阅读说明：本技术 聚酰胺嵌段共聚物和包含其的聚酰胺膜 (Polyamide block copolymer and polyamide film comprising same ) 是由 柳飞悟 朴谆龙 朴永锡 白宽烈 太泳智 崔日焕 于 2019-04-02 设计创作，主要内容包括：本公开内容涉及聚酰胺嵌段共聚物和包含其的聚酰胺膜。根据本公开内容的聚酰胺嵌段共聚物使得可以提供在无色和透明的同时表现出优异的机械特性的聚酰胺膜。(The present disclosure relates to polyamide block copolymers and polyamide films comprising the same. The polyamide block copolymer according to the present disclosure makes it possible to provide a polyamide film that exhibits excellent mechanical properties while being colorless and transparent.)

1. A polyamide block copolymer comprising

A) An amide bond via an aromatic diamino group and a benzene-dicarbonyl group, and

B)

b1) a first polyamide segment in which the ratio of benzene-1, 3-dicarbonyl to the sum of said benzene-1, 3-dicarbonyl and benzene-1, 4-dicarbonyl is 20 mol% or less, and

b2) a second polyamide segment, wherein the ratio of said benzene-1, 3-dicarbonyl to the sum of said benzene-1, 3-dicarbonyl and said benzene-1, 4-dicarbonyl is greater than 20 mol%,

C) wherein the molar ratio of the first polyamide segment to the second polyamide segment is from 1:0.5 to 1: 10.

2. The polyamide block copolymer according to claim 1,

wherein the ratio of the benzene-1, 3-dicarbonyl group to the sum of the benzene-1, 3-dicarbonyl group and the benzene-1, 4-dicarbonyl group is 5 mol% to 25 mol%.

3. The polyamide block copolymer according to claim 1,

wherein the ratio of the benzene-1, 3-dicarbonyl of the first polyamide segment to the sum of the benzene-1, 3-dicarbonyl and the benzene-1, 4-dicarbonyl is 2 mol% to 20 mol%.

4. The polyamide block copolymer according to claim 1,

wherein a ratio of isophthaloyl dichloride of the second polyamide segment to a sum of the benzene-1, 3-dicarbonyl and the benzene-1, 4-dicarbonyl is greater than 20 mol% and 40 mol% or less.

5. The polyamide block copolymer according to claim 1,

wherein the aromatic diamino group has a diamino group derived from at least one selected from the group consisting of: 2,2 ' -bis (trifluoromethyl) -4,4 ' -biphenyldiamine, 2 ' -dimethyl-4, 4 ' -diaminobenzidine, 4 ' -diaminodiphenyl sulfone, 4 ' - (9-fluorenylidene) diphenylamine, bis (4- (4-aminophenoxy) phenyl) sulfone, 2 ', 5,5 ' -tetrachlorobenzidine, 2, 7-diaminofluorene, 4-diaminooctafluorobiphenyl, m-phenylenediamine, p-phenylenediamine, 4 ' -oxydianiline, 2 ' -dimethyl-4, 4 ' -diaminobiphenyl, 2-bis [4- (4-aminophenoxy) phenyl ] propane, 1, 3-bis (4-aminophenoxy) benzene and 4,4 ' -diaminobenzanilide.

6. The polyamide block copolymer according to claim 1,

wherein the weight average molecular weight is from 10,000g/mol to 700,000 g/mol.

7. A polyamide film comprising the polyamide block copolymer of claim 1.

8. The polyamide film according to claim 7,

wherein the haze is 1.0 or less as measured according to ASTM D1003.

9. The polyamide film according to claim 7,

wherein the yellowness index measured according to ASTM E313 is 3.0 or less.

10. The polyamide film according to claim 7,

wherein the modulus measured according to ISO 527-3 is 6.5 or more.

11. The polyamide film according to claim 7,

wherein the elongation measured according to ISO 527-3 is 10% or more.

12. A resin laminate comprising:

a substrate; and

a polymer resin layer comprising the polyamide block copolymer of claim 1.

13. The resin laminate according to claim 12,

wherein the substrate comprises at least one polymer selected from the group consisting of: polyimide-based polymers, polycarbonate-based polymers, polyester-based polymers, polyalkyl (meth) acrylate-based polymers, polyolefin-based polymers, and polycycloolefin-based polymers.

Technical Field

Cross Reference to Related Applications

This application claims the benefit of korean patent application No. 10-2018-.

The present disclosure relates to polyamide block copolymers and polyamide films comprising the same.

Background

The aromatic polyimide resin is a polymer mostly having an amorphous structure, and exhibits excellent heat resistance, chemical resistance, electrical characteristics, and dimensional stability due to its rigid chain structure. Polyimide resins are widely used as electrical/electronic materials.

However, the polyimide resin has many limitations in use because the polyimide resin is dark brown due to the formation of CTC (charge transfer complex) of pi electrons present in an imide chain.

In order to solve the limitation and obtain a colorless and transparent polyimide resin, the following methods have been proposed: by introducing strongly electron-withdrawing groups such as trifluoromethyl (-CF)₃) To restrict the movement of pi electrons by introducing sulfones (-SO) into the backbone₂-) group, ether (-O-) group, etc. to form a bent structure to reduce CTC formation, or to inhibit the formation of a resonance structure of pi electrons by introducing an aliphatic cyclic compound.

However, the polyimide resin according to the proposal is difficult to exhibit sufficient heat resistance due to a bent structure or an aliphatic cyclic compound, and a film prepared using the same still has limitations such as poor mechanical properties.

On the other hand, in recent years, polyamide copolymers having a polyamide unit structure to improve scratch resistance of polyimide have been developed.

However, when a film is formed by coating a polyamide copolymer, haze and a yellow index increase due to high crystallinity of the copolymer. In particular, as the film becomes thicker, the phenomenon becomes severe, and thus a method for improving it is required.

Disclosure of Invention

Technical problem

The present disclosure is to provide a polyamide block copolymer having excellent optical characteristics and at the same time, exhibiting excellent mechanical characteristics.

The present disclosure also provides a polyamide film comprising the polyamide block copolymer.

Technical scheme

In accordance with the present disclosure, there is provided a polyamide block copolymer comprising

A) An amide bond via an aromatic diamino group and a benzene-dicarbonyl group, and

B)

b1) a first polyamide segment in which the ratio of benzene-1, 3-dicarbonyl to the sum of benzene-1, 3-dicarbonyl and benzene-1, 4-dicarbonyl is 20 mol% or less, and

b2) a second polyamide segment in which the ratio of benzene-1, 3-dicarbonyl groups to the sum of benzene-1, 3-dicarbonyl groups and benzene-1, 4-dicarbonyl groups is greater than 20 mol%,

C) wherein the molar ratio of the first polyamide segment to the second polyamide segment is from 1:0.5 to 1: 10.

In accordance with the present disclosure, polyamide films comprising polyamide block copolymers are provided.

Hereinafter, the polyamide block copolymer and the polyamide film including the same according to the exemplary embodiment of the present disclosure will be described in more detail.

Unless explicitly indicated, the terms used refer only to specific embodiments and are not intended to limit the disclosure.

Unless the context indicates otherwise, a singular expression of the present disclosure may include a plural expression.

The terms "comprises," "comprising," "including," and the like, in the present disclosure are used to specify the presence of certain features, regions, integers, steps, operations, elements, and/or components, and these do not preclude the presence or addition of other certain features, regions, integers, steps, operations, elements, and/or components.

According to one embodiment of the present disclosure, there is provided a polyamide block copolymer comprising

A) An amide bond via an aromatic diamino group and a benzene-dicarbonyl group, and

B)

b1) a first polyamide segment in which the ratio of benzene-1, 3-dicarbonyl to the sum of benzene-1, 3-dicarbonyl and benzene-1, 4-dicarbonyl is 20 mol% or less, and

b2) a second polyamide segment in which the ratio of benzene-1, 3-dicarbonyl groups to the sum of benzene-1, 3-dicarbonyl groups and benzene-1, 4-dicarbonyl groups is greater than 20 mol%,

C) wherein the molar ratio of the first polyamide segment to the second polyamide segment is from 1:0.5 to 1: 10.

As a result of the studies of the present inventors, when a polyamide copolymer is formed by reacting the amine moiety of an aromatic diamine monomer with the carbonyl group of a benzene-dicarbonyl-based monomer (e.g., phthaloyl chloride), it was determined that a specific combination of benzene-1, 3-dicarbonyl (or a unit derived from isophthaloyl, IPC) and benzene-1, 4-dicarbonyl (or a unit derived from terephthaloyl; TPC) provides a block copolymer having different benzene-1, 3-dicarbonyl ratios in respective segments, and the copolymer can be used for a flexible display device or the like because it does not have a large loss in strength and hardness while having a flexible structure.

According to one embodiment of the present disclosure, the polyamide block copolymer comprises both: I) an amide repeating unit (hereinafter, referred to as a first amide repeating unit) in which an amine group of the aromatic diamine monomer and a carbonyl group of the isophthaloyl-based monomer form an amide bond, and II) an amide repeating unit (hereinafter, referred to as a second amide repeating unit) in which an amine group of the aromatic diamine monomer and a carbonyl group of the terephthaloyl-based monomer form an amide bond.

In addition, the copolymer comprises a plurality of segments having different compositions and physical properties, and each segment is in the form of a block copolymer comprising both the first amide repeat unit and the second amide repeat unit.

In the segment of the copolymer, a segment in which the ratio of benzene-1, 3-dicarbonyl with respect to the sum of benzene-1, 3-dicarbonyl derived from an isophthaloyl-based monomer and benzene-1, 4-dicarbonyl derived from a terephthaloyl-based monomer is 20 mol% or less is referred to as a first polyamide segment.

Further, among the segments of the copolymer, a segment in which the ratio of benzene-1, 3-dicarbonyl with respect to the sum of benzene-1, 3-dicarbonyl derived from an isophthaloyl-based monomer and benzene-1, 4-dicarbonyl derived from a terephthaloyl-based monomer is more than 20 mol% is referred to as a second polyamide segment.

Referring to the above-mentioned amide repeating units, it can be seen that, in the first polyamide segment, the ratio of the first amide repeating unit to the sum of the first amide repeating unit and the second amide repeating unit is 20 mol% or less, and, in the second polyamide segment, the ratio of the first amide repeating unit to the sum of the first amide repeating unit and the second amide repeating unit is more than 20 mol%.

Here, in the polyamide block copolymer, the molar ratio of the first polyamide segment to the second polyamide segment (or the ratio of amide repeating units) is kept in the range of 1:0.5 to 1: 10.

According to one embodiment of the present disclosure, the ratio of benzene-1, 3-dicarbonyl of the first polyamide segment relative to the sum of benzene-1, 3-dicarbonyl and benzene-1, 4-dicarbonyl may be about 2 mol% to about 20 mol%, preferably about 2 mol% to about 5 mol%.

The ratio of benzene-1, 3-dicarbonyl of the second polyamide segment relative to the sum of benzene-1, 3-dicarbonyl and benzene-1, 4-dicarbonyl may be greater than about 20 mol% and about 40 mol% or less.

Repeating units derived from benzene-1, 3-dicarbonyl (isophthaloyl based monomer (IPC)) can interfere with chain packing and alignment in the polymer due to the tortuous molecular geometry. In addition, it can enlarge the amorphous region in the polyamide copolymer, thereby improving the optical characteristics and folding resistance of the polyamide film.

Repeating units derived from benzene-1, 4-dicarbonyl (terephthaloyl-based monomer (TPC)) can maintain chain packing and alignment in the polymer due to linear molecular geometry. In addition, it can enlarge the crystalline region in the polyamide copolymer, thereby improving the surface hardness and mechanical properties of the polyamide film.

Therefore, the first polyamide segment in which the ratio of benzene-1, 3-dicarbonyl to the sum of benzene-1, 3-dicarbonyl and benzene-1, 4-dicarbonyl is about 20 mol% or less can impart relatively good surface hardness and mechanical properties to the polyimide film.

Further, the second polyamide segment in which the ratio of benzene-1, 3-dicarbonyl to the sum of benzene-1, 3-dicarbonyl and benzene-1, 4-dicarbonyl is greater than about 20 mol% can impart relatively good optical characteristics and folding endurance to the polyimide film.

The polyamide copolymers of the present disclosure comprise both the first and second polyamide segments described above, and in particular, the ratio of the first polyamide segments to the second polyamide segments (or the ratio of amide repeat units) is maintained in the range of about 1:0.5 to about 1:10 throughout the polyamide block copolymer. Therefore, in the polyamide film produced using the polyamide copolymer, the advantages of the respective segments can be very effectively achieved.

In each of the above-mentioned segments, the polymerization type of the aromatic diamine group and the benzene-dicarbonyl group may be a block copolymerization in which some repeating units are alternately repeated, or a random copolymerization without a specific repeating rule.

However, all polyimide copolymers must be in the form of block copolymers containing different segments in which the respective segments satisfy the above-described ratio of benzene-1, 3-dicarbonyl to benzene-1, 4-dicarbonyl.

According to one embodiment of the present disclosure, the ratio of benzene-1, 3-dicarbonyl to the sum of benzene-1, 3-dicarbonyl and benzene-1, 4-dicarbonyl of the polyamide block copolymer may be about 5 mol% to about 25 mol% of the total copolymer.

That is, since the ratio of benzene-1, 3-dicarbonyl groups in the entire copolymer including all segments, and the ratio of benzene-1, 3-dicarbonyl groups and benzene-1, 4-dicarbonyl groups in each segment are within the above range, the above polyamide film may have excellent optical characteristics such as haze and yellow index, and at the same time, excellent mechanical characteristics such as folding resistance and surface hardness.

The above aromatic diamino group may be derived from an aromatic diamine monomer containing two amino groups at the terminal around the aromatic ring. For example, the aromatic diamino group can be derived from at least one selected from the group consisting of: 2,2 ' -bis (trifluoromethyl) -4,4 ' -biphenyldiamine, 2 ' -dimethyl-4, 4 ' -diaminobenzidine, 4 ' -diaminodiphenyl sulfone, 4 ' - (9-fluorenylidene) diphenylamine, bis (4- (4-aminophenoxy) phenyl) sulfone, 2 ', 5,5 ' -tetrachlorobenzidine, 2, 7-diaminofluorene, 4-diaminooctafluorobiphenyl, m-phenylenediamine, p-phenylenediamine, 4 ' -oxydianiline, 2 ' -dimethyl-4, 4 ' -diaminobiphenyl, 2-bis [4- (4-aminophenoxy) phenyl ] propane, 1, 3-bis (4-aminophenoxy) benzene and 4,4 ' -diaminobenzanilide.

More preferably, the aromatic diamine monomer may be 2,2 '-bis (trifluoromethyl) -4, 4' -biphenyldiamine (TFDB) or 2,2 '-dimethyl-4, 4' -diaminobenzidine.

The polyamide block copolymer according to another embodiment of the present disclosure is a carbonyl group forming an amide bond with the above aromatic diamino group, and may include a carbonyl group derived from an aromatic dicarbonyl monomer or a tricarbonyl monomer in addition to benzene-1, 3-dicarbonyl and benzene-1, 4-dicarbonyl.

Examples of the aromatic dicarbonyl monomer include 4, 4' -biphenyldicarbonyl chloride and the like, and examples of the aromatic tricarbonyl monomer include trimesoyl chloride and the like.

In particular, the aromatic tricarbonyl monomer may act as a crosslinking agent in the copolymerization to further improve the mechanical properties of the polyamide block copolymer.

To achieve this effect, the aromatic tricarbonyl monomer may be included in an amount of about 0.01 mol% or greater, about 0.025 mol% or greater, or about 0.05 mol% or greater and about 5.0 mol% or less, about 2.5 mol% or less, about 1.5 mol% or less, or about 1.25 mol% or less of the total carbonyl-derived monomers.

When the aromatic tricarbonyl monomer is used in excess, the optical characteristics of the polyamide block copolymer to be produced may be deteriorated and flexibility may be reduced.

Meanwhile, polymerization conditions for preparing a polyamide comprising an amide bond via an aromatic diamino group and a benzene-dicarbonyl group by polymerizing an aromatic diamine monomer with an aromatic dicarbonyl monomer are not particularly limited. However, the polymerization may be performed two or more times in order to form the above-mentioned first polyamide segment and second polyamide segment, respectively.

Specifically, the polymerization process may comprise the steps of:

b11) mixing a benzene-1, 3-dicarbonyl monomer, a benzene-1, 4-dicarbonyl monomer and an aromatic diamine monomer,

b12) wherein the benzene-1, 3-dicarbonyl monomer is contained in an amount of 20 mol% or less based on the total of the benzene-1, 3-dicarbonyl monomer and the benzene-1, 4-dicarbonyl monomer,

b13) then forming an amide bond between the amine group and the carbonyl group to form a first polyamide segment; and

b21) mixing a benzene-1, 3-dicarbonyl monomer, a benzene-1, 4-dicarbonyl monomer and an aromatic diamine monomer,

b22) wherein the benzene-1, 3-dicarbonyl monomer is contained in an amount of more than 20 mol% based on the total of the benzene-1, 3-dicarbonyl monomer and the benzene-1, 4-dicarbonyl monomer,

b23) then forming an amide bond between the amine group and the carbonyl group to form a second polyamide segment,

wherein the ratio of the monomers can be controlled such that the molar ratio of the first polyamide segment to the second polyamide segment is from 1:0.5 to 1: 10.

The polymerization reaction to form the polyamide may be carried out by solution polymerization under an inert gas atmosphere at a temperature of about-25 ℃ to about 25 ℃, more preferably about-25 ℃ to 0 ℃. Specific examples of the above-mentioned monomers and the like are as described above in the polyamide block copolymer.

Here, as the reaction solvent, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide, acetone, N-methyl-2-pyrrolidone, tetrahydrofuran, chloroform, γ -butyrolactone, or the like can be used.

According to one embodiment of the present disclosure, the polyamide block copolymer may have a weight average molecular weight of from about 10,000g/mol to about 700,000g/mol, from about 10,000g/mol to about 500,000g/mol, from about 100,000g/mol to about 500,000g/mol, or from about 300,000g/mol to about 450,000 g/mol.

Here, the weight average molecular weight may be measured by Gel Permeation Chromatography (GPC).

According to another embodiment of the present disclosure, a film comprising the above polyamide block copolymer is provided.

When a film is produced using the above polyamide block copolymer, flexibility as well as excellent optical and mechanical properties can be exhibited, and thus the film can be used as a material for various molded articles.

For example, the polyamide film can be applied to a substrate for a display, a protective film for a display, a touch panel, a window cover of a foldable device, and the like.

The polyamide film can be produced by a conventional method such as a dry method or a wet method using the polyamide block copolymer.

For example, a polyamide film can be obtained by coating a solution containing the copolymer on an arbitrary support to form a film, and drying the film by allowing the solvent to evaporate. The polyamide film may be stretched and heat-treated, if necessary.

Since the polyamide film is prepared using the above polyamide copolymer, the polyamide film can exhibit excellent mechanical characteristics while being colorless and transparent.

Specifically, the haze of the polyamide film measured according to ASTM D1003 for a sample having a thickness of 50 ± 2 μm may be about 1.0% or less, or about 0.85% or less.

Further, the polyamide film may have a Yellowness Index (YI) of about 3.0 or less, or about 2.85 or less, measured according to ASTM E313 for a sample having a thickness of 50 ± 2 μm.

Further, the polyamide film may have a modulus measured according to ISO 527-3 of about 6.5GPa or greater, preferably about 7.0GPa or greater.

Further, the polyamide film may have an elongation measured according to ISO 527-3 of about 10% or more, preferably about 14% or more.

Further, the pencil hardness of the polyamide film measured according to ASTM D3363 for a sample having a thickness of 50. + -.2 μm is 2H or more.

According to another embodiment of the present disclosure, there is provided a resin laminate including: a substrate; and a polymer resin layer comprising the above polyamide block copolymer.

Here, the polymer resin layer may be formed on one surface or both surfaces of the substrate, and may further include a separate functional layer on the polymer resin layer or between the substrate and the polymer resin layer.

The substrate may comprise at least one polymer selected from the group consisting of: polyimide-based polymers, polycarbonate-based polymers, polyester-based polymers, polyalkyl (meth) acrylate-based polymers, polyolefin-based polymers, and polycycloolefin-based polymers.

Effects of the invention

The polyamide block copolymer according to the present disclosure makes it possible to provide a polyamide film that exhibits excellent mechanical properties while being colorless and transparent.

Detailed Description

Hereinafter, preferred embodiments are provided for better understanding.

However, these examples are for illustrative purposes only, and the present invention is not intended to be limited by these examples.

Preparation of Polyamide Block copolymer