Polyimide and polyimide film, prepared therefrom, for flexible display

Patent metadata

Field	Value
Publication number	US-11319409-B2
Application number	US-201816461601-A
Country	US
Kind code	B2
Filing date	Jan 17, 2018
Priority date	Jan 31, 2017
Publication date	May 3, 2022
Grant date	May 3, 2022

Abstract

Described is a polyimide prepared from a diamine containing a spiro or cardo group in a molecule structure, wherein the dimensional stability of the polyimide can be improved at a high temperature, and thus the polyimide can provide a polyimide film useful for a flexible substrate.

First claim

What is claimed is:

1. A polyimide comprising a polymerized and imidized product of a composition comprising a tetracarboxylic dianhydride and a diamine that is selected from the following formulae 1b to 1e,

wherein, in formulae 1c to 1e,
R 1 and R 2 are each independently a hydrogen atom or a substituent selected from a halogen atom, a hydroxyl group (—OH), a thiol group (—SH), a nitro group (—NO 2 ), a cyano group, an alkyl group having 1 to 10 carbon atoms, a halogenoalkoxy group having 1 to 4 carbon atoms, a halogenoalkyl group having 1 to 10 carbon atoms and an aryl group having 6 to 20 carbon atoms, and
wherein in Formula 1b, R 1 and R 2 are each independently a halogenoalkyl group having 1 to 10 carbon atoms.

2. The polyimide according to claim 1 , wherein the composition comprises the diamine selected from formulae 1b to 1e in an amount of 30 to 100 mol % based on the total content of the diamine.

3. The polyimide according to claim 1 , wherein a coefficient of thermal expansion (CTE) is 50 ppm/° C. or less as measured in the range of 100 to 250° C.

4. The polyimide according to claim 1 , wherein a glass transition temperature (Tg) is 330° C. or higher.

5. The polyimide according to claim 1 , wherein the composition further comprises the diamine of formula 6,

wherein, in formula 6,
R 31 and R 32 are each independently selected from a hydrogen atom, a halogen atom, a hydroxyl group (—OH), a thiol group (—SH), a nitro group (—NO 2 ), a cyano group, an alkyl group having 1 to 10 carbon atoms, a halogenoalkoxy group having 1 to 4 carbon atoms, a halogenoalkyl group having 1 to 10 carbon atoms and an aryl group having 6 to 20 carbon atoms,
n and m are each independently an integer of 0 to 4, and
Q 1 is selected from the group consisting of a single bond, —O—, —CR 18 R 19 -, —C(═O)—, —C(═O)O—, —C(═O)NH—, —S—, —SO 2 -, a phenylene group and a combination thereof, wherein R 18 and R 19 are each independently selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and a fluoroalkyl group having 1 to 10 carbon atoms.

6. A polyimide film for a flexible display comprising the polyimide of claim 5 .

7. A polyimide substrate for an Oxide TFT or LTPS comprising the polyimide of claim 5 .

8. A diamine represented by any one of the following formulae 1b to 1e,

wherein, in formulae 1c to 1e,
R 1 and R 2 are each independently a hydrogen atom or a substituent selected from a halogen atom, a hydroxyl group (—OH), a thiol group (—SH), a nitro group (—NO 2 ), a cyano group, an alkyl group having 1 to 10 carbon atoms, a halogenoalkoxy group having 1 to 4 carbon atoms, a halogenoalkyl group having 1 to 10 carbon atoms and an aryl group having 6 to 20 carbon atoms, and
wherein in Formula 1b, R 1 and R 2 are each independently a halogenoalkyl group having 1 to 10 carbon atoms.

9. The polyimide according to claim 1 , wherein the composition further comprises a diamine comprising one or more divalent organic group selected from the group consisting of following formulae 4a to 4e:

wherein, in formulae 4a to 4e,
R 21 to R 27 are each independently selected from an alkyl group having 1 to 10 carbon atoms, a halogen group, a hydroxy group, a carboxyl group, an alkoxy group having 1 to 10 carbon atoms and a fluoroalkyl group having 1 to 10 carbon atoms,
A 21 and A 22 are each independently selected from a single bond, —O—, —CR′R″—(wherein R′ and R″ are each independently selected from a hydrogen atom, an alkyl group having 1 to 10 carbon atoms and a haloalkyl group having 1 to 10 carbon atoms), —C(═O)—, —C(═O)O—, —C(═O)NH—, —S—, —SO—, —SO 2 -, —O[CH 2 CH 2 O]y (wherein y is an integer of 1 to 44), —NH(C=o)NH—, —NH(C═O)O—, a monocyclic or polycyclic cycloalkylene group having 6 to 18 carbon atoms, a monocyclic or polycyclic arylene group having 6 to 18 carbon atoms, and a combination thereof, and
b 1 , b 4 and b 5 are each independently an integer of 0 to 4, b 2 is an integer of 0 to 6, b 3 is an integer of 0 to 3, b 6 and b 9 are each independently an integer of 0 or 1, and b 7 and b 8 are each independently an integer of 0 to 10.

10. The polyimide according to claim 1 , wherein the diamine comprising one or more divalent organic group is selected from the group consisting of following formulae 5a to 5t,

wherein, in formula 5a to 5t, at least one hydrogen atom present in the divalent organic group is unsubstituted or substituted with a substituent selected from a halogen atom selected from —F, —Cl, —Br and —I, a hydroxyl group (—OH), a thiol group (—SH), a nitro group (—NO 2 ), a cyano group, an alkyl group having 1 to 10 carbon atoms, a halogenoalkoxy group having 1 to 4 carbon atoms, a halogenoalkyl group having 1 to 10 carbon atoms and an aryl group having 6 to 20 carbon atoms.

11. The polyimide according to claim 1 , wherein the tetracarboxylic dianhydride comprises one or more tetravalent organic structure selected from the group consisting of tetravalent organic groups represented by the following formulae 2a to 2e:

wherein, in formulae 2a to 2e,
R 11 to R 17 are each independently a hydrogen atom or a substituent selected from a halogen atom, a hydroxyl group (—OH), a thiol group (—SH), a nitro group (—NO 2 ), a cyano group, an alkyl group having 1 to 10 carbon atoms, a halogenoalkoxy group having 1 to 4 carbon atoms, a halogenoalkyl group having 1 to 10 carbon atoms and an aryl group having 6 to 20 carbon atoms,
a1 is an integer of 0 to 2, a2 may be an integer of 0 to 4, a3 is an integer of 0 to 8, a4 and a5 are each independently an integer of 0 to 3, a6 and a9 are each independently an integer of 0 to 3, and a7 and a8 are each independently an integer of 0 to 9, and
A 11 and A 12 are each independently selected from the group consisting of a single bond, —O—, —CR 18 R 19 -, —C(═O)—, —C(═O)NH—, —S—, —SO 2 -, a phenylene group and a combination thereof, wherein R 18 and R 19 are each independently selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and a fluoroalkyl group having 1 to 10 carbon atoms.

12. The polyimide according to claim 1 , wherein the tetracarboxylic dianhydride comprises a tetravalent organic group selected from the group consisting of the following formulae 3a to 3r in the structure:

wherein, in formula 31, A2 may be selected from the group consisting of a single bond, —O—, —C(═O)—, —C(═O)NH—, —S—, —SO 2 —, a phenylene group and a combination thereof and v is an integer of 0 or 1, and in formula 3r, x is an integer of 1 to 10.

13. The polyimide according to claim 1 , wherein a molar ratio of a total content of

Assignees

• Lg Chemical Ltd

Inventors

• Jeong Hye Won
• Koo Kichul
• Kim Kyungjun

Classifications

• H10D86/411

  characterised by materials, geometry or structure of the substrates · CPC title

• H10D86/60

  wherein the TFTs are in active matrices · CPC title

• G02F1/133305

  Flexible substrates, e.g. plastics, organic film · CPC title

• C08G73/1067 Primary

  Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound · CPC title

• C08G73/1042

  Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds · CPC title