Surface protective coating and methods of use thereof
View Patent ↗A coating composition suitable for providing a thermoformable hardcoat is disclosed. The composition contains a silane-containing oligomer (A), a silane (B) having the general formula R 3 c SiX (4-d) wherein each occurrence of R 3 is independently a C1-C8 alkyl, C2-C8 alkenyl or C6-C20 aryl, each occurrence of X is a halogen atom, C1-C6 alkoxy, C1-C6 acyloxy, C1-C6 alkenoxy or hydroxide; d is 0, 1 or 2, a metal oxide (C) and a condensation catalyst (D) wherein components (A), (B) and (C) are hydrolytically condensed in the presence of component (D) to achieve a T 3 to T 2 ratio of from about 0.3 to about 2.5.
1. A coating composition suitable for providing a thermoformable hardcoat comprising:
(A) at least one silane-containing oligomer having the general formula (1)
wherein each occurrence of R′ is independently a C1-C8 alkyl or C6-C20 aryl; each occurrence of R 2 is independently a C2-C8 alkylene; each occurrence of X is independently a halogen atom, C1-C6 alkoxy, C1-C6 acyloxy, C1-C6 alkenoxy or hydroxide; each occurrence of Y is independently an oxygen or R 2 ; a is an integer between 0 and 30; b is 2 or 3 and c is an integer between 0 and 6, and/or a partial hydrolytic condensate thereof;
(B) at least one silane having the general formula (2):
R 3 e SiX (4-e ) (2)
wherein each occurrence of R 3 is independently a C1-C8 alkyl, C2-C8 alkenyl or C6-C20 aryl, each occurrence of X is a halogen atom, C1-C6 alkoxy, C1-C6 acyloxy, C1-C6 alkenoxy or hydroxide; e is 0, 1 or 2, and/or a partial hydrolytic condensate thereof;
(C) metal oxide; and
(D) condensation catalyst;
wherein components (A), (B) and (C) are hydrolytically condensed in the presence of component (D) to achieve a T 3 to T 2 ratio of from about 0.83 to about 2.5.
2. The coating composition of claim 1 wherein in formula (1), each occurrence of R 1 is independently a C1-C5 alkyl and each occurrence of X is independently a C1-C4 alkoxy.
3. The coating composition of claim 1 wherein in formula (2), each occurrence of R 3 is independently a C1-C5 alkyl, and each occurrence of X is independently a C1-C6 alkoxy group.
4. The coating composition of claim 1 wherein the metal oxide is colloidal silica.
5. The coating composition of claim 1 wherein component (D) is a thermal cure catalyst tetrabutylammonium carboxylate having a structural formula (3)
[(C 4 H 9 ) 4 N + [OC(O)—R] − , (3),
wherein R is selected from the group consisting of hydrogen, alkyl groups containing about 1 to about 8 carbon atoms, and aromatic groups containing about 6 to 20 carbon atoms.
6. The coating composition of claim 5 wherein R is a C1-C4 alkyl.
7. The coating composition of claim 5 wherein component (D) is selected from the group consisting of tetra-n-butylammonium acetate (TBAA), tetra-n-butylammonium formate, tetra-n-butyl ammonium benzoate, tetra-n-butylammonium-2-ethylhexanoate, tetra-n-butylammonium-p-ethylbenzoate, tetra-n-butylammonium propionate and combinations thereof.
8. An article having at least one surface coated with the coating composition of claim 1 .
9. The article of claim 8 wherein said surface of said article has first been primed with a primer composition prior to being coated with said coating composition.
10. The article of claim 8 wherein the article comprises a synthetic organic polymer.
11. The article of claim 10 wherein said organic polymer is a polycarbonate.
12. The article of claim 8 wherein said coating composition has been pre-cured on said surface of said article.
13. The article of claim 12 wherein said coating composition has been cured to provide a cured coating on said surface of said article.
14. The article of claim 12 wherein said article has been thermoformed after said pre-curing of said coating composition.
15. The article of claim 12 wherein said article has been thermoformed in the temperature range of from about 100° C. to about 300° C. for 5 to 30 minutes.
16. The article of claim 8 wherein said coating composition has been pre-cured in the temperature range of 60° C. to 90° C. for 15 to 60 minutes.
17. The article of claim 8 wherein said coating composition has been cured to provide a cured coating on said surface of said article.
18. The article of claim 17 wherein said cured coating has a T g below 150° C. and exhibits less than 20% delta haze after 500 cycles of taber abrasion testing according to ASTM D1044.
19. The article of claim 17 wherein said cured coating exhibits greater than 5% strain and less than 20% delta haze after 500 cycles of taber abrasion testing according to ASTM D1044.
20. The article of claim 17 wherein said article is an automotive glazing that meets ANSI Z26.1 for automotive glazing applications equal to or less than AS2 requirements.
21. The article of claim 17 wherein said cured coating exhibits no cracking or delamination after vibration or cyclic strain loading of said article.
22. The article of claim 8 wherein said article is a window or a solar cell cover.
23. A process for preparing a coated article having a partially cured or fully cured coating comprising the steps of: 1) providing a coating composition according to claim 1 and a substrate, 2) applying said coating composition to said substrate; 3) heating said coating composition to an elevated temperature for a time sufficient to at least partially or fully cure said coating composition, thereby making said coated article having a partially cured or fully cured coating.
24. The process of claim 23 wherein said coating composition is heated at a temperature of from about 60° C. to 90° C. for about 15 to 60 minutes to at least partially cure said coating composition.
25. The process of claim 24 further comprising the steps of heating said article having an at least partially cured coating to a temperature of from about 160° C. to about 180° C. to provide a thermoformable coated article, and forming said thermoformable coated article into a desired shape.
26. The process of claim 23 wherein said coated substrate is heated to a temperature of from about 160° C. to about 180° C. to fully cure said coating composition.
27. The coating composition of claim 1 , further comprising a copolymer of CR 1 R 1 ═CR 1 C(O)OR 1 and CR 1 R 1 ═CR 1 C(O)OR 2 SiX d R 1 (3-d) , wherein each occurrence of R 1 is independently a C1-C8 alkyl or C6-C20 aryl; each occurrence of R 2 is independently a C2-C8 alkylene; each occurrence of X is independently a halogen atom, C1-C6 alkoxy, C1-C6 acyloxy, C1-C6 alkenoxy or hydroxide; and d is 1, 2 or 3.
28. A coating composition suitable for providing a thermoformable hardcoat comprising:
(A) at least one silane-containing oligomer having the general formula (1)
wherein each occurrence of R 1 is independently a C1-C8 alkyl or C6-C20 aryl; each occurrence of R 2 is independently a C2-C8 alkylene; each occurrence of X is independently a halogen atom, C1-C6 alkoxy, C1-C6 acyloxy, C1-C6 alkenoxy or hydroxide; each occurrence of Y is an oxygen or R 2 ; a is an integer between 0 and 30; b is 2 or 3 and c is an integer between 0 and 6, and/or a partial hydrolytic condensate thereof;
(B) at least one silane having the general formula (2):
R 3 e SiX (4-e) (2)
wherein each occurrence of R 3 is independently a C1-C8 alkyl, C2-C8 alkenyl or C6-C20 aryl, each occurrence of X is a halogen atom, C1-C6 alkoxy, C1-C6 acyloxy, C1-C6 alkenoxy or hydroxide; e is 0, 1 or 2, and/or a partial hydrolytic condensate thereof;
(C) metal oxide; and
(D) condensation catalyst;
(E) a UV absorber that is capable of co-condensing with at least one of components (A), (B) or (C);
wherein components (A), (B), (C) and (E) are hydrolytically condensed in the presence of component (D) to achieve a T 3 to T 2 ratio of from about 0.83 to about 2.5.
29. The coating composition of claim 28 wherein the UV absorber is selected from the group consisting of 4-[gamma-(trimethoxysilyl) propoxyl]-2-hydroxy benzophenone, 4-[gamma-(triethoxysilyl)propoxyl]-2-hydroxy benzophenone, 4,6-dibenzoyl-2-(3-triethoxysilylpropyl) resorcinol, and combinations thereof.
30. An article having at least one surface coated with the coating composition of claim 28 .
31. The coating composition of claim 28 , further comprising a copolymer of CR 1 R 1 ═CR 1 C(O)OR 1 and CR 1 R 1 ═CR 1 C(O)OR 2 SiX d R 1 (3-d) , wherein each occurrence of R 1 is independently a C1-C8 alkyl or C6-C20 aryl; each occurrence of R 2 is independently a C2-C8 alkylene; each occurrence of X is independently a halogen atom, C1-C6 alkoxy, C1-C6 acyloxy, C1-C6 alkenoxy or hydroxide; and d is 1, 2 or 3.
32. An article comprising:
a substrate having a surface coated with a coating composition suitable for providing a thermoformable hardcoat comprising:
(A) at least one silane-containing oligomer having the general formula (1)
wherein each occurrence of R′ is independently a C1-C8 alkyl or C6-C20 aryl; each occurrence of R 2 is independently a C2-C8 alkylene; each occurrence of X is independently a halogen atom, C1-C6 alkoxy, C1-C6 acyloxy, C1-C6 alkenoxy or hydroxide; each occurrence of Y is independently an oxygen or R 2 ; a is an integer between 0 and 30; b is 2 or 3 and c is an integer between 0 and 6, and/or a partial hydrolytic condensate thereof;
(ii) a copolymer of CR 1 R 1 ═CR 1 C(O)OR 1 and CR 1 R 1 ═CR 1 C(O)OR 2 SiX d R 1 (3-d) , wherein each occurrence of R 1 is independently a C1-C8 alkyl or C6-C20 aryl; each occurrence of R 2 is independently a C2-C8 alkylene; each occurrence of X is independently a halogen atom, C1-C6 alkoxy, C1-C6 acyloxy, C1-C6 alkenoxy or hydroxide; and d is 1, 2 or 3; and combinations thereof;
(B) at least one silane having the general formula (2):
R 3 e SiX (4-e) (2)
wherein each occurrence of R 3 is independently a C1-C8 alkyl, C2-C8 alkenyl or C6-C20 aryl, each occurrence of X is a halogen atom, C1-C6 alkoxy, C1-C6 acyloxy, C1-C6 alkenoxy or hydroxide; e is 0, 1 or 2, and/or a partial hydrolytic condensate thereof;
(C) metal oxide; and
(D) condensation catalyst;
wherein components (A), (B) and (C) are hydrolytically condensed in the presence of component (D) to achieve a T 3 to T 2 ratio of from about 0.83 to about 2.5,
wherein said coating composition has been pre-cured for about 10 minutes to about 60 minutes at a temperature of from about 60° C. to about 90° C. and wherein said pre-cured coating composition is cooled to ambient temperature and then fully cured at a temperature of from about 160° C. to about 180° C.
33. The coating composition of claim 32 wherein in formula (1), each occurrence of R 1 is independently a C1-C5 alkyl and each occurrence of X is independently a C1-C4 alkoxy.
34. The coating composition of claim 32 wherein in formula (2), each occurrence of R 3 is independently a C1-C5 alkyl, and each occurrence of X is independently a C1-C6 alkoxy group.
35. The coating composition of claim 32 wherein the metal oxide is colloidal silica.
36. The coating composition of claim 32 wherein component (D) is a thermal cure catalyst tetrabutylammonium carboxylate having a structural formula (3)
[(C 4 H 9 ) 4 N + [OC(O)—R] − (3),
wherein R is selected from the group consisting of hydrogen, alkyl groups containing about 1 to about 8 carbon atoms, and aromatic groups containing about 6 to 20 carbon atoms.
37. The coating composition of claim 36 wherein R is a C1-C4 alkyl.
38. The coating composition of claim 36 wherein component (D) is selected from the group consisting of tetra-n-butylammonium acetate (TBAA), tetra-n-butylammonium formate, tetra-n-butyl ammonium benzoate, tetra-n-butylammonium-2-ethylhexanoate, tetra-n-butylammonium-p-ethylbenzoate, tetra-n-butylammonium propionate and combinations thereof.
39. An article comprising:
a substrate having a surface coated with a coating composition suitable for providing a thermoformable hardcoat comprising:
(A) at least one silane-containing oligomer having the general formula (1)
wherein each occurrence of R′ is independently a C1-C8 alkyl or C6-C20 aryl; each occurrence of R 2 is independently a C2-C8 alkylene; each occurrence of X is independently a halogen atom, C1-C6 alkoxy, C1-C6 acyloxy, C1-C6 alkenoxy or hydroxide; each occurrence of Y is independently an oxygen or R 2 ; a is an integer between 0 and 30; b is 2 or 3 and c is an integer between 0 and 6, and/or a partial hydrolytic condensate thereof;
(ii) a copolymer of CR 1 R 1 ═CR 1 C(O)OR 1 and CR 1 R 1 ═CR 1 C(O)OR 2 SiX d R 1 (3-4) , wherein each occurrence of R 1 is independently a C1-C8 alkyl or C6-C20 aryl; each occurrence of R 2 is independently a C2-C8 alkylene; each occurrence of X is independently a halogen atom, C1-C6 alkoxy, C1-C6 acyloxy, C1-C6 alkenoxy or hydroxide; and d is 1, 2 or 3; and combinations thereof;
(B) at least one silane having the general formula (2):
R 3 e SiX (4-e) (2)
wherein each occurrence of R 3 is independently a C1-C8 alkyl, C2-C8 alkenyl or C6-C20 aryl, each occurrence of X is a halogen atom, C1-C6 alkoxy, C1-C6 acyloxy, C1-C6 alkenoxy or hydroxide; e is 0, 1 or 2, and/or a partial hydrolytic condensate thereof;
(C) metal oxide; and
(D) condensation catalyst;
(E) a UV absorber that is capable of co-condensing with at least one of components (A), (B) or (C);
wherein components (A), (B), (C) and (E) are hydrolytically condensed in the presence of component (D) to achieve a T 3 to T 2 ratio of from about 0.83 to about 2.5,
wherein said coating composition has been pre-cured for about 10 minutes to about 60 minutes at a temperature of from about 60° C. to about 90° C. and wherein said pre-cured coating composition is cooled to ambient temperature and then fully cured at a temperature of from about 160° C. to about 180° C.
40. The coating composition of claim 39 wherein the UV absorber is selected from the group consisting of 4-[gamma-(trimethoxysilyl)propoxyl]-2-hydroxy benzophenone, 4-[gamma-(triethoxysilyl)propoxyl]-2-hydroxy benzophenone, 4,6-dibenzoyl-2-(3-triethoxysilylpropyl) resorcinol, and combinations thereof.