# US 11,299,676 B2 · Polymerisable compounds and the use thereof in liquid-crystal displays

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- Number: US 11,299,676 B2
- Document ID: US11299676B2
- Status: Granted
- Kind: B2
- Application number: 16/651,554
- Filed: 2018-09-26
- Published: 2020-08-20
- Granted: 2022-04-12
- Earliest claimed: 2017-09-29
- Assignees: Merck Patent GmbH
- Applicants: Merck Patent GmbH
- Inventors: Qiong Tong; Dmitry Ushakov; Helga Haas; Steffen Gnauck; Thorsten Rachor; Sven Schuepfer; Simon Mundinger
- Web page: https://patentgrep.com/patent/US11299676B2

## CPC

- C09K 19/54: Additives having no specific mesophase {characterised by their chemical composition}
- C09K 19/542: {Macromolecular compounds}
- C09K 19/0208: {Twisted Nematic (T.N.); Super Twisted Nematic (S.T.N.); Optical Mode Interference (O.M.I.)}
- C09K 19/3003: {Compounds containing at least two rings in which the different rings are directly linked (covalent bond)}
- C09K 19/3066: {in which the rings are linked by a chain containing carbon and oxygen atoms, e.g. esters or ethers}
- C09K 19/3405: {the heterocyclic ring being a five-membered ring}
- C09K 19/3486: {the heterocyclic ring containing nitrogen and oxygen atoms}
- C09K 19/56: Aligning agents
- G02F 1/133723: {Polyimide, polyamide-imide}
- C09K 2019/0448: {the end chain group being a polymerizable end group, e.g. -Sp-P or acrylate}
- C09K 2019/122: {Ph-Ph}
- C09K 2019/123: {Ph-Ph-Ph}
- C09K 2019/3004: {Cy-Cy}
- C09K 2019/3006: {Cy-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 2019/3408: {Five-membered ring with oxygen(s) in fused, bridged or spiro ring systems}
- C09K 2019/548: {stabilizing the alignment; Polymer stabilized alignment}
- G02F 1/133742: {for homeotropic alignment}
- 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

The present invention relates to a mixture comprising a not fully aromatic polymerisable compound and a polymerisable photoinitiator, to liquid-crystal (LC) media comprising them, and to the use of the polymerisable compounds and LC media for optical, electro-optical and electronic purposes, in particular in LC displays, especially in LC displays of the polymer sustained alignment type.

## Claims

### Claim 1

A mixture comprising one or more compounds of formula I and 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
R P, P-Sp-, H, F, Cl, Br, I, —CN, —NO2, —NCO, —NCS, —OCN, —SCN, SF5 or straight-chain or branched alkyl having 1 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(R00)—, —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 each be replaced by F, Cl, Br, I, CN, P or P-Sp-,
P a polymerizable group,
Sp a spacer group or a single bond,
A1, A3 straight-chain, branched or cyclic alkylene with 1 to 20 C atoms, wherein one or more non-adjacent CH2-groups are optionally replaced by —CR0═CR00—, —C≡C—, —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 F or Cl,
A2, A4 arylene or heteroarylene having 5 to 20 ring atoms, which optionally contains fused rings, which are optionally substituted by one or more groups L or P-Sp-,
Z1-4 —O—, —S—, —CO—, —CO—O—, —O—CO—, —O—CO—O—, —OCH2—, —CH2O—, —SCH2—, —CH2S—, —CF2O—, —OCF2—, —CF2S—, —SCF2—, —(CH2)n1—, —CF2CH2—, —CH2CF2—, —(CF2)n1—, —CH═CH—, —CF═CF—, —CH═CF—, —CF═CH—, —C≡C—, —CH═CH—CO—O—, —O—CO—CH═CH—, —CH2—CH2—CO—O—, —O—CO—CH2—CH2—, —CR0R00—, or a single bond,
R0, R00 H or alkyl having 1 to 12 C atoms,
L F, Cl, —CN, P-Sp- or straight chain, branched or cyclic alkyl having 1 to 25 C atoms, wherein one or more non-adjacent CH2-groups are optionally replaced by —CR0═CR00—, —C≡C—, —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-Sp-, F or Cl,
R1, R2 straight-chain or branched alkyl with 1 to 6 C atoms,
R3 OH or morpholine-1-yl,
a, b, c, d 0, 1, 2 or 3, with a+c≥1,
g 1, 2, 3 or 4,
n1 1, 2, 3 or 4,
r 0, 1, 2, 3 or 4,
p 1, 2 or 3, with p+r≤5,
and wherein in formula II in case of g≥2 the groups (P-Sp)p and —C(═O)—CR1R2R3 are linked to different terminal benzene rings, and in case of g≥3 all benzene rings are connected with each other via para-positions.

### Claim 2 (depends on 1)

The mixture according to claim 1, wherein in formula I Z1, Z2, Z3 and Z4 are a single bond.

### Claim 3 (depends on 1)

The mixture according to claim 1, wherein in formula I A1 and A3 are trans-1,4-cyclohexylene which is optionally substituted by one or more groups L or P-Sp-, and A2 and A4 are selected from 1,4-phenylene, pyridine and thiophene which is optionally substituted by one or more groups L or P-Sp-.

### Claim 4 (depends on 1)

The mixture according to claim 1, wherein in formula I and II all groups Sp are a single bond.

### Claim 5 (depends on 1)

The mixture according to claim 1, wherein in formula I -(A1-Z1)a-(A2-Z2)b-(A3-Z3)c-(A4-Z4)d— is selected from the following formulae
wherein i is an integer from 1 to 12, and the cyclohexylene and benzene rings are optionally substituted by one or more groups L or P-Sp-.

### Claim 6 (depends on 1)

The mixture according to claim 1, wherein the compounds of formula I are selected from the following subformulae
wherein P, Sp and L have independently of each other, and on each occurrence identically or differently, one of the meanings given in claim 1, i is an integer from 1 to 12 r is 0, 1, 2, 3 or 4, and s is 0, 1, 2 or 3.

### Claim 7 (depends on 1)

The mixture according to claim 1, wherein the compounds of formula II are selected from the following formulae
wherein P, Sp, L, R1-3 and r have the meanings given in claim 1, h is 0, 1 or 2, p1 is 0 or 1, p2 is 0, 1 or 2, with p1+p2≥1 and p1+p2+r≤5.

### Claim 8 (depends on 7)

The mixture according to claim 7, wherein in the compounds of formula II, IIA and IIB the group —C(═O)—CR1R2R3 is selected from the following groups
wherein Me is methyl, the asterisk * denotes the linkage to the benzene ring in formula II, IIA or IIB, and P and Sp have the meanings given in claim 7.

### Claim 9 (depends on 7)

The mixture according to claim 7, wherein the compounds of formula II, IIA and IIB are selected from the following formulae
wherein P, Sp, L, R1-3, r and h have the meanings given in claim 7.

### Claim 10 (depends on 9)

The mixture according to claim 9, wherein the compounds of formula II, IIA, IIB, IIA1-IIA3 and IIB1-IIB5 are selected from the following subformulae
wherein P, Sp, L and r have the meanings given in claim 9 and Me is methyl.

### Claim 11 (depends on 1)

A liquid crystal (LC) medium comprising one or more compounds of formula I and one or more compounds of formula II as defined in claim 1.

### Claim 12 (depends on 11)

The LC medium of claim 11, wherein said medium comprises
a polymerizable component A) comprising one or more compounds of formula I and one or more compounds of formula II, and
a liquid-crystalline LC component B) comprising one or more mesogenic or liquid-crystalline compounds.

### Claim 13 (depends on 11)

The LC medium of claim 11, wherein said medium comprises one or more compounds of the formulae CY and/or PY:
in which a, b
R1, R2, Zx, and L1-4 have the following meanings:
a denotes 1 or 2,
b denotes 0 or 1,
denotes
R1 and R2 each, independently of one another, denote alkyl having 1 to 12 C atoms, where, in addition, one or two non-adjacent CH2 groups may each be replaced by —O—, —CH═CH—, —CO—, —O—CO— or —CO—O— in such a way that O atoms are not linked directly to one another,
Zx denotes —CH═CH—, —CH2O—, —OCH2—, —CF2O—, —OCF2—, —O—, —CH2—, —CH2CH2— or a single bond,
L1-4 each, independently of one another, denote F, Cl, OCF3, CF3, CH3, CH2F, CHF2.

### Claim 14 (depends on 11)

The LC medium according to claim 11, wherein the medium comprises one or more compounds selected from the following formulae:
in which RA1, RA2,
Zx, L1-4, x, and z have the following meanings:
RA1 alkenyl having 2 to 9 C atoms or, if at least one of the rings X, Y and Z denotes cyclohexenyl, RA1 can also be alkyl 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,
RA2 alkyl 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,
Zx —CH2CH2—, —CH═CH—, —CF2O—, —OCF2—, —CH2O—, —OCH2—, —CO—O—, —O—CO—, —C2F4—, —CF═CF—, —CH═CH—CH2O—, or a single bond,
L1-4 each, independently of one another, H, F, Cl, OCF3, CF3, CH3, CH2F or CHF2H,
x 1 or 2,
z 0 or 1.

### Claim 15 (depends on 11)

The LC medium according to claim 11, wherein the medium comprises one or more compounds of the following formula:
in which the individual radicals have the following meanings:
denotes
denotes
R3 and R4 each, independently of one another, denote alkyl 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—, —O—CO— or —CO—O— in such a way that O atoms are not linked directly to one another,
Zy denotes —CH2CH2—, —CH═CH—, —CF2O—, —OCF2—, —CH2O—, —OCH2—, —COO—, —OCO—, —C2F4—, —CF═CF— or a single bond.

### Claim 16 (depends on 11)

The LC medium according to claim 11, wherein the compounds of formula I and II are polymerized.

### Claim 17 (depends on 11)

A process of preparing an LC medium of claim 11, comprising mixing one or more mesogenic or liquid-crystalline compounds with one or more compounds of formula I and II.

### Claim 18 (depends on 11)

An LC display comprising an LC medium as defined in claim 11.

### Claim 19 (depends on 18)

The LC display of claim 18, which is a PSA display or a polymer stabilized SA-VA display.

### Claim 20 (depends on 19)

The LC display of claim 19, which is a PS-VA, PS-OCB, PS-IPS, PS-FFS, PS-UB-FFS, PS-posi-VA, PS-TN, SA-VA or SA-FFS display.

### Claim 21 (depends on 19)

The LC display of claim 19, wherein the display comprises two substrates, at least one 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 an LC medium comprising one or more compounds of formula I and II, wherein the compounds are polymerized between the substrates of the display.

### Claim 22 (depends on 19)

The LC display of claim 19, wherein the display comprises
a first substrate including a pixel electrode defining pixel areas, the pixel electrode being connected to a switching element disposed in each pixel area and optionally including a micro-slit pattern, and optionally a first alignment layer disposed on the pixel electrode,
a second substrate including a common electrode layer, which may be disposed on the entire portion of the second substrate facing the first substrate, and optionally a second alignment layer,
an LC layer disposed between the first and second substrates and including said LC medium.

### Claim 23 (depends on 22)

The LC display of claim 22, wherein the display comprises a first and/or second alignment layer that imparts to the LC molecules homeotropic alignment.

### Claim 24 (depends on 23)

The LC display according to claim 23, wherein the display comprises a first and/or second alignment layer comprising a polyimide which is optionally rubbed or is prepared by a photoalignment method.

### Claim 25 (depends on 21)

A process for the production of an LC display according to claim 21, comprising the steps of providing an LC medium comprising one or more compounds of formula I and II, between the substrates of the display, and polymerizing the compounds, optionally while a voltage is applied to the electrodes at least partially during the polymerization.

### Claim 26 (depends on 25)

The process according to claim 25, wherein the polymerization is carried out in one step.

### Claim 27 (depends on 26)

The process according to claim 26, wherein the polymerization is carried out in a first polymerization step while applying a voltage, and subsequently in a second polymerization step without an applied voltage.

### Claim 28 (depends on 1)

The mixture according to claim 1, wherein R2 is methyl.