Thick polyimide film having improved surface quality and method of manufacturing same

Patent metadata

Field	Value
Publication number	US-11945922-B2
Application number	US-201817276188-A
Country	US
Kind code	B2
Filing date	Nov 22, 2018
Priority date	Oct 19, 2018
Publication date	Apr 2, 2024
Grant date	Apr 2, 2024

Abstract

The present invention provides a polyimide film in which a parameter A for the relationship of the viscosity (V) of a polyamic acid solution, the number average molecular weight (Mn) of polyamic acid, and the thickness (T) of a polyimide film falls within a range from 0.4 to 1.13.

First claim

What is claimed is:

1. A polyimide film manufactured by imidizing a polyamic acid solution, wherein a following parameter A falls within a range from 0.4 to 1.13:
A =log(( V·Mn ) 2 ·√{square root over ( T )})−21

wherein V is a viscosity of the polyamic acid solution and is 200,000 cP to 250,000 cP as measured at 23° C. when a solid content thereof is 18.5 wt %, Mn is a number average molecular weight of polyamic acid dissolved in the polyamic acid solution and is 100,000 g/mole to 150,000 g/mole, and T is a thickness of the polyimide film and is 55 μm to 110 μm.

2. The polyimide film of claim 1 , wherein the polyamic acid has a weight average molecular weight/number average molecular weight ratio (=Mw/Mn) of 1.5 to 1.8.

3. The polyimide film of claim 1 , wherein the polyamic acid comprises:
a first polymer chain having a number average molecular weight of 10,000 g/mole to 80,000 g/mole;
a second polymer chain having a number average molecular weight of greater than 80,000 g/mole to 170,000 g/mole; and
a third polymer chain having a number average molecular weight of greater than 170,000 g/mole to 400,000 g/mole.

4. The polyimide film of claim 3 , wherein, based on a total weight of the polyamic acid,
an amount of the first polymer chain is 5% to 20%,
an amount of the second polymer chain is 70% to 90%, and
an amount of the third polymer chain is 5% to 10%.

5. The polyimide film of claim 1 , wherein when the polyimide film is subjected to corona treatment and is tested using an adhesive, an adhesion of the polyimide film is 1,100 gf/mm or more.

6. The polyimide film of claim 1 , having a modulus of 3.3 Gpa or more, an elongation of 75% or more, a tensile strength of 25 Mpa or more, and 1 or fewer surface defects per 10 cm*10 cm area.

7. The polyimide film of claim 1 , wherein the V is 215,000 cP to 245,000 cP, the Mn is 110,000 g/mole to 140,000 g/mole, and the T is 65 μm to 100 μm.

8. The polyimide film of claim 1 , wherein the parameter A falls within the range from 0.5 to 1.05.

9. The polyimide film of claim 1 , wherein the parameter A falls within the range from 0.6 to 1.00.

10. The polyimide film of claim 1 , wherein the polyamic acid is prepared by polymerizing a dianhydride monomer and a diamine monomer.

11. The polyimide film of claim 10 , wherein the dianhydride monomer is at least one selected from the group consisting of pyromellitic dianhydride (or PMDA), 3,3′,4,4′-biphenyltetracarboxylic dianhydride (or s-BPDA), 2,3,3′,4′-biphenyltetracarboxylic dianhydride (or a-BPDA), oxydiphthalic dianhydride (or ODPA), diphenylsulfone-3,4,3′,4′-tetracarboxylic dianhydride (or DSDA), bis(3,4-dicarboxyphenyl)sulfide dianhydride, 2,2-bis(3,4-dicarboxyphenyl)-1,1,1,3,3,3-hexafluoropropane dianhydride, 2,3,3′,4′-benzophenonetetracarboxylic dianhydride, 3,3′,4,4′-benzophenonetetracarboxylic dianhydride (or BTDA), bis(3,4-dicarboxyphenyl)methane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, p-phenylenebis(trimellitic monoester acid anhydride), p-biphenylenebis(trimellitic monoester acid anhydride), m-terphenyl-3,4,3′,4′-tetracarboxylic dianhydride, p-terphenyl-3,4,3′,4′-tetracarboxylic dianhydride, 1,3-bis(3,4-dicarboxyphenoxy)benzene dianhydride, 1,4-bis(3,4-dicarboxyphenoxy)benzene dianhydride, 1,4-bis(3,4-dicarboxyphenoxy)biphenyl dianhydride, 2,2-bis[(3,4-dicarboxyphenoxy)phenyl]propane dianhydride (or BPADA), 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, and 4,4′-(2,2-hexafluoroisopropylidene)diphthalic dianhydride.

12. The polyimide film of claim 10 , wherein the diamine monomer is at least one selected from the group consisting of 1,4-diaminobenzene (or paraphenylenediamine, PDA, PPD), 1,3-diaminobenzene, 2,4-diaminotoluene, 2,6-diaminotoluene, 3,5-diaminobenzoic acid (or DABA), 4,4′-diaminodiphenyl ether (or oxydianiline, ODA), 3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane (or 4,4′-methylenediamine, MDA), 3,3′-dimethyl-4,4′-diaminobiphenyl, 2,2′-dimethyl-4,4′-diaminobiphenyl, 2,2′-bis(trifluoromethyl)-4,4′-diaminobiphenyl, 3,3′-dimethyl-4,4′-diaminodiphenylmethane, 3,3′-dicarboxy-4,4′-diaminodiphenylmethane, 3,3′,5,5′-tetramethyl-4,4′-diaminodiphenylmethane, bis(4-aminophenyl)sulfide, 4,4′-diaminobenzanilide, 3,3′-dichlorobenzidine, 3,3′-dimethylbenzidine (or o-tolidine), and 2,2′-dimethylbenzidine (or m-tolidine).

13. A method of manufacturing a polyimide film, comprising:
(a) preparing a polyamic acid solution by polymerizing a dianhydride monomer comprising at least one component and a diamine monomer comprising at least one component in an organic solvent; and
(b) imidizing the polyamic acid solution to obtain a polyimide film,
wherein a following parameter A falls within a range from 0.4 to 1.13:
A =log(( V·Mn ) 2 ·√{square root over ( T )})−21

wherein V is a viscosity of the polyamic acid solution and is 200,000 cP to 250,000 cP as measured at 23° C. when a solid content thereof is 18.5 wt %, Mn is a number average molecular weight of polyamic acid dissolved in the polyamic acid solution and is 100,000 g/mole to 150,000 g/mole, and T is a thickness of the polyimide film and is 50 μm to 110 μm.

14. The method of claim 13 , wherein, in step (a), the viscosity is adjusted in a manner in which any one selected from among the dianhydride monomer and the diamine monomer is divided into multiple portions and added two or more times.

15. The method of claim 14 , wherein a total amount of the monomer that is added in multiple portions is 98.8 mol % to 99.3 mol % relative to a total amount of a remaining monomer.

16. The method of claim 13 , wherein step (b) comprises:
(b-1) preparing a film-forming composition by mixing the polyamic acid solution with a dehydrating agent and an imidizing agent;
(b-2) preparing a film intermediate by applying the film-forming composition on a substrate and performing first heat treatment at 50 to 150° C.; and
(b-3) subjecting the film intermediate to second heat treatment at 200 to 600° C.

17. An electronic part comprising the polyimide film of claim 1 as an insulating film.

Assignees

• Pi Advanced Mat Co Ltd

Inventors

• Son Won Ho
• Jo Hyong Sop

Classifications

• C08J5/18 Primary

  Manufacture of films or sheets · CPC title

• C08G73/1032

  characterised by the solvent(s) used · CPC title

• C08G73/1046

  Polyimides containing oxygen in the form of ether bonds in the main chain · CPC title

• C08G73/1071

  Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain · CPC title

• C08L79/08

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