Nanocomposite formulations for optical applications

1. A formulation comprising a dispersion comprised of:

(i) at least partially capped metal oxide nanocrystals;

(ii) an acrylic polymer comprising bisphenol-A glycerolate dimethacrylate;

(iii) 20% to 90% by weight of the total formulation of a solvent,

(iv) a curing agent or an antioxidant, and

(v) at least one of a crosslinking agent, a thickener, an adhesion promoter, a wetting agent, a leveling agent, a dispersing agent, a plasticizer, or a flexibilizer, wherein

the formulation has an optical transmittance at 450 nm in 50% PGMEA by weight of the total formulation as solvent, when measured in a cuvette with 1 cm path length of 99%-95%, or 95%-90%, 90%-85%, or 85%-80%, or 80%-75%, or 75%-65%, or 65%-60%, or 60%-55%, or 55%-50%, or 50%-45%, or 45%-40%, or 40%-35%, or 35%-30%, or 30%-25%, or 25%-20%, or 20%-15%, or 15%-10%, and wherein

the dispersion does not contain benzyl methacrylate (BMA) or trimethylolpropane triacrylate (TMPTA).

2. The formulation of claim 1 , wherein said metal oxide nanocrystals are zirconium oxide, titanium oxide, hafnium oxide, zinc oxide or a mixture of at least two of said oxides, said at least partially capped metal oxide nanocrystals being optionally produced in the presence of water.

3. The formulation of claim 2 , wherein said at least partially capped metal oxide nanocrystals are at least partially capped with at least one capping agent selected from the group consisting of 2-[2-(2-methoxyethoxy) ethoxy]acetic acid, methoxy(triethyleneoxy) propyltrimethoxysilane, 3-(methacryloyloxy)propyl trimethoxysilane, n-octyl trane, dodecyltrimethoxysilane, m,p-ethylphenethyl trimethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-octyltr methoxysilane, n-octyltriethoxysilane, phenyltrimethoxysilane, 2-[methoxy(polyethyleneoxy) propyl]-trimethoxysilane, 3-aminopropyltrimethoxysilane, 3-mercapto propyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-isocyanato propyltrimethoxysilane, and glycidoxypropyltrimethoxysilane, heptanol, hexanol, octanol, benzyl alcohol, phenol, ethanol, propanol, butanol, oleylalcohol, dodecylalcohol, octadecanol and triethylene glycol monomethyl ether, octanoic acid, acetic acid, propionic acid, acetic acid, oleic acid, and benzoic acid.

4. The formulation of claim 1 wherein the at least partially capped metal oxide nanocrystals are present in the formulation in an amount of less than 10% by weight of the acrylic and at least partially capped nanocrystals, or 10%-20% by weight of the of the acrylic and at least partially capped nanocrystals, or 20%-30% by weight of the of the acrylic and at least partially capped nanocrystals, or 30%-40% by weight of the of the acrylic and at least partially capped nanocrystals, or 40%-50% by weight of the of the acrylic and at least partially capped nanocrystals, or 50%-60% by weight of the of the acrylic and at least partially capped nanocrystals, or 60%-70% by weight of the of the acrylic and at least partially capped nanocrystals, or 70%-80% by weight of the of the acrylic and at least partially capped nanocrystals, or 80%-90% by weight of the of the acrylic and at least partially capped nanocrystals, or 90%-95% by weight of the of the acrylic and at least partially capped nanocrystals.

5. The formulation of claim 1 , wherein the viscosity of the dispersion is less than 5 cPs, or 5 cPs-50 cPs, or 50 cPs-200 cPs, or 200 cPs-400 cPs, or 400 cPs-650 cPs, or 650 cPs-1000 cPs, when measured at 25° C. with a Brookfield RVDV II+ cone and plate viscometer.

6. The formulation of claim 1 , wherein the acrylic polymer is selected from the group consisting of biphenyl-2-ol, ethoxylated esters with acrylic acid (OPPEOA), bisphenol A ethoxylate diacrylates, bisphenol A propoxylate diacrylate, bisphenol F ethoxylate (2 EO/phenol) diacrylate, bisphenol A glycerolate diacrylates, bisphenol A ethoxylate dimethacrylate, trimethylolpropane ethoxylate, (1 EO/OH) methyl ether diacrylate, 1,6-hexanediol diacrylate, tri(ethyleneglycol) diacrylate, ethylene glycol diacrylate, poly(ethylene glycol) diacrylate, glycerol 1,3-diglycerolate diacrylate, di(ethylene glycol) diacrylate, tetra(ethylene glycol) diacrylate, poly(propylene glycol) diacrylate, tri(propylene glycol) diacrylate, 1,6-hexanediol ethoxylate diacrylate, ethylene glycol phenyl ether acrylate, and combinations thereof.

7. The formulation of claim 1 , wherein the solvent is selected from the group consisting of alcohols, glycols, methyl acetates, ethyl acetates, esters, ketones, glycol ethers, glycol esters, such as propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), ethylene glycol monobutyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol butyl ether, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, butoxy ethanol, butoxy propanol, ethoxy ethyl acetate, butoxy ethyl acetate, 2-(isopentyloxy)ethanol, 2-(hexyloxy)ethanol, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, triethylene glycol, triethylene glycol monomethyl ether, dipropylene glycol, dipropylene glycol monomethyl ether, and dipropylene glycol monoethyl ether, ethyl acetate, THF, acetone, and combinations thereof.

8. The formulation of claim 1 , wherein the solvent is present in an amount of 20%-30% by weight of the total formulation, or 30%-40% by weight of the total formulation, or 40%-50% by weight of the total formulation, or 50%-60% by weight of the total formulation, or 60%-70% by weight of the total formulation, or 70%-80% by weight of the total formulation, or 80%-90% by weight of the total formulation.

9. The formulation of claim 1 , wherein the formulation is UV curable.

10. The formulation of claim 1 , wherein the formulation is thermally curable.

11. The formulation of claim 1 , wherein the curing agent is at least one selected from the group consisting of tertiary amines, polymeric benzopherone derivatives, benzophenone, mixtures of benzophenone and methylbenzophenone, diphenyl(2,4,6-trimethylbenzoyl)-phosphine oxide, 1-hydroxy cyclohexyl phenyl ketone, dicumyl peroxide, t-butyl perbenzoate, benzoyl peroxide, t-butyl peracetate, 1,1-di(t-butylperoxy)3,3,5-trimethyl cyclohexane, 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne, n-butyl-4,4-bis(t-butylperoxy valerate), 2,2′-azobisisobutyronitrile (AIBN), 1,1′-azobix(cyclohexane-1-carbonitrile, 2,2′-azobix(2-methylbutyronitrile and 2,2′-azobix[2-(2-imidazolin-2-yl) propane.

12. The formulation of claim 1 , wherein the curing agent is present in an amount of less than 0.5% by weight of the polymer, or 0.5%-1% by weight of the polymer, or 1%-2% by weight of the polymer, or 2%-3% by weight of the polymer, or 3%-4% by weight of the polymer, or 4%-5% by weight of the polymer, or 5%-6% by weight of the polymer, or 6%-7% by weight of the polymer, or 7%-8% by weight of the polymer, or 8%-15% by weight of the polymer.

13. The formulation of claim 1 , wherein the adhesion promoter is at least one selected from the group consisting of 3-amino propyltriethoxysilane, 3-[(methacryloyloxy)propyl]trimethoxysilane, ureidopropyltrimethoxysilane, trimethoxy[3-(methylamino)propyl]silane, acrylate/methacrylate oligomer, acidic triacrylate, trifunctional acid esters and modified methacrylate.

14. The formulation of claim 1 , wherein the adhesion promoter is present in an amount of less than 0.5% by weight of the polymer, or 0.5-1% by weight of the polymer, or 1-5% by weight of the polymer, or 5-10% by weight of the polymer, or 10-15% by weight of the polymer, or 15-30% by weight of the polymer.

15. The formulation of claim 1 , wherein the wetting agent is at least one selected from the group consisting of polyether modified dimethylpolysiloxanes and fluorosurfactants.

16. The formulation of claim 1 , wherein the wetting agent is present in an amount of less than 0.05% by weight of the total formulation, or 0.05-0.1% by weight of the total formulation, or 0.1-0.5% by weight of the total formulation, or 0.5-1% by weight of the total formulation, or 1-2% by weight of the total formulation, or 2-5% by weight of the total formulation.

17. The formulation of claim 1 , wherein the anti-oxidant is at least one selected from the group consisting of pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, octadecyl-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, triethylene glycol-bis-3-(3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, tris(2,4-di-tert-butylphenyl) phosphite, tris(2,4-di-tert-butylphenyl)phosphite and polymers of dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidine ethanol.

18. The formulation of claim 1 , wherein the anti-oxidant is present in an amount less than 0.5% by weight of the total formulation, or 0.5%-1% by weight of the total formulation, or 1%-2% by weight of the total formulation, or 2%-3% by weight of the total formulation, or 3%-4% by weight of the total formulation, or 4%-5% by weight of the total formulation, or 5%-6% by weight of the total formulation, or 6%-7% by weight of the total formulation, or 7%-8% by weight of the total formulation.

19. A scattering formulation comprising a binder formulation and further comprising scattering particles, wherein said binder formulation comprises the formulation of claim 1 .

20. The scattering formulation of claim 19 , wherein the average size of said scattering particles is in the range of 50 nm-2 μm, or 50-100 nm, or 100-200 nm, or 200-300 nm, or 300-400 nm, or 400-500 nm, or 500-600 nm, or 600-700 nm, or 700-800 nm, or 800-900 nm or 900 nm to 1 μm, or 1-1.5 μm, or 1.5-2 μm.

21. The scattering formulation of claim 19 , wherein said scattering particles are present in an amount of 0.1-40% by weight of the total weight of the formulation.

22. The scattering formulation of claim 19 , wherein the scattering particles are selected from a polymer, titanium oxide, silicon dioxide, niobium pentoxide, zirconium oxide, zinc oxide, aluminum oxide, cerium oxide or mixtures of any two of a polymer, titanium oxide, silicon dioxide, niobium pentoxide, zirconium oxide, zinc oxide, aluminum oxide and cerium oxide.

23. A nanocomposite film comprising a cured or partially cured formulation of claim 1 .

24. The nanocomposite film of claim 23 , wherein said film has a refractive index of between 1.6-1.62, or 1.62-1.64, 1.64-1.66, or 1.66-1.68, or 1.68-1.70, or 1.70-1.72, or 1.72-1.74, or 1.76-1.78, or 1.78-1.80, or 1.80-1.82, or 1.82-1.84, or 1.84-1.86, or 1.86-1.88, or 1.88-1.90 when measured at 400 nm.

25. The nanocomposite film of claim 23 , wherein said film has a normal transmittance of 99.99%-99%, or 99%-98%, or 98%-97%, or 97%-96%, or 96%-95%, or 95%-90%, or 90%-85%, or 85%-80%, 80%-75%, or 75%-70%, or 70%-65%, or 65%-60%, or 60%-55%, or 55%-50%, or 50%-45%, or 45%-40%, or 40%-35%, or 35%-30%, or 30%-25%, or 25%-20%, or 20%-15%, or 15%-10% for films that are 4.9-5 microns thick, when measured at a wavelength of 450 nm or 650 nm.

26. The nanocomposite film of claim 23 , wherein a film of at least 1 μm has a surface roughness of 5-4 nm, or 4-3 nm, or 3-2 nm, or 2-1 nm, or 1-0.5 nm, or 0.5-0.1 nm.

27. The nanocomposite film of claim 23 , wherein the amount of the at least partially capped nanocrystals in the fi m is 10%-20%, or 20%-30%, or 30%-40%, or 40%-50%, or 50%-60%, or 60%-70%, or 70%-75%, or 75%-80%, or 80%-85%, or 85%-90%, or 90%-93% by weight of the nanocomposite film.

28. A scattering film comprising a cured or partially cured scattering formulation of claim 19 , wherein said cured or partially cured binder formulation forms a nanocomposite binder.

29. The scattering film of claim 28 , wherein said nanocomposite binder has a refractive index of between 1.6-1.62, or 1.62-1.64, 1.64-1.66, or 1.66-1.68, or 1.68-1.70, or 1.70-1.72, or 1.72-1.74, or 1.76-1.78, or 1.78-1.80, or 1.80-1.82, or 1.82-1.84, or 1.84-1.86, or 1.86-1.88, or 1.88-1.90 when measured at 400 nm.

30. The scattering film of claim 28 , wherein a film of at least 1 μm has a surface roughness of 5-4 nm, or 4-3 nm, or 3-2 nm, or 2-1 nm, or 1-0.5 nm, or 0.5-0.1 nm.

31. An OLED device comprising the nanocomposite film of claim 23 .

32. An OLED device comprising the scattering film of claim 28 .