Fluorinated coupling agents and fluorinated (co)polymer layers made using the same

Patent metadata

Field	Value
Publication number	US-12305063-B2
Application number	US-202117997185-A
Country	US
Kind code	B2
Filing date	Apr 27, 2021
Priority date	May 14, 2020
Publication date	May 20, 2025
Grant date	May 20, 2025

Abstract

Fluorinated coupling agents and polymerizable compositions including such fluorinated coupling agents and at least one free-radically polymerizable monomer, oligomer, or mixture thereof. Multilayer films including a substrate and at least a first layer overlaying a surface of the substrate also are described, in which the at least first layer includes a (co)polymer obtained by polymerizing the foregoing polymerizable compositions. Processes for making a multilayer film using the polymerizable composition also are taught. Articles including the multilayer film also are disclosed, in which the article preferably is selected from a photovoltaic device, a display device, a solid-state lighting device, a sensor, a medical or biological diagnostic device, an electrochromic device, light control device, or a combination thereof.

First claim

The invention claimed is:

1. A fluorinated coupling agent having the formula:

wherein R f1 is a monovalent perfluorooxyalkyl;
R 13 is a divalent alkylene group, said alkylene groups optionally containing one or more catenary oxygen atoms;
R 11 is —[OC(O)—NH—R 13 ] m1 OC(O)CR 15 ═CH 2 or —OC(O)—NH—R 16 (—OC(O)CR 15 —CH 2 ) 2 ;
Y is a hydrolysable group;
R 14 is a monovalent alkyl or aryl group;
p is 1, 2, or 3;
R 15 is H or CH 3 ;
R 16 is a polyvalent alkylene group, said polyvalent alkylene group optionally containing one or more catenary oxygen atoms; and
m1 is 1 or 0.

2. A polymerizable composition comprising:
the fluorinated coupling agent of claim 1 ; and
at least one free-radically polymerizable monomer, oligomer, or mixture thereof,
optionally wherein the polymerizable composition is comprised of the fluorinated coupling agent in an amount of at least 0.1 wt. % based on the weight of the polymerizable composition.

3. The polymerizable composition of claim 2 , wherein the free-radically polymerizable monomer, oligomer, or combination thereof is fluorinated, optionally wherein the polymerizable composition is comprised of the fluorinated coupling agent in an amount of no more than about 50 wt. % based on the weight of the polymerizable composition.

4. The polymerizable composition of claim 2 , wherein the free-radically polymerizable monomer, oligomer, or combination thereof has a fluorine content of at least 25 wt. %.

5. The polymerizable composition of claim 2 , wherein the polymerizable composition is comprised of a fluorinated oligomer including a perfluorooxyalkylene group.

6. The polymerizable composition of claim 2 , wherein each hydrolysable group Y is independently selected from an alkoxy group, an acetoxy group, an aryloxy group, and a halogen.

7. The polymerizable composition of claim 2 , wherein the fluorinated coupling agent has a calculated number average molecular weight of no greater than 3000 g/mole.

8. The polymerizable composition of claim 2 , wherein the fluorinated coupling agent has a fluorine content of at least 20 wt. %.

9. The polymerizable composition of claim 2 , further comprising at least one of a (meth)acrylic monomer or oligomer, optionally wherein the at least one (meth)acrylic monomer or oligomer comprises HFPO oligomer diacrylate of the structure CH 2 ═CHC(O)O—H 2 C—(CF 3 )CF—[OCF 2 (CF 3 )CF] s —O(CF 2 ) u O—[CF(CF 3 )CF 2 O] t —CF(CF 3 )—CH 2 —OC(O)CH═CH 2 , wherein u is from 2 to 6 and s and t are independently integers of 2 to 25.

10. A multilayer film comprising:
a substrate; and
at least a first layer overlaying a surface of the substrate,
wherein the first layer comprises a (co) polymer obtained by polymerizing the polymerizable composition of claim 2 ,
optionally wherein the polymerizable composition is comprised of the fluorinated coupling agent in an amount of at least 0.1 wt. % based on the weight of the polymerizable composition.

11. The multilayer film of claim 10 , wherein the polymerizable composition is comprised of the fluorinated coupling agent in an amount of no more than about 50 wt. % based on the weight of the fluorinated polymerizable composition.

12. The multilayer film of claim 10 , wherein the free-radically polymerizable monomer, oligomer, or combination thereof is fluorinated, optionally wherein the free-radically polymerizable monomer, oligomer, or combination thereof has a fluorine content of at least 25 wt. %.

13. The multilayer film of claim 10 , wherein the substrate comprises a flexible transparent polymeric film, optionally wherein the substrate comprises polyethylene terephthalate (PET), polyethylene terephthalate glycol (PETg), polyethylene napthalate (PEN), heat stabilized PET, heat stabilized PEN, polyoxymethylene, polyvinylnaphthalene, polyetheretherketone, a fluoropolymer, polycarbonate, polymethylmeth(meth)acrylate, poly α-methyl styrene, polysulfone, polyphenylene oxide, polyetherimide, polyethersulfone, polyamideimide, polyimide, polyphthalamide, cyclic olefin polymer (COP), cyclic olefin copolymer (COC), triacetate cellulose (TAC), or combinations thereof.

14. The multilayer film of claim 10 , further comprising at least one additional layer adjoining the first layer.

15. The multilayer film of claim 10 , further comprising an adhesion-promoting layer between the substrate and the first layer, the adhesion-promoting layer comprising at least one of an oxide, nitride, carbide, boride or a combination thereof of at least one atomic element selected from Groups IIA, IIIA, IVA, IVB, VA, VB, VIA, VIIA, IB, or IIB; a metal or a combination thereof selected from Groups IIIA, IIIB, IVA, IVB, VB, VIB, VIIIB; a rare-earth metal or a combination thereof; or a (meth)acrylic (co) polymer or a combination thereof, optionally wherein the oxide, nitride, carbide or boride comprises aluminum, indium, silicon, tin, titanium, zirconium, hafnium, vanadium, niobium, tantalum, cerium, strontium or a combination thereof; and the metal or metal alloy comprises aluminum, silicon, germanium, copper, silver, gold, titanium, zirconium, chromium, nickel or a combination thereof.

16. An article incorporating a multilayer film according to claim 10 , wherein the article is selected from a photovoltaic device, a display device, a solid-state lighting device, a sensor, a medical or biological diagnostic device, an electrochromic device, light control device, or a combination thereof.

17. A process for making a multilayer film, comprising:
forming at least one (co) polymer layer overlaying a substrate, wherein the (co) polymer layer is the reaction product of the polymerizable composition of claim 2 ; and
applying at least one adhesion-promoting layer overlaying the substrate, wherein the adhesion-promoting layer comprises an inorganic oxide, nitride, oxynitride, oxycarbide, hydroxylated (co) polymer, or a combination thereof.

18. The process of claim 17 , wherein forming the (co) polymer layer further comprises:
evaporating the polymerizable composition;
condensing the evaporated polymerizable composition or the (co) polymer as a layer overlaying the substrate; and
reacting the polymerizable composition in the layer to form the (co) polymer, optionally wherein the polymerizable composition is comprised of the fluorinated coupling agent in an amount of at least 0.1 wt. % based on the weight of the polymerizable composition.

19. The process of claim 17 , wherein applying the adhesion-promoting layer comprises depositing onto the substrate at least one of a metal oxide, metal oxide precursor, metal nitride, metal nitride precursor, metal oxynitride, metal oxynitride precursor, oxycarbide, oxycarbide precursor, hydroxylated (co) polymer, or hydroxylated (co) polymer precursor, wherein depositing is achieved using sputter deposition, reactive sputtering, thermal evaporation, electron-beam evaporation, chemical vapor deposition, plasma-assisted chemical vapor deposition, atomic layer deposition, plasma-assisted atomic layer deposition, or a combination thereof.

20. The process of claim 17 , wherein reacting the fluorinated coupling agent with at least one free-radically polymerizable monomer, oligomer, or mixture thereof occurs at least in part in the layer overlaying the substrate, optionally wherein the reacting of the fluorinated coupling agent with at least one free-radic

Assignees

• 3M Innovative Properties Company

Inventors

• Homnick Paul J
• Klun Thomas P
• Pietz Brandon R
• Lyons Christopher S
• Stensvad Karl K

Classifications

• C23C14/3464

  using more than one target (C23C14/56 takes precedence) · CPC title

• C23C14/24

  Vacuum evaporation · CPC title

• C23C14/12

  Organic material · CPC title

• C23C14/08

  Oxides (C23C14/10 takes precedence) · CPC title

• C23C14/024

  Deposition of sublayers, e.g. to promote adhesion of the coating (C23C14/027 takes precedence) · CPC title