# US 2017/0283699 A1 · Reactive mesogen formulation with conductive additive

> Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt

- Number: US 2017/0283699 A1
- Document ID: US20170283699A1
- Status: Published application
- Kind: A1
- Application number: 15/630,493
- Filed: 2017-06-22
- Published: 2017-10-05
- Earliest claimed: 2012-02-08
- Assignees: Merck Patent GmbH
- Applicants: Merck Patent GmbH
- Inventors: Graham SMITH; Owain Llyr PARRI; Vicki COOK; Georg BERNATZ; David WILKES; Jonathan Henry WILSON; Mark JAMES; Philip Edward MAY
- Web page: https://patentgrep.com/patent/US20170283699A1

## CPC

- C09K 19/3809: {Polyesters; Polyester derivatives, e.g. polyamides}
- C09K 19/04: characterised by the chemical structure of the liquid crystal components {, e.g. by a specific unit}
- C09K 19/54: Additives having no specific mesophase {characterised by their chemical composition}
- C09K 19/582: {Electrically active dopants, e.g. charge transfer agents}
- G02B 1/08: made of polarising materials
- G02B 5/3083: {Birefringent or phase retarding elements (G02B5/3008, G02B5/3016 take precedence; systems for polarisation control G02B27/286; manufacturing phase modulating patterns by lithographic processes G03F7/001)}
- C09K 2019/0448: {the end chain group being a polymerizable end group, e.g. -Sp-P or acrylate}
- C09K 2019/523: {Organic solid particles}
- C09K 2219/03: in the form of films, e.g. films after polymerisation of LC precursor
- C09K: MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- G02B: OPTICAL ELEMENTS, SYSTEMS OR APPARATUS

## Abstract

The invention relates to a reactive mesogen (RM) formulation comprising a conductive additive, to a polymer film obtained thereof, and the use of the RM formulation and polymer film in optical or electrooptical components or devices, like optical retardation films for liquid crystal displays (LCDs).

## Claims

### Claim at position 1

-25. (canceled)

### Claim 26

A formulation comprising >50% by weight of one or more polymerisable mesogenic compounds, and one or more conductive additives, wherein the conductive additives are selected from ionic organic compounds comprising one or more polymerisable functional groups.

### Claim 27 (depends on 26)

A formulation according to claim 26, wherein the conductive additive contains an organic cation selected from the group consisting of ammonium, phosphonium, sulfonium, uronium, thiouronium, guanidinium and heterocyclic cations.

### Claim 28 (depends on 26)

A formulation according to claim 26, wherein the conductive additives contain an organic cation selected from the group consisting of tetraalkylammonium, tetraalkylphosphonium, N-alkylpyridinium, N,N-dialkylpyrrolidinium, 1,3-dialkylimidazolium or trialkylsulfonium cations.

### Claim 29 (depends on 26)

A formulation according to claim 26, wherein the conductive additives contain an anion selected from the group consisting of halide, borate, imide, phosphate, sulfonate, sulfate, succinate, naphthenate and carboxylate anions.

### Claim 30 (depends on 26)

A formulation according to claim 26, wherein the conductive additives contain an anion selected from the group consisting of the following anions: chloride, bromide, iodide, tetrafluoroborate, tetracyanoborate (TCB), difluoro-dicyano borate, fluoro-tricyano borate, perfluoroalkyl-fluoro-dicyano borate, pentafluoroethyl-fluoro-dicyano borate, perfluoroalkyl-difluoro-cyano borate, pentafluoroethyl-difluoro-cyano borate, perfluoroalkyl-fluoro borate (FAB), perfluoroalkyl-alkoxy-dicyano borate, alkoxy-tricyano borate, methoxy-tricyano borate, ethoxy-tricyano borate, 2,2,2-trifluoroethoxy-tricyano borate, bis(2,2,2-trifluoroethoxy)-dicyano borate, tetraphenylborate (TPB), tetrakis(3,5-bis(trifluoromethyl)phenyl)borate (TFPB), tetrakis(4-chlorophenyl)borate, tetrakis(4-fluorophenyl)borate, tetrakis(pentafluorophenyl)borate, tetrakis(2,2,2-trifluoroethoxy)borate, bis(oxalato)borate, bis(trifluoromethylsulfonyl)imide (NTF), bis(fluorosulfonyl)imide, bis[bis(pentafluoroethyl)phosphinyl]imide (FPI), tris(trifluoromethylsulfonyl)methide, (fluoroalkyl)fluorophosphates, tris(pentafluoroethyl)trifluorophosphate (FAP), bis(pentafluoroethyl)tetrafluorophosphate, (pentafluoroethyl)pentafluorophosphate, tris(nonafluorobutyl)trifluorophosphate, bis(nonafluorobutyl)tetrafluorophosphate, (nonafluorobutyl)pentafluorophosphate, hexafluorophosphate, bis(fluoroalkyl)phosphinate, bis(pentafluoroethyl)phosphinate, bis(nonafluorobutyl)phosphinate, (fluoroalkyl)phosphonate, (pentafluoroethyl)phosphonate, (nonafluorobutyl)phosphonate, nonafluorobutane sulfonate (nonaflate) (NFS), trifluoromethanesulfonate, trifluoroacetate, methanesulfonate, butanesulfonate, butylsulfate, hexylsulfate, octylsulfate, dicyanamide, tricyanomethide, thiocyanate, hydrogensulfate, trifluoroacetate, tosylate, (bis(2-2-ethyl hexyl) sulfosuccinate (AOT), naphthenates, lauryl sulphate, alkyl benzene sulfonates, alkyl naphthalene sulfonate), alkyl aryl ether phosphates, alkyl ether phosphate, and alkyl carboxylates, wherein alkyl is C1-C20 alkyl, fluoroalkyl is fluorinated C1-C20 alkyl, perfluoroalkyl is C1-C20 perfluoroalkyl, and aryl is optionally substituted C5-C8-aryl.

### Claim 31 (depends on 26)

A formulation according to claim 26, wherein the conductive additives are selected from formula 1:
P1-Sp-C+A− 1
wherein P1 is a polymerisable group, Sp is a spacer group or a single bond, C+is a cation, and A− is an anion.

### Claim 32 (depends on 31)

A formulation according to claim 31, wherein the conductive additives are selected from formulae 1a-1c:
P1-Sp-[NRaRbRc]+A− 1a
P1-Sp-[PRaRbRc]+A− 1b
P1-Sp-[SRaRbRc]+A− 1c
wherein P1, Sp and A− are as defined in claim 31, and
Ra, Rb, Rc independently of each other denote straight-chain, branched or cyclic alkyl with 1 to 25 C-atoms, wherein one or more CH2 groups are optionally replaced, in each case independently from one another, by —O—, —S—, —NH—, —NR00—, —CO—, —CH═CH— or —C≡C— in such a manner that O and/or S atoms are not linked directly to one another, and wherein one or more H atoms may also be replaced by F, Cl, Br, I or CN, or two of Ra, Rb and Rc together with the N+ atom form an aliphatic or aromatic ring with 4 to 8 C atoms which is optionally substituted by one or more groups L,
L is P1-Sp-, F, Cl, Br, I, —CN, —NO2, —NCO, —NCS, —OCN, —SCN, —C(═O)NR00R000, —C(═O)X, —C(═O)OR00, —C(═O)R0, NR00R000, OH, —SF5, optionally substituted silyl, aryl or heteroaryl with 1 to 12 C atoms, and straight chain or branched alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy with 1 to 12 C atoms, wherein one or more H atoms are optionally replaced by F or Cl,
R00, R000 independently of each other denote H or alkyl with 1 to 12 C-atoms, and
X is halogen.

### Claim 33 (depends on 32)

A formulation according to claim 32, wherein:
P1 is an acrylate or methacrylate group; and
Ra, Rb and Rc are straight-chain or branched alkyl with 1 to 12 C atoms.

### Claim 34 (depends on 26)

A formulation according to claim 26, which comprises one or more polymerisable mesogenic compounds having only one polymerisable functional group (monoreactive), and one or more polymerisable mesogenic compounds having two or more polymerisable functional groups (di- or multireactive).

### Claim 35 (depends on 32)

A formulation according to claim 32, wherein:
the compounds of formula Ia-c are selected from the compounds of formula 1a1-1c1:
P1—(CH2)t—[NRaRbRc]+A− 1a1
P1—(CH2)c[PRaRbRc]+A− 1b1
P1—(CH2)t[SRaRbRc]+A− 1c1
wherein t is an integer from 1 to 12.

### Claim 36 (depends on 35)

A formulation according to claim 35, wherein:
P1 is an acrylate or methacrylate group; and
Ra, Rb and Rc denote straight-chain or branched alkyl with 1 to 12 C atoms.

### Claim 37 (depends on 31)

A formulation according to claim 31, wherein:
the cation P1-Sp-C+is selected from the group consisting of:
N-[2-(methacryloyloxy)ethyl]-N,N,N-trialkylammonium;
N-[2-(methacryloyloxy)ethyl]-N,N,N-trimethylammonium (MOTMA);
N-[2-(methacryloyloxy)propyl]-N,N,N-trimethylammonium;
N-[2-(methacryloyloxy)ethyl]-N,N,N-trihexylammonium (MOTHA);
N-[2-(methacryloyloxy)propyl]-N,N,N-trihexylammonium;
N-[(2-methacryloxy)-(AO))x-A]-N,N,N-trialkylammonium;
1-[2-(methacryloyloxy)ethyl]-3-butylimidazolium;
1-(2-methacryloxyethyl)-3-methylimidazolium;
1-[(2-methacryloxy)-(AO))x-A]-3-methylimidazolium;
1-[2-(methacryloyloxy)ethyl]-1-butylpyrrolidinium;
1-(2-methacryloxyethyl)-1-methylpyrrolidinium;
1-[(2-methacryloxy)-(AO)x-A]-1-methylpyrrolidinium, wherein (AO)x is a polyalkyl oxide with x=1-10, and A is alkylene;
1-[(2-methacryloxy)-Cy]-3-methylimidazolium;
1-[(2-methacryloxy)-Cy]-1-methylpyrrolidinium, wherein Cy is an alkyl chain with y=1 to 12;
N-(acryloxy-ethyl)-N,N,N-trimethyl ammonium (AOTMA);
N-(acryloxy-ethyl)-N,N,N-trihexyl ammonium (AOTHA);
N-(acryloxy-propyl)-N,N,N-trihexyl ammonium;
N-[3-(methacryloylamino)propyl]-N,N,N-trimethylammonium;
N-[3-(methacryloylamino)propyl]-N,N,N-trihexylammonium;
N,N,N,N-tetraallyl ammonium;
1-allyl-3-methylimidazolium;
1-allyl-1-methylpyrrolidinium;
N-butyl-4-vinyl-pyridinium;
N-ethyl-4-vinyl-pyridinium;
N-methyl-4-vinyl-pyridinium;
N-methyl-2-vinyl-pyridinium;
N,N-diallyl-N,N-dimethyl ammonium; and
N-(vinylbenzyl)-N,N,N-trimethylammonium.

### Claim 38 (depends on 31)

A formulation according to claim 31, wherein the cation P1-Sp-C+ is N-[2-(methacryloyloxy)ethyl]-N,N,N-trimethylammonium (MOTMA) or N-[2-(methacryloyloxy)ethyl]-N,N,N-trihexylammonium (MOTHA).

### Claim 39 (depends on 26)

A formulation according to claim 26, wherein the ionic organic compound comprising one or more polymerisable functional groups is a compounds defined by the following combinations of polymerizable cation and anion:
Polymerisable Cation
Anion
MOTMA- TFPB
MOTHA- TFPB
MOTHA- FAP
[(C2F5)3PF3]−
MOTHA- NFS
[C4F9SO3]−
MOTHA- NTF
[N(SO2CF3)2]−
MOTHA- TCB
[B(CN)4]−
MOTMA- AOT
MOTMA- NTF
[N(SO2CF3)2]−
MOTMA- C
Cl−
MOTMA- MS
[CH3SO3]−.

### Claim 40 (depends on 26)

A formulation according to claim 26, wherein the polymerisable mesogenic compounds comprise one or more reactive mesogen compounds of formula I
P1-Sp1-MG-Sp2-P2 I
wherein P1 and P2 are independently of each other a polymerisable group, Sp1 and Sp2 are independently of each other a spacer group or a single bond, and MG is a rod-shaped mesogenic group of formula II
-(A1-Z1)n-A2- II
wherein
A1 and A2 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,
L is P-Sp-, F, Cl, Br, I, —CN, —NO2, —NCO, —NCS, —OCN, —SCN, —C(═O)NR00R000, —C(═O)X, —C(═O)OR00, —C(═O)R0, NR00R000, OH, SF5, optionally substituted silyl, aryl or heteroaryl with 1 to 12, and straight chain or branched alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy with 1 to 12 C atoms, wherein one or more H atoms are optionally replaced by F or Cl,
P is a polymerisable group,
Sp is a spacer group or a single bond,
R0, R00 and R000 independently of each other denote H or alkyl with 1 to 12 C-atoms,
X is halogen,
Z1 denotes, in case of multiple occurrence independently of one another, —O—, —S—, —CO—, —COO—, —OCO—, —S—CO—, —CO—S—, —O—COO—, —CO—NR″—, —NR00—CO—, —NR00—CO—NR000, —NR00—CO—O—, —O—CO—NR00—, —OCH2—, —CH2O—, —SCH2—, —CH2S—, —CF2O—, —OCF2—, —CF2S—, —SCF2—, —CH2CH2—, —(CH2)n1, —CF2CH2—, —CH2CF2—, —CF2CF2—, —CH═N—, —N═CH—, —N═N—, —CH═CR00—, —CY1═CY2—, —C≡C—, —CH═CH—COO—, —OCO—CH═CH— or a single bond,
Y1 and Y2 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.

### Claim 41 (depends on 40)

A formulation according to claim 40, which comprises one or more reactive mesogen compounds of formula Ia
wherein
P0 is, in case of multiple occurrences independently of one another, a polymerisable group,
Z0 is —COO—, —OCO—, —CH2CH2—, —CF2O—, —OCF2—, —C≡C—, —CH═CH—, —OCO—CH═CH—, —CH═CH—COO—, or a single bond,
L has the meanings given in claim 40,
r is 0, 1, 2, 3 or 4,
x and y are independently of each other 0 or identical or different integers from 1 to 12, and
z is 0 or 1, with z being 0 if the x or y of the adjacent group is 0.

### Claim 42 (depends on 26)

A formulation according to claim 26, wherein the polymerisable mesogenic compounds comprise one or more reactive mesogen compounds of formula III
P1-Sp1-MG-R III
wherein P1 is a polymerisable group, Sp1 is a spacer group or a single bond, and MG is a rod-shaped mesogenic group of formula II
-(A1-Z1)n-A2- II
wherein
A1 and A2 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,
L is P-Sp-, F, Cl, Br, I, —CN, —NO2, —NCO, —NCS, —OCN, —SCN, —C(═O)NR00R000, —C(═O)X, —C(═O)OR00, —C(═O)R0, NR00R000, OH, SF5, optionally substituted silyl, aryl or heteroaryl with 1 to 12 C atoms, and straight chain or branched alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy with 1 to 12 C atoms, wherein one or more H atoms are optionally replaced by F or Cl,
P is a polymerisable group,
Sp is a spacer group or a single bond,
Z1 denotes, in case of multiple occurrence independently of one another, —O—, —S—, —CO—, —COO—, —OCO—, —S—CO—, —CO—S—, —O—COO—, —CO—NR00—, —NR00—CO—, —NR00—CO—NR000, —NR00—CO—O—, —O—CO—NR00—, —OCH2—, —CH2O—, —SCH2—, —CH2S—, —CF2O—, —OCF2—, —CF2S—, —SCF2—, —CH2CH2—, —(CH2)n1, —CF2CH2—, —CH2CF2—, —CF2CF2—, —CH═N—, —N═CH—, —N═N—, —CH═CR00—, —CY1═CY2—, —C≡C—, —CH═CH—COO—, —OCO—CH═CH— or a single bond,
Y1 and Y2 independently of each other denote H, F, Cl or CN,
n is 1, 2, 3 or 4,
n1 is an integer from 1 to 10,
R denotes P-Sp-, F, Cl, Br, I, —CN, —NO2, —NCO, —NCS, —OCN, —SCN, —C(═O)NR00R000, —C(═O)X, —C(═O)OR0, —C(═O)R00, —NR00R000, OH, —SF5, optionally substituted silyl, straight chain or branched alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy with 1 to 12 C atoms, wherein one or more H atoms are optionally replaced by F or Cl,
X is halogen, and
R0, R00 and R000 are independently of each other H or alkyl with 1 to 12 C-atoms.

### Claim 43 (depends on 41)

A formulation according to claim 41, wherein the polymerisable mesogenic compounds comprise one or more reactive mesogen compounds selected from the following formulae:
wherein
P0 is, in case of multiple occurrences independently of one another, a polymerisable group,
L are independently of one another, selected from F, Cl, CN or optionally halogenated alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy with 1 to 5 C atoms,
r is 0, 1, 2, 3 or 4,
x and y are independently of each other 0 or identical or different integers from 1 to 12,
z is 0 or 1, with z being 0 if the x or y of the adjacent group is 0,
R0 is alkyl, alkoxy, thioalkyl, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy with 1 to 15 C atoms which is optionally fluorinated, or denotes Y0 or P—(CH2)y—(O)z—,
X0 is —O, S, CO, COO—, —OCO—, —O—COO—, —CO—NR01—, —NR01—CO—, —NR01—CO—NR01—, —OCH2—, —CH2O—, —SCH2—, —CH2S—, —CF2O—, —OCF2—, —CF2S—, —SCF2—, —CF2CH2—, —CH2CF2—, —CF2CF2—, —CH═N—, —N═CH—, —N═N—, —CH═CR01—, —CF═CF—, —C≡C—, —CH═CH—COO—, —OCO—CH═CH— or a single bond,
Y0 is F, Cl, CN, NO2, OCH3, OCN, SCN, SF5, optionally fluorinated alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy with 1 to 4 C atoms, or mono- oligo- or polyfluorinated alkyl or alkoxy with 1 to 4 C atoms,
A0 is, in case of multiple occurrence independently of one another, 1,4-phenylene that is unsubstituted or substituted with 1, 2, 3 or 4 groups L, or trans-1,4-cyclohexylene,
R01 and R02 are independently of each other H, R0 or Y0,
u and v are independently of each other 0, 1 or 2,
w is 0 or 1,
and wherein the benzene and napthalene rings can additionally be substituted with one or more identical or different groups L.

### Claim 44 (depends on 40)

A formulation according to claim 40, wherein in formula I
P1 and P2 are selected from CH2═CH—COO—, CH2═C(CH3)—COO—, CH2═CF—COO—, (CH2═CH)2CH—OCO—, (CH2═CH)2CH—O—,
W2 being H or alkyl with 1 to 5 C-atoms,
L is P-Sp-, F, Cl, Br, I, —CN, —NO2, —NCO, —NCS, —OCN, —SCN, —C(═O)NR00R000, —C(═O)X, —C(═O)OR00, —C(═O)R0, —NR00R000, —OH, —SF5, optionally substituted silyl, aryl or heteroaryl with 1 to 12, preferably 1 to 6 C atoms, and straight chain or branched alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy with 1 to 6 C atoms, wherein one or more H atoms are optionally replaced by F or Cl,
P is a polymerisable group,
Sp is a spacer group or a single bond,
X is F or Cl,
Z1 is —COO—, —OCO— or a single bond,
n is 1 or 2, and
n1 is 1, 2, 3 or 4.

### Claim 45 (depends on 42)

A formulation according to claim 42, wherein in formula III:
P1 and P2 are selected from CH2═CH—COO—, CH2═C(CH3)—COO—, CH2═CF—COO—, (CH2═CH)2CH—OCO—, (CH2═CH)2CH—O—,
W2 being H or alkyl with 1 to 5 C-atoms,
L is P-Sp-, F, Cl, Br, I, —CN, —NO2, —NCO, —NCS, —OCN, —SCN, —C(═O)NR00R000, —C(═O)X, —C(═O)OR00, —C(═O)R0, —NR00R000, —OH, —SF5, optionally substituted silyl, aryl or heteroaryl with 1 to 6 C atoms, and straight chain or branched alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy with 1 to 6 C atoms, wherein one or more H atoms are optionally replaced by F or Cl,
Z1 is, in case of multiple occurrences independently of one another, —COO—, —OCO— or a single bond,
n is 1 or 2,
n1 is 1, 2, 3 or 4,
R denotes P-Sp-, F, Cl, Br, I, —CN, —NO2, —NCO, —NCS, —OCN, —SCN, —C(═O)NR00R000, —C(═O)X, —C(═O)OR0, —C(═O)R00, NR00R000, —OH, —SF5, optionally substituted silyl, straight chain or branched alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy with 1 to 6 C atoms, wherein one or more H atoms are optionally replaced by F or Cl, and
X is F or Cl.