Polyimide precursor, polyimide precursor composition, polyimide film, method for preparing the same, and use thereof
View Patent ↗Provided are a polyimide precursor, a polyimide precursor solution, a polyimide film, a method for preparing the same, and a use thereof. According to an exemplary embodiment of the present invention, a polyimide film having excellent thermal resistance and satisfying transparency and a low coefficient of linear thermal expansion may be provided, and thus, may be usefully applied in a flexible display field requiring high dimensional stability and the like.
1. A polyimide precursor solution comprising: a polymerization component including a tetracarboxylic acid dianhydride represented by the following Chemical Formula 1 and a diamine; and an organic solvent:
wherein
Q 1 is a single bond, —C(═O)—, —C(═O)O—, —C(═O)NH—, —NR′—, —S—, —SO 2 —, —CH 2 —, or a combination thereof, wherein R′ is hydrogen or C1-C10 alkyl;
R 1 and R 2 are independently of each other a halogen, hydroxy, thiol, nitro, cyano, C1-C10 alkyl, C1-C10 alkoxy, C6-C20 aryl, or a combination thereof, or may be connected to an adjacent substituent to form a ring; and
n and m are independently of each other an integer selected from 0 to 4, and when n and m are an integer of 2 or more, R 1 and R 2 may be the same as or different from each other.
2. The polyimide precursor solution of claim 1 , wherein the tetracarboxylic acid dianhydride is selected from compounds represented by the following Chemical Formulae 2 to 5:
wherein
R 1 , R 2 , R′, n, and m are as defined in Chemical Formula 1 of claim 1 .
3. The polyimide precursor solution of claim 1 , wherein the polyimide precursor solution includes: the polyimide precursor obtained by polymerizing the polymerization component including the tetracarboxylic acid dianhydride represented by Chemical Formula 1 and the diamine.
4. The polyimide precursor solution of claim 1 , wherein the diamine includes a unit represented by the following Chemical Formula 6:
wherein
R 3 is hydrogen, C1-C10 alkyl, or C1-C10 fluoroalkyl; and
p is an integer of 1 or 2.
5. The polyimide precursor solution of claim 1 , wherein the organic solvent is selected from amides.
6. The polyimide precursor solution of claim 5 , wherein the organic solvent is N,N-diethylacetamide, N,N-diethylformamide, N-ethylpyrrolidone, N,N-dimethylpropionamide, N,N-diethylpropionamide, or a combination thereof.
7. The polyimide precursor solution of claim 1 , wherein a tetracarboxylic acid dianhydride selected from compounds represented by the following Chemical Formulae 7 and 8 is further included as the polymerization component:
wherein
Q 2 and Q 3 are a single bond, —O—, —C(═O)—, —C(═O)O—, —C(═O)NH—, —NR′—, —S—, —SO 2 —, phenylene, or a combination thereof, wherein R′ is hydrogen or C1-C10 alkyl.
8. A method for preparing a polyimide film comprising: applying and coating the polyimide precursor solution of claim 1 on a substrate and then performing a heat treatment.
9. The method for preparing a polyimide film of claim 8 , wherein the heat treatment includes:
a first heat treatment performed at 100° C. or lower;
a second heat treatment performed at higher than 100° C. and 300° C. or lower; and
a third heat treatment performed at higher than 300° C. and 500° C. or lower.
10. The method for preparing a polyimide film of claim 8 , wherein the polyimide precursor solution includes 10 to 13 wt % of a solid content, based on a total weight.
11. A polyimide precursor obtained by polymerizing a tetracarboxylic acid dianhydride represented by the following Chemical Formula 1 and a diamine:
wherein
Q 1 is a single bond, —C(═O)—, —C(═O)O—, —C(═O)NH—, —NR′—, —S—, —SO 2 —, —CH 2 —, or a combination thereof, wherein R′ is hydrogen or C1-C10 alkyl;
R 1 and R 2 are independently of each other a halogen, hydroxy, thiol, nitro, cyano, C1-C10 alkyl, C1-C10 alkoxy, C6-C20 aryl, or a combination thereof, or may be connected to an adjacent substituent to form a ring; and
n and m are independently of each other an integer selected from 0 to 4, and when n and m are an integer of 2 or more, R 1 and R 2 may be the same as or different from each other.
12. The polyimide precursor of claim 11 , wherein the polyimide precursor includes a repeating unit represented by the following Chemical Formula a:
wherein
Q 1 is a single bond, —C(═O)—, —C(═O)O—, —C(═O)NH—, —NR′—, —S—, —SO 2 —, —CH 2 —, or a combination thereof, wherein R′ is hydrogen or C1-C10 alkyl;
R a and R b are independently of each other hydrogen or C1-C10 alkyl;
R 1 and R 2 are independently of each other a halogen, hydroxy, thiol, nitro, cyano, C1-C10 alkyl, C1-C10 alkoxy, C6-C20 aryl, or a combination thereof, or may be connected to an adjacent substituent to form a ring;
R 3 is hydrogen, C1-C10 alkyl, or C1-C10 fluoroalkyl;
p is an integer of 1 or 2; and
n and m are independently of each other an integer selected from 0 to 4, and when n and m are an integer of 2 or more, R 1 and R 2 may be the same as or different from each other.
13. The polyimide precursor of claim 12 , wherein the polyimide precursor includes 10 to 100 mol % of the repeating unit represented by Chemical Formula a, based on total repeating units.
14. A polyimide film comprising a repeating unit represented by the following Chemical Formula b:
wherein
Q 1 is a single bond, —C(═O)—, —C(═O)O—, —C(═O)NH—, —NR′—, —S—, —SO 2 —, —CH 2 —, or a combination thereof, wherein R′ is hydrogen or C1-C10 alkyl;
R 1 and R 2 are independently of each other a halogen, hydroxy, thiol, nitro, cyano, C1-C10 alkyl, C1-C10 alkoxy, C6-C20 aryl, or a combination thereof, or may be connected to an adjacent substituent to form a ring;
R 3 is hydrogen, C1-C10 alkyl, or C1-C10 fluoroalkyl;
p is an integer of 1 or 2; and
n and m are independently of each other an integer selected from 0 to 4, and when n and m are an integer of 2 or more, R 1 and R 2 may be the same as or different from each other.
15. The polyimide film of claim 14 , wherein the polyimide film further includes a repeating unit represented by the following Chemical Formula c or d:
wherein
R 3 is hydrogen, C1-C10 alkyl, or C1-C10 fluoroalkyl; and
p is an integer of 1 or 2.
16. The polyimide film of claim 14 , wherein the polyimide film has a coefficient of thermal expansion (CTE) of 50 ppm/° C. or less at 100 to 450° C.
17. The polyimide film of claim 14 , wherein the polyimide film has
a yellow index (YI) in accordance with ASTM E313 of 15 or less;
a haze in accordance with ASTM D1003 of 2 or less; and
a total light transmittance in a region of 380 to 780 nm in accordance with ASTM D1746 of 80% or more.
18. The polyimide film of claim 14 , wherein the polyimide film has a modulus in accordance with ASTM D882 of 5.0 or more and an elongation of 15% or more.
19. The polyimide film of claim 14 , wherein the polyimide film has
a coefficient of thermal expansion of 50 ppm/° C. or less at 100 to 450° C.;
a yellow index (YI) in accordance with ASTM E313 of 15 or less;
a haze in accordance with ASTM D1003 of 2 or less;
an average light transmittance in a region of 380 to 780 nm in accordance with ASTM D1746 of 80% or more; and
a modulus in accordance with ASTM D882 of 8.0 or less and an elongation of 15% or more.
20. A multilayer structure comprising the polyimide film of claim 14 .
21. A photoelectric device comprising the polyimide film of claim 14 as a flexible substrate.
22. A flexible display comprising the polyimide film of claim 14 as a flexible substrate.