Polyimide precursor modified with dicarboxylic acid anhydride, imidized polyimide and liquid crystal aligning agent using it

Patent metadata

Field	Value
Publication number	US-9447240-B2
Application number	US-201214114409-A
Country	US
Kind code	B2
Filing date	Apr 27, 2012
Priority date	Apr 28, 2011
Publication date	Sep 20, 2016
Grant date	Sep 20, 2016

Abstract

To provide a polyimide precursor and/or polyimide which has an excellent solubility in various organic solvents, and with which a liquid crystal alignment film can be obtained which is excellent in a rubbing resistance and which is hardly deteriorated even by irradiation with backlight.
A polyimide precursor having its terminal amino group modified with at least one alicyclic epoxydicarboxylic acid anhydride selected from the group consisting of compounds of the formulae [1] and [2], or a polyimide obtained by imidizing it:

wherein Y is a C 1-2 alkylene or an oxygen atom, and R 1 is a hydrogen atom or an organic group represented by —X 1 —X 2 —X 3 , wherein X 1 is a single bond or —CH 2 —, X 2 is a single bond or —O—, and X 3 is a C 1-20 alkyl group, a C 1-20 haloalkyl group or a C 1-20 alkyl group containing a cyano group.

First claim

The invention claimed is:

1. A polyimide precursor, having its terminal amino group modified with at least one alicyclic epoxydicarboxylic acid anhydride selected from the group consisting of a compound of formulae [1] and a compound of formula [2], or a polyimide thereof:

wherein:
Y is a C 1-2 alkylene or an oxygen atom;
R 1 is a hydrogen atom or an organice group represented by —X 1 —X 2 —X 3 ;
X 1 is a single bond or —CH 2 —;
X 2 is a single bond or —O—; and
X 3 is a C 1-20 alkyl group, a C 1-20 haloalkyl group or a C 1-20 alkyl group containing a cyano group.

2. The polyimide precursor or polyimide according to claim 1 , wherein the alicyclic epoxydicarboxylic acid anhydride is at least one compound selected from the group consisting of a compound represented by formula [A], a compound represented by formula [B], and a compound represented by formula [C]:

wherein R is a C 1-20 alkyl group, a C 1-20 haloalkyl group or a C 1-20 alkyl group containing a cyano group.

3. A liquid crystal aligning agent, comprising at least one of the polyimide precursor, or the polyimide obtained by imidizing the polyimide precursor according to claim 2 .

4. A liquid crystal aligning agent, comprising at least one of the polyimide precursor, or the polyimide obtained by imidizing the polyimide precursor according to claim 1 .

5. A liquid crystal alignment film obtained from the liquid crystal aligning agent of claim 4 .

6. A liquid crystal display device, comprising the liquid crystal alignment film of claim 5 .

7. A method for producing a polyimide precursor having its terminal amino group modified, the method comprising reacting at least one alicyclic epoxydicarboxylic acid anhydride selected from the group consisting of a compound of formulae [1] and a compound of [2] with a polyimide precursor having an amino group at its terminal:

wherein:
Y is a C 1-2 alkylene or an oxygen atom;
R 1 is a hydrogen atom or an organic group represented by —X 1 —X 2 —X 3 ;
X 1 is a single bond or —CH 2 —;
X 2 is a single bond or —O—; and
X 3 is a C 1-20 alkyl group, a C 1-20 haloalkyl group or a C 1-20 alkyl group containing a cyano group; and
wherein said polymide precursor is a polyamic acid or a polyamic acid ester.

8. The method according to claim 7 , wherein the polyimide precursor is a polyimide precursor having from 50 to 100% of its terminal amino groups, relative to the total number of terminal groups, derived from a tetracarboxylic acid and a diamine.

9. A method for producing a polyimide having its terminal amino group modified, the method comprising
imidizing a polyimide precursor selected from the group consisting of a polyamic acid or a polyamic acid ester to obtain a polyimide,
reacting the polyimide with at least one alicyclic epoxydicarboxylic acid anhydride selected from the group consisting of a compound of formulae [1] and a compound of [2] with a polyimide precursor having an amino group at its terminal:

wherein:
Y is a C 1-2 alkylene or an oxygen atom;
R 1 is a hydrogen atom or an organic group represented by —X 1 —X 2 —X 3 ;
X 1 is a single bond or —CH 2 —;
X 2 is a single bond or —O—; and
X 3 is a C 1-20 alkyl group, a C 1-20 haloalkyl group or a C 1-20 alkyl group containing a cyano group.

10. The method according to claim 9 , wherein the polyimide precursor is a polyimide precursor having from 50 to 100% of its terminal amino groups, relative to the total number of terminal groups, derived from a tetracarboxylic acid and a diamine.

11. A compound represented by the formula [1]:

wherein R is a C 1-20 alkyl group, a C 1-20 haloalkyl group or a C 1-20 alkyl group containing a cyano group.

12. The compound according to claim 11 , wherein R is a n-tetradecyl group.

13. A process for producing the compound of claim 11 represented by the formula [1]:

the process comprising:
reacting furfuryl alcohol with a substituted alkyl halide represented by the formula [4]:
RX  [4],

wherein X is a halogen;

in the presence of a base to obtain a compound represented by the formula [5]:

reacting the compound represented by the formula [5] with acetylenedicarboxylic acid to obtain a compound represented by the formula [6]:

oxidizing the compound represented by the formula [6] to obtain a compound represented by the formula [3]:

reducing the compound represented by the formula [3] to obtain a compound represented by the formula [2]:

and
dehydrating the compound represented by formula [2] with a dehydrating agent to form the compound represented by formula [1],
wherein R is a C 1-20 alkyl group, a C 1-20 haloalkyl group or a C 1-20 alkyl group containing a cyano group.

14. The process according to claim 13 , wherein R is a n-tetradecyl group.

15. A compound represented by the formula [2]:

wherein R is a C 1-20 alkyl group, a C 1-20 haloalkyl group or a C 1-20 alkyl group containing a cyano group.

16. The compound according to claim 15 , wherein R is a n-tetradecyl group.

17. A compound represented by the formula [3]:

wherein R is a C 1-20 alkyl group, a C 1-20 haloalkyl group or a C 1-20 alkyl group containing a cyano group.

18. The compound according to claim 17 , wherein R is a n-tetradecyl group.

Assignees

• Suzuki Hideo
• Noda Takahiro
• Nissan Chemical Ind Ltd

Inventors

• Suzuki Hideo
• Noda Takahiro

Classifications

• C08G73/10 Primary

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

• C07D493/22

  in which the condensed system contains four or more hetero rings · CPC title

• C08G73/101

  containing chain terminating or branching agents · CPC title

• C07D493/18 Primary

  Bridged systems · CPC title

• C08G73/1014

  in the form of (mono)anhydrid · CPC title