POLYAMIDE RESIN, PREPARATION METHOD THEREFOF, AND POLYAMIDE FILM AND RESIN LAMINATE COMPRISING THE SAME

Abstract

The present invention relates to a polyamide resin having a main chain having a structure in which two polyamide segments are linked in an alternating way, a preparation method thereof, and a polyamide film and resin laminate including the same.

Claims

1. A polyamide resin which comprises: a first polyamide segment including a repeating unit represented by the following Chemical Formula 1 or a block composed thereof; and a second polyamide segment including a repeating unit represented by the following Chemical Formula 2, or a block composed thereof, wherein the first polyamide segment and the second polyamide segment form a main chain including an alternating repeating unit represented by the following Chemical Formula 3: ##STR00013## in the Chemical Formulae 1 and 2, Ar.sub.1 and Ar.sub.2 are each independently a substituted or unsubstituted arylene group having 6 to 20 carbon atoms, or a substituted or unsubstituted heteroarylene group having 2 to 20 carbon atoms, and in the Chemical Formula 3, A is the first polyamide segment, and B is the second polyamide segment.

2. The polyamide resin according to claim 1, wherein the polyamide resin has a haze measured according to ASTM D1003 of 3.0% or less.

3. The polyamide resin according to claim 1, wherein the polyamide resin has a weight average molecular weight of at least 330000 g/mol.

4. The polyamide resin according to claim 1, wherein the polyamide resin has a relative viscosity of at least 45000 cps.

5. The polyamide resin according to claim 1, comprising the repeating units represented by Chemical Formula 2 Ain an amount of 5 mol % to 60 mol %-based on the total repeating units contained in the polyamide resin.

6. The polyamide resin according to claim 1, comprising based on the total repeating units contained in the polyamide resin, the repeating units represented by Chemical Formula 1 kin an amount of 60 mol % to 90 mol %, and the content of the repeating units represented by Chemical Formula 2 kin an amount of 5 mol % to 40 mol %.

7. The polyamide resin according to claim 1, wherein the first polyamide segment has a number average molecular weight of 100 g/mol or more and 5000 g/mol or less.

8. The polyamide resin according to claim 1, wherein the repeating unit represented by Chemical Formula 2 comprises a repeating unit represented by the following Chemical Formula 2-1; or a repeating unit represented by Chemical Formula 2-2: ##STR00014## in the Chemical Formulae 2-1 to 2-2, Ar.sub.2 is a substituted or unsubstituted arylene group having 6 to 20 carbon atoms, or a substituted or unsubstituted heteroarylene group having 2 to 20 carbon atoms.

9. The polyamide resin according to claim 1, wherein the alternating repeating unit represented by Chemical Formula 3 is a repeating unit represented by the following Chemical Formula 4: ##STR00015## in the Chemical Formula 4, Ar.sub.1 and Ar.sub.2 are each independently a substituted or unsubstituted arylene group having 6 to 20 carbon atoms, or a substituted or unsubstituted heteroarylene group having 2 to 20 carbon atoms, a1 and a2 are each independently an integer of 1 to 10, and b1 and b2 are each independently an integer of 1 to 5.

10. The polyamide resin according to claim 1, wherein the repeating unit represented by Chemical Formula 1 is an amide repeating unit derived from a combination of a 1,4-aromatic diacyl compound and an aromatic diamine compound.

11. The polyamide resin according to claim 10, wherein the 1,4-aromatic diacyl compound comprises terephthaloyl chloride, or terephthalic acid, and the aromatic diamine compound comprises 2,2-bis(trifluoromethyl)-4,4-biphenyldiamine.

12. The polyamide resin according to claim 1, wherein the repeating unit represented by Chemical Formula 2 comprises an amide repeating unit derived from a combination of a 1,2-aromatic diacyl compound and an aromatic diamine compound; or an amide repeating unit derived from a combination of a 1,3-aromatic diacyl compound and the aromatic diamine compound.

13. The polyamide resin according to claim 12, wherein the 1,2-aromatic diacyl compound comprises phthaloyl chloride, or phthalic acid, the 1,3-aromatic diacyl compound comprises isophthaloyl chloride or isophthalic acid, and the aromatic diamine compound includes 2,2-bis(trifluoromethyl)-4,4-biphenyldiamine.

14. A method for preparing a polyamide resin comprising: a step of melt-kneading a compound represented by the following Chemical Formula 7 and a compound represented by the following Chemical Formula 8, and solidifying the melt-kneaded product to form a complex; and a step of reacting the complex with an aromatic diamine monomer: ##STR00016## in the Chemical Formulae 7 to 8, X is a halogen or a hydroxyl group.

15. The method for preparing a polyamide resin according to claim 14, wherein the step of melt-kneading the compound represented by Chemical Formula 7 and the compound represented by Chemical Formula 8, and solidifying the melt-kneaded product to form the complex comprises, a step of mixing the compound represented by Chemical Formula 7 and the compound represented by Chemical Formula 8 at a temperature of at least 50 C.; and a step of cooling the result of the mixing step.

16. The method for preparing a polyamide resin according to claim 14, wherein in the step of melt-kneading the compound represented by Chemical Formula 7 and the compound represented by Chemical Formula 8, and solidifying the melt-kneaded product to form the complex, the compound represented by Chemical Formula 8 is mixed at 5 parts by weight to 60 parts by weight based on 100 parts by weight of the compound represented by Chemical Formula 7.

17. The method for preparing a polyamide resin according to claim 14, wherein the step of reacting the complex with the aromatic diamine monomer comprises, a step of dissolving the aromatic diamine monomer in an organic solvent to prepare a diamine solution; and a step of adding a powder of the complex to the diamine solution.

18. A polymer film comprising: a first polyamide segment including a repeating unit represented by the following Chemical Formula 1 or a block composed thereof; and a second polyamide segment including a repeating unit represented by the following Chemical Formula 2, or a block composed thereof, wherein the first polyamide segment and the second polyamide segment form a main chain including an alternating repeating unit represented by the following Chemical Formula 3: ##STR00017## in the Chemical Formulae 1 and 2, Ar.sub.1 and Ar.sub.2 are each independently a substituted or unsubstituted arylene group having 6 to 20 carbon atoms, or a substituted or unsubstituted heteroarylene group having 2 to 20 carbon atoms, and in the Chemical Formula 3, A is the first polyamide segment, and B is the second polyamide segment.

19. The polymer film according to claim 18, wherein the polymer film has a haze value measured for a specimen having a thickness of 45 m or more and 55 m or less according to ASTM D1003 of 3.0% or less.

20. A resin laminate comprising: a substrate including the first polyamide resin of claim 1; and a hard coating layer formed on at least one side of the substrate.

Description

BRIEF DESCRIPTION OF DRAWINGS

[0136] FIG. 1 shows a .sup.13C-NMR spectrum of the polyamide resin obtained in (I) of Example 1.

[0137] FIG. 2 shows a .sup.13C-NMR spectrum of the polyamide resin obtained in (1) of Example 2.

DETAILED DESCRIPTION OF THE EMBODIMENTS

[0138] Hereinafter, embodiments of the present invention will be described in more detail by way of examples. However, these examples are presented for illustrative purposes only, and are not intended to limit the scope of the present invention.

Preparation Example: Preparation of Acyl Chloride Complex>

Preparation Example 1

[0139] 549.4 g (2.704 mol) of terephthaloyl chloride (TPC; melting point: 83 C.) and 120.6 g (0.594 mol) of isophthaloyl chloride (IPC; melting point: 44 C.) were added to a 1000 mL 4-neck round flask (reactor) equipped with a stirrer, a nitrogen injection device, a dropping funnel and a temperature controller, and the mixture was melt-kneaded at 100 C. for 3 hours and then cooled at 0 C. for 12 hours to prepare a complex of acylchloride (specifically, terephthaloyl chloride and isophthaloyl chloride).

[0140] Subsequently, the acyl chloride complex was grinded with a jaw crusher to prepare a powder having an average particle size of 5 mm.

Preparation Example 2

[0141] An acylchloride complex was prepared in the same manner as in Preparation Example 1, except that 569.5 g (2.803 mol) of terephthaloyl chloride (TPC; melting point: 83 C.) and 100.5 g (0.495 mol) of isophthaloyl chloride (IPC; melting point: 44 C.) were added.

Example: Preparation of Polyamide Resin and Film

Example 1

[0142] (1) Polyamide Resin

[0143] 262 g of N,N-dimethylacetamide (DMAc) was filled into a 500 mL 4-neck round flask (reactor) equipped with a stirrer, a nitrogen injection device, a dropping funnel and a temperature controller while slowly blowing nitrogen into the reactor. Then, the temperature of the reactor was adjusted to 0 C., and 14.153 g (0.0442 mol) of 2,2-bis(trifluoromethyl)-4,4-biphenyldiamine (TFDB) was added and dissolved.

[0144] The mixture was stirred while adding 8.972 g (0.0442 mol) of the acyl chloride complex powder obtained in Preparation Example 1, and subjected to amide formation reaction at 0 C. for 12 hours.

[0145] After completion of the reaction, N,N-dimethylacetamide (DMAc) was added to dilute the solution to a solid content of 5% or less, and the resultant was precipitated with 1 L of methanol. The precipitated solids were filtered and then dried at 100 C. under vacuum for 6 hours or more to prepare a solid-state polyamide resin.

[0146] It was confirmed through .sup.13C-NMR shown in FIG. 1 that the polyamide resin obtained in (1) of Example 1, contained 82 mol % of the first repeating unit obtained by an amide reaction of terephthaloyl chloride (TPC) and 2,2-bis(trifluoromethyl)-4,4-biphenyldiamine (TFDB) and 18 mol % of the second repeating unit obtained by an amide reaction of isophthaloyl chloride (IPC) and 2,2-bis(trifluoromethyl)-4,4-biphenyldiamine (TFDB).

[0147] (2) Polyamide Film

[0148] The polyamide resin obtained in (1) of Example 1 was dissolved in N,N-dimethylacetamide to prepare about 10% (w/v) polymer solution.

[0149] The polymer solution was applied onto a polyimide base film (UPILEX-75s, UBE), and the thickness of the polymer solution was uniformly adjusted using a film applicator.

[0150] Then, after drying for 15 minutes at 80 C. Mathis oven, it was cured for 30 minutes at 250 C. while flowing nitrogen, and peeled from the substrate film to obtain a polyamide film.

Example 2

[0151] (1) Polyamide Resin

[0152] A polyamide resin was prepared in the same manner as in (1) of Example 1, except that the acyl chloride complex powder obtained in Preparation Example 2 was used instead of the acyl chloride complex powder obtained in Preparation Example 1.

[0153] It was confirmed through .sup.13C-NMR shown in FIG. 2 that the polyamide resin obtained in (1) of Example 2, contained 85 mol % of the first repeating unit obtained by an amide reaction of terephthaloyl chloride (TPC) and 2,2-bis(trifluoromethyl)-4,4-biphenyldiamine (TFDB), and 15 mol % of the second repeating unit obtained by an amide reaction of isophthaloyl chloride (IPC) and 2,2-bis(trifluoromethyl)-4,4-biphenyldiamine (TFDB).

[0154] (2) Polyamide Film

[0155] A polyamide film was prepared in the same manner as in (2) of Example 1, except that the polyamide resin obtained in (1) of Example 2 was used instead of the polyamide resin obtained in (1) of Example 1.

Comparatitve Example: Preparation of Polyamide Resin and Film

Comparative Example 1

[0156] (1) Polyamide Resin

[0157] A polyamide resin was prepared in the same manner as in (1) of Example 1, except that instead of the acyl chloride complex powder obtained in Preparation Example 1, 7.358 g (0.0362 mol) of terephthaloyl chloride (TPC) and 1.615 g (0.0080 mol) of isophthaloyl chloride (IPC) were added simultaneously to perform an amide formation reaction.

[0158] (2) Polyamide Film

[0159] A polyamide film was prepared in the same manner as in (2) of Example 1, except that the polyamide resin obtained in (1) of Comparative Example 1 was used instead of the polyamide resin obtained in (1) of Example 1.

Comparative Example 2

[0160] (1) Polyamide Resin

[0161] A polyamide resin was prepared in the same manner as in (1) of Example 1, except that instead of the acyl chloride complex powder obtained in Preparation Example 1, 7.358 g (0.0362 mol) of terephthaloyl chloride (TPC) was first added, and then 1.615 g (0.0080 mol) of isophthaloyl chloride (TPC) was added sequentially at about 5 minute intervals to perform an amide formation reaction.

[0162] (2) Polyamide Film

[0163] A polyamide film was prepared in the same manner as in (2) of Example 1, except that the polyamide resin obtained in (1) of Comparative Example 2 was used instead of the polyamide resin obtained in (1) of Example 1.

Comparative Example 3

[0164] (1) Polyamide Resin

[0165] A polyamide resin was prepared in the same manner as in (1) of Example 1, except that instead of the acyl chloride complex powder obtained in Preparation Example 1, 1.615 g (0.0080 mol) of isophthaloyl chloride (IPC) was first added, and then 7.358 g (0.0362 mole) of terephthaloyl chloride (TPC) was added sequentially at about 5 minute intervals to perform an amide formation reaction.

[0166] (2) Polyamide Film

[0167] A polyamide film was prepared in the same manner as in (2) of Example 1, except that the polyamide resin obtained in (1) of Comparative Example 3 was used instead of the polyamide resin obtained in (1) of Example 1.

Reference Example: Preparation of Polyamide Resin and Film

Reference Example 1

[0168] (1) Polyamide Resin

[0169] 262 g of N,N-dimethylacetamide (DMAc) was filled into a 500 mL 4-neck round flask (reactor) equipped with a stirrer, a nitrogen injection device, a dropping funnel and a temperature controller while slowly blowing nitrogen into the reactor. Then, the temperature of the reactor was adjusted to 0 C., and 7.358 g (0.0362 mol) of terephthaloyl chloride (TPC) and 1.615 g (0.0080 mol) of isophthaloyl chloride (IPC) were dissolved.

[0170] The mixture was stirred while adding 14.153 g (0.0442 mol) of 2,2-bis(trifluoromethyl)-4,4-biphenyldiamine (TFDB), and subjected to amide formation reaction at 0 C. for 12 hours.

[0171] After completion of the reaction, N,N-dimethylacetamide (DMAc) was added to dilute the solution to a solid content of 5% or less, and the resultant was precipitated with 1 L of methanol. The precipitated solids were filtered and then dried at 100 C. under vacuum for 6 hours or more to prepare a solid-state polyamide resin.

[0172] (2) Polyamide Film

[0173] A polyamide film was prepared in the same manner as in (2) of Example 1, except that the polyamide resin obtained in (1) of Reference Example 1 was used instead of the polyamide resin obtained in (1) of Example 1.

Experimental Example

[0174] The following characteristics were measured or evaluated for the polyamide resins or the polyamide films obtained in Examples, Comparative Examples and Reference Examples, and the results are shown in Table 1 below.

[0175] (1) Thickness: The thickness of the polyamide film was measured using a thickness measuring device.

[0176] (2) Yellowness index (Y.I.): The yellowness index of the polyamide film was measured according to the measurement method of ASTM E313 using a COH-400 Spectrophotometer (NIPPON DENSHOKU INDUSTRIES).

[0177] (3) Transmittance: The total light transmittance of the polyamide film was measured using a Shimadzu UV-2600 UV-vis spectrometer. In the measurement results, the transmittance (T, @388 nm) for ultraviolet light at a wavelength of 388 nm and the transmittance (T, @550 nm) for visible light at wavelength of 550 nm were shown.

[0178] (4) Haze: The haze value of the polyamide film was measured according to the ASTM D1003 test method using a COH-400 Spectrophotometer (NIPPON DENSHOKU INDUSTRIES).

[0179] (5) Molecular weight and polydispersity index (PDI): The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the polyamide resin were measured by gel permeation chromatography (GPC, manufactured by Waters), and the polydispersity index (PDI) was calculated by dividing the weight average molecular weight by the number average molecular weight. Specifically, the measurement was performed using a 600 mm long column connecting two Polymer Laboratories PLgel MIX-B Columns (300 mm in length), through Waters 2605 Refractive Index (RI) Detector, wherein the evaluation temperature was 50 to 75 C. (about 65 C.), DMF 100 wt % solvent was used, the flow rate was 1 mL/min, and the sample was prepared at a concentration of 1 mg/mL and supplied in an amount of 100 L for 25 minutes. The molecular weights could be determined using calibration curves formed using polystyrene standards. As the molecular weight of polystyrene standard products, 7 types of 3940/9600/31420/113300/327300/1270000/4230000 were used.

[0180] (6) Bending Property: The folding endurance of the polyamide films was evaluated using an MIT type folding endurance tester. Specifically, a specimen (1 cm*7 cm) of the polyamide film was loaded into the folding endurance tester, and folded to an angle of 135 at a rate 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, until the specimen was bended and fractured. The number of reciprocating bending cycles was measured as the folding endurance.

[0181] (7) Viscosity: Under a constant reflux system at 250.2 C., the viscosity of the solution containing polyamide resin (solvent: dimethylacetamide (DMAc), solid content: 10 wt %) was measured according to ASTM D 2196: test method of non-Newtonian materials by Brookfield DV-2T Rotational Viscometer. As Brookfield silicone standard oil, a number of standard solutions having a viscosity range of 5000 cps to 200000 cps was used. The measurement was performed with a spindle LV-4 (64), 0.3-100 RPM, and the unit was cps (mPa.Math.s).

[0182] (8) Pencil Hardness: The pencil hardness of the polyamide films was measured according to the ASTM D3363 test method using a Pencil Hardness Tester. Specifically, varying hardness values of pencils were fixed to the tester and scratched on the polyamide film, and the degree of occurrence of a scratch on the polyamide film was observed with the naked eye or with a microscope. When more than 70% of the total number of scratches were not observed, a value corresponding to the hardness of the pencil was evaluated as the pencil hardness of the film.

[0183] The pencil hardness is increased in the order of B grade, F grade and H grade. Within the same grade, the higher the number, the higher the hardness. Within the grade, the higher the number, the higher the hardness.

TABLE-US-00001 TABLE 1 Reference Example Example Comparative Comparative Comparative Example Category 1 2 Example 1 Example 2 Example 3 1 Thickness (m) 50 49 51 51 50 50 Y.I. 2.68 2.89 8.55 25.10 4.59 2.28 T (%)@550 nm 88.75 88.50 85.63 75.94 87.57 88.82 T (%)@388 nm 75.3 71.0 51.01 31.62 65.04 74.24 Haze(%) 0.81 0.97 3.43 24.21 1.61 0.40 Mw(g/mol) 512000 463000 412000 350000 382000 321000 Bending 12022 9785 5210 785 4513 6351 property (Cycle) PDI 1.84 2.71 2.05 2.02 1.98 2.00 Viscosity (cps) 110000 174000 54000 24000 28000 18000 Pencil 3H 4H 1H F 1H 2H hardness

[0184] Looking at Table 1 above, the polyamide resin of Examples prepared using the acyl chloride complex powder according to Preparation Examples 1 to 2 had a high weight average molecular weight of 463000 g/mol to 512000 g/mol, and the relative viscosity was measured to be as high as 110000 cps to 174000 cps. Moreover, it was confirmed that the polyamide film obtained from the polyamide resin of Examples had a low yellowness index of 2.68 to 2.89 and a low haze value of 0.81% to 0.97% at a thickness of about 50 m, thereby exhibiting excellent transparency. It was also confirmed that it had a high pencil hardness of 3H to 4H grade and a folding endurance that was broken at the number of reciprocating bending cycles from 9785 to 12022, thereby securing excellent mechanical properties (scratch resistance and folding endurance). Meanwhile, in the case of the polyamide resins of Comparative Examples in which the acyl chloride complex powder according to Preparation Examples 1 to 2 was not used in the synthesis process of the polyamide resin, it had a molecular weight of 321,000 g/mol to 412,000 g/mol which was reduced compared to Examples and it had a viscosity of 18,000 cps to 54,000 cps was reduced compared to Examples.

[0185] On the other hand, in the case of the polyamide films obtained from the polyamide resins of Comparative Examples 1, 2, and 3 in which TPC powder and IPC powder were simultaneously or sequentially added, it was confirmed that the films had a yellowness index of 2.28 to 25.10 and a haze value of 1.61% to 24.21% at a thickness of about 50 m, which increased compared to Examples, resulting in poor transparency. This is considered to be because, in Comparative Examples 1, 2, and 3, due to the difference in solubility and reactivity between the TPC powder and the IPC powder, the block due to TPC was excessively formed, thereby increasing the crystallinity of the polyamide resin.

[0186] Meanwhile, in the case of the polyamide resin of Reference Example 1, in which acyl chloride was dissolved in an amide-based solvent and treated in a solution, it was confirmed that it exhibited a very low molecular weight of 321,000 g/mol, the viscosity was significantly reduced to 18000 cps, it was broken at the number of reciprocating bending cycle of 6351, and the folding endurance was reduced than that of Examples. This is considered to be due to the occurrence of deterioration by moisture and mixing in amide solvents at the time of dissolving acyl chloride in Reference Example 1.