US 11,939,510 B2
Polymerisable liquid crystal material and polymerised liquid crystal film
Eduardo Beltran Gracia, Southampton (GB); Kevin Adlem, Bournemouth (GB); Naomi Weare, Southampton (GB); and Hassan Norouzi-Arasi, Southampton (GB)
Assigned to MERCK PATENT GMBH, Darmstadt (DE)
Appl. No. 16/639,007
Filed by MERCK PATENT GMBH, Darmstadt (DE)
PCT Filed Aug. 13, 2018, PCT No. PCT/EP2018/071896
§ 371(c)(1), (2) Date Feb. 13, 2020,
PCT Pub. No. WO2019/034590, PCT Pub. Date Feb. 21, 2019.
Claims priority of application No. 17001387 (EP), filed on Aug. 15, 2017.
Prior Publication US 2020/0199453 A1, Jun. 25, 2020
This patent is subject to a terminal disclaimer.
Int. Cl. G02F 1/1333 (2006.01); C08F 220/38 (2006.01); C08J 5/18 (2006.01); C09K 19/04 (2006.01); C09K 19/32 (2006.01); C09K 19/38 (2006.01); C09K 19/54 (2006.01)
CPC C09K 19/3861 (2013.01) [C08F 220/387 (2020.02); C08J 5/18 (2013.01); C09K 19/04 (2013.01); C09K 19/32 (2013.01); C09K 19/54 (2013.01); C08F 2800/20 (2013.01); C08J 2333/14 (2013.01); C09K 2019/0444 (2013.01); C09K 2019/0448 (2013.01)] 27 Claims
 
1. A polymerizable LC material comprising:
(a) one or more compounds of formula T
RT1-(AT1ZT1)m1-GT1-(ZT2-AT2)m2-RT2  T
wherein
RT1 and RT2 each and independently from another denotes H or an optionally substituted hydrocarbon group having 1 to 20 carbon atoms in which a carbon atom may optionally be replaced with a heteroatom, and at least one of RT1 and RT2 denotes P-Sp-,
P denotes a polymerizable group
Sp denotes a spacer group,
AT1 and AT2 each and independently and in each occurrence denote a 1,4-phenylene group, a 1,4-cyclohexylene group, a pyridine-2,5-diyl group, a pyrimidine-2,5-diyl group, a naphthalene-2,6-diyl group, a naphthalene-1,4-diyl group, a tetrahydronaphthalene-2,6-diyl group, a decahydronaphthalene-2,6-diyl group, or a 1,3-dioxane-2,5-diyl group, whereby these groups may be unsubstituted or may be substituted with one or more of substituent groups L,
L denotes each and independently in each occurrence F, Cl, Br, I, a pentafluorosulfuranyl group, a nitro group, a cyano group, an isocyano group, an amino group, a hydroxyl group, a mercapto group, a methylamino group, a dimethylamino group, a diethylamino group, a diisopropylamino group, a trimethylsilyl group, a dimethylsilyl group, a thioisocyano group, or a C1-20-linear or C3-20-branched alkyl group, in which one —CH2— or two or more non-adjacent —CH2— may be each independently substituted with —O—, —S—,
—CO—, —COO—, —OCO—, —CO—S—, —S—CO—, —O—CO—O—,
—CO—NH—, —NH—CO—, —CH═CH—COO—, —CH═CH—OCO—,
—COO—CH═CH—, —OCO—CH═CH—, —CH═CH—, —CF═CF—, or —C═C—, and any hydrogen atom in the alkyl group may be substituted by F, or L may denote a group represented by P-Sp-,
ZT1 and ZT2 each independently represent —O—, —S—, —OCH2—, —CH2O—, —CH2CH2—, —CO—, —COO—, —OCO—, —CO—S—, —S—CO—,
—O—CO—O—, —CO—NH—, —NH—CO—, —OCO—NH—, —NH—COO—,
—NH—CO—NH—, —NH—O—, —O—NH—, —SCH2—, —CH2S—, —CF2O—, —OCF2—, —CF2S—, —SCF2—, —CH═CH—COO—, —CH═CH—OCO—, —COO—CH═CH—, —OCO—CH═CH—, —COO—CH2CH2—, —OCO—CH2CH2—, —CH2CH2—COO—,
—CH2CH2—OCO—, —COO—CH2—, —OCO—CH2—, —CH2—COO—,
—CH2—OCO—, —CH═CH—, —N═N—, —CH═N—, —N═CH—,
—CH═N—N═CH—, —CF═CF—, —C═C—, a single bond, or a group represented by —CR01R02O— or —OCR01R02—
whereby these groups may be unsubstituted or substituted with one or more of the substituent groups L as defined above,
T1 denotes a group selected from formulae T1-1 and T1-2 below,

OG Complex Work Unit Chemistry
WT1 denotes a group containing an aromatic group and/or non-aromatic group having 3 to 40 carbon atoms, which may be substituted, the aromatic group may be a hydrocarbon ring or a heterocyclic ring, and the non-aromatic group may be a hydrocarbon group or a group in which any carbon atom in a hydrocarbon group is substituted with a heteroatom provided that, oxygen atoms are not directly connected with each other,
WT2 denotes a hydrogen atom or a C1-20-linear or C3-20-branched alkyl group, in which one —CH2— or two or more non-adjacent —CH2— groups may be each independently substituted with —O—, —S—, —CO—, —COO—, —OCO—, —CO—S—, —S—CO—, —O—CO—O—, —CO—NH—,
—NH—CO—, —CH═CH—COO—, —CH═CH—OCO—,
—COO—CH═CH—, —OCO—CH═CH—, —CH═CH—, —CF═CF—, or
R01 and R02 each independently represent a hydrogen atom, F, Cl, Br, I, or a C1-20-linear or C3-20-branched alkyl group, in which one —CH2— or two or more non-adjacent —CH2— may be each independently replaced with —O—, —S—, —CO—, —COO—, —OCO—, —CO—S—, —S—CO—,
—O—CO—O—, —CO—NH—, —NH—CO—, —CH═CH—COO—,
—CH═CH—OCO—, —COO—CH═CH—, —OCO—CH═CH—,
—CH═CH—, —CF═CF—, or —C═C—, and any hydrogen atom in the alkyl group may be replaced with F or Cl;
GT1 denotes a group selected from formulae M-1 to M-8,

OG Complex Work Unit Chemistry
 —C═C—, and any hydrogen atom in the alkyl group may be replaced with F, or WT2 may denote a group of 2 to 30 carbon atoms, or 3-carbon atoms having at least one aromatic group, and the group may be unsubstituted or may be substituted with one or more of substituent groups L as defined above, or WT2 may denote a group by P-Sp-,
Y denotes a hydrogen atom, F, Cl, Br, I, a pentafluorosulfuranyl group, a nitro group, a cyano group, an isocyano group, an amino group, a hydroxyl group, a mercapto group, a methylamino group, a dimethylamino group, a diethylamino group, a diisopropylamino group, a trimethylsilyl group, a dimethylsilyl group, a thioisocyano group, or a C1-20-linear or C3-20-branched alkyl group, in which one —CH2— or two or more non-adjacent —CH2— may be each independently replaced with —O—, —S—,
—CO—, —COO—, —OCO—, —CO—S—, —S—CO—, —O—CO—O—,
—CO—NH—, —NH—CO—, —CH═CH—COO—, —CH═CH—OCO—,
—COO—CH═CH—, —OCO—CH═CH—, —CH═CH—, —CF═CF—, or
—C═C—, and any hydrogen atom in the alkyl group may be replaced with F, or Y may represent a group represented by P-Sp-,
m1 and m2 each independently represent an integer of 1 to 6,
(b) one or more compounds of formula CO-1,

OG Complex Work Unit Chemistry
wherein
R1 and R2 denotes H, alkyl, alkoxy or mono- oligo- or polyfluorinated alkyl or alkoxy,
L1 denotes H, alkyl, alkoxy, thioalkyl, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy; halogen, CN, NO2, OCN, SCN, or mono- oligo- or polyfluorinated alkyl or alkoxy atoms; or -(Sp31-A31),
L2 to L3 denotes H, alkyl, mono- oligo- or polyfluorinated alkyl, or -(Sp31-A31),
Sp31 denotes a spacer group or a single bond, and
A31 denotes an aryl, heteroaryl, (non-aromatic) alicyclic and heterocyclic group, optionally having one or more substituents, which are—silyl, sulfo, sulfonyl, formyl, amine, imine, nitrile, mercapto, nitro, halogen, C1-12 alkyl, C6-12 aryl, C1-12 alkoxy, hydroxyl, or combinations of these groups,
n denotes 0 or 1,
(c) one or more compounds of formula DRM,
P1-Sp1-MG-Sp2-P2  DRM
wherein
P1 and P2 independently of each other denote a polymerizable group,
Sp1 and Sp2 independently of each other are a spacer group (Sp) or a single bond, and
MG is a rod-shaped mesogenic group,
whereby in DRM the compounds of formula T are excluded, and
(d) at least one monoreactive mesogenic compound of formula MRM,
P1-Sp1-MG-R  MRM
wherein P1, Sp1 and MG have one of the meanings given above in formula DRM,
R is F, Cl, Br, I, —CN, —NO2, —NCO, —NCS, —OCN, —SCN, —C(═O)NRxRy, —C(═O)X, —C(═O)ORx, —C(═O)Ry, —NRxRy, —OH, —SF5, optionally substituted silyl, C1-12-straight chain alkyl or alkoxy or C3-12-branched alkyl or alkoxy, C2-12-straight chain or C3-12-branched alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy, wherein one or more H atoms are optionally replaced by F or Cl,
X is halogen, and
Rx and Ry are independently of each other H or alkyl with 1 to 12 C-atoms.