# US 12,767,889 B2 · Liquid-crystal medium comprising polymerizable compounds

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- Number: US 12,767,889 B2
- Document ID: US12767889B2
- Status: Granted
- Kind: B2
- Application number: 18/986,866
- Filed: 2024-12-19
- Published: 2025-06-26
- Granted: 2026-10-20
- Earliest claimed: 2023-12-21
- Assignees: Merck Patent GmbH
- Applicants: MERCK PATENT GmbH
- Inventors: Min Tzu Chuang; I-Wen Chen; I-Hua Huang; Jer-Lin Chen; Sven Christian Laut
- Web page: https://patentgrep.com/patent/US12767889B2

## CPC

- C09K 19/12: at least two benzene rings directly linked, e.g. biphenyls
- C09K 19/3003: {Compounds containing at least two rings in which the different rings are directly linked (covalent bond)}
- C09K 19/322: {Compounds containing a naphthalene ring or a completely or partially hydrogenated naphthalene ring}
- C09K 19/3402: {having oxygen as hetero atom (sugars C09K19/0422)}
- G02F 1/133354: {Arrangements for aligning or assembling substrates}
- G02F 1/13712: {the liquid crystal having negative dielectric anisotropy}
- G02F 1/13775: {Polymer-stabilized liquid crystal layers}
- C09K 2019/122: {Ph-Ph}
- C09K 2019/123: {Ph-Ph-Ph}
- C09K 2019/124: {Ph-Ph-Ph-Ph}
- C09K 2019/3004: {Cy-Cy}
- C09K 2019/3018: {Ph-Cy-Ph}
- C09K 2019/323: {containing a binaphthyl}
- C09K 2019/3425: {Six-membered ring with oxygen(s) in fused, bridged or spiro ring systems}
- C09K 2219/15: used as a medium, in which chemical reactions take place
- C09K: MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- G02F: OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS

## Abstract

An LC medium (as a subcategory of liquid crystal material) comprising two or more polymerizable compounds, its use for optical, electro-optical and electronic purposes, in particular in LC displays, especially in LC displays of the PSA (polymer sustained alignment) or SA (self-aligning) mode, an LC display of the PSA or SA mode comprising the LC medium, and a process of manufacturing the LC display using the LC medium, especially an energy-saving LC display and energy-saving LC display production process.

## Claims

### Claim 1

An LC medium having negative dielectric anisotropy and comprising one or more compounds of formula L1 and further comprising at least two or more polymerizable compounds of formulae IA, IB, and/or IC:
P-Sp-M1-Sp-P IA
P-Sp-M2-Sp-P IB
P-Sp-M3-Sp-P IC
wherein the individual radicals, independently of each other and on each occurrence identically or differently, have the following meanings
RL1 straight chain alkyl having 1 to 15 C atoms or branched or cyclic alkyl having 3 to 15 C atoms, wherein one or more non-adjacent CH2-groups are optionally replaced by —O—, —S—, —CO—, —CO—O—, —O—CO—, —O—CO—O—, CR0═CR00—, —C═C—,
in such a manner that O- and/or S-atoms are not directly connected with each other, and wherein one or more H atoms are each optionally replaced by F or Cl,
XL F, Cl, CF3 or CHF2,
YL H, F, Cl or CH3,
Y H, F, Cl, CF3, CHF2 or CH3,
P a polymerizable group,
Sp a spacer group or a single bond, which is optionally substituted by La,
R0, R00 H or alkyl having 1 to 12 C atoms,
M1, M2, M3 a group each individually selected from the following formulae
wherein the benzene rings are optionally substituted by one or more groups L or P-Sp-,
L La, Lb, F, Cl, —CN, P-Sp-, or straight chain alkyl having 1 to 25 C atoms or branched or cyclic alkyl having 3 to 25 C atoms, wherein one or more non-adjacent CH2-groups are optionally replaced by —O—, —S—, —CO—, —CO—O—, —O—CO—, —O—CO—O— in such a manner that O- and/or S-atoms are not directly connected with each other, and wherein one or more H atoms are each optionally replaced by P, F or Cl,
La —C(Raa)(Rbb)OH,
Raa, Rbb straight-chain alkyl with 1 to 6 C atoms, or optionally Raa and Rbb together with the C atom to which they are attached form a cyclic alkyl group with 3 to 12 C atoms,
Lb straight-chain or branched alkenyl with 2 to 7 C atoms,
wherein in the compounds of formula IA the group M1 and/or at least one spacer group Sp is at least monosubstituted with La,
and wherein in the compounds of formula IC the group M3 is at least monosubstituted with Lb.

### Claim 2 (depends on 1)

The LC medium according to claim 1, wherein the compounds of formula L1 are selected from the following subformulae:
wherein
RL1 denotes straight chain alkyl having 1 to 15 C atoms or branched or cyclic alkyl having 3 to 15 C atoms, wherein one or more non-adjacent CH2-groups are optionally replaced by —O—, —S—, —CO—, —CO—O—, —O—CO—, —O—CO—O—, CR0═CR00—, —C═C—,
in such a manner that O- and/or S-atoms are not directly connected with each other, and wherein one or more H atoms are each optionally replaced by F or Cl.

### Claim 3

An LC medium having negative dielectric anisotropy and comprising one or more compounds of formula L2, and further comprising at least two or more polymerizable compounds of formulae IA, IB, and/or IC:
P-Sp-M1-Sp-P IA
P-Sp-M2-Sp-P IB
P-Sp-M3-Sp-P IC
wherein the individual radicals, independently of each other and on each occurrence identically or differently, have the following meanings
RL1 straight chain alkyl having 1 to 15 C atoms or branched or cyclic alkyl having 3 to 15 C atoms, wherein one or more non-adjacent CH2-groups are optionally replaced by —O—, —S—, —CO—, —CO—O—, —O—CO—, —O—CO—O—, CR0═CR00—, —C═C—,
in such a manner that O- and/or S-atoms are not directly connected with each other, and wherein one or more H atoms are each optionally replaced by F or Cl,
RL2 a straight-chain alkenyl radical having 2-6 C atoms,
XL F, Cl, CF3 or CHF2,
YL H, F, Cl or CH3,
Y H, F, Cl, CF3, CHF2 or CH3,
P a polymerizable group,
Sp a spacer group or a single bond, which is optionally substituted by La,
R0, R00 H or alkyl having 1 to 12 C atoms,
M1, M2, M3 a group each individually selected from the following formulae
wherein the benzene rings are optionally substituted by one or more groups L or P-Sp-,
L La, Lb, F, Cl, —CN, P—Sp-, or straight chain alkyl having 1 to 25 C atoms or branched or cyclic alkyl having 3 to 25 C atoms, wherein one or more non-adjacent CH2-groups are optionally replaced by —O—, —S—, —CO—, —CO—O—, —O—CO—, —O—CO—O— in such a manner that O- and/or S-atoms are not directly connected with each other, and wherein one or more H atoms are each optionally replaced by P, F or Cl,
La —C(Raa)(Rbb)OH,
Raa, Rbb straight-chain alkyl with 1 to 6 C atoms, or optionally Raa and Rbb together with the C atom to which they are attached form a cyclic alkyl group with 3 to 12 C atoms,
Lb straight-chain or branched alkenyl with 2 to 7 C atoms,
wherein in the compounds of formula IA the group M1 and/or at least one spacer group Sp is at least monosubstituted with La,
and wherein in the compounds of formula IC the group M3 is at least monosubstituted with Lb.

### Claim 4 (depends on 1)

The LC medium according to claim 1, further comprising one or more compounds selected from the group consisting of compounds of the formulae IIA, IIB, IIC and IID
in which the individual radicals, on each occurrence identically or differently, and each, independently of one another, have the following meaning:
R21, R22 H, an alkyl or alkoxy radical having 1 to 15 C atoms or an alkenyl radical having 2 to 15 C atoms, which is unsubstituted or monosubstituted by F, Cl, CN or CF3 and where in addition, one or more CH2 groups in these radicals may be replaced by —O—, —S—, —C═C—, —CF2O—, —OCF2—, —OC—O—, —O—CO—
in such a way that O- and/or S-atoms are not linked directly to one another, wherein in formula IID R21 is different from cyclic alkyl or alkoxy,
L1 to L4 F, Cl, CF3 or CHF2,
Y H, F, Cl, CF3, CHF2 or CH3,
Z1, Z2 a single bond, —CH2CH2—, —CH═CH—, —CF2O—, —OCF2—, —CH2O—, —OCH2—, —COO—, —OCO—, —C2F4—, —CF═CF—, —CH═CHCH2O,
p 0, 1 or 2, and
q 0 or 1.

### Claim 5 (depends on 1)

The LC medium according to claim 1, wherein it additionally comprises one or more compounds of formula III
in which
R31 and R32 each, independently of one another, denote H, an alkyl or alkoxy radical having 1 to 15 C atoms or an alkenyl radical having 2 to 15 C atoms, which is unsubstituted, monosubstituted by F, Cl, CN or CF3 or at least monosubstituted by halogen, where in addition, one or more CH2 groups in these radicals may be replaced by —O—, —S—,
C═C—, —CF2O—, —OCF2—, —OC—O— or —O—CO— in such a way that O atoms are not linked directly to one another,
Y1, Y2 H, F, Cl, CF3, CHF2, CH3 or OCH3,
A3 on each occurrence, independently of one another, denotes
a) 1,4-cyclohexenylene or 1,4-cyclohexylene radical, in which one or two non-adjacent CH2 groups may be replaced by —O— or —S—,
b) a 1,4-phenylene radical, in which one or two CH groups may be replaced by N, or
c) a radical selected from the group consisting of spiro[3.3]heptane-2,6-diyl, 1,4-bicyclo[2.2.2]octylene, naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl, 1,2,3,4-tetrahydro-naphthalene-2,6-diyl, phenanthrene-2,7-diyl and fluorene-2,7-diyl,
wherein the radicals a), b) and c) may be mono- or polysubstituted by halogen atoms,
n denotes 0, 1 or 2,
Z1 on each occurrence independently of one another denotes —CO—O—, —O—CO—, —CF2O—, —OCF2—, —CH2O—, —OCH2—, —CH2—, —CH2CH2—, —(CH2)4—, —CH═CH—CH2O—, —C2F4—, —CH2CF2—, —CF2CH2—, —CF═CF—, —CH═CF—, —CF═CH—, —CH═CH—, —C═C— or a single bond, and
L11 and L12 each, independently of one another, denote F, Cl, CF3 or CHF2, and
W denotes O or S.

### Claim 6 (depends on 1)

The LC medium according to claim 1, wherein it additionally comprises one or more compounds of formula IV-1 to IV-4:
in which
alkyl and alkyl′, independently of one another, denote alkyl having 1 to 7 C atoms,
alkenyl denotes an alkenyl radical having 2 to 5 C atoms,
alkenyl′ denotes an alkenyl radical having 2 to 5 C atoms, and
alkoxy denotes alkoxy having 1 to 5 C atoms.

### Claim 7 (depends on 1)

The LC medium according to claim 1, wherein it comprises two or more compounds of formula M selected from the following formulae:
in which the individual radicals, on each occurrence identically or differently, and each, independently of one another, have the following meaning:
P1, P2, P3 a polymerizable group,
Sp1, Sp2, Sp3 a single bond or a spacer group where, in addition, one or more of the radicals P1-Sp1-, P2-Sp2- and P3-Sp3- may denote RM, with the proviso that at least one of the radicals P1-Sp1-, P2-Sp2 and P3-Sp3- present is different from RM,
RM H, F, Cl, CN or straight-chain alkyl having 1 to 25 C atoms or branched alkyl having 3 to 25 C atoms, in which, in addition, one or more non-adjacent CH2 groups may each be replaced, independently of one another, by —C(R0)═C(R00)—, —C═C—, —N(R0)—, —O—, —S—, —CO—, —CO—O—, —O—CO—, —O—CO—O— in such a way that O and/or S atoms are not linked directly to one another, and in which, in addition, one or more H atoms may be replaced by F, Cl, CN or P1-Sp1-, wherein RM does not denote or contain a group P1, P2 or P3,
R0, R00 H or alkyl having 1 to 12 C atoms,
Ry, Rz H, F, CH3 or CF3,
X1, X2, X3—CO—O—, —O—CO— or a single bond,
ZM1 —O—, —CO—, —C(RyRz)— or —CF2CF2—,
ZM2, ZM3 —CO—O—, —O—CO—, —CH2O—, —OCH2—, —CF2O—, —OCF2— or —(CH2)n—, where n is 2, 3 or 4,
L F, Cl, CN or straight-chain, optionally mono- or polyfluorinated alkyl, alkoxy, thioalkyl, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having 1 to 12 C atoms, optionally mono- or polyfluorinated alkenyl or alkynyl having 2 to 12 C atoms, or branched, optionally mono- or polyfluorinated alkyl, alkoxy, thioalkyl, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having 3 to 12 C atoms,
L′, L″ H, F or Cl,
k 0 or 1,
r 0, 1, 2, 3 or 4,
S 0, 1, 2 or 3,
t 0, 1 or 2,
X 0 or 1.

### Claim 8 (depends on 1)

The LC medium according to claim 1, wherein it additionally comprises one or more additives selected from the group consisting of stabilisers, chiral dopants, polymerization initiators and self-alignment additives.

### Claim 9 (depends on 1)

A process of preparing an LC medium according to claim 1, comprising the steps of mixing the one or more one or more compounds of formula L1 and the two or more polymerizable compounds of formulae IA, IB, and/or IC with one or more compounds of formula II
wherein the individual radicals, independently of each other and on each occurrence identically or differently, have the following meanings
R21 and R22 H, straight chain alkyl or alkoxy having 1 to 20 C atoms or branched or cyclic alkyl having 3 to 25 C atoms, wherein one or more non-adjacent CH2-groups are optionally replaced by —O—, —S—, —CO—, —CO—O—, —O—CO—, —O—CO—O—, CR0═CR00—, —C═C—,
in such a manner that O- and/or S-atoms are not directly connected with each other, and wherein one or more H atoms are each optionally replaced by F, Cl, CN or CF3,
R0, R00 H or alkyl having 1 to 12 C atoms,
A1 and A2 a group selected from the following formulae
Z1 and Z2 —CH2CH2—, —CH═CH—, —CF2O—, —OCF2—, —CH2O—, —OCH2—, —CO—O—, —O—CO—, —C2F4—, —CF═CF—, —CH═CH—CH2O— or a single bond,
L1, L2, L3 and L4 F, Cl, OCF3, CF3, CH3, CH2F or CHF2,
Y H, F, Cl, CF3, CHF2 or CH3,
Lc CH3 or OCH3,
a1 0, 1 or 2,
a2 0 or 1,
one or more compounds of formula III
in which
R31 and R32 each, independently of one another, denote H, an alkyl or alkoxy radical having 1 to 15 C atoms or an alkenyl radical having 2 to 15 C atoms which is unsubstituted, monosubstituted by F, Cl, CN or CF3 or at least monosubstituted by halogen, where in addition, one or more CH2 groups in these radicals may be replaced by —O—, —S—,
C═C—, —CF2O—, —OCF2—, —OC—O— or —O—CO— in such a way that O atoms are not linked directly to one another,
Y1, Y2 H, F, Cl, CF3, CHF2, CH3 or OCH3,
A3 on each occurrence, independently of one another, denotes
a) 1,4-cyclohexenylene or 1,4-cyclohexylene radical, in which one or two non-adjacent CH2 groups may be replaced by —O— or —S—,
b) a 1,4-phenylene radical, in which one or two CH groups may be replaced by N, or
c) a radical selected from the group consisting of spiro[3.3]heptane-2,6-diyl, 1,4-bicyclo[2.2.2]octylene, naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl, 1,2,3,4-tetrahydro-naphthalene-2,6-diyl, phenanthrene-2,7-diyl and fluorene-2,7-diyl, wherein the radicals a), b) and c) may be mono- or polysubstituted by halogen atoms,
n denotes 0, 1 or 2,
Z1 on each occurrence independently of one another denotes —CO—O—, —O—CO—, —CF2O—, —OCF2—, —CH2O—, —OCH2—, —CH2—, —CH2CH2—, —(CH2)4—, —CH═CH—CH2O—, —C2F4—, —CH2CF2—, —CF2CH2—, —CF═CF—, —CH═CF—, —CF═CH—, —CH═CH—, —C═C— or a single bond, and
L11 and L12 each, independently of one another, denote F, Cl, CF3 or CHF2, and
W denotes O or S,
one or more compounds of formula IV
in which
R41 denotes an unsubstituted alkyl radical having 1 to 7 C atoms where, in addition, one or more CH2 groups may be replaced by
or an unsubstituted alkenyl radical having 2 to 7 C atoms, and
R42 denotes an unsubstituted alkyl radical having 1 to 7 C atoms or an unsubstituted alkoxy radical having 1 to 6 C atoms or an unsubstituted alkenyl radical having 2 to 7 C atoms, and/or
one or more compounds of formula V
in which
R51 and R52 independently of one another, denote H, an alkyl or alkoxy radical having up to 15 C atoms or an alkenyl radical having 2 to 15 C atoms, which is unsubstituted, monosubstituted by F, Cl, CN or CF3 or at least monosubstituted by halogen, where, in addition, one or more CH2 groups in these radicals may be replaced by —O—, —S—, —C═C—, —CF2O—, —OCF2—, —OC—O—, —O—CO—
in such a way that O atoms are not linked directly to one another,
identically or differently, denote
Z51 Z52 each, independently of one another, denote —CH2—CH2—, —CH2—O—, —CH═CH—, —C═C—, —COO— or a single bond, and
n is 1 or 2,
and optionally with further liquid-crystalline compounds and/or additives, and optionally polymerizing the polymerizable compounds.

### Claim 10 (depends on 1)

An LC display comprising an LC medium as defined in claim 1.

### Claim 11 (depends on 10)

The LC display according to claim 10, which comprises a PS-VA, PS-IPS, PS-FFS, PS-UB-FFS or SA-VA display.

### Claim 12 (depends on 10)

The LC display according to claim 10, wherein it comprises two substrates, at least one of which is transparent to light, an electrode provided on each substrate or two electrodes provided on only one of the substrates, and located between the substrates a layer of the LC medium, wherein the polymerizable compounds are polymerized between the substrates of the display by UV photopolymerization.

### Claim 13 (depends on 12)

A process of manufacturing an LC display according to claim 12, comprising the steps of providing the LC medium between the substrates of the display, and polymerizing the polymerizable compounds by irradiation with UV light.

### Claim 14 (depends on 3)

The LC medium according to claim 3, wherein the compounds of formula L2 are selected from the following subformulae:
wherein “alkyl” means a straight-chain alkyl group having 1 to 6 C atoms, in which a CH2 group may be replaced by cyclopropane-1,2-diyl or cyclopentane-1,2-diyl.

### Claim 15 (depends on 1)

The LC medium according to claim 1, wherein it comprises at least one polymerizable compound selected from subformula IA and at least one polymerizable compound selected from subformula IB.

### Claim 16 (depends on 1)

The LC medium according to claim 1, wherein the at least one compound of formula IB is selected from compounds of subformulae IBD4, IBD6, IBD7, IBD19, IBD21 and IBD23: