Polyimide precursor composition and optical multilayer structure formed using the same
Provided are polyimide precursor composition including a polyimide precursor including a siloxane structure, and inorganic particles, and an optical multilayer structure including a structure in which a polyimide shatterproof layer formed using the composition is formed on a substrate. The optical multilayer structure according to one implementation is less curled to minimize substrate bending and has significantly improved surface hardness, and thus, has excellent mechanical properties.
1 . A polyimide precursor composition comprising: a polyimide precursor comprising a unit derived from an acid anhydride or a diamine comprising a structure of the following Chemical Formula 1, a unit derived from an acid anhydride represented by the following Chemical Formula 4, inorganic particles, and a mixed solvent of a solvent having a negative distribution coefficient and a solvent having a positive distribution coefficient, wherein a mass ratio between the solvent having a negative distribution coefficient and the solvent having a positive distribution coefficient is 6:4 to 9:1:
wherein
R 1 and R 2 are independently of each other C 1-5 alkyl which is unsubstituted or substituted with one or more halogens;
R 3 and R 4 are independently of each other C 6-10 aryl which is unsubstituted or substituted with one or more halogens;
L 1 and L 2 are independently of each other C 1-10 alkylene; and
x and y are independently of each other an integer of 1 or more:
wherein X 1 is independently of each other a C 3-10 aliphatic ring or a C 4-10 aromatic ring, and Y 1 is a linker comprising a single bond, a substituted or unsubstituted C 1-20 aliphatic chain, a substituted or unsubstituted C 3-10 aliphatic ring and/or a substituted or unsubstituted C 4-10 aromatic ring, and specifically, Y 1 may comprise two or more C 4-10 arylene linked by C 1-20 alkylene, C 1-10 alkylene, C 1-5 alkylene, C 3-10 cycloalkylene, C 4-10 arylene, two or more C 3-10 cycloalkylenes linked by C 1-20 alkylene, or two or more C 4-10 arylene linked by C 1-20 alkylene, and
wherein a curl amount of opposing ends of a polyimide film formed from the polyimide precursor composition on a surface of an ultrathin tempered glass (UTG) substrate is 3.0 mm or less, wherein the curl amount is calculated as an average value of the values measured at each of the opposing ends.
2 . The polyimide precursor composition of claim 1 , wherein the polyimide precursor further comprises a unit derived from a diamine represented by the following Chemical Formula 2:
wherein
R 11 and R 21 are independently of each other hydrogen or a C 1-20 monovalent organic group;
L 11 is —SO 2 —, —O—, or —C(═O)O—, or a C 1-20 divalent organic group comprising any one or more of these bonds; and
Chemical Formula 2 does not comprise a fluorine atom.
3 . The polyimide precursor composition of claim 1 , wherein the polyimide precursor further comprises a unit derived from a fluorine-based diamine.
4 . The polyimide precursor composition of claim 3 , wherein the fluorine-based diamine comprises one or more selected from the group consisting of 2,2′-bis(trifluoromethyl)benzidine (TFMB), 2,2-bis[4-(4-aminophenoxy)phenyl] hexafluoropropane (HFBAPP), 2,2-bis(4-aminophenyl) hexafluoropropane (BAHF), 2,2′-bis(trifluoromethyl)-4,4′-diaminodiphenylether, 4,4′-bis(4-amino-2-trifluoromethylphenoxy) biphenyl, 1,4-bis(4-amino-2-trifluoromethylphenoxy)benzene and mixtures thereof.
5 . The polyimide precursor composition of claim 1 , wherein
R 1 and R 2 are independently of each other C 1-3 alkyl which is unsubstituted or substituted with one or more halogens;
R 3 and R 4 are independently of each other C 6-8 aryl which is unsubstituted or substituted with one or more halogens; and
L 1 and L 2 are independently of each other C 1-5 alkylene.
6 . The polyimide precursor composition of claim 1 , wherein the structure of Chemical Formula 1 is a structure of the following Chemical Formula 3:
wherein
L 1 and L 2 are independently of each other C 1-10 alkylene; and
x and y are independently of each other an integer of 1 or more.
7 . The polyimide precursor composition of claim 2 , wherein
R 11 and R 21 are independently of each other hydrogen or a C 1-10 monovalent organic group; and
L 11 is —SO 2 —, —O—, or —C(═O)O—, or a C 1-15 divalent organic group comprising any one or more of these bonds.
8 . The polyimide precursor composition of claim 2 , wherein L 11 is —SO 2 —, —O—, or —C(═O)O—, or a combination of any one or more of —SO 2 —, —O—, or —C(═O)O— and any one or more selected from the group consisting of C 1-10 alkylene, C 5-18 cycloalkylene, and C 6-18 arylene.
9 . The polyimide precursor composition of claim 1 , wherein the inorganic particles comprise silica, zirconium oxide, titanium oxide, zinc oxide, zinc sulfide, chromium oxide, barium titanate, or a combination thereof.
10 . The polyimide precursor composition of claim 1 , wherein the inorganic particles are comprised at 1 wt % to 30 wt % with respect to the total weight of the polyimide precursor composition.
11 . The polyimide precursor composition of claim 1 , further comprising one or more of blue series pigments and dyes.
12 . The polyimide precursor composition of claim 11 , wherein a maximum absorption wavelength of the blue series pigments and dyes is 520 nm to 680 nm.
13 . A polyimide film formed from the polyimide precursor composition according to claim 1 .
14 . The polyimide precursor composition of claim 1 , wherein the acid anhydride represented by the Chemical Formula 4 is ethylene glycol bis(4-trimellitate anhydride).
15 . An optical multilayer structure comprising:
an ultrathin tempered glass (UTG) substrate;
a shatterproof layer which is formed on the substrate and comprises a polyimide film formed from a polyimide precursor composition comprising: a polyimide precursor comprising a unit derived from an acid anhydride or a diamine comprising a structure of the following Chemical Formula 1, a unit derived from an acid anhydride represented by the following Chemical Formula 4, and inorganic particles; and
a hard coating layer formed on the shatterproof layer;
wherein
R 1 and R 2 are independently of each other C 1-5 alkyl which is unsubstituted or substituted with one or more halogens;
R 3 and R 4 are independently of each other C 6-10 aryl which is unsubstituted or substituted with one or more halogens;
L 1 and L 2 are independently of each other C 1-10 alkylene; and
x and y are independently of each other an integer of 1 or more,
wherein X 1 is independently of each other a C 3-10 aliphatic ring or a C 4-10 aromatic ring, and Y 1 is a linker comprising a single bond, a substituted or unsubstituted C 1-20 aliphatic chain, a substituted or unsubstituted C 3-10 aliphatic ring and/or a substituted or unsubstituted C 4-10 aromatic ring, and specifically, Y 1 may comprise two or more C 4-10 arylene linked by C 1-20 alkylene, C 1-10 alkylene, C 1-5 alkylene, C 3-10 cycloalkylene, C 4-10 arylene, two or more C 3-10 cycloalkylenes linked by C 1-20 alkylene, or two or more C 4-10 arylene linked by C 1-20 alkylene, and
wherein a curl amount of opposing ends of the polyimide film formed from the polyimide precursor composition on a surface of the ultrathin tempered glass (UTG) substrate is 3.0 mm or less, wherein the curl amount is calculated as an average value of the values measured at each of the opposing ends.
16 . The optical multilayer structure of claim 15 , wherein the hard coating layer comprises a siloxane-based compound having an epoxy group.
17 . A method of manufacturing an optical multilayer structure, the method comprising:
applying a polyimide precursor composition comprising: a polyimide precursor comprising a unit derived from an acid anhydride or a diamine comprising a structure of the following Chemical Formula 1, a unit derived from an acid anhydride represented by the following Chemical Formula 4, and inorganic particles on a substrate and drying the composition to form a shatterproof layer; and
applying the composition for forming a hard coating layer on the shatterproof layer and curing the composition to form a hard coating layer:
wherein
R 1 and R 2 are independently of each other C 1-5 alkyl which is unsubstituted or substituted with one or more halogens;
R 3 and R 4 are independently of each other C 6-10 aryl which is unsubstituted or substituted with one or more halogens;
L 1 and L 2 are independently of each other C 1-10 alkylene; and
x and y are independently of each other an integer of 1 or more,
wherein X 1 is independently of each other a C 3-10 aliphatic ring or a C 4-10 aromatic ring, and Y 1 is a linker comprising a single bond, a substituted or unsubstituted C 1-20 aliphatic chain, a substituted or unsubstituted C 3-10 aliphatic ring and/or a substituted or unsubstituted C 4-10 aromatic ring, and specifically, Y 1 may comprise two or more C 4-10 arylene linked by C 1-20 alkylene, C 1-10 alkylene, C 1-5 alkylene, C 3-10 cycloalkylene, C 4-10 arylene, two or more C 3-10 cycloalkylenes linked by C 1-20 alkylene, or two or more C 4-10 arylene linked by C 1-20 alkylene, and
wherein a curl amount of opposing ends of a polyimide film formed from the polyimide precursor composition on a surface of an ultrathin tempered glass (UTG) substrate is 3.0 mm or less, wherein the curl amount is calculated as an average value of the values measured at each of the opposing ends.
18 . A window cover film comprising the optical multilayer structure according to claim 14 .