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

Patent metadata

Field	Value
Publication number	US-12384807-B2
Application number	US-202117997197-A
Country	US
Kind code	B2
Filing date	Apr 27, 2021
Priority date	May 14, 2020
Publication date	Aug 12, 2025
Grant date	Aug 12, 2025

Abstract

Fluorinated photoinitiators and polymerizable compositions including such fluorinated photoinitiators 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 photoinitiator having the formula:

wherein:
X 31 , X 32 , X 33 , X 34 , X 35 are each independently selected from —H, —F, or —CF 3 , with the proviso that at least 3 of X 31 , X 32 , X 33 , X 34 , X 35 are —F, or that at least 1 of X 31 , X 32 , X 33 , X 34 , X 35 is —CF 3 ;
Y 31 , Y 32 , Y 33 , Y 34 , Y 35 are each independently selected from —H, or CH 3 ; and
R 31 is an alkyl group of 1 to 4 carbon atoms.

2. A polymerizable composition comprising:
the fluorinated photoinitiator 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 photoinitiator 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.

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 the fluorinated photoinitiator has a fluorine content of at least 10 wt. %.

7. 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.

8. A multilayer film comprising:
a substrate;
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 .

9. The multilayer film of claim 8 , wherein the free-radically polymerizable monomer, oligomer, or combination thereof is fluorinated.

10. The multilayer film of claim 8 , wherein the free-radically polymerizable monomer, oligomer, or combination thereof has a fluorine content of at least 25 wt. %.

11. The multilayer film of claim 8 , wherein the polymerizable composition is comprised of the fluorinated photoinitiator in an amount of at least 0.1 wt. % based on the weight of the polymerizable composition.

12. The multilayer film of claim 11 , wherein the polymerizable composition is comprised of the fluorinated photoinitiator in an amount of no more than about 10.0 wt. % based on the weight of the polymerizable composition.

13. The multilayer film of claim 8 , wherein the fluorinated photoinitiator has a fluorine content of at least 10 wt. %.

14. The multilayer film of claim 8 , further comprising at least one additional layer adjoining the first layer.

15. The multilayer film of claim 8 , 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.

16. The multilayer film of claim 8 , wherein the adhesion-promoting layer comprises at least one of an oxide, nitride, carbide, boride or a combination thereof of atomic elements 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.

17. An article incorporating the multilayer film according to claim 8 , 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.

18. A process for making a multilayer film, comprising:
forming at least one (co) polymer layer overlaying a major surface of a substrate, wherein the (co)polymer layer is the reaction product of the polymerizable composition of claim 2 , optionally wherein the polymerizable composition is comprised of the fluorinated photoinitiator in an amount of at least 0.1 wt. % based on the weight of the polymerizable composition; and
applying at least one adhesion-promoting layer overlaying the major surface of the substrate.

19. The process of claim 18 , wherein forming the at least one (co) polymer layer further comprises:
evaporating the polymerizable composition;
condensing the evaporated polymerizable composition as a layer overlaying the substrate; and
reacting the polymerizable composition in the layer to form the (co) polymer.

20. The process of claim 18 , wherein reacting the fluorinated photoinitiator with the 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 photoinitiator with the at least one free-radically polymerizable monomer, oligomer, or mixture thereof comprises crosslinking by application of heat, actinic radiation, electron beam radiation, gamma radiation, plasma radiation or a combination thereof.

Assignees

• 3M Innovative Properties Company

Inventors

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

Classifications

• C09D135/02

  Homopolymers or copolymers of esters (C09D135/06, C09D135/08 take precedence) · CPC title

• C09D133/04

  Homopolymers or copolymers of esters {(C09D143/04 takes precedence)} · CPC title

• C09D129/10

  Homopolymers or copolymers of unsaturated ethers (C09D135/08 takes precedence) · CPC title

• C09D5/002

  Priming paints (C09D5/08 takes precedence) · CPC title

• C09D4/00

  Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond {; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16} · CPC title