POLYAMIC ACID COMPOSITION, METHOD FOR PREPARING POLYAMIC ACID COMPOSITION, POLYIMIDE COMPRISING THE SAME AND COATING MATERIAL COMPRISING THE SAME

Abstract

The present application relates to a polyamic acid composition, a method for preparing the polyamic acid composition, a polyimide comprising the same, and a coating material comprising the same, which provides a polyamic acid composition capable of implementing a low permittivity and heat resistance, and insulation properties and mechanical properties in a harsh condition such as a high temperature simultaneously, a method for preparing the polyamic acid composition, a polyimide comprising the same and a coating material comprising the same.

Claims

1. A polyamic acid composition comprising a non-fluorine-based diamine monomer and a non-fluorine-based dianhydride monomer as polymerization units, and comprising at least one of a fluorine-based diamine monomer and a fluorine-based dianhydride monomer as polymerization units, wherein the polyamic acid composition has a permittivity of 3.0 or less after curing, a dielectric breakdown voltage of 10 kV or more and a partial discharge initiation voltage of 800 Vp or more.

2. The polyamic acid composition according to claim 1, wherein the fluorine-based diamine monomer and the fluorine-based dianhydride monomer comprise at least one perfluoroalkyl group in the molecular structure.

3. The polyamic acid composition according to claim 1, wherein the fluorine-based diamine monomer and the fluorine-based dianhydride monomer do not polymerize with each other.

4. The polyamic acid composition according to claim 1, wherein the fluorine-based diamine monomer or the fluorine-based dianhydride monomer has two or more benzene rings.

5. The polyamic acid composition according to claim 1, wherein the fluorine-based diamine monomer is included in a range of 45 to 98 mol % relative to 100 mol % of the diamine monomers.

6. The polyamic acid composition according to claim 1, wherein the fluorine-based dianhydride monomer is included in a range of 5 to 60 mol % relative to 100 mol % of the dianhydride monomers.

7. The polyamic acid composition according to claim 1, wherein the solid contents are in a range of 15 to 40%.

8. The polyamic acid composition according to claim 1, wherein the viscosity measured under conditions of a temperature of 23° C. and a shear rate of 1 s.sup.−1 is 10,000 cP or less.

9. A method for preparing a polyamic acid composition comprising a first step of polymerizing two non-fluorine-based dianhydride monomers to both side amine groups of a fluorine-based diamine monomer; a second step of further polymerizing a non-fluorine-based diamine monomer to the polymerized non-fluorine-based dianhydride monomer and a third step of further polymerizing a fluorine-based or non-fluorine-based dianhydride monomer to the polymerized non-fluorine-based diamine monomer.

10. A method for preparing a polyamic acid composition comprising a first step of polymerizing two non-fluorine-based diamine monomers to both side anhydride groups of a fluorine-based dianhydride monomer; a second step of further polymerizing a non-fluorine-based dianhydride monomer to the polymerized non-fluorine-based diamine monomer and a third step of further polymerizing a fluorine-based or non-fluorine-based diamine monomer to the polymerized non-fluorine-based dianhydride monomer.

11. The method for preparing a polyamic acid composition according to claim 9, wherein in the second step, two non-fluorine-based diamine monomers are polymerized to two non-fluorine-based dianhydride monomers.

12. The method for preparing a polyamic acid composition according to claim 11, wherein in the third step, two fluorine-based or non-fluorine-based dianhydride monomers are polymerized to two non-fluorine-based diamine monomers.

13. The method for preparing a polyamic acid composition according to claim 12, wherein the polymerization units polymerized up to the second step are further polymerized to the two fluorine-based or non-fluorine-based dianhydride monomers.

14. The method for preparing a polyamic acid composition according to claim 10, wherein in the second step, two non-fluorine-based dianhydride monomers are polymerized to two non-fluorine-based diamine monomers.

15. The method for preparing a polyamic acid composition according to claim 14, wherein in the third step, two fluorine-based or non-fluorine-based diamine monomers are polymerized to two non-fluorine-based dianhydride monomers.

16. The method for preparing a polyamic acid composition according to claim 15, wherein the polymerization units polymerized up to the second step are further polymerized to the two fluorine-based or non-fluorine-based diamine monomers.

17. A polyimide which is a cured product of the polyamic acid composition of claim 1.

18. A coating material comprising the polyimide of claim 17.

19. A coated electric wire comprising: an electric wire; and a coating material that the polyamic acid composition according to claim 1 is coated on the surface of the electric wire and imidized.

20. An electronic device comprising the coated electric wire according to claim 19.

Description

BEST MODE

[0046] Hereinafter, the present invention will be described in more detail through Examples according to the present invention and Comparative Examples not according to the present invention, but the scope of the present invention is not limited by Examples presented below.

EXAMPLE 1

[0047] N-methyl-pyrrolidone (NMP) was introduced into a 500 ml reactor equipped with a stirrer and nitrogen injection/discharge tubes while nitrogen was injected thereto, and after the temperature of the reactor was set to 30° C., 2,2-bis[4-(4-aminophenoxyphenyl)]hexafluoropropane (HFBAPP), a fluorine-based monomer, as a diamine monomer and 3,3′,4,4′-benzophenonetetracarboxylic dianhydride (BTDA), a non-fluorine-based monomer, as a dianhydride monomer were introduced to confirm that they were completely dissolved. Subsequently, 4,4′-Oxydianiline (ODA), a non-fluorine-based monomer, as a diamine monomer was introduced, and the polymerization reaction was performed in the same manner. Subsequently, 2,2-bis(3,4-anhydrodicarboxyphenyl)hexafluoropropane (6-FDA), a fluorine-based monomer, as a dianhydride monomer was introduced, and the temperature was raised to 40° C. and stirring was continued for 120 minutes while heating. Subsequently, the temperature was raised to 80° C. under a nitrogen atmosphere and stirring was continued for 2 hours while heating. The polymerization reaction was performed in the same manner to prepare a polyamic acid solution.

EXAMPLES 2 to 4 and 6, and COMPARATIVE EXAMPLES 1 to 4 and 6

[0048] Polyamic acid compositions of Examples 2 to 4 and 6 were prepared in the same method as in Example 1, except that in Example 1, the monomers and their content ratios were changed as shown in Table 1 below. Polyamic acid compositions of Comparative Examples 1 to 4 and 6 were prepared in the same method as in Example 1, except that the monomers and their contents were each changed as shown in Table 1 below, and two types of diamine monomers and two types of dianhydride monomers were simultaneously introduced.

EXAMPLE 5 and COMPARATIVE EXAMPLE 5

[0049] N-methyl-pyrrolidone (NMP) was introduced into a 500 ml reactor equipped with a stirrer and nitrogen injection/discharge tubes while nitrogen was injected thereto, and after the temperature of the reactor was set to 30° C., 4,4′-oxydianiline (ODA), a non-fluorine-based monomer, as a diamine monomer and 3,3′,4,4′-benzophenonetetracarboxylic dianhydride (BTDA), a non-fluorine-based monomer, as a dianhydride monomer were introduced to confirm that they were completely dissolved.

[0050] Subsequently, 2,2-bis(3,4-anhydrodicarboxyphenyl)hexafluoropropane (6-FDA), a fluorine-based monomer, as a dianhydride monomer was introduced, and the temperature was raised to 40° C. and stirring was continued for 120 minutes while heating. Subsequently, the temperature was raised to 80° C. under a nitrogen atmosphere and stirring was continued for 2 hours while heating. The polymerization reaction was performed in the same manner to prepare polyamic acid solutions.

TABLE-US-00001 TABLE 1 Diamine Dianhydride ODA HFBAPP BTDA 6-FDA (mol %) (mol %) (mol %) (mol %) Example 1 10 90 90 10 2 30 70 70 30 3 50 50 50 50 4 50 50 70 30 5 100 0 50 50 6 75 25 75 25 Comparative 1 10 90 90 10 Example 2 30 70 70 30 3 50 50 50 50 4 50 50 70 30 5 100 0 50 50 6 75 25 75 25

[0051] In a coating curing furnace, an electric wire (coated electric wire) comprising a polyimide coating material having a coating material thickness of 33 to 35 μm was prepared in a state where the coating thickness of the polyamic add solution to a copper wire having a conductor diameter of 1 mm was adjusted between 2 and 6 μm per one time, the minimum temperature and maximum temperature of the coating During furnace were adjusted to 350 to 550° C. and the coating rate of the copper wire was adjusted to 12 to 32 m/min.

EXPERIMENTAL EXAMPLE 1

Thickness

[0052] The coating thickness of the prepared polyimide coating material was measured according to KS C 3107 standard.

EXPERIMENTAL EXAMPLE 2

Permittivity and Dielectric Loss Tangent Values

[0053] The permittivity and dielectric loss tangent at 1 GHz of the polyimide coating materials prepared in Examples and Comparative Examples were measured using Keysight's SPDR measuring instrument. As a result, the measured permittivity and dielectric loss tangent values were shown in Table 2 below.

EXPERIMENTAL EXAMPLE 3

Measurement of Dielectric Breakdown Voltage (BDV)

[0054] The specimens prepared in Examples and Comparative Examples were each pretreated in an oven at 150° C. for 4 hours, and then placed in a pressure vessel. The pressure vessel was filled with 1400 g of a refrigerant, the pressure vessel was heated for 72 hours, and then the pressure vessel was cooled, and the specimen was transferred to an oven at 150° C., held for 10 minutes, and cooled to room temperature. The BDV was measured by connecting both ends of the electric wire and increasing the alternating voltage of the test voltage (60 Hz) nominal frequency between the wire conductors at a constant rate from zero.

EXPERIMENTAL EXAMPLE 4

Measurement of Partial Discharge Initiation Voltage (PDIV)

[0055] a sample twisted in two lines is manufactured by applying a load and twist according to ASTM 2275-01 standard to the ends of a pair of specimens of the coated electric wires prepared in Examples and Comparative Examples. Thereafter, a voltage at a frequency of 50 to 60 Hz is applied to the bare conductors at both ends of the sample at a constant rate to record the voltage at which partial discharge (100 pC or more) occurs.

TABLE-US-00002 TABLE 2 Dielectric loss Thickness BDV PDIV Permittivity tangent (μm) (kV) (Vp) (1 GHz) (1 GHz) Example 1 33 13.8  850 2.75 0.0044 2 33 13.9  846 2.80 0.0044 3 33 12.5  875 2.78 0.0041 4 34 12.7  860 2.84 0.0046 5 34 12.3  842 2.85 0.0048 6 33 11.8  830 2.90 0.0050 Comparative 1 33 10.2  780 3.05 0.0054 Example 2 33 9.8 785 3.10 0.0055 3 34 9.4 790 3.14 0.0051 4 35 9.5 772 3.18 0.0062 5 33 9.1 766 3.26 0.0065 6 33 8.5 750 3.35 0.0068