KR20160007427A - Transparent polymer film and electronic device including the same - Google Patents

Abstract

Provided is a transparent film which comprises a polyimide-polybenzoxazole copolymer containing a repeating unit represented by chemical formula 1. In addition, provided are a method for producing the transparent film, and an electronic device comprising the transparent film. In the chemical formula 1: A_1, A_1′, A_2, A_3, m, and n are the same as defined in the present specification.

Description

TECHNICAL FIELD [0001] The present invention relates to a transparent polymer film and an electronic device including the transparent polymer film.

To a transparent polymer film and an electronic device containing the same.

Recently, there is an increasing need for a flexible display that is thin, light in weight, low in power, light in weight, and flexible, regardless of place and time, as a display for visualizing various information and transmitting it to human beings. Among the technologies required to implement flexible displays are flexible substrates, organic and inorganic materials for low temperature processes, flexible electronics, encapsulation and packaging. Among them, the flexible substrate can greatly affect the performance, reliability, and price of the flexible display. On the other hand, a flexible protective film having high transparency is required in an electronic device such as a light emitting diode or a complementary metal oxide semiconductor sensor.

Various polymer films have been proposed as flexible substrates or flexible protective films. Although the polymer can be produced in a relatively easy film form and is advantageous in terms of lightness, the polymer is originally poor in thermal stability (for example, the thermal expansion coefficient is high), and therefore, in order to have usefulness as a flexible substrate or a protective film for an electronic device, And at the same time, have improved optical properties (e.g., high transparency and low yellowing).

One embodiment is directed to a polymer transparency film having improved thermal and optical properties.

Another embodiment is directed to a method of making the polymer transparent film.

Another embodiment is directed to an electronic device comprising the polymeric transparent film.

In one embodiment, the transparent film comprises a polyimide-polybenzoxazole copolymer comprising a repeating unit represented by the following formula (1);

[Chemical Formula 1]

In formula (1)

A ₁ is a substituted or unsubstituted quadrivalent C6 to C24 aliphatic cyclic group, a substituted or unsubstituted quadrivalent C6 to C24 aromatic cyclic group, or a substituted or unsubstituted quadrivalent C4 to C24 heteroaromatic cyclic group, The aliphatic cyclic group, the aromatic cyclic group, or the heteroaromatic cyclic group is present alone; Or two or more rings may be fused together to form a condensed ring; Or two or more rings is a direct bond, -O-, -S-, -C (= O) -, -CH (OH) -, -S (= O) 2 -, -Si (CH 3) 2 -, (CH ₂ ) _p wherein ₁ ? _P ? 10, (CF ₂ ) _q wherein ₁ ? _Q ? 10, -CR ₂ - wherein R is independently hydrogen, aliphatic hydrocarbon groups, C6 to an aromatic hydrocarbon group, or a C6 to C20 alicyclic hydrocarbon group of _{C20), -C (CF 3) 2} -, -C (CF 3) (C 6 H 5) -, or -C ( = O) NH-,

A ₁ 'is a substituted or unsubstituted divalent C6 to C24 aliphatic ring group, a substituted or unsubstituted divalent C6 to C24 aromatic ring group, or a substituted or unsubstituted divalent C4 to C24 hetero aromatic ring group , The aliphatic cyclic group, the aromatic cyclic group, or the heteroaromatic cyclic group is present alone; Or two or more rings may be fused together to form a condensed ring; Or two or more rings is a direct bond, -O-, -S-, -C (= O) -, -CH (OH) -, -S (= O) 2 -, -Si (CH 3) 2 -, (CH ₂ ) _p wherein ₁ ? _P ? 10, (CF ₂ ) _q wherein ₁ ? _Q ? 10, -CR ₂ - wherein R is independently hydrogen, aliphatic hydrocarbon groups, C6 to an aromatic hydrocarbon group, or a C6 to C20 alicyclic hydrocarbon group of _{C20), -C (CF 3) 2} -, -C (CF 3) (C 6 H 5) -, or -C ( = O) NH-,

A ₂ is selected from the following,

-O-, -S-, -C (= O) -, -CH (OH) -, or -CH (OH) -, -S (= O) ₂ -, -Si (CH ₃ ) ₂ -, (CH ₂ ) _p (where ₁ ? _P? 10), (CF ₂ ) _q -CR ₂ - (wherein, R represents, each independently, hydrogen, C1 to C10 aliphatic hydrocarbon group, aromatic hydrocarbon group of C6 to C20, or C6 to C20 alicyclic hydrocarbon group), -C (CF _{3) 2 -, -C (CF 3) (} C 6 H 5) - a, or -C (= O) NH-, * is the part which is connected to the adjacent atom,

A ₃ is a substituted or unsubstituted divalent C6 to C24 aliphatic ring group, a substituted or unsubstituted divalent C6 to C24 aromatic ring group or a substituted or unsubstituted divalent C4 to C24 hetero aromatic ring group, The ring group, the aromatic ring group, or the heteroaromatic ring group may be present singly or two or more rings may be fused to each other to form a condensed ring; More than one ring is a direct bond, -O-, -S-, -C (= O) -, -CH (OH) -, -S (= O) 2 -, -Si (CH 3) 2 -, ( CH _{2) p (where, 1≤p≤10), (CF 2)} q ( where, 1≤q≤10), -CR ₂ - (wherein, R represents, each independently, hydrogen, an aliphatic C1 to C10 -C (CF ₃ ) ₂ -, -C (CF ₃ ) (C ₆ H ₅ ) -, or -C (= C ₃ -C 20) aromatic hydrocarbon group or a C 6 to C 20 alicyclic hydrocarbon group, O) NH-,

m and n are numbers representing the molar ratio between the imide repeating unit and the benzoxazole repeating unit, and n / m is a real number greater than 0 and less than 0.01.

n / m may be more than 0.0005 and not more than 0.006.

n / m may be 0.001 or more and 0.005 or less.

The A ₁ can be selected from the following;

In the above formulas, each of the residues may be substituted or unsubstituted, and each L may be the same or different and each independently represents a direct bond, -O-, -S-, -C (= O) -, -CH (OH) -, -S (= O) 2 -, -Si (CH 3) 2 -, (CH 2) p ( _{where, 1≤p≤10), (CF 2)} q ( where, 1≤q≤ 10), -CR ₂ - (wherein, R represents, each independently, hydrogen, C1 to C10 aliphatic hydrocarbon groups, C6 to C20 aromatic hydrocarbon group, or a C6 to C20 alicyclic hydrocarbon group), -C (CF of ₃ ) ₂ -, -C (CF ₃ ) (C ₆ H ₅ ) - or -C (═O) NH- and * is a moiety connected to an adjacent atom (eg carbon of a carbonyl group)

Z ¹ and Z ² are the same or different and independently represent -N = or -C (R ¹⁰⁰ ) =, R ¹⁰⁰ is hydrogen or a C 1 to C 5 alkyl group, Z ¹ and Z ² are simultaneously -C ¹⁰⁰ ) =,

Z ³ is -O-, -S-, or -NR ¹⁰¹ -, wherein R ¹⁰¹ is hydrogen or a C 1 to C 5 alkyl group.

For example, A ₁ can be selected from the following;

For example, A ₂ can be selected from the following:

A ₃ can be selected from the following:

In the above formulas, each of the residues (e.g., aromatic or alicyclic ring) may be substituted or unsubstituted and L is the same or different and each independently represents a direct bond, -O-, -S-, -C = O) -, -CH (OH ) -, -S (= O) 2 -, -Si (CH 3) 2 -, (CH 2) p ( _{where, 1≤p≤10), (CF 2)} q (Where 1? Q? 10), -CR ₂ -, wherein each R is independently hydrogen, a C1 to C10 aliphatic hydrocarbon group, a C6 to C20 aromatic hydrocarbon group, or a C6 to C20 alicyclic hydrocarbon (= C (= O) NH-), -C (CF ₃ ) ₂ -, -C (CF ₃ ) (C ₆ H ₅ ) Nitrogen of the ring).

For example, A ₃ can be selected from the following:

A ₁ 'can be selected from the following formulas:

In the above formulas, each of the residues may be substituted or non-substituted,

And each L is the same or different, each independently, a single bond, -O-, -S-, -C (= O) -, -CH (OH) -, -S (= O) 2 -, -Si (CH ₃ ) ₂ -, (CH ₂ ) _p wherein ₁ ? _P ? 10, (CF ₂ ) _q wherein ₁ ? _Q ? 10, -CR ₂ - wherein R is independently hydrogen, an aromatic hydrocarbon group of the aliphatic hydrocarbon groups, C6 to C20, or C6 to C20 alicyclic hydrocarbon _{group), -C (CF 3) 2} -, -C (CF 3) (C 6 H 5) -, or -C (= O) NH-,

Z ¹ and Z ² are the same or different and independently represent -N = or -C (R ¹⁰⁰ ) =, R ¹⁰⁰ is hydrogen or a C 1 to C 5 alkyl group, Z ¹ and Z ² are simultaneously -C ¹⁰⁰ ) =,

Z ³ is -O-, -S-, or -NR ¹⁰¹ -, wherein R ¹⁰¹ is hydrogen or a C 1 to C 5 alkyl group,

* Is the moiety to which the moiety is attached to a neighboring atom.

The film may have a transmittance of 85% or more for light having a wavelength in the range of 300 to 800 nm.

The film may have a yellow index of 5.2 or less.

The film may have a coefficient of thermal expansion (CTE) of less than or equal to 12 ppm / ^oC at a temperature of 50 to 300 degrees Celsius.

The film may include a vapor deposition film formed on the surface thereof by vapor deposition, and the vapor deposition film may be formed of silicon oxides, polysilicic acids, alkali metal silicates, alkaline earth silicates, metal silicates, aluminosilicates, silicon nitrides, silicon oxynitrides, silicon carbide, silicon alumina oxynitrides, or combinations thereof.

In another embodiment,

Board;

The above-described film formed on the substrate; And

And a vapor deposition film formed on the film,

The deposition layer may be formed of a material selected from the group consisting of silicon oxides, polysilicic acids, alkali metal silicates, alkaline earth metal silicates, aluminosilicates, silicon nitrides, silicon oxynitrides, Silicon carbide, silicon alumina oxynitride, or combinations thereof.

The surface roughness of the deposited film may be 1 nm to 100 nm.

In another embodiment, a method for producing a transparent film comprising a polyimide-polybenzoxazole copolymer comprising a repeating unit represented by the following formula (1)

A tetracarboxylic acid dianhydride compound represented by the following formula (2); A diamine compound represented by the following formula (3); And a polyamic acid copolymer represented by the following general formula (5), which is a condensation product of a hydroxy diamine compound containing a hydroxy group present in ortho position with respect to an amine group;

Imidizing the composition comprising the polyamic acid copolymer to obtain a film comprising a polyimide copolymer represented by Formula 6;

And thermally treating the film to obtain a transparent film comprising a polyimide-polybenzoxazole copolymer containing a repeating unit represented by the following formula (1)

[Chemical Formula 1]

(2)

(3)

NH ₂ -A ₃ -NH ₂

[Chemical Formula 4]

NH ₂ -A ₂ '-NH ₂

[Chemical Formula 5]

[Chemical Formula 6]

In the above Chemical Formulas 1 to 6,

A ₁ is the same or different and each independently represents a substituted or unsubstituted quadrivalent C6 to C24 aliphatic cyclic group, a substituted or unsubstituted quadrivalent C6 to C24 aromatic ring group, or a substituted or unsubstituted quadrivalent C4 To C24 heteroaromatic ring group, and the aliphatic ring group, the aromatic ring group, or the heteroaromatic ring group may be present singly or two or more rings may be fused to each other to form a condensed ring; More than one ring is a direct bond, -O-, -S-, -C (= O) -, -CH (OH) -, -S (= O) 2 -, -Si (CH 3) 2 -, ( CH _{2) p (where, 1≤p≤10), (CF 2)} q ( where, 1≤q≤10), -CR ₂ - (wherein, R represents, each independently, hydrogen, an aliphatic C1 to C10 -C (CF ₃ ) ₂ -, -C (CF ₃ ) (C ₆ H ₅ ) -, or -C (= C ₃ -C 20) aromatic hydrocarbon group or a C 6 to C 20 alicyclic hydrocarbon group, O) NH-,

A ₁ 'is the same or different, and each independently represents a substituted or unsubstituted divalent C6 to C24 aliphatic cyclic group, a substituted or unsubstituted divalent C6 to C24 aromatic cyclic group, or a substituted or unsubstituted divalent C4-C24 heteroaromatic ring group, said aliphatic ring group, said aromatic ring group, or said heteroaromatic ring group being present alone; Or two or more rings may be fused together to form a condensed ring; Or two or more rings is a direct bond, -O-, -S-, -C (= O) -, -CH (OH) -, -S (= O) 2 -, -Si (CH 3) 2 -, (CH ₂ ) _p wherein ₁ ? _P ? 10, (CF ₂ ) _q wherein ₁ ? _Q ? 10, -CR ₂ - wherein R is independently hydrogen, aliphatic hydrocarbon groups, C6 to an aromatic hydrocarbon group, or a C6 to C20 alicyclic hydrocarbon group of _{C20), -C (CF 3) 2} -, -C (CF 3) (C 6 H 5) -, or -C ( = O) NH-,

A ₂ ' is a hydroxy-containing group selected from the following,

,

,

,

,

,

,

, 또는

, or

Here, L is the same or different and each independently represents a direct bond, -O-, -S-, -C (= O) -, -CH (OH) -, -S (= O) 2 -, -Si (CH ₃ ) ₂ -, (CH ₂ ) _p (wherein 1≤p≤10), (CF ₂ ) _q (where 1≤q≤10), -CR ₂ - , -C (CF ₃ ) ₂ -, -C (CF ₃ ) (C ₆ H ₅ ), or a group of the following formula ) -, or -C (= O) NH-, * is a moiety connected to an adjacent atom (eg nitrogen), and a hydroxyl group (-OH) ≪ / RTI >

A ₂ is selected from the following,

Here, L is the same or different and each independently represents a direct bond, -O-, -S-, -C (= O) -, -CH (OH) -, -S (= O) 2 -, -Si (CH ₃ ) ₂ -, (CH ₂ ) _p (wherein 1≤p≤10), (CF ₂ ) _q (where 1≤q≤10), -CR ₂ - , -C (CF ₃ ) ₂ -, -C (CF ₃ ) (C ₆ H ₅ ), or a group of the following formula ) -, or -C (= O) NH-, and * is a moiety connected to an adjacent atom (e.g., nitrogen or oxygen of the benzoxazole ring)

A ₃ is a substituted or unsubstituted divalent C6 to C24 aliphatic ring group, a substituted or unsubstituted divalent C6 to C24 aromatic ring group or a substituted or unsubstituted divalent C4 to C24 hetero aromatic ring group, The ring group, the aromatic ring group, or the heteroaromatic ring group may be present singly or two or more rings may be fused to each other to form a condensed ring; More than one ring is a direct bond, -O-, -S-, -C (= O) -, -CH (OH) -, -S (= O) 2 -, -Si (CH 3) 2 -, ( CH _{2) p (where, 1≤p≤10), (CF 2)} q ( where, 1≤q≤10), -CR ₂ - (wherein, R represents, each independently, hydrogen, an aliphatic C1 to C10 -C (CF ₃ ) ₂ -, -C (CF ₃ ) (C ₆ H ₅ ) -, or -C (= C ₃ -C 20) aromatic hydrocarbon group or a C 6 to C 20 alicyclic hydrocarbon group, O) NH-,

m and n are numbers representing the molar ratio between the imide repeating unit and the benzoxazole repeating unit, and n / m is a real number larger than 0 and smaller than 0.01.

The tetracarboxylic acid dianhydride compound may be at least one selected from the group consisting of 3,3 ', 4,4'-biphenyl tetracarboxylic dianhydride (BPDA), bicyclic [2.2. 2] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride (bicycle [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, , 3 ', 4,4'-diphenylsulfone tetracarboxylic dianhydride (DSDA), 4,4' - (hexafluoroisopropylidene) dipentaerythritol tetra (4,4'-oxydiphthalic anhydride, ODPA), pyromellitic dianhydride (4,4'-hexafluoroisopropylidene diphthalic anhydride, 6FDA) pyromellitic dianhydride (PMDA), 4 - ((2,5-dioxo tedrahydrofuran-3-yl) -1,2,3,4-tetranaphthalene-1,2-dicarboxylic anhydride - (2,5-dioxotetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride, D TDA), 1,2,4,5-benzenetetracarboxylic dianhydride, 1,2,3,4-benzenetetracarboxylic acid dianhydride, 1,4-bis (2,3-dicarboxyphenoxy) Benzene dianhydride 1,3-bis (3,4-dicarboxyphenoxy) benzene dianhydride 1,2,4,5-naphthalenetetracarboxylic acid dianhydride 1,2,5,6-naphthalenetetracar Naphthalenetetracarboxylic acid dianhydride, 2,3,6,7-naphthalenetetracarboxylic acid dianhydride, 2,6-dichloronaphthalene-1,4,5, Tetracarboxylic acid dianhydride, 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic acid dianhydride, 2,3,6,7-tetrachloronaphthalene-1,4,5,8 - tetracarboxylic dianhydride; 2,2 ', 3,3'-biphenyltetracarboxylic dianhydride; 4,4'-bis (3,4-dicarboxyphenoxy) biphenyl dianhydride; Bis (2,3-dicarboxyphenyl) ether dianhydride; 4,4'-bis (2,3-dicarboxyphenoxy) diphenyl ether dianhydride; 4,4'-bis (3,4-dicarboxyphenoxy) diphenyl ether dianhydride; Bis (3,4-dicarboxyphenyl) sulfide dianhydride; 4,4'-bis (2,3-dicarboxyphenoxy) diphenyl sulfide dianhydride; 4,4'-bis (3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride; Bis (3,4-dicarboxyphenyl) sulfone dianhydride; 4,4'-bis (2,3-dicarboxyphenoxy) diphenylsulfone dianhydride; 4,4'-bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydride; 3,3 ', 4,4'-benzophenone tetracarboxylic acid dianhydride; 2,2 ', 3,3'-benzophenone tetracarboxylic acid dianhydride; 2,3,3 ', 4'-benzophenone tetracarboxylic acid dianhydride; 4,4'-bis (3,4-dicarboxyphenoxy) benzophenone dianhydride; Bis (2,3-dicarboxyphenyl) m ethane dianhydride; Bis (3,4-dicarboxyphenyl) methane dianhydride; 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride; 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride; 1,2-bis (3,4-dicarboxyphenyl) ethane dianhydride; 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride; 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride; 2,2-bis [4- (2,3-dicarboxyphenoxy) phenyl] propane dianhydride; 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride; 2,2- [4- (2,3-dicarboxyphenoxy) -4 '- (3,4-dicarboxyphenoxy) diphenyl] -propane dianhydride; 2,2-bis [4- (3,4-dicarboxyphenoxy-3,5-dimethyl) phenyl] propane dianhydride; 2,3,4,5-thiopentetracarboxylic acid dianhydride; 2,3,5,6-pyrazine tetracarboxylic acid dianhydride; 1,8,9,10-phenanthrenetetracarboxylic acid dianhydride; 3,4,9,10-perylene tetracarboxylic acid dianhydride; 1,3-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride; 1,1-bis (3,4-dicarboxyphenyl) -1-phenyl-2,2,2-trifluoroethane dianhydride; 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] hexafluoropropane dianhydride; 1,1-bis [4- (3,4-dicarboxyphenoxy) phenyl] -1-phenyl-2,2,2-trifluoroethane dianhydride; And 4,4'-bis [2- (3,4-dicarboxyphenyl) hexafluoroisopropyl] diphenyl ether dianhydride.

The diamine compound may be selected from the group consisting of m-phenylenediamine; p-phenylenediamine; 1,3-bis (4-aminophenyl) propane; 2,2-bis (4-aminophenyl) propane; 4,4'-diamino-diphenylmethane; 1,2-bis (4-aminophenyl) ethane; 1,1-bis (4-aminophenyl) ethane; 2,2'-diamino-diethyl sulfide; Bis (4-aminophenyl) sulfide; 2,4'-diamino-diphenyl sulfide; Bis (3-aminophenyl) sulfone; Bis (4-aminophenyl) sulfone; 4,4'-diamino-dibenzylsulfoxide; Bis (4-aminophenyl) ether; Bis (3-aminophenyl) ether; Bis (4-aminophenyl) diethylsilane; Bis (4-aminophenyl) diphenylsilane; Bis (4-aminophenyl) ethylphosphine oxide; Bis (4-aminophenyl) phenylphosphine oxide; Bis (4-aminophenyl) -N-phenylamine; Bis (4-aminophenyl) -N-methylamine; 1,2-diamino-naphthalene; 1,4-diamino-naphthalene; 1,5-diamino-naphthalene; 1,6-diamino-naphthalene; 1,7-diamino-naphthalene; 1,8-diamino-naphthalene; 2,3-diamino-naphthalene; 2,6-diamino-naphthalene; 1,4-diamino-2-methyl-naphthalene; 1,5-diamino-2-methyl-naphthalene; 1,3-diamino-2-phenyl-naphthalene; 4,4'-diamino-biphenyl; 3,3'-diamino-biphenyl; 3,3'-dichloro-4,4'-diamino-biphenyl; 3,3'-dimethyl-4,4'-diamino-biphenyl; 3,4'-dimethyl-4,4'-diamino-biphenyl; 3,3'-dimethoxy-4,4'-diamino-biphenyl; 4,4'-bis (4-aminophenoxy) -biphenyl; 2,4-diamino-toluene; 2,5-diamino-toluene; 2,6-diamino-toluene; 3,5-diamino-toluene; 1,3-diamino-2,5-dichloro-benzene; 1,4-diamino-2,5-dichloro-benzene; 1-methoxy-2,4-diamino-benzene; 1,4-diamino-2-methoxy-5-methyl-benzene; 1,4-diamino-2,3,5,6-tetramethyl-benzene; 1,4-bis (2-methyl-4-amino-pentyl) -benzene; 1,4-bis (1,1-dimethyl-5-amino-pentyl) -benzene; 1,4-bis (4-aminophenoxy) -benzene; o-xylylenediamine; m-xylylenediamine; p-xylylenediamine; 3,3'-diamino-benzophenone; 4,4'-diamino-benzophenone; 2,6-diamino-pyridine; 3,5-diamino-pyridine; 1,3-diamino-adamantane; Bis [2- (3-aminophenyl) hexafluoroisopropyl] diphenyl ether; 3,3'-diamino-1,1'-diadamantane; N- (3-aminophenyl) -4-aminobenzamide; 4-aminophenyl 3-aminobenzoate; 2,2-bis (4-aminophenyl) hexafluoropropane; 2,2-bis (3-aminophenyl) hexafluoropropane; 2- (3-aminophenyl) -2- (4-aminophenyl) hexafluoropropane; 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane; 2,2-bis [4- (2-chloro-4-aminophenoxy) phenyl] hexafluoropropane; 1,1-bis (4-aminophenyl) -1-phenyl-2,2,2-trifluoroethane; 1,1-bis [4- (4-aminophenoxy) phenyl] -1-phenyl-2,2,2-trifluoroethane; 1,4-bis (3-aminophenyl) but-1-en-3-yl; 1,3-bis (3-aminophenyl) hexafluoropropane; 1,5-bis (3-aminophenyl) decafluoropentane; And 4,4'-bis [2- (4-aminophenoxyphenyl) hexafluoroisopropyl] diphenyl ether, diaminocyclohexane, bicyclohexyldiamine, 4,4'-diaminocyclohexylmethane, and And diaminofluorene.

The hydroxydiamine compound may be selected from the group consisting of 3,3'-dihydroxy benzidine; 3,4'-diamino-3'4-dihydroxybiphenyl; 3,4'-diamino-3'4-dihydroxybiphenyl; 3,3'-diamino-4,4'-dihydroxybiphenyl; 3,3'-dihydroxy-4,4'-diamino diphenyloxide; 3,3'-dihydroxy-4,4'-diamino diphenyl oxide; 3,3'-dihydroxy-4,4'-diamino diphenylsulphone; 3,3'-dihydroxy-4,4'-diamino diphenylsulphone; Bis (3-amino-4-hydroxyphenyl) sulfone); 2,2-bis- (3-amino-4-hydroxyphenyl) propane); Bis- (3-hydroxy-4-aminophenyl) methane; bis- (3-hydroxy-4-aminophenyl) methane; 4,6-diaminoresorcinol; 3,3'-dihydroxy-4,4'-diamino-benzophenone; 3,3'-dihydroxy-4,4'-diamino benzophenone; 1,1-bis- (3-hydroxy-4-aminophenyl) ethane); 1,3-bis- (3-hydroxy-4-aminophenyl) propane; 1,3-bis- (3-hydroxy-4-aminophenyl) propane; 2,2-bis- (3-hydroxy-4-aminophenyl) propane; 2,2-bis- (3-hydroxy-4-aminophenyl) propane; And 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoro-propane. .

The molar ratio of the tetracarboxylic dianhydride compound to the diamine compounds may be 0.9 to 1.1.

The molar ratio of the aromatic hydroxydiamine compound to the diamine compound (the aromatic hydroxy diamine compound / the diamine compound) may be more than 0 and less than 0.01.

The polycondensation can be carried out by stirring the monomer composition, optionally under an inert gas atmosphere, at a temperature of 0 to 100 degrees Celsius.

The imidization can be performed by chemical imidization or thermal imidization.

The heat treatment may be carried out in the range of 50 to 500 degrees Celsius (for example, 300 degrees Celsius or more, or 350 degrees Celsius or more and 450 degrees Celsius or less), optionally under an inert gas atmosphere.

In another embodiment, the electronic device may comprise a transparent film as described above.

The electronic device may be a flat panel display, a touch screen panel, a solar cell, an e-window, a heat mirror, a transparent transistor, a flexible display, a complementary metal oxide semiconductor sensor, or a light emitting diode illumination.

In another embodiment, there is provided a composition comprising a polyamic acid represented by the following formula:

[Chemical Formula 5]

A ₁ is the same or different and each independently represents a substituted or unsubstituted quadrivalent C6 to C24 aliphatic cyclic group, a substituted or unsubstituted quadrivalent C6 to C24 aromatic ring group, or a substituted or unsubstituted quadrivalent C4 To C24 heteroaromatic ring group, and the aliphatic ring group, the aromatic ring group, or the heteroaromatic ring group may be present singly or two or more rings may be fused to each other to form a condensed ring; More than one ring is a direct bond, -O-, -S-, -C (= O) -, -CH (OH) -, -S (= O) 2 -, -Si (CH 3) 2 -, ( CH _{2) p (where, 1≤p≤10), (CF 2)} q ( where, 1≤q≤10), -CR ₂ - (wherein, R represents, each independently, hydrogen, an aliphatic C1 to C10 -C (CF ₃ ) ₂ -, -C (CF ₃ ) (C ₆ H ₅ ) -, or -C (= C ₃ -C 20) aromatic hydrocarbon group or a C 6 to C 20 alicyclic hydrocarbon group, O) NH-,

A ₂ 'is selected from the following,

,

,

,

,

,

,

, 또는

, or

Here, L is the same or different and each independently represents a direct bond, -O-, -S-, -C (= O) -, -CH (OH) -, -S (= O) 2 -, -Si (CH ₃ ) ₂ -, (CH ₂ ) _p (wherein 1≤p≤10), (CF ₂ ) _q (where 1≤q≤10), -CR ₂ - , -C (CF ₃ ) ₂ -, -C (CF ₃ ) (C ₆ H ₅ ), or a group of the following formula ) -, or -C (= O) NH-, * is the moiety connected to the adjacent atom (eg, nitrogen), the hydroxy group is in ortho position with respect to the moiety comprising *

A ₃ is a substituted or unsubstituted divalent C6 to C24 aliphatic ring group, a substituted or unsubstituted divalent C6 to C24 aromatic ring group or a substituted or unsubstituted divalent C4 to C24 hetero aromatic ring group, The ring group, the aromatic ring group, or the heteroaromatic ring group may be present singly or two or more rings may be fused to each other to form a condensed ring; More than one ring is a direct bond, -O-, -S-, -C (= O) -, -CH (OH) -, -S (= O) 2 -, -Si (CH 3) 2 -, ( CH _{2) p (where, 1≤p≤10), (CF 2)} q ( where, 1≤q≤10), -CR ₂ - (wherein, R represents, each independently, hydrogen, an aliphatic C1 to C10 -C (CF ₃ ) ₂ -, -C (CF ₃ ) (C ₆ H ₅ ) -, or -C (= C ₃ -C 20) aromatic hydrocarbon group or a C 6 to C 20 alicyclic hydrocarbon group, O) NH-,

m and n are numbers representing the molar ratio between the imide repeating unit and the benzoxazole repeating unit, and n / m is a real number greater than 0 and less than 0.01.

In another embodiment, there is provided a composition comprising a polyimide having the formula:

[Chemical Formula 6]

In the above equations,

A ₁ is the same or different and each independently represents a substituted or unsubstituted quadrivalent C6 to C24 aliphatic cyclic group, a substituted or unsubstituted quadrivalent C6 to C24 aromatic ring group, or a substituted or unsubstituted quadrivalent C4 To C24 heteroaromatic ring group, and the aliphatic ring group, the aromatic ring group, or the heteroaromatic ring group may be present singly or two or more rings may be fused to each other to form a condensed ring; More than one ring is a direct bond, -O-, -S-, -C (= O) -, -CH (OH) -, -S (= O) 2 -, -Si (CH 3) 2 -, ( CH _{2) p (where, 1≤p≤10), (CF 2)} q ( where, 1≤q≤10), -CR ₂ - (wherein, R represents, each independently, hydrogen, an aliphatic C1 to C10 -C (CF ₃ ) ₂ -, -C (CF ₃ ) (C ₆ H ₅ ) -, or -C (= C ₃ -C 20) aromatic hydrocarbon group or a C 6 to C 20 alicyclic hydrocarbon group, O) NH-,

A ₂ ' is selected from the following,

,

,

,

,

,

,

, 또는

, or

Here, L is the same or different and each independently represents a direct bond, -O-, -S-, -C (= O) -, -CH (OH) -, -S (= O) 2 -, -Si (CH ₃ ) ₂ -, (CH ₂ ) _p (wherein 1≤p≤10), (CF ₂ ) _q (where 1≤q≤10), -CR ₂ - , -C (CF ₃ ) ₂ -, -C (CF ₃ ) (C ₆ H ₅ ), or a group of the following formula ) -, or -C (= O) NH-, * is a moiety connected to a neighboring atom (eg, nitrogen), and a hydroxyl group (-OH) ≪ / RTI >

A ₃ is a substituted or unsubstituted divalent C6 to C24 aliphatic ring group, a substituted or unsubstituted divalent C6 to C24 aromatic ring group or a substituted or unsubstituted divalent C4 to C24 hetero aromatic ring group, The ring group, the aromatic ring group, or the heteroaromatic ring group may be present singly or two or more rings may be fused to each other to form a condensed ring; More than one ring is a direct bond, -O-, -S-, -C (= O) -, -CH (OH) -, -S (= O) 2 -, -Si (CH 3) 2 -, ( CH _{2) p (where, 1≤p≤10), (CF 2)} q ( where, 1≤q≤10), -CR ₂ - (wherein, R represents, each independently, hydrogen, an aliphatic C1 to C10 -C (CF ₃ ) ₂ -, -C (CF ₃ ) (C ₆ H ₅ ) -, or -C (= C ₃ -C 20) aromatic hydrocarbon group or a C 6 to C 20 alicyclic hydrocarbon group, O) NH-,

m and n are numbers representing the molar ratio between the imide repeating unit and the benzoxazole repeating unit, wherein n / m is a real number greater than 0 and less than 0.01.

A polymer film having improved thermal properties (e.g., low thermal expansion coefficient) and high transparency can be provided. Such a polymer film can find its usefulness in various flexible protective films used in the manufacture of flexible substrates, LEDs, semiconductor sensors, and the like.

Fig. 1 is a graph showing the results of Experimental Example 1 and Experimental Example 3. Fig.
2 includes a scanning electron microscope image of vapor deposition films (film 1, film 2, vapor deposition film formed on film 3 and vapor deposition films formed on films obtained in Examples 1 to 3) formed in the Si oxide vapor deposition film formation experiment .
3 includes a scanning electron microscope image of vapor deposition films formed in the Si oxide vapor deposition film formation experiment (vapor deposition films formed on the films obtained in Examples 4 to 6).

Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited thereto, and the present invention is only defined by the scope of the following claims.

Unless otherwise specified in the specification, the term "substituted" means that at least one hydrogen atom contained in a given functional group is replaced by a halogen atom (-F, -Cl, -Br or -I), a hydroxyl group, a nitro group, , an amino group ^{_{(NH 2, NH (R 100}} ) , or ^{N (R 101) (R 102} ) , wherein R ^100, R ¹⁰¹ and R ¹⁰² are the same or different, being each independently selected from C1 to C10 alkyl group), amido A substituted or unsubstituted alkyl group, a substituted or unsubstituted alicyclic group (e.g., a cycloalkyl group and the like), a substituted or unsubstituted aryl group (such as a substituted or unsubstituted aryl group), a heterocyclic group A substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted heteroaryl group, and a substituted or unsubstituted heterocyclic group, for example, a benzyl group, a naphthyl group, Substituted by one or more substituents selected from It means, and said substituents may form a ring are connected to each other.

Unless otherwise specified in the specification, "alkyl group" means C1 to C30 alkyl group, specifically C1 to C15 alkyl group, "cycloalkyl group" means C3 to C30 cycloalkyl group, specifically C3 Refers to a C1 to C30 alkoxy group, specifically a C1 to C18 alkoxy group, and an "ester group" means a C2 to C30 ester group, specifically, a C2 to C30 cycloalkyl group, Quot; means a C2 to C30 ketone group, specifically, a C2 to C18 ketone group, and the "aryl group" means a C6 to C30 aryl group, specifically, a C6 to C18 aryl Quot; alkenyl group "means a C2 to C30 alkenyl group, specifically, a C2 to C18 alkenyl group.

In this specification, the terms "polyimide-polybenzoxazole copolymer" and "poly (imide-benzoxazole copolymer)" have the same meaning and are used interchangeably.

The transparent film according to one embodiment includes a polyimide-polybenzoxazole copolymer including a repeating unit represented by the following formula (1);

[Chemical Formula 1]

In formula (1), A ₁ and A ₁ 'is a group derived from a dianhydride compound of formula (2) to be described later.

In formula (1), each A ₁ is the same or different, and each independently represents a substituted or unsubstituted quadrivalent C6 to C24 aliphatic cyclic group, a substituted or unsubstituted quadrivalent C6 to C24 aromatic cyclic group, Unsubstituted quaternary C4 to C24 heteroaromatic ring group. The aliphatic cyclic group, the aromatic cyclic group, or the heteroaromatic cyclic group may be present singly. The aliphatic cyclic group, the aromatic cyclic group, or the heteroaromatic cyclic group may be fused to each other to form a condensed ring. The aliphatic cyclic group, the aromatic cyclic group, or the heteroaromatic cyclic group is a cyclic group in which at least two rings are directly bonded, -O-, -S-, -C (= O) -, -CH (OH) _{= O) 2 -, -Si (} CH 3) 2 -, (CH 2) p ( _{where, 1≤p≤10), (CF 2)} q ( where, 1≤q≤10), -CR ₂ - ( Here, each R is independently hydrogen, a C1 to C10 aliphatic hydrocarbon group (e.g., an alkyl group or an alkenyl group), a C6 to C20 aromatic hydrocarbon group (e.g., an aryl group), or a C6 to C20 alicyclic hydrocarbon group (e. g., cycloalkyl), _{Im), -C (CF 3) 2} - it can be, or -C (= O) is attached by _{NH- -, -C (CF 3)} (C 6 H 5).

Each A ₁ 'represents a substituted or unsubstituted divalent C6 to C24 aliphatic cyclic group, a substituted or unsubstituted divalent C6 to C24 aromatic cyclic group, or a substituted or unsubstituted divalent C4 To C24 heteroaromatic ring group. In one embodiment, the aliphatic cyclic group, the aromatic cyclic group, or the heteroaromatic cyclic group may be present singly. In another embodiment, the aliphatic cyclic group, the aromatic cyclic group, or the heteroaromatic cyclic group is fused to two or more rings to form a condensed ring; Or two or more rings is a direct bond, -O-, -S-, -C (= O) -, -CH (OH) -, -S (= O) 2 -, -Si (CH 3) 2 -, (CH ₂ ) _p wherein ₁ ? _P ? 10, (CF ₂ ) _q wherein ₁ ? _Q ? 10, -CR ₂ - wherein R is independently hydrogen, aliphatic hydrocarbon groups, C6 to an aromatic hydrocarbon group, or a C6 to C20 alicyclic hydrocarbon group of _{C20), -C (CF 3) 2} -, -C (CF 3) (C 6 H 5) -, or -C ( = O) NH-.

In one embodiment, A < ₁ >

In the above formulas, each cyclic moiety may be substituted or unsubstituted; Each L is the same or different, each independently, a direct bond, -O-, -S-, -C (= O) -, -CH (OH) -, -S (= O) 2 -, -Si (CH ₃ ) ₂ -, (CH ₂ ) _p (wherein 1≤p≤10), (CF ₂ ) _q (where 1≤q≤10), -CR ₂ - a, or -C (= O) NH-, - , hydrogen, C1 to C10 aliphatic hydrocarbon group, aromatic hydrocarbon group of C6 to C20, or C6 to alicyclic hydrocarbon groups) of the C20, -C (CF _{3) 2} * Is the moiety connected to the adjacent atom (e. G., The carbon of the carbonyl group)

Z ¹ and Z ² are the same or different and independently represent -N = or -C (R ¹⁰⁰ ) =, R ¹⁰⁰ is hydrogen or a C 1 to C 5 alkyl group, Z ¹ and Z ² are simultaneously -C ¹⁰⁰ ) =,

Z ³ is -O-, -S-, or -NR ¹⁰¹ -, wherein R ¹⁰¹ is hydrogen or a C 1 to C 5 alkyl group,

* Is the moiety to which the moiety is attached to a neighboring atom.

Similarly, in one embodiment, A ₁ 'can be selected from the following formulas:

In the above formulas, each of the residues may be substituted or non-substituted,

And each L is the same or different, each independently, a single bond, -O-, -S-, -C (= O) -, -CH (OH) -, -S (= O) 2 -, -Si (CH ₃ ) ₂ -, (CH ₂ ) _p wherein ₁ ? _P ? 10, (CF ₂ ) _q wherein ₁ ? _Q ? 10, -CR ₂ - wherein R is independently hydrogen, an aromatic hydrocarbon group of the aliphatic hydrocarbon groups, C6 to C20, or C6 to C20 alicyclic hydrocarbon _{group), -C (CF 3) 2} -, -C (CF 3) (C 6 H 5) -, or -C (= O) NH-,

Z ¹ and Z ² are the same or different and independently represent -N = or -C (R ¹⁰⁰ ) =, R ¹⁰⁰ is hydrogen or a C 1 to C 5 alkyl group, Z ¹ and Z ² are simultaneously -C ¹⁰⁰ ) =,

Z ³ is -O-, -S-, or -NR ¹⁰¹ -, wherein R ¹⁰¹ is hydrogen or a C 1 to C 5 alkyl group,

* Is the moiety to which the moiety is attached to a neighboring atom.

For example, A ₁ may be selected from, but is not limited to:

In formula (1), A ₂ is a residue derived from a hydroxy diamine represented by the following formula (4). A ₂ can be selected from the following:

Here, the aromatic ring residue may be substituted or unsubstituted. L is the same or different and each independently represents a direct bond, -O-, -S-, -C (= O) -, -CH (OH) -, -S (= O) 2 -, -Si (CH ₃ ) ₂ -, (CH ₂ ) _p wherein 1≤p≤10, (CF ₂ ) _q (where 1≤q≤10), -CR ₂ - wherein R is independently hydrogen , A C 1 to C 10 aliphatic hydrocarbon group, a C 6 to C 20 aromatic hydrocarbon group, or a C 6 to C 20 alicyclic hydrocarbon group), -C (CF ₃ ) ₂ -, -C (CF ₃ ) (C ₆ H ₅ ) , Or -C (= O) NH-, and * is the moiety connected to the adjacent atom (e.g., nitrogen or oxygen of the benzoxazole ring).

For example, A ₂ may be selected from the following, but is not limited to:

In formula (1), A ₃ is a residue derived from a diamine compound represented by the following formula (3). A ₃ is a substituted or unsubstituted divalent C6 to C24 aliphatic ring group, a substituted or unsubstituted divalent C6 to C24 aromatic ring group or a substituted or unsubstituted divalent C4 to C24 hetero aromatic ring group, The ring group, the aromatic ring group, or the heteroaromatic ring group may be present singly or two or more rings may be fused to each other to form a condensed ring; More than one ring is a direct bond, -O-, -S-, -C (= O) -, -CH (OH) -, -S (= O) 2 -, -Si (CH 3) 2 -, ( CH _{2) p (where, 1≤p≤10), (CF 2)} q ( where, 1≤q≤10), -CR ₂ - (wherein, R represents, each independently, hydrogen, an aliphatic C1 to C10 -C (CF ₃ ) ₂ -, -C (CF ₃ ) (C ₆ H ₅ ) -, or -C (= C ₃ -C 20) aromatic hydrocarbon group or a C 6 to C 20 alicyclic hydrocarbon group, O) NH-. ≪ / RTI >

A ₃ can be selected from the following:

In the above formulas, the aromatic or alicyclic ring may be substituted or unsubstituted, and L may be the same or different and each independently represents a direct bond, -O-, -S-, -C (= O) -, -CH (OH) -, -S (= O) 2 -, -Si (CH 3) 2 -, (CH 2) p ( _{where, 1≤p≤10), (CF 2)} q ( where, 1≤q≤ 10), -CR ₂ - (wherein, R represents, each independently, hydrogen, C1 to C10 aliphatic hydrocarbon groups, C6 to C20 aromatic hydrocarbon group, or a C6 to C20 alicyclic hydrocarbon group), -C (CF of _{3) 2 -, -C (CF} 3) (C 6 H 5) - a, or -C (= O) NH-, * is the part already connected to the nitrogen of the dE loop.

For example, A ₃ may be selected from, but is not limited to:

m and n are numbers representing the molar ratio between the imide repeating unit and the benzoxazole repeating unit and n / m is a number greater than 0 and less than 0.01, for example, from 0.0001 to 0.009, greater than 0.0005, and less than 0.006, or from 0.001 to 0.005. to be. When the poly (imide-benzoxazole) copolymer has an n / m value in the above-mentioned range, the film including the poly (imide-benzoxazole) copolymer can exhibit improved optical properties, excellent thermal stability, and excellent surface properties as described later.

For example, the film may have an average 85% or greater, for example, at least about 86%, at least about 87%, or at least about 87.5% of the average field average transmittance at a wavelength of 300-800 when measured with a UV spectrometer at about 10 [ % ≪ / RTI > The film may have a transmittance of 80.5% or more, for example, 81.0% or more, or 81.1% or more of light with a wavelength of 430nm. The film may have a yellow index of 5.2 or less, such as 5.0 or less, 4.9 or less, 4.8 or less, 4.7 or less, 4.6 or less, or 4.5 or less. The film preferably has a coefficient of thermal expansion (CTE) of less than or equal to 12 ppm / less, such as 8.5 ppm / less, 8.4 ppm / less, 8.2 ppm / less, 8.0 ppm / / Or less, or 6.9 ppm / or less.

Therefore, the above-mentioned film can find utility in a flexible substrate or a flexible protective film which is required to have excellent mechanical properties, thermal stability and optical properties.

Further, the above-mentioned film may further include a vapor deposition film on its surface. The deposition layer may be formed of a material selected from the group consisting of silicon oxides, polysilicic acids, alkali metal silicates, alkaline earth metal silicates, aluminosilicates, silicon nitrides, silicon oxynitrides, Silicon carbide, silicon alumina oxynitride, or a combination thereof.

In one embodiment, such a deposition film may be a material that can be used as a barrier inorganic layer in a flexible substrate or the like. When a metal such as SiO ₂ , SiN, or a quasi metal oxide / nitride film is deposited on a polyimide film, surface curvature phenomenon can not be avoided. Such surface curvature can cause serious problems in application to a flexible substrate or a protective film. In contrast, the above-described films according to one embodiment, including copolymers having a small amount of polybenzoxazole repeating units limited to polyimide, can deposit metal or metalloid oxide / nitride films without surface bending.

In another embodiment, the aforementioned method for producing a transparent film may comprise the following steps:

A tetracarboxylic acid dianhydride compound represented by the following formula (2), a diamine compound represented by the following formula (3), and a condensation product of a hydroxy diamine compound represented by the following formula (4) and containing a hydroxy group at an ortho position with respect to an amine group A composition comprising a polyamic acid copolymer represented by the following formula (5):

Applying the composition comprising the polyamic acid copolymer to a substrate and imidizing the film to obtain a film comprising a polyimide copolymer represented by Formula 6;

And heat treating the film to obtain a transparent film comprising the polyimide-polybenzoxazole copolymer represented by Formula 1:

(2)

(3)

NH ₂ -A ₃ -NH ₂

[Chemical Formula 4]

NH ₂ -A ₂ '-NH ₂

[Chemical Formula 5]

[Chemical Formula 6]

In the above equations,

A ₁ is the same or different and each independently represents a substituted or unsubstituted quadrivalent C6 to C24 aliphatic cyclic group, a substituted or unsubstituted quadrivalent C6 to C24 aromatic ring group, or a substituted or unsubstituted quadrivalent C4 To C24 heteroaromatic ring group, and the aliphatic ring group, the aromatic ring group, or the heteroaromatic ring group may be present singly or two or more rings may be fused to each other to form a condensed ring; More than one ring is a direct bond, -O-, -S-, -C (= O) -, -CH (OH) -, -S (= O) 2 -, -Si (CH 3) 2 -, ( CH _{2) p (where, 1≤p≤10), (CF 2)} q ( where, 1≤q≤10), -CR ₂ - (wherein, R represents, each independently, hydrogen, an aliphatic C1 to C10 -C (CF ₃ ) ₂ -, -C (CF ₃ ) (C ₆ H ₅ ) -, or -C (= C ₃ -C 20) aromatic hydrocarbon group or a C 6 to C 20 alicyclic hydrocarbon group, O) NH-,

A ₂ 'is selected from the following,

,

,

,

,

,

,

, 또는

, or

Here, L is the same or different and each independently represents a direct bond, -O-, -S-, -C (= O) -, -CH (OH) -, -S (= O) 2 -, -Si (CH ₃ ) ₂ -, (CH ₂ ) _p (wherein 1≤p≤10), (CF ₂ ) _q (where 1≤q≤10), -CR ₂ - , -C (CF ₃ ) ₂ -, -C (CF ₃ ) (C ₆ H ₅ ), or a group of the following formula ) -, or -C (= O) NH-, * is the moiety connected to nitrogen, the hydroxy group is present in the ortho position with respect to the moiety comprising *

A ₃ is a substituted or unsubstituted divalent C6 to C24 aliphatic ring group, a substituted or unsubstituted divalent C6 to C24 aromatic ring group or a substituted or unsubstituted divalent C4 to C24 hetero aromatic ring group, The ring group, the aromatic ring group, or the heteroaromatic ring group may be present singly or two or more rings may be fused to each other to form a condensed ring; More than one ring is a direct bond, -O-, -S-, -C (= O) -, -CH (OH) -, -S (= O) 2 -, -Si (CH 3) 2 -, ( CH _{2) p (where, 1≤p≤10), (CF 2)} q ( where, 1≤q≤10), -CR ₂ - (wherein, R represents, each independently, hydrogen, an aliphatic C1 to C10 -C (CF ₃ ) ₂ -, -C (CF ₃ ) (C ₆ H ₅ ) -, or -C (= C ₃ -C 20) aromatic hydrocarbon group or a C 6 to C 20 alicyclic hydrocarbon group, O) NH-,

m and n are numbers representing the molar ratio between the imide repeating unit and the benzoxazole repeating unit, and n / m is a real number greater than 0 and less than 0.01.

The tetracarboxylic acid dianhydride compound may be at least one selected from the group consisting of 3,3 ', 4,4'-biphenyl tetracarboxylic dianhydride (BPDA), bicyclic [2.2. 2] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride (bicycle [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, , 3 ', 4,4'-biphenylsulfone tetracarboxylic dianhydride (DSDA), and 4,4' - (hexafluoroisopropylidene) 4,4'-oxydiphthalic anhydride (ODPA), pyromellitic dianhydride (4,4'-hexafluoroisopropylidene diphthalic anhydride, 6FDA), 4,4'-oxydiphthalic anhydride pyromellitic dianhydride (PMDA), 4 - ((2,5-dioxo tedrahydrofuran-3-yl) -1,2,3,4-tetranaphthalene-1,2-dicarboxylic anhydride 4- (2,5-dioxotetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride, DTDA), 1,2,4,5-benzenetetracarboxylic acid dianhydride, 1,2,3,4-benzenetetracarboxylic acid dianhydride, 1,4-bis (2,3-dicarboxyphenoxy) Benzene dianhydride 1,3-bis (3,4-dicarboxyphenoxy) benzene dianhydride 1,2,4,5-naphthalenetetracarboxylic acid dianhydride 1,2,5,6-naphthalenetetracar Naphthalene tetracarboxylic acid dianhydride, 2,3,6,7-naphthalenetetracarboxylic acid dianhydride, 2,6-dichloronaphthalene-1,4,5, Tetracarboxylic acid dianhydride, 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic acid dianhydride, 2,3,6,7-tetrachloronaphthalene-1,4,5,8 - tetracarboxylic dianhydride; 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride; 2,2 ', 3,3'-biphenyltetracarboxylic dianhydride; 4,4'-bis (3,4-dicarboxyphenoxy) diphenyl dianhydride; Bis (2,3-dicarboxyphenyl) ether dianhydride; 4,4'-bis (2,3-dicarboxyphenoxy) diphenyl ether dianhydride; 4,4'-bis (3,4-dicarboxyphenoxy) diphenyl ether dianhydride; Bis (3,4-dicarboxyphenyl) sulfide dianhydride; 4,4'-bis (2,3-dicarboxyphenoxy) diphenyl sulfide dianhydride; 4,4'-bis (3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride; Bis (3,4-dicarboxyphenyl) sulfone dianhydride; 4,4'-bis (2,3-dicarboxyphenoxy) diphenylsulfone dianhydride; 4,4'-bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydride; 3,3 ', 4,4 "-benzophenone tetracarboxylic acid dianhydride; 2,2 ', 3,3'-benzophenone tetracarboxylic acid dianhydride; 2,3,3 ', 4'-benzophenone tetracarboxylic acid dianhydride; 4,4'-bis (3,4-dicarboxyphenoxy) benzophenone dianhydride; Bis (2,3-dicarboxyphenyl) m ethane dianhydride; Bis (3,4-dicarboxyphenyl) methane dianhydride; 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride; 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride;

1,2-bis (3,4-dicarboxyphenyl) ethane dianhydride; 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride; 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride; 2,2-bis [4- (2,3-dicarboxyphenoxy) phenyl] propane dianhydride; 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride; 4- (2,3-dicarboxyphenoxy) -4 '- (3,4-dicarboxyphenoxy) diphenyl-2,2-propane dianhydride; 2,2-bis [4- (3,4-dicarboxyphenoxy-3,5-dimethyl) phenyl] propane dianhydride; 2,3,4,5-thiopentetracarboxylic acid dianhydride; 2,3,5,6-pyrazine tetracarboxylic acid dianhydride; 1,8,9,10-phenanthrenetetracarboxylic acid dianhydride; 3,4,9,10-perylene tetracarboxylic acid dianhydride; 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride; 1,3-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride; 1,1-bis (3,4-dicarboxyphenyl) -1-phenyl-2,2,2-trifluoroethane dianhydride; 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] hexafluoropropane dianhydride; 1,1-bis [4- (3,4-dicarboxyphenoxy) phenyl] -1-phenyl-2,2,2-trifluoroethane dianhydride; And 4,4'-bis [2- (3,4-dicarboxyphenyl) hexafluoroisopropyl] diphenyl ether dianhydride. These dihydrate compounds are commercially available or are available by known methods. In one embodiment, the tetracarboxylic dianhydride is prepared by reacting 3,3 ', 4,4'-biphenyl tetracarboxylic dianhydride (BPDA) with 3,3', 4,4'-biphenyl tetracarboxylic dianhydride Pyromellitic dianhydride (PMDA) in an amount of about 50 to 95; About 5 to 50, for example about 60 to 90; About 10 to 40, such as about 70 to 80; In a ratio of about 20 to about 30.

The diamine compound may be selected from the group consisting of m-phenylenediamine; p-phenylenediamine; 1,3-bis (4-aminophenyl) propane; 2,2-bis (4-aminophenyl) propane; 4,4'-diamino-diphenylmethane; 1,2-bis (4-aminophenyl) ethane; 1,1-bis (4-aminophenyl) ethane; 2,2'-diamino-diethyl sulfide; Bis (4-aminophenyl) sulfide; 2,4'-diamino-diphenyl sulfide; Bis (3-aminophenyl) sulfone; Bis (4-aminophenyl) sulfone; 4,4'-diamino-dibenzylsulfoxide; Bis (4-aminophenyl) ether; Bis (3-aminophenyl) ether; Bis (4-aminophenyl) diethylsilane; Bis (4-aminophenyl) diphenylsilane; Bis (4-aminophenyl) ethylphosphine oxide; Bis (4-aminophenyl) phenylphosphine oxide; Bis (4-aminophenyl) -N-phenylamine; Bis (4-aminophenyl) -N-methylamine; 1,2-diamino-naphthalene; 1,4-diamino-naphthalene; 1,5-diamino-naphthalene; 1,6-diamino-naphthalene; 1,7-diamino-naphthalene; 1,8-diamino-naphthalene; 2,3-diamino-naphthalene; 2,6-diamino-naphthalene; 1,4-diamino-2-methyl-naphthalene; 1,5-diamino-2-methyl-naphthalene; 1,3-diamino-2-phenyl-naphthalene; 4,4'-diamino-biphenyl; 3,3'-diamino-biphenyl; 3,3'-dichloro-4,4'-diamino-biphenyl; 3,3'-dimethyl-4,4'-diamino-biphenyl; 3,3'-dimethyl-4,4'-diamino-biphenyl; 3,3'-dimethoxy-4,4'-diamino-biphenyl; 4,4'-bis (4-aminophenoxy) -biphenyl; 2,4-diamino-toluene; 2,5-diamino-toluene; 2,6-diamino-toluene; 3,5-diamino-toluene; 1,3-diamino-2,5-dichloro-benzene; 1,4-diamino-2,5-dichloro-benzene; 1-methoxy-2,4-diamino-benzene; 1,4-diamino-2-methoxy-5-methyl-benzene; 1,4-diamino-2,3,5,6-tetramethyl-benzene; 1,4-bis (2-methyl-4-amino-pentyl) -benzene; 1,4-bis (1,1-dimethyl-5-amino-pentyl) -benzene; 1,4-bis (4-aminophenoxy) -benzene; o-xylylenediamine; m-xylylenediamine; p-xylylenediamine; 3,3'-diamino-benzophenone; 4,4'-diamino-benzophenone; 2,6-diamino-pyridine; 3,5-diamino-pyridine; 1,3-diamino-adamantane; Bis [2- (3-aminophenyl) hexafluoroisopropyl] diphenyl ether; 3,3'-diamino-1,1,1'-diadamantane; N- (3-aminophenyl) -4-aminobenzamide; 4-aminophenyl-3-aminobenzoate; 2,2-bis (4-aminophenyl) hexafluoropropane; 2,2-bis (3-aminophenyl) hexafluoropropane; 2- (3-aminophenyl) -2- (4-aminophenyl) hexafluoropropane; 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane; 2,2-bis [4- (2-chloro-4-aminophenoxy) phenyl hexafluoropropane; 1,1-bis (4-aminophenyl) -1-phenyl-2,2,2-trifluoroethane; 1,1-bis [4- (4-aminophenoxy) phenyl] -1-phenyl-2,2,2-trifluoroethane; 1,4-bis (3-aminophenyl) but-1-en-3-yl; 1,3-bis (3-aminophenyl) hexafluoropropane; 1,5-bis (3-aminophenyl) decafluoropentane; And 4,4'-bis [2- (4-aminophenoxyphenyl) hexafluoroisopropyl] diphenyl ether, diaminocyclohexane, bicyclohexyldiamine, 4,4'-diaminocyclohexylmethane, and And diaminofluorene. Such diamine compounds are either commercially available or are available by known methods.

For example, the diamine compound may be a compound having the following structure:

The hydroxydiamine compound may be selected from the group consisting of 3,3'-dihydroxy benzidine; 3,4'-diamino-3'4-dihydroxybiphenyl; 3,3'-diamino-4,4'-dihydroxybiphenyl; 3,3'-dihydroxy-4,4'-diamino diphenyloxide; 3,3'-dihydroxy-4,4'-diamino diphenyl oxide; 3,3'-dihydroxy-4,4'-diamino diphenylsulphone; 3,3'-dihydroxy-4,4'-diamino diphenylsulphone; Bis (3-amino-4-hydroxyphenyl) sulfone); 2,2-bis- (3-amino-4-hydroxyphenyl) propane); Bis- (3-hydroxy-4-aminophenyl) methane; bis- (3-hydroxy-4-aminophenyl) methane; 4,6-diaminoresorcinol; 3,3'-dihydroxy-4,4'-diamino-benzophenone; 3,3'-dihydroxy-4,4'-diamino benzophenone; 1,1-bis- (3-hydroxy-4-aminophenyl) ethane); 1,3-bis- (3-hydroxy-4-aminophenyl) propane; 1,3-bis- (3-hydroxy-4-aminophenyl) propane; 2,2-bis- (3-hydroxy-4-aminophenyl) propane; 2,2-bis- (3-hydroxy-4-aminophenyl) propane; And hexafluoro-2,2-bis- (3-amino-4-hydroxyphenyl) propane). .

The molar ratio of the tetracarboxylic acid dianhydride compound to the diamine compound (i. E. The diamine compound of formula (III) and the hydroxy diamine compound of formula (IV)) may range from 0.9 to 1.1, for example from 0.95 to 1.05. The molar ratio of the aromatic hydroxydiamine compound of Formula 4 to the diamine compound of Formula 3 may be less than 0.01, such as 0.009 or less, 0.008 or less, 0.007 or less, 0.006 or less, or 0.005 or less. The molar ratio of the aromatic hydroxy diamine compound of formula (4) to the diamine compound of formula (3) may be greater than or equal to 0.0001, such as greater than or equal to 0.0003, greater than or equal to 0.0005, or greater than or equal to 0.0005.

The polycondensation can be carried out by stirring the monomer composition at a predetermined temperature in an air atmosphere or an inert gas atmosphere. The polymerization method is not particularly limited and can be appropriately selected. For example, the condensation polymerization may be carried out in a solution containing a condensation polymerization catalyst, if desired. In the case of solution polymerization, the polymerization solvent may be any solvent known for the production of polyamic acid. Examples of the solvent include dipolar aprotic solvents such as N-methylpyrrolidone, dimethylacetamide, dimethylformamide and dimethylsulfoxide, gamma butyrolactone, monochlorobenzene and the like. But is not limited thereto. Examples of the condensation polymerization catalyst include, but are not limited to, organic acids such as para-toluenesulfonic acid, and metal carboxylates such as zinc carboxylate salts. The polymerization time and temperature can be suitably selected without difficulty depending on the kind of the monomers used. For example, the polymerization may be carried out at a temperature of 100 degrees Celsius or less, such as 0 degree Celsius to 100 degrees Celsius, for 1 hour or more, for example, 12 hours or more. The concentration of the monomers in the solution can also be appropriately selected and is not particularly limited.

Imidizing the composition comprising the polyamic acid copolymer represented by the formula (5) to obtain a film comprising the polyimide copolymer represented by the formula (6).

The imidization may be chemical imidization or thermal imidization. Drying may be carried out at a temperature of not more than 250 degrees Celsius, for example, not more than 200 degrees Celsius, or not more than 190 degrees Celsius, for removing the solvent, as needed, before or after imidation.

Conditions for chemical imidization or thermal imidation are known.

For example, chemical imidization may include treating the polyamic acid copolymer with a reagent such as an aliphatic carboxylic acid dianhydride and a tertiary amine, for example, at ambient temperature. Commonly used reagents include acetic anhydride, pyridine, triethylamine, and the like. In this case, the imidization degree may vary depending on the solubility of the polyimide in the imide mixture. The chemical imidized product may be re-dissolved in a suitable solvent (e.g., NMP, DMAc) to produce a film. The resulting film can be heated for a short time (for example, within 3 hours) at a high temperature of, for example, 300 degrees Celsius or more to enhance imidization.

Thermal imidization can be performed by applying the polyamic acid copolymer composition to a substrate (for example, a glass substrate or the like) and heat-treating the substrate. The heat treatment atmosphere for thermal imidization is not particularly limited and can be appropriately selected. In view of the heat treatment method, the polyamic acid copolymer composition may be gradually heated to a target temperature at a predetermined heating rate, or may be heated stepwise at a predetermined temperature for a predetermined time.

The heat treatment temperature for thermal imidization is not particularly limited and can be appropriately selected. For example, the heat treatment temperature for thermal imidation may be at least 50 degrees Celsius, at least 200 degrees Celsius, for example, at least 250 degrees Celsius and at least 280 degrees Celsius. The heat treatment temperature for thermal imidization may be less than 350 degrees Celsius, less than 330 degrees Celsius, less than 320 degrees Celsius, or less than 310 degrees Celsius. For example, the heat treatment temperature for thermal imidization may range from 80 degrees Celsius to 350 degrees Celsius, from 80 degrees Celsius to 320 degrees Celsius, from 80 degrees Celsius to 310 degrees Celsius, but is not limited thereto. The heat treatment method includes a stepwise heat treatment at a constant temperature or a continuous heat treatment at a predetermined heating rate and is not particularly limited. The heating rate is not particularly limited, and may be, for example, 1 degree / min or more, for example, 5 degrees / min or 10 degrees / min or more, but is not limited thereto.

The film containing the polyimide copolymer represented by the formula (6) is heat-treated to obtain a transparent film comprising the polyimide-polybenzoxazole copolymer containing the repeating unit represented by the formula (1).

The heat treatment is not particularly limited as far as the benzoxazole ring can be formed by a cyclization reaction between the imide residue of the polyimide and the hydroxy group present in the adjacent Ar ₂ '. For example, the heat treatment may be performed at a temperature of 350 ° C or more, such as 360 ° C or more, 370 ° C or more, 380 ° C or more, 390 ° C or more, 400 ° C or more. For example, the heat treatment may be performed at a temperature of 500 degrees Celsius or less. The heat treatment time, the heat treatment method, and the atmosphere can be appropriately selected and are not particularly limited. For example, the heat treatment may be performed in an inert gas atmosphere (e.g., nitrogen, argon, etc.).

The above-mentioned production of a polyamic acid copolymer, preparation of a poly (hydroxy) imide copolymer by imidization of a polyamic acid copolymer, and production of a polyimide-polybenzoxazole copolymer are carried out in the presence of a dianhydride Bis (trifluoromethyl) benzidine (TFDB) as a diamine compound of the formula (3) and a hydroxy diamine compound of the formula (4) as biphenyl dianhydride (BPDA) Phenyl) hexafluoropropane (Bis-APAF) as an example, the reaction formula is as follows:

The content of the transparent film obtained by the heat treatment is as described above.

In another embodiment, the electronic device comprises the above-described transparent film. The electronic device may be a flat panel display, a touch panel screen (TSP), a solar cell, an electronic window, a heat mirror, a transparent transistor, a flexible display, a complementary metal oxide semiconductor sensor, or a light emitting diode It does not.

As described in detail above, the transparent film according to one embodiment has improved optical characteristics and thermal stability, and thus can be usefully used as a flexible substrate or a protective film in the manufacture of the above-described electronic device. In particular, when a vapor-deposited film of SiN, Si oxide or the like is to be formed on a flexible substrate, the surface bending phenomenon of the polyimide film can be prevented.

Hereinafter, the present invention will be described in detail with reference to examples. However, the following examples are for illustrative purposes only and are not intended to limit the scope of the present invention.

[Example]

Example 1;

[1] Production of polyamic acid copolymer:

119.65 mL of N-methylpyrrolidone was added to the 250 mL reactor, and 14.599 grams (0.0456 mol) of 2,2'-bis (trifluoromethyl) benzidine; TFDB) and 0.0167 grams (0.0456 millimoles) of 2,2'-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (Bis-APAF) as diamine monomers were completely dissolved with stirring to obtain a diamine mixture solution Prepare. To the diamine mixture solution, 9.398 g (0.0319 mol) of 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride (BPDA) and 2.986 g (0.0137 mol ) Pyromellitic dianhydride (PMDA) is rapidly added thereto and stirred at room temperature for 48 hours to obtain a solution containing a polyamic acid copolymer as a condensation product. The Bis-APAF content ratio to TFDB is 0.1 mole% (i.e., 0.001).

[2] Thermal imidization:

The solution is spin-coated on a glass substrate and heated to 80 degrees C to remove the solvent contained in the coating. Then, the coating is heated up to 300 degrees Celsius at a rate of 10 degrees Celsius / min under a nitrogen atmosphere, and this temperature is maintained for 1 hour to perform thermal imidization to obtain a polyimide copolymer film.

[3] Heat treatment for poly (imide-benzoxazole) copolymer formation:

The obtained polyimide copolymer film was heated to 400 degrees Celsius at 10 degrees C / min in a nitrogen atmosphere, and maintained at this temperature for 30 minutes to obtain a film containing a poly (imide-benzoxazole) copolymer.

Example 2:

As the diamine monomer, 14.567 grams (0.0455 moles) of 2,2'-bis (trifluoromethyl) benzidine (TFDB) and 0.05 grams (0.137 millimoles) of 2,2'bis ) In the same manner as in Example 1, except that hexafluoropropane (Bis-APAF) was used, a film containing poly (imide-benzoxazole) copolymer was obtained. The bis-APAF content ratio to TFDB is 0.3 mol% (0.003).

Example 3:

As the diamine monomer, 14.536 grams (0.0454 moles) of 2,2'-bis (trifluoromethyl) benzidine (TFDB) and 0.0835 grams (0.228 millimoles) of 2,2 ' ) In the same manner as in Example 1, except that hexafluoropropane (Bis-APAF) was used, a film containing poly (imide-benzoxazole) copolymer was obtained. The Bis-APAF content ratio to TFDB is 0.5 mole% (0.005).

Example 4;

14.6 grams (0.0456 moles) of 2,2'-bis (trifluoromethyl) benzidine (TFDB) and 0.0128 grams (0.0456 millimoles) of bis (3- (Imide-benzoxazole) copolymer was obtained in the same manner as in Example 1, except that the poly (amino-4-hydroxyphenyl) sulfone (Bis-APS) The ratio of Bis-APS content to TFDB is 0.1 mole% (0.001).

Example 5;

14.57 grams (0.0455 moles) of 2,2'-bis (trifluoromethyl) benzidine (TFDB) and 0.0384 grams (0.137 millimoles) of bis (3- (Imide-benzoxazole) copolymer was obtained in the same manner as in Example 1, except that the poly (amino-4-hydroxyphenyl) sulfone (Bis-APS) The ratio of Bis-APS content to TFDB is 0.3 mol% (0.003).

Example 6;

14.55 grams (0.0454 moles) of 2,2'-bis (trifluoromethyl) benzidine (TFDB) and 0.064 grams (0.23 millimoles) of bis (3- (Imide-benzoxazole) copolymer was obtained in the same manner as in Example 1, except that the poly (amino-4-hydroxyphenyl) sulfone (Bis-APS) The Bis-APS content ratio to TFDB is 0.5 mol% (0.005).

Comparative Example 1:

A polyimide film was prepared in the same manner as in Example 1, except that 14.615 grams (0.0456 mole) of 2,2'-bis (trifluoromethyl) benzidine (TFDB) was used as the diamine monomer.

Comparative Example 2;

14.457 grams (0.0451 mole) of 2,2'-bis (trifluoromethyl) benzidine (TFDB) and 0.167 grams (0.456 millimoles) of 2,2'- (Imide-benzoxazole) copolymer was obtained in the same manner as in Example 1 except that bis (3-amino-4-hydroxyphenyl) hexafluoropropane (Bis-APAF) . The ratio of Bis-APAF content to TFDB is 1 mole% (about 0.01).

Comparative Example 3;

As the diamine monomer, 14.143 grams (0.0442 mole) of 2,2'-bis (trifluoromethyl) benzidine (TFDB) and 0.5 grams (1.366 millimoles) of 2,2 ' (Imide-benzoxazole) copolymer was obtained in the same manner as in Example 1 except that bis (3-amino-4-hydroxyphenyl) hexafluoropropane (Bis-APAF) . The Bis-APAF content ratio to TFDB is 3 mol%.

Comparative Example 4;

13.83 grams (0.0432 moles) of 2,2'-bis (trifluoromethyl) benzidine (TFDB) and 0.8325 grams (2.273 millimoles) of 2,2'- (Imide-benzoxazole) copolymer was obtained in the same manner as in Example 1 except that bis (3-amino-4-hydroxyphenyl) hexafluoropropane (Bis-APAF) . The bis-APAF content ratio to TFDB is 5 mol%.

Experimental Example 1 : Measurement of transmittance

(%) Of the film obtained from Examples 1 to 3 and Comparative Examples 1 to 4 with respect to light of 300 to 800 nm and the transmittance (%) with respect to light of 430 nm wavelength are measured in the following manner:

A part of the sample was cut into a width of 300 mm and a length of 300 mm, and the transmittance was measured using a Minolta Spectrophotometer CM-3600d.

The results are summarized in Table 1 and FIG.

Experimental Example 2 : Measurement of yellow index

The yellow index (YI) was measured for the films obtained in Examples 1 to 3 and Comparative Examples 1 to 4 in the following manner:

A part of the sample was cut into a width of 300 mm and a length of 300 mm, and the yellow index was measured using a Minolta Spectrophotometer CM-3600d.

The results are summarized in Table 1 below.

Experimental Example 3 : Measurement of Thermal Expansion Coefficient (CTE)

The coefficients of thermal expansion (CTE) of the films obtained in Examples 1 to 3 and Comparative Examples 1 to 4 were measured in the following manner:

A part of the sample is cut into a width of 5 mm and a length of 20 mm, and the coefficient of thermal expansion (CTE) is measured using a TA mechanical thermal apparatus Q400. The sample is placed on a quartz hook and subjected to a force of 0.050 N. The sample is then heated from 30 to 400 at a rate of 10 / min in a nitrogen atmosphere. The thermal expansion coefficient value is obtained within the range of 50 to 300.

The results are summarized in Table 1 and FIG.

Bis-APAF content
(mol%) Transmittance (%) CTE (ppm / ^o C) Propagation factor Transmittance at 430 nm Yellow index (YI) Comparative Example 1 0 87.6 81.5 4.3 6.5 Example 1 0.1 87.5 81.3 4.4 6.5 Example 2 0.3 87.5 81.2 4.4 8.5 Example 3 0.5 87.5 81.2 4.5 8.0 Comparative Example 2 One 87.3 80 5.2 8.4 Comparative Example 3 3 87.3 79.4 5.5 12.6 Comparative Example 4 5 87.3 79.1 5.7 16.1

From the results shown in Table 1 and FIG. 1, it can be seen that the film containing the poly (imide-benzoxazole) copolymer of Examples 1 to 3 has improved transmittance and yellow index Value, and has a low CTE to show good thermal stability.

Example 7:

A film comprising a poly (imide-benzoxazole) copolymer was obtained in the same manner as in Example 1, except that 0.0456 moles of BPDA and no PMDA were used as dianhydride monomers. The ratio of Bis-APAF to TFDB is 0.1 mole% (0.001).

Example 8:

A film comprising a poly (imide-benzoxazole) copolymer was obtained in the same manner as in Example 1, except that 0.0456 moles of PMDA was used as the dianhydride monomer and BPDA was not used. The ratio of Bis-APAF to TFDB is 0.1 mole% (0.001).

Example 9:

Example 2 was repeated except that 0.0456 mole of 1,2,4,5-cyclohexanetetracarboxylic dianhydride (Cas No: 2754-41-8) was used as a dianhydride monomer instead of BPDA and PMDA. (Imide-benzoxazole) copolymer is obtained in the same manner as in (1). The ratio of Bis-APAF to TFDB is 0.1 mole% (0.001).

Example 10:

As the dianhydride monomer, instead of BPDA and PMDA, 0.0456 mole of 4,4 '- (hexafluoroisopropylidene) diphthalic anhydride (6FDA) (CAS Number 1107 -O-2) was used in place of the poly (imide-benzoxazole) copolymer. The ratio of Bis-APAF to TFDB is 0.1 mole% (0.001).

Example 11:

(Imide-benzoxazole) copolymer was used in the same manner as in Example 1, except that 1,4-cyclohexanediamine (CAS No.: 2615-25-0) was used instead of TFDB as the diamine monomer ≪ / RTI > The ratio of the content of Bis-APAF to 1,4-cyclohexanediamine is 0.1 mol% (0.001).

Example 12:

Except that 2,7-diaminofluorene (CAS No.: 525-64-4) was used instead of TFDB as a diamine monomer in the same manner as in Example 1, Benzoxazole) copolymer is obtained. The bis-APAF content ratio to 2,7-diaminofluorene is 0.1 mol% (0.001).

Example 13:

A film comprising a poly (imide-benzoxazole) copolymer was obtained in the same manner as in Example 1, except that 4,4-diaminodicyclohexylmethane was used as the diamine monomer instead of TFDB. The ratio of Bis-APAF content to 4,4-diamino dicyclohexylmethane is 0.1 mol% (0.001).

Experimental Example 4 :

The films obtained in Examples 7 to 13 were measured for light transmittance, yellow index and thermal expansion coefficient in the same manner as the above-mentioned method. As a result, the films had a transmittance and a yellow color It has an improved value in terms of exponent, and has a low CTE to show excellent thermal stability.

Si oxide deposition film formation experiment

[1] Preparation of films containing poly (imide-benzoxazole) copolymers

As the diamine monomer, 2,2'-bis (trifluoromethyl) benzidine (TFDB) and 2,2'-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (Bis-APAF) (Imide-benzoxazole) copolymer was used in the same manner as in Example 1 except that the content of Bis-APAF was changed to 0.01 mol%, 0.03 mol%, and 0.05 mol%, respectively, , And Film 3 are obtained.

[2] Si oxide deposited film formation

An Si oxide deposited film is formed on the films 1, 2, and 3, the films of Examples 1 to 3, and the films of Examples 4 to 6 under the following conditions:

Using a plasma chemical vapor deposition apparatus (BMR's HiDepTm) on each of the film coated on the glass substrate, SiH _4, O _2, and N ₂ under containing atmosphere to perform for 10 minutes deposited stand 350 dossie to form a Si oxide deposition layer .

SEM images of the deposited films formed are shown in FIGS. 2 and 3.

2 shows the Si oxide deposited film formed on the film 1, film 2, and film 3 on the upper side of Fig. 2, and the Si oxide deposited film formed on the films of Examples 1 to 3 on the lower side of Fig. . From the results shown in Fig. 2, it is confirmed that the films of Examples 1 to 3 can include the SiN deposited film on the surface without surface bending phenomenon. In contrast, in the case of Film 1, Film 2, and Film 3, it is confirmed that the surface of the Si oxide deposited film contains a plurality of wrinkles.

Fig. 3 shows a Si oxide deposited film formed on the films of Examples 4 to 6. Fig. From the results shown in Fig. 3, it is confirmed that the films of Examples 4 to 6 can include a SiN deposited film on the surface without surface bending phenomenon.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the present invention is not limited thereto. Those skilled in the art, It will be appreciated that modifications and variations of the disclosed invention and implementations thereof which may be made therein easily are all within the scope of the invention.

Claims (23)

A film comprising a polyimide-polybenzoxazole copolymer containing a repeating unit represented by the following formula (1);
[Chemical Formula 1]

Wherein A ₁ is a substituted or unsubstituted quadrivalent C6 to C24 aliphatic ring group, a substituted or unsubstituted quadrivalent C6 to C24 aromatic ring group, or a substituted or unsubstituted quadrivalent C4 to C24 heteroaromatic ring group , The aliphatic cyclic group, the aromatic cyclic group or the heteroaromatic cyclic group may be present singly or two or more rings may be fused to each other to form a condensed ring; More than one ring is a direct bond, -O-, -S-, -C (= O) -, -CH (OH) -, -S (= O) 2 -, -Si (CH 3) 2 -, ( CH _{2) p (where, 1≤p≤10), (CF 2)} q ( where, 1≤q≤10), -CR ₂ - (wherein, R represents, each independently, hydrogen, an aliphatic C1 to C10 -C (CF ₃ ) ₂ -, -C (CF ₃ ) (C ₆ H ₅ ) -, or -C (= C ₃ -C 20) aromatic hydrocarbon group or a C 6 to C 20 alicyclic hydrocarbon group, O) NH-,
A ₁ 'is a substituted or unsubstituted divalent C6 to C24 aliphatic ring group, a substituted or unsubstituted divalent C6 to C24 aromatic ring group, or a substituted or unsubstituted divalent C4 to C24 hetero aromatic ring group , The aliphatic cyclic group, the aromatic cyclic group, or the heteroaromatic cyclic group is present alone; Or two or more rings may be fused together to form a condensed ring; Or two or more rings is a direct bond, -O-, -S-, -C (= O) -, -CH (OH) -, -S (= O) 2 -, -Si (CH 3) 2 -, (CH ₂ ) _p wherein ₁ ? _P ? 10, (CF ₂ ) _q wherein ₁ ? _Q ? 10, -CR ₂ - wherein R is independently hydrogen, aliphatic hydrocarbon groups, C6 to an aromatic hydrocarbon group, or a C6 to C20 alicyclic hydrocarbon group of _{C20), -C (CF 3) 2} -, -C (CF 3) (C 6 H 5) -, or -C ( = O) NH-,
A ₂ is selected from the following,

-O-, -S-, -C (= O) -, -CH (OH) -, or -CH (OH) _{, -S (= O) 2 -} , -Si (CH 3) 2 -, (CH 2) p ( _{where, 1≤p≤10), (CF 2)} q ( where, 1≤q≤10), - CR ₂ - (wherein, R represents, each independently, hydrogen, C1 to C10 aliphatic hydrocarbon group, aromatic hydrocarbon group of C6 to C20, or C6 to C20 alicyclic hydrocarbon _{group), -C (CF 3) 2} - _{, -C (CF 3) (C} 6 H 5) - a, or -C (= O) NH-, * is the part which is connected to the adjacent atom,
A ₃ is a substituted or unsubstituted divalent C6 to C24 aliphatic ring group, a substituted or unsubstituted divalent C6 to C24 aromatic ring group or a substituted or unsubstituted divalent C4 to C24 hetero aromatic ring group, The ring group, the aromatic ring group, or the heteroaromatic ring group may be present singly or two or more rings may be fused to each other to form a condensed ring; More than one ring is a direct bond, -O-, -S-, -C (= O) -, -CH (OH) -, -S (= O) 2 -, -Si (CH 3) 2 -, ( CH _{2) p (where, 1≤p≤10), (CF 2)} q ( where, 1≤q≤10), -CR ₂ - (wherein, R represents, each independently, hydrogen, an aliphatic C1 to C10 -C (CF ₃ ) ₂ -, -C (CF ₃ ) (C ₆ H ₅ ) -, or -C (= C ₃ -C 20) aromatic hydrocarbon group or a C 6 to C 20 alicyclic hydrocarbon group, O) NH-,
m and n are numbers representing the molar ratio between the imide repeating unit and the benzoxazole repeating unit, and n / m is a real number greater than 0 and less than 0.01. The method according to claim 1,
n / m is greater than 0.0005 and less than or equal to 0.006; The method according to claim 1,
A ₁ is a film selected from the following;

In the above formulas, each of the residues may be substituted or unsubstituted, and each L may be the same or different and each independently represents a direct bond, -O-, -S-, -C (= O) -, -CH (OH) -, -S (= O) 2 -, -Si (CH 3) 2 -, (CH 2) p ( _{where, 1≤p≤10), (CF 2)} q ( where, 1≤q≤ 10), -CR ₂ - (wherein, R represents, each independently, hydrogen, C1 to C10 aliphatic hydrocarbon groups, C6 to C20 aromatic hydrocarbon group, or a C6 to C20 alicyclic hydrocarbon group), -C (CF of _{3) 2 -, -C (CF} 3) (C 6 H 5) - a, or -C (= O) NH-, * is the part to be connected to adjacent atoms,
Z ¹ and Z ² are the same or different and independently represent -N = or -C (R ¹⁰⁰ ) =, R ¹⁰⁰ is hydrogen or a C 1 to C 5 alkyl group, Z ¹ and Z ² are simultaneously -C ¹⁰⁰ ) =,
Z ³ is -O-, -S-, or -NR ¹⁰¹ -, wherein R ¹⁰¹ is hydrogen or a C 1 to C 5 alkyl group. The method of claim 3,
A ₁ is a film selected from the following;

The method according to claim 1,
A ₁ 'is a film selected from the following formulas;

In the above formulas, each of the residues may be substituted or non-substituted,
And each L is the same or different, each independently, a single bond, -O-, -S-, -C (= O) -, -CH (OH) -, -S (= O) 2 -, -Si (CH ₃ ) ₂ -, (CH ₂ ) _p wherein ₁ ? _P ? 10, (CF ₂ ) _q wherein ₁ ? _Q ? 10, -CR ₂ - wherein R is independently hydrogen, an aromatic hydrocarbon group of the aliphatic hydrocarbon groups, C6 to C20, or C6 to C20 alicyclic hydrocarbon _{group), -C (CF 3) 2} -, -C (CF 3) (C 6 H 5) -, or -C (= O) NH-,
Z ¹ and Z ² are the same or different and independently represent -N = or -C (R ¹⁰⁰ ) =, R ¹⁰⁰ is hydrogen or a C 1 to C 5 alkyl group, Z ¹ and Z ² are simultaneously -C ¹⁰⁰ ) =,
Z ³ is -O-, -S-, or -NR ¹⁰¹ -, wherein R ¹⁰¹ is hydrogen or a C 1 to C 5 alkyl group,
* Is the part connected to the neighboring atom. The method according to claim 1,
A ₂ is a film selected from the following;

The method according to claim 1,
A ₃ is a film selected from the following;

In the above formulas, each of the residues may be substituted or unsubstituted, and L is the same or different and each independently represents a direct bond, -O-, -S-, -C (= O) -, -CH ) -, -S (= O) ₂ -, -Si (CH ₃ ) ₂ -, (CH ₂ ) _p (where ₁ ? _P? 10), (CF ₂ ) _q , -CR ₂ - (wherein, R represents, each independently, hydrogen, C1 to C10 aliphatic hydrocarbon groups, C6 to C20 aromatic hydrocarbon group, or a C6 to C20 alicyclic hydrocarbon group), -C (CF _{3) 2 -, -C (CF 3)} (C 6 H 5) - a, or -C (= O) NH-, * is part being connected to the adjacent atoms is the residue. 8. The method of claim 7,
A ₃ is a film selected from the following;

The method according to claim 1,
Wherein the film has a transmittance of 85% or more for light having a wavelength in the range of 300 to 800 nm. The method according to claim 1,
Wherein the film has a yellow index of 5.2 or less. The method according to claim 1,
Wherein the film has a coefficient of thermal expansion (CTE) of 12 ppm or less at a temperature of 50 to 300 degrees Celsius. Board;
The film of claim 1 formed on the substrate; And
And a vapor deposition film formed on the film,
The deposition film may be formed of a material selected from the group consisting of silicon oxides, polysilicic acids, alkali metal silicates, alkaline earth metal silicates, aluminosilicates, silicon nitrides, silicon oxynitrides, Silicon carbide, silicon alumina oxynitride, or a combination thereof. 13. The method of claim 12,
The surface roughness of the vapor deposition film is 1 nm to 100 nm. A composition comprising a polyamic acid represented by the following formula (5): < EMI ID =
[Chemical Formula 5]

A ₁ is the same or different and each independently represents a substituted or unsubstituted quadrivalent C6 to C24 aliphatic cyclic group, a substituted or unsubstituted quadrivalent C6 to C24 aromatic ring group, or a substituted or unsubstituted quadrivalent C4 To C24 heteroaromatic ring group, and the aliphatic ring group, the aromatic ring group, or the heteroaromatic ring group may be present singly or two or more rings may be fused to each other to form a condensed ring; More than one ring is a direct bond, -O-, -S-, -C (= O) -, -CH (OH) -, -S (= O) 2 -, -Si (CH 3) 2 -, ( CH _{2) p (where, 1≤p≤10), (CF 2)} q ( where, 1≤q≤10), -CR ₂ - (wherein, R represents, each independently, hydrogen, an aliphatic C1 to C10 -C (CF ₃ ) ₂ -, -C (CF ₃ ) (C ₆ H ₅ ) -, or -C (= C ₃ -C 20) aromatic hydrocarbon group or a C 6 to C 20 alicyclic hydrocarbon group, O) NH-,
A ₂ 'is selected from the following,

,

, or

Here, L is the same or different and each independently represents a direct bond, -O-, -S-, -C (= O) -, -CH (OH) -, -S (= O) 2 -, -Si (CH ₃ ) ₂ -, (CH ₂ ) _p (wherein 1≤p≤10), (CF ₂ ) _q (where 1≤q≤10), -CR ₂ - , -C (CF ₃ ) ₂ -, -C (CF ₃ ) (C ₆ H ₅ ), or a group of the following formula ) -, or -C (= O) NH-, * is the moiety connected to nitrogen, the hydroxy group is present in the ortho position with respect to the moiety comprising *
A ₃ is a substituted or unsubstituted divalent C6 to C24 aliphatic ring group, a substituted or unsubstituted divalent C6 to C24 aromatic ring group or a substituted or unsubstituted divalent C4 to C24 hetero aromatic ring group, The ring group, the aromatic ring group, or the heteroaromatic ring group may be present singly or two or more rings may be fused to each other to form a condensed ring; More than one ring is a direct bond, -O-, -S-, -C (= O) -, -CH (OH) -, -S (= O) 2 -, -Si (CH 3) 2 -, ( CH _{2) p (where, 1≤p≤10), (CF 2)} q ( where, 1≤q≤10), -CR ₂ - (wherein, R represents, each independently, hydrogen, an aliphatic C1 to C10 -C (CF ₃ ) ₂ -, -C (CF ₃ ) (C ₆ H ₅ ) -, or -C (= C ₃ -C 20) aromatic hydrocarbon group or a C 6 to C 20 alicyclic hydrocarbon group, O) NH-,
m and n are numbers representing the molar ratio between the imide repeating unit and the benzoxazole repeating unit, and n / m is a real number greater than 0 and less than 0.01. 15. The method of claim 14,
The polyamic acid copolymer represented by Formula 5 is a tetracarboxylic acid dianhydride compound represented by Formula 2 below; A diamine compound represented by the following formula (3); And a condensation product of a hydroxydiamine compound represented by the following general formula (4), wherein the hydroxydiamine compound is a hydroxy group present in ortho position with respect to an amine group:
(2)

(3)
NH ₂ -A ₃ -NH ₂
[Chemical Formula 4]
NH ₂ -A ₂ '-NH ₂
In the above equations,
A ₁ is the same or different and each independently represents a substituted or unsubstituted quadrivalent C6 to C24 aliphatic cyclic group, a substituted or unsubstituted quadrivalent C6 to C24 aromatic ring group, or a substituted or unsubstituted quadrivalent C4 To C24 heteroaromatic ring group, and the aliphatic ring group, the aromatic ring group, or the heteroaromatic ring group may be present singly or two or more rings may be fused to each other to form a condensed ring; More than one ring is a direct bond, -O-, -S-, -C (= O) -, -CH (OH) -, -S (= O) 2 -, -Si (CH 3) 2 -, ( CH _{2) p (where, 1≤p≤10), (CF 2)} q ( where, 1≤q≤10), -CR ₂ - (wherein, R represents, each independently, hydrogen, an aliphatic C1 to C10 -C (CF ₃ ) ₂ -, -C (CF ₃ ) (C ₆ H ₅ ) -, or -C (= C ₃ -C 20) aromatic hydrocarbon group or a C 6 to C 20 alicyclic hydrocarbon group, O) NH-,
A ₂ 'is selected from the following,

,

, And

Here, L is the same or different and each independently represents a direct bond, -O-, -S-, -C (= O) -, -CH (OH) -, -S (= O) 2 -, -Si (CH ₃ ) ₂ -, (CH ₂ ) _p (wherein 1≤p≤10), (CF ₂ ) _q (where 1≤q≤10), -CR ₂ - , -C (CF ₃ ) ₂ -, -C (CF ₃ ) (C ₆ H ₅ ), or a group of the following formula ) -, or -C (= O) NH-, * is the moiety connected to the nitrogen of the neighboring moiety, and the hydroxyl group (-OH) is present at the ortho position with respect to the moiety (* and,
A ₃ is a substituted or unsubstituted divalent C6 to C24 aliphatic ring group, a substituted or unsubstituted divalent C6 to C24 aromatic ring group or a substituted or unsubstituted divalent C4 to C24 hetero aromatic ring group, The ring group, the aromatic ring group, or the heteroaromatic ring group may be present singly or two or more rings may be fused to each other to form a condensed ring; More than one ring is a direct bond, -O-, -S-, -C (= O) -, -CH (OH) -, -S (= O) 2 -, -Si (CH 3) 2 -, ( CH _{2) p (where, 1≤p≤10), (CF 2)} q ( where, 1≤q≤10), -CR ₂ - (wherein, R represents, each independently, hydrogen, an aliphatic C1 to C10 -C (CF ₃ ) ₂ -, -C (CF ₃ ) (C ₆ H ₅ ) -, or -C (= C ₃ -C 20) aromatic hydrocarbon group or a C 6 to C 20 alicyclic hydrocarbon group, O) NH-. 16. The method of claim 15,
The tetracarboxylic acid dianhydride compound may be, for example,
3,3 ', 4,4'-biphenyl tetracarboxylic dianhydride (BPDA), bicyclo [2.2.2] oct-7-en- 2,3,5,6-tetracarboxylic dianhydride (BTDA), 3,3 ', 4,4'-tetracarboxylic dianhydride (bicycle [2.2.2] oct- (4,3'4,4'-diphenylsulfone tetracarboxylic dianhydride, DSDA), 4,4 '- (hexafluoroisopropylidene) diphthalic anhydride (4,4'-diphenylsulfone tetracarboxylic dianhydride, 4 '- (hexafluoroisopropylidene) diphthalic anhydride, 6FDA, 4,4'-oxydiphthalic anhydride (ODPA), pyromellitic dianhydride - ((2,5-dioxo tedrahydrofuran-3-yl) -1,2,3,4-tetranaphthalene-1,2-dicarboxylic anhydride (4- (2,5- dioxotetrahydrofuran -3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride, DTDA), 1,2,4,5-benzenetetracarboxylic acid dianhydride (2,3-dicarboxyphenoxy) benzene dianhydride, 1,3-bis (3,4-dicarboxyphenoxy) benzene dianhydride, 1,3- ) Benzene dianhydride, 1,2,4,5-naphthalenetetracarboxylic acid dianhydride, 1,2,5,6-naphthalenetetracarboxylic acid dianhydride, 1,4,5,8-naphthalenetetracarboxylic acid Dianhydrides, 2,3,6,7-naphthalenetetracarboxylic acid dianhydride, 2,6-dichloronaphthalene-1,4,5,8-tetracarboxylic acid dianhydride, 2,7-dichloronaphthalene- Tetracarboxylic acid dianhydride, 2,3,6,7-tetrachloronaphthalene-1,4,5,8-tetracarboxylic acid dianhydride, 2,2 ', 3,3'- Diphenyltetracarboxylic acid dianhydride; 4,4'-bis (3,4-dicarboxyphenoxy) diphenyl dianhydride; Bis (2,3-dicarboxyphenyl) ether dianhydride; 4,4'-bis (2,3-dicarboxyphenoxy) diphenyl ether dianhydride; 4,4'-bis (3,4-dicarboxyphenoxy) diphenyl ether dianhydride; Bis (3,4-dicarboxyphenyl) sulfide dianhydride; 4,4'-bis (2,3-dicarboxyphenoxy) diphenyl sulfide dianhydride; 4,4'-bis (3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride; Bis (3,4-dicarboxyphenyl) sulfone dianhydride; 4,4'-bis (2,3-dicarboxyphenoxy) diphenylsulfone dianhydride; 4,4'-bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydride; 3,3 ', 4,4'-benzophenone tetracarboxylic acid dianhydride; 2,2 ', 3,3'-benzophenone tetracarboxylic acid dianhydride; 2,3,3 ', 4'-benzophenone tetracarboxylic acid dianhydride; 4,4'-bis (3,4-dicarboxyphenoxy) benzophenone dianhydride; Bis (2,3-dicarboxyphenyl) m ethane dianhydride; Bis (3,4-dicarboxyphenyl) methane dianhydride; 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride; 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride; 1,2-bis (3,4-dicarboxyphenyl) ethane dianhydride; 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride; 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride; 2,2-bis [4- (2,3-dicarboxyphenoxy) phenyl] propane dianhydride; 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride; 4- (2,3-dicarboxyphenoxy) -4 '- (3,4-dicarboxyphenoxy) diphenyl-2,2-propane dianhydride; 2,2-bis [4- (3,4-dicarboxyphenoxy-3,5-dimethyl) phenyl] propane dianhydride; 2,3,4,5-thiopentetracarboxylic acid dianhydride; 2,3,5,6-pyrazine tetracarboxylic acid dianhydride; 1,8,9,10-phenanthrenetetracarboxylic acid dianhydride; 3,4,9,10-perylene tetracarboxylic acid dianhydride; 1,3-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride; 1,1-bis (3,4-dicarboxyphenyl) -1-phenyl-2,2,2-trifluoroethane dianhydride; 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] hexafluoropropane dianhydride; 1,1-bis [4- (3,4-dicarboxyphenoxy) phenyl] -1-phenyl-2,2,2-trifluoroethane dianhydride; And 4,4'-bis [2- (3,4-dicarboxyphenyl) hexafluoroisopropyl] diphenyl ether dianhydride,
The diamine compound may be selected from the group consisting of m-phenylenediamine; p-phenylenediamine; 1,3-bis (4-aminophenyl) propane; 2,2-bis (4-aminophenyl) propane; 4,4'-diamino-diphenylmethane; 1,2-bis (4-aminophenyl) ethane; 1,1-bis (4-aminophenyl) ethane; 2,2'-diamino-diethyl sulfide; Bis (4-aminophenyl) sulfide; 2,4'-diamino-diphenyl sulfide; Bis (3-aminophenyl) sulfone; Bis (4-aminophenyl) sulfone; 4,4'-diamino-dibenzylsulfoxide; Bis (4-aminophenyl) ether; Bis (3-aminophenyl) ether; Bis (4-aminophenyl) diethylsilane; Bis (4-aminophenyl) diphenylsilane; Bis (4-aminophenyl) ethylphosphine oxide; Bis (4-aminophenyl) phenylphosphine oxide; Bis (4-aminophenyl) -N-phenylamine; Bis (4-aminophenyl) -N-methylamine; 1,2-diamino-naphthalene; 1,4-diamino-naphthalene; 1,5-diamino-naphthalene; 1,6-diamino-naphthalene; 1,7-diamino-naphthalene; 1,8-diamino-naphthalene; 2,3-diamino-naphthalene; 2,6-diamino-naphthalene; 1,4-diamino-2-methyl-naphthalene; 1,5-diamino-2-methyl-naphthalene; 1,3-diamino-2-phenyl-naphthalene; 4,4'-diamino-biphenyl;3,3'-diamino-biphenyl;3,3'-dichloro-4,4'-diamino-biphenyl;3,3'-dimethyl-4,4'-diamino-biphenyl;3,4'-dimethyl-4,4'-diamino-biphenyl;3,3'-dimethoxy-4,4'-diamino-biphenyl;4,4'-bis (4-aminophenoxy) -biphenyl; 2,4-diamino-toluene; 2,5-diamino-toluene; 2,6-diamino-toluene; 3,5-diamino-toluene; 1,3-diamino-2,5-dichloro-benzene; 1,4-diamino-2,5-dichloro-benzene; 1-methoxy-2,4-diamino-benzene; 1,4-diamino-2-methoxy-5-methyl-benzene; 1,4-diamino-2,3,5,6-tetramethyl-benzene; 1,4-bis (2-methyl-4-amino-pentyl) -benzene; 1,4-bis (1,1-dimethyl-5-amino-pentyl) -benzene; 1,4-bis (4-aminophenoxy) -benzene; o-xylylenediamine; m-xylylenediamine; p-xylylenediamine; 3,3'-diamino-benzophenone;4,4'-diamino-benzophenone;2,6-diamino-pyridine;3,5-diamino-pyridine;1,3-diamino-adamantane; Bis [2- (3-aminophenyl) hexafluoroisopropyl] diphenyl ether; 3,3'-diamino-1,1,1'-diadamantane; N- (3-aminophenyl) -4-aminobenzamide; 4-aminophenyl-3-aminobenzoate; 2,2-bis (4-aminophenyl) hexafluoropropane; 2,2-bis (3-aminophenyl) hexafluoropropane; 2- (3-aminophenyl) -2- (4-aminophenyl) hexafluoropropane; 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane; 2,2-bis [4- (2-chloro-4-aminophenoxy) phenyl hexafluoropropane; 1,1-bis (4-aminophenyl) -1-phenyl-2,2,2-trifluoroethane; 1,1-bis [4- (4-aminophenoxy) phenyl] -1-phenyl-2,2,2-trifluoroethane; 1,4-bis (3-aminophenyl) but-1-en-3-yl; 1,3-bis (3-aminophenyl) hexafluoropropane; 1,5-bis (3-aminophenyl) decafluoropentane; And 4,4'-bis [2- (4-aminophenoxyphenyl) hexafluoroisopropyl] diphenyl ether,
The aromatic hydroxydiamine compound may be selected from the group consisting of 3,3'-dihydroxy benzidine; 3,4'-diamino-3'4-dihydroxybiphenyl;3,3'-diamino-4,4'-dihydroxybiphenyl;3,3'-dihydroxy-4,4'-diaminodiphenyloxide;3,3'-dihydroxy-4,4'-diamino diphenyl oxide; 3,3'-dihydroxy-4,4'-diamino diphenylsulphone; 3,3'-dihydroxy-4,4'-diamino diphenylsulphone; Bis (3-amino-4-hydroxyphenyl) sulfone); 2,2-bis- (3-amino-4-hydroxyphenyl) propane); Bis- (3-hydroxy-4-aminophenyl) methane; bis- (3-hydroxy-4-aminophenyl) methane; 4,6-diaminoresorcinol; 3,3'-dihydroxy-4,4'-diamino-benzophenone;3,3'-dihydroxy-4,4'-diaminobenzophenone; 1,1-bis- (3-hydroxy-4-aminophenyl) ethane); 1,3-bis- (3-hydroxy-4-aminophenyl) propane; 1,3-bis- (3-hydroxy-4-aminophenyl) propane; 2,2-bis- (3-hydroxy-4-aminophenyl) propane; 2,2-bis- (3-hydroxy-4-aminophenyl) propane; And hexafluoro-2,2-bis- (3-amino-4-hydroxyphenyl) propane. 15. The method of claim 14,
A ₁ is selected from the following,

In the above formulas, the aromatic ring may be substituted or unsubstituted and L is the same or different and each independently represents a direct bond, -O-, -S-, -C (= O) -, -CH (OH) _{, -S (= O) 2 -} , -Si (CH 3) 2 -, (CH 2) p ( _{where, 1≤p≤10), (CF 2)} q ( where, 1≤q≤10), - CR ₂ - (wherein, R represents, each independently, hydrogen, C1 to C10 aliphatic hydrocarbon group, aromatic hydrocarbon group of C6 to C20, or C6 to C20 alicyclic hydrocarbon _{group), -C (CF 3) 2} - , Or -C (= O) NH-, and * is the moiety connected to the carbon of the carbonyl group;
A ₃ is a composition selected from:

-O-, -S-, -C (= O) -, -CH (OH) -, -CH (OH) -, -S (= O) ₂ -, -Si (CH ₃ ) ₂ -, (CH ₂ ) _p (where ₁ ? _P? 10), (CF ₂ ) _q -CR ₂ - (wherein, R represents, each independently, hydrogen, C1 to C10 aliphatic hydrocarbon group, aromatic hydrocarbon group of C6 to C20, or C6 to C20 alicyclic hydrocarbon group), -C (CF _{3) 2 -, -C (CF 3) (} C 6 H 5) -, or a -C (= O) NH-, * is part being already connected to the nitrogen of the dE loop. 15. The method of claim 14,
Wherein the molar ratio of said tetracarboxylic acid dianhydride compound to said diamine compound is 0.9 to 1.1. 16. The method of claim 15,
Wherein the molar ratio of the hydroxy diamine compound of Formula 4 to the diamine compound of Formula 3 is greater than 0 and less than 0.01. 16. The method of claim 15,
Wherein the condensation polymerization is carried out by stirring the monomer composition at a temperature of from 0 to 100 degrees Celsius. An electronic device comprising the film of claim 1. 21. The method of claim 20,
The electronic device may be a flat panel display, a touch screen panel, a solar cell, an electronic window, a heat mirror, a transparent transistor, a flexible display, a complementary metal oxide semiconductor sensor, A composition comprising a polyimide represented by the following formula (6):
[Chemical Formula 6]

In the above equations,
A ₁ is the same or different and each independently represents a substituted or unsubstituted quadrivalent C6 to C24 aliphatic cyclic group, a substituted or unsubstituted quadrivalent C6 to C24 aromatic ring group, or a substituted or unsubstituted quadrivalent C4 To C24 heteroaromatic ring group, and the aliphatic ring group, the aromatic ring group, or the heteroaromatic ring group may be present singly or two or more rings may be fused to each other to form a condensed ring; More than one ring is a direct bond, -O-, -S-, -C (= O) -, -CH (OH) -, -S (= O) 2 -, -Si (CH 3) 2 -, ( CH _{2) p (where, 1≤p≤10), (CF 2)} q ( where, 1≤q≤10), -CR ₂ - (wherein, R represents, each independently, hydrogen, an aliphatic C1 to C10 -C (CF ₃ ) ₂ -, -C (CF ₃ ) (C ₆ H ₅ ) -, or -C (= C ₃ -C 20) aromatic hydrocarbon group or a C 6 to C 20 alicyclic hydrocarbon group, O) NH-,
A ₂ 'is selected from the following,

,

, And

Here, L is the same or different and each independently represents a direct bond, -O-, -S-, -C (= O) -, -CH (OH) -, -S (= O) 2 -, -Si (CH ₃ ) ₂ -, (CH ₂ ) _p (wherein 1≤p≤10), (CF ₂ ) _q (where 1≤q≤10), -CR ₂ - , -C (CF ₃ ) ₂ -, -C (CF ₃ ) (C ₆ H ₅ ), or a group of the following formula ) -, or -C (= O) NH-, * is the moiety connected to the nitrogen of the neighboring moiety, and the hydroxyl group (-OH) is present at the ortho position with respect to the moiety (* and,
A ₃ is a substituted or unsubstituted divalent C6 to C24 aliphatic ring group, a substituted or unsubstituted divalent C6 to C24 aromatic ring group or a substituted or unsubstituted divalent C4 to C24 hetero aromatic ring group, The ring group, the aromatic ring group, or the heteroaromatic ring group may be present singly or two or more rings may be fused to each other to form a condensed ring; More than one ring is a direct bond, -O-, -S-, -C (= O) -, -CH (OH) -, -S (= O) 2 -, -Si (CH 3) 2 -, ( CH _{2) p (where, 1≤p≤10), (CF 2)} q ( where, 1≤q≤10), -CR ₂ - (wherein, R represents, each independently, hydrogen, an aliphatic C1 to C10 -C (CF ₃ ) ₂ -, -C (CF ₃ ) (C ₆ H ₅ ) -, or -C (= C ₃ -C 20) aromatic hydrocarbon group or a C 6 to C 20 alicyclic hydrocarbon group, O) NH-,
m and n are numbers representing the molar ratio between the imide repeating unit and the benzoxazole repeating unit, wherein n / m is a real number greater than 0 and less than 0.01.

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