Glass containers with delamination resistance and improved damage tolerance

• US 10,307,334 B2
• Filed: 07/21/2017
• Issued: 06/04/2019
• Est. Priority Date: 11/30/2012
• Status: Active Grant

• Current Assignee: Corning Incorporated
• Original Assignee: Corning Incorporated
• Inventors: Chang, Theresa, Danielson, Paul Stephen, DeMartino, Steven Edward, Fadeev, Andrei Gennadyevich, Morena, Robert Michael, Pal, Santona, Peanasky, John Stephen, Schaut, Robert Anthony, Timmons, Christopher Lee, Venkataraman, Natesan, Verkleeren, Ronald Luce
• Primary Examiner(s): Higgins, Gerard
• Application Number:
  US15/656,634
• Publication Number:
  US 20170320773A1
• Time in Patent Office: 683 Days
• CPC Class Codes: A61J 1/065 Rigid ampoules, e.g. glass ampoules
• CPC Class Codes: A61J 1/1468 Containers characterised by specific material properties
• CPC Class Codes: B32B 17/06 comprising glass as the main or only constituent of a layer, next to another layer of a specific material
• CPC Class Codes: B65D 1/0207 characterised by material, e.g. composition, physical features
• CPC Class Codes: B65D 1/0215 multilayered B65D81/3837 takes precedence
• CPC Class Codes: B65D 1/40 Details of walls other container details B65D23/00, B65D25/00
• CPC Class Codes: B65D 23/02 Linings or internal coatings
• CPC Class Codes: B65D 23/0814 characterised by the composition of the material
• CPC Class Codes: B65D 23/0821 consisting mainly of polymeric materials B65D23/0828 takes precedence
• CPC Class Codes: B65D 25/14 Linings or internal coatings of containers made by folding or erecting blanks made of paper B65D5/56 ; linings for domestic water storage heaters F24H1/183
• CPC Class Codes: B65D 25/34 Coverings or external coatings of containers made by folding or erecting blanks made of paper B65D5/62; for bottles or jars B65D23/08; wrappers B65D65/00
• CPC Class Codes: B65D 65/42 Applications of coated or impregnated materials
• CPC Class Codes: C03B 23/04 Re-forming tubes or rods
• CPC Class Codes: C03C 15/02 for making a smooth surface
• CPC Class Codes: C03C 17/005 Coating the outside
• CPC Class Codes: C03C 17/22 with other inorganic material C03C17/34, C03C17/44 take precedence
• CPC Class Codes: C03C 17/30 with silicon-containing compounds
• CPC Class Codes: C03C 17/32 with synthetic or natural resins C03C17/30 takes precedence
• CPC Class Codes: C03C 17/3405 with at least two coatings of organic materials C03C17/36, C03C17/42 take precedence
• CPC Class Codes: C03C 17/42 at least one coating of an organic material and at least one non-metal coating
• CPC Class Codes: C03C 21/002 : to perform ion-exchange between alkali ions C03C21/005 takes precedence
• CPC Class Codes: C03C 2217/78 : Coatings specially designed to be durable, e.g. scratch-resistant
• CPC Class Codes: C03C 2218/111 : by dipping, immersion
• CPC Class Codes: C09D 179/08 : Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
• CPC Class Codes: Y10T 428/13 : Hollow or container type article [e.g., tube, vase, etc.]
• CPC Class Codes: Y10T 428/131 : Glass, ceramic, or sintered, fused, fired, or calcined metal oxide or metal carbide containing [e.g., porcelain, brick, cement, etc.]
• CPC Class Codes: Y10T 428/1317 : Multilayer [continuous layer]
• CPC Class Codes: Y10T 428/24802 : Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
• CPC Class Codes: Y10T 428/315 : Surface modified glass [e.g., tempered, strengthened, etc.]

Abstract

In embodiments, a delamination resistant glass pharmaceutical package includes a glass body formed from a Type 1 Class glass composition according to ASTM Standard E438-92, the glass body having a wall portion with an inner surface and an outer surface. The glass body may have at least a class A2 base resistance or better according to ISO 695, at least a type HGB2 hydrolytic resistance or better according to ISO 719 and Type 1 chemical durability according to USP <660>. An interior region of the glass body may extend from about 10 nm below the inner surface and have a persistent layer homogeneity. The glass body may also have a surface region extending over the inner surface and having a persistent surface homogeneity such that the glass body is resistant to delamination.

Claims

1. A delamination resistant glass pharmaceutical package comprising:

a glass body formed from a Type 1 glass composition according to ASTM Standard E438-92(2011), the glass body having a wall portion with an inner surface and an outer surface, wherein the glass body forms the inner surface of the glass pharmaceutical package, wherein the glass pharmaceutical package does not comprise a boron-rich layer on the inner surface of the glass body, and wherein the glass body is formed from a glass tube;

the glass body has at least a class A2 base resistance or better according to ISO 695, at least a type HGB2 hydrolytic resistance or better according to ISO 719 and Type 1 chemical durability according to USP <

660>

;

an interior region extending from about 10 nm below the inner surface and having a persistent layer homogeneity such that an extrema in a layer concentration of each constituent component of the glass composition in the interior region is greater than or equal to about 80% and less than or equal to about 120% of a concentration of the same constituent component in the glass composition at the mid-point of the thickness of the glass body when the glass body is in an as-formed condition; and

a surface region extending over the inner surface and having a persistent surface homogeneity such that the glass body is resistant to delamination such that for a discrete point on the inner surface of the glass body, an extrema of a surface concentration of each constituent component of the glass composition in the surface region at the discrete point is greater than or equal to about 70% and less than or equal to about 130% of the same constituent component in the surface region at any second discrete point on the inner surface of the glass body when the glass body is in an as-formed condition.

2. The delamination resistant glass pharmaceutical package of claim 1, wherein the interior region has a thickness T_LR of at least about 100 nm.

3. The delamination resistant glass pharmaceutical package of claim 1, wherein a depth of the surface region is at least about 10 nm.

4. The delamination resistant glass pharmaceutical package of claim 1, wherein a depth of the surface region is at least about 50 nm.

5. The delamination resistant glass pharmaceutical package of claim 1, wherein the glass body was formed at a temperature greater than or equal to 1100°

C. and less than or equal to about 1650°

C.

6. The delamination resistant glass pharmaceutical package of claim 1, wherein the glass body was formed under processing conditions which mitigated vaporization of species in the glass as compared with processing conditions comprising higher temperatures or faster forming speeds.

7. The delamination resistant glass pharmaceutical package of claim 1, wherein the glass body was formed under processing conditions which imparted a uniform temperature history to the inner surface.

8. The delamination resistant glass pharmaceutical package of claim 1, wherein the persistent layer homogeneity of the glass body is determined by dynamic secondary ion mass spectroscopy.

9. The delamination resistant glass pharmaceutical package of claim 1, wherein the glass body was formed from a glass composition which was not phase separated.

10. The delamination resistant glass pharmaceutical package of claim 1, wherein the glass body was formed from a glass composition that was substantially free from species which significantly volatilize at temperatures that correspond to the glass composition having a viscosity in a range from about 200 poise to about 100 kilopoise.

11. The delamination resistant glass pharmaceutical package of claim 1, wherein the glass body is ion-exchange strengthened.

12. The delamination resistant glass pharmaceutical package of claim 1, wherein the glass body has a delamination factor less than or equal to 10.

13. The delamination resistant glass pharmaceutical package of claim 1, wherein

the surface region extends over the inner surface of the glass body to a depth from about 10 nm to about 50 nm from the inner surface of the glass body.

14. The delamination resistant glass pharmaceutical package of claim 13, wherein:

the interior region extends from about 10 nm below the inner surface of the glass body into the thickness of the body and having a thickness T_LR of at least about 100 nm, wherein an extrema in a layer concentration of each constituent component of glass composition in the interior region is greater than or equal to about 80% and less than or equal to about 120% of a concentration of the same constituent component in the glass composition at the mid-point of a thickness of the glass body when the glass body is in an as-formed condition.

15. The delamination resistant glass pharmaceutical package of claim 1, wherein

the interior region extends from about 10 nm below the inner surface of the glass body into the thickness of the glass body and having a thickness T_LR of at least about 100 nm.

16. The delamination resistant glass pharmaceutical package of claim 1, wherein the glass pharmaceutical package comprises one or both of a compressive stress layer or a lubricous coating.

17. A delamination resistant glass pharmaceutical package comprising:

a glass body formed from an ion-exchangeable Type 1 glass composition according to ASTM Standard E438-92(2011), the glass body having a wall portion with an inner surface, an outer surface, and having a thickness with a mid-point therebetween, wherein the glass body forms the inner surface of the glass pharmaceutical package, wherein the glass pharmaceutical package does not comprise a boron-rich layer on the inner surface of the glass body, and wherein the glass body is formed from a glass tube;

the glass body has at least a class A2 base resistance or better according to ISO 695, at least a type HGB2 hydrolytic resistance or better according to ISO 719 and Type 1 chemical durability according to USP <

660>

;

an interior region extending from about 10 nm below the inner surface of the glass body into a thickness of the glass body and having a thickness T_LR of at least about 100 nm, wherein an extrema in a layer concentration of each constituent component of the glass composition in the interior region is within ±

20% of a concentration of the same constituent component in the glass composition at the mid-point of the thickness the glass body when the glass body is in an as-formed condition; and

a surface region extending over the entire inner surface of the glass body to a depth of about 10 nm from the inner surface of the glass body, wherein, for a discrete point on the inner surface of the glass body, an extrema of a surface concentration of each constituent component in the surface region at the discrete point is within ±

30% of a concentration of the same constituent component in the surface region at any second discrete point on the inner surface of the glass body when the glass body is in an as-formed condition.

18. The delamination resistant glass pharmaceutical package of claim 17, wherein the extrema in the layer concentration of each constituent component in the interior region is greater than or equal to about 90% and less than or equal to about 110% of a concentration of the same constituent component at the mid-point.

19. The delamination resistant glass pharmaceutical package of claim 17, wherein the extrema of the surface concentration of each constituent component of the glass composition in the surface region at the discrete point is greater than or equal to about 85% and less than or equal to about 115% of the same constituent component in the surface region at any second discrete point on the inner surface when the glass body is in an as-formed condition.

20. The delamination resistant glass pharmaceutical package of claim 17, wherein the glass body has a delamination factor less than or equal to 10.

21. The delamination resistant glass pharmaceutical package of claim 17, wherein the glass body was formed under processing conditions which mitigated vaporization of species in the glass as compared with processing conditions comprising higher temperatures or faster forming speeds.

22. The delamination resistant glass pharmaceutical package of claim 17, wherein the glass body was formed under processing conditions which imparted a uniform temperature history to the inner surface.

23. The delamination resistant glass pharmaceutical package of claim 17, wherein the glass body was formed from a glass composition which was not phased separated.

24. The delamination resistant glass pharmaceutical package of claim 17, wherein the glass pharmaceutical package comprises one or both of a compressive stress layer or a lubricous coating.

25. A delamination resistant glass pharmaceutical package comprising:

a glass body formed from a Type 1 glass composition according to ASTM Standard E438-92(2011), the glass body having a wall portion with an inner surface, an outer surface, and having a thickness with a mid-point therebetween and comprising a wall portion that transitions to a floor portion through a heel portion, wherein the glass body forms the inner surface of the glass pharmaceutical package, wherein the glass pharmaceutical package does not comprise a boron-rich layer on the inner surface of the glass body, and wherein the glass body is formed from a glass tube;

the glass body has at least a class A2 base resistance or better according to ISO 695, at least a type HGB2 hydrolytic resistance or better according to ISO 719 and Type 1 chemical durability according to USP <

660>

; and

a surface region extending over at least the inner surface and having a depth extending from the inner surface of the glass container into the thickness of the glass body, the surface region having a persistent surface homogeneity such that that for a discrete point on the inner surface of the glass body, an extrema of a surface concentration of each constituent component of the glass composition in the surface region at the discrete point is greater than or equal to about 70% and less than or equal to about 130% of the same constituent component in the surface region at any second discrete point on the inner surface of the glass body when the glass body is in an as-formed condition.

26. The delamination resistant glass pharmaceutical package of claim 25, wherein the glass pharmaceutical package comprises one or both of a compressive stress layer or a lubricous coating.