Optically transparent, superhydrophobic, biocompatible thin film coatings and methods for producing same

• US 9,752,049 B2
• Filed: 02/20/2014
• Issued: 09/05/2017
• Est. Priority Date: 02/20/2014
• Status: Active Grant

• Current Assignee: UT-Battelle LLC
• Original Assignee: UT-Battelle LLC
• Inventors: Armstrong, Beth L., Aytug, Tolga, Paranthaman, Mariappan Parans, Simpson, John T., Hillesheim, Daniel A., Trammell, Neil E.
• Primary Examiner(s): Jolley, Kirsten
• Application Number:
  US14/185,830
• Publication Number:
  US 20150232690A1
• Time in Patent Office: 1,293 Days
• Field of Search: 427240, 427425, 4274211, 4274274
• CPC Class Codes: B05D 1/005 Spin coating
• CPC Class Codes: B05D 1/02 performed by spraying
• CPC Class Codes: C08F 222/322 Alpha-cyano-acrylic acid ethyl ester, e.g. ethyl-2-cyanoacrylate
• CPC Class Codes: C08F 283/10 on to polymers containing more than one epoxy radical per molecule C08F283/004 takes precedence
• CPC Class Codes: C09D 163/00 Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
• CPC Class Codes: C09D 4/06 Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00

Abstract

An optically transparent, hydrophobic coating, exhibiting an average contact angle of at least 100 degrees with a drop of water. The coating can be produced using low-cost, environmentally friendly components. Methods of preparing and using the optically transparent, hydrophobic coating.

Claims

1. A coating composition comprising:

a solvent, in an amount of from 98.5 to 99.3 percent by weight based on the total weight of the coating composition;

a straight-chain fatty acid, in an amount of from 0.1 to 1 percent by weight based on the total weight of the coating composition;

wherein said composition comprises at least one epoxy resin and at least one cyanoacrylate, in an amount of from 0.1 to 0.9 percent by weight based on the total weight of the coating composition; and

wherein when applied to a substrate the coating composition provides a surface exhibiting a contact angle of at least 100 degrees with a drop of water, and

wherein when applied to the substrate the coating is optically transparent.

2. The coating according to claim 1, wherein the surface exhibits a contact angle with a drop of water of at least 150 degrees with a drop of water.

3. The coating according to claim 1, wherein the solvent is selected from the group consisting of ethanol, isopropanol, hexane, acetone, toluene and combinations thereof.

4. The coating according to claim 1, wherein the cyanoacrylate is a cyanoacrylate according to Formula I,

5. The coating according to claim 1, wherein the cyanoacrylate is selected from the group consisting of n-propyl-cyanoacrylate, iso-propyl cyanoacrylate, n-butylcyanoacrylate, sec-butyl-cyanoacrylate, iso-butyl-cyanoacrylate, tert-butyl-cyanoacrylate, n-pentyl-cyanoacrylate, 1-methyl-butyl-cyanoacrylate, 1-ethyl-propyl-cyanoacrylate, neopentyl-cyanoacrylate, n-hexyl-cyanoacrylate, 1-methyl pentyl-cyanoacrylate, n-heptyl-cyanoacrylate, n-octyl-cyanoacrylate, n-nonyl-cyanoacrylate, n-decyl-cyanoacrylate, n-undecyl-cyanoacrylate, n-dodecyl-cyanoacrylate, cyclohexyl-cyanoacrylate, benzyl-cyanoacrylate, phenyl-cyanoacrylate, tetrahydrofurfuryl-cyanoacrylate, allyl cyanoacrylate, propargyl-cyanoacrylate, 2-butenyl-cyanoacrylate, phenethyl-cyanoacrylate, chloropropyl-cyanoacrylate, ethoxyethyl-cyanoacrylate, ethoxypropyl-cyanoacrylate, ethoxy isopropyl-cyanoacrylate, propoxyethyl-cyanoacrylate, isopropoxyethyl-cyanoacrylate, butoxyethyl-cyanoacrylate, methoxypropyl-cyanoacrylate, methoxy isopropyl-cyanoacrylate, methoxy butyl-cyanoacrylate, propoxymethyl-cyanoacrylate, propoxy ethyl-cyanoacrylate, propoxy propyl-cyanoacrylate, butoxymethyl-cyanoacrylate, butoxyethyl-cyanoacrylate, butoxypropyl-cyanoacrylate, butoxyisopropyl-cyanoacrylate, butoxy butyl-cyanoacrylate, iso-nonyl-cyanoacrylate, iso-decyl-cyanoacrylate, cyclohexyl methyl-cyanoacrylate, naphthyl-cyanoacrylate, 2-(2′

-methoxy)-ethoxy ethyl-cyanoacrylate, 2-(2′

-ethoxy)-ethoxy ethyl-cyanoacrylate, 2-(2′

-propyloxy)-ethoxy ethyl-cyanoacrylate, 2-(2′

-butyloxy)-ethoxy ethyl-cyanoacrylate, 2-(2′

-pentyloxy)-ethoxy ethyl-cyanoacrylate, 2-(2′

-hexyloxy)-ethoxy ethyl-cyanoacrylate, 2-(2-methoxy)-propyloxy propyl-cyanoacrylate, 2-(2′

-ethoxy)-propyloxy propyl-cyanoacrylate, 2-(2′

-propyloxy)-propyloxy propyl-cyanoacrylate, 2-(2′

-pentyloxy)-propyloxy propyl-cyanoacrylate, 2-(2′

-hexyloxy)-propyloxy propyl-cyanoacrylate, 2-(2′

-methoxy)-butyloxy butylcyanoacrylate, 2-(2′

-ethoxy)-butyloxy butyl-cyanoacrylate, 2-(2′

-butyloxy)-butyloxy butyl-cyanoacrylate, 2-(3′

-methoxy)-propyloxy ethyl-cyanoacrylate, 2-(3′

-methoxy)-butyloxy ethyl-cyanoacrylate, 2-(3′

-methoxy)-propyloxy propyl-cyanoacrylate, 2-(3′

-methoxy)-butyloxy propyl-cyanoacrylate, 2-(2′

-methoxy)-ethoxy propyl-cyanoacrylate, and 2-(2′

-methoxy)-ethoxy, butyl-cyanoacrylate, and combinations thereof.

6. The coating according to claim 1, wherein the fatty acid is a fatty acid according to Formula II

7. The coating according to claim 1, wherein the fatty acid is selected from the group consisting of Propionic acid, Butyric acid, Valeric acid, Caproic acid, Enanthic acid, Caprylic acid, Pelargonic acid, Capric acid, Undecylic acid, Lauric acid, Tridecylic acid, Myristic acid, Pentadecylic acid, Palmitic acid, Margaric acid, Stearic acid, Nonadecylic acid, Arachidic acid, Heneicosylic acid, Behenic acid, Tricosylic acid, Lignoceric acid, Pentacosylic acid, Cerotic acid, Heptacosylic acid, Montanic acid, Nonacosylic acid, Melissic acid, Henatriacontylic acid, Lacceroic acid, Psyllic acid, Geddic acid, Ceroplastic acid, Hexatriacontylic acid, and combinations thereof.

8. The coating according to claim 1, wherein the epoxy resin is selected from the group consisting of a bisphenol A epoxy resin, a bisphenol F epoxy resin, a novolac epoxy resin, an aliphatic epoxy resin, a glycidylamine epoxy resin, and combinations thereof.

9. A method for providing a surface with a contact angle of at least 100 degrees with respect to a drop of water, the method comprising applying a composition to the surface, the composition comprising

a solvent, in an amount of from 98.5 to 99.3 percent by weight based on the total weight of the coating composition;

a straight-chain, unsubstituted fatty acid, in an amount of from 0.1 to 1 percent by weight based on the total weight of the coating composition;

wherein said composition comprises at least one epoxy resin and at least one cyanoacrylate, in an amount of from 0.1 to 0.9 percent by weight based on the total weight of the coating composition; and

wherein when applied to the surface the composition is optically transparent.

10. The method according to claim 9 wherein the coating composition is applied by one selected from the group consisting of spin coating, spraying, and combinations thereof.

11. The method according to claim 9, wherein the solvent is selected from the group consisting of ethanol, isopropanol, hexane, acetone, toluene and combinations thereof.

12. The method according to claim 9, wherein the cyanoacrylate is a cyanoacrylate according to Formula I,

13. The method according to claim 9, wherein the cyanoacrylate is selected from the group consisting of n-propyl-cyanoacrylate, iso-propyl cyanoacrylate, n-butylcyanoacrylate, sec-butyl-cyanoacrylate, iso-butyl-cyanoacrylate, tert-butyl-cyanoacrylate, n-pentyl-cyanoacrylate, 1-methyl-butyl-cyanoacrylate, 1-ethyl-propyl-cyanoacrylate, neopentyl-cyanoacrylate, n-hexyl-cyanoacrylate, 1-methyl pentyl-cyanoacrylate, n-heptyl-cyanoacrylate, n-octyl-cyanoacrylate, n-nonyl-cyanoacrylate, n-decyl-cyanoacrylate, n-undecyl-cyanoacrylate, n-dodecyl-cyanoacrylate, cyclohexyl-cyanoacrylate, benzyl-cyanoacrylate, phenyl-cyanoacrylate, tetrahydrofurfuryl-cyanoacrylate, allyl cyanoacrylate, propargyl-cyanoacrylate, 2-butenyl-cyanoacrylate, phenethyl-cyanoacrylate, chloropropyl-cyanoacrylate, ethoxyethyl-cyanoacrylate, ethoxypropyl-cyanoacrylate, ethoxy isopropyl-cyanoacrylate, propoxyethyl-cyanoacrylate, isopropoxyethyl-cyanoacrylate, butoxyethyl-cyanoacrylate, methoxypropyl-cyanoacrylate, methoxy isopropyl-cyanoacrylate, methoxy butyl-cyanoacrylate, propoxymethyl-cyanoacrylate, propoxy ethyl-cyanoacrylate, propoxy propyl-cyanoacrylate, butoxymethyl-cyanoacrylate, butoxyethyl-cyanoacrylate, butoxypropyl-cyanoacrylate, butoxyisopropyl-cyanoacrylate, butoxy butyl-cyanoacrylate, iso-nonyl-cyanoacrylate, iso-decyl-cyanoacrylate, cyclohexyl methyl-cyanoacrylate, naphthyl-cyanoacrylate, 2-(2′

-methoxy)-ethoxy ethyl-cyanoacrylate, 2-(2′

-ethoxy)-ethoxy ethyl-cyanoacrylate, 2-(2′

-propyloxy)-ethoxy ethyl-cyanoacrylate, 2-(2′

-butyloxy)-ethoxy ethyl-cyanoacrylate, 2-(2′

-pentyloxy)-ethoxy ethyl-cyanoacrylate, 2-(2′

-hexyloxy)-ethoxy ethyl-cyanoacrylate, 2-(2′

-methoxy)-propyloxy propyl-cyanoacrylate, 2-(2′

-ethoxy)-propyloxy propyl-cyanoacrylate, 2-(2′

-propyloxy)-propyloxy propyl-cyanoacrylate, 2-(2′

-pentyloxy)-propyloxy propyl-cyanoacrylate, 2-(2′

-hexyloxy)-propyloxy propyl-cyanoacrylate, 2-(2′

-methoxy)-butyloxy butylcyanoacrylate, 2-(2′

-ethoxy)-butyloxy butyl-cyanoacrylate, 2-(2-butyloxy)-butyloxy butyl-cyanoacrylate, 2-(3′

-methoxy)-propyloxy ethyl-cyanoacrylate, 2-(3′

-methoxy)-butyloxy ethyl-cyanoacrylate, 2-(3′

-methoxy)-propyloxy propyl-cyanoacrylate, 2-(3′

-methoxy)-butyloxy propyl-cyanoacrylate, 2-(2′

-methoxy)-ethoxy propyl-cyanoacrylate, and 2-(2′

-methoxy)-ethoxy, butyl-cyanoacrylate, and combinations thereof.

14. The method according to claim 9, wherein the fatty acid is a fatty acid according to Formula II

15. The method according to claim 9, wherein the fatty acid is selected from the group consisting of Propionic acid, Butyric acid, Valeric acid, Caproic acid, Enanthic acid, Caprylic acid, Pelargonic acid, Capric acid, Undecylic acid, Lauric acid, Tridecylic acid, Myristic acid, Pentadecylic acid, Palmitic acid, Margaric acid, Stearic acid, Nonadecylic acid, Arachidic acid, Heneicosylic acid, Behenic acid, Tricosylic acid, Lignoceric acid, Pentacosylic acid, Cerotic acid, Heptacosylic acid, Montanic acid, Nonacosylic acid, Melissic acid, Henatriacontylic acid, Lacceroic acid, Psyllic acid, Geddic acid, Ceroplastic acid, Hexatriacontylic acid, and combinations thereof.

16. The method according to claim 9, wherein the epoxy resin is selected from the group consisting of a bisphenol A epoxy resin, a bisphenol F epoxy resin, a novolac epoxy resin, an aliphatic epoxy resin, a glycidylamine epoxy resin, and combinations thereof.

17. A method for preparing a coating composition, the method comprising mixing a solvent, a straight-chain, unsubstituted fatty acid, wherein said composition comprises at least one epoxy resin and at least one cyanoacrylate, to form the coating composition, wherein the solvent is present in an amount of from 98.5 to 99.3 percent by weight based on the total weight of the coating composition, wherein the fatty acid is present in an amount of from 0.1 to 1 percent by weight based on the total weight of the coating composition, wherein the epoxy resin and the cyanoacrylate is present in an amount of from 0.1 to 0.9 percent by weight based on the total weight of the coating composition, and wherein when applied to a substrate, the coating composition provides a surface exhibiting a contact angle of at least 100 degrees with a drop of water, wherein when applied to the substrate the coating composition is optically transparent.

18. The method according to claim 17, wherein the coating composition is applied by one selected from the group consisting of spin coating, spraying, and combinations thereof.

19. The method according to claim 17, wherein the solvent is selected from the group consisting of ethanol, isopropanol, hexane, acetone, toluene and combinations thereof.

20. The method according to claim 17, wherein the cyanoacrylate is a cyanoacrylate according to Formula I,

21. The method according to claim 17, wherein the cyanoacrylate is selected from the group consisting of n-propyl-cyanoacrylate, iso-propyl cyanoacrylate, n-butylcyanoacrylate, sec-butyl-cyanoacrylate, iso-butyl-cyanoacrylate, tert-butyl-cyanoacrylate, n-pentyl-cyanoacrylate, 1-methyl-butyl-cyanoacrylate, 1-ethyl-propyl-cyanoacrylate, neopentyl-cyanoacrylate, n-hexyl-cyanoacrylate, 1-methyl pentyl-cyanoacrylate, n-heptyl-cyanoacrylate, n-octyl-cyanoacrylate, n-nonyl-cyanoacrylate, n-decyl-cyanoacrylate, n-undecyl-cyanoacrylate, n-dodecyl-cyanoacrylate, cyclohexyl-cyanoacrylate, benzyl-cyanoacrylate, phenyl-cyanoacrylate, tetrahydrofurfuryl-cyanoacrylate, allyl cyanoacrylate, propargyl-cyanoacrylate, 2-butenyl-cyanoacrylate, phenethyl-cyanoacrylate, chloropropyl-cyanoacrylate, ethoxyethyl-cyanoacrylate, ethoxypropyl-cyanoacrylate, ethoxy isopropyl-cyanoacrylate, propoxyethyl-cyanoacrylate, isopropoxyethyl-cyanoacrylate, butoxyethyl-cyanoacrylate, methoxypropyl-cyanoacrylate, methoxy isopropyl-cyanoacrylate, methoxy butyl-cyanoacrylate, propoxymethyl-cyanoacrylate, propoxy ethyl-cyanoacrylate, propoxy propyl-cyanoacrylate, butoxymethyl-cyanoacrylate, butoxyethyl-cyanoacrylate, butoxypropyl-cyanoacrylate, butoxyisopropyl-cyanoacrylate, butoxy butyl-cyanoacrylate, iso-nonyl-cyanoacrylate, iso-decyl-cyanoacrylate, cyclohexyl methyl-cyanoacrylate, naphthyl-cyanoacrylate, 2-(2′

-methoxy)-ethoxy ethyl-cyanoacrylate, 2-(2′

-ethoxy)-ethoxy ethyl-cyanoacrylate, 2-(2-propyloxy)-ethoxy ethyl-cyanoacrylate, 2-(2-butyloxy)-ethoxy ethyl-cyanoacrylate, 2-(2-pentyloxy)-ethoxy ethyl-cyanoacrylate, 2-(2′

-hexyloxy)-ethoxy ethyl-cyanoacrylate, 2-(2′

-methoxy)-propyloxy propyl-cyanoacrylate, 2-(2-ethoxy)-propyloxy propyl-cyanoacrylate, 2-(2′

-propyloxy)-propyloxy propyl-cyanoacrylate, 2-(2-pentyloxy)-propyloxy propyl-cyanoacrylate, 2-(2-hexyloxy)-propyloxy propyl-cyanoacrylate, 2-(2-methoxy)-butyloxy butylcyanoacrylate, 2-(2-ethoxy)-butyloxy butyl-cyanoacrylate, 2-(2-butyloxy)-butyloxy butyl-cyanoacrylate, 2-(3′

-methoxy)-propyloxy ethyl-cyanoacrylate, 2-(3′

-methoxy)-butyloxy ethyl-cyanoacrylate, 2-(3′

-methoxy)-propyloxy propyl-cyanoacrylate, 2-(3′

-methoxy)-butyloxy propyl-cyanoacrylate, 2-(2′

-methoxy)-ethoxy propyl-cyanoacrylate, and 2-(2-methoxy)-ethoxy, butyl-cyanoacrylate, and combinations thereof.

22. The method according to claim 17, wherein the fatty acid is a fatty acid according to Formula II

23. The method according to claim 17, wherein the fatty acid is selected from the group consisting of Propionic acid, Butyric acid, Valeric acid, Caproic acid, Enanthic acid, Caprylic acid, Pelargonic acid, Capric acid, Undecylic acid, Lauric acid, Tridecylic acid, Myristic acid, Pentadecylic acid, Palmitic acid, Margaric acid, Stearic acid, Nonadecylic acid, Arachidic acid, Heneicosylic acid, Behenic acid, Tricosylic acid, Lignoceric acid, Pentacosylic acid, Cerotic acid, Heptacosylic acid, Montanic acid, Nonacosylic acid, Melissic acid, Henatriacontylic acid, Lacceroic acid, Psyllic acid, Geddic acid, Ceroplastic acid, Hexatriacontylic acid, and combinations thereof.

24. The method according to claim 17, wherein the epoxy resin is selected from the group consisting of a bisphenol A epoxy resin, a bisphenol F epoxy resin, a novolac epoxy resin, an aliphatic epoxy resin, a glycidylamine epoxy resin, and combinations thereof.