KR102146808B1 - Poly(amide-imide) copolymer, film comprising poly(amide-imide) copolymer, and method for preparing the film - Google Patents

Abstract

A diamine comprising an oligomer having at least one amine end and an oligomer having at least one anhydride end, wherein at least some amine ends of the oligomer having at least one amine end have a pKa value of 3 or less at 25°C A poly(imide-amide) copolymer composition comprising an oligomer substituted with, a poly(imide-amide) copolymer prepared from the composition, and a molded article comprising the copolymer are provided.

Description

A film comprising a poly(imide-amide) copolymer, a poly(imide-amide) copolymer, and a method for producing the film (POLY(AMIDE-IMIDE) COPOLYMER, FILM COMPRISING POLY(AMIDE-IMIDE) COPOLYMER, AND METHOD FOR PREPARING THE FILM}

The present description relates to a poly(imide-amide) copolymer, a film comprising a poly(imide-amide) copolymer, and a method for producing the film.

Colorless and transparent materials are being studied in various ways according to various uses such as optical lenses, functional optical films, disk substrates, etc., but with the rapid miniaturization and weight reduction of information devices or high-definition of display devices, the functions and performances required for the materials themselves are increasingly It is precise and advanced at the same time.

Therefore, currently, research on a colorless transparent material excellent in transparency, heat resistance, mechanical strength and flexibility is being actively conducted.

One embodiment relates to a composition with improved storage stability comprising a poly(imide-amide) copolymer.

Another embodiment relates to a poly(imide-amide) copolymer prepared from the poly(imide-amide) copolymer composition, and a molded article comprising the copolymer.

In one embodiment, (i) a repeating unit represented by the following Formula 1, a repeating unit represented by the following Formula 2, or a combination of a repeating unit represented by the following Formula 1 and an amide repeating unit represented by the following Formula 2, and ( ii) an oligomer comprising an imide repeating unit represented by the following formula (3) or an amic acid repeating unit capable of forming an imide repeating unit represented by the following formula (3) by imidation, wherein at least some of the oligomers are at least Provides a poly(imide-amide) copolymer composition comprising an oligomer substituted with a diamine having a pKa value of 3 or less at 25° C. having one amine end, and some of the at least one amine end:

[Formula 1]

In Formula 1,

R ¹ is the same in each repeating unit or different from each other, and each independently a substituted or unsubstituted C3 to C30 alicyclic organic group, a substituted or unsubstituted C6 to C30 aromatic organic group, a substituted or unsubstituted C2 to C30 A heterocyclic group, or a substituted or unsubstituted C13 to C20 fluorenylene group,

R ² is the same or different from each other in each repeating unit, and each independently a substituted or unsubstituted C6 to C30 aromatic organic group,

R ³ and R ⁴ are the same or different from each other, and each independently a halogen, a hydroxy group, an ether group (-OR ²⁰⁰ , wherein R ²⁰⁰ is a C1 to C10 aliphatic organic group), a silyl group (-SiR ²⁰¹ R ²⁰² R ²⁰³ , wherein R ²⁰¹ , R ²⁰² and R ²⁰³ are the same or different from each other, and each independently hydrogen, a C1 to C10 aliphatic organic group), a substituted or unsubstituted C1 to C10 aliphatic organic group, or a C6 to C20 aromatic organic group,

n1 and n2 are each independently an integer of 0 to 4.

[Formula 2]

In Chemical Formula 2,

R ⁵ is the same or different from each other in each repeating unit, and each independently a substituted or unsubstituted C6 to C30 aromatic organic group,

R ⁶ and R ⁷ are the same or different from each other and are each independently an electron withdrawing group,

R ⁸ and R ⁹ are the same or different from each other, and each independently a halogen, a hydroxy group, an ether group (-OR ²⁰⁴ , wherein R ²⁰⁴ is a C1 to C10 aliphatic organic group), a silyl group (-SiR ²⁰⁵ R ²⁰⁶ R ²⁰⁷ , wherein R ²⁰⁵ , R ²⁰⁶ and R ²⁰⁷ are the same or different from each other, and each independently hydrogen, a C1 to C10 aliphatic organic group), a substituted or unsubstituted C1 to C10 aliphatic organic group, or a C6 to C20 aromatic organic group,

n3 is an integer of 1 to 4, n5 is an integer of 0 to 3, n3+n5 is an integer of 1 to 4,

n4 is an integer of 1 to 4, n6 is an integer of 0 to 3, and n4+n6 is an integer of 1 to 4.

[Formula 3]

In Chemical Formula 3,

R ¹⁰ is the same in each repeating unit or different from each other, and each independently a single bond, a substituted or unsubstituted C1 to C30 aliphatic organic group, a substituted or unsubstituted C3 to C30 alicyclic organic group, a substituted or unsubstituted C6 To C30 aromatic organic group, or a substituted or unsubstituted C2 to C30 heterocyclic group,

R ¹¹ is the same or different from each other in each repeating unit, and each independently includes a substituted or unsubstituted C6 to C30 aromatic organic group, and the aromatic organic group is present alone; Two or more are conjugated to each other to form a condensed ring; Two or more are single bonds, or fluorenylene group, O, S, C(=O), CH(OH), S(=O) ₂ , Si(CH ₃ ) ₂ , (CH ₂ ) _p (here, 1≤p≤10), (CF ₂ ) _q (here, 1≤q≤10), C(CH ₃ ) ₂ , C(CF ₃ ) ₂ or C(=O)NH,

R ¹² and R ¹³ are the same or different from each other, and each independently a halogen, a hydroxy group, an ether group (-OR ²⁰⁸ , wherein R ²⁰⁸ is a C1 to C10 aliphatic organic group), a silyl group (-SiR ²⁰⁹ R ²¹⁰ R ²¹¹ , wherein R ²⁰⁹ , R ²¹⁰ and R ²¹¹ are the same or different from each other, and each independently hydrogen, a C1 to C10 aliphatic organic group), a substituted or unsubstituted C1 to C10 aliphatic organic group, or a C6 to C20 aromatic organic group,

n7 and n8 are each independently an integer of 0 to 3.

In the composition, the diamine of pKa 3 or less may be represented by the following Formula 4:

(Formula 4)

In Chemical Formula 4,

X is a single bond, O, S, C(=O), CH(OH), S(=O) ₂ , Si(CH ₃ ) ₂ , (CH ₂ ) _p (where p is 1≦p≦10), (CF ₂ ) _q (where q is 1≤q≤10), C(CH ₃ ) ₂ , C(=O)NH, or C(CF ₃ ) ₂ , C(CCl ₃ ) ₂ , C(CBr ₃ ) ₂ , or C(CI ₃ ) ₂ ,

Ra to Rh are each independently hydrogen, halogen, hydroxy, ether group (-OR ²⁰⁸ , wherein R ²⁰⁸ is a C1 to C10 aliphatic organic group), silyl group (-SiR ²⁰⁹ R ²¹⁰ R ²¹¹ , wherein R ²⁰⁹ , R ²¹⁰ and R ²¹¹ are the same or different from each other, and each independently hydrogen, a C1 to C10 aliphatic organic group), a substituted or unsubstituted C1 to C10 aliphatic organic group, or a C6 to C20 aromatic organic group,

However, in Formula 4, when X is a single bond, at least two of Ra to Rd and at least two of Re to Rh are not hydrogen.

The diamine having a pKa value of 3 or less at 25° C. may be one or more of the diamines represented by the following Chemical Formulas c to h:

(Formula c)

pKa (25℃): 1.3

pKa (25°C): 1.3

(Formula d)

pKa (25℃): 2.6

pKa (25℃): 2.6

(Formula e)

pKa (25℃): 0

pKa (25℃): 0

(Formula f)

pKa (25℃): 1.8

pKa (25℃): 1.8

(Formula g)

pKa (25℃): 2.8

pKa (25℃): 2.8

(Formula h)

pKa (25℃): 2.5.

pKa (25° C.): 2.5.

The composition may include an oligomer having both ends of an hydride, an oligomer having both ends of an amine, and an oligomer having an hydra at one end and an amine at the other end. Alternatively, the composition may include an oligomer having both ends of an anhydride and an oligomer having both ends of an amine.

In both cases, the composition is present in a molar ratio of about 1:1 total anhydride ends and total amine ends in the composition.

In addition, in the composition, the diamine of pKa 3 or less is a content of about 30% or less of the total number of moles of the repeating unit of Formula 1, the repeating unit of Formula 2, and the repeating unit of Formula 3, for example, about 0.5%. To about 25%.

Each oligomer in the composition may have a weight average molecular weight of about 10,000 g/mol to about 20,000 g/mol.

In the above composition, each oligomer may have the same or similar molecular weight to each other.

In the composition, each oligomer may include about 1 to about 1,000 repeating units represented by Chemical Formulas 1 to 3, respectively.

In Formula 1, R ¹ may be selected from the group consisting of the following formula:

In Formula 2, R ⁶ and R ⁷ are the same as or different from each other, and each independently -CF ₃ , -CCl ₃ , -CBr ₃ , -CI ₃ , -NO ₂ , -CN, C1 to C2 alkanoyl group, Or it may be an electron withdrawing group selected from C1 to C6 ester groups.

The C1 to C2 alkanoyl group may be -COCH ₃ , and the C1 to C6 ester group may be -CO ₂ C ₂ H ₅ .

R ² of Formula 1 and R ⁵ of Formula 2 are the same as or different from each other, and each may be independently selected from the group consisting of the following formula:

In the above formula,

R ¹⁸ to R ²⁹ are the same or different from each other, and each independently a halogen, a substituted or unsubstituted C1 to C10 aliphatic organic group, or a substituted or unsubstituted C6 to C20 aromatic organic group,

n11 and n14 to n20 are each independently an integer of 0 to 4,

n12 and n13 are each independently an integer of 0 to 3.

More specifically, R ² and R ⁵ are the same or different from each other, and each independently may be selected from the group consisting of the following formula:

The repeating unit represented by Formula 3 may include a repeating unit represented by Formula 5 and/or a repeating unit represented by Formula 6:

[Formula 5]

(In Chemical Formula 5,

R ¹¹ , R ¹² , R ¹³ , n7 and n8 are the same as those described in Chemical Formula 3),

[Formula 6]

(In Chemical Formula 6,

R ¹¹ , R ¹² , R ¹³ , n7 and n8 are the same as those described in Chemical Formula 3).

Specifically, the repeating unit represented by Formula 1 may include a repeating unit represented by Formulas 7 to 9, and the repeating unit represented by Formula 2 may include a repeating unit represented by Formulas 10 to 12 below. In addition, the repeating unit represented by Formula 3 may include a repeating unit represented by Formulas 13 and 14 below.

[Formula 7]

[Formula 8]

[Formula 9]

[Formula 10]

[Formula 11]

[Formula 12]

[Formula 13]

[Formula 14]

Another embodiment provides a method of preparing a poly(imide-amide) copolymer comprising polymerizing the composition.

Some oligomers in the composition have at least one amine end, some other oligomers in the composition have at least one anhydride end, and the total anhydride end and the total amine end in the composition have a molar ratio of about 1:1 Since it is present, a poly(imide-amide) copolymer having a higher molecular weight can be prepared by polymerizing these oligomers.

In another embodiment, (i) a repeating unit represented by the following formula (1), a repeating unit represented by the following formula (2), or a combination of a repeating unit represented by the following formula (1) and an amide repeating unit represented by the following formula (2), ( ii) an imide repeating unit represented by the following formula (3), or an amic acid repeating unit that forms an imide repeating unit represented by the following formula (3) by imidation, and (iii) an imide repeating unit represented by the following formula (15) Or, to provide a poly(imide-amide) copolymer comprising an amic acid repeating unit forming an imide repeating unit represented by the following formula (15) by imidation:

[Formula 1]

(In Formula 1,

R ¹ is the same in each repeating unit or different from each other, and each independently a substituted or unsubstituted C3 to C30 alicyclic organic group, a substituted or unsubstituted C6 to C30 aromatic organic group, a substituted or unsubstituted C2 to C30 A heterocyclic group, or a substituted or unsubstituted C13 to C20 fluorenylene group,

R ² is the same or different from each other in each repeating unit, and each independently a substituted or unsubstituted C6 to C30 aromatic organic group,

R ³ and R ⁴ are the same or different from each other, and each independently a halogen, a hydroxy group, an ether group (-OR ²⁰⁰ , wherein R ²⁰⁰ is a C1 to C10 aliphatic organic group), a silyl group (-SiR ²⁰¹ R ²⁰² R ²⁰³ , wherein R ²⁰¹ , R ²⁰² and R ²⁰³ are the same or different from each other, and each independently hydrogen, a C1 to C10 aliphatic organic group), a substituted or unsubstituted C1 to C10 aliphatic organic group, or a C6 to C20 aromatic organic group,

n1 and n2 are each independently an integer of 0 to 4),

[Formula 2]

(In Chemical Formula 2,

R ⁵ is the same or different from each other in each repeating unit, and each independently a substituted or unsubstituted C6 to C30 aromatic organic group,

R ⁶ and R ⁷ are the same or different from each other and are each independently an electron withdrawing group,

R ⁸ and R ⁹ are the same or different from each other, and each independently a halogen, a hydroxy group, an ether group (-OR ²⁰⁴ , wherein R ²⁰⁴ is a C1 to C10 aliphatic organic group), a silyl group (-SiR ²⁰⁵ R ²⁰⁶ R ²⁰⁷ , wherein R ²⁰⁵ , R ²⁰⁶ and R ²⁰⁷ are the same or different from each other, and each independently hydrogen, a C1 to C10 aliphatic organic group), a substituted or unsubstituted C1 to C10 aliphatic organic group, or a C6 to C20 aromatic organic group,

n3 is an integer of 1 to 4, n5 is an integer of 0 to 3, n3+n5 is an integer of 1 to 4,

n4 is an integer of 1 to 4, n6 is an integer of 0 to 3, and n4+n6 is an integer of 1 to 4),

[Formula 3]

(In Chemical Formula 3,

R ¹⁰ is the same in each repeating unit or different from each other, and each independently a single bond, a substituted or unsubstituted C1 to C30 aliphatic organic group, a substituted or unsubstituted C3 to C30 alicyclic organic group, a substituted or unsubstituted C6 To C30 aromatic organic group, or a substituted or unsubstituted C2 to C30 heterocyclic group,

R ¹¹ is the same or different from each other in each repeating unit, and each independently includes a substituted or unsubstituted C6 to C30 aromatic organic group, and the aromatic organic group is present alone; Two or more are conjugated to each other to form a condensed ring; Two or more are connected by a single bond or a fluorenylene group,

R ¹² and R ¹³ are the same or different from each other, and each independently a halogen, a hydroxy group, an ether group (-OR ²⁰⁸ , wherein R ²⁰⁸ is a C1 to C10 aliphatic organic group), a silyl group (-SiR ²⁰⁹ R ²¹⁰ R ²¹¹ , wherein R ²⁰⁹ , R ²¹⁰ and R ²¹¹ are the same or different from each other, and each independently hydrogen, a C1 to C10 aliphatic organic group), a substituted or unsubstituted C1 to C10 aliphatic organic group, or a C6 to C20 aromatic organic group,

n7 and n8 are each independently an integer of 0 to 3),

[Formula 15]

(In Chemical Formula 15,

R ¹⁰ is the same in each repeating unit or different from each other, and each independently a single bond, a substituted or unsubstituted C1 to C30 aliphatic organic group, a substituted or unsubstituted C3 to C30 alicyclic organic group, a substituted or unsubstituted C6 To C30 aromatic organic group, or a substituted or unsubstituted C2 to C30 heterocyclic group,

R ³⁰ is the same or different from each other in each repeating unit, and each independently includes a substituted or unsubstituted C6 to C30 aromatic organic group, wherein two or more of the aromatic organic groups are single bonds or O, S, C (=O) , CH(OH), S(=O) ₂ , Si(CH ₃ ) ₂ , (CH ₂ ) _p (here, 1≤p≤10), (CF ₂ ) _q (here, 1≤q≤10), When C(CH ₃ ) ₂ , C(CF ₃ ) ₂ or C(=O)NH is connected by a functional group, and the two or more aromatic organic groups are connected by a single bond, each aromatic organic group has one More than one halogen is substituted,

R ¹² and R ¹³ are the same or different from each other, and each independently a halogen, a hydroxy group, an ether group (-OR ²⁰⁸ , wherein R ²⁰⁸ is a C1 to C10 aliphatic organic group), a silyl group (-SiR ²⁰⁹ R ²¹⁰ R ²¹¹ , wherein R ²⁰⁹ , R ²¹⁰ and R ²¹¹ are the same or different from each other, and each independently hydrogen, a C1 to C10 aliphatic organic group), a substituted or unsubstituted C1 to C10 aliphatic organic group, or a C6 to C20 aromatic organic group,

n7 and n8 are each independently an integer of 0 to 3).

In the copolymer, the repeating unit represented by Formula 1 may include a repeating unit represented by Formulas 7 to 9, and the repeating unit represented by Formula 2 is a repeating unit represented by Formulas 10 to 12 below. And the repeating unit represented by Formula 3 may include a repeating unit represented by Formulas 13 and 14, and the repeating unit represented by Formula 15 is a repeating unit represented by Formulas 16 and 17 below. Can contain:

[Formula 7]

[Formula 8]

[Formula 9]

[Formula 10]

[Formula 11]

[Formula 12]

[Formula 13]

[Formula 14]

[Formula 16]

[Formula 17]

.

.

In one embodiment, (i) a repeating unit represented by the following formula (10), (ii) a repeating unit represented by the following formula (13), and/or a repeating unit represented by the following formula (14), and (iii) the following formula (16). There is provided a poly(imide-amide) copolymer comprising a repeating unit represented by the following formula (17) and/or a repeating unit represented by the following formula (17):

[Formula 10]

[Formula 13]

[Formula 14]

[Formula 16]

[Formula 17]

.

.

Another embodiment provides an article comprising the poly(imide-amide) copolymer.

The molded article may be a film, fiber, coating material or adhesive.

The molded article may have a total light transmittance of about 80% or more in a wavelength range of about 380 nm to about 750 nm, and a light transmittance of about 55% or more for light having a wavelength of about 400 nm.

Specifically, the molded article may have a light transmittance of about 60% or more for light having a wavelength of about 430 nm.

The molded article may have a coefficient of thermal expansion of about 25 ppm/°C or less.

Specifically, the molded article may have a coefficient of thermal expansion of about 20 ppm/°C or less.

The molded article may have a haze of about 5% or less.

The molded article may have a yellow index (YI) of about 10 or less.

Another embodiment of the present invention provides a display device including the molded article.

In the poly(imide-amide) copolymer composition according to an embodiment, a part of at least one amine end of the oligomer having at least one amine end is substituted with a diamine having a pKa value of 3 or less at 25°C. Storage stability is remarkably improved even when the oligomer having a hydride end is included in a molar ratio of about 1:1, and thus, it can be stored for a long period of time without increasing the viscosity before curing. In addition, since the polymer is present in an oligomer state, it is advantageous for spin coating and the like, and is useful for manufacturing optical films.

1 is a cross-sectional view of an organic light emitting diode according to an embodiment
2 to 4 are graphs showing changes in viscosity over time when the copolymers according to Examples 1 to 3 are stored in a refrigerator (-12°C) and at room temperature.
5 is a graph showing a change in viscosity over time when the copolymers of Examples 1 to 3 and the copolymer of Comparative Example 1 are stored in a refrigerator.
6 is a diagram of a copolymer according to Example 4 prepared by mixing the oligomers of Synthesis Example 3 and Synthesis Example 5, and a copolymer according to Example 5 prepared by mixing the oligomers of Synthesis Example 4 and Synthesis Example 5 , A graph showing the change in viscosity during refrigeration storage over time after mixing.
7 is a graph showing changes in viscosity over time when imide polymerization was performed using the copolymers of Examples 1 to 3 and the copolymer of Comparative Example 1. FIG.

Hereinafter, embodiments of the present invention will be described in detail. However, this is presented as an example, and the present invention is not limited thereby, and the present invention is only defined by the scope of the claims to be described later.

Unless otherwise specified in the specification, "substituted" to "substituted" means that at least one hydrogen atom in the functional groups of the present invention is a halogen atom (F, Br, Cl or I), a hydroxy group, a nitro group, a cyano 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 from each other, and each independently a C1 to C10 alkyl group), amidino Group, hydrazine group, hydrazone group, carboxyl group, ester group, ketone group, substituted or unsubstituted alkyl group, substituted or unsubstituted alicyclic organic group, substituted or unsubstituted aryl group, substituted or unsubstituted alkenyl group, It means substituted with one or more substituents selected from the group consisting of a substituted or unsubstituted alkynyl group, a substituted or unsubstituted heteroaryl group, and a substituted or unsubstituted heterocyclic group, and the substituents are connected to each other to form a ring. It can also be formed.

Unless otherwise specified in the specification, "alkyl group" refers to a C1 to C30 alkyl group, specifically, a C1 to C15 alkyl group, and "cycloalkyl group" refers to a C3 to C30 cycloalkyl group, specifically C3 To C18 cycloalkyl group, "alkoxy group" refers to a C1 to C30 alkoxy group, specifically C1 to C18 alkoxy group, and "ester group" refers to a C2 to C30 ester group, specifically C2 to It means a C18 ester group, "ketone group" means a C2 to C30 ketone group, specifically C2 to C18 ketone group, and "aryl group" means a C6 to C30 aryl group, specifically C6 to C18 aryl It means a group, "alkenyl group" means a C2 to C30 alkenyl group, specifically C2 to C18 alkenyl group, and "alkylene group" refers to a C1 to C30 alkylene group, specifically C1 to C18 It means an alkylene group, and "arylene group" means a C6 to C30 arylene group, and specifically, it means a C6 to C16 arylene group.

In addition, unless otherwise specified in the specification, "aliphatic organic group" refers to a C1 to C30 alkyl group, a C2 to C30 alkenyl group, a C2 to C30 alkynyl group, a C1 to C30 alkylene group, a C2 to C30 alkenylene group, or a C2 to C30 It means an alkynylene group, specifically, a C1 to C15 alkyl group, a C2 to C15 alkenyl group, a C2 to C15 alkynyl group, a C1 to C15 alkylene group, a C2 to C15 alkenylene group, or a C2 to C15 alkynylene group, " The term "alicyclic organic group" means a C3 to C30 cycloalkyl group, a C3 to C30 cycloalkenyl group, a C3 to C30 cycloalkynyl group, a C3 to C30 cycloalkylene group, a C3 to C30 cycloalkenylene group, or a C3 to C30 cycloalkynylene group And, specifically, a C3 to C15 cycloalkyl group, a C3 to C15 cycloalkenyl group, a C3 to C15 cycloalkynyl group, a C3 to C15 cycloalkylene group, a C3 to C15 cycloalkenylene group, or a C3 to C15 cycloalkynylene group, and , "Aromatic organic group" refers to a C6 to C30 aryl group or a C6 to C30 arylene group, specifically, a C6 to C16 aryl group or a C6 to C16 arylene group, and "heterocyclic group" refers to O, S, C2 to C30 cycloalkyl group, C2 to C30 cycloalkylene group, C2 to C30 cycloalke containing 1 to 3 heteroatoms selected from the group consisting of N, P, Si, and combinations thereof in one ring Nyl group, C2 to C30 cycloalkenylene group, C2 to C30 cycloalkynyl group, C2 to C30 cycloalkynylene group, C2 to C30 heteroaryl group, or C2 to C30 heteroarylene group, specifically O , S, N, P, Si, and a C2 to C15 cycloalkyl group containing 1 to 3 heteroatoms selected from the group consisting of one ring in one ring, and a C2 to C15 cycloal A kilen group, a C2 to C15 cycloalkenyl group, a C2 to C15 cycloalkenylene group, a C2 to C15 cycloalkynyl group, a C2 to C15 cycloalkynylene group, a C2 to C15 heteroaryl group, or a C2 to C15 heteroaryl It means Rengi.

Unless otherwise specified in the specification, "combination" means mixing or copolymerization.

In addition, in the present specification, "*" means a part connected to the same or different atoms or chemical formulas.

Poly(imide-aramid) copolymer has excellent thermal, mechanical, and optical properties, so it can be used as a plastic substrate for OLED or LCD. However, the poly(imide-aramid) copolymer is a by-product during the aramid synthesis process, and HCl is generated during the reaction as shown in Scheme 1 below, and the HCl causes corrosion of the equipment, so it must be removed through a precipitation process.

(Scheme 1)

The problem is that during the precipitation process of the poly(imide-aramid) copolymer, a decrease in molecular weight may occur due to cleavage of amic acid with water. In addition, some imidation proceeds during the process of removing water, so that the solubility of the copolymer in the DAMc or NMP solvent decreases, or a portion that does not dissolve may appear. Particularly, the reduction in molecular weight due to the cleavage of amic acid may cause a cloudy phenomenon in which the film becomes cloudy.

In the case of OLED substrates, an oligomer having a low molecular weight is used because a low viscosity solution is required for coating, and in this case, the effect of the terminal group on the film properties is very large. Polyimide is synthesized by reacting a monomer of dianhydride and diamine. In general, when preparing an oligomer having a low molecular weight, an excessive amount of dianhydride or an excessive amount of an amine is added.

The problem is, when the anhydride terminal oligomer is added in excess, the anhydride reacts with water to form a carboxylic acid, and in this case, it is difficult to react with an amine to form a polymer. On the other hand, when the amine-terminated oligomer is added in an excessive amount, oxidation of the amine may occur during precipitation and drying.

When an amine containing amide is used, the precipitation process can be eliminated, and thus the deterioration of the properties of the poly(imide-amide) copolymer due to precipitation can be prevented.

On the other hand, the OLED substrate should maintain colorlessness and transparency at a high temperature of 400° C. or higher, and no out gassing should occur. For-terminated oligomer is oxidized at a high temperature causes the discoloration problem, anhydride terminated oligomers to react with moisture in the air to form a carboxylic acid, in more than 350 ℃ high temperature is CO ₂ is generated by a digital camera reubok misfire reaction out Out gassing problems may appear. In addition, poly(imide-aramid) has a high coefficient of thermal expansion (CTE) at low molecular weight.

In one embodiment, as a solution to the above problem, in the storage state, the oligomers of amide and amic acid exist in the form of oligomers, and when used, the oligomers of the amide and amic acid are polymerized by polymerization and poly( It provides a composition for preparing a poly(imide-amide) copolymer forming an imide-amide) copolymer.

Specifically, the composition includes (i) a repeating unit represented by the following formula (1), a repeating unit represented by the following formula (2), or a combination of a repeating unit represented by the following formula (1) and an amide repeating unit represented by the following formula (2), And (ii) an imide repeating unit represented by Formula 3 below, or an amic acid repeating unit capable of forming an imide repeating unit represented by Formula 3 below by imidization, wherein at least some of the oligomers Is a poly(imide-amide) copolymer composition comprising an oligomer substituted with a diamine having a pKa value of 3 or less at 25° C. having at least one amine end, and some of the at least one amine end:

[Formula 1]

In Formula 1,

R ¹ is the same in each repeating unit or different from each other, and each independently a substituted or unsubstituted C3 to C30 alicyclic organic group, a substituted or unsubstituted C6 to C30 aromatic organic group, a substituted or unsubstituted C2 to C30 A heterocyclic group, or a substituted or unsubstituted C13 to C20 fluorenylene group,

R ² is the same or different from each other in each repeating unit, and each independently a substituted or unsubstituted C6 to C30 aromatic organic group,

R ³ and R ⁴ are the same or different from each other, and each independently a halogen, a hydroxy group, an ether group (-OR ²⁰⁰ , wherein R ²⁰⁰ is a C1 to C10 aliphatic organic group), a silyl group (-SiR ²⁰¹ R ²⁰² R ²⁰³ , wherein R ²⁰¹ , R ²⁰² and R ²⁰³ are the same or different from each other, and each independently hydrogen, a C1 to C10 aliphatic organic group), a substituted or unsubstituted C1 to C10 aliphatic organic group, or a C6 to C20 aromatic organic group,

n1 and n2 are each independently an integer of 0 to 4.

[Formula 2]

In Chemical Formula 2,

R ⁵ is the same or different from each other in each repeating unit, and each independently a substituted or unsubstituted C6 to C30 aromatic organic group,

R ⁶ and R ⁷ are the same or different from each other and are each independently an electron withdrawing group,

R ⁸ and R ⁹ are the same or different from each other, and each independently a halogen, a hydroxy group, an ether group (-OR ²⁰⁴ , wherein R ²⁰⁴ is a C1 to C10 aliphatic organic group), a silyl group (-SiR ²⁰⁵ R ²⁰⁶ R ²⁰⁷ , wherein R ²⁰⁵ , R ²⁰⁶ and R ²⁰⁷ are the same or different from each other, and each independently hydrogen, a C1 to C10 aliphatic organic group), a substituted or unsubstituted C1 to C10 aliphatic organic group, or a C6 to C20 aromatic organic group,

n3 is an integer of 1 to 4, n5 is an integer of 0 to 3, n3+n5 is an integer of 1 to 4,

n4 is an integer of 1 to 4, n6 is an integer of 0 to 3, and n4+n6 is an integer of 1 to 4.

[Formula 3]

In Chemical Formula 3,

R ¹⁰ is the same in each repeating unit or different from each other, and each independently a single bond, a substituted or unsubstituted C1 to C30 aliphatic organic group, a substituted or unsubstituted C3 to C30 alicyclic organic group, a substituted or unsubstituted C6 To C30 aromatic organic group, or a substituted or unsubstituted C2 to C30 heterocyclic group,

R ¹¹ is the same or different from each other in each repeating unit, and each independently includes a substituted or unsubstituted C6 to C30 aromatic organic group, and the aromatic organic group is present alone; Two or more are conjugated to each other to form a condensed ring; Two or more are single bonds, or fluorenylene group, O, S, C(=O), CH(OH), S(=O) ₂ , Si(CH ₃ ) ₂ , (CH ₂ ) _p (here, 1≤p≤10), (CF ₂ ) _q (here, 1≤q≤10), C(CH ₃ ) ₂ , C(CF ₃ ) ₂ or C(=O)NH,

R ¹² and R ¹³ are the same or different from each other, and each independently a halogen, a hydroxy group, an ether group (-OR ²⁰⁸ , wherein R ²⁰⁸ is a C1 to C10 aliphatic organic group), a silyl group (-SiR ²⁰⁹ R ²¹⁰ R ²¹¹ , wherein R ²⁰⁹ , R ²¹⁰ and R ²¹¹ are the same or different from each other, and each independently hydrogen, a C1 to C10 aliphatic organic group), a substituted or unsubstituted C1 to C10 aliphatic organic group, or a C6 to C20 aromatic organic group,

n7 and n8 are each independently an integer of 0 to 3.

Acid dissociation constant Ka is a measure of the strength of an acid in a solution. This is an equilibrium constant for a chemical reaction known as "dissociation" in terms of an acid-base reaction, and the equilibrium state can be represented by the following equation.

(Equation 1)

Wherein, HA is, A in the ^aqueous solution shows a (conjugate base of the acid) and H ⁺ in general the acid to be separated (hydrogen ions, or protons) dissociation (acid).

The acid dissociation constant (Ka) is the molar concentration of the acid in the equilibrium state in which the concentration of these acids, conjugate bases, and hydrogen ions does not change over time because the acid is separated into conjugate bases A ^- and hydrogen ions H ⁺ . -) and hydrogen ions ([a ^{- -} HA]) conjugate base ([a for indicating that the ratio of]), the product of the molar concentration of can be represented by the following formula (2).

(Equation 2)

pKa is expressed as a negative logarithm of the acid dissociation constant Ka, and can be expressed by Equation 3 below.

(Equation 3)

That is, the higher the pKa value, the lower the degree of dissociation of the acid at a given pH, indicating a weaker acid, and the lower the pKa value, the stronger the acid.

It is known that the reactivity of amines is proportional to pKa. That is, the lower the pKa, the lower the reactivity, and in the case of diamine, it was thought that pKa could be reduced by introducing an electron withdrawing group at the center of the molecule.

Thus, in the above embodiment, a composition comprising an oligomer substituted with a diamine having a pKa 3 or less in part of the at least one amine terminal of the oligomer having at least one amine terminal is provided, and such a composition is an example to be described later. As can be seen from, even when the amine end and the anhydride end are included together in a molar ratio of 1:1, it can be seen that the polymerization reaction between them is suppressed and storage stability is remarkably improved.

Accordingly, the composition includes a molar ratio of about 1:1 with all amine ends and all anhydride ends in the composition, and a part of the amine end is substituted with a diamine having a pKa value of 3 or less at 25°C. The diamine having pKa 3 or less may be present in an amount of about 30% or less of the total number of moles of the first repeating unit, the second repeating unit, and the third repeating unit in the composition.

In one embodiment, the diamine of pKa 3 or less may be included in an amount of about 0.5% to about 25% of the total number of moles of the repeating unit of Formula 1, the repeating unit of Formula 2, and the repeating unit of Formula 3.

When a diamine of pKa 3 or less is substituted on at least one end of the oligomer in the above content range, the viscosity hardly increases when the composition containing the amine end and the anhydride end in the composition in a molar ratio of about 1:1 is stored in a refrigerator. It can be easily used for spin coating for preparing poly(imide-amide) polymers.

When the content of diamine of pKa 3 or less exceeds the above range, the composition may not readily undergo a polymerization reaction for preparing a poly(imide-amide) copolymer. In addition, when the content of diamine of pKa 3 or less is less than the above range, storage stability of the composition may not be improved.

A diamine having a pKa value of 3 or less at 25° C. may be represented by Formula 4:

(Formula 4)

In Chemical Formula 4,

X is a single bond, O, S, C(=O), CH(OH), S(=O) ₂ , Si(CH ₃ ) ₂ , (CH ₂ ) _p (where p is 1≦p≦10), (CF ₂ ) _q (where q is 1≤q≤10), C(CH ₃ ) ₂ , C(=O)NH, or C(CH ₃ ) ₂ , C(CF ₃ ) ₂ , C(CCl ₃ ) ₂ , C(CBr ₃ ) ₂ , or C(CI ₃ ) ₂ ,

Ra to Rh are each independently hydrogen, halogen, hydroxy, ether group (-OR ²⁰⁸ , wherein R ²⁰⁸ is a C1 to C10 aliphatic organic group), silyl group (-SiR ²⁰⁹ R ²¹⁰ R ²¹¹ , wherein R ²⁰⁹ , R ²¹⁰ and R ²¹¹ are the same or different from each other, and each independently hydrogen, a C1 to C10 aliphatic organic group), a substituted or unsubstituted C1 to C10 aliphatic organic group, or a C6 to C20 aromatic organic group,

However, in Formula 4, when X is a single bond, at least two of Ra to Rd and at least two of Re to Rh are not hydrogen.

As an example, the diamine having a pKa value of 3 or less at 25° C. may be at least one selected from diamines represented by the following Chemical Formulas c to h, but is not limited thereto:

(Formula c)

pKa (25℃): 1.3

pKa (25°C): 1.3

(Formula d)

pKa (25℃): 2.6

pKa (25℃): 2.6

(Formula e)

pKa (25℃): 0

pKa (25℃): 0

(Formula f)

pKa (25℃): 1.8

pKa (25℃): 1.8

(Formula g)

pKa (25℃): 2.8

pKa (25℃): 2.8

(Formula h)

pKa (25℃): 2.5.

pKa (25° C.): 2.5.

The pKa values of the diamines at 25° C. are calculated using Advanced Chemistry Development (ACD/Labs) software v11.02 (©1994-2012 ACD.Labs).

The composition may include an oligomer having both ends of an hydride, an oligomer having both ends of an amine, and an oligomer having an hydra at one end and an amine at the other end.

Alternatively, the composition may include an oligomer having both ends of an anhydride and an oligomer having both ends of an amine.

In both cases, the composition may include all anhydride ends and all amine ends in the composition in a molar ratio of about 1:1.

The composition according to the above embodiment includes an oligomer having an amine-terminated oligomer and an oligomer having an anhydride-terminal in a molar ratio of about 1:1, so that an excessive amount of amine or anhydride-terminated oligomer was added to maintain the oligomer state. All the disadvantages of the composition can be solved. That is, discoloration due to the addition of an excessive amine, precipitation, or oxidation problems during a drying process can be prevented, and a degassing problem due to the generation of CO2 due to the addition of an excessive anhydride can be solved. In addition, by including the oligomers in a molar ratio of 1:1, when they are polymerized with each other, a polymer having a large molecular weight can be prepared. Polymers with a large molecular weight have the effect of reducing CTE. In addition, poly(imide-amide) copolymer having excellent optical properties by stably storing it in an oligomer state without increasing viscosity during storage, and then easily applying it to spin coating and curing according to a known method when used. Can be easily manufactured.

That is, the composition according to the embodiment is present in an oligomer state by inhibiting polymerization by refrigerating during storage, and polymerization and curing according to known methods such as spin coating when used, poly(imide) having excellent optical properties. -Amide) polymer can be easily prepared.

In the composition, each oligomer may have a weight average molecular weight of about 10,000 g/mol to about 20,000 g/mol.

In the above composition, each oligomer may have the same or similar molecular weight to each other.

In the composition, each oligomer may include about 1 to about 1,000 repeating units represented by Chemical Formulas 1 to 3, respectively.

R ¹ of Formula 1 may be selected from the group consisting of the following formula:

R ⁶ and R ⁷ of Formula 2 are the same as or different from each other, and each independently -CF ₃ , -CCl ₃ , -CBr ₃ , -CI ₃ , -NO ₂ , -CN, C1 to C2 alkanoyl group, or It may be a C1 to C6 ester group. For example, the alkanoyl group may be -COCH ₃ , and the ester group may be -CO ₂ C ₂ H ₅ .

R ² of Formula 1 and R ⁵ of Formula 2 are the same as or different from each other, and each may be independently selected from the group consisting of the following formula:

In the above formula,

R ¹⁸ to R ²⁹ are the same or different from each other, and each independently a halogen, a substituted or unsubstituted C1 to C10 aliphatic organic group, or a substituted or unsubstituted C6 to C20 aromatic organic group,

n11 and n14 to n20 are each independently an integer of 0 to 4,

n12 and n13 are each independently an integer of 0 to 3.

More specifically, R ² and R ⁵ are the same as or different from each other, and each independently may be selected from the group consisting of the following formula:

The repeating unit represented by Formula 3 may include a repeating unit represented by Formula 5 and/or Formula 6:

[Formula 5]

(In Chemical Formula 5,

R ¹¹ , R ¹² , R ¹³ , n7 and n8 are the same as those described in Chemical Formula 3),

[Formula 6]

(In Chemical Formula 6,

R ¹¹ , R ¹² , R ¹³ , n7 and n8 are the same as those described in Chemical Formula 3).

Specifically, the repeating unit represented by Formula 1 may include a repeating unit represented by Formulas 7 to 9, and the repeating unit represented by Formula 2 may include a repeating unit represented by Formulas 10 to 12 below. In addition, the repeating unit represented by Formula 3 may include a repeating unit represented by Formulas 13 and 14 below.

[Formula 7]

[Formula 8]

[Formula 9]

[Formula 10]

[Formula 11]

[Formula 12]

[Formula 13]

[Formula 14]

Meanwhile, the composition may be prepared by mixing and reacting diamine, dianhydride, and diamine of pKa 3 or less in one reactor to prepare a poly(imide-amide) copolymer composition as described above. In this case, even if the oligomer in the prepared composition contains an amine end and an anhydride end in a molar ratio of about 1:1, there is no problem in storage stability of the composition.

Alternatively, if necessary, an oligomer having an amine end and an oligomer having an anhydride end may be separately prepared, and the composition may be prepared by mixing these oligomers when used. At this time, by adding a diamine of pKa 3 or less only when preparing the oligomer having an amine end, an amine-terminated oligomer including an oligomer in which some of the amine ends are substituted with diamines of pKa 3 or less can be prepared.

On the other hand, in the case of separately preparing and storing an oligomer having an amine-terminated oligomer and an oligomer having an anhydride-terminated, the oligomers are mixed as necessary and before polymerization into a poly(imide-amide) copolymer, the anhydride By partially imidizing only the oligomer having a lide end, it may have an effect of further reducing the CTE of the poly(imide-amide) polymer to be produced.

On the other hand, when preparing the oligomer, in the case of preparing a diamine containing amide in advance and reacting it with a dianhydride, for the removal of HCl, which was produced as a reaction by-product when preparing a conventional poly(imide-amide) copolymer The precipitation process can be omitted. That is, as shown in the examples to be described later, in one embodiment, a diamine containing a diamine and a derivative of dicarboxylic acid are reacted to prepare an amide group-containing diamine, and then reacted with other diamines and dianhydrides to prepare poly(imide). -Amide) oligomer was prepared.

Specifically, in Synthesis Example 1, 2,2'-bis (trifluoromethyl) benzidine in N,N-dimethylacetamide, which is an aprotic polar solvent, as shown in Scheme 2 (TFDB: 2,2'-bis(trifluoromethyl)benzidine) was reacted with biphenyl dicarbonyl chloride (BPCl) to prepare an amide group-containing diamine named DA119. In the following examples, a poly(imide-amide) copolymer was prepared by reacting the prepared DA119 diamine with dianhydride and additional diamine. The amide group-containing diamine can be generalized and represented by the following formula (18):

(Chemical Formula 18)

In Formula 18, the biphenylene group between the two amide groups is derived from the dicarboxylic acid derivative, biphenyl dicarbonyl chloride (BPCl), and is connected between the amine groups at both ends of the formula 18 It can be seen that Ar1 and Ar2 are derived from TFDB, which is a diamine, respectively.

That is, as represented by Formula 18, the diamine includes an aramid structure between the ends of the two amine groups, and thus, when preparing'imide' by reacting the diamine with a dianhydride, contained in the diamine Due to the'aramid' structure, the'(imide-aramid)' copolymer is produced at the same time as the'imide' production. Accordingly, there is no need for a separate'aramid' formation process when preparing the poly(imide-aramid) copolymer, and thus HCl, a reaction by-product as in the prior art, is not generated when preparing the poly(imide-aramid) copolymer. . Therefore, when preparing the poly(imide-aramid) copolymer, a conventional precipitation process for removing HCl may be omitted.

Diamine as represented by Formula 18 can be prepared according to a conventional amide production process. That is, for example, it may be prepared using a low-temperature solution polymerization method, an interfacial polymerization method, a melt polymerization method, a solid-phase polymerization method, etc., but is not limited thereto.

Another embodiment provides a method of preparing a poly(imide-amide) copolymer from the composition.

The manufacturing method includes curing the composition.

If necessary, when the composition is to separately prepare and store the oligomer having the amine end and the oligomer having the unhydride end, the composition may include mixing the oligomers before polymerization. In addition, at this time, if necessary, before mixing the oligomers, as described above, the step of imidizing the oligomer having an anhydride end may be further included. By partially or entirely imidizing the oligomer having an anhydride end, the coefficient of thermal expansion (CTE) of the poly(imide-amide) copolymer prepared therefrom can be further reduced.

The poly(imide-amide) copolymer manufactured according to the above method has a low coefficient of thermal expansion (CTE) and can be used as a material for various molded articles requiring transparency. For example, the poly(imide-amide) copolymer may be usefully used in various fields such as a display substrate, specifically, a flexible display substrate, a touch panel, and a protective film for an optical disk.

Accordingly, another embodiment provides a poly(imide-amide) copolymer prepared from the composition. The copolymer,

(i) a repeating unit represented by the following formula (1), a repeating unit represented by the following formula (2), or a combination of a repeating unit represented by the following formula (1) and an amide repeating unit represented by the following formula (2), (ii) by the following formula (3) The imide repeating unit represented, or an amic acid repeating unit forming the imide repeating unit represented by the following formula (3) by imidization, and (iii) the imide repeating unit represented by the following formula (15), or by imidization It may contain an amic acid repeating unit forming an imide repeating unit represented by the following Formula 15:

[Formula 1]

(In Formula 1,

R ¹ is the same in each repeating unit or different from each other, and each independently a substituted or unsubstituted C3 to C30 alicyclic organic group, a substituted or unsubstituted C6 to C30 aromatic organic group, a substituted or unsubstituted C2 to C30 A heterocyclic group, or a substituted or unsubstituted C13 to C20 fluorenylene group,

R ² is the same or different from each other in each repeating unit, and each independently a substituted or unsubstituted C6 to C30 aromatic organic group,

R ³ and R ⁴ are the same or different from each other, and each independently a halogen, a hydroxy group, an ether group (-OR ²⁰⁰ , wherein R ²⁰⁰ is a C1 to C10 aliphatic organic group), a silyl group (-SiR ²⁰¹ R ²⁰² R ²⁰³ , wherein R ²⁰¹ , R ²⁰² and R ²⁰³ are the same or different from each other, and each independently hydrogen, a C1 to C10 aliphatic organic group), a substituted or unsubstituted C1 to C10 aliphatic organic group, or a C6 to C20 aromatic organic group,

n1 and n2 are each independently an integer of 0 to 4),

[Formula 2]

(In Chemical Formula 2,

R ⁵ is the same or different from each other in each repeating unit, and each independently a substituted or unsubstituted C6 to C30 aromatic organic group,

R ⁶ and R ⁷ are the same or different from each other and are each independently an electron withdrawing group,

R ⁸ and R ⁹ are the same or different from each other, and each independently a halogen, a hydroxy group, an ether group (-OR ²⁰⁴ , wherein R ²⁰⁴ is a C1 to C10 aliphatic organic group), a silyl group (-SiR ²⁰⁵ R ²⁰⁶ R ²⁰⁷ , wherein R ²⁰⁵ , R ²⁰⁶ and R ²⁰⁷ are the same or different from each other, and each independently hydrogen, a C1 to C10 aliphatic organic group), a substituted or unsubstituted C1 to C10 aliphatic organic group, or a C6 to C20 aromatic organic group,

n3 is an integer of 1 to 4, n5 is an integer of 0 to 3, n3+n5 is an integer of 1 to 4,

n4 is an integer of 1 to 4, n6 is an integer of 0 to 3, and n4+n6 is an integer of 1 to 4),

[Formula 3]

(In Chemical Formula 3,

R ¹⁰ is the same in each repeating unit or different from each other, and each independently a single bond, a substituted or unsubstituted C1 to C30 aliphatic organic group, a substituted or unsubstituted C3 to C30 alicyclic organic group, a substituted or unsubstituted C6 To C30 aromatic organic group, or a substituted or unsubstituted C2 to C30 heterocyclic group,

R ¹¹ is the same or different from each other in each repeating unit, and each independently includes a substituted or unsubstituted C6 to C30 aromatic organic group, and the aromatic organic group is present alone; Two or more are conjugated to each other to form a condensed ring; Two or more are connected by a single bond or a fluorenylene group,

R ¹² and R ¹³ are the same or different from each other, and each independently a halogen, a hydroxy group, an ether group (-OR ²⁰⁸ , wherein R ²⁰⁸ is a C1 to C10 aliphatic organic group), a silyl group (-SiR ²⁰⁹ R ²¹⁰ R ²¹¹ , wherein R ²⁰⁹ , R ²¹⁰ and R ²¹¹ are the same or different from each other, and each independently hydrogen, a C1 to C10 aliphatic organic group), a substituted or unsubstituted C1 to C10 aliphatic organic group, or a C6 to C20 aromatic organic group,

n7 and n8 are each independently an integer of 0 to 3),

[Formula 15]

(In Chemical Formula 15,

R ¹⁰ is the same in each repeating unit or different from each other, and each independently a single bond, a substituted or unsubstituted C1 to C30 aliphatic organic group, a substituted or unsubstituted C3 to C30 alicyclic organic group, a substituted or unsubstituted C6 To C30 aromatic organic group, or a substituted or unsubstituted C2 to C30 heterocyclic group,

R ³⁰ is the same or different from each other in each repeating unit, and each independently includes a substituted or unsubstituted C6 to C30 aromatic organic group, wherein two or more of the aromatic organic groups are single bonds or O, S, C (=O) , CH(OH), S(=O) ₂ , Si(CH ₃ ) ₂ , (CH ₂ ) _p (here, 1≤p≤10), (CF ₂ ) _q (here, 1≤q≤10), When C(CH ₃ ) ₂ , C(CF ₃ ) ₂ or C(=O)NH is connected by a functional group, and the two or more aromatic organic groups are connected by a single bond, each aromatic organic group has one More than one halogen is substituted,

R ¹² and R ¹³ are the same or different from each other, and each independently a halogen, a hydroxy group, an ether group (-OR ²⁰⁸ , wherein R ²⁰⁸ is a C1 to C10 aliphatic organic group), a silyl group (-SiR ²⁰⁹ R ²¹⁰ R ²¹¹ , wherein R ²⁰⁹ , R ²¹⁰ and R ²¹¹ are the same or different from each other, and each independently hydrogen, a C1 to C10 aliphatic organic group), a substituted or unsubstituted C1 to C10 aliphatic organic group, or a C6 to C20 aromatic organic group,

n7 and n8 are each independently an integer of 0 to 3).

In the copolymer, the repeating unit represented by Formula 1 may include a repeating unit represented by Formulas 7 to 9, and the repeating unit represented by Formula 2 is a repeating unit represented by Formulas 10 to 12 below. And the repeating unit represented by Formula 3 may include a repeating unit represented by Formulas 13 and 14, and the repeating unit represented by Formula 15 is a repeating unit represented by Formulas 16 and 17 below. Can contain:

[Formula 7]

[Formula 8]

[Formula 9]

[Formula 10]

[Formula 11]

[Formula 12]

[Formula 13]

[Formula 14]

[Formula 16]

[Formula 17]

.

.

In one embodiment, (i) a repeating unit represented by the following formula (10), (ii) a repeating unit represented by the following formula (13), and/or a repeating unit represented by the following formula (14), and (iii) the following formula (16). There is provided a poly(imide-amide) copolymer comprising a repeating unit represented by the following formula (17) and/or a repeating unit represented by the following formula (17):

[Formula 10]

[Formula 13]

[Formula 14]

[Formula 16]

[Formula 17]

.

.

Another embodiment provides a molded article comprising the prepared poly(imide-amide) copolymer.

The molded article may be a film, fiber, coating material or adhesive.

The molded article may be manufactured according to the method of manufacturing the poly(imide-amide) copolymer.

For example, when the molded article is a film, it can be prepared by coating the poly(imide-amide) composition on a substrate and curing it.

The molded article including the poly(imide-amide) copolymer may have a total light transmittance of about 80% or more in a wavelength range of about 380 nm to about 750 nm, and a light transmittance of about 55 to light having a wavelength of about 400 nm. May be greater than or equal to %. When the light transmittance of the molded article including the poly(imide-amide) copolymer is within the above range, the molded article including the poly(imide-amide) copolymer may have excellent color reproducibility. Specifically, the molded article including the poly(imide-amide) copolymer may have a total light transmittance of about 80% to about 95% in a wavelength range of about 380 nm to about 750 nm, and light having a wavelength of about 400 nm. The light transmittance for may be about 55% to about 90%.

The molded article including the poly(imide-amide) copolymer may have a coefficient of thermal expansion (CTE) of about 35 ppm/°C or less. When the coefficient of thermal expansion of the molded article is within the above range, it may have excellent heat resistance. Specifically, the molded article may have a coefficient of thermal expansion of about 25 ppm/℃ or less, and more specifically about 15 ppm/℃ or less.

The molded article including the poly(imide-amide) copolymer may have a haze of about 5% or less. When the range of the haze of the molded article is within the above range, the molded article is sufficiently transparent to have excellent clarity. Specifically, the molded article may have a haze of about 3% or less.

The molded article including the poly(imide-amide) copolymer may have a yellow index (YI) of about 10 or less. When the yellowness of the molded article is within the above range, it may appear transparently and colorless. Specifically, the molded article may have a yellowness (YI) of about 0.1 to about 5.

A molded article including the poly(imide-amide) copolymer, for example, a film may have a thickness of about 0.01 μm to about 1,000 μm, but is not limited thereto, and the thickness may be appropriately adjusted according to the use. .

The molded article may have excellent transparency, heat resistance, mechanical strength and flexibility by including a poly(imide-amide) polymer having excellent transparency, heat resistance, mechanical strength and flexibility as described above. Accordingly, the molded product is a device substrate, a display substrate, an optical film, an integrated circuit (IC) package, an adhesive film, a multilayer flexible printed circuit (FRC), a tape, a touch panel, and a protection for an optical disk. It can be used in various fields such as films.

According to another embodiment, a display device including the molded article is provided. Specifically, the display device may include a liquid cryatal display device (LCD), an organic light emitting diode (OLED), and the like, but is not limited thereto.

An organic light emitting diode (OLED) of the display device will be described with reference to FIG. 1. 1 is a cross-sectional view of an organic light emitting diode according to an embodiment.

Referring to FIG. 1, a thin film transistor 320, a capacitor 330, and an organic light emitting device 340 are formed on a substrate 300. The thin film transistor 320 includes a source electrode 321, a semiconductor layer 323, a gate electrode 325, and a drain electrode 322, and the capacitor 330 includes a first capacitor 331 and a second capacitor 332 ), and includes an organic light-emitting device 340, a pixel electrode 341, an intermediate layer 342, and a counter electrode 343.

Specifically, the semiconductor layer 323, the gate insulating film 311, the first capacitor 331, the gate electrode 325, the interlayer insulating film 313, the second capacitor 332, the source electrode on the substrate 300 321 and a drain electrode 322 are formed. The source electrode 321 and the drain electrode 322 are separated from each other and face the gate electrode 325 as the center.

A planarization film 317 is formed on the interlayer insulating film 313, the second capacitor 332, the source electrode 321, and the drain electrode 322, and a contact exposing the drain electrode 322 to the planarization film 317 A sphere 319 is formed.

A pixel electrode 341 made of a transparent conductive material such as ITO or IZO is formed on the planarization layer 317. The pixel electrode 341 is connected to the drain electrode 322 through the contact hole 319.

An intermediate layer 342 and a counter electrode 343 are sequentially formed on the pixel electrode 341.

A pixel defining layer 318 is formed on the planarization layer 317 in a portion where the pixel electrode 341, the intermediate layer 342, and the counter electrode 343 are not formed.

In this case, the substrate 300 may be formed of a molded article including the poly(imide-amide) block copolymer.

Hereinafter, the present invention will be described in more detail through Examples 　 and Comparative Examples, but the following Examples 　 and Comparative Examples are for the purpose of explanation and are not intended to limit the present invention.

Example

Synthesis Example 1: Preparation of aramid monomer DA119 with diamine bonded to both ends

In order to eliminate the problem of HCl generation by reacting diamine and biphenyl chloride in the oligomer or polymer manufacturing process, according to Scheme 2 below, a monomer DA119, which forms an aramid structure by bonding diamine at both ends, was prepared in advance. use.

[Scheme 2]

That is, 2,2'-bis (trifluoromethyl) benzidine (2,2'-bis (trifluoromethyl) benzidine, in 800 g of N,N-dimethylacetamide) as a solvent in a round bottom flask, After dissolving 2 molar equivalents (0.08 mol, 25.6192 g) of TFDB) and 2.2 molar equivalents (0.088 mol, 6.96 g) of pyridine, the remaining TFDB was washed with 80 ml of DMAC, and biphenyl dicarbonyl chloride (BPCl: biphenyl dicarbonyl chloride) 11.1648 g (1 molar equivalent, 0.04 mol) was divided in 4 times, mixed with TFDB solution at 5°C, and stirred vigorously for 15 minutes.

The resulting solution was stirred in a nitrogen atmosphere for 2 hours, and then put in 7 L of water containing 1 kg of NaCl and cooled to 0°C. The resulting mixture was cooled to 0° C. for 12 hours to complete precipitation of organic matter. The solid is filtered, resuspended and re-filtered four times in 1.5 L of deionized water. The final filtrate on the filter is properly pressurized to remove the remaining water as much as possible and dried in a nitrogen stream until a constant weight is reached. The pre-dried product was further maintained for 36 hours in a vacuum desiccator containing sodium hydroxide and nitrogen atmosphere to remove residual water, dried under vacuum at 90° C., and the monomer DA-119 as the product described in Scheme 2 above. Got it.

Example 1: Synthesis of poly(imide-amide) (PAD-622)

DA-119 prepared in Synthesis Example 1, 6.414 g (0.0076 mol), was put into a 250 ml 4-neck double wall reactor equipped with a mechanical stirrer and nitrogen inlet, preheated to 80° C., and 57 ml of NMP was added. . Until DA-119 is completely dissolved, the solution is stirred under a nitrogen atmosphere at 80° C., and thereafter, TFDB (2,2'-bis(trifluoromethyl)benzidine (2,2'-bis(trifluoromethyl)) is added to the solution. )benzidine)), 1.3952 g (0.0044 mol) and DADPS (4,4'-diaminodiphenyl sulfone)), 0.0604 g (0.0002 mol) were added. The temperature was reduced to 20°C. 6 FDA (2,2-bis-(3,4-dicarboxyphenyl)hexafluoropropane dianhydride (2,2-bis-(3,4-dicarboxyphenyl)hexafluoropropane dianhydride)), 1.6227 g (0.0037 mol) and BPDA (3,3',4,4'-biphenyltetracarboxylic dianhydride (3,3',4,4'-biphenyltetracarboxylic dianhydride)), 2.5077 g (0.0085 mol) was slowly added to the diamine solution I did. After 9 ml of NMP was added, the solution was stirred for 48 hours to obtain a poly(amide-amic acid) solution. The DADPS content corresponds to about 0.81 mol% of the total number of reactants.

Example 2: Synthesis of poly(imide-amide) (PAD-623)

DA-119 prepared in Synthesis Example 1, 6.63356 g (0.0075 mol), was put into a 250 ml 4-neck double wall reactor equipped with a mechanical stirrer and nitrogen inlet, preheated to 80° C., and 57 ml of NMP was added. . Until DA-119 was completely dissolved, the solution was stirred at 80° C. under a nitrogen atmosphere, and then TFDB, 1.3779 g (0.0043 mol) and DADPS, 0.1219 g (0.0005 mol) were added to the solution. The temperature was reduced to 20°C. 6FDA, 1.6361 g (0.0037 mol) and BPDA, 2.5285 g (0.0086 mol) were slowly added to the diamine solution. After 9 ml of NMP was added, the solution was stirred for 48 hours to obtain a poly(amide-amic acid) solution. The DADPS content corresponds to about 2 mole percent of the total number of moles of monomers.

Example 3: Synthesis of poly(imide-amide) (PAD-624)

DA-119 prepared in Synthesis Example 1, 6.2553 g (0.0074 mol), was put into a 250 ml four-neck double wall reactor equipped with a mechanical stirrer and nitrogen inlet, preheated to 80° C., and 57 ml of NMP was added. . Until DA-119 was completely dissolved, the solution was stirred at 80° C. under a nitrogen atmosphere, and then TFDB, 1.3607 g (0.0042 mol) and DADPS, 0.1844 g (0.0007 mol) were added to the solution. The temperature was reduced to 20°C. 6FDA, 1.6499 g (0.0037 mol) and BPDA, 2.5497 g (0.0087 mol) were slowly added to the diamine solution. After 9 ml of NMP was added, the solution was stirred for 48 hours to obtain a poly(amide-amic acid) solution. The DADPS content corresponds to about 2.8 mol% of the total number of reactants.

Synthesis Example 2: Synthesis of an amine-terminated oligo (imide-amide) (PAD-625)

DA-119 prepared in Synthesis Example 1, 6.0833 g (0.00718 mol), was put into a 250 ml four-neck double wall reactor equipped with a mechanical stirrer and nitrogen inlet, preheated to 80° C., and 54 ml of NMP was added. . The solution was stirred under a nitrogen atmosphere at 80° C. until DA-119 was completely dissolved, and then TFDB, 3.0109 g (0.0094 mol) and DADPS, 0.2419 g (0.00097 mol) were added to the solution. The temperature was reduced to 20°C. 6FDA, 1.9894g (0.0045 mol) and BPDA, 3.0744g (0.01045 mol) were slowly added to the diamine solution. After addition of 10 ml of NMP, the solution was stirred for 48 hours to obtain an oligo(amide-amic acid) solution.

Synthesis Example 3: Synthesis of an amine-terminated oligo (imide-amide) (PAD-636)

DA-119 prepared in Synthesis Example 1, 6.5493 g (0.0077 mol), was put into a 250 ml four-neck double wall reactor equipped with a mechanical stirrer and nitrogen inlet, preheated to 80° C., and 54 ml of NMP was added. . Until DA-119 was completely dissolved, the solution was stirred at 80° C. under a nitrogen atmosphere, and then TFDB, 1.5846 g (0.0049 mol) and DADPS, 1.2086 g (0.0049 mol) were added to the solution. The temperature was reduced to 20°C. 6FDA, 1.9877 g (0.0045 mol) and BPDA, 3.0718 g (0.0104 mol) were slowly added to the diamine solution. After addition of 10 ml of NMP, the solution was stirred for 48 hours to obtain an oligo(amide-amic acid) solution.

Synthesis Example 4: Synthesis of oligo (imide-amide) having amine ends (PAD-639)

DA-119 prepared in Synthesis Example 1, 6.5493 g (0.0077 mol), was put into a 250 ml 4-neck double wall reactor equipped with a mechanical stirrer and nitrogen inlet, preheated to 80° C., and 54 ml of NMP was added. . The solution was stirred under a nitrogen atmosphere at 80° C. until DA-119 was completely dissolved, and then TFDB, 2.2345 g (0.0070 mol) and DADPS, 0.6777 g (0.0027 mol) were added to the solution. The temperature was reduced to 20°C. 6FDA, 1.9669 g (0.0044 mol) and BPDA, 3.0396 g (0.0103 mol) were slowly added to the diamine solution. After addition of 10 ml of NMP, the solution was stirred for 48 hours to obtain an oligo (amide-amic acid) solution having an amine end.

Synthesis Example 5: Synthesis of an oligo (imide-amide) having an anhydride end (PAD-637)

DA-119 prepared in Synthesis Example 1, 7.4014 g (0.0087 mol), was put into a 250 ml 4-neck double wall reactor equipped with a mechanical stirrer and nitrogen inlet, preheated to 80° C., and 40 ml of NMP and Equamide M100 , 17 ml were added. The solution was stirred under a nitrogen atmosphere at 80° C. until DA-119 was completely dissolved, and then TFDB, 1.8331 g (0.0057 mol) was added to the solution. The temperature was reduced to 20°C. 6FDA, 2.0294 g (0.0046 mol) and BPDA, 3.1362 g (0.0107 mol) were slowly added to the diamine solution. After adding Equamide M100, 7 ml, the solution was stirred for 48 hours to obtain an oligo (amide-amic acid) solution having an unhydrated end.

To carry out chemical imidization for CTE (coefficient of thermal expansion) reduction, acetic anhydride, 2.9537 g (0.0289 mol) was added. After stirring for 30 minutes, 2.2885 g (0.0289 mol) of pyridine was added, and further reacted for 24 hours.

Examples 4 and 5: Preparation of poly(imide-amide) copolymer by copolymerization of oligomers having amine-terminated and anhydride-terminated oligomers

10 g of an oligomer PAD-637-100% CI (100% chemically imidized) solution having an anhydride end prepared in Synthesis Example 5 was put into a glass vial, and the amine-terminated oligomer PAD-636 solution prepared in Synthesis Example 3 2.7148 g were added. The solution was mechanically stirred and left at room temperature to prepare a poly(imide-amide) copolymer having the composition shown in the following table. Here, the content of DADPS is about 3.6 mol% of the total number of moles of monomers (Example 4).

In addition, 10 g of an anhydride-terminated oligomer PAD-637-100% CI (100% chemically imidized) solution prepared in Synthesis Example 5 was put into a glass vial, and the amine-terminated oligomer PAD- prepared in Synthesis Example 4 2.7436 g of 639 solution were added. The solution was mechanically stirred and left at room temperature to prepare a poly(imide-amide) copolymer having the composition shown in the following table. Here, the content of DADPS is about 2 mol% of the total number of moles of monomers (Example 5).

Comparative Example 1: Synthesis of poly(imide-amide)

DA-119 prepared in Synthesis Example 1, 6.498 g (0.0077 mol), was put into a 250 ml 4-neck double wall reactor equipped with a mechanical stirrer and nitrogen inlet, preheated to 80° C., and 57 ml of NMP was added. . The solution was stirred under a nitrogen atmosphere at 80° C. until DA-119 was completely dissolved, and then TFDB, 1.4269 g (0.0045 mol) was added to the solution. The temperature was reduced to 20°C. 6FDA, 1.6227 g (0.0037 mol) and BPDA, 2.5077 g (0.0085 mol) were slowly added to the diamine solution. After 9 ml of NMP was added, the solution was stirred for 48 hours to obtain a poly(amide-amic acid) solution.

evaluation

1. Evaluation of storage stability of the copolymer

In order to confirm the storage stability of the copolymer compositions of Examples and Comparative Examples, the viscosity of the composition was measured when each of the copolymers were stored in a refrigerator and at room temperature. The increase in viscosity of the composition is a result of the oligo(imide-amide) copolymers reacting with each other to form a higher molecular weight polymer. Viscosity was measured with an AR rheometer using a cone (diameter 40 mm, cone angle 2°) and a plate shape.

As can be seen from FIGS. 2 to 4, according to Examples 1 to 3, oligomers containing about 0.81%, 2%, and 2.8% of DADPS with pKa 3 or less based on the total number of moles of monomers were prepared. When the containing composition is stored in a refrigerator at about -12°C, it can be seen that the viscosity of the solution hardly increases even after about 200 hours or more. On the other hand, when the same copolymer composition is stored at room temperature, as shown in Figs. 3 to 5, the viscosity increases rapidly over time from immediately after storage, and the viscosity exceeds 100,000 cP after 50 hours, which is It is a viscosity that cannot be applied at all for spin coating or the like.

In addition, as shown in FIG. 5, when the copolymers according to Examples 1 to 3 and the copolymer of Comparative Example 1 not containing DADPS are stored in a refrigerator at about -12°C, DADPS, a diamine having pKa 3 or less In the case of Examples 1 to 3 including, the viscosity hardly increased until 100 hours elapsed, whereas in the case of the copolymer of Comparative Example 1 not containing DADPS, the viscosity was 30,000 from the time of storage despite being refrigerated. It can be seen that the cP was gradually increased and the viscosity increased more rapidly after 50 hours. This increased viscosity is such that it cannot be applied at all for spin coating or the like. On the other hand, in the case of the compositions according to Examples 1 to 3, the viscosity was maintained between 5,000 and 15,000 cP between 100 and 200 hours, which is a degree to which low viscosity coating is possible. In particular, as the content of DADPS increased, the viscosity was kept low, and in the case of the copolymer of Example 3, the viscosity was maintained at less than 10,000 cP even after 100 hours.

6 is a diagram of a copolymer according to Example 4 prepared by mixing the oligomers of Synthesis Example 3 and Synthesis Example 5, and a copolymer according to Example 5 prepared by mixing the oligomers of Synthesis Example 4 and Synthesis Example 5, It is a graph showing the change in viscosity according to time change during refrigeration after mixing at room temperature. As can be seen from FIG. 6, in the case of the copolymers of Examples 4 and 5, by mixing the amine-terminated oligomer of Synthesis Example 3 or 4 and the anhydride-terminated oligomer of Synthesis Example 5 at room temperature, they were polymerized. Thus, as the copolymer is formed, the viscosity increases rapidly within about 2 hours after initial mixing, but it can be seen that the viscosity hardly increases after polymerization is completed to a certain degree. That is, when a part of the amine-terminated oligomer contains an oligomer end-capped with diamine DADPS having a pKa 3 or less, even if the oligomer is mixed with an unhyde-terminated oligomer, it can be seen that polymerization is inhibited during refrigerated storage, so that the viscosity hardly increases have.

Meanwhile, FIG. 7 is a graph showing a change in viscosity according to reaction time when imide polymerization is performed at room temperature using the copolymers of Examples 1 to 3 and the copolymer of Comparative Example 1. The greater the viscosity increase during the same time period, the faster the polymerization rate. As shown in FIG. 7, when a small amount of DADPS (diamino diphenyl sulfone) having a pka of 3 or less is included, it can be seen that the polymerization rate is significantly reduced compared to the case of using the copolymer of Comparative Example 1 that does not contain it. In particular, it can be seen that the viscosity is kept low as the content of DADPS increases, so it can be seen that the low reactivity of DADPS acts advantageously to improve storage stability.

From these results, according to an embodiment of the present invention, when a part of the oligomer having an amine-terminated oligomer is substituted with a diamine of pKa 3 or less, when the oligomer is included, the amine-terminated oligomer and the anhydride-terminated oligomer are in a molar ratio of 1:1. Even when included together, it can be stored for a long period of time without an increase in viscosity at low temperatures, and thus spin coating is possible, and through its additional polymerization and curing, a poly(imide-amide) copolymer having excellent optical properties can be easily prepared. You can see that you can.

2. Film production and evaluation of optical and thermal properties of films

Film manufacturing

The copolymers prepared in Examples and Comparative Examples were dropped onto a glass substrate (5 X 5 cm) and spin-coated at a speed of 800 rpm. The spin-coating solution was pre-dried on a heating plate at 80° C. for 1 hour to remove excess solvent. The glass substrate was heated at a temperature rising rate of 3° C./min under a nitrogen atmosphere, and annealed at 320° C. for 1 hour to prepare a film.

Optical properties

The optical properties of the prepared film were measured in a transmission opacity/haze mode using a "Konica Minolta CM3600d" spectrophotometer, and the spectrum was recorded for a wavelength range of 360 to 700 nm. The results are shown in Table 1 below.

Thermal properties

The thermal expansion coefficient (CTE) of the film is a fixed tensile strength of 0.05N while heating from 50°C to 400°C at a heating rate of 5°C/min using TMA (thermal mechanical analyzer: TMA Q400, manufactured by TA Instrument). force). The CTE value was determined as a dimensional change in the range of 50°C to 250°C. The results are shown in Table 1 below.

Film thickness
(㎛) Transmittance
(%) Transmittance @ 430nm
(%) Haze
(%) Yellow index
(%) CTE (ppm/℃)
(50~250℃) Tg
(℃) Example 1 10 88.03 83.77 0.34 3.36 16.78 346 Example 2 10 88.1 83.44 0.36 3.64 18.86 353 Example 3 12 87.59 81.97 0.34 4.54 20.15 352 Example 4 14 87.78 83.92 0.49 3.16 17.77 352 Example 5 11 87.86 84.1 0.41 3.02 17.66 335 Comparative Example 1 11 87.68 83.28 0.81 3.56 18.83 354

As can be seen from Table 1 above, the poly(imide-amide) film prepared using the copolymer according to the embodiment of the present invention has high transmittance, and low haze and yellow index, and thus has excellent optical properties, It can be seen that the thermal expansion coefficient (CTE) is low and the glass transition temperature (Tg) is high, so excellent thermal properties are also maintained.

Although the embodiments of the present invention have been described in detail through examples, the present invention is not limited thereto, and various changes and modifications apparent to those skilled in the art are all included in the scope of the present invention.

Claims (19)

A method for producing a film comprising a poly(imide-amide) copolymer comprising curing a composition for producing a poly(imide-amide) copolymer, wherein the composition for producing a poly(imide-amide) copolymer,
(i) a repeating unit represented by the following formula (1), a repeating unit represented by the following formula (2), or a combination of a repeating unit represented by the following formula (1) and an amide repeating unit represented by the following formula (2), and (ii) the following formula (3) An oligomer containing an imide repeating unit represented by, or an amic acid repeating unit capable of forming an imide repeating unit represented by the following formula (3) by imidization, wherein at least some of the oligomers are at least one amine A method for producing a film comprising a poly(imide-amide) copolymer having a terminal, wherein some of the at least one amine terminal is substituted with a diamine having a pKa value of 3 or less at 25°C:
[Formula 1]

(In Formula 1,
R ¹ is the same in each repeating unit or different from each other, and each independently a substituted or unsubstituted C3 to C30 alicyclic organic group, a substituted or unsubstituted C6 to C30 aromatic organic group, a substituted or unsubstituted C2 to C30 A heterocyclic group, or a substituted or unsubstituted C13 to C20 fluorenylene group,
R ² is the same or different from each other in each repeating unit, and each independently a substituted or unsubstituted C6 to C30 aromatic organic group,
R ³ and R ⁴ are the same or different from each other, and each independently a halogen, a hydroxy group, an ether group (-OR ²⁰⁰ , wherein R ²⁰⁰ is a C1 to C10 aliphatic organic group), a silyl group (-SiR ²⁰¹ R ²⁰² R ²⁰³ , wherein R ²⁰¹ , R ²⁰² and R ²⁰³ are the same or different from each other, and each independently hydrogen, a C1 to C10 aliphatic organic group), a substituted or unsubstituted C1 to C10 aliphatic organic group, or a C6 to C20 aromatic organic group,
n1 and n2 are each independently an integer of 0 to 4),
[Formula 2]

(In Chemical Formula 2,
R ⁵ is the same or different from each other in each repeating unit, and each independently a substituted or unsubstituted C6 to C30 aromatic organic group,
R ⁶ and R ⁷ are the same or different from each other and are each independently an electron withdrawing group,
R ⁸ and R ⁹ are the same or different from each other, and each independently a halogen, a hydroxy group, an ether group (-OR ²⁰⁴ , wherein R ²⁰⁴ is a C1 to C10 aliphatic organic group), a silyl group (-SiR ²⁰⁵ R ²⁰⁶ R ²⁰⁷ , wherein R ²⁰⁵ , R ²⁰⁶ and R ²⁰⁷ are the same or different from each other, and each independently hydrogen, a C1 to C10 aliphatic organic group), a substituted or unsubstituted C1 to C10 aliphatic organic group, or a C6 to C20 aromatic organic group,
n3 is an integer of 1 to 4, n5 is an integer of 0 to 3, n3+n5 is an integer of 1 to 4,
n4 is an integer of 1 to 4, n6 is an integer of 0 to 3, and n4+n6 is an integer of 1 to 4),
[Formula 3]

(In Chemical Formula 3,
R ¹⁰ is the same in each repeating unit or different from each other, and each independently a single bond, a substituted or unsubstituted C1 to C30 aliphatic organic group, a substituted or unsubstituted C3 to C30 alicyclic organic group, a substituted or unsubstituted C6 To C30 aromatic organic group, or a substituted or unsubstituted C2 to C30 heterocyclic group,
R ¹¹ is the same or different from each other in each repeating unit, and each independently includes a substituted or unsubstituted C6 to C30 aromatic organic group, and the aromatic organic group is present alone; Two or more are conjugated to each other to form a condensed ring; Two or more are single bonds, or fluorenylene group, O, S, C(=O), CH(OH), S(=O) ₂ , Si(CH ₃ ) ₂ , (CH ₂ ) _p (here, 1≤p≤10), (CF ₂ ) _q (here, 1≤q≤10), C(CH ₃ ) ₂ , C(CF ₃ ) ₂ or C(=O)NH,
R ¹² and R ¹³ are the same or different from each other, and each independently a halogen, a hydroxy group, an ether group (-OR ²⁰⁸ , wherein R ²⁰⁸ is a C1 to C10 aliphatic organic group), a silyl group (-SiR ²⁰⁹ R ²¹⁰ R ²¹¹ , wherein R ²⁰⁹ , R ²¹⁰ and R ²¹¹ are the same or different from each other, and each independently hydrogen, a C1 to C10 aliphatic organic group), a substituted or unsubstituted C1 to C10 aliphatic organic group, or a C6 to C20 aromatic organic group,
n7 and n8 are each independently an integer of 0 to 3). The method of claim 1, wherein the diamine having a pKa value of 3 or less at 25°C is represented by the following formula (4), a film comprising a poly(imide-amide) copolymer:
(Formula 4)

In Chemical Formula 4,
X is a single bond, O, S, C(=O), CH(OH), S(=O) ₂ , Si(CH ₃ ) ₂ , (CH ₂ ) _p (where p is 1≦p≦10), (CF ₂ ) _q (where q is 1≤q≤10), C(CH ₃ ) ₂ , C(=O)NH, or C(CF ₃ ) ₂ , C(CCl ₃ ) ₂ , C(CBr ₃ ) ₂ , or C(CI ₃ ) ₂ ,
Ra to Rh are each independently hydrogen, halogen, hydroxy, ether group (-OR ²⁰⁸ , wherein R ²⁰⁸ is a C1 to C10 aliphatic organic group), silyl group (-SiR ²⁰⁹ R ²¹⁰ R ²¹¹ , wherein R ²⁰⁹ , R ²¹⁰ and R ²¹¹ are the same or different from each other, and each independently hydrogen, a C1 to C10 aliphatic organic group), a substituted or unsubstituted C1 to C10 aliphatic organic group, or a C6 to C20 aromatic organic group,
However, in Formula 4, when X is a single bond, at least two of Ra to Rd and at least two of Re to Rh are not hydrogen. The method of claim 1 wherein the electron withdrawing group is a _{-CF 3, -CCl 3, -CBr 3} , -CI 3, -NO 2, -CN, C1 to C2 alkanoyl group, or a C1 to C6 ester group, poly (already De-amide) a method for producing a film comprising a copolymer. The method of claim 1, wherein the diamine having a pKa value of 3 or less at 25°C is at least one selected from diamines represented by the following Chemical Formulas c to h, poly(imide-amide) copolymers:
(Formula c)

(Formula d)

(Formula e)

(Formula f)

(Formula g)

(Formula h)

. The method of claim 1, wherein the composition comprises an oligomer having both ends of an hydride and an oligomer having both ends of an amine, or an oligomer having an hydride at one end and an amine at the other end, or A method for producing a film comprising a poly(imide-amide) copolymer, comprising a combination of, wherein the total amine terminal and the total anhydride terminal in the composition are present in a molar ratio of 1:1. The composition of claim 1, wherein the composition comprises an oligomer having both ends of an hydride and an oligomer having both ends of an amine, or an oligomer having an hydride at one end and an amine at the other end, or A method for producing a film comprising a poly (imide-amide) copolymer comprising a combination of, wherein the oligomer in which both ends of the composition are anhydride is partially or completely imidized. The method of claim 1, wherein the diamine having a pKa value of 3 or less at 25°C is 30% or less of the total number of moles of the repeating unit of Formula 1, the repeating unit of Formula 2, and the repeating unit of Formula 3 in the composition. A method for producing a film comprising a poly(imide-amide) copolymer contained in an amount of. The method of claim 1, wherein each oligomer in the composition has a weight average molecular weight of 10,000 g/mol to 20,000 g/mol. 3. A method of producing a film comprising a poly(imide-amide) copolymer. The method of claim 1, wherein the oligomer comprises 1 to 1,000 repeating units represented by Chemical Formulas 1 to 3, respectively, by poly(imide-amide) copolymer. The method of claim 1, wherein R ¹ is selected from the group consisting of the following general formulae, which comprises a poly(imide-amide) copolymer:

The method of claim 1, wherein R ² and R ⁵ are the same as or different from each other, and are each independently selected from the group consisting of the following formulas, wherein the film comprises a poly(imide-amide) copolymer:

In the above formula,
R ¹⁸ to R ²⁹ are the same or different from each other, and each independently a halogen, a substituted or unsubstituted C1 to C10 aliphatic organic group, or a substituted or unsubstituted C6 to C20 aromatic organic group,
n11 and n14 to n20 are each independently an integer of 0 to 4,
n12 and n13 are each independently an integer of 0 to 3. The method of claim 11, wherein R ² and R ⁵ are the same or different from each other and are each independently selected from the group consisting of the following formulas, wherein the film comprises a poly(imide-amide) copolymer:

The poly(imide-amide) of claim 1, wherein the repeating unit represented by Formula 3 comprises a repeating unit represented by Formula 5, a repeating unit represented by Formula 6, or a combination thereof. Method for making a film comprising a copolymer:
[Formula 5]

[Formula 6]

(In Chemical Formulas 5 and 6,
R ¹¹ is the same or different from each other in each repeating unit, and each independently includes a substituted or unsubstituted C6 to C30 aromatic organic group, and the aromatic organic group is present alone; Two or more are conjugated to each other to form a condensed ring; Two or more are single bonds, or fluorenylene group, O, S, C(=O), CH(OH), S(=O) ₂ , Si(CH ₃ ) ₂ , (CH ₂ ) _p (here, 1≤p≤10), (CF ₂ ) _q (here, 1≤q≤10), C(CH ₃ ) ₂ , C(CF ₃ ) ₂ or C(=O)NH,
R ¹² and R ¹³ are the same or different from each other, and each independently, a halogen, a hydroxy group, an ether group (-OR ²⁰⁸ , wherein R ²⁰⁸ is a C1 to C10 aliphatic organic group), a silyl group (-SiR ²⁰⁹ R ²¹⁰ R ²¹¹ , Wherein R ²⁰⁹ , R ²¹⁰ and R ²¹¹ are the same or different from each other, and each independently hydrogen, a C1 to C10 aliphatic organic group), a substituted or unsubstituted C1 to C10 aliphatic organic group, or a C6 to C20 aromatic organic group ,
n7 and n8 are each independently an integer of 0 to 3). The method of claim 1,
The repeating unit represented by Formula 1 includes at least one of the repeating units represented by Formulas 7 to 9 below,
The repeating unit represented by Formula 2 includes at least one of the repeating units represented by Formulas 10 to 12 below,
The repeating unit represented by Formula 3 includes at least one of the repeating units represented by Formulas 13 and 14 below,
Method for producing a film comprising a poly(imide-amide) copolymer:
[Formula 7]

[Formula 8]

[Formula 9]

[Formula 10]

[Formula 11]

[Formula 12]

[Formula 13]

[Formula 14]

. The method of claim 1, further comprising coating the composition on a substrate before curing the composition for preparing the poly(imide-amide) copolymer. . The method of claim 15 wherein the coating comprises a spin-coating. 16. The method of claim 15, wherein the coating comprises a poly(imide-amide) copolymer. A film comprising a poly(imide-amide) copolymer prepared according to the method of any one of claims 1 to 16. A display device comprising the film of claim 17. The display device according to claim 18, wherein the display device comprises a liquid cryatal display device (LCD) or an organic light emitting diode (OLED).

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