Polymerisable oligomeric liquid crystal, polymerisable medium and polymerised liquid crystal film

Patent metadata

Field	Value
Publication number	US-12565617-B2
Application number	US-202318532334-A
Country	US
Kind code	B2
Filing date	Dec 7, 2023
Priority date	Dec 8, 2022
Publication date	Mar 3, 2026
Grant date	Mar 3, 2026

Abstract

A polymerisable oligomeric liquid crystal (LC) and a polymerisable LC medium comprising the polymerisable oligomeric LC together with one or more mono-, di- or multireactive mesogenic compounds. Furthermore, a method for the preparation of the oligomeric LC, a birefringent polymer film obtainable from the polymerisable LC medium, and a method of preparation of such a polymer film. Also, the use of the polymer film as optical component, in particular as ultra-thin polariser (UTP) in a liquid crystal display (LCD), for contrast enhancement in an organic light emitting device (OLED), or for AR/AV/VR applications.

First claim

The invention claimed is:

1 . A polymerisable liquid crystal medium comprising one or more mono-, di- or multireactive liquid crystal or mesogenic compounds and one or more polymerisable, oligomeric liquid crystal or mesogenic compounds, wherein the at least one polymerisable oligomeric liquid crystal or mesogenic compound comprises one or more compounds of formula O:
P 1 -Sp 1 -[MG 1 -X 1 -E-X 2 ] n -MG 1 -Sp 2 -P 2   O
wherein P 1 and P 2 independently of each other denote a polymerisable group, Sp 1 and Sp 2 independently of each other are a spacer group or a single bond, X 1 and X 2 independently of each other denote —S—, —O— or NR x , E is alkylene having 2 to 20 C atoms, which is optionally mono- or polysubstituted by F, Cl, Br, I or CN and in which, in addition, one or more non-adjacent CH 2 groups may each be replaced, independently of one another, by —O—, —S—, —NH—, —NR x —, —SiR x R y —, —CO—, —COO—, —OCO—, —OCO—O—, —S—CO—, —CO—S—, —NR x —CO—O—, —O—CO—NR x —, —NR x —CO—NR y —, —CH═CH—or —C═C— in such a way that O and/or S atoms are not linked directly to one another, MG 1 is a rod-shaped mesogenic group, which is selected of formula M
-(A 1 -Z 1 ) a -A 2 -  M

wherein A 1 and A 2 denote, in case of multiple occurrence independently of one another, an aromatic or alicyclic group, which optionally contains one or more heteroatoms selected from N, O and S, and is optionally mono- or polysubstituted by L, L is P-Sp-, F, Cl, Br, I, —CN, —NO 2 , —NCO, —NCS, —OCN, —SCN, —C(═O)NR x R y , —C(═O)OR x , —C(═O)R x , —NR x R y , —OH, —SF 5 , optionally substituted silyl, aryl or heteroaryl with 1 to 12 C atoms, and straight chain alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy with 1 to 12 C atoms or branched alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy with 3 to 12 C atoms, wherein one or more H atoms are optionally replaced by F or Cl, R x and R y independently of each other denote H or alkyl with 1 to 12 C-atoms, Z 1 denotes, in case of multiple occurrence independently of one another, —O—, —S—, —CO—, —COO—, —OCO—, —S—CO—, —CO—S—, —O—COO—, —CO—NR x —, —NR x —CO—, —NR x —CO—NRY, —NR x —CO—O—, —O—CO—NR x —, —OCH 2 —, —CH 2 O—, —SCH 2 —, —CH 2 S—, —CF 2 O—, —OCF 2 —, —CF 2 S—, —SCF 2 —, —CH 2 CH 2 —, —(CH 2 ) n1 , —CF 2 CH 2 —, —CH 2 CF 2 —, —CF 2 CF 2 —, —CH═N—, —N═CH—, —N═N—, —CH═CR x —, —CY 1 =CY 2 —, —C═C—, —CH═CH—COO—, —OCO—CH═CH—or a single bond, Y 1 and Y 2 independently of each other denote H, F, Cl or CN, a is 1, 2, 3 or 4, n1 is an integer from 1 to 10, n is the average number of repeat units per molecule of compound of formula O and is from 1 to 10.

2 . The polymerisable LC medium according to claim 1 , which exhibits a smectic B phase.

3 . The polymerisable LC medium according to claim 2 , which shows a sequence nematic phase—smectic A phase—smectic B phase with decreasing temperature.

4 . The polymerisable LC medium according to claim 1 , wherein the one or more compounds of formula O comprise one or more compounds of formula O1:

wherein n is the average number of repeat units per molecule of compound of formula O1 and is from 1 to 10, e is 1, 2, 3 or 4, R m is H or CH 3 , and M is selected from the following formulae:

wherein L is P-Sp-, F, Cl, Br, I, —CN, —NO 2 , —NCO, —NCS, —OCN, —SCN, —C(═O) NR x R y , —C(═O)OR*, —C(═O)R x , —NR x R y , —OH, —SF 5 , optionally substituted silyl, aryl or heteroaryl with 1 to 12 C atoms, and straight chain alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy with 1 to 12 C atoms or branched alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy with 3 to 12 C atoms, wherein one or more H atoms are optionally replaced by F or Cl, r is 0, 1, 2, 3, or 4, and s is an integer from 1 to 20.

5 . The polymerisable LC medium according to claim 1 , wherein the concentration of the polymerisable oligomeric liquid crystal or mesogenic compound is from 0.05 to 15%.

6 . The polymerisable LC medium according to claim 1 , which contains one or more di- or multireactive mesogenic compounds selected from formula DRM:
P 1 -Sp 1 -MG-Sp 2 -P 2   DRM
wherein MG is a rod-shaped mesogenic group, which is selected of formula M
-(A 1 -Z 1 ) a -A 2 -  M.

7 . The polymerisable LC medium according to claim 1 , wherein the concentration of di- or multireactive mesogenic compounds is from 5 to 70% by weight.

8 . The polymerisable LC medium according to claim 6 , comprising one or more monoreactive mesogenic compounds selected from formula MRM:
P 1 -Sp 1 -MG-R  MRM
wherein R denotes P-Sp-, F, Cl, Br, I, —CN, —NO 2 , —NCO, —NCS, —OCN, —SCN, —C(═O)NR x R y , —C(═O)X, —C(═O)OR x , —C(═O) RY, —NR x R y , —OH, —SF 5 , optionally substituted silyl, straight chain or branched alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy with 1 to 12 1 to 6 C atoms, wherein one or more H atoms are optionally replaced by F or Cl, X is halogen, and R x and R y are independently of each other H or alkyl with 1 to 12 C-atoms.

9 . The polymerisable LC medium according to claim 1 , wherein the concentration of the monoreactive mesogenic compounds is from 1 to 80% by weight.

10 . The polymerisable LC medium according to claim 1 , further comprising one or more dyes or chromophores.

11 . The polymerisable LC medium according to claim 10 , wherein the concentration of the dye(s) is from 0.1 to 10% by weight.

12 . A polymerisable oligomeric liquid crystal or mesogenic compound of formula O1:

wherein n is the average number of repeat units per molecule of compound of O1 and is from 1 to 10, e is 1, 2, 3 or 4, R m is H or CH 3 , and M is selected from the following formulae:

wherein L is P-Sp-, F, Cl, Br, I, —CN, —NO 2 , —NCO, —NCS, —OCN, —SCN, —C(═O)NR x R y , —C(═O)OR x , —C(═O)R x , —NR x R y , —OH, —SF 5 , optionally substituted silyl, aryl or heteroaryl with 1 to 12 C atoms, and straight chain alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy with 1 to 12 C atoms or branched alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy with 3 to 12 C atoms, wherein one or more H atoms are optionally replaced by F or Cl, r is 0, 1, 2, 3, or 4, and s is an integer from 1 to 20.

13 . A process of preparing the polymerisable LC medium of claim 1 , wherein P 1 and P 2 denote an acrylate or methacrylate group, and wherein the compound of formula O is formed by the step of reacting a compound of formula MD
H 2 C═CH—CO—O-Sp 1 -MG 1 -Sp 2 -O—CO—CH═CH 2   MD
wherein R m denotes H or CH 3 , with a compound of formula DT
HX 1 -E-X 2 H  DT

in the presence of catalyst.

14 . The process of claim 13 , wherein the compound of formula MD is selected from subformula MD1
H 2 C=CR m —CO—O-M-O—CO—CR m =CH 2   MD1
wherein M is selected from formulae M-1, M-2 and M-3

and R m is H or CH 3 ,
wherein the compound of formula DT is selected from subformula DT1
HS—(CH 2 CH 2 O) e

Assignees

• Merck Patent Gmbh

Inventors

• Liu Danqing
• Zhan Yuanyuan
• Barmpoutsis Efstathios
• Broer Dirk Jan

Classifications

• C09K2019/0448

  the end chain group being a polymerizable end group, e.g. -Sp-P or acrylate · CPC title

• C09K19/601

  Azoic · CPC title

• C09K2019/2078

  Ph-COO-Ph-COO-Ph · CPC title

• H10K59/8791

  Arrangements for improving contrast, e.g. preventing reflection of ambient light · CPC title

• G02F1/133528

  Polarisers · CPC title