Process for making an anti-reflective coating composition and a porous coating made therefrom
The invention relates to a process of making an anti-reflective coating composition comprising the steps of 1) preparing an oil-in-water emulsion by mixing an apolar organic compound A; a cationic addition copolymer C as emulsion stabilizer; and aqueous medium of pH 2-6; at a mass ratio C/A of 0.1 to 2, to result in 1-50 mass % (based on emulsion) of emulsified droplets of average particle size 30-300 nm; and 2) providing an inorganic oxide shell layer to the emulsified droplets by adding to the emulsion obtained in step 1) at least one inorganic oxide precursor, to result in organic-inorganic core-shell nano-particles with mass ratio core/shell of from 0.2 to 25. An advantage of this process is that the dispersion of nano-particles obtained is stable under different conditions, and allows altering its concentration and solvent system, and addition of different binders and auxiliary components. The invention also relates to a coating composition as obtained with said process, and to a process of applying a porous anti-reflective coating on a substrate using such composition, and to the resulting coated substrate.
1. A process for making an anti-reflective coating composition comprising the steps of:
1) preparing an oil-in-water emulsion by mixing an organic compound A; an emulsion stabilizer C; and aqueous medium of pH 2-6; at a mass ratio C/A of 0.1 to 2, to result in 1-50 mass % based on emulsion of emulsified droplets of particle size 30-300 nm wherein the particle size is the Z-averaged hydrodynamic diameter measured by Dynamic Light Scattering (DLS); and
2) providing an inorganic oxide shell layer to the emulsified droplets by adding to the emulsion obtained in step 1) at least one inorganic oxide precursor, to result in organic-inorganic core-shell nano-particles with mass ratio core/shell of from 0.2 to 25 where the core is the sum of compound A and emulsion stabilizer C and the shell is formed of a metal oxide equivalent consisting of a mass of metal oxide resulting from complete conversion of at least one inorganic metal oxide precursor, wherein
the compound A is an apolar organic compound having a solubility in water of at most 5 kg/m 3 , and the emulsion stabilizer C is a cationic addition copolymer having an overall positive zeta potential and comprising at least one monomer unit having a cationic charge and at least one monomer unit being neutral or non-ionic.
2. The process according to claim 1 , wherein the compound A is a non-polymeric compound.
3. The process according to claim 1 , wherein the at least one inorganic precursor comprises a metal salt, a metal chelate, an organo-metallic compound, or a combination thereof.
4. The process according to claim 1 , wherein the compound A has a boiling point of at least 10° C. and at most 300° C.
5. The process according to claim 1 , wherein the compound A has solubility in water at room temperature of at most 3 kg/m 3 .
6. The process according to 1 , wherein the copolymer C is the reaction product of:
(i) 1-25 mole % of at least one cationic or basic monomer M1;
(ii) 50-99 mole % of at least one non-ionic apolar monomer M2; and
(iii) 0-25 mole % of at least one polar, anionic or acidic monomer M3; with the sum of M1, M2, and M3 being 100%.
7. The process according to claim 5 , wherein the copolymer C is the reaction product of:
(i) 5-15 mole % of at least one monomer M1;
(ii) 75-95 mole % of at least one monomer M2; and
(iii) 0-10 mole % of at least one monomer M3; with the sum of M1, M2, and M3 being 100%.
8. The process according to claim 5 , wherein the copolymer C is the reaction product of 5-15 mole % of at least one monomer M1 selected from the group consisting of amino-functional (meth)acrylates and (meth)acrylamides; and 85-95 mole % of at least one monomer M2 selected from the group consisting of C1-C18 alkyl (meth)acrylates.
9. The process according to claim 1 , wherein the mass ratio C/A is 0.15-1.0.
10. The process according to claim 1 , wherein the emulsified droplets have a particle size of 35-200 nm.
11. The process according to claim 1 , wherein the at least one inorganic precursor comprises an alkoxy silane.
12. The process according to claim 1 , which further comprises
3) adding 2-70 mass % of at least one polymeric or polymerizable compound as binder, wherein mass% is based on the sum of core-shell particles and binder.
13. The process according to claim 11 , further comprising adding 5-50 mass % of at least one compound as binder.
14. The process according to claim 13 , wherein the binder is at least one inorganic oxide precursor.
15. The process according to claim 14 , wherein the inorganic oxide precursor is selected from the group consisting of metal alkoxides, metal chelates, metal salts and mixtures thereof.
16. The process according to claims 14 , wherein the at least one inorganic oxide precursor comprises an alkoxy silane.
17. A process for making an anti-reflective coating on a transparent substrate comprising the steps of:
(a) applying an anti-reflective coating composition to the substrate to form a coating layer thereon; and
(b) drying the coating layer, wherein
the anti-reflective coating comprises organic-inorganic core-shell nano-particles having a particle size of 30-300 nm, wherein the particle size is a Z-averaged hydrodynamic diameter measured by DLS, and wherein
the organic-inorganic core-shell nano-particles have a mass ratio of core/shell of from 0.2 to 25, and wherein
the core is a sum of an organic compound A and an emulsion stabilizer C at a mass ratio C/A of 0.1 to 2, and wherein
the shell is formed of a metal oxide equivalent consisting of a mass of metal oxide resulting from complete conversion of at least one inorganic metal oxide precursor, wherein
the compound A is an apolar organic compound having a solubility in water of at most 5 kg/m 3 , and the emulsion stabilizer C is a cationic addition copolymer having an overall positive zeta potential and comprising at least one monomer unit having a cationic charge and at least one monomer unit being neutral or non-ionic.
18. The process according to claim 17 , wherein the compound A is a non-polymeric compound.
19. The process according to claim 17 , wherein the at least one inorganic precursor comprises a metal salt, a metal chelate, an organo-metallic compound, or a combination thereof.
20. The process according to claim 17 , wherein the compound A has a boiling point of at least 10° C. and at most 300° C.
21. The process according to claim 17 , wherein the compound A has solubility in water at room temperature of at most 3 kg/m 3 .
22. The process according to 17 , wherein the copolymer C is the reaction product of:
(i) 1-25 mole % of at least one cationic or basic monomer M1;
(ii) 50-99 mole % of at least one non-ionic apolar monomer M2; and
(iii) 0-25 mole % of at least one polar, anionic or acidic monomer M3; with the sum of M1, M2, and M3 being 100%.
23. The process according to claim 22 , wherein the copolymer C is the reaction product of:
(i) 5-15 mole % of at least one monomer M1;
(ii) 75-95 mole % of at least one monomer M2; and
(iii) 0-10 mole % of at least one monomer M3; with the sum of M1, M2, and M3 being 100%.
24. The process according to claim 22 , wherein the copolymer C is the reaction product of 5-15 mole % of at least one monomer M1 selected from the group consisting of amino-functional (meth)acrylates and (meth)acrylamides; and 85-95 mole % of at least one monomer M2 selected from the group consisting of C1-C18 alkyl (meth)acrylates.
25. The process according to claim 17 , wherein the mass ratio C/A is 0.15-1.0.
26. The process according to claim 17 , wherein the emulsified droplets have a particle size of 35-200 nm.
27. The process according to any one of claim 17 , wherein the at least one inorganic precursor comprises an alkoxy silane.
28. The process according to any one of claim 17 , which further comprises:
(c) adding 2-70 mass % of at least one polymeric or polymerizable compound as binder, wherein mass % is based on the sum of core-shell particles and binder.
29. The process according to claim 27 , further comprising adding 5-50 mass % of at least one compound as binder.
30. The process according to claim 29 , wherein the binder is at least one inorganic oxide precursor.
31. The process according to claim 30 , wherein the inorganic oxide precursor is selected from the group consisting of metal alkoxides, metal chelates, metal salts and mixtures thereof.
32. The process according to claim 30 , wherein the at least one inorganic oxide precursor comprises an alkoxy silane.
33. The process according to claim 17 , wherein step (ii) comprises drying and curing the applied coating layer.
34. The process according to claim 33 , wherein drying and curing of step (ii) is performed at a temperature of at most 250° C.
35. A method for making organic-inorganic core-shell particles comprising:
(i) preparing an oil-in-water emulsion by mixing an organic compound A; an emulsion stabilizer C; and aqueous medium of pH 2-6; at a mass ratio C/A of 0.1 to 2, to result in 1-50 mass % based on emulsion of emulsified droplets of particle size 30-300 nm wherein the particle size is the Z-averaged hydrodynamic diameter measured by DLS; and
(i) providing an inorganic oxide shell layer to the emulsified droplets by adding to the emulsion obtained in step 1) at least one inorganic oxide precursor, to result in organic-inorganic core-shell nano-particles with mass ratio core/shell of from 0.2 to 25 where the core is the sum of compound A and emulsion stabilizer C and shell is formed of a metal oxide equivalent consisting of a mass of metal oxide resulting from complete conversion of at least one inorganic metal oxide precursor, wherein
the compound A is an apolar organic compound having a solubility in water of at most 5 kg/m 3 , and the emulsion stabilizer C is a cationic addition copolymer having an overall positive zeta potential comprising at least one monomer unit having a cationic charge and at least one monomer unit being neutral or non-ionic.
36. A dispersion comprising organic-inorganic core-shell nano-particles, wherein the organic core comprises a cationic addition polymer C and an apolar organic compound A, and wherein the inorganic shell comprises an inorganic oxide, and wherein copolymer C is a copolymer which is a reaction product of the following monomers:
(a) at least one cationic or basic monomer (M1);
(b) at least one neutral or non-ionic monomer (M2); and
(c) optionally at least one polar, anionic or acidic monomer (M3), wherein the particles have a particle size of at most 300 nm and at least 35 nm wherein the particle size is the Z-averaged hydrodynamic diameter as measured by Dynamic Light Scattering (DLS).
37. A coating composition comprising the dispersion of claim 36 .
38. A coated substrate comprising a substrate and a coating layer on a surface of the substrate, wherein the coating layer comprises the dispersion of claim 36 .
39. The process according to claim 6 , wherein the at least one cationic or basic monomer M1 is a vinyl monomer with a tertiary amine group.
40. The process according to claim 22 , wherein the at least one cationic or basic monomer M1 is a vinyl monomer with a tertiary amine group.