Precursor for polyimide and use thereof

Patent metadata

Field	Value
Publication number	US-11319410-B2
Application number	US-201815867942-A
Country	US
Kind code	B2
Filing date	Jan 11, 2018
Priority date	Jan 11, 2017
Publication date	May 3, 2022
Grant date	May 3, 2022

Abstract

The present invention provides an amic acid ester oligomer having a structure of Formula (1) or (1′):wherein G, P, R, Rx, D, E and m are those as defined in the specification. The present invention also provides a polyimide precursor composition or a photosensitive polyimide precursor composition comprising the amic acid ester oligomer, as well as a polyimide prepared from the composition.

First claim

What is claimed is:

1. An amic acid ester oligomer, having a structure of Formula (1) or (1′) below:

wherein
G is each independently a tetravalent organic group;
P″ is each independently a divalent organic group;
R is C 1 -C 14 alkyl, C 6 -C 14 aryl unsubstituted or substituted with one or more groups selected from the group consisting of hydroxyl and C 1 -C 4 alkyl, or a group having an ethylenically unsaturated bond;
R x is each independently H, C 1 -C 8 alkyl, or a group having an ethylenically unsaturated bond;
D is methyl, ethyl, propyl, butyl, or a group selected from the group consisting of:

 where t is an integer from 1 to 5;
two E are the same or different, and are each independently H, C 1 -C 14 alkyl, alkylamino, alkylthio, C 4 -C 10 cycloalkyl, C 6 -C 14 aryl, nitrogen-containing heterocyclyl, oxygen-containing heterocyclyl, or

 with the provision that two E attached to the same carbon atom are not H at the same time; or two E together with C═N— to which they are attached form

R 16 is each independently halo, hydroxyl, C 1 -C 8 alkoxy, C 1 -C 8 haloalkyl, or —NO 2 ;
i is an integer from 0 to 3;
j is an integer from 0 to 3; and
m is an integer from 1 to 100.

2. The oligomer according to claim 1 , wherein the group having an ethylenically unsaturated bond is selected from the group consisting of: ethenyl, propenyl, methylpropenyl, n-butenyl, iso-butenyl, ethenylphenyl, propenylphenyl, propenyloxymethyl, propenyloxyethyl, propenyloxypropyl, propenyloxybutyl, propenyloxypentyl, propenyloxyhexyl, methylpropenyloxymethyl, methylpropenyloxyethyl, methylpropenyloxypropyl, methylpropenyloxybutyl, methylpropenyloxypentyl, methylpropenyloxyhexyl, and a group of Formula (2):

wherein R 7 is phenylene, C 1 -C 8 alkylene, C 2 -C 8 alkenylene, C 3 -C 8 cycloalkylene, C 1 -C 8 hydroxyalkylene or

 wherein n′ is an integer from 1 to 4; and R 8 is hydrogen or C 1 -C 4 alkyl.

3. The oligomer according to claim 1 , wherein R is selected from the group consisting of:

4. The oligomer according to claim 1 , wherein the tetravalent organic group is each independently selected from the group consisting of:

wherein X is each independently hydrogen, halo, C 1 -C 4 perfluoroalkyl, or C 1 -C 4 alkyl; and A and B at each occurrence are each independently a covalent bond, C 1 -C 4 alkylene unsubstituted or substituted with one or more groups selected from hydroxyl and C 1 -C 4 alkyl, C 1 -C 4 perfluoroalkylene, C 1 -C 4 alkyleneoxy, silylene, —O—, —S—, —C(O)—, —OC(O)—, —S(O) 2 —, —C(═O)O—(C 1 -C 4 alkylene)-OC(═O)—, —CONH—, phenyl, biphenylyl, or

 wherein K is —O—, —S(O) 2 —, C 1 -C 4 alkylene or C 1 -C 4 perfluoroalkylene.

5. The oligomer according to claim 1 , wherein the tetravalent organic group is each independently selected from the group consisting of:

wherein Z is each independently hydrogen, methyl, trifluoromethyl or halo.

6. The oligomer according to claim 1 , wherein the divalent organic group is each independently selected from the group consisting of:

wherein:
R 9 is each independently H, C 1 -C 4 alkyl, C 1 -C 4 perfluoroalkyl, C 1 -C 4 alkoxy, halo, —OH, —COOH, —NH 2 or —SH;
a is each independently an integer from 0 to 4;
b is each independently an integer from 0 to 4; and
R 10 is a covalent bond or a group selected from the group consisting of:

wherein
c and d are each independently an integer from 1 to 20;
R 9 and a are as defined above;
R 12 is —S(O) 2 —, —C(O)—, a covalent group, C 1 -C 4 alkyl or C 1 -C 4 perfluoroalkyl;
R 11 is each independently hydrogen, halo, phenyl, C 1 -C 4 alkyl, or C 1 -C 4 perfluoroalkyl; and
w and y are each an integer from 1 to 3.

7. The oligomer according to claim 6 , wherein the divalent organic group is each independently selected from the group consisting of:

wherein:
a is each independently an integer from 0 to 4; and
Z is each independently hydrogen, methyl, trifluoromethyl or halo.

8. The oligomer according to claim 1 , wherein the two E are each independently H, phenyl,

with the provision that two E are not H at the same time;
or the two E together with C═N— to which they are attached form

9. The oligomer according to claim 1 , wherein m is an integer from 2 to 25.

10. A polyimide precursor composition, comprising an oligomer according to claim 1 and a solvent.

11. The composition according to claim 10 , wherein the solvent is selected from the group consisting of dimethyl sulfoxide, diethyl sulfoxide, phenol, o-cresol, m-cresol, p-cresol, xylenol, halogenated phenol, pyrocatechol, tetrahydrofuran, dioxane, dioxolane, propylene glycol methyl ether, tetraethylene glycol dimethyl ether, diethylene glycol dibutyl ether, methanol, ethanol, butanol, butylcellosolve, γ-butyrolactone, xylene, toluene, hexamethylphosphoramide, propylene glycol methyl ether acetate,

and a mixture thereof;
wherein
R 1 ″ is each independently H, C 1 -C 20 alkyl, C 2 -C 20 alkenyl, or C 2 -C 20 alkynyl;
R 7 ″ is H or C 1 -C 3 alkyl;
R 2 ″ is H, C 1 -C 15 alkyl, or C 4 -C 8 cycloalkyl;
R 3 ″ and R 4 ″ are each independently C 1 -C 10 alkyl, or R 3 ″ and R 4 ″ form, together with the nitrogen atom to which they are attached, a 5- to 6-membered heterocyclic ring; and
R 6 ″ is C 1 -C 15

Assignees

• Eternal Mat Co Ltd

Inventors

• Huang Po-Yu
• Wu Chung-Jen
• Chou Meng-Yen
• Ho Chang-Hong
• Chiang Shun-Jen
• Cheng Chung-Kai

Classifications

• C08G73/101 Primary

  containing chain terminating or branching agents · CPC title

• C08G73/121 Primary

  Preparatory processes from unsaturated precursors and polyamines · CPC title

• G03F7/0046

  with perfluoro compounds, e.g. for dry lithography (G03F7/0048 takes precedence) · CPC title

• C08G73/12 Primary

  Unsaturated polyimide precursors · CPC title

• C08G73/105

  with oxygen only in the diamino moiety · CPC title