Omniphobic compatibilizers for clear coatings, related articles, and related methods

Patent metadata

Field	Value
Publication number	US-11746176-B2
Application number	US-202017624652-A
Country	US
Kind code	B2
Filing date	Jul 3, 2020
Priority date	Jul 5, 2019
Publication date	Sep 5, 2023
Grant date	Sep 5, 2023

Abstract

The disclosure generally relates to omniphobic compatibilizers, which include a polymerization reaction product between a first vinyl monomer, optionally a second vinyl crosslinking monomer, and a functionalized omniphobic polymer. The functionalized omniphobic polymer can include two or more vinyl functional groups or at least one free radical initiator functional group such that the reaction product forming the omniphobic compatibilizer can be a vinyl or free-radical polymerization product. The omniphobic compatibilizer can be incorporated into a UV-curable or a non-UV-curable thermoset omniphobic composition. The UV-curable composition can be a crosslinked polymerization reaction product between the omniphobic compatibilizer, a third vinyl monomer, and a fourth polyvinyl crosslinking monomer. The non-UV-curable composition can be a crosslinked polymerization reaction product between the omniphobic compatibilizer, a first thermosetting component, and a second thermosetting component. The thermoset omniphobic composition can be a coating on a substrate in a corresponding coated article.

First claim

What is claimed is:

1. An omniphobic compatibilizer comprising:
a polymerization reaction product between:
a first vinyl monomer,
a second vinyl crosslinking monomer having a structure according to formula II:
CH 2 ═CR 1 R 3   (II)

where:
R 1 is selected from hydrogen atoms, halogen atoms, alkyl groups, aryl groups, nitrile groups, ester groups, carboxylic acid groups, ketone groups, ether groups, and heteroatom-substituted derivatives of the foregoing groups, and
R 3 comprises (i) a reactive functional group selected from epoxide groups, isocyanate groups, amino groups, hydroxyl groups, carboxylic groups, and combinations thereof, and (ii) a linking group selected from hydrocarbons containing from 1 to 20 carbon atoms and heteroatom-substituted hydrocarbons containing from 1 to 20 carbon atoms, and

a functionalized omniphobic polymer having a glass transition temperature (T g ) of 70° C. or less, the functionalized omniphobic polymer comprising two or more vinyl functional groups;

wherein the polymerization reaction product comprises:
block polymerization segments comprising first vinyl monomer backbone units and optionally second vinyl crosslinking monomer units, but no functionalized omniphobic polymer backbone units; and
random polymerization segments comprising first vinyl monomer backbone units, second vinyl crosslinking monomer units, and functionalized omniphobic polymer backbone units.

2. The omniphobic compatibilizer of claim 1 , wherein:
the first vinyl monomer has a structure according to formula I:
CH 2 ═CR 1 R 2   (I)

where:
R 1 and R 2 are independently selected from hydrogen atoms, halogen atoms, alkyl groups, aryl groups, nitrile groups, ester groups, carboxylic acid groups, ketone groups, ether groups, and heteroatom-substituted derivatives of the foregoing groups.

3. The omniphobic compatibilizer of claim 1 , wherein the functionalized omniphobic polymer is selected from the group consisting of functionalized polysiloxanes, functionalized polyperfluoroethers, functionalized polyisobutenes, functionalized branched polyolefins, functionalized low molecular weight polyolefins, functionalized poly(meth)acrylates, and combinations thereof.

4. The omniphobic compatibilizer of claim 1 , wherein the functionalized omniphobic polymer comprises a di-vinyl functionalized omniphobic polymer.

5. The omniphobic compatibilizer of claim 1 , wherein the functionalized omniphobic polymer has a glass transition temperature in a range from −150° C. to 70° C.

6. The omniphobic compatibilizer of claim 1 , wherein the functionalized omniphobic polymer is a liquid at a temperature in a range from 0° C. to 40° C.

7. The omniphobic compatibilizer of claim 1 , wherein the functionalized omniphobic polymer has a molecular weight ranging from 300 to 50,000 g/mol.

8. The omniphobic compatibilizer of claim 1 , wherein:
the first vinyl monomer is present in the polymerization reaction product in an amount in a range from 1 to 99 wt. % based on the polymerization reaction product;
the second vinyl crosslinking monomer is present in the polymerization reaction product in an amount in a range from 0.5 to 20 wt. % based on the polymerization reaction product; and
the functionalized omniphobic polymer is present in the polymerization reaction product in an amount in a range from 0.05 to 70 wt. % based on the polymerization reaction product.

9. A thermoset omniphobic composition comprising:
a crosslinked polymerization reaction product of a mixture comprising:
an omniphobic compatibilizer comprising a polymerization reaction product between (i) a first vinyl monomer, (ii) optionally a second vinyl crosslinking monomer, and (iii) a functionalized omniphobic polymer having a glass transition temperature (T g ) of 70° C. or less, wherein the functionalized omniphobic polymer comprises (A) two or more vinyl functional groups or (B) at least one free radical initiator functional group,
a third vinyl monomer,
a fourth polyvinyl crosslinking monomer, and
a UV-curing catalyst;

wherein:
the third vinyl monomer is present in the crosslinked polymerization reaction product in an amount in a range from 5 to 98 wt. % based on the crosslinked polymerization reaction product;
the omniphobic compatibilizer is present in the crosslinked polymerization reaction product in an amount in a range from 0.5 to 20 wt. % based on the crosslinked polymerization reaction product; and
the fourth polyvinyl crosslinking monomer is present in the crosslinked polymerization reaction product in an amount in a range from 0.5 to 20 wt. % based on the crosslinked polymerization reaction product.

10. The thermoset omniphobic composition of claim 9 , wherein:
the omniphobic compatibilizer comprises the two or more vinyl functional groups, and
the omniphobic compatibilizer is present in the thermoset omniphobic composition as one or both of (i) a physical blend with the crosslinked reaction product between the third vinyl monomer and the fourth polyvinyl crosslinking monomer, and (ii) a crosslinked reaction product between the omniphobic compatibilizer, the third vinyl monomer, and the fourth polyvinyl crosslinking monomer.

11. The thermoset omniphobic composition of claim 9 , wherein:
the omniphobic compatibilizer comprises the at least one free radical initiator functional group, and
the omniphobic compatibilizer is present in the thermoset omniphobic composition as a physical blend with the crosslinked reaction product between the third vinyl monomer and the fourth polyvinyl crosslinking monomer.

12. The thermoset omniphobic composition of claim 9 , wherein:
the third vinyl monomer has a structure according to formula I:
CH 2 ═CR 1 R 2   (I)

where:
R 1 and R 2 are independently selected from hydrogen atoms, halogen atoms, alkyl groups, aryl groups, nitrile groups, ester groups, carboxylic acid groups, ketone groups, ether groups, and heteroatom-substituted derivatives of the foregoing groups.

13. The thermoset omniphobic composition of claim 9 , wherein the fourth polyvinyl crosslinking monomer is an ester reaction product between (i) an acrylic acid compound and (ii) a polyol selected from the group consisting of polyether polyols, glycerol, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, glycerol, trimethylolpropane, 1,2,6-hexanetriol, pentaerythritol, isosorbide, and combinations thereof.

14. The thermoset omniphobic composition of claim 9 , further comprising one or more additives selected from the group consisting of nanoclay, graphene oxide, graphene, silicon dioxide (silica), aluminum oxide, cellulose nanocrystals, carbon nanotubes, titanium dioxide (titania), diatomaceous earth, biocides, pigments, dyes, thermoplastics, and combinations thereof.

15. A coated article comprising:
(a) a substrate; and
(b) a thermoset omniphobic composition according to claim 9 , coated on a surface of the substrate.

16. The coated article of claim 15 , wherein the substrate is selected from the group of metal, plastics, a different thermoset material, glass, wood, fabric (or textile), and ceramics.

17. The coated article of claim 15 , wherein the thermoset omniphobic composition has a thickness ranging from 0.01 μm to 500 μm.

18. The coated article of claim 15 , wherein the thermoset omniphobic composition coating is scratch-resistant, ink-resistant, a

Assignees

• Univ Michigan State

Inventors

• Rabnawaz Muhammad
• Naveed Muhammad

Classifications

• C08F283/124 Primary

  on to polysiloxanes having carbon-to-carbon double bonds · CPC title

• C08F2/50

  with sensitising agents · CPC title

• C09D5/1675

  Polyorganosiloxane-containing compositions · CPC title

• C08G59/3209 Primary

  obtained by polymerisation of unsaturated mono-epoxy compounds · CPC title

• C09D163/00

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