Anti-smudge and Anti-graffiti Compositions

• US 20160200937A1
• Filed: 10/16/2015
• Published: 07/14/2016
• Est. Priority Date: 10/16/2014
• Status: Active Grant

• Current Assignee: Queen's University At Kingston
• Original Assignee: Queen's University At Kingston
• Inventors: Hu, Heng, Rabnawaz, Muhammad, Liu, Guojun
• Granted Patent: US 10,023,751 B2
• Time in Patent Office: Days
• US Class Current: 1/1
• CPC Class Codes: C08F 2438/01 Atom Transfer Radical Polymerization [ATRP] or reverse ATRP
• CPC Class Codes: C08F 293/005 using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
• CPC Class Codes: C08G 18/61 Polysiloxanes
• CPC Class Codes: C08G 18/6229 Polymers of hydroxy groups containing esters of acrylic or methacrylic acid with aliphatic polyalcohols
• CPC Class Codes: C08G 18/6295 Polymers of silicium containing compounds having carbon-to-carbon double bonds
• CPC Class Codes: C08G 18/792 formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
• CPC Class Codes: C08G 18/798 containing urethdione groups
• CPC Class Codes: C08G 18/8074 Lactams
• CPC Class Codes: C08G 77/442 containing vinyl polymer sequences
• CPC Class Codes: C08G 77/458 containing polyurethane sequences
• CPC Class Codes: C08L 101/02 characterised by the presence of specified groups , e.g. terminal or pendant functional groups
• CPC Class Codes: C08L 63/00 Compositions of epoxy resins; Compositions of derivatives of epoxy resins
• CPC Class Codes: C09D 163/00 Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
• CPC Class Codes: C09D 175/04 Polyurethanes
• CPC Class Codes: C09D 183/10 Block or graft copolymers containing polysiloxane sequences obtained by polymerising a compound having a carbon-to-carbon double bond on to a polysiloxane C09D151/08, C09D153/00
• CPC Class Codes: C09D 5/16 Antifouling paints; Underwater paints

Abstract

Polyurethane-based and epoxy-based coating compositions are described that provide coatings and adhesives that are clear, amphiphobic and durable. Both water and hexadecane readily slide off these surfaces without leaving a residue. Coatings with thicknesses ranging from about 10 nm to about 10 μm exhibited excellent transmittance properties. Such films exhibited durability against abrasion, ink-resistance, anti-graffiti, anti-fingerprint, and strong adhesion to glass surfaces. The coatings are applicable to electronic devices, fabrics, glass, etc. to prepare optically clear, stain-resistant, and smudge-resistant surfaces.

Claims

1. A composition comprising:

a major component that is a polymer that is capable of crosslinking at multiple sites to form a solid material, or a major component that is an engineering plastic; and

a minor component that is a polymer having a first end that is capable of binding to the major component and having a second end that remains unbound;

wherein the composition is adapted to be applied to a substrate and dried and/or cured to form a coating on the substrate, such that;

the second end of at least a portion of the minor component is located at a surface of the coating; and

the coating is amphiphobic.

2. The composition of claim 1, wherein the minor component polymer has a glass transition temperature (Tg) in the range of about −

160°

C. to 25°

C.

3. The composition of claim 1, wherein the major component comprises polyurethane, epoxy resin, Nylon 6, Nylon 6-6, poly(acrylate), polyamide, poly(butylene terephthalate), polycarbonate, poly(etherketone), poly(etheretherketone), polyethylene, poly(ethylene terephthalate), polyimide, poly(methacrylate), poly(oxymethylene), poly(phenylene sulfide), poly(phenylene oxide), polypropylene (isotactic), polysulphone, polystyrene, or a combination thereof.

4. The composition of claim 1, wherein the coating is substantially transparent.

5. The composition of claim 4, wherein the major component comprises polyurethane or epoxy resin.

6. The composition of claim 1, wherein the minor component comprises about 0.1 wt % to about 40 wt % of the composition.

7. The composition of claim 6, wherein the minor component polymer has a Tg of about 25°

C. or less and is selected from perfluoropolyether (PFPE), polysiloxane, poly (ethylene glycol) methyl ether (PEO), polyisobutylene (PIB), polybutadiene (PB), or a polymeric form of;

ethylene (atactic), 1-butene, ethylene, cis-isoprene, trans-isoprene, 1-octene, propylene, vinyl propionate, vinylidene chloride, vinylidene fluoride, cis-chlorobutadiene, trans-chlorobutadiene, benzyl acrylate, butyl acrylate, sec-butyl acrylate, 2-cyanoethyl acrylate, cyclohexyl acrylate, dodecyl acrylate, ethyl acrylate, 2-ethylhexyl acrylate, isobutyl acrylate, 2,2,2-trifluoroethyl acrylate, 2-ethoxyethyl acrylate, isopropyl acrylate (isotactic), benzyl methacrylate, diethylaminoethyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, hexadecyl methacrylate, hexyl methacrylate, octadecyl methacrylate, octyl methacrylate, propyl vinyl ether, methyl vinyl ether, methyl glycidyl ether, isobutyl vinyl ether, ethyl vinyl ether, 2-ethylhexyl vinyl ether, dodecyl vinyl ether, butyl vinyl ether, butyl glydicyl ether, allyl glycidyl ether, ethylene oxide, propylene oxide, tetrahydrofuran, 1,2-epoxybutane, 1,2-epoxydecane, 1,2-epoxyoctane, epibromohydrin, epichlorohydrin, trimethylene oxide, epibromohydrin, epichlorohydrin, tetramethylene terephthalate, tetramethylene adipate, ethylene malonate, ethylene adipate, ε

-caprolactone, dimethylsiloxane, methylphenylsiloxane, formaldehyde, ethylene-trans-1,4-cyclohexyldicarboxylate, acetaldehyde, or poly(1-glycidyl-3-butylimidazolium bis(trifluoromethanesulfonyl)imide) (“

polyGBIMTFSI”

);

or a phosphazene polymer

8. The composition of claim 1, further comprising biocide, embedded particles selected from silica, titanium dioxide, diatomaceous earth, alumina, TiO₂, and/or a pigment.

9. The composition of claim 1, wherein the minor component is a graft copolymer of formula (1) or a block copolymer of formula (2):

10. The composition of claim 9, wherein FS further comprises at least one moiety that links FS to R or Mi of the copolymer.

11. The composition of claim 9, wherein the PFPE moiety is Demnum, Fluorolink Diol, Fomblin Z, Krytox®

, or Aflunox.

12. The composition of claim 9, wherein the minor component comprises:

PFPE-b-P(HEMA-S-MMA);

PDMS-b-[HEMA-S-MMA];

PDMS-b-PGMA;

Polyol-g-PIB;

Polyol-g-PB;

P(S-MMA-MAA-BMA-IBMA-VP-EGEMA-HEMA)-g-PFPE;

P(TFEMA-co-HEMA)-g-PFPE;

P(S-MMA-MAA-BMA-IBMA-VE-EGEMA-HEMA)-g-PDMS;

P(S-alt-MA)-g-PEO₇₅₀;

P(S-alt-MA)-g-PEO₂₀₀₀;

P(S-alt-MA)-g-PEO₅₀₀₀;

PFPE-b-P(HEMA-S-MMA);

PDMS-b-[HEMA-S-MMA];

PDMS-b-PGMA;

Polyol-g-PIB;

Polyol-g-PB;

or any combination thereof.

13. The coating composition of claim 9, wherein FS comprises polydimethylsiloxane.

14. The composition of claim 10, wherein FS comprises:

CH₂═

CH—

CO₂-polysiloxane;

CH₂═

CH—

CO₂—

PDMS;

CH₂═

C(CH₃)—

CO₂-polysiloxane;

CH₂═

C(CH₃)—

CO₂—

PDMS;

CH₂═

CH—

CO₂—

PFPE;

CH₂═

CH—

CO₂—

Krytox;

CH₂═

C(CH₃)—

CO₂—

PFPE;

CH₂═

C(CH₃)—

CO₂—

Krytox;

or CH₂═

C(CH₃)COOCH₂CH₂OOCCF(CF₃)[CF₂—

CF(CF₃)O]_iCF₃.

15. The composition of claim 9, wherein FS comprises a PFPE moiety that comprises a C₁₀ to C₂₀₀₀ perfluoro polyether moiety.

16. The composition of claim 7, wherein the minor component comprises polysiloxane, PFPE, PEO, or PIB, or any combination thereof;

wherein the polysiloxane, PFPE, PEO, PIB, or any combination thereof is grafted to a polymer, wherein the polymer is selected from polyacrylate, polymethacrylate, polyacrylic acid, polymethacrylic acid, polystyrene, polyvinyl ester, polyimine/polyamine, polycarboxylic acid/polyanhydride, or any combination thereof.

17. The composition of claim 9, wherein the FS moiety comprises:

polyacrylate-g-polysiloxane;

polymethacrylate-g-polysiloxane;

poly(acrylic acid)-g-polysiloxane;

poly(methacrylic acid)-g-polysiloxane;

polystyrene-g-polysiloxane;

poly(vinyl ester)-g-polysiloxane;

polyacrylate-g-PFPE;

polymethacrylate-g-PFPE;

poly(acrylic acid)-g-PFPE;

poly(methacrylic acid)-g-PFPE;

polystyrene-g-PFPE;

polyvinyl ester-g-PFPE;

PEI-g-PDMS;

P(S-alt-MA)-g-PDMS;

polyacrylate-b-polysiloxane;

polymethacrylate-b-polysiloxane;

polyacrylic acid-b-polysiloxane;

polymethacrylic acid-b-polysiloxane;

polystyrene-b-polysiloxane;

polyvinyl ester-b-polysiloxane;

polyacrylate-b-PFPE;

polymethacrylate-b-PFPE;

poly(acrylic acid)-b-PFPE;

poly(methacrylic acid)-b-PFPE;

polystyrene-b-PFPE;

poly(vinyl ester)-b-PFPE;

or PDMS-b-PGMA.

24. A polyurethane-based coating composition prepared by combining:

a copolymer that is a polyol, polyamine, polyimine, poly(carboxylic acid), or polyanhydride that comprises a polysiloxane, PFPE, PEO, PM, or PB moiety, or a polymer having a Tg of 25°

C. or less as claimed in claim 7.

25. A composition that comprising:

a major component that is a polymer having a Tg of 120°

C. or higher or is an engineering plastic; and

a minor component that is a polymer having a Tg of 25°

C. or less as claimed in claim 7 and having a first end that is capable of binding to the major component and having a second end that remains unbound;

wherein the composition is adapted to be applied to a substrate and dried and/or cured to form a coating on the substrate, such that;

the second end of at least a portion of the minor component is located at a surface of the coating; and

the coating is amphiphobic.

26. A method comprising:

applying the composition of claim 1 to a substrate;

wherein the composition forms a coating on the substrate;

wherein the coating is amphiphobic.

27. The method of claim 26, further comprising drying and/or curing the composition to form the coating.

18. A polyurethane-based coating composition prepared by combining:

a copolymer that is a polyol, polyamine, polyimine, poly(carboxylic acid), or polyanhydride that comprises a polysiloxane, PFPE, PEO, PIB, or PB moiety;

di-, tri-, or poly-isocyanate; and

, optionally

a polyol, polyamine, polyimine, poly(carboxylic acid), and/or polyanhydride that does not comprise a polysiloxane, PFPE, PEO, PIB, nor PB moiety;

wherein the coating composition comprises about 0.1 wt % to about 40 wt % siloxane, fluorine, PEO, PIB, or PB.

19. The polyurethane-based coating composition of claim 18, wherein the polyol that comprises a polysiloxane, PFPE, PEO, PIB, or PB moiety is Polyol-g-PIB.

20. The polyurethane-based coating composition of claim 20, wherein the polyanhydride that comprises a polysiloxane, PFPE, PEO, PIB, or PB moiety is P(S-alt-MA)-g-PEO.

21. An epoxy-based coating composition prepared by combining:

a polymer comprising at least one functional moiety and at least one of a polysiloxane, PFPE, PEO, PIB, and PB moiety;

an epoxy resin; and

optionally a hardener; and

optionally a solvent.

22. The epoxy-based coating composition of claim 21, wherein the epoxy resin comprises polyglycidyl bisphenol A diglycidyl ether, bisphenol F, bisphenol S, novolac epoxy resin, aliphatic epoxy resin, glycidylamine epoxy resin, or any combination thereof.

23. The epoxy-based coating composition of claim 21 or 22, wherein the polymer comprises:

28. A polyurethane-based coating composition prepared by combining:

a graft or block polymer comprising at least one functional moiety and at least one polysiloxane or PFPE moiety;

isocyanate (bi-, tri- or multi-); and

polyol, polyamine, or a combination of polyol and polyamine;

wherein a coating resulting from application of the coating composition is anti-smudge.

31. The polyurethane-based coating compositions of claim 28, wherein the coating is clear.

34. The polyurethane-based coating compositions of claim 28, wherein the polymer and the isocyanate are allowed to react and then the polyol, polyamine, or combination of polyol and polyamine is added.

29. A polyurethane-based coating composition prepared by combining:

a polymer comprising at least one functional moiety and at least one poly (ethylene glycol) methyl ether (“

PEO”

), polyisobutylene (“

PIB”

), or polybutadiene (“

PB”

) moiety;

isocyanate (bi-, tri- or multi-); and

polyol, polyamine, or a combination of polyol and polyamine;

wherein a coating resulting from application of the coating composition is anti-smudge.

32. The polyurethane-based coating compositions of claim 29, wherein the coating is clear.

35. The polyurethane-based coating compositions of claim 29, wherein the polymer and the isocyanate are allowed to react and then the polyol, polyamine, or a combination of polyol and polyamine is added.

30. A polyurethane-based coating composition prepared by combining:

a polymer comprising polysiloxane and multiple amino groups;

isocyanate (bi-, tri- or multi-); and

oligomeric polyol, oligomeric polyamine, or a combination of oligomeric polyol and oligomeric polyamine,

wherein a coating resulting from application of the coating composition is anti-smudge.

33. The polyurethane-based coating compositions of claim 30, wherein the coating is clear.

36. The polyurethane-based coating compositions of claim 30, wherein the polymer and the isocyanate are allowed to react, and then the polyol, polyamine, or combination thereof is added.

37. The polyurethane-based coating composition of claim 30, wherein the oligomeric polyol comprises acrylic polyol, methacrylic polyol, styrenic polyol, or polyol comprising acryl, styrenyl or methacrylyl units.