Barrier coating of an elastomer and a dispersed layered filler in a liquid carrier and coated articles

• US 6,232,389 B1
• Filed: 06/10/1999
• Issued: 05/15/2001
• Est. Priority Date: 06/09/1997
• Status: Expired due to Term

• Current Assignee: Michelin Recherche et Technique SA (Compagnie Generale DES Etablissements Michelin SCA), Inmat Inc.
• Original Assignee: Michelin Recherche et Technique SA (Compagnie Generale DES Etablissements Michelin SCA), InMat, LLC
• Inventors: Farrell, Michele, Goldberg, Harris A., Feeney, Carrie A., Grah, Michael D., Lu, Mengshi, Tannert, Klaus, Winston, Paul B., Steiner, William G.
• Primary Examiner(s): Hoke, Veronica P.
• Application Number:
  US09/329,423
• Time in Patent Office: 705 Days
• Field of Search: 427/245, 427/412.3, 524/446, 524/447, 524/448, 524/450, 524/791, 524/836, 523/166, 473/352, 473/369, 473/370, 473/378, 570/6, 573/7, 565/53
• US Class Current: 524/450
• CPC Class Codes: B60C 1/00 Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
• CPC Class Codes: B60C 1/0008 Compositions of the inner liner
• CPC Class Codes: B60C 5/14 with impervious liner or coating on the inner wall of the tyre
• CPC Class Codes: C08K 9/04 Ingredients treated with organic substances treated with macromolecular compounds C08K9/08
• CPC Class Codes: C08L 23/20 having four to nine carbon atoms
• CPC Class Codes: C08L 2666/04 Macromolecular compounds according to groups C08L7/00 - C08L49/00, or C08L55/00 - C08L57/00; Derivatives thereof
• CPC Class Codes: C08L 2666/28 Non-macromolecular organic substances
• CPC Class Codes: C08L 2666/54 Inorganic substances
• CPC Class Codes: C09D 123/20 having four to nine carbon atoms
• CPC Class Codes: C09D 123/22 Copolymers of isobutene; Butyl rubber ; Homo- or copolymers of other iso-olefines
• CPC Class Codes: C09D 123/283 Halogenated homo- or copolymers of iso-olefines

Abstract

Applications of barrier coating mixtures containing in a carrier liquid, (a) an elastomeric (preferably butyl-containing) polymer; (b) a dispersed exfoliated layered filler having an aspect ratio greater than 25; and (c) at least one surfactant, wherein the solids content of the mixture is less than 30% and the ratio of polymer (a) to filler (b) is between 20:1 and 1:1 include coated articles, which are elastomeric, e.g., sports balls and inflatable articles. Methods of manufacturing such coated products are also encompassed.

Claims

1. A coated article comprising an elastomeric substrate that contains air or a gas under pressure, and having on an interior or exterior surface of said substrate a barrier coating formed by:

(a) applying to said surface without melt processing or high shear mixing an aqueous solution comprising;

(i) an elastomeric polymer;

(ii) a dispersed exfoliated layered filler having an aspect ratio greater than 25; and

(iii) at least one surfactant,

wherein the solids content of said solution is less than 30% and the weight ratio of said polymer to said filler ranges from 20;

1 to 1;

1; and

(b) drying said solution to form said barrier coating,

wherein said dried barrier coating has a polymer to filler weight ratio, which ranges from 20;

1 to 1;

1 and wherein said coating provides at least 10-fold greater reduction in gas, vapor, and chemical permeability than a coating formed of said polymer alone.

2. The article according to claim 1 selected from the group consisting of tennis balls, basketballs, soccer balls, footballs, volley balls, racket balls, handballs, beach balls and toy balls.

3. The article according to claim 1 which is an inflated product.

4. The article according to claim 3 which is selected from the group consisting of boats, air mattresses, and inflatable beds.

5. The article according to claim 1 wherein said elastomeric substrate is capable of excluding or resisting the penetration of air, water, or other gas or vapors.

6. The article according to claim 1, wherein said polymer is in a form selected from the group consisting of a solution, a dispersion, an emulsion, a suspension and a latex.

7. The article according to claim 1 wherein said polymer is a butyl-containing polymer.

8. The article according to claim 7 wherein said butyl-containing polymer is a co-polymer of (poly)isobutylene and a second polymer, said copolymer being cured, uncured or partially cured.

9. The article according to claim 7 wherein said butyl-containing polymer is a poly(isobutylene) homopolymer.

10. The article according to claim 8 wherein said co-polymer is halogenated.

11. The article according to claim 7 wherein said co-polymer is butyl rubber.

12. The article according to claim 10, wherein said co-polymer is selected from the group consisting of bromobutyl rubber and chlorobutyl rubber.

13. The article according to claim 8 wherein said butyl-containing copolymer contains more than 50% isobutylene.

14. The article according to claim 1 wherein said polymer is present in said solution at between about 1% to about 30% by weight.

15. The article according to claim 1, wherein said filler is selected from the group consisting of bentonite, vermiculite, montmorillonite, nontronite, beidellite, volkonskoite, hectorite, saponite, laponite, sauconite, magadiite, kenyaite, ledikite, and mixtures and solutions of the above silicates.

16. The article according to claim 1 wherein said filler is vermiculite.

17. The article according to claim 1 wherein said dispersed layered filler is present in said solution at between about 1% to about 10% by weight.

18. The article according to claim 1, wherein said solution has a solids content of from about 5% to about 17% by weight.

19. The article according to claim 1 wherein said surfactant is selected from the group consisting of an emulsifier, an anti-foaming agent, a defoaming agent, a dispersing agent, a wetting agent, a leveling agent, and a thickener.

20. The article according to claim 19 wherein said thickener is a polymer containing polyvinyl alcohol.

21. The article according to claim 19 wherein said thickener is lithium chloride.

22. The article according to claim 19 wherein said solution comprises at least two surfactants, which include a wetting agent and an anti-foaming agent.

23. The article according to claim 1 wherein said solution further comprises a component selected from the group consisting of hexane, heptane, toluene, 1-methyl-2-pyrrolidinone, cyclohexanone, ethanol, methanol, other hydrocarbons, and combinations thereof.

24. The article according to claim 1 wherein said solution further comprises curative components which enhance the curing of said barrier coating on said substrate.

25. The article according to claim 1, wherein said dried coating comprises about 45% to about 95% by weight of said polymer, between about 5% to about 55% by weight said dispersed layered filler;

and between about 1.0% to about 15% by weight said surfactant, said filler in said dried coating or film having an effective aspect ratio greater than 25.

26. The article according to claim 25, wherein said filler is present in said dried coating at greater than about 5% by weight.

27. The article according to claim 25, wherein said filler in said dried coating having an effective aspect ratio greater than 50.

28. The article according to claim 25, wherein said filler in said dried coating having an effective aspect ratio greater than 100.

29. The article according to claim 1 wherein said solution is aqueous, said polymer is a butyl-containing polymer latex, said filler is vermiculite having an aspect ratio about 1000 or greater;

and the solids content of said solution is less than 17% by weight.

30. The article according to claim 29, wherein said solution has a solids content of between about 5 to about 15% by weight, and said dried barrier coating comprises between about 65% to about 90% by weight said butyl-containing polymer, between about 10% to about 35% by weight said vermiculite filler, and between about 1.0% to about 15% by weight said surfactant, said filler in said dried coating having an effective aspect ratio of greater than 25.

31. The article according to claim 1 wherein said dried barrier coating comprises about 45% to about 95% by weight of an elastomeric polymer, between about 5% to about 55% by weight of a dispersed exfoliated layered filler;

and between about 1.0% to about 15% by weight of said surfactant, said filler in said dried coating or film having an effective aspect ratio greater than 25, wherein said dried coating reduces the gas, vapor or chemical permeability of said article greater than 10fold the permeability of said substrate coated with said polymer alone.

32. The article according to claim 31 wherein said substrate is flexible or elastomeric and said coating maintains its permeability after repeated mechanical loading and elongation up to about 10% of said substrate.

33. A method of manufacturing an article comprising an elastomeric substrate that contains air or another gas under pressure, comprising:

(a) applying directly on an interior or exterior surface of said substrate a barrier coating mixture, wherein said coating is formed by applying to said surface without melt processing an aqueous solution comprising;

(i) an elastomeric polymer;

(ii) a dispersed exfoliated layered filler having an aspect ratio greater than 25; and

(iii) at least one surfactant,

wherein the solids content of said solution is less than about 30% and the weight ratio of said polymer to said filler ranges from 20;

1 to 1;

1; and

(b) drying said solution to a barrier coating,

wherein said dried barrier coating has a weight ratio of polymer to filler, which ranges from about 20;

1 to about 1;

1 and wherein said coating provides at least 10-fold greater reduction in gas, vapor, and chemical permeability than a coating formed of said polymer alone.

34. The method according to claim 33 wherein said article is selected from the group consisting of tennis balls, basketballs, soccer balls, footballs, volley balls, racket balls, handballs, beach balls and toy balls.

35. The method according to claim 33 wherein said article is selected from the group consisting of an inflated products selected from the group consisting of boats, air mattresses, and inflatable beds.

36. A sports ball comprising an elastomeric substrate that contains air or a gas under pressure, and having on an interior or exterior surface of said ball or at the interface of said surfaces a barrier coating formed by applying to said surface without melt processing an aqueous solution comprising:

(a) an elastomeric polymer;

(b) a dispersed exfoliated layered filler having an aspect ratio greater than 25; and

(c) at least one surfactant,

wherein the solids content of said solution is less than about 30% and the weight ratio of said polymer to said filler ranges from 20;

1 to 1;

1.