KR102326790B1 - Polyamide copolymers and colorless and polyamideimide film comprising the same - Google Patents

Abstract

The present invention relates to a polyamide copolymer and a polyamide film comprising the same. The polyamide copolymer according to the present invention makes it possible to provide a colorless and transparent polyamide film having excellent mechanical properties.

Description

Polyamide copolymer and polyamide film comprising the same

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

Aromatic polyimide resins are mostly polymers having an amorphous structure, and exhibit excellent heat resistance, chemical resistance, electrical properties, and dimensional stability due to a rigid chain structure. Such polyimide resins are widely used as electrical/electronic materials.

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

In order to solve the above limitation and obtain a colorless and transparent polyimide resin, a method of restricting the movement of Pi-electrons by introducing a strong electron-withdrawing group such _{as trifluoromethyl (-CF 3 ) group;} A method of reducing the formation of the CTC by introducing a sulfone (-SO ₂ -) group, an ether (-O-) group, etc. to the main chain to form a curved structure; Alternatively, a method of inhibiting the formation of a resonance structure of Pi-electrons by introducing an aliphatic ring compound has been proposed.

However, it is difficult for the polyimide resin according to the above proposals to exhibit sufficient heat resistance due to a curved structure or an aliphatic cyclic compound, and there is still a limitation in that a film prepared using the same has poor mechanical properties.

Meanwhile, in recent years, in order to improve the scratch resistance of polyimide, polyamide copolymers incorporating a polyamide unit structure have been developed.

However, due to the high crystallinity of the polyamide copolymer, when a film is formed by coating it, the haze value is high and the yellow index is increased. There is a need for a way to do this.

An object of the present specification is to provide a polyamide copolymer capable of exhibiting excellent mechanical properties while having excellent optical properties.

In addition, the present specification is to provide a polyamide film including the polyamide copolymer.

The present specification includes an amide bond by an aromatic diamino group and a benzene-dicarbonyl group;

The aromatic diamino group is

i) an aromatic diamino group represented by the following formula (1); and

ii) containing at least one of an aromatic diamino group represented by the following Chemical Formulas 2 and 3;

The benzene-dicarbonyl group includes a benzene-1,3-dicarbonyl group and a benzene-1,4-dicarbonyl group ;

A polyamide copolymer is provided.

[Formula 1]

[Formula 2]

[Formula 3]

In Formulas 1 to 3,

X11 to X32 are each independently a halogenated alkyl having 1 to 5 carbon atoms or alkyl having 1 to 5 carbon atoms, and the number of substitutions of X11 to X32 in each benzene ring is each independently 1 to 4;

R21 to R32 are each independently alkyl having 1 to 5 carbon atoms, phenyl, alkylphenyl having 7 to 12 carbon atoms, or phenylalkyl having 7 to 12 carbon atoms.

In addition, the present specification provides a polyamide film comprising a polyamide layer formed by the polyamide copolymer.

Hereinafter, the polyamide copolymer and the polyamide film according to embodiments of the present invention will be described in detail.

Unless explicitly stated herein, terminology is for the purpose of referring to specific embodiments only, and is not intended to limit the present invention.

As used herein, the singular forms also include the plural forms unless the phrases clearly indicate the opposite.

As used herein, the meaning of “comprising” specifies a particular characteristic, region, integer, step, operation, element and/or component, and other specific characteristic, region, integer, step, operation, element, component, and/or group. It does not exclude the existence or addition of

According to one embodiment of the present invention,

containing an amide bond by an aromatic diamino group and a benzene-dicarbonyl group;

The aromatic diamino group is

i) an aromatic diamino group represented by the following formula (1); and

ii) containing at least one of an aromatic diamino group represented by the following Chemical Formulas 2 and 3;

The benzene-dicarbonyl group includes a benzene-1,3-dicarbonyl group and a benzene-1,4-dicarbonyl group ;

A polyamide copolymer is provided.

[Formula 1]

[Formula 2]

[Formula 3]

In Formulas 1 to 3,

X11 to X32 are each independently a halogenated alkyl having 1 to 5 carbon atoms or alkyl having 1 to 5 carbon atoms, and the number of substitutions of X11 to X32 in each benzene ring is each independently 1 to 4;

R21 to R32 are each independently alkyl having 1 to 5 carbon atoms, phenyl, alkylphenyl having 7 to 12 carbon atoms, or phenylalkyl having 7 to 12 carbon atoms.

As a result of the present inventors' research, when an amine moiety of an aromatic diamine monomer and a carbonyl group of a benzene-dicarbonyl-based monomer such as phthaloyl chloride react to form a polyamide copolymer, aromatic diamine repeats When both unsubstituted and alkyl-substituted units are used, they have a flexible structure and have no significant loss in strength and hardness, have excellent mechanical properties, and optical properties such as low haze and high transparency It was confirmed that this excellent polyamide copolymer could be prepared.

According to an embodiment of the invention, the polyamide copolymer is, in the aromatic diamino unit constituting one axis of the amide bond, i) one type of aromatic in which only hydrogen exists in the nitrogen atom of the aromatic diamino group constituting the amide bond. The diamino group and ii) one or two aromatic diamino groups in which a substituent other than hydrogen is present at the nitrogen atom of the aromatic diamino group forming the amide bond may be included.

And, in the benzene-dicarbonyl unit, wherein the polyamide copolymer is bonded to the aromatic diamino group to form the other axis of the amide bond, a benzene-1,3-dicarbonyl group (benzene-1,3-dicarbonyl group) group) and a benzene-1,4-dicarbonyl group.

That is, the polyamide copolymer according to an embodiment of the present invention may form an amino bond by two or three kinds of aromatic diamino groups and two kinds of benzene-dicarbonyl units, and thus, a total of 4 species or 6 amide repeat units.

First, the aromatic diamino group will be described.

The aromatic diamino group is

i) an aromatic diamino group represented by the following formula (1); and

ii) At least one of aromatic diamino groups represented by the following Chemical Formulas 2 and 3 is included.

[Formula 1]

[Formula 2]

[Formula 3]

In Formulas 1 to 3,

X11 to X32 are each independently a halogenated alkyl having 1 to 5 carbon atoms or alkyl having 1 to 5 carbon atoms, and the number of substitutions of X11 to X32 in each benzene ring is each independently 1 to 4;

R21 to R32 are each independently alkyl having 1 to 5 carbon atoms, phenyl, alkylphenyl having 7 to 12 carbon atoms, or phenylalkyl having 7 to 12 carbon atoms.

That is, Formula 1 can be viewed as an unsubstituted aromatic diamino group in which only hydrogen exists in both nitrogen atoms constituting an amide bond, and Formula 2 is a hydrogen atom of any one of two nitrogen atoms constituting an amide bond can be seen as a monosubstituted aromatic diamino group substituted by the above-mentioned substituents, and in Formula 3 above, both the hydrogens of the two nitrogen atoms constituting the amide bond are substituted by the above-mentioned substituents. can

Accordingly, the polyamide of the present invention is an unsubstituted aromatic diamino group in which the hydrogen bonded to the nitrogen atom of the amide bond is unsubstituted and the aromatic diamino in which the hydrogen bonded to the nitrogen atom of the amide bond is substituted by another substituent. group must be included simultaneously.

Among them, the aromatic diamino group represented by Formula 1, that is, an aromatic diamino group in which hydrogen bonded to a nitrogen atom is not substituted with another substituent, has an intermolecular bonding force and/or attractive force through an intermolecular or intramolecular hydrogen bond. , to improve the chemical and physical properties of the polyamide copolymer.

In addition, the aromatic diamino group represented by Formula 2, that is, the aromatic diamino group in which only hydrogen bonded to one of the two nitrogen atoms is substituted, is formed through an intermolecular or intramolecular hydrogen bond. It is possible to increase the bonding strength and / or attractive force between molecules, but the number of intermolecular or intramolecular hydrogen bonds is small compared to the structure in which the alkyl group is not substituted, so the bonding strength and / or attractive force is not large, so it can be adjusted to an appropriate level. can

And, the aromatic diamino group represented by Formula 3, that is, the aromatic diamino group in which all hydrogens bonded to two nitrogen atoms are substituted, has a structure in which hydrogen bonding is difficult due to the substituted alkyl group, Although the attractive force is small, the chemical and mechanical properties of the polyamide copolymer can be maintained at the same level as that of the conventional polyamide due to the strong molecular structure of the wholly aromatic.

As described above, the polyamide copolymer according to an embodiment of the present invention comprises an aromatic diamino group in which the hydrogen bonded to the nitrogen atom of the amide bond is unsubstituted and the hydrogen bonded to the nitrogen atom of the amide bond is formed by a different substituent. The substituted aromatic diamino group is necessarily included at the same time to realize excellent light transmittance, and thus, it can be used in a flexible display device or the like.

According to an embodiment of the present invention, in the polyamide copolymer, the value of the substitution ratio of the amine represented by Equation 1 below may be greater than 0 and less than or equal to 0.7.

[Equation 1]

In Equation 1 above,

N1 is the number of moles of the aromatic diamino group represented by Formula 1 included in the polyamide copolymer, and N2 is the number of moles of the aromatic diamino group represented by Formula 2 included in the polyamide copolymer and N3 is the number of moles of aromatic diamino groups, represented by Formula 3, included in the polyamide copolymer; In Equation 1, the number of nitrogen atoms present in the aromatic diamino groups of Formulas 1 to 3 in the polyamide copolymer is the denominator, and the number of substituted nitrogen atoms is the numerator to represent the substitution rate. In addition, since the polyamide copolymer according to an embodiment of the present invention necessarily includes an aromatic diamino group in which a nitrogen atom is substituted, the value of Equation 1 is necessarily greater than 0.

The substitution rate value represented by Equation 1 may be greater than about 0, or 0.01 or more, or 0.05 or more, and may be about 0.7 or less, or 0.5 or less, preferably, about 0.5 or less, or about 0.3 or less.

As the substitution rate value represented by Equation 1 satisfies the above-mentioned range, the polyamide copolymer can maintain high surface hardness when manufactured into a film or the like, and has excellent optical properties, such as a low YI value. be able to have When the substitution rate value is out of the above range, when the polyamide copolymer is prepared as a film, a problem in that the surface hardness value is lowered may occur.

And, X11 to X32, which are substituents substituted on the benzene ring of the aromatic diamino group, are each independently fluorinated alkyl having 1 to 5 carbon atoms, and it is preferable that the substitution ratio of fluorine atoms in the alkyl group is 50% or more. can do.

Such substituents are specifically, for example, difluoromethyl, trifluoromethyl, trifluoroethyl, tetrafluoroethyl, pentafluoroethyl, tetrafluoropropyl, pentafluoropropyl, hexafluoropropyl, Heptafluoropropyl, pentafluorobutyl, hexafluorobutyl, heptafluorobutyl, octafluorobutyl, nonafluorobutyl, hexafluoropentyl, heptafluoropentyl, octafluoropentyl, nonafluoropentyl, and decafluoropentyl or undecafluoropentyl, preferably an alkyl group in which all hydrogens are substituted with fluorine atoms, most preferably trifluoromethyl or pentafluoroethyl. have.

When the fluorine atom substitution ratio as described above is satisfied, the YI value of the polyamide resin is lowered, and excellent optical properties can be realized. If the substitution ratio of the fluorine atom is too low, optical properties such as an increase in YI value may decrease due to an intermolecular or intramolecular charge transfer complex (CTC) effect.

Accordingly, the polyamide copolymer according to an embodiment of the present invention may include, in a preferred form, i) an aromatic diamino group represented by the following Chemical Formula 1-1; and ii) an aromatic diamino group represented by the following Chemical Formulas 2-1 and 3-1.

[Formula 1-1]

[Formula 2-1]

[Formula 3-1]

In Formulas 1-1 to 3-1,

R21 to R32 are each independently alkyl having 1 to 5 carbon atoms, phenyl, alkylphenyl having 7 to 12 carbon atoms, or phenylalkyl having 7 to 12 carbon atoms.

And, according to an embodiment of the invention, R21 to R32 are, each independently, methyl, propyl, isopropyl, butyl, 2-butyl, isobutyl, or tert-butyl, preferably, methyl, propyl, or isopropyl.

When the size of R21 to R32 is too large, the free volume value of the polymer chain may increase due to the steric effect, thereby causing deterioration of physical properties.

Next, a description will be given of a benzene-dicarbonyl group that forms an amide bond by bonding with an amine of the aforementioned aromatic diamino group.

The benzene-dicarbonyl group includes both a benzene-1,3-dicarbonyl group and a benzene-1,4-dicarbonyl group. do.

Benzene-1,3-dicarbonyl group (benzene-1,3-dicarbonyl group), isophthaloyl chloride (isophthaloyl chloride, IPC), isophthalic acid (isophthalic acid, IPA), including isophthaloyl-based It can be seen as a repeating unit derived from a monomer.

The benzene-1,3-dicarbonyl group has a bent molecular structure in which the carbonyl groups are bonded to each other at meta positions centered on the benzene ring, leading to chain packing in the polymer. It has a property of preventing over-alignment, and thus increases the amorphous region in the polyamide copolymer, thereby improving the optical properties and bending strength of the polyamide film.

And, the benzene-1,4-dicarbonyl group (benzene-1,4-dicarbonyl group), including terephthaloyl chloride (terephthaloyl chloride, TPC), terephthalic acid (terephthalic acid, TPA), etc., terephthalo It can be seen as a repeating unit derived from a mono-monomer.

The benzene-1,4-dicarbonyl group has a linear molecular structure in which the carbonyl groups are bonded to each other at the para position around the benzene ring, resulting in chain packing and Alignment can be kept constant, and by increasing the crystalline region in the polyamide copolymer, the surface hardness and mechanical properties of the polyamide film can be improved.

And, according to an embodiment of the invention, in the polyamide copolymer, a benzene-1,3-dicarbonyl group and a benzene-1,4-dicarbonyl group (benzene- The ratio of the benzene-1,3-dicarbonyl group in the total of 1,4-dicarbonyl groups) may be about 30 mol% or less.

And, the ratio may be greater than 0 mole %, or greater than about 0.1 mole %, or greater than about 1 mole %, or greater than about 3 mole %, and less than or equal to about 30 mole %, less than or equal to about 25 mole %, or greater than or equal to about 20 mole %. % or less.

If the ratio of benzene-1,3-dicarbonyl group is relatively low within the above range, excellent surface hardness and mechanical properties can be imparted to the polyamide copolymer or polyamide film. If the ratio of the benzene-1,3-dicarbonyl group is relatively high within the above range, the polyamide copolymer or the polyamide film has relatively excellent optical properties and It can be given the bending resistance property.

The polyamide copolymer of the present invention contains a benzene-1,3-dicarbonyl group and a benzene-1,4-dicarbonyl group in a ratio within the above-mentioned range. -dicarbonyl group), it is possible to implement each advantage very effectively.

In addition, the polyamide copolymer according to an embodiment of the present invention has, in addition to the aromatic diamino group of the above formula, other types of aromatic diamino groups, specifically, for example, 2,2'-dimethyl-4,4 '-diaminobenzidine (2,2'-dimethyl-4,4'-diaminobenzidine), 4,4'-diaminodiphenyl sulfone (4,4'-diaminodiphenyl sulfone), 4,4'-(9-flu Orenylidene) dianiline (4,4'-(9-fluorenylidene)dianiline), bis(4-(4-aminophenoxy)phenyl)sulfone (bis(4-(4-aminophenoxy)phenyl)sulfone), 2 ,2',5,5'-tetrachlorobenzidine (2,2',5,5'-tetrachlorobenzidine), 2,7-diaminofluorene (2,7-diaminofluorene), 4,4-diaminooctafluor Lobbyphenyl (4,4-diaminooctafluorobiphenyl), m-phenylenediamine (m-phenylenediamine), p-phenylenediamine (p-phenylenediamine), m-xylenediamine (m-xylenediamine), p-xylenediamine (p -xylenediamine), 4,4'-oxydianiline (4,4'-oxydianiline), 2,2'-dimethyl-4,4'-diaminobiphenyl (2,2'-dimethyl-4,4'- diaminobiphenyl), 2,2-bis [4- (4-aminophenoxy) phenyl] propane (2,2-bis [4- (4-aminophenoxy) phenyl] propane), 1,3-bis (4-aminophenoxy) C) benzene (1,3-bis (4-aminophenoxy) benzene), and 4,4'-diaminobenzanilide (4,4'-diaminobenzanilide) derived from at least one selected from the group consisting of aromatic dia It may further include a mino group.

When these other types of aromatic diamino groups are included, they may be included in an amount of about 0.01 mol% or more, or about 0.025 mol% or more, or about 0.05 mol% or more, based on the total aromatic diamino group forming an amide bond, and about 5.0 It may be desirable to include less than or equal to about 2.5 mol%, or less than or equal to about 1.5 mol%, or less than or equal to about 1.0 mol%.

In addition, the polyamide copolymer according to another embodiment of the present invention is a carbonyl group forming an amide bond with the aforementioned aromatic diamino group, and includes a benzene-1,3-dicarbonyl group (benzene-1,3-dicarbonyl group). In addition to the dicarbonyl group and the benzene-1,4-dicarbonyl group, it may further include a carbonyl group derived from an aromatic dicarbonyl monomer or a tricarbonyl monomer.

Here, the aromatic dicarbonyl monomer may include 4,4'-biphenyldicarbonyl chloride, 2,6-pyridinedicarbonyl dichloride, and the like. In addition, the aromatic tricarbonyl monomer may include trimesoyl chloride and the like.

In particular, the aromatic tricarbonyl monomer may act as a crosslinking agent in the copolymerization process, thereby further improving the mechanical properties of the polyamide copolymer.

In order to achieve this effect, the aromatic tricarbonyl monomer is preferably contained in an amount of about 0.01 mol% or more, or about 0.025 mol% or more, or about 0.05 mol% or more, of the total carbonyl-derived monomers, and about 5.0 mol% It is preferably included in an amount of less than, or less than about 2.5 mol%, or less than about 1.5 mol%, or less than about 1.25 mol%. When the aromatic tricarbonyl monomer is applied in excess, optical properties of the prepared polyamide copolymer may be reduced, and flexibility may be reduced.

On the other hand, in the polymerization reaction for producing a polyamide comprising an amide bond by an aromatic diamino group and a benzene-dicarbonyl group by polymerizing the aromatic diamine monomer and the aromatic dicarbonyl monomer, the reaction conditions are not particularly limited. . However, the polymerization reaction may be carried out while controlling the ratio of each monomer in order to control the ratio of the repeating units derived from each monomer in the polyamide copolymer.

The polymerization reaction for forming the amide bond may be carried out by solution polymerization under an inert gas atmosphere under a temperature condition of about minus 25° C. to about 25° C., more preferably about minus 25° C. to about 0° C. have.

In this case, as the reaction solvent, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, acetone, N-methyl-2-pyrrolidone, tetrahydrofuran, chloroform, gamma- Butyrolactone and the like may be used.

According to an embodiment of the invention, the polyamide copolymer may have a weight average molecular weight value of from about 100,000 to about 600,000 g/mol, or from about 130,000 to about 500,000 g/mol, or from about 140,000 to about 400,000 g/mol. .

In this case, the weight average molecular weight value may be measured by gel permeation chromatography (GPC).

In this case, the above-described polyamide copolymer may include, as a specific example, repeating units represented by the following Chemical Formulas 11 to 14.

[Formula 11]

[Formula 12]

[Formula 13]

[Formula 14]

In addition, this polyamide copolymer may be a random copolymer in which each repeating unit is arranged without a certain rule, each repeating unit is connected by a constant number of repeats, or a content ratio of each repeating unit is maintained in a segment. , may be a block copolymer.

According to another embodiment of the invention, there is provided a polyamide film comprising a polyamide layer formed by the above-described polyamide copolymer.

When the film is manufactured using the above-described polyamide copolymer, excellent optical and mechanical properties can be realized, and at the same time, flexibility is provided, and thus it can be used as a material for various molded articles. For example, the polyamide film may be applied to a display substrate, a display protective film, a touch panel, a window cover of a foldable device, and the like.

The polyamide film may be prepared by a conventional method such as a dry method or a wet method using the polyamide block copolymer. For example, the polyamide film may be obtained by coating a solution containing the copolymer on an arbitrary support to form a film, and evaporating a solvent from the film to dry it, and if necessary, the polyamide film Stretching and heat treatment for the film may be further performed.

The thickness of the polyamide film may be, for example, from about 10 μm to about 200 μm, preferably from about 10 μm to about 100 μm, or from about 30 μm to about 70 μm, but this may vary depending on the use and properties. As such, the present invention is not necessarily limited thereto.

And in this case, the polyamide film may further include a substrate, and may be manufactured in such a way that the polyamide layer is formed on at least one surface of the substrate.

At this time, the substrate; It may include one or more polymers selected from the group consisting of polyimide-based, polycarbonate-based, polyester-based, polyalkyl (meth)acrylate-based, polyolefin-based, and polycyclic olefin-based polymers.

As the polyamide film is prepared by using the polyamide block copolymer, it may exhibit excellent mechanical properties while being colorless and transparent.

Specifically, the polyamide film has a haze value measured according to ASTM D1003 of about 5% or less, or about 0.1% to about 5%, or from about 0.1% to about 1.0%.

And, the polyamide film has a transmittance value of about 85% or more, or, about 85% to about 95%, or about 85, measured according to ASTM E 313 for a specimen having a thickness of about 50 ± 2 μm. % to about 90%.

And, the polyamide film, a specimen is prepared according to ASTM D882 standard, and a modulus value measured for the specimen may be from about 2.5 GPa to about 7.5 GPa, or from about 5.5 GPa to about 7 GPa.

And, the polyamide film, a specimen is prepared according to ASTM D882 standard, and the elongation value measured for the specimen is about 3% or more, or about 3% to about 20%, preferably about 5% to about 15%.

In addition, the polyamide film is prepared by preparing a specimen having a thickness of about 50 ± 2 μm, and for this, a pencil hardness value measured according to ASTM D3363 may be H or more.

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

^{1 and 2 are 1} H-NMR spectra of the polyamide copolymer obtained in Examples of the present invention.

Hereinafter, preferred embodiments are presented to help the understanding of the invention. However, the following examples are only for illustrating the invention, and do not limit the invention thereto.

<Example>

The weight average molecular weight values of the polyamide copolymers prepared in the following Examples and Comparative Examples were measured by the following method.

Apparatus: Gel Permeation Chromatography GPC (Measuring Instrument Name: GPC-Chloroform; Manufacturer: WATERS)

Column: Mixed B Column 2ro

Flow rate: 1 mL/min

Column temperature: 50°C

Injection volume: 100 μl (Sample concentration: 1 mg/ml)

Samples for standardization: polystyrene standards (4,000; 10,000; 30,000; 100,000; 300,000; 1,000,000; 4,000,000)

In the polyamide copolymers prepared in the following Examples and Comparative Examples, the -CH ₃ substitution rate value of the N atom is calculated through the widths of the _{-NH- peak and the -CH 3} ^{peak in 1} H-NMR spectrum of the sample did.

<Comparative Example: Preparation of polyamide copolymer>

Comparative Example 1

266 g of N,N-dimethylacetamide (DMAc) while slowly blowing nitrogen into a 500 mL 4-neck round flask (reactor) equipped with a stirrer, nitrogen injector, dropping funnel, and temperature controller After filling the reactor and adjusting the temperature of the reactor to about -10 °C, 23.940 g of calcium chloride, 2,2'-bis(trifluoromethyl)-4,4'-biphenyldiamine (2,2'-bis(trifluoromethyl) )-4,4'-biphenyldiamine, TFDB) (0.0442 mol) was dissolved.

To this, terephthaloyl chloride powder (0.0362 mol) was added and stirred, and isophthaloyl chloride powder (0.0080 mol) was added and stirred as soon as terephthaloyl chloride was dissolved. After complete dissolution, amide for 12 hours The formation reaction proceeded.

After completion of the reaction, DMAc was added to dilute the solid content to 5% or less, which was precipitated with 1 L of methanol, the precipitated solid was filtered, and then dried in a vacuum at 100 ° C. for about 6 hours or more. A polyamide copolymer in solid form was prepared. (Mw: 350,000)

Comparative Example 2

266 g of N,N-dimethylacetamide (DMAc) while slowly blowing nitrogen into a 500 mL 4-neck round flask (reactor) equipped with a stirrer, nitrogen injector, dropping funnel, and temperature controller After adjusting the temperature of the reactor to about -10 °C, 23.940 g of calcium chloride, 2,2'-bis(trifluoromethyl)-4,4'-biphenyldiamine (2,2'-bis(trifluoromethyl) -4,4'-biphenyldiamine, TFDB) was dissolved in 14.153 g (0.0442 mol).

Here, isophthaloyl chloride powder (0.0080 mol) was added with stirring, and terephthaloyl chloride powder (0.0362 mol) was added and stirred while the isophthaloyl chloride was dissolved immediately, and after complete dissolution, amide for 12 hours The formation reaction proceeded.

After completion of the reaction, DMAc was added to dilute the solid content to 5% or less, which was precipitated with 1 L of methanol, the precipitated solid was filtered, and then dried in a vacuum at 100 ° C. for about 6 hours or more. A polyamide copolymer in solid form was prepared. (Mw: 412,000)

<Example: Preparation of polyamide copolymer>

Preparation Example 1: Preparation of an acyl chloride complex

Into a 1000 mL 4-neck round flask (reactor) equipped with a stirrer, nitrogen injector, dropping funnel, and temperature controller, terephthaloyl chloride (TPC) (2.136 mol) and isophthaloyl chloride, IPC) (0.469 mol), melt-kneaded at about 100 to about 110° C. for 3 hours, and then dried at about 0° C. for 12 hours, acyl chloride comprising terephthaloyl chloride and isophthaloyl chloride of the complex was prepared.

Thereafter, the acyl chloride complex was crushed with a jaw crusher to prepare a powder having an average particle diameter of about 5 mm.

Preparation Example 1: Preparation of polyamide copolymer

266 g of N,N-dimethylacetamide (DMAc) while slowly blowing nitrogen into a 500 mL 4-neck round flask (reactor) equipped with a stirrer, nitrogen injector, dropping funnel, and temperature controller After adjusting the temperature of the reactor to about -10 °C, 23.940 g of calcium chloride, 2,2'-bis(trifluoromethyl)-4,4'-biphenyldiamine (2,2'-bis(trifluoromethyl) -4,4'-biphenyldiamine, TFDB) (0.0442 mol) was dissolved.

Here, the acyl chloride complex powder (0.0442 mol) obtained in Preparation Example 1 was added and stirred, and the amide formation reaction was carried out at about -10 °C for about 12 hours.

After completion of the reaction, DMAc was added to dilute the solid content to 5% or less, which was precipitated with 1 L of methanol, the precipitated solid was filtered, and the solid was dried in a vacuum at 100° C. for at least 6 hours. A polyamide copolymer of the form was prepared. (Mw: 382,000)

Example 1

262 g of N,N-dimethylacetamide (DMAc) while slowly blowing nitrogen into a 500 mL 4-neck round flask (reactor) equipped with a stirrer, nitrogen injector, dropping funnel, and temperature controller was filled, and the temperature of the reactor was adjusted to about 25° C., and then the polyamide copolymer (0.0647 mol) prepared in Preparation Example 1 was dissolved.

Here, sodium hydroxide (0.0130 mol; about 0.20 equivalents relative to the amine group in the polyamide copolymer) was added and stirred for about 12 hours, and bromomethane (CH ₃ Br) (0.0155 mol; about 1.19 equivalents compared to sodium hydroxide) was added thereto. After addition, the reaction proceeded so that the N atom of the polyamide copolymer was substituted with a methyl group for about 6 hours. (Substitution rate: about 6.5%)

After completion of the reaction, DMAc was added to dilute the solid content to 5% or less, which was precipitated with 1 L of methanol, the precipitated solid was filtered, and then dried in a vacuum at 100 ° C. for about 6 hours or more. A polyamide copolymer in solid form was prepared. (Mw: 352,000)

Example 2

262 g of N,N-dimethylacetamide (DMAc) while slowly blowing nitrogen into a 500 mL 4-neck round flask (reactor) equipped with a stirrer, nitrogen injector, dropping funnel, and temperature controller was filled, and the temperature of the reactor was adjusted to about 25° C., and then the polyamide copolymer (0.0647 mol) prepared in Preparation Example 1 was dissolved.

To this, sodium hydroxide (0.0259 mol; about 0.40 equivalent relative to the amine group in the polyamide copolymer) was added and stirred for about 12 hours, and bromomethane (CH ₃ Br) (0.0311 mol; about 1.20 equivalent compared to sodium hydroxide) was added thereto. After addition, the reaction proceeded so that the N atom of the polyamide copolymer was substituted with a methyl group for about 6 hours. (Replacement rate: about 13.0%)

After completion of the reaction, DMAc was added to dilute the solid content to 5% or less, which was precipitated with 1 L of methanol, the precipitated solid was filtered, and then dried in a vacuum at 100 ° C. for about 6 hours or more. A polyamide copolymer in solid form was prepared. (Mw: 324,000)

Example 3

262 g of N,N-dimethylacetamide (DMAc) while slowly blowing nitrogen into a 500 mL 4-neck round flask (reactor) equipped with a stirrer, nitrogen injector, dropping funnel, and temperature controller was filled, and the temperature of the reactor was adjusted to about 25° C., and then the polyamide copolymer (0.0647 mol) prepared in Preparation Example 1 was dissolved.

Here, sodium hydroxide (0.0388 mol; about 0.60 equivalents relative to the amine group in the polyamide copolymer) was added and stirred for about 12 hours, and bromomethane (CH ₃ Br) (0.0466 mol; about 1.20 equivalents compared to sodium hydroxide) was added thereto. After addition, the reaction proceeded so that the N atom of the polyamide copolymer was substituted with a methyl group for about 6 hours. (Replacement rate: about 22.3%)

After completion of the reaction, DMAc was added to dilute the solid content to 5% or less, which was precipitated with 1 L of methanol, the precipitated solid was filtered, and then dried in a vacuum at 100 ° C. for about 6 hours or more. A polyamide copolymer in solid form was prepared. (Mw: 301,000)

^{1 is a 1} H-NMR spectrum of the substituted polyamide copolymer sample obtained above.

Referring to FIG. 1 , in the polyamide copolymer, it can be seen that the relative ratio of the _{unsubstituted -NH peak is 1.45, and the relative ratio of the -CH 3 peak is 1.25.} Since the number of hydrogens is 1 for the -NH group and _{3 for the} -CH 3 group, according to the above results, the relative ratio of -NH groups is 1.45, and the relative ratio of _{-CH 3 groups is 0.42} and, therefore, it can be seen that the substitution rate is about 22.3%.

Example 4

262 g of N,N-dimethylacetamide (DMAc) while slowly blowing nitrogen into a 500 mL 4-neck round flask (reactor) equipped with a stirrer, nitrogen injector, dropping funnel, and temperature controller was filled, and the temperature of the reactor was adjusted to about 25° C., and then the polyamide copolymer (0.0647 mol) prepared in Preparation Example 1 was dissolved.

To this, sodium hydroxide (0.0647 mol; about 1.00 equivalents relative to the amine group in the polyamide copolymer) was added and stirred for about 12 hours, and bromomethane (CH ₃ Br) (0.0776 mol; about 1.20 equivalents compared to sodium hydroxide) was added thereto. After addition, the reaction proceeded so that the N atom of the polyamide copolymer was substituted with a methyl group for about 6 hours. (Replacement rate: about 68.0%)

After completion of the reaction, DMAc was added to dilute the solid content to 5% or less, which was precipitated with 1 L of methanol, the precipitated solid was filtered, and then dried in a vacuum at 100 ° C. for about 6 hours or more. A polyamide copolymer in solid form was prepared. (Mw: 301,000)

^{Fig. 2 is a 1} H-NMR spectrum of the substituted polyamide copolymer sample obtained above.

Referring to FIG. 2 , in the polyamide copolymer, it can be seen that the relative ratio of the _{unsubstituted -NH peak is 0.61, and the relative ratio of the -CH 3 peak is 3.89.} Since the number of hydrogens is 1 for the -NH group and _{3 for the} -CH 3 group, according to the above results, the relative ratio of -NH groups is 0.61, and the relative ratio of _{-CH 3 groups is 1.30} and, therefore, it can be seen that the substitution rate is about 68.0%.

Polyamide Film Manufacturing

The polyamide copolymer obtained in Examples and Comparative Examples was dissolved in N,N-dimethylacetamide to prepare a polymer solution of about 12% (w/V).

The polymer solution was applied on a polyimide base film (UPILEX-75s, UBE), and the thickness of the polymer solution was uniformly adjusted using a film applicator.

Thereafter, after drying in a Matiz oven at 80° C. for 15 minutes, and curing at 250° C. for 30 minutes while flowing nitrogen, it was peeled from the base film to obtain a polyamide film having a thickness of about 50 μm.

test example

The following properties were measured or evaluated for the polyamide films according to Examples and Comparative Examples, and the results are summarized in the table below.

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

Haziness: The haze value of the film was measured according to the measurement method of ASTM D 1003 using a COH-400 Spectrophotometer (NIPPON DENSHOKU INDUSTRIES).

Transmittance: Using a UV-2600 UV-vis spectrometer (Shimadzu), the transmittance value of the film with respect to 550 nm light was measured according to the measurement method of ASTM E313.

Pencil hardness: The pencil hardness of the film was measured according to the measurement method of ASTM D3363 using a Pencil Hardness Tester. Specifically, after fixing pencils of various hardnesses to the tester and scratching the film, the degree of scratches on the film was observed with the naked eye or a microscope. The corresponding values were evaluated by the pencil path of the film. Table 1 below shows the number of times the film was scratched with a pencil of the corresponding hardness in the test (total 5 times) and the number of scratches among them.

Modulus and Elongation: The modulus (GPa) and elongation (%) of the film were measured according to ASTM D882 using Universal Testing Systems (Instron ^{® 3360).}

Folding endurance: MIT-type folding endurance tester (folding endurance tester) was used to evaluate the bending strength of the film based on ISO 5626.

Specifically, a specimen of the film (1 cm * 7 cm) was loaded into a bend strength tester under 25 ° C, and bent at an angle of 135 °, a radius of curvature of 0.8 mm and a load of 250 g at a speed of 175 rpm on the left and right sides of the specimen. , the number of reciprocating bending cycles (cycle) was measured until the specimen was fractured.

Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 substitution rate
(%) 6.5 13.0 22.3 68.0 0 0 Y.I. 2.89 2.97 3.01 3.55 23.59 3.89 Haze (%) 0.80 0.76 0.52 2.30 92.4 3.45 Transmittance (%) 88.72 88.39 88.63 88.78 63.87 81.20 pencil hardness 2H H H HB F H Modulus (GPa) 6.5 6.3 6.1 3.8 3.2 6.8 Elongation (%) 14 12 13 6 5 14 MIT (0.8R) 7800 7000 6800 500 785 5200 Mw (g/mol) 352k 324k 301k 144k 112k 235k

Referring to Table 1, the polyamide copolymer according to the embodiment of the present invention has very high transmittance and a low haze value, and has excellent optical properties, as well as a modulus value or elongation value, compared to the polyamide copolymer of the comparative example. It can be seen that mechanical properties such as , bending resistance value are also excellent.

In particular, in the case of Comparative Example 1, it can be seen that the haze value is very high, the transmittance value is very low, and the yellow index value is also high, so that the optical properties are very poor, and the mechanical properties are also very poor.

In the case of Comparative Example 2, in terms of mechanical properties, it seems to be improved to some extent compared to Comparative Example 1, but again, haze, transmittance, and yellow index values, etc., are poor compared to Examples of the present application, and excellent optical and mechanical properties was found to be very difficult to achieve at the same time.

In the case of Examples of the present application, depending on the value of the substitution ratio, the optical and mechanical property values show some changes, but they are generally in an excellent range compared to the comparative example, and in particular, the yellow index value is below a specific value, and colorlessness is It was confirmed that it was shown, and it was found that excellent optical properties and mechanical properties could be achieved at the same time.

Accordingly, the polyamide copolymer according to an embodiment of the present invention is considered to be applicable to various industrial fields.

Claims (16)

containing an amide bond by an aromatic diamino group and a benzene-dicarbonyl group;
The aromatic diamino group is
i) an aromatic diamino group represented by the following formula (1); and
ii) containing at least one of an aromatic diamino group represented by the following Chemical Formulas 2 and 3;
The benzene-dicarbonyl group includes a benzene-1,3-dicarbonyl group and a benzene-1,4-dicarbonyl group, and ;
A polyamide copolymer in which the substitution rate value of the amine represented by the following formula (1) is greater than 0 and less than or equal to 0.3:
[Formula 1]

[Formula 2]

[Formula 3]

In Formulas 1 to 3,
X11 to X32 are each independently a halogenated alkyl having 1 to 5 carbon atoms or alkyl having 1 to 5 carbon atoms, and the number of substitutions of X11 to X32 in each benzene ring is each independently 1 to 4;
R21 to R32 are each independently alkyl having 1 to 5 carbon atoms, phenyl, alkylphenyl having 7 to 12 carbon atoms, or phenylalkyl having 7 to 12 carbon atoms;
[Equation 1]

In Equation 1 above,
N1 is the number of moles of aromatic diamino groups represented by Formula 1 included in the polyamide copolymer,
N2 is the number of moles of aromatic diamino groups represented by Formula 2 contained in the polyamide copolymer,
N3 is the number of moles of aromatic diamino groups represented by the above formula (3) included in the polyamide copolymer.
delete According to claim 1,
Wherein X11 to X32 are each independently an alkyl fluoride having 1 to 5 carbon atoms, wherein the substitution ratio of fluorine atoms in the alkyl group is 50% or more.
According to claim 1,
i) an aromatic diamino group represented by the following Chemical Formula 1-1; and
ii) a polyamide copolymer comprising at least one of an aromatic diamino group represented by the following Chemical Formulas 2-1 and 3-1:
[Formula 1-1]

[Formula 2-1]

[Formula 3-1]

In Formulas 1-1 to 3-1,
R21 to R32 are each independently alkyl having 1 to 5 carbon atoms, phenyl, alkylphenyl having 7 to 12 carbon atoms, or phenylalkyl having 7 to 12 carbon atoms.
According to claim 1,
wherein R21 to R32 are each independently methyl, propyl, isopropyl, butyl, 2-butyl, isobutyl, or tert-butyl.
According to claim 1,
Among the sum of the benzene-1,3-dicarbonyl group and the benzene-1,4-dicarbonyl group, the benzene-1,3-dicarbonyl group A polyamide copolymer in which the proportion of benzene-1,3-dicarbonyl groups is 30 mol% or less.
According to claim 1,
A polyamide copolymer having a weight average molecular weight value of 100,000 to 600,000.
According to claim 1,
A polyamide copolymer comprising repeating units represented by the following formulas 11 to 14:
[Formula 11]

[Formula 12]

[Formula 13]

[Formula 14]

The polyamide copolymer according to claim 1 , which is a block or random copolymer.
10. A polyamide film comprising a polyamide layer formed by the polyamide copolymer of any one of claims 1, 3 to 9.
11. The method of claim 10,
further comprising a substrate;
The polyamide film, wherein the polyamide layer is formed on at least one side of the substrate.
12. The method of claim 11,
The description is;
containing one or more polymers selected from the group consisting of polyimide-based, polycarbonate-based, polyester-based, polyalkyl (meth)acrylate-based, polyolefin-based, and polycyclic olefin-based polymers; polyamide film.
11. The method of claim 10,
A polyamide film having a haze value of 5% or less, measured according to ASTM D 1003 standard.
11. The method of claim 10,
A polyamide film having a transmittance value of 85% or more, measured according to ASTM E 313 standard.
11. The method of claim 10,
A polyamide film having a modulus value of 2.5 GPa to 7.5 GPa, measured according to ASTM D882 standard.
11. The method of claim 10,
A polyamide film having an elongation value of at least 3%, measured according to ISO 527-3.

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