POLYAMIDE ACID COMPOSITION AND POLYIMIDE COMPOSITION

Abstract

A polyamide acid composition and a polyimide composition are obtained from a tetracarboxylic acid compound containing an aromatic tetracarboxylic acid compound having a naphthalene skeleton and a diamine compound containing an aromatic diamine compound having a biphenyl skeleton.

Claims

1. A polyamide acid composition comprising: a polyamide acid obtained by polymerization of a: tetracarboxylic acid compound containing 2,3,6,7-naphthalenetetracarboxylic acid dianhydride, and a diamine compound containing 95 to 75 mol % of p-phenylenediamine and 5 to 25 mol % of o-tolidine and/or 2,2-bis(trifluoromethyl)benzidine.

2. The polyamide acid composition according to claim 1, wherein the tetracarboxylic acid compound contains less than 100 mol % and 50 mol % or more of the 2,3,6,7-naphthalenetetracarboxylic acid dianhydride and contains 50 mol % or less and more than 0 mol % of 3,3,4,4-biphenyltetracarboxylic acid dianhydride.

3. A polyamide acid obtained by polymerization of a: tetracarboxylic acid compound containing 2,3,6,7-naphthalenetetracarboxylic acid dianhydride, and a diamine compound containing 95 to 75 mol % of p-phenylenediamine and 5 to 25 mol % of o-tolidine and/or 2,2-bis(trifluoromethyl)benzidine.

4. The polyamide acid according to claim 3, wherein the tetracarboxylic acid compound contains less than 100 mol % and 50 mol % or more of the 2,3,6,7-naphthalenetetracarboxylic acid dianhydride and contains 50 mol % or less and more than 0 mol % of 3,3,4,4-biphenyltetracarboxylic acid dianhydride.

5. A polyimide composition comprising: a polyamide acid obtained by polymerization of a: tetracarboxylic acid compound containing 2,3,6,7-naphthalenetetracarboxylic acid dianhydride, and a diamine compound containing 95 to 75 mol % of p-phenylenediamine and 5 to 25 mol % of o-tolidine and/or 2,2-bis(trifluoromethyl)benzidine.

6. The polyimide composition according to claim 5, wherein the tetracarboxylic acid compound contains less than 100 mol % and 50 mol % or more of the 2,3,6,7-naphthalenetetracarboxylic acid dianhydride and contains 50 mol % or less and more than 0 mol % of 3,3,4,4-biphenyltetracarboxylic acid dianhydride.

7. A polyimide obtained by polymerization of a: tetracarboxylic acid compound containing 2,3,6,7-naphthalenetetracarboxylic acid dianhydride, and a diamine compound containing 95 to 75 mol % of p-phenylenediamine and 5 to 25 mol % of o-tolidine and/or 2,2-bis(trifluoromethyl)benzidine.

8. The polyimide according to claim 7, wherein the tetracarboxylic acid compound contains less than 100 mol % and 50 mol % or more of the 2,3,6,7-naphthalenetetracarboxylic acid dianhydride and contains 50 mol % or less and more than 0 mol % of 3,3,4,4-biphenyltetracarboxylic acid dianhydride.

9. The polyimide according to claim 7, wherein the polyimide has a thermal expansion coefficient of 10 ppm/ C. or less.

10. The polyimide according to claim 8, wherein the polyimide has a thermal expansion coefficient of 10 ppm/ C. or less.

11. The polyimide according to claim 7, wherein the polyimide has a 5% thermal weight loss temperature of 600 C. or higher.

12. The polyimide according to claim 8, wherein the polyimide has a 5% thermal weight loss temperature of 600 C. or higher.

13. The polyimide according to claim 9, wherein the polyimide has a 5% thermal weight loss temperature of 600 C. or higher.

14. The polyimide according to claim 10, wherein the polyimide has a 5% thermal weight loss temperature of 600 C. or higher.

Description

EXAMPLES

[0089] The present disclosure will be specifically described by way of exemplary Examples. However, the present disclosure is not limited to these exemplary Examples.

[0090] The details of the following components are as follows.

[0091] PDA: p-phenylenediamine

[0092] OT: o-tolidine

[0093] TFMB: 2,2-bis(trifluoromethyl)benzidine

[0094] NTCDA: 2,3,6,7-naphthalenetetracarboxylic acid dianhydride

[0095] sBPDA: 3,3,4,4-biphenyltetracarboxylic acid dianhydride

<Evaluation>

[0096] Mechanical properties were evaluated by the following methods The results are shown in Tables.

(Thermal Expansion Coefficient)

[0097] Measurement device: TMA-60, Shimadzu Corporation

[0098] Temperature range: 50 C. to 200 C.

[0099] Heating rate: 10 C./min

(Thermal Decomposition Temperature)

[0100] Measurement device: DTC-60, Shimadzu Corporation

[0101] Heating rate: 10 C./min

[0102] Thermal decomposition temperature: Temperature at which the loss of weight in a measurement chart is 5%.

(Varnish Solubility)

[0103] A precipitate, an insoluble component, and gelation in the varnish were checked visually. A, B, and C in Tables mean as follows.

[0104] A: After completion of the polymerization of the varnish (solid content: 20 wt %), no precipitate and no gelation were found. Even after long-term storage (one month), no precipitate, no gelation, and no thickening were found.

[0105] B. After completion of the polymerization of the varnish (solid content: 20 wt %), no precipitation and no gelation were found. After long-term storage (one month), precipitation, gelation, or thickening was found.

[0106] C: After completion of the polymerization of the varnish (solid content: 20 wt %), precipitation and gelation were found.

Example 1

[0107] 51 g of PDA, 8 g of TFMB, 67 g of NTCDA, and 73 g of sBPDA were added to 850 g of N,N-dimethylacetamide (DMAc), and the mixture was stirred and allowed to react at room temperature and an atmospheric pressure for 3 hours wo obtain a polyamide acid solution (polyamide acid composition).

[0108] 15 g of the polyamide acid solution obtained was applied to a glass plate using a bar coater and heat-cured at 100 C. for 20 minutes, 200 C. for 20 minutes, 300 C. for 20 minutes, and 400 C. for 20 minutes to thereby obtain a polyimide film with a thickness of about 50 m.

[0109] The film obtained was subjected to characteristic evaluation tests, and the results are shown in Table 1. The molar ratio of each component is a molar ratio with respect to the total moles of the aromatic diamine components or the total moles of the tetracarboxylic acid components.

Example 2 to 6

[0110] Polyamide acids and polyimide films were produced following the same procedure as in Example 1 using aromatic diamine components and tetracarboxylic acid components at molar ratios shown in Table 1 and subjected to characteristic evaluation tests. The results are shown in Table 1.

Comparative Example 1 to 9

[0111] Polyamide acids and polyimide films were produced following the same procedure as in Example 1 using aromatic diamine components and tetracarboxylic acid components at molar ratios shown in Table 2 and subjected to characteristic evaluation tests. The results are shown in Table 2.

TABLE-US-00001 TABLE 2 Comp. Comp. Comp. Comp. Comp. Comp. Comp. Comp. Comp. Example Example Example Example Example Example Example Example Example 1 2 3 4 5 6 7 8 9 Molar ratio NTCDA 0.10 1.00 1.00 0.50 0.25 1.00 1.00 1.00 of sBPDA 1.00 0.90 0.50 0.75 monomers PDA 1.00 1.00 0.50 0.50 1.00 1.00 1.00 0.97 0.97 OT 0.50 0.03 TFMB 0.50 0.03 Thermal expansion 18.0 15.0 12.0 11.0 3.5 8.5 coefficient [ppm] Thermal decomposition 595 597 599 598 607 603 temperature [ C.] Varnish solubility A A A A B B C C C

[0112] As is clear from the results shown in the above tables, in a PDA-sBPDA-based polyimide containing no NTCDA (Comparative Example 1), a polyimide containing only a small amount of NTCDA as an acid component and containing no OT and no TFMB as amine components (Comparative Example 2), and polyimides containing NTCDA as an acid component and containing only a small amount of PDA as an amine component (Comparative Examples 3 and 4), the thermal expansion coefficient is high (more than 10 ppm/ C.), and the thermal decomposition temperature is low (lower than 600 C.) in polyimides containing NTCDA as an acid component but containing no OT and no TFMB as amine components or only a small amount of OT or TFMB (Comparative Examples 5 to 9), the thermal expansion coefficient is low (10 ppm/ C.) or lower), and the thermal decomposition temperature is high (600 C. or higher), but the varnish solubility is poor.

[0113] In polyimides containing NTCDA as an acid component and containing PDA and at least one of OT and TFME at the above-described specific ratio as amine components (Examples 1 to 6), the thermal expansion coefficient is low, and the thermal decomposition temperature is high (600 C. or higher). Moreover, the varnish solubility is good.

Industrial Applicability

[0114] The polyamide acid composition. of the present disclosure has good varnish solubility. A polyimide composition obtained by curing the polyamide acid composition of the present disclosure has a low thermal expansion coefficient (10 ppm/ C. or lower) and a high thermal decomposition temperature (600 C. or higher). Polyimide materials obtained using the present disclosure are expected to be effectively used for applications that require thermal dimensional stability and heat resistance equal to or higher than those of conventional polyimide materials (e.g., semiconductor materials and thin-film solar cell materials).