Anti-smudge and Anti-graffiti Compositions

Patent metadata

Field	Value
Publication number	US-2016200937-A1
Application number	US-201514885414-A
Country	US
Kind code	A1
Filing date	Oct 16, 2015
Priority date	Oct 16, 2014
Publication date	Jul 14, 2016
Grant date	—

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.

First claim

We claim:

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

where R 1 and R 2 are CH 3 , C 6 H 5 , OCH 3 , OC 6 H 5 , NR 2 , Cl, Br, F, OCH 2 CF 3 , or OCH 2 C 6 H 5 ;
or any combination thereof.

8 . The composition of claim 1 , further comprising biocide, embedded particles selected from silica, titanium dioxide, diatomaceous earth, alumina, TiO 2 , 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):

where FS is a moiety comprising PFPE, polysiloxane, PEO, PIB, PB, a polymer whose Tg is 25° C. or less as claimed in claim 7 , or any combination thereof;
R is a moiety that comprises a hydroxyl, amine (NH 2 ), imine (NH), carboxyl, glycidyl, isocyanato, or an anhydride functional group that is protected or unprotected;
Mi is a monomer selected from styrene, acrylate, methacrylate, vinyl esters, acrylic acids, methacrylic acids, amine-bearing monomers, anhydride-bearing monomers, polyimine/polyamine, or polycarboxylic acid/polyanhydride;
x is percentage of FS moieties and is from about 0.1% to about 40%;
y is percentage of R moieties and is from about 1% to about 90%;
n is number of repeat units.

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-PEO 750 ; P(S-alt-MA)-g-PEO 2000 ; P(S-alt-MA)-g-PEO 5000 ; 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:
CH 2 ═CH—CO 2 -polysiloxane; CH 2 ═CH—CO 2 —PDMS; CH 2 ═C(CH 3 )—CO 2 -polysiloxane; CH 2 ═C(CH 3 )—CO 2 —PDMS; CH 2 ═CH—CO 2 —PFPE; CH 2 ═CH—CO 2 —Krytox; CH 2 ═C(CH 3 )—CO 2 —PFPE; CH 2 ═C(CH 3 )—CO 2 —Krytox; or CH 2 ═C(CH 3 )COOCH 2 CH 2 OOCCF(CF 3 )[CF 2 —CF(CF 3 )O] i CF 3 .

15 . The composition of claim 9 , wherein FS comprises a PFPE moiety that comprises a C 10 to C 2000 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.

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

Assignees

• Univ Kingston

Inventors

• Hu Heng
• Liu Guojun
• Rabnawaz Muhammad

Classifications

• C08G18/792

  formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates · CPC title

• C09D163/00

  Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins · CPC title

• C08G77/458

  containing polyurethane sequences · CPC title

• C08L63/00

  Compositions of epoxy resins; Compositions of derivatives of epoxy resins · CPC title

• C08G18/798

  containing urethdione groups · CPC title