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

Abstract

The present application relates to a polyamic acid composition, a method for preparing the polyamic acid composition, and a polyimide comprising the same, which provides a polyamic acid composition capable of implementing a low permittivity, and heat resistance and mechanical properties simultaneously, a method for preparing the polyamic acid composition and a polyimide 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 and a glass transition temperature of 340° C. 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 add 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 polyimide film comprising the polyimide of claim 17 in the form of a film or sheet.

Description

BEST MODE

[0045] 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

[0046] N-methyl-pyrrolidone (NW) 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(trifluoromethyl)benzidine (TFMB), a fluorine-based monomer, as a diamine monomer and pyromellitic dianhydride (PMDA), 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

[0047] 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

[0048] 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 pyromellitic dianhydride (PMDA), a non-fluorine-based monomer, as a dianhydride monomer were introduced to confirm that they were completely dissolved.

[0049] 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 TFMB PMDA 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

[0050] Bubbles were removed from the polyamic acid compositions prepared in Examples and Comparative Examples above through high-speed rotation of 1,500 rpm or more. Thereafter, the defoamed polyamic acid compositions were each applied to a glass substrate using a spin coater. Thereafter, it was dried under a nitrogen atmosphere and at a temperature of 120° C. for 30 minutes to produce a gel film, and the temperature of the gel film was raised to 450° C. at a rate of 2° C./min, and it was heat-treated at 450° C. for 60 minutes, and cooled to 30° C. at a rate of 2° C./min to obtain a polyimide film. Thereafter, it was dipped in distilled water to peel the polyimide film from the glass substrate. The physical properties of the produced polyimide film were measured using the following method, and the results were shown in Table 2 below.

Experimental Example—Thickness

[0051] The thickness of the produced polyimide film was measured using Anritsu's electric film thickness tester.

Experimental Example 2—Measurement of Glass Transition Temperature

[0052] Using TA's dynamic mechanical analysis Q800 model, the polyimide film was cut into 4 mm wide and 20 mm long, and then the glass transition temperature was measured under a nitrogen atmosphere at a temperature increase rate of 5° C./min and under the condition of a temperature range from room temperature to 550° C. The glass transition temperature was determined as the maximum peak of tan δ calculated according to the ratio of the storage elastic modulus and the loss elastic modulus.

Experimental Example 3—Permittivity and Dielectric Loss Tangent Values

[0053] The permittivity and dielectric loss tangent at 1 GHz of the polyimide films 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.

TABLE-US-00002 TABLE 2 Glass Dielectric transition loss Thickness temperature Permittivity tangent (μm) (° C.) (1 GHz) (1 GHz) Example 1 19 340 2.8 0.0045 2 18 344 2.75 0.0046 3 21 355 2.84 0.0048 4 19 355 2.87 0.0048 5 20 380 2.86 0.0049 6 19 378 2.97 0.0049 Comparative 1 19 315 3.05 0.0053 Example 2 18 320 3.06 0.0052 3 21 320 3.10 0.0057 4 19 325 3.18 0.0055 5 20 332 3.22 0.0058 6 19 338 3.25 0.0065