to a lyophilization cycle, whereby the coefficient of friction does not increase by more than 30% after the lyophilization cycle.
8. The method of claim 7 , wherein the lyophilization cycle comprises filling the glass container with a liquid that contains protein and then freezing at a temperature of −100° C., followed by water sublimation for 20 hours at −15° C. under vacuum.
9. The method of claim 1 , wherein the glass composition comprises more than or equal to 67 mol. % SiO 2 and less than or equal to about 80 mol. % SiO 2 .
10. A method of manufacturing a glass pharmaceutical container comprising:
providing a glass composition;
melting the glass composition to form a molten glass;
forming the molten glass into the glass pharmaceutical container having an interior surface and an exterior surface, wherein an interior surface of the glass pharmaceutical container does not comprise a boron-rich layer when the glass pharmaceutical container is in an as-formed condition; and
coating the exterior surface of the glass pharmaceutical container with a coating material wherein a portion of the glass pharmaceutical container comprising the coating comprises a coefficient of friction of ≤0.7, the coating material comprising a thickness of ≤100 μm.
11. The method of claim 10 , wherein the glass composition comprises, in mol. %:
SiO 2 68-80%;
Al 2 O 3 2-10%;
alkaline earth oxides 3-10%;
alkali oxides 8-15%;
SnO 2 <1.0%; and
B 2 O 3 0-5%.
12. The method of claim 10 , further comprising the step of subjecting the glass pharmaceutical container to a depyrogenation cycle whereby the coefficient of friction does not increase by more than 30% after the depyrogenation cycle.
13. The method of claim 12 , wherein the depyrogenation cycle comprises heating the glass pharmaceutical container with the coating to a temperature of at least 250° C. for at least 30 minutes.
14. The method of claim 12 , wherein the depyrogenation cycle comprises heating the glass pharmaceutical container with the coating to a temperature of at least 250° C. for up to 72 hours.
15. The method of claim 12 , wherein the depyrogenation cycle comprises heating the glass pharmaceutical container with the coating to a temperature of from about 250° C. to about 400° C. for a time period of from about 30 minutes to about 72 hours.
16. The method of claim 10 , wherein the step of applying a coating comprises:
applying a coupling agent layer in direct contact with the exterior surface; and
applying a polymer layer in direct contact with the coupling agent layer.
17. The method of claim 10 , further comprising subjecting the glass container to a lyophilization cycle, whereby the coefficient of friction does not increase by more than 30% after the lyophilization cycle.
18. The method of claim 17 , wherein the lyophilization cycle comprises filling the glass container with a liquid that contains protein and then freezing at a temperature of −100° C., followed by water sublimation for 20 hours at −15° C. under vacuum.
19. The method of claim 10 , wherein the glass composition comprises more than or equal to 67 mol. % SiO 2 and less than or equal to about 80 mol. % SiO 2 .
20. A method of manufacturing a glass pharmaceutical container comprising:
providing a glass composition;
melting the glass composition to form a molten glass;
forming the molten glass into a tube; and
converting the tube into the glass pharmaceutical container having an interior surface and an exterior surface, wherein an interior surface of the glass pharmaceutical container does not comprise a boron-rich layer when the glass pharmaceutical container is in an as-formed condition; and
coating the exterior surface of the glass pharmaceutical container with a coating material wherein a portion of the glass pharmaceutical container comprising the coating comprises a coefficient of friction of ≤0.7, the coating material comprising a thickness of ≤100 μm.
21. The method of claim 20 , wherein the glass composition comprises, in mol. %:
SiO 2 68-80%;
Al 2 O 3 2-10%;
alkaline earth oxides 3-10%;
alkali oxides 8-15%;
SnO 2 <1.0%; and
B 2 O 3 0-5%.
22. The method of claim 20 , further comprising the step of subjecting the glass pharmaceutical container to a depyrogenation cycle whereby the coefficient of friction does not increase by more than 30% after the depyrogenation cycle.
23. The method of claim 22 , wherein the depyrogenation cycle comprises heating the glass pharmaceutical container with the coating to a temperature of at least 250° C. for at least 30 minutes.
24. The method of claim 22 , wherein the depyrogenation cycle comprises heating the glass pharmaceutical container with the coating to a temperature of at least 250° C. for up to 72 hours.
25. The method of claim 22 , wherein the depyrogenation cycle comprises heating the glass pharmaceutical container with the coating to a temperature of from about 250° C. to about 400° C. for a time period of from about 30 minutes to about 72 hours.
26. The method of claim 20 , wherein the step of applying a coating comprises:
applying a coupling agent layer in direct contact with the exterior surface; and
applying a polymer layer in direct contact with the coupling agent layer.
27. The method of claim 20 , further comprising subjecting the glass container to a lyophilization cycle, whereby the coefficient of friction does not increase by more than 30% after the lyophilization cycle.
28. The method of claim 27 , wherein the lyophilization cycle comprises filling the glass container with a liquid that contains protein and then freezing at a temperature of −100° C., followed by water sublimation for 20 hours at −15° C. under vacuum.
29. The method of claim 20 , wherein the glass composition comprises more than or equal to 67 mol. % SiO 2 and less than or equal to about 80 mol. % SiO 2 .