Polyamide-imide film and process for preparing the same

Patent metadata

Field	Value
Publication number	US-2020407504-A1
Application number	US-201916452803-A
Country	US
Kind code	A1
Filing date	Jun 26, 2019
Priority date	Jun 26, 2019
Publication date	Dec 31, 2020
Grant date	—

Abstract

Embodiments provide a polyamide-imide polymer film, which comprises a polyamide-imide polymer formed by polymerizing a diamine compound, a dianhydride compound, and a dicarbonyl compound; and silica particles, wherein the number of aggregates having an average diameter of 150 to 200 nm observed in a cross-section cut in the thickness direction of the polyamide-imide film is less than 0.5/μm2, and a process for preparing the same.

First claim

1 . A polyamide-imide film, which comprises:
a polyamide-imide polymer formed by polymerizing a diamine compound, a dianhydride compound, and a dicarbonyl compound; and silica particles, wherein the number of aggregates having an average diameter of 150 to 200 nm observed in a cross-section cut in the thickness direction of the polyimide-imide film is less than 0.5/μm 2 .

2 . The polyamide-imide film of claim 1 , wherein the average particle size of primary particles of the silica particles is 10 to 40 nm, and
the average particle size of secondary particles of the silica particles is 30 to 80 nm.

3 . The polyamide-imide film of claim 1 , wherein the ratio of the average particle diameter of the secondary particles to the average particle diameter of the primary particles of the silica particles is 1.2 to 3.0.

4 . The polyamide-imide film of claim 1 , wherein the content of the silica particles is 50 to 600 ppm based on the total weight of the polyamide-imide polymer.

5 . The polyamide-imide film of claim 1 , wherein the number of aggregates having an average diameter of 150 to 200 nm observed in a cross-section cut in the thickness direction of the polyamide-imide film is 0 to 0.3/μm 2 .

6 . The polyamide-imide film of claim 1 , wherein the diamine compound is represented by the following Formula 1,
the dianhydride compound is represented by the following Formula 2, and the dicarbonyl compound is represented by the following Formula 3:

in the above Formulae 1 to 3,
E and J are each independently selected from a substituted or unsubstituted divalent C 6 -C 30 aliphatic cyclic group, a substituted or unsubstituted divalent C 4 -C 30 heteroaliphatic cyclic group, a substituted or unsubstituted divalent C 6 -C 30 aromatic cyclic group, a substituted or unsubstituted divalent C 4 -C 30 heteroaromatic cyclic group, a substituted or unsubstituted alkylene group, a substituted or unsubstituted C 2 -C 30 alkenylene group, a substituted or unsubstituted C 2 -C 30 alkynylene group, —O—, —S—, —C(═O)—, —CH(OH)—, —S(═O) 2 —, —C(CH 3 ) 2 —, and —C(CF 3 ) 2 —,
e and j are each independently selected from integers of 1 to 5,
when e is 2 or more, then the 2 or more Es are the same as, or different from, each other,
when j is 2 or more, then the 2 or more Js are the same as, or different from, each other,
G is a substituted or unsubstituted tetravalent C 6 -C 30 aliphatic cyclic group, a substituted or unsubstituted tetravalent C 4 -C 30 heteroaliphatic cyclic group, a substituted or unsubstituted tetravalent C 6 -C 30 aromatic cyclic group, or a substituted or unsubstituted tetravalent C 4 -C 30 heteroaromatic cyclic group, wherein the aliphatic cyclic group, the heteroaliphatic cyclic group, the aromatic cyclic group, or the heteroaromatic cyclic group is present alone, bonded to each other to form a condensed ring, or bonded by a bonding group selected from a substituted or unsubstituted C 1 -C 30 alkylene group, a substituted or unsubstituted C 2 -C 30 alkenylene group, a substituted or unsubstituted C 2 -C 30 alkynylene group, —O—, —S—, —C(═O)—, —CH(OH)—, —S(═O) 2 —, —Si(CH 13 ) 2 —, —C(CH 3 ) 2 —, and —C(CF 3 ) 2 —, and
X is a halogen atom.

7 . The polyamide-imide film of claim 1 , wherein the dianhydride compound is composed of a compound having a fluorine-containing substituent.

8 . The polyamide-imide film of claim 1 , wherein the dicarbonyl compound comprises at least two dicarbonyl compounds different from each other.

9 . The polyamide-imide film of claim 1 , wherein the polyamide-imide polymer comprises a repeat unit represented by the following Formula A and a repeat unit represented by the following Formula B:

wherein F, G, J, e, and j in the above Formulae A and B are as described in claim 1 .

10 . The polyimide-imide film of claim 9 , wherein in the polyimide-imide polymer, the molar ratio of the repeat unit represented by the above Formula A to the repeat unit represented by the above Formula B is 10:90 to 25:75.

11 . The polyamide-imide film of claim 1 , which, based on a thickness of 50 μm, has a modulus of 5.0 GPa or more, an elongation of 15% or more, a tensile strength of 15 kgf/mm 2 or more, and a haze of 2% or less.

12 . A process for preparing a polyamide-imide film, which comprises:
preparing a silica dispersion in which silica particles are dispersed; introducing the silica dispersion into an organic solvent; polymerizing a diamine compound, a dianhydride compound, and a dicarbonyl compound in the organic solvent to which the silica dispersion has been introduced to prepare a polyamide-imide polymer solution; transferring the polymer solution to a tank; extruding and casting the polymer solution in the tank and then drying the same to prepare a gel sheet; and thermally treating the gel sheet.

13 . The process for preparing a polyamide-imide film of claim 12 , wherein the average particle size of primary particles of the silica particles is 10 to 40 nm, and
the average particle size of secondary particles of the silica particles is 30 to 80 nm.

14 . The process for preparing a polyamide-imide film of claim 12 , wherein the ratio of the average particle diameter of the secondary particles to the average particle diameter of the primary particles of the silica particles is 1.2 to 3.0.

15 . The process for preparing a polyamide-imide film of claim 12 , wherein the silica dispersion. is prepared by introducing the silica particles into an organic solvent and then subjecting them to ultrasonic treatment.

16 . The process for preparing a polyimide-imide film of claim 12 , wherein the content of silica, particles in the silica dispersion is 0.2 to 5% by weight.

17 . The process for preparing a polyimide-imide film of claim 12 , wherein the number of aggregates having an average diameter of 150 to 200 nm observed in a cross-section cut in the thickness direction of the polyamide-imide film is 0 to 0.3/μm 2 .

18 . The process for preparing a polyamide-imide film of claim 12 , wherein the thermal treatment is carried out in a temperature range of 80 to 500° C. at a temperature elevation rate of 2° C./min to 80° C./min for 5 to 40 minutes, and the maximum temperature in the thermal treatment is 300 to 500° C.

19 . The process for preparing a polyimide-imide film of claim 12 , which, after the step of transferring the polymer solution to the tank, further comprises vacuum degassing by depressurizing the internal pressure of the tank to 0.1 to 0.7 bar for 30 minutes to 3 hours; and
purging the tank with nitrogen gas at 1 to 2 atmospheres.

20 . The process for preparing a polyimide-imide film of claim 12 , which, after the thermal treatment step, further comprises lowering the temperature of the thermally treated sheet,
wherein the step of lowering the temperature comprises a first temperature lowering step of reducing the temperature at a rate of 100° C./min to 1,000° C./min and a second temperature lowering step of reducing the temperature at a rate of 40° C./min to 400° C./min, the second temperature lowering step is performed after the first temperature lowering step, and the temperature lowering rate of the first temperature lowering step is faster than the temperature lowering rate of th

Assignees

• Skc Co Ltd

Inventors

• Oh Dae Seong
• Jeong Dawoo
• Kim Sunhwan
• Lee Jin Woo
• Lim Dong Jin

Classifications

• C08J2379/08

  Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors · CPC title

• C08K2201/011

  Nanostructured additives · CPC title

• C08K3/36

  Silica · CPC title

• C08G73/14 Primary

  Polyamide-imides · CPC title

• C08G73/1039

  comprising halogen-containing substituents · CPC title