Polyamide-imide-based film, preparation method thereof, and composite film and display device comprising the same
The embodiments provide a polyamide-imide-based film that comprises a polyamide-imide-based polymer and has an rSE value of 0.8 to 1.25 as represented by the following Equation 1, whereby it is excellent in adhesion to a hard coating layer and light resistance to a UV light source, a process for preparing the same, and a composite film and a display device comprising the same. <Equation 1> rSE=SE1/SE2 In Equation 1, SE1 is the surface energy (dyne/cm) of a first side of the film, and SE2 is the surface energy (dyne/cm) of a second side of the film.
1 . A polyamide-imide-based film, which comprises a polyamide-imide-based polymer and has an rSE value of 0.8 to 1.25 as represented by the following Equation 1,
rSE=SE 1/ SE 2 <Equation 1>
in Equation 1, SE1 is the surface energy (dyne/cm) of a first side of the film, and SE2 is the surface energy (dyne/cm) of a second side of the film,
wherein the polyamide-imide-based film has a dAd value of 13° or less as represented by the following Equation 3,
dAd=|Ad 2− Ad 1 <Equation 3>
in Equation 3, Ad1 is the contact angle (°) of diiodomethane to the first side of the film, and Ad2 is the contact angle (°) of diiodomethane to the second side of the film,
wherein the polyamide-imide-based film is a film prepared by a process comprising:
polymerizing a diamine compound, a dianhydride compound, and a dicarbonyl compound in an organic solvent to prepare a polyamide-imide-based polymer solution;
casting the solution and then drying it to prepare a gel sheet; and
thermally treating the gel sheet,
wherein the process comprises, before casting the polyamide-imide-based polymer solution, stirring the solution,
wherein the step of stirring the solution is carried out at a temperature of 0° C. to 25° C. and at a rotation speed of 120 rpm to 500 rpm,
wherein the step of preparing a polyamide-imide-based polymer solution comprises adding a filler dispersed in an organic solvent, and the filler has a diameter (D50) of 50 nm to 1,000 nm as dissolved in an organic solvent, and the filler contained in the polyamide-imide-based polymer solution has a diameter (D50) of 500 nm to 3,000 nm after the solution is stirred.
2 . The polyamide-imide-based film of claim 1 , wherein SE1 is 35 dynes/cm to 60 dynes/cm, and SE2 is 35 dynes/cm to 60 dynes/cm.
3 . The polyamide-imide-based film of claim 1 , which has a dAp value of 8° or less as represented by the following Equation 2:
dAp=|Ap 2− Ap 1| <Equation 2>
in Equation 2, Ap1 is the contact angle (°) of water to the first side of the film, and Ap2 is the contact angle (°) of water to the second side of the film.
4 . The polyamide-imide-based film of claim 1 , wherein the contact angle (Ap1) of water to the first side of the polyamide-imide-based film is 60° to 83°, and the contact angle (Ap2) of water to the second side of the polyamide-imide-based film is 60° to 85°.
5 . The polyamide-imide-based film of claim 1 , wherein the contact angle (Ad1) of diiodomethane to the first side of the polyamide-imide-based film is 30° to 50°, and the contact angle (Ad2) of diiodomethane to the second side of the polyamide-imide-based film is 30° to 55°.
6 . The polyamide-imide-based film of claim 1 , which further comprises at least one selected from the group consisting of a filler, a blue pigment, and a UVA absorber.
7 . The polyamide-imide-based film of claim 1 , wherein the polyamide-imide-based polymer comprises an imide-based repeat unit and an amide-based repeat unit at a molar ratio of 2:98 to 70:30.
8 . A process for preparing the polyamide-imide-based film of claim 1 , which comprises:
polymerizing a diamine compound, a dianhydride compound, and a dicarbonyl compound in an organic solvent to prepare a polyamide-imide-based polymer solution;
casting the solution and then drying it to prepare a gel sheet; and
thermally treating the gel sheet,
wherein the process comprises, before casting the polyamide-imide-based polymer solution, stirring the solution,
wherein the step of stirring the solution is carried out at a temperature of 0° C. to 25° C. and at a rotation speed of 120 rpm to 500 rpm,
wherein the step of preparing a polyamide-imide-based polymer solution comprises adding a filler dispersed in an organic solvent, and the filler has a diameter (D50) of 50 nm to 1,000 nm as dissolved in an organic solvent, and
wherein the step of preparing a polyamide-imide-based polymer solution comprises adding a filler dispersed in an organic solvent, and the filler contained in the polyamide-imide-based polymer solution has a diameter (D50) of 500 nm to 3,000 nm after the solution is stirred.
9 . A polyamide-imide-based composite film, which comprises a polyamide-imide-based film and a functional layer, wherein the polyamide-imide-based film comprises a polyamide-imide-based polymer and has an rSE value of 0.8 to 1.25 as represented by the following Equation 1,
rSE=SE 1/ SE 2 <Equation 1>
in Equation 1, SE1 is the surface energy (dyne/cm) of a first side of the polyamide-imide-based film, and SE2 is the surface energy (dyne/cm) of a second side of the polyamide-imide-based film,
wherein the polyamide-imide-based film has a dAd value of 13° or less as represented by the following Equation 3,
dAd=|Ad 2− Ad 1| <Equation 3>
in Equation 3, Ad1 is the contact angle (°) of diiodomethane to the first side of the film, and Ad2 is the contact angle (°) of diiodomethane to the second side of the film,
wherein the polyamide-imide-based film is a film prepared by a process comprising:
polymerizing a diamine compound, a dianhydride compound, and a dicarbonyl compound in an organic solvent to prepare a polyamide-imide-based polymer solution;
casting the solution and then drying it to prepare a gel sheet; and
thermally treating the gel sheet,
wherein the process comprises, before casting the polyamide-imide-based polymer solution, stirring the solution,
wherein the step of stirring the solution is carried out at a temperature of 0° C. to 25° C. and at a rotation speed of 120 rpm to 500 rpm,
wherein the step of preparing a polyamide-imide-based polymer solution comprises adding a filler dispersed in an organic solvent, and the filler has a diameter (D50) of 50 nm to 1,000 nm as dissolved in an organic solvent, and the filler contained in the polyamide-imide-based polymer solution has a diameter (D50) of 500 nm to 3,000 nm after the solution is stirred.
10 . The polyamide-imide-based composite film of claim 9 , wherein the functional layer further comprises a hard coating layer, when it is subjected to the cross-hatch test, the adhesion between the polyamide-imide-based film and the hard coating layer is 5 B or more, and when the polyamide-imide-based film is irradiated with a UV ray having a wavelength of 340 nm at a dose of 0.63 W/m 2 and a temperature of 60° C. for 72 hours and then subjected to the cross-hatch test, the adhesion between the polyamide-imide-based film and the hard coating layer is 4 B or more.
11 . A display device, which comprises a display unit; and a cover window disposed on the display unit, wherein the cover window comprises a polyamide-imide-based film and a functional layer, and the polyamide-imide-based film comprises a polyamide-imide-based polymer and has an rSE value of 0.8 to 1.25 as represented by the following Equation 1:
rSE=SE 1/ SE 2 <Equation 1>
in Equation 1, SE1 is the surface energy (dyne/cm) of a first side of the polyamide-imide-based film, and SE2 is the surface energy (dyne/cm) of a second side of the polyamide-imide-based film,
wherein the polyamide-imide-based film has a dAd value of 13° or less as represented by the following Equation 3,
dAd=|Ad 2− Ad 1| <Equation 3>
in Equation 3, Ad1 is the contact angle (°) of diiodomethane to the first side of the film, and Ad2 is the contact angle (°) of diiodomethane to the second side of the film,
wherein the polyamide-imide-based film is a film prepared by a process comprising:
polymerizing a diamine compound, a dianhydride compound, and a dicarbonyl compound in an organic solvent to prepare a polyamide-imide-based polymer solution;
casting the solution and then drying it to prepare a gel sheet; and
thermally treating the gel sheet,
wherein the process comprises, before casting the polyamide-imide-based polymer solution, stirring the solution,
wherein the step of stirring the solution is carried out at a temperature of 0° C. to 25° C. and at a rotation speed of 120 rpm to 500 rpm,
wherein the step of preparing a polyamide-imide-based polymer solution comprises adding a filler dispersed in an organic solvent, and the filler has a diameter (D50) of 50 nm to 1,000 nm as dissolved in an organic solvent, and the filler contained in the polyamide-imide-based polymer solution has a diameter (D50) of 500 nm to 3,000 nm after the solution is stirred.