Hard coating composition and window member having hard coating layer
A hard coating composition according to an embodiment includes a polymer derived from a mixture including a silsesquioxane, a siloxane compound, and inorganic particles which are surface treated with silane. A hard coating layer having high surface hardness and impact resistance, and at the same time, excellent bending properties may be provided.
1. A hard coating composition comprising a polymer represented by the following Formula 1-1 and at least one photoinitiator,
wherein the at least one photoinitiator comprises:
a first photoinitiator configured to be activated by first ultraviolet rays; and
a second photoinitiator configured to be activated by second ultraviolet rays, the second ultraviolet rays having a longer wavelength than the first ultraviolet rays,
wherein the first photoinitiator and the second photoinitiator are comprised in a weight ratio of 1:0.2 to 0.2:1,
wherein in Formula 1-1,
R 1 and R 11 are each independently a hydrogen atom, a deuterium atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms for forming a ring, a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms for forming a ring, a substituted or unsubstituted silyl group, a hydroxyl group, or ((X) b (M) a O *,
X is a hydrogen atom, a deuterium atom, a halogen atom, a substituted or unsubstituted C 1-6 alkyl group, or a hydroxyl group;
M is Si, Al, Ti, Zn, or Zr;
a is 1, when M is Si or Ti, b is 3, when M is Zn, b is 1, when M is Al, b is 2, and when M is Zr, b is 1, 2 or 3;
R 2 and R 22 are each independently a hydrogen atom, a deuterium atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms for forming a ring, a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms for forming a ring, a substituted or unsubstituted silyl group;
R 3 and R 33 are each independently a hydrogen atom, a deuterium atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms for forming a ring, a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms for forming a ring, a substituted or unsubstituted silyl group, or * CH 2 P Y ;
p is an integer of 1 to 6, Y is
R 7 is a hydrogen atom or a methyl group; and
n2, and n3 are each independently an integer of 1 to 100, n1 is an integer of 2 to 100, and at least one R 1 from n1 number of R 1 ((X) b (M) a O *.
2. The hard coating composition of claim 1 , wherein the at least one photoinitiator is comprised in an amount of 1 wt % to 5 wt % based on a total amount of the hard coating composition.
3. The hard coating composition of claim 1 , further comprising a polyfunctional acrylate compound.
4. The hard coating composition of claim 3 , wherein the polyfunctional acrylate compound is comprised in an amount of 3 wt % to 20 wt % based on a total amount of the hard coating composition.
5. The hard coating composition of claim 3 , wherein the polyfunctional acrylate compound comprises at least six acrylate functional groups.
6. The hard coating composition of claim 1 , further comprising at least one of a polyfunctional acrylate monomer or a polyfunctional urethane acrylate oligomer.
7. The hard coating composition of claim 1 , further comprising at least one of an antistatic agent or an ultraviolet absorbent.
8. A hard coating composition comprising a polymer represented by the following Formula 1 and at least one photoinitiator:
wherein in Formula 1,
R 1 is a hydrogen atom, a deuterium atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms for forming a ring, a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms for forming a ring, a substituted or unsubstituted silyl group, a hydroxyl group, or ((X) b (M) a O *, X is a hydrogen atom, a deuterium atom, a halogen atom, a substituted or unsubstituted C 1-6 alkyl group, or a hydroxyl group;
M is Si, Al, Ti, Zn, or Zr;
a is 1, when M is Si or Ti, b is 3, when M is Zn, b is 1, when M is Al, b is 2, and when M is Zr, b is 1, 2 or 3;
R 2 is a hydrogen atom, a deuterium atom, a halogen atom, substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms for forming a ring, a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms for forming a ring, or a substituted or unsubstituted silyl group;
R 3 is a hydrogen atom, a deuterium atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms for forming a ring, a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms for forming a ring, a substituted or unsubstituted silyl group, or * CH 2 P Y ;
p is an integer of 1 to 6, Y is
R 7 is a hydrogen atom or a methyl group;
R 4 , R 5 , and R 6 are each independently a hydrogen atom, a deuterium atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms for forming a ring, a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms for forming a ring, a substituted or unsubstituted silyl group, or an oxygen atom which is connected with an other silicon atom of the polymer represented by Formula 1;
n2, and n3 are each independently an integer of 1 to 100,
n1 is an integer of 2 to 100, and at least one R 1 from n1 number of R 1 is ((X) b (M) a O *,
wherein the at least one photoinitiator comprises:
a first photoinitiator configured to be activated by first ultraviolet rays; and
a second photoinitiator configured to be activated by second ultraviolet rays, the second ultraviolet rays having a longer wavelength than the first ultraviolet rays, and
wherein the first photoinitiator and the second photoinitiator are comprised in a weight ratio of 1:0.2 to 0.2:1.
9. The hard coating composition of claim 8 , wherein X is a hydroxyl group, and M is Si.
10. The hard coating composition of claim 8 , wherein Formula 1 is represented by the following Formula 1-1:
wherein in Formula 1-1,
R 11 is a hydrogen atom, a deuterium atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms for forming a ring, a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms for forming a ring, a substituted or unsubstituted silyl group, a hydroxyl group, or ((X) b (M) a O *;
R 22 is a hydrogen atom, a deuterium atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms for forming a ring, a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms for forming a ring, a substituted or unsubstituted silyl group;
R 33 is a hydrogen atom, a deuterium atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms for forming a ring, a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms for forming a ring, a substituted or unsubstituted silyl group, or * CH 2 P Y ; and
in Formula 1-1, R 1 , R 2 , R 3 , n1, n2, n3, X, M, a, b, Y, and P are a same as defined in Formula 1.
11. The hard coating composition of claim 8 , further comprising a polyfunctional acrylate compound.
12. A window member comprising:
a plastic substrate; and
a hard coating layer on the plastic substrate,
wherein the hard coating layer is formed utilizing a polymer represented by the following Formula 1-1 and at least one photoinitiator,
wherein the at least one photoinitiator comprises:
a first photoinitiator configured to be activated by first ultraviolet rays; and
a second photoinitiator configured to be activated by second ultraviolet rays, the second ultraviolet rays having a longer wavelength than the first ultraviolet rays,
wherein the first photoinitiator and the second photoinitiator are comprised in a weight ratio of 1:0.2 to 0.2:1,
wherein in Formula 1-1,
R 1 and R 11 are each independently a hydrogen atom, a deuterium atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms for forming a ring, a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms for forming a ring, a substituted or unsubstituted silyl group, a hydroxyl group, or ((X) b (M) a O *,
X is a hydrogen atom, a deuterium atom, a halogen atom, a substituted or unsubstituted C 1-6 alkyl group, or a hydroxyl group;
M is Si, Al, Ti, Zn, or Zr;
a is 1, when M is Si or Ti, b is 3, when M is Zn, b is 1, when M is Al, b is 2, and when M is Zr, b is 1, 2 or 3;
R 2 and R 22 are each independently a hydrogen atom, a deuterium atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms for forming a ring, a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms for forming a ring, a substituted or unsubstituted silyl group;
R 3 and R 33 are each independently a hydrogen atom, a deuterium atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms for forming a ring, a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms for forming a ring, a substituted or unsubstituted silyl group, or * CH 2 P Y ;
p is an integer of 1 to 6, Y is
R 7 is a hydrogen atom or a methyl group; and
n2, and n3 are each independently an integer of 1 to 100, n1 is an integer of 2 to 100, and at least one R 1 from n1 number of R 1 is ((X) b (M) a O *.
13. The window member of claim 12 , wherein the plastic substrate comprises:
a first substrate comprising a first polymer resin; and
a second substrate comprising a second polymer resin different from the first polymer resin.
14. The window member of claim 12 , wherein the hard coating layer is disposed on an upper surface of the plastic substrate, and a protective coating layer disposed on a bottom surface of the plastic substrate is further comprised.
15. The hard coating composition of claim 1 , wherein
the first photoinitiator is selected from the group consisting of a-hydroxy ketone, 2,2-dimethoxy-1,2-diphenylethan-1-one, 2-hydroxyl-1-[4-(2-hydroxyethoxy)phenyl]-2-methyl-1-propanone, and 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-1-propionyl)-benzyl]-phenyl}-2-methylpropan-1-one, and
the second photoinitiator is selected from the group consisting of phenylglyoxylate, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, 2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one, 2,4,6-trimethylbenzoyl-diphenyl phosphinate, bis(2,4,6-trimethylbenzoyl)-phenylphosphineoxide, [1-(4-phenylsulfanylbenzoyl)heptylideneamino]benzoate, [1-[9-ethyl-6-(2-methylbenzoyl)carbazol-3-yl]ethylideneamino] acetate, and Bis(2,4-cyclopentadienyl)bis[2,6-difluoro-3-(1-pyrryl)phenyl] titanium(IV).
16. The window member of claim 12 , wherein
the first photoinitiator is selected from the group consisting of a-hydroxy ketone, 2,2-dimethoxy-1,2-diphenylethan-1-one, 2-hydroxyl-1-[4-(2-hydroxyethoxy)phenyl]-2-methyl-1-propanone, and 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-1-propionyl)-benzyl]-phenyl}-2-methylpropan-1-one, and
the second photoinitiator is selected from the group consisting of phenylglyoxylate, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, 2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one, 2,4,6-trimethylbenzoyl-diphenyl phosphinate, bis(2,4,6-trimethylbenzoyl)-phenylphosphineoxide, [1-(4-phenylsulfanylbenzoyl)heptylideneamino]benzoate, [1-[9-ethyl-6-(2-methylbenzoyl)carbazol-3-yl]ethylideneamino] acetate, and Bis(2,4-cyclopentadienyl)bis[2,6-difluoro-3-(1-pyrryl)phenyl] titanium(IV).