Polymerisable liquid crystal material and polymerised liquid crystal film

Patent metadata

Field	Value
Publication number	US-11820932-B2
Application number	US-201716336974-A
Country	US
Kind code	B2
Filing date	Sep 25, 2017
Priority date	Sep 28, 2016
Publication date	Nov 21, 2023
Grant date	Nov 21, 2023

Abstract

A polymerisable LC material comprising at least one di- or multireactive mesogenic compound and at least one compound of formula CO-1,wherein R1, R2, L1, L2, L3, and n have the meanings as given in claim 1. Furthermore, a method for preparation of the LC material, a polymer film with improved thermal durability obtainable from the corresponding polymerisable LC material, a method of preparation of such polymer film, and the use of such polymer film and said polymerisable LC material for optical, electro-optical, decorative or security devices.

First claim

The invention claimed is:

1. A polymerisable LC material comprising at least one di- or multireactive mesogenic compound, at least one compound of formula CO-1,

wherein
R 1 and R 2 each denote alkyl, alkoxy or mono- oligo- or polyfluorinated alkyl or alkoxy,
L 1 denotes H, alkyl, alkoxy, thioalkyl, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy; halogen, CN, OCN, SCN, or mono- oligo- or polyfluorinated alkyl or alkoxy atoms; or -(Sp 31 -A 31 ),
L 2 and L 3 each denote H, alkyl, mono- oligo- or polyfluorinated alkyl, or -(Sp 31 -A 31 ),
Sp 31 denotes a C 1 -C 12 alkylene radical or a single bond,
A 31 denotes an aryl, heteroaryl, (non-aromatic) alicyclic or heterocyclic group, each optionally having one or more substituents, which are selected from the group consisting of silyl, sulfo, sulfonyl, formyl, amine, imine, nitrile, mercapto, nitro, halogen, C 1-12 alkyl, C 6-12 aryl, C 1-12 alkoxy, hydroxyl, and combinations of these groups, and
n denotes 1, and
at least one monoreactive mesogenic compound of the formula

wherein
P 0 is, in case of multiple occurrence independently of one another, an acryl, methacryl, oxetane, epoxy, vinyl, heptadiene, vinyloxy, propenyl ether or styrene group,
x is 0 or identical or different integers from 1 to 12,
z is each and independently, 0 or 1, with z being 0 if the adjacent x is 0,

R 0 is alkyl, alkoxy, thioalkyl, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy with 1 to 15 C atoms for the alkyl and alkoxy portions or denotes Y 0 ,
Y 0 is F, Cl, CN, NO 2 , OCH 3 , OCN, SCN, SF 5 , or mono- oligo- or polyfluorinated alkyl or alkoxy with 1 to 4 C atoms,
w is 0 or 1,
wherein benzene rings are optionally additionally substituted with one or more identical or different groups L, and
L is P-Sp-, F, Cl, Br, I, —CN, —NO 2 , —NCO, —NCS, —OCN, —SCN, —C(═O)NR 00 R 000 , —C(═O)OR 00 , —C(═O)R 00 , —NR 00 R 000 , —OH, —SF 5 , optionally substituted silyl, aryl with 6 to 25 C atoms or heteroaryl with 2 to 25 C atoms, straight chain or branched alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy with 1 to 12 C atoms for the alkyl or alkoxy portions of the straight chain groups and 3-12 atoms for the alkyl or alkoxy portions of the branched groups, wherein one or more H atoms are optionally replaced by F or Cl,
P is a polymerizable group,
Sp is a spacer group or a single bond,
and
R 00 and R 000 independently of each other denote H or alkyl with 1 to 12 C-atoms,
and additionally at least one polymerizable compound of formula ND

wherein
U 1,2 are independently of each other selected from the group consisting of

including their mirror images, wherein the rings U 1 and U 2 are each bonded to the group —(B) q — via the axial bond, and one or two non-adjacent CH 2 groups in these rings are optionally replaced by O and/or S, and the rings U 1 and U 2 are optionally substituted by one or more groups L,

Q 1,2 are independently of each other CH or SiH,
Q 3 is C or Si,
B is in each occurrence independently of one another —C≡C—, —CY 1 ═CY 2 — or an optionally substituted aromatic or heteroaromatic group,
Y 1,2 are independently of each other H, F, Cl, CN or R 0 , q is an integer from 1 to 10, preferably 1, 2, 3, 4, 5, 6 or 7,
A 1-4 are independently of each other non-aromatic, aromatic or heteroaromatic carbocyclic or heterocyclic groups, which are optionally substituted by one or more groups R 5 , and wherein each of -(A 1 -Z 1 ) m —U 1 —(Z 2 -A 2 ) n - and -(A 3 -Z 3 ) o —U 2 —(Z 4 -A 4 ) p - does not contain more aromatic groups than non-aromatic groups,
Z 1-4 are independently of each other —O—, —S—, —CO—, —COO—, —OCO—, —O—COO—, —CO—NR 0 —, —NR 0 —CO—, —NR 0 —CO—NR 00 —, —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 ) 3 —, —(CH 2 ) 4 —, —CF 2 CH 2 —, —CH 2 CF 2 —, —CF 2 CF 2 —, —CH═CH—, —CY 1 ═CY 2 —, —CH═N—, —N═CH—, —N═N—, —CH═CR 0 —, —C≡C—, —CH═CH—COO—, —OCO—CH═CH—, CR 0 R 00 or a single bond,

R 0 and R 00 are independently of each other H or alkyl with 1 to 12 C-atoms,
m and n are independently of each other 0, 1, 2, 3 or 4,
and p are independently of each other 0, 1, 2, 3 or 4, and
R 1-5 are each independently H, halogen, —CN, —NC, —NCO, —NCS, —OCN, —SCN, —C(═O)NR 0 R 00 , —C(═O)X 0 , —C(═O)R 0 , —NH 2 , —NR 0 R 00 , —SH, —SR 0 , —SO 3 H, —SO 2 R 0 , —OH, —NO 2 , —CF 3 , —SF 5 , P-Sp-, optionally substituted silyl, or carbyl or hydrocarbyl with 1 to 40 C atoms that is optionally substituted and optionally comprises one or more hetero atoms, or denote P or P-Sp-, or are substituted by P or P-Sp-, wherein the compounds comprise at least one group R 1 -5 denoting or being substituted by P or P-Sp-.

2. A polymerisable LC material according to claim 1 , wherein the at least one di- or multireactive mesogenic compound is selected from formula DRM
P 1 -Sp 1 -MG-Sp 2 -P 2   DRM

wherein
P 1 and P 2 independently of each other denote a polymerisable group,
Sp′ and Sp 2 independently of each other are a spacer group or a single bond, and
MG is a rod-shaped mesogenic group selected from formula MG
-(A 1 -Z 1 ) n -A 2 -  MG

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 1 ,
L 1 is P-Sp-, F, Cl, Br, I, —CN, —NO 2 , —NCO, —NCS, —OCN, —SCN, —C(═O)NR 00 R 000 , —C(═O)OR 00 , —C(═O)R 00 , —NR 00 R 000 , —OH, —SF 5 , optionally substituted silyl, aryl with 6 to 25 C atoms or heteroaryl with 2 to 25 C atoms, straight chain or branched alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy with 1 to 12 C atoms for the alkyl or alkoxy portions of the straight chain groups and 3-12 C atoms for the alkyl or alkoxy portions of the branched groups, wherein one or more H atoms are optionally replaced by F or Cl,
R 00 and R 000 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 00 —, —NR 00 —CO—, —NR 00 —CO—NR 000 , —NR 00 —CO—O—, —O—CO—NR 00 —, —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 00 —, —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,
n is 1, 2, 3 or 4, and
n1 is an integer from 1 to 10.

3. A polymerisable LC material according to claim 2 , which comprises at least one direactive mesogenic compound selected from the following formulae,

wherein
P 0 is, in case of multiple occurrence independently of one another, an acryl, methacryl, oxetane, epoxy, vinyl, heptadiene, vinyloxy, propenyl ether or styrene group,
L has, on ea

Assignees

• Merck Patent Gmbh

Inventors

• Song Dong-Mee
• Choi Yong-Hyun
• Kang Jae-Hyun
• Yun Yong-Kuk

Classifications

• C09K19/54 Primary

  Additives having no specific mesophase {characterised by their chemical composition} · CPC title

• C08F222/26

  of unsaturated alcohols {(C08F222/1006 takes precedence)} · CPC title

• C09K19/3857

  containing at least one asymmetric carbon atom · CPC title

• C08F2800/20

  as weight or mass percentages · CPC title

• C09K2019/0448

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