Polymer resin composition, polyimide resin film, preparation method of polyimide resin film, flexible metal laminate, and circuit board

1. A polymer resin composition comprising: a polyamic acid including a repeating unit represented by the following Chemical Formula 1; and a tetrahydropyran compound,

wherein, Y 1 is a tetravalent organic functional group, X is a divalent organic functional group, and n is an integer of 1 to 100 ,

wherein the tetrahydropyran compound comprises at least a compound selected from the group consisting of sucrose, cyclodextrin, glucose, and derivatives thereof, or wherein the tetrahydropyran compound comprises at least a compound selected from the group consisting of a polymer compound including a repeating unit of the following Chemical Formula 2 and a compound of the following Chemical Formula 3:

wherein, in Chemical Formula 2, R 1 , R 2 , and R 3 are same as or different from each other and are respectively hydrogen or an alkyl having 1 to 3 carbon atoms, and n is an integer of 1 to 10,

in Chemical Formula 3, R 5 , R 6 , R 7 , R 8 , and R 9 are same as or different from each other and are respectively hydrogen, an alkyl having 1 to 3 carbon atoms, a functional group of the following Chemical Formula 4, or a functional group of the following Chemical Formula 5,

in Chemical Formula 5, R 11 , R 12 , R 13 and R 14 are same as or different from each other and are respectively hydrogen, an alkyl having 1 to 3 carbon atoms, an alkoxy having 1 to 3 carbon atoms, a functional group of the following Chemical Formula 6, or a functional group of the following Chemical Formula 7,

in Chemical Formulae 4 to 7, “*” means a bonding point.

2. The polymer resin composition according to claim 1 , wherein the polyamic acid has a weight average molecular weight of 10,000 to 1,000,000.

3. The polymer resin composition according to claim 1 , wherein Y 1 is a tetravalent organic functional group containing one to three aromatic rings; a tetravalent organic functional group containing one to three aliphatic ring; or a tetravalent aliphatic organic functional group derived from a linear or branched alkyl having 1 to 10 carbon atoms.

4. The polymer resin composition according to claim 1 , wherein Y 1 is a tetravalent functional group selected from the group consisting of the following Chemical Formulae 21 to 35:

wherein, in Chemical Formula 22, Y 1 is single bond, —O—, —CO—, —S—, —SO 2 —, —C(CH 3 ) 2 —, —C(CF 3 ) 2 —, —CONH—, —COO—, —(CH 2 ) n1 —, —O(CH 2 ) n2 O—, or —OCO(CH 2 ) n3 OCO—, and n1, n2, and n3 are respectively an integer of 1 to 10,

wherein, in Chemical Formula 23, Y 2 and Y 3 are same as or different from each other and are respectively a single bond, —O—, —CO—, —S—, —SO 2 —, —C(CH 3 ) 2 —, —C(CF 3 ) 2 —, —CONH—, —COO—, —(CH 2 ) n1 —, —O(CH 2 ) n2 O—, or —OCO(CH 2 ) n3 OCO—, and n1, n2, and n3 are respectively an integer of 1 to 10,

wherein, in Chemical Formula 24, Y 4 , Y 5 , and Y 6 are same as or different from each other and are respectively a single bond, —O—, —CO—, —S—, —SO 2 —, —C(CH 3 ) 2 —, —C(CF 3 ) 2 —, —CONH—, —COO—, —(CH 2 ) n1 —, —O(CH 2 ) n2 O—, or —OCO(CH 2 ) n3 OCO—, and n1, n2, and n3 are respectively an integer of 1 to 10,

5. The polymer resin composition according to claim 1 , wherein X is a divalent organic functional group selected from the group consisting of a divalent organic functional group containing 1 to 5 aromatic rings; a divalent organic functional group containing 1 to 3 aliphatic rings; a divalent organic functional group having a ether functional group or a ester functional group; and a polysiloxane divalent functional group.

6. The polymer resin composition according to claim 1 , wherein X is a divalent functional group selected from the group consisting of compounds of the following Chemical Formulae 36 to 44:

wherein, in Chemical Formula 37, L 1 is a single bond, —O—, —CO—, —S—, —SO 2 —, —C(CH 3 ) 2 —, —C(CF 3 ) 2 —, —CONH—, —COO—, —(CH 2 ) n1 —, —O(CH 2 ) n2 O—, —OCH 2 —C(CH 3 ) 2 —CH 2 O—, or —OCO(CH 2 ) n3 OCO—, and n1, n2, and n3 are respectively an integer of 1 to 10,

in Chemical Formula 38, L 2 and L 3 are the same as or different from each other and are respectively a single bond, —O—, —CO—, —S—, —SO 2 —, —C(CH 3 ) 2 —, —C(CF 3 ) 2 —, —CONH—, —COO—, —(CH 2 ) n1 —, —O(CH 2 ) n2 O—, —OCH 2 —C(CH 3 ) 2 —CH 2 O—, or —OCO(CH 2 ) n3 OCO—, and n1, n2, and n3 are respectively an integer of 1 to 10,

in Chemical Formula 39, L 4 , L 5 , and L 6 are the same as or different from each other and are respectively a single bond, —O—, —CO—, —S—, —SO 2 —, —C(CH 3 ) 2 —, —C(CF 3 ) 2 —, —CONH—, —COO—, —(CH 2 ) n1 —, —O(CH 2 ) n2 O—, —OCH 2 —C(CH 3 ) 2 —CH 2 O—, or —OCO(CH 2 ) n3 OCO—, and n1, n2, and n3 are respectively an integer of 1 to 10,

in Chemical Formula 43, R 1 is an alkylene having 2 to 8 carbon atoms or an arylene, R 2 is alkylene having 2 to 8 carbon atoms, a and b are each 0 or 1, and c is an integer from 1 to 21,

in Chemical Formula 44, R 11 , R 12 , R 13 , and R 14 are the same as or different from each other and are respectively an alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 10 carbon atoms, R 15 and R 16 are respectively a linear or branched chain alkylene group having 1 to 20 carbon atoms, m is an integer of 1 or more, and n is an integer of 0 or more.

7. The polymer resin composition according to claim 1 , further comprising an organic solvent.

8. The polymer resin composition according to claim 1 , further comprising at least one additive selected from the group consisting of a dispersant, a surfactant, an antioxidant, a cure accelerator, a defoaming agent, an organic filler, and an inorganic filler.

9. A polyimide resin film comprising a heat cured product or dried product of the polymer resin composition according to claim 1 .

10. The polyimide resin film according to claim 9 , wherein fine pores having a diameter of 100 nm to 5 μm are distributed in a substrate of a polyimide polymer including a repeating unit of Chemical Formula 11:

wherein, in Chemical Formula 11, Y 1 is a tetravalent organic functional group, X is a divalent organic functional group, and n is an integer of 1 to 100.

11. The polyimide resin film according to claim 10 , having porosity of 5% to 70%.

12. The polyimide resin film according to claim 10 , wherein each of the pores is distributed in an independent state without connecting with other pores.

13. The polyimide resin film according to claim 9 , having a dielectric constant of 2.9 or less.

14. The polyimide resin film according to claim 9 , having a thickness of 5 μm to 100 μm.

15. A preparation method of polyimide resin film, which comprises applying the polymer resin composition according to claim 1 onto a substrate, and heating the polymer resin composition applied on the substrate.

16. The preparation method of polyimide resin film according to claim 15 , wherein the heating is performed at 200° C. to 500° C.

17. The preparation method of polyimide resin film according to claim 15 , wherein the heating is performed at 200° C. to 430° C. for 1 minute to 3 hours.

18. The preparation method of polyimide resin film according to claim 15 , which further comprises drying the polymer resin composition applied on the substrate.

19. The preparation method of polyimide resin film according to claim 18 , wherein the drying is performed at 60° C. to 200° C. for 30 seconds to 30 minutes.

20. A flexible metal laminate including the polyimide resin film according to claim 9 and a metal thin film.

21. The flexible metal laminate according to claim 20 , wherein fine pores having a diameter of 100 nm to 5 μm are distributed in the polyimide resin film, and

each of the pores is distributed in an independent state without connecting with other pores.

22. The flexible metal laminate according to claim 20 , having a porosity of 5% to 70% and a dielectric constant of 2.9 or less.

23. The flexible metal laminate according to claim 20 , comprising a tetrahydropyran compound or a variation formed by heat treatment thereof in a range of 500 ppmw or less.

24. The flexible metal laminate according to claim 20 , which is a copper-clad laminate (CCL) or a flexible copper-clad laminate.

25. A circuit board comprising the polyimide resin film according to claim 9 .

26. The circuit board according to claim 25 , wherein fine pores having a diameter of 100 nm to 5 μm are distributed in the polyimide resin film, and

each of the pores is distributed in an independent state without connecting with other pores.

27. The circuit board according to claim 25 , wherein the polyimide resin film has porosity of 5% to 70% and a dielectric constant of 2.9 or less.

28. The circuit board according to claim 25 , wherein the polyimide resin film comprises a tetrahydropyran compound or a variation formed by heat treatment thereof in a range of 500 ppmw or less.

29. The circuit board according to claim 25 , wherein the polyimide resin film is used as a protection film of the circuit board, a base film of the circuit board, an insulating layer of the circuit board, a solder resist, or an interlayer insulating film of a semiconductor.