Delamination resistant glass containers with heat-tolerant coatings

• US 10,273,049 B2
• Filed: 06/28/2013
• Issued: 04/30/2019
• Est. Priority Date: 06/28/2012
• Status: Active Grant

• Current Assignee: Corning Incorporated
• Original Assignee: Corning Incorporated
• Inventors: Adib, Kaveh, Bookbinder, Dana Craig, Chang, Theresa, Danielson, Paul Stephen, DeMartino, Steven Edward, Drake, Melinda Ann, Fadeev, Andrei Gennadyevich, Hamilton, James Patrick, Morena, Robert Michael, Pal, Santona, Peanasky, John Stephen, Saha, Chandan Kumar, Schaut, Robert Anthony, Schiefelbein, Susan Lee, Timmons, Christopher Lee
• Primary Examiner(s): Higgins, Gerard
• Application Number:
  US13/930,647
• Publication Number:
  US 20140001143A1
• Time in Patent Office: 2,132 Days
• Field of Search: 428410, 428220, 428426, 428336, 428 3692, 428435, 428447, 428457, 428192, 428201, 428212, 428332, 428337, 428 34, 428 344, 428428, 428429, 428446, 428458, 4284735, 428134, 428141, 428179, 428189, 428190, 428191, 4281951, 428213, 428216, 428221, 428324, 428325, 428328, 428331, 428339, 428354, 428 357, 428 366, 428375, 428391, 428412, 428461, 4284744, 4284782, 428480, 428521, 428532, 428687
• 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 1/40 Details of walls other container details B65D23/00, B65D25/00
• CPC Class Codes: B65D 23/0814 characterised by the composition of the material
• 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: C03B 23/047 by drawing C03B23/091 , C03B37/025 takes precedence
• CPC Class Codes: C03C 17/005 Coating the outside
• 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: C03C 3/087 containing calcium oxide, e.g. common sheet or container glass
• CPC Class Codes: C08G 73/105 with oxygen only in the diamino moiety
• CPC Class Codes: C08G 73/1071 Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
• CPC Class Codes: C08K 5/544 containing nitrogen
• CPC Class Codes: C08L 79/08 Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
• CPC Class Codes: C08L 83/04 Polysiloxanes
• CPC Class Codes: C09D 179/08 : Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
• 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.]

Abstract

Delamination resistant glass containers with heat-tolerant coatings are disclosed. In one embodiment, a glass container may include a glass body having an interior surface, an exterior surface and a wall thickness extending from the exterior surface to the interior surface. At least the interior surface of the glass body is delamination resistant. The glass container may further include a heat-tolerant coating positioned on at least a portion of the exterior surface of the glass body. The heat-tolerant coating may be thermally stable at temperatures greater than or equal to 260° C. for 30 minutes.

Claims

1. A glass container comprising:

a glass body formed from an aluminosilicate glass composition having a Class HGA1 hydrolytic resistance when tested according to the ISO 720;

1985 testing standard, the glass body having an interior surface and an exterior surface, wherein at least the interior surface of the glass body has a delamination factor of less than or equal to 10 and a threshold diffusivity of greater than about 16 μ

m²/hr at a temperature less than or equal to 450°

C., and wherein the glass body has an interior region extending between the interior surface of the glass body and the exterior surface of the glass body, the interior region having a persistent layer homogeneity such that an extrema in the concentration of each constituent component in the interior region is greater than or equal to about 80% and less than or equal to about 120% of a bulk concentration of the same constituent component at a mid-point of the thickness of the glass body when the glass container is in an as-formed condition; and

a heat-tolerant coating bonded to at least a portion of the exterior surface of the glass body, wherein the heat-tolerant coating is thermally stable at a temperature of at least 260°

C. for 30 minutes, and wherein the heat-tolerant coating comprises a polymer;

wherein the glass container is a pharmaceutical package, the aluminosilicate glass composition comprises X mol. % of Al₂O₃ and Y mol. % of alkali oxides and a ratio Y;

X is greater than or equal to about 1 and less than or equal to about 2, the aluminosilicate glass composition comprises CaO and MgO in amounts such that a molar ratio of CaO/(CaO+MgO) is less than about 0.5, and a molar ratio of B₂O₃/(R₂O—

Al₂O₃) in the aluminosilicate glass composition is from 0 to about 0.3.

2. The glass container of claim 1, wherein the exterior surface of the glass body with the heat-tolerant coating has a coefficient of friction of less than about 0.7.

3. The glass container of claim 1, wherein the heat-tolerant coating has a mass loss of less than about 5% of its mass when heated from a temperature of 150°

C. to 350°

C. at a ramp rate of about 10°

C./minute.

4. The glass container of claim 1, wherein the interior region has a thickness T_LR of at least about 100 nm.

5. The glass container of claim 1, wherein the interior region extends from 10 nm below the interior surface of the glass body and has a thickness T_LR of at least about 100 nm.

6. The glass container of claim 1, wherein the interior surface of the glass body has a persistent surface homogeneity such that for a discrete point on the interior surface of the glass container, an extrema of the concentration of each constituent component of the glass 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 interior surface of the glass container when the glass container is in an as-formed condition.

7. The glass container of claim 6, wherein the persistent surface homogeneity extends into a wall thickness of the glass body to a depth from about 10 nm to about 50 nm from the interior surface of the glass body.

8. The glass container of claim 1, wherein the glass body has a surface region that extends from the interior surface of the glass body into a wall thickness of the glass body, the surface region having a persistent surface homogeneity.

9. The glass container of claim 8, wherein the surface region extends into a wall thickness of the glass body to a depth of at least 10 nm from the interior surface of the glass body.

10. The glass container of claim 1, wherein the heat-tolerant coating comprises a coupling agent layer.

11. The glass container of claim 10, wherein the coupling agent layer comprises at least one silane.

12. The glass container of claim 10, wherein the heat-tolerant coating further comprises a low-friction layer contacting the coupling agent layer.

13. The glass container of claim 1, wherein the heat-tolerant coating comprises a low-friction layer comprising the polymer.

14. The glass container of claim 1, wherein a light transmission through a coated portion of the glass container is greater than or equal to about 55% of a light transmission through an uncoated glass article for wavelengths from about 400 nm to about 700 nm.

15. The glass container of claim 1, wherein the glass body has at least a class S3 acid resistance according to DIN 12116 dated March 2001.

16. The glass container of claim 1, wherein the glass body has at least a class A2 base resistance according to ISO 695:

1991.

17. The glass container of claim 1, wherein the glass body has at least a type HgB2 hydrolytic resistance according to ISO 719:

1985.

18. The glass container of claim 1, wherein the glass body has a compressive stress greater than or equal to 300 MPa in at least the exterior surface of the glass body and a depth of layer of at least 30 μ

m.

19. The glass container of claim 1, wherein the polymer is selected from the group consisting of polyimides, polybenzimidazoles, polysulfones, polyetheretherketones, polyetherimides, polyamides, polyphenyls, polybenzothiazoles, polybenzoxazoles, polybisthiazoles, polyaromatic heterocyclic polymers, silsesquioxane-based polymers, and silicone resins.

20. The glass container of claim 1, wherein the aluminosilicate glass composition comprises one or more of:

Al₂O₃ in an amount of from about 5 mol. % to about 7 mol. %;

alkali oxides in an amount greater than or equal to about 8 mol. %;

Na₂O in an amount greater than or equal to 8 mol. %;

K₂O in an amount of from about 0.01 mol. % to about 3 mol. %;

alkaline earth oxides in an amount of from about 4 mol. % to about 8 mol. %;

or

CaO in an amount of from 0 mol. % to about 5 mol. %.

21. A glass container comprising:

a glass body formed from an aluminosilicate glass composition having a Class HGA1 hydrolytic resistance when tested according to the ISO 720;

1985 testing standard, the glass body having an interior surface and an exterior surface, wherein at least the interior surface of the glass body has a delamination factor of less than or equal to 10 and a threshold diffusivity of greater than about 16 μ

m²/hr at a temperature less than or equal to 450°

C., and wherein the glass body has an interior region extending from below the interior surface of the glass body and into a wall thickness of the glass body, the interior region having a persistent layer homogeneity such that an extrema in the concentration of each constituent component in the interior region is greater than or equal to about 80% and less than or equal to about 120% of a bulk concentration of the same constituent component at a mid-point of the thickness of the glass body when the glass container is in an as-formed condition; and

a heat-tolerant coating bonded to at least a portion of the exterior surface of the glass body, wherein the exterior surface of the glass body with the heat-tolerant coating has a coefficient of friction of less than about 0.7, and wherein the heat-tolerant coating comprises a polymer;

wherein the glass container is a pharmaceutical package, the aluminosilicate glass composition comprises X mol. % of Al₂O₃ and Y mol. % of alkali oxides and a ratio Y;

X is greater than or equal to about 1 and less than or equal to about 2, the aluminosilicate glass composition comprises CaO and MgO in amounts such that a molar ratio of CaO/(CaO+MgO) is less than about 0.5, and a molar ratio of B₂O₃/(R₂O—

Al₂O₃) in the aluminosilicate glass composition is from 0 to about 0.3.

22. The glass container of claim 21, wherein the heat-tolerant coating is thermally stable at a temperature of at least 260°

C. for 30 minutes.

23. The glass container of claim 21, wherein the heat-tolerant coating is thermally stable at a temperature of at least 320°

C. for 30 minutes.

24. The glass container of claim 21, wherein the interior region extends from 10 nm below the interior surface of the glass body and has a thickness T_LR of at least about 100 nm.

25. The glass container of claim 21, wherein the interior surface of the glass body has a persistent surface homogeneity such that for a discrete point on the interior surface of the glass container, an extrema of the concentration of each constituent component of the glass 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 interior surface of the glass container when the glass container is in an as-formed condition.

26. The glass container of claim 25, wherein the persistent surface homogeneity extends into a wall thickness of the glass body to a depth from about 10 nm to about 50 nm from the interior surface of the glass body.

27. The glass container of claim 21, wherein the glass body comprises an alkali aluminosilicate glass composition.

28. The glass container of claim 21, wherein the glass body is substantially free from boron and compounds containing boron.

29. The glass container of claim 21, wherein the polymer is selected from the group consisting of polyimides, polybenzimidazoles, polysulfones, polyetheretherketones, polyetherimides, polyamides, polyphenyls, polybenzothiazoles, polybenzoxazoles, polybisthiazoles, polyaromatic heterocyclic polymers, silsesquioxane-based polymers, and silicone resins.

30. The glass container of claim 21, wherein the aluminosilicate glass composition comprises one or more of:

Al₂O₃ in an amount of from about 5 mol. % to about 7 mol. %;

alkali oxides in an amount greater than or equal to about 8 mol. %;

Na₂O in an amount greater than or equal to 8 mol. %;

K₂O in an amount of from about 0.01 mol. % to about 3 mol. %;

alkaline earth oxides in an amount of from about 4 mol. % to about 8 mol. %;

or

CaO in an amount of from 0 mol. % to about 5 mol. %.