Durable antireflective film

Abstract

Antireflective films are described having a surface layer comprising a the reaction product of a polymerizable low refractive index composition comprising at least one fluorinated free-radically polymerizable material and surface modified inorganic nanoparticles. A high refractive index layer is coupled to the low refractive index layer. In one emboidiment, the high refractive index layer comprises surface modified inorganic nanoparticles dispersed in a crosslinked organic material. The antireflective film is preferably durable, exhibiting a haze of less than 1.0% after 25 wipes with steel wool using a 3.2 cm mandrel and a mass of 1000 grams.

1 . An antireflective film comprising
 a surface layer comprising the reaction product of a polymerizable low refractive index composition comprising
 at least one fluorinated free-radically polymerizable material, and 
 surface modified inorganic nanoparticles; 
   a high refractive index layer coupled to the low refractive index layer, wherein the high refractive index layer comprises surface modified inorganic nanoparticles dispersed in a crosslinked organic material;   wherein the antireflective film has a haze of less than 1.0% after 25 wipes with steel wool using a 3.2 cm mandrel and a mass of 1000 grams.   
   
   
       2 . The antireflective film of  claim 1  wherein the antireflective film surface has an advancing contact angle with hexadecane of at least 45 degrees. 
   
   
       3 . The antireflective film of  claim 1  wherein the high refractive index layer has a thickness of about 1 micron to about 10 microns. 
   
   
       4 . The antireflective film of  claim 1  wherein the low refractive index layer has an optical thickness of about ¼ wave. 
   
   
       5 . The antireflective film of  claim 1  wherein the antireflective film is free of additional hardcoat layers. 
   
   
       6 . The antireflective film of  claim 1  wherein the low refractive index layer is substantially free of inorganic particles having a diameter of greater than 1 micron. 
   
   
       7 . The antireflective film of  claim 1  wherein the fluorinated free-radically polymerizable material has a fluorine content of at least 25 wt-%. 
   
   
       8 . The antireflective film of  claim 7  wherein the amount of free-radically polymerizable material having a fluorine content of at least 25 wt-% is at least _ wt-% of the polymerizable low refractive index composition. 
   
   
       9 . The antireflective film of  claim 1  wherein the fluorinated free-radically polymerizable material is multi-functional. 
   
   
       10 . The antireflective film of  claim 1  wherein the fluorinated free-radically polymerizable material comprises a fluoropolymer. 
   
   
       11 . The antireflective film of  claim 1  wherein the low refractive index layer composition comprises at least one non-fluorinated crosslinker having at least three multi-acrylate groups. 
   
   
       12 . The antireflective film of  claim 1  wherein the low refractive index polymerizable composition further comprises at least one monofunctional HFPO-fluoropolyether, at least one multifunctional HFPO-fluoropolyether, and mixtures thereof. 
   
   
       13 . The antireflective film of  claim 1  wherein the high refractive index layer comprises at least 5 vol-% surface modified zirconia. 
   
   
       14 . The antireflective film of  claim 1  wherein the high refractive index layer comprises at least 15 vol-% to 40 vol-% of surface modified zirconia. 
   
   
       15 . The antireflective film of  claim 1  wherein the surface modified particles comprise free-radically polymerizable groups selected from acryl groups, methacryl group, and vinyl groups. 
   
   
       16 . The antireflective film of  claim 1  wherein the high refractive index layer is coupled to a light transmissive substrate. 
   
   
       17 . The antireflective film of  claim 16  wherein the substrate comprises a primed surface. 
   
   
       18 . The antireflective film of  claim 7  wherein the primed surface comprises a primed layer having a refractive index that differs from the substrate by less than 0.02 and comprises inorganic oxide nanoparticles having a refractive index of at least 1.60. 
   
   
       19 . The antireflective film of  claim 18  wherein the inorganic oxide nanoparticles are antistatic particles. 
   
   
       20 . The antireflective film of  claim 1  wherein the antireflective film comprises a single low refractive index layer. 
   
   
       21 . The antireflective film or  claim 1  wherein the low refractive index composition comprises at least one amino organosilane ester coupling agent or condensation product thereof. 
   
   
       22 . An optical device comprising the antireflective film of  claim 1 . 
   
   
       23 . An antireflective film comprising
 a low refractive index layer comprising the reaction product of a polymerizable organic composition comprising:   A) a free-radically polymerizable fluorinated polymeric intermediate comprising the reaction product of
 i) at least one multi-functional free-radically polymerizable material having a fluorine content of at least 25 wt-%, and 
 ii) optionally at least one multi-functional free-radically polymerizable material having a fluorine content ranging from 0 to less than 25 wt-%, 
   wherein the total amount of multi-functional materials is at least about 25 wt-% based on wt-% solids of the polymerizable organic composition;   B) at least one fluorinated free-radically polymerizable material; and   C) surface modified inorganic nanoparticles;   a high refractive index layer coupled to the low refractive index layer wherein the high refractive index layer comprises surface modified inorganic nanoparticles dispersed in a crosslinked organic material.   
   
   
       24 . An antireflective film comprising
 a low refractive index layer comprising the reaction product of a polymerizable composition comprising
 at least one free-radically polymerizable fluoropolymer, 
 at least one amino organosilane ester coupling agent or condensation product thereof, 
 at least one non-fluorinated crosslinker having at least three free-radically polymerizable groups, and 
 surface modified inorganic nanoparticles; 
   a high refractive index layer having a thickness of at least 1 micron coupled to the low refractive index layer wherein the high refractive index layer is selected from an inorganic material having a refractive index of at least 1.60 or a crosslinked organic material comprising surface modified inorganic oxide particles.   
   
   
       25 . The antireflective film composition of  claim 24 , wherein the free-radically polymerizable fluoropolymer comprises an amorphous fluoropolymer. 
   
   
       26 . The antireflective film of  claim 22  wherein the amorphous fluoropolymer is selected from the group consisting of a Cl-containing fluoroelastomer, a Br-containing fluoroelastomer, an I-containing fluoroelastomer, and a C═C containing fluoroelastomer. 
   
   
       27 . The antireflective film of  claim 24  wherein the amino organosilane ester coupling agent or condensation product thereof is selected from the group consisting of 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, (amino ethylaminomethyl)phenethyltrimethoxysilane, (amino ethylaminomethyl)phenethyltriethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldiethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane, 4-aminobutyltrimethoxysilane, 4-aminobutyltriethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropyldimethylmethoxysilane, 3-aminopropyldimethylethoxysilane, 2,2-dimethoxy-1-aza-2-silacyclopentane-1-ethanamine, 2,2-diethoxy-1-aza-2-silacyclopentane-1-ethanamine, 2,2-diethoxy-1-aza-2-silacyclopentane, 2,2-dimethoxy-1-aza-2-silacyclopentane, 4-aminophenyltrimethoxy silane, and 3-phenylaminopropyltrimethoxy silane. 
   
   
       28 . An antireflective film comprising
 a light transmissive substrate;   a primer layer comprising antistatic particles coupled to the substrate;   a high refractive index layer coupled to the primer layer; and   a low refractive index layer coupled to the high refractive index layer.   
   
   
       29 . The antireflective film of  claim 28  wherein the primer layer has a refractive index that differs from the substrate by less than 0.02. 
   
   
       30 . The antireflective film of  claim 28  wherein the antistatic particles have a refractive index of at least 1.60.