Laboratory vessel having hydrophobic coating and process for manufacturing same

• US 5,853,894 A
• Filed: 02/03/1997
• Issued: 12/29/1998
• Est. Priority Date: 02/03/1997
• Status: Expired due to Term

• Current Assignee: Cytonix LLC (Thermo Fisher Scientific Incorporated)
• Original Assignee: Cytonix Corporation (Thermo Fisher Scientific Incorporated)
• Inventors: Brown, James F.
• Primary Examiner(s): DUDASH, DIANA L
• Application Number:
  US08/795,316
• Time in Patent Office: 694 Days
• Field of Search: 427/2.1, 427/2.3, 427/2.13, 427/393.4, 427/393.5, 427/407.1, 427/412.3, 427/412.1, 427/412.5, 427/375, 427/2.11, 427/386, 427/265, 427/379, 422/100, 422/102, 422/292, 422/99, 422/919, 422/922, 422/936, 422/942, 436/810, 436/809, 428/444.8, 428/422, 428/409, 428/446, 428/35.7, 428/36.9, 428/426, 435/287, 435/296, 435/310, 526/255, 523/168, 523/169, 523/400, 523/175
• US Class Current: 428/422
• CPC Class Codes: B01L 3/50 Containers for the purpose of retaining a material to be analysed, e.g. test tubes devices for taking samples of blood A61B5/15
• CPC Class Codes: C08L 2205/18 Spheres
• 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 2666/14 Macromolecular compounds according to C08L59/00 - C08L87/00; Derivatives thereof
• CPC Class Codes: C08L 2666/28 Non-macromolecular organic substances
• CPC Class Codes: C08L 2666/54 Inorganic substances
• CPC Class Codes: C08L 27/18 Homopolymers or copolymers or tetrafluoroethene
• CPC Class Codes: C09D 127/18 Homopolymers or copolymers of tetrafluoroethene
• CPC Class Codes: C09D 133/16 Homopolymers or copolymers of esters containing halogen atoms
• CPC Class Codes: Y10S 436/809 Multifield plates or multicontainer arrays
• CPC Class Codes: Y10S 436/81 Tube, bottle, or dipstick
• CPC Class Codes: Y10T 428/31 Surface property or characteristic of web, sheet or block
• CPC Class Codes: Y10T 428/31544 Addition polymer is perhalogenated
• CPC Class Codes: Y10T 428/31587 Hydrocarbon polymer [polyethylene, polybutadiene, etc.]

Abstract

Laboratory vessels are coated on an operational surface thereof with a hydrophobic coating polymer or reactive monomer to form a coating having an exposed surface populated with 30% by area or more terminal trifluoromethyl groups. Laboratory vessels coated with such coating solutions are provided having extremely low surface energies and high resistance to solvent attack. Methods of forming hydrophobic coatings on laboratory vessels are also provided and include methods of forming exposed coating surfaces having populations of from about 30% by area to 100% by area trifluoromethyl groups. The hydrophobic coatings may be prepared from solutions, suspensions or powdered materials containing a fluoroalkyl ethylenically unsaturated monomer substantially free of any crosslinking, having from about 3 to about 20 carbon atoms, and containing at least one terminal trifluoromethyl group, or containing a polymerization product of such a monomer. The trifluoromethyl containing component may instead be preinjected or coinjected onto a surface of a molded vessel.

Claims

1. A laboratory vessel, said vessel comprising a vessel material having a surface intended to contact a liquid and a coating applied to at least a portion of the surface, wherein said coating comprises the polymerization product of at least one substantially non-branched fluorinated monomer, said fluorinated monomer having from about 3 to about 20 carbon atoms and at least one terminal trifluoromethyl group, said coating comprising a coating surface having a surface area populated with 30% by area or more trifluoromethyl groups and a surface energy of about 22 dynes/cm or lower at 20°

C.

2. A laboratory vessel as defined in claim 1, wherein said coating comprises a polymerization product of a perfluoroalkyl ethylenically unsaturated monomer.

3. A laboratory vessel as defined in claim 1, wherein said coating consists essentially of a polymerization product of a perfluoroalkyl ethylenically unsaturated monomer.

4. A laboratory vessel as defined in claim 1, wherein said coating comprises a polymerization product of at least one member selected from the group consisting of perfluorohexyl ethylenically unsaturated monomers, perfluoroheptyl ethylenically unsaturated monomers, perfluorooctyl ethylenically unsaturated monomers, perfluorononyl ethylenically unsaturated monomers, perfluorodecyl ethylenically unsaturated monomers, perfluoroundecyl ethylenically unsaturated monomers, and perfluorododecyl ethylenically unsaturated monomers.

5. A laboratory vessel as defined in claim 1, wherein said coating consists essentially of a polymerization product of at least one member selected from the group consisting of perfluorohexyl methacrylate, perfluorohexyl acrylate, perfluoroheptyl methacrylate, perfluorooctyl methacrylate, perfluorononyl methacrylate, perfluorodecyl methacrylate, perfluoroundecyl methacrylate and perfluorododecyl methacrylate.

6. A laboratory vessel as defined in claim 1, wherein said fluorinated monomer is substantially non-branched and has a carbon chain length of from about 6 to about 12 atoms, and said coating has an exposed surface area populated with 50% by area or more trifluoromethyl groups and a surface energy of about 15 dynes/cm or lower at 20°

C.

7. A laboratory vessel as defined in claim 1, wherein said vessel comprises polypropylene.

8. A laboratory vessel as defined in claim 1, wherein said vessel comprises silicon.

9. A laboratory vessel as defined in claim 1, wherein said vessel is a member selected from the group consisting of pipette tips, microcentrifuge tubes, vials, syringes, microtiter plates, microscope slides, microscope slide assemblies, sample chambers for analytical devices, and tubing.

11. A laboratory vessel as defined in claim 1, wherein said surface area is populated with from about 50% by area to 100% by area trifluoromethyl groups and exhibits a surface energy of about 15 dynes/cm or lower at 20°

C.

12. A laboratory vessel as defined in claim 1, wherein said surface area is populated with at least about 80% by area trifluoromethyl groups and exhibits a surface energy of less than about 10 dynes/cm at 20°

C.

13. A laboratory vessel as defined in claim 1, wherein said coating further comprises the polymerization product of an epoxy monomer, said polymerization product of said epoxy monomer comprising from about 20% by weight to about 95% by weight of said coating.

14. A laboratory vessel as defined in claim 1, wherein said vessel comprises a tubular body having an interior sidewall and a closed lower end having an interior surface, said coating is formed on said interior sidewall, and said interior surface of said closed lower end is substantially free of said coating.

26. A laboratory vessel as defined in claim 13, wherein said epoxy monomer has a functionality of greater than 3 and an epoxy equivalent weight of less than 250.

34. A laboratory vessel as claimed in claim 1, wherein said vessel comprises a pipette tip or a microcentrifuge tube.

37. A laboratory vessel as claimed in claim 1, wherein said coating further comprises the polymerization product of at least one functional monomer selected from the group consisting of acrylate monomers, silicone monomers and urethane monomers.

10. A laboratory vessel, said vessel comprising a vessel material having a surface intended to contact a liquid and a coating applied to at least a portion of the surface, wherein said coating comprises the polymerization product of at least one fluorinated monomer, said fluorinated monomer having from about 3 to about 20 carbon atoms and at least one terminal trifluoromethyl group, said coating having a surface area populated with 30% by area or more trifluoromethyl groups, and a surface energy of about 22 dynes/cm or lower at 20°

C., and further comprising a micropowder which provides a rough surface to said coating.

15. A laboratory vessel, said vessel comprising a vessel material having a surface intended to contact a liquid, a first coating and a second coating, said first coating being applied to at least a portion of the surface, wherein said first coating comprises the polymerization product of at least one fluorinated monomer, said fluorinated monomer having from about 3 to about 20 carbon atoms and at least one terminal trifluoromethyl group, said first coating having a surface area populated with 30% by area or more trifluoromethyl groups, and a surface energy of about 22 dynes/cm or lower at 20°

C., said second coating comprising the polymerization product of a second fluorinated monomer, said second fluorinated monomer having from about 3 to about 20 carbon atoms, at least one terminal trifluoromethyl group, and a micropowder which provides said second coating with a rough surface, said second coating having a surface area populated with 30% by area or more trifluoromethyl groups and a surface energy of about 22 dynes/cm or lower at 20°

C., wherein the second coating forms a sample retaining barrier on said surface for retaining an aqueous sample within said barrier, and said first coating is substantially free of surface roughness and surrounds the second coating.

16. A process for coating a laboratory vessel with a hydrophobic material comprising a polymerization product of a fluorinated monomer, said process comprising the steps of:

providing a laboratory vessel, said vessel having a surface intended to contact a liquid;

applying a first coating solution or suspension to at least a portion of the surface to form a coating on said surface, said coating solution or suspension comprising a polymerization product of a substantially non-branched fluorinated monomer having from about 3 to about 20 carbon atoms and at least one terminal trifluoromethyl group, said coating comprising a coating surface having a surface area populated with at least about 30% by area trifluoromethyl groups and a surface energy of about 22 dynes/cm or lower at 20°

C., said coating solution or suspension further comprising a fluorinated fluorocarbon solvent; and

removing solvent from the coated surface to form a dried hydrophobic coating.

17. The process defined in claim 16, further comprising the step of diluting said first coating solution or suspension with a fluorinated fluorocarbon solvent and applying the diluted solution or suspension to the surface of said vessel, the diluted coating solution or suspension having a solids content of said product of from about 0.01% by weight to about 2% by weight.

19. The process defined in claim 16, wherein said container is a member selected from the group consisting of pipette tips, microcentrifuge tubes, vials, syringes, microtiter plates, microscope slides, microscope slide assemblies, sample chambers for analytical devices, and tubing.

20. The process defined in claim 16, wherein said polymerization product comprises a polyperfluoroalkyl polymer.

22. The process defined in claim 16, wherein said coating solution or suspension further comprises from about 20% by weight to about 95% by weight of an epoxy monomer having a functionality of about 3 or greater and an epoxy equivalent weight of less than 250, said epoxy monomer increasing the chemical resistance of said coating.

35. The process defined in claim 16, wherein said vessel comprises a pipette tip or a microcentrifuge tube.

18. A process for coating a laboratory vessel with a hydrophobic material comprising a polymerization product of a fluorinated monomer, said process comprising the steps of:

providing a laboratory vessel, said vessel having a surface which contacts a liquid;

applying a first coating solution or suspension to at least a portion of the surface to form a coating on said surface, said coating solution or suspension comprising a polymerization product of a fluorinated monomer having from about 3 to about 20 carbon atoms and at least one terminal trifluoromethyl group, said coating having a surface area populated with at least about 30% by area trifluoromethyl groups and a surface energy of about 22 dynes/cm or lower at 20°

C. said coating solution or suspension further comprising a fluorinated fluorocarbon solvent;

removing solvent from the coated surface to form a dried hydrophobic coating; and

subsequently applying a second coating solution or suspension on at least a portion of said surface of said vessel to form a second coating, and removing solvent from the second coating, said second coating solution or suspension being different from said first solution or suspension and comprising a polymerization product of a fluorinated monomer having from about 3 to about 20 carbon atoms and at least one terminal trifluoromethyl group, said second coating comprising a surface having a surface area populated with 30% by area or more trifluoromethyl groups and a surface energy of about 22 dynes/cm or lower at 20°

C.

21. A process for coating a laboratory vessel with a hydrophobic material comprising a polymerization product of a fluorinated monomer, said process comprising the steps of:

providing a laboratory vessel, said vessel having a surface which contacts a liquid;

applying a first coating solution or suspension to at least a portion of the surface to form a coating on said surface, said coating solution or suspension comprising a polymerization product of a fluorinated monomer having from about 3 to about 20 carbon atoms and at least one terminal trifluoromethyl group, a micropowder which provides a rough surface to said coating, and a fluorinated fluorocarbon solvent, said coating having a surface area populated with at least about 30% by area trifluoromethyl groups and a surface energy of about 22 dynes/cm or lower at 20°

C.; and

removing solvent from the coated surface to form a dried hydrophobic coating.

23. A process for coating a laboratory vessel with a hydrophobic material comprising a polymerization product of a fluorinated monomer, said process comprising the steps of:

providing a laboratory vessel, said vessel having a surface which comes in contact with a liquid;

applying a coating formulation to at least a portion of the surface to form a coating on said surface, said coating formulation comprising a polymerization product of a substantially non-branched fluorinated monomer having from about 3 to about 20 carbon atoms and at least one terminal trifluoromethyl group, said coating comprising a surface having a surface area populated with at least about 30% by area trifluoromethyl groups and a surface energy of about 22 dynes/cm or lower at 20°

C.

24. The process defined in claim 23, wherein said coating formulation comprises a micropowder of said polymerization product, and said step of applying comprises coating said portion with said micropowder and melting or sintering said micropowder to form said coating.

25. The process defined in claim 23, wherein said coating formulation comprises from about 20% by weight to about 90% by weight of an epoxy monomer having a functionality of about 3 or greater and an epoxy equivalent weight of less than 250.

27. A process as defined in claim 23, wherein said laboratory vessel is a molded product, said coating formulation comprises a molten coating formulation, and said step of applying comprises coinjecting said molten coating formulation with a molten material comprising said laboratory vessel, to coat a surface of said molten material and provide a surface intended to contact a liquid, said surface comprising said coating formulation.

36. The process defined in claim 23, wherein said vessel comprises a pipette tip or a microcentrifuge tube.

28. A composition of matter comprising at least one fluorinated component, and a micropowder, said at least one fluorinated component comprising a fluorinated monomer or a polymerization product thereof, said fluorinated monomer having from about 3 to about 20 carbon atoms and at least one terminal trifluoromethyl group, said composition being able to provide a coating upon application to a surface of an article, said coating having an exposed surface area populated with 30% by area or more trifluoromethyl groups and a surface energy of about 22 dynes/cm or lower at 20°

C., and wherein said micropowder provides a rough surface to said coating.

29. The composition claimed in claim 28, wherein said micropowder comprises at least one material selected from the group consisting of siliconized glass particles and polytetrafluoroethylene powders.

30. The composition claimed in claim 28, wherein said micropowder has an average particle diameter of about 10 microns or less.

31. The composition claimed in claim 28, further comprising an epoxy resin.

32. The composition claimed in claim 28, further comprising a functional monomer selected from the group consisting of acrylate monomers, silicone monomers, and urethane monomers.

33. An article of manufacture comprising a surface and a coating on said surface, said coating being formed of the composition claimed in claim 28.