# US 11,441,073 B2 · Liquid-crystalline medium

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- Number: US 11,441,073 B2
- Document ID: US11441073B2
- Status: Granted
- Kind: B2
- Application number: 14/832,193
- Filed: 2015-08-21
- Published: 2016-02-25
- Granted: 2022-09-13
- Earliest claimed: 2014-08-22
- Assignees: Merck Patent GmbH
- Applicants: Merck Patent GmbH
- Inventors: Harald Hirschmann; Martina Windhorst; Monika Bauer; Volker Reiffenrath; Matthias Bremer
- Web page: https://patentgrep.com/patent/US11441073B2

## CPC

- C09K 19/3402: {having oxygen as hetero atom (sugars C09K19/0422)}
- 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 19/3098: {Unsaturated non-aromatic rings, e.g. cyclohexene rings}
- C09K 19/32: containing condensed ring systems, i.e. fused, bridged or spiro ring systems
- C09K 19/54: Additives having no specific mesophase {characterised by their chemical composition}
- C09K 19/542: {Macromolecular compounds}
- C09K 2019/122: {Ph-Ph}
- C09K 2019/123: {Ph-Ph-Ph}
- C09K 2019/3004: {Cy-Cy}
- C09K 2019/3009: {Cy-Ph}
- C09K 2019/301: {Cy-Cy-Ph}
- C09K 2019/3016: {Cy-Ph-Ph}
- C09K 2019/3027: {Compounds comprising 1,4-cyclohexylene and 2,3-difluoro-1,4-phenylene}
- C09K 2019/3422: {the heterocyclic ring being a six-membered ring}
- C09K 2019/548: {stabilizing the alignment; Polymer stabilized alignment}
- C09K: MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE

## Abstract

The invention relates to a liquid-crystalline medium which comprises at least one compound of the formula I, wherein the radicals R11, L1, L2, n and A are as defined herein, and to the use thereof for an active-matrix display, in particular based on the VA, PSA, PS-VA, PA-VA, PALC, FFS, PS-FFS, IPS or PS-IPS effect.

## Claims

### Claim 1

A liquid-crystalline medium comprising:
(a) one or more compounds of formula I1,
in which
alkenyl denotes CH2=CH—CH2—CH2—, and
L1 and L2 each, independently of one another, denote F or Cl,
wherein the amount of compounds of formula I1 in the medium is ≥5%;
(b) one or more compounds selected from the compounds of formulae I 3 and one or more compounds selected from the compounds of formulae I4,
in which
alkenyl denotes CH2=CH—, and
L1 and L2 each, independently of one another, denote F or Cl,
wherein the amount of compounds of formula I13 in the medium is ≥5% and the amount of compounds of formula I4 in the medium is ≥6%;
(c) optionally one or more compounds selected from the compounds of formula I2,
in which
alkenyl denotes CH2=CH—, and
L1 and L2 each, independently of one another, denote F or Cl;
the compound of formula CC-n-V
wherein n is 3, in an amount of ≥30% by weight of based on the mixture as a whole, and
(d) one or more compounds selected from formulae L-1 to L-11, EY, and T-1 to T-21:
in which
R, R1 and R2 each, independently of one another, denote H, an alkyl or alkenyl radical having up to 15 C atoms which is unsubstituted, monosubstituted by CN or CF3 or at least monosubstituted by halogen, where, in addition, one or more CH2 groups in these radicals may each be replaced by —O—, —S—,
—C≡—, —CF2 O—, —OCF2—, —OC—O— or —O—CO— in such a way that O atoms are not linked directly to one another,
(O) denotes —O— or a single bond,
alkyl denotes an alkyl radical having 1-6 C atoms, and
s denotes 1 or 2;
in which
R1 denotes H, an alkyl or alkenyl radical having up to 15 C atoms which is un-substituted, monosubstituted by CN or CF3 or at least monosubstituted by halogen, where, in addition, one or more CH2 groups in these radicals may each 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,
L1 and L2 are each independently F or Cl, and
R1* denotes H, an alkyl or alkenyl radical having up to 15 C atoms which is un-substituted, monosubstituted by CN or CF3 or at least monosubstituted by halogen, where, in addition, one or more CH2 groups in these radicals may each 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;
in which
R denotes a straight-chain alkyl or alkoxy radical having 1-7 C atoms,
(O) denotes —O— or a single bond,
m denotes 1-6, and
n denotes 0, 1, 2, 3 or 4.

### Claim 2 (depends on 1)

A liquid-crystalline medium according to claim 1, wherein said medium contains one or more compounds of formula I2

### Claim 3 (depends on 1)

A liquid-crystalline medium according to claim 1, further comprising one or more compounds of formula A,
in which
X and Y each, independently of one another, denote a trans-1,4-cyclohexylene radical or a 1,4-phenylene radical, which in each case is unsubstituted or substituted by one or two identical or different radicals L1,
one of the radicals Rc and Rd denotes an alkenyl radical having 2 to 12 C atoms, and the other of the radicals Rc and Rd denotes an alkyl radical having 1 to 12 C atoms, in which, in addition, one or two non-adjacent CH2 groups may each be replaced by —O—, —CH═CH—, —CO—, —OCO— or —COO— in such a way that O atoms are not linked directly to one another,
L1 denotes F, Cl, CF3, OCF3 or CHF2,
a denotes 1 or 2,
wherein said one or more compounds of formula A are not compounds of formulae A3a and A6a.

### Claim 4 (depends on 1)

A liquid-crystalline medium according to one or more of claim 1, further comprising one or more compounds selected from formulae A3a and A6a:
in which
m denotes 1, 2, 3, 4, 5 or 6,
i denotes 0, 1, 2 or 3, and
Rb1 denotes H, CH3 or C2H5.

### Claim 5 (depends on 1)

A liquid-crystalline medium according to claim 1, further comprising one or more compounds selected from the compounds of formulae IIA, IIB and IIC,
in which
R2A, R2B and R2C each, independently of one another, denote H, an alkyl or alkenyl radical having up to 15 C atoms which is unsubstituted, monosubstituted by CN or CF3 or at least monosubstituted by halogen, where, in addition, one or more CH2 groups in these radicals may each 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,
L1-4 each, independently of one another, denote F or Cl,
Z2 and Z2′ each, independently of one another, denote a single bond, —CH2CH2—, —CH═CH—, —CF2O—, —OCF2—, —CH2O—, —OCH2—, —COO—, —OCO—, —C2F4—, —CF═CF—, or —CH═CHCH2O—,
p denotes 1 or 2,
q denotes 0 or 1, and
v denotes 1 to 6,
with the proviso that the compounds of formulae IIA and IIB are not identical to the compounds of formula I1, I2, I3, or I4.

### Claim 6 (depends on 1)

A liquid-crystalline medium according to one or more of claim 1, further comprising one or more compounds of formula III,
in which
R31 and R32 each, independently of one another, denote a straight-chain alkyl, alkoxyalkyl or alkoxy radical having up to 12 C atoms, and
denotes
Z3 denotes a single bond, —CH2CH2—, —CH═CH—, —CF2O—, —OCF2—, —CH2O—, —OCH2—, —COO—, —OCO—, —C2F4—, —C4H9—, or —CF═CF—.

### Claim 7 (depends on 1)

A liquid-crystalline medium according claim 1, wherein said one or more compounds selected from formulate L-1 to L-11, EY, and T-1 to T-21 are selected from one or more compounds of the formulate L-1 to L-11,
in which
R, R1 and R2 each, independently of one another, denote H, an alkyl or alkenyl radical having up to 15 C atoms which is unsubstituted, monosubstituted by CN or CF3 or at least monosubstituted by halogen, where, in addition, one or more CH2 groups in these radicals may each 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,
(O) denotes —O— or a single bond,
alkyl denotes an alkyl radical having 1-6 C atoms, and
s denotes 1 or 2.

### Claim 8 (depends on 1)

A liquid-crystalline medium according to claim 1, wherein said one or more compounds selected from formulae L-1 to L-11, EY, and T-1 to T-21 are selected from one or more compounds of the formulate T-1 to T-21,
in which
R denotes a straight-chain alkyl or alkoxy radical having 1-7 C atoms,
(O) denotes —O— or a single bond,
m denotes 1-6, and
n denotes 0, 1, 2, 3 or 4.

### Claim 9 (depends on 1)

A liquid-crystalline medium according claim 1, further comprising one or more compounds of formulae O-1 to O-17,
in which
R1 and R2 each, independently of one another, denote H, an alkyl or alkenyl radical having up to 15 C atoms which is unsubstituted, monosubstituted by CN or CF3 or at least monosubstituted by halogen, where, in addition, one or more CH2 groups in these radicals may each 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.

### Claim 10 (depends on 1)

A liquid-crystalline medium according claim 1, further comprising one or more indane compounds of formula In,
in which
R11, R12, R13 each, independently of one another, denote a straight-chain alkyl, alkoxy, alkoxyalkyl or alkenyl radical having 1-5 C atoms,
R12 and R13 additionally can also denote halogen,
denotes
and
i denotes 0, 1 or 2.

### Claim 11 (depends on 1)

A liquid-crystalline medium according to claim 1, further comprising one or more polymerizable compounds.

### Claim 12 (depends on 11)

A liquid-crystalline medium according claim 11, wherein the concentration of the polymerizable compound(s), based on the total weight of the medium, is 0.01-5% by weight.

### Claim 13 (depends on 11)

A liquid-crystalline medium according to claim 11, wherein the polymerizable compound(s) is (are) selected from compounds of formula M
Ra-A1-(Z1-A2)m-Rb M
in which the individual radicals have the following meanings:
Ra and Rb each, independently of one another, denote P, P-Sp-, H, halogen, SF5, NO2, a carbon group or a hydrocarbon group, where at least one of the radicals Ra and Rb denotes or contains a group P or P-Sp-,
P on each occurrence, identically or differently, denotes a polymerizable group,
Sp on each occurrence, identically or differently, denotes a spacer group or a single bond,
A1 and A2 each, independently of one another, denote an aromatic, heteroaromatic, alicyclic or heterocyclic group, preferably having 4 to 25 ring atoms, which may also contain fused rings, and which may also be mono- or polysubstituted by L,
L denotes P-Sp-, H, OH, CH2OH, halogen, SF5, NO2, a carbon group or a hydrocarbon group,
Z1 on each occurrence, identically or differently, denotes —O—, —S—, —CO—, —CO—O—, —OCO—, —O—CO—O—, —OCH2—, —CH2O—, —SCH2—, —CH2S—, —CF2O—, —OCF2—, —CF2S—, —SCF2—, —(CH2)a1-—, —CF2CH2—, —CH2CF2—, —(CF2)n1—, —CH═CH—, —CF═CF—, —C≡C—, —CH═CH—COO—, —OCO—CH═CH—, CR0R00 or a single bond,
R0 and R00 each, independently of one another, denote H or alkyl having 1 to 12 C atoms,
m denotes 0, 1, 2, 3 or 4, and
n1 denotes 1, 2, 3 or 4.

### Claim 14 (depends on 1)

A liquid-crystalline medium according to claim 1, further comprising one or more additives.

### Claim 15 (depends on 14)

A liquid-crystalline medium according to claim 14, wherein said additive is selected from free-radical scavengers, antioxidants and/or stabilizers.

### Claim 16 (depends on 1)

A liquid-crystalline medium according to claim 1, further comprising one or more stabilizers selected from the following:

### Claim 17 (depends on 15)

A liquid-crystalline medium according to claim 15, wherein said medium comprises one or more stabilizers in amounts of 0.001-10% by weight, based on the total weight of the medium.

### Claim 18 (depends on 1)

A process for the preparation of a liquid-crystalline medium according to claim 1, comprising mixing at least one compound of formula I1 with one or more compounds of formula I3, one or more compounds of formula I4, one or more compounds selected from formulae L-1 to L-11, EY, and T-1 to T-21, optionally one or more compounds of formula I2, and optionally adding one or more additives.

### Claim 19 (depends on 18)

A process according to claim 18, further comprising mixing at least one polymerizable compound, and one or more additives are optionally added.

### Claim 20 (depends on 1)

A method of generating an electro-optical effect comprising applying a voltage to a liquid-crystalline medium according to claim 1.

### Claim 21 (depends on 20)

The method according to claim 20 wherein said medium is contained in a VA, PSA, PS-VA, PA-VA, IPS, PS-IPS, FFS, PS-FFS or PALC display.

### Claim 22 (depends on 1)

An electro-optical display having active-matrix addressing comprising, as dielectric, a liquid-crystalline medium according to claim 1.

### Claim 23 (depends on 22)

An electro-optical display according to claim 22, wherein said display is a VA, PSA, PS-VA, PA-VA, IPS, PS-IPS, FFS, UB-FFS, PS-FFS or PALC display.

### Claim 24 (depends on 1)

A liquid-crystalline medium according to claim 1, further comprising one or more compounds selected from formulae BC, CR, PH-1, PH-2, BF-1, BF-2, BS-1 and BS-2:
in which
RB1, R B2, RCR1, RCR2, R1, and R2 each, independently of one another, denote H, an alkyl or alkenyl radical having up to 15 C atoms which is un-substituted, monosubstituted by CN or CF3 or at least monosubstituted by halogen, where, in addition, one or more CH2 groups in these radicals may each 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,
c denotes 0, 1 or 2, and
d denotes 1 or 2.

### Claim 25 (depends on 24)

A liquid-crystalline medium according to claim 24, wherein said one or more compounds selected from formulae BC, CR, PH-1, PH-2, BF-1, BF-2, BS-1 and BS-2 are selected from the following subformulae:
in which
alkyl and alkyl* each, independently of one another, denote a straight-chain alkyl radical having 1-6 C atoms,
alkoxy and alkoxy* each, independently of one another, denote a straight-chain alkoxy radical having 1-6 C atoms, and
alkenyl and
alkenyl* each, independently of one another, denote a straight-chain alkenyl radical having 2-6 C atoms.

### Claim 26 (depends on 7)

A liquid-crystalline medium according to claim 7, wherein said one or more compounds selected from formulae L-1 to L-11 are selected from formulae L-1 to L-4.

### Claim 27 (depends on 1)

A liquid-crystalline medium according to claim 1, wherein said one or more compounds selected from formulae L-1 to L-11, EY, T-1 to T-21 and are selected from formula EY:
in which
R1 denotes H, an alkyl or alkenyl radical having up to 15 C atoms which is un-substituted, monosubstituted by CN or CF3 or at least monosubstituted by halogen, where, in addition, one or more CH2 groups in these radicals may each 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,
L1 and L2 are each independently F or Cl, and
R1* denotes H, an alkyl or alkenyl radical having up to 15 C atoms which is un-substituted, monosubstituted by CN or CF3 or at least monosubstituted by halogen, where, in addition, one or more CH2 groups in these radicals may each 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.

### Claim 28 (depends on 27)

A liquid-crystalline medium according to claim 27, wherein said one or more compounds selected from formula EY are selected from the following compounds:

### Claim 29 (depends on 1)

A liquid-crystalline medium according to claim 1, further comprising one or more compounds selected from formulae Q-1 to Q-9:
in which
RQ and XQ each, independently of one another, denote H, an alkyl or alkenyl radical having up to 15 C atoms which is unsubstituted, monosubstituted by CN or CF3 or at least monosubstituted by halogen, where, in addition, one or more CH2 groups in these radicals may each 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.

### Claim 30 (depends on 11)

A liquid-crystalline medium according to claim 11, wherein said one or more polymerizable compounds are selected from the following compounds:

### Claim 31 (depends on 1)

A liquid-crystalline medium according to claim 1, wherein said medium further contains one or more compounds of formula A1a
wherein
m denotes 1, 2, 3, 4, 5 or 6, and
Rb1 denotes H, CH3 or C2H5,
and wherein said compound of formula A1a is not a compound of formula CC-n-V wherein n is 3.

### Claim 32 (depends on 31)

A liquid-crystalline medium according to claim 31, wherein said one or more compounds of formula Ala are selected from the following compounds

### Claim 33 (depends on 1)

A liquid-crystalline medium according to claim 1, wherein the amount of the compound of formula CC-n-V, wherein n is 3, is 30% to 50% by weight of based on the mixture as a whole.

### Claim 34 (depends on 24)

A liquid-crystalline medium according to claim 24, wherein said one or more compounds selected from formulae BC, CR, PH-1, PH-2, BF-1, BF-2, BS-1 and BS-2 are selected from one or more compounds of the formulae BF-1, BF-2, BS-1 and BS-2.