Flexible thermal cure silicone hardcoats
View Patent ↗The present invention relates to thermal cure silicone hardcoat compositions that are prepared with an aqueous/organic solvent silicone dispersion, partial organoalkoxysilane condensate and silylating agent. The novel heat curable silicone hardcoats are useful on various substrates with improved flexibility.
1. A heat curable silicone hardcoat composition comprising:
a) an aqueous/organic solvent silicone dispersion containing colloidal silica and a partial condensate of at least one organoalkoxysilane said dispersion possessing a T 3 :T 2 ratio from about 0.4 to about 1.3; and, added to said dispersion,
b) at least one monofunctional silylating agent having the general formula:
(R 1 ) 3 Si(X)
wherein,
each occurrence of R 1 is independently a monovalent hydrocarbyl group containing from 1 to about 6 carbon atoms, and optionally includes at least one heteroatom selected from the group consisting of oxygen and fluorine; and
X is a halogen; an alkoxy (—OR 2 ), wherein R 2 is a monovalent hydrocarbyl group containing from 1 to about 6 carbon atoms, and optionally includes at least one heteroatom selected from the group consisting of oxygen and fluorine; a hydroxy (—OH); a carboxylate (—OC(═O)R 3 ), wherein R 3 is a hydrogen or a monovalent hydrocarbyl group containing 1 to 6 carbon atoms, and optionally includes at least one heteroatom selected from the group consisting of oxygen and fluorine: a sulfonate (—OSO 2 R 4 ), wherein R 4 is a monovalent hydrocarbyl containing 1 to 6 carbon atoms, and optionally includes at least one heteroatom selected from the group consisting of oxygen and fluorine; an acetamido (—NR 5 C(═O)R 6 ), wherein R 5 and R 6 are a hydrogen or a monovalent hydrocarbyl containing 1 to 6 carbon atoms, and optionally includes at least one heteroatom selected from the group consisting of oxygen and fluorine; an amino (—NR 7 2 ), wherein R 7 is a hydrogen or a monovalent hydrocarbon radical containing 1 to 6 carbon atoms, and optionally includes at least one heteroatom selected from the group consisting of oxygen and fluorine; or a silazane —NR 8 SiR 1 3 ), wherein each occurrence of R 1 is independently a monovalent hydrocarbyl group containing from 1 to about 6 carbon atoms, and optionally includes at least one heteroatom selected from the group consisting of oxygen and fluorine, and R 8 is a hydrogen or a monovalent hydrocarbyl group containing 1 to 6 carbon atoms, and optionally includes at least one heteroatom selected from the group consisting of oxygen and fluorine.
2. The composition of claim 1 wherein the organoalkoxysilane has the general formula:
(R 9 )Si(OR 10 ) 3
wherein,
R 9 is a monovalent hydrocarbyl group containing 1 to 6 carbon atoms, and optionally includes at least one heteroatom selected from the group consisting of oxygen and fluorine; and,
each occurrence of R 10 is independently a monovalent hydrocarbyl group containing 1 to 6 carbon atoms, a hydrogen, a formyl (—C(═O)H), or an acetyl (—C(═O)CH 3 ) group.
3. The composition of claim 1 wherein the organoalkoxysilane is at least one selected from the group consisting of 3,3,3-trifluoropropyltrimethoxysilane, methyltrimethoxysilane, methyltrihydroxysilane, ethyltrimethoxysilane, methyltriacetoxysilane, ethyltriethoxysilane, methyltriethoxysilane, phenyltriethoxysilane and phenyltrimethoxysilane.
4. The composition of claim 1 further comprising at least one additional organoalkoxysilane having the general formula:
(R 11 ) 2 Si(OR 12 ) 2
wherein
each occurrence of R 11 is independently a monovalent hydrocarbyl group containing 1 to 6 carbon atoms, and optionally includes at least one heteroatom selected from the group consisting of oxygen and fluorine; and,
each occurrence of R 12 is independently a monovalent hydrocarbyl group containing 1 to 6 carbon atoms, a hydrogen, a formyl (—C(═O)H), or an acetyl (—C(═O)CH 3 ) group.
5. The composition of claim 4 wherein the organoalkoxysilane is at least one selected from the group consisting of 3,3,3-trifluoropropylmethyldimethoxysilane, dimethyldimethoxysilane, dimethyldihydroxysilane, diethyldimethoxysilane, dimethyldiacetoxysilane, diethyldiethoxysilane, dimethyldiethoxysilane and methylphenyldimethoxysilane.
6. The composition of claim 1 further comprising at least one additional silylating agent having the general formula:
(R 13 )Si(OR 12 ) 3
wherein
R 13 is a monovalent hydrocarbyl group containing 2 to about 6 carbon atoms, and optionally includes at least one heteroatom selected from the group consisting of oxygen and fluorine, with the proviso that R 13 is not the same as R 11 ; and,
each occurrence of R 12 is independently a monovalent hydrocarbyl group containing 1 to 6 carbon atoms, a hydrogen, a formyl (—C(═O)H), or an acetyl (—C(═O)CH 3 ) group.
7. The composition of claim 1 wherein the silylating agent is at least one selected from the group consisting of trimethylchlorosilane, triethylchlorosilane, phenyldimethylchlorosilane, trimethylacetoxysilane, N-(t-butyldimethylsilyl)-N-methyltrifluoroacetamide, t-butyldimethylsilyltrifluoromethanesulfonate, n-butyldimethyl(dimethylamino)silane, hexamethyldisilazane, divinyltetramethyldisilazane, 3,3,3-trifluoropropyldimethylmethoxysilane, trimethylmethoxysilane, trimethylhydroxysilane, triethylmethoxysilane, 3,3,3-trifluoropropyldimethylacetoxysilane and triethylethoxysilane.
8. The composition of claim 1 wherein the organoalkoxysilane is at least one selected from the group consisting of methyltrimethoxysilane and methyltrihydroxysilane.
9. The composition of claim 1 wherein the silylating agent is hexamethyldisilazane.
10. The composition of claim 1 wherein the aqueous/organic solvent silicone dispersion has a T 3 :T 2 ratio from about 0.8 to about 1.2.
11. The composition of claim 1 wherein the aqueous/organic solvent silicone dispersion has a T 3 :T 2 ratio from about 0.85 to about 1.15.
12. The composition of claim 1 further comprising at least one additional component selected from the group consisting of UV absorbing material, hindered amine light stabilizers, other colloidal metal oxides, antioxidants, dye, flow modifiers, leveling agents and surface lubricants.
13. The composition of claim 1 wherein component (a) is present in an amount that ranges from about 85 to about 99.9 weight percent and component (b) is present in an amount that ranges from about 0.1 to about 15 weight percent of the total composition.
14. The composition of claim 1 wherein component (a) is present in an amount that ranges from about 95 to about 99 weight percent and component (b) is present in an amount that ranges from about 1 to about 5 weight percent of the total composition.
15. The composition of claim 1 wherein component (a) is present in an amount that ranges from about 98 to about 99 weight percent and component (b) is present in an amount that ranges from about 1 to about 2 weight percent of the total composition.
16. The cured silicone hardcoat composition of claim 1 .
17. The cured silicone hardcoat composition of claim 16 possessing a critical strain of at least about 3.0 percent.
18. An article of which at least one component is the cured silicone hardcoat composition of claim 1 .
19. A process for making a heat curable silicone hardcoat composition comprising:
a) preparing an aqueous/organic solvent silicone dispersion containing colloidal silica and a partial condensate of at least one organoalkoxysilane, wherein the dispersion possesses a T 3 :T 2 ratio from about 0.4 to about 1.3;
b) adding to said dispersion at least one monofunctional silylating agent having the general formula:
(R 1 ) 3 Si(X)
wherein,
each occurrence of R 1 is independently a monovalent hydrocarbyl group containing from 1 to about 6 carbon atoms, and optionally includes at least one heteroatom selected from the group consisting of oxygen and fluorine; and,
X is a halogen; an alkoxy (—OR 2 ), wherein R 2 is a monovalent hydrocarbyl group containing from 1 to about 6 carbon atoms, and optionally includes at least one heteroatom selected from the group consisting of oxygen and fluorine; a hydroxy (—OH); a carboxvlate (—OC(═O)R 3 ), wherein R 3 is a hydrogen or a monovalent hydrocarbyl group containing 1 to 6 carbon atoms, and optionally includes at least one heteroatom selected from the group consisting of oxygen and fluorine; a sulfonate (—OSO 2 R 4 ), wherein R 4 is a monovalent hydrocarbyl containing 1 to 6 carbon atoms, and optionally includes at least one heteroatom selected from the group consisting of oxygen and fluorine; an acetamido (—NR 5 C(═O)R 6 ), wherein R 5 and R 6 are a hydrogen or a monovalent hydrocarbyl containing 1 to 6 carbon atoms, and optionally includes at least one heteroatom selected from the group consisting of oxygen and fluorine; an amino (—NR 7 2 ), wherein R 7 is a hydrogen or a monovalent hydrocarbon radical containing 1 to 6 carbon atoms, and optionally includes at least one heteroatom selected from the group consisting of oxygen and fluorine; or a silazane (—NR 8 SiR 1 3 ), wherein each occurrence of R 1 is independently a monovalent hydrocarbyl group containing from 1 to about 6 carbon atoms, and optionally includes at least one heteroatom selected from the group consisting of oxygen and fluorine, and R 8 is a hydrogen or a monovalent hydrocarbyl group containing 1 to 6 carbon atoms, and optionally includes at least one heteroatom selected from the group consisting of oxygen and fluorine; and, optionally,
c) cooling the aqueous/organic solvent silicone dispersion prior to adding the silylating agent to provide the heat curable silicone hardcoat composition.
20. A process for making a silicone hardcoat composition comprising curing the composition resulting from claim 19 with heat to obtain a cured silicone hardcoat.
21. The process of claim 19 wherein the organoalkoxysilane has the general formula:
(R 9 )Si(OR 10 ) 3
wherein, R 9 is a monovalent hydrocarbyl group containing 1 to 6 carbon atoms, and optionally includes at least one heteroatom selected from the group consisting of oxygen and fluorine; and, each occurrence of R 10 is independently a monovalent hydrocarbyl group containing 1 to 6 carbon atoms, a hydrogen, a formyl (—C(═O)H), or an acetyl (—C(═O)CH 3 ) group.
22. The process of claim 19 wherein the organoalkoxysilane is at least one selected from the group consisting of 3,3,3-trifluoropropyltrimethoxysilane, methyltrimethoxysilane, methyltrihydroxysilane, ethyltrimethoxysilane, methyltriacetoxysilane, ethyltriethoxysilane, methyltriethoxysilane, phenyltriethoxysilane and phenyltrimethoxysilane.
23. The process of claim 19 further comprising at least one additional organoalkoxysilane having the general formula:
(R 11 ) 2 Si(OR 12 ) 2
wherein,
each occurrence of R 11 is independently a monovalent hydrocarbyl group containing 1 to 6 carbon atoms, and optionally includes at least one heteroatom selected from the group consisting of oxygen and fluorine; and,
each occurrence of R 12 is independently a monovalent hydrocarbyl group containing 1 to 6 carbon atoms, a hydrogen, a formyl (—C(═O)H), or an acetyl (—C(═O)CH 3 ) group.
24. The process of claim 23 wherein the organoalkoxysilane is at least one selected from the group consisting of 3,3,3-trifluoropropylmethyldimethoxysilane, dimethyldimethoxysilane, dimethyldihydroxysilane, diethyldimethoxysilane, dimethyldiacetoxysilane, diethyldiethoxysilane, dimethyldiethoxysilane and methylphenyldimethoxysilane.
25. The process of claim 19 further comprising at least one additional silylating agent having the general formula:
(R 13 )Si(OR 12 ) 3
wherein R 13 is a monovalent hydrocarbyl group containing 2 to about 6 carbon atoms, and optionally includes at least one heteroatom selected from the group consisting of oxygen and fluorine, with the proviso that R 13 is not the same as R 11 ; and,
each occurrence of R 12 is independently a monovalent hydrocarbyl group containing 1 to 6 carbon atoms, a hydrogen, a formyl (—C(═O)H), or an acetyl (—C(═O)CH 3 ) group.
26. The process of claim 19 wherein the silylating agent is at least one selected from the group consisting of trimethylchlorosilane, triethylchlorosilane, phenyldimethylchlorosilane, trimethylacetoxysilane, N-(t-butyldimethylsilyl)-N-methyltrifluoroacetamide, t-butyldimethylsilyltrifluoromethanesulfonate, -butyldimethyl(dimethylamino)silane, hexamethyldisilazane, divinyltetramethyldisilazane, 3,3,3-trifluoropropyldimethylmethoxysilane, trimethylmethoxysilane, trimethylhydroxysilane, triethylmethoxysilane, 3,3,3-trifluoropropyldimethylacetoxysilane and triethylethoxysilane.
27. The process of claim 19 wherein the organoalkoxysilane is at least one selected from the group consisting of methyltrimethoxysilane and methyltrihydroxysilane.
28. The process of claim 19 wherein the silylating agent is hexamethyldisilazane.
29. The process of claim 19 wherein the aqueous/organic solvent silicone dispersion has a T 3 :T 2 ratio from about 0.8 to about 1.2.
30. The process of claim 19 wherein the aqueous/organic solvent silicone dispersion has a T 3 :T 2 ratio from about 0.85 to about 1.15.
31. The process of claim 19 further comprising at least one additional component selected from the group consisting of UV absorbing material, hindered amine light stabilizers, other colloidal metal oxides, antioxidants, dye, flow modifiers, leveling agents and surface lubricants.
32. The process of claim 19 wherein component (a) is present in an amount that ranges from about 85 to about 99.9 weight percent and component (b) is present in an amount that ranges from about 0.1 to about 15 weight percent of the total composition.
33. The process of claim 19 wherein component (a) is present in an amount that ranges from about 95 to about 99 weight percent and component (b) is present in an amount that ranges from about 1 to about 5 weight percent of the total composition.
34. The process of claim 19 wherein component (a) is present in an amount that ranges from about 98 to about 99 weight percent and component (b) is present in an amount that ranges from about 1 to about 2 weight percent of the total composition.
35. The cured silicone hardcoat obtained from the process of claim 19 .
36. The cured silicone hardcoat obtained from the process of claim 19 possessing a critical strain of at least about 3.0 percent.
37. An article of which at least one component is the cured silicone hardcoat obtained from the process of claim 19 .