Method of forming a coating on an inner surface

• US 6,149,982 A
• Filed: 10/05/1999
• Issued: 11/21/2000
• Est. Priority Date: 02/16/1994
• Status: Expired due to Term

• Current Assignee: The Coca-Cola Company
• Original Assignee: The Coca-Cola Company
• Inventors: Plester, George
• Primary Examiner(s): PIANALTO, BERNARD D
• Application Number:
  US09/412,788
• Time in Patent Office: 413 Days
• Field of Search: 427/491, 427/171, 427/235, 427/237, 427/238, 427/255.23, 427/255.6, 427/296, 427/322, 427/350, 427/371, 427/534, 427/536, 427/551, 427/553, 427/569, 427/575
• US Class Current: 427/491
• CPC Class Codes: B05D 1/62 Plasma-deposition of organic layers plasma deposition in general C23C14/00, C23C16/00
• CPC Class Codes: C23C 16/045 Coating cavities or hollow spaces, e.g. interior of tubes; Infiltration of porous substrates

Abstract

Plasma assisted polymerization and deposition of a very thin inner surface coating in a plastic or metal container without an undesirable increase in container surface temperature is provided to change the surface properties of the internal plastic surface of a container by reaction of the surface with a reactive gas which has been energized to produce a plasma or the surface is activated by a plasma of reactive gas so that it becomes receptive to a further surface reaction. It involves locating the container in an enclosure, inserting means for feeding a reactant gas into the container, selectively controlling the pressure inside the enclosure and inside of the container, cleaning a surface of the container to be coated in situ, pretreating the surface to be coated for enabling a polymer coating subsequently deposited thereon to secure proper adhesion between the coating material and the container material, feeding a reactant gas of predetermined constituency and having barrier properties into the container, generating a plasma of said reactant gas and depositing a relatively thin polymer coating on the surface to be coated, and performing a post polymerization treatment on said polymer coating for eliminating residual monomers and other polymer extractables in situ following deposition of said polymer coating.

Claims

1. In a method of forming a polymer coating on an inner surface of a heat-sensitive, or heat-sensitive, oriented polymer container, comprising,

locating said heat-sensitive or heat-sensitive, oriented polymer container in an enclosure;

controlling the environment within the enclosure an the inside of the container;

feeding reactant gas into the container, said reactant gas fed into the container when reacted, and when said polymer coating is chemically bonded on said container, providing barrier properties including resistance to absorption of liquids or gases beyond the surface of said coating; and

generating a plasma from the reactant gas fed into the container;

the improvement comprising;

controlling the environment by controlling a first pressure inside the enclosure, and independently controlling a second pressure inside of the container, the second pressure being controlled to avoid pressures which permit the formation of plasma in the enclosure outside of the container;

wherein polymer orientation and flexibility of said container is maintained by said method of forming said polymer coating on said surface of said container.

2. The method of claim 1 wherein the step of generating comprises:

generating the plasma of said reactant gas without the presence of silicon-containing gas in sufficient quantities to effect the barrier properties, inside said container to form a cross-linked, stretchable, organic, polymer coating having said barrier properties on the surface to be coated, said polymer coating being present in an amount so as to not contaminate a new container comprising recycled material from said heat-sensitive or heat-sensitive oriented polymer container.

3. The method of claim 1 wherein the step of controlling the environment comprises cleaning in-situ the inner surface of the said container to be coated.

4. The method of claim 3 wherein said cleaning comprises feeding a reactant gas of predetermined constituency and having cleaning properties into said container and generating a plasma thereof.

5. The method of claim 1 wherein the step of controlling the environment comprises pretreating the surface to be coated for enabling the polymer coating to be chemically bonded to the inner surface of said container.

6. The method of claim 5 wherein said pretreating comprises feeding a reactant gas of predetermined constituency and having surface activation properties into said container and generating a plasma thereof for producing free radicals for enhancing coating adhesion to the surface to be coated.

7. The method of claim 1 wherein the step of controlling the environment comprises steps of:

cleaning in-situ the inner surface of the said container to be coated; and

pretreating the surface to be coated for enabling the polymer coating to be chemically bound to the inner surface of said container.

8. The method of claim 7 wherein said cleaning comprises feeding a reactant gas of predetermined constituency and having cleaning properties into said container and generating a plasma thereof.

9. The method of claim 7 wherein said pretreating comprises feeding a reactant gas of predetermined constituency and having surface activation properties into said container and generating a plasma thereof for producing free radicals for enhancing coating adhesion to the surface to be coated.

10. The method of claim 7 further comprising:

pretreating the surface to be coated by feeding a second reactant gas of the mixture having surface activation properties into said container and generating a second plasma thereof for producing free radicals on the surface to be coated;

feeding a third reactant gas of the mixture into the container which when deposited has barrier properties; and

generating a third plasma of said third reactant gas, and forming the cross-linked, stretchable, organic, polymer coating on the surface to be coated.

11. The method of claim 1 wherein the generating of a plasma comprises the use of microwaves, of relatively high frequency AC energy or a DC discharge.

12. The method of claim 1 wherein said post polymerization treatment comprises applying electromagnetic energy to said polymer coating from a relatively high energy source.

13. The method of claim 1 wherein said post polymerization treatment comprises feeding a reactant gas of predetermined constituency into said container and generating a plasma.

14. The method of claim 1 wherein said depositing comprises depositing a polymer coating having a thickness ranging between 25 nm and 1500 nm whereby transparency, flexibility and relative ease of elimination of residual monomers and polymer extractables are provided.

15. The method of claim 1 comprising said container comprising a plastic container.

16. The method of claim 1 comprising said container comprising a narrow-mouthed plastic container.

17. The method of claim 1 comprising a narrow-mouthed container formed from polyethylene terephthalate.

18. The method of claim 1 further comprising:

pretreating the surface to be coated by feeding a second reactant gas of the mixture having surface activation properties into said container and generating a second plasma thereof for producing free radicals on the surface to be coated;

feeding a third reactant gas of the mixture into the container which when deposited has barrier properties; and

generating a third plasma of said third reactant gas, and forming the cross-linked, stretchable, organic, polymer coating on the surface to be coated.

19. The method of claim 18 wherein the second reactant gas is the same as said reactant gas, and said third reactant gas is different from said second reactant gas.

20. The method of claim 18 wherein said second reactant gas is different from said reactant gas, and the third reactant gas is different from both said reactant gas and the second reactant gas.

21. The method of claim 1 wherein the step of controlling the environment comprises applying a vacuum to the enclosure and the inside of the container.

22. The method of claim 1 wherein the reactant gas is a single gas.

23. The method of claim 1 wherein the reactant gas is a mixture of two or more reactant gases.

24. The method of claim 1 further including the step of performing a post polymerization treatment on said polymer coating for eliminating residual monomers or polymer extractables in-situ following deposition of said polymer coating.

25. The method of claim 24 wherein the independent control of the first and second pressures is performed by providing separate control valves in fluid communication with the enclosure and inside of the container, respectively, and separate controllable pressure sources in fluid communication with each separate control valve.

26. The method of claim 1 wherein the independent control of the first and second pressures is performed by providing separate control valves in fluid communication with the enclosure and inside of the container, respectively, and separate controllable pressure sources in fluid communication with each separate control valve.