Modified polyimide and curable resin composition

Patent metadata

Field	Value
Publication number	US-10316128-B2
Application number	US-201615501326-A
Country	US
Kind code	B2
Filing date	Jun 28, 2016
Priority date	Sep 15, 2015
Publication date	Jun 11, 2019
Grant date	Jun 11, 2019

Abstract

The present invention relates to a modified polyimide including a terminal group represented by Formula 1:

wherein D is a heat curable or photocurable functional group, R is a divalent or higher polyvalent organic group, and n is an integer of 1 or greater. The modified polyimide undergoes less reduction in transmittance and is protected from discoloration when cured. Due to these advantages, the modified polyimide can provide a highly transparent colorless polyimide film. Particularly, the modified polyimide is suitable for use in display substrates, interlayer insulating films of semiconductor devices, passivation films, buffer coat films, insulating films for multilayer printed circuit boards, insulating films of OLEDs, and protective films of thin film transistors of liquid crystal display devices. The present invention also relates to a curable composition including the modified polyimide.

First claim

What is claimed is:

1. A modified polyimide comprising a terminal group represented by Formula 1:

wherein D is a heat curable or photocurable functional group, R is a divalent or higher polyvalent organic group, and n is an integer of 1 or greater, and
wherein the modified polyimide is represented by Formula 4:

wherein X 1 , X 2 , X 3 , and X 4 are each independently a tetravalent organic group derived from a tetracarboxylic dianhydride, Y 1 , Y 2 , and Y 3 are each independently a divalent organic group derived from a diamine, p, q, r, and v are each independently an integer of 0 or greater, with the proviso that p, q, r, and v are not simultaneously 0, and D, R, and n are as defined in Formula 1.

2. The modified polyimide according to claim 1 , wherein the terminal group of Formula 1 is derived from the reaction of a terminal acid dianhydride group of a polyimide and a compound of Formula 2:

wherein R, D, and n are as defined in Formula 1.

3. The modified polyimide according to claim 1 , further comprising, in its main chain, one or more repeating structures represented by Formulae 5a to 5c:

wherein R a and R b are each independently selected from the group consisting of aromatic, alicyclic, and aliphatic divalent organic groups,

wherein R c and R d are each independently selected from the group consisting of aromatic, alicyclic, and aliphatic divalent organic groups, and

wherein R e and R f are each independently selected from the group consisting of aromatic, alicyclic, and aliphatic divalent organic groups.

4. The modified polyimide according to claim 1 , wherein D in Formula 1 is selected from the group consisting of vinyl, alkyne, acrylate, carboxyl, amide, amino, epoxy, isocyanate, cyano, acid anhydride, mercapto, silanol, alkoxysilane, hydroxyl, oxazoline groups, and combinations thereof.

5. The modified polyimide according to claim 1 , wherein D in Formula 1 is selected from acrylate, epoxy, isocyanate, mercapto groups, and combinations thereof.

6. The modified polyimide according to claim 1 , wherein in Formula 4, X 1 , X 2 , X 3 , and X 4 are each independently a tetravalent organic group derived from an aromatic tetracarboxylic dianhydride and Y 1 , Y 2 , and Y 3 are each independently a divalent organic group derived from an aromatic diamine.

7. The modified polyimide according to claim 1 , wherein the modified polyimide of Formula 4 is prepared by reacting a polyimide compound represented by Formula 3:

wherein X 1 , X 2 , X 3 , and X 4 are each independently a tetravalent organic group derived from a tetracarboxylic dianhydride, Y 1 , Y 2 , and Y 3 are each independently a divalent organic group derived from a diamine, and w and z are each independently an integer of 1 or greater, with an isocyanate compound represented by Formula 2:

wherein D, R, and n are as defined in Formula 1.

8. The modified polyimide according to claim 1 , wherein modified polyimide has a number average molecular weight of 500 to 80,000 g/mol.

9. The modified polyimide according to claim 1 , wherein in Formula 4, the sum of p+q+r+v is an integer from 5 to 100.

10. The modified polyimide according to claim 1 , wherein the ratio of the weight average molecular weight to the number average molecular weight of the modified polyimide is 1 or greater.

11. The modified polyimide according to claim 2 , wherein the compound of Formula 2 is a compound represented by Formula 2a:

wherein R 1 is a C 1 - C 18 alkylene group, a C 6 - C 24 arylene group or a divalent organic group interrupted by at least one ether, ester, urethane or amide bond as a linker, and R 2 is a hydrogen atom or a C 1 -C 18 alkyl group.

12. The modified polyimide according to claim 7 , wherein the polyimide of Formula 3 is prepared by reacting a tetracarboxylic dianhydride with a diamine in a molar ratio of 1:1 to 1.8:1.

13. A curable resin composition comprising the modified polyimide according to claim 1 , a thermal polymerization or photopolymerization initiator, and a solvent.

14. The curable resin composition according to claim 13 , wherein the solvent is selected from N,N-diethylacetamide (DEAc), N,N-diethylformamide (DEF), N-ethylpyrrolidone, and mixtures thereof.

15. The curable resin composition according to claim 13 , further comprising a polymerizable compound having an ethylenically unsaturated bond, a urethane (meth)acrylate compound or a mixture thereof.

16. A polyimide film obtained by curing the curable resin composition according to claim 13 .

17. The polyimide film according to claim 16 , wherein the polyimide film has a yellowness index (YI) of 7 or less, as measured at a thickness of 10 μm or more.

18. A method for preparing a modified polyimide having terminal curable functional groups, represented by Formula 4:

wherein X 1 , X 2 , X 3 , and X 4 are each independently a tetravalent organic group derived from a tetracarboxylic dianhydride, Y 1 , Y 2 , and Y 3 are each independently a divalent organic group derived from a diamine, p, q, r, and v are each independently an integer of 0 or greater, with the proviso that p, q, r, and v are not simultaneously 0, D is a heat curable or photocurable functional group, R is a divalent or higher polyvalent organic group, and n is an integer of 1 or greater, the method comprising reacting a tetracarboxylic dianhydride with a diamine in a polymerization solvent to prepare a polyamic acid, imidizing the polyamic acid to prepare a polyimide having terminal acid dianhydride groups, represented by Formula 3:

wherein X 1 , X 2 , X 3 , X 4 , Y 1 , Y 2 , and Y 3 are as defined in Formula 4 and w and z are each independently an integer of 1 or greater, and reacting the polyimide of Formula 3 with a compound represented by Formula 2:

wherein D, R, and n are as defined in Formula 4.

19. The method according to claim 18 , wherein the polymerization solvent is selected from N,N-diethylacetamide (DEAc), N,N-diethylformamide (DEF), N-ethylpyrrolidone, and mixtures thereof.

Assignees

• Lg Chemical Ltd

Inventors

• Yun Cheolmin
• Kim Kyungjun

Classifications

• C08G73/1017

  in the form of (mono)amine · CPC title

• C08G73/1025

  polymerised by radiations · CPC title

• C08G73/1032

  characterised by the solvent(s) used · CPC title

• C09D7/20

  Diluents or solvents · CPC title

• C08G73/1053

  with oxygen only in the tetracarboxylic moiety · CPC title