KR20190056887A - Polyamideimide copolymers and colorless and transparent polyamideimide film comprising the same - Google Patents

Abstract

The present invention relates to a polyamide-imide copolymer and a colorless and transparent polyamide-imide copolymer film comprising the same. The polyamide-imide copolymer according to the present invention enables to provide a polyamide-imide film which is colorless and transparent, and also has excellent mechanical properties.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a polyamide-imide copolymer and a colorless transparent polyamide-

The present invention relates to a polyamideimide copolymer and a colorless transparent polyamideimide film comprising the same.

The aromatic polyimide resin is a polymer having mostly an amorphous structure and exhibits excellent heat resistance, chemical resistance, electrical properties, and dimensional stability due to its rigid chain structure. Such a polyimide resin is widely used as an electric / electronic material.

However, the polyimide resin has many limitations in its use because it has a dark brown limit due to the formation of a charge transfer complex (CTC) of π electrons present in the imide chain.

To solve the above limitation, and to obtain a colorless and transparent polyimide resin, a strong electron withdrawing, such as methyl (-CF ₃₎ group, trifluoromethyl group, the introduction of restricting the movement of π electrons; A method of reducing the formation of the CTC by introducing a sulfone (-SO ₂ -) group, an ether (-O-) group or the like into the main chain to form a bending structure; Or introducing an aliphatic cyclic compound to inhibit the formation of resonance structures of? Electrons have been proposed.

However, the polyimide resin according to the above proposals is difficult to exhibit sufficient heat resistance by a bending structure or an aliphatic cyclic compound, and a film produced using the polyimide resin still has a limit to exhibit poor mechanical properties.

On the other hand, in recent years, a polyamideimide copolymer having a polyamide unit structure introduced to improve the scratch resistance of polyimide has been developed.

However, the polyamide-imide copolymer shows a tendency to easily haze when the film is formed by coating it due to its high crystallinity.

Such haze characteristics of the polyamide-imide films are severely manifested as the thickness of the film is thicker, and the yellow index (Y.I.) is also affected, and a method for improving the haze characteristics is required.

In particular, development of a plastic film having optical properties and mechanical properties at a level that can replace glass as a material for displays and window covers of various electronic devices is required.

The present invention is to provide a polyamideimide copolymer which is colorless and transparent and can exhibit excellent mechanical properties.

The present invention further provides a colorless transparent polyamide-imide film comprising the polyamide-imide copolymer.

According to the present invention,

As an imide of a polyamic acid copolymerized with an aromatic diamine monomer, an aromatic dianhydride monomer and an aromatic carbonyl monomer,

Wherein the aromatic carbonyl monomer is contained in an amount of 60.0 mol% or more based on the total moles of the aromatic dianhydride monomer and the aromatic carbonyl monomer,

Wherein the aromatic carbonyl monomer comprises 95.0 to 99.9 mole percent aromatic dicarbonyl monomer and 0.01 to 5.0 mole percent aromatic tricarbonyl monomer.

A polyamideimide copolymer is provided.

Further, according to the present invention, there is provided a film comprising the polyamideimide copolymer.

Hereinafter, a polyamideimide copolymer and a polyamideimide film containing the same according to embodiments of the present invention will be described in detail.

It is to be understood that the terminology is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention, unless explicitly stated herein.

The singular forms as used herein include plural forms as long as the phrases do not expressly contradict it.

Means that a particular feature, region, integer, step, operation, element and / or component is specified, and that other specific features, regions, integers, steps, operations, elements, components, and / And the like.

I. Polyamideimide copolymer

According to one embodiment of the invention,

As an imide of a polyamic acid copolymerized with an aromatic diamine monomer, an aromatic dianhydride monomer and an aromatic carbonyl monomer,

Wherein the aromatic carbonyl monomer is contained in an amount of 60.0 mol% or more based on the total moles of the aromatic dianhydride monomer and the aromatic carbonyl monomer,

Wherein the aromatic carbonyl monomer comprises 95.0 to 99.9 mole percent aromatic dicarbonyl monomer and 0.01 to 5.0 mole percent aromatic tricarbonyl monomer.

A polyamideimide copolymer is provided.

As a result of continuous research by the present inventors, it has been found that, when a polyamideimide copolymer is formed using an aromatic diamine monomer, an aromatic dianhydride monomer and an aromatic carbonyl monomer, It has been confirmed that when aromatic tricarbonyl monomer is used together with an aromatic dicarbonyl monomer as an aromatic carbonyl monomer, a copolymer having colorless transparency and excellent mechanical properties can be formed.

That is, the aromatic carbonyl monomer of a specific composition prescribed according to embodiments of the present invention can minimize crystallization upon copolymerization with aromatic diamine monomers and aromatic dianhydride monomers, thereby providing excellent scratch resistance and low Which enables the formation of a polyamideimide copolymer simultaneously exhibiting haziness.

In particular, the aromatic tricarbonyl monomer acts as a cross-linking agent in the copolymerization process to enable formation of a copolymer having improved mechanical properties.

According to an embodiment of the invention, the polyamideimide copolymer is an imide of the aromatic diamine monomer, the aromatic dianhydride monomer, and the polyamic acid to which the aromatic carbonyl monomer is copolymerized.

The polyamic acid may be a block copolymer or a random copolymer.

For example, the polyamic acid block copolymer may comprise a first unit structure derived from copolymerization of the aromatic dianhydride monomer and the aromatic dianhydride monomer; And a second unit structure derived from copolymerization of the aromatic diamine monomer and the aromatic carbonyl monomer.

And, the polyamic acid random copolymer may include a unit structure in which the aromatic diamine monomer, the aromatic dianhydride monomer, and the aromatic carbonyl monomer each form an amide bond and are randomly copolymerized.

This polyamic acid forms a polyamideimide copolymer having imide bond and amide bond simultaneously by imidization.

According to an embodiment of the present invention, the aromatic carbonyl monomer is contained in an amount of 60.0 mol% or more based on the total molar amount of the aromatic dianhydride monomer and the aromatic carbonyl monomer, thereby forming a copolymer having colorless transparency and excellent mechanical properties .

Preferably, the aromatic carbonyl monomer is at least 60.0 mol%, or at least 70.0 mol%, or at least 80.0 mol%, or at least 90.0 mol%, based on the total moles of the aromatic dianhydride monomer and the aromatic carbonyl monomer .

However, when the aromatic carbonyl monomer is used in an excess amount, the hygroscopicity of the aromatic carbonyl monomer may be lowered or become opaque. Therefore, it is preferable that the aromatic carbonyl monomer is contained in an amount of 99.5 mol% or less based on the total moles of the aromatic dianhydride monomer and the aromatic carbonyl monomer.

In particular, according to an embodiment of the present invention, it is preferable that the aromatic dicarbonyl monomer and the tricarbonyl monomer are applied together with the aromatic carbonyl monomer.

Examples of the aromatic dicarbonyl monomer include 4,4'-biphenyldicarbonyl chloride, isophthaloyl chloride, and terephthaloyl chloride. One or more compounds selected from the group consisting of

The aromatic tricarbonyl monomer may be trimesoyl chloride.

The aromatic tricarbonyl monomer in the carbonyl monomer may act as a crosslinking agent in the copolymerization process to enable formation of a copolymer having improved mechanical properties.

In order to achieve this effect, the aromatic tricarbonyl monomer is preferably contained in the aromatic carbonyl monomer in an amount of 0.01 mol% or more, or 0.025 mol% or more, or 0.05 mol% or more.

However, when the aromatic tricarbonyl monomer is excessively used, the polyamide-imide film may become opaque and the flexibility may be deteriorated. Accordingly, it is preferable that the aromatic tricarbonyl monomer is included in the aromatic carbonyl monomer in an amount of 5.0 mol% or less, or 2.5 mol% or less, or 1.5 mol% or less, or 1.25 mol% or less.

As the aromatic dicarbonyl monomer in the carbonyl monomer, it may be preferable to include isophthaloyl chloride and terephthaloyl chloride.

The isophthaloyl chloride and terephthaloyl chloride are compounds having two carbonyl groups bonded to the meta or para positions relative to the central phenylene group. Therefore, by applying isopthaloyl chloride and terephthaloyl chloride together with the aromatic dicarbonyl monomer to form a polyamideimide copolymer, it is possible to improve the processability due to the meta bond in the copolymer and to improve mechanical properties It is possible to exhibit an advantageous effect for improvement of physical properties.

Specifically, the aromatic carbonyl monomer may preferably be composed of 10 to 20 mol% of isophthaloyl chloride, 75 to 85 mol% of terephthaloyl chloride and 0.01 to 5 mol% of tri-mesyl chloride .

As described above, in the polyamide-imide copolymer according to the embodiment of the present invention, the composition of the aromatic carbonyl monomer must satisfy both of the following two conditions, so that the colorless transparent characteristics (for example, low haze and yellow index) (E.g. high modulus and tensile strength).

(i) the aromatic carbonyl monomer is contained in an amount of at least 60 mol% based on the total moles of the aromatic dianhydride monomer and the aromatic carbonyl monomer

(ii) the aromatic carbonyl monomer comprises 95.0 to 99.9 mol% of aromatic dicarbonyl monomer and 0.01 to 5.0 mol% of aromatic tricarbonyl monomer

According to an embodiment of the present invention, the aromatic diamine monomer and the aromatic dianhydride monomer for forming the polyamideimide copolymer may be applied without any particular limitation to the compounds common in the art to which the present invention belongs .

Specific examples of the aromatic diamine monomer include 2,2'-bis (trifluoromethyl) -4,4'-biphenyldiamine (2,2'-bis (trifluoromethyl) ), 4,4'-diaminodiphenyl sulfone, 4,4 '- (9-fluorenylidene) dianiline, , Bis (4- (4-aminophenoxy) phenyl) sulfone), 2,2 ', 5,5'-tetrachlorobenzidine (2,2', 5 , 5'-tetrachlorobenzidine), 2,7-diaminofluorene, 4,4-diaminooctafluorobiphenyl, m-phenylene diamine (m- phenylenediamine, p-phenylenediamine, 4,4'-oxydianiline, 2,2'-dimethyl-4,4'-diaminobiphenyl (2 Bis [4- (4-aminophenoxy) phenyl] propane, 2'-dimethyl-4,4'-diaminobiphenyl, 2,2- , 1,3-bis (4-aminophenoxy) benzene, 1,3-bis 4,4'-diamino there is at least one fluoride selected from the group consisting of (4,4'-diaminobenzanilide) benzamide compound is not preferably used.

More preferably, the aromatic diamine monomer is selected from the group consisting of 2,2'-bis (trifluoromethyl) -4,4'-biphenyldiamine ).

Examples of the aromatic dianhydride monomer include 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 4,4' - (hexa (4,4'- (hexafluoroisopropylidene) diphthalic anhydride, 2,2'-bis- (3,4-dicarboxyphenyl) hexafluoropropane dianhydride (2, 2'-bis- (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, benzophenone tetracarboxylic dianhydride, pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride Benzophenone tetracarboxylic dianhydride, oxydiphthalic anhydride, cyclobutane-1,2,3,4-tetracarboxylic dianhydride, cyclobutane-1,2,3,4-tetracarboxylic dianhydride, , Cyclopentanetetracarboxyl At least one compound selected from the group consisting of cyclopentane tetracarboxylic dianhydride and bis (3,4-dicarboxyphenyl) sulfone dianhydride is preferably used. .

More preferably, the aromatic dianhydride monomer is selected from the group consisting of cyclobutane-1,2,3,4-tetracarboxylic dianhydride, 3,3 ', 4,4'-tetracarboxylic dianhydride, 4,4'-diphenyl tetracarboxylic acid dianhydride (3,3 ', 4,4'-biphenyltetracarboxylic acid dianhydride) or a mixture thereof.

Particularly, the aromatic diamine monomer, 2,2'-bis (trifluoromethyl) -4,4'-biphenyldiamine (2,2'-bis (trifluoromethyl) Cyclobutane-1,2,3,4-tetracarboxylic dianhydride, which is an aromatic dianhydride monomer, is produced by copolymerization with the aromatic carbonyl monomer Can be advantageously used for the formation of a polyamideimide copolymer satisfying the above-mentioned characteristics.

Preferably, the aromatic carbonyl monomer is used in an amount of 40 mol% or more, or 45 mol% or more, or 50 mol% or more, based on the total moles of the diamine monomer and the aromatic dicarbonyl monomer. Or less, and 65 mol% or less, or 60 mol% or less, or 55 mol% or less may be advantageous for the development of the above-described characteristics.

The polymerization conditions for forming the polyamic acid copolymerized with the aromatic diamine monomer, the aromatic dianhydride monomer and the aromatic carbonyl monomer are not particularly limited.

Preferably, the polymerization for the formation of the polyamic acid can be carried out by solution polymerization under an inert atmosphere at 0 to 100 캜.

Examples of the solvent for forming the polyamic acid include N, N-dimethylformamide, dimethylacetamide, dimethylsulfoxide, acetone, N-methyl-2-pyrrolidone, tetrahydrofuran, chloroform, gamma-butyrolactone Can be used.

Imidization after the formation of the polyamic acid can be performed thermally or chemically. For example, compounds such as acetic anhydride, pyridine may be used for chemical imidization.

According to an embodiment of the invention, the polyamideimide copolymer has a weight average molecular weight of 10,000 to 1,000,000 g / mol, or 50,000 to 1,000,000 g / mol, or 50,000 to 500,000 g / mol, or 50,000 to 300,000 g / mol .

II. Polyamideimide film

According to another embodiment of the present invention, there is provided a film comprising the above-described polyamideimide copolymer.

As a result of continuous research by the inventors of the present invention, it has been found that when the above-described aromatic carbonyl monomer is applied to form a polyamideimide copolymer using an aromatic diamine monomer, an aromatic dianhydride monomer and an aromatic carbonyl monomer, It was confirmed that a copolymer having mechanical properties could be formed.

As a result, the film containing the polyamide-imide copolymer can be used as a material for various molded articles requiring high mechanical properties together with colorless transparency. For example, the polyamide-imide film may be applied to a substrate for a display, a protective film for a display, a touch panel, a window cover of a foldable device, or the like.

The polyamide-imide film can be produced by a conventional method such as a dry method or a wet method using the polyamide-imide copolymer. For example, the polyamideimide film may be obtained by coating a solution containing the copolymer on an arbitrary support to form a film, and drying the film by evaporating the solvent from the film. If necessary, stretching and heat treatment for the polyamideimide film may be performed.

The polyamide-imide film can be colorless and transparent and exhibits excellent mechanical properties as prepared by using the polyamide-imide copolymer.

Specifically, the polyamideimide film may exhibit an yellow index (YI) of 2.80 or less, or 2.75 or less, measured according to ASTM E313 for a specimen having a thickness of 50 +/- 2 mu m.

The polyamideimide film may exhibit a haze of 1.20% or less or 1.15% or less as measured according to ASTM D1003 for a specimen having a thickness of 50 +/- 2 mu m.

The polyamideimide film may exhibit a Pencil Hardness of 3H or higher as measured according to ASTM D3363 for a specimen having a thickness of 50 +/- 2 mu m.

Said polyamideimide film having a modulus of at least 6.00 GPa or at least 6.10 GPa measured according to ISO 527-3 for specimens having a thickness of 50 +/- 2 mu m; And a maximum tensile strength of at least 240 MPa or at least 250 MPa.

The polyamide-imide copolymer according to the present invention makes it possible to provide a polyamide-imide film having colorless and transparent mechanical properties.

BRIEF DESCRIPTION OF THE DRAWINGS Fig. However, the following embodiments are intended to illustrate the invention, but the invention is not limited thereto.

Example  One

42.5 g of N, N-dimethylacetamide (N, N-dimethylacetamide) was charged with slowly blowing nitrogen into a 1000 mL 4-neck round flask (reactor) equipped with a stirrer, a nitrogen injector, a dropping funnel and a temperature controller , The temperature of the reactor was adjusted to 25 ° C, and then 2,2'-bis (trifluoromethyl) -4,4'-biphenyldiamine , TFDB) 4.4886 g (0.01401 mol) was added thereto to completely dissolve it. 0.0200 g (0.0001 mol) of cyclobutane-1,2,3,4-tetracarboxylic dianhydride (CBDA) was added while maintaining the temperature of the solution at 25 占 폚, And the mixture was stirred for a predetermined time to dissolve and react.

After cooling the solution to -10 캜, 0.5336 g (0.002628 mol) of isophthaloyl chloride (IPC), 2.4307 g (0.01197 mol) of terephthaloyl chloride (TPC) and 0.0027 g (0.000010 mol) of trimesoyl chloride (TMC) was added and stirred to obtain a polyamic acid solution having a solid content of 15% by weight.

N, N-dimethylacetamide was added to the polyamic acid solution to dilute the solid content to 5 wt% or less, and the solid content was precipitated with 10 L of methanol. The precipitated solids were filtered and then dried at 100 DEG C under vacuum for 6 hours or more to obtain a polyamide-imide copolymer in the form of solid (weight average molecular weight: about 172,111 g / mol).

Example  2

42.5 g of N, N-dimethylacetamide (N, N-dimethylacetamide) was charged with slowly blowing nitrogen into a 1000 mL 4-neck round flask (reactor) equipped with a stirrer, a nitrogen injector, a dropping funnel and a temperature controller , The temperature of the reactor was adjusted to 25 ° C, and then 2,2'-bis (trifluoromethyl) -4,4'-biphenyldiamine , TFDB) (4.471 g, 0.01396 mol). 0.0200 g (0.0001 mol) of cyclobutane-1,2,3,4-tetracarboxylic dianhydride (CBDA) was added while maintaining the temperature of the solution at 25 占 폚, And the mixture was stirred for a predetermined time to dissolve and react.

After the temperature of the solution was cooled to -10 DEG C, 0.5315 g (0.00261 mol) of isophthaloyl chloride (IPC), 2.4212 g (0.01192 mol) of terephthaloyl chloride (TPC) and 0.0463 g (0.00017 mol) of trimesoyl chloride (TMC) was added and stirred to obtain a polyamic acid solution having a solid content of 15% by weight.

N, N-dimethylacetamide was added to the polyamic acid solution to dilute the solid content to 5 wt% or less, and the solid content was precipitated with 10 L of methanol. The precipitated solids were filtered and then dried at 100 DEG C under vacuum for 6 hours or more to obtain a polyamide-imide copolymer in the form of solid (weight average molecular weight: about 231,454 g / mol).

Comparative Example  One

42.5 g of N, N-dimethylacetamide (N, N-dimethylacetamide) was charged with slowly blowing nitrogen into a 1000 mL 4-neck round flask (reactor) equipped with a stirrer, a nitrogen injector, a dropping funnel and a temperature controller , The temperature of the reactor was adjusted to 25 ° C, and then 2,2'-bis (trifluoromethyl) -4,4'-biphenyldiamine , TFDB) (4.505 g, 0.01407 mol). While keeping the temperature of the solution at 25 占 폚, 0.0201 g (0.0001 mol) of cyclobutane-1,2,3,4-tetracarboxylic dianhydride (CBDA) And the mixture was stirred for a predetermined time to dissolve and react.

After cooling the solution to -10 캜, 0.5355 g (0.00263 mol) of isophthaloyl chloride (IPC) and 2.44 g (0.012 mol) of terephthaloyl chloride (TPC) And stirred to obtain a polyamic acid solution having a solid content of 15% by weight.

N, N-dimethylacetamide was added to the polyamic acid solution to dilute the solid content to 5 wt% or less, and the solid content was precipitated with 10 L of methanol. The precipitated solids were filtered and then dried at 100 ° C under vacuum for 6 hours or more to obtain a polyamide-imide copolymer in the form of solid (weight average molecular weight: about 142,217 g / mol).

Example  3

The copolymer obtained in Example 1 was dissolved in N, N-dimethylacetamide to prepare a polymer solution of about 12% (w / v). The polymer solution was poured into a plastic substrate (UPILEX-75s, UBE Co.), the thickness of the polymer solution was uniformly controlled using a film applicator, dried in a Matze oven at 80 DEG C for 15 minutes, And cured for 30 minutes to obtain a polyamideimide film having a thickness of 50.0 mu m peeled from the substrate.

Example  4

A film having a thickness of 50.8 占 퐉 was obtained in the same manner as in Example 3, except that the copolymer obtained in Example 2 was used instead of the copolymer obtained in Example 1 above.

Comparative Example  2

A film having a thickness of 49.8 占 퐉 was obtained in the same manner as in Example 3, except that the copolymer obtained in Comparative Example 1 was used instead of the copolymer obtained in Example 1 above.

Test Example

The following properties were measured or evaluated for the films according to Examples 3, 4 and Comparative Example 2, and the results are shown in Table 1 below.

(1) Yellow Index (YI): Yellow index (YI) of the film was measured according to the method of ASTM E313 using COH-400 Spectrophotometer (NIPPON DENSHOKU INDUSTRIES).

(2) Pencil hardness: The pencil hardness of the film was measured according to the measurement method of ASTM D3363 using Pencil Hardness Tester. Specifically, when a pencil having various hardnesses is fixed to the tester and scratches on the film, the degree of occurrence of scratches on the film is visually observed with a microscope or microscope. When the scratches are not scratched by more than 70% of the total number of scratches, The corresponding values were evaluated for the pencil path of the film. Table 1 below shows the number of scratches (5 times in total) of the film with the pencil of the hardness in the test and the number of scratches in the film.

(3) Haziness: The haze value of the film was measured according to the measurement method of ASTM D1003 using COH-400 Spectrophotometer (NIPPON DENSHOKU INDUSTRIES).

(4) Modulus and maximum tensile strength: The modulus (GPa) and the maximum tensile strength (MPa) of the film were measured according to ISO 527-3 using Universal Testing Systems (Instron ^® 3360).

(5) Folding endurance: The bending strength of the film according to ISO 5626 was evaluated using an MIT type folding endurance tester.

Specifically, a specimen (1 cm x 7 cm) of the film was loaded into an impact strength tester at 25 ° C and bent at an angle of 135 ° at a speed of 175 rpm on the left and right sides of the specimen, with a radius of curvature of 0.8 mm and a load of 250 g , And the number of reciprocating bends (cycles) was measured until the specimen was broken.

film Example 3 Example 4 Comparative Example 2 Y.I. 2.75 2.71 2.84 Haziness (%) 1.14 0.88 1.38 Modulus (GPa) 6.13 6.40 5.83 Tensile Strength (MPa) 250 271 237 Pencil hardness 3H (0/5);
4H (3/5) 3H (0/5);
4H (2/5) 3H (1/5);
4H (4/5) Folding (cycle) 211,474 212,751 210,547

Referring to Table 1, the films of Examples 3 and 4 exhibited a low haze of 1.20% or less and a low yellowing index of 2.80 or less, and thus were found to have optically colorless and transparent characteristics.

Further, the films of Examples 3 and 4 had a high pencil hardness of 3H grade, and exhibited excellent scratch resistance, exhibited a modulus of 6.00 GPa or more, a maximum tensile strength of 240 MPa or more, and an endurance strength of 211,000 cycles or more, Respectively.

Claims (10)

As an imide of a polyamic acid copolymerized with an aromatic diamine monomer, an aromatic dianhydride monomer and an aromatic carbonyl monomer,
Wherein the aromatic carbonyl monomer is contained in an amount of 60.0 mol% or more based on the total moles of the aromatic dianhydride monomer and the aromatic carbonyl monomer,
Wherein the aromatic carbonyl monomer comprises 95.0 to 99.9 mole percent aromatic dicarbonyl monomer and 0.01 to 5.0 mole percent aromatic tricarbonyl monomer.
Polyamideimide copolymer.
The method according to claim 1,
The aromatic dicarbonyl monomer may be selected from the group consisting of 4,4'-biphenyldicarbonyl chloride, isophthaloyl chloride and terephthaloyl chloride. ≪ / RTI > wherein the polyamide-imide copolymer comprises at least one selected compound.
The method according to claim 1,
Wherein the aromatic tricarbonyl monomer is trimesoyl chloride.
The method according to claim 1,
Wherein the aromatic carbonyl monomer comprises 10 to 20 mole% of isophthaloyl chloride, 75 to 85 mole% terephthaloyl chloride and 0.01 to 5 mole% of trimesoyl chloride ). ≪ / RTI >
The method according to claim 1,
The aromatic diamine monomer may be 2,2'-bis (trifluoromethyl) -4,4'-biphenyldiamine, 4,4'-biphenyldiamine 4'-diaminodiphenyl sulfone, 4,4 '- (9-fluorenylidene) dianiline, bis (4- (4-aminophenoxy) phenyl) sulfone), 2,2 ', 5,5'-tetrachlorobenzidine ), 2,7-diaminofluorene, 4,4-diaminooctafluorobiphenyl, m-phenylenediamine, p- P-phenylenediamine, 4,4'-oxydianiline, 2,2'-dimethyl-4,4'-diaminobiphenyl (2,2'-dimethyl 4,4'-diaminobiphenyl), 2,2-bis [4- (4-aminophenoxy) phenyl] propane, Bis (4-aminophenoxy) benzene, and 4,4'-diami Benz not fluoride (4,4'-diaminobenzanilide) of at least one compound selected from the group consisting of,
Polyamideimide copolymer.
The method according to claim 1,
The aromatic dianhydride monomer may be selected from the group consisting of 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 4,4' - (hexafluoro (4,4'- (hexafluoroisopropylidene) diphthalic anhydride, 2,2'-bis- (3,4-dicarboxyphenyl) hexafluoropropane dianhydride (2,2 ' -bis- (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, benzophenone tetracarboxylic dianhydride, pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride ( benzophenone tetracarboxylic dianhydride, oxydiphthalic anhydride, cyclobutane-1,2,3,4-tetracarboxylic dianhydride, cyclohexane-1,2,3,4-tetracarboxylic dianhydride, Pentane tetracarboxylic At least one compound selected from the group consisting of cyclopentane tetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, and bis (3,4-dicarboxyphenyl) sulfone dianhydride.
Polyamideimide copolymer.
The method according to claim 1,
And a weight average molecular weight of 10,000 to 1,000,000 g / mol.
A film comprising the polyamideimide copolymer of claim 1.
9. The method of claim 8,
Wherein said film exhibits a yellow index of less than 2.80 and a haziness of less than 1.20% as measured according to ASTM D1003, measured according to ASTM E313 for a specimen having a thickness of 50 +/- 2 mu m. .
9. The method of claim 8,
The film exhibited a pencil hardness of at least 3H, a modulus of at least 6.00 GPa measured according to ISO 527-3 and a maximum tensile strength of at least 240 MPa, measured according to ASTM D3363 for specimens having a thickness of 50 +/- 2 mu m , Polyamideimide film.