# US 5,707,544 A · Chromophore-containing photo cross-linkable liquid crystals

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- Number: US 5,707,544 A
- Document ID: US5707544A
- Status: Granted
- Kind: A
- Application number: 08/650,241
- Filed: 1996-05-20
- Granted: 1998-01-13
- Earliest claimed: 1995-06-07
- Assignees: Rolic AG
- Inventors: Stephen Kelly
- Web page: https://patentgrep.com/patent/US5707544A

## CPC

- C09K 19/32: containing condensed ring systems, i.e. fused, bridged or spiro ring systems
- C09B 69/106: {containing an azo dye}
- C09K 19/2007: {the chain containing -COO- or -OCO- groups}
- C09K 19/24: linked by a chain containing nitrogen-to-nitrogen bonds
- C09K 19/26: Azoxy compounds
- C09K: MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09B: ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES {, e.g. PIGMENTS}; MORDANTS; LAKES (fermentation or enzyme using processes to synthesise a desired chemical compound C12P)

## Abstract

The present invention is concerned with chromophore-containing photo cross-linkable liquid crystalline compounds having the formula ##STR1## wherein A.sup.1 and A.sup.2 each represent a cross-linkable, mesogenic group; and A.sup.3 represents a dichroic group. as well as liquid crystalline mixtures which contain such compounds and their use in the cross-linked state as optical components.

## Claims

### Claim 1

A compound of the formula ##STR13## wherein A.sup.1 and A.sup.2 each independently is a cross-linkable, mesogenic group; and
A.sup.3 is a dichroic group.

### Claim 2 (depends on 1)

The compound according to claim 1, wherein A.sup.1 and A.sup.2 each independently is a group of the formula ##STR14## wherein rings C and D each independently is pyridine-2,5-diyl, pyrimidine-2,5-diyl, trans-1,4-cyclohexylene, trans-1,3-dioxane-2,5-diyl, unsubstituted 1,4-phenylene, or 1,4-phenylene which is substituted with at least one substituent selected from the group consisting of halogen, methyl, and cyano;
Z.sup.1 is --CH.sub.2 CH.sub.2 --, --CH.sub.2 O--, --COO--, --OOC--, --(CH.sub.2).sub.4 --, or --(CH.sub.2).sub.3 O--;
Z.sup.2 is a single bond, --CH.sub.2 CH.sub.2 --, --CH.sub.2 O--, --OCH.sub.2 --, --COO--, --OOC--, --(CH.sub.2).sub.4 --, --O(CH.sub.2).sub.3 --, or --(CH.sub.2).sub.3 O--;
Z.sup.3 is --(CY.sub.2).sub.m --, --O(CY.sub.2).sub.m --, --(CY.sub.2).sub.m O--, --(CY.sub.2).sub.m COO--, --(CY.sub.2).sub.m OOC--, --(Si›(CH.sub.3).sub.2 !O).sub.m --, --OCH.sub.2 (Si›(CH.sub.3).sub.2 !O).sub.m ---Si›(CH.sub.3).sub.2 !CH.sub.2 O--, or --NHCH.sub.2 (Si›(CH.sub.3).sub.2 !O).sub.m --Si›(CH.sub.3).sub.2 !CH.sub.2 NH--;
Y is hydrogen or fluorine;
n is 0 or 1;
m is a whole number from 1 to 16 inclusive; and
R.sup.1 is a cross-linkable group.

### Claim 3 (depends on 2)

The compound of claim 2, wherein R.sup.1 is selected from the group consisting of ethylene, acrylate, methacrylate, 2-chloroacrylate, 2-phenylacrylate, acryloylphenylene, acrylamide, methacrylamide, 2-chloroacrylamide, 2-phenylacrylamide, epoxy, itaconic acid ester, vinyl ether, vinyl ester, styrene derivative, siloxane, ethyleneimine derivative, maleic acid derivative, fumaric acid derivative, an unsubstituted cinnamic acid derivative, and a cinnamic acid derivative which is substituted with one or more substituents selected from the group consisting of methyl, methoxy, cyano, and halogen.

### Claim 4 (depends on 2)

The compound according to claim 2, wherein A.sup.1 and A.sup.2 are the same.

### Claim 5 (depends on 1)

The compound according to claim 1, wherein A.sup.3 is a group of the formula ##STR15## wherein rings E and H each independently is pyridine-2,5-diyl, pyrimidine-2,5-diyl, trans-1,4-cyclohexylene, trans-1,3-dioxane-2,5-diyl, unsubstituted 1,4-phenylene, or 1,4-phenylene which is substituted with at least one substituent selected from the group consisting of halogen, methyl, and cyano;
ring F is pyridine-2,5-diyl, pyrimidine-2,5-diyl, unsubstituted 1,4-phenylene, or 1,4-phenylene which is substituted with at least one substituent selected from the group consisting of halogen, methyl, and cyano;
ring G is pyridine-2,5-diyl, pyrimidine-2,5-diyl, 1,4-naphthylene, 2,6-naphthylene, 2,5-pyrazolediyl, 2,5-thiazolediyl, 2,5-benzthiazolediyl, 2,5-imidazolediyl, 2,5-pyrrolediyl, 2,5-thiophenediyl, unsubstituted 1,4-phenylene, or 1,4-phenylene which is substituted with at least one substituent selected from the group consisting of halogen, methyl, dimethylamino, amino, nitro, and cyano;
Z.sup.4 is --CH.sub.2 CH.sub.2 --, --CH.sub.2 O--, --COO--, --OOC--, --(CH.sub.2).sub.4 --, --(CH.sub.2).sub.3 O--, --COO(CH.sub.2).sub.p --, or --COO(CH.sub.2).sub.p O--;
Z.sup.5 and Z.sup.7 each independently is a single bond, --CH.sub.2 CH.sub.2 --, --CH.sub.2 O--, --OCH.sub.2 --, --COO--, --OOC--, --(CH.sub.2).sub.4 --, --O(CH.sub.2).sub.3 --, or --(CH.sub.2).sub.3 O--;
Z.sup.6 is --N.dbd.N--, --N(O).dbd.N--, --CH.dbd.CH--, or --CH.dbd.N--;
n and q each is 0 or 1;
p is a whole number from 1 to 16 inclusive;
r is 0, 1, or 2; and
R.sup.2 is hydrogen, halogen, cyano, --CH.dbd.CHNO.sub.2, --C.dbd.CHCN, --CH.dbd.C(CN).sub.2, nitro, a dialkylamino group, a cyclobutylamino group, an alkyl group, an alkoxy group, an alkanoyloxy group, an alkyl group which is substituted with at least one substituent selected from the group consisting of methoxy, cyano, and halogen, an alkoxy group which is substituted with at least one substituent selected from the group consisting of methoxy, cyano, and halogen, or an alkanoyloxy group which is substituted with at least one substituent selected from the group consisting of methoxy, cyano, and halogen,
provided that, when r=0, R.sup.2 is a group of the formula ##STR16## wherein ring I is pyridine-2,5-diyl, pyrimidine-2,5-diyl, trans-1,4-cyclohexylene, trans-1,3-dioxane-2,5-diyl, unsubstituted 1,4-phenylene, or 1,4-phenylene which is substituted with at least one substituent selected from the group consisting of halogen, methyl, and cyano;
Z.sup.8 is --CH.sub.2 CH.sub.2 --, --CH.sub.2 O--, --COO--, --OOC--, --(CH.sub.2).sub.4 --, --(CH.sub.2).sub.3 O--, --COO(CH.sub.2).sub.p --, or --COO(CH.sub.2).sub.p O--;
Z.sup.9 is a single bond, --COO(CH.sub.2).sub.p N(CH.sub.3)--, --COO(CH.sub.2).sub.p NH--, --CH.sub.2 O--, --OCH.sub.2 --, --COO--, --OOC--, or --NH--;
s is 0 or 1;
p is a whole number from 1 to 16 inclusive; and
R.sup.3,R.sup.4,R.sup.5 and R.sup.6 each independently is hydrogen, halogen, cyano, --CH.dbd.CHNO.sub.2, --CH.dbd.CHCN, --CH.dbd.C(CN).sub.2, nitro, hydroxy, a dialkylamino group, cyclobutylamino group, an alkyl group, an alkoxy group, an alkanoyloxy group, an alkyl group which is substituted with at least one substituent selected from the group consisting of methyl, methoxy, cyano, and halogen, an alkoxy group which is substituted with at least one substituent selected from the group consisting of methyl, methoxy, cyano, and halogen, or an alkanoyloxy group which is substituted with at least one substituent selected from the group consisting of methyl, methoxy, cyano, and halogen.

### Claim 6 (depends on 2)

The compound according to claim 2, wherein A.sup.3 is a group of the formula ##STR17## wherein rings E and H each independently is pyridine-2,5-diyl, pyrimidine-2,5-diyl, trans-1,4-cyclohexylene, trans-1,3-dioxane-2,5-diyl, unsubstituted 1,4-phenylene, or 1,4-phenylene which is substituted with at least one substituent selected from the group consisting of halogen, methyl, and cyano;
ring F is pyridine-2,5-diyl, pyrimidine-2,5-diyl, unsubstituted 1,4-phenylene, or 1,4-phenylene which is substituted with at least one substituent selected from the group consisting of halogen, methyl, and cyano;
ring G is pyridine-2,5-diyl, pyrimidine-2,5-diyl, 1,4-naphthylene, 2,6-naphthylene, 2,5pyrazolediyl, 2,5-thiazolediyl, 2,5-benzthiazolediyl, 2,5-imidazolediyl, 2,5-pyrrolediyl, 2,5-thiophenediyl, unsubstituted 1,4-phenylene, or 1,4-phenylene which is substituted with at least one substituent selected from the group consisting of halogen, methyl, dimethylamino, amino, nitro, and cyano;
Z.sup.4 is --CH.sub.2 CH.sub.2 --, --CH.sub.2 O--, --COO--, --OOC--, --(CH.sub.2).sub.4 --, --(CH.sub.2).sub.3 O--, --COO(CH.sub.2).sub.p --, or --COO(CH.sub.2).sub.p O--;
Z.sup.5 and Z.sup.7 each independently is a single bond, --CH.sub.2 CH.sub.2 --, --CH.sub.2 O--, --OCH.sub.2 --, --COO--, --OOC--, --(CH.sub.2).sub.4 --, --O(CH.sub.2).sub.3 --, or --(CH.sub.2).sub.3 O--;
Z.sup.6 is --N.dbd.N--, --N(O).dbd.N--, --CH.dbd.CH--, or --CH.dbd.N--;
n and q each is 0 or 1;
p is a whole number from 1 to 16 inclusive;
r is 0, 1, or 2; and
R.sup.2 is hydrogen, halogen, cyano, --CH.dbd.CHNO.sub.2, --CH.dbd.CHCN, --CH.dbd.C(CN).sub.2, nitro, a dialkylamino group, a cyclobutylamino group, an alkyl group, an alkoxy group, an alkanoyloxy group, an alkyl group which is substituted with at least one substituent selected from the group consisting of methoxy, cyano, and halogen, an alkoxy group which is substituted with at least one substituent selected from the group consisting of methoxy, cyano, and halogen, or an alkanoyloxy group which is substituted with at least one substituent selected from the group consisting of methoxy, cyano, and halogen, provided that, when r=0, R.sup.2 is a group of the formula ##STR18## wherein ring I is pyridine-2,5-diyl, pyrimidine-2,5-diyl, trans-1,4-cyclohexylene, trans-1,3-dioxane-2,5-diyl, unsubstituted 1,4-phenylene, or 1,4-phenylene which is substituted with at least one substituent selected from the group consisting of halogen, methyl, and cyano;
Z.sup.8 is --CH.sub.2 CH.sub.2 --, --CH.sub.2 O--, --COO--, --OOC--, --(CH.sub.2).sub.4 --, --(CH.sub.2).sub.3 O--, --COO(CH.sub.2).sub.p --, or --COO(CH.sub.2).sub.p O--;
Z.sup.9 is a single bond, --COO(CH.sub.2).sub.p N(CH.sub.3)--, --COO(CH.sub.2).sub.p NH--, --CH.sub.2 O--, --OCH.sub.2 --, --COO--, --OOC--, or --NH--;
s is 0 or 1;
p is a whole number from 1 to 16 inclusive; and
R.sup.3,R.sup.4,R.sup.5 and R.sup.6 each independently is hydrogen, halogen, cyano, --CH.dbd.CHNO.sub.2, --CH.dbd.CHCN, --CH.dbd.C(CN).sub.2, nitro, hydroxy, a dialkylamino group, cyclobutylamino group, an alkyl group, an alkoxy group, an alkanoyloxy group, an alkyl group which is substituted with at least one substituent selected from the group consisting of methyl, methoxy, cyano, and halogen, an alkoxy group which is substituted with at least one substituent selected from the group consisting of methyl, methoxy, cyano, and halogen, or an alkanoyloxy group which is substituted with at least one substituent selected from the group consisting of methyl, methoxy, cyano, and halogen.

### Claim 7 (depends on 1)

The compound according to claim 1, wherein A.sup.3 is a group of the formula ##STR19## wherein ring I is pyridine-2,5-diyl, pyrimidine-2,5-diyl, trans-1,4-cyclohexylene, trans-1,3-dioxane-2,5-diyl, unsubstituted 1,4-phenylene, or 1,4-phenylene which is substituted with at least one substituent selected from the group consisting of halogen, methyl, and cyano;
Z.sup.8 is --CH.sub.2 CH.sub.2 --, --CH.sub.2 O--, --COO--, --OOC--, --(CH.sub.2).sub.4 --, --(CH.sub.2).sub.3 O--, --COO(CH.sub.2).sub.p --, or --COO(CH.sub.2).sub.p O--;
Z.sup.9 is a single bond, --COO(CH.sub.2 ).sub.p N(CH.sub.3)--, --COO(CH.sub.2).sub.p NH--, --CH.sub.2 O--, --OCH.sub.2 --, --COO--, --OOC-- or --NH--;
s is 0 or 1;
p is a whole number from 1 to 16 inclusive; and
R.sup.3,R.sup.4,R.sup.5 and R.sup.6 each independently is hydrogen, halogen, cyano, --CH.dbd.CHNO.sub.2, --CH.dbd.CHCN, --CH.dbd.C(CN).sub.2, nitro, hydroxy, a dialkylamino group, a cyclobutylamino group, an alkyl group, an alkoxy group, an alkanoyloxy group, an alkyl group which is substituted with at least one substituent selected from the group consisting of methyl, methoxy, cyano, and halogen, an alkoxy group which is substituted with at least one substituent selected from the group consisting of methyl, methoxy, cyano, and halogen, or an alkanoyloxy group which is substituted with at least one substituent selected from the group consisting of methyl, methoxy, cyano, and halogen.

### Claim 8 (depends on 2)

The compound according to claim 2, wherein A.sup.3 is a group of the formula ##STR20## wherein ring I is pyridine-2,5-diyl, pyrimidine-2,5-diyl, trans-1,4-cyclohexylene, trans-1,3-dioxane-2,5-diyl, unsubstituted 1,4-phenylene, or 1,4-phenylene which is substituted with at least one substituent selected from the group consisting of halogen, methyl, and cyano; p1 Z.sup.8 is --CH.sub.2 CH.sub.2 --, --CH.sub.2 O--, --COO--, --OOC--, --(CH.sub.2).sub.4 --, --(CH.sub.2).sub.3 O--, --COO(CH.sub.2).sub.p --, or --COO(CH.sub.2).sub.p O--;
Z.sup.9 is a single bond, --COO(CH.sub.2).sub.p N(CH.sub.3)--, --COO(CH.sub.2).sub.p NH--, --CH.sub.2 O--, --OCH.sub.2 --, --COO--, --OOC-- or --NH--;
s is 0 or 1;
p is a whole number from 1 to 16 inclusive; and
R.sup.3,R.sup.4,R.sup.5 and R.sup.6 each independently is hydrogen, halogen, cyano, --CH.dbd.CHNO.sub.2, --CH.dbd.CHCN, --CH.dbd.C(CN).sub.2, nitro, hydroxy, a dialkylamino group, a cyclobutylamino group, an alkyl group, an alkoxy group, an alkanoyloxy group, an alkyl group which is substituted with at least one substituent selected from the group consisting of methyl, methoxy, cyano, and halogen, an alkoxy group which is substituted with at least one substituent selected from the group consisting of methyl, methoxy, cyano, and halogen, or an alkanoyloxy group which is substituted with at least one substituent selected from the group consisting of methyl, methoxy, cyano, and halogen.

### Claim 9 (depends on 5)

The compound according to claim 5, wherein A.sup.1 and A.sup.2 each independently is a group of the formula ##STR21## wherein ring C.sup.1 is phenylene or phenylene which is substituted with fluorine;
Z.sup.11 is --CH.sub.2 CH.sub.2 --, --CH.sub.2 O--, --COO--, --OOC--, --(CH.sub.2).sub.4 --, or --(CH.sub.2).sub.3 O--;
Z.sup.31 is --(CH.sub.2).sub.m' --, --(CH.sub.2).sub.m' O--, --(CH.sub.2).sub.m' COO--, or --(CH.sub.2).sub.m' OOC--;
m' is a whole number from 4 to 12 inclusive; and
R.sup.11 is acrylate, methacrylate, vinyl ether, or epoxy.

### Claim 10 (depends on 7)

The compound according to claim 7, wherein A.sup.1 and A.sup.2 each independently is a group of the formula ##STR22## wherein ring C.sup.1 is phenylene or phenylene which is substituted with fluorine;
Z.sup.11 is --CH.sub.2 CH.sub.2 --, --CH.sub.2 O--, --COO--, --OOC--, --(CH.sub.2).sub.4 --, or --(CH.sub.2).sub.3 O--;
Z.sup.31 is --(CH.sub.2).sub.m' --, --(CH.sub.2).sub.m' O--, --(CH.sub.2).sub.m' COO--, or --(CH.sub.2).sub.m' OOC--;
m' is a whole number from 4 to 12 inclusive; and
R.sup.11 is acrylate, methacrylate, vinyl ether, or epoxy.

### Claim 11 (depends on 1)

The compound according to claim 1, wherein A.sup.3 is a group of the formula ##STR23## wherein rings E.sup.1 and H.sup.1 each independently is 1,4-phenylene or 1,4-phenylene which is substituted with fluorine;
Z.sup.41 is --COO(CH.sub.2).sub.p' -- or --COO(CH.sub.2).sub.p' O--;
Z.sup.51 and Z.sup.71 each independently is a single bond, --CH.sub.2 CH.sub.2 --, --CH.sub.2 O--, --COO--, or --OOC--;
n, q each independently is 0 or 1;
r is 1;
p' is a whole number from 4 to 12 inclusive; and
R.sup.21 is nitro or dimethylamino.

### Claim 12 (depends on 2)

The compound according to claim 2, wherein A.sup.3 is a group of the formula ##STR24## wherein rings E.sup.1 and H.sup.1 each independently is 1,4-phenylene or 1,4-phenylene which is substituted with fluorine;
Z.sup.41 is --COO(CH.sub.2).sub.p' -- or --COO(CH.sub.2).sub.p' O--;
Z.sup.51 and Z.sup.71 each independently is a single bond, --CH.sub.2 CH.sub.2 --, --CH.sub.2 O--, --COO--, or --OOC--;
n, q each independently is 0 or 1;
r is 1;
p' is a whole number from 4 to12 inclusive; and
R.sup.21 is nitro or dimethylamino.

### Claim 13 (depends on 1)

The compound according to claim 1, wherein A.sup.3 is a group of the formula ##STR25## wherein ring I.sup.1 is phenylene, phenylene which is substituted with fluorine, or trans-1,4-cyclohexylene;
Z.sup.81 is --COO(CH.sub.2).sub.p' -- or --COO(CH.sub.2).sub.p' O--;
p' os a whole number from 4 to 12 inclusive;
Z.sup.91 is a single bond, --COO(CH.sub.2).sub.p N(CH.sub.3)--, or --COO(CH.sub.2).sub.p NH--;
s is 0 or 1;
p is a whole number from 1 to 16 inclusive; and
R.sup.3,R.sup.4,R.sup.5, and R.sup.6 each independently is hydrogen, halogen, cyano, --CH.dbd.CHNO.sub.2, --CH.dbd.CHCN, --CH.dbd.C(CN).sub.2, nitro, hydroxy, a dialkylamino group, cyclobutylamino group, an alkyl group, an alkoxy group, an alkanoyloxy group, an alkyl group which is substituted with at least one substituent selected from the group consisting of methyl, methoxy, cyano, and halogen, an alkoxy group which is substituted with at least one substituent selected from the group consisting of methyl, methoxy, cyano, and halogen, or an alkanoyloxy group which is substituted with at least one substituent selected from the group consisting of methyl, methoxy, cyano, and halogen.

### Claim 14 (depends on 2)

The compound according to claim 2, wherein A.sup.3 is a group of the formula ##STR26## wherein ring I.sup.1 is phenylene, phenylene which is substituted with fluorine, or trans-1,4-cyclohexylene;
Z.sup.81 is --COO(CH.sub.2).sub.p' -- or --COO(CH.sub.2).sub.p' O--;
p' is a whole number from 4 to 12 inclusive;
Z.sup.91 is a single bond, --COO(CH.sub.2).sub.p N(CH.sub.3)--, or --COO(CH.sub.2).sub.p NH--;
s is 0 or 1;
p is a whole number from 1 to 16 inclusive; and
R.sup.3,R.sup.4,R.sup.5, and R.sup.6 each independently is hydrogen, halogen, cyano, --CH.dbd.CHNO.sub.2, --CH.dbd.CHCN, --CH.dbd.C(CN).sub.2, nitro, hydroxy, a dialkylamino group, cyclobutylamino group, an alkyl group, an alkoxy group, an alkanoyloxy group, an alkyl group which is substituted with at least one substituent selected from the group consisting of methyl, methoxy, cyano, and halogen, an alkoxy group which is substituted with at least one substituent selected from the group consisting of methyl, methoxy, cyano, and halogen, or an alkanoyloxy group which is substituted with at least one substituent selected from the group consisting of methyl, methoxy, cyano, and halogen.

### Claim 15

A compound of the formula ##STR27## wherein m' is a number from 4 to 12 inclusive;
rings E.sup.1 and H.sup.1 each independently is 1,4-phenylene or 1,4-phenylene which is substituted with fluorine;
Z.sup.41 is --COO(CH.sub.2).sub.p' -- or --COO(CH.sub.2).sub.p' O--;
Z.sup.51 and Z.sup.71 each independently is a single bond, --CH.sub.2 CH.sub.2 --, --CH.sub.2 O--, --COO--, or --OOC--;
n and q each independently is 0 or 1;
r is 1; and
R.sup.21 is nitro.

### Claim 16 (depends on 15)

The compound according to claim 15, wherein q is 0.

### Claim 17

A cross-linkable, liquid crystalline mixture comprising at least 2 components, at least one of which is a compound of the formula ##STR28## wherein A.sup.1 and A.sup.2 each independently is a cross-linkable, mesogenic group; and
A.sup.3 is a dichroic group.

### Claim 18 (depends on 17)

The cross-linkable, liquid crystalline mixture according to claim 17, wherein the mixture comprises at least one compound selected from the group consisting of the formulas ##STR29## wherein X is hydrogen, fluorine, chlorine, bromine, or methyl;
m' is a whole number from 4 to 12 inclusive;
t is a whole number from 2 to 12 inclusive;
Z is --OCH.sub.2 -- or --OOC--;
A is 1,4-phenylene, 2-fluoro-1,4-phenylene, or 3-fluoro-1,4-phenylene;
S is --(CH.sub.2).sub.m' -- or --(CH.sub.2).sub.m' O--; and
R is acrylate, methacrylate, vinyl ether, or epoxy.