Flame activated primer for polyolefinic coatings

• US 6,660,386 B2
• Filed: 05/21/2001
• Issued: 12/09/2003
• Est. Priority Date: 05/21/2001
• Status: Expired due to Fees

• Current Assignee: Polymer Ventures, Inc.
• Original Assignee: Polymer Ventures, Inc.
• Inventors: Haque, Shah A.
• Primary Examiner(s): Dawson, Robert
• Assistant Examiner(s): Feely, Michael J
• Application Number:
  US09/862,134
• Publication Number:
  US 20030031799A1
• Time in Patent Office: 932 Days
• Field of Search: 523/400, 523/440, 523/451, 523/457, 528/87, 528/88, 528/106, 528/116, 528/117, 528/119, 528/120, 528/121, 528/122, 528/123, 528/124, 428/413, 428/414, 428/416, 428/418, 428/500, 428/516, 428/523, 428/332, 427/409, 427/410, 427/421, 427/422, 427/386
• US Class Current: 428/414
• CPC Class Codes: B05D 1/08 Flame spraying
• CPC Class Codes: B05D 7/148 using epoxy-polyolefin systems in mono- or multilayers
• CPC Class Codes: B05D 7/54 No clear coat specified
• CPC Class Codes: C08G 59/18 Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
• CPC Class Codes: C08G 59/50 Amines
• CPC Class Codes: C08J 2363/00 Characterised by the use of epoxy resins; Derivatives of epoxy resins
• CPC Class Codes: C08J 3/243 Two or more independent types of crosslinking for one or more polymers
• CPC Class Codes: Y10T 428/26 Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
• CPC Class Codes: Y10T 428/31511 Of epoxy ether
• CPC Class Codes: Y10T 428/31515 As intermediate layer
• CPC Class Codes: Y10T 428/31522 Next to metal
• CPC Class Codes: Y10T 428/31529 Next to metal
• CPC Class Codes: Y10T 428/31855 Of addition polymer from unsaturated monomers
• CPC Class Codes: Y10T 428/31913 Monoolefin polymer
• CPC Class Codes: Y10T 428/31938 Polymer of monoethylenically unsaturated hydrocarbon

Abstract

A primer for flame sprayed polyolefin comprises an epoxy resin, preferably of low molecular weight and/or low viscosity; and an amine hardener, part of which becomes highly reactive on exposure to open flame, providing near instant cure of the composition under flame spray conditions. The invention is unique that it provides strong adhesion to steel, even where the surface preparation is less than ideal, as well as to concrete and other substrates. The primer eliminates the need to preheat the substrate. The primer has strong adhesion to the topcoat polyolefinic material, especially to a functionalized topcoat. The composition withstands open flame and does not char under polyolefin flame spray conditions, nor does it run or sag, and it is not prone to failure as it cools after the application of the polyolefin.

Claims

1. A coating system comprising

a. a primer composition, and

b. a thermoplastic coating deposited on the primer composition forming a top coat,

wherein the primer composition comprises an epoxy resin cured by a combination of at least one fast acting reactive amine curing agent which has entered into cross-linking reactions with the epoxy resin to provide the partial cure of the epoxy resin, and at least one amine curing agent which has been flame or heat activated to remove a blocking of the amine functionality and which has further caused a complete cure of the epoxy resin, by either stoichiometric reaction or catalysis.

2. A coating system as in claim 1 wherein

the thermoplastic coating comprises an olefinic coating.

3. A coating system as in claim 2 wherein

wherein the olefinic coating contains carboxyl functionality.

4. A coating system as in claim 2 wherein the olefinic coating is selected from the group consisting of a polyolefin and a poly-α

-olefin.

5. A coating system as in claim 4 wherein the polyolefin comprises a polyethylene containing an acrylic acid comonomer.

6. A coating system as in claim 1 wherein the thermoplastic coating has a thickness in the range of from about 1 mil to about 100 mils.

7. A coating system as in claim 1 wherein the thermoplastic coating is flame sprayed onto the primer.

8. A primer composition capable of being flame activated comprising

a. an epoxy resin having terminal epoxy groups,

b. a fast acting amine curing agent for reacting with terminal epoxy groups of the epoxy resin and partially curing the composition;

and

c. an amine curing agent capable of being flame activated and having blocked amine functionality for stoichiometric or catalytic reaction of the remaining portion of the terminal epoxy groups upon being activated and providing a complete cure of the curable primer compositions,

wherein a sufficient amount of the fast acting amine is present to react with in the range of from about 10% to about 90% of the terminal epoxy groups of the epoxy resin.

9. A primer composition as in claim 8 wherein the epoxy resin is Bis-A or Bis-F type.

10. A primer composition as in claim 8 wherein the amine curing agent capable of being flame activated comprises, after flame activation, a reactive curing agent, and said amine curing agent capable of being flame activated is present in adequate amount to provide a near-stoichiometric amount of active amine curing agent, to react all epoxy groups remaining in the composition after reaction with the fast acting amine curing agent.

11. A primer composition as in claim 8, wherein the amine curing agent capable of being flame activated comprises, after activation, a catalytic curing agent, and said amine curing agent capable of being flame activated is present in adequate amount to provide an amount of active amine curing agent, to react all the epoxy groups remaining in the composition after reaction with the fast acting amine curing agent near instantaneously.

12. A primer composition as in claim 8 further comprising from about 0.1 percent to about 10 percent by weight of a fire retardant.

13. An amine curing agent comprising

a. at least one fast acting amine curing agent for reactively crosslinking terminal functional groups of an epoxy resin, and

b. at least one amine curing agent capable of being flame activated and having blocked amine functionality for reacting with or catalyzing reaction of terminal epoxy groups of an epoxy resin after activation by flame.

14. An amine curing agent as in claim 13 wherein

the at least one fast acting amine curing agent comprises a polyamine, a polyamide, or a polyamidoamine having from 6 to 20 carbon atoms and comprising multiple terminal amino groups.

15. An amine curing agent as in claim 13 wherein

the at least one fast acting amine curing agent comprises meta-xylenediamine.

16. An amine curing agent as in claim 13 wherein

the at least one amine curing agent capable of being flame activated comprises multiple terminal amino groups which have been blocked by carbamate or carboxyl functional groups.

17. An amine curing agent as in claim 13 wherein the at least one amine curing agent capable of being flame activated comprises hexamethylene diamine or 4,4′

-methylenebis(cyclohexylamine) blocked by carbamate functional group.

18. An amine curing agent as in claim 13 wherein the amine curing agent capable of being flame activated comprises 2-methyl-4-ethylimidazole.

19. A primed substrate comprising

a. a substrate, and

b. a partly cured curable primer composition on the substrate, wherein said primer composition comprises

i. an epoxy resin having both reactive terminal epoxy groups and reacted terminal epoxy groups, wherein the reacted terminal epoxy groups have been reacted with a fast acting amine curing agent to provide the partial cure of the partly cured primer composition, and

ii. an amine curing agent capable of being flame activated and having blocked amine functionality for reacting with or catalyzing reaction of the reactive terminal epoxy groups of the epoxy resin upon being activated by flame so as to provide a complete and near instantaneous cure of the curable primer composition.

20. A primed substrate as in claim 19 wherein

the substrate comprises steel and the partly cured curable primer composition is on the steel at a thickness in the range of from a monolayer thickness up to about 10 mils.

21. A primed substrate as in claim 20 wherein

the substrate comprises steel and the partly cured curable primer composition is on the steel at a thickness in the range of from a monolayer thickness up to about 1 mil.

22. A primed substrate as in claim 19 wherein

the substrate comprises concrete and the partly cured curable primer composition is on the concrete at a thickness in the range of from about 1 mil to about 100 mils.

23. A primed substrate as in claim 22 wherein

the substrate comprises concrete and the partly cured curable primer composition is on the concrete at a thickness in the range of from about 5 mil to about 50 mils.

24. A method for coating a substrate, said method comprising

a) providing a substrate surface which is substantially free of loose, unsound, poorly adhered, contaminated and/or detrimental matter including oils and grease;

b) applying a layer of primer to said substrate surface, said primer comprising

i. an epoxy resin having terminal epoxy groups,

ii. a fast acting amine curing agent for reacting with a first portion of the terminal epoxy groups of the epoxy resin and partially curing the curable composition; and

iii. an amine curing agent capable of being flame activated and having blocked amine functionality for reacting with or catalyzing reaction of a second portion of the terminal epoxy groups upon being activated and providing a complete cure of the curable primer composition; and

c) flame spraying a layer of molten thermoplastic resin onto the layer of primer under conditions to activate the amine curing agent capable of being flame activated and provide a complete cure of the primer.

25. A method as in claim 24 wherein the substrate is steel which has been lightly cleaned by mechanical means other than heavy sand-blasting.

26. A method as in claim 25 wherein the substrate has some rust bloom.

27. A method as in claim 25 wherein the primer is applied to the substrate to a thickness in the range of from about a monolayer to about 1 mil by spray technique.

28. A method as in claim 26 wherein the substrate is concrete which has been nonmechanically cleaned.

29. A method as in claim 28 wherein the primer is applied to the substrate to a thickness in the range of from about 5 to about 50 mils.

30. A method as in claim 24 wherein the thermoplastic resin comprises an olefinic polymer.

31. A method as in claim 30 wherein the olefinic polymer comprises a copolymer of ethylene and an acrylic acid.

32. A method as in claim 31 wherein the epoxy resin is selected from Bis-A or Bis-F type.

33. A coated substrate comprising

a. a substrate,

b. a primer composition deposited on the substrate, and

c. a thermoplastic coating deposited on the primer composition,

wherein the primer composition comprises an epoxy resin cured by a combination of at least one fast acting reactive amine curing agent which has entered into cross-linking reactions with the epoxy resin to provide the partial cure of the epoxy resin, and

at least one amine curing agent which has been flame activated to remove a physical or electronic blocking of the amine functionality and which has further caused a complete cure of the epoxy resin, by either stoichiometric reaction or catalysis.

34. A coated substrate as in claim 33 wherein

the thermoplastic coating comprises an olefinic coating.

35. A coated substrate as in claim 34 wherein

wherein the olefinic coating contains carboxyl functionality.

36. A coated substrate as in claim 33 wherein the olefinic coating is selected from the group consisting of a polyolefin and a poly-α

-olefin.

37. A coated substrate as in claim 36 wherein the coating is polyethylene containing an acrylic acid comonomer.

38. A coated substrate as in claim 33 wherein the thermoplastic coating has a thickness in the range of from about 1 mil to about 100 mils.

39. A coated substrate as in claim 33 wherein the thermoplastic coating is flame sprayed onto the primer.