Barrier films and quantum dot polymer composite articles including the same

Abstract

A barrier film comprising: a substrate; a first layer disposed on the substrate and comprising an oxidation product of polysilazane; and a second layer disposed directly on the first layer and comprising a thiol-ene polymer, wherein the polysilazane comprises a repeating unit represented by Chemical Formula 1, wherein R 1 and R 2 are each independently hydrogen, an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an alkylsilyl group, an alkylamino group, an alkoxy group, or an aromatic hydrocarbon group, and wherein the thiol-ene polymer is a polymerization product of a monomer combination including a first monomer having at least two thiol groups at its terminal end and a second monomer having at least two carbon-carbon unsaturated bond-containing groups at its terminal end.

What is claimed is: 
     
         1 . A barrier film comprising:
 a substrate;   a first layer disposed on the substrate and comprising an oxidation product of polysilazane; and   a second layer disposed directly on the first layer and comprising a thiol-ene polymer, and   wherein the polysilazane comprises a repeating unit represented by Chemical Formula 1,   
       
         
           
           
               
               
           
         
         wherein R 1  and R 2  are each independently hydrogen, an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an alkylsilyl group, an alkylamino group, an alkoxy group, or an aromatic hydrocarbon group; and 
         wherein the thiol-ene polymer is a polymerization product of a monomer combination comprising a first monomer having at least two thiol groups at its terminal end and a second monomer having at least two carbon-carbon unsaturated bond-containing groups at its terminal end. 
       
     
     
         2 . The barrier film of  claim 1 , wherein the substrate comprises a polymer, a metal oxide, a metal, or a combination thereof. 
     
     
         3 . The barrier film of  claim 1 , wherein the oxidation product of the polysilazane comprises a silicon oxide, a silicon oxynitride, a polysiloxane, a polysiloxazane, or a combination thereof. 
     
     
         4 . The barrier film of  claim 1 , wherein in the oxidation product of the polysilazane, a ratio of a Si—O moiety to a Si—H moiety determined from FTIR analysis data is greater than or equal to about 0.1 and less than or equal to about 15. 
     
     
         5 . The barrier film of  claim 4 , wherein in the oxidation product of the polysilazane, a ratio of a Si—O moiety to a Si—H moiety determined from FTIR analysis data is greater than or equal to about 2 and less than or equal to about 13. 
     
     
         6 . The barrier film of  claim 1 , wherein the oxidation product of the polysilazane is obtained by treating the polysilazane in contact with oxygen or in contact with oxygen and moisture at a temperature of about 20° C. to about 200° C. 
     
     
         7 . The barrier film of  claim 6 , wherein the polysilazane is treated in contact with a catalyst selected from an amine compound, a platinum compound, a palladium compound, a rhodium compound, and a combination thereof. 
     
     
         8 . The barrier film of  claim 6 , wherein the treating comprises UV irradiation, heating, or a combination thereof. 
     
     
         9 . The barrier film of  claim 1 , wherein the first monomer is represented by Chemical Formula 2 and the second monomer is represented by Chemical Formula 3:
   [R 1  k1 L 1 Y 1 —(SH) m ] k2   Chemical Formula 2
   wherein, in Chemical Formula 2,   R 1  is selected from hydrogen; a substituted or unsubstituted C1 to C30 linear or branched alkyl group; a substituted or unsubstituted C6 to C30 aryl group; a substituted or unsubstituted C3 to C30 heteroaryl group; a substituted or unsubstituted C3 to C30 cycloalkyl group; a substituted or unsubstituted C3 to C30 heterocycloalkyl group; a C1 to C10 alkoxy group; a hydroxy group; —NH 2 ; a substituted or unsubstituted C1 to C30 amine group (—NRR′, wherein R and R′ are independently hydrogen or a C1 to C30 linear or branched alkyl group); an isocyanate group; a halogen; —ROR′ (wherein R is a substituted or unsubstituted C1 to C20 alkylene group and R′ is hydrogen or a C1 to C20 linear or branched alkyl group); an acyl halide (—RC(═O)X, wherein R is a substituted or unsubstituted alkylene group and X is a halogen); —C(═O)OR′ (wherein R′ is hydrogen or a C1 to C20 linear or branched alkyl group); —CN; or —C(═O)ONRR′ (wherein R and R′ are independently hydrogen or a C1 to C20 linear or branched alkyl group),   L 1  is a carbon atom, a substituted or unsubstituted C1 to C30 alkylene group, a substituted or unsubstituted C6 to C30 cycloalkylene group, a substituted or unsubstituted C6 to C30 arylene group, or a substituted or unsubstituted C6 to C30 heteroarylene group, wherein at least one methylene (—CH 2 —) group of the substituted C1 to C30 alkylene group is optionally replaced by sulfonyl (—SO 2 —), carbonyl (—CO—), ether (—O—), sulfide (—S—), sulfoxide (—SO—), ester (—C(═O)O—), amide (—C(═O)NR—) (wherein R is hydrogen or a C1 to C10 alkyl group), or a combination thereof,   Y 1  is a single bond; a substituted or unsubstituted C1 to C30 alkylene group; a substituted or unsubstituted C2 to C30 alkenylene group; or a C1 to C30 alkylene group or a C2 to C30 alkenylene group wherein at least one methylene (—CH 2 —) group is replaced by sulfonyl (—S(═O) 2 —), carbonyl (—C(═O)—), ether (—O—), sulfide (—S—), sulfoxide (—S(═O)—), ester (—C(═O)O—), amide (—C(═O)NR—) (wherein R is hydrogen or a C1 to C10 linear or branched alkyl group), imine (—NR—) (wherein R is hydrogen or a C1 to C10 linear or branched alkyl group), or a combination thereof,   m is an integer of 1 or more,   k1 is an integer of 1 or more and k2 is an integer of 1 or more, and   the sum of m and k2 is an integer of 3 or more,   provided that when Y 1  is not a single bond, m does not exceed the valence of Y 1 , and   provided that the sum of k1 and k2 does not exceed the valence of L 1 ;
   [R 21  k3 L 2 Y 2 —(X) n ] k4   Chemical Formula 3
 
   wherein, in Chemical Formula 3,   X is an aliphatic organic group comprising a carbon-carbon double bond or a carbon-carbon triple bond, an aromatic organic group comprising a carbon-carbon double bond or a carbon-carbon triple bond, or an alicyclic organic group comprising a carbon-carbon double bond or a carbon-carbon triple bond,   R 2  is selected from hydrogen; a substituted or unsubstituted C1 to C30 linear or branched alkyl group; a substituted or unsubstituted C6 to C30 aryl group; a substituted or unsubstituted C3 to C30 heteroaryl group; a substituted or unsubstituted C3 to C30 cycloalkyl group; a substituted or unsubstituted C3 to C30 heterocycloalkyl group; a C1 to C10 alkoxy group; a hydroxy group; NH 2 ; a substituted or unsubstituted C1 to C30 amine group (—NRR′, wherein R and R′ are independently hydrogen or a C1 to C30 linear or branched alkyl group); an isocyanate group; a halogen; —ROR′ (wherein R is a substituted or unsubstituted C1 to C20 alkylene group and R′ is hydrogen or a C1 to C20 linear or branched alkyl group); an acyl halide (—RC(═O)X, wherein R is a substituted or unsubstituted alkylene group and X is a halogen); —C(═O)OR′ (wherein R′ is hydrogen or a C1 to C20 linear or branched alkyl group); —CN; or —C(═O)ONRR′ (wherein R and R′ are independently hydrogen or a C1 to C20 linear or branched alkyl group),   L 2  is a carbon atom, a substituted or unsubstituted C1 to C30 alkylene group, a substituted or unsubstituted C6 to C30 cycloalkylene group, a substituted or unsubstituted C6 to C30 arylene group, or a substituted or unsubstituted C3 to C30 heteroarylene group,   Y 2  is a single bond; a substituted or unsubstituted C1 to C30 alkylene group; a substituted or unsubstituted C2 to C30 alkenylene group; or a C1 to C30 alkylene group or a C2 to C30 alkenylene group wherein at least one methylene (—CH 2 —) group is replaced by sulfonyl (—S(═O) 2 —), carbonyl (—C(═O)—), ether (—O—), sulfide (—S—), sulfoxide (—S(═O)—), ester (—C(═O)O—), amide (—C(═O)NR—) (wherein R is hydrogen or a C1 to C10 linear or branched alkyl group), imine (—NR—) (wherein R is hydrogen or a C1 to C10 linear or branched alkyl group), or a combination thereof, n is an integer of 1 or more,   k3 is an integer of 0 or more,   k4 is an integer of 1 or more, and   the sum of n and k4 is an integer of 3 or more,   provided that when Y 2  is not a single bond, n does not exceed the valence of Y 2 , and   provided that the sum of k3 and k4 does not exceed the valence of L 2 .   
     
     
         10 . The barrier film of  claim 1 , wherein the second layer further comprises a plurality of clay particles dispersed in the thiol-ene polymer. 
     
     
         11 . The barrier film of  claim 1 , wherein the first layer has a thickness of greater than or equal to about 50 nanometers and less than or equal to about 2 micrometers, and the second layer has a thickness of greater than or equal to about 5 micrometers and less than or equal to about 300 micrometers. 
     
     
         12 . A quantum dot-polymer composite article comprising:
 a quantum dot-polymer composite comprising a polymer host matrix and a plurality of quantum dots dispersed in the polymer host matrix; and   a barrier film disposed on at least a portion of the surface of the quantum dot-polymer composite,   wherein the barrier film comprises:   a substrate;   a first layer disposed on the substrate and comprising an oxidation product of polysilazane, wherein the polysilazane comprises a repeating unit represented by Chemical Formula 1,   
       
         
           
           
               
               
           
         
         wherein R 1  and R 2  are each independently hydrogen, an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an alkylsilyl group, an alkylamino group, an alkoxy group, or an aromatic hydrocarbon group; and 
         a second layer disposed directly on the first layer and comprising a thiol-ene polymer, the thiol-ene polymer comprising a polymerization product of a monomer combination comprising a first monomer having at least two thiol groups at its terminal end and a second monomer having at least two carbon-carbon unsaturated bond-containing groups at its terminal end, and 
         wherein the barrier film is disposed in such a manner that a surface of the second layer faces at least a portion of a surface of the quantum dot-polymer composite host matrix. 
       
     
     
         13 . The quantum dot-polymer composite article of  claim 12 , wherein the polymer host matrix comprises a thiol-ene polymer, a cross-linked or non-cross-linked poly(meth)acrylate, a melamine(meth)acrylate polymer, an epoxy polymer, an epoxy(meth)acrylate polymer, a silicone polymer, a silicon(meth)acrylate polymer, a polyurethane(meth)acrylate, a vinyl polymer, or a combination thereof. 
     
     
         14 . The quantum dot-polymer composite article of  claim 12 , wherein the quantum dot-polymer composite has a sheet shape, a bar shape, a pipe shape, or a tube shape. 
     
     
         15 . The quantum dot-polymer composite article of  claim 12 , wherein the oxidation product of the polysilazane comprises a silicon oxide, a silicon oxynitride, a polysiloxane, a polysiloxazane, or a combination thereof. 
     
     
         16 . The quantum dot-polymer composite article of  claim 12 , wherein in the oxidation product of the polysilazane, a ratio of a Si—O moiety to a Si—H moiety determined from FTIR analysis data is greater than or equal to about 0.1 and less than or equal to about 15. 
     
     
         17 . An electronic device comprising the quantum dot-polymer composite article of  claim 12 . 
     
     
         18 . The electronic device of  claim 17 , wherein the electronic device is a display, a light emitting device, a memory device, a laser device, or a solar cell. 
     
     
         19 . The electronic device of  claim 17 , wherein the light emitting device comprises a light source and the film positioned on the light source.